UV固化超支化聚酯的合成及性能研究

以马来海松酸(MPA),环氧氯丙烷(ECH)合成了超支化聚酯(HBPE),通过丙烯酸羟乙酯(HEA)对HBPE改性合成了涂料可用UV固化超支化聚酯。采用GPC,FT-IR,DSC等对产物结构进行了表征,研究了原料配比、加料方式和反应温度等对产物的影响,并考察了其光固化行为,测试了固化膜的性能。结果表明,HBPE合成最佳条件:n(MPA)∶n(ECH)=1∶1,反应温度90℃,HBPE与HEA最佳物质的量比为1∶2。该UV固化超支化聚酯固化膜附着力1级,抗冲击力40 kg/cm,铅笔硬度4H,耐甲乙酮100,可作为UV固化涂料中的主体树脂。     

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。     

超支化不饱和树脂改性不饱和聚酯涂料的制备及性能研究

为了进一步提高不饱和聚酯涂料的固化能力和涂膜的综合性能,用三羟甲基丙烷二烯丙基醚与异佛尔酮二异氰酸酯加成物对端羟基超支化聚酯进行改性制得超支化的不饱和树脂,再用所得的超支化不饱和树脂对线性不饱和聚酯进行改性,用傅里叶变换红外(FT-IR)、核磁共振(1H-NMR)、凝胶渗透色谱(GPC)、扫描电子显微镜(SEM)、热重分析(TG)等对产物进行表征与分析,结果表明,当超支化不饱和树脂添加量为30%时,所得涂料具有最优异的综合性能,表干时间39 min,铅笔硬度2H,柔韧性3 mm,耐冲击性45 cm,拉伸强度10.15 MPa,断裂伸长率13.06%,耐热性最好。     

以季戊四醇为核的超支化树脂的研究

以季戊四醇(B4)、2,2-二羟甲基丙酸(AB2)和对甲苯磺酸通过准一步熔融缩聚反应合成了常温为玻璃态的不同代数脂肪族超支化聚酯.采用13C NMR、FI-IR、GPC、DSC等方法对其结构和性能等进行了表征与分析.结果表明得到了高转化率、相对分子质量分布较窄、支化度较高且Tg在60～80℃的超支化聚酯.以甲基丙烯酸为反应试剂,对超支化聚酯进行部分端基改性,得到了粉末状改性超支化树脂,可以进一步为合成UV涂料主体树脂提供指导.     

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。     

环氧树脂改性超支化聚酯的合成及性能

以偏苯三酸酐、环氧氯丙烷及甲基丙烯酸缩水甘油酯为原料合成了超支化聚酯(HBP),再通过超支化聚合物的羧基与环氧树脂环氧基的反应得到环氧改性超支化聚合物;用GPC1、H-NMR、DSC、TGA表征了环氧改性超支化聚合物的结构和热性能;比较了不同环氧树脂用量改性前后树脂的光反应活性以及光固化涂层的耐擦洗性和硬度,测定了凝胶率-曝光时间曲线;以环氧改性超支化聚合物配制了光刻胶,在混合光源以及接触曝光的条件下,分辨率达到2~3μm,且图像十分清晰,断面整齐。环氧树脂用量为HBP羧基物质量的70%左右时,改性的超支化聚酯的光固化活性有明显提高,力学性能得到明显改进。     

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)。     

超支化聚合物改性水性聚氨酯的制备与性能研究

以多官能度聚酯二元醇为软段、HBP(端羟基超支化聚酯)为改性交联剂、IPDI(异佛尔酮二异氰酸酯)和DMPA(二羟甲基丙酸)为硬段,采用原位聚合法制备出稳定的HBPU(超支化水性聚氨酯分散液),并对其结构和性能进行了分析。研究结果表明:经羟基比率为1∶6的HBP改性后,相应HBPU的表面张力降低,说明其对非极性基材的浸润性增强;由于WPU(水性聚氨酯)大分子链之间形成了交联网状结构,故HBPU胶膜的力学性能、硬度和热性能等得到明显改善。     

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。     

一种可功能化的Boltorn型超支化聚酯的合成研究

采用一步法,以季戊四醇(B4单体)为核,2,2-二羟甲基丙酸(AB2单体)为单体,钛酸正丁酯为催化剂,合成了Boltorn型超支化(Hyp-DMPA)。采用FT-IR、NMR和化学滴定等方法对产物进行了表征和分析,并研究了超支化聚酯的缩聚反应动力学。以IR、1H-NMR证实了聚酯结构的存在,13C-NMR谱图上3种季碳的特征峰有力证实了超支化分子结构的存在,MALDI-TOF MS证明了超支化聚酯的成功合成,并计算超支化聚酯的支化度为0.408;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。     

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...     

Preparation and characterization of UV-curable hyperbranched polyurethane acrylate

A series of UV-curable hyperbranched polyurethane acrylate (HBPUA) oligomers were synthesized with isophorone diisocyanate (IPDI), hyperbranched polyester Boltorn H20 (HBP) and hydroxy-ethyl acrylate (HEA). The structure of HBPUA oligomers was characterized by Fourier transform infrared (FTIR) spectroscopy, ¹H nuclear magnetic resonance (¹H-NMR) spectroscopy, and gel permeation chromatography (GPC). The UV-curing kinetics of HBPUA films with Darocur 1173 were investigated, and their heat resistance and mechanical properties (including hardness, adhesion force, flexibility, and impact strength) were measured. The results show that the HBPUA oligomers have superior photosensitivity and the percent conversion of C=C reaches 81% when radiation time is 43 s. The heat resistance of the cured films decreased slightly with the increase in the content of the urethane-acrylate terminal group. Moreover, the mechanical properties of the cured films were influenced by the content of the OH group in HBP that reacted with the first NCO group of IPDI. When the content was 60%, the cured film had excellent overall properties. The hardness, flexibility, adhesion force, and impact strength were 4 H, 2 mm, 0 grade, and 47 kg cm, respectively.     

含三嗪环的超支化聚酯丙烯酸酯的合成和应用

以丙烯酸甲酯和二乙醇胺为原料,制得N,N-二羟乙基-3-胺基丙酸甲酯（DAMP）;接着,用DAMP与三羟乙基异氰脲酸酯（THEIC）经酯交换反应,合成出一种超支化聚酯多元醇;再以该多元醇与丙烯酸通过酯化反应,制备了可UV固化的超支化聚酯丙烯酸酯。实验结果表明：以对甲苯磺酸为催化剂,当THEIC与DAMP的物质的量比为1∶9时,可制得二代超支化聚酯多元醇;该聚酯丙烯酸酯的玻璃化温度为53.0℃,与环氧丙烯酸酯（9104）混合组成的组合物,具有固化速度快、固化膜柔韧性佳的特点;附着力可达0级,摆杆硬度为0.751。     

棕榈酸对脂肪族超支化聚酯的端基改性研究

采用准一步法,以三羟甲基丙烷为核,2,2-二羟甲基丙酸为AB2型单体合成超支化聚酯。为了拓宽其使用范围,用棕榈酸(十六碳酸)对超支化聚酯进行端基改性,成功地找出了提纯的方法,并进行了表征。测试结果表明,聚酯的端羟基大约有97%被酯化,说明方法可行。与用棕榈酰氯进行改性相比,大大节约了成本。     

超支化聚酯的改性及其在牙科修复树脂中的应用

以季戊四醇(B4单体)为核,2,2-二羟甲基丙酸(AB2单体)为单体,对甲苯磺酸为催化剂,通过熔融缩聚反应合成末端为16个羟基的二代Boltorn型超支化聚酯HBP。并进一步用甲基丙烯酰氯、丙酰氯对端羟基进行改性,在HBP末端全部引入双键或部分引入双键,得改性后超支化聚酯GHBP1和GHBP2。在传统牙科修复树脂双酚A甲基丙烯酸缩水甘油酯(Bis-GMA)和二甲基丙烯酸三甘醇酯(TEGDMA)的混合体系中引入不同质量分数的GHBP,考察其对树脂收缩率和双键转化率的影响。结果表明,GHBP改性牙科修复树脂后,树脂的聚合收缩明显降低,且GHBP2具有更优异的减小收缩的性能,但双键转化率无明显变化。     

A morphological investigation of thermosets toughened with novel thermoplastics. I. Bismaleimide modified with hyperbranched polyester

The morphology of a bismaleimide (BMI) toughened with a thermoplastic hyperbranched aliphatic polyester (HBP) was studied by scanning electron microscopy (SEM). The effect of thermoplastic architecture, molecular weight, and end group on the size and arrangement of the dispersed phase was investigated and compared with the thermoset fracture toughness. SEM micrographs showed that higher molecular weight HBP formed roughly spherical dispersed domains of up to ∼ 60 μm, which contained BMI inclusions. Lower molecular weight HBP formed spherical dispersed thermoplastic domains, with diameters up to ∼ 10 μm with no BMI inclusions. A low molecular weight linear polyester with a repeat unit structure, which was similar to that of the HBP, was prepared and used as a control. Within error, BMI toughened with the linear control yielded the same fracture toughness as the best values obtained with HBP‐modified BMI, but the morphology differed. The linear polyester phase separated into particles with a larger average diameter and also possessed some phase‐inverted regions. End group effects were studied by modifying the hydroxy‐terminated HBP to unreactive nitrophenyl, phenyl, and acetyl end groups. The nitrophenyl‐terminated HBP did not phase separate from the thermoset, whereas the nonpolar phenyl‐ and acetyl‐terminated HBP phase separated to form small (≤1 μm and ∼ 2 μm, respectively) spherical domains. Some comparisons were made to other results with HBP thermoplastics in BMI and epoxy thermosets. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1065–1076, 1999     

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.     

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%.     

Effect of tall oil fatty acids content on the properties of novel hyperbranched alkyd resins

Hyperbranched alkyd resins (HBRA) were synthesized by modification of hydroxylated hyperbranched polyester (HBP1‐4) with tall oil fatty acids (TOFA). The core is a hydroxylated hyperbranched polyester of fourth generation with OH groups in the periphery (18), which is endcapped with tall oil fatty acids. The occurrence of these reactions, HBP1‐4 and TOFA, was determined by making use of acid value, nuclear magnetic resonance, and hydroxyl values. The effects of TOFA and HBP1‐4 on properties of the HBRA resins were investigated by vapor pressure osmometry, differential scanning calorimetry, thermogravimetric analysis, friction resistance, and hardness. The resins with higher modification percentage (HBRA4) presented the best thermal and hydrolytic stability, but lower friction resistance and hardness. All HBRA resins presented amorphous characteristics, OH groups, and double bonds in the periphery. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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。