ATRP一步法合成支化聚苯乙烯

以α-溴代异丁酸叔丁酯为引发剂,CuBr/2,2′-联二吡啶为催化体系,双甲基丙烯酸乙二醇酯为支化单体,在80℃经原子转移自由基聚合反应合成了支化聚苯乙烯。用1H-NMR、GC、GPC、MALLS和DSC分别对聚合反应过程及聚合物进行了表征和分析。研究表明,聚合反应初期主要生成带有悬垂双键的线型齐聚物,支化结构主要在反应中后期通过悬垂双键的聚合偶联形成;在单体转化率高达87%的情况下合成了质均分子量高达7.9×105的支化聚苯乙烯,其玻璃化转变温度在100℃左右,略低于线型聚苯乙烯。     

链转移剂单体α-甲基丙烯酸-3-巯基己酯对支化聚苯乙烯悬浮聚合的影响

以α-甲基丙烯酸-3-巯基己酯(MHM)为链转移剂单体,偶氮二异丁腈(AIBN)为引发剂,采用悬浮聚合方法合成支化聚苯乙烯。考察了MHM和AIBN浓度对聚合反应的影响;采用核磁共振氢谱(1H-NMR)、三检测体积排除色谱(TD-SEC)和旋转流变仪对支化聚苯乙烯进行了表征分析。结果表明,当物质的量比n(AIBN)/n(MHM)>1时,可以避免交联制备相对分子质量分布相对较窄的高相对分子质量支化聚苯乙烯(-Mw.MALLS=1.03×106g/mol,PDI=7.76),其Zimm相对支化因子g′为0.51,表现出较高的支化程度;与同相对分子质量的线性聚合物相比较,合成的支化聚合物表现出很低的聚合物熔体黏度,同时未表现出明显的剪切变稀行为。     

链转移剂单体α-甲基丙烯酸-3-巯基己酯对支化聚苯乙烯悬浮聚合的影响EI北大核心CSCD

以α-甲基丙烯酸-3-巯基己酯(MHM)为链转移剂单体,偶氮二异丁腈(AIBN)为引发剂,采用悬浮聚合方法合成支化聚苯乙烯。考察了MHM和AIBN浓度对聚合反应的影响;采用核磁共振氢谱(1H-NMR)、三检测体积排除色谱(TD-SEC)和旋转流变仪对支化聚苯乙烯进行了表征分析。结果表明,当物质的量比n(AIBN)/n(MHM)>1时,可以避免交联制备相对分子质量分布相对较窄的高相对分子质量支化聚苯乙烯(-Mw.MALLS=1.03×106g/mol,PDI=7.76),其Zimm相对支化因子g′为0.51,表现出较高的支化程度;与同相对分子质量的线性聚合物相比较,合成的支化聚合物表现出很低的聚合物熔体黏度,同时未表现出明显的剪切变稀行为。     

二乙烯苯为支化单体的支化聚苯乙烯合成反应

以α-溴代异丁酸叔丁酯(t-BBiB)为引发剂,二乙烯苯(DVB)为支化单体,在90℃的条件下经原子转移自由基聚合(ATRP)合成支化聚苯乙烯。用气相色谱(GC)、核磁共振(1H-NMR)和三检测体积排除色谱(TD-SEC)对聚合反应过程和聚合物进行了分析表征。结果表明,在聚合体系中少量带有贫电子双键的共聚单体甲基丙烯酸丁酯(BMA)存在下,能提高引发剂效率,可以在高单体转化率下(>95%)保证聚合反应体系不交联,合成得到高分子量的支化聚苯乙烯,而且分子量分布相对较窄。     

可逆络合聚合制备含悬垂双键超支化聚合物

在偶氮二异庚腈(V_(65))引发甲基丙烯酸烯丙酯(AMA)的传统自由基聚合体系中加入少量碘单质(I_2)和碘化钠(NaI)就成功实现了AMA的"活性"/可控聚合,一步法制备了含大量悬垂双键的超支化聚合物。通过核磁共振(NMR)和三检测凝胶渗透色谱(TD-GPC)对所得聚合物的结构和聚合反应过程进行了分析和表征。结果表明,在此体系中AMA的转化率为81.9%时无交联反应发生,所得超支化聚合物数均相对分子质量为1.11×10~4,相对分子质量分布为6.62,其特性黏数和流体力学半径均小于相同相对分子质量的线型聚合物,具有明显的支化结构。在聚合反应过程中,单体转化率与反应时间呈一级动力学规律,具有典型的活性聚合特征。     

支化苯乙烯-丙烯腈共聚物的合成

以α-溴代异丁酸叔丁酯(BIBTB)为引发剂,二乙烯苯(DVB)为支化单体,苯乙烯(St)和丙烯腈(AN)为共聚单体,CuBr/2,2′-联二吡啶(Bpy)为催化体系,对60℃经原子转移自由基聚合(ATRP)原位生成自引发单体合成支化苯乙烯-丙烯腈共聚物进行了研究。用1H-NMR、GPC、MALLS、FT-IR分别对聚合反应过程和聚合物进行了表征和分析。结果表明,可以由二乙烯苯为支化单体合成支化苯乙烯-丙烯腈共聚物,以多角激光散射法测定的聚合物绝对分子质量-Mw.MALLS达105以上。     

大投料比自缩合乙烯基共聚合中支化结构的演化

研究了CuBr/N,N,N′,N″,N″-五甲基二乙烯基三胺催化的2-(2-溴代异丁酰氧基)乙基甲基丙烯酸酯(BIEM)与大量甲基丙烯酸-N,N-二甲氨基乙酯(DMAEMA)的自缩合原子转移自由基共聚合。分别利用气相色谱、三检测凝胶渗透色谱测定了聚合反应过程中单体转化率、所得聚合物的分子量与分子量分布及特性黏数等随反应时间的变化。结果表明,支化结构在反应早期就已经形成,但是由于具有支化结构的聚合物链相对于共聚单体浓度太低,因此在转化率不大的情况下,支化结构的聚合物链之间无法互相缩合,只能以向DMAEMA的链增长为主,从而导致在聚合物分子量增长同时支化度反而下降。     

链转移剂单体合成支化聚苯乙烯及其表征

以α-甲基丙烯酸和3-巯基己醇为原料,采用直接酯化法合成了链转移剂单体α-甲基丙烯酸-3-巯基己酯(MMH)。以偶氮二异丁腈(AIBN)为引发剂,在MMH存在下进行苯乙烯的常规自由基聚合反应。通过高效液相色谱、气相色谱、三检测凝胶渗透色谱(TD-GPC)和核磁共振氢谱(1H-NMR)对链转移剂单体、聚合反应过程和聚合物进行了表征分析。结果表明,链转移剂单体MMH的纯度可以达95%以上,以MMH为支化单体,可以通过常规自由基聚合反应合成支化聚苯乙烯,得到的支化聚苯乙烯不但具有相对较高的分子量和相对较窄的分子量分布(-Mw.MALLS=370300,-Mw/-Mn=6.9),而且具有较高的支化程度因而表现出较低的特性黏度(g′=0.427)。     

CuSO4-环己酮氧化还原体系的自由基聚合引发能力

研究了CuSO4-环己酮(CyH)氧化还原体系引发甲基丙烯酸甲酯(MMA)的普通自由基聚合。结果显示,当n(CuSO4)∶n(CyH)=1∶5~1∶200,反应温度在70℃~90℃时反应均可进行,所得聚合物分子量在单体低转化率时已较高,且随单体转化率的增长没有明显变化,符合普通自由基聚合的特征,证实了该体系的氧化还原引发能力。另外还研究了以CuSO4-CyH-CuBr2/络合物引发MMA的反向原子转移自由基聚合,所得聚合物的分子量随转化率的上升而增加,但可控性较差。初步分析聚合机理为:Cu2+将CyH羰基α位的-CH2-氧化成了-C.H-自由基,引发单体聚合。此结果意味着过渡金属离子存在时CyH不能作为聚合溶剂。     

无机纳米粒子表面修饰

在讨论无机纳米粒子团聚机理的基础上综述了纳米粒子表面修饰研究进展。表面修饰包括物理和化学修饰,重点综述了表面聚合物修饰最新研究进展。介绍了以化学键在纳米粒子表面接枝聚合物,其主要方法包括在无机纳米粒子表面引入可聚合碳-碳双键合成大分子单体、此大分子单体与相应乙烯基单体共聚在表面生成聚合物;将引发剂"固定"在纳米粒子表面合成大分子引发剂,以此引发剂引发单体聚合物生成表面接枝聚合物;反应型聚合物链与粒子表面活性基团反应将聚合物链接枝到纳米粒子表面。     

大分子链转移剂活性对聚合物分散液晶电光性能的影响

采用可逆加成-断裂链转移(RAFT)、引发转移终止(Iniferter)、反向原子转移自由基聚合(RATRP)等活性自由基聚合方法,合成了分子量相近而带有不同端基的大分子链转移剂。通过紫外光聚合诱导相分离法制备聚合物分散液晶(PDLC)膜。通过研究大分子链转移剂光引发活性,发现采用RAFT聚合制备的大分子链转移剂具有较高的光活性,带有Iniferter活性基团的大分子链转移剂光活性很低。对不同大分子链转移剂制备的PDLC膜的电光性能进行比较,发现采用RAFT法合成的具有高光活性的大分子链转移剂能够使PDLC膜具有较高的开态透光率和较低的驱动电压。加入大分子链转移剂会导致PDLC记忆效应升高。     

纤维素接枝丙烯酸类吸水剂的制备与应用

用反相悬乳聚合法、反相悬浮聚合法、溶液法制备纤维素接枝丙烯酸类吸水剂,并在多种条件下对吸水性的影响进行了研究.结果表明:以麦杆纤维素为原料,选用反相悬乳聚合法制备的吸水剂吸水倍率达到了1712(g/g),吸盐倍率达163(g/g).     

Interfacial Polymerization, A Useful Method for the Preparation of Polymethylcyanoacrylate Nanoparticles

An interfacial polymerization procedure was developed for the preparation of polymethylcyanoacrylate (PMCA) nanoparticles loaded with triamcinolone acetonide. The nanoparticles were characterized concerning their interior structure, size distribution, drug content, drug release and in vivo distribution. These results (except those for the in vivo distribution) were compared with those obtained with nanoparticles prepared by micell polymerization [5]. Both preparation procedures yielded particles with a mean diameter below 500 nm. The drug content of the nanoparticles prepared by interfacial polymerization ranged from 6,5% w/w to 1,9% w/w depending on the employed monomer concentration in contrast to 0,045% w/w for nanoparticles prepared by micell polymerization [5]. In comparison to microcrystalline substance the drug release from the nanoparticles could be sustained in all cases, but there was no difference in drug release between the nanoparticles prepared by both methods.

After removal of surface adherent drug from nanoparticles prepared by both methods those prepared by interfacial polymerization had an about 12 times higher drug content and the remaining drug amount was released more slowly by these particles. Furthermore, using increasing monomer concentrations during interfacial polymerization (125 - 500 mg/100 ml emulsion) drug release was slowed down, but no further improvement could be achieved for monomer concentrations exceeding 250 mg/100 ml emulsion.

After intravenous injection of ^99mTc labeled PMCA nanoparticles into rats they accumulated predominantly in liver, spleen and kidney, a distribution pattern usually found for colloidal particles.     

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...     

Adsorption behavior of carbon nanotubes on polystyrene surfaces

Polystyrene (PS) was prepared using two different polymerization methods (dispersion polymerization and seed polymerization) to investigate the steric stabilizer effect during the adsorption process of carbon nanotubes (CNTs) on the surface of PS microspheres. Experiments with different microsphere diameters and difference types of CNTs were conducted to analyze the curvature effect of the spheres on the adsorption mechanism. The results showed that PS microspheres prepared through dispersion polymerization exhibited preferable adsorption behavior compared to PS spheres prepared through seed polymerization, suggesting that poly(N-vinylpyrrolidone) led to improved adsorption interactions between the CNTs and the PS microspheres in the CNTs dispersion. Additionally, the PS diameter and CNT curvature were examined with respect to the adsorption behavior between the PS microspheres and the CNTs. Multiwalled carbon nanotubes (MWCNTs) were found to be well adsorbed on the surface of PS microspheres measuring 2 microm. However, the MWCNTs were adsorbed much less on the surface of submicron-sized PS microspheres, compared with thinwalled carbon nanotubes (TWCNTs). On the other hand, TWCNTs were found to be suitable for adsorption on submicron-sized PS microspheres. These results also indicate that the curvature of the CNTs and the polymer microspheres are important to the CNT adsorption process.     

Fabrication and characterization of porous calcium polyphosphate scaffolds

Porous calcium polyphosphate (CPP) scaffolds with different polymerization degree and crystalline phases were prepared, and then analyzed by scanning electron microscopy (SEM), Thermmogravimetry (TG) and X-ray diffraction (XRD). Number average polymerization degree was calculated by analyzing the calcining process of raw material Ca(H₂PO₄)₂, as a polycondensation reaction. Amorphous CPP were prepared by the quenching from the melt of Ca(H₂PO₄)₂ after calcining, and CPP with different polymerization degree was prepared by controlling the calcining time. Meanwhile, CPP with the same polymerization degree was prepared to amorphous or different crystalline phases CPP which was made from crystallization of amorphous CPP. In vitro degradation studies using 0.1 M of tris-buffered solution were performed to assess the effect of polymerization degree or crystalline phases on mechanical properties and weight loss of the samples. With the increase of polymerization degree, the weight loss during the degradation decreased, contrarily the strength of CPP increased. The degradation velocity of amorphous CPP, α-CPP, β-CPP and γ-CPP with the same polymerization degree decreased in turn at the same period. The full weight loss period of CPP can be controlled between 17 days and more than 1 year. The results of this study suggest that CPP ceramics have potential applications for bone tissue engineering.     

PCMS高支化聚合物制备中的若干理论问题探讨——（Ⅰ）ATRP本体聚合时摩尔比n／（p—CMS）／n（CuCl）对聚合物的影响

将原子转移自由基聚合(ATRP)和自缩合乙烯基聚合(SCVP)结合，以对氯甲基苯乙烯p-CMS为引发单体进行ATRP反应，得到具有高支化结构的聚对氯甲基苯乙烯PCMS。文中研究了该反应在本体聚合中引发单体和催化剂的摩尔比n(p—CMS)／n(CuCl)对聚合物PCMS的组成和结构的影响，探讨了产生这些影响的可能原因。用GPC测试了聚合物的分子量及其分布，用核磁共振和元素分析表征了聚合物的结构。     

PCMS高支化聚合物制备中的若干理论问题探讨--(Ⅱ)ATRP溶液聚合时聚合条件对聚合物的影响

将原子转移自由基聚合(ATRP)和自缩合乙烯基聚合(SCVP)结合,以p-CMS为引发单体进行ATRP溶液聚合,得到高支化的聚对氯甲基苯乙烯PCMS。研究了采用不同溶剂时,各种因素对聚合物PCMS组成和结构的影响,讨论了产生这些影响的可能原因。     

含聚氨酯型温度和pH双敏性水凝胶的合成及性能研究

合成了两种阴离子型的端烯基聚氨酯（UAA）预聚物，制备了pH值敏感的水凝胶，比较了它们的PH值响应性，将UAA预聚物与N－异丙基丙烯酰胺（NIPA）共聚，得到具有温度和PH值双重敏感性的水凝胶，研究发现聚氨酯侧链的引入对NIPA的相转变温度（LCST）几乎无影响，聚合温度和组成比对所合成的水凝胶性能有较大的影响。