• 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:
    A method is described for making organic polycarboxylic acids or anhydrides, such as aromatic ether bis(phthalic acid)s, based on a cyclic imide-cyclic anhydride exchange reaction at elevated temperatures in the presence of water. In addition to making organic polycarboxylic acid, organic imides are also generated.
    公开号:SU818478A3
    申请号:SU772527454
    申请日:1977-10-04
    公开日:1981-03-30
    发明作者:Ли Маркезич Рональд；Такекоси Тору
    申请人:Дженерал Электрик Компани (Фирма)；
    IPC主号:
    专利说明:

      t The invention relates to organic synthesis, specifically to a method for producing a dicarboxylic acid or its dianhydride and imide. A method is known for producing, for example, 4-phenoxyphthalic anhydride by treating 4-phenoxy-I-methylphthalimide with hydrazine, followed by oxidizing the obtained hydrazine in the presence of a base and neutralizing the resulting salt of phthalic acid, which is then subjected to dehydration. The disadvantage of this method is its complexity, due to the multi-transition. imide to anhydride. The closest technical essence and the achieved results is the method of obtaining, for example, 2.2-5IS-4- (3,4-dicarboxyphenoxy) -phenyl} propane dianhydride by hydrolysis of 2,2-bis 4- (N-phenylphthalimide-4- oxy) phenyl propane in a 50% NaOH solution at 16 O-175 ° C under a pressure of 11 atm, followed by treatment of the resulting salt with hydrochloric acid, after which 2,2-bisC4- (3,4-Dicar6oxyphenoxy -phenyl propane is subjected to dehydration with acetic anhydride in the medium of acetic acid 1 at boiling {2. . The disadvantage of this method is its multistepness, since it involves initially the hydrol 1se stage, after which the salt formed is converted to tartrakislota, which must be further dehydrated, in the case of anhydride. The purpose of the invention is to simplify the process. i The goal is achieved by the proposed method of obtaining dicarboic acid or its dianhydride and imide by anhydride-imide exchange in a closed system between an imide of the general formula where q is ORP or C (CH)), R is CHH or Ph, and 1 or 2,
    and phthalic anhydride or maleic acid in the presence of water at 150,250 ° C.
    The exchange is carried out in the presence of a catalyst, which is ferric chloride.
    In the process, a mixture of imide and phthalic anhydride is heated in the presence of water or an aqueous catalytic mixture. Heating is performed in a closed system, for example in an autoclave or reactor, in order to maintain the presence of water. The mixture is heated to a temperature of at least 100 ° C with stirring and then allowed to cool to ambient temperature. Then volatile substances or the product of the exchange of bisimide, or imidoacid, or tetraacid can be distilled off from the mixture. In case the distillation of volatiles is performed at temperatures up to under reduced pressure, the resulting residue of the reaction mixture, consisting mainly of the bimimide exchange product, can be mixed with additional phthalic anhydride and water and heated in a closed system as previously described. to further convert bimimide to tetraacid. It was found that, depending on the initial ratio of phthalic anhydride to bimimide and the number of reaction cycles, complete conversion of bimimide to tetraacid can be achieved.
    It has been found that effective ratios are achieved at a ratio of from 1 to 20 mol of phthalic anhydride per mole of bimimide. The temperature is within the SO-ZOO C, preferably 150-250C.
    The ratio varies from about 0.01 to 100 parts of water to 1 part of bisimide and preferably from 0.1 to 10 hours.
    The catalyst, metal halide, is used from 0.01 to 10%, based on the weight of the bimimide.
    The reaction is carried out in a hydrochloride vial, ampoule or closed reaction vessel in order to preserve the presence of water while stirring the mixture. Under certain conditions, the reaction is carried out at atmospheric pressure by passing water vapor into the melt of the mixture.
    Example 1. A mixture of 25.3 parts by weight of 4-phenoxy-N-methylphthalimide, 29.6 parts by weight phthalic anhydride and 50 weight.h. Water is heated in an autoclave for 2 hours at 200 ° C. The mixture is then allowed to cool to ambient temperature, after which it is again heated to atmospheric pressure. The residue is distilled under reduced pressure. Get 18.7. the first fraction boiling at 182 C at 55 mm Hg. and also 9.7 h. second
    fraction boiling at 182 ° C with 50 mm Hg. Art.
    Both fractions are combined and heated to 25 parts by weight. water for 20 minutes under reflux. The mixture is then cooled to room temperature and filtered. The resulting solid is dispersed in 25 parts by weight. methylene chloride and the mixture is boiled for 10 minutes under reflux with stirring, after which it is cooled to room temperature. The precipitate obtained is evaporated to dryness and 7.39 parts by weight are obtained. product. Based on the infrared spectrum, it is determined that the product is N-methylphthalimide. The crystalline precipitate recovered from the initial chloromethylene solution is washed with additional methylene chloride, and 18.3 parts by weight are obtained. phthalic acid, o
    In addition to the described two fractions extracted from the initial reaction mixture of the autoclave containing phthalic acid and N-methylphthalimide, 13.4 parts by weight were also obtained. fractions boiling at 257-258s at 32 mm Hg. In addition to the mentioned fractions, 10.5 parts by weight were also obtained. distillation residue. The fraction consisting of 13.4 lb. mixed with 20 parts of water is refluxed for 20 minutes. The mixture is allowed to cool and mixed with 25 weight.h. methylene chloride. The resulting mixture was filtered. Received 9.6 wt.h. product. Based on the infrared spectrum, the HTO filtration product is 4-phenoxy phthalic acid. The chloromethylene mother liquor was evaporated to dryness, and 4 parts by weight were obtained. the remainder. Infrared spectrum showed that it is pure 4-phenoxy-N-methylphthalimide.
    Found that 10.5 weight.h. The distillation residue of the initial autoclave mixture is a mixture of 61% by weight of 4-phenoxy-phthalic anhydride and 39% by weight of 4-phenoxy-N-methylphthalimide.
    The results show that there is an exchange between 4-phenoxy-N-methylphthalimide and phthal. In anhydride, this gives N-methylphthalimide in 46% yield and 4-phenoxy-phthalic anhydride or acid in 64% -HbW yield. This conversion of 4-fvnoxy-N-methylphthalimide to 4-phenoxyphthalic anhydride has been achieved, without intermediate conversion of 4-phenoxy-S: methyl methyl phthalimides to the corresponding hydrazide and hydrolysis in the presence of a base, to give a metallic salt that needs neutralization and heating to receive ftade, and resulting hydrolysis in the presence of a base, to obtain a metallic salt that needs neutralization and heating of the resulting fctyl hydrolysis.
    Example 2. A mixture of 2 parts by weight maleic acid, 2.23 parts of N-phenylphthalimide and 20 parts of water are heated under pressurized conditions for 2 hours at 180 ° C. The reaction mixture is then cooled to room temperature and distilled under vacuum. Maleic anhydride is prepared first and then phthalic anhydride and N-phenylmaleimide. Phthalic anhydride is obtained with a yield of 15 wt.% And N-phenylmaleimide with a yield of 14.1 wt.%. Example 3. A mixture of 20.71 parts by weight of 2,2-bis-4- {H-methylphthalimide-4-hydroxyphenyl) propane, 125.32 parts by weight phthalic anhydride and 1.35 parts of para-toluenesulfonic acid monohydrate are loaded at 180 ° C under sealed conditions. The mixture is then cooled and distilled at 250 ° C and 60 mm Hg. The distillate is obtained as a mixture of phthalic anhydride and N-methylphthalimide. The residue is analyzed by high-pressure liquid chromatography. 7-wt.% 2,2-bic 4- (3, 4-dicarboxyphenoxy) phenyl 3 propane dianhydride, 40 wt.% (3,4-dicarboxyphenyl) phenyl 2- ( 4 - (M-methylphthalimide-4-hydroxy) phenyl propane anhydride and 53 wt.% 2,2-bis 4- (N-methylphthalmide-4-hydroxy) phenyl propane. Then, the liquid residue is divided into its component parts by liquid chromatography high pressure. The dianhydride was found to have a melting point of 183-187 ° C and an imidoanhydride melting point of 111-116 ° C. The identity of the imidoanhydride having the formula is confirmed its infrared spectrum: anhydride-carbonyls - 1850, 1775 cm, imide carbonyl - 1706 cm, and mass spectroscopy: for CJ N33 calculated 533.146, found 533.148. Example 4. In accordance with example 3, a mixture of 136 parts by weight Bis mid, 148 parts by weight of phthalic anhydride and 2.7 parts by weight of water, are heated for 20 hours at 200 ° C. Then the mixture is cooled and distilled at a pressure of 60 mm Hg for 15 minutes. from phthalic anhydride and N-methylphthalimide. The residue is analyzed by high pressure liquid chromatography. 6% by weight of imide-hydride is obtained in measure 3, in terms of the weight of the bimimide in the starting mixture. The described example is repeated, but in addition to the ingredients in the mix, 8.2 parts by weight are added to the mixture. trichloroacetic acid. In addition, other mixtures are prepared by the same method, differing in that instead of 8.2 parts by weight. trichloroacetic acid and 2.7 wt.h. water, 8.6 parts by weight are used. paratoluenesulfonic and 0.8 weight.h. water. Other mixtures are heated without the addition of a catcher, but with an increased water content. The results obtained in the table. 1, where BRA-YA is 2,2-bis 4- (3,4-dicarboxyphenoxy) phenyl propane dianhydride and BRA-1A corresponding imidic anhydride. The results show the effect of water and the catalyst on the output of ARB and ARB-1A. Water can also be used without a catalyst, but a much larger amount of it is required in order to achieve a satisfactory yield of ARB and BRA-1A. Example 5. Example 1 is repeated; however, various catalysts with water and without water are used to determine the effect of the catalytic mixture on the yield of 4-phenoxyphthalic anhydride. A mixture of 29 weight.h. N-methyl-4- {p-methylphenoxy) phthalylshd and 25 parts by weight phthalic anhydride is heated under pressurized conditions in the presence of 3.6 parts by weight. water or in the presence of a catalyst and water. The results are shown in Table. 2, where the weight units of the aryloxyanhydride are 4-phenoxyphthalic anhydride, based on the weight of the aryloxy substituted phthalimide, used in combination. The results show that in the case of using quantities of water in the absence of a catalyst, the yield of aryloxyanhydride is significantly reduced. Another mixture containing 3.2 parts of iron chloride is heated in the absence of water. 4 wt.% Of aryloxyanhydride is obtained after heating at 180 ° C for 20 hours. Example 6. A mixture of 54.6 parts by weight 2,2-bis 4- (S-methylphthalimide-4-hydroxy) phenyl propane, 148 parts by weight phthalic anhydride and 200 weight.h. water is heated with stirring in an autoclave at 210 s for 3 h and then cooled to room temperature. The mixture is distilled under a pressure of about 50 mm Hg. After the initial selection of water, taken at 180-185 C and 50 mm Hg. a mixture of phthalic anhydride and N-methylphthalimide. Get 52 weight.h. the remainder. The residue consists of 5% by weight of the starting bisimide, 32% by weight of the corresponding monoimide anhydride and 63% by weight of the resulting dianhydride. This process is repeated with a mixture consisting of 52 parts by weight. residue, 128 weight.h. phsycric anhydride and 200 weight.h. water. The reaction mixture is also distilled at 50 mm Hg. to remove volatile fractions. Get 50 hours of residue. NAKDENO that
    it contains 91 wt.% 2,2-bis 4- (3,4-dicarboxyphenoxy) phenylZpropane dianhydride. The crude product is recrystallized from 400 parts of toluene and get 39 parts of the dihydride having t, pl.-185-187 ° C.
    Table
    1) para-toluenesulfonic acid.
    table 2
    权利要求:
    Claims (2)
    [1]
    Claim
    1. A method of producing a dicarboxylic acid or its dianhydride and imide, characterized in that, in order to simplify the process, an imide of the general formula. 45
    0 *
    II о where Q is OP h or С (С (0 Р h,
    R 1 - С Η, or Ph, а = 1 or 2, is subjected to an anhydride-imide exchange in a closed system with phthalic anhydride or maleic acid in the presence of water at 150-250 ° С.
    [2]
    2. The method of pop. ^ characterized in that the exchange is carried out in the presence of a catalyst - ferric chloride.
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