CN115490959B - 一种高强度交联聚丙烯泡棉材料及其制备方法 - Google Patents
一种高强度交联聚丙烯泡棉材料及其制备方法 Download PDFInfo
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 70
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 70
- -1 polypropylene Polymers 0.000 title claims abstract description 64
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- 238000002360 preparation method Methods 0.000 title abstract description 11
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000005187 foaming Methods 0.000 claims abstract description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims abstract description 20
- 239000011701 zinc Substances 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 20
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
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- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
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- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 claims 1
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- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 claims 1
- FKIOYBLZUCCLTL-UHFFFAOYSA-N 4-butyl-2-tert-butyl-5-methylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C=C1C FKIOYBLZUCCLTL-UHFFFAOYSA-N 0.000 claims 1
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Abstract
本发明提供一种高强度交联聚丙烯泡棉材料及其制备方法。该方法采用二氰胺锌为敏化及低温发泡抑制剂,马来酸酐接枝聚丙烯、聚丙烯与线性低密度聚乙烯复配,获得具有高耐热和力学强度的聚丙烯发泡材料。本发明所述的方法具有如下优点:(1)产品耐热性好,可达120℃以上;(2)产品强度高,表观密度小于0.1g/cm3时,厚度1mm时,弹性模量在15MPa以上,邵氏硬度在60D以上;(3)产品粘结性高,电晕表面张力可达38mN/m以上,满足涂胶工艺要求,可维持6个月以上;(4)所得材料在机械抗震、汽车内饰、保温管、电子设备等领域具有广泛应用。
Description
技术领域
本发明涉及一种高强度交联聚丙烯泡棉材料及其制备方法,属于高分子材料技术领域。
背景技术
辐射交联聚乙烯泡沫塑料是一种介于软质(聚氨酯)和硬质(聚苯乙烯)泡沫塑料之间的闭孔结构的新型发泡塑料,具有优越的强韧性、弹性、挠曲性、耐磨性、耐化学腐蚀性、耐低温性和绝缘性好等一系列特性,可作为良好的绝缘、绝热、防震及浮力材料,广泛应用于工业、农业、建筑和交通运输等各个领域。但PE泡沫塑料则因其本身材料力学性能差、耐热性差(最高使用温度仅为80℃左右)以及难易降解等限制了PE发泡材料的应用。聚丙烯(PP)泡沫具有许多优异的性能,包括价格低、耐温性好、熔点高、拉伸模量高、密度低、耐化学性好,成为发泡工业中的“新贵”。就力学性能而言,PP比PE具有更高的静态承载能力,比PS具有更高的冲击韧性。聚丙烯(PP)发泡材料因其优异的耐热性、力学性以及环境友好性等受到了广泛关注,成为欧、美、日等发达国家作为替代PU、PE以及PS泡沫材料的高性能绿色发泡材料。
尽管性能优越,但PP发泡仍困难重重,主要是因为普通PP的分子链是线性结构的,在发泡过程中泡孔壁经受的双轴拉伸作用会使线性链的缠结迅速打开,分子链容易发生相对滑动,因而拉伸黏度较低。即使施加很小的应力作用也会使PP发生很大的形变,因此表现为发泡过程中泡孔壁强度不高,易发生破裂,与此同时气泡内的气体大量逃逸扩散到环境中,最终导致发泡制品的泡孔壁厚、泡孔尺寸不均匀、发泡倍率不高等缺陷。同时,由于PP熔点高,挤出加工温度在140℃以上,在此高温加工过程中,无法采用传统聚乙烯的Ac发泡体系。
发明内容
为解决以上技术问题,本申请提供一种高强度交联聚丙烯泡棉材料及其制备方法,以二氰胺锌为敏化及低温发泡抑制剂,极大提升材料挤出加工温度,保证聚丙烯充分熔融塑化,通过马来酸接枝共聚丙烯、低密度聚乙烯与聚丙烯共混,在合适挤出工艺下形成特定凝聚态结构,促进分子链缠结,并在辐照交联过程接入形成交联网络,提高发泡熔体强度,利用配方中极性组分,提高材料电晕持久性。
该泡棉材料包括35~60重量份聚丙烯、5~20重量份马来酸酐接枝聚丙烯、10~60重量份低密度聚乙烯、2~20重量份偶氮二甲酰胺发泡剂、0.5~5重量份二氰胺锌、0.5~4重量份抗氧化剂制成。该泡棉材料强度高,弹性模量在15MPa以上,邵氏硬度在60D以上,电晕后表面张力在40mN/m以上,可维持6个月以上。同时该泡棉材料具有表观密度为0.05~0.10g/cm3。
在较佳实施例中,所述的马来酸酐接枝聚丙烯主要是聚丙烯与马来酸酐进行接枝共聚而成,首将100质量份聚丙烯、(5~30)质量份马来酸酐、(0.5~2)质量份硫化剂在130~160℃密炼机中进行密炼反应1~4h后,进行造粒挤出,得相应马来酸酐接枝聚丙烯。
在较佳实施例中,所述的二氰胺锌主要是二氰胺钠与氯化锌进行离子交换制备而成,将二氰胺钠溶于50%乙醇水溶液中配成浓度为10%的二氰胺钠溶液,加入50%的氯化锌水溶液,控制二氰胺钠与氯化锌摩尔比为2:1,在50~65℃下进行搅拌反应6~10h后,过滤,乙醇洗涤,干燥得二氰胺锌。
在较佳实施例中,所述的接枝共聚用聚丙烯是共聚聚丙烯,包括乙烯丙稀共聚物、丁烯丙烯共聚物等二元共聚物、乙烯丙烯丁烯三元共聚物中的任一种或多种的混合物,共聚聚丙烯的熔融指数(MI,230℃/2.16kg)为0.5~5g/10min,熔点(MP)为125~140℃;
在较佳实施例中,所述聚丙烯为密度为0.87~0.91g/cm3,熔融指数(MI,230℃/2.16kg)为0.5~10g/10min的一般等规聚丙烯一种或两种以上的组合物。
在较佳实施例中,所述低密度聚乙烯包括为密度为0.901~0.922g/cm3,熔融指数(MI,230℃/2.16kg)为1~6g/10min的一般低密度聚乙烯、密度为0.905~0.930g/cm3,熔融指数(MI,230℃/2.16kg)为0.3~5g/10min的线性低密度聚乙烯中一种或者两种以上的组合物;
本申请还提供一种高强度交联聚乙烯泡棉材料的制备方法,所述制备方法包括以下步骤:
马来酸酐接枝聚丙烯合成阶段:将100质量份聚丙烯、(5~30)质量份马来酸酐、(0.5~2)质量份硫化剂在130~160℃密炼机中进行密炼反应1~4h后,进行造粒挤出,得相应马来酸酐接枝聚丙烯。
二氰胺锌制备阶段:将二氰胺钠溶于50%乙醇水溶液中配成浓度为10%的二氰胺钠溶液,加入50%的氯化锌水溶液,控制二氰胺钠与氯化锌摩尔比为2:1,在50~65℃下进行搅拌反应6~10h后,过滤,乙醇洗涤,干燥得二氰胺锌。
聚丙烯泡棉制备阶段:包括35~60重量份聚丙烯、5~20重量份马来酸酐接枝聚丙烯、10~60重量份低密度聚乙烯、2~20重量份偶氮二甲酰胺发泡剂、0.5~5重量份二氰胺锌、0.5~4重量份抗氧化剂加入螺杆挤出机上进行塑化挤出母片,然后进行对所述母片分别进行电子辐射交联处理、发泡处理和压光处理得到所述泡棉材料。
本申请还提供一种上述辐照交联聚丙烯泡棉材料的用途,该泡棉材料可用作在机械抗震、汽车内饰、保温管、电子设备等领域,所述泡棉材料厚度为0.1~4.5mm,厚度偏差在10%以内;在厚度方向上至少包括2层泡孔。
与现有技术相比,本发明具有以下优点:
(1)产品耐热性好,可达120℃以上;
(2)产品强度高,表观密度小于0.1g/cm3时,厚度1mm时,弹性模量在15MPa以上,邵氏硬度在60D以上;
(3)产品粘结性高,电晕表面张力可达38mN/m以上,满足涂胶工艺要求,可维持6个月以上;
(4)所得材料在机械抗震、汽车内饰、保温管、电子设备等领域具有广泛应用。
本发明采用二氰胺锌为敏化及低温发泡抑制剂,马来酸酐接枝聚丙烯、聚丙烯与线性低密度聚乙烯复配,获得具有高耐热和力学强度的聚丙烯发泡材料,是目前最为合适的方法。
具体实施方式
本发明在聚乙烯泡棉材料配方中引入采用二氰胺锌为敏化及低温发泡抑制剂,马来酸酐接枝聚丙烯、聚丙烯与线性低密度聚乙烯复配,并通过辐照交联和高温发泡形成立体交联网络,制备高耐热和力学强度聚丙烯泡棉材料。
本发明采用二氰胺锌为敏化及低温发泡抑制剂,提升材料挤出加工温度,保证聚丙烯充分熔融塑化,通过马来酸接枝共聚丙烯、低密度聚乙烯与聚丙烯共混,在合适挤出工艺下形成特定凝聚态结构,促进分子链缠结,并在辐照交联过程接入形成交联网络,提高发泡熔体强度,利用配方中极性组分,提高材料电晕持久性。
以下将对本发明的较佳实施例进行详细说明,以便更清楚理解本发明的目的、特点和优点。
基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
其中需要说明的是:
(1)本发明采用GB/T 9341-2008塑料弯曲性能的测定测试弹性模量。
(2)本发明采用GB/T 14216-2008试样的润湿张力测试表面张力。
(3)本发明采用GB/T 3682-2000热塑性塑料熔体质量流动速率和熔体体积流动速率的测定测试熔融指数
(4)本发明采用GB/T1033-1986塑料密度和相对密度试验方法测试材料密度
(5)本发明采用GB/T2411-2008塑料和硬橡胶使用硬度计测定压痕硬度(邵氏硬度)测定材料表面硬度
实施例1
第1步 二氰胺锌合成
将二氰胺钠溶于50%乙醇水溶液中配成浓度为10%的二氰胺钠溶液,加入50%的氯化锌水溶液,控制二氰胺钠与氯化锌摩尔比为2:1,在60℃下进行搅拌反应8h后,过滤,乙醇洗涤,80℃干燥得二氰胺锌;
第2步 马来酸酐接枝聚丙烯制备
将100质量份共聚聚丙烯(PP 5050,台湾塑胶,MI(230℃/2.16kg)5g/10min,MP132℃)、10质量份马来酸酐、1质量份过氧化二异丙苯在140℃密炼机中进行密炼反应2h后,进行造粒挤出,得相应马来酸酐接枝聚丙烯。
第3步 聚丙烯泡棉制备
将50重量份聚丙烯(PP PPC 5660,法国道达尔,0.905g/cm3,MI 7)、15重量份马来酸酐接枝聚丙烯、35重量份低密度聚乙烯(LDPE,2426H,中海壳牌,0.925g/cm3,MI(230℃/2.16kg)1.9g/10min)、10重量份偶氮二甲酰胺发泡剂、2重量份二氰胺锌、1重量份抗氧化剂1010混合均匀后,加入到单螺杆挤出机进行挤出,控制挤出温度在145~155℃、螺杆转速20rpm、模头温度140℃,得到0.2mm厚度的母片;接着,将母片通过电子加速器,进行辐照交联,控制辐照剂量为30kGy,形成交联聚合网络;最后,将交联母片置于发泡炉进行发泡,控制发泡炉温度为180~260℃,交联母片的停留时间为0.3min,得到高强度辐照交联聚乙烯发泡材料,表观密度0.08g/cm3,弹性模量21MPa,邵氏硬度在62D,电晕后表面张力为40mN/m,放置6个月后,表面张力为39mN/m,该聚乙烯泡棉可应用为机械抗震、汽车内饰、保温管、电子设备等领域。
实施例2-6
除以下不同外,其余与实施例1相同,选择不同共聚丙烯。
表1
实施例7-10
除以下不同外,其余与实施例1相同,选择不同低密度聚乙烯。
表2
实施例11-14
除以下不同外,其余与实施例1相同,选择不同聚丙烯。
表3
对比例1
按实施例1,不加二氰胺锌,将50重量份聚丙烯(PP PPC 5660,法国道达尔,0.905g/cm3,MI 7)、15重量份马来酸酐接枝聚丙烯、35重量份低密度聚乙烯(LDPE,2426H,中海壳牌,0.925g/cm3,MI(230℃/2.16kg)1.9g/10min)、10重量份偶氮二甲酰胺发泡剂、1重量份抗氧化剂1010混合均匀后,加入到单螺杆挤出机进行挤出,控制挤出温度在145~155℃、螺杆转速20rpm、模头温度140℃挤出30min后出现了严重发泡剂热分解,无法得到母片。
对比例2
按实施例2,将二氰胺锌换成传统硬脂酸锌,将50重量份聚丙烯(PP PPC 5660,法国道达尔,0.905g/cm3,MI 7)、15重量份马来酸酐接枝聚丙烯、35重量份低密度聚乙烯(LDPE,2426H,中海壳牌,0.925g/cm3,MI(230℃/2.16kg)1.9g/10min)、10重量份偶氮二甲酰胺发泡剂、1重量份抗氧化剂1010混合均匀后,加入到单螺杆挤出机进行挤出,控制挤出温度在145~155℃、螺杆转速20rpm、模头温度140℃挤出5min后出现了严重发泡剂热分解,无法得到母片。
对比例3
按实施例3,将聚丙烯(PP PPC 5660,法国道达尔,0.905g/cm3,MI 7)换成聚丙烯(PP PD702,利安德巴塞尔,0.9g/cm3,MI(230℃/2.16kg)35g/10min),将50重量份聚丙烯(PP PD702,利安德巴塞尔,0.9g/cm3,MI(230℃/2.16kg)35g/10min)、15重量份马来酸酐接枝聚丙烯、35重量份低密度聚乙烯(LDPE,2426H,中海壳牌,0.925g/cm3,MI(230℃/2.16kg)1.9g/10min)、10重量份偶氮二甲酰胺发泡剂、2重量份二氰胺锌、1重量份抗氧化剂1010混合均匀后,加入到单螺杆挤出机进行挤出,控制挤出温度在145~155℃、螺杆转速20rpm、模头温度140℃,得到0.2mm厚度的母片;接着,将母片通过电子加速器,进行辐照交联,控制辐照剂量为30kGy,形成交联聚合网络;最后,将交联母片置于发泡炉进行发泡,控制发泡炉温度为180~260℃,交联母片的停留时间为0.3min,得到高强度辐照交联聚乙烯发泡材料,表观密度0.12g/cm3,弹性模量20MPa,邵氏硬度在58D,电晕后表面张力为39mN/m,放置6个月后,表面张力为37mN/m。采用融指高聚丙烯会导致分子量较低,辐照交联无法较好进行,形成较多降解低分子链,熔体强度较差,易开孔,难形成均匀泡孔结构,形成材料的表观密度偏高,硬度偏低。
本发明的制备方法制得的产品均具有很好的耐热性和力学强度,长效粘结性。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (9)
1.一种高强度交联聚丙烯泡棉材料,其特征在于:包括
35~60重量份聚丙烯
5~20重量份马来酸酐接枝聚丙烯
10~60重量份低密度聚乙烯
2~20重量份偶氮二甲酰胺发泡剂
0.5~5重量份二氰胺锌
0.5~4重量份抗氧化剂
所述低密度聚乙烯包括为密度为0.901~0.922g/cm3,熔融指数MI,230℃/2.16kg为1~6g/10 min的低密度聚乙烯、密度为0.905~0.930g/cm3,熔融指数MI,230℃/2.16kg为0.3~5g/10 min的线性低密度聚乙烯中的的一种或者两种以上的组合物;所述聚丙烯为密度为0.87~0.91g/cm3,熔融指数MI,230℃/2.16kg为0.5~10 g/10 min的等规聚丙烯一种或者两种以上的组合物。
2.根据权利要求1所述的一种高强度交联聚丙烯泡棉材料,其特征在于:所述的马来酸酐接枝聚丙烯主要是聚丙烯与马来酸酐进行接枝共聚而成,将100质量份聚丙烯、5~30质量份马来酸酐、0.5~2质量份硫化剂在130~160℃密炼机中进行密炼反应1~4h后,进行造粒挤出,得相应马来酸酐接枝聚丙烯。
3.根据权利要求2所述的一种高强度交联聚丙烯泡棉材料,其特征在于:所述马来酸酐接枝聚丙烯中的聚丙烯是共聚聚丙烯,包括乙烯丙稀共聚物、丁烯丙烯共聚物等二元共聚物、乙烯丙烯丁烯三元共聚物中的任一种或多种的混合物,共聚聚丙烯的熔融指数MI,230℃/2.16kg为0.5~5g/10min,熔点MP为125~140℃。
4.根据权利要求2所述的一种高强度交联聚丙烯泡棉材料,其特征在于:所述硫化剂为过氧化苯甲酰、过氧化二异丙苯、过氧化苯甲酸、甲乙酮过氧化物、过氧化新癸酸、过氧新戊酸叔丁酯一种或者两种以上的组合物。
5.根据权利要求1所述的一种高强度交联聚丙烯泡棉材料,其特征在于:所述的二氰胺锌主要是二氰胺钠与氯化锌进行离子交换制备而成,将二氰胺钠溶于50%乙醇水溶液中配成浓度为10%的二氰胺钠溶液,加入50%的氯化锌水溶液,控制二氰胺钠与氯化锌摩尔比为2:1,在50~65℃下进行搅拌反应6~10h后,过滤,乙醇洗涤,干燥得二氰胺锌。
6.根据权利要求1所述的一种高强度交联聚丙烯泡棉材料,其特征在于:所述抗氧化剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、β-(3,5二叔丁基-4一羟基苯基)丙酸十八醇酯、1 ,1 ,3-三(2-甲基-4-羟基-5叔丁基苯基)丁烷、1 ,3 ,5-三甲基-2 ,4 ,6-三(3 ,5-二叔丁基-4-羟基苄基)苯、丁基羟基茴香醚、二丁基羟基甲苯、没食子酸丙酯、叔丁基对苯二酚中的任一种或两种以上的组合物。
7.根据权利要求1-6中任意一项的一种高强度交联聚丙烯泡棉材料的制备方法,其特征在于:包括首先,将以下组分混合后,加入到螺杆挤出机中进行混炼挤出得母片;
35~60重量份聚丙烯
5~20重量份马来酸酐接枝聚丙烯
10~60重量份低密度聚乙烯
2~20重量份偶氮二甲酰胺发泡剂
0.5~5重量份二氰胺锌
0.5~4重量份抗氧化剂
然后,将上述步骤得到的母片进行电子辐照交联,电子辐照交联结束后,所得材料进行高温发泡处理,从而得到高耐热高发泡的聚丙烯烯泡棉材料,螺杆挤出机的挤出温度为145~160℃,螺杆转速为10~20rpm,模头温度为140~145℃。
8.根据权利要求7所述的一种高强度交联聚丙烯泡棉材料的制备方法,其特征在于:辐照交联的辐照剂量为4~40kGy。
9.根据权利要求7所述的一种高强度交联聚丙烯泡棉材料的制备方法,其特征在于:所述发泡在发泡炉中进行,发泡炉温度为180~280℃,发泡时间为0.1~3 min。
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JPS62288102A (ja) * | 1986-06-03 | 1987-12-15 | Kyowa Gas Chem Ind Co Ltd | ジシアナミド金属塩の製造方法 |
CA2134187A1 (en) * | 1993-12-10 | 1995-06-11 | Michael W. Barnes | Gas generant compositions using dicyanamide salts as fuel |
CN107768741A (zh) * | 2017-09-18 | 2018-03-06 | 中国科学院青岛生物能源与过程研究所 | 低共熔体电解质及其在二次锌电池中的应用 |
CN110563001A (zh) * | 2019-09-02 | 2019-12-13 | 北京理工大学 | 二氰胺过渡金属盐及其制备方法 |
CN110791024A (zh) * | 2019-12-05 | 2020-02-14 | 万华化学(宁波)有限公司 | 一种用于发泡的改性聚丙烯增强材料及其制备方法和用途 |
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JPS62288102A (ja) * | 1986-06-03 | 1987-12-15 | Kyowa Gas Chem Ind Co Ltd | ジシアナミド金属塩の製造方法 |
CA2134187A1 (en) * | 1993-12-10 | 1995-06-11 | Michael W. Barnes | Gas generant compositions using dicyanamide salts as fuel |
CN107768741A (zh) * | 2017-09-18 | 2018-03-06 | 中国科学院青岛生物能源与过程研究所 | 低共熔体电解质及其在二次锌电池中的应用 |
CN110563001A (zh) * | 2019-09-02 | 2019-12-13 | 北京理工大学 | 二氰胺过渡金属盐及其制备方法 |
CN110791024A (zh) * | 2019-12-05 | 2020-02-14 | 万华化学(宁波)有限公司 | 一种用于发泡的改性聚丙烯增强材料及其制备方法和用途 |
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