CN1179984C - Component for olefinic polymerization loaded on nano carrier as well as its preparing method and application - Google Patents
Component for olefinic polymerization loaded on nano carrier as well as its preparing method and application Download PDFInfo
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- CN1179984C CN1179984C CNB021295468A CN02129546A CN1179984C CN 1179984 C CN1179984 C CN 1179984C CN B021295468 A CNB021295468 A CN B021295468A CN 02129546 A CN02129546 A CN 02129546A CN 1179984 C CN1179984 C CN 1179984C
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Abstract
The present invention provides a catalyst component for olefinic polymerization. A reaction product of a magnesium compound, a transitional metal titanium compound and an electron donor compound is loaded on a carrier, and the average particle diameter of the carrier is smaller than 100 nm. Titanium content in the catalyst component is high, and the catalyst component for ethene polymerization has high polymerization activity. An obtained polymer has narrow particle diameter distribution, and particle diameter magnitude and particle diameter magnitude distribution can be stably controlled. The catalyst component has the advantages of simple synthetic technology, high synthetic yield, great enhancement of a conversion rate of titanium tetrachloride, and catalyst cost reduction.
Description
Technical field
The present invention relates to a kind of catalyst component for olefin and preparation method and application, more particularly, relate to a kind of catalyst component for olefin and preparation method and application that is carried on the nano carrier.
Technical background
The Ti/Mg series catalysts was occupied an leading position in poly synthesizing, and its research core is nothing more than the particle form of the polymerization activity that is catalyzer, catalyzer, the copolymerization performance of catalyzer, the apparent density of polymkeric substance and the cost of catalyzer.In the industrial application of catalyzer, polyvinyl size and size distribution that control is produced are crucial, the different resin trades mark has different particle diameters to require to require between 300～125 microns with poly particle diameter as chlorination, and the particle diameter of ultrahigh molecular weight polyethylene(UHMWPE) requires between 200～100 microns.In polymkeric substance synthetic, thicker polymer beads easily causes line clogging, and fine powder easily causes " airborne dust " phenomenon.The effective means of the size of controlling polymers and size distribution is the particle diameter and the size distribution of control catalyst.
In the prior art, in order to obtain having the catalyzer of single-size diameter and better particle form, people adopt two following class methods to prepare catalyzer usually.
First kind is magnesium compounds such as magnesium chloride to be dissolved in obtain homogeneous solution in some solvent, and then this solution mixed with titanium compound and electron donor, obtain containing the solids of magnesium, titanium and electron donor by sedimentary method, and obtain granules of catalyst after this solids handled with excessive liquid titanium compound.For example disclosed among Chinese patent CN1099041A, CN1229092, the CN85100997 etc.The shortcoming of this traditional method is that the particle diameter and the size distribution of granules of catalyst controlled by precipitation process fully, its stable control ratio is difficulty, and because the use of a large amount of liquid titanium compounds brings very big problem for recovery system and environmental protection aspect, the catalyzer cost is higher.Simultaneously, the size distribution broad of resulting polymers, the difficult control of size distribution.
For example, in patent CN1229092, be carrier with the magnesium chloride, titanium tetrachloride is an active ingredient, the Preparation of catalysts method is as follows: earlier with MgCl
2The dissolving (toluene solvant, electron donor, solubility promoter and precipitation additive) be homogeneous transparent solution, then at low temperatures with TiCl
4Reaction is separated out solid catalyst by slow intensification.The catalyst component that makes is used for vinyl polymerization, has high polymerization activity, and the particle form of polymkeric substance is (BD:＞0.33g/ml better; 20～200 orders:＞90%).The inventor finds in practice, go out in the precipitator method synthetic catalyst in this eutectoid, must use excessive titanium tetrachloride to promote separating out of catalyst component, the fluctuation of heat-up rate, stirring intensity all can influence the particle form of catalyzer, thereby the particle form of impact polymer is difficult to the stably size and the particle size distribution of control catalyst in actually operating, and this technology is in catalyzer synthetic, the transformation efficiency of titanium tetrachloride is lower, the large usage quantity of titanium tetrachloride.
In patent CN1268521, be carrier with the magnesium chloride, titanium tetrachloride is an active ingredient, the Preparation of catalysts method is as follows: at 120 ℃ of dissolving MgCl
2(decane solvent, alcohol compound) is then with the ester compound reaction, again with TiCl
4Reaction, the catalyst component that makes is used for vinyl polymerization, and the polymerization activity of catalyzer is higher, and polymkeric substance has narrower size distribution, and (75～940 μ:＞95%), but the apparent density of polymkeric substance is lower.
Second kind is that the catalyst activity component directly is carried on inert support, and as on the silica gel etc., because the particle diameter of silica gel controls easily, and particle form is better, therefore can obtain evengranular catalyst particle.But because the charge capacity of active ingredient is restricted on the carrier, therefore titanium content is lower in the catalyzer that makes of this method, and polymerization activity is not high.
In patent CN1268520, be carrier with magnesium chloride, silicon-dioxide, titanium tetrachloride is an active ingredient, the Preparation of catalysts method is as follows: with MgCl
2In THF with IiCl
4Reaction is again with the SiO that handled through aluminum alkyls
2Mix, remove behind the THF in hexane solvent and the aluminum alkyls reaction, the catalyzer that makes is used for vinyl polymerization, although use accelerative activator in polymerization, because the titanium content in the catalyzer is lower, polymerization activity is still lower.
Therefore, be starved of provide a kind of catalytic activity height, all even narrow diameter distribution of particle diameter and be easy to control be used for ethylene polymerization catalysts.
Summary of the invention
Inventor's repetition test is found, the carrier that has the specific granule diameter by use, for example particle diameter less than the nano-grade inorganics of 100nm or organism as carrier, and the active constituent loading that will contain magnesium halide carrier is on this carrier, both overcome above-mentioned eutectoid and gone out the catalyst particle size size and the unsettled weakness of control that distributes in the precipitator method, improved the productive rate of catalyzer, reduced the consumption of titanium compound, overcome again and carried the low weakness of titanium (active centre) amount in the above-mentioned patented technology, improved the polymerization activity of catalyzer.
The invention provides a kind of catalyst component that is used for olefinic polymerization, it is the reaction product that load has magnesium compound, transition metal titanium compound and electron donor compound on carrier, and the average particulate diameter＜100nm of described carrier is preferably 30-80nm.This carrier is selected from SiO
2, TiO
2, ZnO, Al
2O
3, MgO, Al (OH)
3, CaCO
3, at least a in the kaolin, polynite, talcum powder or their mixture, wherein preferred SiO
2, CaCO
3, Al (OH)
3
Described magnesium compound is selected from one of them halogen atom in the complex compound, magnesium dihalide molecular formula of water, alcohol of magnesium dihalide, magnesium dihalide by in alkyl or the halogen-oxyl institute metathetical derivative one or more.Be preferably magnesium dichloride, dibrominated magnesium, two magnesium iodides.
Preferably with described magnesium compound, for example magnesium dihalide is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds in implementation process of the present invention.Wherein said organic epoxy compounds comprises at least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halo fat group alkene or diolefine of carbonatoms.Concrete as: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether or tetrahydrofuran (THF).Wherein said organo phosphorous compounds is the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.Concrete as: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate or phosphorous acid benzene methyl.Wherein in every mole of magnesium dihalide: organic epoxy compounds: 0.2-10mol, preferred 0.5～4mol; Organo phosphorous compounds: 0.1～5mol, preferred 0.3～1.0mol mol.In order to make dissolving more abundant, in this solvent system, can randomly add inert diluent, common this inert diluent can adopt hexane, heptane, octane, benzene,toluene,xylene, 1,2-ethylene dichloride, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound are as long as help the magnesium halide dissolved to use.Above-mentioned inert diluent can use separately, use also capable of being combined.
Described titanium compound TiXn (OR)
4-nR is that carbonatoms is 1～20 alkyl in the formula, X is a halogen, n=1～4, a kind of or its mixture in preferred titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium.
Described electron donor is an organic alcohol compound, and it is selected from methyl alcohol, ethanol, Virahol, propyl alcohol or the butanols one or more, is preferably ethanol, propyl alcohol or butanols.
At the catalyst component that is used for olefinic polymerization of the present invention, based on every mole of magnesium compound meter: the electron donor compound is 0.1-100mol, is preferably 0.5-50mol; Titanium compound is 1-20mol, is optimized for 4-10mol; The add-on of nano level carrier is the 0.1-10 gram, is preferably the 0.5-5 gram.
Catalyst component of the present invention can adopt following method preparation:
1. the solution of magnesium halide
In the solvent system that organic epoxy compounds, organo phosphorous compounds and inert diluent are formed, dissolve magnesium halide, behind the transparent homogeneous solution of formation magnesium halide.Solvent temperature: 10-90 ℃, inert solvent comprises: benzene,toluene,xylene, 1,2-ethylene dichloride, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound are as long as help the magnesium halide dissolved to use.Above-mentioned inert diluent can use separately, use also capable of being combined.Preferably described electron donor organic alcohol compound will be contained also in the described magnesium halide solution.Wherein each component is counted with every mole of magnesium halide: inert diluent: 4.5-50mol, and preferred: 10-24mol; Organic epoxy compounds: 0.2-10mol, preferred: 0.5～4; Organo phosphorous compounds: 0.1～5mol, preferred: 0.3～1.0mol; Organic alcohol compound: 0.1-100mol, preferred: 0.5-50mol.
2. the load on second carrier
In the transparent homogeneous solution of above-mentioned magnesium halide, add second carrier compound.Its add-on is in every gram magnesium halide, and add-on is the 0.1-10 gram, is preferably the 0.5-5 gram.
3. titanium compound
Add the magnesium halide solution behind second carrier, with the titanium compound reaction, temperature of reaction is between 20--20 ℃.In every mole of magnesium halide, the add-on of titanium compound: 1-20mol, preferred: 4-10mol.Reaction 10min-3hr.Temperature programming: 10-50-90 ℃.
Remove unreacted reactant and solvent, obtain the solid precipitate,, remove unreacted reactant with above-mentioned inert solvent washing 2-5 time.Vacuum-drying obtains the solid catalyst of flowable state.
The present invention also provides the catalyzer of the copolyreaction of a kind of equal polymerization reaction that is used for ethene or ethene and other alpha-olefin, and alpha-olefin wherein comprises propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, vinylbenzene, vinyl toluene etc.; This catalyzer comprises above-mentioned catalyst component of the present invention and general formula is AlR
nX
3-nOrgano-aluminium compound reaction product and randomly comprise at least a external electronic donor compound, wherein R is a hydrogen, carbonatoms is 1～20 alkyl, X is a halogen, n is the number of 1＜n≤3.This organo-aluminium compound is selected from least a of triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium.
Liquid polymerization can be adopted during polymerization, also vapour phase polymerization can be adopted.
Liquid polymerization medium comprises: hexane, heptane, hexanaphthene, petroleum naphtha, raffinate oil, inert solvent such as aliphatic saturated hydrocarbon such as hydrogenated gasoline, kerosene, benzene,toluene,xylene or aromatic hydrocarbon.Also available alkene itself is as reaction medium.
Can carry out prepolymerization earlier before the polymerization, polymerization methods can adopt intermittent type, semi continuous or continous way.
Polymerization temperature is 0～150 ℃, with 40～100 ℃ for well.
In order to regulate molecular weight, adopt hydrogen to make molecular weight regulator.
It is worthy of note that the titanium content in the catalyzer of the present invention is higher, be used for vinyl polymerization and have quite high polymerization activity that resulting polymers has narrower size distribution, and can stably control size and particle size distribution.And the synthesis technique of catalyst component is simple, the synthetic yield is higher, has improved the transformation efficiency of titanium tetrachloride widely, has reduced the cost of catalyzer.
Embodiment
Example 1
The preparation of catalyst component: in the glass reaction bottle of 500ml (nitrogen replacement), add 4.0gMgCl
2, 100ml toluene, 5.0ml epoxy chloropropane, 6.0ml tributyl phosphate, 3.0ml ethanol, be warming up to 55 ℃, treat MgCl
2Dissolving fully adds 4.9gSiO
2(median size is 40nm) is cooled to-10 ℃, drips 20mlTiCl
4, stirred 0.5 hour, in 2 hours, be warmed up to 90 ℃, the elimination liquids is used toluene, each washed twice of hexane (80ml/ time, room temperature) successively, vacuumizes drying, gets ingredient of solid catalyst 12.7g.Adopt its composition of sem test (weight percentage): Mg:11.8, Si:28.3, Cl:52.4, Ti:6.65.
Example 2
The preparation of catalyst component: remove with SiO
2Add-on replace with outside the 4.0g by 4.9g, all the other are with embodiment 1, ingredient of solid catalyst 11.0g.Adopt its composition of sem test (weight percentage): Mg:12.7, Si:23.4, Cl:56.9, Ti:6.89.
Example 3
The preparation of catalyst component: remove with SiO
2Add-on replace with outside the 3.0g by 4.9g, all the other are with embodiment 1, ingredient of solid catalyst 11.0g.Adopt its composition of sem test (weight percentage) .Mg:14.1, Si:16.1, Cl:59.1, Ti:8.13.
Example 4
The preparation of catalyst component: remove SiO with 4.9g
2Replace with CaCO
35.0g outer, all the other get ingredient of solid catalyst 12.9g with embodiment 1.
Example 5
The preparation of catalyst component: remove SiO with 4.9g
2Replace with Al (OH)
35.0g outer, all the other get ingredient of solid catalyst 13.6g with embodiment 1.
Example 6
In 5L autoclave (through nitrogen replacement), add hexane 2L, triethyl aluminum 5mmol, embodiment 1 catalyst component 11.9mg, be warming up to 70 ℃, feed ethene and keep 1.0Mpa, 70 ℃ of following polymerizations 2 hours.Get polymkeric substance 823g.Catalyst activity: 69kgPE/gcat, polymkeric substance apparent density: 0.36g/ml.Polymkeric substance screening result such as table 1.
Example 7
In 5L autoclave (through nitrogen replacement), add hexane 2L, triethyl aluminum 5mmol, embodiment 1 catalyst component 9.1mg, be warming up to 80 ℃, add hydrogen 0.25Mpa, feed ethene and keep 0.8Mpa, 80 ℃ of following polymerizations 2 hours.Get polymkeric substance 125.7g.Melt index MI:0.48g/10min, polymkeric substance apparent density: 0.31g/ml.Polymkeric substance screening result such as table 1.
Example 8
In 2L autoclave (through nitrogen replacement), add hexane 1L, triethyl aluminum 2mmol, embodiment 2 catalyst component 4.3mg, be warming up to 70 ℃, feed ethene and keep 1.0Mpa, 70 ℃ of following polymerizations 2 hours.Get polymkeric substance 202g.Catalyst activity: 47kgPE/gcat, polymkeric substance apparent density: 0.35g/ml.Polymkeric substance screening result such as table 1.
Example 9
In 2L autoclave (through nitrogen replacement), add hexane 1L, triethyl aluminum 2mmol, embodiment 3 catalyst component 4.2mg, be warming up to 70 ℃, feed ethene and keep 1.0Mpa, 70 ℃ of following polymerizations 2 hours.Get polymkeric substance 273g.Catalyst activity: 65kgPE/gcat, polymkeric substance apparent density: 0.35g/ml.Polymkeric substance screening result such as table 1.
Example 10
In 5L autoclave (through nitrogen replacement), add hexane 3L, triethyl aluminum 5mmol, embodiment 4 catalyst component 18.7mg, be warming up to 70 ℃, add hydrogen 0.25Mpa, feed ethene and keep 0.8Mpa, 70 ℃ of following polymerizations 2 hours.Get polymkeric substance 284g.Melt index MI:0.2g/10min, polymkeric substance apparent density: 0.37g/ml.Polymkeric substance screening result such as table 1.
Example 11
In 5L autoclave (through nitrogen replacement), add hexane 3L, triethyl aluminum 5mmol, embodiment 5 catalyst component 16.8mg, be warming up to 80 ℃, add hydrogen 0.25Mpa, feed ethene and keep 0.8Mpa, 80 ℃ of following polymerizations 2 hours.Get polymkeric substance 258g.Melt index MI:0.31g/10min, polymkeric substance apparent density: 0.37g/ml.Polymkeric substance screening result such as table 1.
Comparative Examples 1
The preparation of catalyst component (not adopting silica-gel carrier):
In the glass reaction bottle of 500ml (nitrogen replacement), add 4.0g MgCl
2, 100ml toluene, 5.0ml epoxy chloropropane, 6.0ml tributyl phosphate, 3.0ml ethanol, be warming up to 55 ℃, treat MgCl
2Dissolving is cooled to-10 ℃ fully, drips 20mlTiCl
4, stirred 0.5 hour, in 2 hours, be warmed up to 90 ℃, the elimination liquids is used toluene, each washed twice of hexane (80ml/ time, room temperature) successively, vacuumizes drying, gets catalyzer 6.1g.
Polymerization:
In 5L autoclave (through nitrogen replacement), add hexane 2L, triethyl aluminum 5mmol, above-mentioned catalyzer 14.3mg, be warming up to 80 ℃, add hydrogen 0.25Mpa, feed ethene and keep 0.8Mpa, 80 ℃ of following polymerizations 2 hours.Get polymkeric substance 425g, catalyst activity: 29.7kgPE/gcat.Melt index MI:0.30g/10min, polymkeric substance apparent density: 0.31g/ml.Polymkeric substance screening result such as table 1.
Comparative Examples 2
The preparation of catalyst component (adopting the silica-gel carrier of conventional particle diameter):
In the glass reaction bottle of 500ml (nitrogen replacement), add 4.0g MgCl
2, 100ml toluene, 5.0ml epoxy chloropropane, 6.0ml tributyl phosphate, 3.0ml ethanol, be warming up to 55 ℃, treat MgCl
2Dissolving fully adds 4.9gSiO
2(Davion948# of U.S. Grace company, median size is about the 40-45 micron) is cooled to-10 ℃, drips 20mlTiCl
4, stirred 0.5 hour, in 2 hours, be warmed up to 90 ℃, the elimination liquids is used toluene, each washed twice of hexane (80ml/ time, room temperature) successively, vacuumizes drying, gets ingredient of solid catalyst 7.3g.
Polymerization:
In 5L autoclave (through nitrogen replacement), add hexane 2L, triethyl aluminum 5mmol, catalyst component 14.0mg, be warming up to 70 ℃, feed ethene and keep 1.0Mpa, 70 ℃ of following polymerizations 2 hours.Get polymkeric substance 552g.Catalyst activity: 39kgPE/gcat, polymkeric substance apparent density: 0.31g/ml.Polymkeric substance screening result such as table 1.
Table 1 polymkeric substance screening result
| Embodiment | ＞20 orders | 20～40 orders | 40～100 orders | 100～200 orders | ＜200 orders |
| Example 6 | 9.3 | 15.0 | 60.4 | 12.6 | 2.8 |
| Example 7 | 7.1 | 6.0 | 71.3 | 14.2 | 1.4 |
| Example 8 | 9.2 | 22.6 | 59.1 | 8.6 | 0.4 |
| Example 9 | 13.6 | 31.6 | 43.6 | 8.3 | 1.4 |
| Example 10 | 15.0 | 18.7 | 49.8 | 12.0 | 4.3 |
| Example 11 | 3.0 | 8.7 | 73.4 | 12.9 | 1.9 |
| Comparative Examples 1 | 26.5 | 14.8 | 56.0 | 3.1 | 0.64 |
| Comparative Examples 2 | 55.6 | 24.5 | 10.5 | 7.8 | 2.2 |
Claims (15)
1, a kind of ethylene polymerization catalysts component that is used for, it is the reaction product that load has magnesium compound, transition metal titanium compound and electron donor compound on carrier, average particulate diameter＜the 100nm of described carrier, in every mole of magnesium compound: electron donor compound: 0.1-100mol, titanium compound is 1-20mol, and the add-on of carrier is the 0.1-10 gram.
2, the ethylene polymerization catalysts component that is used for according to claim 1 is characterized in that, the average particulate diameter 30-80nm of described carrier.
3, the ethylene polymerization catalysts component that is used for according to claim 1 and 2 is characterized in that described carrier is selected from SiO
2, TiO
2, ZnO, Al
2O
3, MgO, Al (OH)
3, CaCO
3, at least a in the kaolin, polynite, talcum powder or their mixture.
4, the ethylene polymerization catalysts component that is used for according to claim 1, it is characterized in that described magnesium compound is selected from one of them halogen atom in the complex compound, magnesium dihalide molecular formula of water, alcohol of magnesium dihalide, magnesium dihalide by in alkyl or the halogen-oxyl institute metathetical derivative one or more.
5, the ethylene polymerization catalysts component that is used for according to claim 1 is characterized in that, described magnesium compound is that magnesium dihalide is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds.
6, the ethylene polymerization catalysts component that is used for according to claim 5, wherein said organic epoxy compounds comprise at least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halogenated aliphatic alkene or diolefine of carbonatoms.
7, the ethylene polymerization catalysts component that is used for according to claim 5, wherein said organic epoxy compounds is oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether or tetrahydrofuran (THF).
8, the ethylene polymerization catalysts component that is used for according to claim 5, wherein said organo phosphorous compounds are the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.
9, the ethylene polymerization catalysts component that is used for according to claim 5, wherein said organo phosphorous compounds is ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate or phosphorous acid benzene methyl.
10, the ethylene polymerization catalysts component that is used for according to claim 5 is wherein in every mole of magnesium dihalide: organic epoxy compounds: 0.2-10mol, organo phosphorous compounds: 0.1～5mol.
11, the ethylene polymerization catalysts component that is used for according to claim 1, it is characterized in that described titanium compound is selected from a kind of or its mixture in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium.
12, the ethylene polymerization catalysts component that is used for according to claim 1 is characterized in that described electron donor is selected from one or more in methyl alcohol, ethanol, Virahol, propyl alcohol or the butanols.
13, a kind of ethylene polymerization catalysts that is used for, it comprises the product of following substance reaction:
(a) each described ingredient of solid catalyst among the claim 1-12;
(b) at least a general formula is AlR
nX
3-nOrgano-aluminium compound, R is a hydrogen in the formula, carbonatoms is 1～20 alkyl, X is a halogen, n is the number of 1＜n≤3; With, randomly,
(c) at least a external electronic donor compound.
14, the described catalyzer of claim 13, wherein organo-aluminium compound (b) is a kind of trialkyl aluminium compound.
15, the described catalyzer of claim 14, wherein trialkyl aluminium compound is selected from triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium.
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| SA3686B1 (en) | 2009-10-16 | 2014-10-22 | China Petroleum& Chemical Corp | Catalyst component for olefin polymerization and catalyst comprising the same |
| EP2716682B1 (en) | 2011-06-03 | 2017-04-26 | Sumitomo Seika Chemicals Co. Ltd. | Polyalkylene oxide particles and production method for same |
| KR101871539B1 (en) | 2011-06-03 | 2018-06-26 | 스미토모 세이카 가부시키가이샤 | Polyalkylene oxide particles and production method for same |
| CN111848845B (en) * | 2020-07-03 | 2023-03-24 | 江苏扬农化工集团有限公司 | Catalyst for preparing low-entanglement ultrahigh molecular weight polyethylene and preparation method thereof |
| CN114249851B (en) * | 2020-09-24 | 2023-03-14 | 中国科学院上海有机化学研究所 | Low bulk density ultra-high molecular weight polyethylene micro-powder |
| CN114133470B (en) * | 2022-01-17 | 2022-12-30 | 中国科学技术大学 | Preparation method and application of alpha-diimine nickel heterogeneous catalyst loaded on aluminum olefine acid salt polymer particles |
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