可生物降解泡沫材料的研究进展

doi:10.16085/j.issn.1000-6613.2022-0785

化工进展 ›› 2023, Vol. 42 ›› Issue (3): 1457-1470.DOI: 10.16085/j.issn.1000-6613.2022-0785

可生物降解泡沫材料的研究进展

蔡举艳¹^,²^,³^,⁴(), 苏琼¹^,²^,³^,⁴(), 王彦斌¹^,²^,³^,⁴, 王鸿灵¹^,²^,³^,⁴, 梁俊玺¹^,²^,³^,⁴, 王忠旭¹^,²^,³^,⁴, 郭丽¹^,²^,³^,⁴, 赵利斌⁵

^1.西北民族大学化工学院，甘肃兰州 730030
^2.环境友好复合材料国家民委重点实验室，甘肃兰州 730030
^3.甘肃省生物质功能复合材料工程研究中心，甘肃兰州 730030
^4.甘肃省高校环境友好复合材料及生物质利用重点实验室，甘肃兰州 730030
^5.北方化学工业股份有限公司，四川泸州 646605

收稿日期:2022-04-29 修回日期:2022-07-03 出版日期:2023-03-15 发布日期:2023-04-10
通讯作者: 苏琼
作者简介:蔡举艳（1997—），女，硕士研究生，研究方向为生物质的综合利用及功能材料的制备。E-mail：2419273474@qq.com。
基金资助:
国家自然科学基金(21968032);甘肃省科技计划(20YF8FA045);中央高校基本科研业务费专项(31920220044);西北民族大学化学学科创新团队建设项目(1110130139);省级一流专业建设项目(2019SJYLZY-08);省级实验教学示范中心项目(2019GSSYJXSFZX-01);甘肃省高校创新创业教育改革项目(2021SJCXCYXM-01);甘肃省教育厅优秀研究生“创新之星”项目(2021CXZX-694)

Research progress on biodegradable foaming materials

CAI Juyan¹^,²^,³^,⁴(), SU Qiong¹^,²^,³^,⁴(), WANG Yanbin¹^,²^,³^,⁴, WANG Hongling¹^,²^,³^,⁴, LIANG Junxi¹^,²^,³^,⁴, WANG Zhongxu¹^,²^,³^,⁴, GUO Li¹^,²^,³^,⁴, ZHAO Libin⁵

^1.School of Chemical Engineering, Northwest Minzu University, Lanzhou 730030, Gansu, China
^2.Key Laboratory of Environment Friendly Composite Materials of the State Ethnic Affairs Commission, Lanzhou 730030, Gansu, China
^3.Gansu Provincial Biomass Functional Composite Materials Engineering Research Center, Lanzhou 730030, Gansu, China
^4.Key Laboratory of Utility of Environmental Friendly Composite Materials and Biomass in Universities of Gansu Province, Lanzhou 730030, Gansu, China
^5.Northern Chemical Industry Co. , Ltd. , Luzhou 646605, Sichuan, China

Received:2022-04-29 Revised:2022-07-03 Online:2023-03-15 Published:2023-04-10
Contact: SU Qiong

摘要/Abstract

摘要：

大量以石化资源为原料的传统有机泡沫材料的使用加剧了此类资源的枯竭，且其废弃物于自然环境中难以降解，严重污染环境。与此相比，可生物降解泡沫具有生物相容性、生物降解性和可再生性，是一种环境友好材料，受到了世界各国的广泛关注。本文对比了挤出发泡、模压发泡和冷冻干燥发泡3种常见可生物降解泡沫材料的发泡工艺及原理、应用及优缺点，介绍了发泡工艺对材料性能及应用的影响，指出利用天然高分子化合物或其他可再生资源模拟天然泡沫的微观化学网络结构制备高性能可生物降解泡沫的工艺具有巨大的发展潜力；综述了天然泡沫、仿生泡沫和生物质泡沫3种泡沫材料的研究现状，重点探讨了草木类、非异氰酸酯类和木质纤维素泡沫材料的研究进展，分析了典型发泡配方及各组分作用，指出绿色介质、提高塑性及配方的进一步开发是未来可生物降解泡沫材料的发展及研究方向。

关键词: 降解, 泡沫材料, 发泡方法, 配方组成, 仿生

Abstract:

The use of a large number of traditional organic foam materials using petrochemical resources as raw materials has aggravated the depletion of such resources and their wastes are difficult to degrade in the natural environment, which seriously pollutes the environment. In contrast, biodegradable foam is biocompatible, biodegradable and renewable, and is an environmentally friendly material that has received extensive attention. This paper compares foaming technologies, principles, applications, advantages and disadvantages of extrusion foaming, molding foaming and freeze-drying foaming, and introduced the influence of foaming process on material properties and application, and thus it has great development potential to prepare high-performance biodegradable foam by using natural polymer compounds or other renewable resources to simulate the microscopic and chemical network structure of natural foam. Then, this review summarizes the related research status on natural foam, bionic green foam and biomass foam, and focused on discussing research progress of plants and wood, non-isocyanate and lignocellulosic foams. Furthermore, the typical foaming formula compositions and functions are analyzed. It is pointed out that the further exploration of green medium, plasticity improving and formula is the future development and research direction of biodegradable foaming materials.

Key words: degradation, foaming materials, foaming technology, formula composition, bionic

中图分类号:

TQ320.1

蔡举艳, 苏琼, 王彦斌, 王鸿灵, 梁俊玺, 王忠旭, 郭丽, 赵利斌. 可生物降解泡沫材料的研究进展[J]. 化工进展, 2023, 42(3): 1457-1470.

CAI Juyan, SU Qiong, WANG Yanbin, WANG Hongling, LIANG Junxi, WANG Zhongxu, GUO Li, ZHAO Libin. Research progress on biodegradable foaming materials[J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1457-1470.

图/表 15

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发泡方法	原理	优缺点	性能特点	应用	参考文献
挤出发泡	物料依次进入进料区、混炼区；加热熔融，气体融入物料，形成气体-聚合物；推进至模具区挤出；快速降压，含有气体的物料区逐渐发泡；冷却、成型	优点：工艺简单、连续；时间短（2~15min）；不需要预成型；黏度、冲击强度和热均质性好缺点：温度高；成本高；孔径难控制；产品中存在残留物	吸声性能高	吸声	[26]
			密度小、热负荷和冷负荷高	低能耗建筑装潢	[27]
			膨胀率高、吸水指数低	轻质缓冲包装	[30]
			孔径大和吸水率高	吸水剂	[31]
模压成型发泡	物料加入模具中；热压、糊化形成厚的糊状物；物料中的水迅速蒸发，糊状物急剧膨胀而发泡；冷却、成型	优点：操作简单；孔隙率高；易于控制孔径和形状缺点：成本较高；制备较厚或较大体积材料时孔径难控制；不适合制备凹陷、侧面斜度等复杂制品	平衡水分能力好、杨氏模量高	半硬质泡沫，食品储藏、保鲜	[28]
			密度较大、热稳定性好、拉伸强度和抗弯强度高	硬质缓冲包装	[33]
			拉伸强度高、热导率低	保温隔热	[34]
冷冻干燥发泡	物料加入模具中；物料低温下快速或缓慢冻结；冷冻干燥，物料中水分子升华；水蒸气逸出发泡	优点：操作简单；孔隙连通均匀；细胞结构由冰晶的大小和分布控制；高冻结速率下形成微孔泡沫，低冻结速率形成介孔泡沫缺点：膨胀率低；孔径不易控制，可能产生片状结构；处理时间长，不适用于所有材料	比表面积大、疏水性好、吸油率高	吸油剂	[29]
			连续三维网络结构、热导率低	保温隔热	[36]
			孔径小、孔隙率高、止血、无毒	药物输送和止血敷料	[37]

发泡方法	原理	优缺点	性能特点	应用	参考文献
挤出发泡	物料依次进入进料区、混炼区；加热熔融，气体融入物料，形成气体-聚合物；推进至模具区挤出；快速降压，含有气体的物料区逐渐发泡；冷却、成型	优点：工艺简单、连续；时间短（2~15min）；不需要预成型；黏度、冲击强度和热均质性好缺点：温度高；成本高；孔径难控制；产品中存在残留物	吸声性能高	吸声	[26]
			密度小、热负荷和冷负荷高	低能耗建筑装潢	[27]
			膨胀率高、吸水指数低	轻质缓冲包装	[30]
			孔径大和吸水率高	吸水剂	[31]
模压成型发泡	物料加入模具中；热压、糊化形成厚的糊状物；物料中的水迅速蒸发，糊状物急剧膨胀而发泡；冷却、成型	优点：操作简单；孔隙率高；易于控制孔径和形状缺点：成本较高；制备较厚或较大体积材料时孔径难控制；不适合制备凹陷、侧面斜度等复杂制品	平衡水分能力好、杨氏模量高	半硬质泡沫，食品储藏、保鲜	[28]
			密度较大、热稳定性好、拉伸强度和抗弯强度高	硬质缓冲包装	[33]
			拉伸强度高、热导率低	保温隔热	[34]
冷冻干燥发泡	物料加入模具中；物料低温下快速或缓慢冻结；冷冻干燥，物料中水分子升华；水蒸气逸出发泡	优点：操作简单；孔隙连通均匀；细胞结构由冰晶的大小和分布控制；高冻结速率下形成微孔泡沫，低冻结速率形成介孔泡沫缺点：膨胀率低；孔径不易控制，可能产生片状结构；处理时间长，不适用于所有材料	比表面积大、疏水性好、吸油率高	吸油剂	[29]
			连续三维网络结构、热导率低	保温隔热	[36]
			孔径小、孔隙率高、止血、无毒	药物输送和止血敷料	[37]

原料	填料	发泡剂	交联剂	成核剂	增塑剂	各组分作用	参考文献
棕榈酸酯纤维素	—	异丁烷	—	滑石粉	异丁烷	棕榈酸酯纤维素具有热塑性，有利于塑化；异丁烷可提高熔体强度；滑石粉可使泡沫的泡孔致密均匀	[25]
玉米淀粉	淀粉酶-镁复合物	水	锌改性壳聚糖	—	—	淀粉酶-镁复合物和锌改性壳聚糖增强淀粉基泡沫的支撑结构，促进大孔前体形成，提高孔隙率和机械强度；合适含水量可提高膨胀率	[31]
纤维素悬浮液（MFC）	—	水、超临界CO₂	聚乙烯醇（PVA）	—	水	MFC与PVA基质复合，提高熔体强度，降低结晶度，有利于加工；水作增塑剂，增加PVA链的迁移率，降低熔融温度；合适含水量可提高膨胀率，超临界CO₂有效促进成核，防止泡孔产生过程中泡孔塌陷	[68]
羟丙基玉米淀粉	纤维素晶体	水	甘油和PVA	—	水	挤出密炼中甘油、PVA与羟丙基玉米淀粉交联，形成三维网络结构；纤维素晶体作成核剂，泡孔均匀，孔壁不易坍塌，提高抗压强度和弹性模量；水作增塑剂，增加PVA链的迁移率；合适含水量可提高膨胀率	[69]
聚乳酸（PLA）	纸浆纤维	异丁烷	环氧扩链剂	滑石粉	—	挤出密炼过程中环氧扩链剂与PLA交联，提高熔体强度；纸浆纤维和异丁烷增大熔体黏度，有利于形成低密度和机械强度高的泡沫；滑石粉使泡沫泡孔致密均匀	[70]

原料	填料	发泡剂	交联剂	成核剂	增塑剂	各组分作用	参考文献
棕榈酸酯纤维素	—	异丁烷	—	滑石粉	异丁烷	棕榈酸酯纤维素具有热塑性，有利于塑化；异丁烷可提高熔体强度；滑石粉可使泡沫的泡孔致密均匀	[25]
玉米淀粉	淀粉酶-镁复合物	水	锌改性壳聚糖	—	—	淀粉酶-镁复合物和锌改性壳聚糖增强淀粉基泡沫的支撑结构，促进大孔前体形成，提高孔隙率和机械强度；合适含水量可提高膨胀率	[31]
纤维素悬浮液（MFC）	—	水、超临界CO₂	聚乙烯醇（PVA）	—	水	MFC与PVA基质复合，提高熔体强度，降低结晶度，有利于加工；水作增塑剂，增加PVA链的迁移率，降低熔融温度；合适含水量可提高膨胀率，超临界CO₂有效促进成核，防止泡孔产生过程中泡孔塌陷	[68]
羟丙基玉米淀粉	纤维素晶体	水	甘油和PVA	—	水	挤出密炼中甘油、PVA与羟丙基玉米淀粉交联，形成三维网络结构；纤维素晶体作成核剂，泡孔均匀，孔壁不易坍塌，提高抗压强度和弹性模量；水作增塑剂，增加PVA链的迁移率；合适含水量可提高膨胀率	[69]
聚乳酸（PLA）	纸浆纤维	异丁烷	环氧扩链剂	滑石粉	—	挤出密炼过程中环氧扩链剂与PLA交联，提高熔体强度；纸浆纤维和异丁烷增大熔体黏度，有利于形成低密度和机械强度高的泡沫；滑石粉使泡沫泡孔致密均匀	[70]

原料	填料	发泡剂	交联剂	增塑剂	脱模剂及其他助剂	各组分作用	参考文献
淀粉	纤维素	水	柠檬酸	—	棕榈蜡作为脱模剂，次亚磷酸钠作为催化剂	热压过程中柠檬酸、淀粉、纤维素在次亚磷酸钠作用下交联，提高机械强度和弹性模量；合适含水量可形成均匀泡孔；棕榈蜡有利于脱模	[33]
木质素（EL）	—	水	BCC、二聚体脂肪二胺（priamine）	—	—	热压阶段BCC、priamine与EL交联、氨甲酰化，形成可裂解动态共价网络，赋予泡沫自修复性和热再加工性；合适含水量可形成均匀泡孔	[49]
玉米淀粉	—	碳酸氢钠、偶氮二甲酰胺	三偏磷酸钠	甘油	液体石蜡作为脱模剂，丙烯酸甲酯和乙酸乙烯酯作为改性剂	热压阶段三偏磷酸钠与淀粉交联，丙烯酸甲酯、乙酸乙烯酯、淀粉接枝共聚，降低结晶度，形成均匀胶体，提高泡沫力学性能，增强韧性；碳酸氢钠、偶氮二甲酰胺受热分解产生泡孔；甘油有利于塑化；液体石蜡有利于脱模	[66]
淀粉	甘蔗渣	水	—	甘油	硬脂酸镁作为脱模剂	甘蔗渣和甘油使淀粉具有流变性，防止泡孔崩塌降低吸水能力，提高伸长率；合适含水量可形成均匀泡孔；硬脂酸镁有利于脱模	[71]
淀粉	纤维素、碳酸钙	水	PLA、瓜尔豆胶	—	硬脂酸镁用作脱模剂，硅酸镁用作填充剂	热压阶段PLA、瓜尔豆胶与淀粉交联，调节黏度，有利于塑化，提高弹性模量；物料中羧基或羟基作用，产生相容界面；硅酸镁作填充剂，有利于提高弯曲强度；合适含水量可形成均匀泡孔；硬脂酸镁有利于脱模	[72]
玉米芯纤维	木薯粉	水	PVA	山梨醇	硬脂酸镁用作脱模剂	添加PVA有利于形成坚韧、有弹性的泡沫；山梨醇作增塑剂，提高物料热均质性和防水性，形成均匀泡孔，改善泡沫综合性能；木薯粉提高泡沫抗压强度；合适含水量形成均匀泡孔；硬脂酸镁有利于脱模	[73]

可生物降解泡沫材料的研究进展

Research progress on biodegradable foaming materials

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原料	发泡剂	交联剂	各组分作用	参考文献
碱处理的天然木块	水	甲基三甲氧基硅烷（MTMS）	MTMS对碱预处理木块疏水改性，利于提高回弹率、抗压强度和疏水性；水升华形成微孔泡沫	[45]
肼基改性纤维素纳米晶（CNC-NHNH₂）	水	端醛基聚乙二醇（OHC-PEG-CHO）	CNC-NHNH₂与OHC-PEG-CHO交联，形成坚韧的网络孔隙结构，提高泡沫力学强度，吸水后提高弹性模量；水升华形成微孔泡沫	[56]
木质纤维素	水	1-烯丙基-3-甲基咪唑氯化物/二甲基亚砜（AmimCl/DMSO）共溶剂	AmimCl/DMSO降低物料黏度，形成物理交联网络结构，提高机械强度；水升华形成微孔泡沫	[62]
纤维素纳米纤维（CNF）	水	N-羟甲基二甲基膦丙酰胺（MDPA）、1,2,3,4-丁烷四羧酸（BTCA）、次亚磷酸钠（SHP）或PVA、聚磷酸铵（MCAPP）	BTCA上的羧基在SHP作用下与CNF、MDPA上羟基酯化，赋予材料柔韧性和回弹性，水升华形成微孔泡沫或CNF链羟基与PVA链羟基形成氢键，与MCAPP链形成酯键，提高杨氏模量	[8,74]
魔芋葡聚糖、马铃薯淀粉、麦秸秆	水	明胶	添加马铃薯淀粉有利于提高泡沫机械强度；麦秸杆减小泡沫孔径；明胶防止麦秸秆沉降，改善隔热性能；水升华形成微孔泡沫	[75]
微晶纤维素悬浮液	水	N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基硅烷（AEAPDMS）、氯化钙	氯化钙使泡孔不易坍塌；微晶纤维素悬浮液与AEAPDMS接枝产生低收缩率和高比表面积泡沫；水升华形成微孔泡沫	[76]

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