Synthesis of poly(chloroprene-co-isobutyl methacrylate) and its compatibilizing effect in polychloroprene/poly(isobutyl methacrylate) blends

A copolymer of chloroprene (CP) and isobutyl methacrylate (iBMA) [poly(CP-co-iBMA)] was prepared in benzene by radical copolymerization. For comparison, the graft copolymer of iBMA onto polychloroprene (CR) [poly(CR-g-iBMA)] was also prepared. The glass transition temperature of the poly(CP-co-iBMA) was about ?32.4°C. The monomer reactivity ratios determined by the Finneman-Ross method were given as r₁ (CP) = 1.80 and r₂ (iBMA) = 0.74 in the copolymerization of CP and iBMA, respectively. Miscibility of blends of CR and poly(isobutyl methacrylate) (PiBMA), prepared by casting from tetrahydrofuran (THF) solution, was investigated by their glass transition temperature behaviors and morphologies. Although the blends of CR and PiBMA were incompatible, the addition of poly(CP-co-iBMA) or poly(CR-g-iBMA) enhanced miscibility between the two base polymers. It was found that the extent of partial miscibility becomes larger when adding poly(CP-co-iBMA) than poly(CR-g-iBMA) as a third component to the CR/PiBMA blend of 50/50 wt % composition. © 1993 John Wiley & Sons, Inc.     

Synthesis of tri-block copolymer based on polyisobutylene and poly(ethylene glycol)

Summary A block copolymer having polyisobutylene (PIB) as hydrophobic segment and poly(ethylene glycol) (PEG) as hydrophilic segments has been synthesized by a two-step process. Polyisobutylene was functionalized with phenol at both ends using BF₃· OEt₂ as catalyst, and then coupled with tosylated monomethoxy PEG. The reaction conditions were established by model studies. The characterization of the reaction product by NMR and PGC verified the formation of block copolymer by the coupling reaction.     

Synthesis of monomethoxy poly(ethylene glycol) without diol poly(ethylene glycol)

Since monomethoxy poly(ethylene glycol) (mPEG) inevitably contains diol PEG and is difficult to get high molecular weight through traditional synthesis at high temperature under high pressure, a novel synthetic technique via anionic solution polymerization was reported in this study. With a new initiating system, potassium naphthalene and methanol, was introduced, the polymerization proceeded at ambient temperature and side reactions were well restrained. Furthermore, a slight excess of potassium naphthalene can effectively remove the trace of water and oxygen in the reaction system. Under this condition, mPEG was nearly quantitatively obtained without containing diol PEG. Its Mn ranged from 1 to 30 kDa and the polydispersity was kept lower than 1.07. Characterization of the mPEG obtained was carried out using GPC to determine the content of diol PEG and ¹H‐NMR and MALDI‐ToF MS spectroscopic analysis to confirm the exact structure. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

聚乙二醇/聚己内酯三嵌段共聚物的合成与表征

以甲苯二异氰酸酯 (TDI)为偶联剂 ,合成了聚乙二醇 (PEG) /聚己内酯 (PCL)两亲性三嵌段共聚物 (PEG-b-PCL -b -PEG ,PECL) ,采用IR、1 H-NMR、DSC和WAXD分析和研究了PECL的结构与性能。实验结果表明 ,PECL的结构和组成与设计相一致 ,结晶度和熔点均低于均聚物 ,且随着PECL中PCL嵌段含量的增加 ,PCL嵌段熔点升高。透射电镜照片显示PECL纳米粒呈核 /壳结构的球形。     

Degradation behavior of poly (caprolactone)–poly(ethylene glycol) block copolymer/low–density polyethylene blends

Blends of poly(carprolactone)-poly(ethylene glycol) block polymer (PCE) with low-density polyethylene (LDPE) were prepared by extrusion followed by compression molding into thin film specimens. The morphology, thermal properties, degradation, and mechanical behavior of the blends were investigated by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), water immersion, static tensile testing, and dynamic mechanical analysis (DMA). The LDPE/PCE blends were immiscible for all chemical compositions. A LDPE/PCE (75/25 wt%) blend exhibited small reductions in weight and tensile strength after immersion in a buffer solution (pH = 5.0) at 50°C for extended periods of time. However, grafting maleic anhydride onto the LDPE/PCE blends improved the compatibility between the LDPE and PCE phases. Consequently, a 75/25 wt% blend of maleated LDPE/PCE exhibited significant losses in weight and tensile strength after immersion in the buffer solution. For comparison, blends of poly(caprolactone) (PCL) with LDPE were fabricated by similar techniques. The effect of compatibilizer on the degradation of LDPE/PCE and LDPE/PCL is discussed.     

Surface modification of polypropylene. I. Surface enrichment of poly(ethylene glycol) on polypropylene/poly(ethylene glycol) blends

The enrichment of poly(ethylene glycol) (PEG) on the surface of poly(ethylene glycol)/polypropylene (PEG/PP) blends was investigated by using attenuated total reflection infrared spectroscopy (ATR‐FTIR), contact angle measurement (CDA), and scanning electron microscopy (SEM). The preferred aggregation of the PEG component on the film surface of PP/PEG blends was affected mainly by the content, the molecular weight, and the segregated domains of PEG. Lower content and dies with higher surface energy favored the surface enrichment of PEG. The PEG with higher molecular weights was distributed in PP with larger phase domains, which resulted in a lower tendency toward preferred aggregation and surface enrichment. J. VINYL ADDIT. TECHNOL, 2008. © 2008 Society of Plastics Engineers     

Biodegradable polymer blends of poly(lactic acid) and poly(ethylene glycol)

Poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG) were melt-blended and extruded into films in the PLA/PEG ratios of 100/0, 90/10, 70/30, 50/50, and 30/70. It was concluded from the differential scanning calorimetry and dynamic mechanical analysis results that PLA/PEG blends range from miscible to partially miscible, depending on the concentration. Below 50% PEG content the PEG plasticized the PLA, yielding higher elongations and lower modulus values. Above 50% PEG content the blend morphology was driven by the increasing crystallinity of PEG, resulting in an increase in modulus and a corresponding decrease in elongation at break. The tensile strength was found to decrease in a linear fashion with increasing PEG content. Results obtained from enzymatic degradation show that the weight loss for all of the blends was significantly greater than that for the pure PLA. When the PEG content was 30% or lower, weight loss was found to be primarily due to enzymatic degradation of the PLA. Above 30% PEG content, the weight loss was found to be mainly due to the dissolution of PEG. During hydrolytic degradation, for PLA/PEG blends up to 30% PEG, weight loss occurs as a combination of degradation of PLA and dissolution of PEG. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1495–1505, 1997     

The effect of poly(ethylene glycol) as plasticizer in blends of poly(lactic acid) and poly(butylene succinate)

The effect of polyethylene glycol (PEG) on the mechanical and thermal properties of poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) blends was examined. Overall, it was found that PEG acted as an effective plasticizer for the PLA phase in these microphase‐separated blends, increasing the elongation at break in all blends and decreasing the T_g of the PLA phase. Significant effects on other properties were also observed. The tensile strength and Young's modulus both decreased with increasing PEG content in the blends. In contrast, the elongation at break increased with the addition of PEG, suggesting that PEG acted as a plasticizer in the polymer blends. Scanning electron microscope images showed that the fracture mode of PLA changed from brittle to ductile with the addition of PEG in the polymer blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43044.     

Thermo-oxidative degradation of poly(ethylene glycol)/poly( -lactic acid) blends

The thermo-oxidative degradation of poly(ethylene glycol)/poly( -lactic acid) (PEG/PLLA) blends was studied by infra-red spectroscopy (IR), differential scanning calorimetry (DSC), gel permeation chromatography (GPC) and thermogravimetry (TGA). The thermo-oxidative degradation of PEG occurred after a period time of aging in air at 80 °C. The mechanism of thermo-oxidative degradation of PEG was found to be the random chain scission of the main chain. As PEG blending with PLLA, the existence of PLLA appeared to enhance the thermo-oxidative degradation of PEG. The enhancement of thermo-oxidative degradation increased first and then decreased with the increase of PLLA. The results could be attributed to the ease of abstraction of the carboxylic hydrogen (–COOH) of PLLA, which enhanced the thermo-oxidative degradation of PEG. Also, the dilution effect of PLLA on the concentration of free radicals was an important factor of the thermo-oxidative degradation.     

Graft copolymers of nylon 6 and polyphenylene oxide: Syntheses and their role in compatibilizing nylon 6/polyphenylene oxide blends

Poly(2,6-dimethyl-p-phenylene) oxides (PPO) grafted with nylon 6 were prepared by first quantitatively brominating the PPO, followed by reacting the brominated products with nylon 6 of different molecular weights. The molecular weights of PPOs were kept intact during bromination. These graft copolymers with well-defined structures were used as compatibilizers for nylon 6/PPO blends. Some compatibilization phenomena were observed, as indicated by the mechanical properties of the blends. The best compatibilization was achieved when the graft copolymer is most block-copolymer-like. © 1994 John Wiley & Sons, Inc.     

异端基遥爪聚乙二醇的合成

采用3种新式引发剂,即2-(苄氧基）乙醇钾、2-(四氢-2H-吡喃-2-氧基)乙醇钾、单丙烯基乙二醇钾引发环氧乙烷阴离子开环聚合,反应条件为25 ℃、48 h、醇与萘钾摩尔比例1∶1,得到3种异端基遥爪聚乙二醇。以2-(苄氧基）乙醇钾引发聚合所得产物为起始物,经一系列反应,得到两种两端均为活性基团的异端基遥爪聚乙二醇,这种方法具有普适性。通过1HNMR及GPC手段,表征了产物的结构、分子量及分子量分布。结果表明可以得到高产率、分子量可控且分布窄的异端基遥爪聚乙二醇。     

The effect of poly(vinyl alcohol) hydrolysis on the properties of its blends with nylon 6

An investigation of the properties of the blends of nylon 6 (PA6) and poly(vinyl alcohol) (PVA) with varying degrees of hydrolysis was conducted. A near disappearance of the characteristics of the α‐form PVA crystals, crystallization exotherms, and hydrogen‐bonded hydroxyl groups and the tensile properties originally associated with the PVA molecules of PA6_xPVA PA6_xPVA, and PA6_xPVA specimens was observed as the PVA contents of the specimens became equal to or less than their corresponding ‘‘critical’’ values at 16.7 wt%, 33.3 wt%, and 50 wt%, respectively. These results support the idea that PVA molecules are miscible with PA6 molecules to some extent at the molecular level as the PVA contents of the blends become equal to or less than their corresponding critical PVA contents. In this article, we have proposed the possible reasons accounting for these properties of the PA6_xPVA_y series specimens with a varying degree of hydrolysis. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

聚丁二酸丁二醇酯/聚乙二醇硬脂酸酯共混物非等温结晶行为

以聚丁二酸丁二醇酯（PBS）和聚乙二醇硬脂酸酯（PEOST）为原料,采用溶液共混法制备了PEOST质量分数分别为10%（POS-10）和30%（POS-30）的两种合金材料。通过差示扫描量热法（DSC）研究了合金材料的非等温结晶行为,用莫志深（Mo）法分析了PBS的非等温结晶动力学,采用Kissinger法和Friedman法计算PBS的结晶活化能,并用红外（FTIR）和偏光显微镜（POM）进行表征。研究结果表明：PBS先结晶形成结晶微区不利于PEOST结晶,而较高含量的PEOST有利于PBS的结晶。受PBS先结晶的影响,POS-10降温DSC曲线没有出现PEOST的结晶峰,而POS-30在低的降温速率情况下出现了PEOST双结晶峰;升温DSC曲线中两试样均出现了PEOST的熔融峰。在相同的冷却速率下,POS-30的PEOST熔融温度（T_m）和熔融焓（△H_m）大于POS-10;POS-30的PBS结晶峰温度（T_p）、结晶焓（△H_c）大于POS-10,而结晶半峰宽（D）值更小;但两者的T_m和△H_m相当。随冷却速率的增加,PBS的D值增大,而PEOST的D值却降低;冷却速率的增加对PBS的T_m值影响不大,但使PEOST的T_m略有减小。Mo法适合用于共混物中PBS的非等温结晶动力学分析。POS-30的PBS绝对值结晶活化能要大于POS-10。POS-30在红外光谱谱图中出现了PEOST结晶的红外响应峰（1109cm^-1和841cm^-1）而POS-10没有。     

聚乳酸/聚乙二醇共混物的结晶与降解行为

针对聚乳酸（PLLA）亲水性差、降解周期长的问题,利用与亲水性高分子聚乙二醇（PEG）共混的方法对其进行改性。采用转矩流变仪制备了不同组成的PLLA/PEG共混物颗粒,系统研究了PLLA/PEG共混物的结晶和熔融、亲水性和在酸碱介质中的降解行为。结果表明,PEG的加入增强了共混物中PLLA的结晶能力,提高了PLLA在降温过程中的熔融结晶温度。PLLA/PEG共混物在等温结晶中表现出比纯PLLA更快的结晶速度。通过改变PLLA/PEG共混物的组成,可调控材料的表面亲水性和降解速率。随着PEG含量的增多,PLLA/PEG共混物的表面接触角降低。PLLA与PLLA/PEG共混物均可在水溶液中降解,共混物的降解速率高于纯PLLA,随着PEG含量的升高和降解液中酸碱浓度的提高,PLLA/PEG共混物的降解速率加快。     

End-group effect on chain conformation of poly(propylene glycol) and poly(ethylene glycol)

A comparison is made of the chain conformational distribution of hydroxy-terminated poly(propylene glycol) (PPG) and poly(ethylene glycol) (PEG) with their methoxy-terminated derivatives. The significant end-group dependence on the glass transition temperature in PPG was observed by differential scanning calorimetry. Raman active skeletal vibrations in the low-frequency region indicated a significant difference in chain conformation distribution between methoxy- and hydroxy-terminated PPGs, yet almost no difference between MPEG and HPEG. The increased chain stiffness in HPPG in comparison to MPPG has been attributed to the hydrogen-bonding interaction associated with the hydroxy end group in HPPG. Furthermore, the structural differences observed between PPG and PEG have been attributed to the differences in the interaction of the hydroxy end group to the ether oxygen in the two polymers. The interaction between the hydroxy end group and ether oxygen differs because the —CH₃ side group is present for one and not for the other. These structural differences are reflected in the glass transitions temperatures measured. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 197–202, 1997     

Structural characterization and luminescent properties of poly(p-phenylene vinylene) and poly(ethylene glycol) blends

The luminescent properties of poly(p-phenylenevinylene) (PPV) blending with poly (ethylene glycol) (PEG) were investigated in terms of their structural formation during sample preparation. The blended systems were prepared from an aqueous solution of water-soluble poly (xylylene tetrahydrothiophenium chloride) (PPV precursor) mixed with PEG, followed by heat treatment to remove the tetrahydrothiophene groups from the PPV precursor. Structural analysis showed that PEG could react with PPV precursor to form C-O-C linkage and carbonyl groups in PPV chains, interrupting their conjugated length as suggested by their Infrared, Raman and UV/vis spectroscopes. Wide angle X-ray scattering (WARS) of blended systems also showed that PPV in blends had less packing. As to luminescent properties, the UV/vis and photoluminescent (PL) spectra show that the energy gap needed to produce the excitons increased along with the increase of PL intensity when PPV was blended with PEG. Similar results were also found for the EL properties of ITO/polyblends/Al devices. The EL light emission from blends was blue-shifted (compared to PPV) with a rather low threshold electric field strength. The EL performance of polyblends was better than that of pure PPV. Among them, the PPV-50PEG showed the highest EL intensity. The improved EL efficiency was attributed to the dilution effect, interrupted conjugated length, and lower packing of PPV chains.     

Biodegradable polymer blends of poly(3-hydroxybutyrate) and poly(DL-lactide)-co-poly(ethylene glycol)

The melting and crystallization behavior and phase morphology of poly(3-hydroxybutyrate) (PHB) and poly(DL-lactide)-co-poly(ethylene glycol) (PELA) blends were studied by DSC, SEM, and polarizing optical microscopy. The melting temperatures of PHB in the blends showed a slight shift, and the melting enthalpy of the blends decreased linearly with the increase of PELA content. The glass transition temperatures of PHB/PELA (60/40), (40/60), and (20/80) blends were found at about 30°C, close to that of the pure PELA component, during DSC heating runs for the original samples and samples after cooling from the melt at a rate of 20°C/min. After a DSC cooling run at a rate of 100°C/min, the blends showed glass transitions in the range of 10–30°C. Uniform distribution of two phases in the blends was observed by SEM. The crystallization of PHB in the blends from both the melt and the glassy state was affected by the PELA component. When crystallized from the melt during the DSC nonisothermal crystallization run at a rate of 20°C/min, the temperatures of crystallization decreased with the increase of PELA content. Compared with pure PHB, the cold crystallization peaks of PHB in the blends shifted to higher temperatures. Well-defined spherulites of PHB were found in both pure PHB and the blends with PHB content of 80 or 60%. The growth of spherulites of PHB in the blends was affected significantly by 60% PELA content. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1849–1856, 1997     

pH/temperature-sensitive 4-arm poly(ethylene glycol)-poly(amino urethane) copolymer hydrogels

A series of novel pH/temperature-sensitive 4-arm poly(ethylene glycol)-poly(amino urethane) copolymers was synthesized via addition polymerization. The resulting copolymers were characterized by ¹H, ¹³C NMR, Fourier transform infrared spectroscopy and gel permeation chromatography. Poly(amino urethane) (PAU) segment acts as a pH/temperature-sensitive block. The copolymer aqueous solutions showed a sol-to-gel-to-aggregation phase transition as a function of pH and temperature when the pH of the copolymer solution is higher than 6.8. The sol-gel phase transition could be controlled by varying the PAU block length and copolymer concentration. The gel window covers the physiological conditions and a white gel was formed rapidly after subcutaneously injecting the copolymer solution (30 wt%) into SD rats. The in vitro release of chlorambucil, an anticancer drug, was sustained over 14 days under physiological conditions.     

Intermolecular interaction in aqueous solution of binary blends of poly(acrylamide) and poly(ethylene glycol)

The interaction between poly(acrylamide) (PAM) and poly(ethylene glycol) (PEG) in their solid mixture was studied by Fourier transform infrared spectroscopy (FTIR); and their interaction in aqueous solution was investigated by nuclear magnetic resonance spectroscopy (NMR). For the solid PAM/PEG mixtures, an induced shift of the >C?O and >N? H in amide group was found by FTIR. These results could demonstrate the formation of intermolecular hydrogen bonding between the amide group of PAM and the ether group of PEG. In the aqueous PAM/PEG solution system, the PAM and PEG associating with each other in water, i.e., the amide group of PAM interacting with the ether group of PEG through hydrogen bonding was also found by ¹H NMR. Furthermore, the effects of different molecular weight of PAM on the strength of hydrogen bonding between PAM and PEG in water were investigated systemically. It was found that the hydrogen bonding interaction between PAM and PEG in water did not increase with the enlargement of the PAM molecular weight as expected. This finding together with the viscosity reduction of aqueous PAM/PEG solution with the PAM molecular weight increasing strongly indicated that PAM molecular chain, especially having high molecular weights preferred to form spherical clews in aqueous PEG solution. Therefore, fewer amide groups in PAM could interact with the ether groups in PEG. Based on these results, a mechanism sketch of the interaction between PAM and PEG in relatively concentrated aqueous solution was proposed. The fact that the phase separation of aqueous PAM/PEG solution occurs while raising the temperature indicates that this kind of hydrogen bonding between PAM and PEG in water is weak and could be broken by controlling the temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Compatibility,steady and dynamic rheological behaviors of polylactide/poly(ethylene glycol) blends

Understanding the rheological behavior of plasticized polylactide (PLA) contributed to the optimization of processing conditions and revealed the microstructure–property relationships. In this study, the morphological, thermal, steady and dynamic rheological properties of the PLA/poly(ethylene glycol) (PEG) blends were investigated by scanning electron microscope, differential scanning calorimeter, and capillary and dynamic rheometers, respectively. The results illuminated that the melt shear flow basically fitted the power law, whereas the temperature dependence of the apparent shear viscosity (η_a) or complex viscosity (η*) followed the Arrhenius equation. Both the neat PLA and PLA/PEG blends exhibited shear‐thinning behavior. Because the incorporation of PEG reduced the intermolecular forces and improved the mobility of the PLA chains, the η_a, η*, and storage and loss moduli of the PLA/PEG blends decreased. The PEG content (W_PEG) ranged from 0 to 10 wt %, both η_a and η* decreased significantly. However, the decrements of η_a and η* became unremarkable when W_PEG exceeded 10 wt %. The reason was attributed to the occurrence of phase separation, which resulted in the decrease in the plasticization and lubrication efficiencies. This study demonstrated that the addition of the right amount of PEG obviously improved the flow properties of PLA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42919.