聚(DL-丙交酯-co-ε-己内酯)的合成、结构与性能研究

以辛酸镁为催化剂催化DL-丙交酯和ε-己内酯本体开环共聚合,制备了一系列不同单体配比的共聚物.13CNMR分析了共聚物微观结构,计算各单元平均序列长度,表明两类酯交换反应存在使得单元序列结构重新分布,并趋向于无规化分布;共聚物组成显著影响单元序列长度,各序列长度随相应单体加入量增加而增长.DSC和XRD分析了共聚物热性能和结晶性,表明共聚物结晶性与单元序列长度密切相关.共聚物只观察到一个玻璃化转变温度,符合无规共聚物的Fox方程,说明所得共聚物为无规共聚物,或者说包含有相容性嵌段成分的共聚物.     

可逆加成-断裂链转移细乳液聚合法制备木质素基嵌段共聚物

以木质素黄原酸酯为链转移剂,进行丙烯酰胺(AM)的可逆加成-断裂链转移(RAFT)自由基聚合,并将得到的木质素-丙烯酰胺接枝共聚物(Lignin-g-PAM)作为大分子链转移剂,加入第二单体甲基丙烯酸甲酯(MMA)进行扩链反应制备木质素基嵌段共聚物(Lignin-g-PAM-b-PMMA)。红外光谱、核磁共振氢谱、凝胶渗透色谱、差示扫描量热及热重分析结果证实了MMA与Lignin-g-PAM反应形成了嵌段共聚物;所得Lignin-g-PAM-b-PMMA的相对分子质量显著增加,相对分子质量分布变宽,初始分解温度及最大质量损失温度提高,玻璃化转变温度介于Lignin-g-PAM与PMMA的玻璃化转变温度之间。     

聚合温度对丙烯腈/丙烯酸甲酯共聚物结构与性能的影响EI

在不同聚合温度下,以水相沉淀聚合法合成了丙烯腈与丙烯酸甲酯共聚物。采用差示扫描量热分析(DSC)、元素分析(EA)、核磁共振波谱分析(NMR)等方法对聚合物的组成和结构进行了表征。结果表明,不同的聚合温度对丙烯腈与丙烯酸甲酯共聚物的热力学行为、组成及序列长度产生一定的影响。相同的单体投料比,随着聚合温度的升高,共聚物中丙烯腈的摩尔含量降低,丙烯腈的数均序列长度减小。     

聚合温度对丙烯腈/丙烯酸甲酯共聚物结构与性能的影响

在不同聚合温度下,以水相沉淀聚合法合成了丙烯腈与丙烯酸甲酯共聚物。采用差示扫描量热分析(DSC)、元素分析(EA)、核磁共振波谱分析(NMR)等方法对聚合物的组成和结构进行了表征。结果表明,不同的聚合温度对丙烯腈与丙烯酸甲酯共聚物的热力学行为、组成及序列长度产生一定的影响。相同的单体投料比,随着聚合温度的升高,共聚物中丙烯腈的摩尔含量降低,丙烯腈的数均序列长度减小。     

N-PMI/丁苯胶乳乳液共聚物的合成及热性能研究

采用乳液共聚合的方法,以N-苯基马来酰亚胺(N-PMI)为耐热改性单体与丙烯腈、苯乙烯、丁苯胶乳(SB)乳液共聚合合成了耐热ABS树脂.用DSC、TBA及TGA热分析方法对不同单体配比共聚物的热性能进行了表征,用GPC测定了共聚物的分子量和分子量分布.结果表明,N-PMI的加入能有效提高ABS的耐热性,玻璃化温度和热分解温度均随N-PMI含量的增加而升高.     

9,9'-双氧杂蒽二醇控制丙烯腈与苯乙烯共聚合的研究

采用9,9′-双氧杂蒽二醇(Bixan)引发丙烯腈与苯乙烯共聚,在苯甲醚溶液中聚合时,分子量增长,分子量分布指数为1.4～1.7。用元素分析法测得共聚物的组成,并用差示扫描量热仪(DSC)法测其玻璃化温度,结果表明其为丙烯腈和苯乙烯的无规共聚物。     

通过高温自由基聚合合成耐热聚甲基丙烯酸甲酯树脂

本文探究了采用乙醇作溶剂,通过高温自由基聚合方法合成耐热甲基丙烯酸甲酯(MMA)与甲基丙烯酰胺(MAAM)共聚物的可行性,研究了聚合温度对Poly(MMA-co-MAAM)共聚物的共聚组成、相对分子质量、相对分子质量分布及共聚物耐热性的影响。结果表明,用乙醇作溶剂,聚合温度在90~120℃范围内可以成功合成高耐热Poly(MMA-co-MAAM)共聚物,其最佳共聚合温度为110℃。在此温度条件下合成的Poly(MMA-co-MAAM)共聚物的相对分子质量分布指数均小于1.5,耐热性最佳,其玻璃化转变温度较同等聚合条件下合成的PMMA均聚物高46℃。     

氧亚甲基连接的聚氧化乙烯统计共聚物的热性能研究EI

研究了统计共聚物(Statistic Copolymer)氧亚甲基连接的聚氧化乙烯(OM-POE)的热力学行为,探索了聚合物链中氧化乙烯链段的平均长度和长度分布对聚合物及其共混物的玻璃化温度、熔点、熔化热及结晶度的影响。结果表明,不同长度的氧化乙烯链段无规地进入分子链中,熔点与组成的关系可用Flory的无规共聚物熔点方程来描述。     

St-BA共聚物玻璃化温度与转化率的关系

用溶液聚合的方法在不同投料比下合成了不同转化率的苯乙烯-丙烯酸丁酯无规共聚物,低转化率下共聚物的组成用1H-NMR测定,聚合物的玻璃化温度(Tg)用差示扫描量热法(DSC)测量。采用非线性最小二乘法(NLLS)计算得到单体的竞聚率rSt=0.831,rBA=0.187,不同转化率瞬时共聚物含量由竞聚率、投料比计算,Tg用前期提出的共聚物Tg-组成关系方程计算,累计产品的Tg由瞬时共聚物Tg用Fox公式加和而得,按此种方法预测的St-BA共聚物Tg-转化率关系与实验结果基本一致。     

L-丙交酯/ε-己内酯配比对共聚物微结构和性能的影响

辛酸亚锡催化下开环聚合制备不同物质的量比L-丙交酯/ε-己内酯(LLA/CL)共聚物。核磁共振(1H和13C-NMR)结果表明,共聚物组成与投料比基本一致,聚合过程中酯交换反应导致序列结构重新分布,二级酯交换系数(TII[CLC])随CL用量增加而增大。共聚物组成明显影响单元序列长度,各序列长度随相应单体投料量增加而增大,CL投料比≤50%的平均序列长度(LLL和LC)与相应的无规序列长度(LRC和LRLL)较接近,共聚物趋于无规分布。差示扫描量热(DSC)和广角X射线衍射(WAXD)表明共聚物是结晶态聚合物,结晶性与单元序列长度密切相关。共聚物组成显著影响其力学性能,随CL物质的量分数增加,且≤35%时表现出屈服形变的特点,具有热塑性弹性体的特征。     

MMA/MPEOMA copolymers as coating materials for improved blood compatibility: protein adsorption study

Surface-induced thrombosis remains one of the main problems in the development of blood-contacting devices. When a foreign surface comes in contact with blood, the initial blood response is adsorption of blood proteins, followed by platelet adhesion and activation, leading to thrombus formation. A particularly effective polymer for the prevention of protein adsorption and platelet adhesion appears to be polyethylene oxide (PEO). In this study, water-insoluble copolymers of methyl methacrylate (MMA) and methoxy PEO monomethacrylates (MPEOMA) with different PEO molecular weights (200, 400, and 1000) and monomer composition were synthesized and characterized by gel permeation chromatography and ¹H-nuclear magnetic resonance spectroscopy. The synthesized copolymers were coated on glass slides by a spin coating method to prepare PEO-rich surfaces as blood-compatible surfaces. The surface properties of the copolymers and their interaction with blood proteins (albumin, γ-globulin, fibrinogen, and plasma proteins) were investigated by the measurement of water contact angles and by electron spectroscopy for chemical analysis, respectively. It was observed that the protein adsorption on the copolymer surfaces decreased with increasing PEO molecular weight and MPEOMA content in the copolymers. The copolymers with long PEO chains in MPEOMA (MMA/MPEO₀₀₀MA copolymers) were effective in preventing protein adsorption, even though their MPEOMA content was less than the copolymers with shorter PEO chains. © 1999 Kluwer Academic Publishers     

Melt-processable acrylonitrile–methyl acrylate copolymers and melt-spun fibers containing MicroPCMs

Acrylonitrile–methyl acrylate (AN–MA molar ratio 85/15) copolymer and copolymers containing 5–25 wt% of microencapsulated phase change materials (MicroPCMs) were synthesized by aqueous redox initiated polymerization. MicroPCMs were incorporated into the copolymer at the step of polymerization. The copolymers were processed by environment friendly, solvent-free melt-spinning. The structures and properties of the copolymers and as-spun fibers containing MicroPCMs were characterized by Nuclear Magnetic Resonance (¹H NMR), Gel Permeation Chromatography (GPC), Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TG), Scanning Electronic Microscope (SEM), X-ray Diffraction (XRD), and Melting Index (MI). The results show that the composition of AN–MA copolymer agrees well with the feeding ratio of AN and MA. The copolymers containing MicroPCMs can be processed at 200 °C. The crystalline enthalpies of the fibers containing 20 and 25 wt% of MicroPCMs are 21 and 25 J/g, respectively; and they increase steadily as the contents of MicroPCMs increase. Tensile strengths of the as-spun fibers are in the range of 1.0–3.2 cN/dtex. The fibers are potentially used as raw materials to fabricate thermo-regulated fabric for comfort clothing.     

液晶基元直接横挂于主链上的液晶共聚物的合成与研究

以含液晶基元的单体２，５－双（４－甲氧基苯甲酰氧基）苯乙与苯乙烯通过自由基共聚合反应，首次合成了一系列含液晶性和非液晶性两种序列结构的共聚物。采用ＤＳＣ、偏光显微镜和Ｘ衍射方法研究了共聚物的液晶行为，发现单体和共聚物（只有ＣＰ－５和ＣＰ－６）有很好的热致液晶性。随共聚物中介晶单体单元含量的增加，共聚物玻璃化转变温度Ｔ和热分解温度Ｔ呈规律变化。     

不同软段长度PBT-co-PCT-b-PEG嵌段共聚物的结构与性能

用熔融缩聚法合成了一系列具有相同软段摩尔含量．不同软段长度的聚对苯二甲酸丁二醇酯(PBT)-co-聚对苯二甲酸环己烷二甲醇酯(PCT)-b-聚乙二醇(PEG)嵌段共聚物(PBCG)。NMR分析表明。共聚物软段质量百分含量随PEG分子量(M^-n(PEG))增加而增加。随PCT摩尔万分数(MPCT)增加而减小;结构中两种硬段呈无规分布,M^-n(PEG)一定。随MPCT增加。PBT平均序列长度战小,而PCT平均序列长度增加。硬段熔点及结晶度在MPCT为20％～30％处达到最小值。TGA分析显示。向体系中引入PCT可提高共聚物热稳定性。     

Synthesis and characterisation of soluble block copolymers from NR and TDI based polyurethanes

Soluble block copolymers from toluene diisocyanate (TDI), with chain extender diols, viz., propylene glycol (PG), 1,4-butane diol (1,4-BDO) and 1,3-butane diol (1,3-BDO), were synthesised for the first time by solution polymerisation. Maintaining low hard segment content and keeping optimum NCO/OH ratio, formation of linear, flexible elastomers is achieved. They were characterised by spectral, thermal, microscopic and stress–strain analysis. The dilute solution properties of these block copolymers dissolved in tetrahydrofuran (THF) are studied by viscometry and gel permeation chromatography (GPC). IR and NMR spectral data support the notion that a chemical reaction leads to block copolymerisation. Differential scanning calorimetric (DSC) analysis showed a soft segment glass transition temperature around −58°C and a hard segment glass transition temperature between 75 and 70°C for these samples. This observation and two-stage thermal decomposition of the samples in thermogravimetric analysis (TGA) clearly indicate that the block copolymers are completely phase-segregated systems. SEM indicates the amorphous heterophase morphology of the samples.     

含噁二唑类与咔唑类共聚物的合成与表征

由2-苯基-5-〔甲基丙烯酰胺基取代苯基〕-1,3,4-噁二唑(OXD)与甲基丙烯酸乙基咔唑酯(CzE-MA)两种单体合成了含噁二唑和咔唑基团的无规共聚物。通过红外、核磁、紫外、荧光、热重、差示扫描量热,凝胶渗透色谱对聚合物进行了表征。测试结果表明共聚物有很好的溶解性,均可溶于常用的有机溶剂,如THF,CHCl2,CHCl3等,其分子量在16950～22500之间。有良好的热稳定性和很高的玻璃化转变温度(Tg=190～222℃),最大吸收波长在220～340nm之间,具有良好的荧光性,其荧光发射波长均在372～451nm范围内,是一类蓝紫色荧光聚合物。共聚物随着CzEMA组分的减少和OXD组分的增加,发射波长蓝移,其中以P(OXD8-CzEMA2)的荧光性最好,荧光量子产率高达0.70。     

Ultra-fast catalytic reduction of dyes by ionic liquid recoverable and reusable mefenamic acid derived gold nanoparticles

We synthesized mefenamic acid (MA) derived gold nanoparticles (MA-AuNps) in aqueous solution (MA-Au sol). Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) of the sol at 1, 5, 15 and 60 min showed changes in size and shape of formed AuNps. Fourier Transform Infrared (FTIR) Spectroscopy revealed the interaction between AuNps and MA. Each Au sol exhibited exceptional catalytic activity for the reduction of Methylene Blue (MB), Rose Bengal (RB) and Eosin B (EB) dye individually as well as collectively. However, complete reduction of dye(s) was accomplished by Au sol of 5 min in just 15s. The catalytic performance of Ma-Au sol was far superior to that adsorbed on glass. AuNps were recovered with the help of water insoluble room temperature ionic liquid and reused with enhanced catalytic potential. This finding is a novel, rapid and highly economical alternative for environmental safety against pollution by dyes and extendable for control of other reducible contaminants as well.     

水平机械研磨酸性镀铜工艺研究

为研究不同研磨珠直径对镀层细化及性能的影响,在硫酸盐酸性镀铜溶液中添加玻璃珠,玻璃珠的运动对A3钢表面产生机械研磨作用(MA),并采用扫描电镜、显微硬度测试仪、电化学工作站等方法对其进行观察和分析.结果表明:与传统硫酸盐酸性镀铜层相比,机械研磨镀铜层的膜厚和孔隙率降低,硬度、耐蚀性、防渗碳性能提高;机械研磨镀铜层的晶粒尺寸大小随着研磨直径的增大先减小后增大;当研磨珠直径为8 mm时,镀层的晶粒尺寸小于2μm,硬度达到168.3 HV,孔隙率为0.6个/cm~2,渗碳层的厚度为40μm.     

苯乙烯/异戊二烯渐变嵌段共聚物的负离子法合成和性能

一次加料延时加入极性结构调节剂四氢呋喃(THF)、以正丁基锂(n-BuLi)为引发剂、环己烷为溶剂,用活性负离子聚合技术合成了具有渐变嵌段结构的苯乙烯(St)/异戊二烯(Ip)共聚物(S/I)。使用核磁共振氢谱(¹H-NMR)和动态粘弹谱(DMA)等仪器表征共聚物的微观结构并测定共聚物的动态力学性能,研究了THF的加入时间和St含量对S/I共聚物微观结构和性能的影响。结果表明,加入THF的时间显著影响共聚物的微观结构、力学和动态力学性能。控制THF的加入时间能调控St和Ip单体的共聚合活性从而调控共聚物的微观结构和共聚物的组成及其分布,生成具有渐变嵌段结构的S/I共聚物,拓宽共聚物的玻璃化转变温度(T_g)区间。对S/I共聚物的结构和性能的变化过程也进行了理论分析。