CN106626202A - 一种膨胀型热塑性聚氨酯弹性体制品的制备方法 - Google Patents

一种膨胀型热塑性聚氨酯弹性体制品的制备方法 Download PDF

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CN106626202A
CN106626202A CN201710028890.0A CN201710028890A CN106626202A CN 106626202 A CN106626202 A CN 106626202A CN 201710028890 A CN201710028890 A CN 201710028890A CN 106626202 A CN106626202 A CN 106626202A
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preparation
thermoplastic polyurethane
binding agent
polyurethane elastomer
expanded thermoplastic
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王光阜
宋红玮
杨冲冲
任光雷
王仁鸿
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Miracll New Material Co Ltd
Miracll Chemicals Co Ltd
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Miracll New Material Co Ltd
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Priority to CN201710028890.0A priority Critical patent/CN106626202A/zh
Priority to PT178917522T priority patent/PT3569647T/pt
Priority to MX2019008486A priority patent/MX2019008486A/es
Priority to KR1020197023983A priority patent/KR102291202B1/ko
Priority to US16/478,290 priority patent/US11530310B2/en
Priority to ES17891752T priority patent/ES2933100T3/es
Priority to PCT/CN2017/074658 priority patent/WO2018129791A1/zh
Priority to EP17891752.2A priority patent/EP3569647B1/en
Publication of CN106626202A publication Critical patent/CN106626202A/zh
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Abstract

本发明涉及一种膨胀型热塑性聚氨酯弹性体制品的制备方法，包括如下步骤：1)涂覆粘结剂：使膨胀型热塑性聚氨酯弹性体粒子的表面附着粘结剂；2)固化成型：步骤1)中所得产品加入到成型模具中后置于硫化机内模压固化成型；3)冷却定型：将步骤2)中成型后的成型模具冷却，即得。本发明的通过在膨胀型热塑性聚氨酯弹性体粒子表面预先附着粘结剂的方式，可以减少粘结剂添加的比例，最大程度地利用膨胀型热塑性聚氨酯弹性体粒子的特性。

Description

一种膨胀型热塑性聚氨酯弹性体制品的制备方法
技术领域
本发明涉及一种热塑性聚氨酯弹性体制品的制备方法，尤其涉及一种膨胀型热塑性聚氨酯弹性体制品的制备方法，属于轻量化材料领域。
背景技术
聚合物发泡材料是以聚合物为基体材料，通过物理或化学方法使聚合物基体内部产生大量的泡孔结构。由于发泡材料独特的泡孔结构赋予了其一系列优良的性能，如密度低、隔热隔音、比强度高、缓冲等，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具有广泛的应用。常用的泡沫材料种类有聚氨酯(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、发泡乙烯-醋酸乙烯(EVA)等。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，发泡EVA采用模压发泡工艺加工，此种工艺设备已经相当成熟，但发泡EVA长时间使用过程中弹性损失严重，并且制备过程中不环保。
热塑性聚氨酯弹性体(TPU)材料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，对环境友好，可回收利用等优点。膨胀型热塑性聚氨酯弹性体粒子在保留热塑性聚氨酯基体优异的性能之外，同时具有优异的回弹性，形状多样性，低密度，可以在较宽的温度范围内使用。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、枕头、床垫)具有非常广泛的应用前景。
CN103371564A公开了采用膨胀型热塑性聚氨酯弹性体粒子(E-TPU)材料生产中底和鞋内底制品的方法，其采用水蒸气模塑设备加工，在特殊设计的模具中，通过水蒸气将发泡热塑性聚氨酯粒子烧结成型，但是此种生产设备工艺复杂，设备成本高，模具设计复杂，成品率低，严重限制了此材料的推广与应用。因而开发一种适用于通用模发泡设备的膨胀型热塑性聚氨酯弹性体材料以及制备方法成为许多公司和研究机构的目标。
发明内容
本发明针对现有膨胀型热塑性聚氨酯加工成型方法上存在的不足，提供一种膨胀型热塑性聚氨酯弹性体制品的制备方法。
本发明解决上述技术问题的技术方案如下：
一种膨胀型热塑性聚氨酯弹性体制品的制备方法，其特征在于，包括如下步骤：
1)附着粘结剂：使膨胀型热塑性聚氨酯弹性体粒子的表面附着粘结剂；
2)固化成型：步骤1)中所得产品加入到成型模具中后置于硫化机内模压固化成型；
3)冷却定型：将步骤2)中成型后的成型模具冷却，即得。
进一步，步骤1)中所述的粘结剂为熔点处于40-200℃的可热熔树脂，其形态为粉体、液体中的一种。
进一步，步骤1)中所述的粘结剂为热塑性聚氨酯弹性体、丙烯酸酯、环氧树脂、单组份聚氨酯、双组份聚氨酯、水性聚氨酯中的一种。
进一步，所述粉体形态的可热熔树脂的粒径为30-5000目，优选50-3000目，特别优选300-2500目；所述液体形态的可热熔树脂其有效固含量为5-100wt％，优选10-80％，特别优选20-50％。
进一步，步骤1)中所述的膨胀型热塑性聚氨酯弹性体粒子的密度为0.001-0.6g/cm3，优选0.05-0.3g/cm3,特别优选0.15-0.25g/cm3，其根据ASTM-D792测试得到。
进一步，步骤1)中于膨胀型热塑性聚氨酯弹性体粒子的表面附着粘结剂的方法为静电吸附、喷涂、干混中的一种，可以采用简单混合器如转鼓式混合器或高混机中进行机械混合或在塑料容器中手动进行混合，得到表面附着粘结剂的膨胀型热塑性聚氨酯弹性体粒子。
进一步，步骤1)中所述的粘结剂与膨胀型热塑性聚氨酯弹性体粒子的质量比为1:1到1：10000。
进一步，步骤2)中硫化机的硫化温度为40-200℃，硫化压力为0.01-1MPa，硫化时间为1-30分钟。
进一步，步骤3)中冷却的温度为10-40℃，冷却时间为1-20min。
本发明的方法采用通用成熟的模压发泡工艺设备，通过调整粘结剂与膨胀热塑性聚氨酯粒子的混合比例以及固化温度，在保留膨胀热塑性聚氨酯粒子优异弹性的前提下，通过粘结剂的固化作用使发泡热塑性聚氨酯粒子相互粘结在一起，使得所制备的制品具有优异的回弹性，耐曲折和压缩变形等性能，从而避免了水蒸气模塑成型工艺中由于水蒸气加热不均匀导致膨胀热塑性聚氨酯粒子之间粘结不牢等缺陷问题。
本发明的有益效果是：
1)通过在膨胀型热塑性聚氨酯弹性体粒子表面预先附着粘结剂的方式，可以减少粘结剂添加的比例，最大程度地利用膨胀型热塑性聚氨酯弹性体粒子的特性；
2)通过控制固化温度，使粘结剂固化膨胀型热塑性聚氨酯粒子成型，无需通过高压高温水蒸气介质熔接膨胀型热塑性聚氨酯粒子，避免了高成本的水蒸气模塑成型设备的投资与相应模具和设备的研发，无需进行设备再投资与改造，生产工艺简单，生产成本低；便于控制，工艺成熟，成品率高；
3)本发明的方法所制备的制品具有优异弹性，拉伸强度，抗曲折弯曲性能，是目前通过水蒸气模塑成型工艺制备的膨胀型热塑性聚氨酯制品材料无法比拟的。
具体实施方式
以下结合实例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。
实施例1：
一种膨胀型热塑性聚氨酯弹性体制品的制备方法，包括如下步骤：
(1)采用静电吸附方式将1重量份的热塑性聚氨酯粉末( H306)涂覆在1重量份的膨胀热塑性聚氨酯粒子表面，其中热塑性聚氨酯粉末的熔点为80-100℃，粒径为30目；发泡热塑性聚氨酯粒子的密度为0.6g/cm3,外观为白色，形状为椭圆形；
(2)称取100g上述表面附着粘结剂的膨胀型热塑性聚氨酯弹性体粒子并装填到制品模具中；
(3)将步骤(2)的制品模具置于平板硫化机中进行模压固化成型，平板硫化机的硫化温度为100℃，硫化压力为0.01Mpa,硫化时间为2分钟；
(4)将上述步骤(3)的制品模具采用冷却水冷却，冷却温度为10℃，冷却时间为1分钟，得到最终的膨胀型热塑性聚氨酯弹性体制品。
实施例2：
一种膨胀型热塑性聚氨酯弹性体制品的制备方法，包括如下步骤：
(1)采用喷涂工艺将1重量份的丙烯酸酯胶(TA-868)涂覆在10000重量份的膨胀热塑性聚氨酯粒子表面，其中丙烯酸酯胶溶液中丙烯酸酯的固含量为5％；发泡热塑性聚氨酯粒子的密度为0.25g/cm3,外观为荧光黄，形状为圆柱形；
(2)称取100g上述表面涂覆粘结剂的膨胀型热塑性聚氨酯弹性体粒子并装填到制品模具中；
(3)将步骤(2)的制品模具置于平板硫化机中进行模压固化成型，平板硫化机的硫化温度为200℃，硫化压力为1Mpa,硫化时间为30分钟；
(4)将上述步骤(3)的制品模具采用冷却水冷却，冷却温度为40℃，冷却时间为20分钟，得到最终的膨胀型热塑性聚氨酯弹性体制品。
实施例3：
一种膨胀型热塑性聚氨酯弹性体制品的制备方法，包括如下步骤：
(1)采用干混工艺将1重量份的环氧树脂胶(2011)涂覆在500重量份的膨胀型热塑性聚氨酯粒子表面，其中所使用的环氧树脂胶的有效固含量为100％，粒径为5000目，膨胀型热塑性聚氨酯粒子的密度为0.3g/cm3,外观为宝石蓝，形状为圆柱形；
(2)称取100g上述表面附着粘结剂的膨胀型热塑性聚氨酯弹性体粒子并装填到制品模具中；
(3)将步骤(2)的制品模具置于平板硫化机中进行模压固化成型，平板硫化机的硫化温度为150℃，硫化压力为0.5Mpa,硫化时间为10分钟；
(4)将上述步骤(3)的制品模具采用冷却水冷却，冷却温度为20℃，冷却时间为5分钟，得到最终的膨胀型热塑性聚氨酯弹性体制品。
实施例4：
一种膨胀型热塑性聚氨酯弹性体制品的制备方法，包括如下步骤：
(1)采用喷涂工艺将1重量份的单组份聚氨酯胶(6091)涂覆在100重量份的膨胀型热塑性聚氨酯粒子表面，其中所使用的单组份聚氨酯胶液体的有效固含量为80％，膨胀型热塑性聚氨酯粒子的密度为0.05g/cm3,外观为荧光黄，形状为圆柱形；
(2)称取100g上述表面涂覆粘结剂的膨胀型热塑性聚氨酯弹性体粒子并装填到制品模具中；
(3)将步骤(2)的制品模具置于平板硫化机中进行模压固化成型，平板硫化机的硫化温度为60℃，硫化压力为1Mpa,硫化时间为5分钟；
(4)将上述步骤(3)的制品模具采用冷却水冷却，冷却温度为30℃，冷却时间为5分钟，得到最终的膨胀型热塑性聚氨酯弹性体制品。
实施例5：
一种膨胀型热塑性聚氨酯弹性体制品的制备方法，包括如下步骤：
(1)采用喷涂工艺将1重量份的双组份聚氨酯胶(8103)涂覆在800重量份的膨胀型热塑性聚氨酯粒子表面，其中双组份聚氨酯胶液体的有效固含量为50％，膨胀热塑性聚氨酯粒子的密度为0.15g/cm3,外观为桃红，形状为圆形；
(2)称取100g上述表面涂覆粘结剂的膨胀型热塑性聚氨酯弹性体粒子并装填到制品模具中；
(3)将步骤(2)的制品模具置于平板硫化机中进行模压固化成型，平板硫化机的硫化温度为70℃，硫化压力为0.8Mpa,硫化时间为10分钟；
(4)将上述步骤(3)的制品模具采用冷却水冷却，冷却温度为25℃，冷却时间为10分钟，得到最终的膨胀型热塑性聚氨酯弹性体制品。
实施例6：
一种膨胀型热塑性聚氨酯弹性体制品的制备方法，包括如下步骤：
(1)采用喷涂工艺将1重量份的水性聚氨酯( PLR8878)涂覆在1000重量份的膨胀型热塑性聚氨酯粒子表面，其中水性聚氨酯乳液的有效固含量为20％，膨胀热塑性聚氨酯粒子的密度为0.25g/cm3,外观为桃红，形状为圆形；
(2)称取100g上述表面涂覆粘结剂的膨胀型热塑性聚氨酯弹性体粒子并装填到制品模具中；
(3)将步骤(2)的制品模具置于平板硫化机中进行模压固化成型，平板硫化机的硫化温度为70℃，硫化压力为0.8Mpa,硫化时间为10分钟；
(4)将上述步骤(3)的制品模具采用冷却水冷却，冷却温度为25℃，冷却时间为10分钟，得到最终的膨胀型热塑性聚氨酯弹性体制品。
为了验证本发明所得的膨胀型热塑性聚氨酯弹性体制品的性能，我们将实施例1-6所得的产品与水蒸汽模塑制品进行了如下测试，具体测试结果数据如表1所示：
表1：实施例1-6所得产品与水蒸汽模塑制品的性能测试数据
其中，拉伸强度的测试标准为ISO179：2008；落球回弹的测试标准为ISO830：2007；耐曲折的测试标准为ASTM D1052(10万次)；压缩变形的测试标准为SATRA TM64。
由表1中的数据可以看出，本发明所制备的产品在拉伸强度，落球回弹性，耐曲折和压缩变形方面都优于市场同类产品。
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 (10)

1.一种膨胀型热塑性聚氨酯弹性体制品的制备方法，其特征在于，包括如下步骤：
1)附着粘结剂：使膨胀型热塑性聚氨酯弹性体粒子的表面附着粘结剂；
2)固化成型：步骤1)中所得产品加入到成型模具中后置于硫化机内模压固化成型；
3)冷却定型：将步骤2)中成型后的成型模具冷却，即得。
2.根据权利要求1所述的制备方法，其特征在于，步骤1)中所述的粘结剂为熔点处于40-200℃的可热熔树脂，其形态为粉体、液体中的一种。
3.根据权利要求2所述的制备方法，其特征在于，步骤1)中所述的粘结剂为热塑性聚氨酯弹性体、丙烯酸酯、环氧树脂、单组份聚氨酯、双组份聚氨酯、水性聚氨酯中的一种。
4.根据权利要求2所述的制备方法，其特征在于，所述粉体形态的可热熔树脂的粒径为30-5000目，所述液体形态的可热熔树脂其有效固含量为5-100wt％。
5.根据权利要求3所述的制备方法，其特征在于，所述粉体形态的可热熔树脂的粒径为50-3000目，所述液体形态的可热熔树脂其有效固含量为10-80wt％。
6.根据权利要求1所述的制备方法，其特征在于，步骤1)中所述的膨胀型热塑性聚氨酯弹性体粒子的密度为0.001-0.6g/cm3。
7.根据权利要求6所述的制备方法，其特征在于，步骤1)中所述的膨胀型热塑性聚氨酯弹性体粒子的密度为0.05-0.3g/cm3。
8.根据权利要求1所述的制备方法，其特征在于，步骤1)中所述的粘结剂与膨胀型热塑性聚氨酯弹性体粒子的质量比为1:1到1:10000。
9.根据权利要求1所述的制备方法，其特征在于，步骤1)中于膨胀型热塑性聚氨酯弹性体粒子的表面附着粘结剂的方法为静电吸附、喷涂、干混中的一种。
10.根据权利要求1-9中任一项所述的制备方法，其特征在于，步骤2)中硫化机的硫化温度为40-200℃，硫化压力为0.01-1MPa，硫化时间为1-30分钟，步骤3)中冷却的温度为10-40℃，冷却时间为1-20min。
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