CN101962474A - Environment-friendly high-flame retardance rigid polyurethane foam and preparation method and application thereof - Google Patents
Environment-friendly high-flame retardance rigid polyurethane foam and preparation method and application thereof Download PDFInfo
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- CN101962474A CN101962474A CN2010102738426A CN201010273842A CN101962474A CN 101962474 A CN101962474 A CN 101962474A CN 2010102738426 A CN2010102738426 A CN 2010102738426A CN 201010273842 A CN201010273842 A CN 201010273842A CN 101962474 A CN101962474 A CN 101962474A
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Abstract
The invention discloses environment-friendly high-flame retardance rigid polyurethane foam and a preparation method and application thereof. The environment-friendly high-flame retardance rigid polyurethane foam is prepared by mixing and reacting polymer polyol, water, a flame retardant, modified cenospheres and polyisocyanate in the presence of a foam stabilizer and/or a catalyst; a rigid polyurethane foaming mixture can be sprayed on a vertical face; and sprayed liquid is not suspended on the vertical face within 4 minutes. The polyurethane foam has the heat conductivity of 0.019 to 0.030 W/(m.K), the closed porosity of over 96.3 percent, the stability of cold and thermal cycle size of less than 2 percent, the level of vertical flame of V-0 level, remarkably reduced water absorption, and better application to the aspect of heat preservation of external walls, pipelines and refrigeration equipment of buildings.
Description
Technical field
The invention belongs to the hard polyurethane foams technical field, be specifically related to a kind of environment-friendly high fire-retardant hard polyurethane foams and its production and application.
Background technology
Rigid polyurethane foam has good heat-proof quality, all has widely in building exterior wall heat preserving, refrigerating plant and pipelines and petrochemical pipelines and uses.
Energy-saving and cost-reducing is the important trend of CHINESE INDUSTRIES policy development, hard polyurethane foams as energy-saving and cost-reducing lagging material need possess following condition: the thermal conductivity that (1) is very low, the thermal conductivity of hard polyurethane foams is mainly by gas phase thermal conductivity, matrix thermal conductivity and the decision of radiation thermal conductivity in the bubble, wherein the gas phase thermal conductivity depends on the stopping property or the flowability of gas conduction coefficient and gas, this requires hard polyurethane foams to have very high rate of closed hole, requires to reach more than 80%; (2) have the good flame performance, this requirement needs aspect building exterior wall heat preserving especially; (3) have very high intensity, and require to vary with temperature to have good dimensional stability; (4) have good water tolerance, because the thermal conductivity of moisture is very big, hard polyurethane foams absorbs a spot of moisture can cause that thermal conductivity raises fast, reduces heat insulation effect.
The whipping agent that the preparation hard polyurethane foams uses is very big to its heat-insulating property influence, traditional chloro fluorocarbon compound is the good whipping agent of hard polyurethane foams, its thermal conductivity is very low, but chloro fluorocarbon compound is quite serious to the destruction of ozonosphere, now ban use of, replace in order to hydrogen fluorocarbon compound or pentane.Patent CN101177474A, CN100363578C and CN101134804A have reported that employing hydrogen fluorocarbon compound makes whipping agent, and prepared hard polyaminoester thermal conductivity is lower than 0.03W/ (mK).CN101177474A has reported that employing water and hydrogen fluorohydrocarbon make whipping agent jointly, and prepared hard polyaminoester thermal conductivity also can be lower than 0.03W/ (mK).Though the hydrogen fluorohydrocarbon has lower ODP value than Chlorofluorocarbons (CFCs), and is little to the atmospheric layer ozone layer destroying, its destructiveness still exists.Patent CN1244618C and CN101085827A adopt Skellysolve A and the mixed use of hydrogen fluorohydrocarbon, as the hard polyurethane foams whipping agent, reduced the consumption of hydrogen fluorohydrocarbon, also can obtain to be lower than the thermal conductivity of 0.03W/ (mK), Skellysolve A has inflammable and explosive characteristic, has very big potential safety hazard as whipping agent.Water and isocyanate reaction produce CO
2, can original position generate polyurethane foam, be the very whipping agent of environmental protection of preparation polyurethane foam, also be a megatrend of polyurethane foam whipping agent.But the CO of full water foamed generation
2Thermal conductivity ratio hydrogen fluorohydrocarbon own and Pentyl alcohol height, full water foamed hard polyaminoester will be less than 0.03W/ (mK) thermal conductivity and have certain difficulty, patent CN100443683C, CN101348551A and CN101544736A etc. have reported full water foamed hard polyurethane foams, overcome CO by improving the foam rate of closed hole
2The high thermal conductivity of bubble, make full water foamed hard polyurethane foams thermal conductivity can be lower than 0.03W/ (mK), but technique scheme does not solve the fire-retardant technical problem of polyurethane foam, can not be applied to require the building heat preservation and the technical fields such as household electrical appliances manufacturing or indoor joint filling sealing of flame-retarding.
Can be more as the fire retardant of hard polyurethane foams, comprise mineral filler, metal oxide, metal hydroxides, expanded graphite, halogen-containing polyvalent alcohol, halogenated phosphate and not halogen-containing organophosphate.Wherein not halogen-containing organophosphate is as the hard polyurethane foams fire retardant, advantage such as have that consumption is few, good flame retardation effect and burning black smoke are few, its shortcoming is that organophosphate can play plastification in hard polyurethane foams, reduce the intensity and the dimensional stability of porous plastics, need to strengthen to obtain well stability.Patent CN1404503A is reported in the tiny balloon that adds massfraction 5～35% in the polyurethane foam, can significantly strengthen porous plastics, adopt this technology to utilize tiny balloon enhanced porous plastics as auto-parts such as column, threshold, roof-rack and roof transversary, this technology does not solve technical problems such as fire-retardant equally, can not be applied to fire-retardant and field of thermal insulation.With regard to existing patented technology, adopting full water foamed hard polyurethane foams to have fine flame retardant resistance, not reduce the report of intensity and dimensional stability again less.Patent CN101316875A has reported a kind of full water foamed flame retardant rigid polyurethane foam, with organophosphate and inorganic combustion inhibitor such as hibbsite, magnesium hydroxide and ANTIMONY TRIOXIDE SB 203 99.8 PCT and be used for improving flame retardant resistance, and the adding filler comprises that inorganic powder and fibrous powder strengthen, description according to patent CN101316875A, its described hard polyurethane foams has good flame, the definite I class rank of alter mode of ASTM E-84 continuous tunnel furnace test can be reached, and electronic housing, building decoration molding product and carrier vehicle inwall can be used for.This technology is characterized in that polyvalent alcohol in the constituent must contain the sucrose polylol of 2 weight～35 weight %, do not comprise polyvalent alcohol based on TriMethylolPropane(TMP), because sucrose polylol hydroxy functionality is quite high, generally be not less than 8, hydroxyl can not be fully in polymerization process and isocyanate reaction, the residual meeting of great amount of hydroxy group causes reacting incomplete and water tolerance is not good, the easy moisture absorption, because the thermal conductivity of moisture is very big, hard polyurethane foams absorbs a spot of moisture will cause that thermal conductivity raises fast, so the heat insulation effect of this technology hard polyurethane foams reduces greatly.
In sum, there is following problem in existing hard polyurethane foams technology:
(1) hard polyurethane foams adopts not environment-friendly foaming agent such as Chlorofluorocarbons (CFCs); (2) full water foamed hard polyurethane foams does not have flame retardant resistance; (3) the flame-retardant hard polyurethane foamy body is low, poor dimensional stability, mostly adopt mineral filler or fibrous material to strengthen the flame-retardant hard polyurethane foam, but mineral filler or fibrous material itself can reduce rigid polyurethane foam frothing percentage and heat-insulating property again; (4) in the many Application Areass of hard polyurethane foams, during particularly building exterior wall heat preserving is used, hard polyurethane foam liquid need be sprayed directly into vertical elevation, and the spraying liquid can not on vertical elevation, produce sagging, prior art all can not reach this requirement on the whole.
Summary of the invention
One object of the present invention is to overcome the deficiency of existing hard polyurethane foams technology, a kind of environment-friendly high fire-retardant hard polyurethane foams is provided, hard polyurethane foams of the present invention has following advantage simultaneously: (1) hard polyurethane foam liquid can spray to vertical elevation, does not produce sagging; (2) the present invention is used to improve the flame-retardant hard polyurethane foamy body with the modification cenosphere, does not reduce its hard polyurethane foams frothing percentage and heat-insulating property simultaneously; (3) has very high rate of closed hole, very low thermal conductivity; (4) has the good flame performance; (5) have very high intensity and good dimensional stability; (6) has good water tolerance.
Another object of the present invention provides the preparation method of described hard polyurethane foams.
A further object of the invention provides the application of described hard polyurethane foams.
Purpose of the present invention is achieved by the following technical programs:
Scheme one, the present invention foams with polyisocyanates the composition of polymer polyatomic alcohol, water, fire retardant, foam stabilizer, modification cenosphere through reaction, obtain the flame-retardant hard polyurethane foam of high comprehensive performance.
More preferred scheme is the flame-retardant hard polyurethane foam that the mixed reaction under foam stabilizer and the common condition that exists of catalyzer of polymer polyatomic alcohol, water, fire retardant, modification cenosphere and polyisocyanates is obtained high comprehensive performance, can successfully realize fast foaming, prevent the facade sagging, be fit to be applied to the foaming enforcement on the throne of buildings.
Described polymer polyatomic alcohol hydroxy functionality is preferably between 2～8, more preferably between 3～6; Hydroxyl value is preferably between 150～800mgKOH/g, more preferably between 200～600mgKOH/g; Described polymer polyatomic alcohol comprises a kind of natural fats and oils base polyester polyol at least, and the massfraction that natural fats and oils base polyester polyol accounts for polymer polyatomic alcohol is between 1～40%, and preferred massfraction is between 3～30%.Importantly, described polymer polyatomic alcohol does not comprise sucrose based polyalcohol polyvalent alcohol.Specifically, the suitable polymers polyvalent alcohol comprises polyether glycol, polyester polyol or natural fats and oils base polyester polyol and their mixture.
Wherein, described polyether glycol can be caused synthesis of epoxy compounds and make in the presence of catalyzer (KOH etc.) by the small molecular alcohol of hydroxy functionality 2～8, for example can select ethylene glycol, butyleneglycol, glycol ether, glycerine, TriMethylolPropane(TMP) and tetramethylolmethane cause oxyethane, a kind of in the polymkeric substance of propylene oxide and tetrahydrofuran (THF) or their arbitrary proportion mixture, can also select glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Xylitol, N.F,USP MANNITOL or sorbyl alcohol a kind of or their arbitrary proportion mixture are made initiator, cause oxyethane, the mixture of a kind of or their arbitrary proportions in the polymkeric substance of propylene oxide and tetrahydrofuran (THF), optional polyoxyethylene glycol, the polyoxytrimethylene triol, the mixture of a kind of or their arbitrary proportions in the polyoxytrimethylene tetrol that tetramethylolmethane causes.Described polyether glycol does not comprise by sucrose makes the polymkeric substance that initiator causes propylene oxide.Preferably glycerine and TriMethylolPropane(TMP) are made the epoxypropane polymer that initiator causes.Described polyether glycol also comprises and contains the tertiary amine groups polyether glycol, can make by polyamine and open loop of epoxy compound reaction, polyamine is diamine and the polyethylene polyamine of carbonatoms between 2～18, preferred quadrol polyoxytrimethylene tetrol or diethylenetriamine polyoxytrimethylene pentol.
Wherein, described polyester polyol obtains by polycondensation at the acid between 2～3 or acid anhydrides and the alcohol of functionality between 2～6 for functionality arbitrarily, wherein acid or the acid anhydrides of functionality between 2～3 can be Succinic Acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, lauric acid, 1,4 cyclohexanedicarboxylic acid, phthalic acid (acid anhydride), m-phthalic acid, terephthalic acid, tetrahydrophthalic acid (acid anhydride), adjacent this dioctyl phthalate (acid anhydride) of six hydrogen, trimellitic acid (acid anhydride), suitable divinyl acid (acid anhydride), fumaric acid or dimer (fatty acid) yl.Suitable polyvalent alcohol comprises ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,3 butylene glycol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,4-hydroxymethyl-cyclohexane, 1,4-cyclohexane diol, neopentyl glycol, 2-methyl isophthalic acid, ammediol, hexanetriol, glycerol, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane, Xylitol, N.F,USP MANNITOL, sorbyl alcohol, glycol ether, Triethylene glycol, dipropylene glycol or tripropylene glycol.Polyprotonic acid preferably contains acid, acid anhydrides or the alkyl ester of aromatic nucleus, between the preferred functionality 2～4 of polyvalent alcohol, the alcohol of carbonatoms between 2～8, ethylene glycol, 1 for example, 2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, neopentyl glycol, glycol ether, Triethylene glycol, dipropylene glycol, tripropylene glycol, glycerol, TriMethylolPropane(TMP) or tetramethylolmethane.
Polyester polyol described in the present invention also comprises natural fats and oils base polyester polyol, natural fats and oils base polyester polyol can prepare through alcoholysis reaction with natural fats and oils and polyvalent alcohol, perhaps the natural fats and oils of alcoholysis and small molecules polyvalent alcohol and small molecules polyprotonic acid are made through esterification, or natural fats and oils is directly passed through esterification with polyvalent alcohol and polyprotonic acid make.The natural fats and oils that is suitable for preparing natural oil base polyester polyol comprises: peanut oil, oleum lini, soya-bean oil, Viscotrol C, sunflower seed oil, tea oil, Oleum Cocois, plam oil, tung oil, lard, butter and sheep oil.Selected small molecules polyvalent alcohol comprises aliphatic diol, alicyclic diol, the glycol that contain aromatic nucleus and/or the glycol condenses of carbonatoms between 2～22, preferred glycol is aliphatics and the alicyclic diol between the carbonatoms 2～12, ethylene glycol, 1 for example, ammediol, 1,2-propylene glycol, 1,4-butyleneglycol, 1,3-butyleneglycol, 1,5-pentanediol, neopentyl glycol, 2-methyl isophthalic acid, ammediol, 1,6-hexylene glycol, 1,4-dihydroxyl hexanaphthene, 1,3-dihydroxyl hexanaphthene, 1,4-hydroxymethyl-cyclohexane or 1,2-ring pentanediol etc.; The preferred glycol ether of glycol condenses, Triethylene glycol or dipropylene glycol etc.Selected small molecules polyprotonic acid comprises aliphatic diacid, alicyclic diacid, aromatic diacid or the hydrogenated aromatic diacid etc. of carbonatoms between 2～22, preferred carbonatoms is at 4～12 diprotic acid, for example oxalic acid, propanedioic acid, Succinic Acid, hexanodioic acid, nonane diacid, certain herbaceous plants with big flowers diacid, 1,2-cyclohexane diacid, 1,4-cyclohexane diacid, tetrahydrochysene phthalic acid, terephthalic acid, phthalic acid or m-phthalic acid etc., preferred acid anhydrides comprises Succinic anhydried, maleic anhydride, Tetra hydro Phthalic anhydride or trimellitic anhydride etc.
Optimized technical scheme of the present invention is that to comprise massfraction in the described polyester polyol be 1～40% natural fats and oils base polyester polyol, and preferred massfraction is 3～30%.The present invention is used in natural fats and oils in the preparation hard polyurethane foams technology, has not only reduced dependence that can't the regenerated petroleum resources, and is simultaneously also more ecological, and more environmental protection is more economical.
Described fire retardant comprises organophosphate and inorganic combustion inhibitor, and wherein, organophosphate does not comprise halogenated phosphoric acid ester.Suitable phosphoric acid ester can be the mixture of a kind of or their arbitrary proportions of dimethyl methyl phosphonate, diethyl ethylphosphate, propyl phosphonic acid methyl ester, ISOPROPYL PHENYL DIPHENYL PHOSPHATE, triethyl phosphate, tricresyl phosphate (butoxyethyl group) ester, triphenylphosphate, Tritolyl Phosphate, Resorcinol two (diphenyl phosphoester) or low polyphosphate; Inorganic combustion inhibitor comprises the mixture of a kind of or their arbitrary proportions of ammonium phosphate, ammonium polyphosphate, ammonium polyphosphate, trimeric cyanamide, trimeric cyanamide urea acid esters, trimeric cyanamide monophosphate, polyphosphoric acid melamine, melamine pyrophosphate, antimony peroxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, magnesium hydroxide or aluminium hydroxide; The arbitrary proportion combination of organophosphate and inorganic combustion inhibitor is also included among the present invention.Through the long-term a large amount of experimental summary of the present invention, obtain the hard polyurethane foams of high comprehensive performance, the consumption of fire retardant is to account for 1%～50% of raw material total mass, and optimizing consumption is 3%～30, and optimum amount is 5%～25%.
Described foam stabilizer is used to reduce surface tension between gas and the matrix resin, any suitable surfactant may be used to the present invention, comprises polyoxyethylene glycol, polyethylene glycol long chain alkyl ester, polyethylene glycol glycerol fatty acid ester, poly ethyldiol modified polysiloxane and the propylene glycol modified polysiloxane of polyethylene glycol-.The polysiloxane of preferred, polyethers modification.Can be used for foam stabilizer of the present invention can obtain from corresponding products of company such as Si Luoke chemical company, air products company (Air product) and Wei Teke.Similarly, through the long-term a large amount of experimental summary of the present invention, obtain the hard polyurethane foams of high comprehensive performance, in technical solution of the present invention, the consumption of foam stabilizer is to account for 0.1%～15% of raw material total mass, and preferable amount is 0.1%～10%.Optimum amount is 0.2～8%.
If employing catalyzer, described catalyzer are a kind of of organotin, organo-bismuth or tertiary amine compounds or their arbitrary proportion miscellanys.Organo-tin compound can be selected the mixture of a kind of or their arbitrary proportions of dibutyl tin laurate, stannous octoate, tin acetate, dibutyltin diacetate or oxalic acid dioctyl tin; Bismuth organic compound can be selected bismuth carboxylate known in the art, for example neodecanoic acid bismuth or tertiary monocarboxylic acid bismuth and composition thereof; Tertiary amine compounds can be selected triethylamine, triethylene diamine, N, the N-diethylethanolamine, N, the N-dimethylethanolamine, the dimethylamino ethoxy ethanol, trolamine, trimethylammonium hydroxyethyl propylene diamine, the trimethylammonium hydroxyethylethylene diamine, N, two (dimethylamino-propyl) Yi Bingchunans of N-, tri-isopropyl amine, tri-isopropanolamine, Tributylamine, two (dimethylaminoethyl) ether, N, the N-dimethylcyclohexylamine, N-methyl bicyclic hexylamine, five methyl diethylentriamine, Tetramethyl Ethylene Diamine, 4-methyl hexamethylene diamine, 2,4,6-three (dimethylamino methyl) phenol, 1,3,5-three (dimethylamino-propyl) Hexahydrotriazine, N-cocoa morpholine, lupetazin, N, the N-dimethyl benzylamine, N, N-dimethyl (hexadecyl) amine, N-methylmorpholine, N-ethylmorpholine, N methyl piperazine, the N-crassitude, the N-picoline, the N-Methylimidazole, N, the N-dimethyl benzylamine, three (dimethylamino-propyl) amine, the tertiary amine that primary amine or secondary amine and epoxy compounds reaction generate.In addition, organotin, organo-bismuth and tertiary amine are also contained in the catalyzer of the present invention with the mixture of arbitrary proportion.In the technical solution of the present invention, catalyst consumption is to account for 0.01%～10% of raw material total mass, and preferable amount is 0.05%～8%, and optimum amount is 0.1%～6%.In amount ranges, can just increase and decrease consumption according to the viscosity of temperature height, mixed material.The temperature height when material viscosity is high, reduces catalyst levels; Temperature is low, when material viscosity is hanged down, strengthens catalyst levels, improves the foaming and the polymerization crosslinking speed of material of the present invention, produces sagging in the time of can effectively avoiding the facade spraying.
Described polyisocyanates comprises unmodified polyisocyanates, polyisocyanate prepolymers, polyisocyanates autopolymer or modified polyisocyanate, and functionality is preferred 2～8, molecular weight preferred 174～800.。Specifically can select isophorone diisocyanate for use, hexamethylene diisocyanate, the decamethylene vulcabond, 1,12-12 carbon vulcabond, 2-methyl-pentane vulcabond, dicyclohexyl methane diisocyanate, 1, the 4-cyclohexyl diisocyanate, the cyclohexanedimethyleterephthalate vulcabond, trimethylammonium-1, the 6-hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, how vulcabond, PPDI, xylylene diisocyanate, the dimethyl diphenyl vulcabond, norborneol vulcabond or tetramethyl-mphenylenedimethylim-vulcabond, many phenyl-polymethylenes-polyisocyanates (thick MDI), trivalent alcohol-vulcabond adds adult, vulcabond dimer and diisocyanate trimer.Preferred TriMethylolPropane(TMP)-tolylene diisocyanate affixture, many phenyl-polymethylenes-polyisocyanates (PAPI or thick MDI), toluene diisocyanate trimer, hexamethylene diisocyanate trimer or liquefaction diphenylmethanediisocyanate, and the mixing of above-mentioned substance arbitrary proportion is used.The polyisocyanates consumption should be controlled at the molar ratio of NCO/ hydroxyl between 1.1: 1～3.0: 1, and preferred ratio is between 1.2: 1～2.5: 1, and optimum ratio is between 1.2: 1～1.8: 1.
Described modification cenosphere is common cenosphere to be carried out modification obtain.Common cenosphere is mainly by SiO
2And Al
2O
3Forming, is a kind of inorganic non-metallic hollow microsphere, and its tap density is at 0.85～1.25g/cm
3Between, real density is 1.9～2.4g/cm
3The spheroid particle diameter is in 2.0～500 micrometer ranges, and ball-type rate 93% has hard shell, in the shell for vacuum or comprise rare gas elementes such as nitrogen, helium, neon and carbonic acid gas, material ultimate compression strength 550～750MPa, refractoriness reaches more than 1450 ℃, and wear resistance is good, chemical stability is good, acid, alkali and salts solution that ability is common, sound insulation, it is heat insulation that (thermal conductivity is 0.09～0.13W/mK).Through having the composition modified of a kind of reactive coupling agent of structure shown in the formula (I) or multiple reactive coupling agent, the structural formula of properties-correcting agent is expressed as follows with the cenosphere top layer in the present invention:
Wherein, a value is 1 or 2; The b value is 1,2 or 3, preferred value 2 or 3; The c value is 0,1 or 2, and preferred value is 0 or 1; The d value is 1,2 or 3; And b+c+d=4;
The feature of Y group be can with the group of hydroxyl or carboxyl reaction, include but are not limited to the reactive group of hydroxyl, epoxy group(ing), isocyanate group or amido; M is Si or Ti atom; X is hydroxyl, contain the alkoxyl group or the ester group of 1～4 carbon atom; Z is an alkyl.
Described reactive coupling agent feature be contain can with the group of carboxyl or polyisocyanates reaction, include but not limited to hydroxyl, epoxy group(ing), isocyanate group and amido.According to a, b, c, d value and M, X, Y, Z changes, the reactive coupling agent component can include but not limited to following compound: the hydroxyethyl Trimethoxy silane, (3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, (3, the 4-epoxycyclohexyl) ethyl triethoxysilane, the glycidyl ether propyl trimethoxy silicane, the glycidyl ether propyl-triethoxysilicane, glycidyl ether propyl group methyl dimethoxysilane, glycidyl ether propyl group tripropoxy silane, glycidyl ether propyl group three isopropoxy silane, glycidyl ether propyl group three butoxy silanes, the isocyanate group propyl trimethoxy silicane, the isocyanate group propyl-triethoxysilicane, the aminocarbonyl propyl Trimethoxy silane, the aminocarbonyl propyl triethoxyl silane, N-phenyl amido propyl trimethoxy silicane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl triethoxysilane, N-(6-ammonia hexyl)-3-aminopropyl triethoxysilane, N-(2-aminoethyl)-11-ammonia undecyl Trimethoxy silane, aminoethyl-aminomethyl-styroyl-Trimethoxy silane, N-3-[amino (polyoxytrimethylene base)]-aminopropyl trimethoxysilane, N-(6-ammonia hexyl)-aminomethyl triethoxyl silane, N-(2-aminoethyl)-3-aminopropyl silanetriol, N-(2-aminoethyl)-3-aminopropyl-methyl-dimethoxy silane, N-(2-aminoethyl)-3-ammonia isobutyl--dimethyl-methoxy silane, (3-Trimethoxy silane base propyl group) diethylenetriamine, isopropoxy-three (2-quadrol base oxethyl)-titanium (IV).
The method of above-mentioned modification is the modification that realizes common cenosphere by reactive coupling agent, less water and cenosphere are mixed; Perhaps adding reactive coupling agent, less water and the reaction of common cenosphere in acetone, methyl alcohol, ethanol or Virahol equal solvent obtains.The consumption of described reactive coupling agent is 0.01%～10% of a cenosphere quality, and preferable amount is 0.05%～5%, and optimum amount is 0.1%～3%; The use of water is in order to increase the even modification of silane coupling agent on the cenosphere surface, and general consumption is about 10% of a cenosphere.
Modification cenosphere of the present invention shared massfraction in the raw material of preparation hard polyurethane foams is 0.1～20%, preferred mass mark 1～15%.
Technical solution of the present invention uses water as whipping agent guaranteeing that foam has on good flame performance and the low thermal conductivity performance basis because adopt, and more possesses the good feature of environmental protection.
Preferably, the present invention more suitably 25 ℃ of viscosity of polymer polyatomic alcohol is 400～4000mPs, and 25 ℃ of viscosity of polyisocyanates are 100～1500mPs.
The present invention provides the preparation method of described environment-friendly high fire-retardant hard polyurethane foams simultaneously,
One of scheme is that polymer polyatomic alcohol, water, fire retardant, modification cenosphere and foam stabilizer are mixed, and the back makes with the foaming of polyisocyanates hybrid reaction.
Two of the preparation scheme of environment-friendly high fire-retardant hard polyurethane foams of the present invention is that polymer polyatomic alcohol, water and fire retardant are mixed, randomly add foam stabilizer and catalyzer one of them, make with polyisocyanates and cenosphere hybrid reaction again;
Three of preparation scheme is that cenosphere is divided into two portions, and wherein a part is dispersed in that one of them gets material A in polymer polyatomic alcohol, water and the flame-retardant mixture; Another part is dispersed in the polyisocyanates, randomly adds foam stabilizer and catalyzer, gets material B; Material A and B hybrid reaction are made hard polyurethane foams.Among the preparation method, cenosphere is divided into two portions, and the strictness of how much not doing of each part amount limits.
No matter use which kind of preparation method, between the hydroxy functionality of polymer polyatomic alcohol component described in the rigid polyurethane foam provided by the invention 2～8, hydroxyl value is between 150～800mgKOH/g, at least the polyester polyol that comprises a kind of natural fats and oils modification, its massfraction does not comprise sucrose based polyalcohol polyvalent alcohol between 1～40%.
No matter with which kind of preparation hard polyurethane foams method provided by the invention, polymer polyatomic alcohol, water, fire retardant, modification cenosphere, foam stabilizer and polyisocyanates mix the back cream time and be preferably 10 seconds～and 3 minutes, gel time is 20 seconds～4 minutes.The liquid starting material mixture of hard polyurethane foams can be sprayed directly into vertical elevation, and foaming mixtures did not produce sagging on the inherent vertical elevation in 4 minutes.
Hard polyurethane foams of the present invention can be used the lagging material as external wall, pipeline and refrigerating plant.
The invention has the beneficial effects as follows:
The present invention adopts full water foamed preparation hard polyurethane foams, does not contain the Chlorofluorocarbons (CFCs) of destroying atmospheric ozone and the Skellysolve A with explosion hazard, has successfully solved the low problem of the full water foamed hard polyaminoester rate of closed hole of flame retardant type; By selecting appropriate catalyst to cooperate overall technical architecture, the hard polyaminoester that is obtained can be sprayed at facade, spraying liquid sagging not on facade in 4 minutes; Described polyurethane foam thermal conductivity 0.019～0.030W/ (mK), rate of closed hole reaches more than 96.3%, cold cycling size sex change rate is less than 2%, vertical combustion reaches the V-0 level, water-intake rate significantly reduces, flame retardant resistance and heat retaining property are all very high, and hard polyurethane foams over-all properties of the present invention is superior, can be applied to external wall, pipeline and refrigerating plant insulation aspect preferably.
Embodiment
Further describe the present invention below in conjunction with the drawings and specific embodiments.According to inventive concept, simple the substituting of allied substances should belong to scope of the present invention.Employed test method is the existing ordinary method in present technique field if no special instructions among the following embodiment; Employed material, reagent etc. if no special instructions, are the reagent and the material that can obtain from commercial channels.For clear explanation, exemplified the producer that part material is produced in an embodiment, but therefore do not limit the scope of the invention to the raw material range that exemplifies among the product of described producer or the embodiment, those skilled in the art specifically can be referring to the detailed description of the technical scheme of summary of the invention part of the present invention.
Embodiment 1
(1) raw material of hard polyurethane foams preparation
1, polyester polyol
A reclaims PET alcoholysis polyester polyol, hydroxyl value 330mgKOH/g, viscosity 3500～4000mPs in the time of 25 ℃;
B polyester polyol PS-380, hydroxyl value 380mgKOH/g, viscosity 1300～1500mPs in the time of 25 ℃ (Qingdao Rui Nuo chemical company);
C polyether glycol 4110, hydroxyl value 410mgKOH/g, viscosity 800～1000mPs (Shandong Lanxing Dongda Chemical Co.,Ltd) in the time of 25 ℃;
D polyether glycol Multranol 9181, quadrol causes epoxypropane polymer, hydroxyl value 770mgKOH/g, viscosity 3000～4000mPs (Beyer Co., Ltd) in the time of 25 ℃;
The E Viscotrol C, hydroxyl value 166mgKOH/g, viscosity 400～500mPs in the time of 25 ℃, (Tonghua Philosamia Chemical Co., Ltd., Tongliao City);
F soybean oil polyvalent alcohol Soyoyl R137, hydroxyl value 212mgKOH/g, viscosity 800～1000mPs in the time of 25 ℃ (U.S. Urethane Soy Systems Co.);
2, fire retardant
G organophosphate FR-707, (Qingdao Lian Mei chemical company);
The reactive organophosphate FR-1m6 of H, (Qingdao Lian Mei chemical company);
I aluminium hydroxide, (the fire-retardant novel material of section company limited in the Hefei);
3, modification cenosphere
J modification hollow ceramic microspheres: (smart Ya Nami novel material company limited, Qingdao seaization fire retardant material company limited or the magnificent Henan of Xinyang, Henan Province Pingqiao District mining industry company limited etc. are converged in Shanghai to add 40 gram hollow ceramic microspheres in the 100 gram water; down together); add 5 donaxine base propyl trimethoxy silicanes in the whipping process; stirred 48 hours; filter; drying gets the modification hollow ceramic microspheres.
K mixes 10 gram hollow ceramic microspheres with 85 gram many phenyl-polymethylenes-polyisocyanates and 5 gram isocyanate group propyl trimethoxy silicanes, be used for foaming.
(smart Ya Nami novel material company limited, Qingdao seaization fire retardant material company limited or the magnificent Henan of Xinyang, Henan Province Pingqiao District mining industry company limited etc. are converged in Shanghai to add 2 gram water and 40 gram hollow glass micropearls in the L 100 gram dehydrated alcohols;); add 8 gram glycidyl ether propyl group methyl dimethoxysilanes in the whipping process; 80 ℃ of reflux 8 hours; filter; drying gets the modification hollow glass micropearl.
4, foam stabilizer
M SK-2015 (Guangzhou Si Luoke company);
The N polyoxyethylene glycol, molecular weight 400;
5, catalyzer
O month silicic acid dibutyl tin;
The P trolamine;
The Q triethylene diamine;
R 2,4,6-three (dimethylamino methyl) phenol;
6, polyisocyanates
The thick MDI of S (Yantai Wanhua Polyurethane Co., Ltd ,-NCO content about 30%), viscosity 150～250mPs in the time of 25 ℃;
T liquefied mdi prepolymer, 100 gram liquefied mdis restrain the TriMethylolPropane(TMP) reactant with 3 gram glycol ethers and 1, viscosity 1300～1500mPs during about 30%, 25 ℃ of-NCO content.
(2) preparation of hard polyurethane foams
1
#
Taking by weighing 60 gram polyester polyol A, 40 gram natural fats and oils polyvalent alcohol F and 2 gram water stirs evenly mixed, add 4 gram fire retardant G, 1 gram modified ceramic microballon J, 1.2 gram foam stabilizer M and 5 gram catalyst P in the whipping process, after treating that all components is evenly mixed, again with the mixed foaming of 116 gram polyisocyanates T, cream time 40 seconds, gel time 2 minutes.
2
#
Taking by weighing 90 gram polyester polyol B, 9 gram polyether glycol D, 1 gram natural fats and oils polyvalent alcohol F and 4 gram water stirs evenly mixed, add 10 gram fire retardant H, 2.7 gram foam stabilizer M, 0.13 gram catalyzer O and 0.13 gram catalyzer Q in the whipping process, obtain component (I), 25 gram modification cenosphere K and 142 gram polyisocyanates S are mixed, obtain component (II), at last with component (I) and the mixed foaming of component (II), cream time 15 seconds, gel time 30 seconds.
3
#
Taking by weighing 90 gram polyester polyol C, 10 gram natural fats and oils polyol Es and 4.6 gram water stirs evenly mixed, add 28 gram fire retardant G, 5 gram modified ceramic microballon L, 3 gram foam stabilizer M, 2 gram catalyst P in the whipping process, after treating that all components is evenly mixed, again with the mixed foaming of 173 gram polyisocyanates S, cream time 40 seconds, gel time 2.8 minutes.
4
#
Taking by weighing 88 gram polyester polyol C, 10 gram polyether glycol D, 2 gram natural fats and oils polyol Es and 4.2 gram water stirs evenly mixed, add 14 gram fire retardant G, 6 gram modified ceramic microballon J and 2 gram foam stabilizer N in the whipping process, after treating that all components is evenly mixed, again with the mixed foaming of 171 gram polyisocyanates S, cream time 3 minutes, gel time 4 minutes.
5
#
Taking by weighing 80 gram polyester polyol C, 20 gram natural fats and oils polyvalent alcohol F and 5 gram water stirs evenly mixed, add 8 gram fire retardant G and 30 gram fire retardant I, 10 gram modified ceramic microballon J, 3 gram foam stabilizer M and 0.3 gram catalyzer R in the whipping process, after treating that all components is evenly mixed, again with the mixed foaming of 171 gram polyisocyanates S, cream time 50 seconds, gel time 3.1 minutes.
6
#
Taking by weighing 85 gram polyester polyol B, 15 gram natural fats and oils polyvalent alcohol F and 3 gram water stirs evenly mixed, add 15 gram fire retardant G and 25 gram fire retardant I, 15 gram modified ceramic microballon L, 3 gram foam stabilizer M and 0.6 gram catalyzer R in the whipping process, after treating that all components is evenly mixed, again with the mixed foaming of 135 gram polyisocyanates S, cream time 35 seconds, gel time 2.6 minutes.
Comparative Examples
Claim that 100 gram polyether glycol C, 4 gram water, 1.3 gram foam stabilizer M and 0.3 gram catalyzer R are mixed, add the mixed foaming of 164 gram polyisocyanates again, cream time 54 seconds, gel time 3.2 minutes.
(3) performance test
With above-mentioned 1
#～6
#And the capable performance test of Comparative Examples product, performance test methods carries out with reference to GB/T3399 plastics thermal conductivity test method-protect flat plate heat method, GB/T 8811 rigid foam dimensional stability test methods, GB/T 8810 rigid foam moisture content test methods.Test result sees Table 1:
Table 1
By table 1 as seen: polyurethane foam flame retardant properties of the present invention all reaches from putting out the V-0 level; Thermal conductivity 0.019～0.030W/ (mK); Rate of closed hole reaches more than 96.3%, up to 98.4%; The cold cycling dimensional stability is less than 2%; Water-intake rate significantly reduces, and environment-friendly high fire-retardant hard polyurethane foams excellent property of the present invention sprays to vertical elevation with foaming mixtures and do not produce sagging in last 4 minute, is suitable for being applied to prepare the lagging material of external wall, electronic housing or refrigerator.
Claims (10)
1. an environment-friendly high fire-retardant hard polyurethane foams is characterized in that it being that the mixed reaction of polymer polyatomic alcohol, water, fire retardant, modification cenosphere, foam stabilizer and polyisocyanates is made; Described modification cenosphere is that the cenosphere top layer is obtained through a kind of reactive coupling agent or the composition modified of multiple reactive coupling agent with structure shown in the formula (I):
Wherein, a value is 1 or 2; The b value is 1,2 or 3, preferred value 2 or 3; The c value is 0,1 or 2, and preferred value is 0 or 1; The d value is 1,2 or 3; And b+c+d=4;
The feature of Y group be can with the group of hydroxyl, isocyanate group or carboxyl reaction, include but are not limited to the reactive group of hydroxyl, epoxy group(ing), isocyanate group or amido; M is Si or Ti atom; X is hydroxyl, contain the alkoxyl group or the ester group of 1～4 carbon atom; Z is an alkyl.
2. an environment-friendly high fire-retardant hard polyurethane foams is characterized in that it being that the mixed reaction under the catalyzer existence condition of polymer polyatomic alcohol, water, fire retardant, modification cenosphere, foam stabilizer and polyisocyanates is made;
Described modification cenosphere is that the cenosphere top layer is obtained through a kind of reactive coupling agent or the composition modified of multiple reactive coupling agent with structure shown in the formula (I):
Wherein, a value is 1 or 2; The b value is 1,2 or 3, preferred value 2 or 3; The c value is 0,1 or 2, and preferred value is 0 or 1; The d value is 1,2 or 3; And b+c+d=4;
The feature of Y group be can with the group of hydroxyl, isocyanate group or carboxyl reaction, include but are not limited to the reactive group of hydroxyl, epoxy group(ing), isocyanate group or amido; M is Si or Ti atom; X is hydroxyl, contain the alkoxyl group or the ester group of 1～4 carbon atom; Z is an alkyl.
3. according to the described environment-friendly high fire-retardant hard polyurethane foams of claim 2, it is characterized in that described catalyzer is a kind of of organotin, organo-bismuth or tertiary amine compounds or their arbitrary proportion miscellanys.
4. environment-friendly high fire-retardant hard polyurethane foams according to claim 1 and 2 is characterized in that described modification cenosphere shared massfraction in preparation hard polyurethane foams raw material is 0.1～20%, preferred mass mark 1～15%.
5. according to claim 1 or 2 described environment-friendly high fire-retardant hard polyurethane foams, it is characterized in that described polymer polyatomic alcohol hydroxy functionality is 2～8, hydroxyl value is 150～800mgKOH/g; And comprise a kind of natural fats and oils base polyester polyol at least, its massfraction is 1～40%; Preferred polymers polyvalent alcohol hydroxy functionality is 3～6, and hydroxyl value is 200～600mgKOH/g, the massfraction preferred 3～30% of described natural fats and oils base polyester polyol.
6. according to claim 1 or 2 environment-friendly high fire-retardant hard polyurethane foams, it is characterized in that fire retardant is the mixture of a kind of or their arbitrary proportions of not halogen-containing organophosphate, ammonium polyphosphate, trimeric cyanamide, antimony peroxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, magnesium hydroxide or aluminium hydroxide; Described foam stabilizer is polyether-modified polysiloxane.
7. according to claim 1 or 2 described environment-friendly high fire-retardant hard polyurethane foams, it is characterized in that described polyisocyanates functionality is 2～8, molecular weight is 174～800.
8. according to claim 1 or 2 described environment-friendly high fire-retardant hard polyurethane foams, viscosity is 400～4000mPs when it is characterized in that 25 ℃ of described polymer polyatomic alcohols; 25 ℃ of viscosity of described polyisocyanates are 100～1500mPs.
9. the preparation method of an environment-friendly high fire-retardant hard polyurethane foams, it is characterized in that it being that polymer polyatomic alcohol, water, fire retardant, modification cenosphere and foam stabilizer are mixed, having in the presence of catalyzer or the catalyst-free, making with the foaming of polyisocyanates hybrid reaction;
Or, add foam stabilizer and catalyzer with polymer polyatomic alcohol, water and fire retardant mixing, make with polyisocyanates and the foaming of modification cenosphere mixture reaction;
Or the part of modification cenosphere is dispersed in polymer polyatomic alcohol, water and the flame-retardant mixture, another part is dispersed in the polyisocyanates, adds foam stabilizer, is having or is not having under the catalyzer existence condition, and the hybrid reaction foaming makes;
The cream time of described foaming is 10 seconds～3 minutes, and gel time is 20 seconds～4 minutes.
10. the application of claim 1 or 2 described environment-friendly high fire-retardant hard polyurethane foams is characterized in that being applied to prepare the lagging material of external wall, electronic housing or refrigerator.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532470A (en) * | 2011-12-30 | 2012-07-04 | 大连亚泰科技新材料有限公司 | Preparation method of environment-friendly inflaming retarding polyurethane rigid foam plastic |
| CN102719086A (en) * | 2012-07-02 | 2012-10-10 | 江苏科泰绝热新材料有限公司 | Flame retarding polyurethane foam and preparation method thereof |
| CN103665317A (en) * | 2013-12-12 | 2014-03-26 | 青岛海洋新材料科技有限公司 | Preparation method of epoxy modified polyurethane filled with hollow glass microbeads |
| CN103865249A (en) * | 2012-12-14 | 2014-06-18 | 财团法人工业技术研究院 | Flexible non-combustible fireproof material |
| CN105837787A (en) * | 2016-04-25 | 2016-08-10 | 苏州亚科塑胶有限公司 | Preparation method of flame-retardant rigid polyurethane foam plastic |
| US9718937B2 (en) | 2014-03-14 | 2017-08-01 | Xiamen University | Inherent flame retardant rigid polyurethane foam |
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| CN110330630A (en) * | 2019-07-16 | 2019-10-15 | 华北电力大学（保定） | A kind of preparation method of the core packing material for composite insulation cross arm |
| CN113072682A (en) * | 2021-03-30 | 2021-07-06 | 北京九天行歌航天科技有限公司 | Heat-insulating foam for aerospace low-temperature storage tank and preparation method thereof |
| US11407874B2 (en) | 2019-10-07 | 2022-08-09 | Covestro Llc | Polyol premixes, thermally insulating rigid polyurethane foams and methods for their production |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4082702A (en) * | 1975-09-18 | 1978-04-04 | Dow Corning Corporation | Flame retardant rigid polyurethane syntactic foam |
| US20020020827A1 (en) * | 2000-02-22 | 2002-02-21 | Herbert Munzenberger | Two-component on-site foam system and its use for foaming openings for the purpose of fire protection |
| CN1339526A (en) * | 2001-09-21 | 2002-03-13 | 刘承晖 | Process for producing hollow micro bead filled resin base composite material |
| CN1470543A (en) * | 2002-06-18 | 2004-01-28 | Composite foam plastic with improved water-resistance, long storage time and short demoulding time | |
| CN101003611A (en) * | 2007-01-16 | 2007-07-25 | 北京理工大学 | Dual components foaming system and products in use for fireproof plugging |
| CN101316875A (en) * | 2005-12-01 | 2008-12-03 | 拜尔材料科学有限公司 | Water-blown, flame retardant rigid polyurethane foam |
| DE502007002394D1 (en) * | 2006-11-29 | 2010-02-04 | Hilti Ag | Two-component polyurethane / vinyl ester hybrid foam system and its use as a flame retardant material and material for foaming openings in buildings |
-
2010
- 2010-09-02 CN CN2010102738426A patent/CN101962474A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4082702A (en) * | 1975-09-18 | 1978-04-04 | Dow Corning Corporation | Flame retardant rigid polyurethane syntactic foam |
| US20020020827A1 (en) * | 2000-02-22 | 2002-02-21 | Herbert Munzenberger | Two-component on-site foam system and its use for foaming openings for the purpose of fire protection |
| CN1339526A (en) * | 2001-09-21 | 2002-03-13 | 刘承晖 | Process for producing hollow micro bead filled resin base composite material |
| CN1470543A (en) * | 2002-06-18 | 2004-01-28 | Composite foam plastic with improved water-resistance, long storage time and short demoulding time | |
| CN101316875A (en) * | 2005-12-01 | 2008-12-03 | 拜尔材料科学有限公司 | Water-blown, flame retardant rigid polyurethane foam |
| DE502007002394D1 (en) * | 2006-11-29 | 2010-02-04 | Hilti Ag | Two-component polyurethane / vinyl ester hybrid foam system and its use as a flame retardant material and material for foaming openings in buildings |
| CN101003611A (en) * | 2007-01-16 | 2007-07-25 | 北京理工大学 | Dual components foaming system and products in use for fireproof plugging |
Non-Patent Citations (2)
| Title |
|---|
| 姜鑫，杨振国: "玻璃微珠表面改性方法及其对硬质聚氨酯泡沫性能的影响", 《复旦学报(自然科学版）》 * |
| 彭智，郑震，王新灵: "全水发泡阻燃聚氨酯硬质泡沫塑料的制备与性能", 《聚氨酯工业》 * |
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| CN102719086A (en) * | 2012-07-02 | 2012-10-10 | 江苏科泰绝热新材料有限公司 | Flame retarding polyurethane foam and preparation method thereof |
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| TWI481664B (en) * | 2012-12-14 | 2015-04-21 | Ind Tech Res Inst | Flexible non-combustible fire-resistant material |
| CN103865249B (en) * | 2012-12-14 | 2016-06-01 | 财团法人工业技术研究院 | Flexible non-combustible fireproof material |
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| US9718937B2 (en) | 2014-03-14 | 2017-08-01 | Xiamen University | Inherent flame retardant rigid polyurethane foam |
| CN105837787A (en) * | 2016-04-25 | 2016-08-10 | 苏州亚科塑胶有限公司 | Preparation method of flame-retardant rigid polyurethane foam plastic |
| CN109400846A (en) * | 2018-10-27 | 2019-03-01 | 濮阳天健生物科技有限公司 | A kind of chemical reaction kettle composite insulation boards and preparation method thereof |
| CN110330630A (en) * | 2019-07-16 | 2019-10-15 | 华北电力大学（保定） | A kind of preparation method of the core packing material for composite insulation cross arm |
| US11407874B2 (en) | 2019-10-07 | 2022-08-09 | Covestro Llc | Polyol premixes, thermally insulating rigid polyurethane foams and methods for their production |
| US11732100B2 (en) | 2019-10-07 | 2023-08-22 | Covestro Llc | Polyol premixes, thermally insulating rigid polyurethane foams and methods for their production |
| CN113072682A (en) * | 2021-03-30 | 2021-07-06 | 北京九天行歌航天科技有限公司 | Heat-insulating foam for aerospace low-temperature storage tank and preparation method thereof |
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