CN107513364A - 一种阻燃耐热聚氨酯胶黏剂 - Google Patents

一种阻燃耐热聚氨酯胶黏剂 Download PDF

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CN107513364A
CN107513364A CN201710888818.5A CN201710888818A CN107513364A CN 107513364 A CN107513364 A CN 107513364A CN 201710888818 A CN201710888818 A CN 201710888818A CN 107513364 A CN107513364 A CN 107513364A
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朱立芳
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ANHUI BIG PINE RESIN Co Ltd
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Abstract

本发明公开了一种阻燃耐热聚氨酯胶黏剂，其原料按重量份包括：聚己二酸‑1,4‑丁二醇酯45‑70份、聚(碳酸1,5‑戊二醇酯)二醇10‑35份、双二茂铁基醇8‑15份、异佛尔酮二异氰酸酯50‑70份、蔗糖2‑10份、扩链剂3‑15份、1‑氨基乙叉‑1,1‑二膦酸3‑12份、海藻酸钙纤维1‑8份、核桃壳粉2‑8份、聚酰亚胺1‑5份、氨基硅油1‑5份、环氧树脂2‑5份、醛酮树脂2‑10份、凹凸棒土3‑9份、纳米氧化铝3‑15份、1,2‑二羟甲基碳硼烷2‑10份、溶剂30‑80份、抗氧剂0.1‑0.8份。本发明提出的阻燃耐热聚氨酯胶黏剂，其具有优异的耐热性和阻燃性，且固化速度快，与基材的粘结强度高。

Description

一种阻燃耐热聚氨酯胶黏剂
技术领域
本发明涉及胶黏剂技术领域，尤其涉及一种阻燃耐热聚氨酯胶黏剂。
背景技术
胶黏剂是指通过界面的黏附和内聚等作用，能使两种或两种以上的制件或材料连接在一起的天然的或合成的、有机的或无机的一类物质，按化学成分可以分为环氧树脂胶黏剂、聚氨酯胶黏剂、聚醋酸乙烯胶黏剂等。
聚氨酯胶黏剂是指在分子链中含有氨基甲酸酯基团或异氰酸酯基的胶粘剂，其分子中含有极性很强、化学活泼性很高的异氰酸酯和氨基甲酸酯基团，与泡沫塑料、木材、皮革、织物、纸张、陶瓷等多孔材料，以及金属、玻璃、橡胶、塑料等表面光洁的材料都有着优良的化学粘合力，且韧性、可调节性好，耐低温性能优良，目前已被广泛应用在了家具制造、电工电子、鞋类、纺织、包装印刷、航空航天等领域。但是现有的聚氨酯胶黏剂其耐热性和阻燃性欠佳，严重限制了聚氨酯胶黏剂在某些特殊领域的使用。
发明内容
基于背景技术存在的技术问题，本发明提出了一种阻燃耐热聚氨酯胶黏剂，其具有优异的耐热性和阻燃性，且固化速度快，与基材的粘结强度高。
本发明提出的一种阻燃耐热聚氨酯胶黏剂，其原料按重量份包括：聚己二酸-1,4-丁二醇酯45-70份、聚(碳酸1,5-戊二醇酯)二醇10-35份、双二茂铁基醇8-15份、异佛尔酮二异氰酸酯50-70份、蔗糖2-10份、扩链剂3-15份、1-氨基乙叉-1,1-二膦酸3-12份、海藻酸钙纤维1-8份、核桃壳粉2-8份、聚酰亚胺1-5份、氨基硅油1-5份、环氧树脂2-5份、醛酮树脂2-10份、凹凸棒土3-9份、纳米氧化铝3-15份、1,2-二羟甲基碳硼烷2-10份、溶剂30-80份、抗氧剂0.1-0.8份。
优选地，所述扩链剂为三乙醇胺、二甲硫基甲苯二胺、二羟甲基丙酸中的一种或者多种的混合物。
优选地，所述凹凸棒土为γ-氨丙基三乙氧基硅烷改性凹凸棒土。
优选地，所述纳米氧化铝为改性纳米氧化铝；所述改性纳米氧化铝按照以下工艺进行制备：将苯酚和多聚甲醛加入甲苯中，搅拌均匀后升温至48-55℃，加入丙烯胺和甲苯的混合溶液，搅拌均匀后回流反应3-8h，反应结束经萃取、过滤得到物料A；将硅烷偶联剂KH-570改性纳米氧化铝、物料A、苯乙烯、丙烯酸丁酯和过氧化苯甲酰加入甲苯中，在氮气的保护下反应30-50min，反应的温度为65-75℃，加入马来酸酐、过氧化苯甲酰、丙酮的混合物，在70-85℃下反应50-80min，反应结束后经沉淀、过滤、干燥得到所述改性纳米氧化铝；
在改性纳米氧化铝的制备过程中，首先以苯酚、多聚甲醛和丙烯胺为原料，使苯酚、多聚甲醛和丙烯胺发生了反应，得到了含烯丙基苯丙噁嗪的物料A，之后将物料A与硅烷偶联剂KH-570改性纳米氧化铝、苯乙烯、丙烯酸丁酯、马来酸酐反应，从而将物料A、苯乙烯、丙烯酸丁酯、马来酸酐引入到了硅烷偶联剂KH-570改性纳米氧化铝的表面，得到了改性纳米氧化铝，将其加入体系中，在体系中分散均匀，与海藻酸钙纤维、氨基乙叉-1,1-二膦酸、凹凸棒土、1,2-二羟甲基碳硼烷具有协同作用，在胶黏剂燃烧的过程中形成了致密的阻隔层，隔绝氧气的热量的传播，赋予胶黏剂优异的阻燃性和耐热性，同时显著提高了胶黏剂与基材的附着力，改善了胶黏剂的粘结性能。
优选地，苯酚、多聚甲醛、丙烯胺的重量比为3-5：2-4：2-5。
优选地，苯酚、多聚甲醛、丙烯胺的重量比为4.7：3.3：2.9。
优选地，硅烷偶联剂KH-570改性纳米氧化铝、物料A、苯乙烯、丙烯酸丁酯、马来酸酐的重量比3-10：2-8：2-5：3-5：0.5-2。
优选地，所述溶剂为丙酮、乙酸乙酯、丁醇中的一种或者多种的混合物。
优选地，所述抗氧剂为受阻酚抗氧剂、亚磷酸酯抗氧剂中的一种或者两种的混合物。
本发明所述阻燃耐热聚氨酯胶黏剂，其原料中，双二茂铁基醇和聚(碳酸1,5-戊二醇酯)二醇与聚己二酸-1,4-丁二醇酯配合，在基体中引入二茂铁和聚碳酸酯结构，显著提升了胶黏剂的热稳定性，增强了胶黏剂的强度，赋予胶黏剂优良的力学性能、耐水解性、耐热性、耐氧化性和耐磨性；海藻酸钙纤维加入体系中，与氨基乙叉-1,1-二膦酸、凹凸棒土、纳米氧化铝、1,2-二羟甲基碳硼烷具有协同作用，在胶黏剂燃烧的过程中形成了致密的阻隔层，隔绝氧气的热量的传播，赋予胶黏剂优异的阻燃性和耐热性；醛酮树脂加入体系中，与聚酰亚胺、氨基硅油、环氧树脂具有优异的协同作用，显著提高了胶黏剂的固化速度、光泽度和粘结强度，同时给予胶黏剂较高的粘结性能和较强的附着力，改善了胶黏剂的耐水性、耐候性、耐热性和耐酸碱性；加入了蔗糖，其与扩链剂配合，增加了体系的交联程度，降低了胶膜的吸水率，显著提高了胶黏剂的耐水性。
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
本发明提出的一种阻燃耐热聚氨酯胶黏剂，其原料按重量份包括：聚己二酸-1,4-丁二醇酯70份、聚(碳酸1,5-戊二醇酯)二醇10份、双二茂铁基醇15份、异佛尔酮二异氰酸酯50份、蔗糖10份、扩链剂3份、1-氨基乙叉-1,1-二膦酸12份、海藻酸钙纤维1份、核桃壳粉8份、聚酰亚胺1份、氨基硅油5份、环氧树脂2份、醛酮树脂10份、凹凸棒土3份、纳米氧化铝15份、1,2-二羟甲基碳硼烷2份、溶剂80份、抗氧剂0.1份。
实施例2
本发明提出的一种阻燃耐热聚氨酯胶黏剂，其原料按重量份包括：聚己二酸-1,4-丁二醇酯45份、聚(碳酸1,5-戊二醇酯)二醇35份、双二茂铁基醇8份、异佛尔酮二异氰酸酯70份、蔗糖2份、扩链剂15份、1-氨基乙叉-1,1-二膦酸3份、海藻酸钙纤维8份、核桃壳粉2份、聚酰亚胺5份、氨基硅油1份、环氧树脂5份、醛酮树脂2份、凹凸棒土9份、纳米氧化铝3份、1,2-二羟甲基碳硼烷10份、溶剂30份、抗氧剂0.8份。
实施例3
本发明提出的一种阻燃耐热聚氨酯胶黏剂，其原料按重量份包括：聚己二酸-1,4-丁二醇酯67份、聚(碳酸1,5-戊二醇酯)二醇19份、双二茂铁基醇13份、异佛尔酮二异氰酸酯55份、蔗糖9份、三乙醇胺7份、1-氨基乙叉-1,1-二膦酸10份、海藻酸钙纤维3份、核桃壳粉6份、聚酰亚胺2.8份、氨基硅油4.2份、环氧树脂3份、醛酮树脂8份、凹凸棒土4.5份、纳米氧化铝12份、1,2-二羟甲基碳硼烷4份、丙酮73份、受阻酚抗氧剂0.2份；
其中，所述凹凸棒土为γ-氨丙基三乙氧基硅烷改性凹凸棒土；
所述纳米氧化铝为改性纳米氧化铝；所述改性纳米氧化铝按照以下工艺进行制备：将苯酚和多聚甲醛加入甲苯中，搅拌均匀后升温至55℃，加入丙烯胺和甲苯的混合溶液，其中，苯酚、多聚甲醛、丙烯胺的重量比为3：4：2，搅拌均匀后回流反应8h，反应结束经萃取、过滤得到物料A；将硅烷偶联剂KH-570改性纳米氧化铝、物料A、苯乙烯、丙烯酸丁酯和过氧化苯甲酰加入甲苯中，在氮气的保护下反应30min，反应的温度为75℃，加入马来酸酐、过氧化苯甲酰、丙酮的混合物，其中，硅烷偶联剂KH-570改性纳米氧化铝、物料A、苯乙烯、丙烯酸丁酯、马来酸酐的重量比3：8：2：5：0.5，在85℃下反应50min，反应结束后经沉淀、过滤、干燥得到所述改性纳米氧化铝。
实施例4
本发明提出的一种阻燃耐热聚氨酯胶黏剂，其原料按重量份包括：聚己二酸-1,4-丁二醇酯50份、聚(碳酸1,5-戊二醇酯)二醇30份、双二茂铁基醇9份、异佛尔酮二异氰酸酯64份、蔗糖4份、二甲硫基甲苯二胺10份、二羟甲基丙酸2份、1-氨基乙叉-1,1-二膦酸6份、海藻酸钙纤维7份、核桃壳粉3份、聚酰亚胺4份、氨基硅油2份、环氧树脂4.3份、醛酮树脂5份、凹凸棒土8份、纳米氧化铝6份、1,2-二羟甲基碳硼烷9份、乙酸乙酯25份、丁醇20份、亚磷酸酯抗氧剂0.6份；
其中，所述凹凸棒土为γ-氨丙基三乙氧基硅烷改性凹凸棒土；
所述纳米氧化铝为改性纳米氧化铝；所述改性纳米氧化铝按照以下工艺进行制备：将苯酚和多聚甲醛加入甲苯中，搅拌均匀后升温至48℃，加入丙烯胺和甲苯的混合溶液，其中，苯酚、多聚甲醛、丙烯胺的重量比为5：2：5，搅拌均匀后回流反应3h，反应结束经萃取、过滤得到物料A；将硅烷偶联剂KH-570改性纳米氧化铝、物料A、苯乙烯、丙烯酸丁酯和过氧化苯甲酰加入甲苯中，在氮气的保护下反应50min，反应的温度为65℃，加入马来酸酐、过氧化苯甲酰、丙酮的混合物，其中，硅烷偶联剂KH-570改性纳米氧化铝、物料A、苯乙烯、丙烯酸丁酯、马来酸酐的重量比10：2：5：3：2，在70℃下反应80min，反应结束后经沉淀、过滤、干燥得到所述改性纳米氧化铝。
实施例5
本发明提出的一种阻燃耐热聚氨酯胶黏剂，其原料按重量份包括：聚己二酸-1,4-丁二醇酯50份、聚(碳酸1,5-戊二醇酯)二醇30份、双二茂铁基醇10份、异佛尔酮二异氰酸酯60份、蔗糖5份、扩链剂12份、1-氨基乙叉-1,1-二膦酸9份、海藻酸钙纤维7份、核桃壳粉6份、聚酰亚胺3份、氨基硅油2份、环氧树脂4份、醛酮树脂6份、凹凸棒土7份、纳米氧化铝8份、1,2-二羟甲基碳硼烷8份、溶剂50份、抗氧剂0.6份；
其中，所述扩链剂为三乙醇胺、二甲硫基甲苯二胺、二羟甲基丙酸的混合物，且三乙醇胺、二甲硫基甲苯二胺、二羟甲基丙酸的重量比为4:5:2；
所述凹凸棒土为γ-氨丙基三乙氧基硅烷改性凹凸棒土；
所述纳米氧化铝为改性纳米氧化铝；所述改性纳米氧化铝按照以下工艺进行制备：将苯酚和多聚甲醛加入甲苯中，搅拌均匀后升温至50℃，加入丙烯胺和甲苯的混合溶液，其中，苯酚、多聚甲醛、丙烯胺的重量比为4.7：3.3：2.9，搅拌均匀后回流反应5h，反应结束经萃取、过滤得到物料A；将硅烷偶联剂KH-570改性纳米氧化铝、物料A、苯乙烯、丙烯酸丁酯和过氧化苯甲酰加入甲苯中，在氮气的保护下反应40min，反应的温度为70℃，加入马来酸酐、过氧化苯甲酰、丙酮的混合物，其中，硅烷偶联剂KH-570改性纳米氧化铝、物料A、苯乙烯、丙烯酸丁酯、马来酸酐的重量比6：5：4：4：1.2，在78℃下反应60min，反应结束后经沉淀、过滤、干燥得到所述改性纳米氧化铝；
所述溶剂为丙酮、乙酸乙酯、丁醇的混合物，且丙酮、乙酸乙酯、丁醇的体积比为3：4：2；
所述抗氧剂为受阻酚抗氧剂、亚磷酸酯抗氧剂的混合物，且受阻酚抗氧剂、亚磷酸酯抗氧剂的3：2。
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)

1.一种阻燃耐热聚氨酯胶黏剂，其特征在于，其原料按重量份包括：聚己二酸-1,4-丁二醇酯45-70份、聚(碳酸1,5-戊二醇酯)二醇10-35份、双二茂铁基醇8-15份、异佛尔酮二异氰酸酯50-70份、蔗糖2-10份、扩链剂3-15份、1-氨基乙叉-1,1-二膦酸3-12份、海藻酸钙纤维1-8份、核桃壳粉2-8份、聚酰亚胺1-5份、氨基硅油1-5份、环氧树脂2-5份、醛酮树脂2-10份、凹凸棒土3-9份、纳米氧化铝3-15份、1,2-二羟甲基碳硼烷2-10份、溶剂30-80份、抗氧剂0.1-0.8份。
2.根据权利要求1所述阻燃耐热聚氨酯胶黏剂，其特征在于，所述扩链剂为三乙醇胺、二甲硫基甲苯二胺、二羟甲基丙酸中的一种或者多种的混合物。
3.根据权利要求1或2所述阻燃耐热聚氨酯胶黏剂，其特征在于，所述凹凸棒土为γ-氨丙基三乙氧基硅烷改性凹凸棒土。
4.根据权利要求1-3中任一项所述阻燃耐热聚氨酯胶黏剂，其特征在于，所述纳米氧化铝为改性纳米氧化铝；所述改性纳米氧化铝按照以下工艺进行制备：将苯酚和多聚甲醛加入甲苯中，搅拌均匀后升温至48-55℃，加入丙烯胺和甲苯的混合溶液，搅拌均匀后回流反应3-8h，反应结束经萃取、过滤得到物料A；将硅烷偶联剂KH-570改性纳米氧化铝、物料A、苯乙烯、丙烯酸丁酯和过氧化苯甲酰加入甲苯中，在氮气的保护下反应30-50min，反应的温度为65-75℃，加入马来酸酐、过氧化苯甲酰、丙酮的混合物，在70-85℃下反应50-80min，反应结束后经沉淀、过滤、干燥得到所述改性纳米氧化铝。
5.根据权利要求4所述阻燃耐热聚氨酯胶黏剂，其特征在于，苯酚、多聚甲醛、丙烯胺的重量比为3-5：2-4：2-5。
6.根据权利要求4或5所述阻燃耐热聚氨酯胶黏剂，其特征在于，苯酚、多聚甲醛、丙烯胺的重量比为4.7：3.3：2.9。
7.根据权利要求4-6中任一项所述阻燃耐热聚氨酯胶黏剂，其特征在于，硅烷偶联剂KH-570改性纳米氧化铝、物料A、苯乙烯、丙烯酸丁酯、马来酸酐的重量比3-10：2-8：2-5：3-5：0.5-2。
8.根据权利要求1-7中任一项所述阻燃耐热聚氨酯胶黏剂，其特征在于，所述溶剂为丙酮、乙酸乙酯、丁醇中的一种或者多种的混合物。
9.根据权利要求1-8中任一项所述阻燃耐热聚氨酯胶黏剂，其特征在于，所述抗氧剂为受阻酚抗氧剂、亚磷酸酯抗氧剂中的一种或者两种的混合物。
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Application publication date: 20171226