CN103753905B - A kind of Halogen-free flame-retardant resin matrix sandwich structure body and preparation method thereof - Google Patents
A kind of Halogen-free flame-retardant resin matrix sandwich structure body and preparation method thereof Download PDFInfo
- Publication number
- CN103753905B CN103753905B CN201310715090.8A CN201310715090A CN103753905B CN 103753905 B CN103753905 B CN 103753905B CN 201310715090 A CN201310715090 A CN 201310715090A CN 103753905 B CN103753905 B CN 103753905B
- Authority
- CN
- China
- Prior art keywords
- halogen
- resin matrix
- free flame
- sandwich structure
- structure body
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Laminated Bodies (AREA)
Abstract
The invention discloses a kind of Halogen-free flame-retardant resin matrix sandwich structure body, described Halogen-free flame-retardant resin matrix sandwich structure body is by core (I) and to be arranged in the Halogen-free flame-retardant resin matrix sandwich structure body (III) that resin matrix fibre reinforcement material (II) of this core (I) upper surface and/or lower surface is constituted, and described core (I) be made up of the material having space；The proportion of described core (I) is 0.03 ~ 2.0, and thickness is 0.1 ~ 5.0mm；Described core (I) is to have the foaming body in space or be made up of modified thermoplastic resin matrix's fibre reinforcement material, intersects to form gap structure by fiber infiltration resin between described thermoplastic resin matrix and long fibre；The Halogen-free flame-retardant resin matrix sandwich structure body flame retardant rating that the present invention prepares is up to UL94 V0, and weatherability is strong, and ultraviolet radiation resisting ability is strong, lightweight, thickness is thin, and rigidity is high, technique is simple, is mainly used in the surface texture sheet materials such as 3C industry, household electric appliances and relevant cabinet.
Description
Technical field
The present invention relates to a kind of Halogen-free flame-retardant resin matrix sandwich structure body and preparation method thereof.
Background technology
Under the overall situation in carbon fibre composite market, resin matrix 80% share being combined with carbon fibre composite
For epoxy resin, the resin matrix of remaining 20% share is phenolic resin, unsaturated-resin and part thermoplastic's resin.But
Compared with epoxy resin, phenolic resin hardness is high, is fragile material, simultaneously cannot dry process carbon fiber prepreg, can only be wet
Prepared by method, thus there is serious severe working environment and produce environmental issue.Unsaturated-resin is compared with epoxy resin
With low cost a lot, but its intensity and environmental problem are also very poor, the most substantially apply in cheap fiberglass industry.
Thermoplastic resin is the most ripe with the combination technology of carbon fiber, also in laboratory development, produces in enormous quantities and also fails to reality
Existing.
Therefore, it is fast that epoxy resin possesses dry fabrication speed in carbon fibre composite is applied, and batch is big, moulding process
Controlled, intensity is high, good toughness, performance can flexible modulation, relative low price, working environment relative clean, the advantage such as environmental protection.
Patent No. 200580029564.7 discloses a kind of sandwich structural body, and this sandwich structural body (III) is by core (I)
With fiber-reinforced material (II) that be arranged in this core (I) two sides, that be made up of continuous reinforcement fiber (A) and matrix resin (B)
Constituting, wherein said core (I) has space.Described space is formed by the bubble of foaming body, or core is by discontinuously strengthening
Fiber and thermoplastic resin are constituted, the space shape that described space is formed by intersecting between the long filament of this reinforcing fiber
Become.This patent is the carbon fibre composite sheet material using common resin forming to become sandwich structural body, is in the market
Common fabrication scheme, but the problem such as it is long to there is also molding cycle, and production automation degree is low, inflammable.
The Normal practice of the general problem solving resin halogen-free flameproof is interpolation halogen-free flame retardants, such as hydrogen-oxygen in resin
Change aluminium powder, but conventional halogen-free flame retardants is immiscible with resin, thus be greatly increased the viscosity of resin, affect the flowing of resin
Property and reduce the intensity of epoxy resin, even accomplishing to mix conventional halogen-free flame retardants and resin, to be also substantially reduced carbon fiber multiple
The strength problem of condensation material and separate out in forming process and affect product surface.
Summary of the invention
In order to overcome the carbon fibre composite on existing market to apply the halogen-free flameproof encountered in 3C industry field
Etc. defect, it is an object of the present invention to provide one and meet that halogen-free flame retardant feature, weatherability be strong, ultraviolet radiation resisting ability
By force, lightweight, thin-walled, the Halogen-free flame-retardant resin matrix sandwich structure body of high rigidity.
It is a further object of the present invention to provide the preparation method of above-mentioned Halogen-free flame-retardant resin matrix sandwich structure body；
Another object of the present invention is to provide the purposes of above-mentioned Halogen-free flame-retardant resin matrix sandwich structure body.
The present invention is achieved by the following technical solution:
A kind of Halogen-free flame-retardant resin matrix sandwich structure body, described Halogen-free flame-retardant resin matrix sandwich structure body is by core
And be arranged in the Halogen resistance that resin matrix fibre reinforcement material (II) of this core (I) upper surface and/or lower surface is constituted (I)
Combustion resin matrix sandwich structural body (III), described core (I) be made up of the material having space；The proportion of described core (I) is
0.03 ~ 2.0, thickness is 0.1 ~ 5.0mm.
Described core (I) is foaming body, described foaming body elastic modelling quantity according to ASTM D 638 test be 10 ~
1000MPa, modulus of shearing is 10 ~ 150MPa according to ASTM D 638 test；Described foaming body proportion is 0.03 ~ 1.0, preferably
It is 0.08 ~ 0.8, more preferably 0.1 ~ 0.6.
Described foaming body is selected from PMI structural foam, CPMI structural foam, SAN fabric foam, PP structural foam, PES structure
Foam, PU structural foam, PET construction foam, phenolic structure foam, melamine structural foam one or more.
A kind of Halogen-free flame-retardant resin matrix sandwich structure body, described Halogen-free flame-retardant resin matrix sandwich structure body is by core
And be arranged in the Halogen resistance that resin matrix fibre reinforcement material (II) of this core (I) upper surface and/or lower surface is constituted (I)
Combustion resin matrix sandwich structural body (III), described core (I) is made up of modified thermoplastic resin matrix's fibre reinforcement material,
Gap structure, described fiber infiltration tree is intersected to form by fiber infiltration resin between described thermoplastic resin matrix and long fibre
Fat length is at more than 10nm；The proportion of described core (I) is 0.1 ~ 2.0, preferably 0.1 ~ 1.0, more preferably 0.2 ~ 0.6.
Described resin matrix fibre reinforcement material (II) is made up of thermosetting resin matrix fibre reinforcement material；Described
Thermosetting resin matrix is the thermosetting resin of halogen-free flameproof, and flame retardant rating reaches more than UL-94 V1 level；Described fiber reinforcement
Body material is selected from continuous print carbon fibre material, glass fiber material, aramid fiber material, the one of basalt fiber material or several
Kind.
Described thermosetting resin matrix is the thermosetting resin of halogen-free flameproof, and flame retardant rating reaches more than UL-94 V1 level,
It is by adding fire-retardant resin group in thermosetting resin macromolecule to reach halogen-free flame retardant feature.The mode added: resistance
The resin group of combustion is linked together with high molecular resin group by polymerization methods；The density of thermosetting resin is 1.05 ~
1.2；In use, the Tg point control of thermosetting resin matrix is at 100 DEG C ~ 160 DEG C.Room temperature 25 DEG C, humidity 55% ~
75%, resin viscosity passes through rotation viscometer testing and control at 1 ~ 30000mpa.s；At temperature 80 DEG C, humidity 55% ~ 75%, resin
Viscosity is by rotation viscometer testing and control at 1 ~ 600mpa.s, and heat curing temperature controls at 120 DEG C ~ 160 DEG C, and the time controls
At 5min ~ 30min；Preferably, heat curing temperature is 140 DEG C ~ 150 DEG C, and hardening time is 5min ~ 10min.
The synthetic method of the thermosetting resin of described halogen-free flameproof, comprises the steps:
1) by thermosetting resin and the curing agent of the typical polymerization reaction directly preparation halogen-free flameproof containing N-P；
2) adding modified-reaction, the polymer by interpolation with fire retarding effect obtains Halogen in ordinary hot thermosetting resin
Fire-retardant 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) synthesis containing P epoxy resin FD: with DOPO with the preparation of bisphenol-f type novolac epoxy resin containing 2wt%P element
FD epoxy resin；
B) synthesis containing N epoxy resin MFP: nitrogen-containing hardener 2,4,6-tri-(hydroxy phenyl benzylidene amino)-s-triazine
(MFP) synthesis: with melamine and phenol reactant, preparing nitrogen content with methyl guanamines modification is 0.5～2.5wt%
Phenolic curing agent MFP；
C) preparation containing P-N epoxy resin solidifying system glue: take the FD epoxy resin containing 2wt%P of certain proportioning and contain
N curing agent MFP is placed in dissolving, curing process in highly polar solvent methyl first peptamine and acetone and makes hot melt adhesive liquid use；
D) synthesis of the FD/MFP epoxy-resin systems containing P-N halogen-free flameproof: actual measurement epoxide number is 0.315mol/100g,
Tg is more than 145 DEG C, and polymer is when Pwt%=2%, and LOI is 33-39, and at 180 DEG C, 2min gel, 7-10min solidifies, to obtain final product.
The synthetic method of described FD/MFP epoxy-resin systems is with reference to such as Publication about Document: Cao Jun, Liang Bing.DOPO type halogen-free flameproof
Epoxy-resin systems research report [J]. New Chemical Materials, 2011,39(8): 7-14；Zheng Cancheng, Zhao Xingmao, Deng Huali.Nothing
The research [J] of halogen fire-retardant copper-clad plate preparation method. Guangdong chemical industry, 2012,39(5): 278-279；Min Yuqin, Fang Lin, Zhang Xinghong,
Qi Guorong.The synthesis of novel halogen-free flame-retardant epoxy resin and performance study [J] .2006,33(4): 429-433；Liu Gang, Li Zhen
Woods, Yan Hui, Yang Bei, model peace.The progress [J] of immunity copper-clad plate Halogenless fire retarded epoxy resin and curing agent thereof. chemistry
With bonding, 2010,32(2): 50-58.
Wherein, described FD/MFP epoxy-resin systems, by TGA and UL94, solidfied material vertical combustion is tested, thermally-stabilised
Performance is good, the synergy of P-N, and fire-retardant rank reaches UL94-V0 level.
The most dated: when making resin streak and testing by UL94 test mode vertical combustion, to basically reach UL94-V0 level
Not, but when containing P-N halogen-free flame-retardant resin by after compound with the continuously reinforcing fiber such as carbon fiber or glass fibre, due to fiber
The factors such as candle wick effect cause a lot of resin all can not be fully achieved V0 rank, and this resin is confirmed by fine adjustments P-N content
Composite reaches UL94-V0 rank；Wherein, described fine adjustments P-N content, is to control the P content containing in P epoxy resin FD
For 2wt%, controlling containing nitrogen content in N epoxy resin MFP is 0.5～2.5wt%, when nitrogen content is less than 0.5wt%, to improving resistance
The contribution of combustion property is little；When nitrogen content is higher than 2.5wt%, the water absorption rate of epoxy-resin systems solidfied material can be made to increase.
Correspondingly, thermosetting resin and fibre reinforcement material by halogen-free flameproof constitute thermosetting resin matrix fiber and increase
Strong material, is preferably containing P-N, FD/MFP epoxy resin base carbon fiber/glass fibre prepreg, can pass through following two system
Preparation Method obtains:
1, wet method (solvent method) preparation is containing P-N, FD/MFP epoxy resin base carbon fiber/glass fibre prepreg: will contain
The FD/MFP epoxy-resin systems of P-N halogen-free flameproof is configured to glue, is then diluted to the lowest the mixing of viscosity by increase acetone
Compound, fine by making after the impregnation-drying to woven cloth such as carbon fibers/fiberglass containing P-N, FD/MFP epoxy resin-matrix carbon
Dimension/glass fibre prepreg.
2, dry method (fusion method) preparation is containing P-N, FD/MFP epoxy resin base carbon fiber/glass fibre prepreg: will contain
The FD/MFP epoxy-resin systems having P-N makes heat molten type glue, by traditional heat molten type preimpregnation machine equipment, viscosity is higher
Make containing P-N, FD/MFP epoxy with the unidirectional UD of carbon fibers/fiberglass or the laminating infiltration of woven cloth after FD/MFP is resin melting
Resin-based carbon fiber/glass fibre prepreg.
Described resin matrix fibre reinforcement material (II) is made up of thermoplastic resin matrix's fibre reinforcement material；Described
Thermoplastic resin is modified halogen-free combustion-proof thermoplastic resin, and flame retardant rating reaches more than UL94 V1 level；Described fibre reinforcement
Material selected from continuous print carbon fibre material, glass fiber material, aramid fiber material, basalt fiber material one or more
Mixture.
Described thermoplastic resin is modified halogen-free combustion-proof thermoplastic resin, and flame retardant rating reaches more than UL94-V1 level, is
By adding fire-retardant resin group in resin macromolecule to reach halogen-free flame retardant feature, its addition manner have blending and modifying and
Polymerisation two kinds；The tg point control of described thermoplastic resin is at 120 DEG C ~ 160 DEG C；Described thermoplastic resin is preferably modified
Halogen-free flameproof PP and/or PE plastics, for the modified halogen-free flameproof of existing product, more preferably JinFa Science Co., Ltd
PP and/or PE plastics.
Correspondingly, thermoplastic resin and fibre reinforcement material by modified halogen-free flameproof constitute thermoplastic resin matrix
Fibre reinforced materials, preferably PP and/or PE plastics base carbon fibre preliminary-dip piece.
The preparation method of a kind of Halogen-free flame-retardant resin matrix sandwich structure body, comprises the steps:
A) Stacking steps: include the upper surface that resin matrix fibre reinforcement material (II) is layered in described core (I)
And/or lower surface is to provide duplexer；
B) applying heat: be included in firm matter flat plate mold and configure the duplexer obtained by step a), heats 100
~ 200 DEG C, it is cooled to rapidly less than 80 DEG C after pressurization maintenance 0.5 ~ 30min and is shaped, prepare Halogen-free flame-retardant resin matrix interlayer
Structure (III).
The Halogen-free flame-retardant resin matrix interlayer that the preparation method of described Halogen-free flame-retardant resin matrix sandwich structure body obtains
Construction 3C industry, household electric appliances and the application of cabinet surface texture sheet material.
The present invention compared with prior art, has the following technical effect that:
1) the Halogen-free flame-retardant resin matrix sandwich structure body flame retardant rating that the present invention prepares is up to UL94-V0, Halogen, nothing
Poison, volatility is little, does not produce toxic gas and secondary pollution during burning.
2) Halogen-free flame-retardant resin matrix sandwich structure body that the present invention prepares has high heat decomposition temperature, and excellent heat is steady
Good ermal physics mechanical performance is kept under qualitative and heating condition.
3) the Halogen-free flame-retardant resin matrix sandwich structure body ultraviolet radiation resisting ability that the present invention prepares is strong.
4) Halogen-free flame-retardant resin matrix sandwich structure body that the present invention prepares is lightweight, and thickness is thin, 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 structure body of the present invention.
Detailed description of the invention
Further illustrating the present invention below by detailed description of the invention, following example are the present invention preferably embodiment party
Formula, but embodiments of the present invention are not limited by following embodiment.
Now the raw material used by embodiment and comparative example are done as described below, 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；
Foaming body as core:
With the FR100 system PET construction foam of Gurit company as core；Similarly, Rohacell company 71WF type PMI knot
Structure foam, phenolic structure foam, melamine structural foam all can use as the foaming body of core.
Embodiment 1
By the FR100 system PET construction foam of Gurit company, (proportion is 100kg/m3) cut into 3.0mm thickness and
The surface size (weight is 24g) of 320mm*250mm using as having the foaming body in space, the elastic modelling quantity of foaming body according to
ASTM D 638 test is 70MPa, and modulus of shearing is 35Mpa；
Will be with thermoplastic resin-based carbon fiber preliminary-dip piece (CFR-2, golden hair carbon fiber new material development Co., Ltd) cutting
Become the surface size (every weight is 35g) of 0.25mm thickness and 320mm*250mm using as resin matrix fibre reinforcement material
Material；Resin matrix fibre reinforcement material is layered in two surfaces up and down of described foaming body to provide duplexer；
Preparing levelness 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, in firm matter flat plate mold, place above-mentioned duplexer, steel flat plate mold is heated to 160 DEG C, pressurization
Maintaining 10-30s, rapid cooling down steel flat plate mold, to less than 80 DEG C, opens mould, takes out the halogen-free flame-retardant resin prepared
Matrix sandwich structure body.
The proportion of the Halogen-free flame-retardant resin matrix sandwich structure body in mensuration embodiment 1, its integral thickness, and add in shaping
The thickness of foaming body under the influence of heat, pressurization, and Halogen-free flame-retardant resin matrix sandwich structure body property indices, specifically test
Data are shown in Table 1.
Embodiment 2
By Rohacell company 71WF type PMI structural foam, (proportion is 70kg/m3) cut into 3.0mm thickness and 320mm*
The surface size (weight is 18g) of 250mm is using as having the foaming body in space, and the elastic modelling quantity of foaming body is according to ASTM D
638 tests are 92Mpa, and modulus of shearing is 42Mpa；
Will be with containing P-N, FD/MFP epoxy resin base carbon fiber prepreg ((CFR-1), golden hair carbon fiber new material development
Co., Ltd) cut into the surface size (every weight is 34g) of 0.26mm thickness and 320mm*250mm using as resin matrix
Fibre reinforcement material；Resin matrix fibre reinforcement material is layered in two surfaces up and down of described foaming body to provide layer
Stack；
Preparing levelness 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, in firm matter flat plate mold, place above-mentioned duplexer, steel flat plate mold is heated to 160 DEG C, pressurization
Maintaining 7-10min, rapid cooling down steel flat plate mold, to less than 80 DEG C, opens mould, takes out the halogen-free flameproof tree prepared
Fat matrix sandwich structure body.
The proportion of the Halogen-free flame-retardant resin matrix sandwich structure body in mensuration embodiment 2, its integral thickness, and add in shaping
The thickness of foaming body under the influence of heat, pressurization, and Halogen-free flame-retardant resin matrix sandwich structure body property indices, specifically test
Data are shown in Table 1.
Embodiment 3
The core being made up of modified thermoplastic resin matrix's fibre reinforcement material, wherein, described thermoplastic resin
Intersect to form gap structure by fiber infiltration resin between matrix and long fibre, described fiber infiltration resin length 10nm with
On；The proportion of described core is 1.0, and thickness is 3.0mm；Cut into 3.0mm thickness and 320mm*250mm*(weight is 24g)；
Will be with thermoplastic resin-based carbon fiber preliminary-dip piece (CFR-2, golden hair carbon fiber new material development Co., Ltd) cutting
Become the surface size (every weight is 35g) of 0.25mm thickness and 320mm*250mm using as resin matrix fibre reinforcement material
Material；Resin matrix fibre reinforcement material is layered in two surfaces up and down of described core to provide duplexer；
Preparing levelness 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, in firm matter flat plate mold, place above-mentioned duplexer, steel flat plate mold is heated to 160 DEG C, pressurization
Maintaining 10-30s, rapid cooling down steel flat plate mold, to less than 80 DEG C, opens mould, takes out the halogen-free flame-retardant resin prepared
Matrix sandwich structure body.
The proportion of the Halogen-free flame-retardant resin matrix sandwich structure body in mensuration embodiment 3, its integral thickness and core are thick
Degree, and the thickness of core under the influence of shaping heating, pressurization, and Halogen-free flame-retardant resin matrix sandwich structure body properties refers to
Mark, concrete test data is shown in Table 1.
Embodiment 4
The core being made up of modified thermoplastic resin matrix's fibre reinforcement material, wherein, described thermoplastic resin
Intersect to form gap structure by fiber infiltration resin between matrix and long fibre, described fiber infiltration resin length 10nm with
On；The proportion of described core is 1.0, and thickness is 3.0mm；Cut into 3.0mm thickness and 320mm*250mm*(weight is 24g)；
Will be with containing P-N, FD/MFP epoxy resin base carbon fiber prepreg ((CFR-1), golden hair carbon fiber new material development
Co., Ltd) cut into the surface size (every weight is 34g) of 0.26mm thickness and 320mm*250mm using as resin matrix
Fibre reinforcement material；Resin matrix fibre reinforcement material is layered in two surfaces up and down of described core to provide stacking
Body；
Preparing levelness 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, in firm matter flat plate mold, place above-mentioned duplexer, steel flat plate mold is heated to 160 DEG C, pressurization
Maintaining 7-10min, rapid cooling down steel flat plate mold, to less than 80 DEG C, opens mould, takes out the halogen-free flameproof tree prepared
Fat matrix sandwich structure body.
The proportion of the Halogen-free flame-retardant resin matrix sandwich structure body in mensuration embodiment 4, its integral thickness and core are thick
Degree, and the thickness of core under the influence of shaping heating, pressurization, and Halogen-free flame-retardant resin matrix sandwich structure body properties refers to
Mark, concrete test data is shown in Table 1.
Comparative example 1
By Rohacell company 71WF type PMI structural foam, (proportion is 70kg/m3) cut into 3.0mm thickness and 320mm*
The surface size (weight is 18g) of 250mm using as having the foaming body of independent closed pore bubble, the elastic modelling quantity root of foaming body
It is 92Mpa according to ASTM D 638 test；Then upper surface and/or lower surface at foaming body the most directly coat thermoplastic resin
Fat glue-line；
By unidirectional orthogonal arrangement, thickness is being formed containing epoxy resin dipping (the most fire-retardant thermosetting resin) of 0.25mm
Prepreg (use east beautiful (strain) system " TORAYCA(registration mark) " prepreg P3052S-12, east beautiful (strain) system
" TORAYCA(registration mark) " T700S, carbon fiber content: 67 weight %, fibre weight: 125g/m2) as fibre strengthening material
Material, the modulus of fiber-reinforced material is 120Gpa；Fiber-reinforced material layers is stacked in two surfaces up and down of foaming body to provide
Duplexer；
Preparing levelness 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, in firm matter flat plate mold, place above-mentioned duplexer, steel flat plate mold is heated to 150 DEG C, pressurization
Maintaining 30min, rapid cooling down steel flat plate mold, to less than 80 DEG C, opens mould, takes out the sandwich structural body prepared.
The proportion of the sandwich structural body in mensuration comparative example 1, its integral thickness, and under the influence of shaping heating, pressurization
The thickness of foaming body, and sandwich structural body property indices, concrete test data is shown in Table 1.
Comparative example 2
The core being made up of modified thermoplastic resin matrix's fibre reinforcement material, wherein, described thermoplastic resin
Intersect to form gap structure by fiber infiltration resin between matrix and long fibre, described fiber infiltration resin length 10nm with
On；The proportion of described core is 1.0, and thickness is 3.0mm；Cut into 3.0mm thickness and 320mm*250mm*(weight is 24g)；
Then at upper surface and/or the lower surface direct coated thermoplastic glue-line respectively of described core；
By unidirectional orthogonal arrangement, thickness is being formed containing epoxy resin dipping (the most fire-retardant thermosetting resin) of 0.25mm
Prepreg (use east beautiful (strain) system " TORAYCA(registration mark) " prepreg P3052S-12, east beautiful (strain) system
" TORAYCA(registration mark) " T700S, carbon fiber content: 67 % weight, fibre weight: 125g/m2) as fibre strengthening material
Material, the modulus of fiber-reinforced material is 120Gpa；It is coated with thermoplastic resin glue-line described in fiber-reinforced material layers being stacked in
Two surfaces up and down of core are to provide duplexer；
Preparing levelness 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, in firm matter flat plate mold, place above-mentioned duplexer, steel flat plate mold is heated to 160 DEG C, pressurization
Maintaining 30min, rapid cooling down steel flat plate mold, to less than 80 DEG C, opens mould, takes out the sandwich structural body prepared.
The proportion of the sandwich structural body in mensuration comparative example 2, its integral thickness and core thickness, and heat in shaping,
The thickness of core and sandwich structural body property indices under the influence of pressurization, concrete test data is shown in Table 1.
Comparative example 3
By Rohacell company 71WF type PMI structural foam, (proportion is 70kg/m3) cut into 3.0mm thickness and 320mm*
The surface size (weight is 18g) of 250mm is using as having the foaming body in space, and the elastic modelling quantity of foaming body is according to ASTM D
638 tests are 92Mpa, and modulus of shearing is 42Mpa；
By to add 20wt% Al (OH)3Common PP base carbon fibre reinforced plastics composite material sheet cut into 0.26mm
The surface size (every weight is 80g) of thickness and 320mm*250mm, is stacked in described foaming body by this carbon fiber composite layer
Two surfaces up and down to provide duplexer；
Preparing levelness 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, in firm matter flat plate mold, place above-mentioned duplexer, steel flat plate mold is heated to 160 DEG C, pressurization
Maintaining 7-10min, rapid cooling down steel flat plate mold, to less than 80 DEG C, opens mould, takes out the halogen-free flameproof tree prepared
Fat matrix sandwich structure body.
The proportion of the sandwich structural body in mensuration comparative example 3, its integral thickness, and under the influence of shaping heating, pressurization
The thickness of foaming body, and sandwich structural body property indices, concrete test data is shown in Table 1.
Comparative example 4
By Rohacell company 71WF type PMI structural foam, (proportion is 70kg/m3) cut into 3.0mm thickness and 320mm*
The surface size (weight is 18g) of 250mm is using as having the foaming body in space, and the elastic modelling quantity of foaming body is according to ASTM D
638 tests are 92Mpa, and modulus of shearing is 42Mpa；
By to add 20wt% Al (OH)3Bisphenol A-type ordinary epoxy resin prepreg cut into 0.26mm thickness and
The surface size (every weight is 80g) of 320mm*250mm, is stacked in the upper and lower of described foaming body by this carbon fiber composite layer
Two surfaces are to provide duplexer；
Preparing levelness 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, in firm matter flat plate mold, place above-mentioned duplexer, steel flat plate mold is heated to 160 DEG C, pressurization
Maintaining 7-10min, rapid cooling down steel flat plate mold, to less than 80 DEG C, opens mould, takes out the halogen-free flameproof tree prepared
Fat matrix sandwich structure body.
The proportion of the sandwich structural body in mensuration comparative example 4, its integral thickness, and under the influence of shaping heating, pressurization
The thickness of foaming body, and sandwich structural body property indices, concrete test data is shown in Table 1.
Table 1 embodiment 1 ~ 4 and the concrete test performance result of comparative example 1 ~ 4
| Embodiment 1 | 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 | The most fire-retardant | The most fire-retardant | UL94- V1 | UL94- V2 |
| Weatherability physical property measurement | Good | Preferably | Good | Preferably | Difference | Difference | Difference | Poor |
| Ultraviolet radiation resisting ability | By force | By force | By force | By force | More weak | Weak | Weak | Weak |
| Appearance | Smooth | Smooth | Smooth | Smooth | Smooth | Smooth | Coarse | Coarse |
Properties method of testing:
Proportion: by GB1033-86, the proportion of test clip laminar structure；
Thickness: test sheet metal thickness by micrometer or slide measure；
Bending modulus: Plastics-Oetermination of flexural properties GB/T9341-2000；
Bending strength: Plastics-Oetermination of flexural properties GB/T9341-2000
Flame retardant rating: test according to the fire-protection rating method of testing of UL94 and 5A；
Appearance: artificial visual detection method (uses magnifying glass) if desired；
Weatherability physical property measurement: by GB/T-16422.3-1997 plastics laboratory light source exposure test method, fluorescent lamp
Irradiate, 1 circulation (-15 DEG C/4h+100 DEG C/4h), cycle heating 21 circulations of cooling, bend by GB/T9341-2000 plastics
Performance test test intensity；
Ultraviolet radiation resisting ability: the fluorescent UV exposure test method of ASTM D4329 plastics.
Claims (15)
1. a Halogen-free flame-retardant resin matrix sandwich structure body, it is characterised in that described Halogen-free flame-retardant resin matrix sandwich
Body is by core (I) and resin matrix fibre reinforcement material (II) structure that is arranged in this core (I) upper surface and/or lower surface
The Halogen-free flame-retardant resin matrix sandwich structure body (III) become, described core (I) be made up of the material having space；Described core (I)
Proportion be 0.03 ~ 2.0, thickness is 0.1 ~ 5.0mm.
Halogen-free flame-retardant resin matrix sandwich structure body the most according to claim 1, it is characterised in that described core (I) is
Foaming body, described foaming body elastic modelling quantity is 10 ~ 1000MPa according to ASTM D 638 test, and modulus of shearing is according to ASTM D
638 tests are 10 ~ 150MPa；Described foaming body proportion is 0.03 ~ 1.0.
Halogen-free flame-retardant resin matrix sandwich structure body the most according to claim 2, it is characterised in that described foaming body proportion
It is 0.08 ~ 0.8.
Halogen-free flame-retardant resin matrix sandwich structure body the most according to claim 2, it is characterised in that described foaming body proportion
It is 0.1 ~ 0.6.
Halogen-free flame-retardant resin matrix sandwich structure body the most according to claim 2, it is characterised in that described foaming body is selected from
PMI structural foam, CPMI structural foam, SAN fabric foam, PP structural foam, PES structural foam, PU structural foam, PET tie
Structure foam, phenolic structure foam, melamine structural foam one or more.
6. a Halogen-free flame-retardant resin matrix sandwich structure body, it is characterised in that described Halogen-free flame-retardant resin matrix sandwich
Body is by core (I) and resin matrix fibre reinforcement material (II) structure that is arranged in this core (I) upper surface and/or lower surface
The Halogen-free flame-retardant resin matrix sandwich structure body (III) become, described core (I) is by modified thermoplastic resin matrix's fiber reinforcement
Body material is constituted, and intersects to form gap structure by fiber infiltration resin, institute between described thermoplastic resin matrix and long fibre
State fiber infiltration resin length at more than 10nm；The proportion of described core (I) is 0.1 ~ 2.0.
Halogen-free flame-retardant resin matrix sandwich structure body the most according to claim 6, it is characterised in that described core (I)
Proportion is 0.1 ~ 1.0.
Halogen-free flame-retardant resin matrix sandwich structure body the most according to claim 6, it is characterised in that described core (I)
Proportion is 0.2 ~ 0.6.
9. according to the Halogen-free flame-retardant resin matrix sandwich structure body described in claim 1 or 6, it is characterised in that described resin base
Body fibre reinforcement material (II) is made up of thermosetting resin matrix fibre reinforcement material；Described thermosetting resin matrix is nothing
The thermosetting resin that halogen is fire-retardant；Described fibre reinforcement material is selected from continuous print carbon fibre material, glass fiber material, aramid fiber fibre
Dimension material, basalt fiber material one or more.
Halogen-free flame-retardant resin matrix sandwich structure body the most according to claim 9, it is characterised in that described halogen-free flameproof
The synthetic method of thermosetting resin, comprise the steps:
1) by thermosetting resin and the curing agent of the typical polymerization reaction directly preparation halogen-free flameproof containing N-P；
2) adding modified-reaction, the polymer by interpolation with fire retarding effect obtains halogen-free flameproof in ordinary hot thermosetting resin
Thermosetting resin.
11. Halogen-free flame-retardant resin matrix sandwich structure body according to claim 10, it is characterised in that described halogen-free flameproof
The synthetic method of thermosetting resin, comprise the steps:
A) synthesis containing P epoxy resin FD: prepare the FD ring containing 2wt%P element with bisphenol-f type novolac epoxy resin with DOPO
Epoxy resins；
B) synthesis containing N epoxy resin MFP: nitrogen-containing hardener 2,4,6-'s tri-(hydroxy phenyl benzylidene amino)-s-triazine (MFP)
Synthesis: with melamine and phenol reactant, prepare, with methyl guanamines modification, the phenolic cure that nitrogen content is 0.5～2.5wt%
Agent MFP；
C) preparation containing P-N epoxy resin solidifying system glue: take the FD epoxy resin containing 2wt%P of certain proportioning and contain N admittedly
Agent MFP is placed in dissolving, curing process in highly polar solvent dimethylformamide and acetone and makes hot melt adhesive liquid use；
D) synthesis of the FD/MFP epoxy-resin systems containing P-N halogen-free flameproof: actual measurement epoxide number is that 0.315mol/100g, tg exist
More than 145 DEG C, polymer is when Pwt%=2%, and LOI is 33-39, and at 180 DEG C, 2min gel, 7-10min solidifies, to obtain final product.
12. according to the Halogen-free flame-retardant resin matrix sandwich structure body described in claim 1 or 6, it is characterised in that described resin base
Body fibre reinforcement material (II) is made up of thermoplastic resin matrix's fibre reinforcement material；Described thermoplastic resin is modified
The thermoplastic resin of halogen-free flameproof；Described fibre reinforcement material is selected from continuous print carbon fibre material, glass fiber material, aramid fiber
Fibrous material, basalt fiber material one or more.
13. Halogen-free flame-retardant resin matrix sandwich structure body according to claim 12, it is characterised in that the nothing of described modification
The fire-retardant thermoplastic resin of halogen is selected from modified halogen-free flameproof PP and/or PE plastics.
The preparation method of 14. Halogen-free flame-retardant resin matrix sandwich structure body as described in claim 1 or 6, comprises the steps:
A) Stacking steps: the upper surface that includes resin matrix fibre reinforcement material (II) is layered in described core (I) and/or
Lower surface is to provide duplexer；
B) applying heat: be included in the firm matter flat plate mold of 5 ~ 13a level fineness and configure the layer obtained by step a)
Stack, heats 100 ~ 200 DEG C, is cooled to rapidly less than 80 DEG C and is shaped, prepare halogen-free flameproof after pressurization maintenance 0.5 ~ 30min
Resin matrix sandwich structural body (III).
The halogen-free flameproof that the preparation method of 15. Halogen-free flame-retardant resin matrix sandwich structure body according to claim 14 obtains
Resin matrix sandwich structural body is in 3C industry, household electric appliances and the application of cabinet surface texture sheet material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310715090.8A CN103753905B (en) | 2013-12-23 | 2013-12-23 | A kind of Halogen-free flame-retardant resin matrix sandwich structure body and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310715090.8A CN103753905B (en) | 2013-12-23 | 2013-12-23 | A kind of Halogen-free flame-retardant resin matrix sandwich structure body and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103753905A CN103753905A (en) | 2014-04-30 |
| CN103753905B true CN103753905B (en) | 2016-09-07 |
Family
ID=50521298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310715090.8A Active CN103753905B (en) | 2013-12-23 | 2013-12-23 | A kind of Halogen-free flame-retardant resin matrix sandwich structure body and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103753905B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| CN111231378B (en) * | 2020-01-13 | 2022-04-05 | 北京邦维高科特种纺织品有限责任公司 | Decorative layer and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1406745A (en) * | 2001-08-22 | 2003-04-02 | 方大集团股份有限公司 | Cyanuramide foam composite plates and manufacture thereof |
| CN102991046A (en) * | 2011-09-09 | 2013-03-27 | 上海杰事杰新材料(集团)股份有限公司 | Light-weight and high-strength plastic steel sandwich board and its making method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002200713A (en) * | 2001-01-06 | 2002-07-16 | Udagawa Reiko | Accordion curtain for ldk |
-
2013
- 2013-12-23 CN CN201310715090.8A patent/CN103753905B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1406745A (en) * | 2001-08-22 | 2003-04-02 | 方大集团股份有限公司 | Cyanuramide foam composite plates and manufacture thereof |
| CN102991046A (en) * | 2011-09-09 | 2013-03-27 | 上海杰事杰新材料(集团)股份有限公司 | Light-weight and high-strength plastic steel sandwich board and its making method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103753905A (en) | 2014-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10590250B2 (en) | Fiber-reinforced plastic molding material, method for producing same, and molded article | |
| US10647849B2 (en) | Epoxy resin composition, prepreg, carbon fiber-reinforced composite material, and manufacturing methods therefor | |
| CN106700548B (en) | A kind of preparation method containing benzoxazine resin composition and the prepreg and laminate being made from it | |
| CN104448698B (en) | A kind of melamine formaldehyde molding compound and preparation method thereof | |
| CN103753905B (en) | A kind of Halogen-free flame-retardant resin matrix sandwich structure body and preparation method thereof | |
| KR20120094163A (en) | Curable epoxy resin compositions and composites made therefrom | |
| JP5280681B2 (en) | Method for producing fiber reinforced hot melt epoxy resin | |
| CN103881309B (en) | Halogen-free non-phosphorus flame-retarded resin composition | |
| CN105367793A (en) | Cyanate ester resin prepolymer with excellent space environment property, and prepreg, preparation method and application thereof | |
| EP3024649B1 (en) | Improvements in or relating to fibre reinforced composites | |
| AU2018300880A1 (en) | Molded article and production method therefor | |
| CN100374487C (en) | Method for producing fiber-reinforced thermoplastic plastic and fiber-reinforced thermoplastic prastic | |
| AU2015362756B2 (en) | Epoxy-based resin composition for composite materials | |
| JP7242628B2 (en) | Improved resin hardener system | |
| CN111349309B (en) | Preparation method and application of powdery halogen-free flame-retardant epoxy resin composition | |
| JP2012025892A (en) | Resin composition, prepreg using the same, and fiber-reinforced composite material | |
| TWI627198B (en) | Thermoplastic epoxy matrix formulation, prepreg, composite and method for manufacturing the same | |
| JP6445389B2 (en) | Prepreg made of continuous fiber reinforced polycarbonate resin | |
| JP2013166927A (en) | Epoxy resin composition, prepreg and film using the same, and fiber reinforced composite material | |
| TWI610974B (en) | Use of a mixture of difunctional epoxy with monofunctional primary amine compound and/or difunctional secondary amine curing agent; composites comprising the mixture and the manufacture method thereof | |
| JP2020069654A (en) | Reinforced plastic molded product with gel coat |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |