CA1066840A - N-cyanosulfonamide resins and intermediates therefor and products thereof - Google Patents

Abstract

Abstract of the Disclosure 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.

Description

~L~16~

T~s invention relates to polysul~onamides which are prepared by the addition polymerization of bis-N-cyanosul:Eonamides.
The bis-N-cyanosulfonamides are novel compounds which are the subject of our Canadian Patent Application Serial No. 218,803, filed January 28, 1975~ from which thls application is dividedO
In accordance with this invention a new class of poly-sulfonamide resins for use in coating~ laminatingl molding and casting applica~ions has been discovered. These resins are dis-tinguished by ~heir easeo fabrication, low raw material cost and exceptional elevated temperature and electrical properties.
These resins are prepared from polymerizable composi-tions which contain organic groups of the formula .
: CN

~ N SO2 : '"

~: ' -which unexpectedly have been found to ~dergo an addition polymerization re-action believed to involve the trimerization of the cyano moiet~.
The polymerizable compositions contain in their molecules two or more of groups CN-N-S0~- c~ttached to one or more divalent aromatic, alipha-tic, cycloaliphatic or heterocyclic radicals.
Accordingly the present invention provides a polymer derived by addition homo-polymerization of a bis-N-cyanosulfonamide of formula I or II:
NC-N-R-N-CN
t I : .
~S2 S2 (I) Rl Rl or NC-N-S02-R-S02-N-CN
Rl Rl wherein R is a divalent aromatic~ aliphatic, cycloaliphatic or heterocylic radical~ and each R~ is independently a monovalent aromatic, aliphatic, cycloaliphatic or heterocyclic radical; by addition co-polymerization with one mole of a bis-N-cyanosulfonamide of formula I or II with 1 to 10 moles of a bia-cyanamide having the formula VII
NC-NH- ~-NH-C~ ~VII) -~
:
wherein ~ is an aromatic, aliphatic~ cycloaliphatic or heterocyclio radical;
or by addition polymerization of an N-cyanosulfonamide co~pound of the form, uIa:
Rt-N-CN~

~ S2 ::
~ 2 -6613g~
wherein R~ is as defined above~ with a bis cyanamide of formula VII defined above.
Compounds whose use in the polymers of the Invention is prefer-red are bis-N-cyanosulfonamides which are characteri~ed by the formula I or II, defined above.

The divalent aromatic radicals may be linked by divalent groups such as CH3 -o- -e- -CH- c- ~ s- -N-, divalent imide o CH3 0 ~:
- 2a -:
~ '' 1~ ~ 6~ ~0 and amide structures ~uch as \ ~ ~ N - and ~ C ~ ~-NH
¦¦ ~ H00 C00 The divalent groups may also be het.ero~yclic such as thi~diazolyl, pyronyl, benzimidazolyl and the likeO Th~
divalent aromatic groups may be s~ubstituted with halogen~ ;.n or~er to achiev~ greater ~ire retardancy. Rn example o~ a compound in this embodiment is showD by the ~ollow~ng ~ruct~.

NC~ N ~ S ~ -0 ~ S- ~-CN

, The divalent.aliphatic and cycl~al.iphati~ ~r~ups may be al~ylene of ~ carbons! preferabl~ 1-7, cycloa~k~len~
o~ 3-7;carbons, and such radicals heari.ng eI~ctronegati~e substituen~s such as halogens, especially fluoro.

, ~

~L~66~41~
The compositio~ containing compouncls o the Eormu-la I or II can be copolymerized with compositions containing a compound of the ~ormula VII:

NC--HN--R~ CN (VII ) wherein R ls a divalent aromatic, aliphatic or heterocyclic radical. The divalent radicals can be linked by a divalent group such as -S- and thos~ descr~bed above. An example o a compolmd o:~ the formula VII ls given by ~he following s tructure, ..: .
NC-N ~ 0 ~ N-CN .-The polylEIerizable compositions may he either pure ~;
compound~ or oligmers that cure by an addition polymeriza- .
, tion me¢hanl~m to yield cr~sslinked re~ins having a high gla~s -~ : transLtlo~ ~empera ure and good ox~da~ve stabil~ a~ ~em-: pera~ure~ up to approximately 260C. ~ppli~tion~ as ~: ~ c~cuit ~oards, enoap~ulati~g xesins or eleo~ al use :
: ~potting compounds), high temperature a~hesives, compre~sion ~ and transfer molding compounds, powder cQa~in~s.and ~esin-~ . . .
m3~ri:0es ~or:inorga~ic;and ~rganic fibe~ eomposites such as ; laminates with~glass, boron , polyamide and ~raphite i.bers, a~ v~sua~lzed.

. - :

According to the invention, the bl~-N-cyanosulonamide compounds of the Eormula I or II

NC - N -R - N--CN NC~ S02- R -SO~--N -CN
21 72 (I) or R' ~' (II) R' R' wherein R i~ a divalent aromatic, aliphatic, cycloaliphatic or heterocyclic radical, and each R' i9 independently a monovalent aromatlc, aliphatic 9 cycloaliphatic or hetero-cyclic radical, are manufactured by a process, which com-prises react~ng a diamine of the ormula III

H2N -R NH2 (III) either firs~ with a cyanogen halide and then with a 3ulfonyl chlor~de of the formula IV
R'~ S02Cl (IV) or vic~-versa, whereby the diamine~ the cyanogen halide and : ~ :
~: the ~ulfonyl chloride are employed in a molar ratio of 1 : 2 : 2, or reacting an amine o~ the ~ormula V

R NH2 : (V) ~: :
: either first with a cyanogen halide and ~hen with a di- .
su1fony1 eh10ride of ~he formula VI
: GLSO~ R -~02Cl ~VI) ~ 5 ~ ~

. .

~L~66~

or vice-versa, whereby the amine, the cyanogen halide and the d;Lsu1:Eonyl chloride are emp1oyed in molar ratio o

2: 2: 1.

The groups R contained within a single molecule may be all the s~me or different, and similarly the groups R' contained within a s1ng1e molecule may be all the ~ame or different. The groups may also be ha1ogenated. Preferred structures cf the N-cyanosulfonamide compQunds ~nclude N~ NC~ ~ CN

(ortho, ~eta or para) ~ortho, meta or para) ~ ;

: ~ ~ O C3 wherein X is ~0-, -CH2-9 -N- , -S-j -S-, -C-, and -C~ and ~ ~

O C . .' H
a ingle bond and n is zero to flve. :

... .

:NC-- --S ~ ~fi-- --C~ ;
: ~ ~ ~ X ~ 3 2 ~ ~ ~ [~
goxtho,: met~ or para) ~36615~

CH
whereln X is -O-, -CH2-, -N- , -S~ C , [~ O O C113 Q O O
Il ,. ..

C~C~ N and O ..

O ~ O
H " ;~f ~, C~ N--HOOC COO}~

~ .
In the structures di~ectly abover th~ ~ group~
oan be replaced by ~ and lo~ or groups wlthout int:er~ee~ing ~ th the c~ncep~
o~ in~ tit~n . S~milarly r ~"3,r o~ the hycl~o~en atoms in thesa benæenoi~l radicals may ba r~placed wi~h chlor~rle, ~irQmin~
or ~luoxine gr~up~ without . less~ning utili y .

- In the synthesi~ of the N-cyanosul~onamide comp~unds o~ the structuxe shown by ~om~ula I, the sulfonyl chloride :: can be reacted with a bi~eyanamid~ derive~L from a diam:ine and cyanog~n halide or fir t reacted wi~h a dLamlne to ~ield .

~6~40 a sulfonamide which i8 then reacted with a cyanogen halide to yield the desired N ~yano~u~fonamide comp~und. Overall yields by either route are In e~ces~ of 80Z. Suitable aromatic sulfonyl chlorides for these reaction sequences include benzene sulfonyl chl.orid~ 9 p-chlorobenzerle sul~onyl chloride J
p-toluene sulonyl chloride, 2-naphthalenesulfonyL chloride and anthracene-2-sulfonyl chloride. Suitable alipha~c and cycloaliphatic sulfonyl chloride~ ar~ me~hane ~ulfonyl chloride, ethane sulfonyl chloride9 trifluoromethylsulfonyl chloride, n and iso propyl sulfonyl chloride, n and iso butyl sulonyl chloridel n and i~o amyl sulfonyl chlor~de9 cyclo-pentane sulfonyl chloride, n hexyl ~ulfQnyl chloride, cyclo-hexane sul~onyl chloride and n-heptyl and n-octyl sulfonyl chlorides. Among the ~uitable he~erocyclic sul~onyl halidas ~re thiophene-2-sul~onyl chlor~de and benzopyran~6-~ulfonyl ~ :
chloride.
-In the synthe~is o th2 N-cyanosulonamide com p~und~ of al~ernat~ structure shown by ~ormula II di~ulonyl chloride~ can ~e reac~ed with an amine like aniline ~o yield the corresponding sulfonamide whi:ch i~ thenreacted with cyano-gen halide or r~acted with a cyanamide to y~eld the des~rat :.
~ompoundO Overall yiel~s by either route are ln ~xces.s o~ fl~%.
8peclfic exampl~ o ~he preferred a~omatic disulfonyl ha~des : u~d i~ the pras~t in~ention include: ben~ene-1~3~disul~o~yl ch~orid~ b~nz~n~-},3~ ul~onyl brc~ld~ 2,~5,~t~tra~hloxo~

; 8 :

~a6~a benzene~l,3-disulfonyl chloride7 naphthal~ne-l,S-di~ulonyl chloride; o-xylene-3,5-disulfonyl chloride; p-xylene-~,6 disulfonyl chloride; naphthalene-2,7-disulfonyl chloride;
d~phenyl-~,4'-disulfonyl ~hloride; diphenyl ether-4,4'-disuJ.w ~onyl chloride; d.iphenyl c;ulid,~-4,~'-disul~onyl chloridei and b~nzophenona-4,4'-disulfonyl chloride. Examples o~
ali~h~ic and ~ycloaliphatic di~ulfonyl halides axe methane disulfonyl chloride; ethane 1,2-disulfonyl chloride; cylo-hexane disulfonyl chloride; propy~-1,3-disulfonyl chloride;
and i~obutylene lJ3-disulfonyl.chloride. Ex~m~les o~ he~ero~
cycl~c disul~onyl halides are dibenzothiophone-3/6 disul~onyl ~hloride; and diphenyl-2,2-sulfonyl-~,4' disul~onyl chloride.
Whe~ the abo~e bis N- cyanssul~onamide compounds are heated above their melting points the ~luid melt becomes in~r~asingly viscous and eventually thermosets to yiela a hard plastic having utility in ~truc ural application~ e., moldingsi castin~s, composites, and ~or protective uses, i.e~
coa~ing5, The temperatur~/t ~ e relationship ~or thermo~etting i8 shown b~lo~Y for 4,4'~meth~1e~ bis (N-benz~ne ~ul~onyl ph~nyl cyanamid~), ~.p. 129C.

' : : :

~ .
~ 9 -.

~066~

Ta~le I
Polymeri~tion of 4,4'-~ethylene bis(N-ben2ene sul~on~l pheny~
cyanamide) _ _ _ Pol~eri2ation Temperature_C. G~l Time 240 3 minute~
200 35 mi.nu~s 1~0 5 hours 185 7 hours 180 10 i~ours A dif~erential t}lermal analysis run with ~his compound showed ~ pol~merization exotherm between approximately lg9-2~0C. which gave a heat of polymerization of 33.7 kilo calJmole.
~he increasP in the glas~ transition temperature (Tg) o~ ~he polymer at various cure ~emperatures and times measured by a Torsional Br~id analy~er i~ shown b~low.

Table II
Tor~ional ~rai~ Ana~ysis o~ Poly-q,4~-Methyl~ne h~s(N-b~nzenR
6ulfonyl ph~nyl cyanamida) Cure Te~perature C. Cuxe ~ime in Hours 200 3 ~ 5 2~i0 - ~ -240 . ~ 0~ 5 2S3 300 0~ 5 25Q
300 lol~ ~50 .

1 C~
, ~OG684~

An elemQntal analy~ run on the monomer be~o~
curing andafter curing at 300DC. is s~lown belo~ i.ndicating that the pol~mer has essellti~lly the same elemental analysis as the monomer and has not evolved ~onden,sation pro~ucts or oxiaized in air at 300C. to any signiicant extent.

Table III

Elemental Analysi~ of Poly-4,4 ? -Methylene bis~N-b~nzene ~ulfonvl ~henYl cvanamide) after 300C. Cure in Air %C 61.9 S3.3 %H 4.11 4.22 %N 10~6 12.8 %S 11.5. 1~.

Heating o~ the compound N-benzene sul~ony} phen~
cy~na~nide at 24ûC. ~Eor 3 hc~ur~ gave a product showing, by infrared absorption, the presen~e o~ the s-triazine ring and a1~sena~ of n~trile group a~orption at 22~0 cm~ mol~cular -weight measurement by ~rapo~ phase osmometry show~d that the molecular weiyht had approximately tripl~d which ~ould indicat~
that a trimerization r~action had ~aken plac~

. .. .
: : A.possible, bu~ not necessarily the onlypolymerization mechanism, for~N- ~ya~osul~on~m~de compounds is illu6trated Wt ;:~

~0~6~

_ ~ ,.
` ~
~ N S2 ~;2

3 NC~N--R--N--CN---- ll ,~ N ~
~C--M ~ N~ C C--N~R--N---C
S02 S 2 ~02S2 ~ ,N N--(~ ~ .~ S~) :"

. ~ ~S~ `: , , ~ C ~ . ~ .

. ' ''. '' ;'~
. . ~ .
. ' . ~ ,.
_. ' . . ' .

~' ::
or alternately ~ ' , .
..
,, : :.
;.

: ~ .
::
:

~ ~ : : ~ 1 2 ~ :

1C~6~

3 NC - N - S 2~ S 2 _ N CN ~
~ ' ~J :
_ ' ' ,, ~il 2 2 oN \ 2 2 ~N~
~5--N ---S--R--S~ S--~S--~--C

. ' 11~ . ' ' ' . ' ' , " . ' : .
. ' ' ~ '', '''~:"
' ,~ C\ ' ' ', `~ ~ .
.. 1 . , .. .
. . . , ," : .. . , . ' whereiD ~ ~is as de~i~ed previou~slyO

he above illustrated polymers are~hL~h mol~cular.
weig~t, thxee-dimensional, cr~sslinked st~uct~res, the r~curing , . . : -aroma~ic and heterocyc~ic rings conferring hi.gh ~hermal sta~
billty,~ohemical~:inertness and water and sol~en~ re~istance.
h~se~polymers do~not soften below their decomposition temp-e~atures~and~have~glass transltion temperatur~s (T~' G) generally above 300CO The pol ~ e~ ~rom~ moDomers o~ struc~1~ I are ;8~

more ri~id and lla~e hi~her T~ ' s th~n the more ~lexibl~ polymers ~rom structure Il` th~t h~ve a ~reater distance betweer1 t:he . .
crosslin];ing sites, Thermogravirnetric analysis in ~ir ~hows that these polymel-s have short term stability up to 300C~ wi.t1 appxo~:imately lO~ or les.s wei~ht loss reached at 350C~ ~hysi~
cal properties o~ these pol~ners are retained durin~J isothermal aging at 260~C. over extended periods o~ time~
'~he ~ol~merization data in T~ble I in~icat~s tha.t . -pol~merization belo~ a temperature o~ ~00C~ takes ,L~lac~ at a rela~iv~ly slow rate~ ~or a number o~ applic~tions it is desirable to pxocess and fabricake thermosett.in~ polym~r~ at a~ low a temperature as possible and as rapidly as possil~1e ~ox econoJnic: rea~ons. On the other hand~ the polymerization o~ -aromatic bi~ cyan~mides containing two or moLe groups ~avin~
~he structux~3 ~;hown in fo:rmula II normally t~kes place very rapidly at low temperature~ even in the æolid state below t}le .
tempex~t:ure a~ ~Yhich the meltiny point ls reached. q~his fac~ ...
ma~es the polymers prepared ~rom aromatic bi5 cyanamid~s oiE
ry llmite~ u~ y ~1na~ th~y a~nn~ot b~ mail~t~ d $n ~ mc31~en ~ate ~c~r a su~fici~n~ pexioc9 1~ shaped or abricated into ~inishea paxts. In i~aat t:he mel~f,ng poi.nts o.~ aro~al:aa l:~i9 c:yanamide.s cQntaining no aliphatic g.roups cannot be o~tained. ;;
has une~pectedly ~en found that l:he - solu~ion to both of these probIems, i.e. ,: nol~melting of ~romatic: bi~
.
: cyanamides and ~Iow polym~riza~ion of the N-cynnosulfonamide :
compounds~ at moàerate temperatures can be solved by th~ GOpOly-',.

merization of the N-cyanosulEonamide compound~ with aromatic bis cyanamides at variou~ molecular ratios. ~t the low~r limit it requires approximately 0.1 mole of ar~mati& .bi~
cyanamide pe~ mole of N~cyanosulfona~ide compound to noticeabl accelerat~ the polymerization rate ~t l~O~C, At th~ upper limit, extremely fast thermosetting composi~ions are a~hieved at 140C. with app~oximately three moles of aromatic bis cya~ami~e to one mole o~ W-cyanosulfonamide compound~ In ordor t~ allow sufficien~ time for m~lt 1OW and removal of solvent, i~ present, while processing between 140-180C., a preferred range of appro~Lmately O.S mole to 3,0 moles o aromatic bis cyanar,lide compound per mole o~ N-cyanosulfonamide has been found op~imal.
In ~ahle IV it is ~hown that lncreas~n~ th~ molar concentration of bis cyanamide in mixtures of N-cyanosulfon-amide bis cyanamide results in a more rapid cure as det~rmlned by Torsional sraid Analysis measurement~ of Tg's.

~able I~
a ~ ~ :
~y pa ~ ~? (MBSPC) ' (~uring Tlm~
in Hxs . at Tg of 2: lJ Tg of 1:1~ Tg o~ 1: 3/
178~C. . M~3SPC:MBPC~ MBSl?C:MBPC MBSPC-MBPC
O ~ S - 177 c o;~!15 C . .
~0 205C~
..
1 .~ 7 5 -- ~ ~7 C ,. ~
, 2.5Q ~78~.227 : : - 15 -~

, . ., . ., .. ., . , . . , , , .. , . . . , ... , .. .. - , . . - .. . ., . . . - . - . . .. ..
, . . . .: ......... ,:;, . , , . . . . , . . :, . ,. . ~ .. . :. , ~66~

By ~t~ldying the reaction between mocl~l compo~nds of:
N-cyanosulfonamide-bis cyanamide mixkures it was demons~ra~ed that both species preferentially react wi.th one another (copol~me.rixe) rather than ~orming a mixture ~f homopolymexs.
N-benzene sul~onyl phenyl cyanamide, (O~n2 mole~), m~p. 59~C.
and phenyl cyanamide ~Ø04 moles), m.p. ~0C. were stirred in the mel~ ~or 3 hours at 82C. at which point ~he melt solldified. ~he reaction m;xtu~e was then dissolved in methyl ethyl~etone and the solution was h~ated at xeflux te~peratures overnlght, The pxoduct waæ isolated by pourin~ the solu~.ion into pentane. It melted at 85C. ana upon mass spectral measurements ~ave a parent ion at.mje 494 ~t.heory 4?0 ~ ~pon heatin~ at 200C~ the product showea ~ inxaxed Analysis th~ presen~e of the isomel~mine ring. El~nental anal~is t ~ound C 65.54, ~ 4.49,.N 17.65, S ~.4~; Theory: ~ 65G60t H ~.46, N 17.00, S 6.48. ~ ;
A possible mechani~m by which the copolym~rLæa~ion reaction be~ween bis cyanami~es and N-cyanosulon~mid~s may take plaoa ~s illu~t~ated below~

NC~ ~-N--ON ~ NC--N~il2~ N-CN

80C./ .

`

lC)G6840 H ~ !
N N

>17~C

_ ~a . .
H~

: ~ ~ ~ C ~ ~ 2 ¦ S 2 ~ ~ 50 1 ~ NETC
: . ~ ~ SO2 : . ' ' ` ~ : ~ ".

~: ~ ~
.:
: n It has been found that the reaction of bis cyanamides and ~-cyanosulfonamide compounds takes place in two stages~
In the first stage a soiuble, meltable precursor i5 fOrmea ~: ~ : which can be des1gnated hy structure A above. A is form d by heat;ing the:two reactants in solution at elevated temper-: atures. ~mong t~e solvents found for this purpose are .:

: ~ - 17 - -:: -:

~ ~;68~

aliphatic keton~s, alc~hols, and e~t~rs.Lamlnating varnlshes containing up to 70~ resin solids concentrations at low solu~ :
tion viscosities can be prepared if ~he r~actant.~ ar~ he~ted ~t reflux in solvents with low boiling points for perlods o~ approxlmatel~ 0,5 to 3 hoursO Preferred solvents for the preparation o these lamin~ting v3rnishes ar~ methyl e~hyl ka~one, acetone, metllanol, ethanol, m~th~l acetate, ethyl acetate, acetonitril~ and methyl Eormate~ Mixtures o~ these solvents can also be employed in various ratios incl~dlng azeotropic compositions. Molding powders can he isolatedfrom the~e solutions by evap~ra~ion of the solvents or by aclding the solution~ to ~ non solvent for the resin. Pre~lerred non-solvents for isolation o~ the molding powders are hydrocarbon~
like pentane, isopentane; cyclopentane, n-hexane, heptane,cyclo-hexane and mixtures such as low boillng petrolcum ether. The molding powdexs of thl5 inven~ion generally melt in the temp-~ erature range between ~5 to 140C, ; ~ Heating o~ these resins within this temperatuxe rang~
aau e~ them to ad~anc~ so that their melt vi~cosi~y increase~
with t~me while still m~intaining s~lubility and ~u~b~lity, , Xn this ækate th~y can most use~ully be processed orfabricated to fini5hed articles by pres5 ~r autoclave molding technique~

Heating of the resins within the temp~ratur~ range approxi- -:mately between 150C. to 3~0C. causes them to crosslinX or oure and achieve a ~tructure similar to that shown by B abov~, I~ thi~ ~tato th~ resin i~ in~olub~ an~ ~n~u~ibl~ an~
:: :

., .

~ID668~
excellent mechanical strengt~l for struc~ural applications and qood electrical properties.
The inE.rared spactra o~ the xesins prepared ~xom the bis c~anamides ~nd N-cyanosulfonamide compounds o this invention .indicate the ~orm~tion o~ s-tria~ine ri.ng format.ion upon curing at temperatures above approximate].y 2ao~c.

It has long been the desire of polymer chernists to provide a method for the convenient process.ing of pol~mers containing only aromat.ic and heterocyclic rings li};e s-triazine ~ecause of their known thermal stabilityr higll tempera~llre physical properties~ and good electrical proper~.ies. Prev.ious investigators (see IJ.S. 3,694,4D8, U.S. 3,654,192 and ~.S. 3,308,101) were able to obtain solutions of polymerizahle precursoxs only in higll boil~
ing solvents like dimethylacetamide or tri~luoromethane sulfonic acid ~rom whence they could cas~ thin films ..
~or evaluation. ~abrication of thick sections with these ..
: resins was extremely difficult if at all pos~ible because o solvent removal prohlems or pxemature gelation o.~ the r~.sin befoxe ~orming it inot the desired shape~ The ~ovel.polymerizable precursors-of this inventi.on, howe~er, : oan be dissolved at ~p to 70% concentration in low boil.in~
:~ ketones, alcohols, or esters to provide a practical method - `of preparing prepreys of ~igh resin cont nt for l.aminating and adhesive applicatlbns. These prepreg~ and tapes h~ve good drape and tack for sha~ing around forms or tools : : ' : .

^-- ~
6~
ana can b~ vacu~-ba-J~ed or au-toclave processe~1 to yield lar~e void free, stru~tural parts. On the oth~r hand, due to ~ha low ~ilin~ point of khese solvenl:s they can be r~moved at lo~ temperatures w.ithou~ causing premature advance~ent or gelakion of the resinO In the solvent free sta-te "dry" prepre~s, adhesive tapes and molding po~ders can be compression molded to yi~ld void ~r2e parts.
A large num~er of b.i~ cyanam:ide~ have been follnd i:o be use~ul in fo~ming copolymers wit.h N~-cyano-sulfonc~lide compounds, Among the preferred aromatic bis ~anamides ar~. included m-phenylene bis cyanc~ide, p-phenylene bi~ cyan~nide, 3,3'-bis cyanamidodipllen~l me~hane, ~ bi~
cyanami.dodiphenylmethane, 4,4~-bis cyanamidodiphenyle~her, m-~ylylene bis cyanamid~, p-xylylenQ bis cyanamide, 2,4-tolyl~
ene bis cyanamide, 2,6~ol~lene bis cyanamide, 4,4~ls c~rana~- :
midod.ipl1enyl, 3,3'- and 4,4'-bis cyan~midol~enzophenone~ 4~ . .
chlo~o-l,3-ph~n~lene b~s cyanam;.de, dicyanamidodu~ene, 4,Ç~ :

.
dimetl1yl-l,3-pheny.~ena ~is;cyanamide, 2,5~dichloxo~ phenyl~ne:
bi~ cyanc~miide, ~,3J5,6~tetr~chloro~l,4-phienylane.bi~ cyanamid , 3,3'-~ime~hy1-4,~-bi~ c~anamidodiphenylme~han~, ~,4'-bis cyanan~idodipl~enyl sulide, 4,4'~h~s cyanami.i.~odi.phenyI ~ul~on~, :

4,~'-bis cyanam.idodi~h nylme~hane, 4,4'-bis cyana3nidodipl1enyl sulf.ide, ~,4'-bis oyanamidodi.phenyl sulfone, 1,~bis(3'-cyana-midobenzoyl) ben~ene, l,3-bis cyanamidonaphkha]ene, ~.,S-h.;.s cyal1amidonaphthalene~ tris(~~cyall~midop}~enyl) me~hane, and 3,3l-dicl1loro~~ -bis cyan~nic~ophenylme~hane. Other suitable is ~yanamides can be d~ivea ~rom ~he struct.ures b~low.

0- .
., ~;6~

NC N~--X ~ CN

Cl O CH
wherein X is -O-, -CH2-, -N- , -S~ , or-C~
O C~3 n is one to ive an~ the ~ group is replaced by either -- or --~ groups..

Any o~ the hydrogen atoms in these ben~enoid radic~ls ma~ be replaced with chloxine, brc~mine, or ~luorine g.~ou~s to ~- .
increase the ire retardancy of the refiins~
~ mong the suitable aliph~ic and ~cloalipha~i~ bis ~yan~nLde~ are pen~am~hylene bis cyanamide; ~etrame~hyl~ne bi~ ~anam~de: biætA,41-di~yanamidocyolohexyl~ m~ n~;
: .
4-oyolohexyl~n~ b1~ cyanam~; he~ameth5rlen~ bi~ ~y*~namide, doae~amethylen~ bls cyanamLde; oct hylene bis a~anami~
~ non~ the suitabJ.c het.~xocyali~ bi~ ~yanamlae~ axe 2, S-b.is ~m-a~anamLdophenyl) -1, 3, ~--oxadiaæole, ~ ~ 5-l:)is~3-c~ana-midoph~nyl~-tl~Lazol~14,S-dll~thLaæole; ~,4'-bis(m-c3~anamidophenyl)- :
2, 2 ' -l:~L~hLazole; and 2, 2 ' -bLs ~m-c~anamidorllenyl ~ -5, 5 ~ ib~næi- :midaæole. .: ; ~
ny o~ e p~lymeri~ composil~ion~ a~ ~his invent:~on :: ~ ~ : : . . :: .
aan ~e blended with~ ~nox~anic filler~ and: ~ibers ox orsani~

~C16~

fi2:er~ to yi~ld reinforced ~ompo3ite~ havin~ either A lowex overall cost or enhanced phy~ical and electrie~l properties.
Additi~n of solutions of the N-cyanosul:Eonarnide.resin~
to a hydrocar~on r.on solvent y elds inely divid~d powders which can be given an electrostatic charge and applied as a coalesa-ble powder ~oating to heal:ed sur~aces.
Sin~e the polymeric precursors of this inventlon mel t within the temperatuxe range from 75C. to approximately 150C. .
they can be fabricated with t}le readily available commercial processing ~quipm~nt utilizin~ low cost toolirlg and ba~ging materials~ Good control can be maintained at the time o~
gelation at the ~ab~ication temperature so that both rapid or ~;low processi~ cycles can be ubtained~ This i5 achieved hy ~rarying the ratio of bis c~anamide to N-c~anosulfonamid~
csmpound - the higher this ratio the ~astex the pol~neric :
aomposil:ions~ thermoset. High ratios axe preferr~ fo~: sapid mc>lding cycles and low ratios ~xa pref~rred ~or tll~ sl~w~:~
vacuum ba~ and autoclave proce~;sin~ eyeles~ ~hus, the mel~ ~
~low in inches of a ~/1 molar ratio o ~, 4 '~m~th~lene ~i~ tN-ben~ene sulfonyl ph~n~l cyanamide) to 4 l 4 ' -methyl~ne bi~ plie~yl cyanan~ide WdS measur~d at two di~eren~ temperatures until the resin thermoset.
It was demonstrated that melt ~low for ~ rication can be maintalned for a lorlg ~s 20 minutas at 178~1, or 5 3;n~nute~ at 240~, with no threat o~ pramatur~ ~el.a~ion.
' ~ "' ' 68~

The ~a~xicated moldings, compo~ites t and coatiny~
can b~ g.iven post cures ~or ~everal hours in an oven a~
t~npera~ures up to 260C. in or~er to maximize their physical propexties. The ~ully cured res;ns are not attack~d 1~
organic solvent~, hav~ a low water absorption, low ~ielectric con.stant, do not support combustion and maintain ~ood mechanical prope~ ie~ up to ~60C. The oxidative stability of these resins in air at 260C. i5 ~ood and the mechanical properties are retained fox lo~ periods in air at elevated te~.peratuxes.
ApplicatiQns in circuit boards, poti:ing compounds, honeycomb panels, structural parts of airplanes ~7here weight ~a~ing is important, hot melt adhesivest and protective ~oatings axe ~isualized as important axeas o~ applicatiorl for these resins.

'. .
The ohje~t and advantages o~ this invention a~e further illustra~ed by the followin~ examples, )~u~ the ; ~particular material~ and amounts xeci~ed in these ex~mples as well as o~her conditions and ~etails~ ~hould n~t be construed à~ limi~ing thi~ invenkion.
.
~ , To a 3 liter 3-neck:ed flas~ equipped with a stirr~r, additional ~unnel, thermometer~and drying tube w~s char~ed 525 ml~ acetone~ 42g ~0~169 mol~ ~ o 4~4-methylen~ bisphenyl-' " , .
_ .

: .. :
, ~66~
, `', .
cyanamide (prepared according to known method~ rom 1 mole 4,4'-methylene bisphenylamine and Z moles cyanogen chloride) ~nd 37.6 g ~0.372 ~ole~) of erieth~l~mine. A ~olu-tion of $9.8g. ~0.33B moles) of benzene ~;ulfonyl chl~ride (99%) in 275 ml. of acetone ~as added drop~ise to the stirred solution while maintaining tl~e temp~ratur~. between 25-35OC.
The resultiny suspension wa~ stirred vigorously ~or o~e hour at room temperature. Tha hydrochloride salt was filtered o~
and washed with acetone unti.l the filter cake was entirely wat~r soluble. ~he filtxate was concentxated to 200 ml. by boilin~
of~ the excess acetone. To the concentra~e was added wi~h ætirring 1 liter of methanol to precipitate the product. The suspension was cooled to 0C. and stirred for one hour and then fil~ered.
~he filter cake was washed with a minimum o~ cold ~.
methan~l, air dried on the ~ilter and then dried at 60C, and .
: 1 mm. in a ~acuum oven for 1 hour to yield 68.4g ~76.5~ o~ -m~thylen~ bis(N,N'-benzene-sulfunyl phenyl cyanamide~, m.p. 123Q-125C. ~he C 61~.3~; ~ 3.82; N 10.59, ~ 12~.11;
~ound: C 61.29; H~4.08~ N 10.34; S 12.09.

:
~ a 100 ml. 3-necked flas~ equipped wi~h a stirrer, : , addition funn~l, thermome~er and drying :tube was char~ed

5.0~ (0.02 rnole~ of ~,4'-oxyblsphenyl cyanamid~@

~ ~ 6 ~ 4~

(prepared accordlng known methods from 1 mole 4,4-oxybl~-phenyLamine and 2 moles cyanogen chloride), 2.50 g ~0.022 mole) of triethylene diamine and 40 ml. of acetone. To the reaction mixture wa6 added dropwise a solution of 7.06g ~0.04 mole~ o benzene sulfonyl chloride in lS ml~ of acetone~
~he r~action mixtuxe was stirred for tw~ hours ancl tllen poured into 750 ml~ ~ rapidly stirred wat~r. The resultincJ precipi-tate was ~iltered off, washed with water and dried. The product was recrystallized from an acetone methanol mixture to gield 8,0 8 o~ pure 6,4'-oxy-bis-~N-benzene sul~onyl phenyl cyanamide~,m.p, 161-162C, Example_3 To a 2 liter 3-necked fla~k equlpped with a ~t~rrer, addltlon unnel, thenmometer and drying tu~e wa~ charged 12.4 g (0.09 mole) o~ meta phenylene bi~cyanamide (prepared ~ccording to known method~ from 1 mole m-phenylene diamlne ~nd 2 mole~ cyanogen chloride)~ 9.9 g (0.088 mole) of tri- -ethylene dia~ine and 475 ml. o~ acetone~ To th~ :
~eaction mixture wa~ added dropwise a solution o~ 3~.2g (0.176 mol~9 of benzene sulfonyl chlorld~ dissolved ~n 40 ml.
of acetone~ The reac~ion mixture was stirxed for 3.5 houxs and then poured into a rapidly stirred soLution ~ 10% aqueous :: ~cdium bicarbonate. ~he resultin~ precipitate was filtered o~i ~ashed wi~h wat~r and r~cry~tail~ze~ ~ro~ ~n ac~ton~-: ~ - 25 -~ 6 ~

methanol mi.xture to yield ~6.5~ ~77.1% y~ld) o~ pure N,N'-benzene sulfonyl~m-phenylene biscyanamide, m.p. 1~3~ C.

ExaMple ~
____ , To a 200 ml. 3-necked ~lask equipped with a stirrer, addition funnel, thermomet~r and d~ying tubc was char~ed 2,36 g (0.02 mole) of phenyl cyanamide (prepared according to known methods from 1 mole aniline and 1 mole ~anogen chlori-ride)~ 1.23 g (O.Qll mole) of triethylene diamine and 25 ml.
of acetone. A solution of 3.67 g (0.01 mole) ~f p,p'-oxy-bi~benzene sulfonyl chloride in 35 ml, of acetone w~s added to the reaction mixture. The resulting suspension was stirred at room te~perature for 5 hours and then poured into 750 ml.
of 10% NaHC03 601ution. The precipitated pr~duct was filtered off, washed with water and dried.

: ~he crude solid was d;~sol~ed in acekon~ and ~
tered. ~he f~ltrate was added to water and the r0~ulting .pre ipitake was collected, ~ashed ~lith water and dried i~ a vacuum oven to yield 4.~0g o~ p,p'-oxybis-(ben~ene sulfonyl N-phenyl cyanamid~l, m.p. 160-161C.

Example 5 -. Two grams:o~ ~,4'-rneth~le~ bi.s(N-benz~ne sul~ns~l --phenyl c~anamide) in a 20 ml. beaker was placed in a Gurin~
ov~n heate~ at a temperature o~ 250~C. ~he compQund mel~ed at 12~C. t~ form an amber liguid which witIIin an hour polymerized to form a rigid disc. rhis disc was pos~ cured

6- :
. ~ :

~ 8 ~

for one hour ak ~50C. followed by one hour at 300C. The di.sc was insoluble in boiling DMF and an in~ra ~ed spec~ral analysis sh~wed that the nitrile absorption peak at 4.5 microns had dis~ppeared during cur.ing. The t~lermo~ravimetric analysis curve showed ini~ial wei.ght loss in ai.r occurred between 350 and ~00C.
-, Example 6 ~ ity grams of 4,4'-methylene bis(N-benzene sul~onyl phenyl cyanamide) in a 100 ml. beaker wa~ pla~ed in a curing oven at lgOC. for four hours. During this period the molten compound became increasingly viscou~. It was then removed ~rom the oven and ound to have a melting point of 9SC. and to :~
be hi~hly ~oluble in polar solvents such as acetone, MEr~, T~F ~ .
and DMF.
A 50% solids solution in acekone was prepared rom this ~ompound and a torsional braid was satur~te~i with the ~301ution ~nd dried and h¢ated at 20 5 ~C . ~or 3 1/2 hours . The la~s t~ansit~on t~npexa~ure o~ th~ po]ymer wa~ 250C, Upc)n he3.ting.a aatu~at~d torsional braid to 30ûC. for on~ hour the ~la6s transition tempe~ature ;was ound to IJe above 3S0t:~.
A film was cast ~rom t}ie acetone solution and cured for 3 hours at 2ûOC. and one hour at 260C. The cured .
ilm was :isothermally aged at 260~C. and ~ound to retain 0.3~ o its weight aft~r 90 hours o~ aging.
~:

: ~ :

.
~ 27- :.

66~
Example 7 .
4,4'-oxy bis(N-benxene sulfonyl ph~nyl cyanamide)y 0.05g, was heated on a Fisher-Jollns m~ltin~ point ~lock.
The compound melted at 161-162C. anA the melt became increasin~J.y viscous a~ the tempexatu~re ~as raised. Within S minutes upon reachin~ a temperature of 245C. the melt solidiied ~o form a hard resin that was insoluble in hot ~MF.

Exam~le 8 ~ . - ...
Bis(N-~enzene su~on~i) m-phenylene dicyan~mide 0.0Sg, was heated on a ~isher~Johns melting point block. ~he compound melted at 1~3-144C. and the melt became noticeably viscous as the temperature increased to 210C. Within S
minutes upon reachi.ng a temperakure of 240Co the mel~ solid-i~ied.

xample 9 One gram o 4,4 ' -oxybis- ~benzene sul~onyl N~phenyl ayanamide) from Example 4 was pl~ced in an aluminum dish in ou~ng ~v~n he~t~ 15~ he ~omp~und melte~ orm a ~olox.le~ ui~ which c~os~link~d wlthin 1 1~2 hour~ to ~orm a hard thermoset resin.that was insoluble in hot ~MF and other solventsO ~ .

' . ~: ' , , .
.:
4'-meth~lene bis~N-benze~ne sul~ol~l pheny~
:: . cyanamide), 355~ ~0.~2 mole) and 4,4'-methylene bis phenyl : -28-: :, ~766~
cyanamide, ~3.5~ (0.33~ mole~ were cli.~isolvecl in 293g of methyl etllyl ketone. The solutic)n was re~luxed fo~ 1~ hollrs and the resultin~ 60% resin solids v~rnish was llsed ko saturate l~lE c31ass cloth (AllO0 fi.nish). ~`he ~lass cloth in a single pass 1:hrou~1l th~ larni.natin~ varn.iJh retained 35 ~y wei.(3ht resin and appro~:imately 2% residual methyl ethyl ketone. ~ twelve ply laminate was prepared ~y the vacuum ba~-autoclave process. The plies were mainta.i~ed und~x vacuum ~or one hour at 38 C . and ther~ heated at a rate o:f 1. . 7 ~C/
minute until a temperature o~ 163C. was hch.ieved w~lerein 90 psig pressure was applied. The temperature was incxeased to 17~C. and held for one hour at 90 psig pressuxe. The laminate o~ 30% resin content was then placed in an oven and post cured for six hours at 250~C. ~'he laminate had a ~lexural stren~th of 72,000 psi and a (1.4) short beam shear ~trength o~ 6000 psi.
- ' .
e 11 (Compari80n) 4,4'-methylene bisphenyl cyAnamide, 5.2gr was re~luxed in 12g o~ methyl ethyl ketone ~or 18 hours. An insolu~le ~ass formed in the bo~tom of the reaction ~lask.
It was ~iltered o~f and dried At 65C./l mm. pressure. This E~olymer was insolub~, did not ïnelt or soft~n when heated to 300"C. and could not be abricated into a structural part~

.
~ Example 12 .
4,4'-methylene bisphenyl cyanamidé, l9~9gy (O.Oû

~oles) and 4,~'~methylene bis(N-~enzene sul~onyl phenyl . .

,: :

Ei6~
cyanami.de), 42.3~, (O.OB mole) ~Yere dissolved in 62g, o methyl ketone and the solution was re~luxed for 3 hollrs.
The solution was t}len cooled to room temper~tllre ~nd poured into 700 ml. o~ rapidly stirred pentane~ ~ wl~ike, powdery res.in prec.ipika~ed which ~s filtered o~f alld dried. This xesin wei~hed 61cJ. Examination of th:is resin on the Di~eren~
tial Scanning calorimeter showed that it melted at ll4DC., showed pol~erization exotherms at 134~C. and ~4C. and ~ave a crosslinked resin wi~h a ylass transition temperature o~
327~
The resin.was blended with 50~ b~ volume of quartæ
powder and the mixture was heated ~or 15 min~tes at 130C.
to advance the resin. This molding powde.r wa.s compres~ion molded or one hour at 238C /3000 psi~ ~he resultin~ pl?.que had a room temperature ~lexural stren~h af ~/640 psi and a ~lexural ~trength at 232C of 5970 psi. The ~lexural modulus at room temperature was 1,133,000 psi.
.

4,4'-methylene bisph~nyl cyanamide~ 16~ tOo~63 mol~) and 4,4'-meth~lene bis(N-benzene sulf~nyL phenyl cyan~lide) 350g~ ~0.633 mole) were refluxed ~or 3 hours in q~O~ of methyl eth~l Xetone to prodilce a l~ninatin~ varnish con~ai.nin~ 60~ resin solids. ~lass cloth, l~lE (amino silane inish) was saturated with this varnish. T~e resultincJ prepre~
conkaining 6~ solvent was tacky and drapable. E.i~ht plies of prepxeg were heated at 130C. or one hour and then layed ~30 A , '.,.

~ o~
up in a nylon v~cuum bag and autoclave proceæs~d for one hour ~t 177C/90 psi. The resulting lamin~te containing 25%
resin had the following physical propertiesO

Flexural Str~ngth, psi ~7,500 Flexural Modulus, psi 3,490,000 Short Beam Shear Strengt}l tl~ psi 6990 Exam~le 1~
~ methylene bis~N~benzene sulfonyl phenyl cy~namide), 355g, (0.67~ mole) and 4,4'~methylene bisphen~l cyanamide, 83.5g (0.336 mole) wer~ refluxed ~or 16 hol-rs i.n 29~cJ of methyl ethyl ketone. Glass cloth (181E) was impregnated with this~ laminating varnish and the resulti~
prepreg containing 3S~4~ resin content wa~ vacuum bag-.
xutocl~ved at 177C/~0 p8i over ~ t~o hour p~r~d~ Th~ la~
nate was then plac~d in an oven and po~t cured for eight hours at 2~0C. The resulting laminate cvntaining 30% resin had the ~ollowing physlcal properties. :

; ~ . Flexural 8trength, psl : 71/80~
Flexural Modulus, psi 2,840tO0~ :
. Short Be~m She~r Strength ~ ), psi 5887 . .
:................................ .
: ~ ~ m ~
~ he lamina~in~ varnish prepared in Exam~le 14 w~s used to prep~re a lBlE glass cloth prepreg that was heated ~ox 30 minutes at 80C. to xemove the solverlt.. I~he dry prepreg :
~ 31-.
. .

~ 6~
was then layed up in 4 plies in a press and laminated a~
177C/500 psi ~or one hour. The laminate was removed from the press and post cured in an oven at 235C. for three hours.This laminat~ contai.n~d 30~ resin con~ent and had ~he following physical properties: :
Flexural Str~n~tl~, psi ~oom Temp. 64,~pO
450Fo SS~100 Flexural ~lod~lus, psi Room T~mp. 3,190,000 450F~ . 3,070,000 Example 16 -.
, A 181E glass cloth laminate cont.ain~ng ~1,3% resin was pxepared according to the pr~cedure of Example 15. Test bars ~or flexural strengt}l tests were cut from thii~ laminat~ -and were placed in a forced draft air oven maintained at a ~emperature o 260~C~ The maln~enan~a of 1e~ral 4t~ng~h of thig l~minate during oxldative~expo~ure ~t 260QC wa observed a~ follows:

ours at 500F.

10~ ` 77 1gO
250~ 59,000 500 ~ ~9,~00 4,4'-me~hylene bis~N-benæene sul~on~l phenyl ~ ~ 6 ~ ~

c~anamide3, 460g, to.n7 mole) and 4,4'-methylene bisphenyl eyanamide, 460g, ~1.85 moles) were dissolved in 1380g of acetone and the solution was refluxed for several minutes.
The hot solution was then pouxed into 15 l:Lters of rap~dly stirred low boiling p~troleum ether. A prepolymer precip:itat~d from the petroleum ether as a ~i~lely divided powd~r. T~e prepol~mer was dri~d overnight under vacuum at room tem,pe~a-ture. The dried prepol~mer weighed ~13g 199.2~ yield).
~ Dierential Thermal Analysis determin~tion on sample o~ this prepol~mer showed that it melted a~ DC. and sho~ed a polymerization exoth~rm that peaked at 133C. A
portion of the prepolymer was compression molded at 130C./
S00 psi for 15 minutes to yield a hard dis~. Thi.s disc was post cured in an oven at 260C for several hour6 to complete the crosslinking reaction and optimize mechanical strength propertles.

...
4,~'-m~lthylene bis(N-benzene sulfonyl phenyl cyanamide), 211.4g, (0,400 mole) and ~ methylene bisphenyl ~y~namide, 99.5q, (0.400 mole~ were dissolved in 257g of methyl e~hyl ketone and the solution ~as heated at reflux for one hour. This laminating varnish was used to saturate a woven abric oomposed of polyamide filaments~ i.e, PRD-49-111.
~h~ aturated ~abric ~7as heAted in an oven at 90~C. ~or 2S
~inutes and then at 1~0Co for 10 minu~es to remov~ sol~ent r~idu~s and 53-~tag~ th~ ra~in. . Tan pli~ of th~ prepreg ~ 3 .. .

~ ~ 6 ~ ~
were compres~ion molded at lOO0 psi by Elrst heating for 1.5 hours at 177C fol.lowed by l.O hour at: 204C. The laminate was removed Erom the press and placed in an OVell to post cure at 232nC or 5 hours. The resulting laminate llad the following physlcal properties:

Wei~ht percent resirl content 50.1 xural ~trenc3th, psi . 42,000 ~lexural modul.us~ p5i 3~3~tO00 Sllo.rt beam shear str~ngth (1:4), psi 3750 EY~am~e 1 9 4,4'-methyl~ne bis~-benzene sul~ol~yl phenyl c~anamide), 230g, (0.~35 mole) and 4,4'-m~tllyl~ne bisphen~l c~anamide, ~30g ~0.925 lnole) were dissolved in a mixture o lSOg of me~hanol and 50~3 o ace~one and the solution ~as heated at the reflw~ temperature ~or 3 hours. I'lle acetone : WA5 the~ x~mov~d from this lamlnatin~ vaxnish by ~istilling off the 8~-12 acetone-methanol azeotrope ~B.P. 55.7C.) whii~ ~dding additional m~thanol to the varnish to maintain a aons~ant volume. ~he res~l~in~ methanol based varnish of

7~ resill content was us~d t~ saturate 1528 glass cloth (Volan A fini~h). The prepre~ containing by weight ~6.~ o~ th~
varnlsh wa~ B~taged for 15 minutes at ~07C.
EL8ht plies of the prepreg were lam~nated to l ounce : TC copper ~oll for 30 minutes at 177C/SOO psi. The laminate :: : : :.

~ 34 : :

6~;84(~

was pos~ curea in an oven ~t 235~C. fcr 24 hours. The copper foil had ~ peel strength of 7 lbs. per-inlch o width as laminated. The laminate had the following electrical prop~r-ties before and after water immersion.

Ater 24 hours immersi~n at Before Xmmersion 25C.

D~electric Cons ant at lMHz;
- (2~C) ~.~5 ~.92 Dissipation ~actor at lM}lz;
(~5C) O. 01~ 0 . 011 ExamPle ?
.
N-benzene sulfonyl phenyl cyan~mide 25. 8g, ~O.lO mole~ -and 4,4l methylene bis phellyl eyanamide, 49.7g, ~0~0 mole~
were dissolved in 72g of methyl ethyl keton~ and ~he solu~ior~
was heated at reflux for 30 minutes. The resultiny 1amina'cin~
vaxnish of 55% resin solid~ cvncentration was used to satura~e a woven ~abric compased of polyamide filam~nt, i.e., PRD-~9-ha prepreg was ~eated at 90C, for 0~5 hour to r~move ~olvent residues and advance the resinO Seven plies oprepreg were~laminated in a press at 1000 psi which whs heated for 90 minutes at 300F. followed by 120 minutes a~ 400~. The lam.in~te containin~ 51.~Q resin solids was post cured ~or 5 hours at ~50F. The post cured laminate had a short beam ...
hear ~trength ~1:4) of 2,240 psi and a ~lexural modulus of 3,~20,00~ psi.

~ - 35 _ .

~ ~ \

3~
A portion of the laminating varnish from Example 20 was used to saturate a torsional braid which ~as used in the Torsional Braid Apparatus to determine the glass transi-tion tempe~ature of the polymer at several heating cycles.
When the braid was heated for 40 minutes at 178C. the glass transition of the polymer was 250C. Further heating for 75 minutes at 250C. oaused the glass transition tempera-ture of the polymer to increase to 275C7 Precipitation of a portion of the laminating varnish of Example 2~ by adding the solution to a rapidly stirred non~solvent, pentane9 ga~e a quantitative recovery of the solid resin which softened at 60C. and ga~a a clear melt at 110C. A sample of the solid resin was cured at 250C~ for 90 minutes and submitted for thermogravimetric analysis. This resin when heated at 5C./minute in air lost 4% of its weight at 350C. and 8b ~f its weight at 400~C. -:
: ~

p-amino benzene sulfonyl N-phenyl cyanamide, 10~9g ; (0.04 mole) and 3~3~p4~4 -benzophenone tetracarboxylic dlanhydridep 6~44gg~(0~02 mole) were dissol~ed in 90 ml. of DMF. The solution was heated at reflux for 3 hours. The :
solution was ehen cooied to room temperature and poured slowly into 600 ml. of rapidly stirred wa~er. The finely dividecl precipitat~ was filtered off ~ashed with water and dried alt : : : ' : .
: : ~ ' - :

~0~6~

185C~ 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 169C. and showed a polymerization e~otherm co~mencing beeween 180-190C.
A torsional braid curing study showed that this polymer had a glass transition temperature of 310C. after a two hour heating period at 300C.
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 250C. for one hour to cure the polymer. T~e cured fllm was oxidatively aged by heating in a forced draft air oYen at SOO~F. After 514 hours o aging the film re~ained 90O3% of its original weight~ ~-.
E~ample 23 To a liter 3-necked flask equipped with a stirrer, additioF funnel~ thermometer~ and drying ~ube was charged 93.1g (l.0 mole) of aniline, lllg (1.1 moles) of triethylene diamine and 250 ml. of tetrahydrofuran. To this reaction ,, . :
~ ~ixture was added dropwise a solution of 176.6g ~1 mole) of ~ . ::
ben~enesulfonyl chloride in 300 mlO of ~e~rahydrofuran. The ::
reaction mixture was stirred at room temperature for ~15 hours -and ~as then filtered~ ~To the filtrate was added lllg of triethylene dlamine and this solution was added dropwise to a : : : .:.

~ :.
: ~
.
~37-~: ' ~6~`~0 solution of 87g (1~41 moles) of cyanogen chiLoride in 100 ml.
of THF which was maintained at -5C. with cooling. Afte~
this addition was complete the stirred reaction mixture w~s allowed to return to room temperature over a 16 1~2 hour period. The reaction mixture was iltered and the filament was added to wa~er to precipitate the product. The product was recrystallized from aqueous methanol to yield 218g (84.7%) of N~benzene sulfonyl phenyl cyanamide, m.p. 65-66C.

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 e~hyl ketone and the solution W8S hea~ed at reflux for one hour. The resulting laminating ~arnish ~as used to prepare a prepreg containing polyamide woven fabric PRD-49-111. The prepreg was dried at room temperature under ~acuum and eight plies were press lamina~ed at 14~VC for 10 minutes ~ollowed by one hour at 204C. This laminate containing 33~4~/O
by weight resi~ was post cured for 5 hours at 232C. The post cured laminate had a short beam interlaminar shear strength (4:1) of 2000 psi.

. . .
: ~e~ "
4,4'-methylene bis ~N-benzene sulfonyl phenyl cyanamide), lO.lg (O.Ol~l mole~ and 494~-methylene bis phenyl cyanamide, 30~0g (0.121 mole) were dissolved in 30g of acetone . ~

: : :

~6~84~ -and the solution was refluxed for 10 minutes. The hot solution was poured into one liter of rapidly stirred low boiling petroleum ~ther to precipitate the prepolymer as a finely divided powder. The dried powder when heated melted at 120C. and within a few seconds ther~oset at this tempcra-ture. A differential thermal analysis showed that th~ poly-merization exotherm peaked between 135 to 145C. and could not be observed above 213C~

~ .
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 l~lg o dimethyl fonmamide. The solution was heated at reflux for 16 hours. A portiDn of this prepolymer solution was used to coat a torsional braid and ~he glass . :.
transition temperature, Tg~ was determined in the torsional :
Braid Apparatus. The Tg was 290C. after heating the braid for 2 hours at 200C. followed by one hour at 260C. -A portion of the prepolymer solution was used to cast a film which was heated for one hour at 260C. to cure the film. The film was isothermally aged in a forced draft air oven ~eated at 260C. After 1~14 hours of aging at 260C
he ilm retained 66~3% of its original weigh~.

:.' ~', ~ . ' :

~' ; -' : `

3L~66~

Exa~ple 27 p,p'-oxybis-(benzene sulfonyl N-phenyl cyanamide) from Example 4 was heated in a ~iffe~entiaL Scanning Calo~i-meter. A melting point was obsexved at 164C.~ the onset of polymerlzation at 210C.7 and a polymerL~ation exothe~m peak a~ 265C~ ~hen heated in air in a Thermal Gravi~etric Analysis Apparatus the cured resin retained 90% of its original weight at 400C.

Exam~le 28 ;~
p,p9-oxybis-(ben~ene sulfonyl N-phe~yl 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 solu~ion was heated at reflux for 16 hours.
The prepolymer was precipitated as a fi~e powder by pouring this 501ut~0n ~nto 500 ml. of rapldly agitated hexane. The dried prepolymer melted at 120C. and ~hermose~ within 15 minutes aEter being held a~ a temperature of 215C. After heating this powder at 300C. the glass transition temperature was 290C.
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pgp'-oxybis-(benzene sulfonyl N-phe~yl cya~amlde, `7A98~ (0~015 mole~ and 4~4'-oxybis phenyl cyanamide, 1.89g (o.0075 mole) were diss31ved in lOg o methyl ethyl ketone and the solu~ion was heate~ at reflux for 16 hour~ This solution was used to case a film which was cured for one hour at 260C. The film ~as isother~ally aged in a fo~ced : : . .

, ~40-lC~66~

draft air oven at 260C and was fo~rld to retain 68% of its original weight after 846 hours of aging in air at this temperature.

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Twenty five grams of N,N'-metha~e sulfonyl-1,6~ .
hexamethylene biscyanam~de in a 50 ml. beaker is placed ~::
in a curing oven at 200C. The liquid becomes increasingly : .-viscous and finally thermDsets within 90 minutes. The :. :
resulting disc is insoluble in boiling DMFo . '.''' ',, Examele 31 '.: . :, N,N'-methane sulfonyl-lg6-hexamethylen~ biscyanamide, .:-3.22g ~0.01 mole) and 3c32 g (0.02 mole) of 1,6-hexame~hylene ::
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biscyanamide are stirred together in the mslt at 90C. for . .. ~.
112 hour to yield a viscous syrup. Ihis syrup is then placed in a curing oven at 177C. for 1 hour. A transparen~, cross~
: ~ linked molding is produced that swells only slightlg in boiling DMF.
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2,5-bis(meta cyanamidophenyl)-1,3,5-oxadiazole, : ~: 3.0g~ ~0.01 mole) and 3~22 g5 (0.01 mole) of the imide pre-polym~r of Example 22 are dissolved in 50 ml of DNF solution and the solùtion is used to ~oat a torsional braid.
: torslonal brai~d curlng study shows ehat this polymer has a glass transition te~pera~ure of 250C~ after a 3 hour cure ~: . :' ' ' ''. ~' .
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at 200C. and a glass transition temperature of 315C. after a two hour heating period at 300C. `

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4,4'-methylene bisphenyl cyanamide~ 248g~ (1.0 mole) and 4,4'-methylene bis(N-be~zene sulfonyl phenyl cyanamide~
248g, (0.47 mole) are dissol~ed in 500 ml~ of acetone and the acetone solution is refluxed for S minutes. The acetone -solution is then poured into 6 liters of rapidly stirred petroleum ether to preclpitate a white~ powdery resin which is filtered off and dried under vacuum at room temperature.
The dried resin is heated for 10 minu~es at 90CO and then placed in a mold and compression molded at 149C/3000 psi or 1 hour. The yellow, transparent plaque is removed from the mold and post cured at 260C for 2 hours. A flexural bar from this post cured resin has a flexural strength of 16,300 .
ysi and flexural ~odulus of 616~000 psi~
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Claims (13)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A polymer derived by addition homo-polymerization of a bis-N-cyanosulfonamide of formula I or II:

(I) or (II) wherein R is a divalent aromatic, aliphatic, cycloaliphatic or heterocyclic radical, and each R' is independently a monovalent aromatic, aliphatic, cycloaliphatic or hererocyclic radical; by addition co-polymerization with one mole of a bis-N-cyanosulfonamide of formula I or II with 1 to 10 moles of a bis-cyanamide having the formula VII:
NC-NH-R1-NH-CN (VII) wherein R1 is an aromatic, aliphatic, cycloaliphatic or heterocyclic radical;
or by addition polymerization of an N-cyanosulfonamide compound of the form-ula:

wherein R' is as defined above, with a bis cyanamide of formula VII defined above.

2. A polymer derived by addition homo-polymerization of a bis-N-cyanosulfonamide of formula I or II, as defined in claim 1 or by addition co-polymerization of 1 mole of a bis-N-cyanosulfonamide of formula I or II with 1 to 10 moles of a bis-cyanamide having the formula VII as defined in claim 1.

3. The polymer of claim 2 wherein R is a divalent aromatic radical selected from the group consisting of phenylene, bisphenylene, naphthylene and the foregoing radicals linked by divalent groups selected from the group consisting of oxa, carbonyl, lower alkylene, lower alkylidene, sulfonyl, thia, arylimino, amido and imido.

4. A laminate comprising a fibrous substrate impregnated with a polymer of claim 1.

5. A laminate according to claim 4 wherein the fibrous substrate comprises fibres of glass, graphite, boron, or aromatic polyamide.

6. A polymer derived by the addition polymerization of an N-cyano-sulfonamide compound of the formula:

wherein each R' is independently a monovalent aromatic, aliphatic, cycloaliphatic or heterocyclic radical, with a bis cyanamide of the formula VII defined in claim 1.

7. A polymer of claim 6 wherein R is an aromatic radical selected from the group consisting of phenylene, bisphenylene, naphthylene and the fore-going radicals linked by divalent groups selected from the group consisting of oxa, carbonyl, lower alkylene, lower alkylidene, sulfonyl, thia, arylimino, amido and imido.

8. A laminate comprising a fibrous substrate impregnated with a polymer of claim 6.

9. A laminate according to claim 8 wherein the fibrous substrate comprises fibres of glass, graphite, boron, or aromatic polyamide.

10. A molded part comprising a polymer according to claim 2.

11. A molded part comprising a polymer according to claim 5.

12. A east film or coating comprising a polymer according to claim 2.

13. A east film or coating comprising polymer according to claim 6.