CN1123798A - Production of hard polyamine ester foaming compound body - Google Patents
Production of hard polyamine ester foaming compound body Download PDFInfo
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- CN1123798A CN1123798A CN95108366.XA CN95108366A CN1123798A CN 1123798 A CN1123798 A CN 1123798A CN 95108366 A CN95108366 A CN 95108366A CN 1123798 A CN1123798 A CN 1123798A
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- polyvalent alcohol
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Abstract
The process for producing hard foam polyurethane complex includes mixing raw resin liquid containing polyol, foamer, catalyst, foaming regulator and other aid with organic polyisocyanate and forming complex of polyurethane foam in enclosed cavities on one or more sheets. Said polyol is partially or fully the one (D) containing phenolic resin polyol (A) and amino phenolic polyol (B), or may be polyol (E) or (F). The weight ratio of (A) to (B) is 0.25-4.0 and hydroxyl value is 180-700 mgKOH/g. Its foamer is selected from hydrogenized chlorofluorohydroxy kind and hydrogenized fluorohydroxy kind of foamers.
Description
The present invention relates to the manufacture method of hard polyamine ester foaming compound body.
More particularly, particularly being in the polyvalent alcohol at phenolic resin, adding amino-phenol is that polyvalent alcohol or polyphenylene polyphenyl (support) dimethyl polyamines are that polyvalent alcohol or poly-methylene polyphenylene polyamines are polyvalent alcohol, and constitute be used for the raw material of polyvalent alcohol of the present invention as urethane resin, and resulting urethane resin, for the minimum whipping agent hydrogenated chloride fluorine of public hazards for hydro carbons (being designated hereinafter simply as HCFC) and hydrogenation fluorinated hydrocarbon (being designated hereinafter simply as HFC), has dissolubility resistent, in addition, use above-mentioned whipping agent can obtain hard polyaminoester foams, and then obtain its complex body.
Because in these goods, especially hard polyaminoester foams have with chlorine fluorinated hydrocarbon (being designated hereinafter simply as CFC) as the equal good physical of the former goods of whipping agent, therefore, be extremely useful as aspects such as the thermal insulation material of refrigerator, electric freezer, heat-insulating shield, boats and ships or vehicle or heat insulating construction materials.
Hard polyaminoester foams; because heat insulating ability and low temperature excellent size stability; so adopt each species complex that it manufactures; be widely used as the thermal insulation material or the structured material of refrigerator, electric freezer, building walls, top ceiling, boats and ships or vehicle etc., and the thermal insulation material of measuring instrument etc. or protective guard etc.
In addition, adopt interruption method or continuous processing to make the method for complex body, extensively carried out.This complex body is that hard polyaminoester foams is being formed on the plane materiel and in the space that surrounds on many plane materiels.
; so far; when making hard polyaminoester; as the foaming means; particularly used the CFC-11 (trichlorine methyl fuoride) that belongs to CFC or CFC-12 (Refrigerant 12) etc., still, these are owing to decompose the ozonosphere of the earth and the greenhouse effect is increased; carried as the material of the very big destruction environment of public hazards, therefore recently to its manufacturing with use restriction has all been arranged.Meanwhile, surrogate as CFC-11 or CFC-12 etc., except HCFC-123 (2,2-two chloro-1,1, the 1-Halothane), HCFC-141b (1,1-two chloro-1-fluoroethanes), beyond the HCFC of HCFC-142b (1-chloro-1,1-C2H4F2 C2H4F2) or HCFC-22 (1-chloro-1,1-methylene fluoride) etc., also has HFC-134a (1,1,1, the 2-Tetrafluoroethane), HFC-152a (1, the 1-C2H4F2 C2H4F2) etc. HFC also is subjected to gazing at of people, but known these HCFC and HFC compare with CFC, have resin dissolves power and increase, the separated foam rate reduces, the tendency that reduces the urethane physicals greatly of foam strength deterioration etc.Particularly, clear and definite by present inventors' research as the insulation effect of the characteristic of polyurethane foaming body since in foaming the separated foam wall in HCFC and the HFC dissolving foam, thereby its obvious results is descended.
In order to solve the above problems, the necessity of developing a kind of novel urethane resin has become people's strong hope, the raw material of the urethane resin before the known conduct and the polyvalent alcohol that uses, increase viscosity degradation along with the add-on of epoxide, thereby the operation of making urethane resin has been become easily, but if add superfluous epoxide, then since urethane resin be dissolved in fully among HCFC and the HFC, so in fact use become impossible.Known, on the contrary, if the add-on of epoxide tails off, then the dissolubility resistent for HCFC and HFC improves a little, but because polyvalent alcohol is solid or undue thickness, so when making urethane resin etc., degenerate etc. with the intermiscibility of other raw material, use the very difficulty that becomes, and can not obtain satisfied goods.
Especially in the manufacturing of hard polyaminoester, the viscosity of polyvalent alcohol and as the whipping agent of other raw material and with the intermiscibility of organic multiple isocyanate be necessary index, in the polyvalent alcohol in the past, also do not see the good viscosity of operability when having such foaming, good for the anti-dissolubility of HCFC and HFC, and the polyvalent alcohol also good with the blending dispersion of HCFC and HFC.
Open clear 57-151613 the spy, the spy opens among the clear 57-151614 and discloses, be the viscosity of the polyol blend of polyvalent alcohol and fragrant family polyester polyol (not addition epoxide) for reducing amine, and low molecular weight polyols carried out the blended method.
Open among the clear 51-105394 the spy, disclosing a kind of is that polyvalent alcohol, aromatic amine are that the hydroxyl value that polyvalent alcohol and aliphatic polyol constitute is the polyol blend of 200-500mgKOH/g by the phenolic varnish resin.In addition, open clear 63-264616 and the spy opens among the flat 1-135824 the spy, disclosing a kind of is polyvalent alcohol (hydroxyl value: 50-350mgKOH/g), the polyol blend that constitutes of polyether glycol and/or polyester polyol by the phenolic varnish resin.But, in foregoing invention, all do not have to disclose and be used for polyvalent alcohol of the present invention, and do not meet when being whipping agent yet with HCFC or HFC, use the explanation of invention of the foam of above-mentioned polyvalent alcohol.
The present invention relates to the manufacture method of the complex body of polyvalent alcohol, urethane resin, hard polyaminoester foams, its manufacture method and this foam.
Be used for polyvalent alcohol of the present invention, containing at phenol resins is in the polyvalent alcohol, cooperating amino phenol is that polyvalent alcohol or polyphenylene polyphenyl (support) dimethyl polyamines are that polyvalent alcohol or poly-methylene polyphenylene polyamines are the polyvalent alcohol of polyvalent alcohol, and with above-mentioned resin, foam and the complex body of this polyvalent alcohol as raw material, for as the hydrogenated chloride fluorine of the minimum whipping agent of public hazards for hydro carbons and hydrogenation fluorinated hydrocarbon, be dissolubility resistent.
Because above-mentioned foam class, with compare as the former product of whipping agent with the chlorine fluorinated hydrocarbon, having equal good physicals, all is being extremely useful aspect the thermal insulation material of refrigerator, electric freezer, heat-insulating shield, boats and ships or vehicle etc. or heat insulating construction material therefore.
Main purpose of the present invention, provide a kind of particularly when making hard polyaminoester foams, as whipping agent, even use minimum HCFC or the HFC of public hazards, operability during the carboxylamine ester foaming and the physicals of foam are compared during with the CFC that uses in the past, the polyvalent alcohol that still has same effect also provides the method for making of foam or foam or the method for making of its complex body.
Present inventors have carried out research with keen determination for achieving the above object, and the result has reached the present invention.
That is, the present invention is the content of following (1)-(6).
(1) polyvalent alcohol (D), this polyvalent alcohol (D) is that polyvalent alcohol (A) is polyvalent alcohol (B) with amino phenol for containing phenol resins, wherein, (A)/(B) mixes mutually for the weight ratio of 0.25-4.0, and makes it to become the polyvalent alcohol that hydroxyl value is 180～700mg KOH/g.
(2) polyvalent alcohol (E), this polyvalent alcohol (E) is that polyvalent alcohol (A) is polyvalent alcohol (C) with polyphenylene polyphenyl (support) dimethyl polyamines for containing phenol resins, wherein, (A)/(C) mix mutually, and make it to become the polyvalent alcohol that hydroxyl value is 180-700mgKOH/g for the weight ratio of 0.25-4.0.
(3) a kind of urethane resin, this urethane resin mixes for making polyvalent alcohol and organic multiple isocyanate, and reaction and when making urethane resin, part or all of this polyvalent alcohol is to use in item (1) said polyvalent alcohol (D) or the urethane resin of said polyvalent alcohol (E) in item (2).
(4) a kind of hard polyaminoester foams, it is characterized in that, contain polyvalent alcohol making, whipping agent, catalyzer, transfer the resin stoste of infusion and other auxiliary agent to mix with organic multiple isocyanate, and make its reaction and produce in the polyurethane foaming body, use is that polyvalent alcohol (A) and poly-methylene polyphenylene polyamines are the polyvalent alcohol (G) that polyvalent alcohol (F) is formed by the said polyvalent alcohol of item (1) (D) or (2) said polyvalent alcohol (E) or phenol resins, as this whipping agent, then use contain from by hydrogenated chloride fluorine for hydro carbons, the whipping agent of one or more that select in the class that the hydrogenation fluorinated hydrocarbon is formed, and use frothing aid as required.
(5) a kind of manufacture method of hard polyaminoester foams, it is characterized in that, contain polyvalent alcohol making, whipping agent, catalyzer, transfer the resin stoste of infusion and other auxiliary agent to mix mutually with organic multiple isocyanate, and it is reacted in the method for producing hard polyaminoester foams, use is that polyvalent alcohol (A) and poly-methylene polyphenylene polyamines are the polyvalent alcohol (G) of polyvalent alcohol (F) formation by the said polyvalent alcohol of item (1) (D) or (2) said polyvalent alcohol (E) or phenol resins, as this whipping agent, be to use contain from by hydrogenated chloride fluorine for hydro carbons, the whipping agent of one or more that select in the class that the hydrogenation fluorinated hydrocarbon is formed, and use frothing aid as required.
(6) a kind of manufacture method of hard polyamine ester foaming compound body, it is characterized in that, contain polyvalent alcohol making, whipping agent, catalyzer, transfer the resin stoste of infusion and other auxiliary agent to mix and make its reaction with organic multiple isocyanate, and on the plane materiel or in the space that on a plurality of plane materiels, is surrounded as, make in the method for the manufacturing complex body that the polymeric polyisocyanate foam forms, part or all of this polyvalent alcohol, being to use by the said polyvalent alcohol of item (1) (D) or (2) said polyvalent alcohol (E) or phenol resins is that polyvalent alcohol (A) and poly-methylene polyphenylene polyamines are the polyvalent alcohol (G) of polyvalent alcohol (F) formation, as this whipping agent, be to use contain from by hydrogenated chloride fluorine for hydro carbons, the whipping agent of one or more that select in the class that the hydrogenation fluorinated hydrocarbon is formed reaches and uses frothing aid as required.
Being used for polyvalent alcohol of the present invention, is above said polyvalent alcohol (D), polyvalent alcohol (E) and polyvalent alcohol (G).
Polyvalent alcohol of the present invention (D), the amino phenol that contains phenol resins as a kind of composition and be polyvalent alcohol (A) and another kind of composition is polyvalent alcohol (B).
Above-mentioned phenol resins is that polyvalent alcohol (A) is represented by following general formula (I) by using, its number-average molecular weight (below be abbreviated as Mn) is for 650-1400's, average functional group number is one or more a mixture of the phenol resins of 3-8, and, hydroxyl with respect to each normal this compound or mixture, the hydroxyl value that adds the epoxide of 1.0-4.5 mole is the polyvalent alcohol (a) of 140-350mgKOH/g, with one or more the active hydrogen base of mixture with respect to the triacontanol amine compound of the following general formula of each equivalent (II) expression, the hydroxyl value that adds the epoxide of 0.5-3.0 mole and obtain is the polyvalent alcohol (b) of 240-800mgKOH/g, or it is normal with respect to each, functional group's number is one or more the hydroxyl of mixture of the aliphatic polyhydroxy compound of 2-8, add the epoxide of 0.8-6.5 mole and the hydroxyl value that obtains to be the polyvalent alcohol (C) of 130-750mgKOH/g formed.
(in the formula, R, expression hydrogen atom, carbonatoms are alkyl, chlorine atom, bromine atoms, fluorine atom or the hydroxyl of 1-9.M is 1-3, and in addition, n is 1～6.X, Y are can be identical or inequality, from by carbonatoms be the divalent base selected the class formed of 1～10 alkylidene group, benzene (support) dimethyl, oxo base, sulfenyl, sulfonyl one or more in conjunction with base.)
NR
2R
2R
3?????????????????????????(II)
(in the formula, R
2And R
3Represent an atom or a kind of group from a class of forming by hydrogen atom, ethanol based, Virahol base, selected respectively.R
2And R
3Be can be the same or different.But, R
2And R
3Be except the situation of hydrogen atom simultaneously.)
So-called phenol resins, for example, make phenols and the aldehydes or the α of phenol, cresols, butylphenol, nonyl phenol, chlorophenol, Resorcinol, quinhydrones, pyrocatechol, hydroxyanisole, dihydroxyphenyl propane, bisphenol S etc., α '-dimethoxy benzene (support) dimethyl or α, α '-dichlorobenzene (support) dimethyl or Sulfur etc. react the phenol resins that makes according to a conventional method and all are suitable for.In addition,, can enumerate as phenol resins, in general formula (I), R
1Be that hydrogen atom, X and Y are methylene radical, (M simultaneously
n) be 650～900, average functional group number is 3～8, softening temperature is 75～120 ℃ novolac resin, as compound preferably.
As being used for epoxy compounds of the present invention is oxyethane, propylene oxide, butylene oxide ring etc., and they also can two or more and usefulness.
Known, if the add-on of epoxide increases, the tendency that then has the dissolubility resistent for HCFC or HFC to degenerate usually, and, when urethane resin is made in the reaction of the phenol resins that makes molecular weight less than 650 and organic multiple isocyanate, all demonstrate the tendency that is dissolved among HCFC and the HFC.(Mn) of phenol resins surpasses at 1400 o'clock, is full-bodied, and bad for the blending dispersion of HCFC and HFC, and the operability when reacting with organic multiple isocyanate worsens.
Be used for polyvalent alcohol of the present invention (a), the epoxide that adds 1.0～4.5 moles with the phenol hydroxyl to each normal phenol resins is suitable.Each equivalent phenol hydroxyl adds discontented 1.0 moles of epoxide, that is to say, remaining of phenol hydroxyl when making polyurethane foaming body, because the physicals of foam is bad, thereby are undesirable more.In addition, when the add-on of epoxide surpasses 4.5 moles, viscosity, thus the blending dispersion of HCFC and HFC is also become good, but urethane resin has completely lost for the dissolubility resistent of HCFC and HFC.
When less than 3 is counted by the average functional group of phenol resins, after the polyvalent alcohol that with alkanolamine or aliphatic polyhydroxy compound is initiator mixes, itself and organic multiple isocyanate are reacted, resulting urethane resin has the tendency that degenerates for the dissolubility resistent of HCFC and HFC, in addition, average functional group number surpasses at 8 o'clock, and itself and organic multiple isocyanate are reacted, resulting urethane resin becomes fragile, and has the shortcoming of the product of the requirement that is not being met.
As being used for alkanolamine of the present invention, specifiable example has monoethanolamine, diethanolamine, trolamine, monoisopropanolamine, diisopropanolamine (DIPA), tri-isopropanolamine etc.
Be used for polyvalent alcohol of the present invention (b), it serves as suitable adding 0.5～3.0 mole of epoxide with the active hydrogen to each normal alkanolamine.During 0.5 mole of the epoxide less than that the active hydrogen of each normal alkanolamine is added, because the remaining performance that the linking agent of alkanolamine is arranged still, therefore when making foam, its physicals degenerates equally.And when surpassing 3.0 moles, the physicals of the foam that makes reduces, so can not be used for foam.
Polyvalent alcohol in the present invention (a), ratio of mixture (b) (a)/(b) is preferably 0.25～4.0.Weight ratio surpasses at 4.0 o'clock, because thickness, thus have the tendency that the blending dispersion with HCFC or HFC degenerates, so because the operational problem that has when making urethane resin is bad.On the other hand, during less than 0.25, the physicals of foam degenerates, and also degenerates for the dissolubility resistent of HCFC or HFC, so also be bad.
Be used for aliphatic polyhydroxy compound of the present invention, with from being that one or more that select the class formed of 2～8 glycols, polyalcohols and polyose serve as suitable by functional group's number.As having that concrete compound can be enumerated: ethylene glycol, Diethylene Glycol, propylene glycol, dipropylene glycol, butyleneglycol, neopentyl glycol, cyclohexanedimethanol, hexanaphthene tetramethyl alcohol are arranged as di-alcohols; As polyvalent alcohol glycerol, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane are arranged; And, methyl glucoside, Sorbitol Powder, mannitol, melampyrum, sucrose etc. are arranged as polyose.
The epoxide that the hydroxyl of each equivalent aliphatic polyhydroxy compound is preferably added 0.5～6.5 mole.When 0.5 mole of less than, when making the carbamate foam, foam has the tendency that becomes fragile, and in addition, when surpassing 6.5 moles, descends as the urethane resin of the raw material dissolubility resistent for HCFC or HFC.
Be that the polyvalent alcohol (a) and the weight ratio (C) (a)/(c) of initiator is preferably 0.1～4.0 with phenol resins and aliphatic polyhydroxy compound respectively.During ratio of mixture less than 0.1, exist the solvability of the anti-HCFC that reacts down when making urethane resin and HFC that the tendency of decline is arranged by catalyzer, and surpassing at 4.0 o'clock, because viscosity is too high, therefore when making urethane resin, have the bad shortcoming of operability.
The amino phenol polyvalent alcohol (B) of other composition is as described below.
A kind of polyvalent alcohol, this polyvalent alcohol is to contain, use is 100～200 by the represented number-average molecular weight of following general formula (III), average functional group number is the one or more kinds of mixtures of 3～6 amino phenol based compound, and is the polyvalent alcohol (d) of 150～700mgKOH/g and said polyvalent alcohol (b) or polyvalent alcohol (c) are constituted in phenol resins polyvalent alcohol (A) polyvalent alcohol to the hydroxyl value that the active hydrogen of the active dydrogen compounds of each normal this compound or mixture adds 1.0～9.0 moles of epoxide.
(in the formula, R
OExpression hydrogen atom, carbonatoms are 1～5 aliphatic alkyl or alicyclic alkyl, and q is 1～2 integer, and in addition, p also is 1～2 integer.)
For the amino phenol based compound, can enumerate having as concrete example: amino-phenol, amino cresols, amino-ethyl phenol, amino butylphenol, aminoresorcinol, amino pyrocatechol, amino Resorcinol, amino high pyrocatechol, amino 2 as good example, 4-cresorcin, amino-5-methyl isophthalic acid, 3-dihydroxy-benzene, diaminophenol, diamino cresols.
Amino phenol is weight ratio of mixture (d)/(b), (d)/(c) of polyvalent alcohol (d), polyvalent alcohol (b) or polyvalent alcohol (c) in the polyvalent alcohol (B), is respectively 0.25～4.0,0.1～4.0.Selected in this case weight ratio of mixture we can say that with phenol resins be that the situation of (a)/(b) under the occasion of polyvalent alcohol, (a)/(c) is identical.
Like this, polyvalent alcohol (D) is that to contain resulting phenol resins be that polyvalent alcohol (A) and amino phenol are polyvalent alcohol (B), and weight ratio (A)/(B) is 0.25～4.0, hydroxyl value is the polyvalent alcohol of 180～700mgKOH/g.
At this moment, even use polyvalent alcohol (A) separately, and with HCFC and/or HFC as whipping agent, the made hard polyaminoester foams that obtains also demonstrates reasonable physicals, but if with polyvalent alcohol (B) and usefulness, then the intensity of thermal conductivity, foam (low temperature dimensional stability, compressive strength) all can become better.
When proportioning (A)/(B) does not meet 0.25～4.0 scope, the physicals of above-mentioned foam will degenerate.
Another kind of polyvalent alcohol of the present invention (E) contains above-mentioned phenol resins as a kind of composition to be polyvalent alcohol (A) and to be polyvalent alcohol (c) as polyphenylene polyphenyl (support) the dimethyl polyamines of other composition.Above-mentioned polyphenylene polyphenyl (support) dimethyl polyamines is that polyvalent alcohol (C) is that each equivalent active hydrogen of containing represented polyphenylene polyphenyl (support) the dimethyl polyamines based compound of useful following general formula I V adds 1.0～9.0 moles of epoxide to make hydroxyl value be the said polyvalent alcohol of polyvalent alcohol (e) and front (b) of 150～700mgKOH/g or a kind of polyvalent alcohol of polyvalent alcohol (c).
(in the formula, R represents hydrogen atom, and carbonatoms is that 1～10 aliphatic alkyl, alicyclic alkyl, Z represent benzene (support) dimethyl.In addition, S is 0～10 integer.)
What above-mentioned polyphenylene polyphenyl (support) dimethyl polyamines based compound can be enumerated has: α, the derivative of α '-two (4-aminophenyl) benzene (support) dimethyl, polyphenylene polyphenyl (support) dimethyl polyamines and their mixture, compound, isomer, oligopolymer etc.
During 1.0 moles of epoxy compounds less thaies that each normal oxygen base adds, that is to say that amino residual quantity is more, reaction when making foaming is difficult to control, and because when making the carbamate foam, the physicals of foam degenerates, so be undesirable.In addition, when the add-on of epoxide surpasses 9.0 moles, viscosity, thus improve for the blending dispersion of HCFC and HFC, but the physicals of foam has degenerated.As the alkanolamine that is used for the present invention as previously described.
Polyvalent alcohol of the present invention (b), it is active hydrogen to each equivalent alkanolamine, the polyvalent alcohol that adds 0.5～3.0 mole epoxide and obtain, active hydrogen to each normal alkanolamine, during 0.5 mole of the epoxide less than that adds, because the residual performance that the linking agent of alkanolamine is arranged, so the physicals when making foam degenerates with material.When surpassing 3.0 moles, with the ratio of mixture (e) of polyvalent alcohol (e) even/(b) surpass 4.0, physicals also can reduce, thereby can not be used as whipping agent.
The ratio of mixture (e)/(b) of polyvalent alcohol among the present invention (e), (b) with 0.2 5～4.0 weight ratio for well.Weight ratio surpasses at 4.0 o'clock, because thickness, thus have the tendency that the blending dispersion with HCFC and HFC degenerates, and owing in making urethane resin, have operational problem, so be not desirable.On the other hand, discontented 0.25 o'clock because the physicals of foam degenerates, also is worthless.
Be used for aliphatic polyhydroxy compound of the present invention such as preceding narration.
For the hydroxyl of each equivalent aliphatic polyhydroxy compound, preferably add 0.5～6.5 mole epoxide.During 0.5 mole of add-on less than, when making the carbamate foam, foam has the tendency that becomes fragile, and in addition, when surpassing 6.5 moles, with this urethane resin as raw material, reduces for the dissolubility resistent of HCFC and HFC.Be that the polyvalent alcohol (e) of initiator and weight ratio of mixture (e)/(c) (c) are preferably 0.1～4.0 with polyphenylene polyphenyl (support) dimethyl polyamines based compound and aliphatic polyhydroxy compound respectively.During ratio of mixture less than 0.1, by reacting in the presence of catalyzer when making urethane resin, its dissolubility resistent for HCFC and HFC has the tendency of reduction, in addition, surpass at 4.0 o'clock,, in making urethane resin, have the bad shortcoming of operability because viscosity is too high.
Polyvalent alcohol (E) is that polyvalent alcohol (A) is mixed with 0.25～4.0 weight ratio of mixture mutually with polyvalent alcohol (C), and makes the hydroxyl value of title complex become a kind of polyvalent alcohol of 180～700mgKOH/g.
Even use polyvalent alcohol (A) separately, use HCFC and/or the resulting foam of HFC also can demonstrate the better physical performance, but if with polyvalent alcohol (C) and time spent, then will obtain better result aspect thermal conductivity and the foam intensity (dimensional stability, compressive strength).But proportioning (A)/(C) is in 0.25～4.0 scope the time, thus be that the physicals of the foam that makes of whipping agent is bad with HCFC or HFC, proportioning (A)/(C) with 0.25～4.0 for well.
Be used to prepare the polyvalent alcohol (G) of hard polyaminoester foams of the present invention and complex body thereof, contain above-mentioned phenol resins as a kind of composition and be polyvalent alcohol (A) and be polyvalent alcohol (F) as the poly-methylene polyphenylene polyamines of another kind of composition.Polyvalent alcohol (F) is the amino with respect to each normal poly-methylene polyphenylene polyamines, add 1.0～9.0 moles of epoxide and the hydroxyl value that obtains to be the polyvalent alcohol (f) of 150～700mgKOH/g form with above-mentioned polyvalent alcohol (b) or polyvalent alcohol (c).
Each weight ratio of mixture (f)/(b), (f)/(c) of this polyvalent alcohol (f) and polyvalent alcohol (b), polyvalent alcohol (f) and polyvalent alcohol (c) is to be respectively 0.25～4.0,0.1～4.0 for well.
Like this, making the weight ratio of mixture (A)/(F) of resulting polyvalent alcohol (F) and above-mentioned polyvalent alcohol (A) is 0.25～4.0, and to make the hydroxyl value of title complex be that a kind of polyvalent alcohol that 180～700mgKOH/g obtains is polyvalent alcohol (G).The physicals of these ratio of mixture (f)/(b), (f)/(c), (A)/(F) and hydroxyl value and resulting polyol blend and urethane, the relation of operability, with effect of polyvalent alcohol (F) and usefulness etc., all the situation with polyvalent alcohol (D), polyvalent alcohol (E) is identical.
For being used for poly-methylene polyphenylene polyamines of the present invention, raw material as poly-methylene polyphenylene polyisocyanates, can use the poly-methylene polyphenylene polyamines of common employed what is called or can use by separate in the poly-methylene polyphenylene polyamines 4,4 '-diaminodiphenyl-methane or their mixture of isomers.
In the present invention, with phenol resins, triacontanol amine compound, aliphatic polyhydroxy compound, in amino phenol based compound, polyphenylene polyphenyl (support) dimethyl polyamines and the poly-methylene polyphenylene polyamines one or two or more kinds be initiator, when adding epoxide employed catalyzer, be with following logical formula V or the amine compound (VI) represented as amine compound.
NR
4R
4R
5????????????????????????(V)
R
4R
5N(CH
2)
tNR
4R
5???????????????????(VI)
(the R in the following formula
4Expression hydrogen atom, carbonatoms are 1～6 alkyl, ethanol based or Virahol base.R
5Be alkyl, ethanol based or the Virahol base of hydrogen atom, carbonatoms 1～4.In addition, t is 1～6.But in logical formula V, R
4And R
5Be except the situation of hydrogen atom simultaneously.)
As amine compound, the example that can enumerate has: dibutylamine, Edamine, tetramethylenediamine, monoethanolamine, diethanolamine, trolamine, Yi Bingchunan, triethylamine, three-just-propylamine, two-just-propylamine, just-propylamine, just-amylamine, N, N-dimethylethanolamine, isobutylamine, isobutylcarbylamine, methyl-diethyl-amine etc.
In addition, as alkali metal hydroxide, specifiable have: lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, hydrated barta etc.
Above-mentioned various catalyzer can use separately also and can more than two kinds and use.
These catalyst consumption are that the initiator of per 100 weight parts adds 0.1～2.0 weight part.
Preparation method as polyvalent alcohol of the present invention, be to join in the autoclave individually or after mixing as phenol resins, alkanolamine, aliphatic polyhydroxy compound, aminophenol compound, polyphenylene polyphenyl (support) dimethyl polyamines based compound and the poly-methylene polyphenylene polyamines of initiator, add catalyzer again, add epoxide then at leisure and react.Temperature of reaction is preferably 90～130 ℃.If less than 90 ℃, then reaction is difficult to carry out.If surpass 130 ℃, the tendency of easy generation side reaction is arranged then.In addition, the polyvalent alcohol that made independent adding of above-mentioned initiator after synthetic, cooperates each by the amount of stipulating separately.
As the manufacture method of the polyvalent alcohol among the present invention, as mentioned above, initiator can be used alone or as a mixture and make polyvalent alcohol.In this case, when making with independent initiator, viscosity uprises, and during the operability variation, preferably uses the mixing initiator of each composition to make salty method from the beginning quickly.
In an embodiment of the present invention, narrated the modulator approach of polyvalent alcohol (D), (E), (G), this method at first is to synthesize polyvalent alcohol (a) and (b), (c), (d), (e) and (f) with each initiator individually.Then modulate each polyhydroxy reactant (A), (B), (C) and (F) by these polyvalent alcohols again, and then by the polyvalent alcohol of these compositions, modulate polyvalent alcohol of the present invention (D), (E) and (G).
For being used for organic multiple isocyanate of the present invention, known before being, do not have really special restriction, specifiable have: aromatic series, aliphatic, alicyclic polyisocyanates and modifier thereof, for example: phenylene diisocyanate, diphenylmethanediisocyanate, rough diphenylmethanediisocyanate, toluene support vulcabond, rough toluene support vulcabond, benzene (support) dimethyl vulcabond, HDI, isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate, hydrogenation toluene support vulcabond, the triisocyanate triphenyl methane, poly-methylene polyphenylene polyisocyanates, performed polymer (the NCO content that modification (carbodiimide etc.) diphenylmethanediisocyanate etc. and their mixture and molecular end are the NCO base, for example be 5～35%) etc., this performed polymer be make the excess quantity of above-mentioned those organic multiple isocyanates and polyvalent alcohol (for example low molecular polylol and/or polymer polyatomic alcohol) with
(equivalence ratio is that 2～20 ratio is reacted and obtained.These organic multiple isocyanates can use separately or two or morely mix use.Its consumption is to become at 0.8～5.0 o'clock with the equivalence ratio that can make the hydroxyl in NCO base and the resin stoste to be advisable.
This equivalence ratio surpasses at 5.0 o'clock, with residual unreacted organic multiple isocyanate is arranged.In addition, during equivalence ratio less than 0.8, on the contrary, because residual more unreacted polyvalent alcohol, so should be with above-mentioned scope.
The whipping agent of Shi Yonging is HCFC and HFC in the present invention.
As HCFC, that can enumerate has: 2, and 2-two chloro-1,1,1-Halothane (HCFC-123), 1,1-two chloro-1-fluoroethanes (HCFC-141b), 1-chloro-1,1-C2H4F2 C2H4F2 (HCFC-142b) or-chlorodifluoromethane (HCFC-22), as having that HFC can enumerate: 1,1,1,2-Tetrafluoroethane (HFC-134a) or 1,1-C2H4F2 C2H4F2 (HFC-152a).These whipping agents can use separately also can mix use.
In addition, as required, also can and water and/or low-boiling compound or contain their frothing aid.
The consumption of water normally adds 0.5～5.0 weight part in the resin stoste of per 100 weight parts.In addition, be methylene dichloride, lower boiling hydro carbons (boiling point is 10～50 ℃) and their mixture as low-boiling compound.In addition, also can also use with former chlorine fluorinated hydrocarbon.
In the present invention, in order to obtain hard polyaminoester foams, as operable foaming catalyzer, for example have: amine urethane catalyzer (triethylamine, tripropyl amine, tri-isopropanolamine, Tributylamine, trioctylamine, hexadecyldimethyl benzyl ammonium amine, N-methylmorpholine, N-ethylmorpholine, N-octadecyl morpholine, monoethanolamine, diethanolamine, trolamine, N methyldiethanol amine, N, the N-dimethylethanolamine, Diethylenetriaminee (DETA), N, N, N ', N '-tetramethyl-Edamine, N, N, N ', N '-tetramethyl-trimethylene diamines, N, N, N ', N '-tetramethyl butane diamine, N, N, N ', N '-tetramethyl--1,3-butane diamines, N, N, N ', N '-tetramethyl-hexamethylene-diamine, two (2-(N, the N-dimethylamino) ether ethyl), N, the N-dimethyl benzyl amine, N, the N-dimethylcyclohexylam,ne, N, N, N ', N ＂, N ＂-pentamethyl-Diethylenetriaminee (DETA), triethylenediamine, the formate of triethylenediamine and other salt, the hydroxyl alkylene affixture of the amido of primary amine and secondary amine, N, the nitrogen heterocyclic of N-dialkyl group _ piperazine and so on, various N, N ', N " trialkyl aminoalkyl group hexahydrotriazine class (the beta-amino phosphinylidyne catalyzer of special public clear 52-043517; the beta-amino nitryl catalyzer of special public clear 53-014279 etc.)); Organo-metallic urethane catalyzer (tin acetate, stannous octoate, oleic acid tin, tin laurate, dibutyl tin diacetate esters, dibutyl tin two lauric acid tin, dibutyl tin dichloride, lead octoate 36, lead naphthenate, nickel naphthenate, cobalt naphthenate etc.) etc.
These catalyzer can use or mix use separately, and its consumption is with respect to the polyvalent alcohol of per 100 weight parts.It is 0.0001～10.0 weight part.
Accent infusion in the present invention, well-known organic silicon surfactant before being, for example, L-520, the L-540 of Japan ュ ニ カ-society's system, L-5340, L-5410, L-5420, L-5710, L-5720 etc., SH-190, SH-192, SH-193, the SH-194 of ト-レ, シ リ コ-Application society system, SH-195 etc., F-305, the F-306 of the シ リ コ of SHIN-ETSU HANTOTAI-Application society system, F-317, F-341, F-345 etc., the TFA-4200 of the シ リ コ of Toshiba-Application society system etc.The consumption that these transfer infusions is that polyvalent alcohol and the organic multiple isocyanate total amount with respect to per 100 weight parts is 0.1～20 weight part.
In addition,, for example, can use as fire retardant, three (2-chloroethyl) phosphoric acid ester, three (two chloropropyls) phosphoric acid ester, three (dibromopropyl) phosphoric acid ester, big eight chemical system CR-505 of society and CR-507,
Network ゾ
The Fyrol-6 of パ Application society system etc.
In addition, can be added on stablizer, tinting materials etc. such as softening agent commonly used in the carbamate chemical, weighting agent, antioxidant, UV light absorber as required.
When making urethane resin of the present invention, the specified amount of main raw material polyvalent alcohol and organic multiple isocyanate is mixed rapidly, and it is flow in the pattern, it is cured at normal temperatures.
When making hard polyaminoester foams, can use polyvalent alcohol, catalyzer, accent infusion, fire retardant, other the auxiliary agent class and as the above-mentioned HCFC and the HFC of whipping agent.
Above-mentioned polyvalent alcohol is to use and contains the said polyvalent alcohol in front (D) or (E) or polyvalent alcohol (G).
Use polyurethane foaming machine, resin stoste and organic multiple isocyanate are mixed rapidly according to a certain percentage continuously.
With resulting hard polyaminoester foams stoste, inject space or pattern.At this moment, regulate the flow of organic multiple isocyanate and resin stoste, so that the equivalence ratio of organic multiple isocyanate and polyvalent alcohol
Become 0.8～5.0.
After the injection, the hard polyurethane foam stoste sclerosis of just foaming in several minutes.
Resulting in the present invention hard polyaminoester foams can be used as the thermal insulation material or the structured material of refrigerator, heat-insulating shield, boats and ships or vehicle etc.
By the following examples and comparative example, the present invention is specifically described.
(preparation of polyvalent alcohol)
Reference example 1
200# novolac resin shown in the 500 gram tables 1 is packed in 2 liters the autoclave, behind the nitrogen replacement, be heated to 120 ℃.Add 2.3 gram triethylamines again and mix the propylene oxide of 274 grams of under 120 ℃, slowly packing into again.After making it to react 3 hours, remove unreacted propylene oxide in the reaction system.Thereby obtain hydroxyl value (OH value) and be the polyvalent alcohol of 339mgKOH/g (a-1) 720 grams.
Reference example 2-9
Change the proportioning raw materials except pressing table 2, identical with reference example 1, synthesize (the a-2～a-9) of the polyvalent alcohol shown in the table 2.The OH value of resulting polyvalent alcohol is shown in table 2.
The physicals of table-1 resol and phenol resin
| Sequence number | Trade mark (#) (chemistry (strain) system is pressed in Mitsui east) | Number-average molecular weight (M n) | Average functional group's number (f) | Softening temperature (℃) |
| ??(1) | ????1000HS | ??867 | ????7.70 | ??115 |
| ??(2) | ????2000 | ??723 | ????6.37 | ??95 |
| ??(3) | ????9000 | ??654 | ????5.62 | ??93 |
| ??(4) | Cresols/phenolic varnish type | ??815 | ????6.71 | ??103 |
| ??(5) | Dihydroxyphenyl propane/nonylphenol type | ??1032 | ????5.18 | ??121 |
Reference example 10～18
Except phenol resins being become trolamine, glycerol or TriMethylolPropane(TMP) or sucrose, and press outside the proportioning shown in the table 3.Identical with reference example 1, synthesize the polyvalent alcohol shown in the table 3 (b-1～b-7 and c-1～c-2).
The OH value of resulting polyvalent alcohol is shown in table 3.
(phenol resins is the modulation of polyvalent alcohol (A))
Reference example 19～27
Use reference example 10～18 synthetic polyvalent alcohol (a) and (b) of the reference example 1～9 press table 2 and table 3 and (c), and to modulate phenol resins in the ratio shown in the table 4 be polyvalent alcohol (A-1～A-9).The OH value and the viscosity of resulting polyvalent alcohol are shown in table 4.
Reference example 28～32
Except the phenol resins with reference example 1 becomes the P-amino phenol, and press outside the proportioning shown in the table 5, identical with reference example 1, synthesize (the d-1～d-5) of the polyvalent alcohol shown in the table 5.The OH value of resulting polyvalent alcohol is shown in table 5.
Reference example 33～37
Except the phenol resins in the reference example 1 is become trolamine or glycerol, and press outside the proportioning shown in the table 6, identical with reference example 1, synthesize the polyvalent alcohol shown in the table 6 (b-8～b-10 and C-3～C-4).The OH value of resulting polyvalent alcohol is shown in table 6.
(modulation of amino phenol polyvalent alcohol (B))
Reference example 38～42
Use the reference example 33-37 synthetic polyvalent alcohol (d), (b) of the reference example 28-32 press table 5 and table 6 and (c), and to modulate amino phenol in the ratio shown in the table 7 be polyvalent alcohol (B-1～B-5).The OH value and the viscosity of resulting polyvalent alcohol are shown in table 7.
Reference example 43～48
Except the phenol resins in the reference example 1 being become polyphenylene polyphenyl (support) dimethyl polyamines, and press outside the proportioning shown in the table 8, identical with reference example 1, synthesize (the e-1～e-6) of the polyvalent alcohol shown in the table 8.The OH value of resulting polyvalent alcohol is shown in Table 8.
Reference example 49～54
Except the phenol resins in the reference example 1 is become trolamine or glycerol, and press outside the proportioning shown in the table 9, identical with reference example 1, synthesize the polyvalent alcohol shown in the table 9 (b-11～b-13 and c-5～c-7).The OH value of resulting polyvalent alcohol is shown in table 9.(polyphenylene polyphenyl (support) dimethyl polyamines is the modulation of polyvalent alcohol (c))
Reference example 55～60
Use reference example 49～54 synthetic polyvalent alcohols (e), (b) of the reference example 43～48 of table 8 and table 9 and (c), and to modulate polyphenylene polyphenyl (support) dimethyl polyamines by the ratio shown in the table 10 be polyvalent alcohol (C-1～C-6).The OH value of resulting polyvalent alcohol is shown in table 10.
Embodiment 1～11
Phenol resins shown in the use table 4 is that (the poly-amino phenol shown in A-1～A-9), the table 7 is that (B-1～B-5) and polyphenylene polyphenyl (support) the dimethyl polyamines shown in the table 10 are polyvalent alcohol (C-1～C-6), and modulate the polyvalent alcohol (D) shown in the embodiment 1～11 and (E) in the ratio shown in the table 11 to polyvalent alcohol to polyvalent alcohol.Resulting OH value and viscosity are shown in table 11.
(poly-methylene polyphenylene polyamines is the preparation of polyvalent alcohol (F))
Reference example 61～66
Phenol resins in the reference example 1 is become poly-methylene polyphenylene polyamines, synthesize (the f-1～f-6) of the polyvalent alcohol shown in the table 12.The OH value of resulting polyvalent alcohol is shown in table 12.
Reference example 67～72
Except the phenol resins in the reference example 1 is become trolamine, glycerol or tetramethylolmethane, and press outside the proportioning shown in the table 13, identical with reference example 1, synthesize the polyvalent alcohol shown in the table 13 (b-14, b-15 and C-8～C-11).The OH value of resulting polyvalent alcohol is shown in Table 13.
Reference example 73-78
Use the reference example 67-72 synthetic polyvalent alcohol (f), (b) of the reference example 61～66 press table 12 and table 13 and (c), and modulate in the ratio shown in the table 14 that to gather methylene polyphenylene polyamines be polyvalent alcohol (F).The OH value and the viscosity of resulting polyvalent alcohol are shown in table 14.
Reference example 79～84
Phenol resins shown in the use table 4 is that the poly-methylene polyphenylene polyamines shown in polyvalent alcohol (A-1～A-3, A-5, A-6 and A-9) and the table 14 is polyvalent alcohol (F-1～F-6), and obtain polyvalent alcohol (G-1～G-6) in the modulation of the ratio shown in the table 15.Resulting OH value and viscosity are shown in table 15.
Table-2
Annotate: PO: propylene oxide OH value JIS K1557 standard
| The reference example sequence number | ??1 | ?2 | ??3 | ??4 | ??5 | ????6 | ???7 | ??8 | ???9 |
| Polyvalent alcohol (a) | ??a-1 | ?a-2 | ??a-3 | ??a-4 | ??a-5 | ???a-6 | ??a-7 | ?a-8 | ??a-9 |
| (NO. is referring to table 1 (g) for phenol resins | ??500(2) | ?500(3) | ??500(2) | ??500(4) | ??500(5) | ???500(1) | ??500(2) | ?500(2) | ??500(3) |
| PO (propylene oxide) (g) | ??274 | ?547 | ??305 | ??320 | ???1231 | ??821 | ?300 | ??547 | |
| EO (oxyethane) (g) | ??537 | ||||||||
| The adding mole number (mole/ The OH equivalent〕 | ?1.0 | ?1.9 | ??2.8 | ??1.2 | ??1.9 | ???4.4 | ??3.1 | ?1.1 | ??1.9 |
| OH value (mgKOH/g) | ??339 | ?250 | ??204 | ??295 | ??182 | ???153 | ??198 | ?320 | ??250 |
EO: oxyethane
Table-3
| The reference example sequence number | ???10 | ??11 | ??12 | ??13 | ??14 | ??15 | ??16 | ??17 | ??18 | ||||||
| Polyvalent alcohol (b) or (c) | ???b-1 | ??b-2 | ??b-3 | ??b-4 | ??b-5 | ??b-6 | ??b-7 | ??C-1 | ??C-2 | ||||||
| Trolamine (g) | ???500 | ??500 | ??500 | ??500 | ??500 | ??500 | ??250 | ||||||||
| Glycerol (g) | ??500 | ||||||||||||||
| Three hydroxyl methane propane (g) | ??500 | ||||||||||||||
| Sucrose (g) | ??250 | ||||||||||||||
| ??PO(g) | ???821 | ??1348 | ??821 | ??706 | ??1752 | ??3530 | ??832 | ??4230 | |||||||
| ??EO(g) | ??268 | ||||||||||||||
| The adding mole number (mole/ The OH equivalent〕 | 0.5 | ??2.1 | ??0.6 | ??0.5 | ??1.1 | ??2.9 | ??4.1 | ??0.8 | ??6.2 | ||||||
| OH value (mgKOH/g) | ???718 | ??327 | ??661 | ??718 | ??496 | ??253 | ??207 | ??730 | ??141 | ||||||
Table-4
| The reference example sequence number | ??19 | ??20 | ??21 | ??22 | ??23 | ??24 | ??25 | ??26 | ??27 | ||
| Polyol blend (A) | ??A-1 | ??A-2 | ??A-3 | ??A-4 | ??A-5 | ??A-6 | ??A-7 | ??A-8 | ??A-9 | ||
| Polyvalent alcohol (a) | ??a-1 | ??a-2 | ??a-3 | ??a-4 | ??a-5 | ??a-6 | ??a-7 | ??a-8 | ??a-9 | ||
| Polyvalent alcohol (b) or (C) | ??b-1 | ??b-2 | ??b-3 | ??b-4 | ??b-5 | ??b-6 | ??b-7 | ??C-1 | ??C-2 | ||
| Ratio (a)/(b) or (a)/(C) (weight ratio) | ??1.0 | ??0.43 | ??1.0 | ??1.0 | ??0.67 | ??1.5 | ??1.0 | ??1.5 | ??3.0 | ||
| OH value (mgKOH/g) | ??532 | ??298 | ??465 | ??507 | ??370 | ??193 | ??460 | ??245 | ??240 | ||
| Viscosity (CP/25 ℃) | ??19700 | ??9670 | ??13000 | ??19700 | ??30300 | ??18900 | ??6300 | ??4900 | ??9750 | ||
(notes): viscosity: the standard method of JIS A1557 item is measured
Table-5
| The reference example sequence number | ??28 | ??29 | ??30 | ??31 | ??32 |
| Polyvalent alcohol (d) | ??d-1 | ??d-2 | ??d-3 | ??d-4 | ??d-5 |
| P-amino-phenol (g) | ??327 | ??327 | ??218 | ??218 | ??373 |
| ??PO(g) | ??522 | ??1044 | ??1044 | ??1566 | |
| ??EO(g) | ??792 | ||||
| Add mole number (mole/OH equivalent) | ??1.0 | ??2.0 | ??3.0 | ??4.5 | ??2.0 |
| OH value (mgKOH/g) | ??595 | ??368 | ??267 | ??189 | ??451 |
Table-6
| The reference example sequence number | ??33 | ??34 | ??35 | ??36 | ??37 | |
| Polyvalent alcohol (b) or (C) | ??C-3 | ??C-4 | ??b-8 | ??b-9 | ??b-10 | |
| Trolamine (g) | ??745 | ??745 | ??298 | |||
| Glycerol (g) | ??92 | ??276 | ??92 | |||
| PO(g) | ??1131 | ??654 | ??453 | ??870 | ??1044 | |
| EO(g) | ||||||
| Add mole number (mole/OH equivalent) | ??6.5 | ??2.0 | ??1.0 | ??0.5 | ??3.0 | |
| OH value (mgKOH/g) | ??137 | ??382 | ??713 | ??521 | ??251 | |
Table-7
| The reference example sequence number | ??38 | ??39 | ??40 | ??41 | ??42 |
| Polyol blend (B) | ??B-1 | ??B-2 | ??B-3 | ??B-4 | ??B-5 |
| Polyvalent alcohol (d) | ??d-1 | ??d-2 | ??d-3 | ??d-4 | ??d-5 |
| Polyvalent alcohol (b) or (c) | ??c-3 | ??c-4 | ??b-8 | ??b-9 | ??b-10 |
| Ratio (d)/(b) or (d)/(c) (weight ratio) | ??0.2 | ??4.0 | ??0.25 | ??4.0 | ??0.5 |
| OH value (mgKOH/g) | ??214 | ??370 | ??625 | ??255 | ??320 |
| Viscosity (CP/25 ℃) | ??700 | ??7200 | ??890 | ??4800 | ??3300 |
Table-8
| The reference example sequence number | ????43 | ??44 | ??45 | ??46 | ????47 | ??48 | |
| Polyvalent alcohol (e) | ????e-1 | ??e-2 | ??e-3 | ??e-4 | ????e-5 | ??e-6 | |
| Polyphenylene polyphenyl (support) is the dimethyl polyamines (g) | ????895 | ??895 | ??448 | ??895 | ????448 | ??895 | |
| ??PO(g) | ????327 | ??654 | ??654 | ??654 | ????1473 | ||
| ??EO(g) | ??497 | ||||||
| Add mole number (mole/OH equivalent) | ????1.0 | ??2.0 | ??4.0 | ??2.0 | ????9.0 | ??2.0 | |
| OH value (mgKOH/g) | ????518 | ??408 | ??287 | ??408 | ????164 | ??455 | |
(notes) polyphenylene polyphenyl (support) dimethyl polyamines: ア ニ リ Network ス _ San Jing East presses chemistry (strain) System product
Table-9
| The reference example sequence number | ??49 | ??50 | ??51 | ??52 | ??53 | ???54 |
| Polyvalent alcohol (b) or (c) | ??c-5 | ??c-6 | ??b-11 | ??c-7 | ??b-12 | ???b-13 |
| Glycerol (g) | ??92 | ??460 | ??276 | |||
| Trolamine (g) | ??1043 | ??1043 | ???1043 | |||
| PO(g) | ??1131 | ??696 | ??609 | ??1044 | ??609 | ???609 |
| EO(g) | ||||||
| Add mole number (mole/OH equivalent) | ??6.5 | ??0.8 | ??0.5 | ??2.0 | ??0.5 | ???0.5 |
| OH value (mgKOH/g) | ??137 | ??727 | ??713 | ??382 | ??713 | ???713 |
Table-10
| The reference example sequence number | ??55 | ??56 | ??57 | ??58 | ??59 | ??60 | |
| Polyol blend (C) | ??C-1 | ??C-2 | ??C-3 | ??C-4 | ??C-5 | ??C-6 | |
| Polyvalent alcohol (e) | ??e-1 | ??e-2 | ??e-3 | ??e-4 | ??e-5 | ??e-6 | |
| Polyvalent alcohol (b) or (c) | ??c-5 | ??c-6 | ??b-11 | ??c-7 | ??b-12 | ??b-13 | |
| Ratio (e)/(b) or (e)/(c) (weight) | ??4.0 | ??2.0 | ??0.25 | ??0.10 | ??0.5 | ??3.0 | |
| OH value (mgKOH/g) | ??441 | ??514 | ??628 | ??384 | ??536 | ??519 | |
| Viscosity (CP/25 ℃) | ??22500 | ??10700 | ??3800 | ??4200 | ??7500 | ??21500 | |
Table-11 polyvalent alcohols (D) and (E)
| The embodiment sequence number | ???1 | ???2 | ???3 | ?4 | ??5 | ??6 | ??7 | ??8 | ???9 | ??10 | ?11 | |
| The polyvalent alcohol sequence number | ??D-1 | ??D-2 | ??D-3 | ?D-4 | ?D-5 | ?E-1 | ??E-2 | ?E-3 | ??E-4 | ??E-5 | ?E-6 | |
| Polyvalent alcohol (A) | ??A-6 | ??A-2 | ??A-5 | ?A-3 | ?A-1 | ?A-6 | ??A-2 | ?A-5 | ??A-3 | ??A-1 | ?A-9 | |
| Polyvalent alcohol (B or C) | ??B-1 | ??B-2 | ??B-3 | ?B-4 | ?B-5 | ?C-1 | ??C-2 | ?C-3 | ??C-4 | ??C-5 | ?C-6 | |
| (A)/(B) or (C) (weight ratio) | ??0.25 | ??2.0 | ??4.0 | ?0.5 | ?4.0 | ?4.0 | ??2.0 | ?0.25 | ??3.0 | ??1.0 | ?0.33 | |
| OH value (mgKOH/g) | ??210 | ??320 | ??420 | ?325 | ?490 | ?243 | ??370 | ?577 | ??445 | ??535 | ?450 | |
| Viscosity (CP/25 ℃) | ??1300 | ??8800 | ??14000 | ?7000 | ?12000 | ?20000 | ??10200 | ?5800 | ??8200 | ??12500 | ?15800 | |
Table-12
| The reference example sequence number | ????61 | ??62 | ???63 | ????64 | ??65 | ???66 |
| Polyvalent alcohol (f) | ????f-1 | ??f-2 | ???f-3 | ????f-4 | ??f-5 | ???f-6 |
| Poly-methylene polyphenylene polyamines (g) | ????594 | ??594 | ???198 | ????594 | ??792 | ???530 |
| ??PO(g) | ????696 | ??696 | ???1044 | ????348 | ??464 | |
| ??EO(g) | ????590 | |||||
| Add mole number (mole/OH equivalent) | ????2.0 | ??2.0 | ???9.0 | ????1.0 | ??1.0 | ????2.58 |
| OH value (mgKOH/g) | ????520 | ??520 | ???180 | ????715 | ??723 | ????516 |
(notes) gather methylene polyphenylene polyamines: chemistry (strain) is pressed in MDA-150 Mitsui east
Table-13
| The reference example sequence number | ??67 | ?68 | ??69 | ?70 | ?71 | ?72 |
| Polyvalent alcohol (b) or (c) | ??c-8 | ?c-9 | ??c-10 | ?c-11 | ?b-14 | ?b-15 |
| Glycerol (g) | ??368 | ?276 | ??92 | |||
| Tetramethylolmethane (g) | ?384 | |||||
| Trolamine (g) | ?596 | ?596 | ||||
| PO(g) | ??696 | ?1566 | ??1131 | ?1392 | ?348 | ?696 |
| EO(g) | ||||||
| Add mole number (mole/OH equivalent) | ??1.0 | ?3.0 | ??6.5 | ?3.0 | ??0.5 | ?1.0 |
| OH value (mgOH/g) | ??630 | ?274 | ??140 | ?253 | ??723 | ?525 |
Table-14 poly-methylene polyphenylene polyamines are polyvalent alcohol (F)
| The reference example sequence number | ??73 | 74 | ??75 | ?76 | ??77 | ?78 |
| Polyol blend (F) | ??F-1 | F-2 | ??F-3 | ?F-4 | ??F-5 | ?F-6 |
| Polyvalent alcohol (f) | ??f-1 | f-2 | ??f-3 | ?f-4 | ??f-5 | ?f-6 |
| Polyvalent alcohol (b) or (c) | ??c-8 | c-9 | ??c-10 | ?c-11 | ??b-14 | ?b-15 |
| Ratio (f)/(b) or (f)/(c) (weight) | ??4.0 | 3.0 | ??0.1 | ?1.0 | ??4.0 | ?1.0 |
| OH value (mgKOH/g) | ??540 | 460 | ??144 | ?404 | ??720 | ?521 |
| Viscosity (CP/25 ℃) | ??15000 | 16500 | ??11200 | ?22500 | ??23000 | ?19400 |
Table-15 polyvalent alcohols (G)
(preparation of urethane resin) (embodiment 12～22)
| The reference example sequence number | ??79 | ????80 | ??81 | ?82 | ??83 | ??84 |
| The polyvalent alcohol sequence number | ??G-1 | ????G-2 | ??G-3 | ?G-4 | ??G-5 | ??G-6 |
| Polyvalent alcohol (A) | ??A-6 | ????A-2 | ??A-5 | ?A-3 | ??A-1 | ??A-9 |
| Polyvalent alcohol (F) | ??F-1 | ????F-2 | ??F-3 | ?F-4 | ??F-5 | ??F-6 |
| (A)/(F) (weight ratio) | ??4.0 | ????0.67 | ??0.25 | ?1.0 | ??0.25 | ??3.0 |
| OH value (mgKOH/g) | ??262 | ????395 | ??190 | ?475 | ??685 | ??310 |
| Viscosity (CP/25 ℃) | ??18000 | ????13100 | ??14000 | ?21000 | ??22500 | ??12500 |
Various polyvalent alcohols and organic multiple isocyanate (Mitsui east pressure chemistry (strain) system MDI-CR that 30.0 grams are made by embodiment 1～11, NCO%=31.0) and 0.10 gram カ オ ラ イ ザ-No.1 (flower king (strain) system, amine catalyst), press the prescription shown in the table 16, by reacting at normal temperatures, make urethane resin.
Obtain about the specific absorption of urethane resin (embodiment 12～22) for CFC or HCFC.Measurement result is shown in table 16.
Table-16 urethane resins
| The embodiment sequence number | ??12 | ??13 | ??14 | ??15 | ??16 | ??17 | ??18 | ??19 | ??20 | ??21 | ??22 | ||||
| The polyvalent alcohol sequence number | ??D-1 | ??D-2 | ??D-3 | ??D-4 | ??D-5 | ??E-1 | ??E-2 | ??E-3 | ??E-4 | ??E-5 | ??E-6 | ||||
| Resin formula (g) | |||||||||||||||
| Polyvalent alcohol (D or E) | ??30 | ??30 | ??30 | ??30 | ??30 | ??30 | ??30 | ??30 | ??30 | ??30 | ??30 | ||||
| ??MDI-CR | ??15.1 | ??23.0 | ??30.1 | ??23.3 | ??35.2 | ??17.4 | ??26.6 | ??41.4 | ??31.9 | ??38.4 | ??32.3 | ||||
| ??カオライザ-No.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ||||
| Whipping agent specific absorption (%) | |||||||||||||||
| ??CFC-11(24hr) | ??0.0 | ??0.0 | ??0.0 | ??0.0 | ??0.0 | ??0.0 | ??0.0 | ??0.0 | ??0.0 | ??0.0 | ??0.0 | ||||
| ??HCFC-123(24hr) | ??0.0 | ??0.0 | ??0.1 | ??0.1 | ??0.0 | ??0.1 | ??0.0 | ??0.1 | ??0.0 | ??0.0 | ??0.0 | ||||
| ??HCFC-141b(24hr) | ??0.0 | ??0.0 | ??0.0 | ??0.0 | ??0.0 | ??0.1 | ??0.0 | ??0.0 | ??0.0 | ??0.0 | ??0.0 | ||||
MDI-CR: thick diphenylmethanediisocyanate (San Jing East presses chemistry (strain) System product)
カ ォ ラ イ ザ-No.1 amine series catalysts (flower king's (strain) System product)
The whipping agent specific absorption: resin is submerged in the fluon, measures the weight increase of the resin after 24 hours
(manufacturing of hard polyaminoester foams) (embodiment 23-39)
Be mixed with in advance by add the resin premixed thing that various CFC or HCFC constituted shown in 1.5 gram water, 1.5 gram silicon accent infusion L-5420 (Japanese ユ ニ カ-(strain) system), amine series catalysts カ オ ラ ィ ザ-No.1 (flower king (strain) system) and table 17 and the table 18 at various polyvalent alcohols 100 grams that make by embodiment 1～11, (chemistry (strain) system is pressed in Mitsui east by making itself and organic multiple isocyanate then, MDI-CR, rough diphenylmethanediisocyanate) mixes and react, make hard polyaminoester foams.When preparation resin prepolymer, the blending dispersion (operability) of observing CFC or HCFC and polyvalent alcohol in addition, is carried out the mensuration of the separated foam rate of prepared hard polyaminoester foams.
Measurement result is shown in table 17 and table 18.
Seen at table 17 and table 18, when with phenol resins be polyvalent alcohol (A) and amino phenol be polyvalent alcohol (B), polyphenylene polyphenyl (support) dimethyl polyamines be polyvalent alcohol (C), poly-methylene polyphenylene polyvalent alcohol (F) and with and the polyvalent alcohol (D) that obtains, (E) and (G), when the carboxylamine ester foaming, as whipping agent, even the equal or better operability when using hydrogenated chloride fluorine also can keep with the chlorine hydrofluoric ether that uses in the past and the physicals of foam for hydrocarbon, hydrogenation fluorinated hydrocarbon.
(manufacturing of hard polyaminoester foams) (table 19-22)
At this, pressing the manufactured hard polyaminoester foams, and confirming its physicals.The resin stoste of the proportioning shown in the preparation table 19-22, again they were mixed for 6 seconds with the organic multiple isocyanate of the specified amount shown in top each table apace with the rotating speed of 5000rpm, inject at once and be of a size of the vertical wooden case of 200 * 200 * 200mm and 380 * 380 * 35 (thick) mm and make its foaming.
Cutting goes out the foam of 80 * 80 * 30mm from the hard polyaminoester foams that is made by the former, and measure its density, compressive strength, low temperature dimensional stability by the method for IS A9514 standard, cutting goes out the foam of 200 * 200 * 25mm from the hard polyaminoester foams that is made by the latter again, and measures its thermal conductivity by the method for JIS A1412 standard.Measurement result is shown in table 19～22.
Operability when table-17 foaies are made and the separated foam rate of foam
L-5420 silicon system transfers infusion (Japanese ユ ニ カ-(strain) system) separated foam rate: Beckman formula air ratio is than specific gravity hydrometer (ベ of Toshiba Star Network マ Application (strain) system) whipping agent: the above-mentioned foam of each embodiment, use CFC-11, HCFC-123, three kinds of materials of HCFC-141b are as whipping agent, thereby obtain each foam, obtain the operability of each foam, the separated foam rate
| The embodiment sequence number | ?23 | ?24 | ??25 | ??26 | ??27 | ??28 | ???29 | ??30 | ??31 | ??32 | ?33 |
| The polyvalent alcohol sequence number | ?D-1 | ?D-2 | ??D-3 | ??D-4 | ??D-5 | ??E-1 | ???E-2 | ??E-3 | ??E-4 | ??E-5 | ?E-6 |
| OH value (mgKOH/g) | ?210 | ?320 | ??420 | ??325 | ??496 | ??243 | ???370 | ??577 | ??445 | ??535 | ?450 |
| Viscosity (CP/25 ℃) | ?1300 | ?8800 | ??14000 | ??7000 | ??12000 | ??20000 | ???10200 | ??5800 | ??8200 | ??12500 | ?15800 |
| Foam prescription (g) | |||||||||||
| Polyvalent alcohol | ?100 | ?← | ??← | ??← | ??← | ??← | ???← | ??← | ??← | ??← | ?← |
| ??H 2O | ?1.5 | ?← | ??← | ??← | ??← | ??← | ???← | ??← | ??← | ??← | ?← |
| ??L-5420 | ?1.5 | ?← | ??← | ??← | ??← | ??← | ???← | ??← | ??← | ??← | ?← |
| ??カオライザ-No.1 | ?1.2 | ?1.2 | ??0.8 | ??0.8 | ??0.8 | ??1.2 | ???1.2 | ??0.8 | ??1.2 | ??0.8 | ?2.0 |
| Whipping agent | ?27.0 | ?31.3 | ??35.3 | ??31.5 | ??38.0 | ??28.3 | ???33.3 | ??40.6 | ??36.3 | ??39.8 | ?36.4 |
| ??MDI-CR | ?79.9 | ?108.8 | ??135.1 | ??110.0 | ??153.5 | ??88.5 | ???122.0 | ??170.6 | ??141.7 | ??165.4 | ?143.0 |
| Operability | Complete good | ||||||||||
| CFC-11 (24 hours) | |||||||||||
| HCFO-123 (24 hours) | |||||||||||
| HCFG-141b (24 hours) | |||||||||||
| Separated foam rate (%) | |||||||||||
| CFC-11 (24 hours) | 87.5 | ?88.0 | ??89.5 | ??88.2 | ??88.3 | ??87.9 | ???88.1 | ??89.5 | ??90.3 | ??89.5 | ?88.2 |
| HCFC-123 (24 hours) | 85.3 | ?89.0 | ??89.0 | ??88.5 | ??85.2 | ??86.3 | ???85.3 | ??86.2 | ??85.3 | ??84.1 | ?86.5 |
| HCFC-141b (24 hours) | 87.5 | ?88.2 | ??87.3 | ??86.3 | ??85.4 | ??86.3 | ???86.5 | ??86.6 | ??85.3 | ??88.2 | ?88.2 |
Operability when table-18 foaies are made and the separated foam rate of foam
| The embodiment sequence number | ??34 | ??35 | ??36 | ??37 | ??38 | ??39 | ||||
| The polyvalent alcohol sequence number | ??C-1 | ??C-2 | ??C-3 | ??C-4 | ??C-5 | ??C-6 | ||||
| OH value (mgKOH/g) | ??262 | ??395 | ??190 | ??475 | ??685 | ??310 | ||||
| Viscosity (CP/25 ℃) | ??18000 | ??13100 | ??14000 | ??21000 | ??22500 | ??12500 | ||||
| Foam prescription (g) | ||||||||||
| Polyvalent alcohol | ??100 | ??← | ??← | ??← | ??← | ??← | ||||
| ??H 2O | ??1.5 | ??← | ??← | ??← | ??← | ??← | ||||
| ??L-5420 | ??1.5 | ??← | ??← | ??← | ??← | ??← | ||||
| ??カオライザ-No.1 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??0.8 | ??1.2 | ||||
| Whipping agent | ??29.0 | ??34.3 | ??26.2 | ??37.4 | ??45.7 | ??30.9 | ||||
| ??MDI-CR | ??93.5 | ??128.5 | ??74.6 | ??149.6 | ??204.8 | ??106.2 | ||||
| Operability | Complete good | |||||||||
| CFC-11 (24 hours) | ||||||||||
| HCFC-123 (24 hours) | ||||||||||
| HCFC-141b (24 hours) | ||||||||||
| Separated foam rate (%) | ||||||||||
| CFC-11 (24 hours) | ??88.5 | ??89.3 | ??89.0 | ??88.0 | ??88.5 | ??90.1 | ||||
| HCFC-123 (24 hours) | ??86.5 | ??87.5 | ??88.0 | ??88.0 | ??87.0 | ??88.5 | ||||
| HCFC-141b (24 hours) | ??87.5 | ??87.5 | ??89.0 | ??87.5 | ??87.5 | ??87.3 | ||||
Table-19 foam physicalies (embodiment 40～53, comparative example 1～7)
| Comparative example | Embodiment | Comparative example | Embodiment | Comparative example | Embodiment | Comparative example | Embodiment | Comparative example | Embodiment | Comparative example | Embodiment | Comparative example | Embodiment | |||||||||||||||||
| ??1 | ??40 | ??41 | ??2 | ??42 | ??43 | ??3 | ??44 | ??45 | ??4 | ??46 | ??47 | ??5 | ??48 | ??49 | ??6 | ??50 | ??51 | ??7 | ??52 | ??53 | ||||||||||
| Raw material is formed (g) | MDI-CR | ??79.9 | ??108.8 | ??135.1 | ??110.1 | ??153.5 | ??135.1 | ??135.1 | ||||||||||||||||||||||
| Polyvalent alcohol D-1 | ??100 | |||||||||||||||||||||||||||||
| Polyvalent alcohol D-2 | ??100 | |||||||||||||||||||||||||||||
| Polyvalent alcohol D-3 | ??100 | ??100 | ??100 | |||||||||||||||||||||||||||
| Polyvalent alcohol D-4 | ??100 | |||||||||||||||||||||||||||||
| Polyvalent alcohol D-5 | ??100 | |||||||||||||||||||||||||||||
| ?H 2O | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | |||||||||||||||||||||||
| L-5420 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | |||||||||||||||||||||||
| カォラィザ-No.1 | ??1.2 | ??1.2 | ??0.8 | ??0.8 | ??0.8 | ??0.8 | ??0.8 | |||||||||||||||||||||||
| Whipping agent | CFC-11 | ??30 | ??31 | ??35 | ??32 | ??23 | ??35 | ??35 | ||||||||||||||||||||||
| HCFC-141b | ??23 | ??27 | ??31 | ??27 | ??20 | ??31 | ??31 | |||||||||||||||||||||||
| HCFC-123 | ??32 | ??38 | ??42 | ??38 | ??28 | ??39 | ??39 | |||||||||||||||||||||||
| HFC-134a | ??5 | |||||||||||||||||||||||||||||
| Iso-pentane | ??5 | |||||||||||||||||||||||||||||
| The physicals of foam | Free foaming density (Kg/m 3〕 | ?25.5 | ??24.9 | ??25.8 | ??24.3 | ??24.0 | ??24.8 | ??25.2 | ??25.0 | ??25.5 | ??24.2 | ??23.9 | ??24.5 | ??25.3 | ??25.0 | ??25.3 | ??25.2 | ??25.0 | ??26.0 | ?25.2 | ??25.0 | ??26.0 | ||||||||
| Compressive strength (Kg/cm 2〕 | ??1.86 | ??1.80 | ??1.80 | ??1.70 | ??1.65 | ??1.60 | ??1.80 | ??1.80 | ??1.75 | ??1.71 | ??1.61 | ??1.60 | ??1.80 | ??1.76 | ??1.70 | ??1.80 | ??18.0 | ??1.70 | ?1.80 | ??1.80 | ??1.70 | |||||||||
| Low temperature dimensional stability (% ,-30 ℃ * 24 hours) | -0.1 | ??-0.3 | ??-0.3 | ??-0.1 | ??-0.2 | ??-0.3 | ??0.0 | ??0.0 | ??-0.2 | ??-0.1 | ??-0.2 | ??-0.4 | ??-0.2 | ??-0.2 | ??-0.3 | ??0.0 | ??0.0 | ??-0.4 | ??0.0 | ??0.0 | ??-0.4 | |||||||||
| Thermal conductivity (Kcal/ mhr℃〕 | ??0.0160 | ??0.0162 | ??0.0165 | ??0.0159 | ??0.0159 | ??0.0163 | ??0.0160 | ??0.0160 | ??0.0163 | ??0.0160 | ??0.0161 | ??0.0163 | ??0.0160 | ??0.0162 | ??0.0163 | ??0.0160 | ??0.0160 | ??0.0165 | ??0.0160 | ??0.0160 | ??0.0165 | |||||||||
| Thermal conductivity * 10 -2W/m·K | ??1.86 | ??1.88 | ??1.92 | ??1.85 | ??1.85 | ??1.90 | ??1.86 | ??1.86 | ??1.90 | ??1.86 | ??1.87 | ??1.90 | ??1.86 | ??1.88 | ??1.90 | ??1.86 | ??1.86 | ??1.92 | ??1.86 | ??1.86 | ??1.92 | |||||||||
The physicals (embodiment 54-67, comparative example 8-14) of table-20 foaies
| Comparative example | Embodiment | Comparative example | Embodiment | Comparative example | Embodiment | Comparative example | Embodiment | Comparative example | Embodiment | Comparative example | Embodiment | Comparative example | Embodiment | |||||||||||
| ??8 | ??54 | ??55 | ??9 | ??56 | ??57 | ??10 | ??58 | ??59 | ??11 | ??60 | ??61 | ??12 | ??62 | ??63 | ??13 | ??64 | ??65 | ??14 | ??66 | ??67 | ||||
| Raw material is formed (g) | MDI-CR | ??88.5 | ??122.0 | ??170.6 | ??141.7 | ??165.4 | ??141.7 | ??141.7 | ||||||||||||||||
| Polyol E-1 | ??100 | |||||||||||||||||||||||
| Polyol E-2 | ??100 | |||||||||||||||||||||||
| Polyol E-3 | ??100 | |||||||||||||||||||||||
| Polyol E-4 | ??100 | ??100 | ??100 | |||||||||||||||||||||
| Polyol E-5 | ??100 | |||||||||||||||||||||||
| H 2O | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | |||||||||||||||||
| L-5420 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | |||||||||||||||||
| カオライザ-No.1 | ??1.2 | ??1.2 | ??0.8 | ??1.2 | ??0.8 | ??1.2 | ??1.2 | |||||||||||||||||
| Whipping agent | CFC-11 | ??28 | ??33 | ??41 | ??36 | ??40 | ??36 | ??36 | ||||||||||||||||
| HCFC-141b | ??25 | ??29 | ??35 | ??31 | ??35 | ??31 | ??31 | |||||||||||||||||
| HCFC-123 | ??34 | ??40 | ??49 | ??44 | ??48 | ??40 | 40 | |||||||||||||||||
| HFC-134a | ??5 | |||||||||||||||||||||||
| Iso-pentane | ??5 | |||||||||||||||||||||||
| The physical property of foaming body | Free foaming density (Kg/m 3〕 | ??24.3 | ??24.1 | ??24.8 | ??24.5 | ??24.2 | ??25.5 | ??25.6 | ??25.4 | ??25.8 | ??25.2 | ??25.0 | ??25.5 | ??25.5 | ??25.2 | ??26.0 | ??25.2 | ??25.0 | ??26.0 | ??25.2 | ??25.0 | ??26.0 | ||
| Compressive strength (Kg/cm 2〕 | ??1.80 | ??1.80 | ??1.73 | ??1.75 | ??1.70 | ??1.70 | ??1.75 | ??1.74 | ??1.74 | ??1.75 | ??1.77 | ??1.74 | ??1.79 | ??1.75 | ??1.77 | ??1.75 | ??1.77 | ??1.70 | ??1.75 | ??1.77 | ??1.71 | |||
| Low temperature dimensional stability (% ,-30 ℃ * 24 hours) | ??-0.3 | ??-0.2 | ??-0.3 | ??-0.0 | ??-0.1 | ??-0.3 | ??-0.2 | ??-0.1 | ??-0.4 | ??-0.1 | ??-0.1 | ??-0.2 | ??-0.1 | ??0.0 | ??-0.3 | ??-0.1 | ??-0.1 | ??-0.3 | ??-0.1 | ??-0.1 | ??-0.3 | |||
| Thermal conductivity (Kcal/ mhr℃?〕 | ??0.0160 | ??0.0163 | ??0.0164 | ??0.0160 | ??0.0162 | ??0.0165 | ??0.0162 | ??0.0163 | ??0.0165 | ??0.0165 | ??0.0166 | ??0.0168 | ??0.0158 | ??0.0159 | ??0.0162 | ??0.0165 | ??0.0166 | ??0.0169 | ??0.0165 | ??0.0166 | ??0.0169 | |||
| Thermal conductivity (W/mK * 10 -2) | ??1.86 | ??1.90 | ??1.91 | ??1.86 | ??1.88 | ??1.92 | ??1.88 | ??1.90 | ??1.92 | ??1.92 | ??1.9 | ??1.95 | ??1.84 | ??1.85 | ??1.88 | ??1.92 | ??1.93 | ??1.97 | ??1.92 | ??1.93 | ??1.97 | |||
Table-21 foam physicalies (embodiment 68-81, comparative example 15-21)
| Comparative example | Embodiment | Comparative example | Embodiment | Comparative example | Embodiment | Comparative example | Embodiment | Comparative example | Embodiment | Comparative example | Embodiment | Comparative example | Embodiment | ||||||||||||||||||||
| ??15 | ??68 | ??69 | ??16 | ??70 | ??71 | ??17 | ??72 | ??73 | ??18 | ??74 | ??75 | ??19 | ??76 | ??77 | ??20 | ??78 | ??79 | ??21 | ??80 | ??81 | |||||||||||||
| Raw material is formed (g) | MDI-CR | ??93.5 | ??128.5 | ??74.6 | ??149.6 | ??204.8 | ??149.6 | ??149.6 | |||||||||||||||||||||||||
| Polyvalent alcohol G-1 | ??100 | ||||||||||||||||||||||||||||||||
| Polyvalent alcohol G-2 | ??100 | ||||||||||||||||||||||||||||||||
| Polyvalent alcohol G-3 | ??100 | ||||||||||||||||||||||||||||||||
| Polyvalent alcohol G-4 | ??100 | ??100 | ??100 | ||||||||||||||||||||||||||||||
| Polyvalent alcohol G-5 | ??100 | ||||||||||||||||||||||||||||||||
| H 2O | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ||||||||||||||||||||||||||
| L-5420 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ||||||||||||||||||||||||||
| カオライザ-No.1 | ??1.5 | ??1.5 | ??1.5 | ??1.5 | ??0.8 | ??1.5 | ??1.5 | ||||||||||||||||||||||||||
| CFC-11 | ??29 | ??34 | ??26 | ??37 | ??31 | ??37 | ??37 | ||||||||||||||||||||||||||
| HCFC-141b | ??25 | ??30 | ??23 | ??32 | 27 | 32 | ??32 | ||||||||||||||||||||||||||
| HCFC-123 | ??35 | ??41 | ??31 | ??45 | ??37 | ??40 | 40 | ||||||||||||||||||||||||||
| HFC-134a | ??5 | ||||||||||||||||||||||||||||||||
| Iso-pentane | 5 | ||||||||||||||||||||||||||||||||
| The physical property of foaming body | Free foaming density (Kg/m 3〕 | ??24.6 | ??24.7 | ??25.2 | ??24.8 | ??25.0 | ??25.5 | ??24.4 | ??24.5 | ??25.5 | ??25.0 | ??25.1 | ??25.8 | ??25.5 | 25.9 | ??26.0 | ??25.0 | 25.1 | ??26.0 | ??25.0 | ??25.1 | 26.2 | |||||||||||
| Compressive strength (Kg/cm 2〕 | ??1.50 | ??1.25 | ??1.19 | ??1.30 | ??1.20 | ??1.15 | ??1.50 | ??1.30 | ??1.25 | ??1.50 | ??1.30 | ??1.25 | ??1.82 | 1.65 | ??1.63 | ??1.50 | 1.30 | ??1.24 | ??1.50 | ??1.30 | 1.23 | ||||||||||||
| Low temperature dimensional stability (% ,-30 ℃ * 24 hours) | ??-0.2 | ??-0.8 | ??-1.0 | ??-0.6 | ??-0.7 | ??-1.0 | ??-0.2 | ??-0.4 | ??-1.0 | ??-0.2 | ??-0.6 | ??-0.6 | ??-0.2 | -0.8 | ??-1.4 | ??-0.2 | -0.6 | ??-0.7 | ??-0.2 | ??-0.6 | -0.8 | ||||||||||||
| Thermal conductivity (Kcal/ mhr℃〕 | ??0.0165 | ??0.0168 | ??0.0170 | ??0.0168 | ??0.0170 | ??0.0172 | ??0.0163 | ??0.0165 | ??0.0167 | ??0.0163 | ??0.0166 | ??0.0168 | ??0.0159 | 0.0168 | ??0.0161 | ??0.0163 | 0.0166 | ??0.0165 | ??0.0163 | ??0.0166 | 0.0169 | ||||||||||||
| Thermal conductivity * 10 -2W/m·K | ??1.92 | ??1.95 | ??1.98 | ??1.95 | ??1.98 | ??2.00 | ??1.90 | ??1.92 | ??1.94 | ??1.90 | ??1.93 | ??1.95 | ??1.85 | 1.90 | ?1.87 | ??1.90 | 1.93 | ??1.97 | ??1.90 | ??1.93 | 1.97 | ||||||||||||
Table-22 foam physicalies (comparative example 22～27)
| Comparative example | |||||||||
| ??22 | ??23 | ??24 | ??25 | ??26 | ??27 | ||||
| Raw material is formed (g) | MDI-CR | ??144 | ??144 | ||||||
| Polyvalent alcohol R-1 | ??100 | ||||||||
| Polyvalent alcohol R-2 | ??100 | ||||||||
| H 2O | ??1.5 | ??1.5 | |||||||
| L-5420 | ??1.5 | ??1.5 | |||||||
| カオライザ-No.1 | ??3.0 | ??3.0 | |||||||
| Whipping agent | ?CFC-11 | ??37 | ??37 | ||||||
| ?HCFC-141b | ??30 | ??30 | |||||||
| ?HCFC-123 | ??44 | ??44 | |||||||
| The physicals of foam | Free foaming density (Kg/m 3〕 | ??24.5 | ??25.1 | ??25.2 | ??25.0 | ??25.2 | ??25.3 | ||
| Compressive strength (Kg/cm 2〕 | ??1.51 | ??0.97 | ??1.01 | ??1.61 | ??0.98 | ??0.95 | |||
| Low temperature dimensional stability (% ,-30 ℃ * 24 hours) | ??-0.5 | ???-3.6 | ??-5.8 | ??-1.0 | ??-4.5 | ??-7.5 | |||
| Thermal conductivity (W/mK) * 10 -2〔Kcal/mhr℃〕 | ??1.98 ??0.0170 | ??2.09 ??0.0180 | ??2.15 ??0.0185 | ??1.92 ??0.0165 | ??2.09 ??0.0180 | ??2.12 ??0.0182 | |||
(1) hard polyamine ester foaming compound body of subsidiary plane materiel
When carrying out above experiment, also tested the manufacturing of the hard polyamine ester foaming compound body of subsidiary plane materiel of the present invention.
In this test, be to use the listed polyvalent alcohol of table 11 and table 23.
Table 23
| Polyvalent alcohol sequence number (No.) | ?R-1 | ??R-2 |
| Polyvalent alcohol | Glycerol | Glycerol シ ェ Network ロ-ス |
| Epoxide | PO | ??PO |
| OH-value (mgKOH/g) | 450 | ??450 |
| Viscosity (CP/25 ℃) | 480 | ??8500 |
(notes) PO: propylene oxide
What is called is used for plane materiel of the present invention, for for example, and corrugated paper, lamination paper, other paper product, polyethylene, polypropylene, polyvinyl chloride, other synthetic resin board, aluminium, iron, other metal sheet.
1) has the manufacturing of the hard polyamine ester foaming compound body of 1 plane materiel.(table 24,25)
The polyvalent alcohol that will be used for this experiment by following condition, carries out atomised jet according to the prescription shown in the table 24 on 1 surface, so that make the hard polyamine ester foaming compound body of subsidiary plane materiel, physical properties of articles is shown in table 25.
Foaming machine: model-FF ヘ ッ De D ガ Application that ガ ス マ-society makes
Output pressure: 50Kg/Cm
2
Fluid temperature: 40 ℃
Plane materiel: corrugated paper
2) has the manufacturing (table 26,27) of the hard polyamine ester foaming compound body of many plane materiels.
The polyurethane foaming body that will be used for this experiment adopts the continuous processing according to following condition by the prescription shown in the table 26, makes the hard polyamine ester foaming compound body of subsidiary two plane materiels.Physical properties of articles is shown in Table 27.
Machine title: the high pressure foaming machine (MQ type) of the band stirring head that ヘ ネ ッ ケ society makes
Linear velocity: 10 meters/minute
Temperature: 30～40 ℃ of starting material
55 ℃ of curing ovens
Goods: wide 1m * thickness 40mm
Foaming layer 35mm
Plane materiel: lamination paper
Be used for plane materiel and following plane materiel
As above experimental result finding, use the occasion of polyvalent alcohol of the present invention, because except having the good characteristic that said foam had in the past, also has suitable reactivity, even so when non-horizontal component carries out atomised jet, before the foaming sclerosis, the liquid sagging phenomenon that starting material liquid does not have stream to hang down yet, good with the cementability of plane materiel, the proterties on atomised jet surface might as well.In addition, can obtain the complex body of the subsidiary plane materiel of good flame resistance, premium properties that thermal conductivity is little.
The stock liquid that uses in this is shown in table 24 and table 25, but be not limited to these starting material liquid, illustrative whole stock liquid all is the operable fact in aforesaid table 11 and the table 15 (using polyvalent alcohol (D), (E), (G)), there is no need to be illustrated from aim of the present invention.
Table-24
(notes) TCEP fire retardant, three (2-chloroethyl) phosphoric acid ester
| Embodiment | Comparative example | |||||
| 82 | 83 | 84 | ??28 | ??29 | ??30 | |
| Cooperate prescription (g) MDI-CR polyalcohol D-5 E-4 R-1 R-2 TCEP H2O ??L-5420 ??カオライザ-No.1 ??LL-690D ??CFC-11 ??HCFC-141b ??HCFC-123 | ? 145.3 ? 100 ? ? ? 10 0.5 1.5 2.4 0.1 ? 32 | ? 145.3 ? 100 ? ? ? 10 0.5 1.5 2.4 0.1 ? ? 44 | ? 133.5 ? ? 100 ? ? 10 0.5 1.5 3.6 0.1 ? ? 42 | ? ??127 ? ? ? ??100 ? ??10 ??0.5 ??1.5 ??5.0 ??0.1 ??19 ? ? ? | ? ??127 ? ? ? ??100 ? ??10 ??0.5 ??1.5 ??5.0 ??0.1 ? ??17 | ? ??127 ? ? ? ? ??100 ??10 ??0.5 ??1.5 ??5.0 ??0.1 ? ? ??23 |
Big eight chemistry (strain) system
The LL-690D catalyzer, the dioctyl phthalate of lead octoate 36
40 weight % solution
Table-25
(notes) (1) liquid sagging phenomenon: when atomised jet foams on axial plane materiel, presclerotic
| Embodiment | Comparative example | |||||
| ??82 | ??83 | 84 | 28 | ??29 | ??30 | |
| Cooperate prescription (in table 24) | (reality) 82 | (reality) 83 | (reality) 84 | (ratio) 28 | (ratio) 29 | (ratio) 30 |
| Reactive (second) no adhesion time | ??4～5 | ??4～5 | 4～5 | 5 | ??5～6 | ??5 |
| Liquid sagging phenomenon superficiality tackiness | Not good | Not good | Not good | Not good | Have good | Have good |
| Foam density (Kg/m 3〕 | ??36.4 | ??36.8 | 36.8 | 38.0 | ??39.0 | ??39.0 |
| Compressive strength (Kg/Cm 2〕 | ??3.34 | ??3.35 | 3.30 | 3.25 | ??3.10 | ??2.95 |
| Thermal conductivity (Kcal/mhr ℃) (W/mK * 10 -2) | ??0.0165 ??1.92 | ??0.0167 ??1.94 | 0.0170 1.98 | 0.0180 2.09 | ??0.0190 ??2.21 | ??0.0188 ??2.19 |
| Incendivity (2) combustion time (second) burning extent (mm) | ? ??22 ??18 | ? ??20 ??17 | ? 21 19 | ? 24 19 | ? ??35 ??20 | ? ??33 ??21 |
The phenomenon that stock liquid drips downwards.
(2) incendivity (flame retardant resistance): press that 1691 standard methods of ASTM D measure.
(3) expression of (reality) in prescription embodiment sequence number, the sequence number of (ratio) expression comparative example
Table-26
| Embodiment | Comparative example | |||||
| ??85 | ??86 | ??87 | ??31 | ??32 | ??33 | |
| Cooperate prescription (g) MDI-CR polyalcohol D-3 E-6 R-1 R-2 TCEP H2O ????L-5420 ????カオライザ-No.1 ????CFC-11 ????HCFC-141b ????HCFC-123 | ? ??135 ? ??100 ? ? ? ??10 ??1.5 ??1.5 ??0.8 ? ??31 | ? ??135 ? ??100 ? ? ? ??10 ??1.5 ??1.5 ??0.8 ? ? ??42 | ? ??143 ? ? ??100 ? ? ??10 ??1.5 ??1.5 ??2.0 ? ? ??43 | ? ??144 ? ? ? ??100 ? ??10 ??1.5 ??1.5 ??3.0 ??37 | ? ??144 ? ? ? ??100 ? ??10 ??1.5 ??1.5 ??3.0 ? ??30 | ? ??144 ? ? ? ? ??100 ??10 ??1.5 ??1.5 ??2.8 ? ? ??44 |
Table-27
| Embodiment | Comparative example | |||||
| ??85 | ??86 | ??87 | ??31 | ??32 | ??33 | |
| Cooperate prescription (in table 26) | ??85 | ??86 | ??87 | ??31 | ??32 | ??33 |
| Tackiness between plane materiel and foaming layer | Well | Well | Well | Well | Well | Well |
| Foam density (Kg/m 3〕 | ??30.3 | ??31.5 | ??31.0 | ??30.0 | ??31.0 | ??31.5 |
| Compressive strength (Kg/cm 2〕 | ??1.64 | ??1.75 | ??1.60 | ??1.55 | ??1.05 | ??1.00 |
| Flexural strength (Kg/cm 2〕 | ??2.50 | ??2.40 | ??2.44 | ??2.45 | ??1.95 | ??1.85 |
| Thermal conductivity (Kcal/mhr ℃) (W/mK * 10 -2) | ??0.0163 ??1.90 | ??0.0165 ??1.92 | ??0.0170 ??1.98 | ??0.0170 ??1.98 | ??0.0185 ??2.15 | ??0.0186 ??2.16 |
| Incendivity combustion time (second) burning extent (mm) | ??22 ??16 | ??21 ??14 | ??21 ??15 | ??23 ??16 | ??30 ??21 | ??31 ??20 |
Subordinate list: the brief description of polyvalent alcohol among the present invention
Polyvalent alcohol (D)=(A)+(B)
(A)=(a)+(b) or (a)+(c)
(B)=(d)+(b) or (d)+(c)
Polyvalent alcohol (E)=(A)+(C)
(A) same as described above
(C)=(e)+(b) or (e)+(c)
Polyvalent alcohol (G)=(A)+(F)
(A) same as described above
(F)=(f)+(b) or (f)+(c)
Wherein:
Polyvalent alcohol (A): phenol resins is a polyvalent alcohol
Polyvalent alcohol (B): amino phenol is a polyvalent alcohol
Polyvalent alcohol (C): polyphenylene polyphenyl (support) dimethyl polyamines is a polyvalent alcohol
Polyvalent alcohol (F): poly-methylene polyphenylene polyamines is a polyvalent alcohol
Polyvalent alcohol (a): phenol resins+AO
Polyvalent alcohol (b): alkanolamine based compound thing+AO
Polyvalent alcohol (c): aliphatic polyhydroxy compound+AO
Polyvalent alcohol (d): amino phenol based compound+AO
Polyvalent alcohol (e): polyphenylene polyphenyl (support) dimethyl polyamines based compound+AO
Polyvalent alcohol (f): poly-methylene polyphenylene polyamines based compound+AO notes-AO: epoxide
Claims (10)
1. the manufacture method of a hard polyamine ester foaming compound body, described method is to make to contain polyvalent alcohol, whipping agent, catalyzer, the resin stoste of accent infusion and other auxiliary agent is mixed with organic multiple isocyanate and is reacted, form the manufacture method of the complex body of polyurethane foaming body again in the space that on 1 plane materiel or on many plane materiels, surrounds, it is characterized in that, part or all of this polyvalent alcohol is to use a kind of polyvalent alcohol (D), it is that polyvalent alcohol (A) and amino phenol are polyvalent alcohol (B) that described polyvalent alcohol (D) contains phenol resins, wherein, (A)/(B) weight ratio is 0.25～4.0, hydroxyl value is 180～700mgKOH/g, and this whipping agent, be to use to contain to be selected from hydrogenated chloride fluorine, and use frothing aid as required for one or more the whipping agent in hydro carbons and the hydrogenation fluorinated hydrocarbon.
2. the manufacture method of a hard ammonia ester foaming volume recombination body, described method is, make and contain polyvalent alcohol, whipping agent, catalyzer, the resin stoste of accent infusion and other auxiliary agent is mixed with organic multiple isocyanate and is reacted, form the manufacture method that urethane is sent out the complex body of foam in the space that on 1 plane materiel or on many plane materiels, surrounds again, it is characterized in that, part or all of this polyvalent alcohol used a kind of polyvalent alcohol (E), it is that polyvalent alcohol (A) and polyphenylene polyphenyl (support) dimethyl polyamines are polyvalent alcohol (C) that this polyvalent alcohol (E) contains phenol resins, and, (A)/(C) be 0.25～4.0 weight ratio, hydroxyl value is 180～700mgKOH/g, to be polyvalent alcohol (A) be made up of polyvalent alcohol (a) and polyvalent alcohol (b) or polyvalent alcohol (c) described phenol resins, wherein, polyvalent alcohol (a) is represented by following general formula (I) for use, number-average molecular weight is 650～1400, average functional group number is one or more a mixture of 3～8 phenol resins, and added 1.0～4.5 moles epoxide and the hydroxyl value that obtains is the polyvalent alcohol of 140～350mgKOH/g with respect to the hydroxyl of this compound of each equivalent or mixture, polyvalent alcohol (b) is the polyvalent alcohol of 240～800mgKOH/g for one or more each equivalent active hydrogen base of mixture of the alkanolamine based compound of following general formula (II) expression adds the hydroxyl value that 0.5～3.0 mole epoxide obtains, polyvalent alcohol (c) is that to add the hydroxyl value that 0.5～6.5 mole epoxide obtains be the polyvalent alcohol of 130～750mgKOH/g to one or more each equivalent hydroxyl of active dydrogen compounds of mixture of 2～8 aliphatic polyhydroxy compound for functional group's number
In the formula (I), R
1Expression hydrogen atom, carbonatoms are 1～9 alkyl, chlorine atom, bromine atoms, fluorine atom or hydroxyl; m is 1～3; in addition; n is 1～6; X; Y is identical or inequality, and it is basic that expression is selected from one or more the combination of divalent radical of the alkylidene group of represent carbonatoms 1～10, benzene (support) dimethyl, oxo base, thio group, sulfonyl
NR
2R
2R
3??????????????????????????????????(II)
In the formula (II), R
2And R
3Expression is selected from the atom or the group of hydrogen atom, ethanol based, Virahol base, R respectively
2And R
3Identical or inequality, still, R
2And R
3Be except the situation of hydrogen atom simultaneously, and this whipping agent is to use to contain and is selected from one or more the whipping agent of hydrogenated chloride fluorine for hydro carbons and hydrogenation fluorinated hydrocarbon, and use frothing aid as required.
3. according to the manufacture method of claim 1 or 2 said hard polyamine ester foaming compound bodies, wherein, make it to form the method for hard polyaminoester foams, by applying, inject or spraying and realize.
4. according to the manufacture method of claim 1 or 2 said hard polyamine ester foaming compound bodies, it is characterized in that part or all branch of organic multiple isocyanate is the prepolymer that contains isocyanate group endways.
5. according to the manufacture method of the hard polyamine ester foaming compound body of claim 1 or 2, wherein, the isocyanate group of organic multiple isocyanate and the equivalence ratio of hydroxyl groups are 0.8-5.0.
6. the manufacture method of a hard polyamine ester foaming compound body, described method is to make to contain polyvalent alcohol, whipping agent, catalyzer, transfer infusion that resin stoste and the organic multiple isocyanate mixture and the reaction of other auxiliary agent are arranged, make hard polyaminoester foams be configured as the manufacture method of complex body in the space that on 1 plane materiel or on many plane materiels, surrounds again, it is characterized in that, it is the polyvalent alcohol (G) of 180～700mgKOH/g that part or all of this polyvalent alcohol used hydroxyl value, it is that polyvalent alcohol (A) and poly-methylene polyphenylene polyamines are polyvalent alcohol (F) that this polyvalent alcohol (G) contains phenol resins, and weight ratio (A)/(F) is 0.25～4.0, described polyvalent alcohol (A) is made up of polyvalent alcohol (a) and polyvalent alcohol (b) or polyvalent alcohol (c), wherein, polyvalent alcohol (a) is represented by following general formula (I) for use, number-average molecular weight is 650～1400, average functional group number is one or more a mixture of 3～8 phenol resins, and added 1.0～4.5 moles epoxide and the hydroxyl value that obtains is the polyvalent alcohol of 140～350mgKOH/g with respect to the hydroxyl of this compound of each equivalent or mixture, polyvalent alcohol (b) is the polyvalent alcohol of 240～800mgKOH/g for one or more each equivalent active hydrogen base of mixture of the alkanolamine based compound of following general formula (II) expression adds the hydroxyl value that 0.5～3.0 mole epoxide obtains, polyvalent alcohol (c) is that to add the hydroxyl value that 0.5～6.5 mole epoxide obtains be the polyvalent alcohol of 130～750mgKOH/g to one or more each equivalent hydroxyl of active dydrogen compounds of mixture of 2～8 aliphatic polyhydroxy compound for functional group's number
In the formula (I), R
1Expression hydrogen atom, carbonatoms are 1～9 alkyl, chlorine atom, bromine atoms, fluorine atom or hydroxyl; m is 1～3; in addition; n is 1～6; X; Y is identical or inequality, expression be selected from carbonatoms 1～10 alkylidene group, benzene (support) dimethyl, oxo base, thio group, sulfonyl divalent radical one or more in conjunction with basic
NR
2R
2R
3????????????????????????????(II)
In the formula (II), R
2And R
3Expression is selected from atom or the group in the class that hydrogen atom, ethanol based, Virahol base form, R respectively
2And R
3Identical or inequality, still, R
2And R
3Be except the situation of hydrogen atom simultaneously, and this whipping agent is to use to contain and is selected from hydrogenated chloride fluorine for one or more the whipping agent in hydro carbons and the hydrogenation fluorinated hydrocarbon, and use frothing aid as required.
7. according to the manufacture method of the said hard polyamine ester foaming compound body of claim 6, it is characterized in that part or all of organic multiple isocyanate is the prepolymer that contains isocyanate group endways.
8. according to the manufacture method of the said hard polyamine ester foaming compound body of claim 6, wherein, the isocyanate group of organic multiple isocyanate and the equivalence ratio of hydroxyl groups are 0.8～5.0.
9. according to the manufacture method of the said hard polyamine ester foaming compound body of claim 6, wherein, the method that forms hard polyaminoester foams is by applying, inject or spraying and realize.
10. according to the manufacture method of claim 6 hard polyamine ester foaming compound body, wherein, poly-methylene polyphenylene polyamines is that polyvalent alcohol (F) is made of polyvalent alcohol (f) and polyvalent alcohol (b) or polyvalent alcohol (c), wherein, polyvalent alcohol (f) is the polyvalent alcohol of 150～700mgLOH/g for the hydroxyl value that the epoxide that adds 1.0～9.0 moles with respect to the active hydrogen of 1 normal poly-methylene polyphenylene polyamines obtains.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29709590A JP3176058B2 (en) | 1990-11-05 | 1990-11-05 | Polyol and its use |
| CN95108366A CN1044483C (en) | 1990-11-05 | 1995-06-30 | Production of hard polyamine ester foaming compound body |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29709590A JP3176058B2 (en) | 1990-11-05 | 1990-11-05 | Polyol and its use |
| CN95108366A CN1044483C (en) | 1990-11-05 | 1995-06-30 | Production of hard polyamine ester foaming compound body |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90109728.4A Division CN1031139C (en) | 1989-12-20 | 1990-11-05 | Polyol and utilization thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1123798A true CN1123798A (en) | 1996-06-05 |
| CN1044483C CN1044483C (en) | 1999-08-04 |
Family
ID=37098768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95108366A Expired - Fee Related CN1044483C (en) | 1990-11-05 | 1995-06-30 | Production of hard polyamine ester foaming compound body |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3176058B2 (en) |
| CN (1) | CN1044483C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100554302C (en) * | 2004-10-20 | 2009-10-28 | 日本聚氨酯工业株式会社 | The manufacture method of polyurethane foaming body |
| CN1995109B (en) * | 2006-01-06 | 2011-04-27 | 广东科龙电器股份有限公司 | Process for preparing rigid polyurethane foams |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9203663A (en) * | 1991-09-20 | 1993-04-20 | Union Carbide Chem Plastic | USE OF CAPEATED SURFACES FOR THE PRODUCTION OF RIGID POLYARETANE FOAMS BLOWED WITH HYDROCHLORO-FLUORCARBONS |
| KR101345075B1 (en) * | 2008-11-06 | 2013-12-26 | 아사히 유키자이 고교 가부시키가이샤 | Expandable composition for polyurethane foam, and polyurethane foam |
| JP5422280B2 (en) * | 2009-07-13 | 2014-02-19 | 旭有機材工業株式会社 | Foamable composition for polyurethane foam and polyurethane foam |
| KR101444042B1 (en) * | 2013-11-22 | 2014-09-23 | 코오롱인더스트리 주식회사 | Novolac Resin, Hardener Comprising the Same and Epoxy Resin Composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US432716A (en) * | 1890-07-22 | Trap-lock | ||
| NL133349C (en) * | 1963-12-30 | |||
| US4195151A (en) * | 1976-11-22 | 1980-03-25 | Union Carbide Corporation | Phenol-aldehyde-amine resin/glycol curative compositions |
| US4107106A (en) * | 1976-11-22 | 1978-08-15 | Union Carbide Corporation | Phenol-aldehyde-amine resin/glycol curatives for energy absorbing polyurethanes |
| US4247655A (en) * | 1979-09-18 | 1981-01-27 | Union Carbide Corporation | Rigid and semiflexible polyurethane foams produced with phenol-aldehyde-amine resins |
| US4607521A (en) * | 1984-11-20 | 1986-08-26 | Sagami Chemical Research Center | Method of improving response characteristics of gas sensor using microwave spectrometer |
| US4769437A (en) * | 1986-12-22 | 1988-09-06 | Blount David H | Process for the production of phenolic resins |
-
1990
- 1990-11-05 JP JP29709590A patent/JP3176058B2/en not_active Expired - Fee Related
-
1995
- 1995-06-30 CN CN95108366A patent/CN1044483C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100554302C (en) * | 2004-10-20 | 2009-10-28 | 日本聚氨酯工业株式会社 | The manufacture method of polyurethane foaming body |
| CN1995109B (en) * | 2006-01-06 | 2011-04-27 | 广东科龙电器股份有限公司 | Process for preparing rigid polyurethane foams |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3176058B2 (en) | 2001-06-11 |
| CN1044483C (en) | 1999-08-04 |
| JPH04170416A (en) | 1992-06-18 |
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