CN1827663A - Soft polyurethane foam production method - Google Patents
Soft polyurethane foam production method Download PDFInfo
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- CN1827663A CN1827663A CN 200610054970 CN200610054970A CN1827663A CN 1827663 A CN1827663 A CN 1827663A CN 200610054970 CN200610054970 CN 200610054970 CN 200610054970 A CN200610054970 A CN 200610054970A CN 1827663 A CN1827663 A CN 1827663A
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Abstract
The invention provides a soft urethane foam which is characterized when compared with current ones by little environmental pollution, long durability and good fire-retardancy. The method for preparing said soft urethane foam is to proceed reaction with organic polyisocyanates (A) and polyatomic alcohol (B) on condition of foaming agent (C), catalyst (D), foam preparing agent (E) and hydrolysis inhibitor (F); and the method is characterized in that: said polyatomic alcohol is substance that contains 50-100% (by weight) of polyester polyol (B1) with the acid value lower than 0.3 mg KOH /g and the glycol contains aliphatic diol of alkyl with 1-5 carbon; catalyst contains active ammonia tertiary amine compound (D1); hydrolysis inhibitor contains carbodiimide compound (F1) and the isocyanate index at beginning of reaction is more than 100.
Description
Technical field
The present invention relates to the manufacture method of the good polyester-containing flexible polyurethane foams of a kind of hydrolytic resistance low in the pollution of the environment, ratio polyester-containing flexible polyurethane foams in the past.
Background technology
All the time, flexible polyurethane foam is used for the various fields such as cushioning material, furniture, bedclothes, carpet, clothing class, sports goods of automobile because of its elastic properties, lightweight etc. are good.Particularly used the flexible polyurethane foam (being designated hereinafter simply as ester class urethane foam) of polyester polyol to compare with the flexible polyurethane foam that has used polyether glycol usually (being designated hereinafter simply as the ethers urethane foam), because mechanical properties such as so-called tensile strength, tear strength are good, and thermotolerance is also good, therefore, skin material that is used for industrial machine material, car seat mostly etc. requires the position of weather resistance.
But intramolecularly contains the ester class urethane foam of many ester bonds, under the environment of humidity, use, and the purposes that directly contacts at people's moisture such as sweat etc., the time one is long, the problem that exists ester bond generation hydrolysis, rerum natura sharply to descend.For example, the ester class urethane foam that use has adopted the polyester polyol of Diethylene Glycol to obtain, because the wetting ability of Diethylene Glycol part, moisture is entered in the foams, under 70 ℃, the hot and humid atmosphere gas of relative humidity 90%, through about about 30 days, rerum natura sharply descended, after about 50 days, then decompose to fully and can not keep shape.
In order to improve such problem, patent documentation 1 and patent documentation 2 have proposed to use in the hydrolysis inhibitor carbodiimide compounds.In addition, patent documentation 3 proposes to have used to utilize the 2-methyl isophthalic acid, the flexible polyurethane foam of the polyester polyol of ammediol (below, slightly be called 2MPD).
[patent documentation 1] spy opens flat 9-208649 communique
[patent documentation 2] spy opens flat 5-194356 communique
[patent documentation 3] spy opens the 2002-105163 communique
But above-mentioned technology can't reach the level that requires of the hydrolytic resistance that requires on the market, the appearance of the ester class urethane foam that the expectation hydrolytic resistance is better.When in addition, foams being made and the environment of foams when using do not take in yet.
Summary of the invention
The present invention can provide a kind of flexible polyurethane foam, compares with ester class urethane foam in the past, and it is low in the pollution of the environment, and weather resistance, flame retardant resistance are good.
The present invention by the specific kind that is used for the polyester polyol of raw polyol, create conditions, hydrolysis inhibitor, catalyzer, provide a kind of low in the pollution of the environment, have the manufacture method of the flexible polyurethane foam of unexistent high-durability in the past.
That is content of the present invention relates to:
A kind of manufacture method of flexible polyurethane foam makes the reaction in the presence of whipping agent (C), catalyzer (D), surfactant (E), hydrolysis inhibitor (F) of organic polymeric polyisocyanate (A) and polyvalent alcohol (B), it is characterized in that,
Polyvalent alcohol (B) be to use the alkyl that has carbon number 1～5 in the diol component non-ethers aliphatic diol, acid number is lower than the material that the polyester polyol (B1) of 0.3mgKOH/g constitutes;
Catalyzer (D) contains isocyanate-reactive tertiary amine compounds (D1);
Hydrolysis inhibitor (F) contains carbodiimide compounds (F1);
Isocyanate index during the reaction beginning surpasses 100.
Embodiment
Be used for organic polymeric polyisocyanate of the present invention (A), be not particularly limited, can use to be generally used for the known polyisocyanate compounds that urethane foam is made.Specifically, can suitably select to use one or more of modified polyisocyanates such as the polymeric polyisocyanate of the fragrant same clan, the alicyclic ring same clan, aliphatic category and these polyurethane-modified bodies thereof, allophanate-modified body, uretdione modification body, the ester modified body of cyamelide, carbodiimide modification body, uretonimine (uretone imine) modification body, urea-modified body, biuret modified body.
Aromatic series class polymeric polyisocyanate for example has: benzylidene vulcabond (simple substance and the mixture that comprise various isomers.In addition, slightly be called TDI below), '-diphenylmethane diisocyanate (simple substance and the mixture that comprise various isomers.In addition, slightly be called MDI below), naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene vulcabond (simple substance and the mixture that comprise various isomers.In addition, slightly be called XDI below), tetramethyl-benzene diformazan vulcabond (simple substance and the mixture that comprise various isomers.In addition, slightly be called TMXDI below), poly methylene poly phenyl poly isocyanate (the following P-MDI that slightly is called) etc.
Alicyclic class polymeric polyisocyanate for example has: cyclohexyl-methane vulcabond, cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenation MDI, hydrogenation TDI, hydrogenation XDI, hydrogenation TMXDI etc.In addition, the aliphatic category polymeric polyisocyanate for example has: hexamethylene diisocyanate, lysinediisocyanate etc.
In these polyisocyanate compounds, the present invention from obtain easily, aspects such as rerum natura reactive, the ester class urethane foam that obtains consider the mixture of preferred MDI, TDI, MDI and P-MDI, preferred especially TDI.
Be used for polyvalent alcohol of the present invention (B), use be the non-ethers aliphatic diol that has the alkyl of carbon number 1～5 in the diol component, the acid number that contains 50～100 quality % in (B) is lower than the polyester polyol (B1) of 0.3mgKOH/g.(B) (B1) content in is lower than down in limited time, and the hydrolytic resistance and the physical strength of the ester class urethane foam that obtains are difficult to equilibrium.In addition, acid number (B1) surpasses last prescribing a time limit, and the hydrolysis rate of ester bond sharply raises, and is difficult to control.
(B1) number-average molecular weight is preferably 1,000～10, and 000, be preferably 1,500～6,000 especially.Its number-average molecular weight is lower than at 1,000 o'clock, and the hardness of the ester class urethane foam that obtains obviously raises, and flexibility descends.It surpasses at 10,000 o'clock, and physical strength is insufficient.In addition, average functional group number (B1) is preferably 2～6.Average functional group number is lower than at 2 o'clock, and the hardness of the ester class urethane foam that obtains is insufficient, and for a long time on foams during stress application, can not recover shape after removing destressing, and the remaining problem of so-called distortion takes place easily.Surpass at 6 o'clock, be difficult to make acid number to be lower than 0.3mgKOH/g, perhaps the number-average molecular weight step-down of (B1).
Need to prove, the average functional group number of so-called polyvalent alcohol among the present invention, be meant what functional group's number of the raw material when being used for polyvalent alcohol and making and mole number calculated, (B1) in, be that functional group's number and the mole number from functional group's number of carboxylic acid composition and mole number, pure composition calculates.
(B1) be that the low molecular polylol of the usually non-ethers aliphatic diol by containing the alkyl with carbon number 1～5 and the polycondensation of polycarboxylic acid (comprising acid anhydrides, sour halogenide) obtain.At this, so-called low molecular polylol is meant that molecular weight is 62～500 polyvalent alcohol.Aliphatic diol with alkyl of carbon number 1～5 for example has: 1, and the 2-propylene glycol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 2, the 3-butyleneglycol, the 2-methyl isophthalic acid, ammediol, 1, the 2-pentanediol, 1, the 3-pentanediol, 1, the 4-pentanediol, 2, the 3-pentanediol, 2, the 4-pentanediol, the 2-methyl isophthalic acid, the 4-butyleneglycol, 1,2-dimethyl-1, ammediol, 1,2,2-trimethylammonium-1, the 3-methyl isophthalic acid, the 2-butyleneglycol, 3-ethyl-1, ammediol, neopentyl glycol, 1, the 2-hexylene glycol, 1, the 3-hexylene glycol, 1, the 4-hexylene glycol, 1, the 5-hexylene glycol, 2, the 3-hexylene glycol, 2, the 4-hexylene glycol, 2, the 5-hexylene glycol, 3, the 4-hexylene glycol, the 2-methyl isophthalic acid, the 5-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 2-methyl-2, the 5-pentanediol, the 2-methyl isophthalic acid, the 3-pentanediol, the 3-methyl isophthalic acid, the 4-pentanediol, 3-methyl-2, the 4-pentanediol, 2,2-dimethyl-1, the 4-butyleneglycol, 2,3-dimethyl-1,4-butyleneglycol, 2-ethyl-1, the 4-butyleneglycol, 2-methyl-2-ethyl-1, ammediol, 2-propyl group-1, ammediol, 2,2-diethyl-1, ammediol, 2,2,4-trimethylammonium-1,3-pentanediol, 2,2,4-trimethylammonium-1, the 5-pentanediol, 2-ethyl-1, the 3-hexylene glycol, the 2-methyl isophthalic acid, the 8-ethohexadiol, 2,4-dimethyl-1, the 5-pentanediol, 2-ethyl-2-butyl-1, ammediol, 2,2-dipropyl-1, ammediol etc.Preferred material among the present invention, considerations such as the ester group concentration of reactivity, hydrolytic resistance and intensity when influencing esterification and during urethane esterification reaction, alkyl concentration, it is the containg branched alkyl radical aliphatic diol that has only 1 grade of hydroxyl, carbon number 1～5, preferred especially 2-methyl isophthalic acid, ammediol, 3-methyl isophthalic acid, 5-pentanediol, neopentyl glycol, 2-ethyl-2-butyl-1, ammediol.
(B1) in, can use other low molecular polylol except that the non-ethers aliphatic diol of alkyl simultaneously with carbon number 1～5.This other low molecular polylol for example has: ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1, straight chain aliphatic diols classes such as 6-hexylene glycol; Alicyclic diol such as cyclohexanediol, cyclohexanedimethanol class; Diethylene Glycol, dipropylene glycol, triethylene glycol, tripropylene glycol etc. contain the ether glycols; Three alcohols such as glycerol, TriMethylolPropane(TMP); Alkamines such as N methyldiethanol amine, N-phenyl dipropanolamine, trolamine; Monoses such as erythroglucin, wood sugar, arabinose, ribulose, glucose, fructose, seminose, semi-lactosi etc.
In the present invention, (B1) the aliphatic diol content of the alkyl with carbon number 1～5 in the diol component in is preferably 50 moles more than the %, is preferably 70 moles especially more than the %.When being lower than 50 moles of %, cause the hydrolytic resistance of the ester class urethane foam that obtains insufficient easily.
(B1) the sour composition in for example has: oxalic acid, succsinic acid, hexanodioic acid, sebacic acid, nonane diacid, dodecanedioic acid, phthalic acid, iso-phthalic acid, terephthalic acid, hexahydro-phthalic acid, fumaric acid, toxilic acid, citric acid, L-glutamic acid, aspartic acid, trihemellitic acid etc.In the present invention, when considering the viscosity of constant big, the polyester that obtains of ester group concentration, preferred hexanodioic acid, sebacic acid, nonane diacid.
Can use (B1) other polyvalent alcohol (hereinafter referred to as other polyvalent alcohol) in addition among the present invention.The number-average molecular weight of other polyvalent alcohol is preferably 1,000～10, and 000, be preferably 1,500～6,000 especially.Its number-average molecular weight is lower than at 1,000 o'clock, and the hardness of the ester class urethane foam that obtains obviously raises, and flexibility descends.It surpasses at 10,000 o'clock, and physical strength is insufficient.In addition, its average functional group number is preferably 2～6.Average functional group number is lower than at 2 o'clock, and the hardness of the ester class urethane foam that obtains is insufficient, and for a long time on foams during stress application, can not recover shape after removing destressing, and the remaining problem of so-called distortion takes place easily.Surpass at 6 o'clock, the hardness of the ester class urethane foam that obtains raises easily.
The whipping agent that uses among the present invention (C) is main component with water.Water and isocyanic ester radical reaction generate carbonic acid gas, and this carbonic acid gas helps foaming.In addition, can use lower boiling organic compound such as pentamethylene, Skellysolve A, iso-pentane, methylene dichloride, HFC-245fa, HFC-365mfc and/or use air, nitrogen, the carbonic acid gas that adopts inflation mechanism simultaneously simultaneously.
The catalyzer that uses among the present invention (D) is a kind of material that contains isocyanate-reactive tertiary amine compounds (D1).Be meant in this so-called " isocyanate-reactive ": for example have the active hydrogen base in the molecular skeleton, perhaps generate active hydrogen base etc. by hydrolysis reaction.That is, be meant final and isocyanate group is reacted with certain form, mix to chemical urethane foam.(D) (D1) content is preferably more than the 30 quality %.The catalyzer of this (D1) type, the urethane foam reacted catalyst activity low (hydrolysis of polyester polyol is inhibited for this reason) that is shaped, in addition, by further mixing in the reaction system, the volatilization and the venting of ozone, ammonia (catalyzer) tail off.
(D1) for example have: N, the N-dimethylethanolamine, N, the N-dimethylisopro panolamine, N, N dimethylamine base oxethyl ethanol, N, N-dimethyl-N '-(2-hydroxyethyl) quadrol, N, N-dimethyl-N '-(2-hydroxyethyl) propylene diamine, two (N, N dimethylamine base propyl group) amine, two (N, N dimethylamine base propyl group) Yi Bingchunan, N, N-dimethyl hexanol amine, N-methyl-N '-(2-hydroxyethyl) piperazine, 1-(2-hydroxyethyl) imidazoles, 1-(2-hydroxypropyl) imidazoles, 1-(2-hydroxyethyl)-glyoxal ethyline, 1-(2-hydroxypropyl)-glyoxal ethyline, N, N ', N "-three (dimethylamino-propyls) six hydrogen-s-triazine etc.The concrete commodity that contain (D1) composition are for example deposited TOYOCAT (registered trademark) HX-63, HX-70, RX-20, RX-21, HP (eastern Cao's system), カ オ one ラ イ ザ one (registered trademark) No.25 (flower king system), DABCO (registered trademark) DMEA, POLYCAT (registered trademark) No.17 (エ ア one プ ロ ダ Network ツ ﹠amp; ケ ミ カ Le ズ system) etc.These catalyzer can use separately, also can be used in combination of two or more.
In addition, the catalyzer that can use simultaneously among the present invention for example has: 1,8-diazabicyclo (5,4,0) undecylene-7, two (2-dimethylamino ethyl) ether, N, N, N ', N '-tetramethyl-hexamethylene-diamine, Triethylene Diamine, triethylamine, tripropyl amine, tri-isopropyl amine, Tributylamine, trioctylamine, N-methylmorpholine ketone, N-ethylmorpholine, lupetazin, N, N dimethylamine base oxethyl ethanol, N, N, N ', N ", N "-the pentamethyl-dipropanetriamine, 1, the 2-methylimidazole, 1-ethyl-glyoxal ethyline, 1-butyl-glyoxal ethyline, and the organic acid salt of these materials etc., also have stannous octoate, dibutyl tin laurate, two lauric acid dioctyl tins, zinc naphthenate, lead naphthenate, Potassium ethanoate, isovaleric acid potassium, potassium octanoate, stannous octoate, tin laurate.These catalyzer can use separately, also can be used in combination of two or more.
Be used for surfactant of the present invention (E), can use known silicone based tensio-active agent at present.Operable such silicone based tensio-active agent for example has: L-520, L-532, L-540, L-544, L-3550, L-5740S, L-5740M, the L-6202 etc. of Japanese ユ ニ カ one system; SH-190, the SH-192 of the beautiful ダ ウ コ one ニ Application グ シ リ コ one Application system in east, SH-193, SH-194, SRX-290, SRX-294A, SRX-298 etc.; TEGOSTAB (registered trademark) B8002, B4900, B8040, B8233, B8229, B8110, B8300, B8317, the B8324 etc. of the F-114 of SHIN-ETSU HANTOTAI's chemical industry system, F-121, F-122, F-230, F-258, F-260B, F-317, F-341, F-601, F-606 go one Le De シ ユ ミ Star ト system.These surfactants can use separately, also can be used in combination of two or more.In the present invention, in order to prevent volatilization and the evaporation of surfactant, preferably has the boiling point active hydrogen base or that removed low molecule oligopolymer and is the material more than 100 ℃ from foams.
Be used for surfactant of the present invention (E), can use known silicone based tensio-active agent at present.Operable such silicone based tensio-active agent for example has: SE-232, the L-520 of Japanese ユ ニ カ one system, L-532, L-540, L-544, L-3550, L-5740S, L-5740M, L-6202 etc.; SH-190, SH-192, SH-193, SH-194, SRX-290, SRX-294A, SRX-298, the PRX-607 etc. of the beautiful ダ ウ コ one ニ Application グ シ リ コ one Application system in east; TEGOSTAB (registered trademark) B8002 of the F-114 of SHIN-ETSU HANTOTAI's chemical industry system, F-121, F-122, F-230, F-258, F-260B, F-317, F-341, F-601, F-606 go one Le De シ ユ ミ Star ト system, B4900, B8040, B8233, B8229, B8110, B8300, B8301, B8317, B8324 etc.These surfactants can use separately, also can be used in combination of two or more.In the present invention, in order to prevent volatilization and the evaporation of surfactant, preferably has the boiling point active hydrogen base or that removed low molecule oligopolymer and is the material more than 100 ℃ from foams.
The invention is characterized in that its hydrolysis inhibitor (F) contains carbodiimide compounds (F1).The carbodiimide-based that exists in the carbodiimide compounds (F1) is present in the end of polyester polyol, and the carboxyl moment that produces with hydrolysis by ester group reacts.In addition, carbodiimide-based also reacts with water.Carbodiimide compounds (F1) helps the raising of the hydrolytic resistance of ester class urethane foam by utilizing such reaction mechanism.In addition, the present invention confirms: by further interpolation carbodiimide compounds (F1), can effectively improve thermotolerance.Can also effectively improve flame retardant resistance.This thinks that reaction has formed crosslinking structure between carbodiimide-based and isocyanate reaction or the carbodiimide-based.In the present invention, the content of the carbodiimide compounds (F1) in the hydrolysis inhibitor (F) is preferably more than the 50 quality %.
Such carbodiimide compounds (F1) is by the decarbonation reaction in the presence of carbodiimide catalyzer such as phospholene oxides of organic isocyanate compound is obtained.Also for example have: the single carbodiimide that obtains from organic single-isocyanate, with the part of organic diisocyanate with single alcohol or the covered polycarbodiimide of monoamine, use organic single-isocyanate and organic diisocyanate and polycarbodiimide of obtaining etc. simultaneously.The organic isocyanate compound for example has: phenyl isocyanate, tertiary butyl-organic single-isocyanates such as 1-phenyl isocyanate, aforementioned organic polymeric polyisocyanate.Concrete commodity for example have: DIPC (Kawaguchi's chemistry), ス バ Star Network ゾ one Le (registered trademark) I (バ イ エ Le), カ Le ボ ジ ラ イ ト (registered trademark) HMV-8CA (day is weaving clearly), エ ラ ス ト ス Block (registered trademark) H01 (エ ラ ス ト グ ラ Application AG) etc.Among the present invention, when the intermiscibility of considering polyvalent alcohol etc., the carbodiimide compounds of preferred TMXDI class.
In addition, among the present invention, can use other additive, for example have: fire retardant, antioxidant, UV light absorber, tinting material, pigment, antiseptic-germicide, deodorizing composition, deodorant, perfume compound etc.
Usually, the polyvalent alcohol Preblend that modulation cooperated organic polymeric polyisocyanate (A) each composition in addition in advance, make itself and organic polymeric polyisocyanate (A) mix, foam, obtain ester class urethane foam, but do not have the material of active hydrogen base also can be matched with in organic polymeric polyisocyanate (A) in surfactant (E) and the additive.In addition, because carbodiimide compounds (F1) changes and the isocyanic ester radical reaction sometimes in time, therefore, preferred (F1) is matched with in the polyvalent alcohol Preblend.
Aforesaid organic polymeric polyisocyanate (A) and polyvalent alcohol (B) are cooperated whipping agent (C), catalyzer (D), surfactant (E), each components in proportions of hydrolysis inhibitor (F), be not particularly limited.
The preferred proportioning of organic polymeric polyisocyanate (A) each composition in addition is: relative polyvalent alcohol (B) 100 mass parts, whipping agent (C) is 0.01～5 mass parts, is preferably 0.2～3 mass parts especially, catalyzer (D) is 0.5～10 mass parts, is preferably 1～8 mass parts especially, surfactant (E) is 0.1～4 mass parts, is preferably 0.4～2.0 mass parts especially, and hydrolysis inhibitor (F) is 0.1～5 mass parts, is preferably 0.3～3 mass parts especially.
The concrete manufacturing sequence of concrete ester class urethane foam of the present invention, the occasion of plate foam body, for example: the foaming machine that uses the multicomponent type of mixing tube with the rotary and high pressure collision hybrid mode of impeller, after all composition mixes in the mixing tube and in the step tempering tank, mixed solution is supplied with foaming with on container and the travelling belt, make the method for its foaming.The occasion of molded foam, for example: in having the low pressure foaming machine of mechanical stirring device, after the whole compositions in the mixing tube are mixed, make in mould that mixed solution injects, the method for foaming; Make isocyanic ester and polyvalent alcohol in mixing tube, collide the method etc. of mixing, foaming with high pressure foaming machine by high pressure.Need to prove that the temperature of preferred mould is adjusted to 30～120 ℃ in advance.
In the present invention, it is prerequisites that the isocyanate index during the reaction beginning surpasses 100, is preferably 102～110.Be meant at this so-called isocyanate index: the mole number of isocyanate group is on duty with 100 value divided by the total mole number of the isocyanate-reactive active hydrogen base that contains water.If isocyanate index is low excessively, then the physical strength of foams can reduce sometimes, in addition, compresses residual deformation sometimes and can become big.And, trace is existed and and the reactivity carboxyl littler of isocyanate group than hydroxyl be present in the ester class urethane foam, this remaining carboxyl plays a role as hydrolyst, can damage the hydrolytic resistance of foams.Need to prove that when isocyanate index was unnecessarily too high, foams had the tendency of hardening, degradation problem under feel deterioration, the shock absorbing capability takes place easily.
The density of the ester class urethane foam that obtains like this is 80kg/m
3Below, be preferably 60kg/m
3Below.Usually ester class urethane foam is compared with the ethers urethane foam with density, because mechanical properties such as intensity and hardness are big, and therefore can low densityization.
Embodiment
Below, embodiments of the invention and comparative example are elaborated, but the present invention is not limited to these embodiment.Be not specifically noted, " % " among the embodiment represents " quality % " respectively.
[synthesizing of polyester polyol]
Synthesis example 1～14
In the reactor that has stirrer, nitrogen ingress pipe, prolong, add the raw material shown in the table 1,2, at reaction conditions shown below, synthesized polyester polyol PES-1～14.
Synthesis under normal pressure: made temperature of reaction be warming up to 200 ℃ (all polyvalent alcohol is common) from 130 ℃ with 9 hours.Need to prove that interior pressure is normal pressure (101.3kPa).
The decompression reaction: behind the synthesis under normal pressure, the reaction of reducing pressure.The decompression reaction conditions is as described below.
PES-1、2、6
→ add the tetrabutyl titanate ester of the 10ppm amount be equivalent to total add-on, the limit makes temperature of reaction remain on 200 ℃, the limit with 9 hours from atmospheric depressurized to 1.3kPa.
Polyester polyol beyond above-mentioned
→ add the tetrabutyl titanate ester of the 10ppm amount be equivalent to total add-on, the limit makes temperature of reaction remain on 200 ℃, the limit with 14 hours from atmospheric depressurized to 1.3kPa.
Table 1
| Synthesis example | |||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | |
| Low molecular polylol (part) 13BD 2M13PD 2M15PD 224TM15PD NPG 14BD TMP | 209.3 274.4 26.8 | 223.9 223.9 26.8 | 207.7 240.0 44.7 | 544.9 44.7 | 418.2 26.8 | 204.4 233.8 67.1 | 411.6 7.1 |
| Dicarboxylic acid (part) AdA SeA | 649.5 | 697.0 | 673.5 | 544.6 | 675.2 | 656.3 | 691.8 |
| Dehydrating amount (part) | 160.0 | 171.7 | 165.9 | 134.1 | 120.2 | 161.7 | 170.4 |
| Title | PES-1 | PES-2 | PES-3 | PES-4 | PES-5 | PES-6 | PES-7 |
| The synthetic average functional group of acid number (mgKOH/g) hydroxyl value (mgKOH/g) number-average molecular weight number as a result | 0.20 56.1 2500 2.5 | 0.25 56.1 2500 2.5 | 0.15 56.1 3000 3.0 | 0.20 56.1 3000 3.0 | 0.20 56.1 2500 2.5 | 0.20 65.5 3000 3.5 | 0.20 65.5 3000 3.5 |
Table 2
| Synthesis example | |||||||
| 8 | 9 | 10 | 11 | 12 | 13 | 14 | |
| Low molecular polylol (part) DEG DPG 13BD 2M13PD 14BD TMP | 335.8 44.7 | 487.8 33.5 | 470.6 33.5 | 488.3 26.8 | 241.1 204.8 53.7 | 447.3 33.5 | 425.9 33.5 |
| Dicarboxylic acid (part) AdA SeA | 753.6 | 635.2 | 613.1 | 643.3 | 664.1 | 688.8 | 690.6 |
| Dehydrating amount (part) | 134.1 | 156.5 | 117.3 | 158.5 | 163.6 | 169.7 | 170.1 |
| Title | PES-8 | PES-9 | PES-10 | PES-11 | PES-12 | PES-13 | PES-14 |
| The synthetic average functional group of acid number (mgKOH/g) hydroxyl value (mgKOH/g) number-average molecular weight number as a result | 0.20 56.1 3000 3.0 | 0.50 70.1 2000 2.5 | 0.50 70.1 2000 2.5 | 0.25 56.1 2500 2.5 | 0.20 67.3 2500 3.0 | 0.20 70.1 2000 2.5 | 0.50 67.3 2500 3.0 |
In synthesis example 1～14, table 1～2,
DEG: Diethylene Glycol
DPG: dipropylene glycol
13BD: 1,3 butylene glycol
2M13PD: 2-methyl isophthalic acid, ammediol
3M15PD: 3-methyl isophthalic acid, 5-pentanediol
224TM15PD:2,2,4-trimethylammonium-1,5-pentanediol
NPG: neopentyl glycol
14BD: 1, the 4-butyleneglycol
TMP: TriMethylolPropane(TMP)
AdA: hexanodioic acid
SeA: sebacic acid
(the manufacturing evaluation of ester class urethane foam)
Embodiment 1～8, comparative example 1～7
With the stock liquid of the modulation of the cooperation shown in the table 3,4 ester class urethane foam, make the plate foam body by isocyanate index with table.Other reaction conditions is as described below.After the reaction, with the ester class urethane foam that obtains after 23 ℃ * 50%RH places 24 hours, cut into the sample shape of regulation, a part is carried out physical property measurement immediately, a part is put into controlled thermohygrostat, take out sample after specified time limit, after 23 ℃ * 50%RH places 24 hours, measure rerum natura.The long duration test condition is as described below.Need to prove, weather resistance is to estimate with half date of value that tensile strength, pull and stretch degree of stretching become the initial stage measured value, transformation period is when measuring between day for certain, draw straight line between measured value, be defined as the date of the half value of expression initial stage measured value on figure by the mensuration Japan and China before and after it.
Foaming condition
Material temperature: 25 ℃
Stirring velocity: 3000rpm
Churning time: 10 seconds
The long duration test condition
Temperature: 70 ℃
Humidity: 90RH%
Measure frequency: per 7 days
Tension test: JIS K6400
Flame retardant test: JIS K6400
Table 3
| Embodiment | |||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | ||
| Polyalcohol premix polyalcohol (part) PES-1 PES-2 PES-3 PES-4 PES-5 PES-6 PES-7 PES-8 blowing agent (part) water catalyst (part) CAT-1 CAT-2 surfactant (part) SUR-1 SUR-2 hydrolysis inhibitor (part) CAR-2 | 627.7 27.0 1.6 1.2 9.4 | 625.8 26.9 1.6 1.2 9.4 | 625.8 26.9 1.6 1.2 9.4 3.1 | 625.8 26.9 1.6 1.2 9.4 3.1 | 611.6 26.3 0.9 0.6 9.2 3.1 | 581.6 25.2 0.6 0.3 8.8 2.9 | 569.6 24.5 0.6 0.3 8.5 2.8 | 548.2 23.6 0.5 0.3 8.2 2.7 | |
| The organic polymeric polyisocyanate of isocyanic ester liquid, (part) TDI-1 MDI-1 PMDI-1 hydrolysis inhibitor, (part) CAR-1 | 333.0 3.1 | 332.0 3.1 | 332.0 | 332.0 | 278.7 69.7 | 188.1 188.1 | 118.1 275.6 | 416.4 | |
| Isocyanate index | 105 | 105 | 105 | 105 | 105 | 105 | 105 | 105 | |
| Density foam (kg/m 3) | 29 | 25 | 25 | 23 | 26 | 27 | 26 | 28 | |
| The endurance test result | Tensile strength initial value (kPa) transformation period (my god) | 158 110 | 159 105 | 180 145 | 177 141 | 219 143 | 198 136 | 180 133 | 183 130 |
| Stretch length initial value (%) transformation period (my god) | 180 119 | 188 123 | 156 161 | 160 158 | 128 144 | 139 148 | 146 133 | 152 130 | |
| Flame retardant resistance | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | |
Table 4
| Comparative example | ||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | ||
| Polyalcohol premix polyalcohol (part) PES-9 PES-10 PES-11 PES-12 PES-13 PES-14 blowing agent (part) water catalyst (part) CAT-1 CAT-2 CAT-3 CAT-4 surfactant (part) SUR-1 | 658.0 28.3 9.9 0.3 9.9 | 615.5 26.5 9.2 0.3 9.2 | 627.7 27.0 1.6 1.2 9.4 | 618.7 26.6 1.6 1.2 9.3 | 658.0 28.3 9.9 0.3 9.9 | 617.3 26.5 9.3 0.3 9.3 | 658.0 28.3 1.6 1.2 9.3 | |
| The organic polymeric polyisocyanate of isocyanic ester liquid (part) TDI-1 hydrolysis inhibitor (part) CAR-1 | 293.6 | 339.2 | 333.0 | 339.6 3.1 | 293.6 | 337.4 | 293.6 3.1 | |
| Isocyanate index | 85 | 105 | 105 | 105 | 85 | 105 | 85 | |
| Density foam (kg/m 3) | 25 | 24 | 26 | 26 | 27 | 26 | 25 | |
| The endurance test result | Tensile strength initial value (kPa) transformation period (my god) | 143 35 | 148 41 | 135 46 | 151 58 | 116 48 | 185 50 | 110 40 |
| Stretch length initial value (%) transformation period (my god) | 154 43 | 153 47 | 187 50 | 166 63 | 117 67 | 140 63 | 102 41 | |
| Flame retardant resistance | Defective | Defective | Defective | Qualified | Defective | Defective | Qualified | |
In the table 3,4,
CAT-1: the DPG solution of ammonia mixed catalyst
C1/C2/DPG=20/50/30 (mass ratio)
The non-reacted tertiary amine compounds of C1 → isocyanic ester
C2 → isocyanate-reactive tertiary amine compounds
DPG → dipropylene glycol
CAT-2: the non-reacted tertiary amine compounds of isocyanic ester (imidazoles)
CAT-3: morpholine class catalyzer
CAT-4: metallic salt catalyzer
SUR-1: hydroxyl silicon class surfactant, hydroxyl value=100mgKOH/g
SUR-2: hydroxyl silicon class surfactant, hydroxyl value=50mgKOH/g
SUR-3: silicon class surfactant, not hydroxyl
CAR-1: carbodiimide oligopolymer
Trade(brand)name: ス バ Star Network ゾ one Le, one I (バ イ エ Le system)
CAR-2:TMXDI class carbodiimide
Trade(brand)name: エ ラ ス ト ス Block H01 (エ ラ ス ト グ ラ Application system)
TDI-1:2,4-TDI/2,6-TDI=80/20 mixture
MDI-1:4,4 '-MDI/ is non-4,4 '-MDI=70/30 mixture
The PMDI-1:MDI/P-MDI=65/35 mixture
4,4 '-MDI/ is non-4,4 '-MDI=70/30
Isocyanate content=31.5%
※ is non-4,4 '-MDI → 2,2 '-MDI and 2, the summation of 4 '-MDI
As known from Table 3, by the flexible polyurethane foam that the present invention obtains,, be the material that hydrolytic resistance is good and flame retardant resistance is good as ester class urethane foam.But, not meeting the comparative example 1～4 of the prerequisite of polyester polyol, the transformation period of its stretching rerum natura is short, and hydrolytic resistance is insufficient.In addition, do not use the flame retardant resistance of comparative example 1～3,5,6 of carbodiimide compounds insufficient.In addition, the comparative example 5,7 that isocyanate index is little is materials that the initial stage rerum natura is low and transformation period rerum natura also lacks of foams.
Claims (1)
1. the manufacture method of a flexible polyurethane foam makes the reaction in the presence of whipping agent (C), catalyzer (D), surfactant (E), hydrolysis inhibitor (F) of organic polymeric polyisocyanate (A) and polyvalent alcohol (B), it is characterized in that,
Polyvalent alcohol (B) is to use the non-ethers aliphatic diol of the alkyl that has carbon number 1～5 in the diol component, and acid number is lower than the material that the polyester polyol (B1) of 0.3mgKOH/g constitutes;
Catalyzer (D) contains isocyanate-reactive tertiary amine compounds (D1);
Hydrolysis inhibitor (F) contains carbodiimide compounds (F1);
Isocyanate index during the reaction beginning surpasses 100.
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| JP2005049860 | 2005-02-25 | ||
| JP2005049860A JP2006233021A (en) | 2005-02-25 | 2005-02-25 | Manufacturing process of flexible polyurethane foam |
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| CN105682983A (en) * | 2013-10-29 | 2016-06-15 | 丰田纺织株式会社 | Method for producing vehicle seat pad |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007099854A (en) * | 2005-10-03 | 2007-04-19 | Yunimatekku Kk | Method for producing polyurethane |
| JP4993962B2 (en) * | 2006-07-24 | 2012-08-08 | 株式会社イノアックコーポレーション | Shock absorber for hard disk drive |
| JP4914855B2 (en) * | 2008-03-18 | 2012-04-11 | 株式会社イノアックコーポレーション | Water treatment carrier |
| JP5519128B2 (en) * | 2008-07-10 | 2014-06-11 | 株式会社イノアックコーポレーション | Polyurethane foam used as a carrier for water treatment |
| JP2015038162A (en) * | 2010-04-20 | 2015-02-26 | 日本ビー・ケミカル株式会社 | Polyester resin and application of the same |
| JP6513340B2 (en) * | 2014-05-21 | 2019-05-15 | 株式会社イノアックコーポレーション | Heat resistant soundproofing material |
| JP6529072B2 (en) | 2015-03-20 | 2019-06-12 | 株式会社イノアックコーポレーション | Flexible polyurethane foam |
| CN112194820B (en) * | 2020-09-25 | 2022-08-23 | 浙江映甫防护科技有限公司 | Preparation method of waterproof high-strength protective material |
| JP7608117B2 (en) | 2020-11-05 | 2025-01-06 | Ｄｉｃグラフィックス株式会社 | Liquid ink composition |
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| JPH0739456B2 (en) * | 1991-07-03 | 1995-05-01 | 東ソー株式会社 | Amine catalyst composition for producing polyurethane and method for producing polyurethane |
| JPH04258630A (en) * | 1991-02-14 | 1992-09-14 | Kao Corp | Polyol composition for urethane and flexible urethane foam |
| DE19710978A1 (en) * | 1997-03-17 | 1998-09-24 | Bayer Ag | Process for the production of semi-hard compact or cellular moldings based on PUR and their stabilization, moldings produced therefrom, and their use |
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