CN85101899B - Diolefin Polymerization Catalyst - Google Patents
Diolefin Polymerization Catalyst Download PDFInfo
- Publication number
- CN85101899B CN85101899B CN85101899A CN85101899A CN85101899B CN 85101899 B CN85101899 B CN 85101899B CN 85101899 A CN85101899 A CN 85101899A CN 85101899 A CN85101899 A CN 85101899A CN 85101899 B CN85101899 B CN 85101899B
- Authority
- CN
- China
- Prior art keywords
- component
- polymerization
- chlorosilane
- catalyzer
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerization Catalysts (AREA)
Abstract
The invention provides a new catalyst, namely chlorosilane, R ↓ [ 1 ] R ↓ [ 2 ] R ↓ [ 3 ] SiCl, and a third component, thereby obtaining a soluble homogeneous catalyst, when the gram atom ratio of chlorine atoms in the chlorosilane to rare earth elements in metal compounds in a catalytic system is controlled to be equal to or more than 0.3, and the mole ratio of aluminum organic compounds to the rare earth compounds is between 30 and 200, butadiene or butadiene can be copolymerized with isoprene at 0 to 200 ℃. The polymerization can be carried out in the presence of a diluent or in bulk, and a polymer having excellent properties can be obtained.
Description
The invention belongs to the research of method for manufacturing diolefine polymerization catalyst.Usually with III in the periodictable
BThe rare earth catalyst that family's metal (ordination number is 21-103) compound and trialkylaluminium or alkyl-al hydride and halogen organic compound are formed makes diolefin carry out tactic polymerization and obtains high-cis-1, the polymkeric substance of 4 content, existing document and patent report use various types of halogen compounds, open (EP) 76535 in Europe discloses the invention of relevant halogenated alkanes such as Italian Carbonaro as the 3rd component of aforementioned rare earth catalyst.In addition, other system all is a nonhomogeneous system under the catalytic activity optimal conditions, and the polyhutadiene that heterogeneous catalyst obtains polymerization in polymerizing butadiene has higher molecular weight and wider molecular weight distribution, shown in embodiment 7.Be to reconcile polymericular weight and distribution thereof, have to increase catalyst levels and reduce the wherein mol ratio of halogen compounds and rare earth compound, but the latter will cause the reduction of catalyst activity.
The objective of the invention is to utilize three component of chlorosilane as catalyzer, form the soluble ree catalyzer with the compound and the alkyl-al hydride (or trialkylaluminium) of rare earth neodymium, make the ratio of each component of catalyzer and operational condition all can in a big way, change.When divinyl carried out polymerization or copolymerization in this class catalyst system, catalyzer of the present invention not only had high reactivity, also has high directionality.
Rare earth of the present invention-chlorosilane homogeneous catalyst is made of following component:
1. rare earth compound is preferably the naphthenate of neodymium (Nd);
2. alkyl-al hydride R
1R
2AlR
3Or trialkylaluminium, be preferably alkyl-al hydride;
3. general formula is R
1R
2R
3The chlorosilane of SiCl, R in the formula
1R
2R
3Can be H, alkyl, aryl, and wherein two groups also all can be the chlorine atom.
Three kinds of components of catalyzer of the present invention can not have directly mixing in the presence of monomer divinyl or the small amounts of monomer divinyl, use behind the ageing certain hour then, the Preparation of catalysts temperature can be between-10-70 ℃, and digestion time was 100 days and does not influence the phase and the activity of system under the room temperature.
Catalyzer of the present invention and the known all kinds of catalyzer that is used for diolefin polymerization compare, though also need ageing, the engagement sequence of each component is little to the final performance impact of polyreaction and product.
Three kinds of component ratios of catalyzer of the present invention are: the ratio (X/Ln) of the grammeatom of chlorine atom metallizing thing middle-weight rare earths element will be equal to or greater than 0.3 in the chlorosilane, and ratio is between 0.5-3.5 preferably; The mole ratio of aluminum organic compound and rare earth compound (Al/Ln) is greater than 20, and ratio is between the 30-200 preferably.
Catalyzer of the present invention can be used for the body of divinyl or polymerization and the copolymerization of thinner under existing is arranged.Thinner can be an aliphatic hydrocarbon, and polymerization temperature can be between 0～200 ℃, and polymerization temperature is with the molecular weight and the molecular weight distribution of impact polymer.
Characteristics of the present invention are to use that chlorosilane is stable than metal halide, safety, and the latter is present most document and patent component utilized.Catalyst system of the present invention does not transform phase with the change of catalyst component engagement sequence, proportioning, ageing temperature, digestion time etc., thereby makes polymerization technique comparatively stable, the catalyst activity height, and the polymkeric substance ash content is low, and product need not washing, deliming.
Another characteristics of the present invention are, when using this system, even divinyl also can carry out mass polymerization or copolymerization reposefully in the presence of diluent free, and can obtain the high-cis 1 of gel-free, the multipolymer of the polyhutadiene of 4 content (cis＞98%) or divinyl and isoprene, and be easy to control the molecular weight and the distribution thereof of product.
Characteristics of the present invention also are, the processing characteristics of resulting polymers, and physical strengths etc. can be compared U.S. with the product that other best rare earth catalyst obtains.
Embodiments of the invention 1.
130 gram divinyl under reduced pressure are added in 600 milliliters the withstand voltage vial, add the catalyzer hexane solution for preparing in advance then and (include the neodymium naphthenate of 0.058 mmole for 1.84 milliliters, 1.74 mmole diisobutyl aluminium hydride, 0.075 the trimethylammonium chlorosilane of mmole), carry out polymerization in 20 ℃ of vibration tanks, after three hours excess butadiene is discharged, polymkeric substance takes out puts drying in the vacuum drying oven, obtain 89 gram polyhutadiene, its (η)
30 ℃ TolueneBe 4.03.
Embodiments of the invention 2.
8.6 gram divinyl and 2.2 gram isoprene are added in 40 milliliters of vials, add the catalyzer hexane solution for preparing then and (include 0.0038 mmole neodymium naphthenate for 0.16 milliliter, 0.19 the mmole diisobutyl aluminium hydride, 0.0076 mmole trimethylammonium chlorosilane).In 30 ℃ of vibration tanks, carry out polymerization, take out polymkeric substance after two hours, dry in the vacuum, get product 9.0 grams, its (η)
30 ℃ TolueneBe 3.64.
Embodiments of the invention 3.
With 170 milliliters of anhydrous hexanes, 20 gram divinyl and 1 milliliter of catalyst solution (include 0.0076 mmole neodymium naphthenate, 0.38 the diisobutyl aluminium hydride of mmole, 0.0076 the dimethyl dichloro-silane of mmole) successively be added in 500 milliliters the vial, in 50 ℃ of waters bath with thermostatic control, carry out polymerization, after 5 hours, mixture is poured in the excessive ethanol that contains anti-aging agent, condensation product 40 ℃ of vacuum-dryings, must be done glue 18.2 grams, (η)
30 ℃ TolueneBe 3.0.
Embodiments of the invention 4.
200 milliliters of hexane-butadiene solutions and 1 milliliter of catalyst solution that will contain 20 gram divinyl (include the neodymium naphthenate of 0.0076 mmole, 0.38 the diisobutyl aluminium hydride of mmole, 0.0076 the diphenyl dichlorosilane of mmole) successively add in 500 milliliters of suction lottles (through nitrogen treatment), in 50 ℃ of waters bath with thermostatic control, carry out polymerization, add ethanol after 5 hours and stop polymerization.Get dry polymer 18.0 grams, its (η)
30 ℃ TolueneBe 3.2,
Embodiments of the invention 5.
200 milliliters of hexane-butadiene solutions and 1 milliliter of catalyst solution that will contain 20 gram divinyl (include the neodymium naphthenate of 0.0076 mmole, the diisobutyl aluminium hydride of 0.38 mmole.0.0076 the trichlorosilane of mmole) successively add in 500 milliliters of vials, in 50 ℃ of waters bath with thermostatic control, carried out polymerization 5 hours, get polymkeric substance 18.2 grams, its (η)
30 ℃ TolueneBe 3.8.
Embodiments of the invention 6.
100 milliliters of hexane-butadiene solutions and 0.5 milliliter of catalyst solution that will contain 10 gram divinyl (contain 0.0038 mmole neodymium naphthenate, 0.19 the diisobutyl aluminium hydride of mmole, 0.011 the trimethylchlorosilane of mmole), successively add in 150 milliliters the vial, in 40 ℃ of waters bath with thermostatic control, carried out polymerization 5 hours, get polymkeric substance 8.4 grams, its (η)
30 ℃ TolueneBe 3.2,
Embodiments of the invention 7.
Other condition is identical with example 6, only a chloro-di-isobutyl aluminum is replaced trimethylchlorosilane, gets polymkeric substance 8.3 grams, but its (η)
30 ℃ TolueneBe 5.0,
=5.5
Claims (5)
1, be used for polymerizing butadiene or divinyl and become to be grouped into by three kinds with the soluble catalyst that isoprene copolymer closes, its first component can be III＜` in the periodictable; ; R`〉compound of family's element, second component can be not halogen-containing organo-aluminium compound R
1R
2AlR＜`; 3; ` 〉, feature of the present invention is that the 3rd component of catalyzer is chlorosilane R＜`; ; 1`〉R＜`; ; 2`〉R＜`; ; 3`〉SiCl, wherein R＜`; ; 1`〉R＜`; ; 2`〉R＜`; ; 3`〉can be identical or different alkyl, aryl, also can be hydrogen, and wherein two groups all can be the chlorine atom.
2, as the described catalyst system of claim 1, it is characterized in that the grammeatom ratio of chlorine atom metallizing thing middle-weight rare earths element in the chlorosilane wherein will be equal to or greater than 0.3, its optimum range is between 0.5-3.5.
3,, it is characterized in that its second component R as the described catalyst system of claim 1
1R
2AlR＜`; 3; `〉in a R is preferably arranged is H, and aluminum organic compound is 30-200 to the best scope of mol ratio of rare earth compound (first component).
When 4, catalyst system of the present invention is characterized in that having carried out two polyamino alkenyls or copolymerization, can carry out having in the presence of the thinner, also can carry out mass polymerization.
5,, it is characterized in that using its polymerization temperature of catalyzer of the present invention can be between 0-200 ℃ as described polymerization of claim 4 and copolyreaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85101899A CN85101899B (en) | 1985-04-01 | 1985-04-01 | Diolefin Polymerization Catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85101899A CN85101899B (en) | 1985-04-01 | 1985-04-01 | Diolefin Polymerization Catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101899B true CN85101899B (en) | 1986-03-10 |
| CN85101899A CN85101899A (en) | 1986-03-10 |
Family
ID=4792128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85101899A Expired CN85101899B (en) | 1985-04-01 | 1985-04-01 | Diolefin Polymerization Catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85101899B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR112013014478B1 (en) | 2010-12-09 | 2020-08-04 | China Petroleum & Chemical Corporation | CATALYST OF RARE LANDS WITH A HOMOGENEAL PHASE BASED ON NEODYME AND PROCESS TO PREPARE A POLYMER OF CONJUGATED DIENO |
-
1985
- 1985-04-01 CN CN85101899A patent/CN85101899B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85101899A (en) | 1986-03-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1193787A (en) | Isobutylene-triene copolymers cross-linkable under ambient humidity conditions, a process for their preparation, and intermediate suitable for this purpose | |
| Cheng | Carbon-13 NMR analysis of ethylene-propylene rubbers | |
| ATE201702T1 (en) | AMORPHIC 1-BUTENE/PROPYLENE COPOLYMERS WITH HIGH EXTENSION | |
| JP2537619B2 (en) | Block copolymer and its production method | |
| Fordyce et al. | Copolymerization. II. The Mechanism of Emulsion Copolymerization of Styrene and Itaconic Acid | |
| WO1991007443A1 (en) | Method for the preparation of a catalyst component for the polymerization of olefins, a polymerization catalyst component produced by the method and use of the same | |
| CN85101899B (en) | Diolefin Polymerization Catalyst | |
| Zeng et al. | Ring opening polymerization of propylene oxide by chitosan‐supported rare earth catalytic system and its kinetics | |
| EP1582536A1 (en) | Preparation of styrene homopolymers and styrene-ethylene copolymers | |
| CA1308513C (en) | Process for preparing a silicon containing polymer | |
| Soga et al. | Copolymerization of ethylene with propylene over SiO 2-supported MgCl 2/TiCl 4 catalyst | |
| CN85102250A (en) | The mass polymerization of isoprene under the rare earth catalyst effect | |
| JPS6335659B2 (en) | ||
| CN107722155B (en) | A kind of alpha olefin-fluorostyrene polymer and preparation method thereof | |
| CA1215962A (en) | Polyolefin polymerization process and catalyst | |
| CA2223859A1 (en) | Functionalized styrene polymers and copolymers | |
| Arnold et al. | Alternating copolymerization of butadiene and propene with the catalyst VO (ONeo) 2 Cl/Al (i‐C4H9) 3, 1 | |
| JPH0225370B2 (en) | ||
| KR890004332B1 (en) | Method for preparation of block copolymer of propylene | |
| Serre et al. | Synthesis of aminotelechelic polymers with the redox system TiCl3NH2OH in hydrochloric aqueous phase: 2. Polymerization of methylmethacrylate. Relation functionality/molecular weight/yield | |
| Jin et al. | Polymerization of olefins with zirconocene catalysts using methylaluminoxane modified with hydroquinone as cocatalyst | |
| JPS61287908A (en) | Production of catalyst component for polymerization of alpha-olefin | |
| WO2024111997A1 (en) | Method for decreasing by-products in olefin oligomerization | |
| US20040254321A1 (en) | Uniform initiation of anionic polymerization using organo-substituted alkali metal initiators | |
| RU2099359C1 (en) | Method for production of cis-1,4-diene rubber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |