CN103289039A - Rigid polyurethane foam polyether composition and rigid polyurethane foam prepared from same - Google Patents
Rigid polyurethane foam polyether composition and rigid polyurethane foam prepared from same Download PDFInfo
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- CN103289039A CN103289039A CN2012100598020A CN201210059802A CN103289039A CN 103289039 A CN103289039 A CN 103289039A CN 2012100598020 A CN2012100598020 A CN 2012100598020A CN 201210059802 A CN201210059802 A CN 201210059802A CN 103289039 A CN103289039 A CN 103289039A
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Abstract
The invention provides a rigid polyurethane foam polyether composition which comprises one or more polyether polyols, one or more polyester polyols and a foam stabilizer, wherein the hydroxyl value of the polyether polyol is 200-800mg KOH/g, and the degree of functionality is 2-8; the hydroxyl value of the polyester polyol is 50-500mg KOH/g, and the degree of functionality is 2-5; and the content of organic silicon of the foam stabilizer is 25-40wt%. The invention also provides rigid polyurethane foam prepared from the polyether composition, wherein the rigid foam has good thermal insulation and flame resistance and can be applied to the thermal insulation of buildings, pipelines, tank bodies, refrigerator cars, refrigerator compartments, refrigeration and freezing equipment, refrigerators and roadbeds.
Description
Technical field
The application relates to a kind of hard polyurethane foam polyether composition, also relates to the hard polyurethane foam by this polyether composition preparation.
Background technology
Rigid polyurethane foams has good mechanical property and lower thermal conductivity, and in light weight, easily cohere, burn with other base material and do not produce molten drop, so be widely used in the insulation of buildings and pipeline.
The loss that brings for the generation that reduces fire and fire, there is certain requirement countries in the world for the flame retardant properties of this class heat insulating polyurethane hard foam material, for example State Council " State Council about strengthen and improve firemanic suggestion " (No. [2011] 46, promulgated by the State Council) is used for exterior-wall heat insulation and forbids to use flame retardant rating B3 material with hard polyurethane foam, the B2 material is used in restriction, recommends to use B1 and A level material.
Therefore, for improving the flame retardant properties of hard polyurethane foam, usually in insulation is filled a prescription with hard polyurethane foam, add fire retardant usually, but the interpolation of fire retardant is limited to the flame retardant properties raising of hard polyurethane foam, and excessive interpolation fire retardant can reduce the mechanical property of the foam that makes.
The another kind of method that improves the Polyurethane Rigid Foam Flame Retardance performance is in the hard polyurethane foam prescription, uses the special type flame retardant polyether glycol, for example available from Su Wei company (Solvay Fluor, IxolB251 German).Though the hard polyurethane foam that this method obtains has good flame retardancy, the special type flame retardant polyether glycol is expensive usually, has significantly improved production cost.
Therefore, still need a kind of have good flame-retardance energy and polyurethane rigid foam material with low cost in this area.
Summary of the invention
One aspect of the invention is to provide a kind of hard polyurethane foam polyether composition, comprises:
(a) one or more polyether glycols, the hydroxyl value of described polyether glycol are 200-800mgKOH/g, and functionality is 2-8;
(b) one or more polyester polyols, the hydroxyl value of described polyester polyol are 50-500mg KOH/g, and functionality is 2-5;
(c) suds-stabilizing agent, the organosilicon content of described suds-stabilizing agent is 25-40wt.%.
In one embodiment of the invention, the weight ratio of described polyester polyol and described suds-stabilizing agent is preferably 100: 0.1-100: 10, more preferably 100: 1.5-100: 6.
In another embodiment, the content of described suds-stabilizing agent is preferably 0.1-10wt.%, 0.5-3wt.% more preferably, based on the weight of described hard polyurethane foam polyether composition by 100wt.%.
In another embodiment of the present invention, described polyether composition also comprises fire retardant, and preferably, described fire retardant is the mixture of liquid flame retardant and solid flame retardant.Preferably, the content of described solid flame retardant is 30-200wt.%, based on said components (a) and weight (b) by 100wt.%.Preferably, described liquid flame retardant is selected from following one or more: three (2-chloropropyl) phosphoric acid ester, three (2-chloroethyl) phosphoric acid ester, three (two chloropropyls) phosphoric acid ester, four (2-chloroethyl) ethylene phosphoric acid ester, dimethyl methyl phosphonate (DMMP) and polybromodiphenyl ether.Preferably, described solid flame retardant is selected from following one or more: trimeric cyanamide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, aluminium hydroxide, magnesium hydroxide, borate, ammonium polyphosphate and three (2,3-dibromopropyl) isomelamine ester, wollastonite and expansible black lead.
The present invention is to provide a kind of hard polyurethane foam on the other hand, and described hard polyurethane foam is the reaction product that comprises the reactive component of above-mentioned polyether composition and isocyanic ester.
In one embodiment of the invention, the weight ratio of described isocyanic ester and polyether composition is 0.5: 1-5: 1.
In another embodiment, the oxygen index of described hard polyurethane foam is 22.8-28.3%, measures according to GB/T 2406-2008.
In another embodiment of the present invention, the thermal conductivity of described hard polyurethane foam is 21.2-25.7mW/m*K, according to GB/T 10294-2008 standard test.
The present invention also is to provide a kind of heat-insulation system on the one hand, and wherein said system comprises above-mentioned hard polyurethane foam.In one embodiment of the invention, described heat-insulation system is selected from buildings, pipeline and tank body, refrigerator car and refrigeration railway carriage or compartment, refrigerating equipment, freezer and roadbed.
The present invention also has been to provide above-mentioned hard polyurethane foam to be used for the purposes of preparation heat-insulation system on the one hand.In one embodiment of the invention, affiliated heat-insulation system is selected from buildings, pipeline and tank body, refrigerator car and refrigeration railway carriage or compartment, refrigerating equipment, freezer and roadbed.
Embodiment
The present patent application people is surprised to find that in practice, be used in combination the flame retardant properties that the suds-stabilizing agent of the pure and mild organosilicon content of polyester polyols between 25-40wt.% improved hard polyurethane foam, it does not need to use the special type flame retardant polyethers, reduce the production cost of hard polyurethane foam, also kept the heat-insulating property of hard polyurethane foam simultaneously.
Rigid polyurethane foaming composition polyether composition
When being used for this paper, " hard polyurethane foam polyether composition " refers to be used to form the composition of one or more polyether glycols of hard polyurethane foam, can also comprise other polyvalent alcohol and other components such as catalyzer, fire retardant, suds-stabilizing agent, whipping agent, weighting material for example in the said composition.
Can be used for polyether glycol of the present invention (a) and comprise the polyether glycol that is made by known method, for example, in the presence of catalyzer, the reaction of alkene oxide and polyvalent alcohol initiator makes, and described catalyzer is alkali metal hydroxide, basic metal alcoxylates, antimony pentachloride, boron fluoride etherate or metal complex catalysts for example.The example of suitable alkene oxide comprises tetrahydrofuran (THF), oxyethane, 1,2 epoxy prapane, 1,2-butylene oxide ring, 2,3-butylene oxide ring and styrene oxide.Described polyether glycol preferably contains uncle OH end group, and also can have secondary OH group.Suitable starter molecules can be selected from polyol, for example water, ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, Diethylene Glycol or TriMethylolPropane(TMP).The hydroxyl value that can be used for polyether glycol of the present invention is 200-800mg KOH/g, and functionality is 2-8.Those skilled in the art know the measuring method of hydroxyl value, for example the measuring method of putting down in writing at GB12008.3-2009.
Can be used for polyether glycol of the present invention can be above-mentioned a kind of polyether glycol, also can be the composition of above-mentioned multiple polyether glycol.In the present invention, the consumption of described polyether glycol can be 10-90wt.%, is preferably 30-80wt.%, and 50-80wt.% more preferably is 100 parts in the gross weight of polyether composition.Can be used for the example of polyether glycol of the present invention, include but not limited to, available from Arcol 3607 and the Desmophen Z450 of Bayer Material Science company limited.
Hard polyurethane foam polyether composition of the present invention also comprises one or more polyester polyols (b).Can be used for polyester polyol of the present invention (b) and comprise the polyester polyol that is made by organic dicarboxylic acid or dicarboxylic anhydride and polyhydroxy-alcohol reaction.Suitable dicarboxylic acid preferably contains the aliphatic carboxylic acid of 2-12 carbon atom, for example, succsinic acid, propanedioic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, decane-dicarboxylic acid, toxilic acid, fumaric acid, phthalic acid, m-phthalic acid and terephthalic acid.Described dicarboxylic acid can be used singly or in combination.Suitable acid anhydrides comprises, for example Tetra hydro Phthalic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid and maleic anhydride.The example of exemplary polyhydroxy-alcohol comprises ethylene glycol, Diethylene Glycol, 1,2-propylene glycol, 1, ammediol, dipropylene glycol, 1,3-methyl propanediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, neopentyl glycol, 1,10-decanediol, glycerol, TriMethylolPropane(TMP), perhaps at least two kinds mixture in these glycol.Also can use the polyester polyol of lactone such as 6-caprolactone.Can be used for polyester polyol of the present invention and also comprise polycarbonate polyol.Described polycarbonate polyol can be by glycol (for example, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, Diethylene Glycol or three oxygen ethyl glycols) make with dialkyl carbonate or diaryl carbonate (for example, diphenyl carbonate or phosgene) reaction.The hydroxyl value that can be used for polyester polyol of the present invention is 50-500mg KOH/g, and functionality is 2-5.
Can be used for polyester polyol of the present invention can be above-mentioned a kind of polyester polyol, also can be the composition of above-mentioned multiple polyester polyol.In the present invention, the consumption of described polyester polyol can be 10-90wt.%, is preferably 20-70wt.%, 20-50wt.% more preferably, in the weight of polyether composition by 100wt.%.The example that can be used for polyester polyol of the present invention includes but not limited to the Stepanpol 3152 available from Nanjing, Nanjing Si Taipan chemistry company limited.
Polyether composition of the present invention also comprises suds-stabilizing agent (c), and described suds-stabilizing agent has definition well-known to those skilled in the art.In one embodiment of the invention, described suds-stabilizing agent is preferably the type siloxane suds-stabilizing agent, and its organosilicon content is 25-40wt.%, is preferably 27-30wt.%.The example that can be used as suds-stabilizing agent of the present invention includes, but are not limited to
DC193 (available from U.S. aerochemistry company).
The amount of employed suds-stabilizing agent is about 0.1-10wt.%, is preferably 0.1-3wt.%, and more preferably 0.5-3wt.% also is preferably 0.5-1.0wt.%, based on the weight of above-mentioned polyether glycol and polyester polyol by 100wt.%.
In the present invention, the combination of above-mentioned polyester polyol (b) and above-mentioned suds-stabilizing agent (c) can improve the flame retardant properties of the hard polyurethane foam that makes, wherein the weight ratio of polyester polyol and suds-stabilizing agent is preferably 100: 0.1-100: 10, more preferably 100: 1.5-100: 6.
Be used for polyether composition of the present invention and can also comprise fire retardant.Described fire retardant can be any known fire retardant in this area.The consumption of fire retardant can be 10-30wt.%, is 100 parts in the gross weight of polyether composition.
In one embodiment of the invention, being used for fire retardant of the present invention is the mixture of liquid flame retardant and solid flame retardant, uses liquid flame retardant and solid flame retardant to can further improve the flame retardant properties of the foam that makes simultaneously.Preferably, the content of solid-state fire retardant is 30-200wt.% in this mixture, is preferably 30-80wt.%, based on the weight of polyether polyatomic alcohol component (a) and polyester polyols alkoxide component (b) by 100wt.%.
In one embodiment of the invention, described liquid combustion inhibitor is selected from following one or more: three (2-chloropropyl) phosphoric acid ester (TCPP), three (2-chloroethyl) phosphoric acid ester (TCEP), three (two chloropropyls) phosphoric acid ester (TDCPP), four (2-chloroethyl) ethylene phosphoric acid ester, dimethyl methyl phosphonate (DMMP) and polybromodiphenyl ether.
In one embodiment of the invention, described solid-state fire retardant is selected from following one or more: trimeric cyanamide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, aluminium hydroxide, magnesium hydroxide, borate, ammonium polyphosphate and three (2,3-dibromopropyl) isomelamine ester, wollastonite and expansible black lead.Preferably, described solid-state fire retardant is trimeric cyanamide.
Polyether composition of the present invention can also comprise binder components such as whipping agent, catalyzer.
Whipping agent of the present invention can be selected various pneumatogens or chemical foaming agent for use, and is preferred but be not limited to water, halohydrocarbon, hydrocarbon compound, gas.Described halohydrocarbon, preferred but be not limited to chlorodifluoronmethane, dichloro one methyl fuoride, dichloro methyl fuoride, trichlorine methyl fuoride or their mixture.Described hydrocarbon compound, preferred but be not limited to butane, pentane, pentamethylene, hexane, hexanaphthene, heptane or their mixture.Described gas, preferred but be not limited to air, CO
2, or N
2Described whipping agent, special preferably water.The consumption of described whipping agent is determined by the desired density that reaches of described urethane.
Catalyzer of the present invention, preferred but be not limited to amines catalyst, organo-metallic catalyst or their mixture.Described amines catalyst, preferred but be not limited to triethylamine, tributylamine, triethylenediamine, N-ethylmorpholine, N, N, N ', N '-tetramethyl--quadrol, pentamethyl-diethylidene-triamine, N, methylphenylamine, N, accelerine or their mixture.Described organo-metallic catalyst, preferred but be not limited to the organic tin compound, for example: tin acetate (II), stannous octoate (II), thylhexoic acid tin, tin laurate, Dibutyltin oxide, dibutyl tin dichloride, dibutyl tin acetate, dibutyl toxilic acid tin, dioctyl oxalic acid tin or their mixture.Described catalyst consumption is 0.001-10wt.%, in polyvalent alcohol in the reaction system (being polyether polyatomic alcohol component (a) and polyester polyols alkoxide component (b)) consumption sum by 100wt.%.
Those skilled in the art can also add other composition according to concrete needs in polyether composition of the present invention, such as but not limited to: auxiliary agents such as pore-creating agent, anti-aging agent and pigment.
Hard polyurethane foam
When being used for this paper, (Zhu Lvmin etc. write according to " urethane foam ", the third edition, Chemical Industry Press, 2005), " hard polyurethane foam " refers to not take place obvious deformation under the certain load effect, can not return to the porous plastics of original state after the excessive generation deformation of load, and above-mentioned disclosed associated viscera is incorporated herein by reference.
Hard polyurethane foam of the present invention is raw material with isocyanic ester and above-mentioned polyether composition, by preparation method well known in the art and instrument preparation, specifically see (the 408th page of explanation in " urethane foam " for details, Zhu Lvmin etc. write, the third edition, Chemical Industry Press, 2005), the full content of the disclosure is incorporated herein by reference.Wherein, the weight ratio of polyether composition and isocyanic ester determines by nco index, described nco index X as shown in the formula define:
The method that can be used for preparing hard polyurethane foam of the present invention for example well known to a person skilled in the art " single stage method ", be about to raw materials such as polyethers or polyester polyol, isocyanic ester, catalyzer, suds-stabilizing agent, whipping agent and all mix through metering, generate the method for rigid foam behind the generation chemical reaction.
Isocyanic ester for the preparation of hard polyurethane foam of the present invention can be used general formula R (NCO)
nThe expression, wherein R represent to contain 2-18 carbon atom aliphatic alkyl, contain the aryl of 6-15 carbon atom or contain 8-15 carbon atom aryl aliphatic hydrocarbyl, n=2-5.
Described isocyanic ester, preferred but be not limited to the vinyl vulcabond, tetramethylene 1, the 4-vulcabond, hexamethylene diisocyanate (HDI), dodecyl-1, the 2-vulcabond, tetramethylene-1, the 3-vulcabond, hexanaphthene-1, the 3-vulcabond, hexanaphthene-1, the 4-vulcabond, 1-isocyanate group-3,3,5-trimethylammonium-5-isocyanate group methylcyclohexane, hexahydrotoluene-2, the 4-vulcabond, hexahydrobenzene base-1, the 3-vulcabond, hexahydrobenzene base-1, the 4-vulcabond, perhydro-ditane-2, the 4-vulcabond, perhydro-ditane-4, the 4-vulcabond, phenylene-1, the 3-vulcabond, phenylene-1, the 4-vulcabond, durene-1, the 4-vulcabond, stibene-1, the 4-vulcabond, 3,3 '-dimethyl-4,4 '-diphenyl diisocyanate, Toluene-2,4-diisocyanate, 4-vulcabond (TDI), Toluene-2,4-diisocyanate, 6-vulcabond (TDI), ditane-2,4 '-vulcabond (MDI), ditane-2,2 '-vulcabond (MDI), ditane-4,4 '-vulcabond (MDI), naphthylene-1 (NDI), their mixture, their isomer, or they and they mixture of isomers.
Described isocyanic ester, also comprise the polyisocyanates with carbonization imines, allophanate or isocyanate-modified gained, preferred but be not limited to '-diphenylmethane diisocyanate, imine modified '-diphenylmethane diisocyanate, their mixture, their isomer or they and they the mixture of isomers of carbonization.
Described isocyanic ester can also be the isocyanic ester performed polymer.The NCO content of described isocyanic ester performed polymer, preferred but be not limited to 5-30wt.%, preferred especially 10-25wt.%, in the weight of described isocyanic ester performed polymer by 100wt.%.
The applicant is surprised to find that, improves the flame retardant properties that can further improve the gained hard polyurethane foam for the preparation of the amount ratio of the isocyanic ester of hard polyurethane foam of the present invention and polyether composition.Preferably, the amount ratio of isocyanic ester and polyether composition is 0.5: 1 to 5: 1, more preferably 0.6: 1 to 3: 1, also is preferably 0.8: 1 to 2: 1.
Hard polyurethane foam of the present invention has good heat-insulating property, and its thermal conductivity is 21.2-25.7mW/m*K, according to GB/T 10294-2008 standard test.
Hard polyurethane foam of the present invention also has good flame retardancy simultaneously, and its oxygen index is 22.8-28.3%, measures according to GB/T 2406-2008.As well known to those skilled in the art in addition, the oxygen index of two kinds of polyurethane rigid foam materials differ 0.3% or more than, represent that then the flame retardant properties of these two kinds of materials has evident difference.
The hard polyurethane foam heat-insulation system
The present invention also provides the heat-insulation system that comprises hard polyurethane foam of the present invention.
When being used for when of the present invention, term " heat-insulation system " is to instigate target compound to maintain system in the specific temperature range in for some time.Heat-insulation system of the present invention is preferably selected from buildings, pipeline and tank body, refrigerator car and refrigeration railway carriage or compartment, refrigerating equipment, freezer and roadbed.To those skilled in the art, the method for using hard polyurethane foam of the present invention to prepare above-mentioned heat-insulation system is known.
Buildings as herein described can be any known civilian, commercial or military building in this area, and wherein polyurethane rigid foam material of the present invention can be used as building slab and building thermal insulation material.Preferably, building of the present invention is building construction.The polyurethane rigid foam material that is included in the building heat insulation system of the present invention can be applied to described building with forms such as the sandwich panel that hard bubbles, spray foam, cast member and single-component filleting foams.An example of building heat insulation system of the present invention is the building exterior wall heat preserving system with following structure: be basic unit, adhesive layer, hard polyurethane foam lagging material of the present invention, finishing mucilage protective layer, glass fiber reticular cloth enhancement layer, flexible putty and the coating ornamental surface layer that substrate is arranged in order with the body of wall.Those skilled in the art can make appropriate change to said structure according to different application and different insulation requirements.
Pipeline as herein described and tank body comprise pipeline and the tank body of carrying cold or thermal medium, and the example is the used pipeline of heating system, industrial hot and cold pipeline and oil pipeline and tank body for example.Polyurethane rigid foam material in pipeline of the present invention and the tank body heat-insulation system can adopt the different modes of production to be applied according to shape and the insulation requirement of used pipeline and tank body.For example, be example for semicircle tube shell and mo(u)lded item, can use cutting machine and cutting machine, massive polyurethane is hard bubbled cut and cut into semicircular tubulose foam element according to size.When adopting the molding foaming method to produce, just can obtain the molding pipe fitting of epidermis densification.According to different needs, housing can coat with bituminous carpet, plastics film or aluminium foil or metal sheet.
Refrigerator car as herein described and refrigeration railway carriage or compartment comprise refrigerator car and the refrigeration railway carriage or compartment of various uses, and the example includes but not limited to railway carriage, conditioned train passenger compartment, container, medical refrigerated car etc.
Refrigerating equipment as herein described comprises various civilian, commercial medical refrigerator and refrigerators, because polyurethane rigid foam plastic intensity height, hard bubble when linking to each other between the housing of equipment and the liner, do not need other propping material, thereby do not have " cold bridge ", guaranteed the insulation effect of equipment.
Freezer as herein described comprises the large-scale and miniature cold storage of various uses, and the example includes but not limited to the freezer for products such as refrigeration or freezing sea-foods, meat, vegetables, fruit, grain.
Roadbed as herein described comprises railway and highway subgrade.Taked the roadbed of heat-preserving anti-freezing measure can avoid roadbed to damage the loss that causes because of frost heave or thaw collapse.
The purposes of hard polyurethane foam
Hard polyurethane foam of the present invention can be for the preparation of heat-insulation system, and described heat-insulation system as defined above.In one embodiment, described heat-insulation system is selected from buildings, pipeline and tank body, refrigerator car and refrigeration railway carriage or compartment, refrigerating equipment, freezer and roadbed.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.But what those skilled in the art should understand that is that these embodiment only are used for explanation the present invention and do not constitute limitation of the scope of the invention.
Use the commercial goods as follows among the embodiment:
Arcol 3607, polyether glycol, and available from Bayer Material Science (China) company limited, hydroxyl value: 430, viscosity 3400, functionality 4.2;
Desmophen Z450, polyether glycol, available from Bayer Material Science (China) company limited, hydroxyl value: 340, viscosity 11000, functionality 4.0;
Stepanpol PS3152, polyester polyol, available from Nanjing, Nanjing Si Taipan chemistry company limited, hydroxyl value: 315, viscosity 2500, functionality 2.0;
Three (2-chloropropyl) phosphoric acid ester (TCPP), liquid combustion inhibitor is available from Jiangsu Yoke Chemical Co., Ltd.;
Trimeric cyanamide, solid-state fire retardant is available from the high letterization glass in Shanghai Instr Ltd.;
DC193, suds-stabilizing agent, organosilicon content are 28wt.%, available from U.S. aerochemistry company;
AK-8830, suds-stabilizing agent, organosilicon content is 55-65wt.%, available from Nanjing Dymatic Shichuang Chemical Co., Ltd.;
POLYCAT-8, the urethane synthetic catalyst is available from air Chemicals (China) company limited;
POLYCAT-41, the urethane synthetic catalyst is available from air Chemicals (China) company limited;
HCFC-141b, whipping agent is available from Zhejiang Sanmei Chemical Industries Co., Ltd..
I.
Each method of the system of hard polyurethane foam
Following be among the embodiment, if no special instructions, hard polyurethane foam of the present invention all adopts following method preparation: classify the component except isocyanic ester as A, classify isocyanate component as B, in whipping appts, the A component is fully mixed, then this mixture is passed through two-pack high pressure foaming machine (HK650, Heng Neiji machinery (Shanghai) Co., Ltd.), be to carry out the urethane high-pressure foam under 20 ℃ the environment in the material temperature, make hard polyurethane foam.
II.
Polyester polyol (components b) is to the Polyurethane Rigid Foam Flame Retardance Effect on Performance
From following table 1 as can be seen, add polyester polyol STEPANPOL PS3152 in the polyether composition, with
DC193 is used in combination the flame retardant properties that can obviously improve the gained hard polyurethane foams.
Table 1 components b is to the influence of flame retardant properties
*The weight ratio of isocyanic ester and polyether composition is 1.8: 1
III.
Suds-stabilizing agent (amount of component b) is to the influence of hard polyurethane foams flame retardant properties
In following table 2, having used organosilicon content among the embodiment 2 is 28% suds-stabilizing agent, be that organosilicon content is the suds-stabilizing agent AK-8830 of 55-65wt.% and comparative example 2 uses, and the oxygen index of the hard polyurethane foam of embodiment 2 is 27.6%, far above comparative example 2 oxygen index.Therefore as can be known, be used in combination the flame retardant properties that polyester polyol (components b) and special suds-stabilizing agent (amount of component b) can improve the gained hard polyurethane foam.
Table 2 suds-stabilizing agent is to the influence of flame retardant properties
*The weight ratio of isocyanic ester and polyether composition is 1.6: 1.
IV.
The amount ratio of isocyanic ester and polyether composition is to the influence of flame retardant properties
In following table 3, the weight ratio of isocyanic ester and polyether composition is 1.6: 1 among the embodiment 3, among the embodiment 4 is 1.8: 1, correspondingly oxygen index rises to 28.3% from 27.6%, and this shows that the weight ratio that improves isocyanic ester and polyether composition can improve the flame retardant properties of gained hard polyurethane foam.
The amount ratio of table 3 isocyanic ester and polyether composition is to the influence of flame retardant properties
*The weight ratio of isocyanic ester and polyether composition was respectively 1.6: 1, and 1.8: 1,2.0: 1
V.
The influence of the flame retardant properties that fire retardant hard bubbles to hard polyaminoester
In following table 4, embodiment 6 does not add fire retardant, the liquid flame retardant TCPP that has added 30 parts among the embodiment 7, the solid flame retardant trimeric cyanamide that has added 30 parts among the embodiment 8, the TCPP and the trimeric cyanamide that have added 15 parts among the embodiment 9 have respectively added 30 parts TCPP and trimeric cyanamide respectively among the embodiment 10.
From embodiment 6-8, can obviously find out, add the flame retardant properties that liquid or solid flame retardant can significantly improve hard polyurethane foam.From embodiment 7-10, can obviously find out, be used in combination the flame retardant properties that liquid flame retardant and solid flame retardant can further improve hard polyurethane foam.
The influence of the flame retardant properties that table 4 fire retardant hard bubbles to hard polyaminoester
*The weight ratio of isocyanic ester and polyether composition is 1.4: 1
The those skilled in the art knows that easily the present invention is not limited only to the detail of previous embodiment, and under the prerequisite that does not break away from spirit of the present invention or main characteristic, the present invention can be embodied as other particular forms.Therefore all should be with described embodiment regarded as illustrative from any angle and nonrestrictive, thereby by claims but not above stated specification is pointed out scope of the present invention; And therefore any change as long as it belongs in the implication and scope of claim equivalent, all should be regarded as and belong to the present invention.
Claims (18)
1. hard polyurethane foam polyether composition comprises:
(a) one or more polyether glycols, the hydroxyl value of described polyether glycol are 200-800mgKOH/g, and functionality is 2-8;
(b) one or more polyester polyols, the hydroxyl value of described polyester polyol are 50-500mgKOH/g, and functionality is 2-5;
(c) suds-stabilizing agent, the organosilicon content of described suds-stabilizing agent is 25-40wt.%.
2. hard polyurethane foam polyether composition according to claim 1, the weight ratio of wherein said polyester polyol and described suds-stabilizing agent is 100: 0.1-100: 10.
3. hard polyurethane foam polyether composition according to claim 2, the weight ratio of wherein said polyester polyol and described suds-stabilizing agent is 100: 1.5-100: 6.
4. hard polyurethane foam polyether composition according to claim 1, the content of wherein said suds-stabilizing agent is 0.1-10wt.%, based on the weight of described hard polyurethane foam polyether composition by 100wt.%.
5. hard polyurethane foam polyether composition according to claim 4, the content of wherein said suds-stabilizing agent is 0.5-3wt.%, based on the weight of described hard polyurethane foam polyether composition by 100wt.%.
6. according to each described hard polyurethane foam polyether composition among the claim 1-5, wherein said hard polyurethane foam polyether composition also comprises fire retardant.
7. hard polyurethane foam polyether composition according to claim 6, wherein said fire retardant comprises the mixture of liquid flame retardant and solid flame retardant.
8. polyurethane composition polyether composition according to claim 7, the content of wherein said solid flame retardant is 30-200wt.%, based on described component (a) and weight (b) by 100wt.%.
9. hard polyurethane foam polyether composition according to claim 7, wherein said liquid flame retardant are selected from following one or more: three (2-chloropropyl) phosphoric acid ester, three (2-chloroethyl) phosphoric acid ester, three (two chloropropyls) phosphoric acid ester, four (2-chloroethyl) ethylene phosphoric acid ester, dimethyl methyl phosphonate and polybromodiphenyl ether.
10. hard polyurethane foam polyether composition according to claim 7, wherein said solid flame retardant is selected from following one or more: trimeric cyanamide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, aluminium hydroxide, magnesium hydroxide, borate, ammonium polyphosphate and three (2,3-dibromopropyl) isomelamine ester, wollastonite and expansible black lead.
11. a hard polyurethane foam is the reaction product that comprises according to the reactive component of each described hard polyurethane foam polyether composition and isocyanic ester among the claim 1-10.
12. hard polyurethane foam according to claim 11, the weight ratio of wherein said isocyanic ester and polyether composition are 0.5: 1-5: 1.
13. according to claim 11 or 12 described hard polyurethane foams, the oxygen index of wherein said hard polyurethane foam is 22.8-28.3%, measures according to GB/T 2406-2008.
14. according to claim 11 or 12 described hard polyurethane foams, the thermal conductivity of wherein said hard polyurethane foam is 21.2-25.7mW/m*K, according to GB/T 10294-2008 standard test.
15. a heat-insulation system, wherein said system comprises each described hard polyurethane foam among the claim 11-14.
16. heat-insulation system according to claim 15, wherein said heat-insulation system are selected from buildings, pipeline and tank body, refrigerator car and refrigeration railway carriage or compartment, refrigerating equipment, freezer and roadbed.
17. be used for the purposes of preparation heat-insulation system according to each described hard polyurethane foam among the claim 11-14.
18. purposes according to claim 17, wherein said heat-insulation system is selected from: buildings, pipeline and tank body, refrigerator car and refrigeration railway carriage or compartment, refrigerating equipment, freezer and roadbed.
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| CN103498537A (en) * | 2013-10-20 | 2014-01-08 | 山东普兰特板业有限公司 | Poly isocyanuric acid ester modified polyurethane roof waterproof thermal-insulation board and producing process thereof |
| CN103497305A (en) * | 2013-10-20 | 2014-01-08 | 山东普兰特板业有限公司 | Metal surface polyisocyanurate modified polyurethane sandwich panel and production method thereof |
| CN103709356A (en) * | 2013-12-27 | 2014-04-09 | 北京碧海舟腐蚀防护工业股份有限公司 | Polyurethane rigid foam composition, heat-insulation layer and heat-insulation pipeline |
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| CN103498537A (en) * | 2013-10-20 | 2014-01-08 | 山东普兰特板业有限公司 | Poly isocyanuric acid ester modified polyurethane roof waterproof thermal-insulation board and producing process thereof |
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| CN105756274A (en) * | 2014-09-22 | 2016-07-13 | 科思创聚合物（中国）有限公司 | Polyurethane based prefabricated concrete thermal insulation element and preparation method thereof |
| CN105199373A (en) * | 2015-10-09 | 2015-12-30 | 蚌埠市天源气体有限责任公司 | Compression-resistant thermal-insulation material for low-temperature pipelines and preparation method thereof |
| CN105368034A (en) * | 2015-10-28 | 2016-03-02 | 界首市兴安塑料制品有限公司 | High pressure tightness foamed product and production process thereof |
| CN107383330A (en) * | 2017-07-31 | 2017-11-24 | 镇江科特新材料有限公司 | A kind of high-flame-resistance environment-friendly insulation material and preparation method thereof |
| CN107299692A (en) * | 2017-08-28 | 2017-10-27 | 天津市奇才防水材料有限公司 | A kind of water-proof heat-preserving integrated plate |
| CN107892740A (en) * | 2017-11-27 | 2018-04-10 | 山东诺威新材料有限公司 | High flame-retardant polyurethane insulation material and preparation method thereof |
| CN108341946A (en) * | 2018-02-01 | 2018-07-31 | 北京工商大学 | A kind of phosphorus base block flame retarding polyether and preparation method thereof and the application in hard polyurethane foams |
| CN109851740A (en) * | 2019-01-22 | 2019-06-07 | 安徽中科都菱商用电器股份有限公司 | The foamed heat-insulating material and preparation method thereof of medical ultra low temperature freezer |
| CN110016113A (en) * | 2019-03-02 | 2019-07-16 | 广州立泰新材料科技有限公司 | A kind of fire-retardant building polyurethane foamed material |
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