含硅水凝胶膜中Na+的渗透性

采用腔膜法测定Na 在γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(KH570)与甲基丙烯酸羟乙酯(HEMA)及N-乙烯基吡咯烷酮(NVP)共聚物水凝胶角膜接触镜材料中的渗透系数,研究了Na 渗透系数的影响因素。结果表明,Na 在水凝胶膜中的扩散过程为稳态扩散,其渗透系数随温度升高而显著增大,但温度超过60℃,Na 渗透系数的增大幅度显著下降;水凝胶膜中Na 的渗透系数随NVP及KH570质量分数增多而增大,但KH570的质量分数超过15%,Na 的渗透系数反而随KH570含量增多而减小,其原因在于Na 被聚合物中的微孔陷阱捕获而无法跳出。     

有机硅改性共聚物水凝胶接触镜材料的合成与性能研究

以N-乙烯基吡咯烷酮(NVP)、甲基丙烯酸羟乙酯(HEMA)以及γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(KH570)为原料单体,N,N’-亚甲基双丙烯酰胺(NMBA)为交联剂,偶氮二异丁氰(AIBN)为引发剂,采用本体聚合法制备有机硅改性共聚物水凝胶接触镜材料,并研究了材料拉伸强度的影响因素。结果表明,所得材料的折光度为1．51,透光率达99%以上;有机硅的引入能显著提高材料的拉伸强度,NVP含量的增加使材料的拉伸强度下降。     

硅水凝胶隐形眼镜材料的合成与性能研究

以甲基丙烯酸羟乙酯（HEMA）、N-乙烯基毗咯烷酮（NVP）和γ-（甲基丙烯酰氧）丙基三甲氧基硅烷（KH-570）为单体,以偶氮二异丁腈（AIBN）为引发剂,通过本体聚合反应合成新型硅水凝胶角膜接触镜.考察了各单体配比、反应温度等对聚合的影响.结果表明,当反应温度为90℃,反应时间为2h,V（HEMA）：V（NVP）：V（KH-570） =8∶ 1∶1时,合成的隐形眼镜透氧量（DK/t）达到64.0×10-9（cm3O2·cm）/（cm2·s·mmHg）,含水量38％,透光率95.5％以上.     

NVP-HEMA-KH570共聚水凝胶的合成及其溶胀性能研究

以N,N’-亚甲基双丙烯酰胺为交联剂,偶氮二异丁氰（AIBN）为引发剂,合成不溶于水的乙烯吡咯烷酮（NVP）／甲基丙烯酸β-羟乙酯（HEMA）／γ-（甲基丙烯酰氧）丙基三甲氧基硅烷（KH-570）共聚水凝胶,研究了PVP水凝胶的平衡溶胀度及脱水性能。结果表明,随着NVP在水凝胶中含量的增大,水凝胶的平衡溶胀度逐渐增大;环境温度升高,KH570、BIS的含量及浸泡溶液的离子浓度增大,水凝胶的平衡溶胀度逐渐减少;在相同的时间内,环境温度越高,水凝胶的脱水率也越大;在同一温度下,HE-MA含量越大,凝胶脱水的速度就越慢,而浸泡的溶液离子浓度越高,脱水率就越大。     

聚硅氧烷-(甲基)丙烯酸酯共聚乳液的制备与性能

八甲基环四硅氧烷（D4）在复合乳化剂的作用下开环形成端羟基线性聚硅氧烷乳液,然后加入γ-甲基丙烯酰氧丙基三甲氧基硅（KH570）,pH=4的条件下KH570水解,再与端羟基线性聚硅氧烷脱水形成含反应双键的长侧链聚硅氧烷,再加入(甲基)丙烯酸酯单体,自由基聚合得到聚硅氧烷-（甲基）丙烯酸酯乳液。通过这种方法,有机硅单体可占到整个单体总量的80%。然后,通过29Si NMR 、FT-IR对含反应双键的聚硅氧烷及聚硅氧烷-（甲基）丙烯酸酯聚合物进行结构表征,并对乳液及其聚合物膜的性能进行了表征,结果表明KH570完全水解后与端羟基聚硅氧烷形成含反应双键的长侧链聚硅氧烷,同时也表明当有机硅用量为80%时乳液涂膜吸水率在最终为5.3%,表面自由能为6.56 mN/m,聚硅氧烷-（甲基）丙烯酸酯共聚聚合物最大热失重速率温度为577℃。聚合物的耐水性和热稳定性能有了很大的提高,因此,可以作为一种具有高疏水性和高耐热性的材料加以应用。     

改性聚天冬氨酸复合水凝胶的制备及性能

以聚琥珀酰亚胺（PSI）、丙烯酸（AA）和丙烯酰胺（AM）为原料,KH550和KH570为联合交联剂,采用水溶液聚合法合成了聚天冬氨酸/聚（丙烯酸-丙烯酰胺）复合水凝胶［KPAsp/P（AA-AM）］;探讨了交联剂用量、原料配比对KPAsp/P（AA-AM）复合水凝胶溶胀性能的影响;采用FTIR和TG对水凝胶进行了表征。结果表明当v（KH550）∶v（KH570）=1∶1和n（PSI）∶n（AA）∶n（AM）=1∶3∶1时,所合成的复合水凝胶溶胀性能最佳,溶胀度达到395。通过吸水动力学研究表明,共聚链的引入改变了水凝胶的吸水行为。研究了复合水凝胶对阿莫西林的控释性能,结果表明,复合水凝胶的载药量可达29.98mg/g;在37℃、pH=1.8的NaCl溶液中,负载了阿莫西林的复合水凝胶在2h对药物的释放率达到57%,24h左右达到85%。     

共聚物水凝胶角膜接触镜材料的初期脱水行为

以N-乙烯基吡咯烷酮、甲基丙烯酸羟乙酯以及甲基丙烯酸甲酯、甲基丙烯酸乙酯或者甲基丙烯酸丁酯为原料,制备共聚物水凝胶角膜接触镜材料,建立了膜状水凝胶材料的脱水模型,采用重量法和热失重法研究了该材料的初期脱水行为.结果表明,水凝胶膜的初期脱水速度与其交联密度的平方成反比;共聚物水凝胶中N-乙烯基吡咯烷酮的含量越大,脱水速率越大;甲基丙烯酸甲酯、甲基丙烯酸乙酯以及甲基丙烯酸丁酯的含量越大,脱水速率越低,以甲基丙烯酸乙酯最明显;在初期脱水阶段,水凝胶膜的脱水行为可用一级动力学描述.     

水在凝胶中的存在状态及其对凝胶力学性能的影响

以偶氮二异丁腈为引发剂,通过化学引发聚合合成甲基丙烯酸β-羟乙酯（HEMA）/N-乙烯基吡咯烷酮（NVP）二元共聚物和HEMA /NVP /甲基丙烯酸甲酯（或甲基丙烯酸丁酯）三元共聚物水凝胶,通过示差扫描量热法（DSC）结合热重法（TG）研究了不同单体配比的共聚物水凝胶中水的状态,证明了凝胶中存在3种不同状态的水：非冻结结合水、可冻结结合水和可冻结自由水.结果发现可冻结水的含量主要由NVP含量所决定,NVP单元基本不能键合水,而非冻结水的含量主要受HEMA含量和疏水性单体甲基丙烯酸酯含量影响.疏水性单体的引入使材料的力学强度提高,对凝胶体系具有增塑作用的是非冻结水而不是可冻结的结合水和自由水.     

共聚物水凝胶接触镜材料与牛血清蛋白亲和性的影响因素

为了评价蛋白质在自行制备的共聚物水凝胶角膜接触镜材料上的沉积行为。将水凝胶膜样品置于牛血清蛋白(BSA)水溶液中,沉积一定时间后,采用染料染色结合分光光度法分析沉积前后牛血清蛋白浓度的变化,计算沉积量。实验发现,随沉积温度升高,牛血清蛋白的沉积量增大;沉积时间超过5天,仍然没有达到饱和沉积;牛血清蛋白的浓度越高,沉积量越大。共聚物水凝胶材料中,N-乙烯吡咯烷酮(NVP)组分的含量越大,沉积量越大;而甲基丙烯酸酯组分则导致牛血清蛋白的沉积量减小,以甲基丙烯酸甲酯(MMA)最为明显。     

原位溶胶-凝胶法改性EPDM及其表征

采用原位溶胶-凝胶反应制备乙丙橡胶/ SiO₂纳米复合材料。分别以乙丙橡胶（EPDM）和γ-甲基丙烯酰氧丙基三甲氧基硅烷（KH570）接枝改性的乙丙橡胶 （EPDM-g-KH570）在前驱体四乙氧基硅烷 （TEOS）中溶胀,再浸入含有正丁胺的催化剂溶液中催化前驱体的原位溶胶-凝胶反应。考察了不同溶剂以及催化剂含量对TEOS转化率和原位生成的SiO₂粒径的影响。采用FT-IR、SEM等测试手段对纳米复合材料进行了表征。结果表明,接枝KH570后,TEOS转化率明显提高,SiO₂粒径明显减小,在材料中的分散性很好。     

Influence of N-vinyl-2-pyrrolidone and methacrylic acid on thermal curing process of 2-hydroxyethyl methacrylate hydrogel

This study investigated the effects of N-vinyl-2-pyrrolidone (NVP) and methacrylic acid (MA) comonomers on the curing characteristics and properties of poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogel for soft contact lenses. A real-time temperature measurement system was devised and the exothermic behaviors of hydrogel contact lenses comprising PHEMA, P(HEMA/NVP), and P(HEMA/MA) during oven-curing condition were analyzed. The results of the real-time temperature measurement were compared with the experimental analysis by using differential scanning calorimetry at different heating rates. NVP and MA content changes affected the HEMA-based hydrogel's equilibrium water content (EWC), contact lens diameter, and gel fraction. HEMA-based hydrogel sheets with varying NVP and MA contents were fabricated and mechanically characterized. The temperature at which the exothermic reaction occurred varied depending on the type of added comonomer and the exothermic reaction of HEMA containing NVP was delayed. When NVP was added, the mechanical strength and EWC were lower than when MA was added. In order to maintain the mechanical properties while improving the equilibrium moisture content of the lens, it was found that the use of MA is more advantageous than the use of NVP. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48622.     

水凝胶-水凝胶复合材料的制备与表征

将聚乙二醇400(PEG400)溶胀的交联N-乙烯吡咯烷酮(NVP)水凝胶微粒浸渍在含有引发剂过氧化苯甲酰(BPO)的甲基丙烯酸-2-羟基乙酯(HEMA)单体中并加热引发聚合反应,制备水凝胶-水凝胶复合材料,研究了产物的溶胀行为,并采用SEM、DSC对产物进行了表征。结果表明,水凝胶-水凝胶复合材料的饱和含水量随交联NVP水凝胶颗粒的含量及饱和含水量增大而增大,两种水凝胶之间的界面结构可分为包埋、部分互穿网络以及完全部分互穿网络等三种,其原因在于HEMA单体部分进入交联NVP水凝胶微粒并进行原位聚合的程度不同;处于分散相的水凝胶与处于连续相的水凝胶的吸水倍率不同,导致水凝胶-水凝胶复合材料吸水溶胀时不同相结构之间互相制约,处于分散相的水凝胶的大分子链不能充分伸展,非冻结水的熔融峰被自由水的熔融峰掩盖,表现为DSC谱图上非冻结水的熔融峰被自由水的熔融峰掩盖。     

NVP接枝壳聚糖水凝胶的合成与溶胀性能

合成了N-乙烯基吡咯烷酮（NVP）接枝壳聚糖（CHI）水凝胶,讨论了NVP/CHI、引发剂、交联剂、聚合温度、乙酸浓度等因素对接枝率及凝胶溶胀性能的影响,NVP∶CHI为6时,接枝率达到300%以上. 溶胀温度、pH值、盐浓度等对凝胶溶胀性能的影响实验表明,凝胶表现出温度敏感性,在40 ℃出现最大平衡溶胀率,并观察到一级相转变;在中性或弱酸性介质中溶胀性能较好;与PVP凝胶相比,NVP接枝CHI凝胶表现出反聚电解质效应. 溶胀动力学研究表明,在溶胀前期,CHI含量较高时,凝胶趋向于非Fick溶胀,说明除了溶剂扩散外,凝胶网络链段弛豫、水分子与凝胶网络间及凝胶高分子链段间相互作用对凝胶溶胀性能的影响至关重要;CHI含量较高时则趋向于Fick溶胀.     

Swelling and dye adsorption study of novel superswelling [Acrylamide/N-vinylpyrrolidone/3(2-hydroxyethyl carbamoyl) acrylic acid] hydrogels

Summary Super swelling acrylamide (Am)/N-vinylpyrrolidone (NVP)/3-(2-hydroxyethyl carbamoyl) acrylic acid (HECA) hydrogels were prepared by free radical polymerization of quaternary mixtures of Am, NVP, HECA and water. The hydrogels were used in experiments on swelling, diffusion and adsorption of some water-soluble monovalent cationic dyes such as Crystal Violet (CV), Malachite Green (MG) and Methylene Blue (MB). In the experiment of the adsorption of dyes from their aqueous solutions type-S adsorption isotherm were found. The diffusion of water within the hydrogel was found to have non Fickian character. The uptake of dyes within the hydrogel increased in the following order: MG > MB > CV. The binding ratio of the hydrogel/dye systems was gradually increased with the increase of HECA content in the AAm/NVP/HECA hydrogel.     

Synthesis of hydrogel for drug delivery studies utilizing photoinitiator‐free photopolymerization based on the donor/acceptor pair,N‐vinylpyrrolidinone and hydroxypentyl maleimide

Photo‐differential scanning calorimetry (photo‐DSC) was used to study the rate of photoinitiator‐free copolymerization of a donor/acceptor pair involving N‐vinylpyrrolidinone (NVP), and a water‐soluble N‐substituted maleimide, hydroxypentyl maleimide (HPMI). Glucose, 1,1‐diethoxy ethane (DEE) and isopropyl alcohol (IPA) were included for the evaluation of their efficiencies as hydrogen donors, and glucose was shown to be the most efficient in enhancing the rate of polymerization. This photoinitiator (PI)‐free system was extended to hydrogel preparation using the radiation method with UV as the radiation source based on the same donor/acceptor pair, ie NVP/HPMI, in the presence of glucose as the hydrogen donor. Swelling and drug release tests showed that this hydrogel exhibited high swelling ability and a rather fast drug release rate when using theophylline as the model drug. These tests also revealed that the drug release kinetics and the water diffusion into this hydrogel did not adhere to the Fickian model. Cytotoxicity testing showed no evidence of this hydrogel being cytotoxic. © 2002 Society of Chemical Industry     

表面修饰凹凸棒石及其在环氧丙烯酸树脂中的应用

旨在提高凹凸棒石在环氧丙烯酸酯中的力学性能及分散性能,以凹凸棒石纳米粉体为载体,采用化学沉淀法制备出包硅凹凸棒石复合纳米材料(Si O2/ATP),再用硅烷偶联剂KH570对Si O2/ATP表面进行有机改性,制得KH570-g-Si O2/ATP复合材料。通过TEM、FTIR、XRD及TG对复合材料进行表征。采用共混法制备了紫外光固化复合涂层,考察了KH570-g-Si O2/ATP的添加量对复合涂层耐冲击力、柔韧性的影响。结果表明,当KH570-g-Si O2/ATP的用量占涂料总重量的5%时,与EA涂层相比,复合涂层的耐冲击力的高度由15 cm增加至35 cm;涂膜的柔韧性由15 mm提升至5 mm;此外,与ATP、Si O2/ATP以及KH570-g-ATP相比,KH570-g-Si O2/ATP在EA涂层中具有良好的分散性,EA涂层的力学性能也得到明显改善。     

Microspheres of copolymeric <Emphasis Type="Italic">N</Emphasis>-vinylpyrrolidone and 2-ethoxyethyl methacrylate for the controlled release of nifedipine

Free radical copolymerization of N-vinyl-2-pyrrolidone (NVP) with 2-ethoxyethyl methacrylate (EOEMA) was carried out with 2,2′-azobisisobutyronitrile (AIBN) initiator in 1,4-dioxane solvent at 60 °C. The resulting copolymers were characterized by FTIR, ¹H-NMR and ¹³C-NMR methods. Microspheres were prepared by varying the amount of NVP with respect to EOEMA. Nifedipine (NFD), a water-insoluble antihypertensive drug, was loaded into these microspheres by the oil in water emulsion technique followed by solvent evaporation. The effect of the proportion of NVP in the NVP/EOEMA copolymer on the controlled release of NFD from the microsphere matrix was investigated. Scanning electron micrographs (SEM) of the microspheres indicated spherical shapes in the size range 17–47 μm, even after loading with NFD. In vitro studies of the release of NFD from the NVP/EOEMA microspheres in pH 7.4 medium showed that the rate of NFD release was enhanced when the NVP content of the copolymer was high; the size of the microspheres also increased with increasing NVP content of the copolymer. Release data were analyzed using an empirical relation in order to elucidate the kinetics of the NFD release. This analysis indicated that a Fickian transport mode operates in this system.