三偏磷酸钠交联壳聚糖膜的制备及其性能研究

将充分溶胀的壳聚糖膜置于一定浓度的三偏磷酸钠溶液中进行交联反应制备出交联壳聚糖膜。用傅立叶变换红外光谱(FT-IR)、X-射线衍射(XRD)和扫描电镜(SEM)表征了其结构,并测试了其吸水率、力学性能和酶降解性能。研究结果表明,交联作用明显提高了膜的抗张强度和抗水性,并有效地降低了溶菌酶对其降解速率。该交联膜有望用作可控降解生物医用材料。     

三偏磷酸钠交联壳聚糖/聚乙烯醇共混膜的制备及其性能研究

将充分溶胀的壳聚糖/聚乙烯醇共混膜置于一定浓度的三偏磷酸钠溶液中进行交联反应制备出交联壳聚糖膜。用红外光谱(FTIR-ATR)、X-射线衍射(XRD)和扫描电镜(SEM)表征了膜的结构,并测试了其吸水率、力学性能、酶降解性能。结果表明,交联作用明显提高了膜的抗张强度和抗水性,并有效地降低了溶菌酶对其降解速率。     

交联羧甲基壳聚糖对铅离子的吸附研究

以壳聚糖为原料,先在氨基上引入羧甲基制备出N-羧甲基壳聚糖,再和环氧氯丙烷发生交联反应,合成出新型交联羧甲基壳聚糖,FTIR表征其结构。研究了交联羧甲基壳聚糖对Pb2+的吸附性能,探讨了交联剂用量、铅离子溶液的pH值、温度、吸附时间等因素对其吸附性能的影响,并考察了交联羧甲基壳聚糖对铅离子吸附动力学和热力学实验。实验结果表明,交联羧甲基壳聚糖对铅离子的吸附量优于壳聚糖,平衡吸附量可达297.6 mg/g。交联羧甲基壳聚糖对铅离子的吸附符合准二级动力学模型和Langmuier等温吸附,吸附主要依靠结构中的羧基和氨基基团。     

壳聚糖交联膜结构及性能的研究

壳聚糖是一种天然生物高分子聚合物，是甲壳素脱乙酰化产物，具有很好的成膜特性．用一种金属离子把壳聚糖分子中的螫合基团络合保护后，用戊二醛交联，并在酸性条件下将该金属离子洗脱，得到了螯合基团依然保留的壳聚糖交联膜．对壳聚糖交联膜的结构及性能进行了研究．结果表明：金属离子有效地保护了壳聚糖分子上的络合基因，该膜的性能较好，对阴离子的选择透过性比较好，并将其应用于元素的分离．     

壳聚糖枝载型偶氮色素的合成及表征

合成色素已被广泛应用到食品及医药行业。但是,以偶氮类为主体的食用合成色素在人体内易降解为芳香胺类化合物,这类化合物毒性较大,具有致癌性和遗传毒性。在天然高分子中,壳聚糖作为唯一碱性多糖,无毒,生物相容性好,且高分子量的壳聚糖在人体内也难以被降解吸收,是很好的食用色素目标载体。本文利用壳聚糖上较为活泼的氨基,制备出壳聚糖枝载偶氮色素。对实验所制备的壳聚糖枝载偶氮色素,利用NaHSO_3在酸性条件下进行还原,发现其抗还原性得到有效提升。选取日落黄、橙黄Ⅱ、柠檬黄、苋菜红、胭脂红5种食用色素,通过与环氧氯丙烷反应改性,再与壳聚糖交联,合成了生物相容性好的壳聚糖枝载型大分子色素。用IR、HNMR对产物结构进行了表征,考察了壳聚糖枝载型大分子色素在NaHSO_3还原体系下的稳定性,发现其抗还原性得到有效提升。     

丙烯酸交联壳聚糖渗透汽化膜研究（Ⅰ）——膜结构及交联机理

报道了一种新型渗透汽化膜－－丙烯酸交联壳聚糖膜，通过溶胀、拉伸、渗透汽化分离以及红外光谱等手段研究了膜的结构和交联机理。实验结果表明，交联反应由两部分组成：丙烯酸的双键和壳聚糖的氨基的加成反应和丙烯酸另一端的羧基和壳聚糖的氨基的酸碱中和反应。     

壳聚糖交联膜电渗析法分离氟、氯、砷的研究

用壳聚糖交联膜电渗析方法，分离去除Ｃｌ－、Ｆ－以及ＡｓＯ－２，并考查了其分离的最佳条件，如槽电压、酸度、浓度等，并通过其对Ｃｌ－、Ｆ－的分离与目前极具权威的ＡＥＭ对Ｆ－、Ｃｌ－分离进行比较看出：两者的分离效果极为相近．所以把壳聚糖交联膜用于工业生产中前景可观．     

交联壳聚糖缩水杨醛螯合树脂的制备及性能研究

以壳聚糖缩水杨醛产品为原料,环氧氯丙烷为交联剂,加入相转移催化剂,合成交联壳聚糖缩水杨醛螯合树脂的新工艺。考察了各种因素驿交联反应的影响及树脂的吸附性能。结果表明,该树脂具有对Ｃｕ（ＩＩ）吸附容量高,吸附选择性系数ＫＣｕ（Ⅱ）／Ｆｃ（Ⅲ）＝１３．５５,经简单再生后重复使用次数多的特点。     

交联黄原酸壳聚糖对铅离子的吸附研究

以壳聚糖为原料,通过交联和黄原酸化反应制备出交联黄原酸壳聚糖,采用FT-IR和XRD表征了其结构,并探讨壳聚糖及交联黄原酸壳聚糖对Pb2+的吸附性能。研究了初始溶液pH值、温度以及吸附时间等因素对Pb2+吸附量的影响。结果表明,在Pb2+起始浓度0.01 M,起始溶液pH=5,室温25℃吸附2h条件下,壳聚糖和交联黄原酸壳聚糖对铅离子的吸附量分别为126.8 mg/g和238.9 mg/g,交联黄原酸壳聚糖吸附能力为壳聚糖的1.89倍。     

硫酸交联壳聚糖膜质子传导行为的研究

制备了硫酸交联壳聚糖膜, 通过研究其质子传导性能、力学性能、化学成分及结构变化, 分析了硫酸与壳聚糖分子间的交联方式, 并对质子传导机理进行了解析. 结果表明, 硫酸交联可显著改善壳聚糖膜的质子传导能力与力学性能, 这种改善作用在交联6 h后趋于稳定, 交联6 h后的壳聚糖湿膜在室温下时质子传导率为0.0472 S• cm^－1, 比未交联的壳聚糖膜提高5倍左右. 硫酸交联壳聚糖膜中的质子传导率与温度的关系符合Arrhenius定律, 质子传导激活能为18 kJ/mol, 其传导机制应属于Grotthus机制. 硫酸对提高壳聚糖膜的质子传导能力主要有两方面的作用: (1) H₂SO₄可使壳聚糖分子中NH₂质子化形成NH₃^＋. (2) 处于两个氨基之间的SO₄^2－在质子传递过程中起离子桥梁作用, 参与以水分子为载体的质子传导过程, 从而减小质子传导的阻力, 提高了质子传导率.     

A NOVEL APPROACH TO SYNTHESIZE CHITOSAN BEADS CROSSLINKED BY EPICHLOROHYDRIN

The present investigation describes a novel method for preparing spherical chitosan particles based on crosslinking with epichlorohydrin.Certain amount of pre-crosslinking agent was added to form chitosan gels by traditional inverse phase suspension polymerization.Then the gels were crosslinked by epichlorohydrin at basic condition to obtain chitosan beads.The effects of reaction conditions,such as crosslinking time,the amount of crosslinking agent and the NaOH concentration,on the physical properties of the chitosan beads were investigated.The beads were found to have more amino groups in the polymer chains than the beads crosslinked by glutaraldehyde.The capacity for copper ions in as high as 40mg/g,The beads have good mechanical strength and can be reused.     

A NOVEL APPROACH TO SYNTHESIZE CHITOSAN BEADS CROSSLINKED BY EPICHLOROHYDRIN

1. INTRODUCTION Chitosan is the deacetylated chitin which is one of the most abundant natural polymers produced from crab, lobster and shrimp shells or fungal fermentation processes [1]. It is a family of deacetylated β1→4 D-glucosamine polymers. Chitosan has properties including bioactivity, biocompatibility and biodegradability, so it is potentially more useful than cellulose for developing advanced of attention not only as an unutilized biomass resource but also as a novel type of sp…     

Studies on the preparation of hydrolyzed starch-g-PAN (HSPAN)/PVA blend films--Effect of the reaction with epichlorohydrin

Absorbent hydrolyzed starch-g-PAN (HSPAN)/polyvinylalcohol (PVA) blend films crosslinked with epichlorohydrin (ECH) were prepared to overcome the phase separation and improve the mechanical properties of blend films. The absorbency of HSPAN/PVA blend films decreased with PVA contents due to the reduction of HSPAN contents which is known to play a major role in absorbing ability of the film. And also the absorbency decreased with the ECH contents due to the crosslinking reaction. As far as the solubility is concerned, it increased with PVA contents which is water soluble. But because of the crosslinking reaction between HSPAN and PVA by ECH, the solubility decreased with ECH contents. In the mechanical properties, the strength as well as the strain at break of the HSPAN/PVA blend films were improved very much if compared with HSPAN film, and those mechanical properties were improved even more by the reaction with ECH. The DSC thermograms of HSPAN films showed two major endothermic peaks at 32 and 128 °C, while those of PVA film showed two major endothermic peaks at 49 and 190 °C. In the non-crosslinked blend films, each four endothermic peak was apparent. But as the ECH content increased, both peaks at 128 and 190 °C disappeared and a new peak appeared at the intermediate temperature. In other words, the compatibility of blend films was increased by the reaction with ECH. Also, from the results of TGA, it was confirmed that the thermal degradation of blend films was decelerated by the crosslinking reaction.     

Effect of Different Crosslinking Strategies on Physical Properties and Biocompatibility of Freestanding Multilayer Films Made of Alginate and Chitosan

Freestanding multilayer films prepared by layer‐by‐layer technique have attracted interest as promising materials for wound dressings. The goal is to fabricate freestanding films using chitosan (CHI) and alginate (ALG) including subsequent crosslinking to improve the mechanical properties of films while maintaining their biocompatibility. Three crosslinking strategies are investigated, namely use of calcium ions for crosslinking ALG, 1‐ethyl‐3‐(‐3‐dimethylaminopropyl) carbodiimide combined with N‐hydroxysuccinimide for crosslinking ALG with CHI, and Genipin for crosslinking chitosan inside the films. Different characteristics, such as surface morphology, wettability, swelling, roughness, and mechanical properties are investigated showing that films became thinner, exhibited rougher surfaces, had lower water uptake, and increased mechanical strength after crosslinking. Changes of wettability are moderate and dependent on the crosslinking method. In vitro cytotoxicity and cell attachment studies with human dermal fibroblasts show that freestanding CHI‐ALG films represent a poorly adhesive substratum for fibroblasts, while studies using incubation of plastic‐adherent fibroblast beneath floating films show no signs of cytotoxicity in a time frame of 7 days. Results from cell experiments combined with film characteristics after crosslinking, indicate that crosslinked freestanding films made of ALG and CHI may be interesting candidates for wound dressings.     

Dialdehyde starch‐crosslinked chitosan films and their antimicrobial effects

For improved mechanical and water‐swelling properties of chitosan films, a series of transparent films were prepared with dialdehyde starch as a crosslinking agent. Fourier transform infrared and X‐ray analysis results demonstrated that the formation of Schiff's base disturbed the crystallization of chitosan. The mechanical properties and water‐swelling properties of the films were significantly improved. The best values of the tensile strength and breaking elongation were 113.1 MPa and 27.0%, respectively, when the dialdehyde starch content was 5%. All the crosslinked films still retained obvious antimicrobial effects toward S. aureus and E. coli, and they showed potential for biomedical applications. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 993–997, 2003     

Crosslinking and characterization of commercially available poly(VDF-co-HFP) copolymers with 2,4,4-trimethyl-1,6-hexanediamine

Fluorinated copolymers are well known for their large range of applications. These applications can be improved by grafting or crosslinking of several agents. The mechanism of crosslinking of hexamethylene diamine and 2,4,4-trimethyl-1,6-hexanediamine is well known and occurs in four different steps. To elaborate a film of commercially available poly(VDF-co-HFP) copolymer crosslinked by 2,4,4-trimethyl-1,6-hexanediamine, a step of press cure under air is necessary. Temperature, time and pressure were optimised by regarding the solubility of the press cured films, the mechanical properties, the swelling rate in methyl ethyl ketone, and the degradation of the films. The best temperature, time and pressure for press cure were 150 °C, from 15 to 30 min, and 20 bars, respectively. Other properties of crosslinked poly(VDF-co-HFP) copolymers containing 10 mol.% and 20 mol.% of HFP were characterized. First, all films were insoluble in concentrated HCl. Secondly, swelling rates of different amounts of diamine crosslinked copolymers were measured in ethylene carbonate/dimethyl carbonate and in methyl ethyl ketone; it was proved that the higher the molar percentage of diamine, the higher the crosslinking density, so the lower the swelling rate. Concerning thermal properties, glass transition temperature mainly increased when the amount of diamine increased. Thermal stability measurements showed a higher decomposition temperature when the percentage of diamine was very low (5 mol.%). Finally, mechanical properties were measured by dynamic mechanical analysis; the storage tensile modulus (E′) of a diamine crosslinked Kynar^® copolymer versus temperature exhibited a high drop because Kynar^® was a highly amorphous copolymer. Moreover, the higher the amount of diamine, the higher the rubbery modulus.     

Ultraviolet‐induced crosslinking of poly(butylene succinate) and its thermal property,dynamic mechanical property,and biodegradability

Crosslinking is an effective way to improve polymer properties. This paper focuses on ultraviolet‐induced crosslinking of poly(butylene succinate) (PBS) in the presence of a photoinitiator and a crosslinking agent at ambient temperature. The effects of the concentration of photoinitiator, the crosslinking agent content, and the irradiation time on the crosslink behavior were investigated. To obtain an appropriate gel fraction in different irradiation times, 3.0 wt% of photoinitiator and 10.0 wt% of crosslinking agent were proved to be the optimum choice. Furthermore, properties such as thermal properties, dynamic mechanical property, and enzymatic degradation of PBS before and after crosslinking were examined. Differential scanning calorimetry (DSC) analysis revealed that glass transition temperature (T_g) increased with increase in gel fraction, while melting temperature (T_m) and the degree of crystallinity decreased. This may be caused by the reduced molecular chain mobility and inhibited molecular motion for crystallization in crosslinked samples. The crosslinked polymer also showed improved thermal stability and dynamic mechanical property. In addition, the introduction of crosslinking retarded the enzymatic degradation rate of PBS, but it was still biodegradable. The improved properties of crosslinked PBS will extend the application of PBS. Copyright © 2009 John Wiley & Sons, Ltd.