CN122341663A - Additive for catalysts - Google Patents

Abstract

A method for preparing a productivity-enhancing bimodal catalyst, the method comprising combining a nonmetallocene precatalyst, a metallocene precatalyst, an effective amount of an activator, and an effective amount of an activity-enhancing compound to activate the nonmetallocene precatalyst and the metallocene precatalyst into a productivity-enhancing bimodal catalyst.

Description

Additive for catalysts

Technical Field

Embodiments of the present disclosure relate to catalysts, and more particularly, embodiments relate to additives for catalysts used to produce bimodal polymers.

Background

The polymers can be used in a variety of products including membranes and pipes, etc. The polymer may be formed by reacting one or more types of monomers in a polymerization reaction. There is a continuing interest in the industry to develop new and improved materials and/or methods that can be used to form polymers for existing products and new products.

Among these polymers, bimodal High Density Polyethylene (HDPE) is of great interest. Bimodal HDPE refers to a class of HDPE polymers having both a high molecular weight component and a low molecular weight component (i.e., a "bimodal" molecular weight distribution). In bimodal HDPE, there are two different sets of molecular weights, typically achieved by a two-stage polymerization process or by a combination of different polymerization conditions. This results in a polymer having a broader molecular weight distribution than conventional unimodal HDPE. The combination of different molecular weights provides advantages such as improved mechanical properties and processability, etc., for blow molding and rotomolding products, pipe applications, and film and packaging applications.

An important consideration in the production of bimodal HDPE is the cost of use (CIU) of the catalyst used to make the bimodal HDPE. CIU is actually the cost of catalyst per unit weight of polymer produced. CIU is typically expressed in cents per pound (cpp) or dollars per ton. CIU is closely related to the productivity of the catalyst, and becomes economically more advantageous as the productivity of the catalyst increases. However, catalysts for bimodal polymer (e.g., bimodal HDPE) production still face CIU challenges, largely due to the low productivity of the high molecular weight portion of the bimodal polymer. The challenge in the art is to achieve an improvement in bimodal HDPE production without changing the polymer/product produced. In other words, there is a need in the art to increase the productivity of catalysts for bimodal polymer production without changing the bimodal polymer and thus the product produced.

Disclosure of Invention

Various methods may be employed to adjust or control the polymerization conditions. Adjusting the polymerization conditions can change the catalyst productivity. However, changing the reaction conditions may have other unintended consequences. For example, changing reaction conditions can also change various polymer characteristics (e.g., mn, mw, MWD, density, etc.), introduce operability problems (e.g., agglomeration, sheeting, etc.), increase catalyst residues in the polymer, and/or increase production costs. Thus, there remains a need for a method of adjusting or controlling catalyst productivity that does not require changing polymerization conditions.

The present disclosure provides a technical solution to the above-described problems by altering the molecular structure of at least the non-metallocene precatalyst in a productivity-enhanced bimodal catalyst with an effective amount of an activity enhancing compound as discussed herein. The activity enhancing compound may be introduced during the preparation of the bimodal catalyst and/or catalyst system (e.g., multimodal catalyst system) in solid or spray dried form with increased productivity. The productivity-enhanced bimodal catalyst and/or a catalyst system comprising the productivity-enhanced bimodal catalyst (e.g., a multimodal catalyst system) can be used in a polymerization reactor to produce polymers at improved productivity levels, as detailed herein, and the productivity-enhanced bimodal catalyst is easy and inexpensive to produce, and still produce polymers having desired characteristics (e.g., molecular weight distribution, etc.). The result is unpredictable.

As provided herein, the present disclosure provides for modifying the material composition of a catalyst system (e.g., non-metallocene pre-catalysts and metallocene pre-catalysts as provided herein) with an activity enhancing compound to produce a bimodal catalyst with improved productivity. The results/features caused by inclusion of an activity enhancing compound to produce the productivity-enhanced bimodal catalysts of the present disclosure include (a) to (g):

(a) Productivity increases, as indicated by the increase in productivity of both the high molecular weight component and the low molecular weight component of the productivity-increased bimodal catalyst (shown in the examples section by comparing productivity of the productivity-increased bimodal catalyst to a comparative catalyst system that does not include an activity enhancing compound).

(B) Bimodal catalysts with increased productivity exhibit higher overall productivity, while controls containing only the activity enhancing compound and the metallocene catalyst only exhibit reduced productivity (e.g., direct combination of the metallocene catalyst and the activity enhancing compound is detrimental).

(C) The activity enhancing compound acts by chemically modifying the active high molecular weight (non-metallocene) component by contacting the high molecular weight non-metallocene pre-catalyst with an activator (e.g., methylaluminoxane ("MAO")) and an additive in a solution, slurry or suspension in an inert hydrocarbon (other components of the bimodal catalyst system may or may not be present). As stated in (b), the activity enhancing compound has a negative effect on the metallocene productivity and also has no effect on the metallocene kinetics.

(D) Bimodal catalysts with increased productivity operate efficiently at reduced turndown catalyst/catalyst ratios, a surprising and unpredictable feature. This is demonstrated in the examples section herein by an increase in the flow index (FI ₂₁) of the polymer, where it is believed that the activity enhancing compound acts to increase the productivity of the HMW component, which increases Mw thereby decreasing FI ₂₁. As productivity increases and FI ₂₁ decreases, this means that both the non-metallocene catalyst component and the metallocene catalyst component of the productivity-enhanced bimodal catalysts of the present disclosure are positively affected (directly or indirectly) by the activity enhancing compound. This suggests that there may be a secondary effect on the metallocene catalyst component, where its productivity also increases (based on changes in the polymer data, possibly even over non-metallocene catalysts). This is believed to be caused by the indirect effect of the activity enhancing compound in increasing the productivity of the metallocene component. From a single catalyst operation, there should be no benefit (and in some cases even a negative impact) on the metallocene, so in the productivity enhanced bimodal catalysts of the present disclosure, less metallocene catalyst is needed despite the higher productivity from the metallocene catalyst, which fact means that metallocene low molecular weight polymer production has higher productivity.

(E) In the semi-batch reactor process of the present disclosure (particularly when no conditioning catalyst is used to adjust the LMW: HMW component ratio), the bimodal HDPE produced by the improved productivity bimodal catalyst has lower Mw and Mn molecular weight from the increased LMW polymer component in the bimodal HDPE. In addition, bimodal HDPE produced by the bimodal catalyst with increased productivity has increased crystallinity as measured by an increase in the enthalpy of fusion of the bimodal HDPE polymer.

(F) Bimodal catalysts with increased productivity also exhibit improved heat control. The presence of the activity enhancing compounds of the present disclosure, despite having increased productivity, reduces the total heat generated by the productivity-enhanced bimodal catalyst. The heat is generated by the polymerization heat and the less heat associated with lower productivity is not surprising. Higher productivity with less calories is a surprising feature of activity enhancing compounds. In the examples section below, this is measured indirectly by the maximum reactor internal temperature (during the semi-batch reactor test method) and the time required to reach the maximum temperature. For bimodal catalysts with increased productivity, the highest reactor temperature is lower relative to the comparative system and longer time is required to reach the highest temperature. This surprising feature also allows for the use of less Induced Condensing Agent (ICA) (e.g., isopentane, iC 5) in forming a bimodal HDPE polymer, e.g., in a fluidized bed, because less heat needs to be removed from the fluidized bed of the polymerization reactor.

(G) The productivity enhanced bimodal catalysts of the present disclosure surprisingly reduce the light-off kinetics of the polymerization reaction that forms the bimodal HDPE, and also allow for the productivity enhanced bimodal catalysts to have a longer lifetime. The ethylene absorption curve of a bimodal catalyst with increased productivity can also show a decrease in the initial ethylene absorption, which can be quantified as a lower ethylene absorption ratio before a certain point in time. This results in delayed or slow light-off. The overall ethylene absorption decay of the bimodal catalyst with increased productivity is slower, i.e. the catalyst lifetime is increased, which contributes to the process with longer residence time to increase productivity. This can also be quantified by the ratio of the percent ethylene absorption to the reaction time point.

As discussed more fully herein, a bimodal catalyst with increased productivity is composed of at least two catalyst systems, described as (i) a solid catalyst system (alternatively a spray dried catalyst system) and (ii) an effective catalyst system. The solid catalyst system for the bimodal catalyst with increased productivity may consist of a non-metallocene catalyst, a metallocene catalyst, an activity enhancing compound, an activator, and a support. As discussed herein, additional metallocene catalysts may also be used in the solid catalyst systems of the bimodal catalysts for increased productivity. These components may be mixed in an inert hydrocarbon solvent as provided herein, followed by spray drying to obtain a solid catalyst system of bimodal catalyst with improved productivity. An effective catalyst system for a solid catalyst system of a bimodal catalyst with increased productivity may comprise contacting a slurry of the solid (or spray dried) catalyst system of a bimodal catalyst with increased productivity (e.g., mineral oil and optionally an inert hydrocarbon) with a conditioning solution of a metallocene compound in an inert hydrocarbon as discussed herein (e.g., preferably in-line into a polymerization reactor). The ratio of the catalyst to the solid catalyst system of the bimodal catalyst with increased productivity is adjusted to a range and can be adjusted to produce different bimodal products or to accommodate process requirements.

Drawings

Fig. 1 is a graph of ethylene (C2) absorption versus time for Example (EX) and Comparative Example (CE) according to one embodiment of the present disclosure.

Fig. 2 is a time to T _max for EX and CE according to one embodiment of the present disclosure.

Fig. 3 is a time to T _max for EX and CE according to one embodiment of the present disclosure.

Fig. 4 is a graph of ethylene (C2) absorption versus time for EX and CE according to one embodiment of the present disclosure.

Fig. 5 is a time to T _max for EX and CE according to one embodiment of the present disclosure.

Detailed Description

The entire contents of the summary of the invention are incorporated by reference into the detailed description. Additional embodiments are provided below, some of which are numbered for ease of reference.

Aspect 1. A method of preparing a bimodal catalyst with improved productivity comprising combining a non-metallocene pre-catalyst, a metallocene pre-catalyst, an effective amount of an activator for activating the non-metallocene pre-catalyst and the metallocene pre-catalyst, and an effective amount of an activity enhancing compound to the bimodal catalyst with improved productivity, wherein the activity enhancing compound has the formula (a):

wherein each of R ⁵、R⁴ and R ³ is independently H, halogen, (C ₁-C₂₀) hydrocarbyl or (C ₁-C₂₀) heterohydrocarbyl, provided that at least one of R ⁵ and R ³ is halogen or haloalkyl, wherein each of R ² and R ¹ is independently H, Halogen, halogen, (C ₁-C₂₀) hydrocarbyl or (C ₁-C₂₀) heterohydrocarbyl, wherein each (C ₁-C₂₀) hydrocarbyl or (C ₁-C₂₀) heterohydrocarbyl is independently unsubstituted or substituted with 1 to 4 substituent groups R ^S; wherein each substituent group R ^S is independently selected from halogen, Unsubstituted (C ₁-C₅) alkyl, -C≡CH, -OH, (C ₁-C₅) alkoxy, -C (=O) - (unsubstituted (C ₁-C₅) alkyl), -NH ₂, -N (H) (unsubstituted (C ₁-C₅) alkyl), -N (unsubstituted (C ₁-C₅) alkyl) ₂、-COOH、-C(=O)-NH₂, -C (=o) -N (H) (unsubstituted (C ₁-C₅) alkyl), -C (=o) -N (unsubstituted (C ₁-C₅) alkyl) ₂, -S- (unsubstituted (C ₁-C₅) alkyl), -S (=o) ₂ - (unsubstituted (C ₁-C₅) alkyl), -S (=o) ₂-NH₂、-S(=O)₂ -N (H) (unsubstituted (C ₁-C₅) alkyl), -S (=o) ₂ -N (unsubstituted (C ₁-C₅) alkyl) ₂, -C (=) S- (unsubstituted (C ₁-C₅) alkyl) and-COO (unsubstituted (C ₁-C₅) alkyl), and wherein the metallocene pre-catalyst has formula (B):

Wherein M is a group 4 element, each X is independently a hydride group, an amide group, a benzyl group, a methyl group, a chloro group, a fluoro group, a methylene (trimethylsilyl) group, a hydrocarbyl group, or a heterohydrocarbyl group, each of R ⁶、R⁷、R⁸、R⁹ and R ¹² is independently a (C ₁-C₁₀) hydrocarbyl group or a (C ₁-C₁₀) heterohydrocarbyl group, and each of R ¹⁰、R¹¹、R¹³、R¹⁴ and R ¹⁵ is independently H, (C ₁-C₁₀) hydrocarbyl group, or a (C ₁-C₁₀) heterohydrocarbyl group.

Aspect 2 the method of aspect 1, wherein each of R ⁵ and R ³ is independently halogen or haloalkyl, each of R ² and R ¹ is H, and R ⁴ is selected from H, hydrocarbyl, halogen and haloalkyl.

Aspect 3. The method of aspect 1, wherein the activity enhancing compound is 3, 5-difluoro-1-ethynylbenzene:

。

Aspect 4. The method of aspect 1, wherein one of R ⁵ and R ³ is halogen or haloalkyl and the other is hydrogen.

Aspect 5. The method of aspect 1, wherein the activity enhancing compound is 3-fluoro-1-ethynylbenzene or3, 4-difluoro-1-ethynylbenzene:

Or (b) 。

Aspect 6 the method of any one of aspects 1 to 5, wherein each of R ¹⁰、R¹¹、R¹³、R¹⁴ and R ¹⁵ is H, each of R ¹²、R⁶、R⁷、R⁸ and R ⁹ is (C ₁-C₅) hydrocarbyl, M is Zr, and each X is a chlorine group or (C ₁-C₃) hydrocarbyl.

Aspect 7. The method of aspect 6, wherein R ¹² is C ₃ hydrocarbyl, each of R ⁶、R⁷、R⁸ and R ⁹ is C ₁ hydrocarbyl, and each X is a chloro group or a methyl group.

Aspect 8 the process according to any one of aspects 1 to 7, wherein the metallocene procatalyst of formula (B) is selected from the group consisting of compound (1):

;

and compound (2):

。

Aspect 9 the process of any one of aspects 1 to 8, wherein the process further comprises combining the non-metallocene pre-catalyst, the metallocene pre-catalyst, an effective amount of the activator, an effective amount of the activity enhancing compound, a support material, and an inert hydrocarbon solvent to form a mixture, and removing the inert hydrocarbon solvent from the mixture, thereby obtaining the productivity-enhanced bimodal catalyst disposed on the support material.

Aspect 10 the method of any one of aspects 1 to 9, wherein the non-metallocene pre-catalyst is a non-metallocene pre-catalyst of formula (C)

Wherein M is a group 4 element, each of R ⁶ to R ¹³ is independently hydrogen or a methyl group, ar is an aryl group or a substituted aryl group, ar' is an aryl group or a substituted aryl group, and each X is independently a hydride group, an amide group, a benzyl group, a methyl group, a chloro group, a fluoro group, a methylene (trimethylsilyl) group, a hydrocarbyl group, or a heterohydrocarbyl group.

Aspect 11 the process of any one of aspects 1 to 10, wherein the non-metallocene pre-catalyst of formula (C) is compound (3):

wherein each X is independently a hydride group, an amide group, a benzyl group, a methyl group, a chloro group, a fluoro group, a methylene (trimethylsilyl) group, a hydrocarbyl group, or a heterohydrocarbyl group.

Aspect 12. The method of aspect 11, the non-metallocene pre-catalyst of formula (C) is compound (4):

。

Aspect 13 the method of any one of aspects 1 to 12, wherein the metal of the non-metallocene pre-catalyst is M, wherein the activator is an organoaluminum compound, and wherein the effective amount of the activator is an Al/M molar ratio of 0.5 to 10,000, alternatively 0.95 to 200, alternatively 1.0 to 150, alternatively 10 to 100, and/or wherein the effective amount of the activity enhancing compound comprises an activity enhancing compound to non-metallocene pre-catalyst molar ratio (AEC/NMC molar ratio) of 0.2:1.0 to 50.0:1.0, alternatively 0.9:1.0 to 20.0:1.0, alternatively 0.9:1.0 to 11:1.0, alternatively 0.95:1.0 to 6:1.0, alternatively 0.95:1.0 to 1.2:1.0.

Aspect 14 the method of any one of aspects 1 to 13, comprising using the metallocene pre-catalyst of compound (2):

as a conditioning catalyst.

Aspect 15. A productivity-enhanced bimodal catalyst prepared by the method of any one of aspects 1 to 14.

Aspect 16. A method of feeding a productivity-enhanced bimodal catalyst to a slurry, solution or gas phase polymerization reactor containing a moving bed of olefin monomer and polyolefin polymer, the method comprising preparing the productivity-enhanced bimodal catalyst according to the method of any one of aspects 1 to 14 outside the reactor, and feeding the productivity-enhanced bimodal catalyst in pure form or in solution or slurry in an inert hydrocarbon liquid or mineral oil to the slurry, solution or gas phase polymerization reactor through a feed line that does not contain olefin monomer.

Aspect 17 the method of aspect 16, further comprising pre-catalyst the metallocene of compound (2):

the use of a bimodal catalyst as a conditioning catalyst with increased productivity of any one of aspects 1 to 12 in a slurry phase, solution phase or gas phase polymerization reactor.

Aspect 18 the catalyst of the process of any one of aspects 16 to 17 such that the productivity enhanced bimodal catalyst has a reduced turndown catalyst requirement compared to a bimodal catalyst without the activity enhancing compound, which can be measured in a continuous process by a reduced turndown catalyst molar amount relative to the base catalyst or by an increased activity in lb PE/mol of the low molecular weight metallocene catalyst, which is accompanied by an increased activity in lb PE/mol of the high molecular weight non-metallocene catalyst.

Aspect 19 the method of any one of aspects 17 to 19, further comprising using a continuity additive with the productivity-enhanced bimodal catalyst in the slurry phase, solution phase, or gas phase polymerization reactor. The increase in activity may be from 5% to 100%, or from 5% to 50%, or from 10% to 90%, or from 10% to 50%, or from 20% to 40%, or from 10% to 25%.

Aspect 20. The method of any one of aspects 1 to 19 using an activity enhancing compound to prepare a bimodal catalyst with increased productivity such that kinetics are improved, as measured by a semi-batch reactor test method, as evidenced by a decrease in the maximum reactor temperature, or independently by an activity enhancing index, AEI, as shown in formula (I):

The AEI can be measured by the semi-batch reactor test described in the examples, t is the time of the batch reactor test in hours, ζ (t) is the measured ethylene uptake or consumption of the catalyst, and additive catalyst is the bimodal catalyst with increased productivity, additive-free catalyst is the bimodal catalyst without the activity enhancing compound, and AEI (0.3) is the activity enhancing index at 0.3 hours, AEI (0.3) > 2.0, alternatively AEI (0.3) > 3.0.

Aspect 21. The method of aspect 20, wherein the continuity additive is CA-300.

Aspect 22. A multimodal catalyst system comprising the productivity enhanced bimodal catalyst prepared by the method of any one of aspects 1 to 16, and at least one second catalyst selected from the group consisting of a different metallocene catalyst and a different non-metallocene catalyst.

Aspect 23. A process for preparing a polyolefin polymer, the process comprising contacting at least one 1-olefin monomer with the productivity-enhanced bimodal catalyst prepared by the process of any one of aspects 1 to 16 or the multimodal catalyst system of aspect 22 under polymerization conditions in a slurry phase, solution phase or gas phase polymerization reactor, thereby preparing the polyolefin polymer.

Aspect 24. A polyolefin polymer produced by the method of producing a polyolefin polymer of aspect 23.

Aspect 25. An article of manufacture made from the polyolefin polymer of aspect 24.

Aspect 26. The method of aspect 19, wherein the High Molecular Weight (HMW) catalyst component, i.e., the non-metallocene catalyst component, has an increased activity of >20% (given in lb PE/mol HMW catalyst).

Aspect 27. The method of aspect 19, wherein the High Molecular Weight (HMW) catalyst component, i.e., the non-metallocene catalyst component, has an increased activity of >20% (given in lb PE/mol HMW catalyst).

Aspect 28. The method of aspect 19, wherein the HMW catalyst component, i.e., the non-metallocene catalyst component, has an increased activity (given in lb PE/mol HMW catalyst) of > 40%.

Aspect 29. The method of aspect 19, wherein the Low Molecular Weight (LMW) catalyst component, i.e., the metallocene catalyst component, has an increased activity of >25% (given as lb PE/mol HMW catalyst).

Aspect 30. The method of aspects 19 to 29, wherein the LMW catalyst component, i.e., the metallocene catalyst component, has an increased activity (given in lb PE/mol HMW catalyst) of > 50%.

Aspect 31. The method of any of aspects 26-30, wherein the activity given in pounds of polyethylene per mole of molecular catalyst component of both the HMW (i.e., non-metallocene) catalyst component and the LMW (i.e., metallocene) catalyst component has increased by >20%.

Aspect 32 the method of any of aspects 26-31, wherein the activity given in pounds of polyethylene per mole of molecular catalyst component of both the HMW (i.e., non-metallocene) catalyst component and the LMW (i.e., metallocene) catalyst component has increased by >40%.

Aspect 33. The method of aspect 19, wherein the ratio of the conditioning catalyst to the dry catalyst is reduced to produce the same polymer as compared to a bimodal catalyst without the activity enhancing compound, and the concentrations of the feed of the conditioning catalyst and the feed of the bimodal catalyst are assumed to be equal.

Aspect 34. The method of aspect 19, wherein less conditioning catalyst is required to adjust the moles of catalyst or to adjust the gram amount of catalyst to make the same polymer using the productivity enhanced bimodal catalyst as compared to the bimodal catalyst without the activity enhancing compound.

Aspect 35 the method of any one of aspects 19-34, wherein the productivity-enhanced bimodal catalyst has an increased catalyst life as shown by having an increased HMW catalyst activity of >50% when compared to the bimodal catalyst without the activity enhancing compound when the residence time is >4 hours.

Aspect 36 the method of any one of aspects 19-34, wherein the productivity-enhanced bimodal catalyst has an increased catalyst life when compared to the bimodal catalyst without the activity enhancing compound when the residence time is >4 hours, as shown by having >50% increased HMW catalyst activity and >50% increased LMW catalyst activity.

Aspect 37 the method of any one of aspects 19 to 34, wherein the productivity-enhanced bimodal catalyst has a higher or equal productivity than the bimodal catalyst without the activity enhancing compound under conditions that induce a reduction in the amount of condensing agent (ICA) by more than 50%.

Aspect 38. The method of aspect 37, wherein the induced condensing agent is isopentane.

Aspect 39 the process of aspect 38, wherein the isopentane feed is <10mol%.

Aspect 40. The process of aspect 38, wherein the isopentane feed is <5mol%.

Aspect 41 the method of any one of aspects 1 to 40, wherein the productivity-enhanced bimodal catalyst can be characterized by an Additive Effectiveness Index (AEI) as shown in formula (I):

The AEI can be measured by the semi-batch reactor test described in the embodiments, and t is the time of the batch reactor test in hours.

Aspect 42. The method of aspect 41, wherein AEI (t) at t = 0.3 hours is greater than 1.8:aei (0.3) > 1.8.

Aspect 43. The method of aspect 41, wherein AEI (t) at t = 0.9 hours is greater than 1.6:aei (0.9) > 1.6.

Aspect 44. The method of aspect 41, wherein AEI (t) at t = 0.1 hours is greater than 1.3:aei (0.1) > 1.3.

Aspect 45. The method of aspect 41, wherein AEI (t) at t = 0.3 hours is greater than 3.5:aei (0.3) > 3.5.

Aspect 46. The method of aspect 41, wherein AEI (t) at t = 0.9 hours is greater than 2.0:aei (0.9) > 2.0.

Aspect 47. The method of aspect 41, wherein AEI (t) at t = 0.1 hours is greater than 2.5:aei (0.1) > 2.5.

Aspect 48 the method of any one of aspects 1 to 47, wherein the bimodal catalyst comprising the activity enhancing compound of formula (a) has a longer catalyst life than the same bimodal catalyst that does not comprise the activity enhancing compound of formula (a).

Aspect 49 the method of aspect 48, wherein the lifetime of the bimodal catalyst comprising an activity enhancing compound of formula (a) is quantified by the amount of ethylene absorption from the semi-batch reactor test method as provided herein, wherein the maximum instantaneous amount of ethylene absorption is less than the amount of ethylene absorption of the bimodal catalyst without the activity enhancing compound of formula (a), but the amount of ethylene absorption at 0.1 hour, 0.3 hour, and 0.9 hour is greater than the amount of ethylene absorption of the bimodal catalyst without the activity enhancing compound of formula (a).

Aspect 50 the method of aspect 49, wherein under the same test conditions, the bimodal catalyst comprising an activity enhancing compound of formula (a) has a ζ (t) greater than the same bimodal catalyst without the activity enhancing compound of formula (a), wherein ζ (t) is defined as the ratio of ethylene to the maximum ethylene absorption ratio of the catalyst at a given time t using the semi-batch test method as provided herein.

Bimodal catalysts with improved productivity. A method of preparing a productivity-enhanced bimodal catalyst includes combining in any order a component consisting essentially of a non-metallocene pre-catalyst, a metallocene pre-catalyst, an effective amount of an activator, and an effective amount of an activity enhancing compound under conditions effective to activate the non-metallocene pre-catalyst and the metallocene pre-catalyst to a productivity-enhanced bimodal catalyst, thereby preparing the productivity-enhanced bimodal catalyst. The activity enhancing compound may be as described in detail herein as formula (a). The metallocene precatalyst may be as detailed herein as a metallocene precatalyst of formula (B). The non-metallocene pre-catalyst may be as detailed herein as a non-metallocene pre-catalyst of formula (C). In some embodiments, for the metallocene precatalyst of formula (B) and/or the non-metallocene precatalyst of formula (C), the metal M is Zr or Hf, alternatively, M is Zr or Ti, alternatively, M is Ti or Hf, alternatively, M is Zr, alternatively, M is Hf, alternatively, M is Ti.

Embodiments of the preparation method may include any one of synthesis schemes 1 to 15.

Synthesis scheme 1. Step (a) non-metallocene pre-catalyst+metallocene pre-catalyst+excess activator- > activated non-metallocene catalyst+activated metallocene catalyst+remaining activator. Step (b) intermediate mixture + effective amount of activity enhancing compound → bimodal catalyst with improved productivity + residual activator.

Synthesis scheme 2 step (a) +non-metallocene precatalyst+metallocene precatalyst+effective amount of activity enhancing compound→intermediate non-metallocene precatalyst+intermediate metallocene precatalyst (non-metallocene precatalyst+metallocene precatalyst+unreacted mixture or reaction product of activity enhancing compound). Step (b) intermediate non-metallocene precatalyst + intermediate metallocene precatalyst + activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) →bimodal catalyst with improved productivity.

Synthetic scheme 3 step (a) non-metallocene pre-catalyst+metallocene pre-catalyst+activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) →activated non-metallocene catalyst+activated metallocene catalyst. Step (b) activated non-metallocene catalyst + activated metallocene catalyst + effective amount of activity enhancing compound→productivity enhancing bimodal catalyst.

Synthesis scheme 4 step (a) an activator (e.g., an alkylaluminoxane, such as methylaluminoxane ("MAO")) + an effective amount of an activity enhancing compound- > an intermediate mixture. Step (b) intermediate mixture + non-metallocene pre-catalyst + metallocene pre-catalyst→bimodal catalyst with improved productivity.

Synthesis scheme 5 step (a) activator- & gt non-metallocene pre-catalyst+metallocene pre-catalyst ≡effective amount of activity enhancing compound (activator and activity enhancing compound are added simultaneously but separately to non-metallocene pre-catalyst+metallocene pre-catalyst) & gt bimodal catalyst with improved productivity. And (b) no step.

Synthesis scheme 6, step (a) non-metallocene pre-catalyst+metallocene pre-catalyst+support material- & gt supported non-metallocene pre-catalyst+supported metallocene pre-catalyst. Step (b) supported non-metallocene pre-catalyst + supported metallocene pre-catalyst + an amount of activator → activation + supported non-metallocene catalyst + supported metallocene catalyst + intermediate mixture of remaining activator disposed on (or in equilibrium with) the support material. Step (c) intermediate mixture + effective amount of activity enhancing compound → bimodal catalyst with improved productivity disposed on (or in equilibrium with) the support material. In some aspects, step (a) further comprises an inert hydrocarbon solvent, and the deposition on the support material is performed by evaporating the solvent (alternatively by spray drying).

Synthesis scheme 7. Step (a) non-metallocene precatalyst+excess activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) →intermediate mixture of activated non-metallocene catalyst+remaining activator. Step (b) intermediate mixture + effective amount of activity enhancing compound → intermediate mixture of additive and activated reaction product of non-metallocene + excess activity enhancing compound. Step (c) intermediate mixture + metallocene pre-catalyst→bimodal catalyst with improved productivity + residual activator. Synthesis scheme 7 may be performed in the presence or absence of a vector as provided herein.

Synthesis scheme 8 step (a) non-metallocene pre-catalyst+excess activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) + support material→intermediate mixture of activated non-metallocene catalyst+remaining activator+support material. Step (b) intermediate mixture + effective amount of activity enhancing compound → intermediate mixture of additive and activated reaction product of non-metallocene + excess activity enhancing compound + support material. Step (c) intermediate mixture + metallocene pre-catalyst→bimodal catalyst disposed on (or in equilibrium with) the support material with improved productivity. In some aspects, step (a) further comprises an inert hydrocarbon solvent, and the deposition on the support material is performed by evaporating the solvent (alternatively by spray drying).

The amount of activator may be a stoichiometric amount (e.g., a molar ratio of 1.0:1.0) relative to the metal M of the non-metallocene catalyst, alternatively a sub-stoichiometric amount (e.g., a molar ratio of 0.1 to 0.94) relative thereto, alternatively an excess (e.g., a molar ratio of 1.1 to 10,000) relative thereto, alternatively the metal M of the non-metallocene pre-catalyst, wherein the activator is an organoaluminum compound as provided herein, and wherein the effective amount of activator is a molar ratio of Al/M of 0.5 to 10,000, alternatively 0.95 to 200, alternatively 1.0 to 150, alternatively 10 to 100, and/or wherein the effective amount of activity enhancing compound comprises a molar ratio of the activity enhancing compound to the non-metallocene pre-catalyst (AEC/NMC molar ratio) of 0.2:1.0 to 50.0:1.0, alternatively 0.9:1.0 to 20.0, alternatively 0.1:1.0 to 0, alternatively 0.95:1 to 0.0, alternatively 0.1:1.0 to 0.95. Examples of such support materials are alumina and hydrophobic fumed silica, alternatively, the hydrophobic fumed silica. The hydrophobic fumed silica can be prepared by surface treating untreated anhydrous fumed silica with an effective amount of a hydrophobic agent. The hydrophobic agent may be dimethyldichlorosilane, a polydimethylsiloxane fluid, or hexamethyldisilazane, alternatively dimethyldichlorosilane. The hydrophobized fumed silica prepared by surface treating untreated anhydrous fumed silica with dimethyldichlorosilane may be CABOSIL ^® TS-610, a fumed silica surface treated with dimethyldichlorosilane.

Synthesis scheme 9. Step (a) non-metallocene pre-catalyst+metallocene pre-catalyst+effective amount of activity enhancing compound+support material- > intermediate mixture of non-metallocene pre-catalyst+metallocene pre-catalyst and activity enhancing compound disposed on (or in equilibrium with) support material. Step (b) is an intermediate mixture + activator (e.g., an alkyl aluminoxane such as methyl aluminoxane ("MAO")) →a bimodal catalyst of increased productivity disposed on (or in equilibrium with) a support material. In some aspects, step (a) further comprises an inert hydrocarbon solvent, and the deposition on the support material is performed by evaporating the solvent (alternatively by spray drying).

Synthetic scheme 10 step (a) non-metallocene pre-catalyst + support material + activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) →activated and supported non-metallocene catalyst and metallocene catalyst disposed on (or in equilibrium with) a support material. Step (b) supported activated non-metallocene catalyst + activated metallocene catalyst + effective amount of activity enhancing compound → bimodal catalyst with improved productivity disposed on (or in equilibrium with) a support material. In some aspects, step (a) further comprises an inert hydrocarbon solvent, and the deposition on the support material is performed by evaporating the solvent (alternatively by spray drying).

Synthesis scheme 11 step (a) an activator (e.g., an alkylaluminoxane, such as methylaluminoxane ("MAO")) + an effective amount of an activity enhancing compound→an intermediate solution. Step (b) intermediate solution + non-metallocene pre-catalyst + support material → bimodal catalyst with improved productivity disposed on (or in equilibrium with) the support material. In some aspects, step (b) further comprises an inert hydrocarbon solvent, and the deposition on the support material is performed by evaporating the solvent (alternatively by spray drying).

Synthesis scheme 12. Step (a) activator- & gt non-metallocene pre-catalyst+metallocene pre-catalyst+support material ≡effective amount of activity enhancing compound (activator and activity enhancing compound are added simultaneously but separately to the mixture of non-metallocene pre-catalyst+metallocene pre-catalyst+support material) & gt bimodal catalyst with improved productivity disposed on (or in equilibrium with) support material. And (b) no step. In some aspects, step (a) further comprises an inert hydrocarbon solvent, and the deposition on the support material is performed by evaporating the solvent (alternatively by spray drying).

Synthetic scheme 13 step (a) a slurry of an activator (e.g., an alkylaluminoxane, such as methylaluminoxane ("MAO")) + a support material (e.g., hydrophobic fumed silica) +an inert hydrocarbon solvent→a supported activator disposed on (or in equilibrium with) the support material. Step (b) spray drying the slurry of step (a) to spray dried supported activator disposed as a dry powder on a support material (e.g., spray dried MAO on hydrophobic fumed silica as a dry powder ("SDMAO" or "sdMAO")). Step (c) of mixing the non-metallocene pre-catalyst + spray-dried supported activator + inert hydrocarbon solvent of step (b) to a suspension of supported non-metallocene catalyst + supported metallocene pre-catalyst disposed on (or in equilibrium with) a support material. Step (d) mixing the suspension from step (c) with an effective amount of an activity enhancing compound to a suspension of the supported productivity enhancing bimodal catalyst disposed on (or in equilibrium with) a support material in an inert hydrocarbon solvent. Optional step (e) of removing inert hydrocarbon solvent from the suspension of supported productivity enhanced bimodal catalyst → supported productivity enhanced bimodal catalyst disposed as a dry powder on a support material. Step (e) may be carried out by conventional evaporation of the inert hydrocarbon solvent from the suspension from step (d) or by spray drying the suspension from step (d).

Synthesis scheme 14 step (a) A slurry of an activator (e.g., an alkylaluminoxane, such as methylaluminoxane ("MAO")) + a support material (e.g., hydrophobic fumed silica) +an inert hydrocarbon solvent→a supported excess activator disposed on (or in equilibrium with) the support material in the inert hydrocarbon solvent. Step (b) mixing a slurry of a non-metallocene pre-catalyst, a supported activated non-metallocene catalyst disposed on (or in equilibrium with) a support material, and a supported excess activator disposed on (or in equilibrium with) the support material in an inert hydrocarbon solvent into the slurry of step (a). Step (c) adding to the slurry of step (b) an effective amount of an activity enhancing compound to a slurry of the chemically modified non-metallocene catalyst disposed on (or in equilibrium with) the support material and the supported excess activator disposed on (or in equilibrium with) the support material in an inert hydrocarbon solvent. Step (d) adding to the slurry of step (c) a metallocene pre-catalyst to a slurry of the supported productivity-enhancing bimodal catalyst disposed on (or in equilibrium with) the support material and a supported excess activator disposed on (or in equilibrium with) the support material in an inert hydrocarbon solvent. Step (e) removing the inert hydrocarbon solvent from the slurry of supported productivity enhanced bimodal catalyst- > the supported productivity enhanced bimodal catalyst disposed as a dry powder on a support material. Step (e) may be carried out by conventional evaporation of the inert hydrocarbon solvent from the suspension from step (d) or by spray drying the suspension from step (d).

Synthetic scheme 15 preparation of multimodal catalyst system comprising a bimodal catalyst with improved productivity and a different catalyst spray dried on a silica support (e.g. a metallocene catalyst) step (a) non-metallocene pre-catalyst + support material + activator (e.g. alkylaluminoxane such as methylaluminoxane ("MAO")) -activated non-metallocene catalyst + activated metallocene catalyst disposed on (or in equilibrium with) support material. Step (b) supported activated non-metallocene catalyst + supported activated metallocene catalyst + effective amount of activity enhancing compound→a bimodal catalyst with improved productivity disposed on (or in equilibrium with) a support material (e.g., a spray dried support material). Step (c) adds a different catalyst and/or pre-catalyst to the productivity enhanced bimodal catalyst disposed on (or in equilibrium with) the support material, which is added together with or subsequently contacted with the activator to form a different catalyst, thereby yielding a multimodal catalyst system. In some aspects, step (a) further comprises an inert hydrocarbon solvent, and the deposition on the support material is performed by evaporating the solvent (alternatively by spray drying). For example, the support material (e.g., fumed silica) and MAO are slurried in a solvent (e.g., toluene). A non-metallocene pre-catalyst is then added. Mix for a period of time (e.g., 1 hour). An activity enhancing compound is then added. And mixed for an additional period of time (e.g., 1 hour). A second, different pre-catalyst (e.g., a metallocene pre-catalyst) is then added. The resulting mixture was spray dried.

The multimodal catalyst system can be fed into a gas phase polymerization reactor. If desired, an additional amount of the productivity-enhancing bimodal catalyst or an additional amount of a second pre-catalyst (e.g., a metallocene pre-catalyst) may be fed separately to the reactor in the form of its solution in an inert hydrocarbon solvent, where it is contacted with the multimodal catalyst system. Such individual catalysts and/or precatalyst solutions are sometimes referred to as conditioning catalysts. Alternatively, the multimodal catalyst system can be contacted with a conditioned catalyst feed in a feed line prior to entering the reactor. In other embodiments, a multimodal catalyst system, such as a trimodal catalyst system, can be prepared in situ in a gas phase polymerization reactor by separately adding a productivity-enhancing bimodal catalyst and at least one second catalyst and/or pre-catalyst to the reactor, where they contact each other, thereby preparing the multimodal catalyst system in situ in the reactor.

The process of any of the above aspects may further comprise the step of transferring particles prepared in the gas phase, solution phase or slurry phase polymerization reactor and containing the fully active productivity-enhanced bimodal catalyst in the polymer particles to a (second) gas phase polymerization reactor.

An activity enhancing compound. The activity enhancing compound may be as described in detail herein as formula (a). As detailed herein, the activity enhancing compounds of formula (a) surprisingly and beneficially increase productivity and do not poison the productivity-increasing bimodal catalyst, particularly the non-metallocene catalyst portion of the productivity-increasing bimodal catalyst, as would be recognized by one of skill in the art in the absence of applicants' surprising discovery herein of an organic compound of formula (a). The compound of formula (a) is an alkyne. The activity enhancing compound does not contain a vinyl functional group (i.e., lacks a group of formula-C (H) =ch ₂). In some embodiments of the activity enhancing compound of formula (a):

Wherein each of R ⁵、R⁴ and R ³ is independently H, halogen, or (C ₁-C₂₀) hydrocarbyl, Or (C ₁-C₂₀) a heterohydrocarbyl group, provided that at least one of R ⁵ and R ³ is halogen or haloalkyl, wherein each of R ² and R ¹ is independently H, Halogen, halogen, Or (C ₁-C₂₀) hydrocarbyl or (C ₁-C₂₀) heterohydrocarbyl, wherein each (C ₁-C₂₀) hydrocarbyl or (C ₁-C₂₀) heterohydrocarbyl is independently unsubstituted or substituted with 1 to 4 substituent groups R ^S; wherein each substituent group R ^S is independently selected from halogen, Unsubstituted (C ₁-C₅) alkyl, -C≡CH, -OH, (C ₁-C₅) alkoxy, -C (=O) - (unsubstituted (C ₁-C₅) alkyl), -NH ₂, -N (H) (unsubstituted (C ₁-C₅) alkyl), -N (unsubstituted (C ₁-C₅) alkyl) ₂、-COOH、-C(=O)-NH₂, -C (=o) -N (H) (unsubstituted (C ₁-C₅) alkyl), -C (=o) -N (unsubstituted (C ₁-C₅) alkyl) ₂, -S- (unsubstituted (C ₁-C₅) alkyl), -S (=o) ₂ - (unsubstituted (C ₁-C₅) alkyl), -S (=o) ₂-NH₂、-S(=O)₂ -N (H) (unsubstituted (C ₁-C₅) alkyl), -S (=o) ₂ -N (unsubstituted (C ₁-C₅) alkyl) ₂, -C (=s) - (unsubstituted (C ₁-C₅) alkyl) and-COO (unsubstituted (C ₁-C₅) alkyl).

For the purposes of this disclosure, each of R ⁵ and R ³ in formula a may be halogen or haloalkyl. For the present disclosure, each of R ² and R ¹ may be H. For the purposes of this disclosure, R ⁴ may be H. For the purposes of this disclosure, the activity enhancing compound may be 3, 5-difluoro-1-ethynylbenzene. Further, for the present disclosure, each of R ³ and R ⁴ in formula a may be halogen or haloalkyl. For the present disclosure, each of R ⁵、R² and R ¹ may be H. For the purposes of this disclosure, the activity enhancing compound may be 3, 4-difluoro-1-ethynylbenzene. Further, for the purposes of this disclosure, R ³ in formula a may be halogen or haloalkyl. For the present disclosure, each of R ⁵、R⁴、R² and R ¹ may be H. For the purposes of this disclosure, the activity enhancing compound may be 3-fluoro-1-ethynylbenzene. Further, for the present disclosure, each of R ³、R⁴ and R ⁵ in formula a may be halogen or haloalkyl. for the present disclosure, each of R ² and R ¹ may be H. For the purposes of this disclosure, the activity enhancing compound may be 3,4, 5-trifluoro-1-ethynylbenzene.

Metallocene precatalyst. As mentioned, the metallocene precatalyst may be combined with the non-metallocene precatalyst, an effective amount of an activator and an effective amount of an activity enhancing compound to activate the metallocene precatalyst and the non-metallocene precatalyst into a bimodal catalyst with increased productivity. The metallocene precatalyst is of the formula (B):

wherein M is a group 4 element, each X is independently a hydride group, an amide group, a benzyl group, a methyl group, a chloro group, a fluoro group, a methylene (trimethylsilyl) group, a hydrocarbyl group, or a heterohydrocarbyl group, each of R ⁶、R⁷、R⁸、R⁹ and R ¹² is independently H, (C ₁-C₁₀) hydrocarbyl or (C ₁-C₁₀) heterohydrocarbyl, and each of R ¹⁰、R¹¹、R¹³、R¹⁴ and R ¹⁵ is independently H, (C ₁-C₁₀) a hydrocarbon group or (C ₁-C₁₀) a heterohydrocarbon group. For the purposes of this disclosure, each of R ¹⁰、R¹¹、R¹³、R¹⁴ and R ¹⁵ is H, each of R ¹²、R⁶、R⁷、R⁸ and R ⁹ is (C ₁-C₅) hydrocarbyl, M is Zr, and each X is a chlorine group or (C ₁-C₃) hydrocarbyl. For the purposes of this disclosure, each of R ¹⁰、R¹¹、R¹³、R¹⁴ and R ¹⁵ is H, each of R ¹²、R⁶、R⁷、R⁸ and R ⁹ is (C ₁-C₃) hydrocarbyl, M is Zr, and each X is a chlorine group or (C ₁-C₃) hydrocarbyl. For the purposes of this disclosure, R ¹² is a C ₃ hydrocarbyl group, each of R ⁶、R⁷、R⁸ and R ⁹ is a C ₁ hydrocarbyl group, and each X is a chlorine group or a methyl group. specific examples of the metallocene precatalyst of formula (B) include compound (1) and compound (2):

。

a non-metallocene pre-catalyst. As mentioned, the non-metallocene precatalyst may be combined with a metallocene precatalyst, an effective amount of an activator, and an effective amount of an activity enhancing compound to activate the non-metallocene precatalyst and the metallocene precatalyst into a bimodal catalyst with increased productivity. The non-metallocene pre-catalyst is of the formula (C)

Wherein M is a group 4 element, each of R ⁶ to R ¹³ is independently hydrogen or a methyl group, ar is an aryl group or a substituted aryl group, ar' is an aryl group or a substituted aryl group, and each X is independently a hydride group, an amide group, a benzyl group, a methyl group, a chloride group, a fluoro group, a methylene (trimethylsilyl) group, a, A hydrocarbyl group or a heterohydrocarbyl group. One or more embodiments provide that each X is independently a silane-containing group. One or more embodiments provide that each X is independently a trihydrocarbylsilylmethyl group. One or more embodiments provide that each X is independently a methylene (trimethylsilyl) group. In some embodiments, at least one X is ((C ₁-C₂₀) alkyl) _3-g - (phenyl) _g Si-, wherein the subscript g is 0, 1, 2, or 3, alternatively wherein the subscript g is 0 or 1, alternatively 0, alternatively 1. In some aspects, at least one X is (C ₆-C₁₂) aryl- ((C ₀-C₁₀) alkylene) -CH ₂ (e.g., benzyl). in some aspects, each X is independently (C ₆-C₁₂) aryl- ((C ₀-C₁₀) alkylene) -CH ₂, alternatively one X is (C ₆-C₁₂) aryl- ((C ₀-C₁₀) alkylene) -CH ₂ (e.g., benzyl), and the other X is F, Cl or methyl, alternatively, each X is benzyl. In some aspects, each X is benzyl, alternatively, one X is benzyl and the other X is F, cl or methyl. In some embodiments, at least one X, alternatively each X is (C ₁-C₆) alkoxy-substituted (C ₆-C₁₂) aryl, or (C ₁-C₆) alkoxy-substituted benzyl.

The activated non-metallocene catalyst is a non-metallocene catalyst of the formula (C-I)

;

Wherein each of the groups R ⁶ to R ¹³, ar' and X is as defined for formula (C), wherein A ^- is an ion (for formally balancing the positive charge of the metal M).

The ligand derived from the activity enhancing compound in the non-metallocene catalyst may be a group R ("ligand R"). The ligand R may have the formula (D): -C (R ¹⁴)=C(X)R¹⁵; wherein X is as defined for formula (C) and the ligands of formula (D) -C (R ¹⁴ and R ¹⁵ of R ⁵)=C(X)R⁶ are each independently H or R ¹⁶, and wherein each R ¹⁶ of the ligands of formula (D) -C (R ⁵)=C(X)R⁶ are each independently (C ₁-C₂₀) hydrocarbyl), (C ₁-C₂₀) heterocarbyl, (C ₁-C₂₀) aryl or (C ₁-C₂₀) heteroaryl, provided that each R ¹⁶ lacks a non-conjugated carbon-carbon double bond. The (C ₁-C₂₀) hydrocarbyl group may be unsubstituted and consist of carbon atoms and hydrogen atoms, or the (C ₁-C₂₀) hydrocarbyl group may be substituted and consist of carbon atoms, hydrogen atoms, and one or more halogen atoms. Each halogen atom is independently selected from F, cl, br and I, alternatively from F, cl and Br, alternatively from F and Cl, alternatively from F, alternatively from Cl. The unsubstituted (C ₁-C₂₀) hydrocarbon group may be unsubstituted (C ₁-C₂₀) alkyl, unsubstituted (C ₃-C₂₀) cycloalkyl, unsubstituted (C ₆-C₁₂) aryl, unsubstituted ((C ₁-C₄) alkyl) _1-3 -phenyl, or unsubstituted (C ₆-C₁₂) aryl- (C ₁-C₆) alkyl. The substituted (C ₁-C₂₀) hydrocarbyl group may be a monofluoro derivative or a difluoro derivative of the aforementioned unsubstituted (C ₁-C₂₀) hydrocarbyl group, such as 2- (3, 4-difluorophenyl) -ethylene-1-yl (having formula (a)).

Each (C ₁-C₁₉) heterocarbyl group in embodiments of R ¹⁴ to R ¹⁶ containing it may be unsubstituted and consist of a carbon atom, a hydrogen atom and at least one heteroatom selected from N and O, or (C ₁-C₁₇) heterocarbyl groups may be substituted and consist of a carbon atom, a hydrogen atom, at least one heteroatom selected from N and O and one or more halogen atoms. Unsubstituted (C ₁-C₁₇) heterocarbyl may be (C ₁-C₁₉) heteroalkyl, (C ₃-C₁₉) heterocycloalkyl, (C ₆-C₁₂) heteroaryl, ((C ₁-C₄) alkoxy) _1-3 -phenyl, or (C ₆-C₁₂) heteroaryl- (C ₁-C₆) alkyl. The substituted (C ₁-C₁₇) heterocarbyl group may be a mono-or difluoro derivative of the aforementioned unsubstituted (C ₁-C₁₇) heterocarbyl group, such as 2- (3, 5-difluorophenyl) -ethen-1-yl (formula (A)).

Non-metallocene catalyst wherein the ligand R is derived from an activity enhancing compound of formula (C-II)

;

Wherein the radicals R ⁶ to R ¹³, ar, Each of Ar' and X is as defined for formula (C), wherein A ^- is an ion (for formally balancing the positive charge of metal M), wherein ligand R may have formula (D): -C (R ¹⁴)=C(X)R¹⁵; wherein X is as defined for formula (C), and each of ligand-C (R ¹⁴ and R ¹⁵ of R ⁵)=C(X)R⁶) of formula (D) is independently H or R ¹⁶, and wherein each R ¹⁶ of ligand-C (R ⁵)=C(X)R⁶) of formula (D) is independently (C ₁-C₂₀) hydrocarbyl, (C ₁-C₂₀) heterocarbyl, (C ₁-C₂₀) aryl or (C ₁-C₂₀) heteroaryl, provided that each R ¹⁶ lacks a non-conjugated carbon-carbon double bond. The (C ₁-C₂₀) hydrocarbyl group may be unsubstituted and consist of carbon atoms and hydrogen atoms, or the (C ₁-C₂₀) hydrocarbyl group may be substituted and consist of carbon atoms, hydrogen atoms, and one or more halogen atoms. Each halogen atom is independently selected from F, cl, br and I, alternatively from F, cl and Br, alternatively from F and Cl, alternatively from F, alternatively from Cl. The unsubstituted (C ₁-C₂₀) hydrocarbon group may be unsubstituted (C ₁-C₂₀) alkyl, unsubstituted (C ₃-C₂₀) cycloalkyl, unsubstituted (C ₆-C₁₂) aryl, unsubstituted ((C ₁-C₄) alkyl) _1-3 -phenyl, or unsubstituted (C ₆-C₁₂) aryl- (C ₁-C₆) alkyl. The substituted (C ₁-C₂₀) hydrocarbyl group may be a mono-or difluoro derivative of the aforementioned unsubstituted (C ₁-C₂₀) hydrocarbyl group, such as 2- (3, 5-difluorophenyl) -ethen-1-yl (formula (A)).

For the purposes of the present disclosure, the non-metallocene catalyst having a ligand R derived from an additive catalyst may be given by either or both of formulas (C-III) and (C-IV):

;

;

Wherein each of the groups R ⁶ to R ¹³, ar' and X is as defined for formula (C), wherein a ^- is an ion (for formally balancing the positive charge of the metal M), wherein the ligand R may have formula (D). The structure of the ligand R is different from the structure of the ligand X of the non-metallocene pre-catalyst and in this connection also from the structure of the anion A ^- of the non-metallocene catalyst formed by the non-metallocene pre-catalyst.

For the purposes of the present disclosure, the first non-metallocene pre-catalyst of formula (C) may be compound (3),

Wherein each X is independently a hydride group, an amide group, a benzyl group, a methyl group, a chloro group, a fluoro group, a methylene (trimethylsilyl) group, a hydrocarbyl group, or a heterohydrocarbyl group. One or more embodiments provide that each X is independently a silane-containing group. One or more embodiments provide that each X is independently a trihydrocarbylsilylmethyl group. One or more embodiments provide that each X is independently a methylene (trimethylsilyl) group. In one or more embodiments, the first non-metallocene pre-catalyst of formula (C) may be compound (1), and each X may be a benzyl group.

For various embodiments, the non-metallocene pre-catalyst of formula (C) may be compound (4):

。

For the various embodiments, the non-metallocene catalyst having a ligand derived from an additive may be either or both of compound (4-A) and compound (4-B):

;

;

Wherein a ^- is an ion (positive charge for formally balancing the metal M).

An effective amount of an Activity Enhancing Compound (AEC). An amount of Activity Enhancing Compound (AEC) is sufficient to produce a bimodal catalyst with improved productivity. The effective amount of AEC may be expressed in terms of absolute values compared to the amount of (pre) catalyst metal M or relative values compared to the productivity performance or in a combination thereof.

In some embodiments, expressed in absolute terms, an effective amount of the activity enhancing compound may be expressed as a ratio of the moles of the activity enhancing compound to the moles of the metal M ("MAEC _mol/M_mol"), where M is M of the non-metallocene pre-catalyst of formula (C), e.g., M is a group 4 metal. In some embodiments, an effective amount of AEC is expressed as AEC _mol/M_mol ≡0.50/1.0, alternatively ≡0.9/1.0, alternatively ≡1.0/1.0, alternatively ≡1.5/1.0, alternatively ≡1.9/1.0, alternatively ≡3/1.0, alternatively ≡5/1.0, alternatively ≡6/1.0, alternatively ≡9/1.0, alternatively ≡10.0/1.0, alternatively ≡20.0/1.0, alternatively ≡30.0/1.0, alternatively ≡40.0/1.0, alternatively ≡50.0/1.0. In other words, the embodiments just mentioned above can be described by expressing the effective amount of AEC as the inverse ratio of the number of moles of metal M to the number of moles of activity enhancing compound ("M _mol/MAEC_mol") as 1.0/0.5, alternatively 1.0/0.9, alternatively 1.0/1.0, alternatively 1.0/1.5, alternatively 1.0/1.9, alternatively 1.0/3.0, alternatively 1.0/5.0, alternatively 1.0/6.0, alternatively 1.0/9.0, alternatively 1.0/10.0, alternatively 1.0/20.0, alternatively 1.0/30.0, alternatively 1.0/40.0, alternatively 1.0/50.0, respectively. In some embodiments MAEC _mol/M_mol is limited to at most 40/1, alternatively at most 30/1, alternatively at most 20/1, alternatively at most 10.0, alternatively at most 6.0, alternatively at most 5.0, alternatively at most 1.5.

Expressed in terms of relative values of productivity properties, an effective amount of an Activity Enhancing Compound (AEC) can provide a productivity enhanced bimodal catalyst with improved productivity. In some embodiments, the productivity-enhanced bimodal catalyst and AEC effective amount are characterized by having improved productivity. In some embodiments, the productivity-enhanced bimodal catalyst is prepared from any of the non-metallocene pre-catalysts of formula (C), such as compound (1) described herein.

Continuity additive/static control agent. In the gas phase polyethylene production process as disclosed herein, it may be desirable to additionally use one or more static control agents to help regulate the static level in the reactor. As used herein, a static control agent is a chemical composition that, when introduced into a fluidized bed reactor, can affect or drive the static charge (negative, positive, or zero) in the fluidized bed. The particular static control agent used may depend on the nature of the static charge, and the choice of static control agent may vary depending on the polymer produced and the single site catalyst compound used. For example, the use of static control agents is disclosed in European patent 0229368 and U.S. Pat. Nos. 4,803,251, 4,555,370 and 5,283,278, and the references cited therein.

Control agents such as aluminum stearate may be employed. The static control agent used may be selected based on its ability to receive static charge in the fluidized bed without adversely affecting productivity. Other suitable static control agents may also include aluminum distearate, ethoxylated amines, and antistatic compositions such as those provided by Innospec inc. For example, ostastat 2000 is a mixture of polysulfone copolymer, polymeric polyamine and oil-soluble sulfonic acid.

Any of the foregoing control agents, as well as control agents such as those chemicals and compositions described in WO 01/44322, listed under the heading "metal carboxylate" and including those listed as antistatic agents, may be used as control agents, either alone or in combination. For example, the metal carboxylate may be combined with an amine-containing control agent (e.g., metal carboxylate with any family member belonging to the KEMAMINE ^® (available from Crompton Corporation) or ATMER ^® (available from ICI AMERICAS inc.) product family).

Other useful continuity additives include ethyleneimine additives useful in the embodiments disclosed herein, which may include polyethyleneimines having the general formula:

Wherein n may be from about 10 to about 10,000. The polyethyleneimine may be linear, branched, or hyperbranched (e.g., forming a dendritic or dendrimer structure). They may be homopolymers or copolymers of ethyleneimine or mixtures thereof (hereinafter referred to as polyethyleneimine). Although linear polymers of the formula- (CH ₂—CH₂ -NH) -may be used as polyethyleneimines, materials having primary, secondary and tertiary branches may also be used.

The commercially available polyethyleneimine may be a compound having a branch of an ethyleneimine polymer. Suitable polyethylenimines are available from BASF Corporation under the trade name Lupasol. These compounds can be prepared in a wide range of molecular weights and product activities. Examples of commercial polyethylenimines sold by BASF suitable for use in the present invention include, but are not limited to, lupasol FG and Lupasol WF. Another useful continuity additive may include a mixture of aluminum distearate and ethoxylated amine compounds such as IRGASTAT AS-990 available from Huntsman (formerly Ciba SPECIALTY CHEMICALS). Other commercial examples of continuity additives include UT-CA-300 (Univation Technologies, LLC), which is a mixture of aluminum distearate and ethoxylated amine compounds. Mixtures of aluminum distearate and ethoxylated amine compounds can be slurried in mineral oils such as Hydrobrite 380. For example, a mixture of aluminum distearate and ethoxylated amine compounds can be slurried in mineral oil such that the total slurry concentration is in the range of about 5 wt.% to about 50 wt.%, or about 10 wt.% to about 40 wt.%, or about 15 wt.% to about 30 wt.%. Other useful static control agents and additives are disclosed in U.S. patent application publication No. 2008/0045663.

The continuity additive or static control agent may be added to the reactor in an amount ranging from 0.05ppm to 200ppm based on the ethylene feed rate or polymer production rate. In some embodiments, the continuity additive may be added in an amount ranging from 2ppm to 100ppm, or in an amount ranging from 4ppm to 50 ppm.

Catalyst productivity. The catalyst productivity of the catalysts provided herein (e.g., the productivity enhanced bimodal catalyst) is determined as the polymerization productivity of the catalyst, expressed as pounds of dry polyolefin product produced per pound of dry bimodal catalyst added (lbPE/lbcat), or alternatively expressed as grams of dry polyolefin product produced per gram of bimodal catalyst added (gPE/gcat). The catalyst activity may be used interchangeably with catalyst productivity.

Catalyst activity. The catalyst activity of a bimodal catalyst is determined as the polymerization productivity of the bimodal catalyst expressed in pounds of dry polyolefin product produced per mole of molecular catalyst component. The catalyst activity may be expressed in terms of two molecular catalyst components of a bimodal catalyst or only in terms of one single molecular catalyst component of a bimodal catalyst, e.g., the activity of a HMW catalyst component or the activity of a non-metallocene catalyst component.

Catalyst structure. Without being bound by theory, it is believed that the molecular structure of the non-metallocene catalyst (formed by the non-metallocene pre-catalyst of formula (C)), the molecular structure of the metallocene pre-catalyst (formed by the metallocene pre-catalyst of formula (B)) and the molecular structure of the productivity-enhanced bimodal catalyst can be determined by conventional analytical methods such as Nuclear Magnetic Resonance (NMR) spectroscopy or gas chromatography/mass spectrometry (GC/MS).

And (3) an activation step. In some embodiments, the method of preparing a bimodal catalyst with increased productivity further comprises an activation step as a preliminary step, which may be completed before the combining step begins. The activating step comprises contacting the non-metallocene pre-catalyst of formula (C) and the metallocene pre-catalyst of formula (B) with an activator under effective activation conditions and with an additive of formula (A) to form a bimodal catalyst with improved productivity. The activation step may be performed in various sequences, such as by contacting the non-metallocene pre-catalyst of formula (C) with an activator under effective activation conditions, followed by the addition of the additive of formula (A) followed by the addition of the metallocene pre-catalyst of formula (B) to the above. The activation step may be performed in the absence of an activity enhancing compound.

An activator. The activator used to activate the metallocene procatalyst of formula (B) and the non-metallocene procatalyst of formula (C) may be an alkylaluminoxane, an organoborane compound, an organoborate compound, or a trialkylaluminum compound. The activator may also be a combination of any two or more thereof. For example, the activator may include alkylaluminoxane and organoborate compounds such as methylaluminoxane and organoborates having the CAS designation "amine, bis (hydrogenated tallow alkyl) methyl, tetrakis (pentafluorophenyl) borate (1-)".

Alkyl aluminoxane (Alkylaluminoxane) also known as alkyl aluminoxane (alkylalumoxane). Partial hydrolysis products of trialkylaluminum compounds. Embodiments may be (C ₁-C₁₀) alkylaluminoxane, alternatively (C ₁-C₆) alkylaluminoxane, alternatively (C ₁-C₄) alkylaluminoxane, alternatively (C ₁-C₃) alkylaluminoxane, alternatively (C ₁-C₂) alkylaluminoxane, alternatively Methylaluminoxane (MAO), alternatively Modified Methylaluminoxane (MMAO). In some aspects, the alkylaluminoxane is MAO. In some embodiments, the alkylaluminoxane is supported on untreated silica (such as fumed silica). The alkylaluminoxane may be obtained from commercial suppliers or prepared by any suitable method. Suitable methods for preparing alkylaluminoxane are well known. Examples of such preparation processes are described in U.S. Pat. Nos. 4,665,208、4,952,540、5,091,352、5,206,199、5,204,419、4,874,734、4,924,018、4,908,463、4,968,827、5,308,815、5,329,032、5,248,801、5,235,081、5,157,137、5,103,031、5,391,793、5,391,529 and 5,693,838, and European patent publications EP-A-0 561 476, EP-B1-0 279 586 and EP-A-0 594 218, and PCT publication WO 94/10180.

The maximum amount of alkylaluminoxane may be selected to be a 5,000-fold molar excess relative to the precatalyst based on the ratio of the number of moles of Al metal atoms in the aluminoxane to the number of moles of metal atoms M (e.g. Ti, zr or Hf) in the precatalyst. The minimum amount of activator to pre-catalyst may be 1:1 molar ratio (Al/M). The maximum value of the molar ratio Al/M may be 150, alternatively 124.

An organoborane compound. Tris (fluoro-functional organic) borane compounds ((fluoro-organic) ₃ B) such as tris (pentafluorophenyl) borane ((C ₆F₅)₃ B), tris [3, 5-bis (trifluoromethyl) phenyl ] borane ((3, 5- (CF ₃)₂-C₆H₃)₃ B), or mixtures of any two or more thereof.

An organoborate compound. A tetrakis (fluorofunctional organic) borate compound ((fluoroorganic) ₄ B) such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, or triphenylcarbonium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, or a mixture of any two or more thereof. The organoborate compound may be a methyldi ((C ₁₄-C₁₈) alkyl) ammonium salt of tetrakis (pentafluorophenyl) borate, which may be obtained from Boulder Scientific or prepared by reacting a long chain trialkylamine (Armeen ^™ M2HT, available from Akzo-Nobel, inc.) with HCl and Li [ B (C ₆F₅)₄ ],. Such preparation is disclosed in US 5,919,983, example 2. The organoborate compound may be used herein without (further) purification. Further, examples include bis (hydrogenated tallow alkyl) methylamine and tetrakis (pentafluorophenyl) borate amine.

The trialkylaluminum compound may be used as an activator for the pre-catalyst or as a scavenger for residual moisture removal from the polymerization reactor prior to start-up thereof. Examples of suitable alkylaluminum compounds are trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum.

Activators, also known as cocatalysts, can affect the molecular weight, branching degree, comonomer content, or other characteristics of the polyolefin polymer. The activator may effect coordination polymerization or cationic polymerization.

Without being bound by theory, it is believed that the choice of activator used to activate the non-metallocene pre-catalyst and/or the metallocene pre-catalyst does not affect the structure of the productivity-enhanced bimodal catalyst prepared from the non-metallocene pre-catalyst and the metallocene pre-catalyst. That is, the structure of the productivity enhanced bimodal catalyst prepared using different activators is expected to be the same.

Effective conditions. The reactions described herein (e.g., combining step, activating step, polymerization) are independently performed under conditions that allow for activation/reaction to proceed. Examples of effective conditions are reaction temperature, atmosphere type (e.g., inert atmosphere), reactant purity, reactant stoichiometry, agitation/mixing of the reactants, and reaction time period. The conditions effective for the activation step and the polymerization step may be those described in the art and well known to those of ordinary skill. For example, effective activation conditions may include techniques for handling the catalyst, such as in-line mixers, catalyst preparation reactors, and polymerization reactors. The activation temperature may be from 0 ℃ to 800 ℃, alternatively from 20 ℃ to 50 ℃. The reaction time may be 10 minutes to 2 hours. Examples of gas phase polymerization conditions are described later herein. Effective conditions for the combined steps to prepare the bimodal catalyst with increased productivity may include a reaction temperature of-50 ℃ to 80 ℃, alternatively 0 ℃ to 50 ℃, alternatively-50 ℃ to 30 ℃, an inert atmosphere (e.g., nitrogen, helium or argon free of water and O ₂), reactants free of water and O ₂ and having a purity of 90% to 100%, an amount of reactants to minimize waste/maximize product yield, stirring or mixing the reactants, and a reaction time period of 1 minute to 24 hours.

Effective reaction conditions for preparing a bimodal catalyst with improved productivity. Such conditions may include techniques for manipulating air-sensitive and/or moisture-sensitive reagents and reactants, such as Schlenk line techniques and inert gas atmospheres (e.g., nitrogen, helium, or argon). Effective reaction conditions may also include sufficient reaction time, sufficient reaction temperature, and sufficient reaction pressure. Each reaction temperature may independently be-78 ℃ to 120 ℃, alternatively-30 ℃ to 30 ℃. Each reaction pressure may independently be 95kPa to 105kPa, alternatively 99kPa to 103kPa. The progress of any particular reaction step can be monitored by analytical methods such as Nuclear Magnetic Resonance (NMR) spectroscopy, mass spectrometry to determine the reaction time effective to maximize the yield of the desired product. Alternatively, each reaction time may independently be 30 minutes to 48 hours.

A metallocene pre-catalyst (e.g., a metallocene pre-catalyst of formula (B)). The metallocene precatalyst may be synthesized according to methods known in the art, including those cited herein. Alternatively, the metallocene precatalyst may be obtained from a precatalyst supplier such as Boulder Scientific. In some aspects, the productivity-enhanced bimodal catalyst is the product of an activation reaction of an activator, an activity enhancing compound, and the foregoing metallocene precatalyst and non-metallocene precatalyst (both as provided herein).

A non-metallocene pre-catalyst (e.g., a non-metallocene pre-catalyst of formula (C)). The non-metallocene precatalyst may be synthesized according to methods known in the art, including those methods mentioned herein. Alternatively, the non-metallocene precatalyst may be obtained from a precatalyst supplier such as bordete science company. In some aspects, the productivity-enhanced bimodal catalyst is the product of an activation reaction of an activator, an activity enhancing compound, and the foregoing metallocene precatalyst and non-metallocene precatalyst (both as provided herein).

The polyolefin polymer is prepared by a polymerization process. When the 1-olefin monomer is a combination of ethylene and propylene, the polyolefin polymer prepared therefrom is an ethylene/propylene copolymer. When the 1-olefin monomer is ethylene alone, the polyolefin polymer prepared therefrom is a polyethylene homopolymer. When the 1-olefin monomer is a combination of ethylene and 1-butene, 1-hexene or 1-octene, the polyolefin polymer produced therefrom is a poly (ethylene-co-1-butene) copolymer, a poly (ethylene-co-1-hexene) copolymer or a poly (ethylene-co-1-octene) copolymer. In some embodiments, the polyolefin polymer prepared from the 1-olefin monomer is a vinyl polymer having a composition of 50 to 100 weight percent (wt%) repeat units derived from ethylene and 50 to 0 wt% repeat units derived from a 1-olefin monomer selected from the group consisting of propylene, 1-butene, 1-hexene, 1-octene, and combinations of any two or more thereof.

In some embodiments, the polymerization process uses a 1-olefin monomer and a comonomer that is a diene monomer (e.g., 1, 3-butadiene). When the 1-olefin monomer is a combination of ethylene and propylene, and diene monomer is also used for polymerization, the polyolefin polymer is an ethylene/propylene/diene monomer (EPDM) copolymer. The EPDM copolymer can be an ethylene/propylene/1, 3-butadiene copolymer.

Multimodal (e.g., trimodal) catalyst systems. The multimodal catalyst system comprises a bimodal catalyst with increased productivity and at least one different olefin polymerization catalyst selected from the group consisting of metallocene catalysts and different non-metallocene catalysts. The multimodal catalyst system produces a multimodal polyethylene composition comprising a HMW polyethylene fraction, a medium MW fraction and a LMW polyethylene fraction in a single reactor.

The process for preparing a bimodal catalyst with improved productivity can be carried out in the presence of different olefin catalysts (e.g., metallocene catalysts or metallocene pre-catalysts). However, when performed in the presence of different precatalysts, the method of activating the non-metallocene precatalyst with an activator also includes activating a different (e.g., metallocene) precatalyst with the same or a different activator. In general, the process for preparing bimodal catalysts with improved productivity is carried out in the absence of different precatalysts.

Unsupported or supported catalysts. The non-metallocene precatalyst, non-metallocene catalyst (prepared from a non-metallocene precatalyst), metallocene precatalyst, metallocene catalyst (prepared from a metallocene precatalyst), bimodal catalyst with improved productivity and multimodal catalyst system may independently be unsupported or disposed on a solid particulate support material. When no support material is present, the non-metallocene pre-catalyst, non-metallocene catalyst, metallocene pre-catalyst, metallocene catalyst, bimodal catalyst with improved productivity, and multimodal catalyst system may be injected into the slurry, solution or gas phase polymerization reactor as a solution in a hydrocarbon solvent. When the non-metallocene precatalyst, non-metallocene catalyst, metallocene precatalyst, metallocene catalyst, bimodal catalyst with increased productivity and multimodal catalyst system are provided on a support material, they may be injected into the slurry phase, solution phase or gas phase polymerization reactor as a slurry suspended in a hydrocarbon solvent or as a dry powder (i.e. dry particulate solid).

The non-metallocene precatalyst, non-metallocene catalyst (prepared from a non-metallocene precatalyst), metallocene precatalyst, metallocene catalyst (prepared from a metallocene precatalyst), bimodal catalyst with improved productivity and/or multimodal catalyst system may be prepared in advance in the absence of a support material and then be arranged onto the support material. Alternatively, the non-metallocene pre-catalyst, non-metallocene catalyst, metallocene pre-catalyst, or metallocene catalyst may be disposed onto a support material, and then the remaining non-metallocene catalyst and/or metallocene catalyst of the bimodal catalyst with increased productivity may be prepared in situ on the support material.

The non-metallocene pre-catalyst, non-metallocene catalyst, metallocene pre-catalyst, metallocene catalyst, productivity-enhanced bimodal catalyst and/or multimodal catalyst system may be prepared by a concentration process by evaporating the hydrocarbon solvent from a suspension or solution of the support material in a solution of the non-metallocene pre-catalyst, non-metallocene catalyst, metallocene pre-catalyst, metallocene catalyst, productivity-enhanced bimodal catalyst and/or multimodal catalyst system in the hydrocarbon solvent. Alternatively, the non-metallocene pre-catalyst, non-metallocene catalyst, metallocene pre-catalyst, metallocene catalyst, bimodal catalyst with improved productivity and/or multimodal catalyst system may be prepared by spray drying a suspension or solution by a spray drying process. In some embodiments, a spray drying process is used. For example, the method can include combining a non-metallocene pre-catalyst, a metallocene pre-catalyst, an effective amount of an activator, an effective amount of an activity enhancing compound, a support material, and an inert hydrocarbon solvent to form a mixture, and removing the inert hydrocarbon solvent from the mixture to obtain a bimodal catalyst disposed on the support material with improved productivity.

A carrier material. The support material is a particulate solid, which may be non-porous, semi-porous or porous. The support material is a porous support material. Examples of support materials are talc, inorganic oxides, inorganic chlorides, zeolites, clays, resins and mixtures of any two or more thereof. Examples of suitable resins are polystyrene, functionalized or crosslinked organic carriers, such as polystyrene divinylbenzene polyolefins. The support material may independently be untreated silica, alternatively calcined untreated silica, alternatively hydrophobized silica, alternatively calcined and hydrophobized silica. The hydrophobic agent may be dichlorodimethylsilane.

The inorganic oxide support material comprises a group 2, 3, 4, 5, 13 or 14 metal oxide. Preferred supports include silica, fumed silica, alumina (see, e.g., PCT publication WO 99/60033), silica-alumina, and mixtures thereof, which may or may not be dehydrated. Other useful supports include magnesia, titania, zirconia, magnesium chloride (U.S. patent 5,965,477), montmorillonite (EP 0 511 665), phyllosilicate, zeolite, talc, clay (U.S. patent 6,034,187), and the like. Furthermore, combinations of these support materials may be used, such as silica-chromium, silica-alumina, silica-titania, and the like. Additional support materials may include those porous acrylic polymers described in EP 0 767 184, incorporated herein by reference. Other support materials include nanocomposites as disclosed in PCT publication WO 99/47598, aerogels as disclosed in PCT publication WO 99/48605, pellets as disclosed in U.S. patent 5,972,510, and polymeric beads as disclosed in PCT publication WO 99/50311.

The support material may have a surface area in the range of about 10m ²/g to about 700m ²/g, a pore volume in the range of about 0.1cm ³/g to about 4.0cm ³/g, and an average particle size in the range of about 5 microns to about 500 microns. The support material may be silica (e.g., fumed silica), alumina, clay, or talc. The fumed silica can be hydrophilic (untreated), alternatively hydrophobic (treated). In some aspects, the support is a hydrophobic fumed silica, which can be prepared by treating untreated fumed silica with a hydrophobic agent (such as dimethyldichlorosilane, a polydimethylsiloxane fluid, or hexamethyldisilazane). In some aspects, the treating agent is dimethyldichlorosilane. In one embodiment, the carrier is Cabosil ^® TS-610.

The one or more precatalysts and/or the one or more activators may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed into, or on, one or more carriers or carrier substances.

The non-metallocene precatalyst and/or the metallocene precatalyst may be spray dried according to the general method described in US 5648310. The support used with the productivity-enhanced bimodal catalyst may be functionalized as generally described in EP 0 802 203, or at least one substituent or leaving group selected as described in US 5688880.

Solution phase polymerization and/or slurry phase polymerization of olefin monomers are well known. See, for example, US8291115B2.

Inert hydrocarbon solvents. Alkanes, arenes, or alkylaromatics (i.e., arylalkanes). Examples of inert hydrocarbon solvents are alkanes such as mineral oil, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, and the like, as well as toluene and xylene. In one embodiment, the inert hydrocarbon solvent is an alkane or a mixture of alkanes, wherein each alkane independently has from 5 to 20 carbon atoms, alternatively from 5 to 12 carbon atoms, alternatively from 5 to 10 carbon atoms. Each alkane may independently be acyclic or cyclic. Each acyclic alkane can independently be linear or branched. The acyclic alkane may be pentane, 1-methylbutane (isopentane), hexane, 1-methylpentane (isohexane), heptane, 1-methylhexane (isoheptane), octane, nonane, decane, or a mixture of any two or more thereof. The cyclic alkane may be cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, methylcyclopentane, methylcyclohexane, dimethylcyclopentane or a mixture of any two or more thereof. Additional examples of suitable alkanes include Isopar-C, isopar-E and mineral oils such as paraffinic oils. In some aspects, the inert hydrocarbon solvent is free of mineral oil. The inert hydrocarbon solvent may consist of one or more (C ₅-C₁₂) alkanes.

Gas Phase Polymerization (GPP). The polymerization uses GPP reactors such as a stirred bed gas phase polymerization reactor (SB-GPP reactor) or a fluidized bed gas phase polymerization reactor (FB-GPP reactor). Such reactors and methods are generally well known. For example, the FB-GPP reactor/process may be a process ：US 3,709,853、US 4,003,712、US 4,011,382、US 4,302,566、US 4,543,399、US 4,882,400、US 5,352,749、US 5,541,270、US 2018/0079836 A1、EP-A-0 802 202, and belgium patent No. 839,380 as described in any of the following documents. These SB-GPP and FB-GPP polymerization reactors and methods mechanically agitate or fluidize the polymerization medium inside the reactor by continuous flow of gaseous monomer and diluent, respectively. Other useful reactors/processes contemplated include tandem or multistage polymerization processes such as described in U.S. Pat. No. 5,627,242, U.S. Pat. No. 5,665,818, U.S. Pat. No. 5,677,375, EP-A-0 794 200, EP-B1-0 649 992, EP-A-0 802 202 and EP-B-634421.

The gas phase polymerization operating conditions are any variable or combination of variables that may affect the composition or characteristics of the polymerization reaction in the GPP reactor or the polyolefin polymer composition product produced therefrom. Variables may include reactor design and size, pre-catalyst composition and amount, reactant composition and amount, molar ratio of the two different reactants, presence or absence of feed gas (such as H ₂), molar ratio of feed gas to reactants, absence or concentration of interfering species (e.g., H ₂ O and/or O ₂), absence or presence of Induced Condensing Agent (ICA), average polymer residence time in the reactor, partial pressure of components, feed rate of monomer, reactor bed temperature (e.g., fluidized bed temperature), nature or sequence of process steps, time period of transition between steps. Variables other than the one/those described or changed by the method or use may remain constant.

In the GPP process, ethylene ("C ₂") Hydrogen ("H ₂") and 1-hexene ("C ₆" or "C _x", where x is 6) or 1-butene ("4" or "C _x", where x is 4) to maintain a fixed comonomer to ethylene monomer gas molar ratio or feed mass ratio (C _x/C₂, e.g., C ₆/C₂) equal to the described value (e.g., 0.004 or 0.0016), a constant hydrogen to ethylene gas molar ratio or feed mass ratio ("H ₂/C₂") equal to the described value (e.g., 0.002 or 0.004), and a constant ethylene ("C ₂") partial pressure equal to the described value (e.g., 1,034kPa or 1586 kPa). The gas concentration was measured by on-line gas chromatography to understand and maintain the composition in the recycle gas stream. The reaction bed of growing polymer particles is maintained in a fluidized state by continuously flowing make-up feed and recycle gas through the reaction zone. An superficial gas velocity of 0.49 meters per second (m/sec) to 0.79 meters per second (1.6 feet per second (ft/sec) to 2.6 feet per second) is used. The FB-GPP reactor was operated at a total pressure of about 2068 kilopascals (kPa) to about 2758 kilopascals (about 300 pounds per square inch gauge (psig) to about 400 psig) and at the described first reactor bed temperature RBT. The fluidized bed is maintained at a constant height by withdrawing a portion of the bed at a rate equal to the production rate of the polyolefin polymer composition in particulate form, which may be from 5,000 kilograms per hour (kg/h) to 150,000 kilograms per hour. The product polyolefin polymer composition is semi-continuously removed through a series of valves into a fixed volume chamber, wherein the removed multimodal (e.g., bimodal or trimodal) ethylene-co-1-hexene copolymer composition is purged to remove entrained hydrocarbons and treated with a humidified nitrogen (N ₂) gas stream to deactivate any trace amounts of residual catalyst.

The bimodal catalyst system can be fed into the polymerization reactor in "dry mode" or "wet mode", alternatively dry mode, alternatively wet mode. The drying mode is dry powder or granule. The wet mode is a suspension in an inert liquid such as mineral oil.

Condensing Agent (ICA) is induced. An inert liquid may be used to cool materials in the GPP reactor. Its use is optional. ICA may be a (C ₃-C₂₀) alkane, alternatively a (C ₅-C₂₀) alkane, such as 2-methylbutane (i.e. isopentane). See US 4,453,399, US 4,588,790, US 4,994,534, US 5,352,749, US 5,462,999 and US 6,489,408. The ICA concentration in the reactor may be 0.1mol% to 25mol%, alternatively 1mol% to 16mol%, alternatively 1mol% to 10mol%.

The GPP conditions can also include one or more additives, such as a chain transfer agent or an accelerator. Chain transfer agents are well known and may be metal alkyls, such as diethyl zinc. Accelerators are known, for example, from US 4,988,783 and may include chloroform, CFCl ₃, trichloroethane and difluoro tetrachloroethane. The scavenger may be used to react with moisture prior to reactor start-up and with excess activator during reactor changeover. The scavenger may be a trialkylaluminum. The GPP can operate without (unintentional addition of) scavengers. The GPP reactor/process can further include an amount (e.g., 0.5ppm to 200ppm based on all feed to the reactor) of one or more static control agents and/or one or more continuity additives, such as aluminum stearate or polyethylenimine. Static control agents may be added to the FB-GPP reactor to inhibit the formation or accumulation of static charges therein.

The GPP reactor can be a commercial scale FB-GPP reactor such as the UNIPOL ^™ reactor or the UNIPOL ^™ II reactor available from the subsidiary You Niwei Constipation, inc. (Univation Technologies, LLC) of Dow chemical company (The Dow Chemical Company, midland, michigan, USA) of Midland, michigan, U.S.A.

1-Olefin monomers. The 1-olefin monomer is a compound of formula H ₂C=C(H)(CH₂)_nR¹⁷, wherein the subscript n is an integer from 0 to 19 and the group R ¹⁷ is H or CH ₃. Examples are ethylene (subscript n is 0 and R ¹⁷ is H), propylene (subscript n is 0 and R ¹⁷ is CH ₃) and (C ₄-C₂₀) alpha-olefins (subscript n is an integer from 1 to 19 and R ¹⁷ is H or CH ₃. In some embodiments, the 1-olefin monomer is ethylene, propylene, 1-butene, 1-hexene, 1-octene, or a combination of any two or more thereof. In some embodiments, the 1-olefin monomer is a combination of ethylene and propylene. In other embodiments, the 1-olefin monomer is ethylene alone or a combination of ethylene and 1-butene, 1-hexene, or 1-octene.

A polyolefin polymer. A product of polymerizing at least one 1-olefin monomer with a bimodal catalyst having improved productivity. A macromolecule or collection of macromolecules having constituent units derived from at least one 1-olefin monomer. For example, when at least one 1-olefin monomer is composed of ethylene, the polyolefin polymer is composed of a polyethylene homopolymer. When at least one 1-olefin monomer consists of ethylene and propylene, the polyolefin polymer consists of an ethylene/propylene copolymer. When the at least one 1-olefin monomer consists of ethylene and a comonomer selected from the group consisting of 1-butene, 1-hexene and 1-octene, the polyolefin polymer is selected from the group consisting of poly (ethylene-co-1-butene) copolymer, poly (ethylene-co-1-hexene) copolymer and poly (ethylene-co-1-octene) copolymer, respectively.

The polyolefin polymer may be a homopolymer or a copolymer. The polyolefin polymer produced from the productivity-enhanced bimodal catalyst has a multimodal (e.g., bimodal) molecular weight distribution and comprises a Higher Molecular Weight (HMW) polyolefin polymer component and a Lower Molecular Weight (LMW) polyolefin polymer component. The HMW polyolefin polymer component and the LMW polyolefin polymer component can be prepared from a bimodal catalyst with improved productivity.

Any compound, composition, formulation, material, mixture or reaction product herein may be free of any of the chemical elements ：H、Li、Be、B、C、N、O、F、Na、Mg、Al、Si、P、S、Cl、K、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、As、Se、Br、Rb、Sr、Y、Zr、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Cd、In、Sn、Sb、Te、I、Cs、Ba、Hf、Ta、W、Re、Os、Ir、Pt、Au、Hg、Tl、Pb、Bi、 lanthanides and actinides selected from the group consisting of the chemical elements required for the compound, composition, formulation, material, mixture or reaction product (e.g., zr required for a zirconium compound, or C and H required for polyethylene, or C, H and O required for an alcohol).

Alternatively, the different embodiments are preceded. ASTM is ASTM international (ASTM International, west Conshohocken, pennsylvania, USA) for the standard organization, west Kang Shehuo ken, pa. Any comparative examples are for illustrative purposes only and should not be prior art. Absence or lack means completely absent, alternatively undetectable. IUPAC is the international association of theory and application chemistry (International Union of Pure AND APPLIED CHEMISTRY) (IUPAC secretary, north Carolina, triangu, USA) (IUPAC Secretariat, RESEARCH TRIANGLE PARK, north Carolina, USA)). The periodic table of elements is the IUPAC version released on day 5, month 1 of 2018. The "may" gives the allowed choice, not necessarily. Operability means functionally capable or efficient. Optionally (optionally) means absent (or excluded), alternatively present (or included). The characteristics may be measured using standard test methods and conditions. Ranges include endpoints, sub-ranges, and integer and/or fractional values contained therein, except for integer ranges excluding fractional values. Room temperature at 23 ± 1 ℃.

Unless otherwise indicated, the term definitions used herein are taken from "IUPAC Compendium of Chemical Technology" ("Jin Pishu") version 2.3.3 of 24, month 2 of 2014. For convenience, some definitions are given below.

As used herein, "hydrocarbyl" or "hydrocarbyl group" includes aliphatic, cyclic, olefinic, acetylenic, and aromatic groups (i.e., hydrocarbon groups) that contain hydrogen and carbon and lack one hydrogen.

As used herein, "alkyl" includes straight, branched, and cyclic alkanyl radicals lacking one hydrogen. Thus, for example, a-CH 3 group ("methyl") and a CH3CH 2-group ("ethyl") are examples of alkyl groups.

As used herein, "haloalkyl" includes any alkyl group in which one or more hydrogen atoms are replaced with halogen atoms.

As used herein, "aryl" groups include phenyl, naphthyl, pyridyl and other groups whose molecules have characteristic ring structures of benzene, naphthalene, phenanthrene, anthracene, and the like. It is understood that the "aryl" group may be a C6 to C20 aryl group. For example, the C6H 5-aromatic structure is "phenyl" and the C6H4 2-aromatic structure is "phenylene".

As used herein, "alkylene" includes straight, branched, and cyclic hydrocarbyl groups lacking two hydrogens. Thus, -CH ₂ - ("methylene") and-CH ₂CH₂ - ("ethylene") are examples of alkylene groups.

Reactor additives. The system or polymerization process using the productivity enhanced bimodal catalyst may optionally have at least one reactor additive other than the activity enhancing compounds provided herein. At least one additive may be a flow aid for preventing agglomeration of dry catalyst particles, an antistatic compound for inhibiting accumulation of charge on polyolefin particles in a floating bed gas phase polymerization reactor, or an anti-fouling compound such as a metal carboxylate for inhibiting reactor fouling.

Bimodal means a molecular weight distribution as determined by GPC having two and only two peaks, where the two peaks may be head-shoulder configurations or double-head configurations with local minima (valleys) therebetween. It may also refer to catalysts that produce such bimodal molecular weight distributions.

Catalyst means herein a material that can polymerize a monomer and optionally a comonomer to produce a polymer. The catalyst may be an olefin polymerization catalyst that can polymerize an olefin monomer (e.g., ethylene) and optionally an olefin comonomer (e.g., propylene and/or (C ₄-C₂₀) a-olefin) to produce a polyolefin homopolymer or an optional polyolefin copolymer, respectively.

The catalyst system is a set of at least two chemical components and/or reaction products thereof that co-act as a unit to increase the reaction rate, wherein at least one of the at least two chemical components is a catalyst. The other chemical components may be independently selected from different catalysts, support materials, excess activators, catalyst additives such as antistatic agents, cocatalysts, metal salts of carboxylic acids, dispersants for preventing particles of the catalyst system from sticking together. The catalyst system may comprise a catalyst and a support material, wherein the catalyst is disposed on the support material, the support material supporting and providing a physical framework for increasing the surface distribution of the catalyst. The catalyst system does not include monomers, comonomers or activity enhancing compounds.

Activating. Bimodal catalysts with improved productivity are prepared by an activated mode. Activation occurs between the non-metallocene pre-catalyst, the metallocene pre-catalyst, an effective amount of an activator, and an effective amount of an activity enhancing compound, which activates the non-metallocene pre-catalyst and the metallocene pre-catalyst to a bimodal catalyst with increased productivity. That is, the productivity-enhanced bimodal catalyst is prepared by converting the non-metallocene procatalyst and the metallocene procatalyst into a productivity-enhanced bimodal catalyst having enhanced polymer production functionality (e.g., having at least improved (higher) productivity). The activity enhancing compound does not contain metal atoms. It is therefore quite surprising that the activity enhancing compounds are capable of increasing the productivity of catalysts prepared from non-metallocene pre-catalysts and metallocene pre-catalysts.

Substantially consisting of does not mean: containing exogenous organometallic compounds. Exogenous organometallic compounds are compositionally different from non-metallocene precatalysts and metallocene precatalysts. Thus, the process of the present invention is not accomplished by the addition of exogenous organometallic compounds or pre-catalyst precursors thereof. Thus, the contacting step of the process is performed in the absence of an exogenous organometallic compound or pre-catalyst precursor thereof. The precatalysts are not self-modifying so that they cannot increase the productivity of themselves or of another compound. In other words, in the absence of the activity enhancing compound, there is no productivity improvement.

Exogenous. Having an external cause or source, or obtained from an external source.

And (5) feeding. The material is transported or physically moved from outside the space (e.g., outside the polymerization reactor) to inside the space (inside the polymerization reactor).

GPC means gel permeation chromatography.

A leaving group. A group bonded to a metal atom of the non-metallocene pre-catalyst and abstracted by the activator during activation of the pre-catalyst to the non-metallocene catalyst. An example of a leaving group is a monodentate group X in formula (C). Each non-metallocene pre-catalyst described herein implicitly has at least one leaving group and typically has two leaving groups.

A ligand. Monovalent, divalent, trivalent or tetravalent and bidentate, tridentate or tetradentate organic groups having two, three or four coordination functionalities, respectively, for bonding to metal atoms of the non-metallocene pre-catalyst or the metallocene pre-catalyst. By activating the respective precatalyst, the ligand remains coordinated to the metal atom in the non-metallocene catalyst or the metallocene catalyst. Thus, the ligand indicates a group in the non-metallocene pre-catalyst and/or the metallocene pre-catalyst that is brought into the corresponding catalyst prepared by activating the pre-catalyst, whereas the leaving group indicates an unstable group, at least one of which is taken up by the activator during activation of the pre-catalyst.

The metal atom means any of the following basic units of groups 1 to 13, groups 14 to 16, groups 3 to 6, groups 17, groups 5 and 6, lanthanides, actinides, all of the periodic table of elements published by IUPAC on month 12, 2018.

By "productivity-improving" or productivity-improving is meant that the productivity of an olefin polymerization catalyst is changed by improving the productivity of the olefin polymerization catalyst as compared to the productivity of an olefin polymerization catalyst under the same polymerization conditions prior to chemically converting the olefin polymerization catalyst.

Multimodal means a molecular weight distribution as determined by GPC having two or more peaks, where two or more peaks may independently be head-shoulder configurations or two or more head configurations with local minima (valleys) therebetween. Examples of multimodal are bimodal and trimodal. It may also refer to catalysts that produce such multimodal molecular weight distribution.

By organic compound is meant a chemical entity consisting of carbon atoms, hydrogen atoms, optionally zero, one or more halogen atoms, and optionally zero, one or more heteroatoms independently selected from O, N, P and Si per molecule. The molecule does not have (i.e., does not contain) a metal atom (i.e., the chemical entity does not include an organometallic compound).

The reaction conditions, including polymerization conditions, are environmental conditions under which chemical transformations (e.g., polymerization) are carried out, such as temperature, pressure, solvents, reactant concentrations, and the like. All chemical transformations described herein are performed under suitable and efficient reaction conditions.

By support material is meant finely divided particulate inorganic solid capable of containing the catalyst.

By trimodal is meant a molecular weight distribution as determined by GPC having three and only three peaks. It may also refer to catalysts that produce such a trimodal molecular weight distribution.

Unsupported means free of inorganic support materials (e.g., silica).

Examples

Additional embodiments of the invention are the foregoing aspects and the claims that follow that describe ranges of process conditions and/or ranges of material properties, wherein in additional embodiments of the invention, endpoints of ranges of process conditions and/or endpoints of ranges of material properties are modified to any of the example process condition values and/or any of the example material property values described below in this section for any of the inventive examples, respectively.

Some embodiments of the present disclosure will now be described in detail in the following examples. All materials used herein were purchased from SIGMA ALDRICH unless otherwise indicated. The comparative or non-inventive examples either do not contain an activity enhancing compound or contain less than an effective amount of an activity enhancing compound.

TABLE 1 materials

In the examples, the following test procedures were used. Density is measured according to ASTM-D-1505. Melt index MI (I ₅) and flow index FI (I ₂₁) were measured at 190℃according to ASTM-1238, condition B. Weight average molecular weight (Mw), number average molecular weight (Mn), mp and Mw/Mn are measured as follows. Particle size was measured using Malvern Mastersizer laser diffraction particle size analyzer (MALVERN PANALYTICAL).

Differential scanning calorimetry

The melting temperature was determined by Differential Scanning Calorimetry (DSC) according to ASTM D3418-08. Typically, a scan rate of 10 ℃ per minute is used for 10mg of the sample, and a second heating cycle is used to determine T _m.

Gel Permeation Chromatography (GPC)

M _w、M_n、M_z、M_p and M _w/M_n (PDI) were measured using a high temperature GPC (Polymer Laboratories) equipped with a differential refractive index Detector (DRI). Three Polymer Laboratories PLgel μm Mixed-B columns were used. The nominal flow rate was 1.0mL/min and the nominal injection volume was 300. Mu.L. Various transfer lines, columns and differential refractometers (DRI detectors) were included in an oven maintained at a temperature of 160 ℃. The solvent used for the experiment was prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2, 4-Trichlorobenzene (TCB). The TCB mixture was then filtered through a 0.1 μm Teflon filter. The TCB is then degassed with an in-line degasser prior to entering the GPC instrument. The polymer solution was prepared by placing the dried polymer in a glass bottle, adding the desired amount of TCB, and then heating the mixture at 160 ℃ and shaking continuously for about 2 hours. All amounts were measured by gravimetric methods. The injection concentration was 0.5mg/ml to 2.0mg/ml, with lower concentrations for higher molecular weight samples. The DRI detector was purged prior to running each sample. The flow rate in the apparatus was then increased to 1.0ml/min and the DRI was allowed to stabilize for 8 hours before the first sample was injected. Molecular weight was determined by combining a generic calibration relationship with column calibration using a series of monodisperse Polystyrene (PS) standards. MW for each elution volume was calculated using the following equation:

wherein variables with subscript "X" represent test samples, and those with subscript "PS" represent PS. In the process of the present invention, in the process, AndAt the same timeAndAre obtained from published literature. Specifically, for polyethylene, a/k=0.695/0.000579, and for polypropylene, a/k=0.705/0.0002288. The concentration c at each point in the chromatogram was calculated from the DRI signal IDRI minus the baseline using the following equation:

wherein KDRI is a constant determined by calibrating the DRI, and (dn/dc) is the refractive index increment of the system. Specifically, dn/dc=0.109 for polyethylene.

Mass recovery was calculated from the ratio of the integrated area of the concentration chromatogram to the elution volume and the injection mass, which is equal to the predetermined concentration times the injection loop volume.

All molecular weights are reported in g/mol unless otherwise indicated.

The comonomer content (i.e., 1-hexene) (wt.% C6) incorporated in the polymer was determined by fast FT-IR spectroscopy of the dissolved polymer in GPC measurements. Comonomer content can be determined with respect to polymer molecular weight by using an infrared detector (such as an IR5 detector) in a gel permeation chromatography measurement as described in Analytical Chemistry 2014, 86(17), 8649-8656.Dean Lee、Colin Li Pi Shan、David M. Meunier、John W. Lyons、Rongjuan Cong and a. Willem deGroot, "absolute chemical composition distribution measurement （Toward Absolute Chemical Composition Distribution Measurement of Polyolefins by High-Temperature Liquid Chromatography Hyphenated with Infrared Absorbance and Light Scattering Detectors）".Analytical Chemistry 2014 86 (17), 8649-8656 for polyolefins by high temperature liquid chromatography combined with infrared absorbance and light scattering detectors.

Pilot test device

General procedure for catalyst preparation

All catalyst slurries were prepared using an oil jacketed 10 gallon Continuous Stirred Tank Reactor (CSTR) and mixed at 40 ℃ under 6 pounds per square inch gauge (psig) (0.414 bar) nitrogen. Throughout the preparation of each catalyst slurry batch, the contents of the stirred tank reactor were continuously stirred at 400 revolutions per minute (rpm). For each batch, the order of addition of the components was toluene, MAO (10 wt% toluene solution), then silica (CAB-O-SIL TS-610 fumed silica), followed by catalyst compound (I). For the catalyst of the present invention, the activity enhancing compound (II-a) is added and the slurry is mixed for one hour before the next component (e.g., catalyst compound (III)) is added, after which the slurry is mixed for another hour. Compound (II-a) was not added in the preparation of the comparative catalyst. After each catalyst compound was added, the addition vessel was rinsed with toluene (1-2 lbs) and then added to the stirred tank reactor.

Each catalyst slurry was then spray dried in batches by transfer to a rotary atomizer four-hole wheel assembly. Fresh toluene was purged through the atomizer bore until the specified outlet temperature was reached and the atomizer was rotated at the speed specified in table 2. The catalyst slurry droplets were flash dried by contact with 130 ℃ recycle gas (nitrogen) upon exiting the atomizer orifice, with an outlet temperature of 84 ℃. The recycle gas is used to transfer the solids to a separation cyclone so that the solid spray-dried catalyst can be collected.

Table 2 catalyst preparation for CE 1, IE 1 and IE 2

Table 3A continuous polymerization reactor data

Table 3B continuous polymerization reactor data

Discussion of the invention

Table 3A/table 3B provides the productivity of CE a and IE 1 from examples CE B, CE C, IE 3 and IE 4. The productivity data are for comparing two different runs of bimodal catalyst CE a with two runs of inventive catalyst IE 1. The production rate of IE was 21% (average) higher than CE (CE aaverage=8,265 lb/lb; IE 1 average=10,008 lb/lb). Table 3A/Table 3B also provides the productivity of IE 2 (IE 5) compared to catalysts CE 1 (CE B and CE C), which shows the productivity data comparing the two different runs of bimodal catalyst CE A and the productivity of the run using catalyst IE 2 of the invention. For the catalyst of the present invention, it has 20% less HMW molecular catalyst component (catalyst compound (I)), with slightly higher productivity, 200 lb/lb or about 3%. This indicates that the increase in productivity of the bimodal polymer is an effect of the increase in productivity of the HMW component. The same product was prepared in all cases, thus confirming an increase in the productivity of compound (I).

Table 3A/table 3B also provides the ratio of the conditioning catalyst (containing catalyst compound (IV)) to the solid catalyst, wherein the two inventive examples using catalyst IE 1 showed an average reduction in conditioning/catalyst ratio of 21% (CE aaverage=16.15, IE 1 average= 12.74). This occurs when the additive increases both the productivity of the HMW compound (catalyst compound (I)) and the overall bimodal polymer while still producing the same product (see table 3A comparing MI ₅、FI₂₁, MFR and density). With higher productivity and the same product, it is generally expected that more conditioning catalyst will be required to make the same product, however with less conditioning catalyst, the present disclosure demonstrates the secondary effect of the activity enhancing compound (II-a) of the present disclosure on the catalyst compound (I) (HMW catalyst). That is, the productivity of the LMW metallocene catalyst component (e.g., catalyst compound (III)) is also improved. This is an unexpected and novel result. While not wanting to be bound by theory, it is believed that this is a result of the kinetic effect of the activity enhancing compound on the HMW compound, reducing light-off and thus reducing the initial heat of polymerization of the particles. The reduction in heat of reaction early in the reaction favors the metallocene, presumably by reducing deactivation or death of the catalyst component.

Table 3A/table 3B also provides the percentage of HMW component of the bimodal polymer, which was obtained from GPC deconvolution of each sample. The activity of each of the HMW catalyst (e.g., non-metallocene catalyst component) and LMW catalyst component (e.g., metallocene catalyst component) is reported in pounds of polyethylene per mole of molecular catalyst component (e.g., lb PE/mol HMW or lb PE/mol LMW), as well as the catalyst and conditioning catalyst feeds. This allows quantification of each fraction, regardless of the conditioning catalyst and catalyst feed concentration used. The average activity of the HMW catalyst components (i.e., non-metallocene catalyst components) of CE A (examples CE B and CE C) was 224,796 lb PE/mol HMW, while the average activity of the LMW catalyst components (i.e., metallocene catalyst components) of CE A (examples CE B and CE C) was 78,094 lb PE/mol LMW. For the bimodal catalyst IE 1 (examples IE 3 and IE 4) with increased productivity, the average activity of the HMW catalyst component (i.e., the non-metallocene catalyst component) was 319,418 lb PE/mol HMW, while the average activity of the LMW catalyst component (i.e., the metallocene catalyst component) was 120,748 lb PE/mol LMW. This quantification of the respective activities of the HMW and LMW catalyst components demonstrates that the activity (and thus the productivity) of each individual molecular catalyst component is improved due to the additive component in the productivity-improved bimodal catalyst. The activity of the HMW catalyst component, i.e., the non-metallocene catalyst component, was increased by 42.1%, while the activity of the LMW catalyst component, i.e., the metallocene catalyst component, was increased by 54.5%.

Table 3A/Table 3B also provides the adjustment/catalyst ratios for IE 5 using the IE 2 catalyst and CE B and CE C using the CE 1 catalyst. The IE 5 tuning/catalyst ratio was reduced by nearly half even though the catalyst had nearly the same productivity and nearly the same LMW metallocene component (catalyst component (III)) on a solid base catalyst. This is also a surprising and novel result, since it is expected that the same product will be produced with the same productivity using the same amount of the conditioning catalyst (since the mechanism of action acts on catalyst compound (I) (HMW compound)). This is demonstrated by the activity measured for each of the HMW and LMW catalyst components, wherein the activity of the HMW catalyst component (i.e., the non-metallocene catalyst component) is increased by 53.1% and the activity of the LMW catalyst component (i.e., the metallocene catalyst component) is increased by 95.4%.

While not wanting to be bound by theory, it is believed that the direct effect of the activity enhancing compounds (II-a) of the present disclosure is to alter or modify the leaving group of the catalyst compound (I), thereby altering the kinetics of the catalyst component. This can be seen in the residence times provided in table 3A/table 3B. For both residence time experiments (comparative and inventive examples), the turndown/catalyst ratio was kept constant and the residence time increased. For comparative catalyst CE a, the productivity increased and the flow index remained constant. For the catalyst of the invention, productivity also increased (relative to the comparative catalyst and shorter residence time) while the flow index decreased from 5.86 to 4.25, which means that the amount of HMW polymer component increased, indicating that the lifetime of catalyst compound (I) (HMW catalyst) increased with the presence of the activity enhancing compound (II-a) of the invention. The activities of the HMW and LMW catalyst components in the residence time experiment were obtained by deconvolution and catalyst and adjustment of the catalyst feed. For the bimodal catalyst with increased productivity (i.e., IE 1, example IE 7), the activity of the HMW catalyst component was increased by 56.0% and the activity of the LMW catalyst component was increased by 51.6% compared to CE a (example CE E).

The mechanism of action of the activity enhancing compound alters the kinetics of catalyst compound (I) and reduces the heat generated by the catalyst of the invention (e.g., lower heat due to slower initial kinetics) in addition to increasing the productivity of the HMW component and bimodal catalyst and reducing the need to adjust the catalyst at higher productivity. To explore the effect of the lower heat generated by the catalyst of the present invention, isopentane (iC 5) feed was reduced from 10.5mol% to 4.8mol%; iC5 was used as an Induced Condensing Agent (ICA) to aid in heat removal in the reactor. For comparative bimodal catalyst CE A, the productivity was reduced from 8,222 lb/lb (CE C) to 7,643 lb/lb (CE D) and the flow index increased from 5.99 to 15.33. For the inventive bimodal catalyst IE 1 with increased productivity, the decrease in iC5 from 10.5mol% to 4.8mol% resulted in a decrease in productivity from 10,237 lb/lb (IE 4) to 9,292 lb/lb (IE 6) and an increase in flow index from 5.86 to 9.72. Looking at the activity of each component, for a bimodal catalyst with increased productivity, the HMW activity was increased by 58.5% while the LMW activity was increased by 43.9%. Experiments to reduce ICA indicated that the productivity of bimodal catalysts was sensitive to heat and also indicated that the inventive catalyst (i.e., IE 1, example IE 6) containing additives could be run at higher productivity at low iC5 compared to the comparative bimodal catalyst (CE a) at high iC5 (example CE D).

Table 3C continuous polymerization reactor data

Table 3D continuous polymerization reactor data

Table 3C/Table 3D provides the polymer characteristics of the examples in Table 3A/Table 3B as determined by GPC. The data underscores that the activity enhancing compounds improve productivity (and alter the kinetics, light-off and heat generated by bimodal catalysts) without altering the polymer produced. The polymers prepared from CE a (examples CE B and CE C) and the productivity enhanced bimodal catalyst IE (examples IE 3 and IE 4) were identical (the variation between repeated runs of the same catalyst (i.e. CE B and CE C or IE 3 and IE 4) was less than the variation between different catalysts).

Semi-batch reactor test

Preparation of comparative catalyst CE F

Spray dried catalyst for CE F was prepared and sprayed in a nitrogen purged glove box. In a oven-dried glass bottle, 1.37g of fumed silica (CAB-O-SIL ^® TS-610 fumed silica) was slurried in 34g of toluene until well dispersed, then 9.2g of a 10 wt% MAO toluene solution and catalyst compound (I) (0.056 g) were added. Catalyst compound (III) (0.033 g) was then added, after which the mixture was stirred for an additional 30 to 60 minutes. The mixture was spray dried using Buchi MINI SPRAY DRYER B-290 with the parameters set to 140℃and outlet temperature 75℃at minimum, aspirator set to 60 and pump speed 130rpm to give a dry sample of CE F.

Preparation of catalyst IE 9 according to the invention

Spray dried catalyst for IE 9 was prepared and sprayed in a nitrogen purged glove box. In a oven-dried glass bottle, 1.37g of fumed silica (CAB-O-SIL ^® TS-610 fumed silica) was slurried in 34g of toluene until well dispersed, then 9.2g of a 10 wt% MAO toluene solution and catalyst compound (I) (0.056 g) were added. The mixture was magnetically stirred for 15 minutes, then the activity enhancing compound (II-a) (0.014 g) was added, and the mixture was stirred for another 30 minutes, then the catalyst compound (III) (0.033 g) was added, and then the mixture was stirred for another 30 to 60 minutes. The mixture was spray dried using Buchi MINI SPRAY DRYER B-290 with the parameters set to 140℃and outlet temperature 75℃at minimum, aspirator set to 60 and pump speed 130rpm to give a dried sample of IE 9.

Preparation of comparative catalyst CE G

Spray dried catalyst for CE G was prepared and sprayed in a nitrogen purged glove box. In a oven-dried glass bottle, 1.38g of fumed silica (CAB-O-SIL ^® TS-610 fumed silica) was slurried in 33g of toluene until well dispersed, then 9.3g of a 10 wt% MAO toluene solution and catalyst compound (I) (0.045 g) were added. Catalyst compound (III) (0.033 g) was then added, after which the mixture was stirred for an additional 30 to 60 minutes. The mixture was spray dried using Buchi MINI SPRAY DRYER B-290 with the parameters set to 140℃and outlet temperature 75℃at minimum, aspirator set to 60 and pump speed 130rpm to give a dry sample of CE G.

Preparation of catalyst IE 10 according to the invention

Spray dried catalyst for IE 10 was prepared and sprayed in a nitrogen purged glove box. In a oven-dried glass bottle, 1.38g of fumed silica (CAB-O-SIL ^® TS-610 fumed silica) was slurried in 33g of toluene until well dispersed, then 9.3g of a 10 wt% MAO toluene solution and catalyst compound (I) (0.056 g) were added. The mixture was magnetically stirred for 15 minutes, then the activity enhancing compound (II-a) (0.011 g) was added, and the mixture was stirred for another 30 minutes, then the catalyst compound (III) (0.033 g) was added, and then the mixture was stirred for another 30 minutes to 60 minutes. The mixture was spray dried using Buchi MINI SPRAY DRYER B-290 with the parameters set to 140℃and outlet temperature 75℃at minimum, aspirator set to 60 and pump speed 130rpm to give a dried sample of IE 10.

Preparation of comparative catalyst CE H

Spray dried catalyst for CE H was prepared and sprayed in a nitrogen purged glove box. In a baked glass bottle, 2.65g of fumed silica (CAB-O-SIL ^® TS-610 fumed silica) was slurried in 70g of toluene until well dispersed, then 22g of a 10 wt% MAO toluene solution and 0.082g of catalyst compound (III) were added. The mixture was stirred for 30 to 60 minutes. The mixture was spray dried using Buchi MINI SPRAY DRYER B-290 with the parameters set to 140℃and outlet temperature 75℃at minimum, aspirator set to 70 and pump speed 130rpm to give a dry sample of CE H.

Preparation of comparative catalyst CE I

Spray dried catalyst for CE I was prepared and sprayed in a nitrogen purged glove box. In a baked glass bottle, 2.65g of fumed silica (CAB-O-SIL ^® TS-610 fumed silica) was slurried in 70g of toluene until well dispersed, then 22g of a 10 wt% MAO toluene solution and 0.082g of catalyst compound (III) were added. The activity-enhancing compound (II-a) (0.029 g) was added, and the mixture was stirred for 30 minutes to 60 minutes. The mixture was spray dried using Buchi MINI SPRAY DRYER B-290 with the parameters set to 140℃and outlet temperature 75℃at minimum, aspirator set to 70 and pump speed 130rpm to give a dry sample of CE I.

Gas phase batch reactor catalyst test procedure:

The gas phase reactor employed was a2 liter stainless steel autoclave equipped with a mechanical stirrer. For the experimental run, the reactor was first dried for 1 hour, 200g of NaCl was added and dried by heating at 100℃for 30 minutes under nitrogen. After baking the reactor, 5g of SMAO (silica supported methylaluminoxane) was introduced under nitrogen pressure as scavenger. After addition of SMAO, the reactor was sealed and the components were stirred. The reactor was then charged with hydrogen (2.50L) and hexene (c6/c2=0.004), then pressurized with ethylene (c2pp=230 psi). Once the system reaches steady state, the catalyst is charged to the reactor at 80 ℃ or 100 ℃ to begin polymerization. The reactor temperature was raised to 100 ℃ and maintained at that temperature, and hydrogen (H2/c2=0.004) and comonomer (c6/c2=0.004) feeds were provided throughout the 3 hour run. At the end of the run, the reactor was cooled, vented and opened. The resulting product mixture was washed with water and methanol and then dried. The polymerization productivity (grams polymer/gram catalyst) is determined as the ratio of the polymer produced to the amount of catalyst added to the reactor.

Results

As can be seen from Table 4A, CE J and IE 11 have the same catalyst consisting of the same components, the only difference being that IE 11 contains the catalyst IE 9 of the invention having the activity enhancing compound (II-a). For IE 9, the productivity increased by more than 3,000g/g (about 30%). Furthermore, the presence of the activity enhancing compound (II-a) affects the "light-off temperature" of the catalyst of IE 11. Rapid light-off may cause overheating of the particles, which in turn may lead to reactor operability problems (e.g., such as caking, agglomeration, and aggregation on the catalyst feed tube). The heat generated by the catalyst light-off can be measured indirectly by an increase in the internal temperature of the reactor, as is done herein. The highest reactor internal temperature (T _max) of comparative catalyst CE F used in CE J was 121.1 ℃, which was reached within 44 seconds using only 6.4mg of catalyst. In contrast, the T _max of the catalyst IE 9 of the present invention used in IE 11 was 111.4 ℃, with a delay of 74 seconds to reach this temperature with only 5.9mg of catalyst. Another feature of the catalyst IE 9 of the invention used in IE 11 is that although the overall productivity is increased by modification of the high MHW catalyst component, the flow index (I ₂₁) is also increased. This means that there is more LMW polymer component, meaning that in the bimodal catalyst comprising IE 9 of the activity enhancing compound (II-a) of the present disclosure, an indirect impact is exerted on the metallocene component, which also becomes more productive. This is an unexpected result (i.e., the activity enhancing compound (II-a) itself has a negative effect on the metallocene, discussed below for CE L and CE M). in continuous (and commercial) reactors, this will be reflected in a reduction in the amount of conditioning catalyst required, as shown in the above-described inventive examples in tables 3A/3B. A further feature of the catalysts of the invention is that the activity enhancing compounds (II-a) alter the kinetics and lifetime (in relation to light-off) of the catalyst. As shown in FIG. 1, the maximum instantaneous ethylene (C2) uptake of catalyst IE 9 (example IE-11) of the invention is lower compared to CE F (example CE-J). In addition, the ethylene absorption curve for comparative catalyst CE-F decays faster, meaning a shorter lifetime. Thus, the catalyst of the present invention has an extended lifetime. Comparing CE K and IE 12 in table 4A (below), the catalyst IE 10 of the present invention again had increased productivity (about 22%). There is a similar decrease in the flow index (I ₂₁) from 6.7 to 7.4, which means that the production rates of both the HMW and LMW components have increased. In terms of light-off, the T _max of comparative catalyst CE G was 120.3 ℃, whereas the catalyst IE 10 of the invention was only 110.7 ℃. In the case of the present invention, the time to reach T _max is also delayed, with IE 10 used in IE 12 being 65 seconds, and CE G used in CE K being 44 seconds. This can be seen in fig. 2. As mentioned above, the kinetics are also modified by the activity-enhancing compound (II-a), the maximum instantaneous ethylene absorption of CE K and the decay of catalyst activity being greater in both cases (see FIG. 1).

CE L and CE M compared catalysts prepared with the metallocene component alone, one without the activity-enhancing compound (II-a) (CE H) and one with the activity-enhancing compound (II-a) (CE I). The direct use of the activity enhancing compound (II-a) in the metallocene does not positively improve productivity, and in practice productivity is significantly reduced by about 30%. There is only a small difference between Tmax and the time to reach Tmax, which can be explained by the lower productivity of CE I in CE M. In contrast, catalysts IE 9 and IE 10 of the present invention have higher productivity, but lower Tmax, which is counterintuitive because polymerization heat generates reactor/reaction temperature. Thus, it is noted that the effect of the activity enhancing compound (II-a) on bimodal polymer production is very unique. For this purpose, fig. 3 shows the almost identical temperature profile of the two catalysts. FIG. 4 shows ethylene absorption curves, which are also nearly identical, indicating that neither the kinetic effect nor the lifetime benefit from the activity enhancing compound (II-a) directly affects the metallocene. Unexpected results only occur in the special case of bimodal polyethylene compounds with catalyst compound (I) and activity enhancing compound (II-a). A comparison of CE J and IE 12 also illustrates this, since the activity enhancing compound (II-a) was chemically modified and the productivity of the catalyst compound (I) was improved. As can be seen from Table 4A, IE 12 using the IE 10 catalyst has a higher productivity (8,088 g/g vs 7,188) than CE J using the CE F catalyst, although it is a less active catalyst component.

TABLE 4A-results of semi-batch reactor test

The conditions were operating temperature=100 ℃, injection temperature=100 ℃, c6/c2=0.004, h2/c2=0.004, c2pp=230 psi, 3 hours of operation time. The C6 wt% is calculated from the absorption of C2 and C6 consumed during operation.

Referring now to Table 4A/4B/4C, polymer data shows that an increase in productivity affects both catalysts IE 9 and IE 10 of the invention, not just catalyst compound (I) undergoing chemical modification with activity enhancing compound (II-a). The activity-enhancing compound (II-a) also has a secondary effect that the increase in productivity is manifested in a slight decrease in Tm from 131.8℃to 131.2℃and an increase in crystallinity of the resulting polymer as the melting enthalpy (. DELTA.H _m) increases from 134.8J/g to 135.9J/g. Likewise, the Tm of IE 12 decreases (from 132.0 ℃ to 131.4 ℃) compared to CE K. The crystallinity of IE 12 is also increased (Δh _m =152.2J/g) compared to CE K (Δh _m = 142.4J/g). The weight average molecular weight (Mw) of the polymer from CE J is also reduced compared to IE 11. Also, the Mw from IE 12 is lower compared to CE K. The decrease in both Mz and Mz/Mw is consistent with an increase in polymer from the LMW component.

TABLE 4B Polymer data for semi-batch reactor test

The conditions were operating temperature=100 ℃, injection temperature=100 ℃, c6/c2=0.004, h2/c2=0.004, c2pp=230 psi, 3 hours of operation time.

TABLE 4C Polymer data for semi-batch reactor test

The conditions were operating temperature=100 ℃, injection temperature=100 ℃, c6/c2=0.004, h2/c2=0.004, c2pp=230 psi, 3 hours of operation time. ^[a] The C6 wt% is calculated from the absorption of ethylene and 1-hexene during the reaction. ^[b] C6 wt% from the composition GPC.

Referring now to Table 5A/5B/5C/5D, additional polymer data of the present disclosure is shown. Comparing CE N and IE 13 (same catalyst components, the only difference being the presence of the activity enhancing compound in IE 9), it can be seen that the productivity of catalyst IE 9 of the present invention is increased. The light-off, measured by Tmax of the early reaction, is also slower and slightly delayed. This is shown in fig. 5. The increase in the flow index (I ₂₁) of IE 9 means that the metallocene component also sees a bimodal increase in productivity, as well as an indirect effect on the metallocene (CE P and CE Q show a negative effect on productivity when only the metallocene and the activity enhancing compound are under these conditions). The kinetics are also positively influenced, the catalyst IE 9 of the invention has a lower initial ethylene uptake, a slower activity decline, and a longer catalyst life. CE G and IE 10 in CE O and IE 14 again show similar trends. In summary, the catalyst IE 10 of the present invention has higher productivity, lower light-off temperature, higher I ₂₁. Dynamics are also positively affected, with lower initial ethylene absorption but slower decay and longer catalyst life. Comparing IE 10 of IE 14 with comparative CE F of CE N, the catalyst IE 10 of the present invention uses 20% less compound (I), but still has higher productivity due to the presence of the activity enhancing compound of the present invention.

Table 5A semi-batch reactor test results

The conditions were operating temperature=100 ℃, injection temperature=80 ℃, c6/c2=0.004, h2/c2=0.004, c2pp=230 psi, 3 hours of operation time. The C6 wt% is calculated from the absorption of C2 and C6 consumed during operation.

Table 5B semi-batch reactor test results

The conditions were operating temperature=100 ℃, injection temperature=80 ℃, c6/c2=0.004, h2/c2=0.004, c2pp=230 psi, 3 hours of operation time. The C6 wt% is calculated from the absorption of C2 and C6 consumed during operation.

Table 5C semi-batch reactor polymer data

The conditions were operating temperature=100 ℃, injection temperature=80 ℃, c6/c2=0.004, h2/c2=0.004, c2pp=230 psi, 3 hours of operation time. ^[a] The C6 wt% is calculated from the absorption of ethylene and 1-hexene during the reaction. ^[b] C6 wt% from the composition GPC.

Table 5D semi-batch reactor polymer data

The conditions were operating temperature=100 ℃, injection temperature=80 ℃, c6/c2=0.004, h2/c2=0.004, c2pp=230 psi, 3 hours of operation time. ^[a] The C6 wt% is calculated from the absorption of ethylene and 1-hexene during the reaction. ^[b] C6 wt% from the composition GPC.

TABLE 6 semi-batch reactor ethylene flow and uptake data (corresponding to TABLE 4A)

The conditions were operating temperature=100 ℃, injection temperature=100 ℃, c6/c2=0.004, h2/c2=0.004, c2pp=230 psi, 3 hours of operation time. ^[a] The C6 wt% is calculated from the absorption of ethylene and 1-hexene during the reaction. ^[b] C6 wt% from the composition GPC. Ethylene uptake was measured in standard liters per minute (slpm) during operation, with an ethylene flow of 1.252g/L.

Table 6 quantifies the ethylene uptake of the catalyst measured during the semi-batch reactor test method. For the catalysts of the invention prepared with an Activity Enhancing Compound (AEC), the maximum C2 uptake achieved during the reactor was lower, i.e. <5.3slpm (examples IE 11 and IE 12), whereas the bimodal catalyst without AEC had a much higher maximum ethylene uptake, reaching a maximum detector reading of >10.3 slpm. Higher maximum ethylene absorption also indicates greater light-off, which corresponds to the highest reactor internal temperature as reported in table 4A.

The ethylene absorption of the catalysts of the present invention in examples IE 11 and IE 12 had lower attenuation than comparative examples CE J and CE K, which may be manifested as having higher ethylene absorption at t=0.1 hours, t=0.3 hours and t=0.9 hours, although the maximum ethylene absorption was lower than the comparative examples. The ratio of ethylene absorption to maximum ethylene absorption at each of these time points is reported in table 6 and is given by general equation (I) and specific equations (II) to (IV):

As shown by the ethylene absorption curve, the effect of AEC additives on the productivity-enhanced bimodal catalyst kinetics can be quantified by the additive effectiveness index AIE, which is the ratio of ζ (t) of the productivity-enhanced bimodal catalyst to ζ (t) of the bimodal catalyst without AEC. AEC can be given by general formula (V) and specific formulas (VI) to (VIII):

The additive effectiveness index (AEI (t)) is given in Table 6. The AEI (t) of each of CE J, IE 11, CE K and IE 12 is compared to the AEI (t) of CE J. AIE (t) < 1.5 (near 1) indicated no change in kinetics, as shown by the ethylene absorption curve. AIE (t) >2 showed a significant effect on the kinetics of the catalyst. For catalyst IE 9 of the invention (example IE 11), AEI (0.1), AEI (0.3) and AEI (0.9) were between 2.66 and 3.83. Also, for catalyst IE 10 of the invention (example IE 12), AEI (0.1), AEI (0.3), and AEI (0.9) were between 2.58 and 3.97, the catalyst had 20% less HMW catalyst component (i.e., non-metallocene catalyst component) and 20% less AIC (i.e., 3, 5-difluoro-1-ethynylbenzene). To demonstrate that the kinetic effect (and associated temperature and productivity effects) is not due solely to the reduction in the amount of HMW catalyst component, the AEI (0.1), AEI (0.3) and AEI (0.9) values of the comparative control catalyst CE G (example CE K), which is additive-free and 20% less in the amount of HMW catalyst component, are between 0.71 and 1.12, much less than 1.5.

AEI (t) can also be used to demonstrate that there is no direct kinetic effect on the metallocene LMW catalyst component, as shown in Table 6A for LMW catalyst CE H with AEC additive (example CE L) and LMW catalyst CE I without AEC (example CE M). AEI (0.1), AEI (0.3) and AEI (0.9) were between 0.87 and 1.1 (CE I compared to CE H), indicating no significant kinetic absorption. The lower maximum ethylene uptake of the LMW metallocene with the AEC additive is the result of lower productivity (table 4A), which indicates a slight poisoning effect on the LMW metallocene compound when it was directly mixed with the AEC additive without the HMW catalyst component.

The catalyst life can be quantified by the same semi-batch reactor test as described above. The comparison must be made under equivalent reaction conditions (i.e., the same process conditions such as temperature, molar ratio of ethylene to comonomer, molar ratio of ethylene to hydrogen, ethylene partial pressure, catalyst loading, etc.). The productivity enhanced bimodal catalyst IE 9 (example IE 11) had a longer lifetime than the comparative catalyst CE F (example CE J), quantified by having a lower maximum instantaneous ethylene absorption (i.e. 5.216slpm versus 10.364 slpm) but a higher (i.e. larger) instantaneous absorption value at the reaction time point. Specifically, the productivity enhanced bimodal catalyst had greater uptake at t=0.1 hours (1.892 slpm versus 1.412 slpm), as well as at t=0.3 hours (0.862 slpm versus 0.447 slpm), and vice versa at t=0.9 hours (0.254 slpm versus 0.183 slpm). Likewise, the same productivity enhanced bimodal catalyst IE 10 (example IE 12) can be compared to a comparative bimodal catalyst CE G (example CE K), where the maximum instantaneous ethylene absorption is half that of the comparative, and the ethylene absorption is greater at t=0.1 hours, t=0.3 hours, and t=0.9 hours, as shown in table 6A. The metallocene compounds containing the additives did not have increased lifetime because the instantaneous ethylene absorption was lower at the maximum point and at the 0.1 hour, 0.3 hour and 0.9 hour time points, consistent with somewhat lower productivity and similar decay curves or catalyst lifetimes.

Lifetime can also be expressed as the ratio of the absorption at a given time (t) and is expressed by the greek letter zeta, ζ (t). The larger values of ζ (0.1), ζ (0.3) and ζ (0.9) correspond to longer catalyst lifetimes, as shown by the improved productivity of bimodal catalyst IE 9 (example IE 11) compared to comparative bimodal catalyst CE F (example CE J). As are other embodiments.

Claims (20)

1. A method of preparing a bimodal catalyst with improved productivity, the method comprising:

Combining a non-metallocene pre-catalyst, a metallocene pre-catalyst, an effective amount of an activator for activating the non-metallocene pre-catalyst and the metallocene pre-catalyst, and an effective amount of an activity enhancing compound into the productivity-enhanced bimodal catalyst, wherein the activity enhancing compound has the formula (a):

wherein each of R ⁵、R⁴ and R ³ is independently H, halogen, (C ₁-C₂₀) hydrocarbyl or (C ₁-C₂₀) heterohydrocarbyl, provided that at least one of R ⁵ and R ³ is halogen or haloalkyl, wherein each of R ² and R ¹ is independently H, Halogen, halogen, (C ₁-C₂₀) hydrocarbyl or (C ₁-C₂₀) heterohydrocarbyl, wherein each (C ₁-C₂₀) hydrocarbyl or (C ₁-C₂₀) heterohydrocarbyl is independently unsubstituted or substituted with 1 to 4 substituent groups R ^S; wherein each substituent group R ^S is independently selected from halogen, Unsubstituted (C ₁-C₅) alkyl, -C≡CH, -OH, (C ₁-C₅) alkoxy, -C (=O) - (unsubstituted (C ₁-C₅) alkyl), -NH ₂, -N (H) (unsubstituted (C ₁-C₅) alkyl), -N (unsubstituted (C ₁-C₅) alkyl) ₂、-COOH、-C(=O)-NH₂, -C (=o) -N (H) (unsubstituted (C ₁-C₅) alkyl), -C (=o) -N (unsubstituted (C ₁-C₅) alkyl) ₂, -S- (unsubstituted (C ₁-C₅) alkyl), -S (=o) ₂ - (unsubstituted (C ₁-C₅) alkyl), -S (=o) ₂-NH₂、-S(=O)₂ -N (H) (unsubstituted (C ₁-C₅) alkyl), -S (=o) ₂ -N (unsubstituted (C ₁-C₅) alkyl) ₂, -C (=) S- (unsubstituted (C ₁-C₅) alkyl) and-COO (unsubstituted (C ₁-C₅) alkyl), and wherein the metallocene pre-catalyst has formula (B):

Wherein M is a group 4 element, each X is independently a hydride group, an amide group, a benzyl group, a methyl group, a chloro group, a fluoro group, a methylene (trimethylsilyl) group, a hydrocarbyl group, or a heterohydrocarbyl group, each of R ⁶、R⁷、R⁸、R⁹ and R ¹² is independently a (C ₁-C₁₀) hydrocarbyl group or a (C ₁-C₁₀) heterohydrocarbyl group, and each of R ¹⁰、R¹¹、R¹³、R¹⁴ and R ¹⁵ is independently H, (C ₁-C₁₀) hydrocarbyl group, or a (C ₁-C₁₀) heterohydrocarbyl group.

2. The method of claim 1, wherein each of R ⁵ and R ³ is independently halogen or haloalkyl, each of R ² and R ¹ is H, and R ⁴ is selected from H, hydrocarbyl, halogen, and haloalkyl.

3. The method of claim 1, wherein the activity enhancing compound is 3, 5-difluoro-1-ethynylbenzene:

4. The method of claim 1, wherein one of R ⁵ and R ³ is halogen or haloalkyl and the other is hydrogen.

5. The method of claim 1, wherein the activity enhancing compound is 3-fluoro-1-ethynylbenzene or3, 4-difluoro-1-ethynylbenzene:

Or (b) 。

6. The method of any one of claims 1 to 5, wherein each of R ¹⁰、R¹¹、R¹³、R¹⁴ and R ¹⁵ is H, each of R ¹²、R⁶、R⁷、R⁸ and R ⁹ is (C ₁-C₅) hydrocarbyl, M is Zr, and each X is a chloro group or (C ₁-C₃) hydrocarbyl.

7. The method of claim 6, wherein R ¹² is C ₃ hydrocarbyl, each of R ⁶、R⁷、R⁸ and R ⁹ is C ₁ hydrocarbyl, and each X is a chloro group or a methyl group.

8. The process according to any one of claims 1 to 7, wherein the metallocene procatalyst of formula (B) is selected from the group consisting of compound (1):

;

and compound (2):

。

9. The method of any one of claims 1 to 8, wherein the method further comprises combining the non-metallocene pre-catalyst, the metallocene pre-catalyst, an effective amount of the activator, an effective amount of the activity enhancing compound, a support material, and an inert hydrocarbon solvent to form a mixture, and removing the inert hydrocarbon solvent from the mixture, thereby resulting in the productivity-enhanced bimodal catalyst disposed on the support material.

10. The process of any one of claims 1 to 9, wherein the non-metallocene pre-catalyst is a non-metallocene pre-catalyst of formula (C)

Wherein M is a group 4 element, each of R ⁶ to R ¹³ is independently hydrogen or a methyl group, ar is an aryl group or a substituted aryl group, ar' is an aryl group or a substituted aryl group, and each X is independently a hydride group, an amide group, a benzyl group, a methyl group, a chloro group, a fluoro group, a methylene (trimethylsilyl) group, a hydrocarbyl group, or a heterohydrocarbyl group.

11. The process of any one of claims 1 to 10, wherein the non-metallocene pre-catalyst of formula (C) is compound (3):

wherein each X is independently a hydride group, an amide group, a benzyl group, a methyl group, a chloro group, a fluoro group, a methylene (trimethylsilyl) group, a hydrocarbyl group, or a heterohydrocarbyl group.

12. The process of claim 11, the non-metallocene pre-catalyst of formula (C) is compound (4):

。

13. The method of any one of claims 1 to 12, wherein the metal of the non-metallocene pre-catalyst is M, wherein the activator is an organoaluminum compound, and wherein the effective amount of the activator is an Al/M molar ratio of 0.5 to 10,000, alternatively 0.95 to 200, alternatively 1.0 to 150, alternatively 10 to 100, and/or wherein the effective amount of the activity enhancing compound comprises an activity enhancing compound to non-metallocene pre-catalyst molar ratio (AEC/NMC molar ratio) of 0.2:1.0 to 50.0:1.0, alternatively 0.9:1.0 to 20.0:1.0, alternatively 0.9:1.0 to 11:1.0, alternatively 0.95:1.0 to 6:1.0, alternatively 0.95:1.0 to 1.2:1.0.

14. The process of any one of claims 1 to 13, comprising using the metallocene pre-catalyst of compound (2):

as a conditioning catalyst.

15. A productivity-enhanced bimodal catalyst prepared by the method of any one of claims 1 to 14.

16. A method of feeding a productivity-enhanced bimodal catalyst into a slurry, solution or gas phase polymerization reactor containing olefin and a moving bed of polyolefin polymer, the method comprising preparing the productivity-enhanced bimodal catalyst according to the method of any one of claims 1 to 14 outside the reactor, and feeding the productivity-enhanced bimodal catalyst in pure form or in solution or slurry in an inert hydrocarbon liquid or mineral oil into the slurry, solution or gas phase polymerization reactor through a feed line free of olefin monomer.

17. The method of claim 18, further comprising pre-catalyst the metallocene of compound (2):

Use of a bimodal catalyst as a conditioning catalyst with an increased productivity according to any one of claims 1 to 12 in a slurry phase, solution phase or gas phase polymerisation reactor.

18. The catalyst of the process of any one of claims 16 to 17 such that the productivity enhanced bimodal catalyst has a reduced regulated catalyst requirement compared to a bimodal catalyst without an activity enhancing compound, which can be measured in a continuous process by a reduced regulated catalyst molar amount relative to the base catalyst or by an increased activity in lb PE/mol of the low molecular weight metallocene catalyst, which is also accompanied by an increased activity in lb PE/mol of the high molecular weight non-metallocene catalyst.

19. The method of any one of claims 17 to 19, further comprising using a continuity additive with the productivity-enhanced bimodal catalyst in the slurry, solution, or gas phase polymerization reactor.

20. The process of any one of claims 1 to 19 using an activity enhancing compound to prepare a bimodal catalyst with increased productivity such that kinetics are improved, as measured by a semi-batch reactor test method, as a decrease in the maximum reactor temperature, or independently as measured by an activity enhancing index, AEI, as shown in formula (I):

The AEI can be measured by the semi-batch reactor test described in the examples, and t is the time of the batch reactor test in hours, ζ (t) is the measured ethylene uptake or consumption of the catalyst, and additive catalyst is the bimodal catalyst with increased productivity, and additive-free catalyst is the bimodal catalyst without the activity enhancing compound, and AEI (0.3) is the activity enhancing index at 0.3 hours, and AEI (0.3) > 2.0, alternatively AEI (0.3) > 3.0.