CN107501595B - 一种非熔融态发泡聚丙烯塑料的方法 - Google Patents

一种非熔融态发泡聚丙烯塑料的方法 Download PDF

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CN107501595B
CN107501595B CN201710727092.7A CN201710727092A CN107501595B CN 107501595 B CN107501595 B CN 107501595B CN 201710727092 A CN201710727092 A CN 201710727092A CN 107501595 B CN107501595 B CN 107501595B
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polypropylene
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陈庆
昝航
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Anhui Dongyuan New Materials Co.,Ltd.
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Abstract

本发明属于性能卓越的高分子材料‑聚丙烯塑料制备技术领域,提供了一种非熔融态发泡聚丙烯塑料的方法。该方法首先通水相保护液和一定的聚合物制得的膨胀微球发泡剂,然后与聚丙烯和软化剂一起加入开炼机中,出片后趁热放入平板硫化机内的模具中,高温压制并冷却后得到非熔融态发泡的聚丙烯塑料。该方法不仅能避免聚丙烯熔体强度低带来的问题,还免去对聚丙烯高温加热熔融的步骤,降低了生产成本。与传统方法相比,本发明采用的发泡方法,发泡特性稳定,泡孔尺寸可控,可得到闭孔结构的聚丙烯泡沫塑料,同时可重复性高,操作简便,可实现规模化生产。

Description

一种非熔融态发泡聚丙烯塑料的方法
技术领域
本发明属于性能卓越的高分子材料-聚丙烯塑料制备技术领域,提供了一种非熔融态发泡聚丙烯塑料的方法。
背景技术
聚丙烯(PP,是英文Poly Propylene开头字母的缩写)是二十世纪五十年代开始大量生产的一种合成树脂,它是丙烯均聚物或丙烯α—烯烃(乙烯、丁烯-1、己烯-1)的共聚物,其分子呈线性结构,密度为0.89~0.91g/cm3,比低密度聚乙烯的密度还低。由于PP具有相对硬度高、比重小、拉伸强度高、透明性好、抗应力开裂和耐化学性能好、耐热挠曲温度高、并具有极好的注塑性能、能随意拉伸和定向、可以与其它材料共混改性等优点,因此PP应用范围不断扩大,在五大通用树脂中需求增长速度最快,已逐渐取代钢铁、木材、纸、聚碳酸酯、ABS、PS、尼龙、聚酯等其它合成材料。
常规方法生产的PP是一种线型半结晶性聚合物,分子链很少支化,分子量分布相对较窄,这导致它的软化点和熔点很接近。在温度达到熔点之前,它基本不流动,当温度超过熔点后,熔体强度急剧下降,这种熔体很难包住气体;此外,聚丙烯从熔融态转变为结晶态会放出大量的热量,由熔体转变为固体所需时间较长;加之聚丙烯透气率高,发泡气体易逃逸。故适于聚丙烯发泡的温度区间窄,发泡过程很难控制,极易造成发泡过程中泡壁破裂、气体逃逸、泡孔坍塌及气泡合并。
EPP(Expanded Polypropylene)即发泡聚丙烯材料,它是一种性能卓越的高结晶型聚合物/气体复合材料,以其独特而优越的性能成为目前增长最快的环保新型抗压缓冲隔热材料。EPP制品具有十分优异的抗震吸能性能、形变后回复率高、很好的耐热性、耐化学品、耐油性和隔热性;同时,其质量轻,可大幅度减轻物品质量;另外,EPP还是一种环保材料,易于发生β降解,且PP泡沫便于回收利用,其环境友好性优于其他泡沫材料,因而被称为“绿色”泡沫。正是由于其表现出来的优异性能,使得EPP成为继聚苯乙烯(EPS)、聚氨酯(EPU)、聚乙烯(EPE)泡沫材料之后更具应用价值和市场潜力的新型泡沫材料。
PP的熔体强度低,极大地限制了其加工范围和应用领域,如在热成型领域,由于PP熔体强度低,造成吸塑成型时容器壁厚不均匀或破裂;在挤出涂布时,普通PP表现出明显的颈缩和熔体共振,因而出现边缘卷曲、收缩等现象;挤出发泡时,微孔壁易发生破裂,发泡倍率低等。因而要想得到高质量的聚丙烯发泡材料,提高其熔体强度是关键。
热膨胀微球是指聚合物外壳包裹碳氢化合物形成的具有核壳结构的颗粒,有着稳定的发泡特性,可有效用于各类材料的发泡膨胀。由于膨胀后的微球具有质轻、均一的发泡倍率等优点,并在隔热、隔声、减震、减重等方面具有特殊作用,在工业中有着广泛的应用。
针对上述情况,并结合热膨胀微球优越发泡性能,我们提出提出一种非熔融态发泡聚丙烯塑料的方法,其特征在于聚丙烯并非在熔融状态下进行发泡。先用适量的低分子量脂肪烃、芳香烃或氯化烃对聚丙烯进行软化,采用膨胀微球作为发泡剂,均匀地分散到发泡体系中。然后对发泡体系进行适当升温,膨胀微球内的烃类发泡剂气化,微球发生膨胀,得到聚丙烯发泡材料。采用该方法不仅能避免聚丙烯熔体强度低带来的问题,还免去对聚丙烯高温加热熔融的步骤,降低了生产成本。
发明内容
本发明的目的是提供一种非熔融态发泡聚丙烯塑料的方法,能避免聚丙烯熔体强度低带来的问题,还免去对聚丙烯高温加热熔融的步骤,降低了生产成本。与传统方法相比,本发明采用的发泡方法,发泡特性稳定,泡孔尺寸可控,可得到闭孔结构的聚丙烯泡沫塑料,同时可重复性高,操作简便,可实现规模化生产。
本发明涉及的具体技术方案如下:
一种非熔融态发泡聚丙烯塑料的方法,首先通水相保护液和一定的聚合物制得的膨胀微球发泡剂,然后与聚丙烯和软化剂一起加如开炼机中,出片后趁热放入平板硫化机内的模具中,高温压制并冷却后得到非熔融态发泡的聚丙烯塑料。具体步骤如下:
(1)按比例将水、氢氧化钠、六水合氧化镁、十二烷基硫酸钠及氯化钠加入搅拌器中,剧烈搅拌,形成稳定的水相保护液。然后将一定量的聚合物单体、偶氮二异丁氰、乙二醇二甲基丙烯酸酯及正己烷混合,搅拌均匀,形成油相。再将油相加入到水相中,通入氮气,将空气全部置换出来后密封,高速搅拌,形成均匀乳液,降低搅拌速度并使其反应一段时间,然后用盐酸洗涤,过滤并干燥,得到膨胀微球发泡剂;
(2)将聚丙烯、软化剂及步骤(1)所得的膨胀微球发泡剂加入开炼机中,在一定温度下混炼5~10min,出片后趁热放入模具中,并放入平板硫化机内,高温下压制5~10min,迅速开模,发泡体弹出后,置于冷水中定型,即可得非熔融态发泡的聚丙烯塑料。
优选的,步骤(1)所述水相保护液中,氢氧化钠的体积浓度为10~15g/L,六水合氧化镁的体积浓度为5~10g/L,十二烷基硫酸钠的体积浓度为3~5g/L,氯化钠的体积浓度为5~10g/L,;
优选的,步骤(1)所述油相中的聚合物单体为丙烯腈、苯乙烯、甲基丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸或丙烯酸正丁酯;
优选的,步骤(1)所述油相中,偶氮二异丁氰的加入量为单体质量的20~30%,乙二醇二甲基丙烯酸酯的加入量为单体质量的5~10%,正己烷的加入量为单体质量的3~6%;
优选的,步骤(1)所述油相与水相的混合体积比为1:10~1:5;
优选的,步骤(1)所述搅拌速度为1000~1200r/min,形成稳定乳液后将为200~250r/min;
优选的,步骤(1)所述反应温度为60~65℃,反应时间为20~24h;
优选的,步骤(1)所述烘干温度为45~50℃,烘干时间为20~24h;
优选的,步骤(2)所述软化剂为低分子量的脂肪烃、芳香烃或氯化烃,如硬脂酸、石蜡、低分子量聚苯乙烯、低分子量聚乙烯蜡等;
优选的,步骤(2)所述软化剂的加入量为聚丙烯质量的5~10%;
优选的,步骤(2)所述膨胀微球发泡剂的加入量为聚丙烯质量的20~30%;
优选的,步骤(2)所述混炼温度为100~110℃,压制温度为140~150℃。
在热膨胀微球的形成过程中,油滴单体在水相中剧烈搅拌,形成不稳定油滴,然后在表面活性剂及无机分散粒子的保护下,经聚并及分散形成稳定的悬浮液滴,当达到反应温度时,单体在每个液滴内发生原位聚合,经链引发、链增长、链转移及链终止等形成聚合物。由于聚合物与发泡剂不相容,聚合物的亲水性更好,于是在反应过程中,聚合物包裹发泡剂形成核壳结构。反应过程中,分散剂的量及搅拌速度不能太低,否则易形成大颗粒或块状物。膨胀微球与聚丙烯混合后,随着温度的升高,外壳软化,内部蒸气压增大,微球体积变大,聚合物外壳的厚度变小,直至破裂,其内部的发泡剂全部逸出,实现对聚丙烯的发泡。对聚丙烯进行软化后,应达到其软化点低于熔点至少20℃,才能实现发泡温度区间的有效控制。若发泡效果较差,可能的原因有以下几个:一是微球粒径太小,聚合物外壳较厚,需要更高的温度才能使微球膨胀;二是发泡剂太少;三是微球外壳热塑性大,外壳具有延展性,使其难以破裂释放发泡剂。为避免上述问题,应合理选择聚合单体、引发剂、交联剂、发泡剂及其配比。
本发明提供了一种非熔融态发泡聚丙烯塑料的方法,与现有技术相比,其突出的特点和优异的效果在于:
1.本发明的制备方法避免了聚丙烯熔体强度低带来的问题,如发泡过程中的泡壁破裂、气体逃逸、泡孔坍塌或气泡合并;
2.本发明的制备方法避免了对聚丙烯高温加热熔融的步骤,降低了能耗,节约了生产成本;
3.本发明采用的发泡方法,发泡特性稳定,泡孔尺寸可控,可得到闭孔结构的聚丙烯泡沫塑料;
4.本发明采用的方法,可重复性高,操作简便,可实现工业化生产。
具体实施方式
以下通过具体实施方式对本发明作进一步的详细说明,但不应将此理解为本发明的范围仅限于以下的实例。在不脱离本发明上述方法思想的情况下,根据本领域普通技术知识和惯用手段做出的各种替换或变更,均应包含在本发明的范围内。
实施例1
一种非熔融态发泡聚丙烯塑料的方法,其膨胀微球的制备及聚丙烯非熔融发泡的具体过程如下:
将100L水、12g氢氧化钠、5g六水合氧化镁、5g十二烷基硫酸钠及10g氯化钠加入搅拌器中,以1000r/min的速度剧烈搅拌,形成稳定的水相保护液。然后将10kg丙烯腈、20g偶氮二异丁氰、7g乙二醇二甲基丙烯酸酯及4g正己烷混合,搅拌均匀,形成油相。再将油相加入到水相中,油相与水相的混合体积比为1:10,再通入氮气,将空气全部置换出来后密封,以1200r/min的速度高速搅拌,形成均匀乳液,降低搅拌速度至200r/min,并使其在60℃下,反应20h,然后用盐酸洗涤,过滤,并在45℃下干燥24h,得到膨胀微球发泡剂;再将10kg聚丙烯、0.5kg硬脂酸及2.5kg膨胀微球发泡剂加入开炼机中,在110℃的温度下混炼5min,出片后趁热放入模具中,并放入平板硫化机内,140℃的高温下压制10min,迅速开模,发泡体弹出后,置于冷水中定型,即可得非熔融态发泡的聚丙烯塑料。
对实施例1得到的发泡聚丙烯塑料,测定其发泡倍数、泡孔尺寸范围,得到的数据如表1所示。
实施例2
一种非熔融态发泡聚丙烯塑料的方法,其膨胀微球的制备及聚丙烯非熔融发泡的具体过程如下:
将100L水、10g氢氧化钠、8g六水合氧化镁、3g十二烷基硫酸钠及7g氯化钠加入搅拌器中,以1200r/min的速度剧烈搅拌,形成稳定的水相保护液。然后将10kg苯乙烯、25g偶氮二异丁氰、8g乙二醇二甲基丙烯酸酯及3g正己烷混合,搅拌均匀,形成油相。再将油相加入到水相中,油相与水相的混合体积比为1:8,再通入氮气,将空气全部置换出来后密封,以1100r/min的速度高速搅拌,形成均匀乳液,降低搅拌速度至230r/min,并使其在60℃下,反应24h,然后用盐酸洗涤,过滤,并在50℃下干燥20h,得到膨胀微球发泡剂;再将10kg聚丙烯、1kg低分子量聚乙烯蜡及3kg膨胀微球发泡剂加入开炼机中,在100℃的温度下混炼8min,出片后趁热放入模具中,并放入平板硫化机内,150℃的高温下压制8min,迅速开模,发泡体弹出后,置于冷水中定型,即可得非熔融态发泡的聚丙烯塑料。
对实施例2得到的发泡聚丙烯塑料,测定其发泡倍数、泡孔尺寸范围,得到的数据如表1所示。
实施例3
一种非熔融态发泡聚丙烯塑料的方法,其膨胀微球的制备及聚丙烯非熔融发泡的具体过程如下:
将100L水、15g氢氧化钠、5g六水合氧化镁、4g十二烷基硫酸钠及10g氯化钠加入搅拌器中,以1000r/min的速度剧烈搅拌,形成稳定的水相保护液。然后将10kg甲基丙烯酸乙酯、30g偶氮二异丁氰、5g乙二醇二甲基丙烯酸酯及5g正己烷混合,搅拌均匀,形成油相。再将油相加入到水相中,油相与水相的混合体积比为1:6,再通入氮气,将空气全部置换出来后密封,以1100r/min的速度高速搅拌,形成均匀乳液,降低搅拌速度至210r/min,并使其在65℃下,反应20h,然后用盐酸洗涤,过滤,并在50℃下干燥20h,得到膨胀微球发泡剂;再将10kg聚丙烯、0.8kg低分子量聚乙烯蜡及2kg膨胀微球发泡剂加入开炼机中,在110℃的温度下混炼7min,出片后趁热放入模具中,并放入平板硫化机内,140℃的高温下压制10min,迅速开模,发泡体弹出后,置于冷水中定型,即可得非熔融态发泡的聚丙烯塑料。
对实施例3得到的发泡聚丙烯塑料,测定其发泡倍数、泡孔尺寸范围,得到的数据如表1所示。
实施例4
一种非熔融态发泡聚丙烯塑料的方法,其膨胀微球的制备及聚丙烯非熔融发泡的具体过程如下:
将100L水、10g氢氧化钠、7g六水合氧化镁、4g十二烷基硫酸钠及8g氯化钠加入搅拌器中,以1000r/min的速度剧烈搅拌,形成稳定的水相保护液。然后将10kg甲基丙烯酸甲酯、25g偶氮二异丁氰、6g乙二醇二甲基丙烯酸酯及4g正己烷混合,搅拌均匀,形成油相。再将油相加入到水相中,油相与水相的混合体积比为1:5,再通入氮气,将空气全部置换出来后密封,以1200r/min的速度高速搅拌,形成均匀乳液,降低搅拌速度至220r/min,并使其在65℃下,反应20h,然后用盐酸洗涤,过滤,并在45℃下干燥24h,得到膨胀微球发泡剂;再将10kg聚丙烯、0.6kg低分子量聚苯乙烯及2.5kg膨胀微球发泡剂加入开炼机中,在110℃的温度下混炼5min,出片后趁热放入模具中,并放入平板硫化机内,140℃的高温下压制10min,迅速开模,发泡体弹出后,置于冷水中定型,即可得非熔融态发泡的聚丙烯塑料。
对实施例4得到的发泡聚丙烯塑料,测定其发泡倍数、泡孔尺寸范围,得到的数据如表1所示。
实施例5
一种非熔融态发泡聚丙烯塑料的方法,其膨胀微球的制备及聚丙烯非熔融发泡的具体过程如下:
将100L水、13g氢氧化钠、6g六水合氧化镁、5g十二烷基硫酸钠及7g氯化钠加入搅拌器中,以1200r/min的速度剧烈搅拌,形成稳定的水相保护液。然后将10kg甲基丙烯酸、20g偶氮二异丁氰、8g乙二醇二甲基丙烯酸酯及6g正己烷混合,搅拌均匀,形成油相。再将油相加入到水相中,油相与水相的混合体积比为1:10,再通入氮气,将空气全部置换出来后密封,以1000r/min的速度高速搅拌,形成均匀乳液,降低搅拌速度至220r/min,并使其在62℃下,反应22h,然后用盐酸洗涤,过滤,并在48℃下干燥23h,得到膨胀微球发泡剂;再将10kg聚丙烯、1kg低分子量聚苯乙烯及2kg膨胀微球发泡剂加入开炼机中,在100℃的温度下混炼10min,出片后趁热放入模具中,并放入平板硫化机内,150℃的高温下压制5min,迅速开模,发泡体弹出后,置于冷水中定型,即可得非熔融态发泡的聚丙烯塑料。
对实施例5得到的发泡聚丙烯塑料,测定其发泡倍数、泡孔尺寸范围,得到的数据如表1所示。
实施例6
一种非熔融态发泡聚丙烯塑料的方法,其膨胀微球的制备及聚丙烯非熔融发泡的具体过程如下:
将100L水、14g氢氧化钠、8g六水合氧化镁、3g十二烷基硫酸钠及6g氯化钠加入搅拌器中,以1000r/min的速度剧烈搅拌,形成稳定的水相保护液。然后将10kg甲基丙烯酸、30g偶氮二异丁氰、5g乙二醇二甲基丙烯酸酯及5g正己烷混合,搅拌均匀,形成油相。再将油相加入到水相中,油相与水相的混合体积比为1:5,再通入氮气,将空气全部置换出来后密封,以1100r/min的速度高速搅拌,形成均匀乳液,降低搅拌速度至240r/min,并使其在60℃下,反应24h,然后用盐酸洗涤,过滤,并在45℃下干燥24h,得到膨胀微球发泡剂;再将10kg聚丙烯、0.8kg硬脂酸及3kg膨胀微球发泡剂加入开炼机中,在100℃的温度下混炼10min,出片后趁热放入模具中,并放入平板硫化机内,140℃的高温下压制10min,迅速开模,发泡体弹出后,置于冷水中定型,即可得非熔融态发泡的聚丙烯塑料。
对实施例6得到的发泡聚丙烯塑料,测定其发泡倍数、泡孔尺寸范围,得到的数据如表1所示。
实施例7
一种非熔融态发泡聚丙烯塑料的方法,其膨胀微球的制备及聚丙烯非熔融发泡的具体过程如下:
将100L水、15g氢氧化钠、5g六水合氧化镁、3g十二烷基硫酸钠及10g氯化钠加入搅拌器中,以1200r/min的速度剧烈搅拌,形成稳定的水相保护液。然后将10kg丙烯酸正丁酯、30g偶氮二异丁氰、10g乙二醇二甲基丙烯酸酯及4g正己烷混合,搅拌均匀,形成油相。再将油相加入到水相中,油相与水相的混合体积比为1:8,再通入氮气,将空气全部置换出来后密封,以1200r/min的速度高速搅拌,形成均匀乳液,降低搅拌速度至250r/min,并使其在65℃下,反应20h,然后用盐酸洗涤,过滤,并在50℃下干燥20h,得到膨胀微球发泡剂;再将10kg聚丙烯、0.6kg硬脂酸及2.8kg膨胀微球发泡剂加入开炼机中,在110℃的温度下混炼7min,出片后趁热放入模具中,并放入平板硫化机内,150℃的高温下压制7min,迅速开模,发泡体弹出后,置于冷水中定型,即可得非熔融态发泡的聚丙烯塑料。
对实施例7得到的发泡聚丙烯塑料,测定其发泡倍数、泡孔尺寸范围,得到的数据如表1所示。
表1:
具体实施例 发泡倍数(倍) 泡孔尺寸范围(mm)
实施例1 33.5 0.80~1.12
实施例2 32.6 0.65~0.98
实施例3 35.7 0.74~0.89
实施例4 32.4 0.83~0.95
实施例5 35.7 0.82~0.96
实施例6 34.8 0.88~1.04
实施例7 32.9 0.91~1.14

Claims (4)

1.一种非熔融态发泡聚丙烯塑料的方法,其特征在于聚丙烯并非在熔融状态下进行发泡;先用适量的低分子量脂肪烃、芳香烃或氯化烃对聚丙烯进行软化,采用膨胀微球作为发泡剂,均匀地分散到发泡体系中;然后对发泡体系进行适当升温,膨胀微球内的烃类发泡剂气化,微球发生膨胀,得到聚丙烯发泡材料;制备的具体步骤如下:
(1)按比例将水、氢氧化钠、六水合氧化镁、十二烷基硫酸钠及氯化钠加入搅拌器中,剧烈搅拌,形成稳定的水相保护液;然后将一定量的聚合物单体、偶氮二异丁氰、乙二醇二甲基丙烯酸酯及正己烷混合,搅拌均匀,形成油相;再将油相加入到水相中,通入氮气,将空气全部置换出来后密封,高速搅拌,形成均匀乳液,降低搅拌速度并使其反应一段时间,然后用盐酸洗涤,过滤并干燥,得到膨胀微球发泡剂;所述水相保护液中,氢氧化钠的体积浓度为10~15g/L,六水合氧化镁的体积浓度为5~10g/L,十二烷基硫酸钠的体积浓度为3~5g/L,氯化钠的体积浓度为5~10g/L;所述油相中,偶氮二异丁氰的加入量为单体质量的20~30%,乙二醇二甲基丙烯酸酯的加入量为单体质量的5~10%,正己烷的加入量为单体质量的3~6%;所述油相中的聚合物单体为丙烯腈、苯乙烯、甲基丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸或丙烯酸正丁酯;
(2)将聚丙烯、软化剂及步骤(1)所得的膨胀微球发泡剂加入开炼机中,在一定温度下混炼5~10min,出片后趁热放入模具中,并放入平板硫化机内,高温下压制5~10min,迅速开模,发泡体弹出后,置于冷水中定型,即可得非熔融态发泡的聚丙烯塑料;所述软化剂为硬脂酸、石蜡、低分子量聚苯乙烯、低分子量聚乙烯蜡中的一种;所述软化剂的加入量为聚丙烯质量的5~10%。
2.根据权利要求1所述一种非熔融态发泡聚丙烯塑料的方法,其特征在于:步骤(1)所述油相与水相的混合体积比为1:10~1:5。
3.根据权利要求1所述一种非熔融态发泡聚丙烯塑料的方法,其特征在于:步骤(1)所述搅拌速度为1000~1200r/min,形成稳定乳液后为200~250r/min;所述反应温度为60~65℃,反应时间为20~24h;所述干燥温度为45~50℃,干燥时间为20~24h。
4.根据权利要求1所述一种非熔融态发泡聚丙烯塑料的方法,其特征在于:步骤(2)所述膨胀微球发泡剂的加入量为聚丙烯质量的20~30%;所述混炼温度为100~110℃,压制温度为140~150℃。
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