Polyurethane dispersoid for water-based bio-based decorative paper ink and preparation method of polyurethane dispersoid
By preparing a combination of modified polyurethane and polyurethane, the problem that the polyurethane dispersion in aqueous bio-based decorative paper ink is easily eroded by bacteria, achieving good antibacterial and flame retardant effects, and extending the service life of the product.
Patent Information
- Application Number
- CN202411735800.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-29
- Publication Date
- 2025-02-25
AI Technical Summary
In existing aqueous bio-based decorative paper inks, polyurethane dispersions are easily eroded by bacteria after long-term placement, resulting in its destruction and affecting its use.
Using a combination of modified polyurethane and polyurethane, a polyurethane dispersion for aqueous bio-based decorative paper ink with good flame retardant and antibacterial effects is prepared by a specific preparation method, including multi-step reaction and the use of a catalyst.
The modified polyurethane dispersion significantly improves the antibacterial effect, can effectively prevent bacterial erosion, extend the service life of the product, and provide better flame retardant performance.
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of paper and ink, and in particular to a water-based bio-based polyurethane dispersion for decorative paper and ink and a preparation method thereof. Background Art
[0002] Water-based bio-based decorative paper ink is an environmentally friendly ink specially used for decorative paper printing. It uses water as a solvent and is made from renewable or bio-based raw materials. It is widely used in the field of decorative paper printing, including but not limited to decorative printing of plastic films such as PVC and PET, as well as printing of non-absorbent materials such as paper and synthetic paper. Polyurethane dispersions show good adhesion on a variety of substrates, including metals, plastics, paper, etc., making it an important adhesive component in paper ink, which can ensure that the ink is firmly attached to the surface of the substrate and is not easy to fall off. However, during long-term storage, bacteria will erode it, causing it to be destroyed, thus affecting its normal use. Therefore, how to avoid this phenomenon is the key to solving the problem. Summary of the invention
[0003] 1. Technical issues to be resolved In view of the deficiencies in the prior art, the present invention provides a water-based bio-based polyurethane dispersion for decorative paper ink and a preparation method thereof, which has good flame retardant and antibacterial effects.
[0004] (II) Technical solution To achieve the above object, the present invention provides the following technical solution: a water-based bio-based decorative paper ink polyurethane dispersion, comprising the following weight components: 30-45 parts by weight of modified polyurethane, 20-40 parts by weight of polyurethane; The preparation method of the modified polyurethane is: (1) Add acetonitrile solvent, N-methyliminodiacetic acid, and 3-chloropropylene to a reactor, react at 50-75°C for 4-8 hours, cool after reaction, and concentrate under reduced pressure. The product is washed with petroleum ether and purified by recrystallization in ethanol to obtain intermediate 1; (2) Add 4-hydroxyethylimidazole and intermediate 1 to N,N-dimethylformamide solvent, stir evenly, continue to add p-toluenesulfonic acid catalyst, react at 65-80°C for 7-9h, and then distill under reduced pressure, wash and dry to obtain intermediate 2; (3) Add 1.2-4.6 parts by weight of purified polyurethane particles to dimethylformamide solvent, stir and dissolve at 90-115°C for 6-10 hours, continue to add 2.2-3.4 parts by weight of methyl methacrylate isothiocyanate, introduce nitrogen for protection, then add 0.01-0.02 parts by weight of triethylamine, and oil bath at 50-75°C. After the reaction, wash with acetonitrile and dry to obtain olefinated polyurethane; (4) Add 3-6 parts by weight of olefinic polyurethane, 4-9 parts by weight of sodium methyl methacrylate, 2-5 parts by weight of intermediate 2, 6-10 parts by weight of acrylic acid, and 4-7 parts by weight of methyl acrylate to N,N-dimethylformamide solvent, add 0.4-0.6 parts by weight of initiator after dissolution, react at 80-110° C. for 3-6 hours, remove the solvent by distillation under reduced pressure after the reaction, filter, wash and dry to obtain modified polyurethane.
[0005] Preferably, the mass ratio of N-methyliminodiacetic acid to 3-chloropropylene in (1) is 1:1.1-1.3.
[0006] Preferably, the mass ratio of 4-hydroxyethylimidazole, intermediate 1, and p-toluenesulfonic acid catalyst in (2) is 0.8-1.2:1:0.01-0.03.
[0007] Preferably, the oil bath time in (3) is 8-11 hours.
[0008] Preferably, the initiator in (4) is ammonium persulfate.
[0009] Preferably, the preparation method of the polyurethane is: S1. Add 4-10 parts by weight of cellulose to a 2-4% sodium hydroxide aqueous solution, then dropwise add 10-15 parts by weight of epichlorohydrin and ethanol solvent, stir and react at 50-70° C. for 2-6 hours to obtain epoxy cellulose, continue to add 7-10 parts by weight of intermediate 2 and 1-1.3 parts by weight of boron trifluoride ether catalyst, react at 70-95° C. for 6-10 hours, filter and wash after the reaction to obtain a modified cellulose chain extender; S2. After removing water from the polyether diol, mix it evenly with hexamethylene diisocyanate, introduce nitrogen, then add dibutyltin dilaurate catalyst dropwise, react at 50-80°C for 2-4h to carry out prepolymerization, then add modified cellulose chain extender, stir to continue chain extension reaction, react at 45-60°C for 3-4h, after the reaction is completed, cool and discharge to obtain polyurethane.
[0010] Preferably, the mass ratio of the polyether diol, hexamethylene diisocyanate, dibutyltin dilaurate catalyst, and modified cellulose chain extender in S2 is 1.2-1.8:1:0.01-0.02:0.4-0.5.
[0011] Preferably, the preparation method of the water-based bio-based decorative paper ink polyurethane dispersion is: adding modified polyurethane and polyurethane into a reactor, stirring for 5-10 minutes, and obtaining the water-based bio-based decorative paper ink polyurethane dispersion.
[0012] 3. Beneficial technical effects The invention obtains water-based bio-based decorative paper ink polyurethane dispersion by adding modified polyurethane and polyurethane into a reactor and stirring.
[0013] The quaternary ammonium salts and imidazoles contained in the modified polyurethane and polyurethane have good antibacterial effects. The bacterial cell wall carries a negative charge, and the positively charged nitrogen atoms in the quaternary ammonium salt can interact with the negative charges on the bacterial cell wall and cell membrane, causing the quaternary ammonium salt to be adsorbed on the bacterial surface, destroying its integrity, causing the bacterial cytoplasmic contents to leak out, and ultimately leading to bacterial death. The imidazole group can interfere with the cross-linking of the bacterial cell wall peptidoglycan, hindering the synthesis of the bacterial cell wall. This effect will cause the structural integrity of the bacterial cell wall to be damaged, ultimately leading to bacterial death. The modified cellulose chain extender has more cellulose grafting sites, which increases the degree of substitution of the quaternary ammonium salt group and the imidazole group, further improving its antibacterial effect. DETAILED DESCRIPTION Example 1
[0014] (1) Add acetonitrile solvent, N-methyliminodiacetic acid, and 3-chloropropylene to a reactor, wherein the mass ratio of N-methyliminodiacetic acid to 3-chloropropylene is 1:1.1, and react at 50°C for 4 hours. After the reaction, cool and concentrate under reduced pressure. The product is washed with petroleum ether and purified by recrystallization in ethanol to obtain intermediate 1; (2) Add 4-hydroxyethylimidazole and intermediate 1 to N,N-dimethylformamide solvent, stir evenly, and continue to add p-toluenesulfonic acid catalyst, wherein the mass ratio of 4-hydroxyethylimidazole, intermediate 1 and p-toluenesulfonic acid catalyst is 0.8:1:0.01, react at 65°C for 7h, and then distill under reduced pressure, wash and dry to obtain intermediate 2; (3) Add 1.2 parts by weight of purified polyurethane particles to dimethylformamide solvent, stir and dissolve at 90°C for 6 hours, continue to add 2.2 parts by weight of methyl methacrylate isothiocyanate, introduce nitrogen for protection, then add 0.01 parts by weight of triethylamine, and place in an oil bath at 50°C for 8 hours. After the reaction, wash with acetonitrile and dry to obtain olefinic polyurethane; (4) adding 3 parts by weight of olefinic polyurethane, 4 parts by weight of sodium methyl methacrylate, 2 parts by weight of intermediate 2, 6 parts by weight of acrylic acid, and 4 parts by weight of methyl acrylate to N,N-dimethylformamide solvent, adding 0.4 parts by weight of ammonium persulfate initiator after dissolution, reacting at 80° C. for 3 hours, and removing the solvent by reduced pressure distillation after the reaction, filtering, washing and drying to obtain a modified polyurethane; (5) Add 4-10 parts by weight of cellulose to a 2% sodium hydroxide aqueous solution, then dropwise add 10-15 parts by weight of epichlorohydrin and ethanol solvent, stir and react at 50° C. for 2 h to obtain epoxy cellulose, then add 7 parts by weight of intermediate 2 and 1 part by weight of boron trifluoride ether catalyst, react at 70° C. for 6 h, filter and wash after the reaction to obtain a modified cellulose chain extender; (6) After removing water from the polyether diol, mix it evenly with hexamethylene diisocyanate, introduce nitrogen, then drop a dibutyltin dilaurate catalyst, react at 50°C for 2 hours to perform prepolymerization, then add a modified cellulose chain extender, wherein the mass ratio of polyether diol, hexamethylene diisocyanate, dibutyltin dilaurate catalyst, and modified cellulose chain extender is 1.2:1:0.01:0.4, stir to continue the chain extension reaction, react at 45°C for 3 hours, and after the reaction is completed, cool and discharge to obtain polyurethane; (7) 30 parts by weight of modified polyurethane and 20 parts by weight of polyurethane were added into a reactor and stirred for 5 minutes to obtain a polyurethane dispersion for water-based bio-based decorative paper ink. Example 2
[0015] (1) Add acetonitrile solvent, N-methyliminodiacetic acid, and 3-chloropropylene to a reactor, wherein the mass ratio of N-methyliminodiacetic acid to 3-chloropropylene is 1:1.3, and react at 75°C for 8 hours. After reaction, cool and concentrate under reduced pressure. The product is washed with petroleum ether and purified by recrystallization in ethanol to obtain intermediate 1; (2) Add 4-hydroxyethylimidazole and intermediate 1 to N,N-dimethylformamide solvent, stir evenly, and continue to add p-toluenesulfonic acid catalyst, wherein the mass ratio of 4-hydroxyethylimidazole, intermediate 1, and p-toluenesulfonic acid catalyst is 1.2:1:0.03, react at 80°C for 9 hours, and then distill under reduced pressure, wash and dry to obtain intermediate 2; (3) Add 4.6 parts by weight of purified polyurethane particles to dimethylformamide solvent, stir and dissolve at 115°C for 10 hours, continue to add 3.4 parts by weight of methyl methacrylate isothiocyanate, introduce nitrogen for protection, then add 0.02 parts by weight of triethylamine, and place in an oil bath at 75°C for 11 hours. After the reaction, wash with acetonitrile and dry to obtain olefinic polyurethane; (4) Add 6 parts by weight of olefinic polyurethane, 9 parts by weight of sodium methyl methacrylate, 5 parts by weight of intermediate 2, 10 parts by weight of acrylic acid, and 7 parts by weight of methyl acrylate into N,N-dimethylformamide solvent, add 0.6 parts by weight of ammonium persulfate initiator after dissolution, react at 110° C. for 6 hours, remove the solvent by distillation under reduced pressure after the reaction, filter, wash and dry to obtain modified polyurethane; (5) Add 10 parts by weight of cellulose to a 4% sodium hydroxide aqueous solution, then dropwise add 15 parts by weight of epichlorohydrin and ethanol solvent, stir and react at 70°C for 6 hours to obtain epoxy cellulose, then add 10 parts by weight of intermediate 2 and 1.3 parts by weight of boron trifluoride ether catalyst, react at 95°C for 10 hours, filter and wash after the reaction to obtain a modified cellulose chain extender; (6) After removing water from the polyether diol, mix it evenly with hexamethylene diisocyanate, introduce nitrogen, then drop dibutyltin dilaurate catalyst, react at 80°C for 4 hours to perform prepolymerization, then add modified cellulose chain extender, wherein the mass ratio of polyether diol, hexamethylene diisocyanate, dibutyltin dilaurate catalyst, and modified cellulose chain extender is 1.8:1:0.02:0.5, stir to continue chain extension reaction, react at 60°C for 4 hours, and after the reaction is completed, cool and discharge to obtain polyurethane; (7) 45 parts by weight of modified polyurethane and 40 parts by weight of polyurethane were added into a reactor and stirred for 10 minutes to obtain a polyurethane dispersion for water-based bio-based decorative paper ink. Example 3
[0016] (1) Add acetonitrile solvent, N-methyliminodiacetic acid, and 3-chloropropylene to a reactor, wherein the mass ratio of N-methyliminodiacetic acid to 3-chloropropylene is 1:1.2, and react at 70°C for 6 hours. After the reaction, cool the mixture and concentrate under reduced pressure. The product is washed with petroleum ether and then purified by recrystallization in ethanol to obtain intermediate 1. (2) Add 4-hydroxyethylimidazole and intermediate 1 to N,N-dimethylformamide solvent, stir evenly, and continue to add p-toluenesulfonic acid catalyst, wherein the mass ratio of 4-hydroxyethylimidazole, intermediate 1 and p-toluenesulfonic acid catalyst is 1.1:1:0.02, react at 75°C for 8h, and then distill under reduced pressure, wash and dry to obtain intermediate 2; (3) Add 3.6 parts by weight of purified polyurethane particles to dimethylformamide solvent, stir and dissolve at 100°C for 8 hours, continue to add 2.8 parts by weight of methyl methacrylate isothiocyanate, introduce nitrogen for protection, then add 0.015 parts by weight of triethylamine, and place in an oil bath at 65°C for 10 hours. After the reaction, wash with acetonitrile and dry to obtain olefinic polyurethane; (4) adding 4 parts by weight of olefinic polyurethane, 6 parts by weight of sodium methyl methacrylate, 4 parts by weight of intermediate 2, 8 parts by weight of acrylic acid, and 6 parts by weight of methyl acrylate to N,N-dimethylformamide solvent, adding 0.5 parts by weight of ammonium persulfate initiator after dissolution, reacting at 90° C. for 5 hours, removing the solvent by reduced pressure distillation after the reaction, filtering, washing and drying to obtain a modified polyurethane; (5) Add 7 parts by weight of cellulose to a 3% sodium hydroxide aqueous solution, then dropwise add 12 parts by weight of epichlorohydrin and ethanol solvent, stir and react at 60°C for 4 hours to obtain epoxy cellulose, then add 8 parts by weight of intermediate 2 and 1.2 parts by weight of boron trifluoride ether catalyst, react at 85°C for 8 hours, filter and wash after the reaction to obtain a modified cellulose chain extender; (6) After removing water from the polyether diol, mix it evenly with hexamethylene diisocyanate, introduce nitrogen, then drop dibutyltin dilaurate catalyst, react at 65°C for 3 hours to perform prepolymerization, then add modified cellulose chain extender, wherein the mass ratio of polyether diol, hexamethylene diisocyanate, dibutyltin dilaurate catalyst, and modified cellulose chain extender is 1.6:1:0.015:0.45, stir to continue chain extension reaction, react at 50°C for 3 hours, and after the reaction is completed, cool and discharge to obtain polyurethane; (7) 36 parts by weight of modified polyurethane and 30 parts by weight of polyurethane were added into a reactor and stirred for 7 minutes to obtain a polyurethane dispersion for water-based bio-based decorative paper ink. Example 4
[0017] (1) Add acetonitrile solvent, N-methyliminodiacetic acid, and 3-chloropropylene to a reactor, wherein the mass ratio of N-methyliminodiacetic acid to 3-chloropropylene is 1:1.1, and react at 50°C for 4 hours. After the reaction, cool and concentrate under reduced pressure. The product is washed with petroleum ether and purified by recrystallization in ethanol to obtain intermediate 1; (2) Add 4-hydroxyethylimidazole and intermediate 1 to N,N-dimethylformamide solvent, stir evenly, and continue to add p-toluenesulfonic acid catalyst, wherein the mass ratio of 4-hydroxyethylimidazole, intermediate 1 and p-toluenesulfonic acid catalyst is 0.8:1:0.01, react at 65°C for 7h, and then distill under reduced pressure, wash and dry to obtain intermediate 2; (3) Add 4.6 parts by weight of purified polyurethane particles to dimethylformamide solvent, stir and dissolve at 115°C for 10 hours, continue to add 3.4 parts by weight of methyl methacrylate isothiocyanate, introduce nitrogen for protection, then add 0.02 parts by weight of triethylamine, and place in an oil bath at 75°C for 11 hours. After the reaction, wash with acetonitrile and dry to obtain olefinic polyurethane; (4) Add 6 parts by weight of olefinic polyurethane, 9 parts by weight of sodium methyl methacrylate, 5 parts by weight of intermediate 2, 10 parts by weight of acrylic acid, and 7 parts by weight of methyl acrylate into N,N-dimethylformamide solvent, add 0.6 parts by weight of ammonium persulfate initiator after dissolution, react at 110° C. for 6 hours, remove the solvent by distillation under reduced pressure after the reaction, filter, wash and dry to obtain modified polyurethane; (5) Add 7 parts by weight of cellulose to a 3% sodium hydroxide aqueous solution, then dropwise add 12 parts by weight of epichlorohydrin and ethanol solvent, stir and react at 60°C for 4 hours to obtain epoxy cellulose, then add 8 parts by weight of intermediate 2 and 1.2 parts by weight of boron trifluoride ether catalyst, react at 85°C for 8 hours, filter and wash after the reaction to obtain a modified cellulose chain extender; (6) After removing water from the polyether diol, mix it evenly with hexamethylene diisocyanate, introduce nitrogen, then drop dibutyltin dilaurate catalyst, react at 65°C for 3 hours to perform prepolymerization, then add modified cellulose chain extender, wherein the mass ratio of polyether diol, hexamethylene diisocyanate, dibutyltin dilaurate catalyst, and modified cellulose chain extender is 1.6:1:0.015:0.45, stir to continue chain extension reaction, react at 50°C for 3 hours, and after the reaction is completed, cool and discharge to obtain polyurethane; (7) 36 parts by weight of modified polyurethane and 30 parts by weight of polyurethane were added into a reactor and stirred for 7 minutes to obtain a polyurethane dispersion for water-based bio-based decorative paper ink.
[0018] Comparative Example 1 Compared with Example 3, this comparative example is different in that no modified polyurethane is added.
[0019] Comparative Example 2 Compared with Example 3, this comparative example is different in that no polyurethane is added.
[0020] A Staphylococcus aureus liquid with a concentration of 2×108 CFU / mL was added to a sterilized culture dish as a test strain, and then a solid agar medium was added and dissolved, cooled to 45°C, and then poured into a culture dish, 20 mL was poured into each plate with an inner diameter of 10 cm, and then the polyurethane dispersions of the embodiments of the present invention and the comparative example (with a diameter of 3 cm and a thickness of 1 mm) were placed on the culture plate, and cultured in a constant temperature incubator for 12 hours at a temperature of 37°C. After culture, the diameter of the inhibition zone was measured. The test results are shown in Table 1.
[0021] Table 1: Antimicrobial testing.
[0022] project Diameter of inhibition zone (mm) Example 1 15.7 Example 2 16.8 Example 3 16.6 Example 4 16.3 Comparative Example 1 12.4 Comparative Example 2 11.5 As can be seen from Table 1, the water-based bio-based polyurethane dispersion for decorative paper ink Examples 1-4 of the present invention have better antibacterial effects than Comparative Examples 1-2.
[0023] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.
Claims
1. A water-based bio-based polyurethane dispersion for decorative paper ink, characterized in that: The invention comprises the following components by weight: 30-45 parts by weight of modified polyurethane and 20-40 parts by weight of polyurethane; The preparation method of the modified polyurethane is: (1) Add acetonitrile solvent, N-methyliminodiacetic acid, and 3-chloropropylene to a reactor, react at 50-75°C for 4-8 hours, cool after reaction, and concentrate under reduced pressure. The product is washed with petroleum ether and purified by recrystallization in ethanol to obtain intermediate 1; (2) Add 4-hydroxyethylimidazole and intermediate 1 to N,N-dimethylformamide solvent, stir evenly, continue to add p-toluenesulfonic acid catalyst, react at 65-80°C for 7-9h, and then distill under reduced pressure, wash and dry to obtain intermediate 2; (3) Add 1.2-4.6 parts by weight of purified polyurethane particles to dimethylformamide solvent, stir and dissolve at 90-115°C for 6-10 hours, continue to add 2.2-3.4 parts by weight of methyl methacrylate isothiocyanate, introduce nitrogen for protection, then add 0.01-0.02 parts by weight of triethylamine, and oil bath at 50-75°C. After the reaction, wash with acetonitrile and dry to obtain olefinated polyurethane; (4) Add 3-6 parts by weight of olefinic polyurethane, 4-9 parts by weight of sodium methyl methacrylate, 2-5 parts by weight of intermediate 2, 6-10 parts by weight of acrylic acid, and 4-7 parts by weight of methyl acrylate to N,N-dimethylformamide solvent, add 0.4-0.6 parts by weight of initiator after dissolution, react at 80-110° C. for 3-6 hours, remove the solvent by distillation under reduced pressure after the reaction, filter, wash and dry to obtain modified polyurethane.
2. The water-based bio-based polyurethane dispersion for decorative paper ink according to claim 1, characterized in that: The mass ratio of N-methyliminodiacetic acid to 3-chloropropylene in (1) is 1:1.1-1.
3.
3. The water-based bio-based polyurethane dispersion for decorative paper ink according to claim 1, characterized in that: The mass ratio of 4-hydroxyethylimidazole, intermediate 1 and p-toluenesulfonic acid catalyst in (2) is 0.8-1.2:1:0.01-0.
03.
4. The water-based bio-based polyurethane dispersion for decorative paper ink according to claim 1, characterized in that: The oil bath time in (3) is 8-11 hours.
5. The water-based bio-based polyurethane dispersion for decorative paper ink according to claim 1, characterized in that: The initiator in (4) is ammonium persulfate.
6. The water-based bio-based polyurethane dispersion for decorative paper ink according to claim 1, characterized in that: The preparation method of the polyurethane is: S1. Add 4-10 parts by weight of cellulose to a 2-4% sodium hydroxide aqueous solution, then dropwise add 10-15 parts by weight of epichlorohydrin and ethanol solvent, stir and react at 50-70° C. for 2-6 hours to obtain epoxy cellulose, continue to add 7-10 parts by weight of intermediate 2 and 1-1.3 parts by weight of boron trifluoride ether catalyst, react at 70-95° C. for 6-10 hours, filter and wash after the reaction to obtain a modified cellulose chain extender; S2. After removing water from the polyether diol, mix it evenly with hexamethylene diisocyanate, introduce nitrogen, then add dibutyltin dilaurate catalyst dropwise, react at 50-80°C for 2-4h to carry out prepolymerization, then add modified cellulose chain extender, stir to continue chain extension reaction, react at 45-60°C for 3-4h, after the reaction is completed, cool and discharge to obtain polyurethane.
7. The water-based bio-based polyurethane dispersion for decorative paper ink according to claim 6, characterized in that: The mass ratio of the polyether diol, hexamethylene diisocyanate, dibutyltin dilaurate catalyst, and modified cellulose chain extender in S2 is 1.2-1.8:1:0.01-0.02:0.4-0.
5.
8. A method for preparing the water-based bio-based polyurethane dispersion for decorative paper ink according to any one of claims 1 to 7, characterized in that: The preparation method of the water-based bio-based decorative paper ink polyurethane dispersion is as follows: adding modified polyurethane and polyurethane into a reactor, stirring for 5-10 minutes, and obtaining the water-based bio-based decorative paper ink polyurethane dispersion.