CN85102292A - High activity catalyst for styrene stereo directed polymerization - Google Patents
High activity catalyst for styrene stereo directed polymerization Download PDFInfo
- Publication number
- CN85102292A CN85102292A CN 85102292 CN85102292A CN85102292A CN 85102292 A CN85102292 A CN 85102292A CN 85102292 CN85102292 CN 85102292 CN 85102292 A CN85102292 A CN 85102292A CN 85102292 A CN85102292 A CN 85102292A
- Authority
- CN
- China
- Prior art keywords
- styrene
- ticl
- ndcl
- polymerization
- catalyzer
- 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.)
- Withdrawn
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 title claims abstract description 11
- 230000000694 effects Effects 0.000 title abstract description 4
- 150000002798 neodymium compounds Chemical class 0.000 claims abstract description 9
- MNDMJXHHYVXIBJ-UHFFFAOYSA-N [Si].ClC=1C(=C(C=CC1)C1=CC=CC=C1)Cl Chemical compound [Si].ClC=1C(=C(C=CC1)C1=CC=CC=C1)Cl MNDMJXHHYVXIBJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000004793 Polystyrene Substances 0.000 abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 abstract description 6
- 229920002223 polystyrene Polymers 0.000 abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 238000003801 milling Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- -1 alkyl cadmium Chemical compound 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
High activity catalyst for styrene stereo directed polymerization.The present invention is the high activated catalyst of styrene stereo directed polymerization or vinylbenzene and other olefin-copolymerizations, by TiCl
4, MgCl
2, SiCl
2φ
2(dichloro phenylbenzene silicon) and neodymium compound are formed, and neodymium compound is generally NdCl
33C
2H
5OH or NdCl
33C
3H
7OH or NdCl
33C
4H
9OH.This catalyzer can make four indices such as styrene polymerization speed, catalytic efficiency, monomer conversion (being productive rate) and polystyrene degree of isotacticity be improved simultaneously.This catalyzer also can be used for vinylbenzene and the copolymerization of general alkene (for example ethene) or the equal polymerization of alkene (for example ethene).
Description
The present invention is the catalyzer of styrene stereo directed polymerization or vinylbenzene and other olefin-copolymerizations.
The catalyzer of existing styrene stereo directed polymerization or vinylbenzene and other olefin-copolymerizations is made of Primary Catalysts and promotor.Primary Catalysts is the compound of transition metals Ti, chromium, vanadium or zirconium etc., and often usefulness is titanium compound; Promotor is an aluminum alkyls, also useful lithium alkylide or alkyl cadmium.When these catalyst systems are used for styrene stereo directed polymerization, slow, low, the not high shortcoming of catalytic efficiency of productive rate (being monomer conversion) of polymerization velocity is arranged all.Wherein effect is preferably as used TiCl in the polystyrene preparation of No. 696064 descriptions of italian patent
3-AlEt
3Catalyst system, monomer whose transformation efficiency are 59%, catalytic efficiency is 445 gram polystyrene/gram titaniums, and be all still not high.
In recent years, people (В ы с о к о м о л e к с о e is arranged
9ъ 1981,23(1), and 52-54; 1983,25(3), 170～173) adopt with MgR
2Make the AlR of promotor
3-MgR
2-TiCl
4Catalyst system (R=C
nH
2n+1, n=6～9), make monomer conversion from TiCl
4-AlEt
3Or TiCl
4-Al(C
5H
13)
313～14% of catalyst system is increased to 14～31%, and the degree of isotacticity of polystyrene is increased to 73～91% from 32～52%.Obviously, the monomer whose transformation efficiency is still not high yet.
Monomer conversion (being productive rate) and catalytic efficiency are not high, seriously influence the development of styrene stereo directed polymerization technology.Therefore, catalytic efficiency, monomer conversion, degree of isotacticity and polymerization velocity four indices are improved simultaneously, this is to wish the problem that solves for a long time in the styrene stereo directed polymerization field.
The purpose of this invention is to provide a kind of catalyzer, it is used for styrene stereo directed polymerization or vinylbenzene and other olefin-copolymerizations, and catalytic efficiency, monomer conversion, degree of isotacticity and polymerization velocity all are improved.
Catalyzer provided by the present invention, its composition comprises TiCl
4, MgCl
2, SiCl
2φ
2(dichloro phenylbenzene silicon) and neodymium compound.Wherein neodymium compound is generally NdCl
33C
2H
5OH or NdCl
33C
3H
7OH or NdCl
33C
4H
9OH.Each composition ratio by weight is generally MgCl
2: SiCl
2φ
2: TiCl
4=1: 0.03～0.15: 0.05～0.20; The content of neodymium compound is generally TiCl
45～25% of mole number, the most frequently used is 7～15%.
Each composition of catalyzer provided by the present invention forms through ground and mixed, and total milling time was generally 20～50 hours, and the most frequently used is 30～40 hours.
Catalyzer provided by the present invention is used for tactic polymerization under the atmospheric styrene, and monomer conversion in two hours (being productive rate) is 86.2%, is up to 97.7%; Catalytic efficiency reaches as high as 2400 gram polystyrene/gram titaniums; The polystyrene degree of isotacticity is 95%, reaches as high as 98.1%.This catalyzer also can be used for vinylbenzene and (for example ethene) copolymerization of other alkene or is used for the equal polymerization of general alkene (for example ethene).
Embodiment 1, MgCl
2: SiCl
2φ
2: TiCl
4=1: 0.03: 0.05(weight), NdCl
33C
2H
5OH content is TiCl
47% of mole number forms each composition ground and mixed, and total milling time is 35 hours.
Embodiment 2, MgCl
2: SiCl
2φ
2: TiCl
4=1: 0.15: 0.15(weight), NdCl
33C
2H
5OH content is TiCl
410% of mole number forms each composition ground and mixed, and total milling time is 35 hours.
Embodiment 3, MgCl
2: SiCl
2φ
2: TiCl
4=1: 0.10: 0.20(weight), NdCl
33C
2H
5OH content is TiCl
415% of mole number forms each composition ground and mixed, and total milling time is 35 hours.
Claims (4)
1, a kind of styrene polymerization catalyzer is with TiCl
4, make Primary Catalysts, it is characterized in that except TiCl
4Also contain neodymium compound, magnesium chloride (MgCl outward,
2) and dichloro phenylbenzene silicon (SiCl
2Φ
2).
2,, it is characterized in that neodymium compound wherein is NdCl according to the described catalyzer of claim 1
33C
2H
5OH or HdCl
33C
3H
7OH or NdCl
33C
4H
9OH.
3,, it is characterized in that each composition ratio by weight is: MgCl according to the described catalyzer of claim 2
2: SiCl
2φ
2: TiCl
4=1: 0.03～0.15: 0.05～0.20; The content of neodymium compound is TiCl
45～25% of mole number.
4,, it is characterized in that wherein the content of neodymium compound is TiCl according to the described catalyzer of claim 3
47～15% of mole number.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85102292 CN85102292B (en) | 1985-04-01 | 1985-04-01 | High activity catalyst for styrene stereo directed polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85102292 CN85102292B (en) | 1985-04-01 | 1985-04-01 | High activity catalyst for styrene stereo directed polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85102292A true CN85102292A (en) | 1986-10-01 |
| CN85102292B CN85102292B (en) | 1987-08-19 |
Family
ID=4792402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85102292 Expired CN85102292B (en) | 1985-04-01 | 1985-04-01 | High activity catalyst for styrene stereo directed polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85102292B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786621A (en) * | 2012-07-19 | 2012-11-21 | 大连理工大学 | Rare earth catalytic system based high-cis styrene/isoprene/butadiene ternary polymer and its preparation method |
-
1985
- 1985-04-01 CN CN 85102292 patent/CN85102292B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786621A (en) * | 2012-07-19 | 2012-11-21 | 大连理工大学 | Rare earth catalytic system based high-cis styrene/isoprene/butadiene ternary polymer and its preparation method |
| CN102786621B (en) * | 2012-07-19 | 2014-12-24 | 大连理工大学 | Rare earth catalytic system based high-cis styrene/isoprene/butadiene ternary polymer and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN85102292B (en) | 1987-08-19 |
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