CN102649866A - Phenolic foam prepared by using incombustible foaming agent and preparation method for phenolic foam - Google Patents
Phenolic foam prepared by using incombustible foaming agent and preparation method for phenolic foam Download PDFInfo
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- CN102649866A CN102649866A CN2012101630729A CN201210163072A CN102649866A CN 102649866 A CN102649866 A CN 102649866A CN 2012101630729 A CN2012101630729 A CN 2012101630729A CN 201210163072 A CN201210163072 A CN 201210163072A CN 102649866 A CN102649866 A CN 102649866A
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- Prior art keywords
- calcium carbonate
- acid
- modified calcium
- phenol formaldehyde
- parts
- Prior art date
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- 239000006260 foam Substances 0.000 title claims abstract description 25
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title description 17
- 239000004088 foaming agent Substances 0.000 title 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 70
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000007787 solid Substances 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000000839 emulsion Substances 0.000 claims abstract description 25
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 21
- 239000000945 filler Substances 0.000 claims abstract description 16
- 239000012188 paraffin wax Substances 0.000 claims abstract description 16
- -1 phenolic resin modified calcium carbonate Chemical class 0.000 claims abstract description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 6
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 6
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 46
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 19
- 229920003986 novolac Polymers 0.000 claims description 19
- 229920003987 resole Polymers 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 239000013543 active substance Substances 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 150000002148 esters Chemical group 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 239000004160 Ammonium persulphate Substances 0.000 claims description 7
- 239000004902 Softening Agent Substances 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 7
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 230000004927 fusion Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 239000006174 pH buffer Substances 0.000 claims description 5
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 5
- 229920000053 polysorbate 80 Polymers 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 4
- 239000000872 buffer Substances 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- 235000012255 calcium oxide Nutrition 0.000 claims description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 4
- 229960001545 hydrotalcite Drugs 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 235000010755 mineral Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 claims description 3
- 238000006392 deoxygenation reaction Methods 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- 229960001708 magnesium carbonate Drugs 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 abstract description 9
- 239000005011 phenolic resin Substances 0.000 abstract description 9
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 229920001169 thermoplastic Polymers 0.000 abstract 1
- 239000004416 thermosoftening plastic Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 235000019256 formaldehyde Nutrition 0.000 description 10
- 238000009835 boiling Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000005187 foaming Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000006261 foam material Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 150000001912 cyanamides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920006327 polystyrene foam Polymers 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- AWOSYAQRZLEZIV-UHFFFAOYSA-N benzenesulfonic acid formaldehyde urea Chemical class C=O.NC(=O)N.C1(=CC=CC=C1)S(=O)(=O)O AWOSYAQRZLEZIV-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses phenolic foam. The phenolic foam is prepared from foamable phenolic resin, surfactant, modified calcium carbonate, filler and curing agent, wherein the modified calcium carbonate is selected from polyacrylate emulsion modified calcium carbonate, rosin modified calcium carbonate, solid paraffin modified calcium carbonate and thermoplastic phenolic resin modified calcium carbonate; and the phenolic foam does not have a smoldering property and has the pH value of 5 to 6.
Description
Technical field
The present invention relates to high molecular foam material, be specifically related to a kind of phenol formaldehyde foam and preparation method thereof.
Background technology
Phenolic foam material is a kind of fire prevention, heat insulation, sound insulation, lightweight, the superior building material of energy-efficient performance.The phenolic foam material thermal conductivity is low; And difficult combustion degree significantly is superior to polystyrene foam and polyurethane foam that present construction industry is used; Phenol formaldehyde foam meet fire do not burn, indeformable, do not distribute toxic gas, no dropping;, be the excellent lagging material of a kind of fire resistance only, be expected to replace traditional organic polymer lagging materials such as polyurethane foam, polystyrene foam in superficial charring.
At present,, require energy-saving and emission-reduction, especially the external wall heat insulating material for external is required not only heat insulation effect excellence, more require material to have the good flame fire resistance for material of construction.Yet because the manufacturing of phenol formaldehyde foam sheet material is mainly passed through inflammable, volatile low-carbon alkanes as whipping agent, being heated volatilization forms small bubbles, resin solidification moulding.The phenol formaldehyde foam of this method manufacturing burns away, until burning totally in case the phenomenon of can glowing behind the flame is left in burning; In a single day there is water to penetrate into thermal insulation layer simultaneously, will produces acidic liq, body of wall and bar construction are produced corrosion, thus the potential safety hazard of bringing.
Therefore, for phenol formaldehyde foam, urgent hope reduces its smolderability and acidity, thereby improves safety in utilization and expanded application scope.
For example, JP61268733 discloses a kind of fire-resistant PREPARATION OF PHENOLIC FOAM method, and is main through adding a large amount of white lakes in this method, at 90 ℃ of following foamings, do not have the phenomenon of glowing during the burning of resulting product.GB1361045 also provides a kind of method for preparing phenol formaldehyde foam, and mainly through adding the phenol formaldehyde foam for preparing of formaldehyde-Phenylsulfonic acid-urea compounds, its density reaches 130kg/m to this method
3, flame does not have the phenomenon of glowing after 5 minutes.CN102229706 also provides a kind of method for preparing phenol formaldehyde foam, and this method is not used inflammable whipping agent, but the gas that carbonate and acid-respons generate, and need be at 15～40kg/cm
2High pressure under carry out.
But, above-mentioned PREPARATION OF PHENOLIC FOAM method all need need comparatively exacting terms, therefore has room for improvement.
Summary of the invention
For smolderability and the peracidity problem that solves phenol formaldehyde foam, the inventor has carried out research with keen determination, and the result finds: do not use inflammable organic cpds as whipping agent; And be to use the lime carbonate of surface-treated, through the degrees of exposure on modification control lime carbonate surface, and then the speed of response and the level of response of lime carbonate and acid in the control foaming process; With dioxide gas that this reaction was produced as whipping agent; And the heat that discharges in this reaction process plays solidification, thereby, the effective acid residues in the reduction/removing phenol formaldehyde foam not only; Significantly reduce acid; And owing to do not use inflammable organic cpds, significantly reduce smolderability, thereby accomplish the present invention as whipping agent.
The object of the present invention is to provide a kind of phenol formaldehyde foam, this phenol formaldehyde foam is processed by following materials of weight proportions:
Foamable resol: 100 parts
Tensio-active agent: 2～8 parts
Modified calcium carbonate: 5～15 parts
Filler: 10～40 parts
Solidifying agent: 10～20 parts
This phenol formaldehyde foam does not have smolderability, and pH is 5～6;
Wherein, said modified calcium carbonate is selected from polyacrylate emulsion modified calcium carbonate, Abietyl modified lime carbonate, solid paraffin modified calcium carbonate and novolac resin modified calcium carbonate;
Described tensio-active agent is selected from Tween-40, tween-80, AK8812, L5400;
Described filler is selected from nano imvite, hydrotalcite, spun glass, nano-calcium carbonate, white lake, Marinco H, Natural manganese dioxide, quicklime;
Described solidifying agent is selected from: mineral acid such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and organic acid such as formic acid, oxalic acid, tosic acid, xylene monosulfonic acid, methylsulphonic acid, Witco 1298 Soft Acid.
Another object of the present invention is to provide above-mentioned phenol formaldehyde foam, it is through mixing foamable resol, tensio-active agent, modified calcium carbonate and filler, adds solidifying agent then and foams, solidifies and make.
According to phenol formaldehyde foam provided by the invention, there is not the phenomenon of glowing, pH reaches 5～6, has improved the safety in utilization of phenol formaldehyde foam, has reduced the corrosion risk of phenolic aldehyde foam thermal insulation material to construction wall simultaneously.
Embodiment
Describe the present invention below, characteristics of the present invention and advantage will become more clear, clear and definite along with these descriptions.
According to an aspect of the present invention, a kind of phenol formaldehyde foam is provided, this phenol formaldehyde foam is processed by following materials of weight proportions:
Foamable resol: 100 parts
Tensio-active agent: 2～8 parts
Modified calcium carbonate: 5～20 parts
Filler: 10～40 parts
Solidifying agent: 10～25 parts
This phenol formaldehyde foam does not have smolderability, and pH is 5～6;
Wherein, said modified calcium carbonate is selected from polyacrylate emulsion modified calcium carbonate, Abietyl modified lime carbonate, solid paraffin modified calcium carbonate and novolac resin modified calcium carbonate;
Described tensio-active agent is selected from Tween-40, tween-80, AK8812, L5400;
Described filler is selected from nano imvite, hydrotalcite, spun glass, nano-calcium carbonate, white lake, Marinco H, Natural manganese dioxide, quicklime;
Described solidifying agent is selected from: mineral acid such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and organic acid such as formic acid, oxalic acid, tosic acid, xylene monosulfonic acid, methylsulphonic acid, Witco 1298 Soft Acid.
In preferred embodiment, phenol formaldehyde foam is processed by following materials of weight proportions:
Foamable resol: 100 parts
Tensio-active agent: 2～4 parts
Modified calcium carbonate: 15～20 parts
Filler: 10～20 parts
Solidifying agent: 15～25 parts.
In the present invention, as foamable resol, not particular requirement can be used any foamable resol.For example, can prepare foamable resol in the following manner:
300 parts of phenol, 160 parts of solid formaldehydes and 100 parts of softening waters are added in the 1L four-hole boiling flask, open and stir and prolong, holding temperature is at 30 ℃～40 ℃; Add 3 parts of sodium hydroxide, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 2h; Add 3 parts of trimeric cyanamides and 15 parts of white lakes, vacuumize dehydration, vacuum tightness-0.08～-0.1MPa; When system viscosity reaches 5000mPaS, cooling discharging, but obtain foamed phenolic resin;
300 parts of phenol, 180 parts of solid formaldehydes and 120 parts of softening waters are added in the 1L four-hole boiling flask, open and stir and prolong, holding temperature is at 30 ℃～40 ℃; Add 3 parts of sodium hydroxide, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 2h; Add 5 parts of urea and 10 parts of white lakes, vacuumize dehydration, vacuum tightness-0.08～-0.1MPa; When system viscosity reaches 3000mPaS, cooling discharging, but obtain foamed phenolic resin; 300 parts of phenol, 190 parts of solid formaldehydes and 140 parts of softening waters are added in the 1L four-hole boiling flask, open and stir and prolong, holding temperature is at 30 ℃～40 ℃; Add 2.1 parts of sodium hydroxide, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 3h; Add 6 parts of trimeric cyanamides, 6 parts of urea and 15 parts of white lakes, vacuumize dehydration, vacuum tightness-0.08～-0.1MPa; When system viscosity reaches 4000mPaS, cooling discharging, but obtain foamed phenolic resin.
But with upper type is known foamed phenolic resin preparation method, for other currently known methodss, does not enumerate one by one at this.
In the present invention, as modified calcium carbonate, can use in polyacrylate emulsion modified calcium carbonate, Abietyl modified lime carbonate, solid paraffin modified calcium carbonate and the novolac resin modified calcium carbonate one or more.Its role is to, react with acid as solidifying agent, the dioxide gas that reaction produces serves as whipping agent, and the heat that produces in the reaction promotes phenol formaldehyde foam to solidify.
As the polyacrylate emulsion modified calcium carbonate,, make polyacrylic ester form coating film and prepare on the lime carbonate surface through polyacrylate emulsion is mixed with lime carbonate water-based dispersion liquid.Preferably, using solid content is the emulsion of the polyacrylic ester of 25%～45%wt.%, further promotes the coating of polyacrylic ester on the lime carbonate surface.Preferably, in order to promote the coating of polyacrylic ester, be that 5%～15%wt.% is suitable for calcium carbonate suspension concentration on the lime carbonate surface.
As polyacrylate emulsion; Not special the qualification; Can use polyacrylate emulsion commonly used; The polyacrylate emulsion that is for example obtained by polymerizations such as monomer methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, vinylformic acid, TEB 3K and glyceral methacrylate can use wherein one or more.
As the preparation method of polyacrylate emulsion, also not special restriction can be used common polyacrylate emulsion polymerization methods, for example anionic initiation polymerization.
As lime carbonate water-based suspension-s, can lime carbonate be disperseed in water, to obtain through under the ultra-sonic dispersion effect.
One preferred embodiment in, the polyacrylate emulsion modified calcium carbonate prepares through following method:
(1) acrylate monomer, initiator, emulsifying agent, pH buffer reagent and deionized water are backed up by following mass percent: acrylate monomer: 20～40%; Initiator: 0.3～1%; Emulsifying agent: 1～2%; Buffer reagent: 0.5～1%; Surplus is a deionized water;
(2) initiator is with the deionized water dissolving of step in 1., wiring solution-forming B;
(3) get step 1. in 5～10wt.%, step emulsifying agent, pH buffer reagent and the residue deionized water in 1. of acrylate monomer mix and add reactor drum, stir and logical nitrogen deoxygenation the preparatory emulsification 30～50min of normal temperature;
(4) with step 3. in the emulsion of gained be warming up to 50～70 ℃; 40～50wt.% the initiated polymerization that adds solution B; After treating that the system blue light occurs; Add residual acrylic acid ester monomer and solution B, and in 1～2h, dropwise, and acrylate monomer dropwises and should finish early than the dropping of solution B;
(5) dropwise continued under nitrogen protection and stirring condition, in 50～70 ℃, continue reaction 1～6h, cooling obtains the emulsion that solid content is the polyacrylic ester of 25%～45%wt.% at last;
(6) with the lime carbonate ultra-sonic dispersion in deionized water; Under the condition of magnetic agitation; Slowly drip and go up the 5. prepared polyacrylate polymers of step, form certain coating on the lime carbonate surface, contact certain slow-release time with acid until polymkeric substance; Contract through overwinding inspissation at last, obtain the solution C of solid content 30～50wt.%;
Wherein, described acrylate monomer is wherein one or more such as methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, vinylformic acid, TEB 3K, glyceral methacrylate;
Described initiator is a kind of among ammonium persulphate, Potassium Persulphate, the AIBA;
Described emulsifying agent be anionic or non-ionic type in one or more;
Described pH buffer reagent is NaCO
3Or NaHCO
3In a kind of.
Gained polyacrylate emulsion modified calcium carbonate is a suspension, can be used as modified calcium carbonate and directly is used to prepare phenol formaldehyde foam.At this moment, the weight of modified calcium carbonate is in the gross weight of suspension-s.
As Abietyl modified lime carbonate, through with rosin, lime carbonate and softening agent fusion, mix, cooling and pulverizing obtain.As softening agent, for example can mention terepthaloyl moietie, polyoxyethylene glycol, glycerine etc. wherein one or more.The Abietyl modified lime carbonate of gained is solid powdery, and for the ease of using, preferably its granularity is less than 0.25mm.For rosin, lime carbonate and plasticizer dosage, those skilled in the art can confirm as required.But, in order to ensure foaming effect, the weight of used lime carbonate is preferably the 40-60% of rosin weight.
As the solid paraffin modified calcium carbonate, through with solid paraffin, lime carbonate and softening agent fusion, mix, cooling and pulverizing obtain.As softening agent, for example can mention terepthaloyl moietie, polyoxyethylene glycol, glycerine etc. wherein one or more.Gained solid paraffin modified calcium carbonate is a solid powdery, and for the ease of using, preferably its granularity is less than 0.25mm.For solid paraffin, lime carbonate and plasticizer dosage, those skilled in the art can confirm as required.But, in order to ensure foaming effect, the weight of used lime carbonate is preferably the 40-60% of solid paraffin weight.
As the novolac resin modified calcium carbonate, through under low pressure, the molten novolac resin is mixed with lime carbonate, cooling, pulverizing obtain.Gained novolac resin modified calcium carbonate is a solid powdery, and for the ease of using, preferably its granularity is 200～400 orders.For the consumption of novolac resin and lime carbonate, those skilled in the art can confirm as required.But, in order to ensure foaming effect, the weight of used lime carbonate is preferably the 40-60% of novolac resin weight.
One preferred embodiment in, the novolac resin modified calcium carbonate prepares through following method:
(1) phenol, liquid formaldehyde adding are had in the reactor drum of prolong, open and stir and prolong, keeping temperature of charge is 30 ℃～40 ℃, and the consumption of liquid solid formaldehyde is 65%～75% of a phenol quality;
(2) add catalyzer, slowly be warming up to 85 ℃～100 ℃, isothermal reaction 2～4h, catalyst consumption is 0.5%～2% of a phenol quality;
(3) vacuumize dehydration, vacuum tightness-0.08～-0.1MPa, when temperature of charge reaches 140～170 ℃, add lime carbonate, high-speed stirring is to evenly, the discharging cooling; The consumption of lime carbonate is 40%～60% of a phenol;
(4) using kibbler that the novolac resin modified calcium carbonate that obtains is crushed to granularity is 200～400 orders,
Wherein, said catalyzer is oxalic acid, boric acid or acetate.
In the present invention, except modified calcium carbonate, also can use other carbonate of modification, like magnesiumcarbonate, barium carbonate etc.But, take all factors into consideration cost, modification mode and foaming effect, preferably use modified calcium carbonate.
In the present invention; As solidifying agent; Use can with the acid of its reaction of lime carbonate, specifically mention mineral acid such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and organic acid such as formic acid, oxalic acid, tosic acid, xylene monosulfonic acid, methylsulphonic acid, Witco 1298 Soft Acid.Wherein any can be used, also multiple combination can be used.
In order to ensure the speed of response of modified calcium carbonate and solidifying agent, guarantee the speed of overflowing and the exothermic heat of reaction speed of carbonic acid gas, thereby guarantee foaming effect; In the present invention; For the foamable resol of 100 weight parts, the consumption of modified calcium carbonate is 20 parts, and solidifying agent is 10～25 parts.Carbonic acid gas overflows excessive velocities/slow excessively, exothermic heat of reaction is too fast if the consumption of modified calcium carbonate and solidifying agent not in this scope, may cause/cross the problem that waits slowly, so that obtain the phenol formaldehyde foam of deterioration.
In the present invention, for tensio-active agent and the not special qualification of filler, can use this area tensio-active agent and filler commonly used.As tensio-active agent, can mention for example Tween-40, tween-80, AK8812 and L5400 etc., can use any one or more combination wherein.As filler, can mention for example polynite, hydrotalcite, spun glass, nano-calcium carbonate, white lake, Marinco H, Natural manganese dioxide and quicklime etc., can use any one or more combination wherein.
According to a further aspect in the invention, above-mentioned PREPARATION OF PHENOLIC FOAM method is provided, this method comprises mixes foamable resol, tensio-active agent, modified calcium carbonate and filler, adds solidifying agent then and foams, solidifies.
One preferred embodiment in; Foamable resol, tensio-active agent, modified calcium carbonate and filler joined in the reaction kettle together stir; Add solidifying agent again and stir fast together, pour into fast in the mould that is preheated to 30～40 ℃ after mixing, the baking oven of putting into 60～80 ℃ foams; Take out cooling and demolding, obtain the phenol formaldehyde foam goods.
Embodiment
Embodiment 1
1) preparation of polyacrylate emulsion modified calcium carbonate
1. with 10g ethyl propenoate (EA), 0.435g ammonium persulphate (APS), 1.739g sodium lauryl sulphate (SDS), 0.87gpH buffer reagent NaHCO
3Mix the adding reactor drum with the 180g deionized water, stir and logical nitrogen deoxygenation the preparatory emulsification 40min of normal temperature;
2. the emulsion that obtains is warming up to 70 ℃; Add ammonium persulphate (APS) aqueous solution and (contain APS0.2g; 15g water), treat that the system blue light occurs after, drip 73.5g ethyl propenoate and 3.5g glycidyl acrylate mix monomer and the APS aqueous solution simultaneously; 1.5h in dropwise, and propenoate mixing monomer dropwises at first;
3. dropwise continued under nitrogen protection and stirring condition, continue reaction 6h down at 70 ℃, cooling obtains the emulsion that solid content is the polyacrylic ester of 30%wt.% at last;
4. be in room temperature under to mix at 3: 1 polyacrylate emulsion and lime carbonate by mass ratio, churning time 30min obtains modified calcium carbonate suspension-s.
2) but foamed phenolic resin synthetic
600g phenol, 228g solid formaldehyde and 240g softening water are added in the 2L four-hole boiling flask, open and stir and prolong, holding temperature is at 30 ℃～40 ℃; Add 3g sodium hydroxide, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 4h; Add 6g trimeric cyanamide and 30g white lake, vacuumize dehydration, vacuum tightness-0.08～-0.1MPa; When system viscosity reaches 2000mPaS, cooling discharging, but obtain foamed phenolic resin.
3) PREPARATION OF PHENOLIC FOAM
With the foamable resol of 100g, 3g tween-80, the above-mentioned modified calcium carbonate suspension-s of 20g; 10g white lake joins together and stirs 3min in the reaction kettle, adds the 20g tosic acid again and stirs fast together, pours in the mould that is preheated to 40 ℃ after mixing fast; Put into 70 ℃ the baking oven 10min that foams, take out cooling and demolding, obtain the phenol formaldehyde foam goods; During the foam burning carbonization takes place, do not have the phenomenon of glowing, its pH is 5.
Embodiment 2
1) preparation of Abietyl modified lime carbonate
17.5g rosin, 17.5g lime carbonate and 0.17gPEG-1000 are put into beaker, be heated to fusion, and fully stir with electric mantle; Pour out cooling; Pulverize it with high speed disintegrator the cooling back, and filter with the mesh screen of 0.25mm, finally obtains desired Abietyl modified lime carbonate.
2) but foamed phenolic resin synthetic
600g phenol, 345g solid formaldehyde and 375g softening water are added in the 2L four-hole boiling flask, open and stir and prolong, holding temperature is at 30 ℃～40 ℃; Add 4.2g Natural manganese dioxide, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 3h; Vacuumize dehydration; Vacuum tightness-0.08～-0.1MPa, when system viscosity reaches 4000mPaS, cooling discharging;
3) PREPARATION OF PHENOLIC FOAM
The foamable resol of 100g, 3gL5400, the Abietyl modified lime carbonate of 15g, 15g white lake joined together stir 3min in the reaction kettle, add 15 parts of tosic acid and vitriolic mixture again, stir fast; Pour into fast in the mould that is preheated to 40 ℃ after mixing, put into 70 ℃ the baking oven 10min that foams, take out cooling and demolding; Obtain the phenol formaldehyde foam goods; During the foam burning carbonization takes place, do not have the phenomenon of glowing, its pH is 5.4.
Embodiment 3
(1) preparation of solid paraffin modified calcium carbonate
30g solid paraffin and 70g lime carbonate are put into beaker, be heated to fusion, and fully stir with electric mantle; Pour out cooling, again with its through the row freezing treatment, with high speed disintegrator it is pulverized at last; And filter with the mesh screen of 0.25mm, finally obtain desired solid paraffin modified calcium carbonate.
2) preparation of foamable resol
600g phenol, 268g solid formaldehyde and 290g softening water are added in the 2L four-hole boiling flask, open and stir and prolong, holding temperature is at 30 ℃～40 ℃; Add 6g sodium hydroxide, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 3h; Add 12g urea, 15g Marinco H and 15g white lake, vacuumize dehydration, vacuum tightness-0.08～-0.1MPa; When system viscosity reaches 4000mPaS, cooling discharging.
3) PREPARATION OF PHENOLIC FOAM
The foamable resol of 100g, 3gAK8812,20g solid paraffin modified calcium carbonate, 15g white lake, 2g terepthaloyl moietie joined together stir 3min in the reaction kettle, add 20 parts of tosic acid again and stir fast together, pour in the mould that is preheated to 40 ℃ after mixing fast; Put into 70 ℃ the baking oven 12min that foams; Take out cooling and demolding, obtain the phenol formaldehyde foam goods, carbonization takes place during the foam burning; Do not have the phenomenon of glowing, its pH is 6.
Embodiment 4
1) preparation of novolac resin modified calcium carbonate
300g phenol, 210g formaldehyde are added in the 1L four-hole boiling flask, open and stir and prolong, holding temperature adds 7.5g oxalic acid at 30 ℃～40 ℃, slowly is warming up to 90 ℃, isothermal reaction 3h; Vacuumize dehydration, vacuum tightness-0.08～-0.1MPa, when temperature of charge reaches 140～170 ℃, add 250g lime carbonate, high-speed stirring is to evenly, the discharging cooling obtains the novolac resin modified calcium carbonate; Using kibbler that modified calcium carbonate is crushed to granularity is 200～400 orders, obtains novolac resin modified calcium carbonate powder.
2) foamable resol is synthetic
600g phenol, 306g solid formaldehyde and 330g softening water are added in the 2L four-hole boiling flask, open and stir and prolong, holding temperature is at 30 ℃～40 ℃; Add 9g sodium hydroxide, slowly be warming up to 80 ℃～90 ℃, isothermal reaction 3h; Add 12g urea, 12g trimeric cyanamide and 60 parts of white lakes, vacuumize dehydration, vacuum tightness-0.08～-0.1MPa; When system viscosity reaches 5000mPaS, cooling discharging.
3) PREPARATION OF PHENOLIC FOAM
With the foamable resol of 100g, 3g tween-80,20g novolac resin modified calcium carbonate powder, 20g white lake; 3g terepthaloyl moietie joins together and stirs 3min in the reaction kettle, adds the 25g tosic acid again and stirs fast together, pours in the mould that is preheated to 40 ℃ after mixing fast; Put into 60～80 ℃ the baking oven 10min that foams, take out cooling and demolding, obtain the phenol formaldehyde foam goods; During the foam burning carbonization takes place, do not have the phenomenon of glowing, its pH is 6.
Test Example
The mensuration of phenolic foam material pH value:
With the surface of the smooth cleaning of the moistening phenol formaldehyde foam sample of deionized water, cover a slice pH value scope and be 1～14 test paper, place observation in 1 minute, measure the pH value.
More than through specific embodiment the present invention is further specified, but these embodiment only are exemplary, protection scope of the present invention are not constituted any restriction.It will be appreciated by those skilled in the art that under the situation that does not exceed spirit of the present invention and protection domain can carry out multiple replacement of equal value, modify or improve technical scheme of the present invention and embodiment thereof, these all should fall in protection scope of the present invention.Protection scope of the present invention is as the criterion with appended claim.
All documents of mentioning in the literary composition are incorporated herein by reference at this in full.
Claims (10)
1. phenol formaldehyde foam, this phenol formaldehyde foam is processed by following materials of weight proportions:
Foamable resol: 100 parts
Tensio-active agent: 2～8 parts
Modified calcium carbonate: 5～20 parts
Filler: 10～40 parts
Solidifying agent: 10～25 parts
This phenol formaldehyde foam does not have smolderability, and pH is 5～6;
Wherein, said modified calcium carbonate is selected from polyacrylate emulsion modified calcium carbonate, Abietyl modified lime carbonate, solid paraffin modified calcium carbonate and novolac resin modified calcium carbonate;
Described tensio-active agent is selected from Tween-40, tween-80, AK8812, L5400;
Described filler is selected from nano imvite, hydrotalcite, spun glass, nano-calcium carbonate, white lake, Marinco H, Natural manganese dioxide, quicklime;
Described solidifying agent is selected from: mineral acid such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and organic acid such as formic acid, oxalic acid, tosic acid, xylene monosulfonic acid, methylsulphonic acid, Witco 1298 Soft Acid.
2. phenol formaldehyde foam according to claim 1, this phenol formaldehyde foam is processed by following materials of weight proportions:
Foamable resol: 100 parts
Tensio-active agent: 2～4 parts
Modified calcium carbonate: 15～20 parts
Filler: 10～20 parts
Solidifying agent: 15～25 parts.
3. phenol formaldehyde foam according to claim 1 and 2, wherein said polyacrylate emulsion modified calcium carbonate make polyacrylic ester form coating film on the lime carbonate surface and prepare through polyacrylate emulsion is mixed with lime carbonate water-based dispersion liquid.
4. phenol formaldehyde foam according to claim 3, wherein said polyacrylate emulsion modified calcium carbonate prepares through following method:
(1) acrylate monomer, initiator, emulsifying agent, p H buffer reagent and deionized water are backed up by following mass percent: acrylate monomer: 20～40%; Initiator: 0.3～1%; Emulsifying agent: 1～2%; Buffer reagent: 0.5～1%; Surplus is a deionized water;
(2) initiator is with the deionized water dissolving in the step (1), wiring solution-forming B;
(3) emulsifying agent, pH buffer reagent and the residue deionized water of the 5～10wt.%, step that gets acrylate monomer in the step (1) in 1. mixes and adds reactor drum, stirs and logical nitrogen deoxygenation the preparatory emulsification 30～50min of normal temperature;
(4) emulsion with gained in the step (3) is warming up to 50～70 ℃; 40～50wt.% the initiated polymerization that adds solution B; After treating that the system blue light occurs; Add residual acrylic acid ester monomer and solution B, and in 1～2h, dropwise, and acrylate monomer dropwises and should finish early than the dropping of solution B;
(5) dropwise continued under nitrogen protection and stirring condition, in 50～70 ℃, continue reaction 1～6h, cooling obtains the emulsion that solid content is the polyacrylic ester of 25%～45%wt.% at last;
(6) with the lime carbonate ultra-sonic dispersion in deionized water; Under the condition of magnetic agitation; Slowly drip and go up the prepared polyacrylate polymers of step (5), form certain coating on the lime carbonate surface, contact certain slow-release time with acid until polymkeric substance; Contract through overwinding inspissation at last, obtain the solution C of solid content 30～50wt.%;
Wherein, described acrylate monomer is wherein one or more such as methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, vinylformic acid, TEB 3K, glyceral methacrylate;
Described initiator is a kind of among ammonium persulphate, Potassium Persulphate, the AIBA;
Described emulsifying agent be anionic or non-ionic type in one or more;
Described pH buffer reagent is NaCO
3Or NaHCO
3In a kind of.
5. phenol formaldehyde foam according to claim 1 and 2, wherein Abietyl modified lime carbonate mixes through with rosin, lime carbonate and softening agent fusion, and cooling and pulverizing obtain,
Wherein softening agent be selected from terepthaloyl moietie, polyoxyethylene glycol, glycerine etc. wherein one or more.
6. phenol formaldehyde foam according to claim 1 and 2, wherein the solid paraffin modified calcium carbonate mixes through with solid paraffin, lime carbonate and softening agent fusion, and cooling and pulverizing obtain.
7. phenol formaldehyde foam according to claim 1 and 2, wherein the novolac resin modified calcium carbonate through under low pressure, mixes the molten novolac resin with lime carbonate, and cooling, pulverizing obtain.
8. phenol formaldehyde foam according to claim 7, wherein the novolac resin modified calcium carbonate prepares through following method:
(1) phenol, liquid formaldehyde adding are had in the reactor drum of prolong, open and stir and prolong, keeping temperature of charge is 30 ℃～40 ℃, and the consumption of liquid solid formaldehyde is 65%～75% of a phenol quality;
(2) add catalyzer, slowly be warming up to 85 ℃～100 ℃, isothermal reaction 2～4h, catalyst consumption is 0.5%～2% of a phenol quality;
(3) vacuumize dehydration, vacuum tightness-0.08～-0.1MPa, when temperature of charge reaches 140～170 ℃, add lime carbonate, high-speed stirring is to evenly, the discharging cooling; The consumption of lime carbonate is 40%～60% of a phenol;
(4) using kibbler that the novolac resin modified calcium carbonate that obtains is crushed to granularity is 200～400 orders,
Wherein, said catalyzer is one or more in oxalic acid, boric acid and the acetate.
9. according to each described phenol formaldehyde foam among the claim 1-8, it is through mixing foamable resol, tensio-active agent, modified calcium carbonate and filler, adds solidifying agent then and foams, solidifies and make.
10. according to each described phenol formaldehyde foam among the claim 1-9, wherein modified calcium carbonate is replaced with modification magnesiumcarbonate or modification barium carbonate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146016A (en) * | 2013-04-03 | 2013-06-12 | 山东轻工业学院 | Method for preparing melamine-formaldehyde foam by taking rosin as pore-foaming agent |
| CN104559044A (en) * | 2014-12-30 | 2015-04-29 | 陕西师范大学 | Non-corrosive, low-density and high-strength phenolic foam |
| CN106366560A (en) * | 2016-08-30 | 2017-02-01 | 江苏德明新材料有限公司 | Epoxy modified pressure-proof phenolic foam plate and preparation method thereof |
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|---|---|---|---|---|
| CN101033307A (en) * | 2006-03-10 | 2007-09-12 | 上海尖端工程材料有限公司 | Method of preparing pnenolic aldehyde foam from modified foamable phenolic resin |
| CN101305034A (en) * | 2005-09-08 | 2008-11-12 | 金斯潘控股有限公司 | A phenolic foam |
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2012
- 2012-05-23 CN CN201210163072.9A patent/CN102649866B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101305034A (en) * | 2005-09-08 | 2008-11-12 | 金斯潘控股有限公司 | A phenolic foam |
| CN101033307A (en) * | 2006-03-10 | 2007-09-12 | 上海尖端工程材料有限公司 | Method of preparing pnenolic aldehyde foam from modified foamable phenolic resin |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146016A (en) * | 2013-04-03 | 2013-06-12 | 山东轻工业学院 | Method for preparing melamine-formaldehyde foam by taking rosin as pore-foaming agent |
| CN104559044A (en) * | 2014-12-30 | 2015-04-29 | 陕西师范大学 | Non-corrosive, low-density and high-strength phenolic foam |
| CN106366560A (en) * | 2016-08-30 | 2017-02-01 | 江苏德明新材料有限公司 | Epoxy modified pressure-proof phenolic foam plate and preparation method thereof |
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