CN107446304B - The method of phenolic resin preimpregnation material and its manufacture phenolic composite - Google Patents

The method of phenolic resin preimpregnation material and its manufacture phenolic composite Download PDF

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Publication number
CN107446304B
CN107446304B CN201610366860.6A CN201610366860A CN107446304B CN 107446304 B CN107446304 B CN 107446304B CN 201610366860 A CN201610366860 A CN 201610366860A CN 107446304 B CN107446304 B CN 107446304B
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phenolic resin
prepreg
phenolic
resin
composite
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CN107446304A (en
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陈精明
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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
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/10—Next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/10—Layered products comprising a layer of natural or synthetic rubber next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/20—Layered products comprising a layer of natural or synthetic rubber comprising silicone rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Textile Engineering (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses the methods of a kind of phenolic resin preimpregnation material and its manufacture phenolic composite, and prepreg includes following components in parts by weight: 50~65 parts of fabric, 20~48 parts of phenolic resin, 1~5 part of thickener.The method of phenolic resin preimpregnation material manufacture phenolic composite uses the cured technique of vacuum bag, uses microporous barrier in the process, and the micropore size of the microporous barrier is 0.1~10um, and with a thickness of between 2~300um, porosity is 50%~80%；Since micropore size is up to ten thousand times of fluid molecule diameter, hundred times smaller than drop diameter, therefore there is excellent moisture-inhibiting, ventilative and anti-drop permeability, escaping gas is extracted when to vacuumize, and liquid resin component will not be extracted, avoiding resin from being extracted leads to the non-uniform problem of resin distribution, reduces waste of material and waste.

Description

The method of phenolic resin preimpregnation material and its manufacture phenolic composite
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of phenolic resin preimpregnation material, phenolic resin preimpregnation material Preparation method and prepreg manufacture phenolic composite method.
Background technique
Phenolic resin is the artificial resin of first commercial applications in human history, because it is with good heat resistance Energy, flame retardant property, corrosion resistance (except oxidisability bronsted lowry acids and bases bronsted lowry), high-temperature creep resistance, are all widely applied, such as so far It is used to prepare a variety of heat resistant articles, anticorrosion material, fire proofing etc..
After phenolic resin curing, aromatic ring is fine and close on molecular structure, encounters high fever and burns the layer of charcoal of densification easy to form, slows down Intrusion of the heat to material internal, has also completely cut off the entrance of oxygen；The cigarette that the calory burning released when therefore burning is low, discharges Mist is few, and the toxicity of smog is low, shows excellent flame retardant property (FST).Due to the anti-flammability of phenolic resin itself Can be splendid, so not needing to add various fire retardants as other flame-retarded resins, such as halogen, nitrogenous class, containing Phosphorus；Or tree The elements such as nitrogen, phosphorus are introduced in the molecular structure of rouge.From various countries to the toxicity requirements of material, such as Britain's rail traffic standard BS6853 Appendix D, Boeing standard BSS7239, all to CO, CO2、HF、HCl、HBr、HCN、NO2、SO2The release of eight kinds of gases is dense Degree is strictly limited.Phenolic resin does not need outer addition fire retardant, so general performance comes out due to the flame-retarding characteristic of itself FST performance be optimal in all organic materials.
Phenolic resin is usually used in preparing aviation, the interior material in rail traffic with its excellent flame retardant property.But phenolic aldehyde Material has its weakness, that is, belongs to fragile material, poor toughness；In addition, material can discharge hydrone during curing molding, these Moisture is generally difficult to whole discharges, and causing material internal, there are many micropores, to influence the mechanical strength of phenolic materials.Therefore Around phenolic materials toughening and intensity is improved, numerous researchers have carried out a large amount of research to it, also achieved many achievements.
In recent years, phenolic resin preimpregnation material is widely used in the preparation of aircraft interior material, phenolic resin preimpregnation material system It is convenient to make product, product strength, flame retardant property are all more satisfactory.
There are mainly two types of ie in solution infusion process and Hot-melt film methods for the preparation method of prepreg.Solution dipping method is by fiber Or fabric is after resin solution impregnates, the technique that the solvent in resin is vapored away, and prepreg is made to reach B-stage；The method Production equipment less investment, the disadvantage is that prepreg resin content is difficult to control accurately, a large amount of solvent volatilizations form environmental pollution.Heat Melten gel embrane method is the glue film that the resin of melting is made to uniform ground first, then by glue film and fiber or fabric in certain temperature With compound dipping is carried out under pressure, obtain qualified prepreg；This technological advantage is that resin content control is accurate, fugitive constituent is few, nothing Environmental pollution；The disadvantage is that equipment investment is high.
For solution dipping method, equipment is simple, less investment, simple production process, as long as being avoided that solvent volatilizees, reduction is waved Hair part content controls prepreg resin content, can form the solution dipping method of improvement.
101735551 A(application number 200810180315.3 of Chinese patent literature CN) one kind is disclosed with high temperature power The heat-insulation composite material and preparation method thereof of performance is learned, is a kind of phenolic aldehyde prepreg on the material, main component is barium phenol Urea formaldehyde, ethyl alcohol and high strength glass fiber sheet.First high strength glass fiber sheet is cut out and is heat-treated when preparation, by barium phenolic aldehyde Resin and ethyl alcohol are mixed into resin adhesive liquid according to 60:40, dry drying after impregnation, obtain phenolic composite prepreg.
It is fire-retardant that 102731960 B of Chinese patent literature CN (application number 201210211451.0) discloses a kind of high tenacity The preparation method of phenolic aldehyde prepreg composite, by introducing thermoplastic polymer and rubber toughener into phenolic resin, The toughness of composite material is substantially increased, while introducing bromine/Sb system fire retardant and compensating under flame retardant property caused by toughener The problem of drop；Ethyl alcohol is used as diluent in disclosed preimpregnation preparation method for material simultaneously, makes phenolic resin, toughener, four The mixed viscosity of bromine bisphenol-A, antimony oxide is lower, is suitble to the impregnation to fibrous material.
104194256 A(application number 201410330863.6 of Chinese patent literature CN) in disclose a kind of toughening type ring Protect the glass fibre prepreg cloth of phenolic resin, including following component: Environmental protection phenol formaldehyde resin, alkali-free glass fiber cloth, coupling agent KH-560, Inner pattern releasing agent applicable, pigment, silica, industrial alcohol, graphite, wollastonite.
Existing solution dipping method prepares in the technology of phenolic resin preimpregnation material and uses ethyl alcohol in above-mentioned three applications As solvent.Phenolic resin curing belongs to polycondensation reaction, can generate small molecule water, and volatilization remains in material not the part gone out In, micropore is formed, to have an adverse effect to material mechanical performance and flame retardant property, so most of phenolic aldehyde prepregs all select With molecular weight phenolic resin as high as possible, to reduce the yield of phenolic aldehyde prepreg moisture when solidifying；But phenolic resin Molecular weight is higher, and viscosity is bigger, is more difficult to be impregnated with glass-fiber-fabric, so all employing ethyl alcohol in above patent document as solvent Or referred to as diluent, the viscosity for reducing phenolic resin go on smoothly impregnation.After completing impregnation, the ethyl alcohol used will lead to The problems such as crossing heating evaporation to fall, doing so " a large amount of solvent volatilizations, environmental pollution " for just producing solution dipping method；Another party Face, the ethyl alcohol in prepreg can not completely be discharged except prepreg, thus to the anti-flammability of phenolic composite have compared with Big influence.
When manufacturing composite material with prepreg, optimal method is autoclave method, and autoclave method is (general simultaneously also in relation with true Empty bag method) lower than 1%, product strength performance is best for the obtained porosity of composite product；But the cost of autoclave is very It is high.Develop the outer curing method of tank, i.e. OoA method again in recent years, vacuum bag pressure method is exactly one of.Vacuum bag pressure method can save The manufacture for removing high-cost autoclave uses common drying chamber.
Since laying can bring a certain amount of gas into existing vacuum bag pressure method technique, so in the curing process of prepreg In, it is usually laid with isolation film with holes on the surface of prepreg, adds inhale rubber mat and airfelt above；It is convenient for so under vacuum, Gas inside prepreg can be smoothly extracted.But it is also higher to inhale glue material cost, while the process for inhaling glue need to be specific In temperature range, Resin Flow cannot be excessive, and otherwise resin is extracted excessively；Resin Flow can not be too small, otherwise gas It is complete that body is not easy discharge；This requires the viscosity temperature characteristic of prepreg is extremely stable, so the control for inhaling glue process is very difficult. Importantly, these moisture are taken out in a manner of steam by inhaling glue-line since phenolic aldehyde prepreg can discharge water in solidification A certain amount of resin would generally be taken when out out of, cause resin content uneven, also result in waste of material and environmental pollution.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of phenol that the phenolic resin by low molecular weight, low viscosity is made The method of urea formaldehyde prepreg, the preparation method of phenolic resin preimpregnation material and prepreg manufacture composite material.
The technical solution for realizing an object of the present disclosure is a kind of phenolic resin preimpregnation material, in parts by weight includes with the following group Point: 50~65 parts of fabric, 20~48 parts of phenolic resin, 1~5 part of thickener.
The phenolic resin is resol, and viscosity is 300~1500mPas；The thickener be magnesia, One of calcium oxide, calcium sulfate, nano-grade aluminum hydroxide, white carbon black, boric acid, zinc borate or more than one composition.
Preferably, further including 1~10 part of curing accelerator, the curing accelerator is imidazolidine, triazine, oxazole Alkane, oxazines, imidazolidine-oxazolidine hybrid, the resorcinol of etherificate, one of the carboxylate of strong acid or more than one group Close object.Wherein the strong acid of synthetic ester is phosphoric acid, polyphosphoric acids, phosphorous acid, sulfuric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, dimethylbenzene sulphur One of acid, phenolsulfonic acid；The alcohol of synthetic ester be ethyl alcohol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerine, One of pentaerythrite, benzyl alcohol, trimethylolpropane, phenol.
It is selectable, it further include 1~8 part of toughener；The toughener is base polyurethane prepolymer for use as, methoxy radical siloxane, gathers One of vinyl alcohol, end hydroxy butadiene, carboxyl-terminated polybutadiene.
The technical solution for realizing the second purpose of the invention is a kind of preparation method of phenolic resin preimpregnation material as described above, The following steps are included:
1. weighed phenolic resin and thickener will be uniformly mixed for use in dispersator according to parts by weight；Phenolic aldehyde Resin is resol, and viscosity is 300~1500mPas；Thickener is magnesia, calcium oxide, calcium sulfate, nanoscale One of aluminium hydroxide, white carbon black, boric acid, zinc borate or more than one composition.
2. fabric is connected on impregnation unit；1. material that step is mixed pours into the resin storage tank of impregnation unit In, resin storage tank temperature control system is at 25 DEG C~80 DEG C；
3. starting impregnation unit, after fabric is impregnated with resin in resin storage tank, extraction is moved through pressure roller, enters increasing with film carrier Thick drying tunnel；Thickening drying tunnel temperature is 40 DEG C~95 DEG C, and the fabric after impregnation is 0.5~5h, thickening by the time of thickening drying tunnel It finishes to obtain phenolic resin preimpregnation material.
As optional, 1. step also weighs 1~10 part of curing accelerator and/or 1~8 part of toughener, will be according to weight The weighed phenolic resin of number, thickener, toughener and/or curing accelerator are uniformly mixed stand-by in dispersator.
The curing accelerator is between imidazolidine, triazine, oxazolidine, oxazines, imidazolidine-oxazolidine hybrid, etherificate One of the carboxylate or more than one composition of benzenediol, strong acid；The toughener is base polyurethane prepolymer for use as, methoxyl group One of siloxanes, polyvinyl alcohol, end hydroxy butadiene, carboxyl-terminated polybutadiene.
The technical solution for realizing third purpose of the present invention is that a kind of phenolic resin preimpregnation material manufacture phenolic aldehyde is compound The method of material, using the cured technique of vacuum bag, comprising the following steps:
1. prepreg is cut by required size, remove release film, lamination is successively completed on mold, is then presoaking Material surface is successively laid with porous release film, microporous barrier, gas permeable material；The micropore size of the microporous barrier is 0.1~10um, thickness Between 2~300um, porosity is 50%~80%；The lamination refers to prepreg is successively completed after obtained stacked body, press Design thickness and prepreg thickness in monolayer according to phenolic composite determine the number of plies of prepreg in lamination.
2. being laid with sealant tape in mold surrounding, one, vacuum tube is touched on gas permeable material, and other end connects external vacuum Pipeline is completed vacuum bag film and is sealed.
3. mold is integrally put into drying chamber, vacuum pump is opened, keeps pressure in -0.085~-0.01MPa；Heating is opened, 90 DEG C~160 DEG C are slowly increased to, Slow cooling demoulds after the completion of material solidification, obtains cured composite material.
Optionally, when 1. step is laid with lamination, between the adjacent two layers prepreg among lamination be laid with foam core material or Honeycomb core material or cork wood, two pieces of prepregs and in-between core material form sandwich structure.
Preferably, step also uses edge sealing member when 1. middle laying has the lamination of core material, the edge sealing member is upper and lower The vertical face thickness of perforative integrated frame shape prefabricated component, the frame shape prefabricated component is identical as the thickness of core material, the width of frame be 1 to 10cm, edge sealing member are the prefabricated profiled phenolic composite of integration.Edge sealing member is bonded the surrounding that core material is arranged in, edge sealing member Surrounding outer rim and composite element edge profile are in same facade；The prepreg lamination below core material is first completed when laying It is laid with, places edge sealing member, the horizontal plane of spread prepreg and edge elevation are compacted with edge sealing member, then core material is filled in frame In the frame of shape edge sealing member, continue the laying of the prepreg above core material and edge sealing member.
It as optional, is laid with before prepreg lamination on mold, is first successively laid with gas permeable material, microporous barrier, with holes Isolation film.
The present invention has the effect of positive:
(1) phenolic resin of the invention preimpregnation material uses the phenolic aldehyde of low viscosity (viscosity is 300~1500mPas) Resin is used directly for impregnation operation or under lower heating temperature since phenolic resin viscosity is low when preparing prepreg Impregnation is carried out, when impregnation does not need using ethyl alcohol or other organic solvent diluting phenolic resin；After the completion of the impregnation of fabric, The molecular weight that thickening improves phenolic resin is carried out at a certain temperature.Phenolic resin preimpregnation material of the invention solidifies in final molding When the moisture that generates it is few, micropore quantity is few in the composite product prepared with prepreg, quality of item is high.
(2) it is easy to operate using the phenolic resin of low molecular weight to prepare prepreg by the present invention, due to not needing using ethyl alcohol Or other organic solvents, therefore the preparation method of prepreg of the present invention solves a large amount of solvents existing for existing solution dipping method and waves The problems such as hair, environmental pollution.In addition, due to, without ethyl alcohol or other organic solvents, avoiding answering for prepreg preparation in prepreg The problem of fire block articles performance caused by dissolvent residual declines in laminate article.
(3) phenolic resin of the invention preimpregnation material uses the phenolic resin of low molecular weight as raw material, due in prepreg The molecular weight that phenolic resin can be improved while thickening operation is carried out containing thickener, after impregnation；Thickening operation is easy to control, control Thickening operation can control the molecular weight of phenolic resin in prepreg simultaneously, to obtain the prepreg of different tack sizes.
(4) curing accelerator uses allow prepreg at 100 DEG C~120 DEG C lower in prepreg of the invention At a temperature of curing molding, the lower temperature be compared with the prior art in phenolic resin 130 DEG C~160 DEG C of relatively high solidification temperature For degree；Lower solidification temperature greatly reduces energy consumption, and reduces the cost of mold.
(5) prepreg Storage period of the invention is long, can store 2 months at 25 DEG C.
(6) the cured technique of vacuum bag is used when manufacturing composite material using prepreg of the invention, the present invention is in the work Microporous barrier is used in skill, the micropore size of the microporous barrier is 0.1~10um, with a thickness of between 2~300um, porosity is 50%~ 80%；Since micropore size is up to ten thousand times of fluid molecule diameter, hundred times smaller than drop diameter, therefore have excellent moisture-inhibiting, Ventilative and anti-drop permeability, so that escaping gas is extracted when vacuumizing, and liquid resin component will not be extracted, and be avoided Resin, which is extracted, leads to the non-uniform problem of resin distribution, reduces waste of material and waste.
(7) it due to the use of microporous barrier when phenolic aldehyde prepreg of the invention manufactures composite material, reduces viscous to prepreg The strict demand of temperature characteristics and solidification temperature.
(8) present invention uses prefabricated edge sealing member, can increase the intensity at composite product edge；Meanwhile may be used also When being laid with solving prepreg, intractable property at the angle R that die edge horizontal plane intersects with facade makes composite wood obtained Material component possesses intact edge quality.
Specific embodiment
(embodiment 1)
The phenolic resin preimpregnation material of the present embodiment includes following components: 58 parts of fabric, phenolic resin in parts by weight 39 parts, 2 parts of thickener, 1 part of curing accelerator.
Fabric in the present embodiment is 800g/m2Bi-axial fabric.
Phenolic resin is resol, and the catalyst of synthetic reaction is sodium hydroxide, viscosity is 300~ It is 900 mPas in 1500mPas(the present embodiment).
The thickener is magnesia, in calcium oxide, calcium sulfate, nano-grade aluminum hydroxide, white carbon black, boric acid, zinc borate One or more kinds of compositions, the thickener of the present embodiment is calcium sulfate.
The curing accelerator is between imidazolidine, triazine, oxazolidine, oxazines, imidazolidine-oxazolidine hybrid, etherificate One of the carboxylate or more than one composition of benzenediol, strong acid.
The carboxylate of strong acid uses after being diluted by ethylene glycol in curing accelerator；The strong acid of synthetic ester is phosphoric acid, poly phosphorus One of acid, phosphorous acid, sulfuric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, xylene monosulfonic acid, phenolsulfonic acid；The alcohol of synthetic ester is second Alcohol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerine, pentaerythrite, benzyl alcohol, trimethylolpropane, in phenol One kind.The curing accelerator of the present embodiment is the triphenyl phosphite and imidazolidine that mass ratio is 1: 1.
The present embodiment phenolic resin preimpregnation material preparation method the following steps are included:
1. will according to above-mentioned parts by weight it is weighed by phenolic resin, thickener and curing accelerator in dispersator It is uniformly mixed stand-by.
2. bi-axial fabric is connected on impregnation unit；1. material that step is mixed pours into the resin of impregnation unit In slot, resin storage tank temperature control system is 35 DEG C~80 DEG C (being 60 DEG C in the present embodiment).
3. starting impregnation unit, after bi-axial fabric is impregnated with resin in resin storage tank, extraction is moved through pressure roller, is entered with film carrier Thicken drying tunnel.Thickening drying tunnel temperature is 40 DEG C~95 DEG C (being 85 DEG C in the present embodiment), and the fabric after impregnation passes through thickening drying tunnel Time be 2h, thickening finishes to obtain the phenolic resin preimpregnation material of the present embodiment.
(embodiment 2)
Remaining is same as Example 1 for the phenolic resin preimpregnation material of the present embodiment, the difference is that further including 2 parts of toughening Agent, toughener are base polyurethane prepolymer for use as.
In addition to the base polyurethane prepolymer for use as being previously mentioned, toughener can also be methoxy radical siloxane, polyvinyl alcohol, terminal hydroxy group One of polybutadiene, carboxyl-terminated polybutadiene.
(embodiment 3)
The phenolic resin preimpregnation material of the present embodiment is composed of the following components in parts by weight: 55 parts of fabric, phenolic aldehyde tree 42 parts of rouge, 3 parts of thickener, 2 parts of curing accelerator.
Wherein fabric is 200g/m2Glass satin fabric.
Phenolic resin is the resol catalyzed and synthesized with barium hydroxide, viscosity 1200mPas.
Thickener is boric acid.
Curing accelerator is the carboxylate and oxazolidine of polyphosphoric acids and trimethylolpropane.
Remaining is same as Example 1 for the preparation method of the phenolic resin preimpregnation material of the present embodiment, the difference is that:
Step 2. resin storage tank temperature control system at 65 DEG C.
3. it is 90 DEG C that step thickens drying tunnel temperature, and the fabric after impregnation is 1h by the time of thickening drying tunnel.
(embodiment 4)
The phenolic resin preimpregnation material of the present embodiment is composed of the following components in parts by weight: 50 parts of fabric, phenolic aldehyde tree 45 parts of rouge, 2 parts of thickener, 3 parts of curing accelerator.
Wherein fabric is 400g/m2Carbon fiber plain cloth.
Phenolic resin is the resol with magnesium oxide catalyzed synthesis, viscosity 1000mPas.
Thickener is zinc borate.
Curing accelerator is diphenyl phosphate and triazine.
Remaining is same as Example 1 for the preparation method of the phenolic resin preimpregnation material of the present embodiment, the difference is that:
Step 2. resin storage tank temperature control system at 63 DEG C.
3. it is 90 DEG C that step thickens drying tunnel temperature, and the fabric after impregnation is 1h by the time of thickening drying tunnel.
(embodiment 5)
The phenolic resin preimpregnation material of the present embodiment is composed of the following components in parts by weight: 2 parts of fabric, phenolic resin 44 parts, 3 parts of thickener.
Wherein fabric is 400g/m2Twill.
Phenolic resin is the resol synthesized with ammonia-catalyzed, viscosity 1400mPas.
Thickener is magnesia.
Curing accelerator is carboxylate and imidazolidine-oxazolidine hybrid of polyphosphoric acids and trimethylolpropane.
Remaining is same as Example 1 for the preparation method of the phenolic resin preimpregnation material of the present embodiment, the difference is that:
Step 2. resin storage tank temperature control system at 60 DEG C.
3. it is 95 DEG C that step thickens drying tunnel temperature, and the fabric after impregnation is 1h by the time of thickening drying tunnel.
(embodiment 6)
The phenolic resin preimpregnation material of the present embodiment is composed of the following components in parts by weight: 51 parts of fabric, phenolic aldehyde tree 41 parts of rouge, 2 parts of thickener, 3 parts of curing accelerator, 3 parts of toughener.
Wherein fabric is 500g/m2Bi-axial fabric.
Phenolic resin be Chinese patent literature CN 104356325A(application number 201410593338.2) disclosed in nanometer layer The modified phenolic resin of shape silicate clay, viscosity 600mPas.
Thickener is the white carbon black and nano-grade aluminum hydroxide that mass ratio is 1:1.
Curing accelerator is the carboxylate and resorcinolformaldehyde resin of polyphosphoric acids and trimethylolpropane.
Toughener is methoxy radical siloxane.
Remaining is same as Example 1 for the preparation method of the phenolic resin preimpregnation material of the present embodiment, the difference is that:
Step 2. resin storage tank temperature control system at 60 DEG C.
3. it is 93 DEG C that step thickens drying tunnel temperature, and the fabric after impregnation is 0.5h by the time of thickening drying tunnel.
(embodiment 7)
The phenolic resin preimpregnation material of the present embodiment is composed of the following components in parts by weight: 50 parts of fabric, phenolic aldehyde tree 45 parts of rouge, 1 part of thickener, 2 parts of curing accelerator, 2 parts of toughener.
Wherein fabric is 250g/m2Twill.
Phenolic resin is the resol with sodium hydroxide catalyzed synthesis, viscosity 1000mPas.
Thickener is the calcium sulfate and zinc borate that mass ratio is 1:1.
Curing accelerator is the carboxylate of strong acid, and the acid of synthetic ester is phosphoric acid, and the alcohol of synthetic ester is polypropylene glycol；When use It is used after carboxylate spent glycol dilution, the mass ratio of carboxylate and ethylene glycol is 5:1.
Toughener is carboxyl-terminated polybutadiene.
Remaining is same as Example 1 for the preparation method of the phenolic resin preimpregnation material of the present embodiment, the difference is that:
Step 2. resin storage tank temperature control system at 60 DEG C.
3. it is 9 DEG C that step thickens drying tunnel temperature, and the fabric after impregnation is 1h by the time of thickening drying tunnel.
Embodiment 1 to 7, which thickens the material finished, can be made into the soft solid coiled material for possessing different viscosity, illustrate thickening effect Fruit is ideal, reaches the Typical physical performance of prepreg.
Performance such as the following table 1 that the phenolic resin preimpregnation of embodiment 1 to embodiment 7 is expected:
Table 1
(embodiment 8, the method that material manufacture phenolic composite is presoaked by phenolic resin)
The present embodiment manufactures phenolic composite and uses the cured technique of vacuum bag, uses the phenolic resin prepolymer of embodiment 1 Leaching material, comprising the following steps:
1. successively completing gas permeable material, microporous barrier, porous release film on mold.
The gas permeable material is one of organic fabrix, inorganic fibre fabric；The micropore membrane material is thermoplastic Property polyurethane, polytetrafluoroethylene (PTFE), one of silicon rubber, the micropore size of microporous barrier is 0.1~10um, with a thickness of 2~100um Between, porosity is 50%~80%；Porous release film is polyethylene film, and aperture is 0.1~0.3mm, punching spacing is 3~ 10mm。
2. the prepreg of embodiment 1 is cut by required size, remove release film, on the porous release film of step 1. Complete lamination (prepreg of 3 layers of embodiment 1 is laid in the present embodiment).The lamination refers to the design according to phenolic composite Thickness and prepreg thickness in monolayer determine the number of plies of prepreg in lamination, the stacked body obtained after prepreg is successively completed.
Further, during above-mentioned laying lamination, bubble can also be overlayed between the adjacent two layers prepreg among lamination Foam core material or honeycomb core material or cork wood, make sandwich structure.
Further, edge sealing member is also used when being laid with the lamination for having core material, the edge sealing member is one up and down Body frame shape prefabricated component, the thickness of the vertical guide of the frame shape prefabricated component is identical as the thickness of core material, and the width of frame is 1 to 10cm, Edge sealing member is the prefabricated phenolic composite of integration.Edge sealing member is fitted in the edge of core material, the edge of edge sealing member Profile and composite element edge profile are in same facade.The bottom prepreg lamination below core material is completed when laying After laying, it will usually which needs are laid at the edge of these bottom prepregs along the facade of die edge upwards, die horizontal face The prepreg at the angle R that intersects with edge elevation is easy to tilt, and places edge sealing member, with edge sealing member by the water of institute's shop fixtures layer prepreg Then core material is filled in the frame of frame shape edge sealing member on the horizontal plane and facade of mold, continues core by plane and facade compacting The laying of prepreg above material and edge sealing member.
Due to the setting of edge sealing member, in the vacuum in later period, core material surrounding is not allowed to be also easy to produce displacement and stitch Gap, so that final composite element be avoided to generate cavitation damage in surrounding facade.
3. step 2. phenolic resin preimpregnation material lamination outer surface on be successively laid with porous release film, microporous barrier, thoroughly Gas material, wherein microporous barrier needs completely to coat prepreg build-up surface.
4. being laid with sealant tape in mold surrounding, one, vacuum tube is touched on gas permeable material, and other end connects external vacuum Pipeline is completed vacuum diaphragm and is sealed.
5. mold is integrally put into drying chamber, vacuum pump is opened, keeps pressure in -0.085~-0.01MPa；Heating is opened, 90 DEG C~160 DEG C (they being 100~120 DEG C in the present embodiment) are slowly increased to, and Slow cooling demoulds after the completion of material solidification, consolidate The phenolic composite of change.
In prepreg used in the present embodiment due to containing curing accelerator, prepreg can 100 DEG C~120 DEG C compared with Curing molding under low temperature, the lower temperature are 130 DEG C~160 DEG C of relatively high solidifications of middle phenolic resin compared with the prior art For temperature；It is the case where for being free of curing accelerator in prepreg, higher at 130 DEG C~160 DEG C when preparing composite material At a temperature of curing molding.
Likewise, according to the method described above, the prepreg of embodiment 2 to embodiment 7 is manufactured into phenolic composite plate； To the method according to embodiment 8 by embodiment 1 to embodiment 7 prepreg manufacture composite material flat plate flame retardant property and machinery Performance is detected:
(1) according to the stretching and punching of GB1447-2005, GB1451-2005 standard detection phenolic resin composite plate Hit performance.
(2) 60 seconds vertical combustions.
Using VC-2 type vertical combustion analyzer, tested by BSS7230.
(3) smoke density.
Using SD-1 type smoke density case, tested by BSS7238.
Above-mentioned 3 testing results see the table below 2:
Table 2
Note: the embodiment 1 of the first row refers to multiple made of the prepreg of embodiment 1 according to the method for embodiment 8 in table 2 Condensation material plate, embodiment 2 to 7 is similarly.
(embodiment 9, the method that material manufacture phenolic composite is presoaked by phenolic resin)
The present embodiment manufactures phenolic composite and uses the cured technique of vacuum bag, uses the phenolic resin prepolymer of embodiment 1 Leaching material, comprising the following steps:
1. prepreg is cut by required size, remove release film, successively completes on mold and be made of 6 layers of prepreg Lamination, be then successively laid with porous release film, microporous barrier, gas permeable material on prepreg surface；Wherein microporous barrier needs will be pre- Leaching material build-up surface coats completely.The micropore size of the microporous barrier is 0.1~10um, with a thickness of between 2~300um, hole Rate is 50%~80%；The lamination refers to prepreg is successively completed after obtained stacked body.
Further, during above-mentioned laying lamination, bubble can also be overlayed between the adjacent two layers prepreg among lamination Foam core material or honeycomb core material or cork wood, make sandwich structure.
Further, edge sealing member described in embodiment 8 is also used when being laid with the lamination for having core material.
2. being laid with sealant tape in mold surrounding, one, vacuum tube is touched on gas permeable material, and other end connects external vacuum Pipeline is completed vacuum diaphragm and is sealed.
3. mold is integrally put into drying chamber, vacuum pump is opened, keeps pressure in -0.085~-0.01MPa；Heating is opened, 90 DEG C~160 DEG C (being 120 DEG C in the present embodiment) are slowly increased to, Slow cooling demoulds after the completion of material solidification, obtains cured Phenolic composite.
Compared with the preparation method of embodiment 8, the present embodiment only lamination side be laid with porous release film, microporous barrier and Another side surface of gas permeable material, lamination is directly contacted with die surface, due to die surface be it is smooth, the present embodiment can be with Obtain the composite material of side shiny surface.
For the preparation method of embodiment 8, due to the two sides of lamination be all provided with auxiliary material i.e. porous release film, microporous barrier and Gas permeable material, therefore obtained composite material both side surface has a texture of auxiliary material, but when two sides are all laid with the mode of auxiliary material and prepare Exhaust or steam discharge effect are more preferable.
For there is the case where core material in lamination, when laying, uses edge sealing member, on the one hand this is because the edge of core material Opposite prepreg is fragile, increases intensity with edge sealing member；Using for another aspect edge sealing member makes in the vacuum in later period, Core material surrounding is not allowed to be also easy to produce displacement and gap occurs, and lacks so that final composite element be avoided to generate hole in surrounding facade It falls into.
(comparative example 1)
This comparative example manufactures phenolic composite and uses the cured technique of conventional vacuum bag, with the phenolic resin of embodiment 1 For prepreg, preparation process the following steps are included:
1. prepreg is cut by required size, remove release film, lamination is successively completed on mold (in this comparative example Be 3 layers), then prepreg build-up surface successively porous release film, inhale rubber mat several layers, gas permeable material.
2. being laid with sealant tape in mold surrounding, one, vacuum tube is touched on gas permeable material, and other end connects external vacuum Pipeline is completed vacuum bag film and is sealed.
3. mold is integrally put into drying chamber, vacuum pump is opened, keeps pressure in -0.085~-0.01MPa；Heating is opened, 120 DEG C are slowly increased to, Slow cooling demoulds after the completion of material solidification, obtains cured phenolic composite.
Microporous barrier is not used in this comparative example, using the exhaust for inhaling rubber mat and carrying out solidification process, air that when laying carries secretly, Solidify the steam released to be extracted by the hole of porous release film.
Rubber mat is inhaled in observation, the portion for inhaling rubber mat observes the resin for being solidified into rufous, is illustrated in air, steam Fraction phenolic resin is carried in exhaust process secretly, these phenolic resin, which are accumulated in, inhales rubber mat layer, absorbs the suction of phenolic resin Rubber mat cannot be recycled.The cured technique of traditional vacuum bag had both caused the waste of prepreg resin, also added into Sheet and waste quantity.

Claims (9)

1. a kind of phenolic resin preimpregnation material, it is characterised in that in parts by weight include following components: 50~65 parts of fabric, phenol 20~48 parts of urea formaldehyde, 1~5 part of thickener, 1~10 part of curing accelerator；
The curing accelerator be imidazolidine, triazine, oxazolidine, oxazines, imidazolidine-oxazolidine hybrid, etherificate isophthalic two One of the carboxylate or more than one composition of phenol, strong acid；
The strong acid for wherein synthesizing carboxylate is phosphoric acid, polyphosphoric acids, phosphorous acid, sulfuric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, dimethylbenzene One of sulfonic acid, phenolsulfonic acid；The alcohol for synthesizing carboxylate is ethyl alcohol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, third One of triol, pentaerythrite, benzyl alcohol, trimethylolpropane, phenol.
2. phenolic resin preimpregnation material according to claim 1, it is characterised in that: the phenolic resin is first rank phenolic aldehyde tree Rouge, viscosity are 300~1500mPas；The thickener is magnesia, calcium oxide, calcium sulfate, nano-grade aluminum hydroxide, hard charcoal One of black, boric acid, zinc borate or more than one composition.
Expect 3. being presoaked according to claim 1 to phenolic resin described in one of 2, it is characterised in that: further include 1~8 part of toughener； The toughener is base polyurethane prepolymer for use as, methoxy radical siloxane, polyvinyl alcohol, end hydroxy butadiene, carboxyl-terminated polybutadiene One of.
4. a kind of preparation method of phenolic resin preimpregnation material as described in claim 1, it is characterised in that the following steps are included:
1. will according to parts by weight weighed phenolic resin, thickener and curing accelerator in dispersator be uniformly mixed to With；Phenolic resin is resol, and viscosity is 300~1500mPas；Thickener be magnesia, calcium oxide, calcium sulfate, One of nano-grade aluminum hydroxide, white carbon black, boric acid, zinc borate or more than one composition；
2. fabric is connected on impregnation unit；1. material that step is mixed pours into the resin storage tank of impregnation unit, Resin storage tank temperature control system is at 25 DEG C~80 DEG C；
3. starting impregnation unit, after fabric is impregnated with resin in resin storage tank, extraction is moved through pressure roller, enters thickening with film carrier and dries Road；Thickening drying tunnel temperature is 40 DEG C~95 DEG C, and the fabric after impregnation is 0.5~5h by the time of thickening drying tunnel, and thickening finishes Obtain phenolic resin preimpregnation material.
5. the preparation method of phenolic resin preimpregnation material according to claim 4, it is characterised in that: 1. step also weighs toughening 1~8 part of agent, will according to parts by weight weighed phenolic resin, thickener, toughener and curing accelerator in dispersator It is uniformly mixed stand-by；
The curing accelerator be imidazolidine, triazine, oxazolidine, oxazines, imidazolidine-oxazolidine hybrid, etherificate isophthalic two One of the carboxylate or more than one composition of phenol, strong acid；The toughener is base polyurethane prepolymer for use as, methoxyl group silicon oxygen One of alkane, polyvinyl alcohol, end hydroxy butadiene, carboxyl-terminated polybutadiene.
6. a kind of method for presoaking material manufacture phenolic composite by phenolic resin described in claim 1, using vacuum bag pressure Curing process, it is characterised in that the following steps are included:
1. prepreg is cut by required size, remove release film, lamination is successively completed on mold, then in prepreg table Face is successively laid with porous release film, microporous barrier, gas permeable material；The micropore size of the microporous barrier is 0.1~10um, with a thickness of 2 Between~300um, porosity is 50%~80%；The lamination refers to the design thickness and preimpregnation material list according to phenolic composite Thickness degree determines the number of plies of prepreg in lamination, the stacked body obtained after prepreg is successively completed；
2. being laid with sealant tape in mold surrounding, one, vacuum tube is touched on gas permeable material, and other end connects external vacuum pipeline, It completes vacuum bag film and seals；
3. mold is integrally put into drying chamber, vacuum pump is opened, keeps pressure in -0.085~-0.01MPa；Heating is opened, slowly 90 DEG C~160 DEG C are risen to, Slow cooling demoulds after the completion of material solidification, obtains cured composite material.
7. the method for phenolic resin preimpregnation material manufacture phenolic composite according to claim 6, it is characterised in that: step 1. be laid with lamination, laying foam core material or honeycomb core material or cork wood between the adjacent two layers prepreg among lamination, two pieces Prepreg and in-between core material form sandwich structure.
8. the method for phenolic resin preimpregnation material manufacture phenolic composite according to claim 7, it is characterised in that: step 1. edge sealing member is also used when being laid with the lamination for having core material in, the edge sealing member is upper and lower perforative integrated frame shape prefabricated component, envelope Edge pieces is bonded the surrounding that core material is arranged in, and the edge profile of edge sealing member is with composite element edge profile same Facade；
Prepreg lamination below core material is first completed when laying to be laid with, places edge sealing member, with edge sealing member by the water of spread prepreg Core material, is then filled in the frame of frame shape edge sealing member by plane and edge elevation compacting, pre- above continuation core material and edge sealing member Soak the laying of material.
9. the method for the preimpregnation material manufacture phenolic composite of the phenolic resin according to one of claim 6 to 8, feature exist In: before being laid with prepreg lamination on mold, first successively it is laid with gas permeable material, microporous barrier, porous release film.
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