Modification of Natural Rubber Latex by Graft Copolymerization of 2-Ethylhexyl Acrylate and Methacrylic Acid

Natural rubber(NR)grafted with 2-ethylhexyl acrylate(2-EHA)and methacrylic acid(MAA,collectively NR-g-PEHA/MAA)was synthesized by emulsion polymerization.Tetraethylenepentamine and cumene hydroperoxide were used as redox initiators.The successful grafting of 2-EHA and MAA onto NR was confirmed by Fourier transform infrared spectroscopy.The morphology of the NR latex particles was observed by transmission electron microscopy.The effects of reaction temperature,initiator dosage,feeding mode,and hard monomer content on the mechanical properties of the modified NR film were investigated.Grafted polymer chains were unevenly wrapped on the outside of NR particles,and smaller particles were more easily grafted.Crosslinking was characterized using a toluene swelling method.Thermal stability and glass transition temperature were examined by differential scanning calorimetry and thermogravimetric analysis.The results showed that the thermal stability of NR-g-PEHA/MAA had been improved,and the glass transition temperature(Tg)was unchanged.

Research on the Marine Antifouling Ability and Mechanism of Acrylate Copolymers and Marine Coatings Based on a Synergistic Effect

Marine biofouling is an urgent global problem in the process of ocean exploitation and utilization.In our work,a series of zinc-based acrylate copolymers(ACZn-x)were designed and synthesized using benzoic acid,zinc oxide(ZnO)and a random quaternion copolymer consisting of ethyl acrylate(EA),butyl acrylate(BA),acrylic acid(AA)and methacrylic acid(MAA)by free radical polymerization and dehydration condensation.The ACZn-x with a zinc benzoate side chain is able to hydrolyze in natural seawater under static conditions,resulting in the formation of a smooth surface.We investigated and confirmed the antifouling(AF)behavior of ACZn-x in the laboratory and revealed that they have better antibacterial(86%for S.aureus and 72%for E.coli)and anti-algal(≥60.1%for N.closterium and≥67.5%for P.subcordiformis)activities.We also assessed the marine AF properties of ACZn-x and corresponding coatings in Qingdao,China;the ACZn-x exhibited ideal AF properties with little silt and biological mucosa adhered to the ACZn-x surface after 6 months,and corresponding coatings exhibited little biofouling after 16 months in the ocean.Importantly,possible AF mechanisms were further proposed at the cellular level.These results could be helpful for the development and application of effective AF coatings.

Studies on Graft Copolymerization of Acrylic Acid onto Ramie Fibers with Chromic Acid Initiation System

The graft copolymerization of acrylic acid (AA) with unswollen and swollen ramie fibers using chromic acid (H 2CrO 4) as the initiator has been studied in the presence of air. The effects of initiator concentration, monomer concentration, perchloric acid (HClO 4) concentration, time of polymerization, reaction temperature, and amount of ramie fibers on the graft percentage have been found out. The graft copolymer was characterized by IR spectra, scanning electron microscopy(SEM), differential thermal analysis (DTA), and thermogravimertric analysis (TGA).

Graft Copolymerization of Ethyl Acrylate onto Hydroxypropyl Methylcellulose Using Potassium Persulfate as Initiator

With potassium persulfate (KPS) as initiator, graft copolymerization of ethyl acrylate (EA) onto water-soluble hydroxypropyl methylcellulose (HPMC) was investigated in aqueous medium. Effects of monomer concentration, initiator concentration, matrix concentration, and reaction temperature on the percentage of grafting (G) and grafting efficiency (G_E) were studied. The results show that G and G_E values both increase with the the increase of EA concentration and KPS concentration; when raising HPMC concentration from 0.12 mmol/L to 0.47 mmol/L, G decreases, while G_E increases;and when raising reaction temperature from 50 ℃ to 65 ℃,G increases, but G_E decreases. In addition, the graft copolymers were characterized by Fourier transform infrared (FTIR) spectra and transmission electron microscopy (TEM) methods.

EFFECT OF TEMPERATURE ON COPOLYMERIZATION PARAMETERS OF HYDROXYETHYL ACRYLATE AND METHYL METHACRYLATE

The copolymerization of 2-hydroxyethyl acrylate (HEA, M//1) and methyl methacrylate (MMA, M//2) in cyclohexanone was studied. The multiple experiments of solution copolymerization with low conversion were carried out at two sensitive composition feed points at 60, 80, 100, 120 and 140 degree C, respectively. The composition of the copolymers was analyzed by **1H-NMR. The reactivity ratios which were estimated by the Error-in-Variable Method (EVM) of Mayo-Lewis equation were found to be r//1 equals 0.328, r//2 equals 1.781 for 60 degree C; 0.375, 1.709 for 80 degree C; 0.406, 1.654 for 100 degree C; 0.439, 1.540 for 120 degree C and 0.455, 1.400 for 140 degree C, and the 95% joint confidence intervals of the reactivity ratios were also determined. According to r//1 and r//2, Arrhenius relations and the activity energy difference between the homo- and cross-propagation were calculated. (Author abstract) 12 Refs.

EFFECTS OF ω-ACRYLOYL POLY (ETHYLENE OXIDE) MACROMONOMER ON EMULSIFIER-FREE EMULSI0N COPOLYMERIZATION OF METHYL METHACRYLATE AND n-BUTYL ACRYLATE

Well-defined nonionic hydrophilic ω-acryloyl poly(ethylene oxide) macro-monomer (PEO-A) has been prepared by living anionic polymerization of ethylene oxidewith diphenyl methyl potassium as the initiator and acryloyl chloride as the reaction termi-nating agent. The polymer was characterized by FTIR and SEC. The emulsifier-free emul-sion polymerization of methyl methacrylate (MMA) and n-butyl acrylate (BA) containingvarious concentrations of PEO-A was studied. In all cases stable emulsion coplymerizationsof MMA and BA were obtained. The stabilizing effect was found to be dependent on themolecular weight and the feed amount of the macromonomer.

Studies on the Graft Copolymerization of Methyl Acrylate and Ethyl Acrylate onto Corn Starch Using Potassium Persulfate-Sodium Thiosulphatc as Initiation System

Grafting copolymerizations of methyl acrylate(MA) and ethyl acrylate(EA) onto corn starch, respectively, initiated by potassium persulfate-sodium thiosulphate (KPS-STS) redox system, were studied. The structures of poly(MA)-g-starch and poly(EA)-g-starch were characterized by IR, SEM and X-ray diffraction. Experimental results show that KPS-STS is an efficient initiation system for grafting of MA and EA onto corn starch. The maximum percent grafting was obtained at [KPS] of 6.0× 10~3 mol/L, [STS] of 1.8× 10 5 mol/L, [M] of 6. 0× 101 mol/L, S:L=4:100 at 40℃ for 6 h. The reactivity order is MA>EA.

Preparation of superabsorbent by graft copolymerization of acrylic acid onto corn starch using K_2S_2O_8 and rare earths as initiators

K2S2O8 and rare earths(RE)were used as initiators to prepare superabsorbents by graft copolymerization of acrylic acid(AA)onto corn starch.The effects of monomer concentration,initiator K2S2O8 concentration,cross-linker concentration,reaction temperature and the concentration ratio of RE and K2S2O8 on the graft copolymerization were studied in terms of the water absorption capacity of superabsorbents.Results indicate that the optimum conditions obtained for the grafting of AA onto 5g starch are as follows:AA of 75.773 g/L,K2S2O8 of 0.437 g/L,RE of 0.874 g/L,cross-linker of 0.381 g/L and temperature of 70 ℃.The maximum water absorption capacity obtained is 740 g/g.The new method of graft polymerization is easily proceeded and controlled.The graft copolymers were characterized by infra-red spectroscopy,scanning electron microscopy and TG.Results characterized by IR and SEM give strong evidence for grafting of AA onto corn starch,and those characterized by TG reveal that the grafting of AA improves the thermostability of corn starch.

PHOTO-INDUCED DOPED POLYANILINE BY THE VINYLIDENE CHLORIDE AND METHYL ACRYLATE COPOLYMER AS PHOTO ACID GENERATOR

The emeraldine base form of polyaniline (PANI) can be doped by a photo-induced doping method. In this method a. copolymer of vinylidene chloride and methyl acrylate (VCMAC) was used as photo acid generator which can release proton when it is exposed to ultraviolet light (lambda = 254 nm). The structure of PANI-VCMAC system before and after irradiation was characterized by elemental analysis, IR, XTP, anti SEM images. Results obtained indicate that the photo-induced doping characteristics, such as doping position and type of charge carriers, are similar to that of PANI doped with HCl. The poor room-temperature conductivity (similar to 10-S-5/cm) of PANI-VCMAC system after irradiation may be due to low doping degree (similar to pH=3) and the difference in morphology as compared with PANI-HCl film.

ESTIMATION OF REACTIVITY RATIOS OF METHYL ACRYLATE WITH N-ARYLMETHACRYL-AMIDE COPOLYMERS BY ~1H NMR METHOD

The copolymerizations of methyl acrylate （MA） with different N- arylmethacrylamide （N-ArMA） were carried out in benzene solution by free radical initiation. The compositions of the copolymers were deter mined by;H NMR method. The monomer reactivity ratios were calculated by the Fineman-Ross （F-R） method. The reactivity ratios and the activity of various N-ArMA with MA were investigated.

BARRIER PROPERTY AND STRUCTURE OF ACRYLONITRILE/ACRYLIC COPOLYMERS

A series of acrylonitrile (AN) copolymers with methyl acrylate (MA) or ethyl acrylate (EA) as comonomer (5-23 wt%) was prepared by free-radical copolymerisation. The permeability coefficients of the copolymers to oxygen and carbon dioxide were measured at 1.0 MPa and at 30 degrees C, and those to water vapor also measured at 100% relative humidity and at 30 degrees C. All the AN/acrylic copolymers are semicrystalline. As the acrylate content increase, the permeability coefficients of the copolymers to oxygen and carbon dioxide are increased progressively, but those to water vapor are decreased progressively. The gas permeability coefficients of the polymers were correlated with free-volume fractions or the ratio of free volume to cohesive energy.

PREPARATION AND MECHANICAL PROPERTIES OF POLY(METHYL METHACRYLATE)/ URETHANE ACRYLATE COPOLYMERS

The urethane acrylate(UA) was made of poly(tetramethylenc oxide), 4,4’-diphenylmethane diisocyanate, and 2-hydroxyethyl methacrylate. A series of poly(methyl methacrylate) / urethane acrylate copolymers was prepared by using a redox initiating system. The copolymers had cross linked structures and two-phase morphologies as indicated by the results of the dynamic mechanical measurement and swelling test.

BARRIER PROPERTIES OF VINYLIDENE CHLORIDE/METHYL ACRYLATE COPOLYMER

A series of vinylidene dichloride (VDC) copolymers with methyl acrylate (MA) as comonomer (3-12wt%), was prepared by free-radical suspension copolymerization. The permeability coefficients of the copolymers to oxygen and carbon dioxide were measured at 1.0 MPa and at 30 degrees C, and those to water vapor were measured at 30 degrees C and 100% relative humidity. All the VDC/MA copolymers studied are semicrystalline. As the MA content increases, the permeability coefficients of the copolymers to oxygen, carbon dioxide, and water vapor are progressively increased, caused by decrease in crystalline fraction and increase in free volume of VDC/MA copolymers.

SYNTHESES OF A NOVEL POLYFLUOROALKYL SUBSTITUTED 2-HYDROXYETHYL ACRYLATE AND ITS COPOLYMERS

Polyfluoroalkyl substituted 2-hydroxyethyl acrylate 6 was synthesized in six steps usingglycerol as a starting material. A preliminary investigation has been taken on the synthesisand characterization of copolymers of 6 and 2-hydroxyethyl methacrylate.

STUDY ON THE STARCH GRAFTED ACRYLATE MONOMERS AND ITS COMPATIBILITY FOR THE BLEND SYSTEM OF STARCH AND POLYETHYLENE

研究采用高温和剪切力的作用直接引发淀粉与丙烯酸酯单体的接枝共聚合反应．讨论了各种反应条件对接枝反应的影响，并进一步研究了接枝物在淀粉聚乙烯共混体系中的增容作用．实验结果表明，高温和剪切作用力可以引发淀粉与丙烯酸酯单体的接枝共聚合反应。接枝物作为增容剂，对淀粉聚乙烯共混体系的力学性能和流变学性能均有所改善．

Study on PVC Grafted with Acrylic Rare Earths

The copolymers were formed by the graft copolymerization of PVC with acrylic rare earth. The principle and method of the graft copolymerization of PVC and acrylic rare earth were discussed. The graft copolymers were characterized by FT-IR spectra and scanning electron microscope (SEM).The thermal stability of the graft-copolymers was studied by thermogravimetric analysis (TG). The experiment results show that the thermal resistance and toughness of the graft copolymers are obviously enhanced.

Reactivity Ratios of Diethyldiallylammonium Chloride with Acrylamide or Acrylic Acid

The compositions of copolymers of diethyldiallylammonium chloride （DEDAAC） with acrylamide （AM）, acrylic acid （AA） or sodium acrylic acid （NaAA） at low conversion were determined by elemental analysis, and the reactivity ratios of monomers in copolymerization were obtained by Kelen-Tudos method. The results showed that the reactivity ratios rDE and rAM are 0.31 and 5.27 for DEDAAC with AM, rDE and rAA are 0.28 and 5.15 for DEDAAC with AA, and roe and rNsAA are 0.40 and 3.97 for DEDAAC with NaAA, respectively. The copolymerizations for DEDAAC with AM, AA or NaAA are non-ideal copolymerization and the products are random copolymers.

Radiation Induced Grafting of Acrylic Acid onto Viscose Rayon Fabrics and Its After-Effects

Radiation induced grafting of various polymers with different monomers proved to be an attractive means to modify the physical or chemical properties of polymeric materials or textile fabrics. In the present work, radiation induced grafting of viscose rayon fabrics, consisting mainly of cellulose fibers, with acrylic acid monomer has been carried out. The grafting yields have been thoroughly studied as a function of different applied experimental parameters. The impact of the graft yield on the physical properties of the fabrics such as tensile strength, elongation, swelling, moisture absorption, crease recovery angle and also the dyeing properties of the fabrics has been studied. The effect of increasing the contact time of the fabric and monomer solution, at room temperature, after stopping irradiation has been studied in detail as well as the effect of temperature on the irradiated samples also after stopping irradiation. The best grafting yield was obtained on irradiating viscose rayon fabric in methanol-water solvent containing acrylic acid monomer, at a dose 20 kGys, then heating for 7 hours at 80℃ and finally keeping the samples at room temperature for about 20 hours. That treatment significantly increased the final graft yield.

Radiation Induced Grafting of Viscose Rayon Fabrics with Some Acrylic Acid Derivatives and Styrene

Radiation induced grafting of viscose rayon fabrics, consisting mainly of cellulose fibers, with some acrylic acid derivatives, namely methyl acrylate, acrylamide and acrylonitrile, and also styrene, has been studied. The resultant graft yields have been determined as a function of the applied different experimental parameters. The impact of the graft yields on the physicochemical properties of viscose rayon fabrics such as swelling, moisture absorption, tensile strength, elongation at break, crease recovery angle and also dyeing ability of the grafted fabrics, has been also studied.

Synthesis and Properties of Poly (n-Octyl Acrylate) with Uniform Polystyrene Grafts

Poly （n-octyl acrylate） with uniform polystyrene grafts （POA-g-PS） was obtained by radical copolymerization of n-octyl acrylate （OA） with PS macromer, in solution. The reactivity ratio and effects of copolymerization conditions on grafting efficiency were studied. The crude products were purified by extraction with cyclohexane and n-butanol successively. POA-g-PS exhibited a very good compatibilizing effect on the acrylic rubber/polystyrene blends. 2﹪-3﹪ of the graft copolymer was enough for enhancing the tensile strength of the blends. DSC and SEM demonstrated the enhancement of compatibility in the presence of the graft copolymer.