4，4’-（4，4’-砜基二苯氧基）二苯甲酰氯（SODBC）的合成

以对甲基苯酚、4,4’-二氯二苯砜为原料，通过亲核取代反应合成了4，4’-二（4-甲基苯氧基）二苯砜，用高锰酸钾将甲基氧化得到4，4’-（4，4’-砜基二苯氧基）二苯甲酸（SoDBA），后者在二氯亚砜和路易斯碱的催化下合成了4，4’-（4，4’-砜基二苯氧基）二苯甲酰氯（SoDBC）白色固体。用FT-IR、H—NMR、3C—NMR、DSC等对其进行了表征，实验证明该化合物具有预期的结构和较高的纯度。     

舒巴坦氧化新工艺研究

研究了一种合成舒巴坦前体二溴代青霉烷砜酸的新工艺。该工艺以双氧水/三氟乙酸作为氧化体系，收率达到92%以上。随后用锌粉将二溴代青霉烷砜酸还原得到舒巴坦，总收率为74%(三步反应),质量满足药用标准。与传统的KMnO₄氧化法相比，该方法具有安全性高，后处理简单和环境友好的特点。     

4-氨基-3′-羟乙基砜基苯甲酰苯胺的合成

研究了对硝基苯甲酰氯和３－（β－羟乙基砜）苯胺合成４－氨基－３′－羟乙基砜基苯甲酰苯胺的工艺,探讨了温度、投料比、酰化反应时间、还原电解质等对产量及品质的影响,通过正交试验得到了最佳的合成条件。提出了用高效液相色谱检验产品纯度的条件。     

4—氨基—3′—羟乙基砜基苯甲酰苯胺的合成

研究了对硝基苯甲酰氯和３－（β－羟乙基砜）苯胺合成４－氨基－３′－羟基基砜基苯甲酰苯胺的工艺,探讨了温度、投料比、酰化反应时间、还原电解质等对产量及品质的影响,通过正交试验得到了最佳的合成条件。提出了用高效液相色谱检验产品纯度的条件。     

硫醚氧化为亚砜和砜的研究进展

亚砜和砜是两类重要的化合物,在化学和生物领域有广泛的应用。虽然有很多方法合成亚砜和砜,但通过控制硫醚的化学选择性氧化是合成亚砜和砜的常用途径之一;常见氧化剂如空气/氧气、双氧水、单过硫酸氢钾复合盐（Oxone）、高碘酸钠等均可以实现硫醚的选择性氧化。本文依据氧化剂的种类对氧化反应进行分类,综述了近年来硫醚氧化制备亚砜和砜的研究进展。     

如何解决环丁砜的变色问题

阐述了用特丁基邻苯二酚代替对苯二酚合成环丁烯砜的较佳工艺条件。试验表明:用特丁基邻苯二酚作阻聚剂合成环丁烯砜,基本上解决了环丁砜贮存过程中的变色问题,提高了产品质量,降低了成本。     

聚乙二醇催化合成二苄砜

聚乙二醇催化合成二苄砜杨建文，俞善信（湖南师范大学化学系，长沙４１００８１）二苄砜为重要的有机合成中间体［１－４］。已在制药，高分子合成及精细化工品制造等方面发挥作用。据报道，二苄砜可作为一种非常有效的细菌生长抑制剂。其传统的合成方法是先由卤代烃与硫...     

对双端炔基四苯醚砜试剂合成的改进

用Marvel的方法合成双端β-氯烯醛四苯醚砜(简称I_b)时生成大量的,不易回收的季铵盐混合液。合成双端炔基四苯醚砜(简称I)时,DMF溶剂的用量较大,有一定毒性。回收时损失25％以上,产品价格难免偏高,废液污染较严重,推广应用受到限制。针对以上问题,在合成反应过程中,对试剂和溶剂的用量,作了认真的考查。用红外、核磁等对产品进行了分析验证。在保证产品质量的情况下,达到了降低成本、提高经济效益的目的。     

4,4′-(4,4′-砜基二苯氧基)二苯甲酰氯(SODBC)的合成

以对甲基苯酚、4,4′-二氯二苯砜为原料,通过亲核取代反应合成了4,4′-二(4-甲基苯氧基)二苯砜,用高锰酸钾将甲基氧化得到4,4′-(4,4′-砜基二苯氧基)二苯甲酸(SODBA),后者在二氯亚砜和路易斯碱的催化下合成了4,4′-(4,4′-砜基二苯氧基)二苯甲酰氯(SODBC)白色固体.用FT-IR、1H-NMR、13C-NMR、DSC等对其进行了表征,实验证明该化合物具有预期的结构和较高的纯度.     

气-液氧化制备2-硝基-4-甲砜基苯甲酸工艺的研究

以2-硝基-4-甲砜基甲苯为原料,应用空气-硝酸联合氧化法合成出2-硝基-4-甲砜基苯甲酸,研究了物料配比、反应温度、反应时间、硝酸的滴加速率、空气的加入速率等工艺参数对合成产品收率的影响,获得了较佳的合成工艺参数。放大实验结果表明,在最佳工艺条件下产品收率达到85%,纯度达到97.1%。     

铬酸铬渣生产铬鞣剂过程除铁技术研究进展

铬鞣剂被认为是目前制造轻革的重要材料,以铬酸铬渣为原料生产铬鞣剂是低成本的生产方法之一,但是以含铁的铬酸铬渣作原料生产铬鞣剂会影响铬鞣剂产品的质量。详细介绍了有机络合法、萃取法等在铬鞣剂生产中除铁的应用,从反应原理、工艺流程和除铁效果等几个方面对各种方法进行了对比,评价使用不同生产方法的技术优劣,并对低含铁铬鞣剂的应用前景做了展望。     

美黑沙龙渐成熟点

介绍了美黑作为一种新的流行理念被越来越多的年轻人所接受。分析了室内美黑床引起的皮肤疾病问题，而这一问题在日益加重。指出规范美黑行业势在必行。     

四羟甲基氯化膦无铬鞣的机理

Tetra-hydroxymethyl phosphonium chloride （THPC） has been considered as an important chrome-free tanning agent. To understand the THPC tanning mechanism, the structure, charge distribution, activity and tanning ability of each phosphorous compound in THPC tanning system were studied, by ^31p NMR, FT-IR spectroscopy, differential scanning calorimetry （DSC） and computational chemistry method, etc. When pH raised to 6.0, the decomposition of THPC would take place, which results in a production of free formaldehyde, tri-hydroxymethyl phosphonium （TrHP） and tri-hydroxymethyl phosphine oxide （TrHPO）. At pH 9.0, THPC will be converted completely to TrHP and most TrHP is further oxidized into TrHPO. It is possible that, in reaction of phosphorous compounds and collagens, both P-C and C-O bonds would break simultaneously or individually. From molecular charge distribution and bond polar properties, it is deduced that, if P-C bonds break, the activity is in order of TrHPO 〉 THPC 〉 TrHE whereas if C--O bonds break, the order is TrHP 〉 THPC 〉 TrHPO. It is more possible that P--C bonds will break in reaction with collagen, and TrHPO may be more active in the THPC tanning system. The results of tanning and DSC also prove the above conclusion. Furthermore, the fact that the shrinkage temperature of THPC tanned leather was below 70℃ when basified to pH 5.0 or lower suggests that the hydroxymethyl groups of THPC and TrHP are less possible to combine directly with amino groups of collagen.     

逆转铬鞣工艺技术的研究进展

消除铬排放是制革工业持续发展迫切需要解决的关键科技问题。采用现有制革技术,铬鞣及其之后的所有水相操作工序都会排放铬,还会产生含铬皮革固体废物,这使得完全消除制革过程的铬排放几乎不可能实现。针对这一问题,本文介绍了以消除铬排放为目标的逆转铬鞣工艺技术。较系统地综述了该技术中的无铬预鞣单元、染整单元、末端铬鞣单元及含铬废水处理等单元过程的研究进展,分析了尚存在的问题和未来的研发方向。提出以“无铬预鞣单元-染整单元-末端铬鞣单元”为核心,通过对制革单元过程实施重组和耦合优化来构建逆转铬鞣工艺技术,可在保证成革品质的同时大幅削减了含铬污染物的产生,并使铬的完全回收和处理变得简单易行,为彻底解决制革工业的铬排放问题提供了参考。     

Influence of ultrasound on Avaram bark (Cassia auriculata) tannin extraction and tanning

Efficient processing methodologies such as ultrasounds which would achieve significant enhancements in processes thereby minimizing sectional stream wastes in one hand and bring about economic benefits on other are necessary. Hence, research studies on application of ultrasound in process industries such as leather, textiles and chemicals are gaining importance. In this regard, a case study has been presented in this paper for solid–liquid tanning extraction and tanning from a plant material. For this purpose, Avaram bark (Cassia auriculata) which contains ingredients such as polyphenolics, useful in stabilization of collagen, which is the main constituent of skins/hides. Avaram bark tannin come under the group of ‘condensed tannins’ useful in main tanning process of leather making. The influence of various process parameters such as ultrasonic power, time and agitation on extraction has been studied. The results show significant 1.6-fold improvement for total extract due to the use of ultrasound, 100 W as compared to magnetic stirring control process, suggesting better mass transfer enhancement in leaching of strongly bound tannins from avaram bark due to ultrasound. Efficacy of tannin extract (10% or 20% offer) has been analyzed through application in tanning process and found to be useful. There has been significant improvement in rate of tannin uptake for ultrasonic extract as compared to control extract by the bovine pelt, suggesting diffusion enhancement of tanning agent through the pelt matrix. Use of ultrasound in avaram extract tanning has also been studied and found to be useful. Therefore, the present study clearly indicates the use of ultrasound in Avaram bark tannin extraction and tanning as a viable option with added advantages even dispensing with external heating.     

皮革废水处理实例

皮革加工废水存在排水量大,水质水量不均,污染物成分复杂的特点。毛皮在鞣制、染色过程中产生的废水不仅含COD,BOD,悬浮物等常见污染物,亦包含大量蛋白质,脂肪,硫化物,氯化物,三价铬盐,此外还有大量细小绒毛;这给皮革废水的处理带来极大难度。文章介绍的实例项目将含铬的复鞣废水与其它废水分开预处理,复鞣废水除铬处理后汇合至综合废水;综合废水经前处理+两级生化处理后达标排放到市政污水管网。     

用高浓度含铬废液制备铬鞣剂

本文论述了利用化工厂高浓度含铬废液制备铬鞣剂,阐述了制备铬鞣剂的工艺过程,调制方法,本工艺所产铬粉主要用于皮革的初鞣。     

Hide tanning with modified natural tannins

Tannin from “Acacia Mearnsii” usually called Mimosa, is largely employed in vegetal tanning of hide even if the quality of the leather is poorer than that obtained using chromium as tanning agents. However, taking into account the natural resources of this product and its reduced environmental impact, mimosa tannin has been modified to obtain leather having improved properties. Tannin was modified using formaldehyde, urea, a sulfonic acid and a sulfiting agent: The new products show a higher molecular weight than mimosa tannin but maintain a good solubility in water. Modified tannins were characterized through physicochemical and technological tests and evaluated as tanning agents. The properties of tanned leathers obtained using the new tannin products and mimosa were compared. Some of the polymers containing phenolsulfonic acid are good tannin agents, especially those with a suitable molecular weight. The technological and sensorial properties of the leather obtained using modified tannins (distension and strength of grain, tensile strength, elongation, and tear load) are better than those obtained using mimosa when an appropriate ratio of the reagents were employed. At the same time the feeling of the tanned leather was improved and the final products show fullness, elasticity, fluency, reactivity, and a thin and fine grain. Some of the tannins modified with naphtalensulfonic acid show poor tanning properties but good penetration in the leather suggesting their use as auxiliary sintans in the pretanning process. A simple procedure to prepare these modified tanning agents in the course of the tannin extraction is suggested. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

HRP/H_2O_2引发制备酚类共聚物及其鞣制性能的研究

对羟基苯甲酸(PHBA)和对羟基苯磺酸(PHSA)在辣根过氧化酶(HRP)/H2O2的引发下进行自由基共聚反应制备酚类共聚物〔poly(PHBA-co-PHSA)〕,考察了酚类单体配比和HRP用量对共聚物鞣制性能的影响,用FTIR、NMR、UV和GPC对酚类共聚物的分子结构进行了表征。结果表明,所得酚类共聚物具有较好的鞣制性能,鞣制后的皮革收缩温度(Ts)达到了78.6℃,复鞣皮革柔软丰满,与铬鞣剂配合使用可减少铬鞣剂用量60%左右,Ts达到了98.63℃。     

制革工业关键清洁技术的研究进展

应用制革清洁技术能够从制革生产的源头削减/消除污染。COD_Cr、氨氮和总铬是制革工业的典型污染物,研发和推广应用其源头减排技术对制革工业实现清洁生产具有重要意义。本文较系统地综述了保毛脱毛技术、鞣前过程废液循环利用技术、无氨脱灰技术、无氨软化技术、高吸收铬鞣技术、铬鞣废液循环利用技术、逆转铬鞣技术和无铬鞣制技术等清洁技术的研究进展及实际应用情况。介绍了这些技术的应用方法和重要控制参数,以及这些技术对源头减少典型污染物的作用。同时,对已有清洁技术的优点和尚存在的问题进行了分析。指出进一步提高单元清洁技术的成熟度和经济实用性,加强单元清洁技术之间的工艺平衡研究,重视单元清洁技术的集成链接,是制革工业清洁技术的未来发展方向。