CN104311983B - 一种发泡倍数可控的高附着力膨胀板及其制备方法 - Google Patents

一种发泡倍数可控的高附着力膨胀板及其制备方法 Download PDF

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CN104311983B
CN104311983B CN201410586537.0A CN201410586537A CN104311983B CN 104311983 B CN104311983 B CN 104311983B CN 201410586537 A CN201410586537 A CN 201410586537A CN 104311983 B CN104311983 B CN 104311983B
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foaming
coefficient
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CN104311983A (zh
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赵雄燕
冯笑颜
王鑫
孙占英
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Hebei University of Science and Technology
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Abstract

本发明涉及一种发泡倍数可控的高附着力膨胀板及其制备方法，所述膨胀板按重量份比以乙烯‑醋酸乙烯共聚物(EVA)、双马来酰亚胺(BMI)树脂和橡胶为原料，然后依次加入发泡剂、交联剂、交联促进剂、粘结促进剂经密炼、开炼、造粒、挤出成型，制得具有高附着力且发泡倍数可控的高性能膨胀板。本发明制备工艺简单、产品发泡倍数可由温度调控、且与钢板粘结性能好、性能稳定、生产过程无污染。

Description

一种发泡倍数可控的高附着力膨胀板及其制备方法
技术领域
本发明涉及一种膨胀板，特别涉及一种发泡倍数可控的高附着力膨胀板及其制备方法。
背景技术
车船等交通行业用膨胀板主要由内层的粘合层、中间的膨胀层和外层的阻燃层构成。在车船焊装工序前先将上述膨胀板固定在车船车身钣金上的孔洞或者钣金之间形成的空腔内，膨胀板在经过烤漆工序的特定温度时，膨胀板的体积会膨胀，具有密封车身钣金上的孔洞或者钣金之间形成的空腔，起到阻隔水、烟尘以及空气噪音传播的目的，同时具有保温、填充密封、减震隔音等功效。
但目前市场上销售的膨胀板发泡倍数较低且发泡倍数不可控，与钢板的粘结性能不好。因此，膨胀板各层之间由于热膨胀系数不同，在受热膨胀过程中，会相互制约，不仅会影响膨胀率，还可能导致层间相互剥离，从而不能充分填满车身钣金上的孔洞或者钣金之间形成的空腔，造成贴合密封不好，导致减震隔音以及耐高温等性能变差，使产品性能大打折扣。因此，开发与钢板的粘结性能好且发泡倍数可调控的新型高性能膨胀板已成为我国车船等交通行业急待解决的难题。
发明内容
本发明针对现有技术的不足，提供一种发泡倍数可控的高附着力膨胀板及其制备方法。它具有生产工艺简单、成本低、产品发泡倍数可控、与钢板粘结性能好等优点。
本发明所采取的技术方案是：
一种发泡倍数可控的高附着力膨胀板，其由下述重量份的原料组成：乙烯-醋酸乙烯共聚物100，双马来酰亚胺树脂5～20，橡胶14～48，发泡剂10～25，交联剂1～8，交联促进剂1～6，粘结促进剂3～12；所述发泡剂为N,N-二亚硝基五次甲基四胺、偶氮二甲酰胺、或4,4’-氧代双苯磺酰肼中的任意一种或几种。
所述橡胶为丁基橡胶、丁苯橡胶、乙丙橡胶或天然橡胶中的一种或几种。
所述的交联剂为过氧化二异丙苯、叔丁基过氧化二异丙苯、三烯丙基异氰脲酸酯、硫磺、过氧化苯甲酸叔丁酯、过氧化苯甲酰、4,4-二(叔丁基过氧化)戊酸正丁酯或2,5-二甲基-2,5-双(叔丁基过氧基)己烷中的一种或几种。
所述的交联促进剂为乙基苯二硫代氨基甲酸锌、二乙基二硫代氨基甲酸锌、二硫代二吗啉、六硫化双五甲撑秋兰姆、四硫化双五甲撑秋兰姆、二甲基二硫代氨基甲酸锌、二硫化四甲基秋兰姆、2-硫醇基苯骈噻唑或三羟甲基丙烷三丙烯酸酯中的一种或几种。
所述的粘结促进剂为硬脂酸钴、硼酰化钴、环烷酸钴中的一种或几种。
上述的发泡倍数可控的高附着力膨胀板的制备方法，它包括下述步骤：
①密炼：按配方重量份，首先将乙烯-醋酸乙烯共聚物、双马来酰亚胺树脂和橡胶加入到密炼机中，在100～130℃下，混合10～20min，然后，依次加入发泡剂、交联剂、交联促进剂和粘结促进剂，并在100～130℃下再混合5～20min，形成均匀混合体。
②开炼：将步骤①中的均匀混合体加入到双辊混炼机中，在110～130℃下，薄通3～12遍，出片，然后粉碎、造粒成粒料。
③成型：将步骤②中的粒料加入到单螺杆或双螺杆挤出机中，于100～120℃下挤出成型，得到板材，所述板材的厚度为1.5mm、或3mm或6mm。经切割、裁剪制成标准尺寸的膨胀板。
④将步骤③制得的膨胀板放入150℃～170℃的烘箱中，发泡30分钟，即得到不同发泡倍数的高附着力发泡产品。
优选的，所述的发泡倍数可控的高附着力膨胀板的制备方法，它包括以下具体步骤：
①密炼：按重量份数计，首先把EVA 100份、BMI 5份、天然橡胶20份加入到密炼机中，在120℃温度下，混合10min，然后依次加入N,N-二亚硝基五次甲基四胺5份、4,4’-氧代双苯磺酰肼5份、叔丁基过氧化二异丙苯1份、硫磺0.2份、三烯丙基异氰脲酸酯3份、二硫化四甲基秋兰姆1.5份、乙基苯二硫代氨基甲酸锌0.5份、三羟甲基丙烷三丙烯酸酯1.5份、硬脂酸钴3份，并在110℃温度下再混合5min，形成均匀混合体；
②开炼：将上述均匀混合体加入到双辊混炼机中，在120℃温度下，薄通5遍，出片，然后用粉碎机粉碎、造粒成粒料；
③成型：将上述粒料加入到单螺杆或双螺杆挤出机中，于105～110℃温度下挤出成型，得到厚度分别为1.5mm、3mm、6mm的板材，经切割裁剪制成各种规格的汽车用膨胀板制品；
④将上述膨胀板制品分别放入150℃、160℃和170℃的烘箱中，发泡30分钟，即得到不同发泡倍数的高附着力发泡产品。
本发明与现有技术相比具有的突出效果为：
本发明将EVA、BMI树脂、橡胶、发泡剂、交联剂、交联促进剂、粘结促进剂通过共混、挤出的方式有机的结合在一起，使膨胀板中各组份间能够充分发挥协同效应，制得的膨胀板为集发泡膨胀、粘结、耐高温等优异性能于一身的质地均匀的高性能膨胀板。采用本发明制备的膨胀板块在经过烤漆工序的特定温度时，可迅速膨胀、交联，形成海绵体并牢固地粘结在车船的钢板上，其发泡倍数可由烘箱温度进行调控，最高可达到3800％以上。
采用本发明技术方案所产生的有益效果还具有：①生产工艺简单、成本低；②产品发泡倍数可控；③与钢板粘结性能好。
具体实施方式
下面结合实施例对本发明作进一步的说明。
说明：本发明实施例中所用的各种原料以及密炼机、双辊混炼机、粉碎机、单螺杆/双螺杆挤出机均为市售产品。
实施例1
(1)密炼：按重量份数计，首先把EVA 100份、BMI 5份、天然橡胶20份加入到密炼机中，在120℃温度下，混合10min，然后依次加入N,N-二亚硝基五次甲基四胺5份、4,4’-氧代双苯磺酰肼5份、叔丁基过氧化二异丙苯1份、硫磺0.2份、三烯丙基异氰脲酸酯3份、二硫化四甲基秋兰姆1.5份、乙基苯二硫代氨基甲酸锌0.5份、三羟甲基丙烷三丙烯酸酯1.5份、硬脂酸钴3份，并在110℃温度下再混合5min，形成均匀混合体。
(2)开炼：将上述均匀混合体加入到双辊混炼机中，在120℃温度下，薄通5遍，出片，然后用粉碎机粉碎、造粒成粒料。
(3)成型：将上述粒料加入到单螺杆或双螺杆挤出机中，于100～120℃温度下挤出成型，得到厚度分别为1.5mm、3mm、6mm的板材，经切割裁剪制成各种规格的车船用膨胀板制品。
(4)将步骤(3)制得的膨胀板分别放入150℃、160℃和170℃的烘箱中，发泡30分钟，即得到不同发泡倍数的高附着力发泡产品。
按浙江吉利汽车有限公司《乘用车用聚乙烯类膨胀胶块》(Q/JLYJ711143-2009)的标准对产品进行测试，结果如表2所示。
实施例2
(1)密炼：按重量份数计，首先把EVA 100份、BMI 7份、乙丙橡胶15份加入到密炼机中，在125℃温度下，混合15min，然后依次加入偶氮二甲酰胺10份、三烯丙基异氰脲酸酯3份、硫磺0.3份、叔丁基过氧化二异丙苯1份、二硫化四甲基秋兰姆1.2份、2-硫醇基苯骈噻唑1份、三羟甲基丙烷三丙烯酸酯1份、硼酰化钴10份，并在125℃温度下再混合8min，形成均匀混合体。
(2)开炼：将上述均匀混合体加入到双辊混炼机中，在130℃温度下，薄通8遍，出片，然后粉碎，造粒成粒料。
(3)成型：将上述粒料加入到单螺杆或双螺杆挤出机中，于100～118℃温度下挤出成型，得到厚度分别为1.5mm、3mm、6mm的板材，经切割裁剪制成各种规格的车船用膨胀板制品。
(4)将步骤(3)制得的膨胀板分别放入150℃、160℃和170℃的烘箱中，发泡30分钟，即得到不同发泡倍数的高附着力发泡产品。
按浙江吉利汽车有限公司《乘用车用聚乙烯类膨胀胶块》(Q/JLYJ711143-2009)的标准对产品进行测试，结果如表2所示。
实施例3
(1)密炼：按重量份数计，首先把EVA 100份、BMI 9份、丁苯橡胶25份加入到密炼机中，在110℃温度下，混合20min，然后依次加入N,N-二亚硝基五次甲基四胺20份、三烯丙基异氰脲酸酯3份、硫磺0.4份、2,5-二甲基-2,5-双(叔丁基过氧基)己烷1.5份、二硫化四甲基秋兰姆1.2份、二硫代二吗啉0.8份、三羟甲基丙烷三丙烯酸酯1份、硼酰化钴3份、环烷酸钴2份，并在105℃温度下再混合20min，形成均匀混合体。
(2)开炼：将上述混合体加入到双辊混炼机中，在115℃温度下，薄通12遍，出片，然后粉碎，造粒。
(3)成型：将上述粒料加入到单螺杆或双螺杆挤出机中，于100～115℃温度下挤出成型，得到厚度分别为1.5mm、3mm、6mm的板材，经切割裁剪制成各种规格的车船用膨胀板制品。
(4)将步骤(3)制得的膨胀板分别放入150℃、160℃和170℃的烘箱中，发泡30分钟，即得到不同发泡倍数的高附着力发泡产品。
按浙江吉利汽车有限公司《乘用车用聚乙烯类膨胀胶块》(Q/JLYJ711143-2009)的标准对产品进行测试，结果如表2所示。
实施例4～8
按照表1的组分及配比配制原料，制备方法与实施例2相同。
表1实施例1-实施例8中的组分及重量份配比
表2实施例1-实施例3的性能测试结果
综上，采用本发明制备的产品其发泡倍数具有温度依赖性，故实际生产中，可根据要求通过改变发泡温度来控制产品的发泡倍数，达到最佳的贴合密封；此外，该产品的耐高温性能及与钢板的粘结性都很好，是一种非常理想的车船用发泡板产品。

Claims (7)

1.一种发泡倍数可控的高附着力膨胀板，其特征在于其由下述重量份的原料组成：乙烯-醋酸乙烯共聚物100，双马来酰亚胺树脂5～20，橡胶14～48，发泡剂10～25，交联剂1～8，交联促进剂1～6，粘结促进剂3～12；所述发泡剂为N,N-二亚硝基五次甲基四胺、偶氮二甲酰胺、或4,4’-氧代双苯磺酰肼中的任意一种或几种；所述的粘结促进剂为硬脂酸钴、硼酰化钴、环烷酸钴中的一种或几种。
2.如权利要求1所述的发泡倍数可控的高附着力膨胀板，其特征在于所述橡胶为丁基橡胶、丁苯橡胶、乙丙橡胶或天然橡胶中的一种或几种。
3.如权利要求1所述的发泡倍数可控的高附着力膨胀板，其特征在于所述的交联剂为过氧化二异丙苯、叔丁基过氧化二异丙苯、三烯丙基异氰脲酸酯、硫磺、过氧化苯甲酸叔丁酯、过氧化苯甲酰、4,4-二(叔丁基过氧化)戊酸正丁酯或2,5-二甲基-2,5-双(叔丁基过氧基)己烷中的一种或几种。
4.如权利要求1所述的发泡倍数可控的高附着力膨胀板，其特征在于所述的交联促进剂为乙基苯二硫代氨基甲酸锌、二乙基二硫代氨基甲酸锌、二硫代二吗啉、六硫化双五甲撑秋兰姆、四硫化双五甲撑秋兰姆、二甲基二硫代氨基甲酸锌、二硫化四甲基秋兰姆、2-硫醇基苯骈噻唑或三羟甲基丙烷三丙烯酸酯中的一种或几种。
5.一种如权利要求1所述的发泡倍数可控的高附着力膨胀板的制备方法，其特征在于它包括下述步骤：
①密炼：按配方重量份，首先将乙烯-醋酸乙烯共聚物、双马来酰亚胺树脂和橡胶加入到密炼机中，在100～130℃下，混合10～20min，然后，依次加入发泡剂、交联剂、交联促进剂和粘结促进剂，并在100～130℃下再混合5～20min，形成均匀混合体；
②开炼：将步骤①中的均匀混合体加入到双辊混炼机中，在110～130℃下，薄通3～12遍，出片，然后粉碎、造粒成粒料；
③成型：将步骤②中的粒料加入到单螺杆或双螺杆挤出机中，于100～120℃下挤出成型，得到板材，经切割、裁剪制成标准尺寸的膨胀板；
④将步骤③制得的膨胀板放入150℃～170℃的烘箱中，发泡30分钟，即得到不同发泡倍数的高附着力发泡产品。
6.如权利要求5所述的发泡倍数可控的高附着力膨胀板的制备方法，其特征在于所述板材的厚度为1.5mm、或3mm或6mm。
7.如权利要求5所述的发泡倍数可控的高附着力膨胀板的制备方法，其特征在于它包括以下具体步骤：
①密炼：按重量份数计，首先把EVA 100份、BMI 5份、天然橡胶20份加入到密炼机中，在120℃温度下，混合10min，然后依次加入N,N-二亚硝基五次甲基四胺5份、4,4’-氧代双苯磺酰肼5份、叔丁基过氧化二异丙苯1份、硫磺0.2份、三烯丙基异氰脲酸酯3份、二硫化四甲基秋兰姆1.5份、乙基苯二硫代氨基甲酸锌0.5份、三羟甲基丙烷三丙烯酸酯1.5份、硬脂酸钴3份，并在110℃温度下再混合5min，形成均匀混合体；
②开炼：将上述均匀混合体加入到双辊混炼机中，在120℃温度下，薄通5遍，出片，然后用粉碎机粉碎、造粒成粒料；
③成型：将上述粒料加入到单螺杆或双螺杆挤出机中，于105～110℃温度下挤出成型，得到厚度分别为1.5mm、3mm、6mm的板材，经切割裁剪制成各种规格的汽车用膨胀板制品；
④将上述膨胀板制品分别放入150℃、160℃和170℃的烘箱中，发泡30分钟，即得到不同发泡倍数的高附着力发泡产品。
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