• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Improved shock-resistant resins are obtained by graft-copolymerizing a monomer selected from among alkenyl aromatics, vinylics, acrylics, their halogenated derivatives or admixtures of same, with maleic anhydride and/or an imide derivative of such anhydride and with a terpolymer composed by ethylene, a higher homolog of ethylene and a polyene having at least one system of conjugated double bonds.
    公开号:SU764611A3
    申请号:SU762406156
    申请日:1976-10-01
    公开日:1980-09-15
    发明作者:Арригетти Серджо；Бранкаччио Альдо；Ческа Себастьяно；Джулиани Джампаоло
    申请人:Аник С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the field of producing impact copolymers, which, moreover, resist aging in the open air and are characterized by a high deformation temperature in the hot state. It is known that impact resistant resins can be obtained by grafting vinylaromatic monomers or halide compounds of vinyl either alone or in a mixture, in general with aryl compounds, as highly unsaturated rubbers, such as polybutadiene and low unsaturated rubbers, such as triple polymers based on ethylene, propylene and polyene ll. The use of rubber-like materials having a low content of unsaturated bonds, such as ethylene and polypropylene-based three-stage polymers in the synthesis of impact-resistant resins, makes it possible to obtain materials that resist aging, undoubtedly higher than those obtained using highly unsaturated rubbers. . However, the limitation for impact materials discussed above is; is that they cannot be used. in the manufacture of products from substitutes (artifacts), which are intended for use at elevated temperatures, above 90-100 ° C, due to the relatively low values of warping temperature under load in a hot condition (hot condition - in accordance with ASTM D648 ), which in the case of ABS resins lies in the range from 80 to, and in the case of olefin-based resins, the three-part polymer reaches values ranging from 90 to 5 6 seconds. Known cnocoiS of obtaining impact-resistant copolymers by radical ooplimerization in the emulsion by heating (0-100 ° C) a mixture of styrene, acrylonitrile and maleimide in the presence of 1-25% by weight of monomers based on a conjugated diene or its mixture with vinyl monomer {2, Lack The method consists in the fact that the known copolymers of possessions are not of sufficiently high strength and have a non-high enough bending modulus. The purpose of the invention is to increase the strength and modulus of flexibility. . The goal is achieved by the fact that in yoso 6e half a half a year, you can find a copolymer ipOB by radical copolymerization in an emulsion with heating1 and a mixture of styrene, acrylonitrile and maleim in the presence of 1-25% by weight of monomers based on conjugated daena. or its mixture with a vinyl monomer, as an elastomer based on a conjugated diene or its siesa, with a vinyl monomer, using an elastomer based on ethyl on propylene and polyene. The grafting reaction to the elastomer can be carried out by copolymerizing the mixture of the above monomers in a block, in suspension, in an emulsion or in solution in an aromatic, aliphatic solvent or in an alkyl or aryoligomer. In addition, mixtures of one or more of these solvents can be used as solvents, as well as mixtures with polar solvents, more preferably with acetone, ketones, ethers, esters, etc. As an initiator, you can choose any catalyst that | It is used for priming (priming β1 radical reactions, tai bai as persulfuric acid, peracetic acid, potassium persulfate, benzoyl peroxide, lauryl peroxide, di-tert-butyl peroxide; azoic acid)., Preparation of impact-resistant resins in accordance with H3o6peTeHHH) / ljBbmpnHHroT in accordance with and in accordance with the rules of procedure, and ihrd from (O-interoiuyns. ItOr and srbtoyuyuyyyyyyyyyyyyyyyyyyayyayyayyayyayyayya maya aya maya no. in relation to the total weight of the response maleic anhydride and / or imide derivative of maleic anhydride - from 1 to 50% by weight, relative to the total weight of 1 reagI13Ange yuyuyust. -.,. ..-- ::. - ..- - ..; -.- - b three-necked flask, with a capacity of 2 liters and equipped with a ball cooler, is charged in a nitrogen atmosphere with 15 g of a three-star polymer prepared from ethylene, propylene and 1-isopropylidene cyclopentadiene, having a trace, vns.% 66, rnli toluene, dl / g1.71 V Double bonds per 1000 atoms s,% 2.4 450 g of a mixture consisting of 50 parts by weight is added. benzene and 50 hours; heptane and stirred at room temperature (until the polymer is dissolved. To the solution of the three-unit polymer then add g: benzoyl peroxide 1,2; styrene 116) acrylonitrile 40, and the reaction is carried out for 8 h when under nitrogen. The reaction product is then precipitated in 3 liters of isopropyl alcohol, filtered off and washed at room temperature under vacuum. 153 g of resin are obtained. Example 2. Follow the procedure of the test of example 1, using 17 g of olefinic three-unit polymer with the same properties as the polymer used in example 1, p with the same amounts of monomers and solvents as in example 1. In the reaction phase in the initial stage 15 g of N-phenylimide maleic acid are added. Upon completion of the reaction, 170 g of resin are obtained. When adding an imide derivative of maleic acid, a resin is obtained, the temperature of hot warping (THC / HOT) in the second is slightly higher than that of the material of example 1, the rigidity is higher and the impact resistance is good. Example 3. The procedure of Example 2 was repeated, with 15 g of maleic acid imide being added at the very beginning. 172 g of resin are obtained. Imide maleinry acid also improves the properties of the resin, especially the modulus and THC. Example 4. The reaction was carried out under the same conditions as in Example 1, c. 5.2% solution only in benzene of a rubbery three-link polymer based on ethylene, propylene and 2- (2,4-dimethylpent-1, 3-dienyl) -norborn-5-yon, having the following properties:, weight. % 60 CRP, toluene, 30 ° С, dl / g V 1.95. Double bonds on the loop of C atoms,% 2.7. . , Before, we begin the reaction, 15 g of Mgtr-butylamide maleic acid is added. Getting; Yiot 161 g of product. Example 5: The procedure of Example 1 was followed. A 6% solution in n-heptane of a three-link polymer in ethylene, propylene and (2-norborn-5-enyl) - (cyclohex- , 3-dienyl-2, 5-trimethyl) methane, smoldering the following properties: C2.H4 / wt.% 62 Cnj, toluene,. ZO-S, dl / g 2.1
    Double bonds on
    1000 C atoms,% 3.0 ,,
    j Before starting the reaction, 16 g of M- (p-naphthyl) imide maleic acid is added.
    Get 155 g of resin, the properties of which are shown in the table.
    Example 6. npkmer 2 was repeated, with 19 g of a three-unit polymer based on ethylene, propylene and 1-ispropylene cyclopynthenylene, by adding 25 g of maleic acid imide.
    177 g of resin are obtained. As can be seen, by increasing the imide supply of maleic acid, it becomes possible to obtain materials that have an even higher TG value.
    Example 7. In 100 ml of n-hexane, 8 g of a three-unit polymer based on ethylene, propylene and 5-ethylidene-norborn-1-ene, having the following properties, are dissolved:
    CdH, wt.% 63
    G | 3, toluene,
    20C, dl / g1,71
    Double bonds on
    1000 atoms of C,% 8,2,
    A solution of the three-unit polymer in hexane is added dropwise to the doazirovanny flask equipped with a stirrer and containing 100 ml of a 2% aqueous solution (by weight) of potassium silicate (salt of a rubber of rubber acids). A very thin suspension is formed, which is emulsified in a monogenizer. The solvent is then removed by steam distillation.
    The resulting latex is settled for 80 hours and separated from the aqueous fraction, which is removed.
    A co-emulsion emulsion was introduced into a deaerated flask equipped with a reflux condenser, a thermometer, and 3 g of tert-butyl peroxypivalate, a solution, formed of 35 g of styrene, 15 g of acrylonitrile, and 5 g of N-phenylimide maleic acid were added. The mixture was heated to this is cooled and the final product is recovered by flocculation when sodium acetate is added.
    51 g of resin are obtained.
    Example. In a three-necked flask, with a capacity of 2 liters, equipped with a reflux condenser and a stirrer, 170 g of solution, consisting of 116 g of styrene,
    15 g of N-phenylimide maleic acid
     5 g of a copolymer, styrene and acrylonitrile, and 20 g of a three-unit polymer based on ethylene, propylene and 5-ethylidene-corborn-1-ene, having the following properties:
    d
    CdH, wt.% 57 Ci 1, toluene,
    ; , - dl / g1,65
    Double bonds per 1000 C atoms,% B-, 5-1
    five
    To the solution, 40 g of acrylonitrile are added dropwise and with vigorous stirring.
    A very thin suspension of the three-stage polymer is obtained in the monomeric
    0 mixture that reacts for 1 hour. After adding 1.35 g of benzoyl peroxide.
    The resulting viscous mass is suspended in 500 ml of water containing
    5 5 g of sodium salts, mixtures of rezinol acids and vigorously stirred until a fine suspension is formed.
    The resulting suspension after adding another 1 g of benzoyl peroxide
    0 is reacted in 2 liters of isopropyl alcohol, filtered and dried. Get a 161 g of resin.
    five
    Example 9. According to the same procedure and under the same conditions as in Example 2, the reaction was carried out using the same three-unit polymer based on 1-isopropylidene and cyclopents1 DNn.
    The reaction mixture is added
    0 20 g of maleic anhydride. At the end of the reaction, 171 g of resin are obtained.
     The properties of the resins in examples 1-9 are shown in the table.
    Mechanical Testing
    5 were carried out after homogenization of the resins in an open mixer () for 10 minutes and direct compression kg / cm, 10 minutes.
    Thus, the invention allows to obtain high-impact copolymers with increased strength and 1 e-module of flexibility.
    22 20 18
    109
    93 117 105 115 100
      . ..-
    In accordance with the ASTM D 256 Specification of Impact Test ps, Ieod with 1/2 inch specimens with 1/8 inch notch (1.27 cm with 0.32 cm). .
    jy
    In accordance with the specification ASTM .., D 790..
    In accordance with the specification ASTM D 785.
    (according to ASTM D 648 specification (warping temperature when heated - load 18.5 Kr / cff).
    t,.
    权利要求:
    Claims (2)
    [1]
    The formula invented:; 4gni as elast (5er based on the co-method of obtaining impact-resistant nil monomer, elastomer imery are used by radical measures based on ethylene, propylene, and polymerization in the emulsion when heated, polyene, nor a mixture of styrene, acrylonitrile, and
    maleimide in the presence of 1-25% of ve-sources of information,
    on the basis of the elastomer monomers taken into account in the examination of a conjugated diene or its mixture with 1. US Patent No. 3358131, a vinyl monster, about tl and h-yukl. 240-1.3, published. 1968. Qi And with the fact that, with the aim of raising
    [2]
    2. Patenten England 1352437, no strength and flexibility module, cl. with 3 G, pub. 1974 (prototype).
    7646118
    Continuation of the tables
    , spine diene or its mixture with vi
    类似技术:
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    同族专利:
    公开号 | 公开日
    DE2644492A1|1977-04-07|
    FR2326436A1|1977-04-29|
    JPS5243896A|1977-04-06|
    DD126282A5|1977-07-06|
    YU239776A|1983-04-27|
    DE2644492B2|1978-07-20|
    LU75918A1|1977-05-06|
    NO763349L|1977-04-05|
    IL50500D0|1976-11-30|
    IT1043117B|1980-02-20|
    DK443676A|1977-04-04|
    SE7610880L|1977-04-04|
    CS196322B2|1980-03-31|
    FR2326436B1|1980-04-18|
    CA1079893A|1980-06-17|
    BE846881A|1977-04-01|
    ZA765466B|1977-08-31|
    GB1543358A|1979-04-04|
    AU1775676A|1978-03-23|
    NL7610972A|1977-04-05|
    US4127617A|1978-11-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2578321C2|2010-10-01|2016-03-27|Сервисьос Административос Пеньолес, С.А. Де К.В.|Novel composition for producing vinyl aromatic materials with impact strength, improved by structure-modifying additive|LU35689A1|1957-01-09|1900-01-01|
    US3708555A|1970-02-24|1973-01-02|Gaylord Ass|Grafting of a mixture of styrene and maleic anhydride onto backbone polymers containing active or labile hydrogen atoms|
    US3687905A|1970-03-16|1972-08-29|Lubrizol Corp|Reaction product of carboxylic acid with degraded ethylene-propylene interpolymer|
    US3882194A|1973-01-26|1975-05-06|Chemplex Co|Cografted copolymers of a polyolefin, an acid or acid anhydride and an ester monomer|
    US3981958A|1973-04-19|1976-09-21|Toyoda Gosei Kabushiki-Kaisha |Graft copolymers and process for producing same|CA1106536A|1977-06-15|1981-08-04|George S. Li|High nitrile resins containing maleic anhydride|
    US4197263A|1977-06-15|1980-04-08|The Standard Oil Company|High nitrile resins containing maleic anhydride|
    US4223096A|1977-12-27|1980-09-16|Monsanto Company|Rubber-modified terpolymer with improved molding characteristics|
    JPS6219446B2|1978-07-24|1987-04-28|Monsanto Co|
    US4381373A|1980-12-11|1983-04-26|Mitsubishi Monsanto Chemical Company|Heat resistant resin composition|
    US4374951A|1981-09-11|1983-02-22|Monsanto Company|Polyblends comprising N-phenylmaleimide copolymers and SAN copolymers|
    US4485215A|1983-05-11|1984-11-27|Atlantic Richfield Company|Molding composition|
    US4504627A|1983-09-12|1985-03-12|Atlantic Richfield Company|Methylmethacrylate/N-phenylmaleimide copolymer-containing polymer alloys|
    JPS6176512A|1984-09-21|1986-04-19|Toa Nenryo Kogyo Kk|Methylstyrene copolymer|
    NL8501660A|1985-06-08|1987-01-02|Dsm Resins Bv|BISMALEIMIDE COMPOSITIONS.|
    JPS63241014A|1986-11-21|1988-10-06|Sumitomo Chem Co Ltd|Modified copolymer rubber and its production|
    EP0628578A3|1993-06-11|1995-09-27|Chemie Linz Gmbh|2,6-Dimethylphenylphenymaleimide as comonomer in the copolymerisation of styrene or vinyl chlorid.|
    DE4321344A1|1993-06-26|1995-01-05|Chemie Linz Deutschland|2,6-dimethylphenylmaleimide as comonomer for styrene copolymers and vinyl chloride homopolymers|
    US6239221B1|1995-09-13|2001-05-29|Bayer Antwerpen S.A./N.V.|Low gloss weatherable polymer composition|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT27951/75A|IT1043117B|1975-10-03|1975-10-03|SHOCK RESINS AND METHOD FOR THEIR AREPARATION|
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