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CN115403816A - 一种可膨胀热塑性发泡微球的制备方法 - Google Patents

一种可膨胀热塑性发泡微球的制备方法 Download PDF

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CN115403816A
CN115403816A CN202211207220.2A CN202211207220A CN115403816A CN 115403816 A CN115403816 A CN 115403816A CN 202211207220 A CN202211207220 A CN 202211207220A CN 115403816 A CN115403816 A CN 115403816A
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CN115403816B (zh
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彭敏
李玉新
熊然
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Hunan Fangrida Technology Co., Ltd.
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Abstract

本发明一种可膨胀热塑性发泡微球的制备方法，包括如下步骤：提供一种通过化学反应生成低沸点气体的固体芯材；采用水溶性高分子聚合物及交联剂包覆固体芯材，并进行交联反应形成可膨胀热塑性发泡微球。所述固体芯材为碳酸氢钠、偶氮二甲酰胺或4,4'‑氧代双苯磺酰肼中的至少一种。本发明具有以下有益效果：1、微球发泡剂外壳分子量分布更窄，制成的微球粒径范围更窄；2、解决了现有技术微球发泡剂支撑力不够，回缩较大等问题，扩大了微球发泡剂使用领域；3、解决了现有技术制备工艺需要过高压力难点，使大规模工业生产成为可能，同时成时间也明显缩短，极大的提高了生产效率。

Description

一种可膨胀热塑性发泡微球的制备方法
技术领域
本发明涉及一种发泡微球技术领域，具体涉及一种可膨胀热塑性发泡微球的制备方法。
技术背景
可膨胀微球发泡剂是一种乳白色的微小球状塑料颗粒，直径10-45微米。当加热到一定温度时，热塑性壳体软化，壳体里面的气体膨胀，发泡剂的体积可以增大到自身的几十倍，同时核壳结构并不破坏，从而达到发泡的效果。
这种特殊的发泡剂是核壳结构，外壳为热塑性丙烯酸聚合物，内核为烷烃气体组成的球状塑料颗粒。它的直径一般在10-30微米，聚合物壳体的厚度在2-15微米，壳体有良好的弹性并可承受较大压力，在加热膨胀之后发泡剂自身并不破裂，同时保持自身的良好性能。
可膨胀微球发泡剂的膨胀原理：可膨胀微球受热后聚合物壳体变软，同时壳体内气体膨胀。壳内的化合物在很短时间内膨胀为原来体积的20-50倍。发泡后的微球外壳并不会破裂，仍保持个完整的密封球体。微球有较高的回弹性，容易压缩，当压力释放后，微球又会回到原来的体积。
现有的可膨胀微球多采用高分子聚合材料包覆低沸点烷烃的方法进行生产。CN109414672 B、US2019233606A，WO2018011182A专利文件公开了可热膨胀热塑性微球及其制备方法，但是该类方法存在着下述弊端：采用的烷烃沸点相对常温较高，如戊烷、已烷等，在常温(低于烷烃沸点)时成为气态的烷烃又会变成液态，对于微球来说表现的是已经膨胀的微球又会回缩一部分，对于已经制成的发泡材料来说则体现出材料没有支撑力，甚至于已经定型的发泡材料在冷却后会不同程度的缩小体积。可以采用沸点较低的乙烷、甲烷甚至是氮气作为微球发泡剂的芯材来解决上述弊端，但这些芯材极难液化，其合成反应必须在较高的压力下进行，极容易导致合成失败。
发明内容
本发明的目的是提供一种可膨胀热塑性发泡微球的制备方法以解决现有技术存在问题。
为了实现上述发明目的，本发明所采用的技术方案是：一种可膨胀热塑性发泡微球的制备方法，包括如下步骤：提供一种通过化学反应生成低沸点气体的固体芯材；采用水溶性高分子聚合物及交联剂包覆固体芯材，并进行交联反应形成可膨胀热塑性发泡微球。
所述固体芯材为碳酸氢钠、偶氮二甲酰胺或4,4'-氧代双苯磺酰肼中的至少一种。
所采用的水溶性高分子聚合物选用聚乙烯醇、聚乙烯吡咯烷酮、丙烯腈和丙烯酸、甲基丙烯酸甲酯共聚物中的至少一种。
所述交联剂为含有两个或三个双键的交联剂。
所采用的交联剂为三烯丙基异氰脲酸酯、三羟甲基丙烷三丙烯酸酯、三官能团丙烯酸酯中的至少一种。
所述的制备方法，还包括将固体芯材进行预处理步骤，具体为：将固体芯材粉碎20-45微米后用液体石蜡进行表面疏水改性以形成致密的疏水层。
本发明一种可膨胀热塑性发泡微球的制备方法，首先将选用的固体芯材进行预处理，使芯材粒径达到1-100微米后用液体石蜡进行表面改性以形成致密的疏水层。
本发明采用的制备方法不直接采用沸点较低的烷烃作为芯材，而是采用常温下为固态的材料作为芯材，被包覆的芯材在高温制备环境中(150-200摄氏度)发生化学反应会生成氮气、二氧化碳等低沸点气体，气体产生的温度高于壳材合成所需的温度，这些气体在产生后即使温度降低也不会因为逆反应使芯材重新回到固体或液体状态，同时，这些低沸点的气体与CN109414672B专利文献所述的芯材(异丁烷、异戊烷等)在相同温度下能够产生更高的蒸汽压，在这样的环境下，合成反应时因为没有低沸点芯材的存在，可以在相对温和的条件下反应，不需要较高的压力来维持芯材的液态条件。因此在常温(0-40摄氏度)能够提高更高的支撑力，而更强的支撑力是微球发泡剂的特质所在。作为发泡材料，这样的优势在于既避免了合成过程中因为芯材沸点过低导致的合成困难，又能保证膨胀后微球的支撑力。
现有的微球发泡剂都采用丙烯腈、甲基丙烯酸甲酯一类的单体进行乳液聚合反应，用于形成微球发泡剂的外壳，该制备存在着反应时间至少需要20小时以上，反应产物成分复杂不容易控制，通常都具有较宽的分子量分布范围，这些都会极大的影响微球发泡剂的使用性能。
本发明采用成熟的聚合工艺将单体制成高分聚合物(聚乙烯醇、丙烯腈与丙烯酸酯共聚物)，然后加入交联剂(三烯丙基异氰脲酸酯、三羟甲基丙烷三甲基丙烯酸酯)、引发剂(双氧水、过硫酸铵、一叔丁基过氧化氢、二叔丁基过氧化氢等)，通过高分子交联反应增大聚合物分子量，反应后生成的外壳分子量分布更窄，制成的微球粒径范围更窄。上述反应过程中，水溶性的高分子材料从水中析出沉积在芯材表面，该析出沉积包裹形成的壳体更加均匀，采用这样的方法反应相对简单，降低了反映难度，更可以使反映时间缩短至10小时以内，提高了生产效率。
当然上述固体芯材必须通过一些方法预处理才能作为芯材在反应中使用。首先是要将固体的芯材通过球磨机粉碎到合适的粒径(20-45微米)也可以通过筛分使得粒径范围更窄，然后将这些合适粒径的固体材料通过喷雾法或者溶剂法进行表面改性，在表面形成致密的疏水层，这些疏水层能够使固体芯材在接下来的反应中稳定的分散在水相体系中。
本发明的制备方法中固体芯材占总重的20～40％，高分子聚合物占总重的的60～80％,交联剂为总重的1.7～2.3％，去离子水为总重的7-8倍，引发剂为总重的2-3％，总重指固体芯材和高分子聚合物的总重量。
本发明与现有技术相比具有以下有益效果：1、采用高分子交联反应形成的微球发泡剂外壳分子量分布更窄，制成的微球粒径范围更窄；2、解决了现有技术微球发泡剂支撑力不够，回缩较大等问题，扩大了微球发泡剂使用领域；3、解决了现有技术制备工艺需要过高压力难点，使大规模工业生产成为可能，同时成时间也明显缩短，极大的提高了生产效率。
具体实施方式
分别称取不同重量的固体芯材，使用超微粉碎机粉碎并过筛，液体石蜡进行喷雾干燥表面疏水处理，分别称取高分子聚合物、交联剂加入去离子水投入到250ml三口烧瓶中，均质机下15000rpm均质5分钟，接上搅拌和冷凝回流装置，物料水浴升温至60℃，滴加引发剂(1g稀释到10g)，半小时内滴加完毕。65℃保温10小时后，过滤，滤饼用正庚烷漂洗2次后60℃烘干致恒重得到固体粉末(粒径DN50 25微米),制备后得到微球。其中，固体芯材占总重的20～40％，高分子聚合物占总重的的60～80％,交联剂为总重的1.7～2.3％，去离子水为总重的7-8倍，引发剂为总重的2-3％，总重指固体芯材和高分子聚合物的总重量。各实施例的具体数值如下：
Figure BDA0003874488240000041
各实施例得到的微球检测数据如下：
实施例 起泡温度 破泡温度 微球粒径
实施例1 150℃ 180℃ DN50 25μm
实施例2 150℃ 180℃ DN50 25μm
实施例3 160℃ 190℃ DN50 20μm
实施例4 160℃ 180℃ DN50 25μm
起泡温度、破泡温度的检测：在显微熔点仪下观察已经布置成单层的微球发泡剂，同时将显微熔点仪加热速率设置为10摄氏度/分钟。当观察到镜头中微球发泡剂出现发泡现象时，记录下当前的温度值，此温度为起泡温度。继续观察微球发泡剂在不同温度下的表现，当镜头下的微球发泡剂全部破掉后，记录下此时的温度，此温度为破泡温度。
上述所有实施例中发泡并冷却至室温后的微球发泡剂在显微镜下观察没有凹陷的现象，仍然可以维持圆润的球形。
将本发明的实施例与CN109414672B专利文献所述的制备方法合成的微球作为对比例，进入如下对比。
对比例微球的制备如下：制备包含水(227份)、用35％甲基丙烯酰胺基丙基甲硅烷基(疏水)表面改性的胶体二氧化硅(Bindzil 40wt％、130m2/g、粒度22nm)(8份)和聚合催化剂过氧二碳酸二(4-叔丁基环己基)酯(0.5份)的分散体并保持在大约4.5的pH下。将该水性分散体与单体丙烯腈(58份)、甲基丙烯酸甲酯(18份)、偏二氯乙烯(24份)和发泡剂异戊烷(16份)和交联剂三羟甲基丙烷三甲基丙烯酸酯(0.35份)的油相混合。搅拌该混合物并在密封容器中在57℃下进行聚合20小时。
一、在相同温度57℃下的所需蒸气压、分子量分布对比
蒸气压 分子量
实施例1 0.13MPa 4-5万
实施例2 0.13MPa 5-6万
实施例3 0.14MPa 5-6万
实施例4 0.15MPa 6-7万
对比例 0.4MPa 5-8万
从表中数据可以看出采用本发明技术方案的制备方法，在相同温度下的蒸气压远远小于对比例制备方法所需的蒸气压，形成的微球发泡剂外壳分子量分布更窄。
二、微球支撑力试验对比：首先将本发明的各实施例和按照对比例所制得的微球分别用1ml量筒量准确取1ml微球，然后倒入100ml量筒中。将量筒放入温度适当的烘箱中(烘箱温度根据微球膨胀的发泡温度调整)，当微球膨胀到最高刻度时，读取量筒上的数值既为发泡倍率N ml,按照公式：N ml/1ml＝N，既为发泡倍率N倍，如量筒上的刻度为100ml，发泡倍率为100倍。然后将量筒冷却至0摄氏度后在量筒上盖一纸板，纸板上加上不同重量的法码得到不同的数据如下：
Figure BDA0003874488240000061
上表中，膨胀倍率后为加法码以后，膨胀倍率前为加法码以前。试验原理如下：在堆积成圆筒状的已发泡的微球上，在相同条件下，施加一个相同大小的压力(法码)，已发泡微球在压力下会有不同程度的缩小，体现在宏观上则是发泡倍率的减小。通过这个试验可以看出在相同压力下发泡倍率减小比较少的支撑力较好。
三、微球用于鞋材产品膨胀效果和支撑力试验对比：
EVA是乙烯-醋酸乙烯共聚物泡沫材料，用EVA塑胶粒子先加热再发泡而成，表面粗糙，常用于慢跑、慢步、休闲鞋、足训鞋中底，一双EVA中底的跑鞋在跑上一定里程经过反复踩踏之后，泡沫中的空气被挤出去，就会导致EVA无法恢复到原来形状，缓冲性能就会明显下降，带来的直观感觉是脚感变得变硬，本发明的微球用于鞋底材料的制备，能使鞋底中包含的泡沫微球在膨胀过程中，内含微型密闭气泡的椭圆形微球的体积将增大几十倍，使鞋底具备弹性，在鞋底与外力(地面)冲击作用下，微球可以最多压缩至原来一半大小，这对于足部减震非常重要，压缩力消失后，微球泡沫又可迅速恢复到原来的形状，本发明微球制成的鞋底经反复踩踏后，仍可长久保持柔软、缓震性能与回弹性，耐疲劳性优异。
将本发明的各实施例与对比例微球用于鞋中底材料的制备，制成的泡沫制品经挤压试验得到对比如下(试验以《HG/T4806-2015胶鞋、鞋底试验方法压缩变形性检测标准》为检测方法)：
变形率500次(％) 变形率1000次(％) 变形率2000次(％)
实施例1 0.6 1.0 1.1
实施例2 0.7 1.2 1..3
实施例3 0.6 0.9 1
实施例4 0.5 0.8 1
对比例 1 1.5 1.8
从上述试验数据可看出本发明技术方案制得的微球的支撑力远远高于对比例，变形率越小代表支撑力越强。
以上实施例仅为本发明部分实施方案，但本发明的保护范围不仅限于此，如本文中公开的本发明的各种方面和实施方案仅是举例说明作出和利用本发明的具体方式。也不因实施例的前后顺序以及具体操作对本发明造成任何限制，任何熟悉本技术领域的科研人员在本发明揭露的技术范围内，可轻易想到的替换和变化都应包含在本发明的保护范围之内。

Claims (6)

1.一种可膨胀热塑性发泡微球的制备方法，其特征在于，包括如下步骤：
提供一种通过化学反应生成低沸点气体的固体芯材；
采用水溶性高分子聚合物及交联剂包覆固体芯材，并进行交联反应形成可膨胀热塑性发泡微球。
2.根据权利要求1所述的制备方法，其特征在于，所述固体芯材为碳酸氢钠、偶氮二甲酰胺或4,4'-氧代双苯磺酰肼中的至少一种。
3.根据权利要求1所述的制备方法，其特征在于，所采用的水溶性高分子聚合物选用聚乙烯醇、聚乙烯吡咯烷酮、丙烯腈和丙烯酸、甲基丙烯酸甲酯共聚物中的至少一种。
4.根据权利要求1所述的制备方法，其特征在于，所述交联剂为含有两个或三个双键的交联剂。
5.根据权利要求4所述的制备方法，其特征在于，所采用的交联剂为三烯丙基异氰脲酸酯、三羟甲基丙烷三丙烯酸酯、三官能团丙烯酸酯中的至少一种。
6.根据权利要求1所述的制备方法，其特征在于，还包括将固体芯材进行预处理步骤，具体为：将固体芯材粉碎至20-45微米后用液体石蜡进行表面疏水改性以形成致密的疏水层。
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