CN106476365A - 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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- CN106476365A CN106476365A CN201610846813.1A CN201610846813A CN106476365A CN 106476365 A CN106476365 A CN 106476365A CN 201610846813 A CN201610846813 A CN 201610846813A CN 106476365 A CN106476365 A CN 106476365A
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- epoxy resin
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- base material
- glass fibre
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- 239000002131 composite material Substances 0.000 title claims abstract description 165
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 148
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 148
- 239000006121 base glass Substances 0.000 title claims abstract description 39
- 239000000835 fiber Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 155
- 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
- 238000000034 method Methods 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
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 6
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract 2
- 239000004593 Epoxy Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000011159 matrix material Substances 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- 239000011152 fibreglass Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000010426 asphalt 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 compound 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
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000002360 explosive Substances 0.000 claims 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
- 229920002725 thermoplastic elastomer Polymers 0.000 description 6
- 238000005516 engineering process Methods 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
- 230000000694 effects Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003756 stirring Methods 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002708 enhancing effect Effects 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
- 230000005540 biological transmission Effects 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
- 238000007599 discharging 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
- 238000010438 heat treatment Methods 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
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration 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
Landscapes
- 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 includes an epoxy resin base material layer and a glass fabric laying being layed on the epoxy resin base material layer, and 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 one or more in liquid crystal material, nano silicon and TPU.The recombiner unit quantity that methods described contains in obtained composite as needed, epoxy resin base material and glass fibre is alternately coated successively or is laid, so that epoxy resin toughened base glass fibre composite is obtained.The epoxy resin toughened base glass fibre composite of the present invention compared with existing pure epoxy resin base glass fibre composite, 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；Plus
Man-hour cubical contraction is little；The outstanding advantages such as with low cost.Therefore in building, communication and traffic transport, sports equipment, electronics electricity
The fields such as device, space flight and aviation are widely used.As global range carries out energy-saving and emission-reduction, greenhouse effects are solved.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 promote section
The realization that can be reduced discharging.Loss of weight is required for automobile use, fuel efficiency reducing energy consumption is improved, in recent years, lightweight is new
Energy automobile has become as the trend of world car development, and the performance for composite requires more and more higher.
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 is toughness reinforcing to become key.Existing common toughening modifying method is exactly interpolation thermoplastic elastic in resin matrix
Body, but the tensile strength for often reducing material while being added in raising impact strength of thermoplastic elastomer (TPE), make to be combined
The tensile property of material is affected, thus there is certain weak point.
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 above-mentioned technical problem, the present invention is adopted the following technical scheme that：A kind of epoxy resin toughened base glass fibers
Dimension composite, including at least one composite unit, each composite unit includes an epoxy resin base material layer
The glass fabric laying being layed on the epoxy resin base material layer with one, the epoxy resin base material include 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 prior art
The technical problem of the tensile strength of material while intensity, 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 as toughener, one side nano-silica of the present invention
SiClx, liquid crystal high polymer material toughener good dispersion, can be evenly dispersed in epoxy resin, fill between epoxy resin
Divide ground absorption, bonding, in the epoxy, the stress for enhancing particle and epoxy resin is transmitted, and then improves shock resistance for crosslinking
Ability so that the impact strength of composite obtained in the present invention is improved compared to the composite for not carrying out toughness reinforcing process
17～35%, on the other hand because the toughener for adopting has rigid structure, permissible while material impact strength is improved
The tensile strength of material is avoided to reduce, solving carries out toughening modifying using thermoplastic elastomer (TPE) in prior art and can reduce material
The technical problem of tensile strength.
Further, when two or more composite units are included, pass through between each two composite unit
The epoxy resin base material layer of one composite unit is fitted tightly with the fiberglass cloth of another composite unit
Form to form the epoxy resin toughened base glass fibre composite to be superimposed.As such, it is possible to make multiple composite units
Fit tightly as an entirety, make the obtained composite shock resistance comprising multiple composite units higher, more suitable
For requiring that material applied in terms of having the automobile component of high impact resistance, aircraft components, wind power generation blade.
Further, including 1～12 composite unit.So, the shock resistance that can either meet material is high, also keeps away
Exempted from including excessive composite unit and reduced the tensile strength of material, dysgenic problem has been brought to tensile property.
Further, the epoxide number of the epoxy resin is 0.48～0.54.
Used 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.Such curing agent is selected, 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.
Used as optimization, the structural formula of the liquid crystal material is as shown in Equation 1：
Using such liquid crystal material, dispersive property more preferably, can be evenly dispersed in epoxy resin, with asphalt mixtures modified by epoxy resin
Fully adsorb between fat, be bonded, increased contact of the particle with epoxy resin and combine, and then improve impact resistance.
Used as another optimization, the density of the glass fabric is 50-200g/m2.Glass fibre using such density
Cloth, the impact strength that composite can be effectively ensured are high, while composite does not allow broken, it is to avoid density excessive and
The low problem of the tensile strength that causes.
A kind of preparation method of epoxy resin toughened base glass fibre composite, comprises the 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) by step 1) epoxy resin that weighs and toughener mixed be incorporated in process 5～40 minutes under ultrasonic wave after, add
Step 1) curing agent that weighs mixed under ul-trasonic irradiation, obtains epoxy resin base material；
3) first coat one layer of step 2 in a mold) obtained in epoxy resin base material, then on the epoxy resin base material upper berth
If layer of glass cloth, the first composite unit is obtained；
4) if prepared is the epoxy resin-matrix glass fiber compound material containing a composite unit, by step
3) the first composite unit for obtaining solidifies 5～24h in 25～200 DEG C, that is, obtain the ring containing a composite unit
Epoxy resin-based glass fiber compound material；
If prepared is the epoxy resin-matrix glass fiber compound material containing two composite units, multiple first
Continue one layer of epoxy resin base material of coating 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 5～24h in 25～200 DEG C, i.e.,
Obtain the epoxy resin-matrix glass fiber compound material containing two composite units；
If prepared is the epoxy resin-matrix glass fiber compound material containing three composite units, multiple second
Continue one layer of epoxy resin base material of coating on the fibrous glass cloth of condensation material unit, then continue laying one on epoxy resin base material
Layer glass fabric, obtains the 3rd composite unit, the 3rd composite unit is solidified 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 one layer of epoxy resin base material of coating on the fibrous glass cloth of the (n-1)th composite unit for obtaining, then in epoxy resin
Continue laying 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
5～24h of solidification, that is, obtain the epoxy resin-matrix glass fiber compound material containing n composite unit；N is required system
The epoxy resin-matrix for obtaining peels off the composite element number included in fibrous composite.
Using epoxy resin base material component formula of the present invention, by composite obtained in said 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 glass fiber material is deposited in the low problem of the local tensile strength for causing at a certain position, be obtained
The impact strength of composite improve 17～35% compared to the composite for not carrying out toughness reinforcing process, tensile strength phase
Compared with not declining for not carrying out the composite of toughening modifying, while achieving good toughening effect, it is to avoid
The reduction of tensile strength.
As optimization, step 2) in during ultrasonication the frequency of ultrasonic wave be 20～100KHz.From such frequency
The ultrasonic wave of rate, can make toughener spread more evenly across in epoxy resin, and avoid the too high destruction component structure of frequency, make
The shock resistance of composite is more preferable.
Used as optimization, obtained epoxy resin toughened base glass fibre total composite thickness is 1～4mm.It is obtained so
The composite of thickness, both can ensure that with good shock resistance, and avoid tensile strength reduction.
Compared to existing technology, the present invention has the advantages that：
1st, the present invention selects the organic-inorganic rigid particles such as nano silicon, liquid crystal high polymer material as toughener,
These toughener good dispersions, can be evenly dispersed in epoxy resin, fully adsorb, be bonded between epoxy resin,
In the epoxy, the stress for enhancing particle with epoxy resin is transmitted, and then improves impact resistance so that the present invention for crosslinking
The impact strength of obtained composite improves 17～35% compared to the composite for not carrying out toughness reinforcing process.
2nd, the toughener that the present invention is adopted has rigid structure, can avoid material while material impact strength is improved
The tensile strength of material reduces, and tensile strength is solved compared to not declining for not carrying out the composite of toughening modifying
The technical problem that toughening modifying can reduce tensile strength of material is carried out using thermoplastic elastomer (TPE) in prior art.
3rd, the preparation method of composite of the present invention is simple, and the raw material for using is easily obtained, and relative low price, has
Good prospects for commercial application and market prospects.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment.The implementation case with the technology of the present invention is being
Under the premise of implemented, now provide detailed embodiment and specific operating process be creative the present invention to be described, but
Protection scope of the present invention is not limited to below example.
Following embodiments using raw material have epoxy resin -51 (epoxide number is 0.48～0.54)；Liquid as shown in Equation 1
Brilliant material；Nano silicon；TPU；4,4'- MDA (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 adopted and is obtained with the following method：
(1) paraphthaloyl chloride and triethylene-glycol are weighed first, the amount for weighing is according to mol ratio 2：1 is weighed；
(2) above medicine is poured in three-necked bottle, and the tetrachloroethanes of 50ml is added as solvent；
(3) temperature of constant-temperature heating magnetic stirring apparatus is set as 80-100 DEG C, and above three-necked bottle is placed in one
Carrying out magnetic agitation makes which react 2 hours, subsequently through back flow reaction 6 hours at 140-160 DEG C；
(4) hydroquinones with triethylene-glycol equimolar amounts is added after in three-necked bottle, afterwards at 140-160 DEG C
Carry out reacting 10 hours under reflux temperature；
(5) with absolute ethyl alcohol come washed product after reaction terminates, for twice, vacuum filtration removes solvent to washing times；
(6) sample for crossing suction filtration 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 dries 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, per
By the epoxy resin base material layer of a composite unit and another composite unit between two composite units
Fiberglass cloth fit tightly 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, adopts and is obtained 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) by step 1) epoxy resin -51 that weighs and liquid crystal material mixing and stirring, in the ultrasound of frequency 40KHz
After processing 30 minutes under ripple, step 1 is added) 593 curing agent that weigh mix 5 minutes to mix under ultrasonication, obtain
To epoxy resin base material；
3) first coat one layer of step 2 in a mold) obtained in epoxy resin base material, then on the epoxy resin base material upper berth
If layer of glass cloth, the first composite unit is obtained；Continue in the fibrous glass cloth laying of the first composite unit
One layer of epoxy resin base material of continuous coating, then continue laying layer of glass cloth on epoxy resin base material, obtain second and be combined
Material cell；Continue one layer of epoxy resin base material of coating in the fibrous glass cloth laying of the second composite unit, then in ring
Continue laying layer of glass cloth on epoxy resin-based material, obtain the 3rd composite unit；... according to same step process,
So that obtain fiveth composite unit of the gross thickness for 2mm；The thickness of each layer of epoxy resin base material coating is (gross thickness -5
× fiberglass cloth material thickness)/5；
4) by step 3) the 5th composite unit that obtains curing process 24h at 25 DEG C, obtain 1# epoxy resin-matrix
Glass fiber compound material.
1# epoxy resin-matrix glass fiber compound material obtained in the present embodiment is cut into 80 × 10 × 2mm's with a chainsaw
Impact batten, carries out shock-testing, and 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, per
By the epoxy resin base material layer of a composite unit and another composite unit between two composite units
Fiberglass cloth fit tightly 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：80 parts of epoxy resins -51, liquid crystal materials of 20 parts of DDM and 3 part of above-mentioned formulas 1.
A kind of preparation method of epoxy resin toughened base glass fibre composite, adopts and is obtained with the following method：
1) component of following mass parts is weighed：80 parts of epoxy resins -51, liquid crystal materials of 20 parts of DDM and 3 part of above-mentioned formulas 1
Material；
2) by step 1) epoxy resin -51 that weighs and liquid crystal material mixing and stirring, in the ultrasound of frequency 40KHz
After processing 20 minutes under ripple, step 1 is added) DDM that weighs mixes 15 minutes to mix under ultrasonication, obtains epoxy
Resin base material；
3) first coat one layer of step 2 in a mold) obtained in epoxy resin base material, then on the epoxy resin base material upper berth
If layer of glass cloth, the first composite unit is obtained；Continue in the fibrous glass cloth laying of the first composite unit
One layer of epoxy resin base material of continuous coating, then continue laying layer of glass cloth on epoxy resin base material, obtain second and be combined
Material cell；Continue one layer of epoxy resin base material of coating in the fibrous glass cloth laying of the second composite unit, then in ring
Continue laying layer of glass cloth on epoxy resin-based material, obtain the 3rd composite unit；... according to same step process,
So that obtain fiveth composite unit of the gross thickness for 2mm；The thickness of each layer of epoxy resin base material coating is (gross thickness -5
× fiberglass cloth material thickness)/5；
4) by step 3) the 5th composite unit that obtains rises high-temperature and kept for 1 hour to 100 DEG C, and 140 DEG C keep 1 little
When, 180 DEG C are kept for 3 hours, obtain 2# epoxy resin-matrix glass fiber compound material.
2# epoxy resin-matrix glass fiber compound material obtained in the present embodiment is cut into 80 × 10 × 2mm's with a chainsaw
Impact batten, carries out shock-testing, and 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, per
By the epoxy resin base material layer of a composite unit and another composite unit between two composite units
Fiberglass cloth fit tightly 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：70 parts of epoxy resins -51, liquid crystal materials of 30 parts of DDM and 5 part of above-mentioned formulas 1.
A kind of preparation method of epoxy resin toughened base glass fibre composite, adopts and is obtained with the following method：
1) component of following mass parts is weighed：70 parts of epoxy resins -51, liquid crystal materials of 30 parts of DDM and 5 part of above-mentioned formulas 1
Material；
2) by step 1) epoxy resin -51 that weighs and liquid crystal material mixing and stirring, in the ultrasound of frequency 40KHz
After processing 30 minutes under ripple, step 1 is added) DDM that weighs mixes 30 minutes to mix under ultrasonication, obtains epoxy
Resin base material；
3) first coat one layer of step 2 in a mold) obtained in epoxy resin base material, then on the epoxy resin base material upper berth
If layer of glass cloth, the first composite unit is obtained；Continue in the fibrous glass cloth laying of the first composite unit
One layer of epoxy resin base material of continuous coating, then continue laying layer of glass cloth on epoxy resin base material, obtain second and be combined
Material cell；Continue one layer of epoxy resin base material of coating in the fibrous glass cloth laying of the second composite unit, then in ring
Continue laying layer of glass cloth on epoxy resin-based material, obtain the 3rd composite unit；... according to same step process,
So that obtain fiveth composite unit of the gross thickness for 2mm；The thickness of each layer of epoxy resin base material coating is (gross thickness -5
× fiberglass cloth material thickness)/5；
4) by step 3) the 5th composite unit that obtains rises high-temperature and kept for 1 hour to 100 DEG C, and 140 DEG C keep 1 little
When, 180 DEG C are kept for 3 hours, obtain 3# epoxy resin-matrix glass fiber compound material.
3# epoxy resin-matrix glass fiber compound material obtained in the present embodiment is cut into 80 × 10 × 2mm's with a chainsaw
Impact batten, carries out shock-testing, and 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 mix 15 minutes under ultrasonication,
Obtain epoxy resin base material；Epoxy resin base material obtained in first coating one layer in a mold, then on the epoxy resin base material
Laying layer of glass cloth, obtains the first composite unit；In the fibrous glass cloth laying of the first composite unit
Continue one layer of epoxy resin base material of coating, then continue laying layer of glass cloth on epoxy resin base material, obtain second multiple
Condensation material unit；One layer of epoxy resin base material of continuation coating in the fibrous glass cloth laying of the second composite unit, then
Continue laying layer of glass cloth on epoxy resin base material, obtain the 3rd composite unit；... at same step
Reason, so that obtain the 5th composite unit；5th composite unit is risen high-temperature kept for 1 hour, 140 DEG C to 100 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 obtained.
Comparative example pure epoxy resin base glass fibre composite is cut into the impact sample of 80 × 10 × 2mm with a chainsaw
Bar, carries out shock-testing, and test result is shown in Table 1.
Embodiment 1,2,3 is carried out Charpy Impact performance test with the composite batten obtained by comparative example, test
Standard is GB/T1451-2005, and carries out tensile strength survey to embodiment 1,2,3 with the composite batten obtained by comparative example
Examination, test result are as shown in table 1 below.
1 embodiment 1,2,3 of table and impact strength and the tensile strength of 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
The tensile strength of composite and comparative example not through the composite of toughness reinforcing process compared with, tensile strength does not reduce even
There is lifting effect slightly, achieve while impact strength is improved and ensure the impregnable unexpected technology of tensile strength
Effect.
Finally illustrate, above example is only unrestricted in order to technical scheme to be described, although with reference to relatively
Good embodiment has been described in detail to the present invention, 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, the objective without deviating from technical solution of the present invention and scope, and which all should be covered at this
In the middle of the right of invention.
Claims (10)
1. a kind of epoxy resin toughened base glass fibre composite, including at least one composite unit, each is combined
Material cell includes the glass fabric paving that an epoxy resin base material layer and are 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 one or more in liquid crystal material, nano silicon and TPU.
2. epoxy resin toughened base glass fibre composite according to claim 1, it is characterised in that when include two or
During two or more composite unit, by 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 fitted tightly 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 epoxy resin
Epoxide number be 0.48～0.54.
5. epoxy resin toughened base glass fibre composite according to claim 1, it is characterised in that the curing agent is
One kind in diethylentriamine and epoxy propane butyl ether addition product, 4,4'- MDA and hexahydrophthalic acid anhydride
Or it is multiple.
6. epoxy resin toughened base glass fibre composite according to claim 1, it is characterised in that the liquid crystal material
Structural formula as shown in Equation 1：
7. 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.
8. 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.
9. a kind of preparation method of base glass fibre composite epoxy resin toughened as described in claim 1～8 is arbitrary, its are special
Levy and be, comprise the steps：
1) according to the arbitrary epoxy resin toughened base glass fibre composite epoxy resin substrate layer of claim 1～8
Component formula weigh raw material；
2) by step 1) epoxy resin that weighs and toughener mixed be incorporated in process 5～40 minutes under ultrasonic wave after, add step
1) curing agent for weighing is mixed under ul-trasonic irradiation, obtains epoxy resin base material；
3) first coat one layer of step 2 in a mold) obtained in epoxy resin base material, then set one on the epoxy resin base material upper berth
Layer glass fabric, obtains the first composite unit；
4) if prepared is the epoxy resin-matrix glass fiber compound material containing a composite unit, by step 3) obtain
The the first composite unit for obtaining solidifies 5～24h in 25～200 DEG C, that is, obtain the asphalt mixtures modified by epoxy resin containing a composite unit
Aliphatic radical glass fiber compound material；
If prepared is the epoxy resin-matrix glass fiber compound material containing two composite units, in the first composite wood
Continue one layer of epoxy resin base material of coating on the fibrous glass cloth of material unit, then continue one layer of glass of laying on epoxy resin base material
Glass fiber cloth, obtains the second composite unit, the second composite unit is solidified 5～24h in 25～200 DEG C, that is, is obtained
Epoxy resin-matrix glass fiber compound material containing two composite units；
If prepared is the epoxy resin-matrix glass fiber compound material containing three composite units, in the second composite wood
Continue one layer of epoxy resin base material of coating on the fibrous glass cloth of material unit, then continue one layer of glass of laying on epoxy resin base material
Glass fiber cloth, obtains the 3rd composite unit, the 3rd composite unit is solidified 5～24h in 25～200 DEG C, that is, 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 one layer of epoxy resin base material of coating on the fibrous glass cloth of the (n-1)th composite unit for obtaining, then in epoxy resin base material
Upper continuation laying layer of glass cloth, obtains the n-th composite unit, the n-th composite unit is solidified in 25～200 DEG C
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.
10. the preparation method of epoxy resin toughened base glass fibre composite according to claim 9, it is characterised in that
Step 2) in during ultrasonication the frequency of ultrasonic wave be 20～100KHz.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109291595A (en) * | 2018-09-21 | 2019-02-01 | 上海华迎汽车零部件有限公司 | Composite material, automobile spare tire lid and preparation method thereof |
| CN111548603A (en) * | 2020-06-10 | 2020-08-18 | 九江科旭复合材料制造有限公司 | Preparation method of improved epoxy resin-based glass fiber composite material |
| 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 |
| CN113550139A (en) * | 2020-04-24 | 2021-10-26 | 深圳市劢全新材料科技有限责任公司 | Preparation method of aromatic polyester electrospun membrane compounded with ceramic |
| CN114057395A (en) * | 2021-12-13 | 2022-02-18 | 苏州市华研富士新材料有限公司 | High-strength high-temperature-resistant glass fiber composite board and production process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153735A (en) * | 2011-02-28 | 2011-08-17 | 桂林理工大学 | Method for preparing biphenyl thermotropic polyester liquid crystals |
| CN102617984A (en) * | 2011-01-26 | 2012-08-01 | 中国科学院理化技术研究所 | Modified epoxy resin base material and modified epoxy resin matrix composite material |
-
2016
- 2016-09-23 CN CN201610846813.1A patent/CN106476365B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617984A (en) * | 2011-01-26 | 2012-08-01 | 中国科学院理化技术研究所 | Modified epoxy resin base material and modified epoxy resin matrix composite material |
| CN102153735A (en) * | 2011-02-28 | 2011-08-17 | 桂林理工大学 | Method for preparing biphenyl thermotropic polyester liquid crystals |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109291595A (en) * | 2018-09-21 | 2019-02-01 | 上海华迎汽车零部件有限公司 | Composite material, automobile spare tire lid and preparation method thereof |
| CN113550139A (en) * | 2020-04-24 | 2021-10-26 | 深圳市劢全新材料科技有限责任公司 | Preparation method of aromatic polyester electrospun membrane compounded with ceramic |
| CN111548603A (en) * | 2020-06-10 | 2020-08-18 | 九江科旭复合材料制造有限公司 | Preparation method of improved epoxy resin-based glass fiber composite material |
| 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 |
| CN114057395A (en) * | 2021-12-13 | 2022-02-18 | 苏州市华研富士新材料有限公司 | High-strength high-temperature-resistant glass fiber composite board and production process thereof |
| CN114057395B (en) * | 2021-12-13 | 2023-09-12 | 苏州市华研富士新材料有限公司 | High-strength high-temperature-resistant glass fiber composite board and production process thereof |
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