含糖聚合物的合成

综述了含糖聚合物合成的研究发展，介绍了化学和酶催化合成不饱合含糖单体的方法，以及含糖聚合物通过自由基、阳离子、阴离子聚合和高分子改性等四种方法制备途径，同时也探讨了这些含糖聚合物在医药、生物材料、水凝胶等领域中的应用。     

结构规整支化聚合物的制备方法

结构规整支化聚合物可以通过主链引发法，大分子单体聚合法和主链－支链偶联法来合成，对结构较为规整的支化聚合物的制备进行总结和评述。     

非甾体类药物含糖乙烯醇酯共聚物制备及药物释放研究

分别利用化学法和酶促法合成了三种药物(萘普生、酮洛芬、布洛芬)乙烯酯和葡萄糖丁二酸乙烯酯(6-O-乙烯丁二酰-D-葡萄糖)两种聚合单体, 通过两种单体的自由基聚合反应制备了具有较高分子量的含糖聚合物前药. 通过IR、NMR对聚合物的结构进行了表征, 用GPC测定共聚物分子量. 含糖聚合物前药的体外释放研究表明, 将小分子原药制备成含糖聚合物前药后, 药物的释放时间大大延长, 达到了缓释的目的. 三种含糖聚合物的药物释放研究表明, 酮洛芬含糖高分子前药的药物释放速率较快, 萘普生含糖高分子前药的药物释放速率较慢. 不同的pH条件下的含糖聚合物的药物释放研究表明, 碱性环境下的药物释放较快, 酸性环境下的药物释放较慢.     

有机相中脂肪酶催化糖酯合成的研究

研究了有机相中脂肪酶催化以单糖和乙酸乙烯酯或乙酸酐为底物的糖脂合成反应。建立了定性、定量检测糖酯的方法，考察了７种脂肪酶催化糖酯合成的活力，发现来自假单孢菌属的ＰＳＬ１的活力最高。研究了ＰＳＬ１对不同单糖底物的选择性，发现对甘露醇的选择性最好，转化率可达９５％。研究了反应体系中的含水量对糖酯合成的影响，探讨了酶浓度和温度对反应的影响。     

PU大分子单体水溶液性质

双亲聚合物一般由亲水和亲油 2种链段构成 ,有嵌段型[1,2 ] 和接枝型[3 ] 2种 ,其中通过大分子单体法合成双亲接枝聚合物备受关注[4] 。如以亲水性大分子单体和亲油性小分子单体共聚 ,大分子单体构成共聚物主链上支链 ,具有较大活动性 ,亲水效能高。采用对氯甲基苯乙烯[5] 或甲基丙烯酰氯[6] 与聚氧化乙烯大分子的一端相反应 ,可得到亲水性大分子单体 ,但其分子量及结构变化有限。本文采用常规条件 ,合成了嵌段式水溶性聚氨酯大分子单体 ,其分子量较大 ,共聚接枝的支链较长。利用该大分子单体具有非离子高分子表面活性剂的性质 ,采用无皂乳…     

新型含双键的胆固醇单体及其液晶聚合物的合成

胆固醇分别与丁二酸酐、邻苯二甲酸酐反应制得带羧基功能基团的胆固醇单酯———丁二酸单胆固醇酯(3a),邻苯二甲酸单胆固醇酯(3b);3与甲基丙烯酸羟乙酯在DCC/DMAP催化下完成酯化反应合成了新型含双键的胆固醇单体(4a和4b);4经抽真空-冷冻-通氮气循环三次后真空封管聚合制得液晶聚合物(5a和5b),其结构经1H NMR,IR表征;5的热性能及液晶形态用DSC,TGA和POM研究。     

氟化钾催化合成糖原酸酯

以葡萄糖,甘露糖和鼠李糖为原料,经羟基保护和溴代制得溴代糖(2a～2e);2在氟化钾催化下与醇反应合成了一系列新颖的单糖原酸酯(5a～5c), 6-O-Ms-单糖原酸酯(5d)和6-O-Ts-单糖原酸酯(5e).2与由半乳糖制得的糖基受体反应合成了糖-糖原酸酯(5a-Ⅵ, 5b-Ⅵ).5的结构经1H NMR, 13C NMR和MS表征.     

脂肪酶在有机溶剂中催化酯合成和酯交换反应

报道了猪胰脂肪酶在冻干时的pH值、有机溶剂的极性、反应系统的含水量、温度以及底物碳链的长度和支链对酶在有机相中催化活性的影响规律。利用该酶合成了具有玫瑰香味的月桂酸香茅酯和辛酸香茅酯。     

新型含酯基结构的具有低线膨胀系数和吸水性的聚酰亚胺的合成

将2种主链中含有酯基结构的二胺单体:二(4-氨基苯基)对苯二甲酸酯(BPTP)和4-氨基苯基-4-氨基对苯甲酸酯(APAB),与几种常见的酸酐聚合,合成了一系列主链中含有酯基结构的新型聚酰亚胺膜材料.结果表明,所制备的聚酰亚胺薄膜表现出优良的热稳定性、机械性能和低吸水性,其中聚合物的表观玻璃化转变温度高达526℃,在空气和N2气气氛下5%的热失重温度分别在498和507℃以上,表明薄膜具有非常优异的热性能.由于聚合物主链中引入酯基结构而表现出低的线膨胀系数和吸水率.     

蔗糖酯的酶催化区域选择性合成

酶可以区域选择性地合成蔗糖酯，枯草杆菌等蛋白酶被用来区域选择性合成 1'-O-蔗糖酯，且通常不接受长链（大于C_(12))脂肪酸作为酰基授体，而脂肪酶可 催化宽范围的脂肪酸，除了脂肪酶和蛋白酶外，研究发现抗体酶也能区域和立体选 择地酰化蔗糖。蔗糖二酯、线型蔗糖酯都可以通过酶催化区域选择性地合成。酶催 化合成蔗糖酯通常在二甲基甲酰胺、二甲基亚砜和吡啶等有毒溶剂中进行。近几年 来，无溶剂条件下酶催化合成蔗糖酯，以及用叔丁醇等毒性较小的溶剂代替毒性较 大的溶剂的研究，也越来越受重视。     

One‐pot synthesis of hyperbranched glycopolymers by RAFT polymerization

Soluble hyperbranched glycopolymers were prepared by copolymerization of glycan monomers with reversible addition‐fragmentation chain transfer polymerization (RAFT) inimers in a simple one‐pot reaction. Two novel RAFT inimers, 2‐(methacryloyloxy)ethyl 4‐cyano‐4‐(phenylcarbonothioylthio)pentanoate (MAE‐CPP) and 2‐(3‐(benzylthiocarbonothioylthio)propanoyloxy)ethyl acrylate (BCP‐EA) were synthesized and used to prepare hyperbranched glycopolymers. Two types of galactose‐based saccharide monomers, 6‐O‐methacryloyl‐1,2:3,4‐di‐O‐isopropylidene‐D ‐galactopyranose (proGal‐M) and 6‐O‐(2′‐acrylamido‐2′‐methylpropanoate)‐1,2:3,4‐di‐O‐isopropylidene‐D ‐galactopyranose (proGal‐A), containing a methacrylate and an acrylamide group, respectively, were also synthesized and polymerized under the mediation of the MAE‐CPP and BCP‐EA inimers, respectively. In addition, hyperbranched poly(proGal‐M), linear poly(proGal‐A), and hyperbranched poly(proGal‐A) were generated and their polymerization kinetics were studied and compared. An unexpected difference was observed in the kinetics between the two monomers during polymerization: the relationship between polymerization rate and concentration of inimer was totally opposite in the two monomer–inimer systems. Branching analysis was conducted by using degree of branching (DB) as the measurement parameter. As expected, a higher DB occurred with increased inimer content. Furthermore, these polymers were readily deprotected by hydrolysis in trifluoroacetic acid solution resulting in water‐soluble polymers. The resulting branched glycopolymers have potential as biomimetics of polysaccharides. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Precise synthesis of heterogeneous glycopolymers with well-defined saccharide motifs in the side chain via post-polymerization modification and recognition with lectin

Heterogeneous glycopolymers with different sugar units in the side chain have been receiving considerable attention due to their potential properties in enhancing molecular recognition abilities toward a specific receptor, yet there are limited synthetic approaches to introduce different sugar motifs into the glycopolymer backbone. Herein, a series of heterogeneous glycopolymers consisting of different sugar units in the side chains were synthesized by post-polymerization modification of activated PFPA ester precursor polymers. The functionalized amines bearing two different sugar motifs have been synthesized by gradient CuAAC reaction, which could serve as a platform for achieving heterogeneous sugar units with functional control in concise steps. Isothermal titration calorimetry (ITC) measurements of the obtained glycopolymers with Concanavalin A indicated that the heterogeneous glycopolymers, poly(Man-βGlu-OH) and poly(Man-βGa-OH) bearing α-D-mannose and other non-binding β-Glucose or β-Galatose units, show higher affinities toward Concanavalin A in comparison to monoglycopolymer poly(Man-Alkyne-OH) in which the non-binding sugar motifs was substituted with non-sugar unit due to synergistic effects of non-binding sugar units. Moreover, this work allows for precise fabrication of a broad variety of glycopolymers in which it significantly broadens the library of accessible polymer structures, either homogeneous or heterogeneous glycopolymers.     

双温度响应性新型糖聚合物的合成与表征

本文采用原子转移自由基聚合法(ATRP), 设计合成了具有双温度响应性质的新型糖聚合物, 并对其在水溶液中的胶束化行为进行了动态光散射研究. 结果表明, 该系列糖聚合物具有双温度响应区间, 并且在水中形成表面呈正电性的胶束, 因此可望将其作为带负电的生物大分子(如单链DNA等)的新型载体.     

Synthesis and Characterization of Photosensitive Phosphorus Based Polymers Containing α,β‐Unsaturated Ketones in the Main Chain

1,3‐Bis(4‐hydroxyphenyl)propenone (BHPP) and 3‐(4‐hydroxy‐3‐methoxy phenyl)‐1‐(4‐hydroxyphenyl)propenone (HMPHPP) were used as monomers for preparing photosensitive phosphorus containing polyesters. The photosensitive monomers BHPP and HMPHPP were prepared respectively by refluxing 4‐hydroxybenzaldehyde and 3‐methoxy‐4‐hydroxybenzaldehyde with 4‐hydroxy acetophenone. The polyesters were synthesized by interfacial polycondensation of photosensitive diols with N‐phenylphosphoramidic dichloride using hexadecyltrimethyl ammonium bromide (HDTMAB) as phase‐transfer catalyst. Copolymers were also prepared by incorporating terephthaloyl chloride in the polymer backbone. The synthesized monomers and polymers were characterized by UV, FT‐IR and ¹H, ¹³C and ³¹P‐NMR spectroscopic techniques. The resulting polymers had inherent viscosities in the range of 0.15–0.51 dL/g and showed good solubility in polar organic solvents. The thermal properties of the polymers were studied by thermogravimetric analysis and differential scanning calorimetry under nitrogen atmosphere. The TGA data revealed that the 10% weight loss occurs at 275–320°C and all the synthesized polymers showed high char residues. DSC studies indicate that these polymers possess T_g in the range of 48 to 64°C. The photosensitive property of the polymers in film and solution state was investigated by ultraviolet spectroscopy. The effect of incorporation of terephthaloyl unit on photocrosslinking and thermal properties of the polymers was also studied.     

New Phosphorus-Containing Flame Retardants for Poly-Urethanes and Polyesters

Abstract

New phosphorus - containing monomers and oligomers from tetrakis(hydroxymetyl)phosphonium chloride and dialkylphosphites are synthesized. On the basis of new products phosphorus-containing polyesters, polyurethanes and polyuretanesemicazbazides with improved fire resistance are obtained. The dependence of fire resistance of the polymers on the structure of the use flame retardants is investigated.     

SYNTHESIS AND CHARACTERIZATION OF TRIAZOLE CONTAINING LIQUID CRYSTALLINE POLYMERS THROUGH 1,3-DIPOLAR CYCLOADDITION POLYMERIZATION

Liquid crystalline polymers containing 1,2,3-triazole units as linking groups have been synthesized from the monomers containing triad ester diazide and flexible dialkyne ester by 1,3-cycloaddition reaction and were characterized. Click reaction of azide and alkyne functionals catalyzed by Cu(I) yielded target polyesters with 1,2,3-triazole groups.The structure of the polymer was confirmed by spectral techniques.GPC analysis reveals that the polymers have moderate molecular weight with narrow distributio...     

Linear polyesters containing isocyanurate rings

Two series of linear polyesters containing isocyanurate rings have been prepared to determine the effect of structural variations on thermal and solubility properties. The polyesters were prepared by the polycondensation reaction of isocyanurate containing difunctional acid and ester monomers with linear diols. The substituent on the isocyanurate ring and the length of the acid side chain have been shown to have considerable effect on the glass transition temperature T_g. Different solubility properties were observed for the series of polyesters in which the pendant substituent was ? C₆H₅ and the acid side-chain was ? CH₂CO₂H. These polymers were insoluble in THF, and the polyester prepared from 1,6-hexanediol was also insoluble in chloroform. Thermal gravimetric analysis (TGA) indicated that structural differences had no significant effect on the thermal stability of these linear polyesters.     

Synthesis of Polyamides and Polyesters Having Various Functional Groups

Polyamides and polyesters having various functional groups have been synthesized either by the polycondensation of functional monomers having a high reactivity or by the modification of unsaturated polymers by means of suitable polymer reactions. Polyamides or polyesters having hydrophilic groups such as hydroxyl group have a high affinity for moisture adsorption and are applicable to membrane uses. Photosensitive polyamides or polyesters were also prepared.     

以亲核取代反应制备质子交换膜用磺化聚酰亚胺

本文先通过缩合反应合成羟端基的二酰亚胺单体, 然后利用亲核缩聚反应, 与4,4′-二氯二苯砜及3,3′-二磺酸钠基-4,4′-二氯二苯砜共聚, 制备聚合物. 该合成路线反应周期短, 对温度和溶剂等条件要求不高, 简便易得.     

一系列新的席夫碱型液晶高分子冠醚的合成与表征

以 4,4′ (α,ω 烷亚甲基二酰氧 )二苯甲醛和二氨基二苯并 1 5 冠 5为单体 ,采用溶液缩聚方法 ,合成了一类新的席夫碱型液晶高分子冠醚 .一种单体采用脂族二酰氯和对羟基苯甲醛反应制备 ,另一种新的单体采用二硝基二苯并 1 5 冠 5 ,在钯 碳催化剂存在下 ,水合肼还原制备 .合成的二硝基和二氨基 二苯并 1 5 冠 5 ,未能从IR和1 H NMR谱图上区分它们的几何异构体 .聚合物的分子量不高 ,Mn 在 1 0 1 0 0～ 1 3 0 0 0之间 .单体的结构通过元素分析、IR、1 H NMR和MS等方法确证 .聚合物的性质采用GPC、DSC、TG和POM等方法进行了研究 .发现所有的聚合物加热到各自的熔融温度 (Tm)以上都能形成液晶态 ,在液晶态可以观察到向列相的丝状织构和纹影织构 .聚合物的玻璃化转变温度 (Tg)、熔融温度和各向同性温度 (Ti)随聚合物分子中柔性间隔基的变化而变化 ,它们有较高的清亮点温度和宽的液晶态温度范围 .WAXD的研究进一步证实了聚合物的液晶性