CN108659402A - 一种低密度软质聚氯乙烯发泡塑料及制备方法 - Google Patents

一种低密度软质聚氯乙烯发泡塑料及制备方法 Download PDF

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CN108659402A
CN108659402A CN201810562140.6A CN201810562140A CN108659402A CN 108659402 A CN108659402 A CN 108659402A CN 201810562140 A CN201810562140 A CN 201810562140A CN 108659402 A CN108659402 A CN 108659402A
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杜诗
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Cofco Technology (yichang) Co Ltd
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Abstract

本发明公开了一种低密度软质聚氯乙烯发泡塑料及其制备方法，属于发泡材料技术领域。该发泡材料由以下重量份的原料制成：聚氯乙烯100份、丁腈橡胶5‑25份、邻苯二甲酸二辛酯40‑75份、偶氮二甲酰胺1‑5份、过氧化二异丙苯0.05‑0.4份、ACR‑401 8‑15份、稳定剂2‑6份、柠檬酸0.1‑0.5份、碱金属碳酸氢盐0.1‑0.6份、柠檬酸盐2‑5份、N,N'‑二亚硝基五亚甲基四胺0.05‑0.3份、二氧化钛0.1‑0.4份、重质碳酸钙0.1‑0.4份和纳米级碳酸钙0.5‑1.5份。该发泡塑料的密度在0.27‑0.29g/cm3，发泡孔径在55‑70μm且成孔均匀完整，力学性能优异符合GB/T3807‑94。

Description

一种低密度软质聚氯乙烯发泡塑料及制备方法
技术领域
本发明涉及发泡材料技术领域，具体涉及一种低密度软质聚氯乙烯发泡塑料及制备方法，尤其涉及一种密度在0.27-0.29g/cm3、孔径为55-70μm和力学性能优异的聚氯乙烯发泡塑料。
背景技术
PVC发泡板又称为雪弗板和安迪板，其化学成分是聚氯乙烯（Polyvinylchloride），所以也称为泡沫聚氯乙烯板。广泛应用于客车、火车车厢顶棚、箱体芯层、内部装潢用板、建筑物外墙板、内装饰用板、办公室、住宅、公共场所建筑物隔间，商用装饰架、无尘室用板、吊顶板、网板印刷、电脑刻字、广告标示、展板、标志用板 相册板 等行业及化工防腐工程、热成型件、冷库用板、特殊保冷工程、环保用板模、运动器材、养殖用材、海滨防潮设施、耐水材料、美工材料及各种轻便隔板代替玻璃天棚等。
发泡材料性能指标 GB/T 3807-94，密度0.2-0.4g/cm3，硬度22-40N，拉伸强度≥2.06MPa，撕裂强度≥15N/mm，断裂伸长率≥130%。常规的聚氯乙烯发泡塑料可由聚氯乙烯、丁腈橡胶、偶氮二甲酰胺、过氧化二异丙苯和ACR-401 制成，密度为0.35-0.38g/cm3，可满足一般使用要求。但是在有些场景（如鞋底），要求密度在0.3g/cm3以下，常规的发泡塑料很难达到这个指标，即使达到该指标，也会以降低产品的力学性能和增大成孔孔径来换取。
发明内容
本发明的目的之一在于提供一种低密度软质聚氯乙烯发泡塑料，该发泡塑料的密度在0.27-0.29g/cm3，发泡孔径在55-70μm且成孔均匀完整，力学性能优异。本发明的目的之二在于提供了前述发泡塑料的制备方法，具有更低的塑炼温度。其技术方案如下：
一方面，本发明提供了一种低密度软质聚氯乙烯发泡塑料，该发泡塑料由以下重量份的原料制成：聚氯乙烯（PVC）100份、丁腈橡胶（NBR）5-25份、邻苯二甲酸二辛酯（DOP）40-75份、偶氮二甲酰胺（AC）1-5份、过氧化二异丙苯（DCP）0.05-0.4份、ACR-401 8-15份、稳定剂2-6份、柠檬酸0.1-0.5份、碱金属碳酸氢盐0.1-0.6份、柠檬酸盐2-5份、N,N'-二亚硝基五亚甲基四胺0.05-0.3份、二氧化钛0.1-0.4份、重质碳酸钙（G-CaCO3）0.1-0.4份和纳米级碳酸钙（N-CaCO3）0.5-1.5份；其中，稳定剂选自硬脂酸钡或硬脂酸铅等，优选为硬脂酸铅，可有效减低N,N'-二亚硝基五亚甲基四胺的分解速度。
其中，偶氮二甲酰胺为发泡偶联剂。
其中，邻苯二甲酸二辛酯为增塑剂，它的添加随用量密度先减小后增大，撕裂伸长率硬度和撕裂强度变化复杂。
其中，过氧化二异丙苯为交联剂。
其中，丁腈橡胶为改性剂，能改善塑料的断裂伸长率，使发泡均匀；它的添加随用量密度先减小后增大。
其中，ACR-401作为泡孔调节剂，能提高强度和延伸率，改善泡孔结构；它的添加随用量发泡倍率先增大后减小，密度是先减小后增大。
其中，稳定剂可以活化引发AC的分解，使它的分解温度与PVC压制发泡温度一致，同时降低N,N'-二亚硝基五亚甲基四胺的分解温度。
其中，柠檬酸随着用量的增加，密度逐渐增大，拉伸强度是先减小后增大，撕裂强度先增大后减小，密度先较小后增大，力学性能优异，尤其是强度比未加时好很多。
其中，本发明中的二氧化钛、重质碳酸钙和纳米级碳酸钙成核剂，有效降低产品的密度，改善材料泡孔结构。其中，纳米级碳酸钙的减重效果显著，则以其为主；增加少量其他成核剂以稍微降低密度而显著改善力学性能。另外，通过三种成核剂提供大范围的颗粒粒径以保证成孔大小和均匀。
具体地，二氧化钛不但能防止PVC光降解，还能使PVC发泡，可稍微提升塑料的拉伸强度。
具体地，重质碳酸钙能提升塑料的硬度和拉伸强度，塑料密度先降低后增大。
具体地，纳米级碳酸钙可降低塑料的密度，增大拉伸强度和撕裂强度，但是会降低塑料的硬度。
其中，碱金属碳酸氢盐与发泡助剂柠檬酸、柠檬酸盐、柠檬酸、N,N'-二亚硝基五亚甲基四胺作为AC的改性成分。
具体地，碱金属碳酸氢盐作为无机吸热发泡剂可部分抵消AC分解时放出的热量，AC具有强放热，突发性强，分解速度快的特点，难控制；碱金属碳酸氢盐对其改性，它的添加使塑料的密度先降低后增加，但塑料的整体力学性能有所降低。
具体地，柠檬酸可加快碱金属碳酸氢盐的分解速度，使其接近AC的分解速度，同时能与AC分解的碱性物质反应。
具体地，柠檬酸盐可降低AC的分解速度，使AC与碱金属碳酸氢盐的分解速度基本一致，从而使发泡体系受热时分解平缓，放热适中；它的添加可增大塑料的密度，提高断裂伸长率。柠檬酸盐使发泡体系里的N,N'-二亚硝基五亚甲基四胺的分解反应提前，AC分解反应滞后，使AC与N,N'-二亚硝基五亚甲基四胺分解速度较为一致，并能使AC分解放热峰变宽。
具体地，N,N'-二亚硝基五亚甲基四胺作为有机放热发泡剂，可降低AC受热时的分解速度，可作为AC的辅助发泡剂，具有发泡效率高和使塑料不变色等优点；更具体地，它能使AC受热时只出现峰形较大的放热峰，并能降低整个发泡体系的分解速度和减小热量释放；它的添加使塑料的密度进一步降低，泡孔均匀细密，并能改善材料的力学性能（尤其能提升撕裂强度和撕裂伸长率）。它的添加使撕裂强度先增大后减小，硬度减小，密度先减小后增大。
但是，需加入硬脂酸盐来降低其分解温度至体系的成型温度。
其中，纳米级碳酸钙的粒度为50-100nm。
其中，二氧化钛的粒度为0.1-0.5μm。
其中，重质碳酸钙的粒度为0.5-5.0μm。
其中，碱金属碳酸氢盐为碳酸氢钠。
其中，柠檬酸盐为柠檬酸钠。
优选地，本发明提供的低密度软质聚氯乙烯发泡塑料由以下重量份的原料制成：聚氯乙烯100份、丁腈橡胶15份、邻苯二甲酸二辛酯55份、偶氮二甲酰胺4份、过氧化二异丙苯0.2份、ACR-401 10份、稳定剂5份、柠檬酸0.3份、碳酸氢钠0.4份、柠檬酸钠4份、 N,N'-二亚硝基五亚甲基四胺0.1份、二氧化钛0.1份、重质碳酸钙0.2份和纳米级碳酸钙0.8份。
另一方面，本发明提供了一种低密度软质聚氯乙烯发泡塑料的制备方法，包括预塑化、塑炼、出片（85-100g）、模压发泡成型和冷压等工序，整个工序与常规的发泡塑料的生产工序基本相同，不同之处在于：预塑化工序为：按配比将聚氯乙烯、邻苯二甲酸二辛酯、ACR-401、二氧化钛、重质碳酸钙、纳米级碳酸钙和60-85wt%的稳定剂混合，于90-105℃（常规为100-110℃）条件下进行预塑化，预塑化时间为20-35分钟；塑炼工序为：将预塑化后的混合料融化后加入丁腈橡胶， 再加入过氧化二异丙苯、偶氮二甲酰胺、柠檬酸、碱金属碳酸氢盐、柠檬酸盐、N,N'-二亚硝基五亚甲基四胺和剩余的稳定剂（15-30%），于110-120℃条件下进行塑炼，塑炼时间为5-10分钟（优选为8分钟）。
优选地，预塑化工序为：每隔3-6min（优选为5min）搅拌一次，总共搅拌4-5次，使邻苯二甲酸二辛酯完全被聚氯乙烯吸收。
进一步地，模压发泡成型工序为：发泡温度为160-185℃（优选为170℃），发泡压力为8-12MPa（优选为10MPa），发泡时间为6-15分钟（优选为9分钟）。
本发明具有以下优点：该发泡塑料的密度在0.27-0.29g/cm3，发泡孔径在55-70μm且成孔均匀完整，力学性能优异符合GB/T 3807-94。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面对本发明实施方式作进一步地详细描述。
实施例1
实施例1提供了一种低密度软质聚氯乙烯发泡塑料的制备方法，包括以下步骤：
(1)预塑化工序为：按配比将聚氯乙烯100g、邻苯二甲酸二辛酯55g、ACR-401 10g、二氧化钛0.1g、重质碳酸钙0.2g、纳米级碳酸钙0.8g和稳定剂4g混合，于90-105℃条件下进行预塑化，每隔5min搅拌一次，总共搅拌5次，使邻苯二甲酸二辛酯完全被聚氯乙烯吸收。
(2)塑炼工序为：将预塑化后的混合料融化后加入丁腈橡胶15g， 再加入过氧化二异丙苯0.2g、偶氮二甲酰胺4g、柠檬酸0.3g、碳酸氢钠0.4g、柠檬酸钠4g、N,N'-二亚硝基五亚甲基四胺0.1g和稳定剂1g，于110-120℃条件下进行塑炼，塑炼时间为8分钟。
(3)出片：称重，85-100g/片。
(4)模压发泡成型工序为：发泡温度为170℃，发泡压力为10MPa，发泡时间为9分钟。
(5)冷压：冷压6min，放置24h后进行测试。
对上述试品进行测试，密度GB/T6343-1995，拉伸强度和撕裂伸长率GB/T6344-1996，撕裂强度 GB/T10808-89，硬度 GB1087-89。其结果如表1所示：
表1
项目 密度g/cm3 拉伸强度MPa 撕裂强度N/mm 断裂强度% 硬度N
指标 0.27 3.45 18.58 187.4 38.2
从表1可以看出，其结果远超GB/T 3807-94。
实施例2-5
其制备方法与实施例1一样，不同之处在于：各原料的配比不同，其配比如表2所示：
表2
实施例2 实施例3 实施例4 实施例5
聚氯乙烯（g） 100 100 100 10
丁腈橡胶（g） 20 5 25 18
邻苯二甲酸二辛酯（g） 60 75 55 40
偶氮二甲酰胺（g） 2.5 1 4 5
过氧化二异丙苯（g） 0.1 0.06 0.35 0.4
ACR-401（g） 10 12 15 8
硬脂酸钡（g） 1 6 4
硬脂酸铅（g） 5 2
柠檬酸（g） 0.1 0.5 0.2 0.2
碳酸氢钠（g） 0.2 0.1 0.5 0.55
柠檬酸钠（g） 2.5 2 4 5
N,N'-二亚硝基五亚甲基四胺（g） 0.1 0.3 0.2 0.2
二氧化钛（g） 0.3 0.1 0.15 0.2
重质碳酸钙（g） 0.1 0.1 0.4 0.2
纳米级碳酸钙（g） 1 1.5 0.5 1.2
对比例1
其制备方法与实施例1基本一致，不同之处在于：由以下原料制成：聚氯乙烯100g、丁腈橡胶15g、邻苯二甲酸二辛酯55g、偶氮二甲酰胺4g、过氧化二异丙苯0.2g、ACR-401 g份、稳定剂5g和柠檬酸0.3g。
对比例2
其制备方法与实施例1基本一致，不同之处在于：由以下原料制成：聚氯乙烯100g、丁腈橡胶15g、邻苯二甲酸二辛酯55g、偶氮二甲酰胺4g、过氧化二异丙苯0.2g、ACR-401 g份、稳定剂5g、柠檬酸0.3g、二氧化钛0.1g、重质碳酸钙0.2g和纳米级碳酸钙0.8g。
对比例3
其制备方法与实施例1基本一致，不同之处在于：由以下原料制成：聚氯乙烯100g、丁腈橡胶15g、邻苯二甲酸二辛酯55g、偶氮二甲酰胺4g、过氧化二异丙苯0.2g、ACR-401 g份、稳定剂5g、柠檬酸0.3g、碳酸氢钠0.4g、柠檬酸钠4g和 N,N'-二亚硝基五亚甲基四胺0.1g。
其结果如表3所示：
表3
项目 密度g/cm3 拉伸强度MPa 撕裂强度N/mm 断裂强度% 硬度N 发泡孔径μm
实施例1 0.27 3.45 18.6 187.4 38.2 65.5
实施例2 0.28 3.49 17.5 184.3 36.9 65.4
对比例1 0.36 3.02 16.4 201.5 32.3 90.5
对比例2 0.31 3.53 17.9 184.1 40.1 62.3
对比例3 0.33 3.37 17.2 157.5 36.3 75.9
从表3可以看出，本专利中各组分的作用复杂，各组分相互作用，本专利在以降低密度的前提下尽可能提升产品的力学性能并减小发泡孔径的大小，即本专利是多种组分相互作用的结果，单独增加或去除该组分或调整该组分的比例都很难得到理想的结果。
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 (10)

1.一种低密度软质聚氯乙烯发泡塑料，其特征在于，其由以下重量份的原料制成：
聚氯乙烯100份、丁腈橡胶5-25份、邻苯二甲酸二辛酯40-75份、偶氮二甲酰胺1-5份、过氧化二异丙苯0.05-0.4份、ACR-401 8-15份、稳定剂2-6份、柠檬酸0.1-0.5份、碱金属碳酸氢盐0.1-0.6份、柠檬酸盐2-5份、N,N'-二亚硝基五亚甲基四胺0.05-0.3份、二氧化钛0.1-0.4份、重质碳酸钙0.1-0.4份和纳米级碳酸钙0.5-1.5份；所述稳定剂选自硬脂酸钡或硬脂酸铅。
2.根据权利要求1所述的低密度软质聚氯乙烯发泡塑料，其特征在于，所述纳米级碳酸钙的粒度为50-100nm。
3.根据权利要求1所述的低密度软质聚氯乙烯发泡塑料，其特征在于，所述二氧化钛的粒度为0.1-0.5μm。
4.根据权利要求1所述的低密度软质聚氯乙烯发泡塑料，其特征在于，所述重质碳酸钙的粒度为0.5-5.0μm。
5.根据权利要求1所述的低密度软质聚氯乙烯发泡塑料，其特征在于，所述碱金属碳酸氢盐为碳酸氢钠。
6.根据权利要求1所述的低密度软质聚氯乙烯发泡塑料，其特征在于，所述柠檬酸盐为柠檬酸钠。
7.根据权利要求1所述的低密度软质聚氯乙烯发泡塑料，其特征在于，其由以下重量份的原料制成：
聚氯乙烯100份、丁腈橡胶15份、邻苯二甲酸二辛酯55份、偶氮二甲酰胺4份、过氧化二异丙苯0.2份、ACR-401 10份、稳定剂5份、柠檬酸0.3份、碳酸氢钠0.4份、柠檬酸钠4份、 N,N'-二亚硝基五亚甲基四胺0.1份、二氧化钛0.1份、重质碳酸钙0.2份和纳米级碳酸钙0.8份。
8.一种低密度软质聚氯乙烯发泡塑料的制备方法，包括预塑化、塑炼、出片、模压发泡成型和冷压；其特征在于，
所述预塑化工序为：按配比将聚氯乙烯、邻苯二甲酸二辛酯、ACR-401、二氧化钛、重质碳酸钙、纳米级碳酸钙和60-85wt%的稳定剂混合，于90-105℃条件下进行预塑化，预塑化时间为20-35分钟；
所述塑炼工序为：将预塑化后的混合料融化后加入丁腈橡胶， 再加入过氧化二异丙苯、偶氮二甲酰胺、柠檬酸、碱金属碳酸氢盐、柠檬酸盐、N,N'-二亚硝基五亚甲基四胺和剩余的稳定剂，于110-120℃条件下进行塑炼，塑炼时间为5-10分钟。
9.根据权利要求8所述的低密度软质聚氯乙烯发泡塑料的制备方法，其特征在于，所述预塑化工序为：每隔3-6min搅拌一次，总共搅拌4-5次，使邻苯二甲酸二辛酯完全被聚氯乙烯吸收。
10.根据权利要求8所述的低密度软质聚氯乙烯发泡塑料的制备方法，其特征在于，所述模压发泡成型工序为：发泡温度为160-185℃，发泡压力为8-12MPa，发泡时间为6-15分钟。
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