CN108715653A - 一种阻燃、耐候的绝热材料及其制备方法 - Google Patents

一种阻燃、耐候的绝热材料及其制备方法 Download PDF

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CN108715653A
CN108715653A CN201810527105.0A CN201810527105A CN108715653A CN 108715653 A CN108715653 A CN 108715653A CN 201810527105 A CN201810527105 A CN 201810527105A CN 108715653 A CN108715653 A CN 108715653A
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agent
parts
weather
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insulating material
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李垂祥
孙振宇
王文华
代娇
徐建华
李树军
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Weifang Master Chemical Co Ltd
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Abstract

本发明公开提供一种阻燃、耐候的绝热材料及其制备方法，属于氯化聚乙烯橡胶制备领域，包括：第一层和第二层组成的制品，所述第一层由第一组合物组成，所述第一组合物原料为：丁腈橡胶、聚氯乙烯、防老剂、填充剂、加工助剂、软化剂、发泡剂、发泡助剂份、促进剂、硫化剂；所述第二层由第二组合物组成，所述第二组合物原料配方按重量份计为：氯化聚乙烯橡胶、吸酸剂、防老剂、填充剂、加工助剂、软化剂、发泡剂、发泡助剂份、交联助剂、交联剂。本发明采用共挤出的方式，制备表面层为氯化聚乙烯、底层或内层为丁腈橡胶及聚氯乙烯的阻燃、耐候绝热材料，其耐热、耐候、耐臭氧、阻燃性能优于传统的绝热材料，同时具有生产成本优势。

Description

一种阻燃、耐候的绝热材料及其制备方法
技术领域
本发明属于氯化聚乙烯橡胶制备领域，具体涉及一种阻燃、耐候的绝热材料及其制备方法。
背景技术
绝热材料通常具有质轻、疏松、多孔、导热系数小的特点，一般用来防止热力设备及管道热量散失，或者在冷冻和低温下使用，因而在我国绝热材料又被称为保温或保冷材料，主要用于建筑围护或者热工设备、阻抗热流传递的材料或者材料复合体。
目前国内用量最大的绝热材料，主体原料为丁腈橡胶和聚氯乙烯，丁腈橡胶大分子链中含有不饱和碳碳双键，生产过程中虽已填加防老剂，但材料的耐热、耐天候、耐臭氧性能仍然较差，尤其是用于室外经过暴晒、雨淋、低温等恶劣环境，容易变硬、发脆，导致材料破裂失去绝热性能，更换周期一般为3～5年。国外的绝热保温材料，大多数是采用三元乙丙橡胶为主体材料生产的，三元乙丙橡胶主链是饱和结构，耐热、耐天候性能好，因此三元乙丙橡胶生产的绝热材料使用寿命长，更换周期长，但其阻燃性较差、生产成本高。
发明内容
本发明为解决现存问题提供一种阻燃、耐候的绝热材料及其制备方法，本发明采用共挤出的方式，制备表面层为氯化聚乙烯、底层或内层为丁腈橡胶及聚氯乙烯的阻燃、耐候绝热材料，其耐热、耐候、耐臭氧性能优于传统的丁腈橡胶及聚氯乙烯绝热材料，阻燃性能优于三元乙丙橡胶绝热材料，同时具有生产成本优势。
本发明解决其技术问题所采用的技术方案为：
本发明提供的一种阻燃、耐候的绝热材料，包括：第一层和第二层组成的制品，
所述第一层由第一组合物组成，所述第一组合物原料配方按重量份计为：丁腈橡胶60～90份、聚氯乙烯40～10份、防老剂Ⅰ0.5～3份、填充剂10～100份、加工助剂1～5份、软化剂Ⅰ10～50份、发泡剂5～15份、发泡助剂5～10份、促进剂1～5份、硫化剂1～5份；
所述第二层由第二组合物组成，所述第二组合物原料配方按重量份计为：氯化聚乙烯橡胶100份、吸酸剂5～10份、防老剂Ⅱ1～5份、填充剂10～100份、加工助剂1～5份、软化剂Ⅱ10～40份、发泡剂5～15份、发泡助剂5～10份、交联助剂1～5份、交联剂1～5份。
优选的，所述制品为绝热板材或管材。
优选的，所述防老剂Ⅰ为防老剂264、防老剂2264、酚类防老剂SP中的一种或几种；所述的填充剂为炭黑N550、炭黑N774、白炭黑、陶土、碳酸钙、滑石粉中的一种或几种；所述的加工助剂为硬脂酸、石蜡、聚乙烯蜡中的一种或几种；所述的软化剂Ⅰ为邻苯二甲酸二辛酯、邻苯二甲酸二丁酯、癸二酸二辛酯、氯化石蜡中的一种或几种；所述的发泡剂为发泡剂H、发泡剂AC、碳酸氢钠中的一种或几种；所述的发泡助剂为硬脂酸锌、氧化锌、碱式碳酸锌中的一种或几种；所述的促进剂为促进剂D、促进剂M、促进剂DM、促进剂PZ中的一种或几种；所述的硫化剂为硫磺。
优选的，所述的氯化聚乙烯橡胶氯的质量百分数为25％～48％、125℃门尼粘度为70～100；所述的吸酸剂为镁铝水滑石；所述的填充剂为炭黑N550、炭黑N774、白炭黑、陶土、碳酸钙、滑石粉中的一种或几种；所述的防老剂Ⅱ为2-硫醇基甲基苯并咪唑锌盐、4-辛基-N-(4-辛基苯基)苯胺、二苯胺类橡胶防老剂Naugard 445；所述的软化剂Ⅱ为邻苯二甲酸二辛酯、尼龙酸二辛酯、己二酸二正己酯、大分子聚酯增塑剂中的一种或几种；所述的交联助剂剂为三烯丙基异氰脲酸酯、三烯丙基氰脲酸酯、甲基丙烯酸镁、N,N′-间苯撑双马来酰亚胺等的一种或几种；所述的交联助剂为过氧化二异丙苯、双叔丁基过氧化二异丙基苯、2，5-二甲基-2，5-双(叔丁基过氧基)己烷中的一种或几种。
优选的，所述制品利用复合挤出机采用二层共挤的方式制备。
一种阻燃、耐候的绝热材料的制备方法，具体步骤为：
(1).首先将第一组合物的各原料按照添加比例准备好物料，然后将丁腈橡胶、聚氯乙烯、防老剂Ⅰ、填充剂、加工助剂、软化剂Ⅰ投入加压式密炼机中，密炼至140℃时加入发泡剂、发泡助剂、促进剂、硫化剂，密炼至150～160℃后将得到的胶料排放到开炼机上，在开炼机上薄通冷却胶料，下成厚度3～8mm及宽度60～120mm的第一胶片；
(2).其次将第二组合物的各原料按照添加比例准备好物料，然后将氯化聚乙烯橡胶、吸酸剂、防老剂Ⅱ、填充剂、加工助剂、软化剂Ⅱ投入加压式密炼机中，密炼至110℃时加入发泡剂、发泡助剂、交联助剂、交联剂，密炼至120～130℃后将得到的胶料排放到开炼机上，在开炼机上薄通冷却胶料，下成厚度3～8mm及宽度60～120mm的第二胶片；
(3).将得到的第一胶片和第二胶片分别喂料到复合挤出机中，通过复合机头挤出复合板材或管材，将挤出的复合板材或管材直接进入到110～180℃四个依次递增的分区的水平烤炉中，在烤炉中完成交联、发泡，即得到新型阻燃、耐候的绝热材料。
与现有技术相比，本发明的有益效果为：
1.本发明提供的一种阻燃、耐候的绝热材料，氯化聚乙烯是聚乙烯通过氯的取代反应制得的无规生成物，可视为乙烯、氯乙烯、1，2-二氯乙烯的三元共聚物，其分子结构中不含对热、化学性不稳定的双键，而且氯原子是沿聚乙烯链无规的结合，因此氯化聚乙烯有优异的耐热、耐臭氧、耐候、耐油、阻燃等性能，同时原料易得，具有生产成本优势。
2.本发明中使用氯化聚乙烯橡胶，造价低，添加镁铝水滑石吸酸剂，镁铝水滑石为阴离子型层状化合物,层间具有可交换的阴离子,具有一定的弱碱性，可吸收氯化聚乙烯橡胶分解产生的氯化氢，从而可对氯化聚乙烯橡胶起到热稳定作用，其结构水合层板羟基及层间离子受热时会以水和二氧化碳的形式脱出，起到降低燃烧气体浓度，阻隔氧气的阻燃作用；软化剂Ⅱ采用邻苯二甲酸二辛酯、尼龙酸二辛酯、己二酸二正己酯、大分子聚酯增塑剂中的一种或几种，使用了新型防老剂Ⅱ对其进行防护，可以赋予该组合物优异的耐高温性能、阻燃性能。
3.本发明将丁腈橡胶和聚氯乙烯，氯化聚乙烯及其它添加剂混炼成厚度3～8mm及宽度60～120mm的胶片，然后利用复合挤出机，采用二层共挤的方式，在丁腈橡胶和聚氯乙烯绝热板材或管材表面复合一层氯化聚乙烯橡胶材料，最后将挤出的复合板材或管材，进入到110～180℃温度分区的水平烤炉中，在烤炉中完成交联、发泡。由于绝热板材或管材表面复合了一层氯化聚乙烯橡胶材料，其分子链为饱和结构且均匀分布氯原子，具有优良的抗紫外线、耐各种天候性能及阻燃性能，可解决室外使用时表面层丁腈橡胶及聚氯乙烯绝热材料的耐热、耐候性差的问题，延长制品使用寿命，同时可解决三元乙丙橡胶阻燃性能差，生产成本高的问题，得到一种综合性能好的阻燃、耐候绝热材料。
附图说明
图1为实施例1的结构示意图；
图2为实施例2的结构示意图；
其中：1为第一层，2为第二层。
具体实施方式
下面结合实施例，更具体地说明本发明的内容。应当理解，本发明的实施并不局限于下面的实施例，对本发明所做的任何形式上的变通和/或改变都将落入本发明保护范围。
在本发明中，若非特指，所有的份、百分比均为重量单位，所有的设备和原料等均可从市场购得或是本行业常用的。若无特别指明，实施例采用的方法为本领域通用技术。
实施例一
结合附图2，本实施例提供一种阻燃、耐候的绝热材料及其制备方法，具体步骤为：
首先将丁腈橡胶70份、聚氯乙烯30份，以及防老剂22643份、炭黑N77410份、白炭黑15份、陶土30份、碳酸钙30份、硬脂酸1.0份、聚乙烯蜡1.0份、邻苯二甲酸二辛酯20份、癸二酸二辛酯10份、氯化石蜡20份、发泡剂AC 12份、发泡助剂碱式碳酸锌6份、促进剂D 1份、促进剂M 1.2份、硫磺1.0份，按照添加比例准备好物料，然后将丁腈橡胶、聚氯乙烯、防老剂2264、炭黑N774、白炭黑、陶土、碳酸钙、硬脂酸、聚乙烯蜡、邻苯二甲酸二辛酯、癸二酸二辛酯、氯化石蜡投入加压式密炼机中，密炼至140℃时加入发泡剂AC、碱式碳酸锌、促进剂D、促进剂M、硫磺，密炼至150℃后将胶料排放到开炼机上，在开炼机上薄通冷却胶料，下成厚度3mm及宽度60mm的第一胶片备用。
其次将氯化聚乙烯橡胶100份、镁铝水滑石10份、防老剂2-硫醇基甲基苯并咪唑锌盐1.5份、炭黑N77410份、白炭黑20份、陶土35份、碳酸钙30份、硬脂酸1.0、石蜡1.0、邻苯二甲酸二辛酯15份、尼龙酸二辛酯10份、大分子聚酯增塑剂20份、发泡剂AC 12份、硬脂酸锌6份、甲基丙烯酸镁3份、过氧化二异丙苯2份，按照添加比例准备好物料，然后将氯化聚乙烯橡胶、镁铝水滑石、防老剂2-硫醇基甲基苯并咪唑锌盐、炭黑N774、白炭黑、陶土、碳酸钙、硬脂酸、石蜡、邻苯二甲酸二辛酯、尼龙酸二辛酯、大分子聚酯增塑剂投入加压式密炼机中，密炼至110℃时加入发泡剂AC、硬脂酸锌、甲基丙烯酸镁、过氧化二异丙苯，密炼至120℃后将胶料排放到开炼机上，在开炼机上薄通冷却胶料，下成厚度3mm及宽度60mm的第二胶片备用。
最后将得到的第一胶片和第二胶片分别喂料到复合挤出机中，通过复合机头挤出表面层为氯化聚乙烯、底层或内层为丁腈橡胶及聚氯乙烯的复合板材，挤出的复合板材或管材，直接进入到一区115℃、二区128℃、三区162℃、四区175℃温度分区的水平烤炉中，在烤炉中完成交联、发泡。
本实施例中，所述氯化聚乙烯橡胶氯的质量百分数为25％，125℃门尼粘度为70。
实施例二
结合附图2，本实施例提供一种阻燃、耐候的绝热材料及其制备方法，具体步骤为：
首先将丁腈橡胶80份、聚氯乙烯20份，以及防老剂22643份、炭黑N77415份、白炭黑15份、陶土30份、碳酸钙30份、硬脂酸1.0份、石蜡1.0份、邻苯二甲酸二辛酯20份、癸二酸二辛酯15份、氯化石蜡10份、发泡剂AC 15份、碱式碳酸锌7份、促进剂D0.5份、促进剂M 1.2份、硫磺1.0份，按照添加比例准备好物料，然后将丁腈橡胶、聚氯乙烯、防老剂、炭黑、白炭黑、陶土、碳酸钙、硬脂酸、石蜡、邻苯二甲酸二辛酯、癸二酸二辛酯、氯化石蜡投入加压式密炼机中，密炼至140℃时加入发泡剂AC、碱式碳酸锌、促进剂D、促进剂M、硫磺密炼至160℃后将胶料排放到开炼机上，在开炼机上薄通冷却胶料，下成厚度8mm及宽度120mm的第一胶片。
其次将氯化聚乙烯橡胶100份、镁铝水滑石10份、防老剂4-辛基-N-(4-辛基苯基)苯胺1.5份、炭黑N77410份、白炭黑20份、陶土30份、碳酸钙35份、硬脂酸1.0、聚乙烯蜡1.0、邻苯二甲酸二辛酯15份、己二酸二正己酯15份、大分子聚酯增塑剂20份、发泡剂AC10份、硬脂酸锌6份、N,N′-间苯撑双马来酰亚胺3份、过氧化二异丙苯2份，按照添加比例准备好物料，然后将氯化聚乙烯橡胶、镁铝水滑石、防老剂4-辛基-N-(4-辛基苯基)苯胺、炭黑N774、白炭黑、陶土、碳酸钙、硬脂酸、聚乙烯蜡、邻苯二甲酸二辛酯、己二酸二正己酯、大分子聚酯增塑剂投入加压式密炼机中，密炼至110℃时加入发泡剂AC、硬脂酸锌、N,N′-间苯撑双马来酰亚胺、2，5-二甲基-2，5-双(叔丁基过氧基)己烷，密炼至130℃后将胶料排放到开炼机上，在开炼机上薄通冷却胶料，下成厚度8mm及宽度120mm的第二胶片。
将得到的第一胶片和第二胶片分别喂料到复合挤出机中，通过复合机头挤出外层为氯化聚乙烯、内层为丁腈橡胶及聚氯乙烯的复合管材。挤出的复合管材，直接进入到一区120℃、二区130℃、三区164℃、四区176℃温度分区的水平烤炉中，在烤炉中完成交联、发泡。
本实施例中，所述氯化聚乙烯橡胶氯的质量百分数为48％，125℃门尼粘度为100。
实施例三
结合附图1，本实施例提供一种阻燃、耐候的绝热材料及其制备方法，具体步骤为：
首先将丁腈橡胶60份、聚氯乙烯40份，以及防老剂2643份、炭黑N77415份、白炭黑15份、陶土30份、滑石粉30份、硬脂酸1.0份、石蜡1.0份、邻苯二甲酸二辛酯20份、癸二酸二辛酯10份、氯化石蜡10份、发泡剂H 12份、氧化锌6份、促进剂D 1份、促进剂M 1.2份、硫磺1.0份，按照添加比例准备好物料，然后将丁腈橡胶、聚氯乙烯、防老剂、炭黑、白炭黑、陶土、滑石粉、硬脂酸、石蜡、邻苯二甲酸二辛酯、癸二酸二辛酯、氯化石蜡投入加压式密炼机中，密炼至140℃时加入发泡剂H、氧化锌、促进剂D、促进剂M、硫磺，密炼至155℃后将得到的胶料排放到开炼机上，在开炼机上薄通冷却胶料，下成厚度5mm及宽度100mm的第一胶片；
其次将氯化聚乙烯橡胶100份、镁铝水滑石10份、二苯胺类橡胶防老剂Naugard4451.5份、炭黑N77410份、白炭黑20份、陶土30份、碳酸钙35份、硬脂酸1.0、聚乙烯蜡1.0、邻苯二甲酸二辛酯15份、己二酸二正己酯15份、大分子聚酯增塑剂20份、发泡剂A C 10份、硬脂酸锌6份、N,N′-间苯撑双马来酰亚胺3份、2，5-二甲基-2，5-双(叔丁基过氧基)己烷2份，按照添加比例准备好物料，然后将氯化聚乙烯橡胶、镁铝水滑石、二苯胺类橡胶防老剂Naugard 445、炭黑N774、白炭黑、陶土、碳酸钙、硬脂酸、聚乙烯蜡、邻苯二甲酸二辛酯、己二酸二正己酯、大分子聚酯增塑剂投入加压式密炼机中，密炼至110℃时加入发泡剂、硬脂酸锌、N,N′-间苯撑双马来酰亚胺、2，5-二甲基-2，5-双(叔丁基过氧基)己烷，密炼至125℃后将得到的胶料排放到开炼机上，在开炼机上薄通冷却胶料，下成厚度5mm及宽度100mm的第二胶片；
将得到的第一胶片和第二胶片分别喂料到复合挤出机中，通过复合机头挤出复合板材，将挤出的复合板材直接进入到110、125、168、180℃四个依次递增的分区的水平烤炉中，在烤炉中完成交联、发泡，即得到新型阻燃、耐候的绝热材料。
本实施例中，所述氯化聚乙烯橡胶氯的质量百分数为35％，125℃门尼粘度为80。
将实施例一、实施例二、实施例三进行性能测试，性能结果见表1：
表1性能结果
除说明书所述的技术特征外，其余技术特征为本领域技术人员的已知技术，为突出本发明的创新特点，其余技术特征在此不再赘述。综上，以上仅为本发明的较佳实施例而已，不应以此限制本发明的范围，即凡是依本发明的权利要求书及本发明说明书内容所作的简单的等效变化与修饰，均应仍属本发明专利涵盖的范围。

Claims (9)

1.一种阻燃、耐候的绝热材料，其特征在于：包括：第一层和第二层组成的制品，
所述第一层由第一组合物组成，所述第一组合物原料配方按重量份计为：丁腈橡胶60～90份、聚氯乙烯40～10份、防老剂Ⅰ0.5～3份、填充剂10～100份、加工助剂1～5份、软化剂Ⅰ10～50份、发泡剂5～15份、发泡助剂5～10份、促进剂1～5份、硫化剂1～5份；
所述第二层由第二组合物组成，所述第二组合物原料配方按重量份计为：氯化聚乙烯橡胶100份、吸酸剂5～10份、防老剂Ⅱ1～5份、填充剂10～100份、加工助剂1～5份、软化剂Ⅱ10～40份、发泡剂5～15份、发泡助剂5～10份、交联助剂1～5份、交联剂1～5份。
2.根据权利要求1所述的一种阻燃、耐候的绝热材料，其特征在于：所述制品为绝热板材或管材。
3.根据权利要求1所述的一种阻燃、耐候的绝热材料，其特征在于：所述防老剂Ⅰ为防老剂264、防老剂2264、酚类防老剂SP中的一种或几种；所述的填充剂为炭黑N550、炭黑N774、白炭黑、陶土、碳酸钙、滑石粉中的一种或几种；所述的加工助剂为硬脂酸、石蜡、聚乙烯蜡中的一种或几种；所述的软化剂Ⅰ为邻苯二甲酸二辛酯、邻苯二甲酸二丁酯、癸二酸二辛酯、氯化石蜡中的一种或几种；所述的发泡剂为发泡剂H、发泡剂AC、碳酸氢钠中的一种或几种；所述的发泡助剂为硬脂酸锌、氧化锌、碱式碳酸锌中的一种或几种；所述的促进剂为促进剂D、促进剂M、促进剂DM、促进剂PZ中的一种或几种；所述的硫化剂为硫磺。
4.根据权利要求1所述的一种阻燃、耐候的绝热材料，其特征在于：所述的氯化聚乙烯橡胶氯的质量百分数为25％～48％、125℃门尼粘度为70～100；所述的吸酸剂为镁铝水滑石；所述的防老剂Ⅱ为2-硫醇基甲基苯并咪唑锌盐、4-辛基-N-(4-辛基苯基)苯胺、二苯胺类橡胶防老剂Naugard 445；所述的软化剂Ⅱ为邻苯二甲酸二辛酯、尼龙酸二辛酯、己二酸二正己酯、大分子聚酯增塑剂中的一种或几种；所述的交联助剂剂为三烯丙基异氰脲酸酯、三烯丙基氰脲酸酯、甲基丙烯酸镁、N,N′-间苯撑双马来酰亚胺等的一种或几种；所述的交联助剂为过氧化二异丙苯、双叔丁基过氧化二异丙基苯、2，5-二甲基-2，5-双(叔丁基过氧基)己烷中的一种或几种。
5.根据权利要求1所述的一种阻燃、耐候的绝热材料，其特征在于：所述制品利用复合挤出机采用二层共挤的方式制备。
6.一种阻燃、耐候的绝热材料的制备方法，其特征在于：具体步骤为：
(1).首先将第一组合物的各原料按照添加比例准备好物料，然后将丁腈橡胶、聚氯乙烯、防老剂Ⅰ、填充剂、加工助剂、软化剂Ⅰ投入加压式密炼机中，密炼至140℃时加入发泡剂、发泡助剂、促进剂、硫化剂，密炼至150～160℃后将得到的胶料排放到开炼机上，在开炼机上薄通冷却胶料，下成第一胶片；
(2).其次将第二组合物的各原料按照添加比例准备好物料，然后将氯化聚乙烯橡胶、吸酸剂、防老剂Ⅱ、填充剂、加工助剂、软化剂Ⅱ投入加压式密炼机中，密炼至110℃时加入发泡剂、发泡助剂、交联助剂、交联剂，密炼至120～130℃后将得到的胶料排放到开炼机上，在开炼机上薄通冷却胶料，下成第二胶片；
(3).将得到的第一胶片和第二胶片分别喂料到复合挤出机中，通过复合机头挤出复合板材或管材，将挤出的复合板材或管材直接进入到水平烤炉中，在烤炉中完成交联、发泡，即得到新型阻燃、耐候的绝热材料。
7.根据权利要求6所述的一种阻燃、耐候的绝热材料的制备方法，其特征在于：所述第一胶片厚度3～8mm及宽度60～120mm。
8.根据权利要求6所述的一种阻燃、耐候的绝热材料的制备方法，其特征在于：所述第二胶片厚度3～8mm及宽度60～120mm。
9.根据权利要求6所述的一种阻燃、耐候的绝热材料的制备方法，其特征在于：所述水平烤炉内的温度为110～180℃四个依次递增的分区。
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