Low-volatility hydrolysis-resistant bisphenol A diphosphate-based flame retardant
By preparing a low-volatility, hydrolysis-resistant bisphenol A bisphosphate-based flame retardant, the flame retardant properties of resin materials are improved by utilizing silicon-oxygen bonds, phosphate esters, and fluorine elements. This solves the problem of flammability of polymer resin materials at high temperatures and achieves higher thermal stability and flame retardant effect.
Patent Information
- Application Number
- CN202511004595.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-21
- Publication Date
- 2025-11-21
AI Technical Summary
Multifunctional polymer resin materials are flammable in high-temperature environments, and existing flame retardants cannot effectively improve their thermal stability and flame retardant properties, limiting their application in more demanding fields.
A method for preparing a low-volatility, hydrolysis-resistant bisphenol A bisphosphate-based flame retardant was adopted. By introducing silicon-oxygen bond structure, phosphate ester structure and fluorine element, the hydrolysis resistance and molecular weight of the flame retardant were improved, and a silicon-carbon layer was formed to inhibit the combustion reaction.
It significantly improves the flame retardant properties of resin materials, reduces volatility, enhances high-temperature stability, and prevents the flame retardant effect from decreasing during combustion.
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Abstract
Description
TECHNICAL FIELD
[0001] The application relates to the field of flame retardants, and particularly relates to a low-volatility hydrolysis-resistant bisphenol A bisphosphate-based flame retardant. BACKGROUND
[0002] Although multifunctional polymer resin materials have been widely applied in many fields such as building, electronics, aerospace and the like due to their excellent performance, the thermal stability and flame retardant performance caused by the carbon-hydrogen skeleton structure of the materials are insufficient, and the materials are prone to thermal decomposition and combustion under high-temperature environment, which becomes a core defect restricting the wider application of the materials. Therefore, developing effective flame retardants to overcome the flammability defect of the materials and improve the high-temperature use safety of the materials is a key technical direction for promoting the expansion of resin materials to higher requirement fields. SUMMARY
[0003] The application aims to provide a multi-solid waste-based composite curing agent and a preparation method thereof to solve the problems in the prior art.
[0004] To achieve the above-mentioned purpose, the application provides the following technical scheme: a preparation method of a low-volatility hydrolysis-resistant bisphenol A bisphosphate-based flame retardant, comprising the following steps:
[0005] S1. Magnesium silicate is added to phosphorus oxychloride, and after ultrasonic oscillation and uniform mixing, 1,1,3,3-tetramethyl-1,3-disiloxane diol is added dropwise in toluene solution under nitrogen atmosphere protection, the dropwise adding time is controlled to be 1-2 h, after the dropwise adding is completed, heating, stirring and reaction are carried out for 2-8 h, and then excess solvent is removed by rotary evaporation to obtain a silicon-modified phosphorus oxychloride intermediate;
[0006] S2. The silicon-modified phosphorus oxychloride intermediate is dispersed into toluene, and after uniform mixing, it is added dropwise into a toluene solution containing bisphenol A, stirring is continuously carried out during the dropwise adding, after the dropwise adding is completed, heating, continuous stirring and reaction are carried out for 12-24 h, then excess solvent is removed by rotary evaporation, and after 1-2 times of water washing with deionized water, vacuum drying is carried out to constant weight to obtain a bisphenol A bisphosphate intermediate;
[0007] S3. The bisphenol A bisphosphate intermediate is dispersed into DMF, and after uniform ultrasonic dispersion, thionyl chloride is continuously added, after uniform mixing and stirring, it is added dropwise into 4-trifluoromethoxybenzoic acid, the dropwise adding time is controlled to be 2-4 h, the temperature of the reaction system is controlled to be 4-10 DEG C during the dropwise adding, after the dropwise adding is completed, heating, stirring and reaction are carried out for 4-6 h, and then excess solvent is removed by rotary evaporation to obtain the low-volatility hydrolysis-resistant bisphenol A bisphosphate-based flame retardant.
[0008] Further, in step S1, the adding amount of each component is 10 parts of phosphorus oxychloride, 0.0005-0.001 parts of magnesium silicate, 4.6-5.6 parts of 1,1,3,3-tetramethyl-1,3-disiloxane diol by weight.
[0009] Further, in step S1, after the dropping is completed, the reaction system is heated to 105-125 DEG C.
[0010] Further, in step S2, the adding amount of each component is 10 parts of silicon modified phosphorus oxychloride intermediate, 15-20.3 parts of bisphenol A by weight.
[0011] Further, in step S2, after the dropping is completed, the reaction system is heated to 105-110 DEG C.
[0012] Further, in step S3, the adding amount of each component is 10 parts of bisphenol A bisphosphate intermediate, 0.005-0.01 parts of thionyl chloride, 5.1-6.7 parts of 4-trifluoromethoxybenzoic acid by weight.
[0013] Further, in step S3, after the dropping is completed, the temperature is raised to 115-140 DEG C.
[0014] Further, a low-volatility hydrolysis-resistant bisphenol A bisphosphate-based flame retardant is prepared by the above method.
[0015] Compared with the prior art, the beneficial effects of the present application are:
[0016] The present application is to improve the flame retardant performance of resin material, and a bisphenol A bisphosphate-based flame retardant with low volatility and hydrolysis resistance is prepared. The present application first uses 1,1,3,3-tetramethyl-1,3-disiloxane diol containing siloxane structure as raw material, reacts with phosphorus oxychloride, replaces chlorine atoms in phosphorus oxychloride with alcohol hydroxyl groups in 1,1,3,3-tetramethyl-1,3-disiloxane diol, introduces siloxane bond structure with high bond energy into the flame retardant, thereby improving the hydrolysis resistance of the flame retardant. On this basis, the present application further reacts with bisphenol A, further replaces chlorine atoms in phosphorus oxychloride structure with phenolic hydroxyl groups in bisphenol A to generate phosphate structure, avoids the reaction and hydrolysis of phosphorus atoms in phosphorus flame retardant due to the high activity of phosphorus oxychloride. On this basis, the present application further reacts with 4-trifluoromethoxy benzoic acid containing fluorine element to introduce fluorine element with high electronegativity into the flame retardant, further improve the water resistance of the flame retardant, avoid the hydrolysis of the flame retardant. In the preparation process, multiple reactions can gradually increase the molecular weight of the flame retardant, reduce its volatility, and the introduced silicon element in the flame retardant can form a silicon-containing carbon layer with the resin during the combustion of the resin material, thereby further preventing the combustion reaction and inhibiting the diffusion of flammable gas, avoiding the decline of the flame retardant effect in the later stage of the flame retardant process. DETAILED DESCRIPTION
[0017] Based on the examples in the present application, all other examples obtained by a person of ordinary skill in the art without creative labor belong to the scope of protection of the present application.
[0018] Example 1. A preparation method of a bisphenol A bisphosphate-based flame retardant with low volatility and hydrolysis resistance, comprising the following steps:
[0019] S1. According to the weight fraction, 0.0008 parts of magnesium silicate is added to 10 parts of phosphorus oxychloride, and then ultrasonic oscillation is performed for mixing, and then nitrogen atmosphere protection is performed, and then a toluene solution containing 4.6 parts of 1,1,3,3-tetramethyl-1,3-disiloxane diol is added dropwise, the dropwise adding time is controlled to be 1.5 hours, after the dropwise adding is completed, the temperature is increased to 115 DEG C, and then stirring is performed for 6 hours, and then excess solvent is removed by rotary evaporation to obtain a silicon-modified phosphorus oxychloride intermediate;
[0020] S2. According to the weight fraction, 10 parts of the silicon-modified phosphorus oxychloride intermediate is dispersed into toluene, and then mixed uniformly, and then added dropwise into a toluene solution containing 15 parts of bisphenol A, and then stirring is continuously performed during the dropwise adding, and then the temperature is increased to 105 DEG C after the dropwise adding is completed, and then stirring is continuously performed for 12-24 hours, and then excess solvent is removed by rotary evaporation, and then washed with deionized water for 1-2 times, and then vacuum dried to constant weight to obtain a bisphenol A bisphosphate intermediate;
[0021] S3. 10 parts of bisphenol A bisphosphate intermediate was dispersed into DMF by weight fraction, after ultrasonic dispersion, 0.008 parts of thionyl chloride was added, after mixing and stirring, it was added dropwise into 5.1 parts of 4-trifluoromethoxy benzoic acid solution, the dropwise time was controlled for 3h, during the dropwise process, the reaction system temperature was controlled for 4~6℃, after the dropwise process, the temperature was increased to 125℃, after stirring for 6h, the excess solvent was removed by rotary evaporation, a low volatile and hydrolysis resistant bisphenol A bisphosphate based flame retardant was obtained.
[0022] Example 2. A preparation method of a low volatile and hydrolysis resistant bisphenol A bisphosphate based flame retardant, comprising the following steps:
[0023] Compared with example 1, the addition amount of 1,1,3,3-tetramethyl-1,3-siloxane diol in step S1 was increased in this example;
[0024] S1. 0.0008 parts of magnesium silicate was added into 10 parts of phosphorus oxychloride by weight fraction, after ultrasonic oscillation and mixing, 5.6 parts of 1,1,3,3-tetramethyl-1,3-siloxane diol solution in toluene was added dropwise, the dropwise time was controlled for 1.5h, after the dropwise process, the temperature was increased to 115℃, after stirring for 6h, the excess solvent was removed by rotary evaporation, a silicon modified phosphorus oxychloride intermediate was obtained;
[0025] S2. 10 parts of silicon modified phosphorus oxychloride intermediate was dispersed into toluene by weight fraction, after mixing, it was added dropwise into 15 parts of bisphenol A solution in toluene, during the dropwise process, it was continuously stirred, after the dropwise process, the temperature was increased to 105℃, after stirring for 12~24h, the excess solvent was removed by rotary evaporation, after washing with deionized water for 1~2 times, vacuum drying to constant weight, a bisphenol A bisphosphate intermediate was obtained;
[0026] S3. 10 parts of bisphenol A bisphosphate intermediate was dispersed into DMF by weight fraction, after ultrasonic dispersion, 0.008 parts of thionyl chloride was added, after mixing and stirring, it was added dropwise into 5.1 parts of 4-trifluoromethoxy benzoic acid solution, the dropwise time was controlled for 3h, during the dropwise process, the reaction system temperature was controlled for 4~6℃, after the dropwise process, the temperature was increased to 125℃, after stirring for 6h, the excess solvent was removed by rotary evaporation, a low volatile and hydrolysis resistant bisphenol A bisphosphate based flame retardant was obtained.
[0027] Example 3. A preparation method of a low volatile and hydrolysis resistant bisphenol A bisphosphate based flame retardant, comprising the following steps:
[0028] Compared with example 2, the addition amount of bisphenol A in step S2 was increased in this example;
[0029] S1. In 10 parts of phosphorus oxychloride, 0.0008 parts of magnesium silicate was added, and then ultrasonic oscillation was performed for mixing. After mixing was completed, 5.6 parts of 1,1,3,3-tetramethyl-1,3-disiloxane diol was dissolved in toluene, and the solution was added dropwise to the mixture under nitrogen atmosphere. The dropwise addition was performed for 1.5 hours. After the dropwise addition was completed, the temperature was increased to 115°C, and stirring was performed for 6 hours. After the reaction, excess solvent was removed by rotary evaporation to obtain a silicon-modified phosphorus oxychloride intermediate.
[0030] S2. In 10 parts of the silicon-modified phosphorus oxychloride intermediate, toluene was added, and then mixing was performed. After mixing was completed, the mixture was added dropwise to a toluene solution in which 20.3 parts of bisphenol A was dissolved. During the dropwise addition, stirring was continuously performed. After the dropwise addition was completed, the temperature was increased to 105°C, and stirring was continuously performed for 12 to 24 hours. After the reaction, excess solvent was removed by rotary evaporation, and then the mixture was washed with deionized water for 1 to 2 times. After drying under vacuum to a constant weight, a bisphenol A bisphosphate intermediate was obtained.
[0031] S3. In 10 parts of the bisphenol A bisphosphate intermediate, DMF was added, and then ultrasonic dispersion was performed for mixing. After mixing was completed, 0.008 parts of thionyl chloride was added, and then mixing and stirring were performed. After mixing and stirring were completed, the mixture was added dropwise to a solution in which 5.1 parts of 4-trifluoromethoxybenzoic acid was dissolved. The dropwise addition was performed for 3 hours. During the dropwise addition, the temperature of the reaction system was controlled to be 4 to 6°C. After the dropwise addition was completed, the temperature was increased to 125°C, and stirring was performed for 6 hours. After the reaction, excess solvent was removed by rotary evaporation to obtain a low-volatility and hydrolysis-resistant bisphenol A bisphosphate-based flame retardant.
[0032] Example 4. A method for preparing a low-volatility and hydrolysis-resistant bisphenol A bisphosphate-based flame retardant, including the following steps:
[0033] Compared with Example 3, the amount of 4-trifluoromethoxybenzoic acid added in step S3 is increased in this example.
[0034] S1. In 10 parts of phosphorus oxychloride, 0.0008 parts of magnesium silicate was added, and then ultrasonic oscillation was performed for mixing. After mixing was completed, 5.6 parts of 1,1,3,3-tetramethyl-1,3-disiloxane diol was dissolved in toluene, and the solution was added dropwise to the mixture under nitrogen atmosphere. The dropwise addition was performed for 1.5 hours. After the dropwise addition was completed, the temperature was increased to 115°C, and stirring was performed for 6 hours. After the reaction, excess solvent was removed by rotary evaporation to obtain a silicon-modified phosphorus oxychloride intermediate.
[0035] S2. In 10 parts of the silicon-modified phosphorus oxychloride intermediate, toluene was added, and then mixing was performed. After mixing was completed, the mixture was added dropwise to a toluene solution in which 20.3 parts of bisphenol A was dissolved. During the dropwise addition, stirring was continuously performed. After the dropwise addition was completed, the temperature was increased to 105°C, and stirring was continuously performed for 12 to 24 hours. After the reaction, excess solvent was removed by rotary evaporation, and then the mixture was washed with deionized water for 1 to 2 times. After drying under vacuum to a constant weight, a bisphenol A bisphosphate intermediate was obtained.
[0036] S3. 10 parts of bisphenol A bisphosphate intermediate was dispersed into DMF by weight fraction, after ultrasonic dispersion, 0.008 parts of thionyl chloride was added, after mixing and stirring, it was added dropwise into 6.7 parts of 4-trifluoromethoxy benzoic acid solution, the dropwise time was controlled for 3h, during the dropwise process, the temperature of the reaction system was controlled for 4~6℃, after the dropwise process, the temperature was increased to 125℃, after stirring for 6h, the excess solvent was removed by rotary evaporation, a low volatile anti-hydrolysis bisphenol A bisphosphate based flame retardant was obtained.
[0037] Comparative Example 1. A preparation method of a low volatile anti-hydrolysis bisphenol A bisphosphate based flame retardant, comprising the following steps:
[0038] Compared with Example 1, the present comparative example does not perform step S3;
[0039] S1. 0.0008 parts of magnesium silicate was added into 10 parts of phosphorus oxychloride by weight fraction, after ultrasonic oscillation and mixing, 4.6 parts of 1,1,3,3-tetramethyl-1,3-disiloxane diol was dissolved in toluene and added dropwise, the dropwise time was controlled for 1.5h, after the dropwise process, the temperature was increased to 115℃, after stirring for 6h, the excess solvent was removed by rotary evaporation, a silicon modified phosphorus oxychloride intermediate was obtained;
[0040] S2. 10 parts of silicon modified phosphorus oxychloride intermediate was dispersed into toluene by weight fraction, after mixing, it was added dropwise into 15 parts of bisphenol A toluene solution, during the dropwise process, it was continuously stirred, after the dropwise process, the temperature was increased to 105℃, after continuous stirring for 12~24h, the excess solvent was removed by rotary evaporation, after washing with deionized water for 1~2 times, vacuum drying to constant weight, a low volatile anti-hydrolysis bisphenol A bisphosphate based flame retardant was obtained.
[0041] Detection: the low volatile anti-hydrolysis bisphenol A bisphosphate based flame retardants prepared by the present application examples 1~4 and comparative example 1 were mixed with polypropylene at a proportion of 15wt%, added into a twin-screw extruder for extrusion molding, according to GB / T2406.2-2009, the limiting oxygen index test was carried out; according to UL-94, the vertical burning grade was tested;
[0042] 0.1mol / L of sodium hydroxide solution was prepared, divided into two parts, and heated to 80℃, the low volatile anti-hydrolysis bisphenol A bisphosphate based flame retardants prepared by the present application examples 1~4 and comparative example 1 were added into the two parts respectively, after treatment for 8h, the phosphorus content retention rate before and after treatment was detected; the phosphorus content was measured by using plasma emission coupled with spectrophotometer;
[0043] The detection results are shown in the following table;
[0044]
[0045] Finally, it should be noted that the above only describes the preferred embodiments of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art will appreciate that modifications can be made to the technical solutions described in the foregoing embodiments, or some of the technical features thereof can be replaced by equivalent features. Any modifications, equivalent replacements, improvements, and the like made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims
1. A process for the preparation of a low volatile, hydrolysis resistant bisphenol A bisphosphate based flame retardant characterized in that, Comprise the following steps: S1. To the phosphorus oxychloride, magnesium silicate was added, ultrasonic oscillation mixed uniformly, under the protection of nitrogen atmosphere, to which was added a solution of 1,1,3,3-tetramethyl-1,3-dioxane diol in toluene, the dropwise addition time was controlled for 1~2h, after the dropwise addition was completed, the temperature was raised, and the reaction was stirred for 2~8h, then the excess solvent was removed by rotary evaporation to obtain a silicon-modified phosphorus oxychloride intermediate; S2. The silicon-modified phosphorus oxychloride intermediate was dispersed in toluene, mixed uniformly, then added dropwise to a solution of bisphenol A in toluene, the dropwise addition was continuously stirred, after the dropwise addition was completed, the temperature was raised, and the reaction was continuously stirred for 12~24h, then the excess solvent was removed by rotary evaporation, and after washing with deionized water for 1~2 times, vacuum drying to constant weight, a bisphenol A bisphosphate intermediate was obtained; S3. The bisphenol A bisphosphate intermediate was dispersed in DMF, ultrasonic dispersion was uniform, then thionyl chloride was added, mixed and stirred uniformly, then added dropwise to a solution of 4-trifluoromethoxy benzoic acid, the dropwise addition time was controlled for 2~4h, the reaction system temperature was controlled for 4~10℃ during the dropwise addition, after the dropwise addition was completed, the temperature was raised, and the reaction was stirred for 4~6h, then the excess solvent was removed by rotary evaporation to obtain a low-volatile hydrolysis-resistant bisphenol A bisphosphate-based flame retardant.
2. A process for the preparation of a low volatile, hydrolysis resistant bisphenol A bisphosphate based flame retardant according to claim 1, characterized by: In step S1, the addition amount of each component was 10 parts of phosphorus oxychloride, 0.0005~0.001 parts of magnesium silicate, and 4.6~5.6 parts of 1,1,3,3-tetramethyl-1,3-dioxane diol, by weight.
3. A process for the preparation of a low volatile, hydrolysis resistant bisphenol A bisphosphate based flame retardant as claimed in claim 1, characterized in that: In step S1, after the dropwise addition was completed, the reaction system was heated to 105~125℃.
4. A process for the preparation of a low volatile, hydrolysis resistant bisphenol A bisphosphate based flame retardant as claimed in claim 1, characterized in that: In step S2, the addition amount of each component was 10 parts of silicon-modified phosphorus oxychloride intermediate, 15~20.3 parts of bisphenol A, by weight.
5. A process for the preparation of a low volatile, hydrolysis resistant bisphenol A bisphosphate based flame retardant as claimed in claim 1, wherein: In step S2, after the dropwise addition was completed, the reaction system was heated to 105~110℃.
6. A process for the preparation of a low volatile, hydrolysis resistant bisphenol A bisphosphate based flame retardant as claimed in claim 1, wherein: In step S3, the addition amount of each component was 10 parts of bisphenol A bisphosphate intermediate, 0.005~0.01 parts of thionyl chloride, and 5.1~6.7 parts of 4-trifluoromethoxy benzoic acid, by weight.
7. The method for preparing a low-volatility, hydrolysis-resistant bisphenol A bisphosphate-based flame retardant according to claim 1, characterized in that: In step S3, after the dropwise addition was completed, the temperature was raised to 115~140℃.
8. A low-volatile hydrolysis-resistant bisphenol A bisphosphate-based flame retardant prepared by the preparation method of any one of claims 1~7.