CN101824108B - Ziegler-Natta catalyst - Google Patents
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- CN101824108B CN101824108B CN2009100791740A CN200910079174A CN101824108B CN 101824108 B CN101824108 B CN 101824108B CN 2009100791740 A CN2009100791740 A CN 2009100791740A CN 200910079174 A CN200910079174 A CN 200910079174A CN 101824108 B CN101824108 B CN 101824108B
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Abstract
The invention discloses a Ziegler-Natta catalyst, which concretely comprises the following components of: (a) 10-25% of magnesium by weight, 1-10% of titanium by weight, 40-60% of halogen by weight and 1-30% of catalyst component of at least one maleic acid ester selected from the general formula (I) by weight; (b) alkyl aluminum compounds; and (c) optionally, an external electron donor. Because a maleic acid ester compound with a special structure is adopted to be the external electron donor, the catalyst with excellent combination property is obtained, when the catalyst is used for propylene copolymerization, satisfactory copolymerization yield can be obtained, and the polymer has higher stereospecificity.
Description
Technical field
The present invention relates to a kind of Ziegler-natta catalyst, particularly a kind of propylene (being total to) polymeric Ziegler-Natta catalyst that is used for.
Background technology
As everyone knows, Ziegler-Natta catalyst is with magnesium, titanium, halogen and the electron donor solid titanium catalyst component as basal component, can be used for CH
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 Ziegler-Natta 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 verivate thereof; Wherein comparatively commonly used is binary aromatic carboxylic acid's ester class, like 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, and 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.
Disclose one type of special dibasic aliphatic carboxylic acid esters and diol-lipid compound recently again, given body (referring to CN1313869A, CN1236373A, CN1236374A, CN1552741A, CN1213080C, CN1542024A, CN1552742A and CN1552740A) as the internal electron of olefin polymerization catalysis like succinate, malonic ester, glutarate, glycol ester, propylene glycol ester, butanediol ester, pentadiol ester and pinakon ester etc.The use of these electron donor compounds not only can improve activity of such catalysts, and the polyacrylic MWD of gained is obviously widened.But when not adopting the external electron donor component, the degree of isotacticity of resulting polymers is still lower.US6818583 and WO2004024785 disclose substituted succinate and have given body as internal electron, not only can improve activity of such catalysts, and the polyacrylic MWD of gained are widened obviously.
Patent EP45977 discloses and has used unsubstituted maleic acid ester to be used for the polyreaction of alkene as the internal electron donor compound, and its result is relatively poor aspect active and stereospecificity.Patent US5436213 has related to and not having replaced and the unsubstituted maleic acid ester of 2-methyl, and the performance of catalyzer is particularly active relatively poor.Japanese Patent JP58-138708 discloses a kind of internal electron donor---and straight chain alcohol and replacement or do not replace the ester that toxilic acid forms, the performance of catalyzer is still undesirable aspect active and stereospecificity.
Patent CN1714105A, EP2002010049 and WO2003022894 disclose a series of single replacements and disubstituted maleic acid ester, and said activity of such catalysts and stereospecificity are all better, but the synthetic difficulty of compound is big, and cost is high.
Summary of the invention
The object of the present invention is to provide a kind of CH of being used for
2The Ziegler-Natta catalyst of=CHR olefinic polymerization, wherein R is hydrogen or the hydrocarbyl group with 1-12 carbon atom.
The contriver is through discovering, the maleic acid ester that contains 5-norbornylene-7-oxa-ring structure can be given body as the internal electron of Ziegler-Natta catalyst effectively, and the compound method of this compound is simple, and is easy to utilize.
Based on above-mentioned research, the present invention proposes a kind of Ziegler-Natta catalyst, specifically comprises:
(a) by weight percentage, the catalyst component that is selected from least a maleic acid ester in the general formula (I) that contains 10～25% magnesium, 1～10% titanium, 40～60% halogens and 1～30%;
(b) alkylaluminium cpd;
(c) randomly, external electron donor,
Wherein, in the general formula (I), radicals X is heteroatomss such as oxygen, sulphur or nitrogen; Radicals R
1And R
2Being same to each other or different to each other, is C
1～C
20Line style or alkyl, alkenyl, naphthenic base, aryl, arylalkyl or the kiki fang alkyl group of branching, the optional heteroatoms that contains; Radicals R
3To R
6Be same to each other or different to each other, be hydrogen or C
1～C
20Line style or alkyl, alkenyl, naphthenic base, aryl, arylalkyl or the kiki fang alkyl group of branching, optional heteroatoms and the R of containing
3～R
6In two or more groups mutually bonding generate one or several condensed ring structure;
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.
In above-mentioned general formula compound, X is preferably Sauerstoffatom.
In above-mentioned general formula compound, R
1And R
2Be preferably C
1～C
10Alkyl, naphthenic base or arylalkyl, further preferred C
1～C
10Alkyl, like methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or neo-pentyl, preferred especially ethyl, normal-butyl or isobutyl-.
In above-mentioned general formula compound, preferred R
3And R
4, R
5And R
6In to have one group of group at least be hydrogen, more preferably, radicals R
3To R
6Be hydrogen.
The instance of suitable above-mentioned general formula compound includes but not limited to:
7-oxabicyclo [2.2.1] heptan-2,5-diene-2,3-dioctyl phthalate dimethyl ester, 7-thia dicyclo [2.2.1] heptan-2,5-diene-2; 3-dioctyl phthalate dimethyl ester, 7 amine-dicyclo [2.2.1], 2,5 diene in heptan, 2,3 dioctyl phthalate dimethyl esters, 7-oxabicyclo [2.2.1] heptan-2,5-diene 2; 3-dicarboxylate, 1,4-dimethyl--7-oxa--dicyclo [2.2.1] heptan-2,5 diene-2,3-dioctyl phthalate di-n-butyl, 5; 6-dimethyl-7-oxa--dicyclo [2.2.1] heptan-2,5-diene-2,3-dioctyl phthalate diisobutyl ester or 1,4; 5,6-tetramethyl--7-oxa--dicyclo [2.2.1] heptan-2,5-diene-2,3-dicarboxylate.
The synthetic of above-mentioned general formula compound can be adopted known method, promptly prepared by esterification and diels-alder reaction (Diels-Alder Reaction).Pertinent literature is referring to Org.Syn.IV, 242.; D.C.Tabor, F.H.White, L.W.Collier, S.A.Evans J.Org.Chem.1983,48 (10), 1638.; Y.Chen, R.Kiattansakul, B.Ma, J.K.Snyder J.Org.Chem.2001,66 (21), 6932..
Magnesium in the catalyzer 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 in heat-eliminating medium, is solidified into microsphere particle obtains, and concrete grammar is referring to the associated description among the US4399054.
Titanium in the catalyzer 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 like 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 catalyst component of the present invention (a) comprising: (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, through filtering, washing obtained after the drying again.
Alkylaluminium cpd in the catalyzer (b) is selected from trialkyl aluminium compound; Like 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 (like 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, naphthenic base or aryl with R ', the optional heteroatoms that contains; R also can be halogen or Wasserstoffatoms.Concrete silicoorganic compound are like trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, 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 according to the 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 Vilaterm and ethene and terminal 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.Hydrogen or other compounds that can play the chain-transfer agent effect can be used for the molecular weight of controlling polymers.
The present invention is owing to adopt the maleic acid ester compound of special unsaturated heterocycle structure to make internal electron donor; Its unique electronic effect makes the high comprehensive performance of catalyzer when being used for propylene (being total to) polymerization, can obtain gratifying polymerization yield rate; And the stereospecificity of polymkeric substance is higher; Catalyzer is also fine to the susceptibility of hydrogen accent simultaneously, and the MWD broad of resulting polymers helps the polymkeric substance developing different numbers.
Embodiment
Embodiment given below is for the present invention is described better, rather than limits the invention.
Testing method:
1, polymericular weight and MWD MWD (MWD=M
w/ M
n): adopt the gel permeation chromatography method, use Alliance-GPCV2000 to measure down at 135 ℃ as solvent with orthodichlorobenzene.
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 1-7
One, the maleic acid ester compound is synthetic
(1) synthetic 7-oxabicyclo [2.2.1] heptan-2,5-diene-2,3-dioctyl phthalate dimethyl ester
In the 100mL flask, add the new furans that steams of 14.2g dimethyl butyn and 50mL, reflux is 12 hours under stirring.After reaction mixture was chilled to room temperature, column chromatography for separation got oily liquids product 19.3g, yield 92%.
1H NMR (TMS, CDCl
3, 400MHz) analytical results: δ 5.79 (q, 2H, alkene H); δ 5.15 (q, 2H, CH); δ 3.73 (s, 6H, CH
3).
(2) synthetic 7-oxabicyclo [2.2.1] heptan-2,5-diene-2,3-dicarboxylate
With 10.5g 7-oxabicyclo [2.2.1] heptan-2,5-diene-2,3-dioctyl phthalate dimethyl ester joins in the beaker that 100mL50% sodium hydroxide is housed, stirring at room 2 hours; Add the Hydrogen chloride acidifying, filter, washing; Weigh after drying, get 9.1g 7-oxabicyclo [2.2.1] heptan-2,5-diene-2; The 3-dioctyl phthalate, yield 99% can directly be used for next step reaction.
In the 100mL flask, add 4.55g 7-oxabicyclo [2.2.1] heptan-2,5-diene-2,3-dioctyl phthalate, 50mL absolute ethyl alcohol and 1.0g tosic acid, reflux is 12 hours under stirring.After reaction mixture is chilled to room temperature, add saturated aqueous common salt, extracted with diethyl ether 3 times, combining extraction liquid is used anhydrous sodium sulfate drying, filters, solvent evaporated, column chromatography for separation gets oily liquids product 5.4g, yield 91%.
1H NMR (TMS, CDCl
3, 400MHz) analytical results: δ 5.83 (q, 2H, alkene H); δ 5.14 (q, 2H, CH); δ 4.21 (q, 4H, CH
2CH
3); δ 1.29 (t, 6H, CH
3).
(3) synthetic 7-oxabicyclo [2.2.1] heptan-2,5-diene-2,3-dioctyl phthalate diisobutyl ester
With 7-oxabicyclo [2.2.1] heptan-2,5-diene-2,3-dioctyl phthalate and dry isobutanol are raw material, adopt aforesaid method to obtain.
(4) synthetic 7-oxabicyclo [2.2.1] heptan-2,5-diene-2,3-dioctyl phthalate di-n-butyl
With 7 oxabicyclos [2.2.1] heptan-2,5-diene-2,3-dioctyl phthalate and anhydrous normal butyl alcohol are raw material, adopt aforesaid method to obtain.
Two, the preparation of catalyst component a
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 maleic acid ester compound 7.4mmol in the table 1 respectively, was warming up to 100 ℃ in 1 hour, kept venting filtrating 2 hours.Add TiCl
4100mL rose to 120 ℃ in 1 hour, kept venting filtrating 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 catalyst component vacuum-drying that obtains.
Comparative example 1-2
Press the preparation method of the foregoing description catalyst component, just internal electron donor is replaced with 2-isobutyl-ethyl maleate and ethyl maleate respectively, the same embodiment of propylene polymerization condition, the result sees table 1.
The propylene polymerization experiment
Catalyst component catalyzing propone polymerization with the foregoing description 1-7 and comparative example 1-2.
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 catalyst component 20mg and the 1.2L hydrogen of the foregoing description 1-12 and comparative example 1-2 again, feeds liquid propene 2.5L, is warming up to 70 ℃, keeps this temperature 1 hour.Cooling, pressure release to 1 normal atmosphere obtains Vestolen PP 7052.Polymerization result is listed in table 1.
Table 1. catalyzing propone polymerization result
The vinyl polymerization experiment
Volume is the stainless steel autoclave of 10L, after high pure nitrogen is fully replaced, starts stirring, under nitrogen protection, progressively in still, adds the catalyst solid constituent and the 5.0mmol promotor AlEt of 2L hexane, 20mg embodiment 2 gained
3, be warming up to 75 ℃ after, 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 Vilaterm 580g after the thorough drying.
Ethene and copolymerization of propylene experiment
Volume is the stainless steel autoclave of 10L, after high pure nitrogen is fully replaced, starts stirring, under nitrogen protection, progressively in still, adds the catalyst solid constituent and the 5.0mmol promotor AlEt of 2L hexane, 20mg embodiment 2 gained
3, feed 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, and make-up ethylene gas makes its dividing potential drop reach 0.75MPa in still then; 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 963g with polymkeric substance after the thorough drying.
Claims (20)
1. Ziegler-Natta catalyst specifically comprises:
(a) by weight percentage, the catalyst component that is selected from least a maleic acid ester in the general formula (I) that contains 10～25% magnesium, 1～10% titanium, 40～60% halogens and 1～30%;
(b) alkylaluminium cpd;
(c) randomly, external electron donor,
Wherein, radicals X is oxygen, sulphur or nitrogen heteroatom in the general formula (I); Radicals R
1And R
2Being same to each other or different to each other, is C
1-C
20Line style or alkyl, alkenyl, naphthenic base, aryl, arylalkyl or the kiki fang alkyl group of branching, the optional heteroatoms that contains; Radicals R
3To R
6Be same to each other or different to each other, be hydrogen or C
1-C
20Line style or alkyl, alkenyl, naphthenic base, aryl, arylalkyl or the kiki fang alkyl group of branching, optional heteroatoms and the R of containing
3-R
6In plural group mutually bonding generate one or several condensed ring structure;
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.
2. catalyzer according to claim 1 is characterized in that in the maleic acid ester general formula compound that X is a Sauerstoffatom.
3. catalyzer according to claim 1 is characterized in that in the maleic acid ester general formula compound R
1And R
2Be C
1-C
10Alkyl, naphthenic base or arylalkyl.
4. catalyzer according to claim 3 is characterized in that in the maleic acid ester general formula compound R
1And R
2Be C
1-C
10Alkyl.
5. catalyzer according to claim 4 is characterized in that in the maleic acid ester general formula compound R
1And R
2Be ethyl, normal-butyl or isobutyl-.
6. catalyzer according to claim 1 is characterized in that in the maleic acid ester general formula compound R
3And R
4, R
5And R
6In to have one group of group at least be hydrogen.
7. catalyzer according to claim 6 is characterized in that in the maleic acid ester general formula compound R
3To R
6Be hydrogen.
8. catalyzer according to claim 1 is characterized in that the maleic acid ester general formula compound is 7-oxabicyclo [2.2.1] heptan-2,5-diene-2,3-dioctyl phthalate dimethyl ester, 7-thia dicyclo [2.2.1] heptan-2; 5-diene-2,3-dioctyl phthalate dimethyl ester, 7-amine-dicyclo [2.2.1] heptan-2,5-diene-2,3-dioctyl phthalate dimethyl ester, 7-oxabicyclo [2.2.1] heptan-2; 5-diene-2,3-dicarboxylate, 1,4-dimethyl--7-oxa--dicyclo [2.2.1] heptan-2,5-diene-2; 3-dioctyl phthalate di-n-butyl, 5,6-dimethyl--7-oxa--dicyclo [2.2.1] heptan-2,5-diene-2; 3-dioctyl phthalate diisobutyl ester or 1,4,5; 6-tetramethyl--7-oxa--dicyclo [2.2.1] heptan-2,5-diene-2,3-dicarboxylate.
9. catalyzer according to claim 1 is characterized in that the magnesium in the catalyst component is provided by the magnesium halide alcohol adduct of size-grade distribution 20～250 μ m, and magnesium halide alcohol adduct satisfies formula M g (OR ')
mX
(2-m)PROH, R ' is C in the formula
1～C
20Alkyl, arylalkyl or aryl; X is a halogen; M is the integer of 0≤m＜2; P is the decimal or the integer of 0＜p＜6; R is C
1～C
20The alkyl or aryl alkyl.
10. catalyzer according to claim 9 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.
11. catalyzer according to claim 10, 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.
12. catalyzer 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 1～20 alkyl in the formula; X is a halogen; N=1～4.
13. catalyzer according to claim 12 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.
14. catalyzer according to claim 13 is characterized in that the titanium in the catalyst component is provided by titanium tetrachloride.
15. catalyzer according to claim 1 is characterized in that alkylaluminium cpd is a trialkyl aluminium compound.
16. catalyzer according to claim 15 is characterized in that alkylaluminium cpd is triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium.
17. catalyzer according to claim 1 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, naphthenic base or aryl with R '.
18. catalyzer according to claim 17; It is characterized in that external electron donor is trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, 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.
19. catalyzer according to claim 18 is characterized in that external electron donor is a cyclohexyl methyl dimethoxy silane.
20. catalyzer according to claim 1 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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| WO2016114668A1 (en) | 2015-01-16 | 2016-07-21 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Method to prepare phenolics from biomass |
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| CN1041162A (en) * | 1988-09-14 | 1990-04-11 | 三井石油化学工业株式会社 | Olefin polymerization catalysis, catalyst component and with the polyolefinic film of method, gained and the injection-molded item thereof of this polymerizing olefins with catalyst |
| US6887817B2 (en) * | 2001-10-09 | 2005-05-03 | Formosa Plastics Corporation, U.S.A. | Olefin polymerization catalyst and process for preparing polyolefins using said catalyst |
| CN1714105A (en) * | 2001-09-13 | 2005-12-28 | 巴塞尔聚烯烃意大利有限公司 | Components and catalysts for the polymerization of olefins |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041162A (en) * | 1988-09-14 | 1990-04-11 | 三井石油化学工业株式会社 | Olefin polymerization catalysis, catalyst component and with the polyolefinic film of method, gained and the injection-molded item thereof of this polymerizing olefins with catalyst |
| CN1714105A (en) * | 2001-09-13 | 2005-12-28 | 巴塞尔聚烯烃意大利有限公司 | Components and catalysts for the polymerization of olefins |
| US6887817B2 (en) * | 2001-10-09 | 2005-05-03 | Formosa Plastics Corporation, U.S.A. | Olefin polymerization catalyst and process for preparing polyolefins using said catalyst |
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