CN106700027B - Polyurethane resin for breathable insoles, and preparation method and application thereof - Google Patents
Polyurethane resin for breathable insoles, and preparation method and application thereof Download PDFInfo
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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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least 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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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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
- C08G18/632—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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
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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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- 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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane resin for a breathable insole, 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 180-100 parts of isocyanate B, 11-30 parts of polyol B, 0.002-0.010 part of a side reaction inhibitor, the resin B2 comprises 2100 parts of isocyanate B, 250-100 parts of polyol B, 0.002-0.010 part of a side reaction inhibitor, the isocyanate B1 is diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate, the polyol B1 is polyoxyethylene-oxypropylene triol, the isocyanate B2 is diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate, and the polyol B2 is polyoxyethylene-oxypropylene diol. The invention can prepare polyurethane insoles with different hardness and has low cost.
Description
Technical Field
The invention relates to polyurethane resin for insoles, 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 insole has the characteristics of light weight, good elasticity, high strength, wide adjustable range of hardness and the like, and is suitable for different manufacturers with different shoe types.
The resins used to produce polyurethane insoles are generally two-component materials-polyol mixtures and prepolymers (AB materials/AB components or black and white materials for short).
Polyurethane insoles with different hardness and different performance requirements need different types of AB materials for matching use. For polyurethane insole production enterprises, raw materials of various types and specifications are required to be prepared to adapt to production of insoles 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 polyurethane resin for a breathable insole, a preparation method and application thereof, so as to overcome the defects in the prior art.
The polyurethane resin for the breathable insole 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:
180-100 parts of isocyanate B;
11-30 parts of 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:
preferably:
the resin B1 comprises the following components in parts by weight:
1100 parts of isocyanate B;
150-90 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor;
preferably:
the resin B2 comprises the following components in parts by weight:
220-80 parts of isocyanate B;
220-80 parts of a polyol B;
0.002-0.010 part of side reaction inhibitor.
The polymeric polyol A 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 9: 11-5: 1.
The polyether polyol is a mixture of polyoxyethylene-propylene oxide triol with the number average molecular weight of 6000-10000 and polyoxypropylene triol with the number average molecular weight of 1000-5000, and the mass ratio of the polyoxyethylene-propylene oxide triol with the number average molecular weight of 6000-10000 to the polyoxypropylene triol with the number average molecular weight of 1000-5000 is 2: 5-5: 2.
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 40-50%.
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;
in the component B1, isocyanate B1 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 triol, preferably polyoxyethylene-propylene oxide triol 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 polyurethane resin for the breathable insole 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 polyurethane resin for the insoles is used for preparing polyurethane insoles with different hardness requirements, excellent air permeability and high physical property, and the preparation method comprises the following steps:
mixing a polyurethane resin A component at the temperature of 20-25 ℃, a polyurethane resin B1 component at the temperature of 20-25 ℃ and a polyurethane resin B2 component at the temperature of 20-25 ℃ in a casting machine, injecting into a 25-35 ℃ box bubble for reaction for 10-15 min for molding, demolding, slicing and hot-pressing to obtain the polyurethane insole.
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 polyurethane resin for insoles comprises a resin A component, a B1 component and a B2 component, and polyurethane insoles which have different hardness requirements, excellent air permeability, high physical property and water washing resistance can be prepared by adjusting the mass ratio of the B1 component to the B2 component. Compared with the common two-component polyurethane resin, the product of the invention does not need to prepare various different raw materials by manufacturers in the process of producing insoles, and only needs to adjust the proportion of the components B1 and B2 when producing insoles with different requirements, thereby saving the production cost, reducing the resource waste and improving the production efficiency, and the polyurethane resin chain segments formed by mixing and reacting two prepolymer components (B1 and B2) with different proportions and the component A are more regular and ordered, and the prepared polyurethane shoe substrate has better performance. The polyurethane insole produced by the method has wide adjustable range of hardness, fine and uniform foam holes, good air permeability, 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
58.8kg of a polyoxyethylene-oxypropylene triol (number average molecular weight: 6000), 65.9kg of a polyoxypropylene triol (number average molecular weight: 1000), 152.4kg of a styrene graft copolymerization oxyethylene-oxypropylene triol (number average molecular weight: 6000), 1.39kg of ethylene glycol, 0.22kg of an ethylene glycol solution of triethylene diamine, 0.89kg of a solution prepared from 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, 2.77kg of water and 0.28kg of a silicone foam stabilizer, reacting at 50 ℃ for 2.5 hours, cooling to 45 ℃, and mixing for 1.0 hour to obtain a polyurethane resin component A.
60.0kg of diphenylmethane diisocyanate, 20.0kg of carbodiimide-modified diphenylmethane diisocyanate, 1.0kg of polyoxyethylene-oxypropylene triol (number average molecular weight: 6000) and 0.002kg of phosphoric acid were reacted at 75 ℃ for 2 hours to obtain a polyurethane resin B1 component.
6.0kg of diphenylmethane diisocyanate, 3.0kg of polyoxyethylene-oxypropylene diol (number average molecular weight of 3000) and 0.0002kg 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 25 ℃, the polyurethane resin B1 component with the temperature of 25 ℃ and the polyurethane resin B2 component with the temperature of 25 ℃ in a casting machine, injecting into a 35 ℃ box bubble for reaction for 10min for molding, demolding, slicing and hot-pressing to obtain the polyurethane insole.
Example 2
58.8kg of a polyoxyethylene-oxypropylene triol (number average molecular weight: 6000), 65.9kg of a polyoxypropylene triol (number average molecular weight: 1000), 152.4kg of a styrene graft copolymerization oxyethylene-oxypropylene triol (number average molecular weight: 6000), 1.39kg of ethylene glycol, 0.22kg of an ethylene glycol solution of triethylene diamine, 0.89kg of a solution prepared from 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, 2.77kg of water and 0.28kg of a silicone foam stabilizer, reacting at 50 ℃ for 2.5 hours, cooling to 45 ℃, and mixing for 1.0 hour to obtain a polyurethane resin component A.
9.19kg of diphenylmethane diisocyanate, 3.06kg of carbodiimide-modified diphenylmethane diisocyanate, 0.15kg of polyoxyethylene-oxypropylene triol (number average molecular weight: 6000) and 0.00032kg of phosphoric acid were reacted at 75 ℃ for 2 hours to obtain a polyurethane resin B1 component.
74.4kg of diphenylmethane diisocyanate, 37.2kg of polyoxyethylene-oxypropylene diol (number average molecular weight of 3000) 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 25 ℃, the polyurethane resin B1 component with the temperature of 25 ℃ and the polyurethane resin B2 component with the temperature of 25 ℃ in a casting machine, injecting into a 35 ℃ box bubble for reaction for 10min for molding, demolding, slicing and hot-pressing to obtain the polyurethane insole.
Example 3
48.08kg of polyoxyethylene-propylene oxide triol (with the number average molecular weight of 10000), 120.19kg of polyoxypropylene triol (with the number average molecular weight of 5000), 33.66kg of acrylonitrile graft copolymerization ethylene oxide-propylene oxide triol (with the number average molecular weight of 10000), 2.02kg of ethylene glycol, 1.01kg of ethylene glycol solution of triethylene diamine, 1.01kg of solution prepared from 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, 3.03kg of water and 4.04kg of organic silicon 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 polyurethane resin A component.
50.8g of diphenylmethane diisocyanate, 12.7kg of carbodiimide-modified diphenylmethane diisocyanate, 12.7kg of polyoxyethylene-oxypropylene triol (number average molecular weight: 10000) and 0.002kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a polyurethane resin B1 component.
4.56kg of diphenylmethane diisocyanate, 3.92kg of polyoxyethylene-oxypropylene diol (7000 in number average molecular weight) and 0.0002kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a polyurethane resin B2 component.
And mixing the polyurethane resin A component with the temperature of 20 ℃, the polyurethane resin B1 component with the temperature of 20 ℃ and the polyurethane resin B2 component with the temperature of 20 ℃ in a casting machine, injecting into a 25 ℃ box bubble for reaction for 15min for molding, demolding, slicing and hot-pressing to obtain the polyurethane insole.
Example 4
48.08kg of polyoxyethylene-propylene oxide triol (with the number average molecular weight of 10000), 120.19kg of polyoxypropylene triol (with the number average molecular weight of 5000), 33.66kg of acrylonitrile graft copolymerization ethylene oxide-propylene oxide triol (with the number average molecular weight of 10000), 2.02kg of ethylene glycol, 1.01kg of ethylene glycol solution of triethylene diamine, 1.01kg of solution prepared from 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, 3.03kg of water and 4.04kg of organic silicon 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 polyurethane resin A component.
8.0kg of diphenylmethane diisocyanate, 2.0kg of carbodiimide-modified diphenylmethane diisocyanate, 2.0kg of polyoxyethylene-oxypropylene triol (number average molecular weight: 10000) and 0.002kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a polyurethane resin B1 component.
58.0kg of diphenylmethane diisocyanate, 50.0kg of polyoxyethylene-oxypropylene diol (7000, number average molecular weight) and 0.010kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a polyurethane resin B2 component.
And mixing the polyurethane resin A component with the temperature of 20 ℃, the polyurethane resin B1 component with the temperature of 20 ℃ and the polyurethane resin B2 component with the temperature of 20 ℃ in a casting machine, injecting into a 25 ℃ box bubble for reaction for 15min for molding, demolding, slicing and hot-pressing to obtain the polyurethane insole.
Example 5
217.6kg of a polyoxyethylene-oxypropylene triol (9000 in number average molecular weight), 87.0kg of a polyoxypropylene triol (3000 in number average molecular weight), 130.6kg of a styrene graft copolymerization oxyethylene-oxypropylene triol (9000 in number average molecular weight), 6.53kg of ethylene glycol, 1.31kg of an ethylene glycol solution of triethylene diamine, 2.61kg of a solution prepared from 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, 5.66kg of water and 4.35kg of a silicone foam stabilizer were reacted at 60 ℃ for 1.5 hours, cooled to 45 ℃ and mixed for 1.0 hour to obtain a polyurethane resin component A.
88.0kg of diphenylmethane diisocyanate, 12.0kg of polyoxyethylene-oxypropylene triol (9000 in number average molecular weight) and 0.008kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a polyurethane resin B1 component.
30.0kg of diphenylmethane diisocyanate, 25.0kg of carbodiimide-modified diphenylmethane diisocyanate, 45.0kg of polyoxyethylene-oxypropylene diol (number average molecular weight of 3000) and 0.008kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain a polyurethane resin B2 component.
And mixing the polyurethane resin A component with the temperature of 25 ℃, the polyurethane resin B1 component with the temperature of 25 ℃ and the polyurethane resin B2 component with the temperature of 25 ℃ in a casting machine, injecting into a 35 ℃ box bubble for reaction for 10min for molding, demolding, slicing and hot-pressing to obtain the polyurethane insole.
Example 6
180.0kg of polyoxyethylene-propylene oxide triol (number average molecular weight 8000), 90.0kg of polyoxypropylene triol (number average molecular weight 3000), 90.0kg of styrene graft copolymerization ethylene oxide-propylene oxide triol (number average molecular weight 8000), 2.88kg of ethylene glycol, 1.08kg of ethylene glycol solution of triethylene diamine, 2.16kg of solution prepared from 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, 4.32kg of water and 4.68kg of silicone foam stabilizer, cooling to 40 ℃ after reacting for 2.5h at 50 ℃, and mixing for 1.5h to obtain the polyurethane resin A component.
85.0kg of diphenylmethane diisocyanate, 5.0kg of polyoxyethylene-oxypropylene triol (number average molecular weight 8000) and 0.005kg of phosphoric acid were reacted at 75 ℃ for 2 hours to obtain a polyurethane resin B1 component.
10.0kg of diphenylmethane diisocyanate, 7.0kg of carbodiimide-modified diphenylmethane diisocyanate, 13.0kg of polyoxyethylene-oxypropylene diol (number average molecular weight 4000) and 0.002kg 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 25 ℃, the polyurethane resin B1 component with the temperature of 25 ℃ and the polyurethane resin B2 component with the temperature of 25 ℃ in a casting machine, injecting into a 35 ℃ box bubble for reaction for 10min for molding, demolding, slicing and hot-pressing to obtain the polyurethane insole.
Comparative example 1
58.8kg of a polyoxyethylene-oxypropylene triol (number average molecular weight: 6000), 65.9kg of a polyoxypropylene triol (number average molecular weight: 1000), 152.4kg of a styrene graft copolymerization oxyethylene-oxypropylene triol (number average molecular weight: 6000), 1.39kg of ethylene glycol, 0.22kg of an ethylene glycol solution of triethylene diamine, 0.89kg of a solution prepared from 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, 2.77kg of water and 0.28kg of a silicone foam stabilizer, reacting at 50 ℃ for 2.5 hours, cooling to 45 ℃, and mixing for 1.0 hour to obtain a polyurethane resin component A.
66.0kg of diphenylmethane diisocyanate, 20.0kg of carbodiimide-modified diphenylmethane diisocyanate, 1.0kg of polyoxyethylene-oxypropylene triol (number average molecular weight of 6000), 3.0kg of polyoxyethylene-oxypropylene diol (number average molecular weight of 3000) and 0.004kg of phosphoric acid were reacted at 75 ℃ for 2 hours to obtain component B of polyurethane resin.
Mixing the polyurethane resin A component with the temperature of 25 ℃ and the polyurethane resin B component with the temperature of 25 ℃ in a casting machine, injecting into a 35 ℃ box bubble for reaction for 10min for molding, demolding, slicing and hot-pressing to obtain the polyurethane insole.
Comparative example 2
48.08kg of polyoxyethylene-propylene oxide triol (with the number average molecular weight of 10000), 120.19kg of polyoxypropylene triol (with the number average molecular weight of 5000), 33.66kg of acrylonitrile graft copolymerization ethylene oxide-propylene oxide triol (with the number average molecular weight of 10000), 2.02kg of ethylene glycol, 1.01kg of ethylene glycol solution of triethylene diamine, 1.01kg of solution prepared from 70 wt% of bis (dimethylaminoethyl) ether and 30 wt% of dipropylene glycol, 3.03kg of water and 4.04kg of organic silicon 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 polyurethane resin A component.
66.0kg of diphenylmethane diisocyanate, 2.0kg of carbodiimide-modified diphenylmethane diisocyanate, 2.0kg of polyoxyethylene-oxypropylene triol (number average molecular weight: 10000), 50.0kg of polyoxyethylene-oxypropylene diol (number average molecular weight: 7000) and 0.012kg of phosphoric acid were reacted at 65 ℃ for 3 hours to obtain polyurethane resin component B.
And mixing the polyurethane resin A component with the temperature of 20 ℃ and the polyurethane resin B component with the temperature of 20 ℃ in a casting machine, injecting into a 25 ℃ box bubble for reaction for 15min for forming, demolding, slicing and hot-pressing to obtain the polyurethane insole.
The polyurethane insoles prepared in examples 1 to 4 and comparative examples 1 to 2 were tested for each property as follows:
TABLE I
From the examples 1 and 2, and 3 and 4, it can be seen that the polyurethane insole with different hardness, excellent air permeability and fine and uniform foam holes can be prepared by simply adjusting the proportion of the component B1 to the component B2 on the premise that the component A of the polyurethane resin is not changed, so that the production efficiency is improved, and meanwhile, the energy consumption and the production cost are saved. As is clear from comparison of example 1 with comparative example 1 and example 4 with comparative example 2, the polyurethane resin for footwear of the present invention can more easily produce footwear having high hardness and good air permeability, or footwear having low hardness and good air permeability.
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 (8)
1. The polyurethane resin for the breathable insole is 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 resin B1 component comprises the following components in parts by weight:
180-100 parts of isocyanate B;
11-30 parts of 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 polymeric polyol B1 is polyether triol;
the isocyanate B2 is one or more of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate or naphthalene diisocyanate;
the polymeric polyol B2 is polyether diol;
the resin A component consists of the following components:
the polymeric polyol A is a mixture of polyether polyol and polymer polyol, and the mass ratio of the polyether polyol to the polymer polyol is 9: 11-5: 1;
the polyether polyol is a mixture of polyoxyethylene-propylene oxide triol with the number average molecular weight of 6000-10000 and polyoxypropylene triol with the number average molecular weight of 1000-5000, and the mass ratio of the polyoxyethylene-propylene oxide triol with the number average molecular weight of 6000-10000 to the polyoxypropylene triol with the number average molecular weight of 1000-5000 is 2: 5-5: 2;
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 40-50%.
2. The polyurethane resin for breathable insole according to claim 1, wherein said resin A component is composed of:
the resin A component consists of the following components in parts by weight:
3. the polyurethane resin for the breathable insole according to claim 1, wherein the resin B1 comprises the following components in parts by weight:
180-100 parts of isocyanate B;
11-20 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 polyol B1 is polyoxyethylene-oxypropylene triol 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 polymeric polyol B2 is polyoxyethylene-oxypropylene diol with the number average molecular weight of 3000-7000, and the side reaction inhibitor is phosphoric acid.
4. The polyurethane resin for breathable insole according to claim 3, wherein the crosslinking agent is one or more of ethylene glycol, 1, 4-butanediol, 1, 3-propanediol, 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.
5. The polyurethane resin for breathable insoles of any one of claims 1 to 4, wherein the mass ratio of the polyurethane resin B1 component to the polyurethane resin B2 component is 1:9 to 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.
6. The method for preparing the polyurethane resin for the breathable insole according to any one of claims 1 to 5, comprising the steps of:
(1) the component A of the polyurethane resin is obtained by 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.
(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.
7. Use of the polyurethane resin for air-permeable shoe insoles according to any one of claims 1 to 5, for preparing polyurethane insoles.
8. Use according to claim 7, characterized in that the method of application comprises the steps of: mixing a polyurethane resin A component at the temperature of 20-25 ℃, a polyurethane resin B1 component at the temperature of 20-25 ℃ and a polyurethane resin B2 component at the temperature of 20-25 ℃ in a casting machine, injecting into a 25-35 ℃ box bubble for reaction for 10-15 min for molding, demolding, slicing and hot pressing to obtain the polyurethane insole.
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| CN108059704A (en) * | 2017-12-18 | 2018-05-22 | 苏州浩洋聚氨酯科技有限公司 | A kind of low density high hardness polyurethane synthetic material |
| CN108530595A (en) * | 2018-04-11 | 2018-09-14 | 东莞市秦粤丰鞋材有限公司 | PU footwear materials and its manufacturing method and application |
| CN109096464B (en) * | 2018-07-05 | 2020-12-18 | 山东一诺威聚氨酯股份有限公司 | Breathable insole and preparation method thereof |
| CN111138624A (en) * | 2019-12-16 | 2020-05-12 | 旭川化学（苏州）有限公司 | Polyurethane resin for high-physical-property breathable insole and preparation method thereof |
| CN111731700A (en) * | 2020-07-01 | 2020-10-02 | 浙江华峰新材料有限公司 | Heat-preservation transfer method for polyurethane stock solution |
| CN113105609A (en) * | 2020-07-01 | 2021-07-13 | 广州冠欣新材料科技有限公司 | Polyurethane cotton material containing traditional Chinese medicine powder and insole |
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