聚丙烯/超支化聚酯酰胺共混物的等温结晶动力学

将超支化聚酯酰胺(HBPEA)与聚丙烯(PP)挤出共混,得到PP/HBPEA共混物。利用差示扫描量热法研究了HBPEA改性PP的结晶行为和等温结晶动力学。结果表明:Avrami方程适用于研究PP/HBPEA共混物的等温结晶动力学,Avrami指数为1.48~2.11,晶体的生长方式为二维盘状方式。加入HBPEA可加快PP的结晶速率,在不同等温结晶温度条件下,HBPEA为0.4 phr时可使半结晶速率提高到纯PP的1.3~2.0倍。使用Hoffmann-Lauritizen理论计算了端表面自由能,发现加入HBPEA可降低垂直于分子链方向的界面自由能,促进PP链折叠,提高PP的结晶能力。     

超支化聚酯在环氧树脂改性中的应用

超支化聚合物是一类具有三维树形结构的高度支化的大分子。由于其独特的结构和性能以及可实现工业化生产的潜力,超支化聚合物已经成为高分子材料领域研究的热点之一,并且得到了越来越多的关注。作为一类非常重要的超支化聚合物,超支化聚酯(HBPE)引起了研究人员的极大兴趣。目前,HBPE已经在众多领域获得应用,特别是在环氧树脂改性中的研究发展迅速。综述了HBPE作为改性剂在环氧树脂中的应用研究进展,同时对HBPE在环氧树脂和其他热固性树脂改性中的应用研究方向作了展望。     

芳香族超支化聚酯的合成

以1,2,4-偏苯三酸酐、二元醇和一元醇为反应单体,采用溶液法和熔融法合成了具有芳香型结构的超支化聚酯.合成产物采用红外、核磁、GPC、粘度等进行了表征,并详细研究了反应条件对合成产物结构的影响.     

超支化聚酯的合成及改性

以三羟甲基丙烷为核分子,二羟甲基丙酸为单体,合成了超支化聚酯。采用了IR、GPC、特性黏数和化学滴定等方法对产物进行了表征和分析。实验表明合成的超支化聚酯具有较窄的分子质量分布和较小的大分子流体力学半径,有类似球形的分子结构;得到的支化聚酯Mn=4.68×103g/mol,Mw=5.4×103g/mol,Mw/Mn=1.15,[η]=5.28 mL/g。进一步用油酸对聚合物进行改性,并研究了固含量与黏度的关系及其漆膜的性能;结果表明该树脂具有良好的成膜性和涂膜性能。     

脂肪族超支化聚酯在涂料中的应用研究进展

脂肪族超支化聚酯因其独特的结构和性能特点,成为目前商业化生产的超支化聚合物之一,已在众多领域获得应用,特别是在涂料工业领域的应用发展迅速.本文综述了脂肪族超支化聚酯在高固体分涂料、UV固化涂料和其他类型涂料中的应用研究进展,同时对超支化聚酯今后的研究方向作了展望.     

超支化聚酯用于负性光致抗蚀剂

采用偏苯三酸酐（TMA），甲基丙烯酸缩水甘油酯（GMA）两种单体经一步法反应制备了一系列超支化聚酯负性光致抗蚀剂。采用GPC、FTIR对超支化聚酯的结构进行了初步表征，探讨了GMA用量、投料方式和反应温度对重均分子质量及其分子量分布的影响。结果表明，增加GMA用量和选用滴加原料的方式将使树脂重均分子量增大、分子量分布变宽，反应温度为90℃时，合适。测得优化工艺所制备的光刻胶的T0（初始曝光时间）为10s，Y　gel（反差值）为2．8。     

超支化聚酯共混聚合物等温结晶动力学研究

采用三羟甲基丙烷、2,2-二羟甲基丙酸、对甲苯磺酸反应制备第2～5代超支化聚酯(HBP),将其按质量分数10%分别与聚丙烯(PP)和聚甲醛(POM)共混,用差示扫描量热法(DSC)研究了共混物的等温结晶动力学。结果表明,用Avrami方程描述PP/HBP和POM/HBP的结晶动力学较理想。在PP中,HBP主要起成核作用;在POM中,HBP主要起稀释作用;第2代HBP成核作用最弱,稀释作用最强,第5代HBP稀释作用最小。     

超支化聚合物对聚丙烯/剑麻纤维复合材料性能影响

为改善剑麻纤维(SF)与聚丙烯(PP)之间的相容性,在PP/SF复合材料中添加超支化聚酯(H101)、超支化环氧树脂(E102),研究了两种超支化聚合物(HBP)的热稳定性及对PP/SF复合材力学性能、熔体流动性和微观形貌的影响。热重分析表明,所使用的HBP均具有较好的热稳定性;扫描电子显微镜分析发现,HBP的加入使基体与纤维结合得更加紧密;力学性能测试表明,H101可不同程度地提高复合材料的拉伸、弯曲及冲击强度;E102可提高复合材料的拉伸及冲击强度,当E102含量为10%时,与PP/SF复合材料相比,冲击强度提高了72.24%。尽管HBP含量较高时复合材料的力学性能提高,但HBP会降低复合材料的熔体流动速率,选择HBP含量时需要综合考虑。     

超支化聚酯在环氧树脂改性中的研究进展

综述了超支化聚酯(HBPE)在环氧树脂改性中的研究进展,首先对端羟基/端羧基/端环氧/端氨基HBPE的制备方法进行了总结;随后对不同端基的HBPE在环氧树脂的增韧改性及其增韧机理的研究进展进行了介绍;然后介绍了不同端基的HBPE对环氧树脂固化性能的影响研究.最后分析了HBPE在环氧树脂改性领域中需要关注的问题,指出未来...     

超支化聚合物涂料

介绍了超支化聚合物的发展、特性，合成的简捷性及在涂料中的应用前景。     

Disperse dyeing of methacrylic acid grafted polypropylene fibres

The dyeing behaviour of methacrylic acid grafted polypropylene fibre with a disperse dye (Dispersol Red B-3B) under infinite dyebath conditions has been evaluated. It was found that uptake of dye by the fibre is considerably improved by grafting. The rate of dyeing and the diffusion coefficient also showed marked increases in the grafted samples. Theresults have been explained in terms of the structural changes in the fibre effected by grafting.     

Relaxation processes in hyperbranched polyesters

Summary Dielectric permittivity and loss have been measured over the frequency range 10^-2 Hz-10 kHz between 100 K and 350 K for samples of 50/50 mixtures of each of two hyperbranched polyesters, one five-generation hydroxy functional (5G-OH) and one threegeneration alkyl-terminated polymer (3G), with dielectrically inactive linear polyethylene. The thermal transitions of the hyperbranched polymers were studied with differential scanning calorimetry. Three relaxation transitions were found in 5G-OH: , the glass-rubber transition and two subglass processes denoted and showing Arrhenius temperature dependence both with an activation energy of 96±2kJ mol^-1. The low temperature process could be assigned to motions of the terminal hydroxyl groups whereas is due to reorientation of the ester groups. Sample 3G showed only a glass transition and one subglass process being assigned to reorientation of the ester groups. The high activation energy (202 kJ mol^-1) of this process indicates that the ester groups are highly constrained in this polymer.     

Enzymatic degradation of hyperbranched polyesters

In this work, the enzyme‐catalyzed degradation of hyperbranched polyesters (HBPEs) was investigated. Enzymatic degradation experiments were performed in a phosphate buffer in the presence of the lipases Candida cylindracea, Pseudomonas cepacia, Novozym 388, Amano CE, Lipomod 34P, and Cal‐B, whereas control experiments were performed in the same system without lipases. The extent of polymer degradation was determined by quantification of the released free fatty acids by gas chromatography. The influence of the alkane chain length and the number of alkane chain end groups on the lipase‐catalyzed hydrolysis of esterified HBPEs was investigated systematically. It was found that the increase in the alkane chain length of the end groups diminished the enzymatic degradation of the polymer, whereas the number of end groups had no influence on the degradation rate. The effect of temperature on the rate of degradation was also described. Surface morphological changes that occurred during the degradation were assessed with reflected electron microscopy. The changes in the crystallinity of the polymers after they were subjected to degradation were qualitatively determined with differential scanning calorimetry through the quantification of the enthalpy of melting. The enthalpy of melting of one HBPE sample increased from 79 to 90 and 94 J/g with and without the action of Lipomod 34P, respectively, in 7 days, showing the changes in the crystallinity of the polymer. The results prove that modified HBPEs are an important new class of biodegradable materials with a predictable degradation mechanism, and the degradation can be adjusted on the basis of the molecular engineering. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Macroscopic self-assembly of hyperbranched polyesters

We utilized melt polycondensation of 2,2-bis(hydroxymethyl) propionic acid (bis-MPA) and 2-ethyl-2-hydroxymethyl-1,3-propanediol (TMP) to synthesize a hyperbranched polyester core and subsequent substitution by reaction of terminal hydroxyl with benzoyl chloride in DMF in the presence of TEA as the acceptors of HCl. It has been found that well-defined macroscopic structures can be formed via hydrogen bonding and π-π stacking interactions. Meanwhile, the molecular structures, the nature of the solvent, the molecular concentration, the volatilizing ratio of solvent, and self-assembly temperature also affected the self-assembly structures. The type of self-assembly method offers a synthetic route to well-defined one-dimensional organic macrostructures.     

Rheological characteristics of hyperbranched polyesters

Summary When the effects of physical aging below T _g are erased, the rheological response of a series of aliphatic hyperbranched polyesters is Newtonian and the melt viscosity scales roughly linearly with M _w at high M _w, indicating entanglement to be absent. The rheological behavior is also highly sensitive to the nature of the terminal groups, suggesting the overall behavior to be close to that of an assembly of compact coreshell "particles". There are therefore strong parallels between the physical behavior of the hyperbranched polyesters in question and that of their ideal dendrimer analogues. Received: 14 April 2002 /Revised: 1 July 2002 / Accepted: 1 July 2002     

Characterization of commercial aliphatic hyperbranched polyesters

Commercially available Boltorn Hx (x=20, 30) hyperbranched (HB) polyesters of different theoretical core/monomer ratio (1/12 for H20 and 1/28 for H30) were characterized with respect to molar mass, composition, and structure. The results were compared to those obtained for the Boltorn H40 with a core/monomer ratio of 1/60 [?agar E, ?igon M. Macromolecules 2002;35:9913 [11]]. The main side reaction in the pseudo one-pot synthesis of Boltorn polymers is a self-condensation of bis-MPA leading to the formation of HB structures without a core molecule. These are actually branches containing an unreacted carboxyl group. The fraction of HB structures without a core molecule increases with decreasing core/monomer ratio due to the decreasing fraction of HB structures with a core molecule. Since HB structures without a core molecule are of lower molar masses than HB structures with a core molecule, they particularly decrease the number average molar masses of the samples compared to the theoretically calculated ones. The polydispersity of Boltorn Hx increases with decreasing core/monomer ratio. Some of the hydroxyl groups were found to react intramoleculary forming ether bonds. Boltorn Hx polyesters have low degrees of branching due to the limited carboxyl group conversions, low DP_n values, the presence of the core unit, and lower reactivity of hydroxyl groups in linear repeat units compared to those in terminal ones. The degree of branching according to Frey increases with decreasing core/monomer ratio.     

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     

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.     

Solution properties of selectively modified hyperbranched polyesters

Simultaneous characterization of the degree of branching and molar mass on a molecular level for hyperbranched polymers is still strongly limited. Therefore model hyperbranched polyesters for development of new chromatographic techniques on the basis of 2,2-bis(hydroxymethyl)propionic acid were synthesized. The two types of OH-functionalities (linear and terminal) of the hyperbranched polymer were selectively modified using different protection groups. The modification of the terminal end groups was carried out using their diol character with the formation of a ketal ring without changing the chemical structure of the linear OH groups. In order to obtain completely non-polar polymer, the linear OH-units were functionalized with an acetyl group. The last modification step was the deprotection of the terminal end groups by removing the ketal ring. Fractions with various molar masses for each modification stage were obtained by preparative fractionation. Extensive characterization by SEC-MALLS, NMR spectroscopy, and viscosity measurements elucidated the dependence of the molecular shape in solution on the polarity. These results were supported by molecular dynamic simulations.     

Synthesis and characterization of glycerol-adipic acid hyperbranched polyesters

The structure and molecular weight of the hyperbranched polyesterification of adipic acid and glycerol were characterized by ¹³C NMR spectroscopy and size-exclusion chromatography as a function of reaction time and reaction stoichiometry. The glycerol substitution patterns and the extent of reaction of both glycerol and adipic acid were determined by NMR. The glycerol species concentrations determined by NMR were used with a Macosko–Miller conditional probability model to predict the hyperbranched polyester weight-average molecular weight. The model accommodated the difference in primary and secondary –OH reactivity and any substituent effects to glycerol –OH reactivity. In all cases, the predicted weight-average molecular weights were in excellent agreement with the absolute molecular weights determined by size-exclusion chromatography with light scattering detection.