CN113943386A - Method for regulating and controlling particle size and particle size distribution of ultrahigh molecular weight polyethylene - Google Patents

Method for regulating and controlling particle size and particle size distribution of ultrahigh molecular weight polyethylene Download PDF

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CN113943386A
CN113943386A CN202111228201.3A CN202111228201A CN113943386A CN 113943386 A CN113943386 A CN 113943386A CN 202111228201 A CN202111228201 A CN 202111228201A CN 113943386 A CN113943386 A CN 113943386A
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particle size
titanium
catalyst
molecular weight
weight polyethylene
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许学翔
鲁立军
邓兆敬
李江涛
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China Chemical Technology Research Institute
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China Chemical Technology Research Institute
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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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/01—High molecular weight, e.g. >800,000 Da.

Abstract

The invention discloses a method for regulating and controlling the particle size and particle size distribution of ultra-high molecular weight polyethylene. The titanium catalyst provided achieves the purpose of controlling the activity efficiency of the catalyst by controlling the content of an active component titanium element, the distribution of a titanium compound in the catalyst and the particle size of the catalyst, and further can control the particle size of ultra-high molecular weight polyethylene particles generated in the ethylene polymerization process. The method for regulating and controlling the ultra-high molecular weight polyethylene powder comprises the steps of adjusting the particle size of the catalyst and the proportion of the catalyst with different particle sizes, and controlling a proper polymerization process, so that the purpose of controlling the particle size and the particle size distribution of the ultra-high molecular weight polyethylene powder is achieved. The requirements of the fiber, the diaphragm for the secondary battery, the filtering material, the compression molding product and other products on the particle size and the particle size distribution of the ultra-high molecular weight polyethylene powder are met.

Description

Method for regulating and controlling particle size and particle size distribution of ultrahigh molecular weight polyethylene
Technical Field
The invention relates to a method for preparing an ultrahigh molecular weight polyethylene catalyst, in particular to a method for preparing ultrahigh molecular weight polyethylene powder with different particle sizes and particle size distributions.
Background
Ultra-high molecular weight polyethylene (UHMWPE), which is a linear structure polyethylene having a very large relative molecular mass, has been widely studied and applied 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 is widely applied in the fields of military industry, national defense and the like. Different from common polyethylene, UHMWPE has special requirements on particle size and particle size distribution. The production of ultra-strong polyethylene fibres places special demands on UHMWPE (CN103865145A), except that the obtained UHMWPE has a lower ash content; meanwhile, the obtained polyethylene has high particle bulk density; the particle size distribution is concentrated. The average particle size is also required to be 200 μm or less, and when the particles are processed into a battery separator, a fiber, or the like, the particles tend to have more excellent processability such as productivity and stretchability. Particles of more than 40 mesh (350 μm) are not contained, and the particle diameter is 1.5 to 12% for particles of 75 μm or less. The particle size should not be too large or too small, and the preferable average particle size is usually 120 to 160 μm. The method disclosed in this patent document is to control the particle size by the conditions in polymerizing polyethylene, and for example, by reducing the polymerization pressure or shortening the residence time in the reactor, the production of polyethylene particles having a particle size of more than 350 μm can be controlled.
For ultra high molecular weight polyethylene powders, not all particles require a concentrated particle size distribution. For example, a filter material, requires a uniform particle size distribution, but does not require concentration. CN102512875A discloses a method for preparing a filter material, which is to sieve the ultra-high molecular weight polyethylene resin powder and classify the ultra-high molecular weight polyethylene resin powder with different particle sizes and meshes. Filling the ultrahigh molecular weight polyethylene resin powder with different particle size distributions into a mould according to a certain assembly rule. This method, while addressing the need for a filter material, is not suitable for commercial production.
CN101245116A provides a catalytic system for the preparation of ultra high molecular weight polyethylene. The molecular weight of the polyethylene can be adjusted by adding an external electron donor into the catalytic system. However, the bulk density of polyethylene is not high, the particle size is about 160 μm, and the requirement of spinning (bulk density greater than 0.45 g/cm) cannot be met3Particle size less than 120 μm). Meanwhile, the method of adjusting the molecular weight by adopting an external electron donor is relatively complex and cannot meet the requirements of industrial production.
CN1569908A discloses a method for preparing ultra-high molecular weight polyethylene, which has good flow rate and processability. However, the ultra-high molecular weight polyethylene resin in the invention has low molecular weight and low mechanical property, and is not suitable for the production of high-strength and high-modulus fibers.
CN1106025A discloses a method for preparing ultra-high molecular weight polyethylene with high bulk density, which adopts gasoline as solvent and provides ultra-high molecular weight polyethylene with high bulk density, wherein the bulk density is in the range of 350-460 g/L. However, the gasoline is used as a solvent, and the ultra-high molecular weight polyethylene has unstable quality and poor mechanical property, so that the preparation of the high-strength polyethylene fiber is not facilitated. In addition, the gasoline distillation range is wide, and the energy consumption and the cost are high, so that the method is not beneficial to industrial production.
CN1189486C provides a catalyst system for preparing UHMWPE with high bulk density and good particle morphology, the catalyst is prepared by preparing magnesium-aluminum solution from magnesium halide and aluminum compound in the presence of alcohol, then adding titanium compound and silicon compound after reacting with electron donor, although the catalyst system has better catalytic activity, the bulk density of the obtained ultrahigh molecular weight polyethylene is not high enough, and the maximum is only 0.40g/cm3The particle size is 152-179 μm, the particle size distribution is wide, and the particle size distribution index is about 0.6. This form of polyethylene powder is not conducive to spinning.
Therefore, it is of great interest to develop new catalysts capable of catalytically preparing UHMWPE.
Disclosure of Invention
In order to improve the technical problem, the invention provides a titanium catalyst which comprises, by mass, 0.5-5% of Ti, 10-20% of Mg, 55-70% of Cl and 0.5-2% of Si;
preferably, the titanium catalyst contains 1.5 to 4.5 percent of Ti, 13 to 18 percent of Mg, 60 to 67 percent of Cl and 1 to 1.5 percent of Si;
for example, the content of Ti is 3.52%, 3.63%, 3.70%;
for example, the content of Mg is 15.9%, 16.1%, 16.5%;
for example, the Cl content is 62.5%, 63.1%, 63.7%;
for example, the Si content is 1.1%, 1.2%, 1.23%.
According to an embodiment of the present invention, the titanium catalyst has an average particle diameter of 2 to 15 μm, preferably 3 to 12 μm; exemplary are 3.1 μm, 5 μm, 6.1 μm, 10 μm, 10.1 μm.
The invention also provides a preparation method of the titanium catalyst, which comprises the following steps:
(1) reacting in-situ active magnesium chloride with an organic alcohol compound in a hydrocarbon solvent to obtain a magnesium alcohol compound reaction solution;
(2) reacting the magnesium alcoholate reaction liquid prepared in the step (1) with an electron donor organosilicon compound and a crystal precipitation agent anhydride;
(3) stirring and mixing the reaction liquid obtained in the step (2) and a titanium compound to carry out a titanium preloading reaction, wherein the stirring speed is preferably 200-1000 rpm;
(4) stirring and mixing the reaction liquid obtained in the step (3) and the electron donor organosilicon compound, reacting, filtering and separating to obtain a preloaded titanium catalyst component, wherein the stirring speed is preferably 200 and 1000 revolutions per minute;
(5) and (3) mixing the preloaded titanium catalyst group prepared in the step (4) with titanium tetrachloride for reaction, eluting the titanium-loaded catalyst, reacting under stirring (preferably reacting for 0.5-4h), and filtering and washing after the reaction is finished to obtain the solid titanium catalyst.
According to an embodiment of the invention, the in situ active magnesium chloride in step (1) is (MgCl)2)(R1MgCl)aMgb[Ti(OR2)4)]c[Si(OR3)4]dWherein R is1、R2、R3May be the same or different and are independently selected from C1-12Alkyl, a is 0.02-1, b is 0-0.5, c is 0-0.8, d is 0-0.8; for example, R1、R2、R3Can be independently selected from C1-4Alkyl groups such as methyl, ethyl, propyl, butyl; for example, a is 0.1 to 0.8, b is 0 to 0.2, c is 0.1 to 0.3, d is 0 to 0.4; illustratively, R1And R2Is butyl, R3Is ethyl, a equals 0.59 or 0.58, b equals 0.08, c equals 0.07, and d equals 0.23.
According to an exemplary embodiment of the invention, the in situ active magnesium chloride may be selected from (MgCl)2)(BuMgCl)0.59Or (MgCl)2)(BuMgCl)0.58Mg0.08[Ti(OC4H9)4)]0.07[Si(OC2H5)4]0.23。
According to the embodiment of the invention, the in-situ active magnesium chloride has the specific surface area of 85-110 m2/g；
According to the embodiment of the invention, the pore volume of the in-situ active magnesium chloride is 50-70 mL/g;
according to the embodiment of the invention, the particle size of the in-situ active magnesium chloride is 2-8 μm.
According to the embodiment of the invention, the in-situ active magnesium chloride in the step (1) is prepared by adopting a preparation method that magnesium powder is activated by elemental iodine and then reacts with chloroalkane, or is prepared by adding elemental iodine to activate and simultaneously adding titanate and silicate to react; the reaction conditions are preferably under the protection of nitrogen and under anhydrous conditions.
According to an embodiment of the present invention, the organic alcohol in step (1) may be selected from at least one of ethanol, propanol, butanol, hexanol, 2-methyl alcohol, n-heptanol, isooctanol, or n-octanol;
according to an embodiment of the present invention, the organosilicon compound in step (2) and step (4) may be selected from: dimethyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, isobutyldimethoxysilane, dibutyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylbutyldimethoxysilane, cyclopentylpropyldimethoxysilane, dicyclopentyldimethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, gamma-chloropropyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltrioxysilane, dimethyldiethoxysilane, dipropyldiethoxysilane, diisopropyldiethoxysilane, isobutyldiethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, At least one of dibutyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylisopropyldiethoxysilane, cyclopentylisobutyldiethoxysilane, cyclopentylisopropyldiethoxysilane, cyclopentylbutyldiethoxysilane, cyclopentylpropyldiethoxysilane, dicyclopentyldiethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, gamma-chloropropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, and mixtures thereof;
according to an embodiment of the present invention, the acid anhydride in the step (2) may be selected from at least one of norbornene acid anhydride, phthalic anhydride, maleic anhydride and a mixture thereof; preferably, the acid anhydride is used in an amount of 0.05 to 1.0 mole per mole of active magnesium chloride.
According to an embodiment of the present invention, the titanium compound in the step (3) may be at least one selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium, and a mixture thereof;
according to an embodiment of the present invention, the stirring speed in steps (3) to (5) may be 100-; for example, 200 to 1000 rpm, preferably 400 and 600 rpm.
In the preparation method of the titanium catalyst, the titanium content of the catalyst is controlled by titanium-carrying elution (step (5)), so that the aim of reducing the activity of the catalyst is fulfilled; meanwhile, titanium tetrachloride is used as a solvent, and when part of alkoxy titanium is eluted, part of alkoxy titanium is combined into the carrier to redistribute the titanium active centers in the catalyst, so that the distance between the titanium active centers is increased, and the catalyst with low titanium loading capacity is obtained integrally. The aim of controlling the particle size of the ultra-high molecular weight polyethylene is achieved by controlling the active ingredients and the active efficiency of the catalyst. Meanwhile, the molecular chain entanglement is reduced, and the crystallinity is improved.
The invention provides application of the titanium catalyst in regulating and controlling the particle size and particle size distribution of ultrahigh molecular weight polyethylene.
The invention also provides a preparation method of the ultra-high molecular weight polyethylene or a method for regulating and controlling the particle size and the particle size distribution of the ultra-high molecular weight polyethylene, which comprises the step of adding the titanium catalyst and the cocatalyst into a polymerization reaction system for preparing the polyethylene to prepare the ultra-high molecular weight polyethylene.
According to an embodiment of the invention, the cocatalyst is a metal-organic compound, preferably an organoaluminium compound R3- nA1XnWherein X is halogen and R is C1-12Alkyl (e.g. being C)1-4Alkyl), n is an integer of 0 to 2; for example, triethylaluminum;
according to an embodiment of the present invention, the molar ratio of aluminum in the cocatalyst to titanium in the titanium catalyst is 10 to 800, preferably 20 to 200, more preferably 30 to 150.
According to an embodiment of the present invention, the titanium catalyst has an average particle diameter of 2 to 15 μm or less, preferably 3 to 12 μm; exemplary are 3.1 μm, 5 μm, 6.1 μm, 10 μm, 10.1 μm.
According to an embodiment of the present invention, the titanium catalyst may be a single average particle size titanium catalyst or a combination of different average particle sizes titanium catalysts. The titanium catalyst may be added or subtracted to a certain particle size depending on the desired particle size distribution of the product. For example, to increase the amount of low mesh product, the proportion of catalyst having a large particle size (e.g., a particle size in excess of 10 μm) is increased; to increase the amount of high number of products, the proportion of catalyst having a small particle size (e.g. a particle size of less than 10 μm, such as 3.1 μm or 5 μm) may be increased.
According to an embodiment of the present invention, the polymerization reaction temperature is 40 to 90 ℃, preferably 50 to 85 ℃; the reaction pressure is as follows: 0.1 to 1.0MPa, preferably 0.2 to 0.8 MPa; the stirring speed can be adjusted according to the different particle sizes of the required polyethylene and can be 100-1600 rpm; for example, 200 to 1000 rpm, and further for example, 400 and 600 rpm.
According to an embodiment of the invention, the titanium catalyst has a catalytic activity of 15000 to 40000gPE/gcat, preferably 25000 to 30000 gPE/gcat.
The invention also provides the ultrahigh molecular weight polyethylene prepared by the method.
Preferably, the bulk density of the ultra-high molecular weight polyethylene is 0.43g/cm3Above, for example, 0.43 to 0.47g/cm3(ii) a Preferably, the particle size of the ultra-high molecular weight polyethylene is adjustable within the range of 120-250 μm; the particle size distribution D50 is adjustable within the range of 0.5-1.0.
Advantageous effects
The titanium catalyst provided by the invention achieves the purpose of controlling the activity efficiency of the catalyst by controlling the content of the active component titanium element, the distribution of the titanium compound in the catalyst and the particle size of the catalyst, and further can control the particle size of the ultra-high molecular weight polyethylene particles generated in the process of polymerizing ethylene. When the catalyst is used for preparing the ultra-high molecular weight polyethylene, the ultra-high molecular weight polyethylene with controllable particle size and particle size distribution can be obtained. The requirements of the fiber, the diaphragm for the secondary battery, the filtering material, the compression molding product and other products on the particle size and the particle size distribution of the ultra-high molecular weight polyethylene powder are met.
Drawings
Fig. 1 is an SEM image of catalyst 1.
Fig. 2 is an SEM image of catalyst 2.
Fig. 3 is an SEM image of catalyst 3.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Preparation example 1: catalyst 1
Putting 0.2mol of magnesium powder into a 500mL three-neck flask replaced by nitrogen, and adding 100mL of decane, 0.02g of iodine and a small amount of n-butyl chloride; heating to 75 deg.C, stirring and activating for 2 hr, dripping 1mol of dried n-butyl chloride, observing obvious reaction, continuing reaction for 3 hr, filtering, washing the obtained solid with hexane, drying to obtain carrier, and analyzing element to show that its carrier composition is (MgCl)2)(BuMgCl)0.59。
0.05mol (calculated by Mg) of the carrier, 20mL of decane and 26mL of isooctanol (0.167mol) are heated to 130 ℃ to react for 60 minutes, the temperature is reduced to 65 ℃, 15mmol of gamma-chloropropyltrimethoxysilane (silane electron donor) and 15mmol of norbornene anhydride are added at the temperature to continue the reaction for 60 minutes, and the mixture is cooled to room temperature. Slowly dropwise added to 200mL of TiC1 at-10 ℃ over a period of 90 minutes4And (2) stirring at the speed of 1000 rpm, keeping the temperature at 0 ℃ for 60 minutes after the dropwise addition is finished, slowly heating to 110 ℃ within 120 minutes, adding 5mmol of the same silane electron donor at the temperature, continuing to react for 120 minutes to obtain the solid catalyst, and finding that the settling speed of solid catalyst particles is high after the stirring is stopped. The solvent is removed by decanting and then 200mL of TiC1 is added4The reaction was continued for one hour at 110 ℃ and this process was also referred to as titanium-supported elution, after which the solid catalyst was filtered off thermally. Washing with hexane, 40mL each time, until the filtrate is basically colorless, wherein the content of free titanium is less than 0.3mg/mL, and drying to obtain the solid catalyst 1. Catalyst 1 is a quasi-sphereElemental analysis of catalyst 1: 3.52% of Ti, 16.5% of Mg, 62.5% of Cl, Si: 1.1 percent; the particle size was 3.1 μm (see FIG. 1).
Preparation example 2: catalyst 2
Catalyst 2 was prepared as in preparation example 1, except that the stirring speed was 600 rpm. Elemental analysis of catalyst 2: 3.63% of Ti, 16.1% of Mg, 63.1% of Cl, Si: 1.2 percent; the particle size was 6.1 μm (see FIG. 2).
Preparation example 3: catalyst 3
Catalyst 3 was prepared as in preparation example 1, except that the stirring speed was 400 rpm. Elemental analysis of catalyst 3: 3.70% of Ti, 15.9% of Mg, 63.7% of Cl, Si: 1.23 percent; the particle size was 10.1 μm (see FIG. 3).
Preparation of ultra-high molecular weight polyethylene Using the catalysts of preparation examples 1 to 3
Example 1
In a 10L stainless steel autoclave, after nitrogen replacement, 6.5L dehydrated hexane, a triethylaluminum hexane solution (according to the molar ratio of Al to Ti of 100) and 160 mg of catalyst are sequentially added, the stirring speed is 1000 r/min, the temperature is raised to 50 ℃, ethylene is introduced until the kettle pressure is 0.8Mpa (gauge pressure), the polymerization reaction is carried out for 2 hours at 65 ℃ under the kettle pressure of 0.8Mp, the temperature is reduced to the room temperature, and the UHMWPE polyethylene product is obtained after discharging and drying. The product polymerized by the catalyst of each example was subjected to catalyst activity measurement, bulk density measurement, viscosity average molecular weight measurement, measurement of average particle diameter and particle diameter distribution, etc., and the results are shown in tables 1 and 2.
The method comprises the following steps: the SEM of the catalyst was tested with Hitachi Regulus 8100. The apparent density was measured by the method of ASTM-D-1895. The polyethylene particle size was determined by a laser particle analyzer (Mastersizer X, Malvern), wherein the D10, D50, and D90 distributions refer to the size of the particles at each percentage of 10, 50, and 90. D50 is defined as the mean particle distribution and the particle size distribution is defined as (D90-D10)/D50. Viscosity average molecular weight was measured by high temperature Ubbelohde viscometer method according to ASTM D4020-05, capillary inner diameter was 0.53mm, and M was usedη＝5.37×104·[η]1.37And (6) performing calculation. Screening was determined according to GB T21843-2008.
Example 2
The same as in example 1, except that the catalyst 2 was used.
Example 3
The same as in example 1, except that the catalyst used was catalyst 3.
Example 4
The same as in example 1, except that the stirring speed was 600 rpm.
Example 5
The same as in example 1, except that the stirring speed was 300 rpm.
Example 6
The same as in example 1, except that 48mg of catalyst 1 and 12mg of catalyst 3 were used.
Example 7
The same as in example 1, except that 42mg of catalyst 1 and 18mg of catalyst 3 were used.
Example 8
The same as in example 7, except that the stirring speed was 500 rpm.
Comparative example 1
The catalyst 1 was prepared by the method except that the titanium supported was used only once and the elution step with titanium supported was not carried out. Drying to obtain the solid catalyst. Elemental analysis results of the catalyst: 7.2% of Ti, 15.5% of Mg, 64.5% of Cl, Si: 1.4 percent; the particle size was 3.5. mu.m.
Comparative example 2
The catalyst 2 was prepared by the method except that the titanium supported was used only once and the elution step with titanium supported was not carried out. Drying to obtain the solid catalyst. Elemental analysis results of the catalyst: 7.3% of Ti, 15.2% of Mg, 64.6% of Cl, Si: 1.4%, particle size 6.7 μm.
Comparative example 3
The catalyst 3 was prepared by the method except that the titanium supported was used only once and the elution step with titanium supported was not carried out. Drying to obtain the solid catalyst. Elemental analysis results of the catalyst: 7.1% of Ti, 16.1% of Mg, 64.2% of Cl, Si: 1.5 percent; the particle size was 11.2. mu.m.
TABLE 1 example polymerization results
Figure BDA0003314950190000091
Figure BDA0003314950190000101
TABLE 2 particle size and particle size distribution
Figure BDA0003314950190000102
From the data in Table 2, it can be seen that as the catalyst particle size increases, the ultra high molecular weight polyethylene particle size increases, and the sieve moves from a large mesh to a small mesh. The particle size of the polyethylene powder can be controlled by regulating and controlling the particle size of the catalyst; from the data of examples 1, 4 and 5, it can be seen that as the stirring speed is reduced, the polyethylene particle size increases and the sieving likewise moves from large to small mesh, indicating that the stirring speed can also change the particle size and particle size distribution. The data of examples 6, 7, 8 show that the particle size distribution of polyethylene powder can be controlled by adjusting the ratio of the two catalysts when mixing two catalysts of different particle size, especially when the particle size difference is large. The particle size of the existing catalyst and the particle size distribution of the ultrahigh molecular weight polyethylene powder produced by the catalyst (i.e. the catalyst provided by the comparative examples 1-3) which has the similar particle size to the embodiment and high content of Ti element do not have obvious regulation rules.
The ultra-high molecular weight polyethylene powder of the present invention has industrial applicability in ultra-high molecular weight polyethylene fiber, battery separator, and filter, and polyethylene particle products with specific particle size ranges can be customized according to the catalyst of the present invention according to the requirements of different fields for polyethylene particles, for example, the polyethylene particles of examples 1, 4, and 5 can be used for preparing lithium battery separator or fiber material, while the large particle polyethylene product of example 3 can be used for filter material.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The titanium catalyst comprises, by mass, 0.5-5% of Ti, 10-20% of Mg, 55-70% of Cl and 0.5-2% of Si;
preferably, the titanium catalyst contains 1.5 to 4.5 percent of Ti, 13 to 18 percent of Mg, 60 to 67 percent of Cl and 1 to 1.5 percent of Si;
preferably, the titanium catalyst has an average particle diameter of 2 to 15 μm, preferably 3 to 12 μm.
2. The method for preparing the titanium catalyst according to claim 1, comprising the steps of:
(1) reacting in-situ active magnesium chloride with an organic alcohol compound in a hydrocarbon solvent to obtain a magnesium alcohol compound reaction solution;
(2) reacting the magnesium alcoholate reaction liquid prepared in the step (1) with an electron donor organosilicon compound and a crystal precipitation agent anhydride;
(3) stirring and mixing the reaction liquid obtained in the step (2) and a titanium compound to carry out a titanium preloading reaction;
(4) stirring and mixing the reaction liquid obtained in the step (3) and an electron donor organosilicon compound, reacting, filtering and separating to obtain a preloaded titanium catalyst component;
(5) and (3) mixing the preloaded titanium catalyst group prepared in the step (4) with titanium tetrachloride for reaction, eluting the titanium-loaded catalyst group, reacting under stirring, and filtering and washing after the reaction is finished to obtain the solid titanium catalyst.
3. The process according to claim 2, wherein the in-situ active magnesium chloride in step (1) is (MgCl)2)(R1MgCl)aMgb[Ti(OR2)4)]c[Si(OR3)4]dWherein R is1、R2、R3Can be combined with each otherAre identical or different and are independently selected from C1-12Alkyl, a is 0.02-1, b is 0-0.5, c is 0-0.8, d is 0-0.8;
preferably, the in situ active magnesium chloride is (MgCl)2)(BuMgCl)0.59Or (MgCl)2)(BuMgCl)0.58Mg0.08[Ti(OC4H9)4)]0.07[Si(OC2H5)4]0.23；
Preferably, the in-situ active magnesium chloride in the step (1) is prepared by a preparation method that magnesium powder is activated by elemental iodine and then reacts with chloralkane, or is prepared by adding elemental iodine to activate and simultaneously adding titanate and silicate ester to react; the preferable reaction condition is under the protection of nitrogen and under anhydrous condition;
preferably, the organic alcohol in step (1) may be selected from at least one of ethanol, propanol, butanol, hexanol, 2-methyl alcohol, n-heptanol, isooctanol, and n-octanol.
4. The production method according to claim 2 or 3, characterized in that the organosilicon compound in step (2) and step (4) is selected from: dimethyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, isobutyldimethoxysilane, dibutyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylbutyldimethoxysilane, cyclopentylpropyldimethoxysilane, dicyclopentyldimethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, gamma-chloropropyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltrioxysilane, dimethyldiethoxysilane, dipropyldiethoxysilane, diisopropyldiethoxysilane, isobutyldiethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, At least one of dibutyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylisopropyldiethoxysilane, cyclopentylisobutyldiethoxysilane, cyclopentylisopropyldiethoxysilane, cyclopentylbutyldiethoxysilane, cyclopentylpropyldiethoxysilane, dicyclopentyldiethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, gamma-chloropropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, and mixtures thereof;
preferably, the acid anhydride in step (2) is selected from the group consisting of norbornene anhydride, phthalic anhydride, maleic anhydride and mixtures thereof; preferably, the acid anhydride is used in an amount of 0.05 to 1.0 mole per mole of active magnesium chloride.
5. The production method according to any one of claims 2 to 4, wherein the titanium compound in the step (3) is at least one selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium, and a mixture thereof;
preferably, the stirring speed in the steps (3) to (5) is 100-; for example, 200 to 1000 rpm, preferably 400 and 600 rpm.
6. Use of the titanium catalyst of claim 1 for regulating the particle size and particle size distribution of ultra-high molecular weight polyethylene.
7. A method for preparing ultra-high molecular weight polyethylene or a method for regulating and controlling the particle size and the particle size distribution of the ultra-high molecular weight polyethylene, which comprises adding the titanium catalyst and the cocatalyst according to claim 1 into a polymerization reaction system for preparing the polyethylene to prepare the ultra-high molecular weight polyethylene;
preferably, the cocatalyst is a metal-organic compound, preferably an organoaluminium compound R3-nA1XnWherein X is halogen and R is C1-12An alkyl group, n is an integer of 0 to 2; for example, triethylaluminum;
preferably, the molar ratio of the aluminum in the cocatalyst to the titanium in the titanium catalyst is 10-800;
preferably, the titanium catalyst has an average particle diameter of 2 to 15 μm or less, preferably 3 to 12 μm.
8. The method of claim 7, wherein the titanium catalyst is a single average particle size titanium catalyst or a combination of different average particle sizes titanium catalysts.
9. The process according to claim 7 or 8, wherein the polymerization temperature is 40 to 90 ℃, preferably 50 to 85 ℃; the reaction pressure is as follows: 0.1 to 1.0MPa, preferably 0.2 to 0.8 MPa; the stirring speed is adjusted according to the different particle sizes of the required polyethylene and can be 100-1600 rpm; for example, 200 to 1000 rpm, and further for example, 400 and 600 rpm.
10. Ultra-high molecular weight polyethylene produced by the process of any one of claims 7 to 9;
preferably, the bulk density of the ultra-high molecular weight polyethylene is 0.43g/cm3Above, for example, 0.43 to 0.47g/cm3(ii) a Preferably, the particle size of the ultra-high molecular weight polyethylene is adjustable within the range of 120-250 μm; the particle size distribution D50 is adjustable within the range of 0.5-1.0.
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