CN111777788A - Double-component stock solution of high-elasticity low-density polyurethane shoe material and preparation method thereof - Google Patents
Double-component stock solution of high-elasticity low-density polyurethane shoe material and preparation method thereof Download PDFInfo
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- CN111777788A CN111777788A CN202010531892.3A CN202010531892A CN111777788A CN 111777788 A CN111777788 A CN 111777788A CN 202010531892 A CN202010531892 A CN 202010531892A CN 111777788 A CN111777788 A CN 111777788A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/0009—Footwear characterised by the material made at least partially of alveolar or honeycomb material
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/14—Footwear characterised by the material made of plastics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/224—Surface treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/06—Polystyrene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Abstract
The invention relates to a polyurethane raw material, in particular to a special polyurethane stock solution for shoe materials, and further in particular to a two-component stock solution for high-elasticity low-density polyurethane shoe materials and a preparation method thereof; the method comprises the following steps of (1) refining expandable polystyrene, treating by using an aminosilane coupling agent, and uniformly dispersing the expandable polystyrene, polyester polyol, light filler, a chain extender, a catalyst, a foaming agent, a foam homogenizing agent and an anti-aging agent to obtain A; prepolymerizing the modified expandable polystyrene micronized particles, diisocyanate and polyether polyol to form a prepolymer B material; the modified expandable polystyrene fine particles are uniformly dispersed in the polyurethane stock solution and tightly combined, and interface defects caused by the foaming of the expandable polystyrene cannot be generated. Used for molding shoe materials in molding to obtain low-density high-elasticity shoe materials. The preparation method is simple, the raw material source is reliable, the method is suitable for direct production and use of the existing polyurethane stock solution production enterprises, the process is easy to control, and the method is suitable for large-scale popularization and use.
Description
Technical Field
The invention relates to a polyurethane raw material, in particular to a special polyurethane stock solution for shoe materials, and further in particular relates to a two-component stock solution for high-elasticity low-density polyurethane shoe materials 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.
Particularly, the polyurethane shoe material is different from the traditional shoe material processing technology, is a two-component raw liquid pouring micro-foaming material, can be prepared by adopting a one-step molding technology, does not need to be bonded, saves labor and time, is beneficial to the production environment, and greatly improves the production efficiency. The polyurethane shoe material is formed by metering a substance with small molecular weight in a liquid state, injecting the liquid into a mold while instantly mixing, reacting rapidly in a mold cavity, rapidly extending the chain of the material molecular weight, and producing a brand new polymer containing a new characteristic group structure at a very high speed. In general, the density of a conventional rubber or polyvinyl chloride shoe material is 1.2g/cm3 or more, and even if foamed, the density is 0.8g/cm3 or more. However, the density of the polyurethane shoe material can be less than 0.6g/cm 3. In addition, polyurethane shoe materials have excellent wear resistance and are widely used in outer soles, mid-soles, heels, toe caps, insoles and the like of many shoes such as golf shoes, baseball shoes, football shoes, ski shoes, tourist shoes, safety shoes and the like.
With the expansion of the application of polyurethane in the field of shoe materials, the cost of polyurethane becomes the most concerned problem for each enterprise. Compared with traditional sole materials such as polyvinyl chloride and the like, the polyurethane has high cost. In order to enhance the application competitiveness of polyurethane in shoe materials, technicians continuously reduce the density of the polyurethane shoe materials, thereby achieving the purpose of reducing the cost. Currently, the densitometer of molded shoe material articles is reduced to 0.4g/cm3, but if the density is further reduced, more negative performance will occur. If more water is used as the foaming agent, the generated closed cell rate is higher, so that the product is easy to shrink, the dimensional stability of the product is reduced, the modulus is reduced, and the bearing capacity is reduced. In particular, although the density of microbubbles formed by using a large amount of water is reduced, the microbubbles tend to form hard segments, which affects the elasticity of the shoe material. The skilled person tries to improve the elasticity by controlling the content of urethane groups in the polyurethane, but the effect is slight. In particular, for polyurethane with a large decrease in density, the modulus and the load-bearing capacity are greatly affected.
Disclosure of Invention
In order to further reduce the density of polyurethane shoe materials, more water foaming agents are used in the prior polyurethane shoe material stock solution, but more water foaming agents are easy to form more hard sections after molding, so that the bearing capacity and the elasticity of the polyurethane shoe materials are influenced. The invention provides a preparation method of a two-component stock solution of a high-elasticity low-density polyurethane shoe material, which utilizes the heating foaming characteristic of expandable polystyrene to micronize the expandable polystyrene and treat the expandable polystyrene by an aminosilane coupling agent, and is used for preparing a material A by polyester polyol; pre-polymerizing the modified expandable polystyrene fine particles, diisocyanate and polyether polyol to form a prepolymer B material; further provides the two-component stock solution prepared by the method. The modified expandable polystyrene fine particles are used for micro-foaming reaction in molding, and the modified expandable polystyrene fine particles are heated and foamed in the polyurethane shoe material to form a support body, so that the density of polyurethane is reduced, and the bearing property and the elasticity of the polyurethane are enhanced.
In order to achieve the above purpose, firstly, a preparation method of a two-component stock solution of a high-elasticity low-density polyurethane shoe material is provided, which is characterized by comprising the following steps:
s1: uniformly mixing expandable polystyrene particles and an aminosilane coupling agent, adding the mixture into a vortex airflow refining machine for refining, and obtaining modified expandable polystyrene fine particles with the particle size of less than 10 mu m through a cyclone separator;
s2: uniformly dispersing polyester polyol with the molecular weight of 2000-3000, modified expandable polystyrene fine particles, light filler, a chain extender, a catalyst, a foaming agent, a foam homogenizing agent and an anti-aging agent to obtain a material A;
s3: putting diisocyanate into a reaction kettle, controlling the temperature of the reaction kettle at 60-70 ℃, then adding the modified expandable polystyrene fine particles, slowly stirring for 3-5min, stopping heating, adding the organic zinc and the polyether polyol, stirring for 15-30min at the rotating speed of 50-100rpm, discharging, cooling to room temperature, sealing and packaging to obtain the prepolymer B material.
The expandable polystyrene particles are particles which can be expanded at 90-100 ℃ and have high expansion ratio. The expandable polystyrene particles are generally commercially available as large particles having a particle size of 1 to 3 mm. The invention selects the commercial expandable polystyrene particles, and takes aminosilane coupling agent as modifier to carry out surface modification while refining by a vortex airflow refiner to obtain modified expandable polystyrene fine particles with the particle size less than 10 mu m. The expandable polystyrene particles modified by refinement can be uniformly dispersed in two components and can be well combined with polyol and diisocyanate. Particularly, when the modified expandable polystyrene fine particles are used for preparing the shoe material through two-component stock solution molding reaction, the modified expandable polystyrene fine particles are foamed to form approximately spherical foamed particles which are uniformly dispersed in the polyurethane shoe material to form good support, so that the excellent elasticity is given to the shoe material, the density of the shoe material is low, the support strength is good, and the purposes of high resilience, low density and high bearing capacity are achieved.
Through experiments, the larger foaming particles formed by the modified expandable polystyrene fine particles with larger particle size in polyurethane influence the tearing resistance of the polyurethane shoe material. The modified expandable polystyrene fine particles with smaller particle size are uniformly dispersed in the polyurethane shoe material, and the formed expanded particles are smaller, so that the tearing property of the shoe material is not influenced. As a preferred aspect of the present invention, the modified expandable polystyrene fine particles having a particle size of < 10 μm are finely screened in a vortex air flow refiner.
The present invention does not specifically limit the equipment for refining expandable polystyrene, but takes into account that expandable polystyrene is a heat-sensitive material, and is not easy to refine because it is degraded by grinding, ball milling, etc. Therefore, the refining equipment preferably adopts a vortex airflow refiner, which makes the expandable polystyrene collide at high speed between a rotor and a stator through the rotor rotating at high speed so as to refine the expandable polystyrene, and makes the aminosilane coupling agent finish the modification of the refined expandable polystyrene. Further, preferably, the rotating speed of the vortex airflow refiner is controlled at 1200-1500 rpm; the classifying rotating speed of the cyclone separator is 800-1200 rpm.
Preferably, the expandable polystyrene particles and the amino silane coupling agent in the S1 are compounded according to the mass ratio of 100: 2-4.
Further preferably, the expandable polystyrene particles are made of expanded polystyrene particles EPS391F type, and the particle size is about 0.8 mm.
Preferably, the aminosilane coupling agent in S1 is at least one selected from the group consisting of γ -aminopropyltriethoxysilane, N- β (aminoethyl) - γ -aminopropyltrimethoxysilane, N- β (aminoethyl) - γ -aminopropyltriethoxysilane, and anilinomethyltriethoxysilane.
Preferably, the polyester polyol, the modified expandable polystyrene fine particles, the light filler, the chain extender, the catalyst, the foaming agent, the foam stabilizer and the anti-aging agent in the S2 are mixed in a mass ratio of 70-80: 1-3:1-3:5-10:0.1-0.3:0.1-0.2:0.5-1: 0.1-0.3 are dispersed evenly.
Further preferably, the polyester polyol in S2 is polyethylene adipate or polybutylene adipate.
Further preferably, the light filler in S2 is selected from one of fumed silica with micropores and microporous glass powder; it is further preferred that the light filler has a particle size of less than 10 μm. The main functions are as follows: on one hand, the polyurethane is assisted in reducing the density, and on the other hand, the wear resistance of the polyurethane shoe material is assisted in improving.
Further preferably, the chain extender in S2 is one of 1, 4-butanediol, ethylene glycol and glycerol.
More preferably, the catalyst used in S2 is at least one of stannous octoate, dibutyl tin dilaurate, and di-n-butyltin diacetate.
Further preferably, the foaming agent in S2 is water.
Further preferably, the foam stabilizer in S2 is dimethyl siloxane.
More preferably, the anti-aging agent in S2 is compounded by an antioxidant and an ultraviolet absorbent in a mass ratio of 1: 1; preferably, the antioxidant is at least one of antioxidant 1010 and antioxidant 168; the ultraviolet absorbent is one of UV-9 and UV-328.
Preferably, the mass ratio of the diisocyanate, the modified expandable polystyrene fine particles, the organic zinc and the polyether polyol in S3 is 100: 1-3:0.1-0.2:50-80.
Preferably, the diisocyanate described in S3 is at least one selected from 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 shoe materials, we recommend to use Toluene Diisocyanate (TDI) or diphenylmethane-4, 4' -diisocyanate (MDI) in terms of price measurement, stable supply and the like through practice.
Preferably, the organic zinc in S3 is zinc isooctanoate provided by shanghai zheng new material science and technology limited.
Preferably, the polyether polyol in S3 is selected from one of polyoxypropylene Polyether Polyol (PPG) and polytetrahydrofuran polyether Polyol (PTMEG) with the molecular weight of 5000-.
The invention also provides the two-component stock solution of the high-elasticity low-density polyurethane shoe material prepared by the method. In order to obtain the polyurethane shoe material with low density and good elasticity and bearing capacity after the stock solution is used for the molding foaming reaction, the invention creatively utilizes the heating foaming characteristic of the expandable polystyrene, micronizes the expandable polystyrene and treats the expandable polystyrene by an aminosilane coupling agent for preparing a material A by the polyester polyol; pre-polymerizing the modified expandable polystyrene micronized particles, diisocyanate and polyether polyol to form a prepolymer B material; its classical use is: mixing the material A and the material B in a mixing tank at a mass ratio of 1.2-1.5:1 at a high speed of 800rpm for 15-30s, uniformly injecting into a metal shoe material mold, foaming and curing at 90-100 ℃ for 5-7min, and heating and foaming the fine expandable polystyrene particles in the polyurethane shoe material to form a support body, so that the polyurethane shoe material has lower density, and meanwhile, the foamed particles are uniformly dispersed in the polyurethane to form a whole body with the polyurethane, thereby endowing the polyurethane shoe material with excellent high elasticity and high bearing property.
Compared with the prior art, the invention has the following excellent effects:
(1) in the prior art, when the cost of polyurethane shoe materials is reduced, the cost is reduced by increasing foaming and reducing the density, but the bearing capacity of the foamed polyurethane is poor, the compression deformation is large, the polyurethane is easy to deform under long-time load and is difficult to recover. Therefore, it is difficult to achieve both low density and high elasticity. The invention effectively overcomes the defects of poor elasticity and poor bearing capacity of the molded microcellular foamed polyurethane shoe material after low density.
(2) The invention can easily disperse in the polyurethane stock solution by the refinement of the expandable polystyrene and the treatment of the aminosilane coupling agent, particularly, the surface of the micronized particles of the modified expandable polystyrene is the aminosilane coupling agent, and the amino of the aminosilane coupling agent promotes the prepolymerization with diisocyanate and polyether polyol to form a prepolymer B material, so that the ultrafine particles of the expandable polystyrene are uniformly dispersed and tightly combined in the polyurethane, and the interface defect caused by the foaming of the expandable polystyrene can be avoided.
(3) The preparation method is simple, the raw material source is reliable, the method is suitable for direct production and use of the existing polyurethane stock solution production enterprises, the process is easy to control, and the method is suitable for large-scale popularization and use. Has positive significance for promoting polyurethane shoe materials to replace polyvinyl chloride and rubber elastomer shoe materials.
Drawings
In order to facilitate understanding of the meaning of the invention for micronizing expandable polystyrene and modifying the expandable polystyrene by using an aminosilane coupling agent for a polyurethane shoe material, the invention is further explained by combining the following drawings:
FIG. 1 is a schematic structural diagram of a two-component stock solution obtained by the present invention for preparing a molded microcellular foamed polyurethane shoe material, wherein 1 is a foamed polyurethane body; 2-fine polystyrene foam.
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
S1: weighing 50kg of expandable polystyrene particles EPS391F with the particle size of 0.8mm provided by Zhongshan Teda; 1.5kg of gamma-aminopropyl triethoxysilane is added into a high-speed mixer to be uniformly mixed, then a vortex airflow refiner is added for refining, and the rotating speed of a main machine is controlled to be 1200 rpm; the grading rotating speed of the cyclone separator is 1000rpm, and modified expandable polystyrene fine particles with the particle size of less than 10 mu m are obtained through the cyclone separator;
s2: uniformly dispersing 80kg of polyethylene glycol adipate with the molecular weight of 2000, 1kg of modified expandable polystyrene fine particles, 1kg of fumed silica, 6kg of chain extender 1, 4-butanediol, 0.1kg of catalyst dibutyl tin dilaurate, 0.1kg of foaming agent water, 0.5kg of foam homogenizing agent dimethyl siloxane, 0.05kg of oxidant 1010 and 0.05kg of ultraviolet absorbent UV-9 to obtain a material A;
s3: 100kg of diphenylmethane-4, 4' -diisocyanate (MDI) is put into a reaction kettle, the temperature of the reaction kettle is controlled at 70 ℃, then 1kg of modified expandable polystyrene superfine particles are added, the mixture is slowly stirred for 5min, the heating is stopped, 0.1kg of zinc isooctanoate and 50kg of polyoxypropylene ether polyol (PPG) with the molecular weight of 5000, which are provided by Shanghai Zhenggui new material science and technology Limited, are added, the mixture is stirred for 30min at the rotating speed of 100rpm, the mixture is discharged until the temperature is reduced to the room temperature, and the prepolymer B material is obtained after sealed packaging.
Example two
S1: weighing 50kg of expandable polystyrene particles EPS391F with the particle size of 0.8mm provided by Zhongshan Teda; 2.0kg of gamma-aminopropyl triethoxysilane is added into a high-speed mixer to be uniformly mixed, then a vortex airflow refiner is added for refining, and the rotating speed of a main machine is controlled to be 1200 rpm; the grading rotating speed of the cyclone separator is 1000rpm, and modified expandable polystyrene fine particles with the particle size of less than 10 mu m are obtained through the cyclone separator;
s2: uniformly dispersing 75kg of polybutylene adipate with the molecular weight of 2000, 2kg of modified expandable polystyrene fine particles, 1kg of fumed silica, 10kg of chain extender 1, 4-butanediol, 0.1kg of catalyst stannous octoate, 0.1kg of foaming agent water, 1kg of foam homogenizing agent dimethyl siloxane, 10100.15kg of oxidant and 0.15kg of ultraviolet absorbent to obtain a material A;
s3: 100kg of Toluene Diisocyanate (TDI) is put into a reaction kettle, the temperature of the reaction kettle is controlled to be 60 ℃, then 2kg of modified expandable polystyrene fine particles are added, the mixture is slowly stirred for 5min, the heating is stopped, 60kg of polytetrahydrofuran ether glycol (PTMEG) with the molecular weight of 5000 and 0.2kg of zinc isooctoate provided by Shanghai Shagui New Material science and technology Limited are added, the mixture is stirred for 15min at the rotating speed of 100rpm, the materials are discharged, the temperature is reduced to the room temperature, and the prepolymer B material is obtained after sealed packaging.
EXAMPLE III
S1: weighing 50kg of expandable polystyrene particles EPS391F with the particle size of 0.8mm provided by Zhongshan Teda; 2.0kg of gamma-aminopropyl triethoxysilane is added into a high-speed mixer to be uniformly mixed, then a vortex airflow refiner is added for refining, and the rotating speed of a main machine is controlled to be 1200 rpm; the grading rotating speed of the cyclone separator is 1000rpm, and modified expandable polystyrene fine particles with the particle size of less than 10 mu m are obtained through the cyclone separator;
s2: uniformly dispersing 75kg of polybutylene adipate with the molecular weight of 2000, 3kg of modified expandable polystyrene fine particles, 1kg of fumed silica, 10kg of chain extender 1, 4-butanediol, 0.1kg of catalyst stannous octoate, 0.1kg of foaming agent water, 1kg of foam homogenizing agent dimethyl siloxane, 10100.15kg of oxidant and 0.15kg of ultraviolet absorbent to obtain a material A;
s3: 100kg of Toluene Diisocyanate (TDI) is put into a reaction kettle, the temperature of the reaction kettle is controlled to be 70 ℃, then 3kg of modified expandable polystyrene fine particles are added, the mixture is slowly stirred for 5min, the heating is stopped, 60kg of polytetrahydrofuran ether glycol (PTMEG) with the molecular weight of 5000 and 0.2kg of zinc isooctoate provided by Shanghai Shagui New Material science and technology Limited are added, the mixture is stirred for 15min at the rotating speed of 100rpm, the materials are discharged, the temperature is reduced to the room temperature, and the prepolymer B material is obtained after sealed packaging.
Comparative example 1
S1: weighing 50kg of expandable polystyrene particles EPS391F with the particle size of 0.8mm provided by Zhongshan Teda; 1.5kg of gamma-aminopropyl triethoxysilane is added into a high-speed mixer to be uniformly mixed, then a vortex airflow refiner is added for refining, and the rotating speed of a main machine is controlled to be 1200 rpm; the classification rotating speed of the cyclone separator is 400rpm, and modified expandable polystyrene fine particles with the particle size of 50-100 mu m are obtained through the cyclone separator.
S2: uniformly dispersing 80kg of polyethylene glycol adipate with the molecular weight of 2000, 1kg of modified expandable polystyrene fine particles, 1kg of fumed silica, 6kg of chain extender 1, 4-butanediol, 0.1kg of catalyst dibutyl tin dilaurate, 0.1kg of foaming agent water, 0.5kg of foam homogenizing agent dimethyl siloxane, 0.05kg of oxidant 1010 and 0.05kg of ultraviolet absorbent UV-9 to obtain a material A;
s3: 100kg of diphenylmethane-4, 4' -diisocyanate (MDI) is put into a reaction kettle, the temperature of the reaction kettle is controlled at 70 ℃, then 1kg of modified expandable polystyrene superfine particles are added, the mixture is slowly stirred for 5min, the heating is stopped, 0.1kg of zinc isooctanoate and 50kg of polyoxypropylene ether polyol (PPG) with the molecular weight of 5000, which are provided by Shanghai Zhenggui new material science and technology Limited, are added, the mixture is stirred for 30min at the rotating speed of 100rpm, the mixture is discharged until the temperature is reduced to the room temperature, and the prepolymer B material is obtained after sealed packaging.
Comparative example No. two
S1: weighing 50kg of expandable polystyrene particles EPS391F with the particle size of 0.8mm provided by Zhongshan Teda; then adding a vortex air flow refiner for refining, and controlling the rotating speed of a main machine to be 1200 rpm; the grading rotating speed of the cyclone separator is 1000rpm, and the fine expandable polystyrene particles with the particle size less than 10 mu m are obtained through the cyclone separator;
s2: uniformly dispersing 75kg of polybutylene adipate with the molecular weight of 2000, 2kg of refined expandable polystyrene particles, 1kg of fumed silica, 10kg of chain extender 1, 4-butanediol, 0.1kg of catalyst stannous octoate, 0.1kg of foaming agent water, 1kg of foam homogenizing agent dimethyl siloxane, 10100.15kg of oxidant and 0.15kg of ultraviolet absorbent to obtain a material A;
s3: 100kg of Toluene Diisocyanate (TDI) is put into a reaction kettle, the temperature of the reaction kettle is controlled to be 60 ℃, then 2kg of refined expandable polystyrene particles are added, the stirring is slowly carried out for 5min, the heating is stopped, 60kg of polytetrahydrofuran ether glycol (PTMEG) with the molecular weight of 5000 and 0.2kg of zinc isooctoate provided by Shanghai Shagui New Material science and technology Limited are added, the stirring is carried out for 15min at the rotating speed of 100rpm, the discharging is carried out, the temperature is reduced to the room temperature, and the sealing and packaging are carried out, so that the prepolymer B material is obtained.
Comparative example No. three
S1: uniformly dispersing 75kg of polybutylene adipate with the molecular weight of 2000, 1kg of fumed silica, 10kg of chain extender 1, 4-butanediol, 0.1kg of catalyst stannous octoate, 0.1kg of foaming agent water, 1kg of foam homogenizing agent dimethyl siloxane, 10100.15kg of oxidant and 0.15kg of ultraviolet absorbent to obtain a material A;
s3: 100kg of Toluene Diisocyanate (TDI) is put into a reaction kettle, the temperature of the reaction kettle is controlled to be 70 ℃, then 0.2kg of zinc isooctanoate provided by Shanghai Zhenggui new material science and technology limited company and 60kg of polytetrahydrofuran ether glycol (PTMEG) with the molecular weight of 5000 are added, the mixture is stirred for 15min at the rotating speed of 100rpm, the mixture is discharged, the temperature is reduced to the room temperature, and the prepolymer B material is obtained by sealing and packaging.
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, uniformly injecting into a metal shoe material mold sprayed with a release agent, foaming and curing at 100 ℃ for 7min, and demolding for 24h to obtain a test 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. Shore hardness is tested according to GB/T531.1-2008 Shore durometer test method No. 1 Shore Durometer (Shore hardness), and the data are shown in Table 1.
5. Heavy load resilience:
cutting a shoe material sample which is slightly foamed in a molding die, wherein the size of the shoe material sample is 8 multiplied by 20 multiplied by 2.5cm, then pressing a lead plate which is 8 multiplied by 20cm and has the weight of 10kg on the shoe material, and the initial thickness of the shoe material is calculated as H0; the thickness of the shoe material after the lead plate is pressed is H1; pressing for 5min, and taking the thickness of the removed lead plate shoe material as H2; pressing for 120min the thickness of the removed lead plate shoe material was measured as H3. As shown in table 2.
Table 1:
table 2:
through the tests, the expandable polystyrene is thinned and treated by the amino silane coupling agent, so that the expandable polystyrene is very easy to disperse in the polyurethane stock solution, particularly, the surface of the micronized particles of the modified expandable polystyrene is the amino silane coupling agent, and the amino group of the micronized particles of the modified expandable polystyrene promotes the prepolymerization with diisocyanate and polyether polyol to form a prepolymer B material, so that the ultrafine particles of the expandable polystyrene are uniformly dispersed in the polyurethane and tightly combined, the density is greatly reduced through foaming in molding, the compression deformation of the polyurethane shoe material is reduced when the polyurethane shoe material bears a heavy object, the polyurethane shoe material is easy to recover from deformation after long-time load, and good resilience is maintained.
Comparative example one in processing expandable polystyrene, adopted lower classification speed, the collected micronized expandable polystyrene particles are larger, because the particles are larger and the uniformity is poorer after the polyurethane system is foamed, the tearing resistance is poorer, and the bearing capacity and elasticity have certain influence. In the second comparative example, no aminosilane coupling agent treatment is added during the micronization treatment of the expandable polystyrene, which affects the dispersion in the polyurethane stock solution, and in the preparation of prepolymer B, because the surface of the micronized expandable polystyrene is not treated by the aminosilane coupling agent, the micronized expandable polystyrene cannot be tightly combined with diisocyanate, so that the polyurethane shoe material has defects, and the tear resistance and the elasticity are affected. In the third comparative example, modified expandable polystyrene fine particles were not added to the material A and the material B, the density of the polyurethane shoe material was high, and the obtained shoe material was easily deformed by a long-term heavy object and had poor resilience.
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. While one or more embodiments of the present invention have been illustrated in the accompanying drawings, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
Claims (8)
1. A preparation method of a two-component stock solution of a high-elasticity low-density polyurethane shoe material is characterized by comprising the following steps:
s1: uniformly mixing expandable polystyrene particles and an aminosilane coupling agent, adding the mixture into a vortex airflow refining machine for refining, and obtaining modified expandable polystyrene fine particles with the particle size of less than 10 mu m through a cyclone separator;
s2: uniformly dispersing polyester polyol with the molecular weight of 2000-3000, modified expandable polystyrene fine particles, light filler, a chain extender, a catalyst, a foaming agent, a foam homogenizing agent and an anti-aging agent to obtain a material A;
s3: putting diisocyanate into a reaction kettle, controlling the temperature of the reaction kettle at 60-70 ℃, then adding the modified expandable polystyrene fine particles, slowly stirring for 3-5min, stopping heating, adding the organic zinc and the polyether polyol, stirring for 15-30min at the rotating speed of 50-100rpm, discharging, cooling to room temperature, sealing and packaging to obtain the prepolymer B material.
2. The method for preparing the two-component stock solution of the high-elasticity low-density polyurethane shoe material according to claim 1, which is characterized in that: in S1, the rotating speed of the vortex airflow refiner is controlled at 1200-1500 rpm; the classifying rotating speed of the cyclone separator is 800-1200 rpm.
3. The method for preparing the two-component stock solution of the high-elasticity low-density polyurethane shoe material according to claim 1, which is characterized in that: compounding the expandable polystyrene particles and the aminosilane coupling agent in the S1 according to the mass ratio of 100: 2-4; the expandable polystyrene particles are of a Zhongshan mountain Taida expandable polystyrene particle EPS391F type, and the particle size of the expandable polystyrene particles is about 0.8 mm; the amino silane coupling agent is at least one of gamma-aminopropyl triethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl trimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl triethoxysilane and aniline methyl triethoxysilane.
4. The method for preparing the two-component stock solution of the high-elasticity low-density polyurethane shoe material according to claim 1, which is characterized in that: the polyester polyol, the modified expandable polystyrene fine particles, the light filler, the chain extender, the catalyst, the foaming agent, the foam homogenizing agent and the anti-aging agent in the S2 are mixed according to the mass ratio of 70-80: 1-3:1-3:5-10:0.1-0.3:0.1-0.2:0.5-1: 0.1-0.3 are dispersed evenly.
5. The method for preparing the two-component stock solution of the high-elasticity low-density polyurethane shoe material according to claim 1, which is characterized in that: the polyester polyol in S2 is polyethylene glycol adipate or polybutylene adipate; the light filler is selected from one of gas-phase silica with micropores and microporous glass powder; the chain extender is one of 1, 4-butanediol, ethylene glycol and glycerol; the catalyst is at least one of stannous octoate, dibutyl tin dilaurate and di-n-butyltin diacetate; the foaming agent is water; the foam homogenizing agent is dimethyl siloxane; the anti-aging agent is compounded by an antioxidant and an ultraviolet absorbent in a mass ratio of 1: 1.
6. The method for preparing the two-component stock solution of the high-elasticity low-density polyurethane shoe material according to claim 1, which is characterized in that: in S3, the mass ratio of the diisocyanate to the modified expandable polystyrene fine particles to the organic zinc to the polyether polyol is 100: 1-3:0.1-0.2:50-80.
7. The method for preparing the two-component stock solution of the high-elasticity low-density polyurethane shoe material according to claim 1, wherein the diisocyanate in S3 is at least one selected from Toluene Diisocyanate (TDI), diphenylmethane-4, 4' -diisocyanate (MDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), p-phenylene diisocyanate (PPDI), and Xylylene Diisocyanate (XDI); the organic zinc is zinc isooctoate provided by Shanghai Zhenggui new material science and technology limited; the polyether polyol is selected from one of polyoxypropylene Polyether Polyol (PPG) and polytetrahydrofuran polyether Polyol (PTMEG) with the molecular weight of 5000-.
8. A two-component stock solution for a high resilience low density polyurethane footwear material prepared by the method of any one of claims 1 to 7.
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Denomination of invention: A two-component stock solution and preparation method for high elasticity and low density polyurethane shoe material Effective date of registration: 20230524 Granted publication date: 20230418 Pledgee: Zhejiang Luqiao Taizhou rural commercial bank Limited by Share Ltd. Pledgor: Taizhou Lantian Enterprise Service Co.,Ltd. Registration number: Y2023330000968 |