CN1065883C - 染色助剂的制备方法 - Google Patents
染色助剂的制备方法 Download PDFInfo
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
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Abstract
本发明描述了一种制备碱性缩聚物的方法,该方法包括(a)使式(1)的胺(其中R1,R2,R3和R4彼此独立地为氢或未取代或被氨基,羟基,氰基或C1-C4烷氧基取代的烷基,A为未取代的或被一个或多个杂原子取代或间隔的亚烷基)与铵盐在无水溶剂存在下反应,和(b)使按照(a)得到的质子化产物与氨基氰在提高的温度下反应。按照本发明方法制备的缩聚物或其盐是特别适宜的后处理剂,可用于增强印染的纺织纤维材料的耐湿性。
Description
本发明涉及一种制备水溶性缩聚物的方法,该方法包括使多官能胺与氨基氰或其衍生物反应,同时除去氨。
已知有许多这样的缩聚物,它们的制备方法及其在增强直接染料的染色坚牢度性能方面的应用。然而,现有技术的方法例如在处理,工艺程序的控制和生态学方面有许多缺点。例如其中一个缺点是反应常常是在金属盐催化剂存在下进行的,在终产物中仍存在痕量催化剂,需通过复杂的纯化方法将其除去。另一种已知的方法是使所有的反应物混合进行批量生产,但由于难以控制除去氨的强烈反应,所以也有问题。已提出的另一种方法是在不加任何溶剂的情况下进行的,但由于反应混合物的高粘性,其可行性是有限的。
令人惊奇的是,现已发现,通过首先使多官能胺与铵化合物反应而转化为质子化形式,然后使质子化化合物与氨基氰反应可简单地制备相应的缩聚物,其操作安全性明显提高。
因此,本发明的目的是提供一种制备碱性缩聚物的方法,该方法包括
(a)使式(1)的胺
其中R1,R2,R3和R4彼此独立地为氢或未取代或被氨基,羟基,氰基或C1-C4烷氧基取代的烷基,A为未取代的或被一个或多个杂原子取代或间隔的亚烷基,与铵盐在无水溶剂存在下反应,和
(b)使按照(a)得到的质子化产物与氨基氰在提高的温度下反应。
式(1)中的A优选为C2-C20亚烷基,其可被-O-,-S-,-NH-或-N(C1-C4烷基)-间隔或被OH取代。A优选为被一个或多个-NH-基团间隔的C2-C20亚烷基。
R1,R2,R3和R4彼此独立地优选为氢或C1-C4烷基。
可适当地用于反应步骤(a)的式(1)化合物的说明性实例典型的有1,4-丁二胺,1,6-己二胺,二亚丙基三胺,N-(2-氨乙基)-1,3-丙二胺,N,N-双(2-氨丙基)甲胺,多亚乙基亚胺或多亚乙基多胺如二亚乙基三胺,三亚乙基四胺,四亚乙基五胺,五亚乙基六胺。步骤(a)中优选的式(1)化合物是多亚乙基多胺,其中最好的是二亚乙基三胺。
适用于本发明方法的铵盐典型的是有机或无机酸的铵盐如氯化铵,硫酸铵,碳酸铵,甲酸铵或乙酸铵。优选使用氯化铵。
无水溶剂典型的是含羟基的溶剂,优选的是沸点在150℃以上的溶剂,特别是沸点在180℃以上的溶剂,或者上述不同溶剂的混合物。其代表性实例是1,2-亚乙基二醇,1,2-或1,3-丙二醇,丁二醇,二-,三-或四亚乙基二醇及其醚,以及分子量通常为600-5000的聚乙二醇,和它们的混合物。
适用于步骤(b)的氨基氰典型的是氨基氰,双氰胺,胍和双胍。在步骤(b)中优选使用双氰胺。
在步骤(a)中,式(1)化合物和铵盐典型的用量摩尔比为1∶0.1-1∶2.5,优选为1∶0.7-1∶2,最好为1∶1-1∶1.5。含羟基溶剂的用量范围很宽,以每摩尔式(1)化合物计,典型的是0.2-20摩尔,优选0.4-5摩尔。
步骤(a)的反应宜在提高的温度如80-200℃,优选100-160℃,最好110-140℃下进行。宜将式(1)化合物加到含控基的溶剂或溶剂混合物中,然后将铵化合物加到该混合物中,在此,该反应步骤宜在惰性条件下,特别是在氮气下进行。
然后使按照(a)得到的式(1)的质子化化合物,以每摩尔式(1)化合物计,与例如0.5-2摩尔,优选0.8-1.5摩尔氨基氰反应。(b)步骤的反应宜在一种或多种上述含羟基的溶剂存在下,在提高的温度下,一般可在80-250℃,优选140-220℃下进行。
优选的步骤是在温度为80-200℃,优选140-180℃下,将氨基氰以增量的方式加入到按照(a)得到的反应混合物中,加完后,在提高的温度下,一般在160-250℃,优选180-220℃下,使反应完成。在反应过程中,反应混合物逐渐变粘,氨被缓慢除去。缩合反应通常进行到氨被完全除去或反应混合物达到所需粘度时停止反应。
本发明的优选实施方案是一种制备碱性缩聚物的方法,该方法包括
(a)在含羟基的溶剂存在下,使二亚乙基三胺在惰性条件下与选自氯化铵,硫酸铵,碳酸铵,甲酸铵或乙酸铵的铵盐反应,和
(b)在提高的温度下使按照(a)得到的质子化产物与双氰胺反应。
本发明特别优选的实施方案是一种制备碱性缩聚物的方法,该方法包括
(a)在0.4-5摩尔当量的1,2-亚乙基二醇,1,2-或1,3-丙二醇,丁二醇,二-,三-或四亚乙基二醇或其醚,或分子量为600-5000的聚乙二醇,或两种或多种所述溶剂的混合物存在下,在110-140℃使1摩尔当量二亚乙基三胺在惰性条件下与1-1.5摩尔当量氯化铵反应,和
(b)在140-180℃将0.5-2摩尔当量双氰胺加入到含有按照(a)得到的式(1)质子化化合物的反应混合物中,加完后,在160-250℃使反应完成。
反应产物在室温下为具有碱性性质的固体熔体,其在水中可形成透明的溶液;用无机或有机酸如盐酸或乙酸中和可使之转化为其水溶性盐。
按照(a)得到的反应混合物最好用水稀释处理,从而将其调节到预定的产物终浓度,该浓度一般可为整个混合物的20-80%(重量),优选35-75%(重量)。
本发明的方法能以几乎定量的产率和高度的操作安全性简单地提供缩聚物。时空产率是极好的。
按照本发明的方法制备的缩聚物或其盐是特别适宜的后处理剂,可用于增强印染的含羟基或氨基的纺织纤维材料,特别是用直接染料或反应性染料染色的天然或再生纤维素制成的纺织材料的耐湿性。
下列实施例可进一步说明本发明。除非另有规定,份数以重量计。
实施例1
在室温和惰性气氛下,将206.4份二亚乙基三胺和55.6份1,2-亚乙基二醇装入反应器并在弱氮气流下加热至120℃。用1小时以增量方式加入128份氯化铵,使反应器中的温度保持在≥118℃。加完后,将反应混合物加热至160℃,用1小时在惰性条件下加入218份双氰胺,使反应器中的温度保持在高于155℃。然后将混合物加热至180-210℃范围内的温度并在此温度下保持约1-5小时。反应完成后,用时约20-25分钟向混合物中加入200份去离子水,得到665份其固体含量为70%的溶液。
实施例2
在室温和氮气气氛下,将206.4份二亚乙基三胺和35.9份1,2-亚乙基二醇装入反应器并在弱氮气流下加热至120℃。用1小时以增量方式加入128份氯化铵,使反应器中的温度保持在≥118℃。加完后,将反应混合物加热至160℃,用1小时在惰性条件下加入218份双氰胺,使反应器中的温度保持在高于155℃。然后将混合物加热至180-185℃范围内的温度并在此温度下保持约3小时。反应完成后,用时约20-25分钟向混合物中加入200份去离子水,得到665份其固体含量为70%的溶液。
实施例3
在室温和惰性气氛下,将206.4份二亚乙基三胺和35.9份1,2-亚乙基二醇装入反应器并在弱氮气流下加热至120℃。用1小时以增量方式加入128份氯化铵,使反应器中的温度保持在≥118℃。加完后,将反应混合物加热至160℃,用1小时在惰性条件下加入218份双氰胺,使反应器中的温度保持在高于155℃。然后将混合物加热至207℃并在此温度下保持约1小时。反应完成后,用时约20-25分钟向混合物中加入200份去离子水,得到665份其固体含量为70%的溶液。
实施例4
在室温和惰性气氛下,将206.4份二亚乙基三胺和102.2份1,2-亚乙基二醇装入反应器并在弱氮气流下加热至120℃。用1小时以增量方式加入128份氯化铵,使反应器中的温度保持在≥118℃。加完后,将反应混合物加热至160℃,用1小时在惰性条件下加入218份双氰胺,使反应器中的温度保持在高于155℃。然后将混合物加热至183℃并在此温度下保持约1小时。反应完成后,用时约20-25分钟向混合物中加入200份去离子水,得到665份其固体含量为70%的溶液。
实施例5
在室温和惰性气氛下,将206.4份二亚乙基三胺和55.3份丙二醇装入反应器并在弱氮气流下加热至120℃。用1小时以增量方式加入128份氯化铵,使反应器中的温度保持在≥118℃。加完后,将反应混合物加热至160℃,用1小时在惰性条件下加入218份双氰胺,使反应器中的温度保持在高于155℃。然后将混合物加热至190℃并在此温度下保持约1小时。反应完成后,用时约20-25分钟向混合物中加入200份去离子水,得到665份其固体含量为70%的溶液。
实施例6
在室温和惰性气氛下,将206.4份二亚乙基三胺和110.5份丙二醇装入反应器并在弱氮气流下加热至120℃。用1小时以增量方式加入128份氯化铵,使反应器中的温度保持在≥118℃。加完后,将反应混合物加热至160℃,用1小时在惰性条件下加入218份双氰胺,使反应器中的温度保持在高于155℃。然后将混合物加热至190℃并在此温度下保持约1小时。反应完成后,用时约20-25分钟向混合物中加入200份去离子水,得到665份其固体含量为70%的溶液。
实施例7
在室温和惰性气氛下,将206.4份二亚乙基三胺和165.75份丙二醇装入反应器并在弱氮气流下加热至120℃。用1小时以增量方式加入128份氯化铵,使反应器中的温度保持在≥118℃。加完后,将反应混合物加热至160℃,用1小时在惰性条件下加入218份双氰胺,使反应器中的温度保持在高于155℃。然后将混合物加热至190℃并在此温度下保持约1小时。反应完成后,用时约20-25分钟向混合物中加入200份去离子水,得到665份其固体含量为70%的溶液。
Claims (15)
2.根据权利要求1的方法,其中式(1)中的A为C2-C20亚烷基,其可被-O-,-S-,-NH-或-N(C1-C4烷基)-间隔或被OH取代。
3.根据权利要求1的方法,其中式(1)的化合物是亚乙基多胺。
4.根据权利要求1的方法,其中铵化合物是氯化铵,硫酸铵,碳酸铵,甲酸铵或乙酸铵。
5.根据权利要求1的方法,其中无水溶剂是含羟基的溶剂。
6.根据权利要求1的方法,其中无水溶剂是1,2-亚乙基二醇,1,2-或1,3-丙二醇,丁二醇,二-,三-或四亚乙基二醇或其醚,分子量为600-5000的聚乙二醇,或一种或多种所述溶剂的混合物。
7.根据权利要求1的方法,其中步骤(b)中的氨基氰是双氰胺。
8.根据权利要求1的方法,该方法包括在步骤(a)中使用其摩尔比为1∶1-1∶1.5的式(1)的化合物和铵盐。
9.根据权利要求1的方法,该方法包括在步骤(a)中将式(1)的化合物加到含羟基的溶剂或溶剂混合物中,加入铵化合物,并在惰性条件下进行反应。
10.根据权利要求1的方法,其中步骤(b)是通过在140-180℃将氨基氰加入到按照(a)得到的反应混合物中,加完后,在160-250℃使反应完成来进行的。
11.根据权利要求1的制备碱性缩聚物的方法,该方法包括
(a)在含羟基的溶剂存在下,使二亚乙基三胺在惰性条件下与选自氯化铵,硫酸铵,碳酸铵,甲酸铵和乙酸铵的铵盐反应,和
(b)在提高的温度下使按照(a)得到的质子化产物与双氰胺反应。
12.根据权利要求1的制备碱性缩聚物的方法,该方法包括
(a)在0.4-5摩尔当量的1,2-亚乙基二醇,1,2-或1,3-丙二醇,丁二醇,二-,三-或四亚乙基二醇或其醚,或分子量为600-5000的聚乙二醇,或两种或多种所述溶剂的混合物条件下,在110-140℃使1摩尔当量二亚乙基三胺在惰性条件下与1-1.5摩尔当量氯化铵反应,和
(b)在140-180℃将0.5-2摩尔当量双氰胺加入到含有按照(a)得到的式(1)质子化化合物的反应混合物中,加完后,在160-250℃使反应完成。
13.根据权利要求2的方法,其中A被一个或多个-NH-基团间隔。
14.根据权利要求3的方法,其中式(1)的化合物是二亚乙基三胺。
15.根据权利要求4的方法,其中铵化合物是氯化铵。
Applications Claiming Priority (3)
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CH2222/1994 | 1994-07-12 | ||
CH2222/94 | 1994-07-12 | ||
CH222294 | 1994-07-12 |
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CN1121915A CN1121915A (zh) | 1996-05-08 |
CN1065883C true CN1065883C (zh) | 2001-05-16 |
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US (1) | US5705605A (zh) |
EP (1) | EP0692511B1 (zh) |
JP (1) | JPH0848769A (zh) |
KR (1) | KR100357800B1 (zh) |
CN (1) | CN1065883C (zh) |
DE (1) | DE59508299D1 (zh) |
DK (1) | DK0692511T3 (zh) |
ES (1) | ES2146301T3 (zh) |
PT (1) | PT692511E (zh) |
TW (1) | TW307804B (zh) |
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TR199900893T2 (xx) * | 1996-11-15 | 1999-07-21 | Clariant International Ltd | Yeni yoğunlaşma ürünleri ve uygulamaları. |
AU4372099A (en) * | 1998-06-11 | 1999-12-30 | Ciba Specialty Chemicals Holding Inc. | Use of basic polycondensates as antimicrobial active substance |
BR0112229B1 (pt) * | 2000-07-04 | 2012-02-22 | processo para redução de perda de corante ou transferência de corante de materiais de fibra têxtil no setor doméstico com um agente de fixação de corante, formulações de lavagem e de amaciante e agente de fixação de corante. | |
KR20040073553A (ko) * | 2002-01-07 | 2004-08-19 | 시바 스페셜티 케미칼스 홀딩 인크. | 염료 고착제를 포함하는 미립자 조성물 |
KR100497908B1 (ko) * | 2002-08-09 | 2005-06-29 | (주)대일화성 | 염색 조제의 제조방법 |
US7141119B2 (en) * | 2003-05-19 | 2006-11-28 | Imation Corp. | Pressure-controlling dispersion delivery system |
US7496481B2 (en) * | 2006-05-19 | 2009-02-24 | Watlow Electric Manufacturing Company | Sensor adaptors and methods |
WO2009090121A1 (en) * | 2008-01-17 | 2009-07-23 | Basf Se | Polymeric hair dyes |
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DE1595651B2 (de) * | 1966-04-23 | 1977-01-20 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung polymerer produkte |
JPS57106782A (en) * | 1980-12-22 | 1982-07-02 | Sanyo Chemical Ind Ltd | Agent and method for increasing wet fastness |
JPS57115421A (en) * | 1980-12-30 | 1982-07-17 | Nippon Carbide Ind Co Ltd | Novel polymer and its production |
JPS5936133A (ja) * | 1982-08-23 | 1984-02-28 | Hitachi Ltd | 熱硬化性組成物 |
CH667360GA3 (zh) * | 1984-07-21 | 1988-10-14 | ||
US5442039A (en) * | 1989-07-17 | 1995-08-15 | The Dow Chemical Company | Mesogenic polycyanates and thermosets thereof |
DE3940481A1 (de) * | 1989-12-07 | 1991-06-13 | Bayer Ag | Basische polykondensationsprodukte sowie deren verwendung als faerbereihilfsmittel |
-
1995
- 1995-06-27 TW TW084106553A patent/TW307804B/zh active
- 1995-07-04 EP EP95810439A patent/EP0692511B1/de not_active Expired - Lifetime
- 1995-07-04 DE DE59508299T patent/DE59508299D1/de not_active Expired - Lifetime
- 1995-07-04 DK DK95810439T patent/DK0692511T3/da active
- 1995-07-04 ES ES95810439T patent/ES2146301T3/es not_active Expired - Lifetime
- 1995-07-04 PT PT95810439T patent/PT692511E/pt unknown
- 1995-07-06 US US08/498,847 patent/US5705605A/en not_active Expired - Lifetime
- 1995-07-06 JP JP7170689A patent/JPH0848769A/ja active Pending
- 1995-07-11 CN CN95109987A patent/CN1065883C/zh not_active Expired - Fee Related
- 1995-07-11 KR KR1019950020253A patent/KR100357800B1/ko not_active IP Right Cessation
Also Published As
Publication number | Publication date |
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KR960004454A (ko) | 1996-02-23 |
US5705605A (en) | 1998-01-06 |
KR100357800B1 (ko) | 2003-01-29 |
EP0692511B1 (de) | 2000-05-10 |
PT692511E (pt) | 2000-11-30 |
CN1121915A (zh) | 1996-05-08 |
EP0692511A1 (de) | 1996-01-17 |
TW307804B (zh) | 1997-06-11 |
DK0692511T3 (da) | 2000-09-18 |
ES2146301T3 (es) | 2000-08-01 |
DE59508299D1 (de) | 2000-06-15 |
JPH0848769A (ja) | 1996-02-20 |
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