CN100413896C - Method for synthesizing cyclopentadiene polymer - Google Patents
Method for synthesizing cyclopentadiene polymer Download PDFInfo
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- CN100413896C CN100413896C CNB2005101148420A CN200510114842A CN100413896C CN 100413896 C CN100413896 C CN 100413896C CN B2005101148420 A CNB2005101148420 A CN B2005101148420A CN 200510114842 A CN200510114842 A CN 200510114842A CN 100413896 C CN100413896 C CN 100413896C
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Abstract
This invention relates to a synthesis method for cyclopentadienes polymers, involving an alkyl aluminoxane catalyst used for homopolymerization of cyclopentadienes monomers and copolymerization of cyclopentadienes monomers and styrene, norbornene and its derivatives. The polymerization catalyst is the single component of alkyl aluminoxane, including a C1-C4 alkyl, such as methylaluminoxane, triisobutylaluminoxane, methyl isobutyl aluminoxane or ethoxy diethyl aluminoxane. It can be a single catalyst, or a composite catalyst or a carried product. The catalyst component is single and easy to get, and the structure of the cyclopentadienes copolymer is clear, mainly as the two structural units of 1, 2-and 1, 4-chain structure. The copolymers of cyclopentadienes monomers and styrenes or norbornenes monomers can be obtained. Polymerization and copolymerization reaction rate and product structure can be controlled through regulating alkyl aluminoxane content, monomer concentration, solvents, polymerization temperature and time, etc. factors.
Description
Technical field
The present invention relates to the synthetic method of cyclopentadiene polymer, particularly a kind of alkylaluminoxane catalyzer is used for the homopolymerization of cyclopentadiene monomer and the copolymerization of cyclopentadiene monomer and vinylbenzene, norbornylene and derivative thereof.
Background technology
At present, the synthetic of polymeric cyclopentadiene causes polyaddition reaction mainly by adding catalyzer in the cyclopentadiene monomers, and employed catalyzer mainly contains the Friedel-Crafts catalyzer, as: AlCl
3, BF
3, Oet
2Deng, the cationic salts catalyzer, as: (C
6H
5)
3C+SbC16-etc. and transition metal complex compound catalyzer comprise Pb, W, Ti, Mo, Mn, Fe, Cr, Ni, Cu, Zn, the coordination compound of metals such as Co, metallocene catalyst and back transition non-metallocene catalyst etc.Generally to use promotor when metallocene catalyst and back transition non-metallocene catalyst catalysis in olefine polymerization, as alkylaluminoxane or organoboron compound.
Among the patent CN1187493, disclose the method for olefinic polymerization generation olefin polymer, the catalyzer that uses in the method is the mixed catalyst system of the compound of metallocene-titanium catalyst, alkylaluminoxane and organoaluminum.
Among the patent US6627714, in the method for disclosed olefinic polyreaction, the catalyzer that polyreaction is used is the composite catalyst of metallocene catalyst and aluminum alkoxide.
Japanese Patent 6211916 discloses a kind of composite polymeric catalyst system that uses aluminum alkoxide etc.
In the prior art there be the main problem that exists: (1) cyclopentadiene homopolymerization and multipolymer number-average molecular weight are lower.(2) the detailed Study on mechanism for promotor is very few.(3) seldom for the study on the synthesis of cyclopentadiene new copolymer and performance study thereof.
Summary of the invention
By cyclopentadiene and derivatives monomer thereof homopolymerization and the copolyreaction of cyclopentadiene and derivatives monomer and other olefinic monomer, the reaction synthesizing cyclopentadiene polymer, use the catalyzer initiated polymerization, catalyzer is the alkylaluminoxane of one-component, do not need other promotors, the copolymers of cyclopentadienes monomer structure that polymerization generates is clear and definite, is mainly 1,2-and 1, two kinds of chain structure unit of 4-structure;
The objective of the invention is to adopt one-component is the catalyzer realization cyclopentadiene of alkylaluminoxane and homopolymerization and cyclopentadiene and derivative and other olefinic monomer copolymerization of derivative thereof.The particular content of invention is:
A kind of method of synthesizing cyclopentadiene polymer, polymerisation catalysts consist of the alkylaluminoxane one-component.The alkyl of described catalyzer is the alkyl that comprises 1～4 carbon atom.Described catalyzer is methylaluminoxane, triisobutyl alumina alkane, methyl-isobutyl aikyiaiurnirsoxan beta or oxyethyl group diethyl aluminum.Described catalyzer comprises a kind of catalyzer of alkylaluminoxane composition and the composite catalyst that alkylaluminoxane is formed.Catalyzer comprises that catalyzer is carried on SiO with various forms
2, MgCl
2, carrier surface such as molecular sieve, polynite, clay or macromolecular compound the load product.
Described polyreaction comprises the copolyreaction of homopolymerization and cyclopentadiene monomer and vinylbenzene, norbornylene or the norbornene derivative of cyclopentadiene monomer.Cyclopentadiene monomer is the compound with following general structure,
Wherein, R
1～R
5Alkyl or aromatic base for H, C1～C4.
Norbornene derivative is dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxylic anhydride, dicyclo [2.2.1] heptan-5-alkene-2, the 3-dimethyl dicarboxylate.
The mol ratio of described copolyreaction cyclopentadiene monomer and vinylbenzene, norbornylene or norbornene derivative is 100: 0～0: 100, preferred 20: 80～50: 50.The mol ratio of polymerization single polymerization monomer and alkylaluminoxane is 0.5: 1～20: 1.Polymeric reaction temperature is-84～30 ℃.Polymerization reaction time is 10 minutes～12 hours.
Prominent feature of the present invention is:
1. catalyst component is single, be simple and easy to;
2. the copolymers of cyclopentadienes monomer structure that obtains is clear and definite, is mainly 1,2-and 1, two kinds of chain structure unit of 4-structure;
3. obtain first cyclopentadiene monomer and vinylbenzene or with the monomeric multipolymer of norbornylene class;
4. can pass through the ground easy to adjust controlled polymerization of factors such as alkylaluminoxane consumption, monomer concentration, solvent species, polymerization temperature, polymerization time and the speed of reaction and the product structure of copolymerization.
Description of drawings
The polymkeric substance that Fig. 1 embodiment of the invention 1 obtains
1The HNMR spectrogram
The polymkeric substance that Fig. 2 embodiment of the invention 15 obtains
1The HNMR spectrogram
Embodiment
Embodiment one:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.05 mole of cyclopentadiene monomers, add 0.005 mole of methylaluminoxane down at-84 ℃, keep-84 ℃ of reactions 10 minutes, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtaining polymer yield is 77%, only contains 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit of 4-structure, wherein 1, the 2-structural content be 50% (
1HNMR spectrum analysis result sees accompanying drawing one), number-average molecular weight 32000.
Embodiment two:
Normal pressure will keep nitrogen atmosphere through 100 milliliters of polyreaction bottles nitrogen replacement twice of thorough drying processing down, add 0.05 mole of cyclopentadiene monomers, add 0.005 mole of methylaluminoxane down at-84 ℃, keep-84 ℃ of reactions 12 hours, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtaining polymer yield is 97%, only contain 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit of 4-structure, wherein 1, the 2-structural content is 57%, number-average molecular weight 43000.
Embodiment three:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.1 mole of cyclopentadiene monomers, 15 milliliters of toluene, add 0.01 mole of methylaluminoxane down at 15 ℃, keep 15 ℃ of reactions 7 hours, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtaining polymer yield is 45%, only contains 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit of 4-structure, wherein 1, the 2-structural content is 40%, number-average molecular weight 31000.
Embodiment four:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.1 mole of cyclopentadiene monomers, 15 milliliters of toluene, add 0.01 mole of methylaluminoxane down at 40 ℃, keep 40 ℃ of reactions 12 hours, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtaining polymer yield is 38%, only contains 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit of 4-structure, wherein 1, the 2-structural content is 40%, number-average molecular weight 28000.
Embodiment five:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.1 mole of cyclopentadiene monomers, 15 milliliters of toluene, add 0.02 mole of methylaluminoxane down at-84 ℃, keep-84 ℃ of reactions 0.5 hour, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtaining polymer yield is 51%, only contains 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit of 4-structure, wherein 1, the 2-structural content is 41%, number-average molecular weight 36000.
Embodiment six:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.1 mole of cyclopentadiene monomers, 15 milliliters of toluene, add 0.005 mole of methylaluminoxane down at-84 ℃, keep-84 ℃ of reactions 0.5 hour, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtaining polymer yield is 22%, only contains 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit of 4-structure, wherein 1, the 2-structural content is 43%, number-average molecular weight 38000.
Embodiment seven:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.05 mole of cyclopentadiene monomers, 17 milliliters of methylene dichloride, add 0.0025 mole of methylaluminoxane down at-84 ℃, keep-84 ℃ of reactions 10 minutes, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtaining polymer yield is 56%, only contains 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit of 4-structure, wherein 1, the 2-structural content is 47%, number-average molecular weight 25000.
Embodiment eight:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.05 mole of cyclopentadiene monomers, 17 milliliters of hexanaphthenes, add 0.0025 mole of methylaluminoxane down at-84 ℃, keep-84 ℃ of reactions 30 minutes, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtaining polymer yield is 10%, only contains 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit of 4-structure, wherein 1, the 2-structural content is 41%, number-average molecular weight 23000.
Embodiment nine:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.1 mole of methyl cyclopentadiene monomer, 15 milliliters of toluene, add 0.01 mole of methylaluminoxane down at 0 ℃, keep 0 ℃ of reaction 12 hours, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtaining polymer yield is 43%, only contains 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit of 4-structure, wherein 1, the 2-structural content is 62%, number-average molecular weight 5300.
Embodiment ten:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.1 mole of tertiary butyl cyclopentadiene monomers, 15 milliliters of toluene, add 0.01 mole of methylaluminoxane down at 0 ℃, keep 0 ℃ of reaction 12 hours, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtaining polymer yield is 51%, only contains 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit of 4-structure, wherein 1, the 2-structural content is 64%, number-average molecular weight 5800.
Embodiment 11:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.1 mole of benzyl cyclopentadiene monomers, 15 milliliters of toluene, add 0.01 mole of methylaluminoxane down at 0 ℃, keep 0 ℃ of reaction 12 hours, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtaining polymer yield is 61%, only contains 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit of 4-structure, wherein 1, the 2-structural content is 59%, number-average molecular weight 6400.
Embodiment 12:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.05 mole of cyclopentadiene monomers, add 0.005 mole of triisobutyl alumina alkane down at-84 ℃, keep-84 ℃ of reactions 12 hours, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtaining polymer yield is 67%, only contain 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit of 4-structure, wherein 1, the 2-structural content is 47%, number-average molecular weight 5300.
Embodiment 13:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.1 mole of cyclopentadiene monomers, 15 milliliters of toluene, add 0.01 mole of modified methylaluminoxane (commercially available prod down at 0 ℃, wherein 30% methyl is replaced by butyl), keep 0 ℃ of reaction 12 hours, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtaining polymer yield is 65%, only contain 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit of 4-structure, wherein 1, the 2-structural content is 58%, number-average molecular weight 6200.
Embodiment 14:
Under nitrogen protection, with 2 gram MgCl
2, 15 milliliters of methylaluminoxane (MAO) and 60 milliliters of toluene stirred 6 hours down in 40 ℃, filtered drying; Normal pressure will keep nitrogen atmosphere through 100 milliliters of polyreaction bottles nitrogen replacement twice of thorough drying processing down, add 0.05 mole of cyclopentadiene monomers, at-84 ℃ of MgCl of adding process down
2The MAO 0.01mol of load, keep-84 ℃ of reactions 12 hours, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtaining polymer yield is 61%, only contains 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit of 4-structure, wherein 1, the 2-structural content is 51%, number-average molecular weight 6400.
Embodiment 15:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.0025 mole of cyclopentadiene monomers, 0.0025 mole of styrene monomer, 7 milliliters of methylene dichloride, add 0.005 mole of methylaluminoxane down at 10 ℃, keep 10 ℃ of reactions 10 minutes, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtain polymer yield and reach 85%, the cyclopentadiene monomers unit is 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit forms of 4-structure (
1The HNMR analytical results is seen accompanying drawing two).
Embodiment 16:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.001 mole of cyclopentadiene monomers, 0.004 mole of norbornene monomer, 6 milliliters of methylene dichloride add 0.005 mole of methylaluminoxane down at 10 ℃, keep 10 ℃ of reactions 30 minutes, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtain polymer yield and reach 51%, by
1The HNMR analytical results, the cyclopentadiene monomers unit is 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit forms of 4-structure, the molar ratio of cyclopentadiene monomers is 64%.
Embodiment 17:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.002 mole of cyclopentadiene monomers, dicyclo [2.2.1] heptan-5-alkene-2,0.003 mole of 3-dicarboxylic anhydride monomer, 6 milliliters of methylene dichloride, add down 0.005 mole of methylaluminoxane at 10 ℃, keeps 0 ℃ to react 6 hours, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtain polymer yield and reach 47%, by
1The HNMR analytical results, the cyclopentadiene monomers unit is 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit forms of 4-structure, the molar ratio of cyclopentadiene monomers is 86%.
Embodiment 18:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.0025 mole of cyclopentadiene monomers, dicyclo [2.2.1] heptan-5-alkene-2,0.003 mole of 3-dimethyl dicarboxylate, 6 milliliters of methylene dichloride, add down 0.005 mole of methylaluminoxane at 10 ℃, keeps 0 ℃ to react 6 hours, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtain polymer yield and reach 52%, by
1The HNMR analytical results, the cyclopentadiene monomers unit is 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit forms of 4-structure, the molar ratio of cyclopentadiene monomers is 82%.
Embodiment 19:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.1 mole of methyl cyclopentadiene monomer, 15 milliliters of toluene, add 0.005 mole of MMAO (methyl-isobutyl aikyiaiurnirsoxan beta, molecular formula [(CH down at-84 ℃
3)
0.7(iso-C
4H
9)
0.3AlO] n), keep-84 ℃ of reactions 1.0 hours, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtaining polymer yield is 42%, only contain 1 in the polymkeric substance, 2-and 1, two kinds of chain structure unit of 4-structure, wherein 1, the 2-structural content is 49%, number-average molecular weight 4700.
Embodiment 20:
Normal pressure will keep nitrogen atmosphere through 100 milliliters of polyreaction bottles nitrogen replacement twice of thorough drying processing down, add 0.05 mole of cyclopentadiene monomers, at room temperature add 0.005 mole of oxyethyl group diethyl aluminum, Et
2AlOEt keeps reaction 6 hours, adds 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, and obtaining polymer yield is 43%, number-average molecular weight 8600.
Embodiment 21:
Normal pressure down will be through twice of nitrogen replacement of 100 milliliters of polyreaction bottles of thorough drying processing, keep nitrogen atmosphere, add 0.0025 mole of phenyl cyclopentadiene monomers, 6 milliliters of methylene dichloride, add down 0.005 mole of methylaluminoxane at 10 ℃, keeps 0 ℃ to react 6 hours, add 20 ml concns then and be 5% ethanol solution hydrochloride termination reaction, obtain polymer yield and reach 63%, the monomeric molar ratio of benzyl ring pentadiene is 86%.
Claims (10)
1. the method for a synthetic polymeric cyclopentadiene is synthesized by the homopolymerization of cyclopentadiene monomers or the copolyreaction of cyclopentadiene monomers and vinylbenzene, norbornylene or norbornene derivative, it is characterized in that:
Polymerisation catalysts consists of the alkylaluminoxane one-component, and described alkyl has 1～4 carbon atom;
Described cyclopentadiene monomers is the compound with following general structure,
Wherein, R
1～R
5Alkyl or aromatic base for H, C1～C4.
2. according to the described method of claim 1, it is characterized in that: described catalyzer is methylaluminoxane, triisobutyl alumina alkane or methyl-isobutyl aikyiaiurnirsoxan beta.
3. according to the described method of claim 1, it is characterized in that: described catalyzer is the oxyethyl group diethyl aluminum.
4. method according to claim 1 is characterized in that: described catalyzer is selected from a kind of catalyzer of alkylaluminoxane composition or the composite catalyst that alkylaluminoxane is formed.
5. method according to claim 1 is characterized in that: described catalyzer is that catalyzer is carried on SiO with various forms
2, MgCl
2, molecular sieve, polynite, clay or macromolecular compound carrier surface the load product.
6. method according to claim 1 is characterized in that: described norbornene derivative is dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxylic anhydride or dicyclo [2.2.1] heptan-5-alkene-2, the 3-dimethyl dicarboxylate.
7. method according to claim 1 is characterized in that: the mol ratio of described copolyreaction cyclopentadiene monomers and vinylbenzene, norbornylene or norbornene derivative is 20: 80～50: 50.
8. method according to claim 1 is characterized in that: the polymerization single polymerization monomer of described polyreaction and the mol ratio of alkylaluminoxane are 0.5: 1～20: 1.
9. method according to claim 1 is characterized in that: described polymeric reaction temperature is-84～30 ℃.
10. method according to claim 1 is characterized in that: described polymerization reaction time is 10 minutes～12 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06211916A (en) * | 1993-01-18 | 1994-08-02 | Asahi Chem Ind Co Ltd | Composite catalyst and polymerization process |
| CN1187493A (en) * | 1997-01-10 | 1998-07-15 | 中国石油化工总公司上海石油化工研究院 | Olefin polymerizing catalyst |
| US6627714B2 (en) * | 2000-11-10 | 2003-09-30 | Maruzen Petrochemical Co., Ltd. | Method for producing an olefin type copolymer having a cyclic structure |
-
2005
- 2005-11-18 CN CNB2005101148420A patent/CN100413896C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06211916A (en) * | 1993-01-18 | 1994-08-02 | Asahi Chem Ind Co Ltd | Composite catalyst and polymerization process |
| CN1187493A (en) * | 1997-01-10 | 1998-07-15 | 中国石油化工总公司上海石油化工研究院 | Olefin polymerizing catalyst |
| US6627714B2 (en) * | 2000-11-10 | 2003-09-30 | Maruzen Petrochemical Co., Ltd. | Method for producing an olefin type copolymer having a cyclic structure |
Non-Patent Citations (2)
| Title |
|---|
| 甲基铝氧烷性能与组成的依赖关系. 韦少义等.材料科学与工艺，第13卷第6期. 2005 |
| 甲基铝氧烷性能与组成的依赖关系. 韦少义等.材料科学与工艺，第13卷第6期. 2005 * |
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