• 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:
    The reaction of metallic tin with hydrogen halide and olefin compound gives organo-tin halides which consist at least partially of organo-tin dihalide and may contain the corresponding organo-tin trihalide. The organo-tin halides obtained can be reacted in a manner known per se with appropriate organic acids or mercaptans or with their derivatives capable of reacting with halogen, to give stabilizer preparations for polymers such as polyvinyl chloride.
    公开号:SU751326A3
    申请号:SU762332707
    申请日:1976-03-17
    公开日:1980-07-23
    发明作者:Эрик Хаттон Рональд；Уильям Бэрлекс Джозеф
    申请人:Акцо Н.В. (Фирма)；
    IPC主号:
    专利说明:

    As a result of the reaction of metallic tin, hydrogen halide and olefin activated by one or more carbonyl groups, a very high yield of the reaction product per tin is achieved even under normal temperature conditions and pressure without using a catalyst. As a hydrogen halide, it is preferable to use relatively inexpensive hydrogen chloride. The reaction can be carried out in a solvent, such as ethers, alcohols, chlorinated or non-chlorinated hydrocarbons. An excess of olefin may also serve as a solvent. Metal tin can be used in any form. It is preferable to use porous tin, since, as a result of the large available surface of tin surface, its reaction rates are great. However, commercially available granulated tin can be directly used. In this case, to increase the reaction rate, it is desirable to slightly increase the reaction temperature. The method is usually accompanied by the formation of functionally substituted organotin two-halide compounds of the general formula (R 2SnX2, where R denotes the indicated radical RI "3 Crc 2 4 X - chlorine or bromine. These new compounds are the initial products of CI for obtaining high-quality new organotin stabilizers for polyvinyl chloride and other polymers using known methods in which the halogen atom is replaced by conventional organic residues, such as an acid thioether or thioalkyl group. examples it is clear that the amount of trihalide in the organotin halide compound may vary in wide ranges, for example, from 0 to 95% by weight. This mixture is usually used in an amount of 5-60% by weight. For the simultaneous formation of an arbitrary identity in the reaction products It is important for the trihalide that the competing reactions between tin and hydrogen halide, on the one hand, and between these compounds and the activated olefin, on the other hand, are directed in the direction of the first of them. The formation of these products can be promoted, especially by changing the ratio of reactants, the order and / or rate of introduction of reactants, the available surface area of tin and (to a lesser extent) by changing the temperature. Thus, the use of, for example, an excess of olefin, the slow introduction of hydrogen halide and a decrease in the available surface area of tin will lead exclusively to the formation of the two-halide (R) 2SnHaH. Changing the reaction conditions in the opposite direction increases the yield of RSnHa trihalide. The following describes methods for the preparation of organotin zigalogen compounds, accompanied or not by the simultaneous formation of trihalide compounds. Example 1. A 500 ml three-neck flask placed in a cooling bath and equipped with a stirrer, a thermometer, a cooler, and a gas outlet, is charged with 60 g of tin powder, 87.4 g of methyl acrylate and l40 ml of diethyl ether as solvent. For 3 hours at 20 ° C, 87 g of dry hydrogen chloride are blown into the mixture while stirring. Thereafter, the ether is evaporated, and the residue is extracted with 300 ml of hot chloroform. From chloroform extract with and pressure of 4 mm Hg. Chloroform is removed, after which 177.2 g of a white crystalline substance remains. After analysis (nuclear spin resonance) of this substance, it was found to be a mixture of organotin two- and trihalide compounds, namely (CH2CH2COOCH3) 2H C1 SnCH CHjCOCCH, (27 wt.%). The output in the calculation of the reacted tin quantitative. After washing the mixture with diethyl ether, in which trichloride dissolves well, a white crystalline substance remains, which after repeated analysis (infrared, nuclear spin resonance, elemental analysis) is identified as pure CE2Sn {CH2CH2COOMe) 2 С, mp. 132 ° C. Example 2. Analogously to example 1, 60 g of powdered tin, 95.7 g of methyl acrylate and 110 ml of diethyl ether are loaded into the reaction flask. 42 kg of dry hydrogen chloride are passed into the mixture for about 14 hours. As in Example 1, the solvent is removed and the residue is extracted, after which 3.7 g of unreacted tin remains, and 167.2 g of a white crystalline substance is recovered from the extract. This substance is a mixture of C125p (CH2CH2COOCH5} 2I,. CijSnCHjCHiCOOCHa (3.3 wt.%). Exit,
    calculated on the amount of tin used, 98%.
    Example 3 Analogously to Example 1, 60 g of powdered tin, 37.1 g of methyl acrylate and 140 ml of hexane are charged into the reaction flask and 46 g of dry hydrogen chloride are blown through the mixture for 12.5 hours. The reaction mixture was filtered, washed with 100 ml of hexane and extracted with hot chloroform, after which 1.5 g of unreacted tin remained, and 173 g of crystalline material was isolated from the extract.
    As a result of the analysis of this compound, it was established that it is a mixture (CHgCHgCOOCHg); and cejSnCHjCOGCHj (15.9 wt.%). Output, calculated on the weight of tin used, 99%.
    Example 4. In the same reaction flask as in example 1, placed 60 g of powdered tin and 95.7 g of methyl acrylate. B for 45 minutes with stirring, 115 g of hydrochloric acid (35.4%) were introduced into the mixture, after which the stirring was continued for another 4 hours. Then the reaction mixture was filtered, washed with water and extracted with chloroform. 14.9 g of unreacted tin remain, and 103.5 g of a solid are obtained from the extract, which, by analysis, is identified as pure CEjSn (CH2CH2COOCH) 2, and the residue is contained in tin chloride in the wash water.
    Example 5. As in Example 1, 60 g of tin powder and 174.2 g of methyl acrylate (which is also a solvent) are charged into the reaction flask. Then within 15 hours 40 g of dry hydrogen chloride are introduced into the mixture. The reaction mixture is filtered and washed with 20 g of methyl acrylate.
    After extraction with chloroform, 5.0 g of unreacted tin remains, and 141.2 g of crystalline product is recovered from the extract, which is pure СEgSn (СН2СН2СООСНз)), which represents 84.6% of the yield calculated for the reacted tin. The filtrate contains 17.3 g of the indicated product, and the total yield is 95%.
    Example 6. Using the method used in Example 1, a bog of tin powder, 95.7 g of methyl acrylate and 140 ml of diethyl ether was charged into the reaction flask, then 110 g of dry bromine hydrogen was introduced into the mixture for 10.5 hours.
    After removal of the solvent, the residue is extracted with 300 ml of hot chloroform, leaving 9.5 g of unreacted # tin.
    After evaporation of the extract, 196.0 g of solid are obtained, which, after analysis, are identified as a mixture of Br ' Sn (CHc, CH7COOCH3J2 (.137C) and Bri SnCHzCHjtCOOCHs (19.7)). The yield is based on quantitative tin.
    Example 7. In the reaction flask, the same as in example 1, load 60 g of powdered tin,
    99.2 g of mesityl oxide and 140 ml of diethyl ether. Then, 70 g of dry hydrogen chloride are added to the mixture over 10.5 hours.
    After filtration and rinsing
    150 ML of ice-cold ether were obtained, the residue was extracted with 300 ml of chloroform. 84.6 g of a light brown crystalline substance CK25p (CMe2CH2COCH3) 2 C, m.p. 158 C.
    The yield calculated for reacted tin is 43%. After evaporation of the ether filtrate, another 89.5 g of a dark brown product is obtained, which, as it turned out,
    contains 40 Uns.%
    CE2Sn C (CH) 2 CH2COCH312 40 wt. % CEjSnC (CH; 2CHgCOCHg. The final total yield of organotin compounds is about 80%.
    Example 8. In the reaction flask, the same as in example 1, load 60 g of powdered tin, 78.0 g of methyl vinyl ketone and 40 ml of diethyl ether. Then for
    14 h. 54 g of dry hydrogen chloride are introduced into the mixture. The reaction mixture is filtered to remove traces of unreacted tin (about 0.1 g) and then evaporated at
    temperature of 100 ° C and a pressure of 4 mm Hg, resulting in a gain of 162.4 g of a dark brown solid. As a result of the analysis, it was found that this substance contains
    about 40 wt.% With CjSn (CHj CHj SOSNE)
    and 40 wt.% CE SnCHJCH CH 2.
    The total yield of organotin compounds is approximately 80%, based on the reacted tin.
    Example 9. In the reaction flask, the same as in example 1, load 60 g of powdered tin, 91.5 g of acryloyl chloride and 140 ml of diethyl ether.
    19.5 hours 60 g dry are added to the mixture.
    hydrogen chloride. After filtering the reaction mixture, 24 g of unreacted tin is removed from it, and then the mixture is evaporated. The residue is extracted with 300 ml of hot chloroform, after which the extract is evaporated and 103 g of a brown solid are obtained. As a result of the analysis, it was established that this substance contains mainly СtgSnCHjСН СОСJ
    to some amount
    CEgSnCCHjCHjCOCE). It turned out to be impossible to determine the exact yield due to the presence of organic material.
    Example 10. In the reaction flask, the same as in example 1, load 60 g of powdered tin, 129.6 g of n-bu hilacrylate and 140 g of diethyl ether. Within 20 hours, 54 g of dry hydrogen chloride was introduced into the flask. After filtering and the reaction mixture, 0.2 g of unreacted tin is separated, after which the filtrate is evaporated and 224 g of pure colorless liquid are obtained, which, as determined by analysis, consists mainly of СtgS (CHgСНСООСдН a and a small amount of
    CE2, -5пСН2 СН2СООС4Н9. The overall yield is about 97% based on the reacted tin.
    Example 11. In the reaction flask, the same as in example 1, load 60 g of powdered tin of 101.2 g of methyl methacrylate and 140 ml of diethyl ether. Then, within 22 hours, 44 g of dry hydrogen chloride are introduced. The reaction mixture is evaporated and the residue is extracted with 300 ml of hot chloroform. As a result, 33.3 g of unreacted tin are separated, and 67.3 g of a crystalline substance is separated from the extract, which consists of СH25п (СНлСНСНэСООСНз) 2 С so pl. and Cf-jSnCHCHgCOOCHg (57.5 wt.%). The total yield based on reacted tin is 84%.
    Example 12. p. In a reaction flask, such as in example 1, equipped with a jacket for heating, load 60 g of granulated tin and 129.6 g of n-butyl acrylate. Then the contents of the flask are heated to 129c, after which 78 g of dry hydrogen chloride are passed through for 12 hours. The reaction mixture is filtered to separate unreacted tin (9.8 g), and the filtrate is evaporated to remove the remaining butyl acrylate and hydrochloric acrylate as by-products. Thereafter, 179.8 g of a pure, almost colorless liquid is obtained, which, as established by analysis, contains mainly
    CEjSn (CH2 CHCOOC4H-f) 2 G The yield per 95% of tin reacted. The final product is slightly contaminated with polybutyl acrylate.
    Properties of the compounds 30 are shown in the table.
    1-5CEgSnCHjCOjCHg 1-5 CE2 $ p (CH2CH2; C02CHe) 2 132 3 pp is a pattern from an example 3 6Bhc 5pCH2CH2C02CNd Bg25p (a CH2CH2C02CH5) 2,137 mixture from an example 6 of CEgSnCMe CHgCOCHg CESEPaCegze2 137 C2S2S2C2CH2P 2 137 Mixture from example 6 34.62 (38.02) (34.1) 19.50 32.58 (32.64) 19.52) 21.83 33.49 38.98 26.29 32.90 36.57 (36.60 ) 32.83) 18.51 30.94 18.30) (30.59) compounds of the general formula (R) 2SnX2 and / or RSnXj R - radical of the structure of Cn-C - X - chlorine or bromine, characterized in that the interaction of metallic, tin / hydrogen halide and. olefin of general formula
    Table continuation. where R. R2 R3 I-CHjj Cd-SOSNe, -COOSNd, -COS or COOC4H9, at a temperature of 20-100 C. Sources of information taken into account during the examination 1. Kochetkov K.A. and others. Methods of organoelemental chemistry. M, science, 1968, p. 181. 2. The patent of the Netherlands No. 144283, cl. C 07 F 7/33, published 1971.
    权利要求:
    Claims (1)
    [1]
    Claim
    A method of producing organotin compounds of the general formula (R) 2 SnX 2 and / or RSnX-j where R is a radical of structure 9 > cn-c—, r 2 k;
    X is chlorine or bromine, characterized in that * 5 conduct the interaction of metallic tin, and hydrogen halide. olefin of the General formula
    Rt K 3 ^ c = c ^ where R | = R 2 = Rj = H or CH 3 ;
    R 4 = —COCH3, —COOCH e , —COCt, or
    C00C 4 H 9 , at a temperature of 20-100 ° C.
    类似技术:
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    同族专利:
    公开号 | 公开日
    ATA142576A|1978-03-15|
    DE2660040B1|1979-11-22|
    CH623333A5|1981-05-29|
    GB1502073A|1978-02-22|
    JPS51113831A|1976-10-07|
    BR7601571A|1976-09-14|
    JPS6338064B2|1988-07-28|
    ES446112A1|1977-06-01|
    DE2607178A1|1976-10-14|
    DE2660040C3|1983-05-11|
    JPS58180495A|1983-10-21|
    AT346363B|1978-11-10|
    FR2306208B1|1980-02-29|
    DE2607178C3|1983-03-03|
    AU1196676A|1977-09-15|
    AU498143B2|1979-02-15|
    ZA761598B|1977-04-27|
    CA1073465A|1980-03-11|
    FR2306208A1|1976-10-29|
    DE2607178B2|1978-04-13|
    JPS5946959B2|1984-11-15|
    NL7503116A|1976-09-21|
    IT1057046B|1982-03-10|
    DD125550A5|1977-05-04|
    BE843387A|1976-10-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3398114A|1964-01-10|1968-08-20|Argus Chem|Light and heat stability of polyvinyl chloride resins|JPS5723704B2|1976-06-14|1982-05-20|
    JPS5720975B2|1976-06-14|1982-05-04|
    JPS535126A|1976-07-01|1978-01-18|Nitto Kasei Kk|Preparation of organotin dihalides having functional group|
    JPS5723705B2|1976-07-30|1982-05-20|
    JPS5717000B2|1976-09-20|1982-04-08|
    US4158669A|1977-05-06|1979-06-19|Ciba-Geigy Corporation|Organo-tin compounds|
    DE2735810B2|1977-08-09|1981-01-29|Hoechst Ag, 6000 Frankfurt|Mixtures of organotin compounds and their use as stabilizers for chlorine-containing polymers|
    DE2735757A1|1977-08-09|1979-02-15|Hoechst Ag|NEW ORGANOCIN HALOGENIDES AND PROCESS FOR THEIR PRODUCTION|
    DE3061387D1|1979-02-28|1983-01-27|Akzo Nv|Process for the preparation of bis-tin dihalides|
    GB2046762A|1979-04-17|1980-11-19|Akzo Chemie Uk Ltd|Resin stabilizer compositions containing sulphur-containing ester tin compounds and ortho-dihydric phenols|
    FR2457298B1|1979-05-23|1982-07-02|Elf Aquitaine|
    FR2458554B1|1979-05-23|1982-07-09|Elf Aquitaine|
    US4701486B1|1981-02-26|1992-05-19|Thiokol Corp|
    US4576984A|1982-02-04|1986-03-18|Morton Thiokol, Inc.|Stabilizer compositions for PVC resins|
    PL147517B1|1985-09-25|1989-06-30|Politechnika Warszawska|Method of obtaining cyanoorganic compounds|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    NL7503116A|NL7503116A|1975-03-17|1975-03-17|PROCEDURE FOR PREPARING ORGANOTIN DIHALOGENIDES AND ORGANOTIN STABILIZERS DERIVED FROM THEREOF.|
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