This invention provides compositions containing polysulfonamides which are prepared by the addition polymerization of bis-N-cyanosulfonamides. The resins are useful in coating, molding, laminating and casting applications.

This invention relates to a new class of nitrogenous polymeric materials. 
More particularly, it relates to polysulfonamides which are prepared by 
the addition polymerization of bis-N-cyanosulfonamides, which are novel 
compounds. 
In accordance with this invention a new class of polysulfonamide resins for 
use in coating, laminating, molding and casting applications has been 
discovered. These resins are distinguished by their ease of fabrication, 
low raw material cost and exceptional elevated temperature and electrical 
properties. 
These resins are prepared from polymerizable compositions which contain 
organic groups of the formula (I) 
##STR1## 
which unexpectedly have been found to undergo an addition polymerization 
reaction believed to involve the trimerization of the cyano moiety. 
In one embodiment of this invention polymerizable compositions are 
described which contain in their molecules two or more of I attached to 
one or more divalent aromatic, aliphatic, cycloaliphatic or heterocyclic 
radicals. 
The divalent aromatic radicals may be linked by divalent groups such as 
##STR2## 
The divalent grops may also be heterocyclic such as thiadiazoyl, pyronyl, 
benzimidazolyl and the like. The divalent aromatic groups may be 
substituted with halogens in order to achieve greater fire retardancy. An 
example of a compound in this embodiment is shown by the following 
structure. 
##STR3## 
The divalent aliphatic and cycloaliphatic groups may be alkylene of 1-18 
carbons, preferably 1-7, cycloalkylene of 3-7 carbons, and such radicals 
bearing electronegative substituents such as halogens, especially fluoro. 
In another embodiment of this invention compositions containing I are 
copolymerized with compositions containing two or more cyanamide groups of 
the formula (II) 
##STR4## 
These cyanamide groups are attached to one or more divalent aromatic, 
aliphatic or heterocyclic radicals. The divalent radicals can be linked by 
divalent groups such as --S-- and those described above. An example of a 
compound containing the cyanamide groups described in the second 
embodiment is given by the following structure. 
##STR5## 
The reaction of such compounds containing two or more cyanamide groups with 
a compound containing only one of I, i.e., monofunctional 
N-cyanosulfonamides, is also encompassed by this embodiment. 
The polymerizable compositions of this invention may be either pure 
compounds or oligmers that cure by an addition polymerization mechanism to 
yield crosslinked resins having a high glass transition temperature and 
good oxidative stability at temperatures up to approximately 500.degree. 
F. Applications as circuit boards, encapsulating resins for electrical use 
(potting compounds), high temperature adhesives, compression and transfer 
molding compounds, powder coatings and resin matrices for inorganic and 
organic fiber composites such as laminates with glass, boron, polyamide 
and graphite fibers, are visualized. 
The N-cyanosulfonamide compounds and cyanamide compounds are prepared by 
the following synthetic routes. The compounds containing two 
N-cyanosulfonamide groups are novel. Their synthesis is illustrated below. 
##STR6## 
In structures A and B above, R' is a monovalent aliphatic, cycloaliphatic, 
aromatic or heterocyclic group and R is a divalent aliphatic, 
cycloaliphatic, aromatic, or heterocyclic group linked by divalent groups 
such as 
##STR7## 
The groups R contained within a single molecule may be all the same or 
different, and similarly the groups R' contained within a single molecule 
may be all the same or different. The groups may also be halogenated. 
Preferred structures of the N-cyanosulfonamide compounds include 
##STR8## 
a single bond and n is zero to five. 
##STR9## 
In the structures directly above the 
##STR10## 
group can be replaced by 
##STR11## 
groups without interfering with the concept of this invention. Similarly, 
any of the hydrogen atoms in these benzenoid radicals may be replaced with 
chlorine, bromine or fluorine groups without lessening utility. 
In the synthesis of the N-cyanosulfonamide compounds by the reaction 
sequences shown under A it is necessary to use a sulfonyl chloride. The 
sulfonyl chloride can be reacted with a biscyanamide derived from a 
diamine or first reacted with a diamine to yield a sulfonamide which is 
then reacted with a cyanogen halide to yield the desired 
N-cyanosulfonamide compound. Overall yields by either route are in excess 
of 80%. Suitable aromatic sulfonyl chlorides for these reaction sequences 
include benzene sulfonyl chloride, p-chlorobenzene sulfonyl chloride, 
p-toluene sulfonyl chloride, 2-naphthalenesulfonyl chloride and 
anthracene-2-sulfonyl chloride. Suitable aliphatic and cycloaliphatic 
sulfonyl chlorides are methane sulfonyl chloride, ethane sulfonyl 
chloride, trifluoromethylsulfonyl chloride, n and iso propyl sulfonyl 
chloride, n and iso butyl sulfonyl chloride, n and iso amyl sulfonyl 
chloride, cyclopentane sulfonyl chloride, n-hexyl sulfonyl chloride, 
cyclohexane sulfonyl chloride and n-heptyl and n-octyl sulfonyl chlorides. 
Among the suitable heterocyclic sulfonyl halides are thiophene-2-sulfonyl 
chloride and benzopyran-6-sulfonyl chloride. 
In the synthesis of the N-cyanosulfonamide compounds of alternate structure 
shown under B disulfonyl chlorides can be reacted with an amine like 
aniline to yield the corresponding sulfonamide which is then reacted with 
cyanogen halide or reacted with a cyanamide to yield the desired compound. 
Overall yields by either route are in excess of 80%. Specific examples of 
the preferred aromatic disulfonyl halides used in the present invention 
include: benzene-1,3-disulfonyl chloride; benzene-1,3-disulfonyl bromide; 
2,4,5,6-tetrachlorobenzene-1,3-disulfonyl chloride; 
naphthalene-1,5-disulfonyl chloride; o-xylene-3,5-disulfonyl chloride; 
p-xylene-2,6-disulfonyl chloride; naphthalene-2,7-disulfonyl chloride; 
diphenyl-4,4'-disulfonyl chloride; diphenyl ether-4,4'-disulfonyl 
chloride; diphenyl sulfide-4,4'-disulfonyl chloride; and 
benzophenone-4,4'-disulfonyl chloride. Examples of aliphatic and 
cycloaliphatic disulfonyl halides are methane disulfonyl chloride; 
ethane-1,2-disulfonyl chloride; cyclohexane disulfonyl chloride; 
propyl-1,3-disulfonyl chloride; and isobutylene-1,3-disulfonyl chloride. 
Examples of heterocyclic disulfonyl halides are 
dibenzothiophene-3,6-disulfonyl chloride; and 
diphenyl-2,2-sulfonyl-4,4'-disulfonyl chloride. 
When the above bis --N-- cyanosulfonamide compounds are heated above their 
melting points the fluid melt becomes increasingly viscous and eventually 
thermosets to yield a hard plastic having utility in structural 
applications, i.e., moldings, castings, composites, and for protective 
uses, i.e., coatings. The temperature/time relationship for thermosetting 
is shown below for 4,4'-methylene bis (N-benzene sulfonyl phenyl 
cyanamide), m.p. 129.degree. C. 
Table I 
______________________________________ 
Polymerization of 4,4'-Methylene bis(N-benzene sulfonyl phenyl 
cyanamide) 
Polymerization Temperature .degree. C. 
Gel Time 
______________________________________ 
240 3 minutes 
200 35 minutes 
190 5 hours 
185 7 hours 
180 10 hours 
______________________________________ 
A differential thermal analysis run with this compound showed a 
polymerization exotherm between approximately 199.degree.-240.degree. C. 
which gave a heat of polymerization of 33.7 kilo cal/mole. The increase in 
the glass transition temperature (Tg) of the polymer at various cure 
temperatures and times measured by a Torsional Braid analyzer is shown 
below. 
Table II 
______________________________________ 
Torsional Braid Analysis of Poly-4,4'-Methylene bis(N-benzene 
sulfonyl phenyl cyanamide) 
Cure Temperature .degree. C. 
Cure Time in Hours 
Tg.degree. C. 
______________________________________ 
200 3.5 250 
240 0.5 253 
300 0.5 290 
300 1.0 350 
______________________________________ 
An elemental analysis run on the monomer before curing and after curing at 
300.degree. C. is shown below indicating that the polymer has essentially 
the same elemental analysis as the monomer and has not evolved 
condensation products or oxidized in air at 300.degree. C. to any 
significant extent. 
Table III 
______________________________________ 
Elemental Analysis of Poly-4,4'-Methylene bis(N-benzene 
sulfonyl phenyl cyanamide) after 300.degree. C. Cure in Air 
Monomer Analysis 
Polymer Analysis after 300.degree. C. Cure 
______________________________________ 
%C 61.9 63.3 
%H 4.11 4.22 
%N 10.6 12.8 
%S 11.5 10.5 
______________________________________ 
Heating of the compound N-benzene sulfonyl phenyl cyanamide at 240.degree. 
C. for 3 hours gave a product showing, by infrared absorption, the 
presence of the s-triazine ring and absence of nitrile group absorption at 
2220 cm.sup..sup.-1. A molecular weight measurement by vapor phase 
osmometry showed that the molecular weight had approximately tripled which 
would indicate that a trimerization reaction had taken place. 
A possible, but not necessarily the only polymerization mechanism, for N-- 
cyanosulfonamide compounds is illustrated below: 
##STR12## 
or alternately 
##STR13## 
wherein R is as defined previously. 
The above illustrated polymers are high molecular weight, 
three-dimensional, crosslinked structures, the recuring aromatic and 
heterocyclic rings conferring high thermal stability, chemical inertness 
and water and solvent resistance. These polymers do not soften below their 
decomposition temperatures and have glass transition temperatures (Tg's) 
generally above 300.degree. C. The polymers from monomers of structure I 
are more rigid and have higher Tg's than the more flexible polymers from 
structure II that have a greater distance between the crosslinking sites. 
Thermogravimetric analysis in air shows that these polymers have short 
term stability up to 300.degree. C. with approximately 10% or less weight 
loss reached at 350.degree. C. Physical properties of these polymers are 
retained during isothermal aging at 260.degree. C. over extended periods 
of time. 
The polymerization data in Table I indicates that polymerization below a 
temperature of 200.degree. C. takes place at a relatively slow rate. For a 
number of applications it is desirable to process and fabricate 
thermosetting polymers at as low a temperature as possible and as rapidly 
as possible for economic reasons. On the other hand, the polymerization of 
aromatic bis cyanamides containing two or more groups having the structure 
shown in formula II normally takes place very rapidly at low temperatures 
even in the solid state below the temperature at which the melting point 
is reached. This fact makes the polymers prepared from aromatic bis 
cyanamides of very limited utility since they cannot be maintained in a 
molten state for a sufficient period to be shaped or fabricated into 
finished parts. In fact the melting points of aromatic bis cyanamides 
containing no aliphatic groups cannot be obtained. 
It has unexpectedly been found that the solution to both of these problems, 
i.e., non-melting of aromatic bis cyanamides and slow polymerization of 
the N-cyanosulfonamide compounds at moderate temperatures can be solved by 
the copolymerization of the N-cyanosulfonamide compounds with aromatic bis 
cyanamides at various molecular ratios. At the lower limit it requires 
approximately 0.1 mole of aromatic bis cyanamide per mole of 
N-cyanosulfonamide compound to noticeably accelerate the polymerization 
rate at 180.degree. C. At the upper limit, extremely fast thermosetting 
compositions are achieved at 140.degree. C. with approximately three moles 
of aromatic bis cyanamide to one mole of N-cyanosulfonamide compound. In 
order to allow sufficient time for melt flow and removal of solvent, if 
present, while processing between 140.degree.-180.degree. C., a preferred 
range of approximately 0.5 mole to 3.0 moles of aromatic bis cyanamide 
compound per mole of N-cyanosulfonamide has been found optimal. 
In Table IV it is shown that increasing the molar concentration of bis 
cyanamide in mixtures of N-cyanosulfonamidebis cyanamide results in a more 
rapid cure as determined by Torsional Braid Analysis measurements of Tg's. 
Table IV 
______________________________________ 
Polymerization of 4,4'-Methylene bis(N-benzene sulfonyl phenyl 
cyanamide) (MBSPC) with 4,4'-Methylene bis phenyl cyanamide 
(MBPC) 
Curing Time 
in Hrs. at Tg of 2:1/ Tg of 1:1/ Tg of 1:3/ 
178.degree. C. 
MBSPC:MBPC MBSPC:MBPC MBSPC:MBPC 
______________________________________ 
0.5 -- 177.degree. C. 
215.degree. C. 
1.0 -- 205.degree. C. 
-- 
1.75 -- 227.degree. C. 
-- 
2.50 178.degree. C. 
227.degree. C. 
-- 
______________________________________ 
By studying the reaction between model compounds of N-cyanosulfonamide-bis 
cyanamide mixtures it was demonstrated that both species preferably react 
with one another (copolymerize) rather than forming a mixture of 
homopolymers. N-benzene sulfonyl phenyl cyanamide, (0.02 moles), m.p. 
59.degree. C. and phenyl cyanamide (0.04 moles), m.p. 40.degree. C. were 
stirred in the melt for 3 hours at 82.degree. C. at which point the melt 
solidified. The reaction mixture was then dissolved in methyl ethylketone 
and the solution was heated at reflux temperatures overnight. The product 
was isolated by pouring the solution into pentane. It melted at 85.degree. 
C. and upon mass spectral measurements gave a parent ion at m/e 494 
(theory 494). Upon heating at 200.degree. C. the product showed by 
infrared analysis the presence of the isomelamine ring. Elemental 
analysis, found C 65.54, H 4.49, N 17.65, S 6.48; Theory: C 65.60, H 4.46, 
N 17.00, S 6.48. 
A possible mechanism by which the copolymerization reaction between bis 
cyanamides and N-cyanosulfonamides may take place is illustrated below: 
##STR14## 
It has been found that the reaction of bis cyanamides and 
N-cyanosulfonamide compounds takes place in two stages. In the first stage 
a soluble, meltable precursor is formed which can be designated by 
structure A above. A is formed by heating the two reactants in solution at 
elevated temperatures. Among the solvents found for this purpose are 
aliphatic ketones, alcohols, and esters. Laminating varnishes containing 
up to 70% resin solids concentrations at low solution viscosities can be 
prepared if the reactants are heated at reflux in solvents with low 
boiling points for periods of approximately 0.5 to 3 hours. Preferred 
solvents for the preparation of these laminating varnishes are methyl 
ethyl ketone, acetone, methanol, ethanol, methyl acetate, ethyl acetate, 
acetonitrile and methyl formate. Mixtures of these solvents can also be 
employed in various ratios including azeotropic compositions. Molding 
powders can be isolated from these solutions by evaporation of the 
solvents or by adding the solutions to a non-solvent for the resin. 
Preferred non-solvents for isolation of the molding powders are 
hydrocarbons like pentane, isopentane, cyclopentane, n-hexane, heptane, 
cyclohexane and mixtures such as low boiling petroleum ether. The molding 
powders of this invention generally melt in the temperature range between 
75.degree. to 140.degree. C. 
Heating of these resins within this temperature range causes them to 
advance so that their melt viscosity increases with time while still 
maintaining solubility and fusibility. In this state they can most 
usefully be processed or fabricated to finished articles by press or 
autoclave molding techniques. Heating of the resins within the temperature 
range approximately between 150.degree. C. to 300.degree. C. causes them 
to crosslink or cure and achieve a structure similar to that shown by B 
above. In this state the resin is insoluble and infusible and has 
excellent mechanical strength for structural applications and good 
electrical properties. 
The infrared spectra of the resins prepared from the bis cyanamides and 
N-cyanosulfonamide compounds of this invention indicate the formation of 
s-triazine ring formation upon curing at temperatures above approximately 
200.degree. C. 
It has long been the desire of polymer chemists to provide a method for the 
convenient processing of polymers containing only aromatic and 
heterocyclic rings like s-triazine because of their known thermal 
stability, high temperature physical properties, and good electrical 
properties. Previous investigators (see U.S. Pat. Nos. 3,694,408, 
3,654,192 and 3,308,101) were able to obtain solutions of polymerizable 
precursors only in high boiling solvents like dimethylacetamide or 
trifluoromethane sulfonic acid from whence they could cast thin films for 
evaluation. Fabrication of thick sections with these resins was extremely 
difficult if at all possible because of solvent removal problems or 
premature gelation of the resin before forming it inot the desired shape. 
The novel polymerizable precursors of this invention, however, can be 
dissolved at up to 70% concentration in low boiling ketones, alcohols, or 
esters to provide a practical method of preparing prepregs of high resin 
content for laminating and adhesive applications. These prepregs and tapes 
have good drape and tack for shaping around forms or tools and can be 
vacuum-bagged or autoclave processed to yield large void free, structural 
parts. On the other hand, due to the low boiling point of these solvents 
they can be removed at low temperatures without causing premature 
advancement or gelation of the resin. In the solvent free state "dry" 
prepregs, adhesive tapes and molding powders can be compression molded to 
yield void free parts. 
A large number of bis cyanamides have been found to be useful in forming 
copolymers with N-cyanosulfonamide compounds. Among the preferred aromatic 
bis cyanamides are included m-phenylene bis cyanamide, p-phenylene bis 
cyanamide, 3,3'-bis cyanamidodiphenyl methane, 4,4'-bis 
cyanamidodiphenylmethane, 4,4'-bis cyanamidodiphenylether, m-xylylene bis 
cyanamide, p-xylylene bis cyanamide, 2,4-tolylene bis cyanamide, 
2,6-tolylene bis cyanamide, 4,4'-bis cyanamidodiphenyl, 3,3'- and 4,4'-bis 
cyanamidobenzophenone, 4-chloro-1,3-phenylene bis cyanamide, 
dicyanamidodurene, 4,6-dimethyl-1,3-phenylene bis cyanamide, 
2,5-dichloro-1,4-phenylene bis cyanamide, 
2,3,5,6-tetrachloro-1,4-phenylene bis cyanamide, 3,3'-dimethyl-4,4'-bis 
cyanamidodiphenylmethane, 4,4'-bis cyanamidodiphenyl sulfide, 4,4'-bis 
cyanamidodiphenyl sulfone, 4,4'-bis cyanamidodiphenylmethane, 4,4'-bis 
cyanamidodiphenyl sulfide, 4,4'-bis cyanamidodiphenyl sulfone, 
1,4-bis(3'-cyanamidobenzoyl) benzene, 1,3-bis cyanamidonaphthalene, 
1,5-bis cyanamidonaphthalene, tris(4-cyanamidophenyl) methane, and 
3,3'-dichloro-4,4'-bis cyanamidophenylmethane. Other suitable bis 
cyanamides can be derived from the structures below. 
##STR15## 
n is one to five and the 
##STR16## 
group is replaced by either 
##STR17## 
groups. 
Any of the hydrogen atoms in these benzenoid radicals may be replaced with 
chlorine, bromine, or fluorine groups to increase the fire retardancy of 
the resins. 
Among the suitable aliphatic and cycloaliphatic bis cyanamides are 
pentamethylene bis cyanamide; tetramethylene bis cyanamide; 
bis(4,4'-dicyanamidocyclohexyl) methane; 1,4-cyclohexylene bis cyanamide; 
hexamethylene bis cyanamide; dodecamethylene bis cyanamide; octamethylene 
bis cyanamide. 
Among the suitable heterocyclic bis cyanamides are 
2,5-bis(m-cyanamidophenyl)-1,3,4-oxadiazole; 
2,5-bis(3-cyanamidophenyl)-thiazolo[4,5-d]thiazole; 
4,4'-bis(m-cyanamidophenyl)-2,2'-bithiazole; and 
2,2'-bis(m-cyanamidophenyl)-5,5'-bibenzimidazole. 
Any of the polymeric compositions of this invention can be blended with 
inorganic fillers and fibers or organic fibers to yield reinforced 
composites having either a lower overall cost or enhanced physical and 
electrical properties. 
Addition of solutions of the N-cyanosulfonamide resins to a hydrocarbon 
non-solvent yields finely divided powders which can be given an 
electrostatic charge and applied as a coalesable powder coating to heated 
surfaces. 
Since the polymeric precursors of this invention melt within the 
temperature range from 75.degree. C. to approximately 150.degree. C. they 
can be fabricated with the readily available commercial processing 
equipment utilizing low cost tooling and bagging materials. Good control 
can be maintained at the time of gelation at the fabrication temperature 
so that both rapid or slow processing cycles can be obtained. This is 
achieved by varying the ratio of bis cyanamide to N-cyanosulfonamide 
compound -- the higher this ratio the faster the polymeric compositions 
thermoset. High ratios are preferred for rapid molding cycles and low 
ratios are preferred for the slower vacuum bag and autoclave processing 
cycles. Thus, the melt flow in inches of a 2/1 molar ratio of 
4,4'-methylene bis(N-benzene sulfonyl phenyl cyanamide) to 4,4'-methylene 
bis phenyl cyanamide was measured at two different temperatures until the 
resin thermoset. 
It was demonstrated that melt flow for fabrication can be maintained for as 
long as 20 minutes at 178.degree. C. or 5 minutes at 240.degree. C. with 
no threat of premature gelation. 
The fabricated moldings, composites and coatings can be given post cures 
for several hours in an oven at temperatures up to 260.degree. C. in order 
to maximize their physical properties. The fully cured resins are not 
attacked by organic solvents, have a low water absorption, low dielectric 
constant, do not support combustion and maintain good mechanical 
properties up to 260.degree. C. The oxidative stability of these resins in 
air at 260.degree. C. is good and the mechanical properties are retained 
for long periods in air at elevated temperatures. 
Applications in circuit boards, potting compounds, honeycomb panels, 
structural parts of airplanes where weight saving is important, hot melt 
adhesives, and protective coatings are visualized as important areas of 
application for these resins.

The object and advantages of this invention are further illustrated by the 
following examples, but the particular materials and amounts recited in 
these examples as well as other conditions and details, should not be 
construed as limiting this invention. 
EXAMPLE 1 
To a 3 liter 3-necked flask equipped with a stirrer, additional funnel, 
thermometer and drying tube was charged 525 ml. acetone, 42g (0.169 moles) 
of 4,4'-methylene bisphenylcyanamide and 37.6g (0.372 moles) of 
triethylamine. A solution of 59.8g. (0.338 moles) of benzene sulfonyl 
chloride (99%) in 275 ml. of acetone was added dropwise to the stirred 
solution while maintaining the temperature between 25.degree.-35.degree. 
C. The resulting suspension was stirred vigorously for 1 hour at room 
temperature. The hydrochloride salt was filtered off and washed with 
acetone until the filter cake was entirely water soluble. The filtrate was 
concentrated to 200 ml. by boiling off the excess acetone. To the 
concentrate was added with stirring 1 liter of methanol to precipitate the 
product. The suspension was cooled to 0.degree. C. and stirred for one 
hour and then filtered. 
The filter cake was washed with a minimum of cold methanol, air dried on 
the filter and then dried at 60.degree. C. and 1 mm. in a vacuum oven for 
1 hour to yield 68.4g (76.5%) of 4,4'-methylene bis(N,N'-benzene-sulfonyl 
phenyl cyanamide), m.p. 123.degree.-125.degree. C. The C 61.30; H 3.82; N 
10.59; S 12.11; Found: C 61.29; H 4.08; N 10.34; S 12.09. 
EXAMPLE 2 
To a 100 ml. 3-necked flask equipped with a stirrer, addition funnel, 
thermometer and drying tube was charged 5.0g (0.02 mole) of 
4,4'-oxybisphenyl cyanamide, 2.50g (0.022 mole) of triethylene diamine and 
40 ml. of acetone. To the reaction mixture was added dropwise a solution 
of 7.06g (0.04 mole) of benzene sulfonyl chloride in 15 ml. of acetone. 
The reaction mixture was stirred for 2 hours and then poured into 750 ml. 
of rapidly stirred water. The resulting precipitate was filtered off, 
washed with water and dried. The product was recrystallized from an 
acetone-methanol mixture to yield 8.0g of pure 4,4'-oxybis-N-benzene 
sulfonyl phenyl cyanamide, m.p. 161.degree.-162.degree. C. 
EXAMPLE 3 
To a 2 liter 3-necked flask equipped with a stirrer, addition funnel, 
thermometer and drying tube was charged 12.4g (0.09 mole) of meta 
phenylene biscyanamide, 9.9g (0.088 mole) of triethylene diamine and 475 
ml. of acetone. To the reaction mixture was added dropwise a solution of 
31.2g (0.176 mole) of benzene sulfonyl chloride dissolved in 40 ml. of 
acetone. The reaction mixture was stirred for 3.5 hours and then poured 
into a rapidly stirred solution of 10% aqueous sodium bicarbonate. The 
resulting precipitate was filtered off, washed with water and 
recrystallized from an acetone-methanol mixture to yield 26.5g (77.1% 
yield) of pure N,N'-benzene sulfonyl-m-phenylene biscyanamide, m.p. 
143.degree.-144.degree. C. 
EXAMPLE 4 
To a 200 ml. 3-necked flask equipped with a stirrer, addition funnel, 
thermometer and drying tube was charged 2.36g (0.02 mole) of phenyl 
cyanamide, 1.23g (0.011 mole) of triethylene diamine and 25 ml. of 
acetone. A solution of 3.67g (0.01 mole) of p,p'-oxybisbenzene sulfonyl 
chloride in 35 ml. of acetone was added to the reaction mixture. The 
resulting suspension was stirred at room temperature for 5 hours and then 
poured into 750 ml. of 10% NaHCO.sub.3 solution. The precipitated product 
was filtered off, washed with water and dried. 
The crude solid was dissolved in acetone and filtered. The filtrate was 
added to water and the resulting precipitate was collected, washed with 
water and dried in a vacuum oven to yield 4.0g of p,p'-oxybis-(benzene 
sulfonyl N-phenyl cyanamide), m.p. 160.degree.-161.degree. C. 
EXAMPLE 5 
Two grams of 4,4'-methylene bis(N-benzene sulfonyl phenyl cyanamide) in a 
20 ml. beaker was placed in a curing oven heated at a temperature of 
250.degree. C. The compound melted at 124.degree. C. to form an amber 
liquid which within an hour polymerized to form a rigid disc. This disc 
was post cured for one hour at 250.degree. C. followed by one hour at 
300.degree. C. The disc was insoluble in boiling DMF and an infra red 
spectral analysis showed that the nitrile absorption peak at 4.5 microns 
had disappeared during curing. The thermogravimetric analysis curve showed 
initial weight loss in air occurred between 350.degree. and 400.degree. C. 
EXAMPLE 6 
Fifty grams of 4,4'-methylene bis(N-benzene sulfonyl phenyl cyanamide) in a 
100 ml. beaker was placed in a curing oven at 180.degree. C. for 4 hours. 
During this period the molten compound became increasingly viscous. It was 
then removed from the oven and found to have a melting point of 95.degree. 
C. and to be highly soluble in polar solvents such as acetone, MEK, THF 
and DMF. 
A 50% solids solution in acetone was prepared from this compound and a 
torsional braid was saturated with the solution and dried and heated at 
205.degree. C. for 3 1/2 hours. The glass transition temperature of the 
polymer was 250.degree. C. Upon heating a saturated torsional braid to 
300.degree. C. for 1 hour the glass transition temperature was found to be 
above 350.degree. C. 
A film was cast from the acetone solution and cured for 3 hours at 
200.degree. C. and 1 hour at 260.degree. C. The cured film was 
isothermally aged at 260.degree. C. and found to retain 80.3% of its 
weight after 90 hours of aging. 
EXAMPLE 7 
4,4'-oxy bis(N-benzene sulfonyl phenyl cyanamide), 0.05g, was heated on a 
Fisher-Johns melting point block. The compound melted at 
161.degree.-162.degree. C. and the melt became increasingly viscous as the 
temperature was raised. Within 5 minutes upon reaching a temperature of 
245.degree. C. the melt solidified to form a hard resin that was insoluble 
in hot DMF. 
EXAMPLE 8 
Bis(N-benzene sulfonyl) m-phenylene dicyanamide 0.05g, was heated on a 
Fisher-Johns melting point block. The compound melted at 
143.degree.-144.degree. C. and the melt become noticeably viscous as the 
temperature increased to 210.degree. C. Within 5 minutes upon reaching a 
temperature of 240.degree. C. the melt solidified. 
EXAMPLE 9 
One gram of 4,4'-oxybis-(benzene sulfonyl N-phenyl cyanamide) from Example 
4 was placed in an aluminum dish in a curing oven heated at 215.degree. C. 
The compound melted to form a colorless liquid which crosslinked within 1 
1/2 hours to form a hard thermoset resin that was insoluble in hot DMF and 
other solvents. 
EXAMPLE 10 
4,4'-methylene bis(N-benzene sulfonyl phenyl cyanamide), 355g (0.672 mole) 
and 4,4'-methylene bis phenyl cyanamide, 83.5g (0.336 mole) were dissolved 
in 293g of methyl ethyl ketone. The solution was refluxed for 18 hours and 
the resulting 60% resin solids varnish was used to saturate 181E glass 
cloth (A1100 finish). The glass cloth in a single pass through the 
laminating varnish retained 35% by weight resin and approximately 2% 
residual methyl ethyl ketone. A twelve ply laminate was prepared by the 
vacuum bag-autoclave process. The plies were maintained under vacuum for 
one hour at 88.degree. C. and then heated at a rate of 1.7.degree. 
C./minute until a temperature of 163.degree. C. was achieved wherein 90 
psig pressure was applied. The temperature was increased to 178.degree. C. 
and held for one hour at 90 psig pressure. The laminate of 30% resin 
content was then placed in an oven and post cured for 6 hours at 
250.degree. C. The laminate had a flexural strength of 72,000 psi and a 
(1:4) short beam shear strength of 6000 psi. 
EXAMPLE 11 
4,4'-methylene bisphenyl cyanamide, 5.2g, was refluxed in 12g of methyl 
ethyl ketone for 18 hours. An insoluble mass formed in the bottom of the 
reaction flask. It was filtered off and dried at 65.degree. C./1 mm. 
pressure. This polymer was insoluble, did not melt or soften when heated 
to 300.degree. C. and could not be fabricated into a structural part. 
EXAMPLE 12 
4,4'-methylene bisphenyl cyanamide, 19.9g, (0.08 moles) and 4,4'-methylene 
bis(N-benzene sulfonyl phenyl cyanamide), 42.3g, (0.08 mole) were 
dissolved in 62g, of methyl ketone and the solution was refluxed for 3 
hours. The solution was then cooled to room temperature and poured into 
700 ml. of rapidly stirred pentane. A white, powdery resin precipitated 
which was filtered off and dried. This resin weighed 61g. Examination of 
this resin on the Differential Scanning calorimeter showed that it melted 
at 114.degree. C., showed polymerization exotherms at 134.degree. C. and 
244.degree. C. and gave a crosslinked resin with a glass transition 
temperature of 327.degree. C. 
The resin was blended with 50% by volume of quartz powder and the mixture 
was heated for 15 minutes at 130.degree. C. to advance the resin. This 
molding powder was compression molded for 1 hour at 460.degree. F./3000 
psi. The resulting plaque had a room temperature flexural strength of 7640 
psi and a flexural strength at 450.degree. F. of 5970 psi. The flexural 
modulus at room temperature was 1,130,000 psi. 
EXAMPLE 13 
4,4'-methylene bisphenyl cyanamide, 164g (0.663 mole) and 4,4'-methylene 
bis(N-benzene sulfonyl phenyl cyanamide) 350g, (0.633 mole) were refluxed 
for 3 hours in 440g of methyl ethyl ketone to produce a laminating varnish 
containing 60% resin solids. Glass cloth, 181E (amino silane finish) was 
saturated with this varnish. The resulting prepreg containing 6% solvent 
was tacky and drapable. Eight plies of prepreg were heated at 130.degree. 
C. for one hour and then layed up in a nylon vacuum bag and autoclave 
processed for 1 hour at 350.degree. F./90 psi. The resulting laminate 
containing 25% resin had the following physical properties. 
Flexural Strength, psi; 67,500 
Flexural Modulus, psi; 3,490,000 
Short Beam Shear Strength (1:4), psi; 6990 
EXAMPLE 14 
4,4'-methylene bis(N-benzene sulfonyl phenyl cyanamide), 355g, (0.672 mole) 
and 4,4'-methylene bisphenyl cyanamide, 83.5g (0.336 mole) were refluxed 
for 16 hours in 294g of methyl ethyl ketone. Glass cloth (181E) was 
impregnated with this laminating varnish and the resulting prepreg 
containing 35.4% resin content was vacuum bag-autoclaved at 350.degree. 
F./90 psi over a 2 hour period. The laminate was then placed in an oven 
and post cured for eight hours at 500.degree. F. The resulting laminate 
containing 30% resin had the following physical properties. 
Flexural Strength, psi; 71,800 
Flexural Modulus, psi; 2,840,000 
Short Beam Shear Strength (1:4), psi; 5887 
EXAMPLE 15 
The laminating varnish prepared in Example 14 was used to prepare a 181E 
glass cloth prepreg that was heated for 30 minutes at 80.degree. C. to 
remove the solvent. The dry prepreg was then layed up in 4 plies in a 
press and laminated at 350.degree. F./500 psi for 1 hour. The laminate was 
removed from the press and post cured in an oven at 235.degree. C. for 3 
hours. This laminate contained 30% resin content and had the following 
physical properties: 
Flexural Strength, psi 
Room Temp.; 64,400 
450.degree. F.; 55,100 
Flexural Modulus, psi 
Room Temp. 3,190,000 
450.degree. F.; 3,070,000 
EXAMPLE 16 
A 181E glass cloth laminate containing 21.3% resin was prepared according 
to the procedure of Example 15. Test bars for flexural strength tests were 
cut from this laminate and were placed in a forced draft air over 
maintained at a temperature of 500.degree. F. The maintenance of flexural 
strength of this laminate during oxidative exposure at 500.degree. F. was 
observed as follows: 
______________________________________ 
Hours at 500.degree. F. 
Flexural Strength, psi 
______________________________________ 
0 104,000 
100 77,100 
250 59,000 
500 39,800 
______________________________________ 
EXAMPLE 17 
4,4'-methylene bis(N-benzene sulfonyl phenyl cyanamide), 460g, (0.87 mole) 
and 4,4'-methylene bisphenyl cyanamide, 460g, (1.85 moles) were dissolved 
in 1380g of acetone and the solution was refluxed for several minutes. The 
hot solution was then poured into 15 liters of rapidly stirred low boiling 
petroleum ether. A prepolymer precipitated from the petroleum ether as a 
finely divided powder. The prepolymer was dried overnight under vacuum at 
room temperature. The dried prepolymer weighed 913g (99.2% yield). 
A Differential Thermal Analysis determination on a sample of this 
prepolymer showed that it melted at 111.degree. C and showed a 
polymerization exotherm that peaked at 133.degree. C. A portion of the 
prepolymer was compression molded at 130.degree. C./500 psi for 15 minutes 
to yield a hard disc. This disc was post cured in an oven at 500.degree. 
F. for several hours to complete the crosslinking reaction and optimize 
mechanical strength properties. 
EXAMPLE 18 
4,4'-methylene bis(N-benzene sulfonyl phenyl cyanamide), 211.4g, (0.400 
mole) and 4,4'-methylene bisphenyl cyanamide, 99.5g, (0.400 mole) were 
dissolved in 257g of methyl ethyl ketone and the solution was heated at 
reflux for one hour. This laminating varnish was used to saturate a woven 
fabric composed of polyamide filaments, i.e. PRD-49-111. The saturated 
fabric was heated in an oven at 90.degree. C. for 25 minutes and then at 
120.degree. C. for 10 minutes to remove solvent residues and B-stage the 
resin. Ten plies of the prepreg were compression molded at 1000 psi by 
first heating for 1.5 hours at 350.degree. F. followed by 1.0 hour at 
400.degree. F. The laminate was removed from the press and placed in an 
oven to post cure at 450.degree. F. for 5 hours. The resulting laminate 
had the following physical properties: 
Weight percent resin content; 50.1 
Flexural strength, psi; 42,000 
Flexural modulus, psi; 3,430,000 
Short beam shear strength (1:4), psi; 3750 
EXAMPLE 19 
4,4'-methylene bis(N-benzene sulfonyl phenyl cyanamide), 230g, (0.435 mole) 
and 4,4'-methylene bisphenyl cyanamide, 230g (0.925 mole) were dissolved 
in a mixture of 150g of methanol and 50g of acetone and the solution was 
heated at the reflux temperature for 3 hours. The acetone was then removed 
from this laminating varnish by distilling off the 88-12 acetone-methanol 
azeotrope (B.P. 55.7.degree. C.) while adding additional methanol to the 
varnish to maintain a constant volume. The resulting methanol based 
varnish of 79% resin content was used to saturate 1528 glass cloth (Volan 
A finish). The prepreg containing by weight 46.9% of the varnish was 
B-staged for 15 minutes at 225.degree. F. 
Eight plies of the prepeg were laminated to 1 ounce TC copper foil for 30 
minutes at 350.degree. F./500 psi. The laminate was post cured in an oven 
at 235.degree. C. for 24 hours. The copper foil had a peel strength of 7 
lbs. per-inch of width as laminated. The laminate had the following 
electrical properties before and after water immersion. 
______________________________________ 
After 24 hours 
Before immersion at 
Immersion 
25.degree. C. 
______________________________________ 
Dielectric Constant at 1MHz; 
(77.degree. F.) 4.85 4.92 
Dissipation Factor at 1MHz; 
(77.degree. F.) 0.012 0.011 
______________________________________ 
EXAMPLE 20 
N-benzene sulfonyl phenyl cyanamide 25.8g, (0.10 mole) and 4,4'-methylene 
bis phenyl cyanamide, 49.7g, (0.20 mole) were dissolved in 72g of methyl 
ethyl ketone and the solution was heated at reflux for 30 minutes. The 
resulting laminating varnish of 55% resin solids concentration was used to 
saturate a woven fabric composed of polyamide filaments, i.e., PRD-49-111. 
The prepreg was heated at 90.degree. C. for 0.5 hour to remove solvent 
residues and advance the resin. Seven plies of prepreg were laminated in a 
press at 1000 psi which was heated for 90 minutes at 300.degree. F. 
followed by 120 minutes at 400.degree. F. The laminate containing 51.4% 
resin solids was post cured for 5 hours at 450.degree. F. The post cured 
laminate had a short beam shear strength (1:4) of 2,240 psi and a flexural 
modulus of 3,020,000 psi. 
EXAMPLE 21 
A portion of the laminating varnish from Example 20 was used to saturate a 
torsional braid which was used in the Torsional Braid Apparatus to 
determine the glass transition temperature of the polymer at several 
heating cycles. When the braid was heated for 40 minutes at 178.degree. C. 
the glass transition of the polymer was 250.degree. C. Further heating for 
75 minutes at 250.degree. C. caused the glass transition temperature of 
the polymer to increase to 275.degree. C. 
Precipitation of a portion of the laminating varnish of Example 20 by 
adding the solution to a rapidly stirred non-solvent, pentane, gave a 
quantitative recovery of the solid resin which softened at 60.degree. C. 
and gave a clear melt at 110.degree. C. A sample of the solid resin was 
cured at 250.degree. C. for 90 minutes and submitted for thermogravimetric 
analysis. This resin when heated at 5.degree. C./minute in air lost 4% of 
its weight at 350.degree. C. and 8% of its weight at 400.degree. C. 
EXAMPLE 22 
p-amino benzene sulfonyl N-phenyl cyanamide, 10.9g (0.04 mole) and 
3,3',4',4 -benzophenone tetracarboxylic dianhydride, 6.44g, (0.02 mole) 
were dissolved in 90 ml. of DMF. The solution was heated at reflux for 3 
hours. The solution was then cooled to room temperature and poured slowly 
into 600 ml. of rapidly stirred water. The finely divided precipitate was 
filtered off washed with water and dried at 185.degree. C. in a vacuum 
oven. The imide prepolymer weighed 16.3g (98% yield), theory, C 62.0, H, 
2.88, N 10.10, S 7.69, found: 60.8, H 3.14, N 10.10, S 7.66. 
Infra red analysis confirmed the presence of the imide ring and nitrile 
group. Differential thermal analysis showed that the imide prepolymer 
melted at 169.degree. C. and showed a polymerization exotherm commencing 
between 180.degree.-190.degree. C. A torsional braid curing study showed 
that this polymer had a glass transition temperature of 310.degree. C. 
after a 2 hour heating period at 300.degree. C. 
The imide prepolymer was dissolved at 30% by weight concentration in 
N-methyl pyrrolidone and the solution was cast as a film. The film was 
heated at 250.degree. C. for 1 hour to cure the polymer. The cured film 
was oxidatively aged by heating in a forced draft air oven at 500.degree. 
F. After 514 hours of aging the film retained 90.3% of its original 
weight. 
EXAMPLE 23 
To a 3 liter 3-necked flask equipped with a stirrer, addition funnel, 
thermometer, and drying tube was charged 93.1g (1.0 mole) of aniline, 111g 
(1.1 moles) of triethylene diamine and 250 ml. of tetrahydrofuran. To this 
reaction mixture was added dropwise a solution of 176.6g (1 mole) of 
benzenesulfonyl chloride in 300 ml. of tetrahydrofuran. The reaction 
mixture was stirred at room temperature for 2.5 hours and was then 
filtered. To the filtrate was added 111g of triethylene diamine and this 
solution was added dropwise to a solution of 87g (1.41 moles) of cyanogen 
chloride in 100 ml. of THF which was maintained at -5.degree. C. with 
cooling. After this addition was complete the stirred reaction mixture was 
allowed to return to room temperature over a 16 1/2 hour period. The 
reaction mixture was filtered and the filament was added to water to 
precipitate the product. The product was recrystallized from aqueous 
methanol to yield 218g (84.7%) of N-benzene sulfonyl phenyl cyanamide, 
m.p. 65.degree.-66.degree. C. 
EXAMPLE 24 
4,4'-methylene bis(N-benzene sulfonyl phenyl cyanamide), 237g (0.448 mole) 
and 4,4'-methylene bis phenyl cyanamide to 335g (1.35 moles) were 
dissolved in 702g of methyl ethyl ketone and the solution was heated at 
reflux for 1 hour. The resulting laminating varnish was used to prepare a 
prepreg containing polyamide woven fabric PRD-49-111. The prepreg was 
dried at room temperature under vacuum and eight plies were press 
laminated at 300.degree. F. for 10 minutes followed by 1 hour at 
400.degree. F. This laminate containing 33.4% by weight resin was post 
cured for 5 hours at 450.degree. F. The post cured laminate had a short 
beam interlaminar shear strength (4:1) of 2000 psi. 
EXAMPLE 25 
4,4'-methylene bis (N-benzene sulfonyl phenyl cyanamide), 10.1g (0.0191 
mole) and 4,4'-methylene bis phenyl cyanamide, 30.0g (0.121 mole) were 
dissolved in 30g of acetone and the solution was refluxed for 10 minutes. 
The hot solution was poured into one liter of rapidly stirred low boiling 
petroleum ether to precipitate the propolymer as a finely divided powder. 
The dried powder when heated melted at 120.degree. C. and within a few 
seconds thermoset at this temperature. A differential thermal analysis 
showed that the polymerization exotherm peaked between 135.degree. to 
145.degree. C. and could not be observed above 213.degree. C. 
EXAMPLE 26 
Bis(N-benzene sulfonyl)m-phenylene dicyanamide, 17.54g (0.04 mole) and 
m-phenylene dicyanamide, 3.16g (0.02 mole) were dissolved in a mixture of 
20.7g of methyl ethyl ketone and 1.1g of dimethyl formamide. The solution 
was heated at reflux for 16 hours. A portion of this prepolymer solution 
was used to coat a torsional braid and the glass transition temperature, 
Tg, was determined in the torsional Braid Apparatus. The Tg was 
290.degree. C. after heating the braid for 2 hours at 200.degree. C. 
followed by one hour at 260 C. 
A portion of the prepolymer solution was used to cast a film which was 
heated for one hour at 260.degree. C. to cure the film. The film was 
isothermally aged in a forced draft air oven heated at 500.degree. F. 
After 1014 hours of aging at 500.degree. F. the film retained 66.3% of its 
original weight. 
EXAMPLE 27 
p,p'-oxybis-(benzene sulfonyl N-phenyl cyanamide) from Example 4 was heated 
in a Differential Scanning Calorimeter. A melting point was observed at 
164.degree. C., the onset of polymerization at 210.degree. C., and a 
polymerization exotherm peak at 265.degree. C. When heated in air in a 
Thermal Gravimetric Analysis Apparatus the cured resin retained 90% of its 
original weight at 400.degree. C. 
EXAMPLE 28 
p,p'-oxybis-(benzene sulfonyl N-phenyl cyanamide), 5.31g, (0.01 mole) and 
4,4'-methylene bis phenyl cyanamide, 1.24g (0.005 mole) were dissolved in 
20 ml. of methyl ethyl ketone and the solution was heated at reflux for 16 
hours. The prepolymer was precipitated as a fine powder by pouring this 
solution into 500 ml. of rapidly agitated hexane. The dried prepolymer 
melted at 120.degree. C. and thermoset within 15 minutes after being held 
at a temperature of 215.degree. C. After heating this powder at 
300.degree. C. the glass transition temperature was 290.degree. C. 
EXAMPLE 29 
p,p'-oxybis-(benzene sulfonyl N-phenyl cyanamide, 7.9g, (0.015 mole) and 
4,4'-oxybis phenyl cyanamide, 1.89g (0.0075 mole) were dissolved in 10g of 
methyl ethyl ketone and the solution was heated at reflux for 16 hours. 
This solution was used to case a film which was cured for one hour at 
260.degree. C. The film was isothermally aged in a forced draft air oven 
at 500.degree. F. and was found to retain 68% of its original weight after 
846 hours of aging in air at this temperature. 
EXAMPLE 30 
Twenty five grams of N,N'-methane sulfonyl-1,6-hexamethylene biscyanamide 
in a 50 ml. beaker is placed in a curing oven at 200.degree. C. The liquid 
becomes increasingly viscous and finally thermosets within 90 minutes. The 
resulting disc is insoluble in boiling DMF. 
EXAMPLE 31 
N,N'-methane sulfonyl-1,6-hexamethylene biscyanamide, 3.22g (0.01 mole) and 
3.32g (0.02 mole) of 1,6-hexamethylene biscyanamide was stirred together 
in the melt at 90.degree. C. for 1/2 hour to yield a viscous syrup. This 
syrup is then placed in a curing oven at 177.degree. C. for 1 hour. A 
transparent, crosslinked molding is produced that swells only slightly in 
boiling DMF. 
EXAMPLE 32 
2,5-bis(meta cyanamidophenyl)-1,3,5-oxadiazole, 3.0g, (0.01 mole) and 3.22 
g, (0.01 mole) of the imide prepolymer of Example 22 are dissolved in 50 
ml of DMF solution and the solution is used to coat a torsional braid. A 
torsional braid curing study shows that this polymer has a glass 
transition temperature of 250.degree. C. after a 3 hour cure at 
200.degree. C. and a glass transition temperature of 315.degree. C. after 
a 2 hour heating period of 300.degree. C. 
EXAMPLE 33 
4,4'-methylene bisphenyl cyanamide, 248g, (1.0 mole) and 4,4'-methylene 
bis(N-benzene sulfonyl phenyl cyanamide) 248g, (0.47 mole) are dissolved 
in 500 ml. of acetone and the acetone solution is refluxed for 5 minutes. 
The acetone solution is then poured into 6 liters of rapidly stirred 
petroleum ether to precipitate a white, powdery resin which is filtered 
off and dried under vacuum at room temperature. The dried resin is heated 
for 10 minutes at 90.degree. C. and then placed in a mold and compression 
molded at 300.degree. F./3000 psi for 1 hour. The yellow, transparent 
plaque is removed from the mold and post cured at 500.degree. F. for 2 
hours. A flexural bar from this post cured resin has a flexural strength 
of 16,300 psi and flexural modulus of 616,000 psi.