CN103965245A - Phosphorus-containing biological based diacid diglycidyl ester and preparation method and application thereof - Google Patents
Phosphorus-containing biological based diacid diglycidyl ester and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a phosphorus-containing biological based diacid diglycidyl ester with a structure as shown in a formula I, wherein n is 0 or 1, and m satisfies the relation of 0<m<=15. In the preparation of epoxy resin, the phosphorus-containing biological based diacid diglycidyl ester can participate in curing, the introduction of DOPO does not consume epoxy groups of epoxy resin, the compatibility of DOPO with epoxy resin can be enhanced, and the strength and the glass transition temperature of epoxy resin will not be decreased but can even be improved. The invention also provides a preparation method of the phosphorus-containing biological based diacid diglycidyl ester. Itaconic acid, fumaric acid or maleic acid with rich biological sources are used as raw materials to modify DOPO, so as to reduce or avoid the use of petrochemical products from the source and realize the double effects of saving resources and environmental protection.
Description
Technical field
The present invention relates to halogen-free flame retardants field, be specifically related to novel halogen-free flame-retardant agent-phosphorous bio-based diacid 2-glycidyl ester being obtained by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and bio-based diacid derivatization reaction and its preparation method and application.
Background technology
There is the features such as performance is good, light weight, easy processing due to macromolecular material, be therefore all widely applied in the every field of national economy.But macromolecular material is inflammable, often need to add fire retardant to reach the requirement of use.Along with European Union is for two large instructions " instruction of waste electronic electrical equipment " (the West Electrical and Electronic Equipment Directive of fire retardant environment aspect, WEEE) (come into force in March, 2003) and " forbidding objectionable impurities instruction in electronic and electrical equipment " (Restriction of HazardousSubstances Directive, RoHS) promulgation, the flame-retardant systems such as traditional halogen are limited by very large.Fire retardant industry faces requires to turn to the pressure of the fire retardant that is considered to more environmental protection.Organophosphorous fire retardant has the high flame retardant of similar halogen flame, and halogen flame toxicity is very low relatively, is the important directions that current fire retardant changes to environment-friendly type.
At present in the organophosphorous fire retardant of report, 9,10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound (DOPO) and derivative thereof are one of greatest concern, and the Chinese patent application that is 201080022026.6 as the application number Chinese patent application that is 201080022027.0 and application number discloses respectively two kinds of different DOPO derivative flame retardants.Although there is P-H key in DOPO molecular structure, can react with two keys, epoxy group(ing) etc., but for thermosetting resin as unsaturated polyester, epoxy resin, the introducing of DOPO can consume two keys and epoxide group, thereby causes the intensity of thermosetting resin and second-order transition temperature to decline.
Along with petroleum resources are day by day exhausted, find sustainable, high-quality, cheap oil substitute is the key of polymer industry Existence and development.Bio-based materials is taking renewable resources as main raw material, in reducing petrochemicals consumption, also reduced the pollution to environment in petroleum base raw material production process, therefore, the fire retardant of exploitation bio-based is also the direction that current fire retardant changes to environment-friendly type.Methylene-succinic acid, maleic acid and FUMARIC ACID TECH GRADE biogenetic derivation are abundant, using methylene-succinic acid, maleic acid and FUMARIC ACID TECH GRADE as properties-correcting agent, be incorporated in DOPO structure, both given the multi-functional character of DOPO, reduced again the consumption of DOPO derivatize to petroleum resources.Although United States Patent (USP) 7342061,20060247344,20100181696 all disclose by the technical scheme of methylene-succinic acid, maleic acid and FUMARIC ACID TECH GRADE modification DOPO, but these technical schemes are all the DOPO derivative that preparation contains two carboxyls, do not relate to for the DOPO derivative containing two two keys or two epoxide groups that can participate in unsaturated polyester and epoxy resin cure directly.
Summary of the invention
The invention provides a kind of phosphorous bio-based diacid 2-glycidyl ester, there are two epoxide groups, in the time preparing epoxy resin, can participate in solidifying, the introducing of DOPO can not consume the epoxide group of epoxy resin, the consistency that can improve DOPO and epoxy resin simultaneously, does not reduce intensity and the second-order transition temperature that even can improve epoxy resin.
A kind of phosphorous bio-based diacid 2-glycidyl ester is the compound of formula I structure;
Formula I;
Wherein, n=0 or 1, m are mean polymerisation degree, 0<m≤15.Further preferably, 0<m≤2.5, now, the oxirane value of this phosphorous bio-based diacid 2-glycidyl ester is higher, and the fire retarding epoxide resin cured article of preparation has higher second-order transition temperature and excellent tensile strength.
The present invention also provides a kind of preparation method of phosphorous bio-based diacid 2-glycidyl ester, taking the abundant methylene-succinic acid of biogenetic derivation, fumaroyl or maleic acid as material modification 9, mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy, first prepare phosphorous bio-based diacid, then react with epoxy halogenopropane by phosphorous bio-based diacid and make phosphorous bio-based diacid 2-glycidyl ester.
A preparation method for phosphorous bio-based diacid 2-glycidyl ester, comprises the following steps:
The phosphorous bio-based diacid of 100 mass parts formula II structures, 20~1500 mass parts epoxy halogenopropanes, 0~500 mass parts organic solvent and 0.5~30 mass parts of catalyst are fully mixed, in 80~130 DEG C of reactions 0.2~5 hour, then by temperature control to 30~90 DEG C, add basic cpd and water, continue reaction 1~7 hour, obtain the phosphorous bio-based diacid 2-glycidyl ester of formula I structure through aftertreatment;
Formula II;
Wherein, the n in n and the formula I in formula II has identical meanings.
In above-mentioned preparation process, the open loop that 80~130 DEG C of reactions of the first step 0.2~5 hour are mainly epoxy halogenopropanes becomes ester reaction, and 30~90 DEG C of reactions of second step 1~7 hour are mainly the reactions that dehydrochlorination closed loop becomes epoxy group(ing).
The phosphorous bio-based diacid of formula II structure, can adopt prior art preparation (C.H.Lin, C.Y.Wuand C.S.Wang, Journal of Applied Polymer Science, 2000,78,228-235.), maleic acid or FUMARIC ACID TECH GRADE are reacted and can be made phosphorous butene dioic acid, be i.e. the phosphorous bio-based diacid of formula II structure with mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy, wherein, n=0.Methylene-succinic acid reacts and can make phosphorous methylene-succinic acid with mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy, i.e. the phosphorous bio-based diacid of formula II structure, wherein, n=1.
As preferably, described epoxy halogenopropane is epoxy chloropropane or epoxy bromopropane, and epoxy halogenopropane makes carboxylic acid chloride smoothly.
As preferably, described organic solvent is one or more (the comprising two kinds) in toluene, dimethylbenzene, butanone, dioxane, DMF, dimethyl sulfoxide (DMSO).Organic solvent plays the effect of dissolving and diluting reaction thing, and reaction is carried out smoothly.
Described catalyzer is phase-transfer catalyst or alkaline aqueous solution, as preferably, described catalyzer is tetramethyl ammonium chloride, Tetrabutyl amonium bromide, benzyltrimethylammonium bromide, benzyl triethyl ammonium bromide, cetyl trimethylammonium bromide, Trimethyllaurylammonium bromide, Cetyltrimethylammonium bromide, six methyne four ammoniums, aqueous sodium hydroxide solution, aqueous sodium carbonate, potassium hydroxide aqueous solution or wet chemical.Catalyzer can promote acyl chloride reaction.
As preferably, described basic cpd is one or more (the comprising two kinds) in lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, hydrated barta, the hydrogenchloride and the hydrogen bromide that can absorption reaction generate, acyl chloride reaction is carried out smoothly, can further improve speed of reaction.
As preferably, the add-on of described basic cpd is 60~120 mass parts, and the add-on of described water is 10~30 mass parts.
As preferably, described aftertreatment comprises washing, except desolventizing and dry, obtains phosphorous bio-based diacid 2-glycidyl ester through aftertreatment.
The present invention also provides a kind of application of phosphorous bio-based diacid 2-glycidyl ester, can be used as fire retardant, can be used for preparing thermosetting resin, makes thermosetting resin possess flame-retarding characteristic.The phosphorous bio-based diacid 2-glycidyl ester of formula I structure has two epoxide groups, in the time preparing epoxy resin (one of thermosetting resin), can participate in solidifying, the introducing of DOPO can not consume the epoxide group of epoxy resin, the consistency that can improve DOPO and epoxy resin simultaneously, does not reduce intensity and the second-order transition temperature that even can improve epoxy resin.
A kind of fire retarding epoxide resin cured article, made by the raw material of following mass parts:
Further preferably, described fire retarding epoxide resin cured article, made by the raw material of following mass parts:
The preparation method of described fire retarding epoxide resin cured article, comprises the following steps:
Phosphorous butene dioic acid 2-glycidyl ester, bisphenol A epoxide resin, HHPA and 2-ethyl-4-methylimidazole are mixed, first solidify 1~3 hour at 140 DEG C~160 DEG C, then solidify 2~5 hours at 170 DEG C~190 DEG C, obtain fire retarding epoxide resin cured article.
Further preferably, the preparation method of described fire retarding epoxide resin cured article, comprises the following steps:
Phosphorous butene dioic acid 2-glycidyl ester, bisphenol A epoxide resin, HHPA and 2-ethyl-4-methylimidazole are mixed, first solidify 2 hours at 150 DEG C, then solidify 3 hours at 180 DEG C, obtain fire retarding epoxide resin cured article.
The present invention has advantages of as follows with respect to prior art:
One, in the present invention, phosphorous bio-based diacid 2-glycidyl ester is structurally different from traditional DOPO derivative, has opened up the new variety of fire retardant.Relatively existing DOPO and derivative thereof, phosphorous bio-based diacid 2-glycidyl ester provided by the invention, has reduced consumption and the reduction CO of fire retardant to petroleum resources
2discharge, DOPO and epoxy resin compatibility have been improved simultaneously, be more suitable for for epoxy resin field, can not reduce physical strength and the thermotolerance of system, not only make the thermosetting resin (as epoxy resin) of preparation possess good flame-retarding characteristic, and can also improve physical strength and the thermotolerance of thermosetting resin.
Two, in the present invention; the preparation method of phosphorous bio-based diacid 2-glycidyl ester; taking the abundant methylene-succinic acid of biogenetic derivation, fumaroyl or maleic acid as raw material is to DOPO modification; reduce or avoided the use of petroleum chemicals from synthetic source, there is the double effects economizing on resources with protection of the environment.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
The preparation of the phosphorous methylene-succinic acid of embodiment 1()
By 100g methylene-succinic acid, 167g9, the isopropyl alcohol solution of chloroplatinic acid (1% refers to the quality percentage composition of Platinic chloride) that mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy, 300g toluene and 10g mass percent are 1%, mix, 120 DEG C of reactions 12 hours, after filtration, washing with acetone and dry after obtain phosphorous methylene-succinic acid, be the phosphorous bio-based diacid of formula II structure, wherein, n=1.
Formula II
The preparation of the phosphorous butene dioic acid of embodiment 2()
By 100g maleic acid or FUMARIC ACID TECH GRADE, 170g9, the isopropyl alcohol solution of chloroplatinic acid (1% refers to the quality percentage composition of Platinic chloride) that mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy, 500g dimethylbenzene and 10g mass percent are 1%, mix, 130 DEG C of reactions 12 hours, after filtration, washing with acetone, obtain phosphorous butene dioic acid after dry, be the phosphorous bio-based diacid of formula II structure, wherein, n=0.
Formula II
Embodiment 3
Phosphorous butene dioic acid, 400g epoxy chloropropane prepared by 100g embodiment 2,200g N, dinethylformamide and 6g palmityl trimethyl ammonium chloride fully mix, in 100 DEG C of reactions 3 hours, then be cooled to 70 DEG C, add 60g calcium hydroxide and 20g water, continue reaction 3 hours, after washing, remove desolventizing, being dried, obtain phosphorous butene dioic acid 2-glycidyl ester.
Phosphorous above-mentioned gained butene dioic acid 2-glycidyl ester is carried out to structural characterization, known according to its hydrogen nuclear magnetic resonance spectrogram,
1h nucleus magnetic resonance (CD
3cl is solvent) in have 7.3~8.3ppm to represent that proton peak, 2.3~3.5ppm on DOPO phenyl ring represents the characterization displacement study of proton on epoxide group and main chain carbon.Record oxirane value as 0.15 taking hydrochloric acid acetone method.Utilize oxirane value to pass through formula:
(n in n and formula I has identical meanings) calculates m=2.22.
Formula I;
Wherein, n=0, m is 2.22.
Embodiment 4
The aqueous sodium hydroxide solution that phosphorous butene dioic acid, 600g epoxy chloropropane, 100g dimethyl sulfoxide (DMSO) and 30g mass percent prepared by 100g embodiment 2 is 5% fully mixes, in 117 DEG C of reactions 1 hour, then be cooled to 80 DEG C, add 20g hydrated barta, 80g salt of wormwood and 10g water, continue reaction 2 hours, after washing, remove desolventizing, being dried, obtain phosphorous butene dioic acid 2-glycidyl ester.
Phosphorous above-mentioned gained butene dioic acid 2-glycidyl ester is carried out to structural characterization, known according to its hydrogen nuclear magnetic resonance spectrogram,
1h nucleus magnetic resonance (CD
3cl is solvent) in have 7.3~8.3ppm to represent that proton peak, 2.3~3.5ppm on DOPO phenyl ring represents the characterization displacement study of proton on epoxide group and main chain carbon.Record oxirane value as 0.26 taking hydrochloric acid acetone method.Utilize oxirane value to pass through formula:
(n in n and formula I has identical meanings) calculates m=0.85.
Formula I;
Wherein, n=0, m is 0.85.
Embodiment 5
Phosphorous methylene-succinic acid, 1500g epoxy chloropropane, 20g mass percent prepared by 100g embodiment 1 is that 15% aqueous sodium carbonate fully mixes, in 105 DEG C of reactions 2 hours, then be cooled to 80 DEG C, add 120g sodium carbonate and 10g water, continue reaction 1 hour, after washing, remove desolventizing, being dried, obtain phosphorous methylene-succinic acid 2-glycidyl ester, oxirane value is 0.42.
Phosphorous above-mentioned gained methylene-succinic acid 2-glycidyl ester is carried out to structural characterization, known according to its hydrogen nuclear magnetic resonance spectrogram,
1h nucleus magnetic resonance (CD
3cl is solvent) in have 7.3~8.3ppm to represent that proton peak, 2.3~3.5ppm on DOPO phenyl ring represents the characterization displacement study of proton on epoxide group and main chain carbon.Record oxirane value as 0.42 taking hydrochloric acid acetone method.Utilize oxirane value to pass through formula:
(n in n and formula I has identical meanings) calculates m=0.05.
Formula I;
Wherein, n=1, m is 0.05.
Embodiment 6
Phosphorous methylene-succinic acid, 900g epoxy chloropropane prepared by 100g embodiment 1,50g toluene and 3g tetramethyl ammonium chloride fully mix, in 90 DEG C of reactions 4 hours, then be cooled to 30 DEG C, add 10g hydrated barta, 20g calcium hydroxide, 5g sodium carbonate and 20g water, continue reaction 7 hours, after washing, remove desolventizing, being dried, obtain phosphorous methylene-succinic acid 2-glycidyl ester.
Phosphorous above-mentioned gained methylene-succinic acid 2-glycidyl ester is carried out to structural characterization, known according to its hydrogen nuclear magnetic resonance spectrogram,
1h nucleus magnetic resonance (CD
3cl is solvent) in have 7.3~8.3ppm to represent that proton peak, 2.3~3.5ppm on DOPO phenyl ring represents the characterization displacement study of proton on epoxide group and main chain carbon.Record oxirane value as 0.38 taking hydrochloric acid acetone method.Utilize oxirane value to pass through formula:
(n in n and formula I has identical meanings) calculates m=0.17.
Formula I;
Wherein, n=1, m is 0.17.
Embodiment 7
Phosphorous methylene-succinic acid, 150g epoxy bromopropane prepared by 100g embodiment 1,100g butanone, the potassium hydroxide aqueous solution of 200g dimethyl sulfoxide (DMSO) and 10g30% fully mixes, in 80 DEG C of reactions 5 hours, then be cooled to 40 DEG C, add 20g lithium hydroxide and 30g water, continue reaction 6 hours, after washing, remove desolventizing, being dried, obtain phosphorous butene dioic acid 2-glycidyl ester.
Phosphorous above-mentioned gained methylene-succinic acid 2-glycidyl ester is carried out to structural characterization, known according to its hydrogen nuclear magnetic resonance spectrogram,
1h nucleus magnetic resonance (CD
3cl is solvent) in have 7.3~8.3ppm to represent that proton peak, 2.3~3.5ppm on DOPO phenyl ring represents the characterization displacement study of proton on epoxide group and main chain carbon.Record oxirane value as 0.09 taking hydrochloric acid acetone method.Utilize oxirane value to pass through formula:
(n in n and formula I has identical meanings) calculates m=4.51.
Formula I;
Wherein, n=1, m is 4.51.
Embodiment 8
Phosphorous butene dioic acid, 20g epoxy chloropropane prepared by 100g embodiment 2,450g dimethylbenzene, 50g dioxane and 0.5g Tetrabutyl amonium bromide fully mix, in 120 DEG C of reactions 5 hours, then be cooled to 50 DEG C, add 25g sodium hydroxide and 50g water, continue reaction 5 hours, after washing, remove desolventizing, being dried, obtain phosphorous butene dioic acid 2-glycidyl ester.
Phosphorous above-mentioned gained butene dioic acid 2-glycidyl ester is carried out to structural characterization, known according to its hydrogen nuclear magnetic resonance spectrogram,
1h nucleus magnetic resonance (CD
3cl is solvent) in have 7.3~8.3ppm to represent that proton peak, 2.3~3.5ppm on DOPO phenyl ring represents the characterization displacement study of proton on epoxide group and main chain carbon.Record oxirane value as 0.028 taking hydrochloric acid acetone method.Utilize oxirane value to pass through formula:
(n in n and formula I has identical meanings) calculates m=17.19.
Formula I;
Wherein, n=0, m is 17.19.
Embodiment 9
Phosphorous methylene-succinic acid, 1200g epoxy bromopropane prepared by 100g embodiment 1,12g benzyl triethyl ammonium bromide fully mixes, in 130 DEG C of reactions 0.2 hour, then be cooled to 60 DEG C, add 40g potassium hydroxide and 50g water, continue reaction 4 hours, after washing, remove desolventizing, being dried, obtain phosphorous methylene-succinic acid 2-glycidyl ester.
Phosphorous above-mentioned gained methylene-succinic acid 2-glycidyl ester is carried out to structural characterization, known according to its hydrogen nuclear magnetic resonance spectrogram,
1h nucleus magnetic resonance (CD
3cl is solvent) in have 7.3~8.3ppm to represent that proton peak, 2.3~3.5ppm on DOPO phenyl ring represents the characterization displacement study of proton on epoxide group and main chain carbon.Record oxirane value as 0.40 taking hydrochloric acid acetone method.Utilize oxirane value to pass through formula:
(n in n and formula I has identical meanings) calculates m=0.10.
Formula I;
Wherein, n=1, m is 0.10.
Application examples 1
Phosphorous butene dioic acid 2-glycidyl ester, 100g bisphenol A epoxide resin (oxirane value is 0.536), 60g HHPA and 0.5g2-ethyl prepared by 20g embodiment 4-4-methylimidazole mixes, first solidify 2 hours at 150 DEG C, solidify 3 hours at 180 DEG C again, obtain fire retarding epoxide resin cured article, the flame retardant properties of this fire retarding epoxide resin cured article reaches UL-94V1 level, second-order transition temperature is 124 DEG C, and tensile strength is 64MPa.
Adopt respectively the phosphorous butene dioic acid 2-glycidyl ester of embodiment 3,5,6,7,8,9 preparations to repeat above-mentioned steps, obtain fire retarding epoxide resin cured article, the flame retardant properties of the fire retarding epoxide resin cured article of preparation all reaches UL-94V1 level.The second-order transition temperature of the fire retarding epoxide resin cured article of embodiment 3 correspondences is 128 DEG C, and tensile strength is 63MPa.The second-order transition temperature of the fire retarding epoxide resin cured article of embodiment 5 correspondences is 122 DEG C, and tensile strength is 67MPa.The second-order transition temperature of the fire retarding epoxide resin cured article of embodiment 6 correspondences is 123 DEG C, and tensile strength is 66MPa.The second-order transition temperature of the fire retarding epoxide resin cured article of embodiment 7 correspondences is 130 DEG C, and tensile strength is 60MPa.The second-order transition temperature of the fire retarding epoxide resin cured article of embodiment 8 correspondences is 132 DEG C, and tensile strength is 58MPa.
Contrast: by 100g bisphenol A epoxide resin (oxirane value is 0.536), 60g HHPA and 0.5g2-ethyl-4-methylimidazole, first solidify 2 hours at 150 DEG C, solidify 3 hours at 180 DEG C again, obtain epoxy resin cured product, the second-order transition temperature of this epoxy resin cured product is 122 DEG C, and tensile strength is 60MPa.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a phosphorous bio-based diacid 2-glycidyl ester, is characterized in that, is the compound of formula I structure;
Formula I;
Wherein, n=0 or 1, m are mean polymerisation degree, 0<m≤15.
2. the preparation method of phosphorous bio-based diacid 2-glycidyl ester according to claim 1, is characterized in that, comprises the following steps:
The phosphorous bio-based diacid of 100 mass parts formula II structures, 20~1500 mass parts epoxy halogenopropanes, 0~500 mass parts organic solvent and 0.5~30 mass parts of catalyst are fully mixed, in 80~130 DEG C of reactions 0.2~5 hour, then by temperature control to 30~90 DEG C, add basic cpd and water, continue reaction 1~7 hour, obtain the phosphorous bio-based diacid 2-glycidyl ester of formula I structure through aftertreatment;
Formula II;
Wherein, the n in n and the formula I in formula II has identical meanings.
3. the preparation method of phosphorous bio-based diacid 2-glycidyl ester according to claim 2, is characterized in that, described epoxy halogenopropane is epoxy chloropropane or epoxy bromopropane.
4. the preparation method of phosphorous bio-based diacid 2-glycidyl ester according to claim 2, it is characterized in that, described organic solvent is one or more in toluene, dimethylbenzene, butanone, dioxane, DMF, dimethyl sulfoxide (DMSO).
5. the preparation method of phosphorous bio-based diacid 2-glycidyl ester according to claim 2, it is characterized in that, described catalyzer is tetramethyl ammonium chloride, Tetrabutyl amonium bromide, benzyltrimethylammonium bromide, benzyl triethyl ammonium bromide, cetyl trimethylammonium bromide, Trimethyllaurylammonium bromide, Cetyltrimethylammonium bromide, six methyne four ammoniums, aqueous sodium hydroxide solution, aqueous sodium carbonate, potassium hydroxide aqueous solution or wet chemical.
6. the preparation method of phosphorous bio-based diacid 2-glycidyl ester according to claim 2, is characterized in that, described basic cpd is one or more in lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, hydrated barta.
7. the preparation method of phosphorous bio-based diacid 2-glycidyl ester according to claim 2, is characterized in that, the add-on of described basic cpd is 60~120 mass parts, and the add-on of described water is 10~30 mass parts.
8. the application of phosphorous bio-based diacid 2-glycidyl ester according to claim 1, is characterized in that, described phosphorous bio-based diacid 2-glycidyl ester is as the application of fire retardant.
9. a fire retarding epoxide resin cured article, is characterized in that, is made up of the raw material of following mass parts:
10. the preparation method of fire retarding epoxide resin cured article according to claim 9, is characterized in that, comprises the following steps:
Phosphorous butene dioic acid 2-glycidyl ester, bisphenol A epoxide resin, HHPA and 2-ethyl-4-methylimidazole are mixed, first solidify 1~3 hour at 140 DEG C~160 DEG C, then solidify 2~5 hours at 170 DEG C~190 DEG C, obtain fire retarding epoxide resin cured article.
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