CN1122066C - 新缩合产物及其应用 - Google Patents

新缩合产物及其应用 Download PDF

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CN1122066C
CN1122066C CN97199711A CN97199711A CN1122066C CN 1122066 C CN1122066 C CN 1122066C CN 97199711 A CN97199711 A CN 97199711A CN 97199711 A CN97199711 A CN 97199711A CN 1122066 C CN1122066 C CN 1122066C
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J·赫勒
A·S·廷德尔
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Clariant Finance BVI Ltd
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Abstract

由多官能胺与氨基氰、其衍生物或聚合物在氨基磺酸存在下的反应所获得的新型水溶性缩聚产物。它们是优异的固色剂,能够改进在纤维素纤维材料、纸张、纸板和无纺织物上具有直接染料的染色物的牢度性能。

Description

新缩合产物及其应用
本发明涉及由多官能胺与氨基氰或其衍生物和聚合物的反应制备的水溶性缩聚产物。
此类反应产物以及它们在改进用直接染料而得到的染色物的牢度上的用途是很早就已知的。DE-A-855 001描述通过在不存在水的情况下加热多官能胺与氨基氰或聚合物或其衍生物,任选在非水溶剂存在下,在除氨状态下反应所获得的缩聚物。根据EP-A-0 431 423,这些产物因其生产方法的原因而含有水不溶性副产物,这一缺点能够在不存在或存在非水溶剂下,优选在有含羟基的和沸点高于180℃的溶剂存在下,让多官能胺与氨基氰或其衍生物或聚合物在铵盐如氯化铵、硫酸铵、碳酸铵、甲酸铵或乙酸铵存在下进行缩合来克服。根据EP-A-0 692 511,该方法的理想改进包括让多官能胺与铵盐在非水溶剂存在下反应,然后加热用氨基氰组分获得的质子化产物;这一实施方案改进了该方法的安全性。
JP-A-60 252 787描述了用于纤维素纤维染色材料的湿牢度增效剂,它包括具有6个或6个以上碳原子的脂族二胺,优选1,6-己二胺或2,2,4-三甲基六亚甲基二胺或其与无机酸或有机酸(例如甲酸、乙酸和氨基磺酸),优选盐酸的盐类,与胍化合物或其盐,优选双氰胺,胍的盐酸盐或胍的硫酸盐的缩聚反应的产物。所得到的缩聚产物据说与从其它二胺获得的类似产物相比,具有改进的牢度性质。
现已发现,如果胺类与氨基氰、其衍生物或聚合物的反应是在每摩尔氨基氰组分0.1~0.7mol的氨基磺酸或其盐存在下进行的话,则能够获得具有优异性能的水溶性缩合产物。
所以,本发明涉及由
组分a)具有通式(I)的胺
其中
A是任选地***杂原子的亚烷基链,和
R1-R4独立地选自氢,任选被OH、CN或C1-C4烷氧基取代的烷基,前提条件是R1-R4中至少一个是氢,
组分b)氨基氰、其衍生物或聚合物,按a∶b=2∶1-1∶2,优选1∶1-1∶1.5的摩尔比,在
组分c)每摩尔b0.1-0.7mol氨基磺酸或其盐存在下,在80-180℃、优选130-160℃的温度下进行反应所得到的水溶性碱性缩聚产物,以及通过用染色技术中常用的无机或有机酸中和所获得的其水溶性盐类。
具有通式(I)的优选胺是满足以下条件的那些:
A是任选被O、S、NH或N-C1-C4烷基***或被OH取代的C2-C20亚烷基链,和
R1-R4独立地是氢或C1-C4烷基,前提条件是R1-R4中至少一个是氢。
合适的多官能胺a的例子是1,4-丁二胺,1,6-己二胺,N-(2-氨基乙基)-1,3-丙二胺,二亚丙基三胺,N,N-双-(2-氨基丙基)-甲基胺,聚乙烯亚胺,和优选多亚乙基多胺如三亚乙基四胺,四亚乙基五胺,五亚乙基六胺和最优选二亚乙基三胺。
合适的组分b是氨基氰,双氰胺,胍和双胍。双氰胺是优选的。
组分c优选是氨基磺酸或其盐类。
组分a与组分b的反应是按2∶1-1∶2,优选1∶1-1∶1.5的摩尔比,在0.1-0.7摩尔氨基磺酸存在下,在80-180℃、优选130-160℃的温度下,在一种使氨被分离出来的熔化状态下进行的。根据这一方法的一个可能变化形式,路易斯酸例如氯化锌可用作催化剂。
还有可能使用合适的溶剂,优选含有羟基且沸点高于180℃的溶剂,以在缩合过程中改进混合物的搅拌性能。一般来说,缩合反应一直氨气或在获得所需粘度之后停止。当在铁质反应器中进行缩合反应时,为了抵消铁离子的影响,建议添加适量的膦酸多价螯合剂。
反应产物是具有碱性的高粘性液体或固体,它能够溶于水中以提供一种透明溶液。优选地,反应产物通过用染色技术中常用的无机或有机酸中和而转变成水溶性盐。优选的酸是硫酸,盐酸和乙酸。
根据本发明的碱性缩聚产物或它们的盐类可用于已用直接染料或活性染料染色或印染的含羟基或氨基的材料的纺织纤维的预处理或后处理。此类纺织纤维也能够由天然和合成纤维的混纺物,例如纤维素和聚酯、聚丙烯腈、聚酰胺或羊毛的混纺物组成。此类纤维用碱性缩聚产物的预处理将会改进它们的可染色性能并使染色物更具尽染性,后处理会改进染色物和印染物的湿牢度,更具体地说是指耐汗、耐水和耐洗涤牢度。
碱性缩聚产物或其盐也可用于纸张、纸板和无纺织物上阴离子染料的固色剂。用此类固色剂的处理将导致染料在纤维或基材上的更好保留率,获得更高的得色量和更透明的回水(backwater)。还有,此类染色物的渗色牢度(bleedfastness)优异于未被固色的染色物的牢度性能。与现有技术的固色剂相比,根据本发明的固色剂的优点是染色物有更亮的色调(对染色物的色调更少影响)和更好的耐光牢度(对这一参数更少的负面影响)。
根据本发明的固色剂,在涂敷到纸张上时,也用于改进用阴离子和阳离子染料(例如阳离子直接染料)着色的两面性(two-sidedness),和改进其中使用回用的粗原料或存在大量填料或细填料的阳离子直接染料的得色量。
为了用根据本发明的固色剂处理基材,该基材用碱性缩聚产物,或优选用其与无机或有机酸的盐的水溶液进行处理。缩聚产物或其盐的量能够在较宽的范围内变化。一般来说,0.1-4wt%、优选0.5-3wt%(基于基材的重量)的量适合获得所需效果。
这一处理是通过将纺织纤维在染色工艺之前或之后浸泡到含有碱性缩聚产物或优选其与无机或有机酸的盐类的水处理浴中。已染色或印染的纤维材料为改进湿牢度的这种处理典型地是在尽染方法中进行的,因此材料需要在含有碱性缩聚产物且PH值例如为4-8、优选5.5-6.5的水浴中在20-70℃的温度下放置20-30分钟。替代地,后处理是以连续方式进行,即由常规方式用轧染施用水浴并进行固色。
如果纸张、纸板或无纺织物用碱性缩聚产物处理,该处理是通过在基材的染色完成之前或之后的几分钟添加固色剂来进行的,一般在继续进行造纸工艺之前在室温下短时间充分搅拌混合物就足够了。
由根据本发明的固色剂处理加以改进的染色物所使用的合适染料是指在《染料索引》(Colour Index),第三版(1971)年,第2卷,第2005-2478页中描述的直接染料和在第1001-1562页中描述的酸性染料。合适的活性染料描述在Venkataraman,《合成染料化学》,第VI卷,活性染料(Academic Press,纽约,伦敦1972年)。
在下面的实施例中份数是重量份数。
实施例1
在750ml的反应器中,将126份双氰胺,103份二亚乙基三胺和48.5份氨基磺酸投入到100份二甘醇中,混合物在氮气气氛的惰性环境下被制备。在良好搅拌2.5小时后,将混合物加热至150℃,之后在150℃下进一步搅拌2.5小时,直至获得粘稠的蜂蜜状物质,从中馏出40份的氨气为止。在混合物被冷却至135℃之后,添加200份的冰,碱性产物用24份硫酸中和。
实施例2
在750ml的反应器中,将92.4份双氰胺,103份二亚乙基三胺和97份氨基磺酸投入到150份二甘醇中。在搅拌下经2.5小时后,将混合物加热至160℃,之后在160℃下进一步搅拌4小时,在此过程中馏出34份氨气。在将混合物冷却至135℃之后,添加65份冰,碱性产物用16份盐酸(36%)中和。
实施例3
在750ml的反应器中,将105份双氰胺,103份二亚乙基三胺和12.1份氨基磺酸投入到100份二甘醇中。在搅拌下经2.5小时后,将混合物加热至160℃,之后在160℃下进一步搅拌30分钟,在此过程中馏出36份的氨气。在混合物被冷却至135℃之后,添加190份的冰,碱性产物用46份硫酸中和。
实施例4
在750ml的反应器中,将92.4份双氰胺,103份二亚乙基三胺,48.5份氨基磺酸和1.4份氯化锌投入到100份二甘醇中。在搅拌下经2.5小时后,将混合物加热至150℃,之后在150℃下进一步搅拌2.5小时,在此过程中馏出38份的氨气。在混合物被冷却至135℃之后,添加150份的冰,碱性产物用28份硫酸中和。
实施例5
在750ml的反应器中,将105份双氰胺,103份二亚乙基三胺和24.2份氨基磺酸投入到150份二甘醇中。经3小时将混合物加热至150℃,之后在150℃下进一步搅拌5小时,在此过程中馏出40份氨气。在将混合物冷却至135℃之后,添加150份冰,碱性产物用31份冰醋酸中和。
实施例6
使用与前面实施例中相同的方法,将105份双氰胺,103份二亚乙基三胺和48.5份氨基磺酸投入到200份二甘醇中。经2小时将混合物加热至150℃,之后在150℃下进一步搅拌7小时,在此过程中馏出40份氨气。在将混合物冷却至120℃之后,混合物用300份水稀释,碱性产物用18份冰醋酸中和。
应用实施例
实施例A
100份棉料用1.35wt%染料C.I.直接黄162(商品形式)对应于1/1标准深度来染色。在染色和漂洗过程之后,棉纤维立即在997份软水中含有3份根据实施例1的产物的处理浴中在40℃下处理20分钟。在移走处理浴之后,棉纤维用新鲜水漂洗一次。获得具有优异湿牢度(耐洗涤和耐水牢度)的黄色染色物。用根据实施例2-6的产物和用下表的用于棉或再生纤维素的染料获得类似结果。以wt%表示的量在所有情况下对应于1/1标准深度。
                  表
染料 以wt%计的量
对于棉料 对于粘胶纤维
直接黄162 1.35 1.40
直接红83∶1 1.75 2.35
Optisal红R SGR 1.40 1.60
直接红227 2.70 1.95
直接紫66 1.30 0.80
直接蓝71 1.00 0.90
直接蓝77 1.35 1.30
直接蓝85 1.30 1.20
直接蓝90 1.60 1.55
直接蓝251 1.25 1.15
沙拉品蓝3RL 2.65 2.45
直接棕240 1.50 2.55
直接黑118 2.20 2.05
实施例B
根据实施例A的染色物的后处理也能够按以下进行:
将干燥过的基材浸泡在实施例1-6的产物的40g/L的水溶液中,挤压掉液体获得80%的轧液率(pick-up),然后基材在120℃下干燥。获得具有优异湿牢度(耐洗涤和耐水牢度)的染色物。
实施例C
制备由以下
     50%漂白软木
     50%漂白硬木组成的配料(造纸纤维的贮料悬浮液),2.5%稠度和20度Schopper-Riegler的游离度(ISO5267/1)。
在恒定搅拌下向这一纤维悬浮液中,以根据所需要的最终色泽深度,例如1/2标准深度的一种浓度添加典型阴离子染料的溶液(在这种情况下色度指数直接黄148∶1)。在5分钟后添加实施例1的固色剂。添加量取决于针对渗色牢度性质、得色量和回水清晰度所要求的最终结果。在这种情况下相对于纤维添加3wt%。在进一步搅拌1分钟后,染色纤维悬浮液被稀释至1%的稠度。使用典型方法从这一悬浮液生产纸张片材,在这种情况下使用手工模具,但机械片材成型器也是同样地好(ISO5269/l或ISO5269/2)。
然后将片材放置在滤纸上,然后在10吨压力(每平方米)在两毡片之间加压2分钟。然后取出纸张并在90℃扁平板式干燥器中干燥10分钟。收集来自染色物的回水并与未固色染色物的回水进行比较。纸张色调和深度与用同样染料和传统固色剂(Cartafix F液体)制备的另一片材进行比较。发现,用该新型化学品制备的片材的色彩要亮丽得多,而且牢度更好。还发现,与未固色染色物对比,渗色牢度性能得到改进,而回水比未固色染色物的更透明。测量以上所述参数的典型方法是:
     渗色牢度测量方法   EN646:1994
     回水级别           EN20105-A03:1992
     耐光性:           EN 20105-B02:1992
     色差:             BS6923:1988
用根据实施例2-6的产物获得类似的结果。

Claims (12)

1、碱性缩聚产物,它是由
组分a)具有通式(I)的胺
其中
A是亚烷基链,和
R1-R4独立地选自氢,任选被OH、CN或C1-C4烷氧基取代的烷基,前提条件是R1-R4中至少一个是氢,
组分b)氨基氰、其衍生物或聚合物,按a∶b=2∶1-1∶2的摩尔比,在
组分c)每摩尔b0.1-0.7mol氨基磺酸或其盐存在下,在80-180℃的温度下进行反应而得到的,以及用染色技术中常用的无机或有机酸中和所获得的其水溶性盐类。
2、根据权利要求1的缩聚产物,其特征在于A是***杂原子的亚烷基链。
3、根据权利要求1的缩聚产物,其特征在于a∶b的摩尔比是1∶1-1∶1.15。
4、根据权利要求1的缩聚产物,其特征在于具有通式(I)的胺用作组分a,其中
A是C2-C20亚烷基链,和
R1-R4独立地是氢或C1-C4烷基,前提条件是R1-R4中至少一个是氢。
5、根据权利要求4的缩聚产物,其特征在于A是被O、S、NH或N-C1-C4烷基***或被OH取代的C2-C20亚烷基链。
6、根据权利要求1的缩聚产物,其特征在于二亚乙基三胺用作组分a。
7、根据权利要求1的缩聚产物,其特征在于双氰胺用作组分b。
8、根据权利要求1的缩聚产物,其特征在于氨基磺酸用作组分c。
9、根据权利要求1的通过在130-160℃的温度和/或在沸点高于180℃的含有羟基的溶剂存在下的反应获得的缩聚产物。
10、根据权利要求1的缩聚产物作为添加剂在染色过程中的用途。
11、根据权利要求1的缩聚产物作为供在纤维素纤维材料上使用直接染料而得到的染色物用的预处理剂或固色剂的用途。
12、根据权利要求1的缩聚产物作为供在纸张、纸板和无纺织物上使用直接染料而得到的染色物用的固色剂的用途。
CN97199711A 1996-11-15 1997-11-13 新缩合产物及其应用 Expired - Fee Related CN1122066C (zh)

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DE10202767A1 (de) * 2002-01-25 2003-08-07 Cht R Beitlich Gmbh Verfahren zur Herstellung von Textilhilfsmittel und deren Verwendung
CN101962442B (zh) * 2009-07-21 2013-03-27 铜陵高聚生物科技有限公司 一种盐酸聚六亚甲基双胍的制备方法
CN105178103A (zh) * 2015-08-13 2015-12-23 合肥龙发包装有限公司 一种碱性染色助剂

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JPS60252787A (ja) * 1984-05-29 1985-12-13 三洋化成工業株式会社 湿潤堅牢度増進剤
US4764585A (en) * 1984-07-21 1988-08-16 Sandoz Ltd. Cationic polycondensates useful for improving the fastness of dyeings on textiles
EP0431423A2 (de) * 1989-12-07 1991-06-12 Bayer Ag Basische Polykondensationsprodukte sowie deren Verwendung als Färbereihilfsmittel
EP0692511A1 (de) * 1994-07-12 1996-01-17 Ciba-Geigy Ag Verfahren zur Herstellung eines Färbereihilfsmittels

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US4439203A (en) * 1981-05-14 1984-03-27 Sandoz Ltd. Process for improving the wetfastness of dyeings, printings and optical brightenings on cellulosic substrates and compositions useful therefor
JPS60252787A (ja) * 1984-05-29 1985-12-13 三洋化成工業株式会社 湿潤堅牢度増進剤
US4764585A (en) * 1984-07-21 1988-08-16 Sandoz Ltd. Cationic polycondensates useful for improving the fastness of dyeings on textiles
EP0431423A2 (de) * 1989-12-07 1991-06-12 Bayer Ag Basische Polykondensationsprodukte sowie deren Verwendung als Färbereihilfsmittel
EP0692511A1 (de) * 1994-07-12 1996-01-17 Ciba-Geigy Ag Verfahren zur Herstellung eines Färbereihilfsmittels

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JP3860220B2 (ja) 2006-12-20
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ID21780A (id) 1999-07-22
HK1024253A1 (en) 2000-10-05
EP0938515A1 (en) 1999-09-01
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DE69706062D1 (de) 2001-09-13
BR9712768A (pt) 1999-10-26

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