CA1317305C - Alpha, alpha', alpha''-tris (4-cyanatophenyl)-1,3,5- triisopropylbenzenes and resins thereof - Google Patents
Alpha, alpha', alpha''-tris (4-cyanatophenyl)-1,3,5- triisopropylbenzenes and resins thereofInfo
- Publication number
- CA1317305C CA1317305C CA 614319 CA614319A CA1317305C CA 1317305 C CA1317305 C CA 1317305C CA 614319 CA614319 CA 614319 CA 614319 A CA614319 A CA 614319A CA 1317305 C CA1317305 C CA 1317305C
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- Canada
- Prior art keywords
- alpha
- cyanato
- maleimide
- amine
- curable resin
- 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.)
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Classifications
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- 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
- C08G73/0644—Poly(1,3,5)triazines
-
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31721—Of polyimide
Abstract
A B S T R A C T
ALPHA, ALPHA', ALPHA"-TRIS(4-CYANATOPHENYL)-1,3,5-TRIISOPROPYLBENZENES AND RESINS THEREOF
Alpha, alpha', alpha"-tris(4-cyanatophenyl)-1,3,5-triisopro-pylbenzenes are new and useful for preparing high heat resistant resins having a low dielectric constant, particularly for electri-cal applications.
ALPHA, ALPHA', ALPHA"-TRIS(4-CYANATOPHENYL)-1,3,5-TRIISOPROPYLBENZENES AND RESINS THEREOF
Alpha, alpha', alpha"-tris(4-cyanatophenyl)-1,3,5-triisopro-pylbenzenes are new and useful for preparing high heat resistant resins having a low dielectric constant, particularly for electri-cal applications.
Description
~3~7~5 ALPHA, ALPHA', ALPHA"-TRIS(4-CYANATOPHENYL)-1,3,5-TRIISOPROPYLBENZENES AND RESINS THEREOF
The present invention relates to novel alpha, alpha', alpha"-tris(4-cyanatophenyl)-1,3,5-triisopropylbenzenes and resins there-of.
Cyanato resins are occasionally found in the art for use in adhesives, coatings and the like. U~S. patent 3,595,900 and a division thereof 3,738,962 describe cyanatophenyl-terminated polyarylene ethers. U.S. patents 3,755,402; 4,110,364; 4,157,360;
4,403,073; and 4,554,346 describe other cyanato esters and resins thereof, including mixtures thereof with (1) a bismaleimide, (2) a thermoplastic polymer, (3) certain polybutadiene, and optionally a maleimide or (4) a hydroxy unsaturated compound. These resins generally describe relatively linear components having only one or two aromatic rings which may or may not be separated by ether oxygens.
There is a need in electrical applications for unique resins having a low dielectric constant, high solubility and low moisture uptake as well as a high glass transition temperature (Tg) in cured laminates, particularly in those applications where a fast electri-cal signal time is required as in advanced computer circuitry and the present invention is directed to new resins possessing such a desirable combination of properties.
The present invention is directed to novel alpha, alpha',alpha"-tris(4-cyanatophenyl)-1,3,5-triisopropylbenzenes of formula I:
The present invention relates to novel alpha, alpha', alpha"-tris(4-cyanatophenyl)-1,3,5-triisopropylbenzenes and resins there-of.
Cyanato resins are occasionally found in the art for use in adhesives, coatings and the like. U~S. patent 3,595,900 and a division thereof 3,738,962 describe cyanatophenyl-terminated polyarylene ethers. U.S. patents 3,755,402; 4,110,364; 4,157,360;
4,403,073; and 4,554,346 describe other cyanato esters and resins thereof, including mixtures thereof with (1) a bismaleimide, (2) a thermoplastic polymer, (3) certain polybutadiene, and optionally a maleimide or (4) a hydroxy unsaturated compound. These resins generally describe relatively linear components having only one or two aromatic rings which may or may not be separated by ether oxygens.
There is a need in electrical applications for unique resins having a low dielectric constant, high solubility and low moisture uptake as well as a high glass transition temperature (Tg) in cured laminates, particularly in those applications where a fast electri-cal signal time is required as in advanced computer circuitry and the present invention is directed to new resins possessing such a desirable combination of properties.
The present invention is directed to novel alpha, alpha',alpha"-tris(4-cyanatophenyl)-1,3,5-triisopropylbenzenes of formula I:
- 2 - ~ 3 ~ ~ 3 ~ ~
OCsN
Rn CH3 ~ C - CH3 (I) 3 ~ 3 ~ CH3 CH3 ~
NsCO OCsN
wherein in each R is independently an alkyl group containing from 1 to 4 carbon atoms, preferably a methyl group, and each n is inde-pendently 0, 1 or 2.
The compounds of formula I are prepared by treating the corresponding known alpha, alpha', alpha"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzenes with a compound which will react with a hydroxy group to yield a cyanato group, e.g., a cyanogen halide such as cyanogen bromide or the like. A slight excess of cyano reactant is preferred.
The reaction is conducted in the presence of a base including alkali metal hydroxides, aliphatic amines and the like, such as triethylamine, sodium hydroxide or the like. It is preferred to adjust the addition rate of the base during the reaction such that always an excess of cyanogen halide over base is present.
The reaction is conducted at low temperatures in view of the exothermic nature of the reaction and the volatility of the cyano-gen halide. For example, the temperature is from -40C to 40C, preferably -20C to 10C. The use of conventional inert liquid organic solvents is preferred, including aromatic hydrocarbons, such as benzenes, toluene or xylene; ethers, such as diethyl ether or tetrahydrofuran; halogenated aliphatic or aromatic hydrocar-bons, such as methylene chloride or chlorobenzene; alcohols such as methanol, ethanol, or isopropyl alcohol; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone and the like.
3L ~ 1 r~ 3 ~ ~
The invention also provides a curable resin composition comprising:
(a) (i) at least one compound according to any one of claims 1 to 3; or (ii) a homopolymeri.zation product of a compound according to any one of claims l to 3; or (iii) the polymerlc product of the reaction of a compound according to any one of claims 1 to 3 with an amine, and optionally at least one of (b) the copolymerizati.on product of a compound according to any one of claims 1 to 3 with a second cyanato ester, with at least one of (1) (i) a second cyanato ester;
(ii) a homopolymerization product of a second cyanato ester;
(iii) a polymeric product of the reaction of a second cyanato ester and with an amine;
(2) an amine, or (c) (i) a ma].eimide component;
(ii) a polymeric product of the reaction of a maleimide and an amine; or (iii) a polymeric product of the reaction of more than one maleimide and an amine.
Because of their unique combination of properties, such curable resin compositions are useful in the preparakion of various articles of manufacture. Thus, the invention also includes prepregs of the above composition as well as shaped '. ~
.` ~
~ 3~73~
-3a- 63293-3167 articles, xeinforced compositions, electrical laminates and the like as hereinafter descrihed from cured or partially cured above resin compositions of the compound of formula I of the invention.
Thus, the cyanato compound of formula I of the present invention in which n is zero is particularly useful as a monomer, intermediate or prepolymer for the preparation of cyanato polymers. Polymerization of the cyanates is accomplished by heating the cyanates of formula I to effect their thermal polymerization. Homopolymers of the cyanates of formula I as well as copolymers of two or more cyanates can be prepared in this fashion.
The thermal polymerization of the cyanates, in accordance with this invention, involves trimerization of terminal cyanato groups to form a cyanate that has a three-dimensional network structure with polyarylene linkages between cyanato rings, the polymerization being illustrated in formula II:
OCsN
Rn CH3 ~ C - CH3 (I) 3 ~ 3 ~ CH3 CH3 ~
NsCO OCsN
wherein in each R is independently an alkyl group containing from 1 to 4 carbon atoms, preferably a methyl group, and each n is inde-pendently 0, 1 or 2.
The compounds of formula I are prepared by treating the corresponding known alpha, alpha', alpha"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzenes with a compound which will react with a hydroxy group to yield a cyanato group, e.g., a cyanogen halide such as cyanogen bromide or the like. A slight excess of cyano reactant is preferred.
The reaction is conducted in the presence of a base including alkali metal hydroxides, aliphatic amines and the like, such as triethylamine, sodium hydroxide or the like. It is preferred to adjust the addition rate of the base during the reaction such that always an excess of cyanogen halide over base is present.
The reaction is conducted at low temperatures in view of the exothermic nature of the reaction and the volatility of the cyano-gen halide. For example, the temperature is from -40C to 40C, preferably -20C to 10C. The use of conventional inert liquid organic solvents is preferred, including aromatic hydrocarbons, such as benzenes, toluene or xylene; ethers, such as diethyl ether or tetrahydrofuran; halogenated aliphatic or aromatic hydrocar-bons, such as methylene chloride or chlorobenzene; alcohols such as methanol, ethanol, or isopropyl alcohol; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone and the like.
3L ~ 1 r~ 3 ~ ~
The invention also provides a curable resin composition comprising:
(a) (i) at least one compound according to any one of claims 1 to 3; or (ii) a homopolymeri.zation product of a compound according to any one of claims l to 3; or (iii) the polymerlc product of the reaction of a compound according to any one of claims 1 to 3 with an amine, and optionally at least one of (b) the copolymerizati.on product of a compound according to any one of claims 1 to 3 with a second cyanato ester, with at least one of (1) (i) a second cyanato ester;
(ii) a homopolymerization product of a second cyanato ester;
(iii) a polymeric product of the reaction of a second cyanato ester and with an amine;
(2) an amine, or (c) (i) a ma].eimide component;
(ii) a polymeric product of the reaction of a maleimide and an amine; or (iii) a polymeric product of the reaction of more than one maleimide and an amine.
Because of their unique combination of properties, such curable resin compositions are useful in the preparakion of various articles of manufacture. Thus, the invention also includes prepregs of the above composition as well as shaped '. ~
.` ~
~ 3~73~
-3a- 63293-3167 articles, xeinforced compositions, electrical laminates and the like as hereinafter descrihed from cured or partially cured above resin compositions of the compound of formula I of the invention.
Thus, the cyanato compound of formula I of the present invention in which n is zero is particularly useful as a monomer, intermediate or prepolymer for the preparation of cyanato polymers. Polymerization of the cyanates is accomplished by heating the cyanates of formula I to effect their thermal polymerization. Homopolymers of the cyanates of formula I as well as copolymers of two or more cyanates can be prepared in this fashion.
The thermal polymerization of the cyanates, in accordance with this invention, involves trimerization of terminal cyanato groups to form a cyanate that has a three-dimensional network structure with polyarylene linkages between cyanato rings, the polymerization being illustrated in formula II:
4 1 3 ~L 7 3 ~ ~
OCN \ /N
x _ o ~ o _ x 3 NCO-- X--OCN ~ / I I I \
N~N (II) O
X
where X is the C~,Cr' ,~"-tris(4-hydroxyphenyl)-1,3,5-triisopropyl-benzene residue of the cyanate defined in formula I above.
Generally, the polymerization or curing of cyanates, in accordance with this invention, will be carried out by first melting the cyanato monomeric material to obtain a homogeneous melt or dissolving in a suitable solvent such as an alcohol, ketone, ester, aromatic hydrocarbon or the like and then raising the temperature to a range of 0 to 300C, preferably 100 to 250C.
Alternatively, this polymerization can be carried out at lower temperatures with the aid of known cyanate polymerization activa-tors, initiators or catalysts. These polymerization promotingagents representatively include Lewis acids, such as aluminium chloride, boron trifluoride, ferric chloride, titanium chloride, and zinc chloride; protonic acids, such as hydrochloric and other mineral acids; salts of weak acids, such as sodium acetate, sodium cyanide, sodium cyanate, potassium thiocyanate, sodium bicarbonate, sodium boronate, and phenylmercuri.c acetate; ancl bases, such as sodium methoxide, sodium hydroxide, pyridine, triethylamine, and the ].ike. Preferred catalysts are non-ionic coordination compounds, such as cobalt, iron, zinc, and copper acetylacetonates. The amount of catalyst used can vary, and generally will be 0.05 to 5 mole per cent, preferably 0.05 to 0.5 mole per cent.
The polymerization of the cyanates can also be carried out by polymerizing them in solution or in suspension, using as a solvent or suspension medium the common organic solvents such as hydrocarbons, ketones, halogenated hydrocarbons, nitrated hydrocar-bons, dimethylsulphoxide, dimethylformamide, ether or the like. The solvent can be removed by distillation or simple evaporation during the course of or at the end of the polymerization.
The various triscyanates of formula I and (co)polymers thereof in accordance with the invention are crystalline or amorphous solids which melt to flowable liquids at convenient working temper-atures. They are soluble in a vari.ety of organic solvents such as methylene chloride, chloroform, benzene, toluene, chlorobenzene, acetone, methyl ethyl ketone, ethyl benzoate, ethyl cellulose, dimethylformamide, and the like. They provide excellent bases for solvent-diluted coatings such as brush, spray, and dip coatings, particularly in the case of the higher molecular weight prepoly-mers. They can be used as one-component cured-in-place resins which show good thermal stability along with resistance to solvents and corrosive chemicals such as dilute acids, and basis. The fabrications of shaped articles from these cyanato (co)polymers is greatly facilitated in that no volatile by-products are liberated during the curing process.
The (co)polymers of this invention have relatively high molecular weight and consequently have low volatility and therefore less toxicity and can be conveniently handled at elevated tempera-tures. Also, reactions involving these cyanates can be controlled readily, in spite of exothermic heat generated, since the active cyanato groups constitute in part a small portion of the overall compound. The cyanato (co)polymers of this invention have improved strength, toughness, and impact resistance and can be used for adhesives, coatings and binders. Resistance to thermal degradation caused by aging at high temperatures is also improved because of a reduced concentration of the relatively less stable cyanato rings.
It is also within the scope of this invention to copolymerize the triscyanate of formula I with one or more mono- or dicyanato esters of the type already well known in the prior art. Preferred are aromatic cyanato esters and such comonomers useful in this invention for this purpose include those of formula III:
~ C~
OCN \ /N
x _ o ~ o _ x 3 NCO-- X--OCN ~ / I I I \
N~N (II) O
X
where X is the C~,Cr' ,~"-tris(4-hydroxyphenyl)-1,3,5-triisopropyl-benzene residue of the cyanate defined in formula I above.
Generally, the polymerization or curing of cyanates, in accordance with this invention, will be carried out by first melting the cyanato monomeric material to obtain a homogeneous melt or dissolving in a suitable solvent such as an alcohol, ketone, ester, aromatic hydrocarbon or the like and then raising the temperature to a range of 0 to 300C, preferably 100 to 250C.
Alternatively, this polymerization can be carried out at lower temperatures with the aid of known cyanate polymerization activa-tors, initiators or catalysts. These polymerization promotingagents representatively include Lewis acids, such as aluminium chloride, boron trifluoride, ferric chloride, titanium chloride, and zinc chloride; protonic acids, such as hydrochloric and other mineral acids; salts of weak acids, such as sodium acetate, sodium cyanide, sodium cyanate, potassium thiocyanate, sodium bicarbonate, sodium boronate, and phenylmercuri.c acetate; ancl bases, such as sodium methoxide, sodium hydroxide, pyridine, triethylamine, and the ].ike. Preferred catalysts are non-ionic coordination compounds, such as cobalt, iron, zinc, and copper acetylacetonates. The amount of catalyst used can vary, and generally will be 0.05 to 5 mole per cent, preferably 0.05 to 0.5 mole per cent.
The polymerization of the cyanates can also be carried out by polymerizing them in solution or in suspension, using as a solvent or suspension medium the common organic solvents such as hydrocarbons, ketones, halogenated hydrocarbons, nitrated hydrocar-bons, dimethylsulphoxide, dimethylformamide, ether or the like. The solvent can be removed by distillation or simple evaporation during the course of or at the end of the polymerization.
The various triscyanates of formula I and (co)polymers thereof in accordance with the invention are crystalline or amorphous solids which melt to flowable liquids at convenient working temper-atures. They are soluble in a vari.ety of organic solvents such as methylene chloride, chloroform, benzene, toluene, chlorobenzene, acetone, methyl ethyl ketone, ethyl benzoate, ethyl cellulose, dimethylformamide, and the like. They provide excellent bases for solvent-diluted coatings such as brush, spray, and dip coatings, particularly in the case of the higher molecular weight prepoly-mers. They can be used as one-component cured-in-place resins which show good thermal stability along with resistance to solvents and corrosive chemicals such as dilute acids, and basis. The fabrications of shaped articles from these cyanato (co)polymers is greatly facilitated in that no volatile by-products are liberated during the curing process.
The (co)polymers of this invention have relatively high molecular weight and consequently have low volatility and therefore less toxicity and can be conveniently handled at elevated tempera-tures. Also, reactions involving these cyanates can be controlled readily, in spite of exothermic heat generated, since the active cyanato groups constitute in part a small portion of the overall compound. The cyanato (co)polymers of this invention have improved strength, toughness, and impact resistance and can be used for adhesives, coatings and binders. Resistance to thermal degradation caused by aging at high temperatures is also improved because of a reduced concentration of the relatively less stable cyanato rings.
It is also within the scope of this invention to copolymerize the triscyanate of formula I with one or more mono- or dicyanato esters of the type already well known in the prior art. Preferred are aromatic cyanato esters and such comonomers useful in this invention for this purpose include those of formula III:
~ C~
S
NC0 - ~ ~ (III) where a is 0 or l and S is cyanato or an aromatic group such as benzene, naphthalene, or biphenyl, which group can have a cyanato group as a ring substitutent. The amount of such aromatic cyanate of formula III which can be copolymerized with the triscyanates of S this invention can vary and generally will be dictated by the particular properties desired to be imparted by them to the cyanato copolymers. For example, the degree of crosslinking of the copoly-mer can be increased in some instances by incorporating such aromatic short chain (di)cyanates. The heat distortion temperature of the copolymer can thereby be increased.
Where a monocyanate is copolymerized with the triscyanate of the invention, copolymeric cyanates are formed in which the network growth and crosslinking density are reduced by the chain-terminat-ing monocyanato monomer. Generally, where used, the second cyanate [component (b)(l)] will amount to 5 to 95 %wt, preferably 5 to 50 ~wt of the cyanato copolymer.
The triscyanates of the invention can also be used in the form of a prepolymer. The prepolymer is prepared by polymerizing the polyfunctional cyanato monomer in the presence of a convention-al catalyst, for example, a mineral acid, a Lewis acid, a salt sucha sodium carbonate or lithium chloride, or a phosphoric acid ester such as tributyl phosphine. The prepolymer contains a triazine ring generally in the molecule as a result of the trimerization of the cyanato group of the triscyanate. Preferred prepolymers are those having an average molecular weight of at least 400, especially up to 6000.
The cyanato ester comonomer can be used in the form of a mixture of the monomer and the prepolymer. For example, many of the comr.ercially available cyanato esters derived from bisphenol A and cyanogen halide are in the form of mixtures of cyanato monomers and prepolymers, and such materials can also be used in the present invention.
~ 3 ~. 7 ~ j,~) i^j A mixture of a prepolymer of the cyanato ester comonomer and an amine may also be used.
Generally, the cyanato ester comonomers can be prepared by known methods including reacting polyhydric phenolic materials with cyanogen halides, such as cyanogen chloride or cyanogen bromide.
Cyanate aromatic esters, which are readily available and preferred for use as comonomers in this invention in view of the properties of the final resin obtained, are those prepared by reacting a symmetrical, fused ring-free dihydric phenol, such as bisphenol A
(2,2-bis[4-hydroxyphenyl]propane) with cyanogen halides. Likewise, cyanato aromatic esters obtained by the reaction of a phenol-formaldehyde precondensate with cyanogen halides can be advanta-geously used. Suitable cyanates disclosed in U.S. patent 4,110,364;
3,595,900; 3,755,402; 4,157,360; 4,403,073; German patents 1,190,184 and 1,195,764; Angew. Chemie, 76, 303 (1964); and Acta Chem. Scand., 18, 826 (1964).
The optional maleimide component of the curable resin composi-tion of this invention, hereinafter referred to as component (c) is selected from maleimides, prepolymers thereof and prepolymers of the maleimides and amines.
The maleimides employed in the present invention are conven-tional organic compounds known in the art having two maleimide groups derived from maleic anhydride and diamines or polyamines.
Suitable maleimides include bismaleimides represen~ed by the following formula (IV) O O
Il l!
~ \ N R2- N = (IV) 1. Il O O
wherein R represents a divalent aromatic (aryl), aliphatic or alicyclic organic group containing 2 to 40 carbon atoms.
r~
NC0 - ~ ~ (III) where a is 0 or l and S is cyanato or an aromatic group such as benzene, naphthalene, or biphenyl, which group can have a cyanato group as a ring substitutent. The amount of such aromatic cyanate of formula III which can be copolymerized with the triscyanates of S this invention can vary and generally will be dictated by the particular properties desired to be imparted by them to the cyanato copolymers. For example, the degree of crosslinking of the copoly-mer can be increased in some instances by incorporating such aromatic short chain (di)cyanates. The heat distortion temperature of the copolymer can thereby be increased.
Where a monocyanate is copolymerized with the triscyanate of the invention, copolymeric cyanates are formed in which the network growth and crosslinking density are reduced by the chain-terminat-ing monocyanato monomer. Generally, where used, the second cyanate [component (b)(l)] will amount to 5 to 95 %wt, preferably 5 to 50 ~wt of the cyanato copolymer.
The triscyanates of the invention can also be used in the form of a prepolymer. The prepolymer is prepared by polymerizing the polyfunctional cyanato monomer in the presence of a convention-al catalyst, for example, a mineral acid, a Lewis acid, a salt sucha sodium carbonate or lithium chloride, or a phosphoric acid ester such as tributyl phosphine. The prepolymer contains a triazine ring generally in the molecule as a result of the trimerization of the cyanato group of the triscyanate. Preferred prepolymers are those having an average molecular weight of at least 400, especially up to 6000.
The cyanato ester comonomer can be used in the form of a mixture of the monomer and the prepolymer. For example, many of the comr.ercially available cyanato esters derived from bisphenol A and cyanogen halide are in the form of mixtures of cyanato monomers and prepolymers, and such materials can also be used in the present invention.
~ 3 ~. 7 ~ j,~) i^j A mixture of a prepolymer of the cyanato ester comonomer and an amine may also be used.
Generally, the cyanato ester comonomers can be prepared by known methods including reacting polyhydric phenolic materials with cyanogen halides, such as cyanogen chloride or cyanogen bromide.
Cyanate aromatic esters, which are readily available and preferred for use as comonomers in this invention in view of the properties of the final resin obtained, are those prepared by reacting a symmetrical, fused ring-free dihydric phenol, such as bisphenol A
(2,2-bis[4-hydroxyphenyl]propane) with cyanogen halides. Likewise, cyanato aromatic esters obtained by the reaction of a phenol-formaldehyde precondensate with cyanogen halides can be advanta-geously used. Suitable cyanates disclosed in U.S. patent 4,110,364;
3,595,900; 3,755,402; 4,157,360; 4,403,073; German patents 1,190,184 and 1,195,764; Angew. Chemie, 76, 303 (1964); and Acta Chem. Scand., 18, 826 (1964).
The optional maleimide component of the curable resin composi-tion of this invention, hereinafter referred to as component (c) is selected from maleimides, prepolymers thereof and prepolymers of the maleimides and amines.
The maleimides employed in the present invention are conven-tional organic compounds known in the art having two maleimide groups derived from maleic anhydride and diamines or polyamines.
Suitable maleimides include bismaleimides represen~ed by the following formula (IV) O O
Il l!
~ \ N R2- N = (IV) 1. Il O O
wherein R represents a divalent aromatic (aryl), aliphatic or alicyclic organic group containing 2 to 40 carbon atoms.
r~
Examples of the divalent organic group R in the formula (IV) include: (i) aromatic, aliphatic or alicyclic hydrocarbon groups containing 3 to 20 and, preferably, 6 to 16 carbon atoms such as isopropylidene, phenylene, naphthylene, xylene, cyclohexylene or hexahydroxylylene; and (ii) organic groups consistin~ of a plurali-ty of aromatic rings bonded to each other directly or through a bridging atom or group, Eor example, those expressed by the follow-ing formula (V) ~ ~ (R )m ~ m ~ // (V) wherein each m is independently zero or 1, n is zero or 1; and each R is independently a divalent aliphatic or aromatic hydrocar-bon group containing up to 14 carbon atoms, an oxygen atom, asulphur atom, a carbonyl group, a sulphonyl group, a sulphinyl group, an alkyleneoxyalkylene group containing up to 4 carbon atoms in each alkylene group, an imino group, a group (VI) containing a phosphorus atom - 0 - P - 0 - or - 0 - P - - ' (VI) or (iii) groups derived from novolac-type phenol or resorcinol resins. In formula (IV), the divalent organic group R may contain an organic group which does not participate in the reaction, such as an alkyl group containing 1 to 4 carbon atoms (e.g., methyl or ethyl), or an alkoxy group containing 1 to 4 carbon atoms (e.g., methoxy or ethoxy), at the aromatic ring when it is an aromatic organic group or at the alicyclic ring when it is an alicyclic organic group. Suitable polymaleimides are derived from maleimides and polyamines. Preferably, the maleimide is methylene dianiline bismaleimide.
Examples of suitable organic groups of formula (V) are those derived from biphenyl, diphenylmethane, ~317~3~-J~
Examples of suitable organic groups of formula (V) are those derived from biphenyl, diphenylmethane, ~317~3~-J~
~,~-dimethylphenylmethane, diphenyl ether, dibenzyl ether, diphenyl thioether, diphenyl ketone, diphenylamine, diphenyl sulphoxide, diphenyl sulphone, triphenylphosphite, and triphenylphosphate and the like.
The maleimide can be prepared by a method known per se which comprises reacting maleic anhydride with diamines or polyamines, and then cyclodehydrating the resulting maleamidic acids. The amines are preferably aromatic diamines in view of the thermal stability of the final resins. When it is desired to improve the flexibility or suppleness of the resin, alicyclic diamines may be used alone or in combination with the aromatic diamines. From the viewpoint of reactivity, the diamines are preferably primary diamines, but secondary diamines can also be used. Examples of suitable diamines are m-phenylenediamine, m-, or p-xylylene-diamine, l,4-cyclohexanediamine, hexahydroxylylenediamine, bis(4-aminophenyl)methane, bis(4-aminophenyl~sulphone, bis(4-amino-3-methylphenyl)methane (MDT), bis(4-amino-3,5-dimethyl-phenyl)methane (MDX), bis(4-aminophenyl)cyclohexane, bis(4-amino~
phenyl)ether, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(4-amino-3-methylphenyl)methane, ~,~-bis(4-aminophenyl)phenylmethane, bis(4-aminophenyl)-p-di'sopropylbenzene and the l:ike.
The maleimides can be used either alone or in admixture of two or more.
Prepolymers of the maleimides, and, preferably, prepolymers of the maleimides and amines can also be used.
As already stated, an amine can be incorporated in the form of a prepolymer of the polyfunctional cyanato ester and the amine as component (b) or a prepolymer of the maleimide component and the amine as component (c). Examples of the amines that can be used in this invention include (i) diamines of the general formula (VII) H N R3 - NH (VII) wherein R is a divalent aromatic or alicyclic organic group, especially those illustrated with regards to the production of ~ 3 ~ 7 '~ ;,, maleimides, and (ii) polyamines such as hexamethylenetetramine, polyethylene imine, polyamino styrene or polyvinyl imidazole;
triethylenediamine; imidazoles such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, l-benzyl-2-methylimidazole, l-propyl-2-methylimidazole, l-cyanoethyl-2-methylimidazole, l-cyanoethyl-2-ethyl-4-methylimidazole, l-cyanoethyl-2-undecylimidazole, l-cyano-ethyl-2-phenylimidazole or l-guanaminoethyl-2-methylimidazole, adducts formed between these imidazoles and trimellitic acid and like polyamines.
When the above-mentioned amines are used in the form of a prepolymer with maleimides, the prepolymer can be produced by reacting the maleimide and the amine, especially l mole of the maleimide and ~ to l mole of the diamine, in a suitable solvent such as ketones under the known conditions, for example, by heating at a temperature of 40~ to 250C for 5 minutes to 5 hours. The prepol.ymer derived from the maleimide and the amine, although differing according to the ratio of the monomers or the degree of polyaddition, are considered to have the structure represented by the following formula (VIII) O O O O O O
~ \ N R2 N / ~ N-R3-NIl \ N-R2-N ~ -R -~ ~ ~ N-R2-N
~ ~/ \ / ~
l i 1 1 ~
O O l O O O O
m (VIII) wherein m is zero or a positive number, generally not more than lO, and R and R are the same as defined hereabove.
When the amines are incorporated in the composition in the form of prepolymers with the cyanato ester, the prepolymers can be produced by reacting the cyanato ester monomer with the diamines, preferably using O.l to l equivalent of the diamines based on the 1 3 3 7 3 ~
cyanato ester monomer, in a suitable solvent such as ketones at a temperature of 0 to 100C for 1 minute to 1 hour.
In either of these cases of adding amines in the form of prepolymers, it is of course permissible to cause free amines to be present in the composition.
When the amines are included in component (b) and/or component (c) in the form of a prepolymer or the like, they are considered to function mainly as a modifier for polymer such as a chain extender.
Suitable maleimides for component (c) are disclosed in ~.S.
patents 4,110,364, 4,298,720, and the like.
The components of the curable resin (co)polymer composition of this invention can be varied over a wide range. Generally, however, the ratio by weight of cyanato component (a) and optionally (b) and/or maleimide component (c) is in the range of from 1:99 to 99:1, preferably 5:95 to 95:5. When preparing heat resistant resin having good toughness, from 10 ~wt of cyanato component to 90 ~wt of cyanato component, preferably 10 ~wt to 50 ~wt, is used on the basis of total weight of all polymerizable components. In order to improve heat resistance of cured resin derived from the cyanato component, it is preferable to use a combined weight of maleimide components ranging from 10 %wt to 90 ~wt, preferably 10 %wt to 50 ~wt, based on the total weight of all polymerizable components.
The curable composition of this invention comprises one or more components which can each be used in any desired form such as solid, solution or dispersion. These components are mixed in solvent or in the absence of a solvent to form the compositions of this invention. For example, the mixing procedure comprises mixing solutions of cyanato component and maleimide or either separately or together in a suitable inert organic solvent, such as for example, ketones such as methyl ethyl ketone, chlorinated hydrocar-bons such as methylene chloride, ethers and the like, and homogeni-zing the resulting mixed solution at room temperature or at an elevated temperature below the boiling point of the solvents to form a composition in the form of a solution. When homogenizing 1 3 ~
these solutions at room temperature or at an elevated temperature, some reactions may take place between the constituent elements. So long as the resins components are maintained in the state of solution without ~elation, such reactions do not particularly affect the operability of the resulting composition in, for exam-ple, a bonding, coating, laminating or moulding operation.
The curable resin compositions of in-vention can be used in the above solution form as adhesives, paint vehicles, moulding materi-als to be impregnated in substrates, or laminating materials. In this case, the concentration of the resin solid in the solution is determined so that the optimum operability can be obtained accord-ing to the desired utility.
The resin compositions of this invention can be used for various purposes in the form of dried powder, pellets, resin-im-pregnated product or compound. For example, compositions with the individual components uniformly mixed can be obtained by uniformly mixing the resin components in solution, and then removing the solvents from the homogeneous solution at reduced pressure or at an elevated temperature. Alternatively, solids components are kneaded at room temperature or at an elevated temperature to form a homoge-nized resin composition.
The curable composition of this invention may be reticulated by heating it alone to form a cured resin having heat resistance.
In general, a catalyst may be used in order to promote crosslinking reaction of the components in the composition.
Examples of the catalysts include imidazoles, such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methyl-imidazole, l-propyl-2-methylimidazole, 1-cyanoethyl-2-methylimida-zole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, l-cyanoethyl-2-phenylimidazole, l-guanaminoethyl-2-methylimidazole and addition product of an imidazole and trimel-litic acid; tertiary amines, such as N,N-dimethyl-benzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, N,N-dimethyl-p-anisi-dine, p-halogeno-N,N-dimethyl-aniline, 2-N-ethylanilino ethanol, - 13 - ~ ~ ~ 7 ~ ~ -tri-n-butylamine, pyridine, quinoli.ne, N-methylmorpholine, triethanolamine, triethylenediamine, N,N,N',N'-tetramethylbutane-diamine, N-methylpiperidine; phenols, such as phenol, cresol, xylenol, resorcinol, and phloro~lucin; organic metal salts, such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, tin oleate, dibutyl tin maleate, manganese naphthenate, cobalt naphthenate, and acetylacetone iron; and inorganic metal salts, such as stannic chloride, zinc chloride and aluminium chloride;
peroxides, such as benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, acetyl peroxide, para-chlorobenzoyl peroxide and di-t-butyl diperphthalate; acid anhydrides, such as maleic anhydride, phthalic anhydride, fumaric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, hexahydropyro-mellitic anhydride and hexahydrotrimellitic anhydride; azo com-pounds, such as azoisobutylonitrile, 2,2'-azobispropane, m,m'-azoxystyrene, hydrozones, and mixtures thereof. The amount of catalyst varies considerably according to the type of catalyst, the utility or during conditions. They can, however, be used in catalytic amo~mts such as, for example, less than 5 %wt of the total composition. The use of zinc octoate is preferred.
A variety of additives may be added to the curable composition to impart specific properties provided that they do not impair the esssntial properties of the resulting resin. Examples of the additives include natural or synthetic resins, fibrous reinforce-ment, fillers, pigments, dyestuffs, thickening agents, wettingagents, lubricants, flame-retardants and the like.
The resin composition of this invention can also contain a white pigment such a titanium dioxide, a coloured pigment such as yellow lead, carbon black, iron black, molybdenum red, prussian blue, ultramarine, cadmium yellow or cadmiwn red, and other various organic or inorganic dyes and pigments in order to colour the compositions. In addition to the above coloured pigments, the resin compositions can also contain a rust-proofing pigment such as zinc chromate, red lead, red iron oxide, zinc flower or strontium chromate, an anti-sag agent such as aluminium stearate, a 14 ~ ~ ~ 7;~3~'`
dispersing agent, a thickener, a coat modifier, a body pigment or a fire retardant, which are known additives for paints.
The monomers will usually contain an amount of a polymeriza-tion inhibitor effective to prevent premature polymerization of the monomer, generally less than 0.5 ~wt, usually less than 0.2 %wt, based on the weight of the monomer. Exampl.es of suitable inhibitors include tert.iary butyl catechol, benzoquinone, hydroquinone and phenothiazine.
The composition is suitable for fibre-reinforced composites applications, for which a fibrous reinforcing material, such as chopped glass, glass fibres, carbon fibre, and the like, in the form of a mat, cloth or continuous fibres, for example, is impreg-nated with the resin system. The impregnated fibres are usually subjected to a relatively mild heat treatment ("B-staged") to partially cure the resin to a flexible, tacky state, or "prepreg."
The prepreg is then subJected to elevated temperature and pressure so as to completely cure the resin to a hard, inflexible state. A
plurality of prepregs can be layered and cured to form a laminate having utility in circuit boards. For such electrical applications, the properties of flame retardants and high Tg are important.
The compositions of this invention are cured by heating after applying it to a substrate as a coating or adhesive layer, or after moulding or laminating in the form of powder, pellet or as impreg-nated in a substrate. The curing conditions of the curable composi-tion of this invention depend on the proportion of components constituting the composition and the nature of the components employed. In general, the composition of this invention may be cured by heating it at a temperature within the range of 0C-300C, preferably 100C-250~C, although differing according to the pres-ence of a catalyst or curing agent or its amount, or the types of the components in the composition. The time required for heating is generally 30 seconds to 10 hours, although considerably differing according to whether the resin composition is used as a thin coating or as moulded articles of relatively large thickness or as laminates or as matrix resins for fibre reinforced composites, ~ 3 ~
particularly for electrical and electronic applications, e.g., when applied to an electrically nonconductive material and subsequently curing the composition. Suitable fi.brous reinforcing materials include glass fibres, quartz fibres, carbon fibres, boron fibres, I'evlar fibres, Teflon. fibres and the ].ike, with woven or continu-ous glass fibres or carbon fibres being preferred. The fibrous or reinforcing material is present in the composition in an amount effective to impart increased strength to the composition for the intended purpose, generally from ~0 to 95 %wt, usually from 50 to ~0 %wt, based on the weight of the total composition. The laminates of the invention can optionally include one or more layers of a different material and in electrical laminates this can include one or more layers of a conductive material such as copper or the like. When the resin composition of this invention is used for producing moulded articles, laminated articles or bonded structures, the curing is desirably effected under pressure. Generally, this pressure is from 10 to lO0 kg/cm (gauge).
The composition of thi.s invention cures rapidly, even under mild conditions, so is especially suitable when quantity production and ease of workability are desired. The cured resin made from the composition not only has excellent adhesive force, bond strength, heat resistance, and electric properties, but also is excellent in mechanical properties and resistance to impact, chemicals, moisture and the like. The composition of this invention has a variety of uses as a coating material for rust prevention, flame resistance, flame retardants and the like; as electrical insulating varnish; as adhesive; in laminates to be used for furnitures, building materi-als, sheathing materials, electrical materials especially where low dielectric content and good thermal properties are desired in a variety of mouldings and the like.
The present invention is further illustrated by the followingexamples.
- 16 ~ ?~
Example 1 - Triscyanato Ester Alpha, alpha', alpha"-tris(4-hydroxyphenyl)-1,3,5-tri-isopro-pylbenzene (1) was obtained from Mitsui Petrochemical Company and used without further purification. Into a five-litre, four-neck round-bottom flask equipped with a stirring rod, thermocouple, condenser, and an addition funnel was added 381.6 gr of cyanogen bromide in 1500 ml of isopropyl alcohol. The solution was cooled to 5C. In a separate container 480 gr of (1) was dissolved in 1000 ml of isopropyl alcohol and cooled to 5C. To the latter 233.9 gr of triethylamine was added with stirring. When the triethylamine addition had been completed, the entire mixture was transferred to the dropping funnel and added dropwise to the cyanogen bromide-iso-propyl alcohol solution. Care was exercised to maintain the temper-ature at 5C or below. After the addition had been completed, the reaction was left to stir overnight and gradually come to room temperature. The triscyanato ester which had crystallized out with the triethylamine hydrobromide salt was washed several times with water and dried in a vacuum oven at 50C to remove the water. The yield was 300 gr. The product was confirmed by both IR and NMR.
Example 2 - Laminate A varnish solution was prepared by dissolving 72 gr of the triscyanato ester in 36 ml of acetone and 2 ml of dimethyl form-amide. 0.2 PHR (parts per hundred parts by weight based on the ester) of 7.inc octoate (8~ solution) was added as a catalyst. The varnish had a gel time of 85 seconds on a hot plate at 171C. The varnish solution was coated on 7628 glass cloth and advanced to a ("B") stage in a forced air oven set at 163C for three minutes.
The prepreg dust had a gel time of 28 seconds at 171C. Eight layers of the prepregs were stacked and pressed into a laminate at 180C and 17.6 kg/cm (25 psi) pressure for 1 hour. The cured laminate was postcured for 2 hours at 220C. The electrical and thermal properties of the laminate (Table 1) were found to be outstanding.
- 17 - 13~7~ ~
Table 1 l.ectrical and Thermal Properties of a Laminate of Triscyanato Ester Resin Flexural Strength, 23C, kg/cm 3,838 Flexural Modulus, 23G, kg/cm 177,898 Dielectric Constant, 23C, D-24/23 3.8 Dissipation Factor, 23C, D-24/23 0.0083 Dielectric Strength, 23C, V/mil 705 Volume Resistivity ~x 10 ohm-cm) 1.46 Surface Resistivity (x 10 ohm-cm) 6.86 Water Absorption, 1 hr 1.05 kg/cm Steam, ~wt 0.24 Tg, DMA* Max Damping, C 265 Tg, DSC,** C 214 *Dynamic mechanical analyzer.
**Differential scanning calorimeter.
The maleimide can be prepared by a method known per se which comprises reacting maleic anhydride with diamines or polyamines, and then cyclodehydrating the resulting maleamidic acids. The amines are preferably aromatic diamines in view of the thermal stability of the final resins. When it is desired to improve the flexibility or suppleness of the resin, alicyclic diamines may be used alone or in combination with the aromatic diamines. From the viewpoint of reactivity, the diamines are preferably primary diamines, but secondary diamines can also be used. Examples of suitable diamines are m-phenylenediamine, m-, or p-xylylene-diamine, l,4-cyclohexanediamine, hexahydroxylylenediamine, bis(4-aminophenyl)methane, bis(4-aminophenyl~sulphone, bis(4-amino-3-methylphenyl)methane (MDT), bis(4-amino-3,5-dimethyl-phenyl)methane (MDX), bis(4-aminophenyl)cyclohexane, bis(4-amino~
phenyl)ether, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(4-amino-3-methylphenyl)methane, ~,~-bis(4-aminophenyl)phenylmethane, bis(4-aminophenyl)-p-di'sopropylbenzene and the l:ike.
The maleimides can be used either alone or in admixture of two or more.
Prepolymers of the maleimides, and, preferably, prepolymers of the maleimides and amines can also be used.
As already stated, an amine can be incorporated in the form of a prepolymer of the polyfunctional cyanato ester and the amine as component (b) or a prepolymer of the maleimide component and the amine as component (c). Examples of the amines that can be used in this invention include (i) diamines of the general formula (VII) H N R3 - NH (VII) wherein R is a divalent aromatic or alicyclic organic group, especially those illustrated with regards to the production of ~ 3 ~ 7 '~ ;,, maleimides, and (ii) polyamines such as hexamethylenetetramine, polyethylene imine, polyamino styrene or polyvinyl imidazole;
triethylenediamine; imidazoles such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, l-benzyl-2-methylimidazole, l-propyl-2-methylimidazole, l-cyanoethyl-2-methylimidazole, l-cyanoethyl-2-ethyl-4-methylimidazole, l-cyanoethyl-2-undecylimidazole, l-cyano-ethyl-2-phenylimidazole or l-guanaminoethyl-2-methylimidazole, adducts formed between these imidazoles and trimellitic acid and like polyamines.
When the above-mentioned amines are used in the form of a prepolymer with maleimides, the prepolymer can be produced by reacting the maleimide and the amine, especially l mole of the maleimide and ~ to l mole of the diamine, in a suitable solvent such as ketones under the known conditions, for example, by heating at a temperature of 40~ to 250C for 5 minutes to 5 hours. The prepol.ymer derived from the maleimide and the amine, although differing according to the ratio of the monomers or the degree of polyaddition, are considered to have the structure represented by the following formula (VIII) O O O O O O
~ \ N R2 N / ~ N-R3-NIl \ N-R2-N ~ -R -~ ~ ~ N-R2-N
~ ~/ \ / ~
l i 1 1 ~
O O l O O O O
m (VIII) wherein m is zero or a positive number, generally not more than lO, and R and R are the same as defined hereabove.
When the amines are incorporated in the composition in the form of prepolymers with the cyanato ester, the prepolymers can be produced by reacting the cyanato ester monomer with the diamines, preferably using O.l to l equivalent of the diamines based on the 1 3 3 7 3 ~
cyanato ester monomer, in a suitable solvent such as ketones at a temperature of 0 to 100C for 1 minute to 1 hour.
In either of these cases of adding amines in the form of prepolymers, it is of course permissible to cause free amines to be present in the composition.
When the amines are included in component (b) and/or component (c) in the form of a prepolymer or the like, they are considered to function mainly as a modifier for polymer such as a chain extender.
Suitable maleimides for component (c) are disclosed in ~.S.
patents 4,110,364, 4,298,720, and the like.
The components of the curable resin (co)polymer composition of this invention can be varied over a wide range. Generally, however, the ratio by weight of cyanato component (a) and optionally (b) and/or maleimide component (c) is in the range of from 1:99 to 99:1, preferably 5:95 to 95:5. When preparing heat resistant resin having good toughness, from 10 ~wt of cyanato component to 90 ~wt of cyanato component, preferably 10 ~wt to 50 ~wt, is used on the basis of total weight of all polymerizable components. In order to improve heat resistance of cured resin derived from the cyanato component, it is preferable to use a combined weight of maleimide components ranging from 10 %wt to 90 ~wt, preferably 10 %wt to 50 ~wt, based on the total weight of all polymerizable components.
The curable composition of this invention comprises one or more components which can each be used in any desired form such as solid, solution or dispersion. These components are mixed in solvent or in the absence of a solvent to form the compositions of this invention. For example, the mixing procedure comprises mixing solutions of cyanato component and maleimide or either separately or together in a suitable inert organic solvent, such as for example, ketones such as methyl ethyl ketone, chlorinated hydrocar-bons such as methylene chloride, ethers and the like, and homogeni-zing the resulting mixed solution at room temperature or at an elevated temperature below the boiling point of the solvents to form a composition in the form of a solution. When homogenizing 1 3 ~
these solutions at room temperature or at an elevated temperature, some reactions may take place between the constituent elements. So long as the resins components are maintained in the state of solution without ~elation, such reactions do not particularly affect the operability of the resulting composition in, for exam-ple, a bonding, coating, laminating or moulding operation.
The curable resin compositions of in-vention can be used in the above solution form as adhesives, paint vehicles, moulding materi-als to be impregnated in substrates, or laminating materials. In this case, the concentration of the resin solid in the solution is determined so that the optimum operability can be obtained accord-ing to the desired utility.
The resin compositions of this invention can be used for various purposes in the form of dried powder, pellets, resin-im-pregnated product or compound. For example, compositions with the individual components uniformly mixed can be obtained by uniformly mixing the resin components in solution, and then removing the solvents from the homogeneous solution at reduced pressure or at an elevated temperature. Alternatively, solids components are kneaded at room temperature or at an elevated temperature to form a homoge-nized resin composition.
The curable composition of this invention may be reticulated by heating it alone to form a cured resin having heat resistance.
In general, a catalyst may be used in order to promote crosslinking reaction of the components in the composition.
Examples of the catalysts include imidazoles, such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methyl-imidazole, l-propyl-2-methylimidazole, 1-cyanoethyl-2-methylimida-zole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, l-cyanoethyl-2-phenylimidazole, l-guanaminoethyl-2-methylimidazole and addition product of an imidazole and trimel-litic acid; tertiary amines, such as N,N-dimethyl-benzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, N,N-dimethyl-p-anisi-dine, p-halogeno-N,N-dimethyl-aniline, 2-N-ethylanilino ethanol, - 13 - ~ ~ ~ 7 ~ ~ -tri-n-butylamine, pyridine, quinoli.ne, N-methylmorpholine, triethanolamine, triethylenediamine, N,N,N',N'-tetramethylbutane-diamine, N-methylpiperidine; phenols, such as phenol, cresol, xylenol, resorcinol, and phloro~lucin; organic metal salts, such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, tin oleate, dibutyl tin maleate, manganese naphthenate, cobalt naphthenate, and acetylacetone iron; and inorganic metal salts, such as stannic chloride, zinc chloride and aluminium chloride;
peroxides, such as benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, acetyl peroxide, para-chlorobenzoyl peroxide and di-t-butyl diperphthalate; acid anhydrides, such as maleic anhydride, phthalic anhydride, fumaric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, hexahydropyro-mellitic anhydride and hexahydrotrimellitic anhydride; azo com-pounds, such as azoisobutylonitrile, 2,2'-azobispropane, m,m'-azoxystyrene, hydrozones, and mixtures thereof. The amount of catalyst varies considerably according to the type of catalyst, the utility or during conditions. They can, however, be used in catalytic amo~mts such as, for example, less than 5 %wt of the total composition. The use of zinc octoate is preferred.
A variety of additives may be added to the curable composition to impart specific properties provided that they do not impair the esssntial properties of the resulting resin. Examples of the additives include natural or synthetic resins, fibrous reinforce-ment, fillers, pigments, dyestuffs, thickening agents, wettingagents, lubricants, flame-retardants and the like.
The resin composition of this invention can also contain a white pigment such a titanium dioxide, a coloured pigment such as yellow lead, carbon black, iron black, molybdenum red, prussian blue, ultramarine, cadmium yellow or cadmiwn red, and other various organic or inorganic dyes and pigments in order to colour the compositions. In addition to the above coloured pigments, the resin compositions can also contain a rust-proofing pigment such as zinc chromate, red lead, red iron oxide, zinc flower or strontium chromate, an anti-sag agent such as aluminium stearate, a 14 ~ ~ ~ 7;~3~'`
dispersing agent, a thickener, a coat modifier, a body pigment or a fire retardant, which are known additives for paints.
The monomers will usually contain an amount of a polymeriza-tion inhibitor effective to prevent premature polymerization of the monomer, generally less than 0.5 ~wt, usually less than 0.2 %wt, based on the weight of the monomer. Exampl.es of suitable inhibitors include tert.iary butyl catechol, benzoquinone, hydroquinone and phenothiazine.
The composition is suitable for fibre-reinforced composites applications, for which a fibrous reinforcing material, such as chopped glass, glass fibres, carbon fibre, and the like, in the form of a mat, cloth or continuous fibres, for example, is impreg-nated with the resin system. The impregnated fibres are usually subjected to a relatively mild heat treatment ("B-staged") to partially cure the resin to a flexible, tacky state, or "prepreg."
The prepreg is then subJected to elevated temperature and pressure so as to completely cure the resin to a hard, inflexible state. A
plurality of prepregs can be layered and cured to form a laminate having utility in circuit boards. For such electrical applications, the properties of flame retardants and high Tg are important.
The compositions of this invention are cured by heating after applying it to a substrate as a coating or adhesive layer, or after moulding or laminating in the form of powder, pellet or as impreg-nated in a substrate. The curing conditions of the curable composi-tion of this invention depend on the proportion of components constituting the composition and the nature of the components employed. In general, the composition of this invention may be cured by heating it at a temperature within the range of 0C-300C, preferably 100C-250~C, although differing according to the pres-ence of a catalyst or curing agent or its amount, or the types of the components in the composition. The time required for heating is generally 30 seconds to 10 hours, although considerably differing according to whether the resin composition is used as a thin coating or as moulded articles of relatively large thickness or as laminates or as matrix resins for fibre reinforced composites, ~ 3 ~
particularly for electrical and electronic applications, e.g., when applied to an electrically nonconductive material and subsequently curing the composition. Suitable fi.brous reinforcing materials include glass fibres, quartz fibres, carbon fibres, boron fibres, I'evlar fibres, Teflon. fibres and the ].ike, with woven or continu-ous glass fibres or carbon fibres being preferred. The fibrous or reinforcing material is present in the composition in an amount effective to impart increased strength to the composition for the intended purpose, generally from ~0 to 95 %wt, usually from 50 to ~0 %wt, based on the weight of the total composition. The laminates of the invention can optionally include one or more layers of a different material and in electrical laminates this can include one or more layers of a conductive material such as copper or the like. When the resin composition of this invention is used for producing moulded articles, laminated articles or bonded structures, the curing is desirably effected under pressure. Generally, this pressure is from 10 to lO0 kg/cm (gauge).
The composition of thi.s invention cures rapidly, even under mild conditions, so is especially suitable when quantity production and ease of workability are desired. The cured resin made from the composition not only has excellent adhesive force, bond strength, heat resistance, and electric properties, but also is excellent in mechanical properties and resistance to impact, chemicals, moisture and the like. The composition of this invention has a variety of uses as a coating material for rust prevention, flame resistance, flame retardants and the like; as electrical insulating varnish; as adhesive; in laminates to be used for furnitures, building materi-als, sheathing materials, electrical materials especially where low dielectric content and good thermal properties are desired in a variety of mouldings and the like.
The present invention is further illustrated by the followingexamples.
- 16 ~ ?~
Example 1 - Triscyanato Ester Alpha, alpha', alpha"-tris(4-hydroxyphenyl)-1,3,5-tri-isopro-pylbenzene (1) was obtained from Mitsui Petrochemical Company and used without further purification. Into a five-litre, four-neck round-bottom flask equipped with a stirring rod, thermocouple, condenser, and an addition funnel was added 381.6 gr of cyanogen bromide in 1500 ml of isopropyl alcohol. The solution was cooled to 5C. In a separate container 480 gr of (1) was dissolved in 1000 ml of isopropyl alcohol and cooled to 5C. To the latter 233.9 gr of triethylamine was added with stirring. When the triethylamine addition had been completed, the entire mixture was transferred to the dropping funnel and added dropwise to the cyanogen bromide-iso-propyl alcohol solution. Care was exercised to maintain the temper-ature at 5C or below. After the addition had been completed, the reaction was left to stir overnight and gradually come to room temperature. The triscyanato ester which had crystallized out with the triethylamine hydrobromide salt was washed several times with water and dried in a vacuum oven at 50C to remove the water. The yield was 300 gr. The product was confirmed by both IR and NMR.
Example 2 - Laminate A varnish solution was prepared by dissolving 72 gr of the triscyanato ester in 36 ml of acetone and 2 ml of dimethyl form-amide. 0.2 PHR (parts per hundred parts by weight based on the ester) of 7.inc octoate (8~ solution) was added as a catalyst. The varnish had a gel time of 85 seconds on a hot plate at 171C. The varnish solution was coated on 7628 glass cloth and advanced to a ("B") stage in a forced air oven set at 163C for three minutes.
The prepreg dust had a gel time of 28 seconds at 171C. Eight layers of the prepregs were stacked and pressed into a laminate at 180C and 17.6 kg/cm (25 psi) pressure for 1 hour. The cured laminate was postcured for 2 hours at 220C. The electrical and thermal properties of the laminate (Table 1) were found to be outstanding.
- 17 - 13~7~ ~
Table 1 l.ectrical and Thermal Properties of a Laminate of Triscyanato Ester Resin Flexural Strength, 23C, kg/cm 3,838 Flexural Modulus, 23G, kg/cm 177,898 Dielectric Constant, 23C, D-24/23 3.8 Dissipation Factor, 23C, D-24/23 0.0083 Dielectric Strength, 23C, V/mil 705 Volume Resistivity ~x 10 ohm-cm) 1.46 Surface Resistivity (x 10 ohm-cm) 6.86 Water Absorption, 1 hr 1.05 kg/cm Steam, ~wt 0.24 Tg, DMA* Max Damping, C 265 Tg, DSC,** C 214 *Dynamic mechanical analyzer.
**Differential scanning calorimeter.
Claims (10)
1. A compound of the formula (I) wherein each R is independently an alkyl group containing from 1 to 4 carbon atoms and each n is independently 0, 1 or 2.
2. A compound according to claim 1 wherein each R is a methyl group.
3. A compound according to claim 1 wherein each n is zero.
4. A curable resin composition comprising:
(a) (i) at least one compound according to any one of claims 1 to 3; or (ii) a homopolymerization product of a compound according to any one of claims 1 to 3; or (iii) the polymeric product of the reaction of a compound according to any one of claims 1 to 3 with an amine, and optionally at least one of (b) the copolymerization product of a compound according to any one of claims 1 to 3 with a second cyanato ester, with at least one of (1) (i) a second cyanato ester;
(ii) a homopolymerization product of a second cyanato ester;
(iii) a polymeric product of the reaction of a second cyanato ester and with an amine;
(2) an amine, or (c) (i) a maleimide compound;
(ii) a polymeric product of the reaction of a maleimide and an amine; or (iii) a polymeric product of the reaction of more than one maleimide and an amine.
(a) (i) at least one compound according to any one of claims 1 to 3; or (ii) a homopolymerization product of a compound according to any one of claims 1 to 3; or (iii) the polymeric product of the reaction of a compound according to any one of claims 1 to 3 with an amine, and optionally at least one of (b) the copolymerization product of a compound according to any one of claims 1 to 3 with a second cyanato ester, with at least one of (1) (i) a second cyanato ester;
(ii) a homopolymerization product of a second cyanato ester;
(iii) a polymeric product of the reaction of a second cyanato ester and with an amine;
(2) an amine, or (c) (i) a maleimide compound;
(ii) a polymeric product of the reaction of a maleimide and an amine; or (iii) a polymeric product of the reaction of more than one maleimide and an amine.
5. A curable resin according to claim 4 wherein component (a) is the component (a)(ii), as defined in claim 4.
6. A curable resin according to claim 4 wherein a second cyanato ester (b) is present as an aromatic cyanate.
7. A curable resin according to claim 4 wherein the maleimide component (c) is a monomer.
8. A curable resin according to claim 7 wherein the monomer is methylene dianiline bismaleimide.
9. A curable resin according to claim 4 wherein the maleimide component (c) is a prepolymer of a maleimide and a diamine.
10. An article of manufacture prepared from a composition according to claim 4 wherein the article is a coating, an electrical varnish, an adhesive, or a laminate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/260,346 US4916210A (en) | 1988-10-20 | 1988-10-20 | Resin from alpha, alpha', alpha"-tris(4-cyanatophenyl)-1,3,5-triisopropylbenzene |
| US260,346 | 1988-10-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1317305C true CA1317305C (en) | 1993-05-04 |
Family
ID=22988799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 614319 Expired - Fee Related CA1317305C (en) | 1988-10-20 | 1989-09-28 | Alpha, alpha', alpha''-tris (4-cyanatophenyl)-1,3,5- triisopropylbenzenes and resins thereof |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4916210A (en) |
| EP (1) | EP0366184B1 (en) |
| JP (1) | JPH02157256A (en) |
| KR (1) | KR900006277A (en) |
| CA (1) | CA1317305C (en) |
| DE (1) | DE68904396T2 (en) |
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| US5516876A (en) | 1983-09-27 | 1996-05-14 | The Boeing Company | Polyimide oligomers and blends |
| US5969079A (en) | 1985-09-05 | 1999-10-19 | The Boeing Company | Oligomers with multiple chemically functional end caps |
| US5512676A (en) | 1987-09-03 | 1996-04-30 | The Boeing Company | Extended amideimide hub for multidimensional oligomers |
| US5705598A (en) | 1985-04-23 | 1998-01-06 | The Boeing Company | Polyester sulfone oligomers and blends |
| US5693741A (en) | 1988-03-15 | 1997-12-02 | The Boeing Company | Liquid molding compounds |
| US5210213A (en) | 1983-06-17 | 1993-05-11 | The Boeing Company | Dimensional, crosslinkable oligomers |
| US5714566A (en) | 1981-11-13 | 1998-02-03 | The Boeing Company | Method for making multiple chemically functional oligomers |
| US5618907A (en) | 1985-04-23 | 1997-04-08 | The Boeing Company | Thallium catalyzed multidimensional ester oligomers |
| US5817744A (en) | 1988-03-14 | 1998-10-06 | The Boeing Company | Phenylethynyl capped imides |
| US5068309A (en) * | 1990-03-29 | 1991-11-26 | Hi-Tek Polymers, Inc. | Low temperature curable dicyanate ester of dihydric phenol composition |
| US5320870A (en) * | 1991-08-28 | 1994-06-14 | The United States Of America As Represented By The Secretary Of The Navy | Fire protective coating and method for applying same to a structure |
| US5292861A (en) * | 1992-12-29 | 1994-03-08 | International Business Machines Corporation | Trifunctional cyanate esters, polymers thereof; use and preparation thereof |
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| KR101990258B1 (en) * | 2008-08-08 | 2019-06-17 | 헨켈 아이피 앤드 홀딩 게엠베하 | Low temperature curing compositions |
| EP2196462B1 (en) | 2008-12-12 | 2011-09-28 | Fujifilm Corporation | Polymerizable compound, lactone-containing compound, method for manufacturing lactone-containing compound and polymer compound obtained by polymerizing the polymerizable compound |
| EP2356516B1 (en) | 2008-12-12 | 2017-10-25 | FUJIFILM Corporation | Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method using the composition |
| JP5377172B2 (en) | 2009-03-31 | 2013-12-25 | 富士フイルム株式会社 | Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method using the same |
| JP5630133B2 (en) * | 2010-08-05 | 2014-11-26 | 三菱瓦斯化学株式会社 | Cyanate ester compound and cured product thereof |
| SG195000A1 (en) * | 2011-05-17 | 2013-12-30 | Huntsman Adv Mat Americas Inc | Halogen free thermoset resin system for low dielectric loss at high frequency applications |
| WO2020105505A1 (en) | 2018-11-22 | 2020-05-28 | 富士フイルム株式会社 | Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, and production method for electronic device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1248667B (en) * | 1963-02-16 | 1967-08-31 | Farbenfabriken Bayer Aktiengesellschaft Leverkusen | |
| US3595900A (en) * | 1968-07-01 | 1971-07-27 | Minnesota Mining & Mfg | Cyanatophenyl-terminated polyarylene ethers |
| US3738962A (en) * | 1971-03-08 | 1973-06-12 | Minnesota Mining & Mfg | Cyanurates of cyanatophenyl-terminated polyarylene ethers |
| US3954693A (en) * | 1973-09-24 | 1976-05-04 | Lockheed Aircraft Corporation | Coating |
| US4110364A (en) * | 1974-03-19 | 1978-08-29 | Mitsubishi Gas Chemical Company, Inc. | Curable resin compositions of cyanate esters |
| US4157360A (en) * | 1978-04-26 | 1979-06-05 | Allied Chemical Corporation | Thermoformable compositions comprising a crosslinked polycyanurate polymer and a thermoplastic polymer |
| US4403073A (en) * | 1980-05-06 | 1983-09-06 | Mitsubishi Gas Chemical Company, Inc. | Curable resin composition |
| JPS6026030A (en) * | 1983-07-22 | 1985-02-08 | Mitsubishi Gas Chem Co Inc | Curable resin composition |
| US4709008A (en) * | 1986-06-30 | 1987-11-24 | Interez, Inc. | Blend of tris (cyanatophenyl) alkane and bis(cyanatophenyl) alkane |
| US4749760A (en) * | 1987-06-30 | 1988-06-07 | Shell Oil Company | Curable resin compositions |
-
1988
- 1988-10-20 US US07/260,346 patent/US4916210A/en not_active Expired - Lifetime
-
1989
- 1989-09-28 CA CA 614319 patent/CA1317305C/en not_active Expired - Fee Related
- 1989-10-16 EP EP19890202623 patent/EP0366184B1/en not_active Expired - Lifetime
- 1989-10-16 DE DE1989604396 patent/DE68904396T2/en not_active Expired - Fee Related
- 1989-10-17 KR KR1019890014949A patent/KR900006277A/en not_active Application Discontinuation
- 1989-10-18 JP JP1269271A patent/JPH02157256A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE68904396T2 (en) | 1993-05-13 |
| EP0366184A1 (en) | 1990-05-02 |
| DE68904396D1 (en) | 1993-02-25 |
| KR900006277A (en) | 1990-05-07 |
| JPH02157256A (en) | 1990-06-18 |
| US4916210A (en) | 1990-04-10 |
| EP0366184B1 (en) | 1993-01-13 |
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