CN1229097A - 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 PDFInfo
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- CN1229097A CN1229097A CN 99101536 CN99101536A CN1229097A CN 1229097 A CN1229097 A CN 1229097A CN 99101536 CN99101536 CN 99101536 CN 99101536 A CN99101536 A CN 99101536A CN 1229097 A CN1229097 A CN 1229097A
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- rare earth
- phase polymerization
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 38
- 238000012685 gas phase polymerization Methods 0.000 title claims abstract description 25
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- -1 rare-earth compound Chemical class 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000001502 aryl halides Chemical class 0.000 claims description 2
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 claims description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 5
- 229920002857 polybutadiene Polymers 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000005062 Polybutadiene Substances 0.000 abstract 1
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 20
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 13
- 238000001035 drying Methods 0.000 description 11
- 239000000499 gel Substances 0.000 description 11
- 238000002203 pretreatment Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000019241 carbon black Nutrition 0.000 description 3
- 238000006424 Flood reaction Methods 0.000 description 1
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A rare-earth catalyst for gas-phase polymerization of butadiene is prepared from rare-earth compound, alkyl aluminium, halides and inertial powder through mixing them uniformly in hydrogenated gasoline or toluene, reaction at 40-80 deg.C for 0.5-24 hr, and removing solvent. It features high catalytic activity, less investment and low energy consumption of polymerization and less pollution. With the catalyst, the polybutadiene with 200000-100000 of molecular weight, gel content of 0.5-18% and cis-1,4 structure content of 95-98% can be obtained.
Description
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, any oxide compound or the oxide compound of praseodymium, neodymium enriched substance and rare earth chloride that the dilute hydrochloric acid reaction makes or praseodymium chloride, neodymium mixture and phenylformic acid (BA) or the naphthenic acid (naph) that is in Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and 15 kinds of rare earth elements of Lu reacts the rare earth carboxylate that forms, perhaps with P
204, P
229, P
507, P
350Prepared rare earth phosphonate, wherein
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 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 acid number are that 180.5～188.5 naphthenic acid is 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 280 M
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 the stirred autoclave of purifying treatment, 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 the stirred autoclave of purifying treatment, 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 the stirred autoclave of purifying treatment, 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 the stirred autoclave of purifying treatment, 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, 40mmolAlH (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 the stirred autoclave of purifying treatment, 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 the stirred autoclave of purifying treatment, 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 (naph) 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 the stirred autoclave of purifying treatment, 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 the stirred autoclave of purifying treatment, 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 210,000, 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
25.0ml add 1.0mmolNd (P in the 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 the stirred autoclave of purifying treatment, 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 the stirred autoclave of purifying treatment, 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 24, 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 the stirred autoclave of purifying treatment, add above-mentioned prepared rare earth catalyst 0.734g, open stirring, feed divinyl gas, control still internal pressure is 0.02～0.10MPa.50 ℃ of down 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 (3)
1. the composition of a butadiene gas-phase polymerization rare earth catalyst 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, any oxide compound or the oxide compound of praseodymium, neodymium enriched substance and rare earth chloride that the dilute hydrochloric acid reaction makes or praseodymium chloride, neodymium mixture and phenylformic acid (BA) or the naphthenic acid (naph) that is in Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and 15 kinds of rare earth elements of Lu reacts the rare earth carboxylate that forms, perhaps with P
204, P
229, P
507, P
350Prepared rare earth phosphonate, wherein
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.
2. method for preparing above-mentioned butadiene gas-phase polymerization rare earth catalyst, it is characterized in that above-mentioned A, B, C, the D component is uniform mixing in hydrogenated gasoline or toluene, in 40～80 ℃ of reaction 0.5～24h, removing solvent then forms, the mol ratio of each component is A: B=1: 5～500, and A: C=1: 1～40, A: D=1: 30～5000.
3. a kind of method for preparing above-mentioned butadiene gas-phase polymerization rare earth catalyst according to claim 2, the mol ratio that it is characterized in that said each component of catalyzer is A: B=1: 20～100, A: C=1: 1～10, A: D=1: 100～500.
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| CN99101536A CN1084337C (en) | 1999-01-21 | 1999-01-21 | Composition and preparation method for butadiene gas-phase polymerization rare earth catalyst |
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| CN103087260A (en) * | 2013-02-28 | 2013-05-08 | 浙江大学 | Method and catalyst for preparing high cis-polybutadiene by gas-phase polymerization |
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| CN103880872A (en) * | 2014-03-28 | 2014-06-25 | 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4334045A1 (en) * | 1993-10-06 | 1995-04-13 | Bayer Ag | Catalyst, its production and use for gas phase polymerization of conjugated dienes |
| 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 |
| JP4067592B2 (en) * | 1996-12-04 | 2008-03-26 | Ｊｓｒ株式会社 | Process for producing conjugated diene polymer |
-
1999
- 1999-01-21 CN CN99101536A patent/CN1084337C/en not_active Expired - Lifetime
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