CN1746197A - Ultrahigh-molecular weight polyethylene catalyst, its preparation and use thereof - Google Patents
Ultrahigh-molecular weight polyethylene catalyst, its preparation and use thereof Download PDFInfo
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- CN1746197A CN1746197A CN 200410054344 CN200410054344A CN1746197A CN 1746197 A CN1746197 A CN 1746197A CN 200410054344 CN200410054344 CN 200410054344 CN 200410054344 A CN200410054344 A CN 200410054344A CN 1746197 A CN1746197 A CN 1746197A
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Abstract
A super-high molecular weight polyethylene catalyst, its production and use are disclosed. The catalyst consists of (A) and (B)) components, (A) component is solid main catalyst and (B) component is auxiliary catalyst, (A) component consists of titanated and silicide components with magniferous compound carrier, and (B) component is organic aluminium compound. It advantages include better catalytic activity, adjustable molecular weight, to increase tap density and decrease fine powder and coarse grain formation.
Description
Technical field
The present invention relates to a kind of extra high-molecular polythene catalyst and preparation method thereof and application, be particularly related to titanium catalyst solid ingredient (A), organo-metallic aluminum compound cocatalyst component (B) that a kind of catalyst system comprises the magnesium-containing carrier load, be used to prepare relative molecular mass 1,000,000 to 1,000 ten thousand, have the good ultrahigh molecular weight polyethylene powder of high-bulk-density and form.
Background technology
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) has performances such as unrivaled shock-resistant, wear-resistant, the self-lubricating of other plastics, low temperature resistant, resistance to chemical attack because of its molecular weight is high.The physical and mechanical properties excellence of UHMWPE is widely used in fields such as machinery, transportation, weaving, papermaking, mining industry, electric power, agricultural, chemical industry and sports movement apparatus, wherein being most widely used with heavy packages container and pipeline.In addition, because UHMWPE has the physiology inertia, use on clinical medicine as heart valve, orthopedics's part, joint prosthesis etc.
CN1033703C has reported a kind of method for preparing ultrahigh molecular weight polyethylene(UHMWPE), by add ZnCl in catalyst system
2Component can be regulated the molecular weight of ultrahigh molecular weight polyethylene(UHMWPE) between 60～6,100,000.Make the matrix component of catalyzer by grinding, then with reaction method handle matrix component and catalyzer.Analyze from the data that embodiment provides, the ultrahigh molecular weight polyethylene(UHMWPE) of preparation has good particle distribution, but does not relate to the method for the ultrahigh molecular weight polyethylene(UHMWPE) class spherical powder that how to prepare high-bulk-density, and this system catalytic activity is lower.
CN1034509C provides a kind of preparation method of ultrahigh molecular weight polyethylene(UHMWPE) of high-bulk-density, and its catalyzer contains organo-aluminium compound and reduces and handle with organo-aluminium compound the titanium component of reduzate gained from Ti (IV) compound.Although can prepare the ultrahigh molecular weight polyethylene(UHMWPE) of high-bulk-density, this catalyst activity is too low, is not suitable for industrial production.
CN1452637A, US2002/0045537A1 have reported and have been used to prepare the catalyzer of ultra-high molecular weight and utilize it to prepare the method for ultrahigh molecular weight polyethylene(UHMWPE).Described catalyzer makes by reaction method, helps to make the ultrahigh molecular weight polyethylene(UHMWPE) with high bulk density and narrow particle distribution.But be not difficult to find out by analyzing embodiment, this catalyzer initial activity height, the reaction times is short, and for industrial production, vinyl polymerization is a strong exothermal reaction, and therefore reaction will be difficult for steadily being controlled.
CN1042834C discloses and has prepared the method and the spherical polyolefinic method that prepare ultra-high molecular weight of polymerization of Alpha-olefin with spherical catalyst.This method makes spherical carrier of catalyst with ammonium dawsonite spraying drying, carries titanium then.Although the ultrahigh molecular weight polyethylene(UHMWPE) of preparation has higher tap density, catalytic activity is low, and molecular weight or limiting viscosity do not specify by embodiment as the most important performance perameter of ultrahigh molecular weight polyethylene(UHMWPE).
Summary of the invention
The purpose of this law invention is to overcome in the past, and ultrahigh molecular weight polyethylene is equipped with the existing deficiency of technology, when guaranteeing that the extra high-molecular polythene catalyst catalytic activity is stable, improve the form of resin, reduce fine powder and coarse particles growing amount, improve tap density, the expansion molecular weight ranges realizes that molecular weight is adjustable.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of extra high-molecular polythene catalyst, it is characterized in that, this catalyzer comprises (A), (B) component, wherein, (A) component is a solid main catalyst, (B) component is a promotor, and described (A) component is made of containing titanium component and containing silicon components of magnesium-containing compound load, and described (B) component is an organo-aluminium compound.
This catalyzer also comprises (C) component, should (C) component be the property regulation component, and described (C) component is silicoorganic compound.
The first step is passed through in containing titanium component and containing silicon components of described magnesium-containing compound load: magnesium-containing compound and organic oxygen-containing compound, inert solvent are at 0～150 ℃, preferred 40～120 ℃ form mixed solution (a) down, second step: the mixing solutions that in mixed solution (a), slowly drips first kind, second kind two kinds of silicon-containing compounds, certain temperature react suspension (b), the 3rd step: titanium compound and/or organic oxygen-containing compound treating suspension (b) obtain after filtering, wash by this area routine techniques.
Described magnesium-containing compound is water, the alcohol complex of magnesium dichloride, dibrominated magnesium, bifluoride magnesium and above-claimed cpd, and perhaps above-claimed cpd and titanium-containing compound are through grinding the complex compound that forms.
Organic oxygen-containing compound in the described the first step is C
1～C
8Monohydroxy-alcohol or dibasic alcohol, comprise being selected from methyl alcohol, ethanol, butanols, ethylene glycol, propylene glycol, 2-Ethylhexyl Alcohol, decyl alcohol; Or epoxy compounds, comprise and be selected from oxyethane, propylene oxide, epoxy chloropropane, tetrahydrofuran (THF), dioxane, butylene oxide ring, epoxy hexane, or monobasic ester, dibasic ester or ternary ester, comprise being selected from ethyl acetate, methyl benzoate, diethyl phthalate, diisobutyl phthalate, triethyl phosphate, tributyl phosphate; Described organic oxygen-containing thing or be two or three mixture in above-mentioned alcohol, epoxy compounds and the ester.
Described inert solvent is C
1～C
10Alkane, naphthenic hydrocarbon, aromatic hydrocarbons, alkane substitute, substituted ring alkane or substituted arene, comprise being selected from normal hexane, normal heptane, iso-pentane, hexanaphthene, decane, toluene, dimethylbenzene, 1 a kind of in 2-ethylene dichloride, chlorocyclohexane, n-propylcarbinyl chloride, the chlorobenzene.
Described first kind of silicon-containing compound has R
nSiCl
4-n(0≤n≤3) structure, R is alkyl, aryl, hydrogen or oxy radical, and representative compounds has silicon tetrachloride, dimethyldichlorosilane(DMCS), diethyl dichlorosilane, diphenyl dichlorosilane, phenylmethyldichloroislane, diphenyl methyl chloro silane, trimethylchlorosilane, dimethoxy dichlorosilane, monomethyl dichlorosilane, chlorodimethyl silane.
Described second kind of silicon-containing compound has RO
nSiR '
4-n(1≤n≤3) structure, R and R ' are respectively C
1-C
10Alkyl, preferred C
1-C
6, more preferably following compounds: a kind of in dimethyldimethoxysil,ne, tetramethoxy-silicane, tetraethoxysilane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, phenyl methyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, dicyclohexyl dimethoxy silane, second, isobutyl dimethoxy silane, cyclopentyl-methyl dimethoxy silane, two cyclopentyl diethoxy silanes, the dicyclopentyl dimethoxyl silane.
Described titanium compound has RO
nTiCl
4-n(0≤n≤4) structure, R is C
1-C
8Alkyl, particular compound comprise titanium tetrachloride, four titanium butoxide, dichloro diethoxy titanium, trichlorine ethanolato-titanium, dichloro dibutoxy titanium.
The organic oxygen-containing thing in described the 3rd step is for containing ethers, the diether compound of " O-" key, preferred compound has: tetrahydrofuran (THF), isoamyl oxide, methyl isoamyl ether, 2,2-dicyclohexyl-1,3-third dme, 2,2-isobutyl--1,3-third dme, 2,2-phenylbenzene-1,3-third dme.
Described complex compound through grind forming is ground altogether by Magnesium Chloride Anhydrous and titanium halide and forms, and is included in to add grinding aid in the grinding system of magnesium chloride and titanium halide and grind; Wherein magnesium/titanium mol ratio is 1～20, and complex compound titaniferous amount is between 0.5%～10% weight, and the mol ratio of grinding aid and titanium halide is 0.1～10.
Described titanium halide has RO
nTiCl
4-n(0≤n≤4) structure, R is C
1-C
8Alkyl, preferred titanium tetrachloride, four titanium butoxide, dichloro diethoxy titanium, trichlorine ethanolato-titanium, dichloro dibutoxy titanium.
Described grinding aid is by having R
nXOR '
4-nCompound of (0≤n≤4) structure and/or organic silicone oil/or the containing hydrogen silicone oil composition, R is C
1～C
8Alkyl, aromatic base or cycloalkyl also can be halogens, R is C
1～C
8Alkyl, X are titanium, silicon.
Described grinding aid is selected from one or more in dimethyldimethoxysil,ne, tetramethoxy-silicane, tetraethoxysilane, dimethoxydiphenylsilane, cyclohexyl methyl dimethoxy silane, dicyclopentyl dimethoxyl silane, dimethoxy dichlorosilane, silicon tetrachloride, tetrabutyl titanate, the iso-butyl titanate.
Described organo-aluminium compound promotor is selected from one or more in triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium, the hydrogen diethyl aluminum.
Described silicoorganic compound are selected from phenylbenzene dihydroxyl silane, the diphenyl methyl silicol, dimethyl dihydroxyl silane, diethyl dihydroxyl silane, trimethyl silanol, dimethyl hydroxyl silicon oil, α, the alpha, omega-dihydroxy dimethyl polysiloxane, in the vinyl hydroxy silicone oil one or more, or be selected from dimethyldimethoxysil,ne, tetramethoxy-silicane, tetraethoxysilane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, phenyl methyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, dicyclohexyl dimethoxy silane, second, isobutyl dimethoxy silane, cyclopentyl-methyl dimethoxy silane, two cyclopentyl diethoxy silanes, in the dicyclopentyl dimethoxyl silane one or more.
A kind of preparation method of extra high-molecular polythene catalyst is characterized in that, this method comprises the preparation of (A) component solid main catalyst, (B) preparation of component organo-aluminium compound promotor;
Described (A) component is made of containing titanium component and containing silicon components of magnesium-containing compound load, and the preparation of being somebody's turn to do (A) component may further comprise the steps:
The first step, magnesium-containing compound and organic oxygen-containing compound, inert solvent are at 0～150 ℃, and preferred 40～120 ℃ form mixed solution (a) down; Wherein, halogenated magnesium compound is complex compounds such as the water, alcohol of magnesium dichloride, dibrominated magnesium, bifluoride magnesium and above-claimed cpd, and perhaps above-claimed cpd and titanium-containing compound are through grinding the complex compound that forms, preferred magnesium dichloride; The organic oxygen-containing thing is C
1～C
8Monohydroxy-alcohol or dibasic alcohol, particular methanol, ethanol, butanols, ethylene glycol, propylene glycol, 2-Ethylhexyl Alcohol, decyl alcohol; Also can be epoxy compounds, optimization ethylene oxide, propylene oxide, epoxy chloropropane, tetrahydrofuran (THF), dioxane, butylene oxide ring, epoxy hexane etc.; Can also be monobasic ester, dibasic ester or ternary ester, ethyl acetate, methyl benzoate, diethyl phthalate, diisobutyl phthalate, triethyl phosphate, tributyl phosphate; The organic oxygen-containing thing is in above-mentioned alcohol, epoxy compounds and the ester during two or three mixture, and result of use is better; Inert solvent is C
1～C
10Alkane, naphthenic hydrocarbon, aromatic hydrocarbons, alkane substitute, substituted ring alkane or substituted arene, preferred normal hexane, normal heptane, iso-pentane, hexanaphthene, decane, toluene, dimethylbenzene, 1 are one of in 2-ethylene dichloride, chlorocyclohexane, n-propylcarbinyl chloride, the chlorobenzene;
Each component feed molar ratio is in every mole of magnesium compound, and the organic oxygen-containing compound total mole number is 0.03～10 mole, preferred 0.1～6 mole;
The complex compound of the magnesium-containing compound through grind forming is ground altogether by Magnesium Chloride Anhydrous and titanium halide and forms, and is included in to add grinding aid in the grinding system of magnesium chloride and titanium halide and grind; Titanium halide has RO
nTiCl
4-n(0≤n≤4) structure, R is C
1-C
8Alkyl, preferred titanium tetrachloride, four titanium butoxide, dichloro diethoxy titanium, trichlorine ethanolato-titanium, dichloro dibutoxy titanium, more preferably titanium tetrachloride;
The magnesium of the complex compound of described magnesium-containing compound/titanium mol ratio is 1～20, preferred 5～8; The titaniferous amount between 0.5%～10%, preferred 1.0%～5.0%;
Described grinding aid is by having R
nXOR '
4-nCompound of (0≤n≤4) structure and/or organic silicone oil (or containing hydrogen silicone oil) are formed, and R is C
1～C
8Alkyl, aromatic base or cycloalkyl also can be halogens, R is C
1～C
8Alkyl, X are titanium, silicon;
Described grinding aid is selected from dimethyldimethoxysil,ne, tetramethoxy-silicane, tetraethoxysilane, dimethoxydiphenylsilane, cyclohexyl methyl dimethoxy silane, dicyclopentyl dimethoxyl silane, dimethoxy dichlorosilane, silicon tetrachloride, tetrabutyl titanate, iso-butyl titanate; Most preferably tetraethoxysilane, dicyclopentyl dimethoxyl silane and/or tetrabutyl titanate are grinding aid;
The mol ratio of grinding aid and titanium halide is 0.1～10, preferred 0.3～1; When grinding aid contains organic silicone oil or containing hydrogen silicone oil; The interpolation weight ratio of contained above-claimed cpd and titanium halide is 0.1～3, preferred 0.5～1; The temperature of grinding system is controlled between 0～120 ℃, preferred 10～60 ℃;
Second step slowly dripped the mixing solutions of two kinds of silicon-containing compounds in mixed solution (a), certain temperature react suspension (b);
First kind of silicon-containing compound has R
nSiCl
4-n(0≤n≤3) structure, R is alkyl, aryl, hydrogen or oxy radical, representative compounds has silicon tetrachloride, dimethyldichlorosilane(DMCS), diethyl dichlorosilane, diphenyl dichlorosilane, phenylmethyldichloroislane, diphenyl methyl chloro silane, trimethylchlorosilane, dimethoxy dichlorosilane, monomethyl dichlorosilane, chlorodimethyl silane, and preferred n value is 2 silicon-containing compound;
Second kind of silicon-containing compound has RO
nSiR '
4-n(1≤n≤3) structure, R and R ' are respectively C
1-C
10Alkyl, preferred C
1-C
6, more preferably following compounds: a kind of in dimethyldimethoxysil,ne, tetramethoxy-silicane, tetraethoxysilane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, phenyl methyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, dicyclohexyl dimethoxy silane, second, isobutyl dimethoxy silane, cyclopentyl-methyl dimethoxy silane, two cyclopentyl diethoxy silanes, the dicyclopentyl dimethoxyl silane;
The dropping temperature of silicon-containing compound solution is-20～60 ℃, preferred-5～40 ℃; The dropping time is 0.2～3 hour, preferred 0.5～1 hour; The insulation reaction temperature is 50～150 ℃, preferred 70～100 ℃; The insulation reaction time is 0.5～6 hour, preferred 1～3 hour; The insulation reaction rear suspension liquid be cooled to-20～80 ℃ standby;
Every mole of magnesium compound meter, total add-on of silicon-containing compound is 0.3～20 mole, preferred 1～10 mole; The mol ratio of first kind of silicon-containing compound and second kind of silicon-containing compound is 0.1～10, preferred 0.3～3;
The 3rd step, titanium compound and/or organic oxygen-containing compound treating suspension (b), after filtering, wash by this area routine techniques ingredient of solid catalyst (A);
Titanium compound has RO
nTiCl
4-n(0≤n≤4) structure, R is C
1-C
8Alkyl, particular compound comprise titanium tetrachloride, four titanium butoxide, dichloro diethoxy titanium, trichlorine ethanolato-titanium, dichloro dibutoxy titanium, preferred titanium tetrachloride and four titanium butoxide;
The organic oxygen-containing thing is for containing ethers, the diether compound of " O-" key; Preferred compound has: tetrahydrofuran (THF), isoamyl oxide, methyl isoamyl ether, 2,2-dicyclohexyl-1,3-third dme, 2,2-isobutyl--1,3-third dme, 2,2-phenylbenzene-1,3-third dme;
The mol ratio of titanium compound and organic oxygen-containing compound is 0.1～10, preferred 0.5～5; Titanium compound and/or organic oxygen-containing thing can drip also and can disposablely join in the suspension (b), and effect is better during dropping; The dropping time should be controlled in 1.0 hours, and treatment temp is-20～100 ℃, preferred 40～80 ℃; 1～5 hour treatment time, preferred 2～3 hours; Handle the back solid-liquid separation, after normal hexane washing solid ingredient four times, vacuum-drying below 40 ℃ gets pulverulent solids component (A);
After the titanium compound in the mixing solutions of two kinds of silicon-containing compounds in above-mentioned second step and the 3rd step and/or organic oxygen-containing compound mixed by above-mentioned material proportion, a step directly was added drop-wise in the mixed solution (a), can make catalyst component (A); Treatment temp is-20～100 ℃, preferred 40～80 ℃; 1～5 hour treatment time, preferred 2～3 hours; Handle the back solid-liquid separation, after normal hexane washing solid ingredient four times, vacuum-drying below 40 ℃ gets pulverulent solids component, i.e. catalyzer (A) component;
Described (B) component is an organo-aluminium compound, is selected among a kind of in triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium, the hydrogen diethyl aluminum one or more, preferred triethyl aluminum.
This method also comprises the preparation of (C) component property adjusting component, described (C) component is silicoorganic compound, be selected from phenylbenzene dihydroxyl silane, the diphenyl methyl silicol, dimethyl dihydroxyl silane, diethyl dihydroxyl silane, trimethyl silanol, dimethyl hydroxyl silicon oil, α, the alpha, omega-dihydroxy dimethyl polysiloxane, in the vinyl hydroxy silicone oil one or more, or be selected from dimethyldimethoxysil,ne, tetramethoxy-silicane, tetraethoxysilane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, phenyl methyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, dicyclohexyl dimethoxy silane, second, isobutyl dimethoxy silane, cyclopentyl-methyl dimethoxy silane, two cyclopentyl diethoxy silanes, in the dicyclopentyl dimethoxyl silane one or more.
A kind of application of extra high-molecular polythene catalyst is characterized in that, when this catalyzer was applied to ultrahigh molecular weight polyethylene and is equipped with, (B), (A) two components join respectively by listed order in the polymeric kettle that contains solvent, the controlled polymerization condition was reacted; This catalyzer is regulated the molecular weight of ultrahigh molecular weight polyethylene(UHMWPE) with hydrogen, and the viscosity-average molecular weight of its ultrahigh molecular weight polyethylene(UHMWPE) is between 100～1,000 ten thousand; The working concentration of described (B) component in polymerization solvent is 5 * 10
-4～2.5 * 10
-2Mol, preferred 1 * 10
-3～1 * 10
-2Mol; The Al/Ti mol ratio is controlled between 20～1000, preferred 30～500.
When this catalyzer is applied to ultrahigh molecular weight polyethylene and is equipped with, comprise that also (C) component property regulates component, (B) (C) (A) three components join respectively by listed order in the polymeric kettle that contains solvent, the controlled polymerization condition is reacted; (A) component before polyreaction earlier with (C) component effect 1～30 minute, and then contact 1～20 minute with (B) component, join better effects if in the polymerization reaction kettle then; This catalyzer is regulated the molecular weight of ultrahigh molecular weight polyethylene(UHMWPE) with hydrogen, and the viscosity-average molecular weight of its ultrahigh molecular weight polyethylene(UHMWPE) is between 100～1,000 ten thousand; The working concentration of described (B) component in polymerization solvent is 5 * 10
-4～2.5 * 10
-2Mol, preferred 1 * 10
-3～1 * 10
-2Mol; The Al/Ti mol ratio is controlled between 20～1000, preferred 30～500; The working concentration of described (C) component in polymerization solvent is 5 * 10
-5～2.5 * 10
-3Mol, preferred 1 * 10
-4～1 * 10
-3Mol.
Catalyst system provided by the invention has the following advantages:
1. being equipped with technology with existing ultrahigh molecular weight polyethylene compares, the present invention is by strengthening the modification of catalytic active center, further improve the energy for growth of polymkeric substance on the catalytic active site, make catalytic performance more stable, improved the hydrogen response of catalyzer, be easy to realize that the ultrahigh molecular weight polyethylene(UHMWPE) molecular weight is adjustable.The present invention can obviously improve the tap density of polyvinyl resin with super-high molecular weight, obviously reduces fine powder and meal amount.Therefore catalyzer of the present invention can prepare the polyvinyl resin with super-high molecular weight (〉=0.38 grams per milliliter) of high bulk density, has good hydrogen regulation performance, is easy to realize that molecular weight is adjustable between 100～1,000 ten thousand.
2. ingredient of solid catalyst of the present invention is only used more a spot of titanium halide or titanium compound, has simplified operating procedure and operational condition, and quantity of three wastes is few, is suitable for industrial production and application.
3. active high when catalyzer of the present invention carries out polymerization, reacting balance, easy control of temperature, not sticking still phenomenon.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
1, the preparation of (A) component in the catalyst system
In through the abundant metathetical reactor of high purity nitrogen, add Magnesium Chloride Anhydrous 0.1mol successively, normal heptane 200mL, ethanol 0.3mol, tributyl phosphate 0.1mol, stirring is warming up to 80 ℃, after insulation for some time, is cooled to 20 ℃, in 1.0h, drip 20 milliliters of diphenyl dichlorosilane and tetraethoxysilane mixing solutionss (mol ratio 2: 0.5), slowly be warming up to 80 ℃ of reaction 2.0h then, in solution dropping and temperature-rise period, have solid precipitation progressively to separate out, form the mud yellow suspension.After being cooled to 50 ℃, in suspension, drip the mixing solutions of 0.2 mole of titanium tetrachloride and 0.2 mole of tetrahydrofuran (THF) in 30 minutes, after dropwising, slowly be warming up to 80 ℃, insulation was handled 2.0 hours, obtain solid sediment after cooling, the filtration, divide the washing solids four times with the 400mL normal hexane, 40 ℃ of vacuum-dryings obtain solid ingredient (A).Solid ingredient titaniferous amount (weight %) 2.55.
2, polyreaction
2L stainless steel polymeric kettle is rinsed well with high purity nitrogen, add 1000 milliliters of No. 120 industrial napthas, 0.002 mole of triethyl aluminum, 10.5 milligrams of 0.00025 mole in dimethyl dihydroxyl silane and above-mentioned ingredients of solid catalyst (A), add hydrogen 500mL (mark attitude), feed ethene, be warming up to 70 ℃ to constant pressure 0.6MPa, reacted 4 hours, and got polymkeric substance 324 grams.Experimental result is seen attached list.
Embodiment 2
1, the preparation of component (A) in the catalyst system
In the ball mill that fully cleans through high purity nitrogen and protect, add 43 gram Magnesium Chloride Anhydrouss and 6.8 gram titanium tetrachlorides; the pre-grinding added 4 milliliters of grinding aid tetraethoxysilanes in grinding system after 6 hours; 4 milliliters of containing hydrogen silicone oils; continue to grind discharging after 24 hours; get yellow powder powder solid; with Magnesium Chloride Anhydrous in a small amount of above-mentioned solid (containing magnesium 0.1mol) alternate embodiment 1; ethanol and tributyl phosphate change 0.03mol and 0.01mol respectively into; other presses embodiment 1 conditional operation; get solid ingredient (A), this solid ingredient titaniferous amount (weight %) 2.91.
2, polyreaction
2L stainless steel polymeric kettle is rinsed well with high purity nitrogen, added 1000 milliliters of No. 120 industrial napthas, 0.001 mole of triethyl aluminum.Get 16.7 milligrams of above-mentioned ingredients of solid catalyst, add 2.5 milliliters of effects of 0.1M dimethyl dihydroxyl silane hexane solution 10 minutes, and then adding 1M triethyl aluminum hexane solution remakes with 10 minutes for 2 milliliters.The above-mentioned suspension that contains ingredient of solid catalyst is transferred in the reactor, feeds ethene, be warming up to 70 ℃, reacted 4 hours, get polymkeric substance 309 grams to constant pressure 0.6MPa.Polymer property is seen attached list.
The comparative example 1
Do not add grinding aid tetraethoxysilane and containing hydrogen silicone oil among the embodiment 2, make solid catalyst, be used for polymerization, the results are shown in subordinate list by embodiment 2 conditions.
The comparative example 2
Prepare catalyzer (A) component by embodiment 2 conditions, prepare ultrahigh molecular weight polyethylene(UHMWPE) by embodiment 1 polymerizing condition then, the results are shown in subordinate list.
The comparative example 3
Do not add the grinding aid tetraethoxysilane among the embodiment 2, but add containing hydrogen silicone oil, make solid catalyst, be used for polymerization, the results are shown in subordinate list by embodiment 2 conditions.
The comparative example 4
Prepare catalyzer (A) component by embodiment 1 condition, prepare ultrahigh molecular weight polyethylene(UHMWPE) by embodiment 2 polymerizing conditions then, the results are shown in subordinate list.
Embodiment 3
Silicon tetrachloride with same amount among the embodiment 1 replaces diphenyl dichlorosilane to prepare ingredient of solid catalyst (A), carries out polyreaction by embodiment 1 condition, the results are shown in subordinate list.
Embodiment 4
Prepare ingredient of solid catalyst (A) with 0.4 mole of mixing solutions that substitutes 0.2 mole of titanium tetrachloride and 0.2 mole of tetrahydrofuran (THF) of titanium tetrachloride among the embodiment 1, carry out polyreaction, the results are shown in subordinate list by embodiment 1 condition.
Embodiment 5
After pressing embodiment 1 preparation ingredient of solid catalyst (A), do not add hydrogen when polyreaction, other condition the results are shown in subordinate list with embodiment 1.
Embodiment 6
Dimethoxy dichlorosilane with same amount among the embodiment 1 replaces diphenyl dichlorosilane to prepare ingredient of solid catalyst (A), carries out polyreaction by embodiment 1 condition, the results are shown in subordinate list.
Embodiment 7
Substitute tetraethoxysilane with dimethoxydiphenylsilane among the embodiment 1 and prepare ingredient of solid catalyst (A), carry out polyreaction, the results are shown in subordinate list by embodiment 1 condition.
Embodiment 8
Substitute tetraethoxysilane with dicyclopentyl dimethoxyl silane among the embodiment 1 and prepare ingredient of solid catalyst (A), carry out polyreaction, the results are shown in subordinate list by embodiment 1 condition.
Embodiment 9
In embodiment 2, substitute tetraethoxysilane with the 4mL tetrabutyl titanate and prepare ingredient of solid catalyst (A), carry out polyreaction by embodiment 2 conditions, the results are shown in subordinate list.
Embodiment 10
Prepare ingredient of solid catalyst (A) with embodiment 1 method, carry out polyreaction by embodiment 1 condition, substitute dimethyl dihydroxyl silane with 0.00025 mole of phenylbenzene dihydroxyl silane in the polyreaction, other condition is constant, and experimental result is seen attached list.
Embodiment 11
Prepare ingredient of solid catalyst (A) with embodiment 2 methods, carry out polyreaction by embodiment 2 conditions, with 2.5 milliliters of alternative dimethyl dihydroxyl solution of silane of 0.1M phenylbenzene dihydroxyl silane hexane solution, other condition is constant in the polyreaction, and experimental result is seen attached list.
Embodiment 12
Prepare ingredient of solid catalyst (A) with embodiment 1 method, carry out polyreaction by embodiment 1 condition, substitute dimethyl dihydroxyl silane with 0.00025 mole of dimethoxydiphenylsilane in the polyreaction, other condition is constant, and experimental result is seen attached list.
Embodiment 13
In through the abundant metathetical reactor of high purity nitrogen, add Magnesium Chloride Anhydrous 0.1mol successively, normal heptane 200mL, ethanol 0.3mol, tributyl phosphate 0.1mol, stirring is warming up to 80 ℃, after insulation for some time, be cooled to 20 ℃, in 1.0h, drip diphenyl dichlorosilane, tetraethoxysilane, titanium tetrachloride and tetrahydrofuran (THF) mixing solutions (mol ratio 2: 0.5: 0.2: 0.2) 40 milliliters, slowly be warming up to 80 ℃ of insulation reaction then 3.0 hours, and in solution dropping and temperature-rise period, had solid precipitation progressively to separate out, form the mud yellow suspension.Cooling obtains solid sediment after filtering, and divides the washing solids four times with the 400mL normal hexane, and 40 ℃ of vacuum-dryings obtain solid ingredient (A).Solid ingredient titaniferous amount (weight %) 2.86.
Get the gained solid ingredient, prepare ultrahigh molecular weight polyethylene(UHMWPE) by embodiment 1 polymerizing condition, experimental result is seen attached list.
Embodiment 14
Press embodiment 1 preparation ingredient of solid catalyst (A), when carrying out polyreaction by embodiment 1, add hydrogen 2500mL (mark attitude), other condition is constant, the results are shown in subordinate list.
Embodiment 15
Press embodiment 1 preparation ingredient of solid catalyst (A), when carrying out polyreaction by embodiment 1, add hydrogen 1500mL (mark attitude), other condition is constant, the results are shown in subordinate list.
Embodiment 16
Press embodiment 1 preparation ingredient of solid catalyst (A), when carrying out polyreaction by embodiment 1, do not add dimethyl dihydroxyl silane, other condition is constant, the results are shown in subordinate list.
Embodiment 17
Press embodiment 2 preparation ingredients of solid catalyst (A), when carrying out polyreaction by embodiment 2, do not add dimethyl dihydroxyl silane hexane solution, other condition is constant, the results are shown in subordinate list.
Subordinate list:
| Embodiment number | Catalyzer titaniferous amount (wt%) | Active (kgPE/gC at) | Viscosity-average molecular weight (1,000,000) | Polymer stacks density (g/mL) | The polymkeric substance particle diameter distributes | |
| 〉=20 orders (%) | ≤ 200 orders (%) | |||||
| 1 | 2.55 | 30.9 | 425 | 0.39 | 5 | 0 |
| 2 | 2.91 | 18.5 | 516 | 0.38 | 7 | 1 |
| Contrast 1 | 3.25 | 5.6 | 340 | 0.25 | 45 | 0 |
| Contrast 2 | 2.91 | 15.7 | 285 | 0.34 | 15 | 3 |
| Contrast 3 | 3.01 | 11.6 | 450 | 0.35 | 12 | 4 |
| Contrast 4 | 2.55 | 26.9 | 950 | 0.37 | 5 | 1 |
| 3 | 2.63 | 25.3 | 440 | 0.38 | 8 | 3 |
| 4 | 2.46 | 17.7 | 420 | 0.39 | 11 | 2 |
| 5 | 2.55 | 35.6 | 850 | 0.42 | 7 | 0 |
| 6 | 2.13 | 28.6 | 405 | 0.41 | 5 | 4 |
| 7 | 2.06 | 27.7 | 452 | 0.36 | 8 | 2 |
| 8 | 2.28 | 30.6 | 460 | 0.38 | 4 | 1 |
| 9 | 3.4 | 15.2 | 650 | 0.40 | 8 | 4 |
| 10 | 2.55 | 34.5 | 520 | 0.37 | 6 | 5 |
| 11 | 2.91 | 22.4 | 730 | 0.39 | 5 | 5 |
| 12 | 2.55 | 33.6 | 527 | 0.37 | 7 | 1 |
| 13 | 2.86 | 30.5 | 450 | 0.38 | 4 | 2 |
| 14 | 2.55 | 27.6 | 153 | 0.40 | 3 | 1 |
| 15 | 2.55 | 28.3 | 307 | 0.38 | 2 | 2 |
| 16 | 2.55 | 26.8 | 436 | 0.39 | 3 | 1 |
| 17 | 2.91 | 16.7 | 508 | 0.41 | 2 | 2 |
Claims (20)
1. extra high-molecular polythene catalyst, it is characterized in that, this catalyzer comprises (A), (B) component, wherein, (A) component is a solid main catalyst, (B) component is a promotor, and described (A) component is made of containing titanium component and containing silicon components of magnesium-containing compound load, and described (B) component is an organo-aluminium compound.
2. a kind of extra high-molecular polythene catalyst according to claim 1 is characterized in that, this catalyzer also comprises (C) component, should (C) component be the property regulation component, and described (C) component is silicoorganic compound.
3. a kind of extra high-molecular polythene catalyst according to claim 1, it is characterized in that, the first step is passed through in containing titanium component and containing silicon components of described magnesium-containing compound load: magnesium-containing compound and organic oxygen-containing compound, inert solvent is at 0～150 ℃, preferred 40～120 ℃ form mixed solution (a) down, second step: in mixed solution (a), slowly drip first kind, the mixing solutions of second kind of two kinds of silicon-containing compound, certain temperature react suspension (b), the 3rd step: titanium compound and/or organic oxygen-containing compound treating suspension (b), filter by this area routine techniques, obtain after the washing.
4. a kind of extra high-molecular polythene catalyst according to claim 3, it is characterized in that, described magnesium-containing compound is water, the alcohol complex of magnesium dichloride, dibrominated magnesium, bifluoride magnesium and above-claimed cpd, and perhaps above-claimed cpd and titanium-containing compound are through grinding the complex compound that forms.
5. a kind of extra high-molecular polythene catalyst according to claim 3 is characterized in that, the organic oxygen-containing compound in the described the first step is C
1～C
8Monohydroxy-alcohol or dibasic alcohol, comprise being selected from methyl alcohol, ethanol, butanols, ethylene glycol, propylene glycol, 2-Ethylhexyl Alcohol, decyl alcohol; Or epoxy compounds, comprise and be selected from oxyethane, propylene oxide, epoxy chloropropane, tetrahydrofuran (THF), dioxane, butylene oxide ring, epoxy hexane, or monobasic ester, dibasic ester or ternary ester, comprise being selected from ethyl acetate, methyl benzoate, diethyl phthalate, diisobutyl phthalate, triethyl phosphate, tributyl phosphate; Described organic oxygen-containing thing or be two or three mixture in above-mentioned alcohol, epoxy compounds and the ester.
6. a kind of extra high-molecular polythene catalyst according to claim 3 is characterized in that, described inert solvent is C
1～C
10Alkane, naphthenic hydrocarbon, aromatic hydrocarbons, alkane substitute, substituted ring alkane or substituted arene, comprise being selected from normal hexane, normal heptane, iso-pentane, hexanaphthene, decane, toluene, dimethylbenzene, 1 a kind of in 2-ethylene dichloride, chlorocyclohexane, n-propylcarbinyl chloride, the chlorobenzene.
7. a kind of extra high-molecular polythene catalyst according to claim 3 is characterized in that, described first kind of silicon-containing compound has R
nSiCl
4-n(0≤n≤3) structure, R is alkyl, aryl, hydrogen or oxy radical, and representative compounds has silicon tetrachloride, dimethyldichlorosilane(DMCS), diethyl dichlorosilane, diphenyl dichlorosilane, phenylmethyldichloroislane, diphenyl methyl chloro silane, trimethylchlorosilane, dimethoxy dichlorosilane, monomethyl dichlorosilane, chlorodimethyl silane.
8. a kind of extra high-molecular polythene catalyst according to claim 3 is characterized in that, described second kind of silicon-containing compound has RO
nSiR '
4-n(1≤n≤3) structure, R and R ' are respectively C
1-C
10Alkyl, preferred C
1-C
6, more preferably following compounds: a kind of in dimethyldimethoxysil,ne, tetramethoxy-silicane, tetraethoxysilane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, phenyl methyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, dicyclohexyl dimethoxy silane, second, isobutyl dimethoxy silane, cyclopentyl-methyl dimethoxy silane, two cyclopentyl diethoxy silanes, the dicyclopentyl dimethoxyl silane.
9. a kind of extra high-molecular polythene catalyst according to claim 3 is characterized in that described titanium compound has RO
nTiCl
4-n(0≤n≤4) structure, R is C
1-C
8Alkyl, particular compound comprise titanium tetrachloride, four titanium butoxide, dichloro diethoxy titanium, trichlorine ethanolato-titanium, dichloro dibutoxy titanium.
10. a kind of extra high-molecular polythene catalyst according to claim 3, it is characterized in that, the organic oxygen-containing thing in described the 3rd step is for containing ethers, the diether compound of " O-" key, preferred compound has: tetrahydrofuran (THF), isoamyl oxide, methyl isoamyl ether, 2,2-dicyclohexyl-1,3-third dme, 2,2-isobutyl--1,3-third dme, 2,2-phenylbenzene-1,3-third dme.
11. a kind of extra high-molecular polythene catalyst according to claim 4, it is characterized in that, described complex compound through grind forming is ground altogether by Magnesium Chloride Anhydrous and titanium halide and forms, and is included in to add grinding aid in the grinding system of magnesium chloride and titanium halide and grind; Wherein magnesium/titanium mol ratio is 1～20, and complex compound titaniferous amount is between 0.5%～10% weight, and the mol ratio of grinding aid and titanium halide is 0.1～10.
12. a kind of extra high-molecular polythene catalyst according to claim 11 is characterized in that described titanium halide has RO
nTiCl
4-n(0≤n≤4) structure, R is C
1-C
8Alkyl, preferred titanium tetrachloride, four titanium butoxide, dichloro diethoxy titanium, trichlorine ethanolato-titanium, dichloro dibutoxy titanium.
13. a kind of extra high-molecular polythene catalyst according to claim 11 is characterized in that described grinding aid is by having R
nXOR '
4-nCompound of (0≤n≤4) structure and/or organic silicone oil/or the containing hydrogen silicone oil composition, R is C
1～C
8Alkyl, aromatic base or cycloalkyl also can be halogens, R ' is C
1～C
8Alkyl, X are titanium, silicon.
14. a kind of extra high-molecular polythene catalyst according to claim 11, it is characterized in that described grinding aid is selected from one or more in dimethyldimethoxysil,ne, tetramethoxy-silicane, tetraethoxysilane, dimethoxydiphenylsilane, cyclohexyl methyl dimethoxy silane, dicyclopentyl dimethoxyl silane, dimethoxy dichlorosilane, silicon tetrachloride, tetrabutyl titanate, the iso-butyl titanate.
15. a kind of extra high-molecular polythene catalyst according to claim 1 is characterized in that, described organo-aluminium compound promotor is selected from one or more in triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium, the hydrogen diethyl aluminum.
16. a kind of extra high-molecular polythene catalyst according to claim 2, it is characterized in that, described silicoorganic compound are selected from phenylbenzene dihydroxyl silane, the diphenyl methyl silicol, dimethyl dihydroxyl silane, diethyl dihydroxyl silane, trimethyl silanol, dimethyl hydroxyl silicon oil, α, the alpha, omega-dihydroxy dimethyl polysiloxane, in the vinyl hydroxy silicone oil one or more, or be selected from dimethyldimethoxysil,ne, tetramethoxy-silicane, tetraethoxysilane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, phenyl methyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, dicyclohexyl dimethoxy silane, second, isobutyl dimethoxy silane, cyclopentyl-methyl dimethoxy silane, two cyclopentyl diethoxy silanes, in the dicyclopentyl dimethoxyl silane one or more.
17. the preparation method of an extra high-molecular polythene catalyst is characterized in that, this method comprises the preparation of (A) component solid main catalyst, (B) preparation of component organo-aluminium compound promotor;
Described (A) component is made of containing titanium component and containing silicon components of magnesium-containing compound load, and the preparation of being somebody's turn to do (A) component may further comprise the steps:
The first step, magnesium-containing compound and organic oxygen-containing compound, inert solvent are at 0～150 ℃, and preferred 40～120 ℃ form mixed solution (a) down; Wherein, halogenated magnesium compound is complex compounds such as the water, alcohol of magnesium dichloride, dibrominated magnesium, bifluoride magnesium and above-claimed cpd, and perhaps above-claimed cpd and titanium-containing compound are through grinding the complex compound that forms, preferred magnesium dichloride; The organic oxygen-containing thing is C
1～C
8Monohydroxy-alcohol or dibasic alcohol, particular methanol, ethanol, butanols, ethylene glycol, propylene glycol, 2-Ethylhexyl Alcohol, decyl alcohol; Also can be epoxy compounds, optimization ethylene oxide, propylene oxide, epoxy chloropropane, tetrahydrofuran (THF), dioxane, butylene oxide ring, epoxy hexane etc.; Can also be monobasic ester, dibasic ester or ternary ester, ethyl acetate, methyl benzoate, diethyl phthalate, diisobutyl phthalate, triethyl phosphate, tributyl phosphate; The organic oxygen-containing thing is in above-mentioned alcohol, epoxy compounds and the ester during two or three mixture, and result of use is better; Inert solvent is C
1～C
10Alkane, naphthenic hydrocarbon, aromatic hydrocarbons, alkane substitute, substituted ring alkane or substituted arene, preferred normal hexane, normal heptane, iso-pentane, hexanaphthene, decane, toluene, dimethylbenzene, 1 are one of in 2-ethylene dichloride, chlorocyclohexane, n-propylcarbinyl chloride, the chlorobenzene;
Each component feed molar ratio is in every mole of magnesium compound, and the organic oxygen-containing compound total mole number is 0.03～10 mole, preferred 0.1～6 mole;
The complex compound of the magnesium-containing compound through grind forming is ground altogether by Magnesium Chloride Anhydrous and titanium halide and forms, and is included in to add grinding aid in the grinding system of magnesium chloride and titanium halide and grind; Titanium halide has RO
nTiCl
4-n(0≤n≤4) structure, R is C
1-C
8Alkyl, preferred titanium tetrachloride, four titanium butoxide, dichloro diethoxy titanium, trichlorine ethanolato-titanium, dichloro dibutoxy titanium, more preferably titanium tetrachloride;
The magnesium of the complex compound of described magnesium-containing compound/titanium mol ratio is 1～20, preferred 5～8; The titaniferous amount between 0.5%～10%, preferred 1.0%～5.0%;
Described grinding aid is by having R
nXOR '
4-nCompound of (0≤n≤4) structure and/or organic silicone oil (or containing hydrogen silicone oil) are formed, and R is C
1～C
8Alkyl, aromatic base or cycloalkyl also can be halogens, R ' is C
1～C
8Alkyl, X are titanium, silicon;
Described grinding aid is selected from dimethyldimethoxysil,ne, tetramethoxy-silicane, tetraethoxysilane, dimethoxydiphenylsilane, cyclohexyl methyl dimethoxy silane, dicyclopentyl dimethoxyl silane, dimethoxy dichlorosilane, silicon tetrachloride, tetrabutyl titanate, iso-butyl titanate; Most preferably tetraethoxysilane, dicyclopentyl dimethoxyl silane and/or tetrabutyl titanate are grinding aid;
The mol ratio of grinding aid and titanium halide is 0.1～10, preferred 0.3～1; When grinding aid contains organic silicone oil or containing hydrogen silicone oil; The interpolation weight ratio of contained above-claimed cpd and titanium halide is 0.1～3, preferred 0.5～1; The temperature of grinding system is controlled between 0～120 ℃, preferred 10～60 ℃;
Second step slowly dripped the mixing solutions of two kinds of silicon-containing compounds in mixed solution (a), certain temperature react suspension (b);
First kind of silicon-containing compound has R
nSiCl
4-n(0≤n≤3) structure, R is alkyl, aryl, hydrogen or oxy radical, representative compounds has silicon tetrachloride, dimethyldichlorosilane(DMCS), diethyl dichlorosilane, diphenyl dichlorosilane, phenylmethyldichloroislane, diphenyl methyl chloro silane, trimethylchlorosilane, dimethoxy dichlorosilane, monomethyl dichlorosilane, chlorodimethyl silane, and preferred n value is 2 silicon-containing compound;
Second kind of silicon-containing compound has RO
nSiR '
4-n(1≤n≤3) structure, R and R ' are respectively C
1-C
10Alkyl, preferred C
1-C
6, more preferably following compounds: a kind of in dimethyldimethoxysil,ne, tetramethoxy-silicane, tetraethoxysilane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, phenyl methyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, dicyclohexyl dimethoxy silane, second, isobutyl dimethoxy silane, cyclopentyl-methyl dimethoxy silane, two cyclopentyl diethoxy silanes, the dicyclopentyl dimethoxyl silane;
The dropping temperature of silicon-containing compound solution is-20～60 ℃, preferred-5～40 ℃; The dropping time is 0.2～3 hour, preferred 0.5～1 hour; The insulation reaction temperature is 50～150 ℃, preferred 70～100 ℃; The insulation reaction time is 0.5～6 hour, preferred 1～3 hour; The insulation reaction rear suspension liquid be cooled to-20～80 ℃ standby;
Every mole of magnesium compound meter, total add-on of silicon-containing compound is 0.3～20 mole, preferred 1～10 mole; The mol ratio of first kind of silicon-containing compound and second kind of silicon-containing compound is 0.1～10, preferred 0.3～3;
The 3rd step, titanium compound and/or organic oxygen-containing compound treating suspension (b), after filtering, wash by this area routine techniques ingredient of solid catalyst (A);
Titanium compound has RO
nTiCl
4-n(0≤n≤4) structure, R is C
1-C
8Alkyl, particular compound comprise titanium tetrachloride, four titanium butoxide, dichloro diethoxy titanium, trichlorine ethanolato-titanium, dichloro dibutoxy titanium, preferred titanium tetrachloride and four titanium butoxide;
The organic oxygen-containing thing is for containing ethers, the diether compound of " O-" key; Preferred compound has: tetrahydrofuran (THF), isoamyl oxide, methyl isoamyl ether, 2,2-dicyclohexyl-1,3-third dme, 2,2-isobutyl--1,3-third dme, 2,2-phenylbenzene-1,3-third dme;
The mol ratio of titanium compound and organic oxygen-containing compound is 0.1～10, preferred 0.5～5; Titanium compound and/or organic oxygen-containing thing can drip also and can disposablely join in the suspension (b), and effect is better during dropping; The dropping time should be controlled in 1.0 hours, and treatment temp is-20～100 ℃, preferred 40～80 ℃; 1～5 hour treatment time, preferred 2～3 hours; Handle the back solid-liquid separation, after normal hexane washing solid ingredient four times, vacuum-drying below 40 ℃ gets pulverulent solids component (A);
After the titanium compound in the mixing solutions of two kinds of silicon-containing compounds in above-mentioned second step and the 3rd step and/or organic oxygen-containing compound mixed by above-mentioned material proportion, a step directly was added drop-wise in the mixed solution (a), can make catalyst component (A); Treatment temp is-20～100 ℃, preferred 40～80 ℃; 1～5 hour treatment time, preferred 2～3 hours; Handle the back solid-liquid separation, after normal hexane washing solid ingredient four times, vacuum-drying below 40 ℃ gets pulverulent solids component, i.e. catalyzer (A) component;
Described (B) component is an organo-aluminium compound, is selected among a kind of in triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium, the hydrogen diethyl aluminum one or more, preferred triethyl aluminum.
18. the preparation method of a kind of extra high-molecular polythene catalyst according to claim 17, it is characterized in that, this method also comprises the preparation of (C) component property adjusting component, described (C) component is silicoorganic compound, be selected from phenylbenzene dihydroxyl silane, the diphenyl methyl silicol, dimethyl dihydroxyl silane, diethyl dihydroxyl silane, trimethyl silanol, dimethyl hydroxyl silicon oil, α, the alpha, omega-dihydroxy dimethyl polysiloxane, in the vinyl hydroxy silicone oil one or more, or be selected from dimethyldimethoxysil,ne, tetramethoxy-silicane, tetraethoxysilane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, phenyl methyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, dicyclohexyl dimethoxy silane, second, isobutyl dimethoxy silane, cyclopentyl-methyl dimethoxy silane, two cyclopentyl diethoxy silanes, in the dicyclopentyl dimethoxyl silane one or more.
19. the application of an extra high-molecular polythene catalyst, it is characterized in that, when this catalyzer was applied to ultrahigh molecular weight polyethylene and is equipped with, (B), (A) two components join respectively by listed order in the polymeric kettle that contains solvent, the controlled polymerization condition was reacted; This catalyzer is regulated the molecular weight of ultrahigh molecular weight polyethylene(UHMWPE) with hydrogen, and the viscosity-average molecular weight of its ultrahigh molecular weight polyethylene(UHMWPE) is between 100～1,000 ten thousand; The working concentration of described (B) component in polymerization solvent is 5 * 10
-4～2.5 * 10
-2Mol, preferred 1 * 10
-3～1 * 10
-2Mol; The Al/Ti mol ratio is controlled between 20～1000, preferred 30～500.
20. the application of a kind of extra high-molecular polythene catalyst according to claim 19, it is characterized in that, when this catalyzer is applied to ultrahigh molecular weight polyethylene and is equipped with, also comprise (C) component property adjusting component, (B) (C) (A) three components join respectively by listed order in the polymeric kettle that contains solvent, and the controlled polymerization condition is reacted; (A) component before polyreaction earlier with (C) component effect 1～30 minute, and then contact 1～20 minute with (B) component, join better effects if in the polymerization reaction kettle then; This catalyzer is regulated the molecular weight of ultrahigh molecular weight polyethylene(UHMWPE) with hydrogen, and the viscosity-average molecular weight of its ultrahigh molecular weight polyethylene(UHMWPE) is between 100～1,000 ten thousand; The working concentration of described (B) component in polymerization solvent is 5 * 10
-4～2.5 * 10
-2Mol, preferred 1 * 10
-3～1 * 10
-2Mol; The Al/Ti mol ratio is controlled between 20～1000, preferred 30～500; The working concentration of described (C) component in polymerization solvent is 5 * 10
-5～2.5 * 10
-3Mol, preferred 1 * 10
-4～1 * 10
-3Mol.
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