CN106810668B - Polyurethane resin for shoe sole and preparation method and application thereof - Google Patents
Polyurethane resin for shoe sole and preparation method and application thereof Download PDFInfo
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- 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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- 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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- 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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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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
- C08G18/6552—Compounds of group C08G18/63
- C08G18/6558—Compounds of group C08G18/63 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6564—Compounds of group C08G18/63 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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- 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
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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
- C08G2410/00—Soles
Abstract
The invention discloses a resin for polyurethane soles, a preparation method and application thereof, wherein the resin comprises a resin A component, a resin B1 component and a resin B2 component, wherein the resin A component comprises a polyol A, a cross-linking agent, a catalyst, a foaming agent and a foam stabilizer; the resin B1 comprises 1100 parts of isocyanate B, 110-40 parts of polyol B, 0.002-0.010 part of side reaction inhibitor, the resin B2 comprises 2100 parts of isocyanate B, 250-100 parts of polyol B, 0.002-0.010 part of side reaction inhibitor, the isocyanate B1 is diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate, the polyol B1 is polyether diol, the isocyanate B2 is diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate, and the polyol B2 is polyether diol. The invention can prepare polyurethane soles with different hardness and excellent performance, and has low cost.
Description
Technical Field
The invention relates to a resin for a polyurethane sole, a preparation method and application thereof.
Background
The full-name polyurethane is a general name of macromolecular compounds containing repeated urethane groups on the main chain, and is a macromolecular compound obtained by the interaction of binary or polybasic organic isocyanate and a polyol compound. The polyurethane sole has the characteristics of light weight, good rebound resilience and the like.
The resin used for producing polyurethane soles is generally a two-component split-charging raw material, namely a polyol mixture and a prepolymer (AB material/AB component or black and white material for short).
Polyurethane soles with different performance requirements need different types of AB materials for matching use. For polyurethane sole manufacturing enterprises, raw materials of various types and specifications are required to be prepared to meet the production of soles with different performance requirements, and a proofing machine table and a material tank body are required to be cleaned when the raw materials are replaced every time, so that the production cost is high.
Disclosure of Invention
The invention aims to provide a resin for a polyurethane sole, a preparation method and application thereof, so as to overcome the defects in the prior art.
The resin for the polyurethane sole comprises a resin A component, a resin B1 component and a resin B2 component;
the resin A component consists of the following components in parts by weight:
the resin B1 comprises the following components in parts by weight:
1100 parts of isocyanate B;
110-40 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor;
the resin B2 comprises the following components in parts by weight:
2100 parts of isocyanate B;
250-100 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor.
Preferably:
the resin A component consists of the following components in parts by weight:
it is preferable that
The resin B1 comprises the following components in parts by weight:
1100 parts of isocyanate B;
112-20 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor;
it is preferable that
The resin B2 comprises the following components in parts by weight:
2100 parts of isocyanate B;
250-90 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor.
The polymeric polyol in the resin A component is a mixture of polyether polyol and polymer polyol, and the mass ratio of the polyether polyol to the polymer polyol is 1: 1-4: 1.
The polyether polyol is polyoxyethylene-propylene oxide dihydric alcohol with the number average molecular weight of 6000-10000;
the polymer polyol is styrene or acrylonitrile graft copolymerization ethylene oxide-propylene oxide trihydric alcohol with the number average molecular weight of 6000-10000, and the solid content is 25-35%.
The cross-linking agent is one or more of ethylene glycol, 1, 4-butanediol, 1, 3-propanediol and 1, 6-butanediol.
The catalyst is a mixture of a triethylene diamine ethylene glycol solution and a solution prepared from 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, and the mass ratio of the triethylene diamine ethylene glycol solution to the solution prepared from 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol is 1: 4-1: 1.
The foaming agent is water;
the foam stabilizer is an organic silicon foam stabilizer;
the isocyanate B1 in the component B1 of the resin is one or more of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate;
in the component B1, the polymeric polyol B1 is polyether diol, preferably polyoxyethylene-propylene oxide diol with the number average molecular weight of 6000-10000;
the side reaction inhibitor in the component B1 is phosphoric acid;
the isocyanate B2 in the component B2 of the resin is one or more of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate;
the component B2 is characterized in that the polymeric polyol B2 is polyether diol, preferably polyoxyethylene-propylene oxide diol with the number average molecular weight of 3000-7000;
the side reaction inhibitor in the component of the resin B2 is phosphoric acid.
The preparation method of the resin for the polyurethane sole comprises the following steps:
(1) reacting a polyol, a cross-linking agent, a catalyst, a foaming agent and a foam stabilizer at 50-60 ℃ for 1.5-2.5 h, cooling to 40-45 ℃, and mixing for 1.0-1.5 h to obtain a polyurethane resin component A;
(2) reacting isocyanate B1, polyol B1 and a side reaction inhibitor at 65-75 ℃ for 2-3 h to obtain a polyurethane resin B1 component;
(3) and (3) reacting the isocyanate B2, the polyol B2 and the side reaction inhibitor at 65-75 ℃ for 2-3 h to obtain the polyurethane resin B2 component.
The resin for the polyurethane sole is used for preparing the high-resilience polyurethane sole, and the preparation method comprises the following steps:
mixing a polyurethane resin A component at the temperature of 40-45 ℃, a polyurethane resin B1 component at the temperature of 40-45 ℃ and a polyurethane resin B2 component at the temperature of 40-45 ℃ in a casting machine, injecting the mixture into a 45-55 ℃ mold for reaction for 3-5 min for molding, demolding, and curing in a 60-75 ℃ oven for 22-24 h to obtain the polyurethane sole.
The mass ratio of the polyurethane resin B1 component to the polyurethane resin B2 component is 1: 9-9: 1;
the ratio of the number of moles of active hydrogen of the A component to the number of moles of isocyanate groups of the B1 component and the B2 component together was 1: 1.
The invention has the beneficial effects that:
the resin for the polyurethane sole comprises a resin A component, a resin B1 component and a resin B2 component, and the polyurethane sole with different hardness and different properties can be prepared by adjusting the mass ratio of the resin B1 component to the resin B2 component. Compared with the common two-component polyurethane resin, in the process of producing the polyurethane sole, a manufacturer does not need to prepare various different raw materials, when producing soles with different requirements, only the proportion of the components B1 and B2 needs to be adjusted, the production cost of the polyurethane sole is saved, the resource waste is reduced, the production efficiency is improved, the polyurethane resin chain segments formed by mixing and reacting the two prepolymer components (B1 and B2) with the component A in different proportions are more regular and ordered, and the prepared polyurethane shoe substrate has better performance. The polyurethane sole produced by the product has wide adjustable range of hardness, low shrinkage rate, good physical property, low cost and high production efficiency, and is more suitable for continuous production operation.
Detailed Description
The following examples are given to illustrate the present invention and should not be construed as limiting the scope of the present invention. The implementation conditions used in the examples may be modified or adjusted according to the conditions and requirements of the particular manufacturer.
Example 1
221.7kg of polyoxyethylene-propylene oxide dihydric alcohol (with the number average molecular weight of 6000), 55.4kg of styrene graft copolymerization ethylene oxide-propylene oxide trihydric alcohol (with the number average molecular weight of 6000), 13.9kg of ethylene glycol, 0.22kg of ethylene glycol solution of triethylene diamine, 0.89kg of solution prepared by 70 weight percent of bis (dimethylaminoethyl) ether and 30 weight percent of dipropylene glycol, 2.77kg of water and 0.28kg of organosilicon foam stabilizer react at 50 ℃ for 2.5h, then the temperature is reduced to 40 ℃, and the mixture is mixed for 1.5h to obtain the component A of the polyurethane resin.
78.4g of diphenylmethane diisocyanate, 26.0kg of carbodiimide-modified diphenylmethane diisocyanate, 1.31kg of polyoxyethylene-oxypropylene diol (number average molecular weight: 6000) and 0.0026kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a polyurethane resin B1 component.
7.64kg of diphenylmethane diisocyanate, 3.92kg of polyoxyethylene-oxypropylene diol (number average molecular weight of 3000) and 0.0003kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a polyurethane resin B2 component.
Mixing the polyurethane resin A component with the temperature of 40 ℃, the polyurethane resin B1 component with the temperature of 40 ℃ and the polyurethane resin B2 component with the temperature of 40 ℃ in a casting machine, injecting into a 45 ℃ mold for 5min for molding, demolding, and curing in a 60 ℃ oven for 24h to obtain the polyurethane sole.
Example 2
221.7kg of polyoxyethylene-propylene oxide dihydric alcohol (with the number average molecular weight of 6000), 55.4kg of styrene graft copolymerization ethylene oxide-propylene oxide trihydric alcohol (with the number average molecular weight of 6000), 13.9kg of ethylene glycol, 0.22kg of ethylene glycol solution of triethylene diamine, 0.89kg of solution prepared by 70 weight percent of bis (dimethylaminoethyl) ether and 30 weight percent of dipropylene glycol, 2.77kg of water and 0.28kg of organosilicon foam stabilizer react at 50 ℃ for 2.5h, then the temperature is reduced to 40 ℃, and the mixture is mixed for 1.5h to obtain the component A of the polyurethane resin.
12.0kg of diphenylmethane diisocyanate, 4.00kg of carbodiimide-modified diphenylmethane diisocyanate, 0.19kg of polyoxyethylene-oxypropylene diol (number average molecular weight: 6000) and 0.0002kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a polyurethane resin B1 component.
97.0kg of diphenylmethane diisocyanate, 48.6kg of polyoxyethylene-oxypropylene diol (number average molecular weight of 3000) and 0.003kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a polyurethane resin B2 component.
Mixing the polyurethane resin A component with the temperature of 40 ℃, the polyurethane resin B1 component with the temperature of 40 ℃ and the polyurethane resin B2 component with the temperature of 40 ℃ in a casting machine, injecting into a 45 ℃ mold for 5min for molding, demolding, and curing in a 60 ℃ oven for 24h to obtain the polyurethane sole.
Example 3
101.0kg of polyoxyethylene-propylene oxide dihydric alcohol (with the number average molecular weight of 10000), 101.0kg of acrylonitrile graft copolymerization ethylene oxide-propylene oxide trihydric alcohol (with the number average molecular weight of 10000), 20.2kg of ethylene glycol, 1.01kg of ethylene glycol solution of triethylene diamine, 1.01kg of solution prepared by 70 weight percent of bis (dimethylaminoethyl) ether and 30 weight percent of dipropylene glycol, 3.03kg of water and 4.04kg of organic silicon foam stabilizer react at 60 ℃ for 1.5h, then the temperature is reduced to 45 ℃, and the mixture is mixed for 1.0h to obtain the component A of the polyurethane resin.
16.4kg of diphenylmethane diisocyanate, 4.10kg of carbodiimide-modified diphenylmethane diisocyanate, 4.10kg of polyoxyethylene-oxypropylene diol (number average molecular weight: 10000) and 0.0025kg of phosphoric acid were reacted at 75 ℃ for 2 hours to obtain a polyurethane resin B1 component.
118.6kg of diphenylmethane diisocyanate, 102.4kg of polyoxyethylene-oxypropylene diol (7000 molecular weight) and 0.022kg of phosphoric acid were reacted at 75 ℃ for 2 hours to obtain a polyurethane resin B2 component.
Mixing the polyurethane resin A component with the temperature of 45 ℃, the polyurethane resin B1 component with the temperature of 45 ℃ and the polyurethane resin B2 component with the temperature of 45 ℃ in a casting machine, injecting into a 55 ℃ mold for 3min for molding, demolding, and curing in a 75 ℃ oven for 22h to obtain the polyurethane sole.
Example 4
101.0kg of polyoxyethylene-propylene oxide dihydric alcohol (with the number average molecular weight of 10000), 101.0kg of acrylonitrile graft copolymerization ethylene oxide-propylene oxide trihydric alcohol (with the number average molecular weight of 10000), 20.2kg of ethylene glycol, 1.01kg of ethylene glycol solution of triethylene diamine, 1.01kg of solution prepared by 70 weight percent of bis (dimethylaminoethyl) ether and 30 weight percent of dipropylene glycol, 3.03kg of water and 4.04kg of organic silicon foam stabilizer react at 60 ℃ for 1.5h, then the temperature is reduced to 45 ℃, and the mixture is mixed for 1.0h to obtain the component A of the polyurethane resin.
103.9g of diphenylmethane diisocyanate, 25.9kg of carbodiimide-modified diphenylmethane diisocyanate, 25.9kg of polyoxyethylene-oxypropylene diol (number average molecular weight: 10000) and 0.016kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a polyurethane resin component B.
9.34kg of diphenylmethane diisocyanate, 8.03kg of polyoxyethylene-oxypropylene diol (7000 molecular weight) and 0.0018kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a polyurethane resin B2 component.
Mixing the polyurethane resin A component with the temperature of 45 ℃, the polyurethane resin B1 component with the temperature of 45 ℃ and the polyurethane resin B2 component with the temperature of 45 ℃ in a casting machine, injecting into a 55 ℃ mold for 3min for molding, demolding, and curing in a 75 ℃ oven for 22h to obtain the polyurethane sole.
Example 5
290.1kg of polyoxyethylene-propylene oxide dihydric alcohol (with the number average molecular weight of 9000), 145.1kg of styrene graft copolymerization ethylene oxide-propylene oxide trihydric alcohol (with the number average molecular weight of 9000), 34.8kg of 1, 4-butanediol, 1.31kg of ethylene glycol solution of triethylene diamine, 2.61kg of solution prepared by 70 weight percent of bis (dimethylaminoethyl) ether and 30 weight percent of dipropylene glycol, 5.66kg of water and 4.35kg of organic silicon foam stabilizer react at 60 ℃ for 1.5h, then the temperature is reduced to 45 ℃, and the mixture is mixed for 1.0h to obtain the polyurethane resin A component.
126.7kg of diphenylmethane diisocyanate, 17.4kg of polyoxyethylene-oxypropylene diol (9000 in number average molecular weight) and 0.012kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a polyurethane resin component B.
43.2kg of diphenylmethane diisocyanate, 36.0kg of carbodiimide-modified diphenylmethane diisocyanate, 65.2kg of polyoxyethylene-oxypropylene diol (number average molecular weight of 3000) and 0.012kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a polyurethane resin B2 component.
Mixing the polyurethane resin A component with the temperature of 45 ℃, the polyurethane resin B1 component with the temperature of 45 ℃ and the polyurethane resin B2 component with the temperature of 45 ℃ in a casting machine, injecting into a 55 ℃ mold for 3min for molding, demolding, and curing in a 75 ℃ oven for 22h to obtain the polyurethane sole.
Example 6
200.0kg of polyoxyethylene-propylene oxide dihydric alcohol (with the number average molecular weight of 8000), 160.0kg of styrene graft copolymerization ethylene oxide-propylene oxide trihydric alcohol (with the number average molecular weight of 8000), 10.0kg of 1, 4-butanediol, 9.20kg of ethylene glycol, 1.08kg of ethylene glycol solution of triethylene diamine, 2.16kg of solution prepared by 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, 4.32kg of water and 4.68kg of organic silicon foam stabilizer react at the temperature of 50 ℃ for 2.5h, then the temperature is reduced to 40 ℃, and the mixture is mixed for 1.5h to obtain the component A of the polyurethane resin.
109.6kg of diphenylmethane diisocyanate, 6.38kg of polyoxyethylene-oxypropylene diol (8000 as number average molecular weight) and 0.007kg of phosphoric acid were reacted at 75 ℃ for 2 hours to obtain a polyurethane resin B1 component.
12.9kg of diphenylmethane diisocyanate, 9.02kg of carbodiimide-modified diphenylmethane diisocyanate, 16.8kg of polyoxyethylene-oxypropylene diol (number average molecular weight 4000) and 0.002kg of phosphoric acid were reacted at 75 ℃ for 2 hours to obtain a polyurethane resin B2 component.
Mixing the polyurethane resin A component with the temperature of 40 ℃, the polyurethane resin B1 component with the temperature of 40 ℃ and the polyurethane resin B2 component with the temperature of 40 ℃ in a casting machine, injecting into a 45 ℃ mold for 5min for molding, demolding, and curing in a 60 ℃ oven for 24h to obtain the polyurethane sole.
Comparative example 1
221.7kg of polyoxyethylene-propylene oxide dihydric alcohol (with the number average molecular weight of 6000), 55.4kg of styrene graft copolymerization ethylene oxide-propylene oxide trihydric alcohol (with the number average molecular weight of 6000), 13.9kg of ethylene glycol, 0.22kg of ethylene glycol solution of triethylene diamine, 0.89kg of solution prepared by 70 weight percent of bis (dimethylaminoethyl) ether and 30 weight percent of dipropylene glycol, 2.77kg of water and 0.28kg of organosilicon foam stabilizer react at 50 ℃ for 2.5h, then the temperature is reduced to 40 ℃, and the mixture is mixed for 1.5h to obtain the component A of the polyurethane resin.
86.04g of diphenylmethane diisocyanate, 26.0kg of carbodiimide-modified diphenylmethane diisocyanate, 1.31kg of polyoxyethylene-oxypropylene diol (number average molecular weight: 6000), 3.92kg of polyoxyethylene-oxypropylene diol (number average molecular weight: 3000) and 0.0029kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a polyurethane resin component B.
Mixing the polyurethane resin A component with the temperature of 40 ℃ and the polyurethane resin B component with the temperature of 40 ℃ in a casting machine, injecting into a 45 ℃ mold for 5min for molding, demolding, and curing in a 60 ℃ oven for 24h to obtain the polyurethane sole.
Comparative example 2
101.0kg of polyoxyethylene-propylene oxide dihydric alcohol (with the number average molecular weight of 10000), 101.0kg of acrylonitrile graft copolymerization ethylene oxide-propylene oxide trihydric alcohol (with the number average molecular weight of 10000), 20.2kg of ethylene glycol, 1.01kg of ethylene glycol solution of triethylene diamine, 1.01kg of solution prepared by 70 weight percent of bis (dimethylaminoethyl) ether and 30 weight percent of dipropylene glycol, 3.03kg of water and 4.04kg of organic silicon foam stabilizer react at 60 ℃ for 1.5h, then the temperature is reduced to 45 ℃, and the mixture is mixed for 1.0h to obtain the component A of the polyurethane resin.
135.0kg of diphenylmethane diisocyanate, 4.10kg of carbodiimide-modified diphenylmethane diisocyanate, 4.10kg of polyoxyethylene-oxypropylene diol (number average molecular weight: 10000), 102.4kg of polyoxyethylene-oxypropylene diol (number average molecular weight: 7000) and 0.0245kg of phosphoric acid were reacted at 75 ℃ for 2 hours to obtain polyurethane resin component B.
Mixing the polyurethane resin A component with the temperature of 45 ℃ and the polyurethane resin B component with the temperature of 45 ℃ in a casting machine, injecting into a 55 ℃ mold for 3min for molding, demolding, and curing in a 75 ℃ oven for 22h to obtain the polyurethane sole.
The polyurethane soles prepared in examples 1-4 and comparative examples 1-2 were tested for the following properties:
TABLE I
From the examples 1 and 2, and 3 and 4, it can be seen that, on the premise that the component A of the polyurethane resin is not changed, the polyurethane soles with different hardness, different tensile strength, different tear strength and other physical properties can be prepared by simply adjusting the proportion of the component B1 to the component B2, so that the production efficiency of the polyurethane soles is improved, the energy consumption is reduced, and the production cost of the polyurethane soles is reduced. Comparing example 1 with comparative example 1, and example 3 with comparative example 2, it is known that it is easier to prepare a shoe sole having a higher hardness and a lower shrinkage or having a lower hardness and a lower shrinkage by using the resin for a polyurethane shoe sole of the present invention.
Although the embodiments of the present invention have been described in detail, the technical aspects of the present invention are not limited to the embodiments, and equivalent changes or modifications made to the contents of the claims of the present invention should fall within the technical scope of the present invention without departing from the spirit and the spirit of the present invention.
Claims (10)
1. A resin for polyurethane shoe soles, characterized by comprising a resin a component, a resin B1 component and a resin B2 component; the resin A component consists of the following components: the foaming agent comprises a polyol A, a cross-linking agent, a catalyst, a foaming agent and a foam stabilizer;
the polymeric polyol A in the resin A component is a mixture of polyether polyol and polymer polyol;
the polyether polyol is polyoxyethylene-propylene oxide dihydric alcohol with the number average molecular weight of 6000-10000;
the polymer polyol is styrene or acrylonitrile graft copolymerization ethylene oxide-propylene oxide trihydric alcohol with the number average molecular weight of 6000-10000, and the solid content is 25-35%;
the cross-linking agent is one or more of ethylene glycol, 1, 4-butanediol, 1, 3-propanediol and 1, 6-butanediol;
the resin B1 component comprises the following components in parts by weight:
1100 parts of isocyanate B;
110-40 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor;
the resin B2 comprises the following components in parts by weight:
2100 parts of isocyanate B;
250-100 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor;
the isocyanate B1 is selected from one or more of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate;
the polyol B1 is polyoxyethylene-oxypropylene diol with the number average molecular weight of 6000-10000;
the isocyanate B2 is one or more of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate;
the polyol B2 is polyoxyethylene-oxypropylene diol with the number average molecular weight of 3000-7000;
the mass ratio of the polyurethane resin B1 component to the polyurethane resin B2 component is 1: 9-9: 1.
2. The resin for polyurethane shoe soles according to claim 1, characterized in that said resin a component consists of:
3. the resin for polyurethane shoe soles according to claim 2, characterized in that said resin a component consists of:
the resin A component consists of the following components in parts by weight:
4. the resin for polyurethane soles according to claim 1, wherein the resin B1 component is composed of the following components in parts by weight:
1100 parts of isocyanate B;
112-20 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor;
the resin B2 comprises the following components in parts by weight:
2100 parts of isocyanate B;
250-90 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor;
the isocyanate B1 is selected from one or more of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate;
the isocyanate B2 is one or more of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate;
the side reaction inhibitor is phosphoric acid.
5. The resin for polyurethane shoe soles according to claim 2, wherein the mass ratio of the polyether polyol to the polymer polyol is 1: 1 to 4: 1.
6. The resin for polyurethane shoe soles according to claim 5, wherein,
the catalyst is a mixture of a triethylene diamine ethylene glycol solution and a solution prepared from 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, and the mass ratio of the triethylene diamine ethylene glycol solution to the solution prepared from 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol is 1: 4-1: 1;
the foaming agent is water;
the foam stabilizer is an organic silicon foam stabilizer.
7. The polyurethane sole resin according to any one of claims 1 to 6, wherein the ratio of the number of moles of active hydrogen of the A component to the number of moles of isocyanate groups of the B1 component and the B2 component is 1: 1.
8. The method for preparing the resin for polyurethane shoe soles according to any one of claims 1 to 7, comprising the steps of:
(1) reacting a polyol, a cross-linking agent, a catalyst, a foaming agent and a foam stabilizer at 50-60 ℃ for 1.5-2.5 h, cooling to 40-45 ℃, and mixing for 1.0-1.5 h to obtain a polyurethane resin component A;
(2) reacting isocyanate B1, polyol B1 and a side reaction inhibitor at 65-75 ℃ for 2-3 h to obtain a polyurethane resin B1 component;
(3) and (3) reacting the isocyanate B2, the polyol B2 and the side reaction inhibitor at 65-75 ℃ for 2-3 h to obtain the polyurethane resin B2 component.
9. Use of the resin for polyurethane shoe soles according to any one of claims 1 to 7, for the preparation of polyurethane shoe soles.
10. Use according to claim 9, characterized in that the method of application comprises the steps of: mixing a polyurethane resin A component at the temperature of 40-45 ℃, a polyurethane resin B1 component at the temperature of 40-45 ℃ and a polyurethane resin B2 component at the temperature of 40-45 ℃ in a casting machine, injecting the mixture into a 45-55 ℃ mold for reaction for 3-5 min for molding, demolding, and curing in a 60-75 ℃ oven for 22-24 h to obtain the polyurethane sole.
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| CN108409934A (en) * | 2018-03-09 | 2018-08-17 | 旭川化学（昆山）有限公司 | Height rebound Low temperature-resistanpolyurethane polyurethane sole raw material and preparation method thereof |
| CN111358115A (en) * | 2020-04-23 | 2020-07-03 | 瑞典立信远东有限公司温州代表处 | Shoe with DuPont paper as vamp and production method thereof |
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| GB9208377D0 (en) * | 1992-04-16 | 1992-06-03 | Ici Plc | Process for preparing flexible polyurethane foams |
| CN1242384A (en) * | 1992-04-16 | 2000-01-26 | 帝国化学工业公司 | Polyisocyanate composition |
| CN1037612C (en) * | 1992-07-20 | 1998-03-04 | 中国科学院化学研究所 | Multi-block polymer material with thermo-recoverable shape |
| US5856372A (en) * | 1996-05-23 | 1999-01-05 | Arco Chemical Technology, L.P. | Microcellular elastomers with improved processability and properties |
| JP4495296B2 (en) * | 2000-03-30 | 2010-06-30 | 倉敷紡績株式会社 | Polyurethane foam |
| US6548564B1 (en) * | 2001-12-13 | 2003-04-15 | Bayer Corporation | Polyether polyols with increased functionality |
| CN1171925C (en) * | 2001-12-27 | 2004-10-20 | 中国科学院山西煤炭化学研究所 | Preparation method of polyether polyarethane microporous elastic body |
| CN100572413C (en) * | 2007-10-31 | 2009-12-23 | 无锡双象化学工业有限公司 | Polyester type ultra-low density polyurethane resin for shoes |
| CN101503500A (en) * | 2008-12-01 | 2009-08-12 | 无锡双象化学工业有限公司 | Resin for polyester type shoes |
| CN101486788B (en) * | 2008-12-30 | 2011-09-14 | 浙江华峰新材料股份有限公司 | Low density high hardness polyurethane micropore elastomer and preparation thereof |
| CN104341578B (en) * | 2014-10-27 | 2016-10-12 | 中国科学院长春应用化学研究所 | A kind of preparation method of wide temperature range modulus stabilizing polyurethane micro-pore elastomer |
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