CN112709083A - Modified water-soluble high-elasticity polyurethane printing coating material and preparation method and application thereof - Google Patents
Modified water-soluble high-elasticity polyurethane printing coating material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112709083A CN112709083A CN202110172651.9A CN202110172651A CN112709083A CN 112709083 A CN112709083 A CN 112709083A CN 202110172651 A CN202110172651 A CN 202110172651A CN 112709083 A CN112709083 A CN 112709083A
- Authority
- CN
- China
- Prior art keywords
- coating material
- preparation
- elasticity
- soluble high
- printing coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5285—Polyurethanes; Polyurea; Polyguanides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/46—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing natural macromolecular substances or derivatives thereof
- D06P1/48—Derivatives of carbohydrates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5271—Polyesters; Polycarbonates; Alkyd resins
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of polyurethane, and particularly relates to a modified water-soluble high-elasticity polyurethane printing coating material, and a preparation method and application thereof. A modified water-soluble high-elasticity printed polyurethane coating material is prepared from acetone, polytetrahydrofuran, tetrabutyl titanate, isophorone diisocyanate, dimethylolpropionic acid, triethylamine, ethylenediamine, a biodegradable additive and deionized water, wherein the biodegradable additive is at least one of natural cellulose, artificially synthesized polycaprolactone, polyvinyl alcohol, aromatic-aliphatic ester polymer, maleic anhydride-based modified polylactic acid (MPLA), butanediamine-based modified polylactic acid (BMPLA), monosaccharide and hexose. The printing coating material has high biodegradation rate, good elasticity, wear resistance and water washing resistance. The preparation method disclosed by the invention is simple, easy to control and suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to a modified water-soluble high-elasticity polyurethane printing coating material and a preparation method thereof.
Background
On some elastic materials, coating materials such as printing, printing and coating various patterns and figures need high elasticity capable of water solubility, and the elastomer has excellent elastic property, hydrophobic property, stain resistance and high-molecular material capable of being cured quickly. For example, when the elongation of the textile high-elasticity fabric is about 200%, the elastic recovery rate of the textile high-elasticity fabric is kept at 100%, and the elasticity of the material for printing, printing and coating on the textile high-elasticity fabric is larger than that of the high-elasticity textile fabric. For this reason, a coating material having high elasticity is required. The modified water-soluble polyurethane has the performance requirement, and is used for printing, printing and coating materials such as high-elasticity fabric, high-elasticity synthetic rubber, TPE (thermoplastic elastomer), EVA (ethylene-vinyl acetate copolymer) and the like.
For the modification synthesis of water-soluble polyurethane, organic silicon modified polyurethane elastic coating materials, epoxy resin modified polyurethane elastic coating materials, inorganic nano particle modified polyurethane elastic coating materials and fluorine-containing acrylate synthesized fluorine modified polyurethane elastic coating materials are available in the market at present. The organosilicon material has the characteristics of longer siloxane bond, shielding effect of methyl connected with silicon atoms on a polysiloxane main chain, weak intermolecular acting force and the like, and the organosilicon material is introduced into the polyurethane elastic coating by a chemical or physical modification method, so that the hydrophobic, weather-resistant, wear-resistant, cold-resistant, biocompatible, ageing-resistant and other properties of the modified polyurethane elastic coating can be obviously improved. Epoxy resin is added into polyurethane elastic coating, a polymerization mixture with interpenetrating network structure and strong entanglement can be formed through copolymerization, the epoxy resin randomly penetrates in the polyurethane, and the two components easily generate synergistic action, so that the polymerization mixture has more excellent performance than a common blend. The inorganic nano particle modified polyurethane elastic coating material adopts the inorganic nano particle modified polyurethane elastic coating, not only improves the mechanical strength of the coating, but also improves the thermal stability and toughness of the coating. Synthesizing fluorine-containing acrylate into a fluorine-containing modified polyurethane elastic coating material, firstly synthesizing isocyanate end-capped polyurethane prepolymer, then end-capping with double-bond terminated compounds such as HEA (ethyl acrylate) to prepare double-bond end-capped polyurethane acrylate resin, and copolymerizing the double-bond end-capped polyurethane acrylate resin with a fluorine-containing acrylate monomer by using the double-bond terminated polyurethane acrylate resin as a matrix to finally obtain the fluorine-containing modified polyurethane.
However, the above modifications are synthetic modifications, have macromolecular structures, and are not biodegradable in nature. New pollution to the environment can be caused.
Therefore, it is highly desirable to develop a biodegradable material to meet the requirement of high elasticity printing.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a modified water-soluble high-elasticity polyurethane printing coating material, the dispersion has good hydrolysis resistance, good color fastness after printing and bright color; the invention also aims to provide a preparation method of the modified water-soluble high-elasticity polyurethane printing coating material, which is simple, easy to control and suitable for large-scale production; the invention further aims to provide application of the modified water-soluble high-elasticity polyurethane printing coating material.
The purpose of the invention is realized by the following technical scheme: the application of the modified water-soluble high-elasticity polyurethane printing coating material is characterized in that the modified water-soluble high-elasticity polyurethane printing coating material is printed on high-elasticity fabric or clothes into high-elasticity lines or patterns through screen printing or 3D printing.
According to the invention, the modified water-soluble high-elasticity polyurethane printing coating material is printed on the high-elasticity fabric or clothes into high-elasticity lines or patterns through screen printing or 3D printing, so that the effects of shaping, lifting and supporting can be achieved.
The modified water-soluble high-elasticity polyurethane printing coating material is prepared from, by weight, 50 parts of acetone, 10-30 parts of polytetrahydrofuran, 10-30 parts of tetrabutyl titanate, 100 parts of isophorone diisocyanate, 30-50 parts of dimethylolpropionic acid, 10-15 parts of triethylamine, 1-3 parts of ethylenediamine, 0.5-5 parts of a biodegradation additive and 500 parts of deionized water, wherein the biodegradation additive is at least one of natural cellulose, artificially synthesized polycaprolactone, polyvinyl alcohol, aromatic-aliphatic ester polymer, modified polylactic acid (BMPLA) based on maleic anhydride modified polylactic acid (MPLA) and butanediamine, monosaccharide and aldohexose.
The biodegradable modified water-soluble high-elasticity polyurethane printing coating material prepared by the formula has good hydrolysis resistance, good color fastness after printing and bright color.
Further, a preparation method of the modified water-soluble high-elasticity polyurethane printing coating material comprises the following steps of (1) sequentially stirring and heating acetone, polytetrahydrofuran, tetrabutyl titanate and a biodegradable additive in a device under the protection of nitrogen, and controlling the temperature to be 40 ℃; (2) slowly and uniformly dripping isophorone diisocyanate, heating to 50 ℃ after dripping, and reacting for 0.5 h; (3) adding dimethylolpropionic acid and triethylamine until the concentration of isocyanate groups is lower than 1.2% to obtain a polyurethane resin prepolymer; (4) adding deionized water, adding ethylenediamine, stirring at high speed for 1h, and cooling to room temperature; (5) carrying out reduced pressure distillation to evaporate redundant organic solvent, and filtering by using a polyvinylidene fluoride membrane with the particle size of 1.0 mu m to obtain the waterborne polyurethane resin; (6) adding deionized water to obtain the biodegradable modified water-soluble high-elasticity polyurethane printing coating material.
The invention ensures full reaction by strictly controlling the reaction temperature and the reaction speed, has high purity of the waterborne polyurethane, is more resistant to washing after being used as a dispersion for printing, has good alkali resistance, and has good biodegradability and wear resistance.
Further, the biodegradable additive is natural cellulose, artificially synthesized polycaprolactone and maleic anhydride-based modified polylactic acid (MPLA) in a ratio of 1: (1-3): (1-3) in the presence of a catalyst.
According to the invention, the biodegradable additive is prepared according to the proportion, so that the biodegradable modified water-soluble high-elasticity polyurethane printing coating material has high degradability.
Further, the biodegradable additive is natural cellulose, artificially synthesized polycaprolactone and maleic anhydride-based modified polylactic acid (MPLA) in a ratio of 1: 1:2, and (b) a mixture of the components.
Further, the structural formula of the natural cellulose is shown in the specification
Further, the polytetrahydrofuran has an average molecular weight of 2000.
According to the invention, polytetrahydrofuran with the average molecular weight of 2000 and the hydroxyl content of 54-57mgKOH/g is adopted, so that the prepared waterborne polyurethane has better elasticity, is soft and flexible in film forming, and is more washable and friction-resistant after printing.
Further, the polytetrahydrofuran is prepared by the following steps of putting tetrahydrofuran into a reaction bottle, cooling to-5 ℃, dropwise adding fuming sulfuric acid under high-speed stirring, reacting for 30min, adding a certain amount of water, heating to 70-90 ℃, evaporating unreacted tetrahydrofuran monomers, standing, layering, neutralizing, filtering and vacuumizing to obtain the polytetrahydrofuran.
The polytetrahydrofuran prepared by the steps has high purity.
Further, in the step (2), the isophorone diisocyanate is slowly added dropwise by using a peristaltic pump, and the adding time is 1-1.5 h.
According to the invention, the isophorone diisocyanate is added by using the peristaltic pump, so that the dropping speed can be accurately controlled, and the reaction is more sufficient.
Further, the dimethylolpropionic acid is prepared by the following steps of mixing n-propionaldehyde and formaldehyde according to a molar ratio of 1:2.5, reacting for 6 hours under the catalysis of an alkaline catalyst, wherein the reaction temperature is 35 ℃, adding hydrogen peroxide after heating to 80 ℃, reacting for 8 hours, and freezing and crystallizing to obtain the dimethylolpropionic acid.
The method for preparing dimethylol propionic acid is easy to control, safe, simple and convenient, the prepared dimethylol propionic acid has high purity, and the dimethylol propionic acid is used as a raw material to prepare the waterborne polyurethane, so that side reactants are few, and the waterborne polyurethane is more easily dispersed.
Further, the basic catalyst is triethylamine and potassium carbonate, and the molar ratio of triethylamine to potassium carbonate is 1: (1-3) in the presence of a catalyst.
The invention uses triethylamine and potassium carbonate in a molar ratio of 1: the mixture formed by the (1-3) is used as a basic catalyst, so that the environmental pollution caused by excessive use of triethylamine is avoided, the cost can be effectively reduced, the conversion rate of the n-propionaldehyde is higher, and the total addition amount of the catalyst is less.
Further, the molar ratio of the hydrogen peroxide to the propionaldehyde is 1.5: 1.
According to the invention, the molar ratio of hydrogen peroxide to propionaldehyde is controlled to be 1.5:1, so that the conversion rate of intermediate dimethylolpropionaldehyde is highest, and the conversion rate of dimethylolpropionic acid is effectively improved.
The invention has the beneficial effects that: the biodegradable modified water-soluble high-elasticity polyurethane printing coating material has good hydrolysis resistance, good color fastness after printing and bright color; the preparation method is simple, easy to control and suitable for large-scale production.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
The modified water-soluble high-elasticity polyurethane printing coating material is prepared from the following raw materials, by weight, 50 parts of acetone, 10 parts of polytetrahydrofuran, 10 parts of tetrabutyl titanate, 100 parts of isophorone diisocyanate, 30 parts of dimethylolpropionic acid, 10 parts of triethylamine, 1 part of ethylenediamine and 500 parts of deionized water.
Further, the method comprises the following steps of (1) sequentially stirring and heating acetone, polytetrahydrofuran, tetrabutyl titanate and a biodegradable additive in a device under the protection of nitrogen, and controlling the temperature to be 40 ℃; (2) slowly and uniformly dripping isophorone diisocyanate, heating to 50 ℃ after dripping, and reacting for 0.5 h; (3) adding dimethylolpropionic acid and triethylamine until the concentration of isocyanate groups is lower than 1.2% to obtain a polyurethane resin prepolymer; (4) adding deionized water, adding ethylenediamine, stirring at high speed for 1h, and cooling to room temperature; (5) carrying out reduced pressure distillation to evaporate redundant organic solvent, and filtering by using a polyvinylidene fluoride membrane with the particle size of 1.0 mu m to obtain the waterborne polyurethane resin; (6) adding deionized water to obtain the biodegradable modified water-soluble high-elasticity polyurethane printing coating material.
Further, the biodegradable additive is natural cellulose, artificially synthesized polycaprolactone and maleic anhydride-based modified polylactic acid (MPLA) in a ratio of 1: 1:2 of a mixture
Further, the polytetrahydrofuran has an average molecular weight of 2000.
Further, the polytetrahydrofuran is prepared by the following steps of putting tetrahydrofuran into a reaction bottle, cooling to-5 ℃, dropwise adding fuming sulfuric acid under high-speed stirring, reacting for 30min, adding a certain amount of water, heating to 80 ℃, evaporating unreacted tetrahydrofuran monomers, standing, layering, neutralizing, filtering and vacuumizing to obtain the polytetrahydrofuran.
Further, the isophorone diisocyanate in the step (2) is slowly added dropwise by using a peristaltic pump, and the adding time is 1 h.
Further, the dimethylolpropionic acid is prepared by the following steps of mixing n-propionaldehyde and formaldehyde according to a molar ratio of 1:2.5, reacting for 6 hours under the catalysis of an alkaline catalyst, wherein the reaction temperature is 35 ℃, adding hydrogen peroxide after heating to 80 ℃, reacting for 8 hours, and freezing and crystallizing to obtain the dimethylolpropionic acid.
Further, the basic catalyst is triethylamine and potassium carbonate, and the molar ratio of triethylamine to potassium carbonate is 1: 1, in a mixture of the components.
Further, the molar ratio of the hydrogen peroxide to the propionaldehyde is 1.5: 1.
Example 2
A modified water-soluble high-elasticity polyurethane printing coating material is prepared from, by weight, 50 parts of acetone, 30 parts of polytetrahydrofuran, 30 parts of tetrabutyl titanate, 100 parts of isophorone diisocyanate, 50 parts of dimethylolpropionic acid, 15 parts of triethylamine, 3 parts of ethylenediamine and 500 parts of deionized water.
Further, the method comprises the following steps of (1) sequentially stirring and heating acetone, polytetrahydrofuran, tetrabutyl titanate and a biodegradable additive in a device under the protection of nitrogen, and controlling the temperature to be 40 ℃; (2) slowly and uniformly dripping isophorone diisocyanate, heating to 50 ℃ after dripping, and reacting for 0.5 h; (3) adding dimethylolpropionic acid and triethylamine until the concentration of isocyanate groups is lower than 1.2% to obtain a polyurethane resin prepolymer; (4) adding deionized water, adding ethylenediamine, stirring at high speed for 1h, and cooling to room temperature; (5) carrying out reduced pressure distillation to evaporate redundant organic solvent, and filtering by using a polyvinylidene fluoride membrane with the particle size of 1.0 mu m to obtain the waterborne polyurethane resin; (6) adding deionized water to obtain the biodegradable modified water-soluble high-elasticity polyurethane printing coating material.
Further, the biodegradable additive is natural cellulose, artificially synthesized polycaprolactone and maleic anhydride-based modified polylactic acid (MPLA) in a ratio of 1: 1: 1, in a mixture of the components.
Further, the polytetrahydrofuran has an average molecular weight of 2000.
Further, the polytetrahydrofuran is prepared by the following steps of putting tetrahydrofuran into a reaction bottle, cooling to-5 ℃, dropwise adding fuming sulfuric acid under high-speed stirring, reacting for 30min, adding a certain amount of water, heating to 70-90 ℃, evaporating unreacted tetrahydrofuran monomers, standing, layering, neutralizing, filtering and vacuumizing to obtain the polytetrahydrofuran.
Further, in the step (2), the isophorone diisocyanate is slowly added dropwise by using a peristaltic pump, and the adding time is 1-1.5 h.
Further, the dimethylolpropionic acid is prepared by the following steps of mixing n-propionaldehyde and formaldehyde according to a molar ratio of 1:2.5, reacting for 6 hours under the catalysis of an alkaline catalyst, wherein the reaction temperature is 35 ℃, adding hydrogen peroxide after heating to 80 ℃, reacting for 8 hours, and freezing and crystallizing to obtain the dimethylolpropionic acid.
Further, the basic catalyst is triethylamine and potassium carbonate, and the molar ratio of triethylamine to potassium carbonate is 1: 3, and (b) a mixture of the components.
Further, the molar ratio of the hydrogen peroxide to the propionaldehyde is 1.5: 1.
Example 3
A modified water-soluble high-elasticity polyurethane printing coating material is prepared from, by weight, 50 parts of acetone, 20 parts of polytetrahydrofuran, 20 parts of tetrabutyl titanate, 100 parts of isophorone diisocyanate, 40 parts of dimethylolpropionic acid, 15 parts of triethylamine, 3 parts of ethylenediamine and 500 parts of deionized water.
Further, the method comprises the following steps of (1) sequentially stirring and heating acetone, polytetrahydrofuran, tetrabutyl titanate and a biodegradable additive in a device under the protection of nitrogen, and controlling the temperature to be 40 ℃; (2) slowly and uniformly dripping isophorone diisocyanate, heating to 50 ℃ after dripping, and reacting for 0.5 h; (3) adding dimethylolpropionic acid and triethylamine until the concentration of isocyanate groups is lower than 1.2% to obtain a polyurethane resin prepolymer; (4) adding deionized water, adding ethylenediamine, stirring at high speed for 1h, and cooling to room temperature; (5) carrying out reduced pressure distillation to evaporate redundant organic solvent, and filtering by using a polyvinylidene fluoride membrane with the particle size of 1.0 mu m to obtain the waterborne polyurethane resin; (6) adding deionized water to obtain the biodegradable modified water-soluble high-elasticity polyurethane printing coating material.
Further, the biodegradable additive is natural cellulose, artificially synthesized polycaprolactone and maleic anhydride-based modified polylactic acid (MPLA) in a ratio of 1: 3: 3, and (b) a mixture of the components.
Further, the polytetrahydrofuran has an average molecular weight of 2000.
Further, the polytetrahydrofuran is prepared by the following steps of putting tetrahydrofuran into a reaction bottle, cooling to-5 ℃, dropwise adding fuming sulfuric acid under high-speed stirring, reacting for 30min, adding a certain amount of water, heating to 70-90 ℃, evaporating unreacted tetrahydrofuran monomers, standing, layering, neutralizing, filtering and vacuumizing to obtain the polytetrahydrofuran.
Further, in the step (2), the isophorone diisocyanate is slowly added dropwise by using a peristaltic pump, and the adding time is 1-1.5 h.
Further, the dimethylolpropionic acid is prepared by the following steps of mixing n-propionaldehyde and formaldehyde according to a molar ratio of 1:2.5, reacting for 6 hours under the catalysis of an alkaline catalyst, wherein the reaction temperature is 35 ℃, adding hydrogen peroxide after heating to 80 ℃, reacting for 8 hours, and freezing and crystallizing to obtain the dimethylolpropionic acid.
Further, the basic catalyst is triethylamine and potassium carbonate, and the molar ratio of triethylamine to potassium carbonate is 1: 3, and (b) a mixture of the components.
Further, the molar ratio of the hydrogen peroxide to the propionaldehyde is 1.5: 1.
In an application example, the modified water-soluble high-elasticity polyurethane printing coating material prepared in the embodiment is added with color paste for printing, and then is subjected to a water washing resistance test according to GB/T5713-2013 and a friction resistance test according to GB/T3920-2008, and is subjected to a degradation performance test according to GB/T2415-1998; the biodegradation rate is as follows: ISO: 14855. the test results are given in the following table:
| example 1 | Example 2 | Example 3 | |
| Rub resistance/grade | 4 | 4 | 4 |
| Water washing resistant grade | 4 | 5 | 4 |
| Elongation (%) | 234 | 230 | 230 |
| Shape recovery after 10 elongations (%) | 100 | 100 | 100 |
| Rate of degradability | More than 80 percent | More than 80 percent | More than 80 percent |
As can be seen from the table above, the modified water-soluble high-elasticity polyurethane printing coating material prepared by the invention can prolong the service life when being applied to printing, and has good friction resistance and water washing resistance.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. The application of the modified water-soluble high-elasticity polyurethane printing coating material is characterized in that: the modified water-soluble high-elasticity polyurethane printing coating material is printed into high-elasticity lines or patterns on high-elasticity fabric or clothes through screen printing or 3D printing.
2. A modified water-soluble high-elasticity polyurethane printing coating material is characterized in that: the biodegradable polyurethane foam material is prepared from the following raw materials, by weight, 50 parts of acetone, 10-30 parts of polytetrahydrofuran, 10-30 parts of tetrabutyl titanate, 100 parts of isophorone diisocyanate, 30-50 parts of dimethylolpropionic acid, 10-15 parts of triethylamine, 1-3 parts of ethylenediamine, 0.5-5 parts of a biodegradable additive and 500 parts of deionized water, wherein the biodegradable additive is at least one of natural cellulose, artificially synthesized polycaprolactone, polyvinyl alcohol, an aromatic-aliphatic ester polymer, maleic anhydride modified polylactic acid (MPLA), modified polylactic acid (BMPLA) of butanediamine, monosaccharide and aldohexose.
3. The preparation method of the modified water-soluble high-elasticity polyurethane printing coating material as claimed in claim 2, characterized in that: the biodegradable additive is natural cellulose, artificially synthesized polycaprolactone and modified polylactic acid (MPLA) based on maleic anhydride, wherein the weight ratio of the biodegradable additive to the polylactic acid is 1: (1-3): (1-3) in the presence of a catalyst.
4. The preparation method of the modified water-soluble high-elasticity polyurethane printing coating material according to any one of claims 2 to 3, characterized in that: the method comprises the following steps of (1) sequentially stirring and heating acetone, polytetrahydrofuran, tetrabutyl titanate and a biodegradable additive in a device under the protection of nitrogen, and controlling the temperature to be 40 ℃; (2) slowly and uniformly dripping isophorone diisocyanate, heating to 50 ℃ after dripping, and reacting for 0.5 h; (3) adding dimethylolpropionic acid and triethylamine until the concentration of isocyanate groups is lower than 1.2% to obtain a polyurethane resin prepolymer; (4) adding deionized water, adding ethylenediamine, stirring at high speed for 1h, and cooling to room temperature; (5) carrying out reduced pressure distillation to evaporate redundant organic solvent, and filtering by using a polyvinylidene fluoride membrane with the particle size of 1.0 mu m to obtain the waterborne polyurethane resin; (6) adding deionized water to obtain the biodegradable modified water-soluble high-elasticity polyurethane printing coating material.
5. The preparation method of the modified water-soluble high-elasticity polyurethane printing coating material as claimed in claim 4, wherein the preparation method comprises the following steps: the polytetrahydrofuran has an average molecular weight of 2000.
6. The preparation method of the modified water-soluble high-elasticity polyurethane printing coating material as claimed in claim 5, characterized in that: the polytetrahydrofuran is prepared by the following steps of putting tetrahydrofuran into a reaction bottle, cooling to-5 ℃, dropwise adding fuming sulfuric acid under high-speed stirring, reacting for 30min, adding a certain amount of water, heating to 70-90 ℃, evaporating unreacted tetrahydrofuran monomers, standing, layering, neutralizing, filtering and vacuumizing to obtain the polytetrahydrofuran.
7. The preparation method of the modified water-soluble high-elasticity polyurethane printing coating material as claimed in claim 6, wherein the preparation method comprises the following steps: in the step (2), the isophorone diisocyanate is slowly added dropwise by using a peristaltic pump, and the adding time is 1-1.5 h.
8. The preparation method of the modified water-soluble high-elasticity polyurethane printing coating material as claimed in claim 7, wherein the preparation method comprises the following steps: the dimethylolpropionic acid is prepared by the following steps of mixing n-propionaldehyde and formaldehyde according to a molar ratio of 1:2.5, reacting for 6 hours under the catalysis of an alkaline catalyst, reacting at 35 ℃, heating to 80 ℃, adding hydrogen peroxide, reacting for 8 hours, and freezing and crystallizing to obtain the dimethylolpropionic acid.
9. The preparation method of the modified water-soluble high-elasticity polyurethane printing coating material as claimed in claim 8, wherein the preparation method comprises the following steps: the basic catalyst is triethylamine and potassium carbonate, and the molar ratio of triethylamine to potassium carbonate is 1: (1-3) in the presence of a catalyst.
10. The preparation method of the modified water-soluble high-elasticity polyurethane printing coating material as claimed in claim 9, characterized in that: the molar ratio of the hydrogen peroxide to the propionaldehyde is 1.5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110172651.9A CN112709083A (en) | 2021-02-08 | 2021-02-08 | Modified water-soluble high-elasticity polyurethane printing coating material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110172651.9A CN112709083A (en) | 2021-02-08 | 2021-02-08 | Modified water-soluble high-elasticity polyurethane printing coating material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112709083A true CN112709083A (en) | 2021-04-27 |
Family
ID=75550083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110172651.9A Pending CN112709083A (en) | 2021-02-08 | 2021-02-08 | Modified water-soluble high-elasticity polyurethane printing coating material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112709083A (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5898049A (en) * | 1996-11-06 | 1999-04-27 | Bayer Aktiengesellschaft | Biodegradable and compostable shaped bodies |
| CN1995086A (en) * | 2006-12-30 | 2007-07-11 | 四川大学 | Method for preparing aqueous nontoxic degradable polyurethane elastomer |
| CN101391113A (en) * | 2008-11-07 | 2009-03-25 | 四川大学 | Polyurethane medical compound film and preparation method thereof |
| JP2009096096A (en) * | 2007-10-18 | 2009-05-07 | Tohcello Co Ltd | Laminated film |
| CN101503501A (en) * | 2009-03-02 | 2009-08-12 | 四川大学 | Biodegradable nontoxic amphipathic multi-block polyurethane material and preparation thereof |
| CN102030882A (en) * | 2010-10-19 | 2011-04-27 | 天津理工大学 | Method for preparing biodegradable polyurethane material with pH responsiveness |
| CN103073692A (en) * | 2013-01-31 | 2013-05-01 | 烟台前进化工有限公司 | Producing method of water-base polyurethane |
| CN103910852A (en) * | 2014-03-04 | 2014-07-09 | 西安工程大学 | Degradable aqueous polyurethane emulsion and preparation method thereof |
| US20140194533A1 (en) * | 2013-01-02 | 2014-07-10 | National Taiwan University | Biocompatible and biodegradable elastomer |
| CN105669942A (en) * | 2016-01-25 | 2016-06-15 | 苏州印丝特纺织数码科技有限公司 | Polyurethane-modified pigment printing binding agent preparation method |
| CN107011494A (en) * | 2017-05-23 | 2017-08-04 | 深圳市润天智数字设备股份有限公司 | A kind of preparation method of aqueous polyurethane dispersion |
-
2021
- 2021-02-08 CN CN202110172651.9A patent/CN112709083A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5898049A (en) * | 1996-11-06 | 1999-04-27 | Bayer Aktiengesellschaft | Biodegradable and compostable shaped bodies |
| CN1995086A (en) * | 2006-12-30 | 2007-07-11 | 四川大学 | Method for preparing aqueous nontoxic degradable polyurethane elastomer |
| JP2009096096A (en) * | 2007-10-18 | 2009-05-07 | Tohcello Co Ltd | Laminated film |
| CN101391113A (en) * | 2008-11-07 | 2009-03-25 | 四川大学 | Polyurethane medical compound film and preparation method thereof |
| CN101503501A (en) * | 2009-03-02 | 2009-08-12 | 四川大学 | Biodegradable nontoxic amphipathic multi-block polyurethane material and preparation thereof |
| CN102030882A (en) * | 2010-10-19 | 2011-04-27 | 天津理工大学 | Method for preparing biodegradable polyurethane material with pH responsiveness |
| US20140194533A1 (en) * | 2013-01-02 | 2014-07-10 | National Taiwan University | Biocompatible and biodegradable elastomer |
| CN103073692A (en) * | 2013-01-31 | 2013-05-01 | 烟台前进化工有限公司 | Producing method of water-base polyurethane |
| CN103910852A (en) * | 2014-03-04 | 2014-07-09 | 西安工程大学 | Degradable aqueous polyurethane emulsion and preparation method thereof |
| CN105669942A (en) * | 2016-01-25 | 2016-06-15 | 苏州印丝特纺织数码科技有限公司 | Polyurethane-modified pigment printing binding agent preparation method |
| CN107011494A (en) * | 2017-05-23 | 2017-08-04 | 深圳市润天智数字设备股份有限公司 | A kind of preparation method of aqueous polyurethane dispersion |
Non-Patent Citations (8)
| Title |
|---|
| 宋小平 等: "《皮革用化学品生产工艺与技术》", 31 October 2017, 科学技术文献出版社 * |
| 朱俐静等: "植物纤维基聚氨酯材料的研究进展", 《生物质化学工程》 * |
| 杨丑伟等: "壳聚糖/聚氨酯复合材料研究进展", 《化学推进剂与高分子材料》 * |
| 梁书恩等: "软段分子链结构对PUF性能的影响", 《聚氨酯工业》 * |
| 王利军等: "水性聚氨酯技术进展", 《皮革科学与工程》 * |
| 甘文君 等: "《高分子化学实验原理与技术》", 31 July 2012, 上海交通大学出版社 * |
| 迈纳琴•莱温 等: "《高技术纤维》", 31 March 1992, 纺织工业出版社 * |
| 黄凤远: "《水溶性纤维素醚的合成与应用》", 31 August 2020, 中国纺织出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100402574C (en) | Polysiloxane-polyether copolymer modified aqueous polyurethane preparation method | |
| CN109679030B (en) | Waterborne polyurethane-polyvinyl acetate resin and preparation method and application thereof | |
| CN101348703B (en) | Aqueous polyurethane adhesive and preparation thereof | |
| CN102827340B (en) | Organosilicon-modified waterborne polyurethane composite material and applications thereof | |
| CN112694591A (en) | Preparation method of silane coupling agent modified solvent-free waterborne polyurethane | |
| CN105037677B (en) | A kind of highly -branched thermoplastic polyurethane elastomer and preparation method thereof | |
| CN109456459B (en) | Method for improving water resistance or solvent resistance of waterborne polyurethane | |
| CN102093530A (en) | Preparation method of organosilicon-modified aqueous polyurethane | |
| TWI740810B (en) | Waterborne polyamide, their chain extension with isocyanates to form cationic waterborne polyureas dispersions and process to make the same | |
| CN109970960B (en) | Polyether diol and application thereof in aqueous interpenetrating network polymer emulsion | |
| CN117447883B (en) | Composite material based on hydroxy acrylic resin and preparation method thereof | |
| CN103709884B (en) | Organic-silicon-modified waterbased urethane priming paint of a kind of VOC free and preparation method thereof | |
| CN103923523B (en) | Multi-arm star-shaped acrylate copolymer-modified polyurethane printing ink and preparation method thereof | |
| CN103059246B (en) | Silicon hybrid waterborne polyurethane derived from natural fatty acid and preparation method for waterborne polyurethane | |
| CN110791237A (en) | Water-based carpet backing adhesive and preparation method thereof | |
| CN108531067B (en) | Polylactic acid embedded polyurethane environment-friendly waterproof coating and preparation process thereof | |
| CN103694442B (en) | Leather fills the preparation method with branched structure polyurethane-polyacrylate compound resin | |
| CN107629188A (en) | A kind of preparation method of combination property high-environmental type modified aqueous polyurethane | |
| TW201630976A (en) | Water dispersible polyamide building blocks | |
| CN114891183A (en) | Waterborne polyurethane modified starch dispersion liquid and preparation method thereof | |
| CN112709083A (en) | Modified water-soluble high-elasticity polyurethane printing coating material and preparation method and application thereof | |
| CN102020746A (en) | Application of epoxy functionalized acrylic ester polymer | |
| He et al. | Enhanced Water Resistance Performance of Castor Oil—Based Waterborne Polyurethane Modified by Methoxysilane Coupling Agents via Thiol-Ene Photo Click Reaction | |
| CN108976860B (en) | Waterproof polyurethane coating for zipper and preparation method thereof | |
| CN108192072B (en) | Aqueous polyurethane dispersion and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |