CN1142513A - Process for preparing open-cellular rigid polyurethane foam - Google Patents
Process for preparing open-cellular rigid polyurethane foam Download PDFInfo
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- CN1142513A CN1142513A CN96107387A CN96107387A CN1142513A CN 1142513 A CN1142513 A CN 1142513A CN 96107387 A CN96107387 A CN 96107387A CN 96107387 A CN96107387 A CN 96107387A CN 1142513 A CN1142513 A CN 1142513A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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Abstract
The invention relates to a process for producing an open-cell rigid polyurethane foam. A polyol mixture comprising 10-60wt.% hydroxyl-terminated reaction product (c) obtained by reacting an organic polyisocyanate (a) with 20-90wt.% polyether polyol (b), as to provide 1.3-10.0 equivalents of the hydroxyl groups of per NCO equivalent is reacted with an organic polyisocyanate having an average functionality of 2.0-2.8. The obtained foam shows excellent in mechanical properties and dimensional stability, and is suitable for congealer as adiabatic material and inside or outside material for architecture.
Description
The present invention relates to a kind of method that under good operational condition and working conditions, prepares open-cell rigid polyurethane foams with very good mechanical properties and dimensional stability.
Hard polyurethane foams generally is widely used as, for example, adiabatic, structured material, the vibration proofing material of refrigerator and packing material etc., for building every cold storage tank, heat insulation storage tank, inside and outside material, insulated piping, insulated cabinet, bathtub and physical culture goods etc.When preparing this hard polyurethane foams, generally in raw material, add whipping agent to regulate blistered degree and foam density etc.In the prior art, some freonll-11, as, Chlorofluorocarbons 11 (CFC-11), fluorochlorohydrocarbon 123 (HCFC-123) and Chlorofluorocarbons (CFCs) 141b (HCFC-141b) have been used as whipping agent.But for freonll-11, present research topic is how to avoid using them.
The known carbonic acid gas that is produced with isocyanic ester and the water reaction that joins in the polyol masses is as whipping agent.The result who uses carbonic acid gas be can be less with or without freonll-11.But on the other hand, the use of big water gaging has reduced foam density (apparent density), and since isocyanic ester and water reaction formation a large amount of, be incorporated into the urea in the urethane resin, the result, the resin of gained has relatively poor fragility.Due to the fact that, in operation with regard to some technical problem, as, peel off on the foam surface, or bonding bad between surfacing and the foam.
In addition, compare with the foam of making as whipping agent with fluorine Lyons with the foam that carbonic acid gas is made as whipping agent, its dimensional stability is bad.This be because, the velocity of diffusion of the carbonic acid gas in the abscess is greater than the penetration speed of air, the abscess in the foam is under the low pressure, the result, certain contraction appearred in foam when foam density was low.
Some prior aries disclose with water makes whipping agent, its make foam improved dimensional stability.For example, Japan special permission bulletin flat 04-487 of No. or special permission disclose flat 6-25375 and have disclosed a kind of method of improving contraction, avoid foam inside and outside pressure difference, make the open-cell polyurethane foam.These methods are characterised in that, the molecular weight that uses each oh group is lower than the polyol blends of 600 polyoxyalkylene polyol as the polyoxyalkylene polyol of 600-2000 and each oh group molecular weight, make open celled foam by form the stronger part of surface tension on forming than weak part or the some parts at pore membrane on the part pore membrane.But, these methods need add in polyol blends greater than each oh group molecular weight of 30wt% greater than 600 polyoxyalkylene polyol, the result is, the root cross-linking density of the urethane resin of gained accordingly descends, and foamy mechanical property such as ultimate compression strength, flexural strength geometric ratio closed-cell foam significantly reduce.
US 5250579 or US 5312846 have disclosed a kind of method of mechanical preparation open celled foam, added not only to be insoluble to polyvalent alcohol but also be insoluble to isocyanic ester, and surface free energy are lower than the trickle composition of 23mJ/m2.But the polyurethane material that has these trickle compositions is inhomogeneous, the difficulty in some processing and the storage often occurs.It is generally acknowledged that trickle composition is when isocyanic ester and polyvalent alcohol mixing, injects as the 3rd composition.But this method need be done very big effort and operating equipment is done a lot of improvement in operation control.In addition, at the fragility of resin surface or bonding with surfacing, also have some unsolved technical problems in the prior art.In other words, a kind of like this method not, can prepare with existing, compare the open-cell rigid polyurethane foams of dimensional stability and foam characteristic excellence as the foam that whipping agent makes with fluorine Lyons; Need not the used equipment of prior art is done any big improvement; Need not any at owing to use water as main whipping agent resin surface fragility or the operation of carrying out with the cementability of surfacing.
The purpose of this invention is to provide a kind of new method, under good work and operational condition, use existing producing apparatus, produce open-cell rigid polyurethane foams with excellent physical properties and dimensional stability.The present invention relates to a kind of preparation open-cell polyurethane foamy method, be at catalyzer, whipping agent and tensio-active agent exist down, make polyol blends (A) and organic multiple isocyanate (B) reaction, polyol blends wherein (A) comprises the mixture of reaction product (c) of the OH-terminal of a kind of 10-60wt%, this product (c) is to be organic multiple isocyanate (a) and the 20-90wt% of 1.6-2.9 by average functionality, average functionality is 2.0-6.0, molecular-weight average is 700-6000, ethylene oxide unit content is prepared with the every NCO equivalent reaction of 1.3-10.0OH equivalent less than the polyether glycol (b) of 10wt%, and organic multiple isocyanate (B) comprises that average functionality is the organic multiple isocyanate of 2.0-2.8.
The used organic multiple isocyanate (a) of the present invention comprises, for example, and poly methylene poly phenyl poly isocyanate, 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 2,2 '-diphenylmethanediisocyanate, 2,4-toluylene group diisocyanate, 2,6-toluylene group diisocyanate, right-phenylene vulcabond ,-Xylene Diisocyanate, 1, the 5-naphthalene diisocyanate, 3,3 '-dimethyl-4,4 '-the diphenylene vulcabond, isophorone diisocyanate, 1, the 6-hexamethylene diisocyanate, the improved polyisocyanates of its carbodiimide, the compound of the NCO-terminal that makes with the compound reaction that contains the hydrogen of isocyanate-reactive.Organic multiple isocyanate can use separately, or wherein at least two mixing are used, and make average functionality reach 1.6-2.9.When the average functionality of organic polyisocyanates (a) is lower than 1.6,, also can not get effective product in order to the open-cell rigid polyurethane foams of preparation size excellent in stability even it reacts with polyvalent alcohol (b).When the average functionality of organic polyisocyanates (a) surpassed 2.9, the viscosity of reaction product becomes too high made serviceability bad.
The polyether glycol (b) that the present invention is used, its average functionality is 2.0-6.0, molecular-weight average is 700-6000, the ethylene oxide unit amount is lower than 10 weight, for example comprise by average functionality be the amine compound of polyfunctional alcohol, hydroxyl of 2.0-8.0 or multifunctional aminocompound etc. with reactions such as oxyalkylene such as ethylene oxide, propylene oxides, make the ethylene oxide unit amount be lower than the resulting polyether glycol of 10wt%.Polyether glycol uses separately or uses with form of mixtures, and average functionality is that the polyfunctional alcohol of 2.0-8.0 for example comprises glycerol, propylene glycol, dipropylene glycol, TriMethylolPropane(TMP), tetramethylolmethane, methyl glucoside, Sorbitol Powder, mannitol, sucrose etc.The aminocompound that contains hydroxyl for example comprises Monoethanolamine MEA BASF, diethanolamine, trolamine etc.The polyfunctional compound for example comprises ethylene diamine, tolylene diamines, diethylenetriamine etc.When the molecular-weight average of polyether glycol (b) is lower than 700, even the reaction of it and organic multiple isocyanate (a) also can not get the effective product in order to the open-cell rigid polyurethane foams of preparation size excellent in stability.When the ethylene oxide unit amount surpasses 10wt%, can not obtain effective product.When the molecular-weight average of polyvalent alcohol and ethylene oxide unit amount are respectively greater than 6000 with during less than 10wt%, potential problem in operation then.
The reaction product (c) of preparation OH-terminal is to make described organic multiple isocyanate (a) and polyether glycol (b) react under the OH group equivalent of the 1NCO of (a) group equivalent to 1.3-10.0 (b) obtain.When the OH of (b) group equivalent less than 1.3 the time because the height polymerization uprises the viscosity of product, potential problems in operation.When the OH of (b) group equivalent surpasses 10.0, do not reach purpose of the present invention.By the way, in the present invention, when organic polyisocyanates (a) reacts with polyether glycol (b), can add softening agent, tensio-active agent, fire retardant, tinting material or catalyzer etc. non-imposedly.
Molecular-weight average is that the polyvalent alcohol (d) that 150-1200, ethylene oxide unit amount are lower than 10wt% for example comprises, oxyalkylene such as oxyethane and propylene oxide added be incorporated into the polyether glycol that makes on the following substances: the polyfunctional alcohol, as glycerol, propylene glycol, dipropylene glycol, TriMethylolPropane(TMP), trolamine, tetramethylolmethane, methyl glucoside, Sorbitol Powder, mannitol and sucrose; The amine compound that contains hydroxyl is as Monoethanolamine MEA BASF and diethanolamine; Polyfunctional aminocompound is as quadrol, tolylene diamines, diethylenetriamine; The polyester polyol that obtains by polyfunctional carboxylic acids and multifunctional hydroxy compounds polycondensation, or obtain the polyester polyol that cyclic esters ring-opening polymerization or ester are converted to by the hydroxycarboxylic acid polycondensation; Poly-(tetramethylene ether) glycol that tetrahydrofuran ring opening polymerization obtains, and their mixture.
In the present invention, polyol blends (A) comprises that the reaction product (c) of 10-60wt% OH terminal and 20-90wt%, molecular-weight average are the mixture that 150-1200, ethylene oxide unit amount are lower than the polyvalent alcohol (d) of 10wt%.When the reaction product (c) of OH-terminal when being less than 10wt%, the foam of gained has excellent size stability but does not have open-celled structure.When the reaction product (c) of OH-terminal during more than 60wt%, the foam of gained is inhomogeneous, and mechanical property comprises that ultimate compression strength, flexural strength etc. are bad.On the other hand, when polyvalent alcohol was less than 20wt%, gained foamy mechanical property was bad, and when polyvalent alcohol (d) during greater than 90wt%, the gained foam has excellent size stability but do not have open-celled structure.
In the present invention, unless will lose advantage of the present invention or effect, polyol blends (A) can contain any polyvalent alcohol except that described polyvalent alcohol (d) or have the compound of reactive hydrogen.Other polyvalent alcohol or the compound with reactive hydrogen for example comprise glycerine, diethanolamine and tolylene diamines etc.These compositions can add to improve the compatibility between foamy intensity or polyol blends and catalyzer, whipping agent or the tensio-active agent etc. non-imposedly.
Average functionality is that the organic multiple isocyanate (B) of 2.0-2.8 for example comprises polymethylene-polyphenyl polyisocyanate, 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 2,2 '-diphenylmethanediisocyanate, 2,4 '-the toluylene group diisocyanate, 2,6-toluylene group diisocyanate, right-phenylene vulcabond, between-Xylene Diisocyanate, l,5 naphthylene diisocyanate, 3,3 ' dimethyl-4,4 '-the biphenylene vulcabond, isophorone diisocyanate, 1, the 6-hexamethylene diisocyanate; The polyisocyanates of carbodiimide modification; The compound of the isocyanate groups terminal that makes with the compound reaction that contains the hydrogen of isocyanate-reactive, or their mixture.
In the present invention, preferably when polyol blends (A) reacts with organic multiple isocyanate (B), use known urethane catalysts,, resemble a tin or a plumbous class catalyzer as amine catalyst or organo-metallic catalyst.Amine is urged through agent and is for example comprised five methyl diethylentriamine, hexamethylene-diamine, and the tetramethyl-hexamethylene-diamine, or the like.Organo-metallic catalyst for example comprises dibutyl tin laurate, stannous octoate etc.
The whipping agent that the present invention preferably uses is a water.The preferred amounts of water is per 100 weight part polyol blends (A) 3-12 weight parts.Can adjust the foam density of final rigid foam product by the amount that changes water.Fluorochlorohydrocarbon is as 1, and 1-diamino-1-fluoroethane, hydrogen fluorine carbon are as 1,1,1, and 2-Tetrafluoroethane or low-boiling point liquid such as pentane, hexane etc. can use with water, also can.Carry one in passing, the present invention also can add known tensio-active agent non-imposedly, as the organo-siloxane multipolymer, or additive such as fire retardant, tinting material etc.
Embodiment
To be described more specifically the present invention in embodiment below and the Comparative Examples, but should be appreciated that the present invention is not limited to the described embodiment of following embodiment.Reacted constituent used in embodiment and the Comparative Examples is as follows.Unless special stipulation, term " weight part " or " % " are all based on weight.
1. the reaction product (c) for preparing the OH-terminal
The reaction product (c) of preparation OH-terminal, with following organic multiple isocyanate (a1)-(a3) and polyether glycol (b1)-(b6), (bA) and (bB).(bA) and (bB) these two kinds of polyether glycols do not belong to the present invention.
-isocyanic ester (a1): 2,4-toluylene group diisocyanate and 2, the mixture of 6-toluylene group diisocyanate (ratio of mixture: 2,4-/2,6-=80/20; Average functionality: 2; NCO content: 48.2%)
-isocyanic ester (a2): 4,4 '-diphenylmethanediisocyanate (average functionality: 2.0; NCO content: 33.6%)
-isocyanic ester (a3): poly methylene poly phenyl poly isocyanate (average functionality: 2.8; NCO content; 31.1%)
-polyvalent alcohol (b1): the polyether glycol (molecular-weight average: 2000 that obtains by dipropylene glycol and propylene oxide addition reaction; OH value: 56mg KOH/g; Average functionality: 2.0)
-polyvalent alcohol (b2): the polyether glycol (molecular-weight average: 3000 that dipropylene glycol and propylene oxide addition reaction obtain; OH value: 37mg KOH/g; Average functionality: 2.0)
-polyvalent alcohol (b3): the polyether glycol (molecular-weight average: 3000 that glycerine and propylene oxide addition obtain; OH value: 56mg KOH/g; Average functionality: 3.0)
-polyvalent alcohol (b4): the polyether glycol (molecular-weight average: 5000 that glycerine and propylene oxide addition obtain; OH value 34mg KOH/g; Average functionality: 3.0)
-polyvalent alcohol (b5): the polyether glycol (molecular-weight average: 900 that tetramethylolmethane and propylene oxide addition obtain; OH value: 250mg KOH/g; Average functionality: 4.0)
-polyvalent alcohol (b6): the polyether glycol (molecular-weight average: 1530 that Sorbitol Powder and propylene oxide addition obtain; OH value: 220mg KOH/g; Average functionality: 6.0)
-polyvalent alcohol (bA): the polyether glycol (molecular-weight average: 600 that glycerine and propylene oxide addition obtain; The OH value; 280mg KOH/g)
-polyvalent alcohol (bB): the polyether glycol (molecular-weight average: 4800 that glycerine and propylene oxide and oxyethane addition reaction obtain; OH value: 34 mg KOH/g; Ethylene oxide unit amount: 16%)
Embodiment 1 to 9 and comparative example A and B
160 weight part polyvalent alcohols (b1) and 240 weight part polyvalent alcohols (b3) are mixed, with this polyol blends heating and remain on 40 ℃.Then, 13.9 weight parts being remained on 40 ℃ isocyanic ester (a1) joins in the polyol blends and stirs.Under nitrogen environment, stir after 8 hours, the container that this mixture is housed is placed in the thermostatic container that keeps 70 ℃ 44 hours, the viscosity of assaying reaction product.Reaction product was further kept 48 hours in thermostatic container, and then carry out viscosimetric analysis.The viscosity of twice mensuration is 3640cp under 25 ℃.Reaction product is decided to be (c1).Reaction product (c1) is the clarifying liquid of homogeneous, and qualitative variation did not take place room temperature in following 3 months.Make product (c2)-(c9), (cA) and (cB) with method same as described above.The amount of each reactant among the embodiment 1-9 and the character of product are listed in table 1.The amount of each reactant among comparative example A and the B and the character of product are listed in table 2.
2. preparation hard polyurethane foams
Make the mixed polyol blends that gets of reaction product (c1-c9) and polyether glycol (d1-d3: see below), in polyol blends, add entry, catalyzer, tensio-active agent and fire retardant then, make each polyhydroxy reactant of embodiment 10-26 at last.
Polyvalent alcohol (d1): the polyether glycol (molecular-weight average: 483 that tolylene diamines and propylene oxide addition obtain; OH value: 465mg KOH/g)
Polyvalent alcohol (d2): the polyether glycol (molecular-weight average: 337 that Monoethanolamine MEA BASF and propylene oxide addition obtain; OH value: 500mg KOH/g)
Polyvalent alcohol (d3): the polyether glycol (molecular-weight average: 351 that quadrol and propylene oxide addition obtain; OH value: 640mg KOH/g)
Catalyst A: tetramethyl-hexamethylene-diamine (name of product: Kaolizer No.1)
Catalyst B: five methyl diethylentriamine (name of product: Kaolizer No.3)
Tensio-active agent: B-8017 (Goldschmit Corp. manufacturing)
Fire retardant: tricresyl phosphate chloropropyl ester
Mix remaining on 20 ℃ polyol component and poly methylene poly phenyl poly isocyanate respectively, immediately mixture was mixed for 5 seconds with 3000rpm, this mixture is poured into inwall and had in the wooden mould of polyethylene film and make foam free.The prescription of polyhydroxy reactant and reactivity worth and gained foamy density are listed in table 3 and 4.With identical method, and the product that makes among use comparative example A and the B (cA, cB), polyvalent alcohol (b1-b3) and polyvalent alcohol (d4, e1; See below) prepare various polyol blends.Prepare different foam frees with these polyol blends.The results are shown in the Comparative Examples C-I of table 5.
Polyvalent alcohol (d4): the polyether glycol (molecular-weight average: 590 that quadrol and propylene oxide addition obtain; OH value: 380mg KOH/g)
Polyvalent alcohol (e1): glycerine and propylene oxide addition obtain polyether glycol (molecular-weight average: 15000; OH value: 12mg KOH/g)
With identical method, use the product that embodiment 2 and 7 obtains (c2, c7) and polyvalent alcohol (d1 d3) makes foam free.But the gained foam in foaming step because gas phase is overflowed collapse.These the results are shown in Comparative Examples J and K in the table 5.By the way, (c2, amount c7) has exceeded scope of the present invention to the product in the polyol blends.
At table 3, in 4 and 5, term " cream time " refers to reaction liquid from being mixed into the time that foaming occurs, and unit be second.Term " sticking time " refers to reaction liquid from being mixed into the foaming obvious terminated time, and unit is second.According to ASTM-D-1622, use from foam centre portions cubes that downcut, about 10cm and measure core density, unit is " kg/m
2".By the way, collapse all takes place at foaming stages in the foam of Comparative Examples J and K.The value of band " * " refers to be mixed into from reaction liquid the time of foam generation collapse, and unit is second.
The following various foams that embodiment 10-26 and Comparative Examples C and I are made are estimated, and the results are shown in table 6.After the foaming, at room temperature foam was remained in the wooden model 30 minutes, the foam surface solidified degree behind the polyethylene film of peeling off is observed in the demoulding then.If state of cure is bad, polyethylene film is local to be peeled off from foams because of sticking at can to observe the foam epidermis." brittleness " estimated with finger friction foam epidermis.Various situations for the degree of surface cure provide " A to D " four grades.The meaning of the grade shown in " A to D " following (A: good, B: medium, C: poor slightly, D: poor) in each table.As for dimensional stability, cut out the 10cm cuboid sample from the foam centre portions, sample was at room temperature placed one day or after a week and 70 ℃ of next weeks, measured the dimensional change on foaming direction and the vertical direction."+" number expression elongation, "-" number expression is shunk.Measure the rate of closed hole that does not shrink in the foam according to ASTM-D-2856.Measure compressive strength according to JIS-A-9514.Because the foam contraction of Comparative Examples C, D, E and F gets terribly, so can't measure rate of closed hole and compressive strength in the foam.As shown in table 6, use water as the open-cell rigid polyurethane foams that whipping agent makes and have excellent size stability and mechanical property, the brittleness of foam epidermis does not reduce.
As mentioned above,, under good working conditions and operational condition, use water as whipping agent, use existing producing apparatus, can prepare open-cell rigid polyurethane foams with excellent in dimension stability and mechanical property according to the present invention.The foam of gained of the present invention is suitable for doing the thermal insulation material of refrigerator or architectural inside and outside material because foam under various envrionment conditionss (as, temperature, humidity etc.) have excellent size stability and shock resistance and/or a compressive strength.In addition,, can improve problems more of the prior art widely according to the present invention, as, relevant use water as the bad problem of foam epidermis brittleness that whipping agent brings, or the problem of peeling off between foam and the surfacing.Therefore, when the compound polyurethane material made from other materials such as paper, aluminium, steel etc., can significantly improve the productivity and the interface adhesion of matrix material.Present technique is implemented in the manufacturing of veneer sheet, applying glue plate easily.Table 1: the reaction product (embodiment 1-9) of preparation OH-terminal
Embodiment
123456789 polyalcohols (b1), 160 300 300 polyalcohols (b2), 300 240 225 polyalcohols (b3), 240 300 300 polyalcohols (b4), 250 polyalcohols (b5) more than 718 are without the preparation (comparative example A and B) of the product of alcohol (b6) 76.5 isocyanates (a1) 13.9 8.7 4.4 8.7 13.9 13.1 5.4 isocyanates (a2) 12.5 isocyanates (a3) 20.4 11.9 equivalent proportions 2.5 3.0 3.0 3.0 2.0 3.0 3.0 2.0 2.0 viscosity 3,640 3,380 3,460 4,980 4,000 4,000 7,940 13,300 8160 product c1 c2 c3 c4 c5 c6 c7 c8 c9 table 2:OH-terminal
A B ( bA ) 300 ( bB ) 240 ( a1 ) 43.6 4.4 3.0 3.0 47800 8200 cA cB3： ( 10-17 ) 10 11 12 13 14 15 16 17 ( c1 ) 20 ( c2 ) 20 30 ( c3 ) 15 ( c4 ) 20 ( c5 ) 30 ( c6 ) 30 ( c7 ) 30 ( d1 ) 56 56 49 59.5 56 49 49 49 ( d2 ) 24 24 21 25.5 24 21 21 21 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0A 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8B 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 20 20 20 20 20 20 20 20PAPI-135 213 213 203 218 213 202 204 204 15 14 17 14 14 14 13 14 59 64 90 60 59 58 62 61 21.7 24.7 24.9 25.0 22.5 25.4 23.6 23.2
4： ( 18-26 ) 18 19 20 21 22 23 24 25 26 ( c1 ) 20 ( c2 ) 15 50 20 20 ( c4 ) 30 ( c8 ) 30 15 ( c9 ) 30 ( d1 ) 59.5 56 56 72 70 49 59.5 49 ( d2 ) 25.5 24 24 8 21 25.5 21 ( d3 ) 50 8.0 8.0 4.0 11.0 4.0 11.0 8.0 8.0 8.0A 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8B 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 20 20 20 20 20 20 20 20 20PAPI-135 219 202 153 258 152 246 202 218 202 14 11 11 17 12 17 15 14 15 58 35 58 71 62 75 72 68 70 23.0 25.3 36.2 18.2 37.0 22.6 25.9 27.0 25.85： ( C-K ) C D E F G H I J K ( cA ) 20 50 ( cB ) 50 ( c2 ) 90 ( c7 ) 80 ( b3 ) 30 50 50 25 ( e1 ) 25 ( d1 ) 56 35 35 49 35 35 20 ( d2 ) 24 15 15 21 15 15 ( d3 ) 10 ( d4 ) 50 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0A 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8B 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 20 20 20 20 20 20 20 20 20PAPI-135 220 197 180 204 184 173 187 138 128 13 13 14 14 15 9 14 12 14 62 64 67 76 66 43 79 42*40
*Core density 21.5 21.5 24.2 21.0 23.1 20.8 20.9--table 6: the character of hard polyurethane foams (embodiment 10-26 and Comparative Examples C-I) embodiment surface cure dimensional change (%) closed pore (%) compressive strength
RT RT 70C
1 day 1 all 1 week (k/cm
2)10 A 0 -0.3 +0.4 5 0.6211 A 0 0 +0.1 6 0.5612 A 0 0 0 5 0.4813 A 0 +0.1 +0.4 8 0.5914 A 0 0 0 4 0.5915 B 0 0 +0.2 4 0.4716 A 0 -0.2 0 4 0.4817 A 0 -0.2 0 6 0.4618 A 0 0 0 6 0.7319 A 0 -0.4 0 4 0.4320 A 0 0 +0.1 7 1.4621 B 0 -0.3 -0.2 3 0.4922 A 0 0 0 5 1.5823 A 0 -0.1 +0.3 5 0.3624 A 0 0 +0.1 3 0.4925 A 0 0 0 4 0.7826 A 0 0 0 4 0.53C C -20 -35 +1.1- -D B -18 -30 +1.4- -E B -26 -42 +2.1- -F B -21 -29 +0.6- -G A 0 -4.1 +0.2 6 0.32H A 0 -4.4 +0.1 88 0.57I B 0 -2.9 +0.3 91 0.62
Claims (2)
1. method for preparing open-cell rigid polyurethane foams, be at catalyzer, whipping agent and tensio-active agent exist down, make polyol blends (A) and organic multiple isocyanate (B) reaction, polyol blends wherein (A) comprises the mixture of reaction product (c) of the OH-terminal of a kind of 10-60wt%, this product (c) is to be that the average functionality of organic multiple isocyanate (a) and the 20-90wt% of 1.6-2.9 is 2.0-6.0 by average functionality, molecular-weight average is 700-6000, ethylene oxide unit content is prepared with the every NCO equivalent reaction of 1.3-10.0 OH equivalent less than the polyether glycol (b) of 10wt%, and organic multiple isocyanate (B) comprises that average functionality is the organic multiple isocyanate of 2.0-2.8.
2. the amount as the water of whipping agent that the process of claim 1 wherein is per 100 weight part polyol blends (A), 3-12 weight part.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7054622A JPH08253549A (en) | 1995-03-14 | 1995-03-14 | Production of open-cell rigid polyurethane foam |
| JP054622/95 | 1995-03-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1142513A true CN1142513A (en) | 1997-02-12 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96107387A Pending CN1142513A (en) | 1995-03-14 | 1996-03-13 | Process for preparing open-cellular rigid polyurethane foam |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH08253549A (en) |
| KR (1) | KR960034251A (en) |
| CN (1) | CN1142513A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307230C (en) * | 2003-02-06 | 2007-03-28 | 东洋橡胶工业株式会社 | Polyol composition for rigid polyurethane foam and method for producing rigid polyurethane foam |
| CN100348400C (en) * | 2004-12-15 | 2007-11-14 | 杭州华东板材有限公司 | Colour steel plate with sandwich of semi-hard polyurethane foam plastic and its production process |
| CN102666628A (en) * | 2009-12-18 | 2012-09-12 | 旭硝子株式会社 | Process for production of rigid open-cell foam |
| CN106232657A (en) * | 2014-04-29 | 2016-12-14 | 米其林集团总公司 | Method by micro-cast preparation polyurethane foam |
| CN109593175A (en) * | 2018-10-23 | 2019-04-09 | 万华化学（宁波）容威聚氨酯有限公司 | A kind of half aperture polyurethane hard bubble composite material of complete water type and preparation method thereof |
| CN110358432A (en) * | 2019-06-11 | 2019-10-22 | 京华派克邯郸机械科技有限公司 | PAPI type bathroom reinforced polyurethane resin and preparation method thereof |
| CN110539442A (en) * | 2019-09-02 | 2019-12-06 | 厦门市锋特新材料科技有限公司 | TPU particle foaming process |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3322852B2 (en) * | 1998-06-26 | 2002-09-09 | 日清紡績株式会社 | Open cell rigid polyurethane foam molding and method for producing the same |
| JP2002293868A (en) * | 2001-03-29 | 2002-10-09 | Mitsui Chemicals Inc | Rigid polyurethane foam and production method thereof |
| DE10357895A1 (en) * | 2003-12-11 | 2005-07-07 | Bayer Materialscience Ag | Polymer dispersions in polyester polyols |
| JP4597773B2 (en) * | 2005-05-30 | 2010-12-15 | 株式会社イノアックコーポレーション | Method for producing flexible polyurethane foam |
| KR101491089B1 (en) * | 2014-06-27 | 2015-02-10 | 주식회사 세림티티시 | Flexible polyurethane foam |
| CN104774316A (en) * | 2015-04-28 | 2015-07-15 | 山东固安特新材料科技股份有限公司 | Polyurethane all-water foaming material for coal mine filling and preparation method thereof |
-
1995
- 1995-03-14 JP JP7054622A patent/JPH08253549A/en active Pending
-
1996
- 1996-03-13 CN CN96107387A patent/CN1142513A/en active Pending
- 1996-03-14 KR KR1019960006764A patent/KR960034251A/en not_active Application Discontinuation
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307230C (en) * | 2003-02-06 | 2007-03-28 | 东洋橡胶工业株式会社 | Polyol composition for rigid polyurethane foam and method for producing rigid polyurethane foam |
| CN100348400C (en) * | 2004-12-15 | 2007-11-14 | 杭州华东板材有限公司 | Colour steel plate with sandwich of semi-hard polyurethane foam plastic and its production process |
| CN102666628A (en) * | 2009-12-18 | 2012-09-12 | 旭硝子株式会社 | Process for production of rigid open-cell foam |
| CN102666628B (en) * | 2009-12-18 | 2014-04-02 | 旭硝子株式会社 | Process for production of rigid open-cell foam |
| CN106232657A (en) * | 2014-04-29 | 2016-12-14 | 米其林集团总公司 | Method by micro-cast preparation polyurethane foam |
| CN109593175A (en) * | 2018-10-23 | 2019-04-09 | 万华化学（宁波）容威聚氨酯有限公司 | A kind of half aperture polyurethane hard bubble composite material of complete water type and preparation method thereof |
| CN110358432A (en) * | 2019-06-11 | 2019-10-22 | 京华派克邯郸机械科技有限公司 | PAPI type bathroom reinforced polyurethane resin and preparation method thereof |
| CN110539442A (en) * | 2019-09-02 | 2019-12-06 | 厦门市锋特新材料科技有限公司 | TPU particle foaming process |
Also Published As
| Publication number | Publication date |
|---|---|
| KR960034251A (en) | 1996-10-22 |
| JPH08253549A (en) | 1996-10-01 |
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