CN1253958A - Cycloolefine ring-opening metathesis polymerization catalyst - Google Patents
Cycloolefine ring-opening metathesis polymerization catalyst Download PDFInfo
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- CN1253958A CN1253958A CN 98122005 CN98122005A CN1253958A CN 1253958 A CN1253958 A CN 1253958A CN 98122005 CN98122005 CN 98122005 CN 98122005 A CN98122005 A CN 98122005A CN 1253958 A CN1253958 A CN 1253958A
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- ring
- opening metathesis
- reaction
- metathesis polymerization
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Abstract
The present invention discloses a cycloolefine ring-opening metathesis polymerization reaction (ROMP) catalyst, and is characterized by that it adopts the solid complex produced by TiCl4 and ligand reaction as main body of catalyst,and combines with alkylaluminium or Grignard reagent to form the ring-opening metathesis polymerization (ROMP) reaction catalyst system, it not only retains the advantage of higher catalytic activity of TiCl4 but also can avoid the defect produced when the liquid TiCl4 is directly used. Said catalyst can be used in ring-opening metathesis polymerization reaction of cycloolefines of dicyclopentadiene and norborneol, etc..
Description
The invention belongs to the polymerization of cycloolefing field, relate to a kind of TiCl of containing
4Cycloolefine ring-opening metathesis polymerization (ROMP) catalysts.
Along with the fast development of petrochemical industry, development research will have crucial realistic meaning by the application of each composition that petroleum cracking produces.Make in the process of ethene C at light oil cracking
5Cut is about 20%, and wherein, cyclopentadiene and dicyclopentadiene account for 17%.For a petroleum chemical plant of producing 300000 tons of ethene per year, dicyclopentadiene just has about 10,000 tons.Cyclopentadiene and dicyclopentadiene are that synthetic main chain is the main raw material of the poly-cycloolefin of ring texture, for example:
(1) dicyclopentadiene can obtain polydicyclopentadiene by ring-opening metathesis polymerization (ROMP) reaction, and reaction formula is:
(2) for norbornylene: at first cyclopentadiene and ethylene reaction synthesing norborene, and then generate polynorbornene through ring opening metathesis polymerization, reaction formula is:
Polydicyclopentadiene and polynorbornene are the very good high molecular polymers of performance, their resistance intensity, performances such as modulus in flexure all than urethane, nylon and so on for good, at car and boat industry, telecommunications and electrical apparatus industry bigger application prospect is arranged.
The ring-opening metathesis polymerization of dicyclopentadiene and norbornylene (ROMP) reaction must be carried out under the condition that catalyzer exists.Ring-opening metathesis polymerization (ROMP) catalyst for reaction is made up of transistion metal compound (normally halogenide) and metal Organoalkyl compound usually, also has activator sometimes.United States Patent (USP) U.S.P.5,034,482 discloses with TiCl
4ROMP catalyst for reaction for main body.Because TiCl
4At room temperature be a liquid of being fuming, especially smog is even more serious when it is exposed in the air, therefore, has all brought many difficult problems for operation, weighing and environment protection.
The objective of the invention is to disclose a kind of with TiCl
4Coordination compound be ring-opening metathesis polymerization (ROMP) catalysts of main body, to overcome by liquid TiCl
4Above-mentioned shortcoming as body of catalyst.
Design of the present invention is such:
The present invention is with TiCl
4The solid complex that generates with ligand reaction is formed ring-opening metathesis polymerization (ROMP) catalysts system as body of catalyst with aluminum alkyls or Grignard reagent, has both kept TiCl
4Advantage with higher catalytic activity has been avoided direct use liquid TiCl simultaneously again
4The time shortcoming.
The said ring-opening metathesis polymerization of the present invention (ROMP) catalysts is a composition, is made up of Primary Catalysts and promotor two portions, and the proportioning of Primary Catalysts and promotor is such:
Primary Catalysts: promotor=1: 1～4 (mol ratio)
(1) said Primary Catalysts is a complex compound, and available following formula is represented:
TiCl
4In the nL formula: n=1～2;
L is a kind of in tetrahydrofuran (THF) (THF), dioxane, arsenic pyridine, the pyridine of methyl arsenic, benzophenone or the oxine etc.;
Said complex compound is a solid, and its preparation method is very easy, and many documents all disclose its preparation method, as: Inorg.Synth.1982,21,135-40 (Eng). repeat no more herein.
(2) said promotor is aluminum alkyls (RLi) or Grignard reagent (RMgX), and wherein: R is an alkyl, as methyl, and ethyl, sec.-propyl, normal-butyl and n-hexyl etc.; X is a halogen, as Cl, and Br and I etc.
Said catalyzer can be used for ring-opening metathesis polymerization (ROMP) reaction of dicyclopentadiene and norbornylene, and its reactions steps and existing ring-opening metathesis polymerization (ROMP) reacting phase are seemingly.
When adopting TiCl
42THF/CH
3Can obtain to be dissolved in the linear polymer of toluene when Li catalyst system catalyzed polymerization dicyclopentadiene and norbornylene, its catalytic activity can be up to 5 * 10
4More than the g polymer/molTi-h; When adopting TiCl
4Also can obtain to be dissolved in the linear polymer of toluene when 2THF/RMgX catalyst system catalyzed polymerization dicyclopentadiene and norbornylene, its catalytic activity can be up to 2 * 10
4More than the gpolymer/molTi-h.
The processing condition of reaction are such:
Polymerization temperature: 10～100 ℃
Polymerization time: 0.1～48 hour
Polymerization time: 0.1-48 hour catalyzer digestion time: 0～2 hour
Catalyzer ageing temperature :-40～80 ℃
Li/Ti in the catalyzer is 1～4 (mol ratio)
Reaction solvent is toluene or benzene
To sum up said, adopt the said catalyst system of the present invention, the catalytic activity height need not strict operational condition, and is simple and easy to do, is easy to industrializing implementation, is a kind of cycloolefine ring-opening metathesis polymerization catalyst that application prospect is arranged.Below will the present invention is further illustrated by embodiment.
Embodiment 1
In the polyreaction bottle, add TiCl
463 milligrams of 2THF, 0.5 milliliter of toluene, CH
3Li 0.375 mmole-20 ℃ of ageings 15 minutes, adds dicyclopentadiene 1.85 grams, and reaction is 12 minutes in 25 ℃, filters, and washing can obtain polydicyclopentadiene 1 gram after the drying.
Embodiment 2
In the polyreaction bottle, add TiCl
467 milligrams of 2THF, 0.5 milliliter of toluene, CH
3Li 0.4 mmole 0 ℃ of ageing 30 minutes, adds norbornylene 1.88 grams, and reaction is 10 minutes in 20 ℃, filters, and washing can obtain polynorbornene 1.62 grams after the drying.
Embodiment 3
In the polyreaction bottle, add people TiCl
463 milligrams of 2THF, 0.5 milliliter of toluene, CH
3MgI 0.375 mmole-20 ℃ of ageings 90 minutes, adds dicyclopentadiene 1.88 grams, and reaction is 10 minutes in 20 ℃, filters, and washing can obtain polycyclopentadiene 1.62 grams after the drying.
Embodiment 4
In the polyreaction bottle, add
72 milligrams, add toluene and make its dissolving back add CH
3Li 0.4 mmole (0.912mol/l) stirred 90 minutes at-20 ℃, added dicyclopentadiene 1.98 grams, and reaction is 2 hours in 20 ℃, filtered, and washing can obtain poly-dicyclopentadiene 1.8 grams after the drying.
Embodiment 5
In the polyreaction bottle, add TiCl
466 milligrams of 2THF, adding toluene adds i-C after making its dissolving again
3H
7MgCl 0.4 mmole stirred 30 minutes at 0 ℃, added norbornylene 1.88 grams, reacted 6 hours down in 80 ℃, filtered, and washing can obtain polynorbornene 0.3 gram after the drying.
Claims (3)
1. cycloolefine ring-opening metathesis polymerization catalyst, it is characterized in that: be made up of Primary Catalysts and promotor two portions, the proportioning between Primary Catalysts and the promotor is:
Primary Catalysts: the said Primary Catalysts in promotor=1: 1～4 (mol ratio) is a complex compound, and available following formula is represented:
TiCl
4·nL
In the formula: n=1～2; L is tetrahydrofuran (THF) (THF), dioxane, arsenic pyridine, the pyridine of methyl arsenic, hexichol
A kind of in ketone or the oxine etc.;
A kind of for among RLi or the RMgX of said promotor, wherein: R is in methyl, ethyl, sec.-propyl, the normal-butyl or n-hexyl a kind of; X is a kind of among Cl, Br or the I.
2. catalyzer as claimed in claim 1 is characterized in that can be used for the reaction that the dicyclopentadiene polymerization generates polydicyclopentadiene.
3. catalyzer as claimed in claim 1 is characterized in that can be used for the reaction that norbornene polymerization generates polynorbornene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98122005 CN1253958A (en) | 1998-11-18 | 1998-11-18 | Cycloolefine ring-opening metathesis polymerization catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98122005 CN1253958A (en) | 1998-11-18 | 1998-11-18 | Cycloolefine ring-opening metathesis polymerization catalyst |
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| CN1253958A true CN1253958A (en) | 2000-05-24 |
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|---|---|---|---|
| CN 98122005 Pending CN1253958A (en) | 1998-11-18 | 1998-11-18 | Cycloolefine ring-opening metathesis polymerization catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995081B (en) * | 2006-12-27 | 2011-07-06 | 上海新天和树脂有限公司 | Double-component catalyst system for dicyclopentadiene loop-opening, replacement and polymerization and its polymerization process |
| CN102234364A (en) * | 2010-04-30 | 2011-11-09 | 青岛伊科思新材料股份有限公司 | Poly (cyclopentadiene-dicyclopentadiene) copolymer and synthesis method thereof |
| CN105294961A (en) * | 2014-05-30 | 2016-02-03 | 帕尔公司 | Self-assembled structure and membrane comprising block copolymer and process for producing the same by spin coating |
| CN113024614A (en) * | 2021-03-08 | 2021-06-25 | 大成普瑞新材料有限责任公司 | Preparation method of organic tungsten catalyst for injection molding of polydicyclopentadiene composite material |
| US11261198B2 (en) | 2016-06-20 | 2022-03-01 | Shionogi & Co., Ltd. | Process for preparing substituted polycyclic pyridone derivative and crystal thereof |
-
1998
- 1998-11-18 CN CN 98122005 patent/CN1253958A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995081B (en) * | 2006-12-27 | 2011-07-06 | 上海新天和树脂有限公司 | Double-component catalyst system for dicyclopentadiene loop-opening, replacement and polymerization and its polymerization process |
| CN102234364A (en) * | 2010-04-30 | 2011-11-09 | 青岛伊科思新材料股份有限公司 | Poly (cyclopentadiene-dicyclopentadiene) copolymer and synthesis method thereof |
| CN105294961A (en) * | 2014-05-30 | 2016-02-03 | 帕尔公司 | Self-assembled structure and membrane comprising block copolymer and process for producing the same by spin coating |
| CN105294961B (en) * | 2014-05-30 | 2018-06-05 | 帕尔公司 | Self-assembled structures and film comprising block copolymer and their method (IVa) is prepared by spin-coating method |
| US11261198B2 (en) | 2016-06-20 | 2022-03-01 | Shionogi & Co., Ltd. | Process for preparing substituted polycyclic pyridone derivative and crystal thereof |
| US11807648B2 (en) | 2016-06-20 | 2023-11-07 | Shionogi & Co., Ltd. | Process for preparing substituted polycyclic pyridone derivative and crystal thereof |
| CN113024614A (en) * | 2021-03-08 | 2021-06-25 | 大成普瑞新材料有限责任公司 | Preparation method of organic tungsten catalyst for injection molding of polydicyclopentadiene composite material |
| CN113024614B (en) * | 2021-03-08 | 2021-11-02 | 大成普瑞新材料有限责任公司 | Preparation method of organic tungsten catalyst for injection molding of polydicyclopentadiene composite material |
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