阅读说明：本技术 具有抗紫外线功能聚丙烯酸酯-聚氨酯复合乳液及其制备方法与应用 (Polyacrylate-polyurethane composite emulsion with ultraviolet resistance function and preparation method and application thereof ) 是由 邓健 粟斯伟 殷国益 梁永红 于泽浩 张圣祖 董会杰 夏明桂 彭雄义 刘仰硕 于 2019-08-28 设计创作，主要内容包括：本发明涉及一种具有抗紫外线功能聚丙烯酸酯-聚氨酯复合乳液及其制备方法与应用,其特征是通过预聚、扩链、接枝、乳化、脱溶剂等方法制备了含木质素磺酸钠的水溶性聚丙烯酸酯乳液,然后,制备了含木质素磺酸钠的聚丙烯酸酯乳液,再将聚丙烯酸酯乳液和聚丙烯酸酯乳液在高速分散匀质机上混合,制备水性聚丙烯酸酯-聚氨酯复合乳液；将棉织物用水性聚丙烯酸酯-聚氨酯复合乳液进行整理,制得抗紫外线棉织物。结果表明：本发明制备的抗紫外线棉织物具有较好的抗紫外线功能,其UPF值达到52以上；经过20次的洗涤后,其UPF值没有明显下降。本发明的具有抗紫外线功能聚丙烯酸酯-聚氨酯复合乳液的制备简单,应用方便,具有广阔的推广前景。(The invention relates to a polyacrylate-polyurethane composite emulsion with an anti-ultraviolet function and a preparation method and application thereof, which are characterized in that a water-soluble polyacrylate emulsion containing sodium lignosulfonate is prepared by the methods of prepolymerization, chain extension, grafting, emulsification, solvent removal and the like, then a polyacrylate emulsion containing sodium lignosulfonate is prepared, and then the polyacrylate emulsion and the polyacrylate emulsion are mixed on a high-speed dispersion homogenizer to prepare the water-based polyacrylate-polyurethane composite emulsion; finishing the cotton fabric with the aqueous polyacrylate-polyurethane composite emulsion to obtain the anti-ultraviolet cotton fabric. The results show that: the ultraviolet-resistant cotton fabric prepared by the method has a good ultraviolet-resistant function, and the UPF value of the ultraviolet-resistant cotton fabric reaches above 52; after 20 washes, the UPF value did not decrease significantly. The polyacrylate-polyurethane composite emulsion with the ultraviolet resistance function has the advantages of simple preparation, convenient application and wide popularization prospect.)

1. The preparation method and the application of the polyacrylate-polyurethane composite emulsion with the ultraviolet resistance function are characterized in that the preparation method and the application method are as follows:

(1) pre-polymerization: adding polyethylene glycol and dimethylolpropionic acid into a reaction kettle, dehydrating for 1-2 h in vacuum at 100-120 ℃, slowly cooling to 50-60 ℃, dropwise adding toluene diisocyanate, butanone and catalyst dibutyltin dilaurate, heating to 80-90 ℃, and reacting for 3-4 h; the molecular weight of the polyethylene glycol is 400, the molar ratio of the polyethylene glycol to the dimethylolpropionic acid to the toluene diisocyanate is 1: 1-2: 3-5, the dosage of dibutyltin dilaurate accounts for 0.01-0.1% of the total amount of the monomers, and the volume-mass ratio of butanone (mL) to the total amount of the monomers (g) is 1: 1-3;

(2) chain extension: cooling the reaction kettle in the step (1) to 40-45 ℃, and adding monohydroxy acrylic acid for 1-1.5 h for multiple times; the molar ratio of the monohydroxy acrylic acid to the dimethylolpropionic acid is 1: 3-5; heating to 60-80 ℃, and reacting for 1-2 h under heat preservation;

(3) grafting: adding sodium lignin sulfonate and an ammonium persulfate aqueous solution into the reaction kettle in the step (2); the mass mol ratio of the sodium lignosulfonate (g) to the monohydroxy acrylic acid (mol) is 1: 1-3, and the concentration of the ammonium persulfate aqueous solution is 0.1-0.5%; finally, naturally cooling;

(4) emulsification: carrying out reverse emulsification on the solution in the step (3) by adopting an emulsification pump with a high shear rate, and simultaneously dropwise adding triethylamine for neutralization; the shearing rate of the emulsifying pump is 6000-15000 r/min;

(5) solvent removal: removing butanone from the emulsion obtained in the step (4) by adopting a reduced pressure low temperature distillation method to obtain a waterborne polyurethane emulsion;

(6) preparation of polyacrylate emulsion: weighing a proper amount of sodium dodecyl benzene sulfonate, an octyl phenol polyoxyethylene ether emulsifier, acrylic acid, ethyl acrylate, sodium lignin sulfonate and ammonium persulfate, wherein the mass-volume ratio of the sodium dodecyl benzene sulfonate (g), the octyl phenol polyoxyethylene ether emulsifier (g), the acrylic acid (mol), the ethyl acrylate (mol), the sodium lignin sulfonate (g) and the ammonium persulfate (g) is as follows: 0.5-1: 1-2: 0.1-0.2: 0.5-1; dissolving all sodium dodecyl benzene sulfonate, an octyl phenol polyoxyethylene ether emulsifier, acrylic acid, ethyl acrylate, sodium lignin sulfonate and an ammonium persulfate initiator which account for 1/3 in total amount in a proper amount of deionized water, uniformly stirring, controlling the temperature to be 75-85 ℃, and stirring for 1-2 hours; then, dissolving the rest 2/3 of acrylic acid, ethyl acrylate, sodium lignin sulfonate and ammonium persulfate initiator in a proper amount of deionized water, and then dropwise adding into the mixed solution which is just stirred, wherein the dropwise adding time is controlled to be 2-3 h, and after the dropwise adding is finished, keeping the temperature for 2-3 h; the emulsion is placed for one month, and the polyacrylate emulsion can be prepared without layering or precipitation;

(7) mixing the emulsion: mixing the polyurethane emulsion prepared in the step (5) with the polyacrylate emulsion prepared in the step (6), wherein the volume ratio of the polyurethane emulsion prepared in the step (5) to the polyacrylate emulsion prepared in the step (6) is 1: 1-2, and stirring the mixed solution on a high-speed dispersion homogenizer for 0.5-1 h at the stirring temperature of 40-45 ℃ to obtain the water-based polyacrylate-polyurethane composite emulsion;

(8) the application comprises the following steps: soaking the cotton fabric into the prepared water-based polyacrylate-polyurethane composite emulsion solution for 1-2 h at 50-60 ℃; then taking out and drying; the concentration of the aqueous polyacrylate-polyurethane composite emulsion solution is 0.1-0.5%.

2. The preparation method and the application of the polyacrylate-polyurethane composite emulsion with the ultraviolet resistance function according to claim 1, wherein the bath ratio of the cotton fabric to the aqueous polyacrylate-polyurethane composite emulsion solution in the step (8) is 1: 20-30.

Technical Field

The invention belongs to the technical field of composite emulsion, and particularly relates to polyacrylate-polyurethane composite emulsion with an ultraviolet resistance function, and a preparation method and application thereof.

Background

The recent research of Qiu's Qing et al (Advanced Functional Materials, 2019, 29 (4)) shows that the lignin has an excellent ultraviolet absorption function, and the polyvinyl alcohol can realize the absorption and shielding of the whole ultraviolet band by only adding 2 ~ 5% of the lignin, and simultaneously can keep better transmittance of visible light.

Polyacrylate emulsion coating agents and polyurethane emulsion coating agents are widely used in the textile field, and can impart a plurality of unique properties to fabrics by adjusting different raw material monomers and compositions, such as: hydrophobicity, ultraviolet resistance, wind resistance, antistatic property and the like. With the increasing living standard of people, people have higher and higher requirements on the ultraviolet resistance of textile clothes. Currently, the anti-uv function of the coating agent can be achieved by incorporating organic anti-uv finishes and inorganic anti-uv finishes, such as: the Chinese patent application No. 201511018203.4 reports a nano-composite ultraviolet-resistant organic coating finishing agent and a preparation method thereof; in addition, chinese patent application No. 201610838910.6 reports a waterproof, ultraviolet-proof, high-strength, light and thin fabric and a method for preparing the same, wherein a coating agent is coated on the surface of the fabric, and the coating agent contains titanium dioxide, silicon dioxide, graphene oxide and the like. Lignosulfonate is a natural renewable resource, has an excellent ultraviolet absorption function, and has a few reports on application in the field of coating agents.

The polyacrylate emulsion and the polyurethane emulsion have advantages and disadvantages in the application aspect of the coating agent and can be mutually complemented, and the preparation of the polyacrylate-polyurethane composite emulsion can effectively supplement the disadvantages of the polyacrylate emulsion and the polyurethane emulsion, so that the advantages of the polyacrylate-polyurethane composite emulsion are more outstanding.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a polyacrylate-polyurethane composite emulsion with an anti-ultraviolet function, a preparation method and application thereof.

The invention aims to provide a polyacrylate-polyurethane composite emulsion with an anti-ultraviolet function, which is prepared by mixing a polyurethane emulsion and a polyacrylate emulsion on a high-speed dispersion homogenizer, wherein the volume ratio of the polyurethane emulsion to the polyacrylate emulsion is 1: 1-2; the polyurethane emulsion and the polyacrylate emulsion both contain sodium lignosulfonate with good ultraviolet resistance, so that the polyacrylate-polyurethane composite emulsion has good ultraviolet resistance.

The invention also aims to provide a preparation method of the polyacrylate-polyurethane composite emulsion with the ultraviolet resistance function, which comprises the following specific steps:

(1) pre-polymerization: adding polyethylene glycol and dimethylolpropionic acid into a reaction kettle, dehydrating for 1-2 h in vacuum at 100-120 ℃, slowly cooling to 50-60 ℃, dropwise adding toluene diisocyanate, butanone and catalyst dibutyltin dilaurate, heating to 80-90 ℃, and reacting for 3-4 h; preferably, the molecular weight of the polyethylene glycol is 400, the molar ratio of the polyethylene glycol to the dimethylolpropionic acid to the toluene diisocyanate is 1: 1-2: 3-5, the amount of dibutyltin dilaurate accounts for 0.01-0.1% of the total amount of the monomers, and the volume-to-mass ratio of butanone (mL) to the total amount of the monomers (g) is 1: 1-3.

(2) Chain extension: cooling the reaction kettle in the step (1) to 40-45 ℃, and adding monohydroxy acrylic acid for 1-1.5 h for multiple times; preferably, the molar ratio of the monohydroxy acrylic acid to the dimethylolpropionic acid is 1: 3-5; heating to 60-80 ℃, and reacting for 1-2 h under heat preservation.

(3) Grafting: adding sodium lignin sulfonate and an ammonium persulfate aqueous solution into the reaction kettle in the step (2); preferably, the mass molar ratio of the sodium lignosulfonate (g) to the monohydroxy acrylic acid (mol) is 1: 1-3, and the concentration of the ammonium persulfate aqueous solution is 0.1-0.5%; and finally, naturally cooling.

(4) Emulsification: carrying out reverse emulsification on the solution in the step (3) by adopting an emulsification pump with a high shear rate, and simultaneously dropwise adding triethylamine for neutralization; preferably, the shear rate of the emulsification pump is 6000 to 15000 r/min.

(5) Solvent removal: and (4) removing butanone from the emulsion obtained in the step (4) by adopting a reduced pressure low temperature distillation method to obtain the waterborne polyurethane emulsion.

(6) Preparation of polyacrylate emulsion: weighing a proper amount of sodium dodecyl benzene sulfonate, an octyl phenol polyoxyethylene ether emulsifier, acrylic acid, ethyl acrylate, sodium lignin sulfonate, ammonium persulfate and the like, wherein the mass-to-volume ratio of the sodium dodecyl benzene sulfonate (g), the octyl phenol polyoxyethylene ether emulsifier (g), the acrylic acid (mol), the ethyl acrylate (mol), the sodium lignin sulfonate (g) and the ammonium persulfate (g) is as follows: 0.5-1: 1-2: 0.1-0.2: 0.5-1; dissolving all sodium dodecyl benzene sulfonate, an octyl phenol polyoxyethylene ether emulsifier, acrylic acid, ethyl acrylate, sodium lignin sulfonate and an ammonium persulfate initiator which account for 1/3 in total amount in a proper amount of deionized water, uniformly stirring, controlling the temperature to be 75-85 ℃, and stirring for 1-2 hours; then, dissolving the rest 2/3 of acrylic acid, ethyl acrylate, sodium lignin sulfonate and ammonium persulfate initiator in a proper amount of deionized water, and then dropwise adding into the mixed solution which is just stirred, wherein the dropwise adding time is controlled to be 2-3 h, and after the dropwise adding is finished, keeping the temperature for 2-3 h; the emulsion is placed for one month, and the polyacrylate emulsion can be prepared without layering or precipitation.

(7) Mixing the emulsion: and (3) mixing the polyurethane emulsion prepared in the step (5) with the polyacrylate emulsion prepared in the step (6), wherein the volume ratio of the polyurethane emulsion prepared in the step (5) to the polyacrylate emulsion prepared in the step (6) is 1: 1-2, and stirring the mixed solution on a high-speed dispersion homogenizer for 0.5-1 h at the stirring temperature of 40-45 ℃ to obtain the water-based polyacrylate-polyurethane composite emulsion.

(8) The application comprises the following steps: soaking the cotton fabric into the prepared water-based polyacrylate-polyurethane composite emulsion solution for 1-2 h at 50-60 ℃; then taking out and drying; preferably, the bath ratio of the cotton fabric to the aqueous polyacrylate-polyurethane composite emulsion is 1: 20-30, and the concentration of the aqueous polyacrylate-polyurethane composite emulsion solution is 0.1-0.5%.

The invention has the following remarkable characteristics:

(1) the invention prepares the water-based polyacrylate-polyurethane composite emulsion, which contains polyacrylate emulsion and polyurethane emulsion, and has complementary advantages and disadvantages, so that the advantages are more prominent.

(2) The polyacrylate emulsion and the polyurethane emulsion prepared by the invention both contain sodium lignosulfonate, and the sodium lignosulfonate has better ultraviolet resistance, so that the polyacrylate-polyurethane composite emulsion has better ultraviolet resistance.

(3) After the cotton fabric is finished by the aqueous polyacrylate-polyurethane composite emulsion prepared by the invention, the UPF value of the cotton fabric reaches more than 52 and is obviously higher than that of the unfinished cotton fabric; after 20 times of washing, the UPF value of the ultraviolet-resistant cotton fabric prepared by the invention is not obviously reduced, which shows that the ultraviolet resistance of the ultraviolet-resistant cotton fabric is not weakened after multiple times of washing.

Detailed Description

The examples described below illustrate the invention in detail.