Improved Hydrophilicity from Poly(ethylene glycol) in Amphiphilic Conetworks with Poly(dimethylsiloxane)

This paper focuses on the improvement of hydrophicility and water content of poly(dimethylsiloxane) (PDMS) by bonding a hydrophilic macromer, hydroxyl-terminated linear poly(ethylene glycol) (PEG), into a highly hydrophobic macromer, hydroxyl-terminated linear PDMS to prepare amphiphilic conetworks (APCNs) with the crosslinkers, tetraethoxysilane (TEOS) and bis[(3-methyldimethoxysilyl)propyl]-polypropylene oxide (BMPPO), which also functioned as a compatibilizer. Fourier transform infrared results clearly demonstrated the occurrence of the hydrolysis reactions between the terminal hydroxyl groups on the terminal of the two polymer chains and the alkoxy groups in TEOS and BMPPO. Differential scanning calorimetry results and X-ray diffraction obviously showed the presence of the two phases in the conetworks. The contact angle (CA) indicated the wettability of the conetworks increased in the surfaces, that is, CA values decreased significantly from 105° in PDMS to 55° in the PEG/PDMS APCN (10/1 mol ratio), and the swelling degrees of the APCNs increased from ca. 0 to 60 % when the PEG/PDMS mol ratio was larger than 4/1. The APCNs with such high hydrophilicity and the good mechanical properties should be useful as biomaterials.     

Carboxylate-Ended Poly(ethylene glycol) Macromonomers and their Copolymers as Inhibitors for Calcium Phosphate and Calcium Sulfate

Carboxylate-ended poly(ethylene glycol) macromonomers, namely allylpolyethoxy carboxylate (APEC), were prepared by means of a carboxy methylation technique with the obvious advantage of energy conservation. APEC and acrylic acid (AA) were then used as monomers to obtain AA/APEC copolymers. Fourier-transform infrared spectra and nuclear magnetic resonance were employed to characterize AA/APEC structure. Observations showed that AA/APEC was a much better inhibitor both for calcium phosphate and calcium sulfate compared to the commercial inhibitors, and it was also an effective inhibitor, even at elevated temperature, pH, Ca²⁺ and Fe²⁺ concentration or in the presence of biocides.     

Polyester-Polyether Block Copolymers II. Thermal and Mechanical Properties of Poly(hexamethylene terephthalate)/Poly(oxytetramethylene) Block Copolymers

The melting and crystallisation behaviour of crystalline phases in poly (hexamethylene terephthalate)/poly(oxytetramethylene) block copolymers have been investigated in relation to copolymer composition and polyether block molecular weight (m.w.). In contrast to that in corresponding homopolymer blends, the polyester crystallinity in the block polymers is greatly reduced by incorporation of polyether units, though some persists even at low polyester contents. Concomitant changes in the glass transition temperatures show part of the polyester component to form a homogeneous component of the amorphous phase. The mechanical properties change with composition in parallel with the changes in copolymer crystallinity and T_g. Copolymers with 20-60 w % of poly(oxytetramethylene) units of m.w. 2000 are highly extensible elastomers. Those with higher m. w. polyether blocks have higher modulus and strength but suffer a serious loss of properties at 60d?C. The observations are interpreted in terms of a model in which polyester crystallites (and polyether crystallites also, for the higher m. w. polyether blocks) are supported within an amorphous matrix by tie-molecules whose nature changes with the copolymer compositions. The results are compared with those for analogous polyester-polyethers having different structural components.     

不同PEG含量对PLA/PEG共混物结晶动力学的影响

采用溶液共混法制备了一系列不同配比的聚乳酸(PLA)/聚乙二醇(PEG)共混物。通过偏光显微镜(POM)、扫描电镜(SEM)和差式扫描量热仪(DSC)研究了不同PEG含量的PLA/PEG共混物在不同结晶温度下,聚乳酸的晶体形貌、球晶生长速率及热力学性能。研究发现,PEG能够显著提高聚乳酸球晶的生长速率。当PEG含量为60%时,PLA/PEG共混物中聚乳酸球晶的生长速率最快,达到23.6μm/min,比纯聚乳酸的最快球晶生长速率(0.5μm/min)高47倍。但是,当PEG含量高于60%时,聚乳酸球晶的生长速率有所降低。同时,PLA/PEG共混物中聚乳酸球晶速率随结晶温度变化的取向,均向低温移动。另外,PLA/PEG共混物中聚乳酸球晶呈现环状花纹。DSC测试结果表明,随着PEG含量的增加,PLA/PEG共混物的玻璃化转变温度明显降低。     

Synthesis and Characterization of Poly(ethylene glycol) grafted Poly(ε-Caprolactone)

Summary A new graft copolymer, poly(ε-caprolactone) (PCL) grafted with poly(ethylene glycol) (PEG), was prepared by one-pot synthesis of ε-caprolactone and modified PEG. Aluminium isopropoxide or potassium tert-butoxide was used as a catalyst for the ring-opening polymerization. Polymerization using potassium tert-butoxide as a catalyst showed very effective graft reaction of PEG onto poly(ε-caprolactone). A slight decrease in the melting temperature was observed with the increase of the PEG graft frequency. Interestingly, considerable changes were observed on the surface property by the introducing PEG side chains compared to that of PCL homopolymer. Measurements of water contact angle showed that the hydrophilic surface of the polymer could be obtained even at a low graft frequency of PEG.     

Polyester-Polyether Block Copolymers III. Supramolecular Texture in Poly(hexamethylene terephthalate)/Poly(oxytetramethylene) Block Copolymers and Related Homopolymers and Blends

Optical and electron microscopy and small-angle X-ray scattering have been used to investigate the texture of poly(hexamethylene terephthalate)/poly(oxtetramethylene) multi-block copolymers. The findings are consistent with a substantial separation of the combined sub-species into separate phases, and with the aggregation of the alkylene terephthalate ‘hard’ segment blocks into crystalline forms analogous to those of the homopolymer alone and connected by microfibrillar units. The observations are correlated with the mechanical properties of the copolymers in terms of a ‘string of beads’ model, and compared with existing knowledge of phase-separation morphology in other families of block copolymers. Some investigation has also been made into the morphology of poly(hexamethylene terephthalate) and poly(oxytetramethylene) homopolymers and their blends crystallised from the melt. The results are considered in relation to the properties of the corresponding copolymers.     

聚乙二醇中共轭烯炔化合物的合成

发展了一种在聚乙二醇介质中末端炔烃与缺电子炔烃选择性生成共轭烯炔化合物的方法。在三苯基膦氯化钯(2mol%)、溴化亚铜(4mol%)、PEG-400(1.0g)和氮气的作用下,1mmol末端炔烃与0.5mmol缺电子炔烃可以顺利地发生交叉偶联反应选择性生成相应的共轭烯炔化合物,该反应产率较高,对环境友好,且催化体系可以适当地重复使用。     

Synthesis of Triblock Copolymers via Photopolymerization of Styrene and Methyl Methacrylate Using Macrophotoinitiators Possessing Poly(ethylene glycol) Units

Macrophotoinitiators based on poly(ethylene glycol)s bearing benzyl tereftalmono amid moieties were synthesized by the reaction of poly(ethylene glycol) (PEG) terminated with terephtaloyl chloride and benzyl amine. The initiators possessing PEG with different molecular weights were used in the photoinduced radical polymerization of styrene (S) and methyl methacrylate (MMA) to yield poly(styrene-b-ethylene glycol-b-styrene) and poly(methyl methacrylate-ethylene glycol-b-methyl methacrylate) triblock copolymers. Characterization of macrophotoinitiators were performed by elemental anlysis, IR and ¹H-NMR spectrum. The elemental analysis results agreed with the theoretical values. The IR and ¹H-NMR spectra showed that the poly(ethylene glycol) units were reacting with the tereftloyl chloride and benzylamine. Characterization of the block copolymers was carried out by spectral measurements, GPC and fractional precipitation methods. The polydispersities of the block copolymers were observed between 1.2–2.32 for poly(methyl methacrylate-ethylene glycol-b-methyl methacrylate) and 1.25–1.90 for poly(styrene-b-ethylene glycol-b-styrene) from GPC measurements.     

二甲基丙烯酸聚乙二醇酯的RAFT交联聚合行为

采用差示扫描量热(DSC)和动态力学分析(DMA)方法研究二甲基丙烯酸聚乙二醇酯(PEGDMA)的可逆加成-断裂链转移(RAFT)自由基交联聚合,探索了交联单体双键间链段长度和链柔性对RAFT交联聚合动力学及其交联结构的影响.实验发现,随着双键间乙二醇单元数由4增加到9,聚合速率加快,当乙二醇单元数由9增加到14,聚合速率不增反降,这种行为是交联网络密度减小后增长自由基浓度下降和悬挂双键反应活性增加共同作用的结果;双键间链段柔性的增加使RAFT交联聚合速率加快:随双键间链段长度增加,交联网络密度和玻璃化转变温度降低,交联网络的均匀性得到改善.     

Synthesis and Characterization of Poly(ethylene glycol) Methacrylate Based Hydrogel Networks for Anti‐Biofouling Applications

A series of hydrogels based on poly(ethylenglycol) methyl ether methacrylate (PEGMEMA) is synthesized using macromonomers of three different molecular weights, in combination with varied degrees of chemical crosslinking. The effects of PEGMEMA, initiator, and crosslinker concentrations on gel yield and swelling properties are studied. In addition, the chemical structure of the gels is characterized by FTIR and solid‐state NMR spectra. The swelling and rheological behaviors of hydrogels as well as protein partitioning into the gels are discussed in terms of the network mesh size. Low protein sorption and bacteria deposition tendencies indicate that PEGMEMA‐based hydrogels could be highly beneficial for uses as fouling‐resistant materials, for instance, as protective coatings for desalination membranes.

     

基于聚3-己基噻吩的嵌段共聚物研究进展

随着全球对新能源、新材料研究领域的战略提升,聚3-己基噻吩(P3HT)作为导电共轭聚合物的相关研究已成为近年来的一个热点,并取得了突飞猛进的进展.P3HT均聚物受其激发子寿命短的影响,其光电转换效率有限,而嵌段共聚物可以实现微相分离,进而可以实现提高有机光伏材料的光电转换效率的目的.总结了近年研究者们合成的嵌段共聚物及...     

Properties of Block Copolymers of Poly(Butylene Terephthalate) and Polyoxytetramethylene Glycol

Synthesis of polyester thermoelastoplasts, block copolymers of polyoxytetramethylene glycol and poly(butylene terephthalate) of the polyblock type, was developed and implemented in pilot industrial conditions. POTM blocks act as flexible molecular decouplings that give the copolymer elasticity, while PBT blocks form physical linkages and are responsible for the mechanical strength and hardness of the material. The composition of the reaction systems, process stage sequence, and synthesis parameters are optimized for block copolymers with a concentration of the flexible POTM block of 65-10 wt. % and a molecular weight of 1000. The structure is investigated, and the physicochemical and mechanical properties of the material obtained are determined. It was found that the concentration of flexible blocks has a determining effect on the physicochemical structure and properties of the block copolymers. For a 40% concentration of the flexible block, the character of the concentration curves of the physicomechanical indexes changes significantly due to phase-structural transformations in the block copolymers.     

Poly(methylphenylphosphazene)–Graft–Poly(methyl Methacrylate) Copolymers Via Atom Transfer Radical Polymerization

Atom transfer radical polymerization (ATRP) was used to graft poly(methyl methacrylate), PMMA, onto poly(methylphenylphosphazene), [(Me)(Ph)PN] _n , PMPP. A two-step process was used to convert a portion of the methyl substituents on [(Me)(Ph)PN] _n to –CH₂C(CH₃)₂OH groups and then to bromoalkyl groups, –CH₂C(CH₃)₂OC(=O)C(CH₃)₂Br, the latter of which served as initiation sites for ATRP of methyl methacrylate (MMA) in the presence of CuCl/bipyridine. Variations in the length of the grafted chains were investigated and the graft copolymers were compared to the parent polymer and blends of similar composition. The new bromoalkyl derivatives of [(Me)(Ph)PN] _n and the PMPP–graft–PMMA copolymers were characterized by elemental analysis, ¹H and ³¹P NMR spectroscopy, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC). We dedicate this paper to Professor Harry R. Allcock for consistently maintaining the highest standards in his creative, pioneering work in inorganic rings and polymers.     

聚丁二酸乙二醇酯合成的研究进展

综述了直接酯化聚合法、丁二酸酐开环聚合法、酯交换聚合法、耦合反应法合成聚丁二酸乙二醇酯(PES)的国内外研究进展,着重介绍了丁二酸和乙二醇酯化聚合法合成PES的催化剂和工艺的研究现状,并展望了PES及其合成工艺的发展前景。     

聚乙二醇增塑聚乳酸复合薄膜的制备与性能研究

通过溶液共混法,以三氯甲烷为溶剂,分别以聚乙二醇200(PEG200)和聚乙二醇1000(PEG1000)作为增塑剂制备了PEG增塑的聚乳酸复合薄膜。通过机械拉伸、热重、XRD和DSC对复合薄膜的力学性能、热稳定性以及热性能进行了表征。结果表明:PEG的加入能有效增强聚乳酸的柔性,断裂伸长率随PEG含量的增大明显升高,拉伸强度则随之降低,且少量添加时PEG200比PEG1000的增塑效率更高;增塑的聚乳酸薄膜低温热稳定性下降,冷结晶温度(t_c)和熔融温度(t_m)降低,结晶能力大幅提高,添加量为15%(质量分数)时PEG200和PEG1000增塑的聚乳酸薄膜结晶度(X_c)分别达到41.06%和50.15%。     

聚乙二醇增塑聚乳酸的等温结晶动力学研究

采用DSC方法对聚乙二醇(PEG)增塑聚乳酸的等温结晶动力学进行了研究。结果表明,PEG的加入提高了聚乳酸的结晶速度,在相同结晶温度下,随着PEG摩尔质量的增大,结晶速率增大,结晶活化能先减小后增大。不同摩尔质量PEG增塑PLA的结晶成核机理和生长方式一样。     

Poly(ethylene naphthalate) formation 1. transesterification of dimethylnaphthalate with ethylene glycol

The transesterification of dimethyl naphthalate (DMN) with ethylene glycol (EG) was kinetically investigated in the presence of various catalysts at 185 °C. The transesterification was assumed to obey first-order kinetics with respect to DMN and EG, and a rate equation was derived. The rate constant of transesterification which calculated from the quantity of methanol distilled from the reaction vessel was used to evaluate each metal compound in its activity. The first-order dependence on the catalyst concentration is valid below a critical concentration which was found to be dependent on the catalyst type. The order of decreasing catalytic activity of various metal ions was found to be: Pb Zn > Co > Mg > Ni Sb. But in the case of highly basic metal salts, the rate constants were found to be extremely large at the initial stage of the reaction, and then rapidly decreased with the progress of the reaction. Effects of reaction temperature were also discussed. The activation energies for zinc acetate and lead acetate were 97.84 and 97.2 KJ/mol, respectively, which were calculated from Arrhenius equation.     

Injectable gel: Poly(ethylene glycol)-sebacic acid polyester

In order to develop an injectable material for drug delivery that has both formulation advantages of a sol-to-gel transition system and minimal burst release of a drug, a soft thermogel of poly(ethylene glycol)-sebacic acid polyester was synthesized. The polymer aqueous solution (25 wt%) undergoes ‘clear sol-to-gel’ transition as the temperature increases from 5 to 65 °C. The drug can be mixed in a low viscous sol state at low temperature (<15 °C). In particular, the thermogel is soft enough to be injected through a 21-gauge syringe needle even as a gel state. The model hydrophilic drug, FITC-dextran (molecular weight: 40,000 Da), was released from the gel over 24 h. The biodegradable poly(ethylene glycol)-sebacic acid polyester soft thermogel is believed to be promising for the hydrophilic drug delivery where an initial burst of a drug might be a concern.     

Synthesis of Biodegradable Poly(butylene terephthalate)/poly(ethylene glycol) (PBT/PEG) Multiblock Copolymers and Preparation of Indirubin Loaded Microspheres

Summary Biodegradable PBT/PEG copolymers were synthesized by macromolecular transesterification method, and were characterized by 1H-NMR and DSC. Alkaline degradation behavior was studied too. Indirubin loaded microspheres were prepared by O/W solvent evaporation method.