CN103012846B - Phosphaphenanthrene derivative flame retardant - Google Patents
Phosphaphenanthrene derivative flame retardant Download PDFInfo
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- CN103012846B CN103012846B CN201210498980.3A CN201210498980A CN103012846B CN 103012846 B CN103012846 B CN 103012846B CN 201210498980 A CN201210498980 A CN 201210498980A CN 103012846 B CN103012846 B CN 103012846B
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- isocyanuric acid
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Abstract
The invention relates to a phosphaphenanthrene derivative flame retardant TGIC-DOPO and a synthetic method thereof. The TGIC-DOPO has a structural formula described in the specification. According to the synthetic method, triglycidyl isocyanurate (TGIC) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) are used as raw materials, ring-opening addition reaction of P-H and epoxy group is realized in an organic solvent or in a molten state, and the TGIC-DOPO compound is obtained by washing, purification and solvent removal.
Description
Technical field
The present invention relates to a kind of fire retardant that utilizes phosphorus-nitrogen containing element prepared by chemical synthesis process, belong to the technical field of utilizing chemical synthesis process to prepare fire retardant material.
Background technology
In recent years, phospho hetero phenanthrene DOPO compound is used widely in fire retarding epoxide resin field, the derivative of phospho hetero phenanthrene DOPO is such as the compounds such as DOPO-HQ, DOPO-ITA, DOPO-MA are also developed successively, and be applied in fire retarding epoxide resin, and give the flame retardant properties of epoxy resin cured product excellence.
New research shows, DOPO is introduced in compound, makes it possess phospho hetero phenanthrene group, and with other functional group's Application of composite with flame-retarding characteristic, can obtain under certain conditions higher flame retarding efficiency, such as HAP-DOPO compound after deliberation; And by phospho hetero phenanthrene group and cyclic lactam structure composite, be another trial of development of new flame retarding construction.
Summary of the invention
The present invention adopts isocyanuric acid three-glycidyl ester (TGIC) and 9,10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound (DOPO) is raw material, by the epoxide group opening in P-H key and TGIC in DOPO, the compound of a kind of phosphorus nitrogen systems obtaining, referred to as TGIC-DOPO.
TGIC-DOPO molecular formula is as follows:
The preparation of TGIC-DOPO adopts isocyanuric acid three-glycidyl ester (TGIC) and 9,10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound is raw material, reaction preparation TGIC-DOPO crude product in organic solvent or under molten state, and TGIC-DOPO crude product is washed in alcoholic solution to purification, after desolvation, obtain TGIC-DOPO product.
Synthesis material used: isocyanuric acid three-glycidyl ester, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; Reaction solvent comprises: methylene dichloride, ethylene dichloride, tetrachloroethane, chloroform, tetracol phenixin, toluene, chlorobenzene, dimethylbenzene, dichlorobenzene; Cleaning solvent comprises: ethanol, hexalin, glycerol, propylene glycol, Virahol, isobutyl alcohol; All raw material is technical grade product.
Synthesis technique
In organic solvent system: by isocyanuric acid three-glycidyl ester and 9, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy joins in organic solvent according to certain ratio, wherein isocyanuric acid three-glycidyl ester and 9, the mol ratio of mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy is 1: 3.0-1: 6.0, the consumption of reaction solvent is the quality of 6-10 times of isocyanuric acid three-glycidyl ester quality used, keep temperature of reaction at 110-150 DEG C, under agitation condition, react 3-10 hour, reaction solvent is methylene dichloride, ethylene dichloride, tetrachloroethane, chloroform, tetracol phenixin, toluene, chlorobenzene, dimethylbenzene, one in dichlorobenzene, underpressure distillation is removed reaction solvent and is obtained TGIC-DOPO crude product.
In molten system: by 9, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy joins in reaction vessel, and be heated 120-150 DEG C of melting, add gradually subsequently isocyanuric acid three-glycidyl ester, the mol ratio of isocyanuric acid three-glycidyl ester and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1: 2.8-1: 6.0, and keep temperature of reaction at 130-200 DEG C, under agitation condition, react 1-8 hour, obtain crude product TGIC-DOPO.
TGIC-DOPO crude product is joined in cleaning solvent, cleaning solvent is the one in ethanol, hexalin, glycerol, propylene glycol, Virahol, isobutyl alcohol, the consumption of solvent is 1-20 times of isocyanuric acid three-glycidyl ester quality, maintain the temperature at 30-150 DEG C, agitator treating, be cooled to room temperature, staticly settle, after filtering drying, obtain product TGIC-DOPO.
The nucleus magnetic hydrogen spectrum figure of accompanying drawing 1TGIC-DOPO
The infrared spectrum of accompanying drawing 2TGIC-DOPO
The differential scanning calorimeter figure of accompanying drawing 3TGIC-DOPO
The hot weightless picture of accompanying drawing 4TGIC-DOPO
Embodiment:
Embodiment 1 is by 14.9g isocyanuric acid three-glycidyl ester (TGIC), 32.9g 9, mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy joins in the there-necked flask that fills 100g chlorobenzene, under agitation condition, be warming up to 130 DEG C, after question response thing dissolves completely, stirring reaction 6 hours, after reaction finishes, underpressure distillation, removes chlorobenzene, cooling after, product is joined and in 100g ethanol, carries out agitator treating, keep 78 DEG C, leave standstill and be cooled to room temperature, filter out product, dry, obtain target product TGIC-DOPO.
Embodiment 2 is by 14.9g isocyanuric acid three-glycidyl ester (TGIC), 32.9g 9, mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy joins in the there-necked flask that fills 100g dimethylbenzene, under agitation condition, be warming up to 140 DEG C, after question response thing dissolves completely, stirring reaction 6 hours, after reaction finishes, underpressure distillation, except removal xylene, cooling after, product is joined and in 100g Virahol, carries out agitator treating, keep 82 DEG C, leave standstill and be cooled to room temperature, filter out product, dry, obtain target product TGIC-DOPO.
Embodiment 3 is by 14.9g isocyanuric acid three-glycidyl ester (TGIC), 32.9g 9, mix-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy joins in the there-necked flask that fills 100g ethylene dichloride, under agitation condition, be warming up to 80 DEG C, after question response thing dissolves completely, stirring reaction 6 hours, after reaction finishes, underpressure distillation, removes ethylene dichloride, cooling after, product is joined and in 100g ethanol, carries out agitator treating, keep 78 DEG C, leave standstill and be cooled to room temperature, filter out product, dry, obtain target product TGIC-DOPO.
Embodiment 4 is by 62.6g 9, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy joins in reaction vessel, and be heated 130 DEG C of meltings, add gradually subsequently 29.7g isocyanuric acid three-glycidyl ester, keep temperature of reaction at 170 DEG C, under agitation condition, react 8 hours, obtain crude product TGIC-DOPO; The product of the first step reaction preparation is joined in 200g washed with isopropyl alcohol solvent, maintain the temperature at 82 DEG C, agitator treating, is cooled to room temperature, staticly settles, and obtains product TGIC-DOPO after filtering drying.
Embodiment 5 is by 31.9g 9, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy joins in reaction vessel, and be heated 130 DEG C of meltings, add gradually subsequently 14.9g isocyanuric acid three-glycidyl ester, keep temperature of reaction at 180 DEG C, under agitation condition, react 3 hours, obtain crude product TGIC-DOPO; The product of the first step reaction preparation is joined in 200g washing with alcohol solvent, maintain the temperature at 78 DEG C, agitator treating, is cooled to room temperature, staticly settles, and obtains product TGIC-DOPO after filtering drying.
Embodiment 6 is by 64.8g 9, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy joins in reaction vessel, and be heated 130 DEG C of meltings, add gradually subsequently 29.7g isocyanuric acid three-glycidyl ester, keep temperature of reaction at 160 DEG C, under agitation condition, react 1 hour, obtain crude product TGIC-DOPO; The product of the first step reaction preparation is joined in 200g washing with alcohol solvent, maintain the temperature at 78 DEG C, agitator treating, is cooled to room temperature, staticly settles, and obtains product TGIC-DOPO after filtering drying.
Claims (5)
1. a phospho hetero phenanthrene derivative flame retardant, is called for short TGIC-DOPO, and its molecular structural formula is:
Wherein, the preparation method of described TGIC-DOPO comprises:
Adopt isocyanuric acid three-glycidyl ester (TGIC) and 9,10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound (DOPO) is raw material, reaction preparation TGIC-DOPO crude product in organic solvent or under molten state, and crude product TGIC-DOPO is washed in alcoholic solution to purification, after desolvation, obtain TGIC-DOPO product.
2. a kind of phospho hetero phenanthrene derivative flame retardant according to claim 1, is characterized by, and the preparation method of described TGIC-DOPO specifically comprises:
In organic solvent, isocyanuric acid three-glycidyl ester and 9, the mol ratio of mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy is 1: 3-1: 6, the consumption of reaction solvent is the quality of 6-10 times of isocyanuric acid three-glycidyl ester quality used, keep temperature of reaction at 110-150 DEG C, under agitation condition, react 3-10 hour;
Wherein, described reaction solvent is the one in methylene dichloride, ethylene dichloride, tetrachloroethane, chloroform, tetracol phenixin, toluene, chlorobenzene, dimethylbenzene, dichlorobenzene.
3. a kind of phospho hetero phenanthrene derivative flame retardant according to claim 1, is characterized in that, the preparation method of described TGIC-DOPO specifically comprises:
Under molten state, react, 9, mix-10-phospho hetero phenanthrene-10-oxide compound of 10-dihydro-9-oxy is heated to 120-150 DEG C of melting in reaction vessel, add gradually subsequently isocyanuric acid three-glycidyl ester, the mol ratio of isocyanuric acid three-glycidyl ester and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1: 2.8-1: 6, and keep temperature of reaction at 130-200 DEG C, under agitation condition, react 1-8 hour, obtain crude product TGIC-DOPO.
4. a kind of phospho hetero phenanthrene derivative flame retardant according to claim 1, is characterized in that, the preparation method of described TGIC-DOPO specifically comprises:
Adopting isocyanuric acid three-glycidyl ester (TGIC) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is raw material, reaction preparation TGIC-DOPO crude product in organic solvent or under molten state;
Crude product is joined in cleaning solvent, and the consumption of solvent is the quality of 1-20 times of isocyanuric acid three-glycidyl ester quality, maintains the temperature at 30-150 DEG C, and agitator treating, is cooled to room temperature, staticly settles, and obtains product TGIC-DOPO after filtering drying.
5. a kind of phospho hetero phenanthrene derivative flame retardant according to claim 4, is characterized in that, described cleaning solvent is the one in ethanol, hexalin, glycerol, propylene glycol, Virahol, isobutyl alcohol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210498980.3A CN103012846B (en) | 2012-11-30 | 2012-11-30 | Phosphaphenanthrene derivative flame retardant |
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| CN201210498980.3A CN103012846B (en) | 2012-11-30 | 2012-11-30 | Phosphaphenanthrene derivative flame retardant |
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| CN103012846B true CN103012846B (en) | 2014-11-19 |
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| CN115073522B (en) * | 2022-07-20 | 2022-11-18 | 上海沪正纳米科技有限公司 | Compound containing silicon, phosphorus and nitrogen based on DOPO group and preparation method and application thereof |
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