CA1092135A - Photocurable imidizable polyene-polythiol compositions - Google Patents

Photocurable imidizable polyene-polythiol compositions

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Publication number
CA1092135A
CA1092135A CA293,767A CA293767A CA1092135A CA 1092135 A CA1092135 A CA 1092135A CA 293767 A CA293767 A CA 293767A CA 1092135 A CA1092135 A CA 1092135A
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Prior art keywords
polyene
carbon atoms
aromatic residue
groups
attached
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CA293,767A
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French (fr)
Inventor
Eckart Mathias
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WR Grace and Co
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WR Grace and Co
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Priority claimed from US05/753,350 external-priority patent/US4103016A/en
Priority claimed from US05/830,225 external-priority patent/US4117196A/en
Priority claimed from US05/851,680 external-priority patent/US4132812A/en
Application filed by WR Grace and Co filed Critical WR Grace and Co
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Publication of CA1092135A publication Critical patent/CA1092135A/en
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Abstract

Abstract of the Disclosure This invention relates to polyenes containing at least two ethylenically unsaturated bonds per molecule formed by reacting in substantially stoichiometric amounts, (1) a primary diamine, (2) a member of the group consisting of a benzenoid-containing dianhydride, acid anhydride and anhydride acid halide and (3) an ethylenically unsaturated alcohol. The thus formed amide-acid polyene either per se or after being cured in combination with a polythiol in the presence of a free radical generator will, upon heating, imidize.

Description

3L~5i This invention relates to a polyene composition, procedures for making same and cured products resulting therefrom. More particularly, this invention relates to an amide-acid polyene, a method of preparing same, as well as curing the polyene with a polythiol in the presence of a free radical generator to solid, cross-linked, solvent-insoluble materials, which on heating will imidize resulting in improved high temperature properties.
I~ is known that polyenes are curable by polythiols in the presence of free radical generators such as actinic radiation ] to solid polythioether-c~ntaining resinous or elastomeric products.
See U. S. 3,661,744. However, high temperature characteristics of the cured product are somewhat lacking due to the aliphatic nature of the polyenes employed. For example, in the wire coat-ing ield present day commercially available polyenes because of their aliphatic structure fail the NEMA specified heat shock and cut-through tests at the upper temperature limits at which these tests are run, thereby negating their operability for this end use. Thus, a coating having good high temperature properties after curing is a desirous element.
In accordance with this ~nvention, An amide-acid polyene of the formula:

O ~ / O O \ O O
-(HOC)k C-NH-R / ~ 1 > \~

(Y~-~A~-OC COHHOC COH / HOC Co-~At-~Y) m ,. \ " "
O ~ \O O / O O
~ / P
- 2 -wherein ~ denotes isomerism, R is a divalent organic moiety remaining after a primary diamine has reacted to form.amide linka~es;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-o o(CH2)d-CR"=CH2, -COCH2CR"=CH2 and -O-~-CR"=CH2 R" is hydrogen or methyl; k and h are O or l; m and d are 1 to 10; and p is O to lO is obtained by reacting in sub-stantially stoichiometric amounts (1) a primary diamine, ~2) a member of the gxoup consisting of a benzoid-containing dian hydride, acid anhydride and anhydride acid halide and (3) an ethylenically unsaturated alcohol.
The thus formed polyene, on heating can be imidized per se to form a polyene with improved high temperature properties of the formula:
O ~ /0 0 \ o O
.(HOC ~ / C ¦ C\ / C\ /C\ ~(COH)h ~ R ~ N-RtN / R' N-R N R ~ + (2~2p)H20 (Y ~ A)-OC C \ C C C CO-(A) ~Y)m O o \O O ~ O O

whe~ein R is a di~alent organic moiety remaining after the di-secondary amide has reacted with adjacent carboxylic aci.d groups to form imide linkages and R', R"l A,Y, k, h, m, d and p are as hereinbefore set forth. Acrylic terminated polyenes, whether imidized or of the amide-acide type, are photopolymerizable per se by U,V. light, preferably in the s presence of a photoinltiator as will be shown by an example hereinafter, Additionally, any of the polyenes herein in combination with a polythiol on exposure to a free radical generator forms a cured polythioether. Imidization which results in improved high temperature properties can be carried out prior concurrent with or subsequent to radiation curing. This polyene and polythiol mixture is a highly reactive composition which is capable of being photocured when exposed to actinic radiation in the presence of a U.V.
sensitizer to insoluble polythioether-con-taining materials.
Additionally, on following the photocure, the cured poly-thioether can be heated preferably in the range 50-250C to imidize the amide-acid thereby irnproving the high temperature properties of the cured material.
Further, in accord with the instant invention, there are provided me-thods of preparing an amide-acid polyene which comprises reacting in substantially stoichiometric amounts (1) at least one primary diamine having the structural formula: H2N-R-NH2 wherein R is a divalent organic moie~y containing at least 2 carbon atoms, the two amino groups of sald diamine each attached to separate carbon atoms of said divalent organic moiety with (2) at least one anhydride-containing member of the group consisting of O O

~C~ ~.C, \C/ \C/, O O

O
/ C\
EIOC-R' /O
O C

() /c\
XC-R \ /O

wherein R' is an aromatic residue attached to at least
3 carboxyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue and X is a halide radical and (3) an ethylenically unsaturated alcohol of the formula: IIO-~A-~Y)m . wherein A is an alkylene group having from 1 to lO carbon atoms;

Y is a member of the group consisting of -CR"=CH2, O O
( 2)d 2' -COC112CR"=CH2 and -O-C-CR"=CH2;
R" is hydroyen or methyl; and m and d are l -to lO.
If desired, when using a dianhydride, a polyamide acid structure containing up tolO repeating-uni-ts can be obtained by reacting sufficient diamine with the dianhydride prior -to reacting the thus formed polymer with the ethylenically unsaturated alcohol.
The procedure for forming the amide-acid from the primary diamine and the anhydride-containing member is well known and conventional. That is, the amide-acid is prepared by mixing at least one primary diamine with at least one anhydride-containing member preferably in an inert organic solvent for at least the product and preferably one reactant under essentially anhydrous conditions for a time preferably of at least 2 minutes and at a temperature not hlgher than 1~0C to provide at least 70% of the corresponding amide-acid. It should be understood that it is not necessary that the resultant prod~ct be totally amide-acid and tllat it is dcsirable that the product contain not morc than 30g~ by wcight of imide, the remainder being the amide-acid. Thus, while the aforementioned conventional process for preparing amide-acid should be conducted pref~rably below 50C
to p-ovide substantially 1006 by wei~ht of the amide-acids, higher temperatures will still provide a product containiny subs~antial amounts of the amide-acid.

In practicing the instant invention all synthesis reactions are carried out in the presence of an iner-t gas (e.g., nitrogen, argon or helium) blanket. Additionally, although all the synthesis reactions can be carried out in the presence of a solvent some of -the reactions can also be carried out in the absence of solvents. The solvents useful for synthesizing the polyenes of the instant invention are organic solvents which do not chemically react with either of the reactants (the amines or the anhydrides) or the final amide-acid product. Additionally, besides being inert to the reaction system and being a solvent for the product, the organic solvent should be a solvent for at least one of the reactants and, preferably, for both of the reactants. The normally liquid organlc solvents of the N,N-dialkylcarboxyl-amide class are useful as solvents in the process of the instant invention. Preferred solvents are low molecular weight members of this class, particularly N,N-dimethyl-formamide and NjN dimethylacetamide. The solvents are readily removed from the amide-acid by evaporation, displace-ment or diffusion. Other useful solvents include, but are not limited to, N,N-dlethylformamide; N,N-diethylacetamide;
N,N-dimethylmethoxyacetamide; N-methyl captolactam; dimethyl-sulfoxide; N-methyl-2-pyrrolidone; tetramethyl urea; pyridine;
dïmethylsulfone; hexamethylphosphoramide; tetramethylene-sulfone; formamide; N-methylformamide; N-acetal-2-pyrrolidone;
and the like. The solvents can be used alone, in a combination of the aforesaid solvents or in combination with poorer solvents such as toluene, benzonitrile, dioxane, butyrol-actone , xylenes, chlorobenzenes and cyclohexane.

2~
.

More specifically, the reaction conditions for forming the various polyenes dependlng on which anhydride-con-taining member is employed are as follows.
To form the dianhydride amide-acid from a dianhydridc and a diamine, each reac-tant is put into solution prior to mixing together. The admixture during reaction is maintained at a temperature in the range from 25~ up to but preferably below 100C. Preferably, the diamin~ is added to the dianhydride but the reaction is operable if the sequence is reversed. In either sequence, the reactants are added to each other slowly to restrict the formation of very high molecular weight polymers. The mole ratio of the dianhydride to the diamine is 2:1 for monomeric amide-acids. A mole ratio of 1:1 can be employed should polyamide~acid be desired. Any mole ratio ~etween these ratios is operational. The amide-acid polyene is formed by addiny an unsaturated alcohol which can be, but need not be, in solution prior to its addition.
The reaction is carried out at temperatures between room temperature and below 100C, preferably 60-80C for periods ranging from 2 minutes to 3 hours. The resultant product is worked up by repeatedly washing the reaction mlxture with a large excess of water while vigourously agitating the admixture. The wa-ter layer is discarded and the resulting viscous gum is then dried by dissolving it in an alcohol/benzene azeotropic mixture and azeotroping off the water. The azeo-tropic solvent used alone or as a mixture of solvents can be of any kind as long as it dissolves the gum and has an azeotropic boiling point below about 100C.

. _ ........................................... .
.

,5 To form a dicarboxylic amide-acid from a diamine and an acid anhydride, the reaction can be carried out in the presence or absence of the aforementioned solvent. If no solvent is used, the reactants are mi~ed in the flask and the flask is heated until the reactants react vigorously at a temperature ranging from 25C up to 180C, preferably 150-175C. If a solvent is employed, the diamine solution is preferably added to the anhydride but the reverse of the sequence is operable. The temperature range of the reaction when a solvent is employed is usually between ~
25C to 100C~ The dicarboxylic acid amide-acid solution is Yigorously washed with water and the resulting viscous gum is then dried by dissolving it into an alcohol~benzene azeotropic mixture and azeotroping-off the water. To form the~ ami~de-acid polyene ~rom this amide-acid, a co~ventional esterific~tion reaction ~s performed. The unsaturated alcohol can act as a solvent per se or additional solvents such as benzene, toluene, isoprp~l alcohol~benzene can be employe~ ~ catalyst such as those well ~nown~ i~ the esteri-fication art, e.g., p-toluene sulfonic acid, methane sulfonic acid, sulfuric acid, phosphoric acid, hydrochloric acid, BF3-etherate, camphor sulfonic acid, organic tin compounds, and the like, may be employed. The solvent and/or unreacted alcohol is stripped off to recover the amide-acid polyene product. With these reactants it is desirable and oftentimes preferable to esterify the acid anhydride with the unsaturated alcohol firstly in the absence of a solvent at a temperature in the range of 100-255C and thereafter react the anhydride groups with the diamine also in the,absence of a solvent at a temperature in the range oE 60-190C.

g ^~ 2~

When the anhydride-containing member is an anhydride acid halide, it is preferable to form the ester anhydride from the reaction of the anhydride acid halide and the unsaturated alcohol prior to reaction with the diamine.
The ester anhydride is formed by putting preferably the anhydride acid halide in solution prior to admixing same with the unsaturated alcohol. The reactants are added in a mole ratio of approximately 1:1. The unsaturated alcohol is added slowly to the anhydride acid halide while the reaction solution is sparged vigorously with a dry inert gas (e.g., nitrogen, argon or helium) to remove the hydrogen halide. The reaction is carried out at slightly below, preferably 10C below, refluxing temperature. After the addition of all the alcohol is complete, the reaction is continued until all the hydrogen halide has been removed.
The diamine with or without a solvent, is added to the ester anhydride (at a diamine to anhydride ratio of 1:2) while maintaining the reaction mixture in a range between 25 to about lOO~C, preferably between 50 and 80C, until the IR absorption bands of the anhydride carbonyl groups disappear.
The amide-acid polyene produc-t is recovered by distilling off the solvent at low pressure using a temperature of pceferably not greater than 100C.
~ The diamines operable in the instant invention are primary diamines having the structural formula H2N-R-NH2 wherein R is a divalent organic moiety dcrived from or containing an aromatic, ali~hatic, cycloalil~hatic, heterocyclic or a combination of aromatic and aliphatic groups containing at least 2 carbon atoms, the 2 amino groups of said diamine are each attached to separate carbon atoms of said divalent organic moiety.

Diamines which are operable in the instant invention include, but are not limited to, 4,4'-diamino-dipllenyl methane; benz.idine; 3,3'-dichlorobenzidine; 4,4'-cliamino-diphenyl sulfide; 3,3'-diamino-diphenyl sulfone; ~,4'-diamino-diphenyl sulfone; 4,4'-diamino-diphenyl ether;
30 1,5-diamino naphthalene; meta-phenylenediamine; 4,4'-diamino-diphenyl propane;
para-phenylene-diamine; 3,3'-dimethyl-4,4'-biphenyl diamine; 3,3'-dimethoxy benzidine; 2,4-bis(beta-amino-t~
butyl)toluene; bis-(para-beta-amino-t-butyl-phenyl) ether; bis-(para-beta-methyl-del-ta-amino-pentyl)l~enzene;
bis-para-(l,l-dimethyl-S-amino-pentyl)benzene; l-isopropyl-2,4-metaphenylene diamine; m-xylylene diamine; p-xylylene diamine; ~li(para-amino-cyclohexyl) methane; hexamethylene diamine; hepta-methylene diamine; octa-methylene diamine, nonamethylene diamine, decamethylene diamine;
3-aminomethyl-3,5,5-trlmethylcyclohexyl amine; 3-methylheptam-ethylene diamine; 4,4-dimethylheptamethylene diamine; 2,11-diaminododecane; 1,2-bis-(3-aminopropoxy ethanc);
2,2-dimethyl propylene diamine; 3-methoxy-hexamethylene diamine; 2,5-dimethylhexamethylene diamine; 2,5-dimethyl-heptamethylenediamine; 3-methylheptamethylene diamine;
5-methylnonamethylenediamine; 2,17-diamino-eicosadecane;
1.,4-diamino-cyclohexane; l,10-diamino-1,10-dimethyl-decane; 1,12-diamino-octadecane; 2,4 toluene diamine;
2,6 toluene diamine; 1,3-bis(aminomethyl)cyclohexane;
N,N'-bis (3-aminopropyl) dim~thyl hydantoin; 112N

~I N(C~12) 3(Cll2)2o(cH2) 3NH2; E12N(C112) 3 2 3 2 2 (C112) 3N(C113) (CH2) 3NH2 and mixtu~res thereof.
The anhydride-containing member useful for forming polyenes in the instant invention is a men~er of the group consisting of: .

3s o o ll ll O / \ R~ \ O
C \C
.. ..
O ,0 O

~OC-R~ \ O
O \C/
... _ . ... , . . O
,' O
~ ~ r.~ . , 0 /C\
. : - XC-R \ jO
~ o C
. .
.' ' O
wherein R' is an aromatlc residue a~tached to at least 3 carboxyl groups at least two of which yroups are attached to adjacent carbon atoms on the aromatic resldue and X is a halide radical- ~nhydride-containing members ... . . .. . . _ . _ . . .. . . .. . .. .. .. . .. .
operable in the instant invention to form amide-acid polyenes include, but are not limited to, pyromelli-tic dianhydride; 2,3,6,7-naphthalene tetracarboxylic dianhydride;
3,3',4,4'-diphenyl tetracarboxylic dianhydride; 1,2,5,6-naphthalene tetracarboxylic dianhydride; 2,2',3,3'-diphenyl tetracarboxylic dianhydridei 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride; bis(3,4-dicarboxyphenyl)sulfone dianhydride; perylene 3,4,9,10-tetracarboxylic acid dianhydride; bis(3,4-dicarboxyphenyl)ether dianhydride;
,,, ",,,,, , , .. . ~ .. _ .. _ .. ...... . . . .. . . . .. ... . . . . .. .. . . .... . ..... .
, . .
~-. bis!(3,4-dicarboxyphenyl) sulfone dianhydride, ethylene ,. tetracarboxylic acid dianhydride; trimelli-tic anhydride ~ acid halide, e. g. trimellitic anhydride acid chloride ;, . benzophenone~etracarboxylic anhydride; trimellitic - . 30 anhydride and the like.;

,~ .
;~ . .

,, ~ , ,.

.

~ 38~

Lthylenically unsa-tura-ted alcohols suitable ~or use in the instant invention to form amide-acid polyenes are those of -the formula: HO-~A-~Y)m wherein A is an alkylelle cJroup having ~rom 1 to 10 carbon atoms;

Y is a men~er of tlle group consistiny of -CR"=CH2, O O
O-(CIE ) -CR"=C~ , -COC112CR =C112;and -O-C-CR"=CH2;

R" is hydrogen or methyl; and m and d and 1 to 10.
10Illustrative of the operable reactive unsaturated alcohols which react with the amide-acid to give the desired polyene include, bu-t are not limited to, allyl and methallyl alcohol, crotyl alcohol,~-undecylenyl alcohol, 2 vinyloxyethanol, vinylhydroxyethyl sulfide, propargyl alcohol, l-allylcyclopentanol, 2-methyl 3-butene-- 2-ol, dially malate and hydroxyl substituted organic ester of acrylic acid or methacrylic acid including, but not limited to, 2-hydroxyethyl acrylate, 1 (or 2) hydroxy propyl acrylate, 1 (or 2) hydroxybutyl acrylate and the corresponding methacrylates thereof. Reactive unsa'~urated derivatives of polyhydric alcohols such as glycols, triols, -tetraols, etc., are also suitable. Representative examples include trimethylolpropane or trimethylolethane diallyl ethers, pentaerythritol triallyl ether and the like.
Mixtures of various reactive unsaturated alcohols are operable as well. Additionally, a suitable ethylenically unsaturated alcohol can be prepared by reacting one mole of a polyvinyl alcohol containing 10 hydroxyl groups with 9 moles of allylchloride to obtain an alcohol having 9 ethylenically unsaturated sites.

2~1~5 - The aimide-acid L~olycnes of thc installt inv~ntion - can be imidized per se by heatiny the polyene in the range 50-250C. Ileating periods at thci low ~nd of the tempera~ure range are necessarily of longer dul-ation than ~3~ those at ~he high end of the range to affect imidization.
The polyenes of the instant invention can also be imidized and cured in combination with a polythiol in the presence of a free radical generating agent.
In some instances the polyene/polythiol composition is cured by adding a photosensitizer to the composition and exposing it to U.V. radiation followed by heating to effect imidization. In other instances the same formulation is heated first to cause imidization and, thereafter, subjected to U.V. radiation to effect curing.
Additionally, both imidization and curing can be effected in one step by adding a chemical free radical generating agent, - e.g. benzpinacol to the polyene/polythiol composition, and thereafter, heating to effect both imidization and curing. Additionally, the polyene per se can be imidized by heating and, thereafter, admixed with a polythiol and photosensitizer for U.V. curing. These methods will be shown in the examples hereinafter.

. ~ ; , ,~ ` .
., . , ' .

, ' t ' . ' . ' .
'.: , . ~ .; ' . i ' ` '~
.. ..
`~

",. . .

' . ' , , , ij `; .' ., .
,` ;`'~ "'.

31.~ L35 Polythiol as used herein referssto simple or complex organic compounds having a multiplicity of pendant or terminally positioned -SH functional groups per average molecule.
On the average the polythiol must contain 2 or more ~SH
groups/molecule and have a viscosity range of essentially 0 to 20 million centipoises (cps) at 70 C as measured by a Brookfield Viscometer either alone or when in the presence of an inert solvent, aqueous dispersion or plasticizer. Operable polythiols in the instant invention usually have molecular weights in the range about 94 to about ?0, 000, and preferably from about 100 to about 10,000.
The polythiols operable in the instant invention may be exemplified by the general formula R8~ SH)n where n is at least 2 and R8 is a polyvalent organic moiety. Thus R8 may contain cyclic groupings and he~ero atoms such as N, P or O and primarily contains carbon carbon, carbon-hydrogen, carbon-oxygen, or silicon-o~ygen containing chain linkages.
One class of polythiols operable with polyenes to obtain-essentially odorless polythioether products are esters of thiol-containing acids of the formula HS-Rg-COOH where Rg is an organic moiety with polyhydroxy compounds of structure Rlo~OH)n where Rlo is an organic moiety and n is 2 or greater. These components will react under suitable conditions to give a polythiol having the general structure:

'' . . , Rlo~OC-Rg-SH)n where Rg and Rlo are organic moieties and n is 2 or greater.

Certain polythiols such as the aliphatic monomeric poly-thiols (ethane dithiol, hexamethylene dithiol, decamethylene dithiol, tolylene-2,4-dithiol, etc. and some polymeric poly-thiols such as a thiol-terminated ethylcyclohexyl dimercaptan polymer, etc. and similar polythiols which are conveniently and .

Z~ 5 ordinarily synthesized on a commercial basis, although having obnoxious odors, are operable in this invention but many of the end products are not widely accepted from a practical, commercial point of view. Examples of the polythiol aompounds preferred for this invention because of their relatively low odor level include but are not limited to esters of thioglycolic acid (HS-CH2COOH), ~-mercaptopropionic acid (HS-CH(CH3)-COOH and ~ -mercaptopropionic acid (HS-CH2CH2COCH) with polyhydroxy com-pounds such as glycols, triols, tetraols, pentaols, hexaols, etc.
Specific e~amples of the preferred polythiols include but are not limitèd to ethylene glycol bis (thioglycolate), ethylene glycol bis (~3 -mercaptopropionate), trimethylolpropane tris (thiogly-colate), trimethylolpropane tris (~ -mercaptopropionate), pentaerythritol tetrakis (thioglycolate) and pentaerythritol tetrakis (~ -mercaptopropionate), all of which are commercially available. A specific example of a preferred polymeric poly-thiol is polypropylene ether glycol bis ( ~ -mercaptopropionate) which is prepared from polypropylene-ether glycol (e.g. Pluracol P2olo~ Wyandotte Chemical Corp.) and ~? -mercaptopropionic acid by esterification.
The preferred polythiol compounds are characterized by a low level of mercaptan-like odor initially, and after reaction, give essentially odorless polythioether end products which are commercially attractive and practically useful resins or elas*
tomers for both indoor and outdoor applications.
Prior to curing, the photocurable polymer may be formu-lated for use as 100% solids, or disposed in organic solvents, or as solutions, disperions or emulsions in aqueous media.
` The photocurable polymer compositions prior to curing may readily be pumped, poured, siphoned, brushed, sprayed, doctored, or otherwise handled as desired. Following applica~ion, curing in place to a solid resin or elastomer may be effected either 2~35 very rapidly or extremely slowly as desired by manipulation of the compounding ingredients and the method of curing.
To obtain the maximum strength, solvent resistance, creep resistance, heat resistance and freedom from tackiness, the reactive components consisting of the polyenes and polythiols are fomulated in such a manner as to give solid, crosslinked, three dimensional network polythioether polymer systems on curing.
In order to achieve such infinite network formation, the individ-ual pol~enes and polythiols must each have a functionalit~ of at leas~ 2 an~ the sum of the functionalities of the polyene and polythiol components must always be greater than 4. ~lends and mixtures of various polyenes and various polythiols containing said functionality are also operable herein.
Functionality as used herein refers to the average number of ene or thiol groups per molecule in the polyene or polythiol, respectively. For example, a triene is a polyene with an average of three reactive carbon to carbon unsaturated groups per molecule, ancl thus has a functionality (f) of three. A dithiol is a poly-thiol with an average of two thiol groups pèr molecule and thus has a functionality (f) of two.
The term reactive unsaturated carbon to carbon groups means groups which will react under proper conditions as sèt forth herein with thiol groups to yield the thioether linkage (-C-S
C-), as contrasted to the term unreactive carbon to carbon unsaturation. which means -C=C- groups found in aromatic nuclei (cyclic structures exemplified by benzene, pyridine, anthracene, and the like) which do not under the same conditions react with thiols to give thioether linkages. For purposes of brevity, this term will hereinafter ~e referred to generally as reactive unsaturation or a reactive unsaturated compound~
As used herein, the term polyvalent means having a valence of two or greater.

2~L~c5 Prior to curing, the polyene and polythiol components are admixed in a suitable manner so as to form a homogeneous curable mixture~ Thus, the polyene and polythiol reactants can ~e admixed without the necessity of using a solvent at room temper-ature or slightly elevated temperatures up to about 80C or, if desired, the reactants may be dissolved in a suitable solvent and, thereafter, the solvent can be removed by suitable means such as evaporation.
The compositions to be cured in accord with the present invention may, if desired, include such additives as antioxidants, accelerators, dyes, inhibitors, activators, fillers, thickeners, pigments, anti-static agents, flame-retardant agents, surface-active agents, e~tending oils, plasticizers, thixotropic agents`
and the like within the scope of this invention. Such additives are usually pre-blended with the polyene or polythiol prior to or during the compounding step. The aforesaid additives may be present in quantities up to 500 or more parts based on 100 parts by weight of the polyene-polythiol curable compositions and preferably 0.005-300 parts on the same basis.
The polythioether-forming components and compositions, prior to ~uring, may be admixed with or blended with reactive diluents t other monomeric and polymeric materials such as thermo-plastic resins, elastomers or thermosetting resin monomeric or polymeric compositions.
Non-limiting reactive diluents operable herein include ethylene glycol diacrylate, ethylene glycol dimethacrylate, di-ethylene glycol diacrylate, diethylene glycol dimethacrylate, trimethylol propane triacrylate, trimethylol propane trimeth-acrylate, pentaerythxitol tetracrylate, pentaerythritol tetra-methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimeth-acrylate, pentaerythritol triacrylate, neopentyl glycol di-acrylate and mixtures thereof. The resulting blend may be - la-~ t5 subjected to conditions for curing or co-curing of the various components of the blend to give cured produc-ts having unusual physical properties.
Although the mechanism of the curing reaction is not completely understood, it appears most likely that the curing reaction may be initiated by most any free radical generating source which disso~iates or abstracts a hydrogen atom from an SH group, or accomplishes the e~uivalent thereof. Generally, the rate of the curing reaction may be increased by increasing the temperature of the composition at the time of initiation of cure. In most applications, however, the curing is accomplished conveniently and economically be operating at ordinary room temperature conditions.
Operable curing initiators or accelerators include radiation such as actinic radiation, e.g., ultraviolet light, lasers; ionizing radiation such as gamma radiation, x-rays, corona discharge, etc.; as well as chemical free radical gener-ating compounds such as azo, ~perox~idici~ etc., compounds.
Azo or peroxidic compounds (with or without amine accel-erators) which decompose at ambient conditions are operable as free radical generating agents capable of accelerating the curing reaction include benzoyl peroxide, di-t-butyl peroxide, cyclohexanone peroxide with dimethyl aniline or cobalt naph-thenate as an accelerator; hydroperoxides such as hydrogen peroxide, cumene hydroperoxide, t-butyl hydroperoxides; peracid compounds such as t-butylperbsnzoate, peracetic acid; persulfates, e.g., ammonium persulfate; azo compounds such as azobis-isobutyronitrile and the like.
These free radical generating agents are usually added in amounts ranging from about 0.001 to 10 percent by weight of the curable solid polyene-poly~hiol composition, preferably .01 to 5 percent.

2~3s~

Additionally, substituted or unsubstituted pinacols such as those set out in U. S. Patent No. 4,020,233 are also operable as free radical generators to form imide-containing cured polythioethers. That is, the amide-acid polyene, poly-thiol and pinacol can be heated to form an imide-containing, solid, cured polythioether as will be shown in an example here-inafter.
The substituted or unsub~tituted pinacols operable herein have the general formula:
1l 13 X Y
wherein Rl and R3 are the same or different substituted or unsubstituted aromatic radicals, R2 and R4 are substituted or unsubstituted aliphatic or aromatic radicals and X and Y which may be the same or different are hydroxyl, alkoxy or aryloxy.
Pre~erred pinacols are those wherein Rl, R2, R3, and R4 are aromatic radicals, especially phenyl radical and X and Y
are hydroxyl.
Examples of this class of compouncls include but are not limited to benzopinacol, ~,4'-dichlorobenzopinacol, 4,4'-dibromobenzopinacol, 4,4'-diiodobenzopinacol, 4,4',4"~,4"'-tetrachlorobenzopinacol, 2,4-2',4'-tetrachlorobenzopinacol,
4,4'-dimethylbenzopinacol, 3,3'-dime~hylbenzopinacol, 2,2'-dimethylbenzopinacol, 3,4-3',4'-tetramethylbenzopinacol, 4,4'-dimethoxybenzopinacol, 4,4' t 4",4"'-tetramethoxybenzopinacol, 4,4'-diphenylbenzopinacol, 4,4'-dichloro-4",4"'-dimethylbenzo-pinacol, 4,4'-dimethyl-4",4"'-diphenylbenzopinacol, xanthon-pinacol, fluorenonepinacol, acetophenonepinacol, 4,4'-dimethyl-acetophenone-pinacol, 4,4'-dichloro-acetophenonepinacol, 1,1,2-triphenyl-propane-1,2-diol, 1,2,3,4-tetraphenylbutane-2,3-diol, 1,2-diphenylcyclobutane-1,2-diol, propiophenone-pinacol, , L3~

4,4'-dimethylpropiophenone-pinacol, 2,2'-ethyl-3,31-dimethoxy-propiophenone-pinacol, 1,1,1,4,4,4-hexafluoro-2,3-diphenyl-butane-2,3-diol.
As further compounds according to the present invention, there may be mentioned: benzopinacol-mono methylether, benzo-pinacol-mono-phenylether, benzopinacol monoisopropyl ether, benzopinacol monoi-sobutyl ether~ benzopinacol mono (diethoxy methyl) ether and the like.
The pinacol is added to the composition in amounts ranging from 0.01 - 5% preferably 0.1 - 3~ bv weight based on the weight of the ethylenically unsaturated compound and the polythiol.
The curing period may be retarded or accelerated from less than 1 minute to 30 days or more.
Conventional curing inhibitors or retarders which ma~ be used in order to stabilize the components or curable compositions so as to prevent premature onset of curing may include hydro-quinone; p-tert-butyl catechol; 2,6-di tert-butyl-p-methylphenol;
phenothiazine; N-phenyl-2-naphthylamine; phosphorous acid;
pyrogallol and the like.
The preferred free radical generator for the curing reaction is radiation.
The curing reaction can be initiated by radiation having an energy greater than 3 electron volts, i.e., either U.V.
radiation or high energy ionizing radiation. The U.V. radiation can be obtained from sunlight or special light sources which emit significant amounts of U.V. light having a wavelength in the range of about 2,000 to about 4,000 Angstrom units. Any type of U.V. light from any source may be used in carrying out the method of this invention. For li~uid photocurable compo-sitions, it is preferred that the light emanate from a point source or in the form of parallel rays, but divergent beams are also operable as a source of radiation.

Various light sources may be used to obtain sufficient U.V. radiation to practice the method of this invention. Such sources include carbon arcs, mercury arcs, fluorescent lamps with special ultraviolet light emitting phosphors, xenon arcs, sunlight, tungsten halide lamps, argon glow lamps, photographic flood lamps, lasers and the like.
When U.V. radiation is used for curing, a photoinitiator is added to the composition to increase the curing rate.
Various photoinitiators, ~.e., photocuring rate acceler-ators are operable and well known to those skilled in the art.Examples of photoinitiators include, but are not limited to, be~zophenone o-methoxybenzophenone, acetophenone, o-methoxy-acetophenone, acenaphthene-quinone, methyl ethyl ketone, valero-phenone, hexanophenone, ~-phenylbutyrophenone, p-morpholino-propiophenone, dibenzosuberone, 4-morpholinobenzophenone, benzoin, ben20in methyl ether, 4'-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone, benzaldehyde, o-methoxybenzaldehyde, ~-tetralone, 9-acetyl-phenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindole, 9~fluorenone, l-indanone, 1,3,5-triacetylbenzene, thioxanthen-9-one, xanthene-9-one, 7-M-benz[dc]anthracen-7-one, l-naphthaldehyde, benzoin tetrahydro-pyranyl ether, 4,4'-bis ~dimethylamino)benzophenone, fluorene-9-one, l'-acetonaphthone, 2'-acetonaphthone, triphenylphosphine, tri-o-tolylphosphine, acetonaphthone and 2,3-butanedione, benz[a]anthracene 7,12 dione, 2,2-dimethoxy-2-phenylacetone, diethoxyacetophenone, dibutoxyacetophenone, etc., which serve to ~ive greatly reduced exposure times and thereby, when used in conjunction with various forms of energetic radiation, yield very rapid, commercially practical time cycles by the practice of the instant invention.

- ~2 -2,~5 These photocuring rate accelerators may range from about 0.005 to 50 percent by weight of the photocurable polyenepoly-thio composition, preferably 0.05 to 25 percent.
The mole ratio of the ene/thiol groups for preparing the curable composition i5 from about 0.2/1.0 to about 8/1.0, and preferably from 0.5/1.0 to about 2/1.0 group ratio.
The radiation curable compositions of the instant invention can also be cured by high energy ionizing irradiation. A
preferred feature of the ionizing irradiation operation of the instant invention is treatment with high energy particle irradi-ation or by gamma-rays or X-rays. Irradiation employing part-s icles in the instant invention includes the use of positive ions (e.g., protons, alpha particles and deuterons), electrons or neutrons. The charged paxticles may be accelerated to high speeds by means of various voltage gradient mechanisms such as a Van de Graaff generator, a cyclotron, a Cockroft Walto~
accelerator, a resonant cavity an accelerator, a betatron, a G. E. resonant transformer, a synchroton or the like. Further-more, particle irradiation may also be supplied ~rom radio-- active isotopes or an atomic pile. Gamma rays or X-rays may be obtained from radioisotopes ~e.g., cobalt 60) or by particle bombardment of suitable target material ~e.g., high energy electrons on a gold metal target)~
The dose rate for the irradiation operable to cure the coating in the instant invention is in the range 0.00001 to 1,000 megarads/second.
The amount of ionizing radiation which is employed in curing the radiation curable material in the instant in~ention can vary between broad limits. Radiation dosages of less than a megarad up to 10 megarads or more for electrons are operable, preferably 0.02 to 5 megarads energy absorbed are employed.
For gamma-rays or X-rays, radiation dosages in the range ~2~3t~

0,0001 to 5.0 megarads energy absorbed are operable. The irradiation step is ordinarily performed under ambient temper-ature conditions but can be performed at temperatures ranying from below room temperature up to temperatures of 90C.
When using ionizing radiation, the depth of penetration is dependent upon the density of the material to be penetrated.
If such penetration is not sufficient to cure the coating to the entire depth desired when,-)beaming the rad~ation from one direction only, one may use multiple radiation sources beaming simultaneously or intermittently from diametrically opposite sides of the coating. Furthermore, shielding can also be employed to increase penetration of the coating on the opposite side away from the radiation source.
The curable amide-acid polyene or imide polyene and poly-thiol compositions are used in preparing solid, cured cross-linked insoluble polythioether polymeric products having many and varied uses, examples of which include, but are not limited to, coatings; adhesives films, molded articles; imaged surfaces, e.g. photoresists; printing plates; e.g. offset, lithographic, letterpress, gravures, etc., silverless photo-graphic materials and the like.
Since the cured materials formed from the polyenepolythiol composition possessvarious desirable properties such as resist-ance to severe chemical and physical environments and have good high temperature properties on imidization, they are particu-larly useful for preparing coatings.
A general method for preparing coatings, comprises coating the curable composition on a solid surface of a substrate such as plastic, rubber, glass, ceramic, metal, paper and the like;
exposing directly to radiation, e.g., U.V. light until the curable composition cures and crosslinks in the exposed areas.

The resulting products are cured coatings on suitable substrates or supports.

In forming the composition comprised of the polythiol and the polyene, it is desirable that the photocurable compos-ition contain a photocuring rate accelerator from about 0.005 to 50 parts by weight based on 100 parts by weight of the afore-mentioned polyene and polythiol.
It is to be understood, however, that when energy sources, e.g., ionizing radiation, other than visible or ultraviolet light, are used to initiate the curing reaction, photocuring rate accelerators (i.e., photosensitizers, etc.) are not required in the formulation.
When U.V. radiation is used, an intensity of 0.0004 to 60.0 watts/cm2 in the 240-400 nanometer region is usually employed.
The following examples will aid in explaining, but should not be deemed limiting, the instant invention. In all cases unless otherwise noted, all parts and percentages are by weight.
The termal shock and thermoplastic flow test were carried out in accord with the procedure set out in National Electric Manufacturers Association (NEMA) standards publication/No. MW
1000-1973.
In all examples herein, unless otherwise noted, the U.V.
radiation from the Addalux lamp had a surface intensity of 13,400 microwatts/cm2 and from the pulsed xenon lamp a surface intensity of 22,000 microwatts/cm2.

- 24a -3~

~XAMPL~ 1 To a 3-necked, 300 ml round bottom flask equipped with stirrer, addition funnel and reflux condenser was charged under a ni-trogen blanket 40.62 g of pyromellitic dianhydride (PMAn) and 75 ml of freshly distilled N-methyl-2-pyrrolidone (NMP). To the addition funnel was added 22.11 g of N,N'-bis-~3-aminopropyl)dimethylhydantoin and 25 ml of NMP. The PM~n was ~irst dissolved in the NMP and then, while the temperature was kept between 40-60C, the diamine was added slowly, dropwise, during a period of 1.5 hours. When the addition was completed, the temperature of the reaction mixture was raised to and kept at between 70-80C while adding 38.71 g of trimethylol-propane dially~ ether during a period of about 20 minutes.
Some more NMP was added to the reaction mixture after addition of each reagent. Once the alcohol was added, the mixture was kept between 70-80C for one hour, after which time it was cooLed and worked up as follows:
The very viscous reaction mixture was dropped in-to a large quantity of water and shaken vigorously. After discarding the water layer, vigorous agitation with water was repeated three more times. The viscous gum was then dissolved in methanol, and the solu-tion was transferred into a round bottom flask, provided with stirring, Dean-Stark trap and a reflux condenser.
130 ml of benzene was then added and the solution was - then boiled vigorously whil.e ais-tilling out most of the methanol alollg wi~h most of the waL~er. The remaining water, methanol and benzene were then distilled off under reduced pressure at a maximum temperature of 80C.

. - 25 -2~

The brown very viscous product weig11ed ~5 cJ. I'he IR
spectra indicated that at.least 75~ of this product was of the formula:

C~13 O O ~ C1-13~ ~
HOC\ ~ /C-NH-~C11 ~-N N-~C11 ) -N11 CH2=cE-lcll2ofH2 ~ 2 3 ~,~ 2 3 C~13CH2C-CH2-OC CO1l '' CH2=CHCH20CH2 1 0 ~
. O O
ll ll -C ~ ~CO11 ¦ o J o Cl~2C~I2CH=C~l2 HOC CO-c~12-CCE~2~H3 CH20CH2C~I=CH2 will hereinafter be referred to as Polyene A.
~XAMPL~ 2 To a 3-necked, 300 ml round bottom flask equipped with stirrer and reflux condenser, was added under a nitrogen blanket 25.67 g of 1,3-bis(aminomethyl)cyclo~
hexane and lO0 ml of dimethylformamide. I`he mixture was heated to approximately 125C and while maintaining the temperature constant, 69.97 g. of trimellitic anhydride (TM~n) was added in three equal por-tions. The reaction was allowed to proceed for 1.-5 hours and thcn was cooled to room temperature. The product was worked up by dropping the reaction mixture.into a large volume of v1gorously stirred water. The water layer was then disc.arded and the vigorous agitatio~ of the yun~ly product with water was repeatecl. After discarding the water . - ~6 -. J. '4 ~, again, 25 ml of acetone was used to break up the cJum while it started solidifying. To this slurry was added 500 ml of chloroform. The solid product was then filtered and reslurried in benzene. This slurry was then dried by azeotropic distillation, the whi-te solid amide-acid was filtered and was th~nkept in a vacuum dissicator containin~ P2O5. To a 3-necked, 300 ml round bottom flask equipped with stirrer, reflux condenser and Dean-Stark trap, was added ~.0 g of the white solid amide-acid supra 50 ml of allyl alcohol and 0.1 g of concentrated H2SO4. The mixture was boiled and while allyl alcohol was distilled out of the flask in increments of about 10 ml, fresh allyl alcohol was added to the flask to replace the removed alcohol. This procedure was continued for several hours until sufficient esterification had occurred. Solids in the reaction mixture were then filtered off and the allyl alcohol in the filtrate was s-tripped under vacuum. The product was a liyht brown, very viscous liquid of the formula:

" I I' 2NHC~
CH2=C~ICH2OC ~ COH O ¦ "
O ~IOC- ~ `CC~2C~I=C~12 O
which will be referred to hereinafter as Polyene B.

~X~MPL~ 3 To a 3-necked, 300 ml round bot-tom flas]c equipped with - stirrer, reflux condenser and a m~dified Dean-Stark -trap, was added under a ni-trogen blanket 10.31 g. of trimelletic anhydride (TMA~ and 6.37 g. of N,N'-bis(3-aminopropyl)dimethylhydantoin.

'''.J, 2~5 While the mixture was purged through with nitrogen, it was heated to about 160-180C~ Soon after the fairly fast reaction occurred, the reaction product was cooled to about 80C. 50 ml of allyl alcohol, 0.009 g. of hydroquinone and 0.224 g. of concentrated H2SO4 was then added to the pot and the Dean-Stark~ trap was filled with alumina so that the alcohol could be recirculated to the reaction flask while being dried by the alumina. The reaction mixture was refluxed for about one hour. Upon completion of the reaction, the excess allyl alcohol was stripped off under vacuum. The final product of the formula:

CH3 ~ ~ O
ll ll C-NH-~CH2~ N~"~N-~CH2)3 ~

" OH HOC CO-CH2-CH=CH2 CH2=CH--CH2-OC ,, O
was a yellow-brown viscous material and will be referred to hereinafter as Polyene C.

To a 3-necked, 300 ml round bottom flask equipped with stirrer, reflux condenser and a modified Dean-Stark trap, was added under a nitrogen blanket 10.31 g. of TMAn and 6.37 g.
of N,N'-bis(3-aminopropyl)dimethylhydantoin. While the mixture was purged through with nitrogen, it was heated to about 160-180C. Soon after the fairly fast reaction occurred, the reaction product was cooled ~L6~ s5 to about 80C. 43.0 g. of allyl alcohol, and 5.56 g. of trimethylolpropane diallyl ether, 0.0009 g. o~ hydroquinone and 0. 224 g. of concentrated H2SO4 was then added to the pot and the Dean-Stark trap was filled with alumina so that the alcohol could be recirculated to the reaction flask while being dried by the alumina. The reaction mixture was refluxed for about one hour. Upon completion of the reac-tion, the excess allyl alcohol was stripped off under vacuum. The final product of the formula:

o CH3 ~

CH2=CHCH2OICH2 O ~ C-NH ~CH2~--3N~"~N (CH2) 3 .

CH2=

Lo C

HOC~\CO--cH2cH=cH2 was a yellow-brown viscous material and will be referred to hereinafter as Polyene D.

To a 3-neck, 5-liter, round bottomed flask equipped with stirrer, addition funnel, thermometer, reflux condenser and a nitrogen sparge tube ~gas disperse system) was added under nitrogen 322.4 g. of trimellitic anhydride acid chloride (TMAn. Cl) and 791 g. benzene. The misture was heated until all the TMAn. Cl dissolved in the benzene. To this solution was added very slowly (via a 2i'~

dropping funnel) a 43% solution of trimethylo:Lprol?ane diallyl ether in benzelle (311.70 g. in 413 g. benzene) while the temperature oE the contents in the reaction flaslc was kept just below 80C with continuous N2-sparging - into the reaction solution. Once all the trimethylol-propane diallyl ether was added, the N2-sparge was continued to remove all the IIC1 in the reaction mixture. 650 g.
cf benzene was then distilled out of the reaction vessel.
The temperature of the reaction mixture was then lowered to about 60C at which time a 49% solution of N,N'-bis (aminopropyl)dimethylhydantoin, in benzene (176.23 g.
in 185 g. benzene) was added at a rate sufficient to sustain a temperature of about 55-70C. Once all the N,N'-bis (aminopropyl)dimetllylhydantoin was added, the reaction mixture was kept a-t 60C until the IR absorption bands of the anhydride carbonyl groups disappeared. Allalysis for unreacted amine groups showed that the amine content was less than 0.2 meq/g. The resultan-t product was obtained by distilling off the benzene under vacuum. The product (741 g) contained 24~ by weight imide and an amide-acid polyene of the formula:

- Cll3 C113~

~ ~C-NII~CII ~N ,N~CII ) -Nll--cll2=cllcl~2o~ll2 ~ 2 ~ ~o 2 3 C113C112('-C112-0C ~COII
cll2=cllc~l2~cll2 -CO~
, ~ C1 1120C1l2cll=cll2 ' ' 110(` CO C112 CIC112C113 cil2Ocll2cll=cll2 _ . ~ . . . , . , . .. _ _ _ _ _ _ _ which will be referred to hereillafter as Polyene ~.

Z~;~5 ~`X~MPI.~ 6 To a 3-necked, 300 ml round bottorn flask eguipped with s-tirrer, addition funnel and reflux condenser was charged under a nitrogen blanket 43.44 g. of pyromellitic dianhydride (PMAn) and 75 ml of freshly distilled N-metllyl-2-pyrrolidone (NMP). To the addition funnel was added 16.50 g.
of isophorone diamine, i. e. 3-aminomethyl-3,5,5-trimethyl-cyclohexylamine and 25 ml of NMP. The PM~n was firs-t dissolved in -the NMP and then, while the temperature was kept between 40-60C, the diamine was added slowly, drop-wise, during a period of 2.0 hours. When the addition was completed, the temperature of the reac-tion mix-ture was raise~ to andkept at between 70-80C while adding 41.41 y.
of trimethylolpropane diallyl ether mixed with 9 ml of NMP
during a period of about 5 minutes. Some more NMP was added to the reaction mixture after addition of ~ach reagent. Once the alcohol was added, the mixture was kept between 70-80C for one hour, after which time it was cooled and worked up as follows:
The very viscous reaction mixture was dropped in-to a large quantity of water and shaken vigorously. ~fter discarding the water layer, vigorous agitation with water was repeated three more times. Thc viscous ~um was then dissolved in methanol, and the solution was transferred into a round bottom flas]c, provided with stirriny, Dean-Stark trap and a reflux condenser. 130 ml of benzene was then added and the solution was then ~oilecl vi~Jorously while distilling out most of the methanol, which carries out most of the water. The remaining water, met}lanol and ben~ene were then distilled off under reduced pressure at a ;'`,)'.

~ ?2135 maximum temperature of 80C. The brown very viscous product wt. about 95 g of the formula:

Cll2=cllcll~ofll~ o ~ ~C-i~ill_________ 2 Cll3cll2c-cll -OC ~COil C~l2=cllcll2ocll2 o C~13 ~o O '~~ ~~~
,.
-C~/\~,(.'OII
~ , I ll2C112CIi=C'il2 110(` ,C'O-C`II;~-f~ 2C~3 '''`' Cll2oclf2c~ ll2 will hercinafter l)e rel~err~ o as l'ol~ c?. F

.5 E~AMPLE 7 To a 4-necked, 1 1. round bottom flask equipped wlth stirrer, addition funnel, thermometer, Dean-Stark trap, and reflux condenser was charged under a nitrogen blanket 16.0 g of N,N'-bis~2-carboxyethyl)-dimethylhydantoin, 1.30 g of p-toluene sulfonic acid as catalyst and 100 ml of benzene. The mixture was refluxed until the Dean-Stark trap was full of benzene, and then 3.50 g of allyl alcohol and 12.91 g of trimethylolpropane diallyl ether in 50 ml of benzene was added during a period of 35 minutes. When no more water was azeotroping into the Dean-Stark trap, the heat was turned off and the product was worked up by washing it twice with 150 ml of water, then twice with 100 ml of 5% aq. NaHCO3, and then again twice with 100 ml of water. The benzene layer containing the product was then dried with anhydrous MgSO4, treated with decolorizing carbon, and then distilled under vacuum until all the benzene was taken off.

The product, i. e., ,Q

CH3 _ Y

O o fH2ocH2cH=cH2 2 2 OC(CH2)2N~"~N(CH2)2cocH2-c-cH2cH3 had a C=C content of 5.80 mmoles/g and will be re~erred to hereinafter as Polyene G.

2~13~

The polyenes of the instant invention can be imidized per se as is shown in the following examples.

A thin film of Polyene A from Example 1 was placed on a sodium chloride IR window and heated for 5 minutes at 210C.
The IR spectrum after heating said polyene showed the disappear-ance of the amide band and a significant increase of the imide band evidencing imidization. The imidized polyene of the formula:

( ~H3 CH3 ~

HOC~ C\ (C 2) 3~ ~ ~N (CH2)3 ,,~ _~ ~,~" . ~ ~
~ll2-1r~ 2 1 2 O O! N~ O
fH3cH2f--cH oc~ ~--o!
CH2=CHCH20CH2 o o .
/ C ~ COH

N ~ o f 2 2 2 C f will hereinafter be referred to as imidized Polyene H.

Example 8 was repeated except that Polyene E from Example 5 was substituted for Polyene A. The results were the same. The imidized polyene of the formula:

2~3~

o 3 ~ f CH2=CHcH2olcH2 ~ C (CH2)-3N\ ~ N (CH2)3 CH3CH2C-CH2-OC C .
CH2=CHCH2OCH2 O
&~ o f E~ 2 OCE~ 2 CH--c~ 2 C CO-CH -CCH CH

CH20CH2C~I=CH2 will hereinafter be referred to as imidized Polyene J.
Example 8 was repeated using Polyenes B, C, D and F from Examples 2, 3, 4 and 6. The IR spectrum after heating said polyenes in each case showed the disappearance of the amlde band and a siynificant increase of the imide band.

.. . _ . . . .. . .. _ .. .. . _ _. _ . . . . . .. _ . . _ .
To a four-neck, one-liter, round-bottomed flask equipped with stirrer, additional unnel, thermometer, heated (approx. 100-110C) Vigreux column, and a nitrogen sparge tube was added under nitrogen 226.32 grams of trimellitic anhydride 248.22 grams of trimethylolpropane-diallyl ether and 2.5 grams of 1,6-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate). While the reaction vessel wa`s slowly purged with nltrogen, the reaction mixture was suddenly heated in an oil bath to ~40C. This tempera-ture was maintained for about 4.5;hrs. while the slow nitrogen purge removed the water generated by the reaction. ~very -35~

~3~ 1L3~i;

40 minutes, the top layer of the distillate was returned to the pot while the lower layer was discarded. The last two returns of the top layer were timed such that they were done about every 15 minutes before the reaction was considered as finished. The reaction mixture was then rapidly cooled to 170c.
The Vigreux column was removed from the round bottomed flask. In its place was pla~ed a short inverted U-shaped tube, To the product made above was added first 0.2 g of hydroquinone and 0.1 g of pyrogallol, and then drop-wise over a 45 minute period 64.32 grams of molten M-phenylene-diamine while slowly purging the reaction ~essel with nitrogen.
The reaction mixture was then kept for one h~ur at 175C, and the nitrogen flow was increased to achieve a rapid removal of the water arising from the imidization of the amide-acid.
The resultant imidized product of the formula;

O' CH2=CHCH20CH2 ~ ~ N O
CH CH -fCH20C C ~ ,,C ~

CH2=CHCH20CH2 ~ C ~ 1l Cl 2 2 2 o COCIi2CCH2CH3 CH20CH2CH=CH2 will hereinafter be referred to as Polyene T.

3~

The following examples show various curable compositions of either the amide-acid polyene or imide polyene in combina-tion with a polythiol and methods of curing to obtain a cured polythioether product.
5.0 g of Polyene E from Example 5 was admixed with 1.57 g of the bis(3-mercaptopropionate) of 1,3-bis (2-hydroxye-thyl)-5,5-dimethylhydantoin, 0.20 g oE
pentaerythritol tetralcis(~-mercaptopropionate~, 0.10 g of trime-thylolpropane tris(~-mercaptopropionate) and 0.137 g of 2,2-dimethoxy-2-phenylacetophenone until homogeneous.
The admixture was exposed to U.V. radia-tion for 15 seconds from Addalux lamp to form a cured polythioether and, thereafter, heated for 5 minutes at about 210C to imidize - the polyene portion. The IR spectrum of the resultant cured solid product showed disappearance of the thiol and amide absorption bands and appearance of the imide absorption bands.

9.~57 g of Polyene E from Example 5 was heated at 210C for 5 minutes to imidize the polyene. 'l'he thus imidized polyene was admixed with 4.14 g of the bis (3-mercaptopropionate) of 1,3-bis(2-llydroxyethyl)-5,5-dimethylhydantoin, 0.40 ~ of pcntaerythritol tctrakis (y-mercaptopropiona-te), 0.20 g of trimethylolpropane tris(~-mercaptopropionate) and 0.147 y of benzoin iso-propyl ether. The admixture was exposed to ~.V. radiation from an ~ddalux lamp for 15 sccon~'s. A cured polythio-ether produc~ resul-ted.

.

Using the formula-tion of ~xamplc llf-the proccdure was reversed and the formulation was heated for 5 minutcs~
at 210C fol.lowed by U.V. curiny for lS seconds under an Addalux lamp. A cured imidized polythioether product resulted.

10 g. of Polyene E from Example 5 was admixed with 4.6 g. of di(2-hydroxyethyl)dimethylhydantoin bis(3-mercapto-propionate), 2,5 g. of pentaerythritol tetrakis(~-mercapto-propionate) and 0.166 g. of benzopinacol until homogeneous.
The adr~lixture was heated at 180C for 5 minutes. A cured solid imidized polythioether product resulted.
The following examples show the'utility of the polyene of the instant inven-tion with a polythiol in forming an imidized cured polythioether coating when subjected to U.V. radiation and heat. When U.V. radiation is used, a photosensitizer or photocuring rate accelerator is usually added to the system along with various convèntional stabilizers to extend shelf life.
The amide-acid polyenes combined with a polythiol' ,will be compared with polyene/polythiol systems in which the polyene is not imidizable or is not imidized and thus does not have the improved higher temperature propcrties such as'are desired,in wire coating.
? EXAMPLE 15, The following formula'tions were made up from accurately weighed ingredients and admixed until homogeneous:

Formulation A
5.00 g. Polyene A from Example 1 3.26 g- tris(hydroxyethyl)isocyanurate tris (3-mcrcapto-- propionate) 0.083 g. benzoin isopropyl ether (photosensitizer) 0.826 g. trimethylolpropane diallyl ether 0.826 g. dimercaptopropionate of N,N'-bis(2-hydroxyetilyl) dimethylhydan-toin 0.083 g. benzopinacol 0.005 g. stabilizer package Formulation B
3.78 g. Polyene A from Example 1 1.22 g. -tris(hydroxyethyl)isocya~urate tris (3-mercapto-propionate) 0.50 g. dimercaptopropiona-te of N,N'-bis(2-hydroxy-ethyl)dimethylhydantoin - 0.25 g. trimethylolpropane diallyl ether 0.10 g. benzoin lsopropyl ether 0.005 g. stabilizer package Formulation C
5.00 g. Polyene D from Example 4 4.28 g. tris(hydroxyethyl)isocyanurate tris (3-mercapto-propionate) 1.41 g. dimercaptopropionate of N,N'-bis(2-hydroxy-ethyl)dimethylhydantoin 0.36 g. trimethylolpropanc diallyl ether 0.186 g. benzoin isopropyl e-ther 0.010 g. stabilizer package Formulation D
10.0 g. Polyene A from ~xample 1 3.25 g. tris(hyclroxyethyl)isocyanurate -tris(3-mercapto-propionate) 0.66 g. dimercaptopropionate of N,N'-bis(2-hydroxyethyl) dimethylhydantoin 0.28 g. benzoin isopropyl e-ther 0.014 g. stabilizér package Formulation E
10.0 g. Polyene F from Example 6 3.02 g. dimethylolpropionic acid bis(3-mercaptopropiollate) 0.33 g. benzoin isopropyl ethcr 0.018 g. stabilizer packagc Formula-tion F
.... . .
5.0 g Polyene E from Example 5 2.07 g dimerc~ptopropiona-te of N,N'-bis(2-hydroxy-ethyl)dimethylhydantoin 0.20 g commercia~ly availablc pentaerytilritol tetrakis - (~-mercaptopropionate) 0.10 g trimethylolpropane tris(~-mercaptopropionate) 0.137 g 2,2-dimethoxy-2-phenylace-tophenon~
0.009 g stabilizer package Formulation G
45.0 g diallyl maleate 82.7 g tris(hydroxyethyl)isocyanurate tris(3-mercapto-propionate~
3.83 g benzoin isopropyl ether 1.99 g s-tabilizer package -- ~0 --Z~L~3rj Formulation ~1 -20.00 g Polyene G from Examplc 7 2.38 g commercially available iso-diallylphthalate 23.66 g tris(hydroxyethyl)isocyanura-te tris(3-mercaPto-propiona-te) 1.38 g benzoin isopropyl ether 201.41 g stabilizer package Formula-tion I
.
20~00 g Polyene T of Example 10 3~01 ~ triallyl isocyanurate 15.25 g pen-taerythrito~ tetrak~s (3-mercaptopropionate~
1,34 g dimercaptopropionate o~ N,N'-bis(2-hydroxyethyl)-d~methylhydantoin 0.792 g 2~2-dimethoxy-2-phenylacetophenone 0~008 g .stabilizer package A 24 AWG copper wire was passed -through a degreasing bath of methylene chloride followed by drying. The wire was cut intolO sections and each wire section was cooled .with one of the Formulations A-I from Examp.le15 with the extra wire section also being coated-with Formulation F, all at ambient conditions.
Each section of the thus coated wire was thell passed through a die to insure a homogencous thickness of 1 mil and -through a surrounding barl]; oE U.V. pulscd ~cnon lamps whose major spectral lines were all above 300 Angstroms 2~

at a speed o~ 20 feet per second for an exposure period of 2 seconds. The sunlamps were so positioned that the surface intensity on the radia-tion curable composition was 22,000 microwatts/cm . All the resulting wire sections had a smooth, cured coating of 1 mil thickness and showed good flexibility and adhesion on bendiny.
The thus cured coated wire sections coated with Formulations A, B, C, D and one section coated with Formulation F were then heated at 210-220C for 5 minutes to affect imidization.
All the wire sections with their cured coating were then subjected to standard NEMA heat shock and -thermoplastic flow test. The results are shown in TABL~ I.
TABL~ I
Formulation Properties of Wire-Coated FormulatioJls Average Cut-Through lleat Shock (20~ S-tretchecl Temperature (C) Wire at 175C for 30 l~inutes ... .
A 220 passed 1 x mandrel B 260C passed 3 x mandrel C - passed 2 x mandrel D 210 passed 2 x mandrel E 200 passed 1 x mandrel F (imidized) 225 passed 3 x mandrel ` F (not imidized)125 passed 2 x mandrel G 255 failed 5 x mandrel H 100~ failed 5 x mandrel I 350 passed 2 x mandrel .-.

;' ,~,' .

~.Q~2~

Thus, as can be seen from the data in TABLE I, the radi-ation curable formulations containing an imidized polyene (Formulations A-F and I~ have improved high temperatures prop-erties over conventional radiation curable polyene/polythiol formulations tFormulations G and H) wherein the polyene is not imidizable and over Formulation F which was not imidized.
The amide-acid polyenes of the instant invention can also be synthesized in polymeric form as shown by the following example:
E~AMPLE 17 To a 3-necked, 300 ml round bottom flask equipped with stirrer, addition funnel, thermometer and nitrogen sparge tube was charged under a nitrogen blanket 24.37 g. of pyromellitic dianhydride (PMAn) and 44 ml of freshly distilled N-methyl-2-pyrrolidone (NMP). The flask was heated to about 90C to dissolve the PMAn, 13.4 g. of N,N'-bis(3-aminopropyl)dimethyl-hydantoin and 15 ml NMP were charged to the addition funnel.
The flask was cooled to 75C and the contents of the addition funnel were added to the flask over a one minute period. The contents of the flask was stirred at 70C for 30 minutes after which 6.29 g. of allyl alcohol were added to the flask. The contents of the flask was then charged into chloroform and filtered. A light brown polymeric polyene product (molecular weight 6600 indicating 6-7 repeating units) resulted. The IR
spectrum showed little or no imide present in the product and a substantial amide band present.
This polymeric polyene will be referred to hereinafter as Polyene K.

2~

5 g of Polyene K were heated for 10 minutes at 220-C. The resultant product was dark brown, indicative of imidization.

5 g of Polyene K were admlxed with 1.96 g of dimethylolpropionic acid bis(3-mercaptopropionate) and 0.139 g. of 2,2-dimethoxy-2-phenylacetophenone. The admixture was exposed to U.V. radiation for 3 1/2 minutes from an Addulux lamp. A cured, solid polythioether resulted.

The formulation of ExampLe 11 was coated to 1 mil thlckness on each of the following substrates: paper, cardboard, aluminum foil, steel plate stock, "Mylar"
polyester film, plywood, ceramic and a concrete block of the type used in-building construction. The thus coated substrates were exposed to U.V. radiation for 30 seconds from an Addelux lamp to form a cured polythio-ether coating and, thereafter, heated for 5 minutes at 210C to imidize the polyene portion.

, , ~3 ~ ?

To a 3-necked, 300 ml round bottom flask equipped with stirrer, addition funnel and an air sparge tube (gas disperse system) was added 50 g of glacial acetic acid, 68.20 g of trimellitic anhydride acid chloride, 0.585 g of 2,6-di-t-butyl-4-methylphenol and 0.0585 g of methyl hydroquinone. After dissolution of the solids, the flask was immersed into an ice/water bath. A mixture of 32.10 g of triethyl amine (TEA) and 45.30 g of hyclroxy-10 butyl acrylate (HBA) was then added dropwise to the coldsolution while continuously purging the reaction mixture with air. Once the HBA/TEA mixture was added (addition took 70 minutes), the cloudy reaction mixture was lef-t standing for 10 minutes. 17.32 g of solid m-phenylene diamine was then added slowly while keeping the reaction mixture at about 35C. The disappearance of -the anhydride group was followed by lnfrared spectroscopy. Once all the anhydride reacted with the amine, the reaction mixture was dropped into a large excess of vigorously agitated 20 water. The viscous gummy product was then dissolved in acetone and the solution was`dried with anhydrous magnesium sulfate and treated with decolorizing carbon.
To~the clear slightly yellow solution was added 0.585 g of 2,6-di-t-butyl-4-methylphenol and 0.0585 g of methyl hydroquinone. The bulk of the acetone was then evaporated off slowly at near-room temperature. Residual acetone was evaporated off at 80C for 0.5 hours.
Interpretation of the IR specti:'um of the final cloudy brick-red waxy material showed that the material 30 contained primarily the compound of the formula:

2~

O o~ \NH~ o CH2=CEiCO ~CH2) 4OC COH NH-C~
o , ~ o o HOC (C 2) 40CCH CH2 ... . . , , ., . .. _ .. , _ . . . . . . . . . . .
hereinafter referred to as Polyene L, and small amounts of the cyclized imide of the compound above.

A portion of the compound made and described under Example 19 was heated to 150C for 0.5 hours to effect imidization of Polyene L.
Interpretation of the IR spectrum of the final light yellow beige glassy solid showed that the material contained primarily the compound of the formula:

O

CH2=CHCO(CH2) 40C~'~ ~ ~C~ O O
~C~ CO ( CH 2 ) 4 OCCH=C~ 2 O .. ..

referred to hereinafter as Polyene M, and small amounts of the uncyclized amide-acid.

, .

~2~iL3S

To a 3-neck, 2 liter, round bottomed flask equipped with stirrer, addition funnel, thermometer, reflux condenser and a nitrogen sparge tube was added under nitrogen 309.30 g of trimellitic anhydride acid chloride (TMAn.Cl) and 425 g toluene. The mixture was heated until all the TMAn.Cl dissolved in the toluene (15-20 minutes).
To this solution was added via a dropping funnel, slowly over a 2 hour period, 296.40 g of trimethylolpropane diaIlyl ether (E) while the temperature of the contents in the reaction flask was kept at about 80C with continuous N2-purging into the reaction solution.
The N2-effluent, carrying much HCl and some toluene, was bubbled through a trap, to condense the toluene, and an aqueous NaOH scrubber, to neutralize the HCl.
Once all the E was added, the reaction mixture was kept at 80C for another 30 minutes. It was then heated to its boiling point (118C), and one half of the toluene was distilled out of the reaction vessel while slowly purging with nitrogenO The removal of the toluene took about 20 minutes. The volume of toluene which WdS distilled out was then replaced with fresh toluene, and the E-ester of-the trimellitic anhydride (TMAn.E)/toluene solution - was then subjected to an intermittent stream of steam while keeping the reaction mixture at a mild reflux.
The water that was distilled ou-t of the vessel was collected and analyzed for HC1. The total time to remove the HCl was about 4.75 hours. The;total amount of water used was about 260 ml.

~ ~,t~

Once the HCl was removed, the TMAn-E/toluene solution was azeotropically dried and then fil-tered.
To the dry TMAn-E/toluene solution was added batchwise, while keeping the temperature down to room temperature, a total of 77.03 g of m-phenylene diamine (PDA). The PDA was added "tricklewise" in 10% increments and,after each addition, time was allowed for the PDA to completely dissolve before the next addition was made. The time between incremental additions (up to 70% of the total addition) was about 10 minutes. This time increased to about 20 minutes for each remaining incremental addition.
Once all the PDA was added and dissolved, the reaction solution was kep-t at 55C for one hour.
The reaction solution was then refluxed for about 4 1/2 hours while removing azeotropically the water that is generated during the imidization of the amide-acid.
Once complete imidization was achieved, the toluene was distilled out at a reduced pressure. When most of the toluene was removed, the temperature of the kettle was increased to 130-140C to reduce the viscosity of the brown product and thus increase the rate of removal of residual toluene. The resultant imidized polyene of the formula:

CH2=c~IcH2oclH2 ~ ~ ~ ~
CH CH C-CH -O-C ,CO N ~ O CH2OCH2CH-CH2 CH2=CHCH2OCH2 O C-O-CH -CCH CH

- 30 will hereinafter be referred to as Polyene N.

,2~

To a 3-neck, 2 li-ter, round bottomed flask equipped with stirrer, addition funnel, thermometer, reflux condenser and a nitrogen sparge tube was added under nitrogen 309.30 g of trimellitic anhydride acid chloride (TMAn.Cl) and 425 g toluene. The mixture was heated until all the TMAn.Cl dissolved in the toluene (15-20 minutes).
To this solution was added via a dropping funnel, slowly over a 2 hour period, 296.40 g of trimethylolpropane diallyl ether (E) while the temperature of the contents in the reaction flask was kept at about 80C with continuous N2-purging into the reaction solution.
The N2-effluent, carrying much HCl and some toluene, was bubbled through a trap, to condense the toluene, and an aqueous NaOH scrubber, to neutralize the HCl.
Once all the E was added, the reaction mixture was kept at 80C for another 30 minutes. It was then heated to its boiling point (118C), and one half of the toluene was distilled out of the reaction vessel while slowly purging with nitrogen. The removal of the toluene took about 20 minutes. The volume of toluene which was distilled out was then replaced with fresh toluene.
~ To the hot E-ester of trimellitic anhydride (TMAn.E)/
toluene solution was added batchwi-se a total of 100 ml of water. The water was added in l0 ml increments and after each addition the water was azeotroped off again.
Each water increment was added at slightly below 100C, and it carried over a large amount ~f the residual HCl left in the TMAn.E/toluene solution. The water increments which were distilled off were titrated for HCl. The total time to remove the HCl was abou-t 4.5 hours.
After the bulk of the last wa-ter-increment was removed (for HCl-content determination), the TMAn.E/toluene solution was azeotroped further (approximately 3-4 hours) to achieve complete dryness of the system. The solution was then filtered.
To the dry TMAn.E/toluene solution was added batchwise, while keeping the temperature down to room temperature, a total of 77.03 g of _-phenylene diamine (PDA). The PDA was added "tricklewise" in 10~ increments and,after each addition, time was allowed for the PDA to completely dissolve before the next addition was made. The time between incremental additions (up to 70~ of the total addition) was about 10 minutes. This time increased to about 20 minutes for each remaining incremental addition.
Once all the PDA was added and dissolved, the reaction solution was kept at 55C for one hour.
The reaction solution was then refluxed for about 4.5 hours while removing azeotropically the water that is generated during the imidization of the amide-acid.
Once complete imidization was achieved, the toluene was distilled out at a reduced pressure. When most of the toluene was removed, the temperature of the kettle was increased to 130-140C to reduce the viscosity of the brown product and thus increase the rate of removal of residual toluene.

.
,?i... ..

The following formulations were made up from accurately weighed ingredients and admixed until homogeneous:~
Formulation I
10.0 g Polyene O (an amide-acid polyene formed from stoichiometric amounts of trimellitic anhydride acid chloride, hexamethylene diamine and hydroxy-butyl acrylate by the procedure in Example 19~
0.44 g dimercaptopropionate of N,N'-bis(2-hydroxyethyl) dimethylhydantoin 0.029 g 2,2-dimethoxy-2-phenylacetophenone 0.006 g stabilizer package Formulation J
10.0 g Polyene P (an imidized polyene formed from stoichio-metric amounts of trimellitic anhydride acid ; chloride, N,N'-bis(3-aminopropyl) dimethylhydantoin : and hydroxybutyl acrylate by the procedure of Example 19) 0.2 g 2,2-dimethoxy-2-phenylacetophenone 0.06 g stabilizer package Formulation ~ .
10.0 g Polyene Q (an amide-acid polyene formed.from stoichiometric amounts of trimellitic anhydride acid chloride, N,N'~bis(3-aminopropyl) dimethyl-hydantoin and hydroxybutyl acrylate by the procedure of Example 19) 1.5 g trimethylolpropane tris(~-mercaptopropionate) 0.23 g 2,2-dimethoxy-2-phenylacetophenone 0.06 g stabilizer package il ~''~21~3S

The formulationsof Example 23 were coated to a thickness of 2-5 mils onto various substrates and exposed under atmospheric condi.tions,unless otherwise stated, to an Addalux U.V. lamp whose major spectral lines were all above 2400 Angstroms whereby the surface intensity of the radiation on the coating was 20 milliwatts/cm2.
In some cases the U.V. cure was followed by a heating step. The results are shown in Table II.

r ~a .~
~ ~ ~ ~a ~a ~a ~a ~a ~a ~ ~a .. ~J u,~ I h ~I h U~ O O O
U~
~ O ~: ~
rl r-l r-l U~ r~ r~
a) ~a ~a ~a c) ~ ra ~a ~a ra ~a o o~ o t) ~ o o o o o ~a o o o x x o o o o o ~ . ~ ~ ~ ~ a ~ ~
~; rl ~ O O O O O O O
E~ O O O
,¢ . ~
a) O r~

a h ~ h H rl ~ ~rl rl rl rl rl -rl rl ~rl H ~Ll (~1 Z rd 11~
1~ ~
~ C) _ ~4~
E~ P Q)-~
~ ~ ~ O O O U~
o o,~ ,~ ~ ~ ~ ~ ~ ,~
X ,~
E~
,~
,~a ~ o ,1:: . rl rl 1~, 0 ~1 U~
Or~
~ O
5~ ~ rl ~ r~
E~ u~ r~
~ rd ~ ~ Q
,~ ~ O O rl r~ r~
u~ ~ ~ ~ O`U t) .

H
H 1~1 H 1~ ~ i X .
30 ~
h Z:~35 To a 3-necked, 300 ml round bo-ttomed flask equipped with stirrer, addition funnel and an air sparge tube (gas disperse system) was added 59 g of glacial acetic acid, 71.72 g of trimellitic anhydride acid chloride, 0.596 g of 2,6-di-t-butyl-4-methylphenol and 0.060 g of methyl hydroquinone. After dissolution of the solids, the flask was immersed into an ice/water bath. A mixture of 37.00 g of triethyl amine (TEA) and ~3.27 g of hydroxy-ethyl methacrylate (HEMA) was then added dropwise to thecold solution while continuously purging the reac-tion mixture with air. Once the EIEMA/TEA mixture was added (addition took 70 minutes), the cloudy reaction mixture was left standing for 10 minutes. 18.15 g of solid m-phenylene diamine was then added slowly while keeping the reaction mixture at about 35C. The disappearance of the anhydride group was followed by infrared spectroscopy.
Once all the anhydride reacted with the amine, the reaction mixture-was dropped into a large excess of vigorously agitated water. The viscous gummy product was then dissolved in acetone and the solution was dried with anhydrous magnesium sulfate and treated with decolorizing carbon. To the clear slightly brown solution was added 0.596 g of 2,6-di-t-butyl-4-methylphenol and 0.060 g of methyl hydroquinone. The bulk of the acetone was then evaporated off slowly at near-room temperature. Residual acetone was evaporated off at 80C for 0.5 hours.
Interpretation of the IR spectrum of the final cloudy tan waxy material showed that the material contained primarily the compound of the formula:

- 5~ --21~5i o C~12=CCO (CH2) 4OC/~ \NH~

CH 3 ~\ "
.... . .. . IiOC C(Ci~2) 4OCC, CH2 hereinafter referred to as Polyene R, and small amounts of the cyclized imide of the compound above.
EXAMPLE~ 2 6 A portion of the compound made and described under Example 25 was heated to 150C for 0.5 hours to effect imidization of Polyene R.
Interpretation of the IR spectrum of the final tan glassy solid showed that the material contained primarily the compound of the formula:
' O
o~LC\ _~
...... H.2 C,C(CH2) 4OC " N~ ~
,~ :,. ; CH 3 ~C V--C O ( CH 2 ) 4 OCC~ CH 2 referred to hereinafter as Polyene S, and small amounts of the uncyclized amide-acid.
Example 2 7 ` ~ A 24 AWG copper wire was coated with bullet dies (two passes, 1.8 mil total build) using Formulation I.
After each pass the coating was cured, for 4 seconds, with a medium pressure mercury lamp. The resulting coating was hard, flexible and well adhered to the copper wire. The coated wire whenisubjected to standard NEMA tests had a heat shock of 2xpass (20% stretched) ~- 55 -L3~5 and a cut through of 350C.

Claims (52)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. An amide-acid polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a primary diamine has reacted to form amide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k.and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10.
2. An imide-containing polyene of the formula:
wherein ? denotes isomerism, R is a divalent organic moiety remaining after a secondary diamide has reacted with adjacent carboxylic acid groups to form imide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;

Y is a member of the group consisting of -CR"=CH2, -O-(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10.
3. A method of preparing an amide-acid polyene which comprises reacting in an inert atmosphere under anhydrous conditions in substantially stoichiometric amounts (1) at least one primary diamine having the structural formula: H2N-R-NH2 wherein R is a divalent organic moiety containing at least 2 carbon atoms, the two amino groups of said diamine each attached to separate carbon atoms of said divalent organic moiety with (2) at least one anhydride-containing member of the group consisting of and wherein R' is an aromatic residue attached to at least 3 carboxyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue and X is a halide radical and (3) an ethylenically unsaturated alcohol of the formula: wherein A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; and m and d are 1 to 10 at a temperature in the range 20 to 100°C in an organic solvent for the amide-acid polyene product.
4. The method according to Claim 3 wherein the anhydride-containing member is a dianhydride.
5. The method according to Claim 3 wherein the anhydride-containing member is an acid anhydride.
6. The method according to Claim 3 wherein the anhydride-containing member is an anhydride acid halide and the halide formed from reacting the anhydride acid halide with the ethylenically unsaturated alcohol is removed prior to reaction with the primary diamine.
7. The process of imidizing the amide-acid polyene of Claim 1 which comprises heating said polyene at a temperature in the range 50-250°C for a time sufficient to cause imidization.
8. The process according to Claim 7 wherein the imidization is carried out in an inert solvent for the amide-acid polyene at a temperature in the range 50-150°C.
9. A photocurable composition comprising (A) an amide-acid containing polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a primary diamine has reacted to form amide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10, (B) a polythiol having a molecular weight in the range from about 94 to 20,000 of the general formula: R8-(SH)n where n is at least 2 and R8 is a polyvalent organic moiety, the sum of m and n being greater than 3, the polyene/polythiol mole ratio being in the range 0.2 to 8.0:1, respectively, and (C) a photocuring rate accelerator.
10. A photocurable composition comprising (A) an imide-containing polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a secondary diamide has reacted with adjacent carboxylic acid groups to form imide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10, (B) a polythiol having a molecular weight in the range from about 94 to 20,000 of the general formula: R8-(SH)n where n is at least 2 and R8 is a polyvalent organic moiety, the sum of m and n being greater than 3, the polyene/polythiol mole ratio being in the range 0.2 to 8.0:1, respectively, and (C) a photocuring rate accelerator.
11. The process of forming a solid cured amide-acid containing polythioether which comprises admixing (A) a polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a primary diamine has reacted to form amide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10, (B) a polythiol having a molecular weight in the range from about 94 to 20,000 of the general formula: R8-(SH)n where n is at least 2 and R8 is a polyvalent organic moiety, the sum of m and n being greater than 3, the polyene/polythiol mole ratio being in the range 0.2 to 8.0:1, respectively, and (C) a photocuring rate accelerator and, thereafter, exposing the mixture to U.V. radiation.
12. The process of forming a solid cured imide containing polythioether which comprises (1) admixing (A) a polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a primary diamine has reacted to form amide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1, m and d are 1 to 10 and p is 0 to 10, (B) a polythiol having a molecular weight in the range from about 94 to 20,000 of the general formula: R8-(SH)n where n is at least 2 and R8 is a polyvalent organic moiety, the sum of m and n being greater than 3, the polyene/polythiol mole ratio being in the range 0.2 to 8.0:1, respectively, and (C) a photocuring rate accelerator, then in either order (2) exposing said admixture to U.V. radiation and (3) heating the admixture at a temperature in the range 50-250°C for a time sufficient to imidize the amide-acid in the polyene.
13. The process of forming a solid cured imide containing polythioether which comprises admixing (A) a polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a primary diamine has reacted to form amide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10, (B) a polythiol having a molecular weight in the range from about 94 to 20,000 of the general formula: R8-(SH)n where n is at least 2 and R8 is a polyvalent organic moiety, the sum of m and n being greater than 3, the polyene/polythiol mole ratio being in the range 0.2 to 8.0:1, respectively, and (C) 0.01-5% by weight of (A) and (B) of a pinacol of the general formula:

wherein R1 and R3 are members independently selected from the group consisting of substituted and unsubstituted aromatic radicals, R2 and R4 are members independently selected from the group consisting of substituted and unsubstituted aliphatic and aromatic radicals and X and Y are members independently selected from the group consisting of hydroxyl, alkoxy and aryloxy and, thereafter, heating the admixture in the range 50-250°C.
14. The process of forming a solid cured imide containing polythioether which comprises admixing (A) an imide containing polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety, remaining after a secondary diamide has reacted with adjacent carboxylic acid groups to form imide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"-CH2, -O-(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10, (B) a polythiol having a molecular weight in the range from about 94 to 20,000 of the general formula: R8-(SH)n where n is at least 2 and R8 is a polyvalent organic moiety, the sum of m and n being great than 3, the polyene/polythiol mole ratio being in the range 0.2 to 8.0:1, respectively, and (C) a photocuring rate accelerator and, thereafter, exposing the mixture to U.V. radiation.
15. The process of forming a solid cured imide containing polythioether which comprises admixing (A) a polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a secondary diamide has reacted with adjacent carboxylic acid groups to form imide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"-CH2, -O-(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10, (B) a polythiol having a molecular weight in the range from about 94 to 20,000 of the general formula: R8-(SH)n where n is at least 2 and R8 is a polyvalent organic moiety, the sum of m and n being greater than 3, the polyene/polythiol mole ratio being in the range 0.2 to 8.0:1, respectively, and (C) 0.01-5% by weight of (A) and (B) of a pinacol of the general formula:

wherein R1 and R3 are members independently selected from the group consisting of substituted and unsubstituted aromatic radicals, R2 and R4 are members independently selected from the group consisting of substituted and unsubstituted aliphatic and aromatic radicals and X and Y are members independently selected from the group consisting of hydroxyl, alkoxy and aryloxy and, thereafter, heating the admixture in the range 50-250°C.
16. A photopolymerizable composition comprising (A) an imide-containing polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a secondary diamide has reacted with adjacent carboxylic acid groups to form imide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10; and (B) a photocuring rate accelerator.
17. An article comprising the composition of Claim 9 as a coating on a substrate.
18. The article according to Claim 17 wherein the substrate is an electrical conductor.
19. An article comprising the composition of Claim 10 as a coating on a substrate
20. The article of Claim 19 wherein the substrate is an electrical conductor.
21. An article comprising a cured imide containing polythioether of Claim 14 as a coating on a substrate.
22. The article according to Claim 21 wherein the substrate is an electrical conductor.
23. The article according to Claim 22 wherein the elec-trical conductor is a wire.
24. The process of coating a substrate which comprises (1) applying to a substrate a curable composition comprising (A) an amide-acid containing polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a primary diamine has reacted to form amide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-(CH2)d-CR"-CH2, -?OCH2CR"=CH2 and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10, and (B) a polythiol having a molecular weight in the range from about 94 to 20,000 of the general formula: R8-(SH)n where n is at least 2 and R8 is a polyvalent organic moiety, the sum of m and n being greater than 3, the polyene/polythiol mole ratio being in the range 0.2 to 8.0:1, respectively, then in either order (2) exposing said curable composition under ambient conditions to a free radical generator to form a solidified, cured polythioether coating on said substrate and (3) heating said cured composition in the range 50-250°C
to imidize the polyene.
25. The process according to Claim 24 wherein the curable composition contains 0.005 to 50% by weight of the polyene and polythiol of said curable composition of a photocuring rate accelerator and the free radical generator is U.V. radiation.
26. The process according to Claim 24 wherein the free radical generator is high energy ionizing radiation.
27. An article comprising the cured composition of claim 24 as a coating on a substrate.
28. The article of claim 27 wherein the substrate is an electrical conductor.
29. A process for forming a continuous flexible adherent cured coating on the surface of an electrical conductor selected from the group consisting of wire and cable which comprises (1) immersing said electrical conductor in a bath of a liquid radiation curable composition comprising (A) an amide-acid containing polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a primary diamine has reacted to form amide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group cons sting of -CR"=CH2, -O-(CH2)d-CR"-CH2, -?OCH2CR"=CH2 and O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10, (B) a polythiol having a molecular weight in the range from about 94 to 20,000 of the general formula: R8-(SH)n where n is at least 2 and R8 is a polyvalent organic moiety, the sum of m and n being greater than 3, the polyene/polythiol mole ratio being in the range 0.2 to 8.0:1, respectively, and (C) a photocuring rate accelerator, thus coating said electrical conductor with said composition, (2) passing said coated electrical conductor through a die, then in either order (3) exposing said coated electrical conductor to U.V. radiation for a time sufficient to cure said coating on said electrical conductor under ambient conditions and (4) heating said coated electrical conductor in the range 50-250°C to imidize the polyene.
30. A photopolymerizable composition comprising (A) an amide-acid containing polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a primary diamine has reacted to form amide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; and m and d are 1 to 10 and p is 0 to 10, and (B) a photocuring rate accelerator.
31. The process of coating a substrate which comprises applying to a substrate a curable composition comprising (A) an amide-acid containing polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a primary diamine has reacted to form amide linkages;

R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-(CH2)d-CR"=CH2, -?OCH2CR"=CH2 and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10, and (B) a polythiol having a molecular weight in the range from about 94 to 20,000 of the general formula: R8-(SH)n where n is at least 2 and R8 is a polyvalent organic moiety, the sum of m and n being greater than 3, the polyene/polythiol mole ratio being in the range 0.2 to 8.0:1, respectively, and there-after exposing said curable composition under ambient conditions to a free radical generator to form a solidified, cured polythioether coating on said substrate.
32. The process according to Claim 31 wherein the curable composition contains 0.005 to 50% by weight of the polyene and polythiol of said curable composition of a photocuring rate accelerator and the free radical generator is U.V. radiation.
33. The process according to Claim 31 wherein the free radical generator is high energy ionizing radiation.
34. A process for forming a continuous flexible adherent cured coating on the surface of an electrical conductor selected from the group consisting of wire and cable which comprises immersing said electrical conductor in a bath of a liquid radi-ation curable composition comprising (A) an amide-acid containing polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a primary diamine has reacted to form amide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-(CH2)d-CR"=CH2, -?OCH2CR"=CH2 and O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10, and (B) a polythiol having a molecular weight in the range from about 94 to 20,000 of the general formula: R8-(SH)n where n is at least 2 and R8 is a polyvalent organic moiety, the sum of m and n being greater than 3, the polyene/polythiol mole ratio being in the range 0.2 to 8.0:1, respectively, and thereafter exposing said curable composition under ambient conditions to a free radical generator to form a solidified, cured polythioether coating on said substrate.
35. The process according to Claim 34 wherein the curable composition contains 0.005 to 50% by weight of the polyene and polythiol of said curable composition of a photocuring rate accelerator and the free radical generator is U.V. radiation.
36. The process according to Claim 34 wherein the free radical generator is high energy ionizing radiation.
37. The process of coating a substrate which comprises applying to a substrate a polymerizable composition comprising (A) an amide-acid containing polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a primary diamine has reacted to form amide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10 and exposing said compositions under ambient conditions to a free radical generator to form a solidified coating on said substrate.
38. The process according to Claim 37 wherein the compos tions contains 0.005 to 50% by weight of the polyene of a photocuring rate accelerator and the free radical generator is U.V. radiation.
39. The process according to Claim 37 wherein the free radical generator is high energy ionizing radiation.
40. A process for forming a continuous flexible adherent coating on the surface of an electrical conductor selected from the group consisting of wire and cable which comprises immersing said electrical conductor in a bath of a liquid polymerizable composition comprising (A) an amide-acid containing polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a primary diamine has reacted to form amide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10, exposing said composition under ambient conditions to a free radical generator to form a solidified coating on said substrate.
41. The process according to Claim 40 wherein the composition contains 0.005 to 50% by weight of the polyene of a photocuring rate accelerator and the free radical generator is U.V. radiation.
42. The process according to Claim 40 wherein the free radical generator is high energy ionizing radiation.
43. The process of coating a substrate which comprises applying to a substrate a polymerizable composition comprising (A) an amide-acid containing polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a primary diamine has reacted to form amide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10, and then in either order (2) exposing said curable composition under ambient conditions to a free radical generator to form a solidified, adherent coating on said substrate and (3) heating said cured composition in the range 50-250°C to imidize the polyene.
44. The process according to Claim 43 wherein the compos-ition contains 0.005 to 50% by weight of the polyene of a photocuring rate accelerator and the free radical generator is U.V. radiation.
45. The process according to Claim 43 wherein the free radical generator is high energy ionizing radiation.
46. A process for forming a continuous flexible adherent coating on the surface of an electrical conductor selected from the group consisting of wire and cable which comprises immersing said electrical conductor in a bath of a liquid photopolymerizable composition comprising (A) an amide-acid containing polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a primary diamine has reacted to form amide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10, and (B) a photocuring rate accelerator, thus coating said electrical conductor with said composition, (2) passing said coated electrical conductor through a die, then in either order (3) exposing said coated electrical conductor to U.V. radiation for a time sufficient to photopolymerize said coating on said electrical conductor under ambient conditions and (4) heating said coated electrical conductor in the range 50-250°C to imidize the polyene.
47. The process of coating a substrate which comprises (1) applying to a substrate a curable composition comprising (A) an amide-acid containing polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a primary diamine has reacted to form amide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;

A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-(CH2)d-CR"=CH2, -?OCH2CR"=CH2 and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10, and (B) a polythiol having a molecular weight in the range from about 94 to 20,000 of the general formula: R8-(SH)n where n is at least 2 and R8 is a polyvalent organic moiety, the sum of m and n being greater than 3, the polyene/polythiol mole ratio being in the range 0.2 to 8.0:1, respectively, and thereafter (2) exposing said curable composition under ambient conditions to a free radical generator to form a solidified, cured imide-containing polythioether coating on said substrate.
48. The process according to Claim 47 wherein the curable composition contains 0.005 to 50% by weight of the polyene and polythiol of said curable composition of a photocuring rate accelerator and the free radical generator is U.V. radiation.
49. The process according to Claim 47 wherein the free radical generator is high energy ionizing radiation.
50. A process for forming a continuous flexible adherent cured coating on the surface of an electrical conductor selected from the group consisting of wire and cable which comprises (1) immersing said electrical conductor in a bath of a liquid radiation curable composition comprising (A) an imide containing polyene of the formula:

wherein ? denotes isomerism, R is a divalent organic moiety remaining after a secondary diamide has reacted with adjacent carboxylic acid groups to form imide linkages;
R' is an aromatic residue attached to at least 3 carbonyl groups at least two of which groups are attached to adjacent carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are 1 to 10 and p is 0 to 10 (B) a polythiol having a molecular weight in the range from about 94 to 20,000 of the general formula: R8-(SH)n where n is at least 2 and R8 is a polyvalent organic moiety, the sum of m and n being greater than 3, the polyene/polythiol mole ratio being in the range 0.2 to 8.0:1, respectively, thus coating said electrical conductor with said composition, (2) passing said coated electrical conductor through a die, and thereafter (3) exposing said coated electrical conductor to radiation having an energy greater than 3 electron volts for a time sufficient to cure said coating on said electrical conductor.
51. The process according to Claim 50 wherein the curable composition contains 0.005 to 50% by weight of the polyene and polythiol of said curable-composition of a photoinitiator and the radiation is U.V. radiation.
52. The process according to Claim 50 wherein the radiation is high energy ionizing radiation.
CA293,767A 1976-12-22 1977-12-22 Photocurable imidizable polyene-polythiol compositions Expired CA1092135A (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US05/753,350 US4103016A (en) 1976-01-19 1976-12-22 Antiinflammatory imidazothiazoles and thiazolopyrimidines
US753,350 1976-12-22
US830,225 1977-09-02
US05/830,225 US4117196A (en) 1976-12-23 1977-09-02 Photocurable imidizable polyene-polythiol compositions
US05/851,680 US4132812A (en) 1977-09-02 1977-11-15 Photocurable imidizable polyene-polythiol compositions
US851,680 1977-11-15

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