DCP引发高全同聚丁烯-1熔融接枝马来酸酐

研究了在双螺杆挤出机中,苯乙烯(St)存在下马来酸酐(MAH)熔融接枝高全同聚丁烯-1(iPB-1)的过程。分别考察了温度、MAH和St用量对接枝率和熔体流动速率(MFR)的影响。结果表明,双螺杆挤出机反应区的适宜温度为170℃,在此温度下,MAH含量到5%时,接枝率达到最大;MAH含量一定时,MAH∶St=1∶1时两种单体可以较好地相互作用,并在引发剂的作用下优先生成苯乙烯与马来酸酐的共聚物(SMA),然后再与iPB-1大分子链自由基或链端自由基发生反应,生成接枝物,此时接枝率达到最大。     

湿固化型SBS胶粘剂的制备及性能

用γ-氨丙基三乙氧基硅烷(KH550)对马来酸酐接枝的苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS-g-MAH)进行改性,制备出具有湿固化性能的SBS胶粘剂。通过红外光谱、热分析以及剥离强度测试探讨了SBS起始浓度、马来酸酐(MAH)、KH550以及萜烯树脂的用量等对产物性能的影响。结果表明,当SBS浓度为0.13 g/mL,SBS∶MAH∶BPO=10∶1∶0.06(质量比),KH550用量为SBS的13.63%,萜烯树脂用量为SBS的90%时,聚乙烯膜的T型剥离强度达到11.2N.25mm-1,同时对极性的聚氯乙烯的剥离强度也有提高。     

改性聚丙烯和聚丙烯包装膜的研究

用双螺杆挤出机研究了马来酸酐(MAH)对聚丙烯(PP)的自由基熔融接枝.采用正交试验优化了熔融接枝条件, 考察了引发剂过氧化二异丙苯DCP、单体MAH用量对马来酸酐接枝率的影响,并对其影响因素作了分析.研究表明改性以后的PP制成的PP膜性能更进一步提高.确定了较佳的原料(质量)配比为PP:MAH:DCP =100:3:0.4.     

MAH等离子体改性PVDF薄膜表面的亲水性研究

以马来酸酐(MAH)低温等离子体接枝聚合的方法对聚偏氟乙烯(PVDF)薄膜表面进行亲水改性.分析了袁面的MAH化学结构;考察了等离子体功率与表面聚合量和表面水接触角的关系;讨论了改性薄膜在热浓硫酸中长期作用的结果.结果表明:等离子体使MAH在表面双键打开并接枝聚合;聚合量随处理功率的增加呈先上升后下降的趋势,30W时最大;经过等离子体处理后,水接触角由97°下降至45°～70°,水解后降低至40°～55°,30W的改性膜表面水接触角最小;改性薄膜在热浓硫酸中作用1000h后,MAH聚合物没有被腐蚀掉,与未浸泡硫酸试样相比,水接触角变化不大.     

马来酸酐/N-乙烯基吡咯烷酮双单体接枝聚丙烯的制备及对聚丙烯微孔膜的亲水改性EI北大核心CSCD

以马来酸酐(MAH)为功能单体,N-乙烯基吡咯烷酮(NVP)为共聚单体,采用熔融接枝法制备两亲性改性剂PP-g-(MAH-co-NVP),并通过热致相分离法制备聚丙烯(PP)亲水微孔膜。通过红外光谱仪和元素分析仪表征了PP-g-(MAHco-NVP)的化学结构和接枝率,使用差示扫描量热仪、X射线衍射仪表征了PP-g-(MAH-co-NVP)的结晶性能。利用接触角、热失重分析、扫描电子显微镜和孔隙率测试对改性前后的PP膜进行研究。结果显示,亲水支链成功接枝到PP大分子链上,相比于MAH作为唯一的接枝单体,NVP的加入使MAH的接枝率增加了270%;且NVP的加入促进了PP分子链的结晶。改性PP微孔膜的热稳定性能提高,膜孔数增多,孔隙率增加了2. 8%。并且改性PP微孔膜的亲水性也得到改善,接触角下降了28. 5%。     

马来酸酐/N-乙烯基吡咯烷酮双单体接枝聚丙烯的制备及对聚丙烯微孔膜的亲水改性

以马来酸酐(MAH)为功能单体,N-乙烯基吡咯烷酮(NVP)为共聚单体,采用熔融接枝法制备两亲性改性剂PP-g-(MAH-co-NVP),并通过热致相分离法制备聚丙烯(PP)亲水微孔膜。通过红外光谱仪和元素分析仪表征了PP-g-(MAHco-NVP)的化学结构和接枝率,使用差示扫描量热仪、X射线衍射仪表征了PP-g-(MAH-co-NVP)的结晶性能。利用接触角、热失重分析、扫描电子显微镜和孔隙率测试对改性前后的PP膜进行研究。结果显示,亲水支链成功接枝到PP大分子链上,相比于MAH作为唯一的接枝单体,NVP的加入使MAH的接枝率增加了270%;且NVP的加入促进了PP分子链的结晶。改性PP微孔膜的热稳定性能提高,膜孔数增多,孔隙率增加了2. 8%。并且改性PP微孔膜的亲水性也得到改善,接触角下降了28. 5%。     

棉织物表面引发聚合亲水性高分子膜的研究

以马来酸酐预接枝修饰纯棉机织物,重点探究了紫外光引发聚合甲基丙烯酸羟乙酯(HEMA)的浓度对其在修饰后棉织物表面聚合膜形貌的影响和膜形貌对织物表面结构和亲水性的影响.研究表明,马来酸酐在DMF/LiCl(5%)体系中,反应温度T=90℃、时间t=4h、浓度为1.5mol/L时,在织物表面的接枝率可达到8.87%;红外光谱分析发现,接枝后的棉织物在1 728cm-1和1 641cm-1处出现了明显的羰基峰和碳碳双键峰.通过场发射扫描电子显微镜和水接触角仪对PHEMA聚合膜在织物表面的形貌结构及亲水性进行了表征.结果表明,PHEMA聚合膜较好地覆盖了纤维之间的孔隙;织物表面的亲水性有所下降,其水接触角最高可达130°左右,但大约16s后全部渗进织物内部.     

悬浮接枝法制备PP-g-MAH纤维及其对水中铜离子的吸附性能

研究了聚丙烯悬浮接枝马来酸酐及其对水体中铜离子的吸附效果。以水为分散介质,二甲苯(Xyl)为界面剂,过氧化苯甲酸叔丁酯(TBPB)为引发剂,考察了聚丙烯(PP)悬浮法接枝马来酸酐(MAH)反应中各反应条件和原料组份对接枝率的影响。当反应条件为PP∶MAH∶TBPB∶Xyl=100∶5∶4.7∶23,反应温度130℃,反应时间4h时,产物接枝率为1.38%。在此基础上,探讨了在PP-g-MAH纤维对水中铜离子的吸附,研究了pH值、吸附时间以及不同铜离子浓度对吸附效果的影响。     

POE-g-SMA的制备及其对PA6/PTFE共混体系的增容作用

通过马来酸酐(MAH)和苯乙烯(St)双单体溶液接枝法制得了增容剂马来酸酐-苯乙烯接枝乙烯-辛烯共聚物(POE-g-SMA),研究发现,接枝率与反应时间、温度、POE/SMA及引发剂用量有关;POE-g-SMA对聚酰胺6/聚四氟乙烯(PA6/PTFE)共混物有很好的增容作用,加入POE-g-SMA后,复合材料的力学性能和摩擦磨损性能得到改善。     

ABS高胶粉接枝马来酸酐及其对ABS/PET合金性能的影响

采用溶液法制备了丙烯腈-苯乙烯-丁二烯高胶粉(ABSHR)接枝马来酸酐(MAH),使用红外光谱表征了ABSHR接枝马来酸酐(ABSHR-g-MA)的结构;探究了MAH、BPO、ABSHR的用量及反应温度和反应时间对ABSHR-g-MA接枝率的影响,以及ABSHR-g-MA作为增容剂对ABS/PET合金性能的影响。结果表明:ABSHR-g-MA接枝率随着MAH和BPO用量的增加而增加,但添加量过高时,接枝率增加缓慢或有所降低;适当升高反应温度和延长反应时间有利于接枝反应的发生;ABSHR-g-MA作为ABS/PET合金增容剂,随着ABSHR-g-MA接枝率的增加缺口冲击强度和断裂伸长率明显增加,分别提高了127%和121%,而拉伸强度和弯曲强度稍有降低;同时随ABSHR-g-MA接枝率的增加合金的耐热性能提高,熔融流动速率有所降低。     

改性β-环糊精微球的制备与表征

采用反相乳液聚合法制备β-环糊精(pCD)微球,再用顺丁烯二酸酐(MAH)改性制得丁烯二酸单酯化β-CD微球,探讨了不同工艺参数对改性β-CD微球粒径、分散性的影响.结果表明,在60℃的温度和200r/min～300r/min的电动搅拌,环氧氯丙烷(EPI)和β-CD的质量比为15∶1,复合乳化剂司盘-80和吐温-20...     

聚乙烯基硅氧烷功能微球的制备研究

采用水解-缩聚两步法以乙烯基三甲氧基硅烷(VTMS)为原料,制备超细聚乙烯基硅氧烷微球,粒径为1~6μm,粒径分布较窄;就反应体系氨水浓度、油水比、反应温度等条件对微球形态、粒径大小及其分布的影响进行了研究。结果表明较优的反应条件为:氨水浓度在0.01%~0.16%之间,投料油水比(VTMS与去离子水的体积比)应小于1∶3;随着油水比的增大和反应体系中氨水浓度的降低,微球的粒径增大,分布变宽。     

pH敏感水凝胶微球的制备及二甲酸钾缓释和抗菌性能分析

二甲酸钾(KDF)为抗生素的新型替代品,但在牲畜饲养中还未大量普及。采用水热法自制P型分子筛(Zeolite P),负载KDF分散在羧甲基纤维素(CMC)溶液中,与FeCl₃交联,利用凝聚法制备壳聚糖-羧甲基纤维素-P型分子筛-二甲酸钾pH敏感水凝胶抗菌微球。通过FT-IR,TGA和SEM分析可知,壳聚糖(CS)和CMC通过离子键形成结构稳定的聚电解质复合物,Zeolite P镶嵌缠绕在CMC基质中。溶胀差异性表明水凝胶微球具有高pH敏感性,可以适用不同pH条件下的持续给药。缓释动力学研究表明:抗菌微球对KDF具有一定的缓释作用,且遵循一级动力学释放模型和Higuchi模型。体外抗菌实验发现,抗菌液浓度为24 mg/mL和48 mg/mL时对大肠杆菌和金黄色葡萄球菌有显著的抗菌性,可以有效地抑制细菌的生长。     

Preparation and evaluation of a novel gastric mucoadhesive sustained-release acyclovir microsphere

Objective: The objective of this study was to prepare a novel gastric mucoadhesive sustained-release acyclovir (AV)-resinate microsphere. Methods: First, AV absorption ratio was quantified in a rat gastrointestinal (GI) tract model. AV-resinate was prepared by bath method and used as cores to prepare microspheres by an emulsion solvent diffusion technique with carbopol 934 as coating material. GI transit test of the prepared microspheres was carried out in rats and beagle dogs, followed by the in vivo bioavailability evaluation of the microspheres in beagle dogs. Results: The AV absorption ratio in different segments of rat's GI track for 3 hours was as following: stomach 9.46 ± 0.62%, duodenum 20.22 ± 1.50%, jejunum 15.7 ± 1.33%, ileum 9.15 ± 1.01%, and colon 4.59 ± 0.48%. These results showed that AV was mainly absorbed in the stomach and upper intestine. The average diameter of the microspheres was 115.3 μm. The microspheres had a drug content of 33.3 ± 0.7% (w/w) and a sustained-release profile for 12 hours in vitro. The mucoadhesive test in rats and beagle dogs showed that most of the microspheres were retained in the stomach 6 hours after oral administration. The in vivo pharmacokinetics test revealed that the microsphere and reference (AV tablets) preparations have no significant difference for C_max. The t_max has increased from 2.33 hours (reference) to 5 hours (test). Meanwhile, the relative bioavailability of AV microspheres was 145%. Conclusion: A novel AV-resinate microsphere was prepared. The microspheres were proved to be gastric mucoadhesive and sustained-release with higher bioavailability.     

Selective laser sintering of porous tissue engineering scaffolds from poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide)/carbonated hydroxyapatite nanocomposite microspheres

This study focuses on the use of bio-nanocomposite microspheres, consisting of carbonated hydroxyapatite (CHAp) nanospheres within a poly(L: -lactide) (PLLA) matrix, to produce tissue engineering (TE) scaffolds using a modified selective laser sintering (SLS) machine. PLLA microspheres and PLLA/CHAp nanocomposite microspheres were prepared by emulsion techniques. The resultant microspheres had a size range of 5-30 mum, suitable for the SLS process. Microstructural analyses revealed that the CHAp nanospheres were embedded throughout the PLLA microsphere, forming a nanocomposite structure. A custom-made miniature sintering platform was installed in a commercial Sinterstation((R)) 2000 SLS machine. This platform allowed the use of small quantities of biomaterials for TE scaffold production. The effects of laser power; scan spacing and part bed temperature were investigated and optimized. Finally, porous scaffolds were successfully fabricated from the PLLA microspheres and PLLA/CHAp nanocomposite microspheres. In particular, the PLLA/CHAp nanocomposite microspheres appeared to be promising for porous bone TE scaffold production using the SLS technique.     

乙烯基胶原蛋白微球的制备及其应用

为了得到带有“-C=C-”的胶原蛋白微球,我们使用甲基丙烯酸酐对胶原蛋白改性,再采用乳化交联法将改性胶原蛋白制备成乙烯基胶原蛋白微球(CMAs),并将微球应用到尼龙基材上。研究了CMAs的制备条件,使用傅里叶红外光谱(FT-IR)、扫描电子显微镜(SEM)、激光粒度分析仪等对CMAs和乙烯基胶原蛋白微球/尼龙(Nylon-CMAs)进行表征。结果表明,当乙烯基胶原蛋白浓度为15%,转速为800 r/min,交联剂用量为0.8 mL,水油体积比为1∶5,乳化剂用量为2%时,制备的乙烯基胶原蛋白微球的平均粒径为21.204μm,形貌规整、圆整度好,表面光滑,粒径分布较窄。接触角结果显示将微球修饰到尼龙上可以使尼龙由原来的疏水织物变为亲水织物,且制备的织物具有较好的水热稳定性能。     

Process and formulation variables of pregabalin microspheres prepared by w/o/o double emulsion solvent diffusion method and their clinical application by animal modeling studies

Pregabalin is an anticonvulsant drug used for neuropathic pain and as an adjunct therapy for partial seizures with or without secondary generalization in adults. In conventional therapy recommended dose for pregabalin is 75?mg twice daily or 50?mg three times a day, with maximum dosage of 600?mg/d. To achieve maximum therapeutic effect with a low risk of adverse effects and to reduce often drug dosing, modified release preparations; such as microspheres might be helpful. However, most of the microencapsulation techniques have been used for lipophilic drugs, since hydrophilic drugs like pregabalin, showed low-loading efficiency and rapid dissolution of compounds into the aqueous continous phase. The purpose of this study was to improve loading efficiency of a water-soluble drug and modulate release profiles, and to test the efficiency of the prepared microspheres with the help of animal modeling studies. Pregabalin is a water soluble drug, and it was encapsulated within anionic acrylic resin (Eudragit S 100) microspheres by water in oil in oil (w/o/o) double emulsion solvent diffusion method. Dichloromethane and corn oil were chosen primary and secondary oil phases, respectively. The presence of internal water phase was necessary to form stable emulsion droplets and it accelerated the hardening of microspheres. Tween 80 and Span 80 were used as surfactants to stabilize the water and corn oil phases, respectively. The optimum concentration of Tween 80 was 0.25% (v/v) and Span 80 was 0.02% (v/v). The volume of the continous phase was affected the size of the microspheres. As the volume of the continous phase increased, the size of microspheres decreased. All microsphere formulations were evaluated with the help of in vitro characterization parameters. Microsphere formulations (P1–P5) exhibited entrapment efficiency ranged between 57.00?±?0.72 and 69.70?±?0.49%; yield ranged between 80.95?±?1.21 and 93.05?±?1.42%; and mean particle size were between 136.09?±?2.57 and 279.09?±?1.97?µm. Pregabalin microspheres having better results among all formulations (Table 3) were chosen for further studies such as differential scanning calorimetry, Fourier transform infrared analysis and dissolution studies. In the last step, the best pregabalin microsphere formulation (P3) was chosen for in vivo animal studies. The pregabalin-loaded microspheres (P3) and conventional pregabalin capsules were applied orally in rats for three days, resulted in clinical improvement of cold allodynia, an indicator of peripheral neuropathy. This result when evaluated together with the serum pregabalin levels and in vitro release studies suggests that the pregabalin microspheres prepared with w/o/o double emulsion solvent diffusion method can be an alternative form for neuropathic pain therapy. Conclusively, a drug delivery system successfully developed that showed modified release up to 10?h and could be potentially useful to overcome the frequent dosing problems associated with pregabalin conventional dosage form.     

Agarose-polymeric microsphere beads: Specific new adsorbents for hemoperfusion

Uniform agarose-polymeric microsphere beads of 1 mm diameter were synthesized by encapsulating appropriate polymeric microspheres in an agarose matrix. The potential use of these beads for hemoperfusion was demonstrated. Agarose provides the high porosity and the biocompatibility of the beads; the encapsulated microspheres are used for the removal of harmful substances from the circulatory system. Two types of polymeric microspheres were prepared: (a) polymercaptal microspheres of 0.8 micrometer average diameter; (b) polyacrolein microspheres of 0.2 micrometer average diameter. Agarose-polymercaptal microsphere beads were designed for the removal of heavy metals by hemoperfusion. As a model, the detoxification of mercury compounds was studied. Agarose-polyacrolein microsphere beads were designed for the removal of antibodies by hemoperfusion, especially in autoimmune diseases. As a model, the removal of anti-BSA from immunized animals was studied.     

苯乙烯/甲基丙烯酸共聚微球的制备及其性能表征

以苯乙烯(St)为单体,甲基丙烯酸(MAA)为功能单体,采用无皂乳液聚合方法制备了聚(苯乙烯-甲基丙烯酸)共聚微球。运用傅立叶红外光谱(FT-IR)、透射电子显微镜(TEM)、场发射扫描电镜(FE-SEM)、电势与纳米粒径分析仪等手段,对微球的组成成分、表面形貌、粒径及其分布、表面电势进行了表征。结果表明,微球粒径均匀,在100～200nm之间,球形度良好且呈单分散性,poly(St-MAA)共聚微球zeta电势为-37.2mV,MAA的亲水性基团和引发剂KPS的残基共同作用提高了共聚微球乳液的稳定性。     

Polymer microspheres with active carboxyl groups: preparation, structure and hydrophilicity

A quantitative research of microspheres, poly(ethylene glycol dimethacrylate-co-acrylic acid) (P(EGDMA-co-AA)) and poly(divinvlbenzene-80-co-acrylic acid) (P(DVB-co-AA)), with active carboxyl groups on surface prepared by distillation-precipitation polymerization was presented in this paper. The loading capacity of active carboxyl group on microspheres which was investigated by titration technique would be increased and the contact angle was decreased following the increase of the feed ratio of acrylic acid (AA) monomer. This phenomenon indicated that the hydrophilicity of particles was mainly determined by the feed ration of hydrophilic AA monomer. However, when the AA fraction was at a fixed level, a slight difference of the loading capacity of carboxyl groups on microsphere surfaces with different crosslinkers existed. The microspheres with EGDMA as crosslinker had a higher loading capacity of carboxyl groups and lower contact angle than those of P(DVB-co-AA) microspheres, which indicated that P(EGDMA-co-AA) microspheres were more hydrophilic than P(DVB-co-AA) microspheres.