聚氯乙烯接枝聚乳酸的合成及生物降解性

以环己酮为溶剂,将聚氯乙烯(PVC)与聚乳酸(PLA)的钠盐进行反应,合成了以PVC为主链、PLA为支链的接枝聚合物(PVC-g-PLA)。讨论了实验条件对产物接枝率的影响,用核磁共振氢谱(1H-NM R)、红外光谱(FT-IR)和凝胶渗透色谱(GPC)对接枝聚合物进行了表征。采用土壤掩埋试验和扫描电镜(SEM)分析的方法,研究了接枝物的生物降解性。     

Release of Ciprofloxacin from Chondroitin 6-Sulfate-Graft-Poloxamer Hydrogel In Vitro for Ophthalmic Drug Delivery

The system was designed to use Poloxamer as a vehicle for ophthalmic drug delivery using in situ gel formation property. To enhance the wound healing and cell adhesion as well as transparency of Poloxamer hydrogel, chondroitin 6-sulfate (C6S) was introduced into Poloxamer. For this purpose, mono amine-terminated Poloxamer (MATP), which was end-capped with ethylene amine group only in one side of terminal hydroxyl groups of Poloxamer, was synthesized. Subsequently, C6S-graft-Poloxamer copolymer (C6S-g-Poloxamer) was prepared by reaction between the amine groups of MATP and carboxyl groups of C6S in the presence of 1-ethyl-3-(3-dimethylaminopropyl)-carboimide (EDC). The coupling of MATP with C6S was clarified by ¹H-NMR and FT-IR spectroscopy. The gelation temperature of graft copolymers was determined by measuring the temperature at which immobility of the meniscus in each solution was first noted. Release behavior of ciprofloxacin from C6S-g-Poloxamer hydrogel in vitro was investigated as a function of C6S content in the graft copolymer by a spectrophotometric assay at 287 nm using an UV spectrophotometer. Differences in the adhesion and morphology of human lens cell between Poloxamer- and C6S-g-Poloxamer-coated surfaces were also investigated. The gelation temperatures of C6S-g-Poloxamer copolymers were lowered with increasing of the concentration of the copolymer and decreasing of C6S content. The release of ciprofloxacin from the graft copolymer was sustained compared with Poloxamer itself and decreased with increasing the content of C6S in the copolymer due to the in situ gel formation of the copolymer and viscous properties of C6S. Human lens cells (B3) adhered to C6S-g-Poloxamer-coated surface were observed as transformed shapes after 2 days. The bioadhesive and thermally gelling of these graft copolymers will be expected to be an excellent drug carrier for the prolonged delivery to surface of the eye.     

乙基纤维素与聚L-乳酸接枝共聚物的合成与表征

以辛酸亚锡为催化剂,乙基纤维素(EC)为接枝骨架,L-丙交酯(L-LA)为接枝单体,在无溶剂条件下本体聚合制备了乙基纤维素-聚L-乳酸接枝共聚物。利用GPC,FTIR,1H NMR对接枝共聚物进行表征。结果表明,L-丙交酯在乙基纤维素残存的羟基上发生开环聚合,将聚乳酸短链引入到乙基纤维素骨架上,所得产物为乙基纤维素与聚L-乳酸接枝共聚物。XRD和偏光显微镜(POM)分析表明,当接枝率大于等于252%时,接枝共聚物开始结晶。     

氯化原位接枝制备酐基官能化CPVC

以氯化原位接枝法制备氯化聚氯乙烯接枝顺丁烯二酸酐的共聚物(CPVC-g-M AH),并用FT-IR、1H-NM R对产物进行表征;同时还讨论了反应温度、原料配比、反应时间以及膨润时间对产物接枝率的影响。     

Biodegradable IPN hydrogel beads of pectin and grafted alginate for controlled delivery of diclofenac sodium

A novel diclofenac sodium (DS) loaded interpenetrating polymer network (IPN) beads of pectin and hydrolyzed polyacrylamide-graft-sodium alginate (PAAm-g-SA) was developed through ionotropic gelation and covalent cross-linking. The graft copolymer was synthesized by free radical polymerization under the nitrogen atmosphere followed by alkaline hydrolysis. The grafting, alkaline hydrolysis, and characterization of beads were confirmed by Fourier transforms infrared spectroscopy. The crystalline structure of drug after encapsulation into IPN beads were evaluated by differential scanning colorimetry and X-ray diffraction analyses. DS encapsulation was up to 96.45 %. The effect of hydrolyzed graft copolymer/pectin ratios and glutaraldehyde concentration on drug release in acidic and phosphate buffer solutions were investigated. The release of drug was significantly increased with increase of pH. The release of drug depends on the extent of cross-linking. The results indicated that IPN beads of hydrolyzed PAAm-g-SA and pectin could be used for sustained release of DS.     

Compatibility studies of natural rubber/poly(methyl methacrylate) blends by viscometry and phase separation techniques

The compatibility of binary blends of natural rubber (NR) and poly(methyl methacrylate) (PMMA) has been analysed from the viscosity behaviour. For this, the equations developed by both Krighbaum and Wall, and their modified forms by Williamson and Wright, were used. The interaction between polymers in solution has been interpreted qualitatively based on the heat of mixing (ΔH) and interaction parameter (X1). Viscometry and spectroscopy studies and calculation of the heat of mixing and the interaction parameter indicated the heterogeneous nature of NR/PMMA blends. The effects of graft copolymer of natural rubber and poly(methyl methacrylate) (NR-g-PMMA) as an emulsifying agent on the interfacial properties of NR/PMMA blends were studied based on the phase separation behaviour. The demixing behaviour is found to be a function of graft copolymer concentration, mode of mixing, nature of solvent and molecular weight of homopolymers and graft copolymers. The demixing behaviour has been studied by noting the phase separation time and volume of the phase separated region. The addition of graft copolymer decreases the demixing behaviour of the blends. This revised version was published online in November 2006 with corrections to the Cover Date.     

木素纤维素吸水材料初探EI

木素纤维素与丙烯腈接枝共聚物经碱溶液水解,可得到具有一定吸水性能的木素纤维素吸水材料。经研究发现该材料的吸水性能与接枝量和水解条件有关。随接枝量的提高,吸水率增加,到一定程度后趋于稳定。在碱性条件下,接枝共聚物中的氰基很快水解成羧酸盐和酰胺基,使接枝物具有一定的吸水性,随水解条件不同,水解产物结构不同,吸水率也不一样,在适当水解条件下可得到能吸收自重60～70倍水的木素纤维素聚合物。     

Centrifugal melt spinning of polyvinylpyrrolidone (PVP)/triacontene copolymer fibres

Polyvinylpyrrolidone/1-triacontene (PVP/TA) copolymer fibre webs produced by centrifugal melt spinning were studied to determine the influence of jet rotation speed on morphology and internal structure as well as their potential utility as adsorbent capture media for disperse dye effluents. Fibres were produced at 72 °C with jet head rotation speeds from 7000 to 15,000 r min^?1. The fibres were characterised by means of SEM, XRD and DSC. Adsorption behaviour was investigated by means of an isothermal bottle point adsorption study using a commercial disperse dye, Dianix AC-E. Through centrifugal spinning nanofibers and microfibers could be produced with individual fibres as fine as 200–300 nm and mean fibre diameters of ca. 1–2 µm. The PVP/TA fibres were mechanically brittle with characteristic brittle tensile fracture regions observed at the fibre ends. DSC and XRD analyses suggested that this brittleness was linked to the graft chain crystallisation where the PVP/TA was in the form of a radial brush copolymer. In this structure, the triacontene branches interlock and form small lateral crystals around an amorphous backbone. As an adsorbent, the PVP/TA fibres were found to adsorb 35.4 mg g^?1 compared to a benchmark figure of 30.0 mg g^?1 for a granular-activated carbon adsorbent under the same application conditions. PVP/TA is highly hydrophobic and adsorbs disperse dyes through the strong “hydrophobic bonding” interaction. Such fibrous assemblies may have applications in the targeted adsorption and separation of non-polar species from aqueous or polar environments.     

聚丙烯酸丁酯接枝共聚物的可控合成及作为相容剂的应用

结合电子转移再生催化剂原子转移自由基聚合(ARGET ATRP)和普通自由基聚合,制备了一系列聚丙烯酸丁酯接枝共聚物,详细研究了其作为苯乙烯-丙烯腈共聚物树脂/丙烯酸酯橡胶(SAN/ACM)共混体系的相容剂,在制备丙烯腈-苯乙烯-丙烯酸酯树脂(ASA树脂)时,不同主链结构、侧链相对分子质量、接枝密度及用量对增容效果的影响。通过傅里叶变换红外光谱仪和凝胶渗透色谱仪对聚合物结构进行测试和表征;采用动态力学分析仪(DMA)和冲击试验机研究了共混物的力学性能。结果表明,成功制备了不同结构的聚丙烯酸丁酯接枝共聚物,以苯乙烯-丙烯腈共聚物(SAN)作为主链比聚丙烯酸丁酯(PBA)作为主链的接枝共聚物具有更好的增容效果。此外,侧链PBA的相对分子质量较小时,侧链与主链摩尔比为3∶1及相容剂用量为3%(质量分数)时,接枝共聚物的增容效果最佳。DMA分析表明添加接枝共聚物后SAN和ACM两组分的玻璃化转变温度相互靠近,聚丙烯酸丁酯接枝共聚物起到了明显的增容作用。     

Release of Ciprofloxacin from Chondroitin 6-Sulfate-Graft-Poloxamer Hydrogel In Vitro for Ophthalmic Drug Delivery

The system was designed to use Poloxamer as a vehicle for ophthalmic drug delivery using in situ gel formation property. To enhance the wound healing and cell adhesion as well as transparency of Poloxamer hydrogel, chondroitin 6-sulfate (C6S) was introduced into Poloxamer. For this purpose, mono amine-terminated Poloxamer (MATP), which was end-capped with ethylene amine group only in one side of terminal hydroxyl groups of Poloxamer, was synthesized. Subsequently, C6S-graft-Poloxamer copolymer (C6S-g-Poloxamer) was prepared by reaction between the amine groups of MATP and carboxyl groups of C6S in the presence of 1-ethyl-3-(3-dimethylaminopropyl)-carboimide (EDC). The coupling of MATP with C6S was clarified by ¹H-NMR and FT-IR spectroscopy. The gelation temperature of graft copolymers was determined by measuring the temperature at which immobility of the meniscus in each solution was first noted. Release behavior of ciprofloxacin from C6S-g-Poloxamer hydrogel in vitro was investigated as a function of C6S content in the graft copolymer by a spectrophotometric assay at 287 nm using an UV spectrophotometer. Differences in the adhesion and morphology of human lens cell between Poloxamer- and C6S-g-Poloxamer-coated surfaces were also investigated. The gelation temperatures of C6S-g-Poloxamer copolymers were lowered with increasing of the concentration of the copolymer and decreasing of C6S content. The release of ciprofloxacin from the graft copolymer was sustained compared with Poloxamer itself and decreased with increasing the content of C6S in the copolymer due to the in situ gel formation of the copolymer and viscous properties of C6S. Human lens cells (B3) adhered to C6S-g-Poloxamer-coated surface were observed as transformed shapes after 2 days. The bioadhesive and thermally gelling of these graft copolymers will be expected to be an excellent drug carrier for the prolonged delivery to surface of the eye.     

Release of ciprofloxacin from chondroitin 6-sulfate-graft-poloxamer hydrogel in vitro for ophthalmic drug delivery

The system was designed to use Poloxamer as a vehicle for ophthalmic drug delivery using in situ gel formation property. To enhance the wound healing and cell adhesion as well as transparency of Poloxamer hydrogel, chondroitin 6-sulfate (C6S) was introduced into Poloxamer. For this purpose, mono amine-terminated Poloxamer (MATP), which was end-capped with ethylene amine group only in one side of terminal hydroxyl groups of Poloxamer, was synthesized. Subsequently, C6S-graft-Poloxamer copolymer (C6S-g-Poloxamer) was prepared by reaction between the amine groups of MATP and carboxyl groups of C6S in the presence of 1-ethyl-3-(3-dimethylaminopropyl)-carboimide (EDC). The coupling of MATP with C6S was clarified by 1H-NMR and FT-IR spectroscopy. The gelation temperature of graft copolymers was determined by measuring the temperature at which immobility of the meniscus in each solution was first noted. Release behavior of ciprofloxacin from C6S-g-Poloxamer hydrogel in vitro was investigated as a function of C6S content in the graft copolymer by a spectrophotometric assay at 287 nm using an UV spectrophotometer. Differences in the adhesion and morphology of human lens cell between Poloxamer- and C6S-g-Poloxamer-coated surfaces were also investigated. The gelation temperatures of C6S-g-Poloxamer copolymers were lowered with increasing of the concentration of the copolymer and decreasing of C6S content. The release of ciprofloxacin from the graft copolymer was sustained compared with Poloxamer itself and decreased with increasing the content of C6S in the copolymer due to the in situ gel formation of the copolymer and viscous properties of C6S. Human lens cells (B3) adhered to C6S-g-Poloxamer-coated surface were observed as transformed shapes after 2 days. The bioadhesive and thermally gelling of these graft copolymers will be expected to be an excellent drug carrier for the prolonged delivery to surface of the eye.     

皂化对于淀粉-MMA接枝共聚物吸水性能影响的研究

对由玉米淀粉(corn starch,CS)与甲基丙烯酸甲酯(MMA)在KMnO4引发下接枝共聚所制得的CS-MMA接枝共聚物进行皂化,制得了高吸水性树脂.研究了不同条件对其吸水性能的影响,确定了制备该高吸水性树脂的最佳工艺条件.在最佳条件下,树脂的吸水率为900g/g.     

溶液接枝共聚合成POE-g-SAN及其表征

合成了POE和苯乙烯(St)-丙烯腈(An)的接枝共聚物(POE-g-SAN)。研究了单体比率及POE和单体比率和溶剂等对接枝共聚合反应的影响。从聚合产物中用丙酮抽提得到接枝共聚物POE-g-SAN,并用傅立叶变换红外光谱(FT-IR)1、H-NMR和差示扫描量热法(DSC)对POE-g-SAN的结构,接枝SAN链的组成及热性能进行了分析。实验证明,St-An已经接枝在POE分子链上,SAN接枝链在一定程度上影响了POE的结晶性。     

甲基丙烯酸甲酯与尼龙接枝共聚反应的研究

研究了过氧化二苯甲酰 (BPO)引发的甲基丙烯酸甲酯与醇溶性尼龙在乙醇中的接枝共聚反应 ,探讨了单体浓度、引发剂浓度对接枝率的影响。并由红外光谱、X射线衍射分析对接枝共聚产物进行了结构表征     

Templated synthesis of Ag-Au bimetallic nanoparticles by amphiphilic PVC-g-PSSA graft copolymer film

Amphiphilic comb-like copolymer consisting of a poly(vinyl chloride) (PVC) backbone and poly(styrene sulfonic acid) (PSSA) side chains, i.e. PVC-g-PSSA at 68:32 wt.% was synthesized via atom transfer radical polymerization (ATRP). This self-assembled graft copolymer film was used to template the growth of Ag-Au bimetallic nanoparticles in the solid state by introducing NaBH₄ as a reducing agent. The in situ formation of Ag-Au bimetallic nanoparticles in the graft copolymer film was confirmed by UV-visible spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). High resolution TEM picture showed the formation of spherical Ag-Au core-shell nanoparticles. To the best of our knowledge, this is the first report on the solid-state synthesis of Ag-Au bimetallic core-shell nanoparticles using amphiphilic comb-like copolymer film.     

聚丙烯／聚苯乙烯共混合金——I．相区分布研究

在PP／PS熔融共混合金中引入一熔融指数与PP相同，质量接枝率为13．5％的PP－g－PS接枝共聚物。SEM和SALS分析结果表明，PP－g－PS改善了PP和PS相的相容性关明显使合金内分散相的相畴分布细化，体系更趋均匀。     

壳聚糖/聚羟基丁酸酯接枝共聚物的合成及血液相容性

以过氧化二苯甲酰为引发剂,在醋酸-二甲基亚砜复合溶剂中进行了聚羟基丁酸酯与壳聚糖的接枝反应,探讨了温度、引发剂用量、用料比、分子量等对接枝率的影响。付里叶红外分光光度法、核磁共振确认了产物的结构。广角X射线衍射及热重分析证实,接枝产物的结晶度和热稳定性好于原料壳聚糖。接枝产物的体外血液相容性评价结果表明,壳聚糖/PHB接枝共聚物表现出溶血率低,复钙化时间长,动态凝血曲线下降平缓,膜表面无血小板粘附,具有良好的血液相容性。     

Controlled release of theophylline through semi-interpenetrating network microspheres of chitosan-(dextran-g-acrylamide)

Semi-interpenetrating network microspheres of chitosan-(dextran-g-acrylamide) were prepared by emulsion-crosslinking method using glutaraldehyde (GA) as a crosslinking agent. Graft copolymerization of dextran with acrylamide (Dx-g-AAm) was carried out by aqueous free-radical polymerization using ceric ammonium nitrate (CAN) as initiator. The grafting efficiency was found to be 92%. Theophylline (TH), antiasthmatic drug, was successfully encapsulated into semi-INP microspheres by varying the ratio of Dx-g-AAm and amount of GA. The laser light scattering technique shows that the particles size increased with increasing amount of graft copolymer and decrease with increasing amount of GA. The % encapsulation efficiency was found to vary between 50 and 78. MPs were characterized by FTIR spectroscopy and differential scanning calorimetry (DSC) techniques to confirm the graft copolymer, formation of semi-IPN structure of MPs and molecular distribution of the drug molecules in the polymer matrix. In vitro release studies of TH from these matrices have been investigated at Ph 1.2 and 7.4 media and the slow release were extended up to 18 h at 37°C. The release rates were fitted to an empirical equation to estimate the diffusion exponent n, which indicated that the release from the MPs follows non-Fickian type.     

HRP引发酚类与淀粉接枝共聚物的制备及结构性能表征

降解淀粉和酚类在辣根过氧化物酶(HRP)/H2O2的催化作用下进行自由基接枝共聚反应,制备了淀粉和酚类接枝共聚物。研究了淀粉降解程度、酚类单体配比、HRP用量、反应温度和pH对接枝改性淀粉结构与性能的影响。研究结果表明,用α-淀粉酶降解后的淀粉15与12g间苯三酚(PG)和20g对羟基苯磺酸钠(HBS)在5mg HRP/H2O2引发体系下,在30℃及pH值为7.0时反应5h制备的酚类与淀粉接枝共聚物具有较好的性能,其水溶液的表面张力为26.6mN/m,所鞣制皮革收缩温度(Ts)达到了78℃。用FT-IR、1 H NMR、UV-Vis和GPC等方法对产物的化学结构进行了表征。     

羟乙基纤维素接枝聚己内酯的生物降解性能

通过三甲基硅(TMS)基团改性保护技术,成功制备了羟乙基纤维素(HEC)接枝聚己内酯(HEC-g-PCL)聚合物,利用红外光谱及核磁共振波谱对合成产物进行了结构验证。利用微生物降解法与活性淤泥法分别对HEC-g-PCL进行了生物降解实验。结果表明,经过霉菌不同时间降解,扫描电子显微镜(SEM)观测产物的表观形貌发生了明显变化;活性淤泥降解HEC-g-PCL产物表明,HEC-g-PCL在中性淤泥状具有自然活性的土壤中,经四周时间,降解率达到8.0%。