CN101870745A - High-efficiency neodymium catalyst for producing synthetic rubber - Google Patents
High-efficiency neodymium catalyst for producing synthetic rubber Download PDFInfo
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- CN101870745A CN101870745A CN 201010204391 CN201010204391A CN101870745A CN 101870745 A CN101870745 A CN 101870745A CN 201010204391 CN201010204391 CN 201010204391 CN 201010204391 A CN201010204391 A CN 201010204391A CN 101870745 A CN101870745 A CN 101870745A
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- neodymium
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- synthetic rubber
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- 229910052779 Neodymium Inorganic materials 0.000 claims abstract 18
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract 18
- 239000003054 catalyst Substances 0.000 claims abstract 14
- -1 aluminum alkyl compound Chemical class 0.000 claims abstract 10
- 150000001993 dienes Chemical class 0.000 claims abstract 8
- 239000002904 solvent Substances 0.000 claims abstract 7
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract 7
- 239000005061 synthetic rubber Substances 0.000 claims abstract 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract 4
- 230000032683 aging Effects 0.000 claims abstract 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 4
- 238000003756 stirring Methods 0.000 claims abstract 2
- 239000002253 acid Substances 0.000 claims 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 6
- 125000005234 alkyl aluminium group Chemical group 0.000 claims 4
- 230000003197 catalytic effect Effects 0.000 claims 4
- 239000000243 solution Substances 0.000 claims 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 2
- 239000004411 aluminium Substances 0.000 claims 2
- 239000012895 dilution Substances 0.000 claims 2
- 238000010790 dilution Methods 0.000 claims 2
- 238000002360 preparation method Methods 0.000 claims 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims 2
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 claims 1
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical class CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims 1
- 239000000084 colloidal system Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims 1
- 230000001804 emulsifying effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 238000010092 rubber production Methods 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 238000010091 synthetic rubber production Methods 0.000 claims 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims 1
- 239000013522 chelant Substances 0.000 abstract 3
- VMLVLKLHQLWCOB-UHFFFAOYSA-H [Nd+3].[Nd+3].[O-]P([O-])=O.[O-]P([O-])=O.[O-]P([O-])=O Chemical compound [Nd+3].[Nd+3].[O-]P([O-])=O.[O-]P([O-])=O.[O-]P([O-])=O VMLVLKLHQLWCOB-UHFFFAOYSA-H 0.000 abstract 2
- 238000003483 aging Methods 0.000 abstract 1
- 238000007865 diluting Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000004945 emulsification Methods 0.000 abstract 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a high-efficiency neodymium catalyst for producing synthetic rubber. The catalyst is prepared by the following steps of: preparing solution of organic neodymium phosphonate, solution of aluminum alkyl compound and solution of chloride by using a solvent; adding conjugated diene, the solution of aluminum alkyl compound and the solution of chloride into the solution of organic neodymium phosphonate in turn so as to prepare a ternary catalyst system chelate; and grinding the ternary catalyst system chelate, feeding the ternary catalyst system chelate and the conjugated diene into a high shear emulsification pump and an ageing kettle in turn, adding the solvent for diluting, and stirring and ageing to obtain the product. The neodymium catalyst has uniform dispersion and does not cluster, so that the molecular weight distribution is more uniform. Therefore, the consumption of the catalyst can be reduced, the cost is saved, and the product quality of the synthetic rubber is improved.
Description
Technical field
The present invention relates to a kind of catalyzer, is a kind of neodymium catalyst that is used for isoprene or butadiene solution polymerization production synthetic polyisoprene, cis-1,4-polybutadiene rubber or fourth polyisoprene rubber specifically.
Background technology
The history that rubber industry is accompanied by the catalyzer development always moves ahead.The particularly appearance of Ziegler-Natta catalyst has brought revolutionary breakthrough for synthesizing cis-1,4-polybutadiene rubber and polyisoprene rubber, for modern rubber industry is laid a good foundation.The application of ziegler catalyst system in the cis-1,4-polybutadiene rubber polymerization such as titanium, cobalt, nickel make the synthetic cis-1,4-polybutadiene rubber have higher cis-content.Along with further developing of Z-type catalyst, at the initial stage sixties, the rare earth ziegler catalyst system, because its distinctive excellent properties, have higher cis-content as the synthetic polymkeric substance, polyreaction is difficult for forming gel etc., and has been subjected to paying attention to widely.China is being walked aspect the research of rare earth catalyst system in the prostatitis in the world, respectively the binary and the three-element catalytic system of organic phospho acid neodymium catalyst system has been carried out extensive studies.Especially the three-element catalytic system that constitutes with organic acid neodymium, aluminum alkyls and halogen agent owing to the catalytic activity height, forms homogeneous phase easily, and is subjected to paying attention to widely.
In three-element catalytic architectural study process, be that the ternary neodymium catalyst system of part has also obtained corresponding attention with the organic phospho acid neodymium.Changchun should be changed institute and study the P that knows clearly as far back as 1975
204, P
507, P
229, P
215Deng the research (see 1980 year Science Press " rare earth catalyst synthetic rubber collected works ") of rare-earth system to the isoprene polymerization catalytic activity, they have shown than the higher activity of other carboxylic acid neodymiums (naphthenic acid, neodecanoic acid, isocaprylic acid etc.).There are many authors to study the catalyzer of making polymerization of conjugated dienes of the phosphonic acids neodymium afterwards again, for example Laubry people such as (01820350.7 and 01820478.3) reported three-way catalyst system with phosphonic acids neodymium preparation synthesized have high by 1, the polyisoprene rubber of 4-cis-structure.
In the above research of making catalyzer with the organic phospho acid neodymium, they have studied the requirement of catalyst proportion and polymerization process condition to the polyisoprene rubber Structural Influence, have demonstrated the great potential of organic phospho acid neodymium catalyst.But, how to exist with the heterogeneous of suspendible because the characteristic of organic phospho acid molecule itself makes the corresponding catalyst system that constitutes be difficult to form uniform and stable homogeneous system.This suspension instability precipitates easily, frequent blocking pipeline in course of conveying, and wall built-up, therefore stifled pumps etc. cause difficulty of transportation, are difficult to operation in the serialization industrial production.On the other hand, this suspension particle diameter is bigger, only there is the neodymium of small part to form catalytic active center, most neodymium is incorporated in the reaction system with invalid impurity form, does not dissolve in organic solvent at the activity of such catalysts center, assemble and form oligomer or gather thing, cause catalyst active center's conglomeration easily, the ratio of the neodymium with catalytic activity is reduced greatly, make product degree of branching height in isoprene or the polymerizing butadiene process, increased the gel content of polymkeric substance, make the range of molecular weight distributions broad, catalyst consumption is big simultaneously, has increased cost, make the ash content of polyisoprene rubber raise the quality product variation again.
Summary of the invention
The purpose of this invention is to provide a kind of stable performance, be uniformly dispersed, having can standing storage and precipitation can not occur, in continuous production, be convenient to pipe-line transportation, not wall built-up, stifled pump is used for the high-efficiency neodymium catalyst that synthetic rubber is produced.This catalyzer is used for the polymerization of conjugated diolefin, comprises isoprene polymerization production polyisoprene rubber, and polymerizing butadiene is produced rare earth polybutadiene rubber and isoprene and butadiene copolymer production fourth polyisoprene rubber etc.
The high-efficiency neodymium catalyst that is used for synthetic rubber production provided by the invention, this catalyzer prepares by following method: be mixed with the organic phospho acid neodymium solution that volumetric molar concentration is 0.08～0.12mol/L, alkylaluminium cpd solution and the chloride soln that volumetric molar concentration is 0.8～1.2mol/L with solvent; Again in the mol ratio 1 of organic phospho acid neodymium and conjugated diene: the ratio of (5～30) adds conjugated diene in organic phospho acid neodymium solution, stirred 3～12 minutes, add alkylaluminium cpd solution, reacted 8～12 minutes down at 30～70 ℃, add chloride soln then, reaction got three-element catalytic system inner complex in 50～70 minutes under 30～70 ℃; Three-element catalytic system inner complex is after pipeline colloid pump grinds, again in organic phospho acid neodymium in the three-element catalytic system inner complex with the mol ratio 1 of conjugated diene: the ratio of (5～30) is sent three-element catalytic system inner complex and conjugated diene into the high-shear emulsifying pump, send into aging reactor afterwards, adding solvent cut to the concentration of neodymium is 0.04～0.06mol/L, stirs ageing 12～36 hours promptly; Wherein organic phospho acid neodymium, alkylaluminium cpd and muriatic mol ratio are 1: (1～10): (1.5～10), preparation and dilution solvent for use are the saturated fatty compounds of group that does not contain monoolefine, diolefin and aromatic essence.
Described organic phospho acid neodymium is selected from the rare-earth salts Nd (P of two (2-ethylhexyl) phosphonic acids and neodymium
204)
3Rare-earth salts Nd (the P of 2-ethylhexyl phosphoric acid list-2-ethylhexyl and neodymium
507)
3In a kind of.
Described alkylaluminium cpd is selected from a kind of in triisobutyl aluminium, diisobutyl aluminium hydride and the ADEH.
Described muriate is chosen a kind of in a chloro-di-isobutyl aluminum, aluminium diethyl monochloride and sesquialter aluminium triethyl.
Described conjugated diolefin is selected from a kind of in divinyl, isoprene and the m-pentadiene.
Preparation and dilution solvent for use all are selected from a kind of in pentane, hexane and the heptane, preferably hexane.
This catalyzer is a kind of " inferior homogeneous phase " liquid relatively uniformly.Here with a kind of between homogeneous phase and heterogeneous between, metastable liquid-phase system is defined as " inferior homogeneous phase " on the kinetics, in order to the homogeneous catalyst system that is different from common clear and the unsettled heterogeneous catalyst system of kinetics of suspendible.
This catalyzer is a kind of very thin effective catalyst structure, this structure increases the active centre in the catalyzer greatly, given full play to the maximum catalytic efficiency of catalyzer, and this catalyzer is uniformly dispersed, not conglomeration, make and reduced the product degree of branching in the isoprene polymerization process, reduced the gel content of polymkeric substance, make molecular weight distribution more even, thereby reduced catalyst consumption, reduce the ash content of polyisoprene rubber, provided cost savings, improved the quality product of polyisoprene rubber again.
Make the catalyst particle size refinement by the pipeline colloidal mill, high speed shear disperse and with the conjugated diolefin reaction after, generate the trickle performed polymer of high dispersing refinement.
This catalyzer is the stable state structure, the catalytic efficiency height: it is 0.1～3 * 10 that the mole number of catalyst n d is counted ratio with the gram of isoprene monomer
-6Mol/g, molecular weight distribution＜3, cis-content＞98%, mooney viscosity are adjustable between 40～100.
The present invention is directed to the acid group part of organic phospho acid as rare earth neodymium, preparation three-element catalytic system is difficult to form the difficult problem of homogeneous catalyst system, adopt the method for pipeline colloidal mill, be aided with conjugate diene monomer, three-element catalytic system to preparation has been processed to form " inferior homogeneous phase " effective catalyst system of dynamic stabilization, thereby has solved a series of difficult problems that this catalyst body ties up to storage, conveying, use aspect.The more important thing is, because the formation of " inferior homogeneous phase " makes that the effective catalytic active center in the catalyst system is able to remarkable increase; Under the condition of lower Al/Nd ratio, still can obtain high catalytic activity.
Embodiment
Embodiment 1:
Be mixed with the Nd (P that volumetric molar concentration is 0.1mol/L with hexane
204)
3Solution, volumetric molar concentration are diisobutyl aluminium hydride solution and the aluminium diethyl monochloride solution of 1mol/L; At the Nd of 100L (P
204)
3Solution adds 50mol divinyl mixing, stirs 5 minutes; Add diisobutyl aluminium hydride solution 28L, 50 ℃ of control reaction temperature, the reaction times is 10 minutes, obtains grass green solution; Add aluminium diethyl monochloride solution 20L then, reacted 60 minutes down in 50 ℃.After pipeline colloid pump grinds, enter the high-shear emulsifying pump with the 30mol divinyl, enter aging reactor at last, adding hexane to the concentration of neodymium is 0.05mol/L, stirs ageing after 24 hours, promptly.
This catalyzer reacts through 12 cube of 3 still successive polymerization, and it is 0.8 * 10 that the mole number of catalyst n d is counted ratio with the gram of isoprene monomer
-6Mol/g, through cohesion, post-processing unit is made polyisoprene rubber.Record mooney viscosity (ML
1+4 100 ℃) be 92.2, molecular weight distribution 1.88, cis-content 98.7%, the every index of product is qualified.
Embodiment 2:
Prepare the Nd (P that volumetric molar concentration is 0.1mol/L respectively with hexane
507)
3Solution, volumetric molar concentration are triisobutyl aluminum solutions and the aluminium diethyl monochloride solution that is 1mol/L; At the Nd of 100L (P
507)
3Add 50mol isoprene mixing in the solution, stirred 5 minutes; Add triisobutyl aluminum solutions 30L again, control reaction temperature is at 30 ℃, and the reaction times is 10 minutes, obtains grass green solution; Add aluminium diethyl monochloride solution 30L then, reacted 60 minutes down in 70 ℃.After pipeline colloid pump grinds, enter the high-shear emulsifying pump with the 60mol isoprene, enter aging reactor at last, adding hexane to the concentration of neodymium is 0.05mol/L, stirs ageing after 12 hours, promptly.
This catalyzer reacts through 12 cube of 3 still successive polymerization, and it is 0.9 * 10 that the mole number of catalyst n d is counted ratio with the gram of isoprene monomer
-6Mol/g, through cohesion, dehydration, briquetting is made polyisoprene rubber.Record mooney viscosity (ML
1+4 100 ℃) be 80.6, molecular weight distribution 2.04, cis-content 98.3%, the every index of product is qualified.
Embodiment 3:
Prepare the Nd (P that volumetric molar concentration is 0.1mol/L respectively with hexane
507)
3Solution, volumetric molar concentration are sesquialter aluminium triethyl solution and the ADEH solution that is 1mol/L; At 1L Nd (P
507)
3In the solution, add 0.7mol isoprene mixing, stirred 5 minutes; Add ADEH solution 0.3L again, control reaction temperature is between 30～70 ℃, and the reaction times is 10 minutes, obtains grass green solution; Add sesquialter aluminium triethyl solution 0.18L then, reacted 60 minutes down in 30～70 ℃.After the colloid pump grinds, enter the high-shear emulsifying pump with the 0.5mol isoprene, enter aging reactor at last, adding hexane to the concentration of neodymium is 0.05mol/L, stirs ageing after 36 hours, promptly.
This catalyzer is through 20 liters of single still polyreactions, and it is 1.2 * 10 that the mole number of catalyst n d is counted ratio with the gram of isoprene monomer
-8Mol/g, washing with alcohol, after the extruding, 40 ℃ of vacuum-dryings of insulation are 24 hours in vacuum drying oven, obtain polyisoprene rubber.Record mooney viscosity (ML
1+4 100 ℃) be 74.2, molecular weight distribution 2.31, cis-content 98.7%, the every index of product is qualified.
Embodiment 4:
Prepare the Nd (P that volumetric molar concentration is 0.1mol/L respectively with hexane
204)
3Solution, volumetric molar concentration are diisobutyl aluminium hydride solution and the sesquialter aluminium triethyl solution that is 1mol/L; At 1L Nd (P
204)
3Add 0.4mol isoprene mixing in the solution, stirred 5 minutes; Add diisobutyl aluminium hydride solution 0.35L again, control reaction temperature is at 30 ℃, and the reaction times is 10 minutes, obtains grass green solution; Add sesquialter aluminium triethyl solution 0.21L then, reacted 60 minutes down in 70 ℃.After the colloid pump grinds, enter the high-shear emulsifying pump with the 1.2mol isoprene, enter aging reactor at last, adding hexane to the concentration of neodymium is 0.05mol/L, stirs ageing after 24 hours, promptly.
This catalyzer is through 20 liters of single still polyreactions, and it is 0.7 * 10 that the mole number of catalyst n d is counted ratio with the gram of isoprene monomer
-6Mol/g, washing with alcohol, after the extruding, 40 ℃ of vacuum-dryings of insulation are 24 hours in vacuum drying oven, obtain polyisoprene rubber.Record mooney viscosity (ML
1+4 100 ℃) be 70.5, molecular weight distribution 1.72, cis-content 98.7%, the every index of product is qualified.
Embodiment 5:
Prepare the Nd (P that volumetric molar concentration is 0.1mol/L respectively with hexane
204)
3Solution, volumetric molar concentration are diisobutyl aluminium hydride solution and a chloro-di-isobutyl aluminum solution that is 1mol/L; At 1L Nd (P
204)
3Add 0.6mol m-pentadiene mixing in the solution, stirred 5 minutes; Add diisobutyl aluminium hydride solution 0.42L again, control reaction temperature is at 70 ℃, and the reaction times is 10 minutes, obtains grass green solution; Add a chloro-di-isobutyl aluminum solution 0.3L then, reacted 60 minutes down in 30 ℃.After the colloid pump grinds, enter the high-shear emulsifying pump with the 0.4mol m-pentadiene, enter aging reactor at last, adding hexane to the concentration of neodymium is 0.05mol/L, stirs ageing after 12 hours, promptly.
This catalyzer is through 20 liters of single still polyreactions, and it is 0.7 * 10 that the mole number of catalyst n d is counted ratio with the gram of isoprene monomer
-6Mol/g, washing with alcohol, after the extruding, 40 ℃ of vacuum-dryings of insulation are 24 hours in vacuum drying oven, obtain polyisoprene rubber.Record mooney viscosity (ML
1+4 100 ℃) be 69.1, molecular weight distribution 2.58, cis-content 98.7%, the every index of product is qualified.
Embodiment 6:
Carry out the polymerization of divinylic monomer according to the catalyzer among the embodiment 1.This catalyzer is through 20 liters of single still polyreactions, and it is 0.3 * 10 that the mole number of catalyst n d is counted ratio with the gram of divinylic monomer
-6Mol/g, washing with alcohol, after the extruding, 40 ℃ of vacuum-dryings of insulation are 24 hours in vacuum drying oven, obtain rare earth polybutadiene rubber.Record mooney viscosity (ML
1+4 100 ℃) be 73.5, molecular weight distribution 1.39, cis-content 98.3%, the every index of product is qualified.
Embodiment 7:
Carry out the polymerization of divinylic monomer according to the catalyzer among the embodiment 3.This catalyzer is through 20 liters of single still polyreactions, and it is 0.7 * 10 that the mole number of catalyst n d is counted ratio with the gram of divinylic monomer
-6Mol/g, washing with alcohol, after the extruding, 40 ℃ of vacuum-dryings of insulation are 24 hours in vacuum drying oven, obtain polyisoprene rubber.Record mooney viscosity (ML
1+4 100 ℃) be 48.2, molecular weight distribution 2.73, cis-content 98.0%, the every index of product is qualified.
Embodiment 8
Carry out the copolymerization of divinyl and isoprene according to the catalyzer among the embodiment 5.The volume ratio of divinyl and isoprene is 2: 8, and this catalyzer is through 20 liters of single still polyreactions, and it is 0.7 * 10 that the mole number of catalyst n d is counted ratio with monomeric gram
-6Mol/g, washing with alcohol, after the extruding, 40 ℃ of vacuum-dryings of insulation are 24 hours in vacuum drying oven, obtain polyisoprene rubber.Record mooney viscosity (ML
1+4 100 ℃) be 65.1, molecular weight distribution 1.92, cis-content 98.3%, the every index of product is qualified.
Claims (7)
1. one kind is used for the high-efficiency neodymium catalyst that synthetic rubber is produced, and it is characterized in that this catalyzer prepares by following method: be mixed with the organic phospho acid neodymium solution that volumetric molar concentration is 0.08～0.12mol/L, alkylaluminium cpd solution and the chloride soln that volumetric molar concentration is 0.8～1.2mol/L with solvent; Again in the mol ratio 1 of organic phospho acid neodymium and conjugated diene: the ratio of (5～30) adds conjugated diene in organic phospho acid neodymium solution, stirred 3～12 minutes, add alkylaluminium cpd solution, reacted 8～12 minutes down at 30～70 ℃, add chloride soln then, reaction got three-element catalytic system inner complex in 50～70 minutes under 30～70 ℃; Three-element catalytic system inner complex is after pipeline colloid pump grinds, again in organic phospho acid neodymium in the three-element catalytic system inner complex with the mol ratio 1 of conjugated diene: the ratio of (5～30) is sent three-element catalytic system inner complex and conjugated diene into the high-shear emulsifying pump, send into aging reactor afterwards, adding solvent cut to the concentration of neodymium is 0.04～0.06mol/L, stirs ageing 12～36 hours promptly; Wherein organic phospho acid neodymium, alkylaluminium cpd and muriatic mol ratio are 1: (1～10): (1.5～10), preparation and dilution solvent for use are the saturated fatty compounds of group that does not contain monoolefine, diolefin and aromatic essence.
2. the neodymium catalyst that is used for rubber production according to claim 1 is characterized in that described organic phospho acid neodymium is selected from a kind of in the rare-earth salts of the rare-earth salts of two (2-ethylhexyl) phosphonic acids and neodymium and 2-ethylhexyl phosphoric acid list-2-ethylhexyl and neodymium.
3. according to claim 1ly be used for the high-efficiency neodymium catalyst that synthetic rubber is produced, it is characterized in that described alkylaluminium cpd is selected from a kind of in triisobutyl aluminium, diisobutyl aluminium hydride and the ADEH.
4. according to claim 1ly be used for the high-efficiency neodymium catalyst that synthetic rubber is produced, it is characterized in that described halogenide chooses a kind of in a chloro-di-isobutyl aluminum, aluminium diethyl monochloride and sesquialter aluminium triethyl.
5. according to claim 1ly be used for the high-efficiency neodymium catalyst that synthetic rubber is produced, it is characterized in that described conjugated diolefin is selected from a kind of in divinyl, isoprene and the m-pentadiene.
6. according to claim 1ly be used for the high-efficiency neodymium catalyst that synthetic rubber is produced, it is characterized in that preparing and dilute solvent for use and be selected from a kind of in pentane, hexane and the heptane.
7. the high-efficiency neodymium catalyst that is used for synthetic rubber production according to claim 6 is characterized in that preparation and dilution solvent for use are hexane.
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| CN103772772A (en) * | 2014-01-21 | 2014-05-07 | 大连理工大学 | Method for preparing latex directly from rare-earth polyisoprene glue solution |
| CN110763528A (en) * | 2018-07-25 | 2020-02-07 | 中国石油天然气股份有限公司 | Method for determining branching degree of rubber |
| CN110903423A (en) * | 2018-09-18 | 2020-03-24 | 中国石油天然气股份有限公司 | Rare earth catalyst, preparation method and application thereof |
| CN113929802A (en) * | 2020-06-29 | 2022-01-14 | 中国石油天然气股份有限公司 | Rare earth catalyst and preparation method and application thereof |
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| CN103772772A (en) * | 2014-01-21 | 2014-05-07 | 大连理工大学 | Method for preparing latex directly from rare-earth polyisoprene glue solution |
| CN110763528A (en) * | 2018-07-25 | 2020-02-07 | 中国石油天然气股份有限公司 | Method for determining branching degree of rubber |
| CN110763528B (en) * | 2018-07-25 | 2022-06-03 | 中国石油天然气股份有限公司 | Method for determining branching degree of rubber |
| CN110903423A (en) * | 2018-09-18 | 2020-03-24 | 中国石油天然气股份有限公司 | Rare earth catalyst, preparation method and application thereof |
| CN110903423B (en) * | 2018-09-18 | 2023-04-07 | 中国石油天然气股份有限公司 | Rare earth catalyst, preparation method and application thereof |
| CN113929802A (en) * | 2020-06-29 | 2022-01-14 | 中国石油天然气股份有限公司 | Rare earth catalyst and preparation method and application thereof |
| CN113929802B (en) * | 2020-06-29 | 2024-04-30 | 中国石油天然气股份有限公司 | Rare earth catalyst and preparation method and application thereof |
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