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WO1992021651A1 - Nouveaux composes aromatiques a fonctionnalisation propenyle - Google Patents

Nouveaux composes aromatiques a fonctionnalisation propenyle Download PDF

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Publication number
WO1992021651A1
WO1992021651A1 PCT/GB1992/000995 GB9200995W WO9221651A1 WO 1992021651 A1 WO1992021651 A1 WO 1992021651A1 GB 9200995 W GB9200995 W GB 9200995W WO 9221651 A1 WO9221651 A1 WO 9221651A1
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WO
WIPO (PCT)
Prior art keywords
propenyl
cyanatidophenyl
compound
bis
cyanate
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/GB1992/000995
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English (en)
Inventor
Ian Hamerton
John Michael Barton
John Charles Stedman
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University of Surrey
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University of Surrey
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Filing date
Publication date
Application filed by University of Surrey filed Critical University of Surrey
Publication of WO1992021651A1 publication Critical patent/WO1992021651A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C261/00—Derivatives of cyanic acid
    • C07C261/02—Cyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/20—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • This invention relates to b ..(3-propenyl-4-cyanatidophenyl) and bis(3,5- ipropenyl-4-cyanatidophenyl) compounds of the general formula
  • R has 1-4 carbon atoms and is alkyl or perfluoroalkyl
  • Y is a direct bond, 0. CO, S, or SO2
  • Z is arylene (preferably para- or mew-phenylenej, each Y and ' /. may be the same or different where occurring more than once, and n is 0 or an integer in the range 1 to about 30 such that the compound has a molecular weight of not more i an 10, 000.
  • ⁇ ' heat resistance, toughness, low dielectric loss and low moisture absorption They have a suitable combination ⁇ ' heat resistance, toughness, low dielectric loss and low moisture absorption, and may serve as matrix resins for structural composites and laminating resins for microelectronic applications, e.g., in the manufacture of printed circuit boards.
  • JP A 1-306405 published 11 December 1989 described some cyanate- i ' unctionalized esters in which the additional functionalization was allyl rather than propenyl, and one of these monomers has been evaluated in this work as a reference standard.
  • the allyl- fimctionalized compounds are believed to react with comonomers such as bis- maleimides by a sequence of ENE/Diels-Alder reactions. They are generally less reactive than the propenyl-functionalized compounds of the present invention which probably undergo a Diels-Alder reaction without a preliminary ENE reaction.
  • the compounds of the present invention which have both cyanate and propenyl functions are obtained as predominantly the trans geometrical isomer (the transxis ratio may vary from 20:1 to 4:1) which may be isolated as a crystalline solid.
  • the compounds of the present invention are conveniently prepared using as starting material a 3.3'-diallyI or 3,3',5,5'-tetra-allylbi5-phenol containing the desired group X, which itself may be made by hearing the bis -phenol by heating with allyl bromide in the presence of sodium hydroxide to give the di-allyl to-phenol and then treating the latter in the same way to give the tetra-allyl bis-phenol.
  • allyl t ⁇ -phenol is then isomerized to the propenyl bw-phenol by heating under reflux with potassium hydroxide in methanol as described in GB 2012781 A published 1st October 1979, and the phenolic groups are esterified to cyanate ester groups using cyanogen bromide and triethylamine.
  • the final products are novel, the chemistry involved in the preparative steps is well known.
  • the comonomers (and catalytic blend if desired, e.g., a transition metal helate or carboxylate such as copper(II) naphthenate, 300 ppm Cu 2+ and an involatile phenol such as nonylphenol, 4 parts per hundred parts resin) are heated gently with stirring until both become molten. The reactants are then quenched to form a prepolymer blend which on further heating may react to form the desired copolymer.
  • the rheological properties may be tailored to the specific application.
  • Infra-red spectra were recorded with a Perkin-Elmer 1750 Fourier transform infra-red spectrometer interfaced with a Perkin-Elmer 7300 computer; the samples were presented as either thin films or as KBr disks depending on the physical state of the material.
  • DSC Dynamic differential scanning calorimetry
  • DMTA Dynamic mechanical thermal analysis
  • the melting points were determined using a Koffler hot-stage microscope.
  • di-allyl or tetra-allyl derivatives prepared from other bzs-phenols such as bis(4- hydroxyphenyl) sulphide, b i , (4-hydroxyphenyl) ether, b j'(4-hydroxyphenyl) ketone and 4.4'-dihydroxy-biphenyl, by heating with allyl bromide in the presence of sodium hydroxide.
  • the reaction mixture was cooled to room temperature, acidified with concentrated hydrochloric acid (20 ml.) and xtracted into dichloromethane (3 x 30 ml).
  • the product thus appeared to exist as two geometric isomers in distinctly different physical states.
  • the rr ⁇ /tf-isomer crystallized as a waxy white solid, while the t zv-isomer remained as a mobile amber oil at room temperature.
  • the FT-IR spectrum of the product displayed the appearance of an intense doublet at 2272 cm" 1 and 221 1 cm - 1 corresponding to the C ⁇ N stretch and enaracteristic of compounds bearing the cyanato group. This was accompanied by the disappearance of the intense broad absorbance at ca. 3300-3600 cm" 1 corresponding to the O-H stretch of t ⁇ -phenols and was of greatest diagnostic use in this respect.
  • the product was prepared substantially as described in example 1.
  • the diallyl ether was first prepared from 5 g (12 mmole) of 2,2'-bj._(4-hydroxyphenyl) hexafluoroisopropylidene (b/s-phenol-AF ⁇ ) by treatment with sodium hydroxide and two molar equivalents of allylbromide in a toluene/water mixture containing a tetramethylammonium bromide - a phase transfer catalyst (and heating the resulting mixture at 50-60°C for twenty hours).
  • the diallyl-b/_ * -phenol was then prepared from the diallyl ether via a Claisen rearrangement by heating at ca. 200-205°C for twenty- four hours.
  • the product was prepared substantially as described in example 1.
  • the diallyl ether was first prepared from 5 g (15 mmole) of to(4-hydroxyphenyl)sulphone (bis- phenol-S) by treatment with sodium hydroxide and two molar equivalents of allylbromide in a toluene/water mixture containing a tetramethylammonium bromide - a phase transfer catalyst (and heating the resulting mixture at 50-60°C for fifteen hours).
  • the diallyl-bw-phenol was then prepared from the diallyl ether via a Claisen rearrangement by heating at ca. 200-205°C for twenty-four hours.
  • Rhone-Poulenc Rhone-Poulenc.
  • the allyl-functionalized cyanate ester (4) was used as a standard against which the properties of the new materials might be gauged. In the first instance, the relative reactivity of the functionalized cyanate esters was assessed using dynamic DSC (Table 1 ). The allyl derivative (4) displays a higher polymerization onset temperature than the propenyl analogue (1) by some 40°C indicating the greater thermal reactivity of the latter.
  • the prepolymer blend (containing the cyanate esters and b s-maleimides) was applied to Courtaulds XAS carbon fibre (containing 1% epoxy size) by solution coating in a volatile transport solvent (dichloromethane or acetone) and then wound onto a drum to form prepreg.
  • the unidirectional laminates were laid up (10- or 18-ply, 0°) and, after drying in an oven at 50°C for one hour to remove residual solvent, underwent the following curing cycle in an autoclave. After lay-up on the bed plate a vacuum was applied (and held overnight).
  • a pressure of 6 bar (100 psi) was applied at the start of the run and the vacuum vented when the pressure reached 2 bar.
  • the temperature was raised at 2°C min *-1 to 180°C and then held at 180°C for 3 hours.
  • the cured panels were then cooled at 3°C min -1 to 65°C before being released from the bed plate.
  • the coarse formulations (Table 2) relates to mixtures containing 50% and 337c of the new material ( 1). It is envisaged that the new propenyl-functionalized cyanate esters will be used in smaller quantities in a BMI blend as toughening modifiers and so a range of formulations was prepared in which the BMI content (6) was fixed at 50% and the ratio of cyanate esters (5 and 1) was varied (Table 3). In this way it was hoped that an optimum ratio of functionalized:commercial cyanate ester might be determined.
  • Laminate cannot be fabricated without excessive void content leading to inconsistent results.

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Nouveaux composés bis(3-propényl-4-cyanatidophenyle) et bis(3,5-dipropenyl-4-cyanatidophényle) de la formule générale respective (I) dans laquelle A est H- ou CH3-CH=CH-, X est -CH2-, -CR2-, -C(=O)-O-, -Y-, ou -Z-(-Y-Z)n, dans laquelle R comporte 1 à 4 atomes de carbone et représente alkyle ou perfluoroalkyle, Y représente une liaison directe, O, CO, S, ou SO2, Z représente arylène (de préférence para- ou méta-phénylène), Y et Z peuvent chacun être identiques ou différents lorsqu'ils se présentent plus d'une fois, et n représente O ou un nombre entier compris dans une plage de 1 à environ 30 de telle façon que le composé possède un poids moléculaire n'excédant pas 10,000. Les composés de la présente invention sont roéparés en utilisant comme produit de départ un diallyle, ou tétra-allylbis-phénol contenant le groupe X désiré, qui est isomérisé pour obtenir le dipropényle ou le tétrapropényle bis-phénol par chauffage sous reflux avec de l'hydroxide de potassium dans le méthanol. Les groupes phénoliques sont estérifiés en groupes ester de cyanate en utilisant du bromure de cyanogéne et une triéthylamine, et le composé possédant à la fois des fonctions cyanate et propényle est obtenu sous la forme de l'isomère géométrique trans. Il peut être polymérisé seul ou de préférence par co-réaction avec des composés bis-maleimides, bis-citraconimides, aspartimides contenant des groupes époxide ou des esters de cyanate. Les produits polymères peuvent servir de résines matricielles pour des composites structuraux et des résines pour stratifiés dans des applications microélectroniques, par ex., dans la fabrication de cartes de circuits imprimés. On a découvert que des stratifiés renforcés par des fibres de carbone incorporant des composés de l'invention avec des bis-maléimides et de monomères d'esters de cyanate de type commercial présentent des propriétés mécaniques améliorées, avec notamment du point de vue de la tenacité à la rupture et de la possiblité de traitement comparé aux homopolymères.
PCT/GB1992/000995 1991-06-04 1992-06-03 Nouveaux composes aromatiques a fonctionnalisation propenyle Ceased WO1992021651A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB919111940A GB9111940D0 (en) 1991-06-04 1991-06-04 Novel propenyl-functionalized aromatic compounds
GB9111940.4 1991-06-04

Publications (1)

Publication Number Publication Date
WO1992021651A1 true WO1992021651A1 (fr) 1992-12-10

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WO (1) WO1992021651A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2318787A (en) * 1996-10-29 1998-05-06 Secr Defence Unsymmetrical alkenyl cyanate oligomers
US6616984B1 (en) 1997-10-10 2003-09-09 Miguel Albert Capote Forming viaholes in composition of cyanate, bismaleimide, epoxy resin and unsaturated aromatic glycidyl
JP2009191218A (ja) * 2008-02-18 2009-08-27 Sumitomo Bakelite Co Ltd 回路基板用樹脂組成物、プリプレグおよび積層板
WO2011005515A3 (fr) * 2009-06-22 2011-05-05 Arbiser Jack I Analogues de bis-trifluorométhyl honokiol et leur utilisation dans le traitement de cancers
CN109982993A (zh) * 2016-11-15 2019-07-05 赢创工业化学有限公司 不对称取代的双烯基二苯醚、它们的制备和用途

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2012781A (en) * 1978-01-20 1979-08-01 Ciba Geigy Ag Hydroxyl-containing compositions and their polymerisation
JPH01306405A (ja) * 1988-06-03 1989-12-11 Hitachi Ltd オルトジアリルビスシアナート系化合物、及び、この化合物を含む組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2012781A (en) * 1978-01-20 1979-08-01 Ciba Geigy Ag Hydroxyl-containing compositions and their polymerisation
JPH01306405A (ja) * 1988-06-03 1989-12-11 Hitachi Ltd オルトジアリルビスシアナート系化合物、及び、この化合物を含む組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 14, no. 96 (C-692)22 February 1990 & JP,A,1 306 405 ( HITACHI LTD. ) 11 December 1989 cited in the application *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2318787A (en) * 1996-10-29 1998-05-06 Secr Defence Unsymmetrical alkenyl cyanate oligomers
WO1998018755A1 (fr) * 1996-10-29 1998-05-07 The Secretary Of State For Defence Oligomeres d'alcenyle-cyanate non symetriques
US6616984B1 (en) 1997-10-10 2003-09-09 Miguel Albert Capote Forming viaholes in composition of cyanate, bismaleimide, epoxy resin and unsaturated aromatic glycidyl
JP2009191218A (ja) * 2008-02-18 2009-08-27 Sumitomo Bakelite Co Ltd 回路基板用樹脂組成物、プリプレグおよび積層板
WO2011005515A3 (fr) * 2009-06-22 2011-05-05 Arbiser Jack I Analogues de bis-trifluorométhyl honokiol et leur utilisation dans le traitement de cancers
US8889744B2 (en) 2009-06-22 2014-11-18 Jack L. Arbiser Bis-trifluoromethyl honokiol analogs and their use in treating cancers
CN109982993A (zh) * 2016-11-15 2019-07-05 赢创工业化学有限公司 不对称取代的双烯基二苯醚、它们的制备和用途
JP2019535640A (ja) * 2016-11-15 2019-12-12 エボニック テクノケミー ゲーエムベーハー 非対称に置換されたビス−アルケニルジフェニルエーテルならびにそれらの製造および使用
CN109982993B (zh) * 2016-11-15 2022-06-07 赢创运营有限公司 不对称取代的双烯基二苯醚、它们的制备和用途

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Publication number Publication date
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