WO2007103571A2

WO2007103571A2 - Nucleating agent additive compositions and methods

Info

Publication number: WO2007103571A2
Application number: PCT/US2007/006099
Authority: WO
Inventors: Weihua Sonya Wolters; Robbie Willem Johan M. Hanssen; Thaneerpandal K. Palanisami; Darin L. Dotson
Original assignee: Milliken and Co
Current assignee: Milliken and Co
Priority date: 2006-03-08
Filing date: 2007-03-08
Publication date: 2007-09-13
Anticipated expiration: 2008-09-08
Also published as: EP1991612B1; CN101400729A; WO2007103571A3; US20070213439A1; EP1991612A2; BRPI0708653A2; US7659336B2; BRPI0708653B1; ATE452934T1; CN101400729B; DE602007003960D1

Abstract

A blend of two different compounds may be applied together to form a nucleating agent additive composition. This additive composition is useful as an additive in thermoplastics, polyolefins and/or polymer resins. A blend of of a bicyclo[2.2.1] heptane dicarboxylate salt and a dicarboxylate calcium metal salt provide useful and beneficial physical property effects in molded polymeric articles in terms of shrinkage and cryatallization temperature of polymer resin compositions.

Description

Title of the Invention

NUCLEATING AGENT ADDITIVE COMPOSITIONS AND METHODS Background of the Invention

5 [0001] Nucleating agents are employed as additives in polymer resin in the manufacture of plastic articles. Such manufacture may be by various methods, including by injection or extrusion molding.

[0002] Solid bicyclo[2.2.1]heptane dicarboxylate salt-containing io thermoplastic nucleating additives are known. One commercially useful nucleating agent sold by Milliken & Company of Spartanburg, South Carolina is Hyperform® HPN-68L. This nucleating agent is of the chemical structure below:

[0003] Hyperform® is useful in manufacturing plastic articles. It enables 0 the polymer to achieve a significant cycle time reduction in the molding process compared to using non-nucleated polypropylene ("PP"). Cycle time reduction can be achieved in part by inducing in the resin a higher T_c (crystallization temperature), which enables the molten resin to harden at higher temperature. This decreases the necessary cooling time and facilitates ejection of the articles 25 from the mold at a faster rate than would be possible without the use of a nucleating agent. A common defect in a process as injection molding is deformation of the molded part as a result of different stresses caused, by polymer orientation. Longer mold residence time is needed to stiffen the material to such an extent that it can withstand these stresses and inhibit the deformation. 30 Cycle time can thus also be reduced by optimizing the shrinkage properties of polypropylene by adjusting the orientation of the polymer crystals by a nucleating agent. Nucleating agents that adjust the shrinkage to be more isotropic, i.e. shrinkage in the machine direction becoming equal to shrinkage in the transverse direction are favorable for reducing cycle time where deformation is the limiting factor in the molding process. Cycle time is very important in the economic viability and profitability of molded part manufacture.

[0004] United States Patent Numbers 6,465,551; 6,562,890; and

6,995,202 disclose dicarboxylate metal salt compositions.

[0005] The use of clarifying agents to reduce haze in articles manufactured from crystalline polyolefin resins is known. Some compounds may serve as both nuceating agents and clarifying agents. Representative acetals of sorbitol and xylitol, which have been employed as clarifying agents, are disclosed generally in the Rekers, United States Patent No. 5,049,605, bis(3,4- dialkylbenzylidene). Among clarifiers based on diacetals of sorbitol and xylitol, Millad 3988® is a commercially successful clarifier for polypropylene. It is a dimethyl substituted dibenzylidene sorbitol ("DMDBS"), 1,3:2,4-bis (3,4 dimethyl benzylideπe sorbitol). Millad 3988® is manufactured and distributed by Milliken & Company of Spartanburg, South Carolina.

[0006] Milliken & Company commercially sells a nucleating agent product known as Hyperform® HPN-20E which employs a calcium metal ion, this compound having the chemical structure:

¹ [0007] Other known compounds useful for nucleation include sodium 2,2'- methylene-bis-(4,6-di-tert-butylphenyl) phosphate (from Asahi Denka Kogyo K.K., known commercially as NA-11®), as shown below:

Such compounds all impart high polyolefin crystallization temperatures; however, each also exhibits its own drawback for large-scale industrial applications. United States Patent Nos. 4,463,113 and 5,342,868 disclose crystalline synthetic resin compositions of cyclic organophosphoric esters. 10008] When a polymer is melted into a thermoplastic article, the force applied in shaping the article creates stress in the article. Polymers typically have long chains and long relaxation times, therefore residual stress exists in such plastic articles. The residual stress will release after the article is shaped which manifests as shrinkage of the article. Generally when a nucleating agent is added, because of short cooling time, the orientation and residual stress from molding process are maintained. Plastic articles with nucleating agents typically have higher shrinkage than articles without nucleating agent. Sometimes there is too much shrinkage and the plastic articles are out of dimensional specifications. To manufacture parts that meet the dimensional specifications, some companies have tried to decrease shrinkage by adding impact modifying compositions or talcum.

[0009] A nucleating agent for polypropylene with a combination of positive material properties, like high Tc, low crystallization half time (t^),, isotropic shrinkage, and high stiffness would be highly desirable. Phosphate ester salts, like NA-11® and NA-21® (manufactured by Asahi Denka Kogyo Kabushiki Kaisha of Japan) are known to incur relatively high stiffness in injection molded articles. However, warpage caused by anisotropic shrinkage is often an undesired side effect of such materials. Such warpage is a disadvantage of using phosphate esters.

[0010] Each nucleating composition has its advantages and disadvantages. This has created a long-felt need in the polyolefin nucleator compound industry to provide compositions that minimize such problems and provide excellent peak crystallization temperatures for the target polyolefin. Unfortunately, it is a significant challenge to find nucleators exhibiting exceptionally high peak crystallization temperatures, low hygroscopicity, excellent thermal stability, high stiffness, and relatively low amounts of shrinkage or warpage in finished articles.

[0011] Blends of more than one nucleator used together have been tried, but are not always successful. Furthermore, this is a highly unpredictable area of the chemical arts, and there is usually no any way of knowing what will be effective until it is tried, and tested, and a relatively substantial amount of work is done.

[0012] United States Patent No. 6,586,007 is directed to a combination of

3,4 - dimethylbenzylidene sorbitol (DBS) and p-methylbenzylidene sorbitol (mDBS). U.S. Patent Nos. 6,521,685 and 6,585,819 are directed to additives that comprise a blend of (a) bicyclic salts, and (b) benzylidene sorbitol acetals.

[0013] A commonly owned application assigned to Milliken and Company is United States Serial Number 11/078,003 to Hanssen. This application is directed to a blended nucleating or clarifying composition for thermoplastics comprising a blend of more than one species of nucleating agent, the blend comprising: (a) a first nucleating agent of a carboxylic acid salt compound; and (b) a second nucleating agent of a phosphate-containing salt compound. [0014] A nucleating agent additive composition that could achieve the remarkable advantage of cycle time reduction for molding processes and also exhibit little shrinkage as compared to current commercial systems would be very desirable, so that the nucleating agent could be easily used by thermoplastic manufacturers. This invention is directed to such a composition and methods for its use in the manufacture of polymeric articles. A nucleating agent composition that afford these advantages is desirable.

Brief Description of the Drawings

The following drawings are provided:

[0015] Figure 1 shows behavior of Compound I (commercial compound

HYPERFORM® HPN-68L) when combined with another nucleating agent sodium benzoate;

[0016] Figure 2 illustrates plaque shrinkage behavior using blends of the invention;

[0017] Figure 3 reveals shrinkage data for blends of Compound I and

Compound Il at 500 ppm in homopolymer;

[0018] Figure 4 shows shrinkage data for blends of Compound I and

Compound Il at 1000 ppm in homopolymer; [0019] Figure 5 shows half time data for such blends;

[0020] Figure 6 shows additional shrinkage data;

[0021] Figure 7 illustrates Tc data for various blends at different concentration levels;

[0022] Figure 8 illustrates flexural modulus data; [0023] Figure 9 indicates shrinkage data for such blends; and

[0024] Figure 10 provides further shrinkage data at different loading levels. Detailed Description of the Invention

[0025] Reference now will be made to the embodiments of the invention, one or more examples of which are set forth below. Each example is provided by way of explanation of the invention, not as a limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in this invention without departing from the scope or spirit of the invention.

[0026] In one aspect of the invention, it has been found that a blend of two different compounds may be applied together to form a nucleating agent additive composition. This additive composition is useful as an additive in thermoplastics, polyolefins and/or polymer resins.

[0027] That is, in one embodiment the invention is a blend of bicyclo[2.2.1]heptane dicarboxylate salt (Hyperform® HPN-68L), i.e. "Compound

Compound I

with the calcium metal salt (Hyperform® HPN-20E), i.e. "Compound II" as shown below:

mpound II

This blend or mixture of these two compounds has been found to provide unexpected results in the nucleation of polymers. Unexpected results have been achieved by using them together to nucleate a polyolefin composition. Physical properties of the resulting molded articles are quite beneficial.

[0028] The composition formed by blending the Compound I with

Compound II, and applying the resulting mixture into a polyolefin, addresses the problem of too much shrinkage in injection molded parts while keeping a high T₀ (potential for cycle time reduction). Further, the parts retain good mechanical properties.

[0029] When mixing Compounds I and II, the nucleated polyolefin article still maintains a relatively short crystallization half time and short cycle time, but the article has significantly less shrinkage than using Compound I alone. This finding is unexpected.

[0030] Compounds I is known as an excellent nucleator and even

"overrides" other nucleators, such as sodium benzoate or other pigment nucleators. That is, it is commonly believed that Compound 1 , when mixed with other nucleating agents, typically provides results in which the behavior of the mixture appears to be much more like Compound I, and very little like the other mixed in nucleating agent. Thus, it may be said that Compound I is believed to "override", or dominate, other nucleating agents when used with other nucleating agents. Figure 1 shows that when Compound I is mixed with sodium benzoate (NaBz), for example, the injection-molded plaque shows the physical property of having Compound I alone, and the presence of NaBz has very little if any effect. This is known as Compound I "overriding" the sodium benzoate. Figure 1 shows the machine direction and transverse direction shrinkage of NaBz and Compound I and blends of NaBz with Compound I in the ratios indicated in the Figure 1. Compound I is known commercially as HYPERFORM® HPN-68L. [0031] In the practice of the invention, however, when mixing Compound It with Compound I₁ physical properties such as shrinkage or Tc of the injection- molded plaque unexpectedly show both the effect of both Compound I and Compound II. Compound I unexpectedly does not override Compound II, which is unexpected given the common understanding of the behavior of

Compound I when mixed with other nucleating agents. One possible reason or theory for this effect is that Compound I orients the b-axis of polypropylene in a different direction than Compound II. However, it is not known if that is in fact the technical cause of the effect, and the invention is not limited to any particular mechanism or action. Because of their unique nucleation and orientation feature, Compound I and Compound II, when combined, do not interfere each other therefore Compound I does not override Compound II, when provides very beneficial results in the practice of the invention.

[0032] The invention is made, in one embodiment, by adding Compounds

I and Il to polypropylene via one of several possible techniques:

1) Addition of nucleating agent powders in various ratios to PP reactor grade resins together with other additives (such as antioxidants and acid scavengers). This combination of materials is then melt-compounded, and subsequently used in a process such as injection molding, sheet extrusion, thermoforming, extrusion blow molding, injection stretch blow molding or film extrusion.

2) Addition of nucleating agent powders in various ratios to PP compounded material together with other additives (such as antioxidant and acid scavengers). This combination of materials is then melt-compounded, and subsequently used in a process such as injection molding, sheet extrusion, thermoforming, extrusion blow molding, injection stretch blow molding or film extrusion.

3) Addition of a combination of a concentrate (masterbatch) and nucleating agent powder in various ratios to either reactor material or compounded material together with other additives. This combination of materials is then melt- compounded, and subsequently used in a process such as injection molding, sheet extrusion, thermoforming, extrusion blow molding, injection stretch blow molding or film extrusion.

4) Addition of a two separate concentrates ("master batches") in various ratios to either reactor material or compounded material together with other additives. This combination of materials may be melt-compounded, and subsequently used in a process such as injection molding, sheet extrusion, thermoforming, extrusion blow molding, injection stretch blow molding or film extrusion.

5) Addition of a combined masterbatch of both nucleating agent Compounds I and Il to a compounded resin. This material may be subsequently used in a process such as injection molding, sheet extrusion, thermoforming, extrusion blow molding, injection stretch blow molding or film extrusion.. A melt- compounding step between addition of the combined master batch and injection molding is yet another option.

[0033] As used herein, the term "thermoplastic" refers generally to a polymeric or polymer material that will melt upon exposure to sufficient heat but will retain its solidified state upon cooling. "Thermoplastic" is used interchangeably herein with "polymer", or "polymeric". Thermoplastic refers to plastics having crystalline or semi-crystalline morphology upon cooling after melt-formation, usually by the use of a mold or like article. Particular types of polymers contemplated within such a definition include, without limitation, polyolefins (such as polyethylene, polypropylene, polybutylene, and any combination thereof), polyamides (such as nylon), polyurethanes, polyester (such as polyethylene terephthalate), and the like (as well as any combinations thereof).

[0034] Thermoplastics have been utilized in a variety of end-use applications, including storage containers, medical devices, food packages, plastic tubes and pipes, shelving units, and the like. Such base compositions, however, must exhibit certain physical characteristics in order to permit widespread use. Specifically within polyolefins, for example, uniformity in arrangement of crystals upon crystallization is a necessity to provide an effective, durable, and versatile polyolefin article. In order to achieve such desirable physical properties, it has been known that certain compounds and compositions provide nucleation sites for polyolefin crystal growth during molding or fabrication. Generally, compositions containing such nucleating compounds crystallize at a much faster rate than un-nucleated polyolefin. Such compounds and compositions that provide faster and or higher polymer crystallization temperatures are popularly known as nucleators. Such compounds provide nucleation sites for crystal growth during cooling of a thermoplastic molten formulation.

Example 1

[0035] Mixing Compounds I and Il for reduced shrinkage. When mixing

Compounds I and II, the machine direction ("MD") and transverse direction ("TD") shrinkage decreases. The shrinkage isotropy improves. The effect is dependent on the types of acid scavengers that are employed. This may be seen in Figure 2.

Example 2

[0036] Lower loadings of Compound I and Compound Il mixture. This example shows that when mixing Compounds I and II, the MD and TD shrinkage decreases, while the shrinkage isotropy improves. Shrinkage may be seen in Figures 3 and 4. Further, the crystallization half time decreases, as seen in Figure 5. The crystallization half time plot with different mixing ratio shows that when mixing a small amount of Compound Il with Compound I₁ the half time does not increase appreciably — but the shrinkage decreases significantly. This is unexpected, and quite beneficial.

[0037] The results indicate that it is possible to add this nucleator blend of

Compound I and Compound Il to a mixture to polyolefins — and thereby improve the article manufacturing cycle time, improve (decrease) warpage — and yet still keep the article dimension within specifications. This is unexpected, and very beneficial.

[0038] The addition of Compound Il to a constant concentration of 500 ppm Compound I has a strong effect on decreasing shrinkage in both machine and transverse directions — while the crystallization temperature remains high. These results are shown in Figure 6.

Example 3

[0039] The results show that mixtures of Compound Il and Compound I retain high Tc's with low relative content of Compound I. Lowering the relative content of Compound I may increase the flexural modulus of manufactured parts by almost 100 MPa. Reference is made to Figures 7 and 8.

Example 4

[0040] Master batches (5%) of Compound II; 5% of Compound I; and combination of both nucleators {in ratios of 3:1, 1:1 and 1:3) were prepared on a Leistitz twin-screw extruder. These master batches were letdown (@ 1 %) in an impact-copolymer polypropylene (Sabic 56M10 with a Melt Flow Rate (MFR) of about 6. Shrinkage, flexural modulus and peak crystallization temperature were measured and recorded in Figure 9. Also, reference is made to Table 1.

Table 1: Physical Properties of Resin Compositions with Nucleating Agents Versus Control Compositions

Compound MD shrinkage TD shrinkage Isotropy Tc ti/2 Flexmod (%) stdev (%) stdev (-) stdev (⁰C) minutes (MPa)

Control 1.060 0.010 1.720 0.024 0.610 0.012 1 10.6 13.22 1 191 Cmpd II only 1.000 0.020 1.550 0.037 0.640 0.020 1 16.9 2.82 1285

75/25 of Cmpd Il/l

1.070 0.010 1.750 0.028 0.610 0.012 1 17.9 2.40 1290

50/50 Cmpd ll/l

J .140 0.020 1.840 0.026 0.620 0.014 1 17.8 2.23 1279

25/75 Cmpd I I/I

1.150 0.010 1.840 0.020 0.620 0.010 119.5 1.53 1261

Cmpd I only 1.250 0.010 1.880 0.018 0.670 0.010 120.1 1.32 1250

[0041] In this system, the difference in Tc between the 3:1 mixture of

Compound Il to Compound I (i.e. "Cmpd ll/l" above) and 100% Compound I is about 2 degrees C. Further, the shrinkage of the 3:1 mixture of Compound I I/Compound I is almost the same as unnucleated ICP PP. The Tc of the 3:1 mixture is still almost 7.5 ⁰C higher than unnucleated ICP PP, offering significant potential for cycle time reduction. This shows the unexpected and useful results of the blends of the invention. The mechanical properties of the material are slightly improved when higher relative amounts of Compound Il are used.

Example 5 [0042] The shrinkage reduction effect also works at very high concentrations, as further shown in Figure 10. The addition of 2000 ppm of Compound Il to PP nucleated with 2000 ppm Compound I causes a shrinkage reduction of 0.1% in the machine direction and 0.2% in the transverse direction. [0043] It is understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention, which broader aspects are embodied in the exemplary constructions. The invention is shown by example in the appended claims.

Claims

Claims:

1. A nucleating composition for thermoplastics comprising: (a) a first nucleating agent as shown

and

(b) a second nucleating agent as shown:

2. A thermoplastic resin composition comprising the composition of claim 1.

3. A thermoplastic article comprising the resin composition of Claim 2.

4. A method of making a molded polymeric article, said method comprising the steps of:

(a) providing a polyolefin composition comprising at least a first and second nucleating agent in said composition, wherein said first nucleating agent is comprised of:

and said second nucleating agent is comprised of:

(b) molding said polyolefin composition to form an article.