CN114106288A - Preparation method and application of waterborne polyurethane dispersant - Google Patents
Preparation method and application of waterborne polyurethane dispersant 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
- C08G18/65—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08G18/65—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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0022—Wet grinding of pigments
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
- C09B67/0066—Aqueous dispersions of pigments containing only dispersing agents
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Abstract
The invention discloses a preparation method and application of a waterborne polyurethane dispersant. Belongs to the field of polymer dispersants, and specifically comprises the following steps: weighing a compound containing isocyanate groups as an initiator, reacting the initiator with polyethylene glycol in the presence of nitrogen and a catalyst to generate a polyurethane prepolymer, and adding an organic solvent into a reaction system to control viscosity; adding a chain extender 1 to perform chain extension reaction for 2 to 2.5 hours at the temperature of between 75 and 80 ℃; adding a chain extender 2 at the temperature of 75-80 ℃ to continue chain extension reaction for 2-2.5 h; cooling to 50-55 ℃, adding an end capping agent for end capping reaction for 1-1.5 h; and after the reaction is finished, adding triethylamine to perform neutralization reaction for 1h, adding deionized water to perform high-speed emulsification for 20-30min, and performing reduced pressure distillation at room temperature to remove the organic solvent to obtain the waterborne polyurethane dispersant. The dispersant with the structure is used for preparing the liquid indigo dye, so that the grinding efficiency is high, and the storage stability of the dye is good.
Description
Technical Field
The invention belongs to the field of high molecular dispersants, and relates to a preparation method of a water-based polyurethane dispersant and application of the water-based polyurethane dispersant in preparation of liquid indigo.
Background
Indigo dyes are a class of dyes with simple structure and extremely low water solubility, which are mainly used for dyeing and printing jeans. At present, the indigo dye is mainly powder, and although the powder disperse dye has the advantages of simple packaging, convenient transportation, good storage stability, strong adaptability to processing equipment and simple operation, most of the dye is concentrated on the surface of fiber due to the weak affinity of the indigo dye to cotton fiber and difficult deep color dyeing, and 20 washing procedures are needed in order to remove the floating color and related auxiliary agents on the surface of fabric in the process of producing jeans in a real factory, so that a large amount of water resource consumption and water resource pollution are caused.
Under the promotion of global green environmental protection tide, the ecological environmental protection concept is gradually merged into all social industries, the life style of returning to nature, green environmental protection and ecological health is promoted by more people, the textile and clothing industry is taken as the traditional industry which people depend on, the ecological pollution problem caused by the life style is always the focus of global attention, and the dyeing and water washing process of the jeans products causes great pollution to the ecological environment as the serious disaster area of the textile and clothing industry. The liquid indigo dye can overcome some defects of powder disperse dyes, a good dispersing effect can be achieved by adopting less dispersing agents, the utilization rate of the dye is improved, in the aspect of dyeing or printing, the dye particles are smaller, the dye uptake can be improved, the dyed deep color can be achieved, meanwhile, the dye can be more easily diffused into the fiber, the surface of the fiber is less in floating color, the subsequent washing procedures are reduced, the discharge of printing and dyeing wastewater is greatly reduced from the source, the dye amount and related auxiliary agents in the dyeing wastewater are reduced, the damage behavior of the dyeing process to the environment is reduced, and the development concept of energy conservation and environmental protection is realized. Therefore, the preparation of liquid dyes has become a focus of research in recent years. However, few researches are carried out in the preparation of the liquid indigo dye at present, and the problems that the grinding efficiency is low, the nano-scale of the prepared nano-scale liquid indigo dye is increased in the storage process, and even coagulation, precipitation and the like occur in the preparation of the liquid indigo dye, so that the problems of uneven dyeing, poor reproducibility and the like exist.
The key factor for solving the problems is the structure of the dispersing agent, and the proper structure of the dispersing agent can not only improve the grinding efficiency of the liquid dye, but also ensure that the liquid dye obtains good stability. At present, most of dispersants for preparing liquid indigo dyes are low-molecular-weight anionic and nonionic dispersants, such as naphthalene-based dispersants, lignosulfonate-based dispersants and different polyoxyethylene ether-based dispersants, and through the dispersants, nano-scale liquid dyes can be prepared, but the problems of low grinding efficiency and poor stability still exist. The polymer dispersant not only has a special anchoring group structure, can be firmly adsorbed on the surface of particles, but also has a solvation chain segment providing system stability, so that people pay attention to the polymer dispersant, and the polymer dispersant has a plurality of beneficial achievements in the aspect of preparing liquid pigments and coatings at present. For example, the chinese invention patent application with application number CN201910844629.7 (publication number CN110540639A) discloses a parallel-type high molecular water-based pigment dispersant, which has a comb-type branched structure and comprises naphthalene ring and a long ethylene oxide/propylene oxide polymer chain at the periphery; the parallel-connection type high-molecular water-based pigment dispersant has excellent dispersion stability, storage stability and redissolution property on organic pigments, high grinding efficiency, strong viscosity reduction property and good color development property. The Chinese patent application with the application number of CN202110585011.0 (with the publication number of CN113278111A) discloses a terpolymer dispersing agent, and the dispersing agent with the structure is used for preparing liquid disperse dye, so that the grinding efficiency is high, and the storage stability of the dye is good. However, the research on the preparation of liquid indigo by the polymer dispersant is less, and further development of new products is urgently needed.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to design and synthesize a preparation method and application of a water-based polyurethane dispersant, and particularly successfully prepare a liquid indigo dye with good stability and storage property by using the synthesized dispersant and a powdery indigo dye through a mechanical grinding means.
The technical scheme is as follows: the preparation method of the waterborne polyurethane dispersant comprises the following specific operation steps:
(1) weighing a compound containing isocyanate group as an initiator, reacting the compound with polyethylene glycol with a certain molecular weight at 75-80 ℃ for 2-2.5h in the presence of nitrogen and a catalyst to generate a polyurethane prepolymer;
wherein, a proper amount of organic solvent is added into a reaction system to control viscosity;
(2) keeping the temperature unchanged, and adding a chain extender 1 to perform chain extension reaction for 2-2.5 hours;
(3) keeping the temperature unchanged, adding a chain extender 2 to continue chain extension reaction for 2-2.5 h;
(4) cooling to 50-55 ℃, adding an end capping agent for end capping reaction for 1-1.5 h;
(5) and after the reaction is finished, adding triethylamine which is equal to the chain extender 1 in mole for neutralization reaction for 1 hour, adding a proper amount of deionized water for high-speed emulsification for 20-30min, and distilling under reduced pressure at room temperature to remove the organic solvent to finally obtain the waterborne polyurethane dispersant.
Further, in the step (1), the initiator is one of hexamethylene diisocyanate and isophorone diisocyanate;
the polyethylene glycol is one of PEG 400 and PEG 600;
the molar ratio of the initiator to the polyethylene glycol is 4: 1-1.2.
Further, in the step (1), the catalyst is dibutyltin dilaurate;
the dosage of the initiator and the polyethylene glycol accounts for 2 to 3 percent of the mass fraction of the initiator and the polyethylene glycol.
Further, in the step (1), the organic solvent is one of acetone or butanone.
Further, in the step (2), the chain extender 1 is one of 2, 2-hydroxymethylpropionic acid or 2, 2-hydroxymethylbutyric acid;
in addition, the molar ratio of the initiator, the polyethylene glycol and the chain extender 1 is 4: 1-1.2: 1.2-1.5.
Further, in the step (3), the chain extender 2 is 1-phenyl-1, 2-glycol;
in addition, the molar ratio of the initiator, the polyethylene glycol, the chain extender 1 and the chain extender 2 is 4: 1-1.2: 1.2-1.5: 1.2.
further, in the step (4), the blocking agent is methyl ethyl ketoxime;
in addition, the molar ratio of the initiator, the polyethylene glycol, the chain extender 1, the chain extender 2 and the end capping agent is 4: 1-1.2: 1.2-1.5: 1.2: 0.2-1.2.
Further, the aqueous polyurethane dispersant prepared by the preparation method is applied to preparation of liquid indigo dye.
Further, the specific process comprises the following steps: mixing the indigo dye, the waterborne polyurethane dispersant and water, pre-grinding for 5-10 min at 1500r/min in a grinding cup, adding zirconia beads, and continuously grinding for 1-2 hours at 3000r/min in a sand mill to obtain the liquid indigo dye.
Furthermore, the water-based polyurethane dispersant accounts for 25-35% of the dry weight of the indigo dye, the dye content in the liquid indigo dye is 25%, the rotating speed of the sand mill is 3000-3500 r/min, and the diameter of zirconia beads is 1-2 mm.
Has the advantages that: compared with the prior art, the invention has the characteristics that 1, the prepared waterborne polyurethane dispersant has transparent appearance and light faint yellow color, while the dispersant used in the preparation process of the liquid indigo in the related literature is a naphthalene-series dispersant and a lignin-series dispersant, and the dispersants have certain colors, so that the prepared liquid indigo dye can hardly cause staining influence on fabrics during subsequent dyeing or printing, and the yellowish transparent waterborne polyurethane can solve the problem to a great extent; 2. the liquid indigo dye prepared by the method can greatly improve the production environment of a factory, and solves the problem that the traditional powdery dye is used in the factory in a large amount in a weighing way and is transportedThe defects of dust pollution, environmental harm and difficulty in accurately controlling metering and quickly batching exist, guarantee can be provided for the physical health of workshop workers, and a foundation is laid for the clean and automatic production of a workshop in the future; 3. the designed and synthesized waterborne polyurethane dispersant introduces a plurality of COOs in the chain extension process-The polyethylene glycol chain end is used as a solvation chain segment to be inserted into the polyurethane dispersant, and the chain end can be used as a good solvation chain end, so that the polyethylene glycol chain end has good compatibility with an aqueous medium, can generate enough steric hindrance, and can effectively prevent the re-flocculation of dye particles. Meanwhile, an N-H, C ═ O structure in a carbamate structure of the polyurethane can form a hydrogen bond with N-H, C ═ O in an indigo dye structure, the bonding force between the dispersing agent and dye particles is further increased, and the introduction of 1-phenyl-1, 2-glycol can introduce a benzene ring structure which has strong planarity and contains pi-pi bonds to further increase the steric hindrance of the dispersing agent, so that the collision and agglomeration among the dye particles are prevented, and a stable system is obtained; 4. the dispersant designed and synthesized by the invention has higher grinding efficiency when preparing liquid disperse dye, and the storage stability of the nano dye is better, and compared with powdery dye, the dyeing property of the nano dye is greatly improved.
Drawings
FIG. 1 is a flow chart of the operation of the present invention;
FIG. 2 is an infrared spectrum of the aqueous polyurethane dispersant prepared in example 1 of the present invention;
fig. 3 is a particle size diagram and SEM image of liquid indigo dye particles in the present invention.
Detailed Description
The invention is further described below with reference to the following figures and specific examples.
As shown in the figure, the preparation method of the waterborne polyurethane dispersant comprises the following specific operation steps:
(1) weighing a compound containing isocyanate group as an initiator, reacting the compound with polyethylene glycol with a certain molecular weight at 75-80 ℃ for 2-2.5h in the presence of nitrogen and a catalyst to generate a polyurethane prepolymer;
wherein, a proper amount of organic solvent is added into a reaction system to control viscosity;
(2) keeping the temperature unchanged (75-80 ℃), adding a chain extender 1 to carry out chain extension reaction for 2-2.5 h;
(3) keeping the temperature unchanged (75-80 ℃), adding the chain extender 2 and continuing the chain extension reaction for 2-2.5 h;
(4) cooling (75-80 ℃) to 50-55 ℃, adding a blocking agent for blocking and reacting for 1-1.5 h;
(5) and after the reaction is finished, adding triethylamine which is equal to the chain extender 1 in mole for neutralization reaction for 1h, adding a proper amount of deionized water for high-speed emulsification for 20-30min, and removing the organic solvent by reduced pressure distillation at room temperature (the common temperature is 25 ℃) to finally obtain the waterborne polyurethane dispersant.
Further, in the step (1), the initiator is one of hexamethylene diisocyanate and isophorone diisocyanate; preferably isophorone diisocyanate;
the polyethylene glycol is one of PEG 400 and PEG 600; preferably PEG 400;
the molar ratio of the initiator to the polyethylene glycol is 4: 1-1.2; preferably 4: 1.
further, in the step (1), the catalyst is dibutyltin dilaurate;
the dosage of the initiator accounts for 2 to 3 percent of the mass fraction of the initiator and the polyethylene glycol; preferably 2%.
Further, in the step (1), the organic solvent is one of acetone or butanone; acetone is preferred.
Further, in the step (2), the chain extender 1 is one of 2, 2-hydroxymethylpropionic acid or 2, 2-hydroxymethylbutyric acid; preferably 2, 2-hydroxymethylbutyric acid;
in addition, the molar ratio of the initiator, the polyethylene glycol and the chain extender 1 is 4: 1-1.2: 1.2-1.5; preferably 4: 1: 1.5: 1.2.
further, in the step (3), the chain extender 2 is 1-phenyl-1, 2-glycol;
in addition, the molar ratio of the initiator, the polyethylene glycol, the chain extender 1 and the chain extender 2 is 4: 1-1.2: 1.2-1.5: 1.2; preferably 4: 1: 1.5: 1.2.
further, in the step (4), the blocking agent is methyl ethyl ketoxime;
in addition, the molar ratio of the initiator, the polyethylene glycol, the chain extender 1, the chain extender 2 and the end capping agent is 4: 1-1.2: 1.2-1.5: 1.2: 0.2-1.2; preferably 4: 1: 1.5: 1.2: 0.6.
further, the aqueous polyurethane dispersant prepared by the preparation method is applied to preparation of liquid indigo dye.
Further, the specific process comprises the following steps: mixing the indigo dye, the waterborne polyurethane dispersant and water, pre-grinding for 5-10 min at 1500r/min in a grinding cup, adding zirconia beads, and continuously grinding for 1-2 hours at 3000r/min in a sand mill to obtain the liquid indigo dye.
Further, the water-based polyurethane dispersant accounts for 25-35% of the dry weight of the indigo dye, and is preferably 27%; the dye content of the liquid indigo dye is 25%, and the rotation speed of the sand mill is 3000-3500 r/min, preferably 3000 r/min; the diameter of the zirconia beads is 1-2 mm; preferably 1 mm.
Example 1:
(1) and synthesizing the aqueous polyurethane dispersant:
according to the mole ratio of 4: 1: 1.5: 1.2: 0.6: 1.5, adding 1mol of polyethylene glycol 400 into a three-neck flask provided with a stirrer and a reflux condenser, fixing the three-neck flask in an oil bath pan, heating to 120 ℃, carrying out vacuum dehydration for 1h, then cooling to 75 ℃, adding 4mol of isophorone diisocyanate and dibutyltin dilaurate with the mass fraction of 2% of the two monomers, introducing nitrogen for 5min, reacting for 2h to generate a polyurethane prepolymer, and adding a proper amount of acetone to control viscosity in the reaction process; keeping the temperature unchanged, adding 1.5mol of chain extender 2, 2-hydroxymethyl butyric acid for chain extension reaction for 2 hours; under the same temperature, 1.2mol of chain extender 1-phenyl-1, 2-glycol is added to continue chain extension reaction for 2 hours; cooling to 50 ℃, adding 0.6mol of methyl ethyl ketoxime for end-capping reaction for 1 h; and after the reaction is finished, adding 1.5mol of triethylamine to perform neutralization reaction for 1h, adding a proper amount of deionized water to perform high-speed emulsification for 20min, and performing reduced pressure distillation at room temperature to remove acetone to obtain the waterborne polyurethane dispersant.
The infrared spectrogram of the aqueous polyurethane dispersant prepared in example 1 is shown in FIG. 2, which shows 1710cm-1The peak is the C ═ O stretching vibration peak on urea bond, urethane bond and DMBA, 2970 cm-1Falling under the antisymmetric stretching vibration peak of C-H in 1-phenyl-1, 2-ethanediol and IPDI, 1090cm-1The peak corresponds to the stretching vibration peak of the polyethylene glycol C-O-C bond, and the characteristic peaks prove the existence of a carbamate structure; 1460cm-1The peak of (A) corresponds to the C-H deformation vibration peak of a methyl group and the C-H shear vibration peak of a methylene group, 1560cm-1The peak at the position corresponds to the mixed peak of C-C stretching vibration, C-N stretching vibration and N-H in-plane bending vibration, 2260cm-1The characteristic absorption peak of-NCO is shown on the left and right, the peak value is weak, and the result shows that-NCO in IPDI almost completely participates in the reaction.
In comparison with the aqueous solution of the conventional dispersant, the aqueous polyurethane dispersant prepared in example 1 generally has a transparent yellowish appearance, while the naphthalene-based and lignin-based dispersants have a blackish brown color.
(2) And the application of the water-based polyurethane dispersant in the preparation of the liquid indigo dye comprises the following steps:
weighing the polymer dispersant prepared in the step (1) and deionized water, placing the polymer dispersant and the deionized water in a grinding cup, pre-grinding for 10min at 1500r/min, adding the indigo dye, adding zirconia beads, and grinding for 1 hour at 3000r/min to obtain the liquid indigo dye. 15g of indigo dye dry weight, 27% of waterborne polyurethane dispersant by weight of the indigo dry weight, adding deionized water to supplement 60g, wherein the dye concentration in the liquid indigo is 25%, and the diameter of zirconia beads is 1 mm;
in the liquid indigo dye prepared by the aqueous polyurethane dispersant in the step (2), the particle size distribution diagram and the SEM image of the dye particles are shown in FIG. 3, so that the liquid indigo suspension D90 is about 280nm, the particle size distribution is uniform, particles with larger particle sizes are not generated, and the SEM image can also show that the particles of the liquid indigo suspension are smaller and have no obvious aggregation phenomenon; the particle size of the prepared liquid indigo dye stored at room temperature for 7d and at 60 ℃ for 7d is shown in table 1. The dispersant with the structure can be used for preparing liquid disperse dye, the grinding efficiency is high, the storage stability of the dye is good, and the particle size of dye particles is not changed greatly before and after storage.
TABLE 1 particle size of liquid indigo dyes for storage at 7d at ambient temperature and 7d at 60 ℃
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention.
Claims (10)
1. A preparation method of a water-based polyurethane dispersant is characterized by comprising the following specific operation steps:
(1) weighing a compound containing isocyanate group as an initiator, reacting the compound with polyethylene glycol with a certain molecular weight at 75-80 ℃ for 2-2.5h in the presence of nitrogen and a catalyst to generate a polyurethane prepolymer;
wherein, a proper amount of organic solvent is added into a reaction system to control viscosity;
(2) keeping the temperature unchanged, and adding a chain extender 1 to perform chain extension reaction for 2-2.5 hours;
(3) keeping the temperature unchanged, adding a chain extender 2 to continue chain extension reaction for 2-2.5 h;
(4) cooling to 50-55 ℃, adding an end capping agent for end capping reaction for 1-1.5 h;
(5) and after the reaction is finished, adding triethylamine which is equal to the chain extender 1 in mole for neutralization reaction for 1h, adding deionized water for high-speed emulsification for 20-30min, and removing the organic solvent by reduced pressure distillation at room temperature to finally obtain the waterborne polyurethane dispersant.
2. The method for preparing the aqueous polyurethane dispersant according to claim 1,
in the step (1), the initiator is one of hexamethylene diisocyanate and isophorone diisocyanate;
the polyethylene glycol is one of PEG 400 and PEG 600;
the molar ratio of the initiator to the polyethylene glycol is 4: 1-1.2.
3. The method for preparing the aqueous polyurethane dispersant according to claim 1,
in the step (1), the catalyst is dibutyltin dilaurate;
the dosage of the initiator and the polyethylene glycol accounts for 2 to 3 percent of the mass fraction of the initiator and the polyethylene glycol.
4. The method for preparing the aqueous polyurethane dispersant according to claim 1,
in the step (1), the organic solvent is one of acetone or butanone.
5. The method for preparing the aqueous polyurethane dispersant according to claim 1,
in the step (2), the chain extender 1 is one of 2, 2-hydroxymethylpropionic acid or 2, 2-hydroxymethylbutyric acid;
in addition, the molar ratio of the initiator, the polyethylene glycol and the chain extender 1 is 4: 1-1.2: 1.2-1.5.
6. The method for preparing the aqueous polyurethane dispersant according to claim 1,
in the step (3), the chain extender 2 is 1-phenyl-1, 2-glycol;
in addition, the molar ratio of the initiator, the polyethylene glycol, the chain extender 1 and the chain extender 2 is 4: 1-1.2: 1.2-1.5: 1.2.
7. the method for preparing the aqueous polyurethane dispersant according to claim 1,
in the step (4), the blocking agent is methyl ethyl ketoxime;
in addition, the molar ratio of the initiator, the polyethylene glycol, the chain extender 1, the chain extender 2 and the end capping agent is 4: 1-1.2: 1.2-1.5: 1.2: 0.2-1.2.
8. Use of the aqueous polyurethane dispersant prepared by the preparation method according to any one of claims 1 to 7 for preparing liquid indigo dye.
9. The application of claim 8, wherein the specific process comprises: mixing the indigo dye, the waterborne polyurethane dispersant and water, pre-grinding for 5-10 min at 1500r/min in a grinding cup, adding zirconia beads, and continuously grinding for 1-2 hours at 3000r/min in a sand mill to obtain the liquid indigo dye.
10. The application of the dye composition as claimed in claim 9, wherein the aqueous polyurethane dispersant accounts for 25-35% of the dry weight of the indigo dye, the dye content in the liquid indigo dye is 25%, the rotation speed of the sand mill is 3000-3500 r/min, and the diameter of the zirconia beads is 1-2 mm.
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| CN202111298675.5A CN114106288B (en) | 2021-11-04 | 2021-11-04 | Preparation method and application of waterborne polyurethane dispersant |
| PCT/CN2022/072840 WO2023077679A1 (en) | 2021-11-04 | 2022-01-20 | Preparation method for waterborne polyurethane dispersing agent and use of waterborne polyurethane dispersing agent |
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| CN (1) | CN114106288B (en) |
| WO (1) | WO2023077679A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114990887A (en) * | 2022-07-07 | 2022-09-02 | 浙江西大门新材料股份有限公司 | Waterborne polyurethane/graphene flame-retardant anti-ultraviolet finishing agent and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1387057A (en) * | 1963-05-06 | 1965-01-29 | Dainichiseika Color Chem | Water- or oil-dispersible coloring matter for dyes, inks, paints and the like as well as method of preparation and method for its application |
| US5273558A (en) * | 1991-08-30 | 1993-12-28 | Minnesota Mining And Manufacturing Company | Abrasive composition and articles incorporating same |
| CN101228201A (en) * | 2005-06-07 | 2008-07-23 | 路博润高级材料公司 | Polyurethane based pigment dispersants which contain reactive double bonds |
| WO2009143433A1 (en) * | 2008-05-23 | 2009-11-26 | E. I. Du Pont De Nemours And Company | Urea-terminated polyurethane dispersants |
| CN105802196A (en) * | 2016-02-19 | 2016-07-27 | 中山大学 | High polymer material with two-way shape memory effect and preparation method thereof |
| KR20160116679A (en) * | 2015-03-31 | 2016-10-10 | 주식회사 빅스 | Water-dispersive polycarbonate polyurethane resin for an air-bag and manufacturing process thereof |
| CN106432681A (en) * | 2015-12-23 | 2017-02-22 | 上海大学 | Nonionic polyurethane aqueous hyperdispersant and preparation method thereof |
| CN111320738A (en) * | 2019-08-30 | 2020-06-23 | 珠海中墨科技有限公司 | Polyurethane dispersant, preparation method thereof and color paste |
| CN111574682A (en) * | 2020-04-17 | 2020-08-25 | 珠海中墨科技有限公司 | Waterborne polyurethane dispersant and color paste containing same for textile digital printing |
-
2021
- 2021-11-04 CN CN202111298675.5A patent/CN114106288B/en active Active
-
2022
- 2022-01-20 WO PCT/CN2022/072840 patent/WO2023077679A1/en unknown
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1387057A (en) * | 1963-05-06 | 1965-01-29 | Dainichiseika Color Chem | Water- or oil-dispersible coloring matter for dyes, inks, paints and the like as well as method of preparation and method for its application |
| US5273558A (en) * | 1991-08-30 | 1993-12-28 | Minnesota Mining And Manufacturing Company | Abrasive composition and articles incorporating same |
| CN101228201A (en) * | 2005-06-07 | 2008-07-23 | 路博润高级材料公司 | Polyurethane based pigment dispersants which contain reactive double bonds |
| WO2009143433A1 (en) * | 2008-05-23 | 2009-11-26 | E. I. Du Pont De Nemours And Company | Urea-terminated polyurethane dispersants |
| KR20160116679A (en) * | 2015-03-31 | 2016-10-10 | 주식회사 빅스 | Water-dispersive polycarbonate polyurethane resin for an air-bag and manufacturing process thereof |
| CN106432681A (en) * | 2015-12-23 | 2017-02-22 | 上海大学 | Nonionic polyurethane aqueous hyperdispersant and preparation method thereof |
| CN105802196A (en) * | 2016-02-19 | 2016-07-27 | 中山大学 | High polymer material with two-way shape memory effect and preparation method thereof |
| CN111320738A (en) * | 2019-08-30 | 2020-06-23 | 珠海中墨科技有限公司 | Polyurethane dispersant, preparation method thereof and color paste |
| CN111574682A (en) * | 2020-04-17 | 2020-08-25 | 珠海中墨科技有限公司 | Waterborne polyurethane dispersant and color paste containing same for textile digital printing |
Non-Patent Citations (1)
| Title |
|---|
| 张苏文等: ""聚氨酯分散剂在液体靛蓝制备中的应用"", 《精细化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114990887A (en) * | 2022-07-07 | 2022-09-02 | 浙江西大门新材料股份有限公司 | Waterborne polyurethane/graphene flame-retardant anti-ultraviolet finishing agent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023077679A1 (en) | 2023-05-11 |
| CN114106288B (en) | 2022-12-06 |
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