棉纤维的N-异丙基丙烯酰胺接枝共聚及产物的温敏性研究

以硝酸铈铵(CAN)、过硫酸钾(KPS)及H2O2/H2A(双氧水/抗坏血酸)为引发体系,采用溶液自由基接枝法制备了具有温敏性的棉纤维N-异丙基丙烯酰胺接枝共聚物(cotton-g-PNIPAAm);在上述3种引发剂作用下的接枝反应可以达到的接枝率(G)排序为G(H2O2/H2A)>G(KPS)>G(CAN);研究了其他因素如引发剂浓度、反应时间、反应温度和单体浓度等对接枝率的影响,得出了优化的接枝反应条件;接枝样品的FTIR分析图谱和SEM观察均表明样品表面已接枝了聚N-异丙基丙烯酰胺;DSC分析显示,棉纤维N-异丙基丙烯酰胺接枝共聚物的低临界溶解温度(LCST)与纯的聚N-异丙基丙烯酰胺凝胶(LCST=32.48℃)相似,约为32~33℃;接枝率的变化对试样LCST的影响很小,但其可逆焓变(ΔH)会随接枝率的提高而增加;采用滴水试验法(AATCC 79)和毛效试验法(FZ/T 01071)检测棉纤维的N-异丙基丙烯酰胺接枝共聚物在不同温度时的吸水性变化,显示试样具有温敏特性,其中接枝率介于25%~45%的试样温敏性较高,过低或过高的接枝率均不利于获得高的温敏性;棉纤维的N-异丙基丙烯酰胺接枝共聚物试样的可逆焓变(ΔH)随试样膨胀/收缩时间变化的研究和分析结果表明,棉纤维的N-异丙基丙烯酰胺接枝共聚物对温度变化的响应比纯聚N-异丙基丙烯酰胺凝胶快.     

含金刚烷基的N-异丙基丙烯酰胺共聚物水凝胶的制备和性能研究

合成了含金刚烷基的甲基丙烯酸金刚烷酯(AdMA)疏水单体,并通过与N-异丙基丙烯酰胺(NIPAM)共聚,制备了温敏性的(P(NIPAM-co-AdMA))共聚物水凝胶.用傅里叶变换红外光谱仪(FTIR)表征了凝胶的化学结构,用环境扫描电镜(ESEM)对凝胶断层结构的形貌进行了观察,用DSC测试了凝胶的体积相转变温度(LCST),并研究了共聚水凝胶的溶胀性能.结果表明,共聚物水凝胶的LCST能够高效地通过改变疏水单体的含量来调节,在实验所考察的范围内,LCST随AdMA含量的增加而线性降低;疏水单体的含量对凝胶的孔洞结构和溶胀性能存在一最优值,在最优的单体配比下,水凝胶具有均匀规整的大孔结构和超快的响应速率.如疏水单体含量为3%(AdMA∶NIPAM=3%)的共聚物水凝胶具有如渔网般均匀的多孔结构,当发生去溶胀时,在5min内就可以失去92%的水,不到10min的时间就可以完全达到去溶胀平衡,水保留率在4%以下.     

多孔聚N-异丙基丙烯酰胺水凝胶的制备与缓释性能

以N-异丙基丙烯酰胺(NIPA)、N,N-亚甲基双丙烯酰胺(MBA)和聚乙二醇(PEG)为原料,以60Co-γ射线为放射源制备了快速响应聚N-异丙基丙烯酰胺(PNIPA)多孔水凝胶。用红外光谱分析了水凝胶的结构,并测定了水凝胶的溶胀动力学、退溶胀动力学和平衡溶胀率。结果表明,PEG分子仅在聚合交联过程中充当成孔剂,不参与反应,反应后可被除去;水凝胶具有明显的温度敏感性,成孔剂的添加提高了水凝胶的溶胀性能和LCST。选用阿司匹林为模型药物,对水凝胶的药物缓释性能进行了初步研究。     

聚(N-异丙基丙烯酰胺)类材料的应用

聚(N-异丙基丙烯酰胺)(PNIPAAm)及其共聚物,在水溶液中表现出最低临界溶液温度(LCST),在LCST附近会发生可逆相转变。利用这种特性,可将热敏性高分子材料应用于生物医学工程、免疫分析、催化、分离提纯等领域。主要综述了热敏性PNIPAAm类高分子材料,在这些领域中的应用情况。     

光化学合成快速响应聚(N,N-二甲基丙烯酰胺-co-N-异丙基丙烯酰胺)水凝胶

通过光化学合成方法分别在高温(50℃)和室温(28℃)下实现了N,N-二甲基丙烯酰胺(DMAA)和N-异丙基丙烯酰胺(NIPAm)的交联共聚,制备了两种不同结构的P(DMAA-co-NIPAm)共聚物水凝胶.对两种温度下制备的P(DMAA-co-NIPAm)共聚物水凝胶的网络结构、溶胀与消溶胀速率和温度敏感性等方面进行了比较研究.结果发现,50℃下制备的P(DMAA-co-NIPAm)共聚物凝胶具有较为疏松的网络结构和相对较快的溶胀速率及温度响应特性.光化学合成方法较传统的热聚合制备方法具有简便、快捷的特点,合成过程仅需2 min.     

含疏水链节的聚N-异丙基丙烯酰胺共聚物的温敏性

采用溶液聚合法合成了一系列N-异丙基丙烯酰胺(NIPAM)与甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯或甲基丙烯酸丁酯的无规共聚物,用浊度观测法和光散射法测定了不同共聚物水溶液的温敏相转变行为.结果表明:所得共聚物的低临界溶解温度(LCST)均低于均聚物PNIPAM的,酯类单体的结构和含量对共聚物的LCST有显著影响,其中酯基上的烷基对共聚物LCST的影响能力大于丙烯酸酯α位上的烷基,前者对增大共聚物的疏水性有更大贡献.通过NIPAM与特定丙烯酸酯单体进行无规共聚可以合成转变温度低于PNIPAM均聚物且具有预设LCST数值的水溶性温敏聚合物.     

交联聚(N-异丙基丙烯酰胺)/(海藻酸钠/聚(N-异丙基丙烯酰胺))半互穿网络水凝胶的制备及其溶胀性能

将线性聚(N-异丙基丙烯酰胺)(PNIPAAm)和海藻酸钠(SA)分子同时引入到PNIPAAm凝胶中,制备了交联聚(N-异丙基丙烯酰胺)/(海藻酸钠/聚(N-异丙基丙烯酰胺))半互穿网络(Cr-PNIPAAm/(SA/PNIPAAm)semi-IPN)水凝胶。在弱碱性条件下(pH=7.4),改变SA与线性PNIPAAm的质量比对Cr-PNIPAAm/(SA/PNIPAAm)semi-IPN水凝胶的溶胀度没有太大的影响。在酸性条件下(pH=1.0),其溶胀度随着SA与线性PNIPAAm质量比的减小而增大。由于亲水性SA与线性PNIPAAm的协同作用,Cr-PNIPAAm/(SA/PNIPAAm)semi-IPN水凝胶的消溶胀速率得到很大提高。     

快速响应的温敏性聚(N-异丙基丙烯酰胺)水凝胶的合成及表征

快速响应的温敏性聚(N-异丙基丙烯酰胺)水凝胶的合成及表征;N-异丙基丙烯酰胺;水凝胶;温敏性;快速响应     

葡萄糖基N-异丙基丙烯酰胺共聚物合成及其温敏性

采用酶促法合成了可聚合的葡萄糖乙烯酯衍生物6-O-乙烯己二酰-D-葡萄糖(OVAG),通过自由基聚合法将N-异丙基丙烯酰胺和OVAG共聚,制备出了温敏含糖共聚物poly(OVAG-co-NIPAAm),通过1H NMR对聚合物的结构进行了表征,用凝胶色谱测定共聚物的相对分子质量。用可见光吸收法测定了poly(OVAG-co-NIPAAm)的低临界溶解温度(LCST),动态光散射测定了聚合物在水溶液中的流体力学直径,静态光散射测定了共聚物在水溶液中的均方旋转半径。结果表明,采用自由基聚合制备的温敏含糖共聚物在水溶液中自组装成近似球形的纳米粒子,其LCST由N-异丙基丙烯酰胺均聚物的32℃提高至39℃,粒径在60 nm左右,粒径分布较窄。     

聚(N-异丙基丙烯酰胺)/聚丙烯酰胺无机/有机互穿网络水凝胶的制备及表征

通过紫外引发聚合方法制备了无机交联的聚(N-异丙基丙烯酰胺)(PNIPAAm)/有机交联的聚丙烯酰胺(PAAm)互穿网络(IPN)水凝胶.利用FTIR和SEM分别表征了凝胶的化学结构和内部形态;测定了凝胶在高温(50℃)时的退溶胀性能;利用DMA和DSC分别研究了凝胶的储能模量随温度的变化及热相转变行为.研究表明,该IPN凝胶具有温度敏感性;与未互穿的无机交联PNIPAAm凝胶相比,IPN凝胶具有多孔的网络结构和超快的响应速率,如10min内失去90%的水;其储能模量增加了3～4倍,相转变行为变弱,而最低临界溶解温度(LCST)提高了1.4℃.     

温度及pH敏感聚(丙烯酸)/聚(N-异丙基丙烯酰胺)互穿聚合物网络水凝胶的合成及性能研究

合成聚（丙烯酸）／聚（Ｎ 异丙基丙烯酰胺）互穿聚合物网络（ＰＡＡｃ／ＰＮＩＰＡＩＰＮ）水凝胶，具有温度及ｐＨ双重敏感特性．这种水凝胶在弱碱性条件下的溶胀率远大于酸性条件下的溶胀率．在酸性条件下，随着温度上升，凝胶的溶胀率也随之逐渐上升；而在弱碱性条件下，温度低于聚（Ｎ 异丙基丙烯酰胺）（ＰＮＩＰＡ）的较低临界溶解温度（ＬＣＳＴ）时，溶胀率也随着温度的上升而上升，当温度达到ＬＣＳＴ时，凝胶的溶胀率突然急剧下降，并随着温度的逐渐上升而下降．     

Thermoresponsive hydrogel of poly(glycidyl methacrylate‐co‐N‐isopropylacrylamide) as a nanoreactor of gold nanoparticles

The synthesis of a thermoresponsive hydrogel of poly(glycidyl methacrylate‐co‐N‐isopropylacrylamide) (PGMA‐co‐PNIPAM) and its application as a nanoreactor of gold nanoparticles are studied. The thermoresponsive copolymer of PGMA‐co‐PNIPAM is first synthesized by the copolymerization of glycidyl methacrylate and N‐isopropylacrylamide using 2,2′‐azobis(isobutyronitrile) as an initiator in tetrahydrofuran at 70 °C and then crosslinked with diethylenetriamine to form a thermoresponsive hydrogel. The lower critical solution temperature (LCST) of the thermoresponsive hydrogel is about 50 °C. The hydrogel exists as 280‐nm spheres below the LCST. The diameter of the spherical hydrogel gradually decreases to a minimum constant of 113 nm when the temperature increases to 75 °C. The hydrogel can act as a nanoreactor of gold nanoparticles because of the coordination of nitrogen atoms of the crosslinker with gold ions, on which a hydrogel/gold nanocomposite is synthesized. The LCST of the resultant hydrogel/gold nanocomposite is similar to that of the hydrogel. The size of the resultant gold nanoparticles is about 15 nm. The hydrogel/gold nanocomposite can act as a smart and recyclable catalyst. At a temperature below the LCST, the thermoresponsive nanocomposite is a homogeneous and efficient catalyst, whereas at a temperature above the LCST, it becomes a heterogeneous one, and its catalytic activity greatly decreases. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2812–2819, 2007     

Effect of temperature cycling on the activity and productivity of immobilized β-galactosidase in a thermally reversible hydrogel bead reactor

The enzyme beta-galactosidase has been immobilized within thermally reversible hydrogel beads that exhibit LCST (lower critical solution temperature) behavior. The hydrogel beads containing the immobilized enzymes swell and expand below the LCST and deswell and shrink above the LCST. This behavior is reversible. The enzyme was physically entrapped in a crosslinked hydrogel of a copolymer of N-isopropylacrylamide (NIPAAm) and acrylamide (AAm), and formed as beads in an inverse suspension polymerization. The beads were placed in a packed bed column reactor which was operated in a continuous, single pass mode, either isothermally at 30 or 35 degrees C, or with temperature cycling between 30 and 35 degrees C. The thermal cycling significantly enhanced overall reactor enzyme activity relative to isothermal operation at either the higher or lower temperature. It is postulated that mass transfer rates within the hydrogel beads are greatly enhanced by the movement of water in and out of the beads during the expansion or collapse of the polymer chain network as temperature is cycled.     

A novel thermoresponsive hydrogel with ion-recognition property through supramolecular host-guest complexation

A novel thermoresponsive hydrogel with ion-recognition property was prepared via free-radical cross-linking copolymerization of N-isopropylacrylamide (NIPAM) with benzo-18-crown-6-acrylamide (BCAm) as host receptor. Both chemical structures and stimuli-sensitive properties of the prepared poly(N-isopropylacrylamide-co-benzo-18-crown-6-acrylamide) P(NIPAM-co-BCAm) hydrogel were characterized. The smart hydrogel could respond to both temperature and ion stimuli. When the crown ether units captured Ba2+ and formed stable BCAm/Ba2+ host-guest complexes, the lower critical solution temperature (LCST) of the hydrogel increased due to the repulsion among charged BCAm/Ba2+ complex groups and osmotic pressure within the hydrogel. Whereas crown ethers captured Cs+, the LCST shifted to a lower temperature because of the formation of 2:1 sandwich complexes. Unexpectedly, the LCST of the cross-linked P(NIPAM-co-BCAm) hydrogel in K+ solution did not shift to a higher temperature, which was definitely different from the previously reported linear P(NIPAM-co-BCAm) copolymer in K+ solution. The results of this work provide valuable information for development of dual thermo- and ion-responsive hydrogels which have potential applications in drug controlled-release systems or biomedical fields.     

Recognition‐Mediated Hydrogel Swelling Controlled by Interaction with a Negative Thermoresponsive LCST Polymer

Most polymeric thermoresponsive hydrogels contract upon heating beyond the lower critical solution temperature (LCST) of the polymers used. Herein, we report a supramolecular hydrogel system that shows the opposite temperature dependence. When the non‐thermosesponsive hydrogel NaphtGel, containing dialkoxynaphthalene guest molecules, becomes complexed with the tetra cationic macrocyclic host CBPQT⁴⁺, swelling occurred as a result of host–guest complex formation leading to charge repulsion between the host units, as well as an osmotic contribution of chloride counter‐ions embedded in the network. The immersion of NaphtGel in a solution of poly(N‐isopropylacrylamide) with tetrathiafulvalene (TTF) end groups complexed with CBPQT⁴⁺ induced positive thermoresponsive behaviour. The LCST‐induced dethreading of the polymer‐based pseudorotaxane upon heating led to transfer of the CBPQT⁴⁺ host and a concomitant swelling of NaphtGel. Subsequent cooling led to reformation of the TTF‐based host–guest complexes in solution and contraction of the hydrogel.     

Temperature-swing solid-phase extraction of heavy metals on a poly(N-isopropylacrylamide) hydrogel

The feasibility of temperature-swing adsorption of heavy metals on a thermosensitive N-isopropylacrylamide (NIPA) hydrogel was examined. We have proposed a novel temperature-swing solid-phase extraction (TS-SPE) technique. First, a metal ion in an aqueous solution is complexed with an extractant. Subsequently, the metal-extractant complexes (or micelles) are adsorbed onto the NIPA hydrogel through a hydrophobic interaction above the lower critical solution temperature (LCST). Finally, the metal-extractant complexes are desorbed from the NIPA hydrogel after it is cooled below the LCST. In a model system consisting of Cu(II) ions, sodium n-dodecylbenzenesulfonate (SDBS), and NIPA hydrogel, the proposed TS-SPE technique has been successfully conducted. The following observations can be made: the amount of adsorbed Cu(II) ions increases with the increase in temperature, the maximum adsorption is attained at a temperature above the LCST, and the hydrogel adsorbs and desorbs Cu(II) ions reversibly due to the temperature-swing between 10 and 40 degrees C. The LCSTs of poly(NIPA) in aqueous SDBS solutions with/without CuCl2 and the surface tensions of their solutions suggest that the hydrophobicity of the complex Cu(DBS)2 is greater than the hydrophobicities of SDBS and DBS. In addition to the separation of heavy metals, TS-SPE is potentially applicable to cases such as the separation of biological molecules by means of metal-ion affinity.     

Synthesis and characteristic of the thermo- and pH-sensitive hydrogel and microporous hydrogel induced by the NP-10 aqueous two-phase system

A series of novel thermo- and pH-sensitive (NP10-AA TPS) hydrogels and microporous (NP10-AA MP) hydrogels, inducing by polyoxyethylene (10) nonyl phenyl ether (NP-10) aqueous two-phase system, was designed and fabricated with acrylic acid (AA) as the monomer for the first time. The resultant NP10-AA TPS hydrogel, compared with the traditional TPS hydrogel, was more advanced in both of the high swelling ratio and the variable lower critical solution temperature (LCST). A simple synthesis technique of the NP10-AA MP hydrogel was developed. The thermo-sensitivity of the NP10-AA TPS hydrogel including the initial swelling ratio, LCST, dehydrated efficiency, was depended strongly on the crosslinker (MBA), initiator (APS), NP-10 and AA concentration. The swelling rate of the NP10-AA MP hydrogel was much higher than that of AA hydrogel dehydrated in the same lyophilization condition.     

温度及pH敏感性共聚物水凝胶的合成及其对辅酶A的控制释放

以N-乙烯基吡咯烷酮(NVP)和甲基丙烯酸-N,N-二甲胺乙酯(DMAEMA)为单体,采用自由基聚合法合成了NVP与DMAEMA的共聚物及其水凝胶。研究发现共聚物的水溶液具有温度及pH双重敏感特性。相分离温度随DMAEMA含量的增加和水溶液浓度的降低而升高,随pH值的增大而减小且相变敏锐。通过对水凝胶溶胀率的考察,发现共聚凝胶在适当的单体浓度及交联剂浓度下,有较敏感的溶胀-退胀行为。在碱性条件下,共聚凝胶随温度的升高迅速退胀。pH=9时,改变温度,对辅酶A有很好的控制释放;而在酸性条件下,则无退胀行为,对辅酶A不能释放。     

单分散CdS纳米晶/PNIPAM复合水凝胶的制备及其温敏荧光特性

采用液体-固体-溶液法(LSS)制备单分散CdS纳米晶;通过自由基聚合制备单分散CdS纳米晶/聚N-异丙基丙烯酰胺(CdS/PNIPAM)复合温敏水凝胶.采用HRTEM、XRD、FTIR、DSC、PL等对CdS纳米晶、CdS/PNIPAM温敏复合凝胶的微观结构与性能进行了表征,变温荧光光谱研究了温度对凝胶荧光性能的影响.结果表明,CdS纳米晶粒径约为2.8 nm,单分散性良好;复合凝胶的荧光发射强度与环境温度存在一定的关联性,且呈可逆性.     

新型pH及温度敏感性水凝胶

水凝胶是由三维交联网络结构的高聚物和介质共同组成的多元体系 ,因其独特的刺激响应行为 ,已在药物释放体系、物料分离、化学机械、人工肌肉等领域显示了良好的应用前景[1,2 ] .在人体体液这种复杂的环境中 ,水凝胶同时受到ｐＨ和温度等多重刺激作用 ,因此 ,研究多重响应性水凝胶具有重要意义 .聚氨酯作为一种广泛应用的高分子材料具有结构易调节、力学性能优异及生物相容性好等特点 ,在生物医学领域可将其用作假肢部件、外科用置入管、隐形眼睛等 .已有文献报道了ｐＨ敏感性聚氨酯水凝胶[3～ 5] ,但对多重响应性聚氨酯基水凝胶的报道还很…