2-溴丙酰基末端对于PLLA成核行为影响的研究

通过研究2-溴丙酰基单封端的PLLA结晶行为,来探讨聚合物结晶过程中的端基效应.首先通过开环聚合的方法(ROP),以苯甲醇为引发剂,合成了聚(L-乳酸)(PLLA).再将PLLA自由末端的羟基转化为2-溴丙酰基,得到2-溴丙酰基单封端的PLLA-Br.研究表明,2-溴丙酰基末端引入后,聚合物链段运动能力受到抑制,PLL...     

以聚乳酸为侧链的光学活性聚苯乙炔的合成与表征

通过4-溴苯甲醇和三甲基硅基乙炔的Sonagashira偶联反应与三甲基硅基的脱除反应,合成4-乙炔基苯甲醇.以4-乙炔基苯甲醇为引发剂,以有机氮杂环化合物DBU为催化剂,常温常压下进行丙交酯的活性开环聚合反应,采用1H-NMR和GPC对产物结构、分子量与分子量分布进行表征分析,结果表明,合成以了苯乙炔为端基的聚乳酸大...     

原位生成三苄氧基钇催化ε-己内酯可控开环聚合

本文研究了以烷基钇[Y(CH2SiMe3)3(THF)2]与苯甲醇原位反应生成的三苄氧基钇为引发剂的ε-己内酯(CL)可控开环聚合。研究结果表明,随着聚合体系中单体/引发剂摩尔比的增大,由1H-NMR计算和GPC测定得到的产物聚己内酯(PCL)的数均分子量均随之线性增加,且分子量分布(Mw/Mn =1.4～1.1)逐渐变窄;1H-NMR计算所得PCL的数均分子量与由单体/引发剂投料比计算得到的理论值一致,表明该体系催化的CL开环聚合具有很好的可控性。1H-NMR分析显示产物PCL的端基分别为苯甲醇酯和醇羟基,由此提出了可能的开环聚合机理。     

TiCl_4共引发异丁烯正离子聚合合成反应活性聚异丁烯

由H2O/TiCl4/甲醇或乙醚体系引发异丁烯在二氯甲烷与己烷混合溶剂中进行正离子聚合,探讨甲醇用量、聚合时间等因素对正离子聚合以及产物分子量、分子量分布和末端基结构的影响,并在此基础上探讨TiCl4共引发混合C4馏分中异丁烯选择性正离子聚合以制备活性聚异丁烯的可行性.结果表明,含氧试剂对聚合反应起到明显的调节作用,可适当稳定碳正离子活性中心,降低链增长速率,降低聚合产物的分子量(Mn=1600~4600),使分子量分布明显变窄(Mw/Mn=1.35~2.05),并可调节大分子链末端基结构及其含量.降低聚合体系中微量单体浓度以及适当延长聚合反应时间,均有利于提高聚异丁烯大分子链末端α-双键结构含量.通过TiCl4共引发异丁烯正离子聚合制备出末端α-双键含量可以达到70%以上的低分子量高反应活性聚异丁烯.此外,该引发体系还可引发混合C4馏分原料中异丁烯进行高选择性正离子聚合,得到Mn=2000、Mw/Mn=2.59、端基α-双键含量为38.9%的聚异丁烯.     

三臂支化PLLA-PDLA嵌段共聚物的合成及立构复合结晶行为

以三羟甲基乙烷为起始剂, 开环聚合L-丙交酯(LLA), 合成三臂支化左旋聚乳酸(PLLA)预聚物. 采用端基活化技术对预聚物进行端羟基活化, 再与D-丙交酯(DLA)进行开环聚合, 合成了不同分子量的三臂支化左旋聚乳酸-右旋聚乳酸(PLLA-PDLA)嵌段共聚物. 采用核磁共振谱和凝胶渗透色谱等对样品的结构和分子量进行测试, 结果表明,合成的嵌段共聚物链结构具有链段立构规整度和高分子量的特点; 通过调节DLA单体与PLLA预聚物的投料比, 可实现对PLLA-PDLA嵌段共聚物的序列结构调控. 差示扫描量热仪和广角X 射线衍射结果表明, 三臂支化PLLA-PDLA嵌段共聚物的异构体分子间生成立构复合晶体, 其熔点高于200℃; 共聚物的嵌段序列结构对材料的凝聚态转变行为有很大的影响.     

端基为巯基的聚己内酯的合成

以三氟甲烷磺酸亚锡为催化剂, 2-巯基乙醇为引发剂, 在温和条件下引发ε-己内酯的开环聚合, 得到端基为巯基的聚己内酯, 其分子量可控且分布较窄. 在此过程中, 巯基不需要保护而不会影响聚酯的结构, 当聚合温度升高时, 聚合物端基结构不发生改变, 但分子量分布变宽. 端基为巯基的聚己内酯能够通过偶合反应生成中间含二硫键的聚己内酯; 同时, 以2-羟乙基二硫化合物为引发剂合成得到分子中间含二硫键的窄分布聚己内酯, 经还原后也可得到端基为巯基的聚己内酯. 这两种方法条件温和, 效率较高, 具有良好的可控性.     

三嵌段聚乳酸在溶剂中结晶驱动自组装

以端羟基聚二甲基硅氧烷(HO-PDMS-OH)为引发剂,引发L-丙交酯(L-LA)开环聚合,合成了4种三嵌段聚合物聚(L-丙交酯)-b-聚二甲基硅氧烷-b-聚(L-丙交酯)(PLLA-b-PDMS-bPLLA)。其中,聚二甲基硅氧烷(PDMS)含有74个结构单元,聚(L-丙交酯)(PLLA)的结构单元数分别是82、150、224和280。用凝胶渗透色谱仪(GPC)表征了聚合物分子量及分子量分布。将这4种三嵌段聚合物分别溶解在N,N-二甲基甲酰胺(DMF)中,在恒温水槽中静置48h,可分别组装成螺旋线聚集体以及"eye-like"聚集体。PLLA-b-PDMS-b-PLLA的组装主要由PLLA嵌段的结晶驱动。最后采用广角X射线衍射(WAXD)、透射电镜(TEM)、原子力显微镜(AFM)对聚集体进行了相关表征。     

三步法合成高封端率端氨基聚乳酸

叔丁氧羰基碳酸酐((Boc)2O)和氨基丙醇反应合成叔丁氧羰基氨基丙醇(Boc-氨基丙醇),以此为引发剂在辛酸亚锡的催化下,引发L-丙交酯开环聚合合成叔丁氧羰基氨基封端聚乳酸(BocNH-PLLA),叔丁氧羰基(Boc)经三氟乙酸处理脱除后得到端氨基聚乳酸(PLLA-NH2).以PLLA-NH2为大分子引发剂,引发ω-苄氧羰基L-赖氨酸-N-羧酸酐(ω-Z-L-Lysine-NCA)开环聚合,合成聚L-乳酸-聚ω-苄氧羰基L-赖氨酸两嵌段共聚物(P(LLA-LLz)).采用红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)、凝胶渗透色谱(GPC)对聚合物结构进行了表征.结果表明:PLLA-NH2端基亲核性明显提高,可引发ω-Z-L-Lysine-NCA开环聚合制备嵌段共聚物,PLLA-NH2的合成方法简便,氨基封端率高,其分子量和单体与引发剂的摩尔比具有良好的线性关系.     

光敏聚合中含二苯酮基高聚物的引发作用

合成了多种不同分子量和不同二苯酮侧基含量的高分子敏化剂PVB,从紫外吸收光谱及发射光谱的测定结果表明,PVB基本保持小分子二苯酮(BP)的光化学特性。采用PVB与叔胺组成光敏引发体系引发MMA光聚合时,聚合速度(R_ο)与小分子相比增加二倍以上。而且R_p随PVB分子中二苯酮基含量的增加而增加,当PVB分子量提高时引发聚合能力加强,这和高分子敏化剂分子链中高效率的能量传递以及色基的密集分布特性有关。     

AB型两亲聚L-谷氨酸-苄酯-聚乙二醇嵌段共聚物的合成与表征

利用L 谷氨酸和苯甲醇反应制备了L 谷氨酸 苄酯 ,然后将其与三聚光气反应制备了N 羧基 L 谷氨酸 环内酸酐 (NCA) .以聚乙二醇单甲醚 (MPEG)为原料 ,制备了端氨基聚乙二醇单甲醚 (MPEG NH2 ) ,并以此作为引发剂 ,引发NCA开环聚合 ,合成了不同分子量的聚L 谷氨酸 苄酯 聚乙二醇单甲醚 (PBGM )嵌段共聚物 .利用IR、1 H NMR、DSC、GPC等方法对共聚物结构进行了表征 .结果表明 ,MPEG NH2 引发NCA开环聚合得到的是嵌段共聚物 ,通过1 H NMR谱得到共聚物组成及数均分子量 ;随着共聚物中MPEG含量的增高 ,聚L 谷氨酸 苄酯的亲水性有所改善     

聚乙二醇-聚L-丙交酯嵌段共聚物结晶形貌研究

用偏光显微镜和原子力显微镜对比研究了PEG-PLLA嵌段共聚物在110℃或120℃等温结晶后的结晶形貌.发现在110℃时只有PEG5000-PLLA2300和PEG5000-PLLA6300在偏光显微镜下呈现环带球晶形貌,在原子力显微镜高度图中显示明显的环带,并具有交替凸凹起伏形貌.而PEG5000-PLLA12000球晶中没有出现环带形貌而是生成了规则的环线.在120℃时,PEG5000-PLLA12000的球晶中才生成了规则的环带图案,原子力显微镜也显示了其球晶具有明显的交替凸凹起伏形貌,说明过冷度直接影响环带球晶的生成.产生周期性凸凹起伏和明暗交替消光是由片晶沿着球晶的半径方向周期性扭转造成的,片晶在凸起部分是Edge-on取向,在凹下部分是Flat-on取向.     

Morphological changes of BTDA/m‐PDA polyimide banded spherulites: The effect of solvent on banding

BTDA/m‐PDA polyimide banded spherulites with different band spacing were observed in the same sandwiched film. Atom force microscopy (AFM) analysis suggested that the banded structure was caused by periodic twisting of radial grown lamella bundles. Based on polarizing light microscopy (PLM) and AFM observation, it was found that spherulites grown near the center of the film exhibited bigger band spacing and consisted of wider lamellae compared with those grown near the fringe, which was suggested to be caused by different solvent amount during imidization and crystallization: the more solvent existed, the wider the lamella would grow and the bigger the band spacing would be. It was further proved by changing the film thickness and PAA solution concentration. SEM observation showed that when crystallized in the solution, the lamella became ultra thick and straight, and formed small particles. Powder X‐ray diffraction revealed that crystal structures of the banded spherulite and the small particle were identical or at least very similar. Another solvent with lower boiling point was used in sample preparation, however, under the same preparation conditions, the grown features of banded spherulites did not change. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 659–667, 2008     

Nonisothermal crystallization behavior, and morphology of poly(trimethylene terephthalate)/polyethylene glycol copolymers

Poly(trimethylene terephthalate)/polyethylene glycol (PTT/PEG) copolymers, with PEG content ranging from 27.2 to 47.4 wt%, were synthesized by melt copolycondensation. Wide-Angle X-ray diffractometer revealed that all copolymers had the same crystal structure of homo-PTT at room temperature. All copolymers could form ring-banded spherulites, and band spacing increased with increasing PEG content at a given crystallization temperature. Nonisothermal crystallization morphology of copolymers was greatly influenced by cooling rate. When the cooling rate was 2.5 °C/min or lower, banded patterns were absent, whereas when the cooling rate was 20 °C/min or higher, a novel crystal morphology composed of non-banded spherulites (central part) and ring-banded spherulites with decreasing band spacing along the radial growth direction was observed. Moreover, the size of the non-banded spherulitic part decreased with increasing cooling rate. Finally, the nonisothermal crystallization kinetics of copolymers were analyzed and only the Mo method was satisfactory to accurately describe this system.     

Formation of new banded spherulites in polyimides

The crystalline morphology and structural development of aromatic polyimides during an optimum continuous thermal imidization procedure were examined by means of polarized optical microscopy and X‐ray diffraction. During thermal imidization, 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride/1,3‐diaminobenzene polyimide samples formed complicated spherulites, which, in addition to zigzag Maltese crosses, also showed concentric extinction rings, which are characteristic of banded spherulites. The factors affecting the formation of banded spherulites were studied. The initial imidization conditions dramatically affected the formation of the banded spherulite morphology: slow heating (0.5 °C/min) or fast heating (20 °C/min) led to relatively small polyimide spherulites and less identifiable extinction rings. The morphological features were also affected by the molecular weight of the polyimide: higher molecular weight samples showed typical banded spherulites, whereas low‐molecular‐weight samples formed degenerated banded spherulites. In all the spherulites formed in 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride/1,3‐diaminobenzene polyimides, special zigzag Maltese crosses, instead of normal Maltese crosses, were observed. The relationship between the imidization procedure and the spherulite morphology formation was also studied. X‐ray and Fourier transform infrared together revealed that after several minutes of thermal treatment, the crystallization was nearly complete, with a 42.5% degree of crystallinity; meanwhile, only some poly(amic acid) converted to the corresponding polyimide, with a 27% degree of imidization. The crystalline morphology and structure formed in the initial stage of the imidization process were maintained during the following imidization processing at an elevated temperature. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1997–2004, 2005     

聚左旋乳酸/聚消旋乳酸共混物的结晶行为

非晶态聚消旋乳酸(PDLLA)对PLLA的结晶行为有较大的影响。本文利用差示扫描量热仪(DSC)和偏光显微镜(POM)对不同分子量PLLA、PDLLA按不同比例制得的共混物结晶进行了系统研究。结果表明随PDLLA含量的增大PLLA冷结晶温度升高,且越接近熔融温度。PDLLA分子量较小时PLLA球晶特征被明显破坏,PDLLA分子量较大时PLLA更易形保持球晶特征且易形成环带球晶形貌,这与结晶速率与非晶组分的扩散速率匹配程度有关。低分子量的PDLLA使PLLA的最大生长速率对应的温度出现在较低温度。     

Synthesis, crystallization and hydrolysis of aromatic-aliphatic copolyester: Poly(trimethylene terephthalate)-co-poly(l-lactic acid)

In this study, poly(trimethylene terephthalate)-co-poly(l-lactic acid) (PTT-co-PLLA) copolyesters with different compositions were synthesized by melt polycondensation. The crystal morphologies of PTT-co-PLLA copolyesters were investigated with polarized light microscope (PLM). It was found that PTT-co-PLLA copolyesters exhibited banded spherulites with smaller band spacing at the same degree of super-cooling compared with PTT homopolymer. The PLLA segments in those copolyesters ranged from 0 to 28.4 mol% and did not form crystals during crystallization. Hydrolysis study on PTT homopolymer and PTT-co-PLLA copolyesters was carried out in buffer solutions. PTT-co-PLLA copolyesters represented pronounced hydrolytic degradation, which increased with the content of lactyl units. And it was concluded that degradation of PTT-co-PLLA was mainly attributed to the scission of PLLA segments.     

Effects of top confinement and diluents on morphology in crystallization of poly(l‐lactic acid) interacting with poly(ethylene oxide)

Effects of top confinement and diluent poly(ethylene oxide) (PEO) on poly(l ‐lactic acid) (PLLA) crystal morphology have been investigated. When crystallized at 120 °C, uncovered neat PLLA sample exhibits higher growth rate ringless spherulites; while the covered sample exhibits lower growth rate ring‐banded spherulites. As PEO is introduced into PLLA, the morphology also undergoes significant changes. For the same T_c,PLLA = 120 °C, the PEO/PLLA blend with PEO composition greater than 25% exhibits ring‐banded patterns even in uncovered sample. However, in much greater PEO composition (>80 wt %), uncovered samples exhibit ring bands diverging into dendritic patterns, while top covered samples tend to maintain the spiral ring‐band patterns. Both PEO inclusion in PLLA and top cover on films impose growth kinetic alterations. Additionally, the top glass cover tends to prevent the lower surface tension PLLA to be accumulated on the surface, resulting in the formation of ring‐band pattern. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1160–1170     

BTDA/m-PDA聚酰亚胺环带球晶形貌与生长影响因素的研究

综述了本课题组BTDA/m-PDA聚酰亚胺环带球晶研究的进展.通过偏光显微镜(PLM),透射电镜(TEM),和原子力显微镜(AFM),研究了球晶中片晶的生长形貌,并探讨了环带形成的机理.考察了环带球晶生长的影响因素,包括:(1)温度:在较低酰亚胺化温度下只能形成不规则的球晶,而在较高温度下形成中心环间距较大的球晶;(2)聚酰胺酸分子量:分子量较低聚酰胺酸不能形成环带球晶;(3)分子链的不对称性:通过不同比例单体共聚发现,分子链上间苯二胺和羰基的不对称性对环带的形成有着决定性的影响;(4)溶剂:随着溶剂含量的增加,环带球晶的环间距增大.     

Isothermal crystallization behavior and unique banded spherulites of hydroxyapatite/poly(L-lactide) nanocomposites

<正>Hydroxyapatite/poly(L-lactide)(HA/PLLA) nanocomposites were prepared by the solvent mixing method.The isothermal crystallization behavior was studied by differential scanning calorimetry(DSC) and polarized optical microscopy (POM).The results show that the crystallization behavior of HA/PLLA composites was strongly affected by the content of HA and crystallization temperature,and the addition of HA could promote nucleation and enhance the crystallization rate. When isothermal crystallization was carried out at 110℃,the HA/PLLA nanocomposite with 1%HA content crystallized most rapidly among all the composites and the half crystallization time was only 1.0 min.Banded spherulites were observed for the HA/PLLA composites,but no banded spherulites were seen in the crystals of PLLA under the same condition.