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    • 专利摘要:
    1441085 Glycidyl methacrylate DEUTSCHE GOLDUND SILBER-SCHEIDEANSTALT 24 April 1975 [14 May 1974] 17009/75 Heading C2C Glycidyl methacrylate is prepared by transesterification of methyl methacrylate with glycidol in the presence of an alkali metal or an alkali-metal compound as catalyst, while distilling off the methanol formed during the reaction. Sodium or lithium are preferred metals and the alcoholates may be methyl, ethyl and propyl. Polymerization inhibitors may be present and oxygen or air passed through the solution.
    公开号:SU942595A3
    申请号:SU752121916
    申请日:1975-04-11
    公开日:1982-07-07
    发明作者:Клееманн Аксель；Колб Хайнц；Шрайер Герд
    申请人:Дегусса Аг (Фирма)；
    IPC主号:
    专利说明:

    (3) METHOD FOR PRODUCING GLYCIDYLMETACRYLATE
    one
    This invention relates to a process for the preparation of glycidyl methacrylate used for the manufacture of varnishes.
    A known method for producing glycidyl methacrylate by reacting methacrylic acid hydride with glycidyl in the presence of hydrogen halide acceptor. However, under these conditions, only glycidyl methacrylate containing chlorine can be obtained. The quality of the products derived from this glycidyl methacrylate is greatly deteriorated.
    In addition, waste in the form of potassium chloride or sodium chloride is formed, resulting in problems associated with the disposal of wastewater.
    The closest to the invention to the technical essence is the method of obtaining glycidyl methacrylate by transesterification of a molar excess of COT of 1.5 - x fold) methyl methacrylate with glycidol at 50-100 ° C. in the presence of a catalyst. phosphine in the amount of 0.05-1 by weight of the reaction mixture in an inert atmosphere.
    The methanol released in the process of transesterification is distilled off from the reaction mixture together with methyl methacrylate. The process is carried out from 2 to h. The yield of the target product and the degree of conversion according to GLC are respectively equal to 62.5-76, and 79-82 mol.% ..
    The disadvantages of this method are the relatively low yield of the target product, as well as the degree of conversion, in addition, the need to use toxic phosphines, which can only be difficult to remove from the system by distillation. Therefore, the final product is usually always contaminated by them.
    The purpose of the invention is to increase the yield of the target product.
    权利要求:
    Claims (2)
    [1]
    This goal is achieved in that according to the method of producing glycidyl methacrylate by transesterification of the molar excess of methyl methacrylate with glycidol at 70-80 s in the presence of an alkali metal or alkylate as a catalyst or an alkali metal hydride and an inhibitor of polymerization by passing oxygen or air. with continuous removal of the methanol formed mixture with methyl methacrylate and isolation of the target product, an alkali metal or hydride or alkali metal alcoholate is used as a catalyst when conducting the process in the presence of a polymerization inhibitor when air or oxygen is supplied. In this case, the catalyst is taken in an amount of 0.1-0.5 weightD. Methyl methacrylate is used in a 5-10 fold molar excess. Moreover, the transesterification process is carried out in vacuum at mm Hg. As a polymerization inhibitor, compounds known for this purpose are hydroquinone, hydroquinone monomethyl ether are used. In carrying out the proposed process, a mixture of glycidol and methyl methacrylate is prepared, to which a catalyst and a polymerization inhibitor are added and oxygen or air is passed through the solution at the same time. During the reaction, the resulting methyl alcohol mixed with methyl methacrylate is distilled from the reaction mixture. After completion of the reaction, the alcohol (the residual amount of methyl methacrylate is distilled off), as well as unreacted glycidol, the crude glycidyl methacrylate formed is purified by fractional distillation in vacuo. Example 1. In a two-liter three-neck flask, 500 g (5 mol) of methyl methacrylate and 37 g (0.5 mol) of glycidol are placed, and 1 g of hydroquinone monomethyl ether is added as a polymerization inhibitor. After that, O, 43 g of lithium methylate (0.5 wt.% Of catalyst, based on the number of reaction components) are added to the prepared mixture and the reaction mixture is heated to a temperature of 70 ° C. When using a packed column with a height of 20 cm (Raschig rings with a diameter of 6 mm) at a pressure of 200 mm Hg. and a reflux ratio of 3: 1, the resulting methyl alcohol is distilled together with methyl methacrylate. Air is passed through the capillary during the reaction. After 2 hours of reaction, the degree of conversion of glycidol is 98.5, and the yield of glycidyl methacrylate CQ is Э5%, which is determined by gas chromatography. After filtering the reaction solution using an apparatus for evaporation in a thin layer, the residues of methyl methacrylate and unreacted glycidol are distilled off in vacuum. The resulting crude glycidyl methacrylate is again distilled under a vacuum of 10 mm Hg. (t. Kip.). The result is glycidyl methacrylate as a colorless liquid, the output being 58 g (82% of the theoretically calculated value). Example 2. Analogously to example 1, 37 g (0.5 mol of glycidol is subjected to transesterification of 250 g; (2.5 mol) of methyl methacrylate by adding 1 g of hydroquinone monomethyl ether as an inhibitor and 0.086 g of lithium methoxide 10.1 weight of catalyst, in the calculation the amount of glycidol is 90.9 and the yield of glycidyl methacrylate is 95.7%. Example 3. Similarly, for example 1, 37 g 0.5 mol; glycidol is subjected to transesterification 500 g ( 5 mol) methyl methacrylate adding 1 g of hydroquinone monomethyl ether as an inhibitor and 0.086 g of lithium hydride (0.1% by weight of catalyst, based on the amount of reagents) as catalyst. After 2 hours, the degree of conversion of glycidol is 98.6, and the yield of glycidyl methacrylate is 95.1 -S. .. Example: The procedure is carried out in the same way as in Example 1, but 0, + 3 g of sodium methoxide is used instead of lithium methylate. Similarly, after the reaction has proceeded for 2 hours, similar results are obtained. Example 5- For comparison, magnesium methoxide is used instead of sodium methoxide. Otherwise, the conditions for performing the experiment are equal to the conditions indicated in examples 1 or 4. After 2 hours, no reaction was observed. EXAMPLE 6 Similarly to Example 1, 500 g of C 5 mol of methyl methacrylate are used with 37 g of glycidol and 1 g of hydroquinone monomethyl ether. 5.9. Add 0.1 g of lithium metal in finely divided form and heat the mixture to 70-80 ° C. After lithium goes into solution in the evolution of hydrogen, vacuum AOO mm Hg is used. and the methanol formed (together with methyl methacrylate) is distilled at a reflux number of 31. Further processing through the capillary is carried out as in Example 1. After 2 hours of reaction, the conversion is 9b, 70 and the yield of glycidyl methacrylate is 97.0 °. Example 7-Carried out analogously to example 6, except that instead of a catalyst based on lithium, metallic sodium is used in a quantity of 0.3 g. The degree of conversion is glycidyl methacrylate and 89.8. Example 8. The procedure was carried out as in Example 1, and 0.48 g of lithium ethylate was used as a catalyst instead of lithium methylate. The degree of conversion is 98.2, yield 96, ° 4. The invention allows to increase the yield of the target product and degree to the version, respectively, up to 86–9 and 91–98% and eliminate the use of toxic phosphines. 5 The claims 1. A method for producing glycidyl methacrylate by transesterification of a molar excess of methyl methacrylate with glycidol at 70-8 (Pc in the presence of a catalyst with continuous distillation of the methanol formed in a mixture with methyl methacrylate, followed by separation of the target product, which also differs from Alkali metal or hydride or alkali metal alcoholate is used as catalyst and the process is carried out in the presence of a polymerization inhibitor under oxygen supply or ear 2. the method according to p. 1, which is characterized by the fact that the catalyst is taken in an amount of 0.1-0.5 weight .. 3. The method according to p. 1, which differs from and that methyl methacrylate is used in 5- 10-fold molar excess. 4. The method according to claim 1, which is distinguished by the fact that the process is conducted in a vacuum of mm Hg Sources of information taken into account during the examination 1. US Patent No. 2680109, class 260-783 , published in 1963.
    [2]
    2. Japan Patent No., Series I, Sat. 29/29, published, 1972 (prototype.
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    同族专利:
    公开号 | 公开日
    GB1441085A|1976-06-30|
    AT341538B|1978-02-10|
    BE829033A|1975-11-13|
    ATA364975A|1977-06-15|
    DE2423405A1|1975-11-27|
    JPS50154205A|1975-12-12|
    FR2271222A1|1975-12-12|
    DE2423405C3|1983-05-19|
    JPS6137268B2|1986-08-22|
    DE2423405B2|1978-03-23|
    DD118413A5|1976-03-05|
    CH599949A5|1978-06-15|
    IT1032669B|1979-06-20|
    CA1061355A|1979-08-28|
    FR2271222B1|1977-07-08|
    NL7505019A|1975-11-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    NL7605330A|1975-06-05|1976-12-07|Degussa|PROCESS FOR PREPARING GLYCIDYL METHA CRYLATE.|
    JPH0470299B2|1980-12-03|1992-11-10|Mitsui Toatsu Chemicals|
    DE3423441C2|1984-06-26|1993-04-29|Roehm Gmbh, 6100 Darmstadt, De|
    US4780555A|1988-01-04|1988-10-25|Dow Corning Corporation|Method for preparing and stabilizing acryl-functional halosilanes|
    DE102009057699A1|2009-12-07|2011-06-09|Kruk, Sandra|Bottom part for flat solar collector, is provided with thermal insulation of insulating material adjacent to its inner side, where part is designed as one-piece multi-layer body having fiber-reinforced polyester layer|
    JP5606132B2|2010-04-12|2014-10-15|三菱レイヨン株式会社|Method for producingacrylic acid ester|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19742423405|DE2423405C3|1974-05-14|1974-05-14|Process for the production of glycidyl methacrylate|
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