CN103753905A - Halogen-free flame-retardant resin matrix sandwich structure body and preparation method thereof - Google Patents
Halogen-free flame-retardant resin matrix sandwich structure body and preparation method thereof Download PDFInfo
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- CN103753905A CN103753905A CN201310715090.8A CN201310715090A CN103753905A CN 103753905 A CN103753905 A CN 103753905A CN 201310715090 A CN201310715090 A CN 201310715090A CN 103753905 A CN103753905 A CN 103753905A
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Abstract
The invention discloses a halogen-free flame-retardant resin matrix sandwich structure body. The halogen-free flame-retardant resin matrix sandwich structure body is composed of a core material (I) and resin matrix fiber reinforced body materials (II) which are configured on the upper surface and/or the lower surface of the core material (I), wherein the core material (I) is composed of materials with clearances; the core material has the specific gravity of 0.03-2.0, and has the thickness of 0.1-5.0mm, and is composed of a foaming body with clearances or modified thermoplastic resin matrix fiber reinforced materials; a thermoplastic resin matrix and a long fiber form a clearance structure by crossing fiber wet resin. The halogen-free flame-retardant resin matrix sandwich structure body prepared by the invention achieve the flame-retardant level as high as UL94-V0, and is high in weather resistance, high in ultraviolet irradiation resistance, light in weight, thin in thickness, high in rigidity, simple in process, and mainly applied to surface structure plates of the 3C industry, the household appliance industry, relevant crates and the like.
Description
Technical field
The present invention relates to a kind of halogen-free flame-retardant resin matrix sandwich structural body and preparation method thereof.
Background technology
Under the overall situation in carbon fibre composite market, resin matrix 80% share of being combined with carbon fibre composite is epoxy resin, and the resin matrix of remaining 20% share is phenolic resins, unsaturated-resin and part thermoplastic resin.But compared with epoxy resin, phenolic resins hardness is high, is fragile material, simultaneously cannot dry process carbon fiber prepreg, can only wet method preparation, so just there is serious severe working environment and generation environmental issue.Unsaturated-resin is with low cost a lot of compared with epoxy resin, but its intensity and environmental problem are also very poor, are substantially applied in cheap fiberglass industry at present.The combination technology of thermoplastic resin and carbon fiber is ripe not enough, also in laboratory development, produces in enormous quantities and also fails to realize.
Therefore, it is fast that epoxy resin possesses dry fabrication speed in carbon fibre composite application, and large in batches, moulding process is controlled, and intensity is high, good toughness, and performance can flexible modulation, relative low price, working environment relative clean, the advantages such as environmental protection.
The patent No. is 200580029564.7 to disclose a kind of sandwich structural body, this sandwich structural body (III) is by core (I) and be configured in fiber-reinforced material (II) formation this core (I) two sides, that consist of continuous reinforcement fiber (A) and matrix resin (B), and wherein said core (I) has space.The bubble of described space by foaming body forms, or core consists of discontinuous reinforcing fiber and thermoplastic resin, and described space is formed by the space that infall forms mutually between the long filament of this reinforcing fiber.This patent is to adopt common resin forming to become the carbon fibre composite sheet material of sandwich structural body, is common fabrication scheme in the market, but also has the problems such as molding cycle is long, and production automation degree is low, inflammable.
The conventional way of the general problem that solves resin halogen-free flameproof is in resin, to add halogen-free flame retardants, such as aluminium-hydroxide powder, but conventional halogen-free flame retardants and resin are immiscible, thereby greatly increase the viscosity of resin, affect the mobility of resin and reduce the intensity of epoxy resin, even accomplish that conventional halogen-free flame retardants and resin mix also can greatly reduce the strength problem of carbon fibre composite and separate out in forming process, affecting product surface.
Summary of the invention
In order to overcome carbon fibre composite on existing market, be applied in the defects such as the halogen-free flameproof that runs in 3C industry field, one object of the present invention is to provide a kind of and meets halogen-free flameproof characteristic, weatherability is strong, ultraviolet radiation resisting ability is strong, lightweight, the halogen-free flame-retardant resin matrix sandwich structural body of thin-walled, high rigidity.
Another object of the present invention is to provide the preparation method of above-mentioned halogen-free flame-retardant resin matrix sandwich structural body;
A further object of the present invention is to provide the purposes of above-mentioned halogen-free flame-retardant resin matrix sandwich structural body.
The present invention is achieved by the following technical solution:
A kind of halogen-free flame-retardant resin matrix sandwich structural body, described halogen-free flame-retardant resin matrix sandwich structural body be by core (I) and be configured in this core (I) upper surface and/or lower surface resin matrix fibre reinforcement material (II) form halogen-free flame-retardant resin matrix sandwich structural body (III), described core (I) consists of the material that has space; The proportion of described core (I) is 0.03 ~ 2.0, and thickness is 0.1 ~ 5.0mm.
Described core (I) is foaming body, and according to ASTM D, 638 tests are 10 ~ 1000MPa to described foaming body elastic modelling quantity, and according to ASTM D, 638 tests are 10 ~ 150MPa to modulus of shearing; Described foaming body proportion is 0.03 ~ 1.0, is preferably 0.08 ~ 0.8, more preferably 0.1 ~ 0.6.
Described foaming body is selected from one or more of PMI structural foam, CPMI structural foam, SAN structural foam, PP structural foam, PES structural foam, PU structural foam, PET structural foam, phenolic structure foam, melamine structural foam.
A kind of halogen-free flame-retardant resin matrix sandwich structural body, described halogen-free flame-retardant resin matrix sandwich structural body be by core (I) and be configured in this core (I) upper surface and/or lower surface resin matrix fibre reinforcement material (II) form halogen-free flame-retardant resin matrix sandwich structural body (III), described core (I) consists of thermoplastic resin matrix's fibre reinforcement material of modification, between described thermoplastic resin matrix and long fibre, by fiber, infiltrate resin and intersect to form gap structure, described fiber infiltrates resin length more than 10nm; The proportion of described core (I) is 0.1 ~ 2.0, is preferably 0.1 ~ 1.0, more preferably 0.2 ~ 0.6.
Described resin matrix fibre reinforcement material (II) consists of thermosetting resin matrix fibre reinforcement material; The thermosetting resin that described thermosetting resin matrix is halogen-free flameproof, more than flame retardant rating reaches UL-94 V1 level; Described fibre reinforcement material is selected from one or more of continuous carbon fibre material, glass fiber material, aramid fiber material, basalt fiber material.
The thermosetting resin that described thermosetting resin matrix is halogen-free flameproof, more than flame retardant rating reaches UL-94 V1 level, is by adding fire-retardant resin group to reach halogen-free flameproof characteristic in thermosetting resin macromolecule.The mode of adding: fire-retardant resin group links together by polymerization methods and high molecular resin group; The density of thermosetting resin is 1.05 ~ 1.2; In use, the Tg point control of thermosetting resin matrix is at 100 ℃ ~ 160 ℃.25 ℃ of room temperatures, humidity 55% ~ 75%, resin viscosity is tested and is controlled at 1 ~ 30000mpa.s by rotation viscometer; 80 ℃ of temperature, humidity 55% ~ 75%, resin viscosity is tested and is controlled at 1 ~ 600mpa.s by rotation viscometer, and heat curing temperature is controlled at 120 ℃ ~ 160 ℃, and the time is controlled at 5min ~ 30min; Preferably, heat curing temperature is 140 ℃ ~ 150 ℃, and be 5min ~ 10min hardening time.
The synthetic method of the thermosetting resin of described halogen-free flameproof, comprises the steps:
1) by conventional polymerisation, directly prepare thermosetting resin and the curing agent containing the halogen-free flameproof of N-P;
2) add modified-reaction, the polymer by interpolation with fire retarding effect is to the thermosetting resin that obtains halogen-free flameproof in ordinary hot thermosetting resin.
Described thermosetting halogen-free flame-retardant resin is preferably FD/MFP epoxy-resin systems.
The synthetic method of described FD/MFP epoxy-resin systems:
A) synthesizing containing P epoxy resin FD: prepare the FD epoxy resin that contains 2wt%P element with DOPO and Bisphenol F type novolac epoxy resin;
B) synthesizing containing N epoxy resin MFP: nitrogen-containing hardener 2,4, synthesizing of 6-tri-(hydroxy phenyl benzylidene amino)-s-triazine (MFP): with melamine and phenol reactant, prepare the phenolic curing agent MFP of nitrogen content as 0.5～2.5wt% take the modification of methyl guanamines;
C) containing the preparation of P-N epoxy resin solidifying system glue: get certain proportioning containing the FD epoxy resin of 2wt%P and containing N curing agent MFP, be placed in the solvent methyl first peptamine of strong polarity and the processing of acetone dissolving, curing and make hot melt adhesive liquid and use;
D) synthetic containing the FD/MFP epoxy-resin systems of P-N halogen-free flameproof: actual measurement epoxide number is 0.315mol/100g, and tg is more than 145 ℃, and polymer is when Pwt%=2%, and LOI is 33-39, at 180 ℃, 2min gel, 7-10min is curing, obtains.
The synthetic method reference of described FD/MFP epoxy-resin systems is as Publication about Document: Cao Jun, Liang Bing.DOPO type Halogenless fire retarded epoxy resin architectural study report [J]. New Chemical Materials, 2011,39(8): 7-14; Zheng Cancheng, Zhao Xingmao, Deng Huali.Halogen-free flameproof copper-clad plate preparation method's research [J]. Guangdong chemical industry, 2012,39(5): 278-279; Min Yuqin, Fang Lin, Zhang Xinghong, Qi Guorong.Synthetic and performance study [J] .2006, the 33(4 of novel halogen-free flame-retardant epoxy resin): 429-433; Liu Gang, Li Zhenlin, Yan Hui, Yang Bei, model peace.The progress [J] of Halogenless fire retarded epoxy resin and curing agent thereof for immunity copper-clad plate. chemistry and bonding, 2010,32(2): 50-58.
Wherein, described FD/MFP epoxy-resin systems, tests solidfied material vertical combustion by TGA and UL94, and thermal stability is good, the synergy of P-N, and fire-retardant rank reaches UL94-V0 level.
Dated especially: when making resin streak and test by UL94 test mode vertical combustion, substantially reach UL94-V0 rank, but when containing P-N halogen-free flame-retardant resin by after compound with the continuous fortifying fibre such as carbon fiber or glass fibre, because the factors such as fiber candle wick effect cause a lot of resins all can not reach V0 rank completely, this resin confirms that by fine adjustments P-N content composite reaches UL94-V0 rank; Wherein, described fine adjustments P-N content, is that controlling containing the P content in P epoxy resin FD is 2wt%, and controlling containing nitrogen content in N epoxy resin MFP is 0.5～2.5wt%, when nitrogen content is during lower than 0.5wt%, little to improving the contribution of anti-flammability; When nitrogen content is during higher than 2.5wt%, can make the water absorption rate of epoxy-resin systems solidfied material increase.
Correspondingly, by thermosetting resin and the fibre reinforcement material of halogen-free flameproof, form thermosetting resin matrix fibre reinforced materials, be preferably containing P-N, FD/MFP epoxy resin base carbon fiber/glass fibre prepreg, can obtain by two kinds of preparation methods below:
1, wet method (solvent method) preparation is containing P-N, FD/MFP epoxy resin base carbon fiber/glass fibre prepreg: the FD/MFP epoxy-resin systems containing P-N halogen-free flameproof is mixed with to glue, then by increasing acetone diluted, become the mixture that viscosity is very low, by to making after the impregnation-oven dry of the woven cloth such as carbon fibers/fiberglass containing P-N, FD/MFP epoxy resin base carbon fiber/glass fibre prepreg.
2, dry method (fusion method) preparation is containing P-N, FD/MFP epoxy resin base carbon fiber/glass fibre prepreg: the FD/MFP epoxy-resin systems that contains P-N is made to heat molten type glue, by traditional heat molten type preimpregnation machine equipment by after the fusing of higher viscosity FD/MFP resin and the unidirectional UD of carbon fibers/fiberglass or the laminating infiltration of woven cloth make containing P-N, FD/MFP epoxy resin base carbon fiber/glass fibre prepreg.
Described resin matrix fibre reinforcement material (II) consists of thermoplastic resin matrix's fibre reinforcement material; Described thermoplastic resin is the halogen-free combustion-proof thermoplastic resin of modification, more than flame retardant rating reaches UL94 V1 level; Described fibre reinforcement material is selected from one or more mixtures of continuous carbon fibre material, glass fiber material, aramid fiber material, basalt fiber material.
Described thermoplastic resin is the halogen-free combustion-proof thermoplastic resin of modification, more than flame retardant rating reaches UL94-V1 level, be by adding fire-retardant resin group to reach halogen-free flameproof characteristic in resin macromolecule, its addition manner has two kinds of blending and modifying and polymerisations; The tg point control of described thermoplastic resin is at 120 ℃ ~ 160 ℃; Described thermoplastic resin is preferably halogen-free flameproof PP and/or the PE plastics of modification, is existing product, the halogen-free flameproof PP of the more preferably modification of JinFa Science Co., Ltd and/or PE plastics.
Correspondingly, by thermoplastic resin and the fibre reinforcement material of the halogen-free flameproof of modification, form thermoplastic resin matrix's fibre reinforced materials, be preferably PP and/or PE plastic base carbon fibre initial rinse sheet.
A preparation method for halogen-free flame-retardant resin matrix sandwich structural body, comprises the steps:
A) stacked step: comprise resin matrix fibre reinforcement material (II) is layered in to the upper surface of described core (I) and/or lower surface so that duplexer to be provided;
B) heating pressurization steps: be included in the duplexer that in firm matter flat plate mold, configuration obtains by step a), heat 100 ~ 200 ℃, pressurization maintains and is cooled to rapidly 80 ℃ after 0.5 ~ 30min and carries out below moulding, makes halogen-free flame-retardant resin matrix sandwich structural body (III).
The halogen-free flame-retardant resin matrix sandwich structural body that the preparation method of described halogen-free flame-retardant resin matrix sandwich structural body obtains is in the application of 3C industry, household electric appliances and cabinet surface texture sheet material.
The present invention compared with prior art, has following technique effect:
1) the halogen-free flame-retardant resin matrix sandwich structural body flame retardant rating that the present invention makes is up to UL94-V0, Halogen, and nontoxic, volatility is little, does not produce toxic gas and secondary pollution during burning.
2) the halogen-free flame-retardant resin matrix sandwich structural body that the present invention makes has high heat decomposition temperature, under excellent heat endurance and heating condition, keeps good hot physical and mechanical properties.
3) the halogen-free flame-retardant resin matrix sandwich structural body ultraviolet radiation resisting ability that the present invention makes is strong.
4) the halogen-free flame-retardant resin matrix sandwich structural body that the present invention makes is lightweight, thin thickness, and rigidity is high, can be applicable to the surface texture sheet materials such as 3C industry, household electric appliances and relevant cabinet.
Accompanying drawing explanation
Fig. 1 is the structural representation of halogen-free flame-retardant resin matrix sandwich structural body of the present invention.
The specific embodiment
Below by the specific embodiment, further illustrate the present invention, following examples are preferably embodiment of the present invention, but embodiments of the present invention are not subject to the restriction of following embodiment.
Now embodiment and comparative example raw material used are done to following explanation, but are not limited to these materials:
Resin matrix fibre reinforcement material:
Thermoplastic resin matrix's fibre reinforcement material: thermoplastic resin-based carbon fiber preliminary-dip piece CFR-2, golden hair carbon fiber new material development Co., Ltd;
Thermosetting resin matrix fibre reinforcement material: containing P-N, FD/MFP epoxy resin base carbon fiber prepreg CFR-1, golden hair carbon fiber new material development Co., Ltd;
As the foaming body of core:
Take the FR100 of Gurit company, be that PET structural foam is as core; Similarly, the 71WF of Rohacell company type PMI structural foam, phenolic structure foam, melamine structural foam all can be used as the foaming body use of core.
By the FR100 of Gurit company, be that (proportion is 100kg/m to PET structural foam
3) cut into 3.0mm thickness and 320mm*250mm surface size (weight is 24g) using the foaming body as thering is space, according to ASTM D 638, test is 70MPa to the elastic modelling quantity of foaming body, modulus of shearing is 35Mpa;
The surface size (every weight is 35g) that will cut into 0.25mm thickness and 320mm*250mm with thermoplastic resin-based carbon fiber preliminary-dip piece (CFR-2, golden hair carbon fiber new material development Co., Ltd) is using as resin matrix fibre reinforcement material; Two surfaces up and down that resin matrix fibre reinforcement material layer is stacked in to described foaming body are to provide duplexer;
Preparation levelness is smooth, fineness is the steel flat plate mold of 5 ~ 13 grades, and steel flat plate mold has male and fomale(M&F), can control thickness 1 ~ 10mm, just placing above-mentioned duplexer in matter flat plate mold, steel flat plate mold is heated to 160 ℃, pressurization maintains 10-30s, rapidly, below cooling down steel flat plate mold to 80 ℃, open mould, take out the halogen-free flame-retardant resin matrix sandwich structural body making.
Measure the proportion of the halogen-free flame-retardant resin matrix sandwich structural body in embodiment 1, its integral thickness, and under the impact of moulding heating, pressurization the thickness of foaming body, and halogen-free flame-retardant resin matrix sandwich structural body property indices, concrete test data is in Table 1.
embodiment 2
By the 71WF of Rohacell company type PMI structural foam, (proportion is 70kg/m
3) cut into 3.0mm thickness and 320mm*250mm surface size (weight is 18g) using the foaming body as thering is space, according to ASTM D 638, test is 92Mpa to the elastic modelling quantity of foaming body, modulus of shearing is 42Mpa;
Will be to contain P-N, the surface size (every weight is 34g) that FD/MFP epoxy resin base carbon fiber prepreg ((CFR-1), golden hair carbon fiber new material development Co., Ltd) cuts into 0.26mm thickness and 320mm*250mm is using as resin matrix fibre reinforcement material; Two surfaces up and down that resin matrix fibre reinforcement material layer is stacked in to described foaming body are to provide duplexer;
Preparation levelness is smooth, fineness is the steel flat plate mold of 5 ~ 13 grades, and steel flat plate mold has male and fomale(M&F), can control thickness 1 ~ 10mm, just placing above-mentioned duplexer in matter flat plate mold, steel flat plate mold is heated to 160 ℃, pressurization maintains 7-10min, rapidly, below cooling down steel flat plate mold to 80 ℃, open mould, take out the halogen-free flame-retardant resin matrix sandwich structural body making.
Measure the proportion of the halogen-free flame-retardant resin matrix sandwich structural body in embodiment 2, its integral thickness, and under the impact of moulding heating, pressurization the thickness of foaming body, and halogen-free flame-retardant resin matrix sandwich structural body property indices, concrete test data is in Table 1.
embodiment 3
The core that thermoplastic resin matrix's fibre reinforcement material by modification is formed, wherein, infiltrates resin by fiber between described thermoplastic resin matrix and long fibre and intersects to form gap structure, and described fiber infiltrates resin length more than 10nm; The proportion of described core is 1.0, and thickness is 3.0mm; Cutting into 3.0mm thickness and 320mm*250mm*(weight is 24g);
The surface size (every weight is 35g) that will cut into 0.25mm thickness and 320mm*250mm with thermoplastic resin-based carbon fiber preliminary-dip piece (CFR-2, golden hair carbon fiber new material development Co., Ltd) is using as resin matrix fibre reinforcement material; Two surfaces up and down that resin matrix fibre reinforcement material layer is stacked in to described core are to provide duplexer;
Preparation levelness is smooth, fineness is the steel flat plate mold of 5 ~ 13 grades, and steel flat plate mold has male and fomale(M&F), can control thickness 1 ~ 10mm, just placing above-mentioned duplexer in matter flat plate mold, steel flat plate mold is heated to 160 ℃, pressurization maintains 10-30s, rapidly, below cooling down steel flat plate mold to 80 ℃, open mould, take out the halogen-free flame-retardant resin matrix sandwich structural body making.
Measure the proportion of the halogen-free flame-retardant resin matrix sandwich structural body in embodiment 3, its integral thickness and core thickness, and the thickness of core under the impact of moulding heating, pressurization, and halogen-free flame-retardant resin matrix sandwich structural body property indices, concrete test data is in Table 1.
embodiment 4
The core that thermoplastic resin matrix's fibre reinforcement material by modification is formed, wherein, infiltrates resin by fiber between described thermoplastic resin matrix and long fibre and intersects to form gap structure, and described fiber infiltrates resin length more than 10nm; The proportion of described core is 1.0, and thickness is 3.0mm; Cutting into 3.0mm thickness and 320mm*250mm*(weight is 24g);
Will be to contain P-N, the surface size (every weight is 34g) that FD/MFP epoxy resin base carbon fiber prepreg ((CFR-1), golden hair carbon fiber new material development Co., Ltd) cuts into 0.26mm thickness and 320mm*250mm is using as resin matrix fibre reinforcement material; Two surfaces up and down that resin matrix fibre reinforcement material layer is stacked in to described core are to provide duplexer;
Preparation levelness is smooth, fineness is the steel flat plate mold of 5 ~ 13 grades, and steel flat plate mold has male and fomale(M&F), can control thickness 1 ~ 10mm, just placing above-mentioned duplexer in matter flat plate mold, steel flat plate mold is heated to 160 ℃, pressurization maintains 7-10min, rapidly, below cooling down steel flat plate mold to 80 ℃, open mould, take out the halogen-free flame-retardant resin matrix sandwich structural body making.
Measure the proportion of the halogen-free flame-retardant resin matrix sandwich structural body in embodiment 4, its integral thickness and core thickness, and the thickness of core under the impact of moulding heating, pressurization, and halogen-free flame-retardant resin matrix sandwich structural body property indices, concrete test data is in Table 1.
comparative example 1
By the 71WF of Rohacell company type PMI structural foam, (proportion is 70kg/m
3) cut into 3.0mm thickness and 320mm*250mm surface size (weight is 18g) using as thering is the independently foaming body of closed pore bubble, according to ASTM D, 638 tests are 92Mpa to the elastic modelling quantity of foaming body; Then at upper surface and/or the lower surface of foaming body, distinguish direct coated thermoplastic glue-line;
By unidirectional orthogonal arrangement, thickness is the prepreg forming containing epoxy resin dipping (common not fire-retardant thermosetting resin) (use east beautiful (strain) system " TORAYCA(registration mark) " prepreg P3052S-12, east beautiful (strain) system " TORAYCA(registration mark) of 0.25mm " T700S, carbon fiber content: 67 % by weight, fibre weight: 125g/m
2) as fiber-reinforced material, the modulus of fiber-reinforced material is 120Gpa; Two surfaces up and down that fiber-reinforced material layers is stacked in to foaming body are to provide duplexer;
Preparation levelness is smooth, fineness is the steel flat plate mold of 5 ~ 13 grades, and steel flat plate mold has male and fomale(M&F), can control thickness 1 ~ 10mm, just placing above-mentioned duplexer in matter flat plate mold, steel flat plate mold is heated to 150 ℃, pressurization maintains 30min, rapidly, below cooling down steel flat plate mold to 80 ℃, open mould, take out the sandwich structural body making.
Measure the proportion of the sandwich structural body in comparative example 1, its integral thickness, and under the impact of moulding heating, pressurization the thickness of foaming body, and sandwich structural body property indices, concrete test data is in Table 1.
comparative example 2
The core that thermoplastic resin matrix's fibre reinforcement material by modification is formed, wherein, infiltrates resin by fiber between described thermoplastic resin matrix and long fibre and intersects to form gap structure, and described fiber infiltrates resin length more than 10nm; The proportion of described core is 1.0, and thickness is 3.0mm; Cutting into 3.0mm thickness and 320mm*250mm*(weight is 24g); Then at upper surface and/or the lower surface of described core, distinguish direct coated thermoplastic glue-line;
By unidirectional orthogonal arrangement, thickness is the prepreg forming containing epoxy resin dipping (common not fire-retardant thermosetting resin) (use east beautiful (strain) system " TORAYCA(registration mark) " prepreg P3052S-12, east beautiful (strain) system " TORAYCA(registration mark) of 0.25mm " T700S, carbon fiber content: 67 % weight, fibre weight: 125g/m
2) as fiber-reinforced material, the modulus of fiber-reinforced material is 120Gpa; Described in being stacked in, fiber-reinforced material layers is coated with two surfaces up and down of core of thermoplastic resin glue-line so that duplexer to be provided;
Preparation levelness is smooth, fineness is the steel flat plate mold of 5 ~ 13 grades, and steel flat plate mold has male and fomale(M&F), can control thickness 1 ~ 10mm, just placing above-mentioned duplexer in matter flat plate mold, steel flat plate mold is heated to 160 ℃, pressurization maintains 30min, rapidly, below cooling down steel flat plate mold to 80 ℃, open mould, take out the sandwich structural body making.
Measure the proportion of the sandwich structural body in comparative example 2, its integral thickness and core thickness, and under the impact of moulding heating, pressurization thickness and the sandwich structural body property indices of core, concrete test data is in Table 1.
comparative example 3
By the 71WF of Rohacell company type PMI structural foam, (proportion is 70kg/m
3) cut into 3.0mm thickness and 320mm*250mm surface size (weight is 18g) using the foaming body as thering is space, according to ASTM D 638, test is 92Mpa to the elastic modelling quantity of foaming body, modulus of shearing is 42Mpa;
By with add 20wt% Al (OH)
3common PP base carbon fibre reinforced plastics composite material sheet cut into the surface size (every weight is 80g) of 0.26mm thickness and 320mm*250mm, two surfaces up and down that this carbon fibre composite is layered in to described foaming body are to provide duplexer;
Preparation levelness is smooth, fineness is the steel flat plate mold of 5 ~ 13 grades, and steel flat plate mold has male and fomale(M&F), can control thickness 1 ~ 10mm, just placing above-mentioned duplexer in matter flat plate mold, steel flat plate mold is heated to 160 ℃, pressurization maintains 7-10min, rapidly, below cooling down steel flat plate mold to 80 ℃, open mould, take out the halogen-free flame-retardant resin matrix sandwich structural body making.
Measure the proportion of the sandwich structural body in comparative example 3, its integral thickness, and under the impact of moulding heating, pressurization the thickness of foaming body, and sandwich structural body property indices, concrete test data is in Table 1.
comparative example 4
By the 71WF of Rohacell company type PMI structural foam, (proportion is 70kg/m
3) cut into 3.0mm thickness and 320mm*250mm surface size (weight is 18g) using the foaming body as thering is space, according to ASTM D 638, test is 92Mpa to the elastic modelling quantity of foaming body, modulus of shearing is 42Mpa;
By with add 20wt% Al (OH)
3bisphenol A-type ordinary epoxy resin prepreg cut into the surface size (every weight is 80g) of 0.26mm thickness and 320mm*250mm, two surfaces up and down that this carbon fibre composite is layered in to described foaming body are to provide duplexer;
Preparation levelness is smooth, fineness is the steel flat plate mold of 5 ~ 13 grades, and steel flat plate mold has male and fomale(M&F), can control thickness 1 ~ 10mm, just placing above-mentioned duplexer in matter flat plate mold, steel flat plate mold is heated to 160 ℃, pressurization maintains 7-10min, rapidly, below cooling down steel flat plate mold to 80 ℃, open mould, take out the halogen-free flame-retardant resin matrix sandwich structural body making.
Measure the proportion of the sandwich structural body in comparative example 4, its integral thickness, and under the impact of moulding heating, pressurization the thickness of foaming body, and sandwich structural body property indices, concrete test data is in Table 1.
The concrete test performance result of table 1 embodiment 1 ~ 4 and comparative example 1 ~ 4
| |
Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Proportion | 1.5 | 1.3 | 1.4 | 1.5 | 1.4 | 1.4 | 2.1 | 2.3 |
| Integral thickness/mm | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Core thickness/mm | 0.57 | 0.54 | 0.56 | 0.56 | 0.54 | 0.55 | 0.50 | 0.51 |
| Skin depth/mm | 0.43 | 0.46 | 0.44 | 0.44 | 0.46 | 0.45 | 0.50 | 0.49 |
| Bending modulus/Gpa | 43 | 47 | 40 | 45 | 43 | 45 | 34 | 23 |
| Bending strength/Mpa | 486 | 512 | 475 | 493 | 487 | 468 | 338 | 237 |
| Flame retardant rating | UL94-V0 | UL94-V0 | UL94-V0 | UL94-V0 | Not fire-retardant | Not fire-retardant | UL94- V1 | UL94- V2 |
| Weatherability physical property measurement | Good | Better | Good | Better | Poor | Poor | Poor | Poor |
| Ultraviolet radiation resisting ability | By force | By force | By force | By force | ? | A little less than | A little less than | A little less than |
| Appearance | Smooth | Smooth | Smooth | Smooth | Smooth | Smooth | Coarse | Coarse |
Properties method of testing:
Proportion: press GB1033-86, the proportion of test sandwich structural body;
Thickness: by micrometer or slide measure test sheet metal thickness;
Bending modulus: Plastics-Oetermination of flexural properties GB/T9341-2000;
Bending strength: Plastics-Oetermination of flexural properties GB/T9341-2000
Flame retardant rating: according to the fire-protection rating method of testing test of UL94 and 5A;
Appearance: artificial visual detection method (using if desired magnifying glass);
Weatherability physical property measurement: press GB/T-16422.3-1997 plastics laboratory light source exposure test method, fluorescent lamp irradiates, 1 circulation (15 ℃/4h-+100 ℃/4h), the cycle is heated cooling 21 circulations, by GB/T9341-2000 Plastics-Oetermination of flexural properties test intensity;
Ultraviolet radiation resisting ability: the fluorescence UV light exposure test method of ASTM D4329 plastics.
Claims (11)
1. a halogen-free flame-retardant resin matrix sandwich structural body, it is characterized in that, described halogen-free flame-retardant resin matrix sandwich structural body be by core (I) and be configured in this core (I) upper surface and/or lower surface resin matrix fibre reinforcement material (II) form halogen-free flame-retardant resin matrix sandwich structural body (III), described core (I) consists of the material that has space; The proportion of described core (I) is 0.03 ~ 2.0, and thickness is 0.1 ~ 5.0mm.
2. halogen-free flame-retardant resin matrix sandwich structural body according to claim 1, it is characterized in that, described core (I) is foaming body, and according to ASTM D, 638 tests are 10 ~ 1000MPa to described foaming body elastic modelling quantity, and according to ASTM D, 638 tests are 10 ~ 150MPa to modulus of shearing; Described foaming body proportion is 0.03 ~ 1.0, is preferably 0.08 ~ 0.8, more preferably 0.1 ~ 0.6.
3. halogen-free flame-retardant resin matrix sandwich structural body according to claim 2, it is characterized in that, described foaming body is selected from one or more of PMI structural foam, CPMI structural foam, SAN structural foam, PP structural foam, PES structural foam, PU structural foam, PET structural foam, phenolic structure foam, melamine structural foam.
4. a halogen-free flame-retardant resin matrix sandwich structural body, it is characterized in that, described halogen-free flame-retardant resin matrix sandwich structural body be by core (I) and be configured in this core (I) upper surface and/or lower surface resin matrix fibre reinforcement material (II) form halogen-free flame-retardant resin matrix sandwich structural body (III), described core (I) consists of thermoplastic resin matrix's fibre reinforcement material of modification, between described thermoplastic resin matrix and long fibre, by fiber, infiltrate resin and intersect to form gap structure, described fiber infiltrates resin length more than 10nm; The proportion of described core (I) is 0.1 ~ 2.0, is preferably 0.1 ~ 1.0, more preferably 0.2 ~ 0.6.
5. according to the halogen-free flame-retardant resin matrix sandwich structural body described in claim 1 or 4, it is characterized in that, described resin matrix fibre reinforcement material (II) consists of thermosetting resin matrix fibre reinforcement material; The thermosetting resin that described thermosetting resin matrix is halogen-free flameproof; Described fibre reinforcement material is selected from one or more of continuous carbon fibre material, glass fiber material, aramid fiber material, basalt fiber material.
6. halogen-free flame-retardant resin matrix sandwich structural body according to claim 5, is characterized in that, the synthetic method of the thermosetting resin of described halogen-free flameproof, comprises the steps:
1) by conventional polymerisation, directly prepare thermosetting resin and the curing agent containing the halogen-free flameproof of N-P;
2) add modified-reaction, the polymer by interpolation with fire retarding effect is to the thermosetting resin that obtains halogen-free flameproof in ordinary hot thermosetting resin.
7. halogen-free flame-retardant resin matrix sandwich structural body according to claim 6, is characterized in that, the synthetic method of the thermosetting resin of described halogen-free flameproof, comprises the steps:
A) synthesizing containing P epoxy resin FD: prepare the FD epoxy resin that contains 2wt%P element with DOPO and Bisphenol F type novolac epoxy resin;
B) synthesizing containing N epoxy resin MFP: nitrogen-containing hardener 2,4, synthesizing of 6-tri-(hydroxy phenyl benzylidene amino)-s-triazine (MFP): with melamine and phenol reactant, prepare the phenolic curing agent MFP of nitrogen content as 0.5～2.5wt% take the modification of methyl guanamines;
C) containing the preparation of P-N epoxy resin solidifying system glue: get certain proportioning containing the FD epoxy resin of 2wt%P and containing N curing agent MFP, be placed in the solvent methyl first peptamine of strong polarity and the processing of acetone dissolving, curing and make hot melt adhesive liquid and use;
D) synthetic containing the FD/MFP epoxy-resin systems of P-N halogen-free flameproof: actual measurement epoxide number is 0.315mol/100g, and tg is more than 145 ℃, and polymer is when Pwt%=2%, and LOI is 33-39, at 180 ℃, 2min gel, 7-10min is curing, obtains.
8. according to the halogen-free flame-retardant resin matrix sandwich structural body described in claim 1 or 4, it is characterized in that, described resin matrix fibre reinforcement material (II) consists of thermoplastic resin matrix's fibre reinforcement material; Described thermoplastic resin is the thermoplastic resin of the halogen-free flameproof of modification; Described fibre reinforcement material is selected from one or more of continuous carbon fibre material, glass fiber material, aramid fiber material, basalt fiber material.
9. halogen-free flame-retardant resin matrix sandwich structural body according to claim 8, is characterized in that, the thermoplastic resin of the halogen-free flameproof of described modification is selected from halogen-free flameproof PP and/or the PE plastics of modification.
10. the preparation method of the halogen-free flame-retardant resin matrix sandwich structural body as described in claim 1 or 4, comprises the steps:
A) stacked step: comprise resin matrix fibre reinforcement material (II) is layered in to the upper surface of described core (I) and/or lower surface so that duplexer to be provided;
B) heating pressurization steps: be included in the duplexer that in the firm matter flat plate mold of 5 ~ 13a level fineness, configuration obtains by step a), heat 100 ~ 200 ℃, pressurization maintains and is cooled to rapidly 80 ℃ after 0.5 ~ 30min and carries out below moulding, makes halogen-free flame-retardant resin matrix sandwich structural body (III).
The halogen-free flame-retardant resin matrix sandwich structural body that the preparation method of 11. halogen-free flame-retardant resin matrix sandwich structural bodies according to claim 10 obtains is in the application of 3C industry, household electric appliances and cabinet surface texture sheet material.
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| CN105563970A (en) * | 2015-04-20 | 2016-05-11 | 广州金发碳纤维新材料发展有限公司 | Composite structure with PMI sandwich as well as preparation method and application of composite structure |
| CN105563971A (en) * | 2015-04-20 | 2016-05-11 | 广州金发碳纤维新材料发展有限公司 | Composite sandwich structural body as well as preparation method and application thereof |
| CN108045050A (en) * | 2017-11-22 | 2018-05-18 | 杭州捷尔思阻燃化工有限公司 | A kind of low VOC foam sandwiches high-strength light halogen-free flame-retardant composite material and preparation method thereof |
| CN105563971B (en) * | 2015-04-20 | 2018-08-31 | 广州金发碳纤维新材料发展有限公司 | A kind of composite material sandwich structure body and its preparation method and application |
| CN109397785A (en) * | 2017-08-16 | 2019-03-01 | 上海杰事杰新材料(集团)股份有限公司 | High-strength light flame-proof weather-resisting continuous fiber reinforcement thermoplastic composite board and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105563970A (en) * | 2015-04-20 | 2016-05-11 | 广州金发碳纤维新材料发展有限公司 | Composite structure with PMI sandwich as well as preparation method and application of composite structure |
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| CN108045050A (en) * | 2017-11-22 | 2018-05-18 | 杭州捷尔思阻燃化工有限公司 | A kind of low VOC foam sandwiches high-strength light halogen-free flame-retardant composite material and preparation method thereof |
| CN111231378A (en) * | 2020-01-13 | 2020-06-05 | 北京邦维高科特种纺织品有限责任公司 | Decorative layer and preparation method thereof |
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| CN103753905B (en) | 2016-09-07 |
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