CN104072716B - Polyurethane elastomer and the sole of being made by it - Google Patents

Polyurethane elastomer and the sole of being made by it Download PDF

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Publication number
CN104072716B
CN104072716B CN201410344065.8A CN201410344065A CN104072716B CN 104072716 B CN104072716 B CN 104072716B CN 201410344065 A CN201410344065 A CN 201410344065A CN 104072716 B CN104072716 B CN 104072716B
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weight
weight portions
polyurethane
weight portion
polyurethane elastomer
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CN104072716A (en
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王振滔
温媛瑛
罗贤忠
刘玲
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Zhejiang Aokang Shoes Co Ltd
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Zhejiang Aokang Shoes Co Ltd
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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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine 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
    • C08G18/40—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
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6212—Polymers of alkenylalcohols; Acetals thereof; Oxyalkylation products thereof
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/6262—Polymers of nitriles derived from alpha-beta ethylenically unsaturated carboxylic acids
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6283—Polymers of nitrogen containing compounds having carbon-to-carbon double bonds
    • 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
    • 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
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C08G18/6755—Unsaturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • 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
    • C08G2110/0008—Foam properties flexible
    • 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)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a kind of polyurethane elastomer, it is by the vulcabond that contains 20 ~ 22 weight portions, the PEPA of 8 ~ 10 weight portions, the polymer polyatomic alcohol of 5 ~ 6 weight portions, 1 of 5 ~ 6 weight portions, 4-butanediol, the liquid end hydroxy styrene-butadiene rubber of 1.8 ~ 2.0 weight portions, the diethyl aminoethyl methacrylate of 1.2 ~ 1.5 weight portions, the triethylenediamine of 0.20 ~ 0.25 weight portion, the water of 0.40 ~ 0.50 weight portion, the composition of the foam stabilizer of 0.25 ~ 0.30 weight portion mixes, then be injected into the interior reaction of mould of preheated reservation shape, solidify to form. polyurethane elastomer of the present invention has microcellular structure, has higher elasticity and intensity compared with common foamed plastics, and not only density is relatively low, and resistance to bend(ing) and ageing-resistant performance excellence.

Description

Polyurethane elastomer and the sole of being made by it
Technical field
The technical field that the present invention relates to resin material and daily living article processing, more particularly, the present invention relates toAnd a kind of polyurethane elastomer and the sole made by it.
Background technology
Footwear are essential articles for use of human lives, and along with the development of human civilization, the kind of footwear is also enriched constantlyGet up, for example, have the various kinds such as playshoes, sport footwear, canvas shoe, chemical footwear, sandals, slippers, medical footwear and safety shoeShoes. As the material for sole of shoe for these footwear, widely used have leather, rubber, polyvinyl chloride and polyurethane etc. daySo material or synthetic material. From light-weighted viewpoint, polyurethane material due to other characteristics such as density is low, resistance to bend(ing) withOther material has advantage thereby is widely used; But for polyurethane elastomer material, as sport footwearIts intensity is insufficient when the purposes, and wearability, resistance to bend(ing) etc. need further to improve.
Summary of the invention
In order to solve existing above-mentioned technical problem in prior art, the object of the present invention is to provide a kind of polyurethaneElastomer and the sole of being made by it.
In order to solve the problems of the technologies described above, a first aspect of the present invention relates to a kind of polyurethane elastomer, and describedElastomer is by the PEPA of the vulcabond that contains 20 ~ 22 weight portions, 8 ~ 10 weight portions, the polymer of 5 ~ 6 weight portionsThe BDO of polyalcohol, 5 ~ 6 weight portions, the EVA copolymer of 1.8 ~ 2.0 weight portions, 1.2 ~ 1.5 weightsDiethyl aminoethyl methacrylate, the triethylenediamine of 0.20 ~ 0.25 weight portion, 0.40 ~ 0.50 weight portion of amount partThe composition of foam stabilizer of water, 0.25 ~ 0.30 weight portion mix, be then injected into the mould of preheated reservation shapeIn tool, react, solidify to form.
Wherein, the trade mark of described PEPA is P-2013, and nominal relative molecular mass is 2000(Japan Kuraray public affairsDepartment).
Wherein, described polymer polyatomic alcohol is with PPOX triol (MN-3050), acrylonitrile, styrene, acrylic acidEthylene oxidic ester and initator azodiisobutyronitrile carry out glycerol polymerization and form under nitrogen protection.
Wherein, in described EVA copolymer, in described copolymer the content of vinylacetate be 35 ~40wt%。
Wherein, described composition can also contain antioxidant, light stabilizer, defoamer, ultra-violet absorber, fillingThe additives such as agent, pigment, heat-resisting stabilizing agent.
A second aspect of the present invention relates to a kind of sole, and described sole is mainly made up of above-mentioned polyurethane elastomer.
Wherein, also have abrasion-proof gauge cortex on the surface of described polyurethane elastomer, described abrasion-proof gauge cortex is by coatingSurface treatment liquid, and solidify to form; Described treatment fluid is the processing being made up of the first polyurethane component and the second polyurethane componentLiquid, and the mass ratio of described the first polyurethane component and described the second polyurethane component is 2:1 ~ 3:1.
Wherein, the first described polyurethane component prepares by following steps: by different the toluene of 10 ~ 12 weight portions twoThe polytrimethylene ether glycol of cyanate (TDI), 3 ~ 4 weight portions, the BDO of 2.0 ~ 2.5 weight portions, 1.8 ~ 2.0 weightEnd hydroxy butadiene-the acrylonitrile (HTBN) of part, the dibutyltin dilaurate of 0.1 ~ 0.2 weight portion mix, and then existAt 70 ~ 80 DEG C, react 1.5 ~ 2.0 hours; Reactant liquor is cooled to the deionized water and 0.8 ~ 1.2 that adds 30 ~ 32 weight portions after room temperatureThe dodecyl sodium sulfate of weight portion, obtains the first described polyurethane component after stirring, disperseing.
Wherein, the second described polyurethane component prepares by following steps: by the benzene of 10 ~ 12 weight portions two methylenesThe polytetrahydrofuran diol of group diisocyanate (XDI), 3 ~ 4 weight portions, the BDO, 1.8 ~ 2.0 of 2.0 ~ 2.5 weight portionsThe polyallylamine resin (PAA-01) of weight portion, the dibutyltin dilaurate of 0.1 ~ 0.2 weight portion mix, then 80 ~At 85 DEG C, react 2.0 hours; Reactant liquor is cooled to the deionized water and 0.8 ~ 1.2 weight portion that add 30 ~ 32 weight portions after room temperatureDodecyl sodium sulfate, stir, disperse to obtain the second described polyurethane component.
Compared with prior art, polyurethane elastomer of the present invention and the sole be made up of it have following usefulTechnique effect: polyurethane elastomer of the present invention has microcellular structure, has higher compared with common foamed plasticsElasticity and intensity, not only density is relatively low, and resistance to bend(ing) and ageing-resistant performance excellence.
Detailed description of the invention
Below in conjunction with specific embodiments to polyurethane elastomer of the present invention and the sole made by itStructure, raw material etc. are described in detail, but specific embodiment is not as the restriction to patent of the present invention.
In the present invention, by the liquid MDI that contains 20 ~ 22 weight portions, (carbodiimides changes described polyurethane elastomerProperty MDI), Kuraray company of the PEPA P-2013(of 8 ~ 10 weight portions Japan), the polymer of 5 ~ 6 weight portions is polynaryThe BDO of alcohol, 5 ~ 6 weight portions, the EVA copolymer of 1.8 ~ 2.0 weight portions (poly-second in copolymerThe content of alkene is 35 ~ 40wt%), the diethyl aminoethyl methacrylate of 1.2 ~ 1.5 weight portions, 0.20 ~ 0.25 weight portionThe composition of the water of triethylenediamine, 0.40 ~ 0.50 weight portion, the foam stabilizer (DC-193) of 0.25 ~ 0.30 weight portion is 100Under the condition of ~ 105 DEG C, mix, be then injected in the mould of preheated reservation shape (preheat temperature is 115 DEG C,The sole of for example designed shape of the shape of mould) react 25 ~ 30 minutes, the demoulding, then within 12 hours, get final product 110 DEG C of slakingsTo described polyurethane elastomer. As required, described composition can also contain antioxidant, light stabilizer, defoamer, purpleThe additives such as outer light absorbers, filler, pigment, heat-resisting stabilizing agent; The interpolation of additive belongs to the state of the art,This repeats no more. And in the present invention and following embodiment and comparative example: the polymer polyatomic alcohol relating to is with 10 qualityThe PPOX triol (MN-3050) of part, the acrylonitrile of 2.0 mass parts, the styrene of 3.0 mass parts, the propylene of 5 mass partsThe initator azodiisobutyronitrile of acid glycidyl ester and 0.8 mass parts carries out glycerol polymerization and forms under nitrogen protection. ToolBody, uses the reactor that is provided with agitating device, backflow cooling tube, nitrogen ingress pipe, thermometer, by above-mentioned raw materials and suitableThe solution forming after the ethyl acetate of amount mixes joins in reactor, under nitrogen atmosphere, reacts 2 under the condition of 120 DEG CHour, after reaction finishes, reduce pressure to remove unreacted monomer.
Embodiment 1
Polyurethane elastomer described in the present embodiment is by MDI, 8 weight portions of the Carbodiimide-Modified that contains 20 weight portionsKuraray company of PEPA P-2013(Japan), the BDO of the polymer polyatomic alcohol of 6 weight portions, 6 weight portions,The EVA copolymer (in copolymer, poly content is 35wt%) of 2.0 weight portions, the first of 1.5 weight portionsThe triethylenediamine of base acrylic acid diethylamino ethyl ester, 0.20 weight portion, the water of 0.40 weight portion, 0.25 weight portion evenThe composition of infusion DC-193 mixes under the condition of 100 DEG C, is then injected into preheat temperature and is the preboarding of 115 DEG CIn the mould of shape, react 25 minutes, then the demoulding can obtain described polyurethane elastomer for 12 hours 110 DEG C of slakings.
Embodiment 2
Polyurethane elastomer described in the present embodiment is by MDI, 10 weight of the Carbodiimide-Modified that contains 22 weight portionsPart Kuraray company of PEPA P-2013(Japan), the polymer polyatomic alcohol of 5 weight portions, the Isosorbide-5-Nitrae-Ding bis-of 5 weight portionsThe EVA copolymer (in copolymer, poly content is 35wt%) of alcohol, 1.8 weight portions, 1.5 weight portionsDiethyl aminoethyl methacrylate, the triethylenediamine of 0.20 weight portion, the water of 0.40 weight portion, 0.25 weight portionThe composition of foam stabilizer DC-193 under the condition of 100 DEG C, mix, be then injected into preheat temperature and be 115 DEG C pre-In the mould of setting shape, react 25 minutes, then the demoulding can obtain described elastic polyurethane for 12 hours 110 DEG C of slakingsBody.
Comparative example 1
Polyurethane elastomer described in this comparative example is by MDI, 8 weight portions of the Carbodiimide-Modified that contains 20 weight portionsKuraray company of PEPA P-2013(Japan), the BDO of 6 weight portions, the polyethylene-acetic acid of 2.0 weight portionsThe methacrylic acid diethylamino second of vinyl ester copolymers (in copolymer, poly content is 35wt%), 1.5 weight portionsThe composition of the foam stabilizer DC-193 of the triethylenediamine of ester, 0.20 weight portion, the water of 0.40 weight portion, 0.25 weight portion existsUnder the condition of 100 DEG C, mix, be then injected into preheat temperature and be in the mould of reservation shape of 115 DEG C, react 25 pointsClock, then the demoulding can obtain described polyurethane elastomer for 12 hours 110 DEG C of slakings.
Comparative example 2
Polyurethane elastomer described in this comparative example is by MDI, 8 weight portions of the Carbodiimide-Modified that contains 20 weight portionsKuraray company of PEPA P-2013(Japan), the BDO of the polymer polyatomic alcohol of 6 weight portions, 6 weight portions,The EVA copolymer (in copolymer, poly content is 35wt%) of 2.0 weight portions, 0.20 weight portionThe composition of the water of triethylenediamine, 0.40 weight portion, the foam stabilizer DC-193 of 0.25 weight portion is mixed under the condition of 100 DEG CClose evenly, be then injected into preheat temperature and be in the mould of reservation shape of 115 DEG C, react 25 minutes, the demoulding is then 110DEG C slaking can obtain described polyurethane elastomer for 12 hours.
The polyurethane elastomer that embodiment 1 ~ 2 and comparative example 1 ~ 2 are prepared carries out performance test, test result asShown in table 1.
Table 1
Embodiment 3
The present embodiment relates to a kind of sole, and described sole is mainly formed by the polyurethane elastomer of embodiment 1, andAt described polyurethane elastomer surface-coated surface treatment liquid, then solidify and process 2 ~ 3 minutes at 100 DEG C, afterwards at 120 DEG CSolidify and process 1 minute again; Be formed with the polyurethane wear resistant layer that thickness is about 0.5mm. Described surface treatment liquid is by the first poly-ammoniaThe treatment fluid of ester component and the second polyurethane component composition; And described the first polyurethane component and described the second polyurethane componentMass ratio be 2:1. The first described polyurethane component is by the TDI-80 of 10 ~ 12 weight portions, the polytrimethylene of 3 ~ 4 weight portionsEther glycol (U.S. CerenolH of DuPont company series), the BDO of 2.0 ~ 2.5 weight portions, 1.8 ~ 2.0 weight portionsThe dibutyltin dilaurate of HTBN, 0.1 ~ 0.2 weight portion mix, deionized water and 0.8 ~ 1.2 weight of 30 ~ 32 weight portionsThe dodecyl sodium sulfate of amount part is made; The second described polyurethane component is poly-by the XDI of 10 ~ 12 weight portions, 3 ~ 4 weight portionsThe BDO of erythritan, 2.0 ~ 2.5 weight portions, the polyallylamine resin (PAA-01) of 1.8 ~ 2.0 weight portions,The bay of the dibutyltin dilaurate of 0.1 ~ 0.2 weight portion, the deionized water of 30 ~ 32 weight portions and 0.8 ~ 1.2 weight portionBase sodium sulfonate, stirs, disperses to obtain the second described polyurethane component.
Embodiment 4
The present embodiment relates to a kind of sole, and described sole is mainly formed by the polyurethane elastomer of embodiment 1, andAt described polyurethane elastomer surface-coated surface treatment liquid, then solidify and process 2 ~ 3 minutes at 100 DEG C, afterwards at 120 DEG CSolidify and process 1 minute again; Be formed with the polyurethane wear resistant layer that thickness is about 0.5mm. Described surface treatment liquid is by the first poly-ammoniaThe treatment fluid of ester component and the second polyurethane component composition; And described the first polyurethane component and described the second polyurethane componentMass ratio be 2:1. The first described polyurethane component is by the TDI-80 of 10 ~ 12 weight portions, the polytrimethylene of 3 ~ 4 weight portionsEther glycol (U.S. CerenolH of DuPont company series), the BDO of 2.0 ~ 2.5 weight portions, 1.8 ~ 2.0 weight portionsThe dibutyltin dilaurate of HTBN, 0.1 ~ 0.2 weight portion mix, deionized water and 0.8 ~ 1.2 weight of 30 ~ 32 weight portionsThe dodecyl sodium sulfate of amount part is made; The second described polyurethane component is poly-by the XDI of 10 ~ 12 weight portions, 3 ~ 4 weight portionsThe BDO of erythritan, 2.0 ~ 2.5 weight portions, the polyallylamine resin (PAA-01) of 1.8 ~ 2.0 weight portions,The bay of the dibutyltin dilaurate of 0.1 ~ 0.2 weight portion, the deionized water of 30 ~ 32 weight portions and 0.8 ~ 1.2 weight portionBase sodium sulfonate, stirs, disperses to obtain the second described polyurethane component.
Comparative example 3
This comparative example relates to a kind of sole, and described sole is mainly formed by the polyurethane elastomer of embodiment 1, andAt described polyurethane elastomer surface-coated surface treatment liquid, then solidify and process 2 ~ 3 minutes at 100 DEG C, afterwards at 120 DEG CSolidify and process 1 minute again; Be formed with the polyurethane wear resistant layer that thickness is about 0.5mm. Described surface treatment liquid is by the first poly-ammoniaThe treatment fluid of ester component and the second polyurethane component composition; And described the first polyurethane component and described the second polyurethane componentMass ratio be 2:1. The first described polyurethane component is by the TDI-80 of 10 ~ 12 weight portions, the polytrimethylene of 3 ~ 4 weight portionsEther glycol (U.S. CerenolH of DuPont company series), the BDO of 2.0 ~ 2.5 weight portions, 0.1 ~ 0.2 weight portionDibutyltin dilaurate mix, the deionized water of 30 ~ 32 weight portions and the dodecyl sodium sulfate institute of 0.8 ~ 1.2 weight portionMake; The second described polyurethane component is by the XDI of 10 ~ 12 weight portions, the polytetrahydrofuran diol, 2.0 ~ 2.5 of 3 ~ 4 weight portionsThe BDO of weight portion, the polyallylamine resin (PAA-01) of 1.8 ~ 2.0 weight portions, the dibutyl of 0.1 ~ 0.2 weight portionThe dodecyl sodium sulfate of the deionized water of tin dilaurate, 30 ~ 32 weight portions and 0.8 ~ 1.2 weight portion, stirs, disperses to obtainThe second described polyurethane component.
Comparative example 4
This comparative example relates to a kind of sole, and described sole is mainly formed by the polyurethane elastomer of embodiment 1, andAt described polyurethane elastomer surface-coated surface treatment liquid, then solidify and process 2 ~ 3 minutes at 100 DEG C, afterwards at 120 DEG CSolidify and process 1 minute again; Be formed with the polyurethane wear resistant layer that thickness is about 0.5mm. Described surface treatment liquid is by the first poly-ammoniaThe treatment fluid of ester component and the second polyurethane component composition; And described the first polyurethane component and described the second polyurethane componentMass ratio be 2:1. The first described polyurethane component is by the TDI-80 of 10 ~ 12 weight portions, the polytrimethylene of 3 ~ 4 weight portionsEther glycol (U.S. CerenolH of DuPont company series), the BDO of 2.0 ~ 2.5 weight portions, 1.8 ~ 2.0 weight portionsThe dibutyltin dilaurate of HTBN, 0.1 ~ 0.2 weight portion mix, deionized water and 0.8 ~ 1.2 weight of 30 ~ 32 weight portionsThe dodecyl sodium sulfate of amount part is made; The second described polyurethane component is poly-by the XDI of 10 ~ 12 weight portions, 3 ~ 4 weight portionsThe BDO of erythritan, 2.0 ~ 2.5 weight portions, the dibutyltin dilaurate, 30 of 0.1 ~ 0.2 weight portion ~The dodecyl sodium sulfate of the deionized water of 32 weight portions and 0.8 ~ 1.2 weight portion, stirs, disperses to obtain the second described polyurethaneComponent.
Comparative example 5
This comparative example relates to a kind of sole, and described sole is mainly formed by the polyurethane elastomer of embodiment 1, andAt described polyurethane elastomer surface-coated surface treatment liquid, then solidify and process 2 ~ 3 minutes at 100 DEG C, afterwards at 120 DEG CSolidify and process 1 minute again; Be formed with the polyurethane wear resistant layer that thickness is about 0.5mm. Described surface treatment liquid is by the first poly-ammoniaThe treatment fluid of ester component and the second polyurethane component composition; And described the first polyurethane component and described the second polyurethane componentMass ratio be 2:1. The first described polyurethane component is by the TDI-80 of 10 ~ 12 weight portions, the polytrimethylene of 3 ~ 4 weight portionsEther glycol (U.S. CerenolH of DuPont company series), the BDO of 2.0 ~ 2.5 weight portions, 0.1 ~ 0.2 weight portionDibutyltin dilaurate mix, the deionized water of 30 ~ 32 weight portions and the dodecyl sodium sulfate institute of 0.8 ~ 1.2 weight portionMake; The second described polyurethane component is by the XDI of 10 ~ 12 weight portions, the polytetrahydrofuran diol, 2.0 ~ 2.5 of 3 ~ 4 weight portionsThe deionized water of the BDO of weight portion, the dibutyltin dilaurate of 0.1 ~ 0.2 weight portion, 30 ~ 32 weight portions andThe dodecyl sodium sulfate of 0.8 ~ 1.2 weight portion, stirs, disperses to obtain the second described polyurethane component.
The sole that embodiment 3 ~ 4 and comparative example 3 ~ 5 are prepared carries out performance test, wherein said shore hardnessRefer to the performance on polyurethane wear resistant layer surface; And resistance to bending refers to that repeatedly carrying out at normal temperatures bend test forms with surfaceNumber of times till the above crackle of 10mm. Result is as shown in table 2.
Table 2
The foregoing is only the preferred embodiments of the present invention, can not be interpreted as limiting scope of the present invention with this, all at thisThe distortion being equal to of making in the claimed scope of claims of invention and the embodiment of change are all in the present inventionIn scope required for protection.

Claims (6)

1. a sole, is made up of polyurethane elastomer, and the surface of described polyurethane elastomer also has abrasion-proof gauge cortex,Described abrasion-proof gauge cortex is by coating surface treatment fluid and solidify to form; It is characterized in that: described treatment fluid is for gathering ammonia by firstThe treatment fluid of ester component and the second polyurethane component composition, and described the first polyurethane component and described the second polyurethane componentMass ratio be 2:1 ~ 3:1; Described the first polyurethane component prepares by following steps: by the toluene of 10 ~ 12 weight portionsThe polytrimethylene ether glycol of vulcabond, 3 ~ 4 weight portions, the BDO of 2.0 ~ 2.5 weight portions, 1.8 ~ 2.0 weightEnd hydroxy butadiene-the acrylonitrile of part, the dibutyltin dilaurate of 0.1 ~ 0.2 weight portion mix, then at 70 ~ 80 DEG CLower reaction 1.5 ~ 2.0 hours; Reactant liquor is cooled to the deionized water and 0.8 ~ 1.2 weight portion that add 30 ~ 32 weight portions after room temperatureDodecyl sodium sulfate, stir, disperse after obtain described the first polyurethane component; Described the second polyurethane component is by following stepSuddenly prepare: by the polytetrahydrofuran diol, 2.0 of the XDI of 10 ~ 12 weight portions, 3 ~ 4 weight portions ~The dibutyl tin February of the BDO of 2.5 weight portions, the polyallylamine resin of 1.8 ~ 2.0 weight portions, 0.1 ~ 0.2 weight portionCinnamic acid ester mixes, and then at 80 ~ 85 DEG C, reacts 2.0 hours; Reactant liquor be cooled to add after room temperature 30 ~ 32 weight portions go fromThe dodecyl sodium sulfate of sub-water and 0.8 ~ 1.2 weight portion, stirs, disperses to obtain described the second polyurethane component.
2. sole according to claim 1, is characterized in that: described polyurethane elastomer is by containing 20 ~ 22 weight portionsIsosorbide-5-Nitrae-the Ding bis-of the PEPA of vulcabond, 8 ~ 10 weight portions, the polymer polyatomic alcohol of 5 ~ 6 weight portions, 5 ~ 6 weight portionsThe EVA copolymer of alcohol, 1.8 ~ 2.0 weight portions, the methacrylic acid diethylamino of 1.2 ~ 1.5 weight portionsThe even bubble of the triethylenediamine of ethyl ester, 0.20 ~ 0.25 weight portion, the water of 0.40 ~ 0.50 weight portion, 0.25 ~ 0.30 weight portionThe composition of agent mixes, and is then injected into reaction in the mould of preheated reservation shape, solidify to form.
3. sole according to claim 2, is characterized in that: the trade mark of described PEPA is P-2013, nominal phaseBe 2000 to molecular mass.
4. sole according to claim 2, is characterized in that: described polymer polyatomic alcohol be with PPOX triol,Acrylonitrile, styrene, glycidyl acrylate and initator azodiisobutyronitrile carry out glycerol polymerization under nitrogen protectionForm.
5. sole according to claim 2, is characterized in that: in described EVA copolymer, described commonIn polymers, the content of vinylacetate is 35 ~ 40wt%.
6. sole according to claim 2, is characterized in that: described composition contains antioxidant, light stabilizer, deaerationAt least one in agent, ultra-violet absorber, filler, pigment or heat-resisting stabilizing agent.
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CN105153400B (en) * 2015-06-30 2017-08-04 晋江市池店镇娇鹏贸易有限公司 Outdoor shoe bottom microporous polyurethane elastomer
CN107417879B (en) * 2016-05-24 2020-06-09 北京化工大学 Solution polymerized styrene-butadiene rubber-polyurethane elastomer material for high-performance tire and preparation method thereof
CN106519174A (en) * 2016-12-07 2017-03-22 田昊立 High resilience, soft, medium and low density polyurethane
CN106832139B (en) * 2017-01-18 2019-10-08 新辉（中国）新材料有限公司 Latex and preparation method thereof comprising polyurethane-modified Carboxy copolymer
CN107136582B (en) * 2017-06-29 2020-05-15 东莞市永存内衣有限公司 Breast support, preparation method thereof, bra using breast support and preparation method thereof
CN107540812B (en) * 2017-09-08 2020-10-27 北京化工大学 Thermoplastic solution-polymerized styrene-butadiene rubber-polyurethane elastomer material and preparation method thereof
JP6961837B2 (en) * 2018-10-11 2021-11-05 三井化学株式会社 Manufacturing method of foamed polyurethane elastomer raw material, foamed polyurethane elastomer, midsole and foamed polyurethane elastomer
CN110903629A (en) * 2019-12-21 2020-03-24 惠安伟盛鞋业有限公司 High-elasticity wear-resistant polyurethane foamed shoe material and preparation method thereof

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