CN104058967A - Unsaturated cyclosubstituted diacid ester compound suitable for preparing olefin polymerization catalyst - Google Patents
Unsaturated cyclosubstituted diacid ester compound suitable for preparing olefin polymerization catalyst Download PDFInfo
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- CN104058967A CN104058967A CN201410265537.0A CN201410265537A CN104058967A CN 104058967 A CN104058967 A CN 104058967A CN 201410265537 A CN201410265537 A CN 201410265537A CN 104058967 A CN104058967 A CN 104058967A
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- acid esters
- dicarboxylic acid
- indenes
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Abstract
The invention provides an unsaturated cyclosubstituted diacid ester compound and a preparation method thereof, and application of the unsaturated cyclosubstituted diacid ester compound in preparing an olefin polymerization catalyst component. When being used for preparing the Ziegler-Natta catalyst component as an electron donor, the compound can enable the catalyst component to have excellent activity and polymer products with high degree of isotacticity can be obtained.
Description
Technical field
The present invention relates to preparation method that a kind of unsaturated ring replaces two ester compounds, this compound with and at CH
2application in the preparation of=CHR olefin polymerization catalysis, wherein R is hydrogen or the hydrocarbyl group containing 1-12 carbon atom.
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 in the sense, is sought the research of better electron donor exactly.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.
But the balance of Ziegler-Natta catalyst component prepared by the employing above-claimed cpd activity/degree of isotacticity when for olefinic polymerization is also unsatisfactory, therefore needs it further to research and develop.
Summary of the invention
The object of the present invention is to provide one to be particularly useful for making CH
2the unsaturated ring of=CHR olefin polymerization catalyst components replaces two ester compounds, and wherein R is hydrogen or the hydrocarbyl group containing 1-12 carbon atom.
Another object of the present invention is to provide the preparation method of this compounds.
A further object of the present invention is to provide this compounds at CH
2application in the preparation of=CHR olefin polymerization catalysis.
In order to realize object of the present invention, the unsaturated ring shown in a kind of logical formula I replaces two ester compounds:
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.
Another object of the present invention is to provide the synthetic method that a kind of unsaturated ring replaces two ester compounds, and the compound shown in logical formula I can be synthetic by various reactions.One of them be by following formula three-step reaction is synthetic (can be referring to US4564700A1; Journal of the Chemical Society, 1949, P2182,2185; Analytical Chemistry, vol.32, NO.4, April1960):
A) ring compound that contains accordingly two hydrogen is reacted to (seeing following formula A1) with carbonic acid gas and alkyl lithium reagents, or react with alkyl-dimethyl ester and sodium hydride and be prepared into cyclic hydrocarbon radical and replace formic acid (seeing following formula A2), each substituting group is with the definition in logical formula I;
B) 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;
C) prepare by upper step product and with the suitable halide precursors addition containing acyloxy.
For example, fluorenes-9-methyl-formiate-9-ethyl formate can react and prepare fluorenes formic acid with n-Butyl Lithium with fluorenes, then adopts step B and C to prepare.Concrete reaction formula is as follows:
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):
For example, fluorenes-9, the preparation feedback formula of 9-dicarboxylate is as follows:
Ring of the present invention replaces two ester compounds at preparation CH
2application in=CHR olefin polymerization catalysis.Wherein R is hydrogen or the hydrocarbyl group containing 1-12 carbon atom.
The present invention adopts the bifunctional compound with ad hoc structure, i.e. unsaturated cyclosubstituted two ester compounds as shown in logical formula I, 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 replaces structure, has steric effect and can fix the steric configuration of diester bifunctional, has positive effect in the formation of participation catalyst active center and to the stereospecificity of raising catalyzer.Through verification experimental verification, in the time that this compounds is prepared to Ziegler-Natta catalyst component for electron donor, can make catalyst component there is good activity, can obtain the polymeric articles of high isotactic by polymerization.
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 two acid esters examples
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.
Embodiment 9
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 10.43g 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) %.
Embodiment 10
The same embodiment of catalyst component preparation process, difference is for to be changed to fluorenes-9 by fluorenes-9-methyl-formiate-9-ethyl formate, and 9-dioctyl phthalate dimethyl ester, obtains ingredient of solid catalyst, analyzing titanium content is 2.9 (wt) %, and fluorenes two acid and esters contents are 13.74 (wt) %.
Embodiment 11
The same embodiment of catalyst component preparation process, difference is for to be changed to fluorenes-9 by fluorenes-9-methyl-formiate-9-ethyl formate, and 9-dicarboxylate, obtains ingredient of solid catalyst, analyzing titanium content is 3.04 (wt) %, and fluorenes two acid and esters contents are 16.50 (wt) %.
Embodiment 12
The same embodiment of catalyst component preparation process, difference is for to be changed to fluorenes-9 by fluorenes-9-methyl-formiate-9-ethyl formate, and 9-dioctyl phthalate di-n-propyl ester, obtains ingredient of solid catalyst, analyzing titanium content is 2.59 (wt) %, and fluorenes two acid and esters contents are 11.19 (wt) %.
Embodiment 13
The same embodiment of catalyst component preparation process, difference is for to be changed to fluorenes-9 by fluorenes-9-methyl-formiate-9-ethyl formate, and 9-dioctyl phthalate diisopropyl ester, obtains ingredient of solid catalyst, analyzing titanium content is 4.07 (wt) %, and fluorenes two acid and esters contents are 5.35 (wt) %.
Embodiment 14
The same embodiment of catalyst component preparation process, difference is for to be changed to fluorenes-9 by fluorenes-9-methyl-formiate-9-ethyl formate, and 9-dioctyl phthalate di-n-butyl, obtains ingredient of solid catalyst, analyzing titanium content is 3.10 (wt) %, and fluorenes two acid and esters contents are 8.47 (wt) %.
Embodiment 15
The same embodiment of catalyst component preparation process, difference is for to be changed to fluorenes-9 by fluorenes-9-methyl-formiate-9-ethyl formate, and 9-dioctyl phthalate diisobutyl ester, obtains ingredient of solid catalyst, analyzing titanium content is 3.47 (wt) %, and fluorenes two acid and esters contents are 11.69 (wt) %.
Embodiment 16
The same embodiment of catalyst component preparation process, difference is for to be changed to fluorenes-9 by fluorenes-9-methyl-formiate-9-ethyl formate, and 9-dioctyl phthalate dibenzyl ester, obtains ingredient of solid catalyst, analyzing titanium content is 3.11 (wt) %, and fluorenes two acid and esters contents are 7.79 (wt) %.
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
Table 2 polymerization result shows, the catalyzer of preparing as internal electron donor with fluorenes two acid esters that are selected from unsaturated ring and replace two ester compounds, 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%.
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 (7)
1. the unsaturated ring shown in a logical formula I replaces two ester compounds:
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. unsaturated ring according to claim 1 replaces two ester compounds, it 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. unsaturated ring according to claim 2 replaces two ester compounds, it 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. unsaturated ring according to claim 1 replaces two ester compounds, it 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. the unsaturated ring described in claim 1-4 any one replaces a preparation method for two ester compounds, it is characterized in that, comprise the steps: by corresponding unsaturated ring substitution compound be prepared into ring replace formic acid, then with corresponding alcohol R
1oH reaction esterification is manthanoate, or with suitable ester class precursor direct addition be that unsaturated ring replaces manthanoate; Obtain product by upper step product and with the suitable precursor addition containing perester radical.
6. the unsaturated ring described in claim 1-4 any one replaces a preparation method for two ester compounds, it is characterized in that, when described unsaturated ring replaces two ester compound R
1and R
2when identical, adopt corresponding unsaturated cyclic cpds directly and lithium reagent and haloformate single step reaction prepare.
7. the unsaturated ring described in claim 1-4 any one replaces two ester compounds in the application of preparing in olefin polymerization catalysis.
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| CN105622416A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Method for preparing fluorenyl group and carboxylic acid ester-combined compound |
| CN105622804A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Solid catalyst component used for olefin polymerization and catalyst used for olefin polymerization and application |
| CN105622797A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Solid catalyst component used for olefin polymerization and catalyst used for olefin polymerization and application |
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Application publication date: 20140924 |