超支化聚酯的合成及共混改性PET流变性的研究

以三羟甲基丙烷作为中心核,邻苯二甲酸为合成组分,苯磺酸作为催化剂,合成超支化聚酯,并对其结构进行了表征。研究了超支化聚酯与PET共混物的流变性能,研究表明超支化聚酯可以有效地降低熔体黏度。     

端基对超支化聚合物改性UHMWPE性能的影响

以3种不同端基的超支化聚酯(HBP)分别对超高相对分子质量聚乙烯(UHMWPE)进行共混改性,研究了HBP的端基类型和用量对UHMWPE/HBP共混物力学性能和流变性能的影响。结果表明:随着端羟基超支化聚酯HBP-OH、端苯基超支化聚酯HBP-Bz及端十六烷基超支化聚酯HBP-C16加入量的增大,UHMWPE/HBP共混物的拉伸强度不断降低,断裂伸长率呈现先增大后减小的趋势。在UHMWPE中加入HBP-C16后,共混物的复数黏度呈现上升的趋势。HBP-OH和HBP-Bz的加入量增大能增强UHMWPE大分子链的活动能力,改善了UHMWPE的加工流动性能。     

端羟基改性超支化聚酯的热稳定性及分解行为

采用热失重方法(TG)研究了端羟基超支化聚酯和端羟基改性超支化聚酯在氮气气氛中的热稳定性及分解行为。端羟基超支化聚酯的热分解过程包括酯基降解和碳碳键断裂2个阶段,随着代数增加,热稳定性有所改善。当端羟基被烷烃链取代后,端羟基超支化聚酯的热分解温度大幅度提高。低代数端羟基改性超支化聚酯的分解以碳碳键断裂为主,高代数热分解仍包括酯基降解和碳碳键断裂2个阶段。端羟基改性超支化聚酯的表观分解活化能明显提高。     

热塑性淀粉/生物降解共聚酯共混物流变性能的研究

研究了热塑性淀粉(TPS)以及TPS/生物降解共聚酯共混物的流变行为,讨论了增翅剂用量、共聚酯用量和熔体温度对流变行为的影响.研究表明,TPS和TPS/生物降解共聚酯共混物熔体呈明显的非牛顿特征;增塑剂的使用可以大幅度改善淀粉的塑化行为,通过调节增塑剂用量,可以在一定范围内控制TPS的流变行为.对于共聚酯和TPS的共混体系而言,在共聚酯用量较低时,流动过程中TPS分子链受到较强剪切力作用而发生断链,共混物熔体表观黏度降低.在共聚酯用量较高时,共混物熔体黏度则表现出对温度有较大的敏感性.TPS的黏流活化能较小,TPS/生物降解共聚酯共混物的黏流活化能随共聚酯用量的增加迅速增大,且随剪切速率的增加迅速降低.     

BoltornTM型超支化聚酯对硬质PVC流变性能的影响

采用HAKKE转矩流变仪,分析并讨论了超支化聚酯BoltornTM的用量和代数以及加工条件对硬质PVC流变性能的影响。结果表明,随着BoltornTMH30用量的增加,PVC塑化时间减少。不同代数的超支化聚酯对PVC的塑化效果不同,BoltornTMH30对PVC的塑化效果最好,塑化时间最短。该超支化聚酯/PVC共混物的最佳加工温度为175℃左右,最佳转速为50~60r/min。     

端环氧型超支化聚酯对聚（3-羟基丁酸戊酸共聚酯）的改性研究

以2,2二羟甲基丙酸（DMPA）和三羟甲基丙烷（TMP）为原料,以对甲苯磺酸（P-TSA）为催化剂,通过“一步法”合成三代超支化聚酯（HBPE）,然后采用环氧氯丙烷对HBPE进行改性,得到了具有端环氧基的三代超支化聚酯（EHBP-G3）目标产物,最后采用熔融共混法制备了EHBP改性的聚（3-羟基丁酸酯-co-3羟基戊酸酯）（PHBV）树脂;通过差示扫描量热仪、偏光显微镜、力学性能和熔体流动速率等分析方法对制备的PHBV/EHBP共混物进行表征。结果表明,加入1.5 %(质量分数,下同)三代超支化聚酯（EHBP-G3）时,PHBV/EHBP共混物的结晶度下降了16.1 %,冲击强度提高了34.3 %。     

端基对脂肪族超支化聚酯性能的影响

用十八酸对端羟基脂肪族超支化聚酯进行改性,采用差示扫描量热分析(DSC)、热重分析(TG)、旋转流变仪研究了不同端基对超支化聚酯的玻璃化转变温度、热稳定性和流变性能的影响.结果表明,端基对超支化聚合物的玻璃化转变和结晶有显著影响,通过端基长链烷烃链段的有序排列可以显著提高超支化聚合物的结晶性能;端羟基超支化聚酯的热分解...     

超支化聚酯的合成及其对PET纤维的改性研究

以三羟甲基丙烷作为中心核,二羟甲基丙酸为合成单体,对甲苯磺酸作为催化剂,采用一步法分别合成了第二代、第三代、第四代不同代数的端羟基超支化聚酯(HBP),并对其结构进行了表征.将不同代数的HBP与聚对苯二甲酸乙二醇酯(PET)共混纺丝制备了HBP/PET共混纤维,研究了纤维的流变性能、力学性能、染色性能和吸湿性能.结果表...     

端羟基超支化聚酯的稳定化改性及热分解行为

以长链烷基酸为改性剂,对以三羟甲基丙烷为核、二羟甲基丙酸为支化单体合成的端羟基超支化聚酯进行端基稳定化改性。采用羟值滴定和核磁共振氢谱(1H-NMR)表征超支化聚酯的改性程度;采用热重-微商热重分析(TG-DTG)研究了代数、端基类型以及改性程度对超支化聚酯热稳定性和热分解行为的影响。结果表明,将不稳定的端羟基转变为热稳定的端烷基后,超支化聚酯的热稳定性明显提高,且改性程度越高,或长烷烃链越短,聚合物的热稳定性越好。超支化聚酯的热分解主要包括两个失重阶段,分别对应于由大量端基所组成的"壳"的破坏以及由大量C-C单键所组成的骨架(即"核")解体。极性端羟基的含量越小或非极性端烷基的含量越大,第一失重峰越不明显。     

UHMWPE/LLDPE/HBP共混体系流变行为研究

为改善超高相对分子质量聚乙烯(UHMWPE)的加工流变性,将超支化聚酯酰胺(HBP)和线性低密度聚乙烯(LLDPE)与UHMWPE共混,研究了不同比例UHMWPE/LLDPE/HBP共混体系的流变行为。结果表明:UHMWPE/LLDPE/HBP共混体系熔体表观粘度随HBP质量分数的增加而减小;共混体系非牛顿指数<1,为典型的切力变稀流体;当剪切速率为10 s-1时,共混体系的粘流活化能较小;结构粘度指数随HBP质量分数增加而下降,随UHMWPE粘均相对分子质量增加而增大。     

端苯基超支化聚酯对PET结晶行为和构象的影响

采用差示扫描量热法(DSC)和衰减全反射傅里叶变换红外光谱(ATR-FTIR)研究了不同代数和含量的端苯基超支化聚酯(HBP)对聚对苯二甲酸乙二醇酯(PET)结晶行为和构象的影响,计算了晶带与内标峰的吸光度比值以及左右式构象的相对含量.其中975 cm?1和1340 cm?1处的吸收峰归属于反式构象,1370 cm?1处归属于左右式构象,793 cm?1和873 cm?1处的吸收峰为内标峰.结果表明,6%的第三代超支化聚酯对PET的结晶促进能力最强.随着超支化聚酯含量或代数的增加,各吸光度比值基本上都呈现出先增大后减小的趋势,左右式构象的含量则表现出先减小后增大的趋势.端苯基超支化聚酯既可以充当成核剂,又可以充当结晶促进剂,因而可以促进PET结晶.     

Rheology of concentrated solutions of hyperbranched polyesters

The solution rheology of different generations of hyperbranched polyesters in N‐methyl‐2‐pyrrolidinone (NMP) solvent was examined in this study. The solutions exhibited Newtonian behavior over a wide range of polyester concentrations. Also, the relative viscosities of poly(amidoamine) (PAMAM) dendrimers in ethylenediamine were compared with those of the hyperbranched polyesters in NMP. Both types of dendritic polymers have relative viscosities that are exponential functions of their molar fraction in solution. The slopes of these relative viscosity curves show a linear relationship with respect to the generation number. PAMAM dendrimers have the greater slopes for each generation, reflecting their relatively larger intrinsic viscosity values.     

Rheological behavior in the molten state and solution of hyperbranched polyester of fourth and fifth generation

The rheological behavior in the molten state and solution of hyperbranched polyol polyesters (HBPs) obtained by one step (HBP4, HBP5), step by step (HBP4P, HBP5P), and combination of both (HBP1‐4, HBP1‐5) was studied. Under conditions of dynamic oscillatory shear, all HBPs presented a shear‐thinning behavior and under steady shear they showed a Newtonian behavior. Also, the steady shear viscosities decreased with increasing temperature. The behavior of HBPs was mainly viscous, except for the HBP4P that showed higher storage modulus and reduction of complex viscosity when increasing the angular frequency. The HBPs presented higher complex viscosity than steady shear and they did not follow the Cox‐Merz rule. The HBPs in solution presented a plateau region at shear rate lower than 40 s⁻¹ but a shear‐thickening behavior at shear rate higher than 40 s⁻¹. The viscosities of HBPs in solution (in the plateau region) and molten state increase in the following order: HBP5P > HBP1‐5 > HBP4P > HBP1‐4 > HBP4 > HBP5. These results are not in agreement with the values of the number average molar mass obtained by vapor pressure osmometry due to different interaction between HBPs molecules. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Melt rheology of aliphatic hyperbranched polyesters

Rheological behavior in melt of aliphatic hyperbranched polyesters (AHBP), synthesized using pseudo‐one‐step and one‐step procedure, was investigated in this work. Three commercially available AHBP were also examined. Because of the presence of relatively strong hydrogen bonds between numerous end hydroxyl groups, AHBP of lower generation number, as well as the sample of tenth pseudo generation, show non‐Newtonian behavior in the entire investigated frequency and temperature region. However, for other examined AHBP, the slope of the frequency dependence of complex viscosity (η* = f(ω)) becomes smaller with the temperature increase. Therefore, samples of fourth, fifth, and sixth pseudo generations show Newtonian behavior at temperatures higher than 70°C. Value of glass transition temperature, melt flow activation energy, fractional free volume, and thermal expansion coefficient were determined for the investigated AHBP. The influence of the type of end groups on rheological properties of AHBP was also examined. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

核分子比例对超支化聚酯结构和涂膜性能的影响

以双季戊四醇为核,二羟甲基丙酸为单体合成了不同代数的超支化聚酯。采用了IR、GPC、13C NMR、DSC和化学滴定等方法对产物进行了表征和分析。试验结果表明聚合物具有较小的多分散性指数(拟两代超支化聚酯M—w/M—n=1.159,拟四代超支化聚酯M—w/M—n=1.028)。通过聚合物的13C NMR分析了超支化聚酯的支化度,表明在超支化聚酯中,端羟基的反应活性大于线性单元中羟基的活性。并用油酸对聚合物进行改性,研究了固含量与黏度的关系及其涂膜的性能;结果表明该树脂具有良好的成膜性和涂膜性能。     

Physical and thermal properties of UV curable waterborne polyurethane dispersions incorporating hyperbranched aliphatic polyester of varying generation number

Three series of novel waterborne hyperbranched polyurethane acrylates for UV curable aqueous dispersions (WHPUD) based on hydroxy-functionalized hyperbranched aliphatic polyesters Boltorn™ of varying generation number were investigated. The effects of the overall composition, including acidic and acrylate groups, and functionality of hyperbranched polyester were studied in terms of particle size, rheology, photopolymerization kinetics, dynamic mechanical thermal as well as thermal degradation behaviors of WHPUDs. The average particle sizes of aqueous dispersions, 43-134 nm, were determined by laser light scattering. The stability and particle size were dependent on the amount of carboxylic acid groups, degree of neutralization, and molecular structure. The rheological features have revealed that all dispersions belong to pseudoplastic fluids. The shear thinning behavior of WHPUDs is more pronounced for lower generation of hyperbranched polyester. The photopolymerization rates of the resins under UV irradiation in the presence of a photoinitiator showed an increasing trend with higher functionality of acrylate. The glass transition temperature (T_g) of UV cured films evaluated by dynamic mechanical thermal analysis (DMTA) showed that the influence of end capping by hard segment consisting of IPDI-HEA is remarkable due to the increase of crosslink density. The T_g, storage modulus and loss modulus increased with increasing generation number from the second to the fourth. The results of TGA for cured WHPUD films indicated good thermal stability with no appreciable weight loss until 200 °C, and that an increase in the hard segment content provoked the increases in thermal degradation temperature. This behavior is rationalized by relating crosslink density dependence of chain end concentration and the generation number of hyperbranched polyester.     

Study on hyperbranched polyesters as rheological modifier for Spandex spinning solution

The rheological behavior of polyurethane (PU)/N,N‐dimethylformamide (DMF) spinning solutions with various contents of hyperbranched polyesters was studied using a RS150L‐controlled stress rotational rheometer. The results showed that the viscosity of the spinning solutions could be greatly reduced by adding hyperbranched polyesters even at 0.5 wt% loading. The zero‐shear viscosity of solutions with hyperbranched polyesters was much lower than that of pure PU/DMF solution, which indicated a lower degree of entanglement when solutions were in a static state. The apparent activation energy of viscous flow and the critical shear rate for shear thinning of solutions with hyperbranched polyesters were much lower than that for pure PU/DMF solution, which indicated a weaker entanglement structure formed. In addition, the effect of hyperbranched polyesters on the mechanical properties of Spandex fiber was discussed. Copyright © 2006 Society of Chemical Industry     

Development of moisture cure polyurethane–urea coatings using 1,2,3-triazole core hyperbranched polyesters

This article reports the development of moisture cure polyurethane–urea coatings. The coating has been developed using different generations of novel 1,2,3-triazole core containing hyperbranched polyester polyols (THBP). For the synthesis of THBP, the core molecule, tetra hydroxyl-terminated di-triazole (THTD), has been synthesized by click reaction involving ethylene diazide and 2-butyne-1,4-diol. The polycondensation reaction between the core THTD and 2,2-bis (hydroxymethyl) propionic acid (Bis-MPA) at different mole ratios has been used to get first (THBPG-1), second (THBPG-2), and third (THBPG-3) generations of triazole core hyperbranched polyesters. The structural investigations of these THBPs have been carried out by ¹H NMR, ¹³C NMR, and FTIR spectroscopy. The different generations of THBPs were further reacted with 1-isocyanato-4-[(4-isocyanatocyclohexyl) methyl] cyclohexane (H₁₂-MDI) at OH:NCO ratio of 1:1.2 to get –NCO terminated triazole core hyperbranched polyurethanes. They were cured under atmospheric moisture to get hyperbranched polyurethane–urea coatings and were named as THBPUG-1, THBPUG-2, and THBPUG-3. FTIR has been used to confirm the formation of polyurethane coatings. The TGA and DMTA have been used to determine the thermal stability and dynamic mechanical properties of the coatings, respectively. The corrosion resistance properties of the coatings have been studied by salt spray and electrochemical test. The coatings were also evaluated for microbial resistance. The results indicate that the thermal stability, glass transition temperature, and corrosion resistance properties increase with an increase in generation number of THBPs used for coating development. All three generations of coating films show excellent antimicrobial activity. Based on overall combined structure–property relationship study, these types of coatings will be useful as multifunctional applications in marine and moist environments.     

Superposed flow properties of ceramic powder‐filled polymer melts

Complicated shape products from ceramic composite materials are nowadays intensively processed via flow molding technologies. Rheological properties of these materials are essential for the clarification of the deformation behavior through channels under various conditions. In this article, ceramic powder (zirconia) was mixed (10–50 vol%) with polypropylene, paraffin, and stearic acid in an elastic extruder. Parallel superposed steady and oscillatory shear flows were measured on a cone‐plate rheometer. Flow properties at high shear rates were evaluated on a capillary rheometer. The effects of powder content, shear rate/angular frequency, and temperature were clarified. The studied filled systems showed highly non‐Newtonian behavior and apparent yield stress; their viscoelastic properties were influenced remarkably under the superposed shear flow at low shear rate and angular frequency, and they showed significantly different behavior from unfilled and fiber‐filled systems. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Preparation and characterization of hyperbranched polyester capillary columns used for the separation of basic proteins

A series of hyperbranched polyesters with pentaerythritol as the core were synthesized and coated on the inner surface of fused‐silica capillaries by chemical bonding. Three kinds of basic proteins were selected for studying the behavior of the adsorption to fused‐silica capillaries. Comparative studies of the coating materials were conducted, and the experimental results showed that the coated columns with hyperbranched polyesters could suppress the electroosmotic flow greatly and effectively prevent adsorption in the pH range of 4–6; they were superior to capillaries coated with traditional hydroxypropyl cellulose. Furthermore, research was conducted to study the effect of hyperbranched polyester generation on the column efficiency. The results showed that higher column efficiency was obtained on a capillary column coated with the sixth generation of the hyperbranched polyester at pH 5.0. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009