CN112708098A - Wet-process polyurethane resin and preparation method and application thereof - Google Patents

Wet-process polyurethane resin and preparation method and application thereof Download PDF

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CN112708098A
CN112708098A CN202011583628.0A CN202011583628A CN112708098A CN 112708098 A CN112708098 A CN 112708098A CN 202011583628 A CN202011583628 A CN 202011583628A CN 112708098 A CN112708098 A CN 112708098A
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polyurethane resin
wet
diisocyanate
diphenylmethane
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CN112708098B (en
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钱建中
钱洪祥
胡大勇
钱迪
黄凯华
陈桂莲
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Shanghai Huide Technology Co ltd
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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
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone 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
    • 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
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
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    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • 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
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/08—Cellulose derivatives
    • C08J2401/14—Mixed esters
    • 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
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
    • C08J2425/12—Copolymers of styrene with unsaturated nitriles

Abstract

The invention provides a wet-process polyurethane resin and a preparation method and application thereof, wherein the wet-process polyurethane resin comprises A, B, C three components, and the preparation raw materials of the component A comprise the following components: polyoxyethylene glycol, resorcinol bis (2-hydroxyethyl) ether, diphenylmethane-4, 4' -diisocyanate and N, N-dimethylformamide; the preparation raw materials of the component B comprise the following components: adipic acid polyester polyol, polycaprolactone diol, aromatic polyester polyol, a small molecular chain extender, diphenylmethane-4, 4' -diisocyanate and N, N-dimethylformamide; the component C comprises cellulose acetate butyrate and SAN resin in a weight ratio of 1: 2-1: 1. The labor protection gloves made of the wet-process polyurethane resin have the advantages of good demolding property, good rebound resilience, good wear resistance, good gas permeability and good wearing comfort.

Description

Wet-process polyurethane resin and preparation method and application thereof
Technical Field
The invention belongs to the field of preparation of polyurethane resin, relates to wet-process polyurethane resin, and a preparation method and application thereof, and particularly relates to wet-process polyurethane resin with good resilience and wear resistance for labor gloves, and a preparation method and application thereof.
Background
The common gloves for labor protection in the current market mainly comprise PVC gloves, latex gloves, butyronitrile gloves, PU (polyurethane) gloves and the like. The PU gloves are the lightest and light gloves, the PU dipping gloves in the market are mainly prepared by taking glove cores made of materials such as polyester, nylon or DYNEEMA as base materials and dipping polyurethane resin on the glove cores, and although the rubber surface is thin, the wear resistance of the PU dipping gloves is outstanding. The PU gloves have the advantages of static electricity resistance, corrosion resistance, skid resistance, wear resistance, good air permeability, lightness, flexibility, comfortable and convenient wearing, no slipping, no dust falling, strong gripping force, no hand injury and the like, thereby having wide application in the fields of industrial and agricultural production, buildings, medical treatment and the like and being a necessary hand protection article. In recent years, PU gloves have become important products in safety gloves in the international market, and the sales volume is increasing.
The PU dipping labor protection gloves have the most basic requirements of good demoulding property in the production process, good demoulding property means the improvement of production efficiency, good resilience means the comfort of wearing gloves, and the demoulding property, the resilience, the wear resistance and the scratch resistance of resin have very close relation with a cellular structure formed by solidifying PU resin in the glove forming process. The larger the cells, the better the release properties of the glove, but the resilience and abrasion and scratch resistance of the glove are deteriorated.
CN106750159A discloses a preparation method of polyurethane resin for a high-wear-resistance labor protection glove, which comprises the steps of reacting polyglycol with a part of diisocyanate to generate isocyanate group-terminated prepolymer, and orderly arranging soft segments and hard segments of the polyurethane resin, so as to control the solidification speed and the size of pores of the resin, and further control the penetration degree of the resin to a glove core, so that the prepared polyurethane resin achieves high wear resistance and is not easy to separate from a mold, but the resilience and the demolding property are further improved.
CN108250399A discloses a wet polyurethane resin for labor gloves with high demolding performance and good wear resistance, which is prepared from polyester polyol, castor oil polyol, isocyanate, a diol chain extender, a hydrophilic chain extender, a solvent, a demolding auxiliary agent and malic acid. The wet-process polyurethane resin for the labor protection gloves has good demolding performance and wear resistance, but the rebound resilience of the wet-process polyurethane resin is still to be further improved.
CN105885664A discloses a preparation method of a high-resilience gum dipping labor protection glove coating, the preparation process of the invention is simple, and the prepared high-resilience gum dipping labor protection glove coating has excellent tensile resilience and low VOC content, is wear-resistant and ultraviolet-resistant, but the mold release performance of the high-resilience gum dipping labor protection glove coating needs to be further improved.
Therefore, how to ensure good rebound resilience and wear resistance of the polyurethane resin for the labor protection glove on the premise of ensuring good demolding performance of the polyurethane resin becomes a technical problem to be solved urgently at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a wet-process polyurethane resin, a preparation method and application thereof, and particularly provides the wet-process polyurethane resin for labor gloves with good rebound resilience and wear resistance, the preparation method and the application thereof. The labor protection gloves made of the wet-process polyurethane resin have the advantages of good demolding property, good rebound resilience, good wear resistance, good gas permeability and good wearing comfort.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a wet-process polyurethane resin, which comprises A, B, C three components, wherein the preparation raw materials of the component A comprise the following components in percentage by weight:
Figure BDA0002865721160000021
the preparation raw materials of the component B comprise the following components in percentage by weight:
Figure BDA0002865721160000031
the component C comprises cellulose acetate butyrate and SAN resin in a weight ratio of 1: 2-1: 1 (such as 1:2, 3:4 or 1: 1).
In the present invention, the polyurethane resin is a block copolymerization type high molecular compound composed of a soft segment (polyol) and a hard segment (chain extender and isocyanate). The soft segment and the hard segment have thermodynamic incompatibility property, which results in a special microphase separation structure, wherein the mechanical property and resilience of the microphase separation structure are changed along with the change of microphase separation degree.
In the invention, the polyoxyethylene glycol in the component A has good hydrophilicity, so that the resin has good hydrophilicity and high resin solidification speed, and is beneficial to generating large and round foam holes, thereby improving the demoulding property of the polyurethane resin; the resorcinol bis (2-hydroxyethyl) ether is used as a chain extender and has low shrinkage, low compression set and good demoulding property.
In the invention, the polycaprolactone polyol in the component B has the characteristics of high strength, good low-temperature flexibility, good elasticity, good hydrolysis resistance and good weather resistance.
In the invention, the component C is a foam hole regulator, wherein the SAN resin is introduced to adjust the microphase separation structure of the polyurethane resin so as to adjust the final solidified foam hole structure of the resin, and the cellulose acetate butyrate has certain hydrophilicity and excellent light resistance and wear resistance.
In the present invention, the amount of polyoxyethylene glycol used in the raw material for the A component may be 19% to 23%, such as 19%, 21%, 23%, etc., and if the amount of polyoxyethylene glycol is less than 19%, such as 15%, the releasability of the polyurethane-impregnated glove made of wet polyurethane is affected, and if the amount of polyoxyethylene glycol is more than 23%, such as 25%, the abrasion resistance and rebound resilience of the polyurethane-impregnated glove made of wet polyurethane is affected.
In the present invention, the resorcinol bis (2-hydroxyethyl) ether may be used in an amount of 1.5% to 4.5%, for example, 1.5%, 3%, 4%, or 4.5%, etc., in the preparation raw material of the a component.
In the present invention, in the raw material for preparing the component a, the amount of the diphenylmethane-4, 4' -diisocyanate may be 7% to 8%, for example, 7%, 7.5%, 8%, or the like.
In the present invention, in the raw material for preparing the component a, the amount of N, N-dimethylformamide may be 66% to 70%, for example, 66%, 67%, 68%, 69%, 70%, etc.
In the present invention, the amount of the adipic acid-based polyester polyol used in the raw material for preparing the B component may be 8% to 12%, for example, 8%, 9%, 10%, 11%, 12%, or the like.
In the invention, the amount of polycaprolactone diol used in the raw material for preparing the component B may be 4% to 7%, for example, 4%, 5%, 6%, 7%, etc.
In the present invention, the aromatic polyester polyol may be used in an amount of 5.5% to 9%, for example, 5.5%, 6%, 7%, 8%, 9%, or the like, in the raw material for preparing the B component.
In the present invention, in the raw material for preparing the B component, the amount of the small molecule chain extender may be 1.2% to 2.1%, for example, 1.2%, 1.4%, 1.6%, 1.8%, 2.1%, etc.
In the present invention, the amount of diphenylmethane-4, 4' -diisocyanate used in the raw material for preparing the B component may be 7.5% to 9%, for example, 7.5%, 8%, 8.5%, 9%, or the like.
In the present invention, in the raw material for preparing the B component, the amount of N, N-dimethylformamide may be 66% to 70%, for example, 66%, 67%, 68%, 69%, 70%, or the like.
In the present invention, the polyoxyethylene glycol has a number average molecular weight of 1000 to 2000g/mol, for example 1000g/mol, 1500g/mol or 2000 g/mol.
In the present invention, the adipic acid-based polyester polyol is an adipic acid-based polyester polyol having a number average molecular weight of 2000 to 4000g/mol (for example, 2000g/mol, 3000g/mol, or 4000 g/mol).
Preferably, the adipic acid-based polyester polyol is selected from any one of or a combination of at least two of polyethylene adipate glycol, polybutylene adipate glycol, polyethylene adipate-butylene glycol, or polyethylene adipate glycol having a number average molecular weight of 2000 to 4000g/mol (for example, 2000g/mol, 3000g/mol, or 4000 g/mol). Combinations of the at least two, such as polyethylene adipate glycol and polybutylene adipate glycol, polyethylene adipate-butylene glycol, and polyethylene adipate glycol, and the like.
In the present invention, the number average molecular weight of the polycaprolactone diol is 1000 to 2000g/mol, such as 1000g/mol or 2000 g/mol.
In the present invention, the aromatic polyester polyol is phthalic anhydride polyester diol having a number average molecular weight of 2000 g/mol.
In the present invention, the small molecule chain extender includes any one of ethylene glycol, 1, 3-propanediol or 1, 4-butanediol or a combination of at least two thereof. Combinations of the at least two, such as ethylene glycol and 1, 3-propanediol, ethylene glycol and 1, 4-butanediol, and the like.
In the invention, the weight ratio of the component A to the component B is 1: 9-1: 3 (such as 1:9, 1:7, 1:5 or 1:3, etc.), if the weight ratio of the component A to the component B is higher than 1:3, such as 1:1, the wear resistance and rebound resilience of the polyurethane impregnated glove prepared from the wet polyurethane resin are affected, and if the weight ratio of the component A to the component B is lower than 1:9, such as 1:12, the demolding property of the polyurethane impregnated glove prepared from the wet polyurethane resin is affected; the C component comprises 1% to 3%, such as 1%, 1.5%, 2%, or 3%, etc., of the total weight of the a and B components, and if the C component comprises more than 3%, such as 5%, of the total weight of the a and B components, the abrasion resistance and resilience of a polyurethane impregnated glove made from wet process polyurethane resin will be affected.
In another aspect, the present invention provides a method for preparing the wet process polyurethane resin as described above, comprising the steps of:
(1) preparation of a component A: uniformly mixing polyoxyethylene glycol, resorcinol bis (2-hydroxyethyl) ether and part of N, N-dimethylformamide, adding part of diphenylmethane-4, 4 '-diisocyanate to the mixture for reaction, and then adding the rest of diphenylmethane-4, 4' -diisocyanate and the rest of N, N-dimethylformamide in batches to react until the viscosity of a reaction solution reaches 100-150 Pa.s (such as 100 Pa.s, 120 Pa.s, 130 Pa.s or 150 Pa.s) at 25 ℃ to obtain a component A;
(2) b, preparation of a component: uniformly mixing adipic acid polyester polyol, polycaprolactone diol, aromatic polyester polyol and part of N, N-dimethylformamide, and adding part of diphenylmethane-4, 4' -diisocyanate into the mixture to perform prepolymerization reaction to obtain a prepolymer; adding a small-molecule chain extender into the prepolymer, adding part of N, N-dimethylformamide, uniformly stirring, adding part of diphenylmethane-4, 4 '-diisocyanate for reaction, adding the rest of diphenylmethane-4, 4' -diisocyanate and the rest of N, N-dimethylformamide in batches, and reacting until the viscosity of the reaction solution reaches 200-350 Pa.s (such as 200 Pa.s, 250 Pa.s, 300 Pa.s or 350 Pa.s) at 25 ℃ to obtain a component B;
(3) and uniformly mixing the component A and the component B, cooling, adding the component C into the mixture, and stirring to obtain the wet-process polyurethane resin.
In the invention, the component B adopts a pre-polymerization synthesis process, so that the arrangement of hard sections and soft sections of the polyurethane resin is more regular, and the excessive concentration of the hard sections is avoided, so that the polyurethane resin can form a relatively ideal microphase separation structure, and the final resin is solidified to form a fine and regular cell structure; the component C adopts cellulose acetate butyrate and SAN to be compounded for use, so that the solidification speed of the resin can be better adjusted, and various performances of the resin can achieve ideal effects. The C component is added after A, B components are uniformly mixed and cooled, because the C component can react with A, B components under the condition of higher temperature, thereby influencing the using effect of the resin.
In the invention, the mixing time in the step (1) is 20-40 min, such as 20min, 25min, 30min, 35min or 40 min.
Preferably, the part of N, N-dimethylformamide in the step (1) is an amount such that the solid content in the reaction solution is 44-46% (e.g., 44%, 45%, 46%, etc.).
Preferably, the partial diphenylmethane-4, 4' -diisocyanate in step (1) is in an amount such that the molar ratio of isocyanate groups to hydroxyl groups in the reaction solution is from 0.92:1 to 0.94:1 (e.g., 0.92:1, 0.93:1, or 0.94: 1).
Preferably, the temperature for adding part of the diphenylmethane-4, 4' -diisocyanate to carry out the reaction in step (1) is 75-85 ℃ (for example, 75 ℃, 80 ℃ or 85 ℃ and the like), and the reaction time is 1-2 h, for example, 1h, 1.5h or 2h and the like.
Preferably, the mixing time in the step (2) is 20-60 min, such as 20min, 30min, 40min, 50min or 60 min.
Preferably, the N, N-dimethylformamide in the step (2) is used in an amount such that the solid content in the prepolymerization reaction solution is 58-62% (e.g. 58%, 59%, 60%, 61%, 62%, etc.).
Preferably, the partial diphenylmethane-4, 4' -diisocyanate in step (2) is in an amount such that the molar ratio of isocyanate groups to hydroxyl groups in the prepolymerization reaction solution is 0.78:1 to 0.82:1 (e.g., 0.78:1, 0.80:1, or 0.82: 1).
Preferably, the temperature of the prepolymerization reaction in the step (2) is 75-85 ℃ (for example, 75 ℃, 80 ℃ or 85 ℃ and the like), and the time of the prepolymerization reaction is 1-2 h, for example, 1h, 1.5h or 2h and the like.
Preferably, the N, N-dimethylformamide portion to be added in step (2) is in an amount such that the solid content in the reaction solution is 44 to 46% (for example, 44%, 45%, 46%, or the like).
Preferably, the amount of the diphenylmethane-4, 4' -diisocyanate to be added in step (2) is such that the molar ratio of the isocyanate group to the hydroxyl group in the reaction solution is 0.92:1 to 0.94:1 (for example, 0.92:1, 0.93:1, or 0.94: 1).
Preferably, the temperature for adding part of the diphenylmethane-4, 4' -diisocyanate to carry out the reaction in the step (2) is 75-85 ℃ (for example, 75 ℃, 80 ℃ or 85 ℃) and the reaction time is 1-2 h, for example, 1h, 1.5h or 2 h.
Preferably, the mixing temperature in the step (3) is 50-70 ℃ (for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃ and the like), and the mixing time is 1-2 h, for example, 1h, 1.5h or 2h and the like.
Preferably, the temperature reduction in step (3) is to be reduced to 50 ℃ or lower, such as 50 ℃, 45 ℃, 30 ℃, 20 ℃ or 10 ℃ or the like.
Preferably, the stirring time in the step (3) is 2-3 h, such as 2h, 2.5h or 3 h.
Preferably, the solid content of the wet-process polyurethane resin in the step (3) is 32-34%, such as 32%, 33%, or 34%.
In a further aspect, the present invention provides the use of a wet process polyurethane resin as described above in the manufacture of a labor glove.
Compared with the prior art, the invention has at least the following beneficial effects:
the A, B components are used in a matching way according to a certain proportion, so that not only can the demoulding property of the resin be ensured, but also the rebound resilience and the wear resistance of the resin can be ensured. The component C of the invention adopts cellulose acetate butyrate and SAN to be compounded for use, so that the solidification speed of the resin can be better adjusted, and various performances of the resin can achieve ideal effects. A. B, C and a reasonable polymerization process is assisted, so that the prepared polyurethane resin has excellent demolding property, good wear resistance (Martindale friction times: 12000-14000) and good rebound resilience.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
In this embodiment, a wet-process polyurethane resin is provided, where the wet-process polyurethane resin includes A, B, C three components, and the preparation raw materials of the component a include the following components in percentage by weight:
Figure BDA0002865721160000091
the preparation raw materials of the component B comprise the following components in percentage by weight:
Figure BDA0002865721160000092
the component C consists of cellulose acetate butyrate and SAN resin in a weight ratio of 1: 2.
Wherein the number average molecular weight of the polyoxyethylene glycol is 2000g/mol, the number average molecular weight of the polyethylene adipate glycol is 4000g/mol, the number average molecular weight of the polycaprolactone glycol is 2000g/mol, and the number average molecular weight of the phthalic anhydride polyester glycol is 2000 g/mol; the weight ratio of the component A to the component B is 1: 6; the component C accounts for 3 percent of the total weight of the component A and the component B.
The preparation method comprises the following steps:
(1) preparation of a component A: mixing polyoxyethylene glycol, resorcinol bis (2-hydroxyethyl) ether and part of N, N-dimethylformamide for 30min, adding part of diphenylmethane-4, 4 '-diisocyanate into the mixture to react so that the solid content of the reaction liquid is 44% and the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.93:1, reacting for 1h at 80 ℃, then adding the rest of diphenylmethane-4, 4' -diisocyanate and the rest of N, N-dimethylformamide in batches, and reacting until the viscosity of the reaction liquid reaches 120 Pa.s at 25 ℃ to obtain a component A;
(2) b, preparation of a component: mixing polyethylene glycol adipate glycol, polycaprolactone glycol, aromatic polyester polyol and part of N, N-dimethylformamide for 30min, adding part of diphenylmethane-4, 4' -diisocyanate into the mixture to perform a prepolymerization reaction, so that the solid content of a prepolymerization reaction liquid is 58%, the molar ratio of isocyanate groups to hydroxyl groups in the prepolymerization reaction liquid is 0.78:1, and reacting for 1h at 80 ℃ to obtain a prepolymer; adding ethylene glycol into the prepolymer, adding part of N, N-dimethylformamide, uniformly stirring, adding part of diphenylmethane-4, 4 '-diisocyanate, reacting at 75 ℃ for 1h to ensure that the solid content of the reaction liquid is 44% and the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.93:1, then adding the rest of diphenylmethane-4, 4' -diisocyanate and the rest of N, N-dimethylformamide in batches, and reacting until the viscosity of the reaction liquid reaches 200 Pa.s at 25 ℃ to obtain a component B;
(3) and (3) mixing the component A and the component B at 60 ℃ for 1h, cooling to 50 ℃, adding the component C into the mixture, and stirring for 2.5h to obtain the wet-process polyurethane resin (the solid content is 32%).
Example 2
In this embodiment, a wet-process polyurethane resin is provided, where the wet-process polyurethane resin includes A, B, C three components, and the preparation raw materials of the component a include the following components in percentage by weight:
Figure BDA0002865721160000101
the preparation raw materials of the component B comprise the following components in percentage by weight:
Figure BDA0002865721160000102
Figure BDA0002865721160000111
the component C consists of cellulose acetate butyrate and SAN resin in a weight ratio of 1: 2.
Wherein the number average molecular weight of the polyoxyethylene glycol is 2000g/mol, the number average molecular weight of the polyethylene adipate glycol is 4000g/mol, the number average molecular weight of the polycaprolactone glycol is 2000g/mol, and the number average molecular weight of the phthalic anhydride polyester glycol is 2000 g/mol; the weight ratio of the component A to the component B is 1: 9; the component C accounts for 3 percent of the total weight of the component A and the component B.
The preparation method comprises the following steps:
(1) preparation of a component A: mixing polyoxyethylene glycol, resorcinol bis (2-hydroxyethyl) ether and part of N, N-dimethylformamide for 25min, adding part of diphenylmethane-4, 4 '-diisocyanate into the mixture to react so that the solid content of the reaction liquid is 45% and the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.92:1, reacting for 1.5h at 75 ℃, then adding the rest of diphenylmethane-4, 4' -diisocyanate and the rest of N, N-dimethylformamide in batches, and reacting until the viscosity of the reaction liquid reaches 150 Pa.s at 25 ℃ to obtain a component A;
(2) b, preparation of a component: mixing polyethylene glycol adipate glycol, polycaprolactone glycol, aromatic polyester polyol and part of N, N-dimethylformamide for 20min, adding part of diphenylmethane-4, 4' -diisocyanate into the mixture to perform a prepolymerization reaction, so that the solid content of a prepolymerization reaction liquid is 60%, the molar ratio of isocyanate groups to hydroxyl groups in the prepolymerization reaction liquid is 0.82:1, and reacting for 2h at 75 ℃ to obtain a prepolymer; adding ethylene glycol into the prepolymer, adding part of N, N-dimethylformamide, uniformly stirring, adding part of diphenylmethane-4, 4 '-diisocyanate, reacting at 80 ℃ for 2 hours to ensure that the solid content of the reaction liquid is 46 percent and the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.94:1, then adding the rest of diphenylmethane-4, 4' -diisocyanate and the rest of N, N-dimethylformamide in batches, and reacting until the viscosity of the reaction liquid reaches 300 Pa.s at 25 ℃ to obtain a component B;
(3) and (3) mixing the component A and the component B at 50 ℃ for 1.5h, cooling to 40 ℃, adding the component C into the mixture, and stirring for 2h to obtain the wet-process polyurethane resin (the solid content is 34%).
Example 3
In this embodiment, a wet-process polyurethane resin is provided, where the wet-process polyurethane resin includes A, B, C three components, and the preparation raw materials of the component a include the following components in percentage by weight:
Figure BDA0002865721160000121
the preparation raw materials of the component B comprise the following components in percentage by weight:
Figure BDA0002865721160000122
the component C consists of cellulose acetate butyrate and SAN resin in a weight ratio of 1: 2.
Wherein the number average molecular weight of the polyoxyethylene glycol is 1000g/mol, the number average molecular weight of the polybutylene adipate glycol is 2000g/mol, the number average molecular weight of the polycaprolactone glycol is 2000g/mol, and the number average molecular weight of the phthalic anhydride polyester glycol is 2000 g/mol; the weight ratio of the component A to the component B is 1: 3; the component C accounts for 3 percent of the total weight of the component A and the component B.
The preparation method comprises the following steps:
(1) preparation of a component A: mixing polyoxyethylene glycol, resorcinol bis (2-hydroxyethyl) ether and part of N, N-dimethylformamide for 20min, adding part of diphenylmethane-4, 4 '-diisocyanate into the mixture to react so that the solid content of the reaction liquid is 46% and the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.94:1, reacting for 2h at 78 ℃, then adding the rest of diphenylmethane-4, 4' -diisocyanate and the rest of N, N-dimethylformamide in batches, and reacting until the viscosity of the reaction liquid reaches 120 Pa.s at 25 ℃ to obtain a component A;
(2) b, preparation of a component: mixing polybutylene adipate glycol, polycaprolactone glycol, aromatic polyester polyol and part of N, N-dimethylformamide for 40min, adding part of diphenylmethane-4, 4' -diisocyanate into the mixture to perform a prepolymerization reaction, so that the solid content of a prepolymerization reaction liquid is 62%, the molar ratio of isocyanate groups to hydroxyl groups in the prepolymerization reaction liquid is 0.8:1, and reacting for 1.5h at 75 ℃ to obtain a prepolymer; adding 1, 4-butanediol into the prepolymer, adding part of N, N-dimethylformamide, uniformly stirring, adding part of diphenylmethane-4, 4 '-diisocyanate to react so that the solid content of the reaction liquid is 45% and the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.92:1, reacting for 1.5h at 78 ℃, then adding the rest of diphenylmethane-4, 4' -diisocyanate and the rest of N, N-dimethylformamide in batches, and reacting until the viscosity of the reaction liquid reaches 350 Pa.s at 25 ℃ to obtain a component B;
(3) and (3) mixing the component A and the component B at 70 ℃ for 2h, cooling to 30 ℃, adding the component C into the mixture, and stirring for 3h to obtain the wet-process polyurethane resin (the solid content is 32%).
Example 4
In this embodiment, a wet-process polyurethane resin is provided, where the wet-process polyurethane resin includes A, B, C three components, and the preparation raw materials of the component a include the following components in percentage by weight:
Figure BDA0002865721160000131
Figure BDA0002865721160000141
the preparation raw materials of the component B comprise the following components in percentage by weight:
Figure BDA0002865721160000142
the component C consists of cellulose acetate butyrate and SAN resin in a weight ratio of 1: 2.
Wherein the number average molecular weight of the polyoxyethylene glycol is 2000g/mol, the number average molecular weight of the poly-diethylene glycol adipate glycol is 2000g/mol, the number average molecular weight of the polycaprolactone glycol is 1000g/mol, and the number average molecular weight of the phthalic anhydride polyester glycol is 2000 g/mol; the weight ratio of the component A to the component B is 1: 6; the component C accounts for 3 percent of the total weight of the component A and the component B.
The preparation method comprises the following steps:
(1) preparation of a component A: mixing polyoxyethylene glycol, resorcinol bis (2-hydroxyethyl) ether and part of N, N-dimethylformamide for 20min, adding part of diphenylmethane-4, 4 '-diisocyanate into the mixture to react so that the solid content of the reaction liquid is 44% and the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.94:1, reacting for 2h at 85 ℃, then adding the rest of diphenylmethane-4, 4' -diisocyanate and the rest of N, N-dimethylformamide in batches, and reacting until the viscosity of the reaction liquid reaches 100 Pa.s at 25 ℃ to obtain a component A;
(2) b, preparation of a component: mixing polydiglycol adipate glycol, polycaprolactone glycol, aromatic polyester polyol and part of N, N-dimethylformamide for 50min, adding part of diphenylmethane-4, 4' -diisocyanate into the mixture to perform a prepolymerization reaction, so that the solid content of a prepolymerization reaction liquid is 59%, the molar ratio of isocyanate groups to hydroxyl groups in the prepolymerization reaction liquid is 0.78:1, and reacting for 2h at 85 ℃ to obtain a prepolymer; adding ethylene glycol into the prepolymer, adding part of N, N-dimethylformamide, uniformly stirring, adding part of diphenylmethane-4, 4 '-diisocyanate, reacting at 85 ℃ for 2 hours to ensure that the solid content of the reaction liquid is 46 percent and the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.94:1, then adding the rest of diphenylmethane-4, 4' -diisocyanate and the rest of N, N-dimethylformamide in batches, and reacting until the viscosity of the reaction liquid reaches 250 Pa.s at 25 ℃ to obtain a component B;
(3) and (3) mixing the component A and the component B at 65 ℃ for 2h, cooling to 40 ℃, adding the component C into the mixture, and stirring for 3h to obtain the wet-process polyurethane resin (the solid content is 33%).
Example 5
In this embodiment, a wet-process polyurethane resin is provided, where the wet-process polyurethane resin includes A, B, C three components, and the preparation raw materials of the component a include the following components in percentage by weight:
Figure BDA0002865721160000151
the preparation raw materials of the component B comprise the following components in percentage by weight:
Figure BDA0002865721160000152
Figure BDA0002865721160000161
the component C consists of cellulose acetate butyrate and SAN resin in a weight ratio of 1: 1.
Wherein the number average molecular weight of the polyoxyethylene glycol is 1500g/mol, the number average molecular weight of the polybutylene adipate glycol is 3000g/mol, the number average molecular weight of the polycaprolactone glycol is 2000g/mol, and the number average molecular weight of the phthalic anhydride polyester glycol is 2000 g/mol; the weight ratio of the component A to the component B is 1: 5; the component C accounts for 2 percent of the total weight of the components A and B.
The preparation method comprises the following steps:
(1) preparation of a component A: mixing polyoxyethylene glycol, resorcinol bis (2-hydroxyethyl) ether and part of N, N-dimethylformamide for 40min, adding part of diphenylmethane-4, 4 '-diisocyanate into the mixture to react so that the solid content of the reaction liquid is 45% and the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.93:1, reacting for 1.5h at 83 ℃, then adding the rest of diphenylmethane-4, 4' -diisocyanate and the rest of N, N-dimethylformamide in batches, and reacting until the viscosity of the reaction liquid reaches 130 Pa.s at 25 ℃ to obtain a component A;
(2) b, preparation of a component: mixing polybutylene adipate glycol, polycaprolactone glycol, aromatic polyester polyol and part of N, N-dimethylformamide for 60min, adding part of diphenylmethane-4, 4' -diisocyanate into the mixture to perform a prepolymerization reaction, so that the solid content of a prepolymerization reaction liquid is 61%, the molar ratio of isocyanate groups to hydroxyl groups in the prepolymerization reaction liquid is 0.82:1, and reacting for 1.5h at 80 ℃ to obtain a prepolymer; adding 1, 3-propylene glycol into the prepolymer, adding part of N, N-dimethylformamide, uniformly stirring, adding part of diphenylmethane-4, 4 '-diisocyanate, reacting at 83 ℃ for 1.5h to obtain a reaction solution with a solid content of 45% and a molar ratio of isocyanate groups to hydroxyl groups of 0.93:1, adding the rest of diphenylmethane-4, 4' -diisocyanate and the rest of N, N-dimethylformamide in batches, and reacting until the viscosity of the reaction solution reaches 200 Pa.s at 25 ℃ to obtain a component B;
(3) and (3) mixing the component A and the component B at 55 ℃ for 1.5h, cooling to 45 ℃, adding the component C into the mixture, and stirring for 2h to obtain the wet-process polyurethane resin (the solid content is 32%).
Example 6
In this embodiment, a wet-process polyurethane resin is provided, where the wet-process polyurethane resin includes A, B, C three components, and the preparation raw materials of the component a include the following components in percentage by weight:
Figure BDA0002865721160000171
the preparation raw materials of the component B comprise the following components in percentage by weight:
Figure BDA0002865721160000172
the component C consists of cellulose acetate butyrate and SAN resin in a weight ratio of 1: 1.
Wherein the number average molecular weight of the polyoxyethylene glycol is 2000g/mol, the number average molecular weight of the poly-diethylene glycol adipate glycol is 4000g/mol, the number average molecular weight of the polycaprolactone glycol is 1000g/mol, and the number average molecular weight of the phthalic anhydride polyester glycol is 2000 g/mol; the weight ratio of the component A to the component B is 1: 4; the component C accounts for 1 percent of the total weight of the components A and B.
The preparation method comprises the following steps:
(1) preparation of a component A: mixing polyoxyethylene glycol, resorcinol bis (2-hydroxyethyl) ether and part of N, N-dimethylformamide for 25min, adding part of diphenylmethane-4, 4 '-diisocyanate into the mixture to react so that the solid content of the reaction liquid is 46% and the molar ratio of isocyanate groups to hydroxyl groups in the reaction liquid is 0.92:1, reacting for 1h at 82 ℃, then adding the rest of diphenylmethane-4, 4' -diisocyanate and the rest of N, N-dimethylformamide in batches, and reacting until the viscosity of the reaction liquid reaches 140 Pa.s at 25 ℃ to obtain a component A;
(2) b, preparation of a component: mixing polydiglycol adipate glycol, polycaprolactone glycol, aromatic polyester polyol and part of N, N-dimethylformamide for 30min, adding part of diphenylmethane-4, 4' -diisocyanate into the mixture to perform a prepolymerization reaction, so that the solid content of a prepolymerization reaction liquid is 60%, the molar ratio of isocyanate groups to hydroxyl groups in the prepolymerization reaction liquid is 0.8:1, and reacting for 1h at 82 ℃ to obtain a prepolymer; adding ethylene glycol into the prepolymer, adding part of N, N-dimethylformamide, uniformly stirring, adding part of diphenylmethane-4, 4 '-diisocyanate, reacting at 82 ℃ for 1h to obtain a reaction solution with a solid content of 44% and a molar ratio of isocyanate groups to hydroxyl groups of 0.92:1, adding the rest of diphenylmethane-4, 4' -diisocyanate and the rest of N, N-dimethylformamide in batches, and reacting until the viscosity of the reaction solution reaches 250 Pa.s at 25 ℃ to obtain a component B;
(3) and (3) mixing the component A and the component B at the temperature of 60 ℃ for 1h, cooling to 30 ℃, adding the component C into the mixture, and stirring for 2.5h to obtain the wet-process polyurethane resin (the solid content is 34%).
Comparative example 1
PFT-311, a commercially available Pofite polyurethane resin, Changzhou.
Comparative example 2
This comparative example differs from example 1 only in that the weight percentage of polyoxyethylene glycol in the A component is 15%. The weight percentage of the preparation raw materials of the component A is as follows:
Figure BDA0002865721160000181
Figure BDA0002865721160000191
comparative example 3
This comparative example differs from example 1 only in that the weight percentage of polyoxyethylene glycol in the A component is 25%. The weight percentage of the preparation raw materials of the component A is as follows:
Figure BDA0002865721160000192
comparative example 4
This comparative example differs from example 1 only in that the weight ratio of the A component and the B component is 1: 1.
Comparative example 5
This comparative example differs from example 1 only in that the weight ratio of the A component and the B component is 1: 12.
Comparative example 6
This comparative example differs from example 1 only in that the C component makes up 5% of the total weight of the a and B components.
The wet-process polyurethane resins prepared in examples 1-6 and comparative examples 2-6, and PFT-311, a Pofite polyurethane resin in comparative example 1, were tested for performance as follows:
(1) and (3) testing the demolding property: polyurethane resin is sleeved on a polyester glove with the same size under the same process condition to prepare a polyurethane impregnated glove, and the demolding performance of the glove is judged according to the force for demolding the glove from a hand mold;
(2) and (3) wear resistance test: the gloves produced in the demoldability test were tested according to the EN388 standard for European protective gloves. The Martindale abrasion resistance tester for the tester is used for testing 180-mesh abrasive paper, and the test load is 9 kPa;
(3) and (3) resilience testing: adding a certain amount of DMF into polyurethane resin to prepare working slurry, respectively scraping films (coating gap is 1.0mm) on a glass plate, placing the glass plate in water for solidification for 10min, taking the formed film off the glass plate, placing the glass plate in hot water at 60 ℃ for soaking for 2h (water is changed once during soaking), and then placing the glass plate in an oven at 120 ℃ for drying. And cutting the dried film into a sample with a square shape of 10 multiplied by 10cm, folding the sample in half at normal temperature, placing a load of 3kg on the sample, placing the sample for 1h, and judging the resilience of the resin by observing the recovery speed of the fold lines.
The results of the performance tests are shown in table 1.
TABLE 1
Name (R) Releasability from mold Number of Martindale rubs Rebound resilience
Example 1 Is excellent in 12600 Good taste
Example 2 Is excellent in 14000 Good taste
Example 3 Is excellent in 12000 Good taste
Example 4 Is excellent in 12800 Good taste
Example 5 Is excellent in 13600 Good taste
Example 6 Is excellent in 13000 Good taste
Comparative example 1 Good wine 8000 In general
Comparative example 2 In general 15000 Good taste
Comparative example 3 Is excellent in 7000 Difference (D)
Comparative example 4 Is excellent in 6800 Difference (D)
Comparative example 5 In general 13000 Good taste
Comparative example 6 Is excellent in 9000 In general
As can be seen from Table 1, the polyurethane impregnated gloves prepared in examples 1 to 6 all had better mold release and abrasion resistance (Martindale number of rubs: 12000 to 14000) than the polyurethane impregnated gloves prepared in comparative example 1, and the polyurethane resins prepared in examples 1 to 6 had better resilience than comparative example 1.
The polyurethane impregnated glove made in comparative example 2 had better abrasion resistance and resilience, but had slightly poorer release properties than the polyurethane impregnated glove made in example 1; the polyurethane impregnated glove made in comparative example 3 showed good release but poor abrasion resistance and resilience compared to the polyurethane impregnated glove made in example 1. This indicates that too little (15%) addition of polyoxyethylene glycol affects the release properties of the polyurethane impregnated glove, while too much (25%) addition of polyoxyethylene glycol affects the abrasion resistance and resilience of the polyurethane impregnated glove.
The polyurethane impregnated glove obtained in comparative example 4 was superior in mold release property, but inferior in abrasion resistance and rebound resilience, compared to the polyurethane impregnated glove obtained in example 1; the polyurethane impregnated glove made in comparative example 5 had better abrasion resistance and rebound resilience and relatively poorer release properties than the polyurethane impregnated glove made in example 1. This shows that too little addition of component B (1: 1 weight ratio of A to B) affects the abrasion resistance and resilience of the polyurethane impregnated glove, while too little addition of component A (1: 12 weight ratio of A to B) affects the release properties of the polyurethane impregnated glove.
The polyurethane impregnated glove made in comparative example 6 was superior in mold release properties, but general in abrasion resistance and rebound resilience, compared to the polyurethane impregnated glove made in example 1. This indicates that too much C component (5% of the total weight of the a and B components) can affect the abrasion resistance and resilience of the urethane impregnated glove.
The applicant states that the present invention is illustrated by the above examples of the wet process polyurethane resin of the present invention and the preparation method thereof, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be implemented by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The wet-process polyurethane resin is characterized by comprising A, B, C components, wherein the preparation raw materials of the component A comprise the following components in percentage by weight:
Figure FDA0002865721150000011
the preparation raw materials of the component B comprise the following components in percentage by weight:
Figure FDA0002865721150000012
the component C comprises cellulose acetate butyrate and SAN resin in a weight ratio of 1: 2-1: 1.
2. The wet process polyurethane resin as claimed in claim 1, wherein the polyoxyethylene glycol has a number average molecular weight of 1000 to 2000 g/mol.
3. The wet process polyurethane resin according to claim 1 or 2, wherein the adipic acid-based polyester polyol is an adipic acid-based polyester polyol having a number average molecular weight of 2000 to 4000 g/mol;
preferably, the adipic acid polyester polyol is selected from any one or a combination of at least two of polyethylene glycol adipate diol, polybutylene adipate diol, polyethylene glycol adipate-butylene glycol adipate diol or polyethylene glycol adipate diol with the number average molecular weight of 2000-4000 g/mol.
4. The wet-process polyurethane resin according to any one of claims 1 to 3, wherein the polycaprolactone diol has a number average molecular weight of 1000 to 2000 g/mol.
5. The wet-process polyurethane resin of any one of claims 1 to 4, wherein the aromatic polyester polyol is a phthalic anhydride polyester diol having a number average molecular weight of 2000 g/mol.
6. The wet process polyurethane resin of any one of claims 1-5, wherein the small molecule chain extender comprises any one of ethylene glycol, 1, 3-propanediol, or 1, 4-butanediol, or a combination of at least two thereof.
7. The wet-process polyurethane resin according to any one of claims 1 to 6, wherein the weight ratio of the A component to the B component is 1:9 to 1: 3; the component C accounts for 1-3% of the total weight of the component A and the component B.
8. The method for preparing a wet-process polyurethane resin according to any one of claims 1 to 7, wherein the preparation method comprises the steps of:
(1) preparation of a component A: uniformly mixing polyoxyethylene glycol, resorcinol bis (2-hydroxyethyl) ether and part of N, N-dimethylformamide, adding part of diphenylmethane-4, 4 '-diisocyanate into the mixture for reaction, then adding the rest of diphenylmethane-4, 4' -diisocyanate and the rest of N, N-dimethylformamide in batches, and reacting until the viscosity of a reaction solution reaches 100-150 Pa.s at 25 ℃ to obtain a component A;
(2) b, preparation of a component: uniformly mixing adipic acid polyester polyol, polycaprolactone diol, aromatic polyester polyol and part of N, N-dimethylformamide, and adding part of diphenylmethane-4, 4' -diisocyanate into the mixture to perform prepolymerization reaction to obtain a prepolymer; adding a small-molecule chain extender into the prepolymer, adding part of N, N-dimethylformamide, uniformly stirring, adding part of diphenylmethane-4, 4 '-diisocyanate for reaction, adding the rest of diphenylmethane-4, 4' -diisocyanate and the rest of N, N-dimethylformamide in batches, and reacting until the viscosity of a reaction solution reaches 200-350 Pa.s at 25 ℃ to obtain a component B;
(3) and uniformly mixing the component A and the component B, cooling, adding the component C into the mixture, and stirring to obtain the wet-process polyurethane resin.
9. The method according to claim 8, wherein the mixing time in step (1) is 20-40 min;
preferably, the part of N, N-dimethylformamide in the step (1) is an amount which enables the solid content in the reaction liquid to be 44-46%;
preferably, the part of diphenylmethane-4, 4' -diisocyanate in step (1) is in an amount such that the molar ratio of isocyanate groups to hydroxyl groups in the reaction solution is from 0.92:1 to 0.94: 1;
preferably, the temperature for adding part of the diphenylmethane-4, 4' -diisocyanate to carry out the reaction in the step (1) is 75-85 ℃, and the reaction time is 1-2 h;
preferably, the mixing time in the step (2) is 20-60 min;
preferably, the part of N, N-dimethylformamide in the step (2) is an amount which enables the solid content in the prepolymerization reaction liquid to be 58-62%;
preferably, the part of diphenylmethane-4, 4' -diisocyanate in the step (2) is in an amount such that the molar ratio of isocyanate groups to hydroxyl groups in the prepolymerization reaction liquid is 0.78:1 to 0.82: 1;
preferably, the temperature of the prepolymerization reaction in the step (2) is 75-85 ℃, and the time of the prepolymerization reaction is 1-2 h;
preferably, the N, N-dimethylformamide added in the step (2) is in an amount which enables the solid content in the reaction liquid to be 44-46%;
preferably, the part of diphenylmethane-4, 4' -diisocyanate to be added in step (2) is in an amount such that the molar ratio of isocyanate groups to hydroxyl groups in the reaction solution is from 0.92:1 to 0.94: 1;
preferably, the temperature for adding part of the diphenylmethane-4, 4' -diisocyanate to react in the step (2) is 75-85 ℃, and the reaction time is 1-2 h;
preferably, the mixing temperature in the step (3) is 50-70 ℃, and the mixing time is 1-2 h;
preferably, the temperature reduction in the step (3) is to be reduced to below 50 ℃;
preferably, the stirring time in the step (3) is 2-3 h;
preferably, the solid content of the wet-process polyurethane resin in the step (3) is 32-34%.
10. Use of the wet process polyurethane resin of any one of claims 1-7 in the manufacture of labor gloves.
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CN114149560A (en) * 2021-12-14 2022-03-08 福建汇得新材料有限公司 Wet-process polyurethane resin and preparation method and application thereof
CN114149560B (en) * 2021-12-14 2023-05-05 福建汇得新材料有限公司 Wet polyurethane resin and preparation method and application thereof

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