CA1098644A - Hydrolysis-stable polytriazines and a process for their production - Google Patents
Hydrolysis-stable polytriazines and a process for their productionInfo
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- CA1098644A CA1098644A CA257,578A CA257578A CA1098644A CA 1098644 A CA1098644 A CA 1098644A CA 257578 A CA257578 A CA 257578A CA 1098644 A CA1098644 A CA 1098644A
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- ortho
- cyanic acid
- polytriazine
- stable
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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
- C08G73/065—Preparatory processes
- C08G73/0655—Preparatory processes from polycyanurates
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Abstract of Disclosure Hydrolysis and temperature-stable, in organic solvents insoluble polytriazine are obtained by polytrimerising polyfunctional aromatic cyanic acid esters containing alkyl or phenyl radicals or halogen atoms, at least in the ortho- and ortho'-positions to at least one -OCN-group, optionally in the presence of polytrimerization-promoting catalysts. The polytriazine may be produced in a single stage or may be interrupted us soluble, highly stable in storage prepolymers are formed and completed at a later moment.
Le A 16 471
Le A 16 471
Description
This invention relates to a hydrolysis-stable polytriazines of polyfunctional aromatic cyanic acid esters having alkyl or phenyl radicals or halogen atoms at least in the ortho and ortho'-positions to at least one -OCN-group, and to a process of their production.
It is known from German Patent No. 1,190,18~ dated April 1, 1965 in the name of Bayer Aktiengesellschaft that high molecular wei~ht poly-triazines can be obtained by polymerising di-functional or polyfunctional aromatic cyanic acid esters at an elevated temperature, optionally in the presence of polymerisation promoters. The polymers are distinguished, for example, by their remarkable stability at elevated temperatures and are duroplastic in character after tempering for a sufficiently long period.
The resistance of the polytriazines to acids and various solvents may also be emphasised. It was not possible to detect any changes in test specimens that had been stored for thrbe months in benzene, dimethyl formamide, super high octane petrol, concentrated acetic acid, trichloroacetic acid, chromic acid, aqueous formaldehyde solution, fuel oil, saturated sodium phosphate solution and concentrated~hydrogen peroxide (cf. Kunststoffe 58, number 19, pages 827 to g32 (1968)).
In addition,~ it was found by V.V. Korchak et al (cf.
20 Vysokomolekulyarnye soedineniya 1974, number 1, pages 15 to 21) that the thermal and thermo-oxidative destruction of polytriazines based on aromatic cyanic acid esters is grea*ly influenced by moisture.
An object of the invention is to improve the polytriazines in regard to their resistance to hydrolysis.
This object is achieved by using polyfunctional aromatic cyanic ; acid esters having alkyl or phenyl radicals or halogen atoms~at least in the ortho, ortho'-position to at least one -OCN-group ~or the polytrimerisation reaction.
:
. . ~ , . . .
~8$~
Accordingly, the present invention relates to a process for the production of a hydrolysis-stable polytria~ine, wh:ich comprises polytrimer-ising a polyfunctional aromatic cyanic acid ester having the general formula:
(NCO ~ ~ ~ L ~ CN)d ll (R)b (R')c in which R represents chlorine or bromine, or Cl-Ca alkyl, the two radicals R not having to be the same, with the proviso that at least the ortho, ortho'-position to at least one cyanic acid ester group is substituted by R;
Rl has the same meaning as R;
A represents a si.ngle bond, oxygen, the sulphonyl group, the carbonyl group, the carboxyl dioxy group, the methylene, ethylene, or 2,2-propylene group C~13 ( - C - ) or the cyclohexylene radical;
a represents the number l where e = l, and the number 2 where e = 0;
b represents the number 2;
c represents the number 2;
d represents the number 0 or l; and e represents the number 0 or l, with the proviso that a + d = 2 or 3.
The invention also relates to the polytriazines obtained by this . .
process.
The~aromatlc cyanic acid.esters preferably correspond to the general formula (I):
A (OCN)n (I) :
: : - 2 --in which A represen-ts an aromatic radical or an aromatic radical interrupted by bridge members having alkyl or phenyl radicals or halogen atoms at least in the ortho and ortho'-positions to at least one -OCN-group, and n is a number from 2 to ~.
The aromatic cyanic acid esters of formula (I) used in accordance with the invention may be obtained by the process according to Canadian Patent number 812,232.
From 1 to 1.1 moles of cyanogen halide ancl 1 mole of a base or base mixture may be used per phenolic hydroxyl group. The reaction tempera-tures are in the range of from--~0C to +65C. Suitable basesare inorganic bases, such as sodium hydroxide, potassium hydroxide, soda, potash or - 2a -.
~ ' .
calcium hydroxide, or tertiary amines such as trimethylamine or triethylamine, whilst suitable solvents or suspending agents include water, alcohols, ketones, hydrocarbons, chlorinated hydrocarbons or mixtures thereof.
The aromatic cyanic acid esters preferably correspond to the general formula (II):
~ A ~OCN)d (Il) Cl~)_ (R ' ~ C
in which R represents halogen, linear or branched Cl-Cg alkyl or phenyl, several radicals R not having to be the same, with the proviso that at least the ortho, ortho'-position to at least one cyanic acid ester group is substituted by R;
R' has the same meaning as R or represents the group (III):
(OCN)d (111) Rb at least the ortho, ortho'-position to at least one cyanic : acid ester group again being substituted by R'; :
A represents a single bond, an alkylene group with from 1 to 9 carbon atoms optionally substituted by Cl-C4 .
~ ..
,~, .
:
.,, : : .
: ~ ~ . ' . ' all~yl or phenyl, a cycloaliphatic or aroma-tic 5-1ne~bered or 6-me~bered ring optionally interrwpted ~y oxygen, oxygen, th0 sulphonyl group (~S02~ the carb~nyl dioxy group (-OC0-) or the carbonyl group;
a = the number 1 or 2, b = a number ~rom 2 to 4 9 c = a number ~rom 2 to 4, d = the number 1 or 2, e = 0 or 1, with the proviso that the sum of a and d is always a number ~rom 2 to 4.
More especially, -the symbols in the formula (II) have the following meanings:
R represents a chlorine or bromine, or Cl-C4 alkyl;
A represents a single bond, oxygen, the sulphonyl group9 the carbonyl group, the carbonyl dioxy group, the methylene, ethylene) or 2~2-propylene group (- C -), or the cyclohexylene radical;
a = the number 1 where e = 19 and the number 2 where e = 0;
b = the num~er 2;
c = the number 2;
d = the number 0 or 1; and e = the number 0 or 1 3 with the proviso that a ~ d = 2 or 3.
The following are mentioned as examples of compounds correspondi:ng to the formula (I):
It is known from German Patent No. 1,190,18~ dated April 1, 1965 in the name of Bayer Aktiengesellschaft that high molecular wei~ht poly-triazines can be obtained by polymerising di-functional or polyfunctional aromatic cyanic acid esters at an elevated temperature, optionally in the presence of polymerisation promoters. The polymers are distinguished, for example, by their remarkable stability at elevated temperatures and are duroplastic in character after tempering for a sufficiently long period.
The resistance of the polytriazines to acids and various solvents may also be emphasised. It was not possible to detect any changes in test specimens that had been stored for thrbe months in benzene, dimethyl formamide, super high octane petrol, concentrated acetic acid, trichloroacetic acid, chromic acid, aqueous formaldehyde solution, fuel oil, saturated sodium phosphate solution and concentrated~hydrogen peroxide (cf. Kunststoffe 58, number 19, pages 827 to g32 (1968)).
In addition,~ it was found by V.V. Korchak et al (cf.
20 Vysokomolekulyarnye soedineniya 1974, number 1, pages 15 to 21) that the thermal and thermo-oxidative destruction of polytriazines based on aromatic cyanic acid esters is grea*ly influenced by moisture.
An object of the invention is to improve the polytriazines in regard to their resistance to hydrolysis.
This object is achieved by using polyfunctional aromatic cyanic ; acid esters having alkyl or phenyl radicals or halogen atoms~at least in the ortho, ortho'-position to at least one -OCN-group ~or the polytrimerisation reaction.
:
. . ~ , . . .
~8$~
Accordingly, the present invention relates to a process for the production of a hydrolysis-stable polytria~ine, wh:ich comprises polytrimer-ising a polyfunctional aromatic cyanic acid ester having the general formula:
(NCO ~ ~ ~ L ~ CN)d ll (R)b (R')c in which R represents chlorine or bromine, or Cl-Ca alkyl, the two radicals R not having to be the same, with the proviso that at least the ortho, ortho'-position to at least one cyanic acid ester group is substituted by R;
Rl has the same meaning as R;
A represents a si.ngle bond, oxygen, the sulphonyl group, the carbonyl group, the carboxyl dioxy group, the methylene, ethylene, or 2,2-propylene group C~13 ( - C - ) or the cyclohexylene radical;
a represents the number l where e = l, and the number 2 where e = 0;
b represents the number 2;
c represents the number 2;
d represents the number 0 or l; and e represents the number 0 or l, with the proviso that a + d = 2 or 3.
The invention also relates to the polytriazines obtained by this . .
process.
The~aromatlc cyanic acid.esters preferably correspond to the general formula (I):
A (OCN)n (I) :
: : - 2 --in which A represen-ts an aromatic radical or an aromatic radical interrupted by bridge members having alkyl or phenyl radicals or halogen atoms at least in the ortho and ortho'-positions to at least one -OCN-group, and n is a number from 2 to ~.
The aromatic cyanic acid esters of formula (I) used in accordance with the invention may be obtained by the process according to Canadian Patent number 812,232.
From 1 to 1.1 moles of cyanogen halide ancl 1 mole of a base or base mixture may be used per phenolic hydroxyl group. The reaction tempera-tures are in the range of from--~0C to +65C. Suitable basesare inorganic bases, such as sodium hydroxide, potassium hydroxide, soda, potash or - 2a -.
~ ' .
calcium hydroxide, or tertiary amines such as trimethylamine or triethylamine, whilst suitable solvents or suspending agents include water, alcohols, ketones, hydrocarbons, chlorinated hydrocarbons or mixtures thereof.
The aromatic cyanic acid esters preferably correspond to the general formula (II):
~ A ~OCN)d (Il) Cl~)_ (R ' ~ C
in which R represents halogen, linear or branched Cl-Cg alkyl or phenyl, several radicals R not having to be the same, with the proviso that at least the ortho, ortho'-position to at least one cyanic acid ester group is substituted by R;
R' has the same meaning as R or represents the group (III):
(OCN)d (111) Rb at least the ortho, ortho'-position to at least one cyanic : acid ester group again being substituted by R'; :
A represents a single bond, an alkylene group with from 1 to 9 carbon atoms optionally substituted by Cl-C4 .
~ ..
,~, .
:
.,, : : .
: ~ ~ . ' . ' all~yl or phenyl, a cycloaliphatic or aroma-tic 5-1ne~bered or 6-me~bered ring optionally interrwpted ~y oxygen, oxygen, th0 sulphonyl group (~S02~ the carb~nyl dioxy group (-OC0-) or the carbonyl group;
a = the number 1 or 2, b = a number ~rom 2 to 4 9 c = a number ~rom 2 to 4, d = the number 1 or 2, e = 0 or 1, with the proviso that the sum of a and d is always a number ~rom 2 to 4.
More especially, -the symbols in the formula (II) have the following meanings:
R represents a chlorine or bromine, or Cl-C4 alkyl;
A represents a single bond, oxygen, the sulphonyl group9 the carbonyl group, the carbonyl dioxy group, the methylene, ethylene) or 2~2-propylene group (- C -), or the cyclohexylene radical;
a = the number 1 where e = 19 and the number 2 where e = 0;
b = the num~er 2;
c = the number 2;
d = the number 0 or 1; and e = the number 0 or 1 3 with the proviso that a ~ d = 2 or 3.
The following are mentioned as examples of compounds correspondi:ng to the formula (I):
2,4-dimethyl_1,3-dicyanatobenzene t 2,6-di-tert.-butyl-1,4-dicyanatobenzene, tetramethyl-1,4~dicyanatobenzene, 2,4,6-: 1~3-dicyanatobenzene, 2,4,6-trimethyl trimethyl~ ,3~5-tricyanatobenzene; 3,3',5,5i-tetramethyl-: Le A 16 471 ~ - 4 .
- . -4,~ dicyanatodiphenyl, 3,3', 5,5'-tetrachloro-4,4'-dicyanatodiphenyl, 3,3', 5,5'-tetramethyl-4,4'-dicyanatodiphenyl ether, 3,3', 5,5'-tetrachloro-4,4'-dicyanatodiphenyl ~ther, 3,3', 5,5'-tetrabromo-4,4'-dicyanatodiphenyl ether, 3,3', 5,5'-tetramethyl-4,4'-dicyanatodiphenyl sulphone, 3,3', 5,5'-tetrachloro-4,4'-dicyanatodiphenyl sulphone, 3,3', 5,5'-tetrabromo-4,4'-dicyanatodiphenyl sulphone, 2,2'-bis-(3,5-dimethyl-4-cyanatophenyl)-propane, 2,2-bis-(3,5-dichloro-4-cyanato-10 phenyl)-propane and 2,2-bis-~3,5~dibromo-4-cyanatophenyl)-propane.
In cases where it is desired to use particularly pure aromatic cyanic acid esters with a high stability in storage, it is advisable to adopt a procedure similar to that described in our Canadian Patents numbers 1,063,129 and 1,055,513 which relate to the production of highly pure polyfunctional cyanic acid esters. According to Canadian Patent number 1,063,129 di- or polytrialkyl ammonium phenolates (for example polytriethyl ammonium phenolates) are reacted with an excess of a cyanogen halide in an organic solvent, optionally in the presence of catalytic quantities of - trialkylamines such as triethylamine, to form the corresponding aromatic cyanic acid esters.
According to our Canadian Paten* number 1,055,513 alkali or alkaline earth metal salts, preferably sodium, potassium, calcium and barium salts, of aromatic dihydroxy or polyhydroxy compounds are reacted with a cyanogen halide in a~solvent, optionally in the presence of catalytic quantities of a tertiary amine.
From 1 to 2 moles and preferably from 1 to 1.4 moles of cyanogen halide, and from 1 to 1.~ moles, preferably from ,,:
"
~: ' I to L 3 Illole~, oL~ a ~a~e or base mixture, may be used ~or ~v~ry ~)henolic hydroxyl group, -the base or the base m-Lxture y~ l~eing usecl in a deficit relative -to the cyanoge~
llalide, Suital)le solven-ts are, tor example, water; lower alipha-tic alcohols such as methanol, ethanol, propanol, isopropanol or bu-tanol; aliphatic ke-tones such as ace-tone, methyl ethyl ketone~ diethyl ketone, methylisopropyl ketone or me-thylisohutyl ke-tone; alipha-tic or aroma-tic hydrocarbons, preferred alipha-tic hydrocarbons being the fractions accumula-ting during distillation o~ naturally occurring mixtures~ such as pe-troleum ether, light petrol or petrol, whilst examples o~ aromatic hydrocarbons are benzene~
-toluene and xylenes; aliphatic and aromatic chlorinated hydrocarbons such as dichloroethane, perchloroethylene, chlorobenzene or dichlorobenzene; ethers such as diethyl ether9 diisopropyl ether, dioxane, tetrahydro~uran or di-sec.-butyl ether; nitrohydrocarbons such as nitromethane~
nitrobenzene or nitrotoluene; amides such as dimethyl ~orm~mide or dimethyl acetamides; and mixtures therao~, ~ Suitable inorganic or organic bases are thosementioned ; in GB-PS 1,007 790.
These processes are generally carried out at temperatures `~ - in the range o~ ~rom -40C to +65~C and pre~erably at temperatures in the range,o~ from QC to 30C. In oases where cyanogen chloride is used, the reaction is preferably carried out below the boiling point ~13C), although where cyanogen bromide is u~ed the reaction may even be carried out at temperatures above 50C.
Tertiary amines, which are used in ca~alytic quantities (0.001 to 10 % by weigh-t9 more especially 0.001 to l.0 ~0 by weight, based on the alkali or alkaline earth phenolate) .-, ~ . ' .
in accordance with our Canadian Patent number 1,055J513 correspond to the general formula:
Rl in which Rl, R2, R3 represent alkyl, aryl and cycloalkyl radicals which do not hava to be the same, with from 1 to 36 carbon atoms, more especially with up to 18 carbon atoms, such as for example trimethylamine, triethylamine, methyl diethylamine, tripropylamine, tributylamine, methyl dibutylamine, dinonyl methylamine, dimethyl stearylamine, dimethyl cyclohexylamine and diethyl aniline.
The aromatic cyanic acid esters may be reacted by heating to about 30C - 250CJ preferably to 50C - 200C, optionally in solu~ion and optionally in the presence of a catalyst or catalyst mixture, to form partially crosslinked prepolymers which are soluble in organic solvents.
The prepolymers represent polymeric cyanate-group-containing triazines of liquid, wax-like or solid consistency and are soluble in organic solvents.
They are highly stable in storage. As shown by the IR-spectrum, they have the band characteristic of the -0-C-N-group at 4.51u in addition to the triazine struc~ure.
The prepolymers may be converted into high molecular weight polymers of triazine structure by heating to a temperature of from 120C to 350C, preferably from 150C to 250C, optionally in solution and optionally in the presence o a catalyst or catalyst mixture. The end products are substantially insoluble in solvents and are :
,~
, ' si~le As shown l)y the IR-spec-tru~, there ~re no ~ther linkage principles in -the ~olymer apart lrom -the triazine structures The polytria~ines may of course also be produced in a sin~le stage.
Suitable catalysts for ~the production of -the prepolymer and the high molecular weigh-t end polymer with -triazine structures include acids J bases, salts, nitrogen and phosphorus compounds 9 ~or example Lewis acids such as 1~) AlC13, BF3, FeC13, TiC14, ZnC12 or SnC14; proton acids such as HCl or H3P04; aromatic hydroxy compounds such as phenol, p-nitrophenol, pyrocatechol or dihydro~y napthalene;
sodium hydroxide, sodium methylate, sodium phenolate, -trimethylamine, triethylamine, tributylamine, diazabicyclo-(2,2,2)-octane, quinoline, isoquinoline; tetrahydroiso~ui~oline, tetraethyl ammonium chloride, pyridine-N-oxide, tributyl phosphine, phospholine- ~3-l-oxa-l-phenyl9 zinc octoate, tin octoate, zinc napthenate, and mixtures thereof~
The catalysts may be used in ~uantities o~ ~rom 0.001 %
by weight to 10 ~ by weight; based on the prepolymer or on the cyanic acid ester containing cyanamide groups 9 or i~
desired in even larger quantities.
The aromatic cyanic acid esters or the prepolymers may be used, in solution in inert solvents such as acetone, benzene, xylene, chlorobenzene, ethylacetate~ tetrahydro~uran, dibutyl ether or dimethyl ~ormamide~ or in powder ~orm3 ~or the produotion o~ coatings on substrates such as metals, oeramios, glass, earthenware, etc., or, in solution in organic solvents, as impregnating lacquers or laminating resins. I~ desired, the prepolymers may be combined with ~illers, pigments, glass ~ibres, metal ~ibres and glass cloths, and may be used for the production o~ mouldings or ~ Le ~ 16 4?1 ~ _ 8 -: ~ ~
lamillates Yellow to brown coloured, -transparent end roducts with ex-treme hardness and a high temperature rosis-tancc are obtained after hardening, The par-t-lcular advantage of the poly-triazines obtained in accordance with the invention9 apart from their high heat resistance, is the fact -that they are unaffected by hydrolysing chemicals such as alkalis.
The percentage contents and par-ts quoted in the following Examples relate to weight unless otherwise indicated.
. . _ 0.03 % by weight of zinc octoate is added to 15 g of bis-2,2-(4-cyanato-3,5-dimethyl phenyl)-propane, followed by hea-ting -to 140C. A clear mel-t is obtained and is kept at 1~0C ~or 8 hours. A~ter cooling, a prepolymer is obtained which is wax like at room temperature and which becomes highly viscous above about 50~C and fluid at above about 80C, ~D90 1.5520-90~ The IR-spectrum of this prepolymer shows the band characteristic o~ the -O-C_N-group at 4.5 ~ and the band characteristic of the s triazine ring at 6.4 ~ and 7.25 p. Hardening in-to an eætremely hard, honey-coloured polytriazine takes place over a period of 6 hours at 200~C.
~ test The polytriazine thus prepared is not dissolved by boiling ~or 120 hours in 40 % NaOH, 25 % ammonia solution or 20 % hydrochloric acid. By contrast, a polytriazine produced from bis-2~2-(4-cyanatophenyl)-propane is split . hydrolytically into cyanuric acid and bisphenol A after ~0 only 5 hoursO
Le A 16 471 _ 9 _ , ., _ 0.1 ~0 by weigh-t of zinc octoate is added to 20 g of bis-2,2-(4-cyanato-3,~-dim0thyl phenyl)-propane~ followed by heating for 3 hours a-t 150C. A clear yellow-colowred mel-t is obtained The -temperature is then increased to 180C and left at that level for 3 hours. An extremely hard, honey-coloured poly-triazine is obtained after cooling 005 ~ by weight of pyrocatechol and 0.5 % by weight of diazabicyclo-(2,2,2)-octane are added to 1 kg of bis-2,2-(4-cyanato-3,5-dime-thyl phenyl)-propane, followed by heating with stirring for 8 hours at 150C. ~he highly viscous melt is then poured out. A pale yellow coloured prepolymer is obtained, I-t is fluid above 80C, nD9 1.5520 90, The I~-spectrum shows the characteristic bands at 4.5 ~ (-0-C-N) and at 6.4 ~ and 7,25 p (s-triazine).
0.1 ~ by weight of tin octoate is added to 15 g of this prepolymer, followed by hardening over a period of 3 hours at 190C to form an extremely hard, light brown poly-triazine.
EX~MPLE 4 0.1 ~ by weight of zinc chloride is added to 10 g of 2,6-di-tertO-butyl hydroquinone dicyanate, followed by heating for 3 hours to 120C. ~he product obtained is then kept at 200C for 3 hours~ A hard, yellow brown coloured polymer is obtained after cooling, showing the bands characteristic of the s-tria~ine ring at 6,4 ~ and ` 7.25 20 g of 2,4,6-trimethyl resorcinol dicyanate are mi~ed with 0.02 ~ by weight of zinc octoate, followed by heating for 5 hours to 150~C. A prepolymer: solidifying slowly at room temperature is obtained (IR~spectrum: -C-C-N
Le A 16 471 - 10 -a-t 4.5 ~, s-triazine ring at ~,4 ~ a:nd 7,Z5 ~). Hardening of this prepolymer into an extremely ha:rd, brown poly-triazine takes place over a pe.riod of 2 hours a-t 220C~
10 g of 2, 3 9 5,6-tetramethyl hydroquinone dicyana-te are heated for 4 hours to 160C with OoOl % by weight o~
tin octoate, The prepolymer obtained is hard and brittle at room temperature and highly viscous above 75C.
Hardening of this prepolymer takes place over a period of 5 hours at 230~Co A very hard, brown polytriazine is obtainedO
10 g of bis-2 ~ 2-(4-cyanato-3,5-dichlorophenyl)-propane are slowly heated to 150~C. After 3 hours the temperature is increased to 180C and af-ter another hour to 220C.
A~ter a total of 5 hours a brown prepolymer is obtained with the characteris$ic s-triazine ring bands in the IR-spectrum~
.
. ~ . .
- . -4,~ dicyanatodiphenyl, 3,3', 5,5'-tetrachloro-4,4'-dicyanatodiphenyl, 3,3', 5,5'-tetramethyl-4,4'-dicyanatodiphenyl ether, 3,3', 5,5'-tetrachloro-4,4'-dicyanatodiphenyl ~ther, 3,3', 5,5'-tetrabromo-4,4'-dicyanatodiphenyl ether, 3,3', 5,5'-tetramethyl-4,4'-dicyanatodiphenyl sulphone, 3,3', 5,5'-tetrachloro-4,4'-dicyanatodiphenyl sulphone, 3,3', 5,5'-tetrabromo-4,4'-dicyanatodiphenyl sulphone, 2,2'-bis-(3,5-dimethyl-4-cyanatophenyl)-propane, 2,2-bis-(3,5-dichloro-4-cyanato-10 phenyl)-propane and 2,2-bis-~3,5~dibromo-4-cyanatophenyl)-propane.
In cases where it is desired to use particularly pure aromatic cyanic acid esters with a high stability in storage, it is advisable to adopt a procedure similar to that described in our Canadian Patents numbers 1,063,129 and 1,055,513 which relate to the production of highly pure polyfunctional cyanic acid esters. According to Canadian Patent number 1,063,129 di- or polytrialkyl ammonium phenolates (for example polytriethyl ammonium phenolates) are reacted with an excess of a cyanogen halide in an organic solvent, optionally in the presence of catalytic quantities of - trialkylamines such as triethylamine, to form the corresponding aromatic cyanic acid esters.
According to our Canadian Paten* number 1,055,513 alkali or alkaline earth metal salts, preferably sodium, potassium, calcium and barium salts, of aromatic dihydroxy or polyhydroxy compounds are reacted with a cyanogen halide in a~solvent, optionally in the presence of catalytic quantities of a tertiary amine.
From 1 to 2 moles and preferably from 1 to 1.4 moles of cyanogen halide, and from 1 to 1.~ moles, preferably from ,,:
"
~: ' I to L 3 Illole~, oL~ a ~a~e or base mixture, may be used ~or ~v~ry ~)henolic hydroxyl group, -the base or the base m-Lxture y~ l~eing usecl in a deficit relative -to the cyanoge~
llalide, Suital)le solven-ts are, tor example, water; lower alipha-tic alcohols such as methanol, ethanol, propanol, isopropanol or bu-tanol; aliphatic ke-tones such as ace-tone, methyl ethyl ketone~ diethyl ketone, methylisopropyl ketone or me-thylisohutyl ke-tone; alipha-tic or aroma-tic hydrocarbons, preferred alipha-tic hydrocarbons being the fractions accumula-ting during distillation o~ naturally occurring mixtures~ such as pe-troleum ether, light petrol or petrol, whilst examples o~ aromatic hydrocarbons are benzene~
-toluene and xylenes; aliphatic and aromatic chlorinated hydrocarbons such as dichloroethane, perchloroethylene, chlorobenzene or dichlorobenzene; ethers such as diethyl ether9 diisopropyl ether, dioxane, tetrahydro~uran or di-sec.-butyl ether; nitrohydrocarbons such as nitromethane~
nitrobenzene or nitrotoluene; amides such as dimethyl ~orm~mide or dimethyl acetamides; and mixtures therao~, ~ Suitable inorganic or organic bases are thosementioned ; in GB-PS 1,007 790.
These processes are generally carried out at temperatures `~ - in the range o~ ~rom -40C to +65~C and pre~erably at temperatures in the range,o~ from QC to 30C. In oases where cyanogen chloride is used, the reaction is preferably carried out below the boiling point ~13C), although where cyanogen bromide is u~ed the reaction may even be carried out at temperatures above 50C.
Tertiary amines, which are used in ca~alytic quantities (0.001 to 10 % by weigh-t9 more especially 0.001 to l.0 ~0 by weight, based on the alkali or alkaline earth phenolate) .-, ~ . ' .
in accordance with our Canadian Patent number 1,055J513 correspond to the general formula:
Rl in which Rl, R2, R3 represent alkyl, aryl and cycloalkyl radicals which do not hava to be the same, with from 1 to 36 carbon atoms, more especially with up to 18 carbon atoms, such as for example trimethylamine, triethylamine, methyl diethylamine, tripropylamine, tributylamine, methyl dibutylamine, dinonyl methylamine, dimethyl stearylamine, dimethyl cyclohexylamine and diethyl aniline.
The aromatic cyanic acid esters may be reacted by heating to about 30C - 250CJ preferably to 50C - 200C, optionally in solu~ion and optionally in the presence of a catalyst or catalyst mixture, to form partially crosslinked prepolymers which are soluble in organic solvents.
The prepolymers represent polymeric cyanate-group-containing triazines of liquid, wax-like or solid consistency and are soluble in organic solvents.
They are highly stable in storage. As shown by the IR-spectrum, they have the band characteristic of the -0-C-N-group at 4.51u in addition to the triazine struc~ure.
The prepolymers may be converted into high molecular weight polymers of triazine structure by heating to a temperature of from 120C to 350C, preferably from 150C to 250C, optionally in solution and optionally in the presence o a catalyst or catalyst mixture. The end products are substantially insoluble in solvents and are :
,~
, ' si~le As shown l)y the IR-spec-tru~, there ~re no ~ther linkage principles in -the ~olymer apart lrom -the triazine structures The polytria~ines may of course also be produced in a sin~le stage.
Suitable catalysts for ~the production of -the prepolymer and the high molecular weigh-t end polymer with -triazine structures include acids J bases, salts, nitrogen and phosphorus compounds 9 ~or example Lewis acids such as 1~) AlC13, BF3, FeC13, TiC14, ZnC12 or SnC14; proton acids such as HCl or H3P04; aromatic hydroxy compounds such as phenol, p-nitrophenol, pyrocatechol or dihydro~y napthalene;
sodium hydroxide, sodium methylate, sodium phenolate, -trimethylamine, triethylamine, tributylamine, diazabicyclo-(2,2,2)-octane, quinoline, isoquinoline; tetrahydroiso~ui~oline, tetraethyl ammonium chloride, pyridine-N-oxide, tributyl phosphine, phospholine- ~3-l-oxa-l-phenyl9 zinc octoate, tin octoate, zinc napthenate, and mixtures thereof~
The catalysts may be used in ~uantities o~ ~rom 0.001 %
by weight to 10 ~ by weight; based on the prepolymer or on the cyanic acid ester containing cyanamide groups 9 or i~
desired in even larger quantities.
The aromatic cyanic acid esters or the prepolymers may be used, in solution in inert solvents such as acetone, benzene, xylene, chlorobenzene, ethylacetate~ tetrahydro~uran, dibutyl ether or dimethyl ~ormamide~ or in powder ~orm3 ~or the produotion o~ coatings on substrates such as metals, oeramios, glass, earthenware, etc., or, in solution in organic solvents, as impregnating lacquers or laminating resins. I~ desired, the prepolymers may be combined with ~illers, pigments, glass ~ibres, metal ~ibres and glass cloths, and may be used for the production o~ mouldings or ~ Le ~ 16 4?1 ~ _ 8 -: ~ ~
lamillates Yellow to brown coloured, -transparent end roducts with ex-treme hardness and a high temperature rosis-tancc are obtained after hardening, The par-t-lcular advantage of the poly-triazines obtained in accordance with the invention9 apart from their high heat resistance, is the fact -that they are unaffected by hydrolysing chemicals such as alkalis.
The percentage contents and par-ts quoted in the following Examples relate to weight unless otherwise indicated.
. . _ 0.03 % by weight of zinc octoate is added to 15 g of bis-2,2-(4-cyanato-3,5-dimethyl phenyl)-propane, followed by hea-ting -to 140C. A clear mel-t is obtained and is kept at 1~0C ~or 8 hours. A~ter cooling, a prepolymer is obtained which is wax like at room temperature and which becomes highly viscous above about 50~C and fluid at above about 80C, ~D90 1.5520-90~ The IR-spectrum of this prepolymer shows the band characteristic o~ the -O-C_N-group at 4.5 ~ and the band characteristic of the s triazine ring at 6.4 ~ and 7.25 p. Hardening in-to an eætremely hard, honey-coloured polytriazine takes place over a period of 6 hours at 200~C.
~ test The polytriazine thus prepared is not dissolved by boiling ~or 120 hours in 40 % NaOH, 25 % ammonia solution or 20 % hydrochloric acid. By contrast, a polytriazine produced from bis-2~2-(4-cyanatophenyl)-propane is split . hydrolytically into cyanuric acid and bisphenol A after ~0 only 5 hoursO
Le A 16 471 _ 9 _ , ., _ 0.1 ~0 by weigh-t of zinc octoate is added to 20 g of bis-2,2-(4-cyanato-3,~-dim0thyl phenyl)-propane~ followed by heating for 3 hours a-t 150C. A clear yellow-colowred mel-t is obtained The -temperature is then increased to 180C and left at that level for 3 hours. An extremely hard, honey-coloured poly-triazine is obtained after cooling 005 ~ by weight of pyrocatechol and 0.5 % by weight of diazabicyclo-(2,2,2)-octane are added to 1 kg of bis-2,2-(4-cyanato-3,5-dime-thyl phenyl)-propane, followed by heating with stirring for 8 hours at 150C. ~he highly viscous melt is then poured out. A pale yellow coloured prepolymer is obtained, I-t is fluid above 80C, nD9 1.5520 90, The I~-spectrum shows the characteristic bands at 4.5 ~ (-0-C-N) and at 6.4 ~ and 7,25 p (s-triazine).
0.1 ~ by weight of tin octoate is added to 15 g of this prepolymer, followed by hardening over a period of 3 hours at 190C to form an extremely hard, light brown poly-triazine.
EX~MPLE 4 0.1 ~ by weight of zinc chloride is added to 10 g of 2,6-di-tertO-butyl hydroquinone dicyanate, followed by heating for 3 hours to 120C. ~he product obtained is then kept at 200C for 3 hours~ A hard, yellow brown coloured polymer is obtained after cooling, showing the bands characteristic of the s-tria~ine ring at 6,4 ~ and ` 7.25 20 g of 2,4,6-trimethyl resorcinol dicyanate are mi~ed with 0.02 ~ by weight of zinc octoate, followed by heating for 5 hours to 150~C. A prepolymer: solidifying slowly at room temperature is obtained (IR~spectrum: -C-C-N
Le A 16 471 - 10 -a-t 4.5 ~, s-triazine ring at ~,4 ~ a:nd 7,Z5 ~). Hardening of this prepolymer into an extremely ha:rd, brown poly-triazine takes place over a pe.riod of 2 hours a-t 220C~
10 g of 2, 3 9 5,6-tetramethyl hydroquinone dicyana-te are heated for 4 hours to 160C with OoOl % by weight o~
tin octoate, The prepolymer obtained is hard and brittle at room temperature and highly viscous above 75C.
Hardening of this prepolymer takes place over a period of 5 hours at 230~Co A very hard, brown polytriazine is obtainedO
10 g of bis-2 ~ 2-(4-cyanato-3,5-dichlorophenyl)-propane are slowly heated to 150~C. After 3 hours the temperature is increased to 180C and af-ter another hour to 220C.
A~ter a total of 5 hours a brown prepolymer is obtained with the characteris$ic s-triazine ring bands in the IR-spectrum~
.
. ~ . .
Claims
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the production of a hydrolysis-stable polytriazine, which comprises polytrimerising a polyfunctional aromatic cyanic acid ester having the general formula:
in which R represents chlorine or bromine, or Cl - Ca alkyl, the two radicals R not having to be the same, with the proviso that at least the ortho, ortho'-position to at least one cyanic acid ester group is sub-stituted by R;
R' has the same meaning as R;
A represents a single bond, oxygen, the sulphonyl group, the carbonyl group, the carbonyl dioxy group, the methylene, ethylene, or 2,2-propylene group C,H3 (- C -), or the cyclohexylene radical;
a represents the number 1 where e = 1, and the number 2 where e = 0;
b represents the number 2;
c represents the number 2;
d represents the number 0 or 1; and e represents the number 0 or 1, with the proviso that a + d = 2 or 3.
2. A process according to claim 1 carried out in the presence of a polytrimerisation-promoting catalyst.
3. A polytriazine when prepared by a process as claimed in
claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752533123 DE2533123A1 (en) | 1975-07-24 | 1975-07-24 | HYDROLYSIS-STABLE POLYTRIAZINE AND A PROCESS FOR THEIR PRODUCTION |
| DEP2533123.1 | 1975-07-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1098644A true CA1098644A (en) | 1981-03-31 |
Family
ID=5952372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA257,578A Expired CA1098644A (en) | 1975-07-24 | 1976-07-22 | Hydrolysis-stable polytriazines and a process for their production |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5214697A (en) |
| BE (1) | BE844389A (en) |
| CA (1) | CA1098644A (en) |
| CH (1) | CH603718A5 (en) |
| DE (1) | DE2533123A1 (en) |
| FR (1) | FR2318890A1 (en) |
| GB (1) | GB1526035A (en) |
| IT (1) | IT1066034B (en) |
| NL (1) | NL7608214A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4528366A (en) * | 1982-09-28 | 1985-07-09 | The Dow Chemical Company | Production of polytriazines from aromatic polycyanates with cobalt salt of a carboxylic acid as catalyst |
| JPS6027497A (en) * | 1983-07-22 | 1985-02-12 | ザボ−ド−ウトウズ，プリ，モスコフスコム，アフトモビルノム，ザボ−デ，イメ−ニ，イ−，ア−，リハチエワ | Press |
| US4713442A (en) * | 1983-11-16 | 1987-12-15 | The Dow Chemical Company | Polyaromatic cyanate |
| US4751323A (en) * | 1983-11-16 | 1988-06-14 | The Dow Chemical Company | Novel polyaromatic cyanates |
| EP0180649B1 (en) * | 1984-10-11 | 1988-11-30 | The Dow Chemical Company | Novel catalysts for the production of polytriazines from aromatic polycyanates |
| US4709008A (en) * | 1986-06-30 | 1987-11-24 | Interez, Inc. | Blend of tris (cyanatophenyl) alkane and bis(cyanatophenyl) alkane |
| US4740584A (en) * | 1986-09-08 | 1988-04-26 | Interez, Inc. | Blend of dicyanate esters of dihydric phenols |
| DE3734986A1 (en) * | 1986-10-17 | 1988-04-28 | Mitsubishi Gas Chemical Co | METHOD FOR PRODUCING A POLYFUNCTIONAL CYAN ACID ESTER POLYMER |
| JPH0337264A (en) * | 1989-07-04 | 1991-02-18 | Mitsubishi Gas Chem Co Inc | Production of cured product of cyanate ester resin |
| CA2115537A1 (en) * | 1993-02-23 | 1994-08-24 | Yasuhiro Endo | Cyanate resin composition and copper-clad laminate using the composition |
-
1975
- 1975-07-24 DE DE19752533123 patent/DE2533123A1/en not_active Withdrawn
-
1976
- 1976-07-21 JP JP8609576A patent/JPS5214697A/en active Pending
- 1976-07-22 IT IT5055776A patent/IT1066034B/en active
- 1976-07-22 CH CH941476A patent/CH603718A5/xx not_active IP Right Cessation
- 1976-07-22 BE BE169127A patent/BE844389A/en unknown
- 1976-07-22 GB GB3059376A patent/GB1526035A/en not_active Expired
- 1976-07-22 CA CA257,578A patent/CA1098644A/en not_active Expired
- 1976-07-23 NL NL7608214A patent/NL7608214A/en not_active Application Discontinuation
- 1976-07-23 FR FR7622565A patent/FR2318890A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| GB1526035A (en) | 1978-09-27 |
| JPS5214697A (en) | 1977-02-03 |
| DE2533123A1 (en) | 1977-02-10 |
| NL7608214A (en) | 1977-01-26 |
| BE844389A (en) | 1977-01-24 |
| FR2318890A1 (en) | 1977-02-18 |
| IT1066034B (en) | 1985-03-04 |
| FR2318890B1 (en) | 1979-07-27 |
| CH603718A5 (en) | 1978-08-31 |
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