CN1329422C - Method for producing polyurethane integral foam materials - Google Patents

Method for producing polyurethane integral foam materials Download PDF

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Publication number
CN1329422C
CN1329422C CNB2004800029080A CN200480002908A CN1329422C CN 1329422 C CN1329422 C CN 1329422C CN B2004800029080 A CNB2004800029080 A CN B2004800029080A CN 200480002908 A CN200480002908 A CN 200480002908A CN 1329422 C CN1329422 C CN 1329422C
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weight
mixture
aethoxy sklerol
organic
ethylene oxide
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CN1771270A (en
Inventor
P·法尔克
H－J·施德尔
U·扎特勒
P·卡佩兰尼
A·特里纳施蒂希
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0033—Foam properties having integral skins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2410/00—Soles

Abstract

The invention relates to a method for producing polyurethane integral foam materials by reacting organic and/or modified organic polyisocyanates (a) with a polyetherol mixture (b) and chain extenders (c) in the presence of water and/or other expanding agents (e) and catalysts (f). The invention is characterized in that the polyetherol mixture (b) has a functionality of 2 to 3 and is comprised of: b1) at least one at least bifunctional polyetherol based on propylene oxide and/or butylene oxide and ethylene oxide with an ethylene oxide proportion of more than 40 % by weight with regard to the used total amount of alkylene oxide with an OH number ranging from 20 to 80 mg KOH/g and; b2) at least one at least bifunctional polyetherol based on propylene oxide and/or butylene oxide with an OH-number of less than 600 mg KOH/g and the reaction ensues with characteristic numbers of less than 110. The total weight of (b1) and (b3) is greater than the weight of (b2), and the proportion of chain extenders (c) is less than 15 % by weight with regard to the total weight of constituents (b) to (f). The invention also relates to polyurethane integral foam materials themselves that are produced according to this method, and to the use thereof for shoe soles, automobile safety parts and in vehicle manufacturing.

Description

Produce the method for polyurethane integral foam materials
Known and the broadly described method that is used to produce urethane foam is the organic multiple isocyanate that makes organic and/or modification, or its separately with the compound of the higher functionality that contains at least 2 hydrogen atoms such as the prepolymer of polyoxyalkylene polyamines, and/or it preferably is the organic polyhydroxy compound of 300-6000 with molecular weight, the prepolymer of Aethoxy Sklerol and suitable particularly also has molecular weight mostly to be about 400 chainextender and/or linking agent most and reacts in the presence of catalyzer, whipping agent, fire retardant, auxiliary agent and/or additive.The Kunststoff-Handbuch (resin handbook) that for example writes for the summary of producing urethane foam referring to doctor R.Vieweg and A.H  doctor chtlen, the VII volume, urethane, first version, the second edition of 1966 and nineteen eighty-three of writing by doctor G.Oertel and the third edition in 1993 (Carl Hanser Verlag, Munich).Mould (integral foams) with duo-lateral core and tight outer shroud is a kind of urethane foam of important kind, and its production is for a long time known, it is described for example referring to DE-A-1694138 DE-A-1955891 and DE-A-1769886.It also is known producing material for sole of shoe by the polyisocyanate polyaddition method, uses the sole that wherein has urethane group in the footwear industry.Make sole and produce the car safety parts and be considered to the sizable application scenario of this type products.
For example, H.Piechota and H.R  hr be at Integral schaumstoffe (integral foam plastics), Carl-Hanser-Verlag, and Munich, Vienna has delivered the summary to the integral polyurethane foams in 1975.
DE-A-19618392 has described integral foams, has wherein required the specific prepolymer as this invention integral part.That these prepolymers have is high by 4,4 '-MDI content, particularly used the Aethoxy Sklerol that contains propylene oxide.
WO-A-98/23659 discloses Aethoxy Sklerol has been used for vest, particularly in the safety shoes.The urethane that is used to produce sole that uses in this document is usually based on polyesterols, because wherein exist the sole of Aethoxy Sklerol to have inadequate oil resistant and petrol-resistance energy.In this document, the density of the outer bottom of production is greater than 800kg/m 3(the middle end, is greater than 400kg/m 3).The ethylene oxide content of these Aethoxy Sklerols that wherein provide is no more than 40 weight %.
US-A-5996253 has proposed to be used to improve the polyurethane elastomer that surging force absorbs, and these elastomericss have low rebound resilience and low hardness.Do not use whipping agent in described method, the result is that sole density is considerably high.
US-A-5996253 attempts by using controlled air cushion to influence the surging force absorptive character at the end in the footwear.Here the perforate PU material of Shi Yonging have around involucrum.
US-A-3793241 discloses the integral foams of water foaming.In this document, method is at first to produce isocyanate component by the polyisocyanates (PMDI) and the blend of TDI-polyoxyethylene glycol prepolymer.Then, the mixture with polypropylene glycol and frozen water makes this isocyanate component foaming.This method is very complicated.
DE3835193 has described the production of integral foams.In order to produce outer closely shroud, use condensable whipping agent, for example pentane.
The integral foams that DE-A-4032148 relates to is that only water foams as whipping agent.The Aethoxy Sklerol that uses is made up of the polymer polyatomic alcohol of polyvalent alcohol with ethylene oxide terminal that contains propylene oxide and filling.
WO-A-99/33893 has described a kind of sole, and owing to reactive reason, it comprises the ethylene oxide terminal of 5-35 weight %.Introduce solid particulate by using a certain amount of polymer polyatomic alcohol.
EP-A-10141098 discloses integral foams.By the feasible polyvalent alcohol that can obtain to have secondary OH group of the prepolymer variant of this working method.
US-A-4559366 uses freonll-11 to produce sole, and also uses ethylene oxide content to be up to the polyvalent alcohol of 50 weight % of used prepolymer simultaneously.
US-A-3839138 and US-A-3781231 disclose the hydrophilic foams as sole.In these files, the polyvalent alcohol that is rich in ethylene oxide is formed to the form of prepolymer.Then, the isocyanate prepolymer of generation and hydrophobicity polyol reaction, this reaction treatment process with complexity of having in the presence of frozen water is carried out.
The production integral foams is all allowed in invention listed in the prior art undoubtedly, but still has sizable improvement possibility in this class material, particularly aspect solvent resistance and surging force absorptive character.
The objective of the invention is to use tolylene diisocyanate or particularly diphenylmethanediisocyanate isomer to produce the integral polyurethane foams, these foams are easy to process and have good solvent resistance and visco-elasticity and surging force absorptive character fully.
We have found that surprisingly, can realize this purpose by using functionality as the Aethoxy Sklerol mixture (b) of 2-3, described Aethoxy Sklerol mixture (b) is composed of the following components:
B1) greater than 40 weight %, its OH value is a 20-80 milligram KOH/ gram based on total consumption of oxyalkylene at least a dual functional at least Aethoxy Sklerol based on propylene oxide and/or oxybutylene and ethylene oxide, its ethylene oxide content,
B2) at least a dual functional at least Aethoxy Sklerol based on propylene oxide and/or oxybutylene, its OH value restrains less than 600 milligrams of KOH/, and suitable,
B3) based on the dual functional at least Aethoxy Sklerol of propylene oxide and/or oxybutylene and ethylene oxide, its ethylene oxide content is lower than 25 weight % based on total consumption of oxyalkylene, its OH value is a 20-160 milligram KOH/ gram, and index is less than 110 when reacting, (b1) and gross weight (b3) greater than the gross weight of (b2), and based on the gross weight of component (b)-(g), the content of chainextender (c) is less than 15 weight %.
Therefore, the invention provides a kind of method that is used to produce the integral polyurethane foams, its organic multiple isocyanate (a) and Aethoxy Sklerol mixture (b) by making organic and/or modification, chainextender (c) and suitable words, have isocyanic ester is other compound (d) of reactive hydrogen atom in water and/or other whipping agent (e), catalyzer (f) and suitable words, other auxiliary agent and additive (g) exist down, and reaction realizes, this method comprises uses the Aethoxy Sklerol mixture (b) of functionality as 2-3, and this Aethoxy Sklerol mixture (b) is composed of the following components:
B1) greater than 40 weight %, its OH value is a 20-80 milligram KOH/ gram based on total consumption of oxyalkylene at least a dual functional at least Aethoxy Sklerol based on propylene oxide and/or oxybutylene and ethylene oxide, its ethylene oxide content,
B2) at least a dual functional at least Aethoxy Sklerol based on propylene oxide and/or oxybutylene, its OH value restrains less than 600 milligrams of KOH/, and suitable,
B3) based on the dual functional at least Aethoxy Sklerol of propylene oxide and/or oxybutylene and ethylene oxide, its ethylene oxide content is lower than 25 weight % based on total consumption of oxyalkylene, its OH value is a 20-160 milligram KOH/ gram, and index is less than 110 when reacting, (b1) and gross weight (b3) greater than the gross weight of (b2), and based on the gross weight of component (b)-(g), the content of chainextender (c) is less than 15 weight %.
The integral polyurethane foams of producing by this method itself also are provided in the present invention and they are in sole, car safety parts and the purposes in vehicle configurations.
Surprisingly, we studies show that, the use of the use of the present invention's combination of the polyvalent alcohol of described index and described ratio (b) and the chainextender of described ratio obtains integral foams, depend on the composition and the index of this system, this integral foams can produce visco-elasticity and damping performance.
On the contrary, the technician expects, uses the polyvalent alcohol of high-load oxygen enrichment ethene will produce the highly shrinkable integral foams with relevant processing problems.
Related component for using in Aethoxy Sklerol mixture (b) according to the present invention, can carry out following explanation:
Component (b1) is made up of at least a dual functional at least Aethoxy Sklerol, its OH value is a 20-80 milligram KOH/ gram based on propylene oxide and/or oxybutylene and ethylene oxide, preferred 25-60 milligram KOH/ gram, the content of ethylene oxide greater than 40 weight %, is preferably greater than 60 weight % based on total consumption of in all cases oxyalkylene.The Aethoxy Sklerol that uses advantageously has content greater than 40%, the uncle OH group of preferred 60-85%.
For this reason, can be as the example of the material of (b1): based on as ethylene glycol, glycerine or the trimethyl propane of initiator and ethylene oxide Aethoxy Sklerol as terminal.The preferred use based on ethylene glycol and/or glycerine and Aethoxy Sklerol with ethylene oxide terminal.
Suitable words except that described Aethoxy Sklerol (b1), can use other dual functional at least Aethoxy Sklerol (b3) simultaneously based on propylene oxide and/or oxybutylene and ethylene oxide, its OH value is a 20-160 milligram KOH/ gram, preferred 25-60 milligram KOH/ gram, and ethylene oxide content is lower than 25 weight % based on total consumption of the oxyalkylene under all situations, is preferably 5-23 weight %.The example that can be used for the material of this purpose is: based on the Aethoxy Sklerol as glycerine, trimethyl propane, glycol ether or the propylene glycol of initiator.
Based on the component of using (b1) and the gross weight of Aethoxy Sklerol (b3), the consumption of these Aethoxy Sklerols of component (b1) preferably is at least 50 weight %, more preferably greater than 60 weight %.
Component (b2) is made up of at least a dual functional at least Aethoxy Sklerol based on propylene oxide and/or oxybutylene, and its OH value restrains less than 600 milligrams of KOH/, preferably less than 150 milligrams of KOH/ grams.
The example that can be used as the material of (b2) here is: based on the Aethoxy Sklerol of propylene glycol, glycerine, ethylene glycol or propylene oxide.The preferred polypropylene glycol that uses based on propylene glycol or glycerine.
According to the present invention, component (b1) and use gross weight (b3) are greater than the operating weight of component (b2).(b1) and the ratio of use gross weight (b3) and (b2) operating weight advantageously greater than 4, be preferably greater than 5.5 especially.
The Aethoxy Sklerol of mentioning is by known method, and those methods that for example hereinafter will describe are produced.
According to the present invention, produce the integral polyurethane foams and will use chainextender and suitable, linking agent (c), the total amount of these reagent is lower than 15 weight % based on the gross weight of component (b)-(g) in all cases, be preferably 2-12 weight %, advantageously 3-10 weight %.
The specific chainextender (c) that uses is a difunctional compound, as glycol, and for example ethylene glycol and glycol ether, 1,4-butyleneglycol, propylene glycol and dipropylene glycol.In component (c), also can use the compound that polymer chain is cross-linked to each other simultaneously.These linking agents have the functionality greater than 2.The example of suitable linking agent is a glycerine.But any other material as chainextender and linking agent description may be used to this purpose in the literature.
Chainextender used according to the invention and suitable, the molecular weight of chain linking agent (c) is preferably 60-200 less than 300.
Except that the Aethoxy Sklerol and chainextender (c) of component (b), also can follow and use a certain amount of other compound (d) that has reactive hydrogen atom for isocyanic ester that contains.
The compound that can be used for this purpose mainly is that those have at least 2 hydrogen atoms and molecular-weight average and are at least 300 compound.Here the compound that can favourablely use is that its functionality is 2-8, and preferred 2-3 and molecular-weight average are 300-8000, those of preferred 500-5000.Here, the hydroxyl value of polyol is generally 20-250, preferred 28-60.
Be used for component (b) and polyether glycol (d) by known method production, for example by using alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or using alkali metal alcoholates such as sodium methylate, sodium ethylate, potassium ethylate or potassium isopropoxide also to add at least a 2-8 of an including hydrogen atoms simultaneously as catalyzer, the anionic polymerisation process of the starter molecules of preferred 2-6 hydrogen atoms is produced; Perhaps by using Lewis acid such as antimony pentachloride, boron fluoride etherate etc., or Fuller's earth is produced as the cationic polymerization process of catalyzer, perhaps in alkylidene group, have the oxyalkylene of 2-4 carbon atom, produce by double metal cyanide-catalyzed by one or more.For specific application scenario, also can be incorporated into the simple function group initiator in the polyether structure.
The example of suitable oxyalkylene is a tetrahydrofuran (THF), 1, and 3-propylene oxide, 1,2-or 2,3-oxybutylene, Styrene oxide 98min., preferred ethylene oxide and 1,2-propylene oxide.Described oxyalkylene can be independently, alternately use in succession or use with the form of mixture.
The example of operable starter molecules is: water, organic dicarboxylic acid such as Succinic Acid, hexanodioic acid, phthalic acid and terephthalic acid, the unsubstituted or N-of aliphatic series or aromatics is single, N, N-or N, the diamines that in alkyl, has 1-4 carbon atom of N '-dialkyl group-replacement, as quadrol unsubstituted or list or dialkyl group-replacement, diethylenetriamine, Triethylenetetramine (TETA), 1, the 3-propylene diamine, 1,3-or 1, the 4-butanediamine, 1,2-, 1,3-, 1,4-, 1,5-or 1, the 6-hexanediamine, phenylenediamine, 2,3-, 2,4-or 2,6-tolylene diamine or 4,4 '-, 2,4 '-or 2,2 '-diaminodiphenyl-methane.The example of operable other starter molecules is: alkanolamine, and as thanomin, N-methyl-or N-ehtylethanolamine, two alkanolamines, as diethanolamine, N-methyl-or N-ethyldiethanolamine, and trialkanolamine, as trolamine and ammonia.Preferred use polyfunctional, the alcohol of particularly two and/or trifunctional, as ethylene glycol, 1,2-propylene glycol, 2, ammediol, glycol ether, dipropylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane.
Polyether glycol, the functionality of preferred polyoxytrimethylene polyvalent alcohol and polyoxytrimethylene polyoxyethylene polyols is preferably 2-8, particularly 2-3, and molecular weight is 300-8000, preferred 300-6000, particularly 1000-5000, the molecular weight of suitable polyoxy tetramethylene glycol is up to about 3500.
Other suitable polyether glycol is the polyether glycol of polymkeric substance-modification, preferred grafted polyether polyol, the polyether glycol of those styrene-baseds and/or vinyl cyanide particularly, pass through vinyl cyanide, the mixture of vinylbenzene or optimization styrene and vinyl cyanide, as weight ratio is 90: 10-10: 90, the polyether glycol that preferred 70: 30-30: 70 mixture in-situ polymerization production obtains, advantageously, above-mentioned polyether glycol is produced by information given in the following patent specification: DE1111394, DE1222669 (US3304273,3383351,3523093), DE1152536 (GB1040452) and 1152537 (GB987618), otherwise be exactly the polyether glycol dispersion liquid, its disperse phase comprises for example polyureas, polyhydrazide, the urethane of tertiary-amino-containing and/or trimeric cyanamide, amount commonly used is 1-50 weight %, preferred 2-25 weight %, for the description of these polyether glycol dispersion liquids referring to for example EP-B-011752 (US4304708), US-A-4374209 and DE-A-3231497.
Except described polyether glycol, also can use the polyvalent alcohol of polyether polyamine for example and/or the other aliphatic polycarbonate that is selected from polyester polyol, polythioether polyvalent alcohol, polyesteramide, hydroxyl, perhaps the mixture of the two or more at least polyvalent alcohols of mentioning.In this case, the hydroxyl value of polyol is 20-80 normally, preferred 28-56.
The example of suitable polyester polyol can be by routine method by organic dicarboxylic acid, preferably prepare by aliphatic dicarboxylic acid with 4-6 carbon atom and polyvalent alcohol, preferred diol with 2-12 carbon atom, preferred 2-6 carbon atom with 2-12 carbon atom.Method commonly used is to make organic poly carboxylic acid and/or its derivative and polyvalent alcohol advantageously with 1: 1-1.8, preferred 1: the mol ratio of 1.05-1.2, do not having in the presence of the catalyzer or preferably in the presence of esterifying catalyst, advantageously in atmosphere such as rare gas element such as nitrogen, carbon monoxide, helium, argon gas, under 150-250 ℃, preferred 180-220 ℃ melt temperature and suitable words, polycondensation under negative pressure, up to the acid number that reaches hope, this acid number advantageously less than 10, preferably less than 2.
The example that can use and comprise the polyacetal of hydroxyl is that those can be by glycol, as glycol ether, triglycol, 4,4 '-compound of dihydroxyl ethoxy diphenyl base dimethylmethane, hexylene glycol and Formaldehyde Production.Suitable polyacetal also can be by the polymerization preparation of cyclic acetal.Having hydroxyl and operable polycarbonate is the polycarbonate of those known types own, for example by making glycol as 1, ammediol, 1,4-butyleneglycol and/or 1,6-hexylene glycol, glycol ether, triglycol or Tetraglycol 99 and diaryl carbonate are as the polycarbonate of diphenyl carbonate or phosgene reaction production.The example of polyesteramide is the condenses of being made by polyfunctional saturated and/or undersaturated carboxylic acid or acid anhydrides and polyfunctional saturated and/or undersaturated amino alcohol that is mainly straight chain, or the mixture of being made by polyvalent alcohol and amino alcohol and/or polyamines.Suitable polyether polyamine can be by above-mentioned polyether glycol by known method production.For example, can mention making the polyoxyalkylene polyol ization earlier, with the hydrogenation of nitriles (US-A-3267050) that forms, perhaps in the presence of hydrogen and catalyzer, make the part or all of amination of polyoxyalkylene polyol (DE-A-1215373) subsequently with amine or ammonia.
The compound of component (d) can use separately or use with the form of mixture.
Integral polyurethane foams of the present invention are by making said components: (b), (c) and suitable words, (d) with the organic multiple isocyanate (a) of organic and/or modification at water and/or other whipping agent (e), catalyzer (f) and suitable, other auxiliary agent and additive (g) exist and react down and produce.
According to the present invention, these foams when producing index less than 110, preferred 90-105.
To be described in detail operable other starting ingredient below.
Can be used for the organic isocyanate (a) of production integral polyurethane foams of the present invention is aliphatic series, cyclic aliphatic, araliphatic isocyanic ester, and preferred known aromatics polyfunctional isocyanate itself.
The specific example that can mention is: the alkylidene group vulcabond that has 4-12 carbon atom in alkylidene group, as dodecane-1, the 12-vulcabond, 2-ethyl tetramethylene-1, the 4-vulcabond, 2-methyl pentamethylene-1, the 5-vulcabond, tetramethylene-1, the 4-vulcabond, preferred hexa-methylene-1,6-vulcabond, cycloaliphatic diisocyanates, as hexanaphthene-1,3-and-1,4 vulcabond, and anyly wish mixture by what these isomer were formed, 1-isocyanate group-3,3,5-trimethylammonium-5-isocyanate group methylcyclohexane (IPDI), hexahydrotoluene 2,4-and 2,6-vulcabond, and corresponding isomer mixture, dicyclohexyl methyl hydride 4,4 '-, 2,2 '-and 2,4 '-vulcabond, and corresponding isomer mixture, preferred aromatics two-and polyisocyanates, as toluene 2,4-and 2,6-vulcabond and corresponding isomer mixture, ditan 4,4-, 2,4 '-and 2,2 '-vulcabond and corresponding isomer mixture, by ditan 4,4 '-and 2,2 '-mixture that vulcabond is formed, polyphenylene polymethylene polyisocyanates, by ditan 4,4 '-, 2,4 '-and 2,2 '-vulcabond and the mixture (thick MDI) of polyphenylene polymethylene polyisocyanates composition and the mixture of forming by thick MDI and tolylene diisocyanate.Organic two-and polyisocyanates can use separately or use with the form of its mixture.
The preferred tolylene diisocyanate that uses, diphenylmethanediisocyanate mixture of isomers, the mixture of diphenylmethanediisocyanate and thick MDI or tolylene diisocyanate and diphenylmethanediisocyanate and/or thick MDI.Preferred especially use contain the above ditan 2,4 of 30 weight % '-mixture of vulcabond.
Also usually use so-called modification polyfunctional isocyanate, promptly by organic two-and/or product of obtaining of the chemical reaction of polyisocyanates.Can mention and comprise two of ester group, urea groups, biuret groups, allophanate group, carbodiimide, isocyanuric acid ester group, uretdion and/or urethane group-and/or polyisocyanates.Operable specific example is: the ditan 4 of modification, 4 '-vulcabond, the ditan 4 of modification, 4 '-and 2,4 '-mixtures of diisocyanates, the thick MDI of modification or toluene 2,4-or 2, the 6-vulcabond, comprising urethane group and NCO content is 43-15 weight % based on gross weight, preferred 31-21 weight %'s is organic, preferred aromatic polyisocyanate, for example low-molecular-weight glycol, triol, two aklylene glycols, three aklylene glycols or molecular weight are up to 6000, particularly molecular weight is up to the reaction product of 1500 polyoxyalkylene diols, wherein these can be separately with two-or the form of polyoxyalkylene diols or use with the form of mixture.The example that can mention is: glycol ether, dipropylene glycol, polyoxyethylene glycol, polyoxypropylene diols, polyoxyethylene polyoxypropylene two pure and mild corresponding triol and/or tetrols.Other suitable material is to comprise the NCO group and NCO content is 25-3.5 weight % based on gross weight, the prepolymer of preferred 21-14 weight %, it is by polyester and/or be preferably as follows described polyether glycol and ditan 4,4 '-vulcabond, ditan 2,4 '-and 4,4 '-mixture of vulcabond, toluene 2,4-and/or 2,6-vulcabond or thick MDI preparation.Being proved to be other material that can successfully use is to comprise carbodiimide group and/or isocyanurate ring and NCO content to be 43-15 weight % based on gross weight, the liquid polyisocyanate of preferred 31-21 weight %, as those based on ditan 4,4 '-, 2,4 '-and/or 2,2 '-vulcabond and/or toluene 2,4-and/or 2, the liquid polyisocyanate of 6-vulcabond.
The polyisocyanates of modification can be mixed with each other or with unmodified organic multiple isocyanate, as ditan 2,4 '-or 4,4 '-vulcabond, thick MDI or toluene 2,4-and/or 2, the 6-vulcabond mixes.
The organic multiple isocyanate that has been proved to be successful especially modification is the prepolymer that contains NCO, it advantageously by at least a portion component (a) and (b) and suitable words, (c), (d) and/or (e), the component reaction that particularly comprises certain at least content component (b1) forms.
According to the present invention, based on the gross weight of component (b)-(e), usage ratio is 1-10 weight % in all cases, preferred 0.1-5 weight %, and the water of preferred especially 0.1-2 weight % is as whipping agent (e).
Water can with the adding that combines of other conventional whipping agent, the example that can be used for the conventional whipping agent of this purpose is known Chlorofluorocarbons (CFCs) of polyurethane chemistry (CFC) and highly fluorinated and/or fluoridized hydrocarbon, but because environment reason, their use will be subjected to serious restriction or by total ban.Except HCFC and HFC, operable in addition whipping agent particularly aliphatic series and/or cyclic aliphatic hydrocarbon, particularly pentane and pentamethylene, perhaps acetal such as methylal.These pneumatogens join in the polyol component of described system usually.But they also can be added in the isocyanate component, perhaps join in the middle of polyol component and the isocyanate component by combined method.Also they and highly fluorinated and/or fluoridized hydrocarbon can be used with the form of polyol component emulsion together.If use emulsifying agent, this emulsifying agent normally its side group are polyoxyalkylene residue and fluoroalkane residue and its fluorine content low-polyacrylates for about 5-30 weight %.This series products is well-known in the plastic chemistry, as knowing from EP-A-0351614.Outside dewatering, whipping agent that uses or the suitable words of the amount of blowing agent blends advantageously are 1-10 weight % based on the gross weight of component (b)-(e) in all cases here, preferred 1-3 weight %.
Especially those can obviously promote hydrogen atoms, particularly component (b), (c), (d) and (e) compound of the reaction of the compound of middle hydroxyl and organic multiple isocyanate (a) (suitable words are modified polyisocyanate (a)) with the compound of the catalyzer that acts on production integral polyurethane foams of the present invention (e).
Can use organometallic compound, preferably have machine tin compound, the tin salt of organic carboxyl acid for example, as the inferior tin of stannous acetate, stannous octoate, ethyl stannous caproate or lauric acid, the perhaps dialkyl tin of organic carboxyl acid (IV) salt is as dibutyltin diacetate, dibutyl tin laurate, toxilic acid dibutyl tin or oxalic acid dioctyl tin.Organometallic compound uses separately, perhaps preferably is used in combination with strong basicity amine.The example that can mention be amidine as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amine such as triethylamine, Tributylamine, dimethyl benzylamine, the N-methyl-, the N-ethyl, N-cyclohexyl morpholine, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N, N ', N '-tetramethyl butane diamine, N, N, N ', N '-tetramethyl--1, the 6-hexanediamine, five methyl diethylentriamine, tetramethyl-diamino ethyl ether, two (dimethylaminopropyl) urea, lupetazin, 1, the 2-methylimidazole, 1-azabicyclo [3.3.0] octane, preferred 1,4-diazabicyclo [2.2.2] octane and amino-alkane alkylol cpd, as trolamine, tri-isopropanolamine, the N-methyl-and N-ethyldiethanolamine and dimethylethanolamine.
Operable other catalyzer is: three (dialkyl aminoalkyl)-s-Hexahydrotriazines, three (N particularly, the N-dimethylaminopropyl)-the s-Hexahydrotriazine, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, alkali metal hydroxide such as sodium hydroxide and alkali metal alcoholates such as sodium methylate and potassium isopropoxide, and have an alkali metal salt that 10-20 carbon atom and suitable words have the longer chain fatty acid of sidepiece OH group.
Based on the gross weight of component (b)-(g), preferably use 0.001-5 weight %, the particularly catalyzer of 0.05-2 weight % or catalyst combination.
Suitable, other auxiliary agent and/or additive (g) also can be incorporated into the reaction mixture that is used for production integral polyurethane foams of the present invention.The example that can mention is a fire retardant, stablizer, and filler, dyestuff, pigment and hydrolysis stabilizer, and make mould material and antibacterial substance.
The example of suitable fire retardant is a Tritolyl Phosphate, tricresyl phosphate (2-chloroethyl) ester, tricresyl phosphate (2-chloropropyl) ester, ethylene phosphoric acid four (2-chloroethyl) ester, the methanephosphonic acid dimethyl esters, diethanolamino methyl-phosphorous acid diethyl ester, and commercially available halogen-containing fire-retardant polyvalent alcohol.Except the phosphoric acid ester of above-mentioned halogen-replacement, can also use inorganic or organic fire-retardant, as red phosphorus, hydrated alumina, ANTIMONY TRIOXIDE SB 203 99.8 PCT, arsenic powder, ammonium polyphosphate and calcium sulfate, expanded graphite or cyanuric acid derivative, as trimeric cyanamide, or the mixture of at least two kinds of fire retardants, as ammonium polyphosphate and trimeric cyanamide, otherwise be exactly suitable words, W-Gum or ammonium polyphosphate, trimeric cyanamide and expanded graphite and/or suitable, aromatic polyester is to provide flame retardant resistance to the polyisocyanate polyaddition product.Add trimeric cyanamide and be proved to be effective especially here.For the component (b)-(g) of per 100 weight parts, use the 5-50 weight part, the preferred mentioned fire retardant of 5-25 weight part has been proved to be favourable usually.
Stablizer especially comprises surfactant, promptly promotes the material of initiator homogenizing and suitable, also is suitable for regulating the foam structure of plastics.For example, can mention emulsifying agent, sodium salt as the Viscotrol C sulfuric ester, or lipid acid, and the salt of lipid acid and amine, as oleic acid diethyl amine salt, the stearic acid diethanolamine salt, the ricinoleic acid diethanolamine salt, sulfonate is as basic metal or ammonium and dodecylbenzene-or the salt of dinaphthyl methane-disulfonic acid and ricinoleic acid; The foams stablizer, as siloxanes-oxyalkylene group multipolymer and other organopolysiloxane, the ethylating alkylphenol of oxygen, the ethylating Fatty Alcohol(C12-C14 and C12-C18) of oxygen, paraffin oil, castor-oil plant grease, ricinoleate ester, sulfonated castor oil and peanut oil, and abscess conditioning agent are as paraffin, Fatty Alcohol(C12-C14 and C12-C18) and dimethyl polysiloxane.The stablizer that uses mainly includes the machine polysiloxane, and they are water miscible.Here, the polydimethylsiloxane group has the grafting polyether chain of being made up of ethylene oxide and propylene oxide in the above.The common usage quantity of surfactant is the 0.01-5 weight part based on the component (b)-(g) of 100 weight parts.
Filler, the filler that particularly has strengthening action are known substances own, and they are conventional organic and mineral fillers, strengthening agent, and weighting agent is used to improve the reagent etc. of the abrasiveness of lacquer, coating composition.Each example that can mention is: mineral filler, and silicate minerals for example, as phyllosilicate, such as antigorite, serpentine, hornblende, amphibole, chrysotile and talcum; Metal oxide, as kaolin, aluminum oxide, titanium dioxide and ferriferous oxide; Metal-salt is as chalk and Schwerspat; Mineral dye is as Cadmium Sulfide and zinc sulphide; And glass etc.Other material that uses is kaolin (potter's clay), the coprecipitate of pure aluminium silicate and barium sulfate and pure aluminium silicate, and natural and synthetic fibering mineral, and as wollastonite, the glass fibre of steel fiber, particularly different lengths, its suitable words can be classified.The example of operable organic filler is: carbon, rosin, cyclopentadienyl resins and graftomer, and cellulosic fibre, tynex, polyacrylonitrile fibre, polyurethane fiber and based on aromatics and/or aliphatic dicarboxylic ester's trevira, particularly carbon fiber.Inorganic and organic filler can be used separately or use as mixture.Weight based on component (a)-(g), although can reach 80 weight % by amount natural or pad, non-woven fabrics and fabric that synthon are made is the highest, but the amount that inorganic and organic filler is incorporated in the reaction mixture advantageously is 0.5-50 weight %, preferred 1-40 weight %.
About the more detailed data of above-mentioned other conventional auxiliary agent and additive can be obtained by technical literature, for example from J.H.Saunders and K.C.Frisch, " superpolymer ", the XVI volume, urethane, the 1st and 2 parts, Verlag Interscience Publishers, obtained in 1962 and 1964, perhaps referring to Kunststoff-handbuch cited above, urethane, the VII volume, Hanser-VerlagMunich, Vienna, 1-3 version.
In order to produce integral foams of the present invention, make the organic multiple isocyanate (a) of organic and/or modification, Aethoxy Sklerol mixture (b), chainextender (c) and suitable words, have other compound (d) and other component (e)-(g) reaction that isocyanic ester are reactive hydrogen atom, index is 90-110, preferred 95-105.Here, the equivalence ratio of total hydrogen atoms is 0.90-1.10 in middle NCO group of polyisocyanates (a) and the component (b)-(g): 1, and preferred 0.95-1.05: 1.
The integral polyurethane foams of the inventive method are advantageously by single injecting method production, for example in the mould of opening or closing, for example in the metal die by high pressure or low-voltage technology production.
Verifiedly particularly advantageous be, use the two-pack method and starting ingredient (b)-(g) is mixed to obtain so-called polyol component (this also often is called component A), with the organic multiple isocyanate (a) that uses organic and/or modification, preferred especially NCO prepolymer or this prepolymer and other polyisocyanates and suitable, the mixture of whipping agent (e) is as isocyanate component (this also often is called B component).
With each starting ingredient 15-90 ℃, preferred 20-60 ℃, particularly mix under 20-35 ℃ the temperature, be incorporated into then in the mould of unlatching, perhaps suitable words are incorporated in the mould of closing under elevated pressure, perhaps under the unitary situation of operate continuously, be incorporated on the travelling belt that receives reaction mixture.Mixing process can be mechanical, for example by agitator, by mixing screw, perhaps mixes by the high pressure mixing with nozzle and realizes.Die temperature advantageously is 20-110 ℃, preferred 30-60 ℃, and particularly 35-55 ℃.
The density of the integral foams of producing by the inventive method is 100-800kg/m 3, preferred 250-600kg/m 3
Their Shore A hardness is lower than 20, is preferably 5-15.The result is the flexible foam body structure that obtains having damping performance.Shore A hardness is measured according to DIN 53505.
The swelling capacity of integral foams in hydrocarbon is lower than 10%, is preferably 1-5%.This means that these foams are suitable for having the occasion of these media.Storing 5 minutes in pentamethylene after, swelling capacity measures (as the increase of volume).
Integral foams of the present invention has good solvent resistance and excellent surging force absorptive character.
They are particularly suitable for sole, perhaps are used for the car safety parts, perhaps are used for vehicle configurations.
The present invention will describe by given embodiment, but they do not constitute any restriction.
Embodiment:
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Polyvalent alcohol b1 PTS (weight) 79.10 74.10 74.10 78.00 74.10
Polyvalent alcohol b3 PTS (weight) 2.00 2.00 2.00 2.00 2.00
Polyvalent alcohol b2 PTS (weight) 12.00 12.00 12.00 12.00 12.00
The silicon stablizer PTS (weight) 2.50 2.50 2.50 2.50 2.50
Lupragen N 201 PTS (weight) 0.40 0.40 0.40 - 0.40
Lupragen N 206 PTS (weight) 0.50 0.50 0.50 0.30 0.50
Water PTS (weight) 0.50 0.50 0.50 0.70 0.50
Ethylene glycol PTS (weight) 3.00 8.00 8.00 -
1, the 4-butyleneglycol PTS (weight) 8.00
Density kg/m 3 435 448 453 428 439
Shore A (after the demoulding) 10 15 13 7 12
Tensile strength kPa 247 741 1132 201 358
Tension strain during fracture ％ 83 234 353 85 136
Tear-resistant extensibility N/mm 0.92 2.58 3.01 0.73 1.19
Swelling capacity ％ 9 ＜1 2 n.d. n.d.
Measure swelling capacity (according to the increase of volume) after in pentamethylene, storing 5 minutes.
Isocyanate component (index of Shi Yonging all is 98 in all cases):
Embodiment 1,2 and 4: isocyanate mixture is by 20 parts of lupranat MI, 20 parts of Lupranat M20A and 60 parts of Lupranat MES forms;
Embodiment 3:NCO content is the NCO prepolymer of 20.5 weight %;
Embodiment 5: isocyanate mixture is by 80 parts of Lupranat MI and 20 parts of Lupranat M20A forms.
Polyvalent alcohol b1: based on the Aethoxy Sklerol of propylene oxide and ethylene oxide (73 weight %), the OH value is 42 milligrams of KOH/ grams, BASF;
Polyvalent alcohol b2: based on the Aethoxy Sklerol of propylene oxide, the OH value is 56 milligrams of KOH/ grams, BASF;
Polyvalent alcohol b3: based on the Aethoxy Sklerol of propylene oxide and ethylene oxide (14 weight %), the OH value is 36 milligrams of KOH/ grams, BASF;
Silicon stablizer-B8409 (deriving from Goldschmidt company);
Lupragen N201, N206-catalyzer (BASF).

Claims (12)

1. method that is used to produce the integral polyurethane foams, comprise the organic multiple isocyanate (a) and Aethoxy Sklerol mixture (b) that make organic and/or modification, chainextender (c) and suitable words, have isocyanic ester is other compound (d) of reactive hydrogen atom in water and/or other whipping agent (e), catalyzer (f) and suitable words, there are reaction down in other auxiliary agent and additive (g), this method comprises uses the Aethoxy Sklerol mixture (b) of functionality as 2-3, and this Aethoxy Sklerol mixture (b) is composed of the following components:
B1) greater than 40 weight %, its OH value is a 20-80 milligram KOH/ gram based on total consumption of oxyalkylene at least a dual functional at least Aethoxy Sklerol based on propylene oxide and/or oxybutylene and ethylene oxide, its ethylene oxide content,
B2) at least a dual functional at least Aethoxy Sklerol based on propylene oxide and/or oxybutylene, its OH value restrains less than 600 milligrams of KOH/, and suitable,
B3) based on the dual functional at least Aethoxy Sklerol of propylene oxide and/or oxybutylene and ethylene oxide, its ethylene oxide content is lower than 25 weight % based on total consumption of oxyalkylene, and its OH value is a 20-160 milligram KOH/ gram,
And index is less than 110 when reacting, (b1) and gross weight (b3) greater than the gross weight of (b2), and based on the gross weight of component (b)-(g), the content of chainextender (c) is less than 15 weight %.
2. the process of claim 1 wherein that the content of the uncle OH group in the component (b1) is greater than 40%.
3. claim 1 or 2 method, wherein difunctional compound is as chainextender (c).
4. claim 1 or 2 method, wherein (b1) and gross weight (b3) and the ratio of (b2) weight are greater than 4.
5. claim 1 or 2 method, index is 90-105 when wherein producing foams.
6. claim 1 or 2 method, use therein organic and/or modification organic multiple isocyanate (a) comprises tolylene diisocyanate, the diphenylmethanediisocyanate mixture of isomers, the mixture of diphenylmethanediisocyanate and polyphenylene polymethylene polyisocyanates, or the mixture of tolylene diisocyanate and diphenylmethanediisocyanate and/or polyphenylene polymethylene polyisocyanates.
7. claim 1 or 2 method, use therein organic multiple isocyanate (a) organic and/or modification comprises by isocyanic ester (a) and Aethoxy Sklerol (b) and suitable, the prepolymer that contains NCO that component (c)-(e) reaction forms.
8. integral polyurethane foams, it can be according to any one described production of claim 1-7.
9. the integral polyurethane foams of claim 8, its Shore A hardness is less than 20.
10. claim 8 or 9 integral polyurethane foams, its swelling coefficient in hydrocarbon is lower than 10%.
11. any one the purposes of integral polyurethane foams in sole or vehicle configurations of claim 8-10.
12. any one the purposes of integral polyurethane foams in the car safety parts of claim 8-10.
CNB2004800029080A 2003-01-27 2004-01-21 Method for producing polyurethane integral foam materials Expired - Fee Related CN1329422C (en)

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ITMI20101084A1 (en) * 2010-06-16 2011-12-16 Dow Global Technologies Inc POLYURETHANE SOLES OF SHOES PREPARE USING PROPYLENE OXIDE-BASED POLYOLS
CN102875766A (en) * 2012-09-24 2013-01-16 吴江市信许塑料鞋用配套有限公司 Preparation method of shock absorption sole material
CN102898618A (en) * 2012-09-24 2013-01-30 吴江市信许塑料鞋用配套有限公司 Preparation method of shock-absorbing sole material
CN103072232A (en) * 2012-12-13 2013-05-01 杨厚基 Processing and equipment for producing polyurethane heat insulation board by discarded leftover bits and pieces
CN105418888A (en) * 2015-12-16 2016-03-23 芜湖馨源海绵有限公司 Sponge for shoe upper and preparation process of sponge
CN111848905A (en) * 2020-06-10 2020-10-30 武汉希睿思新材料科技有限公司 Porous polyurethane foaming damping material and preparation method thereof

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