CN102690494B - Phenolic resin composition and foaming material prepared from same - Google Patents
Phenolic resin composition and foaming material prepared from same Download PDFInfo
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- CN102690494B CN102690494B CN201210189851.6A CN201210189851A CN102690494B CN 102690494 B CN102690494 B CN 102690494B CN 201210189851 A CN201210189851 A CN 201210189851A CN 102690494 B CN102690494 B CN 102690494B
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Abstract
The invention relates to a phenolic resin composition and a foaming material prepared from the same. The phenolic resin composition comprises solid phenolic resin and foaming resin beads, wherein the foaming base resin adopted by the foaming resin beads are resin with thermal deformation temperature higher than 90 DEG C under a 0.45MPa load. The phenolic resin composition has no problem of short storage period. The foaming material provided by the invention comprises a crosslinked phenolic resin matrix and foaming resin beads dispersed in the crosslinked phenolic resin matrix and is prepared from the phenolic resin composition. The foaming material has lower heat conduction coefficient and excellent flame retardant property. A formed material prepared from the foaming material provided by the invention can be used as an insulation material, a sound-proof material, a vibration-absorptive material, a wood-imitating material and the like which do not combust when meeting flame.
Description
Technical field
The present invention relates to a kind of phenol resin composition, further, relate to a kind of foam material prepared by this phenol resin composition.
Background technology
Because building energy consumption is higher, when present energy day is becoming tight, carrying out energy-saving heat preserving to buildings is a required measure.
Phenolic aldehyde foam thermal insulation material good flame retardation effect, does not drip, does not burn, do not have toxic and harmful to release under naked light condition, but its fragility is large, easily efflorescence, makes transport and construction have certain difficulty, limits its application.
The method of current use is by phenol formaldehyde foam and polystyrene foam composition composite foam material, prepares the lagging material simultaneously with the flame retardant resistance of phenolic aldehyde and the heat-insulating property of polystyrene foamed.Because the heat resisting temperature of expanded polystyrene bead is lower than 90 DEG C, so at present in preparation process, the resol adopted is all liquid phenolic resin, namely adopts and the method for expanded polystyrene bead and liquid phenolic resin mixing is prepared the composite foam material of phenol formaldehyde foam and polystyrene foam composition and corresponding sheet material.But due to the obtained structure of final sheet material and the wayward of preparation process; the application of this method is restricted; such as; the resin plate structure that this method obtains is uneven; the density of expanded polystyrene bead is far smaller than liquid phenolic resin, when resol does not solidify completely, especially in the Foaming of phenolic resin stage; expanded polystyrene bead can float, and highdensity resol can sink.Prepared resin plate is cut open and will be found, the expanded polystyrene bead on sheet material top, more than bottom, causes sheet material top frangible.The simultaneously foaming of resol is also uneven, and the expansion phase at sheet material top is more free for bottom, causes the mechanical property on sheet material top poorer.And due to the preservation period of expanded polystyrene bead and liquid phenolic resin composition short, limit the output of expanded polystyrene bead and liquid phenolic resin composition, cannot the corresponding resin plate of large batch of production, cause resin plate to be difficult to suitability for industrialized production.
Patent GB2013209 is in order to overcome the uneven shortcoming of final resin plate structure, liquid towards resol and the component such as solidifying agent and whipping agent thereof have carried out strict regulation, the foaming of resol or expansion process are separated with its curing schedule, simultaneously very strict to the control of the temperature of each step in whole preparation process, so whole preparation process heat-processed is complicated, restriction for temperature is very strict, but the preservation period not solving expanded polystyrene bead and liquid phenolic resin composition is short, cannot produce the shortcoming of corresponding resin plate in large quantity.
Summary of the invention
In order to solve problems of the prior art all sidedly, the present inventor is by systematically studying discovery, solid phenolic resin must be adopted in the process preparing resol/expanded resin beads matrix material, but also must ensure in the melting process of solid phenolic resin, the not softening bubble that collapses of expanded bead of resin material.The resin expanded bead mixing more than 90 DEG C by solid phenolic resin and heat-drawn wire, and by after phenolic resin curing, the foam material of even structure, flame retardant properties and excellent thermal insulation performance just can be prepared.Owing to adopting the heat-drawn wire of solid phenolic resin and expanded resin beads high, so the problem that resol of the present invention/expanded resin beads composition does not have preservation period short, also not by the impact of condition of cure, preparation technology is simple, be easy to industrialization, easy to utilize, the cost of product is not high, excellent performance, can as the incombustible sound-proof material of chance naked light, cushioning material, imitated wood material etc., especially can use as the incombustible lagging material of the chance naked light of various highly effective and safe, such as can be incombustible as the chance naked light of building trade, the heat preservation plate material of safety uses.
Therefore, first object of the present invention is to provide a kind of phenol resin composition, the problem that said composition does not have preservation period short.
Second object of the present invention is to provide a kind of foam material and preparation method thereof, and this foam material has low thermal conductivity and excellent flame retardant properties.
3rd object of the present invention is to provide a kind of formed material, and this formed material can as uses such as the incombustible lagging material of chance naked light, sound-proof material, cushioning material, imitated wood materials.
Phenol resin composition of the present invention, comprise solid phenolic resin and expanded resin beads, the foaming base resin that described expanded resin beads adopts be under 0.45MPa load heat-drawn wire higher than 90 DEG C, preferably higher than 100 DEG C, more preferably higher than the resin of 110 DEG C.
The heat-drawn wire of macromolecular material being used as foaming base resin is tested according to GB/T 1634-2004, and testing load used is 0.45MPa, temperature rise rate (120 ± 10) DEG C/h.
The volume ratio of solid phenolic resin and expanded resin beads is 5 ︰ 95 ~ 95 ︰ 5, preferably 5 ︰ 95 ~ 80 ︰ 20, more preferably 5 ︰ 95 ~ 40 ︰ 60.
Above-mentioned resol is prepared by polycondensation phenol and aldehyde.The kind of the present invention to resol does not limit, and can be heat-reactive phenolic resin, also can be novolac resin.
For the preparation of the phenols of described resol, there is no particular limitation, such as can comprise following in any one: phenol, ortho-cresol, meta-cresol, p-cresol, phlorol, m-ethylphenol, p-ethyl phenol, o-propylphenol, between propylphenol, n-propyl phenol, to sec-butyl phenol, p-tert-butylphenol, p-cyclohexylphenol, para-chlorophenol, o-bromophenol, m-bromoacetophenone, p bromophenol, naphthyl alcohol, 2-Naphthol, Resorcinol, pyrocatechol, Resorcinol, 2, two (4 '-hydroxy phenyl) propane of 2-, two (hydroxy phenyl) methane, two (hydroxynaphenyl) methane, tetramethyl biphenyl phenol, xenol, three (hydroxy phenyl) methane etc.Wherein, preferred phenol.These phenol can be used alone or with it two or more any combination use.
For the preparation of the aldehyde of described resol kind also without any restriction, such as can comprise following in any one: formaldehyde, paraformaldehyde, trioxymethylene, acetaldehyde, paraldehyde, furfural, phenyl aldehyde etc.These aldehyde can be used alone or with it two or more any combination use.
The solid phenolic resin that the present invention uses can be powdery or particulate state, can be commercially available powdered phenol-formaldehyde resin, uses after also commercially available solid phenolic resin can being pulverized with industrial conventional any disintegrating apparatus.
Above-mentioned foaming base resin comprises at least one in following various resin: (1) olefin homo and/or olefin copolymer; (2) poly(4-methyl-1-pentene); (3) polyamide resin and/or its modified product; (4) polycarbonate resin and/or its modified product; (5) homopolymerization and/or copolymerized methanal; (6) different monounsaturated dicarboxylic acid and dibasic alcohol are by the obtained linear polyester of polycondensation; (7) aromatic ring polymer, the i.e. polymkeric substance that is only made up of aromatic ring and linking group of molecule, as polyphenyl, polyphenylene oxide, polyphenylene sulfide, polyarylsulphone, poly aryl ketone, Aromatic polyester, aromatic polyamides; (8) heterocyclic polymer, namely molecular backbone chain also has except aromatic ring the macromolecular material of heterocycle, as polybenzimidazole; (9) fluoropolymer etc.
Foaming base resin preferably includes at least one in olefin homo and/or olefin copolymer, as: (1) alfon and/or propylene copolymer; (2) Alathon and/or ethylene copolymer.
Foaming base resin more preferably comprises at least one in alfon and/or propylene copolymer.
The expansion ratio of above-mentioned expanded resin beads is 0.5 ~ 100 times, preferably 1 ~ 70 times, is more preferably 1 ~ 50 times.
The expansion ratio b of expanded resin beads is by the density p by base resin
1divided by the apparent density ρ of expanded resin beads
2(b=ρ
1/ ρ
2) obtain.The apparent density ρ of expanded resin beads
2be determined as follows: about 5g expanded resin beads is left standstill 48 hours at 23 DEG C in an atmosphere, gets a graduated cylinder, by expanded resin beads in 23 DEG C of water be immersed in this graduated cylinder.From the apparent volume of the increment determination expanded resin beads of this volume (v).The quality (m) of bead just can be obtained apparent density (ρ divided by its apparent volume
2=m/v).
The preparation method of expanded resin beads of the present invention, without any restriction, as long as the requirement meeting expansion ratio is just passable, such as, can adopt extrusion foaming or autoclave foam process to be prepared.
The method wherein adopting extrusion foaming technique to prepare expanded resin beads can adopt method as described in patent CN1188264C, CN1861368A, CN101352923B to carry out.After concrete grammar comprises and one or more base resins (such as one or more polypropylene) and whipping agent being mixed, melt extruded by extrusion system, ensure in extrusion that the temperature and pressure condition of extrusion system is enough to maintenance resin and whipping agent is homogeneous phase molten state or melting dispersion in extrusion, then the resin mixed and whipping agent through extruding dies extrusion foaming and pelletizing, finally obtained expanded resin beads.
The whipping agent used can be pneumatogen or chemical foaming agent.
Pneumatogen can be injected in base resin with the form of gas, supercutical fluid or liquid.Consider the distribution of the toxicity of whipping agent, vapour pressure, process difficulty or ease and the solvability of base resin used, preferably non-combustible, nontoxic, the whipping agent that do not consume ozone is as carbonic acid gas, nitrogen, water, SF
6, nitrous oxide, argon gas, helium, rare gas element as xenon, air (nitrogen and oxygen admixture), and the adulterant of these materials, also can select flammable whipping agent as pentane, butane and other organic materialss.Other suitable pneumatogens comprise, such as hydrofluoric ether (hydrofluorocarbons, HFC), chlorine hydrofluoric ether (hydrochlorofluorocarbons, HCFC) and perfluorination or partially fluorinated ether.
Chemical foaming agent adds in polymkeric substance at lower than the temperature of foaming agent decomposition temperature, generally adds in base resin before entering forcing machine.The chemical foaming agent activation when resin is heated to above foaming agent decomposition temperature, whipping agent decomposes release gas as N
2, CO
2and/or H
2o.Whipping agent can be following material but be not limited only to following material: azo, carbonic ether and hydrazide-based molecules; comprise azodicarbonamide, Diisopropyl azodicarboxylate, benzol sulfohydrazide, 4; 4-oxybenzene sulfonyl base-Urea,amino-, p-toluenesulfonyl-Urea,amino-, Barium azodicarboxylate, N; N '-dimethyl N, N ' dinitroso pentamethylene tetramine and trihydrazinotriazine etc.
Foaming agent consumption regulates according to the expansion ratio of required foamex.
Extrusion foaming technique is adopted to prepare in the process of expanded resin beads and can also add Nucleating Agent as required, Nucleating Agent can be following material but be not limited only to following material: silicon-dioxide, calcium carbonate, talcum powder, zinc oxide, borax, zinc borate, aluminium hydroxide, magnesium oxide, carbon black, phenylformic acid, o-2 potassium acid, terephthalic acid, benzene sulfonic acid sodium salt, Sodium Benzoate, y-bend benzyl sorbitol etc., its consumption is generally 0.01% ~ 5% of base resin weight.
Adopt extrusion foaming technique to prepare in the process of expanded resin beads and can also add conventional general plastic processing additives as required, as oxidation inhibitor, aid anti-oxidants, lubricant, look mother etc., consumption is conventional amount used.
Adopting extrusion foaming technique to prepare expanded resin beads forcing machine used can be one in single screw extrusion machine, two serial single-screw extruders, parallel dual-screw extruding machine, parallel dual-screw extruding machine Series Sheet screw extrusion press, counter rotation twin screw extruder, conical double screw extruder, three-screw extruder.
The method adopting autoclave foam process to prepare expanded resin beads can adopt the method as described in patent CN1474849 to carry out.Such as can adopt and base resin is prepared into resin particle by any applicable known method, then, with whipping agent, this resin particle be foamed, obtain the resin beads of final foaming.Wherein common foaming method can be adopted to carry out by the step that whipping agent makes this resin particle foam, such as in an encloses container, deposit in case at whipping agent, by this dispersing resin microparticles in dispersion medium, then heat whipping agent is flooded in resin particle.Under the pressure and temperature of this encloses container being remained on the pressure condition and temperature condition being enough to this resin particle is foamed, then with this understanding the component in encloses container is discharged in a kind of atmosphere of the pressure lower than the pressure in this encloses container, thus obtains the resin beads of foaming.
Above-mentioned dispersion medium can be any dispersion medium, as long as it can make this dispersing resin microparticles in wherein but do not dissolve this resin particle.The example of this dispersion medium comprises water, ethylene glycol, methyl alcohol, glycerine, ethanol or its mixture.Preferred a kind of aqueous dispersion medium.
In order to prevent each other melt bonded of resin particle in foaming process, a kind of dispersion agent of micro-solid of organic or inorganic generally can also be added in dispersion medium.General employing inorganic powder materials, such as clay mineral (such as kaolin, mica, clay) that is natural or synthesis, alumina, titanium dioxide, magnesium basic carbonate, zinc subcarbonate, calcium carbonate and magnesium oxide etc.For the resin particle of every 100 weight parts, the consumption of dispersion agent is generally 0.001 ~ 5 weight part.
Adopting autoclave foam process to prepare expanded resin beads whipping agent used can be the inorganic pneumatogen of the organic pneumatogen of any one or any one or its mixture.Wherein organic physical blowing agents can be following but be not limited only to following material: propane, butane, pentane, hexane and heptane, alicyclic hydro carbons such as tetramethylene and hexanaphthene, and halogenated hydrocarbon such as chlorofluoromethane, trifluoromethane, 1,2-C2H4F2 C2H4F2,1,2,2,2-Tetrafluoroethane, methyl chloride, ethyl chloride and methylene dichloride.Inorganic pneumatogen can be following but be not limited only to following material: air, nitrogen, carbonic acid gas, oxygen, argon G&W.These organic and inorganic foaming agents can be used alone, and also can use as the mixture of two or more.Consider low cost and the environmental problem of foamex, air or nitrogen are best whipping agent.Water as whipping agent can be the water as the dispersion medium making this dispersing resin microparticles.
The quantity of this whipping agent suitably can regulate according to the kind of this whipping agent, blowing temperature, the expansion ratio of foamex that will produce.
Foam material of the present invention, the expanded resin beads comprising crosslinked phenolic resin matrix and be dispersed in wherein, and be prepared from by above-mentioned phenol resin composition.
The preparation method of foam material of the present invention comprises: each component of above-mentioned phenol resin composition mixed, and make phenolic resin curing.
The mixing equipment that above-mentioned mixing step uses is the mixing equipment that plastics processing industry is conventional, such as homogenizer, planetary mixer, cone-type mixer, V-Mixer, Agravicmixer, double-cone mixer, colter mixer, ribbon mixer, double helical ribbon mixer, vacuum mixer, high speed dispersor, double-shaft paddle continuous mixer, kneader etc.
Above-mentioned mixing step also can add weighting agent conventional in resol manufacture field, such as filler, curing catalyst, lubricant, tinting material, softening agent, processing aid etc.Described filler loading is conventional amount used, or adjusts according to the requirement of practical situation.
Adding of above-described various weighting agent just can add when solid phenolic resin, expanded resin beads mixing, also can adding together with solidifying agent before phenolic resin curing.
Foam material of the present invention is not subject to the impact of phenolic resin curing system, as long as make the solidification value of heat resisting temperature higher than resol of expanded resin beads.Heat resisting temperature be herein expanded resin beads collapse bubble critical temperature.
If use solidifying agent, solidifying agent can be the epoxy-polyester resin and/or other known solidifying agent etc. of various formaldehyde derivatives, hexamethylenetetramine, paraformaldehyde, hexa methoxy trimeric cyanamide, trimellitic acid 1,2-anhydride, epoxy resin, resole, melamine resin, pre-reaction.The consumption of solidifying agent is conventional amount used.By the mixing equipment that the equipment of the solidifying agent of phenol resin composition and resol mixing can adopt foregoing plastics processing industry conventional.
Foam material of the present invention by the impact of phenolic resin curing technique, can not adopt any curing process of resol, such as, can adopt the curing apparatus such as vulcanizing press, tabletting machine, multi-daylight press, baking oven, autoclave, injection moulding machine.
Foam material obtained above, due to the expanded resin beads including crosslinked phenolic resin matrix and be dispersed in wherein, so both maintained the fire-retardant advantage of resol, had also had the feature of expanded bead simultaneously.
Formed material of the present invention, is made up of above-mentioned phenol resin composition, or is made up of above-mentioned foam material, or its manufacture method comprises the step in the preparation method of above-mentioned foam material.Formed material of the present invention can as the incombustible sound-proof material of chance naked light, cushioning material, imitated wood material etc., especially can use as the incombustible lagging material of the chance naked light of various highly effective and safe, such as, can use as the heat preservation plate material that the chance naked light of building trade is incombustible, safe.
Embodiment
Further describe the present invention by embodiment below, but scope of the present invention is not by the restriction of these embodiments.Scope of the present invention is determined by claims.
Embodiment 1
By acrylic resin (Zhenghai refinery, heat-drawn wire 110 DEG C under HMS20Z, 0.45MPa load) 100 weight parts, talcum powder 2 weight part is put into homogenizer and is fully mixed, gained mixture adds in single screw extrusion machine through charging opening, and control die temperature 135 DEG C, pressure is 12MPa.In polypropylene resin composite melt, whipping agent carbonic acid gas is injected with 10MPa pressure by the blowing agent injection port be arranged on extruder barrel.Then by melt through the circular hole die extrusion of diameter 2mm, foaming, obtain expanded polypropylene beads after pelletizing, cooling, drying, expansion ratio is 45 times.
By powdered phenol-formaldehyde resin (Xinxiang Bai Ma sail Industrial Co., Ltd., 2123), expanded polypropylene beads adds in homogenizer and fully mixes, and wherein the volume ratio of resol and expanded polypropylene beads is 10/90.Then add hexamethylenetetramine (technical grade, Beijing Yili Fine Chemicals Co., Ltd. produces) wherein, mix rear discharging, hexamethylenetetramine is 12/100 with phenolic resin weight ratio.
Tabletting machine is warming up to 120 DEG C, above material is put into mould on tabletting machine, carries out mold pressing.The print of gained carries out properties test, records that the results are shown in Table 1.
Thermal conductivity is tested according to GB/T 10297-98 standard.Combustionproperty is then be placed in by print on alcohol blast burner to stand flame spraying after 10 minutes, observes the state of print.
Embodiment 2
Except the volume ratio of powdered phenol-formaldehyde resin and expanded polypropylene beads is except 20/80, all the other are all identical with embodiment 1, record that the results are shown in Table 1.
Embodiment 3
Except the volume ratio of powdered phenol-formaldehyde resin and expanded polypropylene beads is except 30/70, all the other are all identical with embodiment 1, record that the results are shown in Table 1.
Embodiment 4
Except the volume ratio of powdered phenol-formaldehyde resin and expanded polypropylene beads is except 40/60, all the other are all identical with embodiment 1, record that the results are shown in Table 1.
Embodiment 5
Except the volume ratio of powdered phenol-formaldehyde resin and expanded polypropylene beads is except 50/50, all the other are all identical with embodiment 1, record that the results are shown in Table 1.
Embodiment 6
Except the volume ratio of powdered phenol-formaldehyde resin and expanded polypropylene beads is except 80/20, all the other are all identical with embodiment 1, record that the results are shown in Table 1.
Embodiment 7
Except the volume ratio of powdered phenol-formaldehyde resin and expanded polypropylene beads is except 90/10, all the other are all identical with embodiment 1, record that the results are shown in Table 1.
Embodiment 8
Except the volume ratio of powdered phenol-formaldehyde resin and expanded polypropylene beads is except 95/5, all the other are all identical with embodiment 1, record that the results are shown in Table 1.
Embodiment 9
Expansion ratio except expanded polypropylene beads is except 10 times, and all the other are all identical with embodiment 3, records that the results are shown in Table 1.
Embodiment 10
Except powdered phenol-formaldehyde resin changes granular phenol resin (Shandong Shengquan Chemical Industry Co., Ltd. into, PF-1350, use after pulverizing), acrylic resin changes acrylic resin (Yanshan Petrochemical into, heat-drawn wire 90 DEG C under K 7003,0.45MPa load), molding temperature changes into outside 100 DEG C, all the other are all identical with embodiment 2, record that the results are shown in Table 1.
Table 1
| Thermal conductivity | Combustionproperty | |
| Unit | W/m·K | |
| Embodiment 1 | 0.051 | Do not burn |
| Embodiment 2 | 0.069 | Do not burn |
| Embodiment 3 | 0.088 | Do not burn |
| Embodiment 4 | 0.094 | Do not burn |
| Embodiment 5 | 0.117 | Do not burn |
| Embodiment 6 | 0.197 | Do not burn |
| Embodiment 7 | 0.205 | Do not burn |
| Embodiment 8 | 0.219 | Do not burn |
| Embodiment 9 | 0.081 | Do not burn |
| Embodiment 10 | 0.080 | Do not burn |
Claims (21)
1. a phenol resin composition, comprises solid phenolic resin and expanded resin beads, the foaming base resin that described expanded resin beads adopts be under 0.45MPa load heat-drawn wire higher than the resin of 90 DEG C.
2. phenol resin composition according to claim 1, it is characterized in that foaming base resin that described expanded resin beads adopts be under 0.45MPa load heat-drawn wire higher than the resin of 100 DEG C.
3. phenol resin composition according to claim 2, it is characterized in that foaming base resin that described expanded resin beads adopts be under 0.45MPa load heat-drawn wire higher than the resin of 110 DEG C.
4. phenol resin composition according to claim 1, is characterized in that the volume ratio of described solid phenolic resin and expanded resin beads is 5 ︰ 95 ~ 95 ︰ 5.
5. phenol resin composition according to claim 4, is characterized in that the volume ratio of described solid phenolic resin and expanded resin beads is 5 ︰ 95 ~ 80 ︰ 20.
6. phenol resin composition according to claim 5, is characterized in that the volume ratio of described solid phenolic resin and expanded resin beads is 5 ︰ 95 ~ 40 ︰ 60.
7. phenol resin composition according to claim 1, is characterized in that foaming base resin that described expanded resin beads adopts comprises at least one in following various resin: (1) olefin homo and/or olefin copolymer; (2) poly(4-methyl-1-pentene); (3) polyamide resin and/or its modified product; (4) polycarbonate resin and/or its modified product; (5) homopolymerization and/or copolymerized methanal; (6) different monounsaturated dicarboxylic acid and dibasic alcohol are by the obtained linear polyester of polycondensation; (7) aromatic ring polymer; (8) heterocyclic polymer; (9) fluoropolymer.
8. phenol resin composition according to claim 7, is characterized in that foaming base resin that described expanded resin beads adopts comprises at least one in olefin homo and/or olefin copolymer.
9. phenol resin composition according to claim 7, is characterized in that described aromatic ring polymer comprises at least one in polyphenyl, polyphenylene oxide, polyphenylene sulfide, polyarylsulphone, poly aryl ketone, Aromatic polyester and aromatic polyamides; Described heterocyclic polymer comprises polybenzimidazole.
10. phenol resin composition according to claim 1, is characterized in that the expansion ratio of described expanded resin beads is 0.5 ~ 100 times.
11. phenol resin compositions according to claim 10, is characterized in that the expansion ratio of described expanded resin beads is 1 ~ 70 times.
12. phenol resin compositions according to claim 11, is characterized in that the expansion ratio of described expanded resin beads is 1 ~ 50 times.
13. 1 kinds of foam materials, the expanded resin beads comprising crosslinked phenolic resin matrix and be dispersed in wherein, and be prepared from by the phenol resin composition described in any one of claim 1 ~ 12.
14. foam materials according to claim 13, is characterized in that the preparation method of described foam material comprises: each component of described phenol resin composition mixed, and make phenolic resin curing.
15. foam materials according to claim 14, is characterized in that the solidification value of the heat resisting temperature of described expanded resin beads higher than described resol.
The preparation method of 16. 1 kinds of foam materials, comprising: each component of the phenol resin composition described in any one of claim 1 ~ 12 mixed, and make phenolic resin curing.
17. preparation methods according to claim 16, is characterized in that the solidification value of the heat resisting temperature of described expanded resin beads higher than described resol.
18. preparation methods according to claim 16 or 17, is characterized in that the expanded resin beads that the foam material obtained comprises crosslinked phenolic resin matrix and is dispersed in wherein.
19. 1 kinds of formed materials, it is characterized in that it is made up of the phenol resin composition described in any one of claim 1 ~ 12, or be made up of the foam material described in any one of claim 13 ~ 15, or its manufacture method comprises the step in the preparation method of the foam material described in any one of claim 16 ~ 18.
20. formed materials according to claim 19, is characterized in that described formed material is lagging material, sound-proof material, cushioning material or imitated wood material.
21. formed materials according to claim 20, is characterized in that described lagging material is heat preservation plate material.
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| CN201210189851.6A CN102690494B (en) | 2012-06-08 | 2012-06-08 | Phenolic resin composition and foaming material prepared from same |
| PCT/CN2013/076898 WO2013182074A1 (en) | 2012-06-08 | 2013-06-07 | Phenolic resin composition, foam material prepared therewith and preparation method thereof and molding material prepared thereby |
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| CN201210189851.6A CN102690494B (en) | 2012-06-08 | 2012-06-08 | Phenolic resin composition and foaming material prepared from same |
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| WO2013182074A1 (en) * | 2012-06-08 | 2013-12-12 | 中国石油化工股份有限公司 | Phenolic resin composition, foam material prepared therewith and preparation method thereof and molding material prepared thereby |
| CN104788886B (en) * | 2014-01-21 | 2017-06-06 | 中国石油化工股份有限公司 | A kind of phenol resin composition and its expanded material of preparation |
| CN105482357B (en) * | 2014-09-19 | 2018-01-23 | 中国石油化工股份有限公司 | A kind of phenol resin composition and its expanded material and moulding material of preparation |
| CN105482243B (en) * | 2014-09-19 | 2017-11-07 | 中国石油化工股份有限公司 | A kind of phenol resin composition and its expanded material and moulding material of preparation |
| CN105462161B (en) * | 2014-09-19 | 2017-10-03 | 中国石油化工股份有限公司 | A kind of phenol resin composition and its expanded material and moulding material of preparation |
| CN104974466A (en) * | 2015-06-30 | 2015-10-14 | 苏州博利迈新材料科技有限公司 | Phenolic foam plastic and preparation method thereof |
| CN105219055A (en) * | 2015-10-20 | 2016-01-06 | 西南科技大学 | A kind of fretting map luminous reflectance PC mould material and preparation method thereof |
| CN106700428A (en) * | 2016-12-29 | 2017-05-24 | 广东生益科技股份有限公司 | Halogen-free resin composition, adhesive and laminated busbar insulating adhesive film prepared therefrom, and preparation method of insulating adhesive film |
| CN107011623A (en) * | 2017-06-08 | 2017-08-04 | 东莞市联洲知识产权运营管理有限公司 | A kind of fire-retardant polyformaldehyde composite material of environment-friendly high-efficiency and preparation method thereof |
| CN107325482B (en) * | 2017-08-04 | 2019-04-09 | 国网山东省电力公司临沂供电公司 | The method of the high-intensitive prefabricated cabin of integrated type foaming preparation |
| CN107523011A (en) * | 2017-09-14 | 2017-12-29 | 锦州市好为尔保温材料有限公司 | Modified phenolic warming plate using nitrogen as foaming agent |
| CN109229874B (en) * | 2018-08-15 | 2020-12-08 | 湖州达立智能设备制造有限公司 | Preparation method of plastic packaging material for refrigeration |
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| CN101724171A (en) * | 2009-12-10 | 2010-06-09 | 谢建华 | Preparation method of phenolic resin composite for foam |
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