Preparation method and application of nano silicon dioxide modified soap-free fluorine-free cationic polyacrylate waterproof agent

Abstract

The invention discloses a preparation method and application of a nano silicon dioxide modified soap-free fluorine-free cationic polyacrylate waterproof agent. In the preparation process of a fluorine-free long-chain polyacrylate waterproof agent, a reactive quaternary ammonium salt cationic emulsifier and a reactive nonionic emulsifier are utilized for synergistic emulsification and participate in a polymerization reaction; emulsifier molecules, long-chain acrylate, short-chain alkyl acrylate monomers and cross-linking monomers are copolymerized and bonded into waterproof emulsion macromolecular chains, and meanwhile, nano SiO2 particles are introduced into the macromolecular chains under the in-situ hydrolysis effect of an organic silicon reagent and the coupling effect of a silane coupling agent, therefore, the soap-free fluorine-free polyacrylate waterproof emulsion which is high in solid content, small in particle size and uniform and stable in distribution and can endow textiles with excellent waterproofness, durability and antibacterial property is developed.

Description

technical field [0001] The invention relates to the technical field of textile printing and dyeing, in particular to a preparation method and application of a nano-silica-modified non-soap and fluorine-free cationic polyacrylate waterproofing agent. Background technique [0002] With the rapid development of the economy and the improvement of people's lives, "green, healthy, low-carbon, and environmental protection" is the life goal pursued by people. Fluorine-free products that are closely related to people in daily life, such as field military uniforms, firefighting, military special clothing, protective equipment, military tents, sleeping bags, mountaineering clothing, ski clothing, shoe and hat materials, bags, shower curtains, casual windbreakers, medical supplies, etc. Waterproof finished textiles are becoming more and more popular. Improving the water resistance and washability of fluorine-free waterproofing agents will be the development trend of waterproofing finish...

AI Technical Summary

Problems solved by technology

The nanoparticles of the nano-waterproof finishing agent are prone to agglomeration, thus losing the nano-characteristics, and the agglomeration of the particles is particularly prone to sticking to the roll, resulting in a greatly reduced waterproofness of the fabric

Long carbon chain acrylate polymers have good water resistance, solvent resistance, film-forming properties, strong adhesion, simple production process, and low cost. The emulsion-type fluorine-free polyacrylate waterproofing prepared by using it The water repellent agent uses water as the continuous phase, which has the advantages of low cost, safety, non-toxicity, and environmental protection. However, the particle size and distribution range of this type of water repellent emulsion have a great influence on the stability of the emulsion. If the particle size of the emulsion is too large, it will produce gel. phenomenon, which affects its performance. In addition, the molecular structure of the emulsifier used in the preparation of this type of waterproofing agent emulsion will also have a key impact on the durability of the subsequent waterproofing membrane.

[0003] ZL201910777219.5 Introduce cationic monomers into the system of long carbon chain acrylates and other functional monomers, and use a composite emulsification system composed of cationic emulsifiers and nonionic emulsifiers to prepare fluorine-free cationic polyacrylate waterproofing by microemulsion polymerization agent, the waterproofing agent introduces cations into the waterproofing emulsion, which improves the particle size of the waterproofing agent emulsion, prevents the generation of the emulsion gel phenomenon, and improves the stability of the emulsion, but in the waterproofing emulsion system, because Small molecule emulsifiers are used. This type of small molecule emulsifier will precipitate during subsequent use, causing the waterproof film to relax and affecting the durability of the waterproofing agent.

ZL201910903695.7 Introduce long-chain cationic monomers into the system of long-chain acrylates and other functional monomers to participate in the polymerization reaction. In the reaction system, long-chain cationic monomers are used as emulsifiers to prepare fluorine-free cationic polymers by microemulsion polymerization. Acrylate waterproofing agent, although this type of waterproofing agent copolymerizes the emulsifier into the polymer chain segment of the waterproofing agent in the form of a reactive monomer, so that the prepared waterproofing agent has no small molecular emulsifiers in the waterproofing agent film during subsequent use. However, only cationic monomers are used as emulsifiers in this reaction system, and the emulsification effect is not ideal, which will cause the prepared waterproofing agent emulsion to have a large particle size and poor stability. In addition, only relying on waterproofing agent emulsion to introduce a hydrophobic layer on the surface of the fabric improves waterproofing. effect, its waterproof effect is limited

[0004] ZL201810932016.4 In the process of preparing water repellent emulsion by long-chain alkyl acrylate and short-chain alkyl acrylate emulsion copolymerization, SiO modified by silane coupling agent is introduced 2 Preparation of core-shell fluorine-free polyacrylate water repellent from nanoparticles and large-size particles to polymer systems, but ready-made SiO 2 The dispersibility of nanoparticles is not good. Although the silane coupling agent is used for modification, the problem of large agglomerated particles of nanoparticles cannot be overcome. When the large particle size particles are directly added to the polymer reaction system, there is also the problem of poor dispersibility. The polymer emulsion particles will be larger, and the waterproof emulsion is easy to agglomerate to produce gel phenomenon, which affects its performance.

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