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WO1998033787A1 - Procede pour preparer un anhydride carboxylique - Google Patents

Procede pour preparer un anhydride carboxylique Download PDF

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Publication number
WO1998033787A1
WO1998033787A1 PCT/EP1998/000543 EP9800543W WO9833787A1 WO 1998033787 A1 WO1998033787 A1 WO 1998033787A1 EP 9800543 W EP9800543 W EP 9800543W WO 9833787 A1 WO9833787 A1 WO 9833787A1
Authority
WO
WIPO (PCT)
Prior art keywords
carboxylic anhydride
preparation
anhydride
salts
reaction
Prior art date
Application number
PCT/EP1998/000543
Other languages
English (en)
Inventor
Mareki Miura
Yoshinobu Ohnuma
Original Assignee
Shell Internationale Research Maatschappij B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to AU60987/98A priority Critical patent/AU726989B2/en
Priority to KR19997006838A priority patent/KR20000070591A/ko
Priority to NZ336444A priority patent/NZ336444A/xx
Priority to CA002278587A priority patent/CA2278587A1/fr
Priority to EP98905384A priority patent/EP0970068A1/fr
Priority to BR9807293A priority patent/BR9807293A/pt
Publication of WO1998033787A1 publication Critical patent/WO1998033787A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/54—Preparation of carboxylic acid anhydrides
    • C07C51/567—Preparation of carboxylic acid anhydrides by reactions not involving carboxylic acid anhydride groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3

Definitions

  • the present invention relates to a process for the preparation of a carboxylic anhydride.
  • the present invention relates to a process for the preparation of a carboxylic anhydride having a cyclohexane ring which is a liquid at room temperature, which can be employed as a curing agent for epoxy resins, and which is useful in uses such as a liquid encapsulant for semiconductors, a liquid encapsulant for light emission diodes, and optical materials.
  • a liquid encapsulant for semiconductors a liquid encapsulant for light emission diodes, and optical materials.
  • most compounds are obtained as solid products by a Diels-Alder reaction of a diene- hydrocarbon or triene-hydrocarbon having a carbon number of 10 with maleic anhydride.
  • a carboxylic anhydride obtained from alloocimene which is one kind of dimethyl octatrienens, and maleic anhydride is a solid having a melting point of 83 to 85 °C, and is troublesome in handling as a curing agent for epoxy resins.
  • No. 906017 there is also proposed a process in which a solid carboxylic anhydride obtained by a Diels-Alder reaction is liquefied by hydrogenation .
  • the carboxylic anhydride obtained by the process coloration is slight, whereby, it can be employed as a curing agent for the preparation of a cured epoxy resin which can be utilized for the uses such as optical materials.
  • a hydrogenated carboxylic anhydride in a high purity which is obtained by a recrystalliza- tion process is a solid having a melting point of 53 to 55 °C, and it is troublesome in handling as a curing agent for epoxy resins. Accordingly, a liquid state carboxylic anhydride is obtained as a mixture by controlling a ratio of hydrogenation in 70% or so.
  • the process has a problem that a carboxylic anhydride obtained is yellow-colored because of comprising colored unhydrogenated compounds by 30% or so .
  • liquid carboxylic anhydride which is colorless, transparent, and highly pure, with good stability by manufacturing from a hydrocarbon compound of a diene or triene having a carbon number of 10, and maleic anhydride .
  • the present invention aims at providing a carboxylic anhydride which is low hygroscopic, excellent in colorless and transparency and a liquid at room temperature and thus is useful for uses such as a curing agent for epoxy resins, a liquid encapsulant for semiconductors, a liquid encapsulant for light emission diodes, and optical materials.
  • a preferred embodiment of the present invention relates to a process for the preparation of the aforementioned carboxylic anhydride, in which dimethyloctatriene is employed. More preferably alloocimene is employed as the aforementioned dimethyloctatriene .
  • the afore- mentioned stereo-isomerization reaction is carried out in a temperature range of 100 to 250 °C, and preferably from 175-225 °C,and the catalyst for an isomerization is employed under conditions within a range of 0.005 to 5 parts by weight based on 100 parts by weight of the carboxylic anhydride.
  • diene- or triene-hydrocarbon compound to be employed in the present invention for example, there are exemplified alloocimene, ocimene, myrcene, 2 , 7-dimethyl-l, 3, 7-octatriene, and 2, 6-dimethyl-l, 3, 6- octatriene, etc.
  • alloocimene is particularly preferred from a viewpoint of the ready availability and liquid state stability of the obtained carboxylic anhydride.
  • the catalyst for stereo isomerization to be employed in the present invention is a compound or a mixture of more than two kinds of compounds selected from a compound having nitrogen atom (s), a phosphine compound, a salt of an alkaline metal, and a salt of thiocyanic acid.
  • a compound having nitrogen atom (s) there are employed tertiary amines, salts of tertiary amines, imidazoles, salts of imidazoles, and salts of quaternary ammonium.
  • imidazoles for example, there are employed 2-methylimidazole, 2-ethyl-4- methylimidazole, 2-undecylimidazole, 2-phenylimidazole, l-benzyl-2-methylimidazole, and l-cyanoethyl-2- methylimidazole .
  • salts of the tertiary amines and the salts of imidazoles for example, there are employed salts of a mineral acid such as a chloric acid salt and a sulfuric acid salt of tertiary amines and imidazoles, salts of an organic carboxylic acid such as salts of an acetic acid and salts of 2-ethylhexyl acid, and salts of a phenol such as salts of a bisphenol and salts of hydroquinone .
  • a mineral acid such as a chloric acid salt and a sulfuric acid salt of tertiary amines and imidazoles
  • salts of an organic carboxylic acid such as salts of an acetic acid and salts of 2-ethylhexyl acid
  • salts of a phenol such as salts of a bisphenol and salts of hydroquinone .
  • salts of quaternary ammonium for example, there are employed tetramethylammonium chloride, tetraethyl ammonium chloride, tetraethyl- ammonium bromide, tetraethylammonium iodide, tetra- butylammoniu bromide, lauryltrimethylammonium chloride, and benzyltrimethylammonium chloride.
  • triphenylphosphines for example, there are employed triphenylphosphine, tri- tolyl phosphine, and tris (2, 6-dimethoxyphenyl) - phosphine.
  • the salts of quaternary phosphonium for example, there are employed tetramethyl phosphonium chloride, tetraethyl phosphonium chloride, tetraethylphosphonium bromide, tetraethylphosphonium iodide, tetrabutyl phosphonium bromide, lauryltrimethyl phosphonium chloride, and benzyltrimethyl phosphonium chloride, ethyltriphenyl phosphonium iodide, tetraphenyl phosphonium chloride, and tetraphenyl phosphonium bromide .
  • salts of an alkaline metal for example, there are employed halogenated alkaline metals, salts of alkaline metal of an inorganic acid, or salts of an alkaline metal of an organic acid.
  • halogenated alkaline metals for example, there are employed lithium chloride, lithium bromide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, and cesium chloride.
  • Examples of the salts of an alkaline metal of an inorganic acid are lithium sulfate, lithium nitrate, lithium phosphate, lithium carbonate, sodium sulfate, sodium nitrate, sodium phosphate, sodium carbonate, potassium sulfate, potassium nitrate, potassium phosphate, and potassium carbonate.
  • Lithium salts are the preferred ones.
  • the isomerization is a stereo-isomerization of an acid anhydride compound having a cyclohexene ring which is a product in a Diels-Alder reaction.
  • the isomeriza- tion is preferably carried out in a temperature range of 100 to 250 °C and more preferably in a temperature range of from 175-225 °C.
  • the amount of the catalysts for the isomerization is less than 0.005 part by weight, the reaction does not readily proceed, and in the case that it exceeds 5 parts by weight, side reactions readily occur, and color hue of the carboxylic anhydride obtained becomes worse.
  • the hydrogenation reaction in the present invention is a hydrogenation to carbon-carbon double bond.
  • a usual catalytic reduction can be employed for the reaction methods.
  • the reaction is carried out at a temperature of 30 to 200 °C, and preferably 50 to
  • the hydrogenation is carried out until a carboxylic anhydride not having carbon-carbon double bond attains to not less than 90% by weight, and preferably not less than 95% by weight.
  • a carboxylic anhydride not having the double bond is less than 90% by weight, coloration increases, unpreferably resulting in that it cannot be employed for uses such as optical materials .
  • the reaction in order to obtain a desired carboxylic anhydride is carried out by a Diels-Alder reaction method in which a diene or triene is added dropwise in a range of 0.8 to 1.2 mol and preferably in the range of 0.9 to 1.1 mol of a carboxylic anhydride based on 1 mol of the diene-or triene-hydrocarbon compound having a carbon number of 10, while maintaining the reaction temperature in a range of 50 to 180 °C, and preferably 70 to 150 °C .
  • a solid carboxylic anhydride is obtained by carrying out a reaction for aging for 0.5 to 3 hours while maintaining the temperatures . Subsequently, the aforementioned catalyst for isomerization is added, and the isomerization is carried out for 0.1 to 10 hours, preferably 0.5 to 4 hours while maintaining the temperature in a range of 100 to 250 °C and preferably from 175 to 225 °C, to obtain a liquid state carboxylic anhydride.
  • the liquid carboxylic anhydride obtained has an excellent property as a curing agent for epoxy resins, and it can be employed in extensive uses such as a liquid encapsulant for semiconductors, a liquid state encapsulant for emission diodes, and optical materials .
  • Example 1
  • Example 1 was carried out, and a single-stage distillation of an obtained carboxylic anhydride was carried out under the reduced pressure of 0.9 mmHg and collecting distillates at 150 to 165 °C gave 545 g (a yield of 93.2%) of a brownish yellow solid of a carboxylic anhydride.
  • the carboxylic anhydride did not solidify even being stored at the temperature of 5 °C for 3 months after the addition of 1% by weight of a crystal nucleus of a solid maleic anhydride-alloocimene adduct, and it was excellent in stability in a liquid state .
  • Examples 3 to 10 The same operations were carried out as in
  • Example 1 except that the diene or triene, catalysts for isomerization, and conditions for isomerization were changed as described in Table 1 to obtain carboxylic anhydrides which are a colorless and transparent liquid. Results are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Furan Compounds (AREA)
  • Epoxy Resins (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un anhydride carboxylique incolore et transparent ayant une excellente stabilité à l'état liquide à température ambiante, qui est utile dans diverses applications, par exemple comme agent de durcissement pour les résines époxyde, comme encapsulant liquide pour les semi-conducteurs et comme encapsulant liquide pour les diodes luminescentes. Cet anhydride d'acide carboxylique est un liquide à 20 °C comprenant un anhydride d'acide carboxylique n'ayant pas de double liaison carbone - carbone, comme par exemple l'anhydride de l'acide 3-isobutyl-5,6-diméthylcyclohexane-1,2-dicarboxylique, l'anhydride de l'acide 3-(β-méthylbutyl)-5-méthylcyclohexane-1,2-dicarboxylique et l'anhydride de l'acide 4-isohexylcyclohexane-1,2-dicarboxylique. La préparation de l'anhydride se fait en formant un anhydride d'acide ayant un noyau cyclohexène par une réaction de Diels-Alder d'un hydrocarbure diénique ou triénique ayant un nombre d'atomes de carbone égal à 10, avec l'anhydride de l'acide maléique. Cette réaction est suivie par une stéréoisomérisation en présence d'un catalyseur et par une hydrogénation dudit produit de réaction.
PCT/EP1998/000543 1997-01-30 1998-01-29 Procede pour preparer un anhydride carboxylique WO1998033787A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AU60987/98A AU726989B2 (en) 1997-01-30 1998-01-29 Process for the preparation of a carboxylic anhydride
KR19997006838A KR20000070591A (ko) 1997-01-30 1998-01-29 카복실산 무수물의 제조방법
NZ336444A NZ336444A (en) 1997-01-30 1998-01-29 Preparing carboxylic anhydride having a cyclohexane ring useful for semiconductors, light emission diodes and optical materials
CA002278587A CA2278587A1 (fr) 1997-01-30 1998-01-29 Procede pour preparer un anhydride carboxylique
EP98905384A EP0970068A1 (fr) 1997-01-30 1998-01-29 Procede pour preparer un anhydride carboxylique
BR9807293A BR9807293A (pt) 1997-01-30 1998-01-29 ico

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9/29826 1997-01-30
JP9029826A JPH10212285A (ja) 1997-01-30 1997-01-30 無水カルボン酸の製造方法

Publications (1)

Publication Number Publication Date
WO1998033787A1 true WO1998033787A1 (fr) 1998-08-06

Family

ID=12286838

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/000543 WO1998033787A1 (fr) 1997-01-30 1998-01-29 Procede pour preparer un anhydride carboxylique

Country Status (10)

Country Link
EP (1) EP0970068A1 (fr)
JP (1) JPH10212285A (fr)
KR (1) KR20000070591A (fr)
CN (1) CN1246115A (fr)
AU (1) AU726989B2 (fr)
BR (1) BR9807293A (fr)
CA (1) CA2278587A1 (fr)
NZ (1) NZ336444A (fr)
WO (1) WO1998033787A1 (fr)
ZA (1) ZA98646B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002066412A1 (fr) * 2001-02-16 2002-08-29 Basf Aktiengesellschaft Procede de production d'acides cyclohexanedicarboxyliques et leurs derives
US7297738B2 (en) 2001-09-25 2007-11-20 Exxonmobil Chemical Patents Inc. Plasticized polyvinyl chloride
US8710104B2 (en) 2008-11-07 2014-04-29 Triact Therapeutics, Inc. Catecholic butanes and use thereof for cancer therapy
US9381246B2 (en) 2013-09-09 2016-07-05 Triact Therapeutics, Inc. Cancer therapy
US9834575B2 (en) 2013-02-26 2017-12-05 Triact Therapeutics, Inc. Cancer therapy
WO2019213112A1 (fr) * 2018-04-30 2019-11-07 Dow Silicones Corporation Composition réticulée, composition de soins personnels les comprenant, et procédés de formation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1313456C (zh) * 2005-06-22 2007-05-02 河南省科学院化学研究所 一种生产甲基六氢苯酐的新方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB906017A (en) * 1958-10-09 1962-09-19 Heyden Newport Chemical Corp Substituted tetrahydro- and hexahydrophthalic anhydrides and resinous compositions containing the same
JPS5564581A (en) * 1978-11-07 1980-05-15 Mitsubishi Petrochem Co Ltd Liquefaction of solid alloocimene adduct with maleic anhydride
JPS5572184A (en) * 1978-11-22 1980-05-30 Mitsubishi Petrochem Co Ltd Liquefaction of solid maleinized decatriene
JPS55129416A (en) * 1979-03-30 1980-10-07 Mitsubishi Petrochem Co Ltd Curable epoxy resin composition
JPH0632788A (ja) * 1992-07-14 1994-02-08 Tonen Corp 飽和脂環式ジカルボン酸無水物の製造法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4332733A (en) * 1979-02-28 1982-06-01 Mitsubishi Petrochemical Co., Ltd. Process for liquefying acid anhydride

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB906017A (en) * 1958-10-09 1962-09-19 Heyden Newport Chemical Corp Substituted tetrahydro- and hexahydrophthalic anhydrides and resinous compositions containing the same
JPS5564581A (en) * 1978-11-07 1980-05-15 Mitsubishi Petrochem Co Ltd Liquefaction of solid alloocimene adduct with maleic anhydride
JPS5572184A (en) * 1978-11-22 1980-05-30 Mitsubishi Petrochem Co Ltd Liquefaction of solid maleinized decatriene
JPS55129416A (en) * 1979-03-30 1980-10-07 Mitsubishi Petrochem Co Ltd Curable epoxy resin composition
JPH0632788A (ja) * 1992-07-14 1994-02-08 Tonen Corp 飽和脂環式ジカルボン酸無水物の製造法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8026, Derwent World Patents Index; Class A60, AN 80-45604C, XP002066914 *
DATABASE WPI Section Ch Week 8029, Derwent World Patents Index; Class A60, AN 80-50525C, XP002066913 *
DATABASE WPI Section Ch Week 8047, Derwent World Patents Index; Class A21, AN 80-83412C, XP002066915 *
DATABASE WPI Section Ch Week 9410, Derwent World Patents Index; Class A60, AN 94-079977, XP002066916 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002066412A1 (fr) * 2001-02-16 2002-08-29 Basf Aktiengesellschaft Procede de production d'acides cyclohexanedicarboxyliques et leurs derives
US7319161B2 (en) 2001-02-16 2008-01-15 Basf Aktiengesellschaft Method for producing cyclohexane dicarboxylic acids and the derivatives thereof
US7297738B2 (en) 2001-09-25 2007-11-20 Exxonmobil Chemical Patents Inc. Plasticized polyvinyl chloride
US7413813B2 (en) 2001-09-25 2008-08-19 Exxonmobil Chemical Patents Inc. Plasticised polyvinyl chloride
US7585571B2 (en) 2001-09-25 2009-09-08 Exxonmobil Chemical Patents Inc. Plasticised polyvinyl chloride
US8710104B2 (en) 2008-11-07 2014-04-29 Triact Therapeutics, Inc. Catecholic butanes and use thereof for cancer therapy
US9834575B2 (en) 2013-02-26 2017-12-05 Triact Therapeutics, Inc. Cancer therapy
US9381246B2 (en) 2013-09-09 2016-07-05 Triact Therapeutics, Inc. Cancer therapy
WO2019213112A1 (fr) * 2018-04-30 2019-11-07 Dow Silicones Corporation Composition réticulée, composition de soins personnels les comprenant, et procédés de formation
CN111971025A (zh) * 2018-04-30 2020-11-20 美国陶氏有机硅公司 交联组合物，包括其的个人护理组合物和形成方法
CN111971025B (zh) * 2018-04-30 2023-06-09 美国陶氏有机硅公司 交联组合物，包括其的个人护理组合物和形成方法

Also Published As

Publication number Publication date
AU6098798A (en) 1998-08-25
BR9807293A (pt) 2000-03-21
JPH10212285A (ja) 1998-08-11
KR20000070591A (ko) 2000-11-25
EP0970068A1 (fr) 2000-01-12
ZA98646B (en) 1998-07-30
CN1246115A (zh) 2000-03-01
CA2278587A1 (fr) 1998-08-06
NZ336444A (en) 2000-08-25
AU726989B2 (en) 2000-11-30

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