CN106280287B - A kind of resin combination, composite material and preparation method and application - Google Patents
A kind of resin combination, composite material and preparation method and application Download PDFInfo
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- CN106280287B CN106280287B CN201610769669.6A CN201610769669A CN106280287B CN 106280287 B CN106280287 B CN 106280287B CN 201610769669 A CN201610769669 A CN 201610769669A CN 106280287 B CN106280287 B CN 106280287B
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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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- C—CHEMISTRY; METALLURGY
- 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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- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
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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
Abstract
The present invention relates to a kind of resin combination, composite material and preparation method and applications.The present invention provides a kind of resin combinations, comprising: (a) thermosetting resin matrix, (b) graphene, (c) acrylic polymer and optional (d) other additives.There is excellent mechanical property by composite material prepared by the resin combination.
Description
Technical field
The present invention relates to polymer matrix composite preparation fields, in particular to a kind of resin combination, composite wood
Material and its preparation method and application.
Background technique
Fiber reinforced polymer matrix composite has a wide range of applications in actual production and living, passes through various enhancings
The enhancement effect of fiber and fabric can reach very high mechanical strength, can be good in many occasions substitute reinforcing bar,
The metal materials such as aluminium alloy and the weight that final product is effectively reduced.But traditional fiber reinforced polymer matrix composite
Have toughness it is low, not resistant to shearing and easily occur brittle fracture the shortcomings that, very big limits the expansion in such materials'use field.
Therefore, toughening is carried out to fiber reinforced polymer matrix composite by effective means and the mechanics for keeping its high simultaneously is strong
Degree realizes that 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, ultimate strength is
130GPa, stretch modulus can reach 1TPa, be the highest sheet layer material of mechanical strength.But graphene is easy in resin
Reunite, this will affect the performance of composite material.Existing technology is both for molten in polarity small organic molecule by graphene dispersion
Situation in agent (such as ethyl alcohol, DMF) or water, without reference to the dispersion in fluoropolymer resin liquid.Technology also is by stone
Black alkene first disperses that dispersion liquid is mixed into resin again in organic solvent, then vacuumizes removing solvent.This is undoubtedly increased again
The very complicated degree of operation.
In view of this, the present invention is specifically proposed.
Summary of the invention
The purpose of the present invention is to provide a kind of composite materials with excellent mechanical performance.
One aspect of the present invention is related to a kind of resin combination, comprising: (a) thermosetting resin matrix, (b) graphene, (c) third
Olefin(e) acid esters polymer and optional (d) other additives.
According to some embodiments, by weight, (c) the amount Wb of the amount Wc of acrylic polymer and (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 be equal to 4, further preferably greatly
In or equal to 5, most preferably equal to or greater than 6.
According to some embodiments, the resin combination includes: 100 parts by weight of (a) thermosetting resin matrix, (b) stone
Black alkene 0.1-3 parts by weight, (c) acrylic polymer 0.5-10 parts by weight and optional (d) other additives 2-20 weight
Measure part.
Preferably, the resin combination includes: 100 parts by weight of (a) thermosetting resin matrix, (b) graphene 0.5-2 weight
Measure part, (c) acrylic polymer 0.8-5 parts by weight and optional (d) other additives 3-15 parts by weight.
Preferably, the resin combination includes: 100 parts by weight of (a) thermosetting resin matrix, (b) graphene 0.8-1 weight
Measure part, (c) acrylic polymer 1-4 parts by weight and optional (d) other additives 4-10 parts by weight.
Another aspect of the present invention is related to a kind of composite material, especially profile, the solidification including the resin combination
Object and reinforcing fiber materials.
Another aspect of the present invention is related to preparing the method for composite material, includes the following steps: to soak the resin combination
Enter to the reinforcing fiber materials, curing molding.
Another aspect of the present invention is related to composite material as sports goods, furniture parts, office appliance component, 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 component.
There is excellent mechanical property by composite material prepared by the resin combination, there is high-intensitive, anti-shearing, high-ductility
The performance of property.
Specific embodiment
Graphene is the reinforcing material of new generation with excellent mechanical property of discovered in recent years, and ultimate strength is
130GPa, stretch modulus can reach 1TPa, be the highest sheet layer material of mechanical strength.As long as graphene can polymerize
Good dispersion effect is formed in object matrix, just can significantly improve the mechanical property of material, or even also can be improved material
Heat resistance.Therefore in the present invention, graphene is introduced in traditional fiber reinforced polymer matrix composite, makes graphite
Alkene and reinforcing fiber, fabric form good synergistic effect, the double effects of enhancing and toughening are realized, to be obviously improved material
Comprehensive performance.
The purpose of the invention is to provide a kind of polymer matrix composite of graphene activeness and quietness and its preparation side
Method, in particular to thermosetting resin base fiber reinforced composite material, promote the comprehensive mechanical property of material.
I. resin combination
One aspect of the present invention is related to a kind of resin combination, comprising: (a) thermosetting resin matrix, (b) graphene, (c) third
Olefin(e) acid esters polymer and optional (d) other additives.
According to a kind of embodiment, resin combination of the invention includes:
(a) 100 parts by weight of thermosetting resin matrix；
(b) graphene 0.1-3 parts by weight, such as 0.5-2 parts by weight or 0.8-1 parts by weight；
(c) acrylic polymer 0.5-10 parts by weight, such as 0.8-5 parts by weight or 1-4 parts by weight, such as 2 parts by weight；
And
Optional (d) other additives 2-20 parts by weight or 3-15 parts by weight or 4-10 parts by weight.
According to a kind of embodiment, resin combination includes: 100 parts by weight of (a) thermosetting resin matrix, (b) graphene
0.1-3 parts by weight, (c) acrylic polymer 0.5-10 parts by weight and optional (d) other additives 2-20 weight
Part.
According to a kind of embodiment, resin combination includes: 100 parts by weight of (a) thermosetting resin matrix, (b) graphene
0.5-2 parts by weight, (c) acrylic polymer 0.8-5 parts by weight and optional (d) other additives 3-15 parts by weight.
According to a kind of embodiment, resin combination includes: 100 parts by weight of (a) thermosetting resin matrix, (b) graphene
0.8-1 parts by weight, (c) acrylic polymer 1-4 weight and optional (d) other additives 4-10 parts by weight.
In order to realize better dispersion effect, by weight, (c) the amount Wc of acrylic polymer and (b) graphene
The 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 be equal to 3.5,
It is greater than or is equal to 4, 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 for epoxy resin, epoxy acrylic resin, polyurethane, bimaleimide resin,
The one or more of unsaturated polyester resin and phenolic resin.Unsaturated polyester resin can be metaphenylene unsaturated polyester (UP)
One of resin, m-phthalate unsaturated polyester resin are a variety of.
(b) graphene
The piece number of plies of graphene can be 1-10 layers, such as 1-5 layers.Graphene can be selected from single-layer graphene, the double-deck stone
Black alkene and with one of 3-10 layers few layer of graphene or a variety of.Single-layer graphene: refer to by one layer with benzene ring structure (i.e.
Hexagonal honeycomb structure) a kind of periodical two-dimentional carbon material for constituting of closelypacked carbon atom.Bilayer graphene (Bilayer
Graphene): referring to by two layers with the periodically closelypacked carbon atom of benzene ring structure (i.e. hexagonal honeycomb structure) with different heaps
A kind of two-dimentional carbon material that pile mode (including AB stacking, AA stacking, AA ' stacking etc.) stacking is constituted.Few layer graphene (Few-
Layer): referring to by 3-10 layers with the periodically closelypacked carbon atom of benzene ring structure (i.e. hexagonal honeycomb structure) with different stackings
A kind of two-dimentional carbon material that mode (including ABC stacking, ABA stacking etc.) stacking is constituted.
Relative to 100 parts by weight thermosetting resin matrix, the amount of graphene can be 0.1-3 parts by weight, 0.5-2 weight
Part or 0.5-1 parts by weight.
(c) acrylic polymer
In addition, (c) being used cooperatively for acrylic polymer is also an innovative point of the invention.On the one hand the component
Release agent can effectively be played the role of and it is not acid strong, meanwhile, as amphipathy macromolecule, can also effectively mention
The degree that is uniformly dispersed high and that the various fillers (especially graphene) of guarantee are in resin combination, plays the role of dispersing agent,
To also generate active influence to the mechanical property of final product to a certain degree.In short, acrylic polymer is generation
For the excellent selection of organic acid in common release agent.
(c) acrylic polymer can be esters of acrylic acid homopolymer or acrylic acid esters co-polymer, preferably propylene
Acid esters based block copolymer.(c) acrylic acid esters co-polymer can be one or more of: random copolymer, block copolymerization
Object, 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) may include following
One or more monomeric units, for example, at least two kinds of 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 base ester, such as acrylic acid C3-C20Heteroaryl base ester, acrylic acid C4-C15Heteroaryl base ester,
Acrylic acid C5-C10Heteroaryl base ester or acrylic acid C6-C8Heteroaryl base ester；And (viii) methacrylic acid heteroaryl base ester, such as methyl
Acrylic acid C3-C20Heteroaryl base ester, methacrylic acid C4-C15Heteroaryl base ester, methacrylic acid C5-C10Heteroaryl base ester or methyl-prop
Olefin(e) acid C6-C8Heteroaryl base ester.Acrylate based block copolymer may include acrylic acid, methyl acrylate, 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 of ester, amyl acrylate and block copolymer of Hexyl 2-propenoate.Acrylate based block copolymer can
Think one or more of the block copolymer of methacrylic acid, methyl methacrylate, butyl acrylate.
Acrylic polymer number-average molecular weight can control between 5000-50000, as between 6000-40000,
Between 8000-30000, between 10000-20000.
Relative to 100 parts by weight thermosetting resin matrix, the amount of acrylic polymer can be 0.5-10 parts by weight,
Such as 0.8-5 parts by weight, 1-4 parts by weight, 0.5-2 parts by weight or 1-2 parts by weight, 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 parts by weight.
(d) other additives
Other additives can be the conventional additives in resin combination or fiber-resin composite.Other add
Adding agent includes one or more of release agent, initiator, curing agent, release agent, mill base, filler.
Relative to 100 parts by weight thermosetting resin matrix, the amount of other additives can be 0.1-30 parts by weight, such as 1-
25 parts by weight, 2-20 parts by weight or 3-15 parts by weight or 4-10 parts by weight.
II. composite material or profile
The present invention provides a kind of composite material or profiles, have high-intensitive, anti-shearing, high tenacity performance characteristics, from
And improve the comprehensive mechanical property of material.Composite material of the invention is thermosetting resin based composites.
According to a kind of embodiment, the present invention provides a kind of composite material or profiles, by resin combination of the invention
And reinforcing fiber is made.
According to a kind of embodiment, the present invention provides a kind of composite material, including resin combination of the invention and
Reinforcing fiber in resin combination.
According to a kind of embodiment, the present invention relates to a kind of composite material or profile, the solidfied material including resin combination
And reinforcing fiber materials.Reinforcing fiber materials are in the solidfied material of resin combination.
Total weight based on composite material or profile, the amount of reinforcing fiber materials is by weight in composite material or profile
50%-80%, such as 55%-75% or 60%-70%, such as 65%.Resin combination in composite material or profile (or solidification
Object) amount can be 20%-50% by weight, such as 25%-45% or 30%-40%, such as 35%.For example, by weight
Meter, reinforcing fiber materials can also for 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 for 20%, 22%, 25%,
28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48% or 50% etc..
According to some embodiments, reinforcing material is the one or two of continuous fiber and fabric.According to some realities
Mode is applied, the continuous fiber includes glass fibre, basalt fibre, aramid fiber, polysulphonamide fiber, carbon fiber, gathers to benzene
One or more of two formyl p-phenylenediamine fibers (such as Kevlar fiber) and ultra high molecular weight polyethylene fiber.According to one
A little embodiments, continuous fiber yarn are glass fibre, basalt fibre, Fanglun 1414 (such as Kevlar
Fiber) and ultra high molecular weight polyethylene fiber one or more.According to some embodiments, fabric is continuous felt, table
The one or more of face felt and tape edge felt.
III. the method for composite material or profile is prepared
Another aspect of the present invention is related to the method for preparing composite material or profile, comprising the following steps: makes tree of the 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 profile be pultrusion curing molding or
Resin transfer molding (RTM molding).
According to a kind of embodiment, the method for composite material or profile is prepared the following steps are included: by resin of the invention
Composition dipping, pultrusion curing molding.In pultrusion curing molding, the temperature being heating and curing is preferably controlled between 100-160 DEG C.
It after pultrusion curing molding, is dried, dry temperature is preferably controlled between 90-100 DEG C.
According to a kind of embodiment, the method for composite material or profile is prepared the following steps are included: by resin of the invention
Composition injects in preforming reinforcing fiber materials, using resin transfer molding.
The advantage of the invention is that by mature composite material forming method, in optimization thermosetting resin formula
On the basis of (especially the addition of graphene and acrylate based block copolymer be used cooperatively), with most simple and effective way
The fiber reinforced polymer matrix composite of activeness and quietness is prepared, to improve the comprehensive mechanical property of material.
The invention further relates to composite materials or profile as sports goods, furniture parts, office appliance component, 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 component.The purposes of fiber-reinforced resin profile can enumerate fishing rod, golf club, bicycle
The sports goods such as vehicle frame；Automobile, the rack (frame) of aircraft or fuselage material, spacecraft component, blade of wind-driven generator
Deng.In particular, since automobile component, aircraft components, spacecraft component require the mechanical strength of height, fiber of the invention
Reinforced resin formed products are suitable for these purposes.Fiber-reinforced resin composition of the invention is particularly suitable for wind-driven generator leaf
The resin material of piece.
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products obtained can be bought by city.
Embodiment
Primary raw material
Graphene: Shandong holy well new material Co., Ltd 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 sky dragon basalt continuous fiber high and new technology
Co., Ltd.
Ultra high molecular weight polyethylene fiber: 4800Tex, Shanghai Sirui PolymerTechnology Co., Ltd..
Kevlar fiber: KEVLAR 49,2400Tex, DuPont Corporation.
Epoxy acrylic resin: MFE36, East China University Of Science And Technology Huachang Polymer Co., Ltd provide.
Metaphenylene unsaturated polyester resin: MERICAN9406, East China University Of Science And Technology Huachang Polymer Co., Ltd provide.
Bimaleimide resin: BMI-01, Honghu Shuangma New Materials Technology Co., Ltd..
Epoxy resin and curing agent pyromellitic acid anhydride: scientific and technological (Shanghai) limited liability company of favour cypress new material provides,
The epoxy resin trade mark is TF3120.
Thermosetting phenolic resin and corresponding curing agent: PF7003, Shandong holy well new material Co., Ltd provide.
Isocyanates MDI:PM-400, Yantai Wanhua Polyurethane Company Limited provide.
Polyester polyol combination material: QX30, Nanjing Nanjing Si Taipan Chemical Co., Ltd. provide.
Resin initiator: the peroxidating 2 ethyl hexanoic acid tert-butyl ester (TBPO), benzoyl peroxide (BPO), benzoyl peroxide first
Tert-butyl acrylate (TBPB) is that analysis is pure.
Antishrinking agent: DX-700, Foshan Dao Kesi micro mist Co., Ltd.
Triethylene diamine: analysis is pure, and Nanjing Guo Chen Chemical Co., Ltd. provides.
Acrylate based block copolymer: being that Qingdao University of Science and Technology provides.
Inner pattern releasing agent applicable: Pul24, AXEl company of the U.S. provide.
Embodiment 1 (pultrusion)
(1) preparation of raw material and preforming layout
(i) configuration of resin adhesive liquid
The configuration that glue is carried out according to following component, is sequentially added into material, every a kind of material is added to need to stir 10-
15min, revolving speed 2500r/min.100 parts of epoxy acrylic resin, 0.1 part of graphene, methacrylic acid-acrylic acid butyl ester are embedding
0.5 part of section copolymer (molar ratio of two kinds of monomeric units is 1.5:1, number-average molecular weight 50000 in polymer), other routines
15.5 parts of additive (including initiator TBPO/TBPB 3 parts by weight of compounding, 5 parts by weight of talcum powder, 5 parts by weight of powdered whiting,
0.5 part of 1 parts by weight of antishrinking agent, inner pattern releasing agent applicable).Re-ultrasonic dispersion 15min is needed after the completion of stirring.
(ii) preforming layout
Glass fiber yarn (4800Tex) is passed sequentially through into creel, glue dipping tank, preforming tool is imported into and final
Across hot forming tool.By upper layer and lower layer surface of polyester felt by leading felt device, preforming tool, imported into and eventually pass through heat at
Pattern tool.The number of silvalin is adjusted to make the content of glass fiber of final product 80%.
(2) pultrusion produces
Three sections of temperature of hot forming tool are set as one section 105 DEG C, two sections 155 DEG C, three sections 150 DEG C.After temperature is stablized
It is produced.Pultrusion speed is set as 500mm/min.
The glue prepared is imported in glue dipping tank, equipment is started and is produced, i.e., the glass fibre impregnated glue
Yarn and surface of polyester felt are drawn in hot forming tool, are become profile after being heating and curing, are cut into fixed length by cutter device.
Surface is smooth always in process of production for sample, without crackle, scaling-off and unfilled corner, illustrates that release agent works well.Finally by institute
It obtains composite material and is put into post-processing solidification 12h in 100 DEG C of baking ovens.
Embodiment 2 (pultrusion)
Other steps are same as Example 1, and only graphene is 0.5 part, methacrylic acid-acrylic acid butyl ester block copolymerization
Object is 2.5 parts.
Embodiment 3 (pultrusion)
Other steps are same as Example 1, and only graphene is 1 part, methacrylic acid-acrylic acid butyl ester block copolymer
Object is 5 parts.
Embodiment 4 (pultrusion)
Other steps are same as Example 1, and only graphene is 2 parts, and acrylic polymer is methyl methacrylate
Ester-butyl acrylate-butyl methacrylate block copolymer (molar ratio of three kinds of monomeric units is 1:1:1 in polymer,
Number-average molecular weight 35000), parts by weight are 7.5 parts.
Embodiment 5 (pultrusion)
Other steps are same as Example 1, and only graphene is 3 parts, and acrylic polymer is methyl methacrylate
Ester-methacrylic acid-butyl methacrylate block copolymer (the molar ratio of three kinds of monomeric units in polymer are as follows: methyl
Methyl acrylate: methacrylic acid: butyl methacrylate=2:1:1.5, number-average molecular weight 20000), parts by weight 10
Part.
Embodiment 6 (pultrusion)
Other steps are same as Example 2, and only thermosetting resin matrix is changed to epoxy resin and (organizes as parts by weights number
Meter: 50 parts of epoxy resin, 50 parts of curing agent pyromellitic acid anhydride), pultrusion speed 250mm/min is finally compound by gained
Material is put into post-processing solidification 2h in 130 DEG C of baking ovens.
Embodiment 7 (pultrusion)
Other steps are same as Example 2, and only thermosetting resin matrix is changed to metaphenylene unsaturated polyester resin.
Embodiment 8 (pultrusion)
Other steps are same as Example 2, and only thermosetting resin matrix is changed to bimaleimide resin.
Embodiment 9 (pultrusion)
Other steps are same as Example 2, and only thermosetting resin matrix is changed to polyurethane, and wherein polyester forms are as follows: presses
Mass fraction meter, 49.9 parts of isocyanates MDI, 49.9 parts of material of polyester polyol combination, amines catalyst triethylene diamine 0.2
Part.
Embodiment 10 (pultrusion)
Other steps are same as Example 2, and reinforcing fiber is only changed to carbon fiber.
Embodiment 11 (pultrusion)
Other steps are same as Example 2, and reinforcing fiber is only changed to glass fibre/basalt fibre mixture.
Embodiment 12 (pultrusion)
Other steps are same as Example 2, and reinforcing fiber is only changed to ultra high molecular weight polyethylene fiber.
Embodiment 13 (pultrusion)
Other steps are same as Example 2, and reinforcing fiber is only changed to Kevlar fiber.
Embodiment 14 (RTM molding)
(1) preparation of raw material and preforming layout
(i) reinforcing fiber materials are arranged
Glass fibre continuous felt and glass fiber yarn are laid on lower die mold according to setting shape and predetermined amount, simultaneously
Cut off extra leftover pieces (adjusting laying amount makes the reinforcing material content 80% of final product).
(ii) configuration of resin adhesive liquid
The configuration that glue is carried out according to following component, is sequentially added into material, every a kind of material is added to need to stir 10-
15min, revolving speed 2500r/min.100 parts of epoxy acrylic resin, 0.5 part of graphene, methacrylic acid-acrylic acid butyl ester are embedding
2.5 parts of section copolymer (molar ratio of two kinds of monomeric units is 1.5:1, number-average molecular weight 50000 in polymer), other routines
15.5 parts of additive (including 3 parts by weight of initiator B PO, 5 parts by weight of kaolin, 6 parts by weight of powdered whiting, antishrinking agent 1
Parts by weight, 0.5 parts by weight of release agent).Re-ultrasonic dispersion 15min is needed after the completion of stirring.
(2) molding molding
The good lower die of laying and upper mold are closed up and by border seal and fastening.Mold is warming up to 50 DEG C, subsequent 50 DEG C
The lower resin adhesive liquid that will be prepared is injected into mold cavity, pays attention to adjusting injection pressure to ensure that resin can be completely filled with die cavity side by side
Except gas.Simultaneously the temperature of mold is promoted to 145 DEG C in 20min, and keeps the temperature 1h.
(3) it demoulds
Upper and lower mould is separated after being naturally cooling to 50 DEG C, then takes out product.Article removal is good, and surface is smooth, does not have
Crackle, groove and bubble.
Embodiment 15 (RTM molding)
Other steps are identical as embodiment 14, and only thermosetting resin matrix is changed to epoxy resin and (organizes as parts by weights
Number meter: 50 parts of epoxy resin, 50 parts of curing agent), gained composite material is finally put into 130 by pultrusion speed 250mm/min
Post-processing solidification 2h in DEG C baking oven.
Embodiment 16 (RTM molding)
Other steps are identical as embodiment 14, and only thermosetting resin matrix is changed to metaphenylene unsaturated polyester resin.
Embodiment 17 (RTM molding)
Other steps are identical as embodiment 14, and only thermosetting resin matrix is changed to bimaleimide resin.
Embodiment 18 (RTM molding)
Other steps are identical as embodiment 14, and only thermosetting resin matrix is changed to polyurethane, and wherein polyurethane forms are as follows:
As mass fraction, 49.9 parts of isocyanates MDI, 49.9 parts of material of polyester polyol combination, amines catalyst triethylene diamine
0.2 part.
Embodiment 19 (RTM molding)
Other steps are identical as embodiment 14, and reinforcing fiber is only changed to carbon fiber.
Embodiment 20 (RTM molding)
Other steps are identical as embodiment 14, and reinforcing fiber is only changed to glass fibre/basalt fibre and is combined.
Embodiment 21 (RTM molding)
Other steps are identical as embodiment 14, and reinforcing fiber is only changed to ultra high molecular weight polyethylene fiber.
Embodiment 22 (RTM molding)
Other steps are identical as embodiment 14, and reinforcing fiber is only changed to Kevlar fiber.
Comparative example 1 (pultrusion)
Specific process step and the embodiment of the present invention 2 are essentially identical, only remove graphite olefinic constituent.
Comparative example 2 (pultrusion)
Specific process step and the embodiment of the present invention 5 are essentially identical, only remove graphite olefinic constituent.
Comparative example 3 (pultrusion)
Specific process step and the embodiment of the present invention 6 are essentially identical, only remove graphite olefinic constituent.
Comparative example 4 (pultrusion)
Specific process step and the embodiment of the present invention 7 are essentially identical, only remove graphite olefinic constituent.
Comparative example 5 (pultrusion)
Specific process step and the embodiment of the present invention 8 are essentially identical, only remove graphite olefinic constituent.
Comparative example 6 (pultrusion)
Specific process step and the embodiment of the present invention 9 are essentially identical, only remove graphite olefinic constituent.
Comparative example 7 (pultrusion)
Specific process step and the embodiment of the present invention 10 are essentially identical, only remove graphite olefinic constituent.
Comparative example 8 (pultrusion)
Specific process step and the embodiment of the present invention 11 are essentially identical, only remove graphite olefinic constituent.
Comparative example 9 (RTM molding)
Specific process step and the embodiment of the present invention 14 are essentially identical, only remove graphite olefinic constituent.
Comparative example 10 (pultrusion)
Specific process step and the embodiment of the present invention 2 are essentially identical, only remove acrylic polymer component.
Comparative example 11 (pultrusion)
Specific process step and the embodiment of the present invention 4 are essentially identical, only by acrylic polymer constituent mass point
Number is changed to 2 parts.
Comparative example 12 (pultrusion)
Specific process step and the embodiment of the present invention 5 are essentially identical, only by acrylic polymer constituent mass point
Number is changed to 4 parts.
Comparative example 13 (RTM molding)
Specific process step and the embodiment of the present invention 14 are essentially identical, only remove acrylic polymer component.
Table 1 uses the embodiment and comparative example (each group component amount of attaching most importance to part) of pultrusion processes
Note: resin is 100 parts by weight, component (b), (c), (d) amount be amount relative to 100 parts by weight resin.
Table 2 uses the molding embodiment and comparative example of RTM (each group component amount of attaching most importance to part)
Note: resin is 100 parts by weight, component (b), (c), (d) amount be amount relative to 100 parts by weight resin.
Experimental example 1
The performance for the composite material that the embodiment of the present invention, comparative example are prepared is compared.Longitudinal tensile strength and
Modulus test is measured according to method specified in GB/T 1447-2005, and buckling strength and modulus test are according to GB/T
Method specified in 1449-2005 is measured, and the test of short beam shear strength in ASTM D2344/D2344M-13 according to advising
Fixed method is tested, and the test of notch impact strength is measured according to method specified in GB/T 1451-2005.Tool
Body testing result is as shown in table 3 below.
3 the performance test results of table
From experimental result as can be seen that relative to conventional without the fiber-reinforced polymer-matrix composite wood for introducing graphene
Material, the comprehensive mechanical property of resulting product are significantly improved.Firstly, either bending strength or tensile strength are all because of stone
The introducing of black alkene and occur slightly improving, while more valuable is this expression toughness of material of the notch impact strength of material
Index also with graphene introducing and greatly improve, the toughness of display material is enhanced.So through the invention
The polymer matrix composite of preparation method preparation just realizes rigidity-toughness balanced to a certain extent, to be conducive to expand such
The application field of material.
In addition it is worth noting that, the key of graphene activeness and quietness is that it disperses in a polymer matrix, therefore one
As use condition under need to introduce surface active agent composition, such as neopelex, Silane coupling agent KH550 etc..And
On the one hand surfactant that the propylene esters polymer used in the present invention disperses in resin adhesive liquid as help graphene,
The component can also play the role of release agent in material preparation process simultaneously, and it is (opposite to show as seldom release agent additive amount
It is 0.5 mass parts in resin) good stripping result can be obtained.This double action, which has taken into account, ensure that the equal of graphene
The process stabilizing of even dispersion and product preparation, therefore be also the present invention important summary of the invention and innovative point.Pass through comparative example 10-
13 as can be seen that the simple graphene that is added cannot play humidification, this is because the agglomeration traits of graphene result in
The disappearance of activeness and quietness effect, and the relative scale of graphene and acrylic polymer is also particularly significant, acrylate
Quasi polymer addition is very few, can not reach good graphene dispersion effect, so that it is not apparent to show as product properties
It improves.Mechanism is mutually matched this also illustrates graphene and dispersing agent (acrylic polymer).
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (32)
1. a kind of composite material, comprising: the solidfied material and reinforcing fiber materials of resin combination；
The resin combination includes: 100 parts by weight of (a) thermosetting resin matrix, (b) graphene 0.1-3 parts by weight, (c) third
Olefin(e) acid esters polymer 0.5-10 parts by weight and optional (d) other additives 2-20 parts by weight；
Wherein, by weight, (c) the ratio Wc/Wb of the amount Wb of the amount Wc and (b) graphene of acrylic polymer be greater than or
Equal to 2.5.
2. composite material according to claim 1, which is characterized in that by weight, (c) amount of acrylic polymer
The ratio Wc/Wb of the amount Wb of Wc and (b) graphene is greater than or equal to 3.
3. composite material according to claim 2, which is characterized in that by weight, (c) amount of acrylic polymer
The ratio Wc/Wb of the amount Wb of Wc and (b) graphene is greater than or equal to 4.
4. composite material according to claim 3, which is characterized in that by weight, (c) amount of acrylic polymer
The ratio Wc/Wb of the amount Wb of Wc and (b) graphene is greater than or equal to 5.
5. composite material according to claim 4, which is characterized in that by weight, (c) amount of acrylic polymer
The ratio Wc/Wb of the amount Wb of Wc and (b) graphene is greater than or equal to 6.
6. composite material according to claim 1, which is characterized in that the resin combination includes: (a) thermosetting resin
100 parts by weight of matrix, (b) graphene 0.5-2 parts by weight, (c) acrylic polymer 0.8-5 parts by weight and optional
(d) other additives 3-15 parts by weight.
7. composite material according to claim 6, which is characterized in that the resin combination includes: (a) thermosetting resin
100 parts by weight of matrix, (b) graphene 0.8-1 parts by weight, (c) acrylic polymer 1-4 parts by weight and (d) optionally
Other additives 4-10 parts by weight.
8. composite material according to claim 1, which is characterized in that (a) described thermosetting resin matrix be epoxy resin,
The one or more of epoxy acrylic resin, polyurethane, bimaleimide resin, unsaturated polyester resin, phenolic resin.
9. composite material according to claim 1, which is characterized in that the piece number of plies of (b) described graphene is 1-10 layers.
10. composite material according to claim 9, which is characterized in that the piece number of plies of (b) described graphene is 1-5 layers.
11. composite material according to claim 9, which is characterized in that the graphene is selected from single-layer graphene, the double-deck stone
Black alkene and there is one of 3-10 layers of graphene or a variety of.
12. composite material according to claim 1, which is characterized in that (c) described acrylic polymer is acrylic acid
Ester homopolymer or acrylic acid esters co-polymer.
13. composite material according to claim 12, which is characterized in that (c) described acrylic polymer is propylene
Acid esters based block copolymer.
14. composite material according to claim 12, which is characterized in that (c) described acrylic polymer include with
A kind of lower or various of monomer unit: (i) acrylic acid；(ii) methacrylic acid；(iii) alkyl acrylate；(iv) metering system
Acid alkyl ester；(v) benzyl acrylate；(vi) aryl methacrylate；(vii) acrylic acid heteroaryl base ester；And (viii)
Methacrylic acid heteroaryl base ester.
15. composite material according to claim 12, which is characterized in that the acrylic polymer include with down toward
Few two kinds of monomeric units: (i) acrylic acid；(ii) methacrylic acid；(iii) alkyl acrylate；(iv) methacrylate
Ester；(v) benzyl acrylate；(vi) aryl methacrylate；(vii) acrylic acid heteroaryl base ester；And (viii) methyl-prop
Olefin(e) acid heteroaryl base ester.
16. composite material according to claim 14 or 15, which is characterized in that the alkyl acrylate includes acrylic acid
C1-C15Arrcostab.
17. composite material according to claim 14 or 15, which is characterized in that the alkyl acrylate includes acrylic acid
C1-C10Arrcostab.
18. composite material according to claim 14 or 15, which is characterized in that the alkyl methacrylate includes first
Base acrylic acid C1-C15Arrcostab.
19. composite material according to claim 14 or 15, which is characterized in that the alkyl methacrylate includes first
Base acrylic acid C1-C10Arrcostab.
20. composite material according to claim 14 or 15, which is characterized in that the benzyl acrylate includes acrylic acid
C6-C20Aryl ester.
21. composite material according to claim 14 or 15, which is characterized in that the aryl methacrylate includes first
Base acrylic acid C6-C20Aryl ester.
22. composite material according to claim 14 or 15, which is characterized in that the acrylic acid heteroaryl base ester includes propylene
Sour C3-C20Heteroaryl base ester.
23. composite material according to claim 14 or 15, which is characterized in that the methacrylic acid heteroaryl base ester includes
Methacrylic acid C3-C20Heteroaryl base ester.
24. composite material according to claim 14 or 15, which is characterized in that (c) described esters of acrylic acid block copolymerization
Object includes acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, amyl acrylate, Hexyl 2-propenoate, metering system
One or more of acid, block copolymer of methyl methacrylate.
25. composite material according to claim 14 or 15, which is characterized in that (c) described acrylic polymer
Number-average molecular weight is between 5000-50000.
26. composite material according to claim 1, which is characterized in that the composite material is profile.
27. according to claim 1 or composite material described in 26, which is characterized in that the reinforcing fiber materials include continuous fine
One or both of dimension, fabric.
28. composite material according to claim 27, which is characterized in that the continuous fiber includes glass fibre, the Black Warrior
Rock fiber, aramid fiber, polysulphonamide fiber, carbon fiber, Fanglun 1414 and superhigh molecular weight polyethylene
One or more of alkene fiber.
29. composite material according to claim 28, which is characterized in that the continuous fiber includes Kevlar fiber.
30. composite material according to claim 27, which is characterized in that the fabric include continuous felt, surface felt,
And one or more of tape edge felt.
31. the method for preparing -30 described in any item composite materials according to claim 1, which is characterized in that including walking as follows
It is rapid: the resin combination being made to be immersed in the reinforcing fiber materials, curing molding.
32. -30 described in any item composite materials are as sports goods, furniture parts, office appliance portion according to claim 1
Part, automobile component, aircraft components or fuselage material, spacecraft component, blade of wind-driven generator, insulated wall connector, building
The application of material and oil mining part of appliance.
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| CN107286695A (en) * | 2017-06-16 | 2017-10-24 | 东台晨霞新材料科技有限公司 | A kind of multi-layer graphene modified resin/fibrous composite and preparation method thereof |
| CN107418032A (en) * | 2017-06-16 | 2017-12-01 | 东台晨霞新材料科技有限公司 | A kind of graphene-containing/fibre reinforced composites and preparation method thereof |
| 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 |
| CN107286696A (en) * | 2017-06-16 | 2017-10-24 | 东台晨霞新材料科技有限公司 | A kind of single-layer graphene modified resin/fibrous composite and preparation method thereof |
| CN112852143B (en) * | 2017-09-20 | 2022-03-25 | 上海高铁电气科技有限公司 | Graphene polyurethane composite material and preparation method thereof |
| CN108047656A (en) * | 2018-01-11 | 2018-05-18 | 浙江鸿安建设有限公司 | A kind of high-strength building outer wall thermal insulation material and preparation method thereof |
| CN109694554B (en) * | 2018-12-29 | 2021-04-30 | 惠柏新材料科技（上海）股份有限公司 | Resin composition for rapidly pultrusion fiber reinforced composite material |
| CN113115589A (en) * | 2019-11-13 | 2021-07-13 | 远景能源有限公司 | Method and equipment for manufacturing graphene modified fiber reinforced material |
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| CN103242007A (en) * | 2013-05-22 | 2013-08-14 | 陕西科技大学 | Preparation method of graphene oxide modified polymer cement waterproof coating |
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