CN101074275B - Extra high-molecular polythene catalyst and its production - Google Patents
Extra high-molecular polythene catalyst and its production Download PDFInfo
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- CN101074275B CN101074275B CN2007100424687A CN200710042468A CN101074275B CN 101074275 B CN101074275 B CN 101074275B CN 2007100424687 A CN2007100424687 A CN 2007100424687A CN 200710042468 A CN200710042468 A CN 200710042468A CN 101074275 B CN101074275 B CN 101074275B
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Abstract
Ultrahigh molecular weight polyethylene catalyst and its production are disclosed. The catalyst consists of main components of catalyst and catalyst accessory. The process is carried out by reacting halide magnesium compound with alcohol compound and organic titanate compound to obtain magnesium compound solution, reacting with alkyl chlorine aluminum compound to obtain intermediate product, reacting with titanium compound and electron-donating to obtain final product. It has higher activity and better stacking density.
Description
Technical field
The present invention relates to a kind of catalyzer of ultrahigh molecular weight polyethylene(UHMWPE), and this Preparation of catalysts method.
Background technology
According to ASTM4020 definition, ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) is to have 2.30 or the straight linear polyethylene of higher relative viscosity, and this relative viscosity is to measure in the 0.05% perhydronaphthalene solution of 135 ℃ of following 100ml.For other polyethylene, it has high-wearing feature, and fabulous toughness and thermostability are widely used in textile industry, mechanical engineering, chemical industry and mining industry.
For ultrahigh molecular weight polyethylene(UHMWPE), except the big I of molecular weight influences its mechanical property and the processing characteristics, the size of ultrahigh molecular weight polyethylene(UHMWPE) and size distribution have important effect too.So mainly comprise the polymerization activity of (1) raising catalyzer at present for the research of extra high-molecular polythene catalyst; (2) by adjusting the prescription of catalyzer, make molecular weight adjustable within the specific limits; (3) adjust the particle diameter of catalyzer and improve poly particle diameter.
Chinese patent 94105011 discloses dialkyl magnesium and the halogenating agent reaction forms mainly by formula M g-X
2The reactant that constitutes reacts under the electron donor effect with titanium compound again, and described electron donor is selected carboxylicesters, ether, ketone, acid amides or oxygen containing phosphorus or sulfide.Can the prepared sizes narrowly distributing, average particle diameter is at the ultrahigh molecular weight polyethylene(UHMWPE) of 100-200um.Though the size distribution of polymkeric substance is more satisfactory, the polymerization activity of catalyzer is not high.
The preparation method of the disclosed extra high-molecular polythene catalyst of ZL00819563.3 comprises i) make magnesium compound solution by the mixture and the pure contact reacts of halogenated magnesium compound and aluminium or boron compound, the ii) ester cpds of this solution and at least one hydroxyl and have the silicon compound (R of alkoxyl group
nSi (OR ')
4-n) reaction and iii) add titanium compound and silicon compound (R
nSiCl
4-n) mixture prepare solid titanium catalyst.This catalyzer has active preferably, the polyethylene tap density is than higher, but in this Preparation of catalysts process, need to use a large amount of titanium tetrachlorides to carry out aftertreatment, this will bring bigger problem and environmental pollution to aftertreatment work in suitability for industrialized production, simultaneously will carry out prepolymerization during polymerization catalyst.
Different defectives at above prior art existence, the present invention will provide a kind of catalyzer that is used to prepare ultrahigh molecular weight polyethylene(UHMWPE), not only has excellent polymerization activity, and catalyzer just can be directly used in the polymerization of ethene without prepolymerization, poly bulk density is than higher simultaneously, and fine powder content is few.
Summary of the invention
One of technical problem to be solved by this invention provides a kind of extra high-molecular polythene catalyst.
Two of technical problem to be solved by this invention provides a kind of preparation method of extra high-molecular polythene catalyst.
Three of technical problem to be solved by this invention provides the application of a kind of extra high-molecular polythene catalyst in ethylene homo or copolymerization.
A kind of extra high-molecular polythene catalyst, this catalyzer comprises body of catalyst component and promotor, and wherein the preparation of body of catalyst component obtains by following steps:
(1) halogenated magnesium compound and alcohol compound, the reaction of titanate ester compound form magnesium compound solution,
(2) magnesium compound solution and chlorination alkylaluminium cpd reaction obtains an intermediate product,
(3) intermediate product reacts with titanium compound, electron donor again.
Halogenated magnesium compound described in the present invention comprises: magnesium dihalide compound, for example magnesium chloride, magnesium bromide, magnesium iodide or magnesium fluoride; Alkyl halide magnesium compound, for example methylmagnesium-halide, ethyl magnesium halide, propyl group magnesium halide, butyl magnesium halide, isobutyl-magnesium halide, hexyl magnesium halide or amyl group magnesium halide; Alkoxyl group halogenated magnesium compound, for example methoxyl group magnesium halide, oxyethyl group magnesium halide, sec.-propyl halogenation magnesium, butoxy magnesium halide or octyloxy magnesium halide.In the above-claimed cpd, can use a kind of halogenated magnesium compound, also can use the mixture of two or more halogenated magnesium compound.The preferred magnesium dihalide of the present invention, more preferably magnesium chloride.
Alcohol of the present invention comprises the alcohol with 4～20 carbon atoms, preferably has the alcohol of 4～10 carbon atoms, as isopropylcarbinol, 2-Ethylhexyl Alcohol, 2-methyl amyl alcohol, 2-ethyl butanol, octanol etc.More preferably 2-Ethylhexyl Alcohol.
Chlorination alkylaluminium cpd of the present invention can general formula R
1 nAlCl
3-nExpression, wherein R
1Be alkyl with 1～14 carbon atom, 1≤n＜3, operable compound such as aluminium diethyl monochloride, dichloro one aluminium triethyl, chlorination di-isopropyl aluminium, sesquialter ethylaluminium chloride, sesquialter chlorinated butyl aluminium etc., preferred aluminium diethyl monochloride.
Titanate ester compound of the present invention can general formula Ti (OR
2)
bExpression, wherein R
2Be the alkyl with 1～10 carbon atom, b is the integer of 1-4, the just own ester of operable compound such as tetrabutyl titanate, isopropyl titanate, iso-butyl titanate, metatitanic acid, metatitanic acid pentyl ester etc.Preferred tetrabutyl titanate.
Electron donor of the present invention can be selected ethers, ester class, ethers comprises phenyl ether, cresyl ether, ethylbenzene ether etc., the ester class comprises benzoates, phosphoric acid ester, benzoates such as ethyl benzoate, to (neighbour) phthalic acid diisobutyl ester, to (neighbour) phthalic acid di-n-butyl, methyl benzoate, 2 hydroxybenzoic acid ethyl ester, 3-nipagin A, 4-methyl hydroxybenzoate etc.; Phosphoric acid ester comprises tributyl phosphate, triphenyl phosphite etc.; Also can select silane compound as electron donor, comprise dimethyldimethoxysil,ne, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, dimethyldiethoxysilane etc.These two kinds of electron donors also can mix use.The preferred phenyl ether of the present invention, dimethoxydiphenylsilane.
Titanium compound described in the present invention can general formula Ti (OR
3)
mCl
4-mExpression, wherein R
3Be alkyl with 1～10 carbon atom, 0≤m≤4, operable compound such as titanium tetrachloride, tetrabutyl titanate, isopropyl titanate, methoxyl group titanous chloride, dibutoxy titanium dichloride, three butoxy titanium chlorides etc.The present invention can mix use with two kinds of different titanium compounds, for example has at least one OR
3The titanium compound of group and titanium tetrachloride mix use, and the present invention preferably only uses a kind of titanium compound, more preferably titanium tetrachloride.
Promotor described in the present invention is an organo-aluminium compound, comprises triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum etc. or its mixture, preferred triethyl aluminum.
A kind of preparation method of extra high-molecular polythene catalyst comprises following preparation process:
(5) magnesium halide and alcohol compound, titanate ester compound contact reacts in hydrocarbon solvent prepare magnesium compound solution, the add-on of titanate ester and alcohol compound is in the consumption of magnesium halide, be 2～10mol alcohol/mol magnesium halide, 0.03～0.5mol titanate ester/mol magnesium halide;
(6) adding chlorination alkylaluminium cpd, reaction obtain a suspension in above-mentioned magnesium compound solution, and the consumption of chlorination alkylaluminium cpd is 0.3～1.0mol chlorination aluminum alkyls/mol alcohol in the add-on of alcohol;
(7) titanium compound, electron donor and above-mentioned suspension contact reacts, obtain the body of catalyst component, the consumption of titanium compound and the consumption of electron donor are respectively 0.25～2.0mol titanium compound/mol magnesium halide all in the consumption of magnesium halide, 0.1～0.8mol electron donor/mol magnesium halide;
(8) in the body of catalyst component in Ti and the promotor Al according to 1: the mol ratio contact reacts of (30～300).
To describe the preparation method of body of catalyst component below in detail:
Magnesium halide and alcohol compound, titanate ester compound contact reacts in hydrocarbon solvent, described varsol comprises the aliphatic hydrocarbon compounds with 5～10 carbon atoms, as Skellysolve A, iso-pentane, normal hexane, normal heptane, octane, decane; Alicyclic hydrocarbon type is as hexanaphthene, methylcyclohexane; Arene is as benzene, toluene or ethylbenzene.Preferred normal hexane of the present invention and normal heptane.Titanate ester and alcohol can drip or disposable adding, are warmed up to 60～100 ℃ after adding, and stirring reaction 1～4 hour obtains magnesium compound solution, and cool to room temperature is stand-by then.The add-on of alcohol is 2～10mol alcohol/mol magnesium halide in the consumption of magnesium halide, preferred 3～8mol alcohol/mol magnesium halide; The consumption of titanate ester compound is 0.03～0.5mol titanate ester/mol magnesium halide in the consumption of magnesium halide, preferred 0.05～0.8mol titanate ester/mol magnesium halide.Use the titanate ester compound in the present invention, help to improve the tap density of polymkeric substance and reduce fine powder content; And the consumption of titanate ester compound should strict be controlled.
In above-mentioned magnesium compound solution, add the chlorination alkylaluminium cpd, can drip or disposable adding the mode that the present invention preferably drips, the dropping time is 0.5～1 hour, be warmed up to 50～100 ℃ after adding, stirring reaction 1～4 hour obtains having the sedimentary suspension of particulate state.Cool to room temperature, stand-by.The consumption of chlorination alkylaluminium cpd is 0.3～1.0mol chlorination aluminum alkyls/mol alcohol in the add-on of alcohol, preferred 0.5～0.8mol chlorination aluminum alkyls/mol alcohol.
At room temperature, titanium compound contacts with above-mentioned suspension, in order to mix, can add a certain amount of hydrocarbon solvent.Be warmed up to 40～70 ℃, under this temperature, stirring reaction 2～4 hours continues the intensification evaporation drying then, obtains powder catalyst main body component.The consumption of titanium compound is 0.25～2.0mol titanium compound/mol magnesium halide in the consumption of magnesium halide, preferred 0.3～1.0mol titanium compound/mol magnesium halide.
When titanium compound contacts with suspension, can add electron donor and participate in reaction, the consumption of electron donor is 0.1～0.8mol electron donor/mol magnesium halide in the consumption of magnesium halide, preferred 0.2～0.6mol electron donor/mol magnesium halide.
Body of catalyst component and promotor are 1 according to the mol ratio of Al in Ti and the promotor in the body of catalyst component: (30～300) contact reacts.
The body of catalyst component that obtains by above-mentioned preparation method can directly contact homopolymerization or the copolymerization that is used for ethene with promotor.Adoptable comonomer is the aliphatics alpha-olefin with 3～8 carbon atoms, comprises propylene, butene-1, hexene-1, and 4-methylpentene-1, heptene-1, octene-1, preferred alpha-olefin is butene-1 and hexene-1.
Catalyzer of the present invention can be used for slurry polymerization processes and produces ultrahigh molecular weight polyethylene(UHMWPE), and polymerization temperature is 50～100 ℃, and preferred 55～80 ℃, polymerization pressure is 0.5～1.0Mpa.
Compared with prior art, extra high-molecular polythene catalyst of the present invention has following advantage:
1, extra high-molecular polythene catalyst of the present invention is active high, at 0.5Mpa, and 65 ℃ of following polymerizations 4 hours, the polymerization activity of catalyzer can reach 20000 gram polyethylene/more than the gram catalyzer;
2, in the preparation process of body of catalyst component, used the titanate ester compound, can obtain tap density at 0.36～0.4g/cm
3The ultrahigh molecular weight polyethylene(UHMWPE) of scope;
3, catalyzer of the present invention can directly apply to polymerization, does not need prepolymerization;
4, method for preparing catalyst simple possible of the present invention, good work environment.
The test of the analysis of catalyzer main ingredient and polyethylene product salient features adopts following method to carry out among this specification sheets embodiment:
Bulk density is measured according to GB 1636-1979;
The mensuration of viscosity-average molecular weight is at first measured the limiting viscosity of polymkeric substance, [η] and viscosity-average molecular weight M according to GB1841-1980
ηThe pass be [η]=KM
η α, K and α are constant, K=6.67*10
2, α=0.67 can calculate viscosity-average molecular weight M thus
η
Embodiment
Further specify the present invention below by detailed description to specific embodiments of the invention, but embodiment and do not mean that limitation of the present invention.
Embodiment 1:
Have heating system and be furnished with whipping appts and condenser system and in the four-hole boiling flask of the 250ml of purging with nitrogen gas, add Magnesium Chloride Anhydrous 4.3 grams, 80 milliliters of hexanes stir, and measure 0.8 milliliter of 28 milliliters of 2-Ethylhexyl Alcohols and tetrabutyl titanate, be added dropwise in the flask, be warmed up to 65 ℃ then, under this temperature, keep reaction 2 hours, be cooled to room temperature, add 20 milliliters of aluminium diethyl monochlorides again,, be warmed up to 60 ℃, under this temperature, keep reaction 1.5 hours, be cooled to room temperature, obtain the suspension of solids precipitation thing, clean, add 2.0 milliliters of phenyl ether then with hexane solvent, 2 milliliters of titanium tetrachlorides, be warmed up to 60 ℃ after stirring, under this temperature, keep reaction 3 hours, continue then to heat up, and under nitrogen purging heat drying, obtain the powder catalyst main body component of good fluidity.
Polyreaction:
After fully cleaning 2 liters of stainless steel cauldrons with high-purity nitrogen, in reactor, add the industrial hexane of 1200 milliliters of dryings, body of catalyst component and promotor triethyl aluminum, control Al: Ti=200.Be warming up to 50 ℃, add ethene, keeping the reaction stagnation pressure is 0.5MPa.Continue to be warmed up to 65 ℃, under this temperature, keep reaction 4 hours.After the polymerization, stop to add ethene, with reactor cooling and exhaust rapidly.Reclaim polymer slurries, from hexane, isolate polyethylene powders.The result data of polymerization catalyst evaluation sees Table 1, and the size data of polymerization product sees Table 2.
Embodiment 2:
Change phenyl ether into dimethoxydiphenylsilane, consumption is 2.5 milliliters, and all the other are with embodiment 1.
Polyreaction is with embodiment 1.The result data of polymerization catalyst evaluation sees Table 1, and the size data of polymerization product sees Table 2.
Embodiment 3:
The consumption of butyl (tetra) titanate is adjusted into 2.3 milliliters, and all the other are with embodiment 1.
Polyreaction is with embodiment 1.The result data of polymerization catalyst evaluation sees Table 1, and the size data of polymerization product sees Table 2.
Embodiment 4:
The consumption of butyl (tetra) titanate is adjusted into 4.6 milliliters, and all the other are with embodiment 1.
Polyreaction is with embodiment 1.The result data of polymerization catalyst evaluation sees Table 1, and the size data of polymerization product sees Table 2.
The comparative example 1:
Do not add butyl (tetra) titanate, all the other are with embodiment 1.
Polyreaction is with embodiment 1.The result data of polymerization catalyst evaluation sees Table 1, and the size data of polymerization product sees Table 2.
The comparative example 2:
The consumption of butyl (tetra) titanate is adjusted into 0.3 milliliter, and all the other are with embodiment 1.
Polyreaction is with embodiment 1.The result data of polymerization catalyst evaluation sees Table 1, and the size data of polymerization product sees Table 2.
The comparative example 3:
The consumption of butyl (tetra) titanate is adjusted into 18 milliliters, and all the other are with embodiment 1.
Polyreaction is with embodiment 1.The result data of polymerization catalyst evaluation sees Table 1, and the size data of polymerization product sees Table 2.
Table 1:
| The embodiment numbering | Ti(OBu) 4/MgCl 2 mol/mol | Active (gram polyethylene/gram catalyzer) | Bulk density (gram per centimeter 3) | Viscosity-average molecular weight (ten thousand) |
| Embodiment 1 | 0.05 | 20775 | 0.38 | 507 |
| Embodiment 2 | 0.05 | 23276 | 0.40 | 549 |
| Embodiment 3 | 0.42 | 21364 | 0.37 | 491 |
| Embodiment 4 | 0.7 | 26167 | 0.38 | 480 |
| The comparative example 1 | 0 | 8500 | 0.32 | 501 |
| The comparative example 2 | 0.02 | 7531 | 0.29 | 472 |
| The comparative example 3 | 1.2 | 7426 | 0.27 | 494 |
Table 2
| The embodiment numbering | ＜20 orders (wt%) | 20～40 orders (wt%) | 40～75 orders (wt%) | 75～120 orders (wt%) | 120～200 orders (wt%) | ＞200 orders (wt%) |
| Embodiment 1 | 5.6 | 10.3 | 49.8 | 21.3 | 12.7 | 0.3 |
| Embodiment 2 | 7.5 | 9.2 | 50.4 | 19.8 | 12.9 | 0.2 |
| Embodiment 3 | 7.3 | 7.8 | 52.2 | 23.3 | 9.2 | 0.2 |
| Embodiment 4 | 6.5 | 10.1 | 45.9 | 28.4 | 9.0 | 0.1 |
| The embodiment numbering | ＜20 orders (wt%) | 20～40 orders (wt%) | 40～75 orders (wt%) | 75～120 orders (wt%) | 120～200 orders (wt%) | ＞200 orders (wt%) |
| The comparative example 1 | 8.9 | 15.3 | 44.3 | 12.4 | 15.6 | 3.5 |
| The comparative example 2 | 4.1 | 14.2 | 48.2 | 14.1 | 16.2 | 3.2 |
| The comparative example 3 | 5.7 | 13.5 | 47.4 | 20.4 | 9.0 | 4.0 |
Claims (11)
1. extra high-molecular polythene catalyst, this catalyzer comprises body of catalyst component and promotor, and wherein the preparation of body of catalyst component obtains by following steps:
(1) reaction of halogenated magnesium compound and alcohol compound and titanate ester compound forms magnesium compound solution,
(2) magnesium compound solution and chlorination alkylaluminium cpd reaction obtains an intermediate product,
(3) intermediate product reacts with titanium compound and electron donor again;
Wherein said alcohol compound refers to have the alcohol of 4～20 carbon atoms, and described titanium compound is with general formula Ti (OR
3)
mCl
4-mExpression, wherein R
3Be alkyl with 1～10 carbon atom, 0≤m≤4.
2. extra high-molecular polythene catalyst according to claim 1 is characterized in that described halogenated magnesium compound is a magnesium chloride.
3. extra high-molecular polythene catalyst according to claim 1 is characterized in that described alcohol is 2-Ethylhexyl Alcohol.
4. extra high-molecular polythene catalyst according to claim 1 is characterized in that described chlorination alkylaluminium cpd is an aluminium diethyl monochloride.
5. extra high-molecular polythene catalyst according to claim 1 is characterized in that described titanate ester is a tetrabutyl titanate.
6. extra high-molecular polythene catalyst according to claim 1, it is characterized in that described electron donor is selected from ethers, ester class or silane compound, wherein ethers is selected from phenyl ether, cresyl ether or ethylbenzene ether, the ester class is selected from benzoates or phosphoric acid ester, and benzoates is selected from ethyl benzoate, isobutyl terephthalate, diisobutyl phthalate, di-n-butyl terephthalate, n-butyl phthalate, methyl benzoate, 2 hydroxybenzoic acid ethyl ester, 3-nipagin A or 4-methyl hydroxybenzoate; Phosphoric acid ester is selected from tributyl phosphate or triphenyl phosphite; Silane compound is selected from dimethyldimethoxysil,ne, dimethoxydiphenylsilane, phenylbenzene diethoxy silane or dimethyldiethoxysilane.
7. extra high-molecular polythene catalyst according to claim 6 is characterized in that described electron donor is phenyl ether or dimethoxydiphenylsilane.
8. extra high-molecular polythene catalyst according to claim 1 is characterized in that described titanium compound is a titanium tetrachloride.
9. the preparation method of an extra high-molecular polythene catalyst comprises following preparation process:
(1) magnesium halide and alcohol compound, titanate ester compound contact reacts in hydrocarbon solvent prepare magnesium compound solution, the add-on of titanate ester and alcohol compound is in the consumption of magnesium halide, be 2～10mol alcohol/mol magnesium halide, 0.03～0.5mol titanate ester/mol magnesium halide;
(2) adding chlorination alkylaluminium cpd, reaction obtain a suspension in above-mentioned magnesium compound solution, and the consumption of chlorination alkylaluminium cpd is 0.3～1.0mol chlorination aluminum alkyls/mol alcohol in the add-on of alcohol;
(3) titanium compound, electron donor and above-mentioned suspension contact reacts, obtain the body of catalyst component, the consumption of titanium compound and the consumption of electron donor are respectively 0.25～2.0mol titanium compound/mol magnesium halide all in the consumption of magnesium halide, 0.1～0.8mol electron donor/mol magnesium halide;
(4) body of catalyst component and promotor contact reacts, wherein in the body of catalyst component in Ti and the promotor mol ratio of Al be 1: (30～300);
Wherein said alcohol compound refers to have the alcohol of 4～20 carbon atoms, and described titanium compound is with general formula Ti (OR
3)
mCl
4-mExpression, wherein R
3Be alkyl with 1～10 carbon atom, 0≤m≤4.
10. the preparation method of extra high-molecular polythene catalyst according to claim 9 is characterized in that the consumption of the add-on of alcohol in magnesium halide, is 3～8mol alcohol/mol magnesium halide; The consumption of chlorination alkylaluminium cpd is 0.5～0.8mol chlorination aluminum alkyls/mol alcohol in the add-on of alcohol; The consumption of titanium compound is 0.25～2.0mol titanium compound/mol magnesium halide in the consumption of magnesium halide.
11. the purposes of the described extra high-molecular polythene catalyst of claim 1 is characterized in that described catalyzer is applied to the homopolymerization or the copolymerization of ethene.
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| CN101970508B (en) | 2008-03-14 | 2013-03-27 | 沙特基础工业公司 | A catalyst system and a process for the production of polyethylene in the presence of this catalyst system |
| US20110159287A1 (en) * | 2008-04-17 | 2011-06-30 | Saudi Basic Industries Corporation | Process for the Production of Ultra High Molecular Weight Polyethylene |
| CN101831015B (en) * | 2009-03-10 | 2011-12-07 | 中国石油天然气股份有限公司 | Catalyst for preparing ultra-high molecular weight polyethylene |
| EP2284199A1 (en) | 2009-08-14 | 2011-02-16 | Saudi Basic Industries Corporation | A catalyst system and a process for the production of polyethylene |
| CN102796212B (en) * | 2011-05-27 | 2014-04-02 | 中国石油化工股份有限公司 | Catalyst component and catalyst system for olefin polymerization, applications thereof and olefin polymerization method |
| CN102276763B (en) * | 2011-06-23 | 2013-04-24 | 中国石油天然气股份有限公司 | Preparation method of ethylene polymerization catalyst with slurry process |
| CN102863564B (en) * | 2011-07-04 | 2014-12-10 | 中国石油化工股份有限公司 | High activity catalyst used for synthesizing ultrahigh molecular weight polyethylene and preparation method |
| CN102863563B (en) * | 2011-07-04 | 2014-12-10 | 中国石油化工股份有限公司 | Ultrahigh molecular polyethylene catalyst and preparation method |
| CN102952222B (en) * | 2011-08-30 | 2015-02-25 | 中国石油化工股份有限公司 | Ultra-high molecular weight polyethylene resin and preparation method thereof |
| CN103509139B (en) * | 2012-06-27 | 2016-04-13 | 中国石油化工股份有限公司 | The preparation method of extra high-molecular polythene catalyst |
| CN103509140B (en) * | 2012-06-27 | 2016-04-13 | 中国石油化工股份有限公司 | The preparation method of ultrahigh molecular weight polyethylene(UHMWPE) catalyst for synthesizing |
| CN108203481A (en) * | 2016-12-20 | 2018-06-26 | 中国石油天然气股份有限公司 | The production method of ultra-high molecular weight polyethylene |
| CN107556411A (en) * | 2017-08-22 | 2018-01-09 | 上海联乐化工科技有限公司 | A kind of extra high-molecular polythene catalyst and preparation method and application |
| CN107602743A (en) * | 2017-09-27 | 2018-01-19 | 中玺新材料（安徽）有限公司 | A kind of preparation method of extra high-molecular polythene catalyst |
| CN113817083B (en) * | 2021-09-29 | 2023-03-03 | 天津华聚化工科技有限公司 | Temperature-sensitive ultrahigh molecular weight polyethylene catalyst, preparation method and application thereof |
| CN116041577A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component, catalyst system, application and olefin polymerization method |
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| CP03 | Change of name, title or address | ||
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Address after: Shanghai city Putuo District Yunling Road No. 345 Co-patentee after: SHANGHAI LEADER CATALYST Co.,Ltd. Patentee after: SHANGHAI RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. Address before: 200062 Shanghai city Putuo District Yunling Road No. 345 Patentee before: SHANGHAI RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. Address after: 200062 Shanghai city Putuo District Yunling Road No. 345 Patentee after: SHANGHAI RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. Address before: 200062 Shanghai Yunling Road No. 345 Patentee before: Shanghai Research Institute of Chemical Industry |