CN103030781A - Microcellular polyurethane elastomer, its preparation method and application - Google Patents
Microcellular polyurethane elastomer, its preparation method and application Download PDFInfo
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- CN103030781A CN103030781A CN2011102912164A CN201110291216A CN103030781A CN 103030781 A CN103030781 A CN 103030781A CN 2011102912164 A CN2011102912164 A CN 2011102912164A CN 201110291216 A CN201110291216 A CN 201110291216A CN 103030781 A CN103030781 A CN 103030781A
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
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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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0033—Foam properties having integral skins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0066—≥ 150kg/m3
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a microcellular polyurethane elastomer, which is a reaction product of the following components: (a) one or more isocyanate prepolymers; (b) one or more polyols; and (c) one or more foaming agents. Specifically, the isocyanate prepolymers are reaction products the following components: (a1) one or more isocyanates; and (a2) one or more polymer polyether polyols. The invention also provides a preparation method of the microcellular polyurethane elastomer and its application.
Description
Technical field
The present invention relates to microporous polyurethane elastomer, be specifically related to a kind of low density polyurethane micropore elastomer and its production and use.
Background technology
By density less than 400kg/m
3The sole of microporous polyurethane elastomer preparation usually be classified as the low density sole.The low density sole not only can reduce material cost, and end article footwear weight is lighter, has better snugness of fit.
At present, usually reduce the density of gained microporous polyurethane elastomer in this area by the amount that increases whipping agent in the polyurethane formulations, still, along with the microcellular elastomeric volume density is reduced to 400kg/m
3Below, gained microporous polyurethane elastomer physical property and epidermis quality be variation also, and the dimensional stability variation.
In addition, well known in the artly polyether glycol is added into the polyester polyol formula system can improves the elastomeric dimensional stability of low-density polyurethane.For example, US3902959 discloses a kind of low density polyurethane micropore elastomer by polyester type isocyanic ester performed polymer and polyether glycol reaction gained.EP0358328 discloses a kind of isocyanic ester performed polymer composition and polyurethane elastomer prepared therefrom.Although the microporous polyurethane elastomer of these method gained has lower density and good dimensional stability, its physical property and epidermis quality are still undesirable.
US2007/0179208A1 discloses the low density polyurethane micropore elastomer based on polymer polyester polyol, yet, the dimensional stability of microporous polyurethane elastomer is undesirable, and, the viscosity of polymer polyester polyol is very high (for example, the Hoopol PM245 viscosity that Synthesia company produces is up to 5000cps@60deg C), be unfavorable for operation.
CN20101020480 discloses a kind of density and has been about 500kg/m
3Polyurethane elastomer, this polyurethane elastomer adds polyol component and makes with the isocyanate component reaction by containing polyether polyol, the elastomeric physical property and the epidermis quality that still make are still undesirable.
The polyurethane foam pore-creating agent also can be for the preparation of low density polyurethane micropore elastomer.But the elastomerics that the method makes does not have desirable physical property and epidermis quality equally.
Therefore, still need both had lower density at present, have again the microporous polyurethane elastomer of good dimensional stability, physical property and epidermis character.
Summary of the invention
One aspect of the present invention provides a kind of polyurethane elastomer, is the product that comprises the reacted constituent reaction gained of following ingredients (a)-(c):
(a) one or more isocyanic ester performed polymers are the product that comprises following (a1) and the reaction of reacted constituent (a2) gained;
(a1) one or more isocyanic ester; With
(a2) one or more polyether polyols;
(b) one or more polyvalent alcohols; With
(c) one or more whipping agents,
At least a one or more polyester polyols that contains in the reacted constituent of wherein said isocyanic ester performed polymer or the described reacted constituent (b).
In a preferred embodiment, the content of described reacted constituent (a2) is 10%-35%, take the weight of described isocyanic ester performed polymer as 100%.
In a preferred embodiment, the content of the NCO of described reacted constituent (a) is 10%-25%, take the weight of reacted constituent (a) as 100%.
In a preferred embodiment, polymer solids content is 20%-45% in the described reacted constituent (a2), and take the weight of described reacted constituent (a2) as 100%, hydroxyl value is 20-50mgKOH/g.
In a preferred embodiment, described polyester polyol molecular weight is 1000-3000, and functionality is 2.0-3.0.
In a preferred embodiment, the density of described polyurethane elastomer is 120kg/m
3-400kg/m
3
The present invention provides a kind of method for preparing polyurethane elastic body on the other hand, comprises the step that makes the reacted constituent reaction that comprises following ingredients (a)-(c):
(a) one or more isocyanic ester performed polymers are the product that comprises following (a1) and the reaction of reacted constituent (a2) gained;
(a1) one or more isocyanic ester; With
(a2) one or more polyether polyols;
(b) one or more polyvalent alcohols; With
(c) one or more whipping agents,
At least a one or more polyester polyols that contains in the reacted constituent of wherein said isocyanic ester performed polymer or the described reacted constituent (b).
In a preferred embodiment, the content of described reacted constituent (a2) is 10%-35%, take the weight of described isocyanic ester performed polymer as 100%.
In a preferred embodiment, the content of the NCO of described reacted constituent (a) is 10%-25%, take the weight of described reacted constituent (a) as 100%.
In a preferred embodiment, polymer solids content is 20%-45% in the described reacted constituent (a2), and take the weight of described reacted constituent (a2) as 100%, hydroxyl value is 20-50mg KOH/g.
In a preferred embodiment, described polyester polyol molecular weight is 1000-3000, and functionality is 2.0-3.0.
In a preferred embodiment, the density of described polyurethane elastomer is 120kg/m
3-400kg/m
3
The present invention also has been to provide the purposes of above-mentioned polyurethane elastomer for the preparation of sole, carpet, cylinder, sealed strip, coating, tire, wiper, bearing circle or packing ring in an aspect.
The present invention also is to provide a kind of sole in an aspect, and described sole is made by above-mentioned polyurethane elastomer.
Embodiment
In practice, the applicant is surprised to find that polyether polyol is added in the isocyanic ester prepolymer reaction composition that obtained low density polyurethane micropore elastomer has good dimensional stability, physical property and epidermis quality simultaneously.
In the present invention, the low-density polyurethane elastomerics refers to that density is 120kg/m
3-400kg/m
3Polyurethane elastomer.
Microporous polyurethane elastomer
Microporous polyurethane elastomer provided by the invention is the product that comprises the reacted constituent reaction gained of following ingredients (a)-(c):
(a) one or more isocyanic ester performed polymers are the product that comprises following (a1) and the reaction of reacted constituent (a2) gained;
(a1) one or more isocyanic ester; With
(a2) one or more polyether polyols;
(b) one or more polyvalent alcohols; With
(c) one or more whipping agents,
At least a one or more polyester polyols that contains in the reacted constituent of wherein said isocyanic ester performed polymer or the described reacted constituent (b).Be to comprise polyester polyol in the reacted constituent of isocyanic ester performed polymer, perhaps comprise polyester polyol in (b) one or more polyvalent alcohols, perhaps both comprise polyester polyol.
Preferably, the content of the NCO of described isocyanic ester performed polymer is 10%-25%, take the weight of described isocyanic ester performed polymer as 100%.
(a1) of the present invention one or more isocyanic ester can be used general formula R (NCO)
nThe expression, wherein R represent to contain 2-18 carbon atom aliphatic alkyl, contain the aryl of 6-15 carbon atom or contain 8-15 carbon atom aryl aliphatic hydrocarbyl, n=2-5.
Described isocyanic ester, preferred but be not limited to the vinyl vulcabond, tetramethylene 1, the 4-vulcabond, hexamethylene diisocyanate (HDI), dodecyl-1, the 2-vulcabond, tetramethylene-1, the 3-vulcabond, hexanaphthene-1, the 3-vulcabond, hexanaphthene-1, the 4-vulcabond, 1-isocyanate group-3,3,5-trimethylammonium-5-isocyanate group methylcyclohexane, hexahydrotoluene-2, the 4-vulcabond, hexahydrobenzene base-1, the 3-vulcabond, hexahydrobenzene base-1, the 4-vulcabond, perhydro-ditane-2, the 4-vulcabond, perhydro-ditane-4, the 4-vulcabond, phenylene-1, the 3-vulcabond, phenylene-1, the 4-vulcabond, durene-1, the 4-vulcabond, stibene-1, the 4-vulcabond, 3,3 '-dimethyl-4,4 '-diphenyl diisocyanate, Toluene-2,4-diisocyanate, 4-vulcabond (TDI), Toluene-2,4-diisocyanate, 6-vulcabond (TDI), ditane-2,4 '-vulcabond (MDI), ditane-2,2 '-vulcabond (MDI), ditane-4,4 '-vulcabond (MDI), naphthylene-1，5-diisocyanate (NDI), their mixture, their isomer, or the mixture of they and they isomer.
Described isocyanic ester, also comprise the polyisocyanates with carbonization imines, allophanate or isocyanate-modified gained, preferred but be not limited to '-diphenylmethane diisocyanate, imine modified '-diphenylmethane diisocyanate, their mixture, their isomer or the mixture of they and they isomer of carbonization.
Described isocyanic ester can also be the isocyanic ester performed polymer.The NCO content of described isocyanic ester performed polymer, preferred but be not limited to 5-30wt.%, 10-25wt.% particularly preferably, in the weight of described isocyanic ester performed polymer by 100wt.%.
Described polyether polyol is the polyether glycol of polymer modification, preferred grafted polyether polyol, polyether glycol dispersion.Described grafted polyether polyol is preferably based on the grafted polyether polyol of vinylbenzene and/or vinyl cyanide; Described vinylbenzene and/or vinyl cyanide can be formed by the mixture in-situ polymerization of vinylbenzene, vinyl cyanide, vinylbenzene and vinyl cyanide; In the mixture of described vinylbenzene and vinyl cyanide, vinylbenzene is 90 with the ratio of vinyl cyanide: 10-10: 90, preferred 70: 30-30: 70.Described polyether polyol dispersion comprises disperse phase, for example, and without based filler, polyureas, polyhydrazide, contain the urethane of bonding scheme uncle amino group and/or trimeric cyanamide.The amount of described disperse phase is 1-50wt.%, preferred 1-45wt.%, in the weight of polyether polyol by 100wt.%.Preferably polymer solids content is 20%-45% in the polyether polyol, and take described polyether weight as 100%, hydroxyl value is 20-50mgKOH/g.Those skilled in the art know the measuring method of hydroxyl value, for example at Houben Weyl, and Methoden der Organischen Chemie, vol.XIV/2 Makromolekulare Stoffe, p.17, Georg Thieme Verlag; Disclosed among the Stuttgart 1963.The full content of the document is integrated with herein by reference.Preferably, the content of polyether polyol is 10%-35%, take isocyanic ester weight as 100%.
Described polyester polyol is made by di-carboxylic acid or dicarboxylic acid anhydride and polyol reaction.Described di-carboxylic acid, preferred but be not limited to contain the aliphatic carboxylic acid of 2-12 carbon atom, the described aliphatic carboxylic acid that contains 2-12 carbon atom, preferred but be not limited to Succinic Acid, propanedioic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, dodecyl carboxylic acid, maleic acid, FUMARIC ACID TECH GRADE, phthalic acid, m-phthalic acid, terephthalic acid or their mixture.Described dicarboxylic acid anhydride, preferred but be not limited to Tetra hydro Phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride or their mixture.The polyvalent alcohol of described and di-carboxylic acid or di-carboxylic acid anhydride reactant, preferred but be not limited to ethylene glycol, glycol ether, 1,2-propylene glycol, 1, ammediol, dipropylene glycol, 1,3-methyl propanediol, BDO, 1,5-PD, 1,6-hexylene glycol, neopentyl glycol, decamethylene-glycol, glycerol, TriMethylolPropane(TMP) or their mixture.Described polyester polyol also comprises the polyester polyol by the lactone preparation.Described polyester polyol by lactone preparation, preferred but be not limited to 6-caprolactone.Preferably, the molecular weight of described polyester polyol is 1000-3000, and functionality is 2.0-3.0.
Described polyvalent alcohol comprises polyester polyol, polyether glycol, polycarbonate diol or their mixture.
Described polyester polyol as defined above.
Described polyether glycol can by known technological process preparation, for example, in the presence of catalyzer, be made by alkene oxide and initiator reaction.Described catalyzer, preferred but be not limited to alkaline hydrated oxide, alkaline alkoxide, antimony pentachloride, boron fluoride and close ether or their mixture.Described alkene oxide, preferred but be not limited to tetrahydrofuran (THF), oxyethane, 1,2 epoxy prapane, 1,2-butylene oxide ring, 2,3-butylene oxide ring, Styrene oxide 98min. or their mixture.Described initiator, preferred but be not limited to polyol, described polyol, preferred but be not limited to water, ethylene glycol, 1,2-PD, 1,3-PD, glycol ether, TriMethylolPropane(TMP) or their mixture.
Described polycarbonate diol can be made by glycol and dialkyl carbonic ether or diaryl carbonate or phosgene reaction.Described glycol, preferred but be not limited to 1,2-PD, 1,3-PD, BDO, 1,5-PD, 1,6-hexylene glycol, glycol ether, trioxymethylene glycol or their mixture.Described dialkyl carbonic ether or diaryl carbonate, preferred but be not limited to diphenyl carbonate.
Whipping agent of the present invention can be selected various pneumatogens or chemical foaming agent, and is preferred but be not limited to water, halohydrocarbon, hydrocarbon compound, gas.Described halohydrocarbon, preferred but be not limited to chlorodifluoronmethane, dichloro one methyl fuoride, dichloro methyl fuoride, trichlorine methyl fuoride or their mixture.Described hydrocarbon compound, preferred but be not limited to butane, pentane, pentamethylene, hexane, hexanaphthene, heptane or their mixture.Described gas, preferred but be not limited to air, C0
2, or N
2Described whipping agent, particularly preferably water.The consumption of described whipping agent is determined by the desired density that reaches of described urethane.
Needs depending on actual can also comprise chainextender, catalyzer, tensio-active agent, pigment or filler in the prescription of the present invention.
Chainextender of the present invention, usually select molecular weight less than 800 contain the reactive hydrogen atom compound, preferred molecular weight be 18-400 contain the reactive hydrogen atom compound.The described reactive hydrogen atom compound that contains, preferred but be not limited to alkyl diol, two alkylene dibasic alcohol, poly-alkyl polyols or their mixture, for example: ethylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, glycol ether, dipropylene glycol, polyoxyalkylene glycol or their mixture.The described reactive hydrogen atom compound that contains, also can comprise other grafting or undersaturated alkyl diol or their mixture, for example: 1,2-propylene glycol, 2-methyl isophthalic acid, ammediol, 2,2-dimethyl-1, ammediol, 2-butyl-2-ethyl-1, ammediol, 2-butylene-Isosorbide-5-Nitrae-glycol, 2-butyne-Isosorbide-5-Nitrae-glycol, alkanolamine, N-alkyl two alkanolamines; Described N-alkyl two alkanolamines, preferred but to be not limited to thanomin, 2-Propanolamine, 3-amino-2,2-dimethyl propyl alcohol, N methyldiethanol amine, N-ethyldiethanolamine or their mixture.The described reactive hydrogen atom compound that contains can also comprise fatty amine, aromatic amine or their mixture; Described fatty amine, aromatic amine, preferred but be not limited to 1,2-quadrol, 1,3-propylene diamine, Putriscine, 1, the 6-hexanediamine, isophorone diamine, Isosorbide-5-Nitrae-cyclohexanediamine, N, N '-diethyl-phenyl diamines, 2,4-diaminotoluene, 2,6-diaminotoluene or their mixture.The consumption of described chainextender is 1-50wt.%, in the consumption sum of polyvalent alcohol in the reaction system and chainextender by 100wt.%.
Catalyzer of the present invention, preferred but be not limited to amines catalyst, organo-metallic catalyst or their mixture.Described amines catalyst, preferred but be not limited to triethylamine, tributylamine, triethylenediamine, N-ethylmorpholine, N, N, N ', N '-tetramethyl--quadrol, pentamethyl-diethylidene-triamine, N, methylphenylamine, DMA or their mixture.Described organo-metallic catalyst, preferred but be not limited to the organic tin compound, for example: tin acetate (II), stannous octoate (II), thylhexoic acid tin, tin laurate, Dibutyltin oxide, dibutyl tin dichloride, dibutyl tin acetate, dibutyl toxilic acid tin, dioctyl oxalic acid tin or their mixture.The consumption of described catalyzer is 0.001-10wt.%, in polyvalent alcohol consumption sum in the reaction system by 100wt.%.
Tensio-active agent of the present invention, preferred but be not limited to the ethylene oxide derivant of siloxanes.The consumption of described catalyzer is 0.01-8wt.%, in the consumption sum of polyvalent alcohol in the reaction system and chainextender by 100wt.%.
Pigment of the present invention and/or filler, preferred but be not limited to calcium carbonate, graphite, carbon black, titanium dioxide, ferric oxide, alumina trihydrate, wollastonite, glass fibre, trevira, polymer fiber.
Low density polyurethane micropore elastomer density according to prescription and method gained among the present invention is 120kg/m
3To 400kg/m
3, have simultaneously good dimensional stability, physical property and epidermis quality.
The preparation method of microporous polyurethane elastomer
The preparation method of microporous polyurethane elastomer provided by the invention comprises the step that makes the reacted constituent reaction that comprises following ingredients (a)-(c):
(a) one or more isocyanic ester performed polymers are the product that comprises following (a1) and the reaction of reacted constituent (a2) gained;
(a1) one or more isocyanic ester; With
(a2) one or more polyether polyols;
(b) one or more polyvalent alcohols; With
(c) one or more whipping agents,
At least a one or more polyester polyols that contains in the reacted constituent of wherein said isocyanic ester performed polymer or the described reacted constituent (b).
Preferably, the content of described middle polyether polyol is 10%-35%, take the weight of described isocyanic ester performed polymer as 100%
Reacted constituent except isocyanic ester or isocyanic ester performed polymer is mixed by agitator, make blend.
Described blend can be by dual mode and isocyanic ester or isocyanic ester performed polymer hybrid reaction.First kind of way with blend and isocyanic ester or isocyanic ester performed polymer by the agitator hybrid reaction.The second way with described blend and isocyanic ester or isocyanic ester performed polymer by two-pack or Multi-component Polyurethane mixing equipment hybrid reaction.Employed mixing equipment can be high-pressure mixing equipment or low pressure mixing equipment, the preferred lower pressure mixing equipment.This mixing process can be that double fluid mixes, and also can mix by multithread.For example, pigment can add in the mode of the 3rd stream, with the color of quick change mixture.
For those skilled in the art, relevant polyurethane moulded technology and equipment are well-known, can show " polyurethane chemistry and technique " (second section) and Oertel shows academic documents such as " polyurethane handbooks " referring to Saunders and Fish.
In the present invention, isocyanate index X defines according to following:
Polyurethane elastomer provided by the invention can be for the preparation of sole, carpet, cylinder, sealed strip, coating, tire, wiper, bearing circle or packing ring.Be particularly useful for preparing sole.
The present invention also provides the sole by above-mentioned low-density polyurethane elastomerics preparation, and this sole is not only light, and has good snugness of fit.
Embodiment
The following example is used for the explanation preferred embodiment of the invention.It will be understood by those skilled in the art that in the technology disclosed in the following example to have represented contriver's technology that find, that in the present invention's practice, go on well, therefore can be considered to consist of in practice preferred pattern.But under enlightenment of the present disclosure, what those skilled in the art should understand that is when not leaving spirit and scope of the invention, can make many changes and obtain similar result disclosed specific embodiment.
The raw material of mentioning in the context is described as follows:
Polyol 1 (Arcol polyol 24-32): polyether polyol, hydroxyl value 32mg KOH/g, polymer solids content 20%, company limited buys from Bayer Material Science;
Polyol 2 (Bayflex FW30 FXl01): liner polyesterdiols, hydroxyl value 56mgKOH/g, company limited buys from Bayer Material Science;
EG: ethylene glycol
TEOA: trolamine
Dabco EG: amines catalyst, company buys from aerochemistry;
Niax L1500: silicon class tensio-active agent, buy from Mai Tu company;
Water: as whipping agent;
ISO 1 (Desmodur 0926): polyester polyol type isocyanic ester performed polymer, isocyanate content 19.0wt.% can be buied by Bayer Material Science company limited;
ISO 2: by MDI, and the isocyanic ester performed polymer of polyester polyol Polyol 2 and 15% (take isocyanic ester performed polymer weight as 100%) polyether polyol Polyol 1 reaction gained, NCO% is 19.5; Following table 1 is the concrete prescription of ISO2:
ISO 3: by MDI, and the isocyanic ester performed polymer of polyester polyol Polyol 1 and 30% (take isocyanic ester performed polymer weight as 100%) polyether polyol Polyol 2 reaction gained, NCO% is 19.2.Following table 2 is the concrete prescription of ISO3:
*.Desmodur 44C: isocyanate content 33.6wt.%, can be buied by Bayer Material Science company limited;
*.Desmodur CD-C: isocyanate content 29.2wt.%, can be buied by Bayer Material Science company limited;
Select the PENDRAULIK agitator of being buied by PENDRAULIK company as mixing equipment among the embodiment.
Testing method
The density of urethane provided by the present invention is according to DIN EN ISO 845 tests.
The hardness of urethane provided by the present invention is according to DIN 53505 tests.
The tensile strength of urethane provided by the present invention is according to DIN 53504 tests.
The elongation at break of urethane provided by the present invention is according to DIN 53504 tests.
The trousers type tear strength of urethane provided by the present invention is according to DIN ISO 34 tests.
Table 1: microporous polyurethane elastomer prescription and physicals
*: range estimation
The comparative example 1: the low density polyurethane micropore elastomer of polyester polyol and polyester polyol type isocyanic ester prepolymer reaction gained.This micro-pore elastomer shrinkage strain.
The comparative example 2: the low density polyurethane micropore elastomer of the mixture of the pure and mild polyether polyol of polyester polyols and polyester polyol type isocyanic ester prepolymer reaction gained.This micro-pore elastomer physical property and epidermis quality are undesirable.
Embodiment 1 and 2: polyester polyol and the low density polyurethane micropore elastomer that contains the isocyanic ester prepolymer reaction gained of polyether polyol.This micro-pore elastomer has good physical property and epidermis quality simultaneously without contraction.
The those skilled in the art knows that easily the present invention is not limited only to aforesaid detail, and under the prerequisite that does not break away from spirit of the present invention or main characteristic, the present invention can be embodied as other particular forms.Therefore all should be with described embodiment regarded as illustrative from any angle and nonrestrictive, thereby by claims but not above stated specification is pointed out scope of the present invention; And therefore any change as long as it belongs in the implication and scope of claim equivalent, all should be regarded as and belong to the present invention.
Claims (14)
1. polyurethane elastomer is the product that comprises the reacted constituent reaction gained of following ingredients (a)-(c):
(a) one or more isocyanic ester performed polymers are the product that comprises following (a1) and the reaction of reacted constituent (a2) gained;
(a1) one or more isocyanic ester; With
(a2) one or more polyether polyols;
(b) one or more polyvalent alcohols; With
(c) one or more whipping agents,
At least a one or more polyester polyols that contains in the reacted constituent of wherein said isocyanic ester performed polymer or the described reacted constituent (b).
2. polyurethane elastomer according to claim 1, the content of wherein said reacted constituent (a2) is 10%-35%, take the weight of described isocyanic ester performed polymer as 100%.
3. polyurethane elastomer according to claim 1, the content of the NCO of wherein said reacted constituent (a) is 10%-25%, take the weight of described reacted constituent (a) as 100%.
4. the polyurethane elastomer described in according to claim 1, polymer solids content is 20%-45% in the wherein said reacted constituent (a2), take described reacted constituent (a2) weight as 100%, hydroxyl value is 20-50mgKOH/g.
5. polyurethane elastomer according to claim 1, wherein said polyester polyol molecular weight is 1000-3000, functionality is 2.0-3.0.
6. each described polyurethane elastomer according to claim 1-5, the density of wherein said polyurethane elastomer is 120kg/m
3-400kg/m
3
7. method for preparing polyurethane elastic body comprises the step that makes the reacted constituent reaction that comprises following ingredients (a)-(c):
(a) one or more isocyanic ester performed polymers are the product that comprises following (a1) and the reaction of reacted constituent (a2) gained;
(a1) one or more isocyanic ester; With
(a2) one or more polyether polyols;
(b) one or more polyvalent alcohols; With
(c) one or more whipping agents,
At least a one or more polyester polyols that contains in the reacted constituent of wherein said isocyanic ester performed polymer or the described reacted constituent (b).
8. method for preparing polyurethane elastic body according to claim 7, the content of wherein said reacted constituent (a2) is 10%-35%, take the weight of described isocyanic ester performed polymer as 100%.
9. method for preparing polyurethane elastic body according to claim 7, the content of the NCO of wherein said reacted constituent (a) is 10%-25%, take the weight of described reacted constituent (a) as 100%.
10. polymer solids content is 20%-45% in the method for preparing polyurethane elastic body according to claim 7, wherein said reacted constituent (a2), and take described reacted constituent (a2) weight as 100%, hydroxyl value is 20-50mgKOH/g.
11. method for preparing polyurethane elastic body according to claim 7, wherein said polyester polyol molecular weight is 1000-3000, and functionality is 2.0-3.0.
12. each described method for preparing polyurethane elastic body according to claim 7-11, the density of wherein said polyurethane elastomer is 120kg/m
3-400kg/m
3
13. each described polyurethane elastomer is for the preparation of the purposes of sole, carpet, cylinder, sealed strip, coating, tire, wiper, bearing circle or packing ring according to claim 1-6.
14. a sole is made by each described polyurethane elastomer in according to claim 1-6.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110291216.4A CN103030781B (en) | 2011-09-29 | Microporous polyurethane elastomer and its production and use | |
| PCT/EP2012/068799 WO2013045405A1 (en) | 2011-09-29 | 2012-09-24 | Polyurethane microcellular elastomer, the preparation process and the use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110291216.4A CN103030781B (en) | 2011-09-29 | Microporous polyurethane elastomer and its production and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103030781A true CN103030781A (en) | 2013-04-10 |
| CN103030781B CN103030781B (en) | 2016-12-14 |
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| CN103254393A (en) * | 2013-05-24 | 2013-08-21 | 淄博德信联邦化学工业有限公司 | Combined material for polyurethane foam wheel and preparation method thereof |
| CN105683236A (en) * | 2013-10-28 | 2016-06-15 | 巴斯夫欧洲公司 | Low density polyurethane microcellular elastomer |
| CN106700027A (en) * | 2016-12-30 | 2017-05-24 | 浙江华峰新材料股份有限公司 | Polyurethane resin used for breathable insole as well as preparation method and application |
| CN106832203A (en) * | 2016-12-30 | 2017-06-13 | 浙江华峰新材料股份有限公司 | Tire polyurethane resin and preparation method |
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| CN1880356A (en) * | 2005-05-27 | 2006-12-20 | 拜尔材料科学有限公司 | Carbon dioxide blown low density, flexible microcellular polyurethane elastomers |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254393A (en) * | 2013-05-24 | 2013-08-21 | 淄博德信联邦化学工业有限公司 | Combined material for polyurethane foam wheel and preparation method thereof |
| CN103254393B (en) * | 2013-05-24 | 2015-04-15 | 淄博德信联邦化学工业有限公司 | Combined material for polyurethane foam wheel and preparation method thereof |
| CN105683236A (en) * | 2013-10-28 | 2016-06-15 | 巴斯夫欧洲公司 | Low density polyurethane microcellular elastomer |
| CN105683236B (en) * | 2013-10-28 | 2018-11-23 | 巴斯夫欧洲公司 | Low Density Polyurethane Microcellular Elastomer |
| CN106700027A (en) * | 2016-12-30 | 2017-05-24 | 浙江华峰新材料股份有限公司 | Polyurethane resin used for breathable insole as well as preparation method and application |
| CN106832203A (en) * | 2016-12-30 | 2017-06-13 | 浙江华峰新材料股份有限公司 | Tire polyurethane resin and preparation method |
| CN106700027B (en) * | 2016-12-30 | 2020-07-03 | 浙江华峰新材料有限公司 | Polyurethane resin for breathable insoles, and preparation method and application thereof |
| CN106832203B (en) * | 2016-12-30 | 2021-06-08 | 浙江华峰新材料有限公司 | Polyurethane resin for tire and preparation method thereof |
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|---|---|
| WO2013045405A1 (en) | 2013-04-04 |
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