不饱和聚酯酰胺树脂/聚磷酸钙纤维复合材料及性能研究

通过熔融缩聚法合成出一种低成本的不饱和聚酯酰胺树脂并表征了其性能,以此为基体,以聚磷酸钙纤维(CPPF)为增强体,引入20 %的交联剂乙酸乙烯酯、0.1%~0.3%的引发剂过氧化苯甲酰和0.1%~0.3%的促进剂N,N-二甲基苯胺室温交联后在195℃下深度交联成可完全降解不饱和聚酯酰胺树脂/CPPF复合材料,并研究了其力学和降解性能。结果表明, 随着CPPF含量的增加, 不饱和聚酯酰胺树脂/CPPF复合材料的力学性能尤其是冲击强度有大幅度的提高,但当CPPF含量超过60 %（质量分数,下同）时,复合材料的力学性能出现下降的趋势;复合材料在模拟体液环境中降解7周后,降解介质的pH和Ca2+浓度保持一个恒定值,降解3个月后含30 %和50 %CPPF的复合材料的弯曲强度分别能保持143、148 MPa。     

不饱和聚酯酰胺树脂/纳米羟基磷灰石复合材料的制备及性能研究

通过熔融缩聚法合成了一种不饱和聚酯酰胺树脂,并用纳米羟基磷灰石（n-HA）进行增强,研究了其弯曲和降解性能。结果表明,不饱和聚酯酰胺树脂有优良的热稳定性;随n-HA含量增加,复合材料弯曲性能有一定升高,但当n-HA含量超过10 ％时弯曲性能反而降低;在前3个月的降解过程中,高n-HA含量的纳米复合材料更能降低力学性能衰减率及减少质量损失率;纳米复合材料在1.0 mol/L NaOH标准溶液中水解10 d后n-HA含量越高,水解越快。     

丙烯酸接枝淀粉基可降解紫外光固化高吸水性树脂的制备与性能

以丙烯酸接枝淀粉为基体,不饱和聚酯酰胺脲树脂为交联剂制备出一种可降解高吸水性树脂,该树脂不加任何光引发剂即可紫外光固化成膜。研究了树脂的吸水速率及交联剂的加入量、光固化时间对产品吸水率的影响。结果表明,该高吸水性树脂对不同溶液均具有较好的吸收能力,吸水速度较快,在蒸馏水、自来水、0.9%NaCl溶液、0.9%KCl溶液中的吸水率分别为905,3501,00,120 g/g;10 min内对蒸馏水的吸收倍率达200 g。该高吸水性树脂的降解从表面开始,逐渐向里面降解。     

不饱和聚酯树脂的气干性改性及其腻子的制备

以DCPD（双环戊二烯）和TMPDE（三羟甲基丙烷二烯丙基醚）作为不饱和聚酯树脂的气干改性剂,并用合成的树脂制备不饱和聚酯腻子。对不饱和聚酯树脂的改性工艺进行了比较和选择,对不饱和聚酯腻子的影响因素进行了评价。     

不饱和聚酯树脂国内研究进展及其国外背景Ⅱ——涂料、胶粘剂与胶衣树脂

综述了不饱和聚酯胶衣、涂料与胶粘剂的国内研究进展,其中包括:国内胶衣与彩胶树脂市场现状,新型的耐候性阻燃胶衣树脂,抗菌胶衣树脂,紫外光固化胶衣树脂,具防污性的不饱和聚酯凝胶涂料,低单体含量的不饱和聚酯复合型组合物及其制备,3 000 t胶衣树脂生产线改造工程职业病危害预评价,不饱和聚酯耐烧蚀包覆材料,无溶剂浸渍漆,道路标线涂料和树脂锚固剂等。     

不饱和聚酯的亲水性研究

本文研究并合成了用作玻璃纤维浸润剂成膜组分的不饱和聚酯树脂ZR。研究表明,随着树脂水溶液pH值的增大,不饱和聚酯的亲水性提高;采用合适的乳化剂和乳化设备,可使树脂水溶液形成乳化液;在树脂主链中引入醚键,可提高树脂的亲水性;用二乙醇胺改性树脂,亦可提高亲水性。在上述研究的基础上,合成了自乳化的ZR树脂,它是一种理想的水溶性不饱和聚酯树脂。     

医用多孔支架材料的制备及缓释性能分析

采用溶液浇铸法制备了聚己内酯⁃姜黄素（PCL⁃CUR）多孔支架,通过冷场发射扫描电子显微镜（SEM）和热重分析仪（TG）等对支架材料的孔隙率、载药量及缓释性等进行了表征,并分析了其体外释药模型。结果表明,CUR在支架材料中含量为2 %（质量分数,下同）,PCL在醋酸中浓度为10 %,壳聚糖在支架材料中含量为2.86 %时,其释药模型符合1级方程,支架材料的孔隙率达95 %以上,载药量达到1.63 %,在PBS缓冲液中90 h内CUR累计释放率为76.2 %;其他配方的支架材料孔隙率均为95 %以上,90 h内CUR累计缓释率在60 %~87 %之间,表明制得的支架材料具有较理想的孔隙率和明显的CUR药物缓释作用,在组织工程领域有较好的应用前景。     

右旋布洛芬/尿素改性蒙脱土复合物的制备及体外释药性能

以蒙脱土为药物载体,利用尿素固相研磨法将蒙脱土层间距撑大,以提高其载药量;采用溶液插层法实现右旋布洛芬的有效负载,制备右旋布洛芬/尿素改性蒙脱土[S（+）-IBU/urea-MMT]复合物;借助X射线衍射（XRD）和傅里叶红外变换光谱（FT-IR）对复合物进行结构表征;采用透析法研究复合物中药物的体外释药性能;运用3种数学模型对其体外释放行为进行拟合分析,探索释药机理。结果表明,在尿素的作用下,蒙脱土的层间距由1.20 nm增大到1.79 nm,右旋布洛芬的负载量最高可达227.9 mg·g^-1,较改性前提高了30%;S（+）-IBU/urea-MMT复合物具有良好的缓释效果,在人工模拟胃液（pH 1.2）和人工模拟肠液（pH 6.8）中的累计释放量分别为19.2%和88.4%;复合物的释药行为基本符合零级释放动力学模型。     

玉米醇溶蛋白作为阿司匹林缓控释骨架材料的研究

以阿司匹林（Aspirin）为模型药物,玉米醇溶蛋白（Zein）作为骨架材料,采用混合压片法制备了不同配方的药物片剂。紫外比色法测定释放效果,根据药片溶出实验结果进行数理统计,模拟释药方程。结果表明：Zein作为骨架材料的片剂释药时间都达到了6h以上,控制药剂配方中阿司匹林和分散剂淀粉用量的比例,就可以实现不同的控释效果。实验结果表明了玉米醇溶蛋白是一种良好的天然药物缓控释骨架材料。     

含乳酸酯链节的不饱和聚酯

用丙交酯（由乳酸脱水得到）与顺丁烯二酸酐及1，2-丙二醇含成了不饱和聚酯树脂，树脂能与苯乙烯、甲基丙烯酸甲酯相溶混，能用一般不饱合聚酯的交联方法固化，固化后的拉伸强度与普通不饱和聚酯相当，且透明性良好。树脂的合成机理在文中进行了讨论。此研究着眼于树脂的环境降解及资源可再生性考虑。     

New polyanhydrides derived from C12,C13,C14,C15 dibasic acid: synthesis and characterization

Poly(dodecanedioic acid-tetradecandioic acid) (P(DDDA-TA)) copolymers and poly(brassylic acid-pentadecandioic acid) (P(BA-PA)) copolymers have been prepared by melt polycondensation of the corresponding mixed anhydride prepolymers derived from dodecanedioic acid, brassylic acid, tetradecandioic acid and pentadecandioic acid. The copolymers were characterized by FT-IR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), wide angle X-ray powder-diffraction, and thermal gravimetric analysis (TGA). In vitro studies showed that all the copolymers are degradable in phosphate buffer at 37 °C. The release profiles of hydrophilic model drug, ciprofloxcin hydrochloride, from the copolymers, follows first order release kinetics. All the preliminary results suggested that the copolymer might be potentially used as drug delivery devices.     

紫杉醇-SIBS体外药物释放动力学研究

采用聚（苯乙烯-b-异丁烯-b－苯乙烯）三嵌段共聚物（SIPS）作为紫杉醇药物载体,研究了紫杉醇释放动力学行为。对紫杉醇-SILKS载药共聚物进行了差示量热扫描仪分析（DSC）和原子力显微镜（AFM）的表征;研究了不同苯乙烯（St）含量的紫杉醇-SIBS载药共聚物在pH=7．4磷酸缓冲液（PBS）（37℃）中的动力学。结果表明紫杉醇-SIRS载药共聚物随着St含量的增加,紫杉醇的释放率较低,且其释药率在8d以后趋于平稳;在体外释药过程中随着磷酸缓冲液的置换量越大,紫杉醇的释放率越高。     

Preparation and properties of poly(dimer acid-sebacic acid) copolymer

Summary Poly (dimer acid-sebacic acid) P(DA-SA) copolymers have been prepared by melt polycondensation of the corresponding mixed anhydride prepolymers. The copolymers were characterized by FT-IR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). In vitro studies showed that all the copolymers are degradable in phosphate buffer at 37°C, and leaving an oily dimer acid residue after hydrolysis for the copolymer with high content of dimer acid. The release profiles of hydrophilic model drug, ciprofloxcin hydrochloride, from the copolymers, follows first order release kinetics. The in vivo biocompatibility of the copolymer in rabbit brain was also evaluated, macroscopic observation and microscopic analysis demonstrated that the copolymer is biocompatible and well tolerated in vivo. All the preliminary results suggested that the copolymer might be potentially used as drug delivery devices for brain implantation. Received: 4 April 2001/Revised version: 10 May 2001/Accepted: 22 May 2001     

Lipase‐catalyzed synthesis of polymeric prodrugs of nonsteroidal anti‐inflammatory drugs

Because of the potential application of prodrugs of nonsteroidal anti‐inflammatory drugs (NSAIDs), Candida antarctica lipase B (CAL‐B) catalyzed polycondensation of profen‐containing diol monomers and diesters were designed to prepare a series of biodegradable polymeric prodrugs composed of NSAID branches and poly(amide‐co‐ester) backbone. The structure of the products was confirmed by Fourier transform infrared spectroscopy, NMR, and gel permeation chromatography (GPC). The reaction conditions of polymerization, such as the enzyme source, amount of catalyst, and temperature, were optimized. The molecular weights of resultant copolymers were 2170–13,270 g/mol, with corresponding polydispersities from 1.17 to 2.4. The copolymers had relatively high drug loadings of 44.7–59.7 wt % because every repeat unit contained one drug molecule. The strategy of enzymatic polymerization appeared to be quite general and accommodated a large number of comonomer substrates with various chain lengths and substituents. The optically pure (R)‐naproxen monomer was demonstratively incorporated into the corresponding copolymers with the developed synthesis strategy. The in vitro study showed that the polyester could release the drug effectively under physiological conditions with enzyme, which indicated that the obtained product could be a promising prodrug for extending pharmacological effects by delayed drug release. With GPC analysis, we confirmed that the prodrug was completely degradable in aqueous solution. The attractive features of the copolymer were its high drug loading, biodegradability, and biocompatibility. The high tolerance of the CAL‐B toward drug groups, as described in this article, provides a new route for synthesizing polymeric drugs with potential biomedical applications in mild conditions and for reducing environmental impact. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Hot-melt pressure-sensitive adhesives based on SIS-g-PB copolymer for transdermal delivery of hydrophilic drugs

SIS-g-PB copolymers were successfully synthesized by grafting living polybutadiene (PB) lithium macroanions onto epoxidized SIS copolymers. Their molecular structures and thermal properties were characterized by TGA, ¹H-NMR and DSC, respectively. SIS, epoxidized SIS (ESIS) and SIS-g-PB copolymers were melt-blended with tackifiers to develop hot-melt pressure-sensitive adhesives (HMPSAs), respectively (named of H-SIS, H-ESIS and H-SIS-g-PB). Their adhesive performances were measured in terms of 180° peel strength and holding power. A modified Franz type horizontal diffusion cell was used to carry out In vitro drug release experiments, in which geniposides were chosen as hydrophilic model drugs. The results showed that H-SIS-g-PB has two times as high a 180° peel strength as H-SIS. Meanwhile H-SIS-g-PB has a slightly lower drug cumulative release rate than H-ESIS. It is indicated that the PB branches not only could impart good adhesive performance to H-SIS-g-PB via improving the compatibility between the epoxidized main chains and tackifier resins but also provide release channels to hydrophilic drugs by retaining most of the epoxide groups in the SIS-g-PB copolymers.     

生物可降解两亲性嵌段共聚物胶束的制备及其对叶酸的控制释放

以甲氧基聚乙二醇(mPEG)为引发剂,在辛酸亚锡催化下引发ε-环己内酯(CL)开环聚合,合成了聚乙二醇-聚己内酯两亲性嵌段共聚物(mPEG-PCL)。通过FTIR、1H-NMR及GPC等表征手段确定了mPEG-PCL的组成及结构。采用芘荧光探针法、透射电镜和动态激光光散射研究了聚合物在水中的自组装行为。结果表明:聚合物在水溶液中能够自组装形成粒径小于100 nm的规则球状胶束,且具有较低的临界胶束浓度(7.35×10-3 g/L);模型药物(叶酸)成功负载于聚合物纳米胶束内,并且能延缓叶酸的释放,其释药速率受载药量和释放介质pH的影响。     

Progress of photo-responsive drug release systems（Pr-DDS）

响应型药物释放体系（Pr-DDS）可以实现药物的定时、定位释放,是一种洁净、无创、高效的载体材料。本文根据为聚合物提供光敏感性的差异性将其分为：光异构化型（偶氮苯,Azo）、分子内光致成键和断裂型（螺吡喃,Spiro）、光二聚化型（香豆素,Cou）以及光致断裂型（邻硝基苯衍生物）,并对上述4种类型载体材料的研究进展进行综述。在4类光敏感药物载体材料中,以偶氮苯为代表的光异构化型药物载体研究最为广泛,其中涉及胶团、囊泡、水凝胶、脂质体等,而以邻硝基苯衍生物为代表的光致断裂型由于具有双光子响应能力,近年来也引起了广泛的关注。最后总结指出关于光敏感型药物载体的构建,目前虽取已得了长足的发展,但仍然存在诸多的问题,如何提高生物相容性、增加对目标位置的靶向性以及生物体内光控释放的可行性仍然亟待解决。     

Synthesis of thermostable nomex copoly(amide–imide) and their properties

Thermostable Nomex copoly(amide–imide)s with inherent viscosity of 0.72–1.31 dL/g were synthesized by reacting diacid-terminated Nomex prepolymer with various diisocyanate-terminated polyimide prepolymers. The polyimide prepolymer was prepared by using 4,4′-diphenylmethane diisocyanate to react with 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, or 3,3′,4,4′-sulfonyl diphthalic anhydride using a direct one pot method in order to improve their solubility. The copolymers, except B-1, P-1, P-2, D-1, and D-2, could be dissolved in N, N-dimethylacetamide +5% lithium chloride at room temperature or dimethyl sulfoxide at high temperature but were not soluble in N,N-dimethylformamide or pyridine. The solubility is considered to be related to their crystallinity. Those copolymers with crystalline structure displayed poor solubility. All the Nomex copoly(amide–imide)s had glass transition temperatures in the range of 223–352°C and showed a 10% weight loss temperature of 438–574°C in air and 441–585°C in nitrogen atmosphere. The tensile strength, elongation at break, and initial modulus of polymer films ranged 63–118 MPa, 4–9% and 1.67–2.53 GPa, respectively. From the X-ray diffraction studies, copolymers of B-1, P-1, P-2, D-1, and D-2 with high content of PmIA showed a crystalline structure, but the others only displayed an amorphous morphology. © 1996 John Wiley amp; Sons, Inc.     

两亲性三嵌段共聚物的合成、表征及其药控释放行为的研究

以三硫代碳酸双(α,α′-二甲基α-″-乙酸)酯为链转移剂,以苯乙烯(St)或甲基丙烯酸甲酯(MMA)为亲油性单体,以甲基丙烯酸二甲氨基乙酯(DMA)为亲水性单体,AIBN为引发剂,通过可逆加成断裂链转移(RAFT)聚合得到两种两亲性三嵌段共聚物,通过凝胶渗透色谱(GPC)测试其组成分别为PS16-PDMA56-PS16,PMMA11-PDMA38-PMMA11,PMMA15-PDMA40-PMMA15,Mw/Mn分别为1.20、1.27、1.29。并用1HNMR进一步表征了嵌段共聚物结构。TEM及粒度测试研究发现,PS-PDMA-PS在特定溶剂中可以自组装成球形胶束,其尺寸在380 nm左右;而PMMA-PDMA-PMMA自组装成的胶束则呈均匀的球形,胶束分散较好,粒径约在120 nm左右。并研究了3种胶束对水溶性模型药物对羟基苯甲醚(HOA)的缓释效果,发现在同一时间PS-PDMA-PS胶束的累积释放量比其他胶束的小,药物的控释遵循扩散机理,并且胶束尺寸对药物的释放速率影响较大。