CN1084337C - Composition and preparation method for butadiene gas-phase polymerization rare earth catalyst - Google Patents

Composition and preparation method for butadiene gas-phase polymerization rare earth catalyst Download PDF

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CN1084337C
CN1084337C CN99101536A CN99101536A CN1084337C CN 1084337 C CN1084337 C CN 1084337C CN 99101536 A CN99101536 A CN 99101536A CN 99101536 A CN99101536 A CN 99101536A CN 1084337 C CN1084337 C CN 1084337C
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rare earth
catalyst
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phase polymerization
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CN1229097A (en
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沈之荃
张一烽
刘青
李维实
倪旭峰
曾年初
梁爱民
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Beijing Research Institute of Beijing Yanshan Petrochemical Corp
Zhejiang University ZJU
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Beijing Research Institute of Beijing Yanshan Petrochemical Corp
Zhejiang University ZJU
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Abstract

The present invention discloses a composition and a preparation method for a butadiene gas-phase polymerization rare earth catalyst. The composite system is composed of a component A, a component B, a component C and a component D, wherein the component A is a rare earth compound, the component B is aluminum alkyl, the component is halide and the component D is inert powder. The present invention has the preparation method that the component A, the component B, the component C and the component D are uniformly mixed in hydrogenated gasoline or benzene and react for 0.5 to 24 hours at a temperature of 40 to 80 DEG C. Then, a mixture is prepared by removing a solvent. The catalytic activity of the catalyst is high and can be prepared into polybutadiene with molecular weights of 200000 to 1000000, 0.5 to 18% of gel content and 95 to 98% of cis-1, 4 structure content. The present invention has the advantages of low polymerization investment, low energy consumption and little pollution.

Description

The composition of butadiene gas-phase polymerization rare earth catalyst and preparation method
The present invention relates to a kind of composition and preparation method of catalyzer, relate in particular to the composition and the preparation method of butadiene gas-phase polymerization rare earth catalyst.
Cis-rich polybutadiene rubber is widely used in tire and other rubber item, and it is improving the wear resisting property of tire, flex cracking resistance, resistance to low temperature and reduce aspect such as hysteresis loss and play an important role.Butadiene gas-phase polymerization is made the method for high-cis polybutadiene and traditional solution polymerization process relatively has technological process of production weak point, the production efficiency height, and low equipment investment, energy consumption is low, pollutes outstanding advantage such as little grade.
The purpose of this invention is to provide a kind of rare earth catalyst that is suitable for butadiene gas-phase polymerization and preparation method thereof.
The present invention takes following measures in order to achieve the above object:
The composition of butadiene gas-phase polymerization rare earth catalyst is the compound system of A, B, C and four components of D.
The A component means rare earth compound, be the rare earth carboxylate that any or pr-nd enriched product in Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and 15 kinds of rare earth elements of Lu and phenylformic acid (BA) or naphthenic acid (naph) reaction form, perhaps with P 204, P 229, P 507, P 350Prepared rare earth phosphonate, wherein
Figure C9910153600031
The B component means aluminum alkyls, i.e. triethyl aluminum or triisobutyl aluminium or diisobutylaluminium hydride.
The C component means halogenide, i.e. binary halogenated alkane BrCH 2CH 2Br or halogenated aryl hydrocarbon C 6H 5CH 2Cl or alkyl, aryl halide silane R 3SiX, R=-CH 3,-C 2H 5,-C 6H 5, X=Cl, Br or haloalkyl aluminium R 2AlCl, R 3Al 2X 3, R=-CH 3,-C 2H 5,-i-C 4H 9, X=Cl, Br.
The D component means carrier, i.e. silica gel or aluminum oxide or carbon black.
The preparation method of butadiene gas-phase polymerization rare earth catalyst is with above-mentioned A, B, and C, four components of D are uniform mixing in the hydrogenated gasoline of purified processing or toluene, in 40～80 ℃ of reaction 0.5～24h., removes solvent then and forms.The mol ratio of each component of catalyzer is A: B=1: 5～500, and A: C=1: 1～40, A: D=1: 30～5000.
Advantage of the present invention:
This catalyzer is used for butadiene gas-phase polymerization and has polymerization technique flow process weak point, low equipment investment, and the production efficiency height, energy consumption is low, pollutes little.Estimate that butadiene gas-phase polymerization can reduce production costs 24%, can get rid of the energy consumption operation relevant with solvent (solvent refining, reclaim drying etc.), only this is capable of reducing energy consumption 80%, and also can reducing simultaneously founds the factory invests 20%.
Elaborate below in conjunction with embodiment:
The preparation method of A component in the composition of butadiene gas-phase polymerization rare earth catalyst: make rare earth chloride or praseodymium chloride, neodymium mixture by the oxide compound of rare earth element or pr-nd enriched product and dilute hydrochloric acid reaction, then with P 204, P 229, P 507, P 350Or phenylformic acid or naphthenic acid are that extraction agent makes rare earth phosphonate or rare earth carboxylate.The mol ratio of each component of catalyzer is A: B=1: 20～100, and A: C=1: 1～10, A: D=1: 100～500.
Example one,
1) carrier pre-treatment
Carrier S iO 2Pore volume is 155～210M 3/ g, specific surface area is 280M 2/ g through 600 ℃ of calcinations 4 hours, gets 100g and adds the 400ml hydrogenated gasoline before using, and adds 2.0ml (7.89mmol) triisobutyl aluminium, stirs, and floods to separate gasoline solution after 30 minutes, again with fresh hydrogenated gasoline washing 3 times, drying.
2) Preparation of Catalyst
In the 250ml of purifying treatment single port bottle, add 0.48mmol Nd (naph) 3, 50ml toluene, 19.2mmol Al (i-Bu) 3, 0.48mmolAl 2Et 3Cl 3, 0.17molSiO 2, stir, 60 ℃ were reacted 2 hours, left standstill 20 hours.Separate solvent and dry, obtain the micro-yellow powder shape loading type rare earth catalyst of 17.3g good fluidity.
3) butadiene gas-phase polymerization
In purifying treatment and vertical response still with the modified version anchor stirrer, add above-mentioned prepared rare earth catalyst 0.498g, open stirring, feed divinyl gas, control still internal pressure is 0.03～0.10MPa.50 ℃ of down reactions 45 minutes, dry that viscosity-average molecular weight 460,000, molecular weight distributing index 3.1, gel content 1.8%, suitable-1,4 structural content are 97% polyhutadiene 29g through aftertreatment.
Example two,
1) carrier and pre-treatment thereof are with example one.
2) Preparation of Catalyst
Add 0.98mmol Nd (BA) in the 250ml single port bottle 3, 50ml gasoline, 39.2mmol Al (i-Bu) 3, 0.98mmolAl 2Et 3Cl 3And 0.37molSiO 2, stir, 80 ℃ were reacted 1 hour, left standstill 10 hours.Separate solvent, drying obtains having the micro-yellow powder shape catalyzer 32.6g of good fluidity.
3) butadiene gas-phase polymerization
In purifying treatment and vertical response still with the modified version anchor stirrer, add above-mentioned prepared rare earth catalyst 0.624g, open stirring, feed divinyl gas, control still internal pressure is 0.03～0.12MPa.50 ℃ of down reactions 1 hour, dry that viscosity-average molecular weight 860,000, molecular weight distributing index 2.8, gel content 2.3%, suitable-1,4 structural content are 96% polyhutadiene 6.5g through aftertreatment.
Example three,
1) carrier and pre-treatment thereof are with example one.
2) Preparation of Catalyst
Add 0.15mmolNd (naph) in the 250ml single port bottle 3, 100ml toluene, 6mmolAl (i-Bu) 3, 0.45mmolAl (i-Bu) 2Cl, 0.5molSiO 2, stir, 70 ℃ were reacted 0.5 hour, left standstill 16 hours.Separate solvent, drying obtains the micro-yellow powder shape catalyzer 34.7g of good fluidity.
3) butadiene gas-phase polymerization
In purifying treatment and vertical response still with the modified version anchor stirrer, add above-mentioned prepared rare earth catalyst 0.488g, open stirring, feed divinyl gas, control still internal pressure is 0.02～0.15MPa.50 ℃ of down reactions 2 hours, dry that viscosity-average molecular weight 860,000, molecular weight distributing index 2.8, gel content 0.8%, suitable-1,4 structural content are 98% polyhutadiene 21.6g through aftertreatment.
Example four,
1) carrier and pre-treatment thereof are with example one.
2) Preparation of Catalyst
Add 0.91mmolLn (P in the 250ml single port bottle 507) 3(Ln is the Pr-Nd enriched substance) adds 50ml toluene, 54.6mmol Al (i-Bu) 3, 1.21mmolAl 2Et 3Cl 3, 0.33molSiO 2, 40 ℃ were reacted 2 hours, left standstill 24 hours.Separate solvent, the dry micro-yellow powder shape catalyzer 32.3g that gets good fluidity.
3) butadiene gas-phase polymerization
In purifying treatment and vertical response still with the modified version anchor stirrer, add above-mentioned prepared rare earth catalyst 0.575g, open stirring, feed divinyl gas, control still internal pressure is 0.02～0.15MPa.50 ℃ of down reactions 1 hour, dry that viscosity-average molecular weight 570,000, molecular weight distributing index 2.6, gel content 0.8%, suitable-1,4 structural content are 95% polyhutadiene 24.5g through aftertreatment.
Example five,
1) carrier and pre-treatment thereof are with example one.
2) Preparation of Catalyst
Add 1.0mmolGd (P in the 250ml single port bottle 204) 3, 50ml toluene, 40mmolAl H (i-Bu) 2, 3.0mmol AlEt 2Cl, 0.33molSiO 2, 70 ℃ were reacted 2 hours.Separate solvent, drying obtains little yellow catalyst 29.5g of good fluidity.
3) butadiene gas-phase polymerization
In purifying treatment and vertical response still with the modified version anchor stirrer, add above-mentioned prepared rare earth catalyst 0.600g, open stirring, feed divinyl gas, control still internal pressure is 0.02～0.10MPa.50 ℃ of down reactions 1 hour, dry that viscosity-average molecular weight 750,000, molecular weight distributing index 2.6, gel content 8.5%, suitable-1,4 structural content are 96% polyhutadiene 9.0g through aftertreatment.
Example six,
1) carrier and pre-treatment thereof are with example one.
2) Preparation of Catalyst
Add 1.0mmolLa (P in the 250ml single port bottle 507) 3, 50ml toluene, 40mmolAl (i-Bu) 3, 3.0mmolMe 3SiCl, 0.33molSiO 2, stir, 75 ℃ were reacted 3 hours, separated solvent, and drying obtains the little yellow powdered catalyst 32.0g of good fluidity.
3) butadiene gas-phase polymerization
In purifying treatment and vertical response still with the modified version anchor stirrer, add above-mentioned prepared rare earth catalyst 0.498g, open stirring, feed divinyl gas, control still internal pressure is 0.02～0.10MPa.50 ℃ of down reactions 0.5 hour, dry that viscosity-average molecular weight 300,000, molecular weight distributing index 2.1, gel content 0.6%, suitable-1,4 structural content are 95% polyhutadiene 5.6g through aftertreatment.
Example seven,
1) carrier and pre-treatment thereof are with example one.
2) Preparation of Catalyst
Add 0.98mmolNd (napb) in the 250ml single port bottle 3, 50ml toluene, 39.2mmolAl (i-Bu) 3, 19.6mmol Al (i-Bu) 2Cl, 0.34molSiO 2, stir, 50 ℃ were reacted 5 hours, separated solvent, and drying obtains little yellow catalyst 35.3g of good fluidity.
3) butadiene gas-phase polymerization
In purifying treatment and vertical response still with the modified version anchor stirrer, add above-mentioned prepared rare earth catalyst 0.537g, open stirring, feed divinyl gas, control still internal pressure is 0.02～0.10MPa.50 ℃ of down reactions 1.3 hours, dry that viscosity-average molecular weight 1,000,000, molecular weight distributing index 2.3, gel content 11.6%, suitable-1,4 structural content are 97% polyhutadiene 17.6g through aftertreatment.
Example eight,
1) carrier and pre-treatment thereof are with example one.
2) Preparation of Catalyst
Add 1.0mmolNd (P in the 250ml single port bottle 204) 3, 100ml gasoline, 50mmolAlEt 3, 2.5mmolphCH 2Cl, 1.0molSiO 2, stir, 40 ℃ were reacted 12 hours, separated solvent, and drying obtains little yellow catalyst 69.7g of good fluidity.
3) butadiene gas-phase polymerization
In purifying treatment and vertical response still with the modified version anchor stirrer, add above-mentioned prepared rare earth catalyst 0.540g, open stirring, feed divinyl gas, control still internal pressure is 0.02～0.10MPa.50 ℃ of down reactions 2 hours, dry that viscosity-average molecular weight 2l ten thousand, molecular weight distributing index 2.9, gel content 1.2%, suitable-1,4 structural content are 95% polyhutadiene 16.8g through aftertreatment.
Example nine,
1) carrier and pre-treatment thereof are with example one.
2) Preparation of Catalyst
Add 1.0mmolNd (P in the 250ml single port bottle 204) 3, 75ml toluene, 100mmolAl (i-Bu) 3, 1.5mmol BrCH 2CH 2Br, 0.5molSiO 2, stir, 75 ℃ were reacted 3 hours, separated solvent, and drying obtains little yellow catalyst 54.8g of good fluidity.
3) butadiene gas-phase polymerization
In purifying treatment and vertical response still with the modified version anchor stirrer, add above-mentioned prepared rare earth catalyst 0.600g, open stirring, feed divinyl gas, control still internal pressure is 0.02～0.10MPa.50 ℃ of down reactions 1 hour, dry that viscosity-average molecular weight 280,000, molecular weight distributing index 2.7, gel content 0.5%, suitable-1,4 structural content are 95% polyhutadiene 8.9g through aftertreatment.
Example ten,
1) carrier is Al 2O 3Be chemical pure, its pre-treatment is with example one.
2) Preparation of Catalyst
Add 0.96mmolNd (P in the 250ml single port bottle 204) 3, 50ml toluene, 19.3mmolAl (i-Bu) 2H, 2.88mmol Al (i-Bu) 2Cl, 0.51mol Al 2O 3, stir, 75 ℃ were reacted 3 hours, separated solvent, and drying obtains little yellow catalyst 60.7g of good fluidity.
3) butadiene gas-phase polymerization
In purifying treatment and vertical response still with the modified version anchor stirrer, add above-mentioned prepared rare earth catalyst 0.552g, open stirring, feed divinyl gas, control still internal pressure is 0.02～0.10MPa.50 ℃ of down reactions 2 hours, dry that viscosity-average molecular weight 320,000, molecular weight distributing index 2.4, gel content 0.8%, suitable-1,4 structural content are 95% polyhutadiene 12.6g through aftertreatment.
Example 11,
1) carrier pre-treatment
100 order carbon blacks are taken out the pretreated method of carrier triisobutyl aluminium purifying in the roasting back employing example 1 through 90 ℃ of high vacuum.
2) Preparation of Catalyst
Add 0.49mmolNd (P in the 250ml single port bottle 204) 3, 30ml toluene, 34.3mmolAl (i-Bu) 3, 1.47mmol phCH 2Cl, the 0.83mol carbon black, 70 ℃ were reacted 4 hours.Separate solvent, drying obtains catalyzer 16.1g.
3) butadiene gas-phase polymerization
In purifying treatment and vertical response still with the modified version anchor stirrer, add above-mentioned prepared rare earth catalyst 0.734g, open stirring, feed divinyl gas, control still internal pressure is 0.02～0.10MPa.50 times reactions 1.5 hours, dry that viscosity-average molecular weight 500,000, molecular weight distributing index 2.3, gel content 2.6%, suitable-1,4 structural content are 95% polyhutadiene 2.8g through aftertreatment.

Claims (1)

1. the rare earth catalyst that butadiene gas-phase polymerization is used is characterized in that it is the compound system of A, B, C and four components of D,
The A component means rare earth compound, be the rare earth carboxylate that any or pr-nd enriched product in Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and 15 kinds of rare earth elements of Lu and phenylformic acid or naphthenic acid reaction form, perhaps with P 204, P 229, P 507, P 350Prepared rare earth phosphonate, wherein
Figure C9910153600021
The B component means aluminum alkyls, i.e. triethyl aluminum, triisobutyl aluminium and diisobutylaluminium hydride;
The C component means halogenide, i.e. binary halogenated alkane BrCH 2CH 2Br or halogenated aryl hydrocarbon C 6H 5CH 2Cl;
The D component means carrier, i.e. silica gel or aluminum oxide or carbon black;
The mol ratio of said each component of catalyzer is: A: B=1: 20～1: 100, and A: C=1: 1～1: 10, A: D=1: 100～1: 500.
CN99101536A 1999-01-21 1999-01-21 Composition and preparation method for butadiene gas-phase polymerization rare earth catalyst Expired - Lifetime CN1084337C (en)

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MXPA03004070A (en) * 2000-11-09 2004-04-20 Michelin Rech Tech Catalytic system and method for preparing elastomers using same.
CN100448898C (en) * 2005-03-30 2009-01-07 中国石油化工股份有限公司 Rare-earth catalyst and conjugated diene polymerization process
CN101575386B (en) * 2008-05-09 2011-01-12 中国石油天然气股份有限公司 Method for preparing silica gel supported titanium-magnesium catalyst
CN103087260B (en) * 2013-02-28 2014-12-31 浙江大学 Method and catalyst for preparing high cis-polybutadiene by gas-phase polymerization
CN103130938B (en) * 2013-02-28 2015-01-21 浙江大学 Method for preparing high cis-polyisoprene through utilizing gas phase polymerization, and catalyst
CN103483481B (en) * 2013-08-29 2016-03-02 浙江大学 A kind of vapor phase process prepares polymerization system and the application thereof of high-cis polybutadiene
CN103467634B (en) * 2013-09-13 2015-10-21 浙江大学 A kind of vapor phase process prepares polymerization system and the application thereof of high cis-1,4-polyisoprene
CN103772568B (en) * 2014-01-14 2016-01-20 浙江大学 A kind of method regulating vapor phase process polyhutadiene product vinyl structure content
CN103880872B (en) * 2014-03-28 2017-01-11 中国科学院长春应用化学研究所 Preparation method and application of lactic acid rare earth complex and rare earth catalyst

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CN1164242A (en) * 1994-08-02 1997-11-05 联合碳化化学品及塑料技术公司 Gas phase production of polydienes
EP0846707A1 (en) * 1996-12-04 1998-06-10 Japan Synthetic Rubber Co., Ltd. Method for preparing conjugated diene polymer

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