SYNTHESIS AND CHARACTERIZATION OF HYPERBRANCHED POLY(ESTER-AMIDE)S BASED ON GALLIC ACID AND DL-2-AMINOBUTYRIC ACID

A novel AB3-type monomer was prepared from gallic acid and DL-2-aminobutyric acid, and used for the synthesis of the biocompatible hyperbranched poly(ester-amide)s by self-polycondensation. The polymers were characterized via FTIR and NMR spectroscopy and thermal analysis, and the average degree of branching of the polymers was estimated to be 0.75. The polymers with abundant acetyl end groups were found to be amorphous with lower intrinsic viscosity, better thermal stability and excellent solubility.

Preparation and Characterization of Poly(β-Amino Ester) Capsules for Slow Release of Bioactive Material

Network structures from poly(β-amino ester) (PAE) were synthesized for applying as drug delivery matrix via a simplified addition polymerization method. It can hold an active organic compound (drug) that has an effect as antitumor activity in order to control its release. PAE was prepared from piperazine and 1,4-butandiol diacrylate with different molar ratios. The active compound was mixed with the prepared polymer while warming for 15 minutes to obtain the capsule product. The resulting polymer structures and the surface morphology of the PAE capsules before and after encapsulation with the active drug were characterized by FT-IR and SEM, respectively. Swelling and degradation behavior of PAE were studied. The characterization showed that the obtained network structure of PAE depends on the molar ratio between the reactants. The optimum ratio of the reactants was found to be 1:1. Therefore, stable and white product as well as good holding capability for drug produced. The SEM studies illustrate good dispersion and holding properties of the drug into the network structure of the prepared polymer. In vitro, the release results of the drug from the PAE capsules indicated that the capsules were able to give sustained release of drug in DMF up to 10 days at 25°C.

Improving gene transfection efficiency of highly branched poly(β-amino ester)s through the in-situ conversion of inactive terminal groups

Highly branched poly(β-amino ester)s(HPAEs)have emerged as a safe and efficient type of non-viral gene delivery vectors.However,the presence of inactive terminal secondary amine groups compromises their gene transfection capability.In this study,HPAEs with similar topological structures and chemical compositions but varying numbers of terminal secondary 4-amino-1-butanol(S4)and secondary/tertiary 3-morpholinopropylamine(MPA)groups were synthesized.The results demonstrate that an increased number of secondary/tertiary MPA groups in-situ significantly enhances the DNA binding capability of HPAEs,leading to the formation of smaller HPAE/DNA polyplexes with higher zeta potential,ultimately resulting in superior gene transfection efficiency in bladder epithelial cells.This study establishes a sim-ple yet effective strategy to maximize the gene transfection potency of HPAEs by converting the inactive terminal groups in-situ without the need for complex modifications to their topological structure and chemical composition.

Synthesis and Characterization of Thermoplastic Poly(Ester Amide)s Elastomer (TPEaE) Obtained from Recycled PET

A series of thermoplastic polyester elastomer (TPEE) and thermoplastic poly(ester amide)s elastomer (TPEaE)copolymers were obtained by depolymerizing PET (polyethylene terephthalate) by which the waste PET canbe efficiently recovered and recycled into value-added products from a practical and economical point of view.The structure of TPEE and TPEaE was identified using nuclear magnetic resonance (NMR) and Fourier transforminfrared spectroscopy (FT-IR). Differential scanning calorimetry (DSC) data showed that the melting temperature(Tm) decreased with the amide content increased. The glass transition temperature (Tg) was increased as introducingthe amide group, and the formation of amide-ester and amide-amide hydrogen bonds increased the intermolecularchain force. The intrinsic viscosity (η) showed the tendency of increment from TPEE (0.53 dL g^(−1)) to TPEaE-5%(0.72 dL g^(−1)) due to the reinforcement of hydrogen bond and chain entanglement.

Molecular Chain Flexibility and Dielectric Loss at High-Frequency:Impact of Ester Bond Arrangement in Poly(ester imide)s

The evolution of high-frequency communication has accentuated the significance of controlling dielectric properties in polymer media.Traditionally,it has been theorized that rigid molecular chains lead to lower dielectric loss.However,the validity of this proposition at high frequencies remains uncertain.To scrutinize the correlation between chain flexibility and dielectric properties,we synthesized six poly(ester imide)s(PEIs)with systematically varied molecular chain flexibilities by modifying the ester's substitution on the aromatic ring.The introduction of ester bonds bestowed all PEI films with a low dielectric dissipation factor(D_(f)),ranging from 0.0021 to 0.0038 at 10 GHz in dry conditions.The dry D_(f)displayed a pattern consistent with volume polarizability(P/V).Unexpectedly,PI-mmm-T,featu ring the most flexible molecular chain,exhibited the lowest dielectric loss under both dry(0.0021@10 GHz)and hygroscopic(0.0029@10 GHz)conditions.Furthermore,the observed increase in D_(f)after humidity absorption suggests that the high dielectric loss of PEI in applications may be attributed to its hygroscopic nature.Molecular simulations and characterization of the aggregation structure revealed that the smaller cavities within flexible molecular chains,after close stacking,impede the entry of water molecules.Despite sacrificing high-temperature resistance,the precursor exhibited enhanced solubility properties and could be processed into high-quality films.Our research unveils new insights into the relationship between flexibility and highfrequency dielectric loss,offering innovative perspectives on synthesizing aromatic polymers with exceptional dielectric properties.

Composition Dependence of the Thermal Behavior,Morphology and Properties of Biodegradable PBS/PTMO Segment Block Copolymer

A series of aliphatic biodegradable poly（ether-ester）s based on poly（butylene succinate）（PBS）as hard segment and poly（tetramethylene oxide）（PTMO,M_n=1 000 g/mol） as soft segment were synthesized.The composition dependence of thermal behavior,morphology and mechanical properties was investigated by differential scanning calorimetry（DSC）,atomic force microscopy（AFM）,and tensile testing.The crystallization temperature（T_c） and melting temperature（T_m） of the PBS block within poly（ether-ester）s decrease steadily at first,but decrease sharply with PTMO content above 50 wt%.Two crystallization peaks were detected for PTMO in PBSPTMO60 sample,suggesting the occurrence of fractionated crystallization.The crystallization enthalpies（△H_c） and melting enthalpies（△H_m） of PBS block decrease at first,then increase as PTMO content increases further.AFM has demonstrated that phase-separated morphology transforms from a phase of continuous hard matrix to one of continuous soft matrix containing isolated hard domain as PTMO content is increased.Finally,the results of tensile testing show that the poly（ether-ester）s present the behavior of plastics when PTMO content is below 40 wt%,and of thermoplastic elastomers with PTMO content above 50 wt%.By varying the composition of copolymer,the aliphatic poly（ether-ester）s plastics,or especially biodegradable aliphatic poly（ether-ester）s thermoplastic elastomers can be obtained.

Highly branched poly(β-amino ester)s with narrow molecular weight distribution: Fractionation and gene transfection activity

Highly branched poly(β-amino ester)s(HPAEs) have shown their great promise in gene delivery. However, their broad molecular weight distribution(MWD) poses an additional challenge to the mechanistic understanding of the influence of molecular weight(MW) on their gene transfection activity. Using a stepwise precipitation strategy, HPAEs were fractionated. It is shown that MW has a significant effect on the transfection activity and cytotoxicity of HPAEs. The intermediate MW mediates higher transfection efficiency while maintaining high cell viability. Mechanistic studies show that the intermediate MW confers stronger DNA binding affinity to HPAEs, leading to the formulation of polyplexes with a relatively smaller size and more positive zeta potential. This study not only suggests a simple strategy to fractionate HPAEs with narrow MWD but also provides new insights into understanding the structure-property relationship, which would facilitate the clinical translation of HPAEs in gene therapy.

Efficient gene transfection of suspension cells by highly branched poly(β-amino ester)

Suspension cells play a crucial role in many biological processes. However, compared to adherent cells, it is particularly challenging to introduce exogenous genes into suspension cells to regulate their biological functions with non-viral gene vectors, mainly due to the low cellular uptake and endosomal escape of polyplexes. Herein, to improve the interactions of polyplexes with cellular membranes, we design and synthesize highly branched poly(β-amino ester)(HPAE) via an “A2 + B4 + C2” Michael addition strategy.Results show that branching significantly increases DNA condensation of HPAE, cellular uptake and endosomal escape of HPAE/DNA polyplexes. In mast cells(MCs), HPAE exhibits up to 80-fold higher gene transfection efficiency compared to the corresponding linear poly(β-amino ester)(LPAE) and the leading commercial gene transfection reagents PEI25k, jetPEI, and Lipofectamine 3000, without causing obvious cytotoxicity. Our study establishes a reliable non-viral platform for efficient gene transfection of suspension cells.

基于对亚苯基双苯偏三酸酯二酐的聚酯酰亚胺的合成与性能研究

随着柔性光电技术的快速发展,制备出具有优异综合性能的聚酰亚胺成为当前的研究热点。本工作采用自制的对亚苯基双苯偏三酸酯二酐和三种含不同取代基团的4,4′-二氨基二苯基甲烷进行反应,制备了三种聚酯酰亚胺树脂,表征了树脂的热性能、溶解性能、力学性能、光学性能。研究发现:对亚苯基双苯偏三酸酯二酐和2,2′-二(三氟甲基)-4,4′-二氨基二苯基甲烷制备的聚酯酰亚胺薄膜,具有较高的玻璃化转变温度和良好的可见光透过率,有望应用于柔性光电领域。

pH-Responsive supramolecular micelle based on host-guest interaction of poly(β-amino ester) derivatives and adamantyl-terminated poly(ethylene glycol) for cancer inhibition

Supramolecular structures have received growing attention and been widely applied in many fields.Herein, we synthesized hydrophobic β-cyclodextrin-contained poly(β-amino ester)(PAE-β-CD) and hydrophilic adamantyl-terminated poly(ethylene glycol)(PEG-AD) to form a supramolecular micelle via the host-guest interaction. The micelle displayed pH responsive structure change due to the transform of hydrophobic PAE core to hydrophilic form in weakly acid condition. After the anticancer drug curcumin(Cur) was loaded into the micelle, the drug release behavior of the Cur-loaded micelle was studied, and it turned out that the Cur-loaded supramolecular micelle could effectively unload the drug at pH 5.5.Furthermore, the antitumor efficiency of the Cur-loaded micelle was also examined both in vitro and in vivo, indicating considerable inhibition ratio as high as 62.14% against mouse sarcoma 180.

环氧烷烃与硫代内酯交替共聚制备聚酯硫醚及其性能

以金属铬配合物[SalphCr(Ⅲ)Cl]/双-(三苯基正膦基)氯化铵(PPNCl)/叔丁醇锂(tBuOLi)组成三组分催化体系,实现了多种环氧烷烃与γ-硫代丁内酯(TBL)高活性开环共聚。采用^(1)HNMR、^(13)CNMR、ESI-MS及FTIR对聚合物结构进行了表征,考察了不同结构聚酯硫醚的热性能以及光学性能。结果表明,聚合过程中叔丁醇锂可有效稳定链末端硫负离子,抑制其回咬,保证了反应活性以及聚合物相对分子质量。聚酯硫醚均具有完全交替结构且呈现无定形形态,玻璃化转变温度(T_(g))处于-53~-18℃之间,热失重5%温度在258~300℃之间。将叔丁基缩水甘油醚与TBL共聚物中的硫醚结构氧化为亚砜和砜时,其聚合物T_(g)分别提高了49和60℃。顺式2,3-环氧丁烷与TBL的共聚物折射率可达1.59,表明主链中的硫原子赋予聚酯硫醚良好的光学性能。

Synthesis and Characterization of Crystallizable Aliphatic Thermoplastic Poly(ester urethane) Elastomers through a Non-isocyanate Route

A simple non-isocyanate route is developed for synthesizing crystallizable aliphatic thermoplastic poly（ester urethane） elastomers （TPEURs） with good thermal and mechanical properties. Three prepolymers of 1,6-bis（hydroxyethyloxycarbonylamino） hexane （BHCH）, i.e. PrePBHCHs, were prepared through the self-transurethane polycondensation of BHCH. A poly（butylene adipate） prepolymer （PrePBA） with terminal HO-- groups was prepared and used as a polyester glycol. A series of TPEURs were prepared by the co-polycondensation of the PrePBHCHs with PrePBA at 170 ℃under a reduced pressure of 399 Pa. The TPEURs were characterized by gel permeation chromatography, FTIR, 1H-NMR, differential scanning calorimetry, thermogravimetric analysis, wide-angle X-ray diffraction, atomic force microscopy, and tensile test. The TPEURs exhibited Mn up to 23300 g/mol, Mw up to 51100 g/mol, Tg ranging from -33.8 ℃ to -3.1 ℃, Tm from 94.3 ℃ to 111.9 ℃, initial decomposition temperature over 274.7℃, tensile strength up to18.8 MPa with a strain at break of 450.0%, and resilience up to 77.5%. TPU elastomers with good crystallization and mechanical properties were obtained through a non-isocyanate route.

HEAT STABLE AND ORGANOSOLUBLE BENZOXAZOLE OR BENZOTHIAZOLE-CONTAINING POLY(IMIDE-ESTER)S AND POLY(ETHERIMIDE-ESTER)S: SYNTHESIS AND CHARACTERIZATION

Two series of poly（imide-ester）s （PIEs） and poly（ether-imide-ester）s （PEIEs）, having benzoxazole or benzothiazole pendent groups, were conveniently prepared by the diphenylchlorophosphate-activated direct polyesterification of two bis（imide-carboxylic acid）s （1）, such as 2-[3,5-bis（N-trimellitimidoyl）phenyl]benzoxazole （lo） and 2-[3,5-bis（N- trimellitimidoyl）phenyl]benzothiazole （Is） and two bis（imide-ether-carboxylic acid）s （2）, such as 2-[3,5-bis（4- trimellitimidophenoxy）-phenyl]benzoxazole （2o）, and 2-[3,5-bis（4-trimellitimidophenoxy）-phenyl]benzothiazole （2s） with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. The structures, solubilities and thermal properties of obtained polymers were investigated in detail. All of the resulting polymers were characterized by FTIR and IH-NMR spectroscopy and elemental analysis. All of the resulting polymers exhibited excellent solubility in common organic solvents, such as pyridine, tetrahydrofuran and m-cresol, as well as in polar organic solvents, such as N-methyl-2- pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide and dimethyl sulfoxide. The modified polymers were obtained in quantitative yields with inherent viscosities between 0.47 and 0.67 dl·g^-1 Experimental results indicated that all the polymers had glass transition temperature between 198 ℃ and 262 ℃, the decomposition temperature at 10% weight loss between 398 ℃ and 531 ℃ under nitrogen.

Synthesis and characterization of new optically active and organosoluble poly(ester-imide)s based on bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic diimide by direct polycondensation

New optically active poly(ester-imide)s PEIs were prepared from newly synthesized N,N′-(bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic)-bis-L-isoleucine diacid 4 via direct polycondensation with various aromatic diols in a system of tosyl chloride (TsCl), pyridine (Py), and N,N-dimethylformamide (DMF). The reactions with bicyclo TsCl were significantly promoted by controlling alcoholysis with diols, in the presence of catalytic amounts of DMF, to give a series of optically active PEIs, with good yield and moderate inherent viscosity ranging from 0.44 to 0.66 dL/g. The diacid 4 was synthesized by the condensation reaction of [2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride 1 with L-isoleucine 2 in acetic acid. All of these polymers were highly organosoluble in solvents such as N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), and N-methyl-2-pyrrolidone (NMP) at room temperature. They were fully characterized by means of NMR spectroscopy, FTIR spectroscopy, gel permeation chromatography (GPC), elemental analyses, inherent viscosity, solubility test, and specific rotation, and thermal properties of the poly(ester-imide)s were investigated using TGA/DTG.

热致液晶聚(氨酯-酯)的酚羟基氨基甲酸酯的合成

以 2 ,4-甲苯二异氰酸酯 ,对苯二酚为原料 ,以二氧六环 ,N,N-二甲基乙酰胺为溶剂 ,- NCO/- OH=1 /1 0～ 1 /4( mol/mol) ,反应温度 60～ 80℃ ,反应时间 4～ 8h,采用红外定性跟踪反应过程。经红外光谱、1H-核磁共振谱和元素分析等方法的确定 ,合成出了高纯度的氨酯单体 :双 ( 4′-羟苯基 ) - 2 ,4-甲苯二氨酯 ,以氨酯单体、丁二醇和对苯二甲酰氯为原料的溶液聚合得到新型的液晶聚氨酯。这就改变了先合成含酯键的介晶二醇或二酚 ,再与二异氰酸酯反应得到液晶聚氨酯 -酯的传统方法。

聚酯-酰胺的水解降解行为

研究了各种条件下聚酯 -酰胺的水解降解行为及其与结构之间的关系。结果表明 :酯键含量越高 ,质量损失就越快。聚合物的降解受酸、碱催化。根据SEM观察提出了可能发生的降解机理 :表面腐蚀、非晶区腐蚀、晶区破坏到全部降解。

超支化不饱和聚(酰胺-酯)的改性及热分解动力学

采用不同链长的十四酰氯和十八酰氯对超支化不饱和聚(酰胺-酯)(MHBP)的端羟基进行原位端基改性,制备出2种改性超支化聚合物,用傅立叶红外光谱(FTIR)、热重分析(TGA)、黏度法等对其结构及性能进行表征,并研究了它们的热分解行为及其热分解动力学.结果表明,其热分解反应不是一级反应,改性超支化聚合物的热稳定性与末端烷烃链的长度有关,用Ozawa法求出了热分解表观活化能.

一类含萘环结构的聚酯酰亚胺液晶聚合物的结构与性能研究

利用Higashi芳香聚酯直接缩聚法的原理,采用分步投料的方法,以N,N′-1,6-亚己基-双苯偏三酸酰亚胺二酸(IA6)、6-羟基-乙-萘甲酸(HNA)和4,4′-二羟基二苯酮(DHBP)为单体原料,合成了一系列聚酯酰亚胺共聚物.用核磁共振(NMR)、差热分析(DSC)、偏光显微镜(PLM)、广角X射线衍射(WAXD)、热重分析(TGA)等手段对所合成的聚酯酰亚胺的液晶行为、结构以及热性能进行了表征.研究结果表明,当HNA投料量占单体总投料量高于33mol%时,所得聚合物均呈明显的向列型热致液晶特性.但是,此类液晶聚合物仅在升温过程中出现液晶的相转变,而在降温过程中并未观察到液晶的相转变行为.由DSC结果分析可知,此类聚合物具有较高的玻璃化转变温度(Tg)和较低的熔融温度(Tm),有望成为一类既具有较低加工温度又有较高使用温度的液晶聚合物材料.

脂肪族聚酯-酰胺混缩聚物热性能及水解降解性能

为了研究脂肪族聚酯 -酰胺混缩聚物降解过程 ,考察了不同酯 /酰胺含量比聚酯 -酰胺 (PEAs)的热性能、水解降解性和溶解性。结果表明 :示差扫描量热法 (DSC)表明PEAs具有两个熔融峰 ,Tm ,1约 10 5℃ ,Tm ,2 随酰胺链段含量增加而升高 ,PEAs的结构随酯 /酰胺含量比不同从无规向有规过渡。广角X射线衍射 (WAXD)图谱在 2θ =2 1.6°处有一半晶性聚合物特征峰。于 (37± 0 .5 )℃、pH 7.4 0磷酸盐缓冲溶液 (PBS)中的水解实验表明PEAs含酯链段越高 ,降解越快 ;PEAs在不同pH溶液中的降解顺序为碱性 >酸性 >中性 ;PBS中降解时 ,PEAs在 2 5d内粘度下降极快并失去强度。聚合物可溶于甲酸和间甲酚 ,溶解性能将随酯键含量升高而改善。

超支化聚(胺-酯)的合成及在皮革中的应用

以三羟甲基丙烷为中心核分子,N,N-二羟乙基-3-胺基丙酸甲酯为合成单体,在对甲苯磺酸催化下,采用一步法合成了一系列新型超支化聚(胺-酯)复鞣剂(G1、G2和G3),并用红外(IR)光谱、核磁共振(1H-NMR)和羟值测定对其结构进行了表征,结果表明,合成的超支化聚(胺-酯)化学结构与设计的分子结构一致。将其用作皮革复鞣剂,相对传统复鞣剂的复鞣效果,经超支化聚(胺-酯)复鞣后的皮革在抗裂强度和透气性等方面的性能都有明显的提高,且随着代数的增加,效果更加明显。