CN112480354B - Cationic self-repairing waterborne polyurethane and preparation method thereof - Google Patents
Cationic self-repairing waterborne polyurethane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cationic self-repairing waterborne polyurethane and a preparation method thereof, wherein the waterborne cationic polyurethane containing disulfide bonds and acylhydrazone bonds is synthesized by polymer diol, diisocyanate, a hydrophilic chain extender, disulfide bonds and acylhydrazone bond compounds; the invention realizes infinite self-repair of polyurethane by utilizing reversible chemical bonds of disulfide bonds and acylhydrazone bonds and hydrogen bonding action of the polyurethane, and has the advantages of dust prevention, sterilization, environmental protection, excellent mechanical property, good compatibility, easy modification and the like. The polyurethane has the advantages that the framework of the polyurethane is provided with the cationic group which is insensitive to water hardness, so that the polyurethane can be applied under acidic conditions, is particularly suitable for surface treatment of anionic leather, textile, papermaking and glass, and has better application in the fields of leather, coating, adhesive, textile, papermaking and the like.
Description
Technical Field
The invention relates to the technical field of waterborne polyurethane, and particularly relates to cationic self-repairing waterborne polyurethane and a preparation method thereof.
Background
Cationic waterborne polyurethanes are those in which tertiary amine functionality is introduced into the polyurethane chain to form cationic groups on the backbone. Because the ions formed by the method are quaternary ammonium salts, the particles have positive charges, the charges are the same as those of dust in the air, the surfaces have cohesiveness and wettability, and certain dustproof and bactericidal effects, so that the method is particularly suitable for surface treatment of anionic leather, textile, papermaking and glass; is not sensitive to the hardness of water and can be used under acidic conditions.
In the using process of the cationic waterborne polyurethane, the attractiveness of the material can be damaged and the performance of the material can be influenced due to mechanical damage caused by friction, collision and bending, and finally the service life of the material is shortened.
In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.
Disclosure of Invention
In order to solve the technical defects, the invention adopts the technical scheme that the preparation method of the cationic self-repairing waterborne polyurethane comprises the following steps:
s1, heating the polymer polyol to 100-130 ℃, and dehydrating for 1-2 h in vacuum;
s2, carrying out nitrogen protection on the solution obtained in the step S1, cooling to 60-90 ℃, adding polyisocyanate and a catalyst, reacting for 1-3 h, and adding an organic solvent to adjust viscosity;
s3, adding a hydrophilic chain extender into the solution obtained in the step S2, and reacting for 1-3 h at 70-90 ℃;
s4, adding a disulfide bond compound and an acylhydrazone bond compound into the solution obtained in the step S3, and reacting at 40-90 ℃ for 1-3 h;
s5, cooling the solution obtained in the step S4 to 30-50 ℃, adding a salt forming agent, and reacting for 10-30 min;
s6, cooling the solution obtained in the step S5 to 10-30 ℃, adding deionized water, and dispersing at a high speed for 10-30 min;
s7, desolventizing the solution obtained in the step S6 in vacuum degree to prepare the cationic self-repairing aqueous polyurethane emulsion.
Preferably, the preparation raw materials of the sulfonic acid type self-repairing waterborne polyurethane comprise the following components in percentage by weight: 60-120 parts of polymer polyol, 30-60 parts of polyisocyanate, 0.01-0.03 part of catalyst, 30-60 parts of organic solvent, 5-10 parts of hydrophilic chain extender, 5-10 parts of disulfide bond compound, 5-10 parts of acylhydrazone bond compound, 3-10 parts of salt forming agent and 200-400 parts of deionized water.
Preferably, the polymer polyol is one or two of polyether polyol and polyester polyol.
Preferably, the polyisocyanate is one of aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate.
Preferably, the organic solvent is one or a mixture of more than two of acetone, butanone, methyl ethyl ketone, dioxane, N-dimethyl amide, N-methyl pyrrolidone and ethyl acetate.
Preferably, the hydrophilic chain extender is one or a mixture of two or more of diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-benzyldiethanolamine, bis (2-hydroxyethyl) benzylaniline (BHBA), bis (2-hydroxypropyl) aniline (BHPA), tert-butyldiethanolamine, dimethylethanolamine, and 2, 3-dibromosuccinic acid.
Preferably, the disulfide compound is one or a mixture of two or more of 4, 4 '-diaminodiphenyl sulfide, 3' -dihydroxydiphenyl disulfide, 4 '-dihydroxydiphenyl sulfide, 2-aminodiphenyl sulfide, 2' -dithiodiethanol (HEDS), and dihydroxyethyl diethyl thiuram disulfide (TDS diol).
Preferably, the acylhydrazone bond compound is one or two of quinoxalinone hydrazone and diflufenzopyr.
Preferably, the salt forming agent is hydrochloric acid, acetic acid, oxalic acid and CH 3 SO 4 、CH 3 One or a mixture of more than two of I.
Preferably, the cationic self-repairing waterborne polyurethane is prepared by the preparation method of the cationic self-repairing waterborne polyurethane.
Compared with the prior art, the invention has the beneficial effects that: the invention realizes infinite self-repair of polyurethane by utilizing reversible chemical bonds of disulfide bonds and acylhydrazone bonds and hydrogen bonding action of the polyurethane, and has the advantages of dust prevention, sterilization, environmental protection, excellent mechanical property, good compatibility, easy modification and the like. The polyurethane has the advantages that the framework of the polyurethane is provided with the cationic group which is insensitive to water hardness, so that the polyurethane can be applied under acidic conditions, is particularly suitable for surface treatment of anionic leather, textile, papermaking and glass, and has better application in the fields of leather, coating, adhesive, textile, papermaking and the like.
Drawings
FIG. 1 is a flow chart of the preparation method of the cationic self-repairing waterborne polyurethane.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
As shown in fig. 1, fig. 1 is a flow chart of the preparation method of the cationic self-repairing aqueous polyurethane. The preparation method of the cationic self-repairing waterborne polyurethane comprises the following steps of raw materials in parts by mass:
s1, heating 60-120 parts of polymer polyol to 100-130 ℃, and dehydrating in vacuum for 1-2 h;
s2, carrying out nitrogen protection on the solution obtained in the step S1, cooling to 60-90 ℃, adding 30-60 parts of polyisocyanate and 0.01-0.03 part of catalyst, reacting for 1-3 h, and adding 30-60 parts of organic solvent to adjust viscosity;
s3, adding 5-10 parts of hydrophilic chain extender into the solution obtained in the step S2, and reacting for 1-3 h at 70-90 ℃;
s4, adding 5-10 parts of disulfide bond compounds and 5-10 parts of acylhydrazone bond compounds into the solution obtained in the step S3, and reacting at 40-90 ℃ for 1-3 h;
s5, cooling the solution obtained in the step S4 to 30-50 ℃, adding 3-10 parts of a salt forming agent, and reacting for 10-30 min;
s6, cooling the solution obtained in the step S5 to 10-30 ℃, adding 200-400 parts of deionized water, and dispersing at high speed for 10-30 min;
s7, desolventizing the solution obtained in the step S6 in vacuum degree to prepare the cationic self-repairing aqueous polyurethane emulsion.
The polymer polyol is one or two of polyether polyol and polyester polyol.
The polyisocyanate is one of aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate.
The organic solvent is one or a mixture of more than two of acetone, butanone, methyl ethyl ketone, dioxane, N-dimethyl amide, N-methyl pyrrolidone and ethyl acetate.
The hydrophilic chain extender is one or a mixture of more than two of diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-benzyldiethanolamine, bis (2-hydroxyethyl) benzylaniline (BHBA), bis (2-hydroxypropyl) aniline (BHPA), tert-butyldiethanolamine, dimethylethanolamine and 2, 3-dibromo-succinic acid.
The disulfide bond compound is one or a mixture of more than two of 4, 4 '-diaminodiphenyl sulfide, 3' -dihydroxydiphenyl disulfide, 4 '-dihydroxydiphenyl sulfide, 2-aminodiphenyl sulfide, 2' -dithiodiethanol (HEDS) and dihydroxyethyl diethyl thiuram disulfide (TDS glycol).
The acylhydrazone bond compound is one or two of quinoxalin hydrazone and diflufenzopyr.
The salt forming agent is hydrochloric acid, acetic acid, oxalic acid and CH 3 SO 4 、CH 3 One or a mixture of more than two of I.
The catalyst is one or a mixture of more than two of organic tin and tertiary amine.
According to the invention, a disulfide bond and an acylhydrazone bond are introduced into a cationic polyurethane main chain to prepare the cationic self-repairing aqueous polyurethane emulsion, and a disulfide bond and mercaptan can be mutually converted through an oxidation-reduction reaction, namely two mercaptan groups can be oxidized to generate a disulfide bond, and the disulfide bond can also be reduced to two mercaptan groups; and the dynamic exchange reaction of the acylhydrazone bond in the molecular chain segment can realize multiple repairs. The reversible exchange chemical bonds of the disulfide bonds and the acylhydrazone bonds and the hydrogen bond effect of the polyurethane are utilized to realize the repair of material damage, the self-repairing coating has strong self-repairing capability, self-heals cracks and damaged coatings, can effectively improve the low self-repairing rate and limited repairing times of the existing self-repairing coatings, and can realize infinite self-repairing.
The polyurethane has the advantages of insensitive water hardness because the skeleton of the polyurethane is provided with the cationic groups, and can be used under acidic conditions. Has good application prospect in treating substrates with negative charges, such as leather, fabrics, coatings, printing ink and paper surfaces.
Example one
The preparation of the cationic self-repairing waterborne polyurethane comprises the following steps:
s1, adding 100 parts of polytetrahydrofuran diol into a reactor, and carrying out vacuum dehydration treatment at 120 ℃ for 2 h;
s2, at N 2 Under protection, cooling to 80 ℃, adding 44.5 parts of isophorone diisocyanate and 0.03 part of dibutyltin dilaurate, heating to 90 ℃, reacting for 3 hours, and adjusting the viscosity by 40 parts of N-methyl pyrrolidone;
s3, cooling to 70 ℃, adding 9 parts of N-methyldiethanolamine, and reacting for 3 hours;
s4, cooling to 50 ℃, adding 10 parts of 4, 4' -diaminodiphenyl sulfide and 8 parts of quinoxime hydrazone, and reacting for 2 hours;
s5, cooling to 30 ℃, adding 5 parts of acetic acid, and reacting for 130 min;
s6, cooling to 30 ℃, transferring to an emulsification barrel, and adding 200 parts of deionized water to disperse for 30min at a high speed;
s7, finally, desolventizing under vacuum degree to prepare the cationic self-repairing aqueous polyurethane emulsion;
the emulsion obtained had an average particle diameter of 70nm, a pH of 6.0, a solids content of 46% and a viscosity of 50 mPas.
Example two
The preparation of the cationic self-repairing waterborne polyurethane comprises the following steps:
s1, adding 100 parts of polycaprolactone diol into a reactor, and carrying out vacuum dehydration treatment at 120 ℃ for 2 hours;
s2, at N 2 Under protection, cooling to 70 ℃, adding 50 parts of 4, 4-diphenylmethane diisocyanate (MDI) and 0.02 part of stannous octoate, heating to 85 ℃, reacting for 3 hours, and adjusting the viscosity by 40 parts of 20ml dioxane;
s3, cooling to 70 ℃, adding 10 parts of N-ethyldiethanolamine, and reacting for 3 hours;
s4, heating to 50 ℃, adding 10 parts of 4, 4' -dihydroxy diphenyl sulfide and 7-diflufenzopyr, and reacting for 3 hours;
s5, cooling to 30 ℃, adding 10 parts of acetic acid, and reacting for 130 min;
s6, cooling to 30 ℃, transferring to an emulsification barrel, and adding 200 parts of deionized water to disperse for 30min at a high speed;
s7, finally, desolventizing under vacuum degree to prepare the cationic self-repairing aqueous polyurethane emulsion;
the emulsion obtained had an average particle diameter of 90nm, a pH of 6.0, a solids content of 48% and a viscosity of 55 mPas.
EXAMPLE III
The preparation of the cationic self-repairing waterborne polyurethane comprises the following steps:
s1, adding 100 parts of polyoxypropylene glycol into a reactor, and carrying out vacuum dehydration treatment for 2h at 120 ℃;
s2, at N 2 Under protection, cooling to 70 ℃, adding 35 parts of Toluene Diisocyanate (TDI) and dropwise adding 0.02 part of stannous octoate, heating to 85 ℃, reacting for 3 hours, and obtaining 40 parts of 20ml butanone viscosity;
s3, cooling to 80 ℃, and adding 10 parts of diethanolamine for reaction for 3 hours;
s4, heating to 90 ℃, adding 15 parts of 2, 2' -dithiodiethanol and 5 parts of quinoxime hydrazone, and reacting for 3 hours;
s5, cooling to 30 ℃, adding 6 parts of acetic acid, and reacting for 130 min;
s6, cooling to 30 ℃, transferring to an emulsification barrel, and adding 200 parts of deionized water to disperse for 30min at a high speed;
s7, finally, desolventizing under vacuum degree to prepare the cationic self-repairing aqueous polyurethane emulsion;
the emulsion obtained had an average particle diameter of 80nm, a pH of 6.0, a solids content of 44% and a viscosity of 55 mPas.
Pouring the cationic self-repairing waterborne polyurethane obtained in the first, second and third embodiments into a PTFE template, volatilizing water at room temperature to form a film, and vacuum-drying at 50 ℃ for 2 days under 2.66kPa to obtain a film for testing the self-repairing performance of the sample.
Tensile properties are used to characterize the self-healing properties of polyurethanes. Preparation of tensile stress strain Property test specimens according to the standard GB/T528-1988, each set of data is the average of the results of 5 specimens.
Cutting the prepared polyurethane into dumbbell-shaped (100mm multiplied by 10mm multiplied by 1mm) sample strips to be tested according to the specification, equally dividing the sample strips into two parts, and taking one part as an original sample to test the tensile strength;
the other part is cut off by a transverse knife from the middle position of the neck of the sample by medical scissors, and then is immediately spliced and placed in a mould;
according to the experimental conditions, the test specimens were respectively placed at different times and temperatures for self-healing, then taken out and subjected to tensile strength testing, and the maximum tensile strength (σ) was recorded. And comparing the self-healing spline strength with the original spline strength to obtain the self-healing efficiency. Self-repair efficiency (H) is generally defined as:
surface-cationic self-repairing performance test result of self-repairing waterborne polyurethane
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A preparation method of cationic self-repairing waterborne polyurethane is characterized by comprising the following steps:
s1, heating the polymer polyol to 100-130 ℃, and dehydrating for 1-2 h in vacuum;
s2, carrying out nitrogen protection on the solution obtained in the step S1, cooling to 60-90 ℃, adding polyisocyanate and a catalyst, reacting for 1-3 h, and adding an organic solvent to adjust viscosity;
s3, adding a hydrophilic chain extender into the solution obtained in the step S2, and reacting for 1-3 h at 70-90 ℃;
s4, adding a disulfide bond compound and an acylhydrazone bond compound into the solution obtained in the step S3, and reacting at 40-90 ℃ for 1-3 h;
s5, cooling the solution obtained in the step S4 to 30-50 ℃, adding a salt forming agent, and reacting for 10-30 min;
s6, cooling the solution obtained in the step S5 to 10-30 ℃, adding deionized water, and dispersing at a high speed for 10-30 min;
s7, desolventizing the solution obtained in the step S6 in vacuum to prepare a cationic self-repairing aqueous polyurethane emulsion;
the preparation raw materials of the cationic self-repairing waterborne polyurethane comprise the following components in parts by weight: 60-120 parts of the polymer polyol, 30-60 parts of the polyisocyanate, 0.01-0.03 part of the catalyst, 30-60 parts of the organic solvent, 5-10 parts of a hydrophilic chain extender, 5-10 parts of the disulfide bond compound, 5-10 parts of the acylhydrazone bond compound, 3-10 parts of a salt forming agent and 200-400 parts of the deionized water;
the disulfide bond compound is one or a mixture of more than two of 3, 3 '-dihydroxy diphenyl disulfide, 2' -dithiodiethanol and dihydroxyethyl diethyl thiuram disulfide;
the acylhydrazone bond compound is one or two of quinoxalin hydrazone and diflufenzopyr.
2. The method of claim 1, wherein the polymer polyol is one or both of polyether polyol and polyester polyol.
3. The method of claim 1, wherein the polyisocyanate is one of an aromatic polyisocyanate, an aliphatic polyisocyanate, and an alicyclic polyisocyanate.
4. The method of claim 1, wherein the organic solvent is one or a mixture of two or more of acetone, methyl ethyl ketone, dioxane, N-methyl pyrrolidone, and ethyl acetate.
5. The method of claim 1, wherein the hydrophilic chain extender is one or a mixture of two or more of diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-benzyldiethanolamine, bis (2-hydroxypropyl) aniline (BHPA), t-butyldiethanolamine, and dimethylethanolamine.
6. The method of claim 1, wherein the salt forming agent is one or a mixture of two or more of hydrochloric acid, acetic acid, and oxalic acid.
7. A cationic self-healing aqueous polyurethane obtained by the process for preparing a cationic self-healing aqueous polyurethane according to any of claims 1 to 6.
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| CN113292701B (en) * | 2021-05-24 | 2022-08-05 | 中国科学院宁波材料技术与工程研究所 | Self-healing ionic polyurethane, preparation method and application |
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