聚膦腈-g-聚己内酯共聚物的合成与表征

通过三甲基碘硅烷与聚二(2-甲氧基乙氧基)膦腈侧链上的醚键反应后水解得到侧链含部分羟基的聚膦腈,然后利用聚膦腈的侧链羟基在异辛酸亚锡催化作用下,引发己内酯单体开环聚合制备了聚膦腈-g-聚己内酯共聚物.该共聚物中聚己内酯链段的接枝率和侧链长度可通过改变三甲基碘硅烷和己内酯单体的投料来控制.     

聚己内酯接枝淀粉纳米晶的制备

通过异氰酸酯与端羟基聚己内酯反应制备端异氰酸酯基预聚体,再接枝到淀粉纳米晶表面,制备了端基分子量可控的聚己内酯接枝淀粉纳米晶。分别用FTIR和1H NMR对所制备的聚己内酯接枝淀粉纳米晶进行表征,结果表明,有少量聚己内酯接枝到淀粉纳米晶表面。XRD结果表明,接枝了少量聚己内酯后的淀粉纳米晶的晶型和结晶度与未接枝的淀粉纳米晶基本一致。聚己内酯接枝淀粉纳米晶的熔融温度由115℃左右提高到122℃左右,并且温度范围变宽。浸润性实验表明,聚己内酯接枝淀粉纳米晶与水不浸润,其表面已具有疏水性。聚己内酯仅接枝在淀粉纳米晶的表面,改善了淀粉纳米晶表面的疏水性能和与聚酯类聚合物的界面相容性。聚己内酯接枝淀粉纳米晶有望用于可降解聚酯类高分子材料,如聚乳酸(PLA)、聚己内酯(PCL)、聚丁二酸丁二醇酯(PBS)等,改善其力学性能和生物降解性能等。     

β－萘酚取代聚磷腈的合成与表征

β－萘酚取代聚磷腈的合成与表征徐师兵，郑福安，杨永刚（华东理工大学高分子材料所，上海，２００２３７）（吉林大学理论化学研究所）关键词聚氯化磷腈，Ｎ－二氯磷酰Ｐ－三氯单磷腈，β－萘酚取代聚磷腈无机高分子聚氯化磷腈中的氯原子具有很高的反应活性，它可与许多...     

淀粉乙酸酯的阴离子接枝己内酯聚合研究

将淀粉在二甲基甲酰胺、吡啶存在下 ,以乙酸酐进行部分乙酰化 ,制备取代度为 0 7～ 1 9的淀粉乙酸酯 (St Ac) .以萘钠与淀粉乙酸酯中残余的羟基反应 ,将羟基转化为醇盐 (ONa) ,引发己内酯进行阴离子开环接枝聚合 ,合成了淀粉 聚己内酯接枝共聚物 (St g PCL) .采用凝胶渗透色谱法 (GPC)研究了接枝前后聚合物分子量的变化情况 ,并以接枝率、单体转化率对接枝反应进行了表征 .研究了接枝条件如温度、溶剂、引发剂和单体的用量对接枝率及单体转化率的影响 .研究发现随着反应温度升高 ,接枝率、单体转化率呈S曲线变化 ,单体浓度、引发剂浓度的增大有利于接枝反应的进行 .     

聚己内酯接枝淀粉纳米晶的制备

本文通过异氰酸酯与端羟基聚己内酯反应制备端异氰酸酯基预聚体,再接枝到淀粉纳米晶表面,制备了端基分子量可控的聚己内酯接枝淀粉纳米晶。分别用FTIR和1HNMR对所制备的聚己内酯接枝淀粉纳米晶进行表征,结果表明有少量聚己内酯接枝到淀粉纳米晶表面。XRD结果表明,接枝少量聚己内酯的淀粉纳米晶的晶型和结晶度基本不变。聚己内酯接枝淀粉纳米晶的熔融温度由115℃左右提高到122℃左右,并且温度范围变宽。浸润性实验表明,聚己内酯接枝淀粉纳米晶与水不浸润,其表面已具有疏水性。聚己内酯仅接枝在淀粉纳米晶的表面,改善了淀粉纳米     

聚双(2-吡咯基乙氧基磷腈)的合成、氧化交联和导电性研究

有机 /无机杂化聚磷腈具有优良的加工性能和使用性能 ,可以在许多领域获得应用 [1] .具有光电活性的聚磷腈研究也引起了广泛的关注 [2～ 4 ] . Allcock等 [2 ] 合成了具有离子传导特性的聚磷腈 ,可应用于锂离子电池 .具有非线性光学特性的聚合物也有研究报道 [3 ] . L eung等 [4 ] 合成了具有电致发光基团的聚磷腈 ,部分聚合物具有蓝光发射的特征 .合成化学键合的聚 (N -烷基 )吡咯通用聚合物复合膜材料已经得到了重视[5,6] .本文合成了 2 -吡咯基乙醇 ,将其与反应性无机聚合物聚 (二氯 )磷腈进行高分子取代反应 ,合成了含吡咯侧基的聚磷…     

含咔唑基团的有机聚磷腈的合成与表征

含咔唑基团的有机聚磷腈的合成与表征;咔唑;聚磷腈;亲核取代     

一种新型有机无机杂化聚磷腈高分子的制备及表征

通过两步亲核取代反应制备了一种新型有机一无机杂化聚磷腈高分子—丙烯胺苯酚双取代聚磷腈。运用红外光谱、氢核磁共振谱、磷核磁共振谱证实了聚合物的化学组成。热失重研究表明该聚合物具有较好的热稳定性和较高的残留率,800℃时,残炭率高达48.2％。聚合物侧链上的烯丙基基团可通过热引发交联,进一步提高其热稳定性和残炭率。     

侧链末端含荧光基团芘的EC-g-PCL梳形共聚物的合成与性能研究

首先以乙基纤维素(EC)为大分子引发剂引发ε-己内酯(CL)的开环聚合反应(ROP),合成乙基纤维素接枝聚ε-己内酯的梳形共聚物(EC-g-PCL).之后利用N,N'-二环己基碳二亚胺(DCC)做脱水剂将荧光基团芘(Pyr)引入侧链聚ε-己内酯(PcL)末端,经控制投料比,合成不同含量芘端基的乙基纤维素接枝聚ε-己内酯...     

聚β-羟基丁酸酯和聚ε-己内酯的酯交换反应

以辛酸亚锡为催化剂 ,研究了聚 β 羟基丁酸酯 (PHB)与聚ε 己内酯 (PCL)在液相条件下的酯交换反应 .讨论了反应时间 ,反应温度和催化剂浓度对酯交换反应的影响 .采用1 3C NMR ,FTIR ,DSC ,WAXD和TGA等方法对PHB和PCL共聚酯 (PHB co PCL)的结构进行了表征 ,并对其结晶行为、晶体结构和热稳定性进行了研究 .结果表明 ,通过酯交换反应 ,所得到的共聚酯为嵌段共聚物 .提高反应温度和延长反应时间有利于酯交换反应的发生 .随着酯交换量的增加 ,PHB co PCL的结晶行为发生很大的变化 .但是 ,PHB co PCL晶体结构并没有因为PCL链段的引入而发生变化 ,而且它的热稳定性在空气气氛中略有提高     

Lipase‐Catalyzed Transesterification of Polyesters to Ester Copolymers

Lipase‐catalyzed intermolecular transesterification between two different polyesters has been carried out using in toluene. The transesterification of poly(ε‐caprolactone) (PCL) and (1,4‐butylene adipate) took place via catalysis of lipase from Candida antarctica to give an ester copolymer. ¹³C NMR analysis showed that the resulting polymer was not a mixture of the starting polyesters, but a copolymer consisting of both units. The reaction temperature and solvent amount greatly affected the microstructure of the ester copolymer. Under appropriate conditions, the random copolymer was formed. The enzymatic transesterification has been monitored by size exclusion chromatography (SEC) and ¹³C NMR. Ester copolymers were enzymatically obtained from PCL and other poly(α,ω‐alkylene dicarboxylate)s and their microstructure depended on the polyester structure.     

温度和pH值双敏感的生物相容性三嵌段共聚物聚(2-乙基-2-噁唑啉)-b-聚(ε-己内酯)-b-聚(L-谷氨酸)的合成和表征

研究了由温敏的聚(2-乙基-2-噁唑啉)和pH值敏感的聚(L-谷氨酸)组成的三嵌段共聚物,聚(2-乙基-2-噁唑啉)-b-聚(ε-己内酯)-b-聚(L-谷氨酸)的合成方法,(1)以对甲苯磺酸甲酯为引发剂引发2-乙基-2-噁唑啉进行正离子开环聚合反应,得到了羟基封端的聚(2-乙基-2-噁唑啉)(PEOz-OH);(2)以PEOz-OH为引发剂,以辛酸亚锡为催化剂,在氯苯中合成了PEOz-b-聚(ε-己内酯)两嵌段共聚物(PEOz-b-PCL-OH);(3)将PEOz-b-PCL-OH末端的羟基转换为氨基,得到氨基封端的两嵌段共聚物(PEOz-b-PCL-NH2);(4)以PEOz-b-PCL-NH2为引发剂引发γ-苄基-L-谷氨酸-N-羧酸酐(BLG-NCA)开环聚合,得到了PEOz-b-PCL-b-聚(γ-苄基-L-谷氨酸)(PEOz-b-PCL-b-PBLG)三嵌段共聚物;(5)以HBr的醋酸溶液为脱保护剂脱去苄基保护基,得到PEOz-b-PCL-b-聚(L-谷氨酸)(PEOz-b-PCL-b-PLGlu)三嵌段共聚物.采用1H-NMR、GPC和FT-IR表征了各步聚合物的结构、分子量和分子量分布.     

Synthesis and characterization of well‐defined polystyrene and poly(ε‐caprolactone) hetero eight‐shaped copolymers

Well‐defined hetero eight‐shaped copolymers composed of polystyrene (PS) and poly(ε‐caprolactone) (PCL) with controlled molecular weight and narrow molecular weight distribution were successfully synthesized by the combination of ring‐opening polymerization, ATRP, and “click” reaction. The synthetic procedure involves three steps: (1) preparation of a tetrafunctional PS and PCL star copolymer with two PS and two PCL arms using the tetrafunctional initiator bearing two hydroxyl groups and two bromo groups; (2) synthesis of tetrafunctional star copolymer, (α‐acetylene‐PCL)₂(ω‐azido‐PS)₂, by the transition of terminal hydroxyl and bromo groups to acetylene and azido groups through the reaction with 4‐propargyloxybutanedioyl chloride and NaN₃ respectively; (3) intramolecular cyclization reaction to produce the hetero eight‐shaped copolymers using “click” chemistry under high dilution. The ¹H NMR, FTIR, and gel permeation chromatography techniques were applied to characterize the chemical structures of the resulted intermediates and the target polymers. Their thermal behavior was investigated by DSC, and their crystallization behaviors of PCL were studied by polarized optical microscopy. The decrease in chain mobility of the eight‐shaped copolymers restricts the crystallization of PCL and the crystallization rate of PCL is slower in comparison with their corresponding star precursors. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6496–6508, 2008     

Methylated and pegylated PLA–PCL–PLA block copolymers via the chemical modification of di‐hydroxy PCL combined with the ring opening polymerization of lactide

Methylated and pegylated poly(lactide)‐block‐poly(ε‐caprolactone)‐block‐poly(lactide) copolymers, PLA–P(CL‐co‐CLCH₃)–PLA and PLA–P(CL‐co‐CLPEG)–PLA, were prepared in three steps: combining the formation of carbanion‐bearing dihydroxylated‐PCL, the coupling of iodomethane or bromoacetylated α‐hydroxyl‐ω‐methoxy‐poly(ethylene glycol) onto the carbanionic PCL, and finally the ring opening polymerization of DL ‐lactide initiated by the preformed grafted diOH‐PCL copolymers. The resulting block copolymers exhibited lower crystallinity, melting temperature, and hydrophobicity with respect to the original PCL. Degradation of the grafted copolymers was investigated in the presence of Pseudomonas cepacia lipase and compared with that of the triblock copolymer precursor. It is shown that the presence of the grafted substituents affected the enzymatic degradation of PCL segments. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4196–4205, 2005     

聚己内酯/聚缩水甘油醚两亲性超枝状大分子的合成及表征

通过简单的两步反应, 合成出新型超枝状聚己内酯/聚缩水甘油醚嵌段共聚物. 以月桂醇为引发剂, 通过开环聚合反应合成羟基封端的聚己内酯; 将聚己内酯进一步和萘钾反应, 得到基于己内酯的大分子引发剂; 引发缩水甘油醚的聚合, 最终形成聚己内酯/聚缩水甘油醚嵌段共聚物. 通过核磁共振氢谱、红外光谱和葡聚糖凝胶色谱对聚合物进行定性表征. 结果表明, 所得到的聚合物既具有聚己内酯的特征峰, 又有聚缩水甘油醚的特征峰, 通过核磁共振氢谱计算出二者在嵌段共聚物中的比例. 在这些聚合物骨架上存在大量的羟基末端基团, 葡聚糖凝胶色谱表征得到单峰, 进一步证明聚合物为嵌段共聚物. 相对于单纯的聚己内酯, 这种聚合物结构的突出优势在于其具有大量可修饰的高活性端基基团, 通过对端基基团的后修饰, 可实现各类配体及多种药物的偶联, 使这种新型材料有可能应用于多功能靶向药物传递.     

N-异丙基丙烯酰胺类共聚物温敏性研究

制备了N-异丙基丙烯酰胺(NIPAAm)与N,N-二甲基丙烯酰胺(DMAAm)和/或甲基丙烯酸羟乙酯(HEMA)的二元及三元共聚物,研究了组成和链转移剂用量对共聚物温敏性的影响,并在上述三元共聚物上接枝聚己内酯(PCL)得到温敏性两亲聚合物.结果表明,随着DMAAm增加、HEMA减少或共聚物分子量降低,共聚物的最低临界溶解温度升高,且PCL链段的接枝度和长度对聚合物的温敏性影响明显.     

Amphiphilic star‐block copolymers based on a hyperbranched core: Synthesis and supramolecular self‐assembly

Novel amphiphilic star‐block copolymers, star poly(caprolactone)‐block‐poly[(2‐dimethylamino)ethyl methacrylate] and poly(caprolactone)‐block‐poly(methacrylic acid), with hyperbranched poly(2‐hydroxyethyl methacrylate) (PHEMA–OH) as a core moiety were synthesized and characterized. The star‐block copolymers were prepared by a combination of ring‐opening polymerization and atom transfer radical polymerization (ATRP). First, hyperbranched PHEMA–OH with 18 hydroxyl end groups on average was used as an initiator for the ring‐opening polymerization of ε‐caprolactone to produce PHEMA–PCL star homopolymers [PHEMA = poly(2‐hydroxyethyl methacrylate); PCL = poly(caprolactone)]. Next, the hydroxyl end groups of PHEMA–PCL were converted to 2‐bromoesters, and this gave rise to macroinitiator PHEMA–PCL–Br for ATRP. Then, 2‐dimethylaminoethyl methacrylate or tert‐butyl methacrylate was polymerized from the macroinitiators, and this afforded the star‐block copolymers PHEMA–PCL–PDMA [PDMA = poly(2‐dimethylaminoethyl methacrylate)] and PHEMA–PCL–PtBMA [PtBMA = poly(tert‐butyl methacrylate)]. Characterization by gel permeation chromatography and nuclear magnetic resonance confirmed the expected molecular structure. The hydrolysis of tert‐butyl ester groups of the poly(tert‐butyl methacrylate) blocks gave the star‐block copolymer PHEMA–PCL–PMAA [PMAA = poly(methacrylic acid)]. These amphiphilic star‐block copolymers could self‐assemble into spherical micelles, as characterized by dynamic light scattering and transmission electron microscopy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6534–6544, 2005     

Synthesis of four‐armed poly(ε‐caprolactone)‐block‐poly(ethylene oxide) by diethylzinc catalyst

Biodegradable, amphiphilic, four‐armed poly(?‐caprolactone)‐block‐poly(ethylene oxide) (PCL‐b‐PEO) copolymers were synthesized by ring‐opening polymerization of ethylene oxide in the presence of four‐armed poly(?‐caprolactone) (PCL) with terminal OH groups with diethylzinc (ZnEt₂) as a catalyst. The chemical structure of PCL‐b‐PEO copolymer was confirmed by ¹H NMR and ¹³C NMR. The hydroxyl end groups of the four‐armed PCL were successfully substituted by PEO blocks in the copolymer. The monomodal profile of molecular weight distribution by gel permeation chromatography provided further evidence for the four‐armed architecture of the copolymer. Physicochemical properties of the four‐armed block copolymers differed from their starting four‐armed PCL precursor. The melting points were between those of PCL precursor and linear poly(ethylene glycol). The length of the outer PEO blocks exhibited an obvious effect on the crystallizability of the block copolymer. The degree of swelling of the four‐armed block copolymer increased with PEO length and PEO content. The micelle formation of the four‐armed block copolymer was examined by a fluorescent probe technique, and the existence of the critical micelle concentration (cmc) confirmed the amphiphilic nature of the resulting copolymer. The cmc value increased with increasing PEO length. The absolute cmc values were higher than those for linear amphiphilic block copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 950–959, 2004     

Hydrolytic degradation of poly(ε‐caprolactone) with different end groups and poly(ε‐caprolactone‐co‐γ‐butyrolactone): characterization and kinetics of hydrocortisone delivery

Asymmetric telechelic α‐hydroxyl‐ω‐(carboxylic acid)‐poly(ε‐caprolactone) (HA‐PCL), α‐hydroxyl‐ω‐(benzylic ester)‐poly(ε‐caprolactone) (HBz‐PCL), and an asymmetric telechelic copolymer α‐hydroxyl‐ω‐(carboxylic acid)‐poly(ε‐caprolactone‐co‐γ‐butyrolactone) (HA‐PCB) were synthesized by ring‐opening polymerization of ε‐caprolactone (CL). CL and CL/γ‐butyrolactone mixture were used to obtain homopolymers and copolymer respectively at 150°C and 2 hr using ammonium decamolybdate (NH₄) [Mo₁₀O₃₄] (Dec) as a catalyst. Water (HA‐PCL and HA‐PCB) or benzyl alcohol (HBz‐PCL) were used as initiators. The three polylactones reached initial molecular weights between 2000 and 3000 Da measured by proton nuclear magnetic resonance (¹H‐NMR). Compression‐molded polylactone caplets were allowed to degrade in 0.5 M aqueous p‐toluenesulfonic acid at 37°C and monitored up to 60 days for weight loss behavior. Data showed that the copolymer degraded faster than the PCL homopolymers, and that there was no difference in the weight loss behavior between HA‐PCL and HBz‐PCL. Caplets of the three polylactones containing 1% (w/w) hydrocortisone were placed in two different buffer systems, pH 5.0 with citrate buffer and pH 7.4 with phosphate buffer at 37°C, and monitored up to 50 days for their release behavior. The release profiles of hydrocortisone presented two stages. The introduction of a second monomer in the polymer chain significantly increased the release rate, the degradation rate for HA‐PCB being faster than those for HBz‐PCL and HA‐PCL. At the pH studied, only slight differences on the liberation profiles were observed. SEM micrographs indicate that hydrolytic degradation occurred mainly by a surface erosion mechanism. Copyright © 2009 John Wiley & Sons, Ltd.