Heteropolyacids Catalysis in Synthesizing Butylacrylate

The catalytic activities of some heteropolyacids(HPAs) in synthesizing butyl acrylate are reported. It has been demonstrated that 12 tungstophosphoric acid is the most effective catalyst among more than 20 HPA(salts). Various factors concerned in this reaction have been investigated. The optimum conditions have been found, that is, the molar ratio of alcohol to acid is 1.2∶1.0 , the catalyst concentration 1%(mass fraction), the reaction time 2 h, the temperature 98—124 ℃ and a certain amount of polymerization inhibitor exists.

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.

Synthesis and evaluation of poly(N-vinyl caprolactam)-co-tert-butyl acrylate as kinetic hydrate inhibitor

Low dosage kinetic hydrate inhibitors(KHIs)are a kind of alternative chemical additives to high dosage thermodynamic inhibitors for preventing gas hydrate formation in oil&gas production wells and transportation pipelines.In this paper,a new KHI,poly(N-vinyl caprolactam)-co-tert-butyl acrylate(PVCapco-TBA),was successfully synthesized with N-vinyl caprolactam(NVCap)and tert-butyl acrylate.The kinetic inhibition performances of PVCap-co-TBA on the formations of both structureⅠmethane hydrate and structureⅡnatural gas hydrate were investigated by measuring the onset times of hydrate formation under different conditions and compared with commercial KHIs such as PVP,PVCap and inhibex 501.The results indicated that PVCap-co-TBA outperformed these widely applied inhibitors for both structureⅠand structureⅡhydrates.At the same dosage of KHI,the maximum tolerable degree of subcooling under which the onset time of hydrate formation exceeded 24 hours for structureⅠhydrate was much lower than that for structureⅡhydrate.The inhibition strength increased with the increasing dosage of PVCap-co-TBA;The maximum tolerable degree of subcooling for the natural gas hydrate is more than10 K when the dosage was higher than 0.5%(mass)while it achieved 12 K when that dosage rose to0.75%(mass).Additionally,we found polypropylene glycol could be used as synergist at the dosage of 1.0%(mass)or so,under which the kinetic inhibition performance of PVCap-co-TBA could be improved significantly.All evaluation results demonstrated that PVCap-co-TBA was a very promising KHI and a competitive alternative to the existing commercial KHIs.

Synthesis and Characterization of Styrene-Maleic Anhydride-Butyl Acrylate Terpolymer

A novel surface modifying agent and internal compatilizer of inorganic and macromolecule composite materials,P(St/MAH/BA)terpolymer,was synthesized in butanone by solution polymerization method using styrene(St),maleic anhydride(MAH),and butyl acrylate(BA)as monomers and azobisisobutyronitrile(AIBN)as an initiator.Some affecting factors on terpolymers yields such as polymerization time,reaction temperature,solvent volume,initiator content,and reactants ratios were studied.Furthermore,the structure and thermal properties of terpolymers were primarily characterized and determined by Fourier Transform Infrared Spectroscopy(FTIR),nuclear magnetic resonance(NMR),thermogravimetric analysis(TGA),and gel permeation chromatography(GPC).The results indicate that the terpolymers are random polymers and the yields are low,but the thermal decomposed temperature of terpolymers P(St/MAH/BA)is around 220 ℃ and the average molecular weights(Mw)achieve 1.189×105 g·mol-1.

Acrylate Copolymers as Impact Modifi er for Epoxy Resin

P（BA-GMA）（PBG）, having various molecular weights, was synthesized by in situ polymerization of butyl acrylate（BA） and glycidyl methacrylate（GMA）, and further used as a modifier to improve the comprehensive properties of the epoxy curing system. The copolymers were characterized by gel permeation chromatography（GPC）. The effects of various molecular weights of copolymers on the mechanical properties, thermal performance, and phase behavior of the curing system were carefully evaluated. The experimental results of differential scanning calorimetry（DSC） and dynamic mechanical analysis（DMA） showed that glass transition temperature decreased and the tan δ peak shifted to a lower temperature with decreasing molecular weight of copolymer. Mechanical properties analysis of curing films showed that the impact strength and fracture toughness increased significantly upon the addition of PBG, indicating good toughness of the modified epoxy resins. From scanning electron microscopy（SEM） studies of the fracture surfaces of ER/PBG systems, the fracture behavior of epoxy matrix was changed from brittleness to toughness.

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.

COMPUTER SIMULATIONS ON UNPERTURBED CONFIGURATIONAL DIMENSIONS OF POLY (METHYL ACRYLATE)

A full-relaxation optimization of molecule and the popular MM2 force field are employed to obtain the geometry parameters and the conformational energy surface of a meso or a racemic dyad of poly(methyl acrylate) (PMA) with a specified carbonyl-bond orientation in side-groups. It is found that the conformational energy maps calculated here considerably differ from those calculated with the rigid molecular model as reported in the earlier studies. The g(-) state cannot be omitted in the obtained contour maps. Two important conformers tg(-) and g(-t) with energy minima were newly detected for a racemic dyad. The analysis on the conformations with energy minima confirmed that the ester groups are not always perpendicular to the plane defined by the two adjacent skeletal bonds and may change their relative orientations to meet the requirement of lower energies during the conformational state transition. Instead of the early way of adjusting the interaction energy parameters to fit the experimental data, we attempt to predict unperturbed chain dimensions via the reliable force field and the configurational statistical mechanics. The proposed scheme with three rotational states identified from the contour maps allowed us to satisfactorily reproduce the experimental dimensions of random PMA chains.

Rapid Expansion of Supercritical Solution of Poly (1,1,2,2- Tetrahy-droperfluorodecyl Acrylate)

Poly(1,1,2,2- tetrahydroperfluorodecyl acrylate) (poly (TA-N)) was synthesized in laboratory. The resulting morphology of rapid expansion of supercritical solution (RESS) sprays of poly(TA - N) was investigated. At apre - expansion temperature of 45℃), amorphous polymer was formed. At temperature around 60 ℃ to 80 ℃ , fibers were formed. Increase of temperature increasesparticle size slightly. At temperature of 105℃ , most of particles are spheres. The RESS is an attractive process. To apply the polymers desired for coating applications in an organic solvent - free process that is economically viable , and it will have implications for pollution prevention during polymer film

STRUCTURE OF 1-BROMOMETHYL-7, 7-DIMETHYLBICYCLO[2.2.1]HEPT-2-YL ACRYLATE AND THE PROPERTIES OF ITS POLYMER

In this paper, the structure of 1-bromomethyl-7,7-dimethyl btcyclo[2.2.1]hept-2-yl acrylate has been studied by X-ray diffraction, and the relation between the molecular structure and the properties of polymerization and its polymer have been discussed.

Effects of Side-Chain on Conformational Characteristics of Poly(3,5-Dimethyl-Phenyl Acrylate) in Toluene at 40℃

The intrinsic viscosity [η] of poly(3,5-dimethylphenylacrylate) (35PDMPA)solutions were evaluated throughout the measurements of the flow times of toluene and polymer solutions by classical Huggins, and Kraemer’s methods using a Cannon-Ubbelohde semi-micro-dilution capillary viscometer in a Cannon thermostated water bath at 40℃ ± 0.02℃. The values of Huggins’ constant estimated ranged from 0.2 to 0.4 which were within expectations. The intrinsic viscosities and molecular weight relationship was established with the two-parameter classical models of Staudinger-Mark-Houwink-Sakurada and Stockmayer-Fixman. Conformational parameter C∞ and σ indicated 35PDMPA be semi flexible. Also, the rigidity of 35PDMPA was confirmed by Yamakawa-Fuji wormlike theory modified by Bohdanecky. The molecular parameters were estimated and compared. The results showed that 35PDMPA behaves like a semi-rigid polymer in toluene at 40℃ rather than a random coil flexible macromolecule.

Studies on interacting Blends of Acrylated Epoxy resin based Poly(Ester-Amide)s and Vinyl EsterResin

Epoxy resin based Unsaturated poly(ester-amide) resins (UPEAs) can be prepared by many methods but here these were prepared by reported method [1]. These UPEAs were then treated with acrylotl chloride to afford acrylated UPEAs resin (i.e. AUPEAs). Interacting blends of equal proportional AUPEAs and vinyl ester epoxy (VE) resin were prepared. APEAs and AUPEAs were characterized by elemental analysis, molecular weight determined by vapour pressure osmometer and by IR spectral study and by thermogravimetry. The curing of interacting blends was monitored on differential scanning calorimeter (DSC). Based on DSC data in situ glass reinforced composites of the resultant blends have been prepared and characterized for mechanical, electrical and chemical properties. Unreinforced blends were characterized by thermogravimetry (TGA).

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。

微纳层叠技术对ACM/PP热塑性弹性体性能的影响

采用微纳层叠共挤出技术制备了ACM/PP热塑性硫化胶(TPV),研究了动态硫化温度、橡塑比、相容剂含量、炭黑与增塑剂含量对TPV力学性能与耐油性能的影响。结果表明,当动态硫化温度为190℃时,TPV具有较好的力学性能,拉伸强度、断裂伸长率、硬度、压缩永久变形分别为12.83 MPa、104.67%、86.50%、50.00%;随着TPV橡塑比的增大,材料的拉伸强度、断裂伸长率、硬度、耐油性能明显降低;当相容剂PP-g-MAH(马来酸酐接枝聚丙烯)的含量为15份时,TPV的综合力学性能与耐油性能最佳;TPV的拉伸强度、压缩永久变形、硬度随炭黑含量的增加而升高,随增塑剂DOTP含量的增加而降低,TPV的耐油性随炭黑含量的增加而提高,随DOTP含量的增加而变差,TPV的断裂伸长率随炭黑与DOTP含量的增加而降低。

可自愈的聚丙烯酸盐复合材料的制备研究

本研究制备了纳米氯化镁、纳米氯化钙以及纳米颗粒/聚丙烯酸盐复合材料。实验结果表明,制备的纳米颗粒/聚丙烯酸盐复合材料在经历机械损伤或化学损伤后具有良好的自愈修复性能,机械性能和化学性能均可恢复到损伤前的水平。

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。

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.

水性抗氧剂组成以及含量对ASA树脂性能的影响

采用乳液聚合法制备了核壳比为6/4的ASA核壳接枝共聚物胶乳,系统地研究了水性抗氧剂的组成以及含量对ASA接枝共聚物热氧老化性能的影响,并采用熔融共混法制备ASA树脂,探究了水性抗氧剂的组成以及含量对ASA树脂力学性能、表观性能的影响。结果表明,水性抗氧剂的组成CPL/DLTP为2/3时,其ASA接枝共聚物的热氧老化性能最优;随着水性抗氧剂含量的增加,ASA接枝共聚物的氧化诱导期显著增长;水性抗氧剂的加入量超过1%以后,ASA接枝共聚物的氧化诱导期增长不显著;在230℃空气条件下,添加1%水性抗氧剂的ASA接枝共聚物的氧化诱导期可达73.1 min,其抗热氧老化能力是相同条件下不添加水性抗氧剂ASA接枝共聚物的80倍以上;水性抗氧剂的组成及含量对ASA树脂的力学性能无明显影响,对其表观性能如白度影响明显。

非缠结苯乙烯-对叔丁基苯乙烯共聚物的非线性拉伸流变行为

聚焦于苯乙烯和对叔丁基苯乙烯的非缠结聚合物以及其共聚物样品的线性和非线性拉伸流变学性质。所有样品均具有相似的链均库恩链段数(约为30个),表现出相似且符合Rouse模型预测的线性黏弹行为。在单轴拉伸实验中,样品在快速拉伸过程,即韦森堡数大于1的过程中拉伸黏度呈现出随拉伸速率增加先“增稠”后“变稀”的行为,在样品具有相似的最大拉伸比λ_(max)=√n_(K)(≈6)前提下,二者转变的特征韦森堡数随着叔丁基苯乙烯含量的增加而增加。该结果表明,链沿拉伸方向的共同取向导致的链段摩擦系数减少效应随着侧基数量的增加而弱化,侧基具有一定的“溶剂化”作用。

丙烯酸丁酯碘转移细乳液聚合动力学

碘转移聚合(ITP)是一种链调控剂易得的可逆失活自由基聚合法,细乳液ITP具有高的链调控剂使用效率和乳液稳定性。以碘仿为链转移剂、2,2’-偶氮二异丁基脒二盐酸盐(AIBA)为引发剂,进行丙烯酸丁酯(BA)细乳液ITP,研究AIBA浓度、碘仿浓度和聚合温度对BA聚合转化率、反应速率、聚丙烯酸丁酯(PBA)平均分子量和分子量分布的影响。结果表明:BA细乳液ITP反应快,前期符合一级反应特征,表观反应速率常数随AIBA浓度增大和聚合温度升高而增大;碘仿浓度对反应速率影响不大,但影响PBA的分子量,当碘仿相对单体的摩尔浓度由1‰降低到0.25‰时,转化率大于90%的PBA的数均分子量由1.2×10^(5)增大到5.0×10^(5)左右。以PBA为大分子调节剂种子乳液进行甲基丙烯酸甲酯(MMA)扩链(其中BA与MMA物质的量比为1:1),成功制备了分子量和乳胶粒子粒径均增大的PMMA-b-PBA-b-PMMA共聚物乳液。聚合动力学研究和聚合物结构表征证实了BA和MMA细乳液聚合的“活性”特征。

高压电缆半导电屏蔽材料双逾渗网络对电阻率稳定性的影响

半导电屏蔽材料是制造高压电缆的关键组分,但仍存在电阻率高及其稳定性差难题。基于此,该文提出构筑双逾渗网络结构思路,选择乙烯-丙烯酸丁酯共聚物(ethylene-butyl acrylate copolymer,EBA)和低密度聚乙烯(low density polyethylene,LDPE)作为基体、导电炭黑(conductive carbon black,CB)作为导电填料制备半导电屏蔽材料,系统研究半导电屏蔽材料结构演变规律,评价半导电屏蔽材料结晶行为、电学性能、力学性能、表面光洁度等关键性能。实验结果表明:EBA与LDPE质量比为6:4时,半导电屏蔽材料内部形成双逾渗导电网络结构,相比于常规分布结构,其23和90℃的体积电阻率分别降低46.7%和74.4%,对应的正温度系数(positive temperature coefficient,PTC)降低52.1%,表明具有良好的电阻率稳定性。此外,该半导电屏蔽材料还具有优异的力学性能和表面光洁度。该结果可为高压电缆半导电屏蔽材料开发提供一定理论基础与数据支撑。