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    • 专利摘要:
    1519929 Red phosphorus HOECHST AG 27 May 1977 [17 July 1976] 22500/77 Heading C1A Stabilized pulverulent red phosphorus comprises a homogeneous blend of red phosphorus particles with a size of at most about 2mm and as an oxidation stabilizer a metal compound of the second or third group of the Periodic System, the metal compound being the aluminium, magnesium, calcium or zinc salt of an alkyl-, cycloalkyl-, aryl- or aralkyl-phosphonic acid having 1 to 20 carbon atoms, the metal compound being present in the homogeneous blend in a proportion of 0À5 to 5 weight per cent. Red phosphorus particles may-be intimately blended with 0À5 to 5 weight per cent, based on red phosphorus, of an alkyl-, cycloalkyl-, aryl- or aralkyl-phosphonic acid having 1 to 20 carbon atoms; the blend suspended in water and the suspension heated to 60 to 95‹ C.; the suspension gradually admixed with at least stoichiometric proportions of an aqueous solution of a water-soluble aluminium, magnesium, calcium or zinc salt to cause precipitation of the respective phosphoric acid salt from the aqueous suspension at a pH of 3À0 to 6À0 and preferably at a temperature of from 80 to 90‹ C.; the resulting mixture filtered, and the filter residue dried at elevated temperature, suitably at 80 to 130‹ C., and if desired, under reduced pressure. Preferred water-soluble salts are Al 2 (SO 4 ) 3 .18H 2 O, Ca(NO 3 ) 2 .4H 2 O, ZnSO 4 .7H 2 O and MgSO 4 .7H 2 O, which may be used in the form of 5 to 20 weight per cent aqueous solutions. The aluminium salt is suitably precipitated at pH 3À0 to 3À5 and the salts of the other metals at pH 5À0 to 6À0.
    公开号:SU999962A3
    申请号:SU772503099
    申请日:1977-07-15
    公开日:1983-02-23
    发明作者:Штендеке Хорст；Даний Франц-Иозеф；Кандлер Иоахим；Ауэль Теодор；Клозе Вернер
    申请人:Хехст Аг (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR STABILIZATION OF POWDERED RED Phosphorus
    one.
    The invention relates to stabilization of marginal phosphorus, which is widely used in chemical engineering.
    A known method of stabilization of powdered edge phosphorus, including the treatment, is captured with aluminum hydroxide and then with a 10% solution of sodium bicarbonate heated to 55 ° C. Next, the suspension is filtered and the residue is dried 1. (O
    The disadvantage of the long-term method is the high content of impurities in phosphorus introduced during stabilization, which limits the areas of its further use. "5
    There is a method of stabilization of powdered red phosphorus, including the suspension of red phosphorus in water 0.04 n. sodium alkshinat solution, followed by blowing the suspension into JQ for 10 hours with air at 85-9 ° C, filtering the suspension, washing the precipitate and drying it in vacuum C23.
    The disadvantage of the method is low. This is the degree of stabilization of red phosphorus, since at high temperatures the stabilizer cleaves the water, which leads to a decrease in the concentration of phosphate.
    The aim of the invention is to increase the degree of stabilization of powdered red phosphorus.
    The goal is achieved according to a method for stabilizing powdered phosphorus, including treating it with a reagent, followed by separating and drying the product, in which salt selected from the following is taken as a reagent: aluminum sulfate, magnesium sulfate, zinc sulfate, calcium nitrate and propanophosphonic acid or its derivatives : octave-, or dodecab - -, or benzene-, or 2-phenyletha-1-, or 2-phenylethyl -1-, or 2-carboxyethane-1-, or shpsloheksan-, or vinyo-, or 2-chloro9ta -1-, introduced in an amount to ensure the content of the products of the reaction s in a mixture equal to O, 5-5, O wt.%.
    Introduction of an additive less than 0.5 wt.% Does not provide a sufficient degree of stabilization of red phosphorus, the introduction of 3D9 additives more than 5.0 wt.% Is impractical. The proposed method of stabilization allows the use of red phosphorus in plastics at a temperature of 250 ° C. for plastics. Example 1. 100 g of finely divided red phosphorus with an average particle size of 0.05 mm is suspended in 500 ml of water. With stirring, the scientific research institutes are heated to 90 ° C, treated with 2.5 g of octanephosphonic acid and a solution of 5 g of APgC304) 3 aZNHO in 100 ml of water. One hour after the end of the reaction, the aqueous suspension is filtered, the residue is washed with water and dried at 80 ° C in a stream of nitrogen. Red phosphorus will contain 2.8 wt.% Stabilizer. The stability of red phosphorus is determined by placing 1 g of the latter together with 450 ml of water in a three-neck flask equipped with a gas supply tube, a thermometer, a reflux condenser, and a magnetic stirrer. The mixture is heated to 80 ° C and 10 l of oxygen per hour is fed into the flask with constant stirring. The reflux mixture of gases consisting of oxygen and phosphorus hydrogen, which was formed by disproportioning red phosphorus, in addition to phosphoric acids of varying degrees of phosphorus oxidation, is sent through two successively connected bottles that are filled with 100 ml of 5% by weight water. With a solution of mercury chloride (I). In this case, hydrogen phosphide reacts with mercury chloride (s) according to the equation () + knowledge. As an indicator of the stability to the oxidation of red phosphorus, the amount of phosphorus oxoacids contained in an aqueous red suspension of phosphorus, as well as contained in leaching bottles for hydrochloric acid gas, serves. Content of phosphoric acids and sol. Acidic acid is determined by titration. Example 2. The stabilization of phosphorus is carried out according to Example 1. However, instead of octanephosphonic acid, 2.5 g of decanephosphonic acid are introduced. The content of the stabilizer is 2.7 wt.%. 2 Example 3. The phosphorus is stabilized analogously to example 1, however, instead of octanephosphonic acid, 2.5 g of dodecanophosphonic acid is introduced. The content of the stabilizer is 2.8 wt.%. Example 4. YuO g finely ground red powder of phosphorus with an average particle size of 0.05% is packed into 500 ml of water. With stirring, the suspension is preheated until it is treated with 2.5 g of 2-phenylete 1-phosphonic acid and a solution of 5 g of Ae2 (5O) 2-18H2O in 100 ml of water, for -. those injected with a 5% solution of sodium hydroxide and the pH of the mixture adjusted to 3.5. After 1 h after completion of the reaction, the aqueous suspension is filtered, the residue is washed with water and dried at 8 ° C in a stream of nitrogen. The stabilizer content is 2.9 wt.%. Example 5. 100 g of finely ground red phosphorus powder. The average particle size of 0.05 mm is suspended in 50O mm of water. With stirring, the suspension is heated to 9 ° C, treated with 2.5 g of octanephosphonic acid and a solution of 5 g. Ca (LO3) 2 4H2O in OO ml of water, then solutions of 5% sodium hydroxide solution are added and the pH of the mixture is adjusted to 5.5. After 1 h after the end of the reaction, the suspension is filtered, the residue is washed with water and at 8 ° C. a stream of nitrogen. Ct holding the stabilizer is 2.9% by weight. Example 6. The stabilization of phosphorus is carried out according to Example D; however, instead of calcium nitrate, 5 g of MiySO./ X 7H2O are taken. The stabilizer content is 2.7% by weight. EXAMPLE 7 Phosphorus is stabilized according to Example 5, with 5 g of Zn504) 7H2O being taken instead of calcium nitrate. The stabilizer content is 2.8% by weight. Example 8 (comparative). Analogously to example 1, the stability against oxidation of untreated red phosphorus ground into fine powder was tested. Indicators of stability to oxidation of the treated red phosphorus are given in table. one.
    Table 1
    The degree of oxidation of phosphorus is characterized by the amount of phosphorous hydrogen produced (mg).
    The degree of acidity of aqueous phosphorus-containing suspensions is due to the formation of phosphoric acids in the oxidation of red phosphorus (mg KOH / g - h).
    Example 9. 14O g of an aqueous phosphorus-containing gruel containing marginal phosphorus 1OO g is dissolved in 360 ml of water, 5% hydrochloric acid is added to pH 3 and after adding 5 g of 2 g of phenethylethylene-phosphonic acid with constant stirring, the temperature of the mixture is raised before . Then, a solution of South A 82 (304) 3-18H2O in 1OO ml of water is added dropwise within 30 minutes, and the pH is adjusted to 3.5 with 5% sodium hydroxide solution. After 1 h after completion of the reaction, the aqueous suspension is filtered, the residue is washed with water and dried under a stream of nitrogen. The stabilizer content is 2.8% by weight.
    Examples 10-1 €. Stabilization is carried out in accordance with Example 9, and in each case 2-synthetic 8-1-phosphonate acid. take follow-up derivatives of phosphoric acid: dodecanphosphonic acid, stabilizer content -4.8 air-feed.% (example 10); 2 -Erboxy-1-lbfonoic acid, stabilizer content 4.9 wt.% (Example 11); cshslohexanephosphonic acid, stabilizer content 4.7 wt.% (Example 12); viiylphosphonic acid, stabilizer content 4.7 wt.% (Example 13); 2-chloroform & -1-4ophooic acid, content of stabilizer 5, O wt.% (Example 14); propa 1phosphonic acid, the content of the stabilizer; 5, About wt.% (example 16).
    In the example, the stabilizer ve input is
    The indicators of stability against oxidation are processed), thus the red phosphorus is given in table. 2
    权利要求:
    Claims (2)
    [1]
    TABLE 2 79999 Formula of the invention A method of stabilizing powdered red phosphorus, including treating it) with a reagent followed by separating and drying the product, is required in order to increase the degree of stabilization as a reagent take the salt selected from the series - aluminum sulfate, magnesium sulfate, “O zinc sulfate, calcium nitrate and propane phosphonic acid or its derivatives, octane, or dodecane, or benzene, or 2-phenylethyl-1, or 2 Fe; Nilethylene-1-, 628 or 2-carboxyegan-1-, or cyclohexanil vinyl, or 2-chloroethane-1-, introduced in an amount that provides the content of the reaction products in a mixture of 0.5-5, about wt.%. Sources of information taken into account in the examination, (.dtneSins Handbucti der anortjanisclien Ctimie 6. AufP-j-fSH, Phosptior, TeiK B, 5eite 83, VerBa: j Cliitnie, l / eitilieivn / Berc strofie.
    [2]
    2. US patent No. 2359243, cl. 427-215, 1968.
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    同族专利:
    公开号 | 公开日
    DE2632296C2|1979-02-01|
    JPS6037043B2|1985-08-23|
    DD131742A5|1978-07-19|
    DE2632296A1|1978-01-19|
    US4113841A|1978-09-12|
    DE2632296B1|1978-06-01|
    CA1074981A|1980-04-08|
    JPS5311193A|1978-02-01|
    IT1079788B|1985-05-13|
    GB1519929A|1978-08-02|
    SE416540B|1981-01-19|
    SE7708205L|1978-01-18|
    IN146212B|1979-03-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US1433100A|1921-12-22|1922-10-24|Essex Specialty Co Inc|Phosphorus compound|
    US2132996A|1936-02-12|1938-10-11|Samuel D Ehrlich|Ignition and priming compound|
    US2399120A|1941-02-24|1946-04-23|Rohm & Haas|Stable red phosphorus|
    US2635953A|1947-10-08|1953-04-21|Martin S Silverstein|Inflammable compositions including red phosphorus|
    DE1567629B1|1966-06-24|1970-05-27|Knapsack Ag|Process for impregnating red phosphorus|
    DE2249638B2|1972-10-11|1981-01-15|Hoechst Ag, 6000 Frankfurt|Phlegmatized red phosphorus|DE2813151A1|1978-03-25|1979-09-27|Hoechst Ag|STABILIZED RED PHOSPHORUS|
    US4163682A|1978-10-05|1979-08-07|The United States Of America As Represented By The Secretary Of The Navy|Method for disposing of red phosphorus composition|
    DE2945118C2|1979-11-08|1981-12-03|Hoechst Ag, 6000 Frankfurt|Stabilized red phosphorus and process for its manufacture|
    CA1178788A|1982-06-29|1984-12-04|Erco Industries Limited|Stabilization of red phosphorus|
    DE3342640C2|1983-11-25|1987-01-02|Hoechst Ag, 6230 Frankfurt, De|
    GB8611357D0|1986-05-09|1986-06-18|Ciba Geigy Ag|Flame retardent polymer compositions|
    DE3710170A1|1987-03-27|1988-10-13|Hoechst Ag|STABILIZED RED PHOSPHORUS AND METHOD FOR THE PRODUCTION THEREOF|
    US4841865A|1987-06-17|1989-06-27|Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of National Defence|Smoke composition and method of making same|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE2632296A|DE2632296C2|1976-07-17|1976-07-17|Stabilized red phosphorus and process for its manufacture|
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