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.

One step graft copolymerization of acrylic acid and sodium styrene sulfonate onto high-density polyethylene film by preirradiation method

High-density polyethylene (HDPE) films were irradiated by 60Co gamma ray with a dose of 100 kGy in air and then immersed in aqueous solution of acrylic acid (AA) and sodium styrene sulfonate (SSS) at different temperature. The effects of grafting conditions such as temperature, reaction time, Mohr’s salt concentration, and total concentration of monomer on grafting yield were studied. Both grafting yield of AA and SSS onto HDPE respectively increases with total concentration of monomers. The highest grafting yield was observed at 3 mol/L monomers where the grafted PE swelled to the largest extent in the monomers mixture. The grafting yield increases with reaction time and then levels off. At higher temperature, the grafting yield decreases with Mohr’s salt concentration, but increases at low temperature when Mohr’s salt concentration is 0.083%. Which can be interpreted that in the presence of Fe2+ diperoxides and hydroperoxides may decompose at low temperature to form radical which can initiate the grafting. The physical and chemical properties of grafting films were also investigated.

Grafting Copolymerization of Styrene and Acrylic Acid onto Pre-irradiated Polypropylene Fabric

Grafting copolymerization of styrene and acrylic acid onto polypropylene fabric had been studied by using a pre-irradiation technique. The polypropylene fabric Samples were irradiated by Y-ray and electron beam under the conditions of air and nitrogen gas, respectively. The effect of absorbed dose, monomer concentration in solvent, reaction temperature and reaction time on the degree of grafting were determined. The effects of metallic salts and sulphuric acid on the grafting yield of acrylic acid were also examined. The samples irradiated by electron beam give a much higher degree of grafting than those by Y -ray when styrene was grafted to polypropylene fabric. However, the grafting yield of acrylic acid on polypropylene fabric in the presence of metallic salts and sultric acid showed the opposite results from the case of styrene. This effect is reasonably interpreted by assuming that the grafting is dominated by trapped radicals and peroxides in pre-irradiated polypropylene.

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.

Swelling Properties of New Hydrogels Based on the Dimethyl Amino Ethyl Acrylate Methyl Chloride Quaternary Salt with Acrylic Acid and 2-Methylene Butane-1,4-Dioic Acid Monomers in Aqueous Solutions

Hydrogels of dimethylaminoethyl acrylate methyl chloride quaternary salt (Q9) have been synthesized with different monomer ratio by copolymerization of this poorly studied monomer either with acrylic acid or with 2-methylene bu-tane-1,4-dioic acid. Hydrogel swelling was measured as a function of the composition of the hydrogel and of the crosslinking agent ratio. High values of swelling have been obtained at very high crosslinking values (【14 wt %) and the equilibrium swelling was reached at very low time (less than 15 minutes). The swelling isotherms consisted of a steep initial portion and then levelled off as asymptotically to the equilibrium swelling limit. The experimental data suggest clearly that the swelling process obeys second-order kinetics. According to this, the kinetics rate constant and the equilibrium water content were determined at different comonomer composition and crosslinker concentration. The calculated kinetic constants ranged from 0.48 to 3.76 ×10-2 min-1 for poly (acrylic acid-co-Q9) hydrogels and from 0.68 to 4.0 ×10-2 min-1 for poly (2-methylene butane-1,4-dioic acid-co-Q9) hydrogels depending on the hydrogels composition. The diffusion process was evaluated for each hydrogel showing a non-Fickian type diffusion. In all cases was observed a considerable increase in diffusion coefficient as Q9 content increases.

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).

NATURAL PRODUCTIVITY OF ACRYLIC ACID AND DIMETHYL SULPHIDE DURING A SUMMER BLOOM OF PHAEOCYSTIS POUCHETII IN ANTARCTIC COASTAL WATER

Water samples were collected over P. ponchetii bloom period beginning in November 1988, in 15m water column, from 10km offshore of Davis Station, Vestfold Hill, Antarctica. The concentrations of acrylic acid and dimethyl sulphide (DMS), which are toxic compounds in the water samples, were determined by HPLC and GC. The result shows that the concentration of acrylic acid varies in 0. 001 - 0. 510μmol ?L-1 and the concentration of DMS in 0. 003-0. 588 μmol ?L-1 during P. pouchetii bloom. Both the increased since late December 1988 and reached the highest concentration in early January 1989, then they decreased rapidly and returned to lower level from middle January to February in agreement with variation in cell number of the unicell alga P. pouchetii. The correlation coefficients between acrylic acid and P. pouchetii and between DMS and P. pouchetii are all 0. 998. It is undoubted that P. pouchetii produced acrylic acid and DMS. The highest productivity of acrylic acid and DMS were 9. 76X 10-8 umol cell-1 and 13. 09 ×10-8 μmol ?cell-1, respectively, during P. pouchelii bloom. A cellular product, dimethylsulphonium propionate (DMSP), is decomposed into acrylic acid and DMS, and the formation of DMSP is probably from methionine which could be utilized by P. pouchelii.

Oxidation of propane to acrylic acid and acetic acid over alkaline earth-doped Mo-V-Sb-O_x catalysts

Alkaline earth metal （Mg,Ca,Sr and Ba）-doped Mo-V-Sb-O x catalysts,prepared by a dry-up method,have been investigated for their catalytic performance in the oxidation of propane under different reaction conditions.The catalysts have been characterized by N2 adsorption-desorption,temperature-programmed desorption （TPD） of NH3,SEM and XRD.Influence of water vapor on the catalytic performance,particularly on the selectivities to acetic acid and acrylic acid,has also been studied.The selectivity to acrylic acid was improved significantly by the doping of alkaline earth metals to Mo-V-Sb-O x catalysts.The surface acidic sites of the catalyst decreased with the doping of the catalyst with alkaline earth metals,which ultimately was found to be beneficial for obtaining high selectivity to acrylic acid.The catalytic activity and product selectivities were found to be influenced by the reaction temperature,C3H8/O2 ratio and space velocity.A significant improvement in the selectivity to acrylic acid has also been observed by the addition of water vapor in the feed of propane and oxygen in the oxidation of propane.

CONFORMATIONAL CHARACTERISTICS OF POLY(ACRYLIC ACID) AND POLY(METHACRYLIC ACID)

A full-relaxation optimization of molecule and the Dreiding force field are employed to obtain the geometry parameters and the conformational energy surfaces of meso or racemic dyad of poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA). Three different carbonyl-bond orientations of side-groups resulted in the differences in depth of potential wells in their energetic contours for a meso or a racemic dyad. These discrepancies are interpreted as a result of various fine structures corresponding to grid search conformations as well as thereby different interactions. The analysis on the most stable conformations of PMAA confirmed that the ester groups are nearly perpendicular to the plane defined by the two adjacent skeletal bonds but may possibly change their relative orientations to meet the requirement of lower energy during the conformational state transition. For each polymer, two global energy maps of a meso and a racemic dyad were finally constructed from the superposition of energy data for the three kinds of side-group orientations by the Boltzmann factors. From an ensemble average, the proposed scheme with three rotational isomeric states (RIS) allowed us to access the experimentally unperturbed dimensions of PAA chain via the configurational statistical mechanics. Although the calculation was based on the short-range, local interactions, it was interested to note that the experimental characteristic ratios just fell within the range calculated for atactic chains.

Syntheses and Crystal Structures of Two Complexes with 3-(3-Pyridyl)acrylic Acid

The reaction of 3-（3-pyridyl）acrylic acid （H（3-PYA）） with Co（NO3）2.6H2O or MnCl2.4H2O yielded two new complexes： [Co（3-PYA）2（H2O）4.H2O] 1 and [Mn（3-PYA）2（H2O）4] 2. Complex 1 crystallizes in monoclinic, space group C2/c with a = 9.9473（12）, b = 13.7227（16）, c = 14.7376（18） A, β = 99.043（2）°, V = 1986.7（4） A^3, Z = 4, Dc= 1.549 g/cm^3,μ = 0.921 mm^-1, F（000） = 964, R = 0.0786 and wR = 0.1443. Six types of hydrogen bonds and π-π packing interactions connect the mononuclear units [Co（Ⅱ）（3-PYA）2（H2O）4·H2O] into a three-dimensional supramolecular architecture. Complex 2 crystallizes in monoclinic, space group P21/n with a = 11.3630（16）, b = 7.0346（10）, c = 12.1365（18） A, β = 112.545（3）°, V = 896.0（2） A^3, Z = 2, D, = 1.997 g/cm^3,μ = 0.785 mm^-1, F（000） = 438, R = 0.0787 and wR = 0.1550. The discrete entity Mn（Ⅱ）（3-PYD）2（H2O）4 is extended into a 3-D supramolecular architecture by four kinds of hydrogen bonds.

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.

Variations in surface and electrical properties of polytetrafluoroethylene film after plasma-induced grafting of acrylic acid

Polytetrafluoroethylene(PTFE) film was graftpolymerized with acrylic acid(AAc) via a low-temperature plasma technique.The effect of plasma treatment parameters(radio-frequency power and treatment time) on the spin number of free radicals in PTFE film was examined.Attenuated total reflection Fourier transform infrared(ATR-FTIR)spectroscopy,X-ray photoelectron spectroscopy,scanning electron microscopy,and atomic force microscopy were employed to characterize the chemical structure,surface composition,and microstructure of the original PTFE and PTFE-g-PAAc films,respectively,in order to verify the successful graft polymerization of AAc onto a PTFE film surface.Thermogravimetric analysis illustrated that the thermal stability of bulk PTFE film remains unchanged after graft modification.Water contact angle measurements confirmed that the hydrophilicity of PTFE-g-PAAc film was effectively improved as compared to the original PTFE film.The dielectric constant(ε_r) of PTFE-g-PAAc(GD =218 μg/cm^2) film remained invariable,compared to that of the unmodified PTFE film.Nevertheless,the dielectric loss(tanδ) of PTFE film increased considerably,from 0.0002(GD = 0μg/cm^2) to 0.0073(GD = 218 μg/cm^2),which might be due to the increase in surface polarity and moisture resulting from AAc graft modification.In addition,the surface electrical resistance(R_s) of PTFE film decreased slightly,from 131.89(GD = 0 μg/cm^2) to 110.28 Ω cm^2(GD = 218μg/cm^2) after surface modification,but still retained its inherent high impedance.

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.

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.

Flammability and Explosion Property of Gases in the One-Step Process of Propane Oxidation to Acrylic Acid

In order to study the flammability and explosion property of gases during the propane oxidation to acrylic acid process, the explosion limits and the safety oxygen content of gases at the recycle gas compressor outlet, the reactor inlet, and the reactor outlet were theoretically calculated and experimentally tested. Finally, the inert limit was also determined. It showed that gases at the recycle gas compressor outlet and the reactor outlet were nonflammable based on three indicators: the explosion limits, the safety oxygen content and the inert limit. The C3H6 and O2 contents were higher at the reactor inlet, which made the mixed gases easily ignitable. However, the large amount of inert gases suppressed the possibility of explosion effectively. As a consequence, no explosion phenomenon would happen in all three locations. But gases at the reactor inlet are most dangerous, where more supervision on the concentration of gases and more strict control on the temperature and pressure should be implemented. Besides this, open flame, hot surfaces and other sources of ignition are prohibited in working spaces. The experimental results can be applied to similar process for oxidation of propane.

Production of dimethylsulfide and acrylic acid from dimethylsulfoniopropionate during growth of three marine microalgae

We measured the concentrations of dimethylsulfide(DMS),acrylic acid(AA),and dimethylsulfoniopropionate(DMSP) during growth of three microalgae:Prorocentrum micans,Gephyrocapsa oceanica,and Platymonas subcordiformis.The DMSP,AA,and DMS concentrations in culture media varied significantly among algal growth stages,with the highest concentrations in the late stationary growth stage or the senescent stage.In the stationary growth stage,the average DMSP concentration per cell in P.micans(0.066 5 pmol/cell) was 1.3 times that in G.oceanica(0.049 5 pmol/cell) and 20.2 times that in P.subcordiformis(0.003 29 pmol/cell).The average concentrations of AA were0.044 6,0.026 9,and 0.003 05 pmol/cell in P.micans,G.oceanica,and P.subcordiformis,respectively,higher than the concentrations of DMS(0.272,0.497,and 0.086 2 fmol/cell,respectively).There were significant positive correlations between cell density and AA,DMSP,and DMS concentrations.The ratios of DMS/AA and AA/(DMSP+AA) in the three algae differed significantly over the growth cycle.In all three microalgae,the DMS/AA ratios were less than 25%during the growth period,suggesting that the enzymatic cleavage pathway,which generates DMS,was not the main DMSP degradation pathway.The changes in the DMS/AA ratio indicated that there was a higher rate of enzymatic breakdown of DMSP in the early growth period and a lower rate during senescence.In all three microalgae,the AA/(DMSP+AA) ratio(degradation ratio of DMSP) decreased during the exponential growth phase,and then increased.The variations in these ratios can approximately indicate the cleavage mechanism of DMSP at different stages of algal growth.