CN111718575A - Flexible polyurethane shoe material composition and preparation method thereof - Google Patents
Flexible polyurethane shoe material composition and preparation method thereof Download PDFInfo
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- C08J9/125—Water, e.g. hydrated salts
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
The invention belongs to the field of polyurethane shoe materials, and particularly relates to a flexible polyurethane shoe material composition and a preparation method thereof; the flexibility and the strength of the polyurethane shoe material can be improved by pre-dispersing the graphene in the material A and the material B respectively. Compound plastify processing with graphite alkene and wood fiber, further use thermoplastic polybutylene succinate as the carrier, utilize syntropy twin-screw extruder's strong shearing with graphite alkene dispersion wherein, and smash to be the flocculus, then add polyester polyol, through the ball-milling, graphite alkene dispersion is with micellagic dispersion in polyester polyol, this kind of graphite alkene dispersion micelle, not only has good flexibility, and the abundant interface of graphite alkene can effectively promote the mechanical properties promotion of polyurethane, has showing the advantage in the aspect of promoting resistant flexible performance. The preparation method is simple and has significant meaning for upgrading products of polyurethane shoe material production enterprises.
Description
Technical Field
The invention belongs to the field of polyurethane shoe materials, and particularly relates to a flexible polyurethane shoe material composition and a preparation method thereof.
Background
Polyurethane is a multifunctional and versatile synthetic polymeric material, typically prepared by reacting an oligomeric polyol, a polyisocyanate, and a chain extender/crosslinker. Compared with metal materials, polyurethane has the advantages of light weight, low noise, wear resistance, low processing cost, acid corrosion resistance and the like. Compared with plastics, the high-toughness wear-resistant rubber has the advantages of high toughness, high wear resistance and the like. Compared with common rubber, the polyurethane has the advantages of wear resistance, cutting resistance, tearing resistance, high bearing property, ozone resistance and the like, is simple to manufacture, can be encapsulated and poured, and has wide hardness range. The material can be made into hard foam heat-insulating material, soft foam pad material, elastomer material, microporous elastomer shoe material, high-elastic fiber, fabric and leather coating, adhesive, sealant, etc. due to different raw material selection and reaction forming process. Due to the diversification of product forms and manufacturing processes, the product has wide application fields, and has application in heat preservation, cold chain, traffic, buildings, home furnishing, shoe products, mechanical accessories, sports equipment and the like.
Polyurethane has been rapidly developed in recent years as a shoe material in the field of shoe making. At present, most of common shoe materials are made of polyvinyl chloride, and have poor elasticity, poor wear resistance and insufficient softness. Because polyurethane has wear-resisting, antiskid, light characteristic as the shoe material, replace polyvinyl chloride, thermoplastic elastomer, ethylene vinyl acetate copolymer, etc. to become the first choice of the high-quality shoe material gradually in the market at present.
Polyurethane has the characteristics of good buffer performance, light weight, wear resistance, skid resistance and the like, has good processing performance, and becomes an important synthetic material for shoes in the shoe manufacturing industry, and can be used for manufacturing sport shoes, soles, heels and toe caps of baseball shoes, golf balls, football and the like, ski shoes, safety shoes, leisure shoes and the like. The polyurethane material used for the shoe material includes cast microporous elastomer, thermoplastic polyurethane elastomer and the like, and the microporous elastomer sole is taken as the main material. The polyurethane microporous elastomer has light weight and good wear resistance, and is favored by shoe manufacturers. The density of the product is 0.6g/cm3And the shoe material is lighter than the traditional rubber body and PVC shoe material. Moreover, the polyurethane shoe material solves the problems that the plastic sole and the rubber sole are easy to break and the like and the rubber sole is easy to break in China at present. The shoe material industry has great changes in processing technology, forming technology, safety performance, comfort and the like. At present, high-grade shoe materials gradually abandon rubber and begin to use polyurethane materials.
Although the polyurethane material has excellent mechanical properties and good wear resistance and oil resistance, when the polyurethane material is used for sole materials, in order to ensure the strength, the commonly used polyester polyol is used as stock solution of raw materials; the prepared polyurethane shoe material has poor flexibility, and particularly has sharply reduced flexibility at low temperature, so that the polyurethane shoe material cannot provide good flexing resistance. The prior art generally adds a soft segment by compounding part of polyether polyol in the A liquid to increase the flexibility of the polyurethane shoe material. Although polyether polyurethane has better low temperature resistance, the tear resistance and tensile strength of the polyether polyurethane are lower, the basic performance requirements of shoe materials cannot be met, only partial polyester polyurethane can be replaced, and the problem of fundamentally improving the low-temperature flexibility of the polyurethane shoe materials cannot be solved.
The Chinese patent application No. 201810195976.7 discloses a high-resilience low-temperature-resistant polyurethane sole raw material and a preparation method thereof, and the technical scheme provided by the patent is that a polyurethane material obtained by matching and combining a plurality of polyester polyols has high resilience and has sufficient folding resistance under low-temperature conditions.
The Chinese patent application No. 201110408610.1 discloses a polyurethane shoe material containing wood chips and a manufacturing method thereof, and the polyurethane shoe material with light weight, high buffer, high elasticity and high strength is obtained by adding the wood chips.
However, when high-grade shoe materials are prepared, the method has a limit on improving the flexibility of the polyurethane material.
Disclosure of Invention
The polyester polyol polyurethane has higher strength but poorer toughness, and the common polyester polyol polyurethane is difficult to meet the requirements of high-grade shoe materials in some sports shoe base materials with higher requirements. Therefore, the invention provides a flexible polyurethane shoe material composition and a preparation method thereof.
A flexible polyurethane shoe material composition is characterized by comprising 90-100 parts by weight of a material A and 80-90 parts by weight of a material B; wherein:
the material A is obtained by the following method:
uniformly dispersing 3-5 parts by weight of graphene, 5-10 parts by weight of wood fiber and 1-5 parts by weight of polyethylene glycol in a high-speed mixer, adding 20-30 parts by weight of thermoplastic poly (butylene succinate) for uniform premixing, feeding into a double-screw extruder, extruding, mixing and extruding at the temperature of 100 ℃ and 120 ℃ to obtain bulk graphene dispersion;
crushing a graphene dispersion to generate floccule, adding polyester polyol, grinding in a ball mill at 70-80 ℃ for 10-15min, and dispersing the graphene dispersion in the polyester polyol in colloidal particle shape to form polyester polyol containing colloidal particles; then adding a chain extender, a catalyst, a foaming agent and a foam homogenizing agent to disperse uniformly to obtain a material A;
the material B is obtained by the following method:
adding graphene, nano zinc oxide and diisocyanate into a ball mill, grinding and dispersing to obtain fine slurry, then putting the fine slurry into a reaction kettle, controlling the temperature of the reaction kettle to be 80-90 ℃, stirring at the speed of 50-100rpm, simultaneously adding organic bismuth and polyether polyol, stirring and reacting for 20-30min, discharging the materials until the temperature is reduced to room temperature, and sealing and packaging to obtain a prepolymer B material.
Further, a preparation method of the flexible polyurethane shoe material composition is provided, which is characterized by comprising the following steps:
s1: uniformly dispersing 3-5 parts by weight of graphene, 5-10 parts by weight of wood fiber and 1-5 parts by weight of polyethylene glycol in a high-speed mixer, adding 20-30 parts by weight of thermoplastic poly (butylene succinate) for uniform premixing, and feeding the mixture into a double-screw extruder for mixing and extruding at the temperature of 100 ℃ and 120 ℃ to obtain bulk graphene dispersion;
s2, crushing the graphene dispersion to generate floccules, adding polyester polyol, grinding in a ball mill at 70-80 ℃ for 10-15min, and dispersing the graphene dispersion in the polyester polyol in colloidal particles to form polyester polyol containing colloidal particles; then adding a chain extender, a catalyst, a foaming agent and a foam homogenizing agent to disperse uniformly to obtain a material A;
s3: adding graphene, nano zinc oxide and diisocyanate into a ball mill, grinding and dispersing to obtain fine slurry, then putting the fine slurry into a reaction kettle, controlling the temperature of the reaction kettle to be 80-90 ℃, stirring at the speed of 50-100rpm, simultaneously adding organic bismuth and polyether polyol, stirring and reacting for 20-30min, discharging the materials until the temperature is reduced to room temperature, and sealing and packaging to obtain a prepolymer B material.
Preferably, the thermoplastic polybutylene succinate in step S1 is high molecular polybutylene succinate with thermoplastic processability; PBS H1200, supplied by Pasteur, Germany, is preferred.
Preferably, the twin-screw extruder in step S1 is a co-rotating twin-screw extruder, which has high shear dispersion efficiency.
Preferably, the polyethylene glycol in step S1 is at least one of polyethylene glycol 400 and polyethylene glycol 600.
Polyethylene glycol has certain plasticity to wood fiber, because the graphite alkene quantity is less, consequently, at first with graphite alkene and wood fiber complex plasticization processing, further use thermoplastic polybutylene succinate as the carrier, utilize the strong shearing of syntropy twin-screw extruder to disperse graphite alkene wherein, and smash and be the flocculus, then add polyester polyol, through the ball-milling, graphite alkene dispersion is in polyester polyol with the micellar dispersion, this kind of graphite alkene dispersion micelle, have great granule, easily disperse in A material and do not agglomerate, especially graphite alkene dispersion is in the micellar dispersion, not only have good flexibility, and the abundant interface of graphite alkene can effectively promote the mechanical properties promotion of polyurethane, have showing the advantage in the aspect of promoting tear resistance, flexure resistance.
Preferably, in step S2, the graphene dispersion, the polyester polyol, the chain extender, the catalyst, the foaming agent, and the foam stabilizer are, in parts by weight: 1-5 parts of graphene dispersion, 80-85 parts of polyester polyol, 3-5 parts of chain extender, 0.1-0.3 part of catalyst, 0.1-0.4 part of foaming agent and 0.1-0.2 part of foam homogenizing agent.
Further preferably, the polyester polyol in step S2 is polyethylene adipate or polybutylene adipate having a molecular weight of 2000.
Further preferably, the chain extender in S2 is one of 1, 4-butanediol, ethylene glycol, glycerol, diethanolamine, and methyldiethanolamine.
Further preferably, the catalyst in S2 is a compound of triethylene diamine and Dabco KTM60 amine catalyst (provided by air products of america) in a mass ratio of 1:2, which can effectively improve the fluidity of the micro-foaming reaction, so that the polyurethane shoe material is more uniform, and the improvement of flexibility is assisted.
Further preferably, the foaming agent in S2 is water.
Further preferably, the foam stabilizer in S2 is dimethyl siloxane.
Preferably, in step S3, the graphene, the nano zinc oxide, the diisocyanate, the organic bismuth, and the polyether polyol are, in parts by weight: 0.5-1 part of graphene, 5-10 parts of nano zinc oxide, 80-100 parts of diisocyanate, 0.05-0.1 part of organic bismuth and 45-60 parts of polyether polyol.
The graphene is difficult to disperse, the graphene, the nano zinc oxide and the diisocyanate are added into a ball mill for grinding and dispersing, so that less graphene is loaded on the zinc oxide and is pre-dispersed in the diisocyanate through grinding, the nano zinc oxide has tiny particles, large surface area and good dispersibility, is usually used as a reinforcing filler of polyurethane shoe materials, and is compounded with the nano zinc oxide, so that the graphene is better dispersed, and the surface effect of the graphene is fully exerted. And the prepolymerization treatment is further carried out, so that the graphene can be effectively dispersed in polyurethane when the shoe material is prepared by subsequent pouring, and the strength, flexibility and tearing resistance of the polyurethane shoe material are improved.
Preferably, the diisocyanate in step S3 is selected from conventional diisocyanates, such as at least one of Toluene Diisocyanate (TDI), diphenylmethane-4, 4' -diisocyanate (MDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), p-phenylene diisocyanate (PPDI), and Xylylene Diisocyanate (XDI). As a further preference of the shoe material, we recommend to use Toluene Diisocyanate (TDI) and/or diphenylmethane-4, 4' -diisocyanate (MDI) in terms of price measurement, stable supply and the like through practice. In particular, Toluene Diisocyanate (TDI), diphenylmethane-4, 4' -diisocyanate (MDI) are selected according to the mass ratio of 1: 1.5 compounding to obtain the product.
Preferably, the organic bismuth in step S3 is BiCAT 8118 available in the market.
Preferably, the polyether polyol in step S3 is Shanghai Gaoqiao GEP-330N.
Due to the special interface performance, the graphene has excellent effects in the aspects of material reinforcement and toughening. However, graphene is difficult to disperse directly in the material, resulting in a reduction in interfacial properties. The polyurethane shoe material raw materials are two components, and can react by fast mixing when in use, so that the dispersion of directly adding graphene is more difficult. In order to obtain the polyurethane shoe material with good flexibility, the graphene is pre-dispersed in the material A and the material B respectively, so that the graphene is uniformly dispersed in the material A and the material B when the material A and the material B are directly mixed. In particular: in A material, compound plasticization with graphite alkene and wood fiber is handled, use thermoplastic polybutylene succinate as the carrier, utilize syntropy twin-screw extruder's strong shearing to disperse graphite alkene wherein, and smash and be the flocculary, then add polyester polyol, through the ball-milling, graphite alkene dispersion is in polyester polyol with the micellar dispersion, this kind of graphite alkene dispersion micelle, great granule has, easily disperse and do not agglomerate in A material, not only has good flexibility, and the abundant interface of graphite alkene can effectively promote the mechanical properties promotion of polyurethane, has showing the advantage in the aspect of the flexible performance. In the material B, graphene, nano-zinc oxide and diisocyanate are added into a ball mill for grinding and dispersing, so that less graphene is loaded on zinc oxide and is pre-dispersed in diisocyanate through grinding, polyether polyol is further added for pre-polymerization, the nano-zinc oxide has the advantages of small particles, large surface area and good dispersibility, the nano-zinc oxide is often used as a reinforcing filler of polyurethane shoe materials, the graphene and the nano-zinc oxide are compounded, the dispersion of the graphene is better, and the surface effect of the graphene is fully exerted more importantly. The graphene can be effectively dispersed in polyurethane when the shoe material is prepared by subsequent pouring, so that the strength, flexibility and tear resistance of the polyurethane shoe material are improved.
Compared with the prior art, the invention has the following excellent effects:
(1) through pre-dispersing graphene in the material A and the material B respectively, finally, the graphene can be better dispersed in the polyurethane shoe material, so that the flexibility and the strength of the polyurethane shoe material are favorably improved.
(2) According to the invention, graphene and wood fiber are subjected to composite plasticization treatment, thermoplastic polybutylene succinate is further used as a carrier, graphene is dispersed in the graphene by utilizing strong shearing of a co-rotating twin-screw extruder and is crushed to be flocculent, then polyester polyol is added, and graphene dispersion is dispersed in the polyester polyol in a colloidal particle shape through ball milling.
(3) The preparation method is simple and has significant meaning for upgrading products of polyurethane shoe material production enterprises. This technique not only imparts good flexibility to the polyurethane shoe material, but also improves the low-temperature flexing resistance of the polyurethane shoe material as well.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a process flow diagram of a method for preparing a flexible polyurethane shoe material composition according to the present invention.
Fig. 2 is a photograph of a bulk graphene dispersion obtained by extruding, mixing and extruding graphene, wood fiber, polyethylene glycol and thermoplastic polybutylene succinate through a twin-screw extruder in step S1 according to the embodiment 1.
Detailed Description
The present invention is further illustrated by the following examples, which are presently preferred and illustrative, but are not intended to limit the scope of the invention.
Example one
A flexible polyurethane shoe material composition is characterized by comprising 90 parts by weight of a material A and 90 parts by weight of a material B; wherein:
the material A is obtained by the following method:
uniformly dispersing 3 parts by weight of graphene, 5 parts by weight of wood fiber and 3 parts by weight of polyethylene glycol 400 in a high-speed mixer, then adding 30 parts by weight of thermoplastic polybutylene succinate (PBS H1200 provided by Pasteur Germany) for uniform premixing, feeding into a co-rotating double-screw extruder, extruding, mixing and extruding at 100 ℃, and obtaining bulk graphene dispersion; as shown in fig. 1, the bulk graphene dispersion is fluffy.
Crushing 5 parts of graphene dispersion to generate floccule, adding 80 parts of polyester polyol (polyethylene glycol adipate with molecular weight of 2000), grinding in a 70 ℃ ball mill for 10min, and dispersing the graphene dispersion in the polyester polyol in colloidal particles to form polyester polyol containing colloidal particles; then adding 3 parts of chain extender 1, 4-butanediol, 0.1 part of catalyst (a compound of triethylene diamine and Dabco KTM60 amine catalyst in a mass ratio of 1: 2), 0.4 part of foaming agent water and 0.1 part of foam homogenizing agent dimethyl siloxane for uniform dispersion to obtain a material A;
the material B is obtained by the following method:
adding 0.5 part by weight of graphene, 5 parts by weight of nano zinc oxide and 80 parts by weight of diisocyanate (obtained by compounding toluene diisocyanate and diphenylmethane-4, 4' -diisocyanate in a mass ratio of 1: 1.5) into a ball mill, grinding and dispersing to obtain fine slurry, then putting the fine slurry into a reaction kettle, controlling the temperature of the reaction kettle to be 80 ℃, stirring at a speed of 50rpm, simultaneously adding 0.05 part of organic bismuth BiCAT 8118 and 45 parts of polyether polyol (Shanghai Gaoqiao GEP-330N), stirring and reacting for 30min, discharging, cooling to room temperature, sealing and packaging to obtain a prepolymer B material.
Example two
A flexible polyurethane shoe material composition is characterized by comprising 90 parts by weight of a material A and 80 parts by weight of a material B; wherein:
the material A is obtained by the following method:
uniformly dispersing 3 parts by weight of graphene, 10 parts by weight of wood fiber and 2 parts by weight of polyethylene glycol 600 in a high-speed mixer, adding 25 parts by weight of thermoplastic polybutylene succinate (PBS H1200 provided by Pasteur Germany) for uniform premixing, feeding into a co-rotating double-screw extruder, extruding, mixing and extruding at 120 ℃, and obtaining bulk graphene dispersion;
crushing 3 parts of graphene dispersion to generate floccule, adding 805 parts of polyester polyol (polyethylene glycol adipate with molecular weight of 2000), grinding in a 70 ℃ ball mill for 10min, and dispersing the graphene dispersion in the polyester polyol in colloidal particles to form polyester polyol containing colloidal particles; then adding 5 parts of chain extender ethylene glycol, 0.1 part of catalyst (a compound of triethylene diamine and Dabco KTM60 amine catalyst in a mass ratio of 1: 2), 0.3 part of foaming agent water and 0.2 part of foam homogenizing agent dimethyl siloxane for uniform dispersion to obtain a material A;
the material B is obtained by the following method:
adding 1 weight part of graphene, 5 weight parts of nano zinc oxide and 100 weight parts of diisocyanate (obtained by compounding toluene diisocyanate and diphenylmethane-4, 4' -diisocyanate in a mass ratio of 1: 1.5) into a ball mill, grinding and dispersing to obtain fine slurry, then putting the fine slurry into a reaction kettle, controlling the temperature of the reaction kettle at 90 ℃, stirring at a speed of 100rpm, simultaneously adding 0.1 part of organic bismuth BiCAT 8118 and 50 parts of polyether polyol (Shanghai Gaoqiao GEP-330N), stirring and reacting for 20min, discharging, cooling to room temperature, sealing and packaging to obtain a prepolymer B material.
EXAMPLE III
A flexible polyurethane shoe material composition is characterized by comprising 100 parts by weight of a material A and 80 parts by weight of a material B; wherein:
the material A is obtained by the following method:
uniformly dispersing 5 parts by weight of graphene, 10 parts by weight of wood fiber and 5 parts by weight of polyethylene glycol 400 in a high-speed mixer, then adding 30 parts by weight of thermoplastic polybutylene succinate (PBS H1200 provided by Pasteur Germany) for uniform premixing, feeding into a co-rotating double-screw extruder, extruding, mixing and extruding at 120 ℃, and obtaining bulk graphene dispersion;
crushing 5 parts of graphene dispersion to generate floccule, adding 85 parts of polyester polyol (polybutylene adipate with molecular weight of 2000), grinding in a ball mill at 80 ℃ for 15min, and dispersing the graphene dispersion in the polyester polyol in colloidal particles to form polyester polyol containing colloidal particles; then adding 5 parts of chain extender glycerol, 0.1 part of catalyst (a compound of triethylene diamine and Dabco KTM60 amine catalyst in a mass ratio of 1: 2), 0.2 part of foaming agent water and 0.2 part of foam homogenizing agent dimethyl siloxane for uniform dispersion to obtain a material A;
the material B is obtained by the following method:
adding 0.5 part by weight of graphene, 5 parts by weight of nano zinc oxide and 80 parts by weight of diisocyanate (obtained by compounding toluene diisocyanate and diphenylmethane-4, 4' -diisocyanate in a mass ratio of 1: 1.5) into a ball mill, grinding and dispersing to obtain fine slurry, then putting the fine slurry into a reaction kettle, controlling the temperature of the reaction kettle to be 90 ℃, stirring at a speed of 100rpm, simultaneously adding 0.1 part of organic bismuth BiCAT 8118 and 60 parts of polyether polyol (Shanghai Gaoqiao GEP-330N), stirring and reacting for 20min, discharging, cooling to room temperature, sealing and packaging to obtain a prepolymer B material.
Comparative example 1
A flexible polyurethane shoe material composition is characterized by comprising 90 parts by weight of a material A and 90 parts by weight of a material B; wherein:
the material A is obtained by the following method:
uniformly dispersing 5 parts by weight of wood fiber and 3 parts by weight of polyethylene glycol 400 in a high-speed mixer, then adding 30 parts by weight of thermoplastic polybutylene succinate (PBS H1200 provided by Pasteur Germany) for uniform premixing, and feeding the mixture into a co-rotating double-screw extruder for extrusion, and mixing and extruding at 100 ℃ to obtain a bulk dispersion;
crushing 5 parts of the bulk dispersion to generate floccules, adding 80 parts of polyester polyol (polyethylene glycol adipate with molecular weight of 2000), grinding in a ball mill at 70 ℃ for 10min, and dispersing the dispersion in the polyester polyol in granular form to form polyester polyol containing colloidal particles; then adding 3 parts of chain extender 1, 4-butanediol, 0.1 part of catalyst (a compound of triethylene diamine and Dabco KTM60 amine catalyst in a mass ratio of 1: 2), 0.4 part of foaming agent water and 0.1 part of foam homogenizing agent dimethyl siloxane for uniform dispersion to obtain a material A;
the material B is obtained by the following method:
adding 0.5 part by weight of graphene, 5 parts by weight of nano zinc oxide and 80 parts by weight of diisocyanate (obtained by compounding toluene diisocyanate and diphenylmethane-4, 4' -diisocyanate in a mass ratio of 1: 1.5) into a ball mill, grinding and dispersing to obtain fine slurry, then putting the fine slurry into a reaction kettle, controlling the temperature of the reaction kettle to be 80 ℃, stirring at a speed of 50rpm, simultaneously adding 0.05 part of organic bismuth BiCAT 8118 and 45 parts of polyether polyol (Shanghai Gaoqiao GEP-330N), stirring and reacting for 30min, discharging, cooling to room temperature, sealing and packaging to obtain a prepolymer B material.
In the first comparative example, no graphene is added to the wood fiber dispersed bulk, so that the dispersed granular loss enhancement effect is limited to the improvement of the flexibility of polyurethane.
Comparative example No. two
A flexible polyurethane shoe material composition is characterized by comprising 90 parts by weight of a material A and 80 parts by weight of a material B; wherein:
the material A is obtained by the following method:
uniformly dispersing 3 parts by weight of graphene and 2 parts by weight of polyethylene glycol 600 in a high-speed mixer, adding 25 parts by weight of thermoplastic polybutylene succinate (PBS H1200 provided by Pasteur Germany) for uniform premixing, and extruding in a co-rotating double-screw extruder at 120 ℃ for mixing and extruding to obtain bulk graphene dispersion;
crushing 3 parts of graphene dispersion, adding 805 parts of polyester polyol (polyethylene glycol adipate with molecular weight of 2000), grinding in a ball mill at 70 ℃ for 10min, and dispersing the graphene dispersion in the polyester polyol in colloidal particles to form polyester polyol containing colloidal particles; then adding 5 parts of chain extender ethylene glycol, 0.1 part of catalyst (a compound of triethylene diamine and DabcoKTM60 amine catalyst in a mass ratio of 1: 2), 0.3 part of foaming agent water and 0.2 part of foam homogenizing agent dimethyl siloxane for uniform dispersion to obtain a material A;
the material B is obtained by the following method:
adding 1 weight part of graphene, 5 weight parts of nano zinc oxide and 100 weight parts of diisocyanate (obtained by compounding toluene diisocyanate and diphenylmethane-4, 4' -diisocyanate in a mass ratio of 1: 1.5) into a ball mill, grinding and dispersing to obtain fine slurry, then putting the fine slurry into a reaction kettle, controlling the temperature of the reaction kettle at 90 ℃, stirring at a speed of 100rpm, simultaneously adding 0.1 part of organic bismuth BiCAT 8118 and 50 parts of polyether polyol (Shanghai Gaoqiao GEP-330N), stirring and reacting for 20min, discharging, cooling to room temperature, sealing and packaging to obtain a prepolymer B material.
Comparative example No wood fiber was added, and the graphene dispersion was dispersed in the polyester polyol in the form of colloidal particles, which had limited elasticity and affected the elasticity and flexibility of the polyurethane shoe material.
Comparative example No. three
A flexible polyurethane shoe material composition is characterized by comprising 100 parts by weight of a material A and 80 parts by weight of a material B; wherein:
the material A is obtained by the following method:
grinding 0.5 part of graphene and 85 parts of polyester polyol (polybutylene adipate with molecular weight of 2000) in a ball mill at 80 ℃ for 15min, and dispersing the graphene in the polyester polyol; then adding 5 parts of chain extender glycerol, 0.1 part of catalyst (a compound of triethylene diamine and Dabco KTM60 amine catalyst in a mass ratio of 1: 2), 0.2 part of foaming agent water and 0.2 part of foam homogenizing agent dimethyl siloxane for uniform dispersion to obtain a material A;
the material B is obtained by the following method:
adding 0.5 part by weight of graphene, 5 parts by weight of nano zinc oxide and 80 parts by weight of diisocyanate (obtained by compounding toluene diisocyanate and diphenylmethane-4, 4' -diisocyanate in a mass ratio of 1: 1.5) into a ball mill, grinding and dispersing to obtain fine slurry, then putting the fine slurry into a reaction kettle, controlling the temperature of the reaction kettle to be 90 ℃, stirring at a speed of 100rpm, simultaneously adding 0.1 part of organic bismuth BiCAT 8118 and 60 parts of polyether polyol (Shanghai Gaoqiao GEP-330N), stirring and reacting for 20min, discharging, cooling to room temperature, sealing and packaging to obtain a prepolymer B material.
In the comparative example III, graphene is directly dispersed in polyester polyol, and due to easy agglomeration, not only is the polyurethane reinforcement influenced, but also no graphene colloidal particle is formed, and the toughening effect is influenced.
Comparative example No. four
A flexible polyurethane shoe material composition is characterized by comprising 100 parts by weight of a material A and 80 parts by weight of a material B; wherein:
the material A is obtained by the following method:
adding 85 parts of polyester polyol (polybutylene adipate with molecular weight of 2000) into 5 parts of chain extender glycerol, 0.1 part of catalyst (a compound of triethylene diamine and Dabco KTM60 amine catalyst in a mass ratio of 1: 2), 0.2 part of foaming agent water and 0.2 part of foam homogenizing agent dimethyl siloxane, and uniformly dispersing to obtain a material A;
the material B is obtained by the following method:
adding 5 parts by weight of nano zinc oxide and 80 parts by weight of diisocyanate (obtained by compounding toluene diisocyanate and diphenylmethane-4, 4' -diisocyanate in a mass ratio of 1: 1.5) into a ball mill, grinding and dispersing to obtain fine slurry, then putting the fine slurry into a reaction kettle, controlling the temperature of the reaction kettle at 90 ℃, stirring at a speed of 100rpm, simultaneously adding 0.1 part of organic bismuth BiCAT 8118 and 60 parts of polyether polyol (Shanghai Gaoqiao GEP-330N), stirring and reacting for 20min, discharging the materials, cooling the materials to room temperature, sealing and packaging to obtain a prepolymer material B.
Comparative example four no graphene was used and the strength and flexibility of the polyurethane shoe material was lower.
The A, B material obtained in the examples and the comparative examples is used for preparing shoe materials by molding micro-foaming, and the specific method comprises the following steps: mixing the material A and the material B in a mixing tank at a mass ratio of 1.2:1 at a high speed of 800rpm for 20s, injecting the mixture into a mold at 60 ℃ for reaction for 5 minutes and molding; after the mold release, the molded product was aged at room temperature for 24 hours and tested as a sample.
The relevant properties were tested as follows:
1. testing the molding density:
the density was measured by test method A with reference to GB/T533-.
2. And (3) testing tensile strength:
with reference to GB/T6344-2008 "determination of tensile Strength and elongation at Break of Flexible foamed Polymer Material", at least 5 dumbbell-shaped test pieces were cut out with a prototype at a tensile rate of 500. + -.50 mm/mm, and the tensile strength and elongation tested are shown in Table 1.
3. Tear strength:
according to GB/T10808-2006 'determination of tearing strength of high polymer porous elastic material', a sample is cut from a central part, a sample with uniform foam holes is selected, a notch with the length of 40mm is cut at one end, and the length direction of the notch is vertical to the rising direction of the foam holes; the sample is opened, clamped on a clamp of the instrument and applied with a load at a speed of 50 mm/min; the maximum force at which the specimen breaks by 25mm is recorded. The maximum tensile value T/sample thickness d gives the tear strength as shown in Table 1.
4. A shoe material sample microfoamed in a molding die was cut to a size of 8X 20X 1.0cm, and then subjected to a 60 DEG bending test at-25 ℃ with a bending property shown in Table 1.
Table 1:
through the tests, the graphene and wood fiber composite plasticizing treatment is carried out, the thermoplastic polybutylene succinate is further used as a carrier, the graphene is dispersed in the graphene by utilizing strong shearing of a co-rotating double-screw extruder and is crushed to be flocculent, then the polyester polyol is added, and the graphene dispersion is dispersed in the polyester polyol in a colloidal particle shape through ball milling.
It is to be understood that the exemplary embodiments described herein are to be considered as illustrative and not restrictive. Moreover, descriptions of features or aspects in various embodiments should be applicable to other similar features or aspects in other embodiments.
Claims (10)
1. A flexible polyurethane shoe material composition is characterized by comprising 90-100 parts by weight of a material A and 80-90 parts by weight of a material B; wherein:
the material A is obtained by the following method:
uniformly dispersing 3-5 parts by weight of graphene, 5-10 parts by weight of wood fiber and 1-5 parts by weight of polyethylene glycol in a high-speed mixer, adding 20-30 parts by weight of thermoplastic poly (butylene succinate) for uniform premixing, feeding into a double-screw extruder, extruding, mixing and extruding at the temperature of 100 ℃ and 120 ℃ to obtain bulk graphene dispersion;
crushing a graphene dispersion to generate floccule, adding polyester polyol, grinding in a ball mill at 70-80 ℃ for 10-15min, and dispersing the graphene dispersion in the polyester polyol in colloidal particle shape to form polyester polyol containing colloidal particles; then adding a chain extender, a catalyst, a foaming agent and a foam homogenizing agent to disperse uniformly to obtain a material A;
the material B is obtained by the following method:
adding graphene, nano zinc oxide and diisocyanate into a ball mill, grinding and dispersing to obtain fine slurry, then putting the fine slurry into a reaction kettle, controlling the temperature of the reaction kettle to be 80-90 ℃, stirring at the speed of 50-100rpm, simultaneously adding organic bismuth and polyether polyol, stirring and reacting for 20-30min, discharging the materials until the temperature is reduced to room temperature, and sealing and packaging to obtain a prepolymer B material.
2. A preparation method of the flexible polyurethane shoe material composition as claimed in claim 1, which is characterized by comprising the following steps:
s1: uniformly dispersing 3-5 parts by weight of graphene, 5-10 parts by weight of wood fiber and 1-5 parts by weight of polyethylene glycol in a high-speed mixer, adding 20-30 parts by weight of thermoplastic poly (butylene succinate) for uniform premixing, and feeding the mixture into a double-screw extruder for mixing and extruding at the temperature of 100 ℃ and 120 ℃ to obtain bulk graphene dispersion;
s2, crushing the graphene dispersion to generate floccules, adding polyester polyol, grinding in a ball mill at 70-80 ℃ for 10-15min, and dispersing the graphene dispersion in the polyester polyol in colloidal particles to form polyester polyol containing colloidal particles; then adding a chain extender, a catalyst, a foaming agent and a foam homogenizing agent to disperse uniformly to obtain a material A;
s3: adding graphene, nano zinc oxide and diisocyanate into a ball mill, grinding and dispersing to obtain fine slurry, then putting the fine slurry into a reaction kettle, controlling the temperature of the reaction kettle to be 80-90 ℃, stirring at the speed of 50-100rpm, simultaneously adding organic bismuth and polyether polyol, stirring and reacting for 20-30min, discharging the materials until the temperature is reduced to room temperature, and sealing and packaging to obtain a prepolymer B material.
3. The method for preparing a flexible polyurethane shoe material composition according to claim 2, wherein: in the step S1, the thermoplastic poly butylene succinate is PBS H1200 provided by Pasteur Germany; the polyethylene glycol is at least one of polyethylene glycol 400 and polyethylene glycol 600.
4. The method for preparing a flexible polyurethane shoe material composition according to claim 2, wherein: the twin-screw in step S1 is co-rotating twin-screw extrusion.
5. The method for preparing a flexible polyurethane shoe material composition according to claim 2, wherein: in the step S2, the graphene dispersion, the polyester polyol, the chain extender, the catalyst, the foaming agent, and the foam stabilizer are in parts by weight: 1-5 parts of graphene dispersion, 80-85 parts of polyester polyol, 3-5 parts of chain extender, 0.1-0.3 part of catalyst, 0.1-0.4 part of foaming agent and 0.1-0.2 part of foam homogenizing agent.
6. The method for preparing a flexible polyurethane shoe material composition according to claim 2, wherein: in the step S2, the polyester polyol is polyethylene glycol adipate or polybutylene adipate with molecular weight of 2000; the chain extender is one of 1, 4-butanediol, ethylene glycol, glycerol, diethanolamine and methyldiethanolamine; the catalyst is a compound of triethylene diamine and Dabco KTM60 amine catalyst (provided by American air product company) in a mass ratio of 1: 2; the foaming agent is water; the foam homogenizing agent is dimethyl siloxane.
7. The method for preparing a flexible polyurethane shoe material composition according to claim 2, wherein: in the step S3, the graphene, the nano zinc oxide, the diisocyanate, the organic bismuth and the polyether polyol are calculated according to the parts by weight: 0.5-1 part of graphene, 5-10 parts of nano zinc oxide, 80-100 parts of diisocyanate, 0.05-0.1 part of organic bismuth and 45-60 parts of polyether polyol.
8. The method for preparing a flexible polyurethane shoe material composition according to claim 2, wherein: in step S3, the diisocyanate is Toluene Diisocyanate (TDI) and/or diphenylmethane-4, 4' -diisocyanate (MDI).
9. The method for preparing a flexible polyurethane shoe material composition according to claim 2, wherein: and step S3, selecting the organic bismuth from BiCAT 8118 sold in the market.
10. The method for preparing a flexible polyurethane shoe material composition according to claim 2, wherein: and step S3, selecting Shanghai Gaoqiao GEP-330N as the polyether polyol.
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