A method for preparing a hybrid macromolecular phosphorus-containing flame retardant

Abstract

The application relates to a preparation method of a mixed macromolecular phosphorus-containing flame retardant, and belongs to the technical field of flame retardant material production. The method comprises the following steps: S1, placing phosphorus oxychloride and a catalyst in a reaction kettle, replacing the air in the reaction kettle with N2, stirring uniformly, then putting glycidyl ether into the reaction kettle, and reacting at 50-110 DEG C for 4-8 h, and then cooling to room temperature; S2, introducing oxyalkylene into the reaction kettle to react, the temperature in the reaction kettle is increased and maintained at 50-100 DEG C by controlling the feeding speed, and the pressure is increased and maintained at 0.1-0.5 Mpa; S3, sampling in the middle, when the acid value of the product is lower than 0.5 mgKOH / g, the introduction of oxyalkylene is stopped, the reaction is continuously carried out until the pressure in the reaction kettle is reduced to a constant pressure, then aging for 2 h, removing low-boiling substances, and obtaining a crude product; S4, washing to neutral with lye, washing with distilled water, and dehydrating under negative pressure to obtain the product. The preparation process of the flame retardant is simple, the reaction condition is mild, the yield is high, the cost is low, and the migration rates of phosphorus and chlorine in the product are low.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of production of flame-retardant materials, and particularly relates to a production process of a mixed macromolecular phosphorus-containing flame-retardant. BACKGROUND

[0002] Phosphate ester flame retardants are widely used in plastic foam processing due to their low price and abundant resources. The phosphate ester flame retardants on the market at present mostly belong to monophosphate liquid additive flame retardants, such as trichloroethyl phosphate (TCEP), trichloroisopropyl phosphate (TCPP) and the like. However, they have small molecular weight, low decomposition temperature, poor thermal stability and easy migration, and thus are prone to volatilization and decomposition in the application process, which greatly affects the performance of the products.

[0003] Macromolecular phosphates overcome the shortcomings of monophosphates, have large molecular weight, low migration rate, hydrolysis resistance, low fogging and low yellowing, and have gradually become a research hotspot in the field of flame retardants in recent years.

[0004] The macromolecular phosphorus-containing flame retardants that are currently a research hotspot mostly are polymeric flame retardants or monomer macromolecular flame retardants. Patent CN115960330A provides a polymeric macromolecular flame retardant and a preparation method thereof. Dimethyl methylphosphonate and ethylene glycol are subjected to ester exchange and polycondensation reactions in sequence to obtain polyethylene glycol methylphosphonate oligomers, and then the polyethylene glycol methylphosphonate oligomers are subjected to condensation reaction with diphenylmethane diisocyanate carbodiimide to prepare polymeric macromolecular flame retardants with a weight average molecular weight of 5900-20000.

[0005] Patent CN102627771A discloses a preparation method of a pentaerythritol diphosphate dichlorophosphoryl chloride ethylenediamine macromolecular flame retardant. First, pentaerythritol diphosphate dichlorophosphoryl chloride is obtained by reacting phosphorus oxychloride with pentaerythritol. Second, the pentaerythritol diphosphate dichlorophosphoryl chloride is dissolved in dimethylformamide to obtain an intermediate solution, and ethylenediamine is added dropwise to the intermediate solution, which is heated to 150-155℃ and reacted for 2-4 hours. After cooling, filtering, washing and drying, the pentaerythritol diphosphate dichlorophosphoryl chloride ethylenediamine macromolecular flame retardant is obtained.

[0006] The above-mentioned preparation methods of macromolecular phosphorus-containing flame retardants generally have the problems of complex preparation process, high industrialization cost, large acid value or unstable acid value, and the like, which affect the subsequent application. SUMMARY

[0007] The application aims to provide a preparation method of a mixed macromolecular phosphorus-containing flame retardant, which has simple preparation process, mild reaction conditions and high yield.

[0008] The technical scheme to realize the above object is: a preparation method of a mixed macromolecular phosphorus-containing flame retardant, characterized by comprising the following steps:

[0009] S1, placing phosphorus oxychloride and a catalyst in a reaction kettle, replacing the air in the reaction kettle with N2, stirring uniformly, then putting glycidyl ether into the reaction kettle, heating the reaction kettle to 50-110 DEG C under normal pressure, reacting for 4-8 hours at the temperature, and cooling to room temperature after the reaction is completed;

[0010] S2, introducing oxyalkylene into the reaction kettle to control the temperature and pressure in the reaction kettle to slowly rise, and maintain the final temperature of the reaction kettle at 50-100 DEG C and the final pressure at 0.1-0.5 Mpa;

[0011] S3, during the reaction, sampling in the middle, stopping the introduction of oxyalkylene when the acid value of the product is lower than 0.5 mgKOH / g, continuing to react until the pressure in the reaction kettle drops to a constant pressure, then aging for 2 hours, removing low-boiling substances, and obtaining a crude product;

[0012] S4, first washing the crude product with lye until it is neutral, then washing it with distilled water twice, and finally dehydrating under negative pressure to obtain a macromolecular phosphorus-containing flame retardant.

[0013] The main reaction process and product of steps S1 and S2 are as follows:

[0014]

[0015] Further, the molar ratio of phosphorus oxychloride to glycidyl ether in step S1 is (1-4):1.

[0016] Further, the glycidyl ether in step S1 is one or more of 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, 1,2-cyclohexanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, propoxy glycerol triglycidyl ether, glycerol triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0017] Further, the catalyst in step S1 is one of boron trifluoride ether, titanium tetrachloride, tetrabutyl titanate, and aluminum trichloride, and the catalyst is added in an amount of 0.1%-1% (wt) of phosphorus oxychloride.

[0018] Further, the oxyalkylene in step S2 is one or more of ethylene oxide, propylene oxide, epichlorohydrin, and butylene oxide.

[0019] Further, the alkali washing temperature in step S4 is 50-80℃, and the distilled water washing temperature is 50-80℃.

[0020] The present application adopts excess phosphorus oxychloride and polyepoxy glycidyl ether reaction, a single polyepoxy glycidyl ether can react with single or multiple phosphorus oxychloride to generate a macromolecular compound, and the unreacted P-Cl bond can react with an epoxy alkene, so that the acid value of the product can be reduced while the molecular weight of the product is increased, and the product is more stable.

[0021] The present application has the following advantages of the above process:

[0022] (1) The preparation process of the flame retardant is simple, the reaction conditions are mild, the yield is high, and the cost is low, and the phosphorus and chlorine migration rate in the product is low.

[0023] (2) The phosphorus-containing flame retardant prepared by the method has large molecular weight, the molecular weight can be adjusted according to customer demand, and the phosphorus and chlorine migration rate in the product is small. DETAILED DESCRIPTION

[0024] I. Preparation of phosphorus-containing flame retardant:

[0025] The present application will be further described below in conjunction with examples, and it should be noted that the examples do not constitute a limitation on the scope of protection required by the present application.

[0026] The raw materials used in the examples of the present application are all general industrial grade products, and the content of phosphorus and chlorine is determined according to the reference: Xia Zuxi, Zhang Yabo, Su Zhengliang. Influence of temperature and environment on migration behavior of flame retardant in polyurethane soft foam [J]. Plastics Industry, 2008 (10): 40-42.

[0027] Comparative Example 1: Phosphoric acid tris (β-chloroethyl) ester, Yangzhou Chenhua New Material Co., Ltd.

[0028] Comparative Example 2: Phosphoric acid tris (2-chloropropyl) ester, Yangzhou Chenhua New Material Co., Ltd. Example 1

[0029] Put 1530g of phosphorus oxychloride and 15.3g of boron trifluoride ether into the reaction kettle, replace the air in the reaction kettle with N2, stir uniformly, then put 1740g of ethylene glycol diglycidyl ether into the reaction kettle, and heat to 50℃ under normal pressure for 6h, and then cool to room temperature after the reaction is completed.

[0030] The reaction kettle is connected with an epoxy ethane inlet, and the reaction is carried out by controlling the temperature and pressure in the reaction kettle to rise slowly, and the final temperature in the reaction kettle is maintained at 50℃ and the final pressure is maintained at 0.5Mpa.

[0031] Midway sampling, when the product acid value is lower than 0.5 mgKOH / g, stop passing in ethylene oxide, consume ethylene oxide 1100g.

[0032] Continue to react until the pressure in the kettle drops to constant pressure, then age for 2h, remove low boiling point substances under negative pressure to obtain the crude product. Wash the crude product with 50℃ alkali solution until neutral, then wash twice with 50℃ distilled water, and finally dehydrate under negative pressure at 105℃ for 2h to obtain the product 4290g with phosphorus and chlorine content of 32.05%. Example 2

[0033] Put 2295g of phosphorus oxychloride and 5.2g of titanium tetrachloride into the reaction kettle, replace the air in the reaction kettle with N2, stir uniformly, then put 1440g of resorcinol diglycidyl ether into the reaction kettle, and react under normal pressure to 80℃ for 6h, and then cool to room temperature after the reaction is completed.

[0034] Pass in propylene oxide into the reaction kettle to react, control the temperature and pressure in the reaction kettle to slowly rise by the passing-in speed, and maintain the final temperature of the reaction kettle at 80℃ and the final pressure at 0.15Mpa.

[0035] Midway sampling, when the product acid value is lower than 0.5 mgKOH / g, stop passing in propylene oxide, consume propylene oxide 2030g. Continue to react until the pressure in the kettle drops to constant pressure, then age for 2h, remove low boiling point substances under negative pressure to obtain the crude product.

[0036] Wash the crude product with alkali solution at 70℃ until neutral, then wash twice with distilled water at 70℃, and finally dehydrate under negative pressure at 105℃ for 2h to obtain the product 5712g with phosphorus and chlorine content of 36.11%. Example 3

[0037] Put 1836g of phosphorus oxychloride and 4.5g of tetrabutyl titanate into the reaction kettle, replace the air in the reaction kettle with N2, stir uniformly, then put 1140g of glycerol triglycidyl ether into the reaction kettle, and react under normal pressure to 90℃ for 6h, and then cool to room temperature after the reaction is completed.

[0038] Pass in epichlorohydrin into the reaction kettle to react, control the temperature and pressure in the reaction kettle to slowly rise by the passing-in speed, and maintain the final temperature of the reaction kettle at 100℃ and the final pressure at 0.1Mpa.

[0039] Midway sampling, when the product acid value is lower than 0.5 mgKOH / g, stop passing in epichlorohydrin, consume epichlorohydrin 5503g. Continue to react until the pressure in the kettle drops to constant pressure, then age for 2h, remove low boiling point substances under negative pressure to obtain the crude product.

[0040] The crude product is first washed with lye at 80°C until neutral, then washed with distilled water at 80°C for 2 times, and finally dehydrated at 105°C under negative pressure for 2h to obtain the product 5503g with phosphorus and chlorine content of 47.36%. Example 4

[0041] Put 2448g of phosphorus oxychloride and 2.5g of boron trifluoride ether into the reaction kettle, replace the air in the reaction kettle with N2, stir uniformly, then put 1440g of pentaerythritol tetraglycidyl ether into the reaction kettle, and heat to 110°C under normal pressure for 4h. After the reaction is completed, cool to room temperature.

[0042] Introduce ethylene oxide into the reaction kettle to react, control the temperature and pressure in the reaction kettle to slowly rise by the introduction speed, and maintain the final temperature of the reaction kettle at 70°C and the final pressure at 0.1Mpa.

[0043] Take samples in the middle, stop introducing ethylene oxide when the acid value of the product is lower than 0.5 mgKOH / g, consume 1720g of ethylene oxide. Continue to react until the pressure in the kettle drops to the constant pressure, then age for 2h, remove the low boiling point substances under negative pressure to obtain the crude product.

[0044] First wash the crude product with lye at 70°C until neutral, then wash with distilled water at 70°C for 2 times, and finally dehydrate at 105°C under negative pressure for 2h to obtain the product 5544g with phosphorus and chlorine content of 39.68%. Example 5

[0045] Put 1989g of phosphorus oxychloride and 4.2g of aluminum chloride into the reaction kettle, replace the air in the reaction kettle with N2, stir uniformly, then put 1130g of propoxy glycerol triglycidyl ether and 526g of 1,4-butanediol diglycidyl ether into the reaction kettle, heat to 80°C under normal pressure for 8h, and cool to room temperature after the reaction is completed.

[0046] Introduce ethylene oxide into the reaction kettle to react, control the temperature and pressure in the reaction kettle to slowly rise by the introduction speed, and maintain the final temperature of the reaction kettle at 80°C and the final pressure at 0.1Mpa.

[0047] Take samples in the middle, stop introducing ethylene oxide when the acid value of the product is lower than 0.5 mgKOH / g, consume 1392g of ethylene oxide. Continue to react until the pressure in the kettle drops to the constant pressure, then age for 2h, remove the low boiling point substances under negative pressure to obtain the crude product.

[0048] First wash the crude product with lye at 70°C until neutral, then wash with distilled water at 70°C for 2 times, and finally dehydrate at 105°C under negative pressure for 2h to obtain the product 4928g with phosphorus and chlorine content of 36.27%. Example 6

[0049] Put 1683 g of phosphorus oxychloride and 4.9 g of titanium tetrachloride into a reaction kettle, displace the air in the reaction kettle with N2, stir until uniform, then put 612 g of pentaerythritol tetraglycidyl ether and 410 g of diethylene glycol diglycidyl ether into the reaction kettle, heat to 90°C under normal pressure for 8 h, and then cool to room temperature after the reaction is completed.

[0050] Pass propylene oxide into the reaction kettle to control the temperature and pressure in the reaction kettle to slowly rise, and maintain the final temperature at 80°C and the final pressure at 0.2 MPa.

[0051] Take samples in the middle, stop passing propylene oxide when the acid value of the product is less than 0.5 mgKOH / g, consume 1588 g of propylene oxide. Continue to react until the pressure in the kettle drops to a constant pressure, and then age for 2 h, remove the low boiling point material under negative pressure, and obtain the crude product.

[0052] First wash the crude product with lye at 70°C until it is neutral, then wash it with distilled water at 70°C for 2 times, and finally dehydrate it at 105°C under negative pressure for 2 h, to obtain the product 4172 g, with phosphorus and chlorine content of 36.25%.

[0053] II. Application and testing:

[0054] (1) Preparation of flame-retardant polyurethane rigid foam.

[0055] Mix 5 g and 25 g of the flame retardant of the above two comparative examples and six examples respectively with 25 g of white material (obtained by uniformly mixing 100 parts by weight of polyether 4110, 2 parts by weight of catalyst dimethylcyclohexylamine, 1.5 parts by weight of water, 25 parts by weight of blowing agent HCFC-141b and 1.5 parts by weight of silicone oil CGY-1A) uniformly, then add 30 g of black material (diphenylmethane diisocyanate), the material temperature is 25°C, mix uniformly after electric stirring for 5 seconds, then pour into a foaming box with the size of 200 mm x 200 mm x 200 mm (length x width x height) for foaming, a total of 7 rigid foam samples are obtained, which are aged for 72 h, and the flame retardant properties (limiting oxygen index LOI) and the change of phosphorus and chlorine content are measured.

[0056] (2) Determination of limiting oxygen index (LOI) of the sample

[0057] Use JF-3 type limiting oxygen index tester (Shanghai Zhonglu Industry Co., Ltd.), test according to GB / T 2406.2-2009 standard, and the sample size is 100 mm x 10 mm x 10 mm (length x width x thickness).

[0058] (3) Determination of phosphorus and chlorine in polyurethane rigid foam

[0059] Take the above preparation of polyurethane hard foam sample, size is 100 mm x 10 mm x 10 mm (length x width x thickness), after constant temperature and humidity treatment, put in the inner loop of the air drying oven constant temperature 60℃ baking, 1 month sampling once, a total of 3 times sampling, from the length of 100 mm end sampling, each sampling size is 10 mm x 10 mm x 10 mm cross section pattern.

[0060] Sample treatment and phosphorus and chlorine content determination reference: Xia Zuxi, Zhang Yabo, Su Zhengliang. Temperature environment on the migration behavior of polyurethane soft foam flame retardant [J]. Plastic industry, 2008 (10): 40-42.

[0061] The test results are shown in the following table: , the migration rate is the migration rate after 3 months of baking, the mass fraction of phosphorus and chlorine is the sum of the mass fraction of phosphorus and the mass fraction of chlorine

[0062]

[0063] From the above examples and comparative examples for polyurethane hard foam flame retardant effect and the change of the migration of the flame retardant can be seen, the flame retardant effect of the product of the present application and the comparative example is equivalent, but its phosphorus and chlorine migration rate is significantly less than the comparative example.

[0064] The above is only the preferred specific embodiment of the present application, but the protection scope of the present application is not limited to this, any skilled person in the art according to the technical solution and the concept of invention within the scope of the present application, equivalent replacement or change, should be covered in the protection scope of the present application.

Claims

1. A process for the preparation of a hybrid macromolecular phosphorus-containing flame retardant, characterized in that, It comprises the following steps: S1, the phosphorus oxychloride and catalyst are placed in a reaction kettle, the air in the reaction kettle is replaced by N2, then stirred uniformly, and the glycidyl ether is put into the reaction kettle, the normal pressure in the reaction kettle is raised to 50-110℃, the reaction is carried out at the temperature for 4-8h, and then cooled to room temperature after the reaction is completed; the molar ratio of the phosphorus oxychloride to the glycidyl ether is (1-4):1; the glycidyl ether is one or more of 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, 1,2-cyclohexanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, propoxy glycerol triglycidyl ether, glycerol triglycidyl ether, and pentaerythritol tetraglycidyl ether; S2, the oxyalkylene is introduced into the reaction kettle to control the temperature and pressure in the reaction kettle to slowly rise, and the final temperature in the reaction kettle is maintained at 50-100℃, and the final pressure is maintained at 0.1-0.5 Mpa; the oxyalkylene is one or more of ethylene oxide, propylene oxide, epichlorohydrin, and butylene oxide; S3, during the reaction, the product is sampled in the middle, when the acid value of the product is lower than 0.5 mgKOH / g, the introduction of the oxyalkylene is stopped, the reaction is continued until the pressure in the reaction kettle drops to a constant pressure, and then aged for 2h, the low-boiling substances are removed, and the crude product is obtained; S4, the crude product is first washed with lye to neutral, then washed with distilled water for 2 times, and finally dehydrated under negative pressure to obtain the macromolecular phosphorus-containing flame retardant.

2. A process for the preparation of a mixed macromolecular phosphorus-containing flame retardant according to claim 1, characterized in that: The catalyst in step S1 is one of boron trifluoride, titanium tetrachloride, tetrabutyl titanate, and aluminum trichloride, and the catalyst is added in an amount of 0.1 wt %-1 wt % of the phosphorus oxychloride.

3. The process for the preparation of a mixed macromolecular phosphorus-containing flame retardant according to claim 1, characterized in that: The temperature for washing with lye in step S4 is 50-80℃, and the temperature for washing with distilled water is 50-80℃.

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