• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 引用文献
  • 法律状态
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    • 专利摘要:
    Aluminum monoethyl-phosphite, useful for the protection of plants against fungal diseases, is manufactured in a continuous manner by first preparing a mixture of phosphite compounds, containing at least 70 mol % of diethyl phosphite, then saponifying and neutralizing such mixture with an inorganic base, at a temperature of 20 DEG -85 DEG C., at a pH of 4.0-8.5, and finally reacting the residual aqueous solution of alkaline metal monoethyl-phosphite, continuously withdrawn from the preceding operation, with an approximately stoichiometric amount of a water-soluble aluminum salt at 70 DEG -95 DEG C. and a pH of 3.0-4.5.
    公开号:SU971102A3
    申请号:SU792739698
    申请日:1979-03-24
    公开日:1982-10-30
    发明作者:Бернар Андре；Дидье Андре；Руайе Мишель
    申请人:Рон-Пуленк Агрошими(Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the chemistry of organophosphorus compounds, and in particular to an improved method for producing aluminum monoethyl phosphite, which is a highly effective fungicide.
    The closest in technical essence and the achieved results to the proposed is a method for producing aluminum monoethyl phosphite by treating diethyl phosphite with an aqueous-alcoholic solution of the base at the boiling point of the reaction mixture, followed by separation of the obtained alkali metal or ammonium monoethyl phosphite and treating it with hydrated aluminum nitrate (.1].
    The yield of the target product is 60% ..
    The disadvantages of this method are: the use of expensive diethylphosphite as the starting reagent, the yield of the target product is not high enough, and the product is obtained in the form of a powder with a density of 0.4 to 0.6 and a humidity of about 25%, and therefore There are inconveniences when being filtered2, it requires continuous drying and is difficult to handle.
    One invention is to simplify the process, increase the yield and improve the quality of the target product.
    This goal is achieved by the fact that in the method for producing aluminum monoethyl phosphite, a mixture consisting of 76.5 -80 wt.% Diethyl phosphite, 18-22 wt.% Monoethyl phosphite and 1.4 - 2.0 wt.% Are used as a derivative of ethyl 10 phosphorous acid. phosphoric acid, treated with a water-alcohol solution of U base at pH 4-8.5 and temperature
    - 80 ° C, the resulting alkali metal or ammonium monoethyl phosphite is separated and treated with a water-soluble aluminum salt at a pH of 3-4 and a temperature of 80-90 ° C.
    As a base in the process, it is desirable to use sodium hydroxide, potash or ammonium hydroxide.
    It is advisable to use supe3 971102 as a water soluble aluminum sopi 25. aluminum fat, aluminum nitrate or sodium aluminate.
    In order to conduct a continuous process, it is desirable that the reaction products, base and ethanol are continuously removed from the reaction zone, followed by the supply of base and ethanol to the process.
    The proposed method allows to simplify the process of producing monoethyl phosphite of aluminum due to using instead of expensive diethyl phosphite a cheaper mixture consisting of the above amounts of diethyl phosphite, monoethyl phosphite and phosphorous acid, increase the OUTPUT of the target product to 90% and obtain the target product in the form of a uniform powder with a density of 0.7 -0.9 and a moisture content of less than 20%, which facilitates its use in fungicidal formulations.
    The initial mixture of diethyl phosphite, monoethyl phosphite and phosphorous acid is obtained by the reaction of phosphorus trichloride and ethanol, which proceeds according to the scheme
    Pdi 3 + 3d z H 5 oii- * n
    - (NgNeO) ^ + d z H s dl + 2Hdl% and in the case of using ethanol ^ soder (water), according to the scheme:
    Ipdh + zdzHsOH + KgO- * n
    - (d2H 5 o] z ^ + 3Hdi n (d z H 5 o) z P ^ + н г о- * о
    Η
    - * d z H 5 oi-'OH + b g n 5 he
    Η c! 2 h 5 otp ^ + n g o
    About it. The released hydrogen chloride causes the following processes:
    H '(^ Η 5 ο) 2 ρζ + Hdi—.
    about n y g n 5 o-r-on- | -0 g n 5 e1 δ
    ¥ d r n 5 o-r- he + Hd L - o
    but n
    ->^> p x + d 2 H 5 di but h
    The resulting hydrogen chloride and ethyl chloride are at least partially removed from the reaction sphere by distillation and / or neutralization.
    Next, the initial mixture of phosphites is treated with a water-alcohol solution of a base, such as sodium, potassium or ammonium hydroxide, at 4-8.5. This process is X __
    - 80 ° C and pH proceeds according to the scheme:
    Η o
    Η
    C 2 h 5 op- 0M + d z H 5 0H b
    4-MOH n
    d z H 5 o ^ + М0Нн d ^ op- ohm + n 2 о о n
    Hoi-OH + 2MOH δ ¥
    pestilence - ohm + gn o and ό
    jH0-P-0H + MON - * MPO-it 4u о II t < 1 о о
    H (D + MON — Ng o, where Ν 'is the cation of an alkali metal or ammonium.
    The concentration of water-wt% monoethyl phosphite used, 2 wt.% Phosphorous acid and hydrochloric acid, is sent to another reactor, where at a temperature of 75 ° C, maintained by circulating hot water, it is treated with an aqueous 50% sodium hydroxide solution when supplied the latter at a speed of 200 g / h (pH 7.5). The residence time of the reactants in the reactor 10 is about an hour.
    alcohol solution of the base is 20 -50%.
    As a result of the saponification of a mixture of phosphites, ethanol and water are formed as by-products, which are continuously removed from the reaction zone in the form of a water-alcohol mixture and returned to the process.
    The obtained alkali metal or ammonium monoethyl phosphite is subjected to treatment with a water-soluble aluminum salt, such as aluminum sulfate, aluminum nitrate or sodium aluminate, at pH 3-4 and 80 - 90 ° C. The reaction proceeds according to the scheme:
    And d d 2 n 5 op - ohm * 0 ^ z o n
    - * (d g Н 5 OP - o) 3 At + 3 / g to g 0 4 о
    The water-soluble aluminum salt is used either in solid form or in the form of an aqueous solution in a stoichiometric amount, or in excess of 20 mol. %
    Aluminum monoethyl phosphite precipitates, which is filtered off and subjected to hot washing to remove water-soluble salts. The target product is obtained with a yield of up to 90% and higher, with a 95% degree of purity, in the form of a uniform white powder.
    Example 1. Obtaining monoethylphosphite aluminum.
    Phosphorus trichloride is introduced continuously with stirring at a speed of 550 g / h (4 mol / h) and 520 g / h of 90% into a reactor designed to produce a mixture of phosphites at a temperature of 60 ° C, maintained by external dir, cu lation of water. ethyl alcohol (excess 10%). The residence time of the reactants in the reactor is 5 minutes The resulting hydrogen chloride and ethyl chloride are partially removed.
    The reaction product, consisting of a mixture of phosphites: 80 weight. % diethyl phosphite,
    From the obtained reaction mixture containing sodium ethyl phosphite, ethanol, water, sodium chloride and a small amount of sodium phosphite, ethanol is continuously distilled off in the form of a water – alcohol solution (80 wt.% Alcohol). The remainder is an aqueous solution of 2 to 9 wt.% Sodium ethyl phosphite and 11 wt.% Sodium chloride. The output of sodium ethyl phosphite in relation to phosphorus trichloride is 97%.
    The resulting residue at a speed
    1960 g / h at 85 ° C is continuously fed with stirring into the third reactor, into which 28% is introduced at a speed of 864 g / h ! an aqueous solution of aluminum sulfate at the same temperature (an excess of 10 mol% of aluminum sulfate with respect to sodium * sodium phosphite can be used); pH of 3.8. The resulting aluminum ethyl phosphite precipitates. The reaction mixture was incubated for one hour in a precipitation reactor. Then the pulp is drained and separated on the filter. The wet product (residual moisture content of 8%) is washed with hot water and dried at 90 ° C. A dry target product is obtained with a productivity of 400 g / h. The yield of the target product in relation to sodium ethylphosphite is 88% (addition to 100% is in the mother or wash water, returned, if necessary, to the process) and 85% in relation to phosphorus trichloride. The content of aluminum phosphite in the target product is below 2%. Aluminum monoethyl phosphite has the form of a powder with a density of 0.9.
    PRI me R 2. A mixture of phosphites of the composition specified in example 1, is subjected to treatment with an aqueous solution of sodium hydroxide in two reactors: in the first at 30 ° C, pH 4 - 4.5 using a 30% aqueous solution of sodium hydroxide at a feed rate of 1900 g / h; the exposure time is 5 hours, with the withdrawal of the reaction product through the bottom and feeding it to the second reactor at 80 ° C, pH 8 - 8.5 using a 30% sodium hydroxide solution at its speed. feed 100 g / h.
    Ί
    Subsequent operations are carried out, as in example 1. The results of the experiment are the same as in example 1.
    Example 3. The process is carried out, as in example 1, using potash potassium oxide instead of hydrate 5. The results of the experiment are the same as in example 1.
    Example 4. The process is carried out as in example 1, replacing the sodium hydroxide with ammonia, taken in 5% to 10% excess in relation to stoichiometry. Due to the high solubility of ammonium ethyl phosphite in water (65%), a concentrated solution of ammonium ethyl phosphite is obtained. . fifteen
    A 44% aqueous solution of ammonium ethylphosphite and an 18.5% aqueous solution of ammonium chloride are reacted with a 40% solution of aluminum sulfate at 90 ° C. for 1 hour (holding time). The results are similar when using one (temperature less than or equal to 80 ° C and pH · less than or equal to 8.5) or two reactors.
    The yield of aluminum ethyl phosphite in relation to 2S to ammonium ethyl phosphite is 89% and about 86% with respect to the phosphorus trichloride used.
    Example 5. The process is carried out as in Example 1, with the difference that aluminum sulfate in crystalline form A (SO, is used and fed at a rate of 433 g / h. The process is carried out at 180 ° C, holding time 1 h 30 min, g. More than in the case of an aqueous solution, since it is necessary to ensure the dissolution of solid aluminum sulfate • After filtration, washing, drying under the same conditions as in example 1, 42 5 g / h of dry ethyl phosphite are obtained aluminum, with a yield of 93.5% with respect to sodium ethyl phosphite and 90% with respect to phosphorus trichloride.
    Etc. and MER 6. The process is carried out as in example 1, replacing aluminum sulfate with hydrated aluminum nitrate containing 9 HjO, more soluble in water (55% at 80 ° C).
    In addition, the sodium nitrate formed during the reaction, being more soluble than sodium sulfate, contributes to the formation of aluminum ethyl phosphite due to the increased salt effect.
    Under these conditions, the latter is obtained with a yield of 91% with respect to sodium ethylphosphate and 87% with respect to phosphorus trichloride.
    Example 7. The process is carried out as in example 6, however, after processing the mixture 971102 8 si phosphites with an aqueous-alcoholic solution of sodium hydroxide, ethanol is not removed, therefore, the last stage of the process is carried out in an aqueous-alcoholic solution containing 25.5% sodium ethylphosphite, 9.5 % sodium chloride and aluminum nitrate, which is fed at a speed of 800 g / h. The ethyl ethyl phosphite obtained after filtration has a lower moisture content (9%) than the product in Example 1. Example 8. The process is carried out as in Example 1, replacing aluminum sulfate with sodium aluminate INa ^ Qc with the addition of hydrochloric acid necessary to maintain the desired pH.
    Under these conditions, aluminum monoethyl phosphite is obtained in a yield of 60%. Example 9. A mixture of 90 wt.% Diethphosphite and 10 wt.% Phosphorous acid is heated at 150 ° C, get a mixture containing 76.5 wt.% diethyl phosphite, 22 wt.% monoethyl phosphite and 1.4 wt.% phosphorous acid, it is cooled and further processed, as in example 1, but with a lower consumption of sodium hydroxide, since there is no hydrochloric acid in the mixture .
    Example 10. The process is carried out as in example 1, but at the stage of processing sodium ethyl phosphate with aluminum sulfate, sodium sulfate is added to the reaction mixture at a rate of 120 g / h.
    Under these conditions, the yield of aluminum ethyl phosphite is 90% (instead of 88% in example 1) with respect to sodium ethyl phosphite.
    权利要求:
    Claims (3)
    [1]
    aluminum veil, aluminum nitrate or sodium aluminate. In order to carry out an uninterrupted process, it is desirable that the reaction products, the base and ethanol be continuously removed from the reaction zone, followed by feeding of residue and ethanol to the process. The proposed method makes it possible to simplify the process of obtaining aluminum monoethyl phosphite by using a cheaper mixture consisting of diethyl phosphite, monoethyl phosphite and phosphorous acid, instead of expensive diethyl phosphite, to increase the yield of the product to 90% and to obtain the target product in the form of a homogeneous powder with a density of 0.7-0.9 and a moisture content of less than 2O%, which facilitates its use in fungicidal formulations. The initial mixture of diethyl phosphite, monoethyl phosphite and phosphorous acid is obtained by the reaction of phosphorus trichloride and ethanol. Kotor flows according to the Pdis + sdgHsOii p + d2H5di-f 2Hdi (bgNzO) scheme and, in the case of using ethanol that is | water-soluble, according to the following scheme: Ipdig + zdzHgOH + i LgO- / n - (daHsOjgP -hSHdl 0 o zhdH o 0g oHgO + odgH3O-ng (oHgO) + NgO - o dgHgOi -oH + dgHgOR o djHsOP: + NgO o he-Hoi-oH-bdjHsOH oh cus hydrogen chloride produces the following processes: (zHsO) + Hdi dgHsO-p-oH-i-dgHsdi o daHsO OH + Hdi p + d2H5di but 0 combustible hydrogen chloride and pure ethyl are at least partially removed from the reaction site by distillation and neutralization, and then the initial mixture of phosphites is scraped with an aqueous-alcoholic solution of ash, such as sodium hydroxide, ammonium hydroxide, at 30-8 ° C C and pH, 5. This pr The process proceeds according to the following scheme: (dgHsOJgi 4MON d2H50p-OM + d2H50H o dzHsO + MON o2 dHH-p-oM-fH20 o Hoi-OH-f-2MOHMOR-OKN-2NgO IHO-P-OH 4 MON MOR-OH4H-0 and HdH - MON - MC11 + Ng Oh, in the NV range - alkali metal or ammonium cation. The concentration of the hydroalcoholic base solution used is from 2.0 to 50%. As a result of the saponification of phosphite mixtures, ethanol and water are formed as by-products, which are continuously removed from the reaction zone in the form of a water-alcohol mixture and return to the process. The alkaline metal or ammonium monoethyl phosphite obtained is subjected to the treatment with a water soluble aluminum salt, such as aluminum sulfate, aluminum nitrate or sodium aluminate, at pH 3 and 80 -. The reaction proceeds according to schemes 3 with gNz or - OM - Ug A1g (0), (dgH5 OP-OJjAt t Y2Kg O4 O Water soluble aluminum salt is used either in solid form or as an aqueous solution in stoichiometric amount or in excess of 2 Omol .% Monoethyl phosphite aluminum precipitates, which is filtered and subjected to hot washing to remove water-soluble salts. The desired product is obtained in a yield of up to 90% and in a 95% purity yield. Example 1. Preparation monoethyl phosphite aluminum. In a reactor designed for In order to obtain a mixture of phosphites, at a temperature supported by external circulation of water, phosphorus trichloride is continuously added with stirring at a rate of 55 O g / h (4 mol / h) and 520 g / h 9 O% ethanol (excess 1 O% V the reagents stay in the reactor for 5 minutes The resulting hydrogen chloride and ethyl chloride are partially removed.The reaction product consisting of a mixture of phosphites: -80% by weight of diethylphosphite, 18% by weight of monoethylphosphite, 2% by weight. % phosphorous acid and hydrochloric acid are sent to another reactor, where, at a temperature of 75 ° C, maintained by circulating hot water, it is treated with an aqueous 50% sodium hydroxide solution when the latter is fed at a rate of 2OO g / h (pH 7.5). The reagents stay in the reactor for about an hour. Sodium ethylphosphite containing ethanol, water, sodium chloride and a small amount of sodium phosphite are obtained from the resulting reaction mixture, ethanol is continuously distilled off in the form of an aqueous-alcoholic solution (80% by weight of alcohol). The residue is an aqueous solution of 29 wt.% Sodium ethyl phosphite and 11 wt.% Sodium chloride. The yield of sodium ethyl phosphite with respect to phosphorus trichloride is 97%. The residue obtained was continuously fed at a rate of 1960 g / h at 85 ° C with stirring into a third reactor, into which a 28% aqueous solution of aluminum sulfate was introduced at a rate of 864 g / h at the same temperature (an excess of 10 mol% can be used aluminum sulphate relative to ethphosphate sodium); pH of 3.8. The resulting ethyl aluminum phosphate precipitates. The reaction mixture is kept in the precipitation reactor for one hour. Then the pulp is drained and separated on the filter. The wet product (residual moisture content 8%) is washed with hot water and dried at 90 ° C. Dry target product is obtained with a capacity of 400 g / h. The yield of the target product with respect to sodium ethylphosphite is 88% (the addition to 1OO% is in the mother or wash water returned, if necessary, to the process) and 85% with respect to phosphorus trichloride. The content of phosphite-aluminum in the target product is below 2%. Aluminum monoethyl phosphite has the appearance of a powder with a density equal to O, 9. EXAMPLE 2 A mixture of phosphites of the composition specified in Example 1 is treated with an aqueous solution of sodium hydroxide in two reactors: the first one at 30 ° C, pH 4- 4.5 using an aqueous sodium hydroxide ZOR at a feed rate of 19OO g / h; a holding time of 5 hours, with the reaction product being withdrawn through the bottom and feeding it into the second reactor at pH 8-8.5 using 30% sodium hydroxide solution at its speed. feed rate of 100 g / h. 79 The subsequent operations are carried out as in Example 1. The results of the experiment are the same as in Example 1. Example 3. The process is carried out as in Example 1, using potash instead of sodium hydroxide. The results of the experiment are the same as in Example 1. Example 4. The process is carried out as in Example 1, replacing sodium hydroxide with ammonia, taken in 5% excess relative to stoichiometry. Due to the high solubility of ethyl ammonium phosphite in water ( 65%) get a concentrated solution of ammonium ethylphosphite. . A 44% aqueous solution of ammonium ethylphosphite and an 18.5% aqueous solution of ammonium chloride is reacted with a 4-0% solution of aluminum sulphate at 90 ° C for 1 h (holding time). The results are close when using one (the temperature is less than the sludge is 80 ° C and the pH is less than or equal to 8.5) or two reactors. The yield of aluminum ethyl phosphite with respect to ammonium ethyl phosphite is 89% and about 86% with respect to the phosphorus trichloride used. Example 5. The process is carried out as in example 1, with the difference that aluminum sulphate is not used in the curve, (.30) 15 H, jO and is fed at a speed of 433 g / h. The process is carried out at 180 ° C, the exposure time is 1 h 30 min, t, that is, more than in the case of an aqueous solution, since it is necessary to ensure the dissolution of solid aluminum. After filtration, washing, drying under the same conditions as in Example 1, 425 g / h of dry ethyl phosphate aluminum is obtained, with a yield of 93.5% with respect to sodium ethyl phosphite and 9 O% with respect to phosphorus trichloride. Etc. and measure 6. The process is carried out as in Example 1, replacing aluminum sulphate with hydrated aluminum nitrate containing 9, which is more soluble in water (55% at 80 ° C). In addition, sodium nitrate formed during the reaction, being more soluble than sodium sulphate, contributes, by increasing the salt effect, to the formation of ethyl aluminum phosphite. Under these conditions, the latter is obtained in a yield of 91% with respect to sodium ethyl phosphate and 87% with respect to phosphorus trichloride. Example 7. The process is carried out in Example 6, however, after treatment, see cm 028 phosphites with water; ethanol is not removed with a nitrate solution of sodium hydroxide, therefore the last stage of the process is carried out in a water-alcohol solution containing 25.5% sodium ethylphosphite, 9.5% sodium chloride and aluminum nitrate, which is fed at a rate of 800 g / h. Ethylphosphite aluminum obtained after filtration has less moisture (9%) than the product in Example 1. Example 8. The process is carried out, as in Example 1, by replacing aluminum sulphate with sodium aluminate 7.3 with the addition of hydrochloric acid necessary to maintain the desired pH. Under these conditions, aluminum monoethyl phosphite is obtained with a yield of 60%. Example 9. A mixture of 90 wt.% Diethylphosphite and 10 wt.% Phosphorous acid is heated at 150 ° C, get | a mixture containing 76.5% by weight of diethylphosphite, 22% by weight of monoethyl phosphite and 1.4% by weight of phosphorous acid, is cooled and then treated as in example 1, but with less consumption of sodium hydroxide, as there is no salt in the mixture on acid. Example 10 The process is carried out as in Example 1, but at the stage of treating sodium ethyl phosphate with aluminum sulfate, sodium sulfate is added to the reaction mixture at a rate of 120 g / h. Under these conditions, the yield of aluminum ethyl phosphite is 90% (instead of 88% in example 1) with respect to sodium ethyl phosphite. The invention claims 1. A method of producing aluminum monoethyl phosphite by treating an ethyl phosphorous acid derivative with an aqueous alcoholic base solution by heating, followed by separating the alkali metal or ammonium monoethyl phosphite and processing it with a water-soluble aluminum salt, distinguishing from The aim is to simplify the process, increase the yield and improve the quality of the target product, in the quality of an ethyl phosphorous acid derivative, a mixture consisting of 76.5 8 O.W.% diethyl phosphite, 18 - 22 wt.% m . Noetilfosfita and 1.4 -2.0% by weight phosphorous acid, water-treating an alcoholic solution of base is carried out at a pH of 4-8,5 and LP temperature - 80 ° C and processing the resulting monoetilfosfita
    997110210
    alkali metal or ammonium salt4, The method according to PP, 1-3, about tl and aluminum is carried out at a pH of 3-4 and tempered by the fact that, in order to make the process 8O - a continuous process, the products
    [2]
    2, the method of claim 1, the reaction of the reaction, the base and ethanol continuously, and so that sodium hydroxide is used as the base, followed by sodium hydroxide, potash base and ethanol ammonium oxide process, or ammonium hydroxide,
    [3]
    3. Method according to paragraphs. 1 and 2, are different. Sources of information, which are based on the fact that, in the examination of water-soluble aluminum salts, 10 are used. 1. French Patent No. 2288463, aluminum sulfate, aluminum nitrate, cl. And 01 N 9/36, published. 1976 (propended sodium aluminate. Type).
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    同族专利:
    公开号 | 公开日
    SE7902656L|1979-09-25|
    RO77719A|1982-04-12|
    DK146628B|1983-11-21|
    NL188698B|1992-04-01|
    YU41150B|1986-12-31|
    IT1114217B|1986-01-27|
    SE447655B|1986-12-01|
    JPS54132526A|1979-10-15|
    DK120079A|1979-09-25|
    FR2420540B1|1980-08-29|
    CH636624A5|1983-06-15|
    BE875081A|1979-09-24|
    PL214335A1|1980-07-01|
    DE2911516C2|1990-04-19|
    PL126412B1|1983-08-31|
    ES478893A0|1980-06-16|
    AT376223B|1984-10-25|
    IL56936D0|1979-05-31|
    YU69079A|1982-10-31|
    NL7902320A|1979-09-26|
    US4272448A|1981-06-09|
    ZA791379B|1980-04-30|
    ES8107239A1|1980-06-16|
    ATA218779A|1984-03-15|
    IE790636L|1979-09-24|
    IT7921266D0|1979-03-23|
    CA1117967A|1982-02-09|
    LU81073A1|1980-10-08|
    IE47939B1|1984-07-25|
    DD142535A5|1980-07-02|
    JPS6254116B2|1987-11-13|
    PT69389A|1979-04-01|
    GB2017706A|1979-10-10|
    DK146628C|1984-05-07|
    DE2911516A1|1979-10-04|
    NL188698C|1992-09-01|
    BR7901800A|1979-11-20|
    IL56936A|1984-02-29|
    GB2017706B|1982-09-02|
    FR2420540A1|1979-10-19|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE2463046C2|1973-12-14|1984-05-03|PEPRO - Société pour le Développement et la Vente de Spécialités Chimiques, Lyon|Ammonium phosphonate-based fungicidal agents|
    FR2254276B1|1973-12-14|1977-03-04|Philagro Sa|
    DE2513965C3|1975-03-29|1979-05-31|Th. Goldschmidt Ag, 4300 Essen|Process for the preparation of MetaUphosphorigsäuremonoesterverbindungen|
    IE45984B1|1976-11-16|1983-01-12|Philagro Sa|Process for the manufacture of aluminium ethylphosphite|CN1005265B|1985-04-12|1989-09-27|福建师范大学|Novel aluminum system coupling agent|
    JP2747586B2|1988-01-29|1998-05-06|花王株式会社|Method for producing polyaluminum dialkylphosphate salt, oil gelling agent comprising the salt, and external preparation composition containing the salt|
    DE19639657C2|1996-09-27|2000-03-09|Hoechst Ag|Process for the preparation of aluminum dialkylphosphinates|
    CN101525302B|2009-04-30|2012-02-08|山东德浩化学有限公司|Method for coproducing fungicide phosethyl-Al in acetochlor production|
    CN102268033A|2011-06-16|2011-12-07|浙江嘉华化工有限公司|Production method of sodium O-ethyl phosphate|
    CN102766157B|2012-09-05|2015-11-11|利民化工股份有限公司|A kind of method of producing technical-grade fosetyl-aluminum|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7809965A|FR2420540B1|1978-03-24|1978-03-24|
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