CN111909294A - Catalyst of ultra-high molecular weight polyethylene, preparation method and application of catalyst - Google Patents
Catalyst of ultra-high molecular weight polyethylene, preparation method and application of catalyst Download PDFInfo
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Abstract
A catalyst of ultra-high molecular weight polyethylene, a preparation method and application of the catalyst belong to the field of olefin coordination polymerization catalysts and polyolefins. In the invention, an organic polymer elastomer is added in the process of preparing the catalyst, an inorganic magnesium compound and the organic polymer elastomer are uniformly dispersed in an organic solvent to form a solution, a transition metal halide serving as an active component of the catalyst is loaded on a compound of the organic polymer elastomer and the inorganic magnesium compound, partial carbon-carbon double bonds of the organic polymer elastomer and the transition metal generate a coordination complex effect, the density of electron clouds around transition metal atoms is reduced, monomer ethylene or other olefins are coordinated with, inserted into and chain-extended with an active center of the catalyst more stably, and a beta-H elimination reaction of a polyethylene extended chain is more difficult to occur, so that the ultrahigh molecular weight polyethylene is obtained.
Description
Technical Field
The invention belongs to the field of olefin coordination polymerization catalysts and polyolefins, and particularly relates to a catalyst for synthesizing ultrahigh molecular weight polyethylene, a preparation method of the catalyst and application of the catalyst.
Background
In 1957, Ultra High Molecular Weight Polyethylene (UHMWPE), which was first developed by United states chemical company using Ziegler catalyst, is a linear polyethylene having the same structure as HDPE, and the molecular weight is usually 100X 104g/mol, crystallinity of 65-85%, density of 0.92-0.96 g/cm3. Ultra-high molecular weight polyethylene can also be produced using metallocene and non-metallocene catalysts.
The ultra-high molecular weight polyethylene has excellent friction performance, self-lubricating property and impact resistance, excellent chemical stability, surface non-adhesion and thermal performance and no toxicity to organisms, and the product has the advantages of energy absorption, noise absorption, static resistance, neutron shielding capacity, no water absorption and the like.
Ultra-high molecular weight polyethylene (UHMWPE) is a high-performance polymer material, and is listed in the field of 18 polymer material key developments in the coming decade of "2025 manufacture in China" (www.polymer.cn,2015-11-27), the free breaking length of the ultra-high molecular weight polyethylene in water is infinite, the maximum weight of the ultra-high molecular weight polyethylene can be 8 times that of a steel wire rope under the condition of the same thickness, and the density of the ultra-high molecular weight polyethylene is only 0.94-0.97g/cm3(ii) a Better chemical stability and strong chemical inertness: strong acid, strong alkali solution and organic solvent have no influence on the strength; has very muchGood weather resistance and ultraviolet resistance, and the mechanical strength retention rate is still as high as 80% after being dried for 1500 h; the low temperature resistance is good, the brittle temperature is as low as-269 ℃, the melting point is 136 ℃, and the high-temperature-resistant high-temperature-; the abrasion resistance and impact resistance are the top of plastics, and the high impact strength is still achieved even at the temperature of-70 ℃. The bending resistance, tensile fatigue resistance and cutting resistance of the ultra-high molecular weight polyethylene are also the strongest ones of the existing high-performance polymer materials. The molecular weight is 80-120X 104g/mol of ultra-high molecular weight polyethylene is suitable for being used as a special material for a battery diaphragm; the molecular weight is 80-250X 104The g/mol of the ultra-high molecular weight polyethylene is suitable for being used as seats, interior trim parts and the like of airplanes, high-speed rails and the like; molecular weight of 100-4The g/mol ultra-high molecular weight polyethylene is suitable for being used as a material in an oil extraction pipe and a heat-resistant pressure-resistant pipe; the molecular weight is 150-4The g/mol of the ultra-high molecular weight polyethylene is suitable for being made into various fiber materials; the molecular weight is 100-4The g/mol of the ultra-high molecular weight polyethylene is suitable for being used as a ship body, an unmanned aerial vehicle shell, accessories and the like; the molecular weight is 150-450X 104The g/mol of the ultra-high molecular weight polyethylene is suitable for being used as body armor, bullet-proof hat, sports equipment and the like; the molecular weight is 300-4The g/mol of the ultra-high molecular weight polyethylene is suitable for being used as an artificial contraceptive ring and the like; the molecular weight is 400-4The g/mol of the ultra-high molecular weight polyethylene is suitable for being used as a human joint; the molecular weight is 500-900 x 104The g/mol of the ultra-high molecular weight polyethylene is suitable for being used as a hip joint of a human body.
Because the ultra-high molecular weight polyethylene material has good impact resistance and large specific energy absorption, the material can be made into protective clothing material, helmets, bulletproof material, armor protection plates of helicopters, tanks and ships, protective shell covers of radars, missile covers, bullet-proof vests, stab-proof vests, shields and the like in military affairs, and is suitable for wing tip structures, airship structures, buoy airplanes and the like of airplanes. The ultra-high molecular weight polyethylene fiber can also be used as a deceleration parachute for landing of a space plane and a rope for hanging heavy objects on the plane. The product made of the ultra-high molecular weight polyethylene fiber is also suitable for ocean engineering, and can be used for negative force ropes, heavy load ropes, salvage ropes, dragging ropes, sailing ropes, fishing lines and the like. It can also be used for fixing anchor ropes of super oil tankers, ocean operation platforms, lighthouses and the like. The ultra-high molecular weight polyethylene material can also be made into safety helmets, skis, sailing wheel plates, fishing rods, rackets, and sports equipment articles such as bicycles, gliding boards, ultra-light airplane parts and the like. The ultra-high molecular weight polyethylene material can be used as a pressure-resistant container, a conveyor belt, a filter material, an automobile buffer board and the like, can be used as a wall body, a partition board structural member and the like in the aspect of construction, and can be used as a reinforced cement composite material to improve the toughness of cement and improve the shock resistance of the cement.
The application of the ultra-high molecular weight polyethylene material in the field of new energy comprises the following steps: in the construction of lithium ion batteries, the battery separator is one of the key internal layer components. The performance of the separator determines the interface structure, internal resistance and the like of the battery, and directly influences the characteristics of the battery such as capacity, cycle performance, safety performance and the like. The diaphragm with excellent performance plays an important role in improving the comprehensive performance of the battery. The main raw materials of the lithium ion battery diaphragm are polyethylene and polypropylene, and the lithium ion battery diaphragm comprises a single-layer PE, a single-layer PP and a three-layer PP/PE/PP composite film. The production process of the polyolefin diaphragm is divided into a dry process and a wet process, wherein the dry process is further divided into a unidirectional stretching process and a bidirectional stretching process. 60% -70% of the diaphragm is mainly subjected to wet biaxial tension. The dry diaphragm takes polypropylene as a raw material, and the wet diaphragm takes polyethylene as a raw material. Wet membranes are more favored in the market. Compared with the dry method, the wet method film preparation process is relatively easy to regulate and control, and the aperture, the aperture distribution and the porosity can be well controlled. The ultra-high molecular weight polyethylene diaphragm produced by the wet method has good mechanical properties. At present, the wet process is adopted by korea and domestic enterprises increasingly adopt the wet process. The companies using the wet process mainly include japan asahi chemical, eastern fuel chemistry, mitsubishi chemistry, korean SK chemistry, star source materials, and chinese science and technology. With the rapid development of the market of power lithium batteries, the yield of the Chinese wet diaphragm in 2018 reaches 8 hundred million square meters, and the diaphragm occupies more than half of the market share. However, the wet process requires a large amount of organic solvent, and has a heavy environmental impact. Under the boosting of new energy automobiles, the demand of lithium battery diaphragms is greatly increased. The diaphragm accounts for 25 percent of the proportion in the production cost of the whole lithium battery and is positioned at the second place. Although the diaphragm is only a layer of porous plastic film, the diaphragm is the material with the lowest Chinese yield and the highest technical barrier of four key materials of the lithium battery.
The key technology for synthesizing the ultra-high molecular weight polyethylene is a catalyst and a catalyst preparation method. Earlier with TiCl4/Al(C2H5)3As the catalyst, the saturated hydrocarbon of 60-120 deg.C fraction is used as dispersion medium, and ethylene is coordinated and polymerized under the condition of normal pressure or near normal pressure and 5-85 deg.C, so that it can synthesize 500X 10-molecular weight4g/mol of ultra-high molecular weight polyethylene. Patents [ CN201010279310.3, CN201010237796.4 ]]Discloses a method for preparing UHMWPE by catalyzing ethylene to polymerize by a supported Z-N high-efficiency catalyst slurry method, wherein the molecular weight of the polyethylene is 10-900 multiplied by 104Adjustable in g/mol range. Patents [ CN201110109884.0, CN201110109882.1 ]]Discloses the synthesis of ultrahigh molecular weight polyethylene by using a supported non-metallocene catalyst, wherein the branching degree of the polyethylene resin is less than one ten-thousandth.
The invention has surprisingly found that the addition of the organic polymer elastomer in the preparation process of the ultra-high molecular weight polyethylene catalyst can effectively improve the brittleness of catalyst particles and improve the toughness of the catalyst particles, flexible regions are uniformly distributed in the catalyst particles, monomers can easily diffuse into the flexible regions to contact with the active center of the catalyst and carry out olefin polymerization reaction, the catalyst particles are not easy to break after the ethylene polymerization catalyst is prepared, and the obtained polyethylene particles have good shape and uniform distribution. The invention also discloses that the added organic polymer elastomer can form a compound with an inorganic magnesium compound to form a carrier of the ethylene polymerization or copolymerization catalyst. The invention also discovers that the organic polymer elastomer is added in the process of preparing the catalyst, the inorganic magnesium compound and the organic polymer elastomer are uniformly dispersed, and the active component TiCl of the catalyst4The organic polymer elastomer is loaded on a carrier, partial carbon-carbon double bonds of the organic polymer elastomer and transition metal Ti generate a coordination complexing effect, the density of electron cloud around the transition metal Ti atom is reduced, monomer ethylene or other olefins are more stably coordinated, inserted and chain-extended with an active center of a catalyst, and beta-H elimination of a polyethylene extended chain is realizedExcept that the reaction is more difficult to occur and thus ultra high molecular weight polyethylene is obtained. The invention discovers that the catalyst prepared by the method has small particle size, uniform distribution, high catalyst loading (2.0-5.9 wt%), high catalytic efficiency (1.5-4.5 g polyolefin/g catalyst) for catalyzing ethylene polymerization or olefin copolymerization, and the viscosity-average molecular weight of the polyolefin can be 80 multiplied by 104g/mol to 1000X 104g/mol, the melt index of the polyethylene can be adjusted between 0.0002 and 100 g/10 min, and the bulk density of the polyolefin is between 0.30 and 0.47; the catalyst has high loading capacity and high activity, and the catalyst particles and the polyolefin particles are not adhered to the wall of the container; the polymer particles have good shapes, high bulk density and less fine powder; suitable for use in a gas phase polymerization process, a slurry polymerization process, a loop polymerization process, or a combination polymerization process; the catalyst has the advantages of simple preparation process, low cost, low requirement on equipment, low energy consumption and low environmental pollution.
Disclosure of Invention
The invention aims to provide a catalyst for synthesizing ultra-high molecular weight polyethylene, a preparation method and application of the catalyst. The specific purpose is to provide a supported catalyst with high catalytic activity for preparing ultrahigh molecular weight polyethylene by ethylene polymerization or copolymerization, a preparation method of the supported catalyst and application of the supported catalyst.
The catalyst prepared by the method has small particle size, uniform distribution, particle size of between 15 and 60 mu m, high catalyst load (2.0 to 5.9wt percent), high catalytic efficiency (1.5 to 4.5 million grams of polyolefin/gram of catalyst) for catalyzing ethylene polymerization or olefin copolymerization, and polyolefin viscosity-average molecular weight of 80 multiplied by 104g/mol to 1000X 104g/mol, the melt index of the polyethylene can be adjusted between 0.0002 and 100 g/10 min, and the bulk density of the polyolefin is between 0.30 and 0.47; the catalyst has high loading capacity and high activity, and the catalyst particles and the polyolefin particles are not adhered to the wall of the container; the polymer particles have good shapes, high bulk density and less fine powder; suitable for use in a gas phase polymerization process, a slurry polymerization process, a loop polymerization process, or a combination polymerization process; the preparation process of the catalyst is simple, the cost is low, the requirement on equipment is low, the energy consumption is low, and the catalyst is cyclicThe environmental pollution is small.
The organic polymer elastomer is added in the preparation process of the catalyst, so that the brittleness of catalyst particles is effectively improved, the toughness of the catalyst particles is improved, the flexible regions are uniformly distributed in the catalyst particles, monomers are easy to diffuse into the flexible regions to contact with the active center of the catalyst and carry out olefin polymerization reaction, the catalyst particles are not easy to break after the ethylene polymerization catalyst is prepared, and the obtained polyethylene particles are good in shape and uniform in distribution.
The organic polymer elastomer and the inorganic magnesium compound form a compound, and the mass ratio of the organic polymer elastomer to the inorganic magnesium compound is 1: (5-100).
The organic high molecular elastomer is selected from polybutadiene, poly-styrene-butadiene rubber, SBS, SIS, SEBS, NR, SEPS, SIBR, ESBR, SSBR, IIR, IR, BR, CR, EPDM or polyacrylate or a mixture thereof.
In the process of preparing the catalyst, an organic polymer elastomer is added, an inorganic magnesium compound and the organic polymer elastomer are uniformly dispersed in an organic solvent to form a solution, a catalyst active component transition metal halide is loaded on a compound of the organic polymer elastomer and the inorganic magnesium compound, partial carbon-carbon double bonds of the organic polymer elastomer and the transition metal generate a coordination complex effect, the density of electron clouds around transition metal atoms is reduced, monomer ethylene or other olefins are more stably coordinated, inserted and chain-extended with the catalyst active center, and the beta-H elimination reaction of a polyethylene extended chain is more difficult to occur, so that the ultrahigh molecular weight polyethylene is obtained.
The operation steps of dissolving the organic polymer elastomer and the inorganic magnesium compound are as follows: (1) dissolving the organic high molecular elastomer in an organic solvent at 0-80 ℃, and stirring for 0.5-8 hours; (2) adding C to step (1) at 0-60 ℃2-C20An organic alcohol of (4); stirring for 0.5-3 hours; (3) adding an aliphatic organic solvent and an inorganic magnesium compound into the step (2) at 0-60 ℃, heating to 70-180 ℃, and stirring for 1-8 hours to form a solution, wherein the mass ratio of the organic high-molecular marble body to the inorganic magnesium compound is 1: (5-100); wherein the organic polymer isMolecular elastomer and C2-C20The mass ratio of the organic alcohol (b) is 1: (10-100).
The inorganic magnesium compound is represented by the general formula (1) Mg (R)aXbR is selected from C1-C20Aliphatic hydrocarbon group of (C)1-C2Fatty alkoxy group of 0, C3-C20Alicyclic group of or C6-C20An aromatic hydrocarbon group of (1); x is selected from halogen wherein a + b ═ 2, a ═ 0, 1 or 2, b ═ 0, 1 or 2; the inorganic magnesium compound is selected from at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, methoxy magnesium chloride, ethoxy magnesium chloride, propoxy magnesium chloride, butoxy magnesium chloride, phenoxy magnesium chloride, diethoxy magnesium, diisopropoxy magnesium, butoxy ethoxy magnesium, isopropoxy magnesium chloride, butyl magnesium chloride and the like, wherein the magnesium compound is preferably magnesium dichloride or diethoxy magnesium; wherein the magnesium diethoxide is purchased directly from the market or prepared according to the patent CN 201410728055.4; wherein the mass ratio of the organic polymer elastomer to the inorganic magnesium compound is 1 (5-50).
The transition metal halide is selected from the group consisting of Ti (R) represented by the general formula (2)1)4-mXmWherein X is a halogen atom selected from Cl, Br, F; m is an integer of 1 to 4; r1Is selected from C1-C20Aliphatic hydrocarbon group of (C)1-C20Fatty alkoxy radical of (C)1-C20Cyclopentadienyl and its derivatives, C1-C20An aromatic hydrocarbon group of (1); r1Specifically selected from: at least one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, phenyl, methoxy, ethoxy, propoxy, or butoxy; specifically selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium, n-butyl titanate, isopropyl titanate, methoxytitanium trichloride, dibutoxytitanium dichloride, tributoxytitanium chloride, tetraphenoxytitanium, chlorotritoxy titanium, dichlorodiphenoxytitanium and trichlorophenoxytitaniumCombining; among them, titanium tetrachloride is preferred; wherein the mass ratio of the organic polymer elastomer to the transition metal halide is 1: (20-1000).
The organic alcohol is C2-C20The organic alcohol of (a) is selected from ethanol, butanol, ethylene glycol, propanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, nonanol, decanol, dodecanol or octadecanol or a mixture thereof, etc.; organic polymer elastomer and C2-C20The mass ratio of the organic alcohol (b) is 1: (10-100).
The organic solvent is C6-C15The aromatic compound of (3) is preferably selected from benzene, toluene, ethylbenzene, xylene, a mixture thereof, and the like.
The aliphatic organic solvent is C5-C20Alkane or C5-C20Cycloalkane compounds, preferably hexane, heptane, octane, decane, dodecane or cyclohexane or mixtures thereof.
The catalyst is used for ethylene polymerization or ethylene copolymerization, and a cocatalyst is required to be added, wherein the cocatalyst is an alkyl aluminum compound or an alkoxy aluminum compound, preferably triethyl aluminum, triisobutyl aluminum, diethyl aluminum monochloride, ethyl aluminum dichloride, n-hexyl aluminum, MAO, mMAO, ethyl aluminoxane or butyl aluminoxane and the like; the molar ratio of the main catalyst to the cocatalyst is 1: (30-800).
The catalyst is used for ethylene polymerization or ethylene copolymerization to synthesize ultra-high molecular weight polyethylene; wherein the comonomer copolymerized with ethylene is C3-C15Preferably propylene, butene, hexene, octene, nonene, decene or styrene or mixtures thereof, the ultra-high molecular weight polyethylene obtained being from 50 to 1000X 104g/mol, preferably from 80 to 1000X 104g/mol。
The preparation method is characterized by comprising the following steps:
(1) dissolving the organic high molecular elastomer in an organic solvent at 0-80 ℃, and stirring for 0.5-8 hours;
(2) adding C to step (1) at 0-60 ℃2-C20An organic alcohol of (4); stirring for 0.5-3 hours;
(3) adding an aliphatic organic solvent and an inorganic magnesium compound into the step (2) at 0-60 ℃, heating to 70-180 ℃, and stirring for 1-8 hours to form a solution, wherein the mass ratio of the organic high-molecular marble body to the inorganic magnesium compound is 1: (5-100);
(4) cooling the system obtained in the step (3) to-50-40 ℃, adding a transition metal halide serving as an active component of the catalyst, and stirring for reaction for 0.5-4 hours; heating to 50-150 ℃, and stirring for reaction for 1-6 hours, wherein the mass ratio of the organic polymer elastomer to the transition metal halide is 1: (20-500);
(5) cooling the system obtained in the step (4) to 0-80 ℃, filtering, adding an aliphatic organic solvent, adding a catalyst active component transition metal halide, and stirring for reaction for 0.5-4 hours; heating to 40-150 ℃, and stirring for reaction for 1-6 hours, wherein the mass ratio of the organic polymer elastomer to the transition metal halide is 1: (20-500);
(6) and (3) cooling the system obtained in the step (5) to 0-80 ℃, filtering, washing for 2-6 times by using an aliphatic organic solvent, and carrying out vacuum drying for 0.5-4 hours at the temperature of 30-60 ℃ to obtain solid main catalyst particles.
(7) The catalyst obtained in the step (6) is used for ethylene polymerization or ethylene copolymerization to synthesize the ultra-high molecular weight polyethylene, the ethylene pressure is 0.1-10MPa during polymerization, and the molar ratio of the main catalyst to the cocatalyst is 1: (30-800), the polymerization temperature is 20-90 ℃, and the hydrogen pressure is 0-1 MPa.
The content of transition metal in the main catalyst is measured by XPS method.
The morphology of the main catalyst particles was determined by SEM method.
The molecular weight of the ultra-high molecular weight polyethylene is measured by a viscosity method.
Drawings
FIG. 1 SEM photographs of particle morphology of catalysts of examples 1 to 16
FIG. 2 SEM photographs of particle morphology of comparative examples 1 to 3 catalysts
Detailed Description
The present invention will be further described with reference to the following specific embodiments, but the scope of the present invention is not limited to the following examples.
Example 1
Preparation of the main catalyst:
after a 300mL glass reaction bottle is fully replaced by nitrogen, 50mL toluene and 0.2g polybutadiene are added into the reaction bottle at the temperature of 30 ℃, and the mixture is stirred for 3 hours to dissolve the polybutadiene; adding 5mL of isooctanol, and stirring for 2 hours; adding 15mL of decane, adding 1.5g of magnesium chloride, heating to 120 ℃, and stirring for 3 hours; cooling to-5 deg.C, adding TiCl4Stirring for 2 hours at a volume of 30 mL; heating to 90 ℃, and stirring for 3 hours; filtering at 30 ℃, adding 15mL of normal hexane, adding TiCl420mL, stirring for 2 hours; heating to 70 deg.C, and stirring for 3 hr; filtration at 30 ℃ and washing 4 times with 50mL of hexane each time, and vacuum drying at 50 ℃ for 3 hours gave 3.8g of procatalyst particles with 4.1 wt% Ti.
Synthesis of ultra-high molecular weight polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction kettle, 8mg of the main catalyst prepared in example 1 was added, 1mL of triethylaluminum (1M hexane solution) was added, 0.1L of hydrogen was charged, ethylene was charged to a pressure of 0.8MPa, stirring was performed, the temperature was maintained at 75 ℃ for 1 hour, and 284 g of a polymerization product was collected.
Example 2
Preparation of the main catalyst:
after a 300mL glass reaction bottle is fully replaced by nitrogen, 30mL ethylbenzene and 50mL toluene are added into the reaction bottle at 40 ℃, 0.5g ESBR is added, and the mixture is stirred for 2.5 hours to dissolve the ESBR; adding 4.5mL of isooctanol and 8mL of ethanol, and stirring for 3 hours; adding 25mL of decane, adding 2g of magnesium chloride, heating to 110 ℃, and stirring for 3.5 hours; cooling to 0 deg.C, adding TiCl435mL, stirring for 1 hour; heating to 100 deg.c and stirring for 4 hr; filtering at 20 ℃, adding 25mL of heptane, and adding TiCl425mL, stirring for 0.5 hour; heating to 80 deg.C, and stirring for 3 hr; filtration at 30 ℃ and washing 5 times with 60mL of hexane each time, and vacuum drying at 40 ℃ for 3.5 hours gave 4.5g of procatalyst particles with 3.8 wt% Ti.
Synthesis of ultra-high molecular weight polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction kettle, 10mg of the main catalyst prepared in example 2 was added, 1mL of triethylaluminum (1M hexane solution) was added, 0L of hydrogen was charged, ethylene was charged to a pressure of 0.8MPa, stirring was performed, the temperature was maintained at 80 ℃ for 1 hour, and 356 g of a polymerization product was collected.
Example 3
Preparation of the main catalyst:
after a 300mL glass reaction bottle is fully replaced by nitrogen, 80mL dimethylbenzene is added into the reaction bottle at 50 ℃, 0.5g SSBR is added, and the mixture is stirred for 2 hours to dissolve the SSBR; adding 4mL of decanol and 18mL of ethanol, and stirring for 3 hours; adding 30mL of heptane, adding 1.5g of magnesium chloride, heating to 100 ℃, and stirring for 4 hours; cooling to-10 deg.C, adding TiCl440mL, stirring for 4 hours; heating to 110 deg.c and stirring for 4 hr; filtering at 40 ℃, adding 30mL of hexane, adding TiCl435mL, stirring for 1 hour; heating to 70 deg.C, and stirring for 4 hr; filtration at 35 ℃ and washing 5 times with 40mL of hexane each time, and vacuum drying at 50 ℃ for 2.5 hours gave 3.5g of procatalyst particles with 4.3 wt% Ti.
Synthesis of ultra-high molecular weight polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction vessel, 10mg of the main catalyst prepared in example 3 was added, 0.5mL of triethylaluminum (1M hexane solution) was added, 0.05L of hydrogen was charged, ethylene was charged to a pressure of 0.7MPa, stirring was performed, the temperature was maintained at 70 ℃ and the reaction was carried out for 1 hour, and 312 g of the polymerization product was collected.
Example 4
Preparation of the main catalyst:
after a 300mL glass reaction bottle is fully replaced by nitrogen, 80mL benzene and 0.1g SBS are added into the reaction bottle at 50 ℃, and the mixture is stirred for 2 hours to dissolve the SBS; adding 4mL of hexanol and 18mL of ethanol, and stirring for 3 hours; adding 30mL of heptane, adding 1.5g of magnesium chloride, heating to 100 ℃, and stirring for 4 hours; cooling to 35 deg.C, adding TiCl440mL, stirring for 2 hours; heating to 110 deg.c and stirring for 4 hr; filtering at 40 ℃, adding 30mL of hexane, adding TiCl435mL, stirring for 3 hours; heating to 70 deg.C, and stirring for 4 hr; filtration at 35 ℃ and washing 5 times with 40mL of hexane each time, and vacuum drying at 40 ℃ for 3 hours gave 3.3g of procatalyst particles with 4.4 wt% Ti.
Synthesis of ultra-high molecular weight polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction vessel, 10mg of the main catalyst prepared in example 4 was added, 1.5mL of triethylaluminum (1M hexane solution) was added, 0.05L of hydrogen was charged, ethylene was charged to a pressure of 0.9MPa, stirring was carried out, the temperature was maintained at 60 ℃ for reaction for 1 hour, and 362 g of a polymerization product was collected.
Example 5
Preparation of the main catalyst:
after a 400mL glass reaction bottle is fully replaced by nitrogen, 100mL toluene is added into the reaction bottle at 25 ℃, 0.5g SEBS and 0.2g SBS are added, and stirring is carried out for 2 hours to dissolve the SEBS and the SBS; adding 4mL of hexanol and 18mL of ethanol, and stirring for 3 hours; adding 30mL of heptane, adding 2.5g of magnesium chloride, heating to 100 ℃, and stirring for 4 hours; cooling to-10 deg.C, adding TiCl445mL, stirring for 2 hours; heating to 110 deg.c and stirring for 4 hr; filtering at 40 ℃, adding 30mL of hexane, adding TiCl430mL, stirring for 1.5 hours; heating to 70 deg.C, and stirring for 4 hr; filtration at 35 ℃ and washing 5 times with 40mL of hexane each time, and vacuum drying at 40 ℃ for 3 hours gave 5.1g of procatalyst particles with 4.5 wt% Ti.
Synthesis of ultra-high molecular weight polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction vessel, 10mg of the procatalyst prepared in example 5 was added, 0.5mL of triethylaluminum (1M hexane solution) was added, 0.05L of hydrogen was charged, ethylene was charged to a pressure of 0.9MPa, stirring was carried out, the temperature was maintained at 30 ℃ for reaction for 1 hour, and 367 g of a polymerization product was collected.
Example 6
Preparation of the main catalyst:
after a 350mL glass reaction flask was sufficiently purged with nitrogen, 80mL of toluene was added to the reaction flask at 50 ℃ and 0.1g of SIBR and 0.1g of SIS were added and stirred for 2 hoursDissolving the SIBR and SIS; adding 8mL of hexanol and 10mL of ethanol, and stirring for 3 hours; adding 20mL of decane, adding 3.5g of magnesium chloride, heating to 140 ℃, and stirring for 6 hours; cooling to-25 deg.C, adding TiCl440mL, stirring for 2 hours; heating to 145 ℃, and stirring for 4 hours; filtering at 40 ℃, adding 30mL of hexane, adding TiCl430mL, stirring for 1 hour; heating to 100 deg.c and stirring for 5 hr; filtration at 35 ℃ and washing 3 times with 30mL of hexane each time, and vacuum drying at 30 ℃ for 3 hours gave 6.0g of procatalyst particles with 4.6 wt% Ti.
Synthesis of ultra-high molecular weight polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction kettle, 10mg of the main catalyst prepared in example 6 was added, 0.5mL of triethylaluminum (1M hexane solution) was added, 1L of hydrogen was charged, ethylene was charged to a pressure of 0.9MPa, stirring was performed, the temperature was maintained at 70 ℃ for 1 hour, and 303 g of a polymerization product was collected.
Example 7
Preparation of the main catalyst:
after a 350mL glass reaction bottle is fully replaced by nitrogen, 80mL toluene is added into the reaction bottle at 50 ℃, 0.2g NR and 0.1g polybutadiene are added, and the mixture is stirred for 2 hours to dissolve the NR and the polybutadiene; adding 18mL of octanol, and stirring for 3 hours; adding 20mL of decane, adding 3g of magnesium chloride, heating to 110 ℃, and stirring for 4 hours; cooling to 25 deg.C, adding TiCl440mL, stirring for 2 hours; heating to 145 ℃, and stirring for 4 hours; filtering at 40 ℃, adding 30mL of hexane, adding TiCl430mL, stirring for 1 hour; heating to 100 deg.c and stirring for 5 hr; filtration at 35 ℃ and washing 3 times with 30mL of hexane each time, and vacuum drying at 30 ℃ for 3 hours gave 4.6g of procatalyst particles with 4.2 wt% Ti.
Synthesis of ultra-high molecular weight polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction vessel, 10mg of the main catalyst prepared in example 7 was added, 0.8mL of triethylaluminum (1M hexane solution) was added, 0.2L of hydrogen was charged, ethylene was charged to a pressure of 0.7MPa, stirring was performed, the temperature was maintained at 70 ℃ for reaction for 1 hour, and 313 g of a polymerization product was collected.
Example 8
Preparation of the main catalyst:
after a 350mL glass reaction bottle is fully replaced by nitrogen, 80mL toluene is added into the reaction bottle at 50 ℃, 0.3g NR and 0.2g SIBR are added, and the mixture is stirred for 2 hours to dissolve the NR and the SIBR; adding 10mL of octanol, and stirring for 3 hours; adding 20mL of decane, adding 3.5g of magnesium chloride, heating to 110 ℃, and stirring for 4 hours; cooling to-25 deg.C, adding TiCl440mL, stirring for 2 hours; heating to 145 ℃, and stirring for 4 hours; filtering at 40 ℃, adding 30mL of hexane, adding TiCl4Stirring for 2 hours at a volume of 30 mL; heating to 100 deg.c and stirring for 5 hr; filtration at 35 ℃ and washing 3 times with 30mL of hexane each time, and vacuum drying at 30 ℃ for 3 hours gave 5.5g of procatalyst particles with 5.6 wt% Ti.
Synthesis of ultra-high molecular weight polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction kettle, 10mg of the main catalyst prepared in example 8 was added, 0.8mL of triethylaluminum (1M hexane solution) was added, 0.02L of hydrogen was charged, ethylene was charged to a pressure of 0.8MPa, stirring was performed, the temperature was maintained at 30 ℃ for reaction for 1 hour, and 325 g of a polymerization product was collected.
Example 9
Preparation of the main catalyst:
after a 350mL glass reaction bottle is fully replaced by nitrogen, 80mL toluene is added into the reaction bottle at 30 ℃, 0.1g IIR and 0.2g ESBR are added, and the mixture is stirred for 3 hours to dissolve the IIR and the ESBR; adding 10mL of octanol, and stirring for 3 hours; adding 20mL of decane, adding 2.5g of magnesium chloride, heating to 110 ℃, and stirring for 7 hours; cooling to 5 deg.C, adding TiCl440mL, stirring for 2 hours; heating to 145 ℃, and stirring for 4 hours; filtering at 10 ℃, adding 30mL of hexane, adding TiCl4Stirring for 2 hours at a volume of 30 mL; heating to 100 deg.c and stirring for 5 hr; filtration at 35 ℃ and washing 3 times with 30mL of hexane each time, and vacuum drying at 30 ℃ for 3 hours gave 4.2g of procatalyst particles with 3.9 wt% Ti.
Synthesis of ultra-high molecular weight polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction vessel, 10mg of the main catalyst prepared in example 9 was added, 0.8mL of triethylaluminum (1M hexane solution) was added, 0.02L of hydrogen was charged, ethylene was charged to a pressure of 0.8MPa, stirring was performed, the temperature was maintained at 65 ℃ for reaction for 1 hour, and 297 g of a polymerization product was collected.
Example 10
Preparation of the main catalyst:
after a 300mL glass reaction bottle is fully replaced by nitrogen, 80mL toluene is added into the reaction bottle at 30 ℃, 0.2g CR and 0.3g SSBR are added, and the mixture is stirred for 4 hours to dissolve the CR and the SSBR; adding 10mL of octanol, and stirring for 3 hours; adding 20mL of decane, adding 2.5g of magnesium chloride, heating to 110 ℃, and stirring for 4 hours; cooling to-5 deg.C, adding TiCl440mL, stirring for 2 hours; heating to 115 ℃, and stirring for 4 hours; filtering at 10 ℃, adding 30mL of cyclohexane, adding TiCl430mL, stirring for 0.5 hour; heating to 70 deg.C, and stirring for 5 hr; filtration at 15 ℃ and washing 3 times with 30mL of hexane each time, and vacuum drying at 40 ℃ for 3 hours gave 3.9g of procatalyst particles with 3.8 wt% Ti.
Synthesis of ultra-high molecular weight polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction kettle, 10mg of the main catalyst prepared in example 10 was added, 0.8mL of triethylaluminum (1M hexane solution) was added, 0.02L of hydrogen was charged, ethylene was charged to a pressure of 0.8MPa, stirring was performed, the temperature was maintained at 55 ℃ for reaction for 1 hour, and 288 g of a polymerization product was collected.
Example 11
Preparation of the main catalyst:
after a 300mL glass reaction flask was sufficiently replaced with nitrogen, 80mL of toluene and 0.5g of EPDM were added to the reaction flask at 30 ℃ and stirred for 4 hours to dissolve the EPDM; adding 10mL of octanol, and stirring for 3 hours; adding 20mL of decane, adding 2.5g of magnesium chloride, heating to 110 ℃, and stirring for 4 hours; cooling to-25 deg.C, adding TiCl440mL, stirring for 1 hour; heating to 105 ℃, and stirring for 4 hours; filtering at 10 ℃, adding 30mL of hexane, adding TiCl430mL, stirring for 1 hour; then the temperature is raised to 90 DEG CStirring for 6 hours; filtration at 15 ℃ and washing 4 times with 40mL of hexane each time, and vacuum drying at 40 ℃ for 3 hours gave 3.8g of procatalyst particles with 4.0 wt% Ti.
Synthesis of ultra-high molecular weight polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction vessel, 10mg of the main catalyst prepared in example 11 was added, 0.8mL of triethylaluminum (1M hexane solution) was added, 0.01L of hydrogen was charged, ethylene was charged to a pressure of 0.7MPa, stirring was performed, the temperature was maintained at 60 ℃ for reaction for 1 hour, and 293 g of a polymerization product was collected.
Example 12
Preparation of the main catalyst:
after a 300mL glass reaction bottle is fully replaced by nitrogen, 80mL toluene is added into the reaction bottle at 30 ℃, 0.2g EPR and 0.3g SBS are added, and the mixture is stirred for 4 hours to dissolve the EPR and SBS; adding 10mL of octanol, and stirring for 3 hours; adding 20mL of decane, adding 2.5g of magnesium chloride, heating to 110 ℃, and stirring for 4 hours; cooling to-25 deg.C, adding TiCl440mL, stirring for 2 hours; heating to 105 ℃, and stirring for 4 hours; filtering at 10 ℃, adding 30mL of hexane, adding TiCl4Stirring for 2 hours at a volume of 30 mL; heating to 90 deg.C, and stirring for 3 hr; filtration at 15 ℃ and washing 4 times with 40mL of hexane each time, and vacuum drying at 40 ℃ for 3 hours gave 3.7g of procatalyst particles with 4.1 wt% Ti.
Synthesis of ultra-high molecular weight polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction kettle, 10mg of the main catalyst prepared in example 12 was added, 1mL of triethylaluminum (1M hexane solution) was added, 0.1L of hydrogen was charged, ethylene was charged to a pressure of 0.8MPa, stirring was performed, the temperature was maintained at 70 ℃ for 1 hour, and 303 g of a polymerization product was collected.
Example 13
Preparation of the main catalyst:
after a 300mL glass reaction bottle is fully replaced by nitrogen, 80mL toluene is added into the reaction bottle at 30 ℃, 0.5g BR and 0.2g SEPS are added, and the mixture is stirred for 4 hours to dissolve the BR and the SEPS; adding octanol into 10mL, stirring for 3 hoursWhen the current is over; adding 20mL of decane, adding 2.5g of diethoxymagnesium, heating to 110 ℃, and stirring for 4 hours; cooling to-25 deg.C, adding TiCl440mL, stirring for 2 hours; heating to 105 ℃, and stirring for 2 hours; filtering at 30 ℃, adding 30mL of hexane, adding TiCl435mL, stirring for 2 hours; heating to 90 deg.C, and stirring for 3 hr; filtration at 15 ℃ and washing 4 times with 40mL of hexane each time, and vacuum drying at 40 ℃ for 3 hours gave 3.6g of procatalyst particles with 4.3 wt% Ti.
Synthesis of ultra-high molecular weight polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction kettle, 10mg of the main catalyst prepared in example 13 was added, 1mL of triethylaluminum (1M hexane solution) was added, 0L of hydrogen was charged, ethylene was charged to a pressure of 0.8MPa, stirring was performed, the temperature was maintained at 70 ℃ and the reaction was carried out for 1 hour, and 306 g of the polymerization product was collected.
Example 14
Preparation of the main catalyst:
after a 300mL glass reaction flask was sufficiently purged with nitrogen, 80mL of toluene was added to the reaction flask at 5 ℃ and 0.3g of IR and 0.2g of ESBR were added, and stirred for 4 hours to dissolve the IR and ESBR; adding 5mL of octanol, and stirring for 3 hours; adding 20mL of decane, adding 5g of magnesium chloride, heating to 120 ℃, and stirring for 4 hours; cooling to-5 deg.C, adding TiCl440mL, stirring for 2 hours; heating to 105 ℃, and stirring for 5 hours; filtering at 30 ℃, adding 30mL of hexane, adding TiCl435mL, stirring for 2 hours; heating to 100 deg.c and stirring for 3 hr; filtration at 15 ℃ and washing 4 times with 40mL of hexane each time, and vacuum drying at 40 ℃ for 3 hours gave 6.8g of procatalyst particles with 4.1 wt% Ti.
Synthesis of ultra-high molecular weight polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction kettle, 10mg of the main catalyst prepared in example 14 was added, 1mL of triethylaluminum (1M hexane solution) was added, 0.01L of hydrogen was charged, ethylene was charged to a pressure of 0.8MPa, stirring was performed, the temperature was maintained at 70 ℃ for 1 hour, and 311 g of a polymerization product was collected.
Example 15
Preparation of the main catalyst:
after a 300mL glass reaction bottle is fully replaced by nitrogen, 80mL toluene and 0.5g styrene-butadiene rubber are added into the reaction bottle at 5 ℃, and the mixture is stirred for 4 hours to dissolve the styrene-butadiene rubber; adding 5mL of octanol, and stirring for 3 hours; adding 20mL of decane, adding 3g of magnesium chloride, heating to 120 ℃, and stirring for 4 hours; cooling to-5 deg.C, adding TiCl440mL, stirring for 2 hours; heating to 105 ℃, and stirring for 5 hours; filtering at 30 ℃, adding 30mL of hexane, adding TiCl435mL, stirring for 2 hours; heating to 100 deg.c and stirring for 3 hr; filtration at 15 ℃ and washing 4 times with 40mL of hexane each time, and vacuum drying at 40 ℃ for 3 hours gave 4.2g of procatalyst particles with 4.3 wt% Ti.
Synthesis of ultra-high molecular weight polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction kettle, 10mg of the main catalyst prepared in example 15 was added, 1mL of triethylaluminum (1M hexane solution) was added, 0.01L of hydrogen was charged, ethylene was charged to a pressure of 0.8MPa, stirring was performed, the temperature was maintained at 70 ℃ for 1 hour, and 322 g of a polymerization product was collected.
Example 16
Preparation of the main catalyst:
after a 300mL glass reaction bottle is fully replaced by nitrogen, 80mL toluene and 0.5g styrene-butadiene rubber are added into the reaction bottle at 5 ℃, and the mixture is stirred for 4 hours to dissolve the styrene-butadiene rubber; adding 5mL of octanol, and stirring for 3 hours; adding 20mL of decane, adding 3g of magnesium chloride, heating to 120 ℃, and stirring for 4 hours; cooling to-5 deg.C, adding TiCl440mL, stirring for 2 hours; heating to 105 ℃, and stirring for 5 hours; filtering at 30 ℃, adding 30mL of hexane, adding TiCl435mL, stirring for 2 hours; heating to 100 deg.c and stirring for 3 hr; filtration at 15 ℃ and washing 4 times with 40mL of hexane each time, and vacuum drying at 40 ℃ for 3 hours gave 4.2g of procatalyst particles with 4.3 wt% Ti.
Synthesis of ultra-high molecular weight polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction kettle, 10mg of the main catalyst prepared in example 16 was added, 1mL of triethylaluminum (1M hexane solution) was added, 0.5L of 1-butene was added, 0.01L of hydrogen was charged, ethylene was charged to a pressure of 0.8MPa, stirring was carried out, the temperature was maintained at 70 ℃ for 1 hour, and 308 g of a polymerization product was collected.
Comparative example 1
Preparation of the main catalyst:
after a 300mL glass reaction bottle is fully replaced by nitrogen, 80mL toluene and 5mL octanol are added into the reaction bottle at 5 ℃, and the mixture is stirred for 3 hours; adding 20mL of decane, adding 5g of magnesium chloride, heating to 120 ℃, and stirring for 4 hours; cooling to-5 deg.C, adding TiCl440mL, stirring for 2 hours; heating to 105 ℃, and stirring for 5 hours; filtering at 30 ℃, adding 30mL of hexane, adding TiCl435mL, stirring for 2 hours; heating to 100 deg.c and stirring for 3 hr; filtration at 15 ℃ and washing 4 times with 40mL of hexane each time, and vacuum drying at 40 ℃ for 3 hours gave 6.3g of procatalyst particles with 4.3 wt% Ti.
Synthesis of polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction kettle, 10mg of the main catalyst prepared in comparative example 1 was added, 1mL of triethylaluminum (1M hexane solution) was added, 0.01L of hydrogen was charged, ethylene was charged to a pressure of 0.8MPa, stirring was performed, the temperature was maintained at 70 ℃ for 1 hour, and 281 g of a polymerization product was collected.
Comparative example 2
Preparation of the main catalyst:
after a 300mL glass reaction bottle is fully replaced by nitrogen, 80mL toluene and 5mL octanol are added into the reaction bottle at 5 ℃, and the mixture is stirred for 3 hours; adding 20mL of decane, adding 5g of diethoxymagnesium, heating to 120 ℃, and stirring for 4 hours; cooling to-5 deg.C, adding TiCl440mL, stirring for 2 hours; heating to 105 ℃, and stirring for 5 hours; filtering at 30 ℃, adding 30mL of hexane, adding TiCl435mL, stirring for 2 hours; heating to 100 deg.c and stirring for 3 hr; filtration at 15 ℃ and washing 4 times with 40mL of hexane each time, and vacuum drying at 40 ℃ for 3 hours gave 6.5g of procatalyst particles with 4.5 wt% Ti.
Synthesis of polyethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction kettle, 10mg of the main catalyst prepared in comparative example 2 was added, 1mL of triethylaluminum (1M hexane solution) was added, 0L of hydrogen was charged, ethylene was charged to a pressure of 0.8MPa, stirring was carried out, the temperature was maintained at 70 ℃ for 1 hour, and 289 g of a polymerization product was collected.
Comparative example 3
Preparation of the main catalyst:
after a 300mL glass reaction bottle is fully replaced by nitrogen, 80mL toluene and 5mL octanol are added into the reaction bottle at 5 ℃, and the mixture is stirred for 3 hours; adding 20mL of decane, adding 5g of magnesium chloride, heating to 120 ℃, and stirring for 4 hours; cooling to-5 deg.C, adding TiCl440mL, stirring for 2 hours; heating to 105 ℃, and stirring for 5 hours; filtering at 30 ℃, adding 30mL of hexane, adding TiCl435mL, stirring for 2 hours; heating to 100 deg.c and stirring for 3 hr; filtration at 15 ℃ and washing 4 times with 40mL of hexane each time, and vacuum drying at 40 ℃ for 3 hours gave 6.3g of procatalyst particles with 4.3 wt% Ti.
Synthesis of copolymerized ethylene
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-hexane was added to the reaction kettle, 10mg of the main catalyst prepared in comparative example 1 was added, 1mL of triethylaluminum (1M hexane solution) was added, 0.5L of 1-butene was added, 0.01L of hydrogen was charged, ethylene was charged to a pressure of 0.8MPa, stirring was carried out, the temperature was maintained at 70 ℃ for reaction for 1 hour, and 265 g of a polymerization product was collected.
The results are shown in Table 1.
TABLE 1
The catalyst of the ultra-high molecular weight polyethylene and the catalyst particles prepared by the preparation method of the catalystUniform particle distribution, particle size of 15-60 μm, high catalyst loading (2.0-5.9 wt%), high catalytic efficiency for ethylene polymerization or olefin copolymerization, and high polyolefin viscosity-average molecular weight of 80 × 104g/mol to 1000X 104g/mol; the polymer particles have good shape, high bulk density and less fine powder, and the bulk density of the polyolefin is between 0.30 and 0.47; suitable for use in a gas phase polymerization process, a slurry polymerization process, a loop polymerization process, or a combination polymerization process. It is seen from the results of examples 1 to 16 and comparative examples 1 to 3 that the ultra-high molecular weight polyethylene can be effectively obtained by catalyzing the polymerization or copolymerization of ethylene using the catalysts prepared in examples 1 to 15. The catalyst prepared in comparative examples 1-2 is used for catalyzing ethylene polymerization or copolymerization, and the molecular weight of the polyethylene is less than 10 multiplied by 104g/mol, ultra-high molecular weight polyethylene cannot be obtained.
Claims (6)
1. The preparation method of the catalyst of the ultra-high molecular weight polyethylene is characterized in that the catalyst of the ultra-high molecular weight polyethylene comprises an organic polymer elastomer, an inorganic magnesium compound and C2-C20Organic alcohol or transition metal halide of (a); wherein the organic high-molecular marble body is mixed with an inorganic magnesium compound and C2-C20The mass ratio of the organic alcohol or transition metal halide is 1: (5-100): (10-100): (40-1000);
the preparation method comprises the following steps:
(1) dissolving the organic polymer elastomer in the organic solvent A at 0-80 ℃, and stirring for 0.5-8 hours;
(2) adding C to step (1) at 0-60 ℃2-C20An organic alcohol of (4); stirring for 0.5-3 hours;
(3) adding an aliphatic organic solvent and an inorganic magnesium compound into the step (2) at the temperature of 0-60 ℃, heating to 70-180 ℃, and stirring for 1-8 hours to form a solution, wherein the mass ratio of the organic high-molecular marble body to the inorganic magnesium compound is 1: (5-100);
(4) cooling the system obtained in the step (3) to-50-40 ℃, adding a catalyst active component transition metal halide, heating to 50-150 ℃, and stirring for reaction for 1-6 hours; wherein the mass ratio of the organic polymer elastomer to the transition metal halide is 1: (20-500);
(5) cooling the system obtained in the step (4) to 0-80 ℃, filtering, adding an aliphatic organic solvent, adding a catalyst active component transition metal halide, heating to 40-150 ℃, and stirring for reacting for 1-6 hours; wherein the mass ratio of the organic polymer elastomer to the transition metal halide is 1: (20-500);
(6) cooling the system obtained in the step (5) to 0-80 ℃, filtering, washing for 2-6 times by using an aliphatic organic solvent, and carrying out vacuum drying for 0.5-4 hours at 30-60 ℃ to obtain a solid main catalyst;
wherein the organic solvent A is C6-C15The aromatic compound of (1);
wherein the aliphatic organic solvent is C5-C20An alkane or cycloalkane compound of (a).
2. The method of claim 1, wherein the organic polymer elastomer is selected from polybutadiene, styrene-butadiene rubber, SBS, SIS, SEBS, NR, SEPS, SIBR, ESBR, SSBR, IIR, IR, BR, CR, EPDM, polyacrylate, and mixtures thereof.
3. The process according to claim 1, wherein the inorganic magnesium compound is represented by the general formula (1) Mg (R)aXbR is selected from C1-C20Aliphatic hydrocarbon group of (C)1-C20Fatty alkoxy radical of (C)3-C20Alicyclic group of or C6-C20An aromatic hydrocarbon group of (1); x is selected from halogen wherein a + b ═ 2, a ═ 0, 1 or 2, and b ═ 0, 1 or 2.
4. The method according to claim 1, wherein the transition metal halide is selected from the group consisting of Ti (R) represented by the general formula (2)1)4-mXmWherein X is a halogen atom selected from Cl, Br, F; m is an integer of 1 to 4; r1Is selected from C1-C20 aliphatic hydrocarbon group, C1-C20Fatty alkoxy radical of (C)1-C20Cyclopentadienyl and its derivatives, C1-C20An aromatic hydrocarbon group of (1); r1 is specifically selected from: at least one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, phenyl, methoxy, ethoxy, propoxy, or butoxy.
5. The application of the catalyst of the ultra-high molecular weight polyethylene is characterized in that the catalyst is used for ethylene polymerization or ethylene copolymerization, a cocatalyst is required to be added, and the molar ratio of a main catalyst to the cocatalyst is 1: (30-800); wherein the cocatalyst is an alkyl aluminum compound or an alkoxy aluminum compound.
6. The application of the catalyst for the ultra-high molecular weight polyethylene is characterized in that the catalyst is used for the polymerization of ethylene or the copolymerization of ethylene to synthesize the ultra-high molecular weight polyethylene; wherein the comonomer copolymerized with ethylene is C3-C15Alpha-olefins of (a); wherein, the ethylene polymerization or ethylene copolymerization conditions are that the ethylene pressure is 0.1-10MPa, the molar ratio of the main catalyst to the cocatalyst is 1: (30-800), the polymerization temperature is 20-90 ℃, and the hydrogen pressure is 0-1 MPa.
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| CN105859919A (en) * | 2016-04-17 | 2016-08-17 | 北京化工大学 | Complex support type catalyst, preparation method and application |
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| CN105859919A (en) * | 2016-04-17 | 2016-08-17 | 北京化工大学 | Complex support type catalyst, preparation method and application |
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| Title |
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| 司荣双: "复合载体负载型催化剂制备可调变性能UHMWPE的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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