CN1186812A - Preparation of polymer carrier metallocene catalyst - Google Patents
Preparation of polymer carrier metallocene catalyst Download PDFInfo
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- CN1186812A CN1186812A CN96123703A CN96123703A CN1186812A CN 1186812 A CN1186812 A CN 1186812A CN 96123703 A CN96123703 A CN 96123703A CN 96123703 A CN96123703 A CN 96123703A CN 1186812 A CN1186812 A CN 1186812A
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- preparation
- catalyst
- mao
- toluene
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Abstract
The carrier catalyst for ethylene homopolymerization and copolymerization of ethylene and alpha-olefine consists of two components, A and B. Component A has the expression of (R1)mM(R2)n/MAO/L where (R1)mM(R2)n is metallocene compound, MAO is methyl aluminoxyane and L is polymer carrier; and component B is MAO or phenyl-boro pentoxide. The catalyst of the present invention has high catalytic activity to ethylene and is suitable for gaseous and slurry polymerization process at relatively low aluminium rate. Unlike inorganic catalyst, the said catalyst results in product without inorganic ash.
Description
The invention belongs to the preparation method of metallocene catalyst with polymer carrier.
Recently for over ten years, it is found that some metallocene compound, as Cp
2ZrCl
2, Cp
2Zr (CH
3)
2The homogeneous catalysis system of forming Deng (Cp is a cyclopentadienyl) and methylaluminoxane (MAO) has the superelevation catalytic activity to ethene, and the gained polyethylene product has the physicals that is beyond one's reach in the past.German Patent Aprplicaqtion 2,608,863 disclose the olefin polymerization catalysis of a kind of cyclopentadiene titanium compound and methylaluminoxane composition, German Patent Ap-plication 2,608,933 and European Patent Application 0035242 similar metallocene catalyst is disclosed.Above-mentioned catalyzer is used for the ethylene polymerization activity height, the molecular weight of product narrowly distributing, and the big I of molecular weight is by catalyst concn and temperature of reaction control simultaneously.On the other hand, going up in above-mentioned catalyzer is homogeneous phase in reaction system, and the product bulk density is low, and poor morphology can not satisfy the requirement of vapour phase polymerization fluidized-bed process, so the modification of catalyzer has caused people's very big interest.Japanese Laid-open Patent NO.35006,35007 disclose a kind of preparation method of carried catalyst, utilize MAO that metallocene compound is carried on inorganic carrier SiO
2Or Al
2O
3On.United states Patent 5,006,500, European Patent 358,264,367,503,368,644, disclose a kind of preparation method of carried catalyst, utilized the inorganic carrier that contains part moisture content to react with metallocene compound again with the aluminum alkyls reaction earlier, thereby reach the purpose that metallocene compound is immobilized.
The preparation method who the purpose of this invention is to provide a kind of metallocene catalyst with polymer carrier, this method adopts the crosslinked polystyrene copolymerization thing as carrier, with methylaluminoxane pre-treatment carrier, with the metallocene compound reaction, be prepared into polymer supported catalyst more earlier.
The carried catalyst of the present invention's preparation is made up of A and B two components, and the expression formula of A is (R
1)
m(R
2)
nM/MAO/L, wherein (R
1)
m(R
2)
nM/MAO/L is a metallocene compound, and M is transition metal such as titanium, zirconium, hafnium, R
1Be cyclopentadienyl (Cp) indenyl (Ind) or fluorenyl (Flu) and substitution compound and bound, m+n=4, R
2Be CH
3OBu, Cl etc., MAO is a methylaluminoxane, L is a polymer support, comprise poly-(vinylbenzene-acrylamide), poly-(vinylbenzene-vinylformic acid), poly-(vinylbenzene-ethyl propenoate), poly-(vinylbenzene-butyl acrylate), poly-(vinylbenzene-4-vinylpridine), B is methylaluminoxane or B (C
6F
5)
3
Catalyst preparation process is as follows:
1. the preparation of polymer support
The preparation of polymer supported body and function conventional free radical copolymerization process is made initiator with Diisopropyl azodicarboxylate, adds monomer concentration and is 2～15% Vinylstyrene and make linking agent, at copolymer-1-10 below 80 ℃ hour;
2. the preparation of polymer supported catalyst
The all operations of Preparation of Catalyst all carries out under anhydrous, anaerobic and nitrogen protection, (Al/N=1: 1～1000: 1) toluene solution under agitation is added dropwise in the toluene suspension that contains 2-5 g polymer support in room temperature with the methyl alkane of aequum, dropwise, with said mixture restir reaction 2 hours, then reactant is filtered, with toluene wash for several times, to remove unreacted MAO; Above-mentioned solid is made into toluene suspension again, be added dropwise to the toluene solution (Zr/N=1: 100～10: 1) of metallocene compound, stirring reaction, then reactant is filtered, with toluene wash for several times, to remove the metallocene compound that does not carry, vacuum is taken out and is desolvated, and gets the polymer supported catalyst pressed powder.
3. ethene (or ethylene/alpha-olefin) polymerization
Polyreaction is carried out under anhydrous, oxygen free condition, in reaction system, add toluene (or hexane), ethene, methylaluminoxane, carried catalyst successively, in 30-60 ℃ of reaction 1 hour, with the ethanolic soln termination reaction that contains 1% (weight ratio) hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, in 40 ℃ of vacuum-dryings 24 hours.
Embodiment provided by the invention is as follows:
The preparation of embodiment 1 catalyst A component
The MAO toluene solution of 18ml2.5M is added dropwise under agitation in room temperature (the carrier nitrogen content is 1.52wt% in the 50ml toluene suspension that contains poly-(vinylbenzene-acrylamide) carrier of 3g, degree of crosslinking is 5%) dropwise, with above-mentioned reaction mixture restir reaction 2 hours, then reactant is filtered, with toluene wash 3 times, above-mentioned solid is made into the 50ml toluene suspension again, is added dropwise to and contains 0.146g (500 μ mol) Cp
2ZrCl
2The 50ml toluene solution, in 50 ℃ of reactions 1 hour, then reactant is filtered, with toluene wash 5 times, to remove the Cp that does not carry
2ZrCl
2, vacuum is taken out and is desolvated, and gets the solid catalyst powder, and Zr content is 0.41wt%, and Al content is 7.2wt%.
The preparation of embodiment 2 catalyst A components
The MAO toluene solution of 18ml2.5M is added dropwise under agitation in room temperature (the carrier nitrogen content is 2.14wot% in the 50ml toluene suspension that contains poly-(vinylbenzene-acrylamide) carrier of 3g, degree of crosslinking is 5%), all the other steps are poly-with embodiment 1, get polymeric supported dose of A component, Zr content is 0.68wot% in the catalyzer, and Al content is 9.3%.
The preparation of embodiment 3 catalyst A components
The MAO toluene solution of 60ml2.5M is added dropwise under agitation in room temperature (the carrier nitrogen content is 4.20wot% in the 50ml toluene suspension that contains poly-(vinylbenzene-acrylamide) carrier of 3g, degree of crosslinking is 5%), all the other steps are with embodiment 1, get polymer supported catalyst A component, Zr content is 0.97wot% in the catalyzer, and Al content is 14.8wot%.
The preparation of embodiment 4 catalyst A components
The MAO toluene solution of 18ml2.5M is added dropwise under agitation in room temperature (the carrier nitrogen content is 1.87wot% in the 50ml toluene suspension that contains 3g poly-(vinylbenzene-4-vinylpridine), degree of crosslinking is 10%), all the other steps are with embodiment 1, get polymer supported catalyst A component, Zr content is 0.48wot% in the catalyzer, and Al content is 7.4wot%.
The preparation of embodiment 5 catalyst A components
The MAO toluene solution of 18ml2.5M under agitation is added dropwise in the 50ml toluene suspension that contains poly-(vinylbenzene-acrylamide) carrier of 3g (the carrier nitrogen content is 1.52wot%, and degree of crosslinking is 5%), with Cp in room temperature
2ZrCl
2Change Et (H into
4Ind)
2ZrCl
2All the other steps get polymer supported catalyst A component with embodiment 1, and Zr content is 0.32wot% in the catalyzer, and Al content is 6.4wot%.
Embodiment 6 vinyl polymerizations
In 200ml glass reaction bottle, add 100ml toluene, feed the ethylene gas of 0.4 barometric point, under agitation add the MAO toluene solution of 2ml 1M concentration successively and contain the toluene suspension of A component prepared among the embodiment 1 of 2.5 μ molZr, polyreaction was carried out 1 hour in 50 ℃, with the ethanolic soln termination reaction that contains 1% hydrochloric acid, resulting polymers is filtered, washs, in 40 ℃ of vacuum-dryings 24 hours, get product 4.8g, catalytic efficiency is 1.92 * 10
6G PE/molZr.h.
Embodiment 7 vinyl polymerizations
In 2 liters of polymerization reaction kettles; add the 1000ml hexane; add the MAO toluene solution of 4ml2M concentration and contain A component toluene suspension prepared among the embodiment 1 of 16 μ mol Zr under nitrogen protection, polyreaction is carried out under the ethene of 10 barometric points in 50 ℃; reacted 1 hour; with the ethanolic soln termination reaction that contains 1% hydrochloric acid, products therefrom is filtered, washs, in 40 ℃ of following vacuum-dryings 24 hours; get product 264g, catalytic efficiency is 1.64 * 10
7G PE/mol Zr.h.
Embodiment 8 vinyl polymerizations
In 200ml glass reaction bottle, add 100ml toluene, feed the ethylene gas of 0.4 barometric point, under agitation add the triisobutylaluminum toluene solution of 0.75ml1M concentration, the B (C of 2.5 μ mol successively
6F
5)
3Toluene solution and the toluene suspension that contains A component prepared among the embodiment 1 of 2.5 μ mol Zr, all the other steps get product 2.8g with embodiment 6, and catalytic efficiency is 1.12 * 10
6G PE/mol Zr.h.
Embodiment 9 ethylene/hexene copolymerization
In 200ml glass reaction bottle, add 100ml toluene, feed the ethylene gas of 0.4 barometric point, under agitation add successively 0.08mol hexene, 2ml 1M concentration the dark liquid of MAO toluene and contain among the embodiment 1 of 2.5 μ mol Zr the toluene suspension polyreaction of prepared A component carried out 1 hour in 50 ℃, all the other steps are with embodiment 6, get product 4.2g, catalytic efficiency is 1.68 * 10
6/ mol Zr.h.Product is analyzed through IR, contains hexene 9.80mol%, and it is 96.6 ℃ that DSC tests its fusing point, and degree of crystallinity is 19.4%.
Embodiment 10 ethylene/octene copolymerization
Change comonomer into the 0.1mol octene by embodiment 9, get product 3.8g, rate catalyst is 1.52 * 10
6G/mol Zr.h.The multipolymer warp
13CNMR measures, and octene content is 8.11mol%, and the percentage composition of tlv triple sequence (E represents ethylene unit, and O represents the octene unit) (OOO), (EOO), (OEO) is 0 respectively, and it is 84.1 ℃ that DSC measures its fusing point, and degree of crystallinity is 12.8%.
Embodiment 11 ethene/decene copolymerization
Change comonomer into the 0.1mol decene by embodiment 9, get multipolymer 4.1g, catalytic efficiency is 1.64 * 10
6G/mol Zr.h after measured, contains decene 2.59mol% in the multipolymer, fusing point is 118.1 ℃, and degree of crystallinity is 48.4%.
Embodiment 12 ethene/laurylene copolymerization
Change comonomer into the 0.1mol laurylene by embodiment 9, get multipolymer 3.2g, catalytic efficiency is 1.28 * 10
6G/mol Zr.h, after measured, laurylene content is 2.30mol% in the multipolymer.
Claims (1)
1. the preparation method of a metallocene catalyst with polymer carrier is characterized in that catalyzer is made up of A and B two components, and the expression formula of A is (R
1)
mM (R
2)
n/ MAO/L, wherein (R
1)
mM (R
2)
nBe metallocene compound, M is transition metal such as titanium, zirconium, hafnium, R
1Be cyclopentadienyl (Cp), indenyl (Ind) or fluorenyl (Flu) and substitution compound and bound, m+n=4, R
2Be CH
3, OBu, Cl etc., MAO are methylaluminoxane, and L is a polymer support, comprises poly-(vinylbenzene-acrylamide), poly-(vinylbenzene-4-vinylpridine), and B is MAO or B (C
6F
5)
3
Catalyst preparation process is as follows:
(1) preparation of polymer support
The preparation of polymer supported body and function conventional free radical copolymerization process is made initiator with Diisopropyl azodicarboxylate, adds monomer concentration and is 2～15% Vinylstyrene and make linking agent, at copolymer-1-10 below 80 ℃ hour;
(2) preparation of polymer supported catalyst
The all operations of Preparation of Catalyst all carries out under anhydrous, anaerobic and nitrogen protection, (Al/N=1: 1～1000: 1) toluene solution under agitation is added dropwise in the toluene suspension that contains the 2-5g polymer support in room temperature with the methylaluminoxane of aequum, dropwise, with said mixture restir reaction 2 hours, then reactant is filtered, with toluene wash for several times, to remove unreacted MAO; Above-mentioned solid is made into toluene suspension again, be added dropwise to the toluene solution (Zr/N=1: 100～10: 1) of metallocene compound, stirring reaction, then reactant is filtered, with toluene wash for several times, to remove the metallocene compound that does not carry, vacuum is taken out and is desolvated, and gets the polymer supported catalyst pressed powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96123703A CN1074771C (en) | 1996-12-30 | 1996-12-30 | Preparation of polymer carrier metallocene catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96123703A CN1074771C (en) | 1996-12-30 | 1996-12-30 | Preparation of polymer carrier metallocene catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1186812A true CN1186812A (en) | 1998-07-08 |
| CN1074771C CN1074771C (en) | 2001-11-14 |
Family
ID=5127685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96123703A Expired - Fee Related CN1074771C (en) | 1996-12-30 | 1996-12-30 | Preparation of polymer carrier metallocene catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297340C (en) * | 1999-12-16 | 2007-01-31 | 巴塞尔技术有限公司 | Process and apparatus for making supported catalyst systems for olefin polymerisation |
| CN100390207C (en) * | 2004-04-26 | 2008-05-28 | 中国科学院化学研究所 | Process for preparing polyolefin composite materials |
| CN100471881C (en) * | 2004-04-26 | 2009-03-25 | 中国科学院化学研究所 | Process for preparing supported metallocene catalyst |
| CN104892814A (en) * | 2004-06-16 | 2015-09-09 | 陶氏环球技术有限责任公司 | Technique for selecting polymerization modifiers |
| CN101412763B (en) * | 2007-10-19 | 2015-12-16 | 布拉斯科姆股份有限公司 | Produce high and ultra-high molecular weight and wide molecular weight ethene polymers support of the catalyst and carried type metallocene catalyst method for making and product |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL102645A (en) * | 1992-07-26 | 1998-02-22 | Yeda Res & Dev | Chlorophyll and bacteriochlorophyll derivatives, their preparation and pharmaceutical compositions comprising them |
| IT1264680B1 (en) * | 1993-07-07 | 1996-10-04 | Spherilene Srl | SUPPORTED CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
-
1996
- 1996-12-30 CN CN96123703A patent/CN1074771C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297340C (en) * | 1999-12-16 | 2007-01-31 | 巴塞尔技术有限公司 | Process and apparatus for making supported catalyst systems for olefin polymerisation |
| CN100390207C (en) * | 2004-04-26 | 2008-05-28 | 中国科学院化学研究所 | Process for preparing polyolefin composite materials |
| CN100471881C (en) * | 2004-04-26 | 2009-03-25 | 中国科学院化学研究所 | Process for preparing supported metallocene catalyst |
| CN104892814A (en) * | 2004-06-16 | 2015-09-09 | 陶氏环球技术有限责任公司 | Technique for selecting polymerization modifiers |
| CN104892814B (en) * | 2004-06-16 | 2017-11-10 | 陶氏环球技术有限责任公司 | The method of selective polymerization modifying agent |
| CN101412763B (en) * | 2007-10-19 | 2015-12-16 | 布拉斯科姆股份有限公司 | Produce high and ultra-high molecular weight and wide molecular weight ethene polymers support of the catalyst and carried type metallocene catalyst method for making and product |
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| Publication number | Publication date |
|---|---|
| CN1074771C (en) | 2001-11-14 |
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