CN1191223A - Catalyst system for syndiotactic polymerization, its preparing method and use thereof - Google Patents
Catalyst system for syndiotactic polymerization, its preparing method and use thereof Download PDFInfo
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- CN1191223A CN1191223A CN98100597A CN98100597A CN1191223A CN 1191223 A CN1191223 A CN 1191223A CN 98100597 A CN98100597 A CN 98100597A CN 98100597 A CN98100597 A CN 98100597A CN 1191223 A CN1191223 A CN 1191223A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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Abstract
The present invention relates to a catalyst system including 8-hydroxyquinoline titanate as primary catalyst and aluminoxane as cocatalyst for syndiotactic polymerization of styrene. Said 8-hydroxyquinoline titanate is the alkoxyl compound, or phenoxy or substituted phenoxy compound of 8-hydroxyquinoline titanium. For the syndiotactic polystyrene prepared with said catalyst system, its syndiotacticity is 91-98 and its melting point is 264-271 deg.C.
Description
The present invention relates to a kind of catalyst system of syndiotactic polymerization, particularly a kind of catalyst system of syndiotactic polymerization of phenylethylene.
From N Ishihara in 1986 with titanium tetrachloride/methylaluminoxane (MAO) and single luxuriant titanium/MAO synthesis of syndiotactic polystyrene (Macromolecues, 1986,19:2464) since, about the existing more report of syndiotactic polymerization of phenylethylene catalyzer.Eur.Patent Appl.208564 (1989) and US Patent48 081 680 have reported and have adopted single luxuriant titanium (zirconium) compound, acid esters and phenyl compound and the styrene catalyzed syndiotactic polymerization of promotor MAO.Macromol.Chem., Macromol.Symp., 1993,66:203 has reported two (the 6-tertiary butyls-4-methylphenoxy titanium dichloride/MAO synthesis of syndiotactic polystyrene of sulphur bridge.Macromolecues, 1993,26:5822 has reported single indenes titanium (Ind) TiCl
3(Ind: synthesis of syndiotactic polystyrene indenyl).Polym.Bull., 1996,37:719b has reported CpTiCl
2(OPr
i)/MAO (Cp: cyclopentadienyl, Pr
i: styrene catalyzed syndiotactic polymerization sec.-propyl).But above-mentioned luxuriant titanium class catalyst system preparation method complexity, productive rate is low.
We respectively at 1996 at Chinese patent (application number: 96102496.8), 1997 at " polymer journal " (1997, (2): 253) and " synthetic resins and plastics " (1997,14 (2): 8) reported muriate, alkoxy compound, phenoxy group and substituent phenoxy compound as catalyst synthesis of syndiotactic polystyrene with beta diketone titanium.These non cyclopentadienyl catalyst simple synthetic method, productive rate height can make normality between height, dystectic polystyrene with high polymerization activity.1997 " polymer journal " (1997, (6): 746) reported that the muriate/MAO catalyst system with the oxine titanium prepares normality polystyrene between height, but this catalyst system catalytic activity is not high enough.
The present invention has overcome luxuriant titanium class catalyzer synthesis condition complexity, shortcoming that productive rate is low, has further improved the polymerization activity of oxine titanium compound, and a kind of catalyst system of syndiotactic polymerization of phenylethylene is provided.
Syndiotactic polymerization catalyst system of the present invention comprises Primary Catalysts and promotor, and wherein Primary Catalysts is the oxine titanic acid ester, has following general formula:
OR is C
1～C
12Alkoxyl group, phenoxy group or substituent phenoxy.Wherein said alkoxyl group is oxyethyl group, positive propoxy, n-butoxy, n-pentyloxy, isopropoxy, isobutoxy or isopentyloxy.Wherein said substituent phenoxy is 2-methylphenoxy, 4-methylphenoxy, 2,4-dimethyl phenoxy, 2,6-dimethyl phenoxy, 2-methoxyl group phenoxy group, 4-methoxyl group phenoxy group, 2,4-dimethoxy phenoxy group or 2,6-dimethoxy phenoxy group.N is respectively 1,2 or 3.When OR is alkoxyl group, n=1, Primary Catalysts is (oxine) three (oxyethyl group) titanium, (oxine) three (positive propoxy) titanium, (oxine) three (n-butoxy) titanium, (oxine) three (n-pentyloxy) titanium, (oxine) three (isopropoxy) titanium, (oxine) three (isobutoxy) titanium or (oxine) three (isopentyloxy) titanium, n=2, Primary Catalysts is two (oxine) two (oxyethyl group) titaniums, two (oxine) two (positive propoxy) titaniums, two (oxine) two (n-butoxy) titaniums, two (oxine) two (n-pentyloxy) titaniums, two (oxine) two (isopropoxy) titaniums, two (oxine) two (isobutoxy) titaniums or two (oxine) two (isopentyloxy) titaniums, n=3, Primary Catalysts is three (oxine) (oxyethyl group) titaniums, three (oxine) (positive propoxy) titaniums, three (oxine) (n-butoxy) titaniums, three (oxine) (n-pentyloxy) titaniums, three (oxine) (isopropoxy) titaniums, three (oxine) (isobutoxy) titaniums or three (oxine) (isopentyloxy) titaniums.When OR is phenoxy group or substituent phenoxy, n=1, Primary Catalysts is (oxine) three (phenoxy group) titanium, (oxine) three (2-methylphenoxy) titanium, (oxine) three (4-methylphenoxy) titanium, (oxine) three (2, the 4-dimethyl phenoxy) titanium, (oxine) three (2, the 6-dimethyl phenoxy) titanium, (oxine) three (2-methoxyl group phenoxy group) titanium, (oxine) three (4-methoxyl group phenoxy group) titanium, (oxine) three (2,4-dimethoxy phenoxy group) titanium or (oxine) three (2,6-dimethoxy phenoxy group) titanium, n=2, Primary Catalysts is two (oxine) two (phenoxy group) titaniums, two (oxines) two (2-methylphenoxy) titanium, two (oxines) two (4-methylphenoxy) titanium, two (oxine) two (2, the 4-dimethyl phenoxy) titanium, two (oxine) two (2, the 6-dimethyl phenoxy) titanium, two (oxines) two (2-methoxyl group phenoxy group) titanium, two (oxines) two (4-methoxyl group phenoxy group) titanium, two (oxine) two (2,4-dimethoxy phenoxy group) titanium or two (oxine) two (2,6-dimethoxy phenoxy group) titanium, n=3, Primary Catalysts is three (oxine) (phenoxy group) titaniums, three (oxines) (2-methylphenoxy) titanium, three (oxines) (4-methylphenoxy) titanium, three (oxine) one (2, the 4-dimethyl phenoxy) titanium, three (oxines) (2, the 6-dimethyl phenoxy) titanium, three (oxines) (2-methoxyl group phenoxy group) titanium, three (oxines) (4-methoxyl group phenoxy group) titanium, three (oxines) (2,4-dimethoxy phenoxy group) titaniums or three (oxine) (2,6-dimethoxy phenoxy group) titanium.
Preparation of Catalyst of the present invention step is in the following order carried out:
(1) under 25 ℃ with titanium tetrachloride (TiCl
4) with 5～20% Ti (OR)
4(OR is C
1～C
12Alkoxyl group, phenoxy group or substituent phenoxy) toluene solution 1: 3 in molar ratio～3: 1 mixes, and stirs 0.5～1 hour, distills out Ti (OR)
4-nCl
n(n=1,2,3).When OR was phenoxy group or substituent phenoxy, this step can be reduced to: under 25 ℃ with 4～10%TiCl
4Diethyl ether solution mixed with the diethyl ether solution of 5～20% phenol or fortified phenol in 1: 1 in molar ratio～1: 3, stirred 0.5～1 hour.
(2) at 25 ℃ of Ti (OR) that down (1) made
4-nCl
nMixed in 1: 1 in molar ratio～1: 3 with 5～20% oxine (8-HQ) diethyl ether solution, reflux 1～2 hour is removed and is desolvated, and with the ether washing for several times, can obtain the oxine titanic acid ester.
Promotor is an aikyiaiurnirsoxan beta, preferably methylaluminoxane (MAO).The mol ratio of promotor and Primary Catalysts (representing with Al/Ti) is 2000: 1～200: 1, is preferably 1000: 1～300: 1 (mol ratio).
Adopt oxine titanic acid ester of the present invention/MAO catalyst system synthesis of syndiotactic polystyrene: polymerization temperature is 20～100 ℃, is preferably 40～80 ℃.Polymerization time is 0.5～4h, preferably 1～3h.Acidifying ethanol termination reaction, the polymkeric substance that is settled out be through washing, drying, and normality is determined as 91～98% with the acetone extraction process between the syndiotactic polystyrene that makes, and is 264～271 ℃ with DSC mensuration fusing point.Polymerization result sees the following form.Normality Tm between embodiment polymerization catalyst thing
(g) (％) (℃)1 1 0.32 92.8 2642 2 0.26 93.1 2643 3 0.28 93.6 2644 4 0.70 94.2 2655 5 2.53 95.1 2686 6 4.21 96.5 2697 7 5.38 97.3 2708 8 4.49 96.6 2719 9 3.65 95.9 26910 10 4.95 99.6 270
Embodiment 1:
(1) under 25 ℃ with TiCl
4With 5～20% tetraethyl titanate (Ti (OEt)
4) toluene solution mixing in 1: 3 in molar ratio, stirred 0.5～1 hour, distill out three (oxyethyl group) monochlor(in)ate titanium ((OEt)
3TiCl).
(2) following at 25 ℃ with (OEt)
3TiCl mixed with 5～20% oxine diethyl ether solution in 1: 1 in molar ratio, and reflux 1～2 hour is removed and desolvated, and with the ether washing for several times, just can make (oxine) three (oxyethyl group) titanium (8-HQ) Ti (OEt)
3(catalyzer 1).
Polymerization process: at a 100mL in the reaction flask that agitator is housed that nitrogen replacement is crossed, add the toluene that 15mL goes out through sodium Metal 99.5 reflux distillation, be warming up to 80 ℃ under stirring, add 2mLMAO toluene solution (6.0mmol) respectively, stir and add catalyzer 1 toluene solution (12 μ mol) after 5 minutes again, Al/Ti=500, add the distilled styrene monomer of 20mL drying at last, constant temperature stirred 1 hour, add acidifying ethanol (10%HCl) and stop polyreaction, reactant poured into continue in the beaker that excess ethyl alcohol is housed to stir 1 hour, filter, use the washing with alcohol polymkeric substance, 70 ℃ of following vacuum-drying 8 hours, get polymkeric substance 0.32g, a normality is 92.8%, and fusing point is 264 ℃.Embodiment 2～3:
With metatitanic acid orthocarbonate (Ti (OPr)
4) or tetrabutyl titanate (Ti (OBu)
4) replace the Ti (OEt) among the embodiment 1
4, use the synthetic method identical with embodiment 1, can make (oxine) three (propoxy-) titanium (8-HQ) Ti (OPr) respectively
3(catalyzer 2) and (oxine) three (butoxy) titanium (8-HQ) Ti (OBu)
3(catalyzer 3).Polymerizing condition with identical with embodiment 1 carries out styrene polymerization with catalyzer 2～3 respectively.The results are shown in Table.Embodiment 4:
With metatitanic acid four isobutyl esters (Ti (OBu
t)
4) replace the Ti (OEt) among the embodiment 1
4With titanium tetrachloride reaction in 1: 1 in molar ratio, make two (isobutoxy) titanium dichloride ((OBu
t)
2TiCl
2).With (OBu
t)
2TiCl
2With oxine reaction in 1: 2 in molar ratio, can make two (oxine) two (isobutoxy) titaniums (8-HQ)
2Ti (OBu
t)
2(catalyzer 4).Polymerizing condition with identical with embodiment 1 carries out styrene polymerization with catalyzer 4.The results are shown in Table.Embodiment 5:
Under 25 ℃ with 4～10%TiCl
4After diethyl ether solution and 5～20% phenol diethyl ether solutions 1: the 1 in molar ratio reaction, continue by with TiCl
4Mol ratio adds oxine diethyl ether solution at 1: 3, just can make three (oxine) (phenoxy group) titaniums (8-HQ)
3Ti (OPh) (catalyzer 5).Polymerizing condition with identical with embodiment 1 carries out styrene polymerization with catalyzer 5.The results are shown in Table.Embodiment 6～10:
With methylphenol (MePhOH), methoxyphenol (MeOPhOH), 2,4-xylenol (2,4-dmp), 2, and the 6-xylenol (2,6-dmp) or 2,6-syringol (2,6-domp) replace phenol among the embodiment 5, use the synthetic method identical, can make three (oxine) (methylphenoxy) titaniums (8-HQ) respectively with embodiment 5
3Ti (OPhMe) (catalyzer 6), three (oxines) (methoxyl group phenoxy group) titaniums (8-HQ)
3Ti (OPhOMe) (catalyzer 7), three (oxines) (2, the 4-dimethyl phenoxy) titanium (8-HQ)
3Ti (2,4-dmp) (catalyzer 8), three (oxines) (2, the 6-dimethyl phenoxy) titanium (8-HQ)
3Ti (2,6-dmp) (catalyzer 9), three (oxines) (2,4-dimethoxy phenoxy group) titanium (8-HQ)
3Ti (2,4-domp) (catalyzer 10).Polymerizing condition with identical with embodiment 1 carries out styrene polymerization with catalyzer 6～10.The results are shown in Table.
Claims (11)
1, a kind of syndiotactic polymerization catalyst system is characterized in that described catalyst system comprises Primary Catalysts and promotor, and described Primary Catalysts is the oxine titanic acid ester, has following general formula:
OR is C
1～C
12Alkoxyl group, phenoxy group or substituent phenoxy.N is 1,2 or 3, and described promotor is an aikyiaiurnirsoxan beta.
2, a kind of syndiotactic polymerization catalyst system according to claim 1 is characterized in that described OR is oxyethyl group, positive propoxy, n-butoxy, n-pentyloxy, isopropoxy, isobutoxy or isopentyloxy.
3, a kind of syndiotactic polymerization catalyst system according to claim 1, it is characterized in that described OR is phenoxy group, 2-methylphenoxy, 4-methylphenoxy, 2,4-dimethyl phenoxy, 2,6-dimethyl phenoxy, 2-methoxyl group phenoxy group, 4-methoxyl group phenoxy group, 2,4-dimethoxy phenoxy group or 2,6-dimethoxy phenoxy group.
4, the catalyst system of a kind of syndiotactic polymerization according to claim 1 and 2, it is characterized in that when OR is alkoxyl group, n=1, described Primary Catalysts is (oxine) three (oxyethyl group) titanium, (oxine) three (positive propoxy) titanium, (oxine) three (n-butoxy) titanium, (oxine) three (n-pentyloxy) titanium, (oxine) three (isopropoxy) titanium, (oxine) three (isobutoxy) titanium or (oxine) three (isopentyloxy) titanium.
5, the catalyst system of a kind of syndiotactic polymerization according to claim 1 and 2, it is characterized in that when OR is alkoxyl group, n=2, described Primary Catalysts is two (oxine) two (oxyethyl group) titaniums, two (oxine) two (positive propoxy) titaniums, two (oxine) two (n-butoxy) titaniums, two (oxine) two (n-pentyloxy) titaniums, two (oxine) two (isopropoxy) titaniums, two (oxine) two (isobutoxy) titaniums or two (oxine) two (isopentyloxy) titaniums.
6, a kind of syndiotactic polymerization catalyst system according to claim 1 and 2, it is characterized in that when OR is alkoxyl group, n=3, described Primary Catalysts is three (oxine) (oxyethyl group) titaniums, three (oxine) (positive propoxy) titaniums, three (oxine) (n-butoxy) titaniums, three (oxine) (n-pentyloxy) titaniums, three (oxine) (isopropoxy) titaniums, three (oxine) (isobutoxy) titaniums or three (oxine) (isopentyloxy) titaniums.
7, according to claim 1 or 3 described a kind of syndiotactic polymerization catalyst systems, it is characterized in that working as OR is phenoxy group or substituent phenoxy, during n=1, described Primary Catalysts is (oxine) three (phenoxy group) titanium, (oxine) three (2-methylphenoxy) titanium, (oxine) three (4-methylphenoxy) titanium, (oxine) three (2, the 4-dimethyl phenoxy) titanium, (oxine) three (2, the 6-dimethyl phenoxy) titanium, (oxine) three (2-methoxyl group phenoxy group) titanium, (oxine) three (4-methoxyl group phenoxy group) titanium, (oxine) three (2,4-dimethoxy phenoxy group) titanium or (oxine) three (2,6-dimethoxy phenoxy group) titanium.
8, according to claim 1 or 3 described a kind of syndiotactic polymerization catalyst systems, it is characterized in that working as OR is phenoxy group or substituent phenoxy, during n=2, described Primary Catalysts is two (oxine) two (phenoxy group) titaniums, two (oxines) two (2-methylphenoxy) titanium, two (oxines) two (4-methylphenoxy) titanium, two (oxine) two (2, the 4-dimethyl phenoxy) titanium, two (oxine) two (2, the 6-dimethyl phenoxy) titanium, two (oxines) two (2-methoxyl group phenoxy group) titanium, two (oxines) two (4-methoxyl group phenoxy group) titanium, two (oxines) two (2,4-dimethoxy phenoxy group) titaniums or two (oxine) two (2,6-dimethoxy phenoxy group) titanium.
9, according to claim 1 or 3 described a kind of syndiotactic polymerization catalyst systems, it is characterized in that working as OR is phenoxy group or substituent phenoxy, during n=3, described Primary Catalysts is three (oxine) (phenoxy group) titaniums, three (oxines) (2-methylphenoxy) titanium, three (oxines) (4-methylphenoxy) titanium, three (oxine)-(2, the 4-dimethyl phenoxy) titanium, three (oxine) one (2, the 6-dimethyl phenoxy) titanium, three (oxines) (2-methoxyl group phenoxy group) titanium, three (oxines) (4-methoxyl group phenoxy group) titanium, three (oxines) (2,4-dimethoxy phenoxy group) titaniums or three (oxine) (2,6-dimethoxy phenoxy group) titanium.
10, the preparation method of a kind of syndiotactic polymerization catalyst system according to claim 1 is characterized in that step is carried out in the following order:
(1) under 25 ℃, titanium tetrachloride was mixed with the toluene solution of 5～20% tetralkyl titanate, metatitanic acid tetraphenyl ester or metatitanic acid four (substituted-phenyl) ester in 1: 3 in molar ratio～3: 1, stirred 0.5～1 hour.
(2) mixed in 1: 1 in molar ratio～1: 3 with 5～20% oxine diethyl ether solution at 25 ℃ of compounds that down (1) made, reflux 1～2 hour, remove and desolvate, with the ether washing for several times, can obtain the described oxine titanic acid ester of claim 4～9.
11, the purposes of a kind of syndiotactic polymerization catalyst system according to claim 1 is characterized in that being used for synthesis of syndiotactic polystyrene.
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|---|---|---|---|
| CN98100597A CN1067690C (en) | 1998-03-04 | 1998-03-04 | Catalyst system for syndiotactic polymerization, its preparing method and use thereof |
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|---|---|---|---|
| CN98100597A CN1067690C (en) | 1998-03-04 | 1998-03-04 | Catalyst system for syndiotactic polymerization, its preparing method and use thereof |
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| Publication Number | Publication Date |
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| CN1191223A true CN1191223A (en) | 1998-08-26 |
| CN1067690C CN1067690C (en) | 2001-06-27 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440187A (en) * | 2014-08-14 | 2016-03-30 | 中国科学院长春应用化学研究所 | Functional highly-syndiotactic polystyrene and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5637660A (en) * | 1995-04-17 | 1997-06-10 | Lyondell Petrochemical Company | Polymerization of α-olefins with transition metal catalysts based on bidentate ligands containing pyridine or quinoline moiety |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440187A (en) * | 2014-08-14 | 2016-03-30 | 中国科学院长春应用化学研究所 | Functional highly-syndiotactic polystyrene and preparation method thereof |
| CN105440187B (en) * | 2014-08-14 | 2019-02-12 | 中国科学院长春应用化学研究所 | A kind of high syndiotactic polytyrene of functionalization and preparation method thereof |
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