CN109485982A - 一种手机用发泡材料 - Google Patents

一种手机用发泡材料 Download PDF

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CN109485982A
CN109485982A CN201811001047.4A CN201811001047A CN109485982A CN 109485982 A CN109485982 A CN 109485982A CN 201811001047 A CN201811001047 A CN 201811001047A CN 109485982 A CN109485982 A CN 109485982A
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mobile phone
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silane coupling
coupling agent
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陈福珍
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JIAXING BOFA NEW PLASTIC Co Ltd
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Abstract

本发明公开了一种手机用发泡材料，其原料按重量份包括：乙烯‑醋酸乙烯共聚物100份、丁苯橡胶8‑20份、三元乙丙橡胶2‑8份、聚甲醛3‑12份、聚乙烯2‑10份、填料2‑10份、木质素1‑3份、发泡剂1‑2份、氧化锌0.3‑1.3份、硬脂酸1‑1.5份、过氧化苯甲酰0.2‑0.5份、一硫化四甲基秋兰姆0.1‑0.35份、硫磺0.05‑0.28份、三烯丙基异氰脲酸酯0.1‑0.2份、石蜡0.1‑2份、甘油0.1‑1份、硅烷偶联剂0.1‑1份。本发明提出的手机用复合发泡材料，其柔韧性好，硬度低，耐热性和耐老化性能优异。

Description

一种手机用发泡材料
技术领域
本发明涉及手机材料技术领域，尤其涉及一种手机用发泡材料。
背景技术
手机已经成为现代社会中必不可少的通信工具，随着社会的发展，人们对手机用材料的性能也提出了更高的要求。乙烯-醋酸乙烯共聚物(EVA)橡塑制品是新型环保塑料发泡材料，具有良好的耐水、耐腐蚀、加工性、缓冲、抗震、保温、隔热、环保等优点，目前已被广泛用于发泡鞋料、功能性棚膜、包装膜、热熔胶、电线电缆及玩具等领域。但是，现有的乙烯-醋酸乙烯酯共聚物橡塑材料较硬，不易制成较薄的制品，因此无法在手机领域进行广泛的应用，且在手机领域中应用时存在耐老化性和耐热性不是很好的缺陷，限制了其应用。
发明内容
基于背景技术存在的技术问题，本发明提出了一种手机用发泡材料，其柔韧性好，硬度低，耐热性和耐老化性能优异。
本发明提出的一种手机用发泡材料，其原料按重量份包括：乙烯-醋酸乙烯共聚物100份、丁苯橡胶8-20份、三元乙丙橡胶2-8份、聚甲醛3-12份、聚乙烯2-10份、填料2-10份、木质素1-3份、发泡剂1-2份、氧化锌0.3-1.3份、硬脂酸1-1.5份、过氧化苯甲酰0.2-0.5份、一硫化四甲基秋兰姆0.1-0.35份、硫磺0.05-0.28份、三烯丙基异氰脲酸酯0.1-0.2份、石蜡0.1-2份、甘油0.1-1份、硅烷偶联剂0.1-1份。
优选地，在乙烯-醋酸乙烯共聚物中，乙酸乙烯的质量分数为18-20wt％。
优选地，在丁苯橡胶中，苯乙烯的质量分数为24-25wt％。
优选地，所述填料为改性填料；所述改性填料按照以下工艺进行制备：将炭黑、纳米碳酸钙、氧化铁、碳纳米管、水滑石加入乙醇中，搅拌均匀后调节pH值为3-4，加入硅烷偶联剂KH570，搅拌均匀后升温至48-58℃反应15-22h，反应结束后经过滤、洗涤、干燥得到物料A；将物料A加入二甲基甲酰胺中搅拌均匀，升温至70-85℃后加入苯乙烯、丙烯酸丁酯、甲基丙烯酸-2-羟乙酯、乙烯基磷酸二甲酯和偶氮二异丁腈，搅拌均匀后保温反应4-5h，反应结束后加入萘二异氰酸酯，搅拌50-100min，干燥后得到所述改性填料。
优选地，在改性填料的制备过程中，炭黑、纳米碳酸钙、氧化铁、碳纳米管、水滑石、硅烷偶联剂KH570的重量比为15-21：3-9：2-10：1-5：3-14：5-12。
优选地，在改性填料的制备过程中，物料A、苯乙烯、丙烯酸丁酯、甲基丙烯酸-2-羟乙酯、乙烯基磷酸二甲酯、偶氮二异丁腈、萘二异氰酸酯的重量比为3-9：5-12：4-8：3-9：1-5：0.3-0.8：5-16。
优选地，所述改性填料按照以下工艺进行制备：按重量份将18份炭黑、7份纳米碳酸钙、6份氧化铁、3份碳纳米管、9份水滑石加入50份乙醇中，搅拌均匀后调节pH值为3.5，加入10份硅烷偶联剂KH570，搅拌均匀后升温至55℃反应20h，反应结束后经过滤、洗涤、干燥得到物料A；按重量份将8份物料A加入50份二甲基甲酰胺中搅拌均匀，升温至75℃后加入6份苯乙烯、5份丙烯酸丁酯、7份甲基丙烯酸-2-羟乙酯、3份乙烯基磷酸二甲酯和0.5份偶氮二异丁腈，搅拌均匀后保温反应4.5h，反应结束后加入12份萘二异氰酸酯，搅拌80min，干燥后得到所述改性填料。
优选地，所述发泡剂为偶氮二甲酰胺、偶氮二异丁腈、二亚硝基五亚甲基四胺、4,4’-氧代双苯磺酰肼、碳酸氢钠中的一种或多种的混合物。
优选地，所述硅烷偶联剂为硅烷偶联剂KH-550、硅烷偶联剂KH-560、硅烷偶联剂KH-570中的一种或者多种的混合物。
本发明所述手机用发泡材料，其以乙烯-醋酸乙烯共聚物为主料，同时加入了丁苯橡胶、三元乙丙橡胶、聚甲醛、聚乙烯对其进行改性，并调控了五者的比例，使五者发挥最佳的协同作用，赋予复合发泡材料较低的硬度，良好的柔韧性和抗疲劳性；在改性填料的制备过程中，将炭黑、纳米碳酸钙、氧化铁、碳纳米管、水滑石利用硅烷偶联剂KH570改性，从而使硅烷偶联剂KH570与炭黑、纳米碳酸钙、氧化铁、碳纳米管、水滑石发生了接枝反应，将双键引入到了炭黑、纳米碳酸钙、氧化铁、碳纳米管、水滑石中得到了物料A；物料A与苯乙烯、丙烯酸丁酯、甲基丙烯酸-2-羟乙酯、乙烯基磷酸二甲酯在偶氮二异丁腈的作用下发生了聚合反应，与萘二异氰酸酯混合，两者发生了反应，从而将聚氨酯引入到了炭黑、纳米碳酸钙、氧化铁、碳纳米管、水滑石中得到了改性填料，将其加入体系中，一方面，因适当加入了聚氨酯，显著改善了基体的塑性形变，在保持复合发泡材料较高断裂伸长率的同时适当降低了复合发泡材料的硬度，使其能制成较薄的材料，应用于手机领域中，另一方面，其中的聚氨酯结构能与基体中的聚合物发生物理缠绕，形成了网络结构，使炭黑、纳米碳酸钙、氧化铁、碳纳米管、水滑石能够均匀地分散在基体中，提高了填料与基体的结合性，推迟了聚合物大分子的降解，赋予复合发泡材料优异的拉伸强度、撕裂强度、耐热性和耐老化性，同时与乙烯基磷酸二甲酯配合，明显催化了体系成炭，改善炭层结构，赋予体系一定的阻燃性和耐热性；氧化锌、过氧化苯甲酰、一硫化四甲基秋兰姆、硫磺、三烯丙基异氰脲酸酯加入体系中，配合作为硫化体系，硫化速度快，效果好，使得到的发泡材料耐热性和耐老化性能优异。
具体实施方式
下面，通过具体实施例对本发明的技术方案进行详细说明。
实施例1
本发明提出的一种手机用发泡材料，其原料按重量份包括：乙烯-醋酸乙烯共聚物100份、丁苯橡胶20份、三元乙丙橡胶2份、聚甲醛12份、聚乙烯2份、填料10份、木质素1份、发泡剂2份、氧化锌0.3份、硬脂酸1.5份、过氧化苯甲酰0.2份、一硫化四甲基秋兰姆0.35份、硫磺0.05份、三烯丙基异氰脲酸酯0.2份、石蜡0.1份、甘油1份、硅烷偶联剂0.1份。
实施例2
本发明提出的一种手机用发泡材料，其原料按重量份包括：乙烯-醋酸乙烯共聚物100份、丁苯橡胶10份、三元乙丙橡胶8份、聚甲醛3份、聚乙烯10份、填料2份、木质素3份、发泡剂1份、氧化锌1.3份、硬脂酸1份、过氧化苯甲酰0.5份、一硫化四甲基秋兰姆0.1份、硫磺0.28份、三烯丙基异氰脲酸酯0.1份、石蜡2份、甘油0.1份、硅烷偶联剂1份。
实施例3
本发明提出的一种手机用发泡材料，其原料按重量份包括：乙烯-醋酸乙烯共聚物100份、丁苯橡胶18份、三元乙丙橡胶3份、聚甲醛10份、聚乙烯4份、填料8份、木质素1.6份、发泡剂1.7份、氧化锌0.6份、硬脂酸1.3份、过氧化苯甲酰0.3份、一硫化四甲基秋兰姆0.32份、硫磺0.1份、三烯丙基异氰脲酸酯0.17份、石蜡0.8份、甘油0.8份、硅烷偶联剂0.4份；
其中，在乙烯-醋酸乙烯共聚物中，乙酸乙烯的质量分数为20wt％；
在丁苯橡胶中，苯乙烯的质量分数为24wt％；
所述填料为改性填料；所述改性填料按照以下工艺进行制备：将炭黑、纳米碳酸钙、氧化铁、碳纳米管、水滑石加入乙醇中，搅拌均匀后调节pH值为3，加入硅烷偶联剂KH570，搅拌均匀后升温至58℃反应15h，反应结束后经过滤、洗涤、干燥得到物料A；将物料A加入二甲基甲酰胺中搅拌均匀，升温至85℃后加入苯乙烯、丙烯酸丁酯、甲基丙烯酸-2-羟乙酯、乙烯基磷酸二甲酯和偶氮二异丁腈，搅拌均匀后保温反应4h，反应结束后加入萘二异氰酸酯，搅拌100min，干燥后得到所述改性填料；
在改性填料的制备过程中，炭黑、纳米碳酸钙、氧化铁、碳纳米管、水滑石、硅烷偶联剂KH570的重量比为15：9：2：5：3：12；物料A、苯乙烯、丙烯酸丁酯、甲基丙烯酸-2-羟乙酯、乙烯基磷酸二甲酯、偶氮二异丁腈、萘二异氰酸酯的重量比为3：12：4：9：1：0.8：5；
所述发泡剂为偶氮二异丁腈；
所述硅烷偶联剂为硅烷偶联剂KH-550。
实施例4
本发明提出的一种手机用发泡材料，其原料按重量份包括：乙烯-醋酸乙烯共聚物100份、丁苯橡胶14份、三元乙丙橡胶7份、聚甲醛5份、聚乙烯9份、填料5份、木质素2.7份、发泡剂1.3份、氧化锌1份、硬脂酸1.2份、过氧化苯甲酰0.45份、一硫化四甲基秋兰姆0.16份、硫磺0.21份、三烯丙基异氰脲酸酯0.13份、石蜡1.6份、甘油0.2份、硅烷偶联剂0.5份；
其中，在乙烯-醋酸乙烯共聚物中，乙酸乙烯的质量分数为18wt％；
在丁苯橡胶中，苯乙烯的质量分数为25wt％；
所述填料为改性填料；所述改性填料按照以下工艺进行制备：将炭黑、纳米碳酸钙、氧化铁、碳纳米管、水滑石加入乙醇中，搅拌均匀后调节pH值为4，加入硅烷偶联剂KH570，搅拌均匀后升温至48℃反应22h，反应结束后经过滤、洗涤、干燥得到物料A；将物料A加入二甲基甲酰胺中搅拌均匀，升温至70℃后加入苯乙烯、丙烯酸丁酯、甲基丙烯酸-2-羟乙酯、乙烯基磷酸二甲酯和偶氮二异丁腈，搅拌均匀后保温反应5h，反应结束后加入萘二异氰酸酯，搅拌50min，干燥后得到所述改性填料；
在改性填料的制备过程中，炭黑、纳米碳酸钙、氧化铁、碳纳米管、水滑石、硅烷偶联剂KH570的重量比为21：3：10：1：14：5；物料A、苯乙烯、丙烯酸丁酯、甲基丙烯酸-2-羟乙酯、乙烯基磷酸二甲酯、偶氮二异丁腈、萘二异氰酸酯的重量比为9：5：8：3：5：0.3：16；
所述发泡剂为偶氮二甲酰胺；
所述硅烷偶联剂为硅烷偶联剂KH-560。
实施例5
本发明提出的一种手机用发泡材料，其原料按重量份包括：乙烯-醋酸乙烯共聚物100份、丁苯橡胶14份、三元乙丙橡胶6份、聚甲醛9份、聚乙烯7份、填料5份、木质素2份、发泡剂1.6份、氧化锌1份、硬脂酸1.2份、过氧化苯甲酰0.38份、一硫化四甲基秋兰姆0.3份、硫磺0.13份、三烯丙基异氰脲酸酯0.14份、石蜡0.9份、甘油0.6份、硅烷偶联剂1份；
其中，在乙烯-醋酸乙烯共聚物中，乙酸乙烯的质量分数为19wt％；
在丁苯橡胶中，苯乙烯的质量分数为24.6wt％；
所述改性填料按照以下工艺进行制备：按重量份将18份炭黑、7份纳米碳酸钙、6份氧化铁、3份碳纳米管、9份水滑石加入50份乙醇中，搅拌均匀后调节pH值为3.5，加入10份硅烷偶联剂KH570，搅拌均匀后升温至55℃反应20h，反应结束后经过滤、洗涤、干燥得到物料A；按重量份将8份物料A加入50份二甲基甲酰胺中搅拌均匀，升温至75℃后加入6份苯乙烯、5份丙烯酸丁酯、7份甲基丙烯酸-2-羟乙酯、3份乙烯基磷酸二甲酯和0.5份偶氮二异丁腈，搅拌均匀后保温反应4.5h，反应结束后加入12份萘二异氰酸酯，搅拌80min，干燥后得到所述改性填料；
所述发泡剂为偶氮二甲酰胺、偶氮二异丁腈、二亚硝基五亚甲基四胺、4,4’-氧代双苯磺酰肼、碳酸氢钠的混合物，且偶氮二甲酰胺、偶氮二异丁腈、二亚硝基五亚甲基四胺、4,4’-氧代双苯磺酰肼、碳酸氢钠的重量比为4：3：6：2：1；
所述硅烷偶联剂为硅烷偶联剂KH-550、硅烷偶联剂KH-560、硅烷偶联剂KH-570的混合物，且硅烷偶联剂KH-550、硅烷偶联剂KH-560、硅烷偶联剂KH-570的重量比为3:5:2。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (9)

1.一种手机用发泡材料，其特征在于，其原料按重量份包括：乙烯-醋酸乙烯共聚物100份、丁苯橡胶8-20份、三元乙丙橡胶2-8份、聚甲醛3-12份、聚乙烯2-10份、填料2-10份、木质素1-3份、发泡剂1-2份、氧化锌0.2-1.1份、硬脂酸1-1.5份、过氧化苯甲酰0.2-0.5份、一硫化四甲基秋兰姆0.1-0.35份、硫磺0.05-0.28份、三烯丙基异氰脲酸酯0.1-0.2份、石蜡0.1-2份、甘油0.1-1份、硅烷偶联剂0.2-1.3份。
2.根据权利要求1所述手机用发泡材料，其特征在于，在乙烯-醋酸乙烯共聚物中，乙酸乙烯的质量分数为18-20wt％。
3.根据权利要求1或2所述手机用发泡材料，其特征在于，在丁苯橡胶中，苯乙烯的质量分数为24-25wt％。
4.根据权利要求1-3中任一项所述手机用发泡材料，其特征在于，所述填料为改性填料；所述改性填料按照以下工艺进行制备：将炭黑、纳米碳酸钙、氧化铁、碳纳米管、水滑石加入乙醇中，搅拌均匀后调节pH值为3-4，加入硅烷偶联剂KH570，搅拌均匀后升温至48-58℃反应15-22h，反应结束后经过滤、洗涤、干燥得到物料A；将物料A加入二甲基甲酰胺中搅拌均匀，升温至70-85℃后加入苯乙烯、丙烯酸丁酯、甲基丙烯酸-2-羟乙酯、乙烯基磷酸二甲酯和偶氮二异丁腈，搅拌均匀后保温反应4-5h，反应结束后加入萘二异氰酸酯，搅拌50-100min，干燥后得到所述改性填料。
5.根据权利要求4所述手机用发泡材料，其特征在于，在改性填料的制备过程中，炭黑、纳米碳酸钙、氧化铁、碳纳米管、水滑石、硅烷偶联剂KH570的重量比为15-21：3-9：2-10：1-5：3-14：5-12。
6.根据权利要求4或5所述手机用发泡材料，其特征在于，在改性填料的制备过程中，物料A、苯乙烯、丙烯酸丁酯、甲基丙烯酸-2-羟乙酯、乙烯基磷酸二甲酯、偶氮二异丁腈、萘二异氰酸酯的重量比为3-9：5-12：4-8：3-9：1-5：0.3-0.8：5-16。
7.根据权利要求4-5中任一项所述手机用发泡材料，其特征在于，所述改性填料按照以下工艺进行制备：按重量份将18份炭黑、7份纳米碳酸钙、6份氧化铁、3份碳纳米管、9份水滑石加入50份乙醇中，搅拌均匀后调节pH值为3.5，加入10份硅烷偶联剂KH570，搅拌均匀后升温至55℃反应20h，反应结束后经过滤、洗涤、干燥得到物料A；按重量份将8份物料A加入50份二甲基甲酰胺中搅拌均匀，升温至75℃后加入6份苯乙烯、5份丙烯酸丁酯、7份甲基丙烯酸-2-羟乙酯、3份乙烯基磷酸二甲酯和0.5份偶氮二异丁腈，搅拌均匀后保温反应4.5h，反应结束后加入12份萘二异氰酸酯，搅拌80min，干燥后得到所述改性填料。
8.根据权利要求1-7中任一项所述手机用发泡材料，其特征在于，所述发泡剂为偶氮二甲酰胺、偶氮二异丁腈、二亚硝基五亚甲基四胺、4,4’-氧代双苯磺酰肼、碳酸氢钠中的一种或多种的混合物。
9.根据权利要求1-8中任一项所述手机用发泡材料，其特征在于，所述硅烷偶联剂为硅烷偶联剂KH-550、硅烷偶联剂KH-560、硅烷偶联剂KH-570中的一种或者多种的混合物。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3865538A1 (en) * 2020-02-14 2021-08-18 Sika Technology AG Thermally expandable compositions with improved humidity storage resistance
WO2021160852A1 (en) * 2020-02-14 2021-08-19 Sika Technology Ag Thermally expandable compositions with improved humidity storage resistance
CN115087693A (zh) * 2020-02-14 2022-09-20 Sika技术股份公司 具有改进的耐湿气储存性的可热膨胀组合物

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