CN113429645B - 兼具减震功能的温敏响应形状记忆发泡材料及其制备方法和应用 - Google Patents

兼具减震功能的温敏响应形状记忆发泡材料及其制备方法和应用 Download PDF

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CN113429645B
CN113429645B CN202110754530.5A CN202110754530A CN113429645B CN 113429645 B CN113429645 B CN 113429645B CN 202110754530 A CN202110754530 A CN 202110754530A CN 113429645 B CN113429645 B CN 113429645B
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林鸿飞
蔡志杰
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Jinjiang City Shida Plastic Fine Co ltd
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Abstract

本发明涉及一种兼具减震功能的温敏响应形状记忆发泡材料，由如下重量份数计的组分发泡制成：10‑40份反式‑1,4‑聚异戊二烯橡胶、0‑10份富含乙烯支化的苯乙烯嵌段共聚物、10‑20份丙烯‑4‑甲基戊烯共聚物、EVA、POE、滑石粉、过氧化物交联剂、发泡剂、氧化锌、硬脂酸、硬脂酸锌。本发明在EVA和POE基础材料中引入了丙烯‑4‑甲基戊烯共聚物、反式‑1,4‑聚异戊二烯橡胶，尤其是在其中进一步引入富含乙烯支化的苯乙烯嵌段共聚物，能够与丙烯‑4‑甲基戊烯共聚物、反式‑1,4‑聚异戊二烯橡胶及其他组分协同增强，共同提高室温形状固定率、形状回复率和循环使用次数，同时增强减震性能，可以快速实现私人定制产品，周期短、效率高、可重复性、性价比高。

Description

兼具减震功能的温敏响应形状记忆发泡材料及其制备方法和 应用
技术领域
本发明属于记忆材料技术领域，具体涉及一种兼具减震功能的温敏响应形状记忆发泡材料及其制备方法和应用。
背景技术
随着人们生活水平的提高，物质消费大大满足的情况下，人们更多关注自己的身体健康，因此对物质的消费需求提出了更高的要求，个性化的私人定制由此应运而生。
现有市面上的鞋垫、坐垫、靠垫以及枕头基本上都是公版的，但是每个人的足型，臀型，后背以及头型都是千差万别的，如何满足消费者因人而异专属定制需求的矛盾也日益突出。随着电子商务的迅速发展，互联网模式的私人专属定制蓬勃发展，虽然极大程度的满足个人需求，体现个性，但是存在定制周期长，成本高的问题。因此，需要一种性价比高可以快速实现的私人订制。
另外，高分子的减震性能与聚合物的粘弹性息息相关，聚合物在玻璃化转变(Tg)附近形变主要由链段运动产生，链段运动时受内摩擦阻力作用，在交变的应力作用下，链段运动跟不上应力的变化，宏观表现为应变落后于应力，即存在滞后现象。在每一循环过程中，要发生力学耗散而消耗能量即产生内耗。这种由内摩擦导致的滞后内耗将机械能转化为热能的能力，称为材料的阻尼减震性能能力。
温敏响应形状记忆发泡材料的记忆原理：将聚合物材料与各种配合剂进行混炼造粒，而后在模具里进行交联发泡反应并确定一次形状，冷却结晶后即得到初始态，其化学交联结构为固定相,结晶相为可逆相。当温度升高至熔点(Tm)以上时，可逆相熔融软化，在外力的作用下可做成任意的形状保持外力并冷却固定，使分子链沿外力方向取向冻结得到变形态。当温度再升高至Tm以上时，可逆相分子链在熵弹性作用下发生自然卷曲，直至达到热力学平衡状态，从而发生形状回复，形状记忆过程实现可逆循环。
已知，公开专利中温度响应形状记忆材料中，中高VA含量的乙烯-醋酸乙烯酯共聚物(EVA)，由于结晶度略低，存在室温形变固定率不高与热刺激温度高(≥75℃)的问题；反式-1,4-聚异戊二烯橡胶(TPI)，热刺激温度低，但单独使用不宜交联发泡以及含有大量不饱和双键易老化的问题；富含乙烯支化的苯乙烯嵌段共聚物与分子链带有取代基的丙烯与4-甲基戊烯共聚物，减震性能好回弹性能不佳。
发明内容
本发明的发明目的是提供一种兼具减震功能的温敏响应形状记忆发泡材料及其制备方法和应用，热刺激响应温度低，适中的形变率，高的室温形变固定率以及形变回复率，并且减震性能好。
为实现上述发明目的，本发明采用的技术方案是：
兼具减震功能的温敏响应形状记忆发泡材料，由如下重量份数计的组分发泡制成：10-40份反式-1,4-聚异戊二烯橡胶、30-50份EVA、10-20份POE、0-10份富含乙烯支化的苯乙烯嵌段共聚物、10-20份丙烯-4-甲基戊烯共聚物、5-15份滑石粉、0.4-0.6份过氧化物交联剂、2-3份发泡剂、1-2份氧化锌、0.4-0.6份硬脂酸、0.8-1.0份硬脂酸锌。
优选地，所述富含乙烯支化的苯乙烯嵌段共聚物为SIS或SEBS。
优选地，所述富含乙烯支化的苯乙烯嵌段共聚物中的苯乙烯段摩尔含量＜25％。
优选地，所述EVA的VA摩尔含量为20％～40％。
优选地，所述POE的硬度＜82A，结晶度＜20％。
优选地，所述过氧化物交联剂选自过氧化二异丙苯和/或1,4-双叔丁基过氧异丙基苯。
优选地，所述发泡剂选自偶氮二甲酰胺、N,N'-二亚硝基五亚甲基四胺、膨胀微球和4,4-氧代二苯磺酰肼中的一种或多种。
本发明还提供一种兼具减震功能的温敏响应形状记忆发泡材料的制备方法，包括如下步骤：
S1、称料：依据配方，将滑石粉、氧化锌、硬脂酸和硬脂酸锌配为B料，将过氧化物交联剂和发泡剂配为C料，将剩余组分配为A料；
S2、密炼：将机器温度升至90±5℃时将A料倒入密炼机内，并打开机器进行密炼，待温度升到110±5℃时倒入B料；待温度升到120±5℃度时倒入C料，混炼4min-6min后将混好的料倒出，得M料；
S3、开炼：开炼机的滚轮温度设为70±5℃，待温度达到后启动轮台，将密炼混好的M料投入进行开炼，出片温度控制在70℃以下，出片厚度为3mm-5mm；
S4、热压发泡：将混炼好的片放入模压大发泡模具内完成硫化发泡。
优选地，所述步骤S2的密炼时间控制在600±60秒，密炼出料温度为120±5℃。
优选地，所述步骤S4的发泡压力：160kg/cm2～180kg/cm2，发泡温度：170±5℃，发泡时间按模具厚度乘以100±10s/mm计算。
本发明还进一步提供上述兼具减震功能的温敏响应形状记忆发泡材料在鞋垫、坐垫、靠垫或枕头的应用。
与现有技术相比，本发明具有以下有益效果：
本发明在EVA和POE基础材料中引入了丙烯-4-甲基戊烯共聚物、反式-1,4-聚异戊二烯橡胶能够简便快速变形、形变率可调且室温形状固定率和回复率高，尤其是在其中进一步引入富含乙烯支化的苯乙烯嵌段共聚物，能够与丙烯-4-甲基戊烯共聚物、反式-1,4-聚异戊二烯橡胶及其他组分协同增强，共同提高室温形状固定率、形状回复率和循环使用次数，同时增强减震性能，可以快速实现私人定制产品(枕头、坐垫、鞋垫和脚床、靠垫等等)，周期短、效率高、可重复性、性价比高。
具体实施方式
本发明提供一种兼具减震功能的温敏响应形状记忆发泡材料，由如下重量份数计的组分发泡制成：10-40份反式-1,4-聚异戊二烯橡胶、30-50份EVA、10-20份POE、0-10份富含乙烯支化的苯乙烯嵌段共聚物、10-20份丙烯-4-甲基戊烯共聚物、5-15份滑石粉、0.4-0.6份过氧化物交联剂、2-3份发泡剂、1-2份氧化锌、0.4-0.6份硬脂酸、0.8-1.0份
硬脂酸锌。
其中的反式-1,4-聚异戊二烯橡胶的熔点<70℃，牌号可选用Kuraray TP-301(熔点67℃，硬度78A，结晶度36％，日本可乐丽(Kuraray)公司)。
其中的所述EVA的VA摩尔含量为20％～40％，牌号可选用EVA 7360(VA摩尔含量为21％，硬度86A，熔点80℃，软化温度48℃，结晶度32.2％，中国台塑公司)、EVA 6110M(VA摩尔含量为26％，硬度82A，熔点76℃，软化温度43℃，结晶度24.8％，扬子巴斯夫有限责任公司)、EVA 3312(VA摩尔含量33％，硬度65A，熔点64℃，软化温度35℃，结晶度14.5％，中国台湾聚合化学品股份有限公司)。
其中的所述POE的硬度＜82A，结晶度＜20％，牌号选用Fortify C0507D(硬度74A，熔点59℃，结晶度16％，沙特基础工业公司)、Fortify C5070D(硬度63A，熔点62℃，结晶度16％，沙特基础工业公司)。
其中的所述富含乙烯支化的苯乙烯嵌段共聚物为SIS或SEBS，其苯乙烯段摩尔含量＜25％。具体的：SIS的牌号选用HYBRAR 5125(苯乙烯摩尔含量20％，硬度60A，日本可乐丽(Kuraray)公司)、HYBRAR 5127(苯乙烯摩尔含量20％，硬度84A，日本可乐丽(Kuraray)公司)；SEBS的牌号选用SOE 1605(硬度87A，日本旭化成公司)、SOE 1609(硬度87A，日本旭化成公司)。
其中的丙烯-4-甲基戊烯共聚物的牌号可选用ABSORTOMER EP1001(硬度92A，日本三井化学集团)、ABSORTOMER EP1013(硬度69D，日本三井化学集团)。
其中的所述过氧化物交联剂选自过氧化二异丙苯和/或1,4-双叔丁基过氧异丙基苯。所述发泡剂选自偶氮二甲酰胺、N,N'-二亚硝基五亚甲基四胺、膨胀微球和4,4-氧代二苯磺酰肼中的一种或多种。
本发明提供实施例1-8及对比例1-4，配方表参见表1和表2。
表1：本发明实施例1-8的形状记忆发泡材料配方表(重量份数)
示例1 示例2 示例3 示例4 示例5 示例6 示例7 示例8
TP-301 20 40 30 20 40 20 10 10
EVA 7360 _ _ 50 _ 20 _ _ _
EVA 6110M 40 _ _ 40 _ 40 _ _
EVA 3312 _ 40 _ _ 30 _ 50 50
C0507D _ 10 _ _ 10 20 _ _
C5070D 20 _ 15 20 _ _ 20 20
HYBRAR 5125 _ _ _ _ _ _ 10 10
HYBRAR 5127 _ _ _ _ _ 5 _ _
SOE 1605 _ _ _ 10 _ _ _ 5
SOE 1609 _ _ _ _ 10 _ _ _
EP1001 20 10 20 _ 20 10 10
EP1013 _ _ 15 _ 10 _ _ _
滑石粉 10 8 12 10 15 10 10 10
BIBP 14S-FL 0.5 0.4 0.6 0.5 0.6 0.5 0.5 0.5
AC6000H 2.2 2.5 2 2.2 3 2.2 2.2 3
ZnO 997 1.5 2 2 1.5 1.5 1.5 1.5 1
硬脂酸SA1840 0.5 0.5 0.6 0.5 0.6 0.5 0.5 0.4
硬脂酸锌 0.8 0.8 1.0 0.8 1.0 0.8 0.8 0.8
表2：本发明对比例1-4的形状记忆发泡材料配方表(重量份数)
上述实施例1-8和对比例1-4的形状记忆发泡材料均采用如下制备方法，包括如下步骤：S1、称料：依据配方，将滑石粉、氧化锌、硬脂酸和硬脂酸锌配为B料，将过氧化物交联剂和发泡剂配为C料，将剩余组分配为A料；S2、密炼：将机器温度升至90±5℃时将A料倒入密炼机内，并打开机器进行密炼，待温度升到110±5℃时倒入B料；待温度升到120±5℃度时倒入C料，混炼4min-6min后将混好的料倒出，得M料，密炼时间控制在600±60s，密炼出料温度为120±5℃；S3、开炼：开炼机的滚轮温度设为70±5℃，待温度达到后启动轮台，将密炼混好的M料投入进行开炼，出片温度控制在70℃以下，出片厚度为3mm-5mm；S4、热压发泡：将混炼好的片放入模压大发泡模具内完成硫化发泡，发泡压力：160kg/cm2～180kg/cm2，发泡温度：170±5℃，发泡时间按模具厚度乘以100±10s/mm计算。
对上述实施例1～8和对比例1-4提供的形状记忆发泡材料的各项性能进行检测，结果参见表3和表4。
邵氏硬度A0参照GB/T 531.1-2008标准测试；回弹率参照DIN 8307标准测试。
形变率测试方法-压缩测试法：将制作好发泡片材裁成10cm*10cm*1cm(厚度L0)的试片，放入75℃/65℃/55℃/45℃的烘箱中10min，取出后立即用直径为3cm重量为25kg的铁质砝码压头静压试片10min，记录压缩状态下试片的厚度L1，形变率D＝(L0-L1)*100％/L0；
室温形状固定率测试方法：经过压缩测试后的试片置于23℃的恒温环境室内，24h后记录试片的厚度L2。室温形状固定率F＝(L0-L2)*100％/(L0-L1)；
形状回复率测试方法：将经过形变率测试后的试片，放入75℃/65℃/55℃/45℃的烘箱中10min，取出后置于23℃的恒温环境室内，30min后记录此时试片的厚度L3，形状回复率R＝(L3-L1)*100％/(L0-L1)；
可循环使用的次数：将15cm*15cm*0.6cm(厚度L0)的试片，放入60℃的烘箱中10min，取出后立即用直径为3cm重量为25kg的铁质砝码压头静压试片180min，然后23℃恒温环境内放置48h后记录试片的厚度L5，然后放入60℃的烘箱中10min，取出后记录此时试片的厚度L6，形状回复率K＝(L6-L5)*100％/(L0-L5)【K≥85％则定义为可循环使用，M<85％则定义为不可再循环使用。】。以上测试为1个循环即可重复使用的次数为1，依照以上方法进行循环测试，直至M<85％，记录此时的循环数即为可重复使用的次数。
表3：本发明实施例1-8的发泡材料物性测试结果表
项目 示例1 示例2 示例3 示例4 示例5 示例6 示例7 示例8
硬度A0 32 36 30 26 32 30 22 28
回弹率％ 45 50 43 45 44 45 43 46
75℃形变率％ 63.5 61.5 62.1 65.2 65.6 66.1 64.1 64.5
室温形状固定率％ 93.5 94.8 94.5 96.6 97.1 96.8 93.6 94.2
75℃形状回复率％ 96.2 98.1 97.2 99.2 99.4 98.8 96.2 96.7
65℃形变率％ 58.4 57.3 58.6 62.2 62.5 61.8 61.2 61.8
室温形状固定率％ 94.8 94.9 94.2 96.2 96.3 95.8 95.1 95.2
65℃形状回复率％ 91.6 92.8 92.2 95.1 95.5 92.1 91.2 91.5
55℃形变率％ 33.2 31.3 32.6 35.6 37.1 36.2 34.8 35.1
室温形状固定率％ 96.0 96.2 95.6 98.6 98.8 98.4 95.3 95.5
55℃形状回复率％ 86.8 87.2 86.2 90.4 89.8 89.6 86.3 87.2
45℃形变率％ 2.7 1.6 2.2 4.2 3.8 3.7 3.1 3.5
室温形状固定率％ 97.2 98.8 97.6 98.8 98.2 98.6 97.5 98.1
45℃形状回复率％ 60.8 62.8 61.4 63.6 63.5 63.1 59.8 61.2
可循环使用的次数 28 26 28 32 30 31 29 30
表4：本发明对比例1-4的发泡材料物性测试结果表
从上述实验可知，本发明形状记忆发泡材料在EVA和POE基础材料中引入了丙烯-4-甲基戊烯共聚物、反式-1,4-聚异戊二烯橡胶能够简便快速变形、形变率可调且室温形状固定率和回复率高，尤其是在其中进一步引入富含乙烯支化的苯乙烯嵌段共聚物，能够与丙烯-4-甲基戊烯共聚物、反式-1,4-聚异戊二烯橡胶及其他组分协同增强，共同提高室温形状固定率、形状回复率和循环使用次数，同时也赋予发泡材料良好的减震性能。
以上显示和描述了本发明创造的基本原理和主要特征及本发明的优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明创造精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内，本发明要求保护范围由所附的权利要求书及其等效物界定。

Claims (6)

1.兼具减震功能的温敏响应形状记忆发泡材料，其特征在于，由如下重量份数计的组分发泡制成：10-40份反式-1,4-聚异戊二烯橡胶、30-50份EVA、10-20份POE、5-10份富含乙烯支化的苯乙烯嵌段共聚物、10-20份丙烯-4-甲基戊烯共聚物、5-15份滑石粉、0.4-0.6份过氧化物交联剂、2-3份发泡剂、1-2份氧化锌、0.4-0.6份硬脂酸、0.8-1.0份硬脂酸锌；所述富含乙烯支化的苯乙烯嵌段共聚物中的苯乙烯段摩尔含量＜25％；所述EVA的VA摩尔含量为20％～40％；所述POE的硬度＜82A，结晶度＜20％；
该温敏响应形状记忆发泡材料的制备方法，包括如下步骤：
S1、称料：依据配方，将滑石粉、氧化锌、硬脂酸和硬脂酸锌配为B料，将过氧化物交联剂和发泡剂配为C料，将剩余组分配为A料；
S2、密炼：将机器温度升至90±5℃时将A料倒入密炼机内，并打开机器进行密炼，待温度升到110±5℃时倒入B料；待温度升到120±5℃度时倒入C料，混炼4min-6min后将混好的料倒出，得M料；
S3、开炼：开炼机的滚轮温度设为70±5℃，待温度达到后启动轮台，将密炼混好的M料投入进行开炼，出片温度控制在70℃以下，出片厚度为3mm-5mm；
S4、热压发泡：将混炼好的片放入模压大发泡模具内完成硫化发泡。
2.根据权利要求1所述的兼具减震功能的温敏响应形状记忆发泡材料，其特征在于：所述富含乙烯支化的苯乙烯嵌段共聚物为SIS或SEBS。
3.根据权利要求1所述的兼具减震功能的温敏响应形状记忆发泡材料，其特征在于：所述发泡剂选自偶氮二甲酰胺、N,N'-二亚硝基五亚甲基四胺、膨胀微球和4,4-氧代二苯磺酰肼中的一种或多种。
4.根据权利要求1所述的兼具减震功能的温敏响应形状记忆发泡材料，其特征在于：所述步骤S2的密炼时间控制在600±60秒，密炼出料温度为120±5℃。
5.根据权利要求1所述的兼具减震功能的温敏响应形状记忆发泡材料，其特征在于：所述步骤S4的发泡压力：160 kg/cm2～180kg/cm2，发泡温度：170±5℃，发泡时间按模具厚度乘以100±10s/mm计算。
6.如权利要求1至5任一项所述的兼具减震功能的温敏响应形状记忆发泡材料在鞋垫、坐垫、靠垫或枕头的应用。
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