CN114133473B - Special resin powder for chlorinated polyethylene and preparation method and application thereof - Google Patents

Special resin powder for chlorinated polyethylene and preparation method and application thereof Download PDF

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CN114133473B
CN114133473B CN202111545906.8A CN202111545906A CN114133473B CN 114133473 B CN114133473 B CN 114133473B CN 202111545906 A CN202111545906 A CN 202111545906A CN 114133473 B CN114133473 B CN 114133473B
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preparation
antimony
catalyst
reaction kettle
chlorinated polyethylene
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CN114133473A (en
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李允升
徐彦龙
蓝程程
朱文俊
李胜龙
高晴晴
王琪
张建新
张宏科
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Wanhua Chemical Group 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C08F8/22—Halogenation by reaction with free halogens
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a special resin powder for chlorinated polyethylene, a preparation method and application thereof. The special resin powder has relatively low wax content, relatively wide molecular weight distribution and relatively small average particle size, and can effectively solve the problems that the conventional special material is uneven in chlorination, easy to adhere to a kettle and cannot achieve good processability and mechanical properties when being applied to downstream production of chlorinated polyethylene. The invention provides a special resin powder for chlorinated polyethylene, which is polyethylene or copolymer of ethylene and alpha-olefin, and has powder density of 0.945-0.960 g/cm 3 ，MFR 5kg The average grain diameter is 100-300 mu m, the S value is 17-31, and the wax content is less than or equal to 0.5wt% at 0.1-10 g/10 min.

Description

Special resin powder for chlorinated polyethylene and preparation method and application thereof
Technical Field
The invention relates to the technical field of preparation of special resin for chlorinated polyethylene.
Background
Chlorinated polyethylene is a chlorinated random polymer produced by the chlorination substitution reaction of polyethylene resins, and can be regarded as a terpolymer of ethylene, vinyl chloride and 1, 2-dichloroethylene, having the same carbon backbone structure as the polyethylene resins. Its properties are related to the crystallization regularity, molecular weight size and distribution, molecular chain and branched structure, particle size and distribution, melt flow rate and S value of the resin raw material used, and also to chlorine content, chlorination production mode, etc.
The chlorinated polyethylene can be classified into plastic chlorinated polyethylene (chlorine content 15%), elastic chlorinated polyethylene chlorine content (16-25%), elastomer chlorinated polyethylene (26-50%), hard chlorinated polyethylene (51-60%) and highly elastic chlorinated polyethylene (> 60%) according to the chlorine content. The special structure of the chlorinated polyethylene endows the chlorinated polyethylene with excellent flexibility, weather resistance, ozone resistance, chemical corrosion resistance, cold resistance and flame retardance, so the chlorinated polyethylene is widely applied to the fields of plastic doors and windows, PVC pipes and plates, waterproof coiled materials, anti-corrosion coatings, wires and cables and the like.
The production method of chlorinated polyethylene mainly comprises three methods of solution method, suspension method and gas-solid phase method. The solution process was the earliest developed process for the preparation of chlorinated polyethylene and has been essentially eliminated. Suspension methods, including aqueous suspension and solid suspension, are currently the most mature and widely used production methods. The gas-solid phase method is not industrialized at present. The powder resin used in the suspension method can be directly produced by polymerization, or can be obtained by grinding and sieving conventional polyethylene resin.
The conventional special resin for chlorinated polyethylene adopts a Ziegler-Natta catalyst system, and the special resin with wide distribution is obtained through multi-kettle serial polymerization. However, the chlorinated polyethylene-specific resin produced by this method tends to produce too much low molecular wax in the first reaction vessel, and the average size of the resin particles is relatively large. When the content of the oligomer wax in the special resin is too high, the system viscosity is easily caused to be too high by melting in the chlorination process, so that the powder materials are mutually bonded, chlorinated polyethylene products are unevenly chlorinated, and technological safety accidents such as kettle sticking and stopping are easily caused. When the particle size is too large, the chlorination rate is reduced, and the impact strength, production efficiency and processability of the chlorinated product as a downstream blending modifier are low.
Patent CN10451337a discloses a resin powder for chlorinated polyethylene with low mooney viscosity and a preparation method thereof. Under the action of Ziegler-Natta catalyst, n-hexane is used as dispersant, and the polymerization is carried out in a mode of connecting two reaction kettles in series, and the chlorinated polyethylene with narrow particle size distribution and low Mooney viscosity is obtained through the control of technological parameters of a two-reactor. However, the method can produce excessive low molecular wax under the condition of high hydrogen-ethylene ratio in the first reaction kettle, and the prepared special resin has larger average particle size. Meanwhile, the two kettles have great parameter difference, and certain difficulty exists in matching control, so that the quality of the product is easy to fluctuate.
A chlorinated polyethylene-specific resin of controlled wax content is disclosed in patent CN104284912 a. The special resin powder with low wax content is prepared by using a metallocene catalyst system and n-hexane as a dispersing agent in a continuous slurry reaction kettle. However, the special resin prepared by the method has small S value (molecular weight distribution) and can not simultaneously achieve good processing performance and mechanical property.
Disclosure of Invention
The invention provides a special resin powder for chlorinated polyethylene, a preparation method and application thereof. The special resin powder for chlorinated polyethylene provided by the invention has relatively low wax content, relatively wide molecular weight distribution and relatively small average particle diameter, and can be used for obtaining products with the characteristics by optimizing a catalyst system used in the preparation process of the special resin powder for chlorinated polyethylene.
The invention provides the following technical scheme for achieving the purpose:
the invention provides a special resin powder for chlorinated polyethylene, which is polyethylene or copolymer of ethylene and alpha-olefin, and has powder density of 0.945-0.960 g/cm 3 ，MFR 5kg The average grain diameter is 100-300 mu m, the S value is 17-31, and the wax content is less than or equal to 0.5wt% at 0.1-10 g/10 min.
In the art, waxes in chlorinated polyethylene-specific resin powders are generally oligomeric waxes with weight average molecular weights of 500 to 14000.
Further, the alpha-olefin is propylene, butene-1, hexene-1, octene-1 or 4-methylpentene-1.
The present invention also provides a method for preparing the above-described chlorinated polyethylene-specific resin powder, which is prepared by slurry polymerization of ethylene and optionally alpha-olefin in a single slurry reactor in the presence of a catalyst, wherein the catalyst comprises an antimony element modified supported chromium-based catalyst, and the average particle size of the antimony element modified supported chromium-based catalyst is preferably 6-20 μm.
According to the preparation method, the antimony element modified supported chromium catalyst is adopted to produce the resin powder special for chlorinated polyethylene, so that the advantages of low wax content, wide molecular weight distribution and small average particle size can be achieved. Moreover, the reaction can be carried out in a single slurry reaction kettle, so that the process of generating small molecules in the first step in the step-by-step reaction is avoided, and the production of the oligomer wax is reduced; and the reaction is carried out in a single reaction kettle, so that the process parameters are easy to control, and the process control difficulty is greatly reduced. The special resin powder provided by the invention is used for producing chlorinated polyethylene, the chlorination rate is high, the chlorination pressure is stable, the chlorine distribution is uniform, and the obtained chlorinated polyethylene has excellent processability while maintaining good mechanical properties.
Preferably, the antimony element-modified supported chromium-based catalyst is added in an amount of 0.02 to 2mg, preferably 0.03 to 0.2mg, per gram of ethylene.
Further, the catalyst also comprises a cocatalyst, wherein the cocatalyst is aluminum alkyl, preferably the cocatalyst is one or more of triethylaluminum, triisobutylaluminum, ethoxydiethylaluminum, diethylaluminum chloride or methylaluminoxane, more preferably triisobutylaluminum;
preferably, the amount of the cocatalyst is 0.01 to 10mL, preferably 0.05 to 1mL, per mg of the antimony element-modified supported chromium-based catalyst.
Further, the loading amount of the antimony element is 0.01 to 5wt%, preferably 0.02 to 1wt%, based on the total weight of the antimony element-modified supported chromium-based catalyst.
In a preferred embodiment, the preparation step of the antimony element modified supported chromium-based catalyst comprises:
1) Placing a supported chromium catalyst (serving as a carrier) in a tube furnace, loading antimony elements in an antimony compound onto the supported chromium catalyst through vapor deposition, and roasting to obtain a precursor;
2) And (2) carrying out reduction reaction on the precursor obtained in the step (1) in the presence of an organic metal reducing agent, reducing to obtain a catalyst of low-valence active metal element, and drying the obtained reduction product to obtain the antimony element modified supported chromium catalyst.
In some embodiments, step 1) is performed under an inert atmosphere at a flow rate of from 5 to 100mL/min, preferably from 40 to 60mL/min; the reaction temperature in step 1) is 100 to 600 ℃, preferably 300 to 550 ℃; the deposition time is 120 to 480min, preferably 180 to 300min. In the step 1), the roasting is carried out in inert gas, the roasting temperature is 300-1000 ℃, preferably 400-800 ℃ for 1-10 hours, preferably 4-6 hours, and then cooling is carried out; alternatively, the calcination is performed in two stages, a low temperature stage at 100 to 300 ℃ for 1 to 10 hours, preferably 4 to 8 hours, and a high temperature stage at 300 to 900 ℃ for 1 to 10 hours, preferably 4 to 8 hours.
In some embodiments, in step 2), the reduction is carried out under an inert atmosphere at a reduction temperature of 20 ℃ to 100 ℃, preferably 20 ℃ to 70 ℃; the reduction time is 0.5 to 20 hours, preferably 0.5 to 10 hours.
The inert gas used is not particularly limited, and nitrogen is preferable.
In step 1), the supported chromium-based catalyst used may be a commercially available product such as a base company Advent C series catalyst.
In some embodiments, in step 1), the antimony compound is selected from one or more of antimony trioxide, antimony pentoxide, antimony trichloride, antimony pentachloride, sodium antimonate, sodium hexafluoroantimonate, antimony acetate, preferably antimony trioxide.
In some embodiments, in step 2), the organometallic reducing agent is one or more of triethylaluminum, triisobutylaluminum, ethoxydiethylaluminum, diethylaluminum monochloride or methylaluminoxane, preferably diethylaluminum ethoxide; preferably, the molar ratio of aluminum to chromium is preferably 0.01 to 500, more preferably 0.1 to 50, based on the aluminum element in the organometallic reducing agent and the chromium element in the supported chromium-based catalyst.
In some embodiments, the slurry polymerization is carried out in a single slurry reactor in the presence of the catalyst using an alkane solvent as a medium;
the slurry polymerization reaction has a reaction temperature of 70-85 ℃, preferably 75-82 ℃, a reaction pressure of 0.5-1.5Mpa, preferably 0.8-1.2Mpa, a molar ratio of hydrogen to ethylene of 0.01-1, preferably 0.02-0.1, and a molar ratio of alpha-olefin to ethylene of 0-0.1, preferably 0.01-0.04.
In one embodiment, the preparation method of the chlorinated polyethylene special resin powder specifically comprises the following steps:
(1) Adding an alkane solvent into the slurry reaction kettle, starting continuous stirring, and heating the reaction kettle to 70-85 ℃;
(2) Adding hydrogen and optional alpha-olefin into the slurry reactor, wherein the molar ratio of the hydrogen to the ethylene is 0.01-1, and the molar ratio of the alpha-olefin to the ethylene is 0-0.1;
(3) Introducing ethylene into the slurry reaction kettle, and enabling the reaction pressure in the slurry reaction kettle to reach 0.5-1.5MPa;
(4) Adding a catalyst into the slurry reactor to perform slurry polymerization, for example, for 1-5 hours (for example, for 3 hours); during the polymerization reaction, the relatively stable pressure in the reaction kettle is maintained through the introduction of ethylene;
(5) The pressure in the slurry reaction kettle is emptied, and the temperature of materials in the slurry reaction kettle is reduced, for example, to 20 ℃ through jacket water of the reaction kettle;
(6) Discharging polymerization reactant slurry from the bottom of the slurry reaction kettle, and obtaining the special resin powder for chlorinated polyethylene after flash evaporation, centrifugation and drying.
As the polymeric dispersant, an alkane solvent, preferably, one or more of butane, pentane, n-hexane or heptane; n-hexane is preferred.
The invention also provides application of the special resin powder for chlorinated polyethylene in a chlorinated polyethylene preparation process.
The invention adopts the antimony modified supported chromium catalyst, which has multiple active centers, each active center has different chain transfer rate and chain growth constant, the obtained product has the characteristics of high melt strength, wide processability and the like, and no obvious byproduct such as low molecular wax is produced during polymerization. The invention can overcome the problems of high wax content, narrow molecular weight distribution, large product grain diameter and the like of the special resin prepared by the existing chlorinated polyethylene special resin slurry polymerization process through optimizing a catalyst system; the special resin for chlorinated polyethylene is favorable for solving the problems that the traditional special resin is uneven in chlorination, easy to adhere to a kettle and incapable of achieving good processing performance and mechanical performance when being used for producing chlorinated polyethylene at the downstream.
Based on the special resin powder for chlorinated polyethylene, the chlorinated polyethylene is prepared by downstream chlorination, so that the problems of overhigh chlorination pressure, easiness in kettle adhesion, low chlorination rate and the like in the chlorination process can be solved.
Detailed Description
For a better understanding of the technical solution of the present invention, the following examples are further described below, but the present invention is not limited to the following examples.
The performance detection method of the special resin powder for chlorinated polyethylene is as follows:
density: reference GB/T1033.2-2010
MFR 21.6kg And MFR (MFR) 5kg : reference GB/T3682-2000
Bulk density: reference GB/T1636-2008
Wax content: about 10g of a sample of a special resin powder for chlorinated polyethylene was weighed and put into an extraction cartridge of a known weight, and the cartridge and the sample (m 1 ) Put into an extractor with n-heptane together, put the extractor into constant temperature oil bath, and extract for 6 hours at 80 ℃. After extraction, the extraction paper tube containing the residual polymer is placed in a vacuum oven, dried to constant weight at 90 ℃, then transferred into a silica gel drying box, cooled for 30 minutes and weighed as m 2 (to the nearest 0.1 mg), wax content= (m 1 -m 2 )*100％/m 1 。
S value: the S value of the polymer is MFR 21.6kg And MFR (MFR) 5kg Ratio of (2)
Average particle diameter: the particle size measurement is carried out on a Beckman Coulter LS type 230 laser particle size analyzer, and the particle size measurement range is 0.04-2000 microns.
The method for detecting the properties of the chlorinated polyethylene comprises the following steps:
chlorine content/%: reference is made to the B method in GB/T7139-2002.
Mooney viscosity: reference is made to GB/T1232.1-2000.
Shore hardness: reference is made to GB/T531.1-2008.
Tensile strength: reference GB/T528-2009 was made using a type I dumbbell cutter.
Elongation at break: reference is made to GB/T1340.1-2006.
Example 1
Example 1 a chlorinated polyethylene-specific resin powder was prepared according to the following process steps:
(1) Adding an alkane solvent into the slurry reaction kettle, starting continuous stirring, and heating the reaction kettle to 80 ℃; wherein the alkane solvent is normal hexane, and the stirring speed is 500rpm.
(2) Adding hydrogen and alpha-olefin into a slurry reaction kettle, wherein the molar ratio of the hydrogen to the ethylene is 0.04, and the molar ratio of the alpha-olefin to the ethylene is 0.02; wherein the alpha-olefin is hexene-1.
(3) Ethylene is introduced into the slurry reaction kettle, and the reaction pressure in the slurry reaction kettle reaches 0.80MPa;
(4) Adding an antimony element modified supported chromium catalyst and a cocatalyst into a slurry reaction kettle for slurry polymerization reaction (wherein the dosage of the antimony element modified supported chromium catalyst is 20mg, the dosage of the cocatalyst is 3mL, and the cocatalyst is triisobutylaluminum), and reacting for 3 hours; in the polymerization reaction process, the relative stability of the pressure in the reaction kettle is maintained through the introduction of ethylene, and 423g of ethylene is reacted together;
(5) The internal pressure of the slurry reaction kettle is emptied, and the temperature of materials in the slurry reaction kettle is reduced to 20 ℃ through jacket water of the reaction kettle;
(6) Discharging polymerization reactant slurry from the bottom of the slurry reaction kettle, and obtaining the special resin powder for chlorinated polyethylene after flash evaporation, centrifugation and drying.
The properties of the chlorinated polyethylene-specific resin powder obtained in example 1 were as follows: density of 0.949g/cm 3 ，MFR 5kg 2.1g/10min, bulk density 0.41g/cm 3 The wax content was 0.38%, the S value was 25, and the average particle diameter was 259. Mu.m.
Example 2
Example 2a chlorinated polyethylene specific resin powder was prepared according to the following process steps:
(1) Adding an alkane solvent into the slurry reaction kettle, starting continuous stirring, and heating the reaction kettle to 80 ℃; wherein the alkane solvent is normal hexane, and the stirring speed is 500rpm.
(2) Adding hydrogen and alpha-olefin into a slurry reaction kettle, wherein the molar ratio of the hydrogen to the ethylene is 0.02, and the molar ratio of the alpha-olefin to the ethylene is 0.01; wherein the alpha-olefin is butene-1.
(3) Ethylene is introduced into the slurry reaction kettle, and the reaction pressure in the slurry reaction kettle reaches 0.85MPa;
(4) Adding an antimony element modified supported chromium catalyst and a cocatalyst into a slurry reaction kettle for slurry polymerization reaction (wherein the dosage of the antimony element modified supported chromium catalyst is 20mg, the dosage of the cocatalyst is 3mL, and the cocatalyst is triisobutylaluminum), and reacting for 3 hours; during the polymerization reaction, the relatively stable pressure in the reaction kettle is maintained by introducing ethylene, and 486g of ethylene is reacted together;
(5) The internal pressure of the slurry reaction kettle is emptied, and the temperature of materials in the slurry reaction kettle is reduced to 20 ℃ through jacket water of the reaction kettle;
(6) Discharging polymerization reactant slurry from the bottom of the slurry reaction kettle, and obtaining the special resin powder for chlorinated polyethylene after flash evaporation, centrifugation and drying.
The properties of the chlorinated polyethylene-specific resin powder obtained in example 2 were as follows: density of 0.956g/cm 3 ，MFR 5kg 1.1g/10min, bulk density 0.40g/cm 3 The wax content was 0.23%, the S value was 29, and the average particle diameter was 241. Mu.m.
The preparation procedure of the antimony element-modified supported chromium-based catalyst used in examples 1-2 was as follows:
a) The supported chromium catalyst is fully mixed with antimony compound and then placed in a tube furnace, wherein the supported chromium catalyst is Advent C, and the antimony compound is antimony trioxide. The temperature was raised to 500℃at 10℃per minute under a nitrogen atmosphere (flow rate: 50 mL/min) and maintained for 3 hours. And then roasting in nitrogen atmosphere at 600 ℃ for 5 hours, and naturally cooling to obtain the precursor.
b) And c) carrying out a reduction reaction on the precursor obtained in the step a) in the presence of an organic metal reducing agent in a nitrogen atmosphere, and drying the obtained reduction product to obtain the antimony element modified supported chromium catalyst. Wherein the organic metal reducing agent is diethyl aluminum ethoxide, the reduction temperature of the reduction reaction is 20 ℃, the reduction time is 1 hour, and the molar ratio of aluminum to chromium is 40 based on aluminum element in the organic metal reducing agent and chromium element in the supported chromium catalyst.
In the obtained antimony element-modified supported chromium-based catalyst, the amount of the supported antimony element was 0.3wt% based on the total weight of the antimony element-modified supported chromium-based catalyst, and the average particle diameter was 14. Mu.m.
Example 3
Example 3 a chlorinated polyethylene specific resin powder was prepared according to the following process steps:
(1) Adding an alkane solvent into the slurry reaction kettle, starting continuous stirring, and heating the reaction kettle to 80 ℃; wherein the alkane solvent is normal hexane, and the stirring speed is 500rpm.
(2) Adding hydrogen and alpha-olefin into a slurry reaction kettle, wherein the molar ratio of the hydrogen to the ethylene is 0.08, and the molar ratio of the alpha-olefin to the ethylene is 0.02; wherein the alpha-olefin is butene-1.
(3) Ethylene is introduced into the slurry reaction kettle, and the reaction pressure in the slurry reaction kettle reaches 0.85MPa;
(4) Adding an antimony element modified supported chromium catalyst and a cocatalyst into a slurry reaction kettle for slurry polymerization reaction (wherein the dosage of the antimony element modified supported chromium catalyst is 20mg, the dosage of the cocatalyst is 3mL, and the cocatalyst is triethylaluminum), and reacting for 3 hours; in the polymerization reaction process, the pressure in the reaction kettle is maintained relatively stable by introducing ethylene, and 376g of ethylene is reacted together;
(5) The internal pressure of the slurry reaction kettle is emptied, and the temperature of materials in the slurry reaction kettle is reduced to 20 ℃ through jacket water of the reaction kettle;
(6) Discharging polymerization reactant slurry from the bottom of the slurry reaction kettle, and obtaining the special resin powder for chlorinated polyethylene after flash evaporation, centrifugation and drying.
The properties of the chlorinated polyethylene-specific resin obtained in example 3 were as follows: density of 0.952g/cm 3 ，MFR 5kg 2.7g/10min, bulk density 0.41g/cm 3 The wax content was 0.46%, the S value was 24, and the average particle diameter was 255. Mu.m.
Example 4 (unused alpha-olefins)
Example 4 a chlorinated polyethylene-specific resin powder was prepared according to the following process steps:
(1) Adding an alkane solvent into the slurry reaction kettle, starting continuous stirring, and heating the reaction kettle to 80 ℃; wherein, the alkane solvent is normal hexane, and the stirring speed is 500rpm;
(2) Adding hydrogen into the slurry reaction kettle, wherein the molar ratio of the hydrogen to the ethylene is 0.02;
(3) Ethylene is introduced into the slurry reaction kettle, and the reaction pressure in the slurry reaction kettle reaches 0.85MPa;
(4) Adding an antimony element modified supported chromium catalyst and a cocatalyst into a slurry reaction kettle for slurry polymerization reaction (wherein the dosage of the antimony element modified supported chromium catalyst is 20mg, the dosage of the cocatalyst is 3mL, and the cocatalyst is triisobutylaluminum), and reacting for 3 hours; during the polymerization reaction, the relatively stable pressure in the reaction kettle is maintained by introducing ethylene, and 486g of ethylene is reacted together;
(5) The internal pressure of the slurry reaction kettle is emptied, and the temperature of materials in the slurry reaction kettle is reduced to 20 ℃ at room temperature through jacket water of the reaction kettle;
(6) Discharging polymerization reactant slurry from the bottom of the slurry reaction kettle, and obtaining the special resin powder for chlorinated polyethylene after flash evaporation, centrifugation and drying.
The properties of the chlorinated polyethylene-specific resin powder obtained in example 4 were as follows: density of 0.964g/cm3, MFR 5kg 0.96g/10min, bulk density 0.39g/cm 3 The wax content was 0.28%, the S value was 26, and the average particle diameter was 244. Mu.m.
The preparation procedure of the antimony element modified supported chromium-based catalyst used in examples 3 to 4 was as follows:
a) The supported chromium catalyst is fully mixed with antimony compound and then placed in a tube furnace, wherein the supported chromium catalyst is Advent C, and the antimony compound is antimony pentoxide. The temperature was raised to 500℃at 10℃per minute under a nitrogen atmosphere (flow rate: 50 mL/min) and maintained for 3 hours. And then roasting in nitrogen atmosphere at 600 ℃ for 5 hours, and naturally cooling to obtain the precursor.
b) And c) carrying out a reduction reaction on the precursor obtained in the step a) in the presence of an organic metal reducing agent in a nitrogen atmosphere, and drying the obtained reduction product to obtain the antimony element modified supported chromium catalyst. Wherein the organic metal reducing agent is methylaluminoxane, the reduction temperature of the reduction reaction is 20 ℃, the reduction time is 1 hour, and the molar ratio of aluminum to chromium is 40 based on aluminum element in the organic metal reducing agent and chromium element in the supported chromium catalyst.
In the obtained antimony element-modified supported chromium-based catalyst, the amount of the supported antimony element was 0.3wt% based on the total weight of the antimony element-modified supported chromium-based catalyst, and the average particle diameter was 14. Mu.m.
Example 5
Example 5 a chlorinated polyethylene specific resin powder was prepared according to the following process steps:
(1) Adding an alkane solvent into the slurry reaction kettle, starting continuous stirring, and heating the reaction kettle to 80 ℃; wherein the alkane solvent is normal hexane, and the stirring speed is 500rpm.
(2) Adding hydrogen and alpha-olefin into a slurry reaction kettle, wherein the molar ratio of the hydrogen to the ethylene is 0.02, and the molar ratio of the alpha-olefin to the ethylene is 0.01; wherein the alpha-olefin is butene-1
(3) Ethylene is introduced into the slurry reaction kettle, and the reaction pressure in the slurry reaction kettle reaches 0.80MPa;
(4) Adding an antimony element modified supported chromium catalyst and a cocatalyst into a slurry reaction kettle for slurry polymerization reaction (wherein the dosage of the antimony element modified supported chromium catalyst is 20mg, the dosage of the cocatalyst is 3mL, and the cocatalyst is triisobutylaluminum), and reacting for 3 hours; during the polymerization reaction, the relative stability of the pressure in the reaction kettle is maintained by introducing ethylene, and 516g of ethylene is reacted together;
(5) The internal pressure of the slurry reaction kettle is emptied, and the temperature of materials in the slurry reaction kettle is reduced to 20 ℃ at room temperature through jacket water of the reaction kettle;
(6) Discharging polymerization reactant slurry from the bottom of the slurry reaction kettle, and obtaining the special resin powder for chlorinated polyethylene after flash evaporation, centrifugation and drying.
The properties of the chlorinated polyethylene-specific resin powder obtained in example 5 were as follows: density of 0.955g/cm 3 ，MFR 5kg 1.3g/10min, bulk density 0.4g/cm 3 The wax content was 0.23%, the S value was 17, and the average particle diameter was 252. Mu.m.
Example 6
Example 6 a chlorinated polyethylene specific resin powder was prepared according to the following process steps:
(1) Adding an alkane solvent into the slurry reaction kettle, starting continuous stirring, and heating the reaction kettle to 80 ℃; wherein the alkane solvent is normal hexane, and the stirring speed is 500rpm.
(2) Adding hydrogen and alpha-olefin into a slurry reaction kettle, wherein the molar ratio of the hydrogen to the ethylene is 0.02, and the molar ratio of the alpha-olefin to the ethylene is 0.01; wherein the alpha-olefin is butene-1
(3) Ethylene is introduced into the slurry reaction kettle, and the reaction pressure in the slurry reaction kettle reaches 0.80MPa;
(4) Adding an antimony element modified supported chromium catalyst and a cocatalyst into a slurry reaction kettle for slurry polymerization reaction (wherein the dosage of the antimony element modified supported chromium catalyst is 20mg, the dosage of the cocatalyst is 3mL, and the cocatalyst is triisobutylaluminum), and reacting for 3 hours; during the polymerization reaction, the relative stability of the pressure in the reaction kettle is maintained by the introduction of ethylene, and 492g of ethylene is reacted together;
(5) The internal pressure of the slurry reaction kettle is emptied, and the temperature of materials in the slurry reaction kettle is reduced to 20 ℃ at room temperature through jacket water of the reaction kettle;
(6) Discharging polymerization reactant slurry from the bottom of the slurry reaction kettle, and obtaining the special resin powder for chlorinated polyethylene after flash evaporation, centrifugation and drying.
The properties of the chlorinated polyethylene-specific resin powder obtained in example 6 were as follows: density of 0.956g/cm 3 ，MFR 5kg 1.3g/10min, bulk density 0.39g/cm 3 The wax content was 0.25%, the S value was 18, and the average particle diameter was 253. Mu.m.
Example 7
Example 7a chlorinated polyethylene specific resin powder was prepared according to the following process steps:
(1) Adding an alkane solvent into the slurry reaction kettle, starting continuous stirring, and heating the reaction kettle to 80 ℃; wherein the alkane solvent is normal hexane, and the stirring speed is 500rpm.
(2) Adding hydrogen and alpha-olefin into a slurry reaction kettle, wherein the molar ratio of the hydrogen to the ethylene is 0.02, and the molar ratio of the alpha-olefin to the ethylene is 0.01; wherein the alpha-olefin is butene-1
(3) Ethylene is introduced into the slurry reaction kettle, and the reaction pressure in the slurry reaction kettle reaches 0.80MPa;
(4) Adding an antimony element modified supported chromium catalyst and a cocatalyst into a slurry reaction kettle for slurry polymerization reaction (wherein the dosage of the antimony element modified supported chromium catalyst is 20mg, the dosage of the cocatalyst is 3mL, and the cocatalyst is triisobutylaluminum), and reacting for 3 hours; in the polymerization reaction process, the relative stability of the pressure in the reaction kettle is maintained through the introduction of ethylene, and 266g of ethylene is reacted together;
(5) The internal pressure of the slurry reaction kettle is emptied, and the temperature of materials in the slurry reaction kettle is reduced to 20 ℃ at room temperature through jacket water of the reaction kettle;
(6) Discharging polymerization reactant slurry from the bottom of the slurry reaction kettle, and obtaining the special resin powder for chlorinated polyethylene after flash evaporation, centrifugation and drying.
The properties of the chlorinated polyethylene-specific resin powder obtained in example 7 were as follows: density of 0.954g/cm 3 ，MFR 5kg 2g/10min, bulk density of 0.39g/cm 3 The wax content was 0.32%, the S value was 28, and the average particle diameter was 251. Mu.m.
Example 8
Example 8 a chlorinated polyethylene-specific resin powder was prepared according to the following process steps:
(1) Adding an alkane solvent into the slurry reaction kettle, starting continuous stirring, and heating the reaction kettle to 80 ℃; wherein the alkane solvent is normal hexane, and the stirring speed is 500rpm.
(2) Adding hydrogen and alpha-olefin into a slurry reaction kettle, wherein the molar ratio of the hydrogen to the ethylene is 0.02, and the molar ratio of the alpha-olefin to the ethylene is 0.01; wherein the alpha-olefin is butene-1
(3) Ethylene is introduced into the slurry reaction kettle, and the reaction pressure in the slurry reaction kettle reaches 0.80MPa;
(4) Adding an antimony element modified supported chromium catalyst and a cocatalyst into a slurry reaction kettle for slurry polymerization reaction (wherein the dosage of the antimony element modified supported chromium catalyst is 20mg, the dosage of the cocatalyst is 3mL, and the cocatalyst is triisobutylaluminum), and reacting for 3 hours; in the polymerization reaction process, the relatively stable pressure in the reaction kettle is maintained through the introduction of ethylene, and 107g of ethylene is reacted together;
(5) The internal pressure of the slurry reaction kettle is emptied, and the temperature of materials in the slurry reaction kettle is reduced to 20 ℃ at room temperature through jacket water of the reaction kettle;
(6) Discharging polymerization reactant slurry from the bottom of the slurry reaction kettle, and obtaining the special resin powder for chlorinated polyethylene after flash evaporation, centrifugation and drying.
The properties of the chlorinated polyethylene-specific resin powder obtained in example 8 were as follows: density of 0.954g/cm 3 ，MFR 5kg 3.1g/10min, bulk density of 0.4g/cm 3 The wax content was 0.51%, the S value was 31, and the average particle diameter was 247. Mu.m.
The preparation procedure of the antimony element modified supported chromium-based catalysts used in examples 5 to 8 was as follows:
a) The supported chromium catalyst is fully mixed with antimony compound and then placed in a tube furnace, wherein the supported chromium catalyst is Advent C, and the antimony compound is antimony trioxide. The temperature was raised to 500℃at 10℃per minute under a nitrogen atmosphere (flow rate: 50 mL/min) and maintained for 3 hours. And then roasting in nitrogen atmosphere at 600 ℃ for 5 hours, and naturally cooling to obtain the precursor.
b) And c) carrying out a reduction reaction on the precursor obtained in the step a) in the presence of an organic metal reducing agent in a nitrogen atmosphere, and drying the obtained reduction product to obtain the antimony element modified supported chromium catalyst. Wherein the organic metal reducing agent is diethyl aluminum ethoxide, the reduction temperature of the reduction reaction is 20 ℃, the reduction time is 1 hour, and the molar ratio of aluminum to chromium is 40 based on aluminum element in the organic metal reducing agent and chromium element in the supported chromium catalyst.
In the obtained supported chromium-based catalyst modified with antimony element, the supported chromium-based catalyst modified with antimony element was 0.01wt%, 0.02wt%, 1wt% and 5wt% in the order of examples 5 to 8, based on the total weight of the supported chromium-based catalyst modified with antimony element, and the average particle diameter was 14. Mu.m.
Comparative example 1
Comparative example 1 a chlorinated polyethylene-specific resin powder was prepared according to the following process steps:
(1) Adding an alkane solvent into the slurry reaction kettle, starting continuous stirring, and heating the reaction kettle to 80 ℃; wherein, the alkane solvent is normal hexane, and the stirring speed is 500rpm;
(2) Adding hydrogen into the slurry reaction kettle, wherein the molar ratio of the hydrogen to the ethylene is 0.04;
(3) Ethylene is introduced into the slurry reaction kettle, and the reaction pressure in the slurry reaction kettle reaches 0.75MPa;
(4) 20mg of Ziegler-Natta catalyst (Avant Z501) was added to the slurry reactor, and after 1.5 hours of reaction, the gas phase components were vented; during the polymerization reaction, the relatively stable pressure in the reaction kettle is maintained by introducing ethylene, and 517g of ethylene is reacted together;
(5) Hydrogen and alpha-olefin were again fed to the slurry reactor in a hydrogen to ethylene molar ratio of 2.5 and an alpha-olefin to ethylene molar ratio of 0.04. Wherein the alpha-olefin is butene-1;
(6) Ethylene is introduced into the slurry reaction kettle, and the reaction pressure in the slurry reaction kettle reaches 0.25MPa, so that the reaction is carried out for 1.5 hours; during the polymerization reaction, the relatively stable pressure in the reaction kettle is maintained through the introduction of ethylene;
(7) The internal pressure of the slurry reaction kettle is emptied, and the temperature of materials in the slurry reaction kettle is reduced to 20 ℃ through jacket water of the reaction kettle;
(8) Discharging polymerization reactant slurry from the bottom of the slurry reaction kettle, and obtaining the special resin powder for chlorinated polyethylene after flash evaporation, centrifugation and drying.
The properties of the chlorinated polyethylene-dedicated resin powder obtained in comparative example 1 were as follows: density of 0.954g/cm 3 ，MFR 5kg 2.6g/10min, bulk density 0.39g/cm 3 The wax content was 2.73%, the S value was 27, and the average particle diameter was 367. Mu.m.
Comparative example 2 (comparative example 2)
Comparative example 2a chlorinated polyethylene-specific resin powder was prepared according to the following process steps:
(1) Adding an alkane solvent into the slurry reaction kettle, starting continuous stirring, and heating the reaction kettle to 80 ℃; wherein the alkane solvent is normal hexane, and the stirring speed is 500rpm.
(2) Adding hydrogen and alpha-olefin into a slurry reaction kettle, wherein the molar ratio of the hydrogen to the ethylene is 0.02, and the molar ratio of the alpha-olefin to the ethylene is 0.01; wherein the alpha-olefin is butene-1.
(3) Ethylene is introduced into the slurry reaction kettle, and the reaction pressure in the slurry reaction kettle reaches 0.85MPa;
(4) Adding a Metallocene catalyst XCAT metal (manufacturer Univation) cocatalyst into a slurry reaction kettle for slurry polymerization reaction (wherein the dosage of the Metallocene catalyst is 20mg, the dosage of the cocatalyst is 3mL, and the cocatalyst is triisobutylaluminum), and reacting for 3 hours; in the polymerization reaction process, the relative stability of the pressure in the reaction kettle is maintained through the introduction of ethylene, and 590g of ethylene is reacted together;
(5) The internal pressure of the slurry reaction kettle is emptied, and the temperature of materials in the slurry reaction kettle is reduced to 20 ℃ through jacket water of the reaction kettle;
(6) Discharging polymerization reactant slurry from the bottom of the slurry reaction kettle, and obtaining the special resin powder for chlorinated polyethylene after flash evaporation, centrifugation and drying.
The properties of the chlorinated polyethylene-dedicated resin powder obtained in comparative example 2 were as follows: density of 0.956g/cm 3 ，MFR 5kg 1.7g/10min, bulk density 0.41g/cm 3 The wax content was 1.06%, the S value was 8, and the average particle diameter was 220. Mu.m.
Comparative example 3 (comparative example 2)
Comparative example 3 a chlorinated polyethylene-specific resin powder was prepared according to the following process steps:
(1) Adding an alkane solvent into the slurry reaction kettle, starting continuous stirring, and heating the reaction kettle to 80 ℃; wherein the alkane solvent is normal hexane, and the stirring speed is 500rpm.
(2) Adding hydrogen and alpha-olefin into a slurry reaction kettle, wherein the molar ratio of the hydrogen to the ethylene is 0.02, and the molar ratio of the alpha-olefin to the ethylene is 0.01; wherein the alpha-olefin is butene-1.
(3) Ethylene is introduced into the slurry reaction kettle, and the reaction pressure in the slurry reaction kettle reaches 0.85MPa;
(4) Adding a chromium catalyst Advent C and a cocatalyst into a slurry reaction kettle to perform slurry polymerization reaction (wherein the dosage of the chromium catalyst is 20mg, the dosage of the cocatalyst is 3mL, and the cocatalyst is triisobutylaluminum), and reacting for 3 hours; in the polymerization reaction process, the pressure in the reaction kettle is maintained relatively stable by introducing ethylene, and 503g of ethylene is reacted together;
(5) The internal pressure of the slurry reaction kettle is emptied, and the temperature of materials in the slurry reaction kettle is reduced to 20 ℃ through jacket water of the reaction kettle;
(6) Discharging polymerization reactant slurry from the bottom of the slurry reaction kettle, and obtaining the special resin powder for chlorinated polyethylene after flash evaporation, centrifugation and drying.
The properties of the chlorinated polyethylene-dedicated resin powder obtained in comparative example 3 were as follows: density of 0.957g/cm 3 ，MFR 5kg 1.4g/10min, bulk density 0.40g/cm 3 The wax content was 0.27%, the S value was 8, and the average particle diameter was 249. Mu.m.
Example 9
The chlorinated polyethylene-specific resins obtained in the above examples and comparative examples were prepared into chlorinated polyethylene according to the following process steps, respectively:
5L of water and 500g of the chlorinated polyethylene-dedicated resin prepared in the above example or comparative example were added to a reactor, and a dispersant, an emulsifier and an initiator were added to the reactor, and all chlorinated in gaseous chlorine (chlorine excess) at 130℃for 3 hours, to obtain chlorinated polyethylene samples 1 to 11, respectively, with the properties shown in the following Table. In the table, samples 1 to 11 correspond to chlorinated polyethylene samples prepared by reacting chlorinated polyethylene-specific resins of example 1, example 2, example 3, example 4, example 5, example 6, example 7, example 8, comparative example 1, comparative example 2, comparative example 3 in this order.
Wherein the dispersing agent is sodium polymethacrylate, the emulsifying agent is polyvinylpyrrolidone, and the initiator is dibenzoyl peroxide; the dosage of the three components is 14g, 1g and 4g respectively.
Table: chlorinated polyethylene Performance test results
Figure BDA0003415780620000191
Figure BDA0003415780620000201
As can be seen from the results of Table 6, the chlorinated polyethylene prepared from the chlorinated polyethylene-specific resins of examples 1 to 8 according to the scheme of the invention has higher chlorine content and better tensile strength under the same chlorination conditions, which indicates that the chlorinated polyethylene is produced at a fast chlorination rate and with uniform chlorine distribution, and shows excellent production efficiency and stability.
As shown in the results of Table 6, the chlorinated polyethylene special resin obtained by the method has good Mooney viscosity and excellent tensile strength after chlorination, and the obtained product can well give consideration to the processability and mechanical properties of the chlorinated polyethylene and has good application prospect.
Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.

Claims (19)

1.一种氯化聚乙烯专用树脂粉末的制备方法，所述氯化聚乙烯专用树脂粉末的粉料密度为0.945~0.960g/cm3，MFR5kg为0.1~10g/10min，平均粒径为100-300μm，S值为17-31，蜡含量≤0.5wt%；1. A preparation method of special resin powder for chlorinated polyethylene, the powder density of said special resin powder for chlorinated polyethylene is 0.945 ~ 0.960g/cm 3 , MFR 5kg is 0.1 ~ 10g/10min, and the average particle size is 100-300μm, S value 17-31, wax content ≤0.5wt%; 其特征在于，乙烯和任选的α-烯烃在催化剂存在下在单一的淤浆聚合反应釜中通过淤浆聚合反应制得所述氯化聚乙烯专用树脂粉末，其中所述催化剂包括锑元素改性的负载型铬系催化剂。It is characterized in that the special resin powder for chlorinated polyethylene is prepared by slurry polymerization reaction of ethylene and optional α-olefin in a single slurry polymerization reactor in the presence of a catalyst, wherein the catalyst includes antimony modified supported chromium-based catalysts. 2.根据权利要求1所述的制备方法，其特征在于，相对于每克乙烯，所述锑元素改性的负载型铬系催化剂的加入量为0.02-2mg。2. The preparation method according to claim 1, characterized in that, relative to each gram of ethylene, the added amount of the antimony-modified supported chromium-based catalyst is 0.02-2 mg. 3.根据权利要求2所述的制备方法，其特征在于，相对于每克乙烯，所述锑元素改性的负载型铬系催化剂的加入量为0.03-0.2mg。3. The preparation method according to claim 2, characterized in that, relative to each gram of ethylene, the added amount of the antimony-modified supported chromium-based catalyst is 0.03-0.2 mg. 4.根据权利要求1-3任一项所述的制备方法，其特征在于，所述锑元素改性的负载型铬系催化剂的平均粒径6-20μm。4. The preparation method according to any one of claims 1-3, characterized in that the average particle diameter of the antimony-modified supported chromium-based catalyst is 6-20 μm. 5.根据权利要求1-3任一项所述的制备方法，其特征在于，所述催化剂还包括助催化剂，所述助催化剂为烷基铝。5. The preparation method according to any one of claims 1-3, characterized in that, the catalyst further comprises a co-catalyst, and the co-catalyst is an aluminum alkyl. 6.根据权利要求5所述的制备方法，其特征在于，所述助催化剂为三乙基铝、三异丁基铝、乙氧基二乙基铝、一氯二乙基铝或甲基铝氧烷中的一种或多种。6. The preparation method according to claim 5, wherein the cocatalyst is triethylaluminum, triisobutylaluminum, ethoxydiethylaluminum, diethylaluminum chloride or methylaluminum One or more of oxanes. 7.根据权利要求6所述的制备方法，其特征在于，相对于每毫克所述锑元素改性的负载型铬系催化剂，所述助催化剂的用量为0.01-10mL。7. The preparation method according to claim 6, characterized in that, the amount of the co-catalyst is 0.01-10 mL per mg of the antimony-modified supported chromium-based catalyst. 8.根据权利要求7所述的制备方法，其特征在于，相对于每毫克所述锑元素改性的负载型铬系催化剂，所述助催化剂的用量为0.05-1mL。8 . The preparation method according to claim 7 , wherein the amount of the cocatalyst is 0.05-1 mL per milligram of the antimony-modified supported chromium-based catalyst. 9.根据权利要求1-3任一项所述的制备方法，其特征在于，基于所述锑元素改性的负载型铬系催化剂的总重量，所述锑元素的负载量为0.01~5wt%。9. according to the preparation method described in any one of claim 1-3, it is characterized in that, based on the total weight of the supported chromium-based catalyst modified by the antimony element, the loading capacity of the antimony element is 0.01 ~ 5wt% . 10.根据权利要求9所述的制备方法，其特征在于，基于所述锑元素改性的负载型铬系催化剂的总重量，所述锑元素的负载量为0.02~1wt%。10. The preparation method according to claim 9, characterized in that, based on the total weight of the supported chromium-based catalyst modified with the antimony element, the loading amount of the antimony element is 0.02-1wt%. 11.根据权利要求9所述的制备方法，其特征在于，所述锑元素改性的负载型铬系催化剂的制备步骤包括：11. preparation method according to claim 9, is characterized in that, the preparation step of the supported chromium series catalyst of described antimony element modification comprises: 1）将负载型铬系催化剂置于管式炉中，通过气相沉积将锑化合物中的锑元素负载至所述负载型铬系催化剂上，经焙烧得到前驱体；1) Place the supported chromium-based catalyst in a tube furnace, load the antimony element in the antimony compound onto the supported chromium-based catalyst by vapor deposition, and obtain a precursor by roasting; 2）步骤1）得到的所述前驱体在有机金属还原剂存在下进行还原反应，所得还原产物经干燥得到所述锑元素改性的负载型铬系催化剂。2) The precursor obtained in step 1) is subjected to a reduction reaction in the presence of an organometallic reducing agent, and the obtained reduced product is dried to obtain the supported chromium-based catalyst modified with the antimony element. 12.根据权利要求11所述的制备方法，其特征在于，步骤1）在惰性气氛下进行所述气相沉积，惰性气体的流量为5~100mL/min；步骤1）中的反应温度为100~600°C；沉积时间为120~480min；12. The preparation method according to claim 11, characterized in that step 1) carries out the vapor phase deposition under an inert atmosphere, and the flow rate of the inert gas is 5-100mL/min; the reaction temperature in step 1) is 100-100mL/min. 600°C; deposition time is 120~480min; 步骤1）中，所述焙烧在惰性气体中进行，焙烧温度为300～1000℃，时间为1～10h；或者，所述焙烧以低温阶段和高温阶段两个阶段进行，低温阶段在100～300℃进行，持续1～10小时，高温阶段在300～900℃进行，持续1～10小时；In step 1), the calcination is carried out in an inert gas, the calcination temperature is 300-1000°C, and the time is 1-10h; or, the calcination is carried out in two stages: a low temperature stage and a high temperature stage, and the low temperature stage is at ℃ for 1 to 10 hours, high temperature stage at 300 to 900 ℃ for 1 to 10 hours; 步骤2）中，在惰性气氛下进行所述还原反应，还原温度为20℃~100°C；还原时间为0.5~20小时。In step 2), the reduction reaction is carried out under an inert atmosphere, the reduction temperature is 20° C. to 100° C.; the reduction time is 0.5 to 20 hours. 13.根据权利要求12所述的制备方法，其特征在于，步骤1）中，所述惰性气体的流量为40~60mL/min；13. The preparation method according to claim 12, characterized in that, in step 1), the flow rate of the inert gas is 40-60mL/min; 和/或，步骤1）中，所述反应温度为300~550°C；And/or, in step 1), the reaction temperature is 300~550°C; 和/或，步骤1）中，所述沉积时间为180~300min；And/or, in step 1), the deposition time is 180~300min; 和/或，步骤1）中，所述焙烧温度为400～800℃，时间为4～6h；或者，所述低温阶段持续4～8小时，所述高温阶段持续4～8小时；And/or, in step 1), the calcination temperature is 400-800°C, and the time is 4-6 hours; or, the low-temperature stage lasts for 4-8 hours, and the high-temperature stage lasts for 4-8 hours; 和/或，步骤2）中，所述还原温度为20℃~70°C，所述还原时间为0.5~10小时。And/or, in step 2), the reduction temperature is 20°C-70°C, and the reduction time is 0.5-10 hours. 14.根据权利要求12所述的制备方法，其特征在于，步骤1）中，所述负载型铬系催化剂为Basell公司的Advent C催化剂；14. The preparation method according to claim 12, characterized in that, in step 1), the supported chromium-based catalyst is an Advent C catalyst from Basell; 和/或，步骤1）中，所述锑化合物选自三氧化二锑、五氧化二锑、三氯化锑、五氯化锑、锑酸钠、六氟锑酸钠、醋酸锑中的一种或多种；And/or, in step 1), the antimony compound is selected from one of antimony trioxide, antimony pentoxide, antimony trichloride, antimony pentachloride, sodium antimonate, sodium hexafluoroantimonate, antimony acetate one or more kinds; 和/或，步骤2）中，所述有机金属还原剂为三乙基铝、三异丁基铝、乙氧基二乙基铝、一氯二乙基铝或甲基铝氧烷中的一种或多种。And/or, in step 2), the organometallic reducing agent is one of triethylaluminum, triisobutylaluminum, ethoxydiethylaluminum, monochlorodiethylaluminum or methylaluminoxane one or more species. 15.根据权利要求14所述的制备方法，其特征在于，步骤2）中，以所述有机金属还原剂中的铝元素和所述负载型铬系催化剂中的铬元素计，铝/铬摩尔比为0.01~500。15. The preparation method according to claim 14, characterized in that, in step 2), based on the aluminum element in the organometallic reducing agent and the chromium element in the supported chromium-based catalyst, the aluminum/chromium mole The ratio is 0.01~500. 16.根据权利要求15所述的制备方法，其特征在于，所述铝/铬摩尔比为0.1~50。16. The preparation method according to claim 15, characterized in that the aluminum/chromium molar ratio is 0.1-50. 17.根据权利要求1-3任一项所述的制备方法，其特征在于，以烷烃溶剂为介质，在所述催化剂存在下于单一的淤浆反应釜中进行所述淤浆聚合反应；17. The preparation method according to any one of claims 1-3, characterized in that, using an alkane solvent as a medium, the slurry polymerization is carried out in a single slurry reactor in the presence of the catalyst; 所述淤浆聚合反应的反应温度为70-85℃，反应压力为0.5-1.5MPa之间，氢气和乙烯的摩尔比为0.01-1，α-烯烃和乙烯的摩尔比为0-0.1。The reaction temperature of the slurry polymerization reaction is 70-85° C., the reaction pressure is 0.5-1.5 MPa, the molar ratio of hydrogen to ethylene is 0.01-1, and the molar ratio of α-olefin to ethylene is 0-0.1. 18.根据权利要求17所述的制备方法，其特征在于，所述烷烃溶剂为丁烷、戊烷、正己烷或庚烷中的一种或多种。18. The preparation method according to claim 17, characterized in that, the alkane solvent is one or more of butane, pentane, n-hexane or heptane. 19.根据权利要求1-3任一项所述的制备方法，其特征在于，所述α-烯烃为丙烯、丁烯-1、己烯-1、辛烯-1或4-甲基戊烯-1。19. The preparation method according to any one of claims 1-3, wherein the α-olefin is propylene, butene-1, hexene-1, octene-1 or 4-methylpentene -1.
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