PVA增强P(AAEA-co-AA)温度敏感性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)、丙烯酸(AA)以及PVA为原料, 通过自由基溶液聚合法, 制备了PVA-P(AAEA-co-AA)半穿网络型(s-IPN)水凝胶. 红外分析表明, AAEA主要以烯醇式结构存在, 并且由于PAAEA, PAA以及PVA之间较强的氢键作用, 使得PAAEA以及PVA分子上的C-O伸缩振动吸收峰移向了低波数处. 电镜分析表明, PVA能贯穿于P(AAEA-co-AA)交联网络中, 从而有效阻碍凝胶的相分离|而XRD研究发现, 当PVA用量较少时, PVA能均匀的贯穿于凝胶网络中, 形成完善的互穿网络结构, 当PVA用量过高时, PVA不能有效地贯穿于聚合物交联网络中而出现结晶. 采用DSC对s-IPN水凝胶的体积相转变进行了研究, 结果表明, 该s-IPN水凝胶的体积相转变温度(VPTT)在54.0至57.8 ℃之间, 并且随着PVA用量的增加, 凝胶的VPTT逐渐升高. 研究了该s-IPN水凝胶的抗压缩性能, 结果表明, PVA与P(AAEA-co-AA)形成的半互穿网络结构能有效提高凝胶的抗压缩强度, 其最大抗压缩强度可达8.4 MPa. 对凝胶的温度敏感性研究发现, 当外界温度低于VPTT时, 凝胶能保持溶胀状态|而当温度高于VPTT时, 凝胶的平衡溶胀度迅速下降, 表现为温度敏感性.     

大孔PAMPS/PVA半互穿网络型水凝胶的制备及其性能研究

以PEG6000为成孔剂, 合成了大孔聚(2-丙烯酰胺-2-甲基丙磺酸)/聚乙烯醇半互穿网络型(s-IPN)水凝胶. 红外分析表明, PVA与PAMPS之间形成了较强的氢键, 使得PVA分子上的C—O伸缩振动吸收峰移向了低波数处. X射线衍射分析发现, 当PVA用量较高时, 由于部分的PVA结晶, 使得凝胶的半互穿网络结构不均匀. 电镜分析结果表明, 没有使用成孔剂的凝胶表面成褶皱形, 不存在任何孔洞结构; 而以PEG6000为成孔剂的凝胶表面存在相互贯穿的大孔结构. 研究了该水凝胶的溶胀性能, 结果表明, 该水凝胶的平衡溶胀度在116至320之间; 而成孔剂PEG6000的加入能较大幅度提高凝胶的溶胀速率, 凝胶在240 min之内就能达到溶胀平衡. 对凝胶抗压缩性能的研究表明, 当PVA用量为9.1% (w)时, 凝胶的抗压缩强度最大, 可达12.0 MPa; 而成孔剂的加入会在一定程度削弱凝胶的抗压缩强度. 该凝胶具有较好的电场敏感性, 研究发现, 将吸去离子水达到溶胀平衡的凝胶放入施加有电场的0.2 mol•L－1 NaCl溶液中时, 凝胶迅速偏向阳极. 而PVA和成孔剂PGE6000的用量均对凝胶的偏转速度以及最大偏转角存在较大的影响.     

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。     

温度和pH敏感P（NIPA／AA）／黏土互穿网络水凝胶的辐射合成与表征

以N-异丙基丙烯酰胺(NIPA)和丙烯酸(AA)为聚合单体、有机黏土作为改性剂,采用60Co-γ射线为放射源,辐射合成了P(NIPA/AA)/黏土互穿网络(IPN)水凝胶,研究了IPN的表面形貌以及AA浓度、黏土对水凝胶溶胀性能和压缩性能的影响.SEM电镜观察表明:P(NIPA/AA)共聚水凝胶的表面致密,没有明显相分离,而IPN凝胶表面疏松多孔且非连续,有明显的相分离,形成了较好的IPN结构.P(NIPA/AA)IPN水凝胶在碱性和弱碱性溶液中的溶胀率高,且其溶胀速率由网络中高分子链的松弛运动控制;而在酸性介质中,水分子的扩散为水凝胶溶胀的决定过程.P(NIPA/AA)IPN水凝胶具有良好的力学性能,加入黏土后凝胶的压缩性能参数均有不同程度的提高,水凝胶受压时只发生塑性变形,没有被破坏.     

P(AA-DAC)两性聚电解质水凝胶的合成及性质

以丙烯酸(AA)和丙烯酰氧乙基三甲基氯化铵(DAC)为单体, 采用水溶液聚合法制备了P(AA-DAC)聚电解质水凝胶. 采用红外光谱和核磁共振等方法对其结构进行了表征. 研究了不同组成比的聚电解质水凝胶在去离子水、不同pH值溶液以及不同离子强度盐溶液中的溶胀行为. 研究结果表明, 摩尔比为1∶1的聚电解质水凝胶表现出典型的两性聚电解质凝胶的溶胀行为. 离子强度对其溶胀行为有着显著影响, 在溶液离子强度较高时, 凝胶网络的溶胀主要受溶剂向凝胶内部扩散所控制, 满足Fick型扩散规律n≤0.5, 随着溶液离子强度的增加, 凝胶网络平衡含水量增加, 扩散系数增大.     

聚乙烯醇/丙烯酸共聚物水凝胶的制备及溶胀性

制备了具有pH敏感性的聚乙烯醇(PVA)/丙烯酸(AA)共聚物水凝胶,研究了PVA与AA之间配比、交联剂、引发剂用量对凝胶转化率的影响,对水凝胶的溶胀行为和pH敏感性也进行了详细研究.实验表明PVA与AA的质量比为(1∶9)~(3∶7)之间时,引发剂和交联剂分别为PVA和AA总量的0.2%和0.3%时,凝胶转化率高.随着水溶液pH值从3增加到9,凝胶的溶胀比也相应的增加,表现出明显的pH敏感性.     

PVA改性PAMPS-PAM超高力学性能双网络水凝胶的制备

采用紫外光引发聚合制备了聚乙烯醇(PVA)改性的聚(2-丙烯酰胺基-2-甲基丙磺酸)-聚丙烯酰胺(PAMPS-PAM)双网络(DN)水凝胶.测定并比较了PVA改性前后PAMPS-PAM双网络水凝胶的溶胀动力学;通过扫描电子显微镜(SEM)观察了单网络水凝胶的结构;测定PVA改性前后PAMPS-PAM双网络水凝胶的压缩及拉伸性能.结果表明,经PVA改性后的PAMPS-PAM双网络水凝胶有较高的溶胀比;0.82%PVA用量的PAMPS-PAM双网络水凝胶在90%压缩形变率下仍保持完整、最大拉伸应力达到0.5 MPa,大幅提高PAMPS-PAM双网络水凝胶的力学性能.     

先辐射后冻融法制备聚乙烯醇/水溶性壳聚糖/甘油水凝胶的云南白药药物释放性能研究

采用先辐射后冻融的方法制备了一系列聚乙烯醇(PVA)/水溶性壳聚糖/甘油水凝胶,通过浸泡法在水凝胶中载入云南白药,并且研究了溶液pH值、离子强度、冻融次数和PVA浓度对水凝胶溶胀性能和云南白药释放性能的影响.研究发现水凝胶的溶胀度随溶液离子强度的增大而下降,且酸性溶液大于中性溶液.水溶性壳聚糖的加入有利于云南白药载入凝胶,同时使云南白药的释放具有pH和离子强度敏感性.云南白药的释放量在模拟体液中最大,在中性溶液中次之,在水和酸性溶液中最小,与溶胀度变化关系相反.而水凝胶的溶胀度和云南白药释放量均随冻融次数和PVA浓度的增大而下降.分析表明,云南白药在不同介质中的释放量主要取决于药物和溶液中离子的交换能力;在相同介质中,不同凝胶的药物释放量受溶胀度影响明显.凝胶溶胀速率远大于药物释放速率说明后者主要由扩散过程控制.药物释放的pH敏感性表明该水凝胶具备用作云南白药的口服载体的潜力.     

超大孔P(AA-co-AM)/PVA水凝胶的制备及吸附性能研究

采用泡沫分散聚合法,以饱和Na2CO3水溶液为发泡剂,过硫酸铵(APS)及NaHSO3为引发剂,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,聚(氧化乙烯/氧化丙烯)(PF127)为泡沫稳定剂,丙烯酸(AA)和丙烯酰胺(AM)为单体,聚乙烯醇(PVA)为第二网络,制备超大孔半互穿水凝胶P(AA-co-AM)/PVA,并研究其对阳离子兰染料的吸附性能。研究表明,P(AA-co-AM)/PVA具有相互贯穿的超大孔结构;当n(AM):n(AA)=1.5:1,w(PVA)=1.6%时凝胶的平衡溶胀度达186.56g/g;凝胶具有很好的离子响应性,在蒸馏水中的平衡溶胀度为129.16g/g时,在0.1mol/L NaCl溶液中只有31.07g/g;对阳离子兰染料溶液的脱色率达92.17%,吸附容量达17.16mg/g。     

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.     

Synthesis and Properties of IPN Hydrogels Based on Konjac Glucomannan and Poly（acrylic acid）

As a random copolymer of β-(1,4) linked D-mannose and D-glucose, konjac gluco- mannan (KGM) is a naturally occurring water-soluble polysaccharide, and has been paid attention in the field of drug controlled release carriers potentially used in colon1,2. …     

瓜胶/聚丙烯酸互穿聚合物网络水凝胶对模型药物的负载与控制释放

考察了以牛乳清蛋白(BSA)为模型药物,通过相平衡分配法制备载药瓜胶(GG)/聚丙烯酸(PAA)互穿聚合物网络(IPN)水凝胶的工艺条件.借助紫外可见光谱仪研究了载药水凝胶在结肠酶存在下的控制释放行为.结果表明:载药容量(CM)随瓜胶、丙烯酸用量的增加而下降,半IPN水凝胶的Cm较全IPN的略大;结肠酶能明显提高半IPN与全IPN中的BSA释放速率,且提高幅度随GG含量的增加而加快,GG/PAA IPN水凝胶具有结肠定位降解的特性,有望成为靶向结肠给药的理想载体材料.     

PVA/PAA thermo-crosslinking hydrogel fiber: preparation and pH-sensitive properties in electrolyte solution

The preparation of thermo-crosslinking hydrogel fibers composed of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) was presented. The hydrogel fiber was prepared by extruding the spinning dope from in situ polymerization of acrylic acid in the presence of PVA into coagulating bath of saturated ammonium sulfate aqueous solution. The network was formed by thermally heating the dried fibers under vacuum. The final hydrogel fibers exhibit pH-sensitive behavior and show hysteresis loop in the pH range from 2.5 to 12.5. The pH value at which the swelling ratio of the fiber had a jump shifted to lower value with increasing the PAA content within the network. Increasing the heating temperature and time for the fibers, the swelling ratio decreased and the jump point pH shifted to higher pH value. The oscillatory swelling/contracting behavior of the hydrogel fiber exhibited a well reversible pH-responsive property.     

pH敏感的聚(L-谷氨酸)-交联聚丙烯酸水凝胶的合成与性能研究

通过在聚L-谷氨酸侧链部分接枝甲基丙烯酸2-羟乙酯得到含有双键的聚(L-谷氨酸),将其与丙烯酸共聚得到由聚(L-谷氨酸)侧链接枝并交联聚丙烯酸的pH敏感水凝胶.研究水凝胶在不同pH的缓冲溶液中的溶胀性、溶胀动力学,并通过SEM观察水凝胶的微观结构.结果表明,水凝胶在低pH环境下的溶胀率明显低于高pH环境中的溶胀率,不同...     

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.     

Ultrastretchable,Tough, and Notch‐Insensitive Hydrogels Formed with Spherical Polymer Brush Crosslinker

Spherical polymer brushes, poly(acrylic acid) (PAA)‐grafted polystyrene nanoparticle (PAA@PS), are employed as the macro‐crosslinker to prepare PAA hydrogels. Benefitting from the innumerable hydrogen bonds between highly entangled PAA chains both in bulk and on the polymer brush, the PAA/PAA@PS hydrogels combine desirable stretchability, toughness, and notch‐insensitivity. The uniaxial tensile tests show a very high fracture elongation up to 9.1 × 10³% while the fracture toughness reaches 3.0 MJ m⁻³ and the maximum swelling ratio of the hydrogel can be 2.0 × 10³ as well. After being loaded with silver nanoparticles, the PAA/PAA@PS hydrogels are employed as a recyclable catalyst successfully.     

Synthesis,characterization, and swelling behaviors of chitosan‐g‐poly(acrylic acid)/poly(vinyl alcohol) semi‐IPN superabsorbent hydrogels

A series of granulated semi‐interpenetrating polymer network (semi‐IPN) superabsorbent hydrogels composed of chitosan‐g‐poly(acrylic acid) (CTS‐g‐PAA) and poly(vinyl alcohol) (PVA) were prepared by solution polymerization using ammonium persulfate (APS) as an initiator and N,N′‐methylenebisacrylamide (MBA) as a crosslinker. The effects of reaction conditions such as the concentration of MBA, the weight ratio of AA to CTS, and the content of PVA on water absorbency were investigated. Infrared (IR) spectra and differential scanning calorimetry (DSC) analyses confirmed that AA had been grafted onto CTS backbone, and PVA semi‐interpenetrating into CTS‐g‐PAA networks. SEM analyses indicated that CTS‐g‐PAA/PVA has improved porous surface and PVA was uniformly dispersed in CTS‐g‐PAA network. The semi‐IPN hydrogel containing 10 wt% PVA shows the highest water absorbency of 353 and 53 g g^?1 in distilled water and 0.9 wt% NaCl solution, respectively. Swelling behaviors revealed that the introduction of PVA could improve the swelling rate and enhance the pH stability of the superabsorbent hydrogel. Copyright © 2009 John Wiley & Sons, Ltd.     

A pH‐sensitive,strong double‐network hydrogel: Poly(ethylene glycol) methyl ether methacrylates–poly(acrylic acid)

We here describe new double network (DN) hydrogels with excellent mechanical strength and high sensitivity to pH changes. The first polymer network has a bottle brush structure and is formed from oligo‐monomers of poly(ethylene glycol) methyl ether methacrylate (PEGMA). Poly(acrylic acid) (PAA) is used as the second network. This double network features strong intermolecular interactions between the neutral poly(ethylene glycol) (PEG) side chains of PPEGMA and the non‐ionized carboxylic acid groups of the PAA second network. When immersed in solutions with a pH below ～4 the DN hydrogels have a low swelling ratio and are opaque as a result of solvent‐polymer phase separation driven by the formation of dense hydrogen‐bonded clusters. The compression strength (～8 MPa) is at least 14 times higher than the analogous single networks. When immersed in solutions with a pH >4, the hydrogels are transparent and exhibit a high swelling ratio with a compression strength of ～1 MPa. The PEG side chain length can be readily controlled without greatly altering the overall DN topology by choosing PEGMA monomers having different PEG side chain lengths. Longer PEG side branches give higher compression and tensile strengths at pH <4 when hydrogen bonded clusters form. The robust nature of these DN gels over a wide pH range may be useful for applications such as artificial muscles and controlled release devices. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012