CN111286211B - 耐晒型蓝色酸性染料及其制备方法 - Google Patents
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
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- CMKIPUDSZBGVQI-UHFFFAOYSA-N chembl2147998 Chemical group OC1=CC=CC=C1C1=CNN=N1 CMKIPUDSZBGVQI-UHFFFAOYSA-N 0.000 description 1
- UAKMCBRMMSMYLT-UHFFFAOYSA-N chloro(phenyl)methanesulfonic acid Chemical compound OS(=O)(=O)C(Cl)C1=CC=CC=C1 UAKMCBRMMSMYLT-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
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- ALDIVIWLBSDGGN-ONEGZZNKSA-N indigoidine Chemical compound O=C1NC(=O)C(N)=C\C1=C\1C(=O)NC(=O)C(N)=C/1 ALDIVIWLBSDGGN-ONEGZZNKSA-N 0.000 description 1
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- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
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- 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
- C09B57/00—Other synthetic dyes of known constitution
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- 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
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0072—Preparations with anionic dyes or reactive dyes
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- 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
- D06P1/39—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 acid dyes
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- 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
- D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67333—Salts or hydroxides
- D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
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- 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
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/14—Wool
- D06P3/16—Wool using acid dyes
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Abstract
本发明公开了一种耐晒型蓝色酸性染料,其结构通式如下:
Description
技术领域
本发明涉及一种耐晒型蓝色酸性染料及其制备方法。
背景技术
2015年,由美国犹他州立大学的研究人员利用大肠杆菌制造出了一种称为Indigoidine的靛蓝染料,并实现了规模化量产。Indigoidine靛蓝染料具有纯正的蓝色色调,经过纯化后,能充当食品、饮料或化妆品中的染色剂。该蓝色天然染料由于易规模生产、无毒无害、无污染等特性得到染料学者越来越广泛的关注。然而,该染料结构中存在两个伯胺基,耐光性较差,用于染料发色体时获得的染料耐晒牢度较低。此外,Indigoidine在溶剂中的溶解性较差,仅在DMF和DMSO中具有较小的溶解度,难以采用水介质实现染色。因此,将其进行结构改性有可能改善染料的溶解性和耐光稳定性,开发出具有实用价值的染料品种。
酸性染料是指在染料分子中含有磺酸根或羧酸根取代基团的水溶性染料,又称阴离子染料,能与蛋白质纤维(羊毛、蚕丝等)分子中的氨基在酸性条件下以离子键相结合,在酸性、弱酸或中性条件下适用。
一种蓝色酸性染料及其制备方法(CN201811221115.8)曾通过将Indigoidine染料与氯苄磺酸反应制得水溶性染料,对蛋白质纤维实现高效染色,提高了染料对纤维的上染率与色牢度。但该方法改性后的染料耐晒牢度依然未能达到优秀级别,仅为5~5.5级。
发明内容
本发明要解决的技术问题是提供一种耐晒型蓝色酸性染料及其制备方法,该种染料在水中具有较高的溶解度,使其能够在水体系中实现对蛋白质纤维的高效染色,提高染料对纤维的上染率与色牢度,特别是在耐晒牢度方面提升显著。
为了解决上述技术问题,本发明提供一种耐晒型蓝色酸性染料,其分子结构中含有磺酸钠基团和具有紫外线吸收功能的邻羟基苯并***结构,其结构通式如下:
作为本发明耐晒型蓝色酸性染料的改进,其结构式为如下任一:
本发明还同时提供了上述耐晒型蓝色酸性染料的制备方法,其采用Indigoidine染料与含氯水溶性苯并***紫外线吸收剂反应制得,具体包括以下步骤:
1)、将Indigoidine染料研磨后(过400目的筛)分散于水中,得染料悬浮液;
将含氯水溶性苯并***紫外线吸收剂溶于水,得紫外线吸收剂溶液;
将染料悬浮液、紫外线吸收剂溶液、作为缚酸剂的碳酸钾粉末混合后加入水热反应釜中;在(110±10)℃油浴条件下保温反应12~16hr;
所述Indigoidine染料:含氯水溶性苯并***紫外线吸收剂:碳酸钾=1:2:2的摩尔比;
所述Indigoidine染料的结构式为:
2)、向步骤1)所得的反应产物溶液中加入氯化钠直至氯化钠达到饱和状态,析出产物,过滤,并采用DMF-***法除去产物中的盐分,干燥产物,得到耐晒型蓝色酸性染料。
作为本发明制备方法的改进,在本发明的步骤1)中:
每0.01mol的Indigoidine染料配用20±5mL水,得染料悬浮液;
每0.02mol的含氯水溶性苯并***紫外线吸收剂配用40±10ml的水,得紫外线吸收剂溶液。
本发明在Indigoidine染料两个伯胺基上引入两个含有水溶性磺酸钠基团的苯并***型紫外线吸收片段(反应式如下式所示),同时改善染料的水溶性和耐光稳定性,从而开发出耐晒牢度优异的水溶性酸性染料,可应用于羊毛等蛋白质纤维的染色。
本发明在发明过程中发现:Indigoidine染料分子中引入含有紫外线吸收片段的芳环体系和增大分子量,能够提高染料分子和纤维大分子之间的范德华力,有利于提高染料对纤维的上染率和色牢度,特别是耐晒牢度提升显著。此外,在Indigoidine结构中引入磺酸基团能够提升染料水溶性,使改性后的Indigoidine染料满足酸性染料结构特点,用于蛋白质纤维染色。从理论上讲,伯胺基(-NH2)转化为仲胺基(-NH-)后,N上电子云密度提高,容易发生光氧化反应,即,日晒牢度应呈下降。但在本发明中,由于在分子中引入两个效率极高的紫外线吸收片段,可以抑制紫外线对染料的破坏,发现本发明制备所得的蓝色酸性染料耐晒牢度有了显著提升,达到了优异等级。
本发明通过在染料结构中同时引入芳环和磺酸基团能够提高染料对蛋白质纤维的亲和力与水溶性,并提高染料对蛋白质纤维的适用性。此外,Indigoidine染料结构中的伯胺基通过修饰引入两个紫外线吸收片段,显著提高了染料的耐晒牢度。本发明的染料合成工艺简单,通过Indigoidine染料与含氯水溶性苯并***紫外线吸收剂缩合即可制得。由于所开发的蓝色酸性染料对蛋白质纤维具有优异的色牢度,应用前景广阔。
具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此:
实施例1、一种耐晒型蓝色酸性染料的制备方法,依次进行以下步骤:
1)、在500mL水热反应釜中,先加入0.01mol研磨后的Indigoidine染料(400目)和20mL水,室温下搅拌形成染料悬浮液,待用;
将紫外线吸收剂溶液加入至步骤1)所得的染料悬浮液中,随后加入0.02mol碳酸钾作为缚酸剂,110℃反应16hr;
3)、反应完毕后,向反应产物溶液中加入30g(0.504mol)氯化钠固体,此时,氯化钠达到饱和状态,盐析出染料产物,过滤,所得滤饼为含盐染料;
4)、采用DMF-***法除去产物中的盐分,收集并干燥产物,具体如下:
DMF-***法:取步骤3)所得的含盐染料2g,溶解于15mL DMF中,过滤除去盐,在滤液中加入100mL无水***使染料析出,过滤,收集滤饼,于室温下干燥至恒重;得耐晒型蓝色酸性染料I。
该耐晒型蓝色酸性染料I的结构式如下:
1H NMR(400MHz,DMSO-d6):δ11.08(s,2H),10.04(s,2H),7.80(m,6H),7.18(s,2H),7.01(d,2H),6.65(d,2H),6.42(s,2H),4.03(s,2H);ESI MS(m/z,%):412.0([M-2Na]/2-,100)。
实施例2、一种耐晒型蓝色酸性染料的制备方法,依次进行以下步骤:
1)、在500mL水热反应釜中,先加入0.01mol研磨后的Indigoidine染料(400目)和25mL水,室温下搅拌形成染料悬浮液,待用;
将紫外线吸收剂溶液加入至步骤1)所得的染料悬浮液中,随后加入0.02mol碳酸钾作为缚酸剂,110℃反应12hr;
3)、反应完毕后,向反应产物溶液中加入30g(0.504mol)氯化钠固体,此时,氯化钠达到饱和状态,盐析出染料产物,过滤,所得滤饼为含盐染料;
4)、采用DMF-***法除去产物中的盐分,收集并干燥产物,得到耐晒型蓝色酸性染料II。
该耐晒型蓝色酸性染料II的结构式如下:
1H NMR(400MHz,DMSO-d6):δ11.12(s,2H),9.98(s,2H),7.73(d,2H),7.58(m,4H),7.19(s,2H),6.63(d,2H),6.42(s,2H),4.05(s,2H),2.94(m,2H),1.62(m,4H),1.33(d,6H),0.96(t,6H);ESI MS(m/z,%):468.1([M-2Na]/2-,100)。
下面通过实验来说明本发明的耐晒型蓝色酸性染料在蛋白质纤维染色中的应用。
实验1、
参照201811221115.8所述实验方法:取羊毛织物1kg,按照耐晒型蓝色酸性染料2%owf、元明粉5%owf,醋酸调节pH值为4.5~5.0,浴比1:20。
染色结束后,取出染色布样,洗涤,合并染色残液及洗涤液,定容测器吸光度,利用朗伯-比尔定律求解染料的上染率;并测定上述染色布样的耐皂洗牢度、耐干摩擦牢度、耐湿摩擦牢度、耐升华牢度、耐晒牢度。具体所得结果如表1所述。
将耐晒型蓝色酸性染料改成Indigoidine靛蓝染料,其余同上。结果见表1:染料的上染率为4.7%,染色后染色残液由蓝色变为棕色(染料被氧化所致),说明Indigoidine染料的耐氧化性能欠佳。由于Indigoidine染料水溶性差且对羊毛纤维亲和力低,所以在羊毛织物上无法染得深色,各项色牢度无法评级。
由表1可知,经修饰后,本发明染料的各项色牢度均十分优异,特别是耐光稳定性获得极大提升。本发明实施例1、2(对应染料I、II)测定的耐晒牢度均超过7级,达到优异级别,说明染料通过修饰改性后在羊毛上的耐晒牢度好,可以作为酸性染料应用于羊毛织物染色,上染率高,并且各项色牢度优异。
表1、蓝色酸性染料对羊毛织物的染色数据
实验2、对光氧化反应的抑制作用及水中溶解度
参照201811221115.8所述实验方法:配置等摩尔浓度(0.05mol/L)的Indigoidine、耐晒型蓝色酸性染料I、II的DMF溶液,在相同的光照条件下(500W汞灯)照射2小时后,根据染料最大吸收波长下吸光度的变化率计算各染料褪色率,具体数据见表2。Indigoidine、耐晒型蓝色酸性染料I、II在水中溶解度如表2所述。
表2、染料溶解度与其DMF溶液光照后的褪色率
染料 | 水中溶解度(g/L) | 褪色率(%) |
Indigoidine | 0.013 | 87.4 |
I(实施例1) | 87.5 | 0.8 |
II(实施例2) | 75.4 | 0.3 |
III(对比例1) | 108 | 3.5 |
由表2可知,经修饰后,本发明染料的耐光性能获得极大提升,长时间高强度光照后染料的褪色率极低(<1%),说明紫外线吸收片段对Indigoidine发色体的光稳定效果十分显著。此外,分子结构中引入的磺酸基赋予了染料良好的水溶性,使其满足酸性染料的应用要求。
对比例1、
选用蓝色酸性染料及其制备方法(CN201811221115.8)中染色性能和牢度最好的蓝色酸性染料III:
该水溶性蓝色染料III按照上述实验1、实验2进行检测,所得结果如表1、表2所述。
与本发明的染料I、II相比,染料III结构中缺少紫外线吸收片段,并且分子量较低,造成与纤维的亲和力偏低,耐晒牢度偏低。此外,其他各项色牢度以及耐光氧化性也明显低于染料I、II。
对比例2、
该染料相对于本发明的染料Ⅰ而言,为Indigoidine亚氨基(-NH-)和苯并***紫外线吸收片段中间多了两个亚甲基;该染料的耐晒牢度提升不明显,仅能达到6级,低于染料I的耐晒牢度(7级)一级,说明紫外线吸收片段与染料之间的连接方式会影响染料耐晒牢度。
该染料的耐水色牢度、耐干摩擦牢度、耐湿摩擦牢度、耐升华色牢度、耐光氧化性,也均略不如本发明的染料Ⅰ,约比本发明的染料Ⅰ低半级左右。
对比例3、
该染料相对于本发明的染料II而言,为将羟基邻位含有特丁基的苯并***紫外线吸收片段引入Indigoidine染料,该染料的耐晒牢度提升同样不明显,仅能达到6级,低于本发明染料II的耐晒牢度(7-8级)一级半,说明紫外线吸收片段中的烷基种类也会影响染料耐晒牢度。
该染料的耐水色牢度、耐干摩擦牢度、耐湿摩擦牢度、耐升华色牢度、耐光氧化性,也均略不如本发明的染料II;约比本发明的染料II低半级左右。
最后,还需要注意的是,以上列举的仅是本发明的若干个具体实施例。显然,本发明不限于以上实施例,还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形,均应认为是本发明的保护范围。
Claims (5)
4.根据权利要求3所述的耐晒型蓝色酸性染料的制备方法,其特征是所述步骤2)为:在步骤1)所得的反应产物溶液中加入氯化钠直至氯化钠饱和,产生析出物;采用DMF-***法除去析出物中的盐分,干燥,得到耐晒型蓝色酸性染料。
5.根据权利要求3或4所述的耐晒型蓝色酸性染料的制备方法,其特征是所述步骤1)中:
每0.01mol的Indigoidine染料配用20±5mL水,得染料悬浮液;
每0.02mol的含氯水溶性苯并***紫外线吸收剂配用40±10ml的水,得紫外线吸收剂溶液。
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