CN112430288A - 一种可见光引发常压制备膨胀微球的方法 - Google Patents
一种可见光引发常压制备膨胀微球的方法 Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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Abstract
本发明公开了一种可见光引发常压制备膨胀微球的方法,该方法将包含金属光敏剂、光引发剂、低沸点烷烃和烯烃类聚合单体的油相组成物与包含水、无机纳米颗粒和悬浮剂的水相组成物均匀混合形成悬浮液,所述悬浮液通过可见光引发进行悬浮聚合反应,即得;该方法制备的膨胀微球具有膨胀倍率高、聚合时间短、单体转化率高、单体残留率低等优点。
Description
技术领域
本发明涉及一种膨胀微球的制备方法,特别涉及一种可见光引发悬浮聚合制备膨胀微球的方法,属于膨胀微球制备技术领域。
背景技术
膨胀微球是指由热塑性聚合物外壳包裹发泡剂形成的具有核壳结构的微型颗粒物。微球受热至聚合物外壳软化点时,发泡剂产生的蒸气压使微球膨胀,冷却后,微球保持中空状态。由于膨胀微球具有质轻及闭孔发泡的特性,膨胀后的微球在隔热、隔音、减重等方面具有广泛的应用。
目前,常规的膨胀微球制备方法为高温高压下,通过悬浮聚合,并经过长时间反应后制备得到膨胀微球,难以在温和条件下实现膨胀微球的高效合成。如中国专利(CN101554575B)公开膨胀微球可以在常压下进行,但需要高温且反应时间长,且得到的膨胀微球发泡倍率低。受有机合成中光催化策略的影响,研究人员将光引发引入到自由基聚合领域,开发了光控自由基聚合法。该类型反应具有诸多优点,包括反应条件温和,具有一定的氧气兼容性,可通过光催化剂的合理选择实现聚合物的可控生产,但目前很少用于悬浮聚合制备空心微球的技术中来。
总而言之,现有的聚合方法在制备膨胀微球过程中存在一定的局限性:(1)聚合条件苛刻,需要高温高压长时间反应;(2)分子量分布范围不可控;(3)微球发泡倍率低等诸多不足。
发明内容
针对现有技术存在的缺陷,本发明的目的是在于提供一种通过可见光引发自由基悬浮聚合制备膨胀微球的方法,该方法反应条件温和、聚合速率快、单体转化率高、操作简便,有利于大规模工业化生产。
为了实现上述技术目的,本发明提供了一种可见光引发常压制备膨胀微球的方法,该方法是将油相组成物与水相组成物均匀混合形成悬浮液,所述悬浮液通过可见光引发进行悬浮聚合反应,即得;
所述水相组成物包含水、无机纳米颗粒和悬浮剂;
所述油相组成物包含光催化剂、光引发剂、低沸点烷烃和烯烃类聚合单体;
所述烯烃类聚合单体包含丙烯腈类单体和丙烯酸酯类单体。
作为一个优选的方案,所述金属光敏剂为金属铱(Ir)和/或钌(Ru)的金属有机配合物,具体如以下金属有机配合物中至少一种:
本发明的金属光敏剂主要是用于提高光量子效率,在吸收光能后跃迁到激发态,然后将能量传递给光引发剂,诱导产生自由基。优选的金属光敏剂能够在可见光波长范围内被激发,对于可见光的吸收有更高的效率,从而可以实现在可见光下进行光引发聚合。
作为一个优选的方案,所述光引发剂具有以下结构通式:
其中,
R1为C3~C12的脂肪烃基
R2为含有至少一个亲水基团的C3~C60的脂肪烃基。
作为优选,R1可以为饱和脂肪烃基或不饱和脂肪烃基,具体如C3~C12烷基,或者含一个或多个烯基的C3~C12不饱和脂肪烃基,或含有一个或多个炔基的不饱和脂肪烃基;进一步优选R1为C3~C12烷基,烷基包括直链烷基或带支链的烷基。
本发明技术方案选择的硫代引发剂同时包含非亲水的脂肪烃基和富含亲水羧基的基团,具备良好的亲水亲油特性,有利于引发自由基悬浮界面聚合。
作为一个优选的方案,所述无机纳米颗粒为纳米氢氧化镁、纳米二氧化硅、羟基磷酸钙中至少一种。
作为一个优选的方案,所述悬浮剂为聚乙烯醇、羧基纤维素、聚乙烯吡咯烷酮中至少一种。
作为一个优选的方案,所述低沸点烷烃为C5~C15烷烃,包括支链烷烃或直链烷烃。
作为一个优选的方案,水与烯烃类聚合单体的质量比为2~4:1。
作为一个优选的方案,无机纳米颗粒质量为烯烃类聚合单体质量的3~12%。
作为一个优选的方案,悬浮剂质量为烯烃类聚合单体质量的0.5~5%。
作为一个优选的方案,烯烃类聚合单体与光引发剂的摩尔比为1000:(1~100)。
作为一个优选的方案,光催化剂为烯烃类聚合单体摩尔量的0.005~1%。
作为一个优选的方案,低沸点烷烃为聚合单体总重量的20%~40%。
作为一个优选的方案,所述烯烃类聚合单体以烯烃类聚合单体总重量为100%计量,由以下质量百分比组分组成:丙烯腈类单体20%~80%,丙烯酸酯类单体5%~50%,丙烯酰胺类单体0%~30%,丙烯酸类单体0%~30%。
作为一个优选的方案,
所述丙烯腈类单体具有以下结构通式:
所述丙烯酸酯类单体具有以下结构通式:
所述丙烯酰胺类单体具有以下结构通式:
所述丙烯酸类单体具有以下结构通式:
其中,
R3为氢或甲基;
R4为C1~C10烷基(作为优选,烷基可以为直链烷基或者碳原子数超过3时还包括带支链的烷基或环烷基);
R5为氢或C1~C4烷基(作为优选,烷基可以为直链烷基或者碳原子数超过3时还包括带支链的烷基)。
作为一个优选的方案,水相中还包括金属离子络合剂,如EDTA·4Na,用来络合悬浮聚合体系中微量的铜离子、铁离子等,防止这些金属离子阻碍聚合反应的进行,在聚合过程中加入EDTA作为络合剂可排除这些金属离子对聚合反应的影响。
作为一个优选的方案,所述悬浮聚合反应条件为:在氮气氛条件下,保持常压,在25~35℃温度下聚合2~6小时。进一步优选,体系pH控制为3~4。
作为一个优选的方案,所述可见光由1~100W的白色LED灯提供。
本发明的膨胀微球的制备方法,具体步骤如下:
1)将光催化剂、光引发剂、低沸点烷烃和烯烃类聚合单体等组份组成油相组成物;按照摩尔比计,烯烃类聚合单体:光引发剂=1000:(1~100),光催化剂为烯烃类聚合单体摩尔量的0.005~1%;低沸点烷烃为聚合单体总重量的20%~40%。
2)将去离子水、无机纳米颗粒、悬浮剂组成水相组成物;按照重量比计,去离子水用量为烯烃类聚合单体总重量的200~400%,无机纳米颗粒为烯烃类聚合单体总量的3~12%,悬浮剂用量为烯烃类聚合单体总质量的0.1~5%。
3)将步骤1)中油相组成物与步骤2)中水相组成物通过均质乳化机乳化1~5min得到悬浮液,接着将所述悬浮液移入玻璃瓶中,在氮气氛保护下,用白色LED灯泡为光源,对反应混合物进行光照射,在25~35℃温度下,反应2~6小时
4)反应结束后,将反应液进行抽滤、洗涤、干燥,得到膨胀微球,取反应滤液测试水相中的单体残留量。
相对现有技术,本发明技术方案带来的有益技术效果:
1、本发明采用的三硫代化合物同时包含亲水基团和亲油基团,具有较好的亲水亲油特性,有利于引发自由基悬浮界面聚合。
2、本发明的光引发悬浮聚合与常规悬浮聚合相比,在制备膨胀微球过程中,水相无需添加氯化钠,降低了污水处理要求以及减少高盐水对设备的腐蚀,在现有技术中丙烯腈和丙烯酸酯等单体聚合往往需要加入大量氯化钠来起到盐析效应,降低丙烯腈和丙烯酸酯等聚合单体在水中的溶解性,从而降低单体在水相中发生聚合反应,减少副反应的发生和产生块状聚合物的现象。而本发明技术方案通过采用特殊的亲水亲油性光引发剂可有效提高溶解在水相中的聚合单体在微球表面聚合形成壳体的能力,从而避免了使用氯化钠。
3、本发明的光引发悬浮聚合反应在常温常压下进行,有利于反应热的排出,降低了对生产设备的要求。
4、本发明的光引发悬浮聚合反应时间短,提高了生产效率。
5、本发明的光引发悬浮聚合选择的光引发剂和光催化剂光敏性好,反应可控,可通过开/关光源实现反应的启动和停止,防止爆聚现象发生;并且采用可见光来引发聚合,可见光的波长更长,能量更低,具有穿透性强,副反应少,不释放臭氧,辐照安全,对生物无损害等优点,与现有的紫外光相比,紫外光的能量较高,长时间辐照容易引发副反应。
6、本发明的光引发悬浮聚合具有聚合速率快、单体转化率高,单体残留低的特点。
具体实施方式
用下列实施例和比较例具体描述本发明内容,但是本发明权利要求保护范围不限制在这些实施例的范围内。
实施例中,各缩写代表含义如下:
EDTA·4Na:乙二胺四乙酸四钠盐
AIBN:偶氮二异丁腈
AN:丙烯腈;
MAN:甲基丙烯腈;
MMA:甲基丙烯酸甲酯;
MA:丙烯酸甲酯;
MAA:甲基丙烯酸;
EGDMA:二甲基丙烯酸乙二醇酯;
IB:异丁烷;
IP:异戊烷;
IO:异辛烷;
CTT:2-(十二烷基硫基硫代羰基硫基)-2-甲基丙酸;
DDMA-GMA:自制。
原料来源:
有机金属光敏剂1~6(购自梯希爱(上海)化成工业发展有限公司);丙烯腈(齐鲁石油化工有限责任公司);甲基丙烯腈(丸红株式会社);异戊烷(吉林市龙燕化工厂);2-(十二烷基硫基硫代羰基硫基)-2-甲基丙酸(购自上海麦克林生化科技有限公司);其余来自北京华威瑞科试剂有限公司。
DDMA-GMA制备方法:(1)依次称取AIBN(0.050g),CTT(0.508g),二氧六环和丙烯酸(2.445g)于干燥三劲烧瓶中,在氮气气氛下,80℃反应12h;(2)去除反应混合物在真空条件下旋转蒸发,并在真空条件下干燥8h后,得到DDMA-GMA。
测试方法:
在下列实施例和比较例中制备的膨胀微球的各种特性测定如下:
1)平均粒径和粒径分布的测定:
采用LS-POP(9)型激光粒度分析仪(由欧美克仪器有限公司制造),测定膨胀微球的中位粒径(D50值)和粒径分布SPAN。
2)发泡特性分析:
采用TA Instrument公司生产的静态热机械分析仪TMA Q-400测量发泡特性。具体操作如下:由内直径3.4mm且深度14.2mm的铝坩埚放置TMA测试位,设定零位,再将0.5mg膨胀微球放入坩埚,读取探头初始高度,样品温度以20℃/min的升温速度从环境温度升高至300℃,并由探头施加0.06N的力分析通过测量探头垂直位移而进行,得出如下数据:
膨胀初始温度(Tstart),探头位移开始增大时的温度(℃);
发泡最高温度(Tmax),探头位移达到最大时的温度(℃);
最大发泡位移((Dmax):探头位移达到最大时的位移(μm)。
3)单体转化率测定:
样品制备方法:将反应混合物置于阴暗处,在氮气保护下,对反应液进行取样。取250μL样品置于容量瓶中,按比例稀释至250mL,通过移液枪吸取1mL稀释液于样品瓶中,进行测定,记录样品的气相色谱峰信号。通过GC对标准溶液及初始稀释试样进行3次测量取得平均值。
实验仪器:岛津株式会社,GC2014C;
色谱条件:初温40℃,恒温2min,以5℃/min升温速率升至100℃,恒温2min,再以6℃/min升温速率升至200℃,保持5min;检测器温度:250℃;进样器温度:225℃;顶空温度:95℃;平衡时间:20min。
实施例1
在600g去离子水中,加入40g有效成分30%的胶体二氧化硅,1g KURARAY POVAL48-80及1g EDTA·4Na,将所得的混合物搅拌均匀,得到水性分散介质,调节pH值至4.5。混合AN(60.0g),MAN(80.0g),MMA(50.0g),MAA(10.0g),EGDMA(0.4g),IP(70.0g),光敏剂1(20.0g),DDMA-GMA(82.31g)混合均匀制备得到油相混合物。
将水性分散介质与油性混合物混合后冷却至5~10℃,并将所得的混合液利用均质混合机(PRIMIX公司制造,TK均质混合机)以转速7000rpm分散3分钟,制备悬浮液。将该悬浮液移入容量2.0L的圆底烧瓶中,进行氮置换后,在30W白色LED等照射下搅拌反应物,在25℃下,反应聚合4小时,将所得的生成物过滤、干燥,得到膨胀性微球。对所得的膨胀性微球的平均粒径、膨胀起始温度、最大膨胀温度、单体转化率评价,其结果如表1所示。
实施例2~6
具体步骤如实施例1,对原料用量进行调整,具体如表1。
表1
本发明和以往的膨胀微球制备方法相比,能在常温常压下能快速制备得到膨胀微球,且具有操作简便、反应条件温和、聚合速率快、单体转化率高、单体残留量低、反应配方中不使用氯化钠等优点。
Claims (9)
1.一种可见光引发常压制备膨胀微球的方法,其特征在于:将油相组成物与水相组成物均匀混合形成悬浮液,所述悬浮液通过可见光引发进行悬浮聚合反应,即得;
所述水相组成物包含水、无机纳米颗粒和悬浮剂;
所述油相组成物包含金属光敏剂、光引发剂、低沸点烷烃和烯烃类聚合单体;
所述烯烃类聚合单体包含丙烯腈类单体和丙烯酸酯类单体。
4.根据权利要求1所述的一种可见光引发常压制备膨胀微球的方法,其特征在于:
所述无机纳米颗粒为纳米氢氧化镁、纳米二氧化硅、羟基磷酸钙中至少一种;
所述悬浮剂为聚乙烯醇、羧基纤维素、聚乙烯吡咯烷酮中至少一种;
所述低沸点烷烃为C5~C15烷烃。
5.根据权利要求1所述的一种可见光引发常压制备膨胀微球的方法,其特征在于:
水与烯烃类聚合单体的质量比为2~4:1;
无机纳米颗粒的质量为烯烃类聚合单体质量的3~12%;
悬浮剂的质量为烯烃类聚合单体质量的0.5~5%;
烯烃类聚合单体与光引发剂的摩尔比为1000:(1~100);
金属光敏剂为烯烃类聚合单体摩尔量的0.005~1%;
低沸点烷烃为聚合单体总重量的20%~40%。
6.根据权利要求1所述的一种可见光引发常压制备膨胀微球的方法,其特征在于:所述烯烃类聚合单体以烯烃类聚合单体总重量为100%计量,由以下质量百分比组分组成:丙烯腈类单体20%~80%,丙烯酸酯类单体5%~50%,丙烯酰胺类单体0%~30%,丙烯酸类单体0%~30%。
8.根据权利要求1~6任一项所述的一种可见光引发常压制备膨胀微球的方法,其特征在于:所述悬浮聚合反应条件为:在氮气氛条件下,保持常压,在25~35℃温度下聚合2~6小时。
9.根据权利要求1~6任一项所述的一种可见光引发常压制备膨胀微球的方法,其特征在于:所述可见光由1~100W的白色LED灯提供。
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