CN1063188C - Catalyst system for synthesizing syndiotactic polyphenylacetylene and preparation process thereof - Google Patents

Catalyst system for synthesizing syndiotactic polyphenylacetylene and preparation process thereof Download PDF

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CN1063188C
CN1063188C CN96114376A CN96114376A CN1063188C CN 1063188 C CN1063188 C CN 1063188C CN 96114376 A CN96114376 A CN 96114376A CN 96114376 A CN96114376 A CN 96114376A CN 1063188 C CN1063188 C CN 1063188C
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titanium
dppo
diphenylpropane
dione
catalyst system
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CN1185448A (en
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谢光华
许学翔
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Beijing Research Institute of Beijing Yanshan Petrochemical Corp
Institute of Chemistry CAS
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Beijing Research Institute of Beijing Yanshan Petrochemical Corp
Institute of Chemistry CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring

Abstract

The present invention relates to polystyrene with a high syndiotactic degree, which is prepared by a catalyst system which is composed of a titanium (IV) complex compound as a main catalyst and a cocatalyst. The main catalyst is formed by reacting titanium tetrachloride and phenol (or derivatives thereof) with beta-diketon (or derivatives thereof); the cocatalyst is an aluminoxane compound. The catalyst system is used for styrene polymerization to prepare the polystyrene with a high syndiotactic degree of 92 to 98%; a fusing point reaches to 270 to 273 DEG C.

Description

A kind of catalyst system for synthesizing syndiotactic polyphenylacetylene and method for making thereof
The present invention relates to polyolefin catalyst, particularly a kind of synthesis of syndiotactic polystyrene catalyzer and method for making thereof.
To the chain backbone spatial orientation, the polystyrene molecule has random A-PS according to polystyrene molecular side chain phenyl ring, complete same i-PS, three kinds of different steric configurations of rule S-PS.Macromolecules, 19,2464 (1986) have reported a kind of high reactivity syndiotactic polystyrene catalyst Cp TiCl that is proposed by N.Ishihara 3Eur.Pat.APPl.208564 in 1987,1989 U.S.Patent, 48081680 have reported single luxuriant titanium (zirconium) compound of employing, titanate ester and benzyl titanium compound thereof are as catalyzer, 1993 Makromol.Chem., MacromolSymp, 66 203 have reported with two (the 6-tertiary butyl-4-methylphenoxy) titanium dichloride/MAO systems of sulphur bridge and have prepared normality polystyrene resin between height.But above-mentioned catalyst system preparation method is complicated.We disclose " a kind of catalyst system for synthesizing syndiotactic polyphenylacetylene and method for making thereof " (application number 96102496.8) on March 7th, 1996 and have reported with beta diketone titanium/MAO catalyst system normality, dystectic polystyrene between synthetic height, but this catalyst system catalytic activity is not high enough, and productive rate is lower.
The object of the invention provides a kind of simple synthetic method and easily goes, and can make normality between height, the catalyst system of dystectic syndiotactic polystyrene with high polymerization activity again.
Catalyst system of the present invention is made up of Primary Catalysts and two kinds of components of promotor, and wherein Primary Catalysts is a kind of derivative of beta diketone titanium complex compound, has following general formula: R ' is phenyl or substituted-phenyl or C 1～C 12Alkyl.R is C 1～C 12Alkyl or perfluoroalkyl or aryl, wherein said aryl is phenyl or substituted-phenyl, R is preferably methyl or phenyl.N is respectively 1,2 or 3.R ' is a phenyl, and when R was methyl, Primary Catalysts was (methyl ethyl diketone) three (phenoxy group) titanium, two (methyl ethyl diketones) two (phenoxy group) titaniums or tri acetylacetonato one (phenoxy group) titanium.When R ' and R were phenyl, Primary Catalysts was (diphenylpropane-1,3-dione(DPPO)) three (phenoxy group) titanium, two (diphenylpropane-1,3-dione(DPPO)s) two (phenoxy group) titaniums or three (diphenylpropane-1,3-dione(DPPO)) (phenoxy group) titaniums.When R is a phenyl, R ' is 2, during the 6-3,5-dimethylphenyl, Primary Catalysts is (diphenylpropane-1,3-dione(DPPO)) three (2, a 6-xylyloxy) titanium, two (diphenylpropane-1,3-dione(DPPO)) two (2, the 6-xylyloxy) titanium, or three (diphenylpropane-1,3-dione(DPPO)s) (2, the 6-xylyloxy) titanium.
Promotor is an organo-aluminium compound, can be alumina alkane (MAO) or alkylaluminium cpd, and described alumina alkane has following structure:
Figure 9611437600051
R wherein "=-CH 3,-C 2H 5, i-Butyl, n=5～30,
Method for preparing catalyst of the present invention is as follows:
The titanium tetrachloride diethyl ether solution of 4-10% is placed flask, and at 25 ℃ of phenol or 2 with 5-20%, 6-xylenol diethyl ether solution mixed in 1: 1 in molar ratio～1: 3, stirred 0.5～1 hour, best 0.5 hour, continued by TiCl 4Added the beta-diketon diethyl ether solution of 5-15% in 1: 1～1: 3 with the mol ratio of beta-diketon, reflux 1-2 hour, be preferably 1 hour, filter or remove and desolvate, with ether washing three times, can obtain the beta-diketon phenoxide titanium as (methyl ethyl diketone) three (phenoxy group) titanium, two (methyl ethyl diketones) two (phenoxy group) titanium, tri acetylacetonato (phenoxy group) titanium, (diphenylpropane-1,3-dione(DPPO)) three (phenoxy group) titanium, two (diphenylpropane-1,3-dione(DPPO)s) two (phenoxy group) titanium, three (diphenylpropane-1,3-dione(DPPO)s)-(phenoxy group) titanium, or (diphenylpropane-1,3-dione(DPPO)) three (2, the 6-xylyloxy) titanium, two (diphenylpropane-1,3-dione(DPPO)) two (2, the 6-xylyloxy) titanium, three (diphenylpropane-1,3-dione(DPPO)s)-(2, the 6-xylyloxy) titanium.
Above-mentioned beta-diketon is methyl ethyl diketone or diphenylpropane-1,3-dione(DPPO).
Adopt the preparation method of beta-diketon phenoxide titanium of the present invention/MAO catalyst system synthesis of syndiotactic polystyrene as follows:
In the toluene medium, add organo-aluminium compound respectively, methylaluminoxane preferably, with beta-diketon phenoxide titanium catalyzer, its mol ratio remains on 200-2000, be preferably in 500-1000, be preferably under the 20-80 ℃ of temperature at 10-100 ℃ and add styrene monomer and carry out polyreaction, polymerization time 0.5-1h, with acidifying ethanol termination reaction, the polymkeric substance that is settled out is through washing, drying, normality is determined as 92～98% with the acetone extraction process between the syndiotactic polystyrene that makes, and measuring fusing point with DSC is 270～273 ℃.
Catalyst system preparation method of the present invention is easy, and can obtain normality between height by high reactivity, the high-melting-point syndiotactic polystyrene.
Embodiment 1,
Use TiCl 4After diethyl ether solution and phenol diethyl ether solution 1: the 3 in molar ratio reaction, continue by with TiCl 4Mol ratio is 1: 1 adding methyl ethyl diketone diethyl ether solution, just can make (methyl ethyl diketone) three (phenoxy group) titanium acacTi (OPh) 3(catalyzer 1).
Polymerization process: at a 100cc in the reaction flask that agitator is housed that nitrogen replacement is crossed, add the toluene that 25ml distills out after the sodium Metal 99.5 backflow removes moisture content, be warming up to 80 ℃ under stirring, add people 1mlMAO toluene solution (7.5mmole), stir and add catalyzer 1 toluene solution (15 μ mole) .Al/Ti mol ratio 500 after 5 minutes again, add 10ml at last through the dry distilled styrene monomer of the universe, constant temperature stirred 1 hour, add 10ml acidifying ethanol (3%HCl) and stop polyreaction, reactant poured into continue in the beaker that excess ethyl alcohol is housed to stir 1 hour, filter, use the washing with alcohol polymkeric substance, 70 ℃ of following vacuum-drying 4 hours, polymkeric substance 0.64 gram, the acetone extraction process records normality 92.4% between polystyrene, and the DSC method is measured Tm=270.2 ℃ of melting point polymer.
Embodiment 2-3,
Use TiCl 4After the reaction in 1: 2 in molar ratio of the diethyl ether solution of phenol, continue by TiCl 4Add methyl ethyl diketone at 1: 2 with the methyl ethyl diketone mol ratio, can make two (methyl ethyl diketone) two (phenoxy group) titaniums (acac) 2Ti (OPh) 2(catalyzer 2).TiCl 41: 1 in molar ratio follow-up TiCl that presses of reaction of diethyl ether solution with phenol 4Add methyl ethyl diketone at 1: 3 with the methyl ethyl diketone mol ratio and can make tri acetylacetonato one (phenoxy group) titanium (acac) 3Ti (OPh) (catalyzer 3).With the identical polymerizing condition of embodiment 1, use catalyzer 2,3 to carry out styrene polymerization respectively, the results are shown in table 1.
Table 1 embodiment polymerization catalyst thing S-PS Tm (g) (%) (℃) 22 0.99 93.1 270.8 33 2.37 95.8 271.4 embodiment 4-6,
Use PhCOCH 2The methyl ethyl diketone among the routine 1-3 of COPh (dbm) replacement and the TiCl of calculated amount 4, phenol reactant, can make diphenylpropane-1,3-dione(DPPO) phenoxide titanium title complex.Work as TiCl 4With the mol ratio of phenol be 1: 3, TiCl 4With the mol ratio of dbm be 1: 1 o'clock, can make (diphenylpropane-1,3-dione(DPPO)) three (phenoxy group) titanium (dbm) Ti (OPh) 3, (catalyzer 4).Work as TiCl 4With the mol ratio of phenol be 1: 2, TiCl 4With the mol ratio of dbm be 1: 2 o'clock, can make two (diphenylpropane-1,3-dione(DPPO)) two (phenoxy group) titaniums (dbm) 2Ti (OPh) 2(catalyzer 5).Work as TiCl 4With the mol ratio of phenol be 1: 1, TiCl 4With the mol ratio of dbm be 1: 3 o'clock, can make three (diphenylpropane-1,3-dione(DPPO)) (phenoxy group) titaniums (dbm) 3Ti (OPh) (catalyzer 6).With the identical polymerizing condition of embodiment 1, carry out styrene polymerization with catalyzer 4-6 respectively.The results are shown in table 2.
Table 2 embodiment polymerization catalyst thing S-PS Tm (g) (%) (℃) 44 4.14 94.5 271.3 55 5.41 97.0 270.3 66 9.23 96.9 271.4
Embodiment 7-9,
With 2,6-xylenol (dmp) replaces the phenol among the embodiment 4-6, use with embodiment 4-6 in identical synthetic method, can make respectively: (diphenylpropane-1,3-dione(DPPO)) three (2, the 6-xylyloxy) titanium (dbm) Ti (dmp) 3(catalyzer 7), two (diphenylpropane-1,3-dione(DPPO)s) two (2, the 6-xylyloxy) titanium (dbm) 2Ti (dmp) 2(catalyzer 8) and three (diphenylpropane-1,3-dione(DPPO)s) (2, the 6-xylyloxy) titanium (dbm) 3Ti (dmp) (catalyzer 9).With the identical polymerizing condition of embodiment 1, carry out styrene polymerization with catalyzer 7-9 respectively.The results are shown in table 3.
Table 3 embodiment polymerization catalyst thing S-PS Tm (g) (%) (℃) 77 3.98 91.7 273.1 88 9.43 97.8 272.3 99 4.58 94.5 270.1

Claims (10)

1, a kind of catalyst system for synthesizing syndiotactic polyphenylacetylene is characterized in that described catalyst system comprises Primary Catalysts and two kinds of components of promotor, and described Primary Catalysts is that the beta diketone compounds of titanium (IV) has following general formula:
Figure 9611437600021
R is C 1～C 12Alkyl or perfluoroalkyl or phenyl; R ' is phenyl or substituted-phenyl, or C 1～C 12Alkyl, n is 1,2, or 3, described promotor is an organo-aluminium compound.
2, a kind of catalyst system for synthesizing syndiotactic polyphenylacetylene according to claim 1, it is characterized in that R is a methyl, when R ' was phenyl, Primary Catalysts was (methyl ethyl diketone) three (phenoxy group) titanium, two (methyl ethyl diketones) two (phenoxy group) titaniums or tri acetylacetonato one (phenoxy group) titanium.
3, a kind of catalyst system for synthesizing syndiotactic polyphenylacetylene according to claim 1, when it is characterized in that described R and R ' are phenyl, Primary Catalysts is (diphenylpropane-1,3-dione(DPPO)) three (phenoxy group) titanium, two (diphenylpropane-1,3-dione(DPPO)s) two (phenoxy group) titanium, or three (diphenylpropane-1,3-dione(DPPO)s)-(phenoxy group) titanium.
4, a kind of catalyst system for synthesizing syndiotactic polyphenylacetylene according to claim 1, it is characterized in that described R is a phenyl, R ' is 2, during the 6-xylyl, Primary Catalysts is (diphenylpropane-1,3-dione(DPPO)) three (2, a 6-xylyloxy) titanium, two (diphenylpropane-1,3-dione(DPPO)) two (2, the 6-xylyloxy) titanium, or three (diphenylpropane-1,3-dione(DPPO)s) (2,6-diformazan two phenoxy groups) titanium.
5, a kind of preparation method of catalyst system for synthesizing syndiotactic polyphenylacetylene, it is characterized in that step is carried out in the following order: the titanium tetrachloride diethyl ether solution with 4-10% under 25 ℃ mixed with the phenol diethyl ether solution of 5-20% in 1: 1 in molar ratio～1: 3, stirred 0.5～1 hour, the mol ratio by titanium tetrachloride and beta-diketon of continuing is to add 5～15% beta-diketon diethyl ether solution in 1: 1～1: 3, reflux 1～2 hour, remove and desolvate, with the ether washing for several times, can obtain the beta-diketon phenoxide titanium.
6, a kind of preparation method of catalyst system for synthesizing syndiotactic polyphenylacetylene, under 25 ℃ with 2 of the titanium tetrachloride diethyl ether solution of 4-10% and 5-20%, 6-xylenol diethyl ether solution mixed in 1: 1 in molar ratio～1: 3, stirred 0.5～1 hour, the mol ratio by titanium tetrachloride and beta-diketon of continuing is to add 5～15% beta-diketon diethyl ether solution, reflux 1～2 hour in 1: 1～1: 3, remove and desolvate, with the ether washing for several times, can obtain beta-diketon-2,6-xylyloxy titanium.
7,, it is characterized in that described beta-diketon is methyl ethyl diketone or diphenylpropane-1,3-dione(DPPO) according to the preparation method of claim 5 or 6 described a kind of catalyst system for synthesizing syndiotactic polyphenylacetylene.
8, the preparation method of a kind of catalyst system for synthesizing syndiotactic polyphenylacetylene according to claim 7 is characterized in that described beta-diketon phenoxide titanium is (methyl ethyl diketone) three (phenoxy group) titanium, two (methyl ethyl diketones) two (phenoxy group) titaniums or tri acetylacetonato one (phenoxy group) titanium.
9, the preparation method of a kind of catalyst system for synthesizing syndiotactic polyphenylacetylene according to claim 7 is characterized in that described beta-diketon phenoxide titanium is three (diphenylpropane-1,3-dione(DPPO)) (phenoxy group) titaniums, two (diphenylpropane-1,3-dione(DPPO)s) two (phenoxy group) titaniums or (diphenylpropane-1,3-dione(DPPO)) three (phenoxy group) titanium.
10, the preparation method of a kind of catalyst system for synthesizing syndiotactic polyphenylacetylene according to claim 7, it is characterized in that described beta-diketon phenoxide titanium is (diphenylpropane-1,3-dione(DPPO)) three (2, the 6-xylyloxy) titanium, two (diphenylpropane-1,3-dione(DPPO)) two (2, the 6-xylyloxy) titanium, or three (diphenylpropane-1,3-dione(DPPO)) (2, the 6-xylyloxy) titanium.
CN96114376A 1996-12-17 1996-12-17 Catalyst system for synthesizing syndiotactic polyphenylacetylene and preparation process thereof Expired - Fee Related CN1063188C (en)

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CN1118492C (en) * 1999-06-30 2003-08-20 中国科学院化学研究所 Catalyst system for synthesizing syndiotactic polystyrene
CN1119358C (en) * 1999-12-02 2003-08-27 中国石油化工集团公司 Syndiotactic polystyrene catalyst and its preparation and application
EP2477738B1 (en) * 2009-09-15 2019-01-23 Basf Se Photo-latent titanium-chelate catalysts

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Publication number Priority date Publication date Assignee Title
EP0472741A1 (en) * 1990-03-16 1992-03-04 Tonen Corporation Olefin polymerization catalyst
CN1105671A (en) * 1993-10-01 1995-07-26 希蒙特公司 Components and catalysts for the polymerization of olefins

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0472741A1 (en) * 1990-03-16 1992-03-04 Tonen Corporation Olefin polymerization catalyst
CN1105671A (en) * 1993-10-01 1995-07-26 希蒙特公司 Components and catalysts for the polymerization of olefins

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