CN103772568A - Method for adjusting content of vinyl structure of gas-phase polybutadiene product - Google Patents
Method for adjusting content of vinyl structure of gas-phase polybutadiene product Download PDFInfo
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- CN103772568A CN103772568A CN201410015173.0A CN201410015173A CN103772568A CN 103772568 A CN103772568 A CN 103772568A CN 201410015173 A CN201410015173 A CN 201410015173A CN 103772568 A CN103772568 A CN 103772568A
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- catalyst
- vinyl structure
- polyhutadiene
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- phase process
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Abstract
The invention discloses a method for adjusting the content of vinyl structure of a gas-phase polybutadiene product. The method comprises the following steps of adding mixed-type load catalyst into a reaction kettle, introducing butadiene gas, controlling the pressure inside the reaction kettle to be 0.05 to 5MPa, controlling the polymerization reaction temperature at 20 to 40 DEG C, controlling the reaction time to be 0.5h to 1h, and obtaining polybutadiene particles; the mixed-type load catalyst is a composite system consisting of a load catalyst A and a load catalyst B, wherein the catalyst A is rare-earth load catalyst, the catalyst B is the iron load catalyst, and the molar ratio R of main metal of the two catalysts is an arbitrary value. The content of the vinyl structure of the product can be adjusted by adjusting the constitution of the catalyst or the molar ratio R of the main metal. The method has the advantages of short process flow, low cost, low energy consumption, environmental friendliness and the like.
Description
Technical field
The present invention relates to the polymerization field of divinyl, be specifically related to a kind of method that regulates vapor phase process polyhutadiene product vinyl structure content.
Background technology
Traditional conjugated dienes polymerized hydrocarbon is all to adopt the method for solution polymerization to carry out.In contrast to this, gaseous polymerization is as a kind of polymerization process being widely used in polyolefin industry, owing to having saved a large amount of solvents, the shortening of polymerization technique flow process, production efficiency are improved, the most important is that it has avoided the direct or indirect environmental pollution of solution polymerization because using a large amount of organic solvents to cause, and is a kind of polymerization production new technology of environmental protection.Chinese patent ZL99101536.3, and recent disclosed CN103087260A, CN103130938A, CN103483481A and CN103467634A, be successfully applied to vapour phase polymerization technology in the polymerization of diolefin.
Research shows, the macro physical performance of elastomeric material can with the second-order transition temperature T of material
gconnect: along with T
greduction, wear-resisting, elasticity, the resistance to low temperature of material all increase, anti-slippery, processibility decline.In the macromolecular chain of polyhutadiene, conventionally comprise Isosorbide-5-Nitrae-polymerized unit (unsaturated link(age) is positioned at main chain) and 1, two kinds of structures of 2-polymerized unit (unsaturated link(age) is positioned at side group, i.e. vinyl structure).Along with the increase of 1,2-polymerized unit content (being vinyl structure content), the T of polymkeric substance
graise.It is generally acknowledged, want to obtain best over-all properties, the second-order transition temperature of elastomeric material should be between-70 ~-50 ℃, and contents of ethylene is in 35% ~ 55% level.
Therefore, in order to promote the over-all properties of rubber, except by multiple polymers material, for example styrene-butadiene rubber(SBR) and cis-1,4-polybutadiene rubber, carry out outside blend, can also start with from the contents of ethylene that regulates polyhutadiene.By adding conditioning agent can change the contents of ethylene of polymerization product in the polymerization process of specific catalyst system, as Chinese patent ZL200510072438.1, in the butadiene solution polymerization causing to organolithium, add tetrahydrofuran (THF)/ethylene glycol diethyl ether or the tetrahydrofuran (THF)/ethylene glycol dibutyl ether as conditioning agent, can realize control and the adjusting of contents of ethylene.In addition, last century late nineteen eighties occurred utilizing rare earth-transition metal mixed catalyst to realize bibliographical information (the catalysis journal of the adjustable butadiene solution polymerization system of microtexture, the 9th volume, the 2nd phase, the 188th page), by changing the ratio of two kinds of core metal elements, realize the adjusting of product medium vinyl content.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of method that regulates vapor phase process polyhutadiene product vinyl structure content is provided.
Regulate the method for vapor phase process polyhutadiene product vinyl structure content to be: in reactor, to add after mixed type supported catalyst, pass into butadiene gas, control reacting kettle inner pressure is 0.05-5MPa, control polymeric reaction temperature is 20-40 ℃, reaction 0.5-1 hour, obtains polyhutadiene particle; Described mixed type supported catalyst is the compound system being made up of A, two kinds of supported catalysts of B, and wherein, catalyst A is rare earth loaded catalyzer, and catalyst B is that iron is supported catalyst, and the molar ratio R of A, two kinds of catalyzer major metals of B is arbitrary value.
Described rare earth loaded catalyzer is by a
1, b
1, c
1, d
1the compound system that four components form, wherein, component a
1the naphthenate Ln (naph) of rare earth element
3or neodecanoate Ln (vers)
3, b
1one or more of aluminum alkyls, alkyl aluminium hydride, c
1chlorination aluminum alkyls, d
1that carrier is silicon-dioxide; The mol ratio of described four components is a
1: b
1=1:50-75, a
1: c
1=1:1-5, a
1: d
1=1:300-500.
Described iron is that supported catalyst is by a
2, b
2, c
2, d
2the compound system that four components form, wherein, component a
2the naphthenate Fe (naph) of iron
3or neodecanoate Fe (vers)
3, b
2aluminum alkyls or alkyl aluminium hydride, c
2nitrogenous compound, d
2that carrier is silicon-dioxide; The mol ratio of described four components is that the mol ratio of described four components is a
2: b
2=1:30-80, a
2: c
2=1:0.5-2, a
2: d
2=1:300-500.Described rare earth element is Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu.The alkyl of described aluminum alkyls, alkyl aluminium hydride and chlorination aluminum alkyls is ethyl or butyl.Described nitrogenous compound is 1,10-phenanthroline or 2,2-dipyridyl.
The product being prepared by rare earth loaded catalyzer is high-cis polybutadiene, and contents of ethylene can be ignored, and is that the product that supported catalyst prepares is that contents of ethylene is the medium vinyl polybutadiene of 50% left and right by iron.In vapour phase polymerization, use this two kinds of catalyzer simultaneously, can obtain take cis-structure as the polyhutadiene blend product main, vinyl structure content is adjustable.
Control method of the present invention mainly contains following two kinds: determine the composition of two kinds of loaded catalysts, just can directly regulate the content of product vinyl by changing the molar ratio R of two kinds of main metals of catalyzer; Regulate its polymerization activity by the composition that regulates catalyzer, the production that feeds intake in certain proportion, also can realize the adjusting of product contents of ethylene.
Diolefin vapour phase polymerization is compared traditional solution polymerization and is had that technical process is short, cost is low, energy consumption is low, advantages of environment protection.The present invention produces polyhutadiene for gaseous polymerization a kind of simple contents of ethylene control method is provided, according to contacting between microtexture and macro property, can be by regulating the contents of ethylene of product to obtain the polymerisate of excellent combination property, this just lays the foundation for expanding the application of conjugated diolefin vapour phase polymerization technology.In addition, owing to having used multiple catalysts, the various active center in reactor can make the molecular weight distribution of product widen, and this can promote the workability of vapor phase process polyhutadiene product to a certain extent.
Embodiment
Choose some below and regulate the product of contents of ethylene between 25% ~ 45% as embodiment, the present invention is further described, but implementation method is not limited by following instance:
Embodiment 1
1. the preparation of catalyst A and catalyst B
To the Nd (naph) that adds 0.05mmol in single port bottle
3, the Al of 3.50mmol
ibu
3, the Al of 0.05mmol
2et
3cl
3, 0.90g carrier S iO
2and 20mL hexane, under 60 ° of C, react after 2 hours, except desolventizing, obtain the catalyst A of 1.66g good fluidity.
To the Fe (naph) that adds 0.03mmol in single port bottle
3, the Al of 0.90mmol
ibu
3, 1 of 0.03mmol, 10-phenanthroline, 0.72g carrier S iO
2and 20mL hexane, after fully mixing, except desolventizing, obtain the catalyst B of 0.91g good fluidity.
2. the vapour phase polymerization of divinyl
To add above-mentioned catalyst A 0.12g and catalyst B 0.34g(R=0.32 in the reactor of purifying treatment), after fully mixing, pass into butadiene gas, control still internal pressure at 0.05MPa, stirring reaction 1 hour at 20 ℃, be dried to obtain weight-average molecular weight 1,380,000, molecular weight distributing index 4.6,1, the polyhutadiene product 15.5g that 2-paradigmatic structure unit content is 38.7% through aftertreatment.
Embodiment 2
1. the preparation of catalyst A and catalyst B
To the Nd (vers) that adds 0.06mmol in single port bottle
3, the Al of 3.00mmol
ibu
3, the Al of 0.08mmol
2et
3cl
3, 1.44g carrier S iO
2and 20mL hexane, under 60 ° of C, react after 2 hours, except desolventizing, obtain the catalyst A of 2.16g good fluidity.
To the Fe (naph) that adds 0.05mmol in single port bottle
3, the Al of 2.50mmol
ibu
3, 2 of 0.10mmol, 2-dipyridyl, 1.50g carrier S iO
2and 20mL hexane, after fully mixing, except desolventizing, obtain the catalyst B of 2.09g good fluidity.
2. the vapour phase polymerization of divinyl
To add above-mentioned catalyst A 0.20g and catalyst B 0.42g(R=0.55 in the reactor of purifying treatment), after fully mixing, pass into butadiene gas, control still internal pressure at 0.1MPa, stirring reaction 0.5 hour at 40 ℃, be dried to obtain weight-average molecular weight 1,230,000, molecular weight distributing index 3.7,1, the polyhutadiene product 10.3g that 2-paradigmatic structure unit content is 25.9% through aftertreatment.
Embodiment 3
1. the preparation of catalyst A and catalyst B
To the La (vers) that adds 0.05mmol in single port bottle
3, the Al of 2.64mmol
ibu
3, the AlH of 0.66mmol
ibu
2,the Al of 0.10mmol
2et
3cl
3, 1.50g carrier S iO
2and 20mL hexane, under 60 ° of C, react after 2 hours, except desolventizing, obtain the catalyst A of 2.28g good fluidity.
To the Fe (vers) that adds 0.03mmol in single port bottle
3, the Al of 1.80mmol
ibu
3, 1 of 0.02mmol, 10-phenanthroline, 0.54g carrier S iO
2and 20mL hexane, after fully mixing, except desolventizing, obtain the catalyst B of 0.92g good fluidity.
2. the vapour phase polymerization of divinyl
To add above-mentioned catalyst A 0.18g and catalyst B 0.35g(R=0.34 in the reactor of purifying treatment), after fully mixing, pass into butadiene gas, control still internal pressure at 0.1MPa, stirring reaction 0.75 hour at 30 ℃, be dried to obtain weight-average molecular weight 1,030,000, molecular weight distributing index 4.3,1, the polyhutadiene product 12.6g that 2-paradigmatic structure unit content is 43.2% through aftertreatment.
Embodiment 4
1. the preparation of catalyst A and catalyst B
To the Nd (naph) that adds 0.03mmol in single port bottle
3, the AlH of 1.65mmol
ibu
2, the Al of 0.04mmol
2et
3cl
3, 0.59g carrier S iO
2and 20mL hexane, under 60 ° of C, react after 2 hours, except desolventizing, obtain the catalyst A of 0.85g good fluidity.
To the Fe (vers) that adds 0.05mmol in single port bottle
3, the AlEt of 4.00mmol
3, 1 of 0.05mmol, 10-phenanthroline, 0.93g carrier S iO
2and 20mL hexane, after fully mixing, except desolventizing, obtain the catalyst B of 1.35g good fluidity.
2. the vapour phase polymerization of divinyl
To add above-mentioned catalyst A 0.13g and catalyst B 0.54g(R=0.23 in the reactor of purifying treatment), after fully mixing, pass into butadiene gas, control still internal pressure at 0.1MPa, stirring reaction 0.75 hour at 30 ℃, be dried to obtain weight-average molecular weight 1,170,000, molecular weight distributing index 3.6,1, the polyhutadiene product 18.6g that 2-paradigmatic structure unit content is 33.2% through aftertreatment.
Embodiment 5
1. the preparation of catalyst A and catalyst B
To the Nd (vers) that adds 0.05mmol in single port bottle
3, the AlEt of 3.75mmol
3, the Al of 0.07mmol
2et
3cl
3, 1.24g carrier S iO
2and 20mL hexane, under 60 ° of C, react after 2 hours, except desolventizing, obtain the catalyst A of 1.71g good fluidity.
To the Fe (naph) that adds 0.03mmol in single port bottle
3, the AlH of 2.10mmol
ibu
2, 1 of 0.03mmol, 10-phenanthroline, 0.65g carrier S iO
2and 20mL hexane, after fully mixing, except desolventizing, obtain the catalyst B of 0.96g good fluidity.
2. the vapour phase polymerization of divinyl
To add above-mentioned catalyst A 0.11g and catalyst B 0.78g(R=0.13 in the reactor of purifying treatment), after fully mixing, pass into butadiene gas, control still internal pressure at 0.5MPa, stirring reaction 0.75 hour at 30 ℃, be dried to obtain weight-average molecular weight 1,200,000, molecular weight distributing index 4.1,1, the polyhutadiene product 22.9g that 2-paradigmatic structure unit content is 41.4% through aftertreatment.
Embodiment 6
1. the preparation of catalyst A and catalyst B
To the Nd (naph) that adds 0.04mmol in single port bottle
3, the Al of 2.40mmol
ibu
3, the Al of 0.20mmol
ibu
2cl, 0.84g carrier S iO
2and 20mL hexane, under 60 ° of C, react after 2 hours, except desolventizing, obtain the catalyst A of 1.42g good fluidity.
To the Fe (vers) that adds 0.04mmol in single port bottle
3, the AlHEt of 3.20mmol
2, 1 of 0.04mmol, 10-phenanthroline, 0.84g carrier S iO
2and 20mL hexane, after fully mixing, except desolventizing, obtain the catalyst B of 1.15g good fluidity.
2. the vapour phase polymerization of divinyl
To add above-mentioned catalyst A 0.11g and catalyst B 0.56g(R=0.16 in the reactor of purifying treatment), after fully mixing, pass into butadiene gas, control still internal pressure at 1MPa, stirring reaction 0.75 hour at 30 ℃, be dried to obtain weight-average molecular weight 1,360,000, molecular weight distributing index 3.5,1, the polyhutadiene product 17.5g that 2-paradigmatic structure unit content is 39.1% through aftertreatment.
Embodiment 7
1. the preparation of catalyst A and catalyst B
To the Nd (naph) that adds 0.08mmol in single port bottle
3, the Al of 4.80mmol
ibu
3, the AlHEt of 1.20mmol
2, the Al of 0.11mmol
2et
3cl
3, 2.02g carrier S iO
2and 30mL hexane, under 60 ° of C, react after 2 hours, except desolventizing, obtain the catalyst A of 3.19g good fluidity.
To the Fe (vers) that adds 0.10mmol in single port bottle
3, the Al of 6.00mmol
ibu
3, 1 of 0.10mmol, 10-phenanthroline, 2.10g carrier S iO
2and 20mL hexane, after fully mixing, except desolventizing, obtain the catalyst B of 3.45g good fluidity.
2. the vapour phase polymerization of divinyl
To add above-mentioned catalyst A 0.12g and catalyst B 0.70g(R=0.15 in the reactor of purifying treatment), after fully mixing, pass into butadiene gas, control still internal pressure at 1MPa, stirring reaction 0.75 hour at 30 ℃, be dried to obtain weight-average molecular weight 1,420,000, molecular weight distributing index 4.7,1, the polyhutadiene product 23.0g that 2-paradigmatic structure unit content is 41.9% through aftertreatment.
Embodiment 8
1. catalyst A is identical with embodiment 7 with the preparation of catalyst B
2. the vapour phase polymerization of divinyl
To add above-mentioned catalyst A 0.12g and catalyst B 1.02g(R=0.10 in the reactor of purifying treatment), after fully mixing, pass into butadiene gas, control still internal pressure at 2MPa, stirring reaction 0.75 hour at 30 ℃, be dried to obtain weight-average molecular weight 1,400,000, molecular weight distributing index 4.3,1, the polyhutadiene product 39.2g that 2-paradigmatic structure unit content is 44.8% through aftertreatment.
Embodiment 9
1. catalyst A is identical with embodiment 7 with the preparation of catalyst B
2. the vapour phase polymerization of divinyl
To add above-mentioned catalyst A 0.22g and catalyst B 0.58g(R=0.33 in the reactor of purifying treatment), after fully mixing, pass into butadiene gas, control still internal pressure at 2MPa, stirring reaction 0.75 hour at 30 ℃, be dried to obtain weight-average molecular weight 1,400,000, molecular weight distributing index 4.1,1, the polyhutadiene product 25.8g that 2-paradigmatic structure unit content is 34.7% through aftertreatment.
Embodiment 10
1. catalyst A is identical with embodiment 7 with the preparation of catalyst B
2. the vapour phase polymerization of divinyl
To add above-mentioned catalyst A 0.11g and catalyst B 0.22g(R=0.43 in the reactor of purifying treatment), after fully mixing, pass into butadiene gas, control still internal pressure at 5MPa, stirring reaction 0.75 hour at 30 ℃, be dried to obtain weight-average molecular weight 1,430,000, molecular weight distributing index 4.1,1, the polyhutadiene product 10.9g that 2-paradigmatic structure unit content is 27.8% through aftertreatment.
Claims (6)
1. one kind regulates the method for vapor phase process polyhutadiene product vinyl structure content, it is characterized in that: in reactor, add after mixed type supported catalyst, pass into butadiene gas, control reacting kettle inner pressure is 0.05-5MPa, control polymeric reaction temperature is 20-40 ℃, reaction 0.5-1 hour, obtains polyhutadiene particle; Described mixed type supported catalyst is the compound system being made up of A, two kinds of supported catalysts of B, and wherein, catalyst A is rare earth loaded catalyzer, and catalyst B is that iron is supported catalyst, and the molar ratio R of A, two kinds of catalyzer major metals of B is arbitrary value.
2. a kind of method that regulates vapor phase process polyhutadiene product vinyl structure content according to claim 1, is characterized in that: described rare earth loaded catalyzer is by a
1, b
1, c
1, d
1the compound system that four components form, wherein, component a
1naphthenate or the neodecanoate of rare earth element, b
1one or more of aluminum alkyls, alkyl aluminium hydride, c
1chlorination aluminum alkyls, d
1that carrier is silicon-dioxide; The mol ratio of described four components is a
1: b
1=1:50-75, a
1: c
1=1:1-5, a
1: d
1=1:300-500.
3. a kind of method that regulates vapor phase process polyhutadiene product vinyl structure content according to claim 1, is characterized in that: described iron is that supported catalyst is by a
2, b
2, c
2, d
2the compound system that four components form, wherein, component a
2naphthenate or the neodecanoate of iron, b
2aluminum alkyls or alkyl aluminium hydride, c
2nitrogenous compound, d
2that carrier is silicon-dioxide; The mol ratio of described four components is that the mol ratio of described four components is a
2: b
2=1:30-80, a
2: c
2=1:0.5-2, a
2: d
2=1:300-500.
4. a kind of method that regulates vapor phase process polyhutadiene product vinyl structure content according to claim 2, is characterized in that: described rare earth element is Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu.
5. according to a kind of method that regulates vapor phase process polyhutadiene product vinyl structure content described in claim 2 or 3, it is characterized in that: the alkyl of described aluminum alkyls, alkyl aluminium hydride and chlorination aluminum alkyls is ethyl or butyl.
6. a kind of method that regulates vapor phase process polyhutadiene product vinyl structure content according to claim 3, is characterized in that: described nitrogenous compound is 1,10-phenanthroline or 2,2-dipyridyl.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229097A (en) * | 1999-01-21 | 1999-09-22 | 北京燕山石油化工公司研究院 | Composition and preparation method for butadiene gas-phase polymerization rare earth catalyst |
| WO2011147573A2 (en) * | 2010-05-28 | 2011-12-01 | Basell Polyolefine Gmbh | Process for preparing a supported catalyst system for olefin polymerization, the catalyst system and its use |
-
2014
- 2014-01-14 CN CN201410015173.0A patent/CN103772568B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229097A (en) * | 1999-01-21 | 1999-09-22 | 北京燕山石油化工公司研究院 | Composition and preparation method for butadiene gas-phase polymerization rare earth catalyst |
| WO2011147573A2 (en) * | 2010-05-28 | 2011-12-01 | Basell Polyolefine Gmbh | Process for preparing a supported catalyst system for olefin polymerization, the catalyst system and its use |
Non-Patent Citations (1)
| Title |
|---|
| 胡雁鸣等: "铁系催化剂上合成高乙烯基聚丁二烯的研究 I.三苯基磷酸酯的影响", 《催化学报》, vol. 25, no. 8, 30 August 2004 (2004-08-30), pages 664 - 667 * |
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