Preparation of fluoroacrylate nanocopolymer by miniemulsion polymerization used in textile finishing

Latex based on fluoroacrylate (TAN) and other comonomers was prepared via miniemulsion polymerization in the presence of stearyl trimethyl ammonium chloride (STAC) and 2, 2′‐azobis (2‐amidinopropane) dihydrochloride (ABAP) as a water soluble initiator. Light transmittance studies demonstrated that the light transmittance of prepared emulsions increases with the amount of TAN, STAC, cosolvent DPM, and hydrophobe DM. Given suitable reaction temperature and quantities of TAN, STAC, DPM, and DM, a copolymer emulsion of fluoroacylate with a particle size of 50 nm was produced. The water repellency tested on polyester fabrics displayed greater effectiveness than that of commercial products with higher fluorine content. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1466–1472, 2004     

含氟丙烯酸酯共聚乳液的制备及在织物上的应用

用139.21 g端基含氢的含氟醇、47.52 g丙烯酸和一定量的对甲苯磺酸和对苯二酚,回流反应10~12 h,得到含氟丙烯酸酯。含氟丙烯酸酯在复合乳化剂存在下进行乳液共聚,得到稳定的泛蓝光的三元共聚乳液。将其应用于纯棉、涤棉及电力纺3种织物的防水防油处理,防油性能得到明显改善,等级可达90~130。     

Enzymatic improvement of guar‐based thickener for better‐quality silk screen printing

Guar galactomannan (referred to as guar gum) is a versatile polysaccharide, obtained from the seeds of the shrub Cyamopsis tetragonolobus, which finds several applications in either its native or chemically modified form. For textile printing, guar gum can also be partially depolymerised in order to promote dye penetration, improve swelling in water and achieve the desired rheological properties. Guar gum is obtained from guar seeds by a thermo‐mechanical process that leaves ca. 3% of largely insoluble proteins in the gum, originating from the endosperms aleurone layer. When printing silk fabrics with acid or premetallised dyes, guar endogenous insoluble proteins bind tightly to anionic dyes, causing deposition of coloured aggregates on the fabric. This causes imperfections on the printed fabric in the form of tiny, but visible, ‘dots’, which lowers the quality of the final articles. In order to eliminate ‘dotting’, a novel printing thickener composed of depolymerised guar gum mixed with a bioengineered subtilisin protease has been developed. Upon solubilisation of the gum, and during preparation of the printing paste mixture, the protease hydrolyses guar gum insoluble proteins, generating soluble peptides that are washed off by the post‐printing treatments of the fabric. This enzymatic application prevents ‘dotting’ and significantly improves the quality of the silk print, without any measurable tensile strength loss of the fabric.     

Wash fastness of fluorocarbon finishes on polyester fabrics

A fabric's surface tension provides a measure of its ability to repel water and oil, while water penetration can be evaluated from a fabric's hydrostatic pressure, which depends mainly on the pore size and thus on the weave. One way of making a surface hydrophobic is to coat it with fluorinated polymers, which confer a low surface tension, reducing the fabric's wettability while preserving its breathability. We have shown that polyester microfibre fabrics (which already have a tight weave and hence high hydrostatic pressure) can be treated with fluorinated finishes to increase water and oil repellency. Observation of a piece of fluorinated polyester microfibre fabric over a number of washings has shown that a regenerative heat treatment preserved the repellency of the fabric but had little influence on the decrease in hydrostatic pressure that occurs with washing.     

Influence of additives on the fabric stiffness and colour depth of viscose printed with a guar gum thickener and a reactive dye

The effect of additives in a printing paste containing guar gum thickener and bireactive dye for cellulose printing was studied. The efficiency of the additives with respect to their chemical structure and concentration and the efficiency in combination with thickeners of different types (nonsubstituted, different degrees of carboxymethylation) and different concentrations (solid content) was investigated by assessing the fabric stiffness, colour depth, dye penetration, the viscosity and viscoelasticity of the printing paste and the printing paste add-on. Some additives caused a decrease in the fabric stiffness to an acceptable degree with little effect on the colour depth. Dye penetration was found to be exclusively additive-dependent. Spectroscopic and rheological investigations confirmed the reduction of dye/guar gum interactions due to the occurrence of additive/guar gum and additive/dye interactions. The best quality prints were obtained using a printing past containing a nonionic surfactant and a highly carboxymethylated guar gum thickener.     

Convenient method for removing and concentrating hydrophobic organic compounds from water with amphiphilic polymers

A stable fluoroacrylate copolymer emulsion was successfully prepared by miniemulsion polymerization with fluoroacrylate, lauryl methylacrylate, and methyl methacrylate as monomers. Extremely hydrophobic fluoroacrylate, instead of conventional cosurfactants, was used as a reactive cosurfactant to stabilize the miniemulsions. The results indicated that fluoroacrylate retarded Ostwald ripening and allowed the production of stable miniemulsions. The chemical compositions of the copolymer were studied with Fourier transform infrared and ¹H‐NMR. The average composition of the copolymers prepared with miniemulsions was in good agreement with the feed ratio according to ¹H‐NMR from the integration ratios corresponding to typical protons of the individual monomers. The particle size distribution and morphology of the latex particles were determined with laser particle analysis and transmission electron microscopy. The particle size of the latex underwent no change in the process of miniemulsion polymerization, but the particle size distributions were broader than those of conventional emulsion polymerization. The effects of various reaction parameters, including the temperature and concentrations of the emulsifier and initiator, on the miniemulsion polymerization were also investigated, and the polymerization rate and conversion increased with increasing concentrations of nonylphenol polyethoxylate (with an average of 40 ethylene oxide units per molecule), cetyltrimethylammonium, and 2,2′‐azobisisobutyronitrile. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 641–647, 2007     

Microemulsion polymerization of microlatex in sublimation ink for cotton fabric ink jet printing

A novel microlatex of styrene/2‐ethylhexylacrylate (2‐EHA)/2‐hydroxyethyl methacrylate (2‐HEMA)/N‐(isobutoxy methyl) acrylamide (IBMA) copolymer was synthesized and mixed in sublimation inks to be inkjet printed on the cotton fabric to provide soft hand feel and good color fastness after heat‐press. In the optimized microemulsion composition with highest monomer mixture amount, polymerizable maleate surfactants with moderate EO value attained smaller microemulsion droplet size in mono distribution and lower dosage than conventional POE surfactants in combination with anionic surfactants. With adopted semicontinuous process in microemulsion copolymerization at 65°C, the polymerizable surfactants stabilized the growth of microlatex particle size within 70 nm in 240 min and attained 100% of monomer conversion rate with two initiator systems, 2‐2‐azobis(2‐methlypropionamidine dihydrochloride (AAPH) and tert‐butylhydroperoxide (TBHP)/sodium formaldehyde sulfoxylate (SFS). The microlatex particle size of two surfactant systems increased with higher conversion rate and reaction temperature, which synchronized with initiator concentration. High polymer solid content was contributed mainly by IBMA monomer ratio requiring higher amounts of anionic surfactants and 2‐HEMA as a cosurfactant in particle stabilization. Although the optimum ink containing high IBMA microemulsion exhibited small variation in viscosity, pH value and surface tension, disperse dyes in four colors had different interaction with the microlatex to demonstrate distinct printing durability and color performance. The resulted cotton fabric attained high K/S value for color strength, great AATCC grade for color fastness, and nearly zero color difference for negative dye particle diffusion or migration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis,swelling behaviors,and slow‐release characteristics of a guar gum‐g‐poly(sodium acrylate)/sodium humate superabsorbent

Superabsorbents used in agricultural and ecological projects with low‐cost, slow‐release fertilizers and environmentally friendly characteristics have been extensively studied. The use of a natural polymer as the matrix and then further polymerization with some functional material has become the preferred method. In this work, with natural guar gum (GG), partially neutralized acrylic acid, and sodium humate (SH) as the raw materials, ammonium persulfate as the initiator, and N,N′‐methylenebisacrylamide (MBA) as the crosslinker, GG‐g‐poly(sodium acrylate) (PNaA)/SH superabsorbents were synthesized through a solution polymerization reaction and were characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis. The effects of the SH content and MBA concentration on the water absorbency were investigated. The results showed that the introduction of SH into the GG‐g‐PNaA system could improve the water absorbency, swelling rate, pH‐resistant property, and reswelling capability, and the superabsorbent containing 15 wt % SH had the highest water absorbency of 532 g/g of sample in distilled water and 62 g/g of sample in a 0.9 wt % NaCl solution. The slow release in water and water retention in sandy soil tests revealed that the superabsorbent could act as a fertilizer as well as an effective water‐saving material for agricultural applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of silica sol/fluoroacrylate core–shell nanocomposite emulsion

The silica sol/fluoroacrylate core?Cshell nanocomposite emulsion was successfully synthesized via traditional emulsion polymerization through grafting of KH-570 onto silica particles. Comparing the performance of the polyacrylate copolymer, the fluorinated polyacrylate copolymer and the silica sol/fluoroacrylate core?Cshell nanocomposite emulsion, we can come to a conclusion that the silica sol/fluoroacrylate core?Cshell nanocomposite emulsion presents significantly excellent performance in all aspects. The products were characterized by Fourier transform infrared (FTIR), photon correlation spectroscopy (PCS), transmission electron microscopy (TEM), thermogravimetry (TGA), Contact angle and UV?Cvis analyses techniques. The chemical structure of polyacrylate copolymer, fluorinated polyacrylate copolymer and silica sol/fluoroacrylate nanocomposite were detected by FTIR. The size and stability of emulsion latex particles were determined by PCS technique. TEM analysis confirmed that the resultant latex particle has the core?Cshell structure, obviously. The water absorption and contact angle data also showed that the silica sol/fluoroacrylate nanocomposite film has good hydrophobic performance. TGA analysis indicated the weight loss of the silica sol/fluoroacrylate nanocomposite film begins at around 350?°C which testifies its good thermal stability. The UV?Cvis spectroscopy analysis showed that the silica sol/fluoroacrylate nanocomposite film possess UV?Cvis shielding effect when the added volume amount of KH570 modified silica sol is up to 5?mL. Therefore, the excellent properties of hydrophobicity, thermodynamics and resistance to ultraviolet provide the silica sol/fluoroacrylate nanocomposite film with potential applications in variety fields. In addition, the formation mechanism of core?Cshell structure silica sol/fluoroacrylate nanocomposite latex particles was speculated.     

Synthesis and properties of fluorine–silicon modified polyacrylate hybrid latex particles with core–shell structure obtained via emulsifier‐free emulsion polymerization

A core–shell fluorine–silicon modified polyacrylate hybrid latex was successfully prepared via emulsifier‐free emulsion polymerization. The chemical composition and core–shell morphology of the resultant hybrid particles were investigated using ¹H NMR and Fourier transform infrared spectroscopies and transmission electron microscopy (TEM), respectively. TEM analysis indicated that the core–shell hybrid particles were uniform with narrow size distributions. The particle size and zeta potential decreased with an increase of alkylvinylsulfonate surfactant from 2.5 to 6.0 wt%. X‐ray photoelectron spectroscopy revealed that fluorine concentrated preferentially at the film surface during a film‐formation process. The film formed from the fluorine–silicon modified polyacrylate showed much higher thermal stability than a film formed from polyacrylate and fluorine‐modified polyacrylate. Contact angle results showed that a finished fabric had remarkable water repellency. © 2015 Society of Chemical Industry     

瓜尔胶/丙烯酰胺的反相乳液接枝共聚

以硝酸铈铵/硝酸为引发剂,在反相乳液中引发瓜尔胶/丙烯酰胺的接枝共聚反应。考察了m(丙烯酰胺AM)∶m(瓜尔胶GG)、引发剂浓度、反应温度和反应时间对接枝聚合的影响。结果表明,当m(AM)∶m(GG)=3∶2,引发剂浓度为4 mmol/L,反应时间为4 h,反应温度为45℃时,接枝共聚反应的接枝率和单体转化率分别为147.05%和87.7%。接枝共聚物的最大相对分子质量(简称分子量,下同)可达到1.73×106。红外光谱(IR)分析证明了AM确实接枝到GG分子链上,热重分析(TGA)显示接枝的AM单体并未影响GG的热稳定性。     

Studies on the possibility of recycling microencapsulated disperse dye‐bath effluents

The volume of water consumed by human beings has increased dramatically in recent years while water supply has remained constant; both demographic growth and the expansion of industrial activity require more water consumption. The textile industry is undoubtedly one of the most pressured industries that need water intensively. Efficient use of water tends to be a crucial subject for the dyeing industry. In this study, melamine resin microcapsules containing pure disperse dyes were prepared by in situ polymerization. The microcapsules were characterized on the basis of structure, morphologies, mean particle size, and size distribution. The dyeing behaviors of microencapsulated disperse dyes (MDDs) were evaluated on polyester fabrics in the absence of auxiliaries. Its effluent can be reused several times after being simply filtered and can be used as solvent for PET fabric scouring. The treated fabrics exhibited satisfactory levelness and fastness properties. MDDs can be used in dyeing PET, without using surfactants, and the effluents can be recycled and reused. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of silicone oil nanoemulsion softeners using different surfactants and their effect on physical characteristics of polyester fabric

Silicone oil nanoemulsion softeners with different particle sizes can be prepared using different surfactants with various ratios aminosilicone oil, surfactants concentration and time of mixing. The silicone oil nanoemulsion softeners could penetrate well into the polyester fibers; therefore, they can induce desirable physicochemical properties in the fabric. In current study, we first prepared silicone oil nanoemulsion softeners by designing via DOE software and with different particle sizes using nonyl phenol, octyl phenyl ether and fatty alcohol surfactants, and we investigated them using dynamic light scattering (DLS) and transmission electron microscope (TEM) techniques. In DOE software, the effect of various independent variables of emulsification process such as surfactant type, oil weight fraction, surfactant concentration and time of mixing on dependent variables were studied including particle size, z-average and width. Then, we examined the physical characteristics of polyester fabric by applying silicone oil macro, micro and nanoemulsion softeners. The treated fabrics with these softeners were compared with each other through the physical properties. The scanning electron microscopy (SEM) analysis showed the polyester fabric treated with silicone nanoemulsion softeners appeared to have smoother fiber surface. To prove the penetration of silicone particles into the fabric fibers, a cross section was taken from the cross section of polyester fabric by microtome in liquid nitrogen. The TEM images from cross section of fabrics treated with the silicone oil nanoemulsion softeners confirmed that the nanoparticles had penetrated well into the polyester fibers; therefore, they could induce desirable physicochemical properties in the fabric.     

Printing of reactive silicones for surface modification of textile material

For outdoor sports, waterproof breathable materials are widely used to provide protection from environmental factors like rain and wind. The most important techniques to achieve excellent performance use perfluorinated organic substances, which must be replaced in the near future due to health concerns and their environmental persistency. Printing of textile materials with reactive silicone pastes could be an alternative to introduce water repellency without fluorocarbon finishing. In this work, production of barrier textiles through one‐step silicon printing was studied, using a two‐component paste with long pot life and a thermal fixation step. Three different knitted fabrics made from micromodal, polyamide/elastin, and cotton/polyester were used as substrates for the printing. The achieved hydrophobic modification of the fabric was analyzed by determination of water shedding angle, water resistance, water retention values, moisture content, air permeability, tensile properties, and infrared spectroscopy. The results indicate several areas of technical application for the modified fabric, such as barrier textiles with permeability control, localized modification of mechanical properties of fabric and garment. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42594.     

Synthesis and characterization of fluorinated polyacrylate latex emulsified with novel surfactants

The fluorinated polyacrylate latex were successfully prepared with semi- continuous seeded emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA) and hexafluorobutyl methacrylate (HFMA) which was initiated with potassium persulfate (KPS) initiator and emulsified with the novel mixed surfactants of sodium lauryl glutamate (SLG) and alkylphenol ethoxylates (OP-10). The structure of the resultant latex was confirmed by Fourier transform infrared spectroscopy (FTIR). The particle size of the latex was measured by Zetatrac dynamic light scattering detector. The film of latex was tested by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and contact angle (CA). The optimum conditions of preparing the novel fluorinated polyacrylate latex are optimized and the results are as follows: the amount of emulsifiers is 4.0%; mass ratio of SLG to OP-10 is 1:1, the amount of the initiator is 0.6%. The mass ratio of MMA to BA is 1:1 and the amount of HFMA is 7.0%. In this case, the conversion is high and the polymerization stability is good. In addition, the water resistance and thermal properties of the latex films were improved significantly in comparison with the film of the latex prepared without the fluorinated monomer.     

Synthesis and characterization of graft copolymer (guar gum–g–N‐vinyl‐2‐pyrrolidone) and investigation of metal ion sorption and swelling behavior

Graft copolymer of N‐vinyl‐2‐pyrrolidone with guar gum was synthesized and its reaction conditions were optimized for better yield using potassium peroxymonosulfate (PMS) and glycolic acid (GA) as a redox initiator. The effect of PMS, GA, hydrogen ions, guar gum, and N‐vinyl‐2‐pyrrolidone (NVP) along with reaction time and temperature were studied by determining the grafting parameters: grafting ratio, efficiency, conversion, add‐on, homopolymer, and rate of grafting. It was observed that the maximum yield occurred at with a time of 120 min at a temperature of 45°C and a guar gum concentration of 0.4 g/L concentration. The graft copolymer was characterized by infrared spectroscopy and thermal analysis. The activation energy for the grafted and ungrafted gum was calculated. It was observed that the graft copolymer was thermally more stable than the pure gum. The swelling and metal ion sorption behavior of guar gum and guar gum‐g‐N‐vinyl‐2‐pyrrolidone also were studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2480–2489, 2006     

Synthesis and characterization of grafted carboxymethyl guar gum

Graft copolymers of carboxymethyl guar gum (CMGG) and polyacrylamide (PAM) have been synthesized by grafting polyacrylamide chains onto carboxymethyl guar gum backbone using a ceric‐ion‐induced solution polymerization technique. By varying the amount of initiator, three different grades of graft copolymers are synthesized. The characterization of graft copolymer is carried out by FTIR, NMR, intrinsic viscosity measurement, SEM, SLS, DTG, and rheology. A comparison of flocculation efficiency of CMGG and its graft copolymer shows that the graft copolymer exhibits better flocculation performance. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Modification of polyester fabric properties by surfactant‐aided surface polymerization

Poly(methyl methacrylate) (PMMA) was applied to polyester fabric using a surface analog of emulsion polymerization. The admicellar polymerization was carried out using 1.5 mM dodecylbenzenesulfonic acid (DBSA) at pH 4 with 0.15M NaCl, 1 : 8 DBSA:monomer, and 1 : 10 initiator:monomer molar ratio. The PMMA film, which was formed, was characterized by SEM and FTIR. Hydrolysis of the PMMA film on polyester fabric was carried out to introduce carboxylic acid groups to the polyester surface to increase its hydrophilicity. The results show that a PMMA thin film was successfully formed on the polyester fabric. The water contact angle of the PMMA‐coated polyester fabric after hydrolysis by 10M H₂SO₄ for 5 h was reduced from 117.3° to 0° and there was a significant increase in the moisture‐regain value of the treated fabric. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 4059–4064, 2007     

Fluorinated hyperbranched polyester acrylate used as an additive for UV curing coatings

The fluorinated hyperbranched polyester acrylate (FHPA) was synthesized by modifying the hyperbranched polyester Boltorn H20 with fluorinated isocyanate, and characterized with ¹H NMR and FTIR spectroscopic analysis. The water and oil wettability of the UV cured film with FHPA as an additive was investigated by measuring the contact angle. The results showed that an extremely low concentration of FHPA, even below 0.1 wt%, resulted in efficient decrement of the surface tension of UV cured film to 10–15 mN/m, and thus makes the film highly hydrophobic and oleophobic. The film with FHPA addition was stable in acidic and neutral solutions, and still had good water repellency after immersion in a pH 1 solution for several days. The X-ray photoelectron spectroscopic analysis confirmed that the film surface was enriched with fluorinated species. Moreover, the molecule with the highest average number of perfluoroalkyl groups had the highest tendency to aggregate at the surface of the UV cured film.     

Modified guar gum: An alternative source for printing of cotton fabric with reactive dye

The alginate thickener is the thickener frequently used for reactive printing of textile. The thickener responds with reactive pigments and thus does not lead to the fabric composition becoming stiffer. In this study, we prepared oxidised natural guar gum with hydrogen peroxide, sodium hypochlorite and sodium hydroxide. All other polysaccharides comprise reactive hydroxyl units with a stronger reactivity that must be replaced if they are to be used in reactive printing. Guar derivatives were synthesised and verified using Fourier-transform infrared (FTIR) spectroscopy. Natural thickeners, synthetic guar gum derivatives, have been employed in textile printing technique. In comparison to other synthetic thickeners, modified environmental guar gum polymer has been shown to be an ecologically friendly and low-cost thickener. Cotton fabric printed with modified guar thickening with hydrogen peroxide has even stronger colour strength than fabric printed with sodium alginate thickener, which is highly favourable. Penetration properties, colour value, colour strength, colour fastness to washing, light and rubbing was compared with alginate thickener (readily available on the market). Guar gum thickeners showed enhanced features versus sodium alginate for reactive printing. Partially replaced guar gum is an appropriate option due to the colour and physical properties.