一种快速响应电场敏感多孔水凝胶的合成及其性能研究

以4-乙酰基丙烯酰乙酸乙酯(AAEA)、2-丙烯酰胺基-2-甲基-1-丙磺酸(AMPS)为单体,不同分子量的聚乙二醇(PEG)为成孔剂,通过自由基溶液聚合法,合成了新型多孔快速响应电场敏感性水凝胶.结果表明,成孔剂PEG被洗脱后在凝胶内部形成了互相贯穿的孔洞结构,孔径在30～120μm之间.以PEG6000为成孔剂致孔后的多孔凝胶溶胀速率和消溶胀速率最快,在去离子水中30s达到溶胀平衡,在0.1mol/L的NaCl溶液中40min达到消溶胀平衡;电场作用下凝胶的消溶胀速度大大加快,12min内即可达到平衡.凝胶中AMPS含量的增多会加快凝胶在电场中的响应速度;而高温下,随着AAEA含量的增加,凝胶内部疏水基团增多并收缩产生大量的疏水微区,限制了凝胶内部水分的持续排出,因此n(AAEA)∶n(AMPS)=3∶1的凝胶4min内即可排出表面水分达到消溶胀平衡,可保水率却高达75%.同时,增大电解液的pH值、浓度以及提高电解电压,均会加快凝胶的消溶胀行为.     

P(AMPS-co-BMA)水凝胶的电场敏感性及电刺激响应机理

以离子型单体2-丙烯酰胺-2-甲基丙磺酸(AMPS)及非离子型单体甲基丙烯酸丁酯为原料, 偶氮二异丁腈为引发剂, N,N′-亚甲基双丙烯酰胺为交联剂, N,N-二甲基甲酰胺为溶剂, 通过自由基聚合合成了一系列聚离子浓度不同的聚(2-丙烯酰胺-2-甲基丙磺酸-co-甲基丙烯酸丁酯)电场敏感性水凝胶. 研究了其在去离子水及NaCl溶液中的溶胀行为. 结果表明, 该水凝胶在去离子水中的平衡溶胀度在236.4~298.5之间, 其溶胀速率随着AMPS用量的增加而增加; 并且随着凝胶内部聚离子浓度的增加, 凝胶在NaCl溶液中的消溶胀速率及消溶胀度逐渐减小. 凝胶的电刺激响应性能研究结果表明, 在电场存在下, 凝胶在NaCl溶液中的溶胀行为与凝胶内部聚离子浓度和溶液中NaCl浓度的相对大小有关, 当凝胶内部聚离子浓度大于溶液中NaCl浓度时, 凝胶溶胀, 反之则凝胶消溶胀; 而且, 凝胶在电场作用下的偏转行为同样与凝胶内部聚离子浓度和溶液中NaCl浓度的相对大小有关, 当凝胶内部聚离子浓度大于溶液中NaCl浓度时, 偏向阴极, 反之则凝胶偏向阳极. 另外, 在电场存在下, 凝胶在NaCl溶液中的电偏转速度与环境温度密切相关.     

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。     

PAMPS/SiO_2杂化水凝胶的合成及电场敏感性研究

以2-丙烯酰胺-2-甲基丙磺酸(AMPS)为有机原料,正硅酸乙酯(TEOS)为无机原料,过硫酸钾为引发剂,N,N'-亚甲基双丙烯酰胺为交联剂,通过原位-凝胶水溶液聚合法合成了一系列不同二氧化硅含量和不同聚离子浓度的聚(2-丙烯酰胺-2-甲基丙磺酸)/二氧化硅杂化电场敏感性水凝胶.通过扫描电子显微镜(SEM)表征凝胶的结构,研究水凝胶在去离子水以及氯化钠溶液中的溶胀和消溶胀行为.结果表明,系列凝胶的平衡溶胀度介于224.9至325.6之间,复合凝胶的溶胀速率随TEOS用量的增加而降低;除理想杂化凝胶外,随着聚离子浓度的升高,凝胶在氯化钠溶液中的消溶胀速率逐渐减小.对凝胶的电场敏感性研究表明,当聚离子浓度大于氯化钠溶液浓度时,凝胶进一步溶胀,反之则消溶胀,其中杂化凝胶的再溶胀性能减弱,而消溶胀行为变得更为明显.同时制得的理想杂化凝胶,较纯有机凝胶具有更为理想的力学性能,最大抗压缩强度可达23.4 MPa.     

PVP-P(AAEA-co-AA)/纳米金温度-电场双重敏感性凝胶的制备及性能

采用溶液聚合法以聚乙烯吡咯烷酮(PVP)为第二网络,以丙烯酸(AA)、4-乙酰基丙烯酰乙酸乙酯(AAEA)为单体制备PVP-P(AAEA-co-AA)半互穿水凝胶(PVP-SIPN),再通过原位还原法合成PVP-P(AAEA-co-AA)/纳米金复合凝胶(GNPs gel),探讨凝胶的溶胀/消溶胀性能、温度及电场敏感性。研究表明,随PVP用量的增加PVP-SIPN溶胀速率减小,平衡溶胀度降低;当PVP用量低于5%凝胶保水率随PVP用量增加而降低,高于5%时保水率随PVP用量增加而增加;PVP-SIPN相转变温度升高,且凝胶温度敏感性随之减弱。纳米金的加入导致凝胶平衡溶胀度从82.3g/g降低至22.66g/g,在电场作用下,外界离子浓度小于0.2mol/L时,GNPs gel发生溶胀;反之,消溶胀,凝胶消溶胀速率随外界电压增大而增大。     

P(AMPS-co-HEMA)凝胶的合成与吸银性能研究

以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)和甲基丙烯酸羟乙酯(HEMA)为单体,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,过硫酸钾(KPS)为引发剂,采用自由基水溶液聚合法制备P(AMPS-co-HEMA)共聚凝胶,通过傅里叶红外光谱(FT-IR)对材料结构进行了表征.研究单体配比、交联剂的用量、引发剂的用量对共聚凝胶吸水性能的影响,并在此基础上对凝胶的溶胀、吸银及消溶胀性能进行研究.结果表明,当单体摩尔比n(AMPS)∶n(HEMA)=2∶1,交联剂用量ω(MBA)=0.6％,引发剂用量ω(KPS)=0.8％,所制得的凝胶吸水性能最好;凝胶在蒸馏水中的溶胀过程属于松弛平衡扩散;凝胶在AgNO3溶液中60min左右达到消溶胀平衡,且当AgNO3溶液的浓度为0.05mol/L时,银离子吸附量最大,为0.04g/g,消溶胀速率最快.     

聚丙烯酰胺/聚异丙基丙烯酰胺互穿网络水凝胶的制备与性能

采用分步法用电子加速器辐射合成了聚丙烯酰胺(PAAm)/聚异丙基丙烯酰胺(PNIPAAm)互穿网络水凝胶,并考察了温度、pH值、离子强度对其溶胀性能的影响.研究表明:互穿水凝胶具有温度敏感性,且其体积相变与互穿网络中PAAm和PNIPAAm含量有关,随着网络中PAAm含量的增加水凝胶的体积相变趋于平缓,可以通过改变PAAm和PNIPAAm的组成比来控制水凝胶的体积相变行为.此外,互穿水凝胶还具有pH敏感性和一定的抗盐性.     

亲水/疏水半互穿网络凝胶在直流电场作用下的响应

研究了一种亲水 疏水型半互穿网络水凝胶 (PAAc QPVPDgels)对直流电场的刺激应答 .该凝胶中的疏水型N 十二烷基聚 (4 乙烯吡啶 )溴化盐 (QPVPD)高分子链与亲水型聚丙烯酸水凝胶 (PAAc)网络通过物理缠绕复合 .由于疏水力和亲水力的共同作用 ,在接触电场下 ,该凝胶在阳极端发生消溶胀 ,疏水相互作用对消溶胀有一定的影响 ;在非接触电场下 ,该凝胶在弱碱性溶液中迅速向阴极方向弯曲 ,在弱酸性溶液中首先发生消溶胀 ,然后向阳极方向弯曲     

温敏性聚(N-异丙基丙烯酰胺)水凝胶的合成与表征

以不同粒径的硅胶颗粒为致孔剂制备了多孔的聚(N-异丙基丙烯酰胺)(PNIPAAm)水凝胶,用DSC对其相转变温度进行了表征,并测定了不同温度下达到溶胀平衡时水凝胶的溶胀率,研究了水凝胶的退胀机理及收缩凝胶的再溶胀机理。实验证明,多孔凝胶相对于无孔凝胶其溶胀性能有较大提高,孔结构的存在大幅度提高了水凝胶的响应速率,尤其是退胀速率。     

P(AA-co-DMDAAC)/PVA凝胶的制备和吸金性能研究

以丙烯酸(AA)、二甲基二烯丙基氯化铵(DMDAAC)为单体,聚乙烯醇(PVA)为第二网络,通过水溶液聚合法制备P(AA-co-DMDAAC)/PVA半互穿水凝胶(SIPNH)。采用FT-IR、XRD、SEM等对凝胶的结构进行了表征。结果表明,PVA用量为5%时,PVA与P(AA-co-DMDAAC)能形成较完善的半互穿网络结构。探讨了凝胶的抗压缩性能、溶胀/消溶胀性能。结果表明,SIPNH形成的半互穿网络结构可以改善凝胶的抗压缩强度,最大抗压缩强度达到0.37MPa。凝胶的溶胀/消溶胀速率随PVA用量的增加呈下降趋势。着重研究了PVA及氯金酸(HAuCl4)用量对SIPNH吸金能力的影响。结果表明,PVA用量大于5%时,SIPNH的吸金能力明显降低。当HAuCl4浓度为250mg/L时,最大吸附量为108.5mg/g。     

Porous alginate-Ca hydrogels interpenetrated with PNIPAAm networks: Interrelationship between compressive stress and pore morphology

Thermo-sensitive porous hydrogels composed of interpenetrated networks (IPN) of alginate-Ca²⁺ and PNIPAAm have been obtained. The hydrogels were prepared by cross-linking alginate-Na⁺ with Ca²⁺ ions inside PNIPAAm networks. Compressive tests and scanning electron microscopy were used to evaluate gel strength and pore morphology, respectively. IPN hydrogels displayed two distinct pore morphologies under thermal stimuli. Below 30-35 °C, the LCST of PNIPAAm in water, IPN hydrogels were highly porous. The pore size of hydrogel heated above LCST became progressively smaller. Alginate-Ca²⁺ and PNIPAAm hydrogels, used as references, did not present such behaviour, indicating that the porous effect is due to IPN hydrogel. It was verified that higher strength is achieved when the hydrogel presents small pore size and the temperature is increased. It is suggested that at temperatures above LCST, the PNIPAAm chains shrink and pull the alginate-Ca²⁺ networks back. During shrinking, the polymer chains occupy the open spaces (pores from which water is expelled), and therefore, the hydrogel becomes less deformable when subjected to compressive stress. The results presented in this work indicate that the mechanical properties as well as the pore morphologies of these IPN hydrogels can be tailored by thermal stimulus.     

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℃.     

Fast synthesis of temperature-sensitive PNIPAAm hydrogels by microwave irradiation

A novel method, microwave irradiation synthesis, is proposed for the preparation of thermo-sensitive poly(N-isopropylacrylamide) (PNIPAAm) hydrogels. The PNIPAAm hydrogels were separately synthesized by using microwave irradiation method and water-bath heating method. Chemical groups, lower critical solution temperature (LCST) and surface morphology of these PNIPAAm hydrogels were characterized by FT-IR, DSC and SEM. Swelling ratios of the gels were measured gravimetrically in the temperature range from 10.0 to 60.0 °C. Results showed that (1) the use of microwave irradiation can greatly shorten the reaction time required for PNIPAAm hydrogel synthesis from several hours to several minutes in comparison with water-bath heating method, and obviously improve the yields of the PNIPAAm gels, which were up to 99% after a short reaction time; (2) SEM micrographs and textural measurement revealed that the gels synthesized using microwave irradiation had more porous structure, and their average pore sizes and specific surface areas were larger than those of the gels synthesized using water-bath heating method; and (3) the PNIPAAm hydrogels synthesized using microwave irradiation had much higher swelling ratios at 10.0 °C below the LCST, and had lower swelling ratio at 60.0 °C above the LCST compared to the hydrogels synthesized by water-bath method.     

Rapid deswelling of sodium alginate/poly(N-isopropylacrylamide) semi-interpenetrating polymer network hydrogels in response to temperature and pH changes

In this study, temperature-/pH-responsive semi-interpenetrating polymer network (semi-IPN) hydrogels based on linear sodium alginate (SA) and cross-linked poly(N-isopropylacrylamide) (PNIPAAm) were prepared. The semi-IPN hydrogels reached an equilibrium deswelling state within 6 h in response to temperature or pH stimuli. Compared with the conventional PNIPAAm hydrogel, their dewelling rate in response to temperature was improved significantly, owing to the formation of a porous structure within the hydrogels in the presence of ionized SA during the polymerization process. Moreover, the deswelling process could be well described with a first-order kinetics equation and it is possible to design any hydrogel with the desired deswelling behavior through the control of the SA content in the semi-IPN hydrogels.     

Fast responsive poly(N-isopropylacrylamide) hydrogels prepared in phenol aqueous solutions

Fast responsive poly(N-isopropylacrylamide) (PNIPAAm) hydrogels with improved properties were prepared in phenol aqueous solutions with different concentrations. Due to the expanded network structure in water, the resulted hydrogels are capable of absorbing a large amount of water, i.e. exhibits a much increased swelling ratio at room temperature. Importantly, the hydrogels demonstrated much faster response rate than that of traditional PNIPAAm hydrogel upon external temperature increase.     

Effect of the crosslinking level on the properties of temperature‐sensitive poly(N‐isopropylacrylamide) hydrogels

In this study, the effect of the level of crosslinking on the properties of poly(N‐isopropylacrylamide) (PNIPAAm) hydrogels was investigated in terms of their lower critical solution temperature (LCST), interior morphology, equilibrium swelling, and deswelling and swelling kinetics. The thermal analysis showed that PNIPAAm hydrogels, having a wide range of crosslinking levels, exhibited almost the same LCSTs, and this was different from what the conventional theory would have predicted. Scanning electron micrographs revealed that the interior network structure of the PNIPAAm matrix became more porous with an increase in the level of crosslinking. This more porous matrix provided numerous water channels for water diffusion in or out of the matrix and, therefore, an improved response rate to the external temperature changes during the deswelling process and the swelling process. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 582–593, 2003     

Structure and properties of cellulose/poly(N‐isopropylacrylamide) hydrogels prepared by IPN strategy

Interpenetrating polymer network (IPN) strategy was developed to fabricate novel hydrogels composed of cellulose and poly(N‐isopropylacrylamide) (PNIPAAm) with high mechanical strength and adjustable thermosensitivity. Cellulose hydrogels were prepared by chemically cross‐linking cellulose in NaOH/urea aqueous solution, which were employed as the first network. The second network was subsequently obtained by in situ polymerization/cross‐linking of N‐isopropylacrylamide in the cellulose hydrogels. The results from FTIR and solid ¹³C NMR indicated that the two networks co‐existed in the IPN hydrogels, which exhibited uniform porous structure, as a result of good compatibility. The mechanical and swelling properties of IPN hydrogels were strongly dependent on the weight ratio of two networks. Their temperature‐sensitive behaviors and deswelling kinetics were also discussed. This work created double network hydrogels, which combined the advantages of natural polymer and synthesized PNIPAAm collectively in one system, leading to the controllable temperature response and improvement in the physical properties. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of Sodium Alginate on the Properties of Thermosensitive Hydrogels

Sodium alginate (SA ) was combined with poly(N ‐isopropylacrylamide) (PNIPAAm ) to prepare thermosensitive hydrogels through semi‐interpenetrating polymer network (semi‐IPN ) and fully interpenetrating polymer network (full‐IPN ). The thermosensitive, swelling, mechanical, and thermal properties of pure PNIPAAm , SA /PNIPAAm semi‐IPN , and Ca‐alginate/PNIPAAm full‐IPN hydrogels were investigated. The formation of semi‐IPN and full‐IPN significantly improved the hydrogels’ swelling capability and mechanical properties without altering their thermosensitivity. 5‐Fluorouracil (5‐Fu) was selected as a model drug to study the release behaviors of the hydrogels. It was found that in vitro controlled drug release from semi‐IPN hydrogels showed an initial release burst, followed by a slower and sustained release, before reaching equilibrium. Full‐IPN hydrogels showed slow and sustained release during the whole process. Temperature and pH were found to affect the rate of drug release. Ca‐alginate/PNIPAAm full‐IPN hydrogels have potential application as drug delivery matrices in controlled drug release.