CN103421130A - High activity double center metallocene titanium composition - Google Patents

High activity double center metallocene titanium composition Download PDF

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CN103421130A
CN103421130A CN2012101503583A CN201210150358A CN103421130A CN 103421130 A CN103421130 A CN 103421130A CN 2012101503583 A CN2012101503583 A CN 2012101503583A CN 201210150358 A CN201210150358 A CN 201210150358A CN 103421130 A CN103421130 A CN 103421130A
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metallocene titanium
composition
molecular weight
metallocene
titanium
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CN103421130B (en
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沈志刚
赵薇薇
周文乐
宗弘元
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The present invention relates to a double activity center metallocene titanium composition, wherein the problem that the prepared syndiotactic polystyrene has narrow molecular weight distribution so as to difficultly meet processing requirements during application of the previous single activity metallocene titanium compound in styrene syndiotactic polymerization is mainly solved with the present invention. The technical scheme comprises that the composition comprises the following components, by mole: a) 1-10 parts of a CpTi(OR1OR2)3 metallocene titanium compound, b) 1-10 parts of a Cp*Ti(OR3OR4)3 metallocene titanium compound, and c) 100-20000 parts of methyl aluminoxane, wherein the components are mixed and dissolved into a solvent according to a certain ratio to form the composition with double activity centers, Cp is cyclopentadienyl, Cp* is pentamethyl cyclopentadienyl, R1 and R3 are phenyl, R2 and R4 are alkyl containing 1-6 carbon atoms, oxygen atoms are connected between Ti and R1, and Ti and R3, and oxygen atoms are connected between R1, R2, R3 and R4. With the technical scheme, the problem in the prior art is well solved, and the composition can be used for industrial production of syndiotactic polystyrene.

Description

The two centers of high reactivity metallocene titanium composition
Technical field
The present invention relates to double activated metallocene titanium composition.
Background technology
The homogeneous catalysis system that cyclopentadiene titanium compound and promotor methylaluminoxane (MAO) or boron fluorine cpd form, can obtain a normality at the syndiotactic polymer more than 96% for syndiotactic polymerization of phenylethylene.Melting point polymer is up to 270 ℃, and crystallization velocity is fast, chemically-resistant, and good heat resistance, narrow molecular weight distribution, good stability of the dimension, and there is excellent electrical property, its over-all properties can be compared with engineering plastics.The appearance of syndiotactic polystyrene (SPS) has caused that people are to its catalyst system, the particularly research of Primary Catalysts metallocene compound.Document US5252693 and EP210615 have reported that structure is CpTiCl 3And Cp*TiCl 3The catalyst system formed with promotor MAO is for the situation of syndiotactic polymerization of phenylethylene, and wherein Cp is cyclopentadienyl, and Cp* is the pentamethyl-cyclopentadienyl, but its catalytic activity and catalytic efficiency are not high, poor stability, and industrial application value is little.Patent CN00119775.4, US5023222, US5045517 and US5196490 have reported the Cp*Ti (OR that current catalytic efficiency is high 2OR 3) 3And Cp*Ti (OR) 3Type catalyzer (R is alkyl or aryl), specific activity had significantly raising in the past, but the syndiotactic polystyrene molecular weight distribution prepared is narrower, between 1.5～2.5.This very poor than narrow molecular weight distributions syndiotactic polystyrene processing characteristics, restricted the application in hollow container, film, tubing, cable, sheet material field.We gain enlightenment from the development of polyethylene product, because workability and the mechanical property of polyvinyl resin are conflicting, improve molecular weight and can make product there is better mechanical property, but resin becomes again and is difficult to processing simultaneously, and bimodal polyethylene can address this problem well.This product is comprised of High molecular weight polyethylene and low molecular weight polyethylene two portions, wherein High molecular weight polyethylene is in order to guarantee physical mechanics intensity, low molecular weight polyethylene is conflicting in order to workability and the mechanical property of improving the processing characteristics polyvinyl resin, improve molecular weight and can make product there is better mechanical property, but resin becomes again and is difficult to processing simultaneously.The method of producing bimodal polyethylene mainly contains: 1. in same reactor, use 2 kinds of completely different and catalyzer independently, they respectively produce a kind of polyolefine with different molecular weight; 2. adopt at 2 and independently in reactor, carry out sequential polymerisation reactions; 3. polymkeric substance different molecular weight distributed is mixed.But adopt the mode of multiple reactor sequential polymerization to invest greatly, and melt blended cost is high, and is difficult to mix.Therefore single reactor prepares the progress that the bimodal polyethylene technology is regarded as the property changed.
Summary of the invention
Technical problem to be solved by this invention is that the metallocene-titanium catalyst overcome in previous literature all has single active center, cause the narrower problem of syndiotactic polystyrene molecular weight distribution prepared, a kind of new metallocene titanium composition with double activity center is provided.The syndiotactic polystyrene that uses said composition to prepare, have advantages of wide molecular weight distribution.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of double activity center metallocene titanium composition, in molfraction, comprises following component:
A) 1～10 part of CpTi (OR 1OR 2) 3Metallocene titanium compound;
B) 1～10 part of Cp*Ti (OR 3OR 4) 3Metallocene titanium compound;
C) 100～20000 parts of methylaluminoxane;
Wherein Cp is cyclopentadienyl, and Cp* is the pentamethyl-cyclopentadienyl, R 1, R 3For phenyl, R 2, R 4For the alkyl containing 1～6 carbon atom, Ti and a R 1, R 3There is Sauerstoffatom to be connected, R 1, R 2, R 3With R 4Between all have Sauerstoffatom to be connected.
R in technique scheme 2, R 4For methyl, ethyl, propyl group or butyl.A) and b) the component mol ratio is 1:10～10:1.Aluminium and titanium mol ratio are 50 to 2000.
The preparation method of above-mentioned double activity center metallocene titanium composition comprises the following steps: a) 1～10 part of CpTi (OR 1OR 2) 3Metallocene titanium compound; B) 1～10 part of Cp*Ti (OR 3OR 4) 3Metallocene titanium compound; C) 100～20000 parts of methylaluminoxane; Stirring at normal temperature mixed dissolution in solvent in proportion, solvent used is aromatic hydrocarbons or alkane.Comprise at least one in toluene, ethylbenzene, hexane, hexanaphthene, solvent load is not particularly limited, and can all dissolve a, b just can at normal temperatures.Mixing time is 1-60 minute.More preferably scheme is 5-30 minute.
Because traditional syndiotactic polystyrene is the metallocene-titanium catalyst that adopts a kind of single active center, cause the product molecular weight distribution made narrow; Owing to using two kinds of activity to differ larger cyclopentadiene titanium compound, form double activity center's catalyzer, wherein CpTi (OR in the present invention 1OR 2) 3Metallocene titanium spike can prepare the lower molecular weight syndiotactic polystyrene, and Cp*Ti (OR 3OR 4) 3Metallocene can prepare the syndiotactic polystyrene of high molecular, and the catalysis after combination can prepare the wide product of molecular weight distribution.
Experimental data can find out, the molecular weight distribution of traditional syndiotactic polystyrene is generally in 2 left and right, and the bimodal wide molecular weight distribution syndiotactic poly styrene polymer molecular weight distribution in the present invention can be at 15-100.Low 10 ℃ of the syndiotactic polystyrene of the comparable general narrow molecular weight distributions of polymer processing plasticization temperature, improve processing characteristics greatly, obtained good technique effect.
The accompanying drawing explanation
Fig. 1 is traditional syndiotactic polystyrene product G PC curve.
Fig. 2 adopts bimodal wide molecular weight distribution syndiotactic polystyrene product G PC curve in the present invention.
Fig. 1 is obviously unimodal distribution, and molecular weight distribution is very narrow, only has 1.8; Fig. 2 is obviously bimodal distribution, and molecular weight distribution is very wide, can reach 67.
Below by embodiment, the invention will be further elaborated.
 
The present invention utilizes CpTi (OR 2OR 3) 3With metallocene titanium compound Cp*Ti (OR 2OR 3) 3Diverse active centre, CpTi (OR 2OR 3) 3But catalysis obtains the lower molecular weight syndiotactic polystyrene.Cp*Ti (OR 2OR 3) 3But catalysis obtains the high molecular syndiotactic polystyrene, therefore adopt these two kinds of metallocene titanium compounds to be mixed to form by a certain percentage composition, add methylaluminoxane and the triisobutyl aluminium of corresponding proportion to form the catalyzer with double activity center, this type of catalyzer, for styrene catalyzed syndiotactic polymerization the time, can prepare the syndiotactic polystyrene of the wide molecular weight distribution (being distributed in 15～100) with bimodal distribution.
 
Embodiment
[embodiment 1]
In the there-necked flask of 100 milliliters of drying, N 2Pump drainage 3 times, add 0.1 mmole A) CpTi (OC 6H 4OCH 3) 3With 0.1 mmole B) Cp*Ti (OC 6H 4OCH 3) 3, to mix mol ratio A:B=1:1 and add 50 milliliters of toluene, the normal temperature induction stirring makes compound dissolution, adds 60 mmole triisobutyl aluminiums, and 60 mmole methylaluminoxane are uniformly mixed and obtain double activity center's metallocene titanium composition 1.
 
[embodiment 2]
In the there-necked flask of 100 milliliters of drying, N 2Pump drainage 3 times, add 0.02 mmole A) CpTi (OC 6H 4OCH 3) 3With 0.18 mmole B) Cp*Ti (OC 6H 4OCH 3) 3, to mix mol ratio A:B=1:9 and add 50 milliliters of ethylbenzene, the normal temperature induction stirring makes compound dissolution, adds 40 mmole triisobutyl aluminiums, and 120 mmole methylaluminoxane are uniformly mixed and obtain double activity center's metallocene titanium composition 2.
 
[embodiment 3]
In the there-necked flask of 100 milliliters of drying, N 2Pump drainage 3 times, add 0.16 mmole A) CpTi (OC 6H 4OCH 3) 3With 0.04 mmole B) Cp*Ti (OC 6H 4OCH 3) 3, to mix mol ratio A:B=4:1 and add 50 ml n-hexanes, the normal temperature induction stirring makes compound dissolution, adds 40 mmole triisobutyl aluminiums, and 40 mmole methylaluminoxane are uniformly mixed and obtain double activity center's metallocene titanium composition 3.
 
[embodiment 4]
In the there-necked flask of 100 milliliters of drying, N 2Pump drainage 3 times, add 0.15 mmole A) CpTi (OC 6H 4OCH 3) 3With 0.05 mmole B) Cp*Ti (OC 6H 4OCH 3) 3, to mix mol ratio A:B=3:1 and add 50 milliliters of hexanaphthenes, the normal temperature induction stirring makes compound dissolution, adds 60 mmole triisobutyl aluminiums, and 40 mmole methylaluminoxane are uniformly mixed and obtain double activity center's metallocene titanium composition 4.
 
[embodiment 5]
In the there-necked flask of 100 milliliters of drying, N 2Pump drainage 3 times, add 0.025 mmole A) CpTi (OC 6H 4OCH 3) 3With 0.175 mmole B) Cp*Ti (OC 6H 4OCH 3) 3, to mix mol ratio A:B=1:7 and add 50 milliliters of toluene, the normal temperature induction stirring makes compound dissolution, obtains double activity center's metallocene titanium composition 5.
 
[embodiment 6]
In the there-necked flask of 100 milliliters of drying, N 2Pump drainage 3 times, add 0.05 mmole A) CpTi (OC 6H 4OCH 3) 3With 0.15 mmole B) Cp*Ti (OC 6H 4OCH 3) 3, to mix mol ratio A:B=1:3 and add 50 milliliters of toluene, the normal temperature induction stirring makes compound dissolution, adds 30 mmole triisobutyl aluminiums, and 130 mmole methylaluminoxane are uniformly mixed and obtain double activity center's metallocene titanium composition 6.
 
[embodiment 7]
On 5 liters of mechanical stirring kettles, first 90 ℃ of bakings, after 8 hours, lower the temperature, N 2Pump drainage 3 times, add styrene monomer 1188 grams, now the interior temperature of system is 35 ℃, inject the double activity center's metallocene titanium composition 1 containing 0.107 mmole titanium embodiment 1 preparation with syringe, after catalyzer adds, progressively chuck heating, about 40 minutes, make in system temperature to 60 ℃ of polymerization temperatures, at 300 rev/mins of lower stirring reactions, after 4 hours, by ethanol-hydrochloric acid soln stopped reaction, wash, dry powder solid 784 grams that obtain, catalyst efficiency 123 kg of polymer/(gram titanium), a normality 97%, Mw=48 * 10 4, molecular weight distribution mw/mn=79.
 
[embodiment 8]
On 5 liters of mechanical stirring kettles, first 90 ℃ of bakings, after 8 hours, lower the temperature, N 2Pump drainage 3 times, add styrene monomer 1188 grams, now the interior temperature of system is 35 ℃, inject the double activity center's metallocene titanium composition 2 containing 0.107 mmole titanium embodiment 2 preparations with syringe, after catalyzer adds, progressively chuck heating, about 40 minutes, make in system temperature to 60 ℃ of polymerization temperatures, at 300 rev/mins of lower stirring reactions, after 4 hours, by ethanol-hydrochloric acid soln stopped reaction, wash, dry powder solid 802 grams that obtain, catalyst efficiency 126 kg of polymer/(gram titanium), a normality 97%, Mw=59 * 10 4, molecular weight distribution mw/mn=63.
[embodiment 9]
On 5 liters of mechanical stirring kettles, first 90 ℃ of bakings, after 8 hours, lower the temperature, N 2Pump drainage 3 times, add styrene monomer 1188 grams, now the interior temperature of system is 35 ℃, inject the double activity center's metallocene titanium composition 3 containing 0.107 mmole titanium embodiment 3 preparations with syringe, after catalyzer adds, progressively chuck heating, about 40 minutes, make in system temperature to 60 ℃ of polymerization temperatures, at 300 rev/mins of lower stirring reactions, after 4 hours, by ethanol-hydrochloric acid soln stopped reaction, wash, dry powder solid 714 grams that obtain, catalyst efficiency 112 kg of polymer/(gram titanium), a normality 97%, Mw=14 * 10 4, molecular weight distribution mw/mn=62.
 
[embodiment 10]
On 5 liters of mechanical stirring kettles, first 90 ℃ of bakings, after 8 hours, lower the temperature, N 2Pump drainage 3 times, add styrene monomer 1188 grams, now the interior temperature of system is 35 ℃, double activity center's metallocene titanium composition 4 with syringe containing preparation in 0.107 mmole titanium embodiment 4, after catalyzer adds, progressively chuck heating, about 40 minutes, make in system temperature to 60 ℃ of polymerization temperatures, at 300 rev/mins of lower stirring reactions, after 4 hours, by ethanol-hydrochloric acid soln stopped reaction, wash, dry powder solid 726 grams that obtain, catalyst efficiency 114 kg of polymer/(gram titanium), a normality 97%, Mw=20 * 10 4, molecular weight distribution mw/mn=39.
 
[embodiment 11]
On 5 liters of mechanical stirring kettles, first 90 ℃ of bakings, after 8 hours, lower the temperature, N 2Pump drainage 3 times, add styrene monomer 1188 grams, now the interior temperature of system is 35 ℃, inject the double activity center's metallocene titanium composition 5 containing 0.107 mmole titanium embodiment 5 preparations with syringe, after catalyzer adds, progressively chuck heating, about 40 minutes, make in system temperature to 60 ℃ of polymerization temperatures, at 300 rev/mins of lower stirring reactions, after 4 hours, by ethanol-hydrochloric acid soln stopped reaction, wash, dry powder solid 781 grams that obtain, catalyst efficiency 122 kg of polymer/(gram titanium), a normality 97%, Mw=61 * 10 4, molecular weight distribution mw/mn=54.
 
[embodiment 12]
On 5 liters of mechanical stirring kettles, first 90 ℃ of bakings, after 8 hours, lower the temperature, N 2Pump drainage 3 times, add styrene monomer 1188 grams, now the interior temperature of system is 35 ℃, inject the double activity center's metallocene titanium composition 6 containing 0.107 mmole titanium embodiment 6 preparations with syringe, after catalyzer adds, progressively chuck heating, about 40 minutes, make in system temperature to 60 ℃ of polymerization temperatures, at 300 rev/mins of lower stirring reactions, after 4 hours, by ethanol-hydrochloric acid soln stopped reaction, wash, dry powder solid 732 grams that obtain, catalyst efficiency 115 kg of polymer/(gram titanium), a normality 97%, Mw=35 * 10 4, molecular weight distribution mw/mn=68.
 
[comparative example 1]
Except adding the CpTi (OC containing 0.107 mmole titanium 6H 4OCH 3) 3Single active center's metallocene titanium compound replaces
Double activity center's metallocene titanium composition 1, other condition is all identical, and aluminium titanium mol ratio is also identical.Washing, dry powder solid 350 grams, catalyst efficiency 53 kg of polymer/(gram titanium), a normality 97%, Mw=9 * 10 of obtaining 4, molecular weight distribution mw/mn=1.8.
 
[comparative example 2]
Except adding the Cp*Ti (OC containing 0.107 mmole titanium 6H 4OCH 3) 3Single active center's metallocene titanium compound replaces
Double activity center's metallocene titanium composition 2, other condition is all identical, washing, dry powder solid 799 grams, catalyst efficiency 126 kg of polymer/(gram titanium), a normality 97%, Mw=98 * 10 of obtaining 4, molecular weight distribution mw/mn=1.7.

Claims (3)

1. double activity center's metallocene titanium composition, in molfraction, comprises following component:
A) 1～10 part of CpTi (OR 1OR 2) 3Metallocene titanium compound;
B) 1～10 part of Cp*Ti (OR 3OR 4) 3Metallocene titanium compound;
C) 100～20000 parts of methylaluminoxane;
Wherein Cp is cyclopentadienyl, and Cp* is the pentamethyl-cyclopentadienyl, R 1, R 3For phenyl, R 2, R 4For the alkyl containing 1～6 carbon atom, Ti and R 1, R 3Between have Sauerstoffatom to be connected, R 1, R 2, R 3With R 4Between all have Sauerstoffatom to be connected.
2. double activity center's metallocene titanium composition according to claim 1, is characterized in that R 2, R 4For methyl, ethyl, propyl group or butyl.
3. double activity center's metallocene titanium composition according to claim 1, wherein a) and b) the component mol ratio is 1:10～10:1; In composition, aluminium and titanium mol ratio are 50 to 2000.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539878A (en) * 2012-07-12 2014-01-29 中国石油化工股份有限公司 Method for preparing syndiotactic polystyrene polymer with doublet broad molecular weight distribution

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Publication number Priority date Publication date Assignee Title
US5340892A (en) * 1989-09-29 1994-08-23 Idemitsu Kosan Co., Ltd. Process for producing styrene polymers
CN1285362A (en) * 1999-08-19 2001-02-28 中国石油化工集团公司 Catalyst for preparation of syndiotactic polystyrene
CN1352205A (en) * 2000-11-15 2002-06-05 中国石油化工股份有限公司 Catalyst for syndiotatic phenylethylene polymerization
CN1450089A (en) * 2002-04-10 2003-10-22 中国石油化工股份有限公司 Metallocene titanium compound and use thereof

Patent Citations (4)

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CN1285362A (en) * 1999-08-19 2001-02-28 中国石油化工集团公司 Catalyst for preparation of syndiotactic polystyrene
CN1352205A (en) * 2000-11-15 2002-06-05 中国石油化工股份有限公司 Catalyst for syndiotatic phenylethylene polymerization
CN1450089A (en) * 2002-04-10 2003-10-22 中国石油化工股份有限公司 Metallocene titanium compound and use thereof

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Title
马海燕等: "CpTiCl2(OR)/MAO体系催化苯乙烯间规聚合的研究", 《高等学校化学学报》, vol. 22, no. 7, 31 July 2001 (2001-07-31), pages 1259 - 1261 *
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539878A (en) * 2012-07-12 2014-01-29 中国石油化工股份有限公司 Method for preparing syndiotactic polystyrene polymer with doublet broad molecular weight distribution

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