CN109762313A - 一种高倍率聚乳酸发泡片材的制备方法 - Google Patents

一种高倍率聚乳酸发泡片材的制备方法 Download PDF

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CN109762313A
CN109762313A CN201811637504.9A CN201811637504A CN109762313A CN 109762313 A CN109762313 A CN 109762313A CN 201811637504 A CN201811637504 A CN 201811637504A CN 109762313 A CN109762313 A CN 109762313A
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polylactic acid
temperature
sheet material
level
preparation
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CN109762313B (zh
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黄伟伟
王乐军
宋亚男
郑宗强
刘怡宁
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Juhengmei Engineering Technology Ningbo Co ltd
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Hi Tech Bio Based Materials Engineering Technology (ningbo) Co Ltd
Hi Tech Fiber Group Corp
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Publication of CN109762313A publication Critical patent/CN109762313A/zh
Priority to JP2021538466A priority patent/JP7288060B2/ja
Priority to PCT/CN2019/096496 priority patent/WO2020134041A1/zh
Priority to US17/419,308 priority patent/US20220088840A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
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    • B29C44/46—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length
    • B29C44/50—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length using pressure difference, e.g. by extrusion or by spraying
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Abstract

本发明提供一种高倍率聚乳酸发泡片材的制备方法，包括一级挤出、二级挤出、挤出发泡片材；原料由下述成分按重量份组成：聚乳酸88～94份、成核剂1～2份、发泡剂2～5份、助剂2～5份。本发明有效解决了工业生产中使用二氧化碳发泡倍率低、强度不高等难点，制备的高发泡倍率、表面性能优良的聚乳酸片材可以用于食品包装以及一次性全降解餐盒等领域。

Description

一种高倍率聚乳酸发泡片材的制备方法
技术领域
本发明属于聚乳酸发泡技术领域，具体涉及一种制备高倍率聚乳酸发泡片材的方法。
背景技术
针对近几年呈爆发式增长的快递产业及其产生的包装废弃物带来的污染，2016年，国家邮政局出台《推进绿色快递业包装工作实施方案》，2018年2月，国家质检总局、国家标准委发布《快递封装用品》系列国家标准，根据减量化、绿色化、可循环的要求，对快递包装减量提出新要求，要求快递包装袋宜采用生物降解塑料，减少白色污染。2018年是“限塑令”发布十年，国家发改委网站开设“我为塑料垃圾污染防治建言献策”专栏，邀请社会各界人士在1月5日至1月31日期间，围绕不同领域塑料制品的管理要求，提出意见建议。这是继2008年实施《国务院办公厅关于限制生产销售塑料购物袋的通知》以来，国家层面就防治“白色污染”采取的进一步举措。而以美团、饿了么为主体的点餐平台迫于社会压力，正在着手绿色一次性餐具的推广；2018年2月28日，菜鸟联合阿里巴巴公益基金会，中华环境保护基金会、中通、圆通、申通、天天、百世快递、韵达等主要快递公司共同发布“中国绿色物流研发资助计划”，希望用科技的力量助力行业升级，让中国更加绿色、智慧、高效。
聚乳酸是一种来源于可再生资源的全生物降解材料。原料乳酸由木薯、玉米、甜菜等高糖分含量的植物发酵而成，经缩聚生成丙交酯后，再开环聚合为聚乳酸。聚乳酸可以进行注塑、吸塑、吹瓶、吹膜以及纺丝等多种方式进行加工，制品在丢弃后可在土壤中微生物及水氧的作用下分解成二氧化碳和水，又被植物生长所利用。因此，聚乳酸的整个生命周期没有多余的二氧化碳排放，是一种真正意义上的绿色低碳环保材料。聚乳酸本身无毒副作用，无有害物质释放，是一种理想的食品接触安全的包装材料。
目前制约聚乳酸发展的主要是性能和价格这两大方面，将其做成发泡材料能够大大降低其成本，价格可以与市面上常见的PP餐具相媲美，甚至更低，具有明显的竞争优势。在当今以PP和ps为主的塑料市场拥有一席之地。随着石油能源的日益匮乏以及以石油基为主的传统塑料对环境破坏和生态污染日益增重，国内外生物全降解材料特别是聚乳酸发泡材料的需求呈逐年上升趋势，聚乳酸发泡材料可谓是市场潜力巨大。近年来，随着高分子材料科学的不断进步，聚乳酸的问题正不断地被破解，全降解聚乳酸材料将来很有希望全面代替传统石油基塑料，成为市场的主流塑料产品。
CN105038161A公开了一种改性埃洛石、聚乳酸发泡材料及其制备与应用，对埃洛石表面羟基化改性、表面有机硅烷化改性，然后将改性的埃洛石吸附二氧化碳和聚乳酸、交联剂一起制备聚乳酸发泡材料，发泡密度为0.038g/cm3，发泡倍率超过30倍，孔径10～30μm，同时公开了发泡材料的熔融指数、熔融强度、拉伸强度、弯曲强度、缺口冲击强度等。该专利的埃洛石提纯相对而言较为复杂，而且用到的的溶剂大多都是对人体有害的危险品，违背了绿色环保要求，不利于聚乳酸发泡材料的工业化。
CN106967280A公开一种高倍率全生物降解发泡材料的制备方法，将聚乳酸、反应相容剂EC、聚己二酸/对苯二甲酸丁二酯和有机改性蒙脱土进行密炼，获得混合改性母粒，注入超临界二氧化碳发泡制得泡沫密度为0.0155～0.0205g/cm3，发泡倍率为60～80倍的产物。虽然此专利能够得到超高倍率的发泡材料，但是随着倍率的提升，材料的拉伸强度、弯曲强度、缺口冲击强度等机械性能都有明显的下降，这影响了在一次性餐盒领域的应用。
CN106750486A公开了一种超临界流体制备微发泡聚乳酸基木塑复合材料的方法，将聚乳酸、木粉、增韧剂、扩链剂、润滑剂、成核剂混合，采用双螺杆挤出机制备聚乳酸发泡材料，泡孔均匀，发泡倍率为5～50倍，表观密度为0.03～0.3g/cm3，孔直径为10～200微米。该专利中木粉的添加，泡孔尺寸差距较大，
对聚乳酸片材表面的光泽度会产生一定影响。
CN108409985A公开一种通过预等温冷结晶处理提高聚乳酸发泡倍率的方法，制备的聚乳酸发泡材料的发泡倍率最高达17.7倍，泡孔平均直径为18微米，泡孔密度2.2×108个/cm3。该专利通过高压釜设备进行发泡的发泡倍率不易控制，不能得到客户要求的倍率稳定的发泡材料。
现有技术通过二氧化碳发泡气制备的聚乳酸发泡材料，存在以下不足：
（1）保证发泡材料机械性能的同时，发泡倍率低；提高发泡倍率，制备的发泡材料的拉伸强度、弯曲强度、缺口冲击强度等机械性能都有明显的下降。
（2）发泡尺寸和发泡倍率难以控制、泡孔直径大小不均匀，片材厚度不匀。
（3）现有技术制备的发泡材料，表观密度较小，机械强度低，生产时材料易穿孔、易破泡。
发明内容
为了解决现有技术中存在的不足，本发明提供一种高倍率聚乳酸发泡片材的制备方法，具备工业化生产，能够高效地生产出符合市场需求的全降解聚乳酸发泡片材，实现以下发明目的：
（1）提高发泡倍率的同时，提高发泡材料的拉伸强度、弯曲强度。
（2）发泡尺寸和发泡倍率容易控制、泡孔直径均匀，片材厚度均匀。
（3）提高表观密度，材料无穿孔、破泡现象。
为解决上述技术问题，本发明采取以下技术方案：
一种高倍率聚乳酸发泡片材的制备方法，包括以下步骤：
（1）一级挤出
按质量份数计量聚乳酸88～95份、成核剂1～2份、发泡剂2～5份、助剂2～5份注入一级螺杆挤出机中，设定一级螺杆挤出机各区段温度，待原料和发泡剂以液相均匀混合后，得到初步混合熔体。
所述的聚乳酸原料是经过改性的发泡级聚乳酸原料，分子量在12～15万，其聚乳酸含量≥97%。
所述的发泡剂为含氟化合物，为气体状态，是二氟一氯甲烷、三氟三氯乙烷或者四氟二氯乙烷中的任何一种；
所述成核剂为滑石粉，所述助剂为氮气；
由于含氟化合物发泡剂本身压力不足以和聚乳酸熔体很好的融合，需要用到助剂氮气，所述的氮气是高压、高纯度氮气，氮气的注入压力为10～15MPa，其纯度≥99.9%。
所述发泡剂的注入压力为16～20MPa。
所述一级螺杆挤出机从加料到机颈依次一区温度至十一区温度，它们的温度范围控制在为180～200℃之间；
所述一级螺杆挤出机，从加料到机颈依次一区温度为180-185℃、二区温度为182-188℃、三区温度为190℃、四区温度为195℃、五区温度为198-200℃、六区温度为200℃、七区温度为200℃、八区温度为200℃、九区温度为200℃、十区温度为200℃、十一区温度为200℃。
所述的一级螺杆挤出机螺杆直径为135mm，长径比36：1，螺杆起始转速在5～15r/min。
（2）二级挤出
将初步混合熔体注入到二级螺杆挤出机利用模温机进行二次控温混合，设定各个区段模温机温度，让混合熔体进行进一步的融熔、混炼、加压及冷却，使熔体达到的片材生产的理想状态。
所述二级螺杆挤出机温度设定从油温1至机头依次有8个油温机，它们的温度控制在150～170℃之间，熔体压力控制为4-6MPa；二级螺杆挤出机螺杆直径为150mm，长径比36：1，螺杆起始转速在5～7r/min。
所述二级螺杆挤出机温度设定从油温1至机头依次为油温1为165-180℃、油温2为160-168℃、油温3为158-165℃、油温4为156-163℃、油温5为152-160℃、油温6为153-158℃、油温7为152-155℃、油温8为152-155℃。
（3）挤出发泡片材
所述挤出发泡片材，待一级挤出出口的熔体压力达到12～15Mpa、温度达到190℃～200℃，二级挤出出口的熔体压力达到3～6MPa，温度达到150～160℃时，设定一级挤出机转速20-50r/min，优选为20-30 r/min；二级挤出机转速为10-20r/min，经片材模具挤出发泡片材。
（4）冷却成型、剖开、展平、牵引、定型卷绕
经冷却成型装置冷却成型，剖开、展平，再通过牵引机进行冷却牵引，再通过收卷机定型卷绕最终得到PLA发泡片材。
所述的冷却成型装置是防静电冷却定型套，通过两台冷却风机对成型片材进行环形冷却以及成型套内水冷。所述的牵引机为辊式牵引机，牵引速度为8～12m/min。
本发明采用双级串联单螺杆挤出系统，包括一级螺杆挤出机和二级螺杆挤出机。
本发明的有益效果：
本发明采用的是含氟化合物物理发泡剂，结合助剂氮气的使用，并结合二级螺杆挤出工艺设置，实现以下有益效果：
（1）本发明制备的聚乳酸片材发泡倍率为13～16倍，同时拉伸强度为80-88Mpa、弯曲强度120-128Mpa。
（2）本发明制备的聚乳酸发泡材料，泡孔直径均匀，片材厚度均匀。片材厚度为2～5mm，优选为3.8-4.8mm，厚度均一，误差可以控制在±0.1mm，泡孔直径在10～40微米，孔的密度在1～2.7x108个/cm3。
（3）本发明制备的聚乳酸发泡材料，表观密度在0.06～0.18g/cm3，优选为0.075-0.092 g/cm3，材料无穿孔、破泡现象，片材泡孔结构稳定。
（4）本发明采用的135/150双级串联单螺杆挤出系统，根据聚合物物理发泡特点，通过专用螺杆CAD设计软件优化设计，配以自动液压换网，实现高塑化能力的低温稳定挤出。该设备系统能够高效稳定生产出宽幅在1080mm的发泡片材，可以实现聚乳酸发泡的工业化生产。
附图说明
图1为本发明制备高倍率聚乳酸发泡片材的工艺流程图。
具体实施方式
下面结合实施例对本发明做进一步说明
实施例1
（1）一级挤出
按质量份数计量聚乳酸88份、成核剂滑石粉2份、注入一级螺杆挤出机中，待熔体在一级挤出塑化混合后，将发泡剂二氟一氯甲烷5份、助剂氮气5份注入一级挤出机中，发泡剂的注入压力在18Mpa，氮气的注入压力在11Mpa。设定一级螺杆挤出机各区段温度，从加料到机颈依次一区温度为180℃、二区温度为182℃、三区温度为190℃、四区温度为195℃、五区温度为200℃、六区温度为200℃、七区温度为200℃、八区温度为200℃、九区温度为200℃、十区温度为200℃、十一区温度为200℃。设置一级螺杆挤出机的挤出速度为10r/min。待原料和发泡剂以液相均匀混合后，得到初步混合熔体。
（2）二级挤出
将初步混合熔体注入到二级螺杆挤出机利用模温机进行二次控温混合，熔体压力控制在4～6Mpa。温度设定从油温1至机头依次为油温1为165℃、油温2为160℃、油温3为158℃、油温4为158℃、油温5为152℃、油温6为153℃、油温7为153℃、油温8为153℃。设定二级螺杆挤出机转速为5r/min。
让混合熔体进行进一步的融熔、混炼、加压及冷却。
（3）挤出发泡片材
待熔体在一级挤出出口的压力达到15Mpa，温度达到190℃，二级出口的压力在4Mpa，温度要在150℃。
设定一级挤出机转速24r/min，二级挤出机转速13r/min。
调节内口膜螺栓和外口膜螺栓，使得口模间距在至1.5mm，熔体经片材模具桶状挤出发泡片材。
（4）冷却成型、剖开、展平、牵引、定型卷绕
经冷却成型装置冷却成型，剖开、展平。再通过设定牵引机牵引速度为8m/min进行冷却牵引，再通过收卷机定型卷绕最终得到PLA发泡片材。
所得到的发泡片材宽幅在1m，厚度4.8mm，表观密度为0.075g/cm3，发泡倍率在16倍。泡孔直径在30～40微米，孔的密度在1x108个/cm3。拉伸强度80Mpa、弯曲强度128Mpa。
实施例2
（1）一级挤出
按质量份数计量聚乳酸90份、成核剂滑石粉2份、注入一级螺杆挤出机中，待熔体在一级挤出塑化混合后，将发泡剂三氟三氯乙烷4份、助剂氮气4份注入一级螺杆挤出机中，发泡剂的注入压力在18Mpa，氮气的注入压力在12Mpa。设定一级螺杆挤出机各区段温度，从加料到机颈依次一区温度为182℃、二区温度为182℃、三区温度为190℃、四区温度为195℃、五区温度为200℃、六区温度为200℃、七区温度为200℃、八区温度为200℃、九区温度为200℃、十区温度为200℃、十一区温度为200℃。一级螺杆挤出机的挤出速度为10r/min。待原料和发泡剂以液相均匀混合后，得到初步混合熔体。
（2）二级挤出
将初步混合熔体注入到二级螺杆挤出机利用模温机进行二次控温混合，熔体压力控制在4～6Mpa。温度设定从油温1至机头依次为油温1为165℃、油温2为165℃、油温3为163℃、油温4为161℃、油温5为158℃、油温6为155℃、油温7为152℃、油温8为152℃。设定二级螺杆挤出机转速为5r/min。让混合熔体进行进一步的融熔、混炼、加压及冷却。
（3）挤出发泡片材
待熔体在一级挤出口压力达到15Mpa，温度达到195℃；二级出口的压力在4Mpa，温度要在155℃的时候，设定一级挤出机转速24r/min，二级挤出机转速13r/min。调节内口膜螺栓和外口膜螺栓，使得口模间距在至1.4mm，熔体经片材模具桶状挤出发泡片材。
（4）冷却成型、剖开、展平、牵引、定型卷绕
经冷却成型装置冷却成型，剖开、展平。通过设定牵引机牵引速度为10m/min进行冷却牵引，再通过收卷机定型卷绕最终得到PLA发泡片材。
所得到的发泡片材宽幅在1m，厚度4.2mm，表观密度为0.08g/cm3，发泡倍率在15倍。泡孔直径在25～40微米，孔的密度在2x108个/cm3。拉伸强度85Mpa、弯曲强度120Mpa。
实施例3
（1）一级挤出
按质量份数计量聚乳酸91份、成核剂滑石粉2份注入一级螺杆挤出机中，待熔体在一级挤出塑化混合后，将发泡剂四氟二氯乙烷3.5份、助剂氮气3.5份注入一级螺杆挤出机中，发泡剂的注入压力在18Mpa，氮气的注入压力在14Mpa。设定一级螺杆挤出机各区段温度，从加料到机颈依次一区温度为185℃、二区温度为188℃、三区温度为190℃、四区温度为195℃、五区温度为200℃、六区温度为200℃、七区温度为200℃、八区温度为200℃、九区温度为200℃、十区温度为200℃、十一区温度为200℃。一级螺杆挤出机的挤出速度为10r/min。待原料和发泡剂以液相均匀混合后，得到初步混合熔体。
（2）二级挤出
将初步混合熔体注入到二级螺杆挤出机利用模温机进行二次控温混合，熔体压力控制在4～6Mpa。温度设定从油温1至机头依次为油温1为165℃、油温2为160℃、油温3为158℃、油温4为156℃、油温5为154℃、油温6为153℃、油温7为153℃、油温8为153℃。设定二级螺杆挤出机转速为5r/min。让混合熔体进行进一步的融熔、混炼、加压及冷却。
（3）挤出发泡片材
待熔体一级挤出压力达到17Mpa，温度达到192℃；二级出口的压力在5Mpa，温度要在160℃的时候，设定一级挤出机转速24r/min，二级挤出机转速13r/min，调节内口膜螺栓和外口膜螺栓，使得口模间距在至1.4mm，熔体经片材专用模具桶状挤出发泡片材。
（4）冷却成型、剖开、展平、牵引、定型卷绕
经冷却成型装置冷却成型，剖开、展平。再通过设定牵引机牵引速度为10m/min进行冷却牵引，再通过收卷机定型卷绕最终得到PLA发泡片材。
所得到的发泡片材宽幅在1m，厚度4.0mm，表观密度为0.086g/cm3，发泡倍率在14倍。泡孔直径在10～30微米，孔的密度在2.4x108个/cm3。拉伸强度86Mpa、弯曲强度122Mpa。
实施例4
（1）一级挤出
按质量份数计量聚乳酸92份、成核剂滑石粉2份注入一级螺杆挤出机中，待熔体在一级挤出塑化混合后，将发泡剂二氟一氯甲烷3份、助剂氮气3份注入一级螺杆挤出机中，发泡剂的注入压力在18Mpa，氮气的注入压力在15Mpa。设定一级螺杆挤出机各区段温度，从加料到机颈依次一区温度为182℃、二区温度为186℃、三区温度为190℃、四区温度为195℃、五区温度为198℃、六区温度为200℃、七区温度为200℃、八区温度为200℃、九区温度为200℃、十区温度为200℃、十一区温度为200℃。一级螺杆挤出机的挤出速度为10r/min。待原料和发泡剂以液相均匀混合后，得到初步混合熔体。
（2）二级挤出
将初步混合熔体注入到二级螺杆挤出机利用模温机进行二次控温混合，熔体压力控制在4～6Mpa。温度设定从油温1至机头依次为油温1为180℃、油温2为168℃、油温3为165℃、油温4为163℃、油温5为160℃、油温6为158℃、油温7为155℃、油温8为155℃。设定二级螺杆挤出机转速为5r/min。让混合熔体进行进一步的融熔、混炼、加压及冷却。
（3）挤出发泡片材
待熔体一级挤出压力达到18Mpa，温度达到198℃；二级出口的压力在6Mpa，温度要在153℃的时候，设定一级挤出机转速24r/min，二级挤出机转速13r/min，调节内口膜螺栓和外口膜螺栓，使得口模间距在至1.3mm，熔体经片材专用模具桶状挤出发泡片材。
（4）冷却成型、剖开、展平、牵引、定型卷绕
经冷却成型装置冷却成型，剖开、展平。再通过设定牵引机牵引速度为10.5m/min进行冷却牵引，再通过收卷机定型卷绕最终得到PLA发泡片材。
所得到的发泡片材宽幅在1m，厚度3.8mm，表观密度约为0.092g/cm3，发泡倍率在13倍。泡孔直径在20～30微米，孔的密度在2.7x108个/cm3。拉伸强度88Mpa、弯曲强度128Mpa。
本技术方案选择的是氟化物作为发泡剂，能够很好的与聚乳酸熔体进行融合；采用双级串联单螺杆挤出系统，一级挤出是通过电加热方式能够对聚乳酸原料进行快速升温，二级挤出是通过8个油温机，进行各个区段的定点精准温控，使得聚乳酸熔体和发泡剂能够很好的融合。

Claims (10)

1.一种高倍率聚乳酸发泡片材的制备方法，其特征在于：包括一级挤出、二级挤出、挤出发泡片材。
2.根据权利要求1所述的一种高倍率聚乳酸发泡片材的制备方法，其特征在于：所述一级挤出，各原料的质量份数为：聚乳酸88～95份、成核剂1～2份、发泡剂2～5份、助剂2～5份；所述发泡剂为含氟化合物。
3.根据权利要求2所述的一种高倍率聚乳酸发泡片材的制备方法，其特征在于：所述发泡剂为二氟一氯甲烷、三氟三氯乙烷或者四氟二氯乙烷中的任何一种；所述助剂为氮气；所述成核剂为滑石粉。
4.根据权利要求1所述的一种高倍率聚乳酸发泡片材的制备方法，其特征在于：所述挤出发泡片材，待一级挤出出口的熔体压力达到12～15Mpa、温度达到190℃～200℃，二级挤出出口的熔体压力达到3～6MPa，温度达到150～160℃时，设定一级螺杆挤出机的螺杆转速为20-50 r/min，二级螺杆挤出机的螺杆转速为10-20 r/min，经片材模具挤出发泡片材。
5.根据权利要求1所述的一种高倍率聚乳酸发泡片材的制备方法，其特征在于：所述一级挤出，一级螺杆挤出机螺杆直径为135mm，长径比36：1，螺杆起始转速在5～15r/min；从加料到机颈依次设置一区温度至十一区温度，温度范围控制在为180～200℃之间。
6.根据权利要求1所述的一种高倍率聚乳酸发泡片材的制备方法，其特征在于：所述二级挤出，二级螺杆挤出机螺杆直径为150mm，长径比36 ：1，螺杆起始转速在5～7r/min；温度设定从油温1至机头依次有8个油温机，温度控制在150～170℃之间，熔体压力为4～6MPa。
7.根据权利要求2所述的一种高倍率聚乳酸发泡片材的制备方法，其特征在于：所述聚乳酸是经过改性的发泡级聚乳酸原料，分子量在12～15万，聚乳酸含量≥97%。
8.根据权利要求2所述的一种高倍率聚乳酸发泡片材的制备方法，其特征在于：所述氮气的注入压力为10～15MPa，纯度≥99.9%；所述发泡剂的注入压力为16～20MPa。
9.根据权利要求1所述的一种高倍率聚乳酸发泡片材的制备方法，其特征在于：所述方法，还包括冷却成型、剖开、展平、牵引、定型卷绕；所述冷却成型、剖开、展平、牵引、定型卷绕，
经冷却成型装置冷却成型，剖开、展平；再通过设定牵引机的牵引速度进行冷却牵引，再通过收卷机定型卷绕最终得到PLA发泡片材。
10.根据权利要求9所述的一种高倍率聚乳酸发泡片材的制备方法，其特征在于：所述冷却成型的装置是防静电冷却定型套，通过两台冷却风机对成型片材进行环形冷却以及成型套内水冷；
所述的牵引机为辊式牵引机，牵引速度为8～12m/min。
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111040397A (zh) * 2019-08-22 2020-04-21 广州绿徽新材料研究院有限公司 一种组合发泡聚乳酸耐热阻燃改性材料和产品的制备方法
WO2020134041A1 (zh) * 2018-12-29 2020-07-02 恒天纤维集团有限公司 一种高倍率聚乳酸发泡片材的制备方法
CN111848909A (zh) * 2020-07-31 2020-10-30 江苏绿艳高分子材料有限公司 一种ndi基闭孔微孔弹性体及其一步法生产方法
CN112266590A (zh) * 2020-09-19 2021-01-26 恒天生物基材料工程技术（宁波）有限公司 一种聚乳酸/微晶纤维素复合发泡片材及其制备方法
CN113105731A (zh) * 2021-04-15 2021-07-13 山东道恩高分子材料股份有限公司 一种生物降解发泡片材
CN115073898A (zh) * 2022-04-14 2022-09-20 万华化学（宁波）有限公司 一种高熔体强度pla合金、一种发泡料及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230302708A1 (en) * 2022-03-22 2023-09-28 Ricoh Company, Ltd. Resin foam production apparatus and method of producing resin foam

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1600814A (zh) * 2003-09-24 2005-03-30 赖文正 聚乳酸的发泡方法与其发泡体
WO2005042627A1 (en) * 2003-11-03 2005-05-12 Coopbox Europe S.P.A. Pla-based degradable foams and process for their production
US20070141286A1 (en) * 2005-12-19 2007-06-21 Jsp Corporation Foamed sheet of polylactic acid resin, foam molding of polylactic acid resin and method of preparing foam molding
US20070293593A1 (en) * 2006-06-06 2007-12-20 Harfmann Walter R Low density polylactic acid polymeric foam and articles made thereof
CN101959945A (zh) * 2008-03-07 2011-01-26 东丽株式会社 绝热材料
CN102037053A (zh) * 2008-04-30 2011-04-27 自然工作有限责任公司 由具有高分子量和高特性粘数的聚丙交酯制得的挤出泡沫
CN102573818A (zh) * 2009-09-25 2012-07-11 阿科玛股份有限公司 具有改进的尺寸稳定性的生物可降解泡沫
CN103467949A (zh) * 2013-09-25 2013-12-25 张家港保税区冠祥贸易有限公司 基于聚乳酸的塑料生产方法

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0539398A1 (en) * 1990-07-16 1993-05-05 E.I. Du Pont De Nemours And Company Degradable foam materials
JP3376415B2 (ja) * 2000-03-10 2003-02-10 ハッポー化学工業株式会社 生分解性ポリ乳酸発泡ボード
JP4480600B2 (ja) * 2005-02-21 2010-06-16 積水化成品工業株式会社 ポリ乳酸系樹脂発泡シートの製造方法
EP2089460B1 (en) * 2006-12-14 2011-09-07 Pactiv Corporation Expanded and extruded biodegradable and reduced emission foams made with methyl formate-based blowing agents
KR101766947B1 (ko) * 2014-01-23 2017-08-09 (주)엘지하우시스 폴리락트산 발포 성형체 및 그 제조 방법
KR101735887B1 (ko) * 2014-06-02 2017-05-16 (주)엘지하우시스 폴리유산계 수지 발포체 및 그 제조방법
CN106905676B (zh) * 2017-04-21 2019-09-13 桑德（天津）再生资源投资控股有限公司 一种聚乳酸-聚丙烯合金发泡材料的制备方法
CN107337912A (zh) * 2017-06-21 2017-11-10 佛山市高明科力机械有限公司 一种pla聚乳酸生物降解发泡餐盒生产工艺
CN108752734A (zh) * 2018-05-04 2018-11-06 广德祥源新材科技有限公司 一种可降解的抗菌型塑料发泡卷材及制造方法
CN108948698A (zh) * 2018-07-26 2018-12-07 北京化工大学 一种新型挤塑聚乳酸发泡片材生产技术
CN109593332B (zh) * 2018-12-14 2021-02-02 河南青源天仁生物技术有限公司 适用于机械移栽的全生物降解发泡育苗盘及其制备方法
CN109762313B (zh) * 2018-12-29 2020-09-22 恒天纤维集团有限公司 一种高倍率聚乳酸发泡片材的制备方法
CN109852037A (zh) * 2018-12-29 2019-06-07 中粮集团有限公司 聚乳酸发泡片材及其制备方法
CN109776848B (zh) * 2019-01-08 2020-06-30 恒天纤维集团有限公司 聚乳酸聚合熔体直接制备聚乳酸发泡制品的方法及装置
EP4219607A1 (en) * 2022-01-28 2023-08-02 Ricoh Company, Ltd. Foam sheet

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1600814A (zh) * 2003-09-24 2005-03-30 赖文正 聚乳酸的发泡方法与其发泡体
WO2005042627A1 (en) * 2003-11-03 2005-05-12 Coopbox Europe S.P.A. Pla-based degradable foams and process for their production
US20070141286A1 (en) * 2005-12-19 2007-06-21 Jsp Corporation Foamed sheet of polylactic acid resin, foam molding of polylactic acid resin and method of preparing foam molding
US20070293593A1 (en) * 2006-06-06 2007-12-20 Harfmann Walter R Low density polylactic acid polymeric foam and articles made thereof
CN101959945A (zh) * 2008-03-07 2011-01-26 东丽株式会社 绝热材料
CN102037053A (zh) * 2008-04-30 2011-04-27 自然工作有限责任公司 由具有高分子量和高特性粘数的聚丙交酯制得的挤出泡沫
CN102573818A (zh) * 2009-09-25 2012-07-11 阿科玛股份有限公司 具有改进的尺寸稳定性的生物可降解泡沫
CN103467949A (zh) * 2013-09-25 2013-12-25 张家港保税区冠祥贸易有限公司 基于聚乳酸的塑料生产方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020134041A1 (zh) * 2018-12-29 2020-07-02 恒天纤维集团有限公司 一种高倍率聚乳酸发泡片材的制备方法
CN111040397A (zh) * 2019-08-22 2020-04-21 广州绿徽新材料研究院有限公司 一种组合发泡聚乳酸耐热阻燃改性材料和产品的制备方法
CN111040397B (zh) * 2019-08-22 2021-09-24 广州绿徽新材料研究院有限公司 一种组合发泡聚乳酸耐热阻燃改性材料和产品的制备方法
CN111848909A (zh) * 2020-07-31 2020-10-30 江苏绿艳高分子材料有限公司 一种ndi基闭孔微孔弹性体及其一步法生产方法
CN112266590A (zh) * 2020-09-19 2021-01-26 恒天生物基材料工程技术（宁波）有限公司 一种聚乳酸/微晶纤维素复合发泡片材及其制备方法
CN112266590B (zh) * 2020-09-19 2023-02-28 恒天生物基材料工程技术（宁波）有限公司 一种聚乳酸/微晶纤维素复合发泡片材及其制备方法
CN113105731A (zh) * 2021-04-15 2021-07-13 山东道恩高分子材料股份有限公司 一种生物降解发泡片材
CN115073898A (zh) * 2022-04-14 2022-09-20 万华化学（宁波）有限公司 一种高熔体强度pla合金、一种发泡料及其制备方法
CN115073898B (zh) * 2022-04-14 2023-12-19 万华化学（宁波）有限公司 一种高熔体强度pla合金、一种发泡料及其制备方法

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