超支化聚酯的合成及改性环氧树脂的研究

以季戊四醇为核,2,2-二羟甲基丙酸为增长单体,对苯甲磺酸为催化剂,合成了超支化聚酯,通过FI-IR图谱对超支化聚酯进行结构表征,证明得到端基为羟基的超支化聚酯。采用超支化聚酯做增韧剂,研究其对环氧/四氢苯酐固化体系的增韧作用,探讨了超支化聚酯的分子量(代数)、超支化聚酯的含量、固化温度等因素对环氧树脂固化体系力学韧性的影响。     

松香基超支化环氧树脂的合成及性能研究

首先以马来海松酸三缩水甘油酯(MPTGE)和马来海松酸(MPA)为主要原料,一步法合成松香基超支化聚酯(HPR),然后HPR再与环氧氯丙烷(ECH)经开环酯化、闭环反应,得到松香基超支化环氧树脂(HPER)。讨论了开环酯化、闭环反应中各因素对产物性能的影响,采用凝胶色谱仪、红外光谱仪对合成产物进行了表征,并确定了适宜的工艺条件:氯丙烷(ECH)与超支化聚酯(HPR)物质的量比为18∶1,开环反应以四丁基溴化铵为催化剂,用量为反应物总质量的2%,反应温度100℃;闭环反应中以氢氧化钠溶液作为中和剂,50℃下反应3 h。所得环氧树脂的环氧值为0.23 mol/100 g,粘度为850 mPa.s。     

超支化聚酯树脂在有无光敏剂存在下UV固化涂膜性能

丙烯酰氧基化改性的超支化聚酯UV固化速度和涂膜交联密度有较大提高,体现了其优越性。较详细介绍了结构更完整的超支化聚酯——树型聚酯,以它制备的涂料具有高反应活性;丙烯酸酯化树型聚酯在无光敏剂存在下可实行UV固化,且其涂膜具有较好的性能,为不用光敏剂实现UV固化涂料作了有益的探讨。     

端羧基超支化聚酯改性环氧树脂固化体系研究

利用丁二酸酐对端羟基超支化聚酯(AHBP)的端基进行改性,得到新的端羧基超支化聚酯(CHBP),并将其用于环氧树脂体系的增韧。研究了CHBP用量、羧基含量对环氧树脂/甲基四氢苯酐(EP/MeTHPA)固化体系的力学性能和热性能的影响。结果表明,改性后分子末端全部带羧基的CHBP的增韧作用最好,冲击强度可达18.5kJ/m2。CHBP质量分数为15%时,固化物的冲击强度可达18.2 kJ/m2,拉伸强度64.86 MPa,玻璃化温度(Tg)从100℃提高到106℃左右,可满足增韧环氧树脂的同时不降低其耐热性的要求。     

超支化聚酯增韧环氧体系固化动力学

用示差扫描量热仪(DSC)对端羟基超支化聚酯增韧环氧树脂体系的固化反应动力学过程进行分析.动态DSC研究表明,在超支化聚酯增韧环氧体系中,H30的使用导致固化反应峰值减小,反应热降低;随着H30的使用量的增大,羟基对环氧/胺反应的催化效果越明显.利用Malek模型计算0 phr和15 phr两个配比的整个固化过程的反应活化能.比较发现,使用H30的体系固化反应表现活化能在整个固化过程中变化较小,比较平缓,放热比较均匀,有利于降低体系的热应力.等温DSC研究表明,未添加H30和添加H30的体系的固化反应均符合自催化模型,添加15 phr H30的体系初期有较好的反应活性,反应级数由2.06增大到2.42,固化反应速率常数提高.     

端环氧基超支化聚酯的合成及应用

本文以季戊四醇为心核结构、2,2-二羟甲基丁酸为重复单元、对苯甲磺酸为催化剂,合成了端羟基超支化聚酯;然后,采用环氧氯丙烷对超支化聚酯的端羟基进行环氧官能化,合成端环氧基超支化聚酯,采用GPC、13CNMR及1H-NMR图谱对结构进行表征。采用端环氧基超支化聚酯做增韧剂,研究其对双酚A环氧树脂力学性能的影响,探讨了端环氧基超支化聚酯对环氧树脂固化体系力学性能及韧性的影响。     

一种用于喷墨墨水的超支化聚合染料的合成研究(英文)

本论文采用一步法,以季戊四醇作为B4核单体、2,2-二羟甲基丙酸作AB2型单体合成了超支化聚酯内核(HBPE),并对产物进行表征,计算超支化聚酯的支化度为0.41;探讨并建立了超支化聚酯的缩聚反应动力学方程-d[COOH]/dt=K[COOH][OH],该缩聚反应属于二级反应,反应速率由羧基浓度和羟基浓度共同决定。采用月桂酸改性超支化聚酯合成了新的长链烷基化的超支化聚合物(LHBP),并用红外和核磁共振谱图进行结构表征。溶解性质表明月桂酸改性超支化聚酯溶解于极性较弱的溶剂中,较未改性的超支化聚酯具有更好的有机溶剂溶解性。采用改性后的超支化聚酯内核(LHBP)和2-羟乙胺基蒽醌,通过IPDI偶联法合成了超支化聚合染料(R-LHBP)。     

超支化聚酯对环氧 -聚酯混合型粉末涂料耐冲击性的改性研究

首先通过准一步法以三羟甲基丙烷（ TMP）为核,以 2,2-二羟甲基丙酸（ DMPA）为 AB2单体,制备了端羟基超支化聚酯（HBPE-OH）。然后采用邻苯二甲酸酐对端羟基超支化聚酯进行端基改性制备了端羧基超支化聚酯（ HBPE-COOH）。研究了上述 2种超支化聚酯对环氧 -聚酯体系固化性能及环氧 -聚酯混合型粉末涂料增韧效果的影响。研究结果表明： HBPE-COOH可使环氧 -聚酯体系的固化程度增大,而 HBPE-OH使环氧 -聚酯体系的固化程度略有降低。由于超支化聚酯分子内存在大量的空腔, 2种 HBPE均可有效提高涂层的耐冲击性能。其中, HBPE-COOH的增韧效果更佳。     

季戊四醇-偏苯三酸酐-环氧氯丙烷合成超支化聚合物

以季戊四醇为“中心核”，与1，2，4-偏苯三甲酸酐和环氧氯丙烷反应合成超支化碱溶性聚酯，利用合成聚合物分子外围的羧基与甲基丙烯酸缩水甘油酯反应，在超支化聚合物分子外围引入反应性甲基丙烯酰氧基．研究了树脂组成对感光性和碱溶性的影响．结果表明：通过调整分子外围的羧基及反应性甲基丙烯酰氧基含量，可以获得较好的碱溶性和光固化性能。     

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。     

Toughening of an epoxy anhydride resin system using an epoxidized hyperbranched polymer

This paper reports on the use of an epoxidized hyperbranched polymer (HBP) as an additive to an epoxy anhydride resin system. The hyperbranched polymer used was an aliphatic polyester with a molecular weight of around 10 500 g mol^?1. The epoxy resin mixture used was a combination of a difunctional diglycidyl ether of bisphenol A (DGEBA) epoxy and an epoxy novolac, and was cured with a catalysed anhydride curing agent. It has been shown that, at a concentration range of 0 to 20 wt% addition, the HBP is able to almost double the fracture toughness, with little evidence of any deleterious effects upon processing and the durability of the cured resin system. The flexural modulus and stress, however, were found to both decrease by about 30% as a result of HBP addition while the T_g was found to decrease by about 10%. The processability of the uncured resin systems has been investigated by using rheological and calorimetric techniques and it was found that the processability window, as determined by the gel time and viscosity changes, was relatively unaffected by HBP addition. The fracture surfaces were evaluated by using scanning electron microscopy which showed that the unique structure of the HBP facilitates an enhanced interaction with the polymer matrix to achieve excellent toughness enhancement of the polymer matrix. The durability of the epoxy network has been investigated via thermogravimetric analysis (TGA) and solvent uptake, and the HBP has been shown to have little systematic deleterious effect upon the degradation temperatures and the total amount of solvent absorbed. Copyright © 2003 Society of Chemical Industry     

超支化聚酯增韧改性环氧树脂

采用端羧基的超支化聚酯(HBP-SA)和甲基四氢苯酐(MeTHPA)作为混合固化剂固化普通环氧树脂。考察了HBP-SA加入量对环氧固化物性能的影响,发现HBP-SA的加入降低了树脂固化的体积收缩率,提高了环氧固化物的拉伸强度和冲击强度。加入10%的HBP-SA,拉伸强度从22 5MPa提高到64 66MPa,而冲击强度从4 99kJ/m2提高到30 63kJ/m2,分别提高150%和500%,增韧增强效果也明显,但固化物的弯曲强度和耐热性能有所下降。     

Synthesis and application of water‐soluble hyperbranched poly(ester)s from maleic anhydride and glycerol

A water‐soluble hyperbranched polyester with a considerable number of hydroxyl terminal groups was synthesized by reacting maleic anhydride and glycerol in the absence of a solvent. The synthesized intermediate product was converted to the hyperbranched polyester by condensation polymerization, and the water by‐product produced during the esterification reaction may be removed by vacuum distillation. In the synthesis process, the crosslinking reaction occurs readily if maleic anhydride is in excess. The result shows that the product synthesized by this one‐step method is insoluble in water at room temperature, whereas the product of a quasi one‐step method, in which pentaerythritol was added as a core molecule, has good water solubility when pentaerythritol and the raw material have a molar ratio of 1 : 100 or 1 : 150. The resulting hyperbranched polyester was purified by column chromatography and characterized by infrared spectrometry. The synthetic hyperbranched polyester was used at 0.5% as a crosslinking agent for acrylic ester to inform acrylic ester latex film; the water absorption of the film was decreased significantly, the viscosity was increased, and some mechanical properties were improved. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

超支化环氧树脂的研究进展及应用前景

综述了各类超支化环氧树脂的合成工艺,主要包括聚酯型、聚醚型、聚酯聚醚型和聚烷烃超支化环氧树脂.超支化环氧树脂的合成工艺主要有缩水甘油直接法、环氧氯丙烷间接法、原子基团转移聚合法、双键加成法.对每种超支化环氧树脂的合成工艺、产品特征进行分析.提出了超支化环氧树脂在热固性材料、胶粘剂和作为无溶剂树脂等领域的应用前景.     

Synthesis and characterization of novel poly(aryl ether ketone)s containing both biphenylene and 1,4-naphthylene moieties

A novel epoxidized hydroxyl-terminated hyperbranched polymer (HPEEX) was formulated from epichlorohydrin and hydroxy-terminated hyperbranched polyester (HPE) based on trimethylol propane (TMP) and AB₂ monomer. The obtained HPEEX was characterized with FT-IR, ¹HNMR spectroscopy, TG, WAXD and GPC analysis. Results showed that the HPEEX was formulated as expected and its molecular weight and intrinsic viscosity were 3,789 g/mol and 3.96 mL/g, respectively. Meanwhile, the HPEEX was used as cross-linking agent in the preparation of waterborne epoxy resins. Performance of the HPEEX modified epoxy resin aqueous (EP-H) dispersions and their films was evaluated by various tests. It was found that with incorporation of hyperbranched polymer into the epoxy macromolecular chain, the EP-H films exhibited excellent hardness and water-proof performance: the hardness was as high as 96 (Shore A), and the contact angle of water on the surface of this kind of film was as high as 71°, resulting from branched structure, higher functionality of HPEEX, better cross-linking density and large number of hydrogen bonding in this epoxy system.     

松香基UV固化超支化聚酯丙烯酸酯的合成

采用季戊四醇作为聚酯内核与二羟甲基丙酸(DMPA)发生酯化反应后,再与以松香为原料合成的马来海松酸酐(MPA)反应合成富含末端基团的超支化聚酯大分子(HBP),再分别将2-羟乙基丙烯酸酯(2-HEA)和五缩六乙二醇丙烯酸单酯(PEA-6)引入到HBP结构中,得到新型UV固化超支化树脂(HBR)。采用红外光谱对产物结构进行了表征,对固化膜进行了热重分析,通过动态力学谱测试了其粘弹性,并对涂膜的其他基本性能进行了测定。结果表明,所得树脂大都具有较低的粘度,漆膜硬度较好,对金属、塑料底材附着力较好。随着PEA-6用量的增加,产物的硬度和热力学稳定性能下降,柔韧性增加。