TW200540217A - Crosslinking of carboxylated nitrile polymers using compounds with at least two epoxy groups - Google Patents

Abstract

The present invention relates to a polymer compound comprising at least one carboxylated nitrile rubber polymer, that is optionally hydrogenated, at least one epoxidized compound having at least two epoxide functions and at least one filler, a method of inducing curing in a compound comprising at least one carboxylated nitrile rubber polymer, that is optionally hydrogenated, by addition of at least one epoxidized compound having at least two epoxide functions and subsequent curing.

Description

200540217 IX. Description of the invention: [Technical field subject to the invention 3 Field of the invention The present invention relates to a polymer containing at least one carboxylated nitrile rubber polymer 5 (which is selectively hydrogenated), at least one having at least two epoxy functions Epoxidized compound, and at least one filler polymer compound, by adding at least one epoxidized compound having at least two epoxide functions to at least one retarded nitrile rubber polymer (selectively hydrogenated ), A method of inducing a curing reaction in a compound and subsequently curing. 10 [Prior Art] Background of the Invention By carboxylated acrylonitrile-butadiene rubber (nitrile rubber; XNBR), it contains at least one total diene, at least one unsaturated nitrile, at least one carboxylated monomer, and an optional additional copolymer. Carboxylated 15 nitrile rubber (HXNBR) produced by selective hydrogenation of monomers) is a special rubber with excellent heat resistance, excellent ozone and chemical resistance, and excellent oil resistance. Combined with the high mechanical properties of rubber (especially high abrasion resistance), XNBR and HXNBR have not unexpectedly been found to be widely used in automobiles (seals, hoses, bearing gaskets), oils (baffles, wellhead seals, Valve disc), electricity (cable covering), mechanical engineering (wheel, rolling), and 20 shipbuilding (pipe seals, joints) and other industries. I: Summary of the Invention 3 Summary of the Invention In one of its aspects, the present invention relates to a warp ring comprising at least one carboxylated nitrile polymer (which is selectively hydrogenated) and at least one epoxide 200540217 function. Oxidized compounds, and polymer compounds of at least one filler. Preferably, the XNBR is fully or partially hydrogenated (' HXNBR ,,). In particular, the present invention relates to a polymerization comprising at least one carboxylated nitrile polymer (which is selectively hydrogenated), at least one epoxidized 5 compound having at least diepoxide functionality, and at least one filler. Biochemical compounds, which do not further contain crosslinking agents such as peroxides, sulfur, sulfur compounds, and the like. Simple illustration

Figure 1 shows the torque (S,), dN.m, of the compound of Example 3 for the first hour of curing at 1 ° arc and 180 ° C. Embodiment 2 Detailed Description of the Invention When used throughout the specification, the term "carboxylated nitrile polymer, or XNBR" is intended to have a broad meaning, and means to include at least one -/ 5-Unsaturated nitriles, at least one monomer with Weyl group, and optional & one or more copolymerizable monomer derived repeating units Olefins, especially C4-C6 conjugates ~. Preferred conjugated diene-based butadiene, isoprene, isoprene, 2,3, mebutene 20-T teradiene, and Mixtures of these. More preferred C4-C6 conjugated dimerized butadiene, isoprene, and mixtures thereof. Most preferred C4-C6 conjugated diene based butadiene. Α, Bu Bu Yu and nitrile can be any known α, β-unsaturated nitrile, especially <: 3 < 5〇 ^ _; ^^ nitrile. Preferably (^ (: 54_ unsaturated nitrile acrylonitrile, methyl propylene) Dilute riding, hexyl acrylonitrile, and mixtures thereof. The best C3-C5 200540217 α, β-unsaturated nitrile acrylonitrile. The early body with at least -carboxyl group can be any Dilute copolymerized known monomers having at least one carboxyl group. Preferred mono-unsaturated wei acids having at least-. Non-limiting examples of suitable 5 unsaturated carboxylic acids are fumaric acid, maleic acid, acrylic acid. , Methacrylic acid, and mixtures thereof. Preferably, the copolymer comprises from 40 to 85% by weight of a repeating single t1 derived from one or more conjugated diene in the range from 15 to 6G by weight. Unsaturated riding-derived repeating units' and H15% by weight of repeating units derived from one or more monomers having at least one carboxyl group. More preferably, the copolymer contains from 55 to 75% by weight Multiple co-light dilute derived repeat units, 25 to 40% by weight of repeat units derived from one or more unsaturated guesses, and 1 to 7% by weight of one or more monomers derived from at least one carboxyl group Repeating units. 15 Optionally, the copolymer may further include repeating units derived from one or more copolymerizable monomers (such as alkyl acrylate, styrene). From one or more copolymerizable monomers Derived repeat order Nitrile nitrile rubber will replace part or dienes, and for the person skilled in the art clearly needs to be adjusted to the above values result in 100 wt%.

20 The hydrogenation reaction of the present invention is preferably understood to be that more than 50% of the residual double bond (RDB) present in the starting nitrile / NR is hydrogenated, and more preferably that more than 900 / 〇 RDB is hydrogenated More preferably, more than 95% of rDb is hydrogenated, and the best is more than 99 ° /. The RDB is hydrogenated. The present invention is not limited to a special method for manufacturing hydrocarboxylated NBR. For 200540217, the preferred HXNBR system of the present invention can be easily obtained by those disclosed in WO-01 / 77185-A1. For regions where this procedure is permitted, WO-01 / 77185-A1 is hereby incorporated by reference. XNBR and 5 HXNBR forming the preferred components of the polymer compounds of the present invention can be described by standard techniques known in the art. For example, the molecular weight distribution of polymers is obtained by operating the Waters Millenium software version 3.05.01 by gel permeation chromatography (GPC) using Waters 2690 Separation Module and Waters 410 Differential Refractometer. Decide. The sample was dissolved in tetrahydro 10-bitan (THF), which was solubilized with 0.025% BHT. The columns used for the measurements were three sequentially mixed-B gel columns from Polymer Labs. The reference standard used was a polystyrene standard from Americaail Poiymer Standards Corp. The polymer compound of the present invention further comprises a compound which is at least one and which has at least two or more ring-emulsions S which can be oxidized. The epoxidized compound having at least biepoxide functionality is not limited, and any known compound having two or more monomers capable of interacting with at least one carboxyl group under conditions typically used in rubber curing reactions Carboxylated epoxide-functional epoxidized compounds are suitable. Non-limiting examples are epoxidized mineral oils, epoxidized fatty acids, epoxidized oils obtained from natural sources, 20 corresponding oils and fats, fatty acid glycerol vinegar prepared by methods known in the art Epoxidized derivatives. Suitable epoxidized fat 2 acid glycerin vinegar contains epoxidized soybean oil (ESB0). Epoxidized linseed oil, epoxidized corn oil, epoxidized coconut oil, epoxidized cottonseed Oil, epoxidized olive oil, epoxidized plucked oil, epoxidized 200540217 oxidized palm kernel "you, epoxidized peanuts", epoxidized cod liver oil, epoxidized tung oil , Epoxidized tallow, epoxidized, milk and epoxy resins, glycidyl epoxides, and non-glycidyl-based mounting oxides, and mixtures thereof. Preferred is bisphenol-A diglycidyl oleyl ether (DGEBA). The polymer compound of the present invention further comprises at least one filler. This filler may be an active or inactive filler or a mixture thereof. The filler may be in particular j%-a highly dispersed silica prepared by, for example, precipitation of a silicate solution or flame hydrolysis of a silicon halide, having a specific surface area in the range of 5 to 1000 m ^ g , And has a main particle size in the range of 10 to 400 nm; silica can also be selectively mixed with other metal oxides such as A1, Mg, Ca, Ba, Zn, Zr and Ti Oxides are present; synthetic silicates, such as aluminum silicate and earth metal silicates, such as magnesium oxalate or oxalate 4 bow, have a betin ratio of 20 to 400 m 2 / g Surface area and major particle diameters in the range of 10 to 400 nm;%-natural silicates such as kaolin and other naturally occurring; δ xisite;-glass fibers and glass fiber products (mats, extrudate) or glass micro Ball;-carbon black, carbon black to be used here is made by lamp black, furnace black or gas black, and preferably has a 20 BET (DIN66 131) ratio of 20 to 200 m 2 / g Surface area, for example, SAF, ISAF, HAF, FEF or GPF carbon black;-rubber gels, especially polybutadiene, butadiene / Stupid ethylene copolymer, butadiene / acrylonitrile copolymers, polybutadiene, and poly gas; etc., or a mixture. 200540217 Examples of soft bunker mineral fillers include silica, silicate, clay (such as) stone moon, alumina, titanium dioxide, talc, and mixtures thereof. These mineral particles have warp groups on their surface, making them hydrophilic and oleophobic. This deepens the difficulty of achieving good interaction between filler particles and rubber. For many purposes, it is preferred that the Shiguangite be Shixite, especially silica prepared by the precipitation of carbon dioxide by sodium oxalate. The dried amorphous spar suitable for use in accordance with the present invention may have an average agglomerated particle size of mi 00 micrometers, preferably between 10 and 50 micrometers, and most preferably between 10 and 25 micrometers. The car is less than 10 volumes. The agglomerated particles of / () have a size of less than 5 microns or more than 10 to 50 microns. Furthermore, suitable non-crystalline dried silica generally has a bet surface area in the range of 50 to 450 m 2 / g (measured according to din (Deutsche Industrie Norm) 66131), 150 to 400 g / 100 g of stone. DBP absorption in stone range (measured according to mN 53601) and drying loss in the range of 0 to 10 weight 0 / 〇 (measured according to DIN ISO 787/11). Appropriate Shixiite filler 15 is available from PPG Industries under the trade names HiSil⑧210, HiSil® 233 and

HiSil® 243. Also suitable for Vulkasil® S and Vulkasil® N from Bayer AG. Generally, it is advantageous to use carbon black as the filler system. Generally, the carbon black is present in the polymer compound in an amount ranging from 20 to 200 parts by weight, preferably 30 to 150 parts by weight, and more preferably 40 to 100 parts by weight. Furthermore, it may be advantageous to use a mixture of carbon black and mineral filler in the polymer composite of the present invention. In this mixture, the ratio of the mineral filler to the carbon black is generally in the range of 0.05 to 20, preferably 0.1 to 10. The rubber composition according to the present invention may contain additional auxiliary products for rubber such as reaction accelerator, vulcanization reaction accelerator, vulcanization reaction accelerator, antioxidant, foaming agent, anti-aging agent, heat stabilizer, etc. Agent, light stabilizer, ozone stabilizer, processing aid, plasticizer, thickener,-foaming agent, dye, colorant, wax, extender, organic acid, inhibitor, gold, 5 belong to oxidation And activators such as triethanolamine, polyethylene glycol, hexane, triol, etc., which are known in the rubber industry. Rubber additives are used in conventional amounts, depending on the intended use and the like. Conventional content is, for example, 〇1 to weight ° / 〇, which is based on rubber. Preferably, the composition contains organic fatty acids in the range of 0.001 to 20B as auxiliary products, preferably unsaturated fatty acids having 1 to 10, two or more carbon double bonds in the molecule, and more preferably 10 weight % Or more of a conjugated dienoic acid having at least one carbon-carbon double bond in its molecule. Preferably, these fatty acids have carbon atoms in the range of 8-22, more preferably 12-18. Examples include calcium-, zinc-, magnesium-, potassium- and ammonium salts of stearic acid, palmitic acid and oleic acid and the like. Preferably, the composition comprises an acrylate in the range of 5 to 50 ph 15 as an auxiliary product. Suitable acrylates are from EP-A1-0 319 320 (especially lines 16 to% on page 3), • US-5 208 294 (especially lines 2 to 25 to 40) and us_4 983 678 (especially Is column 2 lines 45 to 62). Particularly preferred are zinc acrylate, zinc diacrylate or zinc diacrylic acid acrylate, or a liquid acrylate such as trimethyl 2. Alcohol propane trimethacrylate (TRIM), butanediol dimethylpropane (BDMA) and ethylene glycol dimethacrylate (EDMA). Advantageously, a mixture of different acrylates and / or their metal salts is used. Particularly advantageous are often used with Scorch-moderators (such as sterically hindered phenols (eg, methylphenanthrene, tertiary first methylamine; metal acrylates derived from metadimethyl 200540217). Components of the final polymer composite It is mixed together, suitably in the range of 25. (: to an elevated temperature of 200 ° C. Generally, the mixing time is not more than 1 hour, and the time in the range of 2 to 30 minutes is generally suitable. The mixing system is 5 Internal mixers (such as Banbury mixers, or Haake or Brabender mini-internal mixers) are properly implemented. Two-roll mill mixers also provide good dispersion of additives in the elastomer. Extruders also provide good mixing, and A shorter mixing time is allowed. This mixing can be performed in two or more stages, and the mixing can be performed in different units, for example, one stage is connected to the internal mixer 10 and one stage is connected to the extruder. But Please be careful that unnecessary pre-crosslinking (= coking) occurs during the mixing stage, but the conditions are suitable for the reaction between the epoxidized compound and the retarder. For chemical reactions and vulcanization reactions also see: Encyclopedia of Polymer Science and Engineering (Encyd〇pedia 〇f㈣ Coffee

Science and Engineering), Book 4, page% and others (Chemical Cooperation) 15 and Book 17, page 666 and others (Sulfuration reaction). This method provides heat-reversible cross-linking between polymer chains. Accordingly, the present invention provides a composition comprising at least one retarded rubber polymer (optionally hydrogenated), at least-epoxidized compound having at least diepoxide functionality, and at least-filler. Furthermore, the polymer 20 compound of the present invention can be used for manufacturing a molded article containing the polymer compound of the present invention. Preferred moldings are seals, hoses, bearing gaskets, baffles, wellhead seals, wide disks, slow wire covers, wheels, rollings, line seals, mPlaCegaSkets, or shoe components, which are borrowed Manufactured by injection molding technology. Furthermore, the polymer composite of the present invention is extremely suitable for the manufacture of electric wires and wires. EXAMPLES Examples 1-3 The polymer composite was mixed in a brabender mini internal mixer in a single 5-step mixing step (8 minutes / 3 (TC / 80 rpm). The composite can also be prepared by grinding and mixing. This The composition used in the evaluation is mainly based on the formula according to Table 1. Comparative Example 3 is for comparison. Table 1-Compound Formulation Example 1 Example 2 Comparative Example 3 ARMEEN 18D 0.5 0.5 0.5 THERBANXT8889 100 100 100 carbon black, Ν 660 STERLING-V 50 50 50 NAUGARD 445 1 1 1 PLASTHALL TOTM 5 5 5 DIAK # 7 1.5 EPON resin 828 5 10 STRUKTOLZP1014 7 VULCUP 40KE 7

Armeen ™ 18D is an octadecylamine derived from AkzoNobel and is used to reduce the compound's viscosity to metals. THERBAN ™ XTTM 8889 is HXNBR of Bayer AG.

Naugard ™ 445 (p-dicumyl diphenylamine) is a stabilizer of Uniroyal. Plasthall TOTM ™ (trioctyl trimellitate) is a plasticizer of C.P. Hall. 0 Diak ™ 7 (triallyl isocyanurate) is a common reagent of DuPont. 15 Struktol ™ ZP 1014 (50% zinc peroxide on an inert carrier).

Vulcup 40 KE (α, α · bis (third butylperoxy) diisopropylbenzene), 40% peroxide. Epoxidized molecular system EPOON ™ 828 as a curing agent, a liquid epoxy resin made from bisphenol 13 200540217-A and epichlorohydrin, and obtained from Resolution

Performance Products ° Properties of polymer composites Table 2-MDR curing properties Table 2 shows an overview of the properties of the polymer composites of Examples 1-3. 5 011 curing properties (180 ° (:, 1 ° & 1 ^, 1.7112, 60 minutes) Example 1 Example 2 Comparative Example 3 Maximum Torque (MH, dN.m) 44.19 57.50 35.29 Minimum Torque (ML , dN.m) 1.10 0.83 1.62 AMH-ML (dN.m) 43.09 56.67 33.67 AMH-ML indicates the crosslink density and it increases as a function of the epoxy resin content. I: Simple illustration of the diagram 3 10 1 The figure shows the torque (S ') of the first hour of curing of the compound of Examples 1-3 at 1.arc and 180 ° C, dN.m. [Description of Symbols of Main Components] (None) 14

Claims (1)

200540217 10. Scope of patent application: 1. A polymer compound comprising at least one selectively hydrogenated carboxylated nitrile rubber polymer 'at least epoxidized compound having at least diepoxide function' and at least one filler. 5 2. For the compound of item 1 of the patent scope, in which the polymer is a hydrogenated nitrile rubber. 3. The compound according to item 1 or 2 of the Shengu patent scope, wherein the compound does not include any additional cross-linking or curing agent. 4. The compound according to any one of claims 1 to 3 in the patent application scope, wherein the 10% oxidized compound is a glycidyl epoxy compound. 5. The compound according to any one of claims 1-4, wherein the epoxidized compound is in an amount of 0, t0,20 phr, and more preferably in an amount of 5 to 20, presence. A method for inducing a curing reaction by adding at least one epoxidized compound having at least a diepoxide function to a compound containing at least one selectively carboxylated nitrile rubber polymer which has been hydrogenated, and post-curing the compound . 7. Use of a polymer compound comprising at least one selectively hydrogenated tritiated nitrile rubber polymer, at least one epoxidized compound having at least two epoxides, and at least one filler, It is used to make type 20 objects. 8 · If you apply for a patent _ item 7, it is used to manufacture seals, hoses, bearing gaskets, baffles, wellhead seals, valve disks, cable covers, wheels, rolling, etc. manufactured by injection molding technology. Manufacture of pipeline seals, strips, local loops or shoe components, wires and cables. 15