CN106280287A - A kind of resin combination, composite and its preparation method and application - Google Patents
A kind of resin combination, composite and its preparation method and application Download PDFInfo
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- CN106280287A CN106280287A CN201610769669.6A CN201610769669A CN106280287A CN 106280287 A CN106280287 A CN 106280287A CN 201610769669 A CN201610769669 A CN 201610769669A CN 106280287 A CN106280287 A CN 106280287A
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- 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
- C08L63/10—Epoxy resins modified by unsaturated compounds
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
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- 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
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- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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Abstract
The present invention relates to a kind of resin combination, composite and its preparation method and application.The invention provides a kind of resin combination, including: (a) thermosetting resin matrix, (b) Graphene, (c) acrylic polymer and optional (d) other additives.The composite prepared by this resin combination has the mechanical property of excellence.
Description
Technical field
The present invention relates to polymer matrix composite preparation field, in particular to a kind of resin combination, composite wood
Material and its preparation method and application.
Background technology
Fiber reinforced polymer matrix composite has a wide range of applications, by various enhancings in actual productive life
The enhancement effect of fiber and fabric can reach the highest mechanical strength, a lot of occasions can be good at substitute reinforcing bar,
The metal materials such as aluminium alloy also effectively reduce the weight of end article.But, traditional fiber reinforced polymer matrix composite
Have that toughness is low, not resistant to shearing and the shortcoming of brittle fracture easily occurs, the biggest expansion limiting such materials'use field.
Therefore, by effective means, fiber reinforced polymer matrix composite carried out toughness reinforcing and keep the mechanics that it is high strong simultaneously
Degree, it is achieved rigidity-toughness balanced is just particularly important.
And Graphene is the reinforcing material of new generation with excellent mechanical property of discovered in recent years, its ultimate strength is
130GPa, stretch modulus can reach 1TPa, is the lamellar layer material that mechanical strength is the highest.But Graphene is easily in resin
Reuniting, this can affect the performance of composite.Existing technology is both for graphene dispersion molten at polarity organic molecule
Situation in agent (such as ethanol, DMF etc.) or water, without reference to the dispersion in fluoropolymer resin liquid.The technology also having is by stone
Ink alkene first disperses to be mixed in resin by dispersion liquid the most again, and then evacuation removes solvent.This adds the most again
The very complicated degree of operation.
In view of this, the special proposition present invention.
Summary of the invention
It is an object of the invention to provide a kind of composite with excellent mechanical performance.
One aspect of the present invention relates to a kind of resin combination, including: (a) thermosetting resin matrix, (b) Graphene, (c) third
Olefin(e) acid esters polymer and optional (d) other additives.
According to some embodiments, by weight, amount Wc of (c) acrylic polymer and amount Wb of (b) Graphene
Ratio Wc/Wb be preferably greater than or equal to 2.5, more preferably equal to or greater than 3, further preferably greater than or equal to 4, the most greatly
In or equal to 5, most preferably equal to or greater than 6.
According to some embodiments, described resin combination includes: (a) thermosetting resin matrix 100 weight portion, (b) stone
Ink alkene 0.1-3 weight portion, (c) acrylic polymer 0.5-10 weight portion and optional (d) other additives 2-20 weight
Amount part.
Preferably, described resin combination includes: (a) thermosetting resin matrix 100 weight portion, (b) Graphene 0.5-2 weight
Amount part, (c) acrylic polymer 0.8-5 weight portion and optional (d) other additives 3-15 weight portion.
Preferably, described resin combination includes: (a) thermosetting resin matrix 100 weight portion, (b) Graphene 0.8-1 weight
Amount part, (c) acrylic polymer 1-4 weight portion and optional (d) other additives 4-10 weight portion.
Another aspect of the present invention relates to a kind of composite, particularly section bar, including the solidification of described resin combination
Thing and reinforcing fiber materials.
Another aspect of the present invention relates to the method preparing composite, comprises the steps: to make described resin combination soak
Enter to described reinforcing fiber materials, curing molding.
Another aspect of the present invention relates to composite as sports goods, furniture parts, office appliance parts, automotive department
Part, aircraft components or fuselage material, spacecraft component, blade of wind-driven generator, insulated wall connector, construction material and oil
The application of well winning apparatus parts.
The composite prepared by this resin combination has the mechanical property of excellence, has high intensity, anti-shearing, high-ductility
The performance of property.
Detailed description of the invention
Graphene is the reinforcing material of new generation with excellent mechanical property of discovered in recent years, and its ultimate strength is
130GPa, stretch modulus can reach 1TPa, is the lamellar layer material that mechanical strength is the highest.As long as Graphene can be in polymerization
Thing matrix is formed good dispersion effect, just can significantly improve the mechanical property of material, also even be able to improve material
Heat resistance.The most in the present invention, in traditional fiber reinforced polymer matrix composite, introduce Graphene, make graphite
Alkene and reinforcing fiber, the synergism that formation of fabrics is good, it is achieved strengthen and toughness reinforcing double effects, thus be obviously improved material
Combination property.
The invention aims to provide polymer matrix composite and the preparation side thereof of a kind of Graphene activeness and quietness
Method, particularly to thermosetting resin base fiber reinforced composite material, promotes the comprehensive mechanical property of material.
I. resin combination
One aspect of the present invention relates to a kind of resin combination, including: (a) thermosetting resin matrix, (b) Graphene, (c) third
Olefin(e) acid esters polymer and optional (d) other additives.
According to a kind of embodiment, the resin combination of the present invention includes:
(a) thermosetting resin matrix 100 weight portion；
(b) Graphene 0.1-3 weight portion, such as 0.5-2 weight portion, or 0.8-1 weight portion；
(c) acrylic polymer 0.5-10 weight portion, such as 0.8-5 weight portion, or 1-4 weight portion, such as 2 weight portions；
And
Optional (d) other additives 2-20 weight portion, or 3-15 weight portion, or 4-10 weight portion.
According to a kind of embodiment, resin combination includes: (a) thermosetting resin matrix 100 weight portion, (b) Graphene
0.1-3 weight portion, (c) acrylic polymer 0.5-10 weight portion and optional (d) other additives 2-20 weight
Part.
According to a kind of embodiment, resin combination includes: (a) thermosetting resin matrix 100 weight portion, (b) Graphene
0.5-2 weight portion, (c) acrylic polymer 0.8-5 weight portion and optional (d) other additives 3-15 weight portion.
According to a kind of embodiment, resin combination includes: (a) thermosetting resin matrix 100 weight portion, (b) Graphene
0.8-1 weight portion, (c) acrylic polymer 1-4 weight and optional (d) other additives 4-10 weight portion.
In order to realize more preferable dispersion effect, by weight, amount Wc of (c) acrylic polymer and (b) Graphene
Ratio Wc/Wb of amount Wb be preferably greater than or equal to 2.5, more preferably equal to or greater than 3, further preferably greater than or equal to 3.5,
It is greater than or equal to 4, is yet more preferably greater than or equal to 5, most preferably equal to or greater than 6.
(a) thermosetting resin matrix
Thermosetting resin matrix can be the curable thermosetting resin of free radical or radical polymerization mould assembly thermosetting resin.
Thermosetting resin matrix can be epoxy resin, epoxy acrylic resin, polyurethane, bimaleimide resin,
One or more of unsaturated polyester resin and phenolic resin.Unsaturated polyester resin can be metaphenylene unsaturated polyester (UP)
One or more in resin, adjacent benzene-type unsaturated polyester resin.
(b) Graphene
The sheet number of plies of Graphene can be 1-10 layer, such as 1-5 layer.Graphene can be selected from single-layer graphene, double-deck stone
Ink alkene and one or more during there is few layer graphene of 3-10 layer.Single-layer graphene: refer to by one layer with benzene ring structure (i.e.
Hexagonal honeycomb structure) the most closelypacked carbon atom constitute a kind of Two-dimensional Carbon material.Bilayer graphene (Bilayer
Graphene): refer to by two-layer with benzene ring structure (i.e. hexagonal honeycomb structure) the most closelypacked carbon atom with different heaps
A kind of Two-dimensional Carbon material that buttress mode (including AB stacking, AA stacking, AA ' stacking etc.) stacking is constituted.Few layer graphene (Few-
Layer): refer to by 3-10 layer with benzene ring structure (i.e. hexagonal honeycomb structure) the most closelypacked carbon atom with different stackings
A kind of Two-dimensional Carbon material that mode (including ABC stacking, ABA stacking etc.) stacking is constituted.
Relative to 100 weight portion thermosetting resin matrix, the amount of Graphene can be 0.1-3 weight portion, 0.5-2 weight
Part, or 0.5-1 weight portion.
(c) acrylic polymer
It addition, (c) acrylic polymer with the use of the innovative point being also the present invention.On the one hand this component
Effect and its acidity that can effectively play releasing agent is not strong, and meanwhile, as amphipathy macromolecule, it can also effectively carry
High and that the various fillers of guarantee (especially Graphene) is in the resin combination degree that is uniformly dispersed, plays the effect of dispersant,
Thus the most also the mechanical property of end article is being produced active influence.In a word, acrylic polymer is generation
For the excellent selection of organic acid in common releasing agent.
C () acrylic polymer can be esters of acrylic acid homopolymer or acrylic acid esters co-polymer, preferably propylene
Esters of gallic acid block copolymer.C () acrylic acid esters co-polymer can be one or more of: random copolymer, block copolymerization
Thing, graft copolymer or alternate copolymer, preferred block copolymer.C () acrylic polymer includes at least one (first
Base) acrylate monomeric units.C () acrylic polymer (such as acrylate based block copolymer) can include following
One or more monomeric units, for example, at least two kinds monomeric units: (i) acrylic acid；(ii) methacrylic acid；(iii) acrylic acid
Arrcostab, such as acrylic acid C1-C15Arrcostab, acrylic acid C1-C10Arrcostab, acrylic acid C1-C6Arrcostab or acrylic acid C1-C4Alkane
Base ester；(iv) alkyl methacrylate, such as methacrylic acid C1-C15Arrcostab, methacrylic acid C1-C10Arrcostab, methyl
Acrylic acid C1-C6Arrcostab or methacrylic acid C1-C4Arrcostab；V () benzyl acrylate, such as acrylic acid C6-C20Aryl ester,
Acrylic acid C6-C15Aryl ester, acrylic acid C6-C10Aryl ester or acrylic acid C6-C8Aryl ester；(vi) aryl methacrylate,
Such as methacrylic acid C6-C20Aryl ester, methacrylic acid C6-C15Aryl ester, methacrylic acid C6-C10Aryl ester or methyl-prop
Olefin(e) acid C6-C8Aryl ester；(vii) acrylic acid heteroaryl ester, such as acrylic acid C3-C20Heteroaryl ester, acrylic acid C4-C15Heteroaryl ester,
Acrylic acid C5-C10Heteroaryl ester or acrylic acid C6-C8Heteroaryl ester；And (viii) methacrylic acid heteroaryl ester, such as methyl
Acrylic acid C3-C20Heteroaryl ester, methacrylic acid C4-C15Heteroaryl ester, methacrylic acid C5-C10Heteroaryl ester or methyl-prop
Olefin(e) acid C6-C8Heteroaryl ester.Acrylate based block copolymer can include acrylic acid, acrylic acid methyl ester., ethyl acrylate, third
Olefin(e) acid butyl ester, amyl acrylate, Hexyl 2-propenoate, methacrylic acid, methyl methacrylate, ethyl acrylate, acrylic acid fourth
One or more in the block copolymer of ester, amyl acrylate and Hexyl 2-propenoate.Acrylate based block copolymer can
Think one or more in the block copolymer of methacrylic acid, methyl methacrylate, butyl acrylate.
Acrylic polymer number-average molecular weight can control between 5000-50000, between 6000-40000,
Between 8000-30000, between 10000-20000.
Relative to 100 weight portion thermosetting resin matrix, the amount of acrylic polymer can be 0.5-10 weight portion,
Such as 0.8-5 weight portion, 1-4 weight portion, 0.5-2 weight portion, or 1-2 weight portion, such as 0.6,0.8,1.0,1.2,1.4,1.6,
1.8、2.0、2.2、2.4、2.6、2.8、3.0、3.5、4.0、4.5、5.0、5.5、6.0、6.5、7.0、7.5、8.0、8.5、9.0、
9.5 or 10 weight portions.
(d) other additives
Other additives can be the conventional additives in resin combination or fiber-resin composite.Other add
Add agent and include one or more in releasing agent, initiator, firming agent, releasing agent, mill base, filler.
Relative to 100 weight portion thermosetting resin matrix, the amount of other additives can be 0.1-30 weight portion, such as 1-
25 weight portions, 2-20 weight portion, or 3-15 weight portion, or 4-10 weight portion.
II. composite or section bar
The invention provides a kind of composite or section bar, there is high intensity, anti-shearing, the performance characteristics of high tenacity, from
And improve the comprehensive mechanical property of material.The composite of the present invention is thermosetting resin based composites.
According to a kind of embodiment, the invention provides a kind of composite or section bar, by the resin combination of the present invention
And reinforcing fiber makes.
According to a kind of embodiment, the invention provides a kind of composite, including the present invention resin combination and
Reinforcing fiber in resin combination.
According to a kind of embodiment, the present invention relates to a kind of composite or section bar, including the solidfied material of resin combination
And reinforcing fiber materials.Reinforcing fiber materials is in the solidfied material of resin combination.
It is by weight based on the amount of reinforcing fiber materials in composite or the gross weight of section bar, composite or section bar
50%-80%, such as 55%-75%, or 60%-70%, such as 65%.Resin combination in composite or section bar (or solidification
Thing) amount can be 20%-50% by weight, such as 25%-45%, or 30%-40%, such as 35%.Such as, by weight
Meter, reinforcing fiber materials can also be 50%, 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%,
75%, 78% or 80% etc..By weight, the amount of resin combination (or solidfied material) can also be 20%, 22%, 25%,
28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48% or 50% etc..
According to some embodiments, reinforcing material is one or both of continuous fiber and fabric.Real according to some
Executing mode, described continuous fiber includes glass fibre, basalt fibre, aramid fiber, polysulphonamide fiber, carbon fiber, gathers benzene
One or more in two formyl p-phenylenediamine fibers (such as Kevlar fiber) and superhigh molecular weight polyethylene fibers.According to one
A little embodiments, continuous fiber yarn is that glass fibre, basalt fibre, Fanglun 1414 are (such as Kevlar
Fiber) and one or more of superhigh molecular weight polyethylene fibers.According to some embodiments, fabric is continuous felt, table
One or more of face felt and tape edge felt.
III. the method preparing composite or section bar
Another aspect of the present invention relates to the method preparing composite or section bar, comprises the following steps: make the tree of the present invention
Oil/fat composition is immersed in reinforcing fiber materials, curing molding.
According to a kind of embodiment, the forming method of thermosetting resin based composites or section bar be pultrusion curing molding or
Resin transfer molding (RTM molding).
According to a kind of embodiment, the method preparing composite or section bar comprises the following steps: by the resin of the present invention
Compositions impregnates, pultrusion curing molding.In pultrusion curing molding, the temperature being heating and curing is preferably controlled between 100-160 DEG C.
After pultrusion curing molding, being dried, the temperature being dried is preferably controlled between 90-100 DEG C.
According to a kind of embodiment, the method preparing composite or section bar comprises the following steps: by the resin of the present invention
Compositions is injected in the reinforcing fiber materials of preforming, uses resin transfer molding.
It is an advantage of the current invention that, by ripe composite material forming method, optimizing thermosetting resin formula
On the basis of (especially the interpolation of Graphene and acrylate based block copolymer with the use of), with simple and effective way
Prepare the fiber reinforced polymer matrix composite of activeness and quietness, thus improve the comprehensive mechanical property of material.
The invention still further relates to composite or section bar as sports goods, furniture parts, office appliance parts, automotive department
Part, aircraft components or fuselage material, spacecraft component, blade of wind-driven generator, insulated wall connector, construction material and oil
The application of well winning apparatus parts.The purposes of fiber-reinforced resin section bar, can list Herba Veronicastri, golf clubs, bicycle
The sports goods such as vehicle frame；Automobile, the frame (frame) of airborne vehicle or fuselage material, spacecraft component, blade of wind-driven generator
Deng.Especially, mechanical strength highly, the therefore fiber of the present invention are required due to automobile component, aircraft components, spacecraft component
Strengthen resin forming product and be suitable for these purposes.The fiber-reinforced resin composition of the present invention is particularly suitable for wind-driven generator leaf
The resin material of sheet.
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but those skilled in the art will
Understanding, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.In embodiment unreceipted specifically
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or instrument unreceipted production firm person, be
The conventional products obtained can be bought by city.
Embodiment
Primary raw material
Graphene: Shandong holy well new material company limited provides.
Glass fiber yarn: 4800Tex, Taishan glass fiber Ltd.
Surface of polyester felt: 40g/m2, Lars Science and Technology Ltd. of Beijing section.
Glass fibre continuous felt: 300g/m2, Nanjing Tianming Composite Material Co., Ltd..
Carbon fiber: T300,2400Tex, toray company.
Glass fiber yarn/basalt fibre yarn mixture: 4800Tex, Jiangsu Gekko Swinhonis basalt continuous fiber high and new technology
Company limited.
Superhigh molecular weight polyethylene fibers: 4800Tex, Shanghai Sirui PolymerTechnology Co., Ltd..
Kevlar fiber: KEVLAR 49,2400Tex, du pont company.
Epoxy acrylic resin: MFE36, East China University Of Science And Technology Huachang Polymer Co., Ltd provides.
Metaphenylene unsaturated polyester resin: MERICAN9406, East China University Of Science And Technology Huachang Polymer Co., Ltd provides.
Bimaleimide resin: BMI-01, Honghu Shuangma New Materials Technology Co., Ltd..
Epoxy resin and firming agent pyromellitic acid anhydride: scientific and technological (Shanghai) limited company of favour cypress new material provides,
The epoxy resin trade mark is TF3120.
Thermosetting phenolic resin and corresponding firming agent: PF7003, Shandong holy well new material company limited provides.
Isocyanates MDI:PM-400, Yantai Wanhua Polyurethane Company Limited provides.
PEPA premixed systems: QX30, Nanjing, Nanjing Si Taipan Chemical Co., Ltd. provides.
Resin initiator: the peroxidating 2 ethyl hexanoic acid tert-butyl ester (TBPO), benzoyl peroxide (BPO), benzoyl peroxide first
Tert-butyl acrylate (TBPB), is analytical pure.
Antishrinking agent: DX-700, Foshan Dao Kesi micropowder company limited.
Triethylene diamine: analytical pure, Nanjing Guo Chen Chemical Co., Ltd. provides.
Acrylate based block copolymer: being Qingdao University of Science and Technology provides.
Inner pattern releasing agent applicable: Pul24, AXEl company of the U.S. provides.
Embodiment 1 (pultrusion)
(1) raw-material preparation and preforming layout
The configuration of (i) resin adhesive liquid
Carrying out the configuration of glue according to following component, be sequentially added into material, often adding a kind of material needs to stir 10-
15min, rotating speed is 2500r/min.Epoxy acrylic resin 100 parts, Graphene 0.1 part, methacrylic acid-acrylic acid butyl ester are embedding
Section copolymer (in polymer, the molar ratio of two kinds of monomeric units is 1.5:1, number-average molecular weight 50000) 0.5 part, other are conventional
Additive 15.5 parts (include that initiator TBPO/TBPB compounds 3 weight portions, Pulvis Talci 5 weight portion, ground calcium carbonate 5 weight portion,
Antishrinking agent 1 weight portion, inner pattern releasing agent applicable 0.5 part).Ultrasonic disperse 15min again is needed after having stirred.
(ii) preforming layout
Glass fiber yarn (4800Tex) is passed sequentially through creel, glue maceration tank, preforming tool, imports to and finally
Through hot forming tool.By upper and lower two layers polyester surface felt by leading felt device, preforming tool, import to and eventually pass through heat one-tenth
Mould.The number of regulation silvalin is so that the content of glass fiber of end article is 80%.
(2) pultrusion produces
Set three sections of temperature of hot forming tool as one section 105 DEG C, two-stage nitration 155 DEG C, three sections 150 DEG C.After temperature stabilization
Produce.Set pultrusion speed as 500mm/min.
The glue that prepare being imported in glue maceration tank, the equipment of starting produces, will the glass fibre of glue dipping
Yarn and surface of polyester felt are drawn in hot forming tool, become section bar, be cut into fixed length by cutter sweep after being heating and curing.
Sample surface in process of production is the most smooth, does not has crackle, falls slag and unfilled corner, illustrates that releasing agent is respond well.Finally by institute
Obtain composite and put into post processing solidification 12h in 100 DEG C of baking ovens.
Embodiment 2 (pultrusion)
Other steps are same as in Example 1, and simply Graphene is 0.5 part, methacrylic acid-acrylic acid butyl ester block copolymerization
Thing is 2.5 parts.
Embodiment 3 (pultrusion)
Other steps are same as in Example 1, and simply Graphene is 1 part, methacrylic acid-acrylic acid butyl ester block copolymer
Thing is 5 parts.
Embodiment 4 (pultrusion)
Other steps are same as in Example 1, and simply Graphene is 2 parts, and acrylic polymer is methyl methacrylate
Ester-butyl acrylate-butyl methacrylate block copolymer (in polymer, the molar ratio of three kinds of monomeric units is 1:1:1,
Number-average molecular weight 35000), parts by weight are 7.5 parts.
Embodiment 5 (pultrusion)
Other steps are same as in Example 1, and simply Graphene is 3 parts, and acrylic polymer is methyl methacrylate
(in polymer, the molar ratio of three kinds of monomeric units is ester-methacrylic acid-butyl methacrylate block copolymer: methyl
Acrylic acid methyl ester.: methacrylic acid: butyl methacrylate=2:1:1.5, number-average molecular weight 20000), parts by weight are 10
Part.
Embodiment 6 (pultrusion)
Other steps are same as in Example 2, and simply thermosetting resin matrix is changed to epoxy resin and (consists of mark by weight
Meter: epoxy resin 50 parts, firming agent pyromellitic acid anhydride 50 parts), pultrusion speed is 250mm/min, is finally combined by gained
Post processing solidification 2h in 130 DEG C of baking ovens put into by material.
Embodiment 7 (pultrusion)
Other steps are same as in Example 2, and simply thermosetting resin matrix is changed to metaphenylene unsaturated polyester resin.
Embodiment 8 (pultrusion)
Other steps are same as in Example 2, and simply thermosetting resin matrix is changed to bimaleimide resin.
Embodiment 9 (pultrusion)
Other steps are same as in Example 2, and simply thermosetting resin matrix is changed to polyurethane, and wherein polyester consists of: press
Mass fraction meter, isocyanates MDI 49.9 parts, PEPA premixed systems 49.9 parts, amines catalyst triethylene diamine 0.2
Part.
Embodiment 10 (pultrusion)
Other steps are same as in Example 2, simply change reinforcing fiber into carbon fiber.
Embodiment 11 (pultrusion)
Other steps are same as in Example 2, and reinforcing fiber simply changes into glass fibre/basalt fibre mixture.
Embodiment 12 (pultrusion)
Other steps are same as in Example 2, simply change reinforcing fiber into superhigh molecular weight polyethylene fibers.
Embodiment 13 (pultrusion)
Other steps are same as in Example 2, and reinforcing fiber simply changes into Kevlar fiber.
Embodiment 14 (RTM molding)
(1) raw-material preparation and preforming layout
I () reinforcing fiber materials is arranged
According to setting shape and scheduled volume by laid to glass fibre continuous felt and glass fiber yarn on lower mold mould, simultaneously
Cut off unnecessary leftover pieces (regulating laid amount makes the reinforcing material content of end article be 80%).
(ii) configuration of resin adhesive liquid
Carrying out the configuration of glue according to following component, be sequentially added into material, often adding a kind of material needs to stir 10-
15min, rotating speed is 2500r/min.Epoxy acrylic resin 100 parts, Graphene 0.5 part, methacrylic acid-acrylic acid butyl ester are embedding
Section copolymer (in polymer, the molar ratio of two kinds of monomeric units is 1.5:1, number-average molecular weight 50000) 2.5 parts, other are conventional
Additive 15.5 parts (includes initiator B PO 3 weight portion, Kaolin 5 weight portion, ground calcium carbonate 6 weight portion, antishrinking agent 1
Weight portion, releasing agent 0.5 weight portion).Ultrasonic disperse 15min again is needed after having stirred.
(2) matched moulds molding
The lower mold that laying is good and upper mold are closed up and by border seal and fastening.Mould is warming up to 50 DEG C, 50 DEG C subsequently
Lower the resin adhesive liquid prepared is injected in mold cavity, notes regulating injection pressure to guarantee that resin can be completely filled with die cavity side by side
Degasification body.The temperature of mould is promoted to 145 DEG C in 20min simultaneously, and is incubated 1h.
(3) demoulding
Separate upper and lower mould after being naturally cooling to 50 DEG C, subsequently goods are taken out.Article removal is good, and smooth surface does not has
Crackle, groove and bubble.
Embodiment 15 (RTM molding)
Other steps are identical with embodiment 14, and simply thermosetting resin matrix is changed to epoxy resin and (consists of parts by weights
Number meter: epoxy resin 50 parts, 50 parts of firming agent), pultrusion speed is 250mm/min, finally gained composite is put into 130
Post processing solidification 2h in DEG C baking oven.
Embodiment 16 (RTM molding)
Other steps are identical with embodiment 14, and simply thermosetting resin matrix is changed to metaphenylene unsaturated polyester resin.
Embodiment 17 (RTM molding)
Other steps are identical with embodiment 14, and simply thermosetting resin matrix is changed to bimaleimide resin.
Embodiment 18 (RTM molding)
Other steps are identical with embodiment 14, and simply thermosetting resin matrix is changed to polyurethane, and wherein polyurethane consists of:
In parts by weight, isocyanates MDI 49.9 parts, PEPA premixed systems 49.9 parts, amines catalyst triethylene diamine
0.2 part.
Embodiment 19 (RTM molding)
Other steps are identical with embodiment 14, simply change reinforcing fiber into carbon fiber.
Embodiment 20 (RTM molding)
Other steps are identical with embodiment 14, and reinforcing fiber simply changes into glass fibre/basalt fibre combination.
Embodiment 21 (RTM molding)
Other steps are identical with embodiment 14, simply change reinforcing fiber into superhigh molecular weight polyethylene fibers.
Embodiment 22 (RTM molding)
Other steps are identical with embodiment 14, and reinforcing fiber simply changes into Kevlar fiber.
Comparative example 1 (pultrusion)
Concrete technology step is essentially identical with the embodiment of the present invention 2, simply Graphene component is removed.
Comparative example 2 (pultrusion)
Concrete technology step is essentially identical with the embodiment of the present invention 5, simply Graphene component is removed.
Comparative example 3 (pultrusion)
Concrete technology step is essentially identical with the embodiment of the present invention 6, simply Graphene component is removed.
Comparative example 4 (pultrusion)
Concrete technology step is essentially identical with the embodiment of the present invention 7, simply Graphene component is removed.
Comparative example 5 (pultrusion)
Concrete technology step is essentially identical with the embodiment of the present invention 8, simply Graphene component is removed.
Comparative example 6 (pultrusion)
Concrete technology step is essentially identical with the embodiment of the present invention 9, simply Graphene component is removed.
Comparative example 7 (pultrusion)
Concrete technology step is essentially identical with the embodiment of the present invention 10, simply Graphene component is removed.
Comparative example 8 (pultrusion)
Concrete technology step is essentially identical with the embodiment of the present invention 11, simply Graphene component is removed.
Comparative example 9 (RTM molding)
Concrete technology step is essentially identical with the embodiment of the present invention 14, simply Graphene component is removed.
Comparative example 10 (pultrusion)
Concrete technology step is essentially identical with the embodiment of the present invention 2, simply acrylic polymer component is removed.
Comparative example 11 (pultrusion)
Concrete technology step is essentially identical with the embodiment of the present invention 4, is simply divided by acrylic polymer constituent mass
Number changes 2 parts into.
Comparative example 12 (pultrusion)
Concrete technology step is essentially identical with the embodiment of the present invention 5, is simply divided by acrylic polymer constituent mass
Number changes 4 parts into.
Comparative example 13 (RTM molding)
Concrete technology step is essentially identical with the embodiment of the present invention 14, simply acrylic polymer component is removed.
Table 1 uses embodiment and the comparative example (each group component is weight portion) of pultrusion processes
Note: resin is 100 weight portions, and component (b), (c), the amount of (d) are the amount relative to 100 parts by weight resin.
Table 2 uses embodiment and the comparative example (each group component is weight portion) of RTM molding
Note: resin is 100 weight portions, and component (b), (c), the amount of (d) are the amount relative to 100 parts by weight resin.
Experimental example 1
The performance of the composite embodiment of the present invention, comparative example prepared contrasts.Longitudinal tensile strength and
Modulus test is measured according to the method for regulation in GB/T 1447-2005, and buckling strength and modulus are tested according to GB/T
In 1449-2005, the method for regulation is measured, and the test of short beam shear strength is advised according in ASTM D2344/D2344M-13
Fixed method is tested, and the test of notch impact strength is measured according to the method for regulation in GB/T 1451-2005.Tool
Body testing result is as shown in table 3 below.
Table 3 the performance test results
From experimental result it can be seen that relative to conventional without introduce Graphene fiber-reinforced polymer-matrix composite wood
Material, the comprehensive mechanical property of resulting product is significantly improved.First, it is no matter that bending strength or hot strength are all because stone
The ink introducing of alkene and occur slightly improving, the most valuable is this expression toughness of material of notch impact strength of material
Index occurs being greatly improved also with the introducing of Graphene, and the toughness of display material has strengthened.So by the present invention's
Polymer matrix composite prepared by preparation method achieves rigidity-toughness balanced the most to a certain extent, thus is conducive to expanding this type of
The application of material.
Additionally what deserves to be explained is, Graphene activeness and quietness it is crucial that it disperses in polymeric matrix, therefore one
As use under the conditions of need introduce surface active agent composition, such as dodecylbenzene sodium sulfonate, Silane coupling agent KH550 etc..And
The propylene base polymer used in the present invention on the one hand conduct helps Graphene scattered surfactant in resin adhesive liquid,
This component also can play the effect of releasing agent in material preparation process simultaneously, shows as little releasing agent addition (relatively
In resin, it is 0.5 mass parts) good stripping result can be obtained.This dual function has been taken into account and ensure that the equal of Graphene
Process stabilizing prepared by even dispersion and goods, is the most also the important summary of the invention of the present invention and innovative point.By comparative example 10-
13 can not play potentiation, this is because the agglomeration traits of Graphene result in it can be seen that add merely Graphene
The disappearance of activeness and quietness effect, and Graphene is the most particularly significant with the relative scale of acrylic polymer, acrylate
Base polymer adds very few, can not reach good graphene dispersion effect, thus show as product properties the most significantly
Improve.This also illustrates Graphene and dispersant (acrylic polymer) is mutually matched mechanism.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, at not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy illustrates the most separately.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that without departing substantially from the present invention's
May be made that in the case of spirit and scope many other change and amendment.It is, therefore, intended that in the following claims
Including all such changes and modifications belonged in the scope of the invention.
Claims (10)
1. a resin combination, including: (a) thermosetting resin matrix, (b) Graphene, (c) acrylic polymer, with
And other additives of optional (d).
Resin combination the most according to claim 1, it is characterised in that by weight, (c) acrylic polymer
Amount Wc is preferably greater than or equal to 2.5 with ratio Wc/Wb of amount Wb of (b) Graphene, and more preferably equal to or greater than 3, the most excellent
Choosing, more than or equal to 4, is yet more preferably greater than or equal to 5, most preferably equal to or greater than 6.
Resin combination the most according to claim 1, it is characterised in that described resin combination includes: (a) thermosetting tree
Aliphatic radical body 100 weight portion, (b) Graphene 0.1-3 weight portion, (c) acrylic polymer 0.5-10 weight portion and optionally
(d) other additives 2-20 weight portion；
Preferably, described resin combination includes: (a) thermosetting resin matrix 100 weight portion, (b) Graphene 0.5-2 weight
Part, (c) acrylic polymer 0.8-5 weight portion and optional (d) other additives 3-15 weight portion；
Preferably, described resin combination includes: (a) thermosetting resin matrix 100 weight portion, (b) Graphene 0.8-1 weight
Part, (c) acrylic polymer 1-4 weight portion and optional (d) other additives 4-10 weight portion.
Resin combination the most according to claim 1, it is characterised in that (a) described thermosetting resin matrix is free radical
Curable thermosetting resin；
Preferably, (a) described thermosetting resin matrix is epoxy resin, epoxy acrylic resin, polyurethane, BMI
Resin, unsaturated polyester resin, phenolic resin one or more.
Resin combination the most according to claim 1, it is characterised in that the sheet number of plies of (b) described Graphene is 1-10 layer,
Such as 1-5 layer；Preferably, described Graphene is selected from single-layer graphene, bilayer graphene and the few layer of graphite with 3-10 layer
One or more in alkene.
Resin combination the most according to claim 1, it is characterised in that (c) described acrylic polymer is propylene
Esters of gallic acid homopolymer or acrylic acid esters co-polymer, preferred acrylate based block copolymer；
Preferably, (c) described acrylic polymer includes one or more of monomeric unit, for example, at least two kinds monomers
Unit: (i) acrylic acid；(ii) methacrylic acid；(iii) alkyl acrylate, such as acrylic acid C1-C15Arrcostab, acrylic acid C1-
C10Arrcostab；(iv) alkyl methacrylate, such as methacrylic acid C1-C15Arrcostab, methacrylic acid C1-C10Arrcostab；
V () benzyl acrylate, such as acrylic acid C6-C20Aryl ester；(vi) aryl methacrylate, such as methacrylic acid C6-C20Virtue
Base ester；(vii) acrylic acid heteroaryl ester, such as acrylic acid C3-C20Heteroaryl ester；And (viii) methacrylic acid heteroaryl ester,
Such as methacrylic acid C3-C20Heteroaryl ester；
Preferably, (c) described acrylate based block copolymer includes acrylic acid, acrylic acid methyl ester., ethyl acrylate, acrylic acid
Butyl ester, amyl acrylate, Hexyl 2-propenoate, methacrylic acid, methyl methacrylate, ethyl acrylate, butyl acrylate, third
One or more in the block copolymer of olefin(e) acid pentyl ester and Hexyl 2-propenoate；
Preferably, the number-average molecular weight of (c) described acrylic polymer is between 5000-50000.
7. a composite, especially section bar, including consolidating according to the resin combination described in any one of claim 1 to 6
Compound and reinforcing fiber materials.
Composite the most according to claim 7, it is characterised in that described reinforcing fiber materials includes continuous fiber, fibre
One or both in dimensional fabric；
Preferably, described continuous fiber includes glass fibre, basalt fibre, aramid fiber, polysulphonamide fiber, carbon fiber, gathers
One or more in poly P phenylene diamine terephthalamide fiber such as Kevlar fiber and superhigh molecular weight polyethylene fibers；
Preferably, one or more during described fabric includes continuous felt, surface felt and tape edge felt.
9. preparation is according to the method for the composite described in claim 7 or 8, it is characterised in that comprise the steps: to make described
Resin combination is immersed in described reinforcing fiber materials, curing molding.
10. according to the composite described in claim 7 or 8 as sports goods, furniture parts, office appliance parts, automobile
Parts, aircraft components or fuselage material, spacecraft component, blade of wind-driven generator, insulated wall connector, construction material and
The application of oil mining part of appliance.
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| CN107286694A (en) * | 2017-06-16 | 2017-10-24 | 东台晨霞新材料科技有限公司 | A kind of modified graphene/fibre reinforced composites and preparation method thereof |
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