CN106366578A - Composite material, preparation method and application thereof, thermal insulating wall connecting piece and rod material - Google Patents

Composite material, preparation method and application thereof, thermal insulating wall connecting piece and rod material Download PDF

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Publication number
CN106366578A
CN106366578A CN201610769703.XA CN201610769703A CN106366578A CN 106366578 A CN106366578 A CN 106366578A CN 201610769703 A CN201610769703 A CN 201610769703A CN 106366578 A CN106366578 A CN 106366578A
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long
fatty alcohol
chain fatty
weight portion
composite
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CN106366578B (en
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李枝芳
董诚
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Shandong Shengquan New Material Co Ltd
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Shandong Shengquan New Material Co Ltd
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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
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • 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
    • C08L75/06—Polyurethanes from polyesters
    • 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
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B2/00—Walls, e.g. partitions, for buildings; Wall construction with regard to insulation; Connections specially adapted to walls
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Architecture (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
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Abstract

The invention relates to a composite material, a preparation method and application thereof, a thermal insulating wall connecting piece and a rod material. The composite material provided by the invention is prepared from a cured resin composition and a reinforced fiber material, wherein the resin composition is prepared from a thermosetting resin matrix, a releasing agent with a pH value of 6.0-7.0 and other optional accessory ingredients.

Description

Composite and preparation method thereof, application, insulated wall connector and bar
Technical field
The present invention relates to polymer matrix composite preparation field, in particular to a kind of composite and its preparation Method, application, a kind of insulated wall connector bar and a kind of insulated wall connector.
Background technology
Continuous innovation with construction market and development, novel building energy-conservation walling becomes national main development to be promoted makes Materials for wall.Heat-insulating heat-preserving material is arranged on body of wall hollow part, puts into various adiabators in the air, then for heat-insulated 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 suitably thinning.Due to compound Outstanding advantage in terms of building energy conservation for the body of wall, its application in China's building trade is also more and more extensive.
Sandwich type body of wall be typically necessary using fixedly connected part, inside and outside body of wall and intermediate insulating layer are effectively connected and It is fixed up, traditional connector material is usually to use 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 setting up in combined wall, greatly reduces the heat insulation effect of heat-insulation layer.Therefore pass through The composite using successional reinforcing material/thermosetting resin as framework for certain moulding process preparation is as thermal-insulation connecting piece Excellent core just becomes more satisfactory selection.Such composite is generally the fiber composite of fluoropolymer resin and heat conductivity very little Form, on the basis of ensureing that it has the high intensity similar with reinforcing bar and modulus, the thermal resistance value again making such material is than larger.
It is pointed out that due to the Two-plate sandwich of combined wall, thermal-insulation connecting piece therein generally requires to bear relatively Big shearing force, then the anti-shear performance of its excellent core requires must be excellent, because connector anti-shear performance is more excellent, body of wall Safety coefficient accordingly also can be higher.Therefore the general requirement of composite material base thermal-insulation connecting piece is exactly high intensity, is resisted Shearing, mechanical property will 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 specifically makes With in method, such as cn202248370u, cn204983189u, cn204715667u, cn203924408u, cn202359664u、cn201924463u、cn202644775u、cn202831363u、cn203878809u、us4829733、 In us5519973, us5671574, us6116836, us7266931 patent, but the performance for crucial connector rod core Optimization is rare to be related to, and the optimization of especially mechanical property less relates to.In addition, also having some Patent exploitations with thermoplasticity Resin is the connector (us5673525, us5987834, us6263638) of matrix resin, but is 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.
Content of the invention
The first object of the present invention is to provide a kind of composite, and this composite property is more stable, fully takes into account High intensity, the requirement of the mechanical property such as anti-shearing, substantially prolongs the service life of composite itself.
The second object of the present invention is to provide a kind of composite, has excellent corrosion resistance, particularly alkali resistance.
The third object of the present invention is to provide the compound releasing agent taking into account product propertiess and moulded manufacturability.
One aspect of the present invention provides a kind of composite, the solidfied material including resin combination and reinforcing fiber materials； Wherein resin combination includes: releasing agent for 6.0-7.0 of thermosetting resin matrix, ph value and other optional auxiliary agents.
According to a kind of embodiment, releasing agent at least includes following components: (a) long-chain fatty alcohol and/or long-chain fat ether, (b) acrylic 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 Part 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 portions 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 Amount part and optional acidifying long-chain fatty alcohol 2-7 weight portion.
According to a kind of embodiment, acidifying long-chain fatty alcohol is oxygen-containing inorganic acid long-chain fatty alcohol, and preferably nitrification is long One or more of chain fatty alcohol, phosphorylation long-chain fatty alcohol, sulphation long-chain fatty alcohol, more preferably phosphorylation long-chain fat Alcohol.
According to a kind of embodiment, acrylic polymer includes one or more of monomeric unit, for example, at least Two kinds of monomeric units: (i) acrylic acid；(ii) methacrylic acid；(iii) alkyl acrylate, such as acrylic acid c1-c15Arrcostab, Acrylic acid c1-c10Arrcostab；(iv) alkyl methacrylate, such as methacrylic acid c1-c15Arrcostab, methacrylic acid c1- c10Arrcostab；(v) benzyl acrylate, such as acrylic acid c6-c20Aryl ester；(vi) aryl methacrylate, such as metering system Sour c6-c20Aryl ester；(vii) acrylic acid heteroaryl base ester, such as acrylic acid c3-c20Heteroaryl base ester；And (viii) methacrylic acid Heteroaryl base ester, such as methacrylic acid c3-c20Heteroaryl base ester.
According to a kind of embodiment, acrylic polymer is esters of acrylic acid homopolymer or acrylic ester copolymerization Thing, preferred acrylate based block copolymer.
According to a kind of embodiment, acrylate based block copolymer includes acrylic acid, acrylic acid methyl ester., acrylic acid second Ester, butyl acrylate, amyl acrylate, Hexyl 2-propenoate, methacrylic acid, methyl methacrylate, ethyl acrylate, propylene One or more of block copolymer of acid butyl ester, amyl acrylate and Hexyl 2-propenoate.
According to a kind of embodiment, acrylate based block copolymer includes acrylic acid, methacrylic acid, methacrylic acid One or more of block copolymer of methyl ester and butyl acrylate.
According to a kind of embodiment, the number-average molecular weight of acrylic polymer is between 5000-50000.
According to a kind of embodiment, it is in the long-chain fatty alcohol between 6-20 that described long-chain fatty alcohol includes carbon number One or more.
According to a kind of embodiment, described long-chain fatty alcohol is long linear fatty alcohol.
According to a kind of embodiment, described long-chain fatty alcohol include n-heptanol, n-octyl alcohol, n-nonyl alcohol, Decanol, positive 11 One or more of alcohol, lauryl alcohol, positive tridecanol and tetradecanol.
According to a kind of embodiment, described long-chain fatty alcohol include one of Decanol, n-octyl alcohol and lauryl alcohol or Several.
According to a kind of embodiment, described acidifying long-chain fatty alcohol includes being acidified c6-20Long-chain fatty alcohol, for example, be acidified c6-20 Long linear fatty alcohol.
According to a kind of embodiment, described thermosetting resin matrix includes epoxy acrylic resin, polyurethane, unsaturated poly- One or more of ester resin and bimaleimide resin, preferably epoxy acrylic resin.
According to a kind of embodiment, reinforcing fiber materials include one of continuous fiber, fabric or two kinds.
According to a kind of embodiment, continuous fiber include glass fibre, basalt fibre, aramid fiber, polysulphonamide fiber, One or more of carbon fiber and superhigh molecular weight polyethylene fibers, more preferably glass fibre and basalt fibre Mixture.
According to a kind of embodiment, fabric includes one or more of continuous felt, surface felt and tape edge felt.
Another aspect of the present invention is related to prepare the method for composite, comprises the steps: to make to comprise described releasing agent, heat The resin combination of thermosetting resin matrix and other optional auxiliary agents is immersed in reinforcing fiber materials, curing molding.
According to a kind of embodiment, methods described is carried out using pultrusion curing molding or resin transfer molding.
Another aspect of the present invention is related to composite on insulated wall connector, on construction material and oil mining equipment Application.
Another aspect of the present invention is related to a kind of insulated wall connector bar, is made up of the composite of the present invention.
Another aspect of the present invention is related to a kind of insulated wall connector of employing insulated wall of the present invention connector bar.
The composite of the present invention has excellent corrosion resistance, particularly alkali resistance.
Specific embodiment
In prior art, in building trade, the connector of insulated wall is typically or many using the comparison of reinforcing bar material, but It is that reinforcing bar itself can form heat bridge one by one in combined wall, can greatly reduce heat insulation effect, therefore people in the art Concrete research is conceived to the material which kind of composite replacement reinforcing bar to be used as connector using by member, to solve asking of insulation Topic.Although thermosetting resin based composites excellent thermal insulation performance, each physical property such as intensity of itself still cannot be with The performance of reinforcing bar matches in excellence or beauty, can not really meet the requirement of practical 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, fully simultaneous 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 itself, while greatly improving heat-insulating property, its physical property also 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, and above-mentioned preparation method belongs to compare Preferably preparation method, method has the advantages that the active ingredient that can completely retain raw material in itself, and step linking in front and back is closely, Method is simply easily operated, and operating condition is gentle.
The third object of the present invention is to provide above-mentioned composite in construction material and to have answering in well winning apparatus With, and provide above-mentioned composite as a kind of application of insulated wall connector bar.
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 in order to solve above-mentioned technical problem in prior art, there is provided a kind of thermosetting resin base is combined Material, this composite both ensure that heat-insulating property and and had been guaranteed in physical property, can be with the thing of reinforcing bar Rationality can compare favourably, and this combination property preferably composite did not also have any record, the present invention in the art before Still belong to pioneering.
Why the composite of the present invention has excellent high intensity, the physical property such as anti-shearing, is combined with the present invention The selection of composition of raw materials of material itself is undivided.
Composite of the present invention is mainly made up of reinforcing fiber materials and resin combination.Resin combination includes thermosetting Property resin matrix, the releasing agent of specific ph value, optionally other auxiliary agents.
According to a kind of embodiment, the present invention relates to a kind of composite, the solidfied material including resin combination and enhancing Fibrous material.Reinforcing fiber materials are in the solidfied material of resin combination.
Raw material dosage can also be controlled according to the solution of the present invention.In order to realize further each group divide between reasonable Interworking makes the performance of composite more excellent, and consumption is more excellent to be: by weight, in end article, reinforcing fiber materials are 70- 80% and resin combination be 20-30%.Such as reinforcing fiber materials can also select 71%, 72%, 73%, 74%, 75%, 78%th, 80% etc..The consumption of resin combination can also select 21%, 22%, 24%, 26%, 28%, 30% etc..
Noticeable be, one of the present invention program focus on using specific thermosetting resin matrix species with The compound releasing agent of specific ph carries out interworking.These specific thermosetting resin matrix include epoxy acrylic resin, polyurethane, One or more of unsaturated polyester resin and bimaleimide resin.Prepared composite not only has excellent Mechanical property, also there is very excellent corrosion resistance simultaneously.When the species of thermosetting resin matrix is chosen as propylene oxide During acid resin, it can significantly increase the decay resistance of insulation material itself with compound releasing agent by synergism.Especially As materials for wall concrete typically in alkalescence, therefore the decay resistance of insulated wall connector be it is also proposed certain will Ask.The present invention passes through a large amount of practices and finds to adopt the thermosetting resin matrix of such as epoxy acrylic resin, with ph in 6.0-7.0 Between the particularly compound releasing agent of releasing agent carry out compounding after, decay resistance increases substantially, even if being subject to aqueous alkali Corrode, also still can guarantee that excellent mechanical property.It can be seen that this composite of the present invention passes through successive optimization, finally comprehensive Performance can reach optimum, certainly this substantial amounts of creative work is undivided with inventor.
(1) resin combination
Resin combination includes: releasing agent for 6.0-7.0 of thermosetting resin matrix, ph value 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 to be, 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 can be the curable thermosetting resin of free radical or radical polymerization mould assembly thermosetting resin. In addition, thermosetting resin matrix may include epoxy acrylic resin, polyurethane, unsaturated polyester resin and BMI One or more of resin.As long as reinforcing material and above-mentioned thermosetting resin matrix are all in scope of protection of the present invention Interior.One of major emphasis of the present invention is to carry out with reinforcing fiber materials, thermosetting resin matrix using specific releasing agent After interworking potentiation, to reach the purpose of high performance corrosion-proof.Unsaturated polyester resin can be metaphenylene unsaturated polyester resin With adjacent benzene-type unsaturated polyester resin.
Releasing agent ph value between 6.0-7.0, for example ph value can for 6.0,6.1,6.2,6.3,6.4,6.5,6.6, 6.7th, 6.8,6.9,7.0 etc..The composite being prepared from the releasing agent of above-mentioned ph value, can ensure compliance with material The excellent technological of type prepares the composite with excellent high intensity anti-shear performance simultaneously.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 4.0 about, even lower, so right It is very unfavorable in the solidification of thermosetting resin matrix and the final performance of product.Because the thermosetting tree that this patent is previously mentioned In addition to polyurethane, its curing mechanism is radical polymerization to aliphatic radical body, and acidic materials are to have strong capture for free radical Ability, thus hindering the solidification of resin matrix, and then affects the performance of final products.And conventional amine for polyurethane Curing catalysts are also alkali compoundss and with acidic materials, neutralization reaction can occur.Therefore the present inventor passes through greatly Amount practice discovery controls releasing agent and other raw material interworkings between 6.0-7.0 using ph, effectively alleviates releasing agent The acid adverse effect for resin solidification and product propertiess, greatly improves the combination property of each side of product itself, As mechanical property and corrosion resistance.Further, the present invention also enters to the composition of raw materials of composite and the formula of releasing agent Go further optimization, to improve the combination property of product further.
With respect to the thermosetting resin matrix of 100 weight portions, the consumption of releasing agent generally between 0.5-5 weight portion, example As 0.5-4 weight portion, or 1-3 weight portion.With respect to the thermosetting resin matrix of 100 weight portions, the consumption of releasing agent is acceptable 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 Might have adverse effect very little.Add and do not have stripping result very little thus affecting the manufacturability of material molding, and addition Too many then make to remain excessive release agent components in the final article and show significant plastication to material, lead to material power Learn being greatly reduced of performance.
Other auxiliary agents can include one or more of initiator, filler, antishrinking agent.In one embodiment, Other auxiliary agents can include filler.In one embodiment, other auxiliary agents can include initiator and filler.Implement a kind of In mode, initiator includes radical initiator.
(2) reinforcing fiber materials
Reinforcing fiber materials can be of the prior art those.Reinforcing fiber materials may include continuous fiber, fiber is knitted One of thing or two kinds.Continuous fiber may include glass fibre, basalt fibre, aramid fiber, polysulphonamide fiber, carbon fibre The mixture of one or more of dimension, superhigh molecular weight polyethylene fibers, more preferably glass fibre and basalt fibre.Fine Dimensional fabric may include one or more of continuous felt, surface felt, tape edge felt.As long as conventional reinforcing fiber materials species is equal Within the scope of the present invention.
Ii. releasing agent
Releasing agent releasing agent for 6.0-7.0 for ph value.
Viscosity at 25 DEG C for the releasing agent 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, it is combined and take off Mould agent includes following components: (a) long-chain fatty alcohol, (b) acrylic polymer, 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.In 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 Birds of the same feather flock together compound 12-30 weight portion, (c) is acidified long-chain fatty alcohol 0-10 weight portion.In one embodiment, compound releasing agent bag Include: (a) long-chain fatty alcohol 65-80 weight portion, (b) acrylic polymer 15-30 weight portion and (c) optional acidifying long-chain 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 group that must include is divided into (a) long-chain fatty alcohol or long-chain fat ether and (b) acrylic polymer.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, that is, (a1) long-chain fatty alcohol or (a2) long-chain fat ether or (a3) the combining of long-chain fatty alcohol and long-chain fat ether.
Long-chain fatty alcohol includes one or more of fatty alcohol that carbon number is 6-20.Long-chain fatty alcohol can be c6-20Long-chain fatty alcohol, c8-18Long-chain fatty alcohol or c10-15Long-chain fatty alcohol.Long-chain fatty alcohol can be (i) long linear fat Alcohol or (ii) have the long-chain fatty alcohol of alkyl branches or alkyl substituent.In one embodiment, long-chain fatty alcohol is length Straight-chain 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 of alcohol and tetradecanol.Long-chain fatty alcohol can be Decanol, n-octyl alcohol, one kind 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 be more than or equal to 6, preferably greater than or equal to 8, more preferably greater than or Equal to 10, such as c6-20Long-chain, c8-18Long-chain or c10-15Long-chain；Branched carbon atoms number is preferably lower than or equal to 4, more preferably little In or be equal to 3, after being further preferably no larger than be equal to 2, most preferably be equal to 1.
Viscosity at 25 DEG C for the long-chain fatty alcohol can be in 350-700cps, preferably 400-600cps, most preferably 500- 600cps.
Long-chain fat ether can be with c6-20Long aliphatic hydrocarbon chain, c8-18Long aliphatic hydrocarbon chain or c10-15Long-chain fat The ether of alkyl.According to a kind of embodiment, long-chain fat ether has at least one c6-20Chain alkyl, or at least one c8-18Long Alkyl group or at least one c10-15Chain alkyl.
Viscosity at 25 DEG C for the long-chain fat ether can be in 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, such 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
In addition, (b) acrylic polymer with the use of an innovative point being also the present invention.On the one hand this component The effect of releasing agent can effectively be played and its acidity is not strong, meanwhile, as amphipathy macromolecule, it can also effectively carry High and ensure the degree that is uniformly dispersed in resin combination for the various fillers, thus in the to a certain degree also mechanics to end article Performance produces active influence.In a word, acrylic polymer is that instead of the excellent selection of organic acid in common releasing agent.
B () acrylic polymer can be esters of acrylic acid homopolymer or acrylic acid esters co-polymer, preferably propylene Acid esters based 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 unit, 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, 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 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 of block copolymer of ester, amyl acrylate and Hexyl 2-propenoate.Acrylate based block copolymer can Think one or more of block copolymer of methacrylic acid, methyl methacrylate, butyl acrylate.
Acrylic polymer number-average molecular weight can control between 5000-50000, between such as 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, such as 13 weight portion 16 weight portion, 17 weight portions, 18 weight portions, 19 weight portions, 21 weight portions, 22 weight portions, 23 weight portions or 24 weight portions.
C () is acidified long-chain fatty alcohol
Acidifying long-chain fatty alcohol is optional component.If also comprising in raw material to be acidified 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.For example, (c) acidifying long-chain fatty alcohol can be long for nitrification long-chain fatty alcohol, phosphorylation long-chain fatty alcohol, sulphation The mixing of one or more of chain fatty alcohol.Nitrification long-chain fatty alcohol can be nitrification reagent with long-chain fatty alcohol by one Determine the obtained product of 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, it is acidified long-chain fatty alcohol It is properly termed as long-chain fat alcohol ester.For example, phosphorylation long-chain fatty alcohol is referred to as phosphoric acid long-chain fat alcohol ester.When using many During unit's acid acidifying, acidifying long-chain fatty alcohol can be monoesters, polyester and their mixture.For example, phosphorylation long-chain fat Fat alcohol can be monoesters, diester, three esters or their mixture.
Acidifying long-chain fatty alcohol can be acidifying c6-20Long-chain fatty alcohol, acidifying c8-18Long-chain fatty alcohol or acidifying c10-15 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 part can be which in above-mentioned long-chain fatty alcohol.For example, acidifying long-chain fatty alcohol includes being acidified c6-20 Long-chain fatty alcohol, for example, be acidified c6-20Long linear fatty alcohol.
The amount of acidifying long-chain fatty alcohol can be 0-10 weight portion, for example, 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 be less than or wait In 8 weight portions, or it is less than or equal to 7.5 weight portions, or is less than or equal to 7 weight portions, or be less than or equal to 5 weight portions.
By the compound releasing agent preparing above-mentioned raw materials interworking, different from the general compound demoulding in prior art Agent and the releasing agent of single compound.The present invention prepares composite using this compound releasing agent as raw material, and by former Collaborative interworking effect between material, may finally make the various aspects of performance of composite products reach optimization.
Iii. the method preparing composite
Another aspect of the present invention is related to prepare the method for composite, comprises the following steps: makes to comprise releasing agent, thermosetting The resin combination of resin matrix and other optional auxiliary agents is immersed in reinforcing fiber materials, curing molding.
Composite can be prepared using pultrusion and two kinds of technology of resin transfer moulding (rtm) molding.
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, using 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 is impregnated 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, It is 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, walk including following Rapid:
Reinforcing fiber materials are passed sequentially through creel, glue maceration tank, preforming tool, imports to and eventually pass through heat one-tenth Pattern has.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 adjusting reinforcing fiber materials is so that the content of glass fiber of end article is in 70-80%.
In one embodiment, the preparation of resin combination: by thermosetting resin matrix, releasing agent and other auxiliary agents Order add material, often add a kind of material need stir 10-15min, rotating speed be 2500r/min.
Three sections of temperature setting hot forming tool as one section 105-115 DEG C, 150-160 DEG C of two-stage nitration, three sections 145-155 DEG C. Produced after temperature stabilization, set pultrusion speed as 350-600mm/min, the glue preparing is imported glue maceration tank In, the equipment of starting is produced, will glue dipping glass fiber yarn and surface of polyester felt be drawn in hot forming tool, plus Become section bar after heat cure, fixed length is cut into by cutter sweep.Finally gained composite is put into 90-100 DEG C of baking Post processing solidification 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, using the demoulding after resin transfer molding, cooling, obtains 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 being 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 mould mould, cut off unnecessary corner simultaneously Material (adjusting laid amount and making the reinforcing material content of end article is 70-80%)；
The configuration of glue can be carried out according to following component, by thermosetting resin matrix, compound releasing agent and other auxiliary agents Order add material, often add a kind of material need stir 10-15min, rotating speed be 2500r/min.Lower mould good for laying Close up with upper mould and by border seal and fastening.Mould is warming up to 50 DEG C, at subsequent 50 DEG C, the resin combination preparing is noted Inject in mold cavity, notice that adjusting injection pressure removes gas side by side to guarantee that resin can be completely filled with die cavity.Simultaneously by mould Temperature is promoted to 135-150 DEG C in 20min, and is incubated 10min-3h；Finally it is cooled to less than 50 DEG C and separate upper and lower mould afterwards, with Afterwards product is taken 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 The advantage of part, and there is the advantages of method is simply easily operated, and operating condition is gentle.It is connected closely in front and back between step, often Individual operating procedure is all that inventor passes through to put into practice in a large number and determined, this is the preferably two kinds sides of preparation in numerous preparation methoies certainly Method, does not represent and cannot adopt other preparation methoies.
Above-mentioned composite can be very good to be applied on insulated wall connector, construction material and oil mining equipment On.A kind of insulated wall connector bar can be made using above-mentioned composite, and then this insulated wall connector bar can conduct A part for insulated wall connector.
Compared with prior art, the invention has the benefit that
(1) present invention develops and a kind of new has high intensity, shear-stable composite, by by thermosetting tree Fat, ph value are carried out under certain Optimum proportioning in the compound releasing agent of 6.0-7.0, other auxiliary agents and reinforcing fiber materials Compound, the composite property prepared is more stable, has fully taken into account high intensity, all properties such as anti-shearing, corrosion-resistant will Ask, substantially prolongs the service life of composite itself, and bring considerable economic benefit simultaneously；When thermosetting resin choosing During with epoxy acrylic resin, polyurethane, unsaturated polyester resin and bimaleimide resin, enter with this compound releasing agent Row cooperation, the composite of preparation has excellent mechanical property and corrosion resistance simultaneously；
(2) preparation method of the composite of the present invention has the advantages that the active ingredient that can completely retain raw material in itself, And there is the advantages of method is simply easily operated, and operating condition is gentle；
(3) the above-mentioned composite of the present invention can be applied to insulated wall well as use on connector, and in building Good application is also had 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 is described in detail, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and be not construed as limiting the scope of the present invention.Unreceipted concrete in embodiment Condition person, the condition according to normal condition or manufacturer's suggestion is carried out.Agents useful for same or the unreceipted production firm person of instrument, are 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 1:2 (mol ratio) ratio 50 Stirring reaction 1h at DEG C, is subsequently added suitable quantity of water and is hydrolyzed, and branch vibration layer is extracted to oil reservoir with water, subsequently by oil reservoir Eliminating water is dried obtain 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 analysis pure.
Inorganic filler: ground calcium carbonate, Pulvis Talci, Kaolin etc. be may be selected according to technique.
Antishrinking agent: dx-700, Foshan Dao Kesi micropowder company limited.
Triethylene diamine: analysis is pure, Nanjing Guo Chen Chemical Co., Ltd. provides.
Epoxy resin and firming agent pyromellitic acid anhydride: favour cypress new material science and technology (Shanghai) limited company 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 combination material: qx30, Nanjing Nanjing Si Taipan Chemical Co., Ltd. provides.
Zinc stearate: chemistry is pure, Shijiazhuang City Yongfeng chemical plastic auxiliary reagent factory 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 Pass through hot forming tool eventually, by upper and lower two layers polyester surface felt by leading felt device, preforming tool, import to and eventually pass through heat Mould, adjusts the number of silvalin so that the content of glass fiber of end article is 80%, resin group in end article The content of compound is 20%；
2) carry out the configuration of resin combination: epoxy acrylic resin 100 weight portion according to following component, ph value is 6.0 Compound releasing agent 1.0 weight portion, other auxiliary agents totally 15 weight portions (include initiator tbpo/tbpb compound 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 add a kind of thing Material needs to stir 10-15min, and rotating speed is 2500r/min；
3) it is combined releasing agent to consist 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 be 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 obtains final product；
4) three sections of temperature setting hot forming tool as one section 110 DEG C, 155 DEG C of two-stage nitration, three sections 155 DEG C, treat temperature stabilization After produced, and set pultrusion speed as 500mm/min；
5) by resin combination import glue maceration tank in, the equipment of starting is produced, will glue dipping glass fibers Dimension yarn and surface of polyester felt are drawn in hot forming tool, become section bar, being cut into fixed length by cutter sweep is after being heating and curing Can, surface is smooth all the time in process of production for sample, does not have crackle, scaling-off 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, are simply combined releasing agent and consist of: n-heptanol 80 weight portion, first Base acrylic acid methyl ester .-methacrylic acid-butyl methacrylate block copolymer (the 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.Ph value is 6.6 to compound releasing agent after testing, and the fraction in resin combination is 1.2 weights Amount part.Surface is smooth all the time in process of production for sample, does not have crackle, scaling-off and unfilled corner, illustrates that releasing agent is respond well.
Embodiment 3
Other operating procedures are substantially the same manner as Example 1, are simply combined releasing agent and consist of: n-octyl alcohol 87 weight portion, first The 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.Ph value is 7.0 to compound releasing agent after testing, in resin combination Fraction is 2.2 weight portions.Surface is smooth all the time in process of production for sample, does not have crackle, scaling-off 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, are simply combined releasing agent and consist of: lauryl alcohol 74 weight portion, first Base acrylic acid methyl ester .-methacrylic acid-butyl methacrylate block copolymer (the 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.Ph value is 6.6 to compound releasing agent after testing, in resin group Fraction in compound is 1.2 weight portions.Surface is smooth all the time in process of production for sample, does not have crackle, scaling-off and unfilled corner, explanation Releasing agent is respond well.
Embodiment 5
Other operating procedures are substantially the same manner as Example 1, are simply combined releasing agent and consist 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- Ph value is 6.5 after testing for mould agent, and the fraction in resin combination is 1.2 weight portions.Surface is all the time in process of production for sample Smooth, there is no crackle, scaling-off and unfilled corner, illustrate that releasing agent is respond well.
Embodiment 6
Other operating procedures are substantially the same manner as Example 1, are simply combined releasing agent and consist of: positive ten diether 67 weight portion, Methyl methacrylate-methacrylic acid-methacrylic acid block copolymer (the 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.Ph value is compound releasing agent after testing 6.5, the fraction in resin combination is 1.2 weight portions.Surface is smooth all the time in process of production for sample, does not have 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, are simply combined releasing agent and consist of: lauryl alcohol 30 weight portion, just Ten diether 37 weight portion, 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.Ph value is 6.5 to compound releasing agent after testing, and the fraction in resin combination is 1.2 weight portion.Surface is smooth all the time in process of production for sample, does not have crackle, scaling-off 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 ph value is releasing agent after testing 7.0, the fraction in resin combination is 4.0 weight portions.Surface is smooth all the time in process of production for sample, does not have 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, are simply combined releasing agent and consist of: n-octyl alcohol 70 weight portion, phosphorus Acidifying n-octyl alcohol 20 weight portion.Ph value is 7.0 to releasing agent after testing, and the fraction in resin combination is 1.6 weight portions.Sample Surface is smooth all the time in process of production, does not have crackle, scaling-off 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, Fraction in resin combination is 0.6 weight portion.Surface is smooth all the time in process of production for sample, do not have crackle, scaling-off and Unfilled corner, illustrates that releasing agent is respond well.
Embodiment 11
The preparation method of composite is as follows, and raw material is all in terms of parts by weight:
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%) laid in lower mould mould On, cut off unnecessary leftover pieces (adjusting laid amount and making the reinforcing fiber materials content of end article is 70%), resin group simultaneously The content of compound is 30%；
2) prepare compound releasing agent: 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. , ph value is 6.6 to compound releasing agent after testing；
3) carry out the configuration of resin combination: epoxy acrylic resin 100 weight portion, compound releasing agent according to following component 1.2 weight portions, other auxiliary agent 15 weight portions (initiator bpo3 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 add a kind of material to need to stir 10-15min, rotating speed is 2500r/min；
4) lower mould good for laying and upper mould are closed up and by border seal and fastening.Mould is warming up to 50 DEG C, subsequent 50 At DEG C, the resin combination preparing is injected in mold cavity, notices that adjusting injection pressure can be completely filled with die cavity to guarantee resin Remove gas side by side.The temperature of mould is promoted to 135 DEG C in 20min simultaneously, and is incubated 10min；
5) it is cooled to less than 50 DEG C and separates upper and lower mould afterwards, subsequently product is taken out.Article removal is good, and smooth surface does not have There are crackle, groove and bubble.
Embodiment 12
Concrete technology step is essentially identical with embodiments of the invention 11, simply resin matrix is changed to polyurethane glue, Polyurethane glue consists of: by weight, isocyanates mdi 49.9%, PEPA combination material 49.9%, triethylene two Amine 0.2%.The resulting product demoulding is good, and smooth surface does not have crackle, groove and bubble.
Embodiment 13
Concrete technology step is essentially identical with embodiments of the invention 11, simply resin matrix is changed to metaphenylene unsaturated Polyester resin.The resulting product demoulding is good, and smooth surface does not have crackle, groove and bubble.
Embodiment 14
Concrete technology step is essentially identical with embodiments of the invention 11, simply resin matrix is changed to metaphenylene unsaturated 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 have crackle, groove and bubble.
Comparative example 1
Concrete technology step is essentially identical with embodiments of the invention 2, and simply by ph value, the compound releasing agent for 6.6 is replaced It is about 4 commercial liquid releasing agent (axel company of U.S. pul24) for ph value, concrete consumption is constant.Sample is in process of production Surface is smooth all the time, does not have crackle, scaling-off 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, and simply by ph value, the compound releasing agent for 6.6 is replaced For zinc stearate, concrete consumption is constant.Surface is smooth all the time in process of production for sample, does not have crackle, scaling-off 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 obtain final product, and ph value is 4.9, and concrete consumption is constant.Sample is being given birth to During product, surface is smooth all the time, does not have crackle, scaling-off 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 resin matrix is changed to epoxy composite Thing, composition epoxy resin consists of: by weight, epoxy resin 48.0%, firming agent pyromellitic acid anhydride 52.0%.With When, other auxiliary agents totally 12 weight portions (Pulvis Talci 5 weight portion, ground calcium carbonate 5 weight portion, antishrinking agent 2 weight portion).Gained system Pint mould is good, and smooth surface does not have crackle, groove and bubble.
Table 1 adopts the embodiment of pultrusion processes and the releasing agent (number is weight portion) of comparative example
Table 2 adopts embodiment and the comparative example (number is weight portion) of resin transfer moulding (rtm) method of forming
Note: in table, releasing agent consumption is the consumption of the thermosetting resin matrix with respect to 100 weight portions.
Experimental example 1: performance test
The performance of the composite that embodiment of the present invention 1-14, comparative example 1-4 are prepared is contrasted, longitudinal stretching Intensity and modulus test are measured according to method specified in gb/t 1447-2005, and buckling strength and modulus test are pressed It is measured according to method specified in gb/t 1449-2005, the test of short beam shear strength is according to astm d2344/d2344m- Specified in 13, method 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 the glue other components that the present invention adopts are with the use of reaching Arrive good effect, not (the especially shear resistant of the performance to composite on the premise of ensureing good stripping result Can) produce obvious adverse effect.The performance (especially anti-shear performance) of product prepared by the present invention is significantly higher than by passing Product prepared by system releasing agent.The performance that can be seen that prepared composite by the data of table 3 is very excellent, substantially Maintain an equal level with high performance epoxy resin, tensile strength acts in 1000mpa substantially, the intensity of short beam shear is even up to More than 60mpa.But the releasing agent no matter the use of commercially available ph being 4.0 or zinc stearate be can be seen that by comparative example 1 and 2, All adverse effect is created to the performance of resin.Highly acid firming agent can catch free radical thus affecting resin solidification, The mechanical property of the low product of final decline.Zinc stearate is then to be caused under Mechanical Properties of Products due to the defect that uniform gathering leads to Fall.Meanwhile, by comparative example 3 as 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.
In addition, the performance of comparative example 1,2,3,8 and 9 product can be seen that the mechanical property of embodiment 2 resulting product 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 is minimum falling below to the adverse effect of resin solidification, but is acidified the profit of fatty alcohol in compound release agent components Preferably, the lubricating release effect of the therefore very low compound releasing agent of this component content is not just highly desirable, now will pass through for slip Increase releasing agent introduction volume to solve this problem.But the introducing of a large amount of releasing agents can produce plastication in the final article, Promote to produce sliding between reinforcing fiber and resin matrix, thus showing as the reduction of mechanical property.Meanwhile, by embodiment 10 Although (showing as adding minimal amount as can be seen that being used alone acidifying fatty alcohol and can reaching good effect as releasing agent Releasing agent can obtain good technological effect), but due to lose acrylic polymer special role (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, just become using compound releasing agent proposed by the invention and take into account product propertiess and moulded manufacturability Optimized choice.
Experimental example 2: corrosion resistance test
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 ph value is for 12 sodium hydrate aqueous solution, carries out after being subsequently dried removing surface moisture The retention of Computational Mechanicses 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 testing result
Data from table 4 can be seen that the formula choosing having benefited from the excellent corrosion resistance of specific resinous type, optimizing Select firm adhesion and the uniform dispersity of glue and reinforcing material and resin between, by embodiment of the present invention institute The excellent core of preparation shows the alkali resistant corrosion of brilliance.Experienced after the immersion of 3000h, the mechanical property base of product This does not substantially reduce.By Theoretical Calculation it is known that such experimental result ensure that prepared rod core can be in reality Existing 100 years in concrete construction under the conditions of border and do not have will under obvious mechanical property.And pass through abundant experimental results Also find, carry out compatibility by the compound releasing agent of specific ph and this several thermosetting resin, 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 the optimum organization being used alone glass fibre, show as performance basically identical on the basis of alkali resistance raising.This is because, Basalt fibre main component is various silicate, therefore alkali corrosion is assumed with obvious inertia, compared to glass fibre more Plus resistance to alkali liquid corrosion.Thus, the use of both mixture is more satisfactory selection.
But product is then corroded by alkali liquor in comparative example 4, its mechanical properties decrease is obvious, its power after soaking 3000 Learn performance have nearly 50% reduction, although illustrate epoxy resin-base composite material mechanical property very excellent, its corrosion resistant Erosion is poor.Therefore as thermosetting resin species 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 using cooperatively of specific resin.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that without departing substantially from the present invention's Many other changes can be made in the case of spirit and scope and change.It is, therefore, intended that in the following claims Including all such changes and modifications belonging in the scope of the invention.

Claims (10)

1. a kind of composite, the solidfied material including resin combination and reinforcing fiber materials,
Wherein, described resin combination includes: releasing agent for 6-7 of thermosetting resin matrix, ph value and other optional auxiliary agents.
2. composite according to claim 1 is it is characterised in that described releasing agent at least includes following components: (a) is long Chain fatty alcohol and/or long-chain fat ether, (b) acrylic 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.
3. composite according to claim 2 is it is characterised in that described acidifying long-chain fatty alcohol is oxygen-containing inorganic acid One of long-chain fatty alcohol, preferably nitrification long-chain fatty alcohol, phosphorylation long-chain fatty alcohol, sulphation long-chain fatty alcohol or several 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 base ester, such as acrylic acid c3-c20Heteroaryl base ester；And (viii) methacrylic acid heteroaryl base ester, such as methyl Acrylic acid c3-c20Heteroaryl base 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 of 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 of 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 carbon number is one or more of 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 of tridecanol and tetradecanol；
It is highly preferred that described long-chain fatty alcohol includes one or more of Decanol, n-octyl alcohol and lauryl alcohol；
Preferably, described long-chain fat ether is with c6-20The ether of long aliphatic hydrocarbon chain；
Preferably, described acidifying long-chain fatty alcohol includes being acidified c6-20Long-chain fatty alcohol, for example, be acidified c6-20Long linear fatty alcohol.
4. composite according to claim 1 is it is characterised in that described thermosetting resin matrix includes epoxy acrylic One or more of resin, polyurethane, unsaturated polyester resin and bimaleimide resin, preferably epoxy acrylic Resin.
5. according to claim 1-4 any one described composite it is characterised in that described reinforcing fiber materials include continuously One of fiber, fabric or two kinds；
Preferably, described continuous fiber include glass fibre, basalt fibre, aramid fiber, polysulphonamide fiber, carbon fiber, with One or more of and superhigh molecular weight polyethylene fibers, the more preferably mixture of glass fibre and basalt fibre；
Preferably, described fabric includes one or more of continuous felt, surface felt and tape edge felt.
6. the method for composite according to any one of claim 1-5 for the preparation, comprises the steps: to make to comprise described taking off The resin combination of mould agent, thermosetting resin matrix and other optional auxiliary agents is immersed in reinforcing fiber materials, curing molding.
7. the composite described in claim 6 preparation method it is characterised in that methods described adopt pultrusion curing molding or Resin transfer molding is carried out.
8. the composite described in any one of claim 1-5 on insulated wall connector, construction material and oil mining set Standby upper application.
9. a kind of insulated wall connector bar, the composite described in any one of claim 1-5 is made.
10. the insulated wall connector of the insulated wall connector bar of a kind of employing claim 9.
CN201610769703.XA 2016-08-30 2016-08-30 Composite material and preparation method, application, insulated wall connector and bar Active CN106366578B (en)

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CN109694554A (en) * 2018-12-29 2019-04-30 惠柏新材料科技（上海）股份有限公司 A kind of resin combination of fast pultrusion fibre reinforced composites
CN110539508A (en) * 2019-10-11 2019-12-06 泰安市骏鸣新材料有限公司 High-strength fiber reinforced composite material connecting piece, formula and manufacturing process thereof
CN110790565A (en) * 2019-10-30 2020-02-14 中冶建筑研究总院有限公司 Nonmetal shear connector, preparation method and wall structure using connector

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109694554A (en) * 2018-12-29 2019-04-30 惠柏新材料科技（上海）股份有限公司 A kind of resin combination of fast pultrusion fibre reinforced composites
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
CN110539508A (en) * 2019-10-11 2019-12-06 泰安市骏鸣新材料有限公司 High-strength fiber reinforced composite material connecting piece, formula and manufacturing process thereof
CN110790565A (en) * 2019-10-30 2020-02-14 中冶建筑研究总院有限公司 Nonmetal shear connector, preparation method and wall structure using connector

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