CN110835401B - Waterborne polyurethane surface layer resin and preparation method thereof - Google Patents
Waterborne polyurethane surface layer resin and preparation method 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
- C08G18/28—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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
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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
- C08G18/61—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8054—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
- C08G18/8077—Oximes
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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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- 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
- D06N3/147—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 isocyanates used
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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
- D06N2203/00—Macromolecular materials of the coating layers
- D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06N2203/068—Polyurethanes
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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
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1685—Wear resistance
Abstract
The invention discloses a waterborne polyurethane surface layer resin which is prepared from the following raw materials in parts by weight: 10-30 parts of polymeric polyol, 0-5 parts of polyether modified silicone oil, 0-5 parts of self-made sulfonate polymeric polyol, 10-30 parts of isocyanate, 0.1-2 parts of small molecular polyol, 1-5 parts of hydrophilic chain extender, 0.1-1 part of small molecular amino-terminated compound, 40-60 parts of deionized water, 1-3 parts of self-made closed water-based isocyanate crosslinking agent and 1-5 parts of pH value regulator. The waterborne polyurethane surface resin is an environment-friendly material and meets the environmental protection standard of European Union; the resin has hydrolysis resistance, cold resistance, smoothness and wear resistance, and does not have the bad phenomena of poor adhesive force, even delamination and the like when being matched with solvent-free two-component glue for use.
Description
Technical Field
The invention relates to the field of waterborne polyurethane surface resin for synthetic leather, in particular to preparation of surface resin with good adhesion with solvent-free two-component glue, and specifically relates to waterborne polyurethane surface resin with good adhesion with solvent-free two-component glue, and a preparation method of the resin.
Background
Synthetic leather has been widely used in the daily life of people. The traditional synthetic leather production mode adopts a large amount of toxic and harmful solvents such as DMF, butanone, ethyl acetate and the like, and nowadays, the production and processing mode which takes the cost of sacrificing ecological environment and human health has been resisted and limited by various circles of society at the higher and higher requirements on environmental protection. How to replace the current raw materials and production methods with more harmonious and environmentally friendly raw materials and production methods has become a big issue that the industry must face, and the problem has become very reluctant.
The solvent-free two-component polyurethane replaces the traditional solvent-based adhesive and wet coating, which is an important change in recent years, and the synthetic leather products are relatively mature at present and are greatly popularized in the market. However, due to the limitations of the product structure and the using process of the solvent-free two-component polyurethane, the product is only used as a bonding layer and a wet coating of synthetic leather in large batch at present, and most of the surface layer resin of the synthetic leather still uses solvent type resin.
The waterborne polyurethane resin is used as synthetic leather surface layer resin matched with solvent-free two-component glue, so that comprehensive solvent-free and environment-friendly production process of the synthetic leather is realized, and the waterborne polyurethane resin is a new attempt in recent years. However, the situation of delamination of the surface and the bottom and the like is caused by the poor binding force between the aqueous polyurethane resin and the solvent-free two-component adhesive, and the development of the overall environmental protection progress of the industry is also limited.
The inventor finds that the bottom surface delamination phenomenon is more serious along with the increase of the DMPA dosage in the water-based polyurethane structure through research.
Based on the situation, the invention provides the waterborne polyurethane surface layer resin and the preparation method thereof, which can effectively solve the problems.
Disclosure of Invention
The invention aims to provide an aqueous polyurethane surface layer resin and a preparation method thereof, namely an aqueous polyurethane surface layer resin which is well adhered to a solvent-free two-component adhesive and a preparation method thereof, so as to solve the problems of difficult combination of the existing aqueous polyurethane resin and the solvent-free two-component adhesive and the like.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the waterborne polyurethane surface layer resin is prepared from the following raw materials in parts by weight: 10-30 parts of polymeric polyol, 0-5 parts of polyether modified silicone oil, 0-5 parts of self-made sulfonate polymeric polyol, 10-30 parts of isocyanate, 0.1-2 parts of micromolecule polyol, 1-5 parts of hydrophilic chain extender, 0.1-1 part of micromolecule amino-terminated compound, 40-60 parts of deionized water, 1-3 parts of self-made closed water-based isocyanate cross-linking agent and 1-5 parts of pH value regulator.
The waterborne polyurethane surface resin with good adhesion with the solvent-free two-component adhesive is an environment-friendly material and meets the environmental protection standard of European Union; the waterborne polyurethane surface layer resin with good adhesion with the solvent-free two-component glue belongs to surface layer resins for synthetic leather, has hydrolysis resistance, cold resistance, smoothness and wear resistance, and does not have the bad phenomena of poor adhesion and even delamination and the like when being matched with the solvent-free two-component glue for use.
According to the invention, a sulfonate type polyol raw material is prepared, and the use of the raw material matched with a non-ionic hydrophilic chain extender replaces the use of DMPA, so that the adhesion of the water-based surface layer and the solvent-free two-component adhesive is improved, and the curing time of the solvent-free two-component adhesive is shortened. However, the peel strength still cannot meet the requirements of synthetic leather or microfiber products such as shoe leather, automobile leather and the like with high peeling requirements.
The second key point of the invention is that a closed water-based polyurethane cross-linking agent raw material which can be rapidly deblocked at the temperature of more than 100 ℃ is prepared. NCO groups deblocked from the raw material in the process of high-temperature curing (usually 120-140 ℃) of the solvent-free adhesive can generate a bridging effect between the main chain of the waterborne polyurethane and the solvent-free adhesive, so that the adhesion fastness, namely the peeling strength, of the surface primer is obviously improved.
In addition, by means of organic silicon modification and the like, the waterborne polyurethane surface layer has good adhesive force with the solvent-free adhesive, and also has excellent performances of leveling, smoothness, wear resistance, scratch resistance, cold resistance, folding resistance and the like.
Preferably, the waterborne polyurethane surface layer resin is prepared from the following raw materials in parts by weight: 15-25 parts of polymeric polyol, 3-5 parts of polyether modified silicone oil, 3-5 parts of self-made sulfonate polymeric polyol, 20-30 parts of isocyanate, 0.5-1.5 parts of micromolecule polyol, 2-4 parts of hydrophilic chain extender, 0.3-0.8 part of micromolecule amino-terminated compound, 45-55 parts of deionized water, 2-3 parts of self-made closed water-based isocyanate cross-linking agent and 1-3.5 parts of pH value regulator.
Preferably, the polymeric polyol is any one or more of polyethylene glycol adipate glycol, 1, 4-butanediol adipate glycol, 1, 6-hexanediol adipate glycol, diethylene glycol adipate glycol, polycarbonate glycol, polytetrahydrofuran glycol, polypropylene glycol, polyethylene glycol and N330.
More preferably, the polymeric polyol is any one or more of 1, 4-butanediol adipate diol, polytetrahydrofuran diol and N330.
Preferably, the polyether modified silicone oil is a dihydric alcohol which is formed by graft copolymerization of polyether and dimethyl siloxane and has the relative molecular mass of 1000-2000.
More preferably, the polyether modified silicone oil is polyether modified silicone oil with relative molecular mass of 2000, which is formed by graft copolymerization of polyether and dimethyl siloxane.
Preferably, the homemade sulfonate type polymeric polyol is prepared by the following method: adding hexanediol, adipic acid, trimethylolpropane and a sodium dihydroxy sulfonate solution into a flask, heating to 120 ℃, and reacting for 2-3 h; and then heating to 200 +/-5 ℃ for reaction, removing water in the system under reduced pressure, testing the hydroxyl value and the acid value every 1h, wherein the end point is as follows: the hydroxyl value is 100-120mg KOH/g, and the acid value is less than or equal to 1mg KOH/g.
Preferably, the isocyanate is any one or more of 4,4' -diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and xylylene diisocyanate.
More preferably, the isocyanate is 4,4' -diphenylmethane diisocyanate (HMDI).
Preferably, the small molecular polyol is any one or more of ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1, 6-hexanediol, diethylene glycol, trimethylolpropane, triethanolamine, glycerol, N303 and castor oil.
More preferably, the small molecule polyol is a mixture of butanediol and trimethylolpropane.
Preferably, the micromolecular hydrophilic chain extender is any one or more of a carboxylic acid compound with double hydroxyl groups, a non-ionic hydrophilic agent and sulfamate.
Preferably, the small molecule hydrophilic chain extender is a dihydroxyl nonionic hydrophilic agent.
Preferably, the small molecule amino-terminated compound is any one or more of ethylenediamine, isophoronediamine, hexamethylenediamine, hydrazine hydrate, KH-550 and KH-560.
More preferably, the small molecule amino-terminated compound is ethylenediamine.
Preferably, the self-made blocked water-based isocyanate crosslinking agent is prepared by the following method: toluene Diisocyanate (TDI), Trimethylolpropane (TMP) and sodium dihydroxysulfonate/DMSO solution are fed into a reaction kettle at one step, and the NCO content is tested to be 11 +/-1% by a toluene-di-n-butylamine method; and (3) carrying out blocking reaction for 3 +/-0.5 h at 70-80 ℃ by adopting butanone oxime, and stopping without NCO peak in infrared detection.
The invention also provides a preparation method of the waterborne polyurethane surface layer resin, which comprises the following steps:
1) weighing the raw materials in parts by weight; adding polymeric polyol, polyether modified silicone oil, self-made sulfonate polymeric polyol and a hydrophilic chain extender into a flask, heating to 110-120 ℃, and dehydrating under reduced pressure for 1-2 hours;
2) cooling the mixture obtained in the step 1) to below 70 ℃, adding isocyanate, heating to 85-90 ℃, adding a catalyst, carrying out heat preservation reaction at the temperature for 2 hours, and measuring the NCO content;
3) cooling the mixture obtained in the step 2) to 50 +/-3 ℃, adding small molecular polyol, carrying out heat preservation reaction at the temperature of 75-80 ℃ for 2-4 h, and measuring the NCO content;
4) adding acetone into the mixture obtained in the step 3) to dilute and cool to below 50 ℃;
5) emulsifying and dispersing by using deionized water under a high-speed shearing machine, adding a small molecule amino-terminated compound water diluent for chain extension after complete dispersion, and finally removing acetone in the system under reduced pressure to obtain a waterborne polyurethane emulsion;
6) adding a self-made closed water-based isocyanate type cross-linking agent into the emulsion, uniformly stirring, and adding a pH regulator to regulate the pH value of the emulsion to 8 +/-0.5.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the waterborne polyurethane surface resin with good adhesion with the solvent-free two-component adhesive is an environment-friendly material and meets the environmental protection standard of European Union; the waterborne polyurethane surface layer resin with good adhesion with the solvent-free two-component glue belongs to surface layer resins for synthetic leather, has hydrolysis resistance, cold resistance, smoothness and wear resistance, and does not have the bad phenomena of poor adhesion and even delamination and the like when being matched with the solvent-free two-component glue for use.
The waterborne polyurethane surface resin disclosed by the invention adopts modification means such as organic silicon and the like, so that the wear resistance and the scratch resistance of the resin are improved, and meanwhile, the resin has hand feels such as smoothness and cotton wax.
The waterborne polyurethane surface resin is a negative non-ionic structure, can be used together with other anionic or non-ionic waterborne polyurethane, but can not be used together with cationic polyurethane.
According to the invention, through reasonable material selection and process control, the hardness and softness of the resin can be controlled according to requirements, and various processing requirements can be met.
According to the invention, through the matched use of the sulfonate type polyhydric alcohol and the non-ionic hydrophilic agent, the generation of-COO-groups can be avoided, and the influence on the post-curing process of the solvent-free two-component adhesive is prevented; meanwhile, the waterborne polyurethane emulsion with solid content of about 50 percent and no precipitation after being stably stored for more than 6 months can be prepared, and the drying speed of the waterborne polyurethane surface layer resin is greatly improved.
According to the invention, through the use of the self-made closed water-based isocyanate crosslinking agent, the bridging effect between the solvent-free bi-component glue and the surface layer resin can be increased, so that the adhesion fastness between the surface layer and the bottom layer is improved; in addition, the crosslinking of the surface layer can also improve the performances of wear resistance, hydrolysis resistance, solvent resistance and the like.
The preparation method has simple process and simple and convenient operation, and saves manpower and equipment cost.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.
Example 1
The waterborne polyurethane surface resin with good adhesion with the solvent-free two-component adhesive is composed of the following components in formula: 10-30 parts of polymeric polyol, 0-5 parts of polyether modified silicone oil, 0-5 parts of self-made sulfonate polyol, 10-30 parts of isocyanate, 0.1-2 parts of micromolecule polyol, 1-5 parts of hydrophilic chain extender, 0.1-1 part of micromolecule amino-terminated compound, 40-60 parts of deionized water, 1-3 parts of self-made closed hydrophilic modified polyisocyanate cross-linking agent and 1-5 parts of pH value regulator.
Further, the formula comprises the following components: 15-25 parts of polymerized polyol, 3-5 parts of polyether modified silicone oil, 3-5 parts of self-made sulfonate polyol, 20-30 parts of isocyanate, 0.5-1.5 parts of micromolecule polyol, 2-4 parts of hydrophilic chain extender, 0.3-0.8 part of micromolecule amino-terminated compound, 45-55 parts of deionized water, 2-3 parts of self-made end-capped hydrophilic modified polyisocyanate cross-linking agent and 1-3.5 parts of pH value regulator.
Further, the polymeric polyol is one or more of polyethylene glycol adipate glycol, 1, 4-butanediol adipate glycol, 1, 6-hexanediol adipate glycol, diethylene glycol adipate glycol, polycarbonate glycol, polytetrahydrofuran glycol, polypropylene glycol, polyethylene glycol and N330. Preference is given to 1, 4-butanediol adipate diol, polytetrahydrofuran diol, N330.
Further, the polyether modified silicone oil can be a dihydric alcohol which is formed by graft copolymerization of polyether and dimethyl siloxane and has the relative molecular mass of 500-2000. Polyether-modified silicone oil of 2000 molecular weight is preferred.
Further, the preparation method of the self-made sulfonate type polymeric polyol comprises the following steps: adding metered hexanediol, adipic acid, trimethylolpropane and a sodium dihydroxy sulfonate solution into a flask, heating to 120 ℃, and reacting for 2-3 h. And then heating to about 200 ℃ for reaction, removing water in the system under reduced pressure, and testing the hydroxyl value and the acid value every 1h, wherein the end point is as follows: the hydroxyl value is 100-120mg KOH/g, and the acid value is less than or equal to 1mg KOH/g.
Further, the isocyanate may be one or more of 4,4' -diphenylmethane diisocyanate (HMDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI). HMDI is preferred.
Further, the small molecular polyol is one or more of ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1, 6-hexanediol, diethylene glycol, trimethylolpropane, triethanolamine, glycerol, N303 and castor oil. Preferably, butanediol and trimethylolpropane are used in combination.
Further, the micromolecule hydrophilic chain extender is one or more of a carboxylic acid compound with double hydroxyl groups, a non-ionic hydrophilic agent and sulfamate. Preference is given to dihydroxyl nonionic hydrophilicizing agents.
Further, the small molecule amino-terminated compound is one or more of ethylenediamine, isophoronediamine, hexamethylenediamine, hydrazine hydrate, KH-550 and KH-560. Ethylene diamine is preferred.
Further, the preparation method of the self-made closed water-based isocyanate crosslinking agent comprises the following steps: the measured Toluene Diisocyanate (TDI), Trimethylolpropane (TMP) and sodium salt of dihydroxysulfonate/DMSO solution are fed into a reaction kettle at one time, and the NCO content is about 11 percent by a toluene-di-n-butylamine method. Butanone oxime is adopted to carry out blocking reaction for about 3 hours at the temperature of 70-80 ℃, and NCO peak is not generated in infrared detection.
The invention also provides a preparation method of the waterborne polyurethane surface layer resin with good adhesion with the solvent-free bi-component adhesive, which comprises the following steps:
1) weighing the raw materials in parts by weight; adding polymeric polyol, polyether modified silicone oil, self-made sulfonate polyol and a hydrophilic chain extender into a flask, heating to 110-120 ℃, and dehydrating under reduced pressure for 1-2 hours;
2) cooling the mixture obtained in the step 1) to below 70 ℃, adding isocyanate, heating to 85-90 ℃, adding a small amount of catalyst, carrying out heat preservation reaction at the temperature for 2 hours, and measuring the NCO content;
3) cooling the mixture obtained in the step 2) to about 50 ℃, adding micromolecular polyol, carrying out heat preservation reaction at 75-80 ℃ for 2-4 h, and measuring the NCO content;
4) adding acetone into the mixture obtained in the step 3) to dilute and reduce the temperature to below 50 ℃.
5) And (2) emulsifying and dispersing by using deionized water under a high-speed shearing machine, adding a small molecule amino-terminated compound water diluent for chain extension after complete dispersion, and finally removing acetone in the system under reduced pressure to obtain the aqueous polyurethane emulsion.
6) Adding a proper amount of self-made closed water-based isocyanate type cross-linking agent into the emulsion, uniformly stirring, and adding a small amount of pH regulator to regulate the pH value of the emulsion to 8 +/-0.5.
Example 2
Adding 10 parts of PBA 2000, 10 parts of PTMG2000, 5 parts of self-made sulfonate polyol (molecular weight is 1300), 5 parts of polyether modified silicone oil 1000 and 5 parts of Ymer-N120 into a four-neck flask, and dehydrating at 110-120 ℃ under reduced pressure for 1 h; then cooling to below 70 ℃, adding 25 parts of HMDI, heating to 85-90 ℃, adding a small amount of organic bismuth catalyst, carrying out heat preservation reaction at the temperature for 2 hours, and measuring the NCO content; after the NCO content reaches the standard, cooling to about 50 ℃, adding 0.6 part of ethylene glycol and 0.1 part of trimethylolpropane, carrying out heat preservation reaction at 75-80 ℃, and measuring the NCO content; after the NCO content reaches the standard, adding acetone to dilute and reduce viscosity, and simultaneously reducing the temperature to 50 ℃. And (3) emulsifying and dispersing by using deionized water under a high-speed shearing machine, dripping 1 part of ethylenediamine water diluent for chain extension after the deionized water is completely dispersed, and finally decompressing to remove acetone in the system. 2 parts of self-made closed hydrophilic isocyanate crosslinking agent is added by stirring, and 2 parts of pH regulator is added to regulate the pH to about 7.5. The performance index of the obtained aqueous polyurethane resin is shown in table 1.
Unless otherwise specified, the operation processes and heating methods used in the above preparation processes are all conventional in the art.
Example 3
Adding 10 parts of PCL2000, 10 parts of PTMG2000, 5 parts of polyether modified silicone oil 2000, 5 parts of self-made sulfonate polyol (molecular weight is 1300) and 3 parts of Ymer-N120 into a four-neck flask, and dehydrating at 110-120 ℃ under reduced pressure for 1 h; then cooling to below 70 ℃, adding 25 parts of HMDI, heating to 85-90 ℃, adding a small amount of organic bismuth catalyst, carrying out heat preservation reaction at the temperature for 2 hours, and measuring the NCO content; after the NCO content reaches the standard, cooling to about 50 ℃, adding 1 part of butanediol and 0.2 part of trimethylolpropane, carrying out heat preservation reaction at 75-80 ℃, and measuring the NCO content; and after the NCO content reaches the standard, adding acetone for diluting and reducing viscosity, and simultaneously reducing the temperature to below 50 ℃. And (3) emulsifying and dispersing by using deionized water under a high-speed shearing machine, dripping 2 parts of ethylenediamine water diluent for chain extension after the deionized water is completely dispersed, and finally decompressing to remove acetone in the system. 2 parts of self-made closed hydrophilic isocyanate crosslinking agent is added by stirring, and 2 parts of pH regulator is added to regulate the pH to about 7.5. The performance index of the obtained aqueous polyurethane resin is shown in table 1.
Unless otherwise specified, the operation processes and heating methods used in the above preparation processes are all conventional in the art.
Example 4
Adding 10 parts of PNA 2000, 10 parts of PTMG2000, 3 parts of polyether modified silicone oil 1000, 5 parts of sulfonate type polyol (molecular weight is 1300) and 2 parts of Ymer-N120 into a four-neck flask, and dehydrating under reduced pressure at 110-120 ℃ for 1 h; then cooling to below 70 ℃, adding 25 parts of HMDI, heating to 85-90 ℃, adding a small amount of organic bismuth catalyst, carrying out heat preservation reaction at the temperature for 2 hours, and measuring the NCO content; after the NCO content reaches the standard, cooling to about 50 ℃, adding 1.2 parts of butanediol and 0.2 part of trimethylolpropane for heat preservation reaction at 75-80 ℃, and measuring the NCO content; and after the NCO content reaches the standard, adding acetone for diluting and reducing viscosity, and simultaneously reducing the temperature to below 50 ℃. And (3) emulsifying and dispersing by using deionized water under a high-speed shearing machine, dripping 3 parts of ethylenediamine water diluent for chain extension after the deionized water is completely dispersed, and finally decompressing to remove acetone in the system. 2 parts of self-made closed hydrophilic isocyanate crosslinking agent is added by stirring, and 2 parts of pH regulator is added to regulate the pH to about 7.5. The performance index of the obtained aqueous polyurethane resin is shown in table 1.
Unless otherwise specified, the operation processes and heating methods used in the above preparation processes are all conventional in the art.
Comparative example 1
Adding 10 parts of PBA 2000, 10 parts of PTMG2000, 1 part of dimethylolpropionic acid (DMPA), 5 parts of polyether modified silicone oil 1000 and 5 parts of Ymer-N120 into a four-neck flask, and performing reduced pressure dehydration for 1h at 110-120 ℃; then cooling to below 70 ℃, adding 25 parts of HMDI, heating to 85-90 ℃, adding a small amount of organic bismuth catalyst, carrying out heat preservation reaction at the temperature for 2 hours, and measuring the NCO content; after the NCO content reaches the standard, cooling to about 50 ℃, adding 0.6 part of ethylene glycol and 0.1 part of trimethylolpropane, carrying out heat preservation reaction at 75-80 ℃, and measuring the NCO content; after the NCO content reaches the standard, adding acetone to dilute and reduce viscosity, and simultaneously reducing the temperature to 50 ℃. And (3) emulsifying and dispersing by using deionized water under a high-speed shearing machine, dripping 1 part of ethylenediamine water diluent for chain extension after the deionized water is completely dispersed, and finally decompressing to remove acetone in the system. 2 parts of self-made closed hydrophilic isocyanate crosslinking agent is added by stirring, and 2 parts of pH regulator is added to regulate the pH to about 7.5. The performance index of the obtained aqueous polyurethane resin is shown in table 1.
Unless otherwise specified, the operation processes and heating methods used in the above preparation processes are all conventional in the art.
Comparative example 2
Adding 10 parts of PCL2000, 10 parts of PTMG2000, 5 parts of polyether modified silicone oil 2000, 3 parts of DMPA and 3 parts of Ymer-N120 into a four-neck flask, and performing reduced pressure dehydration for 1h at 110-120 ℃; then cooling to below 70 ℃, adding 25 parts of HMDI, heating to 85-90 ℃, adding a small amount of organic bismuth catalyst, carrying out heat preservation reaction at the temperature for 2 hours, and measuring the NCO content; after the NCO content reaches the standard, cooling to about 50 ℃, adding 1 part of butanediol and 0.2 part of trimethylolpropane, carrying out heat preservation reaction at 75-80 ℃, and measuring the NCO content; and after the NCO content reaches the standard, adding acetone for diluting and reducing viscosity, and simultaneously reducing the temperature to below 50 ℃. And (3) emulsifying and dispersing by using deionized water under a high-speed shearing machine, dripping 2 parts of ethylenediamine water diluent for chain extension after the deionized water is completely dispersed, and finally decompressing to remove acetone in the system. 2 parts of self-made closed hydrophilic isocyanate crosslinking agent is added by stirring, and 2 parts of pH regulator is added to regulate the pH to about 7.5. The performance index of the obtained aqueous polyurethane resin is shown in table 1.
Unless otherwise specified, the operation processes and heating methods used in the above preparation processes are all conventional in the art.
Comparative example 3
Adding 10 parts of PNA 2000, 10 parts of PTMG2000, 3 parts of polyether modified silicone oil 1000, 5 parts of sulfonate type polyol (molecular weight is 1300) and 2 parts of Ymer-N120 into a four-neck flask, and dehydrating under reduced pressure at 110-120 ℃ for 1 h; then cooling to below 70 ℃, adding 25 parts of HMDI, heating to 85-90 ℃, adding a small amount of organic bismuth catalyst, carrying out heat preservation reaction at the temperature for 2 hours, and measuring the NCO content; after the NCO content reaches the standard, cooling to about 50 ℃, adding 1.2 parts of butanediol and 0.2 part of trimethylolpropane for heat preservation reaction at 75-80 ℃, and measuring the NCO content; and after the NCO content reaches the standard, adding acetone for diluting and reducing viscosity, and simultaneously reducing the temperature to below 50 ℃. And (2) emulsifying and dispersing by using deionized water under a high-speed shearing machine, dripping 3 parts of ethylenediamine water diluent for chain extension after the deionized water is completely dispersed, and finally removing acetone in the system under reduced pressure to obtain the waterborne polyurethane emulsion. The performance index of the obtained aqueous polyurethane resin is shown in table 1.
Unless otherwise specified, the operation processes and heating methods used in the above preparation processes are all conventional in the art.
The following performance tests were performed on the waterborne polyurethane top layer resins obtained in examples 2 to 4 of the present invention and comparative examples 1 to 3, and the test results are shown in table 1:
TABLE 1
Note: the test adopts solvent-free two-component glue system HX-NS-8002A & B which is a soft solvent-free product of Zhejiang Hexin science and technology Limited.
As can be seen from the above table, the waterborne polyurethane surface resin of the present invention has the following advantages: the resin (waterborne polyurethane surface layer resin) has hydrolysis resistance, cold resistance, smoothness and wear resistance, and does not have the bad phenomena of poor adhesion force, even delamination and the like when being matched with solvent-free two-component glue for use.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (5)
1. The waterborne polyurethane surface layer resin is characterized by being prepared from the following raw materials in parts by weight: 15-25 parts of polymeric polyol, 3-5 parts of polyether modified silicone oil, 3-5 parts of self-made sulfonate polymeric polyol, 20-30 parts of isocyanate, 0.5-1.5 parts of micromolecule polyol, 2-4 parts of hydrophilic chain extender, 0.3-0.8 part of micromolecule amino-terminated compound, 45-55 parts of deionized water, 2-3 parts of self-made closed water-based isocyanate cross-linking agent and 1-3.5 parts of pH value regulator;
the preparation method of the homemade sulfonate type polymeric polyol comprises the following steps: adding hexanediol, adipic acid, trimethylolpropane and a sodium dihydroxy sulfonate solution into a flask, heating to 120 ℃, and reacting for 2-3 h; and then heating to 200 +/-5 ℃ for reaction, removing water in the system under reduced pressure, testing the hydroxyl value and the acid value every 1h, wherein the end point is as follows: the hydroxyl value is 100-120mg KOH/g, and the acid value is less than or equal to 1mg KOH/g;
the preparation method of the self-made closed water-based isocyanate crosslinking agent comprises the following steps: toluene Diisocyanate (TDI), Trimethylolpropane (TMP) and sodium dihydroxysulfonate/DMSO solution are fed into a reaction kettle at one step, and the NCO content is tested to be 11 +/-1% by a toluene-di-n-butylamine method; blocking and reacting butanone oxime at 70-80 ℃ for 3 +/-0.5 h, and stopping without NCO peak in infrared detection;
the hydrophilic chain extender is a nonionic hydrophilic agent; the small molecule amino-terminated compound is one or more of ethylenediamine, isophoronediamine, hexamethylenediamine and hydrazine hydrate;
the preparation method of the waterborne polyurethane surface layer resin comprises the following steps:
1) weighing the raw materials in parts by weight; adding polymeric polyol, polyether modified silicone oil, self-made sulfonate polymeric polyol and a hydrophilic chain extender into a flask, heating to 110-120 ℃, and dehydrating under reduced pressure for 1-2 hours;
2) cooling the mixture obtained in the step 1) to below 70 ℃, adding isocyanate, heating to 85-90 ℃, adding a catalyst, carrying out heat preservation reaction at the temperature for 2 hours, and measuring the NCO content;
3) cooling the mixture obtained in the step 2) to 50 +/-3 ℃, adding small molecular polyol, carrying out heat preservation reaction at the temperature of 75-80 ℃ for 2-4 h, and measuring the NCO content;
4) adding acetone into the mixture obtained in the step 3) to dilute and cool to below 50 ℃;
5) emulsifying and dispersing by using deionized water under a high-speed shearing machine, adding a small molecule amino-terminated compound water diluent for chain extension after complete dispersion, and finally removing acetone in the system under reduced pressure to obtain a waterborne polyurethane emulsion;
6) adding a self-made closed water-based isocyanate crosslinking agent into the emulsion, uniformly stirring, and adding a pH value regulator to regulate the pH value of the emulsion to 8 +/-0.5.
2. The waterborne polyurethane surface layer resin of claim 1, wherein the polymeric polyol is any one or more of polyethylene glycol adipate glycol, 1, 4-butanediol adipate glycol, 1, 6-hexanediol adipate glycol, diethylene glycol adipate glycol, polycarbonate glycol, polytetrahydrofuran glycol, polypropylene glycol, polyethylene glycol and N330.
3. The waterborne polyurethane surface resin of any one of claims 1 or 2, wherein the polyether modified silicone oil is a diol which is prepared by graft copolymerization of polyether and dimethyl siloxane and has a relative molecular mass of 1000-2000.
4. The waterborne polyurethane surface resin of any one of claims 1 or 2, wherein the isocyanate is any one or more of 4,4' -diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate.
5. The waterborne polyurethane surface layer resin of any one of claims 1 or 2, wherein the small molecular polyol is any one or more of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1, 6-hexanediol, diethylene glycol, trimethylolpropane, triethanolamine, glycerol, and castor oil.
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| CN111732708B (en) * | 2020-06-04 | 2022-04-12 | 旭川化学（苏州）有限公司 | Soft high-resilience aqueous polyurethane resin and preparation method and application thereof |
| CN111621046A (en) * | 2020-06-09 | 2020-09-04 | 施塔希(绍兴)新材料有限公司 | Waterproof starch film with biodegradable polyurethane as coating and preparation method thereof |
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| CN112111047B (en) * | 2020-08-04 | 2023-02-28 | 浙江禾欣科技有限公司 | High-peel hydrolysis-resistant polyurethane resin and preparation method thereof |
| CN112225871A (en) * | 2020-10-20 | 2021-01-15 | 上海华峰新材料研发科技有限公司 | Organic silicon modified bio-based waterborne polyurethane resin composition and preparation method thereof |
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