WO2015123961A1 - 一种挤出发泡热塑性聚氨酯弹性体粒子及其制备方法 - Google Patents

一种挤出发泡热塑性聚氨酯弹性体粒子及其制备方法 Download PDF

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Publication number
WO2015123961A1
WO2015123961A1 PCT/CN2014/082601 CN2014082601W WO2015123961A1 WO 2015123961 A1 WO2015123961 A1 WO 2015123961A1 CN 2014082601 W CN2014082601 W CN 2014082601W WO 2015123961 A1 WO2015123961 A1 WO 2015123961A1
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Prior art keywords
thermoplastic polyurethane
polyurethane elastomer
foaming
weight
parts
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PCT/CN2014/082601
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English (en)
French (fr)
Inventor
黄波
王仁鸿
王光阜
张生
赵玮
Original Assignee
山东美瑞新材料有限公司
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Application filed by 山东美瑞新材料有限公司 filed Critical 山东美瑞新材料有限公司
Priority to EP14883376.7A priority Critical patent/EP3109281B1/en
Priority to ES14883376T priority patent/ES2932412T3/es
Priority to MX2016010761A priority patent/MX2016010761A/es
Priority to KR1020167025521A priority patent/KR102109392B1/ko
Priority to US15/120,084 priority patent/US10137601B2/en
Publication of WO2015123961A1 publication Critical patent/WO2015123961A1/zh

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Abstract

本发明涉及一种挤出发泡热塑性聚氨酯弹性体粒子及其制备方法，所述粒子由以下重量份的成分组成：100重量份的热塑性聚氨酯弹性体，0.01～ 0.5重量份的发泡成核剂，0.01～0.2重量份的抗氧剂，所述制备方法为：先将物料混合，然后将混合物投入挤出机造粒得到适于发泡的珠粒原料，最后将上述珠粒投入发泡专用挤出机，经口模发泡后水下切粒，制得产品粒子。本发明利用挤出法制备热塑性聚氨酯发泡粒子，控制发泡工艺条件，得到密度可控的发泡粒子，粒子泡孔密度分布均匀，整体生产方法操作简单，对设备没有特设限制要求，适合工业连续化生产。

Description

一种挤出发泡热塑性聚氣酯弹性体粒子及其制备方法 技术领域
本发明涉及一种挤出发泡热塑性聚氨酯弹性体粒子及其制备方法，属于
说
发泡材料领域。 背景技术
书
以塑料为基体，通过物理或化学方法在塑料内部填充大量气泡，得到聚 合物发泡材料。 泡沫材料具有密度低，隔热隔音、 比强度高、 缓冲等一列优 点，因此在包装业、 工业、 农业、 交通运输业、 军事工业、 航天工业以及日 用品等领域得到广泛应用。 常用的泡沫塑料品种有聚氨酯（ PU )软质和硬 质泡沫塑料，聚苯乙烯（ PS )泡沫塑料，聚乙烯（ PE )泡沫塑料，聚丙烯 ( PP )泡沫塑料等。 但是聚氨酯泡沫塑料在发泡过程中容易残留异氰酸酯， 对人体有害，并且发泡材料无法回收利用。聚苯乙烯泡沫塑料产品降解困难， 易产生" 白色污染" 问题，联合国环境组织已决定停止使用 PS泡沫塑料产 品。 聚乙烯泡沫塑料耐高温性能较差，不适合在高温领域内应用。
热塑性聚氨酯弹性体（ TPU )具有较宽泛的硬度范围 ，优异的耐磨性、 机械强度、 耐水、 耐油、 耐化学腐蚀、 耐霉菌， 可回收利用等优点。 采用
TPU 制备的泡沫材料在保留原基体优异的性能之外， 同时具备优异的回弹 性，可以在较宽泛的温度范围内使用。基于上述优点，TPU发泡材料在许多 工业领域（汽车工业、 包装材料）以及日常生活领域（鞋材、 地板涂层）具 有非常广泛的应用前景。
目前制备发泡热塑性聚氨酯粒子的工艺主要为间歇式釜压发泡。 其中 ， WO2007/082838公开了一种基于热塑性聚氨酯的泡沫，该工艺采用高压釜 将 TPU颗粒与分散剂，表面活性剂以及正丁烷发泡剂均勻分散在水中 ，升 温至指定温度下保持一定的时间 ，然后将颗粒迅速卸压至大气压得到发泡热 塑性聚氨酯粒子粒，然后经过洗涤烘干等处理，得到水蒸气模压制品的原料。 该间歇式釜压发泡工艺较复杂，成本高。 发明内容
本发明 所要解决的技术问题是提供 一种挤出发泡热塑性聚氨酯弹性体 粒子及其制备方法，该方法可连续化生产 ，发泡材料质量稳定。
本发明解决上述技术问题的技术方案如下：一种挤出发泡热塑性聚氨酯 弹性体粒子，由以下重量份的成分组成： 100重量份的热塑性聚氨酯弹性体 ( TPU ) , 0.01 ~ 0.5重量份的发泡成核剂 ， 0.01 ~ 0.2重量份的抗氧剂。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，所述热塑性聚氨酯弹性体（ TPU )的邵氏硬度为 55A ~ 95A。 硬度是物质受压变形程度或抗刺穿能力的一种物理度量方式。硬度可分 相对硬度和绝对硬度。 绝对硬度一般在科学界使用 ，生产实践中很少用到。 我们通常使用硬度体系为相对的硬度，常用有以下几种标示方法：肖氏（也 叫邵氏，邵尔，英文 SH〇RE)、 洛氏、 布氏三种。 邵氏一般用于橡胶类材料 上。 邵氏硬度也称肖氏（ SHORE )硬度，常用于度量塑料，橡胶的表面抵 抗坚硬物体压入的能力。 肖氏硬度（ HS )和布氏硬度 （ BHN )换算关系为 HS=BHN/10 +12。 邵氏硬度的测试方法：用邵氏硬度计插入被测材料，表 盘上的指针通过弹簧与一个刺针相连，用针刺入被测物表面，表盘上所显示 的数值即为硬度值。
进一步，所述热塑性聚氨酯弹性体（ TPU )的熔体流动速率（ Ml )为 5 ~ 50g/10分钟。 上述数值是根据 ASTM-1238在 180°C施加 5Kg的重量测得。 ASTM指 美国材料与试验†办会 ( American Society for Testing and aterials^ST ) 前身是国际材料试验协会 ( Internationa! Association for Testing Materials, IAT > 19世纪 80年代，为解决采购商与供货商在购销工业材料过程中产 生的意见和分歧，有人提出建立技术委 m会制度，由技术委员会组织各方面 的代表参加技术座谈会，讨论解决有关材料规范、 试验程序等方面的争议问 题。 ASTM 的宗旨就是促进公共健康与安全，提高生活质量； 提供值得信 赖的原料、产品、体系和服务； 推动国家、地区、乃至国际经济。 ASTM-1238 是测试塑料熔体流动速率的美国材料协会的标准。
进一步，所述热塑性聚氨酯弹性体（ TPU )为基于数均分子量为 500 ~ 2000g/mol的聚四氢呋喃或数均分子量为 800 ~ 1200g/mol的聚酯多元醇中 的一种或两种的混合。
数均分子量 （Number-average Molecular Weight)：聚合物是由化学组 成相同而聚合度不等的同系混合物组成的，即由分子链长度不同的高聚物 混合组成。 通常采用平均数分子量表征分子的大小。 按分子数目统计平均， 则称为数均分子量，符号为 (MN)。
聚四氢呋喃，是一种易溶解于醇、 酯、 酮、 芳烃和氯化烃，不溶于酯肪 烃和水的白色蜡状固体。 当温度超过室温时会变成透明液体。
聚酯多元醇，有机物，通常是由有机二元羧酸（酸酐或酯）与多元醇（包 括二醇）縮合（或酯交换）或由内酯与多元醇聚合而成。 二元酸有苯二甲酸 或苯二甲酸酐或其酯、 己二酸、 卤代苯二甲酸等。多元醇有乙二醇、丙二醇、 一縮二乙二醇、 三羟甲基丙烷、 季戊四醇等。 不同品种的聚酯多元醇由于种 类不同或制备工艺不一样，性质也不一样，对于聚酯多元醇比较重要的几个 指标是羟值、 酸值、 水分、 粘度、 分子量、 密度以及色度等。 聚酯多元醇的 特性及用途：聚酯型聚氨酯因分子内含有较多的酯基、氨基等极性基团 ，内 聚强度和附着力强，具有较高的强度、 耐磨性。
进一步，所述发泡成核剂为滑石、 二氧化硅、 碳酸钙、 沸石、 石墨粉、 氧化铝、 氢氧化钙、 氢氧化铝、 硼酸锌中一种或几种的混合。
进一步，所述抗氧化剂为抗氧剂 1010、 抗氧剂 245、 抗氧剂 168、 抗 氧剂 Chinox 20N中一种或几种的混合。
抗氧剂 1010为 ΰ色结晶粉末，化学性状稳定，可广泛应用于通用塑料 , 工程塑料，合成橡胶，纤维 '热镕胶，树脂 '油品 ，墨水，涂料等行业中。 抗氧剂 245 ,名称是二醇双 [β -(3-叔丁基 -4-羟基 -5-甲基苯基)丙酸酯] ,该产 品作为抗氧剂用于 HIPS、 MBS, ABS等苯乙烯聚合物， P〇M、 PA等工程 塑料以及氨纶等聚氨酯的加工和长期热稳定性的改进。 同时在 PVC聚合工 艺中也是有效的链终止剂。本品对聚合物反应无影响，用于高抗冲聚苯乙烯、 聚氯乙烯时，可在聚合前加入单体中。抗氧剂 168名称是三 [2.4-二叔丁基苯 基]亚磷酸酯，本品辅助抗氧剂，与主抗氧剂 zm-1010或 1076复配，有很 好的协同效应，可有效地防止聚丙烯、 聚乙烯在基础注塑中的热降解，给聚 合物额外的长效保护。 抗氧剂 Chinox 20N是本领域内常规抗氧剂，具有优 秀的耐热抗氧化性能，无色污、 耐水解性极佳，对于 TPU有非常好的效果， 还可以应用于 P〇M、 PPR水管料等。
本发明解决上述技术问题的另一技术方案如下：一种挤出发泡热塑性聚 氨酯弹性体粒子的制备方法，包括以下步骤：取 100重量份的热塑性聚氨酯 弹性体（TPU X 0.01 ~ 0.5重量份的发泡成核剂、 0.01 ~ 0.2重量份的抗氧 剂混合均勻，然后将上述混合物投入挤出机造粒得到适于发泡的原料，最后 将上述原料投入发泡专用挤出机，并向挤出机中注入挥发性发泡剂，挤出机 的机头压力为 1 ~ 30MPa ,熔体经口模发泡后水下切粒，制得挤出发泡热塑 性聚氨酯弹性体粒子。
进一步，所述挥发性发泡剂为丙烷、 正丁烷、 异丁烷、 正戊烷、 异戊烷 一种或几种的混合，所述挥发性发泡剂加入的量为 1 ~40重量份。
进一步，所述发泡专用挤出机为单阶单螺杆挤出机、 双阶串联式单螺杆 挤出机、 同向双螺杆挤出机中的一种。
进一步，所述发泡专用挤出机的机头压力为 1MPa~30MPa，机头温度 为 150~185°C ,水下切粒机水温在 40~80°C。
所述的挤出发泡热塑性聚氨酯颗粒的发泡密度为 0.05~0.5g/cm3。
本发明的性能测试：
根据美国试验材料学会标准 ASTM D792-2008测试发泡颗粒发泡密度 p fo
发泡密度计算公式为 ：
p f=W1/(W1+W2-W3)；
其中 ， W1为发泡颗粒在空气中的质量，W2是使发泡颗粒浸渍在水中的 金属帽的重量， W3发泡颗粒在水中的质量。
本发明的有益效果是：本发明利用挤出法制备热塑性聚氨酯发泡粒子， 控制发泡工艺条件，得到密度可控的发泡颗粒，颗粒泡孔密度分布均勻，整 体生产方法操作简单，对设备没有特设限制要求，适合工业连续化生产。 具体实施方式
以下对本发明的原理和特征进行描述，所举实例只用于解释本发明 ，并 非用于限定本发明的范围。
下面通过具体实施例对本发明进行具体描述。
所述热塑性聚氨酯弹性体（ TPU )采用如表 1所示的成分。
表 1
软段 TPU
TPU 组成 （mol) 摩尔质量 组成 （mol)
邵氏硬度 己二酸 1,4-丁 聚四氢 (g/mol) 软段 1,4-丁 4.4-MDI 二醇 呋喃 二醇
A 1 1 - 900 1.00 0.55 1.55 80A
B - - 1 1500 1.00 0.83 1.83 85A 其中 ， TPU的邵氏硬度根据 ASTM D2204-05测定的。
实施例 1 ：
将 100份表 1所示的热塑性聚氨酯（ TPU )颗粒 A , 0.2重量份的滑石， 0.05重量份的抗氧剂 1010混合均勻，然后将上述混合物投入挤出机造粒得 到适于发泡的颗粒原料，最后将上述原料投入单阶单螺杆挤出机。 物料的挤 出速度控制在每小时挤出 55千克， 向挤出机中注入正丁烷的速度控制在每 小时 5千克，模头压力为 13Mpa ,模头温度为 172°C ,水下切粒机水温控制 在 70°C。 可按照上述组分比例连续添加物料，进行连续化生产 ，得到粒子 的发泡密度为 0.215g/cm3。
实施例 2：
将 100份表 1所示的热塑性聚氨酯（ TPU )颗粒 A , 0.3重量份的二氧 化硅， 0.07重量份的抗氧剂 245混合均勻，然后将上述混合物投入挤出机 造粒得到适于发泡的颗粒原料，最后将上述原料投入单阶单螺杆挤出机。 物 料的挤出速度控制在每小时挤出 55千克， 向挤出机中注入丙烷的速度控制 在每小时 7千克，模头压力为 15Mpa ,模头温度为 168°C ,水下切粒机水温 控制在 55°C。 可按照上述组分比例连续添加物料，进行连续化生产 ，得到 粒子的发泡密度为 0.202g/cm3。
实施例 3：
将 100份表 1所示的热塑性聚氨酯（ TPU )颗粒 B , 0.1重量份的碳酸 钙， 0.1 重量份的抗氧剂 1010混合均勻，然后将上述混合物投入挤出机造 粒得到适于发泡的颗粒原料，最后将上述原料投入同向双螺杆挤出机。 物料 的挤出速度控制在每小时挤出 40千克， 向挤出机中注入正戊烷的速度控制 在每小时 7千克，模头压力为 16Mpa ,模头温度为 183°C ,水下切粒机水温 控制在 70°C。 可按照上述组分比例连续添加物料，进行连续化生产，得到 粒子的发泡密度为 0.152g/cm3。
实施例 4：
将 100份表 1所示的热塑性聚氨酯（ TPU )颗粒 B , 0.08重量份的硼 酸锌， 0.1重量份的抗氧剂 1010 , 0.05重量份的抗氧剂 Chinox 20N混合均 勻，然后将上述混合物投入挤出机造粒得到适于发泡的颗粒原料，最后将上 述原料投入同向双螺杆挤出机。物料的挤出速度控制在每小时挤出 40千克， 向挤出机中注入正戊烷和异戊烷混合气的速度控制在每小时 8千克，模头压 力为 18Mpa ,模头温度为 175°C ,水下切粒机水温控制在 65°C。 可按照上 述组分比例连续添加物料 ， 进行连续化生产 ， 得到粒子的发泡密度为
Figure imgf000008_0001
实施例 5：
将 100份表 1所示的热塑性聚氨酯（ TPU )颗粒 B , 0.08重量份的硼 酸锌， 0.1重量份的抗氧剂 1010 , 0.05重量份的抗氧剂 Chinox 20N混合均 勻，然后将上述混合物投入挤出机造粒得到适于发泡的颗粒原料，最后将上 述原料投入同向双螺杆挤出机。物料的挤出速度控制在每小时挤出 40千克， 向挤出机中注入正丁烷和异丁烷混合气的速度控制在每小时 10千克，模头 压力为 20Mpa ,模头温度为 180°C ,水下切粒机水温控制在 65°C。 可按照 上述组分比例连续添加物料，进行连续化生产 ，得到粒子的发泡密度为
Figure imgf000008_0002
对比例：不添加发泡成核剂热塑性聚氨酯发泡粒子的制备
将 100份表 1所示的热塑性聚氨酯（ TPU )颗粒 B , 0.1重量份的抗氧 剂 1010 , 0.05重量份的抗氧剂 Chinox 20N混合均勻，然后将上述混合物 投入挤出机造粒得到适于发泡的颗粒原料，最后将上述原料投入同向双螺杆 挤出机。 物料的挤出速度控制在每小时挤出 40千克， 向挤出机中注入正丁 烷的速度控制在每小时 8千克，模头压力为 19Mpa ,模头温度为 175°C ,水 下切粒机水温控制在 65°C。 可按照上述组分比例连续添加物料，进行连续 化生产，得到颗粒的发泡密度为 0.128g/cm3。
各原料组分的添加比例以及发泡颗粒制备时的模头温度，模头压力 ，粒 子的发泡密度汇总于下表 2中。
表 2
Figure imgf000009_0001
其中 ，上述表格中的成核剂、 抗氧剂、 发泡剂均以重量百分比计（基于
TPU颗粒重量份）b
在实施例 1 ~ 5 中 ，得到的发泡珠粒密度在 0.1 12 ~ 0.215g/cm3之间 ， 颗粒表面光亮，在本发明要求范围内。 但是在对比例中 ，在热塑性聚氨酯颗 粒中没有未发泡成核剂，得到粒子密度为 0.128 g/cm3 ,粒子内部泡孔密度 分布不均勻，有明显的大小气孔存在。
以上所述仅为本发明的较佳实施例，并不用以限制本发明 ，凡在本发明 的精神和原则之内 ，所作的任何修改、 等同替换、 改进等，均应包含在本发 明的保护范围之内。

Claims

权 利 要 求 书
1. 一种挤出发泡热塑性聚氨酯弹性体粒子，其特征在于， 由以下重量 份的成分组成： 100重量份的热塑性聚氨酯弹性体， 0.01 ~ 0.5重量份的发 泡成核剂， 0.01 ~ 0.2重量份的抗氧剂。
2. 根据权利要求 1 所述挤出发泡热塑性聚氨酯弹性体粒子，其特征在 于，所述热塑性聚氨酯弹性体的邵氏硬度为 55A ~ 95A。
3. 根据权利要求 1 所述挤出发泡热塑性聚氨酯弹性体粒子，其特征在 于，所述热塑性聚氨酯弹性体的熔体流动速率为 5 ~ 50g/10分钟。
4. 根据权利要求 1至 3任一项所述挤出发泡热塑性聚氨酯弹性体粒子， 其特征在于 ， 所述热塑性聚氨酯弹性体为基于数均分子量为 500 ~ 2000g/mol的聚四氢呋喃或数均分子量为 800 ~ 1200g/mol的聚酯多元醇中 的一种或两种的混合。
5. 根据权利要求 4所述挤出发泡热塑性聚氨酯弹性体粒子，其特征在 于，所述发泡成核剂为滑石、 二氧化硅、 碳酸钙、 沸石、 石墨粉、 氧化铝、 氢氧化钙、 氢氧化铝、 硼酸锌中一种或几种的混合。
6. 根据权利要求 4所述挤出发泡热塑性聚氨酯弹性体粒子，其特征在 于，所述抗氧化剂为抗氧剂 1010、抗氧剂 245、抗氧剂 168、抗氧剂 Chinox 20N中一种或几种的混合。
7. —种挤出发泡热塑性聚氨酯弹性体粒子的制备方法，其特征在于， 包括以下步骤：取 100重量份的热塑性聚氨酯弹性体、 0.01 ~ 0.5重量份的 发泡成核剂、 0.01 ~ 0.2 重量份的抗氧剂混合均勻，然后将上述混合物投入 挤出机造粒得到适于发泡的原料，最后将上述原料投入发泡专用挤出机，并 向发泡专用挤出机中注入挥发性发泡剂，熔体经口模发泡后水下切粒，制得 挤出发泡热塑性聚氨酯弹性体粒子。
8. 根据权利要求 7所述挤出发泡热塑性聚氨酯弹性体粒子，其特征在 于，所述挥发性发泡剂为丙烷、 正丁烷、 异丁烷、 正戊烷、 异戊烷一种或几 种的混合，所述挥发性发泡剂加入的量为 1 ~ 40重量份。
9. 根据权利要求 7或 8所述挤出发泡热塑性聚氨酯弹性体粒子，其特 征在于，所述发泡专用挤出机为单阶单螺杆挤出机、 双阶串联式单螺杆挤出 机、 同向双螺杆挤出机中的一种。
10.根据权利要求 9所述挤出发泡热塑性聚氨酯弹性体粒子，其特征在 于，所述发泡专用挤出机的机头压力为 1 ~ 30MPa ,机头温度为 150 ~ 185 °C ,水下切粒机水温在 40 ~ 80°C。
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