JPH04500830A - Production method of magnesium oxide-supported Ziegler catalyst modified with acid and higher alkanol and HDPE with narrow molecular weight distribution - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Magnesium oxide-supported Ziegler catalyst modified with acid and higher alkanol and Production method of HDPH with narrow molecular weight distribution Light plate■back amount High-density ethylene homopolymers and copolymers with higher olefins (IIDP E) is widely used in injection molding operations. Preferably, the resin has a narrow molecular weight distribution. (MWD), which is determined mainly by the properties of the catalyst. Applicable Catalysts must also exhibit other properties desirable for industrial applications, such as For example, catalyst productivity may be affected as the resin has a high ratio of polymer to catalyst residue. The particle size of the catalyst should be as high as possible, and the catalyst should be It is also highly desirable to produce, the advantages of which are particularly demanded in gas phase polymerizations. . Slight increase in the amount of hydrogen used in the reactor (to control molecular weight by known methods) high hydrogen response means to add eans) with a significant reduction in molecular weight and high melt index polymers. However, the need for an excess of hydrogen may be due to the use of ethylene and other comonomers. This reduces the reactor volume and therefore productivity.

U.S. Pat. No. 4,167.493 discloses a high-density polyamide resin with a narrow MWD suitable for injection molding. Titanium compounds and aluminum are used to create Ziegler catalysts that produce ethylene. Before impregnation with magnesium compound, magnesium oxide was dissolved in methanol and Lewis base. Processing is disclosed.

Production of high-density polyethylene with narrow molecular weight distribution using magnesium oxide supported catalyst Also disclosed in US Pat. No. 4,288,578. The catalyst of the patent is tetrachloride A mixture of titanium and tetrabutyl titanate, then an organoaluminum compound Manufactured by impregnating a magnesium oxide support with a reducing agent.

According to the present invention, the MgO supported catalyst is treated with an organic acid (Lewis acid), and then Ti(l Treated with the product of Jm and higher alkanol, and finally treated with organic aluminum as a reducing agent. treated with um compounds. The catalyst has a narrow molecular weight distribution and large particle size, which improves productivity and It is particularly suitable for producing HDPE with excellent hydrogen and hydrogen response.

Magnesium oxide is treated with an organic acid and then treated with 0.5 to 1.5 moles of alkanoic acid. and 1 mol of the product of TiCJa, and after i, the organic Treat with aluminum compounds.

The catalyst comprises ethylene polymers and copolymers with narrow MklD and large particle size; It is especially used in the polymerization of HDPH.

The first treatment with an MgO-supported organic acid is carried out using an excess of MgO. organic The acid to MgO ratio is preferably between 0.001 and 0.5, most preferably 0. ．． 005 to 0.1.

Organic acids include aliphatic monocarboxylic acids, aromatic monocarboxylic acids, aliphatic dicarboxylic acids, and or aromatic dicarboxylic acids are preferable.

Suitable aliphatic monocarboxylic acids have the formula R-COOII, where R11H1 carbon atom is an alkyl group having 1 to 17 carbon atoms, or a substituted alkyl group having 1 to 17 carbon atoms For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid , caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, or Stearic acid, preferably formic, acetic or propionic, with acetic acid being most preferred. Delicious.

Suitable aromatic monocarboxylic acids include benzoic acid and alkyl- or alkoxy-substituted amino acids. Zozoic acid, such as 〇-toluic acid, m-toluic acid, P-)ruic acid, 0-eth quinbenzoic acid, m-ethoxybenzoic acid, or p-ethoxybenzoic acid (the latter 3 -ethoxybenzoic acid, 2-ethoxybenzoic acid, or 3-ethoxybenzoic acid, respectively] 0-ethoxybenzoic acid, P-ethoxybenzoic acid or P-ethoxybenzoic acid is preferred, and p-ethoxybenzoic acid is most preferred.

Suitable aliphatic dicarboxylic acids include nouric acid, malonic acid, succinic acid, glutaric acid, These are dipic acid, maleic acid, and dimaric acid.

Suitable aromatic dicarboxylic acids are phthalic acid, isophthalic acid and terephthalic acid. .

Nucleic acids are typically dissolved in an inert organic solvent such as hexane, in which the NGOs are reduced. Let it flow.

After drying, the acid-treated MgO support is again treated with a Schiff 12 alkali having no 5 carbon atoms. The ratio of canol or polyhydroxyalkanol is 0.5 to 1.5 mol of product, preferably 0.8 to 1.2 mol.

After washing and drying, the treated MgO-based catalyst precursor is converted into organoaluminium. The compound is activated by known methods. Particularly suitable aluminum compounds are of the formula R ,,A/Xts-,,+ (wherein R is alkyl, alkenyl, alkylary or aryl alkyl having 1 to 20 carbon atoms, and X is hydrogen or is halogen and n is 1, 2 or 3). R has 1 to 6 carbon atoms Compounds that are alkyl are preferred.

Ethylene can be homopolymerized by any suitable method using the catalyst prepared according to the present invention. or copolymerized with higher olefins. The method involves making %IJ and dissolving There are polymerization methods that are carried out in the vapor phase or in the gas phase. Gas phase polymerization reactions, e.g. stirred reactors, Particularly preferred is a polymerization reaction carried out in a fluidized bed reactor.

The molecular weight of the polymer can be controlled by known methods using hydrogen. present invention The polymerization is carried out at a relatively low temperature, e.g. When carried out with C, the molecular weight can be suitably controlled using hydrogen. this Molecular weight control is achieved through a measurable positive melt index (I2) of the resulting polymer. This can be proven by the change in .

The molecular weight distribution (MWD) of the polymer produced using the catalyst of the present invention is Since it is expressed as the low ratio (?IFR) value (If, /12), the density is 0.940 from about 20 to about 32 for HDPE products of from 0.965 g/cc to about 32 , preferably varies from 21 to 29.

As those skilled in the art will appreciate, such MFR values are determined by the relatively narrow molecular weight distribution of the polymer. This indicates that it is narrow. As also known to those skilled in the art, such MF Polymers with RM exhibit relatively little warpage and shrinkage when the injection molded product is cooled. The MFR value is indicative of the polymer's Vf suitability for injection molding.

Catalysts prepared in accordance with the present invention are extremely active, typically producing 830 ethylene per hour. 1,000 polymer per gram of catalyst per kPa (120 psi) It has an activity of 5,000 grams.

The linear polyethylene polymer produced according to the present invention is a homopolymer of ethylene. or ethyl/one and one or more C, -C. . Copolymers with alpha olefins - can be. Therefore, copolymers with two monomer units are possible. Terpolymers with not only three monomer units are also possible. the polymer Specific examples of ethylene/1-butene copolymer = 1 ethylene/1-hexene Copoly”7-, ethylene/1-octene copolymer, ethylene/4-methyl-1 -Pentene copolymer, ethylene/1-butene/1-hexene copolymer, ethyl ethylene/propylene/1-hexcenter polymer and ethylene/propylene/1 If propylene is used as a comonomer, there is a butene terpolymer. The linear low density polyethylene polymer comprising preferably at least at least one having at least 4 carbon atoms in an amount of 1 percent by weight Contains other alpha olefin comonomers. The most preferred comonomer is 1 -Hexene.

A significant industrial advantage of the catalyst of the present invention is that it is The advantage is that it produces polymers with relatively large particle sizes, larger than 100 yen.

Particularly desirable for producing polyethylene polymers and copolymers according to the present invention The method is a fluidized bed reactor. The reactor and its means of operation are described in Levine et al. U.S. Pat. No. 4,011,382; Karol et al., U.S. Pat. No. 4.011,382; 302, No. 566, and U.S. Pat. No. 4,481,301 to Nowlin et al. It is.

The present invention is illustrated by the following non-limiting examples (all parts are omitted unless otherwise indicated). unit of quantity).

Example 1 (Merck-M Aglite D) 500a! ! In a three-necked flask, the stirred cell was placed in a nitrogen atmosphere. It was dried at 250'C for 16 hours. 3068 grams of this dry MgO support is then Slurried in 2001 Il of dry hexane in a 500 paper three-necked flask. , glacial acetic acid (99.8% purity acetic acid) with a molar ratio of acid to MgO of 0.01 0.44 11Il! The mixture was refluxed for 16 hours. In another flask dry hexane 45- Add 53.5 m (0.494 mol) of pre-dried 1-pentanol to the pen. Tanol diluted? Eight liquids were prepared. 54. To avoid severe fever. , ld net TiCZ4 (0.494 mol) was added dropwise to the 1-pentanol solution. A compound solution was prepared. Treat the solution with acetic acid (1:1 pentanol/T) at room temperature. Reason? Added immediately to IgO. The slurry was rapidly cooled by refluxing at 70°C for 15 hours. .

The catalyst precursor was washed 6 times with 100 d of dry hexane. Solids are dried for 200 d. Reslurried with dry hexane and 25% tri-n-hexyl aluminum ( TIIHAI,) solution 12d (7.66 mmol TNHAL) was gradually added. , 11//Ti ratio of 0.23 was prepared. Do not pass nitrogen through the catalyst6 After drying at 5°C for 16 hours, a smooth light brown powder was obtained. Elemental analysis results , the final catalyst was found to contain 1.1 mmol/g Ti.

implementation drunkenness 21 ki-riyl (J9L1Sl-2 = engineering l = 5-2nd 2) 1 in 13 e-ni-no b3 　Pεji, V ``[''-2! 731j illba ζ3 and tmilo, 8 grams of shame 0 Body sample (Merck-Maglite D) was placed in a 100i Shusink flask. , and dried at 250'C in a nitrogen atmosphere for 16 hours without stirring. Next, add MgO carrier Slurried in 601d dry hexane in a 100d Shusink flask. , 0.26 d of 2-ethoxybenzoic acid (2-ERA) was added to give 0.01 2- 11.8 m of pre-dried 1- as EBA/MgO molar ratio to be refluxed for 2 hours Pentanol (0.109 mol) was added to another flask of dry hexane IO- A dilute pentanol solution was made. To avoid sudden heat generation, 12d pure Ti Add C/, (0.109 mol) drop by drop to the 1-pentanol solution, The (1.:I pentanol/TiCf.) solution was prepared immediately. It was added to 2-EBA-treated MgO at room temperature. The slurry was refluxed at 70°C for 16 hours. and cooled.

The catalyst precursor was washed six times with 60 molar dry hexane. 60m of solids! dried heki Reslurried with San, 26% tri-hexyl aluminum with 2.64+d TNWA+.) fi (1.636 mmol TNHAL) was gradually added. , a catalyst with an AI/Ti ratio of 0.25 was produced.

The catalyst was dried at 70°C for 16 hours under nitrogen to form a free-flowing dark brown powder. I got the end. As a result of elemental analysis, the final catalyst contains 1.34 mmol/g of Ti. I understand.

implementation side 22M of fire and revenge 11.9 grams of MgO (Merck Maglite D-J824) It was dried for 16 hours at 250° C. in a 001 triple round bottom flask. Equipped with a blade stirrer While stirring with an overhead stirrer, add 60 paper sheets of dry hexane and add 0.5-2. - Etquin benzoic acid was forced in and the slurry was refluxed for 2 hours. Another small shushi In a tank flask, add 2.6 Il 1 of 1-pentanol and IM of dry hexane to room temperature. Mix at room temperature and add 2.6 d of Ti(J) drop by drop to avoid further rapid heat generation. added. The solution was stirred for an additional 45 minutes to ensure complete reaction, and then the treated MgO Injected into catalyst flask containing slurry. The slurry was refluxed at 70°C for 2 hours. Add 4.6 m of butane solution (2,8 5 mmol) was injected with stirring using a magnetic stirrer. The slurry was stirred for an additional hour. Stirring ensured completion of this preactivation. Since the catalyst does not pass nitrogen, it is heated at 70°C. After drying for 16 hours, it became a smooth dark brown powder.As a result of six element analysis, the final Ti in the catalyst was found to be 1.31 mmol/g.

Implementation pierced earth Sue with 2 1- person A 1-gallon slurry reactor was heated to 90°C overnight, cooled to room temperature, and reacted. 25% by weight diisobutylaluminum hydride-hebutane solution 1, 8 in the reactor cc and then added 0.42 grams of the catalyst from Example 2 with 2 liters of hexane. Both were transferred to a reactor. While stirring, heat the reactor to 90°C and 1-hexene and a partial pressure of 930 kPa (135 p si) hydrogen was added. Ethylene was continuously fed into the reactor for 80 minutes. The partial pressure of was maintained at 930 kPa (135 psi). The product is 8.5 cc of I Stabilized with rganox 1076 solution (500 ppo+ in hexane) and vacuum Dry in oven for 4 hours. The product has a large average particle size of 335 grams (4 00 microns), I2 is 10.9, Iz+ is 272, MFR is 25, or The polymer had a density of 0.962 (g/cc).

Example i Komidan Souji 1kin Polymerizations were carried out at 90°C using 2 liters of polymerization grade hexane. Example Approximately 0.4 grams of catalyst (TiO, 536 mmol) of 1.2 as a cocatalyst. 8d diisobutylaluminum hydride solution (25% by weight hebutane solution), 5 aj! of 1-hexene comonomer, and 310 kPa (45 psia) of Hydrogen was added to the reactor in this order. Polymerization was performed at an air pressure of 931 kPa (135 psia). Working under tyrene partial pressure, the HDPE products in Table 1 were obtained. Product is 500ppn+ After stabilization with Irganox 1076 stabilizer at 65 °C in vacuum open Dry for an hour. Melt index (I2), flow index (Tz+) , density, and melt viscosity (V2O and V300) were measured. test results Shown in Table I.

Table I Example construction story Implementation story Omega catalyst Madoka MFRV 2° attack promotion prior art” 0.944 3.628.5 12989 548B 2.375 2 0. 96312.924 31962135 1.5* U.S. Patent No. 4,303,7 No. 71, Example 7**V30 in Table 1 shows melting at a shear rate of 30 sec-' Melt viscosity.

* * v3QQ is the melt viscosity at a shear rate of 300 sec-'.

Implementation Fire Day (Sutan Uni Rikin) Polymerization was carried out using the catalyst of Example 2 in the same manner as in Example 5, and the intermediate of the polymer was The influence of the catalyst on the particle size and the hydrogen response of the catalyst were investigated. of hydrogen to ethylene was used. The test results are shown in Table 2, using pentanol. The prepared catalyst of Example 2 showed a high hydrogen response, had a large intermediate particle size, and It can be seen that both are preferable.

Table-1 Polymer Density Hydrogen Response MFR Polymer Intermediate Particle Size in the Examples Below- "lZ L-,,1lxL-AhdhL-Aj...ヱY-2 0.966 16 ．． 1 26.4 331 sharp construction (Implementation 1: 11111) In this example, ethylene was produced in the same manner as in Example 6 using the catalyst of Example 1. and 1-hexene were copolymerized.

Polymerization was carried out using 4 liters of polymerization grade hexane, 8 liters (2 gallons) The experiments were carried out at 90°C in a slurry reactor. Approximately 0.07 g of the catalyst of Example 1 (Ti O,078 mmol) and 3.6d diisobutylaluminum hydride solution solution (25% by weight hebutane solution; Aj 4.53 mmol), 10d of 1-hexane Comonomer and hydrogen were added to the reactor in this order. Polymerization is carried out at 931 kPa (1 The HDPE product was produced using an ethylene partial pressure of 35 psia). H: The molar ratio of C1” was kept at 1:1. The product was 500 pp+l of Irga-nox After stabilization at 1076, it was dried in a vacuum oven at 65°C for 4 hours. Mail root index 0. ), flow index (rz+) and productivity measurement Then, MFR was calculated from the measured values of I2 and I□. The test results are summarized in Table 3 .

Table - Yu i　o　日　q&L'7:0)-h)〉;K''Jl(Example　Example below　Cal Bonic acid hydrogen response MFR productivity XO species tlL--'hL (LtLaL) (i L limb/hour) 6 2 2-EBA 16.1 26.2 1600 (aromatic) 7 1 Acetic acid 20.1 26.4 7260 (aliphatic) The data in Table 3 shows the hydrogen response of the catalysts of Example 1 and Example 2 (i.e., constant H, :　C,” Melt index of polymer made using catalyst at molar ratio ) and the MFR of polymer products made using these two catalysts are comparable. However, the catalyst of Example 1 prepared with acetic acid-modified NGO support shows that The activity of the catalyst of Example 2 prepared on a MgO support modified with 2-ethoxybenzoic acid was This indicates that the activity is significantly greater than the activity.

international search report

Claims (10)

[Claims] 1. Magnesium oxide pretreated with an insufficient molar amount of organic acid for the magnesium oxide support The titanium component and organoaluminum compound reducing agent are supported on the ium carrier. In the olefin polymerization coordination catalyst, the titanium component contains 5 to 12 carbon atoms. It is a reaction product of alkanol with Ticl4, and the alkanol vs. Tic An olefin polymerization coordination catalyst in which the molar ratio of l4 is 0.5 to 1.5. 2. Organic acids include aliphatic monocarboxylic acids, aliphatic dicarboxylic acids, and aromatic monocarboxylic acids. The catalyst according to claim 1, which is an acid or an aromatic dicarboxylic acid. 3. Aliphatic monocarboxylic acids have the formula R-COOH, where R is H or has 1 carbon atom. 3. The catalyst according to claim 2, having from 1 to 17 alkyl groups. 4. 4. The catalyst of claim 3, wherein the aliphatic monocarboxylic acid is acetic acid. 5. Claim 3, wherein the molar ratio of alkanol to Ticl4 is from 0.8 to 1.2. catalyst. 6. The organoaluminum compound has the formula RmAlX(3-n), where R is a carbon atom. 1 to 20 alkyl, alkenyl, alkylaryl, or aryl X is hydrogen or halogen, and n is 1.2 or 3 ) The catalyst of claim 1. 7. Claim 1 wherein the organoaluminum compound is tri-n-hexylaluminum. catalyst. 8. Aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid. 3. The catalyst of claim 2, which is phosphoric acid, maleic acid, or fumaric acid. 9. Aromatic monocarboxylic acids are benzoic acid, alkyl-substituted benzoic acids or alkyl-substituted benzoic acids. 3. The catalyst of claim 2, which is a oxy-substituted benzoic acid. 10. Magnesium oxide support pretreated with insufficient molar amount of organic acid A titanium compound and an organoaluminum compound reducing agent are supported on a nesium carrier. , a titanium compound reacts with an alkanol having 5 to 12 carbon atoms and Ticl4. In the reaction product, the molar ratio of alkanol to Ticl4 is from 0.5 to 1.5. A method for polymerizing olefins consisting of ethylene using a position catalyst.