CZ2001130A3 - Curable epoxy compositions - Google Patents

Abstract

Heat curable compositions comprising: (A) at least one compound which may be cationic polymerize: (B) at least one quaternary ammonium network; aromatic N-heterocyclic cation and non-nucleophilic anion; (C) at least one 1,1, 2,2-substituted-1,2- ethanediol and / or a derivative thereof and (D) optionally other additives; and wherein component (C) is a compound of formula I wherein R b, R 2, R 3 are independently unsubstituted phenyl or have one of the meanings defined for R4; R 4 is substituted phenyl optionally substituted with α-naphthyl or β-phenyl or optionally 1 substituted aromatic heterocyclic ring system; each R 1 and R 2 and / or R 3 and R 4 independently of the others form a group of formula II wherein each R 5 and R 6 is independently to others hydrogen or C 4 alkyl; Ry is - (CH 2) n - or -S or -O-; and n is 0, 1, 2 or 3.

Description

Thermosetting epoxy compositions

Technical field

The present invention relates to. thermosetting cationic polymerizable resin systems comprising an improved initiator composition.

BACKGROUND OF THE INVENTION

The initiation systems used for cationic polymerization are known and are often latent curing agents which provide sufficient storage stability. A significant disadvantage of these initiation systems is that, in order to achieve sufficient shelf life, they often require a relatively high temperature and a longer hardening cycle in the curing process. Thus, there is a need for initiator systems that, when added to a resin composition, allow long shelf life while being highly reactive at a relatively low cure temperature.

The present invention relates to cationic polymerizable resin systems comprising an improved redox initiation system. -—. ...............: topics. The compositions of the present invention have suitable reaction times and are sufficiently stable at room temperature. Furthermore, they are highly reactive at curing temperatures, have a short curing time, and offer properties such as casting, compression, adhesive and impregnation applications.

SUMMARY OF THE INVENTION

The cationic redox initiation system of the present invention consists of a combination of an aromatic nitrogen heterocyclic ammonium salt with selected 1,1,2,2-substituted-1,2-ethanediols and derivatives thereof, wherein the substituents at the 1- and 2-positions are selected or aryl aromatic or heterocyclic ring systems, which are defined below as compounds of formula (I). The basic principle of using a combination of an aromatic nitrogen heterocyclic ammonium salt and 1,1,2,2-tetrafenyl-1,2-ethanediols (benzopinacol) is described in EP-A-0. 066

543. At elevated temperature, benzopinacol forms free radicals. These radicals also reduce the aromatic nitrogen-containing heterocyclic ammonium salt, for example, N-methylquinolinium hexafluorophosphate, to give free H ⁺ (PF ₆ ) which is catalysed by polymerization.

According to the present invention, the selected compound of formula I which are defined by ^one further mixed with known aromatic ^r nitrogenous heterocyclic ammonium salts to form new cationic redox iniciačního.systému. Because they have benzopinacols. used in these new combinations of lower cleavage temperatures is possible for. For example, a lower temperature, cure and / or higher rate of cure can be used for the polymerization of epoxides.

The present invention is defined by the claims. It relates to thermosetting compositions which can be cured by cationic polymerization and which comprise:

(A) at least one compound,. that can. undergo cationic polymerization; '’.

(B) at least one quaternary ammonium salt of an aromatic nitrogen heterocyclic cation containing one or two nitrogen atoms and a non-nucleophilic anion;

(C) at least one 1,1,2,2-substituted-1,2-ethane-diol and / or a derivative thereof, wherein the substituents at positions 1- and 2- are selected from aryl residues or aromatic heterocyclic ring systems ; and (D) optionally further additives;

which is characterized by:

named 'component (B) is selected from the group of anions consisting BFY PF _{with' r} SbF _g 'SbF _s (OH) +, [Β (X) _p (Y) _q]', or CF ₃ (CF _{2) B} SO ₃ ··, .where. ^. p_a.Jcr. ^ 3 ^ zero-sum nehoucelé _čXsl.o ____ 1-to-4-.a-where the sum of - P a kettle and q is always 4;

each X (for p> 1) is independently of the other a halogen atom, preferably a fluorine atom or a chlorine atom or a hydroxyl group, wherein for a halogen atom p is zero. 1> 2 or-3; and for the hydroxyl group, p is zero, 1 or 2;

each Y (for q > 1) is, independently of the others, a phenyl group optionally substituted by at least two halogen atoms, preferably fluorine atoms or one or two electron withdrawing groups, preferably -CF ₃ , -OCF ₃ , nitro, cyano or Y is an aryl group with at least two aromatic rings, preferably naphthyl or biphenyl optionally substituted by one or two halogen atoms, preferably fluorine atoms or one or two electron withdrawing groups, preferably CF ₃ , -OCF ₃ , nitro or cyano; and m is zero or an integer from 1 to 17;

and said component (C) is a compound of formula I:

• · · ·

«· • · · ·

(I) wherein each R _1, R _2, and R ₃ is, independently of the others, an unsubstituted phenyl group; or has one of R ₄ ;

an unsubstituted or branched alkyl group having 1 to 12 carbon atoms; an alkoxyalkyl group containing both 1 to 8 carbon atoms in both the alkoxy moiety and the alkyl moiety; an alkyloxy group. (C až-C 12) alkylthio (C 1-C alkyl) alkylthio group. a group containing in the alkyl moiety 1 to 10; C uhlíku,, C, ky ni, Can, ky, Can,,, H halogenal 1alalal 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1ryryryryryryryryryryryry. 1 to 8 carbon atoms; aryloxy, aryl.thioskupina, benzoyloxy, -beňzoylmethylová group and / or -naphthoyloxy or R ₄ is α-naphthyl group, or a group βnaftylová L · - 2-> or 3-pyridyl, N-substituted (1-, 2- or 3-) pyridyl, α-quinolinyl, β-quinolinyl. a group, an N-substituted (α- or β-) quinolinyl group, and wherein said aryl and heterocyclic rings may be further substituted with a linear or a heterocyclic ring. a branched alkyl group having 1 to 12 carbon atoms or a halogen atom; or.

each R ₁ and R ₂ and / or R ₃ and R ₄ . independently of the others, they form a group of formula II:

• 99 ·· • · 9 · · • · ·· 9 9 9 9 9 9 ··· ·· 99 999 99 999

wherein each R _S and R ₆ independently of the other hydrogen and · · · or an alkyl group containing 1 to 4 carbon atoms; "

R ₇ is - (CH ₂ ) _n - or -S- or group ₇ Or n is 0, 1, 2 or 3; and wherein the weight ratio of component B) to. component C) is between 0.05: 1.0 to 1.0: 0.05. . ¹

The present invention also relates to a method for the thermal polymerization of thermosetting compositions which can be cured by cationic polymerization, wherein the method is characterized in that said compositions. ^{zahřívaj'í:} in the presence of the initiator combination of the components. (B) and (C) as defined above, ... _t ...

The present invention further relates to novel compounds of formula I wherein and R ₃ are independently phenyl or have one of the meanings defined for R ₂ and each of R ₂ and R ₂ is independently of the others. 2-n-butylphenyl, 2-fluorophenyl or 2,6-difluorophenyl.

The present invention further relates to novel N-benzyl-quinolinium salts comprising an N-benzyl-quinolinium cation associated with an anion of formula CF ₃ (CF ₂ ) ₃ SO 4 or an anion A ₄

6 '

Anion A4

4 ™ wherein each 'Ř ₈ ^:' is '' independently '' of the other 'linear' or branched alkyl. C 1 -C 12 -alkoxy, C 1 -C 8 -alkoxy-alkoxyalkyl-C 1 -C 8 -alkyl, C 1 -C 12 -alkyloxy-C 1 -C 12 -alkylcarbonyl, halogen or a hydroxyl group.

The compounds which can be cationic polymerized are. saturated oxygen or sulfur containing heterocyclic compounds, especially those containing 3, 4 or 5 ring members and derivatives thereof. Examples of such compounds are those containing at least one epoxy group. such as ethylene oxide, propyl enoxide, styrene oxide, phenylglycidyl ether or butylglycidyl ether; oxetane, such as trimethylene oxide, 3, 3-dimethyloxetane or 3,3-di (chloromethyl) oxetane; ..oxolany,. as. • is tetrahydrofuran or 2,3-dimethyltetrahydrofuran; cyclic acetals such as trioxane, 1,3-dioxolane or 1,3,6-trioxacyclooctane; cyclic lactones such as β-propiolactone, ε-caprolactone 4 ´ and their alkyl derivatives; thiiranes such as ethylene sulfide id. 1,2-propylene sulfide or thioepichiorhydrin; and thiethanes such as 1,3-propylene sulfide or 3,3-dimethylthioethane.

κ

Other polymerizable compounds of the invention are ethylenically unsaturated compounds that can be polymerized by a cationic mechanism. Such compounds include mono-. or diolefins such as isobutylene, 1-octene, butadiene and isoprene; styrene, allylbenzene or vinylcyclohexane; vinyl ethers (such as vinyl methyl ether, vinyl isobutyl ether or ethylene glycol, coldivinyl ether); vinyl esters such as vinyl acetate or vinyl stearate; and dihydropyran derivatives, e.g., 3,4-dihydro-2H-pyran-2-carboxylic acid esters of 2-hydroxymethyl-3,4,7-dihydro-2H-pyran.

Other polymerizable compounds of the invention. are also prepolymers of phenol-formaldehyde resins, acrylic resins, alkyd resins or polyester resins containing functional groups.

Still other polymerizable compounds of the invention are mixtures of cationic-polymerizable compounds and compounds. polymerizable free radicals, for example mixtures of epoxy resins with monomeric or oligomeric esters of acrylic or mehacrylic acid. In this case, the polymerization takes place through a cationic mechanism and a free-radical mechanism.

Among the compounds mentioned above are. of particular interest are those polymerizable compounds which are prepolymers of mono-, di- and polyepoxides and epoxy resins and which are used for the preparation of epoxy resins. This is usually accomplished by chemical curing with phenols, dicarboxylic acid anhydrides and the like, either at room temperature or with heating. When using the initiator combination of the present invention, the epoxides may be thermally cured without the addition of chemical reactants, i.e. a one-component system may be used.

• ·

The mono-, di- and polyepoxides used for this purpose may be aliphatic. cycloaliphatic or aromatic compounds. Examples of such compounds are glycidyl ethers of aliphatic or cycloaliphatic diols or polyols ^. for example ethylene glycol, propane-1,2-diol, propane-1,3-diol; butane-1,4-diol, diethylene glycol, glycerol, trimethylolpropane or < 1,4-dimethylol-cyclohexane or 2,2-bis- (4-hydroxycyclohexyl) -propane, and glycidyl ethers of di- and polyphenols, for example resorcinol; ^41- dihydroxydiphenylmethane,. 4.4 ^1-enyl -dlhydroxydif _2,2 _-propane or novolacs:

Other glycidyl compounds of technical interest are glycidyl esters of carboxylic acids, in particular di- and polycarboxylic acids. Examples are the glycidyl esters of adipic acid, phthalic acid, tetra- or hexahydrophthalic acid, isophthalic acid or terephthalic acid / or trimellitic acid. .. ..

Examples of polyepoxides that are not glycidyl compounds are vinyl cyclohexene diepoxides. or dicyclopentadiene, glycidyl-3,4-epoxycyclohexanecarboxylate or. 3 ', 4 ¹ -epoxycyklohexylmethyl-3,4-epoxycyklohexankarboxyiát, butadiene diepoxide .or Tísoprendl epoxide., Epoxřdované dérTváby riholove ^ ^ ky with ETI .ny not bb epoxidised polybutadiene.

It is also possible to use ethylenically. unsaturated epoxy compounds which can react polyfunctionally under the conditions of the invention and are thus capable of forming cross-linked resins. Examples of such compounds are allyl glycidyl ether, glycidyl ether of acrylic acid or glycidyl ether of methacrylic acid or unsaturated polyepoxides such as partially acryloyl. bonded or methacrylated epoxy resins.

• ·

β z

Preferred epoxides which can be used according to the present invention are mono-, di- and polyglycidyl ethers of mono-, di- and polyphenols, mono-, di- and polyglycidyl ethers of aliphatic and cycloaliphatic mono- and polyols, glycidyl esters of aromatic and non-aromatic mono- and polycarboxylic acids.

'·. «· ^? \

The mono-, di- and polyepoxides can be used in mixtures with each other. or. with monoepoxides or ve. A compound in mixtures with hydroxyl, which can for example be modified .fyzikální '^ připravenýcu properties pryskyřir ^ j ^ ^I iono'T'a.i ^:: ''^{'= a} ^ a ^ pdTyepoxi'dy s'ě ~ ^_' They can be pre-cured by chemical methods, for example by reaction with diols or dicarboxylic acid anhydrides. The use of these prepolymers for the manufacture of epoxy resin products may have some advantages over the use of mono-, di- and polyepoxides, for example easier storage and handling, faster processing into shaped articles, as well as the possibility of adding additives such as glass fibers or dyes prepolymers, for example, during the preparation of pregels. AND

The thermosetting compositions of the present invention further comprise component (B), i.e. at least one quaternary ammonium, an aromatic nitrogen-containing heterocyclic cation salt containing an α-ug-e-dv-α-allyl-α-γη-β-ω-τ3- τι · θηη ^ 1 ^- θΌΪ1 ^ .τη11ΐΌ ~ 3Ίί ± · ο · ηΐ · α ^__ νγ ^ · selected from the group consisting of BPf, PF _e ', SbF _s ', SbF _s (OH)', [Β (X ) _p (Y) _q 1 'or' CF ₃ (CF ₂ ) _m SO ₃ '· ,. where p, q, X, Y, and m have the meaning <=> defined above. The aromatic heterocyclic compound containing one or two nitrogen atoms carries a positive charge and represents the cationic portion of the salt which is associated with a non-nucleophilic-anion. .

Examples of aromatic heterocyclic nitrogen bases are, in particular, six-membered nitrogen-containing heterocyclic compounds such as pyridine, pyrimidine, pyridazine and pyrazine and their alkyl groups.

999 ·· ·

998 99 · 9. Or aryl derivatives, benzo and naphtho derivatives, for example pi.colin, lutidine, quinoline, isoquinoline, quinoxaline, fthalaziri, quinazoline, acridine, phenanthridine or phenanthroline,

Particularly preferred ammonium salts suitable for use. ^; j as a component. (B), the ammonium salts of cations III, IV and V are:

where

R 8 is an alkyl group having 1 to 12 carbon atoms, an arylalkyl group having a v-alkyl portion of 1 to 12 carbon atoms. (C až-C / a), C 3-Cko aalkoxyalkyl or benzoylmethyl group; · Each R _(o, R _11Z., R ₁₃ and R _{t 4} is independently of the other hydrogen, alkyl of 1 to 4 carbon atoms or a phenyl ..skupina., Or R, _o and R ,, or R _iL and R ₁₂ or R ₁₃ or R ₁₃ or R ₁₃ ^and R 14 together with the two carbon atoms to which they are attached are fused benzo, naphtho, pyridino or quinolino.

R 8 is preferably methyl, ethyl, n-propyl, isobutyl, linear or branched butyl, preferably tert-butyl, dodecyl, octadecyl, benzyl, diphenylmethyl, acetyl or benzoyl, preferably methyl, ethyl, butyl and benzyl.

• · • · n ··· ·· ·· ··· · * ···

Various basic ring systems are possible which may be. further substituted. Some of them are listed as formulas (a) to (i), where A and B are each -CH = or a nitrogen atom:

In said quaternary ammonium salt. is an aromatic heterocyclic cation associated with a non-nucleophilic anion selected from the group consisting of BFy, PFy, SbFf, SbF. (OH) ', [Β (X) _p (Y) _q ] ⁷ ' or CF ₃ (CF ₂ ) _m SO ₃ , wherein X (for p > 1) is preferably an atom. Each Y group (for q &gt; 1) independently of the other is preferably a phenyl group substituted by at least two halogen atoms, preferably fluorine atoms or once or two electron attracting groups, preferably -CF ₃ , OCF ₃ or nitro, and is. preferably pentafluorophenyl, 3,5-difluoromethylphenyl, and the like. 3,5-dinitrophenyl, paratrifluoromethyloxyphenyl ¹ or naphthyl or biphenyl substituted with one or two fluorine atoms or one or two electron withdrawing groups, preferably trifluoromethyl.

Particularly preferred compounds are [Β (X) _p (Y) _q ] 'and preferably''B (Y) ₄ ', wherein Y is a pentafluorophenyl group, a 3,5-difluoromethylphenyl group or a paratrifluoromethyloxyphenyl group. group ^

Some of these ammonium salts are known compounds and some are new. The novel compounds can be prepared analogously _e FTS manner to the known compounds ...

Particular examples of compounds of formulas III, IV and IV are: 1-methylquinolinium hexafluorophosphate, 1-methylquinolinium hexafluorantimonate, 1-methylquinolinium hexafluoroarsenate, 1-methyl- _; · Quinolinium pentafluorohydroxyantimonate, 1-methylquinolinium tetrafluoroborate, 1,2-dimethylquinolinium hexafluorophosphate, 1-ethyl. · Quinolinium hexafluorophosphate, t-butylquinolinium hexafluorophosphate; 1-benzoylmethylquinoliniumumhexafluorophosphate, 1-benzoylmethylchi,. i ·. holinium hexafluorantimonate, 1-methyl-2,3-diphenylpyridinium hexafluorophosphate 1,2-dimethyl-, 3,3'-phenylpyridinium hexafluorophenol osfát.,.,.

1-benzoylmethylpyridinium hexafluorophosphate, 1-ethoxyethylquinolinium hexafluorophosphate, 2-methylisoquinolinium hexafluorophosphate,

10-Methylacridinium hexafluorophosphate, 10-benzoylmethylacridinium hexafluorophosphate, 10-butylacridinium hexafluoroarsenate, 5-z-z-methyl-n-bromo-d-iniu-mh-ex-α-ω-ex. 1-methyl-naphthyridinium hexafluorophosphate, 1-methyl-2,3-diphenylquinoxalinium hexafluorophosphate, 1,2,3-.

trimethylquinoxalinium hexafluorophosphate, 1-methylquinazolinium. hexafluorophosphate ,. .1-methylchirtolinium hexafluorophosphate, 1,2,4,6 * · <

tetramethylpyrimidinium hexafluorophosphate, 1-methyl-2,4-diphenylpy. . rimidinium hexafluorophosphate, ‘1-methyl-3-phenylpyridazinium hexafluorophosphate, 1-methyl-2,5-diphenylpyridazinium hexafluorophosphate, 1-methylphenanthrolinium hexafluorophosphate, 5-butylphenazinium hexane. fluorophosphate, 1-methylquinoxalinium hexafluorophosphate, 1-benzoylmethylquinoxalinium hexafluorophosphate. Particularly preferred compounds. j sou. N-methylquinolinium hexafluoroantimonate, N-benzylquinolinium hexafluoroantimonate, N-benzylquinolium triflate, Nbenzylquinolinium perfluorobutanesulfonate, N-benzylquinolinium tetrakis (3,5-bis-trifluoromethyl) phenyl borate (pentafluoryl) phenyl borate). ''

The compositions of the present invention 'further comprises a compound of Formula I: ¹ ·'

which 'is as defined above.'

Each R _{1 Z} R ₂ and R ₃ independently. for the others preferably a phenyl group, or has one of the meanings defined for R ₄ and preferably has one of the meanings defined for R ₄ . Preferably, R ₄ is a phenyl group substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 1 to 4 carbon atoms in the alkoxy moiety, and an alkyl group having 1 to 4 carbon atoms. 2_atomy ... carbon,. alkyl. . (C1-C4) -alkyl, alkylcarbonyl containing i in the alkyl moiety. up to 4 carbon atoms, fluorine atom, chlorine atom, nitro group, halomethyl group, phenyl group containing from 1 to 2 carbon atoms in the alkyl moiety, phenyloxy, phenylthio, benzoyloxy, benzoylmethyl and / or or naphthoyloxy, or R ₄ is α-naphthyl or β-naphthyl, 1-, 2- or 3-pyridyl, N-substituted (1-, 2- or 3-) pyridyl, wherein the N-substituent has one of the meanings reported for R ₉ , α-quinolinyl

.......

Β-quinolinyl, N-substituted-- (α- or β-) quinolinyl, a group wherein. The N-substituent has one of the meanings given for R 13 wherein said aryl and heterocyclic rings may be further substituted by a linear or branched alkyl group having 1 to 4 carbon atoms or a fluorine atom or a chlorine atom; or each R _x and R ₂ and / or R ₃ and R ₄ independently of each other. the others form a group of formula II:

• ^(II) wherein each R ₅ and R _s independently of the other hydrogen; and R ₇ is -CH ₂ - or -S- or -O-.

In the definitions of all substituents mentioned above, it may be alkyl. straight, ‘or branched. This also applies to alkyl groups of alkoxy, alkylthio, alkoxycarbonyl and other alkyl groups. These alkyl groups preferably contain 1 to 12, more preferably 1 to 8, and more preferably 1 to 4, carbon atoms. ,

The alkyl group is typically methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl,; sec-butyl, tert-butyl and also various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl groups.

- 'I

Haloalkyl groups are typically fluoromethyl, difluromethyl, trifluoromethyl,. 15 is chloromethyl / dichloromethyl, trichloromethyl, 2,2,2, -trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl and also halogenated, preferably fluorinated or chlorinated. isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl as well as various isomeric halogenated pentyl groups, hexyl groups, heptyl groups and octyl groups. pins. The arylalkyl group preferably contains 7 to 12 carbon atoms and especially 7 to 10 carbon atoms. Arylalkyl may be, for example, benzyl, phenethyl, 3-phenylpropyl, alpha-methylbenzyl, 4-phenylbutyl, and alpha, alpha-dimethylbenzyl. .

The aryl group preferably contains 6 to 10 carbon atoms.

Aryl. a phenyl group may be, for example, a phenyl group.

pentalinyl, indenyl, naphthyl, azulinyl, and anthryl.

Alkoxy is typically methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy. sec-butyloxy and tert-butyloxy, isomers of pentyloxy, hexyloxy ,. heptyloxy groups, octyloxy groups, nonyloxy groups, decyloxy groups, undecyloxy groups and dodecyloxy groups.

Halogen means fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine; .. ·

The alkylcarbonyl group may be, for example, methyl, ethyl, tert-butyl, tert-butyl, n-pentyl, isopentyl and n-hexyloxycarbonyl.

Preferred are compounds of formula I wherein each R ₁ , R ₂ . and R _3rd .nezávisle is, on the other phenyl moiety present or has one of the meanings of R ₄ and wherein R ₄ is a phenyl group, · a substituted methyl, ethyl, group, or propyl group. butyl, fluoro, trifluoromethyl or R ₄ is α-naphthyl or β-naphthyl, 1-, 2- or 3-pyridyl, α-quinolinyl or β-quinolinyl.

The most preferred compounds of formula I are those wherein each of R ₁ , R ₂ and R ₃ is independently phenyl or has one of the meanings indicated for R ₄ and wherein R ₄ is 2-methylphenyl, 2-ethylphenyl, 2-n-butylphenyl "2-fluorophenyl", 2,6-difluorophenyl, α-naphthyl, β-naphthyl, 1-, 2- or 3-pyridyl. a group, α-quinolinyl or β-quinolinyl. Particularly preferred are compounds wherein R ₄ is 2-methylphenyl, 2-ethylphenyl, 2-t-butylphenyl, 2-fluorophenyl and 2,6-difluorophenyl. ,. '

Preferred combinations of component (B) with component (C) are benzylquinolinium hexafluorantimonate and 1,2-bis (2-methylphenyl) benzopinacol, benzylquinolinium hexafluorantimonate and 1,2-bis (2-ethylphenyl) benzopinacol, benzylquinolinium -hexafluorantimonate and 1,2-bis (2-fluorophenyl) -benzopinacol, benzylquinolinium hexafluoroantimonate and 1,2-bis (2,6-difluorophenyl) -benzopinacol and combinations. N-benzylquinolinium triflate, N-benzylquinoliniumperfluorobutane sulfonate, N-benzylquinolinium tetrakis (3,5-bis-trifluoromethyl) phenyl borate, benzylquinolinium tetrakis (pentafluorophenyl) borate with the various benzopinacols mentioned above.

Some compounds, formulas The novel compounds may be logical in known ways.

I are known and some are new. The monomer or monomer mixture is mixed with the required amount of two initiating components, i.e., Components (A) and (B). These mixtures are stable at room temperature and can be safely manipulated. In general, no additional activating component is needed before initiating the polymerization, so they are then. single component mixtures, systems that can be hardened at any time. The polymerization itself is carried out by heating the mixture to an elevated temperature. Generally, for this purpose a suitable temperature of 60 to ^200? C and especially 80-160 ° C depending on the material used and the required time 'polymerization. The shorter the required polymerization time is. he must. be. -Polymerization temperature higher. Compared to the systems described in EP-A-0 064 54.3, it is possible to operate under milder curing conditions using the initiator composition described herein; This is necessary, for example, in the processing of heat-sensitive substrates, for example paper coating, wood coating, plastic coating or conformal coating of printed circuit boards to form semiconductor devices. Other applications include encapsulation of electrical coils under conditions. energy saving, adhesive - application and production of epoxy - pressed constructions or laminate constructions.

The polymerization will often be carried out with simultaneous shaping, for example in hot presses or in molds which may be provided with an emitter. The heating may be carried out, for example, in an oven, infrared or microwave radiation.

The thermally initiated polymerization can also be combined with photopolymerization. In this case, the resin initiator composition is used

....... · ··· ··. According to the present invention first irradiated with shortwave light and then irradiated. is heated or heated first and then irradiated. Conventionally UV lamps are suitable for irradiation, and the effect of irradiation can be further enhanced by adding a catalytic amount of photosensitive. Suitable photosensitizers are, for example, organic dyes, condensed aromatic hydrocarbons, for example perylene, anthracene or thioxanthone, and derivatives thereof. are generally known as sensitizers for photochemical processes. - Advantage. of this additional LTV, the radiation is that it can be shortened in this way. time for. thermal curing or the curing temperature may decrease.

A suitable amount of the two initiating components, i.e.. quaternary, amo-. amine salts, defined as component (B). above and the compound of formula I, which is defined as component (C) above, depends on the nature of the material to be polymerized and on. required. polymerization conditions. In general, 0.1 to 10% by weight, preferably. 0.1 to 5% by weight of each of the two initiating components relative to the weight of the compound (A) to be polymerized. 1-5% by weight, preferably 1 to 2% by weight ammonium ^salt: 1 to 2 wt% of the substance forming the thermally radical, i.e. substituted benzo-pinol derivative. The weight ratio of component (B) to component (C) is preferably 0.05: 1.0 to 1.0: 0.05 and most preferably 0.5: 2.0 to 2.0: 0.5.

In addition to the polymerizable compounds and initiator compositions, the composition may also contain other additives commonly used in plastics and resin technology in amounts commonly used in the art. Examples of such additives include. resin extenders, fillers, pigments, dyes, glass fibers or other fibers; stabilizers such as antioxidants or light stabilizers, flame retardants, antistatic agents, blowing agents and / or leveling agents.

········· ··· · · · · · ···

-. . W - ~. - · -ιζ · - * - · '·. ··· e. * Λ Λ - Λ «

2_ ··· ·· ·· ··· · · ··

These additives may be mixed with the polymerizable compounds simultaneously with or independently of the initiating components, in any order. Depending on the consistency, the compositions of the invention are solid or liquid or are highly viscous liquids. For use as a paint, a spreadable or sprayable consistency will be preferred. For use as casting or laminating resins, a castable consistency will be preferred. For use as a composition, for compression a solid consistency will be preferred. · - · <

The final properties of the products (cured) from the compositions of the invention are as good as those cured by conventional methods and are used, for example, to protect surfaces such as adhesives, as electrical insulating compositions and in the manufacture of laminates and moldings or foam products. The choice of polymerizable compounds depends on the intended use. Mixtures of cationically curable compounds can be used to achieve the specific properties of the cured resin. They may be mixtures of compounds of the same chemical type, for example two different polyepoxides or one polyepoxide and monoepoxide or mixtures of compounds of different types, for example a mixture of polyepoxides and tetrahydrofuran or caprolactone.

The invention is further illustrated by examples in which parts and percentages are by weight.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Synthesis of substituted pininacols

The synthesis of the substituted pinin-free polyols is accomplished by the benzopinacol condensation reaction described in Koichi Tanaka, Satoshi Kishigami and Fumio Toda, Journal of Organic Che20.

Master, 55, 2981-2983, (1190), with minor modifications in some cases, which are indicated by the note in Table 1. The starting phenophenones are obtained from Aldrich, Fluka or Lancaster or synthesized according to literature procedures (see notes .. in Table 1). The reaction scheme is as follows: . '

A stirred mixture of 0.015 mol of ortho substituted benzophenone and a mixture of 50 ml of tetrahydrofuran and water (1 / l by volume) was added with 10 g (0.15 mol) of zinc powder and 2 g (0.015 mol) of chloride / zinc chloride. The mixture was stirred and heated under nitrogen at 45-50 ° C for 6-8 hours. The reaction is monitored by TLC on silica gel. When all the starting material (benzophenone) disappears, the reaction is complete. the mixture was evaporated under reduced pressure on a rotary evaporator. Dilute the residue with 25 ml of water.

and filtered. The filtrate (cake) is washed twice with 20 ml of a 1% hydrochloric acid solution and then with 25 ml of water. - Finally, the cake is extracted three times with 50 ml of chloroform. The chloroform extract was dried over anhydrous sodium sulfate and evaporated to give benzopinacol. Yields and analysis results are shown in Table .1. All benzopinacols have IR absorption at about 3400 to about 30000. 3500 cm ^'1. which is characteristic of the OH group is not present and the peak at 1650 to 1700 cm ^1, which matches a characteristic of the keto group.

«*» ·· · ·· ·· 9 9 9 9 ·····

9 9 9 9 9 9 9 'Table 1

Ex. C. CAS c. R . Ri Rl Yield ¹ H NMR ť.t. Noc: 2 ° C 1 424-79-3 F H H 75 6.8-7.3 (m, 16H, Ar-H); 8.05 (m, 2H, Ar-H); 175-77. 2 95950- 06-4 Cl H H 45 6.72 (m, 4H, Ar-H); 7-7.3 (m, 12H, Ar-H); 8.2 (m, 2H, Ar-H); 71-73 ¹ 3 - 20002- 32-8 . Me H , H - 40 1.2 (6H, Ar-CH3), 6.65 (m, 4H, Ar- H), 6.88-7.28 (m, 12H, Ar-H), 7.92 (m, 2, H, Ar-H) 145-47 ¹ . 4 52056- 31-2 ,About me . H H .. 33 3.24 (s, 3H, _OCH3) '3.39 (s ,, 3H, OCH), 6,65-7, .52 (m, 16H, Ar-H), 8.1 (m, 2H, Ar-H). .165-67 5 new - . F, • F · H . 75. 6.25 (m, 2H, Ar-H); 6.6-7.5 (m, · 16H, Ar-H); 130-35 6 Beil. , III ^; Vol. 6 page 5940. Et  , H 'H 20 May 0.8 (t, 6H, -CH3CH3),. 2.2-2.6 (m, 4H, -CH ₂ CH _3), 6.62 (m, 4H, Ar-H), 6.8-7.0 (m, 2H, Ar-H), 7 0-7.4 (m, 12H, Ar-H); 7.9-8.0 (m, 2H, Ar-H) 133-37 ^{2 3} ' ⁴ ' ⁵ 7 new n-Bu H H 30 0. 68 (t, 6H, -CH ₃ ), 0.8-1.6 (m, 8H, -CH ₂ CH ₃ -), 2.2-2.5 (m, 4H, Ar-CH ₂ ) 6.58-6.65 (m, 4H, 1H), 6.8-7.0 (m, 2H, Ar-H), 7.07.4 (m, 10H, 1H-H), 7 9-8, Q (m, 2H, Ar-H) 128-30 · ⁴ ' ⁶

.Comment:

CÁSč. = number in Chemical Abstracts. '

1 .. In the example. 2 and 3, the compounds are purified by column chromatography. on silica gel eluting with hexane / ethyl acetate (1: 1, v / v). No further purification is performed in any other case. - ~ 1 ^:;

2. The starting material for Example 5 was prepared according to the procedure described in J. Am. Chem. Soc., Page 1601.,. (1945).

3. 2-n-Butylbenzophenone (starting material for Example 8) was prepared according to the method described in Arzn. Forschung, 25, page 14 (1975). '.

4. In the case of Examples 7 and 8, in addition to zinc and zinc chloride, 2 g (0.015 mol) of copper chloride are also added in the condensation reaction.

5. In the case of Example 7, the processing method is modified.

The methanol extract is evaporated on a rotary evaporator under vacuum 20

• ·· • · 9 · » • · B B • ·· (B) * · • · • · ·· 99 ·· ··· ·· 99

mm to give a gum which was triturated with hexane to give a solid. It is filtered and dried ..

6. In Example 8, the heating time is extended to 30 hours and after usual processing the cake is extracted with ethyl acetate. After evaporation of ethyl acetate. extract. to give the desired benzopine. col.

Example 2 a) Synthesis of N-benzylquinolinium salts, General Preparation Method

The synthesis of the N-benzylquinolinium salts of the present invention. Climbing is carried out according to the procedures that are. known to those skilled in the art, i.e. by quaternizing the quinoline with benzyl bromide and then by exchanging the bromide anion with the desired anion. , ontěm. Anionty Ά.-Α. are commercially available from various suppliers (e.g., Fluka).

-! ¹

The following N-benzylquinoline salts were investigated:

Anion A4

and.

cation cation 'cation cation

K with SbF _s (Anion Aj, CAS No 142860-23-9 K with CP ₃ SO ₃ '(Anion A ₂ ), CAS No 190078-47-8 K with CF ₃ (CF ₂ ) ₃ SO (Anion A ₃ ), new compound K with anion A ₄ , new compound ·

• ·

b) Influence of substituents on polymerization temperature. - Monitoring procedure in measuring the effect of benzopinacol substituents on. the temperature of the cationic curing of the epoxides

To about 8 g of the epoxy compound was added 0.5 mol% (relative to the epoxy compound) of the N-benzylquinolinium salt, and 1.0. mole% (relative to the epoxy compound) of the corresponding benzopinacol. The mixture was allowed to stir with a magnetic stirrer at a temperature of 40 ° C until all components were completely dissolved. The 5 to 10 mg samples were weighed into an aluminum crucible and analyzed by DSC (differential scanning calorimetry) in a Mettler DSC 12E. The measurement conditions were set to a temperature increase of 10 ° C / minute between room temperature and 300 ° C.

The cure temperature offset is defined as. The shift of the maximum heat flux δΗΗ of the sample measured relative to the maxH _{max of the} standard sample consisting of the corresponding epoxide and the initiator system containing N -benzylquinolinium hexafluoroantonate / parent benzopinacol. 'Efekt.dosažený these: systems in combination with the epoxides A and / or B ¹ is shown in Table 2 and Table 3.

• ·· ·· · · · ·

Table 2

Curing of epoxides A and B initiated by beopinacols / N-benzylquinolinium-SbF _with

Initiation composition Temperature shift "cure" ¹ . (δΗ ^ DSC) in A Temperature shift "cure" ¹ (δΗ _ΜΧ DSC) in B Standard N-benzylquinolinium SbP ₆ / benzopinacol Low: 14 ° C 0 ° c N-Whitequinolinium SbF ₆ / Table 1, No. 3 Mp: -20 ° C and -20 ° C N-benzylquinolinium. SbF ₆ / Table i, No. 5 and -40 to -45. Noc: 2 ° C and -35 to -40 ° C N-benzylquinolinium SbFg / Table 1, No. 6 -40 ° C -30 ° C N-benzylquinolinium SbFg / Table 1, No. 7 -30 ° C and -30 ° C

* 1 = compared to epoxide A initiation. B to the appropriate standard

Table 3 ¹ ; Influence of different ... initiation mixtures of N-benzylohinolinium salt / benzopiriacol on "curing conditions" of epoxide A compared to the standard of N-benzylquinolinium SbF ₆ / benzopinacol SbF _s (5H _max in DSC)

SbFg ' CFjSOj ’ CF ₃ (CF ₂ ) Anion A, ' motherly ± 0 ° C + 25 ° C and + 20 ° C 0 to +5 ° C benzopinacol (standard) Tab. 1, No. 3 (Dimethyl). and - 20 ° C and + 10 '- 15 ° C + 3 ° C and - 20 ° C Table 1, No. 5 (tetrafluor) '~ - 40 áž - High: 32 ° C not measured and - 5 ° C ..eměřeno Tab. 1, No. 6 (Diethyl) and - 40 ° C = + 10-15 ° C . and ± 0.1 ° C and - 30 ° C Tab. i, No. 7 - (Diethyl) and - 20 ° C ~ + 10-15 ° C and ± 0 ° C and - 25 ° C

9 * 99.9 ·. · '··· -

Claims (22)

Thermosetting compositions capable of curing by cationic polymerization, characterized by: comprising: 1. (A) at least one compound that can undergo cationic polymerization; . ..... (B) at least one quaternary. ammonium salt ... of aromatic nitrogen. a heterocyclic cation containing one . Or two nitrogen atoms, and a non-nucleophilic anion; . - / -. . (C) at least one 1,2,2-substituted-1,2-ethanediol and / or a derivative thereof, wherein the substituents at the 1- and 2- positions are selected from aryl residues or aromatic heterocycles ring systems; and '· ·. (D) 'optionally' other cases; ·. and are characterized by:. 'said component (B) is selected from an anoht group containing' BFy, PFy, SbFy, SbF ₅ (OH) /,. [B (X) _p (Y) _q ] 'or CF, (CF · kSO 2, where · p and q are zero or an integer from 1 to 4 and' where the sum of p 'and q is always 4; each X (for p> 1) is, independently of the others, a halogen atom or a hydroxyl group, wherein for a halogen atom, p is zero, 1, 2 or 3; and for a hydroxyl group p is zero, 1 or 2; • ·. • · · · ·· ·. · · T 4 · 4 4 '· ·' 4 4 4 443 44 4 4 4 4 Each Y group (for q > 1) is, independently of the others, a phenyl group optionally substituted by at least two halogen atoms or one or two electron withdrawing groups; or Y is an aryl group with at least two $. aromatic rings optionally substituted with one or two halogen atoms or one or two electron-attracting groups; and m is zero or an integer of 1 to 17; _v . said component (C) is a compound of formula I: X @ 5 wherein each R _HR R _2, and R ₃ is independently 'of the other unsubstituted phenyl or have one of the meanings of R _4; R ₄ is a phenyl group substituted with a linear or branched -. -alkyl-containing-1-to-1-2-carbon atoms -adkoxy-alkyl containing from 1 to 8 carbon atoms in both the alkoxy and alkyl moieties alkylthio having 1 to 12 carbon atoms, alkylthio having 1 to 12 carbon atoms, alkylcarbonyl having 1 to 12 carbon atoms in the alkyl moiety. carbon atoms, halogen atom, nitro group, cyano group, haloalkyl group containing from 1 to 5 carbon atoms; 8 carbon atoms,. an aryl group, an arylalkyl group containing from 1 to 8 carbon atoms in the alkyl moiety, aryloxy, aryl-. thio, benzoyloxy, benzoylmethyl and / or naphthoyloxy or R ₄ is α-naphthyl or β • naphthyl: · 1-, 2- or 3-p-pyrimidyl, N-substituted (1- - 2- or 3-) pyridyl, and ⁱ -quinolinyl, β-quinolinyl, N-substituted (α- or β-) quinolinyl. and wherein said aryl and heterocyclic rings may be further substituted with a linear or branched alkyl group containing 1 to 12 carbon atoms or a halogen atom; or each R _x and R ₂ and / or R ₃ and R ₄ form a group of formula II: independently of the other (II) wherein '\ each of R _s and R _s independently of the other hydrogen or alkyl having 1 to 4 carbon atoms; R ₇ is - (CH ₂ ) _n - or -S- or -O-; · / N is 0,1, 2 or 3; and wherein the weight ratio of component B) to component. C) is between 0.05: 1.0 to 1.0: 0.05. 2. The composition of claim 1. characterized in that component (A) is a saturated oxygen or sulfur-containing heterocyclic compound containing 3, 4 or 5 ring members or a derivative thereof. ^! The composition of any one of claims 1 or 2, wherein component (A) is a compound containing at least one epoxy group. • ·· - · ··. · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·. *. ·. 9 Composition according to any one of claims 1 to 3, characterized in that component (A) is selected from mono-, di- and polyepoxides and epoxy resin prepolymers which are used for the preparation of epoxy resins. Composition according to claim 1, characterized in that component (A) is selected from mono- and diolefins, vinyl ethers, vinyl esters, dihydropyran derivatives, phenol formaldehyde resin prepolymers, acrylic resins, alkyd resins, and / or polyester resins containing functional groups. . · 6 '. The composition of any one of claims 1 to 10. 5, w h e c. s e. wherein component (A) is selected from mixtures of cationic polymerizable compounds and free radical polymerizable compounds. v .. ·. . ' A composition according to any one of claims 1 to 6, characterized in that the aromatic heterocyclic compound of component (B) which carries a positive charge is selected from the group consisting of pyridine, pyrimidine pyridazine and pyrazine and their alkyl or aryl derivatives, benzo and naphtoderivatives, preferably picoline, lutidine, quinoline, isoquinoline, quinoxaline, phthalazine, quinazoline, acridine, phenanthridine or phenanthroline. ,. 8.. The composition of claim 7, wherein the aromatic heterocyclic compound of component (B) is a cation. of formula III, IV. a V: where / R 1 is an alkyl group containing. C 1 -C 12, arylalkyl having 1 to 8 carbon atoms in the alkyl moiety, C 3 -C 15 alkoxyalkyl, or benzoylmethyl each. _{R10, X1, R13} and _R14 independently of the other hydrogen, C 1 -C 4 alkyl or phenyl, or R ¹ group _{on the 10th 1X} and R or R @ ₁ and R @ ₁₂ or R @ ₁₂ and R _13, R ₁₃ or a. R _14, together with -dvěma carbon atoms to which they are attached, are a fused benzo> naphtho, pyridino Hebo chinolinoskupina. . ,. The composition of claim 8, wherein R ₉ . is methyl, ethyl, n-pro-p-yl-o-s-kup-i-na-7-iso-butyl, linear or branched butyl, dodecyl, octadecyl, benzyl a group, a diphenylmethyl group, an acetyl group or a benzoyl group. A composition according to claim 8, wherein the aromatic heterocyclic compound of component (B) is a cation of any one of formulas (a) to (i), wherein A and B are each -CH. = or nitrogen: • «· 9 9 · (f) The composition of any one of claims 1 to 10, you, z. characterized in that it is non-nucleophilic. the anion of component (B) is selected from the group consisting of BFy, PFSbFSbF (OH) [Β (X) _p (Y) _q ] - or 'CF ₃ (CF ₂ ) _m SO ₃ *, where X (for p> 1 ) is a fluorine atom or a hydroxyl group, wherein for the hydroxy group p is 1 and each Y group (for 'q > 1) is independently of one another. other phenyl group substituted with at least. two halogen atoms, or one or two electron withdrawing groups selected from -CF ₃ , -OCF _3, or nitro or naphthyl. or a biphenyl group substituted with one or two fluorine atoms or one or two electron withdrawing groups. The composition according to any one of claims 1 to 11, denotes; ·. 'i ·' The substituent Y in the non-nucleophilic anion of component (B) is a pentafluorophenyl group, a 3,5-trifluoromethylphenyl group, or a para-trifluoromethyloxyphenyl group. . Composition according to any one of claims 1 to 12, characterized in that component (C) is a compound of the formula • · · • · · «Α« - • · · • ·. · · e »· • · · · · · · · · · · · · · · · · • · · · • · · · · • »· · I where each R _{1 Z} R ₂ R ₃ - is. independently of the others, phenyl or has. one of R ₄ and wherein R ₄ is a phenyl group substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 1 to 4 carbon atoms and an alkyl group having 1 to 2 carbon atoms, an alkyloxy group C 1-4 alkyl, C 1-4 alkylcarbonyl, fluorine, chlorine, nitro, halomethyl, phenyl, phenylalkyl containing from 1 to 2 atoms in the alkyl moiety -phenyloxy, phenylthio, benzoyloxy, benzoylmethyl and / or naphthoyloxy, or R ₄ is α-naphthyl. group. or a β ¹ -naphthyl group, a 1-, 2- or 3-pyridyl group, an N-substituted (1-, 2- or 3-pyridyl group). 3-) a pyridyl group wherein. The N-substituent has one of the meanings given for R ₉ , α-quinolinyl, β-quinolinyl ,. A N-substituted - (α- or β-quinolinyl group) wherein the N-substituent has one of the meanings given for R ₉ and wherein said aryl and heterocyclic rings may be further substituted by linear or a branched alkyl group having 1 to 4 carbon atoms or a fluorine atom or a chlorine atom; or - (-) - - - - - - ^; ·--ή each R _x and R ₂ and / or R ₃ and R ₄ independently of the other form a group of the formula · II wherein each _of R and _R is independently of the other hydrogen; and R ₇ is -GH _2- or -S- or -O-. _14th: The composition of claim 13, ICI vyzn.ačuj in that component (C) is a compound of formula I wherein each R ,, R ₂ and R ₃ independently of the others-phenyl or has one of the meanings as defined for R ₄ and wherein R ₄ is phenyl substituted with methyl, ethyl, 3 0 «.v ········································· fluorine ,, trifluoromethyl group or R _4th is α-naphthyl or β-naphthyl, 1-, 2- or 3-pyridyl, α-quinolinyl or β-quinolinyl. A composition according to any one of claims 13 or 14, wherein component (C) is a compound of formula I, wherein each of R 1, R ₂ and R _{3 is} independently of one another. other phenyl or having one of the meanings given for R ₄ and wherein R ₄ is 2-methylphenyl, 2-ethylphenyl, 2-butylphenyl, 2-fluorophenyl. 2,6-difluorophenyl, α-naphthyl, β-naphthyl. . a 1-, 2- or 3-pyridyl group, an α-quinolinyl group, or a β-quinolinyl group. ·,. , 16. Composition. according to any one of claims 1 to 15, characterized by. wherein the combination of component (B) with component (B) is benzylquinolinium hexafluoroantimonate ^; and '1,2-bis' (2-methylphenyl) benzopinacol, benzylquinolinium hexafluoroantimonate a. 1,2-bis (2-ethylphenyl) -benzopinacol, benzylquinolinium-hexa-fluoroantimonate and 1,2-bis (2-fluorophenyl) benzopinacol, benzyl. quinolinium hexafluoroantimonate and 1,2-bis (2,6-difluorophenyl). benzopinacol or a combination of N-benzylquinolinium triflate, Nbenzylquinolinium perfluorobutane sulfonate, N-benzylquinolinium tetrakis (3,5-bis-trifluoromethyl) phenyl borate and / or. benzylquinolinium tetrakis (pentafluorophenyl) borate with the various benzopinacols mentioned above. Composition according to any one of claims 1 to 16, characterized in that component (D) is selected from resin extenders, fillers, pigments, dyes, glass fibers and / or other fibers, stabilizers, preferably antioxidants or stabilizers. Against light, the substances slow down. _______ ······; .. * ·· 0 90 ·· '* ·: ‘- 0 · - 4 0 · 0 990 33. ' . ,, '··· 0 4 0 · 9 ´ 0 »···’ 4' · ·· 000. 40 '·· - * burning, antistatic,. blowing agents, leveling agents. \ and / or a heat stabilizer. I · ' Use of a composition according to any one of claims 1 to 17 in coating, paper, wood coating, plastic coating or. Conformal coating of printed circuit boards for the preparation of semiconductor devices, encapsulation of electrical coils, adhesive applications and production of molded epoxy and / or laminate constructions. . · ''. Use according to claim 18 for. Simultaneously shaping by heat sources, preferably in an oven, infrared radiation or ·. optionally in combination with photopolymerization. Compounds of formula I wherein R _x . and; R ₃ is independently of the other a phenyl group or one of the meanings defined for R ₂ . and each R ₂ . and R; independently of the other is 2-n-butylfe-, ·,, phenyl alkyl group, 2 - fluorophenyl, or 2,6-difluorophenylamino, group each group R ₅ and R _s independently of the other hydrogen or an alkyl group containing 1-4 carbon atoms. 21st benzylchinoliniové N-they are containing salts of N-benzylchinol'inioyý -__- _-: -kat ion associated with anicntemvzorce-CF (CF _{2) 3} SO ₃ 'or anion em " CF3. Anion A4 Kation K L and wherein, each R _a is independently of the others linear. or a branched alkyl group containing 1 to 12 carbon atoms, an alkoxyalkyl group containing 1 to 8 carbon atoms in both the alkoxy moiety and the alkyl portion, 1 to 12 carbon atoms, alkoxycarbonyl having 1 to 12 carbon atoms, halogen or hydroxyl. 22nd Method of Thermal Polymerization of Compositions According to. any of claims 1 to 17; characterized by:. that is, the compositions are heated in the presence of an initiator. combinations of components (B) and (C) as defined above.