• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    N-phosphonomethylglycine is prepared from glycine and parsformaldehyde to obtain an intermediate which is reacted with dialkylphosphite to obtain an ester of the desired compound which is then hydrolyzed.
    公开号:SU1282820A3
    申请号:SU802948398
    申请日:1980-07-08
    公开日:1987-01-07
    发明作者:Брендель Марта；Гулиаш Имре；Дьекер Иштван；Жупан Кальман；Чорвашши Иштван；Шаламон Золтан；Шомодьи Габор；Сент-Кирайи Иштван；Тимар Тибор；Биро Ева；Фодор Иштван；Репаши Янош
    申请人:Алкалоида Ведьесети Дьяр (Инопредприятие)；
    IPC主号:
    专利说明:

    The invention relates to an improved method for the preparation of N-phosphonomethylglycine (glyphosate) of the formula (H0) j P CH "SchSN" COOH, which
    II Oh
    but .
    is an active ingredient in general herbicide with a wide range of action and is used in agriculture.
    A known method for producing N -phosphonmethylglycine by the interaction of glycine with chloromethylphosphonic acid in an aqueous-alkaline medium at the boil for. 20 h.
    However, the duration of the process limits the possibilities of using this method.
    There is also known a method for producing N-phosphonmethylglycine, which consists in the following that L-substituted glycine ester is reacted with phosphorous acid and formaldehyde in an acidic aqueous medium at 100-150 ° C, followed by hydrolysis of N-substituted K-phosphonomethylglycine ether with a hydrogen-hydrated, iodide-iodide, iodide, iodide, iodide, iodide, iodide, iodide, iodide, iodide, iodide, iodide, iodide, iodide, iodide, iodide, iodide, iodide, iodine, iodide, iodide, iodide, iodide, iodine, iodide, iodide, iodide, iodide, iodide, iodide, iodide, iodine water can be hydrolyzed by concentrated hydrochloric acid in a hydrochloric acid; acid at boiling the reaction mixture. The yield of the target product is 41%.
    The disadvantage of this method is the need to obtain an N-substituted glycine ester, which is associated with additional steps, as well as a low yield of N-phosphonmethylglycine.
    The closest to the proposed technical essence and the achieved result is a method for producing N-phosphonomethylglycine by the interaction of glycine with formaldehyde in an aqueous alkaline medium at 0-15 ° C with subsequent treatment of the alkaline salt of N-hydroxymethylglycine dimethyl- or diethylphosphite in an aqueous medium at 90-100 ° C and feeding the obtained ester of N-phosphonomethylglycine to hydrolysis, which is carried out with hydrochloric or hydrobromic acid at 90-100 ° C. The yield of the target product 62-67%.
    The disadvantages of this method include the low selectivity and, in connection with this, the insufficient purity of the target product, which turns out to be contaminated with glycine, bis -Nj, N-phosphonomethylglycine, especially when the process is carried out on a large scale. In this connection, to obtain a product of the required degree of chi
    It must be subjected to additional cleaning.
    The aim of the invention is to increase the yield and purity of the target product.
    The goal is achieved by the method of obtaining N-phosphoiomethylglycine by reacting glycine with formaldehyde in the presence of a basic agent with a molar ratio of the main agent and glycine (0.6-0.9): 1, glycine and formaldehyde 1:: (2.06- 1,1) in the environment of absolute alcohol - methanol followed by treatment of the obtained reaction product with dimethyl or diethyl phosphite at a molar ratio of the latter to glycine equal to (0.66-1.1): temperature 60-80 0, pH 5.8 -8, further acidification with a strong acid to ensure intermediate hydrolysis h-monoalkylphosphono-methylglycine and distillation to isolate the solvent and by-products.
    It is advisable to use 1.9-2 molar equivalents of formaldehyde relative to glycine, while glycine is almost completely converted to N, N-bis-oxyme glycine,
    whereas when using formaldehyde. in an equimolar amount or with a slight excess, a part of the glycine does not react and its
    it is necessary to separate glycine from the reaction mixture by acidification to the iso-electric point and subsequent crystallization.
    The reaction is advisable to carry out
    in a relatively dilute solution, using a 1.1-1.5 molar solution of glycine in an alcohol, mainly methanol.
    Triethylamine, KOH, NaOH, potassium acetate are used as the basic agent to create the required pH of the solution, but this does not limit the range of basic agents used.
    The use of a non-aqueous solvent is very significant. Conducting the interaction of glycine with formaldehyde in an alcohol medium leads to the formation of a new
    intermediate, M, M-bis-oxymethylglycine, which, when converted into a target product, significantly reduces the possibility of side reactions. This leads to a significant increase in yield (up to 80%) and an increase in the purity of the target product (up to 99%), whereas the target product obtained by a known method contains 26% as impurities 5
    ROH 1) 2CH-0 + NH, -CHg-COOH g
    where R is C, -C., is alkyl; R is ethyl;
     H
    0-r
    I
    CHj 4.-N-CH -COOH-NRj S, 5
    where is methyl, ethyl;

    K, M-bisphosphonmeth1 glycine and 6% glycine (overall yield 62-67%).
    The course of the reactions taking place during the process can be reflected by the following scheme:
    NP-PW
    no-fn: "-" gsoo "-".
     About R about fNS1
    3) P-CH. -NH-CH.-COOR Hydrolysis
    HOJ
    P-CH.-NH-CH -COOH - target h
    but. N-phosphonomethylglycine.
    adverse reactions:
    .o.Rn5 no-sdd- ""
    .one
    NR;

    OFI
    about
    ABOUT
    t / heI he
    W2-P (-Cl-CH -Pr
     .on HCV
    51 xP-CHo-NH-CH -COOH-i-HG-CHo-PC BUT Zyyy Q
    HOvV
    BUT

    /
    P-CH.
    but X
    / R-so
    but
    Under the process of interaction between formaldehyde and glycine, observation was carried out using FT-NMR in a reference vessel. NMR spectrum: 0.5 ml CD OD. The concentration ratio is identical to the concentration ratio and the conditions of Example 1 (temperature). The recording was carried out in a Bruker GT-NMR apparatus, 200 MHz. The offsets are indicated on the S-scale in ppm.
    Compound 1 - S, K-bis-hydroxymethylglycine.
    H-NMR spectrum, ppm: (HOCH n) 1 methylene 3.42 s, 2H; flax with, 4H.
    . C-NMR spectrum, ppm; (NOSE) - 54.6; , 0.
    COOH, C-displacement: 178.9 ppm
    22 2 marks
    .eleven
    HC1
    - ""

    OFI hydrolysis
    ABOUT
    At the beginning of the reaction, the water present is involved in the formation of the compound, as a result of which both the yield and the quality of the product are reduced. In this case, directional preparation of this intermediate product is necessary, which contributes to good selectivity of the reaction,
    In the reaction mixture before hydrolysis or after acidification by means of NMR or high-pressure liquid chromatography, the presence of N, N-bic-phosphone-methylglycine or its ester cannot be proven.
    Compound II is a K- (monoalkylphosphonomethyl) -N-alkoxymethylglycine structural formula
    CH2-l; -CH 2.-COOH.lSiB);
    ®СН2
     ,
    0-r
    where R-R is methyl;
    R is ethyl.
    H-NMR spectrum, ppm: 1 methylene 3.38 s, 2H; 2 methylene 4.24 s, 2H;
    3methylene 3.34 d, 3 pp, 14.3 Hz, 2H
    4 methylene 3.77 d, 3
    RSIL
    Rosn; 10.4 Hz.
    CH i - N-CHo-COOH, -NiRa + H70 GG
    I
    CH, I OR
    Y-CH -COOa-NR M-ROH
    n he
    In this regard, it is necessary to carry out the process in absolute alcohol.
    It should be noted that this reaction as a condensation reaction, which takes place in a solvent, is a catalyzed acid (base) process. From this it follows that with this interaction, the pH value of the reaction medium plays an important role.
    The choice of pH in this process can be explained as follows.
    A strongly alkaline medium (a large pH value) promotes the hydrolysis of the dialkyl phosphite formed in the course of the reaction. 1 mole of water.
    During the reaction, the acidic environment contributes to the elimination of water and condensation. However, a strongly acidic medium prevents the formation of a protective group and shifts the equilibrium in an undesirable direction. At the same time, it contributes to the formation of the second phosphonomethyl group. It follows that the selectivity and the yield of the reaction are reduced.
    If the reaction is carried out in the presence of a small amount of R, N (at low pH),
    1282820
     C-NMR spectrum, ppm: C, s; C 89.6 s; C 3 46.4 d, Jp. : 95.9 Hz; C, .53.5 d, J: 6.9 Hz.
    The data presented unambiguously indicate the formation of an intermediate product IT. The protective group (methoxymethyl) prevents further phosphonomethylation.
    The presence of water shifts the equilibrium of the above reaction in an undesirable direction. As a result, the selectivity of the process and the code of the reaction products decrease, which proceeds as follows:
    35
    the amount of N, N-bis-phosphonomethylglycine increases.
    Intermediate 1I is rather unstable.
    Without isolation, acidification of the resulting reaction mixture with a mild acid under mild conditions (10 ° C) and its further evaporation, the following compound can be isolated (from the meta-JQ medium):
    CHjO. tН
    / P-CHo-lS -CH COOH BUT (D (D)
    / H-NMR spectrum, ppm: 1 methylene, 3.63 s, 2H; 2 methylene 3.13 d, J,
    13.1 Hz; 3 methylene 3.62, J
    PCH2
    rpon -1
    10.5 Hz, ZN.
    Under the conditions of a known method, when acidifying with a strong concentrated acid (hydrochloric) in an alcohol medium, the carboxyl group is esterified. The following ether forms:
    ABOUT
    MeO t

    BUT
    / Р-СН2-Ъ1-СН-2-СООИе
    7 1
    P1-NMR spectrum, ppm: 1 methylene 4.10 s, 2H; 2 methyl 2.36 s, ZN; 3 methylene 3.74 d; : 14.1 Hz,
    2H; 4 methyl 3.90 d, J
    ROSN,
    : 11.2 Hz.
    The presence of the carboxyether is demonstrated in the C-NMR spectrum by shifting the C-bands of the carboxyl group in the direction of a greater field strength. An offset of 168.5 ppm was measured (as opposed to an offset of 177.8 ppm of the compound
    P).
    Calculated,%: C 30.46; H 6.14; N 7.10; R 15.71.
    Found,%: C 30.22; H 6.28; N 6.80; R 15.65.
    Under the conditions of a known method, during the distillation of the alcohol and subsequent hydrolysis at a temperature above these ether groups are cleaved, i.e. the yield of the target product is reduced.
    Example 1 30 g (1.0 mol) of para-formaldehyde are added to a solution of 500 ml of methanol and 47 g (0.465 mol) of triethyl amine at 25–30 ° C, after which the mixture is heated to 65–66 ° C and kept at this temperature until the solution will not become clear. After that, 37.5 g (0.5 mol) of glycine is added. The mixture reacts at 66-68 ° C for 5 minutes, after which 55 g (0.5 mol) of dimethyl phosphite are added over 5 minutes. The reaction mixture is stirred for 1 hour at 68-70 ° C, while the pH decreases from 6.3 to 5.8.
    210 ml of hydrochloric acid (34-36%) are added to the mixture over 5 minutes. Methyl alcohol, as well as the resulting methylal and methyl chloride, are removed by distillation at atmospheric pressure. The distillation is started at a reaction temperature of 70 ° C, a vapor temperature of 62 ° C and continued until the temperature of the reaction mixture reaches 115 ° C. 550-560 g (620-630 ml) of distillate are collected. The vapor temperature rises to 106 ° C.
    The hydrolysis of the reaction mixture was carried out at 115-120 ° C with stirring for 1.5 hours. The remaining hydrochloric acid was removed at Reduced Pressure. NII 150 mm Hg vacuum distillation until the internal temperature reaches 115 ° C and the vapor temperature is. About 10 g of distillate is removed. The content of hydrochloric acid is 8-9%.
    The residue obtained after vacuum distillation is between 145 and 155 g. This product is mixed with
    82820
    75 ml of hot water (80 - 00 ° C}, cooled. The precipitated crystalline product - N-phosphonomethylglycine is filtered and washed with water and / or alcohol - 5.
    After separation of the product, the mother liquor is neutralized with sodium hydroxide or potassium hydroxide (pH 10). As a result, triethylamine is released from triethyl-0-amine hydrochloride. Azeotrope with water is distilled off from the basic pH solution. 95% of the introduced triethylamine can be regenerated.
     5 Weight 68 g, yield 80%. M.p. 235- 236 ° C.
    Calculated,%: C 21.31; H 4.77; N 8.28; R 18,32.
    CjHgllOgP (mol. Mass 169.074) 20 Found,%: C 21.2; H 4.65; N 8.3; P 18.5.
    NMR spectrum (in D, 0 at room temperature): P-CH, 3.12 d (1 12 Hz);
    SI, 3.7 s. 25
    IR spectrum is identical with authentic sample. The data from high pressure liquid chromatography and thin layer chromatography are identical to those of an authentic sample 30.
    I
    Product purity: according to the complex titration data after the formation of the nitrosated derivative in accordance with spectrophotometry and polarography (min.) 98, 5%; high pressure liquid chromatography (min.) 98.211.5%.
    Material balance. 40 Injected substances, g:
    Methyl alcohol 400.0 Triethylamine47.0
    Para-Formaldehyde 30.0 Glycine37.5
    45 Dimethyl phosphite 55.0 Sol (acid) (35%) 246.0
    Total 815.0
    Substances obtained by distst 50 g, g:
    Distil t, selected at atmospheric pressure at 62- P5 ° C575.0
    55 Contents
    hydrochloric acid 17.0 methylal 36.6 chloromethyl 27.8 methyl alcohol 350.5
    Vacuum distillation v (66-72 C, 150 mm Hg)
    content
    hydrochloric acid gas produced by distillation Contents
    chloromethyl
    methylal: methyl
    alcohol
    The residue after distillation Contents
    hydrochloride
    triethylamine
    N-phosphonomethylglycine
    glycine
    H, H-bis-phosphonomethylglycine
    hydrochloric acid
    water
    Distillation losses
    815.5 total
    PRI mme R 2. The experiment was carried out by analogy with example 1 using 500 MP of anhydrous methanol containing 10% tetrahydrofuran, 47., 0 g (0.465 mol) of triethylamine, 30 g (1.0 mol) of para-formaldehyde , 37.5 g (0.5 mol) of glycine and 55.0 g (0.5 mol) of dimethyl phosphite. The pH of the reaction medium decreases from 6.3 to 5.8. 66 g of N-phosphonomethylglycine were recovered. Yield 80%. M.p. 229-232 C.
    Example 48.0 g (0.474 mol) of triethylamine and 30.6 g (1.019 mol) of para-formaldehyde are added to 500 ml of anhydrous ethanol at 78-80 ° C. 37.5 g (0.5 mol) of glycine was added to the mixture with stirring. Without isolating the N, N-bis-hydroxymethylglycine obtained in the reaction mixture, it was reacted with 69.0 g (0.5 mol) of diethyl phosphite. The pH of the reaction medium decreases from 6.3 to 5.8. Next, the experiment was carried out as described in Example 1. Yield 62 g (72%). Purity 97,, 5% (spectrometry nitrosated product). M.p. 234-236 ° C.
    - Example 4. In 1000 ml of anhydrous methyl alcohol, 35.0 g (0.875 mol of hydroxide natO) are dissolved.
    . -
    28282010
    During the 5 minutes, 36.0 g (1.2 mol) of para-formaldehyde was added to the solution heated by the evolving heat to 35-40 ° C. Depolymerization 5 occurs within 1-2 minutes. 82.5 g (1.1 mol) of glycine is added to the clear solution, after which the mixture is heated with stirring to.
    110 g (1.0 mol) of dimethylphosphite are added dropwise to the mixture over 5 minutes, and the solution is left standing for one hour at 68-70 ° C. During this time, the pH value decreases from 8.0 to 7, 0 The reaction mixture is cooled to 5 ° C, and the precipitated crystalline glycine is filtered off. 20 g (0.267 mol) of glycine are obtained, which can be reused. The filtrate is acidified with 330 ml (393 g, 4 mol) with 38% hydrochloric acid. The suspension is cooled to 10 ° C, the precipitated salt is filtered and washed with methanol. The dry weight of the obtained sodium chloride is 42 g. Next, the experiment is carried out as in Example 1. The weight of the distillate collected at atmospheric pressure is 1120 ml (1072 g) at a vapor temperature of 63-106 ° C.
    With vacuum distillation at a temp 5
    20
    25
    thirty
    Ature vapor 66-82 C get 46.4 g (45.0 mol) of distillate. The hydrochloric acid content is 6.9%. The residue after istillation is 105 g. In EU, the product is 97.6 g, purity 98.2%. M.p. 230 - 231 ° C. The yield calculated for dimethyl phosphite (DMF), 56.7% calculated for glycine, 68.5%.
    Material balance. Taken with a substance, g Methanol800,0
    Sodium hydroxide 35.0 para-formaldehyde 36.0 glycine82.5
    Dimethyl phosphite 110.0 Methyl alcohol for washing 60.0
    Hydrochloric acid (35%) 393.0
    Total 1516.5 Obtained substances, g Regenerated glycine20.0
    Sodium Chloride 42.0 Distil t obtained at atmospheric
    pressure 63-1About C
    1072.0
    eleven
    Content
    hydrochloric acid 33.2 methylal 24.7 methyl chloride 72.9 methyl alcohol 827.0 Vacuum distillation (66-82 C, 150 mm Hg) 46.4 content of hydrochloric acid 3, 2
    Distilled gas 126.1 Chloride content
    methyl61,4
    methylal 9.1 methanol 55.5 Distilled residue 200, 0 Content
    N-phosphonomethylglycine 122.4 N, K-bis-phosphonomethylglycine 7.9 glycine 6, O sodium chloride 9.1 hydrochloric acid 6.9 water 47.7
    12828
    ten
    /five
    20
    25
    thirty
    Distillation losses
    Total 200.0 10.0
    Total 1516.5 35
    Example5. 36.0 g (0.9 mol) of sodium hydroxide are dissolved in 1200 ml of anhydrous methanol. 48 g (1.6 mol) of para-formaldehyde are added to the solution, heated with heat, up to 35-40 ° C. After stirring for 5 minutes, 112.6 g (1.5 mol) of glycine was added, after which the mixture was heated to 60 ° C and PO (g) (1.0 mol) of dimethyl phosphite was added dropwise. The reaction mixture is heated for one hour at 68-70 ° C, while the pH decreases from 7.3 to 6.7. The reaction mixture is cooled to 28-30 ° C and 10 ml of glacial acetic acid is added dropwise. The precipitated glycine is filtered off for 10 s. 48 g (0.63 mol) of glycine are obtained, which can
    45
    use again. The filtrate is treated as described in Example 4. Product weight 117 g, purity 97%, mp. 228-230 ° C. Output designed for
    , - 55
    1282820
    12
    ten
    /five
    20
    25
    thirty
    35
    , -)
    45
    55
    DMF, 67.1% calculated for glycine, 78.1%.
    Example 37.5 g (0.9 mol) of metallic potassium are dissolved in 1300 ml of anhydrous methanol. 48 g (1.6 mol) of para-formaldehyde was added to the solution heated to 35–40 ° C, after which, after stirring for 5 minutes, .112.6 g (1.5 mol) glycine was added. The mixture is heated to 60 ° C and 110 g (1.0 mol) of dimethylphosphite is added dropwise. The mixture is kept at 68-70 ° C for one hour, while the pH decreases from 7.0 to 6.5. The mixture is cooled to 23 ° C and 10 ml of glacial acetic acid is added dropwise with stirring. The precipitated glycine is filtered at 10 ° C. 43.8 g (0.58 mol) of glycine are obtained, which can be used again. The filtrate is further processed as described in Example 4. The product weight is 124.5 g, purity 97.1%. M.p. 229-231 C. The output calculated for DMF, 75.8%, calculated for glycine, 82.4%.
    Example 7. To a solution of 500 ml of methanol, 98 g (1 mol) of potassium acetate and 30 g (1 mol), para-formaldehyde were added 37.5 g (0.5 mol of glycine) and then 55 g (0.5 mol) of dimethylphosphite, after which the mixture is stirred for one hour at 70 ° C. The solution is cooled to 20 ° C and 167 ml of concentrated hydrochloric acid is added while cooling.The mixture is further stirred at 5 ° C for 15 minutes, and The salt is filtered off. Next, the experiment was carried out as described in Example 1.
    Product weight 54-55 g, purity above 97%. M.p. 228-230 ° C, yield 63%.
    Example8. 19.5 kg (0.35 kmol) of technical purity potassium hydroxide are added to 500 liters of anhydrous methyl alcohol with stirring. 19.1 kg (0.64 kmol) of technical grade paraformaldehyde are added to the methanol base solution. Within 1-2 minutes, the solution becomes clear. 43.3 kg (0.58 kmol) of technical purity glycine is dissolved in the resulting solution, and the temperature of the reaction mixture rises to 60 ° C. To the solution thus obtained was added 42.3 kg (o, 38 kmol of dimethylphosphite during
    20-30 minutes, after which the reaction mixture is heated for one hour at 68-70 C. The pH of the medium decreases from 6.8 to 6.3. The solution is cooled to 28-30 ° C, 7 L of glacial acetic acid is added over 10-15 minutes. The precipitated glycine at 10 ° C slowly crystallizes for 0.5 h, after which it is separated in a centrifuge. After drying, 19 kg are obtained (0.25 kmol glycine, which can be reused.
    The cold solution is mixed with stirring and cooling with 154 kg (1.48 kmol) of a concentrated aqueous solution of technical purity hydrochloric acid. The precipitated potassium chloride crystallizes within 0.5 hours at 10 ° C. After that, it is separated in a centrifuge. Get 25 kg of potassium chloride (active content 94%). The reaction mixture is hydrolyzed for 2.5 hours with an aqueous solution of hydrochloric acid at 110-120 ° C, after which the excess amount of hydrochloric acid is removed by vacuum distillation. The residue after distillation is mixed with 57 liters of hot water (80-100 ° C), stirred, crystallized, centrifuged, and dried. 43.0 kg (0.26 kmol) of product are obtained. Purity 87.8% m.p. 229-232 C, output, calculated
    ABOUT
    five
    0
    five
    0
    on DMF, 68.4%, calculated for glycine, 86.8%.
    Example9. In a mixture of 500 ml of anhydrous methanol and 47 kg (0.465 kmol) of technical grade triethylamine, first 30 kg (1 kmol) of technical grade para-formaldehyde are dissolved and then 37.5 kg (0.5 kmol) of technical grade glycine at 68-70 ° s 55 kg (0.5 kmol) of dimethyl phosphite is added to the solution at 25–30 ° C over 25–30 min, and the reaction mixture is heated to 70 ° C for 1 h, while the pH decreases from 6.4 to 5.9. The resulting reaction mixture was added to 210 L of 30-32% technical hydrochloric acid. The solution is distilled until the mixture reaches a temperature of 100-120 ° C. The mixture is heated for 2 hours with stirring at this temperature, after which the excess amount of hydrochloric acid is removed by vacuum distillation. The residue is mixed with 75 liters of hot water (80-100 ° C) and cooled. The crystalline product is centrifuged and washed with water and methyl alcohol. Get 62-64 kg of product containing 97.8% of the active substance, So pl. 230-232 ° C, yield 73-74%.
    权利要求:
    Claims (3)
    [1]
    1. METHOD FOR PRODUCING N-PHOSPHONOMETHYLGLYCIN by reacting glycine with formaldehyde in the presence of a main agent in a solvent medium, followed by treatment of the obtained product with dimethylphosphite, acid hydrolysis with heating and distillation to isolate the solvent and by-products, characterized in that, in order to increase yield and quality of the target product, the interaction of glycine and formaldehyde is carried out at a molar ratio of the main agent and glycine (0.6-0.93): 1, glycine and formaldehyde 1: (2.06-1.1) in the absolute yutnogo methanol as a solvent, followed by treatment of the resulting reaction product is dimethyl or diethyl phosphite in a molar ratio of the latter to glycine, equal to (0,661,1): 1, at a temperature of 60-80 C, pH 5,8-8, and further acidification with strong acid to providing hydrolysis of the intermediate product - N-mohoalkylphosphonomethylglycine.
    [2]
    2. The method of pop. 1, characterized in that the process uses a 1.1-1.5 molar solution of glycine in methanol.
    [3]
    3. The method according to PP. 1 and 2, characterized in that in the process as the main agent use substances selected from the group: triethylamine, NaOH, KOH, potassium acetate.
    Priority on points 09.07.79 on pp. 1 and 2
    06.30.80 p. 3
    SU .4282820
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    同族专利:
    公开号 | 公开日
    FR2460959B1|1983-05-27|
    DD151945A5|1981-11-11|
    BR8004228A|1981-01-21|
    PL122749B1|1982-08-31|
    AT377263B|1985-02-25|
    YU175980A|1983-01-21|
    JPS6338035B2|1988-07-28|
    DE3025657A1|1981-04-09|
    CS244408B2|1986-07-17|
    HU184601B|1984-09-28|
    FR2460959A1|1981-01-30|
    CS486180A2|1985-09-17|
    PT71518A|1980-08-01|
    US4486359A|1984-12-04|
    JPS5668688A|1981-06-09|
    CH646180A5|1984-11-15|
    DK171469B1|1996-11-11|
    DK294880A|1981-01-10|
    PL225540A1|1981-06-19|
    YU42347B|1988-08-31|
    DE3025657C2|1992-03-05|
    ATA357480A|1984-07-15|
    引用文献:
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    申请号 | 申请日 | 专利标题
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