CN111269486A - 一种以废弃塑料为原料的再生薄膜及其制备方法 - Google Patents
一种以废弃塑料为原料的再生薄膜及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种以废弃塑料为原料的再生薄膜及其制备方法,它由质量百分比30‑53%的废弃塑料、40‑58.4%的聚乙烯、5‑10%的POE‑g‑(GMA‑co‑st)、0.1‑0.5%的交联剂、0.3‑1%的增塑剂、0.1‑0.5%的抗氧剂、0.5‑1%的开口剂所制成。本发明制备方法以废旧垃圾场塑料制品,通过清洗、烘干、破碎等工艺为基础,并与本发明中的组合物共混挤出改性而得,前期生产设备投入和后期生产成本都相对较低,并实现废旧垃圾场塑料可循环性,且产品力学性能好,断裂伸长率≥150%,熔指(MFR,230℃,2.16kg)<3g/10min。
Description
技术领域
本发明涉及再生塑料薄膜领域,具体是一种以废弃塑料为原料的再生薄膜及其制备方法。
背景技术
当今世界最主要的能源便是石油,但随着世界原油用量的增加,原油储量正逐年减少。以石油为基础的相关产业和产品的发展受到将极大限制的同时,不可降解石油基塑料的广泛使用也严重的破坏着我们赖以生存的自然环境。由工业发展而引发的气候问题是当前全球面临的另一大棘手问题。节能减碳、循环再利用和发展低碳经济成为保护全球气候及促进各国经济发展的根本途径。因此,在全球石油资源供给日趋紧张,环保问题日益突出,对低碳经济发展需求日益强烈的严峻形势下,资源回收再利用必然成为一大趋势。
目前,我国的非正规填埋场(2.7万个)和卫生填埋场(1600个)存储了约80亿吨存余垃圾,占地约3亿m2,内含约35亿吨陈腐有机物、15亿吨塑料、10亿吨织物、5亿吨无机惰性物,潜在资源巨大,但污染严重。填埋场中的塑料含量巨大,主要来源是产品包装、购物袋、快餐盒、农田地膜等,主要材质为聚乙烯(PE)、聚丙烯(PP)、聚对苯二甲酸类(PET)、聚苯乙烯(PS)、聚碳酸酯(PC)等。这些材料多难以完全降解,但是塑料的部分降解会形成微塑料,进入土壤甚至水体中,容易进入生物体内,或成为病原菌传播的载体。但是目前对废弃塑料的回收利用基本停留在垃圾塑料进入填埋场以前(废弃塑料常用的处理方式就是填埋或者焚烧,而塑料焚烧又会产生各种有毒气体以及颗粒物),对于存余垃圾中的废弃塑料,缺少对其改性再利用的研究和开发。
因此,面对体量庞大的存余垃圾中的废弃塑料,不应该简单地进行填埋或者焚烧,而应该通过有效的途径和方法通过清洗、回收、改性并再利用。通过本方法对回料进行分离、清洗和提纯,并改性造粒制备出相容性好、力学性能优良的薄膜,可以应用制备垃圾袋、地膜等产品,实现对废弃垃圾场塑料的循环利用,并节能减碳,符合当今世纪环保理念的发展方向。
发明内容
发明目的:针对目前废弃塑料处理成本高、难利用的问题,提出一种以垃圾场废弃塑料为原料,进行改性处理,制备得到能够重复使用的再生薄膜。
为了实现上述目的,本发明公开了一种以废弃塑料为原料的再生薄膜,它由以下按质量百分比的组份制成:
优选地,最佳配方为废弃塑料:45%;mLLDPE:44.5%;POE-g-(GMA-co-st):8%;DCP:0.2%;白油:1%;抗氧剂:0.3%;芥酸酰胺:1%。
具体地,所述废弃塑料中,包含如下质量百分比的组成:
优选地,废弃塑料熔指(MFR,230℃,2.16kg)>15g/10min,断裂伸长率(按GB/T1040.2-2018注塑成哑铃状样条经拉伸测试而得)≤20%。
具体地,配方中聚乙烯为线性低密度聚乙烯,优选茂金属线性低密度聚乙烯。
具体地,所述POE-g-(GMA-co-st)为聚烯烃弹性体(POE,乙烯、丁烯和辛烯三元共聚物)接枝甲基丙烯酸缩水甘油酯(GMA)和苯乙烯(St)材料,通过如下步骤制备:
(1)将聚烯烃弹性体(POE)、甲基丙烯酸缩水甘油酯(GMA)、(苯乙烯St)和过氧化二异丙苯(DCP)按照质量比100:15:7:1加入高速混合机中混合,并加入以上混合原料总质量0.5%的白油,常温搅拌3-5分钟,转速200-300r/min;
(2)将步骤(1)所得混合物加入双螺杆挤出机中,于温度170-190℃,70-80r/min下,共混挤出改性制得。
具体地,所述交联剂为过氧化苯甲酰(BPO)、二叔丁基过氧化物(DTBP)或过氧化二异丙苯(DCP)中的任意一种或几种的组合,优选DCP。
由于垃圾场废旧塑料成分复杂,还含有PE、PP、PET、PS、PC以及无机填料等,使其力学性能低、相容性较差,因此改性制备吹膜料难度较大。通过引入本发明制备的多元改性剂POE-g-(GMA-co-st),其末端含有环氧基团可以与体系中PET、PC等含极性基团材质末端的羧基反应(回料中,PET和PC等极性材质会发生水解,末端羧基含量增加),实现原位增容,此外极性基团与极性基团之间形成的氢键,同样可以有效增加垃圾场废旧塑料体系的相容性,使得PET、PC等含极性基团材质于PE、PP界面分散粒径更小、更均匀,而POE主链又可有效增加复合材料的柔韧性,故此多元改性剂是本发明的最佳改性剂。此外,由于垃圾场废旧回料存在成分复杂,且长期处于受热、光照条件下,导致链段断裂现象严重,分子量明显下降等问题,导致体系熔指较大,薄膜加工过程稳定性不高,而且薄膜较易撕裂,而引入POE-g-(GMA-co-st)更有利于PET、PC等含极性基团材质的粒径分散更小、更均匀,可以有效提高交联效率,从而进一步增加薄膜的撕裂强度和熔体强度。
具体地,,所述增塑剂为白油、环氧大豆油(ESO)、乙酰柠檬酸三正丁酯(ATBC)中的任意一种或几种的组合,优选白油。
具体地,所述抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂10、抗氧剂168或DLTP中的任意一种或几种的组合,抗氧剂优选1010或抗氧剂168。
具体地,所述开口剂为油酸酰胺、芥酸酰胺、滑石粉、二氧化硅、硅藻土、碳酸钙中的任意一种或几种的组合,优选油酸酰胺。
本发明进一步提供上述以废弃塑料为原料的再生薄膜的制备方法,包括如下步骤:
(1)从垃圾场分拣出废旧塑料(包括:垃圾袋、购物袋、一次性餐盒及餐具、饮料瓶等),通过清洗、烘干、破碎,得到5-10mm大小的废弃塑料碎片;
(2)将步骤(1)所得废弃塑料碎片与聚乙烯、POE-g-(GMA-co-st)、交联剂、增塑剂、抗氧剂、开口剂混合,然后送入双螺杆挤出机共混改性,并挤出切粒;
(3)将步骤(2)所得物料颗粒在吹膜机或流延机上成膜收卷,即得。
优选地,步骤(2)中共混改性的温度为160-220℃,优选180-200℃;步骤(3)中成膜温度控制在170-230℃之间,优选190-210℃。
有益效果:
本发明制备方法以废旧垃圾场塑料制品,通过清洗、烘干、破碎等工艺为基础,通过POE-g-(GMA-co-st)对废旧塑料进行改性,提高废弃塑料中成分的相容性,从而使得废弃塑料中各材质粒径分散更小、更均匀,有利于后期交联反应的效率,增加薄膜的撕裂强度和熔体强度。本发明前期生产设备投入和后期生产成本都相对较低,并实现垃圾场废旧塑料可循环性,且产品力学性能好,断裂伸长率≥150%,熔指(MFR,230℃,2.16kg)<3g/10min。
具体实施方式
根据下述实施例,可以更好地理解本发明。
实施例1
从垃圾场分拣出的废旧塑料(包括:垃圾袋、购物袋、一次性餐盒及餐具、饮料瓶等),通过清洗、烘干、破碎,得到5-10mm大小的废弃塑料碎片;测定废弃塑料碎片中各成分含量为PE:42%,PP:31%,PET:13%,PS:2.5%,PC:3.5%、无机填料8%。废弃塑料熔指(MFR,230℃,2.16kg):18.7g/10min,断裂伸长率按GB/T1040.2-2018注塑成哑铃状样条经拉伸测试而得:16.4%。
按如下配比进行原料准备:废弃塑料:53%;mLLDPE:40%;POE-g-(GMA-co-st):5%;白油:0.3%;DCP:0.5%;抗氧剂1010:0.5%;芥酸酰胺:0.7%。
以上混合物首先经过高速混合机预混均匀,然后通过双螺杆挤出机共混改性,并挤出切粒,温度控制180-200℃,收料,烘干。最后,通过高压膜头吹膜机吹膜,吹膜机温度控制在190-210℃。收到薄膜软硬适中,质地光滑,开口性较好。
实施例2
废气塑料碎片中成分组成与实施例1相同。
按如下配比进行原料准备:废弃塑料:45%;mLLDPE:44.5%;POE-g-(GMA-co-st):8%;DCP:0.2%;白油:1%;抗氧剂1010:0.3%;芥酸酰胺:1%。
以上混合物首先经过高速混合机预混均匀,然后通过双螺杆挤出机共混改性,并挤出切粒,温度控制180-200℃,收料,烘干。最后,通过高压膜头吹膜机吹膜,吹膜机温度控制在190-210℃。收到薄膜软硬适中,力学性能较好,质地光滑,开口性较好。
实施例3
废气塑料碎片中成分组成与实施例1相同。
按如下配比进行原料准备:废弃塑料:30%;mLLDPE:58.3%;POE-g-(GMA-co-st):10%;DCP:0.1%;ESO:1%;抗氧剂1010:0.1%;芥酸酰胺:0.5%。
以上混合物首先经过高速混合机预混均匀,然后通过双螺杆挤出机共混改性,并挤出切粒,温度控制180-200℃,收料,烘干。最后,通过高压膜头吹膜机吹膜,吹膜机温度控制在190-210℃。收到薄膜偏软,质地光滑,开口性较好,膜泡稳定性高。
实施例4
废气塑料碎片中成分组成与实施例1相同。
按如下配比进行原料准备:废弃塑料:45%;传统LLDPE:44.5%;POE-g-(GMA-co-st):8%;DCP:0.2%;白油:1%;抗氧剂:0.3%;芥酸酰胺:1%。
以上混合物首先经过高速混合机预混均匀,然后通过双螺杆挤出机共混改性,并挤出切粒,温度控制180-200℃,收料,烘干。最后,通过高压膜头吹膜机吹膜,吹膜机温度控制在190-210℃。收到薄膜软硬适中,力学性能较好,质地光滑,开口性较好。
实施例5
从垃圾场分拣出的废旧塑料(包括:垃圾袋、购物袋、一次性餐盒及餐具、饮料瓶等),通过清洗、烘干、破碎,得到5-10mm大小的废弃塑料碎片;测定废弃塑料碎片中各成分含量为PE:40%,PP:30%,PET:15%,PS:2%,PC:5%、无机填料8%。废弃塑料熔指(MFR,230℃,2.16kg):21.3g/10min,断裂伸长率按GB/T1040.2-2018注塑成哑铃状样条经拉伸测试而得:11.5%。
按如下配比进行原料准备:废弃塑料:53%;mLLDPE:40%;POE-g-(GMA-co-st):5%;白油:0.3%;DCP:0.5%;抗氧剂1010:0.5%;芥酸酰胺:0.7%。
以上混合物首先经过高速混合机预混均匀,然后通过双螺杆挤出机共混改性,并挤出切粒,温度控制180-200℃,收料,烘干。最后,通过高压膜头吹膜机吹膜,吹膜机温度控制在190-210℃。收到薄膜软硬适中,质地光滑,开口性较好。
对比例1
废气塑料碎片中成分组成与实施例1相同。
按如下配比进行原料准备:废弃塑料:53%;mLLDPE:40%;POE:5%;DCP:0.5%;白油:0.3%;抗氧剂1010:0.5%;芥酸酰胺:0.7%。
以上混合物首先经过高速混合机预混均匀,然后通过双螺杆挤出机共混改性,并挤出切粒,温度控制180-200℃,收料,烘干。最后,通过高压膜头吹膜机吹膜,吹膜机温度控制在190-210℃。收到薄膜韧性一般,易撕裂。
对比例2
废气塑料碎片中成分组成与实施例1相同。
按如下配比进行原料准备:废弃塑料:45%;mLLDPE:44.5%;PE-g-MAH:8%;DCP:0.2%;白油:1%;抗氧剂:0.3%;芥酸酰胺:1%。
以上混合物首先经过高速混合机预混均匀,然后通过双螺杆挤出机共混改性,并挤出切粒,温度控制180-200℃,收料,烘干。最后,通过高压膜头吹膜机吹膜,吹膜机温度控制在190-210℃。收到薄膜软硬适中,但相较易撕裂。
对比例3
废气塑料碎片中成分组成与实施例1相同。
按如下配比进行原料准备:废弃塑料:45%;mLLDPE:44.7%;POE-g-(GMA-co-st):8%;白油:1%;抗氧剂:0.3%;芥酸酰胺:1%。
以上混合物首先经过高速混合机预混均匀,然后通过双螺杆挤出机共混改性,并挤出切粒,温度控制180-200℃,收料,烘干。最后,通过高压膜头吹膜机吹膜,吹膜机温度控制在190-210℃。收到薄膜软硬适中,力学性能不错,质地光滑,开口性较好,吹膜稳定性稍有不足。
对比例4
废气塑料碎片中成分组成与实施例1相同。
按如下配比进行原料准备:废弃塑料:45%;mLLDPE:52.5%;DCP:0.2%;白油:1%;抗氧剂:0.3%;芥酸酰胺:1%。
以上混合物首先经过高速混合机预混均匀,然后通过双螺杆挤出机共混改性,并挤出切粒,温度控制180-200℃,收料,烘干。最后,通过高压膜头吹膜机吹膜,吹膜机温度控制在190-210℃。收到薄膜软硬适中,强度较好,但易撕裂,质地光滑,开口性较好,吹膜稳定性稍有不足。
选取实施例1-5和对比实施例1-4得到的样品,进行性能测试,测其中,拉伸强度和断裂伸长率指标按照GB/T 1040.3-2018测试,熔体流动速率(MFR)按照国标GB/T3682-2018测定。试结果如下表1所示:
表1
通过实施例2与对比例1和2的比较,可以发现:POE-g-(GMA-co-st)对于本发明体系的效果要明显好于POE和PE-g-MAH的(从断裂伸长率和熔指两项指标比较),POE仅有增韧作用,无极性基团,起不到增容效果,而PE-g-MAH的活性基团(酸酐)与PET、PC、无机材料等反应活性不如POE-g-(GMA-co-st)的活性基团(环氧基团),与基体废旧塑料形成有效化学键少,故相容性不如POE-g-(GMA-co-st),因此POE-g-(GMA-co-st)是本体系的合适相容增韧改性剂。
通过实施例2与对比例3和4的比较,可以发现:POE-g-(GMA-co-st)和交联剂DCP协同作用要比单独使用其一效果要好(从断裂伸长率和熔指两项指标比较),二者相辅相成,既可以增加改性料的力学性能又可以有效提高其加工稳定性。
从以上组成和结果可以看出,本发明的材料主要基于垃圾场废旧回料,通过本发发明的处理和改性,得到薄膜机械性能较好,可以满足日用薄膜制品类常规性能,而且产品可完全市场化,符合低碳发展经济理念。
本发明提供了一种以废弃塑料为原料的再生薄膜及其制备方法的思路及方法,具体实现该技术方案的方法和途径很多,以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。
Claims (10)
3.根据权利要求1所述的以废弃塑料为原料的再生薄膜,其特征在于,所述聚乙烯为线性低密度聚乙烯。
4.根据权利要求1所述的以废弃塑料为原料的再生薄膜,其特征在于,所述POE-g-(GMA-co-st)为聚烯烃弹性体接枝甲基丙烯酸缩水甘油酯和苯乙烯材料,通过如下步骤制备:
(1)将聚烯烃弹性体、甲基丙烯酸缩水甘油酯、苯乙烯和过氧化二异丙苯按照质量比100:15:7:1加入高速混合机中混合,并加入以上混合原料总质量0.5%的白油,常温搅拌3-5分钟,转速200-300r/min;
(2)将步骤(1)所得混合物加入双螺杆挤出机中,于温度170-190℃,70-80r/min下,共混挤出改性制得。
5.根据权利要求1所述的以废弃塑料为原料的再生薄膜,其特征在于,所述交联剂为过氧化苯甲酰、二叔丁基过氧化物或过氧化二异丙苯中的任意一种或几种的组合。
6.根据权利要求1所述的以废弃塑料为原料的再生薄膜,其特征在于,所述增塑剂为白油、环氧大豆油或乙酰柠檬酸三正丁酯中的任意一种或几种的组合。
7.根据权利要求1所述的以废弃塑料为原料的再生薄膜,其特征在于,所述抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂10、抗氧剂168或DLTP中的任意一种或几种的组合。
8.根据权利要求1所述的以废弃塑料为原料的再生薄膜,其特征在于,所述开口剂为油酸酰胺、芥酸酰胺、滑石粉、二氧化硅、硅藻土或碳酸钙中的任意一种或几种的组合。
9.权利要求1所述以废弃塑料为原料的再生薄膜的制备方法,其特征在于,包括如下步骤:
(1)从垃圾场分拣出的废旧塑料,通过清洗、烘干、破碎,得到5-10mm大小的废弃塑料碎片;
(2)将步骤(1)所得废弃塑料碎片与聚乙烯、POE-g-(GMA-co-st)、交联剂、增塑剂、抗氧剂、开口剂混合,然后送入双螺杆挤出机共混改性,并挤出切粒;
(3)将步骤(2)所得物料颗粒在吹膜机或流延机上成膜收卷,即得。
10.根据权利要求9所述以废弃塑料为原料的再生薄膜的制备方法,其特征在于,步骤(2)中共混改性的温度为160-220℃;步骤(3)中成膜温度控制在170-230℃之间。
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CN116082734B (zh) * | 2022-12-30 | 2024-05-28 | 广东溢达纺织有限公司 | 一种无爽滑剂污染的易开口再生聚乙烯包装材料及其制备方法 |
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