CN100338015C - Glycol ester compound for preparing catalyst for olefinic polymerization - Google Patents

Glycol ester compound for preparing catalyst for olefinic polymerization Download PDF

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CN100338015C
CN100338015C CNB031496989A CN03149698A CN100338015C CN 100338015 C CN100338015 C CN 100338015C CN B031496989 A CNB031496989 A CN B031496989A CN 03149698 A CN03149698 A CN 03149698A CN 100338015 C CN100338015 C CN 100338015C
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phenyl
hydrogen
group
ester compound
dibenzoate
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CN1580033A (en
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李昌秀
王军
高明智
李现忠
刘昆正
杨菊秀
邢凌燕
李新荣
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The present invention relates to a novel dihydric alcohol ester compound disclosed in a general formula (I) and a preparation method thereof and an application of the compound in the preparation of olefin polymerization catalysts, wherein n is larger than or equal to 3, and R1 and R2 are identical or different and are selected from C1 to C20 alkyl, cycloalkyl, aryl, alkaryl, aralkyl and alkylene or fused ring aryl; R3 to R6, R<1> and R<2> groups are identical or different and are selected from hydrogen and halogen or straight-chain or branched-chain C1 to C20 alkyl, cycloalkyl, aryl, alkaryl, aralkyl and alkylene or fused ring aryl, but R <1>, R<2> and R3 to R6 can not be hydrogen or halogen wholly. Groups containing one or a plurality of halogen atoms are optionally selected from R1 to R6 and R<1> to R<2> groups to be used as the substitute of carbon atoms or hydrogen atoms or both carbon atoms and hydrogen atoms.

Description

Be used to prepare the diol ester compound of olefin polymerization catalysis
Technical field
The present invention relates to a kind of new dibasic alcohol ester compound, the preparation method of this compound and this compound are used being used for preparing olefin polymerization catalysis.
Technical background
As everyone knows, with magnesium, titanium, halogen and electron donor solid titanium catalyst component, can be used for CH as basal component 2=CHR olefinic polyreaction, particularly in alpha-olefine polymerizing, can obtain the polymkeric substance of higher yields and higher tacticity with 3 carbon or more carbon atoms, wherein the electron donor compound is one of requisite composition in the catalyst component, and along with the development of internal electron donor compound has caused polyolefin catalyst constantly to update.At present, multiple electron donor compound is disclosed in a large number, for example polycarboxylic acid, monocarboxylic ester or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine etc. and derivative thereof, wherein comparatively commonly used is aromatic carboxylates's class of binary, for example n-butyl phthalate or diisobutyl phthalate etc. can be referring to U.S. Pat 4784983.
In recent years, the electron donor that people attempt to adopt other compound to be used as in the olefin polymerization catalyst components again uses, for example at U.S. Pat 4971937 and the European patent EP 0728769 disclosed catalyst component that is used for olefinic polyreaction, special 1 of two ether groups that contain have been adopted, the 3-diether compound is as electron donor, 2-sec.-propyl-2-isopentyl-1 for example, 3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal and 9,9 '-two (methoxymethyl) fluorenes etc.At the disclosed ingredient of solid catalyst that is used for olefinic polyreaction of Chinese patent CN1054139A, adopted special 1 of two ketone groups that contain, the 3-cyclohexadione compounds is as electron donor, for example 2,2 ', 4,6,6 '-pentamethyl--3,5-heptadione and 2,2 ', 6,6 '-tetramethyl--4-ethyl-3,5-heptadione etc.
The special dibasic aliphatic carboxylic acid ester compound of one class is disclosed again recently, as (referring to WO98/56830, WO98/56834, WO01/57099, WO01/63231 and WO00/55215) such as succinate, malonic ester, glutarates, the use of this class electron donor compound not only can improve activity of such catalysts, and the molecular weight distribution of gained propene polymer is obviously widened.
Yet, the above-mentioned disclosed binary aromatic carboxylic acid's ester compound of above-mentioned employing, contain 1 of two ether groups, the catalyzer that is used for olefinic polymerization of 3-diether compound and the preparation of dibasic aliphatic carboxylic acid ester compound all exists certain defective in actual applications, for example adopt the catalytic activity of catalyzer of binary aromatic carboxylic acid's ester compound lower, and the molecular weight distribution of resulting polymers is also narrower; Adopt 1, though the catalyzer of 3-diether compound is active higher, and catalyzer susceptibility that hydrogen is transferred might as well, the narrow molecular weight distribution of resulting polymers is unfavorable for the exploitation of the different trades mark of polymkeric substance; And adopt the catalytic activity of catalyzer of recent disclosed dibasic aliphatic carboxylicesters still on the low side, and when not adopting the external electron donor component, the degree of isotacticity of resulting polymers is lower.
The inventor has unexpectedly found a kind of polyol ester compound that contains special construction, when it uses as the electron donor in the olefin polymerization catalysis, can obtain the good comprehensive properties catalyzer, when being used for propylene polymerization, can obtain gratifying polymerization yield rate, and the stereospecificity of polymkeric substance is higher, even when not using external electron donor, still can obtain the polymkeric substance of higher degree of isotacticity, catalyzer is also better to the susceptibility of hydrogen accent simultaneously, the molecular weight distribution broad of resulting polymers helps the exploitation of the different trades mark of polymkeric substance.It can obtain still less gel content during especially for second third copolymerization at the copolymerization that is used for alkene in addition, therefore has better copolymerization performance.
Summary of the invention
A kind of dibasic alcohol ester compound with following general formula (I):
Figure C0314969800051
Wherein:
N 〉=3, R 1And R 2Can be identical or inequality, be selected from the C of straight or branched 1-C 20Alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkylene or fused ring aryl, R 3-R 6, R 1And R 2Group can be identical or inequality, is selected from the C of hydrogen, halogen or straight or branched 1-C 20Alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkylene or fused ring aryl, but R 1, R 2, R 3, R 4, R 5And R 6Can not be hydrogen or halogen entirely, and R 1-R 6And R 1-R 2Choose wantonly in the group and comprise one or more halogen atoms as carbon or hydrogen atom or both substituents;
When n=3, R 1, R 2, R 3, R 4, R 5And R 6Have at least two groups not to be hydrogen, when having only two groups not for hydrogen, all the other groups can not be methyl or ethyl entirely, R 1, R 2, R 3-R 6Being connected in the group between the group on the different carbon atoms can not Cheng Huan, but can form two condensed ring, this moment R 1And R 2Can not halogen atom;
When n=4, R 1, R 2, R 3, R 4, R 5And R 6Can not Cheng Huan between group, and when wherein having two during for methyl or phenyl, other groups can not be hydrogen entirely;
When n 〉=5, R 1, R 2, R 3, R 4, R 5And R 6Can not Cheng Huan between group.
Preferably, R 3And R 4, R 5And R 6In to have a group respectively at least be ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, phenyl or halogenated phenyl and can not be simultaneously be phenyl, R 1And R 2Identical or different, be hydrogen or methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, allyl group, phenyl or halogenated phenyl.More preferably, R 3And R 4, R 5And R 6In a group is arranged respectively is hydrogen, and another group is ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, phenyl or halogenated phenyl and can not be phenyl, R simultaneously 1And R 2Identical or different, be hydrogen or methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, allyl group, phenyl or halogenated phenyl.
Work as R 3And R 4, R 5And R 6In a group is arranged respectively is hydrogen, and another group is a methyl, and R 1And R 2Simultaneously for hydrogen or be respectively hydrogen and during methyl, R 1, R 2In have at least one to be the group that contains the phenyl ring that ortho position or a position replaced by halogen or alkyl.
Preferably, R 1, R 2In have at least one to be the group that contains phenyl ring, more preferably, R 1, R 2In have at least one to be phenyl or by C 1-C 20Alkyl or the phenyl that replaces of halogen, most preferably, R 1, R 2All are phenyl or by C 1-C 20Alkyl or the phenyl that replaces of halogen.
Preferably, n=3 in the general formula compound (I), R 1, R 2, R 3, R 4, R 5And R 6Have at least two groups not to be hydrogen, when having only two groups not for hydrogen, all the other groups can not be methyl or ethyl entirely, R 1, R 2, R 3-R 6Being connected in the group between the group on the different carbon atoms can not Cheng Huan, but can form two condensed ring, this moment R 1And R 2Have at least one to be aryl or alkaryl, more preferably R 1And R 2Be aryl or alkaryl.
Preferably, n=4 in the general formula compound (I), R 1, R 2, R 3, R 4, R 5And R 6Can not Cheng Huan between group, and when wherein having two during for methyl, other groups can not be hydrogen entirely, R 1And R 2Have at least one to be that halogen replaces or unsubstituted aryl or alkaryl, more preferably R 1And R 2Being halogen replaces or unsubstituted aryl or alkaryl.
In the above-mentioned general formula (I), preferred such compound, wherein R 3And R 4, R 5And R 6In a group is arranged respectively is hydrogen, and another group is ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, phenyl or halogenated phenyl and can not be phenyl, R simultaneously 1And R 2Identical or different, be hydrogen or methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, allyl group, phenyl or halogenated phenyl, R 1, R 2All are phenyl or by C 1-C 20Alkyl or the phenyl that replaces of halogen, and preferred n=3 or 4.
Dibasic alcohol ester compound of the present invention, optional from following compound:
2,6-dimethyl-2,6-heptanediol dibenzoate, 3,4-dimethyl-2,6-heptanediol dibenzoate, 3,4-dibutyl-2,6-heptanediol dibenzoate, 3,5-dimethyl-2,6-heptanediol dibenzoate, 3,5-dipropyl-2,6-heptanediol dibenzoate, 3,3 '-dimethyl-2,6-heptanediol dibenzoate, 3,3 '-dibutyl-2,6-heptanediol dibenzoate, 3,5-dibutyl-2,6-heptanediol dibenzoate, 3,3 ', 4-trimethylammonium-2,6-heptanediol dibenzoate, 3,3 ', 4-tributyl-2,6-heptanediol dibenzoate, 3,3 ', 5-trimethylammonium-2,6-heptanediol dibenzoate, 3,4,4 '-trimethylammonium-2,6-heptanediol dibenzoate, 3,3 '-dimethyl-2,6-heptanediol dibenzoate, 3,3 ', 4,4 '-tetramethyl--2,6-heptanediol dibenzoate, 3,3 ', 5,5 '-tetramethyl--2,6-heptanediol dibenzoate, 3,3 ', 4,4 ', 5,5 '-hexamethyl-2,6-heptanediol dibenzoate, 2,2 '-dimethyl-1,5-pentanediol dibenzoate, 2,2 '-diethyl-1,5-pentanediol dibenzoate, 2,2 '-dipropyl-1,5-pentanediol dibenzoate, 2,2 '-di-isopropyl-1,5-pentanediol dibenzoate, 2,2 '-dibutyl-1,5-pentanediol dibenzoate, 2,2 '-diisobutyl-1,5-pentanediol dibenzoate, 2,3-dimethyl-1,5-pentanediol dibenzoate, 2,3-diethyl-1,5-pentanediol dibenzoate, 2,3-dipropyl-1,5-pentanediol dibenzoate, 2,3-dibutyl-1,5-pentanediol dibenzoate, 2,4-dimethyl-1,5-pentanediol dibenzoate, 2,4-diethyl-1,5-pentanediol dibenzoate, 2,4-dipropyl-1,5-pentanediol dibenzoate, 2,4-di-isopropyl-1,5-pentanediol dibenzoate, 2,4-diisobutyl-1,5-pentanediol dibenzoate, 2,4-dibutyl-1,5-pentanediol dibenzoate, 2,3,4-trimethylammonium-1,5-pentanediol dibenzoate, 2,3,4-triethyl-1,5-pentanediol dibenzoate, 2,3,4-tripropyl-1,5-pentanediol dibenzoate, 2,3,4-triisopropyl-1,5-pentanediol dibenzoate, 2,3,4-tributyl-1,5-pentanediol dibenzoate, 2,3,4-triisobutyl-1,5-pentanediol dibenzoate, 3,4,5-trimethylammonium-2,6-heptanediol dibenzoate, 2,2 ', 3-trimethylammonium-1,5-pentanediol dibenzoate, 2,2 ', 4-trimethylammonium-1,5-pentanediol dibenzoate, 2,3,3 '-trimethylammonium-1,5-pentanediol dibenzoate, 1,1 '-dibenzoyl oxygen ethylcyclohexane, 3,3 '-dimethyl-1,5-pentanediol dibenzoate, 3,3 '-diethyl-1,5-pentanediol dibenzoate, 3,3 '-dipropyl-1,5-pentanediol dibenzoate, 3,3 '-di-isopropyl-1,5-pentanediol dibenzoate, 3,3 '-diisobutyl-1,5-pentanediol dibenzoate, 3,3 '-dibutyl-1,5-pentanediol dibenzoate, 1,5-phenylbenzene-1,5-pentanediol dibenzoate, 2,4-phenylbenzene-1,5-pentanediol dibenzoate, 1,5-phenylbenzene-2,6-pentanediol dibenzoate, 1,5-phenylbenzene-1,5-pentanediol dipropionate, 1,4-dibenzoyl oxygen methylcyclohexane, 1,4-xylyl alcohol dibenzoate, 2,5-phenylbenzene-1,6-heptanediol dibenzoate, 1,6-hexylene glycol dibenzoate, 2,2 '-biphenyl dimethanol dibenzoate, 2,2 '-biphenyl dimethanol dipropionate, 2,2 '-biphenyl dimethanol two pivalates, 2,2 '-dinaphthalene dimethanol dibenzoate, 2,2 '-methylene bridge binaphthol dibenzoate, 2,3-dimethyl-1,6-hexylene glycol dibenzoate, 2,4-dimethyl-1,6-hexylene glycol dibenzoate, 3,4-dibutyl-1,6-hexylene glycol dibenzoate, 3,3 '-dibutyl-1,6-hexylene glycol dibenzoate, 3,3 '-dimethyl-1,6-hexylene glycol dibenzoate, 2,2 '-dimethyl-1,6-hexylene glycol dibenzoate, 2,5-dibutyl-1,6-hexylene glycol dibenzoate, 3,4-dimethyl-1,6-hexylene glycol dibenzoate, 3,5-dimethyl-1,6-hexylene glycol dibenzoate, 2,5-dimethyl-1,6-hexylene glycol dibenzoate, 2,3,4,5-tetramethyl--1,6-hexylene glycol dibenzoate, 2,5-phenylbenzene-1,6-hexylene glycol dibenzoate, 2,7-ethohexadiol dibenzoate, 3,4-dibutyl-2,7-ethohexadiol dibenzoate, 3,3 '-dibutyl-2,7-ethohexadiol dibenzoate, 3,3 '-dimethyl-2,7-ethohexadiol dibenzoate, 4,4 '-dimethyl-2,7-ethohexadiol dibenzoate, 4,4 '-dibutyl-2,7-ethohexadiol dibenzoate, 3,5-dibutyl-2,7-ethohexadiol dibenzoate, 3,6-dimethyl-2,7-ethohexadiol dibenzoate, 3,4-dimethyl-2,7-ethohexadiol dibenzoate, 3,5-dimethyl-2,7-ethohexadiol dibenzoate, 3,3 ', 4,4 '-tetramethyl--2,7-ethohexadiol dibenzoate, 3,3 ', 5,5 '-tetramethyl--2,7-ethohexadiol dibenzoate, 3,3 ', 6,6 '-tetramethyl--2,7-ethohexadiol dibenzoate, 3,4,5,6-tetramethyl--2,7-ethohexadiol dibenzoate, 3,3 ', 4,4 ', 5,5 ', 6,6 '-prestox-2,7-ethohexadiol dibenzoate, 3,5-phenylbenzene-2,7-ethohexadiol dibenzoate, 3,4-phenylbenzene-2,7-ethohexadiol dibenzoate, 3,6-phenylbenzene-2,7-ethohexadiol dibenzoate.
Dibasic alcohol ester compound of the present invention can be synthetic by various reactions, wherein can make corresponding dibasic alcohol of general formula (I) such as general formula (II) carry out esterification and obtain in the presence of corresponding acid or acyl chlorides:
HO-CR 3R 4-(CR 1R 2) n-CR 5R 6-OH (II)
Wherein n, R 1, R 2, R 3-R 6Definition such as the definition in the general formula (I).
Can synthesizing of the dibasic alcohol of general formula (II) by known method.Also can be referring to the preparation method of disclosed dibasic alcohol among the Chinese patent CN1020448C.
Dibasic alcohol ester compound of the present invention can be applicable to prepare in the olefin polymerization catalysis, can obtain the catalyzer of high comprehensive performance, when being used for propylene polymerization, can obtain gratifying polymerization yield rate, and the stereospecificity of polymkeric substance is very high, the molecular weight distribution broad of resulting polymers helps the exploitation of the different trades mark of polymkeric substance.
Embodiment
Embodiment given below is for the present invention is described, rather than limits the invention.
Testing method
1, fusing point: adopt XT4A micro melting point apparatus (temperature control type).
2, the mensuration of nucleus magnetic resonance: use Bruke dmx300 nmr determination 1H-NMR (300MHz, solvent C DCl 3, TMS is interior mark, measures temperature 300K).
3, molecular weight distribution MWD (MWD=Mw/Mn) employing PL-GPC220 is mensuration (standard specimen: PS, flow velocity: 1.0ml/min, the pillar: 3xPlgel 10umM1xED-B 300 * 7.5nm) of solvent under 150 ℃ with the trichlorobenzene
4, the polymkeric substance degree of isotacticity adopts the heptane extraction process to measure (heptane boiling extracting 6 hours).
Synthesizing of compound
Embodiment 1
2,2 '-dimethyl-1, the preparation of 5-pentanediol dibenzoate
(1) 2,2 '-preparation of dimethylated pentanedioic acid diethyl alcohol ester
0.1mol 2,2 '-adding 0.3mol ethanol, 40ml toluene and the 0.4ml vitriol oil in the dimethylated pentanedioic acid, the stirring and evenly mixing post-heating refluxes.Dewater with water trap, reach Theoretical Calculation amount, stopped reaction up to the water of telling.With the saturated sodium carbonate solution neutralization, ethyl acetate extraction is told upper solution, and the saturated common salt aqueous solution is washed till neutrality, anhydrous sodium sulfate drying.Remove and to desolvate, underpressure distillation get colourless liquid 2,2 '-dimethylated pentanedioic acid diethyl alcohol ester, yield 90%.
2,2 '-dimethylated pentanedioic acid diethyl alcohol ester 1H NMR (TMS, CDCl 3, ppm, δ): 1.18 (6H, s, methyl H), 1.23～1.27 (6H, t, alcoholic acid methyl H), 1.7～1.8 (2H, t, methylene radical H), 2.25～2.29 (2H, t, methylene radical H), 4.0～4.1 (4H, m, alcoholic acid methylene radical H).
(2) 2,2 '-preparation of dimethyl-penten glycol
Add the 100ml anhydrous diethyl ether in the 3g Lithium Aluminium Hydride, the ice bath cooling is vigorous stirring down.Slowly drip 0.05mol 2,2 '-dimethylated pentanedioic acid diethyl alcohol ester, reflux 5h then.The Lithium Aluminium Hydride of cooling back water decomposing excessive filters back extracted with diethyl ether solution, anhydrous sodium sulfate drying.Remove and desolvate, column chromatography gets colourless viscous liquid 2,2-dimethyl-penten glycol, yield 75%.The IR spectrogram is at 3400cm -1There is strong absorption peak at the place, and at 1700cm -1About do not have absorption peak, prove that reduction reaction carries out fully.
(3) 2,2 '-dimethyl-1, the preparation of 5-pentanediol dibenzoate
0.03mol 2,2 '-add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the dimethyl-penten glycol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography, colourless viscous liquid 2,2 '-dimethyl-1,5-pentanediol dibenzoate, yield 93%.
2,2 '-dimethyl-1,5-pentanediol dibenzoate 1H NMR (TMS, CDCl 3, ppm, δ): 1.0 (6H, s, methyl H), 1.3～1.4 (2H, t, methylene radical H), 1.6～1.7 (2H, m, methylene radical H), 4.0～4.3 (4H, m, the methylene radical H of ester group), 7.4～8.1 (10H, m, phenyl ring H).
Embodiment 2
1,1 '-preparation of dibenzoyl oxygen ethylcyclohexane
(1) 1,1 '-preparation of oxalic acid di-alcohol ester group hexanaphthene
0.1mol 1,1 '-adding 0.3mol ethanol, 40ml toluene and the 0.4ml vitriol oil in the oxalic acid hexanaphthene, the stirring and evenly mixing post-heating refluxes.Dewater with water trap, reach Theoretical Calculation amount, stopped reaction up to the water of telling.With the saturated sodium carbonate solution neutralization, ethyl acetate extraction is told upper solution, and the saturated common salt aqueous solution is washed till neutrality, anhydrous sodium sulfate drying.Remove and desolvate, underpressure distillation gets colourless liquid, yield 90%.
1,1 '-oxalic acid di-alcohol ester group hexanaphthene 1H NMR (TMS, CDCl 3, ppm, δ): 1.12～1.13 (6H, t, methyl H), 1.3～1.4 (10H, m, the methylene radical H of hexanaphthene), 2.48 (4H, s, methylene radical H), 4.0～4.1 (4H, m, alcoholic acid methylene radical H).
(2) 1,1 '-preparation of di-alcohol hexanaphthene
Add the 100ml anhydrous diethyl ether in the 3g Lithium Aluminium Hydride, the ice bath cooling is vigorous stirring down.Slowly drip 0.05mol 1,1 '-oxalic acid di-alcohol ester group hexanaphthene, reflux 5h then.The Lithium Aluminium Hydride of cooling back water decomposing excessive, ether stirs extraction solution after-filtration, anhydrous sodium sulfate drying.Remove and desolvate, column chromatography gets colourless viscous liquid 1,1-di-alcohol hexanaphthene, yield 75%.The IR spectrogram is at 3400cm -1There is strong-OH absorption peak at the place, and at 1700cm -1About nothing-CO-absorption peak, prove that reduction reaction carries out fully.
The preparation of (3) 1,1-dibenzoyl oxygen ethylcyclohexanes
0.03mol 1,1 '-add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the di-alcohol hexanaphthene, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography, colourless viscous liquid 1,1 '-dibenzoyl oxygen ethylcyclohexane, yield 93%.
1,1 '-dibenzoyl oxygen ethylcyclohexane 1H NMR (TMS, CDCl 3, ppm, δ): 1.2～1.4 (6H, m, the methylene radical H of hexanaphthene), 1.4～1.5 (4H, t, the methylene radical H of hexanaphthene), 2.0～2.1 (4H, t, methylene radical H), 4.1～4.4 (4H, m, the methylene radical H of ester group), 7.4～8.1 (10H, m, phenyl ring H).
Embodiment 3
1,5-phenylbenzene-1, the preparation of 5-pentanediol dibenzoate
(1) 1,5-phenylbenzene-1, the preparation of 5-pentanediol
Add the 100ml anhydrous tetrahydro furan in the 3g Lithium Aluminium Hydride, the ice bath cooling is vigorous stirring down.Slowly drip 0.05mol 1,5-phenylbenzene-1,5-diacetylmethane, reflux 5h then.The Lithium Aluminium Hydride of cooling back water decomposing excessive stirs extraction solution after-filtration, anhydrous sodium sulfate drying with ethyl acetate.Remove and to desolvate, column chromatography gets white solid 1,5-phenylbenzene-1,5-pentanediol, yield 85%, mp64～67 ℃.The IR spectrogram is at 3400cm -1There is strong-OH absorption peak at the place, and at 1700cm -1About nothing-CO-absorption peak, prove that reduction reaction carries out fully.
(2) 1,5-phenylbenzene-1, the preparation of 5-pentanediol dibenzoate
0.03mol 1,5-phenylbenzene-1 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 5-pentanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography gets colourless viscous liquid 1,5-phenylbenzene-1,5-pentanediol dibenzoate, yield 93%.
1,5-phenylbenzene-1,5-pentanediol dibenzoate 1H NMR (TMS, CDCl 3, ppm, δ): 1.3～1.5 (2H, s, methylene radical H), 1.9～2.1 (4H, m, methylene radical H), 5.94～5.97 (2H, t, the methylene radical H of ester group), 7.2～8.0 (20H, m, phenyl ring H).
Embodiment 4
1,5-phenylbenzene-1, the preparation of 5-pentanediol dipropionate
0.03mol 1,5-phenylbenzene-1 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 5-pentanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography gets colourless viscous liquid 1,5-phenylbenzene-1,5-pentanediol dipropionate, yield 94%.
1,5-phenylbenzene-1,5-pentanediol dipropionate 1H NMR (TMS, CDCl 3, ppm, δ): 1.0～1.1 (6H, m, methyl H), 1.2～1.3 (2H, m, methylene radical H), 1.7～1.9 (4H, m, methylene radical H), 2.2～2.3 (4H, m, the methylene radical H of propyl group), 5.6～5.7 (2H, t, the methylene radical H of ester group), 7.2～7.8 (10H, m, phenyl ring H).
Embodiment 5
1, the preparation of 4-dibenzoyl oxygen methylcyclohexane
0.03mol 1, add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-hydroxymethyl-cyclohexane, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Use ethyl acetate: sherwood oil (2: 1) recrystallization gets white solid 1,4-dibenzoyl oxygen methylcyclohexane.Yield 95%, mp111～113 ℃.
1,4-dibenzoyl oxygen methylcyclohexane 1H NMR (TMS, CDCl 3, ppm, δ): 1.1～1.2 (8H, m, hexanaphthene H), 1.8～1.9 (2H, m, hexanaphthene H), 4.2～4.3 (4H, d, methylene radical H), 7.4～8.1 (10H, m, phenyl ring H).
Embodiment 6
1, the preparation of 4-xylyl alcohol dibenzoate
0.03mol 1, add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-xylyl alcohol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Use ethyl acetate: sherwood oil (1: 1) recrystallization gets white solid 1,4-xylyl alcohol dibenzoate.Yield 95%, mp84～85 ℃.
1,4-xylyl alcohol dibenzoate 1H NMR (TMS, CDCl 3, ppm, δ): 5.3 (4H, s, the methylene radical H of ester group), 7.4～8.1 (10H, m, phenyl ring H).
Embodiment 7
1, the preparation of 5-hexylene glycol dibenzoate
0.03mol 1, add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 5-hexylene glycol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography gets colourless liquid 1,5-hexylene glycol dibenzoate, yield 94%. 1H NMR (TMS, CDCl 3, ppm): δ 1.37～1.38 (3H, d, methyl H), 1.5～1.6 (2H, m, methylene radical H), 1.6～1.7 (2H, m, methylene radical H), 1.7～1.8 (2H, m, methylene radical H), 4.33～4.37 (2H, m, the methylene radical H of ester group), 5.20～5.24 (1H, m, the methyne H of ester group), 7.4～8.0 (10H, m, phenyl ring H)
Embodiment 8
2,2 '-preparation of biphenyl dimethanol dibenzoate
(1) 2,2 '-preparation of biphenyl dicarboxylic acid diethyl alcohol ester
0.1mol 2,2 '-adding 0.3mol ethanol, 40ml toluene and the 0.4ml vitriol oil in the biphenyl dicarboxylic acid acid anhydride, the stirring and evenly mixing post-heating refluxes.Dewater with water trap, reach Theoretical Calculation amount, stopped reaction up to the water of telling.With the saturated sodium carbonate solution neutralization, ethyl acetate extraction is told upper solution, and the saturated common salt aqueous solution is washed till neutrality, anhydrous sodium sulfate drying.Remove and to desolvate, underpressure distillation get colourless liquid 2,2 '-biphenyl dicarboxylic acid diethyl alcohol ester, yield 90%.
(2) 2,2 '-preparation of biphenyl dimethanol
Add the 100ml anhydrous diethyl ether in the 3g Lithium Aluminium Hydride, the ice bath cooling is vigorous stirring down.Slowly drip 0.05mol 2,2 '-biphenyl dicarboxylic acid diethyl alcohol ester, reflux 5h then.The Lithium Aluminium Hydride of cooling back water decomposing excessive filters back extracted with diethyl ether solution, anhydrous sodium sulfate drying.Remove and to desolvate, column chromatography get white solid 2,2 '-the biphenyl dimethanol, yield 75%.M.p.98-103 ℃, the IR spectrogram is at 3400cm -1There is strong absorption peak at the place, and at 1700cm -1About do not have absorption peak, prove that reduction reaction carries out fully.
(3) 2,2 '-preparation of biphenyl dimethanol dibenzoate
0.03mol 2,2 '-add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the biphenyl dimethanol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography, colourless viscous liquid 2,2 '-biphenyl dimethanol dibenzoate, yield 93%.
2,2 '-biphenyl dimethanol dibenzoate 1H NMR (TMS, CDCl 3, ppm, δ): 5.16 (4H, s, the methylene radical H of ester group), 7.2-8.2 (18H, m, phenyl ring H).
Embodiment 9
2,2 '-preparation of biphenyl dimethanol dipropionate
0.03mol 2,2 '-add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the biphenyl dimethanol, under agitation add the 0.075mol propionyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography, colourless viscous liquid 2,2 '-biphenyl dimethanol dipropionate, yield 93%.
2,2 '-biphenyl dimethanol dipropionate 1H NMR (TMS, CDCl 3, ppm, δ): 1.0-1.1 (6H, t, methyl H), 2.2-2.3 (4H, m, methylene radical H), 4.8-4.9 (4H, t, the methylene radical H of ester group), 7.2-7.5 (8H, m, phenyl ring H).
Embodiment 10
2,2 '-preparation of biphenyl dimethanol two pivalates
0.03mol 2,2 '-add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the biphenyl dimethanol, under agitation add the 0.075mol pivalyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na 2SO 4Drying is removed and is desolvated.Column chromatography, colourless viscous liquid 2,2 '-biphenyl dimethanol two pivalates, yield 93%.
2,2 '-biphenyl dimethanol two pivalates 1H NMR (TMS, CDCl 3, ppm, δ): 1.1～1.2 (18H, s, methyl H), 4.84～4.86 (4H, d, the methylene radical H of ester group), 7.3～7.4 (8H, m, phenyl ring H).
Embodiment 11
3,4-dibutyl-1,6-hexylene glycol dibenzoate
In reactor, add 3,4-dibutyl-1,6-hexylene glycol 4.4g, Benzoyl chloride 3.8g, pyridine 4.0g and tetrahydrofuran (THF) 70ml mix, and are heated to backflow.After occurring refluxing, kept 4 hours.Reduce to room temperature then, in reaction system, add water till inorganic mutually transparent.Tell organic phase, merge with organic phase with the inorganic back mutually of extracted with diethyl ether.After washing organic phase with water, with the organic phase drying, after concentrating, isolate product, obtain the 4.3g product with anhydrous sodium sulphate.3,4-dibutyl-1,6-hexylene glycol dibenzoate 1HNMR (TMS, CDCl 3, ppm, δ): 0.8～1.6 (18H), 2.1～2.3 (6H), 4.3～4.5 (4H), 7.4～8.1 (10H).
Embodiment 12
2,2 '-dinaphthalene dimethanol dibenzoate
In reactor, add dinaphthalene diphenol 4.3g, Benzoyl chloride 4g, pyridine 4.5g and tetrahydrofuran (THF) 70ml mix, and are heated to backflow.After occurring refluxing, kept 4 hours.Reduce to room temperature then, in reaction system, add water till inorganic mutually transparent.Tell organic phase, merge with organic phase with the inorganic back mutually of extracted with diethyl ether.After washing organic phase with water, with the organic phase drying, after concentrating, isolate product, obtain the 8.2g product with anhydrous sodium sulphate.2,2 '-dinaphthalene dimethanol dibenzoate 1H NMR (TMS, CDCl 3, ppm, δ): 4.8 (4H), 7.0～8.1 (22H).
Embodiment 13
2,2 '-methylene bridge binaphthol dibenzoate
0.02mol 2,2 '-methylene bridge binaphthol is mixed with 100mlTHF, add 0.05mol Benzoyl chloride and 0.06mol pyridine again.Be heated to backflow, and kept 4 hours.Add the water decomposition solid matter.Isolate organic phase, washing, drying obtains the 8.5g product, productive rate 87% after concentrating.2,2 '-methylene bridge binaphthol dibenzoate 1H NMR (TMS, CDCl 3, ppm, δ): 3.7～3.9 (2H), 6.8～8.1 (22H).
Aggregation test
Adopt embodiment 11,13 resulting compound catalyst components.
(1) preparation of olefins polymerizing solid catalyst component
In through the abundant metathetical reactor of high pure nitrogen, add magnesium chloride 4.8g successively, toluene 95ml, epoxy chloropropane 4ml, tributyl phosphate (TBP) 12.5ml is warming up to 50 ℃ under stirring, and kept 2.5 hours, solid dissolves fully, adds Tetra hydro Phthalic anhydride 1.4g, continues to keep 1 hour.Solution is cooled to below-25 ℃, drips TiCl in 1 hour 456ml slowly is warming up to 80 ℃, separates out solids in temperature-rise period gradually, adds the resulting compound 6mmol of the foregoing description respectively, and holding temperature 1 hour after the filtration, adds toluene 70ml, and the washing secondary obtains solid sediment.Add toluene 60ml then, TiCl 440ml is warmed up to 100 ℃, handles two hours, after the venting filtrate, adds toluene 60ml again, TiCl 440ml is warmed up to 100 ℃, handles venting filtrate two hours.Add toluene 60ml, boiling attitude washing three times adds hexane 60ml again, and boiling attitude washed twice adds hexane 60ml, after the normal temperature washed twice, obtains ingredient of solid catalyst.
(2) propylene polymerization experiment
The catalyst component of above-mentioned gained is carried out propylene polymerization respectively.The propylene polymerization program is: volume is the stainless steel cauldron of 5L, after gaseous propylene is fully replaced, adds AlEt 32.5mmol methylcyclohexyl dimethoxy silane (CHMMS) 0.1mmol adds about 8mg of ingredient of solid catalyst and 1.2L hydrogen that the foregoing description obtains again, feeds liquid propene 2.3L, is warming up to 70 ℃, keeps this temperature 1 hour.Cooling, pressure release obtains the PP powder.Polymerization result such as table 1.
Table 1 embodiment 11 and 13 polymerization result
The dibasic alcohol ester compound kind Polymerization activity (kgPP/gcat) TII (％) MI (g/10min) MWD
3,4-dibutyl-1,6-hexylene glycol dibenzoate 31.5 97.5 2.4 7.5
2,2 '-methylene bridge binaphthol dibenzoate 42.0 98.0 4.8 5.4

Claims (13)

1, the dibasic alcohol ester compound that has following general formula (I):
Figure C031496980002C1
Wherein:
N=3 or 4, R 1And R 2Can be identical or inequality, be selected from the C of straight or branched 1-C 20Alkyl, aryl, R 3-R 6, R 1And R 2Group can be identical or inequality, is selected from the C of hydrogen, straight or branched 1-C 20Alkyl, cycloalkyl, aryl, but R 1, R 2, R 3, R 4, R 5And R 6Can not be hydrogen entirely;
When n=3, R 1, R 2, R 3, R 4, R 5And R 6Have at least two groups not to be hydrogen, when having only two groups not for hydrogen, all the other groups can not be methyl or ethyl entirely, R 1, R 2, R 3-R 6Being connected in the group between the group on the different carbon atoms can not Cheng Huan, but can form two condensed ring, this moment R 1And R 2Can not halogen atom;
When n=4, R 1, R 2, R 3, R 4, R 5And R 6Can not Cheng Huan between group, and when wherein having two during for methyl, other groups can not be hydrogen entirely;
But the dibasic alcohol ester compound of described general formula (I) does not comprise 2,2,4-trimethylammonium-1,5-pentanediol dibenzoate, 2-ethyl-1,6-hexylene glycol dibenzoate and 2,4-dimethyl-1,5-pentanediol dibenzoate.
2, diol ester compound according to claim 1, in its formula of (I), R 3And R 4, R 5And R 6In to have a group respectively at least be ethyl, propyl group, butyl, phenyl or halogenated phenyl and can not be simultaneously be phenyl, R 1And R 2Identical or different, be hydrogen or methyl, ethyl, propyl group, butyl, phenyl or halogenated phenyl.
3, diol ester compound according to claim 1, in its formula of (I), R 3And R 4, R 5And R 6In a group is arranged respectively is hydrogen, and another group is ethyl, propyl group, butyl, phenyl or halogenated phenyl and can not be phenyl, R simultaneously 1And R 2Identical or different, be hydrogen or methyl, ethyl, propyl group, butyl, phenyl or halogenated phenyl.
4, according to the described diol ester compound of one of claim 1-3, wherein R 1, R 2In have at least one to be phenyl.
5, according to the described diol ester compound of one of claim 1-3, wherein R 1, R 2All are phenyl.
6, diol ester compound according to claim 1, in its formula of (I), n=3, R 1, R 2, R 3, R 4, R 5And R 6Have at least two groups not to be hydrogen, when having only two groups not for hydrogen, all the other groups can not be methyl or ethyl entirely, R 1, R 2, R 3-R 6Being connected in the group between the group on the different carbon atoms can not Cheng Huan, but can form two condensed ring, this moment R 1And R 2Have at least one to be aryl.
7, diol ester compound according to claim 6, wherein R 1And R 2Be aryl.
8, diol ester compound according to claim 1, in its formula of (I), n=4, R 1, R 2, R 3, R 4, R 5And R 6Can not Cheng Huan between group, and when wherein having two during for methyl, other groups can not be hydrogen entirely, R 1And R 2Have at least one to be aryl.
9, diol ester compound according to claim 8, wherein R 1And R 2Be aryl.
10, diol ester compound according to claim 1, in its formula of (I), R 3And R 4, R 5And R 6In a group is arranged respectively is hydrogen, and another group is ethyl, propyl group, butyl, phenyl or halogenated phenyl and can not be phenyl, R simultaneously 1And R 2Identical or different, be hydrogen or methyl, ethyl, propyl group, butyl, phenyl or halogenated phenyl, R 1, R 2All are phenyl.
11, dibasic alcohol ester compound according to claim 1, it is selected from following compound:
2,2 '-dimethyl-1,5-pentanediol dibenzoate, 1,5-phenylbenzene-1,5-pentanediol dibenzoate, 1,5-phenylbenzene-1,5-pentanediol dipropionate, 2,2 '-methylene bridge binaphthol dibenzoate, 3,4-dibutyl-1,6-hexylene glycol dibenzoate.
12, the preparation method of the described dibasic alcohol ester compound of one of a kind of claim 1-11 in the presence of corresponding acid or acyl chlorides, makes the dibasic alcohol of general formula (II) carry out esterification and obtains corresponding binary alcohol esters:
HO-CR 3R 4-(CR 1R 2) n-CR 5R 6-OH (II)
Wherein n, R 1, R 2, R 3-R 6Definition such as the definition of claim 1 formula of (I).
13, the application of the described dibasic alcohol ester compound of one of claim 1-11 in the preparation olefin polymerization catalysis.
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CN1259528A (en) * 1998-12-04 2000-07-12 三星综合化学株式会社 Process for alpha-olefine homopolymerization and co-polymerization
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US4608579A (en) * 1984-05-25 1986-08-26 Ricoh Company, Ltd. Thermosensitive recording material
CN1259528A (en) * 1998-12-04 2000-07-12 三星综合化学株式会社 Process for alpha-olefine homopolymerization and co-polymerization
DE19927979A1 (en) * 1999-06-18 2000-10-12 Basf Ag Preparation of alkylenediol dicyclohexanoate, useful as nontoxic plasticizers, by hydrogenation of the dibenzoate over Group 8 metal catalyst on macroporous carrier

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