CN100351312C - Fiber filled phenolic foam plastics - Google Patents
Fiber filled phenolic foam plastics Download PDFInfo
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- CN100351312C CN100351312C CNB2004100758557A CN200410075855A CN100351312C CN 100351312 C CN100351312 C CN 100351312C CN B2004100758557 A CNB2004100758557 A CN B2004100758557A CN 200410075855 A CN200410075855 A CN 200410075855A CN 100351312 C CN100351312 C CN 100351312C
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- Prior art keywords
- fiber
- phenolic foam
- foam plastics
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- filled phenolic
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- 239000000835 fiber Substances 0.000 title claims abstract description 53
- 239000004033 plastic Substances 0.000 title claims abstract description 53
- 229920003023 plastic Polymers 0.000 title claims abstract description 53
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000006260 foam Substances 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 claims description 39
- 239000003365 glass fiber Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 230000008602 contraction Effects 0.000 claims description 14
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 11
- 239000004917 carbon fiber Substances 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 229920006231 aramid fiber Polymers 0.000 claims description 7
- 229920003987 resole Polymers 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 229920001187 thermosetting polymer Polymers 0.000 claims 1
- 230000006835 compression Effects 0.000 abstract description 11
- 238000007906 compression Methods 0.000 abstract description 11
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 9
- 229920001568 phenolic resin Polymers 0.000 abstract description 9
- 238000005187 foaming Methods 0.000 abstract description 7
- 239000005011 phenolic resin Substances 0.000 abstract description 6
- 230000001788 irregular Effects 0.000 abstract 1
- 239000002984 plastic foam Substances 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000001360 synchronised effect Effects 0.000 abstract 1
- 238000009775 high-speed stirring Methods 0.000 description 13
- 238000010792 warming Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 230000003068 static effect Effects 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000013019 agitation Methods 0.000 description 8
- -1 aldehyde compound Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 241000158728 Meliaceae Species 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- 239000006261 foam material Substances 0.000 description 4
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 2
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical class C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 2
- 229920000561 Twaron Polymers 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000136 polysorbate Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004762 twaron Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- HSAOVLDFJCYOPX-UHFFFAOYSA-N 2-[4-(1,3-benzothiazol-2-yl)phenyl]-1,3-benzothiazole Chemical compound C1=CC=C2SC(C3=CC=C(C=C3)C=3SC4=CC=CC=C4N=3)=NC2=C1 HSAOVLDFJCYOPX-UHFFFAOYSA-N 0.000 description 1
- GUCVVHCKEIDUOF-UHFFFAOYSA-N C=O.OC(CC)(C1=CC=CC=C1)O Chemical compound C=O.OC(CC)(C1=CC=CC=C1)O GUCVVHCKEIDUOF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000013305 flexible fiber Substances 0.000 description 1
- FARPFSXQFUYARA-UHFFFAOYSA-N formaldehyde;propane Chemical compound O=C.CCC FARPFSXQFUYARA-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention adopts fiber to fill phenolic foam plastic by aiming at the problems of high forming and shrinking rate and poor size stability of the phenolic foam plastic. An amount of chopped fiber and/or pulp is evenly dispersed in a phenolic resin foaming system, and the foaming and the solidification are carried out in a synchronous mode under a proper technical condition. Compared with plastic foam which is not filled with the fiber, the size shrinking rate and the compression deformation rate of the phenolic foam plastic of the present invention are obviously reduced. The apparent density of the phenolic foam plastic of the present invention is from 80 kg/m<3> to 300 kg/m<3>, and the phenolic foam plastic is especially suitable for large-sized thin-walled parts or thin-walled curved irregular preforming products.
Description
One, technical field
The present invention relates to phenolic foam material, particularly fiber filled phenolic foam plastics and preparation method thereof.
Two, background technology
As low density material, phenolic foamed plastics is except having general porous plastics light weight, heat insulation characteristics, also have fire-retardant, heat-resisting, resistance to chemical attack, low cost and other advantages, be widely used in engineering and the building industry field heat insulation, sound-absorbing, explosion-proof lamp under high temperature, the corrosive environment.Phenolic foamed plastics inherent shortcoming---matter is crisp, dimensional stability is bad, structural strength is not enough has limited its application, and particularly the application facet at large thin-wall or special-shaped thin wall premolding foam article is restricted.Adopt structural additives or fiber filled the existing report of enhancing, Research on Toughening, but do not appear in the newspapers at the research that improves foam materials preformed member dimensional stability to phenolic foam material.
US 20030187086A has introduced a kind of fiber reinforcement phenolic foamed plastics, adopt flexible fiber to strengthen phenolic foamed plastics, under the suitable condition of density, foam materials fragility is improved, structural strength and wear resistance improve, but the dimensional change situation of not mentioned foams.
Three, summary of the invention
The present invention is directed to the problem that molding shrinkage is big, dimensional stability is bad that phenolic foamed plastics exists, adopt fiber that phenolic foamed plastics is carried out modification, enhancing, in the mechanical property that effectively improves material, flame retardant properties, thermal characteristics, reduce the molding shrinkage of phenolic foamed plastics, improve the dimensional stability of phenolic foamed plastics.
The present invention is achieved in that in the foamed phenolic resin system, the fiber that homodisperse is an amount of, and fiber and resin are collaborative in resin expanded process flows, and solidify to form the equally distributed filled phenolic foam plastics of fiber along with resin.
The composition of the phenolic foamed plastics that the present invention relates to comprises resol, fiberfill fibers, tensio-active agent, solidifying agent, whipping agent five parts at least, and preparation process comprises primary processes such as mixing, foaming, curing.
The fiber filled phenolic foam plastics that the present invention relates to, the mass parts of its raw material consists of:
Resol 100
Tensio-active agent 2～8
Solidifying agent 3～40
Whipping agent 2.5～30
Fiberfill fibers 3～30
The preparation process of the phenolic foamed plastics that the present invention relates to may further comprise the steps:
(1) resol and tensio-active agent high-speed stirring is even, make mixture A;
(2) stir down, fiber fill is added mixture A, be stirred to fiberfill fibers to be uniformly dispersed, make mixture B;
(3) down static, solidifying agent and whipping agent are added mixture B, stir rapidly and make mixture C;
(4) mixture C is poured into rapidly in 35 ℃～55 ℃ moulds, closed mold is warming up to 50 ℃～90 ℃ in 1h～2h, solidifies 1h～8h, obtains fiber filled phenolic foam plastics.
The phenolic foamed plastics that the present invention relates to adopts the generalized heat-reactive phenolic resin, can be a kind of in the polycondensation product of aldehyde compound that contains aldehyde radical and the phenolic compound that contains phenolic group such as P-F, cresols-formaldehyde, Resorcinol-formaldehyde, dihydroxyphenyl propane-formaldehyde or two or more composition wherein, resin viscosity is between 3100mPa.s～38500mPa.s, and solids content is between 60%～95%.
The fiberfill fibers that phenolic foamed plastics adopted that the present invention relates to, fiber cross section can be rounded section, special crosssection and/or hollow section.Fiber length ranges is between 0.2mm～20mm.
The used fiberfill fibers of the phenolic foamed plastics that the present invention relates to can be a kind of or wherein several mixture in glass fibre, aramid fiber, Poly-p-phenylene benzobisthiazole (pbo fiber), the carbon fiber.
The used glass fibre of the phenolic foamed plastics that the present invention relates to can be a kind of or wherein several mixture in alkali free glass fibre, medium-alkali glass fibre, resurrection glass fibre, high strength glass fiber, the high-modulus glass fiber.
The used aramid fiber of the phenolic foamed plastics that the present invention relates to can be the aramid fiber of a contraposition virtue acid amides and a position virtue acid amide type, also can be the mixture of two kinds of fibers.
The used pbo fiber of the phenolic foamed plastics that the present invention relates to is one or both the combination in standard type and/or the high-modulus type.
The used carbon fiber of the phenolic foamed plastics that the present invention relates to can be a kind of or wherein several mixture in viscose-based carbon fiber, polyacrylonitrile (PAN) base carbon fibre and the asphalt base carbon fiber, mainly is universal and high-performance carbon fibers.
The tensio-active agent that the present invention uses can be general phenolic resin system foaming tensio-active agent, as a kind of in Sodium dodecylbenzene sulfonate, Tweens (as polyoxyethylene sorbitol acid anhydride monoesters), polyoxyethylene nonylphenol ether class (polyoxyethylene nonylphenol ether), the modified silicon oil or the mixed surfactant system be made up of several tensio-active agents.
The solidifying agent that the present invention relates to can be general phenolic resin system foaming acids solidifying agent, comprising organic acid and mineral acid, can be a kind of in hydrochloric acid, sulfuric acid, o-toluene sulfonic acid, tosic acid, the mahogany acid or by several mixed curing agent systems of forming wherein.
The whipping agent that the phenolic foamed plastics that the present invention relates to uses can be general phenolic resin system whipping agent, comprises a kind of in low molecular weight hydrocarbons, chloro-fluoro-carbon kind whipping agent (as F113, F11), the Hydrochlorofluorocarbons class whipping agent (as 141B) or the mixed foaming system of being made up of several whipping agents wherein.
The phenolic foamed plastics that the present invention relates to, fiberfill fibers is uniform distribution in foams, and under suitable processing condition, foaming and curing are carried out synchronously, and the foams apparent density is between 80kg/m
3～300kg/m
3Between, the dimensional stability and the non-deformability of foams are obviously improved, and dimensional contraction rate and compression deformation rate are reduced to respectively below 3.8% with below 6.1%.
The phenolic foamed plastics that the present invention relates to is specially adapted to the special-shaped preliminary shaping goods processing of large-scale thin wall parts or thin-wall curved-surface.
Four, embodiment
Embodiment 1 (Comparative Examples)
With viscosity is that 9300mPa.s, net content are that 100 parts S-172 resol (five or three production) and 3 parts of DC-193 silicone oil (Dow corning company product) mix under high-speed stirring, stop to stir, add 20 parts of concentration and be aqueous sulfuric acid and 4.5 parts of 141B of 20%, be stirred to and mix; Mixture is poured into rapidly in the mould that is preheating to 50 ℃, and closed mold is warming up to 90 ℃ and solidifies 3h in 1.5h; After the cooling, obtaining apparent density is 142kg/m
3Phenolic foamed plastics.Place that the dimensional contraction rate is 12.2% after 7 days, the compression deformation rate under the 0.2MPa is 8.2%.
Embodiment 2
With viscosity is that 16500mPa.s, net content are that 100 parts phenol-formaldehyde resin and 6.5 parts tween-80 mix under high-speed stirring, stirs down to add 18 parts of hollow alkali free glass fibres that length is 4.5mm, is fully disperseed until chopped strand; 9 parts of concentration of static adding down are 80% the mahogany acid aqueous solution and 10 parts of pentane admixtures (70% Skellysolve A, 30% iso-pentane), are stirred to mix; Mixture is poured into rapidly in the mould that is preheating to 37 ℃, and closed mold is warming up to 60 ℃ and solidifies 5h in 1h; After the cooling, obtaining apparent density is 196kg/m
3Porous plastics.The dimensional contraction rate of placing after 7 days is 0.75%, and the compression deformation rate under the 0.2MPa is 5.7%.
Embodiment 3
With viscosity is that 30500mPa.s, net content are that 100 parts first rank cresol-formaldehyde resin, 2.5 parts of Tween-40s, 1.5 parts of Sodium dodecylbenzene sulfonatees mix under high-speed stirring, stir the TWARON PULP 1099 aramid fibers slurry pool that adds 22 parts of 1mm down (Dutch Aksu company product), fully disperseed until the slurry pool; Static state adds 12 parts of Skellysolve As and 23 part of 65% p-methyl benzenesulfonic acid aqueous solution down, is stirred to mix; Mixture is poured into rapidly in the mould that is preheating to 41 ℃, and closed mold is warming up to 70 ℃ and solidifies 5h in 1h; After the cooling, obtaining apparent density is 150kg/m
3Porous plastics.The dimensional contraction rate of placing after 7 days is 1.18%.
Embodiment 4
With viscosity is that 7260mPa.s, net content are that 100 parts S-167 resin (five or three production), 5 parts of Tween-40s mix under high-speed stirring, the AS555 type pbo fiber (company's product spins in Japanese Japan) that under agitation to add 10 parts of length be 3mm is fully disperseed until fiber; Static state adds 10 parts of CFC-113,32 part of 80% mahogany acid aqueous solution down, is stirred to mix; Mixture is poured into rapidly in the mould that is preheating to 37 ℃, and closed mold is warming up to 80 ℃ in 2h, solidifies 3h; After the cooling, obtaining apparent density is 151kg/m
3Porous plastics.The dimensional contraction rate of placing after 7 days is 0.52%, and the compression deformation rate under the 0.2MPa is 5.3%.
Embodiment 5
With viscosity is that 3100mPa.s, net content are that 100 parts S-172 resin (five or three production), 5 parts of polyoxyethylene nonylphenol ethers 10 mix under high-speed stirring, stir 5 parts of T-700 carbon fibers (toray company product) that length is 6mm of adding down, fully disperseed until fiber; Static state adds 30 part of 10% hydrochloric acid and 15 parts of pentamethylene down, is stirred to mix; Mixture is poured into rapidly in the mould that is preheating to 35 ℃, and closed mold is warming up to 50 ℃ in 1h, solidifies 8h; After the cooling, obtaining apparent density is 112kg/m
3Porous plastics.The dimensional contraction rate of placing after 7 days is 0.92%.
Embodiment 6
With viscosity is that 18200mPa.s, net content are that phenol/resorcinol-formaldehyde resin of 100 parts, 2 parts of Tween-60s mix under high-speed stirring, under agitation add the HTA E30 carbon fiber powder (Japanese Dong Bang company product) of 18 part of 200 μ m, fully disperse until the fiber pruinescence; 20 parts of concentration of static adding down are 10% aqueous hydrochloric acid, 15 part of 80% mahogany acid aqueous solution and 2.5 parts of HCFC-141B, are stirred to mix; Mixture is poured into rapidly in the mould that is preheating to 55 ℃, and closed mold is warming up to 80 ℃ in 1h, solidifies 3h; After the cooling, obtaining apparent density is 300kg/m
3Porous plastics.The dimensional contraction rate of placing after 7 days is 3.8%, and the compression deformation rate under the 0.2MPa is 3.5%.
Embodiment 7
With viscosity is that 38500mPa.s, net content are that 100 parts phenol-formaldehyde resin, 2 parts of Sodium dodecylbenzene sulfonatees, 2 parts of DC-193 silicone oil (Dow corning company product) mix under high-speed stirring, the M40JB carbon fiber (toray company product) that under agitation to add 3 parts of length be 5mm and 15 parts of TWARON PULP 1099 aramid fibers slurry pools (Dutch Aksu company product) are fully disperseed until fiber and slurry pool; Static to add 30 parts of concentration down be that 20% aqueous sulfuric acid, 10 parts of concentration are the p-methyl benzenesulfonic acid aqueous solution and 20 parts of Skellysolve As of 65%, is stirred to mix; Mixture is poured into rapidly in the mould that is preheating to 47 ℃, and closed mold is warming up to 75 ℃ in 1h, solidifies 3h; After the cooling, obtaining apparent density is 136kg/m
3Porous plastics.The dimensional contraction rate of placing after 7 days is 0.91%, and the compression deformation rate under the 0.2MPa is 3.9%.
Embodiment 8
With viscosity is that 3300mPa.s, net content are that 100 parts cresol-formaldehyde resin, 3 parts of Sodium dodecylbenzene sulfonatees and 1 part of DC-193 silicone oil (Dow corning company product) mix under high-speed stirring, the M50J fiber (toray company product) that under agitation to add 3 parts of length be 20mm is fully disperseed until fiber; The sulfuric acid of static following 15 parts of pentane admixtures (70% Skellysolve A, 30% iso-pentane) and 20 part 20% is stirred to and mixes; Mixture is poured into rapidly in the mould that is preheating to 52 ℃, and closed mold is warming up to 90 ℃ in 1h, solidifies 1h; After the cooling, obtaining apparent density is 168kg/m
3Porous plastics.The dimensional contraction rate of placing after 7 days is 1.25%, and the compression deformation rate under the 0.2MPa is 3.1%.
Embodiment 9
With viscosity is that 8500mPa.s, net content are that 100 parts cresol-formaldehyde resin, 6 parts of tween 20s mix under high-speed stirring, and the alkali free glass fibre that under agitation to add 6 parts of length be 12mm is fully disperseed until fiber; Static 45 part of 65% p-methyl benzenesulfonic acid aqueous solution and 18 parts of F113 of adding down, stirring 5min; Mixture is poured into rapidly in the mould that is preheating to 37 ℃, and closed mold is warming up to 80 ℃ in 2h, solidifies 3h; After the cooling, obtaining apparent density is 146kg/m
3Porous plastics.The dimensional contraction rate of placing after 7 days is 0.87%.
Embodiment 10
With viscosity is that 10200mPa.s, net content are that phenol/dihydroxyphenyl propane-formaldehyde resin of 100 parts, 6 parts of Tween-40s and 2 parts of Sodium dodecylbenzene sulfonatees mix under high-speed stirring, the S-2 high strength glass fiber (Nanjing glass fibre research institute product) that under agitation to add 30 parts of length be 1.5mm is fully disperseed until fiber; Static state adds 50 part of 80% mahogany acid aqueous solution and 25 parts of pentamethylene down, is stirred to mix; Mixture is poured into rapidly in the mould that is preheating to 42 ℃, and closed mold is warming up to 75 ℃ in 1h, solidifies 2.5h; After the cooling, obtaining apparent density is 205kg/m
3Porous plastics.The dimensional contraction rate of placing after 7 days is 2.12%, and the compression deformation rate under the 0.2MPa is 3.2%.
Embodiment 11
With viscosity is that 29720mPa.s, net content are that 100 parts phenol-formaldehyde resin, 4 parts of Tween-40s mix under high-speed stirring, under agitation adding 8 parts of length is the leaf cross section alkali free glass fibre (Ovens Corning Incorporated product) of 15mm, is fully disperseed until fiber; Static state adds aqueous sulfuric acid, 20 part of 65% p-methyl benzenesulfonic acid aqueous solution and 30 parts of F-113 of 60 part 20% down, is stirred to mix; Mixture is poured into rapidly in the mould that is preheating to 40 ℃, and closed mold is warming up to 60 ℃ in 1h, solidifies 6h; After the cooling, obtaining apparent density is 172kg/m
3Porous plastics.The dimensional contraction rate of placing after 7 days is 0.85%, and the compression deformation rate under the 0.2MPa is 6.1%.
Embodiment 12
With viscosity is that 26500mPa.s, net content are that 100 parts cresol-formaldehyde resin, 6.5 parts of polyoxyethylene nonylphenol ethers 10 mix under high-speed stirring, under agitation adds the alkali free glass fibre powder of 25 part of 400 μ m, fully disperses until the fiber pruinescence; Static state adds 20 part of 80% mahogany acid aqueous solution and 25 parts of Skellysolve As down, is stirred to mix; Mixture is poured into rapidly in the mould that is preheating to 42 ℃, and closed mold is warming up to 90 ℃ in 1.5h, solidifies 2h; Cooling back opening mold, obtaining apparent density is 80kg/m
3Porous plastics.The dimensional contraction rate of placing after 7 days is 3.69%, and the compression deformation rate under the 0.2MPa is 4.7%.
Claims (8)
1. fiber filled phenolic foam plastics, contain resol, fiberfill fibers, tensio-active agent, solidifying agent, whipping agent five parts in the feedstock composition, it is characterized in that, the dimensional contraction rate of porous plastics is not more than 3.8%, used resol is the thermosetting resin of viscosity between 3100mPa.s～38500mPa.s, and its quality group becomes umber to be:
Resol 100
Tensio-active agent 2～8
Solidifying agent 3～40
Whipping agent 2.5～30
Fiberfill fibers 3～30.
2. the described fiber filled phenolic foam plastics of claim 1, used fiberfill fibers is a kind of or wherein several mixture in glass fibre, aramid fiber, carbon fiber, the pbo fiber.
3. the described fiber filled phenolic foam plastics of claim 1, used fiberfill fibers length is between 0.2mm～20mm.
4. the described fiber filled phenolic foam plastics of claim 1, used fiberfill fibers cross section can be circular, abnormity and/or in aerial a kind of.
5. the described fiber filled phenolic foam plastics of claim 3, used glass fibre is a kind of or wherein several combination in alkali free glass fibre, medium-alkali glass fibre, resurrection glass fibre, high strength glass fiber, the high-modulus glass fiber.
6. the described fiber filled phenolic foam plastics of claim 3, used aramid fiber are one or both the combinations in a contraposition virtue acid amides and/or the position virtue acid amide type.
7. the described fiber filled phenolic foam plastics of claim 3, used pbo fiber are one or both the combinations in standard type and/or the high-modulus type.
8. the described fiber filled phenolic foam plastics of claim 3, used carbon fiber is a PAN-based carbon fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100758557A CN100351312C (en) | 2004-12-31 | 2004-12-31 | Fiber filled phenolic foam plastics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100758557A CN100351312C (en) | 2004-12-31 | 2004-12-31 | Fiber filled phenolic foam plastics |
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| CN100351312C true CN100351312C (en) | 2007-11-28 |
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Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101440193B (en) * | 2007-11-23 | 2010-12-22 | 航天材料及工艺研究所 | Carbon / phenolic heat insulating composite material and manufacturing process thereof |
| CN101269930B (en) * | 2008-05-06 | 2010-06-09 | 福州大学 | Enzymatically hydrolyzed lignin or its derivatives modified phenolic foaming material and preparation method thereof |
| CN101781393A (en) * | 2009-01-19 | 2010-07-21 | 济南圣泉集团股份有限公司 | Resin for high-flame-retardant phenol formaldehyde foam and production method thereof |
| CN102092114B (en) * | 2009-12-09 | 2013-09-25 | 哈尔滨东大林业技术装备有限公司 | Production process and equipment for adding glass fibers in phenolic aldehyde glass fiber reinforced foamed material |
| CN101709136B (en) * | 2009-12-10 | 2011-08-03 | 上海法普罗材料技术有限公司 | Foamed phenolic resin composition |
| CN103834136B (en) * | 2012-11-22 | 2017-05-31 | 合肥杰事杰新材料股份有限公司 | Toughening modifying Foaming of phenolic resin material and preparation method thereof |
| CN102964772B (en) * | 2012-12-05 | 2014-12-03 | 福建天利高新材料有限公司 | Chopped fiber reinforced phenolic resin foam material and preparation method thereof |
| CN103012833A (en) * | 2012-12-26 | 2013-04-03 | 青岛科瑞新型环保材料有限公司 | Phenolic foamed plastic |
| CN105647105B (en) * | 2014-08-15 | 2019-04-23 | 江南大学 | A kind of aramid fiber pulp fiber reinforced phenolic foam composite material and preparation method thereof |
| CN104387541B (en) * | 2014-11-06 | 2016-10-05 | 聊城大学 | A kind of toughening modifying phenol formaldehyde foam and preparation method thereof |
| CN104513453A (en) * | 2015-01-14 | 2015-04-15 | 苏州图纳新材料科技有限公司 | Thermoset phenolic resin composite material and preparation method thereof |
| CN105086348B (en) * | 2015-08-28 | 2017-05-31 | 哈尔滨工业大学 | A kind of layered distribution short fiber reinforced porous phenolic composite and preparation method thereof |
| CN105694352A (en) * | 2016-01-30 | 2016-06-22 | 范洲卫 | Phenolic foam thermal-insulation board and preparation method thereof |
| US10723088B2 (en) * | 2016-09-29 | 2020-07-28 | Toray Industries, Inc. | Fiber-reinforced thermoplastic-resin base and molded article obtained therefrom |
| CN106867193A (en) * | 2017-02-22 | 2017-06-20 | 广西芮芽科技有限公司 | Improve the preparation method of phenolic foam material heat-insulating property |
| CN106883550A (en) * | 2017-02-22 | 2017-06-23 | 广西芮芽科技有限公司 | The preparation method of phenolic foam material |
| CN106928645A (en) * | 2017-02-22 | 2017-07-07 | 广西芮芽科技有限公司 | The preparation method of the phenolic foam material with heat insulating ability high |
| CN107379692A (en) * | 2017-06-27 | 2017-11-24 | 苏州威尔德工贸有限公司 | A kind of polyurethane-modified flexible multi-layered foamed phenolic resin composite and preparation method thereof |
| CN109233191A (en) * | 2018-07-26 | 2019-01-18 | 苏州汉力新材料有限公司 | A kind of preparation method of phenolic resin compound insulating material |
| CN109054423A (en) * | 2018-08-08 | 2018-12-21 | 苏州利波紧固件有限公司 | A kind of fretting map composite polymer material building template and preparation method thereof |
| CN110843271A (en) * | 2019-11-15 | 2020-02-28 | 江苏万华拓谷新材料科技有限公司 | Electromagnetic wave absorbing resin foam plate and preparation method thereof |
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