Investigation of ultraviolet curable waterborne polyurethane acrylate dispersion based on hydroxyl-terminated polybutadiene

A new kind of ultraviolet (UV) curable waterborne polyurethane acrylate dispersion was synthesized based on hydroxyl-terminated polybutadiene (HTPB), poly-(propylene glycol) (PPG), isophorene diisocyanate (IPDI), 2-hydroxy ethyl acrylate (HEA) and dimethylol propionic acid (DMPA) after neutralizing by triethylamine (TEA). 2-Hydroxy-1-[4-2-hydroxyethoxy) phenyl]-2-methyl-1-propanone (Irgacure 2959) was used as a photoinitiator and deionized water as a diluent. Fourier transform infrared (FTIR) analysis was used to identify the chain structure of the UV-curable polyurethane prepolymer based on HTPB and the curing process. Effects of relative content of HTPB and PPG on emulsion stability, resistance to water and ethanol, thermal stability, compatibility of soft and hard segment, as well as the mechanical property of the cured film were investigated. Translated from Polymer Materials Science and Engineering, 2006, 22(3): 199–203 (in Chinese)     

高1, 4-结构端羟基聚异戊二烯遥爪聚合物的合成

本文采用保护基团引发剂法在环己烷溶剂中通过阴离子聚合合成双端羟基聚异戊二烯,并通过GPC、IR、1H NMR、羟值分析方法对其进行了表征。结果表明,聚合物有高的1,4-结构含量,同时聚合物的分子量大小可以控制、分子量分布窄、官能度接近2。     

酰化法测定端羟基聚丁二烯羟值的测量不确定度评定

评定了酰化法测定端羟基聚丁二烯羟值的测量不确定度。分析了测量重复性、称量过程及标准物质稳定性等因素所带来的不确定度分量,采用酰化法测定端羟基聚丁二烯羟值的扩展不确定度为0.01mmol/g。     

Facile Synthesis of Polyhydroxylated Polybutadiene Derived from Hydroxyl-Terminated Polybutadiene via Thiol-Ene Click Reaction

Polyhydroxylated polybutadiene (PHPB) was synthesized via a thiol-ene click reaction between hydroxyl-terminated polybutadiene (HTPB) and 2-mercaptoethanol (ME) with 2,2’-azoisobutyronitrile (AIBN) as initiator. Effects of AIBN content, reaction time and temperature on the click reaction were investigated by determining hydroxyl value of the PHPB. The PHPB was characterized by FT-IR, ¹H-NMR, ¹³C-NMR and GPC. Relative reactivity of three types of C?C double bonds (1,2-vinyl, 1,4-cis and 1,4-trans units) in the HTPB reacting with the ME was discussed. The results showed that the optimal reaction conditions were that the AIBN content, reaction time and temperature were 2.0 wt%, 180 min and 70°C, respectively. Under these conditions, the hydroxyl value of the PHPB was 3.12 mmol·g^?1 when the HTPB/ME mass ratio was 10:2. All three types of C?C double bonds in the HTPB could react with the ME and the reactivity order was: 1,2-vinyl unit > 1,4-cis unit > 1,4-trans unit.     

甲基丙烯酸丁酯微波无皂乳液聚合

以过硫酸钾作为引发剂进行了甲基丙烯酸丁酯的微波无皂化乳液聚合，讨论了单体浓度和引发剂用量对单体转化率，粒子粒径及其分布的影响，并与常规乳液聚合进行了比较。结果表明，通过微波无皂乳液聚合，乳胶粒子的粒径分布没有明显变化，但是聚合速率大为增加。     

原子转移自由基聚合合成(甲基)丙烯酸酯类模型聚合物及其动力学研究

本文采用一种新颖的活性自由基聚合—原子转移自由基聚合（ＡＴＲＰ）的方法，以１－溴代苯乙烷作为引发剂，过渡金属卤化物与配位剂络合物（ＣｕＢｒ／２，２’－联吡啶）为催化体系，环己酮为溶剂，进行了甲基丙烯酸正丁酯（ＢＭＡ）和丙烯酸正丁酯（ＢＡ）的活性聚合。得到具有指定分子量和窄分子量分布（１．２＜Ｍｗ／Ｍｎ＜１．５）的模型聚合物。计算并讨论了两聚合体系的ＡＴＲＰ的动力学数据     

Synthesis and properties of aromatic secondary amine-blocked isocyanates

N-Methylaniline-, diphenylamine-, and N-phenylnaphthylamine-blocked toluene diisocyanates (TDI) were prepared and characterized by IR, NMR spectroscopy, and nitrogen content analyses. The structure–property relationship of these adducts was established by reacting with hydroxyl-terminated polybutadiene (HTPB). The cure rate of the adduct increases from the N-phenylnaphthylamine- to diphenylamine- and to N-methylaniline-blocked TDI adduct. Simultaneous TGA/DTA results also confirm this trend, and the thermal stability of the adduct decreases in the following order: N-phenylnaphthylamine–TDI > diphenylamine–TDI > N-methylaniline–TDI. The gas chromatogram of the amine-blocked isocyanate confirms that the thermolysis products are the blocking agent and isocyanate. The solubilities of the adducts were carried out in polyether, polyester, and hydrocarbon polyols, and it was found that the N-methylaniline–TDI adduct shows higher solubility than the rest and also found that the polyester polyol shows higher solvating power against the adducts than the polyether and hydrocarbon polyols. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1815–1821, 1999     

接枝物EVA-g-PBMA的合成及表征

本文合成了具有端羟基的聚甲基丙烯酸丁酯(PBMA-OH),并通过与MA反应,实现了端羟基转化,为接枝EVA水解产物起到了“搭桥”的作用。通过H^1 NMR对不同水解度的EVA皂化产物进行了序列结构剖析,并合成了新型接枝物EVA-g-PBMA。     

Structural Characterization of Hydroxyl-Terminated Polybutadiene-Bound 2, 2-Thiobis(4-methyl-6-tert-butylphenol) and Its Thermo-Oxidative Aging Resistance for Natural Rubber Vulcanizates

A novel polymeric antioxidant, hydroxyl-terminated polybutadiene-bound 2,2-thiobis(4-methyl-6-tert-butylphenol) (HTPB-IPDI-TPH), was prepared by binding 2, 2-thiobis(4-methyl-6-tert-butylphenol) (TPH) onto hydroxyl-terminated polybutadiene (HTPB) with isophorone diisocyanate (IPDI). Fourier-transform infrared spectroscopy (FTIR), ¹³C nuclear magnetic resonance spectroscopy (¹³C NMR), and gel permeation chromatography (GPC) were used to characterize the structure of HTPB-IPDI-TPH. The thermal stability of HTPB-IPDI-TPH was studied by thermogravimetry analysis (TGA). The effect of HTPB-IPDI-TPH on thermo-oxidative aging resistance of NR vulcanizates was investigated, and the mechanism of thermo-oxidative aging resistance was preliminarily discussed. The results showed that HTPB-IPDI-TPH contributed better thermal stability and thermo-oxidative aging resistance to NR vulcanizates than TPH. The thermo-oxidative aging resistance of HTPB-IPDI-TPH was more remarkable in the later stage of aging. Attenuated total-reflectance Fourier-transform infrared spectroscopy (FTIR-ATR) analysis showed that the relative content of carbonyl groups of NR vulcanizate with HTPB-IPDI-TPH was obviously lower than that with TPH after thermo-oxidative aging. It is suggested that ?NHCOO? groups in HTPB-IPDI-TPH enhanced the ability of trapping alkyl peroxide radicals.     

Synthesis and characterization of the B3-monomer and hyperbranched poly(aryl ether ketone)s

Hyperbranched poly(aryl ether ketone)s were prepared by polymerization of hydroquinone (A₂) and 1,3,5-tris[4-(4-fluorobenzoyl)phenoxy]benzene (B₃). The gelation of hyperbranched poly(aryl ether ketone)s was effectively avoided. Hydroxyl-term inated (HPAEK-OH) and fluoro-terminated (HPAEK-F) hyperbranched poly(aryl ether ketone)s were prepared by using different A₂/B₃ mass ratio. The structure of the B₃ monomer was confirmed by MS, ¹H NMR/IR. The glass transition temperatures of the HPAEK-F and HPAEK-OH are 114°C and 162°C respectively. Thermal stability of HPAEK-F is higher than HPAEK-OH. __________ Translated from Acta Scientianum Naturalium Universitatis Jilinensis, 2005, 5 (in Chinese)