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    1468603 Blends of butadiene-acrylonitrile copolymers and ethylene-containing copolymers E I DU PONT DE NEMOURS & CO 8 May 1974 [8 May 1973] 20349/74 Heading C3P A curable composition comprises a homogeneous blend of (A) 1-30 parts by weight of a butadiene-acrylonitrile copolymer containing 20-50 weight per cent of acrylonitrile and (B) 100 parts by weight of a copolymer of ethylene with a C 1 -C 4 alkyl acrylate or methacrylate containing at least 3À6 moles of ethylene and 2À5-8 moles of the ester per kg. which may contain up to 10% by weight of a third monomer selected from acrylic or methacrylic acid, CO, a vinyl ester, maleic anhydride, acrylonitrile, a C 1 -C 12 alkyl mono (or di) ester of butanedioic acid or an alkyl acrylate or methacrylate where the alkyl group contains at least 5 carbon atoms. The composition may also contain a peroxide, a cocuring agent therefor, an antioxidant system of a phosphorus compound with either a hindered phenol or an amine and a filler. In the examples blends of a copolymer of butadiene and acrylonitrile or a terpolymer thereof with acrylic acid with an ethylene-methyl acrylate copolymer or an ethylene-ethyl or methylacrylate-ethyl hydrogen maleate terpolymer also containing carbon black, barium sulphate, dicumyl peroxide, trisnonylphenyl phosphite, N,N<SP>1</SP>-m-phenylenedimaleimide and in some cases one or more of silica, 1,3,5-trimethyl-2,4,6- tris(3,5-t-bytyl-4-hydroxybenzyl) benzene and 4,4<SP>1</SP> - butylidene - bis(6 - t - butyl - m - cresol) are vulcanized. In comparative experiments (A) is replaced by natural rubber, polychloroprene, SBR, cis-polybutadiene or 1,2-polybutadiene or not present.
    公开号:SU1165237A3
    申请号:SU742026606
    申请日:1974-05-07
    公开日:1985-06-30
    发明作者:Джонсон Льюис Кэтрайн
    申请人:Е.И.Дюпон Де Немур Энд Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the rubber industry, in particular to the development of a rubber mixture based on ethylene copolymer for the production of rubber with improved durability and mechanical properties. A known rubber mixture based on an ethylene copolymer, for example, a copolymer of ethylene with propylene and butadiene, includes 18% acrylonitrile butadiene acrylonitrile rubber, a peroxide volcano group, for example, based on peroximone, an anti-ostarizer, for example, an aromatic amine, a stabilizer, for example, a phenol, for example, based on a peroximone, an anti-ostarizer, for example, an aromatic amine, a stabilizer, for example, a phenol, for example, based on peroximone, an anti-ostarizer, for example, an aromatic amine, a stabilizer, for example, a phenol, for example, based on a peroximone, an anti-ostarizer, for example, an aromatic amine, a stabilizer, for example, a phenol, for example, based on peroximone; - soot l. Rubber vulcanizers from this mixture do not have sufficient durability (low flexibility, high residual compression, insufficient heat resistance and oil resistance) and mechanical properties. The purpose of the invention is to increase the durability and improve the mechanical properties of the vulcanizers from this mixture. The goal is achieved by the fact that a rubber mixture based on ethylene copolymer, including butadiene-acrylonitrile rubber, peroxide vulcanizing group, antioxidant, stabilizer and filler, contains, as an ethylene copolymer, an ethylene ether copolymer selected from the group of: a copolymer of ethylene and methacrylate, ethylene-ether copolymer selected from the group of: ethylene and methacrylate, polystyrene copolymer selected from the group of: ethylene and methacrylate, polystyrene, and headbands, as well as headbands and headbands, as well as headbands and headbands and headwear and headbands and headbands and headbands and headbands and headbands and headbands and headbands and headbands and headbands and headbands and headwear and headbands and headbands and headbands and headbands and headbands and headbands and headbands and headbands and headbands and headbands and headbands and headbands to carry on using the ethylene ester copolymer, ethylene ether copolymer selected from the group of: }.: (3.5-3.9) :( 41.5-45.1) with a melt index of 0.95-1.2; a copolymer of ethylene with methacrylate in a ratio of 50:50 with a melt index of 0.6; copolymer ethylene with ethyl acrylate and monoethyl maleato m in a ratio of 53: 2.3: 44.7 with a melt index of 0.4 ethylene copolymer with vinyl acetate in a ratio of (40-62) :( 38-60) with a melt index of 0-57, as a rubber - butadiene acrylonitrile rubber with acrylonitrile 26.5-41% and Mooney viscosity 42-115 as a peroxide vulcanisation group - a combination of dicumyl peroxide and N, N- (m-phenyl) -dimalimide, as an antioxidant - tris-nonylphenylphosphite, as a stabilizer pa is a stabilizer selected from the group: 4,4-butylidene-bis- (6-tert-buty 72 m-cresol), 1,3,5-trimethyl-2.4 6-trice (3,5-di- tert-butyl-4-oksibenzyl) -benzol, 4.4 - bis- (c, obdimetshI-benzil) diphenylamine, and as a filler - a filler selected from the group: a mixture of furnace black with barium sulfate in a ratio of 10: 110, a furnace black, a mixture of furnace black with a thermal soot in a ratio of 10:40 ; a mixture of furnace black with barium sulfate and anhydrous silica in a ratio of 10: 61: 18.3, with the following ratio of components, wt.h .: Said ethylene ether copolymer100 Butadiene acrylonitrile rubber with an acrylonitrile content of 26.5-41% with a Mooney viscosity of 41- 1155-15 Dicumyl peroxide 5 N, N - (m-phenylene) dimaleimide2 Tris-nonylphenyl phosphite 1 Specified filler 50-120 Specified stabilizer 1-5 The invention is illustrated by examples in which the amounts of all materials are expressed in parts, fractions and percentages. Examples 1-14. In tab. 1 shows the composition of rubber mixtures in examples 1-14, and the content of each component is expressed in parts by weight. The rubber mixtures of Examples 1, 2 and 4-14 are mixed on a 3 × 8 inch (76.2 × 203.2 mm) roll for rubber mixture at room temperature for 10 minutes. First, ethylene-acrylic ether polymer, butadiene-acrylonitrile rubber and fillers are mixed together, and at the end of the mixing cycle, antioxidants and vulcanizing agents are added to the mixture. Plates with a thickness of 75 ml (1.955 mm) are molded from the final mixtures by press vulcanisation at 18 ° C for 30 minutes and a pressure of 640 pounds / dyme, i.e. 44,998 kg / cm, with the forms being heated under load and without load. Test plates are cut from these plates. The ASTM N0 oil volumetric swelling tests at 150 ° C for 3 days were carried out in accordance with the ASTM D-471 method. The tensile strength (Te, psi and relative elongation (Eg,%) is determined in accordance with ASTM Method D-412. The melt index of the original ethylene-acrylic ether copolymers is determined in accordance with ASTM Method D-1238-52T. Rubber The mixture according to Example 3 is prepared by mixing the components in a Banbury compact mixer at 50-60 ° C for 10 minutes. After that, test samples are prepared, which are then subjected to testing according to the foregoing. The results obtained for vulcanized compositions according to the The i-t4 measures are presented in Table 2. The data show that wulanisates, which contain a butadiene-acrylonitrile copolymer, are characterized by a high degree of vulcanization, which is reflected in a low oil-swellability. the type of fillers containing or not containing a butadiene-acrylonitrile copolymer, for example, comparable examples, 7c6 9c8, It, or 12 with to and 14 with t3, respectively. These results crawled, independently, as a terpolymer or copolymer as ethanol-polyacid polymer, and because of which filler was used mainly, namely, non-reinforcing barium sulphate, a highly reinforced furnace soot, which facilitates the extrusion, or weakly reinforces the average soot. Samples containing a butadiene-acryloitrile polymer also exhibit the ability to maintain ultimate tensile strength during aging when heated in comparison with samples containing only one ethylene-acrylate polymer. Test strips for determining the tensile strength are subjected to aging in air ovens at 177 ° C. From a comparison of the same number of examples obviously, h, the percentage ability to retain TB is increased for dimensional mixtures of butadiene-acrylonitrile. This difference is significant for softer blends that contain smaller amounts of reinforcing fillers, in particular, barium sulfate (example 2 or 3 compared to 1) or average thermal soot (example 7 compared to 6), or mixtures that are comonomer contain not methyl acrylate, but ethyl acrylate (example tt or t2 in comparison with example tO) together with furnace soot, which facilitates the extrusion. The ability to maintain elongation at break (IT) increases with the addition of a butadiene-acrylonitrile polymer, which is characteristic of softer blends. Example 15. This example illustrates the effect of the amount of a butadiene-acrylonitrile polymer on the initial properties and properties after aging upon heating with: - a scanner. - -l .: Rubber mixtures are mixed on a 3x8 inch (76.2 x X 203.2 mm) roll mill for rubber mixture at room temperature for 10 minutes. First, ethylene-alkyl acrylate copolymer, nitriplate rubber and fillers are mixed together, and at the end of the mixing cycle, antioxide, is added. danta and vulcanization agents. The final mixtures were press cured to form plates with a thickness of 75 mm at 180 ° C for 30 minutes and a pressure of 640 psi, i.e. 44,998 kg / cm, with forzchy subjected to heating under load and without load. Test plates are cut from these plates. The ASTM N0 volumetric swelling test in oil was carried out for 3 days according to ASTM D-471. The limit of prograncy at break (Tr lb / d) and relative elongation at break (Eg,%) were determined in accordance with ASTM Method D-412. o The composition of rubber compounds and test results are summarized in table. 3. For comparison, the data for the indicated ethylene-alkyl acrylate polymer is also entered into this table. Example 16. This example shows that butadiene acrylonitrile rubber is the only unsaturated elastomer that is acceptable for achieving this degree of improvement as the initial properties.
    and properties after thermal vulcanizate of etipenacrylether polymers,
    In the table below. Figure 4 shows the composition and properties of vulcanizate of different rubber mixtures of ethylene acrylic ether polymers containing another foiu polymer instead of a butadiene acrylonitrile polymer. By comparing the four properties of such rubber compounds with the properties of rubber compounds presented in Table. 2 for ethylene-acrylate ester polymers containing butadena-acrylonitrile polymers, it is quite obvious that the presence of this one gives a more noticeable improvement. This is particularly evident with respect to the test results.
    by definition, an elongation at 77 ° Cf which is an important factor for elastomers. The data obtained are similar to examples 15.
    Example 17. This example shows that the presence of a butadiene-acrylonitrile polymer increases the rate of vulcanization and stabilizes, during thermal aging, vulcanizates obtained from ethylene-vinyl-acetate-polymers (see Table 5). Samples are made and tested in analogy to Examples 1-14.
    Thus, -resins from the proposed mixture are characterized by better mechanical properties, heat resistance, resistance to heat shrinkage and flexibility.
    13
    П6523714
    Table 3
    The composition of the mixtures, and the properties of rubber Composition Ethylene-acrylate polymer Nitrile polymer. Furnace soot, facilitated syringement Barium sulphate Tris-nonylphenylphosphite 4,4-butylidene-bis- (6-trwt-butsh1m-cresol) Dicumylperoxide (40% on calcium carbonate) No., N-m-Fenilendimaleimide The initial properties of vulcanizato TB Volumetric swelling % After aging for 14 days at ITTC. Saving T,% CoxpisHeHHe Eg,%. Etipen-51 wt.% Methyl acrylate-3.9 equals 0.95 (ASTMD-1238-52T); Butadiene - 41 wt.% Acrylonitrile, is 115.,
    Composition and properties of rubber compounds
    , Composition of Ethyl Acrylate Polymer
    Furnace soot facilitating injection
    A) Barium sulphate
    The indicators in examples 16 (option)
    B 1 C I D (E
    100
    100
    100
    100 10
    10 61
    10 61
    10 61
    61
    15
    Anhydrous silica Tris-nonylphenylphosphite
    4,4 -Butylidene bis- (6-tert-butnpm-CREOL)
    Dicumyl peroxide (40Z on calcium carbonate)
    N, N - m-Phenylene-maleimide Natural rubber Styrene-butadiene polsher 1,2-Polybutadiene. Cis-1,4-polybutadiene polychloroprene. The initial properties of ethylene vulcanizate are 55 wt.% Methypacrylate-3.5 AesL is 1.2 (ASTM D-1238-521); Butadiene rubber rubber 1500j Supplied under the trade nanmenovoshtem, Redondobich, Calif.} Delivered under the trade name Nemur Evd Company. inc. ..
    1165237
    sixteen . Continuation of table. 3
    ten
    ten
    ten
    10 monoethyl maleate, melt itdex 2000, Histlé Neve Neoprene N firm E. E, Dupont de
    17
    18
    P65237 Table 5
    .
    I °
    权利要求:
    Claims (1)
    [1]
    RUBBER MIXTURE BASED ON THE ETHYLENE COPOLYMER, including butadiene acrylonitrile rubber, peroxide vulcanizing group, antioxidant, stabilizer and filler, characterized in that, in order to increase durability and improve the mechanical properties of vulcanizing agents from this mixture, the latter contains ethylene copolymer - ethylene copolymer selected from the group: a copolymer of ethylene with methyl acrylate and monoethyl maleate in the ratio (51-55) :( 3.5-3.9):: (41.5-45.1) with a melt index of 0.95-1.2; a copolymer of ethylene with methacrylate in a ratio of 50:50 with a melt index of 0.6, ’a copolymer of ethylene with ethyl acrylate and monoethyl maleate in a ratio of 53: 2.3: 44.7 with a melt index of 0.48; ethyleneAc vinyl acetate copolymer in the ratio (40-62) :( 38-60) with a melt index of 0-57, butadiene-acrylonitrile rubber with acrylonitrile content of 26.5 - 41% and Mooney viscosity 42-115, as a peroxide vulcanizing group as rubber · A combination of dicumyl peroxide and Ν, Ν * (m-phenylene) -dimaleimide, as an antioxidant - tris-nonylphenylphosphite, as a stabilizer, a stabilizer selected from the group: 4,4-butylidene-bis- (6-tert-butyl-m -cresol), 1,3,5-trimethyl-2, 4, 6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 4,4 * -bis- (v, -dimethyl-benzyl ) -diphenyl min, and as a filler - filler selected from the group: furnace black mixture with barium sulfate in a ratio of 10: 110, furnace black, furnace black mixture with thermal carbon black in a ratio of 10:40;
    About with a mixture of furnace black with barium sulfate and anhydrous silica in a ratio of 10: 61: 18.3, in the following ratio, wt.h:
    The specified ethylene ether copolymer Butadiene acrylonitrile rubber with a content of acrylonitrile .26,541% and a Mooney viscosity of 41-115
    Dicumyl peroxide Ν, Ν - (m-Phenylene) -dimaleimide
    Tris Nonylphenyl Phosphite Specified Filler Specified Stabilizer
    100
    5-15
    50-120
    1-5
    1165231
    1 1165237 2
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    优先权:
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    US35837073A| true| 1973-05-08|1973-05-08|
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