聚(对苯二甲酸-1,3-丁二醇酯/对苯二甲酸-1,4-丁二醇酯)/PEG嵌段共聚物的合成及性能研究

用熔融缩聚法合成了一系列聚(对苯二甲酸-1,3-丁二醇酯/对苯二甲酸-1,4-丁二醇酯)/聚乙二醇的嵌段共聚物。用FT-IR,1H-NMR,DSC,TGA,水降解测试等方法表征了材料的结构与性能。FT-IR和1H-NMR分析表明合成得到的共聚物为预期产物;DSC分析显示,共聚聚酯随着1,3-丁二醇在共聚物中比例的增大,熔点(Tm)逐渐降低,由158.24℃下降至104.19℃,玻璃化温度(Tg)逐渐升高,由4.86℃升至24.56℃,合成得到的共聚酯趋向于无定形态;TGA分析表明1,3-丁二醇在共聚酯中比例增大会使聚酯的热稳定性下降,但合成得到的共聚酯依然具有较好的热稳定性,初始分解温度大于310℃,不需要在反应过程中添加热稳定剂;水降解测试结果表明共聚物随1,3-丁二醇比例的增加,降解速率大幅提升。     

生物降解聚丁二酸丁二醇酯／聚乙二醇嵌段共聚物的合成及表征

以2，4-甲苯二异氰酸酯（TDI）为偶联剂，将端羟基聚丁二酸丁二醇酯预聚物（PBs）与低相对分子质量聚乙二醇（PEG）进行多嵌段共聚，得到PBS／PEG多嵌段共聚物。采用FT-IR、^1H—NMR等方法对产物进行结构表征，同时研究物料配比和偶联剂TDI的用量对共聚物性能的影响及共聚物的吸水率和水解降解行为等。结果表明，PEG的引入使得材料的亲水性显著改善，共聚物的降解速率较纯PBS有大幅度提高。     

聚乳酸-聚乙二醇嵌段共聚物的研究进展

综述了聚乳酸-聚乙二醇（PLA-PEG）嵌段共聚物的研究背景及其作为微球载体的优点；重点介绍了其合成方法，包括丙交酯与PEG共聚、乳酸与PEG共聚、丙交酯与环氧乙烷共聚等3种方法。此外对其性能及其在药物控释体系、骨内固定、组织修复材料以及医用手术缝合线等领域中的应用作了简单介绍；对其发展前景进行了展望。     

聚己内酰胺—聚乙二醇嵌段共聚物的结构和性能 Ⅲ.嵌段共聚物的结…

应用ＤＳＣ、热台、扫描电镜以及偏光显微镜等研究了ＰＡ６－ＰＥＧ嵌段共聚物的结晶性能。结果表明，共聚物呈微相分离结构，其中ＰＡ６组分和ＰＥＧ组分分别结晶。两种晶粒在各自的生长过程中彼此影响。随着ＰＥＧ组分含量的增加，晶粒的完整性越来越差。共聚以后ＰＡ６组分的玻璃化转变温度和结晶温度下降，熔融温度范围变宽，结晶能力增强，晶粒尺寸分布变宽。     

聚丁二酸丁二醇酯在不同土壤环境中的降解研究

本文考察聚丁二酸丁二醇酯(PBS)在不同土壤中的降解情况,从当地取堆肥土、污泥土、垃圾土和花园土对PBS进行土埋法降解试验,通过测定降解过程中的失重率变化和对PBS降解前后表面形态观察,得出PBS在不同土壤中的降解顺序,为塑料的可降解性能的进一步研究奠定基础。     

刚柔嵌段共聚物聚苯基喹啉-b-聚苯乙烯的合成

利用原子转移自由基聚合合成了端羧基聚苯乙烯,然后与4-氨基苯乙酮反应,生成末端为乙酰基的聚合物,以P2O5为催化剂,将功能化的聚合物与5-乙酰基-2-氨基二苯甲酮共聚,合成出刚柔嵌段共聚物聚苯基喹啉-b-聚苯乙烯(PPO-b-PS),用红外光谱(IR)、氢核磁共振(1HNMR)和热重分析(TGA)对其结构和性能进行了表征,并在三氟乙酸／二氯甲烷混合溶剂中进行了初步的自组装研究。     

聚对苯二甲酸丁二醇酯共聚己二酸丁二醇酯热降解动力学研究

为了研究对比聚对苯二甲酸丁二醇酯共聚己二酸丁二醇酯(PBAT)、聚己二酸丁二醇酯(PBA)以及聚对苯二甲酸丁二醇酯(PBT)的热稳定性,采用热失重(TG)分析法研究了三种树脂的热降解行为.使用Kinssinger法、Flynn-Wall-Ozawa法以及Coats-Redern法对三种树脂的热降解表观活化能以及反应机理...     

侧链带有手性基团的聚半胱氨酸-b-聚环氧丙烷-b-聚半胱氨酸嵌段共聚物的合成

首次合成了侧链带有手性基团的聚半胱氨酸-b-聚环氧丙烷-b-聚半胱氨酸嵌段共聚物。首先炔丙基溴和L-半胱氨酸反应,合成了S-炔丙基-L-半胱氨酸,产物与三光气反应,合成S-炔丙基-N-羧基-L-半胱氨酸-环内酸酐(NCA);然后用大分子引发剂双端氨基聚环氧丙烷引发S-炔丙基-N-羧基-L-半胱氨酸-环内酸酐(NCA)开环聚合,制得了聚环氧丙烷-聚(S-炔丙基-L-半胱氨酸)嵌段共聚物;最后由N3-L-亮氨酸与共聚物侧链上的炔键发生Click反应,制得了侧链连有手性基团的嵌段共聚物。用1H NMR、IR、GPC和元素分析等方法对所得嵌段聚合物结构进行了表征。     

聚(苯乙烯-co-丙烯腈)-b-聚苯乙烯两嵌段共聚物的合成

以CuBr／N，N，N’，N’，N'-五甲基二亚乙基三胺(简称NNN)为催化体系，研究了原子转移自由基聚合法(ATRP)PS-b-P(S-co-AN)两嵌段聚合物的合成。研究了聚合顺序对相对分子质量及其分布和嵌段效率的影响，并且用聚合物末端C—Br键的断裂能对实验结果进行了初步解释。     

聚乙二醇嵌段长碳链二酸共聚物的合成与酶降解研究

采用长碳链癸二酸代替丁二酸与丁二醇以及不同含量的相对分子质量为200的聚乙二醇(PEG)嵌段共聚,得到了聚癸二酸丁二醇酯聚乙二醇嵌段共聚物(PBSe-PEG),并采用核磁共振波谱仪、凝胶渗透色谱仪、差示扫描量分析仪、热重分析仪、广角X射线衍射仪等分析手段表征了嵌段共聚物的结构和性能,并且研究了固定化南极假丝酵母菌脂肪酶(简称脂肪酶N435)对PBSe-PEG的降解性。结果表明,几种PBSe-PEG是预期产物,其数均相对分子质量在5×104左右;PBSe-PEG与纯PBSe相比晶型结构相似;随着PEG含量增加,PBSe-PEG的熔融温度（Tm）和结晶温度（Tc）逐渐下降;相比PBS,脂肪酶N435对PBSe-PEG具有更好的降解性。     

Poly(butylene terephthalate)/poly(ethylene glycol) blends with compatibilizers

Polymer blend systems offer a versatile approach for tailoring the properties of polymer materials for specific applications. In this study, we investigated the compatibility of polybutylene terephthalate (PBT) and poly(ethylene glycol) (PEG) blends processed using a twin-screw extruder, with the aim of enhancing their compatibility. Phthalic anhydride (PAn) and phthalic acid (PAc) were used as potential compatibilizers at different concentrations to improve interfacial interactions between PBT and PEG. Blend morphologies were characterized using scanning electron microscopy, which revealed improved interfacial compatibility and reduced phase separation with the incorporation of small amounts of PAn and PAc. Differential scanning calorimetry analysis indicated changes in the melting temperature (T_m) and glass transition temperature (T_g) of the blends owing to the compatibilizing effects of PAn and PAc. Dynamic mechanical analysis further corroborated the influence of the compatibilizers on the T_g and viscoelastic behavior. Thermogravimetric analysis demonstrated enhanced thermal stability with the addition of either PAn or PAc. Rheological measurements indicated an increase in complex viscosity with increasing compatibilizer content, indicating improved compatibility. The degradation point (T_d) of PBT/PEG blend increased from 158 to 200 and 319°C with the incorporation of 5 phr PAn and 2 phr PAc, respectively. Mechanical properties, including tensile strength, Young's modulus, and Izod impact strength, were evaluated. For instance, the tensile strength of PBT/PEG blend was enhanced from 43.5 to 48.7 and 49.7 MPa by incorporating 5 phr PAn and 2 phr PAc, respectively. However, the impact strength of PBT/PEG blend increased from 3.0 to 4.3 and 4.2 kJ/m² with the addition of 1 phr PAn and 1 phr PAc, respectively. The findings demonstrated that adding 5 phr PAn or 2 phr PAc to the PBT/PEG blends was advantageous, achieving a harmony of performance benefits and compromises. Rheological observations contributed significantly to the mechanical and thermal properties. Overall, the study highlights the significance of utilizing PAn and PAc as effective compatibilizers for enhancing the properties of PBT/PEG blends, making them potential candidates for various applications.     

Mechanical properties in torsion for poly(butylene terephthalate) and a poly(ether ester) based on poly(ethylene glycol) and poly(butylene terephthalate)

The torsional behavior of poly(ether ester) (PEE) thermoplastic elastomer, based on poly(ethylene glycol) (PEG) and poly(butylene terephthalate) (PBT) was studied and compared with that of PBT itself. Two types of experiments were performed: (1) stress relaxation in torsion, and (2) measurement of intermittent couple-twist responses. It was shown that the relaxation of the torsional couple M could be represented as a sum of several exponential terms in the time, rather than as a simple exponential function. This sum might be called a Prony series on the analogy of the usual stress relaxation which occurs after stretching a sample to a certain deformation and holding it constant. The intermittent couple-twist experiments were carried out by analogy with similar experiments in elongation. For PEE the couple rises steadily with the twist, whereas for PBT it rises abruptly and remains constant within the experimental error for high twists. The residual twist, however, showed a similar trend for both PEE and PBT. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 495–502, 1998     

Biodegradability of poly(ethylene terephthalate) copolymers with poly(ethylene glycol)s and poly(tetramethylene glycol)

Poly(ethylene terephthalate) copolymers were prepared by melt polycondensation of dimethyl terephthalate and excess ethylene glycol with 10–40mol% (in feed) of poly(ethylene glycol) (E) and poly(tetramethylene glycol) (B), with molecular weight (MW) of E and B 200–7500 and 1000, respectively. The reduced specific viscosity of copolymers increased with increasing MW and content of polyglycol comonomer. The temperature of melting (T_m), cold crystallization and glass transition (T_g) decreased with the copolymerization. T_m depression of copolymers suggested that the E series copolymers are the block type at higher content of the comonomer. T_g was decreased below room temperature by the copolymerization, which affected the crystallinity and the density of copolymer films. Water absorption increased with increasing content of comonomer, and the increase was much higher for E1000 series films than B1000 series films. The biodegradability was estimated by weight loss of copolymer films in buffer solution with and without a lipase at 37°C. The weight loss was enhanced a little by the presence of a lipase, and increased abruptly at higher comonomer content, which was correlated to the water absorption and the concentration of ester linkages between PET and PEG segments. The weight loss of B series films was much lower than that of E series films. The abrupt increase of the weight loss by alkaline hydrolysis is almost consistent with that by biodegradation.     

Nonisothermal crystallization kinetics of poly(butylene terephthalate)/poly(ethylene terephthalate)/glass fiber composites

The influences of the glass fiber (GF) content and the cooling rate for nonisothermal crystallization process of poly(butylene terephthalate)/poly(ethylene terephthalate) (PBT/PET) blends were investigated. The nonisothermal crystallization kinetics of samples were detected by differential scanning calorimetry (DSC) at cooling rates of 5°C/min, 10°C/min, 15°C/min, 20°C/min, 25°C/min, respectively. The Jeziony and Mozhishen methods were used to analyze the DSC data. The crystalline morphology of samples was observed with polarized light microscope. Results showed that the Jeziony and Mozhishen methods were available for the analysis of the nonisothermal crystallization process. The peaks of crystallization temperature (T_p) move to low temperature with the cooling rate increasing, crystallization half‐time (t_1/2) decrease accordingly. The crystallization rate of PBT/PET blends increase with the lower GF contents while it is baffled by higher GF contents. POLYM. COMPOS. 36:510–516, 2015. © 2014 Society of Plastics Engineers     

Synthesis and hydrophilicity of poly(butylene 2,6‐naphthalate)/poly(ethylene glycol) copolymers

Poly(butylene 2,6‐naphthalate) (PBN)/poly(ethylene glycol) (PEG) copolymers were synthesized by the two‐step melt copolymerization process of dimethyl‐2,6‐naphthalenedicarboxylate (2,6‐NDC) with 1,4‐butanediol (BD) and PEG. The copolymers produced had different PEG molecular weights and contents. The structures, thermal properties, and hydrophilicities of these copolymers were studied by ¹H NMR, DSC, TGA, and by contact angle and moisture content measurements. In particular, the intrinsic viscosities of PBN/PEG copolymers increased with increasing PEG molecular weights, but the melting temperatures (T_m)_, the cold crystallization temperatures (T_cc)_, and the heat of fusion (ΔH_f) values of PBN/PEG copolymers decreased on increasing PEG contents or molecular weights. The thermal stabilities of the copolymers were unaffected by PEG content or molecular weight. Hydrophilicities as determined by contact angle and moisture content measurements were found to be significantly increased on increasing PEG contents and molecular weights. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2677–2683, 2006     

Sequence analysis of poly(ethylene terephthalate)/poly(butylene terephthalate) copolymer prepared by ester-interchange reactions

The molecular structure of the copolyester formed through the interchange reaction in poly(ethylene terephthalate)/poly(butylene terephthalate) blends was investigated with ¹³C-NMR spectroscopy. The molar fractions of heterolinkage triads in the copolyesters were lower than the values calculated by Bernoullian statistics; this indicates that the sequence of heterolinkages was far from a random distribution at the initial stage of the interchange reaction. However, the randomness increased and the number-average sequence length decreased with reaction time. The solubility of the blend decreased with increasing sequence length, resulting from the formation of block copolymers with long sequence lengths at the initial stage of the interchange reaction. The solubility of the copolyester formed by a dibutyltin dilaurate (DBTDL)-catalyzed reaction was higher than that of the copolyester formed by a titanium tetrabutoxide-catalyzed reaction; this is related to the fact that alcoholysis prevailed in the DBTDL-catalyzed reaction. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 159–168, 2001     

Blends of poly(ethylene terephthalate) and poly(butylene terephthalate)

Commercial grade poly(ethylene terephthalate), (PET, intrinsic viscosity = 0.80 dL/g) and poly(butylene terephthalate), (PBT, intrinsic viscosity = 1.00 dL/g) were melt blended over the entire composition range using a counterrotating twin‐screw extruder. The mechanical, thermal, electrical, and rheological properties of the blends were studied. All of the blends showed higher impact properties than that of PET or PBT. The 50:50 blend composition exhibited the highest impact value. Other mechanical properties also showed similar trends for blends of this composition. The addition of PBT increased the processability of PET. Differential scanning calorimetry data showed the presence of both phases. For all blends, only a single glass‐transition temperature was observed. The melting characteristics of one phase were influenced by the presence of the other. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 75–82, 2005     

Crystallization of poly(butylene terephthalate)/poly(ethylene octene) blends: Nonisothermal crystallization

Poly(ethylene octene) (POE), maleic anhydride grafted poly(ethylene octene) (mPOE), and a mixture of POE and mPOE were added to poly(butylene terephthalate) (PBT) to prepare PBT/POE (20 wt % POE), PBT/mPOE (20 wt % mPOE), and PBT/mPOE/POE (10 wt % mPOE and 10 wt % POE) blends with an extruder. The melting behavior of neat PBT and its blends nonisothermally crystallized from the melt was investigated with differential scanning calorimetry (DSC). Subsequent DSC scans exhibited two melting endotherms (T_mI and T_mII). T_mI was attributed to the melting of the crystals grown by normal primary crystallization, and T_mII was due to the melting of the more perfect crystals after reorganization during the DSC heating scan. The better dispersed second phases and higher cooling rate made the crystals that grew in normal primary crystallization less perfect and relatively prone to be organized during the DSC scan. The effects of POE and mPOE on the nonisothermal crystallization process were delineated by kinetic models. The dispersed phase hindered the crystallization; however, the well‐ dispersed phases of an even smaller size enhanced crystallization because of the higher nucleation density. The nucleation parameter, estimated from the modified Lauritzen–Hoffman equation, showed the same results. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Crystallization of poly(butylene terephthalate)/poly(ethylene octene) blends: Isothermal crystallization

Poly(ethylene‐octene) (POE), maleic anhydride grafted poly(ethylene‐octene) (mPOE), and a mixture of POE and mPOE were added to poly(butylene terephthalate) (PBT) to prepare PBT/POE, PBT/mPOE, and PBT/mPOE/POE blends by a twin‐screw extruder. Observation by scanning electron microscopy revealed improved compatibility between PBT and POE in the presence of maleic anhydride groups. The melting behavior and isothermal crystallization kinetics of the blends were studied by wide‐angle X‐ray diffraction and differential scanning calorimeter; the kinetics data was delineated by kinetic models. The addition of POE or mPOE did not affect the melting behavior of PBT in samples quenched in water after blending in an extrude. Subsequent DSC scans of isothermally crystallized PBT and PBT blends exhibited two melting endotherms (T_mI and T_mII). T_mI was the fusion of the crystals grown by normal primary crystallization and T_mII was the melting peak of the most perfect crystals after reorganization. The dispersed second phase hindered the crystallization; on the other hand, the well dispersed phases with smaller size enhanced crystallization because of higher nucleation density. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nonisothermal crystallization behaviors of biodegradable double crystalline poly(butylene succinate)‐poly(ethylene glycol) multiblock copolymers

Nonisothermal crystallization behaviors of both poly(butylene succinate) (PBS) and poly(ethylene glycol) (PEG) segments within PBS‐PEG (PBSEG) multiblock copolymers were investigated by differential scanning calorimetry (DSC). The nonisothermal crystallization kinetics of both PBS and PEG segments were analyzed by Avrami, Ozawa, and Mo methods. The results showed that both of Avrami and Mo methods were successful to describe the nonisothermal crystallization kinetics of PBS and PEG segments. The results of crystallization kinetics indicated that the crystallization rate of PBS segment decreased with PBS segment content and/or L_PBS, while that of PEG segment decreased with M_n,PEG or F_PEG. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40940.