CN106476365B - A kind of epoxy resin toughened base glass fibre composite and preparation method thereof - Google Patents
A kind of epoxy resin toughened base glass fibre composite and preparation method thereof Download PDFInfo
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- CN106476365B CN106476365B CN201610846813.1A CN201610846813A CN106476365B CN 106476365 B CN106476365 B CN 106476365B CN 201610846813 A CN201610846813 A CN 201610846813A CN 106476365 B CN106476365 B CN 106476365B
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- 239000002131 composite material Substances 0.000 title claims abstract description 154
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 146
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 146
- 239000006121 base glass Substances 0.000 title claims abstract description 36
- 239000000835 fiber Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 163
- 239000004744 fabric Substances 0.000 claims abstract description 52
- 239000003365 glass fiber Substances 0.000 claims abstract description 46
- 239000011521 glass Substances 0.000 claims abstract description 28
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 20
- 239000012745 toughening agent Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000004593 Epoxy Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 31
- 239000011159 matrix material Substances 0.000 claims description 22
- 239000011152 fibreglass Substances 0.000 claims description 9
- 239000010426 asphalt Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002525 ultrasonication Methods 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002924 oxiranes Chemical class 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 230000009267 minimal disease activity Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 239000002360 explosive Substances 0.000 claims 1
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 5
- 239000004433 Thermoplastic polyurethane Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 description 6
- 230000001976 improved effect Effects 0.000 description 5
- 238000005457 optimization Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10064—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising at least two glass sheets, only one of which being an outer layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
- B32B38/164—Drying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The present invention provides a kind of epoxy resin toughened base glass fibre composite and preparation method thereof, the composite includes at least one composite unit, each composite unit, which includes an epoxy resin base material layer and a glass fabric laying being layed on the epoxy resin base material layer, the epoxy resin base material layer, includes the component of following mass parts：40 ~ 90 parts of epoxy resin, 20 ~ 80 parts of curing agent and 1 ~ 25 part of toughener；The toughener is the one or more in liquid crystal material, nano silicon and TPU.The recombiner unit quantity that methods described contains in obtained composite as needed, by epoxy resin base material and glass fibre alternately coats successively or laying, so that epoxy resin toughened base glass fibre composite is made.The epoxy resin toughened base glass fibre composite of the present invention is compared with existing pure epoxy resin base glass fibre composite, and impact strength lifting 17% 35%, tensile strength does not reduce.
Description
Technical field
The invention belongs to glass fiber compound material technical field, and in particular to a kind of epoxy resin toughened base glass fibre
Composite and preparation method thereof.
Background technology
Epoxy resin-matrix glass fiber compound material has excellent mechanical property, corrosion resistance and chemical stability；Add
Man-hour cubical contraction is small；Outstanding advantages of cost is cheap.Therefore in building, communication and traffic transport, sports equipment, electronics electricity
The fields such as device, space flight and aviation are widely used.Because global range carries out energy-saving and emission-reduction, solve greenhouse effects.Composite is big
The application in the fields such as type aircraft, wind power generation blade, automobile component, oil exploitation sucker rod, electrical power transmission cables will be promoted and saved
The realization of energy emission reduction.Loss of weight is required for automobile use, improving fuel efficiency reduces energy consumption, and in recent years, lightweight is new
Energy automobile has become the trend of world car development, and more and more higher is required for the performance of composite.
It is high yet with epoxy resin cure crosslink density, cause the impact strength of composite low, therefore to asphalt mixtures modified by epoxy resin
Resin composite material toughness reinforcing becomes key.Existing common toughening modifying method is exactly that thermoplastic elastic is added in resin matrix
Body, but the addition of thermoplastic elastomer (TPE) often reduces the tensile strength of material while impact strength is improved, and makes compound
The tensile property of material is affected, thus certain weak point be present.
The content of the invention
For deficiencies of the prior art, the technical problem to be solved in the present invention is：For prior art middle ring
The impact strength of epoxy resin composite material is low, and existing toughening modifying method can lower the technology of the tensile strength of composite
Problem, and provide a kind of good toughness, will not reduce tensile strength of material epoxy resin toughened base glass fibre composite and
Its preparation method.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that：A kind of epoxy resin toughened base glass fibers
Composite is tieed up, including at least one composite unit, each composite unit include an epoxy resin base material layer
With a glass fabric laying being layed on the epoxy resin base material layer, the epoxy resin base material includes following quality
The component of part：40~90 parts of epoxy resin, 20~80 parts of curing agent and 1~25 part of toughener；The toughener be liquid crystal material,
One or more in nano silicon and TPU.Composite impact is being improved for toughening modifying method in the prior art
While intensity, the technical problem of the tensile strength of material can be reduced, present invention improves over the component of epoxy resin base material, selects
The organic-inorganic such as nano silicon, liquid crystal high polymer material rigid particles are as toughener, one side nano-silica of the present invention
SiClx, liquid crystal high polymer material toughener good dispersion, can be evenly dispersed into epoxy resin, be filled between epoxy resin
Divide ground absorption, bonding, crosslinking in the epoxy, enhances the stress transmission of particle and epoxy resin, and then raising shock resistance
Ability so that the impact strength of composite produced by the present invention improves compared to the composite for not carrying out toughness reinforcing processing
17~35%, can be with while material impact strength is improved on the other hand because the toughener used has rigid structure
Avoiding the tensile strength of material is reduced, and material can be reduced using thermoplastic elastomer (TPE) progress toughening modifying in the prior art by solving
The technical problem of tensile strength.
Further, when including two or more composite units, pass through between each two composite unit
What the epoxy resin base material layer of one composite unit was brought into close contact with the fiberglass cloth of another composite unit
Form to form the epoxy resin toughened base glass fibre composite to be superimposed.So, multiple composite units can be made
It is brought into close contact as an entirety, makes the obtained composite shock resistance comprising multiple composite units stronger, it is more suitable
For requiring that material is applied in terms of having the automobile component, aircraft components, wind power generation blade of high impact resistance.
Further, including 1~12 composite unit.So, it can either meet that the shock resistance of material is high, also keep away
Exempt to include excessive composite unit and reduce the tensile strength of material, the problem of bringing harmful effect to tensile property.
Further, the epoxide number of the epoxy resin is 0.48~0.54.
As optimization, the curing agent is diethylentriamine and epoxy propane butyl ether addition product, 4,4'- diaminourea hexichol
One or more in methane and hexahydrophthalic acid anhydride.Curing agent as selection, toughener can be made to be crosslinked more in an orderly manner
Fix in the epoxy, and then ensure that the impact strength performance of obtained composite is more preferable.
As optimization, the structural formula of the liquid crystal material is as shown in Equation 1：
Using such liquid crystal material, dispersive property is more preferable, be able to can be evenly dispersed into epoxy resin, with asphalt mixtures modified by epoxy resin
Fully adsorb, be bonded between fat, add contact of the particle with epoxy resin and combine, and then improve impact resistance.
As another optimization, the density of the glass fabric is 50-200g/m2.Using the glass fibre of such density
Cloth, it is high to be effectively ensured the impact strength of composite, while composite does not allow broken, avoid density it is excessive and
Caused by tensile strength it is low the problem of.
A kind of preparation method of epoxy resin toughened base glass fibre composite, comprises the following steps：
1) claim according to the component formula of the epoxy resin toughened base glass fibre composite epoxy resin substrate layer
Take raw material；
2) epoxy resin and toughener that weigh step 1) is mixed be incorporated in and handle 5~40 minutes under ultrasonic wave after, addition
The curing agent that step 1) weighs is well mixed under ul-trasonic irradiation, obtains epoxy resin base material；
3) epoxy resin base material made from one layer of step 2) is first coated in a mold, then on the epoxy resin base material upper berth
If layer of glass cloth, the first composite unit is obtained；
4) if what is prepared is the epoxy resin-matrix glass fiber compound material containing a composite unit, by step
3) the first composite unit obtained solidifies 5~24h in 25~200 DEG C, that is, obtains the ring containing a composite unit
Epoxy resin-based glass fiber compound material；
It is multiple first if what is prepared is the epoxy resin-matrix glass fiber compound material containing two composite units
Continue to coat one layer of epoxy resin base material on the fibrous glass cloth of condensation material unit, then continue laying one on epoxy resin base material
Layer glass fabric, obtains the second composite unit, the second composite unit is solidified into 5~24h in 25~200 DEG C, i.e.,
Obtain the epoxy resin-matrix glass fiber compound material containing two composite units；
It is multiple second if what is prepared is the epoxy resin-matrix glass fiber compound material containing three composite units
Continue to coat one layer of epoxy resin base material on the fibrous glass cloth of condensation material unit, then continue laying one on epoxy resin base material
Layer glass fabric, obtains triplex material cell, triplex material cell is solidified into 5~24h in 25~200 DEG C, i.e.,
Obtain the epoxy resin-matrix glass fiber compound material containing three composite units；
By that analogy, if obtained is the epoxy resin-matrix glass fiber compound material containing n composite unit,
Continue to coat one layer of epoxy resin base material on the fibrous glass cloth of the (n-1)th composite unit of acquisition, then in epoxy resin
Continue to lay layer of glass cloth on base material, the n-th composite unit is obtained, by the n-th composite unit in 25~200 DEG C
Solidify 5~24h, that is, obtain the epoxy resin-matrix glass fiber compound material containing n composite unit；N makes to be required
The epoxy resin-matrix obtained peels off the composite element number included in fibrous composite.
Using epoxy resin base material component formula of the present invention, by composite made from the above method, epoxy can be made
Resin base material and glass fibre are evenly dispersed in obtained composite, make the impact strength at each position of composite all
By force, and it also avoid base material or the problem of local tensile strength caused by glass fiber material is deposited in a certain position is low, be made
The impact strength of composite improve 17~35% compared to the composite for not carrying out toughness reinforcing processing, tensile strength phase
Do not decline for composite compared with no progress toughening modifying, while achieving good toughening effect, avoid
The reduction of tensile strength.
As optimization, the frequency of ultrasonic wave is 20~100KHz during ultrasonication in step 2).From such frequency
The ultrasonic wave of rate, toughener can be made to spread more evenly across in epoxy resin, and avoid the too high destruction component structure of frequency, made
The shock resistance of composite is more preferable.
As optimization, obtained epoxy resin toughened base glass fibre total composite thickness is 1~4mm.It is made so
It the composite of thickness, can both ensure that there is good shock resistance, and avoid tensile strength reduction.
Compared with prior art, the present invention has the advantages that：
1st, the present invention from the organic-inorganic rigid particles such as nano silicon, liquid crystal high polymer material as toughener,
These toughener good dispersions, can be evenly dispersed into epoxy resin, fully adsorb, be bonded between epoxy resin,
Crosslinking in the epoxy, enhances the stress transmission of particle and epoxy resin, and then improve impact resistance so that the present invention
The impact strength of obtained composite improves 17~35% compared to the composite for not carrying out toughness reinforcing processing.
2nd, the toughener that the present invention uses has rigid structure, and material can be avoided while material impact strength is improved
The tensile strength of material reduces, and tensile strength does not decline for the composite compared to no progress toughening modifying, solves
The technical problem of tensile strength of material can be reduced by carrying out toughening modifying using thermoplastic elastomer (TPE) in the prior art.
3rd, the preparation method of composite of the present invention is simple, and the raw material used is easily obtained, and relative low price, is had
Good prospects for commercial application and market prospects.
Embodiment
The present invention is described in further detail with reference to specific embodiment.The implementation case using the technology of the present invention as
Under the premise of implemented, now provide detailed embodiment and specific operating process illustrate the present invention it is creative, but
Protection scope of the present invention is not limited to following embodiment.
The raw material that following embodiments use has epoxy resin -51 (epoxide number is 0.48~0.54)；Liquid as shown in Equation 1
Brilliant material；Nano silicon；TPU；4,4'- MDAs (DDM)；593 curing agent (diethylentriamine and epoxy third
Alkane butyl ether addition product)；Methylhexahydrophthalic anhydride (MHHPA)；Glass fabric (density is 100g/ ㎡).
The liquid crystal material of equation 1 above is made with the following method：
(1) paraphthaloyl chloride and triethylene-glycol are weighed first, and the amount weighed is according to mol ratio 2：1 is weighed；
(2) medicine by more than is poured into three-necked bottle, and adds 50ml tetrachloroethanes as solvent；
(3) temperature of constant-temperature heating magnetic stirring apparatus is set as 80-100 DEG C, and the three-necked bottle by more than is placed in one
Carrying out magnetic agitation makes it react 2 hours, back flow reaction is subsequently passed through at 140-160 DEG C 6 hours；
(4) after in three-necked bottle add and triethylene-glycol equimolar amounts hydroquinones, afterwards at 140-160 DEG C
Reaction 10 hours is carried out under reflux temperature；
(5) with absolute ethyl alcohol come washed product after reaction terminates, washing times are that twice, vacuum filtration removes solvent；
(6) sample filtered is purified with 60 DEG C of apparatus,Soxhlet's acetone reflux 24 hours；
(7) finally product is placed in 70 DEG C of vacuum drying chamber and dried 10 hours, obtain liquid crystal material as shown in Equation 1
Material.
Embodiment 1
A kind of epoxy resin toughened base glass fibre composite, including five composite units, each composite wood
Material unit includes an epoxy resin base material layer and a glass fabric laying being placed on the epoxy resin base material layer, often
Pass through the epoxy resin base material layer and another composite unit of a composite unit between two composite units
Fiberglass cloth be brought into close contact be superimposed form the epoxy resin toughened base glass fibre composite, the asphalt mixtures modified by epoxy resin
Aliphatic radical material includes the component of following mass parts：The liquid crystal of 75 parts of epoxy resins -51,25 part of 593 curing agent and 8 parts of above-mentioned formulas 1
Material.
A kind of preparation method of epoxy resin toughened base glass fibre composite, is made with the following method：
1) component of following mass parts is weighed：75 parts of epoxy resins -51,25 part of 593 curing agent and 8 parts of above-mentioned formulas 1
Liquid crystal material；
2) epoxy resin -51 and liquid crystal material weighed step 1) is mixed evenly, in frequency 40KHz ultrasound
After being handled 30 minutes under ripple, add 593 curing agent that step 1) weighs and 5 minutes are mixed under ultrasonication to be well mixed, obtain
To epoxy resin base material；
3) epoxy resin base material made from one layer of step 2) is first coated in a mold, then on the epoxy resin base material upper berth
If layer of glass cloth, the first composite unit is obtained；In the fibrous glass cloth laying of the first composite unit after
One layer of epoxy resin base material of continuous coating, then continue laying layer of glass cloth on epoxy resin base material, it is compound to obtain second
Material cell；Continue to coat one layer of epoxy resin base material in the fibrous glass cloth laying of the second composite unit, then in ring
Continue to lay layer of glass cloth on epoxy resin-based material, obtain triplex material cell；... according to same step process,
So that obtain the 5th composite unit that gross thickness is 2mm；The thickness of each layer of epoxy resin base material coating is (gross thickness -5
× fiberglass cloth material thickness)/5；
4) the 5th composite unit for obtaining step 3) curing process 24h at 25 DEG C, 1# epoxy resin-matrixes are obtained
Glass fiber compound material.
1# epoxy resin-matrixes glass fiber compound material made from the present embodiment is cut into 80 × 10 × 2mm's with a chainsaw
Batten is impacted, carries out shock-testing, test result is shown in Table 1.
Embodiment 2
A kind of epoxy resin toughened base glass fibre composite, including five composite units, each composite wood
Material unit includes an epoxy resin base material layer and a glass fabric laying being placed on the epoxy resin base material layer, often
Pass through the epoxy resin base material layer and another composite unit of a composite unit between two composite units
Fiberglass cloth be brought into close contact be superimposed form the epoxy resin toughened base glass fibre composite, the asphalt mixtures modified by epoxy resin
Aliphatic radical material includes the component of following mass parts：The liquid crystal material of 80 parts of epoxy resins -51,20 parts DDM and 3 part above-mentioned formula 1.
A kind of preparation method of epoxy resin toughened base glass fibre composite, is made with the following method：
1) component of following mass parts is weighed：The liquid crystal material of 80 parts of epoxy resins -51,20 parts DDM and 3 part above-mentioned formula 1
Material；
2) epoxy resin -51 and liquid crystal material weighed step 1) is mixed evenly, in frequency 40KHz ultrasound
After being handled 20 minutes under ripple, add the DDM that step 1) weighs and 15 minutes are mixed under ultrasonication to be well mixed, obtain epoxy
Resin base material；
3) epoxy resin base material made from one layer of step 2) is first coated in a mold, then on the epoxy resin base material upper berth
If layer of glass cloth, the first composite unit is obtained；In the fibrous glass cloth laying of the first composite unit after
One layer of epoxy resin base material of continuous coating, then continue laying layer of glass cloth on epoxy resin base material, it is compound to obtain second
Material cell；Continue to coat one layer of epoxy resin base material in the fibrous glass cloth laying of the second composite unit, then in ring
Continue to lay layer of glass cloth on epoxy resin-based material, obtain triplex material cell；... according to same step process,
So that obtain the 5th composite unit that gross thickness is 2mm；The thickness of each layer of epoxy resin base material coating is (gross thickness -5
× fiberglass cloth material thickness)/5；
4) the 5th composite unit obtained step 3) raises temperature and is kept for 1 hour to 100 DEG C, and 140 DEG C keep 1 small
When, 180 DEG C are kept for 3 hours, obtain 2# epoxy resin-matrix glass fiber compound materials.
2# epoxy resin-matrixes glass fiber compound material made from the present embodiment is cut into 80 × 10 × 2mm's with a chainsaw
Batten is impacted, carries out shock-testing, test result is shown in Table 1.
Embodiment 3
A kind of epoxy resin toughened base glass fibre composite, including five composite units, each composite wood
Material unit includes an epoxy resin base material layer and a glass fabric laying being placed on the epoxy resin base material layer, often
Pass through the epoxy resin base material layer and another composite unit of a composite unit between two composite units
Fiberglass cloth be brought into close contact be superimposed form the epoxy resin toughened base glass fibre composite, the asphalt mixtures modified by epoxy resin
Aliphatic radical material includes the component of following mass parts：The liquid crystal material of 70 parts of epoxy resins -51,30 parts DDM and 5 part above-mentioned formula 1.
A kind of preparation method of epoxy resin toughened base glass fibre composite, is made with the following method：
1) component of following mass parts is weighed：The liquid crystal material of 70 parts of epoxy resins -51,30 parts DDM and 5 part above-mentioned formula 1
Material；
2) epoxy resin -51 and liquid crystal material weighed step 1) is mixed evenly, in frequency 40KHz ultrasound
After being handled 30 minutes under ripple, add the DDM that step 1) weighs and 30 minutes are mixed under ultrasonication to be well mixed, obtain epoxy
Resin base material；
3) epoxy resin base material made from one layer of step 2) is first coated in a mold, then on the epoxy resin base material upper berth
If layer of glass cloth, the first composite unit is obtained；In the fibrous glass cloth laying of the first composite unit after
One layer of epoxy resin base material of continuous coating, then continue laying layer of glass cloth on epoxy resin base material, it is compound to obtain second
Material cell；Continue to coat one layer of epoxy resin base material in the fibrous glass cloth laying of the second composite unit, then in ring
Continue to lay layer of glass cloth on epoxy resin-based material, obtain triplex material cell；... according to same step process,
So that obtain the 5th composite unit that gross thickness is 2mm；The thickness of each layer of epoxy resin base material coating is (gross thickness -5
× fiberglass cloth material thickness)/5；
4) the 5th composite unit obtained step 3) raises temperature and is kept for 1 hour to 100 DEG C, and 140 DEG C keep 1 small
When, 180 DEG C are kept for 3 hours, obtain 3# epoxy resin-matrix glass fiber compound materials.
3# epoxy resin-matrixes glass fiber compound material made from the present embodiment is cut into 80 × 10 × 2mm's with a chainsaw
Batten is impacted, carries out shock-testing, test result is shown in Table 1.
The preparation of comparative example pure epoxy resin base glass fibre composite
Weigh the component of following mass parts：80 parts of epoxy resins -51,20 parts of DDM are mixed 15 minutes under ultrasonication,
Obtain epoxy resin base material；Epoxy resin base material made from one layer is first coated in a mold, then on the epoxy resin base material
Layer of glass cloth is laid, obtains the first composite unit；In the fibrous glass cloth laying of the first composite unit
Continue to coat one layer of epoxy resin base material, then continue laying layer of glass cloth on epoxy resin base material, it is multiple to obtain second
Condensation material unit；Continue in the fibrous glass cloth laying of the second composite unit coat one layer of epoxy resin base material, then
Continue to lay layer of glass cloth on epoxy resin base material, obtain triplex material cell；... at same step
Reason, so that obtain the 5th composite unit；5th composite unit is raised into temperature to 100 DEG C of holdings 1 hour, 140 DEG C
Kept for 1 hour, 180 DEG C are kept for 3 hours, and comparative example pure epoxy resin base glass fibre composite is made.
Comparative example pure epoxy resin base glass fibre composite is cut into 80 × 10 × 2mm impact sample with a chainsaw
Bar, carries out shock-testing, and test result is shown in Table 1.
Composite batten obtained by embodiment 1,2,3 and comparative example is subjected to Charpy Impact performance test, test
Standard is GB/T1451-2005, and carries out tensile strength survey to the composite batten obtained by embodiment 1,2,3 and comparative example
Examination, test result are as shown in table 1 below.
The impact strength and tensile strength of the embodiment 1,2,3 of table 1 and comparative example
By upper table 1 it can be seen that the epoxy resin toughened base glass fibre composite of the present invention and existing pure epoxy resin base
Glass fiber compound material is compared, and impact strength improves 17%-35%, and the epoxy resin toughened base glass fibre of the present invention
Compared with the comparative example not composite by toughness reinforcing processing, tensile strength does not reduce even the tensile strength of composite
There is lifting effect slightly, achieve the guarantee impregnable unexpected technology of tensile strength while impact strength is improved
Effect.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (7)
1. a kind of epoxy resin toughened base glass fibre composite, including at least one composite unit, each is compound
Material cell includes an epoxy resin base material layer and a glass fabric paving being layed on the epoxy resin base material layer
Layer, it is characterised in that the epoxy resin base material layer includes the component of following mass parts：40~90 parts of epoxy resin, 20~80
Part curing agent and 1~25 part of toughener；The toughener is liquid crystal material；
The epoxy resin is EP-51 epoxy resin, and epoxide number is 0.48~0.54；
The curing agent is diethylentriamine and epoxy propane butyl ether addition product, 4,4'- MDAs and hexahydrobenzene
One or more in dicarboxylic acid anhydride；
The structural formula of the liquid crystal material is as shown in Equation 1：
2. epoxy resin toughened base glass fibre composite according to claim 1, it is characterised in that when including two or
During two or more composite unit, pass through the epoxy resin-matrix of a composite unit between each two composite unit
Material layer to form the flexibilizing epoxy tree with the form that the fiberglass cloth of another composite unit is brought into close contact to be superimposed
Aliphatic radical glass fiber compound material.
3. epoxy resin toughened base glass fibre composite according to claim 1, it is characterised in that including 1~12
Composite unit.
4. epoxy resin toughened base glass fibre composite according to claim 1, it is characterised in that the glass fibre
The density of cloth is 50-200g/m2。
5. epoxy resin toughened base glass fibre composite according to claim 1, it is characterised in that the flexibilizing epoxy
The gross thickness of Matrix Fiberglass Composite Explosive is 1~4mm.
6. a kind of preparation method of epoxy resin toughened base glass fibre composite, it is characterised in that comprise the following steps：
1) according to any epoxy resin toughened base glass fibre composite epoxy resin substrate layer of Claims 1 to 5
Component formula weigh raw material；
2) epoxy resin and toughener that weigh step 1) is mixed be incorporated in and handle 5~40 minutes under ultrasonic wave after, addition step
1) curing agent weighed is well mixed under ul-trasonic irradiation, obtains epoxy resin base material；
3) epoxy resin base material made from one layer of step 2) is first coated in a mold, then sets one on the epoxy resin base material upper berth
Layer glass fabric, obtains the first composite unit；
4) if what is prepared is the epoxy resin-matrix glass fiber compound material containing a composite unit, step 3) is obtained
The the first composite unit obtained solidifies 5~24h in 25~200 DEG C, that is, obtains the asphalt mixtures modified by epoxy resin containing a composite unit
Aliphatic radical glass fiber compound material；
If what is prepared is the epoxy resin-matrix glass fiber compound material containing two composite units, in the first composite wood
Continue to coat one layer of epoxy resin base material on the fibrous glass cloth of material unit, then continue one layer of glass of laying on epoxy resin base material
Glass fiber cloth, the second composite unit is obtained, the second composite unit is solidified into 5~24h in 25~200 DEG C, that is, obtained
Epoxy resin-matrix glass fiber compound material containing two composite units；
If what is prepared is the epoxy resin-matrix glass fiber compound material containing three composite units, in the second composite wood
Continue to coat one layer of epoxy resin base material on the fibrous glass cloth of material unit, then continue one layer of glass of laying on epoxy resin base material
Glass fiber cloth, triplex material cell is obtained, triplex material cell is solidified into 5~24h in 25~200 DEG C, that is, obtained
Epoxy resin-matrix glass fiber compound material containing three composite units；
By that analogy, if obtained is the epoxy resin-matrix glass fiber compound material containing n composite unit, obtaining
Continue to coat one layer of epoxy resin base material on the fibrous glass cloth of the (n-1)th composite unit obtained, then in epoxy resin base material
On continue lay layer of glass cloth, obtain the n-th composite unit, by the n-th composite unit in 25~200 DEG C solidification
5~24h, that is, obtain the epoxy resin-matrix glass fiber compound material containing n composite unit；N is required obtained
Epoxy resin-matrix peels off the composite element number included in fibrous composite.
7. the preparation method of epoxy resin toughened base glass fibre composite according to claim 6, it is characterised in that step
It is rapid 2) in during ultrasonication the frequency of ultrasonic wave be 20~100kHz.
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| CN112063107A (en) * | 2020-08-06 | 2020-12-11 | 黑龙江科技大学 | Metal glass fiber/epoxy resin composite material and preparation method thereof |
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