环氧树脂-聚醚-三乙烯四胺嵌段聚合物的表面活性研究

本文对含有环氧树脂分子链段、聚醚链段及三乙烯四胺链段的系列多嵌段聚合物（TETA-DGEPG-EPON828、TETA-DGEPG-EPON834及TETA-DGEPG-EPON1001加成物）进行了合成与表征。其HLB的估算值分别为16.6、15.8、13.0;浊点分别为91.0℃、89.0℃、81.0℃,它们能将水溶液表面张力从74mN•m-1降低到36.4~39.4mN•m-1。通过其理化性能的研究,结果表明TETA-DGEPG-EPON834具有优良的水溶性和良好的表面活性。选用它作为相反转乳化剂,可制备出稳定的纳米级的CARDURA E-10封端的EPON828-TETA加成物的水性环氧固化剂胺基分散体乳液。     

环氧树脂-聚醚-三乙烯四胺嵌段聚合物的表面活性

对含有环氧树脂分子链段、聚醚链段及三乙烯四胺链段的系列多嵌段聚合物(TETA-DGEPG-EPON828、TETA-DGEPG-EPON834及TETA-DGEPG-EPON1001加成物)进行了合成与表征. 其HLB的估算值分别为16.6、15.8和13.0,浊点分别为91.0、89.0和81.0 ℃. 合成物能将水溶液表面张力从74 mN/m降低至36.4～39.4 mN/m. 理化性能研究结果表明,TETA-DGEPG-EPON834具有优良的水溶性和良好的表面活性,用它作为相反转乳化剂,可制备出稳定的纳米级CARDURA E-10封端的EPON828-TETA加成物水性环氧固化剂胺基分散体乳液.     

水性环氧树脂的研制及其固化性能研究

采用端甲氧基聚乙二醇、马来酸酐、E-44环氧树脂合成了反应型环氧树脂乳化剂MeO-PEG-Ma-E-44,以相反转乳化技术制备E-44水性环氧树脂,研究了工艺条件对其性能的影响。结果表明:酯化率达98.5%的MeO-PEG-Ma-E-44,用量为E-44的ω=16.5%-20%得到的水性环氧树脂乳液最稳定。DSC和TG分析结果表明:乳化前后的E-44环氧树脂都能室温条件2h内很好的固化,固化后热性能基本不变,分解温度约在380℃,热失重率89%,其玻璃转变温度有所降低,韧性有所提高,其它性能基本不受影响。     

自乳化水性环氧树脂乳液的研制

利用化学改性的方法制备自乳化型水性环氧树脂乳液。采用二乙醇胺部分开环环氧树脂,并采用聚醚多胺进行扩链,制备可自分散的阳离子水性环氧树脂乳液。本文研究了乳液研制时共溶剂丙二醇甲醚、环氧树脂分子量、二乙醇胺用量、不同的聚醚多胺、聚醚多胺D-230用量、HAC用量对乳液稳定性的影响。并对乳液性能进行测试,结果表明,该乳液具有良好的贮存稳定性,VOC含量低,涂膜综合性能优良等特点,该乳液为环保型产品。     

含柔性间隔基的扩链脲增韧环氧树脂性能研究——环氧树脂／扩链脲／双氰双胺体系性能研究

合成了含不同分子量柔性间隔基的扩链脲（Ｕｉ），并对其与双氰双胺共同固化环氧树脂体系的反应活性、抗冲击性能、动态力学性能、形态结构及贮存性能进行了考察。结果表明：含分子量为４００的聚乙二醇柔性链的扩链脲／双氰双胺／环氧树脂固化体系的抗冲击强度较单纯双氰双胺／环氧树脂固化体系提高了７倍左右，其冲击试样断面电镜照片呈韧性断裂的特征。扩链脲的反应活性基本不受分子中聚乙二醇链段分子量的影响。环氧树脂／扩链脲／双氰双胺体系在５０℃下贮存期可达１～２天。     

三羟甲基十一烷的合成与表征

三羟甲基烷烃是用于醇酸树脂、聚氨酯树脂、表面活性剂、合成润滑油等的原料[1-3].三羟甲基十一烷(化学结构见图1)作为三羟甲基烷烃中直碳链最长的一员,不仅具有亲水性(分子中含三个亲水基),而且具有疏水性(含一个长直碳链亲油基),因此可用作表面活性剂.不仅如此,与同样用作乳化剂的一般高级脂肪醇(如十六烷醇)相比,可以在化妆品用的乳液中加入三羟甲基十一烷作乳化剂,以降低乳液的黏度,防止乳液中由于大量加入高级脂肪醇而导致产品黏度过高以至不能在皮肤上被充分涂抹开的状况发生[4].为制备智能芳香缓释型聚氨酯微胶囊壳材[5],需要设计聚氨酯的分子结构中含有能与相变石腊和油溶性香料有良好相容性的疏水链(三羟甲基十一烷与六亚甲基二异氰酸酯的加成物).因此,本文合成并表征了三羟甲基十一烷.     

环氧树脂水基分散体系的相反转乳化

以聚乙二醇－邻苯二甲酸酐－环氧树脂Ｅ－４４多元嵌段共聚体为乳化剂,将环氧树脂Ｅ－４乳化成水包油的稳定水基乳液。用乳液体系电导率和粘度的变化表征了相反转乳化过程。研究了乳化剂浓度、三元多嵌段共聚体中亲水嵌段分子量和乳化温度对相反转乳化过程的影响。实验结果表明,体系在较高乳化剂浓度（９．１％）下为完全相反转,在低乳化剂浓度（４．１％）下为不完全相反转。相反转时水与环氧树脂Ｅ－４４的重量比值随乳化剂浓度     

水性环氧复合乳化剂的合成及性能

以环氧树脂E-44、2-氨基-5-磺酸基苯甲酸、乙二醇丁醚和正丁醇为原料,合成一种新型阴离子环氧乳化剂EP-D;同时,E-44和聚乙二醇(PEG6000)以摩尔比2∶1反应,合成端环氧基非离子环氧乳化剂EP-PEG;将EP-D与EP-PEG按不同质量比复配获得不同配比的EP-D/EP-PEG水性环氧复合乳化剂。 分别研究了EP-D/EP-PEG及EP-PEG在环氧树脂中加入质量分数为6%~12%时的乳化性能及形成乳液的表面张力、电导率和胶粒的Zeta电位、粒径。 结果表明,当EP-D和EP-PEG以质量比3∶5复配,总加入质量分数为9%时,制备的环氧乳液性能最佳。 与EP-PEG形成的环氧乳液相比,复配环氧乳化剂用量少,乳液铺展性好、稳定性高,且乳液在相反转时的固含量提高了10%以上。 复配环氧树脂乳液中胶粒的Zeta电位为-41.9 mV、粒径为342 nm、表面张力为25.5 mN/m、粘度为14 mPa·s。 这表明利用乳化剂EP-D与EP-PEG复配新合成的EP-D/EP-PEG水性环氧复合乳化剂可制备稳定性好,固含量高的乳液。     

非离子型活性乳化剂及其水性环氧树脂的制备和性能

以α-甲氧基-ω-N-异丙醇基-对苯甲胺基聚乙二醇和酚醛环氧树脂F51为原料合成了非离子型活性乳化剂(PEGF51),并与F51混合,通过相反转法制备了分散相粒径为纳米级的PEGF51/F51水乳液.通过红外光谱和凝胶渗透色谱(GPC)分析了PEGF51的结构,研究了PEGF51浓度对PEGF51/F51水乳液分散相粒子粒径和D230-PEGF51/F51固化产物的力学性能、断面形貌和耐水性能的影响规律.结果表明:在环氧树脂分子结构中引入化学连接的PEG链段有利于提高环氧树脂链段的亲水性和应变松弛速率.增加PEGF51浓度,制备的PEGF51/F51水乳液分散相粒子粒径减小,粒度分布变窄;D230-PEGF51/F51固化产物的玻璃化转变温度和室温下的刚度和拉伸强度降低,冲击强度、断裂应变和吸水率增加.PEGF51与F51物质的量的比为1∶3时可制备出同时具有优异的拉伸强度、模量、断裂应变、冲击性能和低吸水率的D230-PEGF51/F51环氧树脂.     

双组分水性环氧树脂涂料

简述了双组分水性环氧树脂涂料的特点及其用途，分别介绍了水性环氧树脂乳液和水性环氧固化剂的制备方法、双组分水性环氧树脂涂料的分类、混合体系的固化成膜机理和适用期的判断。最后给出了对水性环氧树脂涂料进行配方设计时应考虑的因素。     

Trans-limonene dioxide,a promising bio-based epoxy monomer

Vast quantities of the natural terpene (R)-limonene can be collected from food waste. Epoxidation of its two double bonds provides limonene dioxide (LDO), a difunctional epoxy monomer. However, LDO is a mixture of four isomers, two of which (trans-LDO) are actually difunctional while the others (cis-LDO) have one epoxide group which is significantly less reactive, as revealed by Fourier transformed infrared spectroscopic analysis of formulations cross-linked with polyethylene imine. These results are also confirmed when preparing epoxy formulations using respectively cis or trans isomers. From DFT calculations, the reactivity of each epoxide group of LDO has been assessed in model reactions with primary and secondary amines, in the presence of amine or alcohol hydrogen-bond donors. The kinetics of cross-linking has also been probed by differential scanning calorimetry. As measured by dynamic mechanical analysis, the resulting epoxy resins based on trans isomers have a storage modulus of ca 1GPa at room temperature and a glass transition temperature (T_g) of 70°C. These results demonstrate that trans LDO is a promising bio-based epoxy monomer, which could be used as an alternative to petroleum-based epoxy monomers.     

Preparation and thermal properties of diglycidylether sulfone epoxy

A diglycidylether sulfone monomer (sulfone type epoxy monomer, SEP) was prepared from bis(4-hydroxyphenyl) sulfone (SDOL) and epichlorohydrin without any NaOH or KOH as basic catalyst. FT-IR, ¹H NMR, ¹³C NMR and mass spectroscopic instruments were utilized to determine the structure of the SEP monomer. The cured SEP epoxy material exhibited not only a higher T_g (163.81 °C) but also a higher T_g than pristine DGEBA (from 111.25 °C to 139.17 °C) when the SEP monomer moiety had been introduced into the DGEBA system. The thermal stability of cured epoxy herein was investigated by thermogravimetric analysis (TGA). The results demonstrated that the sulfone group of the cured SEP material decomposed at lower temperatures and formed thermally stable sulfate compounds, improving char yield and enhancing resistance against thermal oxidation. Additionally, the IPDT and char yield of the cured SEP epoxy (IPDT = 1455.75, char yield = 39.67%) exceeded those of conventional DGEBA epoxy (IPDT = 667.27, char yield = 16.25%).     

氨丙基封端聚氰丙基甲基硅氧烷改性环氧树脂——两相相溶性及表界面形态研究

本文针对聚二甲基硅氧烷改性环氧树脂相溶性太差,性能不够理想等问题,提出用氰丙基替代部分甲基以减小聚硅氧烷与环氧树脂的溶度参数差,改善两相的相溶性。采用氨丙基封端的聚氰丙基甲基硅氧烷低聚体(表1)单独或与二乙烯三胺(固化剂)一同与双酚A环氧树脂反应,合成了一系列不同聚硅氧烷分子量和重量百分比的样品(表2)。并用示差扫描量热计(DSC)、动态力学谱(DMA)、光电子能谱(XPS)、接触角仪、扫描电子显微镜(SEM)、电子拉力试验机对其进行研究。结果表明在聚硅氧烷软段中引入氰丙基可提高两相的相溶性并使增韧效果明显改善。     

Poly(dopamine) assisted epoxy functionalization of hexagonal boron nitride for enhancement of epoxy resin anticorrosion performance

Hexagonal boron nitride (h‐BN) is modified by a simple and green method based on self‐oxidation of dopamine and epoxy groups functionalized silane (KH560) grafting. The surface modification and microstructure of h‐BN are characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. The poly(dopamine) and epoxy groups not only increase the compatibility of the h‐BN and enhance its interaction with epoxy matrix but also exhibit a remarkable superiority in enhancing the anticorrosion performance of epoxy coatings. In addition, the anticorrosion mechanisms of h‐BN@PDA‐KH560 are tentatively discussed. Copyright © 2016 John Wiley & Sons, Ltd.     

FTIR法研究环氧树脂固化反应动力学

用傅里叶红外光谱（ＦＴＩＲ）法研究了双酚Ｓ环氧树脂和甲溴双酚Ａ环氧树脂分别与二胺基二苯砜在恒温条件下的固化反应动力学,得出了各反应的表观活化能。     

The synthesis and cationic polymerization of multifunctional silicon-containing epoxy monomers and oligomers

Several series of multifunctional silicon-containing epoxide monomers and oligomers have been prepared using rhodium catalyzed hydrosilation reactions. Dialkyl and diarylsilanes can be condensed with vinyl epoxides to give high yields of the desired diepoxides while the hydrosilation of alkyl and aryl silanes yields a mixture of di and tri epoxy substituted products. The condensation of αω,? Si? H difunctional compounds with vinyl epoxides can be carried out regioselectively to give α-hydrogen-ω-epoxy intermediates, which can be further reacted with di and tri olefins bearing terminal double bonds to give a series of well characterized epoxy functional oligomers. An investigation of the photoinitiated cationic polymerization of the monomers and oligomers, which were prepared during the course of these studies, was carried out. © 1994 John Wiley & Sons, Inc.     

Monte Carlo Study of Binary Copolymerizations. 2. The Determination of Reactivity Ratios,Applications

This paper discusses an improved and efficient version of the MEMØRY-7 computer program described in a previous paper. The program, called MEMØRY-7/1, implements a Monte Carlo algorithm to compute reactivity ratios in binary irreversible copolymerizations. For the copolymerization of acrylic acid and methyl acrylate, the computed r₁, r₂ values (r₁ = 1.374, r₂ = 1.038) compare quite well with experimentally determined ones (r₁ = 1.4, r₂ = 1.0; Eldridge and Treloar).     

Synthesis of novel benzoxazines containing glycidyl groups: A study of the crosslinking behavior

Benzoxazines derived from aniline and 4‐hydroxybenzoic acid and from phenol and 4‐aminobenzoic acid were prepared with two different synthetic approaches. When the carboxylic group reacted with epichlorohydrin, glycidylic derivatives M‐1 and M‐2 , respectively, were obtained. The ring opening of benzoxazine and epoxy took place simultaneously with no catalyst for both monomers. Likewise, both ring‐opening polymerizations took place when boron trifluoride monoethylamine (BF₃·MEA) or 4‐(N,N‐dimethylamino)pyridine was used as a catalyst for M‐1 . However, for M‐2 , when BF₃·MEA was used as a catalyst, the epoxy and benzoxazine ring openings could be distinguished, and a polyether intermediate containing benzoxazine side chains could be obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1529–1540, 2006