聚氨酯聚二甲基硅氧烷半IPN透气性研究

近年来,互穿聚合物网络(IPN)的开发受到了广泛的关注。以聚氨酯为一组分,聚丙烯腈、聚酯及环氧树脂等为另一组分的IPN体系的研究已有报道,而聚氨酯与有机硅的IPN体系的研究报道很少。在本文中,我们对聚氨酯(PU)与聚二甲基硅氧烷(PDMS)半IPN的透气性与结构的关系进行了研究。     

壳聚糖-丝心蛋白合金膜的研究(Ⅱ)──半互穿聚合物网络型膜对pH和离子的敏感性

研究了壳聚糖-丝心蛋白半互穿聚合物网络型膜对pH值和离子的敏感性,发现该膜在pH<3.3时溶胀度剧烈增加;在pH=2时,是否出现溶胀极大值与膜组分的含量及交联剂的含量有关;膜在不同pH值溶液中可交替溶胀和收缩,且这种溶胀-收缩行为重复可逆。同时,该膜在不同离子溶液中的溶胀度亦不同;在相同离子强度的溶液中,此膜在3价离子中的溶胀度最大。     

In situ synthesis of polysaccharide nanoparticles via polyion complex of carboxymethyl cellulose and chitosan

Biocompatible polymer-magnetite hybrid nanoparticles were prepared by means of in situ synthesis of magnetite within polysaccharide hydrogel nanoparticles. Hydrogel nanoparticles were first fabricated by blending high-molecular-weight carboxymethyl cellulose as an anionic polymer, and low-molecular-weight chitosan as a cationic polymer to form polyion complexes (CC particles). These polyion complexes were then chemically crosslinked using genipin, a bio-based cross-linker, to form stable nanoparticles having a semi-IPN structure (CCG particles). Magnetite was lastly synthesized within CCG particles by the coprecipitation method to obtain polymer-magnetite hybrid nanoparticles (CCGM particles). The formations of CC, CCG and CCGM particles were mainly observed by transmittance, absorbance of genipin and TEM, respectively, and their hydrodynamic diameters and zeta-potentials were analyzed. It was confirmed that the hydrodynamic diameters and the zeta-potentials of these particles were significantly influenced by pH of the suspension, which was attributed to the charges of polymers. The diameters of CCGM particles were smaller than 200 nm at any pH conditions, suggesting the possibility to apply them as drug delivery carriers. CCGM particles exhibited the responsiveness to a magnetic field in addition to their high dispersion stability, indicating their potential to be utilized as a biomaterial for hyperthermia.     

磁性半互穿网络智能水凝胶的合成及性质评价

以甲基丙烯酸(MAA)、N-异丙基丙烯酰胺(NIPAAm)、丙烯酰胺(AM)为原料,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,利用IPN技术并结合磁性的γ-Fe2O3增强剂,在水溶液中制备了半互穿网络水凝胶(PMAA/PAM-NIPAAm/γ-Fe2O3),研究了水凝胶的溶胀性﹑热稳定性和电磁性。实验表明,水凝胶形成稳定的IPN互穿网络结构且该水凝胶具温度、pH双重敏感性和顺电磁性。所合成的水凝胶在低临界溶解温度31℃以下,具有明显正向温敏性,高于此温度,水凝胶的温度敏感性会逐渐减弱。产品成功克服了NIPAAm类水凝胶的温缩性。     

高强度PAM/PVP半互穿网络凝胶制备及力学性能

以过硫酸铵为引发剂通过一步溶液聚合制备了由化学交联的聚丙烯酰胺(PAM)与聚乙烯吡咯烷酮(PVP)贯穿形成的PAM/PVP半互穿网络(semi-IPN)凝胶,着重研究了凝胶的机械性能。红外光谱、热重分析及拉伸实验分析可知PAM与PVP之间存在氢键作用。拉伸实验表明:在PAM中引入PVP,凝胶拉伸强度明显提高,m(PVP)/m(AM)=7.51%时制备的PAM/PVP semi-IPN凝胶拉伸强度比单纯化学交联的PAM增大64.67%;当AM=6mol/L,n(MBA)/n(AM)=1.67×10-4,m(PVP)/m(AM)=7.51%时,制备的凝胶机械性能较好,拉伸强度达到1.84MPa,断裂伸长率可达3322%;随着含水率增加,凝胶拉伸强度及断裂伸长率均有所降低。     

干燥方式对含直链淀粉半互穿网络水凝胶溶胀和降解的影响

以4,4′-二甲基丙烯酰胺基偶氮苯(BMAAB)为交联剂,制备了丙烯酸-丙烯酰胺-甲基丙烯酸酯共聚物和直链淀粉半互穿网络水凝胶.以冷冻干燥和空气干燥两种方式,研究了干凝胶在pH2.2和pH7.4时的溶胀和降解性能.结果表明采用两种干燥方式的凝胶在不同pH的介质中都遵循二级溶胀动力学.凝胶内部水的扩散均为非Fickian机理,即扩散和链松弛协同作用的机理.但经历冷冻干燥的凝胶其扩散机制占优势.在pH=7.4的介质中,冷冻干燥凝胶的平衡溶胀比(SR)显著增大,而在pH=2.2时则无明显变化.扫描电镜(SEM)和降解实验发现,在结肠内容物的作用下,冷冻干燥凝胶在5天内降解率可达35.3%,而空气干燥凝胶的降解率为28.1%,表明冷冻干燥的方式可在一定程度上促进凝胶在结肠环境下的降解.     

淀粉和生物降解大分子间的半互穿聚合物网络的耐水性研究

以淀粉和可生物降解的PCL或PHBV等疏水性脂肪族聚酯为原料, 制备了淀粉基的Semi-IPN材料. 加入PCL或PHBV等疏水性大分子的使淀粉基Semi-IPN材料的耐水性能相对于原淀粉有很大的改善, 通过热处理和溶剂化作用能使Semi-IPN的耐水性进一步提高.     

Morphology and properties of semi-IPNs of polyetherimide and bisphenol A dicyanate

Semi-interpenetrating polymer networks (semi-IPNs) were synthesized from mixtures of polyetherimide (PEI) and bisphenol A dicyanate (BPACY) at different compositions and different cure temperatures. The phase separation behavior during cure was analyzed in terms of glass transtion temperature (T_g) behavior of fully cured semi-IPNs and the morphology–property relationship was also studied. The mixtures of PEI and BPACY monomer showed upper critical solution temperature behavior and their semi-IPNs showed sea-island morphology in 1–14 wt% PEI composition, dual-phase morphology in 15–19 wt% PEI composition and nodular morphology in 20–60 wt% PEI composition, respectively. The sea-island morphology was formed via nucleation and growth, while the other morphologies were predominantly formed via spinodal decomposition. Cure temperature did not influence the macroscopic morphology, but the domain size changed with temperature. As cure temperature was increased, the PEI domain size in the sea-island morphology decreased, while the BPACY nodule size increased in the nodular morphology. Mechanical and thermal properties were so strongly dependent upon the morphology that they changed dramatically near the phase inversion point.     

Formation and thermal stability of BMI-based interpenetrating polymers for gas separation membranes

Semi-interpenetrating polymer networks (semi-IPNs) were prepared by sol–gel technique through in situ polymerization of bismaleimide (BMI) in thermoplastic polyetherimide (PEI) as well as in polysulfone (PSF). This synthesis route allows arresting thermoset/thermoplastic phase separation at an early stage by solidifying the semi-IPNs through membrane phase inversion. The phase separation could be observed visually in the casting solution or by optical microscope on the surface of the produced membranes. These semi-IPNs with a density lower than their thermoplastic base polymer allowed easier water penetration during membrane phase inversion. This led to improved membrane morphology that was confirmed by scanning electron microscopy. Membranes fabricated from these semi-IPN materials had thinner skin layers and longer straight fingers perpendicular to membrane surface. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) showed that these semi-IPNs membranes have improved glass transition temperatures but a lower thermal stability. However, at ambient conditions, these membranes with their improved structure and morphology showed superior gas separation characteristics compared to base polymers. For example, the permeance was increased by 12–15 times without a significant decrease in the selectivity of oxygen over nitrogen in air separation experiments.     

Preparation and release profiles of pH/temperature-responsive carboxymethyl chitosan/P(2-(dimethylamino) ethyl methacrylate) semi-IPN amphoteric hydrogel

Thermo- and pH-responsive semi-IPN polyampholyte hydrogels were prepared by using carboxymethyl chitosan and P(2-(dimethylamino) ethyl methacrylate) with N N'-Methylenebisacrylamide (BIS) as crosslinking agent. It was found that the semi-IPN hydrogel shrunk most at the isoelectric point (IEP) and swelled when pH deviated from the IEP. Its swelling ratio dramatically decreased between 30 and 50 °C at pH 6.8 buffer solution. It also showed good reversibility. The UV results showed that when the pH values of drug release medium were 3.7, 6.8, and 9 at 25 °C, the cumulative release rates reached 83.1, 51.5, and 72.2%, respectively. The release rate of coenzyme A (CoA) was higher at 50 °C than 37 and 25 °C at pH 6.8 solution. The release rate decreased with increasing the content of carboxymethyl chitosan at 25 °C in pH 6.8 solution. The results showed that semi-IPN hydrogel seems to be of great promise in pH/temperature drug delivery systems.