CN1051784C - 纤维-反应性双偶氮染料及其制备方法和应用 - Google Patents
纤维-反应性双偶氮染料及其制备方法和应用 Download PDFInfo
- Publication number
- CN1051784C CN1051784C CN93117835A CN93117835A CN1051784C CN 1051784 C CN1051784 C CN 1051784C CN 93117835 A CN93117835 A CN 93117835A CN 93117835 A CN93117835 A CN 93117835A CN 1051784 C CN1051784 C CN 1051784C
- Authority
- CN
- China
- Prior art keywords
- compound
- hydrogen
- formula
- base
- independently
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 65
- 238000004043 dyeing Methods 0.000 claims abstract description 26
- 150000003839 salts Chemical group 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004627 regenerated cellulose Substances 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims description 47
- 229910052739 hydrogen Inorganic materials 0.000 claims description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 29
- 239000000460 chlorine Substances 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 16
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- -1 methoxyl group Chemical group 0.000 claims description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 7
- 150000001721 carbon Chemical group 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 6
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 150000005699 fluoropyrimidines Chemical class 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 3
- 229920000742 Cotton Polymers 0.000 abstract description 15
- 238000007639 printing Methods 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 7
- 239000000835 fiber Substances 0.000 abstract description 4
- 239000004753 textile Substances 0.000 abstract description 4
- 239000004952 Polyamide Substances 0.000 abstract description 2
- 239000010985 leather Substances 0.000 abstract description 2
- 229920002647 polyamide Polymers 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 2
- 239000000975 dye Substances 0.000 description 28
- 239000002585 base Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 239000000985 reactive dye Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000001118 alkylidene group Chemical group 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000005185 salting out Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical class NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- 150000002499 ionone derivatives Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/022—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring the heterocyclic ring being alternatively specified
- C09B62/026—Azo dyes
- C09B62/03—Disazo or polyazo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/20—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a pyrimidine ring
- C09B62/24—Azo dyes
- C09B62/25—Disazo or polyazo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0046—Mixtures of two or more azo dyes
- C09B67/0055—Mixtures of two or more disazo dyes
- C09B67/0057—Mixtures of two or more reactive disazo dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coloring (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
通式如下的纤维-反应性双偶氮化合物
其中的符合如说明书中所定义,此化合物是游离酸型或盐型,以及它们的混合物。这类化合物适用于含羟基或含氮的有机基质物,例如皮革和包含天然或合成聚酰胺或天然或再生纤维素的纤维材料;最优选的基材是含棉纺织品的材料。
Description
本发明涉及纤维—反应性双偶氮染料及其生产方法。在任何通常的染色或印染过程中,这些化合物适用作为纤维—反应性染料。
每个R1独立地是氢,C1-4烷基或取代的C1-4烷基,
每个R2和R4独立地是氢,C1-4烷基,C1-4烷氧基,
-NHCOC1-4烷基,或-NHCONH2,
每个R3和R5独立地是氢,C1-4烷基或C1-4烷氧基,以及
Z是或
在其中,
n是零或整数1至4,
R6是氢,C1-4烷基,C1-4烷氧基,羧基或磺基,
R7是氢,C1-4烷基,C1-4烷氧基,羧基或-NHCOCH3,
p是0,1或2,
q是1或2,
r是1,2或3,
t是0或1,以及
T1是氢,氯或氰基,而
两个T2彼此相同,而且每个是氟或氯。
在说明书中,任何存在的烷基,烷氧基或亚烷基是直链的或支化的,除非另有指出。在任何连接到氮原子上的羟基取代烷基或亚烷基中,此羟基优选键合到并不直接连接在氮原子上的碳原子上。在任何被(Q则被连接到氮原子上)中断的亚烷基链中,Q优选被键合到碳原子上,而碳原子不被直接连到氮原子上。
当R1是一个已取代烷基时,它优选是被羟基,氰基或氯单取代的。
每个R1是优选R1a,这里每个R1a独立地是氢,甲基,乙基或2-羟乙基;更优选的是,每个R1是R1b,这里每个R1b独立地是氢或甲基。最优选的是每个R1是氢。
R2和R4优选是R2a和R1a,这里每个R2a和R4a独立地是氢,甲基,甲氧基,-NHCOCH3,或-NHCONH2。R2和R4更优选为R2b和R4b,这里每个R2b和R4b独立地是氢或甲基;R4最优选为氢。
R3优选为R3a,这里R3a是氢,甲基或甲氧基。
R5优选为R5a,这里R5a是氢或甲基;R5最优选是氢。
Hal最优选是氯。
R6优选是R6a,这里R6a是氢,甲基,甲氧基,羧基或磺基;更优选的是它是R5b,这里R6b是氢或磺基。
R7优选是R7a,这里R7a是氢,甲基,甲氧基或羧基。R7最优选是氢。
其中m独立地是0或1。
如下的通式Ia化合物是甚至更优选的,其中
(1)R1b是氢;
(2)R2a是R2b,而R4a是R4b;
(3)在其中的R4a和R5a均是氢的(2)的那些化合物;
(4)W1b是W1c;
(5)在其中的Da是(a′)基,R7a是氢的(1)-(4)的那些化合物;
当一种通式I的化合物是盐型时,与磺基或任何羧基相连的阳离子是不严格的,而且可以是纤维一反应性染料领域中的任何一种非发色阳离子。这类阳离子的例子是碱金属阳离子,以及未取代的和已取代的铵阳离子,例如,锂,钠,钾,铵,单一,双一,三和四一甲铵,三一乙铵和单一,双一和三一乙醇铵。
优选的阳离子为碱金属阳离子和铵,而钠是最优选的。
在一种通式I的化合物中,磺基和任何羧基的阳离子可以相同或不同,即它们也可以是上述阳离子的混合物,这意味着通式I化合物可以是混合盐的形式。
本发明还提供相应于通式I的化合物或其混合物的制法:
其中D是(a)基或(b)基的通式I化合物的制法包括使至少1摩尔2,4,6-三氟嘧啶与1摩尔通式IIa或IIb的化合物起反应:式中R1至R5,Hal和W1如上所定义,而Dx是如上所定义的基团(a)或(b);
此外,其中的D是(c)基或(d)基,Z和Z1均为的通式I化合物的制法包括使至少2摩尔2,4,6-三氟嘧啶与1摩尔通式IV化合物起反应:式中R1至R5和Dy如上所定义。
这些缩合反应按照公知的方法来制备,优选20-50℃的温度范围,更优选30-40℃,并在PH4-5之下。
通式I化合物按照公知的方法来分离,例如使用碱金属盐的通常盐析法,过滤以及在也可以是真空和稍高的温度下进行干燥。
根据反应和分离条件,通式I化合物以游离酸或优选以盐型或甚至是含例如上述阳离子中的一种或多种的混合盐型而获得。它可以按通常方法从游离酸变为盐型或盐型的混合物,或者反过来,或者从一种盐型变为另一种盐型。
一般说来,优选使用所得的染料混合物而不借助分离成供使用的单一异构体,但这应要求它易于用通常方法来取得。
通式IIa,IIb,III和IV化合物的原料化合物或者是已知的,或者是易于从已知原料用已知的采用通常重氮化,偶合和/或缩合反应的制法来制得。
通式I化合物及其混合物适用作染色或印染含羟基或含氮的有机基质物的纤维—反应性染料。优选的基质物是皮革及包含天然或合成聚酰胺以及特别是天然或再生纤维素例如棉,粘胶纤维及人造棉纱的纤维材料。最优选的基质物是包含棉的纺织材料。
染色和印染按照纤维—反应性染料领域通用的公知方法进行。优选的是,对通式I化合物来说,使用浸染方法,温度为30°-80℃,特别是50°-60℃,浴液对物料的比例采用6∶1至30∶1,而更优选为10∶1至20∶1。
本发明化合物与公知的纤维—反应性染料具有良好的相容性;它们可以单独用,或与同类的适当纤维—反应性染料合用,后者具有类似的染色性能例如共同的坚牢性和共同的从浴液转移到纤维上的能力,用这处混合染料得到的染色具有好的坚牢度并可与由单一染料所得的相比较。
通式I化合物当用作染料时产生好的浸染性和固色性。此外,未固着的染料易于从基质物上洗去。从通式I化合物所产生的染色和印染显示良好的耐光牢度和良好的耐湿牢度性例如耐洗涤,水、海水及耐汗牢度。它们亦显示良好的耐氧化剂例如氯水,次氯酸盐漂白剂,过氧化物漂白剂和耐含过硼酸盐洗涤剂洗涤的性能。
下列实施例解释了本发明。在实施例中份数和百分数均是指重量,除非指出是其他情况,而且所有的温度均以摄氏度表示。
实施例1
将30.3份2-氨基萘-1,6-二磺酸溶于250份水中,得到一种其PH小于1的溶液。在0-5°加入25份4N亚硝酸钠溶液以进行重氮化。将如此得到的重氮化合物在0-5℃和PH5下与13.7份1-氨基-2-甲氧基-5-甲基苯反应。反应完成之后,加入50体积份的30%的盐酸和25体积份的4N亚硝酸钠溶液。随后,在不超过10℃温度和PH4.5下,一次加入20.5份苯胺-ω-甲烷磺酸。偶合反应完成后(用薄层色谱法进行鉴控),加入30%氢氧化钠溶液把反应混合物的PH值调到13。然后将反应混合物加热到30°,慢慢滴入17体积份40%过氧化氢溶液。皂化结束后,在35°和PH4.5下,将已被游离的氨基与14.7份2,4,6-三氟代嘧啶起反应。如此获得的染料相应于下面通式(表示为游离酸形式):并可以用盐析法以通常方法从反应混合物中把它分离出来。它把棉织品染成橙色。这些棉织品染色物显示好的坚牢性,并耐氧化性影响。
实施例2
往在500份水的含44份下列通式化合物的溶液中,加入相应数量的30%盐酸以调节PH值为4.3至4.8。之后,在20℃滴加入29.4份2,4,6-三氟代嘧啶,在此同时加入20%碳酸钠溶液使PH维持在4.3至4.8。温度同时升至40°。反应完成后,把所得到的染料自反应介质中盐析出,过滤,在真空下在50℃下干燥,使用所得到的相应于下式的染料可制得橙色的染色和印染,它们显示高的耐光牢度和耐湿牢度,并耐氧化性影响。
实施例3-49
以与实施例1或2相似的方法,使用合适的原料化合物可制得通式I的另一些化合物,后者列于表1和2中。它们相应于通式(T1)主(T2),式中的符号如表1和2中所定义。
在表2中,-W1-栏中带标记的氮原子被连接到三嗪的碳原子上。
此外,在表中使用了下述符号ZTa到ZTc,其中ZTa是
ZTb是
及ZTc是
实施例3-49的化合物,采用通常的浸染方法,或通常的印染方法,可用于包含纤维织物的基质物,特别是包含棉织品的纺织材料,得到橙色的染色物和印染物。这种在棉织品上的染色物和印染物显示良好的耐光牢度及耐湿牢度,和耐氧化影响。
表1.通式(T1)化合物,实施例3-23实施例号 DT1 R2 R3 R4 R5 R13
H H H H H4 同上 CH3 H H H H5
H H H CH3 H6 同上 CH3 H CH3 H CH37 同上 -NHCOCH3 H H H H8
H H CH3 H H9 同上 H OCH3 H H H10
H H H H H11 同上 -NHCOCH3 H H H H12 同上 -NHCONH2 H H H H13 同上 CH3 OCH3 H H H
表1(续)实施例号 DT1 R2 R3 R4 R5 R114
CH3 OCH3 CH3 H H15
同上 同上 同上 H H16
同上 同上 H H H17
同上 同上 H H H18
同上 同上 H H H19
同上 同上 H H H20
同上 同上 H H H21 同上 H H H H H22 同上 CH3 CH3 H H CH323
H H H H H
表2.通式(T2)的化合物,实施例24-49实施例号 DT2 R2 R3 R4 R5 R1 -W1-24
CH3 H CH3 H H
25 同上 -NHCOCH3 H H H H -NHCH2CH2CH2NH-26 同上 CH3 H H H H
27
H H H H H 同上28 同上 CH3 H CH3 H CH3 同上29 同上 同上 OCH3 H H H
30
同上 H H H H 同上31 同上 H H H H H
32 同上 CH3 H H H H
33 同上 同上 OCH3 H H H 同上34 同上 H H H H H 同上
表2(续)实施例号 DT2 R2 R3 R4 R5 R1 -W1-35
CH3 OCH3 H H H
36
H H H H H 同上37
-NHCOCH3 H H H H -NHCH2CH2CH2NH-38
-NHCONH2 H H H H
39
CH3 OCH3 H H H 同上40 同上 -NHCOCH3 H H H CH3 同上41 同上 同上 同上 -NHCOCH3 CH3 H 同上42
H H CH3 H CH3
43 同上 CH3 OCH3 H H H 同上
表2(续)实施例号 DT2 R2 R3 R4 R5 R1 -W1-44
CH3 OCH3 -NHCONH2 H H
45
H H H H H 同上46 同上 CH3 OCH3 H H H
47
同上 同上 H H H 同上48
CH3 H CH3 H CH3 同上49
-NHCOCH3 H H H 同上 同上采用实施例1和2中所述的制法,制得了实施例1-49的钠盐形式的化合物。改变反应或分离条件,或使用其他公知方法,可以生成游离酸型式或其他盐型或混合盐型的化合物,它们含有一个或多个上述的阳离子。
如以上所指出的实施例1-49的染料(以及相应游离酸型或其他盐型)含有涉及基的两种异构化合物;一种化合物在其嘧啶环上的浮动氟取代基是在2位置上,而另一相应化合物则在6-位置上,ZTb基和ZTc基也以类似方式出现在就浮动氟或氯取代基而言的两类适宜的异构体形式中,所得的异构体染料混合物可用于通常的染色法或印染方法中;对使用来说单一异构体的分离通常是不必要的。
在下面的实施例中,说明了本发明化合物的应用。
应用实施例A
把0.3份实施例1的染料溶于100份软化水中,并加入8份芒硝(煅烧过的)。将染浴加热至50°,然后加入10份棉织品织物(漂白过的),在50°加热30分钟后,加入0.4份碳酸钠(煅烧过的)并保持温度在50°。随后,把染浴加热至60℃,并使染色在60°再进行1小时。
然后将已染色的织物用流动冷水漂洗3分钟,而且随后用流动热水又漂洗3分钟。把染色物在有0.25份马赛皂的500份软水中在煮沸下洗涤15分钟。在用流动热水漂洗(3分钟)和离心后,将染色物在约70°在柜式干燥器中干燥。获得了显示良好坚牢性特别是高的耐湿牢度的橙色棉织品染色物,后者对氧化性的影响是稳定的。
应用实施例B
往含有100份软化水和5份芒硝(煅烧过的)的染浴中,加入10份棉织品(漂白过),在10分钟内把染浴加热至50°,加入0.5份实施例1的染料。在50°再加热30分钟后,加入1份碳酸钠(煅烧过的)。然后将染浴加热至60°并使染色在60°再继续45分钟。
把已染色纺织品先用流动冷水再用流动热水漂洗,按应用实施例A给出的方法煮沸洗涤。漂洗和干燥后,得到具有与应用实施例A所指出的同样好的坚牢度的橙色棉织品染色物。
相似地,实施例2-49的染料或所例举的染料的混合物,可按应用实施例A或B所述的方法,用于染棉织品。如此获得的棉织品的染色物是橙色的,并显示良好的坚牢性。
应用实施例C
按照通常印染法,把含
40份实施例1的染料
100份尿素
350份水
500份4%藻酸钠增稠剂,以及
10份碳酸氢钠
共1000份的印染浆用于绵织品的染色。
将已印染的织物在102-104°蒸汽中干燥和固定4-8分钟。先在冷水后在热水中漂洗,煮沸下洗涤(按照应用实施例A所述的方法)并干燥。得到具有良好坚牢性能的橙色印染物。
相似地,实施例2-49的染料或所例举的染料的混合物,可按应用实施例C所给出的方法用于印染棉织物。所得到的所有的印染物均为橙色并显示良好的坚牢性。
Claims (18)
1.通式I的化合物及其盐 或这些化合物或盐的混合物,式中:
R1独立地是氢,或C1-4烷基,
R2和R4各自独立地是氢,C1-4烷基,C1-4烷氧基,-NH-COC1-4烷基,或-NHCONH2,
Hal是氟或氯,以及
W1是-NR1-B1-NR1-,式中B1是C2-3亚烷基或被羟基单取代的C3-4亚烷基,而R1的定义如上所述,
R7是氢,
p是0,1或2,
q是1或2,
r是1,2或3,
t是0或1,以及
Z1是式中
T1是氢,氯或氰基,而
两个T2彼此相同,而且每个T2是氟或氯。
2.根据权利要求1的化合物,其中R1是R1a,而R1a独立地是氢或甲基。
3.根据权利要求1的化合物,R2和R4是R2a和R4a,而R2a和R4a各自独立地是氢,甲基,甲氧基,-NHCOCH3,或-NHCONH2;R3是R3a,而R3a是氢,甲基或甲氧基,R5是R5a,而R5a是氢或甲基。
4.根据权利要求3的化合物,其中R4和R5各自为氢。
6.根据权利要求5的化合物,其中Z1′是
8.根据权利要求7的化合物,其中每个R1b是氢。
9.根据权利要求7的化合物,其中每个R2a和R4a独立地是氢或甲基。
10.根据权利要求9的化合物,其中每个R4a和R5a是氢。
12.根据权利要求7的化合物,其中Da是(a′)基,其中R7a是氢。
17.含羟基或含氮有机基质物的染色或印染方法,包括把根据权利要求1-13中的任一项的化合物或它们的混合物用于该基质物。
18.根据权利要求17的方法,其中该基质物是包含天然或再生纤维素的纤维材料。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4226918 | 1992-08-14 | ||
DEP4226918.0 | 1992-08-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1085923A CN1085923A (zh) | 1994-04-27 |
CN1051784C true CN1051784C (zh) | 2000-04-26 |
Family
ID=6465541
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN93117835A Expired - Fee Related CN1051784C (zh) | 1992-08-14 | 1993-08-13 | 纤维-反应性双偶氮染料及其制备方法和应用 |
Country Status (15)
Country | Link |
---|---|
US (1) | US5554732A (zh) |
JP (1) | JP3657625B2 (zh) |
KR (1) | KR100294993B1 (zh) |
CN (1) | CN1051784C (zh) |
BR (1) | BR9303266A (zh) |
CH (1) | CH685705A5 (zh) |
ES (1) | ES2103167B1 (zh) |
FR (1) | FR2694763B1 (zh) |
GB (1) | GB2269596B (zh) |
IT (1) | IT1261516B (zh) |
MX (1) | MX9304886A (zh) |
PT (1) | PT101335B (zh) |
TR (1) | TR26932A (zh) |
TW (1) | TW264503B (zh) |
ZA (1) | ZA935939B (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9509159D0 (en) * | 1995-05-05 | 1995-06-28 | Sandoz Ltd | Organic compounds |
DE19636272A1 (de) * | 1996-09-06 | 1998-03-12 | Star Gmbh | Linearführungseinrichtung |
GB9710611D0 (en) * | 1997-05-23 | 1997-07-16 | Clariant Int Ltd | New disazo dyestuffs |
US6084077A (en) * | 1997-05-23 | 2000-07-04 | Clariant Fianance (Bvi) Limited | Disazo dyestuffs |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2219804A (en) * | 1988-06-14 | 1989-12-20 | Sandoz Ltd | Reactive dyes with cyanodihalopyrimidyl and chlorotriazinyl groups |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1225788B (de) * | 1963-03-06 | 1966-09-29 | Badische Anilin- &. Soda-Fabrik Aktiengesellschaft, Ludwigshafen/Rhem | Verfahren zur Herstellung von Dihalogenpyrimidylfarbstoffen |
DE1644171A1 (de) * | 1966-09-10 | 1970-07-30 | Bayer Ag | Reaktivfarbstoffe und Verfahren zu deren Herstellung |
CH643583A5 (de) * | 1979-08-16 | 1984-06-15 | Sandoz Ag | Reaktivfarbstoffe sowie deren herstellung. |
DE3010161A1 (de) * | 1980-03-17 | 1981-09-24 | Bayer Ag, 5090 Leverkusen | Farbstoffe, verfahren zu ihrer herstellung sowie ihre verwendung zum faerben hydroxylgruppen- oder stickstoffhaltiger materialien |
JPS56155250A (en) * | 1980-04-10 | 1981-12-01 | Nippon Kayaku Co Ltd | Reactive dis-azo compound, production thereof and dyeing method employing the same |
DE3477802D1 (en) * | 1983-06-10 | 1989-05-24 | Ciba Geigy Ag | Reactive dyes, their preparation and their use |
EP0131543B1 (de) * | 1983-06-14 | 1988-07-13 | Ciba-Geigy Ag | Reaktivfarbstoffe, deren Herstellung und Verwendung |
GB8530024D0 (en) * | 1985-12-05 | 1986-01-15 | Ici Plc | Reactive dyes |
FR2609468B1 (fr) * | 1987-01-14 | 1989-07-13 | Sandoz Sa | Nouveaux composes monoazoiques, leur preparation et leur utilisation comme colorants reactifs |
US5227476A (en) * | 1987-01-14 | 1993-07-13 | Sandoz Ltd. | 2-(3,6,8-trisulfonaphth-2-ylazo)-5-[2-chloro-4-[2-(5-chloro-2,4-difluoropyrimid-6-ylamino)-2-methyl-ethyl]amino-1,3,5-triazin-6-ylamino]phenyl urea salts thereof |
ES2053804T3 (es) * | 1987-09-21 | 1994-08-01 | Ciba Geigy Ag | Procedimiento para teñir o estampar materiales de fibras poliamidicas naturales o sinteticas con colorantes reactivos. |
US5227477A (en) * | 1988-06-14 | 1993-07-13 | Sandoz Ltd. | Dyes having one or two 2,4- or 4,6-dichloro-5-cyanopyrimidyl groups linked through bridging radicals containing at least two nitrogen atoms to chloro-1,3,5-triazinyl groups |
ES2075071T3 (es) * | 1988-10-20 | 1995-10-01 | Sandoz Ag | Colorantes azoicos reactivos con fibras. |
DE59007148D1 (de) * | 1990-02-17 | 1994-10-20 | Bayer Ag | Reaktivfarbstoffe. |
EP0495753B1 (de) * | 1991-01-16 | 1997-07-16 | Ciba SC Holding AG | Reaktivfarbstoffe, Verfahren zu deren Herstellung und deren Verwendung |
DE59206979D1 (de) * | 1991-05-15 | 1996-10-02 | Bayer Ag | Reaktivfarbstoffe |
DE4125266A1 (de) * | 1991-07-31 | 1993-02-04 | Bayer Ag | Reaktivfarbstoffe |
DE4125754A1 (de) * | 1991-08-03 | 1993-02-04 | Bayer Ag | Fluorpyrimidin-reaktivfarbstoffe |
-
1993
- 1993-08-02 BR BR9303266A patent/BR9303266A/pt not_active IP Right Cessation
- 1993-08-06 FR FR9309800A patent/FR2694763B1/fr not_active Expired - Fee Related
- 1993-08-10 GB GB9316572A patent/GB2269596B/en not_active Expired - Fee Related
- 1993-08-12 TR TR00717/93A patent/TR26932A/xx unknown
- 1993-08-12 ES ES09301791A patent/ES2103167B1/es not_active Expired - Fee Related
- 1993-08-12 CH CH2393/93A patent/CH685705A5/de not_active IP Right Cessation
- 1993-08-12 MX MX9304886A patent/MX9304886A/es unknown
- 1993-08-13 CN CN93117835A patent/CN1051784C/zh not_active Expired - Fee Related
- 1993-08-13 KR KR1019930015721A patent/KR100294993B1/ko not_active IP Right Cessation
- 1993-08-13 PT PT101335A patent/PT101335B/pt not_active IP Right Cessation
- 1993-08-13 ZA ZA935939A patent/ZA935939B/xx unknown
- 1993-08-13 IT ITRM930559A patent/IT1261516B/it active IP Right Grant
- 1993-08-13 JP JP20161993A patent/JP3657625B2/ja not_active Expired - Fee Related
- 1993-08-16 TW TW082106544A patent/TW264503B/zh active
-
1995
- 1995-05-02 US US08/431,651 patent/US5554732A/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2219804A (en) * | 1988-06-14 | 1989-12-20 | Sandoz Ltd | Reactive dyes with cyanodihalopyrimidyl and chlorotriazinyl groups |
Also Published As
Publication number | Publication date |
---|---|
KR100294993B1 (ko) | 2001-12-05 |
US5554732A (en) | 1996-09-10 |
MX9304886A (es) | 1994-06-30 |
JP3657625B2 (ja) | 2005-06-08 |
TW264503B (zh) | 1995-12-01 |
BR9303266A (pt) | 1994-03-08 |
CN1085923A (zh) | 1994-04-27 |
PT101335B (pt) | 1999-10-29 |
ES2103167A1 (es) | 1997-08-16 |
FR2694763A1 (fr) | 1994-02-18 |
FR2694763B1 (fr) | 1995-09-22 |
KR940004015A (ko) | 1994-03-14 |
IT1261516B (it) | 1996-05-23 |
GB2269596A (en) | 1994-02-16 |
JPH06184454A (ja) | 1994-07-05 |
PT101335A (pt) | 1994-06-30 |
ITRM930559A1 (it) | 1995-02-13 |
ES2103167B1 (es) | 1998-04-01 |
GB2269596B (en) | 1995-11-08 |
ZA935939B (en) | 1995-02-13 |
ITRM930559A0 (it) | 1993-08-13 |
TR26932A (tr) | 1994-08-24 |
CH685705A5 (de) | 1995-09-15 |
GB9316572D0 (en) | 1993-09-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1054868C (zh) | 活性染料及其制备方法和用途 | |
CN1055941C (zh) | 纤维-反应性染料及其制备和应用 | |
CN1097076C (zh) | 活性染料、它们的制备及用途 | |
CN1118520C (zh) | 用于对有机基质进行染色的三苯基二䓬嗪染料 | |
CN1090655C (zh) | 染料 | |
KR20090083926A (ko) | 반응성 염료의 혼합물 및 삼색 염색 또는 인쇄에서의 이들의 용도 | |
CN1051784C (zh) | 纤维-反应性双偶氮染料及其制备方法和应用 | |
KR20020079999A (ko) | 섬유 반응성 디스아조 화합물 | |
CN1052024C (zh) | 制备具有杂环反应性基因的酞菁类化合物其盐或其混合物的方法 | |
CN1075100C (zh) | 染料混合物,它们的制备方法和它们的用途 | |
CN1054869C (zh) | 纤维-反应性偶氮染料 | |
CN1145934A (zh) | 纤维活性染料 | |
US5410041A (en) | Bisreactive dyes having a disulfophenylene bridging member | |
JP4138877B2 (ja) | 繊維反応性染料 | |
CN1636038A (zh) | 偶氮染料 | |
CN1157823A (zh) | 纤维活性染料、它们的制备及应用 | |
CN1503828A (zh) | 纤维-反应性单偶氮基染料 | |
CN1056634C (zh) | 二重氮化合物及它的制备方法和其在染色或印染中的应用 | |
CN1047608C (zh) | 纤维反应性单偶氮化合物及其制备方法和用途 | |
KR20040045493A (ko) | 유기 화합물 | |
CN1149265C (zh) | 新的双偶氮染料 | |
CN1092441A (zh) | 纤维活性酞菁染料 | |
CN1289610C (zh) | 新的甲活性染料 | |
CN1325427A (zh) | 活性染料混合物及其用途 | |
GB2151251A (en) | Triazinyl disazo dyes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C53 | Correction of patent of invention or patent application | ||
CB02 | Change of applicant information |
Address after: The British Virgin Islands Applicant after: Krairi Anter Finanace (BVI) Co., Ltd. Address before: Basel, Switzerland Applicant before: Sandoz Ltd. |
|
COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: SANDOZ CO., LTD. TO: CLERIDES ANTROBUS FINANCE(BVI)LTD. |
|
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20000426 Termination date: 20100813 |