CN117384512A - 基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法 - Google Patents
基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法 Download PDFInfo
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Abstract
本发明属于高分子材料技术领域,涉及一种基于碳量子点修饰部分异氰酸酯基的无溶剂型反‑斯托克斯光变光油的制备方法,包括(1)植物多糖类物质制备碳量子点、(2)碳量子点亲电加成修饰部分异氰酸酯基团、(3)含碳量子点异氰酸酯用于制备聚(氨酯‑乙烯醇‑丙烯酸酯)预聚物、(4)反‑斯托克斯光变光油的制备。本发明所制得的光油经荧光光谱表征具备较好的上转换发光特性,可以广泛应用于特种印刷、防伪、信息传递等技术领域;此外,由于在制备聚(氨酯‑乙烯醇‑丙烯酸酯)预聚物阶段即完成了溶剂的去除,因此成品的反‑斯托克斯光变光油几乎不含有任何溶剂残留,满足当前环保需要,具备较好的市场前景。
Description
技术领域
本发明属于高分子材料技术领域,涉及聚(氨酯-乙烯醇-丙烯酸酯)预聚物,尤其涉及一种基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法。
背景技术
有消息称,美国科学家在2007年首次发现碳量子点具备上转换荧光的特性,他们用800nm飞秒脉冲激光激发碳量子点,结果发现其发出可见光;之后,众多研究小组也观察到由完全不同的合成途径合成出来的碳量子点具有转化荧光的性能。例如,S.Zhu,J.Zhang,X.Liu,B.Li,X.Wang,S.Tang,Q.Meng,Y.Li,C.Shi,R.Hu,B.Yang,RSC Adv.2012,2,12-23.报道了通过一步碱或酸辅助超声处理直接从葡萄糖合成单分散的水溶性荧光碳量子点,经测试发现长波长光在700~1000nm激发后的的碳量子点具有的光致发光光谱特性,并且上转换发射位于450~750nm的范围内。
若是将碳量子点上转换荧光特性应用于高分子材料技术领域,通过其表面众多活性基团改性或修饰预聚体,或许可以制备一款反-斯托克斯光变光油。
发明内容
本发明的目的在于公开一种基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,包括(1)植物多糖类物质制备碳量子点、(2)碳量子点亲电加成修饰部分异氰酸酯基团、(3)含碳量子点异氰酸酯用于制备聚(氨酯-乙烯醇-丙烯酸酯)预聚物、(4)反-斯托克斯光变光油的制备。
技术方案
一种基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,包括如下步骤:
(1)植物多糖类物质制备碳量子点
将植物多糖、金属氧化物装入管式炉内,连接N2并置换管内空气,管内气压1.0~4.5GPa,N2流速0.2~6.0cm3/min,升温至240~870℃维持2~10h,冷却至室温并确保处于N2氛围中,去离子水冲反应产物,抽滤至滤液呈中性,收集滤饼用去离子水充分分散,在4000r/min转速离心10~30min,收集管底固体物质经干燥得到碳量子点;
所述植物多糖是葡聚糖、木聚糖、甘露聚糖,优选葡聚糖;
所述金属氧化物是γ-Al2O3、α-FeOOH、Mn/TiO2、Cr/TiO2,优选Mn/TiO2;
所述植物多糖与金属氧化物的反应物料比是10~20g:0.01mg;
进一步优选地,当植物多糖为葡聚糖、金属氧化物为Mn/TiO2时,两者反应物料比为17g:0.01mg;
进一步优选地,当植物多糖为葡聚糖、金属氧化物为Mn/TiO2时,两者反应物料比为17g:0.01mg,调节管内气压2.2GPa、N2流速4.0cm3/min,调节温度至620℃维持5h;冷却管式炉至室温并确保处于N2氛围中,去离子水冲反应产物并抽滤直至滤液呈中性,收集滤饼用去离子水充分分散,在4000r/min转动速率下离心处理25min,收集管底固体物质经干燥得到碳量子点;
(2)碳量子点亲电加成修饰部分异氰酸酯基团
称取所制得碳量子点、多异氰酸酯、溶剂于容器内置于冰水浴中,连接N2并置换体系气体氛围,300r/min搅拌速率下调节温度至-5~10℃,加入路易斯酸后维持反应25~90min,反应产物经3.0μm级透析膜透析6~14h除杂,得到碳量子点修饰后的多异氰酸酯溶液;
所述多异氰酸酯是4,4ˊ,4〞-三苯甲烷三异氰酸酯、己二异氰酸酯缩二脲、4-氯-6-甲基间苯基二异氰酸酯、3,3-二氯代联苯4,4-二异氰酸酯,优选4,4ˊ,4〞-三苯甲烷三异氰酸酯;
所述溶剂是1,3-二氧戊环、N,N-二甲基甲酰胺、甲苯、甲基叔丁基醚,优选1,3-二氧戊环;
所述路易斯酸是苯磺酸、氯化铁、甲酸,优选氯化铁;
所述碳量子点、多异氰酸酯、溶剂与路易斯酸的反应物料比是0.01~0.5mg:50~100g:50~100mL:0.001mg,优选0.4mg:80g:90mL:0.001mg;
进一步优选地,称取上述碳量子点、多异氰酸酯、溶剂于容器内置于冰水浴中,连接N2并置换体系气体氛围,300r/min搅拌速率下调节温度至5℃,加入路易斯酸后维持反应45min,反应产物经3.0μm级透析膜透析12h除杂,得到碳量子点修饰后的多异氰酸酯溶液;
(3)含碳量子点异氰酸酯用于制备聚(氨酯-乙烯醇-丙烯酸酯)预聚物
称取多元羟基烷烃、聚合多元醇、溶剂于容器内并置于油浴中,连接N2并置换体系气体氛围、调节搅拌速率300r/min至原料溶解,加入催化剂,20~90min内程序性升温至50~95℃,升温过程中将所制得的碳量子点修饰后的多异氰酸酯溶液通过恒压滴液漏斗加完毕,调节温度至70~110℃加入扩链剂,维持1~6h后再加入封端剂;维持N2气氛降至室温,停止搅拌,得到的澄清透明液经加压蒸馏即得到聚(氨酯-乙烯醇-丙烯酸酯)预聚物;
所述多元羟基烷烃是1,2,6-己三醇、1,3-丁二醇、2,3-丁二醇、1,2-己二醇、1,2,3-己三醇,优选1,2,6-己三醇;
所述聚合多元醇是聚酯多元醇、聚醚多元醇、聚乙烯醇,优选聚醚多元醇;
所述溶剂是N,N-二甲基甲酰胺、二甲苯、甲基叔丁基醚、丙酮,优选丙酮;
所述催化剂是N-甲基咪唑、双吗啉基二乙基醚、异辛酸钾、二丁基氧化锡,优选双吗啉基二乙基醚;
所述扩链剂是二乙醇胺、三异丙醇胺、缩水甘油烯丙基醚、过氧化二异丙苯,优选二乙醇胺;
所述封端剂是甲基丙烯酸羟乙酯、丙烯酸甲酯、丙烯酸苄酯、甲基丙烯酸苯酯,优选甲基丙烯酸羟乙酯;
所述聚合多元醇、碳量子点修饰后的多异氰酸酯、多元羟基烷烃、扩链剂、催化剂、封端剂、溶剂的反应物料比例是0.1~1mmol:1mmol:0.05~0.1mmol:0.01~0.06mmol:0.001~0.01mg:0.03~0.05mmol:80~180mL,优选0.9mmol:1mmol:0.08mmol:0.02mmol:0.007mg:0.04mmol:160mL;
进一步优选地,以上述优选物料,向体系中加入催化剂并于50min内匀速升温至85℃,升温过程中将碳量子点修饰后的多异氰酸酯溶液通过恒压滴液漏斗同时加入完毕,调节温度至105℃后加入扩链剂,维持4h后再加入封端剂,维持N2气氛降至室温,停止搅拌;
(4)反-斯托克斯光变光油的制备
避光环境中,将所制得聚(氨酯-乙烯醇-丙烯酸酯)预聚物持续搅拌下依次加入丙烯酸单体、消泡剂、流平剂、防沉剂与微量光引发剂,维持搅拌10~70min,即得到反-斯托克斯光变光油,密封避光保存;
所述丙烯酸单体是2-甲基丙烯酸烯丙酯、甲基丙烯酸乙酯、苯乙烯、丙烯酸2-乙基己酯、甲基丙烯酸甲基烯丙酯、二缩三丙二醇二丙烯酸酯,优选2-甲基丙烯酸烯丙酯;
所述消泡剂是磷酸三丁酯、聚二甲基硅氧烷、聚丙二醇单丁基醚,优选聚二甲基硅氧烷;
所述流平剂是H810(CAS NO.128192-17-6)、H850(CAS NO.157479-55-5)、H633(CAS NO.67762-85-0),优选H810;
所述防沉剂是有机膨润土、聚烯烃蜡、改性氢化蓖麻油、改性聚脲N-甲基吡咯烷酮、聚酰胺蜡,优选聚烯烃蜡;
所述光引发剂是2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮、2,4,6-三甲基苯甲酰基苯基膦酸乙酯、2-羟基-2-甲基-1-[4-(叔丁基)苯基]-1-丙酮、2-羟基-2-甲基-1-[4-(叔丁基)苯基]-1-丙酮、2-羟基-2-甲基-1-苯基-1-丙酮,优选2,4,6-三甲基苯甲酰基苯基膦酸乙酯;
所述聚(氨酯-乙烯醇-丙烯酸酯)预聚物、丙烯酸单体、消泡剂、流平剂、防沉剂、光引发剂的反应物料比例是50~100g:5g:0.05~0.1mg:0.2~1.0mg:0.1~20.0mg:80~180μg,优选80g:5g:0.06mg:0.4mg:11mg:92μg;
进一步优选地,依次向体系中加入丙烯酸单体、消泡剂、流平剂、防沉剂与微量光引发剂,维持搅拌45min为最佳。
实验方法
(1)红外光谱测试
采用傅里叶变换红外(FI-IR)分析测试仪(ATAVAR360型,美国Nicolet公司)对实施例1中制取的碳量子点表面官能团进行测试。测试时,扫描波长为500~4000nm,平均分辨率2cm-1,扫描不低于32次。
(2)荧光性能测试
利用荧光光谱仪(JYFM-4型,美国哈希公司)测试实施例1制取的反-斯托克斯光变光油的发光性能,并用980nm激光(MDL-N-980,中国)作为激发源;测试前吸取1mL左右反-斯托克斯光变光油均匀涂敷于聚四氟乙烯表面皿中,自然光下晾干2h使其简单固化成膜。
有益效果
本发明利用植物多糖作为碳源前驱体制备得到具有丰富活性氢的碳量子点,通过亲核加成方式与多异氰酸酯键合,形成碳量子点修饰部分异氰酸酯基,将其作为硬单体制备得到的聚(氨酯-乙烯醇-丙烯酸酯)预聚物再与丙烯酸单体、消泡剂、流平剂、防沉剂与微量光引发剂混合并最终形成反-斯托克斯光变光油,该种光油经荧光光谱表征具备较好的上转换发光特性,可以广泛应用于特种印刷、防伪、信息传递等技术领域;此外,由于在制备聚(氨酯-乙烯醇-丙烯酸酯)预聚物阶段即完成了溶剂的去除,因此成品的反-斯托克斯光变光油几乎不含有任何溶剂残留,满足当前环保需要,具备较好的市场前景。
附图说明
图1.实施例1制得的碳量子点红外光谱图;
图2.实施例1制取的反-斯托克斯光变光油荧光光谱图。
具体实施方式
下面结合具体实施例对本发明进行详细说明,以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范畴。
实施例1
一种基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,包括如下步骤:
称取17g葡聚糖、0.01mgMn/TiO2装入管式炉内,连接N2并置换管内空气;调节管内气压2.2GPa、N2流速4.0cm3/min后调节温度至620℃,维持5h;冷却管式炉至室温并确保体系始终处于N2气体氛围中;去离子水冲反应产物并抽滤直至滤液呈中性,收集滤饼并用100mL去离子水充分分散,在4000r/min转动速率下离心处理25min,收集管底固体物质经干燥即得到碳量子点;
称取0.4mg上述碳量子点、80g 4,4ˊ,4〞-三苯甲烷三异氰酸酯、90mL 1,3-二氧戊环置于250mL三口烧瓶内,三口烧瓶配备有冷凝管、磁力搅拌、温度计、三通逆止阀并置于冰水浴中;连接N2并置换体系气体氛围;300r/min搅拌速率下调节温度至5℃,加入0.001mg氯化铁后维持反应45min;反应产物经3.0μm级透析膜透析12h去除固体杂质,即得到碳量子点修饰后的多异氰酸酯溶液;
称取0.08mmol 1,2,6-己三醇、0.9mmol聚醚多元醇、160mL丙酮置于250mL四口烧瓶内,四口烧瓶配备有冷凝管、恒压滴液漏斗、磁力搅拌、温度计、三通逆止阀并置于油浴中;连接N2并置换体系气体氛围、调节搅拌速率300r/min直至原料全部溶解;向体系中加入0.007mg双吗啉基二乙基醚并设置50min内匀速升温至85℃,升温过程中将上述1mmol碳量子点修饰后的多异氰酸酯溶液通过恒压滴液漏斗同时间加入完毕;调节温度至105℃后加入0.02mmol二乙醇胺,维持4h后再加入0.04mmol甲基丙烯酸羟乙酯;维持N2气体氛围条件下调节体系温度至室温、停止搅拌,得到的澄清透明液经加压蒸馏即得到聚(氨酯-乙烯醇-丙烯酸酯)预聚物;
室温、避光环境中,将上述80g聚(氨酯-乙烯醇-丙烯酸酯)预聚物转移至500mL锥形瓶内并维持磁力搅拌100r/min;依次向体系中加入5g 2-甲基丙烯酸烯丙酯、0.06mg聚二甲基硅氧烷、0.4mg H810、11mg聚烯烃蜡与92μg 2,4,6-三甲基苯甲酰基苯基膦酸乙酯,维持搅拌45min,即得到反-斯托克斯光变光油,密封避光保存。
实施例2
一种基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,包括如下步骤:
称取10g葡聚糖、0.01mgMn/TiO2装入管式炉内,连接N2并置换管内空气;调节管内气压1.0GPa、N2流速0.2cm3/min后调节温度至240℃,维持2h;冷却管式炉至室温并确保体系始终处于N2气体氛围中;去离子水冲反应产物并抽滤直至滤液呈中性,收集滤饼并用100mL去离子水充分分散,在4000r/min转动速率下离心处理10min,收集管底固体物质经干燥即得到碳量子点;
称取0.01mg上述碳量子点、50g 4,4ˊ,4〞-三苯甲烷三异氰酸酯、50mL 1,3-二氧戊环置于250mL三口烧瓶内,三口烧瓶配备有冷凝管、磁力搅拌、温度计、三通逆止阀并置于冰水浴中;连接N2并置换体系气体氛围;300r/min搅拌速率下调节温度至-5℃,加入0.001mg氯化铁后维持反应25min;反应产物经3.0μm级透析膜透析6h去除固体杂质,即得到碳量子点修饰后的多异氰酸酯溶液;
称取0.05mmol 1,2,6-己三醇、0.1mmol聚醚多元醇、80mL丙酮置于250mL四口烧瓶内,四口烧瓶配备有冷凝管、恒压滴液漏斗、磁力搅拌、温度计、三通逆止阀并置于油浴中;连接N2并置换体系气体氛围、调节搅拌速率300r/min直至原料全部溶解;向体系中加入0.001mg双吗啉基二乙基醚并设置20min内匀速升温至50℃,升温过程中将上述1mmol碳量子点修饰后的多异氰酸酯溶液通过恒压滴液漏斗同时间加入完毕;调节温度至70℃后加入0.016mmol二乙醇胺,维1h后再加入0.03mmol甲基丙烯酸羟乙酯;维持N2气体氛围条件下调节体系温度至室温、停止搅拌,得到的澄清透明液经加压蒸馏即得到聚(氨酯-乙烯醇-丙烯酸酯)预聚物;
室温、避光环境中,将上述50g聚(氨酯-乙烯醇-丙烯酸酯)预聚物转移至500mL锥形瓶内并维持磁力搅拌100r/min;依次向体系中加入5g 2-甲基丙烯酸烯丙酯、0.05mg聚二甲基硅氧烷、0.2mg H810、0.1mg聚烯烃蜡与80μg 2,4,6-三甲基苯甲酰基苯基膦酸乙酯,维持搅拌10min,即得到反-斯托克斯光变光油,密封避光保存。
实施例3
一种基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,包括如下步骤:
称取20g葡聚糖、0.01mgMn/TiO2装入管式炉内,连接N2并置换管内空气;调节管内气压4.5GPa、N2流速6.0cm3/min后调节温度至870℃,维持10h;冷却管式炉至室温并确保体系始终处于N2气体氛围中;去离子水冲反应产物并抽滤直至滤液呈中性,收集滤饼并用100mL去离子水充分分散,在4000r/min转动速率下离心处理30min,收集管底固体物质经干燥即得到碳量子点;
称取0.5mg上述碳量子点、100g 4,4ˊ,4〞-三苯甲烷三异氰酸酯、100mL 1,3-二氧戊环置于250mL三口烧瓶内,三口烧瓶配备有冷凝管、磁力搅拌、温度计、三通逆止阀并置于冰水浴中;连接N2并置换体系气体氛围;300r/min搅拌速率下调节温度至10℃,加入0.001mg氯化铁后维持反应90min;反应产物经3.0μm级透析膜透析14h去除固体杂质,即得到碳量子点修饰后的多异氰酸酯溶液;
称取0.1mmol 1,2,6-己三醇、1mmol聚醚多元醇、180mL丙酮置于250mL四口烧瓶内,四口烧瓶配备有冷凝管、恒压滴液漏斗、磁力搅拌、温度计、三通逆止阀并置于油浴中;连接N2并置换体系气体氛围、调节搅拌速率300r/min直至原料全部溶解;向体系中加入0.01mg双吗啉基二乙基醚并设置90min内匀速升温至95℃,升温过程中将上述1mmol碳量子点修饰后的多异氰酸酯溶液通过恒压滴液漏斗同时间加入完毕;调节温度至110℃后加入0.06mmol二乙醇胺,维持6h后再加入0.05mmol甲基丙烯酸羟乙酯;维持N2气体氛围条件下调节体系温度至室温、停止搅拌,得到的澄清透明液经加压蒸馏即得到聚(氨酯-乙烯醇-丙烯酸酯)预聚物;
室温、避光环境中,将上述100g聚(氨酯-乙烯醇-丙烯酸酯)预聚物转移至500mL锥形瓶内并维持磁力搅拌100r/min;依次向体系中加入5g 2-甲基丙烯酸烯丙酯、0.1mg聚二甲基硅氧烷、1.0mg H810、20.0mg聚烯烃蜡与180μg 2,4,6-三甲基苯甲酰基苯基膦酸乙酯,维持搅拌70min,即得到反-斯托克斯光变光油,密封避光保存。
实施例4
一种基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,包括如下步骤:
称取11g木聚糖、0.01mgγ-Al2O3装入管式炉内,连接N2并置换管内空气;调节管内气压1.2GPa、N2流速0.8cm3/min后调节温度至270℃,维持3h;冷却管式炉至室温并确保体系始终处于N2气体氛围中;去离子水冲反应产物并抽滤直至滤液呈中性,收集滤饼并用100mL去离子水充分分散,在4000r/min转动速率下离心处理15min,收集管底固体物质经干燥即得到碳量子点;
称取0.2mg上述碳量子点、60g己二异氰酸酯缩二脲、70mL N,N-二甲基甲酰胺置于250mL三口烧瓶内,三口烧瓶配备有冷凝管、磁力搅拌、温度计、三通逆止阀并置于冰水浴中;连接N2并置换体系气体氛围;300r/min搅拌速率下调节温度至2,加入0.001mg苯磺酸后维持反应30min;反应产物经3.0μm级透析膜透析8h去除固体杂质,即得到碳量子点修饰后的多异氰酸酯溶液;
称取0.06mmol 1,3-丁二醇、0.2mmol聚酯多元醇、120mL二甲苯置于250mL四口烧瓶内,四口烧瓶配备有冷凝管、恒压滴液漏斗、磁力搅拌、温度计、三通逆止阀并置于油浴中;连接N2并置换体系气体氛围、调节搅拌速率300r/min直至原料全部溶解;向体系中加入0.008mg异辛酸钾并设置60min内匀速升温至75℃,升温过程中将上述1mmol碳量子点修饰后的多异氰酸酯溶液通过恒压滴液漏斗同时间加入完毕;调节温度至94℃后加入0.03mmol三异丙醇胺,维持2h后再加入0.05mmol丙烯酸甲酯;维持N2气体氛围条件下调节体系温度至室温、停止搅拌,得到的澄清透明液经加压蒸馏即得到聚(氨酯-乙烯醇-丙烯酸酯)预聚物;
室温、避光环境中,将上述60g聚(氨酯-乙烯醇-丙烯酸酯)预聚物转移至500mL锥形瓶内并维持磁力搅拌100r/min;依次向体系中加入5g甲基丙烯酸乙酯、0.07mg磷酸三丁酯、0.7mg H850、19.0mg改性氢化蓖麻油与104μg 2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮,维持搅拌22min,即得到反-斯托克斯光变光油,密封避光保存。
实施例5
一种基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,包括如下步骤:
称取18g木聚糖、0.01mgCr/TiO2装入管式炉内,连接N2并置换管内空气;调节管内气压3.4GPa、N2流速5.8cm3/min后调节温度至448℃,维持8h;冷却管式炉至室温并确保体系始终处于N2气体氛围中;去离子水冲反应产物并抽滤直至滤液呈中性,收集滤饼并用100mL去离子水充分分散,在4000r/min转动速率下离心处理28min,收集管底固体物质经干燥即得到碳量子点;
称取0.09mg上述碳量子点、65g 3,3-二氯代联苯4,4-二异氰酸酯、80mL甲基叔丁基醚置于250mL三口烧瓶内,三口烧瓶配备有冷凝管、磁力搅拌、温度计、三通逆止阀并置于冰水浴中;连接N2并置换体系气体氛围;300r/min搅拌速率下调节温度至0℃,加入0.001mg甲酸后维持反应80min;反应产物经3.0μm级透析膜透析10h去除固体杂质,即得到碳量子点修饰后的多异氰酸酯溶液;
称取0.04mmol 1,2,3-己三醇、0.8mmol聚乙烯醇、150mL甲基叔丁基醚置于250mL四口烧瓶内,四口烧瓶配备有冷凝管、恒压滴液漏斗、磁力搅拌、温度计、三通逆止阀并置于油浴中;连接N2并置换体系气体氛围、调节搅拌速率300r/min直至原料全部溶解;向体系中加入0.003mg二丁基氧化锡并设置40min内匀速升温至80℃,升温过程中将上述1mmol碳量子点修饰后的多异氰酸酯溶液通过恒压滴液漏斗同时间加入完毕;调节温度至102℃后加入0.05mmol过氧化二异丙苯,维持3.5h后再加入0.05mmol甲基丙烯酸苯酯;维持N2气体氛围条件下调节体系温度至室温、停止搅拌,得到的澄清透明液经加压蒸馏即得到聚(氨酯-乙烯醇-丙烯酸酯)预聚物;
室温、避光环境中,将上述90g聚(氨酯-乙烯醇-丙烯酸酯)预聚物转移至500mL锥形瓶内并维持磁力搅拌100r/min;依次向体系中加入5g丙烯酸2-乙基己酯、0.09mg聚丙二醇单丁基醚、0.6mg H633、17.0mg聚酰胺蜡与104μg 2-羟基-2-甲基-1-苯基-1-丙酮,维持搅拌61min,即得到反-斯托克斯光变光油,密封避光保存。
以实施例1为例,制取的碳量子点经红外光谱表征,如图1所示。3240cm-1处有较宽的吸收峰,主要来源于O—H伸缩振动;2980cm-1处有明显吸收峰,主要归因于C—H伸缩振动;1610cm-1与1010cm-1两处明显的吸收峰来源于N—H的弯曲振动;1420cm-1处的吸收峰可以归因于O—H弯曲振动;1300cm-1处的吸收峰大致可以判定为C—O伸缩振动和弯曲振动;1160cm-1处有明显的吸收峰主要源自于C—N伸缩振动;由此可见碳量子点表面富含众多端氨基与醇羟基,为异氰酸酯基团的亲核加成提供了充足的活性氢原子。
以实施例1为例,制取的反-斯托克斯光变光油经980nm激发形成的荧光光谱曲线,如图2所示。样品有两处明显的荧光跃迁行为,其中位于635nm处的发射峰属于2H11/2→4I15/2,位于672nm处的发射峰属于4F9/2→4I15/2跃迁,由此可见该样品具备一定强度的上转换发光特性。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书所作的等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (10)
1.一种基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,其特征在于,包括如下步骤:
(1)将植物多糖、金属氧化物装入管式炉内,连接N2并置换管内空气,管内气压1.0~4.5GPa,N2流速0.2~6.0cm3/min,升温至240~870℃维持2~10h,冷却至室温并确保处于N2氛围中,去离子水冲反应产物,抽滤至滤液呈中性,收集滤饼用去离子水充分分散,4000r/min转速离心10~30min,收集管底固体物质经干燥得到碳量子点;
(2)称取所制得碳量子点、多异氰酸酯、溶剂于容器内置于冰水浴中,连接N2并置换体系气体氛围,300r/min搅拌速率下调节温度至-5~10℃,加入路易斯酸后维持反应25~90min,反应产物经3.0μm级透析膜透析6~14h除杂,得到碳量子点修饰后的多异氰酸酯溶液;
(3)称取多元羟基烷烃、聚合多元醇、溶剂于容器内并置于油浴中,连接N2并置换体系气体氛围、调节搅拌速率300r/min至原料溶解,加入催化剂,20~90min内程序性升温至50~95℃,升温过程中将所制得的碳量子点修饰后的多异氰酸酯溶液通过恒压滴液漏斗加完毕,调节温度至70~110℃加入扩链剂,维持1~6h后再加入封端剂;维持N2气氛降至室温,停止搅拌,得到的澄清透明液经加压蒸馏即得到聚(氨酯-乙烯醇-丙烯酸酯)预聚物;
(4)避光环境中,将所制得聚(氨酯-乙烯醇-丙烯酸酯)预聚物持续搅拌下依次加入丙烯酸单体、消泡剂、流平剂、防沉剂与微量光引发剂,维持搅拌10~70min,即得。
2.根据权利要求1所述的基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,其特征在于:步骤(1)中,所述植物多糖是葡聚糖、木聚糖、甘露聚糖,优选葡聚糖;所述金属氧化物是γ-Al2O3、α-FeOOH、Mn/TiO2、Cr/TiO2等,优选Mn/TiO2。
3.根据权利要求1所述的基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,其特征在于:步骤(1)中,所述植物多糖与金属氧化物的反应物料比是10~20g:0.01mg。
4.根据权利要求1所述的基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,其特征在于:步骤(2)中,所述多异氰酸酯是4,4ˊ,4〞-三苯甲烷三异氰酸酯、己二异氰酸酯缩二脲、4-氯-6-甲基间苯基二异氰酸酯、3,3-二氯代联苯4,4-二异氰酸酯,优选4,4ˊ,4〞-三苯甲烷三异氰酸酯;所述溶剂是1,3-二氧戊环、N,N-二甲基甲酰胺、甲苯、甲基叔丁基醚,优选1,3-二氧戊环;所述路易斯酸是苯磺酸、氯化铁、甲酸,优选氯化铁。
5.根据权利要求1所述的基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,其特征在于:步骤(2)中,所述碳量子点、多异氰酸酯、溶剂与路易斯酸的反应物料比是0.01~0.5mg:50~100g:50~100mL:0.001mg,优选0.4mg:80g:90mL:0.001mg。
6.根据权利要求1所述的基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,其特征在于:步骤(3)中,所述多元羟基烷烃是1,2,6-己三醇、1,3-丁二醇、2,3-丁二醇、1,2-己二醇、1,2,3-己三醇,优选1,2,6-己三醇;所述聚合多元醇是聚酯多元醇、聚醚多元醇、聚乙烯醇,优选聚醚多元醇;所述溶剂是N,N-二甲基甲酰胺、二甲苯、甲基叔丁基醚、丙酮,优选丙酮;所述催化剂是N-甲基咪唑、双吗啉基二乙基醚、异辛酸钾、二丁基氧化锡,优选双吗啉基二乙基醚;所述扩链剂是二乙醇胺、三异丙醇胺、缩水甘油烯丙基醚、过氧化二异丙苯,优选二乙醇胺;所述封端剂是甲基丙烯酸羟乙酯、丙烯酸甲酯、丙烯酸苄酯、甲基丙烯酸苯酯,优选甲基丙烯酸羟乙酯。
7.根据权利要求1所述的基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,其特征在于:步骤(3)中,所述聚合多元醇、碳量子点修饰后的多异氰酸酯、多元羟基烷烃、扩链剂、催化剂、封端剂、溶剂的反应物料比例是0.1~1mmol:1mmol:0.05~0.1mmol:0.01~0.06mmol:0.001~0.01mg:0.03~0.05mmol:80~180mL,优选0.9mmol:1mmol:0.08mmol:0.02mmol:0.007mg:0.04mmol:160mL。
8.根据权利要求1所述的基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,其特征在于:步骤(4)中,所述丙烯酸单体是2-甲基丙烯酸烯丙酯、甲基丙烯酸乙酯、苯乙烯、丙烯酸2-乙基己酯、甲基丙烯酸甲基烯丙酯、二缩三丙二醇二丙烯酸酯,优选2-甲基丙烯酸烯丙酯;所述消泡剂是磷酸三丁酯、聚二甲基硅氧烷、聚丙二醇单丁基醚,优选聚二甲基硅氧烷;所述流平剂是H810(CAS NO.
128192-17-6)、H850(CAS NO.157479-55-5)、H633(CAS NO.67762-85-0),优选H810;所述防沉剂是有机膨润土、聚烯烃蜡、改性氢化蓖麻油、改性聚脲N-甲基吡咯烷酮、聚酰胺蜡,优选聚烯烃蜡;所述光引发剂是2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮、2,4,6-三甲基苯甲酰基苯基膦酸乙酯、2-羟基-2-甲基-1-[4-(叔丁基)苯基]-1-丙酮、2-羟基-2-甲基-1-[4-(叔丁基)苯基]-1-丙酮、2-羟基-2-甲基-1-苯基-1-丙酮,优选2,4,6-三甲基苯甲酰基苯基膦酸乙酯。
9.根据权利要求1所述的基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,其特征在于:步骤(4)中,所述聚(氨酯-乙烯醇-丙烯酸酯)预聚物、丙烯酸单体、消泡剂、流平剂、防沉剂、光引发剂的反应物料比例是50~100g:5g:0.05~0.1mg:0.2~1.0mg:0.1~20.0mg:80~180μg。
10.根据权利要求1所述的基于碳量子点修饰部分异氰酸酯基的无溶剂型反-斯托克斯光变光油的制备方法,其特征在于:步骤(4)中,所述聚(氨酯-乙烯醇-丙烯酸酯)预聚物、丙烯酸单体、消泡剂、流平剂、防沉剂、光引发剂的反应物料比例是80g:5g:0.06mg:0.4mg:11mg:92μg。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109097038A (zh) * | 2018-09-29 | 2018-12-28 | 太原理工大学 | 一种固态黄色荧光碳量子点及其制备方法 |
CN109504368A (zh) * | 2018-11-19 | 2019-03-22 | 太原科技大学 | 一种CDs/TPU荧光纳米复合材料制备方法 |
CN113480713A (zh) * | 2021-06-30 | 2021-10-08 | 上海交通大学 | 一种聚脲量子点荧光微球的制备方法 |
CN116217883A (zh) * | 2023-01-03 | 2023-06-06 | 万华化学集团股份有限公司 | 一种碳量子点修饰的荧光水性聚氨酯及其制备方法 |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109097038A (zh) * | 2018-09-29 | 2018-12-28 | 太原理工大学 | 一种固态黄色荧光碳量子点及其制备方法 |
CN109504368A (zh) * | 2018-11-19 | 2019-03-22 | 太原科技大学 | 一种CDs/TPU荧光纳米复合材料制备方法 |
CN113480713A (zh) * | 2021-06-30 | 2021-10-08 | 上海交通大学 | 一种聚脲量子点荧光微球的制备方法 |
CN116217883A (zh) * | 2023-01-03 | 2023-06-06 | 万华化学集团股份有限公司 | 一种碳量子点修饰的荧光水性聚氨酯及其制备方法 |
Non-Patent Citations (2)
Title |
---|
姜时锋;罗珍;许戈文;黄毅萍;鲍俊杰;熊潜生;: "碳点/水性聚氨酯复合材料的制备及性能", 精细化工, no. 01 * |
田振等: "微波合成含氮掺杂碳量子点改性水性聚氨酯的制备与性能", 《化工进展》, vol. 39, no. 10, 31 July 2020 (2020-07-31), pages 4127 - 4133 * |
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