CN105693970A - Polyether-type microporous hard polyurethane shoe sole combination raw solution and polyurethane shoe sole - Google Patents
Polyether-type microporous hard polyurethane shoe sole combination raw solution and polyurethane shoe sole Download PDFInfo
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- CN105693970A CN105693970A CN201610061732.0A CN201610061732A CN105693970A CN 105693970 A CN105693970 A CN 105693970A CN 201610061732 A CN201610061732 A CN 201610061732A CN 105693970 A CN105693970 A CN 105693970A
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- polyether
- sole
- stock solution
- polyurethane shoe
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 52
- 239000004814 polyurethane Substances 0.000 title claims abstract description 52
- 239000012948 isocyanate Substances 0.000 claims abstract description 38
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 38
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 20
- 229920000570 polyether Polymers 0.000 claims abstract description 20
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000004088 foaming agent Substances 0.000 claims abstract description 10
- 239000004970 Chain extender Substances 0.000 claims abstract description 9
- 239000011550 stock solution Substances 0.000 claims description 27
- 150000005846 sugar alcohols Polymers 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 20
- 150000001298 alcohols Chemical class 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000006260 foam Substances 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000002932 luster Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 2
- 239000003995 emulsifying agent Substances 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 description 1
- 102100020895 Ammonium transporter Rh type A Human genes 0.000 description 1
- 101100301844 Arabidopsis thaliana RH50 gene Proteins 0.000 description 1
- 101710130081 Aspergillopepsin-1 Proteins 0.000 description 1
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 101150107345 Rhag gene Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
Classifications
-
- 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
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Abstract
The invention discloses a polyether-type microporous hard polyurethane shoe sole combination raw solution and a polyurethane shoe sole, belonging to the technical field of microporous hard polyurethane molding products. The combination raw solution comprises a component A, a component B and a component C. The component A contains polyether glycol, polymer polylol, a chain extender, a catalyst, a foaming agent, an emulsifier, an antioxidant and the like. The component B is composed of a prepolymer synthesized from polyether glycol and isocyanate, multiple isocyanates, a stabilizer and the like. The component C is composed of low-molecular dibasic alcohol and a catalyst. The polyether-type microporous hard polyurethane shoe sole is portable and durable, and has the characteristics of high strength, high hardness, high toughness, hydrolysis resistance and mildew resistance.
Description
Technical field
The present invention relates to micropore hard polyurethane-moulded articles technical field, be specifically related to a kind of polyether-type micropore hard polyurethane shoe-sole combination stock solution and polyurethane shoe-sole。
Background technology
Polyurethane is well known as new function shaped material, high-performance, high added value, the eurytopicity excellent due to its product and technique is simple and direct, the low input of frock (equipment or mould), makes polyurethane material ascend rapidly one of world's six major projects plastics。Particularly micropore semi-hard polyurethane material, the performance such as the tolerance to cold of its excellence, wearability, absorption impact, obtain extensive use at shoe-making industry and automotive upholstery industry。
Polyurethane shoe-sole stock solution is divided into polyester-type and polyether-type two class。Commercial polyurethane sole 70% is polyester-type。And polyether-type sole is just to list in recent years, owing to having stronger hydrolysis, anti-mildew becomes, resistance to subdue and the performance such as low temperature resistant, overcomes some defect of PAUR sole, and with low cost。Thus it is subject to a large amount of selections of people。Especially at the area of awful weather (such as cold, moist, sleet is many) and working environment, the application of polyether-type micropore semi-hard polyurethane sole instead of polyester-type micropore semi-hard polyurethane sole completely。
Along with the extensive use of polyether-type micropore semi-hard polyurethane sole, the research and development of polyether-type micropore hard polyurethane shoe-sole, part replaces polyester-type micropore hard polyurethane shoe-sole, arises at the historic moment as new problem。The complete polyether-type product of this project system, does not contain any PEPA。Thus with low cost, intensity index is equal to PAUR sole, and overcomes some defect of PAUR sole, has prominent hydrolysis, anti-mildew becomes, characteristic at the bottom of the polyether type polyurethane shoes such as low temperature resistant。
Summary of the invention
It is an object of the invention to provide a kind of polyether-type micropore hard polyurethane shoe-sole combination stock solution and polyurethane shoe-sole, this combination stock solution is nontoxic, environmental protection, adopt micropore hard polyurethane shoe-sole prepared by this kind of Polyether urethane shoe sole raw liquorbasic solution, light, durable, and there is the characteristics such as high intensity, high rigidity, high tenacity, hydrolysis, anti-mildew change。
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of polyether-type micropore hard polyurethane shoe-sole combination stock solution, this combination stock solution is made up of component A, B component and C component, wherein: the part by weight of component A and C component is 100:(1.3-1.5)；The total amount of component A and C component and the part by weight of B component are 100:(100-120)；In described combination stock solution, component A includes the following component counted by weight:
Polyhydric alcohol I 68～78 parts；
Polyhydric alcohol II 2～3 parts；
Polymer polyatomic alcohol 10～12 parts；
Foam stabiliser 0.3～0.5 part；
0.1～0.3 part of antioxidant；
Chain extender 10～12 parts；
Foaming agent 0.4～0.5 part；
In described combination stock solution, B component includes the following component counted by weight:
Isocyanate prepolymers body 70～77 parts；
Isocyanates II 18～20 parts；
Isocyanates III 5～8 parts；
In described combination stock solution, C component includes the following component counted by weight:
Dihydroxylic alcohols 65～70 parts；
Amines catalyst 30～35 parts。
In described component A, described polyhydric alcohol I is two degree of functionality polyether polyol, its molecular weight 3000-5000。
In described component A, described polyhydric alcohol II is four degree of functionality polyether polyol, its molecular weight 200-500。
In described component A, described polymer polyatomic alcohol is three-functionality-degree polymer polyatomic alcohol, and its hydroxyl value is 18-25KOH/mg。
In described component A, foam stabiliser is silicone surfactant；Antioxidant is organic phosphite antioxidant, has good color and luster protective effect；Foaming agent is water。
In described B component, Isocyanate prepolymers body is that pure MDI prepares through chemical reaction with low molecular polyether dihydroxylic alcohols, liquefied mdi, stabilizer; concrete preparation process is: after pure MDI heating is melted to transparence (material temperature is 45-50 DEG C); add stirring in reactor; low molecular polyether dihydroxylic alcohols, isocyanates II (liquefied mdi) and stabilizer it is sequentially added into after 5 minutes; control reaction temperature at 70-80 DEG C; pre-polymerization 1-2 hour under nitrogen protection atmosphere; after detection-NCO content is qualified, Isocyanate prepolymers body is prepared complete；Wherein: the part by weight of low molecular polyether dihydroxylic alcohols and pure MDI is 50:91, the part by weight of isocyanates II (liquefied mdi) and pure MDI is 1:20, and the part by weight of stabilizer and pure MDI is 1:200；The NCO percentage composition of gained Isocyanate prepolymers body is 18-20%, and the molecular weight of described low molecular polyether dihydroxylic alcohols is 800-1500, and described stabilizer is chemical pure phosphoric acid。
In described B component, isocyanates II is liquefied mdi, and isocyanates III is polymeric MDI。
In described C component, dihydroxylic alcohols is ethylene glycol, and amines catalyst is ethylene diamine。
The process that combinations thereof stock solution prepares polyurethane shoe-sole is utilized to comprise the steps:
(1) preparation of component A: polyhydric alcohol I, polyhydric alcohol II and polymer polyatomic alcohol are heated to 60-70 DEG C, then put into successively in reactor in described ratio, chain extender, antioxidant, foam stabiliser and foaming agent is sequentially added after stirring 0.5 hour, 3-4 hour is stirred at constant temperature 60-70 DEG C, when detection water content is 0.4-0.5wt.%, component A is prepared complete；
(2) preparation of B component: isocyanates II and isocyanates III that Isocyanate prepolymers body, material temperature are 50-60 DEG C are added reactor, constant temperature 60-70 DEG C in described ratio, stirs 1 hour, namely obtain B component；
(3) preparation of C component: added by dihydroxylic alcohols in reactor, controls material temperature 65-70 DEG C, adds amines catalyst, stirs 30 minutes, and after catalyst is completely dissolved, constant temperature stands 1 hour, filters subpackage, and namely C component has been prepared；
(4) preparation of polyurethane shoe-sole: by component A with C component by 100:(1.3-1.5) part by weight mix after, press 100:(100-120 with B component again) part by weight mixed-forming, namely obtain polyurethane sole materials, after being further processed into required form, be polyurethane shoe-sole。
Design principle of the present invention is as follows:
First EU stock solution in the present invention, need to prepare and can be polymerized formation micropore, the component A of hard material, B component, C component。
The raw material of described component A includes multiple polyhydric alcohol, polymer polyatomic alcohol, stabilizer, antioxidant, chain extender, foaming agent。Wherein polyhydric alcohol, polymer polyatomic alcohol are polyether-type。The selection of multiple polyhydric alcohol, considerably increases the crosslink density of reactant (micropore hard polyurethane shoe-sole) so that micropore hard polyurethane shoe-sole has high intensity, high rigidity, high tenacity and the characteristic such as hydrolysis, anti-mildew change。
The raw material of described B component includes multiple isocyanates, polyether polyol, stabilizer。The performed polymer that end group is isocyanates prepared wherein is reacted by two kinds of isocyanates and polyether polyol。The selection of three kinds of isocyanates, increases the hard segment content of reactant (micropore hard polyurethane shoe-sole), it is ensured that the hardness of sole and intensity index significantly。
The raw material of described component C includes little molecule dihydroxylic alcohols and amines catalyst, and C component has the stability of excellence, high activity and good manufacturability。
The present invention has the following advantages and beneficial effect:
1, the molecular weight of polyether Glycols of the present invention is preferably 800-1500, is used for making B component performed polymer, reduces cost of material, it is thus achieved that good combination property, manufacturability, stability and highly active performed polymer。
2, currently preferred polyhydric alcohol is entirely polyether polyol, thus the lower cost for material of shoe sole article。
3, Isocyanate prepolymers body prepared by preferred molecular weight dihydroxylic alcohols of the present invention, viscosity height low, active and technique is simple and direct, stable。Contribute to the enhancing of shoe sole article, toughness reinforcing, Hardening；Contribute to strengthening the anti-mildew change of polyether-type sole, hydrolysis and weatherability。
4, soles system B component of the present invention is formulated in proportion by performed polymer, isocyanates II, isocyanates III, mixes cast micropore hard polyurethane shoe-sole with soles system component A。Polyether-type micropore hard polyurethane shoe-sole is light, durable, and has the characteristic of high intensity, high rigidity, high tenacity, hydrolysis, anti-mildew change, is particularly suitable for making woman style thick end fashion shoe, wedge heel, woman sandal。Due to woman style polyether-type micropore hard sole modern design, simply, productive temp is quick, and mould is prone to the type that turns over and makes；Therefore of all shapes and colors, fashion is attractive in appearance, the modish women's shoes of adapted polyether-type micropore hard polyurethane shoe-sole, becomes market new lover, be subject to more and more youth and like to be beautiful the favor of women and choosing。
Detailed description of the invention
Below in conjunction with embodiment in detail the present invention is described in detail。
Embodiment 1
In the present embodiment, polyether-type micropore hard polyurethane shoe-sole combination stock solution is ep-type material nontoxic, " 0 " ODP, VOC free, is made up of component A, B component and C component, and composition and the content of each component are as shown in table 1 below。
Table 1
| Sole structure combinations stock solution | The composition (wt.%) of each component |
| Component A | Polyhydric alcohol I: 68～78%；Polyhydric alcohol II: 2～3%；Polymer polyatomic alcohol: 10～12%；Foam stabiliser: 0.3～0.5%；Antioxidant: 0.1～0.3%；Chain extender: 10～12%；Foaming agent: 0.4～0.5% |
| B component | Isocyanate prepolymers body: 70%～77%；Isocyanates II: 18%～20%；Isocyanates III: 5%～8%； |
| Component C | Polyhydric alcohol: 65%～70%；Catalyst: 30%～35% |
1. the preparation of soles system component A
Heating polyhydric alcohol to 60 70 DEG C, weighing polyhydric alcohol I be that 73.7g, polyhydric alcohol II put into reactor for 3.5g, polymer polyatomic alcohol 10g, and feeding in raw material in stirring mixes；Add chain extender 10.5g, antioxidant 0.2g, foam stabiliser 0.45g, foaming agent 0.45g, C component 1.2g, keep constant temperature 60 70 DEG C, stirring mixing 2 hours, sample analysis water content。The adjustment if deficiency adds water, surveys water content after should mixing 1 hour, until qualified。Namely component A is prepared complete。
If set water content as: 0.45%, then by formula (1) calculate water addition:
(formula 1)
In formula 1: a polyhydric alcohol I inventory；
B polyhydric alcohol II inventory；
C polymer polyatomic alcohol inventory；
D stabilizer inventory；
E chain extender inventory；
F antioxidant inventory；
W add water before content of water in system (%)。
2. the preparation of soles system B component
Pure MDI heating melts to transparent (45-50 DEG C): weighing 9100g and put in still, material temperature keeps 40-45 DEG C。Molecular weight 800-1500 polyether Glycols: 5000g, MDI2:480g are preheated to 40 DEG C, in stirring, (100 turns/min) are simultaneously introduced in still with phosphoric acid (measuring by 30ppm)。Control reaction temperature 70-80 DEG C, inflated with nitrogen protection pre-polymerization 2 hours。Detection-NCO content is qualified, can add MDI2:2740g, MDI3:913g that material temperature is 50-60 DEG C。Constant temperature 60-70 DEG C, stirs 1 hour。Namely B component is prepared complete。
3. the preparation of soles system C component
Ethylene glycol 335g puts into reactor, controls material temperature and is 65-70 DEG C, adds triethylene diamine crystal 165g, stir 30 minutes (crystal is completely dissolved), and constant temperature stands 1 hour, uses after filtration。
Namely C component is prepared complete。
4. the making of polyether-type micropore hard polyurethane test piece
Component A (C component adds component A by the proportioning of 1.3-1.5%), B component being preheated to 45 DEG C, puts into A, B batch can of polyurethane low-pressure casting machine respectively, circulate more than 20 minutes, in machine, material temperature controls at 40 DEG C。A, B of making test piece expect that proportioning carries out cast test piece in the ratio of 100:115,100:120,100:125,100:130。Namely ripening can be taken off test piece in 4-6 minute, after room temperature is placed 72 hours, cuts out sample and carries out physical and mechanical properties detection。Test piece mold temperature: 45-50 DEG C, mould specification: 22cmX22cmX0.6cm。
Material temperature can be risen to 40 DEG C by hand dropping test piece, more near 25 DEG C, carry out pouring operation, namely obtain micropore hard polyurethane sole materials, its technical specification such as table 2 below。
Table 2 polyether-type micropore hard polyurethane shoe-sole technical specification
| Project | Technical specification (23 ± 2 DEG C of RH50 ± 10%) |
| Density kg/m3 | 500-600 |
| Hardness shore A (72h) | 65-75 |
| Hot strength MPa (72h) | ≥4.5 |
| Percentage elongation % (72h) | ≥250 |
| Tearing strength kN/m (72h) | ≥20 |
Although embodiment of the present invention are disclosed as above, but listed utilization that it is not restricted in description and embodiment, it can be applied to various applicable the field of the invention completely, for those skilled in the art, it is easily achieved other amendment, therefore, under the general concept limited without departing substantially from claim and equivalency range, the present invention is not limited to specific details and shown here as the embodiment with description。
Claims (9)
1. a polyether-type micropore hard polyurethane shoe-sole combination stock solution, it is characterised in that: this combination stock solution is made up of component A, B component and C component, wherein: the part by weight of component A and C component is 100:(1.3-1.5)；The total amount of component A and C component and the part by weight of B component are 100:(100-120)；In described combination stock solution, component A includes the following component counted by weight:
Polyhydric alcohol I 68～78 parts；
Polyhydric alcohol II 2～3 parts；
Polymer polyatomic alcohol 10～12 parts；
Foam stabiliser 0.3～0.5 part；
0.1～0.3 part of antioxidant；
Chain extender 10～12 parts；
Foaming agent 0.4～0.5 part；
In described combination stock solution, B component includes the following component counted by weight:
Isocyanate prepolymers body 70～77 parts；
Isocyanates II 18～20 parts；
Isocyanates III 5～8 parts；
In described combination stock solution, C component includes the following component counted by weight:
Dihydroxylic alcohols 65～70 parts；
Amines catalyst 30～35 parts。
2. polyether-type micropore hard polyurethane shoe-sole according to claim 1 combination stock solution, it is characterised in that: described polyhydric alcohol I is two degree of functionality polyether polyol, its molecular weight 3000-5000。
3. polyether-type micropore hard polyurethane shoe-sole according to claim 1 combination stock solution, it is characterised in that: described polyhydric alcohol II is four degree of functionality polyether polyol, its molecular weight 200-500。
4. polyether-type micropore hard polyurethane shoe-sole according to claim 1 combination stock solution, it is characterised in that: described polymer polyatomic alcohol is three-functionality-degree polymer polyatomic alcohol, and its hydroxyl value is 18-25KOH/mg。
5. polyether-type micropore hard polyurethane shoe-sole according to claim 1 combination stock solution, it is characterised in that: in described component A, foam stabiliser is silicone surfactant；Antioxidant is organic phosphite antioxidant, has good color and luster protective effect；Foaming agent is water。
6. polyether-type micropore hard polyurethane shoe-sole according to claim 1 combination stock solution; it is characterized in that: in described B component, the preparation process of Isocyanate prepolymers body is: pure MDI is heated to 45-50 DEG C melt to transparence after; add stirring in reactor; low molecular polyether dihydroxylic alcohols, isocyanates II and stabilizer it is sequentially added into after 5 minutes; control reaction temperature at 70-80 DEG C; pre-polymerization 1-2 hour under nitrogen protection atmosphere, Isocyanate prepolymers body is prepared complete；Wherein: the part by weight of low molecular polyether dihydroxylic alcohols and pure MDI is 50:91, the part by weight of isocyanates II and pure MDI is 1:20, and the part by weight of stabilizer and pure MDI is 1:200；The NCO percentage composition of gained Isocyanate prepolymers body is 18-20%, and the molecular weight of described low molecular polyether dihydroxylic alcohols is 800-1500, and described stabilizer is chemical pure phosphoric acid。
7. the polyether-type micropore hard polyurethane shoe-sole combination stock solution according to claim 1 or 6, it is characterised in that: in described B component, isocyanates II is liquefied mdi, and isocyanates III is polymeric MDI。
8. polyether-type micropore hard polyurethane shoe-sole according to claim 1 combination stock solution, it is characterised in that: in described C component, dihydroxylic alcohols is ethylene glycol, and amines catalyst is ethylene diamine。
9. one kind utilizes polyurethane shoe-sole prepared by combination stock solution described in claim 1, it is characterised in that: this sole preparation process comprises the steps:
(1) preparation of component A: polyhydric alcohol I, polyhydric alcohol II and polymer polyatomic alcohol are heated to 60-70 DEG C, then put into successively in reactor in described ratio, chain extender, antioxidant, foam stabiliser and foaming agent is sequentially added after stirring 0.5 hour, 3-4 hour is stirred at constant temperature 60-70 DEG C, when detection water content is 0.4-0.5wt.%, component A is prepared complete；
(2) preparation of B component: isocyanates II and isocyanates III that Isocyanate prepolymers body, material temperature are 50-60 DEG C are added reactor, constant temperature 60-70 DEG C in described ratio, stirs 1 hour, namely obtain B component；
(3) preparation of C component: added by dihydroxylic alcohols in reactor, controls material temperature 65-70 DEG C, adds amines catalyst, stirs 30 minutes, and after catalyst is completely dissolved, constant temperature stands 1 hour, filters subpackage, and namely C component has been prepared；
(4) preparation of polyurethane shoe-sole: by component A with C component by 100:(1.3-1.5) part by weight mix after, press 100:(100-120 with B component again) part by weight mixed-forming, namely obtain polyurethane sole materials, after being further processed into required form, be polyurethane shoe-sole。
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| CN108530595A (en) * | 2018-04-11 | 2018-09-14 | 东莞市秦粤丰鞋材有限公司 | PU footwear materials and its manufacturing method and application |
| CN108948320A (en) * | 2018-06-19 | 2018-12-07 | 旭川化学（昆山）有限公司 | It is a kind of for manufacturing the combination material of polyurethane sole materials |
| CN109111560A (en) * | 2018-06-19 | 2019-01-01 | 旭川化学（昆山）有限公司 | A kind of production technology of the sandals that high-strength bending-resistant is curved polyester sole material |
| CN110746562A (en) * | 2019-11-11 | 2020-02-04 | 湖北可兴鞋业有限公司 | Synthetic rubber and preparation method thereof |
| CN111548471A (en) * | 2020-05-29 | 2020-08-18 | 叶正芬 | Polyurethane stock solution for high-elasticity sports shoe sole and preparation method thereof |
| CN112940217A (en) * | 2021-02-07 | 2021-06-11 | 福建美明达鞋业发展有限公司 | Shock-absorbing sole of sports shoe and preparation method thereof |
| CN113150533A (en) * | 2021-05-10 | 2021-07-23 | 广东足迹鞋业有限公司 | Polyurethane cotton insole and preparation method thereof |
| CN114456347A (en) * | 2022-02-28 | 2022-05-10 | 赢聚化学技术研发(南京)有限公司 | Preparation method of anti-slip polyurethane sole transparent sole attaching material |
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| CN108530595A (en) * | 2018-04-11 | 2018-09-14 | 东莞市秦粤丰鞋材有限公司 | PU footwear materials and its manufacturing method and application |
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| CN109111560A (en) * | 2018-06-19 | 2019-01-01 | 旭川化学（昆山）有限公司 | A kind of production technology of the sandals that high-strength bending-resistant is curved polyester sole material |
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| CN112940217A (en) * | 2021-02-07 | 2021-06-11 | 福建美明达鞋业发展有限公司 | Shock-absorbing sole of sports shoe and preparation method thereof |
| CN113150533A (en) * | 2021-05-10 | 2021-07-23 | 广东足迹鞋业有限公司 | Polyurethane cotton insole and preparation method thereof |
| CN113150533B (en) * | 2021-05-10 | 2022-07-29 | 广东足迹鞋业有限公司 | Polyurethane cotton insole and preparation method thereof |
| CN114456347A (en) * | 2022-02-28 | 2022-05-10 | 赢聚化学技术研发(南京)有限公司 | Preparation method of anti-slip polyurethane sole transparent sole attaching material |
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