• 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 novel process for producing alkenyl phenols, which comprises continuously feeding a dihydroxydiphenyl alkane such as 2,2-(4,4'-dihydroxydiphenyl)propane, 2,2-(4,4'-dihydroxy-3,3'-dimethyldiphenyl)propane, 2,2-(4,4'-dihydroxydiphenyl)butane, 2,2-(4,4'-dihydroxydiphenyl)-4-methylpentane, 1,1,1-(4,4'-dihydroxytriphenyl)ethane and 1,1-(4,4'-dihydroxydiphenyl)cyclohexane into a high-boiling inert organic reaction medium such as an alkylnaphthalene containing a basic catalyst and heated at 150 DEG to 250 DEG C. under 10 to 100 mmHg while maintaining the concentration of the dihydroxydiphenyl alkane in the reaction medium at not more than 30% by weight, thereby cleaving it in the reaction medium; and continuously distilling off the cleavage product out of the reaction system and recovering it. This process can afford the corresponding highly pure alkenyl phenol as a monomer and/or its polymer almost quantitatively.
    公开号:SU971089A3
    申请号:SU792803956
    申请日:1979-08-14
    公开日:1982-10-30
    发明作者:Като Нобукацу；Такасе Цутомо；Моримото Есио；Юаса Теруо；Хаттори Минору
    申请人:Мицуи Тоацу Кемикалз Инк(Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR OBTAINING PHENOL AND CR-SAT-ALKENYLPHENOL The invention relates to a process for the production of phenol and C-Se-alkylphenol, which can be used as intermediates for the preparation of plasticizers of polymers, insecticides from dioxydiphenyl-alkanes-C2-S.  A known method of producing phenol and isopropylphenol by thermal cleavage of waste production of diphenylolpropane at 150-250 ° C and a pressure of 5-50 mm Hg.  Art.  in the presence of 0.01-0.5 wt. % sodium hypophosphite as a catalyst with simultaneous distillation of the resulting phenol and p-isopropenylphenol.  The degree of conversion of raw material is 60-70%, the content of phenol in the distillate is 23–28%, and p-isopropylshphenol is 21–23% 1.  The disadvantage of this method is the low degree of conversion of the feedstock (60-70%).  The closest in technical essence to the present invention is a method for producing phenol and isopropyl lphenol by thermally splitting the waste products of diphenylolpropane containing diphescholpropane at 150-300 ° C, pressure 5-150 mm Hg.  Art.  in the presence of 0.1-5 wt. % sodium hydroxide as a catalyst with simultaneous distillation of the target products and their subsequent separation.  The degree of conversion of the feedstock 76 79, 5%.  The yield of the target products is 72-75% 2.  The disadvantage of the method lies in the insufficiently high yield of the target products (72-75%). The purpose of the invention is to increase the yield of the target products.  The goal is achieved according to the method of producing phenol and Cj-Се-alkylphenol by thermal cleavage of 2-30% solutions of dioxydiphenylalkanes Cj-Се at 150-250 ° С, pressure 10-100 mm Hg.  Art.  in the presence of 0.01-5 wt. % of catalyst selected from the group: alkali or alkaline earth metal hydroxide alkali metal phenol, alkali metal bisphenol, in a solvent selected from the group: bottom distillation of a diphenylolpropane distillation column, novolac resin with softening temperature of 90-150 ° С , Cs-Cio-alkyl naphthalers with 1-3 alkyl radicals, with simultaneous distillation of the target products and their subsequent separation.  Distinctive features of the method are carrying out the process of splitting 2-30% solutions of dioxydiphenyl-alkanes-Cs-Ce in the presence of a catalyst selected from the group of alkali or alkaline earth metal hydroxide, alkali metal phenol of alkali metal in a solvent selected from the group: the bottoms of the distillation column of diphenylolpropane, novolac resin with a softening temperature of 90-150 ° C, Cs-Cio-alkyl naphthalenes with the number of alkyl radicals from 1 to 3.  To decompose dioxydiphenylalkane, the solvent must be heated to a temperature sufficient to smoothly react the decomposition of dioxiphenylalkane to phenol and alkenylphenol.  This temperature is in the range of 150-250 ° C.  If the temperature of the solvent is below 150 ° C, the decomposition of dioxydiphenylalkane slows down noticeably and the reaction time increases.  In addition, part of the dioxiphenylalkane is distilled off in a non-decomposable state and is shifted to the reaction product, as a result of which the purity of the target product is reduced.  If the temperature of the reaction medium is above 250 ° C, then working reactions take place, for example, dealkylation of the resulting alkenylphenol during the conversion of the starting material and / or product to the resin, which leads to a decrease in the yield and purity of the product.  A temperature range of 200-240 ° C is preferred, since this reduces the formation of side products and the decomposition reaction proceeds smoothly.  In addition, when carrying out the above decomposition reaction, the decomposition product must be quickly removed from the reaction system after formation.  For this, the reaction medium should be maintained under reduced pressure.  The degree of pressure reduction depends on the decomposition reaction temperature, but usually the pressure during decomposition is in the range of 10-100 mm Hg.  Art.  If the pressure is below 10 mm Hg.  Art. part of the starting dioxydiphenylalkane or part of the inert organic reaction medium is distilled off along with the product, decomposed and mixed with this product, which leads to a decrease in its purity.  If the pressure is above 100 mm Hg.  Art. It is difficult to ward off the decomposition product from the reaction system and, consequently, the residence time of the product in the reaction system increases.  Therefore, side reactions occur, for example, the resulting alkylphenol is diachuted, which leads to a decrease in the yield of the target product, and, in addition, the by-products can be mixed with the desired product, causing a decrease in its purity.  In order for the decomposition product to be quickly discharged from the reaction system and the reaction proceeded smoothly, it is necessary to keep the pressure in the range of 50-100 mm Hg.  Art. , contijeTHee in the range of 50-80 mm Hg.  Art.  In order to carry out the decomposition reaction of dioxyphenylalkane at the indicated temperature and pressure, a high boiling inert organic solvent with a melting or softening point no higher than 150 ° C and a vapor pressure lower than the vapor pressure of the obtained alkenylphenol at the decomposition temperature of dipheniphenylalkane should be selected as the solvent.  Examples of such organic solvents are hydrocarbon coolants, for example, Cj-Cio-alkylnaphthalenes (KSK-O1 and.  NeO-SK OiB, marketed by Sou ken Kagaku, high boiling point distillation residues from the distillation column of diphenylolpropane distillation and novolach-type phenolic resins with a softening temperature according to Л SK-2581 (L S-Japanese npoMbiufennye standards) from 60 to 150 ° C, obtained by the condensation of formaldehyde with an excess of phenol or cresol in the presence of: guvium acid.  These reaction media dissolve dioxyphenylalkanes well at the above decomposition reaction temperatures.  The bottoms of the diphenylolpropane distillate of the dione column is the residue that forms at the bottom of the distillation column when distilled off separates diphenylolpropane (bisphenol A), which is obtained by reacting phenol with acetone in the presence of an acid catalyst.  This residue is a tar-like product containing polycyclic compounds, which even when heated from 200 to 250 ° C and a residual pressure of 2 to 10 mm Hg.  Art.  never forms distillate.  The residue after the bisphenol A distillation column includes: 1) isomers of bisphenol A (1-15 wt. % 2,2-bis (2-hydroxyphenyl) -propane and 1-15 wt. 9b 2 (2-hydroxyphenyl) -2- (4hydroxyphenyl) propane; 2) chromane compound (common name chroman 1) 1-W wt. %; 3) a polyphenolic compound (with 2-6 drami) and 4) a resinous high molecular weight substance.  Molecular weight 3) and 4) is in the range of 300-3000.  Novolac-type phenolic resin is a softening temperature from 60 to 150 ° C, obtained by removing low-boiling material from the product resulting from the condensation of phenol, in particular phenol or cresol, with formaldehyde at a molar ratio between formaldehyde and phenol equal to less than 1.0 in the presence of an acid catalyst, in particular hydrochloric or oxalic acid.  Novolac-type phenolic resin has a number average molecular weight of 400-2000 or a weight average molecular weight of 1000-SOO. The degree of branching is 5-20%.  The decomposition reaction of the dioxydiphenyl alkane according to the proposed method is carried out by feeding the reaction medium and the main catalyst to the reactor equipped with an inlet for the starting material, a distillation opening for the decomposition reaction product, a thermometer and (optionally) a mixing device, maintaining the reaction medium containing the main catalyst, at elevated temperature (150-250 ° C) and reduced pressure (10-100 mm Hg.  Art. ), and supplying dioxyl diphecylalkane. As a result, dioxydiphenylalkane is dissolved in the reaction medium and decomposed in the presence of a basic catalyst dissolved in the reaction medium to form the corresponding alkenylphenol and phenol.  Etipro; The products evaporate and quickly distill from the reaction system.  When performing the operation described above, the supply of dioxydiphyl alkane to the reaction medium is carried out continuously at such a rate that the concentration of dioxydiphenyl alkane in the reaction medium is maintained at a level of 2-30 wt. %  If dioxydiphenylalki is fed at such a high rate that its concentration in the reaction medium exceeds 30 wt. %, increases the distillation of the decomposed starting material.  In addition, in this case, it is not possible to bring enough heat to distill the decomposition product, therefore the amount of decomposition product which is folded in the reaction system increases and causes side reactions, such as conversion of the product to the resin or its dealkylation, to result in reduced reaction yields.  The decomposition reaction of the dioxydiphenylalkane and the distillation of the decomposition product proceed particularly smoothly with good results if the concentration of the dioxydiphenylalkane in the reaction medium is in the range of 2-15 wt. %  Mixing the reaction medium with the starting material and the catalyst can be carried out in the usual mechanical way. However, according to the proposed method, bubbling of an inert gas, for example, carbon dioxide, gels or argon, and black reaction medium is advisable.  Therefore, the reaction medium is stirred to ensure a smooth decomposition reaction and to facilitate the distillation of the decomposition product from the reaction system.  The decomposition product, which is distilled off from the reaction medium, is a mixture of phenol and alkenylphenol.  It can be easily removed by cooling and condensation.  At this time, a portion of the alkenylphenol may polymerize into the alkenylphenol polymer.  Thus, by implementing: decomposition of dioxydiphenylalkane in the reaction medium while maintaining its concentration 2-30 weight. % increases the efficiency of heat transfer, which makes it possible to easily bring a large amount of energy required for the reaction of decomposition and distillation of the resulting decomposition product.  In addition, it is possible to avoid local overheating, it is easy to regulate the decomposition temperature of phenylalkane dioxydcg.  Consequently, the reaction of decomposition of dioxydiphenylalkane proceeds smoothly, and the resulting alkylphenol is quickly distilled from the reaction system, without being delayed for a long time.  Example 1  Into an I liter reactor (equipped with an inlet for the source material, a distillate, an outlet for the decomposition product, an inert gas (inlet) tube and a thermometer) are loaded with 80 g (fluid bed 3.0 cm) (product from Sou ken Kagaku ) and 0.08 g of sodium hydroxide.  Maintain a temperature of KSK-Oi 240 ° C and a pressure in the reactor of 50 mm Hg.  Art.  Molten bisphenol A is continuously fed to KSK-Oii through the inlet at a rate of 400 g / h.  At the same time, nitrogen gas is fed through the inlet (bubbling) pipe at a rate of 4 l / min and it is bubbled through KSK-Git.  As a result, the decomposition of bisphenol A and the distillation of the decomposition product from the reactor proceed smoothly, the concentration of bisphenol A in KSK-Git is maintained at an average of 12.6%.  The decomposition product distilled from the reactor is cooled to condense and recovered.  The reaction lasts 1-0 hours, 4000 g of bisphenol A are decomposed.  3980 g of decomposition product were obtained with a yield of 99.5%.  The decomposition product was found to consist of 41.0% phenol,; 27.1% of p-isopropylphenol, 30.6% of p-isopropenylphenol dimer and 1.3% of p-isopropenylphenol trimer.  Example 2  In the reactor described in example 1, load 80 g (height of the layer.  liquids 2.9 cm) of residue after distilling off biofiol A and 0.08 g of sodium hydroxide.  Undergoes decomposition in the reactor under the conditions described in Example 1, 4000 g of bisphenol A.  Maintain a 13% concentration of bisphenol A in the reaction medium.  3990 g of decomposition product is obtained with a yield of 99.8%.  The decomposition product was found to consist of 41.1% phenol, 27.5% n-isopropenylphenol, 31.1% p-isopropenylphenol dimer and 0.3% three measure of p-isopropenylphenol.  Examples 3-5.  80 g (liquid bed 2.9 cm height) of the residue after distillation of bisphenol A and bisphenol A is decomposed into the reactor described in example 1 (decomposition temperature indicates the temperature of the residue after distillation of bisphenol A, and pressure - pressure in the reactor).  During the reaction, nitrogen gas was introduced through the inlet pipe at a rate of 4.0 l / h, and it was bubbled through the residue after distillation of bisphenol A.  In tab.  1 are given; the conditions of decomposition performed in examples 3-5; in tab.  2 decomposition results.  Example 6  80 g (liquid bed 2.9 cm in height) of a Novolac resin with a K-2531 softening temperature of 90 ° C and 0.08 g of g; sodium troxide are loaded into the reactor described in example 1.  4000 g of bisphenol A is decomposed under the conditions described in Example 1.  The concentration of bisphenol A in the reaction medium is maintained at 12.5%.  3950 g of decomposition product are obtained with a yield of 98.8%.  The decomposition product was found to consist of 41.0% phenol, 27.0% p-isopropylphenol, 30.9% p-isopropenylphenol dimer, 1.1% p-isopropenylphenol trimer.  Comparative example 1.  In the reactor described in Example 1, 0.08 g of sodium hydroxide is charged.  In the reactor, the temperature is maintained at 240 ° C and the pressure is 50 mm Hg.  Art.  Molten bisphenol A is continuously charged at a rate of 400 g / h through the inlet.  After processing 800 g of bisphenol in the manner described above, the amount of the decomposition product obtained is only 500 g and 300 g of resinous substance are formed in the reactor.  The product yield is 62.5%.  The resulting decomposition product was found to consist of 55.5% phenol, 5.1% pisopropenylphenol, 4.2% p-isopropenyl dimer phenol and 35.2% high boiling point substances.  Comparative example 2.  2000 g of bisphenol A is treated under the conditions described in Example 1, then with the exception that the feed rate of bisphenol A is 2000 g / h, the concentration of bis phenol A in the reaction medium is maintained at 50%.  1676 g (yield 83.8%) of decomposition product was obtained.  The decomposition product was found to consist of 33.6% phenol, 20% bisphenol, 23.9% p-isopropenylphenol and 22.5% p-isopropenylphenol dimer.  Example 7  80 g (you (2.9 cm liquid layer) of the residue from distillation of bispheno A and 0.08 g of sodium hydroxide and n {) and the conditions described in example 1 are decomposed into the reactor described in example 1 and decomposed 1400 g 2 , 2- (4,4-dioxy-3,3-dimethylphenyl) propane.  Maintain a 15% concentration of parent plant in the reaction medium.  Received 3990 g of product collapse with a yield of 99.75%.  The decomposition product was found to consist of 42.0% o-cresol, 54.2% p-isopropenyl-o-cresol, 4.06% p-isopropenyl-o-cresol dimer and 1.74% p-isopropenyl-o trimer -cresol  I. Example 8  80 g (height of a layer of liquid 3.0 cm) KSK-Oif (a product of Souke Kagaku) and 0.08 g of sodium hydroxide are charged to the reactor described in example 1.  Under the conditions given in Example 1, 4000 g of 2,2- (4,4-dioxy-3-methyldiphenyl) propane are decomposed.  The concentration of the starting material in the reaction medium is maintained at 13%.  3995 g of decomposition product are obtained with a yield of 99.8%.  The decomposition product was found to consist of 18.2% phenol, 28.0% o-cresol, 31.3% p-isopropenylphenol and 22.5% p-isopropenyl-o-cresol.  Example 9  80 g (the height of the liquid layer is 2.9 cm) of the residue after distillation of bisphenol A and 0.08 g of sodium hydroxide are charged to the reactor described in example 1.  Under decomposition conditions described in Example 1, 4000 g of 2,2- (4,4-dioxydiphenyl) butane are subjected to decomposition.  The concentration of the starting material in the reaction medium is maintained at 15%.  3960 g of decomposition product are obtained with a yield of 99.0%.  The decomposition product was found to consist of 38.9% phenol and 61.5% 2- (4-hydroxyphenyl) -butane-2.  Example 10  80 g (the height of the liquid layer is 2.9 cm) of the residue after distillation of bisphenol A and 0.08 g of sodium hydroxide are charged to the reactor described in example 1.  Under decomposition conditions described in Example 1, 4000 g of 2,2- (4,4-dioxydiphenyl) -4-methylpentane are subjected to decomposition.  The concentration of the starting material in the reaction medium is maintained at 20%.  This gives 3970 g of decomposition product with 99.3% strength.  The decomposition product was found to consist of 26% phenol and 74% 2- (4-hydroxyphenyl) -4-methylpentane-2.  Example I.  In the reactor described in example 1, load 80 g (the height of the liquid layer 2.9 cm) residue; after distillation of bisphenol A and 0.08 g of sodium hydroxide.  Under decomposition under the conditions described in Example 1, 4000 g of 1,1,1- (4,4-dioxydiphenyl) titanium.  The concentration of the starting material in the reaction medium is maintained at 20%.  3990 g of decomposition product was obtained with a yield of 99.8%.  The decomposition product was found to consist of 32.4% phenol and 67.6% - (p-hydroxyphenyl) -styrene.  Example 12  Under the conditions described in Example 1, 1.19 - (4,4-dioxydiphenyl) cyclohexane is decomposed.  The output of the product is 99.9%.  The decomposition product was found to consist of 35.9% phenol and 64.1% 1- (4-hydroxy-yl) -cyclohexane-1.  Examples 13-15.  A 1 liter tank equipped with means for introducing raw materials, means for distillation distillation to isolate the product is fed into the reactor with an inlet tube (a bubble tube) for supplying inert gas and a thermometer; -Oif (product of Soyken Kagaku Co., Inc.) and 0.008 g of sodium hydroxide.  The temperature of the KSK-O product is maintained at a level of 240 ° C, and a pressure of 50 mm Hg is maintained inside the reactor.  Art.  The molten bisphenol A is continuously supplied from the input material for 10 hours at a rate of 300 g / h to the KSK-Oit product. The concentration of bisphenol A in the reaction medium is maintained at a level of from 15 to 20%.  In the meantime, nitrogen gas was passed through an introductory tube at a rate of 4 liters / min and passed through KSK-Oif.  Then, the procedure that is described below is completely repeated, except for that.
    T and in p in I
    The total NUMP of loaded bisphenol A, 910 is that instead of 0.008 g of sodium hydroxide, 0.008 g of phenol and sodium are used. In tab. 3 shows the results obtained in examples 13-15. The following examples show that differences in the composition of the coolant do not cause differences in product yield. Example 16. The reaction of bisphenol A cleavage is carried out according to the method of Example 2, varying the composition of the coolant. In tab. 4 shows the variants of the composition of the coolant; in tab. 5 - splitting results: From the table it can be seen that the results of the reaction do not depend on the composition of the heat-transfer agent. Example 17. The bisphenol A cleavage reaction is carried out according to the method of Example 1, using an alkyl naphthalium mixture from mono-Cs alkylene naphthalene, di-Cs alkyl naphthalene and tri-0 $ alkyl naphthalene, or an alkyl naphthalene mixture from mono-C alkyl naphthalene, di- Xu alkylnaphthalene and tri-CIo alkylnaphthalene. In tab. 6 shows the results of splitting in Example 17.
    o.p
    thirty
    210
    KOH
    Natric salt
    245
    70 bisfe ola a 031
    100
    250
    0) 8
    NaOH Monomer, dimer and trimer denote monomer, dimer and
    28
    300
    there
    ten
    15
    500
    ten
    5,000
    ten
    5,000
    500
    Table 2 Trimer p-isopropylphenol.
    Hydroxide
    2,2-bis (2-hydroxyphenyl) propane
    2- (2-hydroxyphenyl) -2- (Hydroxyphenyl) propane
    Chroman, 1 Polyphenols
    - / PIPE - p-isopropenylphenol,
    Table 3
    15O
    15
    O10
    709083
    Table 5
    xz: i: i :: i 2I 3
    41
    41.3
    41.1
    25,926.3
    27.5
    36,531,9
    31.1
    1.6
    0.5
    0.3
    Phenol
    PIPE
    权利要求:
    Claims (2)
    [1]
    PIPE dimer PIPE trimer. Formula of the invention. Method of producing phenol and Cr-Sb-alkenylphenol by thermal cleavage of dioxydiphenyl-alkane-Ca-Sb at 150-250 ° C, pressure of 10-100 mm Hg. Art. in the presence of 0.015 wt.% of the catalyst with simultaneous distillation of the target products and their subsequent separation, characterized in that, in order to increase the yield of the target products, 2-30% solutions of dioxydiphenylalkanes-C-Сb in a solvent selected from the group are subjected to splitting; distillation bottom of the distillation column of diphenylolpropane, novolac resin with softening temperature 90 41
    40,8
    27.0
    26.7
     31.0 b
    30.6 1.4 150 ° C, C5-C1O-alkylnaphthalenes with the number of alkyl radicals of 1-3, and a substance selected from the group of alkali or alkaline-earth metal hydroxide, alkali-metal phenolate of alkali metal bisphenol is used as catalysis agent. Sources of information taken into account in the examination 1.Patent of France N 2364195, cl. C 07 C 31/14, published 04/07/78.
    [2]
    2. USSR author's certificate number 303314, l. C 07 C 39/18, 1979 (prototype).
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    同族专利:
    公开号 | 公开日
    YU188879A|1982-08-31|
    YU41033B|1986-10-31|
    DD145527A5|1980-12-17|
    FR2433501B1|1985-08-23|
    NL181729C|1987-10-16|
    BR7905187A|1980-05-20|
    GB2031407A|1980-04-23|
    BE878235A|1979-12-03|
    DE2932954C2|1983-10-27|
    CS213393B2|1982-04-09|
    CH639930A5|1983-12-15|
    FR2433501A1|1980-03-14|
    IT7924928D0|1979-08-03|
    GB2031407B|1982-10-27|
    ES483354A1|1980-04-16|
    IN151891B|1983-08-27|
    AU4961979A|1980-02-21|
    DE2932954A1|1980-02-28|
    MX150964A|1984-08-29|
    JPS5527108A|1980-02-27|
    US4245128A|1981-01-13|
    IT1122431B|1986-04-23|
    NL7906168A|1980-02-18|
    HU181914B|1983-11-28|
    JPS5814410B2|1983-03-18|
    CA1133017A|1982-10-05|
    AU526065B2|1982-12-16|
    AR223842A1|1981-09-30|
    NL181729B|1987-05-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR69895E|1956-01-31|1959-01-09|Distillers Co Yeast Ltd|Improvements in the recovery of phenols|
    GB880895A|1958-12-31|1961-10-25|Bayer Ag|Process for the hydrolysis of condensation products of phenols with aldehydes or ketones|
    DE1235894B|1959-08-18|1967-03-09|Bayer Ag|Process for the preparation of alkenylphenols from dihydroxydiarylalkanes|
    DE2064108B2|1969-12-31|1974-09-26|Union Carbide Corp., New York, N.Y. |Process for the production of phenol and p-isopropenylphenol from 2.4'-bisphenol A.|
    PL103054B1|1976-09-12|1979-05-31|Instytut Ciezkiejsyntezy Organic|METHOD OF PROCESSING WASTE FROM THE PROCESS OF MANUFACTURING DIPHENYLOLPROPANE|US4594459A|1985-03-25|1986-06-10|The Dow Chemical Company|Preparation of p-isopropenyl phenol and related compounds|
    US4717777A|1985-09-20|1988-01-05|The Dow Chemical Company|Process for preparing p-isopropenyl phenol|
    US4657890A|1985-09-20|1987-04-14|The Dow Chemical Company|Catalyst for preparing p-isopropenyl phenol|
    JPS632810U|1986-06-20|1988-01-09|
    DE3721853A1|1987-07-02|1989-01-12|Bayer Ag|METHOD FOR PRODUCING MONOMERAL ALKENYLPHENOLS FROM DIHYDROXYDIPHENYLALKANES|
    EP0461388B1|1990-05-24|1996-09-04|Sumitomo Chemical Company, Limited|Positive resist composition|
    DE4202804A1|1992-01-31|1993-08-05|Man Technologie Gmbh|Fibre composite ceramic article with durable surface - made by applying ceramic foil or consolidation material onto article surface|
    JP3364727B2|1993-10-22|2003-01-08|イハラケミカル工業株式会社|2,2-bispropane derivative, method for producing the same, and method for producing pyrogallol using the derivative|
    JP4447076B2|1999-07-06|2010-04-07|三井化学株式会社|Method for cleaving bisphenols|
    US6303835B1|2000-09-11|2001-10-16|General Electric Company|Method for recovering material values from bisphenol tars|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP53098268A|JPS5814410B2|1978-08-14|1978-08-14|
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