CN104072716A - Polyurethane elastomer and sole made from same - Google Patents
Polyurethane elastomer and sole made from same Download PDFInfo
- Publication number
- CN104072716A CN104072716A CN201410344065.8A CN201410344065A CN104072716A CN 104072716 A CN104072716 A CN 104072716A CN 201410344065 A CN201410344065 A CN 201410344065A CN 104072716 A CN104072716 A CN 104072716A
- Authority
- CN
- China
- Prior art keywords
- weight parts
- polyurethane elastomer
- polyurethane
- parts
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C08G18/70—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
Landscapes
- 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)
- Polyurethanes Or Polyureas (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a polyurethane elastomer. The polyurethane elastomer is formed by uniformly mixing the following ingredients in parts by weight: 20-22 parts of diisocyanate, 8-10 parts of polyester polyol, 5-6 parts of 1,4-butanediol, 1.8-2.0 parts of hydroxy-terminated butadiene, 1.2-1.5 parts of diethylaminoethyl methacrylate, 0.20-0.25 part of triethylenediamine, 0.40-0.50 parts of water, and 0.25-0.30 parts of foam stabilizer, and injecting the mixture a preheated pre-shaped die for reaction and curing. The polyurethane elastomer provided by the invention has micropore structures, has relatively high elasticity and strength compared with a conventional foamed plastic, is relatively low in density, and is excellent in bendability resistance and aging resistance.
Description
Technical field
The present invention relates to the technical field of resin material and daily living article processing, more particularly, the sole that the present invention relates to a kind of polyurethane elastomer and 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 constantly, such as the shoes that have the various kinds such as playshoes, sports shoes, canvas shoes rope soled shoes, chemical footwear, sandals, slippers, medical footwear and safety shoes.As the material for sole of shoe for these footwear, widely used have natural materials or synthetic materialss such as leather, rubber, polyvinyl chloride and urethane.From light-weighted viewpoint, polyurethane material is because other characteristics such as density is low, resistance to bend(ing) and other material have advantage thereby be widely used; But for polyurethane elastomer material, during as purposes such as sports shoess, its intensity is insufficient, and wear resistance, 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 sole that the object of the present invention is to provide a kind of polyurethane elastomer and 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 described elastomerics is by the vulcabond that contains 20 ~ 22 weight parts, the polyester polyol of 8 ~ 10 weight parts, the polymer polyatomic alcohol of 5 ~ 6 weight parts, 1 of 5 ~ 6 weight parts, 4-butyleneglycol, the EVA multipolymer of 1.8 ~ 2.0 weight parts, the diethyl aminoethyl methacrylate of 1.2 ~ 1.5 weight parts, the triethylenediamine of 0.20 ~ 0.25 weight part, the water of 0.40 ~ 0.50 weight part, the composition of the foam stabilizer of 0.25 ~ 0.30 weight part mixes, then be injected into the interior reaction of mould of preheated predetermined shape, solidify to form.
Wherein, the trade mark of described polyester polyol is P-2013, and nominal relative molecular mass is 2000(Japan Kuraray company).
Wherein, described polymer polyatomic alcohol is with polyoxytrimethylene triol (MN-3050), vinyl cyanide, vinylbenzene, glycidyl acrylate and initiator Diisopropyl azodicarboxylate, carries out graft polymerization and form under nitrogen protection.
Wherein, in described EVA multipolymer, in described multipolymer, the content of vinyl acetate is 35 ~ 40wt%.
Wherein, described composition can also contain the additives such as antioxidant, photostabilizer, deaerating agent, UV light absorber, weighting 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 by above-mentioned polyurethane elastomer.
Wherein, on the surface of described polyurethane elastomer, also have abrasion-proof gauge cortex, described abrasion-proof gauge cortex passes through coating surface treatment solution, and solidify to form; Described treatment solution is the treatment solution being comprised of the first polyurethane component and the second polyurethane component, 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 1 of the polytrimethylene ether glycol of the tolylene diisocyanate of 10 ~ 12 weight parts (TDI), 3 ~ 4 weight parts, 2.0 ~ 2.5 weight parts, the dibutyltin dilaurate of the hydroxy-terminated polybutadienes-vinyl cyanide of 4-butyleneglycol, 1.8 ~ 2.0 weight parts (HTBN), 0.1 ~ 0.2 weight part mixes, and then at 70 ~ 80 ℃, reacts 1.5 ~ 2.0 hours; Reaction solution adds the deionized water of 30 ~ 32 weight parts and the sodium laurylsulfonate of 0.8 ~ 1.2 weight part after being cooled to room temperature, after stirring, disperseing, obtains the first described polyurethane component.
Wherein, the second described polyurethane component prepares by following steps: by 1 of the polytetrahydrofuran diol of the xylylene diisocyanate of 10 ~ 12 weight parts (XDI), 3 ~ 4 weight parts, 2.0 ~ 2.5 weight parts, the polyallylamine resin (PAA-01) of 4-butyleneglycol, 1.8 ~ 2.0 weight parts, the dibutyltin dilaurate of 0.1 ~ 0.2 weight part mix, and then at 80 ~ 85 ℃, react 2.0 hours; Reaction solution adds the deionized water of 30 ~ 32 weight parts and the sodium laurylsulfonate of 0.8 ~ 1.2 weight part after being cooled to room temperature, stirs, disperses to obtain the second described polyurethane component.
Compared with prior art, polyurethane elastomer of the present invention and the sole of being made by it have following useful technique effect: polyurethane elastomer of the present invention has microvoid structure, compare and there is higher elasticity and intensity with common porous plastics, not only density is relatively low, and resistance to bend(ing) and ageing-resistant performance excellence.
Embodiment
Below in conjunction with specific embodiments the structure of polyurethane elastomer of the present invention and the sole made by it, 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, described polyurethane elastomer is by the liquid MDI that contains 20 ~ 22 weight parts (MDI of Carbodiimide-Modified), the polyester polyol P-2013(Japan Kuraray company of 8 ~ 10 weight parts), the polymer polyatomic alcohol of 5 ~ 6 weight parts, 1 of 5 ~ 6 weight parts, 4-butyleneglycol, the EVA multipolymer of 1.8 ~ 2.0 weight parts (in multipolymer, poly content is 35 ~ 40wt%), the diethyl aminoethyl methacrylate of 1.2 ~ 1.5 weight parts, the triethylenediamine of 0.20 ~ 0.25 weight part, the water of 0.40 ~ 0.50 weight part, the composition of the foam stabilizer of 0.25 ~ 0.30 weight part (DC-193) mixes under the condition of 100 ~ 105 ℃, then be injected into that in the mould of preheated predetermined shape, (preheating temperature is 115 ℃, the shape of mould is the sole of designed shape for example) react 25 ~ 30 minutes, the demoulding, then 110 ℃ of slakings, within 12 hours, can obtain described polyurethane elastomer.As required, described composition can also contain the additives such as antioxidant, photostabilizer, deaerating agent, UV light absorber, weighting agent, pigment, heat-resisting stabilizing agent; The interpolation of additive belongs to the state of the art, does not repeat them here.And in the present invention and following embodiment and comparative example: the polymer polyatomic alcohol relating to is polyoxytrimethylene triol (MN-3050), the vinyl cyanide of 2.0 mass parts, the glycidyl acrylate of the vinylbenzene of 3.0 mass parts, 5 mass parts and the initiator Diisopropyl azodicarboxylate of 0.8 mass parts with 10 mass parts, carries out graft polymerization and form under nitrogen protection.Specifically, use is provided with the reactor of whipping appts, reflux cooling pipe, nitrogen ingress pipe, thermometer, above-mentioned raw materials and the appropriate rear solution forming of ethyl acetate mixing are joined in reactor, under nitrogen atmosphere, under the condition of 120 ℃, react 2 hours, after reaction finishes, reduce pressure to remove unreacted monomer.
embodiment 1
Polyurethane elastomer described in the present embodiment is by the MDI of the Carbodiimide-Modified that contains 20 weight parts, the polyester polyol P-2013(Japan Kuraray company of 8 weight parts), the polymer polyatomic alcohol of 6 weight parts, 1 of 6 weight parts, 4-butyleneglycol, the EVA multipolymer of 2.0 weight parts (in multipolymer, poly content is 35wt%), the diethyl aminoethyl methacrylate of 1.5 weight parts, the triethylenediamine of 0.20 weight part, the water of 0.40 weight part, the composition of the foam stabilizer DC-193 of 0.25 weight part mixes under the condition of 100 ℃, then be injected into preheating temperature and be in the mould of predetermined shape of 115 ℃, react 25 minutes, then the demoulding can obtain described polyurethane elastomer for 12 hours 110 ℃ of slakings.
embodiment 2
Polyurethane elastomer described in the present embodiment is by the MDI of the Carbodiimide-Modified that contains 22 weight parts, the polyester polyol P-2013(Japan Kuraray company of 10 weight parts), the polymer polyatomic alcohol of 5 weight parts, 1 of 5 weight parts, 4-butyleneglycol, the EVA multipolymer of 1.8 weight parts (in multipolymer, poly content is 35wt%), the diethyl aminoethyl methacrylate of 1.5 weight parts, the triethylenediamine of 0.20 weight part, the water of 0.40 weight part, the composition of the foam stabilizer DC-193 of 0.25 weight part mixes under the condition of 100 ℃, then be injected into preheating temperature and be in the mould of predetermined shape of 115 ℃, react 25 minutes, then the demoulding can obtain described polyurethane elastomer for 12 hours 110 ℃ of slakings.
comparative example 1
Polyurethane elastomer described in this comparative example is by the MDI of the Carbodiimide-Modified that contains 20 weight parts, the polyester polyol P-2013(Japan Kuraray company of 8 weight parts), 1 of 6 weight parts, 4-butyleneglycol, the EVA multipolymer of 2.0 weight parts (in multipolymer, poly content is 35wt%), the diethyl aminoethyl methacrylate of 1.5 weight parts, the triethylenediamine of 0.20 weight part, the water of 0.40 weight part, the composition of the foam stabilizer DC-193 of 0.25 weight part mixes under the condition of 100 ℃, then be injected into preheating temperature and be in the mould of predetermined shape of 115 ℃, react 25 minutes, then the demoulding can obtain described polyurethane elastomer for 12 hours 110 ℃ of slakings.
comparative example 2
Polyurethane elastomer described in this comparative example is by the MDI of the Carbodiimide-Modified that contains 20 weight parts, the polyester polyol P-2013(Japan Kuraray company of 8 weight parts), the polymer polyatomic alcohol of 6 weight parts, 1 of 6 weight parts, 4-butyleneglycol, the EVA multipolymer of 2.0 weight parts (in multipolymer, poly content is 35wt%), the triethylenediamine of 0.20 weight part, the water of 0.40 weight part, the composition of the foam stabilizer DC-193 of 0.25 weight part mixes under the condition of 100 ℃, then be injected into preheating temperature and be in the mould of predetermined shape of 115 ℃, react 25 minutes, then the demoulding can obtain described polyurethane elastomer for 12 hours 110 ℃ of slakings.
The polyurethane elastomer that embodiment 1 ~ 2 and comparative example 1 ~ 2 are prepared carries out performance test, and test result is as shown in table 1.
Table 1
embodiment 3
The present embodiment relates to a kind of sole, described sole is mainly formed by the polyurethane elastomer of embodiment 1, and at described polyurethane elastomer surface coated surface treatment liquid, then 100 ℃ of solidification treatment 2 ~ 3 minutes, afterwards 120 ℃ of solidification treatment 1 minute again; Be formed with the polyurethane wear resistant layer that thickness is about 0.5mm.Described surface treatment liquid is the treatment solution being comprised of the first polyurethane component and the second polyurethane component; And the mass ratio of described the first polyurethane component and described the second polyurethane component is 2:1.The first described polyurethane component by the TDI-80 of 10 ~ 12 weight parts, the polytrimethylene ether glycol of 3 ~ 4 weight parts (the Cerenol H of U.S. DuPont company series), the BDO of 2.0 ~ 2.5 weight parts, the dibutyltin dilaurate of the HTBN of 1.8 ~ 2.0 weight parts, 0.1 ~ 0.2 weight part mixes, the deionized water of 30 ~ 32 weight parts and the sodium laurylsulfonate of 0.8 ~ 1.2 weight part made; The second described polyurethane component by the XDI of 10 ~ 12 weight parts, the polytetrahydrofuran diol of 3 ~ 4 weight parts, 2.0 ~ 2.5 weight parts 1, the polyallylamine resin (PAA-01) of 4-butyleneglycol, 1.8 ~ 2.0 weight parts, the dibutyltin dilaurate of 0.1 ~ 0.2 weight part, the sodium laurylsulfonate of the deionized water of 30 ~ 32 weight parts and 0.8 ~ 1.2 weight part, stir, disperse to obtain the second described polyurethane component.
embodiment 4
The present embodiment relates to a kind of sole, described sole is mainly formed by the polyurethane elastomer of embodiment 1, and at described polyurethane elastomer surface coated surface treatment liquid, then 100 ℃ of solidification treatment 2 ~ 3 minutes, afterwards 120 ℃ of solidification treatment 1 minute again; Be formed with the polyurethane wear resistant layer that thickness is about 0.5mm.Described surface treatment liquid is the treatment solution being comprised of the first polyurethane component and the second polyurethane component; And the mass ratio of described the first polyurethane component and described the second polyurethane component is 2:1.The first described polyurethane component by the TDI-80 of 10 ~ 12 weight parts, the polytrimethylene ether glycol of 3 ~ 4 weight parts (the Cerenol H of U.S. DuPont company series), the BDO of 2.0 ~ 2.5 weight parts, the dibutyltin dilaurate of the HTBN of 1.8 ~ 2.0 weight parts, 0.1 ~ 0.2 weight part mixes, the deionized water of 30 ~ 32 weight parts and the sodium laurylsulfonate of 0.8 ~ 1.2 weight part made; The second described polyurethane component by the XDI of 10 ~ 12 weight parts, the polytetrahydrofuran diol of 3 ~ 4 weight parts, 2.0 ~ 2.5 weight parts 1, the polyallylamine resin (PAA-01) of 4-butyleneglycol, 1.8 ~ 2.0 weight parts, the dibutyltin dilaurate of 0.1 ~ 0.2 weight part, the sodium laurylsulfonate of the deionized water of 30 ~ 32 weight parts and 0.8 ~ 1.2 weight part, stir, disperse to obtain the second described polyurethane component.
comparative example 3
This comparative example relates to a kind of sole, described sole is mainly formed by the polyurethane elastomer of embodiment 1, and at described polyurethane elastomer surface coated surface treatment liquid, then 100 ℃ of solidification treatment 2 ~ 3 minutes, afterwards 120 ℃ of solidification treatment 1 minute again; Be formed with the polyurethane wear resistant layer that thickness is about 0.5mm.Described surface treatment liquid is the treatment solution being comprised of the first polyurethane component and the second polyurethane component; And the mass ratio of described the first polyurethane component and described the second polyurethane component is 2:1.The first described polyurethane component by the TDI-80 of 10 ~ 12 weight parts, the polytrimethylene ether glycol of 3 ~ 4 weight parts (the Cerenol H of U.S. DuPont company series), the BDO of 2.0 ~ 2.5 weight parts, the dibutyltin dilaurate of 0.1 ~ 0.2 weight part mixes, the deionized water of 30 ~ 32 weight parts and the sodium laurylsulfonate of 0.8 ~ 1.2 weight part made; The second described polyurethane component by the XDI of 10 ~ 12 weight parts, the polytetrahydrofuran diol of 3 ~ 4 weight parts, 2.0 ~ 2.5 weight parts 1, the polyallylamine resin (PAA-01) of 4-butyleneglycol, 1.8 ~ 2.0 weight parts, the dibutyltin dilaurate of 0.1 ~ 0.2 weight part, the sodium laurylsulfonate of the deionized water of 30 ~ 32 weight parts and 0.8 ~ 1.2 weight part, stir, disperse to obtain the second described polyurethane component.
comparative example 4
This comparative example relates to a kind of sole, described sole is mainly formed by the polyurethane elastomer of embodiment 1, and at described polyurethane elastomer surface coated surface treatment liquid, then 100 ℃ of solidification treatment 2 ~ 3 minutes, afterwards 120 ℃ of solidification treatment 1 minute again; Be formed with the polyurethane wear resistant layer that thickness is about 0.5mm.Described surface treatment liquid is the treatment solution being comprised of the first polyurethane component and the second polyurethane component; And the mass ratio of described the first polyurethane component and described the second polyurethane component is 2:1.The first described polyurethane component by the TDI-80 of 10 ~ 12 weight parts, the polytrimethylene ether glycol of 3 ~ 4 weight parts (the Cerenol H of U.S. DuPont company series), the BDO of 2.0 ~ 2.5 weight parts, the dibutyltin dilaurate of the HTBN of 1.8 ~ 2.0 weight parts, 0.1 ~ 0.2 weight part mixes, the deionized water of 30 ~ 32 weight parts and the sodium laurylsulfonate of 0.8 ~ 1.2 weight part made; The second described polyurethane component by the XDI of 10 ~ 12 weight parts, the polytetrahydrofuran diol of 3 ~ 4 weight parts, 2.0 ~ 2.5 weight parts 1, the sodium laurylsulfonate of the deionized water of the dibutyltin dilaurate of 4-butyleneglycol, 0.1 ~ 0.2 weight part, 30 ~ 32 weight parts and 0.8 ~ 1.2 weight part, stirs, disperses to obtain the second described polyurethane component.
comparative example 5
This comparative example relates to a kind of sole, described sole is mainly formed by the polyurethane elastomer of embodiment 1, and at described polyurethane elastomer surface coated surface treatment liquid, then 100 ℃ of solidification treatment 2 ~ 3 minutes, afterwards 120 ℃ of solidification treatment 1 minute again; Be formed with the polyurethane wear resistant layer that thickness is about 0.5mm.Described surface treatment liquid is the treatment solution being comprised of the first polyurethane component and the second polyurethane component; And the mass ratio of described the first polyurethane component and described the second polyurethane component is 2:1.The first described polyurethane component by the TDI-80 of 10 ~ 12 weight parts, the polytrimethylene ether glycol of 3 ~ 4 weight parts (the Cerenol H of U.S. DuPont company series), the BDO of 2.0 ~ 2.5 weight parts, the dibutyltin dilaurate of 0.1 ~ 0.2 weight part mixes, the deionized water of 30 ~ 32 weight parts and the sodium laurylsulfonate of 0.8 ~ 1.2 weight part made; The second described polyurethane component by the XDI of 10 ~ 12 weight parts, the polytetrahydrofuran diol of 3 ~ 4 weight parts, 2.0 ~ 2.5 weight parts 1, the sodium laurylsulfonate of the deionized water of the dibutyltin dilaurate of 4-butyleneglycol, 0.1 ~ 0.2 weight part, 30 ~ 32 weight parts and 0.8 ~ 1.2 weight part, 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, and wherein said shore hardness refers to the performance on polyurethane wear resistant layer surface; And resistance to bending refers to that repeatedly carrying out at normal temperatures pliability test forms the number of times till the above crackle of 10mm with surface.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, the embodiment of all distortion being equal to of making in the claimed scope of claims of the present invention and change is all in the present invention's scope required for protection.
Claims (10)
1. a polyurethane elastomer, it is characterized in that: by the vulcabond that contains 20 ~ 22 weight parts, the polyester polyol of 8 ~ 10 weight parts, the polymer polyatomic alcohol of 5 ~ 6 weight parts, 1 of 5 ~ 6 weight parts, 4-butyleneglycol, the EVA multipolymer of 1.8 ~ 2.0 weight parts, the diethyl aminoethyl methacrylate of 1.2 ~ 1.5 weight parts, the triethylenediamine of 0.20 ~ 0.25 weight part, the water of 0.40 ~ 0.50 weight part, the composition of the foam stabilizer of 0.25 ~ 0.30 weight part mixes, then be injected into the interior reaction of mould of preheated predetermined shape, solidify to form.
2. polyurethane elastomer according to claim 1, is characterized in that: the trade mark of described polyester polyol is P-2013, and nominal relative molecular mass is 2000.
3. polyurethane elastomer according to claim 1; it is characterized in that: described polymer polyatomic alcohol is with polyoxytrimethylene triol, vinyl cyanide, vinylbenzene, glycidyl acrylate and initiator Diisopropyl azodicarboxylate, under nitrogen protection, carry out graft polymerization and form.
4. polyurethane elastomer according to claim 1, is characterized in that: in described EVA multipolymer, in described multipolymer, the content of vinyl acetate is 35 ~ 40wt%.
5. polyurethane elastomer according to claim 1, is characterized in that: described composition contains at least one in antioxidant, photostabilizer, deaerating agent, UV light absorber, weighting agent, pigment or heat-resisting stabilizing agent.
6. a sole, is characterized in that: described sole is made by the polyurethane elastomer described in claim 1 ~ 5 any one.
7. sole according to claim 6, is characterized in that: the surface at described polyurethane elastomer also has abrasion-proof gauge cortex, and described abrasion-proof gauge cortex passes through coating surface treatment solution, and solidify to form.
8. sole according to claim 7, is characterized in that: described treatment solution is the treatment solution being comprised of the first polyurethane component and the second polyurethane component, and the mass ratio of described the first polyurethane component and described the second polyurethane component is 2:1 ~ 3:1.
9. sole according to claim 8, it is characterized in that: the first described polyurethane component prepares by following steps: by 1 of the polytrimethylene ether glycol of the tolylene diisocyanate of 10 ~ 12 weight parts, 3 ~ 4 weight parts, 2.0 ~ 2.5 weight parts, the dibutyltin dilaurate of the hydroxy-terminated polybutadienes-vinyl cyanide of 4-butyleneglycol, 1.8 ~ 2.0 weight parts, 0.1 ~ 0.2 weight part mixes, and then at 70 ~ 80 ℃, reacts 1.5 ~ 2.0 hours; Reaction solution adds the deionized water of 30 ~ 32 weight parts and the sodium laurylsulfonate of 0.8 ~ 1.2 weight part after being cooled to room temperature, after stirring, disperseing, obtains the first described polyurethane component.
10. sole according to claim 8, it is characterized in that: the second described polyurethane component prepares by following steps: by 1 of the polytetrahydrofuran diol of the xylylene diisocyanate of 10 ~ 12 weight parts, 3 ~ 4 weight parts, 2.0 ~ 2.5 weight parts, the polyallylamine resin of 4-butyleneglycol, 1.8 ~ 2.0 weight parts, the dibutyltin dilaurate of 0.1 ~ 0.2 weight part mix, and then at 80 ~ 85 ℃, react 2.0 hours; Reaction solution adds the deionized water of 30 ~ 32 weight parts and the sodium laurylsulfonate of 0.8 ~ 1.2 weight part after being cooled to room temperature, stirs, disperses to obtain the second described polyurethane component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410344065.8A CN104072716B (en) | 2014-07-18 | 2014-07-18 | Polyurethane elastomer and the sole of being made by it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410344065.8A CN104072716B (en) | 2014-07-18 | 2014-07-18 | Polyurethane elastomer and the sole of being made by it |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104072716A true CN104072716A (en) | 2014-10-01 |
| CN104072716B CN104072716B (en) | 2016-05-11 |
Family
ID=51594348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410344065.8A Active CN104072716B (en) | 2014-07-18 | 2014-07-18 | Polyurethane elastomer and the sole of being made by it |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104072716B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153400A (en) * | 2015-06-30 | 2015-12-16 | 晋江市池店镇娇鹏贸易有限公司 | Polyurethane microporous elastomer for outdoor soles |
| CN106519174A (en) * | 2016-12-07 | 2017-03-22 | 田昊立 | High resilience, soft, medium and low density polyurethane |
| CN106832139A (en) * | 2017-01-18 | 2017-06-13 | 新辉（中国）新材料有限公司 | Latex comprising polyurethane-modified Carboxy copolymer and preparation method thereof |
| CN107136582A (en) * | 2017-06-29 | 2017-09-08 | 东莞市永存内衣有限公司 | Brassiere, its preparation method of a kind of breast support, its preparation method and application breast support |
| CN107417879A (en) * | 2016-05-24 | 2017-12-01 | 北京化工大学 | A kind of high-performance tire solution polymerized butadiene styrene rubber-polyurethane elastomer material and preparation method |
| CN107540812A (en) * | 2017-09-08 | 2018-01-05 | 北京化工大学 | A kind of thermoplasticity solution polymerized butadiene styrene rubber polyurethane elastomer material and preparation method |
| 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 |
| JPWO2020075651A1 (en) * | 2018-10-11 | 2021-05-13 | 三井化学株式会社 | Manufacturing method of foamed polyurethane elastomer raw material, foamed polyurethane elastomer, midsole and foamed polyurethane elastomer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914192A (en) * | 2010-08-27 | 2010-12-15 | 旭川化学（苏州）有限公司 | Mildew-proof and antibacterial sole polyurethane stock solution and production process of polyurethane sole |
| CN102863603A (en) * | 2012-09-24 | 2013-01-09 | 吴江市信许塑料鞋用配套有限公司 | Preparation method of high-elasticity sole material |
-
2014
- 2014-07-18 CN CN201410344065.8A patent/CN104072716B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914192A (en) * | 2010-08-27 | 2010-12-15 | 旭川化学（苏州）有限公司 | Mildew-proof and antibacterial sole polyurethane stock solution and production process of polyurethane sole |
| CN102863603A (en) * | 2012-09-24 | 2013-01-09 | 吴江市信许塑料鞋用配套有限公司 | Preparation method of high-elasticity sole material |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153400A (en) * | 2015-06-30 | 2015-12-16 | 晋江市池店镇娇鹏贸易有限公司 | Polyurethane microporous elastomer for outdoor soles |
| 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 |
| CN107417879A (en) * | 2016-05-24 | 2017-12-01 | 北京化工大学 | A kind of high-performance tire solution polymerized butadiene styrene rubber-polyurethane elastomer material and preparation method |
| 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 |
| CN106832139A (en) * | 2017-01-18 | 2017-06-13 | 新辉（中国）新材料有限公司 | Latex comprising polyurethane-modified Carboxy copolymer and preparation method thereof |
| 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 |
| CN107136582A (en) * | 2017-06-29 | 2017-09-08 | 东莞市永存内衣有限公司 | Brassiere, its preparation method of a kind of breast support, its preparation method and application breast support |
| CN107540812A (en) * | 2017-09-08 | 2018-01-05 | 北京化工大学 | A kind of thermoplasticity solution polymerized butadiene styrene rubber polyurethane elastomer material and preparation method |
| 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 |
| JPWO2020075651A1 (en) * | 2018-10-11 | 2021-05-13 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104072716B (en) | 2016-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104072716A (en) | Polyurethane elastomer and sole made from same | |
| CN107698860B (en) | High-resilience composition foaming material for soles and preparation method thereof | |
| CN104448791B (en) | High-rigidity transparent polyurethane elastomer and preparation method thereof | |
| TWI738922B (en) | Thermoplastic polyurethane resin for foaming and its production method and molded product | |
| CN106700029B (en) | Polyurethane resin for shoe sole and preparation method and application thereof | |
| EP3581603A1 (en) | Thermoplastic organosilicone-polyurethane elastomer and preparation method therefor | |
| WO2013037179A1 (en) | Auto-crusting microporous elastomer composition for use in polyurethane foam-filled tire | |
| JP2016518506A (en) | Thermoplastic polyurethanes made from prepolymers of low free monomers | |
| US11725075B2 (en) | Thermoplastic polyurethane | |
| EP3409705B1 (en) | Composition for polyurethane foam containing polyrotaxane, polyurethane foam derived from composition, and method for producing polyurethane foam | |
| CN1961016A (en) | Low-density polyurethane foam materials and their use in shoe soles | |
| JP5408772B2 (en) | insole | |
| CN104140520A (en) | Super-soft high-elasticity hydrolysis resistance high-stripping wet polyurethane resin and preparation method thereof | |
| CN107417874A (en) | A kind of end-sealed type double component solvent-free waterproof moisture-penetrating urethane resin and preparation method thereof | |
| CN104163909A (en) | Polyurethane resin for hydrolysis-resistant sofa leather and preparation method thereof | |
| CN101565495A (en) | Polyurethane elastomer as well as preparation method and usage thereof | |
| CN106497008A (en) | A kind of ultralight PU foaming composite sheet and preparation method thereof | |
| TW201938683A (en) | Elastic composite material process and product produced therefrom enabling the overall structure to be light-weighted and having an effect of maintaining a certain structural strength | |
| CN102181037A (en) | Method for preparing 3,3'-dimethyl-4,4'-biphenyl diisocyanate (TODI)-based thermoplastic polyurethane elastomer | |
| CN113754857A (en) | Polyurethane elastomer for quickly-formed low-temperature-resistant shoe material and preparation method thereof | |
| CN108440783A (en) | A kind of polyurethane foam bead and preparation method thereof | |
| CN106674474A (en) | Polyurethane shoe material capable of demoulding quickly at room temperature, and preparation method of polyurethane shoe material | |
| CN106432687B (en) | Low-density mirror surface microporous polyurethane elastomer resin and application method | |
| CN103965433B (en) | The soft low-density polyurethane foam materials of sole | |
| KR20150081035A (en) | Polyurethane resin composition and synthesizing process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |