N-异丙基丙烯酰胺/丙烯酸十八酯共聚物水溶液胶束及相分离行为研究

合成了N异丙基丙烯酰胺(NIPAM)和丙烯酸十八酯(ODA)的共聚物.利用荧光探针和滴重法研究了NIPAMODA共聚物在水溶液中的胶束形成过程.同时还利用荧光探针法研究了共聚物水溶液在温度升高时出现的LCST(LowerCriticalSolutionTemperature)现象,表明该高分子在温度升高时存在着相分离现象.利用LB技术测量共聚物不溶单分子膜的PA曲线,发现随着温度升高共聚物的单分子膜越来越凝聚的反常现象,这从另一个侧面证实了共聚物NIPAMODA的相分离行为,并对此现象作了讨论.     

水溶性疏水缔合型聚(丙烯酰胺-丙烯酸十六酯)溶液性质的研究

采用沉淀聚合法制备水溶性的丙烯酰胺－丙烯酸十六疏水缔合型共聚物,研究了共聚物水溶液的性质及其影响因素。随着疏水基团含量增加,共聚物在纯水中及NaCl溶液中的特性粘数[η]均减小,疏水基团临界缔合浓度降低。共聚物溶液浓度高于监界缔合浓度时,溶液表现粘度急剧增加,表明溶液中分子间缔合大量形成。     

粘度和光谱方法研究二元阴离子型丙烯酰胺共聚物(P3A)在不同pH水溶液中的构象变化

采用粘度和光谱方法,研究了强酸性和弱酸性2种阴离子型单体与丙烯酰胺的三元共聚物(P3A)在稀水溶液中pH诱发的构象变化,P3A聚合物由丙烯酰胺(AM)和强酸性离子单体(AMPS)及弱酸性离子单体(AA)组成.试验结果表明P3A聚合物溶液的粘度随pH呈现非单调的增长关系,在pH为4～5范围内产生急剧的升高,这现象归因于聚合物链团从紧密状态向膨胀状态迅速的转变.这两种状态的溶液粘度变化幅度和聚合物P3A中AMPS和AA组合比例紧密相关,芘探针在聚合物P3A溶液中的荧光强度和pH的关系呈现类似粘度变化的结果.在低pH值时,发现单一弱酸离子共聚物(P2AA)溶液发生相分离,然而在含有强酸单元(AMPS)的P3A聚合物情况下,这种现象不再产生.     

表面活性剂对纤维素接枝共聚物溶液粘度性质的影响

研究了阴离子十二烷基硫酸钠(SDS)、阳离子十六烷基三甲基溴化铵(CTAB)和非离子聚乙二醇辛基苯基醚(OP)等三种不同类型的表面活性剂对疏水化水溶性两性纤维素接枝共聚物(CGAO)溶液粘度性质的影响.结果表明,在SDS和OP的临界胶束浓度(cmc)附近，CGAO溶液粘度最大，SDS引起CGAO粘度的变化大于OP；即使在CTAB的cmc附近，随着CTAB浓度的增加，CGAO的粘度一直呈下降趋势；非疏水改性的纤维素接枝共聚物的溶液粘度随SDS或CTAB浓度的增加而下降，但几乎不随OP浓度的增大而变化.此外，通过凝胶渗透色谱法测得的保留时间证实了SDS、CTAB和OP与CGAO之间的疏水缔合作用.     

超临界CO2中丙烯酸含氟酯疏水改性聚丙烯酸的合成

研究了在超临界二氧化碳条件下 ,丙烯酸 1,1 二氢全氟辛酯 (FOA)对聚丙烯酸疏水改性的共聚反应 .发现与通常聚合方法相比含氟丙烯酸酯的产率得到提高 ;反应时间从 2 4h缩短到 4h ;所得产物的后处理也更容易 .同时发现温度对反应有影响 ,含氟酯单体在低温 (T <5 5 0℃ )时活性高于丙烯酸单体 ,在高温 (T >6 0 0℃ )时丙烯酸活性提高较大 .而共聚物水溶液粘度随pH值变化先上升后下降 ,在pH =5 0出现峰值 ,显示其中有分子间缔合存在 .与改性聚丙烯酰胺不同 ,改性聚丙烯酸水溶液粘度随FOA含量的增加而单调上升 ,也证明了分子间缔合的存在     

亚铁离子对驱油聚合物溶液黏度的影响及其降黏机理

采用NaOH沉淀法去除胜坨油田T28区污水含有的亚铁离子(Fe2+),使配制的聚合物溶液黏度增加,通过红外光谱仪(IR)、荧光光谱仪及扫描电子显微镜(SEM)对Fe2+的降黏机理进行了分析。 结果表明,采用NaOH沉淀法处理Fe2+含量为5.9 mg/L的污水,控制pH=9,聚合物溶液的黏度可由19.17 mPa·s提高到92.50 mPa·s。 Fe2+使聚合物大分子发生断链,分子间的缔合作用减弱,破坏了分子链间形成的空间网络结构,导致溶液黏度显著降低;当用NaOH处理Fe2+后形成了Fe(OH)2沉淀而析出,同时使聚合物分子链间形成致密的空间网络结构。     

无皂乳液聚合制备含铕荧光共聚物乳液的研究及其表征

以丙烯酸(AA)为第一配体、邻菲罗啉(Phen)为第二配体、Eu3+为中心离子,合成了一种可聚合的稀土铕配合物.以配合物单体、甲基丙烯酸甲酯、丙烯酰胺和对苯乙烯磺酸钠为共聚单体,通过无皂乳液聚合的方法,制备了含铕荧光共聚物乳液.采用红外光谱对共聚物的结构进行了表征,并探讨了配合物单体含量对共聚物乳液性能的影响.透射电子显微镜(TEM)和激光光散射粒度仪(PCS)测试结果表明,共聚物乳液形成了相对均一的球状结构,但随着配合物单体含量增加,共聚物微球粒径逐渐增大、分散性变差.采用荧光分光光度计测试了共聚物乳液的荧光性能,在594和619 nm处出现Eu3+的特征发射光谱,且荧光强度随着配合物单体含量增加而增强.     

三嵌段共聚物EO20PO70EO20相分离行为的耗散粒子动力学模拟

采用耗散粒子动力学(DPD)方法研究了嵌段共聚物EO₂₀PO₇₀EO₂₀(P123)在水、乙醇/水溶液及二氧化硅溶胶体系中的相分离行为. 不同质量分数的P123在水溶液中共形成4种相分离状态: 球状胶束(10%); 椭球胶束(20%)、棒状胶束(30%)和三维立方胶束(50%). 在模板剂质量分数为10%的乙醇/水溶液中, 模板剂胶束稳定性随着乙醇含量的增加而变差. 在二氧化硅溶胶体系中, 模板剂质量分数低于5%时无胶束形成; 模板剂质量分数增至10%时, P123发生相分离形成三维球状胶束; 随着模板剂质量分数的进一步增加, 模板剂分子夹含着水分子形成三维椭球状结构(20%)、三维立方结构(40%)和层状结构(60%). 模拟结果与实验结果一致, 说明DPD模拟可以从计算角度推测模板剂对介孔材料结构的影响.     

离子交联聚氯乙烯的结构与性能

由氯乙烯/丙烯酸悬浮共聚合成了不同羧基含量的PVC树脂,采用溶液反应和熔融加工法制备离子交联PVC,对其结构和性能进行了研究.结果表明,共聚物中羧基主要以二聚体形式存在,用金属离子中和能形成部分络合结构;用Ca²⁺、Mg²⁺离子络合的羧基含量较高的VC/AA共聚物存在离子对聚集态结构;离子对含量、金属离子种类和增塑剂浓度影响离子聚集相的比例和稳定性,离子聚集具有热可逆性;离子交联使PVC的T_g、熔体粘度和回弹性提高.     

丙烯酰胺-苯乙烯双亲嵌段共聚物的微结构及水溶液行为

通过改变丙烯酰胺(AM)与苯乙烯(St)的投料比、苯乙烯与表面活性剂的加入量之比及引发剂加入量,在微乳液中制备了分子链微结构系列变化的丙烯酰胺-苯乙烯双亲嵌段共聚物(PAM-b-PSt),用荧光探针法与表面活性测定法详细地研究了共聚物中PSt嵌段长度、含量及分子量等微结构因素对共聚物在水溶液中的疏水缔合性与表面活性的影响.结果表明,当共聚物水溶液的浓度高于临界缔合浓度时,PAM-b-PSt的疏水缔合作用以分子间的缔合为主.若共聚物中PSt嵌段含量及分子链长一定时,随着PSt疏水嵌段长度增长,PAM-b-PSt的疏水缔合性增强,而对共聚物的表面活性影响很小.若共聚物中PSt疏水嵌段长度及分子链长一定时,PAM-b-PSt的疏水缔合性随着PSt嵌段含量的变化而变化,当PSt嵌段含量一定时,使大分子链之间产生最强的疏水缔合作用;而其表面活性则随着PSt嵌段含量的增大而增强.若共聚物中PSt疏水嵌段长度及含量一定时,分子量对其表面活性有较大的影响,分子量越高,表面活性越差;同时,在较稀的溶液浓度范围内,分子量对PAM-b-PSt的疏水缔合性的影响则很小.     

Novel approach to synthesizing hydrophobically associating copolymer using template copolymerization: the synthesis and behaviors of acrylamide and 4-(omega-propenoyloxyethoxy) benzoic acid copolymer

Hydrophobically associating copolymers of acrylamide (AM) with a small amount of 4-(omega-propenoyloxyethoxy) benzoic acid (PEBA, <2.5%) were synthesized by template copolymerization in the presence of poly(allylammonium chloride) (PAAC) as a template in an aqueous medium. These template copolymers exhibited remarkable thickening properties due to the effective hydrophobic association, which were similar to those copolymers with a multiblock structure obtained by the micellar process. The pH of the reaction medium and the molecular weight of the template strongly influenced the thickening properties of the products. In the experimental range, the higher the PEBA content, the larger the thickening capacity of these hydrophobic copolymers. The aggregate behaviors of these copolymers were studied by fluorescence, transmission electron microscopy (TEM), and light scattering techniques. The apparent critical interpolymer aggregate concentration (cac) of the copolymer solution was about 0.5 g/dL. As the concentration of the copolymer became higher than the cac, the aggregates changed their morphology from small hollow spheres to big flower-shaped aggregates. All the above results indicated that the template copolymerization gave access to a very simple and powerful means for the preparation of hydrophobically associating copolymers and other functional polymer materials.     

部分水解聚丙烯酰胺-羟乙基纤维素的水相pH响应性自组装

为考察无规共聚物在全水相环境中的自组装行为, 合成了结构类似于无规共聚物的低相对分子质量的部分水解聚丙烯酰胺(HPAM). 尝试改变水溶液pH值来诱导HPAM与羟乙基纤维素(HEC)发生自组装, 采用透射电子显微镜(TEM)观察到不同pH值时分别获得了100 nm的似正方体胶束, 200 nm×100 nm的类椭球胶束, 100 nm的串珠状胶束以及500 nm×300 nm×50 nm的半月形胶束等pH响应性核壳型聚合物胶束. 建立了金在胶束表面原位还原耦合TEM表征方法, 用于检测低衬度聚合物胶束的纳米细节; 配合电子探针X射线微区分析(EPMA)和扫描电子显微镜(SEM), 证实了半月形聚合物胶束的精致分级构造为亲水性内囊@疏水性连续囊壁@亲水性外壳的多泡囊泡, 并证实pH=0.9时多泡囊泡崩解为疏水性内核@亲水性外壳的10 nm类球体小胶束. 通过分析链节质子化状态的pH响应性, 结合zeta电位和吸光度测定结果, 阐释了不同pH值时组成聚合物胶束的核和壳的链段归属, 获得了全水相中HPAM自组装驱动力和形貌方面的全新知识.     

聚烯丙基氯化铵模板对AM/AA共聚物结构的影响

采用IR,1H-NMR和13C-NMR研究了聚烯丙基氯化铵(PAAC)模板对丙烯酰胺(AM)/丙烯酸(AA)共聚产物结构的影响,发现这种模板对共聚物P(AM/AA)序列结构和分子量有重要影响.由于共聚合体系中AA单体在PAAC模板聚合物上预组装,使得模板体系共聚物比无模板体系共聚物的AA和AM序列长度显著增加.这种类似多嵌段结构得到pKa′测定的进一步验证.另外模板分子量大小,模板和AA单体摩尔比,AM和AA摩尔比对共聚物结构的影响也进行了研究.应当指出这种模板聚合产物分离模板后仍有少量不能分离掉的PAAC聚合物存在.     

Temperature, pH, and ionic strength induced changes of the swelling behavior of PNIPAM-poly(allylacetic acid) copolymer microgels

The volume phase transition of colloidal microgels made of N-isopropylacrylamide (NIPAM) is well-studied and it is known that the transition temperature can be influenced by copolymerization. A series of poly( N-isopropylacrylamide- co-allylacetic acid) copolymers with different contents of allylacetic acid (AAA) was synthesized by means of a simple radical polymerization approach. The thermoresponsive behavior of these particles was studied using dynamic light scattering (DLS). Further characterization was done by employing transmission electron microscopy (TEM) and zeta potential measurements. TEM observations reveal the approximately spherical shape and low polydispersity of the copolymer particles. In addition, the measured zeta potentials provide information about the relative surface charge. Since these copolymers are much more sensitive to external stimuli such as pH and ionic strength than their pure PNIPAM counterparts, the volume phase transition was investigated at two different pH values and various salt concentrations. At pH 10 for the copolymer microgels with the highest AAA content, a significant shift of the volume phase transition temperature toward higher values is found. For higher AAA content, a change in pH from 8 to 10 can induce a change in radius of up to 100 nm making the particles interesting as pH controlled actuators.     

Stimuli‐responsive ABC triblock copolymers by sequential living cationic copolymerization: Multistage self‐assemblies through micellization to open association

Stimuli‐responsive ABC triblock copolymers with three segments with different phase‐separation temperatures were synthesized via sequential living cationic copolymerization. The triblock copolymers exhibited sensitive thermally induced physical gelation (open association) through the formation of micelles. For example, an aqueous solution of EOVE₂₀₀‐b‐MOVE₂₀₀‐b‐EOEOVE₂₀₀ [where EOVE is 2‐ethoxyethyl vinyl ether, MOVE is 2‐methoxethyl vinyl ether and EOEOVE is 2‐(2‐ethoxy)ethoxyethyl vinyl ether; the order of the phase‐separation temperatures was poly(EOVE) (20 °C) < poly(EOEOVE) (41 °C) < poly(MOVE) (70 °C)] underwent multiple reversible transitions from sol (<20 °C) to micellization (20–41 °C) to physical gelation (physical crosslinking, 41–64 °C) and, finally, to precipitation (>64 °C). At 41–64 °C, the physical gel became stiffer than similar diblock or ABA triblock copolymers of the same molecular weight. Furthermore, the ABC triblock copolymers exhibited Weissenberg effects in semidilute aqueous solutions. In sharp contrast, another ABC triblock copolymer with a different arrangement, EOVE₂₀₀‐b‐EOEOVE₂₀₀‐b‐MOVE₂₀₀, scarcely exhibited any increase in viscosity above 41 °C. The temperatures of micelle formation and physical gelation corresponded to the phase‐separation temperatures of the segment types in the ABC triblock copolymer. No second‐stage association was observed for AB and ABA block copolymers with the same thermosensitive segments found in their ABC counterparts. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2601–2611, 2004     

Preparation of monodispersed vinylpyridine–divinylbenzene porous copolymer resins and their application to high-performance liquid chromatographic separation of aromatic amines

For the separation of aromatic amines, two types of monodispersed porous polymer resins were prepared by the copolymerization of 2-vinylpyridine and 4-vinylpyridine with divinylbenzene in the presence of template silica gel particles (particle size 5 μm), followed by dissolution of the template silica gel in an alkaline solution. The transmission electron micrographs and the scanning electron micrograph revealed that these templated polymer resins have a spherical morphology with a good monodispersity and porous structure. Using these monodispersed polymer resins, the high-performance liquid chromatographic separation of aromatic amines in the mobile phases of pHs 2.0, 2.9, 4.1, 7.2 and 11.7 were carried out. The 2-vinylpyridine–divinylbenzene copolymer resins showed slightly stronger retentions for aromatic amines than the 4-vinylpyridine–divinylbenzene copolymer resins. Under acidic conditions (around pH 2.0), aniline and the toluidines showed no retention on these copolymer resins due to the repulsion between the cationic forms of these amines and pyridinium cations in the stationary phase, whereas less basic aromatic amines or non-basic acetanilide showed slight retentions. Above pH 4.1, the separation of aromatic amines with these polymer resins showed a typical reversed-phase mode separation. Therefore, the separation patterns of aromatic amines are effectively tunable by changing the pH value of the mobile phases. A good separation of eight aromatic amines was achieved at pH 2.9 using the 2-vinylpyridine–divinylbenzene copolymer resins.     

pH Responsivity and micelle formation of gradient copolymers of methacrylic acid and methyl methacrylate in aqueous solution

A series of gradient copolymers of methacrylic acid (MAA)/methyl methacrylate (MMA) with four end-to-end composition profiles (uniform, linear gradient, triblock with linear gradient midblock, and diblock) but all having an average chain composition of ?F(MMA) ≈ 0.5 and an average chain length of 200 were synthesized via model-based, computer-programmed, semibatch atom-transfer radical copolymerization (ATRcoP). These samples allowed us to investigate systematically the effects of the gradient composition profile on the pH responsivity and micelle formation of the copolymers in an aqueous solution. Measurements included light transmittance, TEM, AFM, DLS, (1)H NMR, and pH titration. It was found that linear gradient, triblock, and diblock copolymers formed spherical micelles at high pH. The micelles of the linear gradient copolymer contained MMA units in their hydrophilic shells, and those of the triblock and diblock copolymers had all of their MMA units residing in their cores. The composition profile showed a strong effect on the degree of acid dissociation at a given pH. The conformational transition of the copolymer chains was determined by both the pH value and composition profile. Copolymers having sharper gradients required a lower pH to trigger the conformational transition and a narrower pH range to complete the transition.     

甜菜碱型两性离子聚合物P(AM-DMAPAAS)的盐溶液性质

将丙烯酰胺丙基二甲基胺（DMAPAA）和1,3-丙基磺内酯,在55 ℃下反应20 h,合成了3-（丙烯酰胺丙基二甲胺基）丙磺酸盐（DMAPAAS）,将其在盐溶液中与丙烯酰胺（AM）单体进行自由基共聚合反应,获得净电荷为零的磺基甜菜碱型两性离子共聚物P(AM-DMAPAAS);对该两性离子共聚物进行了表征和溶解性评价。 研究结果表明,共聚物在NaCl溶液中的粘度比在纯水中的大,在Mg2+和Ca2+盐溶液中的粘度更大,且随着溶液浓度的增大而增大,表现出明显的反聚电解质溶液性质。 升高相同温度,两性离子共聚物的粘度保留率是普通聚丙烯酰胺的1.4倍。     

Radical methyl methacrylate—methacrylic acid copolymerization in isopropyl alcohol,acetone, and their mixtures. Application of the copolymer products for microencapsulation of ampicylline trihydrate

The copolymerization ratios of radical methyl methacrylate (MMA)-methacrylic acid (MA) copolymerization in mixtures of isopropyl alcohol (IPA) with acetone (A), xylene (X), and water (W) are determined. Their values and those in IPA are smaller than unity. The established alternating tendency of the monomer parts in the obtained copolymers is somewhat larger than the theoretically expected one and this is explained by the donor-acceptor interaction either between comonomers or between them and the propagating radicals. It is suggested that the reason for this tendency is the difference in H-bond formation between comonomers and solvents used. The dependencies of the apparent mass average molecular weight of the copolymers (M_{w, ap}) on their composition are also determined as well as the -composition of the A-heptane (H) mixture for these copolymers. These data are used for ampicyl line trihydrate (AT) microencapsulation by phase separation of the AT suspension in copolymer solutions in A after H addition. The AT microencapsulation characteristics (yield, degree and efficiency) as dependent on the copolymer composition as well as the influence of this composition on the solution kinetics of the microencapsulated AT at pH=4.5 and 6.5 and temperature of 37°C are established.     

pH快速响应PNIPAAm-co-PAAc水凝胶的制备及溶胀动力学

pH快速响应PNIPAAm-co-PAAc水凝胶的制备及溶胀动力学;N-异丙基丙烯酰胺;pH敏感性;溶胀历史