Preparation,characterization and in vitro drug release properties of polytrimethylene carbonate/polyadipic anhydride blend microspheres

Polyadipic anhydride (PAA), an aliphatic polyanhydride, and polytrimethylene carbonate (PTMC), an aliphatic polycarbonate, were synthesized via ring opening polymerization of oxepan‐2,7‐dione and melt‐condensation of trimethylene carbonate (1,3 dioxan‐2‐one), respectively. PTMC–PAA blend microspheres containing different ratios of buprenorphine HCl (2, 5, and 10%) were prepared by an oil‐in‐oil emulsion solvent removal method. Microspheres with different ratios of PTMC–PAA (85/15, 70/30, and 55/45) containing 5% buprenorphine HCl were prepared. Microspheres were spherical with visible cracks and pores on the surface. The average particle size of microspheres was around 200 μm for all microspheres. Drug loading efficiency of PTMC–PAA microspheres (85/15, 70/30, and 55/45) was 97.2, 95.2, and 70.2%, respectively. With the increase in the PTMC ratio, the melting point and the enthalpy of melting were both decreased. The mechanism for drug release from PTMC–PAA blend microspheres were generally a combination of drug diffusion through polymers and biodegradation of the polymers. In first three days, the release from microspheres followed zero order kinetics and was dependent on the PAA content. After three days the drug release from microspheres followed first order kinetics. In conclusion it was demonstrated that buprenorphine HCl release from microspheres could be successfully controlled by using different ratios of PTMC–PAA blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2377–2383, 2006     

新型非离子型反应性乳化剂的合成及其应用

马来酸酐与饱和脂肪醇酯化反应得到马来酸酐单酯羧酸;聚乙二醇和丙烯酸反应得到聚乙二醇丙烯酸单酯;二者在催化剂的作用下反应,得到马来酸酐-丙烯酸型的非离子型反应性乳化剂。进行提纯后,经红外鉴定目标产物,结构正确。将合成的反应性乳化剂用于St/MMA/BA的乳液聚合中,得到的苯丙乳液单体转化率为95.8%,凝胶率0.09%,固含量42.5%,粒径为80~100 nm。作为对比,将传统乳化剂十二烷基硫酸钠(SDS)应用到该聚合中,结果发现,由反应性乳化剂制的苯丙乳液的耐电解质稳定性和储存稳定性等得到较大提高。     

Synthesis and properties of poly(amide–imide)s based on N,N′‐bis(4‐carboxyphenyl)‐4,4′‐oxydiphthalimide,p‐aminobenzoic acid and various aromatic diamines

A new diimide–diacid monomer, N,N′‐bis(4‐carboxyphenyl)‐4,4′‐oxydiphthalimide (I), was prepared by azeotropic condensation of 4,4′‐oxydiphthalic anhydride (ODPA) and p‐aminobenzoic acid (p‐ABA) at a 1:2 molar ratio in a polar solvent mixed with toluene. A series of poly(amide–imide)s (PAI, III_a–m) was synthesized from the diimide–diacid I (or I′, diacid chloride of I) and various aromatic diamines by direct polycondensation (or low temperature polycondensation) using triphenyl phosphite and pyridine as condensing agents. It was found that only III_k–m having a meta‐structure at two terminals of the diamine could afford good quality, creasable films by solution‐casting; other PAIs III using diamine with para‐linkage at terminals were insoluble and crystalline; though III_g–i contained the soluble group of the diamine moieties, their solvent‐cast films were brittle. In order to improve their to solubility and film quality, copoly(amide–imide)s (Co‐PAIs) based on I and mixtures of p‐ABA and aromatic diamines were synthesized. When on equimolar of p‐ABA (m = 1) was mixed, most of Co‐PAIs IV had improved solubility and high inherent viscosities in the range 0.9–1.5 dl g^?1; however, their films were still brittle. With m = 3, series V was obtained, and all members exhibited high toughness. The solubility, film‐forming ability, crystallinity, and thermal properties of the resultant poly(amide–imide)s were investigated. © 2002 Society of Chemical Industry     

偏苯三酸三（2-乙基）己酯（TOTM）中和水洗实验研究

通过采用钛酸四异丙酯(TPT)为催化剂,偏苯三酸酐和2-乙基己醇为原料催化合成增塑剂偏苯三酸三异辛酯(TOTM)的基础上。通过正交试验研究了生成产物中和水洗的最佳条件。     

Interfacial adhesion reaction of polyethylene and starch blends using maleated polyethylene reactive compatibilizer

The interfacial reaction of the polyethylene (PE)/starch blend system containing the reactive compatibilizer maleated polyethylene (m‐PE) was directly characterized by Fourier transform infrared (FTIR) spectroscopy. A significant amount of anhydride groups on m‐PE existed as hydrolyzed forms, resulting in a large amount of carboxyl groups. Using a vacuum‐heating‐cell designed in the laboratory, the carboxyl groups were successfully transformed into the dehydrolyzed state (i.e., anhydride group). This result enabled the direct spectroscopic observation of chemical reaction occurring at the interface. For the PE/starch blend system containing m‐PE, the chemical reaction at the interface was verified by the evolution of ester and carboxyl groups in the FTIR spectra. The effect of the reactive compatibilizer on the interfacial morphology was also examined by scanning electron micrography (SEM). Enhanced interfacial adhesion was clearly observed for the blend system containing reactive compatibilizer. Tensile strengths of blend systems containing m‐PE also increased noticeably compared with the corresponding system without compatibilizer. A similar observation was made for the breaking elongation data. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 767–776, 2002     

苯甲酰丙烯酸乙酯中主要杂质的定性分析与转化

顺丁烯二酸酐与苯在三氯化铝的存在下,经傅-克反应生成苯甲酰丙烯酸,在强酸性水介质中,若温度高于35℃,则部分发生与水的加成反应生成苯甲酰乳酸。含苯甲酰乳酸的苯甲酰丙烯酸在浓硫酸的存在下与无水乙醇反应,可分别生成苯甲酰丙烯酸乙酯和苯甲酰乳酸乙酯。而苯甲酰乳酸乙酯在二甲苯中回流可脱去一分子水而转变为苯甲酰丙烯酸乙酯,从而使苯甲酰丙烯酸乙酯的纯度从85%提高到93%。     

Functionally substituted tetramethylcyclopentadienes: Synthesis of 1-(p-hydroxyphenyl)-2,3,4,5-tetramethylcyclopentadiene and its use in the synthesis of an organometallic polymer

Reaction of 2,3,4,5-tetramethylcyclopent-2-enone (1) withp-LiC₆H₄OC-Me₂OMe, followed by treatment with aqueous acid afforded 1-(p-hydroxyphenyl)-2,3,4,5-tetramethylcyclopentadiene (2). This new ligand was then used in the synthesis of the functionally substituted organomolybdenum reagent (⁵-C₅Me₄-p-C₆H₅OH)Mo(CO)₂(NO) (3). Treatment of a preformed 1/1 styrene/maleic anhydride copolymer ( ) with 5 mol% 3 led to chemical incorporation of the organometallic species into the polymer. The final product contained 3 mol% of the organometallic moiety.     

聚羧酸助磨剂合成及其性能

利用水泥粉磨过程中的机械力促使水解聚马来酸酐（HPMA）与聚乙二醇单甲醚（MPEG）进行酯化反应形成聚羧酸助磨剂。试验研究了HPMA、MPEG、HPMA与MPEG的混合物、HPMA与MPEG的反应合成物对水泥助磨效果以及对砂浆性能的影响。结果表明,HPMA与MPEG都有一定的助磨性,HPMA与MPEG的混合物和反应合成物具有更佳的助磨性能,且可以改善水泥砂浆的流动性能和显著提高水泥砂浆的早期强度。激光拉曼光谱测试表明HPMA与MPEG的混合物和反应合成物与水泥共同粉磨后吸附在水泥颗粒表面,具有相似的拉曼位移图谱。     

大豆浓缩磷脂的马来酸酐酰化改性研究

以马来酸酐为酰化试剂,与大豆浓缩磷脂进行酰化改性反应,探讨了马来酸酐用量、反应时间、反应温度等对浓缩磷脂酰化改性的影响.结果表明:酰化试剂用量为5%,时间为30 min,温度为55℃时,浓缩磷脂的酸价从18.45 mg/g升至58.85 mg/g,酰化率达87.35%,再用碱中和酰化磷脂降低酸价.由红外光谱测定酰化改性磷脂结构可知:在1 500~1 700 cm-1有吸收峰,即酰胺基团的引入;比拟法测定HLB值达5~7,乳化性能有明显的提高和改善.     

苯乙烯-马来酸酐交替共聚的合成研究

本实验以偶氮二异丁腈(AIBN)为引发剂,甲苯为溶剂,采用溶液沉淀聚合工艺合成了苯乙烯-马来酸酐共聚物,并详细考察了单体配比、单体浓度对聚合反应的产率和分子量的影响,对比了链转移剂对聚合产物分子量的影响.进一步通过红外,聚合物粘均分子量测定,对共聚物进行表征.