WO2023077679A1 - 一种水性聚氨酯分散剂的制备方法及其应用 - Google Patents

一种水性聚氨酯分散剂的制备方法及其应用 Download PDF

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WO2023077679A1
WO2023077679A1 PCT/CN2022/072840 CN2022072840W WO2023077679A1 WO 2023077679 A1 WO2023077679 A1 WO 2023077679A1 CN 2022072840 W CN2022072840 W CN 2022072840W WO 2023077679 A1 WO2023077679 A1 WO 2023077679A1
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preparation
chain extender
reaction
initiator
polyethylene glycol
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殷允杰
张苏文
王潮霞
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江南大学
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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
    • 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
    • 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
    • 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
    • C08G18/667—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
    • 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
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0022—Wet grinding of pigments
    • 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

Definitions

  • the invention belongs to the field of polymer dispersants, and relates to a preparation method of an aqueous polyurethane dispersant and its application in the preparation of liquid indigo.
  • Indigo dye is a kind of dye with simple structure and extremely low water solubility, which is mainly used for dyeing and printing of jeans.
  • indigo dyes are mainly powders.
  • powder disperse dyes have the advantages of simple packaging, convenient transportation, good storage stability, strong adaptability to processing equipment, and simple operation, due to the weak affinity of indigo dyes to cotton fibers, It is not easy to dye dark colors, causing most of the dyes to concentrate on the fiber surface.
  • the powder indigo dye has the disadvantages of dust pollution and inaccurate mixing or liquid weighing during the chemical material process, which will cause certain harm to people's health.
  • Liquid indigo dyes can overcome some shortcomings of powder disperse dyes. It uses less dispersant to achieve a good dispersion effect, and the utilization rate of dyes is improved. In terms of dyeing or printing, the dye particles are smaller and the dye uptake rate can be improved.
  • the deep color can be dyed, and at the same time, it can make it easier for the dye to diffuse into the fiber, so that the floating color on the surface of the fiber is less, thereby reducing the subsequent washing process, and greatly reducing the discharge of printing and dyeing wastewater from the source, so that the amount of dye in the dyeing wastewater and related The amount of additives is reduced, so that the damage to the environment in the dyeing process is reduced, and the development concept of energy saving and environmental protection is realized. Therefore, the preparation of liquid dyes has become a research hotspot in recent years.
  • a suitable dispersant structure can not only improve the grinding efficiency of the liquid dye but also make the liquid dye obtain good stability.
  • most of the dispersants for preparing liquid indigo dyes are anionic and nonionic dispersants with low molecular weight, such as naphthalene series, lignin sulfonates and different polyoxyethylene ether dispersants. Although they can be used to prepare nanometer Grade liquid dyes, but still have the problems of low grinding efficiency and poor stability.
  • Polymer dispersants not only have a special anchoring group structure, can be firmly adsorbed on the surface of particles, but also have a solvated segment that provides system stability, which has attracted people's attention.
  • the Chinese invention patent application discloses a parallel-type polymer water-based pigment dispersant.
  • the synthesized parallel-type polymer water-based pigment dispersant has a comb-shaped branch structure.
  • the naphthalene ring and the peripheral ethylene oxide/propylene oxide polymer long chain; the parallel polymer water-based pigment dispersant has excellent dispersion stability, storage stability and resolubility for organic pigments, high grinding efficiency, and reduced Strong viscosity and good color development.
  • the application number is CN202110585011.0 (the publication number is CN113278111A).
  • the Chinese invention patent application discloses a terpolymer dispersant.
  • the dispersant with this structure has high grinding efficiency for preparing liquid disperse dyes, and the storage stability of the dyes is relatively high. good.
  • there are few studies on the preparation of polymer dispersants in liquid indigo and further research and development of new products is urgently needed.
  • the purpose of the present invention is to design and synthesize a preparation method and application of a water-based polyurethane dispersant.
  • a synthetic dispersant and powdery indigo dye are successfully prepared by mechanical grinding means and have good storage stability.
  • liquid indigo dye is a synthetic dispersant and powdery indigo dye.
  • the initiator is one of hexamethylene diisocyanate and isophorone diisocyanate;
  • polyethylene glycol is a kind of in PEG 400 and PEG 600;
  • the molar ratio of the initiator to polyethylene glycol is 4:1-1.2.
  • the catalyst is dibutyltin dilaurate
  • the dosage thereof accounts for 2% to 3% of the mass fraction of the two monomers of the initiator and the polyethylene glycol.
  • the organic solvent is one of acetone or butanone.
  • the chain extender 1 is one of 2,2-hydroxymethyl propionic acid or 2,2-hydroxymethyl butyric acid;
  • the molar ratio of the initiator, polyethylene glycol and chain extender 1 is 4:1-1.2:1.2-1.5.
  • step (3) the chain extender 2 is 1-phenyl-1,2-ethylene glycol
  • the molar ratio of the initiator, polyethylene glycol, chain extender 1 and chain extender 2 is 4:1-1.2:1.2-1.5:1.2.
  • the end-capping agent is methyl ethyl ketone oxime
  • the molar ratio of the initiator, polyethylene glycol, chain extender 1, chain extender 2, and end-capping agent is 4:1-1.2:1.2-1.5:1.2:0.2-1.2.
  • the specific process includes: mixing indigo dye, water-based polyurethane dispersant, and water, first pre-grinding in a grinding cup at 1500r/min for 5-10min, then adding zirconia beads, and then continuing to grind in a sand mill at 3000r/min min milling for 1-2 hours to obtain liquid indigo dye.
  • the water-based polyurethane dispersant accounts for 25% to 35% of the dry weight of the indigo dye, the dye content in the liquid indigo dye is 25%, the speed of the sand mill is 3000 to 3500r/min, and the zirconia The diameter of the beads is 1-2mm.
  • the present invention has the characteristics of the present invention: 1, the water-based polyurethane dispersant prepared by the present invention is transparent in appearance, and the color is only very light pale yellow, while the liquid indigo used in the preparation process of liquid indigo in the current related literature
  • the dispersants used are naphthalene-based and lignin-based dispersants. These dispersants themselves have a certain color.
  • the prepared liquid indigo dye will inevitably cause staining on the fabric during subsequent dyeing or printing, while the light yellow and transparent water-based Polyurethane can solve this problem to a large extent;
  • the liquid indigo dye prepared by the present invention can greatly improve the production environment of the factory, solve the dust pollution that exists when traditional powdery dyes are weighed, used and transported in large quantities in the factory, and endanger the environment At the same time, it is not suitable to accurately control the disadvantages of metering and rapid batching, which can provide protection for the health of workshop workers and lay the foundation for future clean and automated production in workshops;
  • the water-based polyurethane dispersant designed and synthesized by the present invention introduces multiple A COO - acts as an anchoring group.
  • the multi-point anchoring of polymer dispersants can greatly improve its anchoring effect with dyes, and at the same time, the polyethylene glycol chain end is inserted as a solvated segment
  • the chain end can be used as a good solvating chain end, which not only has good compatibility with the aqueous medium, but also can generate sufficient steric hindrance, which can effectively prevent the re-flocculation of dye particles.
  • the present invention The designed and synthesized dispersant has high grinding efficiency when preparing liquid disperse dyes, and the storage stability of nanoscale dyes is better, and its dyeing performance is greatly improved compared with powdered dyes.
  • Fig. 1 is the operation flowchart of the present invention
  • Fig. 2 is the infrared spectrogram of the aqueous polyurethane dispersant prepared by the embodiment of the present invention 1;
  • Fig. 3 is the particle size diagram and SEM diagram of liquid indigo dye particles in the present invention.
  • 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 polyethylene glycol is 4:1-1.2; preferably 4:1.
  • the catalyst is dibutyltin dilaurate
  • the amount thereof accounts for 2%-3% of the mass fraction of the two monomers of the initiator and polyethylene glycol; preferably 2%.
  • the organic solvent is one of acetone or butanone; preferably acetone.
  • the chain extender 1 is one of 2,2-hydroxymethyl propionic acid or 2,2-hydroxymethyl butyric acid; preferably 2,2-hydroxymethyl butyric acid;
  • the molar ratio of the initiator, polyethylene glycol and chain extender 1 is 4:1-1.2:1.2-1.5; preferably 4:1:1.5:1.2.
  • step (3) the chain extender 2 is 1-phenyl-1,2-ethylene glycol
  • the molar ratio of the initiator, polyethylene glycol, chain extender 1 and chain extender 2 is 4:1-1.2:1.2-1.5:1.2; preferably 4:1:1.5:1.2.
  • the end-capping agent is methyl ethyl ketone oxime
  • the molar ratio of the initiator, polyethylene glycol, chain extender 1, chain extender 2 and 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.
  • the specific process includes: mixing indigo dye, water-based polyurethane dispersant, and water, first pre-grinding in a grinding cup at 1500r/min for 5-10min, then adding zirconia beads, and then continuing to grind in a sand mill at 3000r/min min milling for 1-2 hours to obtain liquid indigo dye.
  • the water-based polyurethane dispersant accounts for 25% to 35% of the dry weight of the indigo dye, preferably 27%; the dye content in the liquid indigo dye is 25%, and the speed of the sand mill is 3000 to 3500r /min, preferably 3000r/min; the diameter of the zirconia beads is 1-2mm; preferably 1mm.
  • the molar ratio of six monomers is 4:1:1.5:1.2:0.6:1.5.
  • aqueous polyurethane dispersant aqueous solution prepared by embodiment 1 is compared with the aqueous solution of traditional dispersant, and under normal circumstances, the aqueous polyurethane dispersant appearance presents transparent light yellow, and naphthalene series and lignin dispersant then present dark brown.
  • step (1) Weigh the polymer dispersant and deionized water prepared in step (1) and put them in the grinding cup, pre-grind at 1500r/min for 10min, add indigo dye, add zirconia beads, grind at 3000r/min for 1 hour, Obtain liquid indigo dye.
  • Indigo dye dry weight 15g water-based polyurethane dispersant accounts for 27% of indigo dry weight mass, add deionized water to make up to 60g, dye concentration in liquid indigo is 25%, zirconia bead diameter size is 1mm;
  • Step (2) adopts the liquid indigo dye prepared by water-based polyurethane dispersant, the particle size distribution figure and the SEM figure of the dye particle are as shown in Figure 3, it can be seen that the liquid indigo suspension D90 is about 280nm, and the particle size distribution is uniform, without Larger particle size, SEM images can also be seen that the liquid indigo suspension particles are small, and there is no obvious aggregation phenomenon; the particle size of the prepared liquid indigo dye stored at room temperature for 7 days and stored at 60 ° C for 7 days is shown in Table 1. It can be concluded that the dispersant with this structure has a higher grinding efficiency for preparing liquid disperse dyes, and the storage stability of the dyes is better, and the particle size of the dyes does not change much before and after storage.
  • Table 1 The particle size of liquid indigo dye stored at room temperature for 7 days and at 60°C for 7 days

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

一种水性聚氨酯分散剂的制备方法及其应用。属于高分子分散剂领域，具体步骤：称取含异氰酸酯基的化合物作为引发剂，与聚乙二醇在氮气和催化剂存在下生成聚氨酯预聚体，反应体系加入有机溶剂控粘；75-80℃下，加入扩链剂1进行扩链反应2-2.5h；75-80℃下，加入扩链剂2继续扩链反应2-2.5h；降温至50-55℃，加入封端剂封端反应1-1.5h；反应结束后，加入三乙胺进行中和反应1h，加去离子水高速乳化20-30min，于室温下减压蒸馏除去有机溶剂得到水性聚氨酯分散剂。该结构的分散剂制备液体靛蓝染料具有较高的研磨效率，且染料的贮存稳定性能较好。

Description

一种水性聚氨酯分散剂的制备方法及其应用 技术领域
本发明属于高分子分散剂领域，涉及一种水性聚氨酯分散剂的制备方法、及其在液体靛蓝制备中的应用。
背景技术
靛蓝染料是一类结构简单，水溶性极低的染料，其主要是用作牛仔裤的染色与印花。目前靛蓝染料主要以粉体为主，虽然粉体分散染料具有包装简单、运输方便、贮存稳定性好、对加工设备适应能力强、操作简单的优点，但由于靛蓝染料对棉纤维亲和力不强，不易染得深色，造成染料大部分集中在纤维表面，现实工厂生产牛仔裤过程中为了去除织物表面浮色和相关助剂，需要经过20多道水洗工序，这造成大量水资源的消耗与水资源的污染，此外，粉体靛蓝染料存在化料过程中会产生粉尘污染和调浆或配液称量不准确的弊端，对人们的健康产生一定的危害。
在全球绿色环保风潮的推动下，生态环保理念逐渐融入了社会的各行各业，“回归自然、绿色环保、生态健康”的生活方式开始被更多的人提倡，纺织服装行业作为人民十分依赖的传统产业，其导致的生态污染问题一直是全球的关注重点，而作为纺织服装行业污染的重灾区，牛仔产品的染色及水洗过程造成了生态环境的极大污染。而液体靛蓝染料能够克服粉体分散染料的一些缺点，它采用较少的分散剂即可达到良好的分散效果，染料利用率提高，在染色或印花方面，其染料颗粒较小可以提高上染率进而染的深色，同时可以使染料更易向纤维内部扩散，使纤维表面浮色较少，进而减少后道水洗工序，从源头上大幅降低印染废水的排放，从而使得染色废水中染料量和相关助剂的量减少，使染色过程对环境的破坏行为下降，实现节能环保的发展理念。因此，液体染料的制备成为近年来的研究热点。但是目前液体靛蓝染料制备方面研究得很少，而且液体染料在制备中存在研磨效率低、制备的纳米级液体靛蓝染料在贮存过程中纳米尺度变大，甚至出现凝聚、沉淀等问题，导致染色不匀和重现性差等问题。
解决上述问题的关键因素是分散剂的结构，合适的分散剂结构不仅能够提高液体染料的研磨效率还能够使液体染料获得良好的稳定性。目前制备液体靛蓝染料的分散剂大多是一些低分子量的阴离子和非离子型分散剂，如萘系、木质素磺酸盐类以及不同聚氧乙烯醚型分散剂，通过它们虽然能够制备纳出米级的液体染料，但是仍然存在研磨效率低、稳定性能较差的问题。高分子分散剂不仅具有特殊的锚固基团的结构，可以牢牢的吸附在颗粒表面而且还具有提供体系稳定的溶 剂化链段而受到人们的关注，目前高分子分散剂在制备液体颜料、涂料方面已经有很多有益成果。如申请号为CN201910844629.7(公开号为CN110540639A)中国发明专利申请公开了一种并联型高分子水性颜料分散剂，合成的该并联型高分子水性颜料分散剂具有梳型的分支结构，由包括的萘环和外围的环氧乙烷/环氧丙烷聚合物长链；并联型高分子水性颜料分散剂对有机颜料具有优异的分散稳定性、贮存稳定性和再溶解性，研磨效率高，降粘性强，展色性好。申请号为CN202110585011.0(公开号为CN113278111A)中国发明专利申请公开了一种三元共聚物分散剂，该结构的分散剂制备液体分散染料具有较高的研磨效率,且染料的贮存稳定性能较好。但是，目前高分子分散剂在液体靛蓝制备的研究较少，亟需进一步研发新的产品。
发明内容
发明目的：本发明目的是设计合成了一种水性聚氨酯分散剂的制备方法及其应用，其具体的是将合成的分散剂与粉状靛蓝染料通过机械研磨手段成功制备了一种稳定储存性良好的液体靛蓝染料。
技术方案：本发明所述的一种水性聚氨酯分散剂的制备方法，具体操作步骤如下：
(1)、称取含异氰酸酯基的化合物作为引发剂，与一定分子量的聚乙二醇在氮气和催化剂存在下于75-80℃反应2-2.5h后，生成聚氨酯预聚体；
其中，在反应体系中加入适量的有机溶剂控粘；
(2)、保持温度不变，加入扩链剂1进行扩链反应2-2.5h；
(3)、保持温度不变，加入扩链剂2继续扩链反应2-2.5h；
(4)、降温至50-55℃，加入封端剂封端反应1-1.5h；
(5)、反应结束后，加入与扩链剂1等摩尔的三乙胺进行中和反应1h，加入适量的去离子水高速乳化20-30min，在室温下减压蒸馏除去有机溶剂最终得到水性聚氨酯分散剂。
进一步的，在步骤(1)中，所述的引发剂为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种；
所述聚乙二醇为PEG 400与PEG 600中的一种；
所述引发剂与聚乙二醇的摩尔比为4：1-1.2。
进一步的，在步骤(1)中，所述的催化剂为二月桂酸二丁基锡；
其用量占引发剂、聚乙二醇两种单体的质量分数2％～3％。
进一步的，在步骤(1)中，所述有机溶剂为丙酮或丁酮中的一种。
进一步的，在步骤(2)中，所述的扩链剂1为2，2-羟甲基丙酸或2，2-羟 甲基丁酸中的一种；
另外，所述引发剂、聚乙二醇与扩链剂1的摩尔比为4：1-1.2：1.2-1.5。
进一步的，在步骤(3)中，所述的扩链剂2为1-苯基-1，2-乙二醇；
另外，所述引发剂、聚乙二醇、扩链剂1与扩链剂2的摩尔比为4：1-1.2：1.2-1.5：1.2。
进一步的，在步骤(4)中，所述的封端剂为甲乙酮肟；
另外，所述引发剂、聚乙二醇、扩链剂1、扩链剂2与封端剂的摩尔比为4：1-1.2：1.2-1.5：1.2：0.2-1.2。
进一步的，所述的制备方法制备的水性聚氨酯分散剂在制备液体靛蓝染料中的应用。
进一步的，具体过程包括：将靛蓝染料以及水性聚氨酯分散剂、水混合，先在研磨杯中以1500r/min预磨5～10min，之后加入氧化锆珠，然后继续在砂磨机中以3000r/min研磨1-2小时，从而得到液体靛蓝染料。
进一步的，所述的水性聚氨酯分散剂占靛蓝染料干重质量的25％～35％，液体靛蓝染料中染料含量为25％，所述的砂磨机的转速为3000～3500r/min，氧化锆珠直径大小为1～2mm。
有益效果：本发明与现有技术相比，本发明的特点:1、本发明制备的水性聚氨酯分散剂外观透明，颜色仅为很浅的淡黄色，而目前相关文献中液体靛蓝制备过程中所用的分散剂为萘系和木质素类分散剂，这些分散剂本身带有一定的颜色，制备的液体靛蓝染料在后续染色或印花时，难免会对织物造成沾色影响，而淡黄透明的水性聚氨酯则可很大程度上解决这一问题；2、本发明制备的液体靛蓝染料可以大幅改善工厂的生产环境，解决传统粉状染料在工厂大量称量使用及运输时存在的粉尘污染，危害环境，同时也不宜精确控制计量和快速配料的弊端，可以为车间工人的身体健康提供保障，为未来车间清洁自动化生产奠定基础；3、本发明设计合成的水性聚氨酯分散剂在扩链过程中引入多个COO -充当锚固基团，相比于传统分散剂的单点锚固，高分子分散剂多点锚固可以大大提高其与染料锚固效果，同时将聚乙二醇链端作为溶剂化链段接入到聚氨酯分散剂中，该链端可以作为一种良好的溶剂化链端，既与水性介质有良好的相容性，又能产生足够的空间位阻，可有效防止染料颗粒的再次絮凝。同时聚氨酯的氨基甲酸酯结构中的N-H、C＝O结构可与靛蓝染料结构中的N-H、C＝O形成氢键，进一步增加分散剂与染料颗粒间的结合力，引入1-苯基-1，2-乙二醇可以引入平面性强且含有π-π键的苯环结构进一步增加分散剂的空间位阻，从而阻止染料颗粒间的碰撞团聚，从而获得稳定的体系；4、本发明设计合成的分散剂在制备液体分散染料时具有 较高的研磨效率，且纳米级染料的贮存稳定性能较好，且相比于粉状染料，其染色性能大幅提高。
附图说明
图1是本发明的操作流程图；
图2是本发明实施例1制备的水性聚氨酯分散剂的红外光谱图；
图3是本发明中液体靛蓝染料颗粒的粒径图与SEM图。
具体实施方式
以下结合附图和具体实施例，对本发明做出进一步说明。
如图所述，本发明所述的一种水性聚氨酯分散剂的制备方法，具体操作步骤如下：
(1)、称取含异氰酸酯基的化合物作为引发剂，与一定分子量的聚乙二醇在氮气和催化剂存在下于75-80℃反应2-2.5h后，生成聚氨酯预聚体；
其中，在反应体系中加入适量的有机溶剂控粘；
(2)、保持温度不变(75-80℃)，加入扩链剂1进行扩链反应2-2.5h；
(3)、保持温度不变(75-80℃)，加入扩链剂2继续扩链反应2-2.5h；
(4)、降温(75-80℃)至50-55℃，加入封端剂封端反应1-1.5h；
(5)、反应结束后，加入与扩链剂1等摩尔的三乙胺进行中和反应1h，加适量的去离子水高速乳化20-30min，在室温(通常的温度是25℃)下减压蒸馏除去有机溶剂最终得到水性聚氨酯分散剂。
进一步的，在步骤(1)中，所述的引发剂为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种；优选为异佛尔酮二异氰酸酯；
所述聚乙二醇为PEG 400与PEG 600中的一种；优选为PEG 400；
所述引发剂与聚乙二醇的摩尔比为4：1-1.2；优选为4：1。
进一步的，在步骤(1)中，所述的催化剂为二月桂酸二丁基锡；
其用量占引发剂、聚乙二醇两种单体的质量分数2％～3％；优选为2％。
进一步的，在步骤(1)中，所述有机溶剂为丙酮或丁酮中的一种；优选为丙酮。
进一步的，在步骤(2)中，所述的扩链剂1为2，2-羟甲基丙酸或2，2-羟甲基丁酸中的一种；优选2，2-羟甲基丁酸；
另外，所述引发剂、聚乙二醇与扩链剂1的摩尔比为4：1-1.2：1.2-1.5；优选为4：1：1.5：1.2。
进一步的，在步骤(3)中，所述的扩链剂2为1-苯基-1，2-乙二醇；
另外，所述引发剂、聚乙二醇、扩链剂1与扩链剂2的摩尔比为4：1-1.2： 1.2-1.5：1.2；优选为4：1：1.5：1.2。
进一步的，在步骤(4)中，所述的封端剂为甲乙酮肟；
另外，所述引发剂、聚乙二醇、扩链剂1、扩链剂2与封端剂的摩尔比为4：1-1.2：1.2-1.5：1.2：0.2-1.2；优选为4：1：1.5：1.2：0.6。
进一步的，所述的制备方法制备的水性聚氨酯分散剂在制备液体靛蓝染料中的应用。
进一步的，具体过程包括：将靛蓝染料以及水性聚氨酯分散剂、水混合，先在研磨杯中以1500r/min预磨5～10min，之后加入氧化锆珠，然后继续在砂磨机中以3000r/min研磨1-2小时，从而得到液体靛蓝染料。
进一步的，所述的水性聚氨酯分散剂占靛蓝染料干重质量的25％～35％，优先为27％；液体靛蓝染料中染料含量为25％，所述的砂磨机的转速为3000～3500r/min，优选为3000r/min；氧化锆珠直径大小为1～2mm；优选为1mm。
实施例1：
(1)、水性聚氨酯分散剂合成：
按引发剂、聚乙二醇、扩链剂1、扩链剂2、封端剂、中和剂六种单体的摩尔比为4：1：1.5：1.2：0.6：1.5计算，向装有搅拌器、回流冷凝管的三口烧瓶中加入1mol聚乙二醇400，将三口烧瓶固定于油浴锅中，升温至120℃下真空脱水1h，然后降温至75℃，加入4mol异佛尔酮二异氰酸酯和上述两种单体质量分数2％的二月桂酸二丁基锡，通氮气5min后反应2h生成聚氨酯预聚体，反应过程中加适量丙酮控粘；保持温度不变，加入1.5mol扩链剂2，2-羟甲基丁酸进行扩链反应2h；同一温度下，加1.2mol扩链剂1-苯基-1，2-乙二醇继续扩链反应2h；降温至50℃，加入0.6mol甲乙酮肟封端反应1h；反应结束后，加入1.5mol三乙胺进行中和反应1h，加适量去离子水高速乳化20min，于室温下减压蒸馏除去丙酮得到水性聚氨酯分散剂。
实施例1制备的水性聚氨酯分散剂的红外光谱图如图2所示，可以看出1710cm -1处为脲键、氨酯键和DMBA上的C＝O伸缩振动峰，2 970cm -1处归属于1-苯基-1，2-乙二醇和IPDI中C—H的反对称伸缩振动峰，1090cm -1处的峰对应聚乙二醇C—O—C键伸缩振动峰，这些特征峰证明了氨基甲酸酯结构的存在；1460cm -1的峰对应于甲基的C—H变形振动峰和亚甲基的C—H剪切振动峰，1560cm -1处的峰对应C—C伸缩振动，C—N伸缩振动及N—H面内弯曲振动的混合峰，2260cm -1左右为—NCO的特征吸收峰，峰值微弱，说明IPDI中的—NCO几乎完全参与了反应。
实施例1制备的水性聚氨酯分散剂水溶液与传统分散剂的水溶液相比较，通 常情况下，水性聚氨酯分散剂外观呈现透明淡黄色，而萘系和木质素类分散剂则呈现黑褐色。
(2)、水性聚氨酯分散剂在液体靛蓝染料制备中的应用：
称取步骤(1)中制备的高分子分散剂、去离子水置于研磨杯中，先以1500r/min预研磨10min后，加入靛蓝染料，加入氧化锆珠，于3000r/min研磨1小时，得到液体靛蓝染料。靛蓝染料干重15g，水性聚氨酯分散剂占靛蓝干重质量的27％，加去离子水补至60g，液体靛蓝中染料浓度为25％，氧化锆珠直径大小为1mm；
步骤(2)采用水性聚氨酯分散剂制备的液体靛蓝染料，染料颗粒的粒径分布图与SEM图如图3所示，可以看出液体靛蓝悬浮液D90为280nm左右，且粒径分布均匀，无较大粒径颗粒，SEM图也可以看出液体靛蓝悬浮液颗粒较小，且无明显聚集现象；制备的液体靛蓝染料的常温储存7d和60℃下储存7d的粒径大小如表1。可以得出该结构的分散剂制备液体分散染料具有较高的研磨效率，且染料的贮存稳定性能较好，染料颗粒粒径储存前后变化不大。
表1 液体靛蓝染料的常温储存7d和60℃下储存7d的粒径
Figure PCTCN2022072840-appb-000001
以上仅是本发明的优选实施方式，本发明的保护范围并不仅局限于上述实施例，凡属于本发明思路下的技术方案均属于本发明的保护范围。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理前提下的若干改进和润饰，应视为本发明的保护范围。

Claims (10)

  1. 一种水性聚氨酯分散剂的制备方法，其特征在于，具体操作步骤如下：
    (1)、称取含异氰酸酯基的化合物作为引发剂，与一定分子量的聚乙二醇在氮气和催化剂存在下于75-80℃反应2-2.5h后，生成聚氨酯预聚体；
    其中，在反应体系中加入适量的有机溶剂控粘；
    (2)、保持温度不变，加入扩链剂1进行扩链反应2-2.5h；
    (3)、保持温度不变，加入扩链剂2继续扩链反应2-2.5h；
    (4)、降温至50-55℃，加入封端剂封端反应1-1.5h；
    (5)、反应结束后，加入与扩链剂1等摩尔的三乙胺进行中和反应1h，加入去离子水高速乳化20-30min，在室温下减压蒸馏除去有机溶剂最终得到水性聚氨酯分散剂。
  2. 根据权利要求1所述的一种水性聚氨酯分散剂的制备方法，其特征在于，
    在步骤(1)中，所述的引发剂为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种；
    所述聚乙二醇为PEG 400与PEG 600中的一种；
    所述引发剂与聚乙二醇的摩尔比为4：1-1.2。
  3. 根据权利要求1所述的一种水性聚氨酯分散剂的制备方法，其特征在于，
    在步骤(1)中，所述的催化剂为二月桂酸二丁基锡；
    其用量占引发剂、聚乙二醇两种单体的质量分数2％～3％。
  4. 根据权利要求1所述的一种水性聚氨酯分散剂的制备方法，其特征在于，
    在步骤(1)中，所述有机溶剂为丙酮或丁酮中的一种。
  5. 根据权利要求1所述的一种水性聚氨酯分散剂的制备方法，其特征在于，
    在步骤(2)中，所述的扩链剂1为2，2-羟甲基丙酸或2，2-羟甲基丁酸中的一种；
    另外，所述引发剂、聚乙二醇与扩链剂1的摩尔比为4：1-1.2：1.2-1.5。
  6. 根据权利要求1所述的一种水性聚氨酯分散剂的制备方法，其特征在于，
    在步骤(3)中，所述的扩链剂2为1-苯基-1，2-乙二醇；
    另外，所述引发剂、聚乙二醇、扩链剂1与扩链剂2的摩尔比为4：1-1.2：1.2-1.5：1.2。
  7. 根据权利要求1所述的一种水性聚氨酯分散剂的制备方法，其特征在于，
    在步骤(4)中，所述的封端剂为甲乙酮肟；
    另外，所述引发剂、聚乙二醇、扩链剂1、扩链剂2与封端剂的摩尔比为4：1-1.2：1.2-1.5：1.2：0.2-1.2。
  8. 权力要求1-7任一项所述的制备方法制备的水性聚氨酯分散剂在制备液 体靛蓝染料中的应用。
  9. 根据权利要求8所述的应用，其特征在于，具体过程包括：将靛蓝染料以及水性聚氨酯分散剂、水混合，先在研磨杯中以1500r/min预磨5～10min，之后加入氧化锆珠，然后继续在砂磨机中以3000r/min研磨1-2小时，从而得到液体靛蓝染料。
  10. 根据权利要求9所述的应用，其特征在于，所述的水性聚氨酯分散剂占靛蓝染料干重质量的25％～35％，液体靛蓝染料中染料含量为25％，所述的砂磨机的转速为3000～3500r/min，氧化锆珠直径大小为1～2mm。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101228201A (zh) * 2005-06-07 2008-07-23 路博润高级材料公司 含反应性双键的聚氨酯基颜料分散剂
WO2009143433A1 (en) * 2008-05-23 2009-11-26 E. I. Du Pont De Nemours And Company Urea-terminated polyurethane dispersants
CN111320738A (zh) * 2019-08-30 2020-06-23 珠海中墨科技有限公司 一种聚氨酯分散剂及其制备方法和一种色浆
CN111574682A (zh) * 2020-04-17 2020-08-25 珠海中墨科技有限公司 一种水性聚氨酯分散剂及含其的纺织数码印花用的色浆

Family Cites Families (5)

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FR1387057A (fr) * 1963-05-06 1965-01-29 Dainichiseika Color Chem Matière colorante dispersable dans l'eau ou dans l'huile pour teinture, encres, peintures et analogues ainsi que procédé de préparation et procédé pour son application
US5273558A (en) * 1991-08-30 1993-12-28 Minnesota Mining And Manufacturing Company Abrasive composition and articles incorporating same
KR101737762B1 (ko) * 2015-03-31 2017-05-19 주식회사 빅스 에어백용 수분산 폴리우레탄 수지 및 그 제조방법
CN106432681B (zh) * 2015-12-23 2019-06-04 上海大学 非离子型聚氨酯类水性超分散剂及其制备方法
CN105802196B (zh) * 2016-02-19 2018-08-07 中山大学 一种具有双程形状记忆效应的高分子材料及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101228201A (zh) * 2005-06-07 2008-07-23 路博润高级材料公司 含反应性双键的聚氨酯基颜料分散剂
WO2009143433A1 (en) * 2008-05-23 2009-11-26 E. I. Du Pont De Nemours And Company Urea-terminated polyurethane dispersants
CN111320738A (zh) * 2019-08-30 2020-06-23 珠海中墨科技有限公司 一种聚氨酯分散剂及其制备方法和一种色浆
CN111574682A (zh) * 2020-04-17 2020-08-25 珠海中墨科技有限公司 一种水性聚氨酯分散剂及含其的纺织数码印花用的色浆

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