磺酸型水性聚氨酯的合成及改性研究进展

介绍了磺酸型水性聚氨酯(SWPU)的合成方法及其最新的研究进展,重点从磺酸基团的引入方式上进行了分类介绍。同时简单介绍了对有机硅、有机氟、环氧树脂改性SWPU的研究进展情况,并对SWPU的发展方向做了展望。     

磺酸盐型水性聚氨酯的研究进展

介绍了磺酸盐型水性聚氨酯(SWPU)的主要特点,综述了近年来其合成及改性的研究进展,并对SWPU未来的发展方向进行了展望。     

DHPA扩链剂合成磺酸型水性聚氨酯的性能研究

合成了一种新型磺酸型扩链剂1,2-二羟基-3-丙磺酸钠(DHPA),并通过红外光谱法证明了其化学结构。利用这种扩链剂与异佛尔酮二异氰酸酯、聚醚多元醇等反应,制备出固含量高、热稳定性好和力学性能好的磺酸型水性聚氨酯(SWPU)乳液及薄膜。与同时合成的羧酸型水性聚氨酯(CWPU)对比发现,SWPU乳液的固体质量分数可达50%以上,而CWPU乳液固体质量分数不超过40%;SWPU乳液的粒径比CWPU小,粒径分布窄;SWPU薄膜具有更好的热稳定性和弹性模量;SWPU薄膜耐溶剂性比CWPU薄膜好,但耐水性比CWPU薄膜差。     

新型液态磺酸型扩链剂及其水性聚氨酯的合成与表征

合成了一种新型液态磺酸型扩链剂1,2-二羟基-3-丙磺酸(DHPS),通过红外光谱、质谱等方法证明了其化学结构,并用其与异佛尔酮二异氰酸酯(IPDI)、聚醚多元醇及不同成盐剂反应制备了磺酸型水性聚氨酯(SWPU),并对乳液进行了表征。结果表明,所制得的SWPU乳液的粒径较小,平均粒径约25~30 nm,粒径分布窄;SWPU乳液的临界固含量Sη均较高,其中Na OH成盐的SWPU的Sη高达63%。     

4,4-二氨基二苯乙烯-2,2-二磺酸改性水性聚氨酯的制备及性能研究

以异佛尔酮二异氰酸酯（IPDI）及聚己内酯二元醇（PCL1000）为主要原料,二羟甲基丙酸（DMPA）为亲水扩链剂,制得一系列水性聚氨酯预聚体。利用4,4-二氨基二苯乙烯-2,2-二磺酸（DSD酸）作为扩链剂进行改性,得到荧光水性聚氨酯（SWPU）。采用FTIR、DLS、XRD、UV-vis、荧光光谱、力学性能、热重分析等手段对聚氨酯进行了结构表征与性能测试。FT-IR、DLS分析表明,4,4-二氨基二苯乙烯-2,2-二磺酸（DSD酸）已引入到聚氨酯分子链中,随着DSD酸质量分数的增加,乳液粒径先减小后增大,当w（DSD酸）%=2%时,SWPU乳液的平均粒径适中(72.80 nm)。XRD、UV-vis、荧光光谱结果表明,SWPU具有明显结晶性;SWPU具有一定的紫外吸收且发生了红移;SWPU发出较强的蓝色荧光且发生浓度猝灭。与WPU相比,SWPU的力学性能及热稳定性明显提高,当w（DSD酸）%=3%时,最大拉伸强度为48.43 Mpa,断裂伸长率为366.42%;最大分解温度由301.48 ℃提高到328.05 ℃。     

4,4'-二氨基二苯乙烯-2,2'-二磺酸改性水性聚氨酯的制备及性能

以异佛尔酮二异氰酸酯(IPDI)及聚己内酯二元醇(PCL1000)为主要原料,二羟甲基丙酸(DMPA)为亲水扩链剂,制得了一系列水性聚氨酯预聚体。利用4,4'-二氨基二苯乙烯-2,2'-二磺酸(DSD酸)作为扩链剂进行改性,得到荧光水性聚氨酯(SWPU)。采用FTIR、DLS、XRD、UV-Vis、荧光光谱、力学性能分析、热重分析对荧光聚氨酯进行了结构表征与性能测试。FTIR、DLS分析表明:DSD酸已引入到聚氨酯分子链中,随着DSD酸质量分数的增加,乳液粒径先减小后增大,当DSD酸质量分数为2%时,制备的SWPU2乳液粒径最小(44.61nm)。XRD、UV-Vis、荧光光谱结果表明:SWPU有紫外吸收且发生了红移,发出较强的蓝紫色荧光并发生浓度猝灭。与WPU相比,SWPU的力学性能及热稳定性明显提高,SWPU2荧光强度最强为434568.94 a.u.,胶膜的最大拉伸强度为48.43 MPa,断裂伸长率为389.40%;最大分解温度也由301.48℃提高到328.05℃。     

用于高得率浆纸张增白的二苯乙烯型水性聚氨酯荧光乳液的合成及其性能

为了改善二苯乙烯型荧光增白剂的光异构现象及在高得率浆纸表面的吸附性，以三聚氯氰为交联单体，将4,4'-二氨基二苯乙烯-2,2'-二磺酸、乙醇胺和对氨基苯磺酸依次引入同一个分子中制得荧光单体（SFBs），进一步将其作为扩链剂制备了二苯乙烯型水性聚氨酯荧光(SWPU)乳液。采用¹H NMR、FTIR、UV-vis、荧光光谱、乳液粒径分析仪和稳定性分析仪等对所制备的荧光单体和乳液的结构和性能进行表征，最后其SWPU乳液用于高得率（杨木化机浆APMP）纸张表面施胶，通过紫外光加速老化试验对比了空白纸样和经SWPU乳液涂布后纸样的白度值，通过抗张强度检测、纸样吸水性Cobb值检测对比纸样的物理性能变化。结果发现，制备的二苯乙烯型水性聚氨酯荧光乳液粒径分布窄，平均粒径为66.78nm，乳液稳定性良好，经SWPU乳液涂布后的纸样初始白度比空白纸样增加了15.6%(ISO)；经48h光老化处理，空白纸样白度降低了17.56%(ISO)，而涂布纸样的白度只降低了13.39%(ISO)；另外，涂布后纸样的抗张强度增大，Cobb值减小；说明制得的SWPU乳液在高得率浆纸表面有良好的吸附性，并具有一定的增白、抑制纸张返黄和提高纸张物理强度效果。     

可控交联度的大豆油基水性聚氨酯的制备与研究

以丙烯酸(AA)作为开环试剂,与环氧大豆油(ESO)反应制备可控羟基数的多元醇(AESO),再与聚醚二醇(PPG)、异氰酸酯(IPDI)、亲水单体二羟甲基丙酸(DMPA)、扩链剂三羟甲基丙烷(TMP)和中和剂三乙醇胺(TEA)等原料,制备出性能良好的大豆油基水性聚氨酯乳液(SWPU)。通过傅里叶变换红外分析、热重分析和机械测试研究了涂膜的结构和物理性能,研究了AESO和PPG相对含量的变化对SWPU的黏度和稳定性以及涂膜的耐水性、热稳定性及力学性能的影响。结果表明:成功地以AESO改性水性聚氨酯,得到的SWPU乳液具有较好的稳定性,涂膜耐水性得到改善,且具有较好的热稳定性,拉伸强度得到提高,断裂伸长率有所下降。     

一种磺酸型水性聚氨酯扩链剂的合成、表征及应用

以自制的中间体N,N-二(2-羟乙基)-2-氨基丙烯为原料,对其进行磺化反应,控制温度、时间和摩尔比反应合成磺酸型水性聚氨酯扩链剂N,N-二(2-羟乙基)-2-氨基丙磺酸钠,借助核磁氢谱(¹H NMR)、红外光谱(FTIR)、元素分析、X射线衍射(XRD)等手段对合成产物进行了组成、结构和结晶性表征,用热重分析仪表征了产物的热稳定性。根据产物的磺化度确定最佳的合成工艺:反应温度为90℃,反应时间为8 h,N,N-二(2-羟乙基)-2-氨基丙烯和亚硫酸氢钠(NaHSO₃)的物料比为1:2.5,磺化率可达到94%以上。分别以二羟甲基丙酸(DMPA)和自制磺酸型单体作为亲水扩链剂制备羧酸型水性聚氨酯(CWPU)和磺酸型水性聚氨酯(SWPU),其性能对比结果表明:SWPU相比于CWPU具有较好的亲水性和耐热性能;固含量及稳定性方面,SWPU也是优于CWPU的。     

含硫扩链剂改性水性聚氨酯的制备及其性能

以2-巯基乙醇(2-ME)和丙烯酸羟乙酯(HEA)为原料,通过巯基-烯"点击"反应合成了含硫二元醇ME-HEA。并以其为扩链剂,与聚氧化丙烯二醇(PPG)、异佛尔酮二异氰酸酯(IPDI)等合成系列含硫水性聚氨酯(SWPU)。采用纳米粒度仪、红外光谱仪、电子拉力机等对乳液的粒径、胶膜的热性能、力学性能以及耐水性进行了分析。结果表明:随着ME-HEA质量分数的增加,SWPU胶膜的耐热性能和力学性能有明显的提升。当ME-HEA质量分数为4.3%时,乳液粒径为41.7 nm,胶膜拉伸强度和断裂伸长率分别为34.3 MPa和911.2%,在120℃热氧降解处理后的拉伸强度为处理前的拉伸强度的90.09%,有较好的耐热氧降解性能。     

Preparation and surface-active properties of the sodium soaps,mono- and diethanolamides and diol and triol sulfates of cycloaliphatic C21 Di- and C22 Tricarboxylic acids

Cycloaliphatic C₂₁ di- and C₂₂ tricarboxylic acids were prepared by the Diels-Alder reaction of dehydrated castor oil (DCO) fatty acids (containing 48% conjugated and 42% nonconjugated dienes) with acrylic and fumaric acids, respectively. The reaction temperature, time, catalyst concentration, and mole ratio of reactants were varied to get maximum yields of the di- and tricarboxylic acids. The unreacted DCO fatty acids were removed from the products by partition between aqueous methanol and n-hexane. The products were converted to methyl esters and characterized as the substituted cyclohexene derivatives before and after dehydrogenation with Pd/C in xylene, hydrogenation with Pd/C in decalin and oxidation with periodate-permanganate reagent and by mass and proton nuclear magnetic resonance spectrometry. The acids were converted to sodium soaps, mono- and diethanolamides and the corresponding diol and triol sulfates, and the resulting products were evaluated for their surface-active properties. The sodium soaps showed better calcium tolerance and poorer foaming power than sodium oleate. The diethanolamides were inferior to lauroyl diethanolamide in wetting and emulsifying power. The monoethanolamides were better than the respective diethanolamides and lauroyl diethanolamide in wetting property. The diol and triol sulfates were poorer in wetting and emulsifying ability and better in calcium tolerance than sodium lauryl sulfate.     

民用工业中复合材料桁架的应用和发展

本文叙述了复合材料桁架的构造、分类和计算方法,突出了复合材料桁架的优越性能和在民用工业中的应用前景;在分析大量文献资料的基础上阐述复合材料桁架杆件的多种加工工艺,并比较不同截面形式对杆件性能的影响;探讨复合材料杆件的破坏机理和分析方法,介绍节点的类型和各自的特点,提出节点及连接部位存在的关键问题;根据国内外复合材料桁架的研究和应用现状,阐述了复合材料桁架的性能和不同的设计方法,总结归纳影响复合材料桁架性能的关键因素和设计中存在的一些问题,并提出改进杆件设计、节点设计和优化复合材料桁架的建议。     

熟料岩相试样制作方法及典型岩相特征的形成原因

熟料的岩相分析有助于熟料质量的判断及生产过程控制调整。根据多年实践经验,总结了手工和机械磨制岩相试样的方法及注意事项,并对几种熟料岩相特征(孔洞、游离氧化钙、A矿包裹B矿和f-Ca O、晶体尺寸不均和矿巢)进行了举例和形成原因分析。     

Effects of Extraction Temperature and Preservation Method on Functionality of Soy Protein

The effects of extraction temperature and preservation method on the functional properties of soy protein isolate (SPI) were determined. Four extraction temperatures (25, 40, 60, and 80 °C) were used to produce SPI and yields of solids and protein contents were determined. Three preservation methods were also tested (spray-drying, freeze-drying, and freezing–thawing) and compared to fresh (undried) samples for each extraction temperature. No differences in yields of solids and protein were observed among SPIs extracted at 25, 40, and 60 °C; however, SPI extracted at 80 °C yielded significantly less solids and protein. Extraction temperature significantly affected SPI functionality. As extraction temperature increased, solubility and emulsification capacity decreased; surface hydrophobicities, emulsification activities and stabilities, and dynamic viscosities increased; and foaming properties improved. Preservation method also significantly affected SPI functionality. Drying method did not affect the denaturation enthalpies of SPIs, but spray-dried SPIs had higher solubilities, surface hydrophobicities, and emulsification stabilities, and lower viscosities, emulsification activities and rates of foaming than freeze-dried SPI exhibited. Emulsification and foaming capacities and foaming stabilities were similar for both methods of drying. There was significant interaction between extraction temperature and preservation method for all functional properties except emulsification capacity.     

Enzymes-Assisted Extraction of Plants for Sustainable and Functional Applications

The scientific community and industrial companies have discovered significant enzyme applications to plant material. This rise imparts to changing consumers’ demands while searching for ‘clean label’ food products, boosting the immune system, uprising resistance to bacterial and fungal diseases, and climate change challenges. First, enzymes were used for enhancing production yield with mild and not hazardous applications. However, enzyme specificity, activity, plant origin and characteristics, ratio, and extraction conditions differ depending on the goal. As a result, researchers have gained interest in enzymes’ ability to cleave specific bonds of macroelements and release bioactive compounds by enhancing value and creating novel derivatives in plant extracts. The extract is enriched with reducing sugars, phenolic content, and peptides by disrupting lignocellulose and releasing compounds from the cell wall and cytosolic. Nonetheless, depolymerizing carbohydrates and using specific enzymes form and release various saccharides lengths. The latest studies show that oligosaccharides released and formed by enzymes have a high potential to be slowly digestible starches (SDS) and possibly be labeled as prebiotics. Additionally, they excel in new technological, organoleptic, and physicochemical properties. Released novel derivatives and phenolic compounds have a significant role in human and animal health and gut-microbiota interactions, affecting many metabolic pathways. The latest studies have contributed to enzyme-modified extracts and products used for functional, fermented products development and sustainable processes: in particular, nanocellulose, nanocrystals, nanoparticles green synthesis with drug delivery, wound healing, and antimicrobial properties. Even so, enzymes’ incorporation into processes has limitations and is regulated by national and international levels.     

Self-Assembly of Diamondoid Molecules and Derivatives (MD Simulations and DFT Calculations)

We report self-assembly and phase transition behavior of lower diamondoid molecules and their primary derivatives using molecular dynamics (MD) simulation and density functional theory (DFT) calculations. Two lower diamondoids (adamantane and diamantane), three adamantane derivatives (amantadine, memantine and rimantadine) and two artificial molecules (ADM•Na and DIM•Na) are studied separately in 125-molecule simulation systems. We performed DFT calculations to optimize their molecular geometries and obtained atomic electronic charges for the corresponding MD simulation, by which we predicted self-assembly structures and simulation trajectories for the seven different diamondoids and derivatives. Our radial distribution function and structure factor studies showed clear phase transitions and self-assemblies for the seven diamondoids and derivatives.     

Role of Douglas fir (Pseudotsuga menziesii) carbohydrates in resistance to budworm (Choristoneura occidentalis)

The current year's growth of Douglas fir contains galactose, unusual in that this carbohydrate makes up 78.7% of the total carbohydrate fraction. An agar diet study was undertaken to determine the effects of galactose, other carbohydrates, and terpenes on western spruce budworm larval mortality, growth rate, and adult biomas production. All concentrations of the carbohydrates and terpenes tested, as well as other mineral elements not tested, were typical of the current year's foliage of Douglas fir. In experiment I, the diet containing 5.61% total carbohydrate did not significantly affect larval mortality when compared to the control diet. However, diets containing 9.45% and 15% total carbohydrate concentrations significantly increased larval mortality 64% and 96.1%, respectively, when compared to the control. Also in experiment I, terpenes alone (78.9% morality) and terpenes in combination with 9.45% and 15% total carbohydrates significantly increased larval mortality (97.2% and 100%, respectively) when compared to mortality on the control diet (44%). To determine which carbohydrate was causing the adverse effect, 6% glucose, 6% fructose, and 6% galactose were placed individually and in combination with terpenes in diets in experiment II. The 6% galactose diet significantly increased larval mortality and reduced growth rate when compared to the control, glucose, and fructose diets. Glucose resulted in 16% less larval mortality, significantly enhanced female larval growth rate and pupal weight, but did not affect male larval growth rate and pupal weight, when compared to the control. Fructose resulted in a significant decrease in larval mortality and a general trend of enhanced female and male larval growth rate and pupal weight. Larval mortality on terpenes alone was not significantly different from the control, but terpenes with 6% galactose increased larval mortality and decreased female and male growth rate and pupal weight significantly when compared to glucose-terpene and fructose-terpene diets. No significant interactions were found between carbohydrates and terpenes in either experiment.     

COMBINED INNOVATIVE HEAT PUMP DRYING TECHNOLOGIES AND NEW COLD EXTRUSION TECHNIQUES FOR PRODUCTION OF INSTANT FOODS

There is an increased demand for convenient foods including ready-to-eat and instant products. These products are desired with minimum concentration of synthetic chemicals. This creates challenges for the food industry and dryers manufactures to develop new technologies to process difficult-sensitive materials and to supply final products with high quality and improved properties. Fruits and vegetables are mainly composed of water, carbohydrates, proteins and lipids. Due to modification of chemical and physical bonds the compounds the material becomes viscous and sticky during processing. Conventional dryers have limitations in handling such sensitive materials. Heat pump dryers have been applied in the production of a diversity of ready-to-eat foods and dried instant products for the last five years at SINTEF-NTNU. Besides being energetically efficient and environmentally friendly, the heat pump drying technology provides a wide range of drying conditions as required to produce powders with improved characteristics. This work describes the new technologies and processing line for the production of instant foods as well as the measurements on the properties and quality attributes for raw, intermediate and final instant products.     

Environment and colour: The technological interface

Technology and colour are viewed as interfaces between the environment, humans and human activity. Examples are provided of ways of facilitating and improving access to and use of colours by commercial users of colour coatings through improvements in the accuracy of measuring and displaying colour. By analogy, the task of providing effective interfaces within the coatings industry, between the coatings industry and the environment and between the coatings industry and the public and political domain are discussed. Examples of information shortfalls are cited to illustrate how distortions arise. Examples of more effective, integrated technological, organisational and political interfacing are culled from the author's experiences.     

毒死蜱、联苯菊酯在室内和室外土壤中的消解动态及土壤化学屏障研究

[目的]探讨毒死蜱和联苯菊酯在室内外土壤中的消解动态,并预测2种农药作为土壤化学屏障防治白蚁的有效期。[方法]采用气相色谱法测定不同时期土壤中毒死蜱和联苯菊酯的残留量并采用土壤穿透法测定2种农药在土壤中的生物活性。[结果]毒死蜱在室内和室外的半衰期分别为51.3、39.5 d,联苯菊酯在室内和室外的半衰期分别为31.3、44.5 d。毒死蜱和联苯菊酯抗白蚁穿透的最低有效质量分数分别为6.15、5.78 mg/kg,并结合消解动态方程预测出毒死蜱和联苯菊酯作为土壤化学屏障中有效成分的有效期在室内分别为195、29.1 d,在室外则分别为158.4、56.1 d。[结论]得到的白蚁防治有效期结果较好,为白蚁的化学防治提供理论依据。