CN104262898A - Organic-inorganic composite modified flame-retardant phenolic foam - Google Patents
Organic-inorganic composite modified flame-retardant phenolic foam Download PDFInfo
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- CN104262898A CN104262898A CN201410462630.0A CN201410462630A CN104262898A CN 104262898 A CN104262898 A CN 104262898A CN 201410462630 A CN201410462630 A CN 201410462630A CN 104262898 A CN104262898 A CN 104262898A
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- 239000006260 foam Substances 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000004202 carbamide Substances 0.000 claims abstract description 31
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 31
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003607 modifier Substances 0.000 claims abstract description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 12
- 238000005187 foaming Methods 0.000 claims abstract description 7
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 31
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 19
- 239000011159 matrix material Substances 0.000 claims description 17
- 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 class 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 claims description 12
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 3
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 claims description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 3
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 238000009830 intercalation Methods 0.000 abstract description 2
- 230000002687 intercalation Effects 0.000 abstract description 2
- 229920001568 phenolic resin Polymers 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000004088 foaming agent Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 229920001187 thermosetting polymer Polymers 0.000 abstract 1
- 239000003063 flame retardant Substances 0.000 description 9
- 229920003987 resole Polymers 0.000 description 9
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000004566 building material Substances 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses organic-inorganic composite modified flame-retardant phenolic foam. Modified thermosetting phenol-formaldehyde resin is synthesized through formaldehyde, phenol and an organic modifier under an alkali environment, then is subjected to vacuum dewatering to a certain viscosity, and is subjected to foaming by uniformly mixing with the addition of a surfactant, a foaming agent, a curing agent and an inorganic modifier, wherein the organic modifier is a long-chain polyfunctional glycidyl ether, which can improve the brittleness of the conventional phenolic foam and reduce the residue rate of the foam; and the inorganic modifier is urea intercalation nano-montmorillonite, and reinforces the flame retardancy of the organic modified phenolic foam as well as improves the mechanical properties of the foam. According to the organic-inorganic composition modifying method, the phenolic foam with excellent mechanical properties, low residue rate and good flame retardancy is finally obtained.
Description
Technical field
The present invention relates to a kind of Organic-inorganic composite modified flame-retardant phenol formaldehyde foam, be mainly used in building exterior wall heat preserving.
Background technology
Resol is one of industrialized resin the earliest.Resol synthesis the earliest can trace back to for 20 beginnings of the century, from Belgian chemist L.H.bankcland in the lab first time novolak resin, and preliminary parsing and research have been carried out to the synthesis mechanism of resol.The fifties in last century, resol just in West Europe, North America, Japan Area use widely.Resol is widely used in multiple industry because of advantages such as its good insulativity, thermal insulation, high strength, mainly comprises: the manufacture of heat preserving and insulating material, wood-based plate, fire-proof and thermal-insulation coating, high abrasion plastic prod etc.
In recent years, flourish along with China's building trade, many urban architectures due to external-wall heat-insulation material flame retardant rating not up to standard, cause fire to occur, cause a tremendous loss of lives.2009 and national " outer heat preservation system and decoration of exterior wall fire prevention temporary provisions " (public logical word [No. 2009146] and " notice of further clear and definite covil construction heat insulating material for external fire supervision management relevant requirements " (public affairs disappear [No. 2011165]) of issuing in 2011, strict requirement is proposed to the flame retardant properties of building materials, the leading indicator oxygen index OI index < 22 of material is inflammable material, 22 < OI index < 27 are combustible matls, OI index > 28 is nonflammable materials, OI index be greater than 32 be B
1level flame-retardant thermal insulation material, phenol formaldehyde foam reaches B
1level fire retardant foam standard, simultaneously it cheap, synthesis technique simple, in building materials lagging material, have irreplaceable status.But the phenyl ring of rigid structure occupies a large amount of ratios in phenol formaldehyde foam, phenyl ring pile up in a large number connect cause phenol formaldehyde foam poor toughness, development that shortcoming that Pulverization ratio is high limits phenol formaldehyde foam.
The modification of resol mainly contains physically modified and chemical modification two kinds, wherein physically modified in resin, mainly add that various elasticity is high, modulus is high, liquid, powder, the filamentary material good with resin compatible, reach enhancing, toughness reinforcing object, but all the flame retardant properties of foam is had a significant impact.Chemical modification is mainly divided into two large classes: one is replace part phenol and formaldehyde to react with various phenolic compound, phenolic compound with specified property can be linked among resol, chemical structure is modified resol, but due to the existence of phenyl ring in phenolic compound, toughening effect is not obvious.Two is allow carry out synthesis modification resol with the compound of soft segment and phenol, formaldehyde copolymer.The people such as Liang Mingli use base polyurethane prepolymer for use as and phenol formaldehyde foam to carry out chemical reaction, the soft segment of urethane is allowed to be linked among phenol formaldehyde foam, a small amount of performed polymer add the Pulverization ratio that significantly can reduce foam, but thisly sharply to decline with polyurethane-modified foam oxygen index.Within 2005, first Yang.H synthesizes a kind of polyether compound of phosphorous high molecular, then uses this compound to carry out modification to phenol formaldehyde foam, introduces the oxygen index that phosphorous group improves modification foam in phenol formaldehyde foam.The foam oxygen index finally obtained has rise to a certain degree, reaches B
1the demand of level fire retardant foam, but this method of modifying cost is very high, is difficult to apply.
Summary of the invention
The invention discloses a kind of Organic-inorganic composite modified flame-retardant phenol formaldehyde foam, by the heat-reactive phenolic resin of formaldehyde, phenol, organic modifiers synthesis modification in the basic conditions, then after vacuum hydro-extraction to certain viscosity, add tensio-active agent, whipping agent, solidifying agent, inorganic modifier, stir and foam.Wherein organic modifiers is the polyfunctionality glycidyl ether of long-chain, it can improve the fragility of traditional phenol formaldehyde foam, and that reduces foam falls slag rate, and inorganic modifier is the nano imvite of urea intercalation, while the organically-modified phenol formaldehyde foam flame retardant resistance of reinforcement, improve the physical and mechanical properties of foam.Finally obtain good mechanical performance by the method for this Organic-inorganic composite modification, fall the phenol formaldehyde foam that slag rate is low, flame retardant properties is good.
A kind of Organic-inorganic composite modified flame-retardant phenol formaldehyde foam, it is characterized in that: after comprising dehydration, viscosity is matrix resin 100 weight part, tensio-active agent 5 weight part, whipping agent 5 weight part, solidifying agent 10 weight part, the inorganic modifier 0-10 weight part of 4000-6000mpa.s, after mechanical stirring is even, pour in mould, foam 3 hours at 70 DEG C; Tensio-active agent is tween 80; Whipping agent is Skellysolve A; Solidifying agent is phosphoric acid; Inorganic modifier is urea intercalated montmorillonite;
Wherein matrix resin comprises phenol, formaldehyde, polyfunctionality glycidyl ether, basic catalyst; Wherein phenol 100 weight part, mass percent are the formalin of 37%: 130-170 weight part, polyfunctionality glycidyl ether: 3-10 weight part, basic catalyst are 30wt% aqueous sodium hydroxide solution: 8-15 weight part.
Polyfunctionality glycidyl ether is polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidylether, 1, one of 4-ethylene glycol diglycidylether, neopentyl glycol diglycidyl glyceryl ether, 1,6-hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, glycerin triglycidyl ether.
Inorganic modifier is urea intercalated montmorillonite, preparation method is as follows: pulverize after being dried by urea, 200 order urea powder are obtained after sieving, then by urea powder and polynite powder Homogeneous phase mixing, urea add-on is the 10-40% of polynite weight part, finally finely dispersed mixture is put into 90 DEG C of baking ovens and activate 2h, obtain urea intercalated montmorillonite.
Described phenol formaldehyde foam preparation method is as follows:
1) under the state stirred, phenol 100 weight part, mass percent are the formalin of 37%: 130-170 weight part, basic catalyst 30wt% aqueous sodium hydroxide solution 8-15 weight part, polyfunctionality glycidyl ether 3-10 weight part add in reactor, stir speed (S.S.) is 600r/min, insulation reaction 30min after being warming up to 60 DEG C;
2) be warming up to 90-98 DEG C, cool after insulation reaction 30-90min at this temperature;
3) obtain with after vacuum pump dehydration 60-120min the modified matrix resin that viscosity is 4000-6000mpa.s;
4) by modified matrix resin 100 weight part, tensio-active agent 5 weight part, whipping agent 5 weight part, solidifying agent 10 weight part, inorganic modifier 3-10 weight part, after mechanical stirring is even, pour in mould, at 70 DEG C, foaming obtains modified phenolic foam in 3 hours.
The present invention by the method for Organic-inorganic composite modification, improvement phenol formaldehyde foam fragility and fall slag many while ensure its flame retardant properties, control the cost of product simultaneously.
Accompanying drawing explanation
The polynite sample XRD of the different urea content of Fig. 1 characterizes
Along with the increase gradually of urea addition, 001 crystal face interlamellar spacing of polynite also increases gradually, obtains maximum spacing when urea add-on is 30% of polynite weight part.
Embodiment
Embodiment 1
Inorganic modifier is urea intercalated montmorillonite, preparation method is as follows: pulverize with high speed disintegrator after being dried by urea, 200 order urea powder are obtained after sieving, then the Homogeneous phase mixing under high speed dispersor by urea powder and polynite powder, urea add-on is 10% of polynite weight part, finally finely dispersed mixture is put into 90 DEG C of baking oven high-temperature activation 2h, obtain urea intercalated montmorillonite.
The preparation of phenol formaldehyde foam: under the state stirred, phenol 100 weight part, mass percent are the formalin of 37%: 130 weight parts, basic catalyst 30wt% aqueous sodium hydroxide solution 8 weight part, polyethyleneglycol diglycidylether: 3 weight parts add in reactor, stir speed (S.S.) is 600r/min, insulation reaction 30min after being warming up to 60 DEG C; Be warming up to 90 DEG C.Cool after insulation reaction 30min at this temperature; Dewater under-0.1MPa vacuum tightness after 60min with vacuum pump and obtain the modified matrix resin that viscosity is 4000mpa.s; Modified matrix resin 100 weight part, tensio-active agent 5 weight part, whipping agent 5 weight part, solidifying agent 10 weight part, inorganic modifier 3 weight part, after mechanical stirring is even, pour in mould, and at 70 DEG C, foaming obtains modified phenolic foam in 3 hours.
Embodiment 2
In the preparation method of present embodiment inorganic modifier urea intercalated montmorillonite, urea add-on is 20% of polynite add-on, and other are identical with embodiment 1.
Embodiment 3
In the preparation method of present embodiment inorganic modifier urea intercalated montmorillonite, urea add-on is 30% of polynite add-on, and other are identical with embodiment 1.
Embodiment 4
In the preparation method of present embodiment inorganic modifier urea intercalated montmorillonite, urea add-on is 40% of polynite add-on, and other are identical with embodiment 1.
Embodiment 5
In the preparation process of present embodiment phenol formaldehyde foam, formalin add-on is 150 weight parts, and other are identical with embodiment 1.
Embodiment 6
In the preparation process of present embodiment phenol formaldehyde foam, formalin add-on is 170 weight parts, and other are identical with embodiment 1.
Embodiment 7
In the preparation process of present embodiment phenol formaldehyde foam, 30wt% aqueous sodium hydroxide solution add-on is 12 weight parts, and other are identical with embodiment 1.
Embodiment 8
In the preparation process of present embodiment phenol formaldehyde foam, 30wt% aqueous sodium hydroxide solution add-on is 15 weight parts, and other are identical with embodiment 1.
Embodiment 9
In the preparation process of present embodiment phenol formaldehyde foam, polyethyleneglycol diglycidylether add-on is 6 weight parts, and other are identical with embodiment 1.
Embodiment 10
In the preparation process of present embodiment phenol formaldehyde foam, polyethyleneglycol diglycidylether add-on is 10 weight parts, and other are identical with embodiment 1.
Embodiment 11
In the preparation process of present embodiment phenol formaldehyde foam, polyfunctionality glycidyl ether is polypropylene glycol diglycidyl ether, and other are identical with embodiment 1.
Embodiment 12
In the preparation process of present embodiment phenol formaldehyde foam, polyfunctionality glycidyl ether is ethylene glycol diglycidylether, and other are identical with embodiment 1.
Embodiment 13
In the preparation process of present embodiment phenol formaldehyde foam, polyfunctionality glycidyl ether is Isosorbide-5-Nitrae-ethylene glycol diglycidylether, and other are identical with embodiment 1.
Embodiment 14
In the preparation process of present embodiment phenol formaldehyde foam, polyfunctionality glycidyl ether is neopentyl glycol diglycidyl glyceryl ether, and other are identical with embodiment 1.
Embodiment 15
In the preparation process of present embodiment phenol formaldehyde foam, polyfunctionality glycidyl ether is 1,6-hexanediol diglycidyl ether, and other are identical with embodiment 1.
Embodiment 16
In the preparation process of present embodiment phenol formaldehyde foam, polyfunctionality glycidyl ether is trihydroxymethylpropanyltri diglycidyl ether, and other are identical with embodiment 1.
Embodiment 17
In the preparation process of present embodiment phenol formaldehyde foam, polyfunctionality glycidyl ether is glycerin triglycidyl ether, and other are identical with embodiment 1.
Embodiment 18
In the preparation process of present embodiment phenol formaldehyde foam, the second step temperature of reaction of matrix resin is 95 DEG C, and other are identical with embodiment 1.
Embodiment 19
In the preparation process of present embodiment phenol formaldehyde foam, the second step temperature of reaction of matrix resin is 98 DEG C, and other are identical with embodiment 1.
Embodiment 20
In the preparation process of present embodiment phenol formaldehyde foam, the second step reaction times of matrix resin is 60min, and other are identical with embodiment 1.
Embodiment 21
In the preparation process of present embodiment phenol formaldehyde foam, the second step temperature of reaction of matrix resin is 90min, and other are identical with embodiment 1.
Embodiment 22
3rd step vacuum hydro-extraction 90min of matrix resin in the preparation process of present embodiment phenol formaldehyde foam, obtain resin viscosity 5000mpa.s, other are identical with embodiment 1.
Embodiment 23
3rd step vacuum hydro-extraction 120min of matrix resin in the preparation process of present embodiment phenol formaldehyde foam, obtain resin viscosity 6000mpa.s, other are identical with embodiment 1.
Embodiment 24
In the preparation process of present embodiment phenol formaldehyde foam, in foaming process, inorganic modifier add-on is 6 weight parts, and other are identical with embodiment 1.
Embodiment 25
In the preparation process of present embodiment phenol formaldehyde foam, in foaming process, inorganic modifier add-on is 10 weight parts, and other are identical with embodiment 1.
Comparative example 1
Present embodiment does not add polyfunctionality glycidyl ether in matrix resin in the preparation process of phenol formaldehyde foam, does not add inorganic modifier in foaming process, and other are identical with embodiment 1.
Table 1 embodiment sample test performance
Claims (4)
1. an Organic-inorganic composite modified flame-retardant phenol formaldehyde foam, it is characterized in that: after comprising dehydration, viscosity is matrix resin 100 weight part, tensio-active agent 5 weight part, whipping agent 5 weight part, solidifying agent 10 weight part, the inorganic modifier 0-10 weight part of 4000-6000mpa.s, after mechanical stirring is even, pour in mould, foam 3 hours at 70 DEG C; Tensio-active agent is tween 80; Whipping agent is Skellysolve A; Solidifying agent is phosphoric acid; Inorganic modifier is urea intercalated montmorillonite;
Wherein matrix resin comprises phenol, formaldehyde, polyfunctionality glycidyl ether, basic catalyst; Wherein phenol 100 weight part, mass percent are the formalin of 37%: 130-170 weight part, polyfunctionality glycidyl ether: 3-10 weight part, basic catalyst are 30wt% aqueous sodium hydroxide solution: 8-15 weight part.
2. phenol formaldehyde foam according to claim 1, it is characterized in that: polyfunctionality glycidyl ether is polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidylether, 1, one of 4-ethylene glycol diglycidylether, neopentyl glycol diglycidyl glyceryl ether, 1,6-hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, glycerin triglycidyl ether.
3. phenol formaldehyde foam according to claim 1, it is characterized in that: inorganic modifier is urea intercalated montmorillonite, preparation method is as follows: pulverize after being dried by urea, 200 order urea powder are obtained after sieving, then by urea powder and polynite powder Homogeneous phase mixing, urea add-on is the 10-40% of polynite weight part, finally finely dispersed mixture is put into 90 DEG C of baking ovens and activates 2h, obtain urea intercalated montmorillonite.
4. phenol formaldehyde foam according to claim 1, is characterized in that preparation method is as follows:
1) under the state stirred, phenol 100 weight part, mass percent are the formalin of 37%: 130-170 weight part, basic catalyst 30wt% aqueous sodium hydroxide solution 8-15 weight part, polyfunctionality glycidyl ether 3-10 weight part add in reactor, stir speed (S.S.) is 600r/min, insulation reaction 30min after being warming up to 60 DEG C;
2) be warming up to 90-98 DEG C, cool after insulation reaction 30-90min at this temperature;
3) obtain with after vacuum pump dehydration 60-120min the modified matrix resin that viscosity is 4000-6000mpa.s;
4) by modified matrix resin 100 weight part, tensio-active agent 5 weight part, whipping agent 5 weight part, solidifying agent 10 weight part, inorganic modifier 3-10 weight part, after mechanical stirring is even, pour in mould, at 70 DEG C, foaming obtains modified phenolic foam in 3 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106432653A (en) * | 2016-08-30 | 2017-02-22 | 江苏德明新材料有限公司 | Environment-friendly phenolic foam insulation board and preparation method thereof |
| CN107057288A (en) * | 2017-05-22 | 2017-08-18 | 安徽三义和能源科技有限公司 | A kind of preparation method of Pressure-resistant fireproof plate |
| CN111793314A (en) * | 2020-07-23 | 2020-10-20 | 安徽中通电缆科技有限公司 | Irradiation crosslinking low-smoke halogen-free flame-retardant fire-resistant insulated wire |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734679A (en) * | 2008-11-18 | 2010-06-16 | 北京化工大学 | Microwave method for peeling laminar inorganic material quickly |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734679A (en) * | 2008-11-18 | 2010-06-16 | 北京化工大学 | Microwave method for peeling laminar inorganic material quickly |
Non-Patent Citations (1)
| Title |
|---|
| 张鑫等: ""活性环氧稀释剂改性酚醛泡沫的制备与性能研究"", 《塑料工业》, vol. 42, no. 7, 31 July 2014 (2014-07-31), pages 23 - 26 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN106432653A (en) * | 2016-08-30 | 2017-02-22 | 江苏德明新材料有限公司 | Environment-friendly phenolic foam insulation board and preparation method thereof |
| CN107057288A (en) * | 2017-05-22 | 2017-08-18 | 安徽三义和能源科技有限公司 | A kind of preparation method of Pressure-resistant fireproof plate |
| CN111793314A (en) * | 2020-07-23 | 2020-10-20 | 安徽中通电缆科技有限公司 | Irradiation crosslinking low-smoke halogen-free flame-retardant fire-resistant insulated wire |
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| CN104262898B (en) | 2016-08-17 |
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