Cross-linking agents for the protection of lyocell against fibrillation: synthesis, application and technical assessment of 2,4-diacrylamidobenzenesulphonic acid

A novel, colourless, water soluble, anionic cross-linking agent, 2,4-diacrylamidobenzenesulphonic acid, has been synthesised, applied to lyocell by a pad–steam method and the wet abrasion resistance measured. The agent furnished cross-linked lyocell fibres with good wet abrasion resistance and stable lyocell–agent bonds to subsequent hot exhaust reactive dyeing conditions. Surprisingly, the fibre–agent bonds showed some instability to polyester dyeing conditions at pH 4.5 and 5.0. This is rationalised in terms of hydrolysis of the amide bond ortho to the sulphonic acid group via a neighbouring group participation mechanism.     

Functionalisation of lyocell. Part 1: Amination of lyocell with m-phenylenediaminesulphonic acid derivatives

A series of four colourless, water-soluble agents, based on m -phenylenediaminesulphonic acid, and designed to aminate lyocell, have been synthesised. Each agent carried one or two aromatic amino groups ortho to a water solubilising sulphonic acid group, together with one or two electrophilic groups. The electrophilic groups studied were dichlorotriazinyl, monochlorotriazinyl, vinylsulphonyl and triazinyl betaine. The agents were applied to lyocell by padding techniques, and neutral-exhaustion dyeing of the aminated fibres, with low, medium and high reactivity reactive dyes, in the presence of salt, were performed. Only the high reactivity dichlorotriazinyl dye gave encouraging results. The aminated fabrics, containing aromatic amino groups with an o -sulphonic acid, were insufficiently nucleophilic to allow significant covalent bonding with the low/medium reactivity dyes at both 60 and 80 °C.     

Protection of lyocell against fibrillation. Part 2: Application of 4,6-(p-β-sulphatoethylsulphonyl)anilino-1,3,5-triazin-2(1H)-one to lyocell by an exhaust process

An exhaust application method for 4,6-( p - β -sulphatoethylsulphonyl)anilino-1,3,5-triazin-2(1 H )-one to dried lyocell fibre has been developed. The procedure employs a temperature gradient technique with all of the salt and alkali present at the start. This method gives consistent wet abrasion resistance values with a standard deviation only marginally inferior to Tencel A100. Subsequent dyeing of lyocell fibres, in turn with two reactive dyes, gave build-up profiles indistinguishable from untreated fibre. The lyocell–agent bonding was stable to high temperature polyester dyeing conditions at pH 6, but unexpectedly showed some instability (as evidenced by a fall in wet abrasion resistance values) when subjected to base-catalysed reactive dyeing conditions.     

Halochromism of acrylic fibres dyed with some disperse dyes

Anomalous dyeing behaviour has been found when regular acrylic fibre treated in hydrochloric acid, in which the sulphonic acid group was present entirely in the acid form, was dyed in neutral condition with azo and anthraquinone disperse dyes. In the very early stages of dyeing there was an abnormally high degree of dye exhaustion, with bathochromic (azo) or hypsochromic (anthraquinone) colour changes on the fibre. These phenomena gradually disappeared after prolonged dyeing, with normal adsorption equilibria and colours eventually being obtained. The results were explained on the basis of protonation by the sulphonic acid groups of treated fibre which occurs at the azo nitrogen or the amino nitrogens of the substituents in the 1 — or 1,4-positions of anthraquinone. The normal adsorption equilibria after prolonged dyeing was attributed to hydrolysis of the cyano side group to form carboxylic acid. This produces ammonia to liberate neutral dye from the protonated dye cation adsorbed electrostatically by the sulphonic acid anion of the treated fibre.     

Dyeing and finishing of lyocell union fabrics: an industrial study

Lyocell union fabrics, namely lyocell/silk and lyocell/polyester fabrics, were woven in different fabric constructions and dyed with reactive dyes, acid dyes and a disperse dye. The resulting dyed fabrics were given a resin finishing treatment and their wash fastness was measured. With appropriate dye selection and control of dyeing conditions, some bright solid shades and effective cross‐dyed shades were obtained. The dyed and finished fabrics had a smooth, lustrous handle, ideal for lightweight garments.     

天成HN型活性染料涤/棉一浴一步法染色

天成HN型活性染料是一系列高温染色中性反应固着型具有季胺型吡啶甲酸基团的三嗪型活性染料,具有较高的染色牢度和良好的染色性能。本文研究了HN型活性染料用于涤/棉的一浴一步法染色工艺。工艺宽容性大,染色重现性好。     

聚酰胺/聚酯皮芯复合纤维的研究开发

聚酯纤维具有模量高、价格低廉的优点,但是存在静电和不易着色;而聚酰胺纤维具有较好的染色性、吸湿性等优点,但是模量较低且成本较高。为充分利用聚酰胺和聚酯的优点而克服因两者相容性差导致的成形问题,从原料黏弹性、挤出成形温度、热拉伸等多个方面入手,探讨提高聚酰胺/聚酯皮芯复合纺丝稳定性的技术方案。流变和纺丝试验结果表明:缩小熔体温度差,使聚酯和聚酰胺熔体黏度相近时,可制备结构稳定、性能较好的皮芯复合纤维;在拉伸温度偏向聚酯组分的拉伸温度时,聚酰胺/聚酯皮芯复合纤维的皮层和芯层组分更易做到同步拉伸;所制备的复合纤维平衡回潮率>2%,并且可以采用常规酸性染料染色,避免了常规聚酯纤维高温高压染色且因染色过程中碱减量造成的环境污染。     

The rate of hydrolysis of temporarily solubilised disperse dyes

Four temporarily solubilised disperse dyes were synthesised. To obtain the optimum application conditions for dispersant-free polyester dyeing, their conversion rates into insoluble derivatives were measured using HPLC and found to be more dependent on pH than on temperature. The results showed that it was possible to use these dyes in dispersant-free polyester dyeing for which the optimum application pH was between pH 5 and 6 at which the hydrolysis rate of the dyes was moderate.     

On the mechanism of the acid-catalysed arylation of anthraquinones

Schmidt discovered in 1925 that an unusual arylation occurred when 1,5-diamino-4,8-dihydroxyanthraquinone-3,7-disulphonic acid dissolved in conc, sulphuric acid containing boric acid was treated with phenols or anisole. Schmidt incorrectly assumed that the p-hydroxyphenyl or anisyl group replaced a sulphonic acid group. It has now been shown that this reaction is a stereospecific Friedel-Crafts type arylation, the aryl moiety entering ortho to the amino group and trans to the sulphonic acid group. The corresponding 3-monosulphonic acid undergoes the same reaction.     

活化硼氢化钠在有机合成中的应用

介绍了有机合成反应中NaBH4与添加剂共同作用的反应,其中包括烯烃和炔烃的还原,羧酸的还原,氨基酸及其衍生物的还原,羧酸酯的还原,酰胺的还原,腈基的还原,酰氯的还原,硝基化合物的还原,醛酮的还原等。与LiAIH4的还原相比较,其反应条件更温和,反应过程更安全、易操控、易放大。     

Beiträge zur Synthese von Orthocarbonsäureamiden

The formamidinium salts 11a, c as well as the nitrile 12 react with sodiumhydride/dimethylamine in the presence of trimethylborate to give the ortho formic acid amide 3a . The orthoamides 6a and 16 can be prepared from the iminium salts 15 and 14 , resp. by the same procedure. Treatment of the azavinylogous formamidinium salt 15 with sodiumhydride and piperidine or morpholine in the presence of trime‐thylborate affords the orthoamides 6c and 6d , resp. By transamination of the azavinylogous aminalester 5a are accessible the orthoamides 6b—d . The vinylogous orthocarbonic acid derivative 17 can be obtained from the salt 14 and sodium alcoholates. The action of sodiumhydride, dimethylamine and trimethylborate on the iminium salt 18 produces a mixture of the orthocarbonic acid derivatives 7a, 8a, 9a . When the guanidinium salt 20 is treated with the same reagents the ortho‐amides 3a and 10a are obtained. The reduction of the salt 20 with sodiumhydride in the presence of several activating reagents (e.g. tetrabutyl orthotitanate, aluminiumisopropylate, trimethylborate) affords the orthoamide 3a . The reduction of the iminium salts 18 and 24 does not proceed clean, giving mixtures of various orthoformic acid derivatives. The form‐amidine 25 can be prepared by reduction of the salt 15 with sodiumhydride/trimethylborate with good yields. By the action of the corresponding carbanions on the guanidinium salt 20 can be obtained the carboxylic acid orthoamides 26—33 . By the same procedure the orthoamides of alkyne carboxylic acids 36a—h, j—n are accessible.     

含羧甲磺酰基水溶性分散染料的研究

本文提出一类含有羧甲磺酰基（—SO_2CH_2COOH）的新的水溶性分散染料。利用应用时的高温,它转变为不溶性的分散染料。因此,在成品加工时不必进行砂磨,不需要扩散剂。它在弱酸、中性和碱性中都可使用,并适用于纯涤纶和涤/棉织物的印花和轧染。     

Dyeability improvement of polyester pretreated with some alkoxides

The influence of some alkoxides in alcoholic media, having various dielectric constants, on the physical and mechanical properties was thoroughly studied in a previous work to attain silk‐like polyester fibers. In this investigation, the dyeability behavior of this silk‐like polyester is tried. Both immersion and padding techniques are applied in the treatment. The dyeability of the pretreated polyester fabric with disperse dyes shows some progressive improvements with lowering the dyeing temperature and/or decreasing the time of dyeing attained. Ethoxide is found to be more effective in enhancing the dyeability of polyester fabric than either methoxide or propoxide. Dyeing of the pretreated polyester fabric at the boil without using carriers or conducting high temperature/high pressure dyeing is also possible. Washing and crocking fastness are relatively enhanced. Physicochemical investigations of the dyeing process and a mathematical analysis for evenness are given. A decrease in the half dyeing time and an increase in the rate of dyeing of the pretreated polyester as compared with the untreated one are noticed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

我国水性聚氨酯鞋用胶黏剂技术发展近况

简述鞋用胶黏剂发展历程以及我周水性聚氨酯（WPU）鞋用胶黏剂技术进展和取得的初步成果,重点介绍该胶黏剂所用原料和工艺。优选混合聚酯型多元醇、混合脂肪族型多异氰酸酯、磺酸和羧酸混合基内乳化剂为主要原料,强调应重视各类助剂的使用。采用连续法工艺,可获得高质量水性鞋用胶黏剂。     

Studies on dyeing method and dyeing properties of a sulphur black dye containing carboxylic acid groups on cotton

In this study the dyeing method of a sulphur black dye containing carboxylic acid groups on cotton was investigated. A dip–pad–bake dyeing process was applied and dyeing conditions were examined in detail. Thermal gravimetric analysis was used to determine both the baking temperature and the dehydrant selection. Fastness properties of the sulphur black dye containing carboxylic acid groups were tested. It is concluded that the sulphur black dye not only has good dyeing performance, but also possesses good fastness properties.     

Acid dyeable and printable acrylic fabrics treated with cationic aqueous polyurethane

An acid dyeable acrylic fabric has been obtained by the pretreatment with cationic aqueous polyurethane, containing different amounts of quaternary nitrogen. Cationic polyurethane has the ability to interact with the carboxylic groups in the acrylic fabrics, as well as providing basic sites suitable for acid dyeing. The prepared polyurethane has been identified with FTIR, and the effect of the pretreatment conditions on the dyeability and printability of the fabrics has been investigated. The color strength values and the fastness properties of the dyed and printed samples, reveal the ionic interaction between the sulphonic groups in the acid dye molecules and the quaternary nitrogen on the fabrics. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and properties of novel aziridinyl azo dyes from 2-aminothiophenes—Part 2: Application of some disperse dyes to polyester fibres

A series of yellow to greenish-blue aziridinyl azo dyes and their azo precursors containing a thienyl coupling moiety has been applied to conventional polyester fibre as well as microdenier polyester by high temperature exhaust dyeing. Heat transferability of these dyes onto polyester fibre has also been examined, using conventional heat-transfer printing techniques. The relevant dyeing characteristics, heat transferability, build-up, dyeability on microfibre polyester, washfastness and lightfastness are given. These aziridinyl dyes are reactive to polyester fibres under HT dyeing conditions. Fabrics dyed with aziridinyl dyes are more resistant to solvent extraction than those dyed with conventional dyes. Residual liquors showed only a pale colour when fabric dyed with aziridinyl dyes was dissolved and then precipitated, whereas a coloured polyester precipitate was obtained.     

青黛在涤纶织物上染色性能的研究

采用天然染料青黛对涤纶织物进行染色,研究了各因素对染色效果的影响.结果表明:pH值4～5,温度120～130℃,时间30分钟,染色效果最好.载体可实现青黛对涤纶在100℃下的低温染色.青黛对涤纶染色后具有较高的水洗牢度和摩擦牢度.     

原液着色环保聚酯纤维的开发

筛选了耐高温、色牢度优良的环保染料,将环保染料与溶剂、分散剂、润湿剂调配成原液着色的液态色浆,构建了一种耐高温、色牢度优良、能够稳定分散、环保、操作简便的染色体系,并以此开发了原液着色纤维。制成的原液着色纤维具有颜色均匀、色牢度高、色彩饱满、耐水洗、抗摩擦的效果,兼具成本低、绿色环保的特点。     

Determining the effect of enzymatic pretreatment on the low temperature dyeability of polyamide fabrics

In this study, by pretreating polyamide 6/elastane knitted fabrics with serine-type protease enzyme, the aim was to reduce dyeing temperatures. It is known that the elasticity of elastane fibres is damaged in dyeing at high temperatures. On the other hand, to enable efficient dyeing, it is necessary to use boiling temperatures in synthetic fibres such as polyamide, or even mild high temperature conditions, to support more uniform dyeing. Protease enzymes are enzymes that hydrolyse amide bonds, and consequently, new amine and carboxyl groups are released in fibre macromolecules, resulting in an increase in the functional group content to which anionic dyes can bind. In this study, to compensate for the loss of colour yield caused by lowering the dyeing temperature, an increase in the functional groups was provided by enzymatic pretreatment. For this purpose, the fabrics were pretreated with a commercial serine-type protease enzyme then dyed with 1:2 metal complex dyes at different temperatures. The effects of enzymatic pretreatment on colour, fastness, fibre surface characteristics and fabric strength were investigated.