CN109535095B - 适用于蚕丝的芳伯胺荧光增白剂及其制备方法 - Google Patents
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- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
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Abstract
本发明公开了一种适用于蚕丝的芳伯胺荧光增白剂,为荧光增白剂P‑1、荧光增白剂P‑2。本发明还同时提供了上述2种芳伯胺荧光增白剂的合成方法:于惰性气体保护下,RF‑1/RF‑2、无水碳酸钾、对苯二胺以及溶剂先于冰浴条件下反应50~70min,再于室温遮光反应22~24h;所得反应产物经后处理,得荧光增白剂P‑1/荧光增白剂P‑2。本发明将对苯二胺引入反应性二苯乙烯荧光增白剂两端,从而合成两个新型水溶性芳伯胺荧光增白剂P‑1、P‑2,通过Mannich反应修饰的方法以共价键结合到蚕丝上;该方法染色条件温和、节能环保,并且能够从根本上解决蚕丝纤维的耐湿处理牢度问题。
Description
技术领域
本发明涉及一种适用于蚕丝的芳伯胺荧光增白剂及其制备方法。
背景技术
蚕丝是由熟蚕结茧时分泌丝液凝固而成的连续长纤维,蚕丝外观美丽轻盈,质地柔软平滑,具有良好的吸湿、透气性能,在高档纺织品面料中占有重要地位。然而,蚕丝纤维中含有少量黄色色素,即使漂白处理后仍然带有部分黄光,影响品质。
荧光增白剂是“染料索引”中的一个类别,也可认为是一种“白色染料”。荧光增白剂能够吸收肉眼不可见的紫外线(330-380nm),使分子进入激发态,激发态分子为了返回到低能态,就会将能量以400-480nm的蓝色荧光方式释放。由于纺织品、纸张、塑料等材料通常会吸收少量450-480nm左右的蓝色光从而造成白色材料蓝光不足,因此在视觉上会产生微黄色的感觉。荧光增白剂作用于这些材料后会吸收紫外线并发射出与黄光互补的蓝色荧光,从而达到增白增亮的效果。荧光增白剂作为一种高附加值的精细化学品广泛应用于纺织、洗涤和造纸等行业。荧光增白剂应用于纺织行业有70多年的历史,它可以有效改善织物的光学品质,提高织物附加值。但是,市场上适用于蚕丝的荧光增白剂品种较少,并且存在耐洗牢度差等问题。
蚕丝中含有大量的酪氨酸残基,这些酪氨酸残基能够与醛类物质、芳伯胺化合物在温和的条件下发生三组份反应,使三种物质通过共价键牢固结合,这类反应称为Mannich反应,可用于蚕丝修饰改性。
发明内容
本发明要解决的技术问题是提供一种能与蚕丝形成牢固共价键结合的反应性荧光增白剂及其制备方法。
为了解决上述技术问题,本发明提供一种适用于蚕丝的芳伯胺荧光增白剂(即,含芳伯胺基团的荧光增白剂,能与蚕丝通过Mannich反应形成牢固共价键结合的反应性荧光增白剂):为荧光增白剂P-1、荧光增白剂P-2;
本发明还同时提供了上述适用于蚕丝的芳伯胺荧光增白剂的制备方法,包括如下步骤:
于冰浴条件下,先在容器内放入RF-1(CAS:33963-93-8)或者RF-2(CAS:2116527-08-1),以及放入无水碳酸钾,对容器进行惰性气体(例如氮气)置换后,在惰性气体保护和搅拌条件下向容器内加入对苯二胺以及溶剂进行反应,先于冰浴条件下反应50~70min,再于室温(15~25℃)遮光反应22~24h;
RF-1/RF-2:无水碳酸钾:对苯二胺=1:2:4的摩尔比;
反应结束后抽滤(除盐),所得滤液加入丙酮析出固体,将析出物经冲洗除去过量的对苯二胺,重结晶,得荧光增白剂P-1/荧光增白剂P-2;
RF-1的结构式为:
作为本发明的适用于蚕丝的芳伯胺荧光增白剂的合成方法的改进:
所述溶剂为DMF;采用乙酸乙酯进行冲洗,利用乙醇/水=10:1体积比的混合液进行重结晶。
本发明将对苯二胺引入反应性二苯乙烯荧光增白剂两端,合成两个新型水溶性芳伯胺荧光增白剂P-1、P-2,通过Mannich反应修饰的方法以共价键结合到蚕丝上。该方法染色条件温和、节能环保,并且能够从根本上解决蚕丝纤维的耐湿处理牢度问题。
本发明利用Mannich反应将芳伯胺荧光增白剂(P-1、P-2)与蚕丝纤维通过C-N桥基牢固结合的染色方法的反应式如下所示:
本发明根据构效关系设计合成了两种荧光增白剂,通过Mannich反应修饰的方法上染蚕丝,应用性能结果如下:
(1)以两种反应性荧光增白剂为原料,分别键合对苯二胺合成2种芳伯胺荧光增白剂P-1和P-2。用质谱、傅立叶红外光谱和核磁氢谱对最终产物进行了表征,确定P-1和P-2的结构。
(2)通过紫外-可见吸收光谱和荧光发射光谱,确定了荧光增白剂P-1和P-2最大吸收波长分别为353nm和343nm,激发波长分别为431nm和425nm,荧光激发强度分别为5.5×104和1.5×104。
(3)研究了两种荧光增白剂不同用量对白度的影响,并对比了处理前后的反射率和UPF值,结果表明:经过相同处理,P-1可以使得蚕丝织物蓝光白度由67.59提高到73.28,DMF剥色后织物蓝光白度由对比样的66.42提高到71.61;P-2使得蚕丝织物蓝光白度提高到74.32,DMF剥色后织物蓝光白度为73.70;经过0.5%owf的荧光增白剂P-1和P-2整理后,蚕丝织物的UPF值由原来的10.99分别提高到34.38和39.21。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细说明。
图1是荧光增白剂p-1的合成路线图;
图2是P-1的质谱图;
图3是P-1的红外光谱图;
图4是荧光增白剂P-1的核磁氢谱谱图;
图5是P-1的紫外吸收-荧光发射光谱图;
图6是荧光增白剂P-2的合成路线图;
图7是P-2的质谱图;
图8是P-2的红外光谱图;
图9是荧光增白剂P-2的核磁氢谱图;
图10是P-2的紫外吸收-荧光发射光谱图;
图11是P-1修饰蚕丝的反射率曲线对照图;
图12是P-2修饰蚕丝的反射率曲线对照图;
图13是荧光增白剂用量与白度的关系图;
图14是Mannich反应修饰蚕丝的透过率曲线。
具体实施方式
实施例1、荧光增白剂P-1,
荧光增白剂P-1的合成路线如图1所示,其制备方法具体如下:
在冰浴条件下,称取RF-1(CAS:33963-93-8)(5.41g,5mmol)、无水碳酸钾(1.39g,10mmol)于250mL三口烧瓶中,氮气置换后(抽真空/氮气置换反复3次,从而除氧除水蒸气)后,在N2保护和搅拌条件下加入对苯二胺(2.16g,20mmol),然后加入30mL无水DMF作为溶剂进行反应,反应1h后撤去冰浴,室温(15~25℃)遮光反应23h;反应结束后抽滤除盐,所得滤液加入丙酮90ml使得固体析出,静置0.5h后过滤,所得滤饼用乙酸乙酯(10ml×3)冲洗除去过量的对苯二胺,所得滤饼经重结晶(利用乙醇/水=10:1体积比的混合液进行重结晶)后,得产物P-1。
荧光增白剂P-1的结构表征与分析:
1、荧光增白剂P-1的质谱分析
图2为荧光增白剂P-1的质谱谱图,该化合物在m/z 1081.19处有强的[M-H]-准分子离子峰,这是产物失去一个H后得到的分子量,在m/z 1147.04处的离子峰,这是产物3个磺酸基变为磺酸钠然后失去一个H所得到的分子量,在m/z 562.28处的离子峰,是产物2个磺酸基变为磺酸钠然后失去2个H后得到的分子量,在m/z 540.30处有很强的[M-2H]2-/2分子离子峰,这是产物失去两个H后得到的分子量,在m/z 367.31处有很强的[M-4H+Na]3-/3分子离子峰,这是产物3个磺酸基变为磺酸钠然后失去3个H所得到的分子量,与荧光增白剂P-1的理论相对分子量1082.17相符。
2、荧光增白剂P-1的傅立叶红外光谱分析
图3为P-1的红外光谱图,3439cm-1为-N-H的伸缩振动峰,1602cm-1为-NH的面外弯曲振动峰,1176cm-1、1034cm-1为磺酸基中的-S=O的伸缩振动峰,1492cm-1为苯环上C=C的骨架振动峰,1393cm-1为烯烃上-C-H的弯曲振动峰,1356cm-1为-C-N的伸缩振动峰,由此证明苯环、氨基、磺酸基等官能团的存在,其特征峰与P-1的结构相符合。
3、荧光增白剂P-1的核磁共振氢谱分析
图4为荧光增白剂P-1的核磁氢谱谱图。图中δ7.93上的双峰为1号和2号上的氢,由于受到吸电子性强的磺酸基的影响,其化学位移处于最低场;δ7.67上的单峰为9号氢所出的峰,其在苯环上没有相邻氢的影响;δ7.29上的双峰为11号氢所出的峰,而δ7.07上的双峰为10号氢所出的峰,受邻位胺基供电性的影响,10号氢处于高场;δ7.01和δ6.86上的双峰为3号氢和4号氢所出的峰;δ6.49上的双峰为7号和8号氢所出的峰,δ6.13上的双峰为5号和6号氢所出的峰,受伯胺供电子性的影响,5号和6号氢处于高场;δ4.93和δ5.10上的峰是12号氢和12’号氢所出的峰;胺基为活泼氢,其出峰在δ4.43和δ4.16位置。
荧光增白剂P-1的氢质子归属如下表1所示。
表1、荧光增白剂P-1的氢质子归属
4、荧光增白剂P-1的紫外吸收-荧光发射光谱分析
图5为P-1的紫外可见-荧光发射光谱图,200-600nm的曲线表示荧光增白剂的紫外可见吸收曲线,其纵坐标表示为吸光度/摩尔浓度所得的激发强度,400-600nm的曲线为荧光增白剂的荧光发射曲线,纵坐标为其荧光发射强度。从图5可以看出,P-1的紫外可见吸收光谱在250-400nm之间具有二苯乙烯-均三嗪型荧光增白剂特有的马鞍峰,这就说明荧光增白剂P-1具有顺反异构体,在353nm波峰处的紫外吸收为荧光增白剂的反式异构体的吸收峰,是具有荧光特性的部分。再以353nm为激发波长,获得最大荧光发射波长为431nm,斯托克斯位移λ=78nm,可以说明荧光增白剂P-1具有吸收紫外线并转换为蓝色荧光的性能,这主要是因为荧光增白剂P-1具有较好的平面性和共轭体系。P-1发出的蓝色荧光可以与蚕丝织物上的黄色互补为白光,起到使蚕丝织物更白、更亮的作用。
实施例2、荧光增白剂P-2
荧光增白剂P-2的合成路线如图6所示,其制备方法具体如下:
在冰浴条件下,称取RF-2(CAS:2116527-08-1)(5.24g,0.005mol)、无水碳酸钾(1.39g,0.01mol)于250mL三口烧瓶中,氮气置换后(抽真空/氮气置换反复3次,从而除氧除水蒸气)后,在N2保护和搅拌条件下加入对苯二胺(2.16g,0.02mol),再加入30mL无水DMF作为溶剂进行反应,反应1h后撤去冰水浴,室温遮光反应23h。反应结束后,将反应所得溶液进行过滤除盐,所得滤液加入丙酮90ml使得固体析出,静置0.5h后再次抽滤,所得滤饼用乙酸乙酯(10ml×3)冲洗除去过量的对苯二胺,所得滤饼经重结晶(利用乙醇/水=10:1体积比的混合液进行重结晶)后得产物P-2。
荧光增白剂P-2的结构表征与分析
1、荧光增白剂P-2的质谱分析:
图7为荧光增白剂P-2的质谱图,由图可知,该化合物在m/z 1047.59处有很强的[M-H]-准分子离子峰,这是产物失去一个H后得到的分子量,在m/z 1069.56处有[M-2H+Na]-离子峰,这是产物一个磺酸钠盐失去1个H后得到的分子量,与荧光增白剂P-1的理论相对分子量1048.46符合。
2、荧光增白剂P-2的傅立叶红外光谱分析
图8为荧光增白剂P-2的红外光谱谱图,从图中可以看出,3445cm-1,3330cm-1为-N-H的伸缩振动峰,1602cm-1为-NH的面外弯曲振动峰,2929cm-1为烷基中-C-H的伸缩振动峰,1658cm-1为烯烃-C=C-的伸缩振动峰,1492cm-1为苯环上-C=C-的骨架振动峰,862cm-1为苯环上-C-H面外弯曲振动峰,1179m-1、1024cm-1为磺酸基中的-S=O的伸缩振动峰,由此证明苯环、烷基、烯烃双键、氨基和磺酸基等官能团的存在,其特征峰与P-2的结构相符合。
3、荧光增白剂P-2的核磁共振氢谱分析
图9为荧光增白剂P-2的核磁氢谱谱图。图中δ8.07的单峰为5号氢所出的峰,其相邻碳上没有氢,受到邻位强吸电性的磺酸基的影响,其化学位移在最低场;δ7.72的双峰为7号氢上的峰,δ7.50上的峰为6号氢上的峰,受邻位胺基的影响,6号氢位于高场;δ7.81上的双峰为3号和4号氢所出的峰,δ6.58上的氢为1号和2号氢所出的峰,由于受到胺基强供电性的影响,邻位的1号和2号氢移向高场;δ5.14上的峰是8号氢和9号氢所出的峰,δ4.22的单峰为18号磺酸基上的氢;δ4.84为14和15号氢所出的峰,δ4.50为16号氢所出的峰,δ4.03为17号氢所出的峰,δ3.19为13号氢所出的峰;δ3.59的多重峰为10号氢所出的峰,δ2.04和δ0.87为受阻胺上11号位所出的峰,受平伏键和直立键的干扰,其化学位移存在差别,δ1.31出的峰为12号位4个甲基上24个氢所出的峰。
荧光增白剂P-2的氢质子归属,如下表2所示。
表2、荧光增白剂P-2的氢质子归属
4、荧光增白剂P-2的紫外吸收-荧光发射光谱分析
图10为荧光增白剂P-2的紫外吸收-荧光发射光谱图,200-600nm的曲线表示荧光增白剂的紫外可见吸收曲线,其纵坐标表示为吸光度/摩尔浓度所得的激发强度,400-600nm的曲线为荧光增白剂的荧光发射曲线,纵坐标为其荧光发射强度。从图10中可以看出,在P-2的紫外吸收光谱图中343nm处为荧光增白剂的反式异构体的吸收峰,是具有荧光特性的部分。以343nm为激发波长,得到最大荧光发射波长为425nm,斯托克斯位移λ=82nm,可以说明荧光增白剂P-2具有吸收紫外线并转换为蓝色荧光的性能,P-2发出的蓝色荧光可以与蚕丝织物具有的黄光进行互补为白光,起到使蚕丝织物更白、更亮的作用。
综上:通过紫外吸收-荧光发射光谱看出两种荧光增白剂P-1和P-2的最大吸收波长分别为353nm和343nm,最大荧光发射波长分别为431nm和425nm,其荧光发射强度分别为5.5×104和1.5×104。
本发明涉及的Mannich反应修饰、剥色工艺如下:
(1)Mannich反应修饰工艺
Mannich反应修饰法工艺配方及条件如表3所示:
表3、Mannich反应修饰法修饰配方及条件
在恒温震荡水浴锅中使用Mannich反应修饰法对蚕丝织物进行染色,其浴比为1:50,处理温度为30℃,染料与甲醛的摩尔比为1:3,经过10h的震荡处理,取出蚕丝布样进行水洗,水洗完成后进行DMF剥色处理。
(2)剥色工艺
剥色工艺配方及条件如表4所示:
表4、剥色配方及条件
剥色工艺采用的剥色剂为DMF,因为染料和蚕丝之间通过Mannich反应以共价键结合,使用DMF剥色不会破坏共价键。而染料和蚕丝之间的离子键则在DMF溶液中解离,温度越高,解离效果越明显。
实验1、
1、荧光增白剂用量对蚕丝白度的影响
为了研究两种荧光增白剂(荧光增白剂P-1与P-2)的最佳用量,以不同用量的荧光增白剂用Mannich反应修饰的方法上染蚕丝,以蓝光白度为指标对实验进行优化,检测方法为GB/T23979.1-2009(荧光增白剂增白强度和色光的测定棉织物染色法),数据如表5所示。
表5、荧光增白剂用量对蚕丝蓝光白度的影响
注:%owf代表荧光增白剂对织物蚕丝的重量百分比。
荧光增白剂的增白效果受到荧光增白剂用量的影响很大。在一定的范围内,随着用量的增加,荧光增白剂的所发射的蓝色荧光强度也会增加。当荧光增白剂的用量达到最佳使用量的时候,其发射出的蓝色荧光的强度刚好与蚕丝织物的黄光相同,达到了最好的增白效果。但当荧光增白剂的用量继续增加时,其发射的蓝色荧光强度大于蚕丝织物所能吸收的蓝色荧光强度,织物所发出的蓝光就强于黄光,反而会使织物的白度下降。从表5可以看出,当修饰后的蚕丝水洗干燥后,荧光增白剂P-1的用量在0.75%owf时,白度最高(73.28);P-2的用量在0.25%owf时,织物的白度最高(75.31)。为了将未共价键合到蚕丝上的荧光增白剂剥离下来,采用高温进行剥色,剥色的同时会造成蚕丝的损伤而白度下降,但是为了验证单纯荧光增白剂修饰对蚕丝白度的影响,本实验以荧光增白剂用量为0的蚕丝作为对照,结果表明:剥色后荧光增白剂P-1的用量在0.25%owf时,白度最高(71.61);荧光增白剂P-2的用量在0.75%owf时,蚕丝的白度最高(73.70)。
2、荧光增白修饰后织物反射率
图11为原蚕丝及其经过皂洗、剥色处理与P-1修饰蚕丝剥色后的反射率曲线。从图11可以看出,皂洗后对比样的反射率与原蚕丝相比差异不大,这说明了蚕丝经过60℃皂洗对蚕丝的荧光白度影响不是很大。而经过100℃DMF剥色后对比样蚕丝的反射率曲线较原蚕丝下降了许多,这说明高温的剥色会使蚕丝白度受损。使用了荧光增白剂P-1修饰的蚕丝织物在420-480nm的波段范围内,有明显的一处突起峰,在这个波段范围内,经过P-1修饰的蚕丝织物的反射率高于原蚕丝和对比样,这是因为荧光增白剂P-1能够吸收不可见的紫外线发射出可见的蓝光,增加了420-480nm范围内的反射率,从而起到了增加白度的效果。在400-420nm范围内,随着荧光增白剂用量的增加,反射率曲线是下降的,这一部分对蚕丝的白度增加是不利的。虽然在420-480nm范围内用量为0.25%owf时反射率增加的不是最多,但是从400-420nm范围内可以看出P-1的用量为0.25%owf的时候反射率下降是最少的。因此,从综合考虑两部分的差值考虑,P-1的用量在0.25%owf时,可以起到相对较好的增白效果。
图12为原蚕丝及其经过皂洗、剥色处理与P-2修饰蚕丝剥色后的反射率曲线。从图12中可以看出,经过P-2修饰后的蚕丝在420-500nm范围内有明显的凸起峰,同样,皂洗完成后的对比样反射率相较于原蚕丝降低了一点,这说明了蚕丝经过皂洗后白度会有所降低。而经过DMF剥色后的对比样白度较原蚕丝下降了许多。使用了荧光增白剂P-2的蚕丝织物明显在400-480nm的波段范围内,有明显的一处突起峰,在这个波段范围内,1%owf修饰的凸起峰最高,0.5%owf修饰的凸起峰最低,而在400-420nm范围内,0.25%owf修饰的反射率曲线最高,2%owf修饰的反射率曲线最低。与原蚕丝相比,P-2的修饰使得交点右边的反射率提高,而使得交点左边的反射率降低。因此,从综合考虑两部分的差值考虑,P-2的用量在0.75%owf时,可以起到相对较好的增白效果。
本发明找到荧光增白剂P-1和P-2对蚕丝的适宜用量,获得荧光增白剂用量对蚕丝白度的影响规律,如图13所示,Mannich反应修饰后,P-1用0.25%owf的用量蚕丝白度最高,P-2用0.75%owf的用量蚕丝白度最高;但当近一步剥色后,0.25-0.75%owf用量的白度变化不大,其白度最大差值仅为0.29和1.00。因此,统一选择0.5%owf的用量来研究荧光增白剂P-1和P-2的其它应用性能。
3、荧光增白修饰蚕丝后织物的UPF
图14为荧光增白剂经Mannich反应修饰蚕丝的透过率曲线。P-1和P-2用量都为0.5%owf,30℃修饰,60℃皂洗,100℃DMF剥色,其中对比样也是经过同样Mannich反应修饰法,而不加入荧光增白剂。从图中可以看出,经过荧光增白剂处理后,在300-400nm范围内,蚕丝的透过率下降很多,而且基本上在5%以下,说明修饰荧光增白剂后,蚕丝的紫外线防护性能得到了明显的改善,其具体数据如表6所示。
表6、处理织物的UPF值
从图14和表6中可以发现,经过甲醛处理的蚕丝的UPF值比原蚕丝要高3.43,这是因为甲醛使蚕丝收缩,布更紧密,紫外透过率变小,UPF值变高。而经过P-1和P-2(0.5%owf)修饰的蚕丝UPF值提升到了34.38和39.21,较原蚕丝有明显的提升,说明荧光增白剂提高了蚕丝的白度的同时,也使得蚕丝的紫外线防护性能得到了提高。
对比实验:
将上述T1和T2、以及RF-1、RF-2按照上述实验方法进行检测,与P-1和P-2的性能对比如下表7所示。
表7
非反应性荧光增白剂T1、T2和P-1、P-2间只有氨基的微小差别,但按Mannich反应修饰法染色后,再用DMF剥色,蓝光白度差异很大,P-1、P-2固色率较好,T1、T2被全部剥除。即:T1和T2荧光增白剂处理蚕丝织物后,白度有所提升,但DMF剥色后,白度恢复到未处理前的白度值。而P-1和P-2处理后蚕丝的白度显著提高,DMF剥色后白度变化不大。
RF-1和RF-2作为一氯均三嗪型反应性荧光增白剂,可以参照活性染料染色方法与蚕丝反应形成共价键合,但其反应温度较高(90℃),与室温可反应的P-1和P-2相比,能耗更高,并且从剥色前后的白度方面看也缺乏优势(见表7)。
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 (3)
3.根据权利要求2所述的适用于蚕丝的芳伯胺荧光增白剂的合成方法,其特征是:
所述溶剂为DMF;采用乙酸乙酯进行冲洗,利用乙醇/水=10:1体积比的混合液进行重结晶。
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