DE2123110A1 - Vulcanizable mixture of fluorine-substituted elastomers - Google Patents

Description

EI DlT POHT DE NEMOURS AND COMPANY 10th and Market Streets, Wilmington, Delaware 19 898, V.St.A ₀

Vulcanizable mixture of fluorine-substituted elastomers

The invention relates to a vulcanizable mixture of a fluorine-substituted elastomer and a method for vulcanizing of such mixtures.

Highly fluorine-substituted elastomers are enjoying more extensive Use in special areas such as high temperature resistant sealing rings, seals, diaphragms and Hoses. Moldings made of fluorine-substituted elastomers withstand temperatures of about 250 to 350 ° C without doing their job losing good elasticity.

Purely for many purposes, e.g. for the seals of high-temperature reactors, the products must be elastic and only have a slight permanent compression deformation (permanent deformation after compression). This is achieved by vulcanisation of the product, wherein the elastomer is crosslinked.

109849/1873

So far, "well-known method of vulcanizing τοπ fluorsubsti- ■ fcuierten Elastoraeren mainly make τοπ aliphatic diamine as a crosslinking agent *! Use, or let the vulcanization Brzeugimg free ladikale, _ζ β Β · in the presence of organic peroxides or by irradiation with high-energy radiation ,, run · The Biaaiine generally have too strong a tendency to scorch and have recently been replaced by carbamates © of the aminocarbamic acids ο Organic peroxides cause rapid gel development, and the mixtures with additives - in which they are contained _- cannot be reliably enough Irradiating with ensurgisher radiation is a slow® process ₈ in which a completely vulcanized material is not immediately distorted. "Besides, this process is quite expensive" There is therefore a need for a process for the preparation of fluorine-substituted elastomers n * in which good Vulkanig-a '& ionsgsschwindig & eiten and a good processing reliability are achieved and the unvulcanized mixtures, a good durability ai ?.fweis@n, and the vulcanized Polyiaerisat® hold good tension3 ~ elongation behavior and lower lasting bias results.

In the broadest sense, the invention relates to a vulcanizable one Mixture of a fluorine-substituted elastomer, in which a elastomere ^ Gopolyraerisat from Tinjüdesfliiorid and at least another, fluorine-substituted monomers iia mixture with Ingredients is present that improve the vulcanization properties, and that is characterized by the fact that they are used as the vulcanization properties improving constituents metal compounds ρ is all divalent metal oxides or hydroxides, optionally in a mixture with metal solutions of weak acids, one as a crosslinking agent for the copolymer effective aromatic polyhydric compounds and one als Valkanisatioasbeschleii.Kiger wirl: @ nd © quartlre Aanaoniumverbindungen the allgeiaeinesa Pormsl

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R ₄ -NR,

or

-N-Rc

contains where

and R ^ independently of one another

C ₁ - to CgQ-alkyl radicals, fluoroalkyl, aralkyl, polyoxyalkylene or polyoxyfluoroalkylene radicals, with the proviso that at least two of these radicals are alkyl or aralkyl radicals, R ^ is a C ₁ - to OgQ-alkyl radical and X is a Hydroxyl, halogen, sulfate, sulfite, carbonate, pentachlorothiophenolate, tetrafluoborate, hexafluorosilicate, hexafluorophosphate, dimethyl phosphate or C ₁ - to CgQ alkyl, aralkyl or aryl carboxylate or dicarboxylate ion . In the latter two formulas for the vulcanization accelerator, the nitrogen atom forms part of a ring structure.

The invention also relates to a method of vulcanizing of mixtures of the elastomeric copolymer, the metal compound, the crosslinking agent and the vulcanization accelerator by heating this mixture.

For most uses, the vulcanizable Mixture preferably per 100 parts by weight of copolymer about 1 to 15 parts by weight of metal compound, about 0.1 to 5.0 Parts by weight of crosslinking agent and about 0.1 to 2.0 parts by weight of vulcanization accelerator; are particularly preferred Mixtures having a content of the metal compound of about 2 to 10 parts by weight, a content of the crosslinking agent from about 0.6 to 2 parts by weight and a content of the vulcanization accelerator from about 0.2 to 0.6 parts by weight per 100 parts by weight of copolymer

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The elastomeric copolymer is preferably a copolymer of vinylidene fluoride and hexafluoropropylene, a copolymer of vinylidene fluoride and Kosoohlortrifluoräthylen, a CopoljTserisat of vinylidene fluoride ₉ hexafluoropropylene and .Tetrsfluoräthylen ocei? EIA O-emic are preferred for more such copolymers »· Eesosäsrs swa 85 s 15 present copolymers of vinylidene fluoride and hexafluoropropylene," in which the monomers in Molverhälteis WGII to 5Οϊ5Ο. The Gopolyiflerigat taxm Miok another fluorine-substituted elastomer be to useful IASS sieä, Vulcanize products «Hiersii include aB, copolymers voa Yinyli-

with Bielilcir-difliiisxäthylea. ? or Monociilormonofluormit Fluo3 siibstitui © rten Tinylestern, with derivatives of "BBTfluGTBQTjlBäMTQ © ier bit fluoro-substituted Alkylvinylatfc, © rii | Example © fio di © latter are Gopolymerisate of vinylidene \ m & siaes perfluoroalkyl perfluorovinyl ether as in-USA ^ Eateatselirift?; are described 3,136,745, UNAE ©© polymerisat® from Tiaylidenfluorid, Setrafluoräthylen and Deia said HHä & Tv ^ i® ³ ^ ^e ^ ⁿ ^ · ^{@ Ε} US Patent 3,235,537 lseseiirieiieE s ± aä _o Sas "other fluorine-substituted Monoiäers ⁵³ d @ e G © polj © esfa.se.ts is a precautionary ethylene-unsaturated KonpiaereEg "Eat as many fluorine atoms as cobleiast © f £ at © ae"

Bie! Fetall ¥ erfeimdmig AEET Aemen Misohimgen is a divalent metal oxide, wi © IlagEesiucioxid, zinc oxide, calcium oxide, or lead oxide, or aw @ iwertiges metal hydroxide or a GeiBiseli from the Osid IMD / o & er the hydroxide with a metal salt © iaer ecliwaelisa B'äw ? e ₉ such as z * B »© in a mixture which contains about 1 to 70 G © wissiitgp5? Gäi5! it ketsllsalz. To the in this sense veiwem & baxes metallic salts of weak acids belong barium-, latrium = - ^ Eialinm- ,. Lead and calcium stearate, -hen soat, "-carbpnat," Salat wnä -phosphit "The amount of metal compound to be added is generally about 1 to 15 parts by weight and preferably about 2 to 6 parts by weight

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per 100 parts by weight of fluorine-substituted elastomer · One to some extent "affects the concentration of the metal compound the rate of vulcanization, and below the preferred amount range, the rate of vulcanization may be reduced too much. If larger than the preferred amounts are added, the elastic ones suffer Properties of the vulcanized fluorine-substituted elastomer progressively, and it is therefore advantageous not to use excessive amounts of the metal compound.

The metal compound has two tasks · It absorbs certain gaseous and acidic substances that are produced during vulcanization develop and chemically attack and weaken the fluorine-substituted elastomers. Perner gives them to the mixture a long-term shelf life. If you work with a metal oxide, this can be incorporated into the mixture of the fluorine-substituted Elastomers as free metal oxide or as complex compounds or chelates with organic complexing agents and ligands, such as cyclic polyethers, amines, phosphines, ketones, alcohols, phenols or carboxylic acids.

As a crosslinking agent can be used in the vulcanizable mixture use the known aromatic polyhydroxy compounds, which are useful as crosslinking agents for elastomeric copolymers suitable. For example, di-, tri-, tetrahydroxybenzenes, naphthalenes or anthracenes and bisphenols can be used as crosslinking agents the general formula

n (H0) (0H) n

use, in which A is a bifunctional aliphatic, oycloaliphatic or aromatic radical with 1 to 13 carbon atoms or a thio, oxy, carbonyl, sulfinyl or

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Sulphonyl radical "and can optionally be substituted by at least one chlorine or pluoratoii, χ has the value 0 or 1, η has the value 1 or 2 and each aromatic · · ring of the polyhydroxy bond optionally by at least one Chios-, Fluor ™ or BEaisatoja © & ®r at least one garbosyl or aoyl radical (adU a radical -00H ₉ - u with R a hydrogen atom or jie C «~ to O« -alkyl, ax-yl »© which can be oyeloalkylgmippe ) substituted m® in" can ο From the above definition it follows that the £> E ° -temppez ?. in any ring at 3 @ de "any® Steliimg (from ε sr des» position Hr * 1) be tied Sco * 2m @ n. Maai can also use ßsslscii © from truer Solcaer connections, lias © ier w © str © llstea TeifnstgiingsiEittel is called "Bisphenol A3? ^K helmmiis® bisphenol compound, namely Hezafluorisopropylid @ a «bis-C4-13järosyb © ns5Ol). Also, the compounds 4 _s 4 ⁵ -3i! Iyär "O ^ -diph © rijlettl £ 0n (bisphenol S) and isopropylidene«> bis- (4-hyfiro ^ benzol) (bisphenol A) can be used as cross-linking agents ¥ © K. ' eaast tieiydesc, Eia other valuable a laxative is hydrosliiaen "¥ eit®r @ Temiierungsinmittel are sB" Biliydroxjr likewisei © ₉ as E2? eaae & tecMii _s resorcin., 2-methylresorcins; 5 ~ Methj3, E3 £ 3rcia ₉ 2. 2 Methylhjdro ₉ 2 , 5-Dimethylhyörochinon UMI 2-tert _e Butylhyd: ^i> ceMnon _sl further Terbisdimgen such as 1 _p S-Bihydi'ssysi & phthglizi tmd 9 ₅ 10 Bihydrozyaatliracen More ve ^ © Ver -fesiflbar-aetsimgssiittei are t "4 ₉ 9." 10 -fetraliyaroxjaatlis-aeea _} 2 _ε 2S4 $, 4 '~ fetrahydroxybenzo-

4 s 4 ^r »Bihydroxytetraphenylmeth & n.« 2 ₉ β-Bihydroiiyan 3 _S 6 »2) iJiydrozy2: ai3itlä.oa _r Pyroiaellitic acid-bis-Cp-hydrozyphenyliiaid), 2,4-Dihydroxyacetophenon, 4,4» «-Bihyaroxybenzophenon, 414 * -BihydroxydipheaylsiiJ-foxid _$ 2 _? 4 ~ Dlbenzoylresoroin, 2.4 _t 5-2rihydr0zybutyrGph © 2Mm and 2 ₈ 4-biliydroxybene aldehyde.

When looking at a given set of sines: crosslinking agents going on to the other, will asas the duration and temperature the vulcanization so that you get a © for the Suitable for use in the Viillaal sationa speed receives.

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If A in the above general bisphenol formula denotes an alkylene radical, this can, for example, be methylene, ethylene, chloroethylene, puoroethylene, difluoroethylene, 1,3-propylene, 1,2-propylene, tetramethylene, monochlorotetramethylene, Monofluorotetramethylene, Trifluortetränethylene, 2-methyl-1,3-propylene, 2-methyl-1 »2-propylene, pentamethylene, pentachloropentamethylene, pentafluoropentamethylene or hexamethylene. If A is an alfcylidene radical, this can be, for example, an ethylidene, dichloroethylidene, difluoroethylidene, propylidene, isopropylidene, trifluoroisopropylidene, hexafluoroisopropylidene, hexafluoroisopropylidene, butylidene, heptachlorobutylidene, heptafluorobutylidene or 1,1-hexylidene, pentylidene, -Cyclohexylidenrest be. If A is a cycloalkylene radical, this can, for example, be 1,4-cyclohexylene, 2-chloro-1,4-cyclohexylene, 2-fluorine-1,4-cyclohexylene, 1,3-cyclohexylene, cyclopentylene , Monochlorcyclopentyleii-, Monofluorcyclopentylen- or Cycloheptylenrest be. When A represents an arylene group, this may be a m-Phenylsn-, p-phenylene ~, 2 ~ 0hlor _1-f 4-phenylene, 2-Pluor-1,4-phenylene _f methylphenylene, Dimethylphenylen-, ÜJrimethylphenylen-, Tetramethylphenylene, 1,4-haphthylene, 3-fluoro-1,4-naphthylene, S-chloro-i ^ -naphthylene, 1,5-haphthylene or 2,6-haphthylene.

Cross-linking of highly fluorine-substituted polymers with aromatic polyhydroxy compounds must be in the presence a catalyst can be carried out. Catalysts that accelerate the vulcanization of elastomers are generally used referred to as a vulcanization accelerator · Ss is a essential feature of the invention that a quaternary ammonium compound is used as a vulcanization accelerator. It is surprising that these compounds found such effective VuI-canization accelerators for fluorine-substituted elastomers in the presence of the metal compound and the crosslinking agent and that some of the best results according to the invention with a polymerization accelerator content of only

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about 0.2 to 0.8 parts by weight can be achieved for every 100 parts by weight of elastomer. A particularly preferred accelerator consists of methyl trioctylammonium chloride or a mixture of the same with 1 to 50 percent by weight of another quaternary ammonium compound in the context of the above description, based on the total weight of the accelerator Other preferred polymerization accelerators are laurylpyridinium chloride, Tetraheptylammonium chloride and tetrabutylammonium stearate. Examples of further polymerisation accelerators are tetramethylammonium hydroxide, tetramethylammonium pentachlorothiophenolate, Lauryl dimethyl naphthyl methyl ammonium chloride, lauryl isoquinolinium chloride, distearyl dimethyl ammonium chloride, Tetrahexylammonium tetrafluoborate, methyl trioctylammonium oxalate, hexadeeylpyridinium chloride, Benzyl-trioctylammonium chloride, M-irifluoromethylbenzyl-trioctylammonium chloride, Diisobutylphenoxyethoxyethyl-dimethylbenzylammonium chloride, Methoxyethoxyethyl-trioctylammonium chloride and 2,2,3 »3-tetrafluoropropyl-trioctylammonium chloride · Quaternary salts which can be used as vulcanization accelerators can be prepared by known methods, such as by Ion exchange or neutralization of a quaternary ammonium hydroxide with the appropriate acid, produce

Before the polymerization accelerator with the other ingredients is mixed into the mixture, it is often convenient to mix it with fine particles of pesticide that come with the vulcanization accelerator or any other ingredient do not enter into a harmful reaction. This is how the tulcanisation accelerator can e.g., adsorbed on finely divided calcium carbonate, calcium silicate, silicon dioxide or the like or be absorbed.

The mixtures according to the invention can be those mentioned above Contain vulcanization accelerators as the only accelerator, or they can be mixtures of the vulcanization

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faster and one or more already as vulcanization accelerators contain compounds known for the copolymer.

The metal compound, the crosslinking agent and the vulcanization accelerator can with the elastomeric copolymer in known for the production of rubber mixtures Mixing devices are mixed, e.g. on the roller mill .or ie Banbury mixers. The mixtures can be known per se FSlIstaffe, pigments, pore formers and other additives be added. Furthermore, the mixture can be mixed with a solvent for the copolymer, and this liquid mixtures can be used as adhesives, coatings, films, and the like. Among the preferred Solvents include acetone, methyl ethyl ketone, ethyl acetate, Amyl acetate and tetrahydrofuran.

The initial vulcanization of the vulcanizable mixture takes place - preferably by heating for about 1 to 30 minutes to 149 to 204- ° C, and you can use conventional Rubber milcanizing presses, molding, extrusion and the like use that are equipped with suitable heating devices. If you want a product with the highest possible heat and wants to produce resistance to roughness, the product is preferably post-vulcanized by leaving it for a further 1 to 4-8 hours ia oven is heated to 204 to 260 ° C. The for the respective Purpose of use best vulcanization time and temperature depend on factors such as the type and amount of ingredients and the desired properties of the end product.

The new mixtures are suitable for the manufacture of products from. lower permanent deformation, e.g. of heat-resistant, elastic packing rings, shaft seals for oil wells, other seals, hoses and the like For the purposes of the invention, products can be manufactured, oils from aerea the advantages of rapid vulcanization,

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have better durability and better flowability in the unvulcanized state (no premature gel formation) and a satisfactory stress-strain behavior. Further advantages will look from the circumstance that some of the most effective _f Yulkanisationsfceschleuniger are less expensive and skin of working with them people travel less than gewissa widespread known Yulkanisationsbeschleuniger.

In the following examples, all quantities refer to unless otherwise stated, on the weight »

Examples 1 bJ3 3

There are three blends of fluorine-substituted elastomers made according to the invention, vulcanized and tested ^ the compositions, and the Yersuoh results are found in Table I. The blends differ from one another in terms of their vulcanization accelerator content. They are suitable for the purposes described above.

saber Example 1 e I. 2 3 composition t Parts by weight Liquid-bonded elastomer
Magnesia ("Maglite D")
Calcium hydroxide
Buss
accelerator
Hydroquinone
Kooney Attachment Test 1 100
3
6th
30th
O l _t 1
1 100
S.
30th
1.2 minimum
Minutes to climb
by 5 points
Mooney Attendance Test 2 100
3
6th
30th
ί ' 34
30+ 33
30+ minimum
Min. To increase by 5 points
* _m η η η κ | q it
- 10
109849/16 35
30+ 39
13th
16 42
9
It 37
18th
24
73

LC-1332 / 1332A Λ example ί 2 71 4.6 71 2123110 cm «kg 8.1 - 72 Tabel ODR vulcanization test Torque, 49 29 57 59 59 ain I (continued) 119 77 119 3 102 133 5 1 3.5 180 106 160 113 170 7.5 11.5 6ö 114 59 118 59 10 37 15th 90 36 25th 21st 30th 113 After vulcanizing 20th 18th 19th according to procedure 1 Shore hardness " 100 5 ^ module, kg / cuT ₂ 72 71 69 Tensile strength, kg / cm 62 70 70 Elongation at break, i » 133 137 133 Yerzley-Elasticity 170 170 160 Permanent compression set, Test 1 36 23 20th Permanent compression set, Test 2 16 16 17th After vulcanizing according to procedure 2 Shore hardness " 32 39 46 100 jUModul, kg / ciT « 95 98 98 Tensile strength, kg / approx 215 195 170 Elongation at break,? 6 Permanent compression set, Test 1 Permanent compression set, Test 2 Do the vulcanization according to procedure 3 100 jC module, kg / approx ² " Tensile strength, kg / approx Elongation at break, jC

You quantities of the individual ingredients are in the table in Parts by weight given. In all of the mixtures, the fluorine-substituted elastomer is a copolymer of 60 parts by weight of vinylidene fluoride and 40 parts by weight of hexafluoropropylene ■ it has a Mooney viscosity (ML-10 at 100 ° C) of 60. The

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EGG. du Pont de Uemours and Comp. LC-1332 / '332A

The type of soot used is "Thermax MT". A methyl trioctylammonium eliloride of 88 percent purity, which has a small amount of decyl groups ("Aliquat 336" from General Mille, Inc. "), absorbs on hydrated silicon dioxide (" Silene D ^!! } in a weight ratio of methyl "serves as the vulcanization accelerator -trioctylammonium chloride to silicon dioxide of 33:67. With regard to the active ingredient, the content of vulcanization accelerator in the mixture of Example 1 is only Q ', 53 parts -trioctylammonium chloride is much less hygroscopic and more economical and has less tendency to irritate the skin.

They are given in Table I mixtures by. Mixing of the ingredients on the two-roll mill at 25 ° C. The Mooney burn test 1 is carried out at 121 ° G on a freshly prepared mixture according to ASTM test standard D-1646-63. The Mooney Burn Test 2 is carried out using the same method on a sample that has been aged for 3 days at 38 ° C. and 100% relative humidity. The values for the scorch test show the excellent processing reliability of the mixtures. In the ODR vulcanization test, which indicates the rate of vulcanization, a visual vibrating disc rheometer is used at 168 ° C. Here, letting a grooved _s doppelkegelfömige disc over an angular swing away, being tightly between two pieces of the sample © total presses is to measure the relative viscosity, and in certain time intervals with the progress of vulcanization (cure time is in the left column Table given in minutes) as a measure of the viscosity of the viscosity. The torque recorded in cm kg that is required to make the disk vibrate * The values obtained in this way can be used to produce vulcanization curves by plotting the viscosity values against time;

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BATH ORIGINAL

LC-1332 / 1332A **

the vulcanization speed then results from the slope of the curve at its steepest point.

The Shore hardness (durometer A) is according to the ASTM Erüfnorm D-676 determined. In vulcanization method 1, the samples are vulcanized in the press at 168 ° C. for 10 minutes and Post-vulcanized in an oven at 232 ° C for 6 hours. The vulcanization process 2 is the same with the difference that the roof vulcanization takes 24 hours. The vulcanization process 3 is the same as vulcanization process 2, but with • the difference that the samples also remain in the for 70 hours. Oven to be aged at 276 ° C. The vulcanization for manufacturing the vulcanized sample is carried out at a pressure of 18,200 kg. Post-vulcanization and heat aging take place in an oven in which a fan circulates the air leaves. Modulus, tensile strength and elongation at break are determined at room temperature according to ASTM test standard D-412-66. the Values for the permanent compression set according to test 1 are according to ASTM test standard D-395-61, method B, using j of 0.353 cm packing rings with a round cross-section over the course of 70 hours at 204 ° C. The values for the remaining

j de compression set according to test 2 are determined in the same way, but with the packing rings using Yerzley elasticity pills 1.27 cm thick and 1.9 cm in diameter can be replaced. The Yerzley elasticity values will be determined at 25 ° C according to ASTM test standard D-945-59.

Examples 4 and 4A

The two elastomer blends given in Table II are prepared and tested. The mixture according to the example 4A is not within the scope of the invention since it contains the aromatic polyhydroxy compound essential to the invention as a crosslinking agent does not contain. In both blends, the fluorine-substituted elastomer, the Ruse, and the mixing process are the ones same as for the mixtures according to Table I.

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eationsbeschleuniger serves methyl-trioctylaamoniurabroiaid absorbed to Calciumsilisat at a £ ewichtsverhältnis of methyl trioetylanrajaniuiBbroiaid to öaleimasilieat 67s of 33. The tests werdexn, wi © described in fabeile 1 following, durohgeriSirt2 with the difference that the samples home Vulkanisisrvsrfaireen 4 45 Miniatsn vulcanized in the press at 168 ° C and Sann. 24 hours at 232 ° C in the oven

become «,! Peat 5 & \ i £ permanent® pressure relief

is the same as Seat 2, with the difference that this one Test tang 24 stands at 160 ° G is carried out.

As Table II shows, the mixed breed according to Example 4 far exceeds the mixture according to Example 4A in terms of its vulcanization speed and its properties after tulcanisation. As a result of the incomplete tulcanisation of the latter, no meaningful values are obtained in the three specified tests, even if the test for permanent brucicvar deformation is carried out under mild test conditions.

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is

Tabel

II

example Examples 4th 4A 100 100 3.5 * composition Parts by weight 2 2 3.5 Fluorine-substituted elastomer 6th 6th 4.6 magnesia 30th 30th 4.6 Calcium hydroxide 1.5 1.5 5.8 Soot 1 "·. 5.8 accelerator Torque, cm · kg Hydroquinone ODR vulcanization test 28 19th Min. 114 56 5 120 810 10 124 - 15th 131 20th 135 - 30th 60 - After vulcanizing 89 • according to procedure 4 112 100 lb module, kg / cm ² ₂ 125 Tensile strength, kg / cm 77 Elongation at break, i » Shore hardness 36 Permanent compression set according to test 2 10 Permanent compression set 5 and 5A according to test 3

The two elastomer blends given in Table III are prepared and examined to determine the importance of the combination of crosslinking agents and vulcanization accelerators. The composition of the mixture according to the example 51 is not within the scope of the invention as it is used as a crosslinking agent a diamine (dicinnamylidene-hexamethylenediamine) instead the essential aromatic polyhydroxy compound (in Example 5 hydroquinone) contains. With these mixes ! 2nd applies to those of the other examples

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109 84.9 / 167 3

21231IQ

IC-1332 / 1332A / ί

the same fluorine-substituted elastomers, the same carbon black and the same mixing process as in Examples 1 "to 3. In both mixtures, the vulcanization accelerator consists of 67 percent by weight of methyl trioctylammonium carbonate and 33 percent by weight of calcium silicate, in which the ammonium salt is absorbed 4 (45 minutes vulcanization in the press at 168 0 and 24 hours post-vulcanization in the oven at 232 ° C), test 3 for permanent compression set (pills, 24 hours, 160 ° G) and test 2 for permanent compression set (pills, 70 Hours, 204 ° C) is described above Compression set test 4 is the same as test 3 except that it is performed at 160 ° C for 72 hours.

From Table III it can be seen that the mixture of Example 5 (according to the invention) with regard to their vulcanization rate and their properties after vulcanization are those of Example 5A (which do not fall within the scope of the invention lies) far exceeds.

Tabel

III

example 5 4 -
5A 100
2
6th
30th
0.75
1.5 - 16 - 8th
21
30th
39
53
63 composition Parts by weight Torque, cm · kg 109849/1673 Fluorine substituted
magnesia
Calcium hydroxide
Soot
accelerator
Hydroquinone
Diamine Elastomer 100
2
6th
30th
0.75
1.0 ODR vulcanization test 102
117
120
121
122
123 Min. 5
10
15th
20th
30th
60

LC-1332 / 1332A
Tabel ti
III (Continuation) 2123110 example 5 5A After vulcanizing according to procedure 4 100 # module, kg / em ^
Permanent compression set
according to test 3
Permanent compression set
according to test 4
Permanent compression set
according to test 2
B is ρ i e 1 e 74
4th
7th
16
6 to 10 32
16
26th
40

The five elastomer blends given in Table IV are, are manufactured and studied for the use of others to show quaternary ammonium compounds as vulcanization accelerators for the purposes of the invention. The following vulcanization accelerators are used in these examples:

Example active ingredient of the vulcanization accelerator

6 methyl trioctyl ammonium oxalate

1 methyl trioctylammonium acetate

8 methyl trioctylammonium hydroxide

9 methyl trioctylammonium stearate 10 methyl trioctylammonium iodide

For all the mixtures given in Table IV in which the vulcanization accelerator is 67 percent by weight of active ingredient and 33% by weight of calcium silicate, into which the active ingredient is absorbed, refer to the in the amounts given in the table on the active ingredient itself. Vulcanization process 2 (45 minutes vulcanization in the Press at 168 ° C and post-vulcanization in the oven at 232 ° C for 24 hours) and test 1 for permanent compression set (Packing rings, 70 hours, 204 ° C) are described above.

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21231 IC-1332 / 1332A 5? After vulcanizing 63 10 /1 le IV 9 4.6 100 10 6th according to procedure 2 95 e 1 8th Parts by weight 36 3 example 100 jS module, kg / cm ² ₂ 140 away 7th 85 6th composition Tensile strength, kg / cm 100 99 30th 100 Eluosubstituted 100 Elongation at break, # 3 108 0.83 3 Elastomer 3 100 S. 1.0 6th magnesia 6th 3 30th 3in »kg 30th Calcium hydroxide 30th 6th , 53 0.40 63 0.67 Soot 0, 30th , Ο 1.0 126 6.9 1.0 accelerator It 0, Torque, < 160 106 Hydroquinone 40 116 ODR vulcanization test O 107 117 3.5 Min. 11t 122 120 6.9 5 97 124 28 10 108 5 124 71 15th 110 124 70 107 20th 114 119 30th 160 81 44 116 70 130 145

Permanent compression deformation according to
Test 1

14th

26th

26th

27

Similar favorable results are obtained if 0.6 to 1.0 part of an accelerator is used in Example 6, which is 67 percent by weight of active ingredient and 33 percent by weight of calcium silicate using the following active ingredients:

Propyl-trioctylammonium chloride, T e traheptylammonium chloride,

Lauryl-dimethyl-naphthylmethylammonium chloride,

lauryl isoquinolinium saccharinate, hexadecylpyridinium chloride, distearyl dimethylammonium chloride, di- ¹¹ SQ ja "-dimethylammonium chloride,

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212311b

LC-1332 / 1332A Jß

Diisobutylphenoxy-äth.ojcyäthyl-dimetliyl'beiizylainiDoniiimchlorid, Me thyldodecylbenzyl-trimethylammoniumchlorid, Methyldodecyl-xylene-bis- (trimethylammoniumehlorid), H-alkyl- ( ^c -ι ρ * ° 14 ' ^C 16 ^ "" ^d * ^me thyl- benzylammonium chloride, benzyl trimethylammonium hydroxide,
Tetrabutylaramoniura hydroxide,
Bibenzyl-dimethylammonium hydroxide,
Benzyl-te tradecyl-dimethylammonium hydroxide, letramethylammonium hydroxide,
TetralratylaimDonium pentachlorothiophenolate, TetramethylajimioniumpentachlorthiopheiiQlat, Benzyl-triBethylammonium terephthalat.

Examples 11 Ms 13

The three elastomer mixtures given in Table Y are prepared and examined to illustrate the use of other metal compounds in the context of the invention. Lead oxide and lead phosphite are used without magnesia and in varying amounts together with magnesia. Red lead is known as lead orthoplumbate (2 PbO · PbO ₂ ), and lead phosphite is sometimes referred to as lead (II) phosphite. The ODR vulcanization test is carried out at 177 ° C instead of 168 ° C. Compression Set Test 1A is a rigorous test performed over 336 hours at 204 ° C bit packing rings. Otherwise, this test corresponds to test 1 for permanent compression set. Mooney burning test 1 (121 ° C, freshly prepared mixture), vulcanization process 2 (vulcanization in the press at 168 ° C for 10 minutes and post-vulcanization in the oven at 232 ° C for 24 hours), test 1 for permanent compression set ( Packing rings, 70 hours, 204 ° C) and test 2 for compression set (pills, 70 hours, 204 ° C) are described above.

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109849/1673

212311 LC-1332 / 1332A T a example B e i s ρ i 0 η e 1 e e V 12th 14 to 23 13th Composition bell Parts by weight Fluorine-substituted s 11 Elastomer 100 100 Hennige 8th 4th Lead phosphite too 8th 4th magnesia 8th 3 3 Buss 8th 30th 30th Accelerator (according to - Example 1) 30th 0 1.0 1.0 Hydroquinone 8 0.8 0.8 Mooney Burn Test 1 1, minimum 0, 38 35 Minutes to climb by 5 points 30th 30+ 30+ ODR vulcanization test Torque, cm »kg Min. 304 5 5 9.2 3.5 to 89 22nd 15th 3, 112 71 20th 43 115 94 30th 102 117 105 Kach the vulcanization. 105 according to procedure 2 107 Shore hardness ₉ 71 69 100 # module, kg / cm ₂ 60 43 Tensile strength, kg / cm 71 126 112 Elongation at break, fi 46 170 180 Permanent compression set 112 according to test 1 180 27 29 Permanent compression set according to test 1A 36 67 61 Permanent compression set according to test 2 72 23 18th 43

Ten blends of the fluorine-substituted elastomer are made to avoid the use of other crosslinking agents to explain within the scope of the invention. The results can be found in Table VI. As the crosslinking agent, there are the following used:

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109849/1673

LC-1332/1332 ff

Example crosslinking agent

H 4,4'-biphenol

15 isopropylidene bis (4-hydroxybenzene)

16 hexafluoroisopropylidene-bis- (4-hy-

droxybenzene)

17 4,4'-dihydroxydiphenyl sulfone

18 2,4-dihydroxybenzophenone

19 2,4-dihydroxyacetophenone

20 4-chlororesorcinol

21 phloroglucine

22 2,4-dihydroxybenzoic acid

23 1,419,10-tetrahydroxyanthracene.

In Examples 14 and 16, the same accelerator is used as in Example 1 (33 parts of methyl trioctylammonium chloride and 67 parts of silica); in Example 15, the vulcanization accelerator consists of 67 percent by weight Tetraheptylammonium chloride, absorbed at 33 percent by weight Calcium silicate, "and in Examples 17-23 there is the 67 weight percent vulcanization accelerator made from methyltrioctylammonium chloride and 33 weight percent silica. The ODR vulcanization test is used in the examples 14 to 23 performed at 177 ° 0.

In Examples 14 and 16, 15 minutes at 177 ° G in the Press vulcanized and post-vulcanized in the oven at 232 ° C for 24 hours; in example 15 the same vulcanization process is used with the difference that vulcanization in the press only takes 7 minutes; in Examples 17 to 20 vulcanization is carried out in the press at 177 ° C. for 20 minutes and Post-vulcanized in an oven at 260 ° C for 18 hours; in Examples 21 to 23 it is 15 minutes in the press at 177 ° C vulcanized and post-vulcanized in an oven at 260 ° C for 18 hours.

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1098 ^ 9/1673

LC-1332 / 1332A

The test specimens for permanent compression set are as follows carried out:

Test 1: packing ring, 70 hours, 204 ° C

Test 1As packing ring, 336 hours, 204 ° C

Test IB: packing ring, 70 hours, 232 ° C

Test 2: pills, 70 hours, 204 ° C

Test 2B: pills, 70 hours, 232 ° C.

Table VI

example 14th 15th 16 17th Parts by weight 100 2, 0 100 0 18th composition 3 4, 0 3 0 Fluorosubstituted 100 6th 69 6th Elastomer 100 3 30th 138 30th 100 magnesia 3 6th 1. 161 3 1, 3 3 Calcium hydroxide 6th 30th 3, 6th 2, 8th 6th Soot 30th 0.7 Torque 75 cm. kg 30th accelerator 1.0 1.5 83 0.6 Crosslinking agents 1.7 4.6 120 2, 1.5 ODR vulcanization test 98 140 5, Min. 99 47 5 8th 100 2.3 10 83 101 18th 94 40 15th 114 32 74 20th 117 72 72 30th 120 48 52 95 After vulcanizing 88 126 Shore hardness _? 75 160 180 73 100 # module, kg / cm ₂ 69 56 Tensile strength, kg / cm 115 137 Elongation at break, $> 150 37 180 Permanent pressure 53 53 shaping according to 52 Test 1 29 ⁿ 1A 54 60 "1B 58

2 B

27

42

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109849/16 73

21st LC-1332 / 1332A 2311 example 19th 0 _ΛΛ VI 20th (Port setting) 22nd Parts by weight 100 , 5 28 100 • 24 composition Vl 3 , 2 43 3 58 Tabel Fluorine substituted 21st 6th 47 6th 60 Elastomer 100 100 30th 53 30th 23 62 magnesia 3 3 1.0 2.0 Calcium hydroxide 6th 6th 1.4 74 1.2 78 Soot 30th 30th , 6 Torque, < 47 im-kg 100 58 accelerator 0.6 0 , 2 94. 3 98 Crosslinking agents 1.0 1 3 185 31 6th 170 ODR vulcanization test 9 86 30th Min. 21st 95 1.8 5 11.5 43 78 99 1.5 92 10 68 64 80 15th 72 70 40 80 • 63 30th 98 30th 94 After vulcanizing 101 105 Shore hardness ₀ 72 250 110 100 SG module, kg / cni ₂ 67 Tensile strength, kg / cm 126 Elongation at break, $> 155 84 83 Remaining pressure 79 71 shaping according to 50 60 Test 1A 70 "IB 64 " 2 B 40

109849/1673

Claims (21)

Claims Vulcanizable mixture of a fluorine-substituted elastomer in which an elastomeric copolymer of vinylidene fluoride and at least one other, fluorine-substituted monomer is present in admixture with constituents which have the Improve vulcanization properties, characterized in that they improve the vulcanization properties Components divalent metal oxides or hydroxides, optionally mixed with metal salts of weak acids, an aromatic polyhydroxy compound acting as a crosslinking agent for the copolymer and a quaternary amino compound acting as a vulcanization accelerator the general formula or and R, independently of one another R ₂ E ₁ -NR, contains, wherein R ₁ , R ₂ , ^
C ₁ - to C ₂₀ -alkyl, lluoroalkyl, aralkyl, polyoxyalkylene or polyoxyfluoroalkylene radicals, with the proviso that at least two of these radicals are alkyl or aralkyl radicals, R ^ a G ₁ - to C ₂₀ -alkyl radical and X is a hydroxyl, ₉ halogen, sulfate, sulfite, carbonate, pentachlorothiophenolate «, fetrafluoborate, hexafluorosilicate, - 24 - 1 09849/1 673 LC-1332 / 1332Α Hexafluorophosphate, dimethyl phosphate, C ₁ - to gQ aralkyl or aryl carboxylate or dicarboxylate ion. 2. Vulcanizable mixture according to claim 1, characterized in that that they per 100 parts by weight of copolymer about 1 to 15 parts by weight of metal compound, about 0.1 to Contains 5.0 parts by weight of crosslinking agent and about 0.1 to 2.0 parts by weight of vulcanization accelerator. 3. Vulcanizable mixture according to claim 2, characterized in that that it contains the vulcanization accelerator in amounts of 0.2 to 0.8 parts by weight. 4. Vulcanizable mixture according to claim 2, characterized in that that the copolymer is a copolymer of vinylidene fluoride and hexafluoropropylene, a copolymer of vinylidene fluoride and monochlorotrifluoroethylene or a copolymer of vinylidene fluoride, hexafluoropropylene and Is tetrafluoroethylene. 5. Vulcanizable mixture according to claim 4, characterized in that that the crosslinking agent is a di-, tri- or tetrahydroxybenzene, naphthalene or anthracene or a Bisphenol of the general formula ^{n (H0)} (0H) n is where A is a bifunctional aliphatic, cycloaliphatic or aromatic radical with 1 to 13 carbon atoms or a thio, oxy, carbonyl, sulfinyl or Sulphonyl radical and can optionally be substituted by at least one chlorine or fluorine atom, χ den Value 0 or 1, η has the value 1 or 2 and every aromatic - 25 - 109849/1673 LC-1332 / 1332A review ring of polyhydroxy compound if necessary at least one glilorine, fluorine or bromine atom or at least is substituted by a carboxyl or acyl radical. 6. Vulcanizable mixture according to claim 5, characterized in that that the crosslinking agent is hydroquinone. 7. Vulcanizable mixture according to claim 5, characterized in that that the crosslinking agent hexafluoroisopropylidene-bis (4-hydroxybenzene) is, 8. Vulcanizable mixture according to claim 5, characterized in that that the crosslinking agent is 4,4'-dihydroxydiphenyl sulfone is. 9. Vulcanizable mixture according to claim 4, characterized in that that the vulcanization accelerator consists of 50 to 100 percent by weight of methyl trioctylammonium chloride. 10. Process for vulcanizing elastomeric copolymers of vinylidene fluoride and at least one other,
fluorine-substituted monomers in the presence of constituents which improve the vulcanization properties, characterized in that divalent metal oxides are used as constituents which improve the vulcanization properties
and / or hydroxides, optionally mixed with metal salts of weak acids, one as a crosslinking agent
aromatic dihydroxy compound acting for the copolymer and a quaternary affinity compound of the general formula which acts as a vulcanization accelerator R ₁ -IT-I V Vi X "or - 26 - 109843/1673 LC-1332 / 1332A ^J. used and mixed with the Copoiymerisat, wherein R ^, R ₂ , R ₅ and R. independently of one another C ₁ - to C ₂₀ -AIkVl-, fluoroalkyl, aralkyl, polyoxyalkylene or polyoxyfluoroalkylene can mean, with the proviso that at least two of these radicals are alkyl or aralkyl radicals, R, - a Ο ..- to C ₂ Q-alkyl radical and X a hydroxyl, halogen, sulfate, sulfite, carbonate, pentachlorothiophenolate, tetrafluoborate, hexafluorosilicate, hexafluorophosphate , Di- ■ ethyl phosphate, C ₁ - to C ₂₀ alkyl, aralkyl or aryloarboxylate or dicarboxylate ion means, and that the mixture is heated for vulcanization. 11 · Vulcanized mixture, produced according to claim 10. 12. The method according to claim 10, characterized in that a mixture is used which contains about 1 to 15 parts by weight of metal compound per 100 parts by weight of copolymer, contains about 0.1 to 5.0 parts by weight of crosslinking agent and about 0.1 to 2.0 parts by weight of vulcanization accelerator. 13. The method according to claim 12, characterized in that the copolymer is a copolymer of vinylidene fluoride and hexafluoropropylene, a copolymer of vinylidene fluoride and monochlorotrifluoroethylene or a copolymer from vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene are used. 14. The method according to claim 13, characterized in that the crosslinking agent used is a compound according to claim used. 15 · The method according to claim 14, characterized in that hydroquinone is used as the crosslinking agent. 16. The method according to claim 14, characterized in that Ban as a crosslinking agent hexafluoroisopropylidene-bis- (4-hydroxybenzene) used. - 27 - 109849/1673 LC-1332 / 1332A 17. Procedure according to. Claim 14, characterized in that the crosslinking agent used is 4,4 ^f -dihydroxydiphenyl sulfone
used. 18. The method according to claim 13, characterized in that a vulcanization accelerator is used, which to
about 50 to 100 percent by weight consists of methyl trioethylammonium chloride. 19. Vulcanized mixture produced according to claim 18. 20. The method according to claim 12, characterized in that; man di
heats. the mixture is heated to 149 "to 204 ° C for 1 to 30 minutes 21. The method according to claim 20, characterized in that the mixture for a further 1 to 48 hours to 204 to
260 ° G heated. - 28 - 109849/1673