CN105504695B - A kind of corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of high-strength and high-modulus and preparation method thereof - Google Patents
A kind of corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of high-strength and high-modulus and preparation method thereof Download PDFInfo
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- B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
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Abstract
The invention discloses corrosion-resistant vinyl ester resin SMC sheet shape moulding compounds of a kind of high-strength and high-modulus and preparation method thereof.Its raw material includes：Phenolic epoxy vinyl ester resin, high modulus fibre combination, graphene oxide powder, shrinking agent, thickener, inorganic mineral filler, wetting dispersing agent, coupling agent, curing agent, the releasing agent composition of oxidable magnesium thickening.It is made by preparation graphite alkylene vinyl ester resin sizing material, preparation thickener, resin paste preparation, dipping, laying, maturation stage, product preparation method is simple, easily operated.Product can be good at corrosion-resistant, solvent resistant；There is high intensity, high-modulus simultaneously；And heat, power, electricity etc. superior performance.
Description
Technical field
The present invention relates to polymeric material field, especially a kind of corrosion-resistant vinyl ester resin SMC sheet shape of high-strength and high-modulus
Moulding compound and preparation method.
Background technology
Sheet molding compound（SMC）It is the high strength composite that domestic development gets up in recent years.The content of the material fiber
Height applies continuous fiber or oriented alignment long fibre, to improve the mechanical strength of material.The exploitation of sheet molding compound
It is inseparable for producing the needs of energy consumption in light-weight fuel-saving automobile and reduction production process in recent years with auto industry.
Target is to replace vehicle body major part metallic structural components, Ru Menliang, shell, bumper and vehicle with part made from lower cost
Wheel etc..Sheet molding compound light-weight, that performance is good is also required in aviation, shipbuilding, weapon industry, to further promote it
Development.
The fiberfill fibers of SMC material are glass fibre at present, and content is higher.In comparison, high modulus carbon fiber and height
Modulus basalt fibre also has high heat-resisting, low-density, high heat conduction, highly conductive in addition to lightweight, high strength characteristics（Carbon fiber
Dimension）, the characteristics such as low thermal coefficient of expansion.But all the reinforcing fiber using carbon fiber as SMC, price are again too expensive.And nothing
The features such as although alkali Non-twisting glass fibre has good dispersion, boundling is good, and cuttability is good, immersion good, and price is relatively low.Therefore,
It selects several fibers for capableing of complementation in performance and price to make reinforcing material, respective advantage can not only be played, can also be reduced
Cost, the SMC production technologies enhanced using carbon fiber, basalt fibre and glass fiber hybrid are a good selecting partys
Case.
Vinyl ester resin is made by opening by epoxy resin and unsaturated monoacid, and ring is combined
The advantages of oxygen resin and unsaturated polyester resin, with low, the excellent mechanical property of density, superior heat resistance, corrosion resistance with
And the characteristics of rapid curing.The MgO thickening effects of Natural ethylene base ester resin are simultaneously bad, with going deep into for resin research and development, market
On had it is highly developed can MgO thickenings vinyl ester resin.
The abundant functional group of the huge specific surface area of graphene oxide and surface assigns its excellent composite performance, is passing through
Nano-dispersion can be formed in a polymer matrix after modified and reduction, in addition, graphene oxide is of low cost, raw material is easy to get,
It is mainly used in fuel cell hydrogen storage material, the microporous catalyst carrier of synthetic chemical industry, conductive plastics, conductive painting at present
Material etc., is rarely reported in the application of field of compound material.Graphene oxide is introduced into duroplastic moulding materials composite material
In, the comprehensive performances such as the high heat-resisting, high heat conduction of existing product certainly will be greatly improved.
In fields such as electronics, electric appliances, many precise parts require material small in 120 DEG C of coefficient of thermal expansion below, reach
10-6/ K is even lower, the heat resistance of glass fiber reinforced nylon material, and the thermal expansivity of aluminium alloy has obvious shortcoming, compels in the market
It is essential and wants the product of the characteristics such as good, heat-resisting, the low linear expansion of height of mechanical property.Carbon fiber, glass fiber hybrid enhance
Composite material makes it that can not only meet the precision under high fever working environment with its superior heat-stability energy, good designability
The requirement of parts physical mechanical property, and its moulding process and product low thermal coefficient of expansion, high heat-resisting etc. can be met
It is required that.
Invention content
The present invention propose regarding to the issue above a kind of corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of high-strength and high-modulus and
Preparation method, with graphene oxide to vinyl ester resin carry out graphite alkylene, then with carbon fiber, basalt fibre and alkali-free without
The vinyl ester resin after glass fiber hybrid enhancing graphite alkylene is twisted, SMC sheet shape moulding compound, molded composite material are prepared into
Product can realize the performance requirements such as high-strength, Gao Mo, corrosion-resistant, low linear expansion coefficient, high heat-resisting, high heat conduction.
To achieve the goals above, the technical solution adopted in the present invention is a kind of corrosion-resistant vinyl esters of high-strength and high-modulus
Resin SMC sheet shape moulding compound, raw material include by weight：60~100 parts of epoxy vinyl ester resin, 100~140 parts
High modulus fibre composition, 5~30 parts of graphene oxide powder, 30~50 parts of low profile agent, 1~5 part of thickening
Agent, 50~100 parts of inorganic mineral filler, 5~10 parts of mill base, 1~4 part of wetting dispersing agent, 1~5 part of coupling agent, 1
~4 parts of curing agent, 2~10 parts of releasing agent.
The epoxy vinyl ester resin is the epoxy vinyl ester resin of oxidable magnesium thickening.
One or more combinations below may be selected in the epoxy vinyl ester resin of the oxidable magnesium thickening：It is oxidable
Magnesium thickens bisphenol A-type vinylester resin, oxidable magnesium thickening toughening type bisphenol A-type vinylester resin, oxidable magnesium and thickens phenolic aldehyde
Type vinylester resin；Preferred mass number is 70~90 parts.
The high modulus fibre is combined as carbon fiber and glass fiber hybrid object or basalt fibre and glass fibre are mixed
Sundries, and carbon fiber, basalt fibre and glass fibre are using individually dipping system；Carbon fiber, basalt fibre are all warp
Silane based coupling agents processing is crossed, specification is 3K~60K；Glass fibre is through the non-twist glass of the processed alkali-free of silane based coupling agents
Glass silvalin, specification are 2400TEX or 4800TEX.Preferred mass number is 110~130 parts.
The graphene oxide powder is nano level, and preferred mass number is 10~20 parts.
One or more combinations in PVAc, PS or PMMA may be selected in the low profile agent, and preferred mass number is 35
~45 parts.
The thickener is pasted for magnesia, and raw material is calculated as 60~65 parts of styrene by weight：Active oxidation magnesium powder
33~38 parts, 1~3 part of zinc stearate, the preferred addition mass fraction of magnesia paste is 2~4 parts, further, preferably, oxidation
Magnesium paste raw material is calculated as 64 parts of styrene by weight：35 parts of active oxidation magnesium powder, 1 part of zinc stearate
The inorganic mineral filler is appointing in calcium carbonate, aluminium hydroxide, talcum powder, kaolin, bentonite or mica
One or more, preferred mass number are 70~90 parts.
The wetting dispersing agent is the copolymer containing acid group, and preferred mass number is 1~2 part.
The coupling agent is the response type coupling agent containing styryl, and preferred mass number is 1~3 part.
The curing agent is TBPB or TBPB and TBPO composite initiation systems, and the wherein weight proportion of TBPB/TBPO is
2/1, the total additive amount preferred mass number of curing agent is 1~2 part.
The releasing agent is any one in zinc stearate or calcium stearate, and preferred mass number is 3~5 parts.
The preparation method of the corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of high-strength and high-modulus as described above, including it is following
Step：
A. graphite alkylene vinyl ester resin sizing material is prepared：Graphene oxide is placed in supersonic oscillations 1h in styrene,
Then vinyl ester resin is added, then ultra-sonic vibrates 1h, it is spare as graphite alkylene vinyl ester resin sizing material；
B. thickener is prepared：Styrene, active oxidation magnesium powder, zinc stearate are weighed in proportion, put into agitator tank successively
In, start high speed dispersor, speed is adjusted to 1000~1500r/min, after stirring evenly, with not less than 100 mesh stainless (steel) wires
Filtering, viscosity control are spare as thickener in 15000~25000cps；
C. resin paste is prepared：Graphite alkylene vinyl ester resin sizing material, mill base, low profile agent, nothing are weighed by metering proportion
Filler, wetting dispersing agent, releasing agent, coupling agent, the curing agent of machine mineral put into high shear mixers and are sufficiently stirred, and turn
In 1000~1500r/min, temperature is controlled at 34~38 DEG C, is stirred 15 minutes, is evacuated to system spare pressure not for speed control
It higher than 0.08atm, then is stirred under vacuum not less than stirring after 5min, is stopped, rapidly the thickener of input metering, high-speed stirred 1~
2min, the resin paste fast transfer after stirring evenly are discarded in two storage paste slots of SMC machine group；
D. it impregnates：On the upper and lower polyethylene film of walking on even application 2~4mm thickness resin paste, continuous carbon fibre
Yarn and glass fiber yarn are cut into chopped single fiber by cutter, are uniformly scattered in lower-layer resin and paste over；
E. laying：First doctor gap of adjustment is 0.5~0.7mm, by resin paste and chopped carbon fiber in SMC machine group
Upper dipping, the mass parts ratio for controlling resin paste and chopped carbon fiber is (30~80):(70~20), preferably 50:50, adjustment second
A doctor gap be 1.0~1.3mm, resin paste is impregnated with short glass fiber in SMC machine group, control resin paste with it is short
The mass parts ratio for cutting glass fibre is (30~80):(70~20), preferably 50:50, the short glass fiber of dipping is equably set
It is synchronous by forcing press above the chopped carbon fiber of dipping, so that resin paste is impregnated with fiber and mixes one, then adjusted roll spacing
Air is excluded, SMC sheet is made, rolling device is coiled into SMC volumes or packing-box design；
F. it cures：The SMC sheet of winding or packing-box design is put into curing chamber thickening, curing temperature is 35~40 DEG C, is made
Resin is thoroughly impregnated fiber, obtains product.
Preferably, the single fiber length that is chopped in the step d is 22~26mm.
Preferably, the compacting machine speed of service is 3~18m/min in the step e, pressure is 30~45psi.
Preferably, SMC sheet 2.0~2.4mm of thickness in the step e, substance is 1800~2500g/ ㎡'s.
Using the present invention, has the following advantages：
1. carbon fiber and glass fiber hybrid, basalt fibre and glass fiber hybrid, collect the advantage of different fibers, meet
The requirement of the high-strength of sheet molding compound, Gao Mo, high performance-price ratio；
2. can MgO thickening vinyl ester resin impart the excellent acid-alkali-corrosive-resisting of sheet molding compound, organic solvent-resistant
The performances such as swelling, heat-resisting；
3. the abundant functional group of the huge specific surface area of graphene oxide and surface assigns sheet molding compound excellent heat（It is high
Heat-resisting, high heat conduction）, power（High intensity, high-modulus）, electricity（Electrical property）Etc. performance；
4. manufacturing method is simple, three-waste free discharge, at low cost, on-line mixing, production efficiency are high.
Specific implementation mode
The predetermined purpose reached for the present invention is further explained and technological means and effect are with reference to embodiments, right
Specific embodiments of the present invention are described in detail.
Embodiment 1：A kind of its original of the corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of high-strength and high-modulus provided in this embodiment
Material include by weight：（A）The vinyl ester resin selection OY-8978 of oxidable magnesium thickening can thicken bisphenol A-type vinyl acetate tree
Fat, parts by weight are 80 parts；(B) high modulus fibre composition selection carbon fiber and glass fiber hybrid object, and carbon fiber and glass
Glass fiber is using individually dipping system；Carbon fiber is to be handled by silane based coupling agents, specification 24K；Glass fibre is warp
The processed alkali-free Non-twisting glass fibre yarn of silane based coupling agents, specification 2400TEX.Parts by weight are 120 parts；(C) it aoxidizes
Graphene powder is nano level, and parts by weight are 15 parts；(D) low profile agent is PVAc, and parts by weight are 40 parts；(E) thickener is
Magnesia is pasted, specially styrene/active oxidation magnesium powder/zinc stearate=64 part/35 part/1 part, and it is 3 that magnesia, which pastes parts by weight,
Part；(F) inorganic mineral filler is the mixture of calcium carbonate and aluminium hydroxide, and parts by weight are 80 parts；(G) wetting dispersing agent be containing
The copolymer of acid group, parts by weight are 2 parts；(H) mill base selects vinyl ester resin for the grey mill base of vector resin, weight
Part is 8 parts；(I) it is 3 parts that coupling agent, which selects γ-methacryloxypropyl trimethoxy silane, parts by weight,；(J) curing agent
For the compound system of TBPB and TBPO, TBPB is 2/1 with TBPO weight proportions, and the total additive amount of curing agent is 2 parts；(K) it demoulds
Agent is zinc stearate, and parts by weight are 6 parts.
A kind of preparation method of the corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of high-strength and high-modulus as described above, step
Suddenly include：
A. graphite alkylene vinyl ester resin sizing material is prepared：Graphene oxide is placed in supersonic oscillations 1h in styrene,
Then OY-8978 vinyl ester resins are added, then ultra-sonic vibrates 1h, it is standby as graphite alkylene vinyl ester resin sizing material
With；
B. thickener is prepared：By the weight ratio of styrene/active oxidation magnesium powder/zinc stearate=64 part/35 part/1 part
Material is weighed, is put into agitator tank successively, starts high speed dispersor, speed is adjusted to 1000~1500r/min, is stirred evenly
Afterwards, it is filtered with not less than 100 mesh stainless (steel) wires, viscosity control is spare as thickener in 15000~25000cps；
C. resin paste is prepared：Graphite alkylene vinyl ester resin sizing material, grey mill base, the low wheels of PVAc are weighed by metering proportion
Wide agent, calcium carbonate, aluminium hydroxide, wetting dispersing agent, zinc stearate, γ-methacryloxypropyl trimethoxy silane,
TBPB and TBPO composite curing agents, put into high shear mixers and are sufficiently stirred, and rotating speed is controlled in 1000~1500r/min,
Temperature is controlled at 34~38 DEG C, is stirred 15 minutes, is evacuated to system spare pressure and is not higher than 0.08atm, then is stirred under vacuum not
After 5min, stop stirring, the thickener of input metering, 1~2min of high-speed stirred, the resin paste after stirring evenly are fast rapidly
Speed transfer is discarded in two storage paste slots of SMC machine group；
D. it impregnates：On the upper and lower polyethylene film of walking on even application 2~4mm thickness resin paste, continuous carbon fibre
It is the chopped single fibers of 22~26mm that yarn and glass fiber yarn are cut into length by cutter, is uniformly scattered in lower-layer resin and pastes over；
E. laying：First doctor gap of adjustment is 0.5~0.7mm, by resin paste and chopped carbon fiber in SMC machine group
Upper dipping, the mass parts ratio for controlling resin paste and chopped carbon fiber is 50:50；Second doctor gap of adjustment be 1.0~
1.3mm impregnates resin paste with short glass fiber in SMC machine group, controls the mass parts of resin paste and short glass fiber
Than for (30~80):(70~20)；The short glass fiber of dipping is uniformly placed in above the chopped carbon fiber of dipping, is synchronized logical
Excess pressure rod（The compacting machine speed of service is 3~18m/min, and pressure is 30~45psi）, so that resin paste is impregnated with fiber and mix one
Body, then adjusted roll spacing exclude air, 2.0~2.4mm of thickness are made, substance is the SMC sheet of 1800~2500g/ ㎡, through receiving
Winding apparatus is coiled into SMC volumes or packing-box design；
F. it cures：The SMC sheet of winding or packing-box design is put into curing chamber thickening, curing temperature is 35~40 DEG C, is made
Resin is thoroughly impregnated fiber, obtains product.
The average hardness Barcol that product obtains the composite material after testing is more than 55HBa, average bending strength 380MPa, bending
Modulus 13.5GPa, tensile strength 250Mpa, 300 DEG C of heat distortion temperature, linear expansion coefficient 1 × 10-6/ K, shrinking percentage zero.
Embodiment 2：A kind of corrosion-resistant sheet molding compound of high-strength and high-modulus（SMC material）Its raw material includes：(A) oxidable magnesium
(MgO) the vinyl ester resin selection OY-8976 thickened can thicken toughening type bisphenol A-type vinylester resin, and parts by weight are 90 parts；
(B) high modulus fibre composition selection basalt fibre and glass fiber hybrid object, and basalt fibre is adopted with glass fibre
With independent dipping system；Basalt fibre is to be handled by silane based coupling agents, specification 48K；Glass fibre is through silane
The alkali-free Non-twisting glass fibre yarn that base coupling agent treatment is crossed, specification 4800TEX.Parts by weight are 130 parts；(C）Graphite alkene
Powder is nano level, and parts by weight are 20 parts；(D) low profile agent is PS, and parts by weight are 45 parts；(E) thickener is pasted for magnesia,
Specially styrene/active oxidation magnesium powder/zinc stearate=60 part/38 part/2 part, it is 4 parts that magnesia, which pastes parts by weight,；(F) inorganic
Mineral filler is aluminium hydroxide, and parts by weight are 90 parts；(G) wetting dispersing agent is the copolymer containing acid group, parts by weight 1
Part；(H) mill base selects vinyl ester resin for the green mill base of vector resin, and parts by weight are 10 parts；(I) coupling agent selects γ-
Methacryloxypropyl trimethoxy silane, parts by weight are 3 parts；(J) curing agent is TBPB, and the total additive amount of curing agent is
4 parts；(K) releasing agent is calcium stearate, and parts by weight are 5 parts.
A kind of corrosion-resistant sheet molding compound of high-strength and high-modulus（SMC material）Preparation method, step includes：
A. graphite alkylene vinyl ester resin sizing material is prepared：Graphene oxide is placed in supersonic oscillations 1h in styrene,
Then OY-8976 vinyl ester resins are added, then ultra-sonic vibrates 1h, it is standby as graphite alkylene vinyl ester resin sizing material
With；
B. thickener is prepared：By the weight ratio of styrene/active oxidation magnesium powder/calcium stearate=60 part/38 part/2 part
Material is weighed, is put into agitator tank successively, starts high speed dispersor, speed is adjusted to 1000~1500r/min, is stirred evenly
Afterwards, it is filtered with not less than 100 mesh stainless (steel) wires, viscosity control is spare as thickener in 15000~25000cps；
C. resin paste is prepared：Graphite alkylene vinyl ester resin sizing material, green mill base, PS low profiles are weighed by metering proportion
Agent, aluminium hydroxide, wetting dispersing agent, calcium stearate, γ-methacryloxypropyl trimethoxy silane, TBPB curing agent,
It is sufficiently stirred in input high shear mixers, rotating speed control is controlled at 34~38 DEG C, stirred in 1000~1500r/min, temperature
It mixes 15 minutes, is evacuated to system spare pressure and is not higher than 0.08atm, then be stirred under vacuum not less than after 5min, stopping stirring is fast
The thickener of speed input metering, 1~2min of high-speed stirred, the resin paste fast transfer after stirring evenly are discarded to SMC machine group
In two storage paste slots；
D. it impregnates：On the upper and lower polyethylene film of walking on even application 2~4mm thickness resin paste, continuous basalt
Silvalin and glass fiber yarn are cut into chopped single fiber by cutter, are uniformly scattered in lower-layer resin and paste over；
E. laying：First doctor gap of adjustment is 0.5~0.7mm, by resin paste and chopped basalt fibre in SMC
It is impregnated on unit, the mass parts ratio of control resin paste and chopped basalt fibre is (30~80):(70~20) adjust second
Doctor gap is 1.0~1.3mm, and resin paste is impregnated with short glass fiber in SMC machine group, controls resin paste and is chopped
The mass parts ratio of glass fibre is (30~80):The short glass fiber of (70~20), dipping is uniformly placed in being chopped for dipping
It is synchronous to pass through pressure rod above basalt fibre（The compacting machine speed of service is 3~18m/min, and pressure is 30~45psi）, make
Resin paste is impregnated with fiber mixes one, then adjusted roll spacing excludes air, is made 2.0~2.4mm of thickness, and substance is 1800~
The SMC sheet of 2500g/ ㎡, rolling device are coiled into SMC volumes or packing-box design；
F. it cures：The SMC sheet of winding or packing-box design is put into curing chamber thickening, curing temperature is 35~40 DEG C, is made
Resin is thoroughly impregnated fiber, obtains product.
The average hardness Barcol for obtaining the composite material after testing is more than 55HBa, average bending strength 420MPa, bending modulus
13.8GPa, tensile strength 300Mpa, 300 DEG C of heat distortion temperature, linear expansion coefficient 1 × 10-6/ K, shrinking percentage zero.
Embodiment 3：A kind of corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of high-strength and high-modulus, raw material is by weight
Including：（A）The vinyl ester resin selection OY-8978 of oxidable magnesium thickening thickens phenol aldehyde type vinylester resin, parts by weight 70
Part；(B) high modulus fibre composition selection carbon fiber and glass fiber hybrid object, and carbon fiber uses individually with glass fibre
Dipping system；Carbon fiber is to be handled by silane based coupling agents, specification 12K；Glass fibre be through silane based coupling agents at
The alkali-free Non-twisting glass fibre yarn managed, specification 2400TEX.Parts by weight are 110 parts；(C) graphene oxide powder is to receive
Meter level, parts by weight are 10 parts；(D) it is 1 to 1 to combine by weight with PVAc that low profile agent, which is PMMA, and parts by weight are 35 parts；
(E) thickener is pasted for magnesia, specially styrene/active oxidation magnesium powder/zinc stearate=65 part/33 part/3 part, magnesia paste
Parts by weight are 2 parts；(F) inorganic mineral filler is talcum powder and kaolinic mixture, and parts by weight are 70 parts；(G) wetting and dispersing
Agent is the copolymer containing acid group, and parts by weight are 1 part；(H) mill base selects vinyl ester resin for the grey of vector resin
Mill base, parts by weight are 5 parts；(I) it is 1 part that coupling agent, which selects γ-methacryloxypropyl trimethoxy silane, parts by weight,；
(J) curing agent is the compound system of TBPB and TBPO, and TBPB is 2/1 with TBPO weight proportions, and the total additive amount of curing agent is 2
Part；(K) releasing agent is zinc stearate, and parts by weight are 3 parts.
Embodiment 4：A kind of corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of high-strength and high-modulus, raw material is by weight
Including：Oxidable 40 parts of magnesium thickening toughening type bisphenol A-type vinylester resin, oxidable magnesium thickening phenol aldehyde type vinylester resin 60
Part, 140 parts of high modulus fibre composition are the impurity of carbon fiber and basalt fibre and glass fibre, carbon fiber and the Black Warrior
Rock fiber is all to be handled by silane based coupling agents, specification 60K；Glass fibre is through the processed nothing of silane based coupling agents
Alkali Non-twisting glass fibre yarn, specification 4800TEX, 30 parts of graphene oxide powder, 15 parts of PVAc, 15 parts of PS, 20 parts
PMMA, 5 parts of thickener, 30 parts of kaolin, 45 parts of bentonites, 25 parts of micas, 10 parts of mill base, 4 parts of wetting dispersing agent, 5
The coupling agent, 4 parts of curing agent, 10 parts of releasing agent of part.
Embodiment 5：A kind of corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of high-strength and high-modulus, raw material is by weight
Including：60 epoxy vinyl ester resin, 100 parts of high modulus fibre composition, for the impurity for carbon fiber and glass fibre,
Carbon fiber is by silane based coupling agents processing, specification 3K, 5 parts of nano graphene oxide powder, 30 parts of low profile agent, 1
Part thickener, 50 parts of inorganic mineral filler, 5 parts of mill base, 1 part of wetting dispersing agent, 1 part of coupling agent, 1 part consolidate
Agent, 2 parts of releasing agent.
As described above, only present pre-ferred embodiments, thus appoint it is all without departing from this programme technology contents, according to this hair
Bright technical spirit makes any simple change, equivalent variations and modification to above example, still falls within the technology of the present invention
The range of scheme.
Claims (15)
1. a kind of corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of high-strength and high-modulus, which is characterized in that its raw material is by weight
Including：
(A) 60~100 parts of epoxy vinyl ester resin；
(B) 100~140 parts of high modulus fibre composition；
(C) 5~30 parts of graphene oxide powder；
(D) 30~50 parts of low profile agent；
(E) 1~5 part of thickener；
(F) 50~100 parts of inorganic mineral filler；
(G) 5~10 parts of mill base；
(H) 1~4 part of wetting dispersing agent；
(I) 1~5 part of coupling agent；
(J) 1~4 part of curing agent；
(K) 2~10 parts of releasing agent；
Component (A) epoxy vinyl ester resin is the epoxy vinyl ester resin of oxidable magnesium thickening, and described is oxidable
The epoxy vinyl ester resin of magnesium thickening selects one or more combinations below：Oxidable magnesium thickens bisphenol type epoxy ethylene
Base ester resin, oxidable magnesium thicken phenolic epoxy vinyl ester resin；Component (E) thickener is pasted for magnesia, former
Material is calculated as 60~65 parts of styrene by weight：33~38 parts of active oxidation magnesium powder, 1~3 part of zinc stearate；
The component（B）High modulus fibre composition is carbon fiber and glass fiber hybrid object or basalt fibre and glass fibre
Impurity, and carbon fiber, basalt fibre and glass fibre are using individually dipping system；Carbon fiber, basalt fibre are all
It is handled by silane based coupling agents, specification is 3K~60K；Glass fibre is non-twist through the processed alkali-free of silane based coupling agents
Glass fiber yarn, specification are 2400TEX or 4800TEX；
Described (I) coupling agent is the response type coupling agent containing styryl.
2. the corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of a kind of high-strength and high-modulus according to claim 1, feature exist
In：Magnesia paste addition mass fraction is 2~4 parts.
3. the corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of a kind of high-strength and high-modulus according to claim 1, feature exist
In：The component（B）Mass fraction is 110~130 parts.
4. the corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of a kind of high-strength and high-modulus according to claim 1, feature exist
In：Component (C) graphene oxide powder is nano level.
5. the corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of a kind of high-strength and high-modulus according to claim 4, feature exist
In：Component (C) mass fraction is 10~20 parts.
6. the corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of a kind of high-strength and high-modulus according to claim 1, feature exist
In：Low profile agent selects one or more combinations in PVAc, PS or PMMA.
7. the corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of a kind of high-strength and high-modulus according to claim 6, feature exist
In：Low profile agent mass fraction is 35~45 parts.
8. the corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of a kind of high-strength and high-modulus according to claim 1, feature exist
In：Inorganic mineral filler is any one of calcium carbonate, aluminium hydroxide, talcum powder, kaolin, bentonite or mica or several；
Wetting dispersing agent is the copolymer containing acidic-group；Curing agent is TBPB or TBPB and TBPO composite initiation systems, wherein
The weight proportion of TBPB/TBPO is 2/1；Releasing agent is any one in zinc stearate or calcium stearate.
9. the corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of a kind of high-strength and high-modulus according to claim 1 or 8, special
Sign is：Inorganic mineral filler mass fraction is 70~90 parts；Wetting dispersing agent mass fraction is 1~2 part；Coupling agent mass parts
Number is 1~3 part；The total additive amount of curing agent is 1~2 part；Releasing agent mass fraction is 3~5 parts.
10. the corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of a kind of high-strength and high-modulus according to claim 1, feature
It is：The epoxy vinyl ester resin mass fraction of the oxidable magnesium thickening is 70~90 parts.
11. a kind of corrosion-resistant vinyl ester resin SMC sheet shape molding of the high-strength and high-modulus prepared as described in claim 1-10 is any
The method of material, which is characterized in that include the following steps：
A. graphite alkylene vinyl ester resin sizing material is prepared：Graphene oxide is placed in supersonic oscillations 1h in styrene, then
Epoxy vinyl ester resin, then supersonic oscillations 1h is added, it is spare as graphite alkylene vinyl ester resin sizing material；
B. thickener is prepared：Styrene, active oxidation magnesium powder, zinc stearate are weighed in proportion, are put into agitator tank, are opened successively
Dynamic high speed dispersor, 1000~1500r/min is adjusted to by speed, after stirring evenly, is filtered with not less than 100 mesh stainless (steel) wires,
Viscosity control is spare as thickener in 15000~25000cps；
C. resin paste is prepared：Graphite alkylene vinyl ester resin sizing material, mill base, low profile agent, inorganic mine are weighed by metering proportion
Object filler, wetting dispersing agent, releasing agent, coupling agent, curing agent put into high shear mixers and are sufficiently stirred, rotating speed control
In 1000~1500r/min, temperature is controlled at 34~38 DEG C, is stirred 15 minutes, is evacuated to system spare pressure and is not higher than
0.08atm, then be stirred under vacuum not less than after 5min, stopping is stirred, the thickener of rapid input metering, 1~2min of high-speed stirred,
Resin paste fast transfer after stirring evenly is discarded in two storage paste slots of SMC machine group；
D. it impregnates：On the upper and lower polyethylene film of walking on even application 2~4mm thickness resin paste, continuous carbon fibre yarn and
Glass fiber yarn is cut into chopped single fiber by cutter, is uniformly scattered in lower-layer resin and pastes over；
E. laying：First doctor gap of adjustment is 0.5~0.7mm, and resin paste is soaked with chopped carbon fiber in SMC machine group
Stain, the mass parts ratio for controlling resin paste and chopped carbon fiber is (30~80):(70~20)；Second doctor gap of adjustment is
1.0~1.3mm impregnates resin paste with short glass fiber in SMC machine group, controls the matter of resin paste and short glass fiber
Amount part is compared for (30~80):(70~20)；The short glass fiber of dipping is uniformly placed in above the chopped carbon fiber of dipping, together
Step makes resin paste be impregnated with fiber and mixes one, then adjusted roll spacing excludes air, and SMC sheet is made, through receiving by compacting machine
Winding apparatus is coiled into SMC volumes or packing-box design；
F. it cures：The SMC sheet of winding or packing-box design is put into curing chamber thickening, curing temperature is 35~40 DEG C, makes resin
It is thoroughly impregnated fiber, obtains product.
12. a kind of preparation of the corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of high-strength and high-modulus according to claim 11
Method, it is characterised in that：Resin paste and the mass parts of chopped carbon fiber ratio are 50 in the step e:50.
13. a kind of preparation of the corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of high-strength and high-modulus according to claim 11
Method, it is characterised in that：The single fiber length that is chopped in the step d is 22~26mm.
14. a kind of preparation of the corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of high-strength and high-modulus according to claim 11
Method, it is characterised in that：The compacting machine speed of service is 3~18m/min in the step e, and pressure is 30~45psi.
15. a kind of preparation of the corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of high-strength and high-modulus according to claim 11
Method, it is characterised in that：SMC sheet 2.0~2.4mm of thickness in the step e, substance are 1800~2500g/ ㎡.
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| WO2022140691A1 (en) * | 2020-12-23 | 2022-06-30 | Magna Exteriors Inc. | Graphene enhanced sheet molding compound |
| CN112724608A (en) * | 2021-01-29 | 2021-04-30 | 河北铭特环保设备科技有限公司 | Bisphenol A type SMC (sheet molding compound) molding resin composition and preparation method thereof |
| CN114381107B (en) * | 2022-01-07 | 2023-09-22 | 江西增鑫科技股份有限公司 | SMC composite sheet for pig house leak boards and preparation method thereof |
| CN115141461B (en) * | 2022-07-22 | 2023-06-13 | 合肥荣事达电子电器集团有限公司 | SMC material and preparation process thereof |
| CN115449190A (en) * | 2022-08-23 | 2022-12-09 | 东南大学 | Modified resin for fiber reinforced polymer rib and preparation method thereof |
| CN117143436B (en) * | 2023-10-31 | 2024-02-13 | 达斯玛环境科技（北京）有限公司 | Epoxy resin composition, carbon fiber product, impeller, and preparation method and application of impeller |
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