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.

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.

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.

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.

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.

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.

GRAFT POLYMERIZATION OF ACRYLAMIDE ONTO HOMOPOLYMER OF 5-METHYL-5-HEXEN-2, 4-DIONE INITIATED BY CERIC ION

The homopolymerization of 5-methyl-5-hexen-2,4-dione (methacryloylacetone, MAA), a vinyl monomer having beta-diketone group, was carried out in the presence of benzophenone (BP)/N, N-dimenthyl-4-toluidine (DMT) system. Graft polymerization of acrylamide initiated by eerie ion onto the homopolymer film was investigated and the mechanism of the grafting reaction was proposed on the basis of ESR study. The grafted copolymer was characterized by means of grafting percentage, water absorption, XPS spectra and scanning electron photomicrographs.

Radiation-Induced Graft Polymerization of Sodium 4-Styrene Sulfonate onto Multiwalled Carbon Nanotubes and Their Application as Electrogenerated Chemiluminescence Biosensors

Sulfonate groups were introduced to the surfaces of multiwalled carbon nanotubes by the radiation-induced graft polymerization of sodium 4-styrene sulfonate for the use as biosensor supports. Alcohol dehydrogenase was immobilized onto a sulfonated nanotube-supporting electrode with tris（2,2＇-bipyridyl） ruthenium（II） complex to form an electrogenerated chemilluminesce sensor of alcohol. When it was used to detect alcohol in cyclic voltammetric measurements, the sensor showed the linearity over the range of 1.0 × 10^-4 M-5.0 ×10^-2 M, with a correlation coefficient of 0.992 and a detection limit of 1.9 ×10^-6 M. In electrogenerated chemilluminesce detection, it showed linearity over 5.0 × 10^-4 M-1.0 × 10^-2 M, with a correlation coefficient of 0.986 and a detection limit of 1.0 × 10^-6 M. The sensor was demonstrated to be able to detect ethanol in commercial drinks.

Emulsion Graft Polymerization of Methyl Methacrylate onto Cellulose Nanofibers

Methyl methacrylate (MMA) was successfully grafted onto cellulose nanofibers (CNFs) at room temperature in an emulsion system using a diethyl(1,10-phenanthroline N1,N10)zinc(II) complex (Phen-DEZ) with oxygen as the radical initiator. The effects of reaction temperature, initiator concentration, and monomer content on the grafting reaction were investigated. The molecular weight of the non-grafted PMMA, which was produced during graft polymerization, was more than 1 million, as determined by size exclusion chromatography. The PMMA-grafted CNFs were analyzed by Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy, which confirmed the grafting of PMMA on the nanofiber surface. The study presents a strategy for the grafting of high-molecular weight PMMA onto CNFs in an emulsion system using Phen-DEZ and O2.

Synthesis of PGMA Microspheres with Amino Groups for High-capacity Adsorption of Cr(VI) by Cerium Initiated Graft Polymerization

Abstract A novel polyglycidylmethacrylate （PGMA） microspheres with high adsorption capacity of Cr（VI） was prepared by cerium（IV） initiated graft polymerization of tentacle-type polymer chains with amino group on polymer microspheres with hydroxyl groups. The micron-sized PGMA microspheres were prepared by a dispersion polym erization method and subsequently modified by ring-opening reaction to introduce functional hydroxyl groups. The polymer microspheres were characterized by scanning electron microscopy （SEM） and Fourier transform infrared spectroscopy （FTIR）. The results indicated that the polymer microspheres had an average diameter of 5 m with uniform size distribution. The free amino group content was determined to be 5.13 mmol·g^-1 for g;PGMA-NH2 microspheres by potentiometric and conductometric titration methods. The Cr（VI） adsorption results indicated that the graft polymerization of tentacle-type polymer chains on the polymer microspheres could produce adsorbents with high adsorption capacity （500 mg-g-l）. The polymer microspheres with grafted tentacle polymer chains have potenial application in large-scale removal of Cr（VI） in aqueous solution.

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.

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.

Radiation induced graft polymerization of multi-walled carbon nanotubes for superhydrophobic composite membrane preparation

Highly soluble multi-walled carbon nanotubes （MWNTs） were prepared by radiation-induced free radical graft polymerization of vinyl acetate （VAc） onto pristine MWNT surfaces. High resolution transmission electron microscopy （HR-TEM）, Fourier transform infrared （FT1R） spectroscopy, and micro-Raman spectroscopy were used to confirm that poly（vinyl acetate） （PVAc） had been successfully grafted onto the surface of the MWNTs. The effects of experimental parameters on the degree of graft- ing （DG） of PVAc were also investigated, including adsorbed dose, dose rate, initial monomer concentration, and solvents. The grafted MWNTs （MWNTs-g-PVAc） exhibited good solubility in common organic solvents at high mass fraction. In addition, a superhydrophobic composite membrane could be readily fabricated by vacuum filtration of MWNTs-g-PVAc onto a support- ing membrane, as was confirmed by water contact angle testing and visualization by scanning electron microscopy.

MICRON CORE-SHELL PARTICLES PREPARED BY GRAFTING POLYMERIZATION OF METHYL METHACRYLATE FROM NARROW DISPERSE SURFACE OF CHLOROMETHYLATED POLYDIVINYLBENZENE VIA ATRP

Grafting of poly(methyl methacrylate)from narrow disperse polymer particles by surface-initiated atom transferradical polymerization(ATRP)was investigated.Polydivinylbenzene(PDVB)particles were prepared by dispersionpolymerization with poly(N-vinyl pyrrolidone)(PVP)as the stabilizer.Chloromethylated PDVB was used as initiating coresites for subsequent ATRP of methyl methacrylate with CuBr/bpy as catalyst system.It was found that poly(methylmethacrylate)was grafted not only from the particle surfaces but also from within a thin shell layer,leading to particles sizeincreases from 2.38-3.00 μm with a core-shell structure particles.The grafted core-shell particles were characterized withFTIR,SEM,DSC.

Polycaprolactone (PCL) Chains Grafting on the Surface of Cellulose Nanocrystals (CNCs) during <i>In Situ</i>Polymerization of <i>ε</i>-Caprolactone at Room Temperature

This work aimed at investigating the feasibility of surface modification of cellulose nanocrystals (CNCs) using in situ ring opening polymerization of ε-caprolactone (ε-CL) at room temperature. Residues of flax and milkweed (Asclepias syriaca) stem fibers were used as a source of cellulose to obtain and isolate CNCs. The cationic ring opening polymerization (CROP) of the monomer ε-CL was used to covalently graft polycaprolactone (PCL) chains at the CNCs surface. Silver hexafluoroantimonate (AgSbF6) was used in combination with the extracted CNCs to initiate, at room temperature, the polymerization and the grafting reactions with no other stimulus. Fourier-Transform InfraRed (FTIR), X-ray Photoelectron Spectrometry (XPS), UV/visible absorption and Gel Permeation Chromatography (GPC) analyses evidenced the presence of PCL chains covalently grafted at CNCs surface, the formation of Ag(0) particles as well as low or moderate molecular weight free PCL chains.

Anti-fouling ultrafiltration membrane prepared from polysulfone-graft-methyl acrylate copolymers by UV-induced grafting method

Membrane fouling is one of the most important challenges faced in membrane ultrafiltration operations. The copolymers of polysulfone-graft-methyl acrylate were synthesized by homogeneous photo-initiated graft copolymerization. The variables affecting the degree of grafting, such as the time of UV （Ultraviolet-visible） irradiation and the concentrations of the methyl acrylate and photoinitiator, were investigated. The graft copolymer membranes were prepared by the phase inversion method. The chemical and morphological changes were characterized by attenuated total reflection-Fourier transform infrared spectroscopy （ATR/FT-IR）, scanning electron microscopy, and water contact angles measurements. Results revealed that methyl acrylate groups were present on the membranes and the graft degree of methyl acrylate had remarkable effect on the performance of membranes. Pure water contact angle on the membrane surface decreases with the increase of methyl acrylate graft degree, which indicated that the hydrophilicity of graft copolymer membranes was improved. The permeation fluxes of pure water and bovine serum albumin solution were measured to evaluate the antifouling property of graft copolymer membranes, the results of which have shown an enhancement of antifouling property for graft copolymer membranes.

Plasma Induced Grafting of PMMA onto Titanium Dioxide Powder

Grafting of polymer of methyl methacrylate （PMMA） onto titanium dioxide powder is investigated in this paper. The graft polymerization reaction is induced by dielectric-barrier- discharge produced N2 plasma treatment of titanium dioxide surfaces. IR, XPS and TGA results show that PMMA is grafted onto the surfaces of titanium dioxide powder. And crystal structure of the titanium dioxide powder observed with XRD spectra is unchanged after plasma graft polymerization.

Plasma graft of poly(ethylene glycol) methyl ether methacrylate (PEGMA) on RGP lens surface for reducing protein adsorption

Poly（ethylene glycol） methyl ether methacrylate（PEGMA） was grafted on fluorosilicone acrylate rigid gas permissible contact lens surface by means of argon plasma induced polymerization to improve surface hydrophilicity and reduce protein adsorption.The surface properties were characterized by contact angle measurement,x-ray photoelectron spectroscopy（XPS） and atomic force microscopy respectively.The surface protein adsorption was evaluated by lysozyme solution immersion and XPS analysis.The results indicated that a thin layer of PEGMA was successfully grafted.The surface hydrophilicity was bettered and surface free energy increased.The lysozyme adsorption on the lens surface was reduced greatly.

LAMINATION OF POLYMER FILMS BY BULK SURFACE PHOTOGRAFTING PROCESS AND PROPERTIES

A new process for lamination of polymer films by 'bulk surface photografting' has been developed. The chemical component of the invention is that the curing of reactive solution between two substrates is initiated by the surface free radicals produced by aromatic ketones and surface-hydrogen of substrates. Using the new approach, two or more polymer films are bonded together by a grafted polymer network which is grafted to adjacent substrate surfaces. The technique has been applied to film substrates of different polymers such as polyolefins, polyesters, and polyamides which have abstractable hydrogens at the surface. The photolaminated film composites containing carrier films and an intermediate functional film of low permeability give strong laminates with high barrier properties, e.g, for oxygen and air.

GRAFTING OF PEROXIDE-INITIATED MALEIC ANHYDRIDE ON SPHERICAL PE/PPIN-REACTOR BLEND GRANULES

Spherical polyethylene/polypropylene (PE/PP) in-reactor blend granules with various ethylene/propylene molar ratios and high porosity were synthesized using a high yield TiCVMgCl2 supported catalyst. A solution of benzoyl peroxide (BPO)/maleic anhydride (MAH)/xylene (interfacial reagent) or BPO/MAH/St (comonomer) was absorbed onto the PE/PP in- reactor blend granules, and solid phase graft polymerization of MAH on PE/PP was conducted. The amount of grafted MAH on PE/PP was measured through chemical titration. The results showed that solid phase graft polymerization of MAH in PE/PP in-reactor blend granules produced graft copolymer with high amount of grafted MAH, and the amount of grafted MAH was raised slightly when St was introduced as comonomer. The graft in-reactor blend was fractionated into five fractions through temperature-gradient extraction fractionation (TGEF), and the fractions were analyzed by FTIR. The results revealed that MAH is mainly grafted on the PE segments, whereas MAH was predominantly grafted on the PP segments when St was present in the graft polymerization system. In addition, the final product is still in the form of regular spherical granules, which is beneficial for industrial processing.