CN101824105A - Solid titanium catalytic component and catalyst - Google Patents
Solid titanium catalytic component and catalyst Download PDFInfo
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- CN101824105A CN101824105A CN200910079175A CN200910079175A CN101824105A CN 101824105 A CN101824105 A CN 101824105A CN 200910079175 A CN200910079175 A CN 200910079175A CN 200910079175 A CN200910079175 A CN 200910079175A CN 101824105 A CN101824105 A CN 101824105A
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Abstract
The invention relates to a solid titanium catalytic component, which adopts tartaric acid diamide in a general formula (I) as an internal electron donor. When the catalytic component is used for olefin (copolymerization) polymerization, particularly propylene (copolymerization) polymerization, the polymer with high stereoselectivity can be obtained. The invention also discloses a catalyst comprising the catalytic component.
Description
Technical field
The present invention relates to a kind of solid titanium catalyst component and catalyzer, particularly a kind of propylene (being total to) polymeric catalyst component and catalyzer of being used for.
Background technology
As everyone knows, with magnesium, titanium, halogen and electron donor solid titanium catalyst component, can be used for CH as basal component
2=CHR olefinic polyreaction particularly can obtain the polymkeric substance of higher yields and higher tacticity in the alpha-olefine polymerizing with 3 carbon or more carbon atoms.Wherein, electron donor is one of requisite composition in the catalyst component, and along with the development of electron donor compound has caused polyolefin catalyst constantly to update.
Previously, reported multiple electron donor compound in the document in a large number, for example polycarboxylic acid, monobasic or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine etc. and derivative thereof, wherein comparatively commonly used is binary aromatic carboxylic acid's ester class, as n-butyl phthalate or diisobutyl phthalate (CN85100997A) etc.
In recent years, people attempt adopting other compounds as the electron donor in the olefin polymerization catalyst components, US4971937, US2004014597 and EP728769 have adopted special 1, the 3-diether compound is as electron donor, as 2, and 2-diisobutyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal and 9,9-two (methoxymethyl) fluorenes etc. also can be referring to CN1042547A, CN1143651A, US2003027715 and WO03076480.The disclosed catalyst component that is used for olefinic polyreaction of CN1054139A, it is special 1 to adopt, and the 3-cyclohexadione compounds is as electron donor, as 2,2,6,6-tetramethyl--3,5-heptadione and 2,2,4,6,6-pentamethyl--3,5-heptadione etc.
Special dibasic aliphatic carboxylic acid esters and the diol-lipid compound of one class disclosed again recently, as (referring to CN1313869A, CN1236373A, CN1236374A, CN1552741A, CN1213080C, CN1542024A, CN1552742A and CN1552740A) such as succinate, malonic ester, glutarate, glycol ester, propylene glycol ester, butanediol ester, pentadiol ester and hexylene glycol esters.CN1313869A, US6818583 and WO2004024785 disclose the succinate that replaces is given body as the internal electron of the catalyst component that is used for olefinic polymerization application.The use of these electron donor compounds not only can improve activity of such catalysts, and the polyacrylic molecular weight distribution of gained is obviously widened.
Summary of the invention
The object of the present invention is to provide a kind of CH of being used for
2The solid titanium catalyst component of=CHR olefinic polyreaction, wherein R is hydrogen or the hydrocarbyl group with 1-12 carbon atom.Another object of the present invention provides the catalyzer that contains above-mentioned catalyst component.
Solid titanium catalyst component of the present invention by weight percentage, comprises 10-25% magnesium, 1-10% titanium, 40-60% halogen and 1-30% internal electron donor, and described internal electron donor is selected from least a tartrate diamide in the general formula (I):
Wherein, radicals R
1To R
4Being same to each other or different to each other, is C
1-C
20Line style or alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or the kiki fang alkyl group of branching; Radicals R
5And R
6Be same to each other or different to each other, be hydrogen or C
1-C
20Line style or alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or the kiki fang alkyl group of branching, and R
5And R
6Can be joined together from forming ring.
In above-mentioned tartrate diamide general formula compound, R
1To R
4Be preferably C
1-C
10Alkyl, cycloalkyl or arylalkyl, preferred especially C
1-C
10Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or neo-pentyl, further preferable methyl, ethyl or sec.-propyl.
In above-mentioned tartrate diamide general formula compound, R
5And R
6Preferred aryl groups, arylalkyl or kiki fang alkyl group.
The examples of compounds of suitable above-mentioned general formula includes but not limited to:
N, N, N ', N '-tetramethyl--1-diacetyl tartaric acid diamide, N, N, N '-trimethylammonium-d-diacetyl tartaric acid diamide, N, N-dimethyl-N ', N '-ethyl-d1-diacetyl tartaric acid diamide, N, N-dimethyl-N '-ethyl-meso-diacetyl tartaric acid diamide, N, N, N ', N '-tetraethyl--1-two phenylacetyl tartrate diamide, N, N, N '-triethyl-d-two phenylacetyl tartrate diamide, N, N, N ', N '-tetraethyl--d1-phenyl methyl ketone acetyl tartrate diamide, N, N-dimethyl-N ', N '-ethyl-meso-phenyl methyl ketone acetyl tartrate diamide, N-ethyl-N '-sec.-propyl-d-dibenzoyl tartaric acid diamide, N, N-di-isopropyl-d1-dibenzoyl tartaric acid diamide, meso-dibenzoyl tartaric acid diamide, N, N, N ', N '-tetramethyl--phthalyl tartrate diamide, phthalyl tartrate diamide or N, N, N '-triethyl-phthalyl tartrate diamide.
The preparation of above-mentioned tartrate diamide compound can be adopted prior art, is starting raw material with corresponding tartrate promptly, synthesizes by esterification and acylation reaction, and the esterification preparation process can be referring to document Org.Synth.IV, 242.; Org.Synth.IV, 304.; Org.Synth.72,86. relevant report.Acylation reaction can be referring to following document: E.Pretsch, D.Amnmn, H.F.Oaaward, et al.Helv.Chim.Act a.1980,65 (1), 191.; Burnt Megrez, Wang Yanbo, Tan Xiaomei, etc. synthetic chemistry 1999,7 (2), 207..
Magnesium in the catalyst component can be by size-grade distribution 20～250 μ m, and general formula is Mg (OR ') mX
(2-m)The magnesium halide alcohol adduct of pROH provides, and R ' is C in the formula
1～C
20Alkyl, arylalkyl or aryl; X is a halogen; M is the integer of 0≤m＜2; N is the decimal or the integer of 0＜p＜6; R is C
1-C
20The alkyl or aryl alkyl.
Magnesium halide in the magnesium halide alcohol adduct is selected from a kind of in magnesium dichloride, dibrominated magnesium, chloro magnesium methylate or the chloro magnesium ethylate, preferred magnesium dichloride; Alcohol in the magnesium halide alcohol adduct is selected from a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or the isopropylcarbinol, preferred alcohol.
After magnesium halide alcohol adduct adopts magnesium halide and alcohol to be total to heat of solution, high pressure ejection or high-speed stirring, the method that is solidified into microsphere particle in heat-eliminating medium obtains, and concrete grammar is referring to the associated description among the US4399054.
Titanium in the catalyst component can be TiX by general formula
n(OR)
4-nCompound provide, R is that carbonatoms is the alkyl of 1-20 in the formula; X is a halogen; N=1-4.Concrete compound is as titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium or trichlorine one ethanolato-titanium, preferred titanium tetrachloride.
The preparation method of solid titanium catalyst component of the present invention comprises: (1) joins spherical magnesium halide alcohol adduct in-40～10 ℃ the titanium compound, reacts 1～4 hour, and the mol ratio of magnesium and titanium is 1: 5～1: 50; (2) be warming up to 30～80 ℃, add the internal electron donor compound, the mol ratio of magnesium and internal electron donor compound is 2: 1～15: 1; (3) be warming up to 100～150 ℃ again, reacted 1～4 hour; (4) add titanium compound with step (1) same amount after filtering again, in 110～130 ℃ of reactions 1～4 hour, more after filtration, washing obtained after the drying.
With above-mentioned solid titanium catalyst component is main ingredient, and the present invention also can further be provided for the catalyzer of olefinic polymerization.Catalyzer specifically comprises:
(a) contain magnesium, titanium, halogen and be selected from the catalyst component of at least a tartrate diamide in the general formula (I);
(b) alkylaluminium cpd;
(c) randomly, external electron donor,
With titanium: aluminium: the molar ratio computing between the external electron donor compound, the amount ratio in the catalyzer between each component are 1: 5～1000: 0～500.
Wherein, alkylaluminium cpd (b) is selected from trialkyl aluminium compound, as the mixture of triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum or tri-n-octylaluminium, trialkylaluminium and aluminum alkyl halide or alkyl aluminum hydride, or alkylaluminoxane.
The external electron donor component can add as required selectively.Obtain the olefin polymer of taxis very high (as isotactic index greater than 99%) for needs, suggestion adds the external electron donor compound.
It is R that external electron donor can be selected general formula
nSi (OR ')
4-nSilicoorganic compound, the integer of 0≤n in the formula≤3; R is of the same race or different alkyl, cycloalkyl or aryl with R ', the optional heteroatoms that contains; R also can be halogen or hydrogen atom.Concrete silicoorganic compound are as the trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, cyclohexyl methyl dimethoxy silane, methyl-t-butyldimethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane or two (cyclobutylmethyl) dimethoxy silane, preferred cyclohexyl methyl dimethoxy silane.
With titanium: aluminium: the molar ratio computing between the external electron donor compound (c), the amount ratio in the catalyzer between each component be preferably 1: 25～and 100: 25～300.
Catalyzer of the present invention is used for olefinic polymerization, can access the polymkeric substance of very high isotactic index when the equal polymerization of special propylene or the copolymerization of propylene and other alkene.Simultaneously, do not get rid of the copolymerization that is applicable to production polyethylene and ethene and alpha-olefin such as propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene or 1-octene yet.
Can adopt the whole bag of tricks of the prior art when being used for propylene polymerization, can in liquid phase or gas phase, carry out, also can under the combination operation of liquid and gas polymerization stage, carry out.Polymerization is carried out at 0～150 ℃ usually, preferred 40～90 ℃.Polymerization pressure is 0.01～10MPa.The hydrogen of chain-transfer agent effect or other compounds can be played and the molecular weight of controlling polymers can be used for.
The present invention is by adopting novel internal electron donor tartrate diamide compound, can obtain the catalyzer of high comprehensive performance, when being used for propylene (being total to) polymerization, can obtain gratifying polymerization yield rate, and the stereospecificity height of polymkeric substance, catalyzer is also fine to the susceptibility of hydrogen accent simultaneously, and the molecular weight distribution broad of resulting polymers helps the exploitation of the different trades mark of polymkeric substance.
Embodiment
Embodiment given below is for the present invention is described better, rather than limits the invention.
Testing method:
1, polymericular weight and molecular weight distribution MWD (MWD=M
w/ M
n): adopting the gel permeation chromatography method, is that solvent is measured down at 135 ℃ with the orthodichlorobenzene with Alliance-GPCV2000.
2, polymkeric substance degree of isotacticity: adopt the heptane extraction process to measure (heptane boiling extracting 8 hours), promptly 1 restrain the exsiccant polymer samples, be placed in the extractor with the extracting of boiling heptane after 8 hours, the polymer weight (g) that residuum is dried to the constant weight gained is degree of isotacticity with 1 ratio.
3, the mensuration of melt index (MI): measure according to μ PXRZ-400C.
4, the mensuration of titanium percentage composition: according to spectrophotometry.
5, the mensuration of internal electron donor percentage composition: according to the Autosystem XL of PE company gas chromatograph for determination.
Embodiment 1-14
One, the tartrate amide compound is synthetic
1. synthetic winestone acid anhydrides
(1) synthetic d-diacetyl tartaric acid acid anhydride
In the 100mL flask, add 12.0g d-tartrate, the 0.4mL vitriol oil and 40mL diacetyl oxide, reflux 10 minutes, reaction is 1 hour under the room temperature, filters, and filter cake is used the ether recrystallization after washing with benzene again, gets the 13.6g crystal, yield 79%.
The synthetic method of the used acid anhydrides of internal electron donor of synthetic embodiment 1,3-6 and 9-11 similarly.
(2) synthetic meso-phenyl methyl ketone acetyl winestone acid anhydrides
In the 100mL flask, add 15.0g meso-tartrate, the 0.5mL vitriol oil, 5.1g diacetyl oxide and 12.7g phenylacetic anhydride, reflux 30 minutes, reaction is 2 hours under the room temperature, filter, filter cake is used the ether recrystallization after washing with benzene again, gets the 21.3g crystal, yield 73%.
The synthetic method of the used acid anhydrides of internal electron donor of synthetic embodiment 7 similarly.
(3) synthetic phthalyl winestone acid anhydrides
In the 100mL flask, add 15.0g meso-tartrate, the 0.5mL vitriol oil and 14.8g Tetra hydro Phthalic anhydride, reflux 40 minutes, reaction is 2 hours under the room temperature, filters, and filter cake is used the ether recrystallization after washing with benzene again, gets the 18.6g crystal, yield 71%.
2. synthetic tartrate acid amides
(1) synthetic N, N, N '-trimethylammonium-d-diacetyl tartaric acid diamide (embodiment 2)
In the 100mL flask, add the homemade diacetyl tartaric acid acid anhydride of 2.16g, the aqueous solution that contains the 0.45g dimethylamine, the aqueous solution that contains the 0.31g methylamine and 30mL methylene dichloride, room temperature reaction 12h filters the filter cake ethyl alcohol recrystallization, get crystal product 2.6g, yield 95%.
1H NMR (TMS, CDCl
3, 400MHz) analytical results: δ 8.03 (s, 1H, NH); δ 5.70 (s, 2H, CH); δ 2.91 (s, 6H, CH
3); δ 2.66 (s, 3H, CH
3); δ 1.99 (s, 6H, CH
3).
The synthetic method of the internal electron donor that embodiment 3,4,6,8,9 and 14 is used similarly.
(2) synthetic N, N, N ', N '-tetraethyl--1-two phenylacetyl tartrate diamide (embodiment 5)
Add the homemade two phenylacetyl tartrate acid anhydrides of 3.68g, 2.2g diethylamine and 30mL methylene dichloride in the 50mL flask, room temperature reaction 12h filters, and the filter cake ethyl alcohol recrystallization gets crystal product 4.6g, yield 93%.
1H NMR (TMS, CDCl
3, 400MHz) analytical results: δ 7.04-7.15 (m, 10H, Ph); δ 5.73 (s, 2H, CH); δ 3.51 (s, 4H, CH
2); δ 3.26 (q, 8H, CH
2CH
3); δ 1.19 (t, 12H, CH
3).
The synthetic method of the internal electron donor that embodiment 1,7 and 12 is used similarly.
(3) synthetic N, N-di-isopropyl-d1-dibenzoyl tartaric acid diamide (embodiment 10)
Add the homemade d1-dibenzoyl tartaric acid of 3.40g acid anhydride, 1.01g Diisopropylamine and 0.30g urea in the 50mL flask, room temperature reaction 6h is warming up to 160 ℃ of reaction 4h, is warming up to 220 ℃ again, reaction 5min.Use ethyl alcohol recrystallization, get crystal product 3.06g, yield 70%.
1H NMR (TMS, CDCl
3, 400MHz) analytical results: δ 7.34-7.97 (m, 10H, Ph); δ 6.05 (s, 2H, NH
2); δ 5.69 (s, 2H, CH); δ 3.91 (m, 2H, CH); δ 2.66 (s, 12H, CH
3).
(4) synthetic phthalyl tartrate diamide (embodiment 13)
In the 50mL flask, add 2.62g homemade phthalyl winestone acid anhydrides and 0.90g urea, be warming up to 160 ℃ of reaction 4h, be warming up to 220 ℃ again, reaction 5min.Use ethyl alcohol recrystallization, get crystal product 2.11g, yield 76%.
1H NMR (TMS, CDCl
3, 400MHz) analytical results: δ 7.57-7.99 (m, 4H, fragrant H); δ 6.09 (s, 4H, NH
2); δ 5.77 (s, 2H, CH).
The synthetic method of the internal electron donor that embodiment 11 is used similarly.
Two, the preparation of spherical catalyst component
Under the anhydrous and oxygen-free condition, in the abundant metathetical 500mL four neck round-bottomed flasks of process high pure nitrogen, add TiCl
4100mL and toluene 60mL are cooled to-20 ℃, add 10.0gMgCl
22.8CH
3CH
2OH ball type carrier (according to the method preparation of USP4399054).Rise to 0 ℃ in 1 hour, continuing to heat up rose to 20 ℃ in 2 hours, and continuing to heat up rose to 40 ℃ in 1 hour, added corresponding tartrate diamide compound 7.4mmol in the table 1 respectively, was warming up to 100 ℃ in 1 hour, kept venting filtrate 2 hours.Add TiCl
4100mL rose to 120 ℃ in 1 hour, kept venting filtrate 2 hours.Add anhydrous hexane 60mL, boiling attitude washing 5 times adds anhydrous hexane 60mL then, and normal temperature washing 3 times is at last with the solid catalytic component vacuum-drying that obtains.
Comparative example 1-2
Press the preparation method of the spherical catalyst component of the foregoing description, just internal electron donor is replaced with n-butyl phthalate and meso-dibenzoyl tartaric acid dimethyl ester respectively.
Three, propylene polymerization experiment
The spherical catalyst component of the foregoing description 1-14 and comparative example 1-2 is carried out propylene polymerization respectively.Usually step is: volume is the stainless steel autoclave of 10L, after high pure nitrogen is fully replaced, adds AlEt
35.0mmol external electron donor methylcyclohexyl dimethoxy silane (CHMMS) 0.2mmol adds ingredient of solid catalyst 20mg and the 2.4L hydrogen of the foregoing description 1-24 again, feeds liquid propene 2.5L, is warming up to 70 ℃, keeps this temperature 1 hour.Cooling, pressure release to 1 normal atmosphere obtains polypropylene.Polymerization result is listed in table 1.
Table 1 propylene polymerization result
Four, vinyl polymerization experiment
Volume is the stainless steel autoclave of 10L, after high pure nitrogen is fully replaced, starts stirring, progressively adds the catalyst solid constituent and the 5.0mmol promotor AlEt of 2L hexane, 20mg embodiment 5 gained under nitrogen protection in still
3After being warming up to 75 ℃, in still, replenish an amount of high-purity hydrogen, make that hydrogen partial pressure is 0.3Mpa in the still, after 5 minutes in still make-up ethylene gas make its dividing potential drop reach 0.75MPa, the dividing potential drop of keeping ethylene gas is constant, make system temperature keep 80 ℃, after 3 hours, cooling discharge, polymkeric substance except that desolvating, is obtained polyethylene 561g after the thorough drying.
Five, ethene and copolymerization of propylene experimental result
Volume is the stainless steel autoclave of 10L, after high pure nitrogen is fully replaced, starts stirring, progressively adds the catalyst solid constituent and the 5.0mmol promotor AlEt of 2L hexane, 20mg embodiment 5 gained under nitrogen protection in still
3Feed liquid propene 2.5L, be warming up to 75 ℃ after, in still, replenish an amount of high-purity hydrogen, making the interior hydrogen partial pressure of still is 0.3MPa, make-up ethylene gas makes its dividing potential drop reach 0.75MPa in still then, and the dividing potential drop of keeping ethylene gas is constant, makes system temperature keep 80 ℃, after 3 hours, cooling discharge except that desolvating, obtains polymer powders 977g with polymkeric substance after the thorough drying.
Claims (17)
1. solid titanium catalyst component, by weight percentage, comprise 10%～25% magnesium, 1%～10% titanium, 40%～60% halogen and 1%～30% internal electron donor, it is characterized in that described internal electron donor is selected from least a tartrate diamide in the general formula (I):
Wherein, radicals R
1To R
4Being same to each other or different to each other, is C
1～C
20Line style or alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or the kiki fang alkyl group of branching; Radicals R
5And R
6Be same to each other or different to each other, be hydrogen or C
1～C
20Line style or alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or the kiki fang alkyl group of branching, and R
5And R
6Can be joined together from forming ring.
2. catalyst component according to claim 1 is characterized in that in the tartrate diamide general formula compound R
1To R
4Be C
1～C
10Alkyl, cycloalkyl or arylalkyl; R
5And R
6Be aryl, arylalkyl or kiki fang alkyl group.
3. catalyst component according to claim 2 is characterized in that in the tartrate diamide general formula compound R
1To R
4Be C
1～C
10Alkyl.
4. catalyst component according to claim 3, it is characterized in that tartrate diamide general formula compound is N, N, N ', N '-tetramethyl--1-diacetyl tartaric acid diamide, N, N, N '-trimethylammonium-d-diacetyl tartaric acid diamide, N, N-dimethyl-N ', N '-ethyl-d1-diacetyl tartaric acid diamide, N, N-dimethyl-N '-ethyl-meso-diacetyl tartaric acid diamide, N, N, N ', N '-tetraethyl--1-two phenylacetyl tartrate diamide, N, N, N '-triethyl-d-two phenylacetyl tartrate diamide, N, N, N ', N '-tetraethyl--d1-phenyl methyl ketone acetyl tartrate diamide, N, N-dimethyl-N ', N '-ethyl-meso-phenyl methyl ketone acetyl tartrate diamide, N-ethyl-N '-sec.-propyl-d-dibenzoyl tartaric acid diamide, N, N-di-isopropyl-d1-dibenzoyl tartaric acid diamide, meso-dibenzoyl tartaric acid diamide, N, N, N ', N '-tetramethyl--phthalyl tartrate diamide, phthalyl tartrate diamide or N, N, N '-triethyl-phthalyl tartrate diamide.
5. catalyst component according to claim 1 is characterized in that magnesium in the catalyst component by size-grade distribution 20～250 μ m, and general formula is Mg (OR ') mX
(2-m)The magnesium halide alcohol adduct of pROH provides, and R ' is C in the formula
1～C
20Alkyl, arylalkyl or aryl; X is a halogen; M is the integer of 0≤m＜2; N is the decimal or the integer of 0＜p＜6; R is C
1-C
20The alkyl or aryl alkyl.
6. catalyst component according to claim 5 is characterized in that providing in the magnesium halide alcohol adduct of magnesium, and magnesium halide is a kind of in magnesium dichloride, dibrominated magnesium, chloro magnesium methylate or the chloro magnesium ethylate; Alcohol in the magnesium halide alcohol adduct is a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or the isopropylcarbinol.
7. catalyst component according to claim 6, it is characterized in that providing the magnesium halide in the magnesium halide alcohol adduct of magnesium is magnesium dichloride; Alcohol in the magnesium halide alcohol adduct is ethanol.
8. catalyst component according to claim 1 is characterized in that the titanium in the catalyst component is TiX by general formula
n(OR)
4-nCompound provide, R is that carbonatoms is the alkyl of 1-20 in the formula; X is a halogen; N=1-4.
9. catalyst component according to claim 8 is characterized in that the titanium in the catalyst component is provided by titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium or trichlorine one ethanolato-titanium.
10. catalyst component according to claim 9 is characterized in that the titanium in the catalyst component is provided by titanium tetrachloride.
11. a catalyzer that comprises one of the described catalyst component of claim 1 to 10 is characterized in that catalyzer comprises:
A) one of the described catalyst component of claim 1 to 10;
B) alkylaluminium cpd;
C) randomly, external electron donor component.
12. catalyzer according to claim 11 is characterized in that alkylaluminium cpd is a trialkyl aluminium compound.
13. catalyzer according to claim 12, it is characterized in that alkylaluminium cpd is the mixture of triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium, trialkylaluminium and aluminum alkyl halide or alkyl aluminum hydride, or alkylaluminoxane.
14. catalyzer according to claim 11 is characterized in that external electron donor is that general formula is R
nSi (OR ')
4-nSilicoorganic compound, the integer of 0≤n in the formula≤3; R is of the same race or different alkyl, cycloalkyl or aryl with R '.
15. catalyzer according to claim 14, it is characterized in that external electron donor is the trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, cyclohexyl methyl dimethoxy silane, methyl-t-butyldimethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane or two (cyclobutylmethyl) dimethoxy silane.
16. catalyzer according to claim 15 is characterized in that external electron donor is a cyclohexyl methyl dimethoxy silane.
17. catalyzer according to claim 11 is characterized in that with titanium: aluminium: the molar ratio computing of external electron donor compound, the consumption between each component are 1: 25～100: 25～300.
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| CN103665220B (en) * | 2012-09-18 | 2016-08-10 | 中国石油天然气股份有限公司 | A kind of ingredient of solid catalyst for preparing ultra-high molecular weight polyethylene |
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