CN110194830B - Isocyanate prepolymer mixture for solvent-free polyurethane shoe leather and preparation method and application thereof - Google Patents
Isocyanate prepolymer mixture for solvent-free polyurethane shoe leather and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- C08G18/4825—Polyethers containing two hydroxy groups
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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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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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
- C08G18/61—Polysiloxanes
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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Abstract
The invention discloses an isocyanate prepolymer mixture for solvent-free polyurethane shoe leather, a preparation method and application thereof, wherein the isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather is obtained by mixing polyether modified isocyanate prepolymer B1 and organic silicon modified isocyanate prepolymer B2 and then diluting the mixture by a reactive diluent S; wherein B1 is prepared from isocyanate and polyether diol, and B2 is prepared from isocyanate and organic silicon diol. The invention also provides the application of the isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather: the solvent-free polyurethane coating can be prepared by matching polyester type, polycarbonate type or polyether type polyhydric alcohol, is applied to the processing of solvent-free polyurethane shoe leather, can be prepared into solvent-free polyurethane shoe leather products which can be shaped, prevent rebound and have no wrinkle, and solves the post-processing problem of the solvent-free polyurethane shoe leather products.
Description
Technical Field
The invention relates to the field of synthetic leather, in particular to an isocyanate prepolymer mixture for solvent-free polyurethane shoe leather, a preparation method and application thereof.
Background
The solvent-free polyurethane synthetic leather technology is used as a new environment-friendly production and manufacturing technology in the synthetic leather industry, and is rapidly researched and applied by various synthetic leather enterprises in recent years. The prepared solvent-free polyurethane synthetic leather product has the characteristics of environmental protection, health, excellent durability and durability (generally, the durability and durability can reach more than 5-10 years), and the like, so that the solvent-free polyurethane synthetic leather product is widely applied to the fields of sofa furniture materials, massage chair materials, case materials, automobile interior materials, and the like, and gradually obtains the market approval for the quality and the post-processing applicability of the solvent-free polyurethane synthetic leather product.
Polyurethane shoe leather is an important class in synthetic leather products, and the requirements of environmental protection performance are gradually raised by various international brands in recent years. However, the shoe leather material has great difference from the sofa furniture material, the massage chair material, the luggage leather material and the automobile interior material in the post-processing application link, and has extremely high requirements on the aspects of setting property, rebound prevention, no wrinkling of the leather surface and the like, so that the solvent-free polyurethane shoe leather has no great breakthrough at present.
The solvent-free polyurethane synthetic leather product is prepared from solvent-free polyurethane resin, and the structural difference of the solvent-free polyurethane resin compared with the solvent-based polyurethane resin is mainly as follows: the network structure of the solvent-free resin coating is prepared through the crosslinking degree in the formula, so that the problem of insufficient mechanical properties caused by insufficient molecular weight of the solvent-free polyurethane resin is solved. Due to the existence of the cross-linked reticular structure, the solvent-free polyurethane synthetic leather has strong thermosetting property, poor plasticity and high rebound resilience, and the prepared solvent-free polyurethane shoe leather product has the problems of difficult shaping, easy rebound and the like in the post-processing process, thereby limiting the popularization and application of the solvent-free polyurethane shoe leather.
Under the background, an isocyanate prepolymer mixture for heat-settable, anti-rebound and non-wrinkling solvent-free polyurethane shoe leather is developed, and is matched with polyol components of different types to prepare a polyurethane resin material for the solvent-free shoe leather, so that the problems of difficult setting, easy rebound, easy wrinkling and the like in the post-processing process of the solvent-free polyurethane shoe leather are solved, and the method has extremely important significance. The research and development breakthrough of the invention is one of the important links for popularizing the solvent-free polyurethane synthetic leather technology and expanding the application in the shoe leather field.
The problem of strong thermosetting property of the solvent-free polyurethane resin coating is solved, and the main idea is to reduce the thermosetting property and improve the thermoplastic property of the solvent-free polyurethane resin coating. The invention mainly solves the problem from the development of isocyanate prepolymer: firstly, the molecular weight of the solvent-free polyurethane resin is improved, and the problems are mainly solved by reducing the percentage content of isocyanate in the isocyanate prepolymer, reducing the content of free isocyanate in the isocyanate prepolymer and improving the molecular weight of the isocyanate prepolymer; and secondly, a certain amount of organosilicon material with extremely low glass transition temperature and extremely high plasticity is introduced into the isocyanate prepolymer to improve the plasticity of the isocyanate prepolymer. Most of isocyanate prepolymers in the current market and the reports are modified by polyether polyol, polyester polyol, polycarbonate polyol and the like, most of the isocyanate prepolymers are isocyanate prepolymer materials with high free isocyanate content, the isocyanate prepolymer materials are applied to the preparation of solvent-free polyurethane resin coatings, and the formed polyurethane resin coatings have good structural elasticity and strong crosslinking and are difficult to meet the production and manufacture of solvent-free polyurethane shoe leather materials with high post-processing application requirements. The organosilicon material has been gradually researched and developed for application in isocyanate prepolymer material due to its unique properties such as excellent low temperature resistance, extremely low glass transition temperature, etc.
The invention patent CN107936216A reports 'an organic silicon modified isocyanate prepolymer for solvent-free synthetic leather and a preparation method thereof': the method comprises the steps of firstly preparing hydrogen-terminated methylphenyl polysiloxane by adopting octamethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane and tetramethyldihydrodisiloxane, then reacting with allylamine to prepare amino-terminated methylphenyl polysiloxane, finally reacting with isocyanate monomer to prepare organic silicon modified isocyanate prepolymer, and applying the organic silicon modified isocyanate prepolymer to the preparation of the solvent-free polyurethane synthetic leather so as to solve the problem of improving the air permeability and moisture permeability of the modified solvent-free polyurethane synthetic leather. The invention patent CN108503789A reports an open-cell polyurethane high-resilience foam composition and a preparation method thereof: the isocyanate composition is characterized by firstly preparing hydrogen-terminated polydimethylsiloxane from octamethylcyclotetrasiloxane and tetramethyldihydrodisiloxane, then reacting the hydrogen-terminated polydimethylsiloxane with allylamine to prepare amino-terminated polydimethylsiloxane, finally reacting the amino-terminated polydimethylsiloxane with an isocyanate monomer to prepare an organic silicon modified isocyanate prepolymer, and applying the isocyanate prepolymer to an open-cell high-resilience polyurethane foam composition to prepare the isocyanate composition which is not easy to delaminate. The invention patent CN108641059A reports 'a solvent-free middle layer polyurethane resin for cold-resistant automobile leather, a preparation method and application thereof': the preparation method comprises the steps of firstly synthesizing polycarbon type organic silicon polyol through modification, then reacting with isocyanate to prepare polycarbon type organic silicon polyol modified isocyanate prepolymer, applying the polycarbon type organic silicon polyol modified isocyanate prepolymer to the preparation of solvent-free polyurethane resin for cold-resistant automobile leather, and finally applying the polycarbon type organic silicon polyol modified isocyanate prepolymer to automobile interior leather materials to meet the requirement of high cold resistance of the automobile interior leather materials. We have recently reported the invention patent of "a solvent-free middle layer polyurethane resin for super soft synthetic leather and its preparation method": the organic silicon polyether diol with the molecular weight of 2000 and the organic silicon diamine with the molecular weight of 2000 are modified according to the mass ratio of 8/2-9/1 to prepare isocyanate prepolymer, and the isocyanate modified organic silicon diol is matched to prepare the solvent-free middle layer polyurethane resin for the super-soft synthetic leather, and the solvent-free middle layer polyurethane resin is applied to the preparation of the solvent-free polyurethane synthetic leather, so that the super-soft solvent-free polyurethane synthetic leather product with excellent low-temperature cold resistance can be prepared.
In the patent reports of the isocyanate prepolymer containing the organosilicon material, the problems of difficult shaping, easy rebound, easy wrinkling and the like in the subsequent processing are not related.
Disclosure of Invention
The invention aims to provide an isocyanate prepolymer mixture for solvent-free polyurethane shoe leather, a preparation method and application thereof, and aims to solve the problems of difficult shaping, easy rebound and easy wrinkling of leather surfaces in the post-processing process of solvent-free polyurethane shoe leather products.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a solvent-free isocyanate prepolymer mixture for polyurethane shoe leather is characterized in that: polyether modified isocyanate prepolymer B1 and organic silicon modified isocyanate prepolymer B2 are mixed according to the mass ratio of 9/1-4/6 and then diluted by reactive diluent S to obtain the modified isocyanate prepolymer;
the polyether modified isocyanate prepolymer B1 is obtained by reacting 21.5-64 parts by mass of isocyanate and 100 parts by mass of polyether diol, and the mass percentage of isocyanate in the polyether modified isocyanate prepolymer B1 obtained after the reaction is 4-8%;
the organic silicon modified isocyanate prepolymer B2 is obtained by reacting 100 parts by mass of isocyanate with 174-432.5 parts by mass of organic silicon dihydric alcohol, and the isocyanate content in the organic silicon modified isocyanate prepolymer B2 obtained after the reaction is 4-8% by mass.
The isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather is characterized by comprising the following components in parts by weight: the reactive diluent S is propylene carbonate.
The isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather is characterized by comprising the following components in parts by weight: in the polyether modified isocyanate prepolymer B1, the isocyanate is aliphatic isocyanate or aromatic isocyanate, specifically MDI and H12Any one of MDI.
The isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather is characterized by comprising the following components in parts by weight: in the polyether modified isocyanate prepolymer B1, the polyether diol is polyoxypropylene diol or polyoxypropylene diol-ethylene oxide diol copolymer with the molecular weight of 1000-4000.
The isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather is characterized by comprising the following components in parts by weight: in the organic silicon modified isocyanate prepolymer B2, isocyanate is formed by mixing carbodiimide modified MDI and MDI-30 according to the mass ratio of 95/5-70/30.
The isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather is characterized by comprising the following components in parts by weight: in the organic silicon modified isocyanate prepolymer B2, the organic silicon dihydric alcohol is hydroxyl-terminated organic silicon dihydric alcohol with the molecular weight of 2000-4000.
A preparation method of an isocyanate prepolymer mixture for solvent-free polyurethane shoe leather is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing polyether modified isocyanate prepolymer B1:
adding the selected isocyanate and polyether diol in parts by weight into a reaction kettle, heating to 70-90 ℃, stirring for reaction for 2-4 hours, detecting that hydroxyl groups in a reaction product are basically disappeared by infrared groups and the mass percentage content of the isocyanate meets the requirement, and cooling to 30-40 ℃ to obtain a polyether modified isocyanate prepolymer B1;
(2) preparing an organic silicon modified isocyanate prepolymer B2:
adding the selected isocyanate and the selected organic silicon dihydric alcohol into a reaction kettle according to respective mass parts, heating to 80-100 ℃, stirring for reaction for 3-5 hours, detecting that hydroxyl groups in a reaction product basically disappear through infrared groups and the mass percentage content of the isocyanate meets the requirement, and cooling to 30-40 ℃ to obtain an organic silicon modified isocyanate prepolymer B2;
(3) adding the polyether modified isocyanate prepolymer B1 prepared in the step (1) and the organic silicon modified isocyanate prepolymer B2 prepared in the step (2) into a reaction kettle according to the mass ratio of 9/1-4/6, heating to 40-60 ℃, adding a reactive diluent S, diluting to 90-60% of solid content and 3000-viscosity of 5000mPa.S/25 ℃, and cooling to 30-40 ℃ to obtain the solvent-free isocyanate prepolymer mixture for polyurethane shoe leather.
The application of the isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather is characterized in that: the solvent-free polyurethane shoe leather is prepared by reacting the isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather with polyester type, polycarbonate type or polyether type combined polyol, and the solvent-free polyurethane coating is applied to the production of the solvent-free polyurethane shoe leather, so that the solvent-free polyurethane shoe leather product can be shaped, prevent rebound and prevent wrinkling.
The application of the isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather is characterized in that: the reaction process comprises the steps of mixing the polyester type or polycarbon type or polyether type combined polyol with the isocyanate prepolymer mixture according to the designed theoretical proportion, fully stirring, and curing at the temperature of 100-130 ℃ for 5-10min to obtain the solvent-free polyurethane coating applied to the shoe leather.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention reports a technical scheme of an isocyanate prepolymer mixture which is provided for solving the problems of difficult sizing, easy rebound, easy wrinkling and the like in the post-processing process of a solvent-free polyurethane shoe leather product and is effectively applied to the solvent-free polyurethane shoe leather product for the first time.
2. The isocyanate prepolymer mixture provided by the invention can improve the molecular weight of the isocyanate prepolymer, improve the plasticity of the isocyanate prepolymer and reduce the thermosetting property of the isocyanate prepolymer mixture by reducing the percentage content of isocyanate of the isocyanate prepolymer mixture to 4-8%, thereby solving the basic premise that a solvent-free polyurethane shoe leather product can be shaped, prevent rebound and prevent wrinkling in the processing process.
3. In order to ensure that the isocyanate prepolymer mixture is easy to shape and prevent rebound in the post-processing process of a solvent-free polyurethane shoe leather product, polyether diol with 2 functionality and organic silicon diol are used for modification in the formula, so that the isocyanate prepolymer mixture with poor thermosetting property and excellent thermoplastic property is prepared; the polyether diol can only select polypropylene oxide diol or polypropylene oxide-ethylene oxide copolymer with low crystallinity and good flexibility, and can not select polytetrahydrofuran diol or polyester diol, polycarbonate diol and other materials with high crystallinity and good strength.
4. The isocyanate prepolymer mixture provided by the invention adopts a mode of cooperatively combining the polyether modified isocyanate prepolymer and the organic silicon modified isocyanate prepolymer, and is an optimal scheme for effectively solving the processing problems of heat setting, rebound prevention, no wrinkling and the like of a solvent-free shoe leather finished product; if only polyether modified isocyanate prepolymer is adopted, the applied solvent-free shoe leather finished product is rebound-proof and wrinkle-free, but the shaping performance is difficult to achieve; if only the organic silicon modified isocyanate prepolymer is adopted, the applied solvent-free shoe leather finished product can be subjected to heat setting and rebound prevention, but the leather surface is difficult to be free from wrinkling.
5. The isocyanate prepolymer mixture designed by the invention has lower percentage content of isocyanate and larger molecular weight, so the viscosity is larger, and the isocyanate prepolymer mixture is difficult to adapt to the processing viscosity requirement (generally the requirement is lower than 5000mPa.s/25 ℃) of low-pressure solvent-free polyurethane foaming equipment; the propylene carbonate serving as a reactive diluent with better isocyanate diluting performance is selected in the test, and the viscosity of the mixture can be controlled within the range of 3000-5000mPa.s/25 ℃ by diluting the solid content of the isocyanate prepolymer mixture to be 90-60%, so that the processing requirement of solvent-free equipment is met; in the matching reaction process of the isocyanate prepolymer mixture and the polyol A component, propylene carbonate can participate in the reaction with the polyol, so that the problem of insufficient environmental protection caused by the residue of the propylene carbonate in a solvent-free polyurethane resin coating is solved.
Detailed Description
The present invention is further illustrated by the following specific examples, but it should be noted that the specific material ratios, process conditions, results, etc. described in the examples of the present invention are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Example 1:
a solvent-free isocyanate prepolymer mixture for polyurethane shoe leather is prepared by mixing polyether modified isocyanate prepolymer B1 and organic silicon modified isocyanate prepolymer B2 according to a mass ratio of 9/1, and then diluting the mixture by a reactive diluent S until the solid content is 90 percent and the viscosity is 3000-5000mPa.S/25 ℃;
the polyether modified isocyanate prepolymer B1 is a mixture with the isocyanate mass percentage of 8%, and comprises the following components in parts by mass:
64 parts of MDI (diphenyl-methane-diisocyanate),
100 parts of DDL-1000D;
the organic silicon modified isocyanate prepolymer B2 is a mixture with isocyanate mass percent of 8%, and comprises the following components in parts by mass:
95 parts of MDI-100L (diphenyl-methane-diisocyanate),
MDI-305 parts of (methyl diphenyl methane-diisocyanate),
tech-2120174 parts;
the reactive diluent S is a Jeffsol propylene carbonate product produced by Huntsman company in the United states; MDI is a pure 4,4 ' -diphenylmethane diisocyanate product produced by Nicotiana Vanhua chemical company, MDI-100L is a carbodiimide modified isocyanate product produced by Nicotiana Vanhua chemical company, and MDI-30 is a mixture product of 30 mass percent of 4,4 ' -diphenylmethane diisocyanate and 70 mass percent of 2,4 ' -diphenylmethane diisocyanate produced by Nicotiana Vanhua chemical company; DDL-1000D is a polyoxypropylene diol product having a molecular weight of 1000 produced by Federal, Dengxin, Shandong; tech-2120 is a 2000 molecular weight silicone glycol product from Shanghai tag Polymer technology, Inc.
The preparation method of the solvent-free isocyanate prepolymer mixture for polyurethane shoe leather comprises the following steps:
(1) adding MDI (64 parts) and DDL-1000D (100 parts) into a reaction kettle, heating to 70 ℃, stirring for reaction for 4 hours, detecting that hydroxyl groups basically disappear by infrared detection, cooling to 30 ℃ after the percentage content of isocyanate meets the requirement (8 +/-0.2 percent), and discharging to obtain a component B1;
(2) adding MDI-100L (95 parts), MDI-30(5 parts) and organosilicon diol Tech-2120(174 parts) into a reaction kettle, heating to 100 ℃, stirring for reaction for 5 hours, reducing the temperature to 30 ℃ after hydroxyl groups are basically disappeared by infrared group detection and the percentage content of isocyanate meets the requirement (8 +/-0.2%), and discharging to obtain a component B2;
(3) adding the prepared component B1 and the prepared component B2 into a reaction kettle according to the mass ratio of 9/1, heating to 40 ℃, adding a reactive type reactive diluent S to dilute until the solid content is 90 percent, cooling to 30 ℃ after the viscosity is detected to be qualified (3000 plus 5000mPa. S/25 ℃), and discharging to obtain an isocyanate prepolymer mixture;
mixing the prepared isocyanate prepolymer mixture with polyester type combined polyol according to a designed theoretical proportion, fully stirring, and curing at 100 ℃ for 10min to obtain the solvent-free polyurethane coating applied to shoe leather.
Example 2:
a solvent-free isocyanate prepolymer mixture for polyurethane shoe leather is prepared by mixing polyether modified isocyanate prepolymer B1 and organic silicon modified isocyanate prepolymer B2 according to a mass ratio of 4/6, and then diluting the mixture by a reactive diluent S until the solid content is 60 percent and the viscosity is 3000-5000mPa.S/25 ℃;
the polyether modified isocyanate prepolymer B1 is a mixture with isocyanate content of 4% by weight, and comprises the following components in parts by weight:
21.5 parts of H12MDI (diphenylmethane diisocyanate),
100 parts of DDL-4000D,
the organic silicon modified isocyanate prepolymer B2 is a mixture with isocyanate content of 4% by mass, and comprises the following components in parts by mass:
70 parts of MDI-100L (diphenyl-methane-diisocyanate),
MDI-3030 part of (MDI-3030),
tech-2140432.5 parts by weight of a catalyst,
h12MDI is a hydrogenated 4, 4' -diphenylmethane diisocyanate product produced by Nicotiana Vanhua chemical company; DDL-4000D is a polyoxypropylene diol product of molecular weight 4000 produced by Shandong Dexin Federal; tech-2140 is a 4000 molecular weight silicone glycol product from Shanghai Tager Polymer technology, Inc.
The preparation method of the isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather comprises the following steps:
(1) adding H12MDI (21.5 parts) and DDL-4000D (100 parts) into a reaction kettle, heating to 90 ℃, stirring for reaction for 2 hours, detecting that hydroxyl groups basically disappear by infrared, cooling to 40 ℃ after the percentage content of isocyanate meets the requirement (4 +/-0.2 percent), and discharging to obtain a component B1;
(2) adding MDI-100L (70 parts), MDI-30(30 parts) and organic silicon dihydric alcohol Tech-2140(432.5 parts) into a reaction kettle, heating to 80 ℃, stirring for reaction for 3 hours, detecting that hydroxyl groups basically disappear by infrared groups, cooling to 40 ℃ after the percentage content of isocyanate meets the requirement (4 +/-0.2 percent), and discharging to obtain a component B2;
(3) adding the prepared component B1 and the prepared component B2 into a reaction kettle according to the mass ratio of 4/6, heating to 60 ℃, adding a reactive type reactive diluent S to dilute until the solid content is 60 percent, cooling to 40 ℃ after the viscosity is detected to be qualified (3000 plus 5000mPa. S/25 ℃), and discharging to obtain an isocyanate prepolymer mixture;
mixing the prepared isocyanate prepolymer mixture with the polycarbonate type combined polyol according to a designed theoretical proportion, fully stirring, and curing at 130 ℃ for 5min to obtain the solvent-free polyurethane coating applied to shoe leather.
Example 3:
a solvent-free isocyanate prepolymer mixture for polyurethane shoe leather is prepared by mixing polyether modified isocyanate prepolymer B1 and organic silicon modified isocyanate prepolymer B2 according to a mass ratio of 7/3, and then diluting the mixture by a reactive diluent S until the solid content is 80% and the viscosity is 5000mPa.S/25 ℃;
the polyether modified isocyanate prepolymer B1 is a mixture with isocyanate content of 6% by weight, and comprises the following components in parts by weight:
37 parts of MDI (diphenylmethane diisocyanate),
100 parts of DP-2000E,
the organic silicon modified isocyanate prepolymer B2 is a mixture with isocyanate content of 6% by weight, and comprises the following components in parts by weight:
80 parts of MDI-100L,
MDI-3020 parts of (diphenyl-methane-diisocyanate),
tech-2140295 parts by weight of a catalyst,
DP-2000E is a polyoxypropylene-oxyethylene copolyol product of molecular weight 2000 produced by Kunshan Country chemical;
the preparation method of the isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather comprises the following steps:
(1) adding MDI (37 parts) and DP-2000E (100 parts) into a reaction kettle, heating to 80 ℃, stirring for reaction for 3 hours, detecting that hydroxyl groups basically disappear by infrared detection, cooling to 35 ℃ after the percentage content of isocyanate meets the requirement (6 +/-0.2 percent), and discharging to obtain a component B1;
(2) adding MDI-100L (80 parts), MDI-30(20 parts) and organic silicon dihydric alcohol Tech-2140(295 parts) into a reaction kettle, heating to 90 ℃, stirring for reaction for 4 hours, detecting that hydroxyl groups basically disappear by infrared groups, cooling to 35 ℃ after the percentage content of isocyanate meets the requirement (6 +/-0.2 percent), and discharging to obtain a component B2;
(3) adding the prepared component B1 and the prepared component B2 into a reaction kettle according to the mass ratio of 7/3, heating to 50 ℃, adding a reactive type reactive diluent S to dilute until the solid content is 80 percent, cooling to 35 ℃ after the viscosity is detected to be qualified (3000 plus 5000mPa. S/25 ℃), and discharging to obtain an isocyanate prepolymer mixture;
mixing the prepared isocyanate prepolymer mixture with polyether type combined polyol according to a designed theoretical proportion, fully stirring, and curing at 120 ℃ for 8min to obtain the solvent-free polyurethane coating applied to shoe leather.
Comparative example 1:
an isocyanate prepolymer mixture for heat-setting, anti-rebound, non-wrinkling and solvent-free polyurethane shoe leather consists of polyether modified isocyanate prepolymer B1, and is diluted by reactive diluent S to reach the solid content of 90 percent and the viscosity of 3000-plus 5000mPa.S/25 ℃;
the polyether modified isocyanate prepolymer B1 is a mixture with the isocyanate mass percentage of 8%, and comprises the following components in parts by mass:
64 parts of MDI (diphenyl-methane-diisocyanate),
100 parts of DDL-1000D,
the preparation method comprises the following steps:
(1) adding MDI (64 parts) and DDL-1000D (100 parts) into a reaction kettle, heating to 70 ℃, stirring for reaction for 4 hours, detecting that hydroxyl groups basically disappear by infrared detection, cooling to 30 ℃ after the percentage content of isocyanate meets the requirement (8 +/-0.2 percent), and discharging to obtain a component B1;
(2) adding the prepared component B1 into a reaction kettle, heating to 40 ℃, adding a reactive type reactive diluent S to dilute to 90% of solid content, cooling to 30 ℃ after detecting that the viscosity is qualified (3000-;
mixing the prepared isocyanate prepolymer mixture with polyester type combined polyol according to a designed theoretical proportion, fully stirring, and curing at 100 ℃ for 10min to obtain the solvent-free polyurethane coating applied to shoe leather.
Comparative example 2:
an isocyanate prepolymer mixture for heat-setting, anti-rebound, non-wrinkling and solvent-free polyurethane shoe leather consists of organosilicon modified isocyanate prepolymer B2, and is diluted by reactive diluent S to reach the solid content of 60 percent and the viscosity of 3000-plus 5000mPa.S/25 ℃;
the organic silicon modified isocyanate prepolymer B2 is a mixture with isocyanate content of 4% by mass, and comprises the following components in parts by mass:
70 parts of MDI-100L (diphenyl-methane-diisocyanate),
MDI-3030 part of (MDI-3030),
tech-2140432.5 parts by weight of a catalyst,
the preparation method comprises the following steps:
(1) adding MDI-100L (70 parts), MDI-30(30 parts) and organic silicon dihydric alcohol Tech-2140(432.5 parts) into a reaction kettle, heating to 80 ℃, stirring for reaction for 3 hours, detecting that hydroxyl groups basically disappear by infrared groups, cooling to 40 ℃ after the percentage content of isocyanate meets the requirement (4 +/-0.2 percent), and discharging to obtain a component B2;
(2) adding the prepared component B2 into a reaction kettle, heating to 60 ℃, adding a reactive type reactive diluent S to dilute to 60% of solid content, cooling to 40 ℃ after the viscosity is detected to be qualified (3000-;
mixing the prepared isocyanate prepolymer mixture with the polycarbonate type combined polyol according to a designed theoretical proportion, fully stirring, and curing at 130 ℃ for 5min to obtain the solvent-free polyurethane coating applied to shoe leather.
Comparative example 3:
an isocyanate prepolymer mixture for heat-setting, anti-rebound and non-wrinkling solvent-free polyurethane shoe leather is prepared by mixing polyether modified isocyanate prepolymer B1 and organic silicon modified isocyanate prepolymer B2 according to mass ratio of 3/7, and then diluting the mixture by reactive diluent S to solid content of 60 percent and viscosity of 3000-plus 5000mPa.S/25 ℃;
the polyether modified isocyanate prepolymer B1 is a mixture with isocyanate content of 4% by weight, and comprises the following components in parts by weight:
21.5 parts of H12MDI (diphenylmethane diisocyanate),
100 parts of DDL-4000D,
the organic silicon modified isocyanate prepolymer B2 is a mixture with isocyanate content of 4% by mass, and comprises the following components in parts by mass:
70 parts of MDI-100L (diphenyl-methane-diisocyanate),
MDI-3030 part of (MDI-3030),
tech-2140432.5 parts by weight of a catalyst,
the preparation method comprises the following steps:
(1) adding H12MDI (21.5 parts) and DDL-4000D (100 parts) into a reaction kettle, heating to 90 ℃, stirring for reaction for 2 hours, detecting that hydroxyl groups basically disappear by infrared, cooling to 40 ℃ after the percentage content of isocyanate meets the requirement (4 +/-0.2 percent), and discharging to obtain a component B1;
(2) adding MDI-100L (70 parts), MDI-30(30 parts) and organic silicon dihydric alcohol Tech-2140(432.5 parts) into a reaction kettle, heating to 80 ℃, stirring for reaction for 3 hours, detecting that hydroxyl groups basically disappear by infrared groups, cooling to 40 ℃ after the percentage content of isocyanate meets the requirement (4 +/-0.2 percent), and discharging to obtain a component B2;
(3) adding the prepared component B1 and the prepared component B2 into a reaction kettle according to the mass ratio of 3/7, heating to 60 ℃, adding a reactive type reactive diluent S to dilute until the solid content is 60 percent, cooling to 40 ℃ after the viscosity is detected to be qualified (3000 plus 5000mPa. S/25 ℃), and discharging to obtain an isocyanate prepolymer mixture;
mixing the prepared isocyanate prepolymer mixture with the polycarbonate type combined polyol according to a designed theoretical proportion, fully stirring, and curing at 130 ℃ for 5min to obtain the solvent-free polyurethane coating applied to shoe leather.
Comparative example 4:
an isocyanate prepolymer mixture for heat-setting, anti-rebound and non-wrinkling solvent-free polyurethane shoe leather is prepared by mixing polyether modified isocyanate prepolymer B1 and organic silicon modified isocyanate prepolymer B2 according to mass ratio of 9/1, and then diluting the mixture by reactive diluent S to solid content of 90 percent and viscosity of 3000-plus 5000mPa.S/25 ℃;
the polyether modified isocyanate prepolymer B1 is a mixture with the isocyanate mass percentage of 8%, and comprises the following components in parts by mass:
64 parts of MDI (diphenyl-methane-diisocyanate),
1000100 parts of PolyTHF (PolyTHF) (PolyTHF preparation),
the organic silicon modified isocyanate prepolymer B2 is a mixture with isocyanate mass percent of 8%, and comprises the following components in parts by mass:
95 parts of MDI-100L (diphenyl-methane-diisocyanate),
MDI-305 parts of (methyl diphenyl methane-diisocyanate),
tech-2120174 parts by weight of a catalyst,
PTMG-1 is a polytetrahydrofuran diol product having a molecular weight of 1000, produced by BASF corporation, Germany.
The preparation method comprises the following steps:
(1) adding MDI (64 parts) and PolyTHF 1000(100 parts) into a reaction kettle, heating to 70 ℃, stirring for reaction for 4 hours, detecting by infrared that hydroxyl groups basically disappear, cooling to 30 ℃ after the percentage content of isocyanate meets the requirement (8 +/-0.2 percent), and discharging to obtain a component B1;
(2) adding MDI-100L (95 parts), MDI-30(5 parts) and organosilicon diol Tech-2120(174 parts) into a reaction kettle, heating to 100 ℃, stirring for reaction for 5 hours, reducing the temperature to 30 ℃ after hydroxyl groups are basically disappeared by infrared group detection and the percentage content of isocyanate meets the requirement (8 +/-0.2%), and discharging to obtain a component B2;
(3) adding the prepared component B1 and the prepared component B2 into a reaction kettle according to the mass ratio of 9/1, heating to 40 ℃, adding a reactive type reactive diluent S to dilute until the solid content is 90 percent, cooling to 30 ℃ after the viscosity is detected to be qualified (3000 plus 5000mPa. S/25 ℃), and discharging to obtain an isocyanate prepolymer mixture;
mixing the prepared isocyanate prepolymer mixture with polyester type combined polyol according to a designed theoretical proportion, fully stirring, and curing at 100 ℃ for 10min to obtain the solvent-free polyurethane coating applied to shoe leather.
Comparative example 5:
an isocyanate prepolymer mixture for heat-setting, anti-rebound and non-wrinkling solvent-free polyurethane shoe leather is prepared by mixing polyether modified isocyanate prepolymer B1 and organic silicon modified isocyanate prepolymer B2 according to mass ratio of 9/1, and then diluting the mixture by reactive diluent S to solid content of 90 percent and viscosity of 3000-plus 5000mPa.S/25 ℃;
the polyether modified isocyanate prepolymer B1 is a mixture with the isocyanate mass percentage of 8%, and comprises the following components in parts by mass:
45.5 parts of MDI (diphenylmethane diisocyanate),
SP-2313100 parts of a mixture of (S-I),
the organic silicon modified isocyanate prepolymer B2 is a mixture with isocyanate mass percent of 8%, and comprises the following components in parts by mass:
95 parts of MDI-100L (diphenyl-methane-diisocyanate),
MDI-305 parts of (methyl diphenyl methane-diisocyanate),
tech-2120174 parts by weight of a catalyst,
SP-2313 is an adipic acid polyester diol product with the molecular weight of 2300 produced by Hefei anli polyurethane new material Co.
The preparation method comprises the following steps:
(1) adding MDI (45.5 parts) and SP-2313(100 parts) into a reaction kettle, heating to 70 ℃, stirring for reaction for 4 hours, detecting that hydroxyl groups basically disappear by infrared detection, cooling to 30 ℃ after the percentage content of isocyanate meets the requirement (8 +/-0.2 percent), and discharging to obtain a component B1;
(2) adding MDI-100L (95 parts), MDI-30(5 parts) and organosilicon diol Tech-2120(174 parts) into a reaction kettle, heating to 100 ℃, stirring for reaction for 5 hours, reducing the temperature to 30 ℃ after hydroxyl groups are basically disappeared by infrared group detection and the percentage content of isocyanate meets the requirement (8 +/-0.2%), and discharging to obtain a component B2;
(3) adding the prepared component B1 and the prepared component B2 into a reaction kettle according to the mass ratio of 9/1, heating to 40 ℃, adding a reactive type reactive diluent S to dilute until the solid content is 90 percent, cooling to 30 ℃ after the viscosity is detected to be qualified (3000 plus 5000mPa. S/25 ℃), and discharging to obtain an isocyanate prepolymer mixture;
mixing the prepared isocyanate prepolymer mixture with polyester type combined polyol according to a designed theoretical proportion, fully stirring, and curing at 100 ℃ for 10min to obtain the solvent-free polyurethane coating applied to shoe leather.
Comparative example 6:
an isocyanate prepolymer mixture for heat-setting, anti-rebound and non-wrinkling solvent-free polyurethane shoe leather is prepared by mixing polyether modified isocyanate prepolymer B1 and organic silicon modified isocyanate prepolymer B2 according to mass ratio of 9/1, and then diluting the mixture by reactive diluent S to solid content of 90 percent and viscosity of 3000-plus 5000mPa.S/25 ℃;
the polyether modified isocyanate prepolymer B1 is a mixture with the isocyanate mass percentage of 8%, and comprises the following components in parts by mass:
47.5 parts of MDI (diphenylmethane diisocyanate),
100 parts of CD-220PL (basic polystyrene),
the organic silicon modified isocyanate prepolymer B2 is a mixture with isocyanate mass percent of 8%, and comprises the following components in parts by mass:
95 parts of MDI-100L (diphenyl-methane-diisocyanate),
MDI-305 parts of (methyl diphenyl methane-diisocyanate),
tech-2120174 parts by weight of a catalyst,
CD 220PL is a 2000 molecular weight polycarbonate diol product of Daiiol from Japan K.K.
The preparation method comprises the following steps:
(1) adding MDI (47.5 parts) and CD-220PL (100 parts) into a reaction kettle, heating to 70 ℃, stirring for reaction for 4 hours, detecting that hydroxyl groups basically disappear by infrared detection, cooling to 30 ℃ after the percentage content of isocyanate meets the requirement (8 +/-0.2 percent), and discharging to obtain a component B1;
(2) adding MDI-100L (95 parts), MDI-30(5 parts) and organosilicon diol Tech-2120(174 parts) into a reaction kettle, heating to 100 ℃, stirring for reaction for 5 hours, reducing the temperature to 30 ℃ after hydroxyl groups are basically disappeared by infrared group detection and the percentage content of isocyanate meets the requirement (8 +/-0.2%), and discharging to obtain a component B2;
(3) adding the prepared component B1 and the prepared component B2 into a reaction kettle according to the mass ratio of 9/1, heating to 40 ℃, adding a reactive type reactive diluent S to dilute until the solid content is 90 percent, cooling to 30 ℃ after the viscosity is detected to be qualified (3000 plus 5000mPa. S/25 ℃), and discharging to obtain an isocyanate prepolymer mixture;
mixing the prepared isocyanate prepolymer mixture with polyester type combined polyol according to a designed theoretical proportion, fully stirring, and curing at 100 ℃ for 10min to obtain the solvent-free polyurethane coating applied to shoe leather.
The isocyanate prepolymer mixture for the heat-settable, anti-rebound and non-wrinkling solvent-free polyurethane shoe leather prepared in the embodiment and the comparative example is applied as follows: firstly, taking the prepared isocyanate prepolymer mixture as a component B, matching with a component A of polyol for a solvent-free surface layer, and reacting to prepare a solvent-free polyurethane surface layer coating; secondly, taking the prepared isocyanate prepolymer mixture as a component B, matching with a polyol component A for a solvent-free middle layer, and reacting to obtain a solvent-free polyurethane middle layer coating; and finally, matching the prepared solvent-free polyurethane surface layer coating and the prepared solvent-free polyurethane middle layer coating with base cloth for shoe leather to prepare a solvent-free polyurethane shoe leather product. And respectively carrying out post-processing tests on the prepared solvent-free polyurethane shoe leather products, detecting whether the solvent-free polyurethane shoe leather products have the effects of heat setting, rebound prevention, no wrinkling and the like, and avoiding the defects of post-processing.
The post-processing results of the solvent-free polyurethane shoe leathers obtained in examples 1 to 3 and comparative examples 1 to 6 are shown in Table 1:
TABLE 1 processing results table
Note: the detection result is detected by special shoe material processing and shaping equipment.
According to the above detection results, it can be found that: in comparative example 1, if only polyether modified isocyanate B1 is used as the B component, the post-processing process is difficult to shape, although the anti-rebound and non-wrinkling process can be realized; in comparative example 2, if only organosilicon modified isocyanate B2 is used as the component B, although the post-processing process is easy to shape and prevent rebound, the wrinkling of the shoe leather surface is obvious; in the comparative example 3, when the content of the organosilicon modified isocyanate B2 is increased, namely the content of B1/B2 is increased from 4/6 to 3/7, the shoe leather surface is slightly wrinkled on the premise of good setting property and anti-rebound effect; in comparative examples 4 to 6, when the component B1 was changed to polytetrahydrofuran diol-modified isocyanate, polyester diol-modified isocyanate, or polycarbonate diol-modified isocyanate, the shoe leather surface did not wrinkle, but the different degrees of difficult setting and rebound occurred. Thus, by way of a comprehensive comparison, the application of examples 1-3 to the preparation and post-processing of solvent-free polyurethane shoe leather provides the best solution.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (6)
1. A solvent-free isocyanate prepolymer mixture for polyurethane shoe leather is characterized in that: polyether modified isocyanate prepolymer B1 and organic silicon modified isocyanate prepolymer B2 are mixed according to the mass ratio of 9/1-4/6 and then diluted by reactive diluent S to obtain the modified isocyanate prepolymer;
the polyether modified isocyanate prepolymer B1 is obtained by reacting 21.5-64 parts by mass of isocyanate and 100 parts by mass of polyether diol, and the mass percentage of isocyanate in the polyether modified isocyanate prepolymer B1 obtained after the reaction is 4-8%;
the organic silicon modified isocyanate prepolymer B2 is obtained by reacting 100 parts by weight of isocyanate with 174-432.5 parts by weight of organic silicon dihydric alcohol, and the isocyanate content in the organic silicon modified isocyanate prepolymer B2 obtained after the reaction is 4-8% by weight;
in the polyether modified isocyanate prepolymer B1, the isocyanate is MDI and H12Any one of MDI;
in the polyether modified isocyanate prepolymer B1, the polyether diol is polyoxypropylene diol or polyoxypropylene diol-ethylene oxide diol copolymer with the molecular weight of 1000-4000;
in the organic silicon modified isocyanate prepolymer B2, isocyanate is formed by mixing carbodiimide modified MDI and MDI-30 according to the mass ratio of 95/5-70/30.
2. The isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather as claimed in claim 1, wherein: the reactive diluent S is propylene carbonate.
3. The isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather as claimed in claim 1, wherein: in the organic silicon modified isocyanate prepolymer B2, the organic silicon dihydric alcohol is hydroxyl-terminated organic silicon dihydric alcohol with the molecular weight of 2000-4000.
4. A method for preparing the isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather according to claim 1, which is characterized in that: the method comprises the following steps:
(1) preparing polyether modified isocyanate prepolymer B1:
adding the selected isocyanate and polyether diol in parts by weight into a reaction kettle, heating to 70-90 ℃, stirring for reaction for 2-4 hours, detecting that hydroxyl groups in a reaction product are basically disappeared by infrared groups and the mass percentage content of the isocyanate meets the requirement, and cooling to 30-40 ℃ to obtain a polyether modified isocyanate prepolymer B1;
(2) preparing an organic silicon modified isocyanate prepolymer B2:
adding the selected isocyanate and the selected organic silicon dihydric alcohol into a reaction kettle according to respective mass parts, heating to 80-100 ℃, stirring for reaction for 3-5 hours, detecting that hydroxyl groups in a reaction product basically disappear through infrared groups and the mass percentage content of the isocyanate meets the requirement, and cooling to 30-40 ℃ to obtain an organic silicon modified isocyanate prepolymer B2;
(3) adding the polyether modified isocyanate prepolymer B1 prepared in the step (1) and the organic silicon modified isocyanate prepolymer B2 prepared in the step (2) into a reaction kettle according to the mass ratio of 9/1-4/6, heating to 40-60 ℃, adding a reactive diluent S, diluting to 90-60% of solid content and 3000-viscosity of 5000mPa.S/25 ℃, and cooling to 30-40 ℃ to obtain the solvent-free isocyanate prepolymer mixture for polyurethane shoe leather.
5. The use of the isocyanate prepolymer mixture for solvent-free polyurethane shoe leather according to claim 1, wherein the isocyanate prepolymer mixture comprises: the solvent-free polyurethane shoe leather is prepared by reacting the isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather with polyester type, polycarbonate type or polyether type combined polyol, and the solvent-free polyurethane coating is applied to the production of the solvent-free polyurethane shoe leather, so that the solvent-free polyurethane shoe leather product can be shaped, prevent rebound and prevent wrinkling.
6. The use of the isocyanate prepolymer mixture for the solvent-free polyurethane shoe leather as claimed in claim 5, wherein: the reaction process comprises the steps of mixing the polyester type or polycarbon type or polyether type combined polyol with the isocyanate prepolymer mixture according to the designed theoretical proportion, fully stirring, and curing at the temperature of 100-130 ℃ for 5-10min to obtain the solvent-free polyurethane coating applied to the shoe leather.
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