CA1086891A - Polytriazines and a process for their production - Google Patents
Polytriazines and a process for their productionInfo
- Publication number
- CA1086891A CA1086891A CA257,557A CA257557A CA1086891A CA 1086891 A CA1086891 A CA 1086891A CA 257557 A CA257557 A CA 257557A CA 1086891 A CA1086891 A CA 1086891A
- Authority
- CA
- Canada
- Prior art keywords
- mol
- formula
- cyanamide
- prepolymer
- sulphonyl
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Abstract of Disclosure Mixtures of aliphatic, cycloaliphatic or aromatic poly-functional N-cyanosulphonamides and aliphatic, arali-phatic or heterocyclic, polyfunctional cyanamides may be converted in a first step at a temperature of 30°C to 150& into a prepolymer (polymeric N-cyano-N-sulphonyl guanidines) soluble in organic solvents or into a fusible prepolymer and in a second step at a temperature of 150°C to 350°C into a high molecular weight polymer of polytriazone structure which is substantially insoluble in solvents.
Description
10~8gl This invention relates to high molecular weight polytriazines and to a process for their production by heat-treating soluble, polymeric N-cyano-N-sulphonyl guanidines which in turn have been obtained by the poly-addition of polyvalent N-cyanosulphonamides and polyvalen~
cyanamides.
It is known from German PS 1,190,184 that high molecular weight polytriazines can be obtained by p~lymeris-ing difunctional or polyfunctional aromatic cyanic acid esters at elevated temperature, optionally in the presence of polymerisation promoters.
According to a ~apanese Application filed by Sugino and published as 6265/66 on April 4, 1966, primary diamines are reacted with cyanogen halide to form di(cyanamides~
which are then processed into polymers.
The polymerisation of polyfunctional cyanamides of secondary amines with catalytic to more than molar quan-tities of mono- or poly-hydroxyl and/or thiol compounds at temperatures of from 50 to 250C to form polymeric products, is also known, cf. German OS 1,595,651.
Finally, a process for the production of macromole-cular polyguanidines by reacting N,N'-dicyanamides of the formula NC-NH-R-NH-CN on their own or with an N,N'-dicyanamide of the formula NC-NR'-R-NR'CN (R and R' represent hydrocarbon radicals), is known from Netherlands Patent No. 55 826.
It has now been found that high molecular weight polytriazines can be obtained by converting N-cyanosulphon-amides corresponding to the general formula (I):
A(S02-NH-CN)n (I) '. . '' - ' ~ ~ '.
1~8fiB9~
in which A represents alipha-tic, cycloaliphatic or aromati.c polyvalent radicals and n is a number from 2 to 5, with poly~unctional cyanamides corresponding to the general formula (II):
NC-N-R-N-CN (II) R' R"
in which R' and R" are the same or different and represent aliphatic or araliphatic radicals or9 together with the ~N-R-N-group, form a heterocyclic ring, and R represents an alkylene, cycloalkylene or arylene radical or two or more such radicals which may be attached by arylene or alkylene radicals or by hetero atoms, R optionally containing further ; radicals of the formula:
-N-CN
R~
at elevated temperatures into a prepolymer soluble in organic solvents or into a fusible prepolymer, and allowing the prepolymer to react to completion at elevated temperatures to form a high molecular weight polymer of polytriazine structure which is substantially insoluble in solvents.
It is preferred to react from 30 to 70 mol % of N-cyanosulphonamides of formula (I) with from 70 to 30 mol %
of cyanamides of formula (II).
The present invention also relates to mixtures of A) N-cyanosulphonamides of general formula (I) and B) cyan~mides o~general formula (II), which can be converted into high molecular weight polymers of polytriazine structure which are substantially insoluble Le A 16 549 -2-1~6E~91 in solvents.
The mixtures preferably consist o$ $rom 30 to 70 mol ~ of N-cyanosulphonamides o$ formula (I) and of from 70 to 30 mol ~ of cyanamides o~ formula (II).
The process according to the invention i~ illu~trated by the following exemplary equation (in which x > 2), the terminal groups being cyanamide groups:
Le A 16 549 _3_ - , . . .
NC-HNO"S ~\~, S 02NHCN ~
W + NC--N N--CN
~ 30C to 150C
_~ CN Nll NE}
x x,> 2 (A) 150C to 350C
~`
\ I
N=C ~ N
l{N--502~ --C~
~N~
J
b' N
(B) Le A 16 549 _4_ 1~)8~91 q`he symbols in formula (I~ pre~erably have the following ~eaning;
A represents a polyvalent~ aliphatic~ straight chain or branclled-chain, saturated or unsaturated radical with from 1 tc 20 carbon atoms, more especially with ~rom 2 to 12 carbon atoms;
a polyvalent cycloalipha$ic radical w:ith from 4 to 12 carbon atoms, more especially a 5- or 6-membered, cycloaliphatic, polyvalent radical; a polyvalent cycloaliphatic radical with from 4 to 12 carbon atoms, more especially with from 5 to 10 carbon atoms, interrupted by Cl to C4-alkylene groups or by phenyl or by hetero atoms (0~ S); a polyvalent~ aromatic radical with from 6 to 14 carbon atoms, more especially with from 6 to 10 carbon atoms; a polyvalent aromatic ring with from 6 to 14 carbon atoms, more especially with 6 carbon atoms, interrupted by Cl to C4-alkylene~ by oxygen, by the carbonyl group (-C0-), by the carbonyl dioxy group l~ ~ by the sulphonyl group (-OCO-) (-S02-)~ by a cycloaliphatic or aromatic 5-membered or 6-membered carbocyclic ring or by a single bond; and n is the number 2 or 3, more especially the number 2.
N-cyanosulphonamides of the formula (I), in which A repre-sents the aromatic radicals defined above~ are particularly preferred.
The following compounds are mentioned by way of example:
25 hexane-di-(sulphonyl cyanamide)-1,6 and isomers~
benzene-di-(sulphonyl cyanamide)-1,3; -1,4, benzene-tri-(sulphonyl cyanamide)-1,3,5, naphthalene-di-(sulphonyl cyanamide)-1,3 and isomers, naphthalene-tri-(sulphonyl cyanamide)-1,3,5;
-1,3,6; -1,3,7;
naphthalene-tetra-(sulphonyl cyanamide)-1~3~5~7 diphenyl-di-(sulphonyl cyanamide)-2~2' (-4~4'; -3,3', -2,4') Le A 16 549 _5_ ~08~891 diphenyl methane-di-(sulphonyl cyanamide)-4,4'-, 2,4' diphenyl diphenyl methane-di-(sulphonyl cyanamide)-4~4'-and isomers, diphenyl sulphone-di-(sulphonyl cyanamide)-3,3'- and isomers, ben~ophenone-di-(sulphonyl cyanamide)-3,3'- and isomers, diphenyl ether-di-(sulphonyl cyan~mide)-4,4' andisomers, cyclohexane-di-(sulphonyl cyanamide).
In the context of the invention, isomers are position isomers.
The N-cyanosulphonamides of formula (I) used in accordance with the invention may be obtained by reacting the corresponding sulphonic acid chlorides with cyanamide in accordance with Schotten-Baumann (cfo Methoden der Organischen Chemie9 Houben-Weyl, 4th Edition, VolO 8~ page 177) or in accordanee with Herbenstreit (J. PrO [2]~ Vol. 41~ pages 99 and 105). These eompounds may also be obtained by reaeting the eorresponding sulphonamides with eyanogen halide in the presenee of bases at temperatures o~ up to 650C.
Polyfunetional oyanamides o~ the formulA (II) may be obtained by reaeting the corresponding amines with eyanogen halide in solvents whieh are inert -to eyanogen halide at temperatures o~ ~rom -40 to ~65~C, optionally in the presenee o~ an inorganie base as a hydrogen halide aeeeptor~ and ~` ~ ~.~,r~an are deseribed in ~OS 1,595~651.
The symbols in formula (II) pre~erably have the following meaning:
- R~ and R~ represent straight-ehain or branehed-ehain, saturated or unsaturated, optionally eyelie aliphatic hydroearbons with ~rom 1 to 20 earbon atoms, and R' and R", together with -N-R-N-9 irom the piperazine ring;
R pre~èrably repre5ents a linear or branehed-ehain, saturated or unsaturated alkyl radieal with from, 2 to 18 Le A 16 ~49 -6-, ... .
' ' ` :
carbon atom~ ~ a cyclohexylene ra~lical (-C6Hlo~) or two cyclohexylene radicals attached by Cl-C3-alkylene, the phenylene or naphthylene radical or two phenylene radicals attached by Cl to C3-alkylene or by hetero atom~ (0, S) or by a carbonyl, sulphonyl or carbonyl dioxy group or by a cyclohexenyl radicalO
The bis-cyanamides of the following diamines for example may be used as polyfunctional cyanamides of ~ormula (II): N,N'-dimethyl ethylene diamine, N,N~-diethyl-, N,N'-di-_- or -isopropyl-, N,N~-di-n- or iso- or -tertO-butyl-~ N,N'-dihexyl-~
N,N'-dicyclohexyl-, N,N'-didodecyl-, N,N'-dioctadecyl-, N,N'-dibenzyl-, N,N9-diallyl-, N,N'-di- propargyl-ethylene diamine, also similarly substituted propylene diamines, butylene diamines, butenylene diamines~ butinylene diamines~ hexamethylene diamines~
decamethylene diamines, o.ctadecamethylene diamines, ~3- or 1,4-phenylene diamines~ 1,3- or ~4- or 1,5- or 1,6- or 1,7-or 2,6- or 2,7-naphthylene diamines, bis-methylaminobenzenes, 4~4~-bis-aminobisphenyl methanes, 4,4'-bis-amino-phenyl-1~1-and 1,2-ethunes, 4,4'-bis-amino-bis-phenyl-1,2-ethylenes, 4,4'-bis-amino~phenyl-1,3- or 2,2-propanes, 4,4'-bis-amino-diphenyl o~ides, 4,4' -bis-aminodiphenyl sulphides or sulphones;
also piperazineO Polycyanamides of N~N'~Nn-tris-N-alkyl-tris-aminotriphenyl methanes and N,N',N~-tris-N-aralkyl-tris-aminotriphenyl methanes, are also mentioned as e~amples of polyfunctional cyanamides of the ~ormula (II).
The process according to the invention may be carried out by heating the N-cyanosulphonamides o~ ~ormula (I) and the c.yanamides oi formula (II) as such or in solution, optionally in the presence oi a catalyst or catalyst mixture, at temperatures ~n the range of from 30 to 150C and preferably at temperatures in the range of from 50 to 100C, uncrosslinked prepolymers (A) (= N-sulphonyl-N-cyanoguanidines) Le A 16 549 _7_ :::
,~.~'' , ~0~3Si891 soluble in organic solvents being formed These prepolymers have a wax-lik~ or solid consi~tency and, a9 shown by the IR-spectrum~ contain hardly any tria~ine ~tructures, but instead show the bands of the -S02-N-C - N-group at 404 ~ and of the -N--N-C,NH-group at 5.9 ~.
The prepolymers may be converted into high molecular weight polymers (B) o~ triazine structure by heating to approximately 150 - 350C~ preferably 150 - 300C, optionally in solution and optionally in the presence of a catalyst or cataly~t mixture The end products are substantially insoluble in sol~ents and in~usible. As shown by the IR-spectrum, the polymer contains no other crosslinking principles apar-t from triazine structures. The ~ormation o~ the high molecular weight polymers with triazine structures is indicative oi the fact that N-cyanosulphonamide and cyanamide groups have participated equally in iormation of the triazine ring.
The polymers of triazine structure may also be produced ~rom the starting materials in a single stageO
Catlaysts suitable ~or use in the production o~ the prepolymer and high molecular weight end polymer with triazine structures include acids, bases~ salts~ nitrogen and phosphorus compounds~ ~or example Lewis acids such as AlC13, BF3, FeC13~ TiC14, ZnC12 or SnC14~ proton acids such as HCl or H3P04; aromatic hydroxy compounds such as phenol~ P-nitrophenol~ pyroGatechol or dihydroxy naphthalene; sodium hydroxide, sodium methylate~ sodium phenolate~
triethylamine t~imethylamine,/tributylami~e, diazabicyclo-(2,2~2)-octane, quinoline~
isoquinoline~ tetrahydroisoquinoline~ tetraethyl ammonium chloride~
pyridine-N-oxide, tributylphosphine, phospholine- ~ 3-1-oxa-1-phenyl, zinc, octoate, tin octoate, zinc naphthenate and mixturesthereofO
Le A 16 549 -8-'rhe cat;alysts may be uscd in ~luan~ities o~ from 0.001%
~y w~ight to 10 ~ by weight, based on the l)repolymer, or if desired in even larger quantities.
The prepolymers or the starting materials may be used in solution in inert solvents, such as acetone, benzene xylene, chlorobenzene, ethyl acetate~ tetrahydro~uran, dibutyl ether or dimethylformamide, or in powder form, ~or the production o~ coatings on substrates such as metals, ceramics, glags, earthenware, etc., or in solution in organic solvents as impreg-nating lacquers or laminating resins~ If desired, the prepolymers or the starting materials may be combined with fillers~ pigments~
glass fibres, metal ~ibres and glass cloths and used ~or the production o~ shaped articles or laminatesO Yel}ow to brown coloured, transparent, extremely hard and temperature-resistant end products are obtained after hardening.
The percentage contents and parts quoted in the Examples relate to weight unless otherwise indicated, 28.6 g (0.1 mol) of benzene-di-(sulphonyl cyanamide)-1~3 and 13.6 g (0.1 mol) of N~N~-dicyanopiperazine are boiled under reflux ior 3 hours in 100 ml o~ isopropanol. Removal of the solvent by distillation leaves the polymeric N-sulphonyl-N-cyanoguanidine with the characteristic IR-bands at 4,4 p -S02N-CeN~ and at 509 ,u - C=NH). Conversion o~ this prepolymer into a honey-coloured polytriazine (IR_spectrum s-triazine bands at 6.4 ~ and 7~25 p) is carried out over a period oi 7 hours at 200C iollowing the addition o~ 0.1~ by weight of zinc octoateO
A wax-like prepolymer (IR-spectrum: -S02-N-CeN
Le A 16 549 - 9 -~08~891 404 ~, -N-C-=N: 4.5 u~ -C=N~I; 5 9 ~) is obtained as in Example 1 from 28.6 g tO.l mol) of benzene-di-(sulphonyl cyanamide)-1,3 and 2702 g (0.2 mol) of N,N~-dicyanopiperazineO Hardening is carried out over a period of 7 hours at 200C in the presence of Ool~ by weight of zinc octoateO A polytriazine is obtained (IR = s-triazine bands at 604 ~ and 7 25 ~.
3602 g (0.1 mol) o~ diphenyl-di-(sulphonyl cyanamide)-4,4' and 13.8 g (0.1 mol) o~ N,N'-dicyano-N,N~-dimethyl ethylene diamine are boiled under reflux for 3 hours in 100 ml of ethanol. Removal oi the solvent by distillation gives the polymeric N-cyanoguanidine in a quantitAtive yieldO
(IR-spectrum: -S02-N-C--N at 4.4 ~, -N=NR at 5.9 ~).
Hardening to for~ a hard polytriazine is carried out over a period of 6 hours at 220C iollowing the addition oi 0.5~
by weight of pyrocatechol and 0.5% of diaza-bicyclo-(2,2,2)-octaneO
3708 g ( ~1 mol) o~ diphenyl oxide-di-(sulphonyl cyanamide)- 4~4~ and 27D6 g (0~1 mol) oi 4~4'-bis-(N-methyl-N-cyanoamino~-diphenyl methane are boiled under reflux for 4 hours in 300 ml oi toluene in the presence of 0.01 ~ by weight of triethylamineO Removal o$ the solvent by distillation leaves a prepolymer with the characteristic IR-bands at 404 ~
(S02-NC-) and 509 ~ (-C=NH)o Hardening of this prepolymer to form a hard polytriazine takes place over a period oi 6 hours at 230Co 42.6 g (0~1 mol) of diphenyl sulphone -di-(sulphonyl cyanamide)-3,3' and 30.4 g (0.1 mol) o~ 4,4'-di-(N-cyano-N-methylamino)-3~3'-dimethyl diphenyl methane are boiled under reilux for 4 hour~ in 400 ml oi methylethyl ketone. The Le A 16 549 -10-. ' , ~
~3689~
polymeric N-cyanoguanidine is obtalned in a quantitative yield after removal of the solvent by distlllation.
(IR-spectrum: -S02-N-C-N: 4.4 ~; -C=NH: 5.9 ~).
Hardening of this prepolymer to form an extremely hard brown polytriaæine takes place over a period of 7 hours at 190C in the presence of 0.1 ~ by weight of zinc chloride. ~-~3.6 g (0.1 mol) of naphthalene-di-(sulphonyl cyanamide)-1~ 2,6 and 28.8 g (0.1 mol) of 4,4l-bis-(N-methyl-N-cyanoamlno)-dicyclohexyl methane are boiled under reflux for 4 hours in 250 ml of isopropanol. The prepolymer i8 obtained in a quantitative yield following removal of the solvent by distillation. (IR-spectrum: -S02-N-C-N at 4,4~u; -C=N~
at 5.9 ~u)0 Hardening to form a hard, honey-coloured poly-triazine takes place over a period of 6 hours at 220C
following the addition of 0.1 % by weight of tin octoate.
Le A 16 549 - 11 -
cyanamides.
It is known from German PS 1,190,184 that high molecular weight polytriazines can be obtained by p~lymeris-ing difunctional or polyfunctional aromatic cyanic acid esters at elevated temperature, optionally in the presence of polymerisation promoters.
According to a ~apanese Application filed by Sugino and published as 6265/66 on April 4, 1966, primary diamines are reacted with cyanogen halide to form di(cyanamides~
which are then processed into polymers.
The polymerisation of polyfunctional cyanamides of secondary amines with catalytic to more than molar quan-tities of mono- or poly-hydroxyl and/or thiol compounds at temperatures of from 50 to 250C to form polymeric products, is also known, cf. German OS 1,595,651.
Finally, a process for the production of macromole-cular polyguanidines by reacting N,N'-dicyanamides of the formula NC-NH-R-NH-CN on their own or with an N,N'-dicyanamide of the formula NC-NR'-R-NR'CN (R and R' represent hydrocarbon radicals), is known from Netherlands Patent No. 55 826.
It has now been found that high molecular weight polytriazines can be obtained by converting N-cyanosulphon-amides corresponding to the general formula (I):
A(S02-NH-CN)n (I) '. . '' - ' ~ ~ '.
1~8fiB9~
in which A represents alipha-tic, cycloaliphatic or aromati.c polyvalent radicals and n is a number from 2 to 5, with poly~unctional cyanamides corresponding to the general formula (II):
NC-N-R-N-CN (II) R' R"
in which R' and R" are the same or different and represent aliphatic or araliphatic radicals or9 together with the ~N-R-N-group, form a heterocyclic ring, and R represents an alkylene, cycloalkylene or arylene radical or two or more such radicals which may be attached by arylene or alkylene radicals or by hetero atoms, R optionally containing further ; radicals of the formula:
-N-CN
R~
at elevated temperatures into a prepolymer soluble in organic solvents or into a fusible prepolymer, and allowing the prepolymer to react to completion at elevated temperatures to form a high molecular weight polymer of polytriazine structure which is substantially insoluble in solvents.
It is preferred to react from 30 to 70 mol % of N-cyanosulphonamides of formula (I) with from 70 to 30 mol %
of cyanamides of formula (II).
The present invention also relates to mixtures of A) N-cyanosulphonamides of general formula (I) and B) cyan~mides o~general formula (II), which can be converted into high molecular weight polymers of polytriazine structure which are substantially insoluble Le A 16 549 -2-1~6E~91 in solvents.
The mixtures preferably consist o$ $rom 30 to 70 mol ~ of N-cyanosulphonamides o$ formula (I) and of from 70 to 30 mol ~ of cyanamides o~ formula (II).
The process according to the invention i~ illu~trated by the following exemplary equation (in which x > 2), the terminal groups being cyanamide groups:
Le A 16 549 _3_ - , . . .
NC-HNO"S ~\~, S 02NHCN ~
W + NC--N N--CN
~ 30C to 150C
_~ CN Nll NE}
x x,> 2 (A) 150C to 350C
~`
\ I
N=C ~ N
l{N--502~ --C~
~N~
J
b' N
(B) Le A 16 549 _4_ 1~)8~91 q`he symbols in formula (I~ pre~erably have the following ~eaning;
A represents a polyvalent~ aliphatic~ straight chain or branclled-chain, saturated or unsaturated radical with from 1 tc 20 carbon atoms, more especially with ~rom 2 to 12 carbon atoms;
a polyvalent cycloalipha$ic radical w:ith from 4 to 12 carbon atoms, more especially a 5- or 6-membered, cycloaliphatic, polyvalent radical; a polyvalent cycloaliphatic radical with from 4 to 12 carbon atoms, more especially with from 5 to 10 carbon atoms, interrupted by Cl to C4-alkylene groups or by phenyl or by hetero atoms (0~ S); a polyvalent~ aromatic radical with from 6 to 14 carbon atoms, more especially with from 6 to 10 carbon atoms; a polyvalent aromatic ring with from 6 to 14 carbon atoms, more especially with 6 carbon atoms, interrupted by Cl to C4-alkylene~ by oxygen, by the carbonyl group (-C0-), by the carbonyl dioxy group l~ ~ by the sulphonyl group (-OCO-) (-S02-)~ by a cycloaliphatic or aromatic 5-membered or 6-membered carbocyclic ring or by a single bond; and n is the number 2 or 3, more especially the number 2.
N-cyanosulphonamides of the formula (I), in which A repre-sents the aromatic radicals defined above~ are particularly preferred.
The following compounds are mentioned by way of example:
25 hexane-di-(sulphonyl cyanamide)-1,6 and isomers~
benzene-di-(sulphonyl cyanamide)-1,3; -1,4, benzene-tri-(sulphonyl cyanamide)-1,3,5, naphthalene-di-(sulphonyl cyanamide)-1,3 and isomers, naphthalene-tri-(sulphonyl cyanamide)-1,3,5;
-1,3,6; -1,3,7;
naphthalene-tetra-(sulphonyl cyanamide)-1~3~5~7 diphenyl-di-(sulphonyl cyanamide)-2~2' (-4~4'; -3,3', -2,4') Le A 16 549 _5_ ~08~891 diphenyl methane-di-(sulphonyl cyanamide)-4,4'-, 2,4' diphenyl diphenyl methane-di-(sulphonyl cyanamide)-4~4'-and isomers, diphenyl sulphone-di-(sulphonyl cyanamide)-3,3'- and isomers, ben~ophenone-di-(sulphonyl cyanamide)-3,3'- and isomers, diphenyl ether-di-(sulphonyl cyan~mide)-4,4' andisomers, cyclohexane-di-(sulphonyl cyanamide).
In the context of the invention, isomers are position isomers.
The N-cyanosulphonamides of formula (I) used in accordance with the invention may be obtained by reacting the corresponding sulphonic acid chlorides with cyanamide in accordance with Schotten-Baumann (cfo Methoden der Organischen Chemie9 Houben-Weyl, 4th Edition, VolO 8~ page 177) or in accordanee with Herbenstreit (J. PrO [2]~ Vol. 41~ pages 99 and 105). These eompounds may also be obtained by reaeting the eorresponding sulphonamides with eyanogen halide in the presenee of bases at temperatures o~ up to 650C.
Polyfunetional oyanamides o~ the formulA (II) may be obtained by reaeting the corresponding amines with eyanogen halide in solvents whieh are inert -to eyanogen halide at temperatures o~ ~rom -40 to ~65~C, optionally in the presenee o~ an inorganie base as a hydrogen halide aeeeptor~ and ~` ~ ~.~,r~an are deseribed in ~OS 1,595~651.
The symbols in formula (II) pre~erably have the following meaning:
- R~ and R~ represent straight-ehain or branehed-ehain, saturated or unsaturated, optionally eyelie aliphatic hydroearbons with ~rom 1 to 20 earbon atoms, and R' and R", together with -N-R-N-9 irom the piperazine ring;
R pre~èrably repre5ents a linear or branehed-ehain, saturated or unsaturated alkyl radieal with from, 2 to 18 Le A 16 ~49 -6-, ... .
' ' ` :
carbon atom~ ~ a cyclohexylene ra~lical (-C6Hlo~) or two cyclohexylene radicals attached by Cl-C3-alkylene, the phenylene or naphthylene radical or two phenylene radicals attached by Cl to C3-alkylene or by hetero atom~ (0, S) or by a carbonyl, sulphonyl or carbonyl dioxy group or by a cyclohexenyl radicalO
The bis-cyanamides of the following diamines for example may be used as polyfunctional cyanamides of ~ormula (II): N,N'-dimethyl ethylene diamine, N,N~-diethyl-, N,N'-di-_- or -isopropyl-, N,N~-di-n- or iso- or -tertO-butyl-~ N,N'-dihexyl-~
N,N'-dicyclohexyl-, N,N'-didodecyl-, N,N'-dioctadecyl-, N,N'-dibenzyl-, N,N9-diallyl-, N,N'-di- propargyl-ethylene diamine, also similarly substituted propylene diamines, butylene diamines, butenylene diamines~ butinylene diamines~ hexamethylene diamines~
decamethylene diamines, o.ctadecamethylene diamines, ~3- or 1,4-phenylene diamines~ 1,3- or ~4- or 1,5- or 1,6- or 1,7-or 2,6- or 2,7-naphthylene diamines, bis-methylaminobenzenes, 4~4~-bis-aminobisphenyl methanes, 4,4'-bis-amino-phenyl-1~1-and 1,2-ethunes, 4,4'-bis-amino-bis-phenyl-1,2-ethylenes, 4,4'-bis-amino~phenyl-1,3- or 2,2-propanes, 4,4'-bis-amino-diphenyl o~ides, 4,4' -bis-aminodiphenyl sulphides or sulphones;
also piperazineO Polycyanamides of N~N'~Nn-tris-N-alkyl-tris-aminotriphenyl methanes and N,N',N~-tris-N-aralkyl-tris-aminotriphenyl methanes, are also mentioned as e~amples of polyfunctional cyanamides of the ~ormula (II).
The process according to the invention may be carried out by heating the N-cyanosulphonamides o~ ~ormula (I) and the c.yanamides oi formula (II) as such or in solution, optionally in the presence oi a catalyst or catalyst mixture, at temperatures ~n the range of from 30 to 150C and preferably at temperatures in the range of from 50 to 100C, uncrosslinked prepolymers (A) (= N-sulphonyl-N-cyanoguanidines) Le A 16 549 _7_ :::
,~.~'' , ~0~3Si891 soluble in organic solvents being formed These prepolymers have a wax-lik~ or solid consi~tency and, a9 shown by the IR-spectrum~ contain hardly any tria~ine ~tructures, but instead show the bands of the -S02-N-C - N-group at 404 ~ and of the -N--N-C,NH-group at 5.9 ~.
The prepolymers may be converted into high molecular weight polymers (B) o~ triazine structure by heating to approximately 150 - 350C~ preferably 150 - 300C, optionally in solution and optionally in the presence of a catalyst or cataly~t mixture The end products are substantially insoluble in sol~ents and in~usible. As shown by the IR-spectrum, the polymer contains no other crosslinking principles apar-t from triazine structures. The ~ormation o~ the high molecular weight polymers with triazine structures is indicative oi the fact that N-cyanosulphonamide and cyanamide groups have participated equally in iormation of the triazine ring.
The polymers of triazine structure may also be produced ~rom the starting materials in a single stageO
Catlaysts suitable ~or use in the production o~ the prepolymer and high molecular weight end polymer with triazine structures include acids, bases~ salts~ nitrogen and phosphorus compounds~ ~or example Lewis acids such as AlC13, BF3, FeC13~ TiC14, ZnC12 or SnC14~ proton acids such as HCl or H3P04; aromatic hydroxy compounds such as phenol~ P-nitrophenol~ pyroGatechol or dihydroxy naphthalene; sodium hydroxide, sodium methylate~ sodium phenolate~
triethylamine t~imethylamine,/tributylami~e, diazabicyclo-(2,2~2)-octane, quinoline~
isoquinoline~ tetrahydroisoquinoline~ tetraethyl ammonium chloride~
pyridine-N-oxide, tributylphosphine, phospholine- ~ 3-1-oxa-1-phenyl, zinc, octoate, tin octoate, zinc naphthenate and mixturesthereofO
Le A 16 549 -8-'rhe cat;alysts may be uscd in ~luan~ities o~ from 0.001%
~y w~ight to 10 ~ by weight, based on the l)repolymer, or if desired in even larger quantities.
The prepolymers or the starting materials may be used in solution in inert solvents, such as acetone, benzene xylene, chlorobenzene, ethyl acetate~ tetrahydro~uran, dibutyl ether or dimethylformamide, or in powder form, ~or the production o~ coatings on substrates such as metals, ceramics, glags, earthenware, etc., or in solution in organic solvents as impreg-nating lacquers or laminating resins~ If desired, the prepolymers or the starting materials may be combined with fillers~ pigments~
glass fibres, metal ~ibres and glass cloths and used ~or the production o~ shaped articles or laminatesO Yel}ow to brown coloured, transparent, extremely hard and temperature-resistant end products are obtained after hardening.
The percentage contents and parts quoted in the Examples relate to weight unless otherwise indicated, 28.6 g (0.1 mol) of benzene-di-(sulphonyl cyanamide)-1~3 and 13.6 g (0.1 mol) of N~N~-dicyanopiperazine are boiled under reflux ior 3 hours in 100 ml o~ isopropanol. Removal of the solvent by distillation leaves the polymeric N-sulphonyl-N-cyanoguanidine with the characteristic IR-bands at 4,4 p -S02N-CeN~ and at 509 ,u - C=NH). Conversion o~ this prepolymer into a honey-coloured polytriazine (IR_spectrum s-triazine bands at 6.4 ~ and 7~25 p) is carried out over a period oi 7 hours at 200C iollowing the addition o~ 0.1~ by weight of zinc octoateO
A wax-like prepolymer (IR-spectrum: -S02-N-CeN
Le A 16 549 - 9 -~08~891 404 ~, -N-C-=N: 4.5 u~ -C=N~I; 5 9 ~) is obtained as in Example 1 from 28.6 g tO.l mol) of benzene-di-(sulphonyl cyanamide)-1,3 and 2702 g (0.2 mol) of N,N~-dicyanopiperazineO Hardening is carried out over a period of 7 hours at 200C in the presence of Ool~ by weight of zinc octoateO A polytriazine is obtained (IR = s-triazine bands at 604 ~ and 7 25 ~.
3602 g (0.1 mol) o~ diphenyl-di-(sulphonyl cyanamide)-4,4' and 13.8 g (0.1 mol) o~ N,N'-dicyano-N,N~-dimethyl ethylene diamine are boiled under reflux for 3 hours in 100 ml of ethanol. Removal oi the solvent by distillation gives the polymeric N-cyanoguanidine in a quantitAtive yieldO
(IR-spectrum: -S02-N-C--N at 4.4 ~, -N=NR at 5.9 ~).
Hardening to for~ a hard polytriazine is carried out over a period of 6 hours at 220C iollowing the addition oi 0.5~
by weight of pyrocatechol and 0.5% of diaza-bicyclo-(2,2,2)-octaneO
3708 g ( ~1 mol) o~ diphenyl oxide-di-(sulphonyl cyanamide)- 4~4~ and 27D6 g (0~1 mol) oi 4~4'-bis-(N-methyl-N-cyanoamino~-diphenyl methane are boiled under reflux for 4 hours in 300 ml oi toluene in the presence of 0.01 ~ by weight of triethylamineO Removal o$ the solvent by distillation leaves a prepolymer with the characteristic IR-bands at 404 ~
(S02-NC-) and 509 ~ (-C=NH)o Hardening of this prepolymer to form a hard polytriazine takes place over a period oi 6 hours at 230Co 42.6 g (0~1 mol) of diphenyl sulphone -di-(sulphonyl cyanamide)-3,3' and 30.4 g (0.1 mol) o~ 4,4'-di-(N-cyano-N-methylamino)-3~3'-dimethyl diphenyl methane are boiled under reilux for 4 hour~ in 400 ml oi methylethyl ketone. The Le A 16 549 -10-. ' , ~
~3689~
polymeric N-cyanoguanidine is obtalned in a quantitative yield after removal of the solvent by distlllation.
(IR-spectrum: -S02-N-C-N: 4.4 ~; -C=NH: 5.9 ~).
Hardening of this prepolymer to form an extremely hard brown polytriaæine takes place over a period of 7 hours at 190C in the presence of 0.1 ~ by weight of zinc chloride. ~-~3.6 g (0.1 mol) of naphthalene-di-(sulphonyl cyanamide)-1~ 2,6 and 28.8 g (0.1 mol) of 4,4l-bis-(N-methyl-N-cyanoamlno)-dicyclohexyl methane are boiled under reflux for 4 hours in 250 ml of isopropanol. The prepolymer i8 obtained in a quantitative yield following removal of the solvent by distillation. (IR-spectrum: -S02-N-C-N at 4,4~u; -C=N~
at 5.9 ~u)0 Hardening to form a hard, honey-coloured poly-triazine takes place over a period of 6 hours at 220C
following the addition of 0.1 % by weight of tin octoate.
Le A 16 549 - 11 -
Claims (4)
1. A mixture which can be converted into a high molecular weight polymer of polytriazine structure which is substantially insoluble in solvents, comprising A) an N-cyanosulphonamide corresponding to the general formula (I):
A(SO2-NHCN)n (I) in which A represents an aliphatic, cycloaliphatic or aromatic radical, and n is a number from 2 to 5 and B) a cyanamide corresponding to the general formula (II):
(II) in which R1 and R" are the same or different and each represents and aliphatic or araliphatic radical or R' and R", together with the -N-R-N-group, form a heterocyclic ring, and R represents an alkylene, cycloalkylene or arylene radical or two or more such radicals which may be attached by one or more arylene or alkylene groups or by one or more hetero atoms, R optionally containing at least one further radical of the formula .
A(SO2-NHCN)n (I) in which A represents an aliphatic, cycloaliphatic or aromatic radical, and n is a number from 2 to 5 and B) a cyanamide corresponding to the general formula (II):
(II) in which R1 and R" are the same or different and each represents and aliphatic or araliphatic radical or R' and R", together with the -N-R-N-group, form a heterocyclic ring, and R represents an alkylene, cycloalkylene or arylene radical or two or more such radicals which may be attached by one or more arylene or alkylene groups or by one or more hetero atoms, R optionally containing at least one further radical of the formula .
2. A mixture as claimed in Claim 1, which comprises from 30 to 70 mol % of component A and from 70 to 30 mol %
of component B.
of component B.
3. A process for the production of a high molecular weight polymer of polytriazine structure which is substantially insoluble in solvents, which comprises converting a compound corresponding to the general formula (I) as de-fined in Claim 1 and a compound corresponding to the general formula (II) as defined in Claim 1 at an elevated temperature into a prepolymer soluble in organic solvents or into a fusible prepolymer, and allowing the prepolymer to react to completion at an elevated temperature to form a high molecular weight polymer of polytriazine structure which is substantially insoluble in solvents.
4. A process as claimed in Claim 3, wherein from 30 to 70 mol % of the N-cyanosulphonamide of formula (I) are reacted with from 70 to 30 mol % of the cyanamide of formula (II.)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2533127.5 | 1975-07-24 | ||
| DE19752533127 DE2533127A1 (en) | 1975-07-24 | 1975-07-24 | POLYTRIAZINE AND A PROCESS FOR THE PREPARATION |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1086891A true CA1086891A (en) | 1980-09-30 |
Family
ID=5952376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA257,557A Expired CA1086891A (en) | 1975-07-24 | 1976-07-22 | Polytriazines and a process for their production |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5214700A (en) |
| BE (1) | BE844392A (en) |
| CA (1) | CA1086891A (en) |
| CH (1) | CH603719A5 (en) |
| DE (1) | DE2533127A1 (en) |
| FR (1) | FR2318893A1 (en) |
| GB (1) | GB1526036A (en) |
| NL (1) | NL7608216A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61276712A (en) * | 1985-05-31 | 1986-12-06 | Toshikazu Okuno | Rolling mill for wire |
| DE19741635A1 (en) * | 1997-09-22 | 1999-03-25 | Hoechst Marion Roussel De Gmbh | Biphenylsulfonylcyanamides, process for their preparation and their use as a medicament |
| CN114790286A (en) * | 2022-03-30 | 2022-07-26 | 绍兴文理学院 | Preparation method of covalent triazine framework polymer microspheres |
-
1975
- 1975-07-24 DE DE19752533127 patent/DE2533127A1/en active Pending
-
1976
- 1976-07-21 JP JP8609876A patent/JPS5214700A/en active Pending
- 1976-07-22 GB GB3059476A patent/GB1526036A/en not_active Expired
- 1976-07-22 CH CH941676A patent/CH603719A5/xx not_active IP Right Cessation
- 1976-07-22 BE BE169130A patent/BE844392A/en unknown
- 1976-07-22 CA CA257,557A patent/CA1086891A/en not_active Expired
- 1976-07-23 NL NL7608216A patent/NL7608216A/en not_active Application Discontinuation
- 1976-07-23 FR FR7622569A patent/FR2318893A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| NL7608216A (en) | 1977-01-26 |
| CH603719A5 (en) | 1978-08-31 |
| GB1526036A (en) | 1978-09-27 |
| JPS5214700A (en) | 1977-02-03 |
| FR2318893B1 (en) | 1979-07-27 |
| DE2533127A1 (en) | 1977-02-10 |
| FR2318893A1 (en) | 1977-02-18 |
| BE844392A (en) | 1977-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Oishi et al. | Preparation and properties of novel soluble aromatic polyimides from 4, 4′‐diaminotriphenylamine and aromatic tetracarboxylic dianhydrides | |
| CA1326084C (en) | Polyarylene sulfide block copolymers, method for making, and use | |
| CA2230047C (en) | Imide oligomers and co-oligomers containing pendent phenylethynyl groups and polymers therefrom | |
| US4066631A (en) | Process for preparation of linear polyamide-imides from aromatic tricarboxylic acid anhydrides and diamines | |
| US5856421A (en) | Polyetherimide preparation method including addition of macrocyclic polyetherimide oligomers | |
| CA1068696A (en) | Catalytic trimerization of aromatic nitriles and triaryl-s-triazine ring cross-linked high temperature resistant polymers and co-polymers made thereby | |
| CA1086891A (en) | Polytriazines and a process for their production | |
| Hsiao et al. | Synthesis and characterization of new diphenylfluorene‐based aromatic polyamides derived from 9, 9‐bis [4‐(4‐carboxy‐phenoxy) phenyl] fluorene | |
| EP0311387B1 (en) | Aromatic amine resins, their production process and thermosetting resin compositions making use of the same | |
| CA1098644A (en) | Hydrolysis-stable polytriazines and a process for their production | |
| US4031067A (en) | Polytriazines and a process for their production | |
| Hsiao et al. | Preparation and characterization of aromatic polyamides based on ether‐sulfone‐dicarboxylic acids | |
| EP0342943B1 (en) | Thermosetting resin composition | |
| Saegusa et al. | Synthesis and characterization of 1, 3, 4‐oxadiazole‐containing polyazomethines | |
| Liou et al. | Preparation and properties of aromatic polyamides from 2, 2′‐bis (p‐carboxyphenoxy) biphenyl or 2, 2′‐bis (p‐carboxyphenoxy)‐1, 1′‐binaphthyl and aromatic diamines | |
| US4059567A (en) | High molecular weight polytriazines of soluble polymeric N-cyano-isourea ethers | |
| JPS5845454B2 (en) | S - Triazine | |
| KR920000697B1 (en) | Aromatic polymer and a process for its preparation | |
| US4066577A (en) | High molecular weight polytriazines of soluble polymeric n-cyano-isourea ethers | |
| Dokoshi et al. | Cyclopolycondensation. XIII. New synthetic route to fully aromatic poly (heterocyclic imides) with alternating repeating units | |
| Yang et al. | New poly (amide‐imide) s syntheses, 6. Preparation and properties of poly (amide‐imide) s derived from 2, 7‐bis (4‐aminophenoxy) naphthalene, trimellitic anhydride and various aromatic diamines | |
| Choi et al. | Synthesis and Characterization of New Aromatic Polyamides with N, N′‐Di (4‐n‐alkylphenyl) benzodiimide Unit on the Main Chain | |
| Hsiao et al. | Synthesis and properties of aromatic polyamides based on 4, 4′‐(2, 7‐naphthalenedioxy) dibenzoic acid | |
| Neamţu et al. | Copolyimides new polybenzoxazinone‐imides | |
| Srinivasan et al. | Preparation and properties of polybenzimidazoles containing cardo groups |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |