CN1314636C - Method for selectively catalyst synthesizing AMS cyclic dimeric polymer and linear polymer - Google Patents

Method for selectively catalyst synthesizing AMS cyclic dimeric polymer and linear polymer Download PDF

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CN1314636C
CN1314636C CNB031291376A CN03129137A CN1314636C CN 1314636 C CN1314636 C CN 1314636C CN B031291376 A CNB031291376 A CN B031291376A CN 03129137 A CN03129137 A CN 03129137A CN 1314636 C CN1314636 C CN 1314636C
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CN1490285A (en
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单永奎
李静
戴立益
杨建国
何鸣元
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East China Normal University
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Abstract

The present invention discloses a method for selectively catalyzing and synthesizing AMS cyclic dimer and linear dimer, which belongs to the technical field of organic chemistry synthesis. Alpha-methylstyrene is used as a raw material, amine salt ionic liquid is used as a catalyst, the raw material is added to the catalyst, the mixture is stirred, heated and returned, AMS cyclic dimer is obtained by selective catalysis and synthesis, the AMS cyclic dimer is cooled, settled and separated, and products of AMS cyclic dimer 1, 3, 3-trimethyl-1-phenylindane or 1, 1, 3-trimethyl-3-phenylindane can be obtained; the raw material is dropped into the mixed liquid of ionic liquid and selective solvent, the mixed liquid is stirred, heated and returned, AMS linear chloride dimer is obtained by selective catalysis and synthesis, the AMS cyclic dimer is cooled and settled, and products of AMS linear chloride dimer 2, 4-diphenyl-1-methyl-1-pentene and 2, 4-diphenyl-1-methyl-2-pentene are obtained. The method has the advantages of mild reaction conditions, simple technology, easy operation, etc., products can be obtained by optional oriented synthesis, the conversion rate of the raw material is 100%, the yield is from 92 to 100%, and the solvent and the catalyst do not generate pollution.

Description

Selectively the method for AMS cyclic dimer and linear dimeric is synthesized in catalysis
Technical field
The present invention relates to the method for synthetic AMS cyclic dimer of a kind of selectively catalysis and linear dimeric, exactly, relate to a kind of selectively catalyzed synthesizing alpha-vinyl toluene cyclic dimer 1,3,3-trimethylammonium-1-phenyl indan or 1,1,3-trimethylammonium-3-phenyl indan and linear dimeric 2,4-phenylbenzene-1-Methyl-1-pentene and 2, the method for 4-phenylbenzene-1-methyl-2-amylene belongs to organic chemistry synthetic technical field.
Background technology
Oligomerization can take place in alpha-methyl styrene (AMS) under acidic conditions, generate AMS cyclic dimer 1,3,3-trimethylammonium-1-phenyl indan, AMS linear dimeric 2,4-phenylbenzene-1-Methyl-1-pentene and 2,4-phenylbenzene-1-methyl-2-amylene and AMS trimer 2,4,6-trimethylammonium-4,6-dimethyl-1-hexene etc.AMS cyclic dimer 1,3,3-trimethylammonium-1-phenyl indan can be used the softening agent, modifier of intermediate, plastics and the rubber of molecular weight regulator in synthetic of material, the polymkeric substance of making synthetic lubricating oil, fire retardant FR 1808 etc. widely; AMS linear dimeric 2,4-phenylbenzene-1-Methyl-1-pentene is used as chain-transfer agent or relative molecular weight conditioning agent etc. in polymer production.Background technology mostly adopts activated clay, toluene sulfonic acide and MCM-41 mesopore molecular sieve, Zeo-karb Nafion etc. to make catalyzer when the AMS dipolymer is synthesized in catalysis.The shortcoming of this technology is higher 120～180 ℃ an of temperature of reaction, uses volatile organic solvents such as chloroform, ether in the reaction, and conversion of raw material and reaction yield are lower, uses the synthetic a kind of product of a kind of catalyzer etc.
Summary of the invention
The technical problem to be solved in the present invention is the method that proposes synthetic AMS cyclic dimer of a kind of selectively catalysis and linear dimeric.The technical scheme that the present invention takes is to be raw material with the alpha-methyl styrene, it is characterized in that amine salt type ionic liquid is a catalyzer, the former is dripped in the latter, stir, heating, reflux, selectively the synthetic AMS cyclic dimer of catalysis cools off, sedimentation separates, and gets product A MS cyclic dimer 1,3,3-trimethylammonium-1-phenyl indan or 1,1,3-trimethylammonium-3-phenyl indan drips raw material in the mixed solution of ionic liquid and selective solvent, stirs, heating, reflux selectively synthetic AMS linear dimeric, cooling, sedimentation, get product A MS linear dimeric 2,4-phenylbenzene-1-Methyl-1-pentene and 2,4-phenylbenzene-1-methyl-2-amylene.
Now describe technical scheme of the present invention in detail: the method for synthetic AMS cyclic dimer of a kind of selectively catalysis and linear dimeric is a raw material with the alpha-methyl styrene, it is characterized in that, and with the general molecular formula R 3NHX-M aX bAmine salt type ionic liquid and the general molecular formula alcohol or the ether that are ROR ' make catalyzer and selective solvent respectively, wherein R represents C 2～C 10Alkyl, R ' expression H, C 2～C 10Alkyl, HX are mineral acid or organic acid, M aX bBe inorganic acid salt or organic acid salt, selectively the synthetic AMS cyclic dimer of catalysis: one have stir and the three-necked flask of reflux in adding catalyzer R 3NHX-M aX b, add-on is 4～36% of a raw material weight, drips the raw material alpha-methyl styrene then in three-necked bottle, control reaction temperature was reacted 5～30 minutes at 25～100 ℃, after reaction finishes, with reactant cooling, sedimentation, isolate catalyzer and white crystals shape material, catalyzer is reusable, product is an AMS cyclic dimer 1,3,3-trimethylammonium-1-phenyl indan or 1,1,3-trimethylammonium-3-phenyl indan, conversion of raw material is 100%, and productive rate is 92%～100%; The synthetic AMS linear dimeric of catalysis selectively: one have stir and the three-necked flask of reflux in adding catalyzer R 3NHX-M aX bAdd-on is 4～36% of a raw material weight, solvent ROR ' then brings Selection In, add-on is 5～60% of a raw material weight, then in three-necked bottle, drip the raw material alpha-methyl styrene, control reaction temperature was reacted 20～150 minutes at 25～100 ℃, after reaction finishes, with reactant cooling, sedimentation, isolate catalyzer and product, catalyzer is reusable, and product is the AMS linear dimeric, and 2,4-phenylbenzene-1-Methyl-1-pentene and 2,4-phenylbenzene-1-methyl-2-amylene, conversion of raw material is 100%, productive rate is 92%～100%.
Above-mentioned catalytic synthesis equation skeleton symbol is:
Be further characterized in that HX is mineral acid: H 2SO 4, HCl, HNO 3, HF, HBr, HBF 4, HPF 6, or organic acid: R " COOH, wherein R " is C 1～C 4Saturated hydrocarbyl; M aX bBe inorganic acid salt: M a(SO 4) b, M aCl b, M a(NO 3) b, M aF b, M aBr b, M a(BF 4) bAnd M a(PF 6) b, or organic acid salt: M a(R " COO) b, wherein M is K +, Na +, NH 4 +, Ca 2+, Ba 2+, Al 3+, Zn 2+, Fe 3+, a, b are equal to 1～3.
Compare with background technology, the present invention has following outstanding effect:
1. reaction conditions gentleness, temperature of reaction is 25～100 ℃, pressure is normal pressure.
2. regulate by selective solvent and can make the selectively directed synthetic product of reaction: AMS cyclic dimer and linear dimeric can carry out reaction according to operator's intention.
3. technology is simple, processing ease, and conversion of raw material is 100%, productive rate is 92～100%.
4. reaction raw materials is easy to get, and production cost is low.
5. without volatile organic solvent, ammonium salt type ionic liquid is not only made solvent but also make catalyzer, makes the greenization of production process realization solvent and catalyzer, has improved the economic benefit and the social benefit of production process.
Embodiment
All embodiment operate according to above-described synthetic method fully.
Embodiment one
Selectively the AMS cyclic dimer is synthesized in catalysis: catalyzer is (CH 3CH 2CH 2CH 2CH 2) 3NHPF 6-NaPF 6, add-on is 3.5g, and the raw material add-on is 14.6g, and conversion of raw material is 100%, AMS cyclic dimer 1,3, the productive rate of 3-trimethylammonium-1-phenyl indan is 96.3%; Selectively the AMS linear dimeric is synthesized in catalysis: catalyzer is (CH 3CH 2CH 2CH 2CH 2) 3NHPF 6NaPF 6, add-on is 3.5g, selective solvent is CH 3CH 2CH 2OH, add-on is 6g, the raw material add-on is 14.6g,, conversion of raw material is 100%, AMS linear dimeric 2, and the productive rate of 4-phenylbenzene-1-Methyl-1-pentene is 92.9%, AMS linear dimeric 2, the productive rate of 4-phenylbenzene-1-methyl-2-amylene is 0.6%.Two kinds of materials that the present invention relates to, catalyzer and selective solvent, its structure and quality do not change before and after reaction, and its kind can change within the specific limits, and catalyzer can be (CH 3CH 2CH 2CH 2CH 2) 3NH 2SO 4-ZnSO 4, (CH 3CH 2CH 2CH 2CH 2) 3NHNO 3-Ba (NO 3) 2, (CH 3CH 2CH 2CH 2CH 2) 3NHBr-CaBr 2, (CH 3CH 2CH 2CH 2CH 2) 3NHCl-FeCl 3, (CH 3CH 2CH 2CH 2CH 2) 3NHBF 4-NH 4BF 4, (CH 3CH 2CH 2CH 2CH 2) 3NHCl-AlCl 3, (CH 3CH 2CH 2CH 2CH 2) 3NHOOCCH 3-KOOCCH 3Or (CH 3CH 2CH 2CH 2CH 2) 3NHOOCCH 2CH 2CH 2CH 3-KOOCCH 2CH 2CH 2CH 3, add-on is 3.5g; Selective solvent can be (CH 3CH 2CH 2CH 2) 2O, (CH 3) 2C (OH) CH 2CH 3, CH 3CH 2CH 2CH 2OH, CH 3CH 2CH 2OCH 2CH (CH 3) CH 2CH 2CH 2CH 2CH 3, CH 3CH 2OCH 2CH 3Or CH 3CH 2CH 2C (CH 3) 2CH 2CH 2CH 2OH, add-on is 6g.
Embodiment two
Selectively the AMS cyclic dimer is synthesized in catalysis: catalyzer is (CH 3CH 2CH 2) 3NHPF 6-NaPF 6, add-on is 1g, and the raw material add-on is 25g, and conversion of raw material is 100%, AMS cyclic dimer 1,3, the productive rate of 3-trimethylammonium-1-phenyl indan is 92.8%; Selectively the AMS linear dimeric is synthesized in catalysis: catalyzer is (CH 3CH 2CH 2) 3NHPF 6-NaPF 6, add-on is 1g, selective solvent is CH 3CH 2CH 2OH, add-on is 4g, and the raw material add-on is 25g, and conversion of raw material is 100%, AMS linear dimeric 2, the productive rate of 4-phenylbenzene-1-Methyl-1-pentene is 92.6%, AMS linear dimeric 2, the productive rate of 4-phenylbenzene-1-methyl-2-amylene is 0.6%.Two kinds of materials that the present invention relates to, catalyzer and selective solvent, its structure and quality do not change before and after reaction, and its kind can change within the specific limits, and catalyzer can be (CH 3CH 2CH 2) 3NH 2SO 4-ZnSO 4, (CH 3CH 2CH 2) 3NHNO 3-Ba (NO 3) 2, (CH 3CH 2CH 2) 3NHBr-CaBr 2, (CH 3CH 2CH 2) 3NHCl-FeCl 3, (CH 3CH 2CH 2) 3NHBF 4-NH 4BF 4, (CH 3CH 2CH 2) 3NHCl-AlCl 3, (CH 3CH 2CH 2) 3NHOOCCH 3-KOOCCH 3Or (CH 3CH 2CH 2) 3NHOOCCH 2CH 2CH 2CH 3-KOOCCH 2CH 2CH 2CH 3, add-on is 1g; Selective solvent can be (CH 3CH 2CH 2CH 2) 2O, (CH 3) 2C (OH) CH 2CH 3, CH 3CH 2CH 2CH 2OH, CH 3CH 2CH 2OCH 2CH (CH 3) CH 2CH 2CH 2CH 2CH 3, CH 3CH 2OCH 2CH 3Or CH 3CH 2CH 2C (CH 3) 2CH 2CH 2CH 2OH, add-on is 4g.
Embodiment three
Selectively the AMS cyclic dimer is synthesized in catalysis: catalyzer is (CH 3CH 2) 3NHPF 6-NaPF 6, add-on is 2g, and the raw material add-on is 18g, and conversion of raw material is 100%, AMS cyclic dimer 1,3, the productive rate of 3-trimethylammonium-1-phenyl indan is 94.5%; Optionally the AMS linear dimeric is synthesized in catalysis: catalyzer is (CH 3CH 2) 3NHPF 6-NaPF 6, add-on is 2g, selective solvent is CH 3CH 2CH 2OH, add-on is 3.2g, and the raw material add-on is 18g, and conversion of raw material is 100%, AMS linear dimeric 2, the productive rate of 4-phenylbenzene-1-Methyl-1-pentene is 95.3%, AMS linear dimeric 2, the productive rate of 4-phenylbenzene-1-methyl-2-amylene is 0.4%.Two kinds of materials that the present invention relates to, catalyzer and selective solvent, its structure and quality do not change before and after reaction, and its kind can change within the specific limits, and catalyzer can be (CH 3CH 2) 3NH 2SO 4-ZnSO 4, (CH 3CH 2) 3NHNO 3-Ba (NO 3) 2, (CH 3CH 2) 3NHBr-CaBr 2, (CH 3CH 2) 3NHCl-FeCl 3, (CH 3CH 2) 3NHBF 4-NH 4BF 4, (CH 3CH 2) 3NHCl-AlCl 3, (CH 3CH 2) 3NHOOCCH 3-KOOCCH 3Or (CH 3CH 2) 3NHOOCCH 2CH 2CH 2CH 3-KOOCCH 2CH 2CH 2CH 3, add-on is 2g; Selective solvent can be (CH 3CH 2CH 2CH 2) 2O, (CH 3) 2C (OH) CH 2CH 3, CH 3CH 2CH 2CH 2OH, CH 3CH 2CH 2OCH 2CH (CH 3) CH 2CH 2CH 2CH 2CH 3, CH 3CH 2OCH 2CH 3Or CH 3CH 2CH 2C (CH 3) 2CH 2CH 2CH 2OH, add-on is 3.2g.
Embodiment four
Optionally the AMS cyclic dimer is synthesized in catalysis: catalyzer is (CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 2) 3NHPF 6-NaPF 6, add-on is 5g, raw material add-on 14g, and conversion of raw material is 100%, AMS cyclic dimer 1,3, the productive rate of 3-trimethylammonium-1-phenyl indan is 93.7%; Optionally the AMS linear dimeric is synthesized in catalysis: catalyzer (CH 3CH 2CH 2CH 2CH 2CH 2) 3NHPF 6-NaPF 6, add-on is 5g, selective solvent is CH 3CH 2CH 2OH, add-on is 8g, and the raw material add-on is 14g, and conversion of raw material is 100%, AMS linear dimeric 2, the productive rate of 4-phenylbenzene-1-Methyl-1-pentene is 93.8%, AMS linear dimeric 2, the productive rate of 4-phenylbenzene-1-methyl-2-amylene is 1.1%.Two kinds of materials that the present invention relates to, catalyzer and selective solvent, its structure and quality do not change before and after reaction, and its kind can change within the specific limits, and catalyzer can be (CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 2) 3NH 2SO 4-ZnSO 4, (CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 2) 3NHNO 3-Ba (NO 3) 2, (CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 2) 3NHBr-CaBr 2, (CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 2) 3NHCl-FeCl 3, (CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 2) 3NHBF 4-NH 4BF 4, (CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 2) 3NHCl-AlCl 3, (CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 2) 3NHOOCCH 3-KOOCCH 4Or (CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 2) 3NHOOCCH 2CH 2CH 2CH 3-KOOCCH 2CH 2CH 2CH 3, add-on is 5g; Solvent can be (CH 3CH 2CH 2CH 2) 2O, (CH 3) 2C (OH) CH 2CH 3, CH 3CH 2CH 2CH 2OH, CH 3CH 2CH 2OCH 2CH (CH 3) CH 2CH 2CH 2CH 2CH 3, CH 3CH 2OCH 2CH 3Or CH 3CH 2CH 2C (CH 3) 2CH 2CH 2CH 2OH, add-on is 8g.
Embodiment five
Selectively the AMS cyclic dimer is synthesized in catalysis: catalyzer is (CH 3CH 2CH 2CH 2) 3NHPF 6-NaPF 6, add-on is 3g, and the raw material add-on is 18g, and conversion of raw material is 100%, AMS cyclic dimer 1,3, the productive rate of 3-trimethylammonium-1-phenyl indan is 95.7%; Selectively the AMS linear dimeric is synthesized in catalysis: catalyzer is (CH 3CH 2CH 2CH 2) 3NHPF 6-NaPF 6, add-on is 3g, selective solvent is CH 3CH 2CH 2OH, add-on is 4g, and the raw material add-on is 18g, and conversion of raw material is 100%, AMS linear dimeric 2, the productive rate of 4-phenylbenzene-1-Methyl-1-pentene is 93.6%, AMS linear dimeric 2, the productive rate of 4-phenylbenzene-1-methyl-2-amylene is 1.2%.Two kinds of materials that the present invention relates to, catalyzer and selective solvent, its structure and quality do not change before and after reaction, and its kind can change within the specific limits, and catalyzer can be (CH 3CH 2CH 2CH 2) 3NH 2SO 4-ZnSO 4, (CH 3CH 2CH 2CH 2) 3NHNO 3-Ba (NO 3) 2, (CH 3CH 2CH 2CH 2) 3NHBr-CaBr 2, (CH 3CH 2CH 2CH 2) 3NHCl-FeCl 3, (CH 3CH 2CH 2CH 2) 3NHBF 4-NH 4BF 4, (CH 3CH 2CH 2CH 2) 3NHCl-AlCl 3, (CH 3CH 2CH 2CH 2) 3NHOOCCH 3-KOOCCH 3Or (CH 3CH 2CH 2CH 2) 3NHOOCCH 2CH 2CH 2CH 3-KOOCCH 2CH 2CH 2CH 3, add-on is 3g; Solvent can be (CH 3CH 2CH 2CH 2) 2O, (CH 3) 2C (OH) CH 2CH 3, CH 3CH 2CH 2CH 2OH, CH 3CH 2CH 2OCH 2CH (CH 3) CH 2CH 2CH 2CH 2CH 3, CH 3CH 2OCH 2CH 3Or CH 3CH 2CH 2C (CH 3) 2CH 2CH 2CH 2OH, add-on is 4g.

Claims (2)

1, the method for a kind of catalyzed synthesizing alpha-vinyl toluene linear dimeric is a raw material with the alpha-methyl styrene, is R with the general molecular formula 3NHX-M aX bAmine salt type ionic liquid make catalyzer, wherein R represents C 2～C 10Alkyl, HX are mineral acid or organic acid, M aX bFor inorganic acid salt or organic acid salt, it is characterized in that, with the general molecular formula ether of the ROR ' solvent that elects, wherein R represents C 2～C 10Alkyl, R ' represents C 2～C 10Alkyl, catalyzed synthesizing alpha-vinyl toluene linear dimeric: one have stir and the three-necked flask of reflux in adding catalyzer R 3NHX-M aX bAdd-on is 4～36% of a raw material weight, solvent ROR ' then brings Selection In, add-on is 5～60% of a raw material weight, then in three-necked flask, drip the raw material alpha-methyl styrene, control reaction temperature is at 25～100 ℃, reacted 20～150 minutes, after reaction finishes, with reactant cooling, sedimentation, isolate catalyzer and product, catalyzer is reusable, product is an alpha-methyl styrene linear dimeric 2,4-phenylbenzene-1-Methyl-1-pentene and 2,4-phenylbenzene-1-methyl-2-amylene, conversion of raw material is 100%, and productive rate is 92～100%.
2, the method for catalyzed synthesizing alpha according to claim 1-vinyl toluene linear dimeric is characterized in that, HX is mineral acid: H 2SO 4, HCl, HNO 3, HF, HBr, HBF 4, HPF 6, or organic acid: R " COOH, wherein R " be C 1～C 4Saturated hydrocarbyl; M aX bBe inorganic acid salt: M a(SO 4) b, M aCl b, M a(NO 3) b, M aF b, M aBr b, M a(BF 4) bAnd M a(PF 6) b, or organic acid salt: M a(R " COO) b, wherein M is K +, Na +, NH 4+, Ca 2+, Ba 2+, Al 3+, Zn 2+, Fe 3+, a, b are equal to 1～3.
CNB031291376A 2003-06-09 2003-06-09 Method for selectively catalyst synthesizing AMS cyclic dimeric polymer and linear polymer Expired - Fee Related CN1314636C (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2074161C1 (en) * 1993-01-11 1997-02-27 Амирханов Камиль Шакирович METHOD FOR PRODUCTION OF DIMMERS OF α-METHYLSTYRENE
CN1364751A (en) * 2001-12-28 2002-08-21 华东师范大学 Method for preparing 2,4-diphenyl-4-methyl-1-amylene in ion liquid [Hmim]+BF4-
CN1384084A (en) * 2002-06-11 2002-12-11 华东师范大学 Catalytic synthesis of AMS cyclic dimer 1,3,3-trimethyl-1-phenyl indane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2074161C1 (en) * 1993-01-11 1997-02-27 Амирханов Камиль Шакирович METHOD FOR PRODUCTION OF DIMMERS OF α-METHYLSTYRENE
CN1364751A (en) * 2001-12-28 2002-08-21 华东师范大学 Method for preparing 2,4-diphenyl-4-methyl-1-amylene in ion liquid [Hmim]+BF4-
CN1384084A (en) * 2002-06-11 2002-12-11 华东师范大学 Catalytic synthesis of AMS cyclic dimer 1,3,3-trimethyl-1-phenyl indane

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