CN1116320C - Catalyst for syndiotatic phenylethylene polymerization - Google Patents
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- CN1116320C CN1116320C CN 00127437 CN00127437A CN1116320C CN 1116320 C CN1116320 C CN 1116320C CN 00127437 CN00127437 CN 00127437 CN 00127437 A CN00127437 A CN 00127437A CN 1116320 C CN1116320 C CN 1116320C
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Abstract
The present invention relates to a catalyst for styrene syndiotactic polymerization, which mainly solves the problems of low catalytic activity and low content of obtained syndiotactic polystyrene in the process that catalysts made of cyclopentadiene titanium compounds are used for styrene polymerization existed in the original document. By adopting the technical scheme that the styrene syndiotactic polymerization catalysts are formed from the indenyl metal titanium compounds of which the structural formula is IndTiCl2 (OR), and aluminum alkyl oxygen alkane, the problems are solved well. The present invention can be used for the industrial production of styrene syndiotactic polymerization.
Description
Technical field
The present invention relates to a kind of catalyzer of syndiotactic polymerization of phenylethylene.
Background technology
(Polystyrene is a kind of unregulated polymer PS) to the polystyrene that obtains by radical polymerization, and matter is hard, transparent, rigidity, electrical insulating property, cheap, dyeing has become one of current five big general-purpose plastics easily, be widely used in packing, building, medicine, electronics, automobile, industries such as daily necessities.But because the randomness of structure causes it frangible, thermo-labile, not resistance to chemical attack.
Introduced a kind of polystyrene of high tacticity in the European patent EP 210615, wherein the syndiotactic structure arrangement is pressed in the phenyl ring replacement.This crystalline material no longer has the shortcoming of unregulated polymer, is dissolved in any organic solvent hardly, and has high fusing point (250～280 ℃), heat-resisting, resistance to chemical attack, and its performance can compare favourably with polyester, polymeric amide etc.
The catalyst system that is generally used for syndiotactic polymerization of phenylethylene is made up of two portions, i.e. transition metal organometallic compound, especially Ti, and the compound of Zr, and with methylaluminoxane (MAO) and B (C
6F
5)
3Promotor for representative.
Common catalyzer comprises the various halogenide of titanium in the document, four alkoxy compounds (methoxyl group, oxyethyl group, propoxy-, isopropoxy etc.), a metallocene compound (luxuriant trichlorine titanium, one luxuriant trialkyl titanium, one luxuriant tri-alkoxy titanium, and replace luxuriant all cpds), tetraalkyl titanium and corresponding zirconium compounds.
Metallocene catalyst is since the fifties, it is the research focus of catalysis in olefine polymerization always, the beginning of the eighties, the discovery catalyzed polymerization that promotes alkene especially of Kaminsky promotor methylaluminoxane entered new research climax, and wherein the catalyst system of compositions such as half sandwich compound and methylaluminoxane has the catalytic activity of stipulating tropism and Gao between significant to the catalyzed polymerization of styrene monomer.After this, the patent that relates to various half-sandwich compounds occurs in succession.
European patent EP 0796875 (1997) (Process for the preparation of crystalline vinylaromaticpolymers with a predominant syndiotactic structure) discloses a structural formula class indenes titanium catalyst as follows:
Typical compound is Ind ' TiCl
3,
Ind ' Ti (OR
1)
3, Ind ' Ti (R
2)
3, (Ind '=4-methyl indenes, 4-ethyl indenes, 5-methyl indenes,
The 5-phenylindan, 4,5-dimethyl indenes, 4,5-diethyl indenes;
R
1＝Me，Et，Pr，Bu，Ph；R
2＝Me，Et，
iBu，Bz)
In the embodiment, the catalytic activity of such catalyzer reaches 2.5 * 10
6Gram PS/ (mole Ti mole S hour), normality reaches 99.4% between the gained polystyrene.But the tri-alkoxy class, the catalyzer of trialkyl class is not reported performance.According to document, the synthetic of the compound of this type is to obtain by the compound of trichlorine one indenes titanium and pure accordingly the reaction in the presence of triethylamine, and the polar phase of the product of raw alcohol and generation seemingly easily mixes with product mutually, is difficult to separate purification.
Summary of the invention
The objective of the invention is to have the not high shortcoming of catalytic effect in order to overcome catalyzer that the metallocene compound introduced in the document in the past makes and to be used for the syndiotactic polymerization of phenylethylene process, a kind of catalyzer of new syndiotactic polymerization of phenylethylene is provided.When this catalyzer is used for the syndiotactic polymerization of phenylethylene process, has the catalytic activity height, excellent catalytic effect, the syndiotactic polystyrene content height of acquisition, the characteristics that the resulting polymers fusing point is high.
The objective of the invention is to realize by following technical scheme: a kind of catalyzer of syndiotactic polymerization of phenylethylene comprises following active constituent:
a)IndTiCl
2(OR)；
B) alkylaluminoxane;
Wherein: Ind is an indenyl;
R is the alkyl of straight chain, side chain or the ring texture of 3～6 carbon atoms;
With molar ratio computing, alkylaluminoxane/IndTiCl
2(OR) be 300～4100.
In the technique scheme, the preferred version of alkylaluminoxane is a methylaluminoxane, with molar ratio computing, and alkylaluminoxane/IndTiCl
2(OR) preferable range is 300～2100.
Preparation of catalysts of the present invention got final product with general the mixing.
The present invention is owing to adopt a kind of novel indenyl titanium compound and alkylaluminoxane composition catalyzer, and it is a styrene monomer syndiotactic polymerization catalyzer efficiently.When being used for syndiotactic polymerization of phenylethylene, activity of such catalysts reaches as high as 1.39 * 10
7Gram PS/ mole Ti mole S hour, the rule weight content is up to 99.6% between catalysis gained polystyrene, and melting point polymer is 273～277 ℃, has obtained effect preferably.
Embodiment
The invention will be further elaborated below by embodiment: [embodiment 1]
Polyreaction is carried out in the ampere bottle of a baking argon filling three times.2 milliliters of vinylbenzene, 3.4 milliliters of toluene, the methylaluminoxane toluene solution of 6.6 ml concns, 1.53 mol, and 0.05 milliliter 0.05 mol Compound I ndTiCl
2(OMe) toluene solution is injected in the ampere bottle successively, is positioned in the oil bath of constant temperature to 50 in advance ℃ polymerization 1 hour.Stop polyreaction with the ethanol that is 10%HCl by weight percentage, after filtration, after the carrying out washing treatment, resulting polymers in 80 ℃ of following vacuum-dryings 24 hours to constant weight, 0.1616 gram polystyrene, catalytic activity is 3.72 * 10
6Gram PS/ (mole Ti mole S hour).Refluxed 2 hours in butanone, remove random polystyrene, recording the syndiotactic polystyrene weight content is 99.3%, and the resulting polymers fusing point is 277 ℃.[embodiment 2]
2 milliliters of vinylbenzene, 3.4 milliliters of toluene, the methylaluminoxane toluene solution of 6.6 ml concns, 1.53 mol, and 0.1 milliliter 0.05 mol Compound I ndTiCl
2(OMe) toluene solution is injected in the ampere bottle successively, and wherein Me is a methyl, is positioned in the oil bath of constant temperature to 50 in advance ℃ polymerization 1 hour, 0.1955 gram polystyrene, catalytic activity is 2.25 * 10
6Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 95.8%.[embodiment 3]
11 milliliters of vinylbenzene, 0.5 ml concn are the methylaluminoxane toluene solution of 1.53 mol, and 0.05 milliliter 0.05 mol Compound I ndTiCl
2(OMe) toluene solution is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 50 in advance ℃ polymerase 10 .5 hour, 1.5709 gram polystyrene, catalytic activity is 1.31 * 10
7Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 90.1%.[comparative example 1]
11 milliliters of vinylbenzene, 0.5 ml concn are the methylaluminoxane toluene solution of 1.53 mol, and 0.05 milliliter 0.05 mol IndTiCl
3Toluene solution be injected into successively in the ampere bottle, be positioned in the oil bath of constant temperature to 50 in advance ℃ polymerase 10 .5 hour, 1.0996 gram polystyrene, catalytic activity is 9.19 * 10
6Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 86.4%.[embodiment 4]
11 milliliters of vinylbenzene, 1 ml concn are the methylaluminoxane toluene solution of 1.53 mol, and 0.1 milliliter 0.05 mol Compound I ndTiCl
2(OMe) toluene solution is injected in the ampere bottle successively, is positioned in the oil bath of constant temperature to 90 in advance ℃ polymerization 2 hours, 1.8724 gram polystyrene, catalytic activity is 1.96 * 10
6Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 87.7%.[embodiment 5]
11 milliliters of vinylbenzene, 1 ml concn are the methylaluminoxane toluene solution of 1.53 mol, and 0.1 milliliter 0.05 mol Compound I ndTiCl
2(OMe) toluene solution is injected in the ampere bottle successively, is positioned in the oil bath of constant temperature to 70 in advance ℃ polymerization 1 hour, 1.6544 gram polystyrene, catalytic activity is 3.46 * 10
6Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 90.3%.[comparative example 2]
11 milliliters of vinylbenzene, 1 ml concn are the methylaluminoxane toluene solution of 1.53 mol, and 0.1 milliliter 0.05 mol IndTiCl
3Toluene solution be injected into successively in the ampere bottle, be positioned in the oil bath of constant temperature to 70 in advance ℃ polymerization 1 hour, 1.4586 gram polystyrene, catalytic activity is 3.05 * 10
6Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 86.6%.[embodiment 6]
11 milliliters of vinylbenzene, 1 ml concn are the methylaluminoxane toluene solution of 1.53 mol, and 0.1 milliliter 0.05 mol Compound I ndTiCl
2(OMe) toluene solution is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 25 in advance ℃ polymerase 10 .5 hour, 0.9766 gram polystyrene, catalytic activity is 4.08 * 10
6Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 85.2%.[embodiment 7]
2 milliliters of vinylbenzene, 8.5 milliliters of toluene, the methylaluminoxane toluene solution of 1.6 ml concns, 1.53 mol, and 0.24 milliliter 0.0025 mol Compound I ndTiCl
2(OMe) toluene solution is injected in the ampere bottle successively, is positioned in the oil bath of constant temperature to 50 in advance ℃ polymerization 1 hour, 0.1337 gram polystyrene, catalytic activity is 1.28 * 10
7Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 98.1%.[embodiment 8]
(preparation of compd A): under argon shield; the normal hexane and the tetrahydrofuran (THF) mixing solutions of alkyl alcohol (wherein R is an ethyl) are slowly dripped in the hexane solution of n-Butyl Lithium; the mol ratio of alkyl alcohol and butyllithium is 1: 1.2; the lithium salt solution that reaction generates is chilled to-50 ℃, with the IndTiCl of mole number such as alkyl alcohol
3Dichloromethane solution slowly drip in this solution, dripped off in 0.5 hour, rise to 30 ℃ naturally, stirring reaction 16 hours filters, clear liquid is drained, the gained solid is with methylene dichloride and normal hexane recrystallization, the scarlet crystal yield be 58%.The analytical test result is as follows
Molecular formula: C
11H
12Cl
2OTi; Mass spectrum demonstration molecular ion peak 278 (5, M
+).
Ir data (cm
-1): 3300s, 1620m, 1460w, 1390w, 1050w, 880s, 825s.
Nuclear magnetic data (
1H NMR, ppm): 7.79 (dd, 2H, J=6.3Hz, J=3.0Hz), 7.45 (dd, 2H, J=6.3Hz, J=3.0Hz), 6.84 (d, 2H, J=3.4Hz), 6.80 (t, 1H, J=3.4Hz), 4.60 (q, 2H, J=5.3Hz), 1.31 (t, 3H, J=5.3Hz).
Ultimate analysis data: actual measurement, C:47.21% H:4.29%
Calculate C:47.36% H:4.34%[embodiment 9]
(preparation of compd B): under argon shield; the hexane solution of alkyl alcohol (wherein R is a sec.-propyl) is slowly dripped in the hexane solution of n-Butyl Lithium; the mol ratio of alkyl alcohol and butyllithium is 1: 1; the lithium salt solution that reaction generates is chilled to-60 ℃, with the alkyl alcohol mol ratio be 1: 1.2 IndTiCl
3Dichloromethane solution slowly drip in this solution, dripped off in 0.5 hour, rise to 35 ℃ naturally, stirring reaction 16 hours filters, clear liquid is drained, the gained solid is with methylene dichloride and normal hexane recrystallization, the scarlet crystal yield be 76%.The analytical test result is as follows
Molecular formula: C
12H
14Cl
2OTi; Mass spectrum demonstration molecular ion peak 292 (2, M
+).
Ir data (cm
-1): 3330s, 1613m, 1458w, 1392w, 1360w, 1315w, 1200w, 1168w, 1114w, 1050w, 884s, 768s.
Nuclear magnetic data (
1H NMR, ppm): 7.80 (dd, 2H, J=6.3Hz, J=3.1Hz), 7.45 (dd, 2H, J=6.3Hz, J=3.1Hz), 6.82 (d, 2H, J=3.4Hz), 6.78 (t, 1H, J=3.4Hz), 4.92 (m, 1H, J=6.1Hz), 1.38 (d, 6H, J=6.1Hz).
Ultimate analysis data: actual measurement, C:48.81% H:4.76%
Calculate C:49.19% H:4.82%[embodiment 10]
(preparation of Compound C): under argon shield; the hexane solution of alkyl alcohol (wherein R is a cyclohexyl) is slowly dripped in the hexane solution of n-Butyl Lithium; the mol ratio of alkyl alcohol and butyllithium is 1: 1.1; the lithium salt solution that reaction generates is chilled to-60 ℃, with the alkyl alcohol mol ratio be 1: 1.2 IndTiCl
3Dichloromethane solution slowly drip in this solution, dripped off in 0.5 hour, rise to 30 ℃ naturally, stirring reaction 16 hours filters, clear liquid is drained, the gained solid is with methylene dichloride and normal hexane recrystallization, the orange crystal yield be 61%.The analytical test result is as follows
Molecular formula: C
15H
18Cl
2OTi; Mass spectrum demonstration molecular ion peak 332 (0.6, M
+).
Ir data (cm
-1): 3300s, 2930m, 2865m, 1615m, 1460w, 1398w, 1370w, 1055m, 1020w, 885s, 770s.
Nuclear magnetic data (
1H NMR, ppm): 7.78 (dd, 2H, J=6.4Hz, J=3.0Hz), 7.41 (dd, 2H, J=6.4Hz, J=3.0Hz), 6.82 (d, 2H, J=3.4Hz), 6.79 (t, 1H, J=3.4Hz), 4.70 (m, 1H), 2.3～1.0 (m, 10H).
Ultimate analysis data: actual measurement, C:53.93% H:5.35%
Calculate C:54.09% H:5.45%[embodiment 11]
Polyreaction is carried out in the ampere bottle of a baking argon filling three times.2 milliliters of vinylbenzene, 3.4 milliliter toluene, 6.6 the methylaluminoxane toluene solution of ml concn 1.53 mol, and the toluene solution of 0.05 milliliter 0.05 mol compd A is injected in the ampere bottle successively was positioned in the oil bath of constant temperature to 50 in advance ℃ polymerization 1 hour.The ethanol that contains 10%HCl with weight concentration stops polyreaction, after filtration, after the carrying out washing treatment, resulting polymers in 80 ℃ of following vacuum-dryings 24 hours to constant weight, 0.2109 gram polystyrene, catalytic activity is 4.85 * 10
6Gram PS/ (mole Ti mole S hour).Refluxed 2 hours in butanone, remove random polystyrene, recording the syndiotactic polystyrene weight content is 99.6%, and the resulting polymers fusing point is 275 ℃.[embodiment 12]
2 milliliters of vinylbenzene, 3.4 milliliter toluene, 6.6 the methylaluminoxane toluene solution of ml concn 1.53 mol, and the toluene solution of 0.05 milliliter 0.05 mol compd B is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 50 in advance ℃ polymerization 1 hour, get 0.1736 gram polystyrene, catalytic activity is 3.99 * 10
6Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 99.1%, the fusing point of polymkeric substance is 273 ℃.[embodiment 13]
11 milliliters of vinylbenzene, 0.5 ml concn is the methylaluminoxane toluene solution of 1.53 mol, and the toluene solution of 0.05 milliliter 0.05 mol compd A is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 50 in advance ℃ polymerase 10 .5 hour, get 1.6676 gram polystyrene, catalytic activity is 1.39 * 10
7Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 90.1%.[comparative example 3]
11 milliliters of vinylbenzene, 0.5 ml concn are the methylaluminoxane toluene solution of 1.53 mol, and 0.05 milliliter 0.05 mol IndTiCl
3Toluene solution be injected into successively in the ampere bottle, be positioned in the oil bath of constant temperature to 50 in advance ℃ polymerase 10 .5 hour, 1.0996 gram polystyrene, catalytic activity is 9.19 * 10
6Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 86.4%.[embodiment 14]
11 milliliters of vinylbenzene, 1 ml concn is the methylaluminoxane toluene solution of 1.53 mol, and the toluene solution of 0.1 milliliter 0.05 mol compd A is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 50 in advance ℃ polymerase 10 .5 hour, get 1.5117 gram polystyrene, catalytic activity is 6.32 * 10
6Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 88.4%.[embodiment 15]
11 milliliters of vinylbenzene, 1 ml concn is the methylaluminoxane toluene solution of 1.53 mol, and the toluene solution of 0.1 milliliter 0.05 mol compd A is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 70 in advance ℃ polymerization 1 hour, get 1.7452 gram polystyrene, catalytic activity is 3.65 * 10
6Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 91.2%.[comparative example 4]
11 milliliters of vinylbenzene, 1 ml concn are the methylaluminoxane toluene solution of 1.53 mol, and 0.1 milliliter 0.05 mol IndTiCl
3Toluene solution be injected into successively in the ampere bottle, be positioned in the oil bath of constant temperature to 70 in advance ℃ polymerization 1 hour, 1.4586 gram polystyrene, catalytic activity is 3.05 * 10
6Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 86.6%.[embodiment 16]
11 milliliters of vinylbenzene, 1 ml concn is the methylaluminoxane toluene solution of 1.53 mol, and the toluene solution of 0.1 milliliter 0.05 mol compd A is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 90 in advance ℃ polymerization 2 hours, get 2.2418 gram polystyrene, catalytic activity is 2.34 * 10
6Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 90.7%.[embodiment 17]
11 milliliters of vinylbenzene, 1 ml concn is the methylaluminoxane toluene solution of 1.53 mol, and the toluene solution of 0.1 milliliter 0.05 mol compd A is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 25 in advance ℃ polymerase 10 .5 hour, get 0.9050 gram polystyrene, catalytic activity is 3.78 * 10
6Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 83.1%.[embodiment 18]
11 milliliters of vinylbenzene, 1 ml concn is the methylaluminoxane toluene solution of 1.53 mol, and the toluene solution of 0.1 milliliter 0.05 mol compd B is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 50 in advance ℃ polymerase 10 .5 hour, get 0.9711 gram polystyrene, catalytic activity is 4.06 * 10
6Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 85.2%.[embodiment 19]
11 milliliters of vinylbenzene, 1 ml concn is the methylaluminoxane toluene solution of 1.53 mol, and the toluene solution of 0.1 milliliter 0.05 mol Compound C is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 50 in advance ℃ polymerase 10 .5 hour, get 0.7794 gram polystyrene, catalytic activity is 3.26 * 10
6Gram PS/ (mole Ti mole S hour), recording the syndiotactic polystyrene weight content is 79.2%.
Claims (3)
1, a kind of catalyzer of syndiotactic polymerization of phenylethylene comprises following active constituent:
a)IndTiCl
2(OR)；
B) alkylaluminoxane;
Wherein Ind is an indenyl;
R is the alkyl of straight chain, side chain or the ring texture of 3～6 carbon atoms;
With molar ratio computing, alkylaluminoxane/IndTiCl
2(OR) be 300～4100.
2,, it is characterized in that alkylaluminoxane is a methylaluminoxane according to the catalyzer of the described syndiotactic polymerization of phenylethylene of claim 1.
3,, it is characterized in that with molar ratio computing alkylaluminoxane/IndTiCl according to the catalyzer of the described syndiotactic polymerization of phenylethylene of claim 1
2(OR) be 300～2100.
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|---|---|---|---|
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| CN103421130B (en) * | 2012-05-16 | 2016-01-13 | 中国石油化工股份有限公司 | High activity double center metallocene titanium composition |
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