Metal amine complex containing fluoropolymer compositions

the present invention relates to fluoropolymer compositions with Nitrile group-containing cure-site.

fluorine -Containing polymers (also known as "fluoropolymers") are a commercially useful Substance class. Among the fluoropolymers include, for example, cross-linked Fluoroelastomers and semi-crystalline or amorphous fluoroplastics. fluoroplastics have a high thermal stability and are generally at high temperatures particularly useful. You can well as extreme toughness and flexibility exhibit at very low temperatures. Some have a very low dielectric loss and high dielectric strength and can have unique low friction properties.

fluoroelastomers have substantial Tolerance to high temperatures and harsh chemical environments. Therefore they are particularly well suited for use as seals, closures and other molded parts in systems that elevated temperatures and / or corrosive chemicals are exposed. Such parts find u. a. wide application in the chemical processing industry, the semiconductor industry, the aerospace industry and the oil industry.

fluoroelastomers often contain a cure site to facilitate the curing in the presence of a catalyst. One class of suitable cure-site contains Nitrile-containing monomers. As curing catalysts organotin catalysts generally used. Such catalysts however, are toxic and can in cured unwanted product extractable metal residues left behind.

in one aspect, the invention provides a composition comprising (a) a fluoropolymer having interpolymerized units derived from itself a cure derived with a nitrile group; and (b) a catalyst composition comprising a compound having the formula: <img img-content="cf" img-format="tif" he="32" wi="80" file="00020001.tif" />where M is a divalent metal, X is a anionic group, and n 2 to 6, preferably 3 to 5, is.

in yet another aspect, the invention provides a method for hardening this composition and the cured compositions.

the Compositions retain the advantages of the use of nitrile containing cure site, such as the high temperature performance properties and chemical resistance, the with the use of organotin compounds as a catalyst system with such cure site typically be achieved. At the same time, the compositions have significantly improved in compression set. compositions suitable for Applications in which the polymer stability (eg. As thermal stability) and / or chemical resistance are important. They are also suitable for use in the manufacture of silicon wafers.

the Details of one or more embodiments of the invention In the accompanying drawings and the description below set forth. Other features, objects, and advantages of the invention will be apparent from the description and the claims.

Suitable Fluoropolymers include interpolymerized units derived of a nitrile group-containing monomer, and preferably at least two principal monomers derived. Examples of suitable candidates for the principal monomer are perfluoroolefins (for. example, tetrafluoroethylene and hexafluoropropene), Perfluorovinyl (z. B. perfluoroalkyl and perfluoroalkoxy) and hydrogen-containing monomers such as olefins (for. example, ethylene, Propylene, and the like) and partially-fluorinated olefins such as vinylidene fluoride.

&lt;?page 3?&gt;

Suitable perfluorinated vinyl ethers include those of the formula: <st32:che xmlns:st32="http://lighthouseip.com/">CF₂= CFO (R '_fO)_a(R ''_fO)_bR_f (1)</st32:che>wherein R '_f and R ''_f for equal or different linear or branched perfluoroalkylene 1-6 Carbon atoms; a and b independently represent 0 or is an integer 1-10 and R_f a perfluoroalkyl group 1-6 Carbon atoms.

A preferred class of perfluoroalkyl vinyl ethers includes compositions of the formula: <st32:che xmlns:st32="http://lighthouseip.com/">CF₂= CFO (CF₂CFXO)_nR_f (2)</st32:che>wherein X F or CF₃ stands; n is 0-5 and R_f a perfluoroalkyl group 1-6 Carbon atoms.

All Particularly preferred are those perfluoroalkylvinylether, in where when referring to the above formula 1 or 2 n is 0 or Is 1 and R_f 1-3 carbon atoms. Examples for such perfluorinated ethers are perfluoromethyl, perfluoroethyl Perfluorpropylvinylether.

Other useful perfluorinated monomers include those compounds of formula: <st32:che xmlns:st32="http://lighthouseip.com/">CF₂= CFO [(CF₂)_m(CFZ)_uO]_nR_f (3)</st32:che>where R_f For a perfluoroalkyl group having 1-6 Carbon atoms, m represents 0-2, u for 0 or 1, n is 0-5, with the proviso that both m and n are not equal to zero, and Z is F or CF₃ stands. Preferred Members of this class are those in which R_f for C₃F₇ or CF₃, M 0 and n 1 stands.

More in the context of the invention useful Perfluoralkylvinylethermonomere are those of formula: <st32:che xmlns:st32="http://lighthouseip.com/">CF₂= CFO [(CF₂CF (CF₃)O)_G(CF₂)_k(OCF₂)_p] C_xF_{2x + 1} (4)</st32:che>where g is 0 or is an integer of 1-10 is, for k an integer from 1-6 stands for p 0-3 and x 1-5 is, with the proviso that, if k 0, p is also 0 stands. Preferred members of this class include compounds in which n 0 or 1, m represents Is 0 or 1 and x 1 stands.

in the Scope of the invention useful perfluoroalkoxy are u. a those of the formula.: <st32:che xmlns:st32="http://lighthouseip.com/">CF₂= CFO (CF₂)_t(CFZ)_uO (CF₂O)_wC_XF_{2x + 1} (5)</st32:che>in which Z for F or CF₃ is, t is 1-3, u is 0-1, w is 0-3 and x 1-5 and preferably 1 stands. As representative examples for useful perfluoroalkoxy were in single CF₂= CFOCF₂OCF₂CF₂CF₃. CF₂= CFOCF₂OCF₃, CF₂= CFO (CF₂)₃OCF₃ and CF₂= CFOCF₂CF₂OCF₃ called.

one Mixtures of perfluoroalkyl vinyl ethers and Perfluoralkoxyvinylethern can use.

in the Scope of the invention include those useful perfluoroolefins of the formula: <st32:che xmlns:st32="http://lighthouseip.com/">CF₂= CF-R⁵_f (6)</st32:che>where R⁵_f fluorine or perfluoroalkyl of 1 to 8 and preferably 1 to 3 carbon atoms stands.

Of Furthermore, in the fluoropolymer of the invention partially-fluorinated monomers or hydrogen-containing monomers such as Olefins (for. Example, ethylene, propylene and the like) and vinylidene fluoride be used.

On example for a useful fluoropolymer is tetrafluoroethylene and at least a perfluoroalkyl constructed as principal monomer units. In such copolymers, the copolymerized perfluorinated make Ether about 15 to about 50 mole percent (mol%) (especially preferably 15 to 35 &lt;?page 4?&gt;mol%) of total monomer units present in the polymer out.

in the fluoropolymer having interpolymerized units derived from itself a cure with a nitrile derived, can one or more other fluoropolymers are incorporated. Furthermore may include one or more fluoropolymers (which is one or more copolymers may contain) with the fluoropolymer (which may comprise a copolymer) having interpolymerized Units derived from a cure derived having a nitrile mix. Such other fluoropolymers, which are useful in a blend and / or copolymer, include the entire collection described above. The other Fluoropolymer or the other fluoropolymers may or may not interpolymerized units derived from a cure derive a nitrile group, and / or to a selected curative system parked reactive centers contained. So you can, for example, two different fluoropolymers, each having interpolymerized contain units from a cure with it a Nitrile deduce mix to fluoropolymer according to the invention provide.

On Another fluoropolymer may together with another curing agent, such as described below, also used to provide special properties will. Thus, for example, a suitable for peroxide cure Fluoropolymer and a peroxide curative concomitantly used in order to improve the chemical stability. such Blend balances the thermal stability and the chemical stability of the resulting Mixture of and may also provide economic benefits. These other hardener can also for curing a mixture of nitrile containing fluoropolymers used be without one a fluoropolymer must concomitantly without nitrile.

the Fluoropolymers can be prepared by processes known per se. Thus, the Polymerization by free radical polymerization of the monomers to be carried out, z. B. in solutions Emulsions or dispersions in an organic solvent or water. Because of the rapid and almost complete implementation of monomers, easy removal of polymerization and ease of isolation of the polymer is the polymerization in aqueous emulsion or suspension often prefers. In the emulsion polymerization is in Usually monomers in an aqueous medium in the presence of a radical initiator system, z. B. a persulfate, such as ammonium persulfate, potassium permanganate, or organic peroxides, frequently in the presence of reducing agents and a fluorinated nichttelogenen Surfactant, such as APFO (ammonium perfluorooctanoate).

the aqueous emulsion can be carried out continuously under steady-state conditions, being carried out at, for example, monomers, water, surfactants, buffers and Catalysts continuously a stirred reactor under optimum pressure and temperature conditions supplies, while the resulting emulsion or suspension continuously withdrawn becomes. An alternative technique is the discontinuous or semi-continuous Polymerization, in which the ingredients into a stirred reactor Recorded and at a fixed temperature determined over a period submitted are allowed to react or components in the reactor and the monomer to maintain a constant pressure in the reactor is added until a desired formed polymer amount Has.

the radical polymerization may also be in the presence of a Perfluorsulfinats and an oxidizing agent to improve the processability of the resulting fluoropolymer composition can be performed. Such oxidizing agents are water soluble and can convert it into a sulfinate Sulfonylgruppierung. It is believed that the resulting sulfonyl SO₂ eliminate and a fluorinated radical can form, which polymerization the ethylenically unsaturated Monomers initiated. A number of useful oxidizing agents known as <patcit><text>U.S. Patents 5,285,002</text></patcit> and <patcit><text>5,639,837</text></patcit> teach. Representative examples for such useful oxidizing agents are sodium, potassium and Ammonium persulfates, perphosphates, perborates, percarbonates, -bromate, chlorates and hypochlorites. Other useful oxidizing agents include cerium (IV) - compounds, such as (NH₄)₂Ce (NO₃)₆, The used Amount of oxidizing agent may vary depending on the oxidizing agent used in each case and sulfinate vary. Usually one uses an equimolar Amount or less (based on the Sulfinatmenge).

Perfluorsulfinate, the for this purpose are suitable, inter alia, are those of the <patcit><text>US-PS 5,285,002</text></patcit>, by the following general formula are shown: <st32:che xmlns:st32="http://lighthouseip.com/">R³_fSO₂M_{l / x} (7)</st32:che>or &lt;?page 5?&gt;<st32:che xmlns:st32="http://lighthouseip.com/">R²_f[SO₂M_{1 / x}]_j (8th)</st32:che>where R³_f for one monovalent fluoroaliphatic radical having, for example, 1-20 carbon atoms, preferably 4 to 10 carbon atoms group; R²_f For a polyvalent, preferably divalent fluoroaliphatic Radical having for example 1 to 20 carbon atoms and preferably 2 to 10 carbon atoms group; M represents a hydrogen atom or a cation of valence x, which is 1 or 2; and j 1 to 4 and preferably 1 or 2.

Next the sulfinate can Other reducing agents may be present, such as sodium, potassium or Ammonium sulfites, bisulfite, metabisulfite, hyposulfite, -thiosulfit, phosphite, sodium or Kaliumformaldehydsulfoxylat or -hypophosphit. It can also activators such as iron (II) -, copper (I) - and silver salts, may be present.

the used in the polymerization amount of fluoroaliphatic sulfinate for example, depending on the desired molecular weight of the Polymer vary. Preferably the amount of fluoroaliphatic Sulfinate 0.001 to 50 mole percent and most preferably .01 to 10 mole percent of sulfinate compound based on the total amount of monomers.

the Type and quantity of end groups is for the success in curing the Fluoroelastomer not critical. Thus, the polymer can, for example, generated by an APS / sulfite system SO₃^(-)-terminated included, or the polymer may be generated by an APS initiator system COO^(-)contain end groups or the fluoroelastomer can be "neutral" end groups, z. B. by using Fluorsulfinat initiator systems or organic Peroxides end groups produced exhibit. The number of end groups can be prepared by chain transfer agent Every effort will be considerably reduced. If desired, such as for improved Processing, can be the presence of strong polar end groups such as SO₃^(-) minimize and Case of COO^(-)End groups, the amount reduce by finishing operations (decarboxylation).

the cure site is to cure the fluoropolymer capable. The cure site includes generally at least one nitrile-containing cure site.

the cure site may be partially or fully fluorinated. Useful nitrile-containing cure site include nitrile-containing fluorinated olefins and nitrile containing fluorinated vinyl ethers according to the following illustration: <st32:che xmlns:st32="http://lighthouseip.com/">CF₂= CFO (CF₂)_lCN (9)</st32:che><st32:che xmlns:st32="http://lighthouseip.com/">CF₂= CFO [CF₂CF (CF₃)O]_q(CF₂)_yOCF (CF₃) CN (10)</st32:che><st32:che xmlns:st32="http://lighthouseip.com/">CF₂= CF [OCF₂CF (CF₃)]_rO (CF₂)_tCN (11)</st32:che> in which with reference to the above formulas: l = 2-12; q = 0-4; r = 1-2; y = 1-6 and t = 1-10. Representative examples for a such a monomer include perfluoro (8-cyano-5-methyl-3,6-dioxa-1-octene), CF₂= CFO (CF₂)₅CN and CF₂= CFO (CF₂)₃OCF (CF₃) CN.

the are fluoropolymer compositions having an amine complex compound of a divalent metal represented by the following general formula is reproduced: <img img-content="cf" img-format="tif" he="31" wi="66" file="00100001.tif" />where M is a divalent metal, X is a anionic group, and n 2 to 6, preferably 3 to 5, and particularly preferably 3 or 5, is cured. examples for Suitable divalent metals are magnesium, nickel, zinc, cobalt, Lead, iron, tin, cadmium and calcium, with magnesium and zinc are preferred. Suitable anionic groups are halide (eg. As chloride, bromide or iodide), Hydroxylat-, alkoxylate, carboxylate, Phenoxyid-, sulfonate, sulfate, sulfite, carbonate, and nitrate groups, said halides, &lt;?page 6?&gt;are as chlorides, are preferred. This formula includes, for example, Complexes of 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU) and 1,5-diazabicyclo [4,3,0] non-5-ene (DBN). These complexes can be for example, by reacting DBU or DBN with a metal salt (Z. B. a metal halide) in an organic solvent, such as methanol or acetone according to the procedure according to the <patcit><text>US-PS 4,833,212</text></patcit> getting produced. In some embodiments, of the present invention is more than one such metal amine complex used.

In addition, with the metal amine complexes of the invention Alcohols are used. Such alcohols preferably have Boiling points of at least 70 ° C. Preferred alcohols are ethanol and octanol. The used Amount of alcohol is in the range of about 0 to 100 weight percent, based on the amount of metal amine complex compounds. That is, at 100 Weight percent of the weight of alcohol and amidine are equivalent are.

the Fluoropolymer compositions can with one or more Peroxidhärtern in addition to the amine catalyst complexes of divalent metals are cured. Suitable peroxide are generally those radicals at curing temperatures form. Particularly preferred are dialkyl and bis (dialkyl peroxide), which decompose each at temperatures above 50 ° C. In many cases is to use a di-t-butylperoxide with one of the Peroxy oxygen atom bonded tertiary carbon atom are preferred. Among the most useful peroxides of this type are 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3 and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane. Other peroxides can from compounds such as dicumyl peroxide, dibenzoyl peroxide, tert-butyl perbenzoate, a, a'-bis (t-butylperoxydiisopropylbenzol) and di [1,3-dimethyl-3- (t-butylperoxy) butyl] carbonate selected will. In general, from about 1 to 3 parts of peroxide per 100 parts of fluoropolymer.

the Fluoropolymer compositions can any of the in-curable Fluoropolymer formulations customary Aids. Thus, for example, mixed with a Fluoropolymer composition as a part of Peroxidhärtungssystems frequently a coagent (which is sometimes also referred to as co-curative), the of a polyunsaturated Link is such that for the cooperation with the hardener Provision is capable of a useful cure. These coagents can generally present in an amount between 0.1 and 10 parts per hundred Parts fluoropolymer, preferably between 1 and 5 parts per hundred parts Fluoropolymer may be added. Examples of useful coagents are triallyl; triallyl; Trimethylallylisocyanurat; Tris (diallylamine) -s-triazine; triallyl phosphite; N, N-diallyl acrylamide; hexaallyl phosphoramide; N, N, N ', N'-Tetraalkyltetraphthalamid; N, N, N ', N'-tetraallyl malonamide; trivinyl isocyanurate; 2,4,6-trivinyl methyltrisiloxane; and tri (5-norbornene-2-methylene) cyanurate. Particularly useful is triallyl.

Other Suitable coagents include the bis-olefins according <patcit><text>EPA 0661304 A1</text></patcit>. <patcit><text>EPA 0784064 A1</text></patcit> and <patcit><text>EPA 0769521 A1</text></patcit>,

the Fluoropolymer compositions can by using other types of curing agents which are known in curing useful nitrile fluoropolymers contained, in addition to the amine complex catalysts divalent metals are cured, if any undesirable Features of the known curing system is tolerable. examples for such hardeners are peroxides, aromatic amino compounds including aromatic Aminophenols Bisaminophenole (z. B. in accordance <patcit><text>US-PS 5,767,204</text></patcit> and <patcit><text>US-PS 5,700,879</text></patcit>) Bisamidrazonen, Bisamidooximen (z. B. in accordance <patcit><text>US-PS 5,621,145</text></patcit>) And ammonium salts (Z. B. in accordance <patcit><text>US-PS 5,565,512</text></patcit>). It come organometallic compounds of arsenic, antimony and tin in Considered, for example in accordance with the <patcit><text>US Patents 4,281,092</text></patcit> and <patcit><text>5,554,680</text></patcit>, specific examples are allyl, propargyl, triphenyl-, allenyl and tetraphenylstannane and Triphenylzinnhydroxyd. These additional Harder are preferably added in an amount such that hardener total amounts to (Imidatkatalysator plus other hardener) from 0.05 to 10 phr, and most preferably reaches 0.1 to 5 phr.

It may be advantageous to the fluoropolymer compositions or more onium add. Examples of suitable onium salts are in the <patcit><text>US-PS 4,882,390</text></patcit> described. Examples include triphenylbenzyl phosphonium chloride in detail, Tributylalkylphosphoniumchlorid, tributylbenzyl, Tetrabutylammonium and triarylsulfonium called. Prefers are the phosphonium.

the Combination of metal amine complex compound (s) and other hardener or other hardeners, provided present is generally from about 0.01 to about 10 mol% (more preferably about 0.1 to about 5 mol%) of the total fluoropolymer amount.

&lt;?page 7?&gt;

additives such as carbon black, Stabilizers, plasticizers, lubricants, fillers, and processing aids, which are usually used in the Fluorpolymercompoundierung, can be incorporated into the compositions, provided that they have a sufficient stability for the have foreseen operating conditions. In particular, the Low temperature performance be enhanced by incorporation of perfluoropolyethers. Please refer for example <patcit><text>US-PS 5,268,405</text></patcit>,

In addition, in fluoropolymers as a rule, carbon black fillers as a means to balance of modulus, tensile strength, elongation, hardness, abrasion resistance, conductivity and processability of the compositions used. Suitable Examples are thermal medium Blacks (MT Black) with the label N-991, N-990, N-908 and N-907; FEF N-550 and large-particle Furnace blacks. Using Coarse Soot are 1-70 phr generally sufficient.

in the compositions may also fluoropolymer fillers be present. In general, from 1 to 50 parts of filler per hundred parts fluoropolymer base resin of one or more fluoropolymer fillers. The fluoropolymer can be used as solid at the highest Temperature which in the production and curing of the fluoroelastomer composition applied, be finely divided and easily dispersed. With Solids is meant that the filler, if it is partially crystalline, a crystalline melting temperature above the processing temperature (s) of the fluoroelastomer or of the fluoroelastomers having. The preferred way of incorporating fluoropolymer is the blending of latexes; This process and various Kinds of fluoropolymer fillers are described in the filed on 1 February 2000 USSN 09 / 495.600.

Such fillers generally have melting points in the range of 100 to 300 ° C. Examples of suitable fillers are low molecular weight polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoropropyl vinyl ether copolymer (PFA), and Tetrafluoroethylene-hexafluoropropene copolymer (FEP).

the formulations may are added, however, also with one or more acid acceptors, if the presence of extractable metallic compounds is undesirable (As for Semiconductor applications) the use of inorganic acid acceptors should be minimized and preferably avoided altogether. common Acid acceptors for example, tin oxide, calcium hydroxide, calcium carbonate, Magnesium oxide, etc. These compounds are generally used in the fluoropolymer formulation to bind any HF or other acids, where the function at the high temperatures, fluoropolymers have to, are produced, used.

the curable inventive Fluoropolymer together tions can with other curable Fluoropolymer compositions such as peroxide-curable fluoropolymer compositions, be combined. These additional curable use fluoropolymer compositions typically small amounts of cure site as a comonomer. Suitable cure site are those which, when combined with a hardener (z. B. a peroxide) and preferably a co-agent provide a cured composition. This cure site preferably containing at least one halogen group (eg. as a Bromine or an iodo group).

the curable Fluoropolymer compositions can by mixing the fluoropolymer, the amine complex catalyst of divalent metal, the chosen Additive or the selected Additives, the additional Harder (If available) and the other tools, if any, in conventional Rubber processing devices are produced. The desired Quantities of compounding ingredients and other conventional Aids or ingredients may the uncured fluorocarbon rubber base material added and using one of the usual Rubber mixing devices such as internal mixers (for. Example, Banbury mixers), rolling mills or other convenient mixing device, intimately mixed therewith or compounded. For the best Results should the temperature of the mixture during mixing typically no over about 120 ° C rise. During mixing, it is advantageous for the purpose of effectively curing the Components and assistants uniformly distributed through the rubber.

the Mixture is then processed and shaped, for example by Extrusion (for example in the form of a hose or hose lining) or of a molded body (For example in the form of an O-ring seal). The molded body then to cure of the rubber composition and form a cured article are heated.

The Pressing of the compounded mixture (that is Preßhärten) is generally at a temperature &lt;?page 8?&gt;between about 95 ° C and about 230 ° C, preferably between about 150 ° C and about 205 ° C, for a Period of 1 minute to 15 hours, usually 5 minutes to carried out for 30 minutes. Usually exercises one on the compounded mixture in the mold a pressure between about 700 kPa and about 20,600 kPa from. The forms can initially be coated a mold release agent and prebaked. The molded vulcanizate is then usually at a temperature of usually between about 150 ° C and about 300 ° C, usually at about 232 ° C, for a Period of about 2 hours to 50 hours or more, depending on the Cross-sectional thickness of the article, post-cured (eg. As in the furnace). For thick Cross-sections, the temperature during the post cure is usually gradual from the lower limit of the range increases to the desired maximum temperature. The Maximum temperature used is preferably about 300 ° C, and is about 4 hours or more kept at this value.

the Fluoropolymer compositions suitable for the production of articles such as O-rings, seals, hoses and seals. Such articles are prepared by reacting a compounded formulation of the fluoropolymer composition formed with various additives under pressure, curing the part, and then a post-cure cycle subjects. The formulated without inorganic acid acceptors curable Compositions are particularly well suited for applications such as seals and closures for the production of semiconductor devices, and in seals for high temperature automotive applications.

the Invention will now be described in more detail by the following examples.

EXAMPLES

Test methods

in the following examples, indicated results with the following test condition: cure rheology: were Härtungsrheologieprüfungen on uncured, compounded samples on a Moving Die Rheometer (MDR) Model D 2000 by Monsanto in accordance with ASTM 5289-93a at 177 ° C without preheating 30 minutes elapsed time and 0.5 degree arc performed. There were both the minimum torque (M_L) and the highest Torque during a predetermined time period is reached when no plateau or obtain maximum torque (M_H) listed. It was also the time until the increase in torque of 2 units above M_L ( "T_s2 "), the time for the torque to have a value of M_L + 0.5 (M_H - M_L) Reached ( "t'50"), and the time until the torque M_L + 0.9 (M_H - M_L) Achieved ( "t'90") measured.

Press-hardening: Provided otherwise noted, 150 x, 150 x 2.0 mm plates for determining the physical properties by pressing about 6.9 Mega Pascal (MPa) over a period of 30 minutes at 177 ° C.

Post cure: post-cured sample sheets under nitrogen using the following six stages of conditions exposed to heat: 25-200 ° C over a period of 6 hours; 200 ° C for 16 hours; 200-250 ° C over a Period of 2 hours; 250 ° C for 8 hours; 250-300 ° C over a Period of 2 hours and 300 ° C for 16 Hours. The samples were returned before testing to ambient temperature.

Physical Strength: The tear strength, elongation at break and the modulus at 100% elongation were measured according to ASTM D 412-92 on samples consisting of Preßhärtungs- or Nachhärtungsplatte with ASTM The D were excised, determined. The results were recorded in psi and converted to the indicated MPa values.

Heat aging: Preßgehärtete and postcured were sample plates in the air 70 hours heated at 290 ° C and then before the test returned to ambient temperature.

Hardness: Samples were in accordance with ASTM D 2240-85, method A, measured with a Shore Durometer Type A-2. The units are in points on the Shore A scale.

Compression set: O-ring samples were measured according to ASTM 395-89, Method B, measured. The O-rings had a cross-sectional thickness of 0.139 inches (3.5 mm). The results are expressed as a percentage of the permanent deformation indicated.

&lt;?page 9?&gt;

example 1

By with APS-initiated aqueous emulsion polymerization a fluoroelastomer was prepared which contained 62.1 mole% of tetrafluoroethylene, 36.8 mol% perfluoromethylvinylether and 1.1 mol% of a nitrile containing cure site, CF₂= CFO (CF₂)₅CN contained. The polymer obtained (100 g) was mixed with 15 g of carbon black FEF N550, and 2.5 g of a by that of Example 1 <patcit><text>US-PS 4,833,212</text></patcit> illustrated method prepared DBU MgCl₂Complex compounded.

At the uncured, compounded sample were made Härtungsrheologieprüfungen. A Plate from the compounded mixture dignity cured and tested. the Results are shown in the tables below.

example 2

It The procedure of Example 1, but with the modification that it is wherein the amine complex of a divalent metal to 1.25 g of DBU-ZnCl₂Prepared according to Example 1 of <patcit><text>US PS4,833,212</text></patcit>But with ZnCl₂ instead of MgCl₂. acted. Samples were tested as in Example 1, and the results are listed in the tables below. Furthermore, was the elapsed time in the 60 Härtungsrheologieprüfungen Minutes.

Examples 3

It The procedure of Example 2, but with the exception that it is at the curing catalyst 1.25 g DBU ZnCl₂ combined with 0.75 g triphenylbenzylphosphonium acted. Samples were prepared as tested in Example 1 and the results are listed in the tables below. Of another was the elapsed time in the 30 Härtungsrheologieprüfungen Minutes.

Comparative Example VE-1

It The procedure of Example 1, but with the modification that, instead of the amine complex of a divalent metal 2.0 g tetraphenyltin as a curing catalyst has been used. Samples were tested as in Example 1, and the results are listed in the tables below. Table 1: cure rheology<tables><table frame="all"><tgroup cols="5" colsep="1" rowsep="1"><colspec colname="1" colwidth="3*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><colspec colname="5" colwidth="1*" /><tbody><row><entry colname="2">Ex.1</entry><entry colname="3">Ex.2</entry><entry colname="4">EX3</entry><entry colname="5">VE-1</entry></row><row><entry colname="1">M_L (N-m)</entry><entry colname="2">0,229</entry><entry colname="3">0.143</entry><entry colname="4">0,167</entry><entry colname="5">0,228</entry></row><row><entry colname="1">M_H (N-m)</entry><entry colname="2">0.891</entry><entry colname="3">1,126</entry><entry colname="4">1,026</entry><entry colname="5">1,773</entry></row><row><entry colname="1">t_s2 (min)</entry><entry colname="2">5.72</entry><entry colname="3">14,39</entry><entry colname="4">4.52</entry><entry colname="5">0.48</entry></row><row><entry colname="1">T'50 (min)</entry><entry colname="2">8.23</entry><entry colname="3">25.4</entry><entry colname="4">7.11</entry><entry colname="5">0.76</entry></row><row><entry colname="1">T'90 (min)</entry><entry colname="2">16,84</entry><entry colname="3">45</entry><entry colname="4">19,87</entry><entry colname="5">5.75</entry></row></tbody></tgroup></table></tables> Table 2: press-cured and post-cured <tables><table frame="all"><tgroup cols="5" colsep="1" rowsep="1"><colspec colname="1" colwidth="3*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><colspec colname="5" colwidth="1*" /><tbody><row><entry colname="2">Ex.1</entry><entry colname="3">Ex.2</entry><entry colname="4">EX3</entry><entry colname="5">VE-1</entry></row><row><entry colname="1">tensile strength (MPa)</entry><entry colname="2">11,80</entry><entry colname="3">16,78</entry><entry colname="4">17,81</entry><entry colname="5">13,75</entry></row><row><entry colname="1">elongation (%)</entry><entry colname="2">123</entry><entry colname="3">123</entry><entry colname="4">130</entry><entry colname="5">144</entry></row><row><entry colname="1">100% modulus (MPa)</entry><entry colname="2">8.16</entry><entry colname="3">11.86</entry><entry colname="4">11,14</entry><entry colname="5">7.39</entry></row><row><entry colname="1">Shore A hardness</entry><entry colname="2">75</entry><entry colname="3">73</entry><entry colname="4">71</entry><entry colname="5">72</entry></row></tbody></tgroup></table></tables>&lt;?page 10?&gt; Table 3: Compression Set (%) <tables><table frame="all"><tgroup cols="5" colsep="1" rowsep="1"><colspec colnum="1" colname="1" colwidth="3*" /><colspec colnum="2" colname="5" colwidth="1*" /><colspec colnum="3" colname="6" colwidth="1*" /><colspec colnum="4" colname="7" colwidth="1*" /><colspec colnum="5" colname="8" colwidth="1*" /><tbody><row><entry colname="5">Ex.1</entry><entry colname="6">Ex.2</entry><entry colname="7">EX3</entry><entry colname="8">VE-1</entry></row><row><entry colname="1">70 h at 200 ° C</entry><entry colname="5">15.1</entry><entry colname="6">20.1</entry><entry colname="7">18.4</entry><entry colname="8">59.5</entry></row><row><entry colname="1">70 h at 230 ° C</entry><entry colname="5">18.2</entry><entry colname="6">27.0</entry><entry colname="7">20.8</entry><entry colname="8">76.6</entry></row><row><entry colname="1">22 at 300 ° C h</entry><entry colname="5">ng</entry><entry colname="6">39.5</entry><entry colname="7">29.6</entry><entry colname="8">100.0</entry></row><row><entry colname="1">44 at 300 ° C h</entry><entry colname="5">ng</entry><entry colname="6">46.9</entry><entry colname="7">36.4</entry><entry colname="8">ng</entry></row><row><entry colname="1">70 at 300 ° C h</entry><entry colname="5">ng</entry><entry colname="6">51.6</entry><entry colname="7">40.8</entry><entry colname="8">ng</entry></row></tbody></tgroup></table></tables>

in Table 3, "ng" means that the sample was not measured. Table 4: heat aged<tables><table frame="all"><tgroup cols="5" colsep="1" rowsep="1"><colspec colname="1" colwidth="3*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><colspec colname="5" colwidth="1*" /><tbody><row><entry colname="2">Ex.1</entry><entry colname="3">Ex.2</entry><entry colname="4">EX3</entry><entry colname="5">VE-1</entry></row><row><entry colname="1">tensile strength (MPa)</entry><entry colname="2">10,11</entry><entry colname="3">10.77</entry><entry colname="4">12,08</entry><entry colname="5">11.86</entry></row><row><entry colname="1">elongation (%)</entry><entry colname="2">195</entry><entry colname="3">218</entry><entry colname="4">214</entry><entry colname="5">250</entry></row><row><entry colname="1">100% modulus (MPa)</entry><entry colname="2">4.19</entry><entry colname="3">5.24</entry><entry colname="4">5.96</entry><entry colname="5">3.65</entry></row><row><entry colname="1">Shore A hardness</entry><entry colname="2">71</entry><entry colname="3">73</entry><entry colname="4">72</entry><entry colname="5">71</entry></row></tbody></tgroup></table></tables>

Out the results indicate that under Using the Aminkomplexhärtungskatalysators of compositions divalent metal produced compared to under Using a Organozinnhärtungskatalysators Compositions produced have improved properties. Especially shown that with an amine complex of a divalent metal cured Catalysts much better (lower) compression set values on.