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。     

超支化聚酯型环氧树脂的合成及表征

用多元酸酐与环氧氯丙烷开环聚合制备了端羟基超支化聚酯,在碱作用下对羟基封端的超支化聚酯进行了闭环反应合成了超支化聚酯型环氧树增,研究了碱及碱的用量对闭环反应的影响,通过DSC考察了超支化聚酯型环氧树脂/邻苯二甲酸酐固化体系的固化行为,计算出固化过程的2个固化反应活化能Ea分别为64 35kJ/mol和91 12kJ/mol,频率因子lnA分别为21 8和26 8。     

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。     

超支化聚酯的合成及光固化性能研究

通过甲基四氢苯酐和环氧丙醇的开环聚合反应，一步法制备超支化聚酯，聚酯的数均摩尔质量为1450～2600g／mol，支化度在0．41～0．71之间。用甲基丙烯酸缩水甘油酯改性，合成了UV固化超支化聚酯，并对其光固化性能进行了初步研究，发现超支化聚酯能有效降低固化膜的线收缩率，聚酯的官能度越高，固化膜的硬度越大，固化速度越快，在约1s的固化时问内凝胶率超过75％。     

含羧基超支化聚酯丙烯酸酯的合成及其性能研究

以季戊四醇为"核",二羟甲基丙酸为AB2单体,利用逐步聚合方法合成了不同代数超支化聚酯。将得到的不同代数超支化聚酯用丁二酸酐和六亚甲基二异氰酸酯与丙烯酸羟乙酯的半加成产物按不同比例进行改性,得到了含羧基超支化聚酯丙烯酸酯。对得到的含羧基超支化聚酯丙烯酸酯的结构用傅里叶红外光谱、核磁共振波谱等手段进行了表征。紫外光谱表明,所有超支化低聚物在210 nm处有强紫外吸收;差示扫描结果表明,所有超支化聚酯丙烯酸酯都具有低的玻璃化转变温度;热重分析测试结果显示,随着超支化聚酯代数增加,超支化聚酯丙烯酸酯固化膜耐热性能提高。     

二元醇为核单体的超支化聚酯的合成与性能

分别以乙基丁基丙二醇(BEPD)、1,4-丁二醇(BDO)和新戊二醇(NPG)为核单体,二羟甲基丙酸为AB2型单体,对甲苯磺酸为催化剂,采用准一步法合成了第三代超支化聚酯(HBP-1、HBP-2和HBP-3)。采用FT-IR、1H-NMR和GPC对其结构和分子量进行表征并测定了超支化聚酯的特性黏度。以甲苯二异氰酸酯加成物为固化剂,研究了超支化聚酯的固化涂膜性能,使用热重分析仪(TGA)考察了超支化聚酯涂膜的热稳定性能。结果表明,三种核单体成功合成了超支化聚酯,以BEPD为核单体的超支化聚酯HBP-1具有最高的支化度达到0.55。GPC测得的分子量与理论分子量接近,且以BEPD为核的HBP-1分子量分布最低为1.68。超支化聚酯在极性溶剂中有较好的溶解性能,在非极性溶剂中不溶,其中HBP-1具有更好的溶解性能和较低的特性黏度(4.24 mL g 1)。超支化聚酯的固化涂膜具有较好的热稳定性、优异的附着力、柔韧性和较高的硬度。     

辅助材料

UV固化涂料用含氟超支化聚酯丙烯酸酯添加剂 以含氟异氰酸酯改性超支化聚酯Boltorn H20制备含氟超支化聚酯丙烯酸酯（FHPA）,并用1H-NMR谱和FTIR光谱分析其特点。以测量接触角的方法测试了FHPA作为添加剂的UV固化涂膜的水油湿润性。     

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。     

环氧封端的超支化聚酯醚增韧环氧树脂研究

以1,6-二溴己烷为A2单体、3,5-二羟基苯甲酸为CB2单体,通过亲核取代聚合反应合成末端为酚羟基的超支化聚酯醚(HBPEE-OH),再加入等当量的环氧溴丙烷得到末端为环氧基团的超支化聚酯醚(HBPEE-epoxy)。将HBPEE-epoxy添加到环氧/酸酐体系中,采用示差扫描量热仪研究了其对环氧树脂固化过程的影响,发现HBPEE-epoxy的添加会促进体系固化,使起始固化温度前移。对固化物的力学性能及热性能的研究发现当HBPEE-epoxy添加质量分数为4.0%时,固化物的冲击强度、弯曲强度、热分解温度、玻璃化转变温度分别提高了70.66%,19.77%,7.8℃和1.4℃。     

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.     

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。     

光固化超支化聚氨酯丙烯酸酯的合成及其固化膜性能

以新戊二醇为核,二羟甲基丙酸为支化单体合成得到每个分子中含有16个端羟基的超支化脂肪族聚酯,将其与自制甲苯-2,4-二异氰酸酯.丙烯酸羟丙醅单体的NCO端基团反应,获得新型可紫外光固化的超支化聚氨酯丙烯酸醑.应用红外光谱分别对超支化聚酯、超支化聚氨酯丙烯酸酯及其紫外光固化胶膜的化学结构进行分析,同时应用力学性能测试、差示扫描量热分析、热重分析等手段对单体官能度及用量对固化膜物理性能和热性能的影响进行研究.结果表明:随着活性单体用量的增加,固化膜的抗冲击强度增加,硬度减小,活性单体官能度的增加有利于提高其硬度;热重分析结果表明固化膜具有两个热分解温度,初始分解温度大于200℃,另一分解温度约为375℃;差示扫描量热分析结果显示,固化膜具有两个玻璃化转变温度(Tg.s,Tg.h),随着活性单体官能度的增加,Tg.s降低,Tg.h升高,有利于相分离,而其用量的增加却不利于相分离;利用红外和凝胶法分析对比研究超支化聚氨酯丙烯酸酯的光固化行为,结果表明其不饱和双键的最终转化率高达90%.     

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)。     

Mechanical and thermal properties of UV cured mixtures of linear and hyperbranched urethane acrylates

The properties of urethane acrylate resin mixtures based on the linear and hyperbranched aliphatic polyesters were examined. Linear polyester was synthesized from neopentil glycol and adipic acid. Hyperbranched polyester of the third generation was synthesized from 2,2-bis(hydroxymethyl)propionic acid and di-trimethylol propane. The modification of 60% of hyperbranched aliphatic polyester OH end groups was carried out with isononanoic acid or with soybean fatty acids. Two hyperbranched urethane acrylates, with the same degree of acrylation, and one linear urethane acrylate were obtained by reaction of appropriate polyester and isophorone diisocyanate and 2-hydroxyethyl acrylate. The influence of added amount of HUA and nature of non-acrylic end groups on the rheological, mechanical and thermal properties of the uncured and UV cured mixtures diluted with 20 wt.% hexanediol diacrylate was examined. The nature of non-acrylic end groups have great effect on the interaction between linear and hyperbranched urethane acrylates, which further has a crucial influence on the examined properties of uncured and UV cured mixture samples.     

含氟超支化聚酯的合成及其性能研究

利用十三氟辛酸对超支化聚酯进行端基改性,得到了含氟超支化聚酯。采用傅里叶变换红外光谱仪、差示扫描量热分析仪等对聚合物进行了表征和分析。结果表明:十三氟酸成功接枝到超支化聚酯上,含氟超支化聚酯的玻璃化转变温度为-20.5℃,含氟超支化聚酯溶液在固含量高达70%时仍具有较低的黏度,该聚合物成膜性好,涂膜的附着力为1级,柔韧性为1 mm,铅笔硬度2 H,抗冲击强度4.9 J/cm2,与水的接触角为105°,具有良好的表面疏水性。     

Synthesis and characterization of a thermotropic liquid crystalline hyperbranched polyester

BACKGROUND: Hyperbranched polymers have received increasing attention in the fields of medicine, homogeneous catalysis and materials science. Hydroxyl‐functional aliphatic polyesters are one of the most widely investigated families of hyperbranched polymers. The research reported here is based on the preparation of a novel hyperbranched polyester and the modification of its terminal hydroxyl groups by biphenyl mesogenic units. RESULTS: 2,2,6,6‐Tetramethylolcyclohexanol as a core and 8‐[4′‐propoxy(1,1‐biphenyl)yloxy]octanoic acid as a mesogenic unit were synthesized. A hyperbranched polyester (HPE) was synthesized in one step and subsequently substituted by reaction of its terminal hydroxyl groups with the biphenyl mesogenic units to yield a novel liquid crystalline hyperbranched polyester (HPE‐LC). The chemical structures of all compounds were confirmed using Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopy. The thermal behavior and the mesogenic properties of the biphenyl mesogenic unit and HPE‐LC were investigated using differential scanning calorimetry, polarized optical microscopy and wide‐angle X‐ray diffraction. The results demonstrated that the degree of branching of the HPE is ca 0.63. Both HPE‐LC and the biphenyl mesogenic unit exhibit mesomorphic properties, but HPE‐LC has a lower isotropic transition temperature and a wider transition temperature range than the biphenyl mesogenic unit. CONCLUSION: A novel liquid crystalline hyperbranched polyester was successfully synthesized, which exhibits mesomorphic properties. This polymer has good solubility in highly polar solvents and good thermal stability. Copyright © 2009 Society of Chemical Industry     

Hyperbranched polyesters with internal and exo‐presented hydrogen‐bond acidic sensor groups for surface acoustic wave sensors

Three hyperbranched aromatic polyesters carrying both internal and exo‐presented hydrogen‐bond acidic phenol, carboxylic acid, or mixed phenol/acetoxy groups were coated onto 500 MHz surface acoustic wave (SAW) sensor platforms, and sensor responses to the nerve agent simulant dimethyl methylphosphonate (DMMP) and the explosives simulant dinitrotoluene (DNT) were studied. All three hyperbranched polyesters gave strong responses to DMMP, and the hyperbranched polyester carrying carboxylic acid groups gave a particularly strong response. The hyperbranched polyester carrying phenol groups gave the best response to DNT of the three polymers studied. The DMMP and DNT responses of the three hyperbranched polyesters were also compared with hyperbranched SAW sensor polymers carrying exo‐presented phenolic sensor groups only, and also with linear SAW sensor polymers carrying phenolic sensor groups. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

有机硅烷偶联剂改性紫外光固化超支化聚醚基水性聚氨酯的性能

采用超支化聚酯Boltorn H 20与丁二酸酐反应,制备了亲水性超支化聚酯,然后与甲基丙烯酸酯基改性的聚醚基聚氨酯预聚体和3-异氰酸酯基丙基三乙氧基硅烷(IPTS)反应,合成了有机硅烷偶联剂改性紫外光固化聚醚基超支化水性聚氨酯(WHPU)。考察了有机硅烷偶联剂用量对WHPU的耐酸性、固化时间、凝胶质量分数、附着力、水接触角、水吸附率、乳液粒径分布及热稳定性的影响。结果表明,当IPTS与Boltorn H 20中羟基的摩尔比为6/16时,固化后的WHPU膜的凝胶质量分数为92%,在玻璃表面的附着力达到0级;与不含有机硅烷偶联剂的WHPU相比,该涂膜的水接触角和热稳定性分别提高了34°和22℃,其吸水率从13.8%降低到4.3%。     

Synthesis and self-assembly of hyperbranched polyester peripherally modified by touluene-4-sulfonyl groups

In this paper, hyperbranched polyesters (HPs) were synthesized in the molten state from 2,2-bis(hydroxymethyl) propionic acid (bis-MPA) and 2-ethyl-2-hydroxymethyl-1,3-propanediol (TMP) using acid catalysis. The modified hyperbranched polyesters were obtained through the chemical modification of the hyperbranched polyester cores by substituting a controlled fraction of the terminal hydroxyl groups with touluene-4-sulfonyl chloride using triethylamine (TEA) as an acceptor of HCl. The resultant polyesters were characterized by ¹H NMR, ¹³C NMR, FT-IR, UV and GPC and their self-assembly behaviors were investigated. The results revealed that self-assembled structures could be formed in selected solvents (trichloromethane/acetone or trichloromethane/n-hexane).     

聚酯水性化技术及水性聚酯稳定性研究进展

综述了4种含有不同亲水单体的聚酯水性化技术,包括传统型的以偏苯三酸酐为亲水性单体的水性聚酯、二羟甲基丙酸为亲水性单体的水性聚酯、紫外固化超支化水性聚酯以及磺酸盐型单体的水性聚酯。在此基础上,叙述了提高水性聚酯耐水解稳定性的方法及原理,并指出了水性聚酯的发展趋势。