CN107200736B - 一种喹吖啶酮甜菜碱衍生物及其制备方法和应用 - Google Patents
一种喹吖啶酮甜菜碱衍生物及其制备方法和应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- -1 Quinacridone betaine derivative Chemical class 0.000 title claims abstract description 23
- 239000000049 pigment Substances 0.000 claims abstract description 38
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims abstract description 8
- 125000004103 aminoalkyl group Chemical group 0.000 claims abstract description 7
- WIWJFWANKMRGGS-UHFFFAOYSA-N 3,4-dimethyl-1,6-dioxecane-2,5,7,10-tetrone Chemical compound C1(CCC(=O)OC(C(C(C(=O)O1)C)C)=O)=O WIWJFWANKMRGGS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002270 dispersing agent Substances 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
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- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 4
- 239000012022 methylating agents Substances 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
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- BFWYZZPDZZGSLJ-UHFFFAOYSA-N 4-(aminomethyl)aniline Chemical compound NCC1=CC=C(N)C=C1 BFWYZZPDZZGSLJ-UHFFFAOYSA-N 0.000 claims description 2
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- SDHWNDQQYQOORG-UHFFFAOYSA-N 2-anilinocyclohexa-1,4-diene-1,4-dicarboxylic acid Chemical compound C1C(C(=O)O)=CCC(C(O)=O)=C1NC1=CC=CC=C1 SDHWNDQQYQOORG-UHFFFAOYSA-N 0.000 description 2
- HBBWQVPXGBHVPE-UHFFFAOYSA-N 3-(2-aminoethyl)aniline;hydrochloride Chemical compound Cl.NCCC1=CC=CC(N)=C1 HBBWQVPXGBHVPE-UHFFFAOYSA-N 0.000 description 2
- XKLXSHQEFPJNEL-UHFFFAOYSA-N 4-(aminomethyl)aniline;hydrochloride Chemical compound Cl.NCC1=CC=C(N)C=C1 XKLXSHQEFPJNEL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- 239000000853 adhesive Substances 0.000 description 1
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- 125000003545 alkoxy group Chemical group 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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Abstract
本发明涉及一种喹吖啶酮甜菜碱衍生物及其制备方法,所述的喹吖啶酮甜菜碱衍生物的结构如式(P)所示:
Description
技术领域
本发明属于有机颜料、高档涂料领域,涉及一种高档颜料喹吖啶酮系列颜料的衍生物及其制备方法。
背景技术
喹吖啶酮(quinacridone,QA)全称为喹啉并[2,3-b]-吖啶-5,12-二氢-7,12-二酮,1935年由H.Liebermann首先合成。由于其具有良好的光、热及化学稳定性,因此是一类性能优异的橙、红色系颜料。喹吖啶酮分子具有高度的共轭的大π键并能形成平面结构,使其作为有机光电材料包括有机电致发光器件、太阳能电池、场效应晶体管获得了广泛的应用。
在高性能有机颜料的生产和应用过程中,采用颜料衍生物作为分散剂来提高产品的性能有着广泛应用。如在吡咯并吡咯二酮颜料(DPP颜料)的生产过程中,采用DPP衍生物来提高产品的分散性、色力和耐溶剂性能等(US5380870,US4791204,US5973146A等);在酞菁颜料制备水性涂料、色浆、油墨和喷墨墨水的的过程中,采用酞菁颜料衍生物作为助剂会有较好的效果(CN200410048800.7,CN99810382.9,CN99111517.1,CN96111095.3,CN97198494.8等)。
在众多的QA颜料生产中,利用QA颜料衍生物作为助剂来提高QA颜料的使用性能是一种重要方法(蔡小飞,王利民,王峰等.喹吖啶酮类颜料及其功能化研究进展.染料与染色,2013,50(3):24-27)。
在喹吖啶酮颜料衍生物的制备方面,专利CN201210260009.7中介绍了一种喹吖啶酮硼酸酯衍生物及其制备方法和应用;专利CN201210377815.2中介绍了一种五苯基苯基喹吖啶酮衍生物及其在作为荧光材料方面应用;专利CN201110102802.X介绍了一种N上烷基、烷氧基或卤代烷取代,2号位上芳环基及杂环基取代的喹吖啶酮衍生物制备方法及其应用;专利CN03127617.2介绍了一系列N上取代及苯环上被取代的QA颜料衍生物的制备方法及其在有机电致发光器件中的应用;专利CN200580021864.0中介绍了一系列具有荧光性能的喹吖啶酮衍生物的制备方法。
美国专利US3386843,US6494948,US6284890,US6264733和US20020078860中介绍了一种2,9-二磺酰胺基喹吖啶酮及2,9-二磺酸钠喹吖啶酮的制备方法。
发明内容
不同于以上专利中所述的喹吖啶酮衍生物及其制备方法,本发明提供一种具有两性表面活性剂性质的喹吖啶酮颜料衍生物及其制备方法。
本发明所涉及的喹吖啶酮颜料衍生物具有良好的水溶性、表面活性和乳化分散能力,可以用作喹吖啶酮颜料粗品后处理加工时的添加剂,也可以用作喹吖啶酮颜料制备色浆、涂料时的分散剂和乳化剂,所制备的喹吖啶酮颜料分散剂色力高,分散性和应用性能好。
本发明所涉及的喹吖啶酮颜料甜菜碱衍生物制备方法简单,合成条件温和,原料便宜易得,反应物收率高。
本发明的目的之一在于提供一种可以用于喹吖啶酮颜料分散体的喹吖啶酮甜菜碱衍生物。本发明的喹吖啶酮甜菜碱衍生物,其具有如式(P)所示的结构:
其中,m为1或2。
本发明的目的之二是提供此喹吖啶酮颜料甜菜碱衍生物的制备方法,包括如下步骤:
第1步,在乙腈做溶剂和碳酸氢钾做缚酸剂的情况下,利用卤代烃类甲基化试剂,由式(I)所示的化合物制备化合物(II),m为1或2;
第2步,氯乙酸钠在乙醇做溶剂和氢氧化钠溶液做催化剂的情况下,与化合物(II)反应,回流加热制备目标化合物(P),m为1或2;
上述制备方法中,式(I)所示的化合物通过以下两种方法中的任意一种制备得到:
第1种:以式(III)所示的胺烷基取代苯胺和丁二酰丁二酸二甲酯为原料,先经过脱水反应,再在聚磷酸的作用下进行环合反应,最后再用间硝基苯磺酸钠氧化,得到式(I)所示的胺烷基取代喹吖啶酮,m为1或2;
第2种:用对胺甲基苯胺与丁二酰丁二酸二甲酯作为反应原料制备。
所述的第1步中,卤代烃类甲基化试剂选自碘甲烷或者溴乙烷。
所述的第1步中,式(I)所示的化合物与卤代烃类甲基化试剂的摩尔比范围是1:3~5,更优选是1:4;反应时间范围是2~6h,更优选是4h。
所述的第2步中,氯乙酸钠和式(I I)所示的化合物摩尔比范围是1:1~3,更优选是1:2,反应过程中反应温度控制在60~80℃,反应过程体系的pH控制在8~8.5。
本发明的目的之三是提供式(P)所示的结构的喹吖啶酮甜菜碱衍生物在制备喹吖啶酮颜料粗品后处理加工时的添加剂、色浆、涂料或者水性墨中的应用。
有益效果
本发明所设计和合成出一系列尚未报道的喹吖啶酮甜菜碱衍生物,并且研究了合成此类衍生物的方法学。本发明所制备的喹吖啶酮甜菜碱衍生物(P)在水中有良好的溶解性和表面活性,可以用作喹吖啶酮颜料粗品后处理加工时的添加剂,也可以用作喹吖啶酮颜料制备色浆、涂料、水性墨时的分散剂和乳化剂,所制备的喹吖啶酮颜料分散剂色力高,分散性和应用性能好。
具体实施方式
实施例1
(1)利用对氨基苄胺盐酸盐和丁二酰丁二酸二甲酯制备出2,9-二胺甲基喹吖啶酮(Ⅰ-1),制备方法如专利US3386843和专利CN98112582.4中所述。将对氨基苄胺盐酸盐(0.2mol,31.6g)和丁二酰丁二酸二甲酯(22.8g,0.1mol)加入到乙醇(200ml)和浓盐酸(10ml,37%)的混合溶剂,在高温高压反应釜中加压,90℃反应4小时,冷却后,过滤,水洗,甲醇重结晶得到2,5-二-(4’-胺甲基)苯胺基-3,6-二氢对苯二甲酸(36.74g,0.09mol)。将2,5-二-(4’-胺甲基)苯胺基-3,6-二氢对苯二甲酸(40.82g,0.1mol)在多聚磷酸(200g,117%磷酸)下,110-135℃缩合得到2,9-二胺甲基-6,13-二氢喹吖啶酮(37.2g,0.1mol),2,9-二胺甲基-6,13-二氢喹吖啶酮(37.2g,0.1mol)进一步在间硝基苯磺酸钠(45.2g,0.2mol)、氢氧化钾(16g,0.285mol)和去离子水(500ml)下回流氧化2小时,用稀盐酸(10%)酸化中和,水洗过滤,得到2,9-二胺甲基喹吖啶酮(Ⅰ-1)(31.5g,0.085mol)。产物(Ⅰ-1)氢核磁共振检测结果,1HNMR(CDCl3,500MHz)δ(ppm):2.0(s,2H),3.01(s,2H),4.01(m,2H),4.5(s,1H),6.44(s,1H),6.75(s,1H),7.01(s,1H),7.25(s,1H)。
(2)在装有冷凝管的四口烧瓶中,加入乙腈(50ml),边搅拌边加入2,9-二胺甲基喹吖啶酮(Ⅰ-1)(0.01mol,3.70g),再加入碘甲烷(5.68g,0.04mol),碳酸氢钾5g,加料完毕后,加热至80℃,回流4小时,冷却至室温,旋转蒸发,回收乙腈,再加入水中,过滤,得到产物(Ⅱ-1)。
(3)将产物(Ⅱ-1)(4.26g,0.01mol)就加入到30ml乙醇中,加热至80℃,搅拌。同时在滴液漏斗中缓慢加入氯乙酸钠(2.33g,0.02mol)的水溶液,同时滴加氢氧化钠溶液维持体系pH值为8-8.5,继续搅拌反应一段时间,反应完成后减压蒸馏除去溶剂。粗产物用乙醇重结晶,抽滤等红色滤饼,真空干燥后即为产物(P-1),共制得产物(P-1)4.6g,此步反应收率为84%。
产物(P-1)氢核磁共振检测结果,1HNMR(CDCl3,500MHz)δ(ppm):3.3(s,6H),4.0(s,1H),4.35(m,2H),4.5(d,2H),6.44(s,1H),6.75(s,1H),7.01(s,1H),7.25(s,1H)。
实施例2
(1)利用间氨基苯乙胺盐酸盐制备出3,8-二胺乙基喹吖啶酮(Ⅰ-2),制备方法同实施例1.
(2)在装有冷凝管的四口烧瓶中,加入乙醇(30ml),加热至70℃,边搅拌边加入3,8-二胺乙基喹吖啶酮(Ⅰ-2)(0.01mol,3.98g),再加入碘甲烷(5.68g,0.04mol),碳酸氢钾5g,加料完毕后,加热至80℃,回流4小时,冷却至室温,旋转蒸发,回收乙腈,再加入水中,过滤,得到产物(Ⅱ-2)。
(3)将产物(Ⅱ-2)(4.54g,0.01mol)就加入到30ml乙醇中,加热至80℃,搅拌。同时在滴液漏斗中缓慢加入氯乙酸钠(2.33g,0.02mol)的水溶液,同时滴加氢氧化钠溶液维持体系pH值为8-8.5,继续搅拌反应一段时间,反应完成后减压蒸馏除去溶剂。粗产物用乙醇重结晶,抽滤等红色滤饼,真空干燥后即为产物(P-2),共制得产物(P-2)5.4g,此步反应收率为89.4%。
产物(P-2)氢核磁共振检测结果,1HNMR(CDCl3,500MHz)δ(ppm):2.99(t,2H)3.3(s,6H),3.57(t,2H),4.0(s,1H),4.35(s,2H),6.42(s,1H),6.58(s,1H),6.75(s,1H),7.41((s,1H)。
实施例3
如实施例2,先利用间氨基苯乙胺盐酸盐制备出3,8-二胺甲基喹吖啶酮(Ⅰ-3)。然后产物Ⅰ-3依次在乙腈溶剂中进一步与碘甲烷反应,和在乙醇中与氯乙酸钠反应,制得产物P-3,收率84.3%。
产物(P-3)氢核磁共振检测结果,1HNMR(CDCl3,500MHz)δ(ppm):3.3(s,6H),4.0(s,1H),4.35(m,2H),4.5(d,2H),6.36(s,1H),6.52(s,1H),6.75(s,1H),7.33(s,1H)。
实施例4
实验方法如实施例3,所不同的是,在第二步反应中用溴乙烷取代碘甲烷,最终得产物P-4如下图所示。
实施例5
实验方法如实施例3,所不同的是,在第一步反应中所用药品为对氨乙基苯胺,在第二步反应中用溴乙烷,最终所得产物P-5。
性能检测
1.C.I.颜料红122水性乳液的配制及性能测试
将37gC.I.颜料红122,3g以上实施例和对照例的超分散剂和60g的去离子水加入玻璃瓶中,密封好后,放入震荡仪中震荡3小时,然后进行各项性能测试。
2.粘度测试
在25℃下用旋转粘度计(NDJ-1,上海平轩科学仪器有限公司有)测各个分散剂所制备的水性颜料乳液的粘度。
3.色力测试
取20g水性颜料乳液加入到30g的含粘合剂的涂料印花用白浆中,搅拌混合均匀后,用印花刮刀在白色棉织物上进行涂料印花实验。待印花织物自然晾干后,用Datacolor测色配色仪测试K/S值,并以HPD296的样品为标准进行比较。
4.乳液高温稳定性实验
取20ml颜料红122水性乳液至25ml试管中,密封好试管口,将试管放在烘箱中,并保持温度为60℃,静置2周,2周后取出试管内最上层2ml溶液检测乳液的固含量,并与原乳液固含量进行比较。
其中,S1为静置后试管中上层乳液固含量;
S0为原乳液固含量
5.乳液冻融稳定性实验
取20ml颜料红122水性乳液至25ml试管中,密封好试管口,将试管放在冰箱中,并保持温度为-5℃,放置1周,1周后取出试管,并在40℃解冻,然后40℃静置1周后,取试管内上层2ml溶液检测乳液的固含量,并与原乳液固含量进行比较。
其中,S1为经冻融后试管中上层乳液固含量;
S0为原乳液固含量
表1产品P-1制备颜料红122水性乳液的性能对比结果
表2对照产品水性乳液的性能对比结果
Claims (8)
4.根据权利要求3所述的喹吖啶酮甜菜碱衍生物的制备方法,其特征在于:式(III)所示的胺烷基取代苯胺为对胺甲基苯胺。
5.根据权利要求2所述的喹吖啶酮甜菜碱衍生物的制备方法,其特征在于:所述的第1步中,卤代烃类甲基化试剂选自碘甲烷或者溴乙烷。
6.根据权利要求2所述的喹吖啶酮甜菜碱衍生物的制备方法,其特征在于:所述的第1步中,式(I)所示的化合物与卤代烃类甲基化试剂的摩尔比范围是1:3~5;反应时间范围是2~6h。
7.根据权利要求2所述的喹吖啶酮甜菜碱衍生物的制备方法,其特征在于:所述的第2步中,氯乙酸钠和式(II)所示的化合物摩尔比范围是1:1~3,反应过程中反应温度控制在60~80℃,反应过程体系的pH控制在8~8.5。
8.权利要求1所述的喹吖啶酮甜菜碱衍生物在用作喹吖啶酮颜料粗品后处理加工时的添加剂,或用作喹吖啶酮颜料制备色浆、涂料、水性墨时的分散剂和乳化剂的应用。
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