• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 引用文献
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    • 专利摘要:
    1455916 Modified elastomers POLYSAR Ltd 7 Nov 1974 [8 Nov 1973] 48274/74 Heading C3P Rubbery conjugated C 4-6 diene polymers containing 0À5-10 millimoles of tertiary amine groups per 100 grams of polymer are reacted with an organic compound containing at least two halogen atoms capable of forming quaternary ammonium salts with said tertiary amine groups. The products have improved green strength, and may be blended with other polymers and with conventional compounding ingredients. In examples, the polymer is SBR or nitrile rubber each containing units of dimethylaminoethyl methacrylate, and the organic compound is 1,4 - dibromobutene- 2, 1,4 - dichlorobutene - 2, α,α<SP>1</SP> - dibromo - pxylene, dibromosorbic acid or the sodium salt thereof, or liquid dibromo-polybutadiene. In Example 3, a composition of such a modified polymer with polybutadiene is described.
    公开号:SU1169544A3
    申请号:SU742073008
    申请日:1974-11-06
    公开日:1985-07-23
    发明作者:Ласис Эвальдс；Дже Баклер Эрнест
    申请人:Полисар Лимитед (Фирма)；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION The invention relates to the rubber industry, in particular to the rubber mixture based on unsaturated rubber. The aim of the invention is to increase the cohesive strength of the mixture. Example 1. Copolymers are prepared by polymerizing a mixture of monomers, including 71 May, h. 1,3 butadiene, 28 ma.ch. styrene and various amounts (0.3 - 0.7 wt.h.) dimethylaminoethyl methacrylate. The monomer mixture is emulsified in a 152 reactor with constant stirring at 185 wt.h. 3% aqueous solution of rosin sodium salt. The polymerization reaction is carried out at about 60% in the presence of a redox catalyst. After removal of the residual monomer, 37.5 wt. Parts was added. hydrocarbon mineral oil at 100 ma.ch. rubber in the latex stage (the process is carried out in parallel for three samples: A, B, C). Samples are coagulated and cleaned to obtain a solid rubber-like polymer. Infrared analysis shows that sample A contains 0.30 wt.% Of tertiary amino groups attached to the copolymer, sample B - 0.34 wt.% And sample C - 0.77 wt.%. Sample A has a Mooney viscosity (ML - 4 at) about 53, sample B has about 63, sample C - 83, and it contains no oil. Rubber samples A, ViC and control sample D — standard amino styrene-butadiene rubber, not containing amino groups, but prepared and filled with oil as above, have a mass ratio of butadiene to styrene 77/23 and Mooney 50 viscosity, are biased in a laboratory mill according to the following recipe, us, h .: Rubber Resistance to abrasion furnace soot Zinc oxide Stearic acid N-tper -Nutil-2-benzothiazole sulfenamide Sulfur 1,4-Libbrombsh1en-2 Dosage varies All mixtures are well treated in rolls at about 7s . The properties of the months with respect to the deformations are followed in the unvulcanized (raw) state at room temperature on the tester at a rate of separation of the clamps of 50 cm / min. The effect of the composition on the results of the investigations is presented in Table. 1. Example 2. Samples of the oil-filled rubbers described in Example 1 are used to make blends as described above, but various chlorine and bromo compounds are used to form unstable bonds. The strength of the crude mixture is investigated analogously to example 1. The results of the research are presented in table. 2. Example 3. A rubber specimen. B, described in B of Example 1, containing 37.5 ma.ch. on 100 ma.ch. the mineral oil polymer and having 0.34 wt.% of the bound tertiary amino groups are mixed with the polymerized polybutadiene solution. Equal parts of oil-filled rubber B and polybutadiene are used, mixed in accordance with the recipe given in Example 1. This recipe includes 0.1 wt.h. 1,4-dibromobutylene-2 on YuOmas.ch. rubber B. Stress properties - strain for raw mix according to this recipe: 100% modulus, kg / cm - 2.8 200% modulus, kg / cm2. 3.4 LM,% + 21.2 Elongation at the time of destruction,% 380 Tensile strength at break, kg / cm 3.5 The presence of an admixture of the second rubber in the mixture does not prevent the increase in the strength of the raw mixture. Example 4 The oil-filled rubber samples of Example 1 are mixed according to the recipe of Example 1, including various amounts of 1,4-dibromobutylene-2 or dibromodimethylbenzene, and vulcanized under standard conditions. Vulcanized samples examined in comparison with the vulcanized control sample D according to example 1. The results of the research are presented in table. 3. As can be seen from the data table. 3, the vulcanization properties proposed
    The compositions differ slightly from the properties of the known polymers.
    Example 5. A rubber-like terpolymer of butadiene (71 May, parts of styrene (28 parts per hour) and dimethylaminostilmethacrylate (0.7 parts per hour) is prepared according to Example 1 and divided into three portions. The polymer is not filled It has a Mooney viscosity of 57. Portions are mixed in a laboratory mill according to the recipe of Example 1, but instead of 1,4-dibromobutadiene-2, different amounts of dibromopolybutadiene are used, mol.m. 2000. Dibromopolybutadiene is a polymer, butadiene, having essentially two the final bromoallyl groups on the polymer molecular.
    The strength of the raw mixture of the resulting rubbers is presented in table. four.
    Example 6. Nitrile rubber is obtained, for which a mixture of monomers containing 67 wt. 1,3-butadiene, 33 ma.ch. acrylonitrile and 0.5 ma.ch. dimethylaminoethylacrylate is loaded into the reactor and polymerized by the method of free radical emulsion.
    polymerization catalyzed by the redox system. The resulting terpolymer is recovered in the usual manner, after which it is mixed with 0.3 parts by weight. 1,4-dibromobutylene-2 at 100ma.h. rubber in a laboratory mill, using recipe 1, but the amount of stearic acid is reduced to 0.5 wt.h. The mixture is greeted with its stress-strain deformation in a fresh form at room temperature on a tetor with a dilution of the clamps of 50 s / min. 1005 rubber module 12.0kg / em2, 200% modulus 13.8 kg / em 4m 15%, tensile strength at rupture 7.5 kg / e, elongation at the moment of rupture 980%. This is comparable to regular ethane. darn nitrile rubber containing 67% by weight of 1.3-butadiene and 33 wt.h. Acrylonitrile, non-containing tretaminomonomer, which is mixed and cooled by the same drugs, 100% module 7.2 kg / e, 200% module 6.0 kg / e, DM 16.7%, elongation of the gap 550%, tensile strength at break 3 , 5 kg / eat.
    Content of components, m
    tertiary amino groups
    1,4-dibromobutylene-2
    on 100 ma.ch. eopolymer
    and maela
    100% module, kg / cm
    200% modulus, kg / cm 4M,% Break extension,%
    Strength limit when discharged
    kg / cm
    0.70
    0.34
    10.9
    1.8
    2.4
    0.3 0.3
    dib romp olib ut ad n (per 100 lbs. rubber and maela)
    one
    dibromeorbine kielota (per 100 mah.ch. of rubber and maela)
    sodium eibol dibromeorbine kielota (per 100 m of rubber and oil)
    100% module, kg / eat 200% module, kg / eat
    , 4M,% Elongation,%
    Tensile strength at break,
    kg / cm 3,753.6 Component content, m.ch .: 1,4-dibromobut1-1-2, “-dibromparadimethylbenzene Tensile strength, kg / cm, after 25-minute vulcanization 215 210 238 226 215 235 50-minute
    Table. 2
    0.34 0.34 0.34
    0.123 .0.025
    0.25
    0.20,4
    0.4
    4.8
    3.8
    4.4
    5.8
    -1-20,8-И5,8
    640700
    7.96.2 0.1 0.15 0.2 0.3 0.45 0.123 0.18 235 218 230 206 222 224 230 213 215 217 224 225
    Shore hardness
    A-2 after curing
    Continuation of table 3
    权利要求:
    Claims (1)
    [1]
    RUBBER MIXTURE BASED ON UNSATURATED RUBBER, including carbon black, stearic acid and digaloid · containing an organic compound, characterized in that, in order to increase the cohesive strength of the mixture, it contains a copolymer of 61-71 parts by weight as rubber. butadiene, 28 parts by weight styrene or 33 parts by weight acrylonitrile and 0.3-0.7 wt.h. dimethylaminoethyl methacrylate, abrasion resistant soot, as a carbon black, a compound selected from the group as a dihaloid-containing organic compound
    1,4-dibromobutylene-2, d, c ^ -dibromo-para-dimethylbenzene, liquid dibromopolybutadiene mol.m 2000, dibromosorbic acid, sodium salt of dibromosorbic acid, and additionally contains zinc oxide, N-rper-butyp-2-benzothiazole sulfenamide, sulfur in the following ratio of components, parts by weight:
    Rubber 100 Furnace soot resistant to is- wound fifty Zinc oxide 3 Stearin acid 1 N-tert-butyl-2- benzothiazole sulfenamcd 1 Sulfur 1.75 Digaloid-containing organic soy yarn selected from the group: 1,4-dibromobutylene-2 0.1-0.45 tl, οΖ-dibromapara- dimethylbenzene 0.025-0.185 liquid dibrom- polybutadiene mol.m. 2000 0.25-6.0 dibromosorbic acid 0.2-0.4 sodium salt dibromosorbic acid 0.4
    SU „.1169544>
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    同族专利:
    公开号 | 公开日
    ES431647A1|1976-11-01|
    IN141959B|1977-05-14|
    IT1024756B|1978-07-20|
    JPS545826B2|1979-03-22|
    ZA747150B|1976-05-26|
    CA1014296A|1977-07-19|
    DE2452931C2|1981-10-08|
    AR205005A1|1976-03-31|
    DE2452931A1|1975-05-22|
    AU7500874A|1976-05-06|
    NL7414462A|1975-05-12|
    FR2250769B1|1984-08-10|
    GB1455916A|1976-11-17|
    FR2250769A1|1975-06-06|
    BE821867A|1975-05-05|
    JPS5075635A|1975-06-20|
    US3969330A|1976-07-13|
    NL174048C|1984-04-16|
    NL174048B|1983-11-16|
    引用文献:
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    US6148748A|1998-05-22|2000-11-21|Flexi-Coil Ltd.|In-line seed treating unit for air seeders|US2965594A|1953-10-30|1960-12-20|Ciba Ltd|Carboxylic acid ester containing a quaternar y nitrogen atom in the alcohol portion, and polymerization products thereof|
    US3011996A|1957-04-15|1961-12-05|Exxon Research Engineering Co|Process of reacting a tertiary amine with a halogenated copolymer of an isoolefin monomer and a multiolefin monomer, and product thereof|
    US3178398A|1960-10-24|1965-04-13|Phillips Petroleum Co|Production and curing of polymers containing terminally reactive nitrogen|
    US3527744A|1965-05-11|1970-09-08|Natural Rubber Producers|Vulcanization of rubber with complex of monochloroborane and tertiary amine or triphenyl phosphine|CA1042330A|1976-01-13|1978-11-14|Yung-Kang Wei|Radial ply pneumatic tires and process for their manufacture|
    DE2613051C2|1976-03-26|1983-04-28|Polysar Ltd., Sarnia, Ontario|Process for producing a synthetic rubber with improved green strength|
    DE2613050C2|1976-03-26|1984-01-05|Polysar Ltd., Sarnia, Ontario|Process for producing a synthetic rubber with improved green strength|
    CA1100732A|1977-10-27|1981-05-12|George J. Briggs|Processing green strength polymers|
    US4454304A|1981-04-22|1984-06-12|Copolymer Rubber & Chemical Corp.|Method and material for producing high green strength rubber compounds|
    US4677182A|1985-11-25|1987-06-30|Minnesota Mining And Manufacturing Co.|Ionene elastomers|
    US5292813A|1992-10-02|1994-03-08|Exxon Research & Engineering Co.|Fullerene-grafted polymers and processes of making|
    DE10049804A1|2000-10-09|2002-04-18|Bayer Ag|Agent containing synergistic mixture comprising phenyl-pyrroline ketoenol derivatives with fungicides and acaricides useful especially in plant protection|
    US7019058B2|2000-10-11|2006-03-28|Exxonmobil Chemical Patents, Inc.|Halogenated elastomeric compositions having enhanced viscosity|
    US6552108B1|2000-10-11|2003-04-22|Exxonmobil Chemical Patents Inc.|Rubber blends having improved stability and green strength|
    RU2305690C2|2000-10-11|2007-09-10|Эксонмобил Кемикэл Пейтентс Инк.|Halogenated elastomeric compositions showing elevated viscosity|
    US20060189774A1|2005-02-18|2006-08-24|Agency For Science, Technology And Research|Modifiable polyunsaturated polymers and processes for their preparation|
    US7820765B2|2005-07-20|2010-10-26|Bridgestone Corporation|Amine functionalized polymers|
    EP3042786B1|2014-12-19|2017-11-22|The Goodyear Tire & Rubber Company|Functionalized elastomer|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CA185,359A|CA1014296A|1973-11-08|1973-11-08|Amine modified polymers|
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