Synthesis of cationic fluorinated polyacrylate copolymer by RAFT emulsifier-free emulsion polymerization and its application as waterborne textile finishing agent

doi:10.1016/j.dyepig.2016.11.035

Dyes and Pigments

Volume 139, April 2017, Pages 102-109

https://doi.org/10.1016/j.dyepig.2016.11.035 Get rights and content

Highlights

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Cationic hybrid latex was synthesized via ab initio RAFT emulsion polymerization.
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The treated fabrics showed good water repellency.
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The treated fabric had good antibacterial property against E. coli and S. aureus.

Abstract

Cationic fluorinated polyacrylate emulsifier-free emulsion was synthesized by ab initio RAFT emulsifier-free emulsion polymerization using fluorine-containing amphiphilic block copolymer poly (2-(dimethylamino) ethyl methacrylate)-b-poly (hexafluorobutyl acrylate) (PDMAEMA-b-PHFBA) macro-RAFT agent as a stabilizer, and (2-(acryloyloxy)ethyl)trimethylammonium chloride (DMC) as a cationic monomer. The critical micelle concentration (CMC) of PDMAEMA-b-PHFBA is much smaller than the CMC of SDS, suggesting the excellent micelle-forming ability of PDMAEMA-b-PHFBA in water. The influence of the amount of DMC on emulsion polymerization and finished fabric properties was investigated. The latex particle size and its distribution decreased as the amount of DMC increased from 0 wt% to 2.25 wt%, and then increased afterwards. The cationic fluorinated polyacrylate showed much higher thermal stability than polyacrylate. The water contact angle of the finished fabric decreased with the increase of the amount of DMC. The cationic fluorinated polyacrylate emulsifier-free emulsion was deposited on the surface of fabric characterized by SEM-EDX, and the finished fabrics showed good water repellency. In addition, the finished fabric with fluorinated polyacrylate emulsifier-free emulsion had good antibacterial property against E. coli and S. aureus.

Graphical abstract

Introduction

Cationic fluorinated polyacrylate copolymers have gained ever-increasing attention of many investigators due to their high adhesion to anionic substrates, low surface energy, high resistances to thermal and chemical attack, and good flexibility [1], [2], [3], [4], etc. Therefore, they are widely used in numerous industrial fields such as surface coatings for paper, leather, textile, and walls of buildings. Up to now, a number of ways are avialable to synthetize cationic fluorinated polyacrylate copolymers. Among them, emulsifier-free emulsion polymerization is an effective way for the purpose. Compared with the conventional emulsion polymerization, the emulsifier-free emulsion polymerization with amphiphilic block copolymer as a stabilizer can exhibit many excellent properties [5], [6], [7], such as excellent emulsion stability and no residual emulsifier migration during film formation process [8]. In addition, in contrast to the traditional low molecular weight emulsifiers, amphiphilic block copolymers have a very low critical micelle concentration (CMC) and a low diffusion coefficient. For instance, the concentration range of the CMCs of amphiphilic block copolymers has been reported to be between 10⁻⁹ and 10⁻⁴ mol/L [5], [9], [10], whereas that of low molecular weight emulsifiers is between 10⁻³ and 1 mol/L [11].

Recently, the synthesis of amphiphilic block copolymer is greatly simplified as the result of the development of controlled/living radical polymerization (CLRP), including atom transfer radical polymerization (ATRP), nitroxidemediated radical polymerization (NMP) and reversible addition-fragmentation chain transfer (RAFT) polymerization [12], [13]. Among them, RAFT polymerization has many advantages due to its compatibility with a wide range of monomers, functional groups and convenient experimental conditions [14]. Therefore, RAFT polymerization is considered to be one of the controlled radical polymerizations having considerable potential for industrial polymers and processes. Synthesis of fluorine-containing amphiphilic block copolymers via RAFT polymerization has been reported, and micellization behaviors in aqueous solutions have been extensively studied [15], [16]. For instance, Skrabania et al. [17] synthesized linear amphiphilic triblock copolymers of poly (ethylene oxide)-b-poly (butyl acrylate)-b-poly (tetrahydroperfluorodecyl acrylate) (PEO-b-PBA-b-PFA) and poly (ethylene oxide)-b-poly (2-ethylhexyl acrylate)-b-poly (tetrahydroperfluorodecyl acrylate) (PEO-b-PEHA-b-PFA) by the RAFT polymerization in two successive steps using a PEO macro-CTA, and found that the PEO-b-PBA-b-PFA and PEO-b-PEHA-b-PFA could self-assemble in water into spherical micellar aggregates. Meanwhile, cryogenic transmission electron microscopy revealed that micellar cores of aggregates could undergo local phase separation to form a unique ultra-structure. In our previous work [18], fluorine-containing amphiphilic block copolymer poly (acrylic acid)-b-poly(hexaflurobutyl acrylate) (PAA-b-PHFBA) was successfully synthesized via RAFT polymerization, and fluorinated polyacrylate emulsifier-free emulsion was prepared by using PAA-b-PHFBA as a stabilizer. The fluorinated polyacrylate latex film showed good water repellency. However, to the best of our knowledge, there has been no report on preparation and antibacterial property of cationic fluorinated polyacrylate emulsifier-free emulsion by fluorine-containing amphiphilic block copolymer as a stabilizer, although cationic fluorinated polyacrylate is known to have good water repellency and antibacterial property.

The environment-friendly waterborne textile finishing agent with multifunction has recently aroused particular enthusiasm in modern textile industry. Among various kinds of purchasable waterborne textile finishing agents in the market, the cationic fluorinated polyacrylate emulsion is endowed with excellent water repellency and antibacterial activity due to fluorinated segments with the special low surface energy and cationic groups with excellent antibacterial activity and adsorbability to textile fiber, and showed great potential for practical application in textile industry. The traditional waterborne cationic fluorinated polyacrylate textile finishing agent was generally synthesized by emulsion polymerization in the presence of low molecular weight emulsifiers [19], [20], [21]. However, the residual emulsifiers in emulsion could easily migrate to the fabric surface during the fabric finishing process, resulting in the decrease of the water repellency of the finished fabric. Compared with the traditional cationic fluorinated polyacrylate emulsion, the cationic fluorinated polyacrylate emulsifier-free emulsion using amphiphilic block copolymer as a stabilizer has the advantage of no emulsifier migration during film formation, which can endow the finished fabric with excellent water repellency.

Hence, in this work, cationic fluorinated polyacrylate emulsifier-free emulsion was synthesized using poly(2-(dimethylamino) ethyl methacrylate)-b-poly (hexafluorobutyl acrylate) (PDMAEMA-b-PHFBA) both as a stabilizer and a RAFT agent. In addition, cationic fluorinated polyacrylate emulsifier-free emulsion was used as a fabric finishing agent. The influence of the amount of (2-(acryloyloxy)ethyl)trimethylammonium chloride (DMC) on emulsion polymerization and finished fabric properties was studied. The cationic fluorinated polyacrylate latex particles were characterized by dynamic laser scattering (DLS). The surface morphology of the finished fabrics was observed by scanning electron microscopy (SEM). The water repellency and antibacterial properties of the finished fabrics were also investigated.

Section snippets

Materials

2-(Dimethylamino) ethyl methacrylate (DMAEMA) was purchased from Feixiang Group of Companies and passed through an alumina column to remove inhibitor prior to use. Hexafluorobutyl acrylate (HFBA), hexafluorobutyl methacrylate (HFBMA) supplied by XEOGIA Fluorine-Silicon Chemical Company, went through alkaline alumina chromatographic column to remove inhibitor before use. Butyl acrylate (BA), styrene (St) were purchased from Tianjin Kemiou Chemical Co. Ltd, and used as received. Stearyl acrylate

Synthesis and characterization of poly(2-(dimethylamino) ethyl methacrylate)-b-poly (hexafluorobutyl acrylate)

Fluorine-containing amphiphilic diblock copolymer poly(2-(dimethylamino) ethyl methacrylate)-b-poly (hexafluorobutyl acrylate) (PDMAEMA-b-PHFBA) was synthesized by a two-step RAFT solution polymerization, as shown in Scheme 1. The structure of PDMAEMA-b-PHFBA was characterized by ¹H-NMR. As shown in Fig. 1, the PDMAEMA-b-PHFBA was dissolved in dimethylsulfoxide-d₆. There appear feature signals of PDMAEMA segment (δ = 2.50 ppm ((CH₃)₂NCH₂CH₂-), δ = 2.22 ppm ((CH₃)₂NCH₂CH₂-)) [23], and PHFBA

Conclusions

Cationic fluorinated polyacrylate emulsifier-free emulsion was successfully synthesized using amphiphilic block copolymer PDMAEMA-b-PHFBA as stabilizer and (2-(acryloyloxy)ethyl)trimethylammonium chloride (DMC) as a cationic monomer via ab initio RAFT emulsion polymerization. Surface tension of PDMAEMA-b-PHFBA decreased rapidly with the increase of the PDMAEMA-b-PHFBA concentration. The CMC and γ_CMC of PDMAEMA-b-PHFBA was lower than those of SDS. The latex particle size and its distribution

Acknowledgments

This work was supported by the National Natural Science Fund of China (No. 21206088), the Industrialization Cultivation Item of Shaanxi Province Educational Department (No. 16JF006), the Key Scientific Research Group of Shaanxi Province (No. 2013KCT-08), and the Scientific Research Group of Shaanxi University of Science and Technology (No. TD12-03).

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View full text

Synthesis of cationic fluorinated polyacrylate copolymer by RAFT emulsifier-free emulsion polymerization and its application as waterborne textile finishing agent

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials

Synthesis and characterization of poly(2-(dimethylamino) ethyl methacrylate)-b-poly (hexafluorobutyl acrylate)

Conclusions

Acknowledgments

Preparation and investigation of waterborne fluorinated polyacrylate/silica nanocomposite coatings

Prog Org Coat

Spherical and core-shell fluorinated polyacrylate latex particles: preparation and characterization

Colloid Polym Sci

Preparation and characterization of nano-SiO2/fluorinated polyacrylate composite latex via nano-SiO2/acrylate dispersion

Colloids Surfaces A

Surface topography and hydrophobicity of waterborne fluorinated acrylic/silica hybrid coatings

Colloids Surfaces A

Fluorinated amphiphilic block copolymers via RAFT polymerization and their application as surf-RAFT agent in miniemulsion polymerization

RSC Adv

Amphiphilic block copolymers as stabilizers in emulsion polymerization: effects of the stabilizing block molecular weight dispersity on stabilization performance

Macromolecules

Controllable synthesis of new polymerizable macrosurfactants via CCTP and RAFT techniques and investigation of their performance in emulsion polymerization

Langmuir

Amphiphilic poly(ethylene oxide) macromolecular RAFT agent as a stabilizer and control agent in ab initio batch emulsion polymerization

Macromolecules

Organic solvent-free low temperature method of preparation for self assembled amphiphilic poly (ε-caprolactone)-poly (ethylene glycol) block copolymer based nanocarriers for protein delivery

Colloid Surf B

Micellar assembly of a photo-and temperature-responsive amphiphilic block copolymer for controlled release

Polym Chem

Block copolymers in emulsion and dispersion polymerization

Macromol Rapid Commun

Atom transfer radical polymerization (ATRP): current status and future perspectives

Macromolecules

Living free-radical polymerization by reversible addition-fragmentation chain transfer: the RAFT process

Macromolecules

A guide to the synthesis of block copolymers using reversible-addition fragmentation chain transfer (RAFT) polymerization

Chem Soc Rev

Hydrophobic films of acrylic emulsion by incorporation of fluorine-based copolymer prepared through the RAFT emulsion copolymerization

J Fluor Chem

Block copolymers of dodecafluoroheptyl methacrylate and butyl methacrylate by RAFT miniemulsion polymerization

J Polym Sci Pol Chem

Synthesis and micellar self-Assembly of ternary hydrophilic-lipophilic-fluorophilic block copolymers with a linear PEO chain

Langmuir

Preparation and characterization of nano-SiO₂/fluorinated polyacrylate composite latex via nano-SiO₂/acrylate dispersion