药和缓释材料的合成与性能

研究了聚氨酯／聚醚半互穿网络聚合物的合成、溶胀行为和释放性能，特别是疏水组成、线型聚醚结构和温度对网络的溶胀平衡和溶胀动力学的影响。同时还测量了大分子肝素在填充时的分配系数和释放速度，并对肝素从溶胀的互穿网络聚合物中释放的机理进行了探讨。     

蓖麻油型聚氨酯/PS同步IPNs的协同效应研究

采用同步互穿网络技术,制备了一系列蓖麻油型聚氨酯/聚苯乙烯（COPU/PS）互穿网络聚合物（IPNs）,研究了它们的力学性能和溶胀性能.结果表明,当PS/COPU、BPO（过氧化二苯甲酰）/St（苯乙烯）质量分数分别为30%和1.5%时,三羟甲基丙烷（TMP）和蓖麻油羟基的摩尔比、NCO与OH的摩尔比分别为0.2和1.3时,互穿网络材料的相容性好,协同效应明显,此时力学性能最佳.当COPU/PS的IPNs材料中PS质量分数为20%～40%时,由于两相的互穿作用,使二甲苯对IPNs材料的溶胀趋缓;并且随着交联剂TMP的增加,平衡溶胀增重率增幅变小,到TMP和蓖麻油的羟基摩尔比值大于0.2后,平衡溶胀增重率基本不变.     

丙烯酸丁酯/VAE互穿聚合物乳液的研究

以互穿聚合物网络(IPN)方法合成丙烯酸丁酯与VAE共聚物乳液。研究了乳化剂、交联剂、溶胀时间、反应时间等条件对转化率的影响。以红外光谱、透射电子显微镜表征互穿共聚物乳胶膜的微观结构。通过吸水性及乳胶膜对水接触角的测定，证明其耐水性较VAE乳胶膜明显增强。。YEM照片表明互穿聚合物胶粒形态结构较VAE乳胶粒发生了明显变化。     

新型三元互穿聚合物网络阻尼材料的研制

采用平衡溶胀工艺,合成了具有宽温域、高阻尼值的新型三元互穿聚合物网络.透射电镜证明了乳液交联反应的发生和互穿网络的结构.分别通过对乳液及乳胶膜性能的测试和比较,发现三元互穿聚合物网络相容性和阻尼性均优于二元互穿聚合物网络.     

聚丙烯酰胺水凝胶的PH敏感性研究

高分子凝胶是大分子链经交联聚合而成的三维网络或互穿网络与溶剂(通常是水)组成的体系,具有智能响应的能力。研究聚丙烯酰胺水凝胶的pH敏感性对胶体的药物释放控制有积极的指导意义。分析了pH敏感性的变化规律,探讨了离子型水凝胶pH敏感性的溶胀机理。由研究表明,聚丙烯酰胺(PAAM)水凝胶的pH值敏感性变化过程可以分为3个阶段,得到了在pH值影响下的胶体溶胀比的计算公式。     

戊二醛对壳聚糖-聚醚水凝胶溶胀动力学的影响

以壳聚糖和聚醚为原料、戊二醛为交联剂合成了壳聚糖-聚醚水凝胶。研究了壳聚糖-聚醚水凝胶溶胀机理,探讨了戊二醛浓度对该水凝胶的溶胀度、溶胀速率和溶胀动力学的影响。结果表明,戊二醛浓度不仅是影响水凝胶溶胀度的主要因素,随着戊二醛浓度的增大,壳聚糖-聚醚水凝胶的溶胀度逐渐减小,而且影响其溶胀动力学类型,当戊二醛浓度为0.107 mol·L^-1,该水凝胶的溶胀过程属于Fickian类型,当戊二醛浓度为0.320、0.533 mol·L^-1,其溶胀过程属于non-Fickian类型。     

温度和pH值对智能水凝胶溶胀行为的影响

以N-马来酰化壳聚糖(N-MACH)为交联剂,N-异丙基丙烯酰胺(NIPAAm)为单体,羧甲基纤维素钠(CMC)为半互穿材料,分别合成了PNIPAAm和PNIPAAm/CMC半互穿网络智能水凝胶,研究了两种水凝胶在不同温度的去离子水和不同pH值的缓冲溶液中的溶胀现象,结果表明介质温度和pH值对水凝胶的溶胀行为有显著影响。在温度和pH值一定时,水凝胶的溶胀率随着交联剂用量的增加而下降,随着CMC用量的增加而上升。     

聚苯乙烯互穿聚合物网络研究进展

综述了聚苯乙烯互穿聚合物网络的研究进展,阐述了分步互穿聚合物网络、同步互穿聚合物网络、半互穿聚合物网络和胶乳互穿聚合物网络的制备方法,介绍了组成和制备方法对PS互穿聚合物网络的相态结构和互穿聚合物网络相容性的影响。阐述了PS互穿聚合物网络的组成和结构对于力学性能、热力学性能、流变性能、气体透过率和吸附性的影响,最后综述PS互穿聚合物网络存在的问题及发展趋势。     

丙烯酸酯互穿网络聚合物的合成和性能

以十二烷基硫酸钠为乳化剂、丙烯酸乙酯为软单体、苯乙烯为硬单体 ,二乙烯基苯或三乙二醇二丙烯酸酯为交联剂 ,先以两步法合成软单体聚合物网络 ,随后加入硬单体溶胀并聚合。研究了软硬单体配比、交联剂和聚合条件对乳液聚合稳定性、放置稳定性和转化率等的影响 ,测定了互穿聚合物网络的 Tg和形态结构、加工和性能。结果表明 ,这种互穿聚合物网络为可以反复可塑加工、并具较高力学性能新型热塑性弹性体     

硝酸酯基聚醚聚氨酯的老化降解：Ⅲ.溶胀法研究降解动力学

运用聚合物的溶胀理论和化学反应动力学,研究了硝酸酯基聚醚聚氨酯的老化降解过程。结果表明,这类聚氨酯的降解遵从一级反应规律,MDI和TDI基聚氨酯的耐老化能力至少比HDI的强6倍。     

Thermal and pH dual‐responsive hydrogels based on semi‐interpenetrating network of poly(N‐isopropylacrylamide) and collagen nanofibrils

Hydrogels with environment‐sensitive properties have great potential applications in the controlled drug release field. In this paper, hybrid hydrogels with semi‐interpenetrating polymer networks (semi‐IPNs), composed of poly(N‐isopropylacrylamide) (PNIPAM) as the thermo‐sensitive component by in situ polymerization and self‐assembled collagen nanofibrils as the pH‐sensitive framework, were prepared for controlled release of methyl violet as a model drug. From Fourier transform infrared spectroscopy and scanning electron microscopy, it was indicated that the crosslinking of PNIPAM in the presence of collagen nanofibrils led to the formation of semi‐IPNs with homogeneous porous structure, and the semi‐IPNs showed improved thermal stability and elastic properties compared with the native collagen as determined using differential scanning calorimetry and rheologic measurements. Furthermore, the semi‐IPNs possessed swelling behaviors quite different from those of neat collagen or PNIPAM hydrogel under various pH values and temperatures. Correspondingly, as expected, the drug release behavior in vitro for semi‐IPNs performed variously compared with that for single‐component semi‐IPNs, which revealed the tunable performance of semi‐IPNs for release ability. Finally the thermo‐ and pH‐responsive mechanism of the semi‐IPNs was illuminated to provide guidance for the application of the thermo‐ and pH‐sensitive collagen‐based hybrid hydrogels in controlled drug delivery systems. © 2019 Society of Chemical Industry     

In vitro degradation and protein release of semi‐IPN hydrogels consisted of poly(acrylic acid‐acrylamide‐methacrylate) and amylose

The enzymatic degradation mechanism of semi‐interpenetrating network (semi‐IPN) hydrogel of poly (acrylic acid‐acrylamide‐methacrylate) crosslinked by azocompound and amylose in vitro was investigated in the presence of Fungamyl 800L (α‐amylase) and rat cecum content (cecum bacteria). The degradation mechanism involves degradable competition, i.e., reduction of azo crosslinkage is dominant in the earlier period of degradation. Subsequently, the degradation of gels is continued by combination of reduction of azo crosslinkage and hydrolysis of amylose. The cumulative release ratios of Bovine serum albumin (BSA, as a model drug) loaded semi‐IPN gels are 25% in pH 2.2 buffer solutions and 74% in pH 7.4 buffer solutions within 48 h. Moreover, the release behavior of BSA from the semi‐IPN gels indicates that it follows Fickian diffusion mechanism in pH 2.2 media and non‐Fickian diffusion and polymer chains relaxation mechanism in pH 7.4 media. The results indicate that the release of BSA from the semi‐IPN gels was controlled via a combined mechanism of pH dependent swelling and specificity to enzymatic degradation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation,characterization, and drug‐release properties of pH/temperature‐responsive poly(N‐isopropylacrylamide)/chitosan semi‐IPN hydrogel particles

Novel poly(N‐isopropylacrylamide) (PNIPAAm)/chitosan (CS) semi‐interpenetrating polymer network hydrogel particles were prepared by inverse suspension polymerization. The prepared particles were sensitive to both temperature and pH, and they had good reversibility in solution at different temperatures and pH values. The swelling ratios of PNIPAAm/CS hydrogel particles decreased slightly with the addition of CS, which did not shift the lower critical solution temperature. The drug‐release behavior of the particles was investigated using cyclic adenosine 3′,5′‐monophosphate (cAMP) as a model drug. The release of cAMP from the hydrogel particles was affected by temperature, pH, and the CS content in the particles. These results showed that semi‐IPN hydrogel particles appeared to be of great promise in pH‐ and temperature‐sensitive oral drug release. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and Swelling Properties of Temperature‐Sensitive Semi‐Interpenetrating Polymer Networks Composed of Poly[(N‐tert‐butylacrylamide)‐co‐acrylamide] and Hydroxypropyl Cellulose

Summary: Temperature‐responsive hydrogels based on linear HPC and crosslinked P(NTBA‐co‐AAm) were prepared by the semi‐IPN technique. The structure of these semi‐IPN hydrogels was investigated by FT‐IR spectroscopy. An increase in normalized band ratios (A₂₉₈₀/A₁₆₆₅) was observed with increasing HPC content in the initial mixture. The swelling kinetics and water transport mechanism of these semi‐IPN hydrogels were examined and their temperature responsive behaviors were also investigated by measuring equilibrium swelling ratios and pulsatile swelling experiments. The results showed that these semi‐IPN hydrogels underwent a volume phase transition between 18 and 22 °C irrespective of the amounts of MBAAm and HPC. However, below the volume phase transition temperature, their equilibrium swelling ratios were affected by the amount of MBAAm and HPC. The pulsatile swelling experiments indicated that the lower the MBAAm and the higher HPC contents in semi‐IPN hydrogels the faster the response rate temperature change.

Equilibrium swelling ratios of the semi‐IPN P(NTBA‐co‐AAm)/HPC hydrogels in water shown as a function of temperature.     

Swelling and diffusion characteristics of novel semi‐interpenetrating network hydrogels composed of poly[(acrylamide)‐ co‐(sodium acrylate)] and poly[(vinylsulfonic acid), sodium salt]

A series of novel semi‐interpenetrating polymer networks (IPNs) composed of poly[(acrylamide)‐co‐(sodium acrylate)] with varying amounts (5, 10, and 15 wt%) of poly[(vinylsulfonic acid), sodium salt] was synthesized. The semi‐IPN hydrogels were characterized by infrared spectroscopy. The swelling behavior of these IPNs was studied in distilled water/physiological solutions/buffer solutions/salt solutions. As the amount of poly[(vinylsulfonic acid), sodium salt] increased in the network, the swelling capacity of the semi‐IPNs increased considerably. The swelling and diffusion characteristics such as water penetration velocity (v), diffusion exponent (n), and diffusion coefficient (D) were calculated in distilled water, as well as in other physiological solutions. The highest swelling capacity was noted in urea and glucose solutions. The semi‐IPN hydrogels followed non‐Fickian diffusion behavior in water and physiological fluids, whereas Fickian behavior was observed in buffer solutions. The stimuli‐responsive characteristics towards physiological fluids, salt concentration, and temperature of these semi‐IPN hydrogels were also investigated. The swelling behavior of the semi‐IPNs decreased markedly with an increase of the concentration of the salt solutions. Copyright © 2006 Society of Chemical Industry     

Preparation of alginate/poly(N‐isopropylacrylamide) semi‐interpenetrating and fully interpenetrating polymer network hydrogels with γ‐ray irradiation and their swelling behaviors

Semi‐interpenetrating polymer network (semi‐IPN) and fully interpenetrating polymer network (full‐IPN) hydrogels composed of alginate and poly(N‐isopropylacrylamide) were prepared with γ‐ray irradiation. The semi‐IPN hydrogels were prepared through the irradiation of a mixed solution composed of alginate and N‐isopropylacrylamide (NIPAAm) monomer to simultaneously achieve the polymerization and self‐crosslinking of NIPAAm. The full‐IPN hydrogels were formed through the immersion of the semi‐IPN film in a calcium‐ion solution. The results for the swelling and deswelling behaviors showed that the swelling ratio of semi‐IPN hydrogels was higher than that of full‐IPN hydrogels. A semi‐IPN hydrogel containing more alginate exhibited relatively rapid swelling and deswelling rates, whereas a full‐IPN hydrogel showed an adverse tendency. All the hydrogels with NIPAAm exhibited a change in the swelling ratio around 30–40°C, and full‐IPN hydrogels showed more sensitive and reversible behavior than semi‐IPN hydrogels under a stepwise stimulus. In addition, the swelling ratio of the hydrogels continuously increased with the pH values, and the swelling processes were proven to be repeatable with pH changes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4439–4446, 2006     

Insolubilization of sodium chondroitin sulfate by forming a semi‐interpenetrating polymer network with acrylic acid: A potential carrier for colon‐specific drug delivery

To reduce the highly hydrophilic property of chondroitin sulfate (ChS), a semi‐interpenetrating polymer network (semi‐IPN) of chondroitin sulfate/polyacrylic acid (PAA) was prepared as a drug carrier by crosslinking acrylic acid with diethyleneglycol diacrylate. The swelling properties of the semi‐IPNs with different concentrations of crosslinking agent were correlated. The moisture sorption profiles were evaluated using differential thermal analysis. Ketoprofen was used as a drug probe to evaluate the performance of the drug released from the semi‐IPN matrices. The prepared semi‐IPNs demonstrated significant swelling reduction properties with both gastric and intestinal fluids compared with those of both the pure ChS and the ChSAA blend without the crosslinking agent. The amount of accumulated drug released from the semi‐IPNs was less than 30 wt % at pH 1.2 and up to 80 wt % at pH 7.4. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 114–122, 2002     

Swelling characterizations of chitosan and polyacrylonitrile semi‐interpenetrating polymer network hydrogels

Temperature‐ and pH‐responsive semi‐interpenetrating polymer network (semi‐IPN) hydrogels constructed with chitosan and polyacrylonitrile (PAN) were studied. The characterizations of semi‐IPN hydrogels were investigated using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). IPN hydrogels exhibited a relatively high swelling ratio, 23.31%–145.20% at room temperature. The swelling ratio of hydrogels depends on pH and temperature. DSC was used to determine the amount of free water in IPN hydrogels. The amount of free water increased with increasing chitosan content in the semi‐IPN hydrogels. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2011–2015, 2003     

Novel thermo‐responsive semi‐interpenetrating network microspheres of gellan gum‐poly(N‐isopropylacrylamide) for controlled release of atenolol

Thermoresponsive microspheres of gellan gum‐poly(N‐isopropylacrylamide), i.e., GG‐P(NIPAAm) semi‐interpenetrating polymer networks (semi‐IPNs) have been prepared by ionic crosslinking and used to study the controlled release (CR) of atenolol (ATL), an antihypertensive drug. Interaction of the drug with polymers was studied by Fourier transform infrared (FTIR) spectroscopy. Differential scanning calorimetry (DSC) was used to confirm the polymorphism and molecular level dispersion of ATL. Scanning electron microscopy (SEM) indicated spherical nature and smooth surfaces of the microspheres with some debris attached on their surfaces. Mean particle size measured by laser light diffraction ranged between 34 and 76 μm. Equilibrium swelling performed at 25°C and 37°C in pH 7.4 phosphate buffer exhibited thermoresponsive nature of the polymers. In vitro drug release performed at 25°C and 37°C indicated temperature‐dependency of ATL release, which was extended up to 12 h. In vitro release profiles at both the temperatures confirmed thermoresponsive nature of the polymers giving pulsatile trends. The % cumulative release data have been fitted to an empirical equation to estimate transport parameters and to understand the nature of drug release. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of pH‐ and temperature‐responsive semi–interpenetrating polymer network hydrogels based on linear sodium alginate and crosslinked poly(N‐isopropylacrylamide)

In this study, pH‐ and temperature‐responsive hydrogels based on linear sodium alginate (SA) and crosslinked poly(N‐isopropylacrylamide) (PNIPAAm) were prepared by semi‐interpenetrating network (semi‐IPN) technique. The dually responsive hydrogels were characterized by FTIR, DSC, and SEM, and their temperature‐ and pH‐responsive behaviors were investigated by measuring equilibrium swelling ratios and pulsatile swelling experiments. The results showed that these hydrogels underwent volume phase transition at around 33°C irrespective of the pH value of the medium, but their pH sensitivity was evident only below their volume phase transition temperature. Under basic conditions, the swelling ratios of SA/PNIPAAm semi‐IPN hydrogels were greater than that of pure PNIPAAm hydrogel and increased with increasing SA content incorporated into the hydrogels, but the case was inverse under acidic conditions. The pulsatile swelling experiments indicated that the higher the SA content in SA/PNIPAAm semi‐IPN hydrogels, the faster the response rate to both pH and temperature change. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1931–1940, 2005