CN111286072B - PU sole stock solution, preparation method thereof and preparation method of corresponding sole - Google Patents

PU sole stock solution, preparation method thereof and preparation method of corresponding sole Download PDF

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Publication number
CN111286072B
CN111286072B CN202010090434.0A CN202010090434A CN111286072B CN 111286072 B CN111286072 B CN 111286072B CN 202010090434 A CN202010090434 A CN 202010090434A CN 111286072 B CN111286072 B CN 111286072B
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component
sole
parts
stock solution
mold
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CN111286072A (en
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李滨男
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Wenzhou Yicheng Shoes Material Co ltd
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Wenzhou Yicheng Shoes Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/145—Halogen containing compounds containing carbon, halogen and hydrogen only only chlorine as halogen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D35/00—Producing footwear
    • B29D35/02—Producing footwear made in one piece using a moulding technique, e.g. by injection moulding or casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D35/00—Producing footwear
    • B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
    • B29D35/122—Soles
    • 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
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    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • 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
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/40—High-molecular-weight compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/6633—Compounds of group C08G18/42
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    • 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
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    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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    • 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
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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Abstract

The invention provides a PU sole stock solution, which comprises a component A, a component B and a component C, wherein: the component A comprises: 5-10 parts of adipic acid; 5-10 parts of ethylene glycol; 25-45 parts of MDI; and B component: 32-37 parts of microcrystalline cellulose; 12-25 parts of hydroxymethyl cellulose; 0.2-0.5 part of foaming agent; 0.1-0.3 part of foam stabilizer; 1-2 parts of pure water; and C, component C: 2-5 parts of ethylene glycol; 0.1-0.2 part of triethylene diamine. The invention adopts cellulose as the polyester-polyether polyol material, has the advantages of good hydrolytic stability, liquid at normal temperature, low viscosity, wide foaming range, convenient operation and the like, the prepared PU sole stock solution has excellent mechanical properties of high tearing strength, high tensile strength and high tensile rate, and the polyether type sole stock solution has the characteristics of low viscosity and hydrolysis resistance, thereby having good application value, and the prepared PU sole is integrally formed, has large adhesive force between the outer sole and the inner sole, is not easy to degum and has strong practicability.

Description

PU sole stock solution, preparation method thereof and preparation method of corresponding sole
Technical Field
The invention relates to the technical field of polymer synthesis, in particular to PU sole stock solution, a preparation method thereof and a corresponding sole preparation method.
Background
Polyurethane (PU) resin for shoe soles, also called as polyurethane shoe sole stock solution, is a raw material for preparing polyurethane shoe soles, the yield of the polyurethane shoe soles only accounts for about 5% of all polyurethane products, but the polyurethane shoe soles are excellent materials which have unique properties, are developed rapidly and are irreplaceable in cost.
At present, the polyester polyol and the polyether polyol are mainly used for PU soles. The polyester type sole has the characteristics of high strength, good wear resistance, good adhesion with the vamp and the like, and occupies more than 80 percent of the market share of the polyurethane sole material. However, the polyester type sole material also has its own drawbacks: poor hydrolysis resistance and poor temperature resistance, is solid or high-viscosity liquid at normal temperature, is inconvenient to operate and the like. The mechanical property of the polyether type sole material is poorer than that of polyester type, but the polyether type sole material is more and more rapidly developed in the polyurethane sole material due to the characteristics of good hydrolysis resistance and stability, liquid at normal temperature, low viscosity, wide foaming range, convenience in operation, good economy, easily available raw materials and the like.
Disclosure of Invention
The invention provides a PU sole stock solution, a preparation method thereof and a corresponding sole, and aims to provide the PU sole stock solution which has the advantages of good hydrolytic stability, liquid at normal temperature, low viscosity, convenience in operation, good economy, easiness in obtaining raw materials and the like.
The invention provides PU sole stock solution, which comprises a component A, a component B and a component C, wherein:
the component A comprises:
5-10 parts of adipic acid;
5-10 parts of ethylene glycol
25-45 parts of MDI;
and B component:
32-37 parts of microcrystalline cellulose;
12-25 parts of hydroxymethyl cellulose;
0.2-0.5 part of foaming agent;
0.1-0.3 part of foam stabilizer;
1-2 parts of water;
and C, component C:
2-5 parts of ethylene glycol;
0.1-0.2 part of triethylene diamine.
As a further improvement of the invention, the paint also comprises a component D: 5-10 parts of anti-yellowing agent and 2-5 parts of hardening agent.
As a further improvement of the invention, the foaming agent is selected from one of HCFC-141B or dichloromethane; the foam stabilizer is selected from one or a mixture of PU-1230, XHG-293, H420, DC190 and PU-1253.
As a further improvement of the invention, the anti-yellowing agent is selected from one or a mixture of more of an anti-yellowing agent L9322, an anti-yellowing agent UVK-CL, an anti-yellowing agent UVK-CL2 and an anti-yellowing agent L-1268; the hardener is 3,3 '-dichloro-4, 4' -diaminodiphenylmethane.
The invention further provides a preparation method of the PU sole stock solution, which comprises the following steps:
s1, mixing adipic acid and ethylene glycol in proportion, heating to 180 ℃ and 220 ℃ for reaction for 2-3h, evaporating by-product water, reducing the temperature to 75-85 ℃, adding MDI (diphenylmethane diisocyanate), and stirring for reaction for 1-2h to obtain a component A;
s2, uniformly mixing microcrystalline cellulose, hydroxymethyl cellulose, a foaming agent, a foam stabilizer and water in proportion to obtain a component B;
s3, adding triethylene diamine into ethylene glycol according to a proportion, and uniformly mixing to obtain a component C;
and S4, fully and uniformly mixing the component A, the component B and the component C, pouring the mixture into a test piece mold or a sole mold, carrying out curing reaction for 3-5min, opening the mold, and naturally curing at room temperature for 24h to obtain the PU sole stock solution.
The invention further provides a preparation method of the PU sole stock solution, which comprises the following steps:
s1, mixing adipic acid and ethylene glycol in proportion, heating to 180 ℃ and 220 ℃ for reaction for 2-3h, evaporating by-product water, reducing the temperature to 75-85 ℃, adding MDI (diphenylmethane diisocyanate), and stirring for reaction for 1-2h to obtain a component A;
s2, uniformly mixing microcrystalline cellulose, hydroxymethyl cellulose, a foaming agent, a foam stabilizer and water in proportion to obtain a component B;
s3, adding triethylene diamine into ethylene glycol according to a proportion, and uniformly mixing to obtain a component C;
s4, grinding the anti-yellowing agent and the hardening agent, and uniformly mixing to obtain a component D;
s5, fully and uniformly mixing the component A, the component B, the component C and the component D, then pouring the mixture into a test piece mold or a sole mold, carrying out curing reaction for 3-5min, opening the mold, and naturally curing at room temperature for 24h to obtain the PU sole stock solution.
The invention further provides a preparation method of the PU sole, which comprises the following steps:
s1, preparing a mixture by adopting color powder and the PU sole stock solution, spraying the mixture on a mold of a casting machine, and forming an outer sole;
s2, pouring a foamed PU material into the cavity of the mold, heating to obtain a molded inner sole, and integrally molding the whole sole.
The invention further provides a preparation method of the PU sole, which comprises the following steps:
s1, preparing a mixture by adopting color powder and the PU sole stock solution, spraying the mixture on a mold of a casting machine, and forming an outer sole;
s2, pouring a foamed PU material into the cavity of the mold, heating to obtain a molded inner sole, and integrally molding the whole sole.
As a further improvement of the invention, the preparation method of the mixture is that the color powder and the PU sole stock solution are heated by a heating open mill to 200 ℃ and are uniformly mixed; the mixture was sprayed at a rate of 100mL per minute; the heating temperature in step S2 is 180-220 ℃.
The invention further protects the PU sole prepared by the preparation method of the PU sole, and the outer sole and the inner sole are integrally formed.
The invention has the following beneficial effects: the prepared PU sole stock solution has the advantages of high tearing strength, high tensile rate, high mechanical property and low viscosity and hydrolysis resistance of polyether type sole stock solution, and has good application value;
the PU sole manufactured by the invention is integrally formed, the adhesive force of the outer sole and the inner sole is large, the PU sole is not easy to come unstuck, and the practicability is strong.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
EXAMPLE 1 preparation of PU shoe sole stock solution
The raw materials comprise the following components in parts by weight:
the component A comprises:
5 parts of adipic acid;
ethylene glycol 5 parts
25 parts of MDI;
and B component:
32 parts of microcrystalline cellulose;
12 parts of hydroxymethyl cellulose;
0.2 part of foaming agent; the foaming agent is dichloromethane;
0.1 part of foam stabilizer; the foam stabilizer is PU-1230;
1 part of pure water;
and C, component C:
ethylene glycol 2 parts
0.1 part of triethylene diamine.
The preparation method of the PU sole stock solution comprises the following steps:
s1, mixing adipic acid and ethylene glycol in proportion, heating to 180 ℃ for reaction for 2 hours, evaporating a byproduct of water, cooling to 75 ℃, adding MDI (diphenyl-methane-diisocyanate), and stirring for reaction for 1 hour to obtain a component A;
s2, uniformly mixing microcrystalline cellulose, hydroxymethyl cellulose, a foaming agent, a foam stabilizer and pure water in proportion to obtain a component B;
s3, adding triethylene diamine into ethylene glycol according to a proportion, and uniformly mixing to obtain a component C;
and S4, fully and uniformly mixing the component A, the component B and the component C, pouring the mixture into a test piece mold or a sole mold, carrying out curing reaction for 3min, opening the mold, and naturally curing at room temperature for 24h to obtain the PU sole stock solution.
EXAMPLE 2 preparation of PU shoe sole stock solution
The raw materials comprise the following components in parts by weight:
the component A comprises:
10 parts of adipic acid;
10 portions of ethylene glycol
45 parts of MDI;
and B component:
37 parts of microcrystalline cellulose;
18 parts of hydroxymethyl cellulose;
0.5 part of foaming agent; the foaming agent is dichloromethane;
0.3 part of foam stabilizer; the foam stabilizer is PU-1230;
2 parts of pure water;
and C, component C:
ethylene glycol 5 parts
0.2 part of triethylene diamine.
The preparation method of the PU sole stock solution comprises the following steps:
s1, mixing adipic acid and ethylene glycol in proportion, heating to 210 ℃ for reaction for 3 hours, evaporating a byproduct of water, cooling to 82 ℃, adding MDI (diphenyl-methane-diisocyanate), and stirring for reaction for 2 hours to obtain a component A;
s2, uniformly mixing microcrystalline cellulose, hydroxymethyl cellulose, a foaming agent, a foam stabilizer and pure water in proportion to obtain a component B;
s3, adding triethylene diamine into ethylene glycol according to a proportion, and uniformly mixing to obtain a component C;
and S4, fully and uniformly mixing the component A, the component B and the component C, pouring the mixture into a test piece mold or a sole mold, carrying out curing reaction for 4min, opening the mold, and naturally curing at room temperature for 24h to obtain the PU sole stock solution.
EXAMPLE 3 preparation of PU shoe sole stock solution
The raw materials comprise the following components in parts by weight:
the component A comprises:
5 parts of adipic acid;
ethylene glycol 5 parts
25 parts of MDI;
and B component:
32 parts of microcrystalline cellulose;
20 parts of hydroxymethyl cellulose;
0.2 part of foaming agent; the foaming agent is dichloromethane;
0.1 part of foam stabilizer; the foam stabilizer is PU-1230;
1 part of pure water;
and C, component C:
ethylene glycol 2 parts
0.1 part of triethylene diamine;
and (D) component:
5 parts of an anti-yellowing agent; the anti-yellowing agent is anti-yellowing agent L9322;
2 parts of a hardening agent; the hardener is 3,3 '-dichloro-4, 4' -diaminodiphenylmethane.
The preparation method of the PU sole stock solution comprises the following steps:
s1, mixing adipic acid and ethylene glycol in proportion, heating to 190 ℃ for reaction for 2 hours, evaporating a byproduct of water, cooling to 78 ℃, adding MDI (diphenyl-methane-diisocyanate), and stirring for reaction for 1 hour to obtain a component A;
s2, uniformly mixing microcrystalline cellulose, hydroxymethyl cellulose, a foaming agent, a foam stabilizer and pure water in proportion to obtain a component B;
s3, adding triethylene diamine into ethylene glycol according to a proportion, and uniformly mixing to obtain a component C;
s4, grinding the anti-yellowing agent and the hardening agent, and uniformly mixing to obtain a component D;
and S5, fully and uniformly mixing the component A, the component B, the component C and the component D, pouring the mixture into a test piece mold or a sole mold, carrying out curing reaction for 4min, opening the mold, and naturally curing at room temperature for 24h to obtain the PU sole stock solution.
EXAMPLE 4 preparation of PU shoe sole stock solution
The raw materials comprise the following components in parts by weight:
the component A comprises:
10 parts of adipic acid;
10 portions of ethylene glycol
45 parts of MDI;
and B component:
37 parts of microcrystalline cellulose;
18 parts of hydroxymethyl cellulose;
0.5 part of foaming agent; the foaming agent is dichloromethane;
0.3 part of foam stabilizer; the foam stabilizer is PU-1230;
2 parts of pure water;
and C, component C:
ethylene glycol 5 parts
0.2 part of triethylene diamine;
and (D) component:
10 parts of an anti-yellowing agent; the anti-yellowing agent is anti-yellowing agent L9322;
5 parts of a hardening agent; the hardener is 3,3 '-dichloro-4, 4' -diaminodiphenylmethane.
The preparation method of the PU sole stock solution comprises the following steps:
s1, mixing adipic acid and ethylene glycol in proportion, heating to 210 ℃ for reaction for 3 hours, evaporating a byproduct of water, cooling to 82 ℃, adding MDI (diphenyl-methane-diisocyanate), and stirring for reaction for 2 hours to obtain a component A;
s2, uniformly mixing microcrystalline cellulose, hydroxymethyl cellulose, a foaming agent, a foam stabilizer and pure water in proportion to obtain a component B;
s3, adding triethylene diamine into ethylene glycol according to a proportion, and uniformly mixing to obtain a component C;
s4, grinding the anti-yellowing agent and the hardening agent, and uniformly mixing to obtain a component D;
and S5, fully and uniformly mixing the component A, the component B, the component C and the component D, pouring the mixture into a test piece mold or a sole mold, carrying out curing reaction for 4min, opening the mold, and naturally curing at room temperature for 24h to obtain the PU sole stock solution.
Comparative example 1 preparation of PU shoe sole stock solution
Compared with the example 4, the microcrystalline cellulose is not added, and other raw materials and the preparation method are consistent.
The raw materials comprise the following components in parts by weight:
the component A comprises:
10 parts of adipic acid;
10 portions of ethylene glycol
45 parts of MDI;
and B component:
55 parts of hydroxymethyl cellulose;
0.5 part of foaming agent; the foaming agent is dichloromethane;
0.3 part of foam stabilizer; the foam stabilizer is PU-1230;
2 parts of pure water;
and C, component C:
ethylene glycol 5 parts
0.2 part of triethylene diamine;
and (D) component:
10 parts of an anti-yellowing agent; the anti-yellowing agent is anti-yellowing agent L9322;
5 parts of a hardening agent; the hardener is 3,3 '-dichloro-4, 4' -diaminodiphenylmethane.
The preparation method of the PU sole stock solution comprises the following steps:
s1, mixing adipic acid and ethylene glycol in proportion, heating to 210 ℃ for reaction for 3 hours, evaporating a byproduct of water, cooling to 82 ℃, adding MDI (diphenyl-methane-diisocyanate), and stirring for reaction for 2 hours to obtain a component A;
s2, uniformly mixing hydroxymethyl cellulose, a foaming agent, a foam stabilizer and pure water in proportion to obtain a component B;
s3, adding triethylene diamine into ethylene glycol according to a proportion, and uniformly mixing to obtain a component C;
s4, grinding the anti-yellowing agent and the hardening agent, and uniformly mixing to obtain a component D;
and S5, fully and uniformly mixing the component A, the component B, the component C and the component D, pouring the mixture into a test piece mold or a sole mold, carrying out curing reaction for 4min, opening the mold, and naturally curing at room temperature for 24h to obtain the PU sole stock solution.
Comparative example 2
Compared with example 4, no hydroxymethyl cellulose is added, and other raw materials and preparation methods are consistent.
The raw materials comprise the following components in parts by weight:
the component A comprises:
10 parts of adipic acid;
10 portions of ethylene glycol
45 parts of MDI;
and B component:
55 parts of microcrystalline cellulose;
0.5 part of foaming agent; the foaming agent is dichloromethane;
0.3 part of foam stabilizer; the foam stabilizer is PU-1230;
2 parts of pure water;
and C, component C:
ethylene glycol 5 parts
0.2 part of triethylene diamine;
and (D) component:
10 parts of an anti-yellowing agent; the anti-yellowing agent is anti-yellowing agent L9322;
5 parts of a hardening agent; the hardener is 3,3 '-dichloro-4, 4' -diaminodiphenylmethane.
The preparation method of the PU sole stock solution comprises the following steps:
s1, mixing adipic acid and ethylene glycol in proportion, heating to 210 ℃ for reaction for 3 hours, evaporating a byproduct of water, cooling to 82 ℃, adding MDI (diphenyl-methane-diisocyanate), and stirring for reaction for 2 hours to obtain a component A;
s2, uniformly mixing microcrystalline cellulose, a foaming agent, a foam stabilizer and pure water in proportion to obtain a component B;
s3, adding triethylene diamine into ethylene glycol according to a proportion, and uniformly mixing to obtain a component C;
s4, grinding the anti-yellowing agent and the hardening agent, and uniformly mixing to obtain a component D;
and S5, fully and uniformly mixing the component A, the component B, the component C and the component D, pouring the mixture into a test piece mold or a sole mold, carrying out curing reaction for 4min, opening the mold, and naturally curing at room temperature for 24h to obtain the PU sole stock solution.
EXAMPLE 5 preparation of PU shoe soles
The method comprises the following steps:
s1, preparing a mixture by adopting a color powder and the PU sole stock solution prepared in the embodiment 2, wherein the preparation method of the mixture comprises the steps of heating the color powder and the PU sole stock solution in an open mill to 200 ℃ and uniformly mixing; the mixture was sprayed at a rate of 100mL per minute; the heating temperature in step S2 is 180 ℃; spraying the mixture on a mold of a casting machine to form an outsole;
s2, pouring a foamed PU material into the cavity of the mold, heating to obtain a molded inner sole, and integrally molding the whole sole.
EXAMPLE 6 preparation of PU shoe soles
The method comprises the following steps:
s1, preparing a mixture by adopting a color powder and the PU sole stock solution prepared in the embodiment 4, wherein the preparation method of the mixture comprises the steps of heating the color powder and the PU sole stock solution in an open mill to 200 ℃ and uniformly mixing; the mixture was sprayed at a rate of 100mL per minute; the heating temperature in step S2 is 220 ℃; spraying the mixture on a mold of a casting machine to form an outsole;
s2, pouring a foamed PU material into the cavity of the mold, heating to obtain a molded inner sole, and integrally molding the whole sole.
Comparative example 3 preparation of PU shoe sole
The method comprises the following steps:
s1, preparing a mixture by adopting color powder and the PU sole stock solution prepared in the comparative example 1, wherein the preparation method of the mixture comprises the steps of heating the color powder and the PU sole stock solution in an open mill to 200 ℃ and uniformly mixing; the mixture was sprayed at a rate of 100mL per minute; the heating temperature in step S2 is 220 ℃; spraying the mixture on a mold of a casting machine to form an outsole;
s2, pouring a foamed PU material into the cavity of the mold, heating to obtain a molded inner sole, and integrally molding the whole sole.
Comparative example 4 preparation of PU shoe sole
The method comprises the following steps:
s1, preparing a mixture by adopting color powder and the PU sole stock solution prepared in the comparative example 2, wherein the preparation method of the mixture comprises the steps of heating the color powder and the PU sole stock solution in an open mill to 200 ℃ and uniformly mixing; the mixture was sprayed at a rate of 100mL per minute; the heating temperature in step S2 is 220 ℃; spraying the mixture on a mold of a casting machine to form an outsole;
s2, pouring a foamed PU material into the cavity of the mold, heating to obtain a molded inner sole, and integrally molding the whole sole.
Test example 1
The soles prepared in examples 5 and 6 and comparative examples 3 and 4 were subjected to performance tests, and the results are shown in table 1.
TABLE 1
Figure BDA0002383527830000141
As can be seen from the above table, the PU soles prepared in examples 5 and 6 of the present invention have better overall performance, i.e., better mechanical properties (wear resistance), lower density (light weight), and lower hardness (softer) compared with commercially available elastic soles.
The PU stock solution prepared in the comparative example 1 is adopted in the comparative example 3, the PU stock solution prepared in the comparative example 2 is adopted in the comparative example 4, the mechanical property, the density and the hardness are greatly reduced, and therefore, the addition of the microcrystalline cellulose and the carboxymethyl cellulose has obvious enhancement on the performance of the PU sole and has a synergistic effect.
Compared with the prior art, the invention adopts the cellulose as the polyester-polyether polyol material, has the advantages of high strength, good wear resistance, good adhesion with the vamp and the like of the polyester polyol, has the advantages of good hydrolysis resistance and stability of the polyether polyol, is liquid at normal temperature, low in viscosity, wide in foaming range, convenient to operate, good in economy, easy to obtain raw materials and the like, and the prepared PU sole stock solution has excellent mechanical properties of high tearing strength, high tensile strength and high tensile rate, and the polyether type sole stock solution has the characteristics of low viscosity and hydrolysis resistance, thereby having good application value;
the PU sole manufactured by the invention is integrally formed, the adhesive force of the outer sole and the inner sole is large, the PU sole is not easy to come unstuck, and the practicability is strong.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The PU sole stock solution is characterized by comprising a component A, a component B and a component C, wherein the component A comprises the following components in parts by weight:
the component A comprises:
5-10 parts of adipic acid;
5-10 parts of ethylene glycol
25-45 parts of MDI;
and B component:
32-37 parts of microcrystalline cellulose;
12-25 parts of hydroxymethyl cellulose;
0.2-0.5 part of foaming agent;
0.1-0.3 part of foam stabilizer;
1-2 parts of water;
and C, component C:
2-5 parts of ethylene glycol;
0.1-0.2 part of triethylene diamine.
2. The PU sole stock solution according to claim 1, further comprising component D in parts by weight: 5-10 parts of anti-yellowing agent and 2-5 parts of hardening agent.
3. The PU sole stock solution according to claim 1, wherein the blowing agent is selected from one of HCFC-141B or methylene chloride; the foam stabilizer is selected from one or a mixture of PU-1230, XHG-293, H420, DC190 and PU-1253.
4. The PU sole stock solution according to claim 2, wherein the anti-yellowing agent is selected from one or more of anti-yellowing agent L9322, anti-yellowing agent UVK-CL, anti-yellowing agent UVK-CL2, and anti-yellowing agent L-1268; the hardener is 3,3 '-dichloro-4, 4' -diaminodiphenylmethane.
5. A method for preparing the PU sole stock solution of claim 1 or 3, comprising the steps of:
s1, mixing adipic acid and ethylene glycol in proportion, heating to 180 ℃ and 220 ℃ for reaction for 2-3h, evaporating by-product water, reducing the temperature to 75-85 ℃, adding MDI (diphenylmethane diisocyanate), and stirring for reaction for 1-2h to obtain a component A;
s2, uniformly mixing microcrystalline cellulose, hydroxymethyl cellulose, a foaming agent, a foam stabilizer and water in proportion to obtain a component B;
s3, adding triethylene diamine into ethylene glycol according to a proportion, and uniformly mixing to obtain a component C;
and S4, fully and uniformly mixing the component A, the component B and the component C, pouring the mixture into a test piece mold or a sole mold, carrying out curing reaction for 3-5min, opening the mold, and naturally curing at room temperature for 24h to obtain the PU sole stock solution.
6. A method for preparing the PU sole stock solution according to claim 2 or 4, which comprises the following steps:
s1, mixing adipic acid and ethylene glycol in proportion, heating to 180 ℃ and 220 ℃ for reaction for 2-3h, evaporating by-product water, reducing the temperature to 75-85 ℃, adding MDI (diphenylmethane diisocyanate), and stirring for reaction for 1-2h to obtain a component A;
s2, uniformly mixing microcrystalline cellulose, hydroxymethyl cellulose, a foaming agent, a foam stabilizer and water in proportion to obtain a component B;
s3, adding triethylene diamine into ethylene glycol according to a proportion, and uniformly mixing to obtain a component C;
s4, grinding the anti-yellowing agent and the hardening agent, and uniformly mixing to obtain a component D;
s5, fully and uniformly mixing the component A, the component B, the component C and the component D, then pouring the mixture into a test piece mold or a sole mold, carrying out curing reaction for 3-5min, opening the mold, and naturally curing at room temperature for 24h to obtain the PU sole stock solution.
7. A preparation method of PU shoe soles is characterized by comprising the following steps:
s1, preparing a mixture by adopting color powder and the PU sole stock solution of claim 1 or 3, spraying the mixture on a mold of a casting machine, and forming an outsole;
s2, pouring a foamed PU material into the cavity of the mold, heating to obtain a molded inner sole, and integrally molding the whole sole.
8. A preparation method of PU shoe soles is characterized by comprising the following steps:
s1, preparing a mixture by adopting color powder and the PU sole stock solution of claim 2 or 4, spraying the mixture on a mold of a casting machine, and forming an outsole;
s2, pouring a foamed PU material into the cavity of the mold, heating to obtain a molded inner sole, and integrally molding the whole sole.
9. The method for preparing PU shoe sole according to claim 7 or 8, wherein the mixture is prepared by heating color powder and PU shoe sole stock solution in an open mill to 200 ℃ and mixing them uniformly; the mixture was sprayed at a rate of 100mL per minute; the heating temperature in step S2 is 180-220 ℃.
10. The PU sole according to any one of claims 7 to 9, wherein the outer sole and the inner sole are integrally formed.
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CN103570908A (en) * 2012-07-19 2014-02-12 旭川化学（昆山）有限公司 Polyurethane sole material raw liquid
CN105461915A (en) * 2015-12-24 2016-04-06 山东一诺威新材料有限公司 Polyester-polyether polyol for microporous PU (polyurethane) shoe sole and preparation method of polyester-polyether polyol as well as PU shoe sole stock solution prepared from polyester-polyether polyol and preparation method of PU shoe sole stock solution

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Publication number Priority date Publication date Assignee Title
CN103570908A (en) * 2012-07-19 2014-02-12 旭川化学（昆山）有限公司 Polyurethane sole material raw liquid
CN105461915A (en) * 2015-12-24 2016-04-06 山东一诺威新材料有限公司 Polyester-polyether polyol for microporous PU (polyurethane) shoe sole and preparation method of polyester-polyether polyol as well as PU shoe sole stock solution prepared from polyester-polyether polyol and preparation method of PU shoe sole stock solution

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