CN116769087A - Preparation method of catalyst for preparing ultra-high molecular weight polyethylene - Google Patents

Preparation method of catalyst for preparing ultra-high molecular weight polyethylene Download PDF

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CN116769087A
CN116769087A CN202310860411.7A CN202310860411A CN116769087A CN 116769087 A CN116769087 A CN 116769087A CN 202310860411 A CN202310860411 A CN 202310860411A CN 116769087 A CN116769087 A CN 116769087A
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catalyst
molecular weight
preparing
high molecular
titanium
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杜华
黄敬宇
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Hubei Yuhong High Tech Material Technology Co ltd
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Hubei Yuhong High Tech Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene

Abstract

The invention provides a preparation method of a catalyst for preparing ultra-high molecular weight polyethylene, which comprises the following steps: step 1, generating a magnesium compound solution through the contact reaction of a magnesium chloride compound and an organic alcohol compound; step 2, adding a compound of pyrromethene-aniline and unsaturated fatty acid ester containing at least one hydroxyl group into the generated magnesium compound solution to supply an electron body; and step 3, further adding a titanium compound for reaction to prepare the required catalyst. The ultra-high molecular weight polyethylene prepared by the method has good fluidity, high bulk density, uniform and fine particle size distribution, high and controllable molecular weight and high tensile strength, and the catalyst is suitable for preparing high-strength ultra-high molecular weight polyethylene fibers and high-strength lithium battery diaphragms.

Description

Preparation method of catalyst for preparing ultra-high molecular weight polyethylene
Technical Field
The invention belongs to the field of polyethylene preparation, and particularly relates to a preparation method of a catalyst for preparing ultra-high molecular weight polyethylene.
Background
Ultra High Molecular Weight Polyethylene (UHMWPE) is a linear structure polyethylene of extremely large relative molecular mass, and has been widely studied and used due to its many excellent properties different from those of general-purpose polyethylene. The UHMWPE fiber is a high-performance fiber prepared from UHMWPE raw materials by a gel spinning method, has high strength and modulus and excellent mechanical properties, and has been widely applied in the fields of military industry, national defense and the like. In general, the relative molecular mass distribution, particle morphology, particle size distribution, etc. of UHMWPE powder are affected by factors such as catalyst, polymerization process, etc., which in turn affect the processability of the polymer powder and thus the product properties. Therefore, in order to obtain UHMWPE fibers having excellent properties, it is necessary to investigate both from the UHMWPE raw material and the fiber preparation. The preparation of ultra-strong polyethylene fibers has special requirements on UHMWPE, and besides the molecular weight of the ultra-strong polyethylene fibers is higher than 300 ten thousand, the catalytic activity of the ultra-strong polyethylene fibers is also required to be high, so that the obtained UHMWPE has lower ash content; meanwhile, the obtained polyethylene has high particle bulk density; the distribution is uniform, and the particle size distribution is less than 0.8; the particle size cannot be too large nor too small, and the average particle size is usually 80 to 130. Mu.m.
To obtain high strength ultra high molecular weight polyethylene fibers, there are generally two approaches: the first route uses ultra-high molecular weight polyethylene of higher molecular weight, the higher the strength. However, the higher the molecular weight of the ultra-high molecular weight polyethylene, the lower the solubility in the solvent, and the dissolution residue of the powder is generated. Resulting in clogging of the extruder screen. Even if spinning is possible, there is a problem that undissolved components become breaking points and breakage occurs at the time of drawing. Therefore, the dissolution and residue of the powder cause defects of broken filaments during production, which is a serious problem. The second approach is to increase the tensile strength of ultra-high molecular weight polyethylene, but how to increase the tensile strength without increasing the molecular weight has been a difficult problem.
The invention patent application publication No. CN101245116A provides a catalytic system for preparing ultra-high molecular weight polyethylene. The catalyst system can be used for regulating the molecular weight of polyethylene by adding an external electron donor. However, polyethylene has a low bulk density and a particle size of about 160 μm, and cannot meet the spinning demand. Meanwhile, the method for adjusting the molecular weight by adopting the external electron donor is troublesome and cannot meet the requirement of industrial production.
The invention patent application with the application number of CN200410024103.8 discloses a preparation method of ultra-high molecular weight polyethylene, and the ultra-high molecular weight polyethylene prepared by the method has good flow rate and processability. However, the ultra-high molecular weight polyethylene resin has low molecular weight and low mechanical property, and is not suitable for producing high-strength and high-modulus fibers.
The invention patent application with publication number of CN1106025A discloses a preparation method of ultra-high molecular weight polyethylene with high bulk density, gasoline is adopted as a solvent, and the ultra-high molecular weight polyethylene with high bulk density is provided, wherein the bulk density is in the range of 350-460 g/L. But adopts gasoline as solvent, the ultra-high molecular weight polyethylene has unstable quality and poor mechanical property, and is unfavorable for preparing high-strength polyethylene fiber. In addition, the gasoline has wide distillation range, high energy consumption and high cost, and is unfavorable for industrial production.
The invention patent application publication No. CN1033703C provides a method for preparing UHMWPE, which mainly comprises the step of adding ZnCl into a catalyst system 2 The molecular weight of UHMWPE can be regulated between 60 and 610 ten thousand by controlling the Zn/Ti molar ratio. With this catalyst a good particle distribution of UHMWPE is obtained. However, the catalyst is complicated to prepare, the catalyst is prepared by a polishing method, the Zn/Ti molar ratio is required to be regulated to prepare UHMWPE with different molecular weights, and the catalytic activity of the system is low.
The patent application of the invention with publication No. CN1189486C provides a catalyst system for preparing UHMWPE with high bulk density and good particle morphology, which is prepared by preparing magnesium-aluminum solution by magnesium halide and aluminum compound in the presence of alcohol, then reacting with electron donor, adding titanium compound and silicon compound, and preparing the catalyst, although the catalyst system has better catalytic activity, the bulk density of the obtained UHMWPE is not high enough, at most only 0.40g/cm 3 The particle size is 152-179 μm, and the particle size distribution is relatively wide. Polyethylene powder in this form is disadvantageous for spinning.
The invention patent application publication No. CN1746197A provides a catalytic system for preparing UHMWPE with high bulk density, and the catalyst is formed by preparing a carrier and then carrying titanium, so that the catalyst is complicated to prepare. The so-called property regulator, silicon compound, was added in the preparation of UHMWPE. Although the UHMWPE produced has a higher molecular weight, it does not provide an average particle size of the polymer particles, nor is it very high in catalytic activity, and the polymerization time is about 4 hours, with only about 3 ten thousand times the catalytic activity.
In summary, the preparation of UHMWPE at present not only requires a higher catalytic activity of the catalyst, but also has dynamic stability and long-acting property, so that the occurrence of oversized particles or undersized particles of the polymer can be prevented to the greatest extent, and ash content of the polymer is reduced, which is more important especially in the preparation of ultra-strong polyethylene fibers and lithium battery separators. At the same time, it is also desirable that the polymer be of a controlled molecular weight and have a good morphology to stabilize the process and to enhance the performance of the operation. This is the direction of development of ultra-high molecular weight polyethylene catalysts in the future, requiring catalysts with higher mechanical attrition strength and good particle morphology.
In recent years, there has been an increasing demand for further improvement in productivity while improving properties of molded articles such as fibers, secondary battery separators, compression molded articles, and plunger molded articles using ultra-high molecular weight polyethylene, but the catalyst activity of the ultra-high molecular weight polyethylene catalyst currently existing is low, and the produced ultra-high molecular weight polyethylene cannot meet the demands for downstream applications in terms of properties such as particle morphology, molecular weight grade, and viscosity. In view of the above problems of the prior art, the present invention is intended to provide a method for producing a catalyst for producing ultra-high molecular weight polyethylene, which is used for producing ultra-high molecular weight ethylene-based polymers to improve the performance and productivity of molded articles such as secondary battery separators, fibers, compression molded articles, plunger extrusion products, fiber knits, textiles and the like using ultra-high molecular weight polyethylene.
[ N, N ] commonly used for polypropylene catalysts]The electron donor can prepare high-strength ultra-high molecular weight polyethylene. The ultra-high molecular weight polyethylene catalyst is different from the ordinary polyethylene catalyst, and he needs to inhibit the catalytic activity to obtain high molecular weight polyethylene. The pyrrole formaldehyde anilide is very good [ N, N ]]The electron donor is also a good ligand. Publication number CN1840549A reports that the coordination of pyrrole-formaldehyde anilide with titanium forms a non-metallocene complex which catalyzes the polymerization of ethylene, but has a lower activity of only 2.78X10 6 gPE/mol.Ti.h, only about 2600 g of polyethylene can be produced per g of catalyst. And bulk density of only 0.21g/cm 3 The demand for producing ultra-high molecular weight polyethylene cannot be satisfied. However, if the pyrrole formaldehyde aniline and at least one hydroxyl unsaturated fatty acid ester are compounded to be used as an electron donor, very high catalytic activity can be obtained, the highest catalytic activity can be 7.9 ten thousand times, and the bulk density can be 0.49g/cm 3 The above. When the pyrrole formaldehyde aniline is used as an electron donor alone, the catalytic activity can reach 4 ten thousand times, and the bulk density can reach 0.40g/cm 3 . Importantly, the resulting ultra-high molecular weight polyethylene has a higher tensile strength than the commercially available products. The particle morphology is also improved to a great extent, and the particle size can be controlled to be below 80-130 mu m according to the process.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention adopts the following technical scheme for solving the problems existing in the prior art:
a method for preparing a catalyst for preparing ultra-high molecular weight polyethylene, comprising the steps of:
step 1, generating a magnesium compound solution through the contact reaction of a magnesium chloride compound and an organic alcohol compound;
step 2, adding a compound electron donor of pyrrole formaldehyde-aniline and unsaturated fatty acid ester containing at least one hydroxyl group into the generated magnesium compound solution;
and step 3, further adding a titanium compound for reaction to prepare the required catalyst.
The organic alcohol compound in the step 1 is R A OH, wherein R is A Is C 2 ～C 16 An alkyl group; such as ethanol, propanol, butanol, hexanol, 2-methyl-forming alcohol, n-heptanol, isooctanol, or n-octanol, or mixtures thereof.
The structural formula of the pyrrolaformaldehyde-aniline in the step 2 is as follows:
r is monosubstituted or polysubstituted substituent on pyrrole ring, and is selected from hydrogen and C1-C12 alkyl respectively; r is R 1 ～R 3 Respectively selected from hydrogen and C1-C6 alkyl; r' is selected from hydrogen and C1-C6 alkyl.
The pyrrolaldehyde-aniline is one or a combination of a plurality of pyrrolaldehyde aniline, pyrrolaldehyde aniline formal 2, 6 dimethylaniline, pyrrolaldehyde aniline formal 2, 6 diisopropylaniline, pyrrolaldehyde aniline formal 2, 4, 6 trimethylaniline, pyrrolaldehyde aniline formal 2, 4, 6 triisopropylamine.
The unsaturated fatty acid ester containing at least one hydroxyl in the step 2 is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate and pentaerythritol triacrylate; aliphatic mono-and polyesters containing at least one hydroxyl group, for example 2 hydroxyethyl acetate, methyl 3-hydroxybutyrate, ethyl 3-hydroxybutyrate, methyl 2 hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl 3-hydroxy-2-methylpropionate, 2-dimethyl-3-hydroxypropionate, ethyl 6-hydroxycaproate, tert-butyl 2-hydroxyisobutyrate, ethyl 3-hydroxyto-di-ate, ethyl lactate, isopropyl lactate, butyl isobutyl lactate, ethyl mandelate , dimethyl ethyl tartrate, dibutyl tartrate, diethyl citrate, triethyl citrate, ethyl 2-hydroxycaproate, or diethyl bis (hydroxymethyl) malonate: aromatic ester compounds containing at least one hydroxyl group, such as 2-hydroxyethyl benzoate, methyl salicylate 2-hydroxyethyl 4- (hydroxymethyl) benzoate, methyl 4-hydroxybenzoate, ethyl 3-hydroxybenzoate, 4-methyl salicylate, ethyl salicylate, phenyl salicylate, propyl 4-hydroxybenzoate, phenyl 3-hydroxynaphthoate, a combination of one or more of monoethylene glycol monobenzoate, diethylene glycol monobenzoate, triethylene glycol benzoate, or cycloaliphatic esters containing at least one hydroxyl group, such as hydroxybutyl lactone, for efficient preparation of catalysts for UHMWPEI having a high bulk density, a narrow particle distribution to avoid oversized or undersized particles.
The molar ratio of the pyrrole formaldehyde aniline in step 2 to the titanium in the catalyst component is 1 to 10, preferably 1.5 to 5; the molar ratio of the unsaturated fatty acid ester containing at least one hydroxyl group to titanium in the catalyst component is 1 to 10, preferably 1.5 to 5.
The titanium compound in the step 3 is (R) B O) m TiCl 4-m Wherein R is B Is alkyl, m is an integer from 0 to 4; the amount of the titanium compound is 0.1 to 200mol per 1mol of the magnesium compound. The titanium compound is titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, titanium trichloromonoethoxy or a mixture thereof.
The magnesium chloride in the step 1 is dissolved in an organic alcohol hydrocarbon solvent in the hydrocarbon solvent, and the hydrocarbon solvent is C 4～18 Aliphatic hydrocarbons, preferably C 6～12 Aliphatic hydrocarbons; preferably, the reaction temperature is 50-180 ℃, and the reaction time is preferably 0.5-5 hours; wherein the molar ratio of magnesium to alcohol is 1:0.5-6, preferably 1:2-4; 0.2 to 1.0 liter of hydrocarbon solvent is used per mole of magnesium compound.
The temperature of the magnesium alcoholate contact reaction in the step 1 is-30-10 ℃, preferably-20-0 ℃ and most preferably-10-0 ℃; the reaction time is 0.5 to 5 hours, preferably 0.5 to 3 hours.
The reaction temperature in the step 2 is 20-100 ℃, preferably 40-70 ℃.
And (3) heating the obtained reaction liquid to 60-130 ℃ within 1-4 hours in the step (3), continuing to react for 1-6 hours, filtering the obtained reaction liquid, washing with a solvent, and drying to obtain the solid catalyst.
In the step 2, a crystallization precipitation agent is required to be added, wherein the crystallization precipitation agent is phthalic anhydride or maleic anhydride or a mixture thereof; the amount of the crystallization precipitating agent is 0.05 to 0.1 mol per mol of the active magnesium chloride raw material, and the crystallization precipitating agent can promote the crystallization of magnesium chloride and enable the crystallization to be better and the crystallization to be stronger.
The invention further provides a catalyst system, which specifically comprises:
a) A catalyst component prepared based on the aforementioned preparation method;
b) Cocatalysts which are metal-organic compounds, preferably organoaluminum compounds R C 3-n A1X n Wherein X is halogen, R C Is C1-C12 alkyl, n is an integer of 0-2; wherein the molar ratio of aluminum in the cocatalyst to titanium in the catalyst active component is from 10 to 100, preferably from 30 to 80, more preferably from 20 to 50.
The average particle diameter of the catalyst is preferably 0.1 μm or more and 20 μm or less, more preferably 0.2 μm or more and 16 μm or less, and still more preferably 0.5 μm or more and 10 μm or less. If the average particle diameter is 0.1 μm or more, problems such as scattering and adhesion of the obtained ethylene polymer particles tend to be prevented. When the average particle diameter is 10 μm or less, problems such as sedimentation of the ethylene polymer particles in the polymerization system due to excessive size and clogging of the pipeline in the post-treatment step of the ethylene polymer can be prevented. The catalyst is preferably as narrow as possible in particle size distribution, and fine particles and coarse particles can be removed by means of sieves, centrifugal separation, cyclone separators.
The catalyst prepared by the method is applied to the preparation of the ultra-high molecular weight polyethylene, and the polymerization reaction temperature is 30-90 ℃, preferably 40-85 ℃; the reaction pressure is as follows: 0.1 to 1.0MPa, preferably 0.2 to 0.8MPa. The prepared ultra-high molecular weight polyethylene (UHMWPE) has the following properties: an intrinsic viscosity (. Eta.) of greater than 4dl/g, a median particle diameter D50 of between 100 and 150m, at least 450kg/m 3 The apparent bulk density of 43-51 mPa (depending on the molecular weight) and the ultra-high molecular weight polyethylene ash content is less than 200ppm.
The invention has the following advantages:
1. the catalyst prepared by the method can solve a plurality of problems existing in the preparation of ultra-high molecular weight polyethylene fiber materials and membrane materials, has the catalyst precursor for controlling the dynamics of the catalyst and the molecular weight of the polymer, has the advantages of firm particles, high catalytic activity, stable and controllable dynamics curve and the like, and the ultra-high molecular weight polyethylene prepared by using the catalyst has high bulk density, uniform and fine particle size distribution, high and controllable molecular weight.
2. The ultra-high molecular weight ethylene polymer powder prepared by the catalyst shortens the cooling procedure time of the molded body, particularly the diaphragm, the fiber, the compression molded product and the plunger extrusion product for the secondary battery, and the ultra-high molecular weight ethylene polymer powder has good swelling state and shortens the extrusion time. The use of the ultra-high molecular weight ethylene polymer powder can reduce the average pore diameter of the secondary battery separator and make it uniform, thereby improving the performance of the secondary battery separator and prolonging the service life of the product.
Detailed Description
The technical scheme of the invention is further specifically described by the following examples.
The invention provides a preparation method of a catalyst for preparing ultra-high molecular weight polyethylene, which comprises the steps of dissolving magnesium chloride in organic alcohol to form a uniform solution, adding pyrrole formaldehyde aniline and an unsaturated fatty acid ester compound internal electron donor containing at least one hydroxyl group, mixing the solution with titanium tetrahalide or a derivative thereof, maintaining for a period of time at a low temperature, heating and heating, when a crystal precipitation agent exists in a reaction system, precipitating solids, treating with titanium tetrahalide or an inert diluent, and finally filtering, washing and drying to obtain the solid catalyst comprising components such as titanium, magnesium, halogen, electron donor and the like.
All air sensitive materials in the examples below were operated using standard vacuum double-line anhydrous anaerobic methods of operation. The reagent is used after refining treatment. The tensile strength of the polymer was measured according to national standard GB/T1040-2006. Apparent density was measured by ASTM-D-1895. The catalyst particle size was measured by Hitachi ultra-high resolution scanning electron microscopy (Regulus 8100). Polyethylene particle size was determined by a laser particle analyzer (Mastersizer X, malvern), where D10, D50 and D90 distributions refer to the particle sizes at each of the percentages 10, 50 and 90. D50 is defined as the average particle distribution, and the particle size distribution is defined as(d 90-d 10)/d 50. Viscosity average molecular weight was determined by high Wen Xingwu viscometer method according to ASTM D4020-05, capillary inner diameter of 0.53mm, and M was used η ＝5.37×10 4 ·[η] 1.49 And (5) performing calculation. The determination of ultra high molecular weight polyethylene ash was in accordance with GBT 9345.1-2008. The preparation of the pyrrole formaldehyde aniline derivatives is according to CN101255204A.
Example 1
0.5mol of anhydrous MgC1 2 300mL decane and 300mL isooctanol are heated to 130 ℃ to react for 120 minutes until the solid is completely dissolved, 14g phthalic anhydride is added, the reaction is continued for 1 hour, the temperature is reduced to 65 ℃, 0.15mol pyrrole formaldehyde polyaniline and 0.15mol 2-hydroxyethyl methacrylate are added at the temperature, the reaction is continued for 60 minutes, and the reaction is cooled to room temperature. Slowly dripping 2000mL TiC1 at 0deg.C for 90 min while maintaining the temperature at not more than 1deg.C 4 After the dripping is finished, the temperature is kept at 0 ℃ for 60 minutes, then the temperature is slowly increased to 110 ℃ for 120 minutes, the reaction is continued for 120 minutes, the solid catalyst is obtained, and the sedimentation speed of the solid catalyst particles is found to be very high after the stirring is stopped. After the reaction, the solid catalyst was filtered off by heating. Washing with hexane 400mL each time until the filtrate is substantially colorless, wherein the free titanium content is less than 0.3mg/mL, and drying to obtain a solid. The titanium content of the catalyst thus obtained was 6.2%, and N was 1.2%. Catalyst particle size: 2.8 μm.
Example 2
As in example 1, only the compound pyrrolormaldehyde polyaniline in the example was replaced with pyrrolormaldehyde 2, 6 dimethylaniline, and the titanium content of the catalyst thus obtained was 5.7%, and N was 1.1%. Catalyst particle size: 2.7 μm.
Example 3
As in example 1, only the compound pyrrolaformaldehyde polyaniline in the example was replaced with pyrrolaformaldehyde 2, 6 diisopropylaniline, and the titanium content of the catalyst thus obtained was 5.9%, and N was 1.14%. Catalyst particle size: 2.85 μm.
Example 4
As in example 1, only the compound pyrrolaformaldehyde polyaniline in example was replaced with pyrrolaformaldehyde 2, 4, 6-trimethylaniline, and the titanium content of the catalyst thus obtained was 5.4%, and N was 1.05%. Catalyst particle size: 2.63 μm.
Example 5
As in example 1, only the compound pyrrolaformaldehyde polyaniline in the example was replaced with pyrrolaformaldehyde 2, 4, 6 triisopropylamine, and the titanium content of the catalyst thus obtained was 6.1%, and N was 1.2%. Catalyst particle size: 2.91 μm.
Example 6
As in example 1, only 2-hydroxyethyl methacrylate was replaced with 2-hydroxyethyl acetate, and the titanium content of the catalyst thus obtained was 6.5% and N was 1.25%. Catalyst particle size: 2.73 μm.
Comparative example 1
The same as in preparation example 5, except that the electron donors were all condensed with 0.03mol of pyrrole formal 2, 4, 6 triisopropylaniline, elemental analysis: 4.8% of Ti and 1.8% of N. Catalyst particle size: 4.3 μm.
Comparative example 2
The same as in preparation example 1, except that the electron donors were all prepared with 0.03mol of 2-hydroxyethyl methacrylate, elemental analysis: 4.6% of Ti. Catalyst particle size: 5.1 μm.
Preparation of ultra-high molecular weight polyethylene Using the catalysts of examples 1-6 and comparative examples 1 and 2 in a 4 cubic meter stainless steel autoclave, after nitrogen substitution, dehydrated hexane (water content: less than or equal to 8 ppm) 2.8 cubic meters, triethylaluminum hexane solution (30 in terms of AI/Ti molar ratio) and 10g of the catalyst prepared in the above example were sequentially added, stirring was carried out at a speed of 500 rpm, heating to 60℃and then introducing ethylene to a autoclave pressure of 0.6MPa (gauge pressure), maintaining the autoclave pressure at 75℃for 3 hours, cooling to room temperature after polymerization, discharging and drying to obtain an UHMWPE polyethylene product. The catalyst activity measurement, bulk density measurement, viscosity average molecular weight measurement, measurement of average particle diameter and particle diameter distribution, etc. were performed on the products polymerized by the catalysts of each example, and the results are shown in Table 1 in detail.
TABLE 1 results of product Performance test obtained by polymerization of the catalysts of examples 1-6 and two comparative examples
As can be seen from the data in Table 1, the catalytic activity can be improved up to 7.6 ten-thousand times by using a complex electron donor of a pyrrolidonal-aniline and an unsaturated fatty acid ester containing at least one hydroxyl group. Bulk density can also reach 0.50g/cm 3 The above. The grain size of the polyethylene can be controlled in the range of 116-125 mu m. The molecular weight is above 500 ten thousand. Can meet the requirement of high-strength fiber.
The following examples polymerized in a different manner with the catalyst of example 5:
example 5-1
In a 4-cubic meter stainless steel autoclave, after nitrogen substitution, dehydrated hexane (water content less than or equal to 5 ppm) 2.8 cubic meters, a hexane solution of triethylaluminum (30 according to AI/Ti molar ratio) and 8g of the catalyst prepared in example 5 are sequentially added, stirring speed is 500 revolutions per minute, heating to 60 ℃, introducing ethylene until the kettle pressure is 0.6Mpa (gauge pressure), polymerizing at 65 ℃ and the kettle pressure is kept at 0.6Mp for 3 hours, cooling to room temperature, discharging and drying to obtain an UHMWPE polyethylene product. The results are detailed in Table 2.
Example 5-2
The same as in example 5-1, except that the polymerization temperature was maintained at 70 ℃. The results are detailed in Table 2.
Examples 5 to 3
The same as in example 5-1, except that the polymerization temperature was maintained at 75 ℃. The results are detailed in Table 2.
Examples 5 to 4
The same as in example 5-1, except that the polymerization temperature was maintained at 80 ℃. The results are detailed in Table 2.
Examples 5 to 5
In a 4-cubic meter stainless steel autoclave, dehydrated hexane (water content: 10 ppm) 2.8 cubic meters, a hexane solution of triethylaluminum (30 in terms of mole ratio of AITi) and 10g of the catalyst prepared in example 5 were sequentially added after nitrogen substitution, stirring speed was 500 rpm, heating to 60℃and then introducing ethylene and hydrogen in a mass ratio of ethylene/hydrogen of 4000:1, until the kettle pressure is 0.6Mpa (gauge pressure), at 85 ℃, keeping the kettle pressure at 0.6Mp, carrying out polymerization reaction for 3 hours, cooling to room temperature, discharging and drying to obtain the UHMWPE product. The results are detailed in Table 2.
TABLE 2 Properties of the product prepared based on example 5- (1-5)
As can be seen from the data in Table 2, the molecular weight of the polyethylene can be adjusted by changing the polymerization temperature using the same catalyst, and the molecular weight can be adjusted in the range of 500 to 1000 ten thousand. After hydrogen is added (examples 5-5), the molecular weight can be controlled at 165 ten thousand, and the product index completely accords with the Seranis GUR4112 lithium battery separator material.
Table 3 shows the tensile strengths of ultra high molecular weight polyethylenes of various molecular weights, and for comparison purposes, commercially available Seranis GUR products were used, and the tensile strength data of the GUR products were selected from the product specifications.
TABLE 3 tensile Strength test of the products prepared in example 5- (1-5) and comparative examples
From the data in Table 3, it can be seen that the ultra-high molecular weight polyethylene prepared by the novel catalyst has higher tensile strength, and the high tensile strength can make the ultra-high molecular weight polyethylene fiber have higher strength and the lithium battery membrane has higher strength. Is very favorable for producing ultra-high molecular weight polyethylene fibers and lithium battery diaphragms.
The protective scope of the invention is not limited to the embodiments described above, but it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention. It is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.

Claims (10)

1. A method for preparing a catalyst for preparing ultra-high molecular weight polyethylene, comprising the steps of:
step 1, generating a magnesium compound solution through the contact reaction of a magnesium chloride compound and an organic alcohol compound;
step 2, adding a compound electron donor of pyrrole formaldehyde-aniline and unsaturated fatty acid ester containing at least one hydroxyl group into the generated magnesium compound solution;
and step 3, further adding a titanium compound for reaction to prepare the required catalyst.
2. A method for preparing a catalyst for preparing ultra-high molecular weight polyethylene according to claim 1, wherein: the organic alcohol compound in the step 1 is R A OH, wherein R is A Is C 2 ～C 16 An alkyl group.
3. A method for preparing a catalyst for preparing ultra-high molecular weight polyethylene according to claim 1, wherein: the structural formula of the pyrrolaformaldehyde-aniline in the step 2 is as follows:
r is monosubstituted or polysubstituted substituent on pyrrole ring, and is selected from hydrogen and C1-C12 alkyl respectively; r is R 1 ～R 3 Respectively selected from hydrogen and C1-C6 alkyl; r' is selected from hydrogen and C1-C6 alkyl;
the pyrrolaldehyde-aniline is one or a combination of a plurality of pyrrolaldehyde aniline, pyrrolaldehyde aniline formal 2, 6 dimethylaniline, pyrrolaldehyde aniline formal 2, 6 diisopropylaniline, pyrrolaldehyde aniline formal 2, 4, 6 trimethylaniline, pyrrolaldehyde aniline formal 2, 4, 6 triisopropylamine.
4. A method for preparing a catalyst for preparing ultra-high molecular weight polyethylene according to claim 1, wherein: the unsaturated fatty acid ester containing at least one hydroxyl in the step 2 is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate and pentaerythritol triacrylate; aliphatic mono-and polyesters containing at least one hydroxy group, such as 2 hydroxyethyl acetate, methyl 3-hydroxybutyrate, ethyl 3-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl 3-hydroxy-2-methylpropionate, 2-dimethyl-3-hydroxypropionate, ethyl 6-hydroxycaproate, t-butyl 2-hydroxyisobutyrate, 3-hydroxy-to-diethyl salicylate, ethyl lactate, isopropyl lactate, butyl isobutyl lactate, ethyl mandelate , dimethyl ethyl tartrate, dibutyl tartrate, diethyl citrate, triethyl citrate, ethyl 2-hydroxycaproate, or diethyl bis (hydroxymethyl) malonate aromatic ester compounds containing at least one hydroxy group, such as 2-hydroxyethyl benzoate, methyl 2-hydroxyethyl 4- (hydroxymethyl) benzoate, methyl 4-hydroxybenzoate, ethyl 3-hydroxybenzoate, 4-methyl salicylate, ethyl salicylate, phenyl salicylate, propyl 4-hydroxybenzoate, phenyl monoglycol benzoate, or a combination of at least one or more of the following the above.
5. A method for preparing a catalyst for preparing ultra-high molecular weight polyethylene according to claim 1, wherein: the molar ratio of the pyrrole formaldehyde aniline in the step 2 to the titanium in the catalyst component is 1-10; the molar ratio of the unsaturated fatty acid ester containing at least one hydroxyl group to titanium in the catalyst component is 1 to 10.
6. A method for preparing a catalyst for preparing ultra-high molecular weight polyethylene according to claim 1, wherein: the titanium compound in the step 3 is (R) B O) m TiCl 4-m Wherein R is B Is alkyl, m is an integer from 0 to 4; the amount of the titanium compound is 0.1 to 200mol of the titanium compound per 1mol of the magnesium compound, and the titanium compound is one or a mixture of a plurality of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxy, titanium chlorotriethoxy, titanium dichlorodiethoxy and titanium trichloromonoethoxy.
7. A method for preparing a catalyst for preparing ultra-high molecular weight polyethylene according to claim 1, wherein: the magnesium chloride in the step 1 is dissolved in an organic alcohol hydrocarbon solvent in the hydrocarbon solvent, and the hydrocarbon solvent is C 4～18 Aliphatic hydrocarbon, the reaction temperature is 50-180 ℃ and the reaction time is 0.5-5 hours; wherein the molar ratio of magnesium to alcohol is 1:0.5-6; 0.2 to 1.0 liter of hydrocarbon solvent is used per mole of magnesium compound;
the temperature of the magnesium alkoxide solution contact reaction in the step 1 is-30-10 ℃ and the reaction time is 0.5-5 hours;
the reaction temperature of the step 2 is 20-100 ℃;
and (3) heating the obtained reaction liquid to 60-130 ℃ within 1-4 hours in the step (3), continuing to react for 1-6 hours, filtering the obtained reaction liquid, washing with a solvent, and drying to obtain the solid catalyst.
8. A method for preparing a catalyst for preparing ultra-high molecular weight polyethylene according to claim 1, wherein: adding a crystallization precipitation agent in the step 2, wherein the crystallization precipitation agent is phthalic anhydride or maleic anhydride or a mixture thereof; the amount of the crystallization agent used is 0.05 to 0.1 mol per mol of the active magnesium chloride raw material.
9. A method for preparing a catalyst for preparing ultra-high molecular weight polyethylene according to claim 1, wherein: the invention further provides a catalyst system, which specifically comprises: a catalyst component prepared based on the aforementioned preparation method; and a promoter, the promoter being goldAn organic compound, preferably an organoaluminum compound R C 3-n A1X n Wherein X is halogen, R C Is C1-C12 alkyl, n is an integer of 0-2; wherein the molar ratio of aluminum in the cocatalyst to titanium in the catalyst active component is 10-100, and the average particle diameter of the catalyst is 0.1 μm or more and 20 μm or less.
10. A method for preparing a catalyst for preparing ultra-high molecular weight polyethylene according to claim 1, wherein: when the catalyst prepared by the method is used for preparing the ultra-high molecular weight polyethylene, the polymerization temperature is 30-90 ℃, and the reaction pressure is as follows: 0.1-1.0 MPa.
CN202310860411.7A 2023-07-13 2023-07-13 Preparation method of catalyst for preparing ultra-high molecular weight polyethylene Pending CN116769087A (en)

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CN1452637A (en) * 2000-04-24 2003-10-29 三星综合化学株式会社 Catalyst for producing ultra high molecular weight polyethylene and method for producing ultra high molecular weight polyethylene using same
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