CN109518463A - pH响应缓控释的聚合物纳米香料及其制备方法 - Google Patents
pH响应缓控释的聚合物纳米香料及其制备方法 Download PDFInfo
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Abstract
一种pH响应缓控释的聚合物纳米香料及其制备方法和应用,包括如下步骤:首先,通过可逆加成‑断裂链转移聚合(RAFT)反应制备了pH响应两亲嵌段共聚物;然后,通过和阳离子表面活性剂进行酸铵缩合反应,制备了阳离子pH响应两亲嵌段共聚物;最后,将阳离子两亲嵌段共聚物负载香料,得到pH响应缓控释的聚合物纳米香料。本发明不仅解决了香料的不稳定、易挥发、香料释放过程的不可控问题,而且香料的负载率高,香气释放均匀,缓慢,留香时间久,并且纳米香料使用方便、制备方法简单,可广泛应用于丝绸、皮革等表面带负点的基材附香。
Description
技术领域
本发明涉及精细化工技术领域,尤其涉及一种纳米香料技术领域,具体涉及一种pH响应缓控释的聚合物纳米香料及其制备方法。
背景技术
随着社会文明的进步,人们生活品质的提高,芳香的气味逐渐被人们所推崇。香料已广泛地应用于化妆品蚕丝、皮革和墙纸等领域。但香料主要是挥发性小分子化合物,成分不稳定、易挥发。香料长效性差的重要原因是,香料释放过程的不可控,因此精确可控的释放香料是本发明拟解决的技术问题。为了解决香料易挥发、不稳定和香料长效性差的问题,本发明通过精准自组装,对香料进行纳米化,并赋予其pH响应的缓控释性能,发展纳米香料自组装体系的构建技术,对香料的挥发性进行改善。
发明内容
有鉴于此,本发明提供了一种pH响应缓控释的聚合物纳米香料及其制备方法,以期至少部分地解决上述提及的技术问题中的至少之一。
为实现上述目的,作为一个方面,本发明提供一种pH响应缓控释的聚合物纳米香料的制备方法,包括以下步骤:
(1)将羧基甜菜碱单体、甲基丙烯酸己酯单体和含末端羧基的链转移剂在引发剂作用下通过可逆加成-断裂链转移聚合反应制备pH响应两亲嵌段共聚物;
(2)将所述pH响应两亲嵌段共聚物中的所述末端羧基和阳离子表面活性剂通过酸铵缩合反应制备阳离子pH响应两亲嵌段共聚物,其中阳离子表面活性剂为氨基酸类表面活性剂;
(3)将所述阳离子pH响应两亲嵌段共聚物负载香料,得到pH响应缓控释的聚合物纳米香料。
作为另一个方面,本发明还提供了一种使用如上所述的制备方法所制得的pH响应缓控释的聚合物纳米香料,其平均粒径为50~300nm,载香量为35.21~40.55%。
与现有技术相比,本发明的有益效果是:
(1)本发明采用阳离子两亲嵌段共聚物对香料进行包载,制备了pH响应缓控释香料,解决了香料的不稳定、易挥发、香料释放过程的不可控问题;
(2)香料的负载率高,香气释放均匀,缓慢,留香时间久;
(3)纳米香料使用方便、制备方法简单,可广泛应用于日化、纺织、皮革、墙纸等各个领域。
附图说明
图1是本发明实施例1~3制备的不同亲疏水比例的pH响应缓控释的聚合物纳米香料的粒径;
图2是本发明实施例1~3制备的不同亲疏水比例的pH响应缓控释的聚合物纳米香料的表而电位;
图3(a)是本发明实施例1~3制备的不同亲疏水比例的pH响应缓控释的聚合物纳米香料在PH为5时的响应释放;
图3(b)是本发明实施例1~3制备的不同亲疏水比例的pH响应缓控释的聚合物纳米香料在PH为7时的响应释放;
图3(c)是本发明实施例1~3制备的不同亲疏水比例的pH响应缓控释的聚合物纳米香料在PH为7时的响应释放。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,以下结合具体实施例,并参照附图,对本发明作进一步的详细说明。
本发明的原理是采用两亲性嵌段共聚物体系作为香料载体,通过两亲性嵌段共聚物和疏水性香料的亲疏水作用力,将香料包载在内核,自组装成纳米聚合物。含阳离子pH响应的两亲嵌段共聚物,在酸性条件下,高分子链膨胀,促进释放香料分子。在碱性条件下,高分子链收缩,抑制香料分子释放。
具体地,本发明提供了一种pH响应缓控释的聚合物纳米香料的制备方法,包括如下步骤:
(1)将羧基甜菜碱单体、甲基丙烯酸己酯单体和含末端羧基的链转移剂在引发剂作用下通过可逆加成-断裂链转移聚合反应制备pH响应两亲嵌段共聚物;
(2)将所述pH响应两亲嵌段共聚物中的所述末端羧基和阳离子表面活性剂通过酸铵缩合反应制备阳离子pH响应两亲嵌段共聚物,其中阳离子表面活性剂为氨基酸类表面活性剂;
(3)将所述阳离子pH响应两亲嵌段共聚物负载香料,得到pH响应缓控释的聚合物纳米香料。
其中步骤(1)中,所述羧基甜菜碱单体通过将甲基丙烯酸二甲氨基乙酯和β-丙内酯反应制备。
其中步骤(1)中,所述可逆加成-断裂链转移聚合反应的步骤具体包括以下子步骤:子步骤(11)将含末端羧基的链转移剂,羧基甜菜碱单体与引发剂溶于有机溶剂中,按照“冷冻-抽真空-通氮气-复融”步骤重复处理,然后进行加热反应后透析纯化得到不同分子量的pH响应高分子聚羧基甜菜碱;子步骤(12)将纯化后的所述pH响应高分子聚羧基甜菜碱与甲基丙烯酸己酯单体和引发剂溶于有机溶剂中,按照“冷冻-抽真空-通氮气-复融”步骤重复处理,然后在进行加热反应后透析纯化得到不同分子量的pH响应两亲嵌段共聚物。
其中所述含末端羧基的链转移剂为4-氰基-4-(十二烷基硫烷基硫代羰基)硫烷基戊酸;所述引发剂为偶氮二异丁腈;
所述羧基甜菜碱单体、甲基丙烯酸己酯单体和含末端羧基的链转移剂的质量比为10~20∶2.75∶1。
其中步骤(2)具体包括:将所述pH响应两亲嵌段共聚物、缩合剂,碱催化剂和阳离子表面活性剂溶于有机溶剂中进行加热反应后,通过透析纯化得到阳离子pH响应两亲嵌段共聚物。
其中所述缩合剂为六氟磷酸苯并三唑-1-基-氧基三吡咯烷基磷;所述碱催化剂为三乙胺;所述阳离子表面活性剂为L精氨酸或赖氨酸。
其中步骤(3)具体包括以下子步骤:子步骤(31)将所述阳离子pH响应两亲嵌段共聚物和香料溶于有机溶剂中,并在剧烈搅拌中逐滴加入到去离子水中;子步骤(32)进行超声沉淀;子步骤(33)通过透析除去有机溶剂及未包载的香料,得到pH响应缓控释的聚合物纳米香料。
其中子步骤(31)中:所述香料为疏水性香料,选自花香、木香或果香;所述pH响应两亲嵌段共聚物和香料的质量比为1~5∶1。
其中子步骤(33)中,所述透析使用截留分子量为7000的透析袋,透析液为去离子水。
本发明还提供了一种使用如上所述的制备方法所制得的pH响应缓控释的聚合物纳米香料,其平均粒径为50~300nm,载香率为35.21~40.55%。
下面列举几个具体的实施例,以便对本发明的实施和技术效果作更进一步的说明。下述实施例中,所用实验材料均可以从常规市售途径获得,或者通过本领域常规的生产厂家生产制备得到;其中,有关搅拌、透析、冷冻和真空干燥的操作均为本领域常规的实验方法。
实施例1
在本实施例中,通过以下步骤制备pH响应缓控释的聚合物纳米香料:
(1)、通过可逆加成-断裂链转移聚合(RAFT)反应制备pH响应两亲嵌段共聚物:
1、10.4g甲基丙烯酸二甲氨基乙酯与5.7gβ-丙内酯溶于无水二氯甲烷,冰浴并氮气保护下反应5h,用乙醚沉淀并抽滤,得羧基甜菜碱单体。2、403mg 4-氰基-4-(十二烷基硫烷基硫代羰基)硫烷基戊酸,5503mg羧基甜菜碱单体与67mg偶氮二异丁腈溶于甲醇中,重复“冷冻-抽真空-通氮气-复融”步骤三次后,65℃反应24h,透析,冻干,得pH响应高分子聚羧基甜菜碱。3、将纯化后的pH响应高分子聚羧基甜菜碱与1106mg甲基丙烯酸己酯和67mg偶氮二异丁腈溶于甲醇中重复“冷冻-抽真空-通氮气-复融”步骤三次后,65℃反应24h,透析,冻干,得到亲、疏链段聚合度比例为20∶5的pH响应两亲嵌段聚合物。
(2)、通过酸铵缩合反应制备阳离子pH响应两亲嵌段共聚物:
1、370mg pH响应两亲嵌段聚合物与40mg六氟磷酸苯并三唑-1-基-氧基三吡咯烷基磷,30mg三乙胺和20mg L-精氨酸溶于N,N-二甲基甲酰胺(DMF)溶液中,40℃反应24h。2、用DMF与水透析24h,冻干,得纯化后的阳离子两亲嵌段共聚物。
(3)、阳离子pH响应两亲嵌段共聚物负载香料:
1、100mg阳离pH响应子两亲嵌段共聚物和80mg芳樟醇香料溶于二甲基亚砜中,并在剧烈搅拌中逐滴加入到50ml去离子水中。2、超声0.5h,3、最后通过透析除去有机溶剂及未包载的香料。其中透析袋截留分子量为7000,透析液为去离子水。最终得到pH响应缓控释的聚合物纳米香料。
以上通过可逆加成-断裂链转移聚合反应与酸铵缩合反应,制备了阳离子两亲嵌段共聚物。利用纳米共沉淀法,将阳离子两亲嵌段共聚物与芳樟醇自组装成纳米香料。如图1所示,所得产物粒径在100nm左右。所得纳米香料的载香率达到了40.55%,且电位达到了25mV左右(如图2所示),适合应用于丝绸、皮革等表面带负点的基材附香。同时,如图3所示,所得纳米香料展现了优异的pH缓控释性能,12小时在pH 5,pH 7和pH 8条件下的香料释放率分别为11.84%,2.52%和1.64%。
实施例2
在本实施例中,通过以下方法制备pH响应缓控释的聚合物纳米香料:
(1)、通过可逆加成-断裂链转移聚合(RAFT)反应制备pH响应两亲嵌段共聚物:
1、10.4g甲基丙烯酸二甲氨基乙酯与5.7gβ-丙内酯溶于无水二氯甲烷,冰浴并氮气保护下反应5h,用乙醚沉淀并抽滤,得羧基甜菜碱单体。2、403mg 4-氰基-4-(十二烷基硫烷基硫代羰基)硫烷基戊酸,4127mg羧基甜菜碱单体与67mg偶氮二异丁腈溶于甲醇中,重复“冷冻-抽真空-通氮气-复融”步骤三次后,65℃反应24h,透析,冻干,得pH响应高分子聚羧基甜菜碱。3、将纯化后的pH响应高分子聚羧基甜菜碱与1106mg甲基丙烯酸己酯和67mg偶氮二异丁腈溶于甲醇中重复“冷冻-抽真空-通氮气-复融”步骤三次后,65℃反应24h,透析,冻干,得亲、疏链段聚合度比例为15∶5的pH响应两亲嵌段聚合物。
(2)、通过酸铵缩合反应制备阳离子pH响应两亲嵌段共聚物:
1、300mg pH响应两亲嵌段聚合物与40mg六氟磷酸苯并三唑-1-基-氧基三吡咯烷基磷,30mg三乙胺和20mg L-精氨酸溶于N,N-二甲基甲酰胺(DMF)溶液中,40℃反应24h。2、用DMF与水透析24h,冻干,得纯化后的阳离子两亲嵌段共聚物。
(3)、阳离子pH响应两亲嵌段共聚物负载香料:
1、100mg阳离pH响应子两亲嵌段共聚物和80mg芳樟醇香料溶于二甲基亚砜中,并在剧烈搅拌中逐滴加入到50ml去离子水中。2、超声0.5h,3、最后通过透析除去有机溶剂及未包载的香料。其中透析袋截留分子量为7000,透析液为去离子水。最终得到pH响应缓控释的聚合物纳米香料。
上述所得的pH响应缓控释的聚合物纳米香料所得产物粒径在200nm左右。所得纳米香料的载香率达到了35.55%。
实施例3
在本实施例中,通过以下方法制备pH响应缓控释的聚合物纳米香料,具体包括以下步骤:
(1)、通过可逆加成-断裂链转移聚合(RAFT)反应制备pH响应两亲嵌段共聚物:
1、10.4g甲基丙烯酸二甲氨基乙酯与5.7gβ-丙内酯溶于无水二氯甲烷,冰浴并氮气保护下反应5h,用乙醚沉淀并抽滤,得羧基甜菜碱单体。2、403mg 4-氰基-4-(十二烷基硫烷基硫代羰基)硫烷基戊酸,6695mg羧基甜菜碱与67mg偶氮二异丁腈溶于甲醇中,重复“冷冻-抽真空-通氮气-复融”步骤三次后,65℃反应24h,透析,冻干,得pH响应高分子聚羧基甜菜碱。3、将纯化后的pH响应高分子聚羧基甜菜碱与1106mg甲基丙烯酸己酯和67mg偶氮二异丁腈溶于甲醇中重复“冷冻-抽真空-通氮气-复融”步骤三次后,65℃反应24h,透析,冻干,得到亲、疏链段聚合度比例为25∶5的pH响应两亲嵌段聚合物。
(2)、通过酸铵缩合反应制备阳离子pH响应两亲嵌段共聚物:
1、320mg pH响应两亲嵌段聚合物与40mg六氟磷酸苯并三唑-1-基-氧基三吡咯烷基磷,30mg三乙胺和20mg L-精氨酸溶于N,N-二甲基甲酰胺(DMF)溶液中,40℃反应24h。2、用DMF与水透析24h,冻干,得纯化后的阳离子两亲嵌段共聚物。
(3)、阳离子pH响应两亲嵌段共聚物负载香料:
1、100mg阳离pH响应子两亲嵌段共聚物和80mg芳樟醇香料溶于二甲基亚砜中,并在剧烈搅拌中逐滴加入到50ml去离子水中。2、超声0.5h,3、最后通过透析除去有机溶剂及未包载的香料。其中透析袋截留分子量为7000,透析液为去离子水。最终得到pH响应缓控释的聚合物纳米香料。
上述所得的pH响应缓控释的聚合物纳米香料所得产物粒径在300nm左右。所得纳米香料的载香率达到了36.65%。
应用实施例
丝绸样品(25cm2)浸泡在上述实施例1制备的pH响应缓控释的聚合物纳米香料水溶液中搅拌12h,其中搅拌速率为1200rpm。且芳樟醇浓度为1mg/mL。随后自然晾干。加香后的丝绸样品实现了香气分子在碱性条件稳定,酸性条件释放。解决了香料释放过程的不可控的问题,而且香气释放均匀,缓慢,留香时间久,效果明显。
此外,在本发明的上述实施例中,所述的有机溶剂还可以是本领域其他性质类似的有机溶剂,其也能实现基本相当的效果,并不以此为限。
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种pH响应缓控释的聚合物纳米香料的制备方法,其特征在于,所述制备方法包括以下步骤:
(1)将羧基甜菜碱单体、甲基丙烯酸己酯单体和含末端羧基的链转移剂在引发剂作用下通过可逆加成-断裂链转移聚合反应制备pH响应两亲嵌段共聚物;
(2)将所述pH响应两亲嵌段共聚物中的所述末端羧基和阳离子表面活性剂通过酸铵缩合反应制备阳离子pH响应两亲嵌段共聚物,其中阳离子表面活性剂为氨基酸类表面活性剂;
(3)将所述阳离子pH响应两亲嵌段共聚物负载香料,得到pH响应缓控释的聚合物纳米香料。
2.如权利要求1所述的制备方法,其特征在于,步骤(1)中,所述羧基甜菜碱单体通过将甲基丙烯酸二甲氨基乙酯和β-丙内酯反应制备。
3.如权利要求1所述的制备方法,其特征在于,步骤(1)中,所述可逆加成-断裂链转移聚合反应的步骤具体包括以下子步骤:
子步骤(11),将含末端羧基的链转移剂,羧基甜菜碱单体与引发剂溶于有机溶剂中,按照“冷冻-抽真空-通氮气-复融”步骤重复处理,然后进行加热反应后透析纯化得到pH响应高分子聚羧基甜菜碱;
子步骤(12),将纯化后的所述pH响应高分子聚羧基甜菜碱与甲基丙烯酸己酯单体和引发剂溶于有机溶剂中,按照“冷冻-抽真空-通氮气-复融”步骤重复处理,然后在进行加热反应后透析纯化得到pH响应两亲嵌段共聚物。
4.如权利要求3所述的制备方法,其特征在于:
所述含末端羧基的链转移剂为4-氰基-4-(十二烷基硫烷基硫代羰基)硫烷基戊酸;
所述引发剂为偶氮二异丁腈;
所述羧基甜菜碱单体、甲基丙烯酸己酯单体和含末端羧基的链转移剂的质量比为10~20∶2.75∶1。
5.如权利要求1所述的制备方法,其特征在于,步骤(2)具体包括:将所述pH响应两亲嵌段共聚物、缩合剂,碱催化剂和阳离子表面活性剂溶于有机溶剂中进行加热反应后,通过透析纯化得到阳离子pH响应两亲嵌段共聚物。
6.如权利要求5所述的制备方法,其特征在于:
所述缩合剂为六氟磷酸苯并三唑-1-基-氧基三吡咯烷基磷;
所述碱催化剂为三乙胺;
所述阳离子表面活性剂为L精氨酸或赖氨酸。
7.如权利要求1所述的制备方法,其特征在于:步骤(3)具体包括以下子步骤:
子步骤(31),将所述阳离子pH响应两亲嵌段共聚物和香料溶于有机溶剂中,并在剧烈搅拌中逐滴加入到去离子水中;
子步骤(32),进行超声沉淀;
子步骤(33),通过透析除去有机溶剂及未包载的香料,得到pH响应缓控释的聚合物纳米香料。
8.如权利要求7所述的制备方法,其特征在于:子步骤(31)中:
所述香料为疏水性香料,选自花香、木香或果香;
所述pH响应两亲嵌段共聚物和香料的质量比为1~5∶1。
9.如权利要求7所述的制备方法,其特征在于,子步骤(33)中,所述透析使用截留分子量为7000的透析袋,透析液为去离子水。
10.一种使用如权利要求1至9任意一项所述的制备方法所制得的pH响应缓控释的聚合物纳米香料,其平均粒径为50~300nm,载香率为35.21~40.55%。
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