CN110643014A - Production and manufacturing process method of polyurethane insole - Google Patents
Production and manufacturing process method of polyurethane insole Download PDFInfo
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- CN110643014A CN110643014A CN201910480562.3A CN201910480562A CN110643014A CN 110643014 A CN110643014 A CN 110643014A CN 201910480562 A CN201910480562 A CN 201910480562A CN 110643014 A CN110643014 A CN 110643014A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B17/00—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
- A43B17/14—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined made of sponge, rubber, or plastic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
- C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/631—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyesters and/or polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Abstract
The invention discloses a production and manufacturing process method of a polyurethane insole, which comprises a component A and a component B, wherein the component A comprises the following components: 20-80% of polyester polyol A1 and 20-80% of polymer polyester polyol A2, wherein the unit is weight percentage; the polyester polyol foam stabilizer also comprises 0.1-0.8% of a cross-linking agent, 5-40% of a dihydric alcohol chain extender, 1-3% of a catalyst, 0.3-1.2% of an organic silicon foam stabilizer and 1-2% of water, wherein the unit is the weight percentage of the total dosage of the polyester polyol A1 and the polymer polyester polyol A2; the polyester polyol A1 is polyester polyol with the molecular weight of 1500-1850, which is prepared by the ester exchange reaction of one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 3-propanediol and trihydroxy methyl propane and adipic acid.
Description
Technical Field
The invention relates to the technical field of chemistry, in particular to a manufacturing process method for a polyurethane insole.
Background
Polyurethane soles are increasingly popular with consumers because of their characteristics of portability, wear resistance, good elasticity, continuous sole, skid resistance, oil resistance, comfortable wearing, etc. China has the largest shoe making industry in the world, 70 hundred million double shoes are produced in 2003, which accounts for 50% of the global yield, 78 hundred million double shoes are exported in 2006, and 90 hundred million double shoes are expected to be produced in 2010. At present, the materials for shoes mainly comprise leather, rubber, polyvinyl chloride (PVC), Ethylene Vinyl Acetate (EVA), Styrene Butadiene Styrene (SBS), thermoplastic polyurethane elastomer (TPU) and the like. In recent years, the market of polyurethane stock solution in China is influenced by the price of raw materials and the anti-tipping event of European Union to Chinese shoe products, the growth speed is slowed down, the proportion of the existing polyurethane shoe soles is less than 6%, and the polyurethane shoe soles in developed countries account for more than 50% of the market share, so the market space of the polyurethane shoe soles in China is still large, the polyurethane shoe materials in the market mainly comprise polyester polyols and account for about 80%, but the existing polyurethane shoes in the market are manufactured, and the high hardness of the polyurethane shoes is greatly reduced due to the low density of the polyurethane shoes.
Disclosure of Invention
The invention aims to provide a production and manufacturing process method of a polyurethane insole, which has the advantage that the polyurethane sole can still keep high hardness under the condition of low density, and solves the problem that the polyurethane sole has high hardness under the condition of low density.
In order to achieve the purpose, the invention provides the following technical scheme: a production and manufacturing process method of a polyurethane insole comprises a component A and a component B, wherein the component A comprises the following components: 20-80% of polyester polyol A1 and 20-80% of polymer polyester polyol A2, wherein the unit is weight percentage; the polyester polyol foam stabilizer also comprises 0.1-0.8% of a cross-linking agent, 5-40% of a dihydric alcohol chain extender, 1-3% of a catalyst, 0.3-1.2% of an organic silicon foam stabilizer and 1-2% of water, wherein the unit is the weight percentage of the total dosage of the polyester polyol A1 and the polymer polyester polyol A2;
the polyester polyol A1 is polyester polyol with the molecular weight of 1500-1850, which is prepared by the ester exchange reaction of one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 3-propanediol and trihydroxy methyl propane and adipic acid;
the polymer polyester polyol A2 is polymer polyester polyol which is prepared by free radical polymerization of one or more of styrene, acrylonitrile and methyl methacrylate and polyester polyol A1, has the viscosity of 1000-5000 mpa & s at 40 ℃ and the solid content of 20-40%;
the component B comprises: 50-80% of polyisocyanate, 15-40% of polyester polyol B1 and 1-20% of polyether polyol B2; the units are weight percentages.
Preferably, the glycol chain extender is one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol and 1, 3-propanediol.
Preferably, the cross-linking agent is one or more of trimethylolpropane, glycerol, diethanolamine and triethanolamine.
Preferably, the catalyst is a tertiary amine catalyst; the organic silicon foam stabilizer is polyether modified organic silicon surfactant.
Preferably, the polyisocyanate is one or more of 4, 4 '-diphenylmethane diisocyanate, toluene diisocyanate, carbodiimide-modified 4, 4' -diphenylmethane diisocyanate.
Preferably, the polyester polyol B1 is a polyester polyol with a molecular weight of 2000-2500, which is prepared by performing ester exchange reaction on one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol and 1, 3-propanediol and adipic acid.
Preferably, the polyether polyol B2 is polyether polyol with the functionality of 2-3 and the molecular weight of 3000-5000.
Preferably, the preparation of the component A comprises the following steps: introducing nitrogen into a reaction kettle at normal temperature, sequentially adding polyester polyol A1, polymer polyester polyol A2, a dihydric alcohol chain extender, a cross-linking agent, an organic silicon foam stabilizer, a catalyst and water into the reaction kettle, keeping the temperature of the reaction kettle at 50-65 ℃, stirring for 3-5 hours, fully mixing, discharging, and sealing for storage to obtain a component A; b, preparation of a component: introducing nitrogen into a reaction kettle at the temperature of 50-60 ℃, putting polyisocyanate into the reaction kettle, adding polyester polyol B1 and polyether polyol B2 into the reaction kettle for 3-4 times, keeping the temperature of the reaction kettle at 65-75 ℃, reacting for 3-5 hours, cooling to 40-50 ℃ after sampling and detecting are qualified, discharging, introducing nitrogen, and sealing and storing to obtain the component B.
Preferably, the component A and the component B are foamed on a polyurethane foaming machine, injected into a shoe mold, and demolded after 3-5 minutes to prepare the polyurethane product, wherein the temperature of the shoe mold is 50-60 ℃, and the temperatures of the component A and the component B are both 40-42 ℃.
Preferably, the molding density of the polyurethane resin for shoes is 0.20-0.38 g/cm3, and the hardness is Shore A55-97.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below with reference to the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "inner", "outer", "front", "rear", "both ends", "one end", "the other end", etc., indicate orientations or positional relationships based on which are used only for convenience of description and simplification of description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "disposed," "connected," and the like are to be construed broadly, such as "connected," which may be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The standard parts used in the application document can be purchased from the market, and can be customized according to the record of the specification, the specific connection mode of each part adopts conventional means such as mature bolts, rivets and welding in the prior art, and machines, parts and equipment adopt conventional models in the prior art.
The first embodiment is as follows:
a production and manufacturing process method of a polyurethane insole comprises a component A and a component B, wherein the component A comprises the following components: 20-80% of polyester polyol A1 and 20-80% of polymer polyester polyol A2, wherein the unit is weight percentage; the polyester polyol foam stabilizer also comprises 0.1-0.8% of a cross-linking agent, 5-40% of a dihydric alcohol chain extender, 1-3% of a catalyst, 0.3-1.2% of an organic silicon foam stabilizer and 1-2% of water, wherein the unit is the weight percentage of the total dosage of the polyester polyol A1 and the polymer polyester polyol A2; the polyester polyol A1 is polyester polyol with the molecular weight of 1500-1850, which is prepared by the ester exchange reaction of one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 3-propanediol and trihydroxy methyl propane and adipic acid; the polymer polyester polyol A2 is polymer polyester polyol which is prepared by free radical polymerization of one or more of styrene, acrylonitrile and methyl methacrylate and polyester polyol A1, has the viscosity of 1000-5000 mpa & s at 40 ℃ and the solid content of 20-40%; the component B comprises: 50-80% of polyisocyanate, 15-40% of polyester polyol B1 and 1-20% of polyether polyol B2; the unit is weight percentage, the dihydric alcohol chain extender is one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol and 1, 3-propanediol, the cross-linking agent is one or more of trimethylolpropane, glycerol, diethanolamine and triethanolamine, and the catalyst is tertiary amine catalyst; the organic silicon foam stabilizer is a polyether modified organic silicon surfactant, the polyisocyanate is one or more of 4, 4 '-diphenylmethane diisocyanate, toluene diisocyanate and carbodiimide modified 4, 4' -diphenylmethane diisocyanate, the polyester polyol B1 is polyester polyol with the molecular weight of 2000-2500, which is prepared by performing ester exchange reaction on one or more of ethylene glycol, diethylene glycol, 1, 4 butanediol and 1, 3 propanediol and adipic acid, the polyether polyol B2 is polyether polyol with the functionality of 2-3 and the molecular weight of 3000-5000, and the component A is prepared by the following steps: introducing nitrogen into a reaction kettle at normal temperature, sequentially adding polyester polyol A1, polymer polyester polyol A2, a dihydric alcohol chain extender, a cross-linking agent, an organic silicon foam stabilizer, a catalyst and water into the reaction kettle, keeping the temperature of the reaction kettle at 50-65 ℃, stirring for 3-5 hours, fully mixing, discharging, and sealing for storage to obtain a component A; b, preparation of a component: introducing nitrogen into a reaction kettle at the temperature of 50-60 ℃, firstly putting polyisocyanate into the reaction kettle, then adding polyester polyol B1 and polyether polyol B2 into the reaction kettle for 3-4 times, keeping the temperature of the reaction kettle at 65-75 ℃, reacting for 3-5 hours, cooling to 40-50 ℃ after sampling and detecting are qualified, discharging, introducing nitrogen, sealing and storing to obtain a component B, foaming the component A and the component B on a polyurethane foaming machine, injecting the component A and the component B into a shoe mold, demolding after 3-5 minutes to obtain a polyurethane product, wherein the temperature of the shoe mold is 50-60 ℃, the molding density of the polyurethane shoe resin for 40-42 ℃ of both the component A and the component B is 0.20-0.38 g/cm3, and the hardness is Shore A55-97;
example two:
a production and manufacturing process method of a polyurethane insole comprises a component A and a component B, wherein the component A comprises the following components: 30% of polyester polyol A1, 30% of polymer polyester polyol A2, the unit is weight percentage; the polyester polyol foam stabilizer also comprises 0.2% of a cross-linking agent, 15% of a dihydric alcohol chain extender, 1.3% of a catalyst, 0.5% of an organic silicon foam stabilizer and 1.2% of water, wherein the unit is the weight percentage of the total dosage of the polyester polyol A1 and the polymer polyester polyol A2; the polyester polyol A1 is polyester polyol with the molecular weight of 1500-1850, which is prepared by the ester exchange reaction of one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 3-propanediol and trihydroxy methyl propane and adipic acid; the polymer polyester polyol A2 is polymer polyester polyol which is prepared by free radical polymerization of one or more of styrene, acrylonitrile and methyl methacrylate and polyester polyol A1, has the viscosity of 1000-5000 mpa & s at 40 ℃ and the solid content of 20-40%; the component B comprises: 50-80% of polyisocyanate, 15-40% of polyester polyol B1 and 1-20% of polyether polyol B2; the unit is weight percentage, the dihydric alcohol chain extender is one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol and 1, 3-propanediol, the cross-linking agent is one or more of trimethylolpropane, glycerol, diethanolamine and triethanolamine, and the catalyst is tertiary amine catalyst; the organic silicon foam stabilizer is a polyether modified organic silicon surfactant, the polyisocyanate is one or more of 4, 4 '-diphenylmethane diisocyanate, toluene diisocyanate and carbodiimide modified 4, 4' -diphenylmethane diisocyanate, the polyester polyol B1 is polyester polyol with the molecular weight of 2000-2500, which is prepared by performing ester exchange reaction on one or more of ethylene glycol, diethylene glycol, 1, 4 butanediol and 1, 3 propanediol and adipic acid, the polyether polyol B2 is polyether polyol with the functionality of 2-3 and the molecular weight of 3000-5000, and the component A is prepared by the following steps: introducing nitrogen into a reaction kettle at normal temperature, sequentially adding polyester polyol A1, polymer polyester polyol A2, a dihydric alcohol chain extender, a cross-linking agent, an organic silicon foam stabilizer, a catalyst and water into the reaction kettle, keeping the temperature of the reaction kettle at 50-65 ℃, stirring for 3-5 hours, fully mixing, discharging, and sealing for storage to obtain a component A; b, preparation of a component: introducing nitrogen into a reaction kettle at 50-60 ℃, putting polyisocyanate into the reaction kettle, adding polyester polyol B1 and polyether polyol B2 into the reaction kettle for 3-4 times, keeping the temperature of the reaction kettle at 65-75 ℃, reacting for 3-5 hours, cooling to 40-50 ℃ after sampling and detecting are qualified, discharging, introducing nitrogen, sealing and storing to obtain a component B, foaming the component A and the component B on a polyurethane foaming machine, injecting the component A and the component B into a shoe mold, demolding after 3-5 minutes to obtain a polyurethane product, wherein the temperature of the shoe mold is 50-60 ℃, the molding density of the polyurethane shoe resin at 40-42 ℃ of both the component A and the component B is 0.22g/cm3, and the hardness is Shore A570;
example three:
a production and manufacturing process method of a polyurethane insole comprises a component A and a component B, wherein the component A comprises the following components: 50% of polyester polyol A1, 50% of polymer polyester polyol A2, the unit is weight percentage; the polyester polyol foam stabilizer also comprises 0.5% of a cross-linking agent, 25% of a glycol chain extender, 1.8% of a catalyst, 0.8% of an organic silicon foam stabilizer and 1.5% of water, wherein the unit is the weight percentage of the total dosage of the polyester polyol A1 and the polymer polyester polyol A2; the polyester polyol A1 is polyester polyol with the molecular weight of 1500-1850, which is prepared by the ester exchange reaction of one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 3-propanediol and trihydroxy methyl propane and adipic acid; the polymer polyester polyol A2 is polymer polyester polyol which is prepared by free radical polymerization of one or more of styrene, acrylonitrile and methyl methacrylate and polyester polyol A1, has the viscosity of 1000-5000 mpa & s at 40 ℃ and the solid content of 20-40%; the component B comprises: 50-80% of polyisocyanate, 15-40% of polyester polyol B1 and 1-20% of polyether polyol B2; the unit is weight percentage, the dihydric alcohol chain extender is one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol and 1, 3-propanediol, the cross-linking agent is one or more of trimethylolpropane, glycerol, diethanolamine and triethanolamine, and the catalyst is tertiary amine catalyst; the organic silicon foam stabilizer is a polyether modified organic silicon surfactant, the polyisocyanate is one or more of 4, 4 '-diphenylmethane diisocyanate, toluene diisocyanate and carbodiimide modified 4, 4' -diphenylmethane diisocyanate, the polyester polyol B1 is polyester polyol with the molecular weight of 2000-2500, which is prepared by performing ester exchange reaction on one or more of ethylene glycol, diethylene glycol, 1, 4 butanediol and 1, 3 propanediol and adipic acid, the polyether polyol B2 is polyether polyol with the functionality of 2-3 and the molecular weight of 3000-5000, and the component A is prepared by the following steps: introducing nitrogen into a reaction kettle at normal temperature, sequentially adding polyester polyol A1, polymer polyester polyol A2, a dihydric alcohol chain extender, a cross-linking agent, an organic silicon foam stabilizer, a catalyst and water into the reaction kettle, keeping the temperature of the reaction kettle at 50-65 ℃, stirring for 3-5 hours, fully mixing, discharging, and sealing for storage to obtain a component A; b, preparation of a component: introducing nitrogen into a reaction kettle at 50-60 ℃, putting polyisocyanate into the reaction kettle, adding polyester polyol B1 and polyether polyol B2 into the reaction kettle for 3-4 times, keeping the temperature of the reaction kettle at 65-75 ℃, reacting for 3-5 hours, cooling to 40-50 ℃ after sampling and detecting are qualified, discharging, introducing nitrogen, sealing and storing to obtain a component B, foaming the component A and the component B on a polyurethane foaming machine, injecting the component A and the component B into a shoe mold, demolding after 3-5 minutes to obtain a polyurethane product, wherein the temperature of the shoe mold is 50-60 ℃, the molding density of the polyurethane shoe resin at 40-42 ℃ of both the component A and the component B is 0.30g/cm3, and the hardness is Shore A75;
example four:
a production and manufacturing process method of a polyurethane insole comprises a component A and a component B, wherein the component A comprises the following components: 70% of polyester polyol A1, 70% of polymer polyester polyol A2, the unit is weight percentage; the polyester polyol foam stabilizer also comprises 0.7% of a cross-linking agent, 35% of a dihydric alcohol chain extender, 2.6% of a catalyst, 1.1% of an organic silicon foam stabilizer and 1.8% of water, wherein the unit is the weight percentage of the total dosage of the polyester polyol A1 and the polymer polyester polyol A2; the polyester polyol A1 is polyester polyol with the molecular weight of 1500-1850, which is prepared by the ester exchange reaction of one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 3-propanediol and trihydroxy methyl propane and adipic acid; the polymer polyester polyol A2 is polymer polyester polyol which is prepared by free radical polymerization of one or more of styrene, acrylonitrile and methyl methacrylate and polyester polyol A1, has the viscosity of 1000-5000 mpa & s at 40 ℃ and the solid content of 20-40%; the component B comprises: 50-80% of polyisocyanate, 15-40% of polyester polyol B1 and 1-20% of polyether polyol B2; the unit is weight percentage, the dihydric alcohol chain extender is one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol and 1, 3-propanediol, the cross-linking agent is one or more of trimethylolpropane, glycerol, diethanolamine and triethanolamine, and the catalyst is tertiary amine catalyst; the organic silicon foam stabilizer is a polyether modified organic silicon surfactant, the polyisocyanate is one or more of 4, 4 '-diphenylmethane diisocyanate, toluene diisocyanate and carbodiimide modified 4, 4' -diphenylmethane diisocyanate, the polyester polyol B1 is polyester polyol with the molecular weight of 2000-2500, which is prepared by performing ester exchange reaction on one or more of ethylene glycol, diethylene glycol, 1, 4 butanediol and 1, 3 propanediol and adipic acid, the polyether polyol B2 is polyether polyol with the functionality of 2-3 and the molecular weight of 3000-5000, and the component A is prepared by the following steps: introducing nitrogen into a reaction kettle at normal temperature, sequentially adding polyester polyol A1, polymer polyester polyol A2, a dihydric alcohol chain extender, a cross-linking agent, an organic silicon foam stabilizer, a catalyst and water into the reaction kettle, keeping the temperature of the reaction kettle at 50-65 ℃, stirring for 3-5 hours, fully mixing, discharging, and sealing for storage to obtain a component A; b, preparation of a component: introducing nitrogen into a reaction kettle at 50-60 ℃, putting polyisocyanate into the reaction kettle, adding polyester polyol B1 and polyether polyol B2 into the reaction kettle for 3-4 times, keeping the temperature of the reaction kettle at 65-75 ℃, reacting for 3-5 hours, cooling to 40-50 ℃ after sampling and detecting are qualified, discharging, introducing nitrogen, sealing and storing to obtain a component B, foaming the component A and the component B on a polyurethane foaming machine, injecting the component A and the component B into a shoe mold, demolding after 3-5 minutes to obtain a polyurethane product, wherein the temperature of the shoe mold is 50-60 ℃, the molding density of the polyurethane shoe resin at 40-42 ℃ of both the component A and the component B is 0.38g/cm3, and the hardness is Shore A97;
in summary, the four embodiments, the preferred embodiment four, have the advantage that the polyurethane sole can still maintain high hardness under the condition of low density.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A production and manufacturing process method of a polyurethane insole comprises a component A and a component B, and is characterized in that: the component A comprises: 20-80% of polyester polyol A1 and 20-80% of polymer polyester polyol A2, wherein the unit is weight percentage; the polyester polyol foam stabilizer also comprises 0.1-0.8% of a cross-linking agent, 5-40% of a dihydric alcohol chain extender, 1-3% of a catalyst, 0.3-1.2% of an organic silicon foam stabilizer and 1-2% of water, wherein the unit is the weight percentage of the total dosage of the polyester polyol A1 and the polymer polyester polyol A2;
the polyester polyol A1 is polyester polyol with the molecular weight of 1500-1850, which is prepared by the ester exchange reaction of one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 3-propanediol and trihydroxy methyl propane and adipic acid;
the polymer polyester polyol A2 is polymer polyester polyol which is prepared by free radical polymerization of one or more of styrene, acrylonitrile and methyl methacrylate and polyester polyol A1, has the viscosity of 1000-5000 mpa & s at 40 ℃ and the solid content of 20-40%;
the component B comprises: 50-80% of polyisocyanate, 15-40% of polyester polyol B1 and 1-20% of polyether polyol B2; the units are weight percentages.
2. The manufacturing process method of polyurethane insole as claimed in claim 1, wherein: the dihydric alcohol chain extender is one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol and 1, 3-propanediol.
3. The manufacturing process method of polyurethane insole as claimed in claim 1, wherein: the cross-linking agent is one or more of trimethylolpropane, glycerol, diethanolamine and triethanolamine.
4. The manufacturing process method of polyurethane insole as claimed in claim 1, wherein: the catalyst is tertiary amine catalyst; the organic silicon foam stabilizer is polyether modified organic silicon surfactant.
5. The manufacturing process method of polyurethane insole as claimed in claim 1, wherein: the polyisocyanate is one or more of 4, 4 '-diphenylmethane diisocyanate, toluene diisocyanate and carbodiimide modified 4, 4' -diphenylmethane diisocyanate.
6. The manufacturing process method of polyurethane insole as claimed in claim 1, wherein: the polyester polyol B1 is prepared by performing ester exchange reaction on one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol and 1, 3-propanediol and adipic acid to obtain polyester polyol with the molecular weight of 2000-2500.
7. The manufacturing process method of polyurethane insole as claimed in claim 1, wherein: the polyether polyol B2 is polyether polyol with the functionality of 2-3 and the molecular weight of 3000-5000.
8. The manufacturing process of polyurethane insole as claimed in claim 1, wherein: preparation of the component A: introducing nitrogen into a reaction kettle at normal temperature, sequentially adding polyester polyol A1, polymer polyester polyol A2, a dihydric alcohol chain extender, a cross-linking agent, an organic silicon foam stabilizer, a catalyst and water into the reaction kettle, keeping the temperature of the reaction kettle at 50-65 ℃, stirring for 3-5 hours, fully mixing, discharging, and sealing for storage to obtain a component A; b, preparation of a component: introducing nitrogen into a reaction kettle at the temperature of 50-60 ℃, putting polyisocyanate into the reaction kettle, adding polyester polyol B1 and polyether polyol B2 into the reaction kettle for 3-4 times, keeping the temperature of the reaction kettle at 65-75 ℃, reacting for 3-5 hours, cooling to 40-50 ℃ after sampling and detecting are qualified, discharging, introducing nitrogen, and sealing and storing to obtain the component B.
9. The manufacturing process method of polyurethane insole as claimed in claim 1, wherein: foaming the component A and the component B on a polyurethane foaming machine, injecting the foamed components into a shoe mold, demolding after 3-5 minutes to obtain a polyurethane product, wherein the temperature of the shoe mold is 50-60 ℃, and the temperature of the component A and the temperature of the component B are both 40-42 ℃.
10. The manufacturing process method of polyurethane insole as claimed in claim 9, wherein: the molding density of the polyurethane resin for shoes is 0.20-0.38 g/cm3, and the hardness is Shore A55-97.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250820A (en) * | 2020-10-21 | 2021-01-22 | 盐城市恒丰海绵有限公司 | Sinking-bottom expanded polyurethane with high tearing property and preparation method thereof |
| CN117106154A (en) * | 2023-10-25 | 2023-11-24 | 山东一诺威聚氨酯股份有限公司 | Low-temperature-resistant and dirt-resistant polyurethane sole resin and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735597A (en) * | 2009-12-07 | 2010-06-16 | 无锡双象化学工业有限公司 | Resin for polyurethane shoe with extremely-low density and high hardness and preparation method thereof |
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- 2019-06-04 CN CN201910480562.3A patent/CN110643014A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735597A (en) * | 2009-12-07 | 2010-06-16 | 无锡双象化学工业有限公司 | Resin for polyurethane shoe with extremely-low density and high hardness and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250820A (en) * | 2020-10-21 | 2021-01-22 | 盐城市恒丰海绵有限公司 | Sinking-bottom expanded polyurethane with high tearing property and preparation method thereof |
| CN117106154A (en) * | 2023-10-25 | 2023-11-24 | 山东一诺威聚氨酯股份有限公司 | Low-temperature-resistant and dirt-resistant polyurethane sole resin and preparation method and application thereof |
| CN117106154B (en) * | 2023-10-25 | 2024-03-08 | 山东一诺威聚氨酯股份有限公司 | Low-temperature-resistant and dirt-resistant polyurethane sole resin and preparation method and application thereof |
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