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1.
二醋酸纤维素接枝丙交酯共聚物的合成与表征   总被引:1,自引:0,他引:1  
以二醋酸纤维素为接枝骨架,在辛酸亚锡的催化下,通过L-丙交酯的开环接枝聚合反应,合成了二醋酸纤维素和聚丙交酯接枝共聚物(CDA-g-PLA),并采用GPC、FTIR、1H-NMR和DSC对接枝共聚物进行表征.研究了原料质量比、催化剂用量、反应时间、反应温度对单体转化率(C%)、接枝率(G%)的影响.结果表明:反应温度150℃,单体丙交酯与二醋酸纤维素质量比为4:1,反应时间30min,催化剂辛酸亚锡与二醋酸纤维素的质量比为1%时,产物的接枝率较高.  相似文献   

2.
不同旋光度PLGA的制备及其结晶性能研究   总被引:1,自引:0,他引:1  
以消旋丙交酯、左旋丙交酯和乙交酯为原料,以辛酸亚锡为引发剂,在高真空条件下本体熔融开环聚合,制得一系列不同旋光度的丙交酯乙交酯共聚物(PLGA),其结构经1H NMR, IR, XRD和DSC表征.并采用DSC研究了PLGA的熔体结晶行为,结果表明其结晶性能随其旋光度的减少而显著降低,甚至不结晶.  相似文献   

3.
官能团化己内酯与丙交酯无规共聚物的合成与降解性能   总被引:1,自引:1,他引:0  
研究了官能团化新型己内酯单体的合成及其与丙交酯无规共聚物的降解性能. 首先, 环己酮和N-异丙基丙烯酰胺通过Michael加成反应合成了2-(N-异丙基酰胺乙烯基)-环己酮; 然后, 以间氯过氧化苯甲酸为氧化剂, 通过Baeyer-Villiger氧化反应, 制备带有酰胺官能团的己内酯单体6-(N-异丙基酰胺乙烯基)-ε-己内酯; 最后, 在异辛酸亚锡[Sn(Oct)2]的催化下与丙交酯开环聚合, 得到新型己内酯与丙交酯的无规共聚物. 采用1H NMR, SEC和DSC表征了聚合物的结构和热力学性能. 同时通过黏度法、失重法和SEM对该聚合物的降解性能进行了表征. 结果表明, 该共聚物的降解速率明显增快, 材料降解2个月后, 材料的质量损失达到28.1%, 特性黏度降低近40%.  相似文献   

4.
赵衡柱  杨青芳  艾莉  马强 《合成化学》2005,13(4):368-371
以辛酸亚锡为催化剂催化丙交酯开环聚合DL-乳酸(PDLLA)。研究了影响PDLLA分子量的因素包括丙交酯单体的纯度、催化剂的浓度、反应温度、反应时间及真空度等。用DSC,TGA分析了不同分子量PDLLA的警警化转变和热失重。结果表明,PDLLA是热不稳定聚合物,残留的单体、催化剂及低聚物是影响PDLLA热稳定性的因素,除去其中残留的单体、催化剂及低聚物可以提高PDLLA的热稳定性。  相似文献   

5.
以辛酸亚锡为催化剂,十八醇为引发剂,分别以右旋丙交酯和左旋丙交酯与乙交酯为原料,在真空条件下经本体熔融开环聚合制备了系列右旋丙交酯聚合物(E)和左旋丙交酯乙交酯共聚物(F),其结构经1H NMR和IR表征。利用DSC研究了E和F共混物(M)的结晶性能,结果表明,E和F能形成具有较高熔点的立构复合物(SC),其形成能力随E分子量的增加而降低,且SC的含量在E和F共混比为49∶51附近出现极大值。  相似文献   

6.
稀土复合氧化物催化合成丙交酯的研究   总被引:7,自引:0,他引:7  
以新型稀土La—Ti复合氧化物作为催化剂,催化乳酸合成丙交酯,考察了催化剂对反应体系粘度、丙交酯产率、反应时间、反应温度的影响,获得了较佳的反应工艺条件:减压下,70~90℃脱自由水1.5h;随后加入催化剂,用量为乳酸重量的0.8%,缓慢升温到120~140℃进行缩聚反应3~4h;再在170~260℃,保持升温速率为4℃/10min进行裂解,产物纯度和结构分别由Thiele管和红外光谱进行测定,丙交酯粗产率达88.5%,纯产率为40.2%,表明该催化剂具有良好的催化性能。  相似文献   

7.
一锅法合成甲基丙烯酰基封端的PLA-PEG-PLA大分子单体   总被引:2,自引:0,他引:2  
以辛酸亚锡[Sn(Oct)2]为催化剂、聚乙二醇为引发剂引发丙交酯开环聚合,用水终止反应后再加入甲基丙烯酸酐反应即可得到甲基丙烯酰基封端的PLA-PEG-PLA大分子单体。上述两步反应可一锅进行,操作简便、收率高。采用GPC、FTIR、^1H-NMR、TG、XRD等分析手段表征了大分子单体的结构和性质。所得大分子单体的水溶液在光引发剂存在下,能被UV引发光聚合形成水凝胶。该水凝胶作为可降解生物材料可用于药物控释栽体和组织工程支架。  相似文献   

8.
聚乳酸-聚乙二醇-聚乳酸三嵌段共聚物的降解性能   总被引:15,自引:3,他引:12  
以辛酸亚锡为引发剂,聚乙二醇大分子为共引发剂进行现交酯开环聚合,制备了系列聚乳酸(PLA)-聚乙二醇(PEG)-聚乳酸(PLA)三嵌段共聚物。从共聚物在生理盐水 中降解时特性粘度[η],质量和热行为的变化,考察了PEG分子量和丙交酯/PEG(摩尔比)对共聚物降解行为的影响,结果表明,PEG嵌段对共聚物的降解速率有重要影响,丙交酯/PEG一定时,PEG分子量越大,共聚物越容易降解,PEG嵌段长度一定时,丙交酯/PEG越大,共聚物降解速率越小。  相似文献   

9.
以L型丙交酯(LLA)、乙交酯(GA)和三亚甲基碳酸酯(TMC)为原料,辛酸亚锡为催化剂,通过开环聚合制备了丙交酯-三亚甲基碳酸酯二元共聚物(PLT)和丙交酯-三亚甲基碳酸酯-乙交脂(PLTG)三元共聚物。采用核磁共振氢谱、傅里叶红外光谱、体积排阻色谱、差热扫描、力学性能测试、血液相容性实验表征了产物的结构与性能,研究了共聚物组成对其结晶能力、热性能和力学性能的的影响。结果表明:所得聚合物的数均分子量均在8×10~4以上,多分散系数在2.0以下。共聚物中的TMC和GA链段使其结晶能力、玻璃化转变温度和拉伸强度与L型聚丙交酯相比均有所下降。三元共聚物PLTG的拉伸强度可达到22.3 MPa,断裂伸长率达到168.7%。另外,共聚物的血液相容性优良。  相似文献   

10.
以辛酸亚锡催化L-丙交酯(L-LA)和ε-己内酯(ε-CL)通过酯交换反应完成本体开环聚合制得可降解的生物医用材料聚(L-丙交酯-co-ε-己内酯)(PLLCA),其结构和热性能经1H NMR,高效凝胶色谱和差示扫描量热分析表征。研究了酯交换反应条件对PLLCA力学性能的影响,结果表明,提高聚合温度有利于酯交换反应进行,L-LA和ε-CL的平均嵌段长度减小,PLLCA的玻璃化转变温度(Tg)和拉伸强度也随之减小,断裂伸长率则单调增大;增大ε-CL的投料摩尔分数同样有利于酯交换反应的进行,L-LA的平均嵌段长度随之减小而ε-CL的平均嵌段长度则增大,Tg和拉伸强度均随之减小。  相似文献   

11.
Ring‐opening polymerization of ?‐caprolactone was carried out smoothly and effectively with constant microwave powers of 170, 340, 510, and 680 W, respectively, with a microwave oven at a frequency of 2.45 GHz. The temperature of the polymerization ranged from 80 to 210 °C. Poly(?‐caprolactone) (PCL) with a weight‐average molar mass (Mw) of 124,000 g/mol and yield of 90% was obtained at 680 W for 30 min using 0.1% (mol/mol) stannous octanoate as a catalyst. When the polymerization was catalyzed by 1% (w/w) zinc powder, the Mw of PCL was 92,300 g/mol after the reaction mixture was irradiated at 680 W for 270 min. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1749–1755, 2002  相似文献   

12.
To fulfill the diverse requirements in surgery and medicine, biomedical polymers have been drawing interests and attentions increasingly since the last decade1. In these fields, aliphatic carbonates have been proved to be a kind of material with excellent…  相似文献   

13.
Poly (lactic acid) (PLA) is an important member of the polyesters which are used as biomedical materials in bioresorbable suture, implantates and drug controlled release systems1. PLA is prepared by two routs2: ring-opening polymerization of dimeric cyclic lactide or direct polycondensation of lactic acid. The ring-opening polymerization has attracted much more scientific and industrial interests than the later one, but both methods need long time for the polymerization reactions to be compl…  相似文献   

14.
以环氧丙烷聚醚三元醇(PPO)为起始剂,开环聚合D型丙交酯(DLA),合成三臂环氧丙烷聚醚三元醇-聚右旋乳酸(PPO-PDLA)嵌段预聚体.采用端基活化技术对预聚体进行端羟基活化,再与L型丙交酯(LLA)进行逐步开环聚合,合成了不同分子量的三臂环氧丙烷聚醚三元醇-聚右旋乳酸-聚左旋乳酸(PPO-PDLA-PLLA)嵌段共聚物.采用红外(FTIR)、核磁(NMR)和凝胶渗透色谱(GPC)等对三臂PPO-PDLA-PLLA嵌段共聚物的测试表明,合成的嵌段共聚物分子链具有很高的立构规整度;通过调节LLA单体与PPO-PDLA预聚体的投料比,不仅可控制产物的分子序列结构,而且样品的数均分子量可大于100 kDa.差示扫描量热仪(DSC)和广角X射线衍射(WAXD)结果显示,三臂PPO-PDLA-PLLA嵌段共聚物的异构体链段分子间生成立构复合晶体,其熔点约为200℃,且没有PLLA均聚物链段结晶现象.实验结果表明,这是一类具有实际应用价值的新型耐热聚乳酸(PLA)材料.  相似文献   

15.
Using a semi-empirical molecular orbital method, PM3, and 2-propanol as an example, the dehydration and the dehydrogenation processes of alcohol on oxide catalysts were studied. The catalysts addressed here were four kinds of oxides (Al2O3, SiO2, ZnO, CdO) whose reaction selectivities had been experimentally determined. The usual models consisting of a surface metal ion, several oxide ions and an isopropoxy group were used in calculations. For the dehydration, heats of formation of the models were calculated at each point of the process where the distance between a β-hydrogen of the group and a basic site (i.e. oxygen of the group or a surface oxide ion) or a metal ion was gradually shortened, or where the length of the C–O bond of the group was gradually increased. A reasonable dehydration mechanism was estimated by comparing activation energies calculated from the transitions of the heats of formation. The most probable dehydrogenation mechanism was also estimated in a similar way by gradually making an -hydrogen close to a surface oxide ion, the metal ion or a surface proton. It was concluded that the dehydration proceeds by scission of the C–O bond of the group after its oxygen was attacked by some electrophile on the surface and that the dehydrogenation proceeds by a mechanism in which an -hydrogen of the group was extracted by the metal ion.

Based on the dehydration mechanism thus deduced, alkoxy groups generated by adsorption of the primary, secondary and tertiary alcohols on SiO2 were calculated in order to estimate the activation energies of their decompositions. In result, the order of the energies was found to be in good agreement with that of the decomposition rates experimentally determined by Kitahara. This agreement gives support to the validity of the mechanism deduced for the dehydration of alcohol.  相似文献   


16.
A one‐step process is reported to directly synthesize blends of poly(trimethylene carbonate) (PTMC) with a modified granular starch. Trimethylene Carbonate (TMC) ring‐opening polymerization is performed in the presence of native starch particles in bulk conditions at 150 °C and the efficiency of metal‐free organic catalysts (TBD and phosphazene superbases P1‐t‐Oct, P2‐t‐bu, and P4‐t‐bu) are investigated to replace the organo‐metallic stannous octanoate initiator. TMC monomer is successively converted into PTMC and the robustness of organic catalysts is highlighted with significant activities at very low concentrations (<100 ppm), where stannous octanoate is inefficient. Reactivity of starch toward TMC ROP is deeply investigated by NMR techniques and a starch‐graft‐PTMC is indirectly evidenced. Starch substitution degree reaches 0.9% indicating that PTMC grafting only occurs at the surface of swollen granular starch. PTMC graft length from the starch surface remained low in the range 2–12 and model ROP reactions highlight the role of TMC hydrolysis on PTMC graft length. Despite low PTMC grafts, a fine dispersion of intact starch particles into the PTMC matrix is evidenced. Consequently, metal‐free organic catalysts at low concentrations are promising candidates for synthesizing blends of PTMC with high loadings of surface‐modified starch (32% by weight) in 2 min within a one‐step process. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 493–503  相似文献   

17.
张胜寒  檀玉  梁可心 《电化学》2011,(2):212-216
应用电化学方法研究了锌离子注入(zinc injection)技术对核电站结构材料,如304L不锈钢、316L不锈钢和600合金在高温水中形成氧化膜的电化学性能影响.锌离子注入压水堆(PWR)一回路技术可有效减少材料应力腐蚀破裂(stress corrosion cracking)和职业辐照.用动电位扫描法检测材料氧化...  相似文献   

18.
负载型ZnO/SiO2及ZnO-SiO2溶胶凝胶催化剂的表面结构研究   总被引:2,自引:0,他引:2  
催化剂的表面结构不仅影响催化剂的催化活性, 而且还影响反应产物的选择性[1]. 制备催化剂的方法不同, 其表面结构及表面性质也不同[2~4]. 浸渍法简单实用, 有利于得到高分散、晶粒细小的高比表面催化剂, 而溶胶-凝胶法则由于其制备温度较低, 易于形成无定形的或介态的氧化物相[5]而可达到分子级的混合, 其活性组分能有效地嵌入网状结构中, 不易受外界的影响而聚集或长大, 因此对催化剂的稳定性更为有利[6,7].  相似文献   

19.
功能聚碳酸酯的合成及表征   总被引:2,自引:0,他引:2  
脂肪族聚碳酸酯作为生物材料已引起普遍关注,由于其良好的生物相容性、表面溶蚀性和无毒性,在医学领域中得到越来越广泛的应用.迄今已报道的许多脂肪族聚碳酸酯的降解速率相对较慢,如聚三亚甲基碳酸酯的降解速率比聚乳酸和聚己内酯慢很多.但是,如果在聚碳酸酯的侧链上引入亲水性功能基团,其降解速率将会明显提高.  相似文献   

20.
Periodontal diseases like gingivitis and periodontitis are primarily caused by dental plaque. Several antiplaque and anti-microbial agents have been successfully incorporated into toothpastes and mouthwashes to control plaque biofilms and to prevent and treat gingivitis and periodontitis. The aim of this article was to review recent developments in the antiplaque, anti-gingivitis, and anti-periodontitis properties of some common compounds in toothpastes and mouthwashes by evaluating basic and clinical studies, especially the ones published in the past five years. The common active ingredients in toothpastes and mouthwashes included in this review are chlorhexidine, cetylpyridinium chloride, sodium fluoride, stannous fluoride, stannous chloride, zinc oxide, zinc chloride, and two herbs—licorice and curcumin. We believe this comprehensive review will provide useful up-to-date information for dental care professionals and the general public regarding the major oral care products on the market that are in daily use.  相似文献   

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