MTBTM／VAc和MTBTM／MA共聚物水解的研究

本文合成一系列有机锡含量不同的顺丁烯二酸甲基三丁基锡酯与乙酸乙烯酯及丙烯酸甲酯的共聚物。研究了共聚物中锡含量不同及水解条件不同对共聚物水解速度的影响。结果表明:两种共聚物水解速度均随着锡含量、水解介质的温度和pH值的增大而增大。同时还研究了共聚物水解的表观活化能。     

含氟丙烯酸酯共聚物改性环氧涂层的制备与性能

采用半连续滴加的乳液聚合法制备了甲基丙烯酸十二氟庚酯-丙烯酸十八酯-甲基丙烯酸甲酯(DFMA-SA-MMA)三元共聚物,并将其加入到环氧涂料中,制备了具有极高疏水性能的环氧涂层.考察了含氟丙烯酸酯无规共聚物的加入量对涂层的接触角和表面能的影响.结果表明,共聚物的加入显著降低了涂层的表面能,接触角明显增大,当共聚物的用量...     

偶联法制备聚羟基丁酸酯/聚乙二醇共聚物及其性能

利用二异氰酸酯为偶联剂,采用不同分子量的聚乙二醇(PEG)与聚羟基丁酸酯(PHB)进行偶联反应,制备一系列聚羟基丁酸酯/聚乙二醇共聚物。利用红外光谱(FT-IR)、差示扫描量热(DSC)、广角X射线衍射(WAXD)、表面水相接触角及力学性能实验对共聚物进行了分析研究。结果表明,偶联聚乙二醇后,PHB链的规整度降低,PHB的结晶度下降,非结晶区增大,同时表面亲水性变好,当采用高分子量的PEG后,共聚物的拉抻应力-应变曲线中出现了明显的屈服点,断裂伸长率也有了较大的提高,达到了11%,韧性得到改善,力学性能有一定程度的提高。     

UV固化含氟聚丙烯酸酯的制备

以甲基丙烯酸十二氟庚酯、丙烯酸-2-乙基己酯、甲基丙烯酸羟乙酯、苯乙烯为聚合单体,偶氮二异丁腈为引发剂,通过溶液聚合制得了含氟羟基聚丙烯酸酯共聚物(PGHES),以含异氰酸酯的不饱和单体HIp与共聚物PGHES侧链上的羟基反应制得光敏性含氟聚丙烯酸酯(U-PGHES)。用傅立叶红外光谱(FT-IR)、核磁共振氢谱(1 H-NMR)表征聚合物结构;用凝胶渗透色谱(GPC)及差示扫描量热仪(DSC)表征聚合物分子量及玻璃化转变温度;用光学接触角测量仪测量了聚合物固化膜接触角并计算得到表面能。结果表明,固化膜表面能随U-PGHES中含氟量的增加而降低,当含氟量达到9%时,表面能降低趋缓。     

分子量对非离子型壳聚糖表面活性剂表面活性的影响

以四种不同分子量的壳聚糖(粘均分子量分别为4.00×105,1.09×105,7.15×104和3.42×104)为原料,先在相同反应条件下分别与环氧丙烷反应制得相应的水溶性衍生物——羟丙基壳聚糖(HPCHS),再进一步在催化剂存在条件下与十二烷基缩水甘油醚反应制得相应的功能性壳聚糖衍生物——非离子型壳聚糖表面活性剂,即(2-羟基-3-十二烷氧基)丙基-羟丙基壳聚糖(HDP-HPCHS)。实验结果表明,不同分子量的HDP-HPCHS产物均具有良好的水溶性和表面活性,且其表面活性随分子量的改变而呈规律性变化。在实验分子量范围内,HDP-HPCHS水溶液的最低表面张力随其分子量的降低而减小;其临界胶束浓度呈现先随分子量的降低而增大后又减小的变化趋势。     

聚乙二醇-聚硅氧烷哑铃形嵌段共聚物的合成与表征

金属钾和聚乙二醇1000在THF中反应生成醇钠,再加入环氧氯丙烷得到环氧基端基的聚乙二醇,经水解,重复以上步骤,分别得到了具有4和8羟基端基的聚乙二醇中间体。将不同数目羟基端基聚乙二醇和KOH、D4在100℃～140℃条件下进行开环聚合,即得具有线性-树状结构的聚乙二醇-聚硅氧烷哑铃形共聚物。用核磁共振、凝胶渗透色谱和原子力扫描电镜对所得共聚物的结构、性能及其在亲水表面的排列方式作了详细研究。结果表明,4和8羟基端基聚乙二醇的羟基官能度分别为3.96和7.70;共聚物的绝对数均分子量分别为4300g/mol、4700g/mol和5900g/mol;哑铃形共聚物在亲水介质表面可形成形态学不均一、表面较为粗糙的硅膜。     

阳离子型含氟丙烯酸酯的制备及防水防油性能

以甲基丙烯酸十二氟庚酯(FM)、丙烯酸丁酯(BA)、苯乙烯(St)、甲基丙烯酰氧乙基三甲基氯化铵(DMC)、丙烯酸十八酯(ODA)为原料,采用无皂乳液聚合制得了阳离子含氟丙烯酸酯多元共聚物乳液。对聚合物的结构、组成进行了表征研究,研究了共聚乳液膜表面的性质。结果表明,随着共聚物中全氟单体含量的增加,共聚物膜的表面能显著降低,当全氟单体的含量达到25%(质量分数)时,其表面能降低到19.99 mJ/m;并通过热处理表明了含氟单体随温度、时间增大更容易向表面富集的现象,当达到60min,120℃时水和油接触角分别达到了110°和83°。     

三硫代碳酸酯引发的苯乙烯活性自由基光聚合

合成了一种可逆加成-断裂链转移聚合(RAFT)链转移试剂S,S′-二(α,α′-甲基α-″-乙酸)三硫代碳酸酯(TR IT),对以TR IT为链转移剂,苯乙烯(S t)等单体室温下的紫外光引发聚合进行了研究。得到了分布比较窄的PS t(M-w/M-n=1.10~1.14)。研究了S t光聚合过程,ln[M]0/[M]随聚合时间的延长呈线性增加,分子量随转化率也呈线性增长。用FT-IR、NM R等方法对所得聚合物的结构进行了研究,结果表明,聚合物分子链中含有三硫代碳酸酯基。以合成的含有三硫代碳酸酯基的PS t-S-C(=S)-S-PS t为大分子引发剂,在相同的光聚合条件下引发丙烯酸丁酯(BA),得到了分子量分布窄的PS t-PBA-PS t三嵌段共聚物。     

聚乳酸的降解研究

探讨了聚乳酸水解以及超声波降解情况,利用傅立叶红外光谱(FT-IR)和凝胶渗透色谱仪测定其基团及相对分子质量变化。研究结果表明:聚乳酸超声波降解同其水解均为酯键断裂导致的,并且是酯键的任意断裂,在水解过程中聚乳酸质量损失快慢为盐酸溶液>磷酸缓冲液>去离子水;聚乳酸在水解过程中,相对分子量随降解时间的延长而减小,但在超声波作用30min下其质量有一定程度的损失而相对分子量反而增大,推断其可能发生了部分交联反应。     

高性能含硅、氟甲基丙烯酸酯共聚物的研究

制备了γ-甲基丙烯酰氧基丙基三(三甲基硅基)硅烷W D、γ-甲基丙烯酰氧基丙基三乙氧基硅烷及其与甲基丙烯酸异冰片酯、甲基丙烯酸异丁酯和含氟甲基丙烯酸酯的共聚物,通过IR、水接触角、吸水率、铅笔硬度和DSC等手段研究了共聚工艺、含氟单体、硅烷单体及催化交联剂对共聚物膜表面性能和力学性能的影响。延迟滴加有机硅单体尤其是W D和含氟单体可使低用量硅氟单体下的共聚物膜表面憎水性大大增强;催化交联剂可使共聚物的玻璃化温度从31.21℃提高到53.12℃,膜的铅笔硬度达到4H以上。     

甘氨酸接枝酶解木质素的制备及表征

以酶解木质素（EHL）、甘氨酸（Gly）和甲醛为原料,采用Mannich反应制备了甘氨酸接枝酶解木质素（EHL-g-Gly）。研究了反应温度与时间,甲醛/甘氨酸物质的量比对接枝产物的产率和接枝率的影响。结果表明,在反应温度为90℃、反应时间3h、甘氨酸/EHL质量比为1∶1、甲醛/甘氨酸物质的量比为2∶1时接枝率可达2...     

Bisphenol A imprinted polymer adsorbents with selective recognition and binding characteristics

Imprinted copolymers, which highly recognized and bound bisphenol A (Bis A), were synthesized by using covalent imprinting technique. Bisphenol A dimethacrylate (BADM) was used as a template monomer in the copolymerization with a crosslinkable monomer of divinyl benzene (DVB), ethylene glycol dimethacrylate (EGDM) or N,N’-methylenebisacrylamide (MBAA). The resultant copolymer was hydrolyzed in acidic or basic condition. It was found that the Bis A imprinted copolymers of EGDM and MBAA had no selectivity to Bis A, because the crosslinker dissociated by the hydrolysis reaction and thus comprehensive imprinted sites were not formed. On the other hand, imprinted copolymer of DVB showed excellent selectivity to differentiate Bis A from bisphenol E and bisphenol F (Bis F). Characterization of the copolymers suggested that the DVB copolymer had resistance to the acid and alkali conditions. Effect of recognition by the Bis F imprinted polymer was also compared with that of the Bis A imprinted polymer, when DVB and bisphenol F dimethacrylate were copolymerized. The Bis F imprinted copolymer was able to recognize Bis F in ethanol solution, however showed higher binding capacity for both Bis A and Bis F in water solution without recognition. Therefore, hydrophobic interaction between Bis A and the imprinted site enhanced the binding capacity with high selectively for the BADM-co-DVB imprinted copolymer.     

淀粉与聚乳酸接枝共聚物的制备与表征

采用三甲基硅烷基(TMS)保护淀粉作为大分子引发剂,辛酸亚锡催化,制备聚乳酸与淀粉的接枝共聚物.红外光谱和核磁共振氢谱分析证实了共聚物的形成.接触角测试结果表明亲水性糖基的引入使共聚物具有较好的亲水性.在pH=7.2的PBS缓冲液中,共聚物膜能较快降解,6d后失重率接近50%,10d后完全降解.对聚乳酸进行糖基化改性,将大大拓展聚乳酸类材料在生物医学领域的应用范围.     

一种新型可降解共聚物薄膜的制备与性能研究

在氩气环境下,以丁二酸、己二酸、1,4-丁二醇和尿素为原料,通过高温熔融缩聚和扩链反应合成了一种新型可降解丁二酸/己二酸-1,4-丁二醇-尿素聚酯酰脲共聚物,并用压延成膜法制备了共聚物薄膜.采用红外光谱、热重分析、差示量热扫描及万能拉力机对共聚物薄膜的结构与性能进行了表征.结果表明,随着己二酸含量的增加,聚合物薄膜的熔点、结晶度和结晶温度均明显下降.当n（SA）∶n（AA）=1∶1时,共聚物大部分为无定形区域,结晶性能大大降低,水解速率最快,薄膜的降解性能最好.通过调节丁二酸与己二酸添加的物质的量之比,可使聚酯酰脲薄膜在热学性能、力学性能和降解性能之间达到一定程度的可控性.     

添加正十八烷微胶囊的丙烯腈与甲基丙烯酸甲酯共聚物的合成与表征

采用氧化还原引发剂合成了含有正十八烷微胶囊的丙烯腈/甲基丙烯酸甲酯共聚物。测试表明,丙烯腈和甲基丙烯酸甲酯单体发生了共聚,共聚物中丙烯腈成分的实测含量略低于理论含量;试样中的微胶囊的吸热和放热温度与纯微胶囊的吸热放热温度接近,随着微胶囊含量的增加,共聚物中微胶囊的热效率逐渐增大;随着微胶囊含量的增加,试样中共聚物的结晶度增大。     

Enhancement of corrosion protection efficiency of iron by poly(aniline-co-amino-naphthol-sulphonic acid) nanowires coating in highly acidic medium

Nanowires of copolymers film based on aniline and 1-amino-2-naphthol-4-sulphonic acid were electrochemically synthesized on the iron electrode by cyclic voltammetry using oxalic acid as a supporting electrolyte. Protective properties of copolymer film on the iron surface in 1.0 M HCl solution was investigated by chronoamperometry, potentiodynamic polarization technique and electrochemical impedance spectroscopy (EIS). The results showed that the copolymer film showed the significant shifting in the corrosion potential and greater charge transfer resistance. Moreover, the copolymer showed the larger degree of surface coverage onto the iron surface, reflecting the higher protection for corrosion of the iron in acidic medium. In addition, the film constitutes a physical as well as a chemical barrier layer due to the presence of -OH and -NH groups in ANSA unit, which provides passivity protection in polymer coatings. The mechanism of corrosion protection of iron by these copolymers was investigated by surface morphology and EIS techniques. In addition, by using scanning electron microscopy, the effect of morphology of copolymer on corrosion protection of metal was investigated.     

可熔融丙烯腈共聚物的组成及流变性与热性能

分别采用水相沉淀聚合法和乳液聚合法制备了丙烯腈-丙烯酸甲酯共聚物（AN/MA,投料比为85/15（物质的量比））,采用傅里叶变换红外光谱（FT-IR）、元素分析（EA）、乌氏黏度计、高级扩展流变仪（TA）、差示扫描量热仪（DSC）、热重分析仪（TG）对共聚物的组成、流变行为和热性能进行了研究。结果表明,水相沉淀聚合法和...     

Layer‐by‐Layer Fabrication of Covalently Crosslinked and Reactive Polymer Multilayers Using Azlactone‐Functionalized Copolymers: A Platform for the Design of Functional Biointerfaces

We report a method for modulating the physicochemical properties of surfaces that is based on the reactive layer‐by‐layer fabrication of covalently crosslinked thin films using azlactone‐functionalized copolymers. We demonstrate that copolymers containing different molar ratios of methyl methacrylate (MMA) and 2‐vinyl‐4,4‐dimethylazlactone (VDMA) can be alternately deposited with poly(ethyleneimine) to assemble covalently crosslinked thin films. Characterization using ellipsometry demonstrates that, in general, film growth and thickness decrease as the content of reactive, azlactone functionality in the copolymer used to assemble the film decreases. Reflective infrared spectroscopy experiments demonstrate that films fabricated from MMA:VDMA copolymers contain residual azlactone functionality and that these reactive groups can be exploited to modify film‐coated surfaces. Fabricating films from MMA:VDMA copolymers containing different compositions permitted modulation of the density of reactive groups within the films and, thus, the extent to which the films are functionalized by exposure to small molecule amines. For example, functionalization of MMA:VDMA copolymer films with the small molecule D ‐glucamine resulted in films with water contact angles that varied with the composition of the copolymer used to fabricate the film (e.g., as the azlactone content in the film increased, glucamine‐modified films became more hydrophilic). We demonstrate further that treatment of copolymer‐containing films with glucamine resulted in changes in the numbers of mammalian cells that grow on the surfaces of the films. Our results suggest the basis of methods that could be used to modulate or tune the density of chemical and biological functionality presented on surfaces of interest in a variety of fundamental and applied contexts.     

新型水分散有机硅-聚氨酯共聚物的结构与性能

合成出含量为0%~12%的以二端羟丁基聚二甲基硅氧烷(DHPDMS)为部分软链段的新型水分散有机硅-聚氨酯共聚物(DHPDMS-PU)。NMR和FT-IR分析表明DHPDMS链段已被化学键入共聚物分子链中。比较透射和全反射衰减红外光谱发现,在含硅氧烷软链段的试样中,硅氧烷在成膜过程中逐渐向膜表面扩散,从而使材料具有较好的表面性能。随DHPDMS含量升高,DHPDMS-PU膜的水接触角增大,表面能减小;当DHPDMS含量超过7%时接触角渐趋于恒定。由分峰拟合发现氢键化的N-H含量随DHPDMS的增加而降低。     

含氟硅低表面能共聚物的制备与表征

将丙烯酸六氟丁酯和γ-甲基丙烯酰氧基丙基三甲氧基硅烷与(甲基)丙烯酸(酯)进行共聚,合成含氟硅共聚物.用红外光谱(FT-IR)、X射线光电子能谱(XPS)和热重分析(TGA)对共聚物的结构和性能进行表征,并测试了共聚物膜的吸水率及对水和油的接触角.XPS结果表明,共聚物膜表面的F和Si元素相对物质的量明显高于150 n...