CN105237957A - Nano flame-retardant epoxy resin composite material and preparation method thereof - Google Patents
Nano flame-retardant epoxy resin composite material and preparation method thereof Download PDFInfo
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- CN105237957A CN105237957A CN201510784632.6A CN201510784632A CN105237957A CN 105237957 A CN105237957 A CN 105237957A CN 201510784632 A CN201510784632 A CN 201510784632A CN 105237957 A CN105237957 A CN 105237957A
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Abstract
The invention relates to a nano flame-retardant epoxy resin composite material and a preparation method thereof, and belongs to the technical field of epoxy resin flame-retardant modification. According to the preparation method, a nano core-shell structure flame retardant which takes a carbon nanotube as a core and a polymer containing phosphorus and nitrogen as a shell is selected to perform flame-retardant modification on epoxy resin. The preparation method is simple, is easy to implement after treatment and is low in energy consumption, and the prepared nano flame-retardant epoxy resin composite material does not contain halogen and is less in additive volume and significant in flame-retardant effect. Compared with pure epoxy resin, the limit oxygen index of the nano flame-retardant epoxy resin composite material is obviously increased, and the heat release rate peak value, the total heat release amount and the total smoke release amount are obviously reduced.
Description
Technical field
The present invention relates to a kind of nano flame retardant epoxy resin composite material and preparation method thereof, belong to the technical field of ethoxyline resin antiflaming modification.
Background technology
Epoxy resin is the important thermosetting resin of a class, and the U.S. took the lead in realizing suitability for industrialized production in nineteen forty-seven, so far existing more than 60 year history.Due to it, there is excellent adhesive property, mechanical property, erosion resistance, chemical stability, insulativity and cure shrinkage is low, good stability of the dimension, be easy to the advantages such as machine-shaping, be widely used in the every field such as electric, building, traffic, coating, sizing agent.But because ordinary epoxy resin has inflammableness, can not be applied directly to many special dimensions, therefore, the flame-retardant modified research of epoxy resin receives the extensive concern of researcher.
In the work of ethoxyline resin antiflaming study on the modification, improve the flame retardant resistance of epoxy resin mainly through following three approach: (1), by the mode of physical blending, directly adds additive flame retardant in epoxy resin-base; (2) inherent flame retardant epoxy molecule structure is built; (3) fire-retarded epoxy resin solidifying agent molecular structure is built.Report in Chinese invention patent CN103435780A: adopt tetrabromo-bisphenol and 10-(2,5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound is as fire retardant, prepared a kind of phosphorus bromine composite flame-proof epoxy resin, the method production cost is low and productive rate is high.Report in Chinese invention patent CN103525004A: use iron cpd to carry out composite as fire retarding synergist and expansion type flame retardant, be applied in ethoxyline resin antiflaming modification, improve the defect that ordinary epoxy resin combustion heat burst size is larger with raw smoke which.
But epoxy resin composite material prepared by above-mentioned report, exists that flame retarding efficiency is not high, the shortcoming such as mechanical properties decrease and contaminate environment in use and removal process.Therefore, research and develop a kind of Halogen highly effective flame-retardant epoxy resin composite material and there is important theory value and realistic meaning.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part, provide a kind of nano flame retardant epoxy resin composite material and preparation method thereof, adopt Halogen efficient nano nucleocapsid structure fire retardant, addition is few and flame retardant effect is obvious.
Nano flame retardant epoxy resin composite material of the present invention, comprises following composition: resin, fire retardant and solidifying agent.
Described resin be selected from bisphenol A type epoxy resin, bisphenol-s epoxy resin, novolac type epoxy resin, o-cresol formaldehyde type epoxy resin one or more.
Described solidifying agent be selected from amine, imidazoles, anhydrides, metallic salt one or more.
Wherein, the mass ratio of described resin and described fire retardant is 1:0.01-0.25, and the mass ratio of described resin and described solidifying agent is 1:0.15-0.65.
Preferably, the mass ratio of described resin and described fire retardant is 1:0.01-0.15, and the mass ratio of described resin and described solidifying agent is 1:0.15-0.45.
Described fire retardant is a kind of is core with carbon nanotube, phosphorus-nitrogen containing element polymkeric substance is the nano-core-shell structure fire retardant of shell, nucleocapsid structure phosphorus nitrogen system nano-meter flame retardants, phosphenyl oxychloride and 4, the polymkeric substance that the polycondensation of 4'-diaminodiphenylmethane obtains is coated to carbon nano tube surface by pi-pi accumulation effect, forms composite material of core-shell structure.Fire retardant synthesis material used: carbon nanotube, phosphenyl oxychloride, 4,4'-diaminodiphenylmethane, acid binding agent and organic solvent.Described carbon nanotube is multi-walled carbon nano-tubes or Single Walled Carbon Nanotube.Described acid binding agent is organic amine, carbonate, any one in pyridines; Preferably, described acid binding agent is any one in triethylamine, sodium carbonate, salt of wormwood.Described organic solvent is any one in tetrahydrofuran (THF), toluene, dimethylbenzene, acetone, acetonitrile, methyl alcohol, ethanol.Wherein, the mass concentration of described carbon nanotube and described organic solvent is 0.5-10.0g/L, the mol ratio of described phosphenyl oxychloride and described acid binding agent is 1:1.0-2.5, and the mol ratio of described phosphenyl oxychloride and described 4,4'-diaminodiphenylmethane is 1:0.5-1.5.Shell thickness can be regulated and controled by the proportioning between feed change, nucleocapsid structure phosphorus nitrogen system nano-meter flame retardants of the present invention massfraction shared by shell is divided into 3 grades, is respectively nano-core-shell structure fire retardant-1, nano-core-shell structure fire retardant-2, nano-core-shell structure fire retardant-3; Nano-core-shell structure fire retardant-1, shell massfraction is 70%-80%, and does not comprise 80%; Nano-core-shell structure fire retardant-2, shell massfraction is 80%-90%, and does not comprise 90%; Nano-core-shell structure fire retardant-3; Shell massfraction is 90%-95%.
The synthesis technique of fire retardant:
The first step: described carbon nanotube, acid binding agent and the part organic solvent that occupies machine total solvent volume 70-85% are mixed together evenly and carry out supersound process, power is 200-300W, and the time is 30-360min;
Second step: add phosphenyl oxychloride in the reaction mixture that the first step obtains, Keep agitation makes it mix;
3rd step: drip the mixed solution that 4,4'-diaminodiphenylmethane is made into residue organic solvent in the reaction mixture that second step obtains, keeps temperature of reaction system to be-10-20 DEG C simultaneously;
4th step: after dropwising, temperature of reaction system is risen to 40-100 DEG C, continues reaction 8-14h;
5th step: carry out suction filtration to the reaction mixture that the 4th step obtains, then uses organic solvent and deionized water wash 2-5 time respectively, finally under 50-90 DEG C of vacuum state, dries gained solid product to constant weight and get final product.
The synthesis technique of matrix material:
The first step: in mass ratio nano-core-shell structure fire retardant is slowly joined in resin, mixture is progressively warming up to 100-200 DEG C, and continue stirring until fire retardant and mix in resin;
Second step: add solidifying agent in the mixture obtained to the first step in mass ratio, and be stirred to solidifying agent and dissolve completely, fully mix;
3rd step: the mixture that second step obtains is placed in 100-200 DEG C of vacuum drying oven and vacuumizes 2-4min, the gas in removing system;
4th step: the mixture that the 3rd step obtains is poured into rapidly in the mould of preheating, first Procuring 1-4h at 100-150 DEG C, then 3-6h is solidified at 150-200 DEG C, naturally cool to room temperature and namely obtain product.
Nano flame retardant epoxy resin composite material prepared by the present invention is compared with prior art: (1) is not halogen-containing, little to environmental influence; (2) preparation technology is simple, and aftertreatment is easy and energy consumption is lower; (3) flame retardant effect significantly and addition is few, can meet the service requirements of more special dimension.
Embodiment
Below by specific embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited to following embodiment.Within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Comparative example 1
100g bisphenol A type epoxy resin is heated to 100 DEG C, adds 25.3g4,4'-diaminodiphenylmethane solidifying agent, and be stirred to solidifying agent and dissolve completely, fully mix; Be placed in 100 DEG C of vacuum drying ovens and vacuumize 3min, the gas in removing system; Then be poured into rapidly in the mould of preheating, first Procuring 2h at 120 DEG C, then solidify 4h at 170 DEG C, naturally cool to room temperature and namely obtain epoxy resin samples.
Embodiment 2
2.6g nano-core-shell structure fire retardant-1 (its shell massfraction is 77.1%) is slowly joined in 100g bisphenol A type epoxy resin, is progressively warming up to 100 DEG C, and continue stirring until fire retardant and mix in resin; Then add 25.3g4,4'-diaminodiphenylmethane solidifying agent, and be stirred to solidifying agent and dissolve completely, fully mix; Be placed in 100 DEG C of vacuum drying ovens and vacuumize 3min, the gas in removing system; Then be poured into rapidly in the mould of preheating, first Procuring 2h at 120 DEG C, then solidify 4h at 170 DEG C, naturally cool to room temperature and namely obtain nano flame retardant epoxy resin samples.
Embodiment 3
2.6g nano-core-shell structure fire retardant-2 (its shell massfraction is 80.8%) is slowly joined in 100g bisphenol A type epoxy resin, is progressively warming up to 100 DEG C, and continue stirring until fire retardant and mix in resin; Then add 25.3g4,4'-diaminodiphenylmethane solidifying agent, and be stirred to solidifying agent and dissolve completely, fully mix; Be placed in 100 DEG C of vacuum drying ovens and vacuumize 3min, the gas in removing system; Then be poured into rapidly in the mould of preheating, first Procuring 2h at 120 DEG C, then solidify 4h at 170 DEG C, naturally cool to room temperature and namely obtain nano flame retardant epoxy resin samples.
Embodiment 4
2.6g nano-core-shell structure fire retardant-3 (its shell massfraction is 92.7%) is slowly joined in 100g bisphenol A type epoxy resin, is progressively warming up to 100 DEG C, and continue stirring until fire retardant and mix in resin; Then add 25.3g4,4'-diaminodiphenylmethane solidifying agent, and be stirred to solidifying agent and dissolve completely, fully mix; Be placed in 100 DEG C of vacuum drying ovens and vacuumize 3min, the gas in removing system; Then be poured into rapidly in the mould of preheating, first Procuring 2h at 120 DEG C, then solidify 4h at 170 DEG C, naturally cool to room temperature and namely obtain nano flame retardant epoxy resin samples.
Embodiment 5
5.2g nano-core-shell structure fire retardant-2 (its shell massfraction is 80.8%) is slowly joined in 100g bisphenol A type epoxy resin, is progressively warming up to 100 DEG C, and continue stirring until fire retardant and mix in resin; Then add 25.3g4,4'-diaminodiphenylmethane solidifying agent, and be stirred to solidifying agent and dissolve completely, fully mix; Be placed in 100 DEG C of vacuum drying ovens and vacuumize 3min, the gas in removing system; Then be poured into rapidly in the mould of preheating, first Procuring 2h at 120 DEG C, then solidify 4h at 170 DEG C, naturally cool to room temperature and namely obtain nano flame retardant epoxy resin samples.
Epoxy resin samples embodiment 1 to embodiment 5 prepared carries out flame retardant properties test.By ASTMD2863-97 standard, carry out limiting oxygen index(LOI) test; By ISO5660 standard, carry out cone calorimetry test, surface heat flow rate is 50kW/m
2.Result is as shown in table 1.
The flame retardant properties of table 1 nano flame retardant epoxy resin composite material
| Test event | Comparative example 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Limiting oxygen index(LOI) (%) | 26.3 | 29.8 | 32.3 | 31.9 | 32.8 |
| Heat release rate peak value (kW/m 2) | 1420.3 | 1135.6 | 754.2 | 994.7 | 589.9 |
| Total heat release (MJ/m 2) | 143.6 | 96.0 | 101.5 | 100.8 | 89.7 |
| Total smoke release (m 2·m -2) | 5905.9 | 3604.7 | 4628.5 | 3992.0 | 5864.3 |
[0039]
Claims (7)
1. a nano flame retardant epoxy resin composite material, is characterized in that, raw material comprises following composition: resin, fire retardant and solidifying agent; Fire retardant is a kind of is core with carbon nanotube, phosphorus-nitrogen containing element polymkeric substance is the nano-core-shell structure fire retardant of shell, the polymkeric substance that phosphenyl oxychloride and the polycondensation of 4,4'-diaminodiphenylmethane obtain is coated to carbon nano tube surface by pi-pi accumulation effect, forms nucleocapsid structure.
2., according to a kind of nano flame retardant epoxy resin composite material of claim 1, it is characterized in that, described resin be selected from bisphenol A type epoxy resin, bisphenol-s epoxy resin, novolac type epoxy resin, o-cresol formaldehyde type epoxy resin one or more.
3., according to a kind of nano flame retardant epoxy resin composite material of claim 1, it is characterized in that, described solidifying agent be selected from amine, imidazoles, anhydrides, metallic salt one or more.
4. according to a kind of nano flame retardant epoxy resin composite material of claim 1, it is characterized in that, the mass ratio of described resin and described fire retardant is 1:0.01-0.25, and the mass ratio of described resin and described solidifying agent is 1:0.15-0.65.
5. according to a kind of nano flame retardant epoxy resin composite material of claim 1, it is characterized in that, the mass ratio of described resin and described fire retardant is 1:0.01-0.15, and the mass ratio of described resin and described solidifying agent is 1:0.15-0.45.
6. according to a kind of nano flame retardant epoxy resin composite material of claim 1, it is characterized in that, nucleocapsid structure phosphorus nitrogen system nano-meter flame retardants massfraction shared by shell is divided into 3 grades, is respectively nano-core-shell structure fire retardant-1, nano-core-shell structure fire retardant-2, nano-core-shell structure fire retardant-3; Nano-core-shell structure fire retardant-1, shell massfraction is 70%-80%, and does not comprise 80%; Nano-core-shell structure fire retardant-2, shell massfraction is 80%-90%, and does not comprise 90%; Nano-core-shell structure fire retardant-3; Shell massfraction is 90%-95%.
7. prepare the method for the nano flame retardant epoxy resin composite material described in any one of claim 1-6, it is characterized in that, comprise the following steps:
The first step: in mass ratio nano-core-shell structure fire retardant is slowly joined in resin, mixture is progressively warming up to 100-200 DEG C, and continue stirring until fire retardant and mix in resin;
Second step: add solidifying agent in the mixture obtained to the first step in mass ratio, and be stirred to solidifying agent and dissolve completely, fully mix;
3rd step: the mixture that second step obtains is placed in 100-200 DEG C of vacuum drying oven and vacuumizes 2-4min, the gas in removing system;
4th step: the mixture that the 3rd step obtains is poured into rapidly in the mould of preheating, first Procuring 1-4h at 100-150 DEG C, then 3-6h is solidified at 150-200 DEG C, naturally cool to room temperature and namely obtain product.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105694370A (en) * | 2016-04-08 | 2016-06-22 | 西南石油大学 | Toughened-flame-retardant epoxy resin material and preparation method thereof |
| CN107629192A (en) * | 2017-09-21 | 2018-01-26 | 上海稳优实业有限公司 | The preparation method of fire-retardant electrically epoxy-resin systems |
| CN108587041A (en) * | 2018-03-17 | 2018-09-28 | 东莞市新征程信息技术有限公司 | It is a kind of to be used to manufacture flame retardant plastics of li battery shell and preparation method thereof |
| CN108727782A (en) * | 2018-06-12 | 2018-11-02 | 北京工商大学 | A kind of phosphorus nitrogen system nano flame retardant epoxy resin composite material and preparation method thereof |
| CN109553929A (en) * | 2018-11-30 | 2019-04-02 | 北京工商大学 | A kind of nano flame retardant epoxy resin composite material and preparation method thereof |
| CN109553928A (en) * | 2018-11-30 | 2019-04-02 | 北京工商大学 | A kind of silicon bromine system clad structure nano-meter flame retardants and preparation method thereof |
| CN110819033A (en) * | 2019-11-11 | 2020-02-21 | 内蒙古民族大学 | Nano high polymer material and preparation method thereof |
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| CN103304777A (en) * | 2013-07-04 | 2013-09-18 | 苏州瀚海高分子有限公司 | Titanium dioxide nanotube-epoxy resin composite flame retardant material and preparation method thereof |
| CN104356393A (en) * | 2014-10-24 | 2015-02-18 | 沈阳化工大学 | Polymer-type phosphorus and nitrogen-containing flame retardant and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102702687A (en) * | 2012-06-26 | 2012-10-03 | 华东理工大学 | Inflaming retarding epoxy resin nanometer composite material |
| CN103304777A (en) * | 2013-07-04 | 2013-09-18 | 苏州瀚海高分子有限公司 | Titanium dioxide nanotube-epoxy resin composite flame retardant material and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694370A (en) * | 2016-04-08 | 2016-06-22 | 西南石油大学 | Toughened-flame-retardant epoxy resin material and preparation method thereof |
| CN105694370B (en) * | 2016-04-08 | 2017-11-24 | 四川天策聚材科技有限公司 | A kind of toughening flame-proof type epoxide resin material and preparation method thereof |
| CN107629192A (en) * | 2017-09-21 | 2018-01-26 | 上海稳优实业有限公司 | The preparation method of fire-retardant electrically epoxy-resin systems |
| CN108587041A (en) * | 2018-03-17 | 2018-09-28 | 东莞市新征程信息技术有限公司 | It is a kind of to be used to manufacture flame retardant plastics of li battery shell and preparation method thereof |
| CN108727782A (en) * | 2018-06-12 | 2018-11-02 | 北京工商大学 | A kind of phosphorus nitrogen system nano flame retardant epoxy resin composite material and preparation method thereof |
| CN108727782B (en) * | 2018-06-12 | 2020-08-07 | 北京工商大学 | Phosphorus-nitrogen nanometer flame-retardant epoxy resin composite material and preparation method thereof |
| CN109553929A (en) * | 2018-11-30 | 2019-04-02 | 北京工商大学 | A kind of nano flame retardant epoxy resin composite material and preparation method thereof |
| CN109553928A (en) * | 2018-11-30 | 2019-04-02 | 北京工商大学 | A kind of silicon bromine system clad structure nano-meter flame retardants and preparation method thereof |
| CN110819033A (en) * | 2019-11-11 | 2020-02-21 | 内蒙古民族大学 | Nano high polymer material and preparation method thereof |
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