CN106700029A - Resin for polyurethane sole as well as preparation method and application of resin - Google Patents
Resin for polyurethane sole as well as preparation method and application of resin Download PDFInfo
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- CN106700029A CN106700029A CN201611272193.1A CN201611272193A CN106700029A CN 106700029 A CN106700029 A CN 106700029A CN 201611272193 A CN201611272193 A CN 201611272193A CN 106700029 A CN106700029 A CN 106700029A
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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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The invention discloses a resin for a polyurethane sole as well as a preparation method and application of the resin. The resin comprises a resin component A, a resin component B1 and a resin component B2, wherein the resin component A comprises polyalcohol A, a cross-linking agent, a catalyst, a foaming agent and a foam stabilizer; the resin component B1 comprises 100 parts of isocyanate B1, 10-40 parts of polyalcohol B1 and 0.002-0.010 part of a side reaction arrester; the resin component B2 comprises 100 parts of isocyanate B2, 50-100 parts of polyalcohol B2 and 0.002-0.010 part of a side reaction arrester; isocyanate B1 refers to methylene diphenyl diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocynate or naphthalene diisocyanate; polyalcohol B1 refers to poly(polyol adipate); isocyanate B2 refers to methylene diphenyl diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocynate or naphthalene diisocyanate; and polyalcohol B2 refers to polyether polyol. According to the resin disclosed by the invention, the polyurethane soles of different water resisting properties can be prepared, and the cost is low.
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-
Urethane sole have light weight, elastic good, intensity high, oil resistant, it is wear-resisting, comfortable and easy to wear the features such as, by more and more consumers
Favor.Polyurethane shoe-sole can be divided into polyether-type sole and polyester type shoes bottom by the difference of its polyol starting material used, wherein poly-
Ether footwear sole flexibility is preferable, hydrolytic resistance is stronger, and physical and mechanical properties is poor；Polyester type shoes bottom physical and mechanical properties is more excellent,
Anti-hydrolytic performance is poor.In order to reach stronger physical and mechanical properties and hydrolytic resistance, generally simultaneously using PPG and
PEPA, i.e., in double-component sole resin raw material, be used in mixed way in polyol-mixture component or performed polymer component
PPG and PEPA.
The polyurethane shoe-sole of different performance requirement needs different types of polyol-mixture component and performed polymer component to match somebody with somebody
Conjunction is used.For polyurethane shoe-sole manufacturing enterprise, it is necessary to be equipped with the raw material of various different model different sizes to adapt to dissimilarity
The production of the sole that can be required, and changing raw material every time 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, to overcome prior art to exist
Defect.
Polyurethane shoe-sole resin of the present invention, comprising Resin A component, the component of resin B 1, 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；
12~20 parts of polyvalent alcohol B1；
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 A is the mixing of PPG, PEPA and polymer polyatomic alcohol in the Resin A component
Thing；The PPG and PEPA gross mass and the mass ratio of polymer polyatomic alcohol are 1: 1~4: 1；The polyethers
The mass ratio of polyalcohol and PEPA is 1: 9~9: 1；The PPG is number-average molecular weight 6000~10000
Polyethylene glycol oxide-propylene oxide dihydroxylic alcohols；The PEPA gathers for the polyadipate system of number-average molecular weight 1000~3000
One or more mixtures and adipic acid in ester dihydroxylic alcohols, preferably ethylene glycol, diethylene glycol, BDO are common by condensation
Poly- polyadipate system polyester diol；The polymer polyatomic alcohol is the styrene of number-average molecular weight 6000~10000
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 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；
In the component of the resin B 1 polyvalent alcohol B1 be polyadipate system PEPA, preferably ethylene glycol, diethylene glycol,
The polyadipate system polyester diol that one or more mixtures in BDO pass through condensation copolymerization with adipic acid,
Number-average molecular weight is 1000~3000；
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 PPG in the component of the resin B 2, preferred polyethylene glycol oxide-propylene oxide dihydroxylic alcohols,
Number-average molecular weight is 3000~7000；
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 A, 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 polyurethane shoe-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, you can the polyurethane shoe-sole of the different performance requirements such as different hardness difference hydrolytic resistance is obtained.Compared to it is general
Logical dual-component polyurethane resin, product of the present invention manufacturer during polyurethane shoe-sole is produced need not configure various differences
Raw material, produces different when requiring sole, it is only necessary to adjust the proportioning of B1 and B2 components, save production cost, reduce the wasting of resources, carry
High efficiency, and utilize two kinds of performed polymer components (B1 and B2) of different proportion and the poly- ammonia of component A hybrid reaction formation
Ester resin segment is more regular in order, and obtained polyurethane shoe-sole physical property is more excellent.Polyurethane shoe-sole using present invention production is hard
Degree adjustable extent is wide, and anti-hydrolytic performance and physical property intensity can be more suitable for continuous production operation, cost with production requirement quick shift
Low, 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
Polyadipate ethylene glycol diethylene glycol esterdiol (number-average molecular weight is 1000) of 80.0kg, the polyoxygenated of 80.0kg
Ethylene oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 6000), the styrene-grafted copolymerization ethylene oxide-propylene oxide of 40.0kg
Trihydroxylic alcohol (number-average molecular weight is 6000), the ethylene glycol of 4.00kg, the BDO of 6.00kg, the triethylene diamine of 0.50kg
Ethylene glycol solution, double (dimethylaminoethyl) ethers of the 70wt% of 1.50kg are molten with what 30wt% dipropylene glycols were made into
After liquid, 0.20kg water and 0.60kg 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 45.7g, the isocyanide of Carbodiimide-Modified diphenyl methane two of 15.2kg
Acid esters, polyadipate ethylene glycol diethylene glycol esterdiol (number-average molecular weight is 1000) and the phosphoric acid of 0.0012kg of 7.44kg exist
65 DEG C of reaction 3h, obtain final product polyurethane resin B1 components.
By the methyl diphenylene diisocyanate of 6.77kg, (number is equal for the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols of 1.35kg
Molecular weight is that the phosphoric acid 3000) with 0.00009kg 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
Polyadipate ethylene glycol diethylene glycol esterdiol (number-average molecular weight is 1000) of 80.0kg, the polyoxygenated of 80.0kg
Ethylene oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 6000), the styrene-grafted copolymerization ethylene oxide-propylene oxide of 40.0kg
Trihydroxylic alcohol (number-average molecular weight is 6000), the ethylene glycol of 4.00kg, the BDO of 6.00kg, the triethylene diamine of 0.50kg
Ethylene glycol solution, double (dimethylaminoethyl) ethers of the 70wt% of 1.50kg are molten with what 30wt% dipropylene glycols were made into
After liquid, 0.20kg water and 0.60kg 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 4.81kg, the isocyanide of Carbodiimide-Modified diphenyl methane two of 1.61kg
Acid esters, polyadipate ethylene glycol diethylene glycol esterdiol (number-average molecular weight is 1000) and the phosphoric acid of 0.00008kg of 1.28kg
3h is reacted at 65 DEG C, polyurethane resin B1 components are obtained final product.
By the methyl diphenylene diisocyanate of 57.7kg, (number is equal for the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols of 11.5kg
Molecular weight is that the phosphoric acid 3000) with 0.0012kg 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
Polyadipate ethylene glycol diethylene glycol esterdiol (number-average molecular weight is 2000) of 50kg, the polyoxyethylene of 50.0kg
Alkene-propylene oxide dihydroxylic alcohols (number-average molecular weight is 8000), the styrene-grafted copolymerization ethylene oxide-propylene oxide of 100.0kg
Trihydroxylic alcohol (number-average molecular weight is 8000), the ethylene glycol of 10.4kg, the BDO of 9.60kg, the triethylene diamine of 1.50kg
Ethylene glycol solution, double (dimethylaminoethyl) ethers of the 70wt% of 1.50kg are molten with what 30wt% dipropylene glycols were made into
After liquid, 1.00kg water and 1.40kg organosilicons foam stabilizer react 1.5h at 60 DEG C, 45 DEG C are cooled to, mix 1.0h, gathered
Urethane Resin A component.
By the methyl diphenylene diisocyanate of 17.0kg, the polyadipate ethylene glycol diethylene glycol esterdiol of 6.82kg
The phosphoric acid of (number-average molecular weight is 2000) and 0.0024kg reacts 2h at 75 DEG C, obtains final product polyurethane resin B1 components.
By the methyl diphenylene diisocyanate of 85.2kg, (number is equal for the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols of 34.1kg
Molecular weight is that the phosphoric acid 7000) with 0.012kg reacts 2h at 75 DEG C, obtains final product polyurethane resin B2 components.
It is 47 by polyurethane resin component A, the polyurethane resin B1 components that temperature is 47 DEG C and temperature that temperature is 52 DEG C
DEG C polyurethane resin B2 components, after mixing in the casting machine, injection mould 7min shapings, the demoulding is cured in 70 DEG C of baking ovens
22h obtains final product described polyurethane shoe-sole.
Embodiment 4
Polyadipate ethylene glycol diethylene glycol esterdiol (number-average molecular weight is 2000) of 50kg, the polyoxyethylene of 50.0kg
Alkene-propylene oxide dihydroxylic alcohols (number-average molecular weight is 8000), the styrene-grafted copolymerization ethylene oxide-propylene oxide of 100.0kg
Trihydroxylic alcohol (number-average molecular weight is 8000), the ethylene glycol of 10.4kg, the BDO of 9.60kg, the triethylene diamine of 1.50kg
Ethylene glycol solution, double (dimethylaminoethyl) ethers of the 70wt% of 1.50kg are molten with what 30wt% dipropylene glycols were made into
After liquid, 1.00kg water and 1.40kg organosilicons foam stabilizer react 1.5h at 60 DEG C, 45 DEG C are cooled to, mix 1.0h, gathered
Urethane Resin A component.
By the methyl diphenylene diisocyanate of 87.3g, the polyadipate ethylene glycol diethylene glycol esterdiol (number of 34.9kg
Average molecular weight is that the phosphoric acid 2000) with 0.012kg reacts 2h at 75 DEG C, obtains final product polyurethane resin B1 components.
By the methyl diphenylene diisocyanate of 17.5kg, (number is equal for the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols of 6.98kg
Molecular weight is that the phosphoric acid 7000) with 0.0024kg 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 5
Polyadipate ethylene glycol diethylene glycol esterdiol (number-average molecular weight is 3000) of 15.0kg, the polyoxy of 135.0kg
Change ethylene oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 10000), the styrene-grafted copolymerization ethylene oxide-oxidation of 50.0kg
Propylene trihydroxylic alcohol (number-average molecular weight is 10000), the ethylene glycol of 8.00kg, the BDO of 8.00kg, three second of 0.60kg
The ethylene glycol solution of alkene diamines, double (dimethylaminoethyl) ethers of the 70wt% of 1.80kg are made into 30wt% dipropylene glycols
Solution, after 2.00kg water and 2.00kg organosilicons foam stabilizer react 1.5h at 60 DEG C, be cooled to 45 DEG C, mix 1.0h, obtain
To polyurethane resin component A.
By the methyl diphenylene diisocyanate of 47.2kg, the polyadipate ethylene glycol diethylene glycol esterdiol of 14.2kg
The phosphoric acid of (number-average molecular weight is 3000) and 0.004kg reacts 3h at 65 DEG C, obtains final product polyurethane resin B1 components.
By the methyl diphenylene diisocyanate of 47.2kg, (number is equal for the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols of 14.2kg
Molecular weight is that the phosphoric acid 7000) with 0.004kg 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 6
Polyadipate ethylene glycol diethylene glycol esterdiol (number-average molecular weight is 2000) of 135.0kg, the polyoxy of 15.0kg
Change ethylene oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 8000), the styrene-grafted copolymerization ethylene oxide-oxidation third of 50.0kg
Alkene trihydroxylic alcohol (number-average molecular weight is 9000), the ethylene glycol of 4.00kg, the BDO of 8.00kg, the triethylene two of 1.20kg
The ethylene glycol solution of amine, double (dimethylaminoethyl) ethers of the 70wt% of 1.20kg are molten with what 30wt% dipropylene glycols were made into
After liquid, 1.20kg water and 1.40kg 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 40.5kg, the polyadipate ethylene glycol diethylene glycol esterdiol of 12.2kg
The phosphoric acid of (number-average molecular weight is 2000) and 0.003kg reacts 2h at 75 DEG C, obtains final product polyurethane resin B1 components.
By the methyl diphenylene diisocyanate of 32.4kg, the isocyanide of Carbodiimide-Modified diphenyl methane two of 8.10kg
Acid esters, the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 6000) of 16.2kg and the phosphoric acid of 0.003kg 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
Polyadipate ethylene glycol diethylene glycol esterdiol (number-average molecular weight is 1000) of 80.0kg, the polyoxygenated of 80.0kg
Ethylene oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 6000), the styrene-grafted copolymerization ethylene oxide-propylene oxide of 40.0kg
Trihydroxylic alcohol (number-average molecular weight is 6000), the ethylene glycol of 4.00kg, the BDO of 6.00kg, the triethylene diamine of 0.50kg
Ethylene glycol solution, double (dimethylaminoethyl) ethers of the 70wt% of 1.50kg are molten with what 30wt% dipropylene glycols were made into
After liquid, 0.20kg water and 0.60kg 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 52.47g, the isocyanide of Carbodiimide-Modified diphenyl methane two of 15.2kg
Acid esters, polyadipate ethylene glycol diethylene glycol esterdiol (number-average molecular weight is 1000) of 7.44kg, the polyoxyethylene of 1.35kg
The phosphoric acid of alkene-propylene oxide dihydroxylic alcohols (number-average molecular weight is 3000) and 0.00129kg reacts 3h at 65 DEG C, obtains final product polyurethane tree
Fat 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
Polyadipate ethylene glycol diethylene glycol esterdiol (number-average molecular weight is 2000) of 50kg, the polyoxyethylene of 50.0kg
Alkene-propylene oxide dihydroxylic alcohols (number-average molecular weight is 8000), the styrene-grafted copolymerization ethylene oxide-propylene oxide of 100.0kg
Trihydroxylic alcohol (number-average molecular weight is 8000), the ethylene glycol of 10.4kg, the BDO of 9.60kg, the triethylene diamine of 1.50kg
Ethylene glycol solution, double (dimethylaminoethyl) ethers of the 70wt% of 1.50kg are molten with what 30wt% dipropylene glycols were made into
After liquid, 1.00kg water and 1.40kg organosilicons foam stabilizer react 1.5h at 60 DEG C, 45 DEG C are cooled to, mix 1.0h, gathered
Urethane Resin A component.
By the methyl diphenylene diisocyanate of 102.2kg, the polyadipate ethylene glycol diethylene glycol esterdiol of 6.82kg
(number-average molecular weight is 2000), the polyethylene glycol oxide-propylene oxide dihydroxylic alcohols (number-average molecular weight is 7000) of 34.1kg and
The phosphoric acid of 0.0144kg reacts 2h at 75 DEG C, obtains final product polyurethane resin 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
Note：The conservation rate of tensile strength is represented after hydrolytic resistance is tested 2 weeks with jungle.
By embodiment 1 and embodiment 2, embodiment 3 and embodiment 4 understand, in the premise that polyurethane resin component A is constant
Under, different anti-hydrolytic performance requirements can be obtained for the ratio of the simple adjustment component of resin B 1 and B2 components or different mechanical performances will
The polyurethane shoe-sole asked, improves production efficiency, while energy saving is consumed, saves production cost.Comparative example 1 and contrast
Example 1, embodiment 3 and comparative example 2 understand, using polyurethane shoe-sole resin of the present invention under the conditions of identical raw material, are more easy to
It is obtained that anti-hydrolytic performance is more preferable or the more preferable sole of mechanical performance.
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 polyadipate system PEPA；
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 PPG.
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 of ester, toluene di-isocyanate(TDI) or naphthalene diisocyanate；
The polyvalent alcohol B1 is that one or more mixtures and adipic acid in ethylene glycol, diethylene glycol, BDO are logical
Cross condensation copolymerization and form polyadipate system polyester diol, number-average molecular weight is 1000~3000；
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 the mixture of PPG, PEPA and polymer polyatomic alcohol；The PPG and the total matter of PEPA
Amount is 1: 1~4: 1 with the mass ratio of polymer polyatomic alcohol, and the mass ratio of the PPG and PEPA is 1: 9~9
∶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 PEPA is the polyadipate system polyester diol of number-average molecular weight 1000~3000；
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, 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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| 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 |
| CN108485242A (en) * | 2018-03-16 | 2018-09-04 | 上海汇得科技股份有限公司 | A kind of high astringent sense wet polyurethane resin and preparation method |
| CN109438667A (en) * | 2018-11-06 | 2019-03-08 | 苏州环明电子科技有限公司 | It is coated with production polyurethane foamed composite material |
| CN109897365A (en) * | 2017-12-09 | 2019-06-18 | 王龙 | A kind of Low temperature-resistanpolyurethane polyurethane footwear material resin 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 |
| CN112608442A (en) * | 2020-12-09 | 2021-04-06 | 黎明化工研究设计院有限责任公司 | Polyurethane sole stock solution and preparation method and use method thereof |
| CN115894938A (en) * | 2021-09-30 | 2023-04-04 | 浙江华峰新材料有限公司 | Carbon hydroxyl organic silicon polyether copolymer, polyurethane resin and preparation method thereof |
| CN115926101A (en) * | 2023-02-14 | 2023-04-07 | 旭川化学（苏州）有限公司 | Low-temperature-resistant polyurethane sole resin and preparation method and application thereof |
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| CN109897365A (en) * | 2017-12-09 | 2019-06-18 | 王龙 | A kind of Low temperature-resistanpolyurethane polyurethane footwear material resin and preparation method thereof |
| 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 |
| CN108485242A (en) * | 2018-03-16 | 2018-09-04 | 上海汇得科技股份有限公司 | A kind of high astringent sense wet polyurethane resin and preparation method |
| CN108485242B (en) * | 2018-03-16 | 2020-12-04 | 上海汇得科技股份有限公司 | High-astringency wet-process polyurethane resin and preparation method thereof |
| CN109438667A (en) * | 2018-11-06 | 2019-03-08 | 苏州环明电子科技有限公司 | It is coated with production polyurethane foamed composite material |
| 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 |
| CN112608442A (en) * | 2020-12-09 | 2021-04-06 | 黎明化工研究设计院有限责任公司 | Polyurethane sole stock solution and preparation method and use method thereof |
| CN112608442B (en) * | 2020-12-09 | 2022-07-08 | 黎明化工研究设计院有限责任公司 | Polyurethane sole stock solution and preparation method and use method thereof |
| CN115894938A (en) * | 2021-09-30 | 2023-04-04 | 浙江华峰新材料有限公司 | Carbon hydroxyl organic silicon polyether copolymer, polyurethane resin and preparation method thereof |
| CN115894938B (en) * | 2021-09-30 | 2024-02-02 | 浙江华峰新材料有限公司 | Carbon hydroxyl organic silicon polyether copolymer, polyurethane resin and preparation method thereof |
| CN115926101A (en) * | 2023-02-14 | 2023-04-07 | 旭川化学（苏州）有限公司 | Low-temperature-resistant polyurethane sole resin and preparation method and application thereof |
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