Plasma-induced graft polymerization on the surface of aramid fabrics with improved omniphobicity and washing durability

Durable superomniphobic surfaces are desirable for their practical applications,including selfcleaning,non-fouling,protective clothing and the separation of liquids.The plasma-induced polymerization of environmentally friendly C6 from a perfluoralkyl methlacrylate copolymer emulsion,AG-E081,was performed and a durable omniphobic fabric was achieved.C6 is an ecological alternative to C8(eight CF2 groups)fluorinated compounds,and it was thereafter successfully incorporated into aramid fabric to achieve a durable superomniphobic surface.The fabric became water and oil repellent with an extremely high water contact angle of 180°.As tested by the water spray AATCC test and hydrocarbon resistance test,the as-prepared fabric gained 100°(ISO 5)and grade number 4 respectively.Furthermore,the fabrics also showed significantly improved washing durability after ten washing cycles.By scanning electron microscopy(SEM),Fourier-transform infrared spectroscopy(FTIR)and x-ray photoelectron spectroscopy(XPS)tests,it is indicated that the durable superomniphobicity can be attributed to the roughness and activation of the aramid surface by the plasma pre-treatment,which induces more adsorption and chemical graft of the C6 copolymer.

THE EFFECTS OF PLASMA-INDUCED GRAFT COPOLYMERIZATION WITH ACRYLIC ACID ON THE STRUCTURE AND DYEING PROPERTIES OF MULBERRY SILK

The effects of plasma-induced graft copolymerization with acrylic acid (AAc) on the structure and dyeing properties of mulberry silk are investigated. Through the transmission infrared spectroscopy(IR) , attenuated total reflection infrared spectroscopy(ATR-IR) and X-ray photoelectron spectroscopy(XPS) studies, changes of the surface structure and composition are observed. The results show that plasma-induced graft copolymerization has a different meehanism from that of chemical graft copolymerization. The plasma graft copolymerization brings AAc branch polymers into the surface of silk through the initiation of some kinds of oxygen and nitrogen groups created by plasma. That is just the reason that the dyeing ability and color fastness of plasma-grafted silk for cationic dyestuff increase and its mechanical properties have not been changed significantly.

UV-induced Self-initiated Graft Polymerization of Acrylamide onto Poly(ether ether ketone)

Photo-grafting of hydrophilic monomer was used to enhance the hydrophilicity of poly（ether ether ketone） （PEEK） with the aim of extending its applications to biological fields. PEEK sheets were surface modified by grafting of acrylamide（AAm） with ultraviolet（UV） irradiation in the presence or absence of benzophenone（BP）. The effects of BP, irradiation time and monomer concentration on the surface wettability of PEEK were investigated. Characteriza tion of modified PEEK using scanning electron microscopy（SEM）, energy-disperse spectrometer（EDS） and water contact angle measurements shows that AAm was successfully grafted on PEEK surface both in presence and absence of BP. With the increase in irradiation time and monomer concentration, contact angles decrease to as low as 30°, demonstrating a significant improvement of surface hydrophilicity. In agreement with the decrease in contact angle, under identical conditions, the nitrogen concentration increases, suggesting the increase in grafting degree of the grafting polymerization. This investigation demonstrates a self-initiation of PEEK due to its BP-like structure in the backbone of the polymer. Though the graft polymerization proceeds more readily in the presence of BP, the self-initiated graft polymerization is clearly observed.

PHOTO-INDUCED GRAFT POLYMERIZATION OF ACRYLAMIDE ON POLYPROPYLENE MEMBRANE SURFACE IN THE PRESENCE OF DIBENZYL TRITHIOCARBONATE

Ultraviolet （UV）-induced graft polymerization of acrylamide （AAm） on polypropylene substrates was successfully conducted using dibenzyl trithiocarbonate （DBTTC） as photoinitiator. It was confirmed by chemical analysis and surface morphology observation with attenuated total reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. A possible mechanism for this graft process was presented, which suggested that, under UV irradiation, the C： S bond in DBTTC could split and abstract a hydrogen from the polypropylene surface and a surface free radical was then formed, and initiated the graft polymerization of AAm.

SURFACE MODIFICATION OF MICROPOROUS POLYPROPYLENE MEMBRANES BY GRAFT POLYMERIZATION OF N,N-DIMETHYLAMINOETHYL METHACRYLATE

Surface modification of microporous polypropylene hollow fiber membranes was performed by radical-induced graft polymerization of N,N-dimethylaminoethyl methacrylate (DMAEMA). The influences of temperature, monomer concentration and pre-adsorbed amount of benzoyl peroxide on grafting degree were studied respectively. It was found that the appropriate graft temperature was 75 'C, at which the grafting degree was the highest and the hydrolytic decomposition of DMAEMA the lowest. Scanning electron photomicrography and the average pore diameters of the modified membranes demonstrated that part of the micropores on the membrane surface was plugged by the grafted polyDMAEMA chains, especially at high grafting degree. Contact angle and water swelling experiments showed that a moderate grafting degree could improve the hydrophilicity of the membranes. In the range of 11.3%-12.0% grafting degree, the water swelling percentage reached its maximum (51.1%) and the contact angle reached its minimum (74 degrees). The bovine serum albumin (BSA) adsorption experiment indicated that the grafted polyDMAEMA had a dual effect on protein adsorption. At the first stage, the BSA adsorption decreased with increasing of DMAEMA grafting degree. As the interaction between BSA and polyDMAEMA on membrane surface increased, the BSA adsorption increased with increasing of DMAEMA grafting degree.

PREPARATION OF NOVEL POLYETHYLENE-graft-POLY(4-VINYLPYRIDINE)-SUPPORTED METALLOCENE CATALYSTS FOR ETHYLENE POLYMERIZATION

Polyethylene (PE) grafting 4-vinylpyridine copolymers has been produced as powders of different rushes by theirradiation method. After treatment with methylaluminoxane (MAO), the copolymers were used as supports for Cp_2ZrCl_2catalyst Results of X-ray photoelectron spectroscopy, Fourier transforms infrared spectroscopy, ultraviolet spectroscopy andscanning electron microscope measurements show that the catalytic sites have been linked through MAO on the PE-graft-4-vinylpyridine (PEVP). The percentages of grafting 4-vinylpyridine and supported Cp_2ZrCl_2 depend on the size ofpolyethylene powder. The smaller the polyethylene powder, the more percent of 4-vinylpyridine groups and Cp_2ZrCl_2 existon the polyethylene chains, and the PEVP-supported catalyst has a relatively high activity for ethylene polymerization.

Ultravilolet-radiation-induced graft polymerization of acrylamide onto the melt-blown polypropylene filter element by dynamic method

By dynamic method under UV irradiation, commercial melt-blown polypropylene （PPMB） filter element was modified with acrylamide （AAm） using benzophenone （BP） as initiator. Attenuated total reflection-Fourier transform infrared spectroscopy and scanning electron microscope verified that polyacrylamide chain was grafted on the fiber surface of PPMB filter element. Elemental content analysis with energy dispersive X-ray of fibers revealed that the polymerization content in the inner part of filter element was relatively higher than that in the outer. Degree of grafting changed with initiator concentration, monomer concentration, reaction temperature and reached 2.6% at the reaction condition： CBp=0.06 mol/L, CAAm=2.0 mol/L, irradiation time： 80 min, temperature： 60℃. Relative water flux altered with the hydrophilicity and pore size of filter element. In the antifouling test, the modified filter gave greater flux recovery （approximately 70%） after filtration of the water extract of Liuweidihuang, suggesting that the fouling layer was more easily reversible due to the hydrophilic nature of the modified filter.

Graft Copolymerization of N,N-Dimethylacrylamide to Cellulose in Homogeneous Media Using Atom Transfer Radical Polymerization for Hemocompatibility

In homogeneous media, N,N-Dimethylacrylamide (DMA) was grafted copolymerization to cellulose by a metal-catalyzed atom transfer radical polymerization (ATRP) process. First, cellulose was dissolved in DMAc/LiCl system, and it reacted with 2-bromoisobutyloyl bromide (BiBBr) to produce macroinitiator (cell-BiB). Then DMA was polymerized to the cellulose backbone in a homogeneous DMSO solution in presence of the cell-BiB. Characterization with FT-IR, NMR, and GPC measurements showed that there obtained a graft copolymer with cellulose backbone and PDMA side chains (cell-PDMA) in well-defined structure. The proteins adsorption studies showed that the cellulose membranes modified by the as-prepared cell-PDMA copolymer owns good protein adsorption resistancet.

Grafting Methyl Methacrylate onto Silk via Emulsion Graft Copolymerization Using a Diethylzinc Complex Initiator

Methyl methacrylate (MMA) was grafted onto silk fiber in a one-step emulsion system using a diethylzinc and 1,10-phenanthroline complex. The reaction conditions were investigated by varying temperature and initiator to monomer ratio. Fourier transform infrared (FTIR) spectrum, thermogravimetric analysis (TGA), and scanning electron microscopy (SEC) techniques were used to characterize the structure, thermal stability, and surface morphology of the obtained product, respectively. Grafting of MMA onto silk increased the thermal stability of silk. The FTIR spectrum and SEM images provided further evidence that MMA has been successfully grafted onto the silk fiber. A peak ascribed to the C=O stretching vibration of MMA was detected in the FTIR spectrum of grafted silk fiber, which was not present in the spectrum of pure silk fiber. Moreover, the SEM images illustrated the increase in diameter and surface roughness of grafted silk compared with pure silk. Lastly, the dyeing performance of the modified silk was significantly increased.

SURFACE MODIFICATION OF POLYPROPYLENE MICROFIBRE BY PLASMA-INDUCED VAPOR GRAFTING WITH ACRYLIC ACID

The hydrophilicity, dyeing and antistatic ability of polypropylene microfibre (PPMF) were improved by plasma-induced vapor grafting with acrylic acid. The effects of plasma discharge time, power, liquid phase acrylic acid temperature and environmental temperature on grafting yield were investigated. The existence of grafted polyacrylic acid (PAA) was verified by ESCA and ATR FT-IR. The morphology of grafted PAA was directly observed by SEM. The wicking test shows that the hydrophilicity of modified PPMF is greatly enhanced. The dyeability test of modified PPMF was carried out using Dispersion Yellow. It was found that the dye uptake ratio is linear to the weight percent of grafting. The antistatic ability was indicated by specific resistance. The specific resistance of modified PPMF was reduced to 10(6) similar to 10(7) Ohm . cm, thus the antistatic ability was considerably improved.

Plasma-induced grafting of acrylic acid on bentonite for the removal of U(VI) from aqueous solution

Fabrication of reusable adsorbents with satisfactory adsorption capacity and using environmentfriendly preparation processes is required for the environment-related applications. In this study,acrylic acid（AA） was grafted onto bentonite（BT） to generate an AA-graft-BT（AA-g-BT）composite using a plasma-induced grafting technique considered to be an environment-friendly method. The as-prepared composite was characterized by scanning electron microscopy, x-ray powder diffraction, thermal gravity analysis, Fourier transform infrared spectroscopy and Barrett–Emmett–Teller analysis, demonstrating the successful grafting of AA onto BT. In addition, the removal of uranium（VI）（U（VI）） from contaminated aqueous solutions was examined using the as-prepared composite. The influencing factors, including contact time,p H value, ionic strength, temperature, and initial concentration, for the removal of U（VI） were investigated by batch experiments. The experimental process fitted best with the pseudo-secondorder kinetic and the Langmuir models. Moreover, thermodynamic investigation revealed a spontaneous and endothermic process. Compared with previous adsorbents, AA-g-BT has potential practical applications in treating U（VI）-contaminated solutions.

Adsorbent for Arsenic(V) Removal Synthesized by Radiation-Induced Graft Polymerization onto Nonwoven Cotton Fabric

A fibrous adsorbent for arsenic (As) removal was synthesized with nonwoven cotton fabric as a trunk polymer. 2-hydroxyethyl methacrylate phosphoric acid monomer which composed of phosphoric acid mono (50%) and di (50%) ethyl methacrylate ester was introduced with radiation-induced graft polymerization onto nonwoven cotton fabric. The degree of grafting of 130% was obtained at irradiation dose of 20 kGy with 5% of monomer solution for 2 hours reaction time at 40?C reaction temperature. After the grafted material was contacted with 10 mmol/L of zirconium (Zr) solution at pH 1, 0.38 mmol/g of Zr was loaded on phosphoric units as a functional group for As(V) removal. The resulting adsorbent was evaluated by column mode adsorption with 1 mg/L of As(V) solution at various pH with space velocity 200 h–1. The maximum capacity of As(V) adsorption was 0.1 mmol/g at pH 2.

Synthesis of Amine-type Adsorbents with Emulsion Graft Polymerization of 4-hydroxybutyl Acrylate Glycidylether

Radiation induced graft polymerization on polymeric matrix followed by functionalization is widely accepted for the preparation of metal adsorbents. In this paper, a pre-irradiation method was used for emulsion graft polymerization of 4-hydroxybutyl acrylate glycidylether (4-HB) onto polyethylene/polypropylene (PE/PP) nonwoven fabric. The degree of grafting (Dg) which can be calculated by weight increment was determined as a function of reaction time, irradiation dose, and monomer concentration. After 30 kGy irradiation, with 4-HB concentration of 5%, surfactant Span 20 of 0.5% at 40°C for 2 h, the trunk polymer was made grafted at a Dg of 135%. 4-HB-grafted PE/PP nonwoven fabric was modified by ethylenediamine (EDA) in isopropyl alcohol (IPA) as a solvent at 60°C. With a Dg of 135%, the amine group density of the adsorbent is 2.8 mmol/g. The adsorption test was carried out by batch experiment in several metal ion solutions, and the removal ratio from the EDA modified adsorbent of the metal ions is in the order of Cu2+ > Pb2+ > Zn2+ > Ni2+ > Li+. Compared with glycidyl methacrylate (GMA) which is a typical functional monomer for graft polymerization, 4-HB-grafted adsorbent exhibited not only better mechanical property but also higher adsorption capacity of Cu2+ and Pb2+.

Adsorption behavior of uranyl ions onto amino-type adsorbents prepared by radiation-induced graft copolymerization

Amino-type adsorbents(ATAs) were prepared by radiation-induced graft copolymerization of 4-hydroxybutyl acry late glycidyl ether(HB) onto a polyethylene-coated polypropylene(PE/PP) duplex fiber of a non-woven fabric,and modified with different amines of ethylenediamine(EDA),diethylenetriamine(DETA),triethylenetetramine(TETA) and diethylamine(DEA).The adsorption behavior of uranyl ions onto the ATAs was studied in batch experiments.The effects of the contact time,initial concentration of the ions,temperature,and pH value.The salinity were investigated along with the adsorption kinetics and the adsorption isotherms.The kinetic experimental data followed the pseudo second-order kinetic model,and the adsorption isotherms correlated well with the Langmuir model.The ATAs showed good efficiency in adsorbing uranyl ions,with the best saturation adsorption capacity being 64.26 mg g^(-1) for ATA-DETA within 120 min.The temperature dependence of ATADETA was quite abnormal and the quickest behavior was obtained at 25 ℃.ATAs showed good adsorption capacity over a wide pH range of 4.0-8.5,and HCl could be used in the elution process.Salinity of the solution had great effect on the adsorption capacity,3.5%salinity resulted in a 55%loss of capacity from ATA-DETA.The selectivity of ATA-DETA showed an order of:UO_2^(2+)≈Fe^(3+)> Zn^(2+) > VO_3^- > Co^(2+) > Ni^(2+).

Grafting of 2-Hydroxyethyl Methacrylate onto Silk by Atom Transfer Radical Polymerization

Silk was grafted using 2-hydroxyethyl methacrylate(HEMA)by atom transfer radical polymerization(ATRP)method.The amino groups and hydroxyl groups on the side chains of the silk fibroin was reacted with 2-bromoisobutyryl bromide(BriB-Br)to obtain efficient macroinitiator for ATRP.And the macroinitiator was grafted with HEMA in water aqueous using CuBr/N,N,N',N",N"-pentamethyldiethylenetriamine(PMDETA)as catalyst system.The effects of monomer concentration,the proportion of CuBr and PMDETA,grafting temperature and time on the silk grafting were discussed,and the optimal grafting technology was obtained.FT-IR characterization of the grafted silk showed a peak corresponding to HEMA,which indicated that HEMA was grafted onto the surface of silk.ATRP method could be applied on the silk modification and this technique provided a new way for silk grafting.

Graft co-polymerization of maleic acid and vinyl acetate onto poly(vinylidene fluoride) powder by pre-irradiation technique

Binary monomers of maleic acid and vinyl acetate are grafted onto poly(vinylidene fluoride) (PVDF) powder by pre-irradiation induced graft polymerization technique in emulsion solution. The co-grafting of binary monomers is successfully proved by FT-IR spectroscopy analysis. The influences of the absorbed dose, reaction temperature, reaction time, total concentration of monomers, and feed ratio of binary monomers on the degree of grafting are investigated. The thermal property of grafted PVDF powder was characterized by differential scanning calorimetry (DSC) and thermo-gravimetry analysis (TGA).

Graft Polymerization of Acrylic Acid and Acrylamide onto BOPET Corona Films

The graft polymerization of acrylic acid(A) and acrylamide(B) was carried out onto bi-oriented polyester BOPET corona film.The influence of monomer concentration,reducer concentration and reaction time on the graft polymerization was investigated.The surface tension of the films increased with an increase of monomer concentration,till the concentration of monomer A reached 1.5×10^(-2)g/mL and the concentration of monomer B reached 4.0×10^(-2)g/mL.The surface tension of the films reached a maximum value at 7×10^(-4)M of reducer concentration and subsequently decreased with further increase in reducer concentration.The surface tension of the films increased with the increase of the reaction time apparently within 50min.The grafted corona BOPET films were characterized with IR and XPS.The presence of graft on the film surface was confirmed.The attenuation experiments on grafted corona BOPET films in air at 50℃ and in water were carried out to investigate the persistence of graft polymerization of acrylic acid and arylamide onto BOPET corona films.

Reversible addition-fragmentation chain transfer graft polymerization of acrylonitrile onto PE/PET composite fiber initiated by γ-irradiation

Reversible addition-fragmentation chain transfer(RAFT) mediated grafting of acrylonitrile onto Polyethylene/Poly(ethylene terephthalate)(PE/PET) composite fibers was performed using γ-irradiation as the initial source at ambient temperature. Different initial concentrations of 2-cyanoprop-2-yl dithiobenzonate were used as the chain transfer agent. The kinetics of graft polymerization is in accordance with the living RAFT polymerization. The successful grafting of acrylonitrile is proved by Fourier transform infrared spectroscopy analysis.The results of monofilament tensile test show that mechanical properties of the fibers change slightly after grafting. Scanning electronic microscopy images of the fibers show that the surface of RAFT grafted fibers is smoother than that of fibers grafted conventionally.

Construction of coal pitch-based HA-K grafted poly condensates and their excellent anti-temperature and viscosity-reducing properties

Humic acids(HAs)are widely used as filtrate and viscosity reducers in drilling fluids.However,their practical utility is limited due to poor stability in salt resistance and high-temperature resistance.Hightemperature coal pitch(CP)is a by-product from coal pyrolysis above 650℃.The substance's molecular structure is characterized by a dense arrangement of aromatic hydrocarbon and alkyl substituents.This unique structure gives it unique chemical properties and excellent drilling performance,surpassing traditional humic acids in drilling operations.Potassium humate is prepared from CP(CP-HA-K)by thermal catalysis.A new type of high-quality humic acid temperature-resistant viscosity-reducer(Graft CP-HA-K polymer)is synthesized with CP-HA-K,hydrolyzed polyacrylonitrile sodium salt(Na-HPAN),urea,formaldehyde,phenol and acrylamide(AAM)as raw materials.The experimental results demonstrate that the most favorable conditions for the catalytic preparation of CP-HA-K are 1 wt%catalyst dosage,30 wt%KOH dosage,a reaction temperature of 250℃,and a reaction time of 2 h,resulting in a maximum yield of CP-HA-K of 39.58%.The temperature resistance of the Graft CP-HA-K polymer is measured to be 177.39℃,which is 55.39℃ higher than that of commercial HA-K.This is due to the abundant presence of amide,hydroxyl,and amine functional groups in the Graft CP-HA-K polymer,which increase the length of the carbon chains,enhance the electrostatic repulsion on the surface of solid particles.After being aged to 120℃ for a specified duration,the Graft CP-HA-K polymer demonstrates significantly higher viscosity reduction(42.12%)compared to commercial HA-K(C-HA-K).Furthermore,the Graft CP-HA-K polymer can tolerate a high salt concentration of 8000 mg.L-1,measured after the addition of optimum amount of 3 wt%Graft CP-HA-K polymer.The action mechanism of Graft CP-HA-K polymer on high-temperature drilling fluid is that the Graft CP-HA-K polymer can increase the repulsive force between solid particles and disrupt bentonite's reticulation structure.Overall,this research provides novelty insights into the synthesis of artificial humic acid materials and the development of temperature-resistant viscosity reducers,offering a new avenue for the utilization of CP resources.

Superhydrophobic melamine sponge prepared by radiation-induced grafting technology for efficient oil-water separation

This paper presents a superhydrophobic melamine(ME)sponge(ME-g-PLMA)prepared via high-energy radiation-induced in situ covalent grafting of long-alkyl-chain dodecyl methacrylate(LMA)onto an ME sponge for efficient oil–water separation.The obtained ME-g-PLMA sponge had an excellent pore structure with superhydrophobic(water contact angle of 154°)and superoleophilic properties.It can absorb various types of oils up to 66–168 times its mass.The ME-g-PLMA sponge can continuously separate oil slicks in water by connecting a pump or separating oil underwater with a gravity-driven device.In addition,it maintained its highly hydrophobic properties even after long-term immersion in different corrosive solutions and repeated oil adsorption.The modified ME-g-PLMA sponge exhibited excellent separation properties and potential for oil spill cleanup.