US20040229999A1 - HXNBR-rubber as a cross-linking agent - Google Patents

HXNBR-rubber as a cross-linking agent Download PDF

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Publication number
US20040229999A1
US20040229999A1 US10/842,983 US84298304A US2004229999A1 US 20040229999 A1 US20040229999 A1 US 20040229999A1 US 84298304 A US84298304 A US 84298304A US 2004229999 A1 US2004229999 A1 US 2004229999A1
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hxnbr
triphenylphosphine
molecularly dispersed
rubber
cross
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Dirk Achten
Hans-Rafael Winkelbach
Martin Mezger
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Lanxess Deutschland GmbH
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Assigned to BAYER AKTIENGESELLSCHAFT reassignment BAYER AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MEZGER, MARTIN, ACHTEN, DIRK, WINKELBACH, HANS-RAFAEL
Publication of US20040229999A1 publication Critical patent/US20040229999A1/en
Assigned to LANXESS DEUTSCHLAND GMBH reassignment LANXESS DEUTSCHLAND GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BAYER AG
Priority to US11/977,310 priority Critical patent/US7572861B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/005—Hydrogenated nitrile rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/66—Substances characterised by their function in the composition

Definitions

  • the present invention relates to the hydrogenated carboxylated nitrile-butadiene rubber (HXNBR) which contains molecularly dispersed triphenylphosphine as cross-linking agent for elastomers, plastics and/or adhesive systems and products which are obtainable from the HXNBR having molecularly dispersed triphenylphosphine and elastomer, plastics and/or adhesive systems.
  • HXNBR hydrogenated carboxylated nitrile-butadiene rubber
  • the present invention also relates to a composition containing HXNBR having molecularly dispersed triphenylphosphine and further non-molecularly dispersed activators, a process for the preparation of the composition as well as the use of HXNBR having molecularly dispersed triphenylphosphine as an elasticizing agent for elastomers, plastics and/or adhesive systems.
  • compositions which are useful as cross-linking agents in totally disparate media such as elastomer, plastics and/or adhesive systems and which can optionally be used simultaneously as elasticizing agents in these media.
  • carboxylated polymers can be used as contact adhesives on account of their ability to form reversible ionic cross-linkages with MgO, which leads to an improvement in the initial adhesion rate at both high and low temperatures.
  • a cross-linking or elasticizing of this type by direct reaction of the elastomer, plastics or adhesive systems with HXNBR rubber in the presence of activators such as triphenylphosphine and/or others is not known in the art.
  • activators such as triphenylphosphine and/or others.
  • the utilization of HXNBR rubber which contains molecularly dispersed activators and optionally further activators, as a cross-linking agent and/or elasticizing agent is furthermore also not known.
  • the object of the present invention is therefore to provide a substance or a composition which, where required, enables peroxidic, photochemical, sulfur and ionic cross-linking reactions to take place as well as addition and condensation reactions with cross-linking-active and coupling-active groups of elastomer, plastics, and/or adhesives.
  • the present invention relates to hydrogenated carboxylated nitrile-butadiene rubber (HXNBR), in which triphenylphosphine is molecularly dispersed, as a cross-linking agent for elastomer, plastics and/or adhesive systems.
  • HXNBR hydrogenated carboxylated nitrile-butadiene rubber
  • the present invention is also directed HXNBR rubber having molecularly dispersed triphenylphosphine as a cross-linking agent, wherein from 0.1 to 10 wt. % of molecularly dispersed triphenylphosphine in the HXNBR rubber is preferred.
  • the present invention also includes HXNBR which contains molecularly dispersed triphenylphosphine and further contains, a non-molecularly dispersed, activator.
  • Cross-linking agent wherein the elastomers, plastics and/or adhesive systems which are to be cross-link-ed can be selected from polyurethanes, polyureas, polyesters, polyamides, poly(meth)acrylates, polyepoxides, polyepichlorohydrin, the products prepared from bifunctional or polyfunctional epoxides, thiiranes, isocyanates or carbodiimides with bifunctional or polyfunctional amines, alcohols formaldehyde-phenolic resins, rubbers which are cross-linked by way of radical generators, and ionically cross-linkable mixtures, are preferred.
  • the present invention also provides a product which is prepared by mixing a hydrogenated carboxylated nitrile-butadiene rubber (HXNBR) in which triphenylphosphine is molecularly dispersed, with an elastomer, plastic and/or adhesive systems.
  • HXNBR hydrogenated carboxylated nitrile-butadiene rubber
  • the present invention also provides a composition containing
  • HXNBR hydrogenated carboxylated nitrile-butadiene rubber
  • the composition preferably comprises from 10 to 99.9 wt. % of the component a) and from 0.1 to 90 wt. % of the component b).
  • the activator of the composition is preferably selected from ethanolamine, primary aliphatic or aromatic amines, secondary aliphatic or aromatic amines, organic phosphorus compounds, acid catalysts and mixtures of these compounds.
  • the composition preferably contains from 0.1 to 10 wt. % of molecularly dispersed triphenylphosphine in the HXNBR rubber.
  • the composition preferably also contains from 0 to 90 wt. % of further additives selected from organic solvents, stabilizers, emulsifiers, water, plasticizers processing aids and fillers.
  • the present invention also provides a process for the preparation of the composition, which includes
  • the present invention also provides the use of HXNBR rubber having molecularly dispersed triphenylphosphine, as an elasticizing agent for elastomers, plastics and/or adhesive systems.
  • HXNBR rubber as an elasticizing agent for elastomers, plastics and/or adhesive systems is preferable when the HXNBR rubber also contains further non-molecularly dispersed activator.
  • the composition according to the present invention contains from 10 to 99.9 wt. %, preferably 60 to 99.9 wt. %, of hydrogenated carboxylated nitrile-butadiene rubber (HXNBR) and from 0.1 to 90 wt. %, preferably 0.1 to 40 wt. %, of activator and from 0 to 90 wt. % of additives.
  • HXNBR hydrogenated carboxylated nitrile-butadiene rubber
  • the composition according to the present invention includes a mixture of HXNBR having molecularly dispersed triphenylphosphine, and further additional activators.
  • a hydrogenated carboxylated nitrile-butadiene rubber is understood to be ally copolymers known to those skilled in the art, which are derived from the monomers butadiene, acrylonitrile, methacrylic acid as well as further acrylic and/or vinylic monomers which are prepared by an emulsion polymerization to obtain an XNBR (carboxylated nitrile-butadiene rubber), as described in WO-A 01/77185, and are subsequently hydrogenated to obtain the HXNBR.
  • This method of preparation equips the HXNBR rubber in direct manner with a molecularly dispersed activator, triphenylphosphine. Activation for addition and condensation reactions is achieved with low concentrations of the activator on account of its molecular dispersion. The reactivity may be adjusted, controlled and increased by the addition of further quantities of activators.
  • triphenylphosphine is understood to be a triphenyl-phosphine which is dissolved in the HNBR.
  • the triphenylphosphine is dispersed such that no differences in concentration occur between HNBR and triphenylphosphine on a dimensional scale greater than 1 micrometer.
  • such a uniform dispersion cannot be achieved when triphenylphosphine is mixed mechanically into HNBR, with the quality of the dispersion of the triphenyl-phosphine in the HNBR being dependent on the duration of mixing, the mixing temperature as well as the general composition of the mixture.
  • the further acrylic and/or vinylic monomers are understood to be any acrylic and/or vinylic monomers known to those skilled in the art.
  • the following are preferred: vinyl benzenes, acrylates, methacrylates as well as free acids thereof.
  • the following are more preferred: styrene, divinylbenzene, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methacrylonitrile, acrylmethacylic acid, maleic anhydride, fumaric acid and itaconic acid.
  • Highly hydrogenated HXNBR rubbers are preferably used. “Highly hydrogenated” as applied to HXNBR rubbers is understood to mean having a double bond content of less than 40 double bonds per 1000 carbon atoms, preferably less than 15 double bonds per 1000 carbon atoms. Double bond content within the range 0.2 to 15 double bonds per 1000 carbon atoms is preferred.
  • HXNBR rubber The preparation of a highly hydrogenated HXNBR rubber is described in WO-A 01//77185.
  • the HXNBR rubber is prepared starting from XNBR by hydrogenation in a solution process, with this being convertible subsequently to solid rubber.
  • the monomer units may be distributed in both random and in block manner. A random distribution is preferred.
  • the HXNBR rubber which is utilized in the composition according to the present invention and contains molecularly dispersed triphenylphosphine and can also be used without further addition of activators as an elasticizing agent and/or cross-linking-active component for elastomers, plastics and/or adhesive systems, has a nitrile group content within the range 10 to 50 wt. %, preferably within the range 15 to 45 wt. %, and a methacrylic acid content within the range 0.1 to 20 wt. %, preferably within the range 1 to 10 wt. %, in relation to the total proportion of HXNBR rubber.
  • the HXNBR rubber contains from 0.1 to 10 wt. %, preferably 0.1 to 5 wt. %, of molecularly dispersed triphenylphosphine.
  • composition according to the present invention a further activator can be added to the HXNBR rubber which already contains molecularly dispersed triphenylphosphine.
  • activators are frequently be added.
  • the term “activators” is understood to be any activators known to those skilled in the art. Activators can also be utilized for XNBR rubbers are preferred. Basic or acid catalysts are preferred.
  • acid catalysts such as para-toluenesulfonic acid, salicylic acid, activated ⁇ -A
  • composition according to the present invention prepared from HXNBR rubber which contains molecularly dispersed triphenylphosphine and has additional activator, and also in the HXNBR rubber which contains molecularly dispersed triphenylphosphine and has no additional activator.
  • further additives can be selected from organic solvents, stabilizers, emulsifiers, water and plasticizers, processing aids and fillers.
  • Preferred organic solvents are chlorobenzene, acetone, methyl ethyl ketone, methylene chloride, chloroform, tetrahydrofuran, toluene or mixtures of the same.
  • Preferred stabilizers are any antioxidants known to those skilled in the art. 2,2′-methylene-bis-(4-methyl-6-tert.-butylphenol), 2-mercaptobenzimidazole, N-isopropyl-N′-phenyl-paraphenylene diamine are more preferred.
  • Preferred emulsifiers are any emulsifiers known to those skilled in the art such as fatty acids and alkali metal and alkaline earth metal salts thereof, (disproportionated) rosin acids and salts thereof, alkylsulfonic acids and arylsulfonic acid, organic sulfates as well as the class of nonionic emulsifiers.
  • the sodium stearates and potassium stearates, oleates, organic sodium and potassium sulfates and sulfonates and rosin acids are more preferred.
  • Preferred plasticizers are trioctyl phosphate, benzyloctyl adipate, polyphthalates, tri(2-ethylhexyl) trimellitate, aromatic polyetheresters and thioetheresters.
  • Preferred processing aids ale stearyl amines and zinc stearate.
  • Preferred fillers are carbon black, silica, talcum, alumina silicat and calcium carbonate.
  • the HXNBR rubber which contains molecularly dispersed triphenylphosphine, is mixed with the additional activator in the manner known to those skilled in the art.
  • Mixing rolls are preferably used for mixing, but internal mixers and compounding extruders are also possible, as is mixing in solution or in dispersion.
  • Both the HXNBR rubber having molecularly dispersed triphenylphosphine without additional activator and also the composition according to the present invention, in which the HXNBR rubber is utilized with molecularly dispersed triphenylphosphine and additional activators, can be used both as a cross-linking agent and as an elasticizing agent for elastomer, plastics and/or adhesive systems, since the HXNBR rubber, in each case having molecularly dispersed triphenylphosphine but with and without additional activator, also has, in addition to a cross-linking property, an elasticizing effect on elastomers, plastics and/or adhesive systems.
  • the term “elastomer” is understood to be any elastomers known to those skilled in the art. Any polymeric compounds having a glass transition point below room temperature (20° C.) are preferred. Polychloroprene, ethylene propylene diene rubber, polyacrylates, polybutadienes, polyacrylonitrile butadiene, fluororubbers, chlorosulfonated rubbers, halogenated and unhalogenated butyl rubber, and styrene butadiene rubber are preferred.
  • the term “plastics” is understood as any thermoplastics and thermoset materials (cross-linked, non-meltable thermoplastics) known to those skilled in the art.
  • thermoplastics and/or thermoset materials selected from the group consisting of polyurethanes, polyureas, polyesters, polyamides, polyacrylates, polymethacrylates, polyepoxides, polyepichlorohydrins are preferred.
  • adhesive systems is understood to be any adhesives and/or adhesive systems as well as surfacing agents such as lacquers and coatings, which are known to those skilled in the art.
  • Preferred adhesive systems include those prepared from bifunctional or polyfunctional epoxides/thiiranes/isocyanates/carbodiimides in combination with bifunctional or polyfunctional amines/alcohols/carboxylic acids, formaldehyde-phenolic resins, or products which arise from the reaction of cross-linkable functional (meth)acrylates and/or rubbers with radical generators.
  • Adhesive systems are additionally understood to be ionic networks having basic frameworks selected from the group consisting of polyfunctional sulfonates, polyfunctional carboxylates, polyfunctional nitrogen compounds and polyfunctional phosphorus compounds or chelate compounds, which are reacted with strongly polar ions.
  • Radical generators are understood to be any initiators known to those skilled in the art, which can generate radicals.
  • the radical generators selected from the group consisting of photoinitiators, peroxides, azides and redox initiators are preferred.
  • Cross-linkable functional (meth)acrylates are understood to be preferably hydroxyethyl methacrylate and zinc di(meth)acrylate.
  • Rubbers which can be reacted with the radical generators are understood to be preferably nitrile rubber, chloroprene rubber, ethylene-propylene-diene rubber, ethylene-acrylate rubber (AEM), fluororubber (FKM), chlorosulfonated polyethylene and styrene-butadiene rubber.
  • Ionic networks are understood to be combinations of polyfunctional sulfonates, carboxylates, polyfunctional nitrogen compounds, polyfunctional phosphorus compounds or polyfunctional chelate compounds halving strongly polar ions. Strongly polar ions are understood to be monovalent and polyvalent ions.
  • Monovalent and polyvalent ions selected from the group consisting of H, Li, Mg, Ca, Al, Ba, Ti, Mn, Fe, Cu, Zn and Sn are understood to be preferred.
  • Preferred polyfunctional sulfonates are polystyrene sulfonic acid and chlorosulfonated polyethylene.
  • Preferred carboxylates are carboxylated butadiene-nitrile rubber (NBR), carboxylated styrene-butadiene rubber (XSBR), maleic anhydride-grafted ethylene-propylene copolymer (EPM), ethylene-propylene-diene copolymer (EPDM) or polypropylene (PP) and ethylene-acrylate rubbers (AEM).
  • Polyfunctional nitrogen compounds and phosphorus compounds or chelate compounds are understood to be preferably polyvinyl pyrrolidone, polyphosphates, EDTA (ethylenediamine triacetic acid or the sodium salt of this acid) and nucleic acids.
  • the HXNBR rubber having the molecularly dispersed triphenylphosphine or the composition according to the present invention prepared from HXNBR, which contains the molecularly dispersed triphenylphosphine and a further activator the HXNBR rubber having molecularly dispersed triphenylphosphine can be present in solid form, in a suitable organic solvent or in an aqueous dispersion.
  • HXNBR rubber having molecularly dispersed triphenylphosphine both with and without additional activator are not only the elasticizing properties, but also the breadth of application, not only to a peroxidic but also to a photochemical, sulfur-induced or ionic cross-linking reaction as well as addition and condensation reactions with the cross-linking-active and coupling-active groups of the elastomers, plastics and/or adhesive systems which are cross-linked by the HXNBR rubber-which contains molecularly dispersed triphenylphosphine, or by the composition according to the present invention.
  • the HXNBR rubber having molecularly dispersed triphenylphosphine, to which activator has or has not been added, can furthermore be utilized as an elasticizing agent, compatibilizer and adhesive/lacquer raw material.
  • a further advantage is the blends which are stable and resistant to oil, high temperatures, oxidation and chemicals, which are obtainable as a result of mixing with HXNBR rubber having molecularly dispersed triphenylphosphine or the composition according to the present invention.
  • Therban ® VP KA 8889 hydrogenated acrylonitrile-butadiene-methacrylic acid terpolymer (HXNBR), from Bayer AG, acrylonitrile content 32 wt. %
  • Therban ® C3407 hydrogenated acrylonitrile-butadiene copolymer (HNBR),, from Bayer AG, acrylonitrile content 34 wt. % Vanfre ® VAM organic phosphate ester, free acid, from Vanderbilt, density at 25° C. 0.97 g/cm 3 Rhenofit ® DDA-70 70 wt.
  • polycarbodiimide density 1.01 g/cm 3 at 25° C.
  • Polydispersion ® T VC 40P di-(tert.-butylperoxyisopropyl) benzene, 40 wt. %, from Rheinchemie, density 1.10 g/cm 3 at 25° C.
  • Perkalink ® 301 triallyl isocyanurate from Akzo Nobel, density 1.16 g/cm 3 at 25° C.
  • Triphenylphosphine* dissolved molecularly in the rubber Epoxy ® 4 methylene-bis-(N,N-glycidylaniline), from Bakelite AG DER RESIN ® 332 aromatic diallyl epoxide, from Dow Epoxy ® 3 N,N-bis(2,3-epoxypropyl)4-(2,3-epoxypropoxy) aniline, from Bakelite AG DER ® 732 polyglycol diepoxide, from Dow Triphenylphosphine 97% pure, from Aldrich Vestamid ® polyamide 12, from Degussa Durethan ® polyamide 66, from Bayer AG Trogamid ® polyamide 63, from Degussa AG Krynac ® X7.40 acrylonitrile-butadiene-methacrylic acid terpolymer (XNBR), from Bayer, acrylonitrile content 26.5 wt.
  • Epoxy ® 4 methylene-bis-(N,
  • Vulkasil S active silica precipitated, pH 6, surface area approx. 175 m 2 /g, from Bayer AG
  • Siliquest ® RC-1 Silane vinyl silane from Witco Aluminum stearate aluminum stearate from Riedel de Haen AG, density 0.95 g/cm 3 at 25° C.
  • Resin ® SP 1045 heat-active octylphenol formaldehyde resin with methylol groups from Schenectady International Tin dichloride >98% pure, from Fluka
  • composition of mixture 1 2 3 4 5 6 7# 8 9 10 11 12#
  • Therban ® VP K.A 8889 100 100 100 100 100 50 — 100 100 100 50 — Therban ® A3407 — — — — — 50 100 — — — 50 100 Vanfre ® V AM 1.0 1.0 1.0 1.0 1.0 1.0 — — 1.0 1.0 1.0 1.0 1.0 Rhenofit ® DDA-70 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 Corax ® N 550 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Diplast ® TM 8-10/ST 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Vulkanox ® ZMB2 0.4 0.4 0.4 0.4 — — 0.4 0.4 0.4 — — 0.4 0.4 0.4 — — 0.4 0.4 0.4 — — 0.4 0.4 0.4
  • the roll temperature is 60° C.
  • HXNBR-containing mixtures line Fmax-Fmin
  • diisocyanates such as Desmodur® 15/44/TT
  • polycarbodiimides such as Rhenogran® P50
  • peroxidic cross-linking with Polydispersion® TVC 40P.
  • TABLE 3 Results of physical testing of vulcanizate properties at room temperature on aged/non-aged samples. Ageing was in a hot-air drying cabinet or by storage in various media. In addition to tensile stress-elongation curves in accordance with DIN 53504, volume swelling and Shore A hardness in accordance with DIN 53 505 were tested.
  • Vulcanization was at 170° C. for the respectively indicated duration at approx. 30 bar pressure.
  • Vulcanizate properties ISO test piece 2 (from 2 mm sheet) Mix- ture: 8 9 10 11 12# 170° C. (min) 30 30 20 20 24 heating times: F (MPa) 20.7 19 21 22 24 D (%) 200 425 370 345 365 S 50 (MPa) 4.3 3.3 2.2 2.3 1.6 S 100 (MPa) 10 5.6 4.4 4.9 4.0 S 150 (MPa) 15.9 8.3 7.6 8.9 8.5 S 200 (MPa) 20.7 10.9 11.4 13.4 13.5 S 250 (MPa) —/— 13.2 15 17.3 18.1 S 300 (MPa) —/— 15.3 18 20.6 21.5 H (Shore A) 82 80 73 73 66 (Stab) Following storage in hot air at 125° C.
  • HXNBR Therban® KA8889
  • HXNBR Therban® A 3407
  • TABLE 7 Formulations for the cross-linking of HXNBR mixtures with various epoxides and different quantities of triphenylphosphine. The constituents of the mixture are indicated as parts by weight (%) in relation to the total quantity of rubber utilized (HXNBR/HNBR).
  • the roll temperature is 60° C. TABLE 8 Results of vulcanizing tests performed on the mixtures in a Monsanto Rheometer MDR 2000 E at 200° C. and 30 min. Monsanto Rheometer MDR 2000 E: 200° C.
  • Table 8 shows the influence of the respective epoxy type, the quantity of epoxide used and the quantity of triphenylphosphine utilized on the cross-linking speed and cross-link density of HXNBR with epoxides. Only in the presence of activators was cross-linking of HXNBR with the epoxides which are listed successful at acceptable temperatures ⁇ 200° C. and within acceptable times (T 95) ⁇ 30 min. TABLE 9 Results of physical tests on vulcanizate properties at room temperature. In addition to tensile stress-elongation curves in accordance with DIN 53504 the Shore A hardness in accordance with DIN 53 505 is tested. Vulcanizing was at 180/200° C. for the duration indicated in each case, at approx.
  • Vulcanizate properties ISO test piece 2 (from 2 mm sheet) at 23° C. Mixture: 21 22 23 24 25 26 27 28 29 200° C. heating times: (min) 35 — — 40 — — — — — — 180° C.
  • Polyfunctional epoxides can react with HXNBR in the presence of suitable activators, with cross-linking.
  • the quantity of activator can be kept to a minimum by the utilization of molecularly dissolved triphenylphosphine.
  • TABLE 10 Formulations for the cross-linking of HXNBR and XNBR mixtures with various quantities of polyvalent ions (aluminum stearate) and various fillers (carbon black/silica). The constituents of the mixture are indicated as parts by weight (%) in relation to the total quantity of rubber utilized (HXNBR/XNBR).
  • Vulcanizate properties ISO test piece 2 (from 2 mm sheet) at 23° C. Mixture: 30 31 32 33 34# 35# 36# 37# 38 39 160° C. heating times: (min) 30 30 25 20 30 30 30 30 30 30 30 30 30 F (MPa) 8 10.4 12 15.4 0.7 2.3 5.5 9.4 2.4 9.6 D (%) 892 766 548 397 1315 961 471 251 1713 675 S 100(MPa) 2.0 2.3 3.6 7.2 1 1.4 2.4 5.5 0.8 2.2 S 200(MPa) 3.2 3.9 6.6 12.3 1.1 1.9 4 8.7 0.71 3.1 S 300(MPa) 4.5 5.7 9.4 14.7 1.2 2.3 5.2 — 0.7 4.2
  • Carboxyl group-containing polymers such as XNBR (carboxylated nitrile-butadiene rubber) and HXNBR can react with polyvalent ions, with cross-linking.
  • HXNBR carboxylated nitrile-butadiene rubber
  • TABLE 13 Formulations for the cross-linking of HXNBR and HNBR mixtures with formaldehyde-phenol cross-linking systems.
  • composition of mixture 40# 41 Therban ® A 3407 100 Therban ® KA 8889 100 Rhenofit ® DDA-70 1.4 1.4 Corax ® N 550 50 50 Resin ® SP1045 4 4 Tin dichloride 0.5 0.5 Triphenylphosphine* 1 1
  • HXNBR has a markedly higher cross-linking speed and cross-link density than HNBR when cross-linked by heat-activatable formaldehyde-phenol cross-linking systems such as are typically used for the cross-linking of, for example, butyl rubber (isoprene-isobutylene copolymer) but not for the cross-linking of HNBR.

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070055018A1 (en) * 2005-09-06 2007-03-08 Dirk Achten Crosslinkable compositions, thermoplastic elastomers obtainable therefrom and their use
US20080280715A1 (en) * 2004-10-01 2008-11-13 Central Glass Company, Limited Coating Liquid for Covering Glass Fiber and Rubber-Reinforcing Glass Fiber Using Same
US20080306199A1 (en) * 2007-06-08 2008-12-11 Sumitomo Rubber Industries, Ltd. Rubber composition for tire, and tire
US9091325B2 (en) 2004-10-01 2015-07-28 Central Glass Company, Limited Coating liquid for covering glass fiber and rubber-reinforcing glass fiber using same
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US20080280715A1 (en) * 2004-10-01 2008-11-13 Central Glass Company, Limited Coating Liquid for Covering Glass Fiber and Rubber-Reinforcing Glass Fiber Using Same
US8455097B2 (en) * 2004-10-01 2013-06-04 Central Glass Company, Limited Coating liquid for covering glass fiber and rubber-reinforcing glass fiber using same
US9091325B2 (en) 2004-10-01 2015-07-28 Central Glass Company, Limited Coating liquid for covering glass fiber and rubber-reinforcing glass fiber using same
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US8258224B2 (en) * 2007-06-08 2012-09-04 Sumitomo Rubber Industries, Ltd. Rubber composition for tire, and tire
US11072696B2 (en) * 2017-03-29 2021-07-27 Zeon Corporation Nitrile group-containing copolymer rubber and nitrile group-containing copolymer rubber cross-linked product

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WO2004101671A1 (de) 2004-11-25
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CN1823128B (zh) 2010-12-29
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JP4675901B2 (ja) 2011-04-27
US7572861B2 (en) 2009-08-11
JP2007503517A (ja) 2007-02-22
TW200505983A (en) 2005-02-16
US20080108753A1 (en) 2008-05-08
EP1633814B1 (de) 2014-04-02
KR20060009351A (ko) 2006-01-31
CN1823128A (zh) 2006-08-23
TWI351418B (en) 2011-11-01
DE10321875A1 (de) 2004-12-02
ES2466381T3 (es) 2014-06-10

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