CN104045748A - Solid catalyst component for olefin polymerization and catalyst - Google Patents
Solid catalyst component for olefin polymerization and catalyst Download PDFInfo
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- CN104045748A CN104045748A CN201410265458.XA CN201410265458A CN104045748A CN 104045748 A CN104045748 A CN 104045748A CN 201410265458 A CN201410265458 A CN 201410265458A CN 104045748 A CN104045748 A CN 104045748A
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Abstract
The invention provides a solid catalyst component for olefin polymerization. The catalyst component comprises Mg, Ti, halogen and an electron donor, wherein the electron donor is selected from at least one unsaturated ring-substituted acid ester compound in a general formula (I) and at least one single-functional group or multi-functional group electron donor compound of ether, ester, ketone or amine. The invention also provides a catalyst containing the solid catalyst compound and application of the catalyst in olefin polymerization reaction, especially application in propylene polymerization reaction. The solid catalyst component disclosed by the invention has excellent activity, and the high isotactic polyolefin product can be obtained.
Description
Technical field
The present invention relates to contain at least two kinds of electron donor compounds for CH
2the ingredient of solid catalyst of=CHR olefinic polymerization, wherein R is hydrogen or the hydrocarbyl group containing 1-12 carbon atom, electron donor compound wherein a kind of unsaturated ring that is selected from specific type replaces two ester compounds, and another kind is selected from simple function group or the polyfunctional group electron donor compound of ether, ester, ketone or amine.
Background technology
Electron donor compound can change the character in olefinic polymerization Ziegler-Natta catalyst active centre most possibly, thereby farthest change the performance of catalyzer, therefore the research of efficient Ziegler-Natta catalyst is exactly the research of seeking better electron donor in the sense.At present mainly concentrate on traditional fatty acid ester and aromatic esters compound for the research of internal electron donor both at home and abroad; Two ethers (for example EP0361493, EP0728724) and succinate compound (for example WO9856834, WO0063261, WO03022894) compound; And diol-lipid (for example CN1580033, CN1580034, CN1580035) compound etc.
But above-claimed cpd all exists certain problem in actual applications as the electron donor of olefin polymerization catalyst components, the molecular weight distribution of the catalyst system resulting polymers that as used prepared by diether compound is narrower, and the polymeric articles molecular weight distribution of succinate compound catalyst system is wider, the activity of diol-lipid catalyst system is often not as two ethers system ideals.In order to make catalyzer can obtain the comparatively over-all properties of balance, develop various novel compounds and be applied to and prepared Ziegler-Natta catalyst.
Each internal electron donor has its unique performance, also respectively has certain deficiency, therefore can be by composite two or more electron donors use to reaching desirable over-all properties.LyondellBasell adopts ethyl benzoate and two kinds of composite uses of electron donor of diisobutyl phthalate (WO03002617), with the racemic form of DIBP with two kinds of compounds of meso-form are composite has prepared catalyzer (WO2004013193) etc. as internal electron donor.Mo Lini etc. (WO9957160) are by composite to 1,3-, bis-ethers electron donors and malonic ester compounds, and the propene polymer that described catalyst component can be produced not only has the degree of isotacticity of wide region but also have Senior Two toluene insoluble numerical value.Mo Lini etc. (CN1798774) are applied to production two-way stretch PP film (BOPP) field by the catalyst component from succinate and the composite preparation of other electron donor compounds (as succinate and and the composite WO0230998 of phthalic ester) again, can obtain the polymkeric substance of Senior Two toluene insoluble, high stereoblock content and wide molecular weight distribution.Dow chemical company and TOTAL petroleum chemicals company etc. have also carried out the exploitation of electron donor compounded technology.A Lansitan Dare top grade (CN101472963, CN101479304) is by diether compounds and the direct or indirect composite Kaolinite Preparation of Catalyst of succinate compound.Utilize feature that diether narrowly distributing, orientation property are high and the wide feature of succinate molecular weight distribution to obtain that orientation property is high, molecular weight distribution is wide, the propene polymer of good fluidity.The composite mode of this electron donor can be applicable in a reactor and produces bimodal polypropylene, gained polypropylene demonstrate good flow, contraction and processing behavior.
But on the whole, the balance of Ziegler-Natta catalyst component prepared by the various composite internal electron donors activity/degree of isotacticity when for olefinic polymerization is very not satisfactory, therefore still needs it further to research and develop.
Summary of the invention
The polyfunctional compound with ad hoc structure provided by the invention, the unsaturated ring as shown in logical formula I replaces two ester compounds, this compounds contains the bifunctional that can participate in coordination, and has specific ring texture to play the steric configuration of steric hindrance and fixing bifunctional.
Contriver finds, in the time that this compounds is prepared to Ziegler-Natta catalyst component for electron donor, can make catalyst component have good activity and degree of isotacticity.In addition, in the time that the catalyzer that adopts single internal electron donor to prepare cannot meet the particular requirement of polypropylene product, can be in the time of preparation Z-N catalyzer, use two or more internal electron donor simultaneously, and improve the over-all properties of Z-N catalyzer by adjusting the content of different internal electron donors in Z-N catalyzer.
The object of the present invention is to provide a kind of unsaturated ring replace two ester compounds be internal electron donor and with other composite prepared ingredient of solid catalyst of internal electron donor compound openly.
Another object of the present invention is to provide the preparation method of this ingredient of solid catalyst.
A further object of the present invention is to provide this ingredient of solid catalyst at CH
2application in the preparation of=CHR olefin polymerization catalysis.
In order to realize object of the present invention, the invention provides the ingredient of solid catalyst for olefinic polyreaction, (CH
2=CHR alkene, wherein R is hydrogen or the hydrocarbyl group containing 1-12 carbon atom), it comprises Mg, Ti, halogen and a kind of electron donor, this electron donor replaces two ester compounds at least one the unsaturated ring in (i) is selected from logical formula I, and (ii) simple function group or the polyfunctional group electron donor compound of at least one ether, ester, ketone or amine:
Wherein, A, B, C, D and E are all selected from carbon atom or are selected from the heteroatoms in N, O and S; W, X, Y, Z and m are 0 or 1; Condition is
In the time that n equals 0:
V) A, B, C and D are carbon atom, and X, Y, Z and W are 1; Or
VI) A is nitrogen-atoms, and B, C and D are carbon atom, and W is that 0, X, Y and Z are 1; Or
VII) A and D are nitrogen-atoms, and B and C are carbon atom, and W and Z are that 0, X and Y are 1; Or
VIII) D is nitrogen-atoms, and A, B and C are carbon atom, and Z is that 0, W, X and Y are 1; Or
In the time that n equals 1:
Iv) A, B, C, D and E are carbon atom, and m is that 2, W, X, Y and Z are 1; Or
V) E is nitrogen-atoms, and A, B, C and D are carbon atom, and m is that 1, W, X, Y and Z are 1; Or
Vi) E is Sauerstoffatom, and A, B, C and D are carbon atom, and m is that 0, W, X, Y and Z are 1; Or
Iii) E is sulphur atom, and A, B, C and D are carbon atom, and m is that 0, W, X, Y and Z are 1; Or
Iv) D and E are nitrogen-atoms, and A, B and C are carbon atom, and m is that 1, W, X and Y are that 1, Z is 0.
R
1and R
2for identical or not identical C
1-C
20alkyl, such as C
1-C
20straight or branched alkyl, alkenyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl and C
7-C
20aralkyl; Identical or different R
3-R
7hydrogen atom, halogen atom, Sauerstoffatom, sulphur atom and C
1-C
20alkyl, such as C
1-C
20straight or branched alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl and C
7-C
20aralkyl;
Above-mentioned R
1-R
7at random comprise one or several R atom as carbon atom or hydrogen atom or both substituents, R atom is heteroatoms, the C of straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl and C
7-C
20aralkyl; Wherein R
1-R
7any two groups mutually bonding generate one or more volutions, condensed ring structure.
The specific examples that is included in the compound in logical formula I is:
3,5-phenylbenzene 2H pyrroles-2,2-dicarboxylate; 3-(3-chloro-phenyl-)-5-methyl-pyrroles-2,2-dicarboxylate; 3-(3-bromophenyl)-5-methyl-pyrroles-2,2-dicarboxylate; Diethyl-3-(to chlorobenzene)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Fluorenes-9,9-dioctyl phthalate dimethyl ester; Fluorenes-9,9-dicarboxylate; Fluorenes-9,9-dioctyl phthalate di-n-propyl ester; Fluorenes-9,9-dioctyl phthalate diisopropyl ester; Fluorenes-9,9-dioctyl phthalate di-n-butyl; Fluorenes-9,9-dioctyl phthalate diisobutyl ester; Fluorenes-9,9-dioctyl phthalate two n-pentyl esters; Fluorenes-9, the just own ester of 9-dioctyl phthalate two; Fluorenes-9, the positive heptyl ester of 9-dioctyl phthalate two; Fluorenes-9,9-dioctyl phthalate di-n-octyl; 9-methyl-formiate-9-ethyl formate-fluorenes; 9-methyl-formiate-9-formic acid n-propyl-fluorenes; 9-methyl-formiate-9-isopropyl formate-fluorenes; 9-methyl-formiate-9-n-buty formate-fluorenes; 9-methyl-formiate-9-tetryl formate-fluorenes; 9-ethyl formate-9-formic acid n-propyl-fluorenes; 9-ethyl formate-9-isopropyl formate-fluorenes; 9-ethyl formate-9-n-buty formate-fluorenes; 9-ethyl formate-9-tetryl formate-fluorenes dimethyl 4H-benzo <g> thia <2,3-e> indazole-4,4-dicarboxylic acid esters; 2H-pyrroles-2, diethyl-5-phenyl-3 (to toluene), 2-manthanoate; Diethyl-3 (to anisole)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Diethyl 5-(to nitro)-3-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Diethyl-2,3-phenylbenzene-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(4-chlorobenzene)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(4-p-methoxy-phenyl)-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-(4-methylbenzene)-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-3-(4-oil of mirbane)-1H-indenes-1,1-dicarboxylic acid esters; Dimethylamino-4-five methoxycarbonyl-1,2,3,5,5-, five methoxycarbonyl cyclopentadiene; 3-phenyl-indenes-1,1-dioctyl phthalate methyl esters; Dimethyl-5-(to chlorobenzene) 3-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Dimethyl 3,4-bis-(to chlorobenzene) 2H-pyrroles-dicarboxylic acid esters; Dimethyl 3-(p-oil of mirbane)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Dimethyl 3-(m-oil of mirbane)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Dimethyl 5-(m-oil of mirbane)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Dimethyl 5,6-dimethyl-5H, 6H-encircles penta 2 indoles-11,11-dicarboxylic acid esters; 1-(2-oil of mirbane sulphur)-2,3,4,5,5-methyl-formiate-cyclopentadiene; 1-(2,4-dinitrobenzene)-2,3,4,5,5-five methyl-formiates-cyclopentadiene; Methyl-2-the tertiary butyl-3-methyl isophthalic acid H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-methyl-2-trimethyl silicane-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-methyl-2-phenyl-indenes-1,1-dicarboxylic acid esters; Diethyl-2,3-bis--n-propyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-3-methylol-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-2-the tertiary butyl-5,6-dimethoxy-3-methyl isophthalic acid H-indenes-1,1-dicarboxylic acid esters; Dimethyl-2-phenyl-3-(thia-2-yl)-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-3-(2-toluene) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-(2-methoxycarbonyl phenyl)-2 phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-(4-trifluoromethylbenzene) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-(4-phenyl methyl ketone) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-2-(hexamethylene 1-alkene)-3-(4-phenyl methyl ketone)-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 2-[(ethoxy acyl group) methyl]-1H-indenes-1,1-dicarboxylic acid esters; 1,1-diethyl-1H-indenes-1,1-dicarboxylic acid esters; The chloro-5 methyl-pyrazoles of 7-[4,3-d] pyrimidine-3,3-dioctyl phthalate ethyl ester; The chloro-7-methyl-pyrazoles of 5-[4,3-d] pyrimidine-3,3-dioctyl phthalate ethyl ester; 5-amino-7-methyl-pyrazoles [4,3-d] pyrimidine-3,3-dioctyl phthalate ethyl ester; 7-methoxyl group-5-methyl-pyrazoles [4,3-d] pyrimidine-3,3-dioctyl phthalate ethyl ester; 1-p-totuidine base-2,3,4,5,5-, five methoxycarbonyl cyclopentadiene; Dimethyl-3H-phenanthro-< 9,10-c > pyrazoles-3,3-dicarboxylic acid esters; 3,3-bis-(methoxycarbonyl)-3H-indazole; 3,3-bis-(ethoxycarbonyl) 3H-indazole; 1-trichloromethyl-2,3,4,5,5-, five methoxycarbonyl cyclopentadiene; 1-(2-methyl-4-oil of mirbane)-five methoxycarbonyl cyclopentadiene; 1-(the iodo-4-oil of mirbane of 2-)-five methoxycarbonyl cyclopentadiene; 2-(the iodo-4-oil of mirbane of 2-)-1,3,4,5,5-five methoxycarbonyl cyclopentadiene; 1-(2,4-dinitrobenzene)-2,3,4,5,5-five methoxycarbonyl cyclopentadiene; 4-benzyl-1, poly-(methoxycarbonyl) cyclopentadiene of 2,3,5,5-five; 3-benzyl-1, poly-(methoxycarbonyl) cyclopentadiene of 2,4,5,5-five; 2-(trifluoromethyl)-5-carbonyl-3,3-bis-(methoxycarbonyl)-3H-indoles; 2-(trifluoromethyl)-5-carbonyl-7-methyl-3,3-bis-(methoxycarbonyl)-3H-indoles; 3-(trifluoromethyl)-5-hydroxyl-7-methoxyl group-3,3-bis-(methoxycarbonyl)-3H-indoles; 2H-pyrroles-2, diethyl-3-phenyl-5 (to toluene), 2-dicarboxylic acid esters; Diethyl-2-(4-chlorobenzene)-5-morpholine-4H-imidazoles-4,4-dicarboxylic acid esters; 4,5,5-tricarboxylic acid methyl esters-1,2,3-trichlorine cyclopentadiene; Methyl-3-methyl-4-trimethyl silicane-ring penta-2,4-diene-1,1-dicarboxylic acid esters; Diethyl-2,5-phenylbenzene-4H-imidazoles-4,4-dicarboxylic acid esters; Diethyl-3-benzyl-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-3-(4-(methoxycarbonyl) phenyl) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-3-(4-acetylbenzene) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-methoxyl methyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-2-the tertiary butyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-the tertiary butyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 2-normal-butyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl 2-normal-butyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl 2-n-hexyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(3-cyano group-1-propyl group)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-diethoxy methyl isophthalic acid H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(4-methoxyphenyl)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(1-tetrahydrobenzene)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(cyclohexyl)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-3-(3-toluene)-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-3-(3-oil of mirbane)-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl 13H-indeno [1,2-e]-Fei-13,13-dicarboxylic acid esters; Diethyl-2-hexyl-3-(4-methoxyphenyl) 1H-indenes-1,1-dicarboxylic acid esters; Ring penta [c] thia-5,5-dioctyl phthalate ethyl ester; 4-[4-[4-(methylsulphonic acid) benzene] 1,1-bis-(methoxyl group) ring penta-2,4-diene-3-yl] pyridine; Fluorenes-4,9, the 9-dioctyl phthalate-4-tertiary butyl-9,9-dimethyl ester; 4-(4-amino-pyridine-3-base carbamyl)-fluorenes-9,9-dioctyl phthalate methyl esters; 4-(3-amino-pyridine-4-base carbamyl)-fluorenes-9,9-dioctyl phthalate dimethyl ester; The iodo-2-phenyl-1H-of diethyl-3-indenes-1,1-dicarboxylic acid esters; The iodo-2-n-pentyl-1H-of diethyl-3-indenes-1,1-dicarboxylic acid esters; The iodo-2-of diethyl-3-(3 methoxyphenyl)-1H-indenes-1,1-dicarboxylic acid esters; The iodo-2-of diethyl-3-(naphthalene-2-yl)-1H-indenes-1,1-dicarboxylic acid esters; Di-n-hexyl-fluorenes-9,9-dicarboxylic acid esters; Two n-heptyls-fluorenes-9,9-dicarboxylic acid esters; Diethyl-2-benzene-3H-indenes-3,3-dicarboxylic acid esters; The bromo-1H-of diethyl-2-indenes-1,1-dicarboxylic acid esters;
1-ethyl-1-methyl-cyclohexyl-2,5-diene-1,1-dicarboxylic acid esters; N, 4,4-, tri-ethoxy carbon back-Isosorbide-5-Nitrae-dihydro-pyridines; 2,6-phenylbenzene-4,4-dimethoxycarbonyl-4H-pyrans; 2,6-phenylbenzene-4,4-dimethoxycarbonyl-Isosorbide-5-Nitrae-dihydropyridine; 2,6-bis-(4-chlorobenzene)-4,4-dimethoxycarbonyl-4H-pyrans; 2,6-bis-(4-methoxyphenyl)-4,4-dimethoxycarbonyl-4H-pyrans; 2,6-bis-(4-chlorobenzene)-4,4-dimethoxycarbonyl-Isosorbide-5-Nitrae-dihydropyridine; 2,6-bis-(4-methoxyphenyl)-4,4-dimethoxycarbonyl-Isosorbide-5-Nitrae-dihydropyridine; 1-cyclopentyl-4,4-bis-(methoxycarbonyl)-Isosorbide-5-Nitrae-dihydropyridine; 1-n-hexyl-4,4-bis-(methoxycarbonyl)-Isosorbide-5-Nitrae-dihydropyridine; 1-methoxy-6,6-bis-methanoyl methyl-cyclohexyl-Isosorbide-5-Nitrae-diene; Dimethyl Isosorbide-5-Nitrae-dihydronaphthalene-1,1-dicarboxylic acid esters; 2,6-bis-(4-chlorobenzene)-4,4-dimethoxy acyl group-4H-thiapyran; Diethyl-3-bromo-Isosorbide-5-Nitrae-dihydro-1-methyl pyridazino[3,4-b] quinoxaline-4,4-dicarboxylic acid esters; The bromo-3-of diethyl-5-phenyl-Isosorbide-5-Nitrae-dihydrogen dazin-4,4-dicarboxylic acid esters; Three hexyls-3-phenyl-Isosorbide-5-Nitrae-dihydrogen dazin-4,4,5-front three acid esters; 1-styroyl-bis-(methoxy acyl group) Isosorbide-5-Nitrae-dihydropyridine; Diethyl-2-methyl-6-benzene (4H-pyrans) 4,4-dicarboxylic acid esters; 1-(2-menaphthyl)-4,4-bis-(methoxy acyl group)-Isosorbide-5-Nitrae-dihydropyridine; Dimethyl-3-ethanoyl-1-toluquinoline-4,4 (1H)-dicarboxylic acid esters.
The compound of logical formula I preferably includes the compound of logical formula II:
Wherein R
1-R
6group is as the definition in logical formula I.
The compound of logical formula II preferably includes the compound of logical formula III:
Wherein R
1, R
2group is as the definition in logical formula I, and R ' is the C of identical or not identical hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl and C
7-C
20aralkyl.
In 5-membered ring compounds shown in logical formula II or (III), more suitable particular compound example has:
Fluorenes-9,9-dioctyl phthalate dimethyl ester; Fluorenes-9,9-dicarboxylate; Fluorenes-9,9-dioctyl phthalate di-n-propyl ester; Fluorenes-9,9-dioctyl phthalate diisopropyl ester; Fluorenes-9,9-dioctyl phthalate di-n-butyl; Fluorenes-9,9-dioctyl phthalate diisobutyl ester; Fluorenes-9,9-dioctyl phthalate two n-pentyl esters; Fluorenes-9, the just own ester of 9-dioctyl phthalate two; Fluorenes-9, the positive heptyl ester of 9-dioctyl phthalate two; Fluorenes-9,9-dioctyl phthalate di-n-octyl; 9-methyl-formiate-9-ethyl formate-fluorenes; 9-methyl-formiate-9-formic acid n-propyl-fluorenes; 9-methyl-formiate-9-isopropyl formate-fluorenes; 9-methyl-formiate-9-n-buty formate-fluorenes; 9-methyl-formiate-9-tetryl formate-fluorenes, 9-ethyl formate-9-formic acid n-propyl-fluorenes; 9-ethyl formate-9-isopropyl formate-fluorenes; 9-ethyl formate-9-n-buty formate-fluorenes; 9-ethyl formate-9-tetryl formate-fluorenes.
Unsaturated ring of the present invention replaces malonic ester can be synthetic by various reactions.One of them is synthetic by following formula three-step reaction: steps A is to react with carbonic acid gas and alkyl lithium reagents encircling accordingly substitution compound, or reacts with alkyl-dimethyl ester and sodium hydride and be prepared into cyclic hydrocarbon radical replacement formic acid (can referring to US4564700A1); Step B is by upper step product and corresponding alcohol R
1oH reaction esterification is manthanoate, or with suitable ester class precursor direct addition be that cyclic hydrocarbon replaces formic acid fat (can referring to Journal of the Chemical Society, 1949, P2182,2185); Step C be by upper step product with prepare (can referring to Analytical Chemistry, vol.32, NO.4, April1960) with the precursor addition of suitable haloformate.
In addition, when unsaturated ring replaces two ester compound R
1and R
2when identical, available corresponding unsaturated ring substitution compound directly prepares with lithium reagent (as n-Butyl Lithium or lithium diisopropyl amido) and haloformate single step reaction, and each substituting group leads to together definition in formula I (can referring to Tetrahedron Letters50 (2009) 6057-6059):
Ingredient of solid catalyst of the present invention replaces two ester compounds except the unsaturated ring that contains described logical formula I, also comprise at least another kind of electron donor compound, this compound is selected from the Lewis alkali that contains one or more electronegativity groups, electron donor atom is wherein selected from the group of N, O, S, P, As or Sn composition, preferably from the electron donor compound of two ethers, ester class, diones and Diamines.In the time that unsaturated ring replaces two ester compounds and uses, can obtain the catalyzer that performance can regulate together with other above-mentioned published internal electron donor compounds.
The unsaturated ring of logical formula I replaces another kind of electron donor compound outside two ester compounds preferably, is selected from 1 of logical formula IV, 3-the third two ethers:
Wherein: R, R
1, R
2, R
3, R
4and R
5can be identical or different, represent H or have straight chain or branched-alkyl, cycloalkyl, aryl, alkaryl or the aralkyl of 1-18 carbon atom; R
6and R
7can be identical or different, representative has the straight chain of 1-20 carbon atom or branched-alkyl, the cycloalkyl of a 3-20 carbon atom, the aryl of a 5-20 carbon atom, alkaryl and the aralkyl of a 7-20 carbon atom; R-R
7in one or more groups can link formation ring texture, all can comprise the one or more heteroatomss that are selected from halogen, N, O, S, P and Si.
The concrete example of the ethers that can advantageously use comprises: 2-(2-ethylhexyl) 1, 3-Propanal dimethyl acetal, 2-sec.-propyl-1, 3-Propanal dimethyl acetal, 2-butyl-1, 3-Propanal dimethyl acetal, 2-sec-butyl-1, 3-Propanal dimethyl acetal, 2-cyclohexyl-1, 3-Propanal dimethyl acetal, 2-phenyl-1, 3-Propanal dimethyl acetal, the 2-tertiary butyl-1, 3-Propanal dimethyl acetal, 2-cumyl-1, 3-Propanal dimethyl acetal, 2-(2-phenylethyl)-1, 3-Propanal dimethyl acetal, 2-(2-cyclohexyl ethyl)-1, 3-Propanal dimethyl acetal, 2-(rubigan)-1, 3-Propanal dimethyl acetal, 2-(diphenyl methyl)-1, 3-Propanal dimethyl acetal, 2 (1-naphthyls)-1, 3-Propanal dimethyl acetal, 2 (to fluorophenyl)-1, 3-Propanal dimethyl acetal, 2 (1-decahydro naphthyls)-1, 3-Propanal dimethyl acetal, 2 (to tert-butyl-phenyl)-1, 3-Propanal dimethyl acetal, 2, 2-dicyclohexyl-1, 3-Propanal dimethyl acetal, 2, 2-diethyl-1, 3-Propanal dimethyl acetal, 2, 2-dipropyl-1, 3-Propanal dimethyl acetal, 2, 2-dibutyl-1, 3-Propanal dimethyl acetal, 2, 2-diethyl-1, 3-di ethyl propyl ether, 2, 2-bis-cyclopentyl-1, 3-Propanal dimethyl acetal, 2, 2-dipropyl-1, 3-di ethyl propyl ether, 2, 2-dibutyl-1, 3-di ethyl propyl ether, 2-methyl-2-ethyl-1, 3-Propanal dimethyl acetal, 2-methyl-2-propyl-1, 3-Propanal dimethyl acetal, 2-methyl-2-benzyl-1, 3-Propanal dimethyl acetal, 2-methyl-2-phenyl-1, 3-Propanal dimethyl acetal, 2-methyl-2-cyclohexyl-1, 3-Propanal dimethyl acetal, 2-methyl-2-methylcyclohexyl-1, 3-Propanal dimethyl acetal, 2, two (rubigan)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the 2-phenylethyls)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the 2-cyclohexyl ethyls)-1 of 2-, 3-Propanal dimethyl acetal, 2-methyl-2-isobutyl--1, 3-Propanal dimethyl acetal, 2-methyl-2-(2-ethylhexyl)-1, 3-Propanal dimethyl acetal, 2, two (the 2-ethylhexyls)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (p-methylphenyl)-1 of 2-, 3-Propanal dimethyl acetal, 2-methyl-2-sec.-propyl-1, 3-Propanal dimethyl acetal, 2, 2-diisobutyl-1, 3-Propanal dimethyl acetal, 2, 2-phenylbenzene-1, 3-Propanal dimethyl acetal, 2, 2-dibenzyl-1, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-cyclopentyl-1, 3-Propanal dimethyl acetal, 2, two (cyclohexyl methyl)-1 of 2-, 3-Propanal dimethyl acetal, 2, 2-diisobutyl-1, 3-di ethyl propyl ether, 2, 2-diisobutyl-1, 3-dibutoxy propane, 2-isobutyl--2-sec.-propyl-1, 3-Propanal dimethyl acetal, 2, 2-bis--sec-butyl-1, 3-Propanal dimethyl acetal, 2, 2-bis--tertiary butyl-1, 3-Propanal dimethyl acetal, 2, 2-di neo-pentyl-1, 3-Propanal dimethyl acetal, iso-propyl group-the 2-of 2-isopentyl-1, 3-Propanal dimethyl acetal, 2-phenyl-2-benzyl-1, 3-dimethoxy _ _ base propane, 2-cyclohexyl-2-cyclohexyl methyl-1, 3-Propanal dimethyl acetal.Two (the methoxymethyl)-cyclopentadiene of 1,1-; Two (methoxymethyl)-2,3,4 of 1,1-, 5-tetramethyl-ring pentadiene; Two (methoxymethyl)-2,3,4 of 1,1-, 5-tetraphenyl cyclopentadiene; Two (methoxymethyl)-2,3,4 of 1,1-, 5-ptfe ring pentadiene; Two (methoxymethyl)-3 of 1,1-, 4-bis-cyclopentyl cyclopentadiene; Two (methoxymethyl) indenes of 1,1-; Two (methoxymethyl)-2 of 1,1-, 3-dimethyl indenes; Two (methoxymethyl)-4,5,6 of 1,1-, 7-tetrahydroindene; Two (methoxymethyl)-2,3,6 of 1,1-, 7-tetrafluoro indenes; Two (methoxymethyl)-4 of 1,1-, 7-dimethyl indenes; Two (methoxymethyl)-3 of 1,1-, 6-dimethyl indenes; Two (the methoxymethyl)-4-phenylindan of 1,1-; Two (the methoxymethyl)-4-phenyl-2-methyl indenes of 1,1-; Two (the methoxymethyl)-4-cyclohexyl indenes of 1,1-; Two (methoxymethyl)-7-(3,3, the 3-trifluoro propyl) indenes of 1,1-; Two (the methoxymethyl)-7-trimethyl silyl indenes of 1,1-; Two (the methoxymethyl)-7-trifluoromethyl indenes of 1,1-; Two (methoxymethyl)-4 of 1,1-, 7-dimethyl-4,5,6,7-tetrahydroindene; Two (the methoxymethyl)-7-methyl indenes of 1,1-; Two (the methoxymethyl)-7-cyclopentyl indenes of 1,1-; Two (the methoxymethyl)-7-sec.-propyl indenes of 1,1-; Two (the methoxymethyl)-7-cyclohexyl indenes of 1,1-; Two (the methoxymethyl)-7-tertiary butyl indenes of 1,1-; Two (the methoxymethyl)-7-tertiary butyl-2-methyl indenes of 1,1-; Two (the methoxymethyl)-7-phenylindan of 1,1-; Two (the methoxymethyl)-2-phenylindan of 1,1-; Two (methoxymethyl)-1H-benzo [e] indenes of 1,1-; Two (methoxymethyl)-1H-2-methyl benzo [e] indenes of 1,1-; Two (methoxymethyl) fluorenes of 9,9-; Two (methoxymethyl)-2,3,6 of 9,9-, 7-tetramethyl-fluorenes; Two (methoxymethyl)-2,3,4,5,6 of 9,9-, 7-hexafluoro fluorenes; Two (methoxymethyl)-2 of 9,9-, 3-benzofluorene; Two (methoxymethyl)-2,3,6 of 9,9-, 7-dibenzo fluorenes; Two (methoxymethyl)-2 of 9,9-, 7-di-isopropyl fluorenes; Two (methoxymethyl)-1 of 9,9-, 8-dichloro fluorenes; Two (methoxymethyl)-2 of 9,9-, 7-bis-cyclopentyl fluorenes; Two (methoxymethyl)-1 of 9,9-, 8-difluoro fluorenes; Two (methoxymethyl)-1,2,3 of 9,9-, 4-tetrahydrochysene fluorenes; Two (methoxymethyl)-1,2,3,4,5,6,7 of 9,9-, 8-octahydro fluorenes; Two (the methoxymethyl)-4-tertiary butyl fluorenes of 9,9-.
The another kind of electron donor compound that the unsaturated ring of logical formula I replaces outside two ester compounds is preferably monocarboxylic ester or polycarboxylic acid ester compound, and concrete example is aromatic binary carboxylic acid compound and aliphatic chain di-carboxylic acid ester compound:
The diester of aromatic binary carboxylic acid, as Bisphthalate or bis--terephthalate.Bisphthalate comprises: dimethyl phthalate, diethyl phthalate, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate, Methyl Benzene-o-dicarboxylate ethyl ester, Methyl Benzene-o-dicarboxylate isopropyl ester, Methyl Benzene-o-dicarboxylate n-propyl, the positive butyl ester of ethyl phthalate(DEP), ethyl phthalate(DEP) isobutyl ester, amyl phthalate, di-iso-amyl phthalate, dihexyl phthalate, heptyl phthalate ester, dinoctyl phthalate, dimixo-octyl phthalate, phthalic acid (2,2-dimethyl hexyl) diester, phthalic acid (2-ethylhexyl) diester, 2-nonyl-phthalate ester, Di Iso Decyl Phthalate, phthalic acid (2,2-dimethyl heptyl) diester, n-butyl phthalate isohexyl ester, n-butyl phthalate (2-ethylhexyl) ester, the just own ester of phthalic acid n-pentyl ester, phthalic acid n-pentyl ester ester in the different ninth of the ten Heavenly Stems, isoamyl phthalate ester in the positive last of the ten Heavenly stems, phthalic acid n-pentyl ester undecane ester, phthalic acid isopentyl isohexyl ester, the just own ester of phthalic acid (2-methyl polyhexamethylene), phthalic acid n-hexyl (2-(ethyl hexyl) ester), the just own ester of phthalic acid (different the ninth of the ten Heavenly Stems ester), phthalic acid n-hexyl (positive the last of the ten Heavenly stems ester), the positive heptyl ester of phthalic acid (2-(ethyl hexyl) ester), the positive heptyl ester of phthalic acid (different the ninth of the ten Heavenly Stems ester), the positive heptyl ester of phthalic acid ester in the new ninth of the ten Heavenly Stems and phthalic acid 2-ethylhexyl (different the ninth of the ten Heavenly Stems ester).These esters can independent or multiple mixing use.Bis--terephthalate comprises: dimethyl terephthalate (DMT), diethyl terephthalate, terephthalic acid di-n-propyl ester, terephthalic acid diisopropyl ester, di-n-butyl terephthalate, di-n-butyl terephthalate, isobutyl terephthalate, terephthaldehyde's acetoacetic ester methyl esters, terephthalic acid methyl esters isopropyl ester, terephthaldehyde's acetoacetic ester (n-propyl), terephthaldehyde's acetoacetic ester (positive butyl ester), terephthaldehyde's acetoacetic ester (isobutyl ester), terephthalic acid two n-pentyl esters, terephthalic acid diisoamyl ester, terephthalic acid dihexyl, the positive heptyl ester of terephthalic acid two, terephthalic acid di-n-octyl, the different n-octyl of terephthalic acid two, terephthalic acid two (2,2-dimethyl hexyl) ester, terephthalic acid two (2-ethylhexyl) ester, terephthalic acid two ester in the positive ninth of the ten Heavenly Stems, terephthalic acid dinonyl, terephthalic acid two isodecyl esters, terephthalic acid two (2,2-dimethyl ethyl heptyl) ester, the positive butyl ester dissident of terephthalic acid ester, the positive butyl ester of terephthalic acid (2 ethylhexyl) ester, the just own ester of terephthalic acid n-pentyl ester, terephthalic acid n-pentyl ester dissident ester, terephthaldehyde's isoamyl valerate (heptyl ester), terephthalic acid, terephthalic acid n-pentyl ester (2-ethylhexyl) ester, terephthalic acid n-pentyl ester (different the ninth of the ten Heavenly Stems ester), terephthaldehyde's isoamyl valerate (positive the last of the ten Heavenly stems ester), terephthalic acid n-pentyl ester undecane ester, terephthaldehyde's isoamyl valerate dissident ester, terephthalic acid n-hexyl (2-(ethyl hexyl) ester), terephthalic acid n-hexyl (different nonyl ester), the just own ester of terephthalic acid (positive the last of the ten Heavenly stems ester), terephthalic acid n-heptyl (2-(ethyl hexyl) ester), terephthalic acid n-heptyl (different nonyl ester), terephthalic acid n-heptyl (new the last of the ten Heavenly stems ester), with terephthalic acid 2-ethylhexyl (different nonyl ester).These esters can independent or multiple mixing use.
Recommendation diethyl phthalate in these diester, dipropyl phthalic butyl ester, terephthalic acid diisopropyl ester, n-butyl phthalate, diisobutyl phthalate, dinoctyl phthalate, dimixo-octyl phthalate, di-n-butyl terephthalate, isobutyl terephthalate, terephthalic acid di-n-octyl, terephthalic acid di-isooctyl, the mixing of one or more in terephthalic acid two (2-ethylhexyl) ester or Di Iso Decyl Phthalate.
In polycarboxylic acid ester compound, particularly preferably, be selected from the succinate compounds of general formula (V):
Wherein, radicals R
1and R
2, be same to each other or different to each other, be C
1-C
20line style or branched-alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkylaryl group, optionally comprise heteroatoms; R
3-R
6in at least two groups be different from hydrogen and be selected from C
1-C
20line style or branched-alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkylaryl group, optionally contain heteroatoms, in addition, and radicals R
3-R
6can link together and form a ring.R
1and R
2preferably C
1-C
8alkyl, cycloalkyl, aryl, aralkyl and alkylaryl group.Particularly preferably be such compound, wherein R
1and R
2be selected from primary alkyl, particularly branched primary alkyl.Suitable R
1and R
2example be methyl, ethyl, n-propyl, normal-butyl, isobutyl-, neo-pentyl, 2-ethylhexyl.Particularly preferably be ethyl, isobutyl-and neo-pentyl.
One of preferred compounds category that general formula (V) is described is such, wherein R
3-R
5hydrogen and R
6branched-alkyl, cycloalkyl, aryl, aralkyl and the alkylaryl group with 3-10 carbon atom.Particularly preferably be such compound, wherein R
6branched primary alkyl group or the group of naphthene base with 3-10 carbon atom.The object lesson of suitable monosubstituted succinate compound is sec-butyl ethyl succinate, hexyl ethyl succinate, cyclopropyl ethyl succinate, norcamphyl ethyl succinate, perhydro-ethyl succinate, trimethyl-succinic acid diethyl ester, methoxyl group ethyl succinate, p-methoxyphenyl ethyl succinate, rubigan ethyl succinate, phenylsuccinic acid diethyl ester, cyclohexyl ethyl succinate, benzyl ethyl succinate, cyclohexyl methyl ethyl succinate, tertiary butyl ethyl succinate, isobutyl-ethyl succinate, sec.-propyl ethyl succinate, neo-pentyl ethyl succinate, isopentyl ethyl succinate, (1-trifluoromethyl ethyl) ethyl succinate, fluorenyl ethyl succinate, phenylsuccinic acid (1-oxyethyl group carbonyl diisobutyl ester) (1-(ethoxycarbo diisobutyl phenylsuccinate), sec-butyl di-iso-octyl succinate, hexyl di-iso-octyl succinate, cyclopropyl di-iso-octyl succinate, norcamphyl di-iso-octyl succinate, perhydro-di-iso-octyl succinate, trimethyl silyl di-iso-octyl succinate, methoxyl group di-iso-octyl succinate, p-methoxyphenyl di-iso-octyl succinate, to chlorophenoxy di-iso-octyl succinate, cyclohexyl di-iso-octyl succinate, benzyl di-iso-octyl succinate, cyclohexyl methyl di-iso-octyl succinate, tertiary butyl di-iso-octyl succinate, isobutyl-di-iso-octyl succinate, sec.-propyl di-iso-octyl succinate, neo-pentyl di-iso-octyl succinate, isopentyl di-iso-octyl succinate, (1-trifluoromethyl ethyl) di-iso-octyl succinate, fluorenyl di-iso-octyl succinate, sec-butyl succsinic acid two peopentyl esters, hexyl succsinic acid two peopentyl esters, cyclopropyl succsinic acid two peopentyl esters, norcamphyl succsinic acid two peopentyl esters, perhydro-succsinic acid two peopentyl esters, trimethyl silyl succsinic acid two peopentyl esters, methoxyl group succsinic acid two peopentyl esters, p-methoxyphenyl succsinic acid two peopentyl esters, rubigan succsinic acid two peopentyl esters, phenylsuccinic acid two peopentyl esters, cyclohexyl succsinic acid two peopentyl esters, benzyl succsinic acid two peopentyl esters, cyclohexyl methyl succsinic acid two peopentyl esters, tertiary butyl succsinic acid two peopentyl esters, isobutyl-succsinic acid two peopentyl esters, sec.-propyl succsinic acid two peopentyl esters, neo-pentyl succsinic acid two peopentyl esters, isopentyl succsinic acid two peopentyl esters, (1-trifluoromethyl ethyl) succsinic acid two peopentyl esters, fluorenyl succsinic acid two peopentyl esters.
In the middle of compound in general formula (V), another kind of preferred compound is such, wherein R
3-R
6in at least two groups be different from hydrogen and be selected from C
1-C
20line style or branched-alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkylaryl group, optionally contain heteroatoms.Particularly preferably be such compound, wherein the group of two non-hydrogen is connected on same carbon atom.The two suitable object lessons that replace succinate are: 2,2-dimethyl succinate diethyl ester, 2-Ethyl-2-Methyl ethyl succinate, 2-benzyl-2-sec.-propyl ethyl succinate, 2-cyclohexyl methyl-2-isobutyl-succsinic acid diethyl _ _ ester, 2-cyclopentyl-2-normal-butyl ethyl succinate, 2,2-diisobutyl ethyl succinate, 2-cyclohexyl-2-ethyl ethyl succinate, 2-sec.-propyl-2-methylsuccinic acid diethyl ester, 2-tetradecyl-2-ethyl ethyl succinate, 2-isobutyl--2-ethyl ethyl succinate, 2-(1-trifluoromethyl ethyl)-2-methylsuccinic acid diethyl ester, 2-isopentyl-2-isobutyl-ethyl succinate, 2-phenyl-2-normal-butyl ethyl succinate, 2,2-dimethyl succinate diisobutyl ester, 2-Ethyl-2-Methyl di-iso-octyl succinate, 2-benzyl-2-sec.-propyl di-iso-octyl succinate, 2-cyclohexyl methyl-2-isobutyl-di-iso-octyl succinate, 2-cyclopentyl-2-normal-butyl di-iso-octyl succinate, 2,2-diisobutyl di-iso-octyl succinate, 2-cyclohexyl-2-ethyl di-iso-octyl succinate, 2-sec.-propyl-2-methylsuccinic acid diisobutyl ester, 2-tetradecyl-2-ethyl di-iso-octyl succinate, 2-isobutyl--2-ethyl di-iso-octyl succinate, 2-(1-trifluoromethyl ethyl)-2-methylsuccinic acid diisobutyl ester, 2-isopentyl-2-isobutyl-di-iso-octyl succinate, 2-phenyl-2-normal-butyl di-iso-octyl succinate, 2,2-dimethyl succinate, two peopentyl esters, 2-Ethyl-2-Methyl succsinic acid two peopentyl esters, 2-benzyl-2-sec.-propyl succsinic acid two peopentyl esters, 2-cyclohexyl methyl-2-isobutyl-succsinic acid two peopentyl esters, 2-cyclopentyl-2-normal-butyl succsinic acid two peopentyl esters, 2,2-diisobutyl succsinic acid, two peopentyl esters, 2-cyclohexyl-2-ethyl succsinic acid two peopentyl esters, 2-sec.-propyl-2-methylsuccinic acid two peopentyl esters, 2-tetradecyl-2-ethyl succsinic acid two peopentyl esters, 2-isobutyl--2-ethyl succsinic acid two peopentyl esters, 2-(1-trifluoromethyl ethyl)-2-methylsuccinic acid two peopentyl esters, 2-isopentyl-2-isobutyl-succsinic acid two peopentyl esters, 2-phenyl-2-normal-butyl succsinic acid two peopentyl esters.
In addition, also such compound particularly preferably, wherein the group of at least two non-hydrogen is connected to different carbon atoms, i.e. R
3and R
5or R
4and R
6.The object lesson of suitable compound is 2,3-bis-(trimethyl silyl) ethyl succinate, 2-sec-butyl-3-methylsuccinic acid diethyl ester, 2-(3,3,3-trifluoro propyl)-3-methylsuccinic acid diethyl ester, 2,3-bis-(2-ethyl-butyl) ethyl succinate, 2,3-diethyl-2-sec.-propyl ethyl succinate, 2,3-di-isopropyl-2-methylsuccinic acid diethyl ester, 2,3-dicyclohexyl-2-methylsuccinic acid diethyl ester, 2,3-dibenzyl ethyl succinate, 2,3-di-isopropyl ethyl succinate, 2,3-bis-(cyclohexyl methyl) ethyl succinate, 2,3-di-t-butyl ethyl succinate, 2,3-diisobutyl ethyl succinate, 2,3-di neo-pentyl ethyl succinate, 2,3-diisoamyl ethyl succinate, 2,3-bis-(1-trifluoromethyl ethyl) ethyl succinate, 2,3-bis-(tetradecyl) ethyl succinate, 2,3-, bis-fluorenyl ethyl succinates, 2-sec.-propyl-3-isobutyl-ethyl succinate, the 2-tertiary butyl-3-sec.-propyl ethyl succinate, 2-sec.-propyl-3-cyclohexyl ethyl succinate, 2-isopentyl-3-cyclohexyl ethyl succinate, 2-tetradecyl-3-cyclohexyl ethyl succinate, 2-cyclohexyl-3-cyclopentyl ethyl succinate, 2,2,3,3-tetramethyl-ethyl succinate, 2,2,3,3-tetraethyl-ethyl succinate, 2,2,3,3-tetrapropyl ethyl succinate, 2,3-diethyl-2,3-di-isopropyl ethyl succinate, 2,2,3,3-tetrafluoro ethyl succinate, 2,3-bis-(trimethyl silyl) di-iso-octyl succinate, 2-sec-butyl-3-methylsuccinic acid diisobutyl ester, 2-(3,3,3-trifluoro propyl)-3-methylsuccinic acid diisobutyl ester, 2,3-bis-(2-ethyl-butyl) di-iso-octyl succinate, 2,3-diethyl-2-sec.-propyl di-iso-octyl succinate, 2,3-di-isopropyl-2-methylsuccinic acid diisobutyl ester, 2,3-dicyclohexyl-2-methylsuccinic acid diisobutyl ester, 2,3-dibenzyl di-iso-octyl succinate, 2,3-di-isopropyl di-iso-octyl succinate, 2,3-bis-(cyclohexyl methyl) di-iso-octyl succinate, 2,3-di-t-butyl di-iso-octyl succinate, 2,3-diisobutyl di-iso-octyl succinate, 2,3-di neo-pentyl di-iso-octyl succinate, 2,3-diisoamyl di-iso-octyl succinate, 2,3-bis-(1-trifluoromethyl ethyl) di-iso-octyl succinate, 2,3-bis-(tetradecyl) di-iso-octyl succinate, 2,3-, bis-fluorenyl di-iso-octyl succinates, 2-sec.-propyl-3-isobutyl-di-iso-octyl succinate, the 2-tertiary butyl-3-sec.-propyl di-iso-octyl succinate, 2-sec.-propyl-3-cyclohexyl di-iso-octyl succinate, 2-isopentyl-3-cyclohexyl di-iso-octyl succinate, 2-tetradecyl-3-cyclohexyl methyl di-iso-octyl succinate, 2-cyclohexyl-3-cyclopentyl di-iso-octyl succinate, 2,2,3,3-tetramethyl-di-iso-octyl succinate, 2,2,3,3-tetraethyl-di-iso-octyl succinate, 2,2,3,3-tetrapropyl di-iso-octyl succinate, 2,3-diethyl-2,3-dipropyl di-iso-octyl succinate, 2,2,3,3-tetrafluoro di-iso-octyl succinate, 2,3-bis-(trimethyl silyl) succsinic acid, two peopentyl esters, 2-sec-butyl-3-methylsuccinic acid two peopentyl esters, 2-(3,3,3-trifluoro propyl)-3-methylsuccinic acid two peopentyl esters, 2,3-bis-(2-ethyl-butyl) succsinic acid, two peopentyl esters, 2,3-diethyl-2-sec.-propyl succsinic acid, two peopentyl esters, 2,3-di-isopropyl-2-methylsuccinic acid, two peopentyl esters, 2,3-dicyclohexyl-2-methylsuccinic acid, two peopentyl esters, 2,3-dibenzyl succsinic acid, two peopentyl esters, 2,3-di-isopropyl succsinic acid, two peopentyl esters, 2,3-bis-(cyclohexyl methyl) succsinic acid, two peopentyl esters, 2,3-di-t-butyl succsinic acid, two peopentyl esters, 2,3-diisobutyl succsinic acid, two peopentyl esters, 2,3-di neo-pentyl succsinic acid, two peopentyl esters, 2,3-diisoamyl succsinic acid, two peopentyl esters, 2,3-(1-trifluoromethyl ethyl) succsinic acid two peopentyl esters, 2,3-bis-(tetradecyl) succsinic acid, two peopentyl esters, 2,3-, bis-fluorenyl succsinic acid two peopentyl esters, 2-sec.-propyl-3-isobutyl-succsinic acid two peopentyl esters, the 2-tertiary butyl-3-sec.-propyl succsinic acid two peopentyl esters, 2-sec.-propyl-3-cyclohexyl succsinic acid two peopentyl esters, 2-isopentyl-3-cyclohexyl succsinic acid two peopentyl esters, 2-tetradecyl-3-cyclohexyl methyl succsinic acid two peopentyl esters, 2-cyclohexyl-3-cyclopentyl succsinic acid two peopentyl esters, 2,2,3,3-tetramethyl-succsinic acid, two peopentyl esters, 2,2,3,3-tetraethyl-succsinic acid, two peopentyl esters 2,2,3,3-tetrapropyl succsinic acid two peopentyl esters, 2,3-diethyl-2,3-di-isopropyl succsinic acid two peopentyl esters, 2,2,3,3-tetrafluoro succsinic acid, two peopentyl esters.
As mentioned, be connected to the radicals R on same carbon atom above
3-R
6in two or four compounds of general formula (V) that form rings that link together be also preferred.The object lesson of suitable compound is 1-(ethoxycarbonyl)-1-(oxyethyl group acetyl)-2; 6-dimethyl cyclohexane, 1-(ethoxycarbonyl)-1-(oxyethyl group acetyl)-2,5-dimethylcyclopentane, 1-(ethoxycarbonyl)-1-(oxyethyl group ethanoyl methyl)-2-methylcyclohexane, 1-(ethoxycarbonyl)-1-(oxyethyl group ethanoyl cyclohexyl) hexanaphthene.
Compound above-mentioned can pure isomer form or with the form of mixtures of enantiomorph, or use with the form of mixtures of positional isomers and enantiomorph.In the time will using pure isomer, generally adopt common technology well known in the art to be separated.Particularly, in succinate of the present invention, some can be used as pure racemize or meso-form, or alternatively uses with the mixture of these two kinds of forms.
The another kind of electron donor compound that the unsaturated ring of logical formula I replaces outside two ester compounds one is preferably the diol ester compound that leads to formula VI again:
R in formula
1-R
6, R
1-R
2for the C of identical or different hydrogen, halogen or replacement or unsubstituted straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl, C
7-C
20aralkyl, C
2-C
10alkylene or C
10-C
20fused ring aryl; But R
1and R
2not hydrogen, R
3-R
6and R
1-R
2in one or morely optionally become ring or Cheng Huan not.
Described diol-lipid compound specifically can adopt: 1,3-PD dibenzoate, 2-methyl isophthalic acid, ammediol dibenzoate, 2-ethyl-1,3-PD dibenzoate, 2-propyl group-1,3-PD dibenzoate, 2-butyl-1,3-PD dibenzoate, 2，2-dimethyl-1，3-propanediol dibenzoate, 2-ethyl-2-butyl-1,3-PD dibenzoate, 2,2-diethyl-1,3-PD dibenzoate, 2-methyl-2-propyl-1,3-PD dibenzoate, 2-sec.-propyl-2-isopentyl-1,3-PD dibenzoate, 2,4-pentanediol dibenzoate, 3-methyl-2,4-pentanediol dibenzoate, 3-ethyl-2,4-pentanediol dibenzoate, 3-propyl group-2,4-pentanediol dibenzoate, 3-butyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate, 2-methyl isophthalic acid, 3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2-methyl isophthalic acid, 3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-propyl group-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2-methyl isophthalic acid, 3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2,2,4-trimethylammonium-1,3-pentanediol dibenzoate, 3-methyl-3-butyl-2,4-pentanediol dibenzoate, 2,2-dimethyl-1,5-PD dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate etc.Preferably pentadiol ester and heptanediol ester.
Ingredient of solid catalyst for olefinic polymerization of the present invention, comprise at least one unsaturated ring that titanium compound, magnesium compound, (i) be selected from logical formula I and replace two ester compounds, (ii) simple function group of at least one ether, ester, ketone or amine or polyfunctional group electron donor compound, the precursor of described magnesium compound is selected from least one: Mg (OR)
2, X
nmg (OR)
2-n, MgCl
2mROH, R
2-nmgX
n, MgR
2, MgCl
2/ SiO
2, MgCl
2/ Al
2o
3, or the mixture of magnesium halide and alcohol titanium, the number that in formula, m is 0.1-6,0<n<2, X is halogen, R is C
1-C
20alkyl; The general formula of described titanium compound is TiX
n(OR)
4-n, in formula, R is that carbonatoms is the alkyl of 1-20, X is halogen, n=1-4.
Magnesium compound of the present invention preferably adopts magnesium alkoxide compound.
Another preferably adopts the alcohol adduct of magnesium dihalide magnesium compound of the present invention.
Magnesium compound of the present invention one preferably adopts liquid magnesium compound again.
Titanium compound of the present invention comprises titanium tetrachloride, titanium tetrabromide, titanium tetra iodide or alkyl halide titanium, and alkyl halide titanium is as methoxyl group titanous chloride, oxyethyl group titanous chloride, propoxy-titanous chloride, n-butoxy titanous chloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, two n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride or three n-Butoxyl titanium-chlorides.In these halogenated titaniums, can apply one or more and mix use.Wherein preferably adopt titanium tetrachloride.
The preparation of ingredient of solid catalyst of the present invention can be carried out according to several method.
According to a kind of method wherein, use TiCl
4or the aromatic hydrocarbons of titanium alkoxides (such as toluene, dimethylbenzene etc.) solution can react with two magnesium alkoxide compounds such as dialkoxy magnesium or two aryloxy magnesium, and carry out halogenation at 80-130 DEG C at-25-0 DEG C.Use TiCl
4the processing carried out of aromatic hydrocarbons solution can repeat one or many, and once or in batches add logical formula I in repeatedly such processing-the unsaturated ring of (III) replaces two ester compounds and electron donor compound (ii).For example can be prepared with reference to the preparation method of disclosed solids containing titanium catalyst component in US5077357: add successively magnesium ethylate, purity titanium tetraethoxide, ortho-cresol, ethanol and chlorobenzene, stir; By TiCl
4/ chlorobenzene solution adds in aforesaid liquid fast, heats up until completely dissolved, continues to be warming up to specified temp; Utilize N
2bubbling continues to stir certain hour after taking away ethanol synthesis thing, then adopts hot chlorobenzene to wash once, octane-iso washed twice, then N
2dry up and can obtain carrier.Or according to another example: successively by TiCl
4, purity titanium tetraethoxide, magnesium ethylate and ortho-cresol add in chlorobenzene, stir; Add ethanol, under high temperature, after magnesium ethylate dissolves, continue to stir 3h; Then filtered while hot adopts warm chlorobenzene to wash once, and octane-iso washs once, last N
2dry.
According to another kind of method, the alcoholate of magnesium or chlorohydrin and the unsaturated ring that contains logical formula I-(III) in solution replace the excessive TiCl of two ester compounds and electron donor compound (ii)
4at the temperature of 80-135 DEG C, react.According to preferred method, can be TiX by general formula
n(OR)
4-ntitanium compound, in formula, R is that carbonatoms is the alkyl of 1-20, X is halogen, n=1-4; Preferably TiCl
4, and be MgCl from general formula
2the adducts of mROH reacts and prepares ingredient of solid catalyst, the number that in formula, m is 0.1-6, and preferably 2-3.5, and R is the alkyl with 1-20 carbon atom.Adducts can be made spherical by the following method aptly: under not existing with the miscible unreactive hydrocarbons of adducts, alcohol and magnesium chloride are mixed, make the rapid chilling of this emulsion, thereby adducts is solidified with the form of spheroidal particle.The spherical MgCl preparing according to this process
2the example of mROH adducts is described and is found in US4399054 and US4469648.The adducts so obtaining can directly react with titanium compound, or its can be in advance through dealcoholization (80-130 DEG C) of thermal control to obtain a kind of adducts, wherein the mole number of alcohol is generally lower than 3, preferably between 0.1-2.5.Can be by adducts (dealcoholysis or itself) be suspended in to cold TiCl
4in (general-25-0 DEG C), carry out and the reacting of titanium compound; Mixture is heated to 80-130 DEG C and keep 0.5-2 hour at this temperature.Use TiCl
4the processing of carrying out can be carried out once or repeatedly.Using TiCl
4during processing, can add the unsaturated ring of logical formula I-(III) to replace two ester compounds and electron donor compound (ii) is processed, this processing can repeat once or repeatedly.
The another kind of method of preparation ingredient of solid catalyst of the present invention comprises, the electron donor compound that Magnesium Chloride Anhydrous and the unsaturated ring of logical formula I-(III) is replaced to two ester compounds and (ii) occur under the condition of activation at magnesium dichloride together with grinding.The product so obtaining can be with excessive TiCl at the temperature of 80-130 DEG C
4process one or many.After processing with the washing of hydro carbons volume until chloride ion-containing not.According to further method, the unsaturated ring of the magnesium dichloride by anhydrous state, titanium compound and logical formula I-(III) is replaced to two ester compounds and carry out the product that common grinding obtains, adopt and process such as the halohydrocarbon of 1,2-ethylene dichloride, chlorobenzene, methylene dichloride and so on.This processing is carried out 1-4 hour at 40 DEG C to the temperature between halohydrocarbon boiling point.Then conventionally wash and obtain product with the inertia hydro carbons volume of hexane and so on.
According to another kind of method, magnesium dichloride is activated in advance according to the method for knowing, then at the temperature of about 80-135 DEG C with excessive TiCl
4process, the unsaturated ring that wherein contains logical formula I-(III) in solution replaces two ester compounds and electron donor compound (ii).Use TiCl
4process repeatedly and solid cleaned to remove any TiCl for reaction with hexane
4.
Further method comprises, also can be prepared with reference to the preparation method of disclosed solids containing titanium catalyst component in CN1208045: first under a kind of compound that is selected from alcohol, phenol, ketone, aldehyde, ether, amine, pyridine and ester exists, liquid magnesium compound is contacted with liquid titanium compound at low temperatures, be settled out solid, be generally-70-200 DEG C of temperature when contact, be preferably-30-130 DEG C, in contact process, replace two ester compounds and electron donor compound treatment (ii) with the unsaturated ring of logical formula I-(III).
The another kind of method of ingredient of solid catalyst of the present invention comprises: magnesium compound is dissolved in the solvent system being made up of organic epoxy compounds, organo phosphorous compounds and inert diluent, after forming homogeneous solution, mix with titanium compound, under the existence of precipitation additive, wash out solids; This solids replaces two ester compounds and electron donor compound treatment (ii) with the unsaturated ring of logical formula I-(III), it is carried on solids, if desired, process and obtain with titanium tetrahalide and inert diluent again, wherein precipitation additive is the one in organic acid anhydride, organic acid, ether, ketone.Described each component is in every mole of magnesium halide, and organic epoxy compounds is 0.2-10 mole, and organo phosphorous compounds is 0.1-3 mole, and precipitation additive is 0.03-1.0 mole, and the halogenide of transition metal Ti and derivative thereof are 0.5-150 mole.
Ingredient of solid catalyst of the present invention, can also adopt at SiO
2, the magnesium compound of load is prepared as carrier on the inorganic oxide such as aluminum oxide or porous resin, then activate by the method for knowing, then at the temperature of about 80-135 DEG C with excessive TiCl
4process, in treating processes, adding has logical formula I-and the unsaturated ring of (III) replaces two ester compounds and electron donor compound (ii).
Above-mentioned reaction cause form be activity morphology magnesium halide (general crystal magnesium halide compound with regular structure, portative Ti is little, thereby catalytic activity is low, prepare highly active supported catalyst, magnesium halide must pass through activation treatment.Activating treatment process comprise with physics and/or chemistry method be made into crystallite so that active centre is carried on magnesium halide surface, edge and fault location, the magnesium halide crystallite that is suitable for load Ti of this processing is " magnesium halide in active ").Except these reactions, the method that is also known to other in document makes to form by the compound initial substance that is different from magnesium halide the magnesium halide that is activity morphology.
In any preparation method, above-mentioned electron donor compound can directly add with itself or be undertaken by optional mode, for example make by adopting suitable precursor to carry out original position, in this suitably front resonable electron donor compound of thinking of physical efficiency, for example rely on such as the known chemical reaction of esterification, transesterify etc. and complete conversion.Conventionally, with respect to MgCl
2, with 0.01-5, preferably 0.05-2.0 mole recently use above-mentioned electron donor compound.
In any preparation method, the unsaturated ring of logical formula I-(III) replaces two ester compounds and electron donor compound (ii) can add at the same time or separately with random order arbitrary combination in preparation process.
Ingredient of solid catalyst of the present invention is by reacting to change into the catalyzer for olefinic polymerization by currently known methods and organo-aluminium compound.Especially, one object of the present invention is to provide a kind of for alkene CH
2the catalyzer of=CHR polymerization, wherein R is hydrogen or the hydrocarbyl group containing 1-12 carbon atom, this catalyzer comprises the product of following substance reaction:
(a) at least one unsaturated ring that the Mg of containing of the present invention, Ti and halogen, (i) are selected from logical formula I replaces two ester compounds, (ii) simple function group of at least one ether, ester, ketone or amine or polyfunctional group electron donor compound
(b) at least one general formula is AlR
nx
(3-n)organo-aluminium compound, in formula, R is the alkyl of hydrogen, carbonatoms 1-20; X is halogen, the integer that n is 0≤n≤3; With, optionally,
(c) at least one external donor compound.
Preferably, organo-aluminium compound (b) is selected from the trialkyl compound such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, trioctylaluminum.Also likely use trialkylaluminium and aluminum alkyl halide, alkyl aluminum hydride or such as AlEt
2cl and Al
2et
3cl
3and so on the mixture of alkylaluminium sesquichloride, can also use alkyl chloride oxygen alkane.
For the application of the good degree of isotacticity of needs, can use external donor compound.It is R that external donor compound is selected from general formula
nsi (OR
1)
4-nsilicone compounds, R and R in formula
1for C
1-C
18alkyl, optionally also have heteroatoms; N is the integer of 0≤n≤3.
Described silicone compounds specifically can be: trimethylammonium methoxy silane, trimethylethoxysilane, three n-propyl methoxy silane, three n-propyl Ethoxysilanes, three normal-butyl methoxy silane, triisobutyl Ethoxysilane, thricyclohexyl methyl-monosilane, thricyclohexyl Ethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diη-propyl dimethoxy silane, diisopropyl dimethoxy silane, diη-propyl diethoxy silane, di-isopropyl diethoxy silane, di-n-butyl diethoxy silane, diisobutyl diethoxy silane, di-t-butyl dimethoxy silane, di-t-butyl dimethoxy silane, di-n-butyl dimethoxy silane, second, isobutyl dimethoxy silane, di-t-butyl diethoxy silane, di-n-butyl diethoxy silane, n-butylmethyldimethoxyforane, two (2-ethylhexyl) dimethoxy silane, two (2-ethylhexyl) diethoxy silane, Dicyclohexyldimethoxysilane, dicyclohexyl diethoxy silane, dicyclopentyl dimethoxyl silane, two cyclopentyl diethoxy silanes, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl methyl diethoxy silane, cyclohexyl ethyl dimethoxy silane, cyclohexyl sec.-propyl dimethoxy silane, cyclohexyl ethyl diethoxy silane, cyclopentyl-methyl dimethoxy silane, cyclopentyl ethyl diethoxy silane, cyclopentyl sec.-propyl diethoxy silane, cyclopentyl isobutyl-dimethoxy silane, cyclohexyl n-propyl dimethoxy silane, cyclohexyl n-propyl diethoxy silane, cyclohexyl normal-butyl diethoxy silane, amyl group methyl dimethoxysilane, amyl group methyldiethoxysilane, amyl group ethyl dimethoxy silane, amyl group ethyl diethoxy silane, cyclohexyl dimethyl methyl TMOS, cyclohexyl diethyl methoxy silane, cyclohexyl diethyl methoxy silane, cyclohexyl diethyl Ethoxysilane, 2-ethylhexyl Trimethoxy silane, cyclohexyl dimethoxy silane, cyclohexyl diethoxy silane, 2-ethylhexyl triethoxyl silane, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, sec.-propyl Trimethoxy silane, sec.-propyl triethoxyl silane, normal-butyl Trimethoxy silane, isobutyl-Trimethoxy silane, tert-butyl trimethoxy silane, ne-butyltriethoxysilaneand, cyclohexyl trimethoxy silane, cyclohexyltriethyloxysilane, cyclopentyl-trimethoxy-silane, cyclopentyl triethoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, 2-ethylhexyl Trimethoxy silane, 2-ethylhexyl triethoxyl silane, amyltrimethoxysilane, amyl triethoxysilane, tetramethoxy-silicane, tetraethoxysilane, cyclohexyl ring amyl group dimethoxy silane, cyclohexyl ring amyl group diethoxy silane, cyclohexyl ring amyl group dipropoxy silane, 3-methylcyclohexyl cyclopentyl dimethoxy silane, 4-methylcyclohexyl cyclopentyl dimethoxy silane, 3,5-Dimethylcyclohexyl cyclopentyl dimethoxy silane, 3-methylcyclohexyl cyclohexyl dimethoxy silane, two (3-methylcyclohexyl) dimethoxy silane, 4-methylcyclohexyl cyclohexyl dimethoxy silane, two (4-methylcyclohexyl) dimethoxy silane, 3,5-Dimethylcyclohexyl cyclohexyl dimethoxy silane, two (3,5-Dimethylcyclohexyl) dimethoxy silane, tetrapropoxysilane, four butoxy silanes.First-selected in these silicoorganic compound: diη-propyl dimethoxy silane, diisopropyl dimethoxy silane, di-n-butyl dimethoxy silane, second, isobutyl dimethoxy silane, di-t-butyl dimethoxy silane, di-n-butyl diethoxy silane, tert-butyl trimethoxy silane, Dicyclohexyldimethoxysilane, dicyclohexyl diethoxy silane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl ethyl diethoxy silane, cyclohexyl ethyl dimethoxy silane, cyclohexyl ethyl diethoxy silane, cyclopentyl-methyl dimethoxy silane, cyclopentyl-methyl diethoxy silane, cyclopentyl ethyl dimethoxy silane, cyclohexyl ring amyl group dimethoxy silane, cyclohexyl ring amyl group diethoxy silane, 3-methylcyclohexyl cyclopentyl dimethoxy silane, 4-methylcyclohexyl cyclopentyl dimethoxy silane and 3, 5-dimethylcyclopentyl dimethoxy silane etc.These Compound C can be used separately or mix use.
The example of preferred silicon compound has Cyclohexyl Methyl Dimethoxysilane; Diisopropyl dimethoxy silane; Di-n-butyl dimethoxy silane; Second, isobutyl dimethoxy silane; Dimethoxydiphenylsilane; Phenyl triethoxysilane; Methyl-t-butyldimethoxysilane; Dicyclopentyl dimethoxyl silane; 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane and (the fluoro-2-propyl group of 1,1,1-tri-)-2-ethyl piperidine base dimethoxy silane and (the fluoro-2-propyl group of 1,1,1-tri-)-methyl and methoxy silane, cyclohexyl trimethoxy silane; Tert-butyl trimethoxy silane and tertiary hexyl Trimethoxy silane.
Catalyzer of the present invention can be used for alkene CH
2in=CHR (being total to) polymerization, described alkene is ethene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene and 1-octene.
For the catalyzer of applying in the present invention carries out olefinic polymerization, homopolymerization and copolymerization can be applied above-mentioned by component a, b, the prepared catalyzer of c.Conventionally the mol ratio of components b and component a is that the every mol of 1-1000mol is contained in the titanium atom in component a, is preferably the every mol of 50-800mol and is contained in the titanium atom in component a; The mol ratio of amount of component b and component a is 0.002-10, is preferably 0.01-2, is preferably 0.01-0.5.
The order of addition(of ingredients) of each component is arbitrarily, joins at first in paradigmatic system with components b, then adds amount of component b, and it is good finally adding component a.
Polymerization technique in the present invention can carry out in the situation that having solvent or there is no solvent.Olefinic monomer can be gas phase or liquid phase.Further add hydrogen to can be used as molecular weight regulator.Certainly polymerization also can be carried out in the situation that there is no molecular weight regulator.Polymerization temperature is higher than 200 DEG C, preferably 20-100 DEG C, the more preferably temperature of 40-80 DEG C.Polymerization pressure does not exceed 10MPa, preferably 1-5MPa.Successive polymerization or batchwise polymerization technique can be applied.And polyreaction can divide a step, two steps or multistep to carry out.
Apply the alkene that catalyzer of the present invention carries out homopolymerization or copolymerization and comprise, normal olefine: ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-nonene, 1-decene; Branched-chain alkene is as 3-methyl-1-butene and 4-methyl-1-pentene; Diolefine is as divinyl, vinyl cyclopentenes and vinyl cyclohexene.Catalyzer of the present invention is preferably applied in polyethylene and polypropylene.These alkene can independent or multiple mixing use.
Apply the polymerization (referring to main body polymerization here) of the alkene that catalyst component a of the present invention, b, c carry out, recommend degree of isotacticity, the particle properties etc. of the reactive polymer that carries out the incompatible increase catalyzer of pre-polymerization.This prepolymerization technology equally can be for vinylbenzene homopolymerization.
In prepolymerization technology, the order of addition(of ingredients) of each component and monomer is arbitrarily.Preferably first components b is joined and contain inertia and maybe will carry out in the alkene gas of polymerization, then after component a, add one or more alkene of wanting polymerization adding.In the prepolymerized process of alkene of application organosilane, suggestion joins components b in the prepolymerization system of olefin gas that rare gas element maybe will carry out polymerization, then adds amount of component b, then adds component a, finally adds alkene again.
The present invention adopts the bifunctional compound with ad hoc structure, the unsaturated ring as shown in logical formula I replaces two ester compounds, because the oxygen of ester bond has stronger coordination effect, and relatively stable in the preparation process of catalyzer, therefore the activity to catalyzer and degree of isotacticity play active and effective effect.The contained specific ring of this compounds of the present invention replaces structure, has steric effect and can fix the steric configuration of ester bifunctional, has positive effect in the formation of participation catalyst active center and to the stereospecificity of raising catalyzer.
The inventor finds in experiment, in the time that this compounds is prepared to Ziegler-Natta catalyst component for electron donor, can make catalyst component have good activity and stereospecificity.Further improve the catalyst system of catalyzer degree of isotacticity for needs, or need the adjustable catalyst system of catalytic activity and degree of isotacticity, this compounds and existing published all kinds of electron donor compounds can be carried out in catalyst preparation process compositely, obtain having the catalyst system of best over-all properties.The inventor finds, in the time adopting different composite electron donor compounds and different compound proportions to use together with electron donor compound of the present invention, the charge capacity of electron donor in catalyzer, activity and the stereospecificity of catalyzer, can obtain adjusting in various degree, the catalyzer to producing with specific indexes has active and effective effect.
Embodiment
Further describe the present invention with embodiment below, be conducive to the understanding to the present invention and advantage thereof, better effects if, but described embodiment is only for illustrating the present invention instead of restriction the present invention.
unsaturated ring replaces the preparation of two ester compounds
Synthesizing of embodiment 1 fluorenes-9-methyl-formiate-9-ethyl formate
Steps A: add successively 18g sodium hydride, 50g fluorenes, 150mL toluene in 1000mL there-necked flask under nitrogen protection, open mechanical stirring, be warming up to 125 DEG C of backflows, keep reaction 4h; Be cooled to 90 DEG C, in flask, slowly drip 146.1g diethyl carbonate, in 1.5h, drip off, drip off rear continuation reaction 3h; Be cooled to 20 DEG C, slowly splash into the mixture of 60g concentrated hydrochloric acid and 75g water, and control temperature and be no more than 40 DEG C; Filter, isolate organic phase, wash with water to neutrality, organic phase is revolved steaming, obtains reddish-brown liquid; Reflux and spend the night revolving together with the hydrochloric acid that steams gained liquid and 157.4g acetic acid and 63g10%; Mixture is down to 20 DEG C, separatory; Organic phase adds 30%NaOH solution after revolving steaming, regulates pH value to 8～9, is extracted with ethyl acetate, and retains water.Water adds concentrated hydrochloric acid to regulate pH value to be extracted with ethyl acetate to 5-6, retains organic phase, and organic phase is revolved steaming; Product acetic acid ethyl dissolution, freezing recrystallization; Filter, thick product washs with hexane.Obtain the about 10g of clear crystal, fusing point: 228～230 DEG C.
In step B:250mL there-necked flask, add 9-formic acid fluorenes 2g (9.5mmol), methyl alcohol (30mL), the vitriol oil (0.2mL); Reflux 2h; Be cooled to room temperature; Reaction solution is poured in saturated sodium bicarbonate solution, and ethyl acetate extraction secondary (30mL*2) merges organic phase, saturated common salt washing (30mL*1), underpressure distillation, obtains yellow solid, oil pump is drained, and obtains the thick product of 1.8g, fusing point 62-65 DEG C.
In tri-mouthfuls of round-bottomed flasks of step C:250mL, add methyl alcohol (20mL), sodium Metal 99.5 (0.12g, 5mmol), under ice bath, after sodium Metal 99.5 dissolves emerge without bubble completely, add 9-methyl-formiate fluorenes (0.56g, 2.5mmol), dissolve completely, be yellow, after stirring 5min, add Vinyl chloroformate (0.8g, 7.5mmol); Stir 30min, pour in the aqueous solution, merge organic phase with using ethyl acetate extracting twice (50mL*2) after dichloromethane extraction (20mL*2) instead, saturated common salt washing (50mL*1), revolve and steam liquid, hexane washing, crude product sherwood oil recrystallization, obtain product, 106-109 DEG C.
Fluorenes-9-methyl-formiate-9-ethyl formate
1h-NMR (CDCl
3) δ (ppm): 0.982-1.014 (t, 3H, methyl hydrogen), 3.758 (s, 3H, the adjacent methyl hydrogen of oxygen), 4.130-4.156 (m, 2H, the adjacent methylene radical hydrogen of oxygen), 7.356-7.388 (t, 2H, aromatic ring hydrogen), (7.439-7.470 t, 2H, aromatic ring hydrogen), (7.714-7.728 d, 2H, aromatic ring hydrogen), (7.790-7.7804 d, 2H, aromatic ring hydrogen).
Embodiment 2 fluorenes-9,9-dicarboxylate synthetic
By (1.6M, n-Butyl Lithium/hexane solution 15mmol) is added drop-wise in the 20mL tetrahydrofuran solution that contains 16mmol diisopropylamine at-78 DEG C, above-mentioned solution stirs 45 minutes at-78 DEG C, and at 0 DEG C, stirs after 20 minutes and cool to-78 DEG C again.At-78 DEG C, the 20mL tetrahydrofuran solution that contains 7.0mmol fluorenes was added drop-wise in the above-mentioned solution stirring in 30 minutes, the Vinyl chloroformate of 33mmol is added in said mixture.Reaction system is warming up to room temperature, and at room temperature stirs 3 hours.Above-mentioned reaction mixture is poured in 100mL water, and by extracted with diethyl ether (three extractions, each 50mL ether), organic phase dried over mgso, the concentrated rear thick product of gained sherwood oil recrystallization, obtains product, 100-101 DEG C.
Fluorenes-9,9-dicarboxylate
1h-NMR (CDCl
3) δ (ppm): 0.932-0.962 (t, 6H, methyl hydrogen), 4.132-4.158 (m, 4H, the adjacent methylene radical hydrogen of oxygen), (7.392-7.424 t, 2H, aromatic ring hydrogen), (7.448-7.480 t, 2H, aromatic ring hydrogen), (7.734-7.748 d, 2H, aromatic ring hydrogen), (7.890-7.906 d, 2H, aromatic ring hydrogen)
Embodiment 3 fluorenes-9,9-dioctyl phthalate dimethyl ester synthetic
Synthesis step is with embodiment 2, and difference is for to be changed to methyl-chloroformate by Vinyl chloroformate.
Fluorenes-9,9-dioctyl phthalate dimethyl ester
1h-NMR (CDCl
3) δ (ppm): 3.759 (s, 6H, methyl hydrogen), (7.359-7.392 t, 2H, aromatic ring hydrogen), (7.443-7.475 t, 2H, aromatic ring hydrogen), 7.720-7.735 (d, 2H, aromatic ring hydrogen), 7.799-7.7814 (d, 2H, aromatic ring hydrogen).
Embodiment 4 fluorenes-9,9-dioctyl phthalate di-n-propyl ester synthetic
Synthesis step is with embodiment 2, and difference is for to be changed to chloroformic acid n-propyl by Vinyl chloroformate.
Fluorenes-9,9-dioctyl phthalate di-n-propyl ester
1h-NMR (CDCl
3) δ (ppm): 0.936-0.966 (t, 6H, methyl hydrogen), 1.664-1.735 (m, 4H, methylene radical hydrogen), 4.171-4.197 (t, 4H, the adjacent methylene radical hydrogen of oxygen), 7.389-7.421 (t, 2H, aromatic ring hydrogen), (7.449-7.481 t, 2H, aromatic ring hydrogen), (7.737-7.752 d, 2H, aromatic ring hydrogen), (7.887-7.902 d, 2H, aromatic ring hydrogen).
Embodiment 5 fluorenes-9,9-dioctyl phthalate diisopropyl ester synthetic
Synthesis step is with embodiment 2, and difference is for to be changed to isopropyl chlorocarbonate by Vinyl chloroformate.
Fluorenes-9,9-dioctyl phthalate diisopropyl ester
1h-NMR (CDCl
3) δ (ppm): 1.282-1.295 (t, 12H, methyl hydrogen), 5.012-5.062 (m, 4H, the adjacent methyne hydrogen of oxygen), (7.215-7.295 t, 2H, aromatic ring hydrogen), (7.307-7.354 t, 2H, aromatic ring hydrogen), (7.356-7.371 d, 2H, aromatic ring hydrogen), (7.654-7.686 d, 2H, aromatic ring hydrogen).
Embodiment 6 fluorenes-9,9-dioctyl phthalate di-n-butyl synthetic
Synthesis step is with embodiment 2, and difference is for to be changed to butyl chloroformate by Vinyl chloroformate.
Fluorenes-9,9-dioctyl phthalate di-n-butyl
1h-NMR (CDCl
3) δ (ppm): 0.937-0.967 (t, 6H, methyl hydrogen), (1.363-1.438 m, 4H, methylene radical hydrogen), (1.642-1.699 m, 4H, methylene radical hydrogen), 4.220-4.246 (oxygen faces methylene radical hydrogen for t, 4H), 7.394-7.426 (t, 2H, aromatic ring hydrogen), 7.447-7.479 (t, 2H, aromatic ring hydrogen), 7.734-7.749 (d, 2H, aromatic ring hydrogen), (7.889-7.904 d, 2H, aromatic ring hydrogen).
Embodiment 7 fluorenes-9,9-dioctyl phthalate diisobutyl ester synthetic
Synthesis step is with embodiment 2, and difference is for to be changed to isobutyl chlorocarbonate by Vinyl chloroformate.
Fluorenes-9,9-dioctyl phthalate diisobutyl ester
1h-NMR (CDCl
3) δ (ppm): 0.919-0.932 (d, 12H, methyl hydrogen), 1.936-2.016 (m, 2H, methyne hydrogen), 3.982-3.995 (d, 4H, the adjacent methylene radical hydrogen of oxygen), 7.372-7.405 (t, 2H, aromatic ring hydrogen), (7.440-7.473 t, 2H, aromatic ring hydrogen), (7.728-7.743 d, 2H, aromatic ring hydrogen), (7.868-7.883 d, 2H, aromatic ring hydrogen).
Embodiment 8 fluorenes-9,9-dioctyl phthalate dibenzyl ester synthetic
Synthesis step is with embodiment 2, and difference is for to be changed to benzyl chloroformate by Vinyl chloroformate.
Fluorenes-9,9-dioctyl phthalate dibenzyl ester
1h-NMR (CDCl
3) δ (ppm): 5.186-5.212 (s, 4H, methylene radical hydrogen), 7.372-7.405 (t, 2H, aromatic ring hydrogen), 7.384-7.426 (t, 6H, aromatic ring hydrogen), 7.440-7.473 (t, 2H, aromatic ring hydrogen), (7.478-7.602 d, 4H, aromatic ring hydrogen), (7.728-7.743 d, 2H, aromatic ring hydrogen), (7.868-7.883 d, 2H, aromatic ring hydrogen).
Table 1 encircles substituted fluorene ether-ether example
| Embodiment | ID-numbering | ID title |
| 1 | Ⅰ | Fluorenes-9-methyl-formiate-9-ethyl formate |
| 2 | Ⅱ | Fluorenes-9,9-dicarboxylate |
| 3 | Ⅲ | Fluorenes-9,9-dioctyl phthalate dimethyl ester |
the preparation of ingredient of solid catalyst
In embodiment, the operation of Kaolinite Preparation of Catalyst is all carried out under high pure nitrogen protection.Specific embodiment is as follows.
Comparative example 1
In 5 mouthfuls of flasks with stirring of fully replacing through nitrogen at 500ml, add 10g diethoxy magnesium and the prepare suspension of 80mL toluene, then maintain-15 DEG C and drip titanium tetrachloride 20mL, after system being slowly warming up to 10 DEG C after dropwising, drip titanium tetrachloride 60mL, slowly be warming up to again 80 DEG C afterwards, add 3.5g fluorenes-9-methyl-formiate-9-ethyl formate, then continue to be warming up to 120 DEG C of constant temperature 2 hours, then by clean liquid press filtration, elimination liquid, the solid of gained washs 3 times at 125 DEG C with 120mL titanium tetrachloride.The solid of gained washs 2 times at 60 DEG C with 150mL hexane, room temperature washing 2 times, elimination liquid is also dry, obtains 10.34g pressed powder and is ingredient of solid catalyst, analyzing titanium content is 3.96 (wt) %, and fluorenes two acid and esters contents are 10.29 (wt) %.
Comparative example 2
In 5 mouthfuls of flasks with stirring of fully replacing through nitrogen at 500ml, add 10gMgCl
22.5C
2h
5oH microballoon and the prepare suspension of 150mL titanium tetrachloride, then maintain-15 DEG C 1 hour, slowly be warmed up to 80 DEG C, add 4g fluorenes-9-methyl-formiate-9-ethyl formate, then continue to be warming up to 110 DEG C of constant temperature 1 hour, then by clean liquid press filtration, elimination liquid, the solid of gained with 120mL titanium tetrachloride 125 DEG C of washings 3 times.The solid of gained is with 150mL hexane 60 DEG C of washings 4 times, and elimination liquid is also dry, obtains 4.73g pressed powder and is ingredient of solid catalyst, and analyzing titanium content is 3.15 (wt) %, and fluorenes two acid and esters contents are 13.46 (wt) %.
Comparative example 3
Catalyst component preparation process is with comparative example 1, and difference is for to be changed to fluorenes-9 by fluorenes-9-methyl-formiate-9-ethyl formate, 9-dicarboxylate.
Comparative example 4
Catalyst component preparation process is with comparative example 1, and difference is for to be changed to fluorenes-9 by fluorenes-9-methyl-formiate-9-ethyl formate, 9-dioctyl phthalate dimethyl ester.
Comparative example 5
Catalyst component preparation process is with comparative example 1, and difference is for to be changed to n-butyl phthalate by fluorenes-9-methyl-formiate-9-ethyl formate.
Embodiment 9
Preparation method is with comparative example 1, and difference is 3.5g fluorenes-9-methyl-formiate-9-ethyl formate to be changed to 3.0g fluorenes-9-methyl-formiate-9-ethyl formate and 0.5g n-butyl phthalate.
Embodiment 10
Preparation method is with comparative example 1, and difference is 3.5g fluorenes-9-methyl-formiate-9-ethyl formate to be changed to 3.0g fluorenes-9-methyl-formiate-9-ethyl formate and 0.5g9,9-methoxyl methyl fluorenes.
Embodiment 11
Preparation method is with comparative example 1, and difference is 3.5g fluorenes-9-methyl-formiate-9-ethyl formate to be changed to 3.0g fluorenes-9-methyl-formiate-9-ethyl formate and 0.5g2,3-di-isopropyl ethyl succinate.
Embodiment 12
Preparation method is with comparative example 1, and difference is 3.5g fluorenes-9-methyl-formiate-9-ethyl formate to be changed to 3.0g fluorenes-9,9-dicarboxylate and 0.5g n-butyl phthalate.
Embodiment 13
Preparation method is with comparative example 1, and difference is 3.5g fluorenes-9-methyl-formiate-9-ethyl formate to be changed to 3.0g fluorenes-9,9-dicarboxylate and 0.5g9,9-methoxyl methyl fluorenes.
Embodiment 14
Preparation method is with comparative example 1, and difference is 3.5g fluorenes-9-methyl-formiate-9-ethyl formate to be changed to 3.0g fluorenes-9,9-dicarboxylate and 0.5g2,3-di-isopropyl ethyl succinate.
Embodiment 15
Preparation method is with comparative example 1, and difference is 3.5g fluorenes-9-methyl-formiate-9-ethyl formate to be changed to 3.0g fluorenes-9,9-dioctyl phthalate dimethyl ester and 0.5g n-butyl phthalate.
Embodiment 16
Preparation method is with comparative example 1, and difference is 3.5g fluorenes-9-methyl-formiate-9-ethyl formate to be changed to 3.0g fluorenes-9,9-dioctyl phthalate dimethyl ester and 0.5g9,9-methoxyl methyl fluorenes.
Embodiment 17
Preparation method is with comparative example 1, and difference is 3.5g fluorenes-9-methyl-formiate-9-ethyl formate to be changed to 2.0g fluorenes-9,9-dioctyl phthalate dimethyl ester and 1.5g2,3-di-isopropyl ethyl succinate.
Embodiment 18
Preparation method is with comparative example 1, and difference is 3.5g fluorenes-9-methyl-formiate-9-ethyl formate to be changed to 1.5g fluorenes-9,9-dicarboxylate and 2.0g fluorenes-9,9-dioctyl phthalate dimethyl ester.
Embodiment 19
Preparation method is with comparative example 2, and difference is 4g fluorenes-9-methyl-formiate-9-ethyl formate to be changed to 2.0g fluorenes-9,9-dicarboxylate and 1.5g n-butyl phthalate.
Embodiment 20
Preparation method is with comparative example 2, and difference is 4g fluorenes-9-methyl-formiate-9-ethyl formate to be changed to 3.0g fluorenes-9,9-dioctyl phthalate dimethyl ester and 0.8g n-butyl phthalate.
Embodiment 21
Preparation method is with comparative example 2, and difference is 4g fluorenes-9-methyl-formiate-9-ethyl formate to be changed to 2.0g fluorenes-9,9-dicarboxylate and 2.0g fluorenes-9,9-dioctyl phthalate dimethyl ester.
Embodiment 22
Preparation method is with comparative example 1, and difference is 3.5g fluorenes-9-methyl-formiate-9-ethyl formate to be changed to 2.5g fluorenes-9-methyl-formiate-9-ethyl formate and 1.0g n-butyl phthalate.
Embodiment 23
Preparation method is with comparative example 1, and difference is 3.5g fluorenes-9-methyl-formiate-9-ethyl formate to be changed to 1.0g fluorenes-9-methyl-formiate-9-ethyl formate and 2.5g n-butyl phthalate.
Embodiment 24
Preparation method is with comparative example 1, and difference is 3.5g fluorenes-9-methyl-formiate-9-ethyl formate to be changed to 0.5g fluorenes-9-methyl-formiate-9-ethyl formate and 3.0g n-butyl phthalate.
polymerization
Component using solid catalyst as olefin polymerization catalysis is carried out polymerization evaluation:
At 5L stainless steel cauldron after nitrogen is fully replaced, adding 5mL concentration is the triethyl aluminum hexane solution of 0.5mol/L and Cyclohexylmethyldimethoxysilane (CMMS) hexane solution that 1mL concentration is 0.1mol/L and the catalyzer 10mg of preparation, then add 10mL hexane to rinse charge line, add again 2L (under standard state) hydrogen, with the refining propylene of 2.5L, control reaction 20 DEG C of pre-polymerizations 5 minutes, be warming up to 70 DEG C, polyreaction 1 hour at this temperature.After reaction finishes, reactor is lowered the temperature and stop stirring and discharge reaction product, drying obtains polymkeric substance.(tap density of polymkeric substance adopts JB/T2412-2008 method, and degree of isotacticity adopts JB/T3682-2000 method.)
Table 2 catalyst performance
DNBP: n-butyl phthalate
Diether: 9,9-methoxyl methyl fluorenes
Succinate: 2,3-di-isopropyl ethyl succinate
Upper table polymerization result shows, in comparative example 1-4, adopt separately a kind of fluorenes two acid esters of unsaturated ring replacement diester compound as internal electron donor, adopt the different prepared catalyzer of catalyst preparation process, during for propylene polymerization, can obtain the activity of higher level, and under standard polymerization conditions, coordinate the prepared polypropylene of Cyclohexylmethyldimethoxysilane external electron donor to there is the degree of isotacticity higher than 97% substantially, illustrate that this compounds can be applicable to various typical catalyzer syntheti c routes as internal electron donor, and make catalyzer bring into play outstanding polymerization, obtain higher catalytic activity and the polypropylene product of high isotactic.And, in the time that such ring replacement ether acid ester cpds is selected from the composite uses of internal electron donor such as diether, succinate, phthalate with another, under identical catalyst preparation process prerequisite, compare the catalyzer of independent use DNBP or ring replacement ether esters of gallic acid internal electron donor, activity increases mostly, and the degree of isotacticity of gained polypropylene product is higher.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (21)
1. for the ingredient of solid catalyst of olefinic polymerization, this catalyst component comprises Mg, Ti, halogen and electron donor, this electron donor replaces two ester compounds at least one the unsaturated ring in (i) is selected from logical formula I, and (ii) simple function group or the polyfunctional group electron donor compound of at least one ether, ester, ketone or amine:
Wherein, A, B, C, D and E are all selected from carbon atom or are selected from the heteroatoms in N, O and S; W, X, Y, Z and m are 0 or 1; Condition is
In the time that n equals 0:
I) A, B, C and D are carbon atom, and X, Y, Z and W are 1; Or
II) A is nitrogen-atoms, and B, C and D are carbon atom, and W is that 0, X, Y and Z are 1; Or
III) A and D are nitrogen-atoms, and B and C are carbon atom, and W and Z are that 0, X and Y are 1; Or
IV) D is nitrogen-atoms, and A, B and C are carbon atom, and Z is that 0, W, X and Y are 1; Or
In the time that n equals 1:
I) A, B, C, D and E are carbon atom, and m is that 2, W, X, Y and Z are 1; Or
Ii) E is nitrogen-atoms, and A, B, C and D are carbon atom, and m is that 1, W, X, Y and Z are 1; Or
Iii) E is Sauerstoffatom, and A, B, C and D are carbon atom, and m is that 0, W, X, Y and Z are 1; Or
I) E is sulphur atom, and A, B, C and D are carbon atom, and m is that 0, W, X, Y and Z are 1; Or
Ii) D and E are nitrogen-atoms, and A, B and C are carbon atom, and m is that 1, W, X and Y are that 1, Z is 0.
R
1and R
2for identical or not identical C
1-C
20alkyl, such as C
1-C
20straight or branched alkyl, alkenyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl and C
7-C
20aralkyl; Identical or different R
3-R
7hydrogen atom, halogen atom, Sauerstoffatom, sulphur atom and C
1-C
20alkyl, such as C
1-C
20straight or branched alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl and C
7-C
20aralkyl;
Above-mentioned R
1-R
7at random comprise one or several R atom as carbon atom or hydrogen atom or both substituents, R atom is heteroatoms, the C of straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl and C
7-C
20aralkyl; Wherein R
1-R
7any two groups mutually bonding generate one or more volutions, condensed ring structure.
2. ingredient of solid catalyst according to claim 1, is characterized in that, the compound of described logical formula I comprises the compound of following logical formula II:
Wherein R
1-R
6group is as the definition in logical formula I.
3. ingredient of solid catalyst according to claim 2, is characterized in that, the compound of described logical formula II comprises the compound of following logical formula III:
Wherein R
1, R
2group is as the definition in logical formula I, and R ' is the C of identical or not identical hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl and C
7-C
20aralkyl.
4. ingredient of solid catalyst according to claim 1, is characterized in that, the compound described in logical formula I is selected from following compounds:
3,5-phenylbenzene 2H pyrroles-2,2-dicarboxylate; 3-(3-chloro-phenyl-)-5-methyl-pyrroles-2,2-dicarboxylate; 3-(3-bromophenyl)-5-methyl-pyrroles-2,2-dicarboxylate; Diethyl-3-(to chlorobenzene)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Fluorenes-9,9-dioctyl phthalate dimethyl ester; Fluorenes-9,9-dicarboxylate; Fluorenes-9,9-dioctyl phthalate di-n-propyl ester; Fluorenes-9,9-dioctyl phthalate diisopropyl ester; Fluorenes-9,9-dioctyl phthalate di-n-butyl; Fluorenes-9,9-dioctyl phthalate diisobutyl ester; Fluorenes-9,9-dioctyl phthalate two n-pentyl esters; Fluorenes-9, the just own ester of 9-dioctyl phthalate two; Fluorenes-9, the positive heptyl ester of 9-dioctyl phthalate two; Fluorenes-9,9-dioctyl phthalate di-n-octyl; 9-methyl-formiate-9-ethyl formate-fluorenes; 9-methyl-formiate-9-formic acid n-propyl-fluorenes; 9-methyl-formiate-9-isopropyl formate-fluorenes; 9-methyl-formiate-9-n-buty formate-fluorenes; 9-methyl-formiate-9-tetryl formate-fluorenes; 9-ethyl formate-9-formic acid n-propyl-fluorenes; 9-ethyl formate-9-isopropyl formate-fluorenes; 9-ethyl formate-9-n-buty formate-fluorenes; 9-ethyl formate-9-tetryl formate-fluorenes; Dimethyl 4H-benzo <g> thia <2,3-e> indazole-4,4-dicarboxylic acid esters; 2H-pyrroles-2, diethyl-5-phenyl-3 (to toluene), 2-manthanoate; Diethyl-3 (to anisole)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Diethyl 5-(to nitro)-3-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Diethyl-2,3-phenylbenzene-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(4-chlorobenzene)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(4-p-methoxy-phenyl)-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-(4-methylbenzene)-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-3-(4-oil of mirbane)-1H-indenes-1,1-dicarboxylic acid esters; Dimethylamino-4-five methoxycarbonyl-1,2,3,5,5-, five methoxycarbonyl cyclopentadiene; 3-phenyl-indenes-1,1-dioctyl phthalate methyl esters; Dimethyl-5-(to chlorobenzene) 3-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Dimethyl 3,4-bis-(to chlorobenzene) 2H-pyrroles-dicarboxylic acid esters; Dimethyl 3-(p-oil of mirbane)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Dimethyl 3-(m-oil of mirbane)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Dimethyl 5-(m-oil of mirbane)-5-phenyl-2H-pyrroles-2,2-dicarboxylic acid esters; Dimethyl 5,6-dimethyl-5H, 6H-encircles penta 2 indoles-11,11-dicarboxylic acid esters; 1-(2-oil of mirbane sulphur)-2,3,4,5,5-methyl-formiate-cyclopentadiene; 1-(2,4-dinitrobenzene)-2,3,4,5,5-five methyl-formiates-cyclopentadiene; Methyl-2-the tertiary butyl-3-methyl isophthalic acid H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-methyl-2-trimethyl silicane-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-methyl-2-phenyl-indenes-1,1-dicarboxylic acid esters; Diethyl-2,3-bis--n-propyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-3-methylol-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-2-the tertiary butyl-5,6-dimethoxy-3-methyl isophthalic acid H-indenes-1,1-dicarboxylic acid esters; Dimethyl-2-phenyl-3-(thia-2-yl)-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-3-(2-toluene) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-(2-methoxycarbonyl phenyl)-2 phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-(4-trifluoromethylbenzene) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 3-(4-phenyl methyl ketone) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-2-(hexamethylene 1-alkene)-3-(4-phenyl methyl ketone)-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 2-[(ethoxy acyl group) methyl]-1H-indenes-1,1-dicarboxylic acid esters; 1,1-diethyl-1H-indenes-1,1-dicarboxylic acid esters; The chloro-5 methyl-pyrazoles of 7-[4,3-d] pyrimidine-3,3-dioctyl phthalate ethyl ester; The chloro-7-methyl-pyrazoles of 5-[4,3-d] pyrimidine-3,3-dioctyl phthalate ethyl ester; 5-amino-7-methyl-pyrazoles [4,3-d] pyrimidine-3,3-dioctyl phthalate ethyl ester; 7-methoxyl group-5-methyl-pyrazoles [4,3-d] pyrimidine-3,3-dioctyl phthalate ethyl ester; 1-p-totuidine base-2,3,4,5,5-, five methoxycarbonyl cyclopentadiene; Dimethyl-3H-phenanthro-< 9,10-c > pyrazoles-3,3-dicarboxylic acid esters; 3,3-bis-(methoxycarbonyl)-3H-indazole; 3,3-bis-(ethoxycarbonyl) 3H-indazole; 1-trichloromethyl-2,3,4,5,5-, five methoxycarbonyl cyclopentadiene; 1-(2-methyl-4-oil of mirbane)-five methoxycarbonyl cyclopentadiene; 1-(the iodo-4-oil of mirbane of 2-)-five methoxycarbonyl cyclopentadiene; 2-(the iodo-4-oil of mirbane of 2-)-1,3,4,5,5-five methoxycarbonyl cyclopentadiene; 1-(2,4-dinitrobenzene)-2,3,4,5,5-five methoxycarbonyl cyclopentadiene; 4-benzyl-1, poly-(methoxycarbonyl) cyclopentadiene of 2,3,5,5-five; 3-benzyl-1, poly-(methoxycarbonyl) cyclopentadiene of 2,4,5,5-five; 2-(trifluoromethyl)-5-carbonyl-3,3-bis-(methoxycarbonyl)-3H-indoles; 2-(trifluoromethyl)-5-carbonyl-7-methyl-3,3-bis-(methoxycarbonyl)-3H-indoles; 3-(trifluoromethyl)-5-hydroxyl-7-methoxyl group-3,3-bis-(methoxycarbonyl)-3H-indoles; 2H-pyrroles-2, diethyl-3-phenyl-5 (to toluene), 2-dicarboxylic acid esters; Diethyl-2-(4-chlorobenzene)-5-morpholine-4H-imidazoles-4,4-dicarboxylic acid esters; 4,5,5-tricarboxylic acid methyl esters-1,2,3-trichlorine cyclopentadiene; Methyl-3-methyl-4-trimethyl silicane-ring penta-2,4-diene-1,1-dicarboxylic acid esters; Diethyl-2,5-phenylbenzene-4H-imidazoles-4,4-dicarboxylic acid esters; Diethyl-3-benzyl-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-3-(4-(methoxycarbonyl) phenyl) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-3-(4-acetylbenzene) 2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-methoxyl methyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl-2-the tertiary butyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-the tertiary butyl-1H-indenes-1,1-dicarboxylic acid esters; Dimethyl 2-normal-butyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl 2-normal-butyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl 2-n-hexyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(3-cyano group-1-propyl group)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-diethoxy methyl isophthalic acid H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(4-methoxyphenyl)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(1-tetrahydrobenzene)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-2-(cyclohexyl)-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-3-(3-toluene)-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl-3-(3-oil of mirbane)-2-phenyl-1H-indenes-1,1-dicarboxylic acid esters; Diethyl 13H-indeno [1,2-e]-Fei-13,13-dicarboxylic acid esters; Diethyl-2-hexyl-3-(4-methoxyphenyl) 1H-indenes-1,1-dicarboxylic acid esters; Ring penta [c] thia-5,5-dioctyl phthalate ethyl ester; 4-[4-[4-(methylsulphonic acid) benzene] 1,1-bis-(methoxyl group) ring penta-2,4-diene-3-yl] pyridine; Fluorenes-4,9, the 9-dioctyl phthalate-4-tertiary butyl-9,9-dimethyl ester; 4-(4-amino-pyridine-3-base carbamyl)-fluorenes-9,9-dioctyl phthalate methyl esters; 4-(3-amino-pyridine-4-base carbamyl)-fluorenes-9,9-dioctyl phthalate dimethyl ester; The iodo-2-phenyl-1H-of diethyl-3-indenes-1,1-dicarboxylic acid esters; The iodo-2-n-pentyl-1H-of diethyl-3-indenes-1,1-dicarboxylic acid esters; The iodo-2-of diethyl-3-(3 methoxyphenyl)-1H-indenes-1,1-dicarboxylic acid esters; The iodo-2-of diethyl-3-(naphthalene-2-yl)-1H-indenes-1,1-dicarboxylic acid esters; Di-n-hexyl-fluorenes-9,9-dicarboxylic acid esters; Two n-heptyls-fluorenes-9,9-dicarboxylic acid esters; Diethyl-2-benzene-3H-indenes-3,3-dicarboxylic acid esters; The bromo-1H-of diethyl-2-indenes-1,1-dicarboxylic acid esters;
1-ethyl-1-methyl-cyclohexyl-2,5-diene-1,1-dicarboxylic acid esters; N, 4,4-, tri-ethoxy carbon back-Isosorbide-5-Nitrae-dihydro-pyridines; 2,6-phenylbenzene-4,4-dimethoxycarbonyl-4H-pyrans; 2,6-phenylbenzene-4,4-dimethoxycarbonyl-Isosorbide-5-Nitrae-dihydropyridine; 2,6-bis-(4-chlorobenzene)-4,4-dimethoxycarbonyl-4H-pyrans; 2,6-bis-(4-methoxyphenyl)-4,4-dimethoxycarbonyl-4H-pyrans; 2,6-bis-(4-chlorobenzene)-4,4-dimethoxycarbonyl-Isosorbide-5-Nitrae-dihydropyridine; 2,6-bis-(4-methoxyphenyl)-4,4-dimethoxycarbonyl-Isosorbide-5-Nitrae-dihydropyridine; 1-cyclopentyl-4,4-bis-(methoxycarbonyl)-Isosorbide-5-Nitrae-dihydropyridine; 1-n-hexyl-4,4-bis-(methoxycarbonyl)-Isosorbide-5-Nitrae-dihydropyridine; 1-methoxy-6,6-bis-methanoyl methyl-cyclohexyl-Isosorbide-5-Nitrae-diene; Dimethyl Isosorbide-5-Nitrae-dihydronaphthalene-1,1-dicarboxylic acid esters; 2,6-bis-(4-chlorobenzene)-4,4-dimethoxy acyl group-4H-thiapyran; Diethyl-3-bromo-Isosorbide-5-Nitrae-dihydro-1-methyl pyridazino[3,4-b] quinoxaline-4,4-dicarboxylic acid esters; The bromo-3-of diethyl-5-phenyl-Isosorbide-5-Nitrae-dihydrogen dazin-4,4-dicarboxylic acid esters; Three hexyls-3-phenyl-Isosorbide-5-Nitrae-dihydrogen dazin-4,4,5-front three acid esters; 1-styroyl-bis-(methoxy acyl group) Isosorbide-5-Nitrae-dihydropyridine; Diethyl-2-methyl-6-benzene (4H-pyrans) 4,4-dicarboxylic acid esters; 1-(2-menaphthyl)-4,4-bis-(methoxy acyl group)-Isosorbide-5-Nitrae-dihydropyridine; Dimethyl-3-ethanoyl-1-toluquinoline-4,4 (1H)-dicarboxylic acid esters.
5. according to the ingredient of solid catalyst described in any one in claim 1-4, it is characterized in that, except the unsaturated ring that contains described logical formula I replaces two ester compounds, also comprise at least another kind of electron donor compound, this compound is selected from the Lewis alkali that contains one or more electronegativity groups, electron donor atom is wherein selected from the group of N, O, S, P, As or Sn composition, for example, be selected from the electron donor compound of two ethers, ester class, diones and Diamines.
6. ingredient of solid catalyst according to claim 5, is characterized in that, described diether compound is selected from 1 of logical formula IV, 3-the third two ethers:
Wherein: R, R
1, R
2, R
3, R
4and R
5can be identical or different, represent H or have straight chain or branched-alkyl, cycloalkyl, aryl, alkaryl or the aralkyl of 1-18 carbon atom; R
6and R
7can be identical or different, representative has the straight chain of 1-20 carbon atom or branched-alkyl, the cycloalkyl of a 3-20 carbon atom, the aryl of a 5-20 carbon atom, alkaryl and the aralkyl of a 7-20 carbon atom; R to R
7in one or more groups can link formation ring texture, all can comprise the one or more heteroatomss that are selected from halogen, N, O, S, P and Si.
7. ingredient of solid catalyst according to claim 5, is characterized in that, described ester compound is monocarboxylic ester or polycarboxylic acid ester compound.
8. ingredient of solid catalyst according to claim 7, is characterized in that, described ester compound is selected from the diester of aromatic binary carboxylic acid, as Bisphthalate or bis--terephthalate.
9. ingredient of solid catalyst according to claim 7, is characterized in that, described ester compound is selected from the succinate compounds of general formula (V):
Wherein, radicals R
1and R
2, be same to each other or different to each other, be C
1-C
20line style or branched-alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkylaryl group, optionally comprise heteroatoms; R
3-R
6in at least two groups be different from hydrogen and be selected from C
1-C
20line style or branched-alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkylaryl group, optionally contain heteroatoms, in addition, and radicals R
3-R
6can link together and form a ring.
10. ingredient of solid catalyst according to claim 7, is characterized in that, described ester compound is selected from the diol ester compound of logical formula VI:
R in formula
1-R
6, R
1-R
2for the C of identical or different hydrogen, halogen or replacement or unsubstituted straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl, C
7-C
20aralkyl, C
2-C
10alkylene or C
10-C
20fused ring aryl; But R
1and R
2not hydrogen, R
3-R
6and R
1-R
2in one or morely optionally become ring or Cheng Huan not.
11. according to the ingredient of solid catalyst described in claim 1-10 any one, it is characterized in that, the unsaturated ring that comprises titanium compound, magnesium compound and be selected from described logical formula I replaces the reaction product of two ester compounds, and the precursor of described magnesium compound is selected from least one: Mg (OR)
2, X
nmg (OR)
2-n, MgCl
2mROH, R
2-nmgX
n, MgR
2, MgCl
2/ SiO
2, MgCl
2/ Al
2o
3, or the mixture of magnesium halide and alcohol titanium, the number that in formula, m is 0.1-6,0<n<2, X is halogen, R is hydrogen or C
1-C
20alkyl; The general formula of described titanium compound is TiX
n(OR)
4-n, in formula, R is that carbonatoms is the alkyl of 1-20, X is halogen, n=1-4.
12. 1 kinds of methods of preparing described in claim 11 for the ingredient of solid catalyst of olefinic polymerization, it is characterized in that, comprise: make magnesium compound and titanium compound and the ring that is selected from described logical formula I replace ether acid ester internal electron donor compound and contact, thereby obtain ingredient of solid catalyst.
The preparation method of 13. ingredients of solid catalyst for olefinic polymerization according to claim 12, it is characterized in that, described magnesium compound is the one in the derivative that in magnesium dihalide molecular formula, wherein at least one halogen atom is replaced by-oxyl or halo-oxyl; Or described magnesium compound is alkoxyl magnesium or aryloxy magnesium; Or the described magnesium compound alcohol adduct that is magnesium dihalide; Or described magnesium compound is to make general formula R under a kind of existence of the compound that is selected from alcohol, phenol, ketone, aldehyde, ether, amine, pyridine and ester
2-nmgX
nliquid magnesium compound contact redeposition with liquid titanium compound and separate out solid.
14. 1 kinds for alkene CH
2the catalyzer of=CHR polymerization, wherein R is hydrogen or the hydrocarbyl group containing 1-12 carbon atom, it is characterized in that, comprises the product of following substance reaction:
(a) ingredient of solid catalyst described in any one in claim 1-11;
(b) at least one general formula is AlR
nx
(3-n)organo-aluminium compound, in formula, R is the alkyl of hydrogen, carbonatoms 1-20; X is halogen, the integer that n is 0≤n≤3; With, optionally,
(c) at least one external donor compound.
15. catalyzer according to claim 14, is characterized in that, described organo-aluminium compound (b) is a kind of trialkyl aluminium compound.
16. catalyzer according to claim 15, is characterized in that, described trialkyl aluminium compound is selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, trioctylaluminum.
17. catalyzer according to claim 14, is characterized in that, it is R that described external donor compound (c) is selected from general formula
nsi (OR
1)
4-nsilicone compounds, R and R in formula
1for C
1-C
18alkyl, optionally also have heteroatoms; N is the integer of 0≤n≤3.
18. 1 kinds for alkene CH
2the pre-polymerized catalyst of=CHR polymerization, wherein R is hydrogen or the hydrocarbyl group containing 1-12 carbon atom, it is characterized in that, described pre-polymerized catalyst comprises a kind of prepolymer that carries out prepolymerization gained according to the ingredient of solid catalyst described in any one in claim 1-11 and alkene.
19. according to the pre-polymerized catalyst of claim 18, it is characterized in that, carrying out prepolymerized alkene is ethene or propylene.
20. for alkene CH
2the method of=CHR polymerization, comprises homopolymerization, pre-polymerization and copolymerization, and wherein R is hydrogen or the hydrocarbyl group containing 1-12 carbon atom, and the catalyzer in claim 14-19 described in any one or pre-polymerized catalyst carry out under existing.
21. methods according to claim 20, is characterized in that, described alkene is normal olefine, and described normal olefine is selected from ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-nonene, 1-decene; Described alkene is also branched-chain alkene, and described branched-chain alkene is selected from: 3-methyl-1-butene or 4-methyl-1-pentene; Described alkene is also diolefine, and described diolefine is selected from: divinyl, vinyl cyclopentenes or vinyl cyclohexene.
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| CN105085745A (en) * | 2015-09-29 | 2015-11-25 | 李海燕 | Internal electron donor of olefinic polymerization catalyst, catalyst ingredient, and preparation method |
| CN107129547A (en) * | 2016-02-29 | 2017-09-05 | 中国石油化工股份有限公司 | Ingredient of solid catalyst, catalyst and application for olefinic polymerization |
| CN107129549A (en) * | 2016-02-29 | 2017-09-05 | 中国石油化工股份有限公司 | Ingredient of solid catalyst, catalyst and application for olefinic polymerization |
| CN107417818A (en) * | 2016-05-23 | 2017-12-01 | 北京利和知信科技有限公司 | It is a kind of for the catalytic component of olefinic polymerization, preparation method and catalyst |
| CN108570119A (en) * | 2017-03-10 | 2018-09-25 | 北京利和知信科技有限公司 | A kind of ingredient of solid catalyst containing naphthylenediamine class compound, catalyst and its application |
| CN109251258A (en) * | 2017-07-13 | 2019-01-22 | 中国石油天然气股份有限公司 | Wide-distribution polypropylene catalytic component, preparation method of component and catalyst thereof |
| CN113754802A (en) * | 2020-06-05 | 2021-12-07 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization reaction and prepolymerization catalyst composition |
| CN114716591A (en) * | 2022-03-23 | 2022-07-08 | 任丘市利和科技发展有限公司 | Catalyst component for propylene polymerization, preparation method and application thereof |
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| CN107129547A (en) * | 2016-02-29 | 2017-09-05 | 中国石油化工股份有限公司 | Ingredient of solid catalyst, catalyst and application for olefinic polymerization |
| CN107129549A (en) * | 2016-02-29 | 2017-09-05 | 中国石油化工股份有限公司 | Ingredient of solid catalyst, catalyst and application for olefinic polymerization |
| CN107417818A (en) * | 2016-05-23 | 2017-12-01 | 北京利和知信科技有限公司 | It is a kind of for the catalytic component of olefinic polymerization, preparation method and catalyst |
| CN107417818B (en) * | 2016-05-23 | 2021-09-21 | 北京利和知信科技有限公司 | Catalyst component for olefin polymerization, preparation method and catalyst |
| CN108570119A (en) * | 2017-03-10 | 2018-09-25 | 北京利和知信科技有限公司 | A kind of ingredient of solid catalyst containing naphthylenediamine class compound, catalyst and its application |
| CN108570119B (en) * | 2017-03-10 | 2020-07-31 | 北京利和知信科技有限公司 | Solid catalyst component containing naphthalenediamine compound, catalyst and application thereof |
| CN109251258A (en) * | 2017-07-13 | 2019-01-22 | 中国石油天然气股份有限公司 | Wide-distribution polypropylene catalytic component, preparation method of component and catalyst thereof |
| CN109251258B (en) * | 2017-07-13 | 2021-06-01 | 中国石油天然气股份有限公司 | Wide-distribution polypropylene catalytic component, preparation method of component and catalyst thereof |
| CN113754802A (en) * | 2020-06-05 | 2021-12-07 | 中国石油化工股份有限公司 | Catalyst system for olefin polymerization reaction and prepolymerization catalyst composition |
| CN114716591A (en) * | 2022-03-23 | 2022-07-08 | 任丘市利和科技发展有限公司 | Catalyst component for propylene polymerization, preparation method and application thereof |
| CN114716591B (en) * | 2022-03-23 | 2024-05-28 | 任丘市利和科技发展有限公司 | Catalyst component for propylene polymerization, preparation method and application thereof |
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