• 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:
    Phosphorus containing flame retardants are prepared by a two step process having as essential steps: 1. reacting diorgano organophosphonate with reactant comprising phosphorus oxide reagent to yield a metaphosphate/phosphonate reaction product, and thereafter; 2. reacting the reaction product of step (1) with reactant comprising epoxide to yield poly(oxyorganophosphate/phosphonate) product. Selected novel poly(oxyorganophosphate/phosphonate) products contain a backbone structure of repeating units represented by the average formula: wherein m is an integer from 1 to 50; R, R1, and R2 are individually selected from saturated hydrocarbon radical, alkaryl radical, aralkyl radical, and aryl radical; and R3 is: wherein R4 R5, R6, and R, are individually selected from hydrogen atom, hydrocarbon radical, and halogenated hydrocarbon radical. Articles and compositions such as textiles and polyurethanes are rendered flame retardant by incorporation of poly(oxyorganophosphate/phosphonate) prepared by the process of the invention particularly products of Formula (I).
    公开号:SU952110A3
    申请号:SU792754154
    申请日:1979-04-19
    公开日:1982-08-15
    发明作者:Бертон Фиринг Ральф
    申请人:Стауффер Кемикал Компани (Фирма)；
    IPC主号:
    专利说明:

    () METHOD OF OBTAINING POLYES (OXYORGAN Phosphate) The invention relates to methods for producing flame retardants based on phosphonates and can be used to create fire resistant polymeric materials. A known method for the preparation of phosphorus-containing flame inhibitors, which are formed as a result of the condensation of beta-haloalkyl esters of ACIDS, containing pyvalent phosphorus 1. The closest to the proposed chemical structure of the resulting inhibitors is a method for producing polyorganophosphate phosphonates by condensation of beta-haloalkyl phosphate and dialkyl phosphonate, which results in a condensation product that does not contain halogen f23 In the known methods for the preparation of combustion inhibitors, condensation-type reactions that do not include all of the starting reagents are used in the final product. Organic compounds
    PHOSPHONATE follicles are cleaved during the reaction, therefore in this case a purification step or a step of extracting such products is necessary. Reactions of the type of condensation in, preferably proceed at elevated, ambient temperatures. Since these reactions are endothermic, additional energy is required in the reaction system. The purpose of the invention is to simplify the process technology. The goal is achieved by the fact that according to the method of producing poly (oxioorganophosphate) phosphonate by reacting a dialkyl alkyl phosphonate with a phosphorus-containing compound, dimethyl methyl phosphonate (DMMP) is used as a dialkyl alkyl phosphonate and a phosphoric acid is needed for a phosphoric acid phosphate phosphate. with phosphoric anhydride or with phosphoric anhydride, followed by treatment with alcohol at a molar ratio of DMMP and phosphorus 1-2.5 1, and in the second stage, the metaphosphate phosphonate (-MFc) obtained in the first stage is reacted with ethylene oxide or a mixture of ethylene oxide and alcohol. Preferably, the first stage is carried out using an alcohol in an amount not exceeding 1 mole of hydroxyl groups per 3 mol of the anhydride structural unit metaphosphate phosphonate. i Preferably, the second stage is carried out at a ratio of 0.8-1.3 mo of ethylene oxide per 1 gram-atom of phosphorus in the metaphosphate phosphonate, the first and second stages are carried out by heating in the temperature range of 25 Л20 ° C. The first step is carried out in the presence of a catalytically active Lewis acid or Lewis base. It is also preferable to use alcohols, identical or different, used in the first and second stages to choose from the group including primary monohydric aliphatic alcohols, halogenated alcohols and phenols. Phosphoric anhydride serves to break polymer chains, and does not take part in the reaction in the first stage. The relative proportions of the reagents, expressed in molar ratio of diorganoorganophosphonate to, generally vary in the range from 1: 1 to not more than 2.5: 1. A certain choice of reagent proportions is one way of providing the necessary degree of polymerization of the reaction product in the first stage. Small proportions give high molecular weight and high viscosity products. The minimum average number of phosphorus atoms a reaction product should contain in the first stage is three, but there is no upper limit for this indicator, except for some practical reasons for the convenience of working with the product obtained. Another way to provide the required degree of polymerization for the first stage of the reaction product is to introduce alcohol into the reaction system. Alcohol acts as a catalyst for the formation of a meta-ester reaction product. It also has a low molecular weight structure. The reaction with alcohol can be illustrated using the equation 000oo IIII II con 11II P-0-P-O-P- -P-0 -HO-P-0IIIII CHj QCH, OCitj --- JJ 3 Alcohol can be added as and after the reaction of diorganoorganophosphonate and Rj Od-. Alcohol should be used in proportions not exceeding 1 mol of hydroxyl groups per 3 mol of phosphoric anhydride blocks in the polymer chain in order to maintain a minimum average content of chains containing three phosphorus atoms in the final product. The first stage reaction product contains -P / 0 / -0-P- / 0 / - as the main chain and is a viscous liquid. In general, it is not necessary to purify the reaction product obtained in the first stage before using it in the reactions in the second stage. In the second stage, the metaphosphate / phosphonate ester is reacted with a heterocyclic reagent, i.e. ethylene oxide. The reaction product from the first stage can also react with both alcohol and epoxide at the same time, resulting in the formation of substituted phosphorus polyesters. Epoxides are presumably attached to the metaphosphate / phosphonate ester, resulting in the formation of poly (hydroxyorganophosphate phosphonate - structures such as -P- (OK) -0 - P- and -P- (OR) -OH Reacting to the second The steps can be carried out using only epoxide and metaphosphate / phosphonate ester as reagents. In order to change the structure of the final product, compounds containing a hydroxyl group, such as water or alcohols, can preferably be added to the second stage reaction system. sfat / phosphonates are easily saturated with alcohols, resulting in a reaction product with a higher content of hydroxyl groups and a lower molecular weight. Other necessary end groups, such as branched chains containing carbon or halogen, can also be obtained from the structure of the alcohol. Specific alcohols that are used in accordance with the inventive method are methanol, dibromopropanol, dibromoopentylene glycol, ethoxylated tetra bromobisphenol A, pentaerythritol t. The use of alcohols to remove acidic structures is known. I. The reaction can proceed without a catalyst, if it is necessary to obtain a product containing high concentrations of groups of cyclic esters. The use of a catalyst in the presence of an epoxide reveals cyclic esters and attaches them to the poly / oxyorganophosphate / phosphonate backbone. The use of a catalyst further reduces the time and temperature required to achieve the desired reaction rates. Lewis acids and bases are used as catalyst in amounts from about 0.01 to about 10% by weight. Suitable catalysts include the following compounds: aluminum chloride, alkali metal oxide hydrates, tetrads, isopropyl) titanate, alkali metal ethylate, sodium methyl carbonate, butyl lithium, alkali metal phosphate, boron trifluoride etherate, tr1 boron fluoride, zinc chloride, antimony trifluoride, sodium borohydride. The reaction time in both the first and second stages can vary from a few minutes to several days. Pressure is not a decisive factor, and both the first and second stages generally proceed at atmospheric pressure. For some reagents, such as ethylene oxide, it is preferable to use an elevated pressure, since all the reagents are liquid. The residual acidity of the reaction product obtained in the second stage can be neutralized. help of post-treatment with alkylene oxides. The undesired color of the reaction product can be removed by incorporating from about 0.01 to about 2.0 weight in the reaction mixture 06; organic phosphite, for example trimethylphosphite. The progress of the reaction can be traced through sample extraction and property studies, such as viscosity, density or reaction heat release rate. The reactions in the first and second stages are carried out in the liquid phase using the reagents themselves as the reaction medium. Inert compounds such as liquid aliphatic, aromatic and halogenated carbons can be used as the reaction medium. After completion of the reaction, poly (the hydroxyorganophosphate phosphonate ester can be purified using various known methods. The by-products, inert reaction medium and unreacted materials, if any, can be removed using known methods such as sparging, distillation. Under vacuum, distillation steam, thermal fractionation and solvent extraction. The proposed method can be implemented using known reaction vessels having inlets, outlets, means t The materials are exported and the necessary means for mixing, ensuring the specified temperatures and pressures. As a result of this process, a polyoxyorganophosphate) phosphonate is formed with repeating units having the formula O00 IIII -OC HCO-OOCO OO-OC tti O snE0 3 Jm where 1 to 50. The molecular weight, viscosity, phosphorus content and purpose of the products obtained according to the inventive method can vary widely. The main properties of the products and the boundaries for the composition of the compositions are as follows: Viscosity, cP600-60000 Phosphorus content, weight.– 13-23
    795
    Hydroxyl number
    Acid number 0.5-10
    or higher
    Preferred products include poly (oxyorganophosphate) phosphonates, which are non-functional or have low hydroxyl functionality, i.e. hydroxyl numbers from 1 to 50,
    Poly (oxyorganophosphate) phosphonates are used to impart flammable properties to flammable materials. Typical materials that require flame retardants (flame retardants) are molds, castings or laminates, coatings, sheeting, bonding agents, structural materials, elastomers, foams, interlayers and textiles. Effective amounts of a flame inhibitor that must be used to process a particular material can be easily determined using one or more experiments (standard incineration texts). The product, the total content of phosphorus in which exceeds 0.7 wt., Has the property of inhibiting the flame. Inhibitors C flame retardants can be used in combination with other flame retardants, antistatic agents, water repellents, dyes, etc.
    Poly (oxyorganophosphates) phosphonates can be chemically or physically applied to materials that may be exposed to fire. A physical combination can be obtained simply by mixing or dissolving a poly (oxyorganophosphate) phosphonate, a flame inhibitor in other materials.
    Poly (hydroxyorganophosphate) phosphonates can also be used as substantially non-volatile impregnating materials for porous products or cellulose products such as paper, wood, plywood, boards, chips, and other similar materials.
    Example 1.8 A 12-liter 3-necked glass flask was charged with 2710 g DMMA (21.85 mol and 2710 g Pj Or 19.08 mol). The reaction proceeds slowly with stirring at 25-80 0. Then for 1 h the temperature is maintained at 60-90 C, for SL / 60 C, the obtained meta 108
    phosphate phosphonate is treated with 620 g of ethylene glycol (10 mol; trimethyl phosphite (1 g) is added to the mixture to remove the color. The temperature is then maintained at 70- 80 ° C for 1 hour, then ethylene oxide is fed into the reaction zone for approximately 15 hours at 50-60 ° C. Al g of tin-divalent octoate is added to the mixture, and the flow of ethylene oxide continues until acid number 3 is reached. The yield is g, the hydroxyl number is 129. The product contains 20 phosphorus.
    Example 2. Dimethylmethylphosphonate, 5 g, 5. mol) is gradually charged at 25-80 ° C with individual portions of phosphorus pentoxide {total weight 677.5 G, 77 mol). Then for 1 h, the temperature is maintained at 87C. The metaphosphonate / methylphosphonate is slowly treated at 50-55 ° C using ethylene glycol Q155 g, 2.5 mol). To remove the color, 1 cm of trimethyl phosphite is added to the mixture. Ethylene oxide is fed to the mixture for about 15 hours at 60-65 ° C, resulting in the formation of 2290 g of product with an acid number of 13.2 and a hydroxyl number of 130. The phosphorus content is 20.3%.
    Example 3. 3000 g of DMMP (2.2 mol) are reacted in portions with 3000 g of P (2, mol, heated and maintained at 97-99 ° C for 1 hour. Then ethylene glycol is slowly added (678, g, 11, 1 mol at 56-60 0 and the mixture is kept for 1 hour. Ethylene glycol is fed at 57 C. Further, before the end of the reaction, this stage is catalyzed by adding 50 g of divalent tin octoate, followed by the addition of ethylene oxide, the acid number decreases to 1 ,. the product is 10720 g, the hydroxyl number is 126, the phosphorus content is 19.9.
    An example. Methylmetaphosphate methylphosphonate is prepared in accordance with Example 1 from the same amounts of DMMP and. Then, 660 g of this anhydride containing 2.66 mol of methylphosphonate and 65 mol of phosphorus in the form of phosphate are heated together with portions of ethoxylated tetrabromobisphenol A at 60-70 C. In total, 5b9 g (0.9 mol) of this diol is used. 9. Ethyl oxide is added at the same time during the addition to reduce the high viscosity of the mixture. After that, 8 g of divalent tin octoate is added as a catalyst and everything is completed with a stage of neutralization with ethylene oxide at 100 ° C. 1b23 g of the product is diluted with 7 g of isopropanol. The product contains TK, phosphorus and 17.1 bromine. Example 5. Dimethylmethylphosphonate (g, 2 mol) reacts in portions at 30-C0 C with 285 g of phosphorus pentoxide (2 mol). The resulting metaphosOat / methylphosphone is further heated to 92 ° C and maintained at this temperature for 1 hour, then heated to 120 ° C for a short time. The mixture is then cooled to 75 ° C, 217 g of di-bromopropanol (1 mol) and then for another 1 h maintain the temperature at 80–30 ° C. Ethylene oxide is fed at 95 10P-C. When the acid value with methanol drops to 0, 2k CM of concentrated hydrochloric acid is added dropwise to the product at 50 ° C in order to remove 1 mol of methyl ester groups. After keeping the mixture for 3 hours at 50-8 ( ) With a vacuum of 20 mm Hg. The acid number is increased to 105. Neutralization with ethylene oxide lowers the acid number to 0.8 mg KOH / g. The product yield is g. It holds 16.2% phosphorus,% bromine. The hydroxyl number is increased by an acid hydrolysis step to more than 170 mg KOH / g. Example 6. 500 g of dibromopropyl polyethylene phosphonate from Example 5 are heated to, treated with 13 g of concentrated hydrochloric acid. After maintaining the temperature for 2 hours and reduced pressure, the product is neutralized at 80-100 with ethylene oxide, with 0.5% divalent tin octoate being used as the catalyst. The yield is 552 g with an acid number of 1.0. The product contains k, 6 ° phosphorus and 12; 6 | bromine. Example 7. DMMP (g, b MOL) is subjected to interaction in portions with 709 g of P1 molar phosphate, After incubation for 1 hour at 85 ° C, part of the mixture (8 g) is treated at 70-8 ° C 0.10. in portions (a total of 283 g of dibromoneopentylene glycol for 3 / h. After keeping the mixture for 1 hour at IO-83 ° C, ethylene oxide is fed at 80 ° C until the reaction is complete, and for a short time the mixture is heated to 100 C. The yield of the product is 983 g (which corresponds to approximately 1.29 mol of epoxide per 1 phosphorus atom.) The acid number of the product is 15 mg of phosphorus and bromine. Example 8. DMNP (659 g, 5.3 mol) is processed in portions mi (628 g, (, 42 mol) at 25–70s with p-hydroxy oxide. After aging for 1, 5 h at 79 C this anhydride is slowly treated at 6 ° C with methanol (, 2 g, 2.32 mol). Even after 1 hour, during which the temperature is maintained at 70 ° C, the mixture is treated with a stream of ethylene oxide at 3–6 ° C. The ethoxylation is carried out just before completion. Reactions. Finally, 1 O g of divalent tin octoate is added and neutralization is continued until the acid number is 5.5. The product has a weight of 1986 g and the consumption of ethylene oxide is 1. 5 mol. The product contains 20.5 phosphorus, hydroxyl number. 61. Example 9. 962.8 g (10.6 grammatoms of phosphorus metaphosphate / phosphonate from the first stage of Example 7 are slowly treated at 70-120 ° C with 20 g of pentaerythritol (1.5 mol). Trimethyl phosphite C1 is added to remove color cm). Ethylene oxide is served at 70-100 ° C. Next, 5.6 g of divalent tin octoate is added. After oxyethylation, nitrogen sparging is carried out, 15 g of a known diepoxide stabilizer are added and a yield of 1827 g of phosphorus-containing product is obtained, with an acid number of 4.0 and a hydroxyl number of 220. Example 10. 10 mol (g, dimethyl methyl phosphonate is treated with 3.33 mol (73 d) phosphorus pentoxide and the reaction is carried out for 1 hour at 80 ° C. The reaction mixture is then treated with oxide, ethylene at 60-100 ° C. The acid number of Sme-, then HCl) is 8.2. Unreacted DMF 280 g) is distilled from the reaction product.
    119521
    resulting in a ratio of DMMP to phosphorus pentoxide equal to 2.32, Next (ethylene glycol 6.7 g) is added to the reaction mixture, and then ethylene oxide is fed. The final S product has an acid number of 3.5, a viscosity of 650 cP, a hydroxyl number of 12.2, and a phosphorus content of 21, (and in this example, as in others, the percentages are by weight).
    (Formula of invention
    权利要求:
    Claims (6)
    [1]
    1. A method of producing poly (oxyorganophosphate of a phosphonate by reacting a dialkyl alkyl phosphonate to a citrus-based ctop compound, characterized in that, in order to simplify rexHOrtcwHijA-n ouecca, dimethyl (41-methylphosphate) is used as a phosphoryl alkyl phosphonate, as phosphoryl alkyl phosphonate, dimethyl (41-methylphosphate) is used as phosphor alkyl sulfonate, with phosphoryl alkyl phosphonate being dimethyl | , in the first stage, dimethylmethylphosphonate is reacted with phosphoric anhydride or with phosphoric anhydride, followed by treatment with alcohol at a molar ratio of dimethyl . Methylphosphonate and phosphoric anhydride, equal to U-2.5): 1, and in the second stage, the metaphosphate phosphonate obtained in the first stage is subjected to interaction with ethylene oxide or a mixture of ethylene oxide and alcohol.
    1012
    [2]
    2. The method according to claim 1, wherein the first stage is carried out using an alcohol in an amount not exceeding 1 mol of hydroxyl groups per 3 mol of the anhydride structural unit of the metaphosphate phosphonate.
    [3]
    3. The method according to claim 1, wherein the second stage is carried out at a ratio of 0.8-1.3 mol of ethylene oxide to 1 gram-atom of phosphorus in the metaphosphate phosphonate.
    [4]
    4. Pop-up method, 1, which is characterized by the fact that the first and second stages of the process are carried out with heating in the temperature range of 25-120 seconds.
    [5]
    5. Method pop. 1, and in that the first step is carried out in the presence of a catalytically active Lewis acid or Lewis base.
    [6]
    6. The method according to claim 1, which is distinguished by the fact that alcohols, the same or different, used in the first and second stages, are selected from the group including primary mono-polyhydric aliphatic alcohols, halogenated alcohols and phenols.
    Sources of information taken into account in the examination
    To US Patent No. 3891727, CLO 260-928, published. 1976.
    2. UK Patent If 1 68053 cl. C 2 P, pub. 1977 (prototype)
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    同族专利:
    公开号 | 公开日
    EP0005329B1|1982-06-09|
    EP0005329A1|1979-11-14|
    DE2963057D1|1982-07-29|
    ZA791374B|1980-04-30|
    IL56877D0|1979-05-31|
    CA1140567A|1983-02-01|
    IL56877A|1982-09-30|
    JPS5853657B2|1983-11-30|
    DK162979A|1979-10-21|
    DD143076A5|1980-07-30|
    JPS58117272A|1983-07-12|
    US4199534A|1980-04-22|
    JPS54140000A|1979-10-30|
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    US3099676A|1961-11-03|1963-07-30|Union Carbide Corp|Hydroxyalkyl polyphosphates|
    US3639545A|1968-03-26|1972-02-01|Dow Chemical Co|Process for making cyclic alkylene phosphate alkylene esters|
    BE789815A|1970-03-27|1973-04-06|Stauffer Chemical Co|VINYLPHOSPHONATES COPOLYCONDENSES AND THEIR USE AS INFLAMMATION-DELAYING AGENTS|
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    AR206903A1|1973-11-12|1976-08-31|Stauffer Chemical Co|COPOLICONDENSATION PRODUCT OF A TRIS-BETA-HALOALKYLPHOSPHATE AND A DIALKYL PHOSPHONATE USEFUL AS A FIRE RETARDING AGENT|
    US3959415A|1974-05-28|1976-05-25|Stauffer Chemical Company|Methods of preparing stable condensation products and products therefrom using an alkylene oxide treatment|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/898,241|US4199534A|1978-04-20|1978-04-20|Polyand process for preparing|
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