CN117797740A - 一种改善干粉团聚的可膨胀微球制备方法 - Google Patents
一种改善干粉团聚的可膨胀微球制备方法 Download PDFInfo
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- CN117797740A CN117797740A CN202311675443.6A CN202311675443A CN117797740A CN 117797740 A CN117797740 A CN 117797740A CN 202311675443 A CN202311675443 A CN 202311675443A CN 117797740 A CN117797740 A CN 117797740A
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Abstract
本发明提供了一种改善干粉团聚的可膨胀微球制备方法,包括以下步骤:(1)将单体、引发剂、交联剂和挥发性膨胀剂混合,获得油相;(2)将水性分散介质、无机盐、分散稳定剂、分散稳定助剂混合,获得水相;(3)将所述的油相和水相搅拌分散油相和水相,获得悬浮溶液;(4)将获得的悬浮溶液,在惰性气氛中,40‑80℃下,0.1~0.5MPa的压力下,聚合反应15~25小时后,将微球浆料温度降低至室温,加入一定量的分散剂搅拌分散0.5‑1小时,过滤并干燥得到干粉团聚改善的可膨胀微球;所述分散剂具有亲水性基团和亲油性基团。本发明的干粉团聚改善明显,同时也不影响可膨胀微球的发泡性能,拓宽了可膨胀微球的应用领域。
Description
技术领域
本发明涉及高分子材料领域,尤其涉及一种改善干粉团聚的可膨胀微球制备方法。
背景技术
可膨胀微球是由热塑性聚合物为壳内包可膨胀物质如脂肪族烃等挥发性膨胀剂所构成的具有核壳结构的微球体。可膨胀微球作为一种轻重填料已成功应用到橡皮泥,印花浆,塑料,弹性体等领域。然而可膨胀微球在制备完成进行干燥后却容易出现干粉团聚现象,最终直接导致微球在各种应用中的分散性不理想。
目前公开的专利中,关于微球自身干粉团聚的解决方案很少,在可膨胀微球聚合反应结束后引入处理剂和相关助剂在一定的温度条件下进行反应后可以改善可膨胀微球干粉团聚现象,但需要延长反应时间和增加能耗,生产成本相对要高、生产效率相对要低。
发明内容
为了解决上述问题,本发明提供了一种改善干粉团聚的可膨胀微球制备方法。
本发明提供了一种改善干粉团聚的可膨胀微球制备方法,包括以下步骤:
(1)将单体、引发剂、交联剂和挥发性膨胀剂混合,获得油相;
(2)将水性分散介质、无机盐、分散稳定剂、分散稳定助剂混合,获得水相;
(3)将所述的油相和水相搅拌分散油相和水相,获得悬浮溶液;
(4)将获得的悬浮溶液,在惰性气氛中,40-80℃下,0.1~0.5MPa的压力下,聚合反应15~25小时后,将微球浆料温度降低至室温,加入一定量的分散剂搅拌分散0.5-1小时,过滤并干燥得到干粉团聚改善的可膨胀微球。
进一步地,所述分散剂具有亲水性基团和亲油性基团。
进一步地,所述分散剂为壬基酚聚氧乙烯醚(NPEO)、辛基酚聚氧乙烯醚、十二烷基酚聚氧乙烯醚、聚氧乙烯壬基酚磷酸酯、吐温60、吐温61、吐温80中的任意一种。
进一步地,所述步骤(3)是通过用均质混合机在7000rpm下搅拌2分钟来分散油相和水相,从而制备悬浮溶液。
进一步地,所述的可膨胀微球包括热塑性外壳和包裹在所述的热塑性外壳中的挥发性膨胀剂。
进一步地,所述单体,包括如下重量份数的组份:
腈类单体 40~90份;
丙烯酸类单体 0~60份;
丙烯酸酯类单体 5~50份。
进一步地,所述腈类单体为丙烯腈、甲基丙烯腈、α-氯丙烯腈、α-乙氧基丙烯腈或富马腈中的一种或几种;所述丙烯酸类单体为丙烯酸、甲基丙烯酸、巴豆酸、肉桂酸、α-甲基肉桂酸马来酸、衣康酸、富马酸和柠康酸中的一种或几种;所述丙烯酸酯类单体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、二环戊烯基丙烯酸酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯或异冰片基甲基丙烯酸酯中的一种或几种。
进一步地,所述挥发性膨胀剂的沸点不高于所述热塑性外壳的软化温度,为C4~C12脂肪族烃类化合物。
优选地,所述挥发性膨胀剂为C4~C8直链或支链饱和烃类化合物。
更进一步地,所述挥发性膨胀剂为异辛烷、异戊烷、异丁烷、新戊烷、正己烷、庚烷、石油醚等低分子量烃、四甲基硅烷、三甲基乙基硅烷、三甲基异丙基硅烷、三甲基-正丙基硅烷中的一种或几种。
优选地,所述挥发性膨胀剂为异辛烷、异戊烷、异丁烷、正己烷、石油醚中的一种或几种。
优选地,以所述腈类单体、丙烯酸酯类单体总重量计:所述热塑性外壳,还包括如下重量百分比的组份:
进一步地,所述交联剂为二乙烯基苯、乙二醇二(甲基)丙烯酸酯、二(乙二醇)二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三烯丙基缩甲醛三(甲基)丙烯酸酯、甲基丙烯酸烯丙酯、三羟甲基丙烷三(甲基)丙烯酸酯、三丁二醇二(甲基)丙烯酸酯、PEG#200二(甲基)丙烯酸酯、PEG#400二(甲基)丙烯酸酯、PEG#600二(甲基)丙烯酸酯、3-丙烯酸氧基二醇单丙烯酸酯、三酰基缩甲醛、三烯丙基异氰酸酯、三烯丙基异氰脲酸酯、二乙烯基醚、乙二醇二乙烯基醚、二乙二醇二乙烯基醚、三乙二醇二乙烯基醚、或四乙二醇二乙烯基醚中的一种或几种;所述引发剂为二(十六烷基)过氧化二碳酸酯、二(4-叔丁基环己基)过氧化二碳酸酯、过氧化二辛酸、过氧化二碳酸二-(2-乙基己基)酯、过氧化二苯甲酸、过氧化二月桂酸、过氧化二癸酸、叔丁基过乙酸酯、叔丁基过月桂酸酯、叔丁基过氧化苯甲酸酯、氢过氧化叔丁基、二异丙基羟基二羧酸酯、2,2’-偶氮双((2,4-二甲基戊腈)、2,2’-偶氮双(异丁腈)、1,1’-偶氮双(环己烷-1-腈)、二甲基2,2,-偶氮双(2-甲基丙酸酯)、或2,2’-偶氮双[2-甲基-N-(2-羟乙基)-丙酰胺]中的一种或几种;所述分散稳定剂为胶体二氧化硅、胶体粘土、碳酸钙、磷酸钙、硫酸钙、草酸钙或碳酸钡中的一种或几种;所述分散稳定助剂为甲基纤维素、甲基羟丙基纤维素、聚乙烯醇、明胶、聚乙烯吡咯烷酮、聚环氧乙烷、氯化二烷基二甲基铵、氯化烷基三甲基铵、烷基硫酸钠、烷基磺酸钠、烷基二甲基氨基醋酸甜菜碱或烷基二羟基乙基氨基醋酸甜菜碱中的一种或几种。
优选地,所述热塑性外壳是在含有分散稳定剂和或分散稳定助剂的水性分散介质中进行悬浮聚合的,所述水性分散介质为水,其中还可以添加无机盐,所述无机盐为氯化钠、硫酸钠。
本发明所提供干粉团聚改善的可膨胀微球可用于各种应用中,如各种塑料,弹性体,橡皮泥、纸/纸板等,具体应用包括:PVC塑料,SBS弹性体,超轻粘土,盲文纸张,轻质水泥,中空陶瓷,乳化炸药等。
本发明人发现,在可膨胀微球中,通过在聚合反应结束后引入分散剂,分散剂具有亲水性基团的同时还具有亲油性基团,亲油性基团和微球表面的腈基、酯基、羧基具有很好的亲和作用,室温条件下分散剂可以很好的分散到微球和浆料水溶液的液固界面,有效隔离微球之间的羧基等基团的氢键作用,最终得到干粉团聚改善的可膨胀微球。
本发明的有益效果是:
本发明的干粉团聚改善明显,同时也不影响可膨胀微球的发泡性能,拓宽了可膨胀微球的应用领域。
附图说明
图1为空白实施例制备的可膨胀微球形貌图。
图2为实施1例制备的可膨胀微球形貌图。
图3为实施2例制备的可膨胀微球形貌图。
图4为实施3例制备的可膨胀微球形貌图。
图5为实施4例制备的可膨胀微球形貌图。
图6为实施5例制备的可膨胀微球形貌图。
具体实施方式
下面通过实施例对本发明作进一步阐述。在所列实施例中,除非另有说明,实施例中所有份数和百分率是指以重量计的份数和百分率,及可热膨胀性微球的分析采用下列方法及仪器:(1)粒径分布特性分析:
微球的粒径分布是通过Bekman coulter公司生产的粒径分布激光衍射分析仪LS13320测量,平均直径测量为体积平均粒径。
(2)发泡特性分析:
热膨胀性微球的特性通过TA Instrument公司生产的热机械分析仪TMA Q-400测量。由直径6.7mm且深度4.5mm的铝盘中容纳的1.0mg热膨胀性微球制备样品。然后,所述铝盘用直径6.5mm且深度4.0mm的铝盘密封。根据TMA扩展探头类型,样品温度以20℃/min的升温速度从环境温度升高至280℃,并由探头施加0.1N的力。分析通过测量探头垂直位移而进行。
-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(℃)。
-发泡密度(Dmin):微球添加量与发泡后体积的比值(kg/m3)
(3)干粉团聚评价方法:实验仪器是珠海欧美克仪器有限公司的欧美克颗粒图像处理仪-生物显微镜,型号是PIP8.1,对干粉进行10倍放大的观察分析。
微球浆料加入分散剂分散结束后取100克浆料,将抽滤后的滤饼放入烘箱,设定50℃干燥16小时。干燥结束后用研磨进行研磨,过150目筛。将筛下的干粉进行形貌和TMA分析。我们将通过空白实施例和实施例1~5进行对比。
空白可膨胀微球制备实施例
水相:
油相:
通过用均质混合机在7000rpm下搅拌2分钟来分散油相和水相,从而制备悬浮溶液。立刻将悬浮溶液注入1升高压反应釜中,通氮气替换空气,并对反应釜增压以达到0.3MPa的初始压力。然后,在50-70℃下进行聚合反应20小时。聚合完成后,通过过滤、洗涤、干燥得到基础可膨胀微球,微球相关性能见表1。
表1
表1中,(腈类单体)AN:丙烯腈,(丙烯酸酯类单体)MAA:甲基丙烯酸,甲基丙烯酸甲酯,TMPDMA:三羟甲基丙烷三甲基丙烯酸酯,LPO:过氧化十二酰,IP:异戊烷。
实施例1
制备空白实施例反应结束后加入3克NPEO室温分散0.5小时。将得到的产品过滤并干燥,从而获得干粉团聚改善的可膨胀微球,相关测试数据列于表2中。
实施例2
制备空白实施例反应结束后加入6克NPEO室温分散0.5小时。将得到的产品过滤并干燥,从而获得干粉团聚改善的可膨胀微球,相关测试数据列于表2中。
实施例3
制备空白实施例反应结束后加入9克NPEO室温分散0.5小时。将得到的产品过滤并干燥,从而获得干粉团聚改善的可膨胀微球,相关测试数据列于表2中。
实施例4
制备实施例中油相组成中加入6克NPEO室温分散1小时。将得到的产品过滤并干燥,从而获得干粉团聚改善的可膨胀微球,相关列于表2中。相关测试数据列于表2中。
实施例5
制备实施例中油相组成中加入6克吐温61室温分散0.5小时。将得到的产品过滤并干燥,从而获得干粉团聚改善的可膨胀微球,相关测试数据列于表2中。
通过表2的数据我们首先发现:加入分散剂室温分散后,微球的膨胀性能均无较大的影响。
通过附图中空白实施例和实施2、实施例5制备的可膨胀微球形貌图我们可以发现:在聚合反应结束后,室温条件下,加入分散剂后,借助分散剂特有的亲水亲油性,分散剂可以很好的分散到微球和浆料水溶液的液固界面,有效隔离微球之间的羧基等基团的氢键作用,微球的干粉团聚现象出现明显改善。另外,对比实施2、实施例5我们还可以发现:分散的种类不同时,干粉微球团聚改善的效果差异较大,NPEO分子结构中亲油性基团包括苯环、烷基且含量相对较高,吐温61中分子结构中的亲水性基团醚键含量较高,NPEO在浆料中更易向微球表面迁移而覆盖到微球表面对羧基、羟基起到隔离作用,因此分散剂NPEO的干粉微球团聚改善效果相对较好。
通过附图中实施例1、实施例2、实验例3制备可膨胀微球形貌图我们可以发现:不同分散剂用量条件下的干粉团聚改善情况不同,当分散剂用量较少时,微球的干粉团聚改善效果相对要差,增加分散剂用量后团聚改善效果持续增加,当超过一定数量后,干粉团聚改善的效果基本稳定,即分散剂需要尽可能覆盖到浆料中微球和水溶液的固液表面才能起到隔离微球之间的羧基作用,分散剂用量过量后,覆盖到微球表面的分散剂已经饱和,因此对微球干粉团聚改善的效果不会显著提高。
通过附图中实施例2、实施例4我们可以发现:不同的分散时间条件下,干粉微球团聚改善的效果差异不大,分散剂在浆料水溶液中迁移到微球表面需要一定的时间,当覆盖完全后,延长分散过程的时间对微球表面分散剂的覆盖量没有明显影响,因此干粉微球团聚改善的效果差异不大。
表2
根据上述说明所给出的方法,是本领域技术人员能够想到本发明的多种修改和其他实施方式。因此,本发明的保护范围并不限于披露的实施例,任何所属技术领域的技术人员对其所做的适当变化或修饰,皆应视为不脱离本发明的专利范畴。
Claims (5)
1.一种改善干粉团聚的可膨胀微球制备方法,其特征在于,包括以下步骤:
(1)将单体、引发剂、交联剂和挥发性膨胀剂混合,获得油相;
(2)将水性分散介质、无机盐、分散稳定剂、分散稳定助剂混合,获得水相;
(3)将所述的油相和水相搅拌分散油相和水相,获得悬浮溶液;
(4)将获得的悬浮溶液,在惰性气氛中,40-80℃下,0.1~0.5MPa的压力下,聚合反应15~25小时后,将微球浆料温度降低至室温,加入一定量的分散剂搅拌分散0.5-1小时,过滤并干燥得到干粉团聚改善的可膨胀微球;
所述分散剂具有亲水性基团和亲油性基团。
2.根据权利要求1所述的改善干粉团聚的可膨胀微球制备方法,其特征在于,所述分散剂为壬基酚聚氧乙烯醚(NPEO)、辛基酚聚氧乙烯醚、十二烷基酚聚氧乙烯醚、聚氧乙烯壬基酚磷酸酯、吐温60、吐温61、吐温80中的任意一种。
3.根据权利要求1所述的改善干粉团聚的可膨胀微球制备方法,其特征在于,所述步骤(3)是通过用均质混合机在7000rpm下搅拌2分钟来分散油相和水相,从而制备悬浮溶液。
4.根据权利要求1所述的改善干粉团聚的可膨胀微球制备方法,其特征在于,所述的可膨胀微球包括热塑性外壳和包裹在所述的热塑性外壳中的挥发性膨胀剂。
5.根据权利要求1所述的改善干粉团聚的可膨胀微球制备方法,其特征在于,所述单体,包括如下重量份数的组份:
腈类单体40~90份;
丙烯酸类单体0~60份;
丙烯酸酯类单体5~50份。
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