CN106810668A - Polyurethane shoe-sole resin and preparation method and application - Google Patents
Polyurethane shoe-sole resin and preparation method and application Download PDFInfo
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- CN106810668A CN106810668A CN201611272201.2A CN201611272201A CN106810668A CN 106810668 A CN106810668 A CN 106810668A CN 201611272201 A CN201611272201 A CN 201611272201A CN 106810668 A CN106810668 A CN 106810668A
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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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- 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
- C08G18/40—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
- C08G18/4833—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
- C08G18/28—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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- 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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- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of polyurethane shoe-sole resin and preparation method and application, the resin includes Resin A component, the component of resin B 1 and the component of resin B 2, and Resin A component includes polyvalent alcohol A, crosslinking agent, catalyst, foaming agent and foam stabilizer；Resin B 1 includes 100 parts of isocyanates B1, 10~40 parts of polyvalent alcohol B1, 0.002~0.010 part of side reaction inhibitor, resin B 2 includes 100 parts of isocyanates B2, 50~100 parts of polyvalent alcohol B2, 0.002~0.010 part of side reaction inhibitor, isocyanates B1 is methyl diphenylene diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene di-isocyanate(TDI) or naphthalene diisocyanate, polyvalent alcohol B1 is polyether Glycols, isocyanates B2 is methyl diphenylene diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene di-isocyanate(TDI) or naphthalene diisocyanate, polyvalent alcohol B2 is polyether Glycols.The present invention can be obtained the polyurethane shoe-sole of different hardness excellent performance, low cost.
Description
Technical field
The present invention relates to a kind of polyurethane shoe-sole resin and preparation method and application.
Background technology
The full name polyurethanes of polyurethane, is to contain the macromolecular compound for repeating carbamate groups on main chain
It is referred to as, is the macromolecular compound as obtained from binary or polynary organic isocyanate interact with polyol compound.It is poly-
The features such as urethane sole has light weight, resilience good.
Resin generally double-component subpackage type raw material --- polyol blends and pre-polymerization for producing polyurethane shoe-sole
Thing (abbreviation AB material/AB components or black and white material).
The polyurethane shoe-sole of different performance requirement needs different types of AB material to use cooperatively.Produced for polyurethane shoe-sole
Enterprise is, it is necessary to be equipped with the raw material of various different model different sizes to adapt to the production of the sole of different performance requirement, and often
Secondary replacing raw material needs cleaning to draw a design board and material tank body, and production cost is high.
The content of the invention
It is an object of the invention to provide a kind of polyurethane shoe-sole resin and preparation method and application, to overcome existing skill
The defect that art is present.
Polyurethane shoe-sole resin of the present invention, comprising Resin A component, the component of resin B 1 and the component of resin B 2；
The Resin A component is made up of the component of following parts by weight：
The component of the resin B 1 is made up of the component of following parts by weight：
100 parts of isocyanates B1；
10~40 parts of polyvalent alcohol B1；
0.002~0.010 part of side reaction inhibitor；
The component of the resin B 2 is made up of the component of following parts by weight：
100 parts of isocyanates B2；
50~100 parts of polyvalent alcohol B2；
0.002~0.010 part of side reaction inhibitor.
Preferably：
The Resin A component is made up of the component of following parts by weight：
Preferably
The component of the resin B 1 is made up of the component of following parts by weight：
100 parts of isocyanates B1；
1 12~20 parts of polyvalent alcohol B；
0.002~0.010 part of side reaction inhibitor；
Preferably
The component of the resin B 2 is made up of the component of following parts by weight：
100 parts of isocyanates B2；
50~90 parts of polyvalent alcohol B2；
0.002~0.010 part of side reaction inhibitor.
Polyvalent alcohol is the mixture of PPG and polymer polyatomic alcohol in the Resin A component, and the polyethers is more
The mass ratio of first alcohol and polymer polyatomic alcohol is 1: 1~4: 1.
The PPG is the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols of number-average molecular weight 6000~10000；
The polymer polyatomic alcohol is styrene or acrylonitrile graft copolymer the oxidation second of number-average molecular weight 6000~10000
Alkene-propylene oxide trihydroxylic alcohol, solid content is 25~35%.
The crosslinking agent is ethylene glycol, BDO, 1,3-PD, one kind or one kind in 1,6- butanediol with
On.
The catalyst for the ethylene glycol solution of triethylene diamine and double (dimethylaminoethyl) ethers of 70wt% with
The mixture of the solution that 30wt% dipropylene glycols are made into, the ethylene glycol solution of the triethylene diamine and 70wt%'s is double
The mass ratio of the mixture of the solution that (dimethylaminoethyl) ether is made into 30wt% dipropylene glycols is 1: 4~1: 1.
The foaming agent is water；
The foam stabilizer is organosilicon foam stabilizer；
Isocyanates B1 is methyl diphenylene diisocyanate, Carbodiimide-Modified diphenyl in the component of the resin B 1
One or more in methane diisocyanate, toluene di-isocyanate(TDI) or naphthalene diisocyanate；
Polyvalent alcohol B1 is polyether Glycols in the component of the resin B 1, preferred number average molecular weight 6000~10000 it is poly-
Ethylene oxide-propylene oxide dihydroxylic alcohols；
Side reaction inhibitor is phosphoric acid in the component of the resin B 1；
Isocyanates B2 is methyl diphenylene diisocyanate, Carbodiimide-Modified diphenyl in the component of the resin B 2
One or more in methane diisocyanate, toluene di-isocyanate(TDI) or naphthalene diisocyanate；
Polyvalent alcohol B2 is polyether Glycols, the polyoxy of preferred number average molecular weight 3000~7000 in the component of the resin B 2
Change ethylene oxide-propylene oxide dihydroxylic alcohols；
Side reaction inhibitor is phosphoric acid in the component of the resin B 2.
The preparation method of described polyurethane shoe-sole resin, comprises the following steps：
(1) polyvalent alcohol, crosslinking agent, catalyst, foaming agent and foam stabilizer are reacted into 1.5~2.5h at 50~60 DEG C
Afterwards, 40~45 DEG C are cooled to, mix 1.0~1.5h, obtain described polyurethane resin component A；
(2) isocyanates B1, polyvalent alcohol B1 and side reaction inhibitor are reacted into 2~3h at 65~75 DEG C, obtains final product poly- ammonia
The component of ester resin B 1；
(3) isocyanates B2, polyvalent alcohol B2 and side reaction inhibitor are reacted into 2~3h at 65~75 DEG C, obtains final product poly- ammonia
The component of ester resin B 2.
The polyurethane shoe-sole resin, for preparing high-rebound polyurethane sole, preparation method comprises the following steps：
By polyurethane resin component A that temperature is 40~45 DEG C, the polyurethane resin B1 components that temperature is 40~45 DEG C and
Temperature is 40~45 DEG C of polyurethane resin B2 components, after mixing in the casting machine, reaction 3 in 45~55 DEG C of moulds of injection~
5min is molded, the demoulding, after curing 22~24h in 60~75 DEG C of baking ovens, obtains final product described polyurethane shoe-sole.
The mass ratio of polyurethane resin B1 components and polyurethane resin B2 components is 1: 9~9: 1；
Component A reactive hydrogen molal quantity is 1: 1 with the ratio between B1 components and the total isocyanate groups molal quantity of B2 components.
Present invention has the advantages that：
Polyurethane shoe-sole of the present invention includes Resin A component, B1 components and B2 components with resin, by adjusting B1 components and B2
The mass ratio of component, can be obtained the polyurethane shoe-sole of different hardness different performance.Compared to common dual-component polyurethane resin,
Product of the present invention manufacturer during polyurethane shoe-sole is produced need not configure various different materials, and production is different to require sole
When, it is only necessary to adjust the proportioning of B1 and B2 components, save polyurethane shoe-sole production cost, reduce the wasting of resources, improve production efficiency,
And the polyurethane resin segment that the two kinds of performed polymer components (B1 and B2) using different proportion are formed with component A hybrid reaction is more
Plus it is regular orderly, obtained polyurethane shoe-sole physical property is more preferably.Using the adjustable model of polyurethane shoe-sole hardness of production of the present invention
Width is enclosed, shrinkage factor is low, physical property is good, is more suitable for continuous production operation, and low cost, production efficiency is high.
Specific embodiment
The present invention is specifically described below by embodiment, is served only for being further described the present invention, no
It is understood that to be limiting the scope of the present invention.The implementation condition used in embodiment can according to the condition of specific producer and
It is required that doing some nonessential modifications and adaptations.
Embodiment 1
The polyethylene glycol oxide of 221.7kg-propylene oxide dihydroxylic alcohols (number-average molecular weight is 6000), the styrene of 55.4kg connects
Branch copolymerization ethylene oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 6000), 13.9kg ethylene glycol, the triethylene two of 0.22kg
The ethylene glycol solution of amine, double (dimethylaminoethyl) ethers of the 70wt% of 0.89kg are molten with what 30wt% dipropylene glycols were made into
After liquid, 2.77kg water and 0.28kg organosilicons foam stabilizer react 2.5h at 50 DEG C, 40 DEG C are cooled to, mix 1.5h, gathered
Urethane Resin A component.
By the methyl diphenylene diisocyanate of 78.4g, the isocyanide of Carbodiimide-Modified diphenyl methane two of 26.0kg
Acid esters, the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 6000) of 1.31kg and the phosphoric acid of 0.0026kg are 65
DEG C reaction 3h, obtain final product polyurethane resin B1 components.
By the methyl diphenylene diisocyanate of 7.64kg, (number is equal for the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols of 3.92kg
Molecular weight is that the phosphoric acid 3000) with 0.0003kg reacts 3h at 65 DEG C, obtains final product polyurethane resin B2 components.
It is 40 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 40 DEG C and temperature that temperature is 40 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 5min shapings, the demoulding, in 60 DEG C of baking ovens in 45 DEG C of moulds of injection
Middle curing 24h obtains final product polyurethane shoe-sole.
Embodiment 2
The polyethylene glycol oxide of 221.7kg-propylene oxide dihydroxylic alcohols (number-average molecular weight is 6000), the styrene of 55.4kg connects
Branch copolymerization ethylene oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 6000), 13.9kg ethylene glycol, the triethylene two of 0.22kg
The ethylene glycol solution of amine, double (dimethylaminoethyl) ethers of the 70wt% of 0.89kg are molten with what 30wt% dipropylene glycols were made into
After liquid, 2.77kg water and 0.28kg organosilicons foam stabilizer react 2.5h at 50 DEG C, 40 DEG C are cooled to, mix 1.5h, gathered
Urethane Resin A component.
By the methyl diphenylene diisocyanate of 12.0kg, the isocyanide of Carbodiimide-Modified diphenyl methane two of 4.00kg
Acid esters, the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 6000) of 0.19kg and the phosphoric acid of 0.0002kg are 65
DEG C reaction 3h, obtain final product polyurethane resin B1 components.
By the methyl diphenylene diisocyanate of 97.0kg, (number is equal for the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols of 48.6kg
Molecular weight is that the phosphoric acid 3000) with 0.003kg reacts 3h at 65 DEG C, obtains final product polyurethane resin B2 components.
It is 40 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 40 DEG C and temperature that temperature is 40 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 5min shapings, the demoulding, in 60 DEG C of baking ovens in 45 DEG C of moulds of injection
Middle curing 24h obtains final product polyurethane shoe-sole.
Embodiment 3
The polyethylene glycol oxide of 101.0kg-propylene oxide dihydroxylic alcohols (number-average molecular weight is 10000), the acrylonitrile of 101.0kg
Graft copolymerization ethylene oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 10000), 20.2kg ethylene glycol, three second of 1.01kg
The ethylene glycol solution of alkene diamines, double (dimethylaminoethyl) ethers of the 70wt% of 1.01kg are made into 30wt% dipropylene glycols
Solution, after 3.03kg water and 4.04kg organosilicons foam stabilizer react 1.5h at 60 DEG C, be cooled to 45 DEG C, mix 1.0h, obtain
To described polyurethane resin component A.
By the methyl diphenylene diisocyanate of 16.4kg, the isocyanide of Carbodiimide-Modified diphenyl methane two of 4.10kg
Acid esters, the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 10000) of 4.10kg and the phosphoric acid of 0.0025kg are 75
DEG C reaction 2h, obtain final product polyurethane resin B1 components.
By the methyl diphenylene diisocyanate of 118.6kg, polyethylene glycol oxide-propylene oxide dihydroxylic alcohols (number of 102.4kg
Average molecular weight is that the phosphoric acid 7000) with 0.022kg reacts 2h at 75 DEG C, obtains final product polyurethane resin B2 components.
It is 45 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 45 DEG C and temperature that temperature is 45 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 3min shapings, the demoulding, in 75 DEG C of baking ovens in 55 DEG C of moulds of injection
Middle curing 22h obtains final product polyurethane shoe-sole.
Embodiment 4
The polyethylene glycol oxide of 101.0kg-propylene oxide dihydroxylic alcohols (number-average molecular weight is 10000), the acrylonitrile of 101.0kg
Graft copolymerization ethylene oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 10000), 20.2kg ethylene glycol, three second of 1.01kg
The ethylene glycol solution of alkene diamines, double (dimethylaminoethyl) ethers of the 70wt% of 1.01kg are made into 30wt% dipropylene glycols
Solution, after 3.03kg water and 4.04kg organosilicons foam stabilizer react 1.5h at 60 DEG C, be cooled to 45 DEG C, mix 1.0h, obtain
To described polyurethane resin component A.
By the methyl diphenylene diisocyanate of 103.9g, the isocyanide of Carbodiimide-Modified diphenyl methane two of 25.9kg
Acid esters, the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 10000) of 25.9kg and the phosphoric acid of 0.016kg are 65
DEG C reaction 3h, obtain final product polyurethane resin B component.
By the methyl diphenylene diisocyanate of 9.34kg, (number is equal for the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols of 8.03kg
Molecular weight is that the phosphoric acid 7000) with 0.0018kg reacts 3h at 65 DEG C, obtains final product polyurethane resin B2 components.
It is 45 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 45 DEG C and temperature that temperature is 45 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 3min shapings, the demoulding, in 75 DEG C of baking ovens in 55 DEG C of moulds of injection
Middle curing 22h obtains final product polyurethane shoe-sole.
Embodiment 5
The polyethylene glycol oxide of 290.1kg-propylene oxide dihydroxylic alcohols (number-average molecular weight is 9000), the styrene of 145.1kg
Graft copolymerization ethylene oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 9000), the BDO of 34.8kg, 1.31kg's
The ethylene glycol solution of triethylene diamine, double (dimethylaminoethyl) ethers and the 30wt% dipropylene glycols of the 70wt% of 2.61kg
After the solution being made into, 5.66kg water and 4.35kg organosilicons foam stabilizer react 1.5h at 60 DEG C, 45 DEG C, mixing are cooled to
1.0h, obtains polyurethane resin component A.
By the methyl diphenylene diisocyanate of 126.7kg, polyethylene glycol oxide-propylene oxide dihydroxylic alcohols (number of 17.4kg
Average molecular weight is that the phosphoric acid 9000) with 0.012kg reacts 3h at 65 DEG C, obtains final product polyurethane resin B component.
By the methyl diphenylene diisocyanate of 43.2kg, the isocyanide of Carbodiimide-Modified diphenyl methane two of 36.0kg
Acid esters, the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 3000) of 65.2kg and the phosphoric acid of 0.012kg are at 65 DEG C
Reaction 3h, obtains final product polyurethane resin B2 components.
It is 45 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 45 DEG C and temperature that temperature is 45 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 3min shapings, the demoulding, in 75 DEG C of baking ovens in 55 DEG C of moulds of injection
Middle curing 22h obtains final product polyurethane shoe-sole.
Embodiment 6
The polyethylene glycol oxide of 200.0kg-propylene oxide dihydroxylic alcohols (number-average molecular weight is 8000), the styrene of 160.0kg
Graft copolymerization ethylene oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 8000), the BDO of 10.0kg, 9.20kg second
Glycol, the ethylene glycol solution of the triethylene diamine of 1.08kg, double (dimethylaminoethyl) ethers of the 70wt% of 2.16kg with
After the solution that 30wt% dipropylene glycols are made into, 4.32kg water and 4.68kg organosilicons foam stabilizer react 2.5h at 50 DEG C,
40 DEG C are cooled to, mix 1.5h, obtain polyurethane resin component A.
By the methyl diphenylene diisocyanate of 109.6kg, polyethylene glycol oxide-propylene oxide dihydroxylic alcohols (number of 6.38kg
Average molecular weight is that the phosphoric acid 8000) with 0.007kg reacts 2h at 75 DEG C, obtains final product polyurethane resin B1 components.
By the methyl diphenylene diisocyanate of 12.9kg, the isocyanide of Carbodiimide-Modified diphenyl methane two of 9.02kg
Acid esters, the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 4000) of 16.8kg and the phosphoric acid of 0.002kg are at 75 DEG C
Reaction 2h, obtains final product polyurethane resin B2 components.
It is 40 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 40 DEG C and temperature that temperature is 40 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, 5min shapings, the demoulding, in 60 DEG C of baking ovens in 45 DEG C of moulds of injection
Middle curing 24h obtains final product polyurethane shoe-sole.
Comparative example 1
The polyethylene glycol oxide of 221.7kg-propylene oxide dihydroxylic alcohols (number-average molecular weight is 6000), the styrene of 55.4kg connects
Branch copolymerization ethylene oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 6000), 13.9kg ethylene glycol, the triethylene two of 0.22kg
The ethylene glycol solution of amine, double (dimethylaminoethyl) ethers of the 70wt% of 0.89kg are molten with what 30wt% dipropylene glycols were made into
After liquid, 2.77kg water and 0.28kg organosilicons foam stabilizer react 2.5h at 50 DEG C, 40 DEG C are cooled to, mix 1.5h, gathered
Urethane Resin A component.
By the methyl diphenylene diisocyanate of 86.04g, the isocyanide of Carbodiimide-Modified diphenyl methane two of 26.0kg
Acid esters, the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 6000) of 1.31kg, the polyethylene glycol oxide of 3.92kg-
The phosphoric acid of propylene oxide dihydroxylic alcohols (number-average molecular weight is 3000) and 0.0029kg reacts 3h at 65 DEG C, obtains final product polyurethane resin B
Component.
By the polyurethane resin component A that temperature is 40 DEG C and the polyurethane resin B component that temperature is 40 DEG C, in casting machine
After mixing, 5min shapings in 45 DEG C of moulds of injection, the demoulding, curing 24h obtains final product polyurethane shoe-sole in 60 DEG C of baking ovens.
Comparative example 2
The polyethylene glycol oxide of 101.0kg-propylene oxide dihydroxylic alcohols (number-average molecular weight is 10000), the acrylonitrile of 101.0kg
Graft copolymerization ethylene oxide-propylene oxide trihydroxylic alcohol (number-average molecular weight is 10000), 20.2kg ethylene glycol, three second of 1.01kg
The ethylene glycol solution of alkene diamines, double (dimethylaminoethyl) ethers of the 70wt% of 1.01kg are made into 30wt% dipropylene glycols
Solution, after 3.03kg water and 4.04kg organosilicons foam stabilizer react 1.5h at 60 DEG C, be cooled to 45 DEG C, mix 1.0h, obtain
To described polyurethane resin component A.
By the methyl diphenylene diisocyanate of 135.0kg, the Carbodiimide-Modified diphenyl methane two of 4.10kg is different
Cyanate, the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 10000) of 4.10kg, the polyoxyethylene of 102.4kg
The phosphoric acid of alkene-propylene oxide dihydroxylic alcohols (number-average molecular weight is 7000) and 0.0245kg reacts 2h at 75 DEG C, obtains final product polyurethane tree
Fat B component.
By the polyurethane resin component A that temperature is 45 DEG C and the polyurethane resin B component that temperature is 45 DEG C, in casting machine
After mixing, 3min shapings in 55 DEG C of moulds of injection, the demoulding, curing 22h obtains final product polyurethane shoe-sole in 75 DEG C of baking ovens.
The properties test of the polyurethane shoe-sole obtained by embodiment 1~4 and comparative example 1~2 is as follows：
Table I
By embodiment 1 and embodiment 2, embodiment 3 and embodiment 4 understand, in the premise that polyurethane resin component A is constant
Under, the ratio of the simple adjustment component of resin B 1 and B2 components can be obtained the things such as different hardness, different tensile strength, tearing strength
Property different polyurethane shoe-sole, improve the production efficiency of polyurethane shoe-sole, while having saved energy resource consumption, save polyurethane shoe
The production cost at bottom.Comparative example 1 and comparative example 1, embodiment 3 and comparative example 2 are understood, are used using polyurethane shoe-sole of the present invention
Resin is more easy to be obtained that hardness high shrinkage is relatively low, or the hardness excellent performance relatively low compared with low-shrinkage sole.
Although above-described embodiment is described in detail to technical scheme, technical side of the invention
Case is not limited to above example, in the case of thought of the invention and objective is not departed from, to scope of the present invention patent
The equivalent change or modification that content is made, all should be technology category of the invention.
Claims (10)
1. polyurethane shoe-sole resin, it is characterised in that comprising Resin A component, the component of resin B 1 and the component of resin B 2；The tree
Fat component A is made up of following component：Polyvalent alcohol A, crosslinking agent, catalyst, foaming agent and foam stabilizer；
The component of the resin B 1 contains by the component of following parts by weight：
100 parts of isocyanates B1；
10~40 parts of polyvalent alcohol B1；
0.002~0.010 part of side reaction inhibitor；
The component of the resin B 2 is made up of the component of following parts by weight：
100 parts of isocyanates B2；
50~100 parts of polyvalent alcohol B2；
0.002~0.010 part of side reaction inhibitor；
Described isocyanates B1 is selected from methyl diphenylene diisocyanate, Carbodiimide-Modified diphenylmethane diisocyanate
One or more in ester, toluene di-isocyanate(TDI) or naphthalene diisocyanate；
The polyvalent alcohol B1 is polyether Glycols；
The isocyanates B2 be methyl diphenylene diisocyanate, carbodiimide modified diphenylmethane diisocyanate,
One or more in toluene di-isocyanate(TDI) or naphthalene diisocyanate；
The polyvalent alcohol B2 is polyether Glycols.
2. polyurethane shoe-sole resin according to claim 1, it is characterised in that the Resin A component is by following component
Composition：
3. polyurethane shoe-sole resin according to claim 2, it is characterised in that the Resin A component is by following component
Composition：
The Resin A component is made up of the component of following parts by weight：
4. polyurethane shoe-sole resin according to claim 1, it is characterised in that the component of the resin B 1 is by following weight
The component composition of number：
100 parts of isocyanates B1；
12~20 parts of polyvalent alcohol B1；
0.002~0.010 part of side reaction inhibitor；
The component of the resin B 2 is made up of the component of following parts by weight：
100 parts of isocyanates B2；
50~90 parts of polyvalent alcohol B2；
0.002~0.010 part of side reaction inhibitor；
Described isocyanates B1 is selected from methyl diphenylene diisocyanate, Carbodiimide-Modified diphenylmethane diisocyanate
One or more in ester, toluene di-isocyanate(TDI) or naphthalene diisocyanate；
The polyvalent alcohol B1 is the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols of number-average molecular weight 6000~10000；；
The isocyanates B2 be methyl diphenylene diisocyanate, carbodiimide modified diphenylmethane diisocyanate,
One or more in toluene di-isocyanate(TDI) or naphthalene diisocyanate；
The polyvalent alcohol B2 is the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols of number-average molecular weight 3000~7000；
The side reaction inhibitor is phosphoric acid.
5. polyurethane shoe-sole resin according to claim 2, it is characterised in that polyvalent alcohol A in the Resin A component
It is PPG and the mixture of polymer polyatomic alcohol；The mass ratio of the PPG and polymer polyatomic alcohol is 1: 1
~4: 1.
6. polyurethane shoe-sole resin according to claim 5, it is characterised in that the PPG is the equal molecules of number
Polyethylene glycol oxide-propylene oxide the dihydroxylic alcohols of amount 6000~10000；
The polymer polyatomic alcohol for number-average molecular weight 6000~10000 styrene or acrylonitrile graft copolymer ethylene oxide-
Propylene oxide trihydroxylic alcohol, solid content is 25~35%；
The crosslinking agent is ethylene glycol, BDO, 1,3-PD, one or more in 1,6- butanediol；
The catalyst is the ethylene glycol solution of triethylene diamine and double (dimethylaminoethyl) ethers of 70wt% and 30wt% mono-
The mixture of the solution that contracting DPG is made into, the ethylene glycol solution of the triethylene diamine and double (dimethylaminos of 70wt%
Ethyl) mass ratio of the mixture of solution that is made into of ether and 30wt% dipropylene glycols is 1: 4~1: 1；
The foaming agent is water；
The foam stabilizer is organosilicon foam stabilizer.
7. the polyurethane shoe-sole resin according to any one of claim 1~6, it is characterised in that the polyurethane resin
The mass ratio of B1 components and polyurethane resin B2 components is 1: 9~9: 1；Component A reactive hydrogen molal quantity and B1 components and B2 components
The ratio between total isocyanate groups molal quantity is 1: 1.
8. the preparation method of the polyurethane shoe-sole resin according to any one of claim 1~7, it is characterised in that including
Following steps：
(1) after polyvalent alcohol A, crosslinking agent, catalyst, foaming agent and foam stabilizer being reacted into 1.5~2.5h at 50~60 DEG C, drop
Temperature mixes 1.0~1.5h to 40~45 DEG C, obtains described polyurethane resin component A；
(2) isocyanates B1, polyvalent alcohol B1 and side reaction inhibitor are reacted into 2~3h at 65~75 DEG C, obtains final product polyurethane tree
Fat B1 components；
(3) isocyanates B2, polyvalent alcohol B2 and side reaction inhibitor are reacted into 2~3h at 65~75 DEG C, obtains final product polyurethane tree
Fat B2 components.
9. according to the application of the polyurethane shoe-sole resin described in any one of claim 1~7, it is characterised in that poly- for preparing
Urethane sole.
10. application according to claim 9, it is characterised in that application process, comprises the following steps：By temperature be 40~
45 DEG C of polyurethane resin component A, the polyurethane resin B1 components that temperature is 40~45 DEG C and the poly- ammonia that temperature is 40~45 DEG C
The component of ester resin B 2, after mixing in casting machine, reacts 3~5min shapings, the demoulding, 60~75 in 45~55 DEG C of moulds of injection
After curing 22~24h in DEG C baking oven, described polyurethane shoe-sole is obtained final product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1078725A (en) * | 1992-04-16 | 1993-11-24 | 帝国化学工业公司 | The method for preparing flexible polyurethane foam |
| CN1083076A (en) * | 1992-07-20 | 1994-03-02 | 中国科学院化学研究所 | Multi-block polymer material with thermo-recoverable shape |
| CN1219942A (en) * | 1996-05-23 | 1999-06-16 | 阿科化学技术公司 | Microcellular elastomers with improved processability and properties |
| CN1242384A (en) * | 1992-04-16 | 2000-01-26 | 帝国化学工业公司 | Polyisocyanate composition |
| JP2001278942A (en) * | 2000-03-30 | 2001-10-10 | Kurabo Ind Ltd | Polyurethane foam |
| US6548564B1 (en) * | 2001-12-13 | 2003-04-15 | Bayer Corporation | Polyether polyols with increased functionality |
| CN1428359A (en) * | 2001-12-27 | 2003-07-09 | 中国科学院山西煤炭化学研究所 | Preparation method of polyether polyarethane microporous elastic body |
| CN101148493A (en) * | 2007-10-31 | 2008-03-26 | 无锡双象化学工业有限公司 | Polyester type ultra-low density polyurethane resin for shoes |
| CN101486788A (en) * | 2008-12-30 | 2009-07-22 | 浙江华峰新材料股份有限公司 | Low density high hardness polyurethane micropore elastomer and preparation thereof |
| 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 |
| CN104341578A (en) * | 2014-10-27 | 2015-02-11 | 中国科学院长春应用化学研究所 | Preparation method of wide-temperature-range stable-modulus polyurethane microporous elastomer |
-
2016
- 2016-12-30 CN CN201611272201.2A patent/CN106810668B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1078725A (en) * | 1992-04-16 | 1993-11-24 | 帝国化学工业公司 | The method for preparing flexible polyurethane foam |
| CN1242384A (en) * | 1992-04-16 | 2000-01-26 | 帝国化学工业公司 | Polyisocyanate composition |
| CN1083076A (en) * | 1992-07-20 | 1994-03-02 | 中国科学院化学研究所 | Multi-block polymer material with thermo-recoverable shape |
| CN1219942A (en) * | 1996-05-23 | 1999-06-16 | 阿科化学技术公司 | Microcellular elastomers with improved processability and properties |
| JP2001278942A (en) * | 2000-03-30 | 2001-10-10 | Kurabo Ind Ltd | Polyurethane foam |
| US6548564B1 (en) * | 2001-12-13 | 2003-04-15 | Bayer Corporation | Polyether polyols with increased functionality |
| CN1428359A (en) * | 2001-12-27 | 2003-07-09 | 中国科学院山西煤炭化学研究所 | Preparation method of polyether polyarethane microporous elastic body |
| CN101148493A (en) * | 2007-10-31 | 2008-03-26 | 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 |
| CN101486788A (en) * | 2008-12-30 | 2009-07-22 | 浙江华峰新材料股份有限公司 | Low density high hardness polyurethane micropore elastomer and preparation thereof |
| CN104341578A (en) * | 2014-10-27 | 2015-02-11 | 中国科学院长春应用化学研究所 | Preparation method of wide-temperature-range stable-modulus polyurethane microporous elastomer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| CN106810668B (en) | 2021-05-04 |
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