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.

Removal of manganese from waste water by complexation-ultrafiltration using copolymer of maleic acid and acrylic acid

Copolymer of maleic acid and acrylic acid （PMA-100）, combining with polyvinyl butyral （PVB） ultrafiltration membrane was used for the removal of Mn（II） from waste water by complexation-ultrafiltration. The carboxylic group content of PMA-100 and the rate of complexation reaction were measured. Effects of the mass ratio of PMA-100 to Mn（II） （n）, pH, background electrolyte, etc on the rejection rate （R） and permeate flux （J） were investigated. The results show that carboxylic group content of PMA-100 is 9.5 mmol/g. The complexation of Mn（II） with PMA-100 is rapid and completed within 5 min at pH 6.0. Both R and J increase with pH increasing in the range of 2.5-7.0, and R increases with the increase of n at pH 6.0 while J is little affected. The background electrolyte leads to the decrease of R, and CaCl2 has much greater effect on R than NaCl at the same ionic strength.

PREPARATION AND SURFACE PROPERTIES OF ACRYLIC COPOLYMERS CONTAINING FLUORINATED MONOMERS

A series of copolymers comprising butylmethacrylate, styrene, butylacrylate, hydroxypropyl acrylate and perfluoroalkyl methacrylate were synthesized by the free radical polymerization using BPO as an initiator. The surface property of the copolymer films was subsequently characterized. The contact angle measurements and energy dispersive analysis of X-ray （EDAX） show that the length and content of perfluoroalkyl side chains in the copolymers are crucial for the preparation of the film with low surface energy. At a given content of fluorinated monomers in the copolymers, the longer the perfluoroalkyl side chain, the larger the water contact angle of the copolymer films will be. On the other hand, the higher the content of fluorinated monomers, the lower the surface energy is. The water contact angle increases with the increase of the fluorinated monomer content and reaches a plateau at 3 wt% of fluorinated monomer content.

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.

Effect of Structural Units on the Adhesion of Acrylic Copolymers to Fibers for Warp Sizing

Radical copolymerization of acrylic acid(AA)with acrylamide(AM)or acrylamide/acrylonitrile(AM/AN)was initiated with ammonium persulfate as initiator to produce acrylic copolymers such as bicopolymer poly(AM-co-AA)and tercopolymer poly(AM-co-AN-co-AA)for revealing the effects of the structural units of the copolymers on the adhesion of the copolymers to polyester or cotton fibers for warp sizing.The adhesion was evaluated in terms of tensile strength and work-to-break of a roving impregnated with the copolymer solution.It was found that the adhesion strongly depended on type and amount of the units incorporated into the copolymeric chains.Whether the fiber is cotton or polyester,the adhesion of the bicopolymer poly(AM-co-AA)is greater than that of polyacrylic acid or polyacyamide.Excessively increasing the amount of AM or AA unit in poly(AM-co-AA)lowers the adhesion.To enhance the adhesion of the bicopolymer,a favorable mole ratio of AM to AA is 70/30.Based on this mole ratio,incorporation of acrylonitrile units into poly(AM-co-AA)to form tercopolymer enhances the adhesion.

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.

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.

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.

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.

Effect of the Side Chain Structure on Hydrolysis Degradation of Zinc Acrylate Copolymers

In this report,zinc acrylate copolymers were synthesized by used different organic acid as the side chain structure.These copolymers were further characterized by GPC,DSC and Water absorption analysis respectively,and then the effects of the chain structure of organic acid on hydrolysis degradation and copper release rate were also discussed.In the meantime,the result shows that the biocide release rate could be controlled by used different chain structure of organic acid.

Investigation on Mechanical Properties of CMSLDS/Acrylate Copolymeric Blending Films for Warp Sizing

Carboxymethyl starch with lower degree of substitution was, blended with acrylate copolymer for revealing the relation between mechanical properties and chemical structure of blending film. Effects of carboxymethylation of starch, acrylate constituent units of acrylate copolymers, and copolymer content of the film on the properties were investigated. The mechanical properties were evaluated in terms of tensile strength, breaking elongation, abrasion resistance, and flex-fatigue resistance. Film morphology was examined with X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and atomic force microscope （AFM）. It was found that the properties depended on the degree of substitution of carboxymethyl starch, chemical structure of acrylate units, and content of acrylate copolymer. Phase-separation of the two ingredients occurred within film matrix and the separation was decreased after starch carboxymethylation. Breaking elongation and flex-fatigue resistance of the film reached maximmns when acrylate copolymer content was 50%. Excessively increasing the content of acrylate copolymer reduced the film properties.

An Approach to the Flame Retardancy of EVA Copolymer by Plasma Treatmentc2

An attempt was made in the paper aiming at imparting flame retardancy to polymers by plasma grafting technique Based on EVA copolymers with different VA contents the author tried to use the Ar plasma followed by grafting with/without subsequent saponification and metal ion exchange expediting the charring of polymers upon heationg Characterization of the flammability of the plasma treated EVA copolymers grafted with acrylic monomers(MAA,AA and AAm)indicates that this approach turns out to be a promising way and worthy doing whatever in research and/or applications

Synthesis and application of lignin-based copolymer LSAA on controlling non-point source pollution resulted from surface runoff

In this article,alkali lignin separated from paper pulp waste was grafted into a novel copolymer LSAA (a copolymer of lignin,starch, acrylamide,and acrylic acid).Its practical application effect and environmental safety were studied.The results of field simulation experiment indicated that the application of LSAA significantly affected the output of the runoff and pollutants.The runoff quantity was decreased by 16.67%-47.00%and the loads of total suspended solids (TSS),chemical oxygen demand (COD),total nit...

Comparison of selective flocculation of low grade goethitic iron ore fines using natural and synthetic polymers and a graft copolymer

This study aims to beneficiate low grade goethitic iron ore fines using a selective flocculation process. Selective flocculation studies were conducted using different polymers such as starch amylopectin(AP), poly acrylic acid(PAA), and a graft copolymer(AP-g-PAA). The obtained results were analyzed; they indicate the enhancement of the iron ore grade from 58.49% to 67.52% using AP-g-PAA with a recovery of 95.08%. In addition, 64.45% Fe with a recovery of 88.79% was obtained using AP. Similarly, using PAA, the grade increased to 63.46% Fe with a recovery of 82.10%. The findings are also supported by characterizing concentrates using X-ray diffraction(XRD) and electron probe microanalysis(EPMA) techniques.

NANOSTRUCTURES OF FUNCTIONAL BLOCK COPOLYMERS

Nanostructure fabrication from block copolymers in my group normally involves polymer design, synthesis, self-assembly, selective domain crosslinking, and sometimes selective domain removal. Preparation of thin films withnanochannels was used to illustrate the strategy we took. In this particular case, a linear triblock copolymer polyisoprenc-block-poly(2-cinnamoylethyl methacrylate)-block-poly(t-butyl acrylate), PI-b-PCEMA-b-PtBA, was used. Films, 25 to50 μm thick, were prepared from casting on glass slides a toluene solution of PI-b-PCEMA-b-PtBA and PtBA homopolymer,hPtBA, where hPtBA is shorter than the PtBA block. At the hPtBA mass faction of 20% relative to the triblock or the totalPtBA (hPtBA and PtBA block) volume fraction of 0.44, hPtBA and PtBA formed a seemingly continuous phase in the matrixof PCEMA and Pl. Such a block segregation pattern was locked in by photocrosslinking the PCEMA domain. Nanochannelswere formed by extracting out hPtBA with solvent. Alternatively. larger channels were obtained from extracting out hPtBAand hydrolyzing the t-butyl groups of the PtBA block. Such membranes were not liquid permeable but had gas permeabilityconstants ～6 orders of magnitude higher than that of low-density polyethylene films.

Solvent-Induced Phase-Inversion and Electrical Actuation of Dielectric Copolymer Films

Block copolymers posses inherently the ability of form a variety of phase-separated microdomain structures. The lengths of block segments and the selectivity of the solvent are primary factors affecting the resultant morphology. This paper investigated the effect of casting solvents on the morphologies and electrical actuation of poly(methyl methacrylate)-poly(n-butyl acrylate)-poly(methyl methacrylate) (PMMA-PnBA-PMMA) triblock copolymer films comprising PMMA hard segment and PnBA soft segment. Transmission electron microscopy and confocal laser scanning microscopy observation revealed that PMMA and PnBA segments were assembled into various micro- and nano-sized phase structures where either of them formed continuous phase. This implies that continous phase could be inversed by used casting solvents. Solvent-dependent phase morphologies had a significant effect on the electrical actuation results. Increase of the PnBA contents and the continuous phases of PnBA soft segments improved both of electrical actuation and dielectric constant, indicating that solvent-induced phase separation modulates the electrical actuation of dielectric films. The significance of the role of solvent selectivity and the major continuous phase of the polymer in defining the morphology and electrical actuation of the self-assembled block copolymer structure are discussed.

3D打印工艺参数对PLA/PTW共混物力学性能影响的研究

采用3D打印中的熔融沉积成型(FDM)工艺制备了聚乳酸/乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯共聚物(PLA/PTW),通过单因素实验探究了3D打印工艺参数(喷头温度、打印平台温度和打印速度)对PLA/PTW共混物力学性能的影响,并在此基础上设计了三因素三水平正交实验,优化了3D打印的工艺参数。结果表明,共混物的冲击强度和拉伸强度均随喷头温度的增加呈现先上升后下降、均随打印平台温度的增加而增加、均随打印速度的增加出现下降的趋势。各工艺参数对PLA/PTW共混物综合力学性能的影响从大到小依次为:喷头温度、打印速度、打印平台温度,且当喷头温度为210℃、打印平台温度为80℃以及打印速度为40 mm/s时,打印出的PLA/PTW共混物的综合力学性能最佳。

中高压半导电屏蔽电缆料的性能研究

采用热重分析仪、差示扫描量热仪、核磁共振波谱仪、傅里叶变换红外光谱仪、电线电缆半导电橡塑电阻测试仪和熔体流动速率仪等对中高压半导电屏蔽电缆料的基础树脂组成、聚合物分子链结构和电性能等进行剖析。结果表明:进口料和国产料虽然含有大量的炭黑填料,仍具有良好的加工流动性,且在23,90℃下的体积电阻率均较低。

加工型ACR的合成及在PVC中的应用

针对聚氯乙烯(PVC)/CaCO_(3)在混炼过程中存在的塑化困难、共混时间较长、不完全塑化等加工难点以及制品表面粗糙、无光泽等市场痛点,以叔十二烷基硫醇(TDDM)为链转移剂,设计并合成了一种加工型丙烯酸酯类共聚物(ACR-P)。探究了TDDM和ACR-P的添加量对PVC/CaCO_(3)/ACR-P复合材料力学性能、流变性能、微观形貌及塑化效果的影响。结果表明,随着TDDM添加量的增加,ACR-P特性黏度逐渐下降,PVC/CaCO_(3)/ACR-P复合材料的拉伸强度和储能模量明显提高,塑化时间大幅缩短,同时冲击强度略有增加。当TDDM添加质量分数为0.8%时,PVC/CaCO_(3)/ACR-P复合材料的拉伸强度达到52.79 MPa,与PVC/CaCO_(3)相比,提高了50.27%;塑化时间由71 s缩至32 s。ACR-P添加量的增加显著地影响了PVC/CaCO_(3)/ACR-P复合材料的力学性能和加工性能,当ACR-P添加量为10份时,复合材料的拉伸强度达到61.12 MPa,与PVC/CaCO_(3)相比,提高了87.6%;塑化时间由115 s缩至25 s。动态热机械分析测试显示PVC/ACR-P复合材料只有一个玻璃化转变峰,说明PVC树脂和ACR-P两相是一个相容体系。从扫描电子显微镜可以观察到PVC/CaCO_(3)复合材料中两相界面清晰,ACR-P的引入使复合材料的界面变得模糊,这表明复合材料的相容性得到改善,力学性能和加工性能得到提升。

碘转移本体聚合制备PS-b-PBA-b-PS共聚物:聚合动力学、结构和性能

以碘仿为链转移剂、偶氮类化合物为引发剂,通过碘转移本体聚合合成碘封端聚丙烯酸丁酯(I-PBA-I),并以其调节苯乙烯扩链聚合,制得聚苯乙烯-b-聚丙烯酸丁酯-b-聚苯乙烯(PS-b-PBA-b-PS)共聚物,研究了聚合动力学、共聚物结构和性能。发现丙烯酸丁酯均聚和苯乙烯扩链聚合均符合活性自由基聚合特征,反应初始BA与CHI3物质的量比n_(BA,0)/n_(CHI3,0)从100/1增至1 000/1时,I-PBA-I数均分子量由15 000增大到134 500;以数均分子量为28 400的I-PBA-I为大分子链转移剂,反应初始BA与St物质的量比n_(BA,0)/n_(St,0)为1/1、1/2、1/3和1/4时扩链得到数均分子量分别为46 000、69 000、97 500、127 000的PS-b-PBA-b-PS共聚物;嵌段共聚物微相分离,在增韧的同时保持一定的透光率,PS与PBA物质的量比n_(PS)/n_(PBA)为3.85/1的嵌段共聚物抗冲强度与商品化阴离子活性聚合苯乙烯-丁二烯嵌段共聚树脂相当。