CA1118550A - Heat curable composition containing a dialkylhydroxy arylsulfonium salt and an organic oxidant - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Macbecin derivatives are produced by bringing Macbecins into contact with a microorganism, or its processed matter, of the genus Streptomyces or Nocardia. The Macbecin derivatives are useful as antibacterial, antifungal or antiprotozoal agents.

Description

~185SO RD-10800 The present invention relates to heat curable compositions comprising a cationically polymerizable organic material, for example, an epoxy resin, a dialkyl hydroxy-arylsulfonium salt and an organic oxidant.
As shown in U.S. Patent No. ~ Y~ , issued ~ SJ~ , Crivello and assigned to the same assignee as the present invention, organic resins, for example, epoxy resins can be thermally cured by using an effective amount of an aromatic onium salt such as an aryl iodonium salt and a reducing agent, for example, a thiophenol.
The present invention is based on the discovery that such organic resin also can be thermally cured with an organic oxidant, such as an organic peroxide in combination with an :~
effective amount of certain hydroxyaryldialkyl sulfonium salts, for example, OH

3 l 3 \[~~/ ' f\ : .

dimethyl-~-hydroxy-3, 5-dimethylphenyl sulfonium hexafluoroarsenate.
There is provided by the present invention, heat curable compositions comprising (a) a cationically polymerizable organic material, (b) an effective amount of a thermal curing agent consisting essentially of an organic oxidant and a dialkyl hydroxy aryl sulfonium salt.
Included by the dialkylhydroxyarylsulfonium salts which can be used in the practice of the present invention are compounds having the formula, - 1- ~

(1) [R (R )a Sl [Y]
where R is a C(6 20) aromatic radical having from 1 to 3 nuclearly bonded hydroxy radicals, Rl can be the same or different C(l 8) alkyl radical or an alkylene radical capable of forming a cycloaliphatic or heterocyclic ring, Y is a non-nucleophilic anion, a is an integer equal to 1 or 2, and when Rl is alkyl, a is 2, and when Rl is alkylene, a is 1.
Radicals included by R of formula (1) are, for example, OH OH

dO ~ _ , ~ Od ~ , OH HO H3,C OH C,H3 C33 ~ C~3 H5C6 ~ C6d5 ~ , etc.

R radicals include CH3-~ -C4Hg-~ C2H5-, CH30-, (CH3)3C-, 6 5CH2 ~ (CH2)4 , -(CH2)5-, -cH2-cH2-o-cH2-cH2-~ ;
-CH2-CH2-S-CH2-CH2-, etc Preferably, the salts included by formula (1), are

(2) ~0 ~ 5~ ~ ~MQd ~

where Rl is as previously defined, M is a metal or a metalloid, Q is a halogen selected from fluorine and chlorine, d is an integer equal to 4 to 6 inclusive, and R -R are monovalent radicals selected from hydrogen, C(l 8) alkyl, C(l 8) alkoxy, nitro, chloro, etc.
Dialkyl hydroxyphenylsulfonium salts included by . ~ . :

11~8SS~ -formulas (1) and (2) are, OH OH +~CH
CH~ CH3~ ASF6 ~S~ PF6- ~ CH3 \ , OH OH

[~OH
~S~ SbF6 , ~S\ BF4 OH OH

CH3 ~CH36_ ~ CH3O~ AsF6 C6H5-CH2~ CH2-C6H5 CH3 CH3 OH OH
(CH3) 3C~ C (CH3) 3 CH3 ~ CH3 AsF6 , ~ 1 AsF6 ., , , ,, . . . . ; ;., -OH OH OH

~ CH2 ~ ~ ~H30 ~ OC 3 PF6-S S 6 ' S+ 6 ' Methods for making some of the dialkyl hydroxy aryl sulfonium salts of formulas (1) and (2) are shown in U.S. Patents No.4,058,400 and 4,058,401 - issued November 15, 1977 - Crivello, and U.S. Patent No. 4,161,478 - issued July 17, 1979 - Crivello and U.S. Patent No. ~ ~ bi 9 issued ~G Q~lC~ q,~9go - Crivello~ A¦
Organic oxidants which can be used in the practice of the invention incombination with the dialkylhydroxy arylsulfonium salts of formulas 1 and 2 to effect the cure of the cationically polymerizable organic material are, for example, organic peroxides such as ketone peroxides, peroxy acids, dibasic acid peroxides, aldehyde peroxides, alkyl peroxides, hydroperoxides, alkyl peroxyesters, diperoxide derivatives, for example, t-butyl peroxypivalate, 2, 4-dichlorobenzoyl peroxide, caprylyl peroxide, lauroyl peroxide, decanoyl peroxide, propionyl peroxide, acetyl peroxide, t-butyl peroxyisobutyrate, p-chlorobenzoyl peroxide, benzoyl peroxide, hydroxyheptyl peroxide, cyclohexanone peroxides, 2,5-dimethylhexyl-2,5-di (peroxybenzoate), di-t-butyl diperphthalate, t-butyl peracetate, t-butyl-perbenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butyl-peroxy)hexane, t-butyl hydroperoxide, di-t-butyl peroxide, methyl ethyl ketone peroxide, p-methane hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexyl-2, 5-dihydroperoxide, t-butyl-hydroperoxide, peracetic acid, ~118550 perbenzoic acid, m-chloroper-benzoic acid, etc.
In addition to organic peroxides, organic oxidants which also can be used in the practice of the invention include azo-bis alkyl nitriles and other azo zompounds, such :
as CH -C-N=N-C-CH3 , CH3-C-N=N ~ , ~ CN C

, 3 , 3 (C6H5)3C N N C(C6H5)3 ~ 3 , , 3 ,3 ,3 C H5-C-N=N-C-C2H5 , etc.;
CN CN

quinones, such as O O CH CH
Cl ~ N Cl~ ~ ~O ~ ~ -:
)~. \ ' ~ ' S~= ' ` :' Cl ¦ ¦ CN Cl I Cl O Cl CH3 C 3 Cl ~ Cl Cl ~ Cl , etc.;

~ 35SV RD-10~00 iodoso aromatic compounds, such as iodosobenzene, 4-nitroiodoso-benzene, iodosobenzene diacetate, 4,chloroiodosobenzene, 4-meth-oxyiodosobenzene, 4-iodosobiphenyl, 2-chloroiodosobenzene di-acetate, etc.-Cationically polymerizable organic materials whichcan be used to make the heat curable compositions of the present invention include epoxy resins, thermosetting organic condensation resins of formaldehyde, vinyl organic prepolymers, cyclic ethers, etc.
The term "epoxy resin" as utilized in the descrip-tion of the cationically polymerizable compositions of the-present invention, includes any monomeric, dimeric or oligo-meric or polymeric epoxy material containing one or a plural-ity of epoxy functional groups. For example, those resins which result from the reaction of bisphenol-A (4,4'-isopro-pylidenedipheno~) and epi_hlorohydrin, or by the reaction^of low molecular weight phenol formaldehyde resin (No~olak resin) with epichlorohydrin, can be used alone or in combination with an epoxy containing compound as a reactive diluent. Such diluents as phenyl glycidyl ether, 4-vinylcyclohexene dioxide, limonene dioxide, 1,2-cyclohexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide, allyl glycidyl ether, etc., may be added as viscosity modifying agents.
In addition, the range of these compounds can be extended to include polymeric materials containing terminal or pendant epoxy groups. Examples of these compounds are vinyl copolymers containing glycidyl acrylate or methàcrylate as one of the comonomers. Other classes of epoxy containing polymers amenable to cure using the above catalysts are epoxy-:

~ 550 RD-10800 siloxane resins, epoxy-polyurethanes and epoxy-polyesters.
Such polymers usually have epoxy functional groups at the ends of their chains. Epoxy-siloxane resins and method for making are more particularly shown by E.P. Plueddemann and G. Fanger, J.Am. Chem. Soc. 802632-5 (1959). AS described in the literature, epoxy resins can also be modified in a number of standard ways such as reaction with amines, carboxylic acids, thiols, phenols, alcohols, etc., as shown in U.S. Patent No.
2,935,488 - issued May 3, 1960 - Phillips et al; U.S. Patent 10 No. 3,235,620 - issued February 15, 1966 - Phillips et al;
U.S. Patent No. 3,369,055 - issued February 13, 1968 - :~
Salyer et al; U.S. Patent No. 3,379,653 - issued April 23, 1968 - Ernst et al; U.S. Patent No. 3,398, 211 - issued August 20, 1968 - Ramos; U.S. Patent 3,403,199 - issued September 24, 1968 - Ramos; U.S. Patent No. 3, 563,840 - issued February 16, 1971 - Stine; U.S. Patent No. 3,567,797 - issued March 2, 1971 - Mango et al; U.S. Patent No. 3,677,995 - `
issued July 18, 1972 - Earing; etc. Further coreactants which -~
can be used with epoxy resins are hydroxy terminated 20 flexibilizers such as hydroxyl terminated polyethers, hydroxy terminated polyesters, etc., shown in the Encyclopedia of Polymer Science and Technology Vol. 6, 1967, Interscience Publishers, New York, pp. 209-271 and particularly p. 238.
Included by the thermosetting organic condensation reeins of formaldehyde which can be used in the practice of the present invention are, for example, urea type resins, such as [CH2=N-CONH2] X.H20 =NCoNH2~ XcH3cooH

, ' . ~

1118~ RD- 10 8 0 0 CH2=NCONHCH2NHCONHCH20H 2 phenol-formaldehyde type resin, such as OH
H- O-CH2 ~ CH2 OH

CH - - H

E~l OCH2--~ C ~2t where x and n are integers having a value of 1 or greater;

~ ~ ~!
N

N ~ ~ N

2\ ~ N ~ /CH20H

C4HgOCH2 /CH2H
N

N ~ N

HO-CH2 ~ ~ /CH2-H ,etc.
C4Hg-O-CH2 N CH20-C4Hg alkoxy silanes having the formula, (R o)mSi (R )n where R7 is a C(l 7) alkyl radical, R8 is selected from R7 ~ RD-10800 radicals and C(6 13) aryl radicals and halogenated derivatives, m is an integer equal to 1 to 4, n is an integer equal to 0 to 3 inclusive and m + n is equal to 4.
In addition, there can be used melamine thiourea resins, melamine, or urea aldehyde resins, cresol-formaldehyde resins and combinations with other carboxy, hydroxyl, amino and mercapto containing resins, such as polyesters, alkyds and polysulfides.
Some of the vinyl organic prepolymers which can be used to make the polymerizable compositions of the present invention are, for example, CH2=CH-O-(CH2-CH2O)n,-CH=CH2, where n' is a positive integer having a value up to about 1000 or higher; multi-functional vinylethers, such as 1,2,

3-propane trivinylether, trimethylolpropane trivinylether, prepolymers having the formula, ~ C~ _ , and CH=CH2 ., :
low molecular weight polybutadiene having a viscosity of from 200 to 10,000 centipoises at 25c, etc. Products resulting from the cure of such compositions can be used as printing inks and other applications typical of thermosetting resins.
A further categary of the organic materials which can be used to make the polymerizable compositions are cyclic ethers which are convertible to thermoplastics. Included by such cyclic ethers are, for example, oxetanes such as 3, 3-bis-chloromethyloxetane, alkoxyoxetanes as shown by U.S. Patent No. 3,673,216 - issued June 27, 1972 - Schroeter, assigned to the same assignee as the present invention;

,, _ g _ ~ S50 RD-10800 oxolanes such as tetrahydrofuran, oxepanes, oxygen containing spiro compounds, trioxane, dioxolane, etc.
In addition to cyclic ethers there are also included cyclic esters such as B-lactones, for example propiolactone, cyclic amines, such as 1, 3, 3-trimethyl-azetidine and organosilicone cyclics, for example, materials included by the formula, - I

4 R2sio~
p where R" can be the same or different monovalent organic radical such as methyl or phenyl and p is an integer equal to 3 to 8 inclusive. An example of an organosilicon cyclic is hexamethyl trisiloxane, octamethyl tetrasiloxane, etc. The products made in accordance with the present invention are high molecular weight oils and gums.
The heat curable compositions of the present invention can be made by blending the cationically polymerizable organic material with an effective amount of the thermal curing agent.
There can be used 0.1 to 10 percent by weight of the dialkyl hydroxyarylsulfonium salt based on the weight of cationically polymerizable organic material. With respect to the combination of organic oxidant and dialkylhydroxyaryl-sul~onium salt, there can be used from 1 to 100 parts of organic oxidant, per part of dialkyl hydroxy arylsulfonium salt.
The resulting curable composition can be in the form of a varnish having a viscosity of from 1 to 100,000 centipoises at 25C or a free flowing powder, depending upon the nature of the cationically polymerizable organic material.
The curable compositions can be applied to a variety of substrates by conventional means and cured to the tack-free state within 0.5 to 20 minutes, depending upon the temperature employed.
In certain instances, an organic solvent, such as nitromethane, acetonitrile, can be used to facilitate the mixing of various ingredients. The dialkyl hydroxy arylsulfonium salts can be formed in situ if desired. In addition, the curable compositions may contain inactive ingredients, such as silica, talc, clay, glass fibers, extenders, hydrated alumina, carbon fiber process aids, etc., in amounts of up to 500 parts of filler per 100 parts of cationically polymerizable organic material. The curable compositions can be applied to such substrates as metal, rubber, plastic, molded parts or films, paper, wood, glass, cloth, concrete, ceramic, etc.
Some of the applications in which the curable compositions of the present invention can be used are, for example, protective, decorative and insulating coatings, potting compounds, printing inks, sealants, adhesives, molding compounds, wire insulation, textile coatings, laminates, impregnated tapes, varnishes, etc.
In order that those skilled in the art will be better able to practice the invention, the following examples are given by way of illustration and not by way of limitation.
All parts are by weight.

A mixture of three parts of dimethyl-4-hydroxy-3,

5-dimethoxyphenyl sulfonium hexafluoroarsenate, three parts of benzoylperoxide and 94 parts of Shell Epon 828, a diglycidyl ether of bisphenol-A, was stirred and heated to 160C. The mixture gelled and hardened within 2.5 minutes.

~ S~o RD-10800 The procedure of Example 1 was repeated, except A that Celanese SU8, epoxy novolak resin was substituted for the diglycidyl ether bisphenol-A epoxy resin. The resuting heat curable composition required eight minutes to harden ;
at 120C.

A series of mixtures were prepared utilizing 100 parts of 3,4-epoxycyclohexylmethyl-3, 4-epoxy cyclohexane carboxylate, 3 parts of a hexafluoroantimonate salt of the formula, HO ~ S+~ sbF6- ' ~ -and 3 parts of various organic oxidants, The mixtures were then heated to 130C to determine gel times. The following -results were obtained:
Organic oxidant Gel Time ~;
None ~7 min.
benzoyl peroxide 1 min., 30 sec.
cumene hydroperoxide 2 min., 50 sec.

20 2,3-dichloro-5,6-dicyano-quinone 40 sec.
azo-bisisobutyronitrile 6 min. 15 sec.
lauroyl peroxide 4 min. 5 sec. -In accordance with the procedure of Example 3, heat curable mixtures were prepared utilizing 100 parts of ERL
4221 (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate), 3 parts of ;

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

~85~ RD-10800 OH

3 ~ 3 ~S+

and 3 parts of various organic oxidants. The mixtures were heated to 150C to determine when the mixtures changed from a fluid condition to the solid cured state. The following results were obtained:
Organic oxidant Gel Time None 25 min.
methylethyl ketone peroxide 11 min.
t-butyl hydroperoxide 3 min.

A mixture composed of 100 parts of 1,4-butanediol diglycidyl ether, 3 parts of t-butyl hydroperoxide and 3 parts of dimethyl-3, 5-dimethoxy-4-hydroxyphenylsulfonium hexafluoroarsenate was heated at 150C. The mixture cured to a hard crosslinked resin after 18 minutes. The same mixture free of the t-butyl hydroperoxide did not gel after it was heated for 60 minutes at 140C.

Mixtures were prepared having 100 parts of diethyleneglycol divinyl ether and 3 parts of HO

S+

There was added 3 parts of t-butyl hydroperoxide to one of the mixtures, Both mixtures were thoroughly stirred and then .
.

~ 85~ RD-10800 heated to 140C. The mixture containing the peroxide cured after 5 minutes, while the mixture free of peroxide required 15 minutes to cure to a tack-free condition.

Mixtures of lO0 parts of Methylon resin (a phenolformaldehyde resole of the General Electric Company) and 3 parts of HO
( 3)3 ~ C(CH3)3 ~+
S AsF6 (CH2)4 were thoroughly stirred. There was added 3 parts of t-butyl hydroperoxide to one of the mixtures. The mixtures were then heated at 150C. The mixture having the t-butyl hydroperoxide cured to a hard crosslinked insoluble resin.
The mixture free of the organic oxidant remained substantially unchanged.
Although the above examples are directed to only a few of the very many heat curable compositions included by the present invention, it should be understood that the present invention includes a much broader class of heat curable material as shown by the description preceding these examples.

Claims (8)

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. Heat curable compositions comprising (A) a cationically polymerizable organic material (B) an effective amount of a thermal curing agent capable of effecting the cure of the cationically polymerizable organic material and consisting essentially of an organic oxidant selected from the class consisting of organic peroxides, azo-bis-alkylnitriles, and quinones selected from the class consisting of p-chloranil and 3,3',-5,5'-tetramethyl-4,4'-diphenoquinone and a dialkyl hydroxyarylsulfonium salt having an anion of the formula MQd, where M is a metal or a metalloid, Q is a halogen selected from fluorine and chlorine, and d is an integer equal to 4 to 6 inclusive.

2. A heat curable composition in accordance with claim 1, where the cationically polymerizable organic material is an epoxy resin.

3. A heat curable composition in accordance with claim 1, where the organic oxidant is benzoyl peroxide.

4. A heat curable composition in accordance with claim 2, where the dialkyl hydroxyarylsulfonium salt is dimethyl-4-hydroxy-3,5-dimethoxyphenylsulfonium hexa-fluoroarsenate.

5. A heat curable composition in accordance with claim 1, where the cationically polymerizable organic material is a phenolformaldehyde resin.

6. A heat curable composition in accordance with claim 1, where the cationically polymerizable organic material is a diglycidyl ether of bisphenol-A.

7. A heat curable composition in accordance with claim 1, where the cationically polymerizable organic material is a divinyl ether.

8. A heat curable composition in accordance with claim 1, where the dialkylhydroxyarylsulfonium salt is dimethyl-4-hydroxy-3,5-dimethylphenylsulfonium hexafluoroantimonate.