CN103619898A - Polyurethane rigid foams - Google Patents

Abstract

The invention is directed to polyurethane rigid foams which can be prepared by reacting a) polyisocyanates with b) compounds having at least two hydrogen atoms which are reactive toward isocyanate groups in the presence of c) blowing agents and d) at least one flame retardant, wherein the compounds having at least two hydrogen atoms which are reactive toward isocyanate groups b) comprise at least one polyether polyol bi) and at least one polyester polyol bii) and the flame retardant d) comprises expandable graphite di).

Description

Hard polyurethane foams

The present invention relates to have the hard polyurethane foams, a kind of by making polyisocyanates and thering are at least two compounds that isocyanate group are to reactive hydrogen atom react the method for preparing this foam under at least one fire retardant exists of improved flame retardant resistance, and a kind of polyol component that comprises described fire retardant.

Hard polyurethane foams known for a long time and be mainly used in isolated cold and hot, for example for refrigeration equipment, for hot water storage, for district heating pipe or for buildings and building.The heat insulation of buildings implemented by spraying technology conventionally.The preparation of hard polyurethane foams and the summary of application can be referring to for example Kunststoff-Handbuch, the 7th volume, and Polyurethane, by doctor R.Vieweg and A.

doctor edit 1966 the 1st edition, the nineteen eighty-three the 2nd edition of being edited by G ü nter doctor Oertel and by G ü nter doctor Oertel, edited 1993 the 3rd edition, Carl Hanser Verlag, Munich, in Vienna.

The important requirement that hard polyurethane foams must meet is that lower thermal conductivity, good mobility, foam are to tectal gratifying binding property and good mechanical property.

Another challenge being always present in hard polyurethane foams application is the flame retardant resistance of improving foam.For this reason, conventionally in foam, add fire retardant.The interpolation of fire retardant can change mechanical property and the processing characteristics of foam.In addition, for environment reason, wish restriction fire retardant, particularly based on halogen, especially application in hard polyurethane foams based on those of bromine.

The known expansible black lead that uses in polyurethane foam is as fire retardant.Expansible black lead be very effective fire retardant and can be used for flexible foam and rigid foam in.

WO00/35999 has described a kind of expansible black lead that uses and as fire retardant, has prepared the method for hard polyurethane foams.Described expansible black lead under the reactive compounds of halogen atom exists with other fire retardants, preferably P contained compound is used in combination.Polyvalent alcohol for the preparation of described polyurethane foam is polyether glycol.

DE19912988 has described the resistance combustion polyurethane foam that comprises filler material.Described filler material is the mixture that inorganic high-temp is stablized filler, micropore high-temperature stable filler and the heat-activatable filler (as expansible black lead) with expansion.These fillers can be by tackiness agent, preferably by organophosphate as ammonium phosphate or melamine phosphate gluing bonding.

DE10310006 has described the halogen-free flameproof hard polyurethane foams that comprises expansible black lead and ABC fire fighting powder.

ABC fire fighting powder is described as the mixture of ammonium salt as ammonium phosphate and volatile salt, and it can further comprise mineral filler as silicon-dioxide.Expansible black lead is sneaked in isocyanate component, ABC fire fighting powder is sneaked in polyol component.Do not describe described polyol component in detail, in embodiment, polyvalent alcohol used is polyether glycol.

The hard polyurethane foams that the object of this invention is to provide the flame retardant resistance with improvement, it can be used for the heat insulation of buildings.Described foam must be able to apply by spraying technology.Each component, especially polyol component should be stable.The binding property that described foam reply base material is as good in concrete has (especially when using foam spraying technology to apply), and there is good mechanical property.

Described object is by being used expansible black lead as fire retardant and using Aethoxy Sklerol and polyesterols to realize as polyol component.

Therefore, the invention provides a kind of hard polyurethane foams, it can be by making

A) polyisocyanates with

B) there are at least two compounds that isocyanate group are to reactive hydrogen atom,

C) whipping agent and

D) at least one fire retardant

There is lower reaction and obtain;

Wherein there are at least two compound b that isocyanate group are to reactive hydrogen atom) comprise at least one polyether glycol bi) and at least one polyester polyol bii), and fire retardant d) comprise expansible black lead di).

The present invention further provides a kind of method of preparing described hard polyurethane foams.The present invention further provides a kind of polyol component for the production of described hard polyurethane foams.

For the present invention, rigid foam is preferably the foam according to DIN7726, be that described foam has to 10% compression the 80kPa of being more than or equal to according to DIN53421/DIN EN ISO604, preferably greater than or equal to 150kPa, be particularly preferably more than or equal to stress under compression or the compressive strength of 180kPa.In addition, according to the closed pore ratio in rigid foam described in DIN ISO4590, be greater than 85%, be preferably greater than 90%.

For the present invention, flame-retardant foam is that its flame height is the foam that is not more than 15cm according to EN ISO11925-2GB/T8626-2007.The average combustion residue of hard polyurethane foams is greater than 150mm, and minimum combustion residue is greater than 0mm, and average flue-gas temperature is lower than 200 ℃, according to DIN4201 part 1 or GB/T8625-2005.According to GB/T8627-2007, the smoke density grade of hard polyurethane foams is less than 75.Hard polyurethane foams meets above-mentioned standard and is classified as nonflammable material (B1 level).

In a preferred embodiment of the invention, expansible black lead di), with 2-25 % by weight, preferred 5-20 % by weight, more preferably the amount of 8-15 % by weight is used, based on components b), c) and weight d).The particle diameter of described expansible black lead is 0.01-0.5mm, is preferably 0.1-0.5mm.The rate of expansion of described expansible black lead when being heated above 400 ℃ is 150-500.

Can be by expansible black lead di) as unique fire retardant.In preferred embodiments, expansible black lead di) with other fire retardants dii) be used in combination.

Fire retardant dii) can with isocyanate reaction or not with isocyanate reaction.In one embodiment, be fire retardant dii) P contained compound.

The example of these compounds is oxyalkylated alkyl phosphonic acid.These compounds can with isocyanate reaction.

Another kind of P contained compound be not with the lower molecular weight phosphonium flame retardant of isocyanate reaction.These compounds preferably have lower than 300g/mol, especially lower than 300g/mol, preferably lower than 200g/mol, the molar mass of 150-190g/mol particularly preferably, and in molecule, preferably have and be less than 4 phosphorus atom, be especially less than 3, more particularly be less than 2, especially 1 phosphorus atom.Preferred phosphonic acid ester and/or phosphoric acid ester.Particularly preferably be selected from phosphoric acid ester and the phosphonic acid ester of ethane diethyl phosphonate (DEEP), propyl phosphonic acid methyl ester (DMPP) and triethyl phosphate (TEP); Particularly preferably be selected from those of ethane diethyl phosphonate (DEEP) and triethyl phosphate (TEP); Use especially ethane diethyl phosphonate (DEEP).The consumption of these fire retardants is preferably 5-80 % by weight, and 5-60 % by weight particularly preferably, 10-50 % by weight particularly preferably, based on fire retardant d) gross weight.

Another kind of do not have high molecular with the P contained compound of isocyanate reaction, preferably has the molar mass higher than 300g/mol.Preferably it has at least 1 phosphorus atom in molecule.Preferred phosphonic acid ester and/or phosphoric acid ester, especially phosphoric acid ester.These preferred embodiment is diphenyl tolyl phosphate (DPC) and/or triphenylphosphate, particularly diphenyl tolyl phosphate.The consumption of these compounds is preferably 0.5-80 % by weight, is particularly preferably 10-70 % by weight, is particularly preferably 20-60 % by weight or 30-50 % by weight, particularly 35-45 % by weight, based on fire retardant d) gross weight.

Other examples of P contained compound are ammonium phosphate and ammonium polyphosphate.

In a preferred embodiment of the invention, phosphonium flame retardant dii) be selected from diethyl ethylphosphate, propyl phosphonic acid methyl ester, triethyl phosphate and tricresyl phosphate (2-chloro isopropyl) ester.

The fire retardant dii that other are possible) be the reaction product of melamine and melamine.

In another embodiment of the present invention, described extra fire retardant is halogen atom, preferably chlorine and/or bromine atoms, the more preferably compound of bromine atoms.Example is p chloromethylbenzoic acid substituted alkyl ester, bromine neo-pentyl propane, dibromo neo-pentyl propane, phthalate bromine ester (brominephtalyc acid ester), dibromopropane.

In another embodiment of the present invention, fire retardant dii) be phosphorous and compound halogen.Example is p chloromethylbenzoic acid substituted alkyl ester, is preferably tricresyl phosphate (2-chloro isopropyl) ester.

Fire retardant dii) can use with the form of one-component.In a preferred embodiment of the invention, be fire retardant dii) mixture of at least two kinds of components.

In one embodiment, be fire retardant dii) mixture of at least one phosphonium flame retardant and at least one halogen containing flame-retardant.In preferred embodiments, fire retardant dii) be the mixture of at least one phosphonium flame retardant and at least one phosphorous halogen fire retardant.

Fire retardant dii), preferably with 5-40 % by weight, be that the amount of 5-25 % by weight is used especially, based on components b), c) and weight d).

Described hard polyurethane foams by polyisocyanates a) with there are at least two compound b that isocyanate group are to reactive hydrogen atom) at whipping agent, fire retardant d), react under the existence of catalyzer and conventional auxiliary agent and/or additive and prepare.Raw materials used details is as follows.

Spendable organic multiple isocyanate be any known organic two-and polyisocyanates, preferably aromatics polyfunctional isocyanate.

Each example that can mention is toluene 2,4-and 2,6-vulcabond (TDI) and corresponding isomer mixture, ditane 4,4 '-, 2,4 '-and 2,2 '-vulcabond (MDI) and corresponding isomer mixture, by ditane 4,4 '-with 2, the mixture that 4 '-vulcabond forms, polyphenyl polymethylene polyisocyanates, by ditane 4,4 '-, 2,4 '-and 2, the mixture that 2 '-vulcabond and polyphenyl polymethylene polyisocyanates form (thick MDI) and the mixture being formed by thick MDI and tolylene diisocyanate.Described organic two-and polyisocyanates can be used alone or use with form of mixtures.

Conventionally also use so-called modification polyfunctional isocyanate, by organic two-and/or product of obtaining of the chemical reaction of polyisocyanates.For example, can mention and comprise two of uretdion, carbamate groups, isocyanurate group, carbodiimide, allophanate group and/or urethane groups-and/or polyisocyanates.Suitable, described modified polyisocyanate can be mixed with each other or with unmodified organic multiple isocyanate as ditane 2,4 '-or 4,4 '-vulcabond, thick MDI or toluene 2,4-and/or 2,6-vulcabond mix.

Also can use the reaction product of polyfunctional isocyanate and polyvalent alcohol herein, or these and other two-and the mixture of polyisocyanates.

Confirmed that especially successfully organic multiple isocyanate is thick MDI, particularly NCO content be the viscosity at 29-33 % by weight and 25 ℃ be 150-1000mPas those.

Polyester polyol bii used) mainly by polyvalent alcohol and the polyvalent carboxylic acid condensate with 2-12 carbon atom, prepare.

In one embodiment, described polyvalent alcohol is for having 2-12 carbon atom, preferably the dibasic alcohol of 2-6 carbon atom, for example ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, BDO or 1,3 butylene glycol.Can use a small amount of 3 or higher official can alcohol, as glycerine or TriMethylolPropane(TMP).

Described polycarboxylic acid is for example succsinic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, decane dicarboxylic acid, toxilic acid, fumaric acid, or preferably phthalic acid, m-phthalic acid, terephthalic acid, or isomery naphthalic acid.Most preferably hexanodioic acid, phthalic acid, m-phthalic acid and terephthalic acid.

In another embodiment of the present invention, polyester polyol bii) can pass through phthalic ester, preferably the preparation of reacting of polyethylene terephthalate and alcohol.

Polyester polyol bii) preferably there is the hydroxyl value that is preferably 160-750mg KOH/g.Polyesterols bii used) mostly there is the functionality of 2-4.

In a preferred embodiment of the invention, polyester polyol bii) based at least one aromatic substance, mainly based on aromatic carboxylic acid.

In particularly preferred embodiments, be polyester polyol bii) esterification products of following material:

B1) 10-70 % by mole of dicarboxylic acid composition, it comprises:

B11) 50-100 % by mole of one or more aromatic dicarboxylic acid or derivatives thereof,

B12) 0-50 % by mole of one or more aliphatic dicarboxylic acid or derivatives thereof;

B2) 2-30 % by mole of one or more lipid acid or derivatives thereof;

B3) 10-70 % by mole one or more have 2-18 carbon atom aliphatic series or alicyclic dibasic alcohol or its alcoxylates;

B4) polyether glycol of 2-50 % by mole of functionality >=2, it can obtain by the alkoxylate of polyvalent alcohol.

Preferably, components b 11) comprise the compound that at least one is selected from following group: terephthalic acid, dimethyl terephthalate (DMT) (TMP), polyethylene terephthalate (PET), phthalic acid, Tetra hydro Phthalic anhydride and m-phthalic acid.Especially, components b 11) comprise the compound that at least one is selected from following group: terephthalic acid, dimethyl terephthalate (DMT), polyethylene terephthalate and Tetra hydro Phthalic anhydride.Very particularly preferably, components b 11) comprise Tetra hydro Phthalic anhydride, terephthalic acid or its mixture.

Described aliphatic dicarboxylic acid or derivatives thereof is conventionally with 0-30 % by mole, and preferably the amount of 0-10 % by mole is present in described dicarboxylic acid composition.In particularly preferred embodiments, dicarboxylic acid composition b11) not containing aliphatic dicarboxylic acid or derivatives thereof, and formed by one or more aromatic dicarboxylic acid or derivatives thereofs of 100 % by mole.

Preferably, components b 2), with 3-20 % by mole, more preferably the amount of 5-18 % by mole exists.

Preferably, components b 3), with 20-60 % by mole, more preferably the amount of 25-55 % by mole, particularly 30-45 % by mole exists.

Preferably, components b 4), with 2-40 % by mole, more preferably the amount of 8-35 % by mole, particularly 15-25 % by mole exists.

In a preferred embodiment of the invention, lipid acid or derivatives thereof is selected from oil, raisin seed oil, Nigella damascena L. oil, Semen Cucurbitae oil, Borrago officinalis seed oil, soybean oil, wheatgerm oil, rapeseed oil, Trisun Oil R 80, peanut oil, sweet almond oil, Pistacia vera oil, Prunus amygdalus oil, sweet oil, Queensland nut oil, Lipoval A, Oleum Hippophae, sesame oil, cannabis oil, hazelnut oil, primrose oil, wild rose oil, Thistle oil, the walnut oil of Viscotrol C, plam oil, polyhydrony fatty acid, ricinolic acid, hydroxyl modification; Based on Oleomyristic acid, Zoomeric acid, stearic acid, palmitinic acid, oleic acid, vaccenic acid, petroselinic acid, cis-9-20 carbon acid, erucic acid, Selacholeic acid, linolic acid, α-and gamma-linolenic acid, therapic acid, arachidonic acid, ten carbon 5 alkene acids, 22 carbon-4, lipid acid and the fatty acid ester of the hydroxyl modification of 7,11-triolefin-18-acetylenic acid and docosahexenoic acid.

In particularly preferred embodiments, lipid acid or derivatives thereof b2) be selected from oleic acid, biofuel, soybean oil, raisin seed oil and butter (leaf fat), particularly oleic acid.

Very particularly preferably, components b 2) not containing any triglyceride level.Particularly preferably, components b 2) be the mixture of lipid acid itself or its alkyl monoester or lipid acid and its alkyl monoester.

Preferably, aliphatic series or alicyclic diol b3) be selected from following group: ethylene glycol, glycol ether or propylene glycol, 1,3-propane diol, 1,4-butanediol, 1,5-pentane diol, 1,6-hexane diol, 2-methyl isophthalic acid, 3-propane diol and 3-methyl isophthalic acid, 5-pentane diol and alcoxylates thereof.Particularly preferably monoethylene glycol and glycol ether, particularly glycol ether.

Preferably, polyether glycol b4) be selected from following group: the reaction product of polyoxyethylene glycol (PEG) and glycerine, TriMethylolPropane(TMP) (TMP) or tetramethylolmethane and oxyalkylene.

Especially, use is by the polyether glycol b4 of functionality >=2 of the alkoxylate acquisition of the polyvalent alcohol of functionality >=3).Preferably, polyether glycol b4) functionality >=2.7, more preferably >=2.9.The functionality of described polyether glycol conventionally≤6, more preferably≤5, particularly preferably≤4.

In one embodiment, polyether glycol b4), by making polyvalent alcohol and ethylene oxide and/or the propylene oxide of functionality >2, particularly ethylene oxide reacts and obtains.

In another preferred embodiment, polyether glycol b4) by alkoxylate, preferably ethoxylation is selected from the polyvalent alcohol of following group and obtains: Sorbitol Powder, TriMethylolPropane(TMP), glycerine, Polyglycerine and composition thereof.Particularly preferably polyvalent alcohol is selected from TriMethylolPropane(TMP) and glycerine.

Polyether glycol b4) by currently known methods, prepare, for example, by propylene oxide or ethylene oxide, the anionoid polymerization of preferential oxidation ethene and preparing, is wherein used alkali metal hydroxide or alkali metal alcoholates or amine catalyst as dimethylethanolamine and imidazoles, particularly imidazoles.

In highly preferred embodiment, polyether glycol b4) by glycerine and ethylene oxide and/or propylene oxide, particularly form with the reaction product of ethylene oxide.In another highly preferred embodiment, polyether glycol b4) by TriMethylolPropane(TMP) and ethylene oxide and/or propylene oxide, particularly form with the reaction product of ethylene oxide.

Preferably, polyether glycol b4) OH value is 150-1250mg KOH/g, and more preferably 300-950mg KOH/g, is particularly preferably 500-800mg KOH/g.

In another preferred embodiment, based on every kg B component, use at least 200mmol, preferred 400mmol at least, more preferably 600mmol at least, 800mmol at least particularly preferably, particularly 1000mmol compound b4 at least).

In embodiment very particularly preferably of the present invention, polyether glycol b4) be dihydroxy methylpropane or glycerine, the reaction product of preferably glycerine and ethylene oxide, its OH value is 500-800mgKOH/g, preferred 500-600mg KOH/g, it is by using imidazoles to obtain as the alkoxylation of catalyzer.

In another particularly preferred embodiment, polyether glycol b4) be TriMethylolPropane(TMP) or glycerine, the reaction product of preferably glycerine and ethylene oxide, its OH value is 500-800mg KOH/g, be preferably 500-650mg KOH/g, it is by using imidazoles to obtain as the alkoxylation of catalyzer; Aliphatic or alicyclic dibasic alcohol b3) be glycol ether, and lipid acid or derivatives thereof b2) be oleic acid.

The special polyether glycol bi using) those for preparing by currently known methods, for example, by catalyzer, preferred alkali metal hydroxide or DMC catalysts (dmc catalyst) make oxyalkylene anionoid polymerization under existing to H functional initiator material and prepare.

Oxyalkylene used is mainly ethylene oxide or propylene oxide, or tetrahydrofuran (THF), various oxybutylene or styrene oxide, preferably pure 1,2-propylene oxide.Described oxyalkylene can be separately, with alternating sequence or with form of mixtures, use.

The special initiator material using is for to have at least 2 in molecule, preferred 2-8 hydroxyl or have the compound of at least 2 primary aminos.

Used has at least 2 in molecule, and preferably the initiator material of 2-8 hydroxyl is preferably TriMethylolPropane(TMP); Glycerine; Tetramethylolmethane; Sugar compounds is as glucose sugar, Sorbitol Powder, mannitol and sucrose; Polyphenol; Phenol-formaldehyde A, the oligomeric condenses for example being formed by phenol and formaldehyde; And the Mannich condensate being formed by phenol, formaldehyde and two alkanolamines; And melamine.

The initiator material in molecule with at least 2 primary aminos used is preferably aromatics two-and/or polyamines, as phenylenediamine, and 2,3-, 2,4-, 3,4-and 2,6-tolylene diamine, 4,4 '-, 2,4 '-and 2,2 '-diaminodiphenylmethane, and aliphatic series two-and polyamines as quadrol.

Polyether glycol bi) functionality is preferably 2-8, and its hydroxyl value is preferably 25-800mgKOH/g, particularly 150-570mg KOH/g.

In a preferred embodiment of the invention, polyether glycol bi) functionality is 2-3, most preferably is 2.The hydroxyl value of these polyether glycols is 110-570mg KOH/g.

In particularly preferred embodiments, be polyether glycol bi) polyoxyethylene glycol.

Polyether glycol bi) preferably with the amount of 3-20 % by weight, use, based on components b), c) and weight d).

Having at least two other compounds that isocyanate group is to reactive hydrogen atom is linking agent and the chainextender that suitable words can be used simultaneously.Susceptible of proof add difunctionality chainextender, trifunctional or more these mixture of the linking agent of high functionality or suitable words for changing mechanical property, be favourable.The chainextender preferably using and/or linking agent be alkanolamine, especially molecular weight lower than 400, be preferably glycol and/or the triol of 60-300.

In a preferred embodiment of the invention, polyesterols bii), with 30-60 % by weight, preferably the amount of 32-48 % by weight is used, Aethoxy Sklerol bi) with the amount of 3-20 % by weight, use, based on components b), c) and weight d).

Spendable whipping agent is chemical foaming agent, and as water and/or formic acid, thereby these and isocyanic ester radical reaction discharge respectively carbonic acid gas and carbonic acid gas and carbon monoxide.The compound that is known as pneumatogen also can preferably and water be used in combination or preferably replace water.These,, for be the compound of inertia with respect to initiation component, are mostly at room temperature in a liquid state and evaporate under urethane reaction condition.The boiling point of these compounds is preferably lower than 50 ℃.Pneumatogen is also for being at room temperature gaseous state and introducing under pressure or be dissolved in the compound in starting ingredient, and example is carbonic acid gas, lower boiling paraffinic hydrocarbons and fluoro paraffinic hydrocarbons.

Whipping agent is mainly selected from paraffinic hydrocarbons, formic acid and/or has the naphthenic hydrocarbon of at least 4 carbon atoms, dialkyl ether, ester, ketone, acetal, has the fluoro paraffinic hydrocarbons of 1-8 carbon atom and in alkyl chain, have tetraalkyl silane, the especially tetramethylsilane of 1-3 carbon atom.

The example that can mention is propane, normal butane, Trimethylmethane, tetramethylene, Skellysolve A, iso-pentane, pentamethylene, hexanaphthene, dimethyl ether, methyl ethyl ether, methyl butyl ether, methyl-formiate, acetone and can be at troposphere degraded and the fluoro paraffinic hydrocarbons therefore not damaging the ozone layer as trifluoromethane, methylene fluoride, 1,1,1,3,3-3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-Tetrafluoroethane, C2H4F2 C2H4F2 and heptafluoro-propane.Described pneumatogen can be separately or with any required being used in combination each other.

The common consumption of whipping agent component is 1-55 % by weight, be preferably 1-40 % by weight, be particularly preferably 2-30 % by weight, 5-25 % by weight especially, the gross weight based on following component: polyvalent alcohol, whipping agent, catalyst system and any suds-stabilizing agent, fire retardant and other additives.

The amount of water is preferably 0.1-2.0 % by weight, based on components b), c) and weight d).

Catalyzer used especially comprises remarkable promotion isocyanate group and the compound reacting that isocyanate group is to reactive group.The example of these catalyzer is basic amine, and for example aliphatic secondary amine, imidazoles, amidine class and alkanolamine, Lewis acid or organometallic compound, especially based on those of tin.The catalyst system that also can use the mixture by various catalyzer to form.

If introduce isocyanurate group in described rigid foam, need specific catalyzer.Conventionally isocyanurate catalyst used is metal carboxylate, particularly potassium acetate and solution thereof.Described catalyzer can be separately or is used with any desired mixt form each other if required.

Described system should comprise catalyzer, and it makes foaming, gelling and trimerization reaction speed reach balance, thereby makes described spraying chemical system have suitable expansion rate, therefore improves the final performance of foam.

Spendable auxiliary agent and/or additive for example, for originally becoming known for the material of this object, tensio-active agent, suds-stabilizing agent, abscess conditioning agent, filler, pigment, dyestuff, antioxidant, hydrolysis stabilizer, static inhibitor, fungistatic agent and fungistat.

With for implementing the relevant further details of raw material, whipping agent, catalyzer and the auxiliary agent of the inventive method and/or additive referring to for example Kunststoffhandbuch[plastics handbook], the 7th volume, " Polyurethane " [urethane], Carl-Hanser-Verlag Munich, 1966 the 1st edition, nineteen eighty-three the 2nd edition and 1993 the 3rd edition.

In order to prepare hard polyurethane foams, make polyisocyanates a) and there are at least two compound b that isocyanate group are to reactive hydrogen atom) so that the isocyanate index of described polyurethane foam is 100-400, be preferably the quantitative response of 150-350.

Described hard polyurethane foams can be by known mixing device intermittence or continuous production.Known mixing device can be used for each starting ingredient to mix.

Hard isocyanate group foam of the present invention a) is produced by two-pack method conventionally.In the method, by described, there are at least two compounds that isocyanate group are to reactive hydrogen atom and mix with whipping agent, catalyzer and other auxiliary agents and/or additive, thereby obtain so-called polyol component, and make this polyol component and polyisocyanates or the mixture (also referred to as isocyanate component) that consists of polyisocyanates and suitable words whipping agent reacts.

Conventionally by described starting ingredient at 5-70 ℃, preferably at the temperature of 20-65 ℃, mix.Described reaction mixture can be used high pressure or low pressure feed machine to mix.

In a preferred embodiment of the invention, described foam is prepared by foam spraying technology.This technology is known and is for example described in Kunststoffhandbuch[plastics handbook], the 7th volume, " Polyurethane " [urethane], Carl-Hanser-Verlag Munich, 1966 the 1st edition, nineteen eighty-three the 2nd edition and 1993 the 3rd edition, in 333-335 page.By liquid ingredient a) and b) in nozzle, combine and be sprayed on the region of stand-by described foam coverage.Then make described foam harden on this surface.

The density of prepared rigid foam is preferably 10-400kg/m ³, be preferably 20-200kg/m ³, be in particular 30-100kg/m ³.

Foam of the present invention, especially described spray foam has good mechanical property and meets GB/T50404.

The flame height of described foam is preferably no more than 15cm according to EN ISO11925-2 or GB/T8626-2007.

The average combustion residue of described hard polyurethane foams is greater than 150mm conventionally, and its minimum combustion residue is greater than 0mm, and average flue-gas temperature is lower than 200 ℃, according to DIN4201 part 1 or GB/T8625-2005.

The smoke density of described hard polyurethane foams is less than 75 conventionally according to GB/T8627-2007.

embodiment 1-5 and comparative example C1:

Use following component:

Aethoxy Sklerol 1: the polyethylene oxide adduct of quadrol, OH value is 470;

Aethoxy Sklerol 2: the ethylene oxide/propylene oxide adducts of ortho-toluene diamine, OH value is that 405, EO content is 15.3 % by weight;

Aethoxy Sklerol 3: polyoxyethylene glycol, OH value is 190;

Polyesterols 1: the aromatic polyester polyols based on phthalic ester and glycol ether, OH value is 40;

Polyesterols 2: the aromatic polyester polyols based on phthalic ester and glycol ether, OH value is 175;

TEP: triethyl phosphate;

TCCP: tricresyl phosphate (chloro isopropyl) ester;

APP: ammonium polyphosphate;

Tensio-active agent 1: polysiloxane type tensio-active agent (DC193, available from Air Product);

Tensio-active agent 2: the non-silicone type tensio-active agent (LK443, available from Air Product) that comprises NVP;

Catalyzer 1: tin catalyst (Dabco120, available from Air product);

Catalyzer 2: amine catalyst (PT303, available from Air product);

Catalyzer 3: amine catalyst (PT304, available from Air product);

Catalyzer 4: the potassium acetate in monoethylene glycol;

The chloro-1-fluoroethane of whipping agent: 1,1-bis-;

Expansible black lead A has the mean particle size of 0.18mm;

Expansible black lead B has the mean particle size of 0.15mm;

Expansible black lead C has the mean particle size of 0.17mm.

Expansible black lead, by natural flake graphite is immersed in chrome acid bath, then immerses in the vitriol oil, and subsequent drying is also ground to different size and prepares.

The composition of embodiment 1-5 and comparative example C1 (% by weight) is summarized in table 1.

Table 1

Embodiment	1	2	3	4	5	C1
							Expansible black lead	A	B	B	A	C	?
Spraying temperature [℃]	50	60	60	50	50	40
							Aethoxy Sklerol 1	?	?	4.90	?	?	?
Polyesterols 1	?	?	34.10	?	?	?
							APP	?	?	?	?	7.00	?
Expanded graphite	16.38	10.79	13.04	25.48	15.00	?
							Aethoxy Sklerol 2	?	?	9.80	0.00	0.00	?
Polyesterols 2	44.44	46.62	?	38.52	41.77	50.12
							Aethoxy Sklerol 3	4.27	4.48	?	3.70	4.02	?
TEP	4.27	4.48	?	5.93	4.02	?
							TCPP	4.27	4.48	12.25	3.70	4.02	19.76
Tensio-active agent 1	0.43	0.45	0.49	0.37	0.40	0.54
							Tensio-active agent 2	0.85	0.90	0.49	0.74	0.80	0.54
Catalyzer 1	0.24	0.25	0.24	0.22	0.22	0.27
							Catalyzer 2	1.28	1.34	1.43	1.11	1.20	1.45
Catalyzer 3	2.36	2.47	2.39	2.15	2.27	2.65
							Catalyzer 4	1.37	1.43	?	1.19	1.29	1.54
Water	0.34	0.33	0.43	0.30	0.32	0.48
							Whipping agent	19.49	21.97	20.43	16.59	17.67	22.65

Amount to

100

100

100

100

100

100

The polyol component A of table 1 and isocyanate component B are mixed and be sprayed on surface under the relevant temperature shown in table 1.Isocyanate component B is that NCO content is the polymeric MDI of 31.2 % by weight." ratio of mixture " is the mass ratio of isocyanate component and polyol component.The nco index calculating provides in table 2.

Foaming properties is summarized in table 2.Oxygen index is the minimum concentration in the atmosphere of support material sustained combustion, with per-cent, represents.

Table 2

embodiment 6

Polyol component and isocyanate component are mixed and be sprayed on surface at the temperature of 60 ℃.

The raw material of described polyol component is listed in table 3, and foaming properties is listed in table 4.Isocyanic ester used is polymeric MDI, and under the 357.4NCO index calculating, NCO content is 31.2 % by weight.

Table 3

Component	Weight part
		Expansible black lead	20
Polyester polyol A	30
		Polyether glycol B	8.52
Phosphonium flame retardant	10
		Tensio-active agent	1.31
Gel catalyst	0.24
		Kicker	1.31
Catalyst for trimerization	3.79
		Water	0.52
HCFC141b?HF	21.35
		Amount to	100.00

Polyester polyol A: aromatic polyester polyols, OH value is that 175mg KOH/g and functionality are 2;

Polyether glycol B: polyether glycol, OH value is that 190mg KOH/g and functionality are 2, initial by ethylene glycol.

Table 4

Parameter	Embodiment 6
		Foam core density [kg/m 3]	37.4
Compressive strength [Mpa]	0.167
		Tensile strength [Mpa]	0.4
Thermal conductivity [mw/m*k]	20.63
		Water-intake rate [%]	2.4
The B2-test of catching fire	6

Length dimension stability [%] at 80 ℃	-0.3
		Width [%]	0
Thickness [%]	0
		Length dimension stability [%] at 80 ℃	-0.1
Width [%]	0.2
		Thickness [%]	-0.9
With concrete bond strength [Mpa]	0.15
		B1 grade (difficult combustion)	Obtain

Claims (21)

1. hard polyurethane foams, it can be by making

A) polyisocyanates with

B) there are at least two compounds that isocyanate group are to reactive hydrogen atom,

C) whipping agent and

D) at least one fire retardant

There is lower reaction and obtain;

Wherein there are at least two compound b that isocyanate group are to reactive hydrogen atom) comprise at least one polyether glycol bi) and at least one polyester polyol bii), and fire retardant d) comprise expansible black lead di).

2. according to the hard polyurethane foams of claim 1, expansible black lead di wherein) with the amount of 2-25 % by weight, use, based on components b), c) and weight d).

3. according to the hard polyurethane foams of claim 1 or 2, polyether glycol bi wherein) with the amount of 3-20 % by weight, use, based on components b), c) and weight d).

4. according to the hard polyurethane foams of any one in claim 1-3, wherein polyester polyol bii) with the amount of 30-60 % by weight, use, based on components b), c) and weight d).

5. according to the hard polyurethane foams of any one in claim 1-4, wherein polyether glycol bi) hydroxyl value be 110-570mg KOH/g.

6. according to the hard polyurethane foams of any one in claim 1-5, wherein polyether glycol bi) functionality be 2-3.

7. according to the hard polyurethane foams of any one in claim 1-6, wherein polyester polyol bii) hydroxyl value be 160-750mg KOH/g.

8. according to the hard polyurethane foams of any one in claim 1-7, wherein polyester polyol bii) functionality be 2-4.

9. according to the hard polyurethane foams of any one in claim 1-8, wherein polyester polyol bii) be the esterification products of following material:

B1) 10-70 % by mole of dicarboxylic acid composition, it comprises:

B11) 50-100 % by mole of one or more aromatic dicarboxylic acid or derivatives thereof,

B12) 0-50 % by mole of one or more aliphatic dicarboxylic acid or derivatives thereof;

B2) 2-30 % by mole of one or more lipid acid or derivatives thereof;

B3) 10-70 % by mole one or more have 2-18 carbon atom aliphatic series or alicyclic dibasic alcohol or its alcoxylates;

B4) polyether glycol of 2-50 % by mole of functionality >=2, it can obtain by the alkoxylate of polyvalent alcohol.

10. according to the hard polyurethane foams of any one in claim 1-9, wherein fire retardant d) comprise additional component dii).

11. according to the hard polyurethane foams of claim 10, wherein additional component dii) for containing phosphorus component.

12. according to the hard polyurethane foams of claim 11, wherein additional component dii) be selected from diethyl ethylphosphate, propyl phosphonic acid methyl ester, triethyl phosphate and tricresyl phosphate (2-chloro isopropyl) ester.

13. according to the hard polyurethane foams of any one in claim 1-12, and its flame height is not more than 15cm, according to EN ISO11925-2 or GB/T8626-2007.

14. according to the hard polyurethane foams of any one in claim 1-13, and its average combustion residue is greater than 150mm, and its minimum combustion residue is greater than 0mm, and average flue-gas temperature is lower than 200 ℃, according to DIN4201 part 1 or GB/T8625-2005.

15. according to the hard polyurethane foams of any one in claim 1-14, and its smoke density grade is less than 75, according to GB/T8627-2007.

Prepare according to the method for the hard polyurethane foams of any one in claim 1-15 for 16. 1 kinds, wherein by fire retardant d) sneak into components b) in.

17. according to the method for claim 16, and wherein said foam is prepared by bubble jet coating method.

18. 1 kinds of polyol components, it comprises:

Bi) polyether glycol,

Bii) polyester polyol,

C) whipping agent,

D) fire retardant d),

Fire retardant d wherein) comprise expansible black lead.

19. according to the polyol component of claim 18, wherein fire retardant d) comprise containing phosphorus component as additional component dii).

20. according to the polyol component of claim 18 or 19, wherein additional component dii) be selected from diethyl ethylphosphate, propyl phosphonic acid methyl ester, triethyl phosphate and tricresyl phosphate (2-chloro isopropyl) ester.

21. according to the polyol component of any one in claim 18-20, wherein polyester polyol bii) be the esterification products of following material:

B1) 10-70 % by mole of dicarboxylic acid composition, it comprises:

B11) 50-100 % by mole of one or more aromatic dicarboxylic acid or derivatives thereof,

B12) 0-50 % by mole of one or more aliphatic dicarboxylic acid or derivatives thereof;

B2) 2-30 % by mole of one or more lipid acid or derivatives thereof;

B3) 10-70 % by mole one or more have 2-18 carbon atom aliphatic series or alicyclic dibasic alcohol or its alcoxylates;

B4) polyether glycol of 2-50 % by mole of functionality >=2, it can obtain by the alkoxylate of polyvalent alcohol.