CN103059265A - Halogen-free flame retardant epoxy resin containing naphthalene ring structure and preparation method thereof - Google Patents
Halogen-free flame retardant epoxy resin containing naphthalene ring structure and preparation method thereof Download PDFInfo
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- CN103059265A CN103059265A CN2013100204714A CN201310020471A CN103059265A CN 103059265 A CN103059265 A CN 103059265A CN 2013100204714 A CN2013100204714 A CN 2013100204714A CN 201310020471 A CN201310020471 A CN 201310020471A CN 103059265 A CN103059265 A CN 103059265A
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- ZNQGTQPOORPLDI-UHFFFAOYSA-N O=P(c1ccccc1)(Oc1c(cccc2OCC3OC3)c2ccc1)Oc1cccc2c1cccc2OCC1OC1 Chemical compound O=P(c1ccccc1)(Oc1c(cccc2OCC3OC3)c2ccc1)Oc1cccc2c1cccc2OCC1OC1 ZNQGTQPOORPLDI-UHFFFAOYSA-N 0.000 description 1
- OSSHPYDEYVVXIF-UHFFFAOYSA-N Oc1cccc2c1cccc2OP(c1ccccc1)(Oc1cccc2c1cccc2O)=O Chemical compound Oc1cccc2c1cccc2OP(c1ccccc1)(Oc1cccc2c1cccc2O)=O OSSHPYDEYVVXIF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to halogen-free flame retardant epoxy resin based on a phenyl di-naphthoxy oxygen phosphorus structure and a preparation method thereof, and belongs to the technical field of novel-structure and high-performance epoxy resin. The preparation method comprises the following steps: adopting phenyl dichloro oxygen phosphorus and 1,5-naphthalenediol as raw materials to synthesize phenyl di-naphthoxy oxygen phosphorus; reacting the obtained phenyl di-naphthoxy oxygen phosphorus with epoxy chloropropane and sodium hydroxide to obtain the halogen-free flame retardant epoxy resin containing a naphthalene ring structure: phenyl di-naphthoxy oxygen phosphorus glycidyl ether epoxy resin. The obtained epoxy resin has the characteristics of excellent flame retardant property and good heat resistance; and after being cured by 4,4'-diamino diphenyl sulphone, a glass-transition temperature of a cured object reaches more than 210 DEG C; and the inflaming retarding grades of products obtained by curing through adopting DDS (4,4'-diamino diphenyl sulphone) and a dicyandiamide curing agent reach UL94 V-0 grades.
Description
Technical field
The present invention relates to the Resins, epoxy technical field, particularly a kind of naphthalene ring Halogenless fire retarded epoxy resin and preparation method thereof that contains.
Background technology
The thermosetting resin that Resins, epoxy one class is important, have excellent adhesiveproperties, wear resisting property, mechanical property, electrical insulation capability, chemical stability, high and low temperature resistance, and low, the easy machine-shaping of shrinking percentage and the advantage such as with low cost, be used widely in fields such as electronic instrument, light industry, building, machinery, space flight and aviation, coating, electric insulating material and advanced composite materials.
Epoxy resin cured product has good electrical insulation properties and physical and mechanical property, however its oxygen index only have about 19.8, without fire-retardant performance, can't use in the occasion that fire-retardant requirement is arranged.At present, the existing relevant trade mark product of fire-retardant epoxy resin, using maximum is brominated Resins, epoxy.Yet, comprise that the halogen series flame retardant material of brominated Resins, epoxy runs into the puzzlement of Dioxins problem, be that the halogen series flame retardant material is when Pintsch process and burning, produce poisonous polybrominated dibenzo-furan and brominated diphenyl Dioxins, this is that a class can be damaged skin and internal organ, and has the material that promotes body deformity and carcinogenesis.Therefore, the Halogen flame retarded polymeric material fails to obtain the environmental protection sign in Europe, and China also uses problem in the restriction of considering brominated Resins, epoxy at present, and therefore, the research and development Halogenless fire retarded epoxy resin is significant.
The Halogenless fire retarded epoxy resin of open report mainly concentrates on the phospho hetero phenanthrene compound both at home and abroad at present, and 9,10-dihydro-9-oxy is mixed-the assorted phenanthrene of 10-phosphinylidyne-10-oxide compound.Use DOPO and derivative thereof and dihydroxyphenyl propane Racemic glycidol ether type epoxy obtain to have phosphor-containing structure by addition reaction Resins, epoxy, its cured article has good flame-retarding characteristic.Yet, being applied in when emphasizing high oxygen index, high flame retardant grade of fire retarding epoxide resin, the raising of its thermostability also has important Practical significance, yet few for the report that contains large size naphthalene nucleus rigid structure phosphorous epoxy resin.The naphthalene ring Halogenless fire retarded epoxy resin that contains involved in the present invention, by Molecular Structure Design and modification, when giving the Resins, epoxy high flame resistance, significantly improved the resistance toheat of Resins, epoxy, be of great significance and using value at copper-clad plate technical field of composite materials tool.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of naphthalene ring Halogenless fire retarded epoxy resin and preparation method thereof that contains, a kind of naphthalene ring Halogenless fire retarded epoxy resin that contains, and its molecular structural formula is as follows:
The described naphthalene ring Halogenless fire retarded epoxy resin that contains, its epoxy equivalent (weight) is 277-301g/mol;
The described naphthalene ring Halogenless fire retarded epoxy resin that contains, can adopt following processing step preparation:
(1) with 5-20 weight part phenyl two chlorethoxyfos, 20-50 weight part 1, the 5-naphthalenediol, hybrid reaction in the 20-200 parts by weight solvent, 110 ℃-180 ℃ of temperature of reaction, reaction times 4-8h, reaction finishes the rear desolvation of cooling and unreacting material, obtain phenyl two naphthyloxy oxygen phosphorus, its molecular structure is as follows:
(2) with 25-40 weight part phenyl two naphthyloxy oxygen phosphorus, 40-60 weight part epoxy chloropropane, 0-15 part solubility promoter, 0.5-3 a portion phase-transfer catalyst mixes to get clear solution, slowly add 12-15 part sodium hydroxide, react 6-8h under 65 ℃ of-135 ℃ of conditions, reaction finishes the sodium-chlor that cooling removes by filter generation, unreacted epoxy chloropropane and solubility promoter are removed in the washing underpressure distillation, obtain the Halogenless fire retarded epoxy resin based on phenyl two naphthyloxy oxygen phosphorus structures.
Described naphthalene ring Halogenless fire retarded epoxy resin preparation process (1) solvent for use that contains is selected one or more of benzene,toluene,xylene, methyl iso-butyl ketone (MIBK);
The described used solubility promoter of naphthalene ring Halogenless fire retarded epoxy resin preparation process (2) that contains is selected one or both of Virahol, isopropylcarbinol;
The described used phase-transfer catalyst of naphthalene ring Halogenless fire retarded epoxy resin preparation process (2) that contains is selected a kind of of benzyl trimethyl ammonium chloride, benzyltrimethylammonium bromide, ethyl triphenyl brometo de amonio or any several mixture.
The present invention compared with prior art, its beneficial effect is: preparation contain the naphthalene ring Halogenless fire retarded epoxy resin, resin has certain organophosphorus content, thereby can generate rapidly organophosphorus oxide-isolated material in when burning contacts with air and reaches flame retardant effect, resinous molecular structure is rich in the two keys of aromatic nucleus planar conjugate simultaneously, local arrangements is regular and be easy to accumulation, can suppress sub-chain motion, has good resistance toheat.
A kind of naphthalene ring Halogenless fire retarded epoxy resin preparation method that contains involved in the present invention adopts 1,5 '-naphthalenediol, and phenyl two chlorethoxyfos, epoxy chloropropane are main raw material, with low cost, technique is simple; The preparation feedback process need not to carry out separation of by-products, is applicable to suitability for industrialized production.
The inventive method is prepared contains the naphthalene ring Halogenless fire retarded epoxy resin, has wide range of applications.Adopting DDS is that the prepared resin solidification casting matrix of solidifying agent second-order transition temperature reaches more than 220 ℃, has good resistance toheat, and the right hand oxygen index 32 of the limit reaches UL94V-0 level flame-retardant standard.Adopting DICY is 412 ℃ of the initial heat decomposition temperatures of the prepared resin solidification casting matrix of solidifying agent, and 800 ℃ of carbon residue rates 23.1% have good thermostability, and limit burns oxygen index 35 reaches UL94V-0 level flame-retardant standard.
Description of drawings
The invention will be further described below in conjunction with the drawings and specific embodiments.
Fig. 1 is the phenyl two naphthyloxy oxygen phosphorus molecular structures among the present invention.
Fig. 2 is the phenyl two naphthyloxy oxygen phosphorus tetraglycidel ether epoxy resin molecular structures among the present invention.
Embodiment
Embodiment 1
In being equipped with the four-hole boiling flask of mechanical stirring, thermometer, reflux condensing tube and nitrogen gatherer, 1000mL adds 290g1,5-naphthalenediol and 200g dimethylbenzene, slow rising oil bath temperature to 125 ℃, treat 1, after the 5-naphthalenediol dissolves fully, 80g phenyl two chlorethoxyfos are added drop-wise in the reaction system, 2h is reinforced to be finished, temperature of reaction is controlled at 125 ℃, continues reaction 8h.After reaction finishes thickening filtration remove unreacted 1, the 5-naphthalenediol, 80 ℃ of deionized waters washings 5 times, underpressure distillation desolventizing and excessive moisture obtain brown thick liquid product.With gained brown thick liquid product 41g, the 100g epoxy chloropropane, 15g Virahol mixed dissolution is in the 250ml four-hole boiling flask with stirring, reflux exchanger and thermometer, and 75 ℃ of oil bath temperatures are with 30g, the 30wt% aqueous sodium hydroxide solution slowly splashes into, drip off in the 1h, oil bath temperature is increased to 80 ℃, continue reaction 4h, cold filtration was removed the sodium-chlor that generates, underpressure distillation desolvation after reaction finished.With the toluene dissolving, deionized water washing 3 times behind the desolvation, obtains the brown color solid product with the methylene dichloride recrystallization.Adopting the hydrochloric acid acetone method to test its epoxy equivalent (weight) is 281g/mol.
Adopting the 100g of above-mentioned preparation to contain the naphthalene ring Halogenless fire retarded epoxy resin mixes with 22gDDS, be dissolved in 250ml acetone and 250mlN, in the dinethylformamide mixed solvent, the underpressure distillation desolvation obtained resin and curing agent mixture 122.4g, 120 ℃ of 1h, 180 ℃ of 1h after dissolving was finished, after solidifying, 220 ℃ of 2h obtain resin cured matter, 212.5 ℃ of second-order transition temperatures, limiting oxygen index(LOI) 32.1, UL94-V0 flame-retardant standard.
Embodiment 2
In being equipped with the four-hole boiling flask of mechanical stirring, thermometer, reflux condensing tube and nitrogen gatherer, 250mL adds 120g1,5-naphthalenediol and 100g methyl iso-butyl ketone (MIBK), slow rising oil bath temperature to 110 ℃, treat 1, after the 5-naphthalenediol dissolves fully, 24g phenyl two chlorethoxyfos are added drop-wise in the reaction system, 1h is reinforced to be finished, temperature of reaction is controlled at 115 ℃, continues reaction 6h.Desolvation after reaction finishes adds dimethylbenzene 100g condensing crystal, remove by filter unreacted 1, the 5-naphthalenediol, with deionized water washing 5 times, underpressure distillation obtains brown thick liquid product except removal xylene and excessive moisture.With gained brown thick liquid product 21.5g, 100g epoxy chloropropane mixed dissolution is in the 250ml four-hole boiling flask with stirring, reflux exchanger and thermometer, 80 ℃ of oil bath temperatures, with 11.1g, the 40wt% aqueous sodium hydroxide solution slowly splashes into, and drips off in the 1h, keep 80 ℃ of oil bath temperatures, continue reaction 4h, cold filtration was removed the sodium-chlor that generates, underpressure distillation desolvation after reaction finished.With the toluene dissolving, deionized water washing 3 times behind the desolvation, obtains the brown color solid product with the methylene dichloride recrystallization.Adopting the hydrochloric acid acetone method to test its epoxy equivalent (weight) is 285g/mo l.
Adopting the 20g of above-mentioned preparation to contain the naphthalene ring Halogenless fire retarded epoxy resin mixes with 2.2gDICY, be dissolved in 50ml acetone and 50mlN, in the dinethylformamide mixed solvent, the underpressure distillation desolvation obtained resin and curing agent mixture 22.6g after dissolving was finished, 160 ℃ of 1h, 200 ℃ of 1h, after solidifying, 240 ℃ of 2h obtain resin cured matter, the thermogravimetric analysis result shows, under air atmosphere, cured article 5% weightless temperature is 412 ℃, 800 ℃ of carbon residue rates 36.1%, limiting oxygen index(LOI) 33.1, the UL94-V0 flame-retardant standard.
Embodiment 3
In being equipped with the four-hole boiling flask of magnetic agitation, thermometer, reflux condensing tube and nitrogen gatherer, 250mL adds 120g1,5 naphthalenediols and 100g toluene, slow rising oil bath temperature to 120 ℃, treat 1, after 5 naphthalenediols dissolve fully, adopt the micro-sampling pump to join in the reaction system 24g phenyl two chlorethoxyfos, 2h is reinforced to be finished, temperature of reaction is controlled at 120 ℃, continues reaction 8h.It is unreacted 1 that reaction finishes the condensing crystal remove portion, the 5-naphthalenediol, and toluene and excessive moisture are removed in underpressure distillation, obtain brown thick liquid product.With gained brown thick liquid product 21.5g, 100g epoxy chloropropane mixed dissolution is in the 250ml four-hole boiling flask with stirring, reflux exchanger and thermometer, 80 ℃ of oil bath temperatures, with 11.1g, the 40wt% aqueous sodium hydroxide solution slowly joins in the reaction system with the micro-sampling pump, drips off in the 2h, keep 80 ℃ of oil bath temperatures, continue reaction 4h, cold filtration was removed the sodium-chlor that generates, underpressure distillation desolvation after reaction finished.With the toluene dissolving, deionized water washing 3 times behind the desolvation, obtains the brown color solid product with the methylene dichloride recrystallization.Adopting the hydrochloric acid acetone method to test its epoxy equivalent (weight) is 279g/mol.
Adopting the 20g of above-mentioned preparation to contain the naphthalene ring Halogenless fire retarded epoxy resin mixes with 2.2gDICY, 0.1g2-Methylimidazole, be dissolved in 50ml acetone and 50mlN, in the N dimethyl formamide mixed solvent, the underpressure distillation desolvation obtained resin and curing agent mixture 22.8g after dissolving was finished, 160 ℃ of 1h, after solidifying, 200 ℃ of 1h obtain resin cured matter, the thermogravimetric analysis result shows, under nitrogen atmosphere, cured article 5% weightless temperature is 401.8 ℃, 800 ℃ of carbon residue rates 25.7%, limiting oxygen index(LOI) 33.5, UL94-V0 flame-retardant standard.
Embodiment 4
In being equipped with the enamel reaction still of electric heating oil bath chuck, mechanical stirring, thermometer, reflux condensing tube and nitrogen gatherer, 5L adds 1500g1,5-naphthalenediol and 1000g dimethylbenzene, slow rising Heating temperature to 135 ℃, stir 15min, treat that 1,5-naphthalenediol dissolves fully after, 300g phenyl two chlorethoxyfos are added drop-wise in the reactor, 1h is reinforced to be finished, and temperature of reaction is controlled at 135 ℃, continues reaction 6h.It is unreacted 1 that naturally cooling discharging after reaction finishes, thickening filtration are removed, the 5-naphthalenediol, and underpressure distillation desolventizing and excessive moisture obtain the brown viscous liquid product.With gained brown viscous liquid product 1000g, the 2000g epoxy chloropropane, 500g Virahol mixed dissolution is in the enamel reaction still with electric heating oil bath chuck, mechanical stirring, thermometer, reflux condensing tube and nitrogen gatherer, and 80 ℃ of Heating temperatures are with 580g, the 30wt% aqueous sodium hydroxide solution slowly splashes into, drip off in the 1h, oil bath temperature is increased to 90 ℃, continue reaction 2h, cold filtration was removed the sodium-chlor that generates, underpressure distillation desolvation after reaction finished.With the toluene dissolving, deionized water washing 3 times behind the desolvation, obtains the brown color solid product with the methylene dichloride recrystallization.Adopting the hydrochloric acid acetone method to test its epoxy equivalent (weight) is 287g/mol.
Adopting the 100g of above-mentioned preparation to contain the naphthalene ring Halogenless fire retarded epoxy resin mixes with 22gDDS, be dissolved in 250ml acetone and 250mlN, in the dinethylformamide mixed solvent, the underpressure distillation desolvation obtained resin and curing agent mixture 122.4g after dissolving was finished, 120 ℃ of 1h, 180 ℃ of 1h, after solidifying, 220 ℃ of 2h obtain resin cured matter, 211.7 ℃ of second-order transition temperatures, limiting oxygen index(LOI) 32.5, UL94-V0 flame-retardant standard, solidify casting matrix tensile strength 28.7MPa, tensile modulus 3570MPa, three-point bending strength 51.3MPa, modulus in flexure 3010MPa.
Claims (6)
1. one kind contains the naphthalene ring Halogenless fire retarded epoxy resin, it is characterized in that molecular structural formula is as follows:
2. a kind of naphthalene ring Halogenless fire retarded epoxy resin that contains as claimed in claim 1, it is characterized in that: epoxy equivalent (weight) is 277-301g/mol.
3. a kind of naphthalene ring Halogenless fire retarded epoxy resin that contains as claimed in claim 1 is characterized in that adopting following processing step preparation:
(1) with 5-20 weight part phenyl two chlorethoxyfos, 20-50 weight part 1, the 5-naphthalenediol, hybrid reaction in the 20-200 parts by weight solvent, 110 ℃ 180 ℃ of temperature of reaction, reaction times 4-8h, reaction finishes the rear desolvation of cooling and unreacting material, obtain phenyl two naphthyloxy oxygen phosphorus, its molecular structure is as follows:
(2) with 25-40 weight part phenyl two naphthyloxy oxygen phosphorus, 40-60 weight part epoxy chloropropane, 0-15 part solubility promoter, 0.5-3 a portion phase-transfer catalyst mixes to get clear solution, slowly add 12-15 part sodium hydroxide, react 6-8h under 65 ℃ of-135 ℃ of conditions, reaction finishes the sodium-chlor that cooling removes by filter generation, unreacted epoxy chloropropane and solubility promoter are removed in the washing underpressure distillation, obtain the Halogenless fire retarded epoxy resin based on phenyl two naphthyloxy oxygen phosphorus structures.
4. a kind of naphthalene ring Halogenless fire retarded epoxy resin preparation technology that contains as claimed in claim 3, it is characterized in that: described solvent is one or more mixtures of benzene,toluene,xylene, methyl iso-butyl ketone (MIBK).
5. a kind of naphthalene ring Halogenless fire retarded epoxy resin preparation technology that contains as claimed in claim 3, it is characterized in that: described solubility promoter is one or both mixtures of Virahol, isopropylcarbinol.
6. a kind of naphthalene ring Halogenless fire retarded epoxy resin preparation technology that contains as claimed in claim 3 is characterized in that: described phase-transfer catalyst is one or more mixture of benzyl trimethyl ammonium chloride, benzyltrimethylammonium bromide, ethyl triphenyl brometo de amonio.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104163817A (en) * | 2014-02-12 | 2014-11-26 | 安徽善孚新材料科技有限公司 | Epoxy resin containing furan self-repairing group and preparation method thereof |
| CN104193994A (en) * | 2014-08-30 | 2014-12-10 | 海安南京大学高新技术研究院 | Flame-retardant heat-resistant bismaleimide resin and preparation method thereof |
| CN110922394A (en) * | 2019-11-21 | 2020-03-27 | 中国科学院宁波材料技术与工程研究所 | Bio-based intrinsic flame-retardant epoxy resin precursor based on natural flavonoid compound and preparation method and application thereof |
| CN113045864A (en) * | 2021-04-26 | 2021-06-29 | 上海方乾科技有限公司 | Halogen-free flame-retardant epoxy resin containing naphthalene ring structure and preparation method thereof |
| CN113844130A (en) * | 2021-09-13 | 2021-12-28 | 山东金宝电子股份有限公司 | Preparation method of high-Tg high-frequency copper-clad plate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104163817A (en) * | 2014-02-12 | 2014-11-26 | 安徽善孚新材料科技有限公司 | Epoxy resin containing furan self-repairing group and preparation method thereof |
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| CN113045864A (en) * | 2021-04-26 | 2021-06-29 | 上海方乾科技有限公司 | Halogen-free flame-retardant epoxy resin containing naphthalene ring structure and preparation method thereof |
| CN113844130A (en) * | 2021-09-13 | 2021-12-28 | 山东金宝电子股份有限公司 | Preparation method of high-Tg high-frequency copper-clad plate |
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Application publication date: 20130424 |