Controlled destruction of residual crosslinker in a silicone elastomer for drug delivery

In drug delivery systems that use silicone elastomers as a diffusion matrix for the active drug, it is common to crosslink the material by the hydrosilylation reaction. In this platinum‐catalyzed reaction, vinyl groups on a polymer add to the methyl siloxane hydride (MHS) groups on a low molecular mass crosslinker. With an excess of crosslinker, a fast curing is achieved and a fully crosslinked material is formed. Unreacted MHS groups were shown to remain in the elastomer after curing because of the excess crosslinker. In this work, a simple procedure was developed to eliminate the unreacted MHS groups from the final product. We found that storage of the product at +40°C and 75% relative humidity for a few weeks will effectively destroy the residual MHS groups in the elastomer. The effects of varying levels of humidity, oxygen, and temperature on this postcuring procedure were studied. The amount of MHS groups was measured with NMR and IR spectroscopy. We also found that the hardness of the material increased by approximately 25% as a consequence of this postcuring treatment. This increase is probably due to a secondary crosslinking reaction between MHS and silanol groups. Heat treatment at higher temperatures led to an even further increase in the hardness and compression modulus. Because no MHS groups remained in the elastomer when this heat treatment was started, it is apparent that another secondary crosslinking reaction is occurring, probably silanol condensation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2254–2264, 2002     

过氧化甲乙酮合成研究

研究了在酸性催化剂存在下，以邻苯二甲酸二丁酯作溶剂，由双氧水和甲乙酮作用制取过氧化甲乙酮溶液的工艺，并得到最佳工艺条件。结果表明，产品性能优良。     

Physical agglomeration behavior in preparation of cellulose‐N‐methyl morpholine N‐oxide hydrate solutions by simple mixing

The different melting temperatures of N‐methyl morpholine N‐oxide (NMMO) hydrates in the cellulose–NMMO hydrate solution may be explained by the rather different crystal structures of NMMO hydrates, which are determined by the amount of the hydrates. The preparative process of cellulose–NMMO hydrate solution may result in cellulose structural change from cellulose I to cellulose II, depending on the amount of the hydrate. Mixtures of cellulose and NMMO hydrate in a blender was changed from the granules to slurry with increasing mixing time at 60–70°C, which is below the melting point of the NMMO hydrate. In the case of 15 wt % cellulose–NMMO hydrate granules, which were made by mixing for 20 min, the melting points of various NMMO hydrates were obtained as 77.8°C (n = 0.83), 70.2°C (n = 0.97), and 69.7°C (n = 1.23), respectively, depending on the hydrate number. However, the melting points of cellulose–NMMO hydrate slurry and solution were shifted lower than those of cellulose granules, while the mixing time of slurry and solution are 25 and 35 min, respectively. These melting behaviors indicate instantaneous liquefaction of the NMMO hydrate and the diffusion of the NMMO hydrate into cellulose during mixing in a blender. When cellulose was completely dissolved in NMMO hydrate, the crystal structure of cellulose showed only cellulose II structure. In the cellulose–NMMO products of granules or slurry obtained by high‐speed mixing, which is a new preparation method, they still retained the original cellulose I structure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1687–1697, 2004     

Kinetic and molecular weight control for methyl methacrylate semibatch polymerization. II. Open control

The gel effect will bring a violent increase of conversion for methyl methacrylate (MMA) polymerization in a short time. It will be very dangerous for the reactor, as it causes an increase of molecular weight and broadens the molecular weight distribution. To unify the kinetics, molecular weight, and its distribution, on the basis of the mathematical models for semibatch polymerization of MMA, three controlled objectives that are the heat load distribution index, the change in molecular weight, and molecular weight distribution index are presented. Three materials (monomer, solvent, and chain transfer agent) and their flow rate and feeding mode are analyzed for the open control of kinetics, molecular weight, and its distribution. The optimum flow rate and mode are obtained. The heat load distribution index and molecular weight distribution index are even less than 2.0 and 2.2, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4399–4405, 2006     

微波促进二氯菊酸甲酯的水解新工艺研究

采用微波技术对二氯菊酸甲酯在NaOH溶液中水解为二氯菊酸工艺进行了研究。结果表明,微波促进下最佳水解条件为:反应温度90℃,功率100 W,反应时间10 m in,物质的量比n(二氯菊酸甲酯)∶n(C2H5OH)∶n(NaOH)=1∶4∶1.5,重结晶后收率高达99.6%。与传统条件相比,时间缩短30倍,收率提高24.6%,无水乙醇用量减少60%,NaOH用量减少17%。并用红外光谱和熔点对二氯菊酸进行表征。     

精对苯二甲酸装置乙酸甲酯回收与利用

介绍了精对苯二甲酸装置对二甲苯氧化反应过程中副产物乙酸甲酯回收与利用，乙酸甲酯回收不仅可以减少排放到大气和污水中的有机物，而且可以返回到氧化反应系统，改善反应状况，降低醋酸消耗。     

Graft copolymerization of 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid onto carboxymethylcellulose (sodium salt) by H2O2/Fe+2 redox pair

The effect of the reaction conditions on the grafting parameters during grafting of 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid onto sodium carboxymethylcellulose using H₂O₂/Fe⁺² redox pair are studied at 30°C. The grafting ratio, add on, and conversion initially increase with the H₂O₂ concentration in the range of (10.0–15.0) × 10^?2 mol dm^?3. Thereafter, these parameters decrease with the H₂O₂ concentration. The grafting ratio, add on, and conversion increase when increasing the ferrous ion concentration from (0.5 to 4.0) × 10^?2 mol dm^?3 and decrease with a further increase in the concentration. It is observed that the grafting ratio and add on increase with the monomer concentration, whereas the conversion decrease. The hydrogen ions seem to be facilitating the grafting reaction up to a certain concentration and after this concentration seem to be retarding the process. The grafting ratio, add on, and conversion decrease with the sodium carboxymethylcellulose concentration. When increasing the time period from 60 to 90 min, the grafting parameters increase but decrease thereafter. Similarly, when increasing the temperature from 25 to 30°C, the grafting parameters increase and decrease thereafter. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4819–4825, 2006     

Synthesis,characterization, and thermal behavior study of methyl methacrylate polymers containing 4‐carbazole substitutes

A new polymerizable monomer, [4‐(9‐ethyl)carbazolyl]methyl methacrylate ( 2 ), was synthesized by reacting of methacrylic acid and 4‐hydroxymethyl‐9‐ethyl carbazole ( 1 ) by esterification procedure in the presence of N,N′‐dicyclohexylcarbodiimide. The resulting monomer was then polymerized free‐radically to form the poly(methyl methacrylate) containing 4‐(9‐ethyl)carbazolyl pend ent groups. Also, copolymerization of monomer 2 with various acrylic monomers such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, and n‐butyl acrylate by azobisisobutyronitrile as a free radical polymerization initiator gave the related copolymers in high yields. The structure of all the resulted compounds was characterized and confirmed by FTIR and ¹H NMR spectroscopic techniques. The average molecular weight of the obtained polymers was determined by gel permeation chromatography using tetrahydrofurane as the solvent. The thermal gravimetric analysis and differential scanning calorimeter instruments were used for studying of thermal properties of polymers. It was found that, with the incorporation of bulky 4‐(9‐ethyl)carbazolyl substitutes in side chains of methyl methacrylate polymers, thermal stability and glass transition temperature of polymers are increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4989–4995, 2006     

丙烯酰胺与2-丙烯酰胺基-2-甲基丙磺酸反相乳液聚合的研究

采用Span-80为乳化剂，白油为分散介质，（NH4）2S2O8-Na2SO3为引发剂，研究了丙烯酰胺（AM）与2-丙烯酰胺基-2-甲基丙磺酸（AMPS）的反相乳液共聚反应，合成出了高相对分子质量的共聚物。讨论了引发剂用量、乳化剂用量、水油比、单体浓度等因素对共聚物相对分子质量的影响。引发剂用量为单体质量的0．2‰，乳化剂为油相的6．7％，水油比为1：1．5，单体浓度为37．5％时可获得高相对分子质量的共聚物，且聚合反应平稳易控制。     

水溶液中纳米二氧化钛光催化降解甲基橙的影响因素

用沸腾回流直接水解法制备了粒径为25～35 nm纯锐钛矿型纳米二氧化钛(TiO2).用X射线衍射和透射电镜表征材料的结构与形貌.用该催化剂催化降解甲基橙,研究了催化剂用量、甲基橙的起始浓度、溶液pH值、光强度、溶液中添加金属离子的影响.结果表明:在较强紫外光照射下,当甲基橙的起始浓度为0.02 g/L,TiO2用量为1.0g/L,光催化效率最高.酸性条件有利于光催化降解甲基橙.掺加Fe3 或Zn2 的光催化效率显著增加.掺加Mn2 或Ca2对光催化活性没有影响.在紫外光区域(366 nm),样品对催化降解水溶液中甲基橙的活性较高.