DE2255169C3 - Thermosetting fluoropolymer composition and process for the production of moldings - Google Patents

Description

R ₄

R ₁ N N'R ₃

(1)

R ₃

2X

(2)

R ₄

R ₄

N - Β— Ν

N ¹ R ₃

R,

2X

(3)

R ₄

R ₁ NNR ₃ R ₂

X '' ¹

(4)

R ₄

R ₃

'«N

-N

R ₁

N ¹ »-

NR ₁

R ₅

2X ^f

(5)

R ₄

Rs

N-B - N

N "'R ₃

R,

2X

(6)

wherein Ri is an alkyl group with 1 to 20 carbon

atoms, a carbocyclic group, a heterocyclic group or an aralkyl group with 7 to 20 carbon atoms, R ₂ a hydrogen atom, an alkyl group with 1 to 12 carbon atoms, a carbocyclic group, a heterocyclic group, a phenyl group, a substituted phenyl group, an aralkyl group with 7 up to 12 carbon atoms, an alkoxy group with 1 to 12 carbon atoms, a benzyloxy group, a hydroxyl group, a carboxy group, an alkoxycarbonyl group, an acyl group, a benzoyl group or a cyclohexylcarbonyl group, R3 an alkyl group with 1 to 20 carbon atoms or an aralkyl group with 7 to 20 carbon atoms, R4 and R5 are hydrogen atoms or lower alkyl groups, A is an alkylene group or a phenyl group, B is an alkylene group, and X ^{s is} an anion.

2. Composition according to claim 1, characterized in that it also contains 0.1 to 10 parts by weight Water, based on 100 parts by weight of A, or 0.5 to 30 parts by weight, based on 100 parts by weight A, a metal salt which forms water by reaction with hydrogen fluoride.

3. A process for the production of molded bodies from the masses according to patent claims 1 and 2, characterized in that this mass is ground and brought into a shape at a temperature of 100 to 200 ^° C. under a pressure of 20 to IOC kg / cm ² cures over a period of 10 to 180 minutes, takes it out of the mold and cures in an oven at a temperature of 150 to 300 "C for a time of up to / u 30 hours.

The present invention relates to a thermosetting fluoropolymer composition and a method for Production of moldings from this mass. These moldings are characterized by a low permanent Compression deformation and excellent elastic properties.

Under the term "fluoroelastomer" used here is to be understood as a highly fluorinated, elastic copolymer, while here The term "fluororubber" used the cured one obtained when the fluoroelastomer was cured Copolymer is to be understood.

A fluororubber has excellent heat resistance, excellent resistance to low temperatures and chemicals on and is suitable for the production of seals, sealing means, diaphragms, pipelines and the like.

It is known that a fluororubber by curing a fluoroelastomer in the presence of a Hardening agent (crosslinking agent) can be produced. The fluororubber is said to be practical at its Uses both excellent elastic properties and low permanent compression set exhibit. In general, however, a conventional one deteriorates by curing Preparation made fluororubber the compression set, if the elastic properties are guaranteed, and on the other hand, its elastic properties deteriorate if the permanent Compression deformation is suppressed. Therefore one strives to find a fluoroelastonier preparation, which provides a fluororubber, the excellent

has elastic properties with at the same time low permanent compression deformation.

Recently, various fluoroelastomer formulations from which fluororubbers are made have been proposed can be produced with a low permanent compression set. These fluoroelastomer formulations are partially effective for reducing the permanent pressure deformation however, poor elastic properties.

The present invention is based on the object of a new fluoroelasiomer preparation to indicate the production of a fluororubber with a low permanent compression set and excellent elastic properties can be used. The invention is particularly the task is based on specifying a fluoroelastomer preparation, which within a short Time can be cured with certainty and in the non-cured state an excellent shelf life having.

The invention is accordingly a thermosetting fluoropolymer compound, consisting of:

A. a copolymer of vinylidene fluoride with at least one fluoroolefin and possibly low Amounts of copolymerizable monomers,

B. oxides or hydroxides of divalent metals or mixtures of these metal oxides and / or Metal hydroxides with metal salts of divalent metals of weak acids,

C. an aromatic polyhydroxy compound,

D. customary fillers, if applicable,

which is characterized in that the compositions, as curing accelerators, are based on 0.2 to 10 parts by weight to 100 parts by weight of A, a quaternary ammonium compound represented by the following general formula

R ₅

R ¹

• Ν

R,

R ₁ NN ^ R ₃

R ₃

2X

R ₄

R ₅

R ^ N N - B - N

R ₁

2X- (3)

Vi *

R ₁ N

R ₃

• Ν

VA-
-Ν ^{χ Χ} Ν-

R ₅ R ₁

R ₁ R ₅

2Χ

(5)

and

R ₅

R ₁ NN - Β - NN ^ft; R,

2Χ '

(6)

wherein Ri is an alkyl group having 1 to 20 carbon atoms, a carbocyclic group, a heterocyclic group or an aralkyl group having 7 to 20 carbon atoms, R _{2 is} a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a carbocyclic group, a heterocyclic group, a phenyl group, a substituted phenyl group, an aralkyl group having 7 to 12 carbon atoms, a 2s alkoxy group having 1 to 12 carbon atoms, a benzyloxy group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, an acyl group, a benzoyl group or a cyclohexylcarbonyl group, R ₃ an alkyl group having 1 to 20 Carbon atoms or an aralkyl group having 7 to 20 carbon atoms, R4 and R5 are hydrogen atoms or lower alkyl groups, A is an alkylene group or a phenyl group, B is an alkylene group and Χ ^{θ is} an anion.

Examples of the anion X "are a halide, hydroxylate, alkoxylate, phenolate, carboxylate, sulfonate, Sulphate, sulphite and carbonate ion.

By adding water or a metal salt which easily forms water on reaction with hydrogen fluoride, the curing rate of the preparation can be accelerated without the elastic properties being impaired. The composition according to the invention is therefore preferably characterized in that it additionally contains 0.1 to 10 parts by weight of water, based on 100 parts by weight of A, or 0.5 to 30 parts by weight, based on 100 parts by weight of A, of 0.1 to 10 parts by reaction with hydrogen fluoride Parts by weight based on 100 parts by weight of A water-forming metal salt contains.
The present invention also relates to a process for the production of moldings from the above-defined masses, which is characterized in that these masses are ground, brought into a mold, at a temperature of 100 to 200 ⁰ C under a pressure of 20 to 100 kg / cm ² over a period of 10 ^b: i hardens 180 minutes taking out from the mold and be a temperature of 150 to 300 ⁰ C in a time of Bi; hardens in an oven for 30 hours.

The molded articles produced according to the invention

fto have excellent elastic properties, at

for example an excellent module at eini

100% elongation, excellent tensile strength

Elongation and hardness and a low permanent "

Compression deformation at room temperature or at high altitude

(15 rer temperature. If, for example, the inventive

fluoro rubber in oil printing machines use severe conditions as a sealing material

this must be because of the excellent

Properties of the fluororubber according to the invention, in particular its low permanent compression set and its excellent elastic properties, does not need to be repeatedly sealed to a Prevent oil or gas leakage, like that at a common fluororubber is the case. In addition, the fluoroelastomer preparation according to the invention can safely handled and processed. For example, when handling occurs before the Hardly curing a scorch. Due to the advantageous flow properties during curing Complicated moldings can easily be produced from it under pressure, without any rearward Edge or any other disadvantage showing. Finally, the preparation according to the invention can also with a good curing speed. In addition, the preparation according to the invention has the The advantage that they have an excellent shelf life compared to conventional fluoroelastomer preparations having.

It is important for the present invention that the above component (D) is a quaternary ammonium compound of imidazole or imidazole. When imidazole or imidazoline themselves or their salts of Mineral acids or organic acids are used, these can have excellent effects in the Handling or processing as achieved according to the invention cannot be obtained.

In the case of the fluoroelastomer which forms component (A) in the preparation according to the invention and a represents highly fluorinated elastic copolymer, it can be, for example, a copolymer of vinylidene fluoride and at least one fluoroolefin, such as. B.

Hexafluoropropene, pentafluoropropene,
Trifluoroethylene, trifluorochloroethylene,
Tetrafluoroethylene, vinyl fluoride,
Perfluoro (methyl vinyl ether),
Perfluoro (propyl vinyl ether) or the like.
A vinylidene fluoride / hexafluoropropene copolymer and a vinylidene fluoride / tetrafluoroethylene / hexafluoropropene terpolymer are preferably used. In particular, it is advantageous to use a copolymer in which the molar ratio of vinylidene fluoride to hexafluoropropene is 92: 8 to 66:34, or to use a terpolymer whose composition is within the rectangular range resulting from the four molar ratios of vinylidene fluoride to tetrafluoroethylene Hexafluoropropene of 85.7: 5: 9.3, 59.7: 5: 35.3. 28:30:42 and 54:30:16, which is obtained by polymerization in suspension at low temperature. It can also be used with advantage such polymers that by copolymerization of a small amount of a monomer, such as. B. a vinyl compound, an olefin, a diene or an oc, /? - Ethylenically unsaturated carboxylic acid in addition to the above-mentioned monomers.

The invention is explained in more detail by the following description with reference to the drawing. Therein, the figure means a graphic representation which shows the curing curves of an inventive Fluoroelastomer preparation or those of comparative fluoroelastomer preparations shows.

Suitable examples of component (B) of the preparation according to the invention are divalent metal oxides, ζ. B. MgO, CaO, PbO or ZnO, metal hydroxides, e.g. B. Mg (OH) ₂ , Ca (OH) ₂ . Pb (OH) ₂ or Zn (OH) ₂ and mixtures of the above-mentioned metal oxides and / or metal hydroxides with metal salts, which are obtained from rental metals, such as. B. Ba, Na, K, Pb and Ca, and weak acids such as. B. stearic acid, benzoic acid, carbonic acid, oxalic acid and phosphorous acid are formed.

Examples of constituent (C) of the preparation according to the invention, which is an aromatic one Polyhydroxy compounds are the following:

ίο 2,2-bis (4-hydroxyphenyl) propane (Bisphenol A),

2,2-bis (4-hydroxyphenyl) perfluoropropane (bisphenol AF),

Resorcinol, 1,3,5-trihydroxybenzene, 1,7-dihydroxynaphthalene,

2,7-dihydroxynaphthalene,

1,6-dihydroxynaphthalene,

4,4'-dihydroxydiphenyl,

4,4'dihydroxystilbene,
2,6-dihydroxyanthracene,

Hydroquinone, catechol,

2,2 bis (4-hydroxyphenyl) butane (bisphenol B),

4,4-bis- (4-hydroxyphenyl) pentanoic acid, 2,2-bis- (4-hydroxyphenyl) tetrafluorodichloropropane,

4,4'-dihydroxydiphenyl sulfone,

4,4'-dihydroxydiphenyl ketone,

Tri- (4-hydroxyphenyl) methane,
3,3 ', 5,5'Tetrachlorobisphenol A, 3,3'.5,5'Tetrabromobisphenol A and the like.

Hydroquinone, bisphenol A, bisphenol B and bisphenol AF are particularly preferred, but they can also be Alkali metal salts or alkaline earth metal salts of the above-mentioned aromatic polyhydroxy compounds are used will.

Examples of constituent (D) of the preparation according to the invention, which is a quaternary Ammonium compound are the following:

l, 3-dimethyl-2-heptylimidazolium iodide, l, 3-dimethyl-2-nonylimid-azolium iodic !, 1,3-dimethyl-2-undecylimidazolium iodide, 1,3-dimethyl-2-heptadecylimidazolium chloride, 1,3-diethyl-2-heptadecylimidazolium chloride, 1,3-dipropyl-2-heptadecylimidazolium chloride, 1 - dodecyl-S-propylimidazolium iodide, 1 -dodecyl ^ -dimethylimidazolium-p-toluenesulfonate,

1,3-didodecyl-2-methylimidazolium chloride, 1-decyl-2,3-dimethyl'imidazolium iodide, 1 -decyl-2,3-dimethylimidazolium bromide, l-tetradecyl ^ S-dirnethylimidazolium iodide, 1-tetradecyl - ^ - dimethylimidazolium hydroxide, 1 - Dodecyl-2-undecyl-3-methylimidazolium sulfate, 1 ^ -Dihexadecyl ^ -heptadecylimidazolium chloride,
l-Hydroxyäthyl ^ -methyl-S-dodecyl-imidazolium-

p-toluenesulfonate,

!, S-Didodecyl ^ -phenylimidazoliumchloricl, l-Dodecy] -2,4-dimethyl-3-benzylimidazolium chloride,
i ^ -Dihexadecyl ^ -phenyM-methylimidazolium-

chloride,

1-vinyl-2-methyl-3-dodecylimidazolium chloride, 1-vinyl-1-methyl-S-hexadecylimidazolium chloride.

i-Allyl ^ -methylO-dodecylimidazolium chloride.

l- (y-aminopropyl) -2-methyl-3-dodccyl imidazolium chloride.

l-Undecenyl ^ -octyl-S-ethylimidazolium bromide.

i-Eicosyl ^ -eieosenyl ^ -decylimida / .olium bromide.

i-Dodecyl ^ -iv.ethyl-S-benzylimidazole dichloride.

l, 3-dibenz \ i-2-methylimidazolium chloride, l ^ -dibenzyl ^ -methylimidazolium hydroxide.

1-Benzyl ^ -methyl-S-dodecylimidazolium chloride.

1-Dodccyl ^ -methyl-S-benzylimidazolium chloride.

1-butyl ^ -heptylO-benzylimidazolium chloride.

l-tetradecyl ^ -methyl ^ -benzylimidazolium bromide,

i-Dodecyl ^ -phenyl-S-benzyl-imidazolium bromide,

l-Benzyl ^ -undecyl ^ -methylimidazolium methyl sulfate,

i-Amyl ^ -undecyl-S-benzyl-imid-azolium bromide, l-dodecyl ^ .S-dimethyl ^ -benzylimidazolium chloride,

l-dodecyl ^ -phenyl ^ -benzyl ^ -methylimidazolium bromide,

l- (2'-pyrimidyl) -2,3-dimethylimidazolium chloride,

1,4-butylene-bis- [l'-ethyl-3'-dodecylimidazolium- (2 ')] dichloride, 1,4-phenylene-bis- [l'-dodecyl-3'benzyl-4'-methylimidazolium- (2 ')] dichloride, 1,4-phenylene-bis- [l'-dodecyl-3'-dibenzyl-4'-methylimidazolium- (2 ')] dibromide, 1,4-butylene-bis [2'-ethyl-3'-dodecyl- 4'-methylimidazolium (r)] dichloride, 1,4-butylene-bis- [2'-methyl-3'-hydroxyäthylimidazolium- (r)] dichloride,

1,2-ethylene-bis- [2 ', 3'-climethylimidazolium- (l')] dichloride; !, S-dimethyl ^ -heptylimidazolinium iodide, !, S-dimethyl ^ -nonylimidazolinium iodide, !, S-dimethyl ^ -undecylimidazolinium iodide, !, i-dimethyl ^ -heptadecylimidazolinium chloride,

l.S-diethyl ^ -heptadecylimidazolinium chloride,

l.S-Dipropyl ^ -heptadecylimidazolinium chloride,

l-dodecyl-S-propylimidazolinium iodide, i-Dodecyl ^ .S-dimethylimidazolinium p-toluenesulfonate.

l ^ -Didodecyl ^ -methylimidazolinium chloride, l-decyl ^^ - dimethyl-imidazolinium iodide, l-decyl ^ -dimethylimidazolinium bromide, l-tetradecy] -2,3-dimethylimidazolinium iodide, i-Tetradecyl ^ S-dimethylimidazoIiniumhydroxyd,

1-Dodecyl ^ -undecyl-S-methylimidazoline methyl sulfate

!, S-Dihexadecyl ^ -heptadecylimidazoline chloride.

1-hydroxyethyl ^ -methyl-S-dodecylimidazolinium-p-toluenesulfonate.

LS-Didodecyi ^ -phenylimidazoliniumchlorid, l-dodecyl-2,4-dimethyl-3-benzylimidazolinium chloride,

l.B-Dihexadecyl ^ -phenyl ^ -methylimidazolinium chloride.

1-vinyl ^ -methyl ^ -dodecylimidazolinium chloride.

l-vinyl-2-methyl-3-hexadccyliniidazoliniunv chloride,

l-allyl ^ -methyl-S-dodccylimidazolinium chloride,

l - () '- Aminopropyl) -2-methyl-3-dodecylimidazolinium chloride,

l-Undecenyl ^ -octyl-S-ethylimidazolinium bromide.

i-Eicosyl ^ -eicoscnyl-S-decylimidazolinium bromide,

i-Dodecyl ^ -methyl-S-benzylimidazolinium chloride.

I.S-dibenzyl ^ -methylimidazolinium chloride, I. S-Dibenzyl ^ -methylimidazolinium hydroxide.

i-Benzyl ^ -methyl-S-dodecylimidazolinium chloride,

i-Dodecyl ^ -methyl-S-benzylimidazolinium chloride.

i-Butyl ^ -heptyl-S-benzyl-imidazolinium chloride.

i-Tetradecyl ^ -methyl-S-benzylimidazolinium bromide,

i-Dodecyl ^ -phenyl-S-benzylimidazolinium bromide,

i-Benzyl ^ -undecyl-S-methylimidazolinium methyl sulfate,

i-Amyl ^ -undecyl-S-benzylimidazolinium bromide, l-dodecyl ^ .S-dimethyl-S-benzylimidazolinium chloride,

l-dodecyl ^ -phenyl-S-benzyl ^ -methylimidazolinium bromide,

l- (2'-pyrimidyl) -2,3-dimethylimidazolinium chloride,

1,4-butylene-bis- [1'-ethyl-S'-dodecylimidazolinium- (2 ') dichloride,

1,4-phenylene-bis- [l'-dodecyl-3'-benzyl-4'-methylimidazolinium- (2 ')] dichloride, 1,4-phenylenebis [l'-dodecy l-3'-dibenzyl-4'-methylimidazolinium- (2 ')] dibromide, 1,4-butylene-bis- [2'-ethyl-3 '-dodecyl-4'-methylimidazolinium- (r)] dichloride, 1,4-butylene, bis- [2'-methyl-3'-hydroxyethylimidazolinium (l ')] dichloride and l, 2-ethylene-bis- [2', 3'-dimethyi-

imidazolinium (r)] dichloride.

The water that may be present in the mass, can be present directly or in the form of metal salt hydrates of the fluoroelastomer preparation, the Metal salt hydrates contain the water in a form that is harmless during hardening, such as. B.

MgSO ₄ · _{7H 2} O, CuSO ₄ · _{5H 2} O and FeSO ₄ · _{7H 2} O.

As a metal salt which easily forms water by reaction with hydrogen fluoride, metal hydroxides, such as. B. Mg (OH) ₂ , Pb (OH) ₂ and Ca (OH) ₂ can be used. In the case of using these metal hydroxides, the addition of the component (B) can be omitted.

As for the amount of the above ingredients of the preparation according to the invention used, based on 100

<> 5 parts by weight of the fluoroelastomer applies to so they are expediently 2 to 30, preferably 5 to 20 parts by weight for component (B), 0.5 to 5, preferably 1 to 2 parts by weight for the ingredient

709 623/197

(C) or 0.2 to 10 parts by weight, preferably 0.5 to 1 parts by weight for component (D). In the case that the amount of the component (D) is less than the above range indicated, the curing of the fluoroelastomer preparation proceeds not satisfactory. On the other hand, the elastic properties of the Fluorkaulschuks obtained are impaired. when the component (D) is present in an amount which is above the range given above. The amount of water added is 0.1 to 10, preferably 0.5 to 5 parts by weight c. based on 100 Gev. ichtpeile of the fluoroelastomer. The amount of Metal salt varies with the kind thereof and ranges from 0.5 to 30, preferably 2 to 10 parts by weight, based on 100 parts by weight of the fluoroelastomer.

The composition according to the invention can also, as required, fillers such as carbon black, silicon dioxide, clay, Diatomaceous earth or talc can be added. If necessary, the mass can also be one or more Usual hardening agents (crosslinking agents) can be added if this is necessary for the present invention is conducive. In addition, plasticizers and colorants can be added.

The fluoroelastomer composition thus obtained can be cured (crosslinked) by the following method. The preparation is ground, for example, by means of mixer rollers and the resulting mass is placed in a mold and cured under pressure and then the shaped body formed is removed from the mold and then cured in an oven. In general, the curing under pressure at a temperature of 100 to 200 ⁰ C under a pressure of 20 to 100 kg / cm ² is carried out over a period of 10 to 130 minutes, and curing in an oven is performed at a temperature of 150 to 300 ° C carried out over a period of 0 to 30 hours. It. other curing methods can also be used, e.g. B. a method in which the curing after preforming, for example by injection molding or extrusion molding, is carried out, or a method in which by dissolving or dispersing the fluoroelastomer preparation in a solvent, such as. B. a ketone, such as methyl ethyl ketone, acetone and cyclohexanone, an ether, such as methyl ether, diethyl ether, dioxane and tetrahydrofuran, or a mixture thereof, a coating composition and prepared on the surface of a paper, a fiber, a film, a foil, a board , a pipe, a pipeline, a container, a large boiler or another shaped body (made of cellulose derivatives, synthetic resin, metal or another material) and then cured.

The fluororubber produced from the fluoroelastomer preparation according to the invention has advantageous properties Properties on, e.g. B. excellent heat resistance, excellent resistance to low temperatures and chemicals, such as the one from fluororubber made of a common fluoroelastomer formulation, and furthermore it has the above proved to have excellent properties that cannot be achieved with a conventional fluoroelastomer formulation can be.

The invention is further illustrated by the following examples. In the following examples Unless otherwise stated, parts and percentages given relate to weight.

Reference example

A 3-1 stainless steel autoclave was used with 1000 Share demineralized and oxygen-free water

s sends. The air inside the autoclave was through pure nitrogen gas and then replaced with tetrafluoroethylene. The autoclave was 96 parts of a Monomer mixture, consisting of 27.1% vinylidene fluoride, 63.5% from hexafluoropropene and 9.4% from

ίο tetrafluoroethylene. loaded. The temperature was raised to 100 ^° C. with stirring, and the polymerization was initiated ^{under a pressure of 12 kg / cm 2} by adding 10 parts of a 6% strength aqueous solution of ammonium sulfate.

is The polymer was in the form of an emulsion receive. A 10% strength magnesium chloride solution was added to the autoclave to remove the polymer to coagulate. The polymer was washed with water and dried, and 423 parts were obtained of the colorless elastic terpolymer.

Reference example 2

A 3 liter stainless steel autoclave fitted with a magnetic stirrer was charged with 1 liter of oxygen-free water and 0.3 g of methyl cellulose (50 cPs) was added. After the air inside the autoclave had been replaced by pure nitrogen gas and then evacuated, the autoclave was filled with 300 ecm of lU-trichloro-U ^ -trifluoroethane, then with 300 g of a monomer mixture consisting of hexafluoropropene, vinylidene fluoride and tetrafluoroethylene in a molar ratio of 50 , 6: 44.9: 4.5, charged and kept ^{at 40 ° C. with stirring.}

A 125cc container cooled by dry ice

is was with 50 ecm of a 1.97% solution of

Di- (3,5,6-trichloro-2,2,3,4,4,5,6,6-octafluorohexanoyl) peroxide in l, l, 2-trichloro-l, 2,2-trifluoroethane charged and the solution was poured into the Autoclave introduced to initiate polymerization.

Another 20-1 autoclave was charged with a continuous charge monomer mixture consisting of hexafluoropropene, vinylidene fluoride and tetrafluoroethylene in a molar ratio of 20:68:12 and connected to the first autoclave. The monomer mixture was introduced into the autoclave in such a way that a constant pressure between 9 and 10 kg / cm ² (G) was maintained. In addition, 50 ecm of the polymerization initiator solution was added, and after about 5 hours of polymerization, it was obtained

such as about 300 g of a fluoroelastomer in the form of small white granules.

Reference example 3

A 3-1 stainless steel autoclave fitted with a magnetic stirrer was de-oxygenated with 1 liter Water and 0.3 g methyl cellulose (50 cps) are charged after the air inside the autoclave has passed through pure Nitrogen gas had been replaced and then evacuated, the autoclave was filled with 300 ecm l, l, 2-trichloro-l, 2 l -trifluoroethane and then with 300 g of a monomer mixture consisting of hexafluoropropene and vinylidene fluoride in a molar ratio of 58:42. This mixture was kept at 30 ° C. with stirring. A 125 ccm container, cooled by dry ice, was filled with 50 ecm of a 1.97% solution of Di-pS ^ -trichlor ^^ SeeflhlJer

Dip.S ^ -trichlor- ^^. S.e.e-octafluorohexanoyl peroxide charged in 1.l, 2-trichloro-l, 2,2-trinuoroethane and the solution was poured into the

22 55 1 (39

Autoclave introduced to initiate polymerization. Another 20-1 stainless steel autoclave was charged with a continuous feed monomer mixture consisting of hexafluoropropene and vinylidene fluoride in a molar ratio of 25:75 and connected to the first autoclave. The monomer mixture was introduced into the autoclave in such a way that the polymerization pressure / was maintained between 8 and 9 kg / cm ² (G). The polymerization was carried out for about 5 hours. The remaining monomers were then withdrawn to give about 140 g of a fluoroelastomer composed of small granules.

Examples 1 to 3

To that in Reference Example 1 by interpolymerization of vinylidene fluoride, hexafluoropropene and tetrafluoroethylene in a molar ratio of 66.5: 16.0: 17.5 produced vinylidene fluoride / hexafluoropropene / tetrafluoroethylene terpolymer soot with an average particle size of about 450 ΐημ, Magnesium oxide, calcium hydroxide, hydroquinone and 1,3-dibenzyl-2-methylimidazolium chloride in that order added in the amounts given in Table I below. The preparation was made using a mixing roller at room temperature mixed (ground) and the resulting masses were over Left at night. After remixing it became

Table I.

the preparation is poured into a mold and cured at a temperature of 170 ° C. under a pressure of 55 kg / cm ² (G) for 30 minutes to form a film or a block. The received

The molded article was taken out of the mold and kept at a temperature of 230 ° C. for 24 hours hardened (example 1).

Then the module at an elongation of 100%, the tensile strength, the elongation and the hardness of the

ίο the resulting fluororubber sheet and the permanent one Compression deformation of the fluororubber block obtained was measured. Another curing attempt was made Carried out with the preparation and using a Curelastometer were after The stresses (stresses) are measured after a certain time.

In addition, the procedure of Example 1 was repeated, this time instead of 1,3-dibenzyl-2-methylimidazolium chloride 1, dodecyl ^ -methylO-benzylimidazolium chloride was used (example 2) and where water was also added (example 3), no quaternary ammonium compound was used (Comparative Example 1) and instead of 1.3-dibenzyl-2-methylimidazolium chloride and hydroquinone N.N'-dicinnamylidene-i ^ -hexanediamine as usual Hardening agent was used (Comparative Example 2). The quantities used and the The results obtained are shown in Table 1 below.

Components Magne medium Calci Hydro- I.3-Diben / \ I- - I-dodecyl N.N'-Di- water Endurance test fluorine sium Thermal umhy chinnn 2-methylimide- 2-methyl- cinnamylid I min 2 mil elasto oxide Carbon droxyd azolium 3-benzylimide 1,6-hexane meres chloride azolium chloride diamine 10 20th 1 1 (kgl Ikgl example 1 100 10 20th 3 1 1.5 0.45 0.60 Example 2 100 10 20th 1 0.8 1.5 0.60 0.65 Example 3 100 10 20th -> 1 ._ 0.70 1.40 Ver 100 not equal hardened example 1 15th 20th 3 - Ver 100 0.50 0.70 equal example 2

Table I (continued)

1 Endurance test 4th 5 1.80 10 15th 20th properties Tensile strength strain hardness Permanent compression set 200 ° C-24h 2 3 mm. min. min. min. mm. Module at speed (%) 3 min. 100% 30 ° C · 24 h 20th (kg) (kg) (kg) (kg) (kg) strain (kg / cm ² ) (%) (%) 21 (kg) 1.75 3.35 3.65 3.70 3.70 (kg / cm ² ) 155 180 78 10 25th example 1 0.80 1.60 2.50 3.30 3.40 3.40 68 150 160 82 15th example 0.75 2.25 2.55 3.50 - 4.00 88 159 170 82 12th example 1.90 hardened 81 Ver 2 not 35 equal example 1.40 2.70 3.05 3.10 180 290 76 33 Ver 1.10 50 equal example

(1) The module at an elongation of 10O ¹¹ Zi .. the tensile strength and the elongation were ken with dumbbell pieces (No. 3). which had been produced from cured film samples, measured using a universal tensile strength tester (type UTM-IlI) from To> o Sokki Kabushiki Kaisha in accordance with the regulation) IS K 6301.

(2) The hardness was measured using a hardness tester (Asker type |) of the company Kobunshi Keiki Kabushiki Kaisha.

(3) The permanent compression set was measured with disk-shaped with test specimens, which had been produced from the hardened block specimens, in accordance with the regulation] 1S K 6301 measured as follows:

The test samples were incubated for 24 hours retained under a compression of 25% at 30 ° C and 20O ⁰ C and then at room temperature for 30 minutes allowed to stand to carry out the measurement with a thickness gauge for rubber from Peacock type Kabushiki Kaisha Ozaki Seisakusho. The permanent compression set was calculated from the thickness of the specimens using the following equation:

permanent compression deformation (%)

100.

IO

20th

where (o the thickness (mm) before compression, ii the thickness (mm) after compression and fc (mm) is the thickness of the, spacer mean.

(4) The hardening test was carried out on a 34 mm 7 mm χ 2 mm sample below Use of a Curelastometer () SR Curelasiometer Type No. 11). The test sample was placed in a molding chamber and at a temperature of 180 ° C, a frequency of 6 cycles per minute and an amplitude of 3 ° and tested then after a certain time the Tension (stress) measured.

Example 4

The curing procedure of Example 1 was carried out using the methods given in Table II below

Table II

indicated preparation repeated and the curing test was carried out, the in the Results given in Table II below were obtained. The F i g. 1 of the accompanying drawings shows the curing curves of Example 4 and the comparative examples recorded by means of the Curelastometer 4 and 5.

As can be seen from Table II of Fig. 1, the 1 - Dodecyl ^ -methyl-S-benzylimidazolium chloride containing preparation according to the invention a satisfactory induction period and an excellent one Processability on and can be compared to the imidazole itself or its hydrochloride containing Preparations (comparative examples) are cured with a good hanging speed.

Examples 5 to 9

The curing procedure of Example 1 was followed by the procedure given in Table 11 below. specified preparation repeated and the properties were determined. The results obtained are shown in Table III below specified.

Examples 10 to 12

Using those in Reference Example 1 for Example 10. In Reference Example 2 for Example 11 and fluoroelastomers obtained in Reference Example 3 for Example 12 were subjected to the curing process of Example 1 with the preparation given in Table IV below and repeated the properties of the rubber obtained thereby were determined. The results are in the following Table IV given.

Components

Fluorine Magne Medium Calcium

clastosium oxide thermal cium-

mcres carbon hydroxyd

Hydro-2-methyl-I-dodecylquinone imidazole 2-methylimidazole

1-dodecyl- I-dodecyl-

2-methylimide-2-methylazole hydrochloride 3-benzylimidazolium chloride

Example 4 100 10 20th 3 Comparison 100 10 20th 2 example 3 Comparison 100 10 20th 2 example 4 Comparison 100 10 20th 2 example 5

1.2

Table II (continued)

Endurance test 3 min 4 min 5 min 10 min 20 min 30 min I min 2 min (kg) (kgl (kg) (kg) (kg) (kg) (kg) (kg)

Example 4 0.45 0.50

Comparative not hardened

0.70

0.85 1.75

3.10

3.20

15th

Continuation Be Hardening tesi 2 min 3 min 4 min 5 well 10 min 20 min ϊι) min 1 min <kgl Ikü) Ikgi tkgi tkg) (kg) Ikgi lkl! l 0.55
0.60 0.60
0.70 0.65
0.75 0.70
0.77 1.05
1.00 2.90
2.25 3.00
2.75 0.50
0.50 Comparison
example 4
Comparison
example 5 Table 111 components

Kluor Magne Medium Calcium Bisphenol Λ Potassium Sal / 1,3-Dibenzyl- 1-Dodecyl-

elastosium oxide thermal hydroxide of bis- 2-methylimide- 2-methyl-

^ITleres carbon phenol A azolium chloride 3-benzylimide

azolium chloride

water

example 5 100 10 20 2 -> example 6th 100 10 20 3 T example 7th 100 10 20th 2 example 8th 100 10 20th 2 example 9 KK) 10 20th table IU (Continuation) 'n tensile strength strain properties Module at 100 ". strain

(kg / cm ² )

hardness

permanent compression set 30 "C-24h 2 (X) C ■ 24h

(kü.'cnr)

Example 5 75 Components ! 58 170 82 12th 20th Example 6 72 Fluoroelastonic res 151 170 80 13th 21 Example 7 62 155 180 78 12th 19th Example <p 61 152 170 77 14th 22nd Example 9 80 155 180 81 14th 23 Table IV Magnesia Medium thermal Calcium hydroxide Hydroquinone 1,3-D

Carbon 2-methylimide

azolium chloride

Example 10 100

Example 11 100

Example 12 100

Table IV (continued)

10 20th 2 1 0.8 10 20th 2 1 1 10 20th 2 1 1

Properties Module at 100% tensile strength

(kg / cm ² )

(kg / cm ² )

strain

hardness

Permanent compression set 30 ^° C 24h 200 "C-24 h

example 10 90 example 11th 85 example 12th 98

161 158 163

170 180 160

77
77
87

1 sheet of drawings

11th
12th
11th

21

23 22

709 623/197

Claims (1)

Patent claims: 1. Thermosetting fluoropolymer composition consisting of A. a copolymer of vinylidene fluoride with at least one fluoroolefin and possibly small amounts of copolymerizable monomers, B. oxides or hydroxides of divalent metals or mixtures of these metal oxides and / or metal hydroxides with metal salts of divalent metals of weak acids, C an aromatic polyhydroxy compound, D. customary fillers, if applicable, characterized in that the mass as a hardening accelerator 0.2 to 10 parts by weight, based on 100 parts by weight of A, a quaternary Ammonium compound represented by the following general formula