WO1990008796A1 - Phenols polyhydriques servant de prolongateurs de chaine pour certaines resines de bismaleimide - Google Patents

Phenols polyhydriques servant de prolongateurs de chaine pour certaines resines de bismaleimide Download PDF

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Publication number
WO1990008796A1
WO1990008796A1 PCT/US1990/000543 US9000543W WO9008796A1 WO 1990008796 A1 WO1990008796 A1 WO 1990008796A1 US 9000543 W US9000543 W US 9000543W WO 9008796 A1 WO9008796 A1 WO 9008796A1
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WO
WIPO (PCT)
Prior art keywords
chain
group
hydroxyphenyl
bmi
phenol
Prior art date
Application number
PCT/US1990/000543
Other languages
English (en)
Inventor
Raymond J. Swedo
Joseph J. Zupanaic
Original Assignee
Allied-Signal Inc.
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 Allied-Signal Inc. filed Critical Allied-Signal Inc.
Priority to KR1019900702119A priority Critical patent/KR910700290A/ko
Publication of WO1990008796A1 publication Critical patent/WO1990008796A1/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
    • 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
    • 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
    • C08G73/124—Unsaturated polyimide precursors the unsaturated precursors containing oxygen in the form of ether bonds in the main chain
    • 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
    • C08G73/125—Unsaturated polyimide precursors the unsaturated precursors containing atoms other than carbon, hydrogen, oxygen or nitrogen in the main chain

Definitions

  • Michael addition generally is a base-catalyzed reaction, and since amines as bases serve as their own catalysts this is one reason why amines usually are quite reactive in Michael addition.
  • the reaction with nitrogen-substituted maleimides requires a .base catalyst as an additional component; A. Renner et al., Helv. Chim. Acta., 61, 1443 (1978).
  • the pu ⁇ ose of this invention is to prepare bismaleimide resins chain extended with polyhydric phenols in the absence of a catalyst.
  • An embodiment comprises the reaction of certain di-ortho-substituted BMIs, as exemplified by 1,2-bis(2-maleimidophenylthio) ethane, with polyhydric phenols in the absence of any third component as catalyst.
  • the polyhydric phenol is a dihydric phenol.
  • the dihydric phenol is hexafluorobisphenol A.
  • thermosetting resin which is the chain-extended reaction product of certain di-ortho-substituted bismaleimides such as 1,2-bis(2-maleimidophenylthio)ethane with polyhydric phenols and which contains no third component
  • thermosetting resin which is the chain-extended reaction product of certain di-ortho-substituted bismaleimides such as 1,2-bis(2-maleimidophenylthio)ethane with polyhydric phenols and which contains no third component
  • Yet another embodimerit is the cured resin resulting from thermal treatment of the preceding thermosetting resin.
  • R a and R b each independently is hydrogen, an alkyl or alkoxy group containing up to 4 carbon atoms, chlorine, or bromine, or R a and R b together form a fused 6-membered hydrocarbon aromatic ring, with the proviso that R a and R b are not t-butyl or t-butoxy, where X is O, S, or Se, i is 1-3, and the alkylene bridging group is optionally substituted by 1-3 methyl groups or by fluorine.
  • the bismaleimide is 1,2-bis(2-maleimidophenytthio)ethane.
  • polyhydric phenol a compound haying at least 1 aromatic ring and having at least 2 hydroxyl groups attached to the aromatic ring(s) in the compound.
  • the most important class of polyhydric phenols is that of dihydric phenols, and within this class the subset of broadest availability is that of the resorcinols, i.e., 1,3-dihydroxybenzenes optionally substituted with one or more alkyl groups on the aromatic ring, particularly where the alky group contains from 1 through about 6 carbon atoms.
  • Examples include 2-methyiresorcinol, 4-methyiresorcinol, 5-methyiresorcinol 6-methylresorcinol 4-ethyiresorcinol, 4-propyiresorcinol, 5-pentyiresorcinol, 5-hexyiresorcinol 2,4-dimethyiresorcinol, 2,5-dimethyiresorcinol, 4,5-dimethylresorcinol, 4,6-di methylresorcinol, and so forth.
  • Illustrative examples include pyrocatechol, 3-methylpyrocatechol, 4-methylpyrocatechol, the ethylpyrocatechols, propylpyrocatechols, butyipyrocatechols, pentylpyrocatechols, hexylpyrocatechols, hydroquinone, the alkyl-substituted hydroquinones where the alkyl group contains from 1 through 6 carbon atoms, the dialkyl-substiluted hydroquinones, and so on.
  • dihydric phenols is that of the dihydroxynaphthalenes where the hydroxyl groups may be on the same or on different rings.
  • Illustrative members of this class include 1,2-dihydroxynaphthalene, 1,3-dihydroxy-naphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-di-hydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxy-naphthalene, etc.
  • phenols which are at least trihydric may be mentioned tetraphenolethane (1,1,2,2-tetrakis(hydroxyphenyl)ethane), 1,1,1-tris(hydroxyphenyl)ethane, tris(hydroxyphenyl)methane, tetrakis(hydroxyphenyl)methane,
  • the polyhydric phenol will be used in a molar proportion relative to the bismaleimide as little as about 0.05 and as great as about 2. That is, the molar ratio of BMI to polyhydric phenol used in the preparation of the chain-extended BMI may be as great as 20:1 or as little as 0.5:1. Quite often little change is seen in the resulting product when less than about 0.1 molar proportion of polyhydric phenol is employed, and the glass transition temperature often is adversely affected when more than 1 molar proportion is employed. Consequently a molar proportion of polyhydric phenol relative to BMI which is preferred in the practice of our invention is from about 0.1 to about 1.0.
  • the resulting chain-extended BMIs begin to undergo thermal polymerization in the range from about 170°C up to at least 250°C. However, polymerization peaks at a temperature between about 250°C up to at least 320°C Thermal curing is perhaps most preferably done in an inert atmosphere, such as nitrogen.
  • the dielectric constant and loss factors for our chain-extended BMIs are superior to those of either the non-extended BMI or to a typical diamine chain-extended BMI.
  • the coefficient of thermal expansion of all of our cured chain-extended BMIs are comparable to the parent or diamine chain-extended BMIs, as are water and methylene chlo ride absorption properties.
  • Flexural data show that polyhydric phenol chain extension has reduced brittleness and improved toughness of the cured resin over that of the cured non-extended BMI.
  • the chain-extended BMIs of our invention also have broader processing windows than their diamine chain-extended counterparts, exhibiting a difference of at least 100°C between their melting point and the onset of thermal polymerization.
  • chain extension with polyhydric phenols produces BMI resins having properties which are comparable or superior to those of diamine chainextended counterparts, but without the complications of aromatic diamine toxicity and carcinogenicity.
  • TPE 1,1,2,2,-tetrakis(hydroxyphenyl)ethane
  • Dielectric constants ( ⁇ ) and loss factors (tans) were determined using a Digibridge system at 1MHz and 23°C. Samples were preequilibrated at 0% and 50% relative humidity prior to testing.
  • Flexural Properties were determined by the 4 point bend te»st at room temperature following ASTM-D790. A loading span of 1.016", and a support span of 2.032" were used.
  • Tables 1-4 summarize some salient characteristics of chain extended resins and the cured resins therefrom.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Pyrrole Compounds (AREA)

Abstract

Une classe de bismaléimides di-ortho-substituées subit une addition de Michael non catalysée à des phénols polyhydriques afin d'obtenir des bismaléimides à chaîne prolongée présentant une capacité de traitement beaucoup plus étendue que le parent non prolongé. Les résines entièrement polymérisées présentent une meilleure ténacité à la rupture, et se caractérisent généralement par une constante diélectrique et une perte diélectrique comparables ou supérieures, et ne présentent pas de dégradation en ce qui concerne d'autres propriétés telles que la résistance à l'humidité, au chlorure de méthylène, et le coefficient de dilatation thermique.
PCT/US1990/000543 1989-02-02 1990-01-30 Phenols polyhydriques servant de prolongateurs de chaine pour certaines resines de bismaleimide WO1990008796A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019900702119A KR910700290A (ko) 1989-02-02 1990-01-30 다가페놀을 이용한 비스말레이미드 수지의 쇄확장방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US30600289A 1989-02-02 1989-02-02
US306,002 1989-02-02

Publications (1)

Publication Number Publication Date
WO1990008796A1 true WO1990008796A1 (fr) 1990-08-09

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Country Status (5)

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EP (1) EP0456717A1 (fr)
JP (1) JPH04503082A (fr)
KR (1) KR910700290A (fr)
CA (1) CA2009018A1 (fr)
WO (1) WO1990008796A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4100140A (en) * 1975-06-19 1978-07-11 Ciba-Geigy Corporation Process for the manufacture of crosslinked polymers which contain imide groups
US4288583A (en) * 1978-12-29 1981-09-08 Ciba-Geigy Corporation Curable mixtures based on maleimides and 1-propenyl-substituted phenols
US4464520A (en) * 1982-08-12 1984-08-07 The United States Of America As Represented By The United States Department Of Energy Delayed cure bismaleimide resins
US4564683A (en) * 1982-08-12 1986-01-14 The United States Of America As Represented By The United States Department Of Energy Bismaleimide compounds
EP0296112A2 (fr) * 1987-06-18 1988-12-21 Ciba-Geigy Ag Compositions durcissables stable au stockage

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4100140A (en) * 1975-06-19 1978-07-11 Ciba-Geigy Corporation Process for the manufacture of crosslinked polymers which contain imide groups
US4288583A (en) * 1978-12-29 1981-09-08 Ciba-Geigy Corporation Curable mixtures based on maleimides and 1-propenyl-substituted phenols
US4464520A (en) * 1982-08-12 1984-08-07 The United States Of America As Represented By The United States Department Of Energy Delayed cure bismaleimide resins
US4564683A (en) * 1982-08-12 1986-01-14 The United States Of America As Represented By The United States Department Of Energy Bismaleimide compounds
EP0296112A2 (fr) * 1987-06-18 1988-12-21 Ciba-Geigy Ag Compositions durcissables stable au stockage

Also Published As

Publication number Publication date
KR910700290A (ko) 1991-03-14
CA2009018A1 (fr) 1990-08-02
EP0456717A1 (fr) 1991-11-21
JPH04503082A (ja) 1992-06-04

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