CN106280286A

CN106280286A - A kind of composite and application thereof and insulated wall connector

Info

Publication number: CN106280286A
Application number: CN201610767885.7A
Authority: CN
Inventors: 李枝芳; 董诚
Original assignee: Shandong Shengquan New Material Co Ltd
Current assignee: Shandong Shengquan New Material Co Ltd
Priority date: 2016-08-30
Filing date: 2016-08-30
Publication date: 2017-01-04

Abstract

The present invention relates to a kind of composite and application thereof and insulated wall connector.The present invention provides a kind of composite, including resin cured matter and reinforcing fiber materials, it meets at least one in following mechanical property (i) to (v): (i) longitudinal tensile strength >=740MPa, (ii) longitudinal tensile >=40GPa, (iii) buckling strength >=900MPa, (iv) buckling modulus >=39GPa, (v) short beam shear strength >=57MPa；Wherein this composite is at 23 ± 2 DEG C, pH value be 12 NaOH aqueous solution in soak after 3000h, at least one retention >=80% in mechanical property (i), (ii), (iii), (iv), (v).

Description

A kind of composite and application thereof and insulated wall connector

Technical field

The present invention relates to polymer matrix composite preparation field, in particular to a kind of composite and application thereof With insulated wall connector.

Background technology

Along with continuous innovation and the development of construction market, the energy-conservation walling of novel building becomes country's main development popularization to be made Materials for wall.Heat-insulating heat-preserving material is arranged on body of wall hollow part, aloft puts into various adiabator, be then heat insulation Material sandwich heat insulation system.Compared with homogenous material exterior wall, the combination of this wall structure rationally, has higher coefficient of thermal insulation, energy Preferably play the effect of insulation material.Meanwhile, on the premise of meeting load-bearing requirements, brick wall can be the most thinning.Due to compound Body of wall outstanding advantage in terms of building energy conservation, its application in China's building trade is more and more extensive.

Sandwich type body of wall be typically necessary the fixing connector of utilization inside and outside body of wall and moderate soak layer are effectively connected and Being fixed up, traditional connector material is usually with reinforcing bar (bar-mat reinforcement).But the heat conductivity of reinforcing bar is very big, perfoliate Reinforcing bar is equivalent to the heat bridge one by one set up in combined wall, greatly reduces the heat insulation effect of heat-insulation layer.Therefore pass through Certain moulding process preparation composite using successional reinforcing material/thermosetting resin as framework is as thermal-insulation connecting piece Rod core just becomes more satisfactory selection.This type of composite is generally the fiber composite that fluoropolymer resin is the least with heat conductivity Forming, on the basis of ensureing that it has the high intensity similar with reinforcing bar and modulus, the thermal resistance value making again this type of material is bigger.

It is pointed out that the Two-plate sandwich due to combined wall, thermal-insulation connecting piece therein generally require and bear relatively Big shearing force, then the anti-shear performance of its rod core requires must be excellent, because connector anti-shear performance is the most excellent, body of wall Safety coefficient the most also can be the highest.Therefore the general requirement for composite material base thermal-insulation connecting piece is exactly high intensity, resists Shearing, mechanical property to be got well.

In prior art, domestic and international patent is all concentrated mainly on the design of the contour structures of thermal-insulation connecting piece and concrete making With in method, such as CN202248370U, CN204983189U, CN204715667U, CN203924408U, CN202359664U、CN201924463U、CN202644775U、CN202831363U、CN203878809U、US4829733、 In US5519973, US5671574, US6116836, US7266931 patent, but for the performance of crucial connector rod core Optimizing the rarest relating to, the especially optimization of mechanical property less relates to.It addition, also have some Patent exploitations with thermoplasticity Resin is the connector (US5673525, US5987834, US6263638) of matrix resin, but based on thermoplastic resin itself The inferior position of performance, preparation-obtained connector is extremely difficult to the physical property close with reinforcing bar.

In view of this, the special proposition present invention.

Summary of the invention

Present invention aim at providing a kind of composite, there is excellent corrosion resistance, particularly alkali resistance.

The present invention relates to a kind of composite, including resin cured matter and reinforcing fiber materials, it is characterised in that described multiple Condensation material meets at least one in following mechanical property (i), (ii), (iii), (iv) and (v):

(i) longitudinal tensile strength >=740MPa,

(ii) longitudinal tensile >=40GPa,

(iii) buckling strength >=900MPa,

(iv) buckling modulus >=39GPa, and

(v) short beam shear strength >=57MPa；

Described composite at 23 ± 2 DEG C, pH value be 12 NaOH aqueous solution in soak after 3000h, described mechanical property At least one retention >=80% in energy (i), (ii), (iii), (iv) and (v).

Another aspect of the present invention relates to composite on insulated wall connector, on construction material and oil mining equipment Application.

Another aspect of the present invention relates to a kind of insulated wall connector, such as insulated wall connector bar, answering by the present invention Condensation material is made.

The composite of the present invention has excellent corrosion resistance, particularly alkali resistance.

Detailed description of the invention

In prior art, in building trade, the connector of insulated wall is typically or the comparison of employing reinforcing bar material is many, but It is that reinforcing bar itself can form heat bridge one by one in combined wall, heat insulation effect, therefore people in the art can be reduced greatly Specifically research is conceived to use which kind of composite to replace reinforcing bar to be used as the material of connector, to solve asking of insulation by member Topic.Although thermosetting resin based composites excellent thermal insulation performance, but each physical property such as intensity of itself cannot be with The performance of reinforcing bar matches in excellence or beauty, can not really meet the requirement of actual application, this composite of this drawbacks limit further Application.

The first object of the present invention is to provide a kind of composite, by by thermosetting resin, releasing agent, other help Agent, reinforcing material are combined under certain Optimum proportioning, and the composite property prepared is more stable, the most double Turn round and look at high intensity, the requirement of the mechanical property such as anti-shearing, substantially prolongs the service life of composite itself, compensate for steel The defect of muscle heat preservation and insulation difference own, while being greatly improved heat-insulating property, its physical property the most completely can be with steel The physical property of muscle matches in excellence or beauty, and brings considerable economic benefit.

The second object of the present invention is to provide the preparation method of above-mentioned composite, above-mentioned preparation method to belong to compare Preferably preparation method, method itself has the advantage of the active ingredient that can completely retain raw material, and step linking front and back is closely, Method is the most easily operated, and operating condition is gentle.

The third object of the present invention is to provide above-mentioned composite at construction material and to have answering in well winning apparatus With, and provide the application as a kind of insulated wall connector bar of the above-mentioned composite.

The fourth object of the present invention is to provide composite to connect as the insulated wall of above-mentioned insulated wall connector bar Part.The thermal-insulation connecting piece of this composite has the high intensity similar with reinforcing bar and a modulus, each side excellent physical properties, completely Meet actually used situation, it is seen that the composite of the present invention is applied widely.

I. composite

The present invention is to solve the technical problem of above-mentioned existence in prior art, it is provided that a kind of thermosetting resin base is combined Material, this composite both ensure that heat-insulating property and have also been obtained guarantee in physical property, can be with the thing of reinforcing bar Rationality can compare favourably.

One aspect of the present invention relates to a kind of composite, including resin cured matter and reinforcing fiber materials, this composite Meet at least one in following mechanical property (i), (ii), (iii), (iv) and (v), preferably at least two, more preferably at least Three, further preferably at least four, whole five:

(i) longitudinal tensile strength >=740MPa, preferably >=750MPa, more preferably >=760MPa, further preferably >= 770MPa, most preferably >=780MPa,

(ii) longitudinal tensile >=40GPa, preferably >=41GPa, more preferably >=42GPa, further preferably >=43GPa, Most preferably >=44GPa,

(iii) buckling strength >=900MPa, preferably >=910MPa, more preferably >=920MPa, further preferably >= 930MPa, most preferably >=940MPa,

(iv) buckling modulus >=39GPa, preferably >=39.5GPa, more preferably >=40GPa, further preferably >= 41GPa, most preferably >=42GPa, and

(v) short beam shear strength >=57MPa, preferably >=57.5MPa, more preferably >=58MPa, further preferably >= 58.5MPa, most preferably >=59MPa；

Wherein, described composite at 23 ± 2 DEG C, pH value be 12 NaOH aqueous solution in soak after 1000h, described power Learn at least one in performance (i), (ii), (iii), (iv) and (v), preferably at least two, more preferably at least three, enter One step preferably at least four, whole five retention >=85%, or >=87%, or >=90%, or >=91%, or >= 92%, or >=93%；

Or

Described composite at 23 ± 2 DEG C, pH value be 12 NaOH aqueous solution in soak after 3000h, described mechanical property At least one in energy (i), (ii), (iii), (iv) and (v), preferably at least two, more preferably at least three, further Preferably at least four, whole five retention >=80%, or >=82%, or >=85%, or >=87%, or >=90%, Or >=91%, or >=92%, or >=93%.

In one embodiment, the present invention provides a kind of fiber reinforced polymer matrix composite, and its hot strength >= 750MPa, stretch modulus >=40GPa, bending strength >=900, bending modulus >=39GPa, interlaminar shear strength >=57MPa；And 23 At ± 2 DEG C, pH value be 12 NaOH aqueous solution in soak after 3000h, above-mentioned performance retention is all >=93%.

In one embodiment, (i) longitudinal tensile strength >=740MPa, the preferably >=750MPa of composite, more excellent Choosing >=760MPa, further preferably >=770MPa, most preferably >=780MPa.

In one embodiment, (ii) longitudinal tensile >=40GPa, the preferably >=41GPa of composite, more preferably >=42GPa, further preferably >=43GPa, most preferably >=44GPa.

In one embodiment, (iii) buckling strength >=900MPa, the preferably >=910MPa of composite, more Preferably >=920MPa, further preferably >=930MPa, most preferably >=940MPa.

In one embodiment, (iv) buckling modulus of composite >=39GPa, preferably >=39.5GPa, more excellent Choosing >=40GPa, further preferably >=41GPa, most preferably >=42GPa.

In one embodiment, the short beam shear strength >=57MPa of composite, preferably >=57.5MPa, more preferably >= 58MPa, further preferably >=58.5MPa, most preferably >=59MPa.

Longitudinal tensile strength and modulus are measured according to the method for regulation in GB/T 1447-2005, buckling strength Being measured according to the method for regulation in GB/T 1449-2005 with modulus, short beam shear strength is according to ASTM D2344/ In D2344M-13, the method for regulation is tested.

In one embodiment, composite at 23 ± 2 DEG C, pH value be 12 NaOH aqueous solution in soak 1000h After, at least one in mechanical property (i), (ii), (iii) and (iv), preferably at least two, more preferably at least three, enter Preferably four retention >=80% of one step, or >=82%, or >=85%, or >=87%, or >=90%, or >=91%, or >= 92%, or >=93%.

In one embodiment, composite at 23 ± 2 DEG C, pH value be 12 NaOH aqueous solution in soak 1000h After, at least mechanical property (i) retention >=80%, or >=82%, or >=85%, or >=87%, or >=90%, or >=91%, Or >=92%, or >=93%.

In one embodiment, composite at 23 ± 2 DEG C, pH value be 12 NaOH aqueous solution in soak 1000h After, at least mechanical property (ii) retention >=80%, or >=82%, or >=85%, or >=87%, or >=90%, or >=91%, Or >=92%, or >=93%.

In one embodiment, composite at 23 ± 2 DEG C, pH value be 12 NaOH aqueous solution in soak 1000h After, at least mechanical property (iii) retention >=80%, or >=82%, or >=85%, or >=87%, or >=90%, or >= 91%, or >=92%, or >=93%.

In one embodiment, composite at 23 ± 2 DEG C, pH value be 12 NaOH aqueous solution in soak 1000h After, at least mechanical property (iv) retention >=80%, or >=82%, or >=85%, or >=87%, or >=90%, or >=91%, Or >=92%, or >=93%.

In one embodiment, composite at 23 ± 2 DEG C, pH value be 12 NaOH aqueous solution in soak 3000h After, at least at least one in mechanical property (i), (ii), (iii) and (iv), preferably at least two, more preferably at least three , whole four retention >=80%, or >=82%, or >=85%, or >=87%, or >=90%, or >= 91%, or >=92%, or >=93%.

In one embodiment, composite at 23 ± 2 DEG C, pH value be 12 NaOH aqueous solution in soak 3000h After, at least mechanical property (i) retention >=80%, or >=82%, or >=85%, or >=87%, or >=90%, or >=91%, Or >=92%, or >=93%.

In one embodiment, composite at 23 ± 2 DEG C, pH value be 12 NaOH aqueous solution in soak 3000h After, at least mechanical property (ii) retention >=80%, or >=82%, or >=85%, or >=87%, or >=90%, or >=91%, Or >=92%, or >=93%.

In one embodiment, composite at 23 ± 2 DEG C, pH value be 12 NaOH aqueous solution in soak 3000h After, at least mechanical property (iii) retention >=80%, or >=82%, or >=85%, or >=87%, or >=90%, or >= 91%, or >=92%, or >=93%.

In one embodiment, composite at 23 ± 2 DEG C, pH value be 12 NaOH aqueous solution in soak 3000h After, at least mechanical property (iv) retention >=80%, or >=82%, or >=85%, or >=87%, or >=90%, or >=91%, Or >=92%, or >=93%.

According to a kind of embodiment, resin cured matter is thermosetting resin cured matter.According to a kind of embodiment, resin is solid Compound is the solidfied material of the resin combination including following components: thermosetting resin matrix, pH value are the releasing agent of 6.0-7.0.

According to a kind of embodiment, composite of the present invention is mainly made up of reinforcing fiber materials and resin combination. Resin combination includes thermosetting resin matrix, the releasing agent of certain ph, optionally other auxiliary agents.According to a kind of embodiment party Formula, the present invention relates to a kind of composite, including solidfied material and the reinforcing fiber materials of resin combination.Reinforcing fiber materials exists In the solidfied material of resin combination.

Raw material dosage can also be controlled according to the solution of the present invention.Reasonable in order to realize between each component further Interworking makes the performance of composite more excellent, and consumption is more excellent is: by weight, and in end article, reinforcing fiber materials is 70- 80% and resin combination be 20-30%.Such as reinforcing fiber materials can also select 71%, 72%, 73%, 74%, 75%, 78%, 80% etc..The consumption of resin combination can also select 21%, 22%, 24%, 26%, 28%, 30% etc..

Noticeable be, of the present invention program focus on using specific thermosetting resin matrix kind with The compound releasing agent of specific pH carries out interworking.These specific thermosetting resin matrix include epoxy acrylic resin, polyurethane, One or more in unsaturated polyester resin and bimaleimide resin.Prepared composite not only has excellence Mechanical property, the most also there is the most excellent corrosion resistance.When the kind of thermosetting resin matrix is chosen as propylene oxide During acid resin, it passes through synergism with compound releasing agent can be obviously enhanced the decay resistance of insulation material itself.Especially Concrete as materials for wall is typically alkalescence, and therefore the decay resistance to insulated wall connector it is also proposed certain wanting Ask.The present invention finds to use this thermosetting resin matrix of epoxy acrylic resin by a large amount of practices, with pH 6.0-7.0 it Between releasing agent be particularly combined releasing agent carry out compounding after, decay resistance increases substantially, even if being invaded by aqueous alkali Erosion, the most still can guarantee that excellent mechanical property.This composite of the visible present invention passes through successive optimization, the most comprehensive Can reach optimum, this creative work substantial amounts of with inventor is undivided certainly.

(1) resin combination

Resin combination includes: thermosetting resin matrix, pH value are the releasing agent of 6.0-7.0 and other optional auxiliary agents. Preferably, resin combination includes thermosetting resin matrix 100 weight portion, releasing agent 0.5-5 weight portion, other auxiliary agents 1-20 weight Amount part.The raw material dosage of resin combination is more excellent is, resin combination includes thermosetting resin matrix 100 weight portion, releasing agent 1-3 weight portion, optional other auxiliary agents 1-20 weight portion.

Thermosetting resin matrix (or thermosetting resin) can be the curable thermosetting resin of free radical or radical polymerization Mould assembly thermosetting resin.It addition, thermosetting resin matrix (or thermosetting resin) can include epoxy acrylic resin, polyurethane, One or more in unsaturated polyester resin and bimaleimide resin.As long as reinforcing material and above-mentioned thermosetting tree Aliphatic radical body is all in scope of protection of the present invention.One of major emphasis of the present invention is to use specific releasing agent and enhancing After fibrous material, thermosetting resin matrix carry out interworking potentiation, to reach the purpose of high performance corrosion-proof.Unsaturated polyester resin Can be metaphenylene unsaturated polyester resin and adjacent benzene-type unsaturated polyester resin.

Releasing agent pH value between 6.0-7.0, such as pH value can also be 6.0,6.1,6.2,6.3,6.4,6.5,6.6, 6.7,6.8,6.9,7.0 etc..Select the composite that the releasing agent of above-mentioned pH value prepares, it is possible to ensuring compliance with material The excellent technological composite simultaneously preparing the high intensity anti-shear performance with excellence of type.Of the prior art de- Mould agent is generally the combination of all kinds of organic acid or organic ester, so pH value all can maintain about 4.0, even lower, the most right It is the most disadvantageous in the solidification of thermosetting resin matrix and the final performance of goods.Because the thermosetting tree that this patent is previously mentioned Aliphatic radical body is in addition to polyurethane, and its curing mechanism is radical polymerization, and acidic materials are to have strong capture for free radical Ability, thus hinder the solidification of resin matrix, and then affect the performance of final products.And amine conventional for polyurethane Curing catalysts is also alkali compounds and can occur to neutralize reaction with acidic materials.Therefore the present inventor is by big Amount practice finds releasing agent and other raw material interworkings using pH to control between 6.0-7.0, effectively alleviates releasing agent Acidity, for resin solidification and the adverse effect of product properties, greatly improves the combination property of each side of goods itself, Such as mechanical property and corrosion resistance.Further, the composition of raw materials of composite and the formula of releasing agent are also entered by the present invention Go further optimization, to improve the combination property of goods further.

Relative to the thermosetting resin matrix of 100 weight portions, the consumption of releasing agent generally between 0.5-5 weight portion, example Such as 0.5-4 weight portion, or 1-3 weight portion.Relative to the thermosetting resin matrix of 100 weight portions, the consumption of releasing agent is all right It is chosen as 1 weight portion, 1.5 weight portions, 2.3 weight portions, 4.1 weight portions, 4.5 weight portions, 5 weight portions etc..Dosage too many or There may be adverse effect very little.Addition does not has stripping result very little thus affects the manufacturability of material molding, and addition Too many then make to remain too much release agent components in the final article and material list is revealed significant plastication, cause material power Learn being greatly reduced of performance.

Other auxiliary agents can include one or more in initiator, filler, antishrinking agent.In one embodiment, Other auxiliary agents can include filler.Other auxiliary agents can include initiator and filler.Initiator includes radical initiator.

(2) reinforcing fiber materials

Reinforcing fiber materials can be of the prior art those.Reinforcing fiber materials can include that continuous fiber, fiber are knitted One or both in thing.Continuous fiber can include that glass fibre, basalt fibre, aramid fiber, polysulphonamide fiber, carbon are fine The mixture of one or more in dimension, superhigh molecular weight polyethylene fibers, more preferably glass fibre and basalt fibre.Fine Dimensional fabric can include one or more in continuous felt, surface felt, tape edge felt.As long as conventional reinforcing fiber materials kind is equal Within the scope of the present invention.

II. releasing agent

Releasing agent be pH value be the releasing agent of 6.0-7.0.

Releasing agent viscosity at 25 DEG C can be 350-700cps, such as 400-600cps, or 500-600cps.

Releasing agent can be compound releasing agent.Compound releasing agent comprises following components: (a) long-chain fatty alcohol and/or long-chain Aliphatic ether, (b) acrylic polymer, and optional (c) acidifying long-chain fatty alcohol.In one embodiment, compound de- Mould agent includes following components: (a) long-chain fatty alcohol, and (b) acrylic polymer is, and optional (c) acidifying long-chain fatty alcohol.

In one embodiment, compound releasing agent includes: (a) long-chain fatty alcohol and/or long-chain fat ether 60-90 weight Part, (b) acrylic polymer 12-30 weight portion, (c) is acidified long-chain fatty alcohol 0-10 weight portion.At a kind of embodiment In, compound releasing agent includes: long-chain fatty alcohol and/or long-chain fat ether 65-80 weight portion, acrylic polymer 15-30 Weight portion and optional acidifying long-chain fatty alcohol 1-8 weight portion.In one embodiment, compound releasing agent includes: (a) long-chain Fatty alcohol and/or long-chain fat ether 72-78 weight portion, (b) acrylic polymer 15-25 weight portion, and optional (c) Acidifying long-chain fatty alcohol 2-7 weight portion.

In one embodiment, compound releasing agent includes: (a) long-chain fatty alcohol 60-90 weight portion, (b) acrylate Base polymer 12-30 weight portion, (c) is acidified long-chain fatty alcohol 0-10 weight portion.In one embodiment, compound releasing agent bag Include: the acidifying long-chain that (a) long-chain fatty alcohol 65-80 weight portion, (b) acrylic polymer 15-30 weight portion are optional with (c) Fatty alcohol 1-8 weight portion.In one embodiment, compound releasing agent includes: (a) long-chain fatty alcohol 72-78 weight portion, (b) Acrylic polymer 15-25 weight portion, and optional (c) acidifying long-chain fatty alcohol 2-7 weight portion.

The component that must include is (a) long-chain fatty alcohol or long-chain fat ether and (b) acrylic polymer.Pass through A compound releasing agent that () long-chain fatty alcohol or two kinds of raw material interworkings of long-chain fat ether and (b) acrylic polymer are prepared PH value can be made to control between 6.0-7.0.

(a) long-chain fatty alcohol/long-chain fat ether

Component (a) is long-chain fatty alcohol and/or long-chain fat ether, i.e. (a1) long-chain fatty alcohol or (a2) long-chain fat ether or (a3) long-chain fatty alcohol and the combination of long-chain fat ether.

Long-chain fatty alcohol includes one or more in the fatty alcohol that carbon number is 6-20.Long-chain fatty alcohol can be C_6-20Long-chain fatty alcohol, C_8-18Long-chain fatty alcohol or C_10-15Long-chain fatty alcohol.In one embodiment, long-chain fatty alcohol is Long linear fatty alcohol.Long-chain fatty alcohol include n-heptanol, n-octyl alcohol, n-nonyl alcohol, Decanol, positive undecyl alcohol, lauryl alcohol, positive 13 One or more in alcohol and tetradecanol.Long-chain fatty alcohol can be Decanol, n-octyl alcohol, the one of lauryl alcohol or several Kind.Long-chain fatty alcohol can also be the long-chain fatty alcohol with alkyl branches or alkyl substituent.If long-chain fatty alcohol has Alkyl branches or alkyl substituent, preferably backbone c atoms number are more than or equal to 6, preferably greater than or equal to 8, more preferably greater than or Equal to 10, such as C_6-20Long-chain, C_8-18Long-chain or C_10-15Long-chain；Branched carbon atoms number is preferably lower than or equal to 4, the least In or equal to 3, equal to 2 after being further preferably no larger than, most preferably equal to 1.

Long-chain fatty alcohol viscosity at 25 DEG C can be at 350-700cps, preferably 400-600cps, most preferably 500- 600cps。

Long-chain fat ether can be to have C_6-20Long aliphatic hydrocarbon chain, C_8-18Long aliphatic hydrocarbon chain or C_10-15Long-chain fat The ether of alkyl.According to a kind of embodiment, long-chain fat ether has at least one C_6-20Chain alkyl, or at least one C_8-18Long Alkyl group or at least one C_10-15Chain alkyl.

Long-chain fat ether viscosity at 25 DEG C can be at 350-700cps, preferably 400-600cps, most preferably 500- 600cps。

The amount of long-chain fatty alcohol and/or long-chain fat ether can be 60-90 weight portion, such as 65-85 weight portion, 70-80 Weight portion, or 72-78 weight portion, as 67 weight portions, 70 weight portions, 71 weight portions, 73 weight portions, 74 weight portions, 75 weight portions, 76 weight portions, 77 weight portions, 78 weight portions, 80 weight portions, 87 weight portions.

(b) acrylic polymer

It addition, (b) 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 ensure the various fillers degree that is uniformly dispersed in resin combination, thus at the most also mechanics to end article Performance produces active influence.In a word, the excellent selection of organic acid during acrylic polymer is that instead of common releasing agent.

B () acrylic polymer can be esters of acrylic acid homopolymer or acrylic acid esters co-polymer, preferably propylene Esters of gallic acid block copolymer.B () acrylic acid esters co-polymer can be one or more of: random copolymer, block copolymerization Thing, graft copolymer or alternate copolymer, preferred block copolymer.B () acrylic polymer includes at least one (first Base) acrylate monomeric units.B () 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.

The amount of acrylic polymer can be 12-30 weight portion, such as 15-28 weight portion, 15-25 weight portion, or 20-25 weight portion, as 13 weight portion 16 weight portions, 17 weight portions, 18 weight portions, 19 weight portions, 21 weight portions, 22 weight portions, 23 weight portions or 24 weight portions.

(c) acidifying long-chain fatty alcohol

Acidifying long-chain fatty alcohol is optional component.If raw material also comprises acidifying long-chain fatty alcohol, then (c) is acidified Long-chain fatty alcohol can include inorganic acidifying long-chain fatty alcohol or organic acidifying long-chain fatty alcohol, such as oxygen-containing inorganic acid long-chain Fatty alcohol.Such as, (c) acidifying long-chain fatty alcohol can be that nitrification long-chain fatty alcohol, phosphorylation long-chain fatty alcohol, sulphation are long The mixing of one or more in chain fatty alcohol.Nitrification long-chain fatty alcohol can be nitrification reagent with long-chain fatty alcohol by one Determine the product obtained by molar ratio reaction.Phosphorylation long-chain fatty alcohol can be phosphorylation agent (such as phosphorus pentoxide, oxygen Phosphorus chloride) press the product obtained by certain mol proportion example is reacted with long-chain fatty alcohol.Sulphation long-chain fatty alcohol can be sulfonic acid Change reagent and press the product obtained by certain mol proportion example is reacted with long-chain fatty alcohol.In the present invention, acidifying long-chain fatty alcohol is also It is properly termed as long-chain fat alcohol ester.Such as, phosphorylation long-chain fatty alcohol is referred to as phosphoric acid long-chain fat alcohol ester.Many when using During unit's acid acidifying, acidifying long-chain fatty alcohol can be monoesters, polyester and their mixture.Such as, phosphorylation long-chain fat Fat alcohol can be monoesters, diester, three esters or their mixture.

Acidifying long-chain fatty alcohol can be acidifying C_6-20Long-chain fatty alcohol, acidifying C_8-18Long-chain fatty alcohol or acidifying C_10-15 Long-chain fatty alcohol.In one embodiment, acidifying long-chain fatty alcohol is acidifying long linear fatty alcohol.In acidifying long-chain fatty alcohol Long-chain fat alcohol moiety can be which in above-mentioned long-chain fatty alcohol.Such as, acidifying long-chain fatty alcohol includes being acidified C_6-20 Long-chain fatty alcohol, such as, be acidified C_6-20Long linear fatty alcohol.

The amount of acidifying long-chain fatty alcohol can be 0-10 weight portion, such as, 0-8 weight portion, or 0.5-9 weight portion, or 1-8 Weight portion, or 2-7 weight portion, such as 1 weight portion, 2 weight portions, 3 weight portions, 4 weight portions, 5 weight portions, 6 weight portions.

(d) other release agent components

Compound releasing agent can also include other release agent components, such as liquid paraffin, lecithin etc..Other releasing agent groups The amount divided can be 0.01-10 weight portion, such as 0.1-9 weight portion, or 1-8 weight portion, or 2-7.5 weight portion, or 3-7 weight Part.The amount of other release agent components can be less than or equal to 10 weight portions, e.g., less than or equal to 9 weight portions, or less than or etc. In 8 weight portions, or less than or equal to 7.5 weight portions, or less than or equal to 7 weight portions, or less than or equal to 5 weight portions.

By compound releasing agent above-mentioned raw materials interworking prepared, it is different from the compound demoulding general in prior art Agent and the releasing agent of single compound.The present invention uses this compound releasing agent to prepare composite as raw material, and by former Collaborative interworking effect between material, may finally make the various aspects of performance of composite products reach to optimize.

III. the method preparing composite

Another aspect of the present invention relates to the method preparing composite, comprises the following steps: make to comprise releasing agent, thermosetting The resin combination of resin matrix and other optional auxiliary agents is immersed in reinforcing fiber materials, curing molding.

Pultrusion and resin transfer moulding (RTM) forming technique can be used to prepare composite.

According to a kind of embodiment, the method preparing composite comprises the following steps: by reinforcing fiber materials with comprising The resin combination dipping of described releasing agent, thermosetting resin matrix and other optional auxiliary agents, pultrusion curing molding.

According to a kind of embodiment, the method preparing composite comprises the following steps: will comprise described releasing agent, thermosetting Property resin matrix and other optional auxiliary agents resin combination inject preforming reinforcing fiber materials in, use resin pass Pass molded.

The present invention, except providing the formula of high performance composite, additionally provides the several more excellent of above-mentioned composite Preparation method, one of which concrete technology step comprises the steps:

Releasing agent, thermosetting resin matrix, other optional auxiliary agents are mixed to form resin combination, then will strengthen fibre Dimension material impregnates with described resin combination, 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 preparation method of composite can be pultrusion preparation method, including following step Rapid:

Reinforcing fiber materials is passed sequentially through creel, glue maceration tank, preforming tool, imports to and eventually pass through heat one-tenth Mould.By upper and lower two layers polyester surface felt by leading felt device, preforming tool, import to and eventually pass through hot forming tool. The number of regulation reinforcing fiber materials is so that the content of glass fiber of end article is at 70-80%.

In one embodiment, the preparation of resin combination: by thermosetting resin matrix, releasing agent and other auxiliary agents Order add material, often adding a kind of material needs to stir 10-15min, and rotating speed is 2500r/min.

Set three sections of temperature of hot forming tool as one section 105-115 DEG C, two-stage nitration 150-160 DEG C, three sections 145-155 DEG C. Producing after temperature stabilization, set pultrusion speed as 350-600mm/min, the glue that will prepare imports glue maceration tank In, the equipment of starting produces, will glue dipping glass fiber yarn and surface of polyester felt be drawn in hot forming tool, add Become section bar after heat cure, be cut into fixed length by cutter sweep.Finally gained composite is put into 90-100 DEG C of baking Post processing solidification about 15h in case.

Present invention also offers another composite material and preparation method thereof, comprise the steps:

Compound releasing agent and thermosetting resin matrix, other auxiliary agents are mixed to form resin combination, then by resin group Compound injects in the reinforcing fiber materials of preforming, uses the demoulding after resin transfer molding, cooling, to obtain final product.Resin transmits In molded, the temperature closing film forming process can control at 135-150 DEG C, is incubated 10min-3h, it is further preferable that be cooled to Less than 50 DEG C, more preferably cool between 30-40 DEG C.

In one embodiment, the preparation method of composite can be the preparation of resin transfer moulding (RTM) molding Method, comprises the following steps:

According to setting shape and scheduled volume by laid for reinforcing fiber materials on lower mold mould, cut off unnecessary corner simultaneously Material (regulating laid amount makes the reinforcing material content of end article be 70-80%)；

The configuration of glue can be carried out, by thermosetting resin matrix, compound releasing agent and other auxiliary agents according to following component Order add material, often adding a kind of material needs to stir 10-15min, and rotating speed is 2500r/min.The lower mold that laying is good Close up with upper mold and by border seal and fastening.Mould is warming up to 50 DEG C, the resin combination note that will prepare at 50 DEG C subsequently Inject in mold cavity, note regulating injection pressure to guarantee that resin can be completely filled with die cavity degasification body side by side.Simultaneously by mould Temperature is promoted to 135-150 DEG C in 20min, and is incubated 10min-3h；Upper and lower mould is separated after being finally cooled to less than 50 DEG C, with After by goods take out.

Several preparation methoies of the composite according to embodiment of the present invention have the effective one-tenth that can completely retain raw material Part advantage, the advantages such as and it is the most easily operated to have method, and operating condition is gentle.Front and back between step, linking is tight, often Individual operating procedure is all that inventor passes through to put into practice in a large number to be determined, the preferably two kinds sides of preparation during this is numerous preparation method certainly Method, does not represent and cannot use other preparation methoies.

Above-mentioned composite can well be applied on insulated wall connector, construction material and oil mining equipment On.Use above-mentioned composite can make a kind of insulated wall connector bar, and then this insulated wall connector bar can conduct A part for insulated wall connector.

Compared with prior art, the invention have the benefit that

(1) present invention develops and a kind of novel has high intensity, shear-stable composite, by by thermosetting tree Fat, pH value are carried out under certain Optimum proportioning in compound releasing agent, other auxiliary agents and the reinforcing fiber materials of 6.0-7.0 Compound, the composite property prepared is more stable, has fully taken into account high intensity, all properties such as anti-shearing, corrosion-resistant is wanted Ask, substantially prolongs the service life of composite itself, and bring considerable economic benefit simultaneously；When thermosetting resin selects During with epoxy acrylic resin, polyurethane, unsaturated polyester resin and bimaleimide resin, enter with this compound releasing agent Row coordinates, and the composite of preparation has mechanical property and the corrosion resistance of excellence simultaneously；

(2) preparation method of the composite of the present invention itself has the advantage of the active ingredient that can completely retain raw material, And it is the most easily operated to have method, the advantages such as operating condition is gentle；

(3) the above-mentioned composite of the present invention can well be applied to insulated wall as on connector use, and building Also having well application on material and oil mining equipment, it has the high intensity similar with reinforcing bar and modulus, each side thing Reason excellent performance, fully meets actually used situation, it is seen that the composite of the present invention is widely used, is worth promoting and carries out Application.

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 Can be by the commercially available conventional products bought and obtain.

Embodiment

Raw material and reagent:

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..

Basalt fibre yarn mixture: 4800Tex, Jiangsu Tianlong Xuanwu CBF High-Technology Co., Ltd..

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.

Span carrys out amide resin: BMI-01, Honghu Shuangma New Materials Technology Co., Ltd..

Phosphorylation straight-chain fatty alcohol: self-control, by phosphorus pentoxide and straight-chain fatty alcohol in the ratio of 1:2 (mol ratio) 50 At DEG C, stirring reaction 1h, is subsequently added suitable quantity of water and is hydrolyzed, and oil reservoir is extracted, subsequently by oil reservoir by branch vibration layer with water It is dried except water and get final product.

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.

Inorganic filler: may select ground calcium carbonate, Pulvis Talci, Kaolin etc. according to technique.

Antishrinking agent: DX-700, Foshan Dao Kesi micropowder company limited.

Triethylene diamine: analytical pure, Nanjing Guo Chen Chemical Co., Ltd. provides.

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.

Acrylate based block copolymer: being Qingdao University of Science and Technology provides.

Isocyanates MDI:PM-400, Yantai Wanhua Polyurethane Company Limited provides.

PEPA premixed systems: QX30, Nanjing, Nanjing Si Taipan Chemical Co., Ltd. provides.

Zinc stearate: chemical pure, chemical plastic auxiliary reagent factory, Shijiazhuang City Yongfeng provides.

Embodiment 1

The preparation method of composite is as follows, and raw material is all in terms of parts by weight:

1) glass fiber yarn (4800Tex) is passed sequentially through creel, glue maceration tank, preforming tool, import to and Eventually 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 Mould, regulation silvalin number so that the content of glass fiber of end article is 80%, resin group in end article The content of compound is 20%；

2) configuration of resin combination is carried out according to following component: epoxy acrylic resin 100 weight portion, pH value is 6.0 Compound releasing agent 1.0 weight portion, other auxiliary agents totally 15 weight portions (include that initiator TBPO/TBPB compounds 3 weight portions, Talcum Powder 5 weight portion, ground calcium carbonate 5 weight portion, antishrinking agent 2 weight portion), it is sequentially added into material successively, often adds a kind of thing Material needs to stir 10-15min, and rotating speed is 2500r/min；

3) compound releasing agent consists of: lauryl alcohol 70 weight portion, methacrylic acid-acrylic acid butyl ester block copolymer are (poly- In compound, the molar ratio of two kinds of monomeric units is 1.5:1, number-average molecular weight 50000) 24 weight portions, phosphorylation n-heptanol 4 weight Amount part, phosphorylation lauryl alcohol 4 weight portion, mixing and stirring and get final product；

4) three sections of temperature of hot forming tool are set as one section 110 DEG C, two-stage nitration 155 DEG C, three sections 155 DEG C, treat temperature stabilization After produce, and set pultrusion speed as 500mm/min；

5) being imported in glue maceration tank by resin combination, the equipment of starting produces, will glue dipping glass fibers Dimension yarn and surface of polyester felt are drawn in hot forming tool, become section bar after being heating and curing, and are cut into fixed length i.e. by cutter sweep Can, 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 will Post processing solidification 15h in 100 DEG C of baking ovens put into by gained composite.

Embodiment 2

Other operating procedures are substantially the same manner as Example 1, and the most compound releasing agent consists of: n-heptanol 80 weight portion, first Base acrylic acid methyl ester .-methacrylic acid-butyl methacrylate block copolymer (mol ratio of three kinds of monomeric units in polymer Example is: methyl methacrylate: methacrylic acid: butyl methacrylate=2:1:1.5, number-average molecular weight 35000) 22 weight Part, phosphorylation Decanol 3 weight portion.Compound releasing agent pH value after testing is 6.6, and the mark in resin combination is 1.2 weights Amount part.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.

Embodiment 3

Other operating procedures are substantially the same manner as Example 1, and the most compound releasing agent consists of: n-octyl alcohol 87 weight portion, first Base methyl acrylate-acrylic acid butyl ester-butyl methacrylate block copolymer (mol ratio of three kinds of monomeric units in polymer Example is 1:1:1, number-average molecular weight 35000) 13 weight portions.Compound releasing agent pH value after testing is 7.0, in resin combination Mark is 2.2 weight portions.Sample surface in process of production is the most smooth, does not has crackle, falls slag and unfilled corner, illustrates that releasing agent is imitated Fruit is good.

Embodiment 4

Other operating procedures are substantially the same manner as Example 1, and the most compound releasing agent consists of: lauryl alcohol 74 weight portion, first Base acrylic acid methyl ester .-methacrylic acid-butyl methacrylate block copolymer (mol ratio of three kinds of monomeric units in polymer Example is: methyl methacrylate: methacrylic acid: butyl methacrylate=1.5:1:1.5, number-average molecular weight 50000) 24 weights Amount part, phosphorylation tetradecanol 3 weight portion, liquid paraffin 5 weight portion.Compound releasing agent pH value after testing is 6.6, in resin group Mark in compound is 1.2 weight portions.Sample surface in process of production is the most smooth, does not has crackle, falls slag and unfilled corner, explanation Releasing agent is respond well.

Embodiment 5

Other operating procedures are substantially the same manner as Example 1, and the most compound releasing agent consists of: cetyl alcohol 37 weight portion, N-octyl alcohol 40 weight portion, methyl methacrylate-methacrylic acid-methacrylic acid block copolymer (three kinds of lists in polymer The molar ratio of body unit is: methyl methacrylate: methacrylic acid: butyl methacrylate=1.5:1:1.5, and number is divided equally Son amount 10000) 23 weight portions, phosphorylation n-octyl alcohol 3 weight portion, liquid paraffin 5 weight portion, lecithin 2.5 weight portion.Compound de- Mould agent pH value after testing is 6.5, and the mark in resin combination is 1.2 weight portions.Sample surface in process of production is all the time Smooth, there is no crackle, fall slag and unfilled corner, illustrate that releasing agent is respond well.

Embodiment 6

Other operating procedures are substantially the same manner as Example 1, and the most compound releasing agent consists of: positive ten diether 67 weight portions, Methyl methacrylate-methacrylic acid-methacrylic acid block copolymer (molar ratio of three kinds of monomeric units in polymer For: methyl methacrylate: methacrylic acid: butyl methacrylate=1.5:1:1.5, number-average molecular weight 10000) 23 weight Part, phosphorylation n-heptanol 3 weight portion, liquid paraffin 5 weight portion, lecithin 2.5 weight portion.Compound releasing agent pH value after testing is 6.5, the mark in resin combination is 1.2 weight portions.Sample surface in process of production is the most smooth, does not has crackle, falls Slag and unfilled corner, illustrate that releasing agent is respond well.

Embodiment 7

Other operating procedures are substantially the same manner as Example 1, and simply compound releasing agent consists of: lauryl alcohol 30 weight portion, just Ten diether 37 weight portions, butyl polyacrylate (number-average molecular weight 20000) 23 weight portions, phosphorylation lauryl alcohol 3 weight portion, liquid Paraffin 5 weight portion, lecithin 2.5 weight portion.Compound releasing agent pH value after testing is 6.5, and the mark in resin combination is 1.2 weight portion.Sample surface in process of production is the most smooth, does not has crackle, falls slag and unfilled corner, illustrates that releasing agent effect is good Good.

Embodiment 8

Other operating procedures are substantially the same manner as Example 1, and simply releasing agent uses n-octyl alcohol, and releasing agent pH value after testing is 7.0, the mark in resin combination is 4.0 weight portions.Sample surface in process of production is the most smooth, does not has crackle, falls Slag and unfilled corner, illustrate that releasing agent is respond well.

Embodiment 9

Other operating procedures are substantially the same manner as Example 1, and the most compound releasing agent consists of: n-octyl alcohol 70 weight portion, phosphorus Acidifying n-octyl alcohol 20 weight portion.Releasing agent pH value after testing is 7.0, and the mark in resin combination is 1.6 weight portions.Sample Surface is the most smooth in process of production, does not has crackle, falls slag and unfilled corner, illustrates that releasing agent is respond well.

Embodiment 10

Other operating procedures are substantially the same manner as Example 1, and simply releasing agent is phosphorylation lauryl alcohol, and detection pH value is 6.9, Mark in resin combination is 0.6 weight portion.Sample surface in process of production is the most smooth, do not have crackle, fall slag and Unfilled corner, illustrates that releasing agent is respond well.

Embodiment 11

1) according to setting shape and scheduled volume by glass fibre continuous felt and glass fiber yarn/basalt fibre yarn mixture (proportion of composing of mixture is: in terms of weight content, glass fibre 80%, basalt fibre 20%) is laid at lower mold mould On, cut off unnecessary leftover pieces (regulating laid amount makes the reinforcing fiber materials content of end article be 70%), resin group simultaneously The content of compound is 30%；

2) the compound releasing agent of preparation: lauryl alcohol 72 weight portion, methyl methacrylate-methacrylic acid-acrylic acid butyl ester (in polymer, the molar ratio of three kinds of monomeric units is block copolymer: methyl methacrylate: methacrylic acid: methyl-prop Olefin(e) acid butyl ester=1.5:1:1.5, number-average molecular weight 35000) 20 weight portions, phosphorylation n-octyl alcohol 3 weight portion, stir i.e. , compound releasing agent pH value after testing is 6.6；

3) configuration of resin combination is carried out according to following component: epoxy acrylic resin 100 weight portion, compound releasing agent 1.2 weight portions, other auxiliary agent 15 weight portions (initiator B PO3 weight portion, Kaolin 5 weight portion, ground calcium carbonate 6 weight portion, Antishrinking agent 1 weight portion), it is sequentially added into material successively, often adding a kind of material needs to stir 10-15min, and rotating speed is 2500r/min；

4) lower mold good for laying with upper mold is closed up and by border seal and fastening.Mould is warming up to 50 DEG C, subsequently 50 At DEG C, the resin combination prepared is injected in mold cavity, notes regulating injection pressure to guarantee that resin can be completely filled with die cavity Degasification body side by side.The temperature of mould is promoted to 135 DEG C in 20min simultaneously, and is incubated 10min；

5) separate upper and lower mould after being cooled to less than 50 DEG C, subsequently goods are taken out.Article removal is good, and smooth surface does not has There are crackle, groove and bubble.

Embodiment 12

Concrete technology step is essentially identical with embodiments of the invention 11, and resin matrix simply changes into polyurethane glue, Polyurethane glue consists of: by weight, isocyanates MDI 49.9%, PEPA premixed systems 49.9%, triethylene two Amine 0.2%.The resulting product demoulding is good, and smooth surface does not has crackle, groove and bubble.

Embodiment 13

Concrete technology step is essentially identical with embodiments of the invention 11, resin matrix simply changes metaphenylene unsaturated into Polyester resin.The resulting product demoulding is good, and smooth surface does not has crackle, groove and bubble.

Embodiment 14

Concrete technology step is essentially identical with embodiments of the invention 11, resin matrix simply changes metaphenylene unsaturated into Polyester/span carrys out amide resin mixture, consists of: by weight, metaphenylene unsaturated polyester resin 50.0%, double maleoyl Imide resin 50.0%.The resulting product demoulding is good, and smooth surface does not has crackle, groove and bubble.

Comparative example 1

Concrete technology step is essentially identical with embodiments of the invention 2, is simply replaced by the compound releasing agent that pH value is 6.6 Be about the commercial liquid releasing agent (AXEl company of U.S. PUL24) of 4 for pH value, concrete consumption is constant.Sample is in process of production Surface is the most smooth, does not has crackle, falls slag and unfilled corner, illustrates that releasing agent is respond well.

Comparative example 2

Concrete technology step is essentially identical with embodiments of the invention 2, is simply replaced by the compound releasing agent that pH value is 6.6 For zinc stearate, concrete consumption is constant.Sample surface in process of production is the most smooth, does not has crackle, falls slag and unfilled corner, explanation Releasing agent is respond well.

Comparative example 3

Concrete technology step is essentially identical with embodiments of the invention 1, simply consisting of compound releasing agent: n-octyl alcohol 25 weight portions, lauryl alcohol 25 weight portion, methyl methacrylate-butyl acrylate block copolymer (number-average molecular weight 50000) 10 weight portions, phosphorylation n-nonyl alcohol 25 weight portion mixing and stirring and get final product, pH value is 4.9, and concrete consumption is constant.Sample is being given birth to During product, surface is the most smooth, does not has crackle, falls slag and unfilled corner, illustrates that releasing agent is respond well.

Comparative example 4

Concrete technology step is essentially identical with embodiments of the invention 11, simply changes resin matrix into epoxy composite Thing, composition epoxy resin consists of: by weight, epoxy resin 48.0%, firming agent pyromellitic acid anhydride 52.0%.With Time, other auxiliary agents totally 15 weight portions (include that initiator TBPO/TBPB compounds 3 weight portions, Pulvis Talci 5 weight portion, ground calcium carbonate 5 weight portions, antishrinking agent 2 weight portion).The resulting product demoulding is good, and smooth surface does not has crackle, groove and bubble.

Table 1 uses the embodiment of pultrusion processes and the releasing agent (number is weight portion) of comparative example

Table 2 uses embodiment and the comparative example (number is weight portion) of pultrusion processes

Note: in table, releasing agent consumption is the consumption of the thermosetting resin matrix relative to 100 weight portions.

Experimental example 1: performance test

The performance of composite embodiment of the present invention 1-14, comparative example 1-4 prepared contrasts, longitudinal stretching Intensity and modulus test are measured according to the method for regulation in GB/T 1447-2005, and buckling strength and modulus test are pressed Being measured according to the method for regulation in GB/T 1449-2005, the test of short beam shear strength is according to ASTM D2344/D2344M- In 13, the method for regulation is tested, and concrete testing result is as shown in table 3 below:

Table 3 performance test results

From the results shown in Table 3, compound releasing agent and other components of glue that the present invention uses with the use of reaching Arrive good effect, ensure on the premise of good stripping result not performance (especially shear resistant to composite Can) produce obvious adverse effect.The performance (especially anti-shear performance) of product prepared by the present invention is significantly higher than by passing System goods prepared by releasing agent.By the data of table 3 it can be seen that the performance of prepared composite is the most excellent, substantially Maintaining an equal level with high performance epoxy resin, hot strength is substantially in 1000MPa effect, and the intensity of short beam shear is even up to More than 60MPa.But by comparative example 1 and 2 it can be seen that the releasing agent that no matter uses commercially available pH to be 4.0 or zinc stearate, All the performance of resin is created adverse effect.Highly acid firming agent can catch free radical thus affect resin solidification, The mechanical property of the low goods of final decline.Zinc stearate is then that the defect caused due to uniform gathering causes under Mechanical Properties of Products Fall.Meanwhile, by comparative example 3 it can be seen that the formula of compound releasing agent need to be controlled, be otherwise unable to reach pH 6.0-7.0 it Between requirement, thus will also result in the reduction of Mechanical Properties of Products.

It addition, the performance of comparative example 1,2,3,8 and 9 goods is it can be seen that the mechanical property of embodiment 2 resulting product The highest, this explanation also needs the overall manufacturability considering formula in addition to the pH value of releasing agent to be considered.Although, pH7.0's is compound Releasing agent falls below the adverse effect solidifying resin minimum, but is acidified the profit of fatty alcohol in compound release agent components Slip is best, and therefore the lubricating release effect of the compound releasing agent that this component content is the lowest is the most highly desirable, now will pass through Strengthen releasing agent introduction volume and solve this problem.But the introducing of a large amount of releasing agents can produce plastication in the final article, Promote to produce between reinforcing fiber and resin matrix sliding, thus show as the reduction of mechanical property.Meanwhile, by embodiment 10 also Although it can be seen that be used alone acidifying fatty alcohol as releasing agent can reach good effect (show as add minimal amount Releasing agent can obtain good technological effect), but owing to losing the special role of acrylic polymer (uniformly Adsorption moisture on dispersed filler and parcel filler), therefore the performance of resulting product is in a slight decrease also relative to embodiment 1.

In a word, use compound releasing agent proposed by the invention just to become and take into account product properties and moulded manufacturability Optimized choice.

Experimental example 2: corrosion resistance is tested

At 23 ± 2 DEG C, by embodiment 1-3,11 and comparative example 4 prepared by building combined wall board with thermal-insulation connecting piece rod Core soaks 1000h and 3000h respectively in the sodium hydrate aqueous solution that pH value is 12, carries out after being subsequently dried removing surface moisture The retention of Computational Mechanics intensity after the test of longitudinal tensile strength and modulus and buckling strength and modulus.Gained and tie Fruit is as shown in table 4.

Table 4 corrosion resistance result

Data from table 4 are it can be seen that have benefited from the formula choosing of the excellent corrosion resistance of specific resinous type, optimization Select adhesion firm between the uniform dispersity of glue and reinforcing material and resin, by embodiment of the present invention institute The excellent core of preparation shows the alkali resistant corrosion of brilliance.Experienced by after the immersion of 3000h, the mechanical property base of goods This most substantially reduces.By Theoretical Calculation it is known that such experimental result ensure that prepared rod core can be in reality Concrete construction under the conditions of border exists 100 years and does not has under obvious mechanical property to incite somebody to action.And pass through abundant experimental results Also find, carry out compatibility by the compound releasing agent of specific pH and these several thermosetting resins, improve simultaneously mechanical property and Corrosion resistance, when using epoxy acrylic resin, decay resistance can reach most preferably.

Meanwhile, by the data of embodiment 11 it can also be seen that being used in mixed way of basalt fibre/glass fibre is to compare In being used alone the optimum organization of glass fibre, show as performance basically identical on the basis of the raising of alkali resistance.This is because, Basalt fibre is mainly composed of various silicate, therefore alkali corrosion presents obvious inertia, compared to glass fibre more The resistance to alkali liquid corrosion added.Thus, the mixture using both is more satisfactory selection.

But goods are then corroded by alkali liquor in comparative example 4, its mechanical properties decrease is obvious, its power after soaking 3000 Learn performance and have the reduction of nearly 50%, although illustrating that the mechanical property of epoxy resin-base composite material is the most excellent, but its corrosion resistant Lose poor.Therefore as thermosetting resin kind of the present invention, preferably epoxy acrylic resin, polyurethane, bismaleimide One or more of polyimide resin, optimum selection is epoxy acrylic resin.One of core content of the present invention is compound releasing agent With specific resin with the use of.

From the point of view of experimental result, by rational technique and the formula of optimization, composite prepared in embodiment is all Reach the highest level, hot strength >=750MPa, stretch modulus >=40GPa, bending strength >=900, bending modulus >= 39GPa, especially interlaminar shear strength >=57MPa.This index is for several radically curing trees to mention in the present invention For fat is the composite of matrix, it it has been the highest index.It is known that in polymer based thermoset composite What resin matrix was the most general is epoxy resin, the highest, wherein using it as the composite materials property prepared by resin matrix Interlaminar shear strength can reach more than 60MPa.And for other kind resin composites as matrix, its interlayer shear Intensity is extremely difficult to or close to this magnitude.But the interlayer shear by the polymer matrix composite prepared by the present invention Intensity all at more than 57MPa, local optimum can be higher than 60MPa, be fully achieved or be sufficiently close to epoxy resin as matrix Composite, this is the most valuable.Trace it to its cause, be in the present invention use of compound releasing agent.The present invention is made With releasing agent, its PH is 6.0-7.0, partial neutral, and this is totally different from commercially available main flow acidity releasing agent.And based on resin freely The mechanism of base solidification, acid releasing agent as free radical scavenger often solidification to resin matrix produce very adverse influence, Show as the Mechanical Properties of Products reduction that resin state of cure causes not.Therefore use the releasing agent of partial neutral be evade above-mentioned The optimum selection of adverse effect.

Meanwhile, releasing agent present invention further introduces polyacrylate based block copolymer.By long-term experiment, I Find that such oily matter also is able to play good stripping result, owing to it is not significantly acid yet, the most also will not The mechanical property of goods is had a negative impact.And, essence based on its amphipathy macromolecule so that it can be at resin glue Various filler grains are formed strong coating function by liquid, thus hinder the agglomeration between filler grain, promote its In resin adhesive liquid dispersed, this also contribute to improve goods mechanical strength.Meanwhile, just because of this coating function, also The hydrone likely brought in filler grain is also wrapped by, thus avoids connecing of hydrone and free radical Touch, evaded the adverse effect that resin is solidified by the hydrone adsorbing on filler or combining in turn, more ensure that goods Mechanical property.And by the innovation in terms of these, we achieve the preparation of high strength composite.

By table 4 it can be seen that the alkali corrosion resistance of composite prepared by the present invention is the most excellent, up to 3000h Strong base solution soak after also have more than 93% performance retention.And it is known that, although epoxy resin-base composite material Good mechanical performance, but it is weak to alkali liquid corrosion, as shown in Table 2, have lost the mechanical property of nearly 50% after dipping by lye Can, illustrate have obvious degradation reaction to occur in immersion process.In conjunction with mechanical property and resistance to alkali liquid corrosion data, can see Go out by the present invention, be prepared for a kind of polymer matrix composite having strong mechanical performance and excellent alkali corrosion resistance concurrently, and this Plant and take into account the innovative point that the present invention is maximum just.

Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this The thought of invention, it should be considered as content disclosed in this invention equally.

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

1. a composite, including resin cured matter and reinforcing fiber materials, it is characterised in that described composite meet with In lower mechanical property (i), (ii), (iii), (iv) and (v) at least one:

(i) longitudinal tensile strength >=740MPa,

(ii) longitudinal tensile >=40GPa,

(iii) buckling strength >=900MPa,

(iv) buckling modulus >=39GPa, and

(v) short beam shear strength >=57MPa；

Described composite at 23 ± 2 DEG C, pH value be 12 NaOH aqueous solution in soak after 3000h, described mechanical property At least one retention >=80% in (i), (ii), (iii), (iv) and (v).

Composite the most according to claim 1, it is characterised in that described composite is at 23 ± 2 DEG C, and pH value is 12 NaOH aqueous solution in soak after 3000h, at least two in described mechanical property (i), (ii), (iii), (iv) and (v) , more preferably at least three, further preferably at least four, whole five retention >=80%, or >=82%, or >= 85%, or >=87%, or >=90%, or >=91%, or >=92%, or >=93%.

Composite the most according to claim 1, it is characterised in that described composite is at 23 ± 2 DEG C, and pH value is 12 NaOH aqueous solution in soak after 3000h, at least one in mechanical property (i), (ii), (iii) and (iv), the most extremely Few two, more preferably at least three, whole four retention >=80%, or >=82%, or >=85%, or >= 87%, or >=90%, or >=91%, or >=92%, or >=93%.

Composite the most according to claim 1, it is characterised in that

Described composite meets in following mechanical property (i), (ii), (iii), (iv) and (v) at least two, more preferably At least three, further preferably at least four, whole five:

(i) longitudinal tensile strength >=740MPa, preferably >=750MPa, more preferably >=760MPa, further preferably >=770MPa, Preferably >=780MPa,

(ii) longitudinal tensile >=40GPa, preferably >=41GPa, more preferably >=42GPa, further preferably >=43GPa, optimum Choosing >=44GPa,

(iii) buckling strength >=900MPa, preferably >=910MPa, more preferably >=920MPa, further preferably >=930MPa, Most preferably >=940MPa,

(iv) buckling modulus >=39GPa, preferably >=39.5GPa, more preferably >=40GPa, further preferably >=41GPa, Preferably >=42GPa, and

(v) short beam shear strength >=57MPa, preferably >=57.5MPa, more preferably >=58MPa, further preferably >=58.5MPa, Preferably >=59MPa.

5. according to any one described composite of claim 1-4, it is characterised in that described resin cured matter is thermosetting tree Fat solidfied material.

6. according to any one described composite of claim 1-4, it is characterised in that described resin cured matter is resin combination The solidfied material of thing, described resin combination includes: thermosetting resin matrix, pH value are the releasing agent of 6.0-7.0；

Preferably, described releasing agent includes following components: (a) long-chain fatty alcohol and/or long-chain fat ether, (b) esters of acrylic acid Polymer, and optional (c) acidifying long-chain fatty alcohol；

Preferably, long-chain fatty alcohol and/or long-chain fat ether 60-90 weight portion, acrylic polymer 12-30 weight portion and Acidifying long-chain fatty alcohol 0-10 weight portion；

It is further preferred that long-chain fatty alcohol and/or long-chain fat ether 65-80 weight portion, acrylic polymer 15-30 weight Amount part and optional acidifying long-chain fatty alcohol 1-8 weight portion；

It is highly preferred that long-chain fatty alcohol and/or long-chain fat ether 72-78 weight portion, acrylic polymer 15-25 weight portion With optional acidifying long-chain fatty alcohol 2-7 weight portion.

Composite the most according to claim 6, it is characterised in that described acidifying long-chain fatty alcohol is oxygen-containing inorganic acid One or several in long-chain fatty alcohol, preferably nitrification long-chain fatty alcohol, phosphorylation long-chain fatty alcohol, sulphation long-chain fatty alcohol Kind, more preferably phosphorylation long-chain fatty alcohol,

Preferably, acrylic polymer includes one or more of monomeric unit, for example, at least two kinds monomeric units: (i) acrylic acid；(ii) methacrylic acid；(iii) alkyl acrylate, such as acrylic acid C₁-C₁₅Arrcostab, acrylic acid C₁-C₁₀Alkane Base ester；(iv) alkyl methacrylate, such as methacrylic acid C₁-C₁₅Arrcostab, methacrylic acid C₁-C₁₀Arrcostab；(v) third Olefin(e) acid aryl ester, such as acrylic acid C₆-C₂₀Aryl ester；(vi) aryl methacrylate, such as methacrylic acid C₆-C₂₀Aryl ester； (vii) acrylic acid heteroaryl ester, such as acrylic acid C₃-C₂₀Heteroaryl ester；And (viii) methacrylic acid heteroaryl ester, such as methyl Acrylic acid C₃-C₂₀Heteroaryl ester；

Preferably, acrylic polymer is esters of acrylic acid homopolymer or acrylic acid esters co-polymer, preferred acrylate Based block copolymer；

Preferably, acrylate based block copolymer include acrylic acid, acrylic acid methyl ester., ethyl acrylate, butyl acrylate, third Olefin(e) acid pentyl ester, Hexyl 2-propenoate, methacrylic acid, methyl methacrylate, ethyl acrylate, butyl acrylate, acrylic acid penta One or more in the block copolymer of ester and Hexyl 2-propenoate；

Preferably, acrylate based block copolymer includes acrylic acid, methacrylic acid, methyl methacrylate and propylene One or more in the block copolymer of acid butyl ester；

Preferably, the number-average molecular weight of acrylic polymer is between 5000-50000；

Preferably, described long-chain fatty alcohol includes that carbon number is one or more in the long-chain fatty alcohol between 6-20；

Preferably, described long-chain fatty alcohol is long linear fatty alcohol；

It is highly preferred that described long-chain fatty alcohol includes n-heptanol, n-octyl alcohol, n-nonyl alcohol, Decanol, positive undecyl alcohol, lauryl alcohol, just One or more in tridecanol and tetradecanol；

It is highly preferred that described long-chain fatty alcohol includes one or more in Decanol, n-octyl alcohol and lauryl alcohol,

Preferably, described acidifying long-chain fatty alcohol includes being acidified C_6-20Long-chain fatty alcohol, such as, be acidified C_6-20Long linear fatty alcohol；

Preferably, described thermosetting resin matrix includes epoxy acrylic resin, polyurethane, unsaturated polyester resin and span One or more in bismaleimide resin, preferably epoxy acrylic resin.

Composite the most according to claim 1, it is characterised in that described composite is section bar.

9. the composite described in any one of claim 1-8 on insulated wall connector, construction material and oil mining set Standby upper application.

10. an insulated wall connector, such as insulated wall connector bar, it is characterised in that by any one of claim 1-8 institute The composite stated is made.