无钴干燥系统的发展过程外文文献翻译、中英文翻译

附录一外文译文无钴干燥系统的发展过程Johan H.bielemanSasol Servo BV ,the Netherlands摘要在空气干燥机用于干燥涂层系统，以催化聚合的过程，其中钴羧酸是使用最广泛的干燥剂。然而，化合物钴很可能是在美国国家毒理学计划中研究的致癌因素，例如硫酸亚铁钴。因此，德国已不再给含钴油漆授予蓝色天使奖。其他过渡金属羧酸如锰或铁基很低的催化效果表明，钴不能平等作为自氧化聚合反应的催化剂。干涂料的实验调查的各种有机螯合配体对自氧化过程中的锰催化性能的影响。锰的活动受有机配体的强烈影响。 新锰基于无钴，显示良好的干燥性能和改进的颜色保留干涂料的配位化合物。1简介空气干燥醇酸涂料包含除了主要成分、 醇酸、 色素和溶剂少量的干燥剂。 在干燥加快的漆膜，在自氧化的不饱和脂肪酸含量存在的醇酸树脂成分作为基于氧化交联过程。烘干机，也指在解决方案中，防水剂添加剂是有机物溶剂和粘合剂中可溶性有机金属化合物。化学，属于金属皂类的干燥和它们添加到吹干涂料系统，以加速或促进后应用固体阶段在一个适当的时间内从液膜转化。 转换发生的的联编程序系统一个的过程将金属阳离子的阴离子的干燥机、催化氧化交联作为承运人联编程序系统中的一部分。钴数十年来一直活动主要的干燥机使用中干涂料。但是最近的研究与七水合钴硫酸事务局疗效为钴化合物会遵守重新分类程序。继最近公布委托指令 2001 年/59/Ecof 欧洲共同体。 氧化物分类使用以下风险提示：R 22/R 43/R 50/R 53。相关的钴烘干机烘干机没有更改还，因为它是尚不清楚如果像七水合钴硫酸，水溶性化合物毒性数据作为找到的钴的分类。干燥机制造商已启动几个测试程序以收集数据的生物利用度钴，用作涂料。还是一个干燥机、无钴替代方案以取代钴烘干机的压力。在某些情况下含钴成分不会获得批准获得环境奖项，如德国蓝色天使奖。2干燥过程及干燥影响醇酸漆的干燥过程是缓慢蒸发中挥发性的结果，在第二个步骤中化学干燥会发生。醇酸树脂的氧化交联过程发生的 H-原子中的自由基反应从亚油酸的双亚甲组提取的葡萄酒，结果基采取了大气氧和从过氧化物。在过氧化物与钴催化剂降低到烷氧基和过氧自由基。 这些自由基窗体交联的重组过程称为自氧化交联过程(图 2)。图 1“自氧化”反应方程式显然自氧化一词已被定义为一个无催化氧化反应的过程。图 2在自氧化交联过程中醇酸树脂的反应变化但是，自氧化反应发生重大率仅在面前的一种催化剂，如过渡金属提涂料的干燥、自氧化过程通过添加烘干机的加速。没有这些干燥的催化剂漆层可能要几个月后才能完成干燥。更详细化学干燥氧化法可以通过结合在一起的四个步骤来表示:l 步骤 1： 诱导期l 步骤 2：过氧化物形成l 步骤 3: 过氧化物分解自由基l 步骤 4: 聚合从这种涂料应用直到电影开始吸收空气中的氧的时间测量诱导步骤。吸收的氧窗体过氧化物跨联编程序(步骤 2) 中的共轭双键。当该过氧化物开始分解时，就形成了交联站点。交联在聚合过程中随着粘度迅速增加。第 2 和第 4 步最有效地进行树脂含共轭的双键 ；但是，非共轭树脂显示还有些反应。在这种情况下多个的双键可能会导致激活的各种亚甲组重新排列位置的非共轭双键、取决于双键的原始位置。步骤 1 和 2 使干燥的速度大大提高。由于他们对氧化还原反应的敏感性的氧进行作为干燥机系统中的金属。烘干机也激活的过氧化物形成；假定是多价金属是以双键，增加氧化易感性的关联。钴干燥机的增加减少了能源所需使一个不饱和树脂氧吸收激活。活性氧渗透倾向于过氧化物的形成。不久，过氧化被形成及其烷氧基催化反应中的分解(图 3)图 3自氧化交联过程中的反应基于长油醇酸树脂的环境照顾装饰涂料的干燥系统通常使用一个钴/锆/钙组合干燥机。钴是活性干燥剂, 但是，为了改善通过干燥、硬度和稳定性，锆和钙的辅助干燥中正在使用钴结合。钴烘干机的潜在替代产品的基本特征。基本上，干燥机金属可分为两个组：活动烘干机和辅助干燥。这种差异应视为任意它们之间不存在大量的重叠。在环境温度氧摄取、过氧化形成和过氧化分解推广活动烘干机。辅助烘干机不显示催化自己在周围的温度下，但提高活动的干燥机金属的活动。原发性干燥机性能报告了各种过渡金属。 但是，仅锰找到了大量的实际使用。没有该替代烘干机-为金属羧酸-类似于中钴的性能。但是，反应以及对颜色相同的过渡金属的影响等属性与主要是有关化学成分的复合金属。由于自由金属阳离子并不存在于解决方案，这是可以理解的。金属离子始终围绕阴离子、溶剂分子或其他配体组。纯羧酸的大多是数商业烘干机。但是，对于某些应用程序锰基于强螯合配体与组成如找到了商业使用、配体将扮演重要的角色的这种化合物催化氧化干燥。强螯合配体对催化活性通过改变电子密度的复杂的离子等金属中心及其潜在的氧化还原。下一节将对干燥机的各种锰的成分，使用有机配体。3实验性3.1 过程和使用的材料对涂料的各种干燥的影响已被计算，使用不同干等体系的涂料。在指定为标准漆的长油油漆组成如表 1 所示。干燥剂被添加到下阶段。这两个商用油漆无干燥机由这次测试的厂商提供，以及准备进行系统新鲜色漆和清漆用漆基已被使用。干燥性能已确定根据 ASTM 或使用干燥的录像机的类似过程。下面的过程使用了：1干燥的录音机。干燥条件：23/50 相对湿度。使用的仪器是直线的录像机。后干燥阶段被考虑。阶段 a：涂料流一起、 湿边缘时间。阶段 b：一条线是可见，油漆开始聚合：无尘。阶段 c：使翻录电影：以自由或表面干。阶段 d：表面路径： 通过干或总干。2干燥进一步成立的拇指测试，并根据 ASTM D1640。电影的 Konig 硬度被评估通过钟摆阻尼测试根据 DIN53157。一个玻璃面板是涂有 60 湿膜，在 23，相对湿度 50，硬度条件下保持发展的时间与一科尼格摆监测。振荡时间的测量，以减少从最初的 6 3 是在几秒钟内给出偏转。钴-锆-钙干燥机组合已作为参考，使用金属比率后，除非另有说明。0.06 Co 0.3zr 0.1Ca这种组合是基于对 10 钴，锆，钙 18 10 商用级别的混合物。这两个商业，以及金属配合物作为实验已被使用。详情将载于表和数字。3.2 结论和讨论3.2.1 钴与锰干燥机在下面的表 1 中显示演示与干燥机在白宫漆，制定根据这种标准的漆，表 1 中的锰钴催化作用直接比较。表 1在白色醇酸树脂漆中 Mn 与 Co 效果活泼的干燥剂辅助干燥剂无尘 ( 小时)无轨 ( 小时)总共干燥 时间白度指数硬度(s/k)0.08Co0.4zr0.2Ca1.302.003.3078520.08Mn0.4zr0.2Ca7.159.4515.157329钴与锰在同一金属剂量对干燥机干燥性能有不利影响，白度和硬度。显然 不宜以改变。出于实际应用的 7 个小时以上的无尘时间将导致尘埃粒子附着在干燥涂层。此外，长期粘性，无干燥时间的增加，总的赔偿风险增加。3.2.2 锰-联吡啶配合物锰配合物已被报告为有效干涸。锰化合物和螯合剂的化合物得到了广泛的商业应用，在聚氨酯清漆醇酸树脂的实例，以及在水性醇酸树脂漆。这些锰的化合物，而不是钴催干剂使制定的浅色聚氨酯醇酸清漆。最近，锰的复杂活动特殊性已被确定，作者对 Mn-bipy 复杂的结构，提出了投影图 4。图 4Mn-biby 的结构在钴催干剂与聚氨酯配合使用清晰的深色清漆醇酸树脂和光的原因是缺乏吸引力。以 Mn - hipy 色彩，而不是在相当大的改进合作的结果。这种改善只是在液体清漆可见; 没有在硬化涂层的差异已被发现。相对于锰羧酸在干燥速度显着改善可以看到(见表 2)。该锰hipy 复杂也适用于水性涂料的基础上的短油醇酸树脂乳液。这两种树脂体系，聚氨酯醇酸树脂和短油醇酸树脂乳液，有共同的物理干燥是非常重要的，而交联的膜的形成和硬度的贡献是相当低，而对劳醇酸树脂为基础的系统。表 2Mn-bipy 在含有基醇酸聚氨酯的家具中的影响活泼的干燥剂辅助干燥剂总共干燥时间(小时)固体漆0.06Co0.3Zr0.1Ca2.00150.06Mn0.3Zr0.1Ca5.3060.03Mn-bipy0.3Zr0.1Ca1.306干燥速度使用锰 hipy 已记录在色素漆的基础上，聚氨酯醇酸树脂(见表 3)相似的积极影响。然而，Mn-hipy 有负面影响的白度。表 3在白色醇酸树脂漆中 Mn-bipy 在聚氨酯醇酸树脂中的影响效果活泼的干燥剂辅助干燥剂总共干燥时间(小时)白度0.06Co0.3Zr0.1Ca4.45790.06Mn0.3Zr0.1Ca9.30770.03Mn-bipy0.3Zr0.1Ca4.1573此外，比较数据已被记录在一个标准的白色油漆，醇酸树脂的基础上 (见表 4)。尽管在干燥时间可以看到同样的改善，但整体表现仍然不足，需要进一步改善。像在聚氨酯醇酸树脂漆，一个复杂的联吡啶上的白度产生负面影响已经确定，也是在劳醇酸油漆。此外，漆膜仍太软。表 4在白色醇酸树脂漆中 Mn-bipy 在罗醇氨树脂中的影响效果活泼的干燥剂辅助干燥剂无尘(小时)无轨(小时)总共干燥时间白度指数硬度(s/k)0.08Co0.3Zr0.1Ca2.002.304.4580360.08Mn0.3Zr0.1Ca10.0013.0015.1578290.03Mn-bipy0.3Zr0.1Ca5.007.0010.007221显然，锰催化效率提高利用联吡啶配体。但是，进一步的改善是必要的，以便能够使用和锰，钴，而不是基于干燥器。3.2.3 锰-聚配体复合物配体与配体成分变化大评估。联吡啶是一种典型的强场配体，形成稳定的复合物与锰。在干燥特性的进一以步改善将达到使用两个或两个以上配体组成：通常是强场配体和一个弱场配体。下一步改善干燥特性的另一个优点是使用混合配体储存稳定性的改善，低粘度，使高浓度达到少雨成分，而在复杂的金属浓度为 6锰。下面的测试结果证明了“聚配型锰配合物”的“锰小巴指出”起生效。对干燥，硬度以及颜色速度是积极的影响使用聚配体为基础，而不是仅仅联吡啶锰(表 5)表 5在白色醇酸树脂漆中 Mn-Plb 在聚氨酯醇酸树脂中的影响效果活泼的干燥剂辅助干燥剂无尘(小时)无轨(小时)总共干燥时间白 度 指数硬度(s/k)0.06Co0.3Zr0.1Ca2.002.304.4580360.06Mn0.3Zr0.1Ca10.0013.0015.1578290.03Mn-bipy0.3Zr0.1Ca5.007.0010.0076210.03Mn-blp0.3Zr0.1Ca4.205.458.007724醇酸树脂涂料在罗湖干燥仍稍逊使用锰，钴。进一步改善完成修改树脂组成;利用介质油醇酸或劳混合醇酸树脂和醇酸树脂莫。在密苏里州的干燥特性醇酸树脂涂料是为锰，钴作为干燥器乘客联络小组(表中 的提法比较 6 和 7)。利用与锰乘客联络小组一起辅助干燥器作用是有限的使用剂量不能保证在评估这些醇酸树脂涂料莫。因此，在干燥催化剂总额可能减少 2.4至 0.3(表 6)。表 6白漆在中期油基醇酸干燥机中活跃的干燥剂固体中活跃的干燥剂干燥原料成本指数Sb=2 9.7%总共干燥时间3 月后在 23 的干燥时间硬度(s/k)W-ICo-Zr-Ca1.2%Co0.0751001.864.3076380Mn-plg6%Mn0.04600.40565781.5表 7半光泽黑色漆的基础上，连锁停止中等油醇酸树脂干燥机中活跃的干燥 剂固体中活跃的干燥剂干燥原料成本指数Sb=29.7%总共干燥时间3 月后在23 的干燥时 间硬度(s/k)Co-Zr-Ca1.2%Co0.091002.7844106Mn-plg6%Mn0.091061.11961134. 结论有机配合物的前途在于提供锰钴催化剂作为替代的功能。在测试的配方，新锰聚配体干燥介质提供了类似的石油总干醇酸树脂涂料的特点，而不会造成液体或固化涂料的不利影响。新的干燥性能优于传统的锰对干燥器。附录二外文原文Progress in the Development of Cobalt-free Drier SystemsJohan H.bielemanSasol Servo BV ,the NetherlandsSummaryDriers are used in air-drying coating systems to catalyze the polymerization process. cobalt-carboxylates are the most widely used driers . However , cobalt cornpounds may indirectly be implicated as carcinogen suspects as aresult of studies in the U.S.A , in the national toxicology program using cobalt sulphate heptahydrate . Hence , Germany is no longer granting the Blue Angel award to cobalt-containing paints . Other transition metal carboxylates such as based on manganese or iron show much lower catalytic effects and cannot equalize cobalt as a catalyst in autoxidation polymerization reactions . The effect of various organic chelating ligands on the catalytic properties of manganese in autoxidation processes was investigated experimentally in air-drying paints . The activity of manganese is strongly effected by organic ligands . New manganese based coordination compounds enable the formulation of co-free air-drying paints , which show good drying performances and improved color retention .1 IntroductionAir drying alkyd paints contain besides the main constituents , alkyd resins(binders) , pigment and solvents small amounts of driers . The driers speed up the oxidative cross- linking process of a paint film , based on the autoxidation of the unsaturated fatty acids , which are present as constituents of alkyd resins .Driers , also referred to as siccatives when in solution , are organo-metallic compounds soluble in organic solvents and binders . Chemically , driers belong to the class of metal soaps and they are added to air-drying coating systems to accelerate or promote after application the transformation from the liquid film into the solid stage within an appropriate time . The transformation occurs by oxidative cross-linking of the binder system , a process , which is catalysed by the metallic cation of the drier .The anionic part of the drier molecule serves as the carrier , to solubilize the drier in the binder system .For deCADes cobalt has been the main active drier used in air-drying paints . However as the result of recent studies with cobalt sulphate heptahydrate , cobalt compounds are subject to reclassification procedures . Following the recently published commissionDirective 2001/59/Ecof the European Community . Cobalt oxide is classified using following risk phrases : R 22/R 43/R 50/R 53 . The classification for cobalt driers have not been changed yet , as it is still unclear if the toxicity data as found for water soluble compounds like Cobalt sulphate heptahydrate , are relevant for cobalt driers .Drier manufacturers have initiated several test-procedures in order to collect data for the bioavailability of cobalt , used as a drier in paints .Nevertheless , the pressure to replace cobalt driers with cobalt-free alternatives is growing . In some case cobalt-containing compositions will not be granted for environment awards ,like for the Blue Angel Germany .2 The drying process and the effect of driersThe drying process of alkyd paint is the result of the slow evaporation of the volatile compoments and in a second step chemical drying takes place . The oxidative cross-linking process of alkyd resins occurs vin a radical reaction in which H-atoms are abstracted from the double methylene group of linoleic acid . The resulting radicals take up atmospheric oxygen and from hydroperoxides . The hydroperoxides degrade with cobalt catalyst into alkoxy and peroxy radicals . These radicals form cross-links by recombination . This process is known as “the autoxidation cross-link process” (figure 2) .Apparently the term “ autoxidation ” has been defined as an non-catalyzed oxidation reaction of a substrate exposed to the oxygen of the air .Figure 1.General reactions for “autoxidation ” reactions .Figure 2.Schematic presenation of the autoxidation cross-linking process of alkyd resinsHowever , autoxidation reactions occur at significant rates only in presence of a catalysts , such as a transition metal ref . 1 , 3 , 4 .The autoxidation process referring to the drying of paints is accelerated by addition of driers . Without these drying catalysts the paint layer may dry only after some months ; with driers this is accomplished within a few hours .More in a detail , chemical drying by oxidation can be through as a combination of four steps :l Step 1 : Induction periodl Step 2 : Peroxide formationl Step 3 : Peroxide decomposition into free radicalsl Step 4 : PolymerizationThe induction step is measured from the time the coating is applied until the film begins to absorb oxygen from the air . The absorbed oxygen forms peroxides across the conjugated double bonds in the binder (Step 2) .When the peroxides start to decompose , active cross-linking sites are formed . As crosslinking proceeds during the polymerisation , the viscosity increases rapidly .Step 2 and 4 proceed most effectively with resins containing conjugated double bonds ; however , non-conjugated but poly-unsaturated resins show also some reactivity . In such a case the multiple double bonds may cause the activation of the various methylene groups , to rearrange the position of the non- conjugated double bonds , depending on the original position of the double bonds .The step 1 and 2 are accelerated dramatically by the presence of driers .The mutivalent metals in the drier system act as oxygen carries because of their susceptibility to redox reactions . Driers also activate the formation of peroxides ; assumed is the multivalent metal is associated to the double bonds , increasing the oxidation susceptibility . The addition of cobalt drier reduces the energy , which is necessary for the activation of the oxygen absorption by an unsaturated resin , with a factor 10 ref . 1 , 5 .The penetration of activated oxygen into the film favors the peroxide formation . As soon as peroxide are formed their decomposition in a metal-catalysed reaction to alkoxy (RO ) and peroxy radicals (ROO ) takes palace (figure 3) .Figure 3 . Reactions during the autoxidation cross-linking processDrier systems for ambient cared decorative paints based on long oil alkyd resins are usually siccativated using a cobalt / zirconium / calcium combination drier . Cobalt is the active drier . However , in order to improve through-drying , hardness and stability , auxiliary driers , like zirconium and calcium , are being used in conjunction with cobalt .General characteristics of potential alternatives to cobalt driers .Essentially , drier metals can be divided into two groups : active driers and auxiliary driers . This difference should be considered arbitary as a considerable amount of overlap exists between them .Active driers promote at ambient temperatures oxygen uptake ,peroxide formation and peroxide decomposition .Auxiliary driers do not show catalytic themselves at ambient temperatures , but enhance the activity of the active drier metals .Next to cobalt ,various transition metals have been reported as having primary drier properties . However , only manganese has found substantial practical use .None of the alternative driers-as metal carboxylates-resemble in performance to cobalt . The limitations of the alternatives in relation to the application in paints are summarized as follows :However , the reactivity as well as properties like effect on colour of the same transition metal are largely related to the chemical composition of the metal compound ref . 6 . This is understandable as “ free metallic cations ” do not exist in solution . The metal ions are always surrounded by anions , by solvent molecules or by other ligand groups .Most commercial driers are pure carboxylates . However , for some applications manganese based compositions with strong chelating ligands such as bipyridine have found commercial use .The ligand plays an important role in the catalytic oxidative drying of these compounds (ref . 7) . Strongly chelating ligands effect the catalytic reactivity by altering the electron density at the metallic center of a complex ion and so its redox potential .Next section will be addressed to the performance as a drier various manganese based compositions , using organic ligands .3 Experimental3.1 Procedure and used materialsThe effect of various driers on the drying of paints has been evaluated , using different air-drying paint systems . The composition of the long-oil paint , designated as standard paint , is shown in table 1 . The drier is added to the paint during the let-down stage .As paint systems both commercially available paints , supplied by the manufacturer for this test without drier , as well as prepared “ fresh paints and varnishes ” have been used .The drying performance was determined according to ASTM or similar procedures , using a drying recorder .Following procedures have been used :1: the drying recorder . Drying condition : 23/50 relative humidity . The used instrument is a straight-line recorder . Following drying stage are being considered :Stage a the paint flows together , the wet-edge time .Stage b a line is visible , the paint begins to polymerize : dust-free . Stage c ripped film : take-free or surface-dry .Stage d surface path : through dry or total dry .2: the drying was further established by the “ thumb-test ” and according to ASTM D1640 .The Konig hardness of the films was assessed by using the pendulum damping testaccording to DIN53157 . A glass panel was coated with a 60mm wet film ,kept underconditions of 23 and 50% RH and the hardness development in time was monitored with a Konig pendulum . The oscillation time measured to reduce the deflection from initial 6to 3is given in seconds .A cobalt-zirconium-calcium drier combination has been used as reference , using following metal ratio , unless otherwise indicated .0.06 Co 0.3zr 0.1CaThis combination is based on a mixture of commercially available grades of Co 10 , Zr 18 and Ca 10 .Both commercial as well as experimental metal complexes have been used . Details will be presented in the tables and figures .3.2 Results and discussion3.2.1 Co vs Mn drierA direct comparison demonstrating the catalytic effect of Co versus Mn drier in a white house paint , formulated according to the standard paint according to table 1 is shown in following table 1 .Replacing Co drier with Mn drier at same metal dosage has a detrimental effect on the drying performance , whiteness and hardness .Obviously Mn is unsuitable to replace Co drier .For practical application a dust-free time of over 7 hours will result in adhesion of dust particles in the dried coating . Moreover , the long tack-free and total dry time increase the risk of damages to the paint film and the appearance .3.2.2 Manganese-bipyridine complexesManganese complexes have been reported as effective dries ref . 6 . Compounds of Mn and chelating compounds , like 1 , 10-phenantroline and bipyridine , have found widespread commercial application , for instance in urethane alkyd varnishes as well as in waterborne alkyd paints . The application of these manganese compounds instead of cobalt driers enables the formulation of light colored urethane alkyd varnishes .Recently the active speciesc of the Mn-bipy complex has been determined as beingMn4O2 (2ethylhexanoate)6 (bipy)2 ref . 7 .A projection of the structure of the Mn-hipy complex is presented in figure 4 .Figure 4 . StructureMn-hipy complex .The use of Co driers in conjunction with clear urethane alkyd resins in dark colored varnishes and are for optical reasons less attractive . Using Mn-hipy instead of Co results in considerable improvement in color . This improvement is just visible in the liquid varnish ; noDifferences in the hardened coating have been found . Compared to the Mn carboxylate remarkable improvement in drying speed can be noticed (table 2 ) . The Mn-hipy complex is also applicable in waterborne coating , based on short-oil alkyd emulsions .Both resin systems , urethane alkyd and short-oil alkyd emulsions , have in common that the physical drying being very important and the