WO1996001865A1 - Oxyde d'oligophenylene a fonction multihydroxy - Google Patents

Oxyde d'oligophenylene a fonction multihydroxy Download PDF

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Publication number
WO1996001865A1
WO1996001865A1 PCT/NL1995/000242 NL9500242W WO9601865A1 WO 1996001865 A1 WO1996001865 A1 WO 1996001865A1 NL 9500242 W NL9500242 W NL 9500242W WO 9601865 A1 WO9601865 A1 WO 9601865A1
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WO
WIPO (PCT)
Prior art keywords
oligophenylene
functional
hydroxyaryl
multihydroxy
oxide
Prior art date
Application number
PCT/NL1995/000242
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English (en)
Inventor
Henk Oevering
Gerard Hidde Werumeus Buning
Egbert Willem Meijer
Hubertus Adrianus Maria Van Aert
Gerardus Jacobus Joseph Out
Original Assignee
Dsm N.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.)
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Publication date
Application filed by Dsm N.V. filed Critical Dsm N.V.
Priority to AU28092/95A priority Critical patent/AU2809295A/en
Publication of WO1996001865A1 publication Critical patent/WO1996001865A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/14—Preparation of ethers by exchange of organic parts on the ether-oxygen for other organic parts, e.g. by trans-etherification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups

Definitions

  • the invention relates to multihydroxy-functional oligophenylene oxide.
  • Mono- and dihydroxy-functional oligophenylene oxides are known from GB-A-1,119,914. This publication describes mono- and difunctional oligophenylene oxides that are prepared by a reaction between poly-(l,4-phenylene oxide) and a mono- or diphenol. This reaction is activated by the presence of an initiator, such as a peroxide or a catalyst containing a cupper compound.
  • the aim of the invention is the preparation of multihydroxy-functional oligophenylene oxides.
  • these compounds are prepared by reacting a compound containing hydroxyaryl comprising at least three hydroxyaryl groups according to the formula
  • R 1 an aromatic, aliphatic or cycloaliphatic group containing 1-50 carbon atoms
  • R 2 , R 3 H or an aromatic, aliphatic or cycloaliphatic group containing 1-50 carbon atoms, or two of the R 1 , R 2 or R 3 groups together constitute a ring structure containing 4-50 carbon atoms, with a polyphenylene oxide in the presence of a catalystcomplex containing a transition metal and an amine, This results in the preparation of multihydroxy- functional oligophenylene oxide in a practically pure form.
  • the multihydroxy-functional oligophenylene oxide has a high mechanical stability, in contrast with mono- and dihydroxy-functional oligophenylene oxides.
  • the spherical multihydroxy-functional oligophenylene oxides obtained by reaction of, for instance a calixarene or a dendrimer with polyphenylene oxide are very suitable for use as a fluidity improving agent in other polymers, such as polyphenylene oxide and mixtures containing polyphenylene oxide.
  • the reaction between the compound containing hydroxyaryl and the polyphenylene oxide is carried out in the presence of a catalyst complex containing a transition metal and an amine.
  • the catalyst complex may contain aliphatic amines or compounds containing pyridine, such as diethylamine, dibutylamine, tetramethylene diamine, oligomeric amines, polyvinyl pyridine, pyridine and dimethylaminopyridine.
  • aliphatic amines or compounds containing pyridine such as diethylamine, dibutylamine, tetramethylene diamine, oligomeric amines, polyvinyl pyridine, pyridine and dimethylaminopyridine.
  • the catalyst complex contains dimethylaminopyridine.
  • the catalyst complex also contains a transition metal.
  • the transition metal is chosen from groups 8-11 of the Periodic System of the Elements (Handbook of Chemistry and Physics, 70th edition, CRC Press, 1989-1990).
  • the transition metal is chosen from the group comprising copper, manganese, iron and cobalt.
  • the catalyst complex contains copper.
  • copper compounds which can be used are copper(I) chloride, copper(I) acetate or copper(I) carboxylate.
  • the halides, acetates and carboxylates of copper(II) may also be used.
  • Transetherification is understood to mean: the redistribution of the phenol monomers constituting the polyphenylene oxide among the hydroxyaryl groups of the compound containing hydroxyaryl so that oligophenylene oxides with the same number-average molecular weight are formed.
  • An oligophenylene oxide is formed as an 'arm' onto the compound containing hydroxyaryl.
  • Oligophenylene oxide' is understood to mean an oligomer of phenol monomers containing at least one chain of monomers that comprises between 2 and 70 monomer units.
  • all compounds containing hydroxyaryl can be used as the compounds containing hydroxyaryl comprising at least three hydroxyaryl groups as defined by the above formula.
  • Examples of compounds containing hydroxyaryl comprising at least three hydroxyaryl groups are: star-shaped phenols, phenolic resins and other phenol-modified polymers, calix- (n)arenes and dendrimers containing terminal hydroxyaryl groups.
  • star-shaped phenols are: 2,6-bis- (4 '-hydroxy-3 ',5 '-dimethylbenzyl)-4-tertiary-butylphenol, 2,6-bis-(4 '-hydroxy-3 ' ,5 '-dimethylbenzyl)-4-octylphenol, 2,6-bis-(4 '-hydroxy-3 ',5 '-dimethylbenzyl)-4- isooctylphenol, 2,6-bis-(4 '-hydroxy-3 ',5 '-dimethylbenzyl)- 4-isopropylphenol, 2,4,6-tri-(4'-hydroxy-3 ',5 '- dimethylbenzyl)phenol, (3,3 ',5,5 '-tetra(4"-hydroxybenzyl)- 4,4 '-dihydroxyphenyl)methane, (3,3',5,5 '-tetra(4"-hydroxy- 3" ,5"-dimethylbenzyl)-4,4
  • Resols and novolaks can be mentioned as phenolic resins.
  • phenol-modified polymers examples include: poly(p-hydroxystyrene) , copolymers of p-hydroxystyrene and other monomers, terminal-hydroxyaryl-containing polycarbonate, polyetherimide and polysulphone.
  • Calixarenes are metacyclophanes with a hydroxyl group at each 2 position. They are prepared via a base-catalysed condensation reaction of a p-alkylphenol and formaldehyde. They are for example described in 'Calixarenes, CD. Gutsche, The Royal Society of Chemistry, Cambridge (1989)".
  • Tertiary-butylcalix(4)arene, tertiary-butylcalix(6)arene and tertiary-butylcalix(8)arene can for example be mentioned as calixarenes.
  • Dendrimers are three-dimensional, highly branched oligomeric and polymeric molecules with an exactly defined chemical structure. Dendrimers are generally composed of a core, a number of generations of branches and an external surface.
  • the generations of branches are composed of structural units repeating themselves, which are radially bound to the core.
  • the external surface is composed of the functional groups of the last generation. Examples of suitable dendrimers are for example described in Angew. Chem. Int. Ed. Engl. 29 (1990), pp. 138-175 and PCT/NL93/00008.
  • the functional groups in the external surface the dendrimers that can be used according to the invention contain the hydroxyaryl groups according to the above formula.
  • Examples of these dendrimers are: 4- cascade: 1, -diaminobutane[4] :N-T-BOC-L-tyrosine- propylamide, 8-cascade: 1,4-diaminobutane[4] : (1- azabutylidene) :N-T-BOC-L-tyrosine-propylamide) , 16- cascade: 1,4-diaminobutane[4] : (l-azabutylidene) 12 :N-T-BOC- L-tyrosine-propylamide) , 32-cascade: 1,4- diaminobutane[4] : (l-azabutylidene) 28 :N-T-BOC-L-tyrosine- propylamide) and 64-cascade: l,4-diaminobutane[4] : (1- azabutylidene) 60 :N-T-BOC-L
  • polyphenylene oxide use can be made of all the known polyphenylene oxides, as for example described in 'Encyclopedia of polymer science and engineering, Vol. 13, John Wiley & Sons, Inc. (1988), pp 1-30'.
  • Hydroxyl-functional oligophenylene oxides can be used in a wide field of applications.
  • the spherical multihydroxyl-functional oligophenylene oxides can for example be used as fluidity improving agents in other polymers. Also conceivable is a mixture of polyphenylene oxide and (a) multifunctional oligophenylene oxide(s) that makes the polyphenylene oxide better processable.
  • the multi-hydroxy-functional oligophenylene oxides can also be used as fluidity improving agents in mixtures of polyphenylene oxide with other polymers, such as polystyrene, polyamide-6,6 and polypropylene. Spherical multihydroxy-functional oligophenylene oxdies are better mixable with other polymers than polyphenylene oxide.
  • the oligophenylene oxides also possess a high chemical resistance.
  • thermosets such as epoxy resin, (meth)acrylates, polyesters and silicons.
  • multihydroxy-functional oligophenylene oxides improve the flame-retardant properties of thermosets.
  • low-molecular-weight PPO a PPO with an M n of
  • the number-average molecular weight of the oligophenylene oxide formed was 11590.
  • the polymers obtained were characterised with 'H-NMR and gelpermeation chromatography combined with a viscosity detector.
  • the Zimm-Stockmayer theory teaches that the value of the ratio between [h ⁇ tar /thlii n indicates the degree of branching.
  • Example VI 0.150 g DAB(PA) 8 -tyrosine in 2 ml dimethylsulfoxide (DMSO) was slowly added to a solution of
  • Example VI was repeated with DAB(PA) 32 -tyrosine and DAB(PA) 64 -tyrosine instead of DAB(PA) ⁇ -tyrosine.
  • Example VI was repeated with 0.12 g DAB(PA) 64
  • Chloroform was used as a solvent for the dendrimer. - 11 -
  • Example IX was repeated with 0.32 g DAB(PA) 64 (50% L-tyrosine; 50% d-phenylalanine) and 1.16 g PPO. 9.7 mg CuCl and 19.5 mg DMAP were added as the catalyst
  • Example IX was repeated with 0.12 g DAB(PA) 64 (20% L-tyrosine; 80% d-phenylalanine) and 0.33 g PPO. 3.5 mg CuCl and 6.7 mg DMAP were added as the catalyst.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyethers (AREA)

Abstract

Oxyde d'oligophénylène à fonction multihydroxy obtenu par la mise en réaction entre, d'une part, d'un composé renfermant un hydroxyaryle comportant au moins trois groupes hydroxyaryle répondant à la formule (I), dans laquelle R1 représente un groupe aromatique, aliphatique ou cycloaliphatique contenant 1 à 50 atomes de carbone, R2 et R3 représentent H ou un groupe aromatique, aliphatique ou cycloaliphatique contenant 1 à 50 atomes de carbone, ou deux des groupes R?1, R2 et R3¿ constituent ensemble une structure cyclique contenant 4 à 50 atomes de carbone, et d'autre part, d'un oxyde de polyphénylène, ladite réaction s'effectuant en présence d'un complexe catalytique comportant un métal de transition et une amine.
PCT/NL1995/000242 1994-07-11 1995-07-10 Oxyde d'oligophenylene a fonction multihydroxy WO1996001865A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU28092/95A AU2809295A (en) 1994-07-11 1995-07-10 Multihydroxy-functional oligophenylene oxide

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE9400644 1994-07-11
BE9400644 1994-07-11

Publications (1)

Publication Number Publication Date
WO1996001865A1 true WO1996001865A1 (fr) 1996-01-25

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WO (1) WO1996001865A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998036015A1 (fr) * 1997-02-14 1998-08-20 General Electric Company Redistribution d'ethers de polyphenylene et ethers de polyphenylene a nouvelle structure
WO2001079352A1 (fr) * 2000-04-13 2001-10-25 General Electric Company Compositions a fluidite elevee d'ether de polyphenylene et de polymeres dendritiques
US6794450B2 (en) 2002-03-06 2004-09-21 General Electric Company High flow compositions of compatibilized poly(arylene ether) polyamide blends
KR100470692B1 (ko) * 1999-10-12 2005-03-07 르 라보레또레 쎄르비에르 시아노-인돌 세로토닌 재흡수 억제 화합물, 이의 제조방법 및 이를 함유하는 약제 조성물
EP1832617A2 (fr) 2006-03-10 2007-09-12 Mitsubishi Gas Chemical Company, Inc. Oligomère d'éther de phénylène polyfonctionnel, son dérivé, composition de résine les contenant et leur utilisation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1119914A (en) * 1966-05-03 1968-07-17 Gen Electric Improvements in "equilibration of poly-(1,4-phenylene ethers)"
NL6803930A (fr) * 1967-03-22 1968-09-23
EP0215257A1 (fr) * 1985-08-14 1987-03-25 Bayer Ag Procédé pour la préparation d'oligo(oxydes de phénylène) monofonctionnels ou bifonctionnels
EP0550209A2 (fr) * 1991-12-31 1993-07-07 General Electric Company Résines d'éther de polyphénylène

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1119914A (en) * 1966-05-03 1968-07-17 Gen Electric Improvements in "equilibration of poly-(1,4-phenylene ethers)"
NL6803930A (fr) * 1967-03-22 1968-09-23
EP0215257A1 (fr) * 1985-08-14 1987-03-25 Bayer Ag Procédé pour la préparation d'oligo(oxydes de phénylène) monofonctionnels ou bifonctionnels
EP0550209A2 (fr) * 1991-12-31 1993-07-07 General Electric Company Résines d'éther de polyphénylène

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
D. M. WHITE: "The synthesis of 4-hydroxyarylene ethers by the equilibration of phenols with poly(2,6-dimethyl-1,4-phenylene ether)", JOURNAL OF ORGANIC CHEMISTRY., vol. 34, no. 2, February 1969 (1969-02-01), EASTON US, pages 297 - 303 *
G. D. COOPER ET AL: "The redistribution of hydroxyarylene ethers", AM. CHEM. SOC. DIV. POLYMERS CHEM. PREPRINTS, vol. 7, no. 1, 1966, pages 166 - 172 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998036015A1 (fr) * 1997-02-14 1998-08-20 General Electric Company Redistribution d'ethers de polyphenylene et ethers de polyphenylene a nouvelle structure
US5880221A (en) * 1997-02-14 1999-03-09 General Electric Company Redistribution of polyphenylene ethers and polyphenylene ethers with novel structure
KR100470692B1 (ko) * 1999-10-12 2005-03-07 르 라보레또레 쎄르비에르 시아노-인돌 세로토닌 재흡수 억제 화합물, 이의 제조방법 및 이를 함유하는 약제 조성물
WO2001079352A1 (fr) * 2000-04-13 2001-10-25 General Electric Company Compositions a fluidite elevee d'ether de polyphenylene et de polymeres dendritiques
US6414084B1 (en) 2000-04-13 2002-07-02 General Electric Company High flow polyphenylene ether formulations with dendritic polymers
US6809159B2 (en) 2000-04-13 2004-10-26 General Electric Company High flow polyphenylene ether formulations with dendritic polymers
CN1315946C (zh) * 2000-04-13 2007-05-16 通用电气公司 有枝状聚合物的高流动性聚苯醚配方
US6794450B2 (en) 2002-03-06 2004-09-21 General Electric Company High flow compositions of compatibilized poly(arylene ether) polyamide blends
EP1832617A2 (fr) 2006-03-10 2007-09-12 Mitsubishi Gas Chemical Company, Inc. Oligomère d'éther de phénylène polyfonctionnel, son dérivé, composition de résine les contenant et leur utilisation
EP1832617A3 (fr) * 2006-03-10 2013-10-16 Mitsubishi Gas Chemical Company, Inc. Oligomère d'éther de phénylène polyfonctionnel, son dérivé, composition de résine les contenant et leur utilisation

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