Article(id=1320881091876073548, tenantId=1146029695717560320, journalId=1260987677001138203, issueId=1320880625310085394, articleNumber=null, orderNo=null, doi=10.13386/j.issn1002-0306.2025080246, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1756051200000, receivedDateStr=2025-08-25, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1792852193087, onlineDateStr=2026-10-24, pubDate=1788192000000, pubDateStr=2026-09-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792852193087, onlineIssueDateStr=2026-10-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792852193087, creator=13701087609, updateTime=1792852193087, updator=13701087609, issue=Issue{id=1320880625310085394, tenantId=1146029695717560320, journalId=1260987677001138203, year='2026', volume='47', issue='17', pageStart='1', pageEnd='596', issueExtLink='null', onlineDate='null', pubDate='1788192000000', pubDateStr='2026-09-01', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792852081848, creator='13701087609', updateTime=1792852081848, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext=null, issueFiles=null, downloadFileDto=null}, startPage=159, endPage=165, ext={EN=ArticleExt(id=1320881092173869133, articleId=1320881091876073548, tenantId=1146029695717560320, journalId=1260987677001138203, language=EN, title=Influence of Different Contents of Polyhydroxy Polymers on the Performance of Polyethylene Spontaneous Modified Atmosphere Packaging Films, columnId=1261336277291548795, journalTitle=Science and Technology of Food Industry, columnName=Research and Investigation, runingTitle=null, highlight=null, articleAbstract=

The low gas barrier and water vapor permeability of polyethylene (PE) packaging film limit the regulation of respiratory metabolism and humidity within the packaging environment. Consequently, this can accelerate the aging and mold growth of fruits and vegetables. To enhance the gas barrier properties and water vapor transmission rate of PE bags, in this study, PE served as the base material, with varying amounts of polyhydroxy polymers incorporated. The composite films (P0, P2, P4, P6, P8) were prepared via melt blending and granulation blow film processes. Their structure, crystallinity, optical properties, mechanical properties, and barrier performance were characterized to identify the optimal formulation for spontaneous modified atmosphere packaging films. The results indicated that the P4 composite film exhibited increases of 82.38% and 222.84% in elongation at break (transverse direction) and water vapor permeability, respectively, compared to the PE film. Its contact angle, carbon dioxide and oxygen permeability decreased by 21.46%, 10.59% and 34.24%, respectively. In summary, the P4 composite film demonstrates excellent gas barrier properties and water vapor permeability. Its composition can readily create an environment characterized by low oxygen, high carbon dioxide, and low humidity, providing a theoretical basis for developing fruit and vegetable preservation films.

, authors=Daoye CHEN, Fanwei DAI, Yingbin PAN, Feiping CHEN, Ling WANG, Yulong CHEN*, authorsList=Daoye CHEN, Fanwei DAI, Yingbin PAN, Feiping CHEN, Ling WANG, Yulong CHEN, authorCompany=null, correspAuthors=Yulong CHEN, authorNote=null, correspAuthorsNote=null, copyrightStatement=Copyright © 2026 Science and Technology of Food Industry. All rights reserved., copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1320881094405238877, articleId=1320881091876073548, tenantId=1146029695717560320, journalId=1260987677001138203, language=CN, title=不同多羟基聚合物含量对聚乙烯自发气调包装膜性能的影响, columnId=1261336277849391232, journalTitle=食品工业科技, columnName=研究与探讨, runingTitle=null, highlight=null, articleAbstract=

聚乙烯(Polyethylene,PE)包装膜的气体阻隔性和水蒸气透过率低,不利于调节果蔬的呼吸代谢及内包装环境的湿度,容易加速果蔬的衰老、长霉。为了提高PE袋的气体阻隔性、水蒸气透过率,本研究以PE为基材,添加不同量的多羟基聚合物,采用熔融共混合造粒吹膜工艺得到P0、P2、P4、P6、P8复合膜,对其结构、结晶度、光学、力学及阻隔性能进行测试,得到自发气调包装膜的最佳配方。结果表明,P4复合膜的断裂伸长率(横向)、水蒸气透过量较PE膜分别提升82.38%、222.84%,接触角、二氧化碳透过量、氧气透过量分别下降21.46%、10.59%、34.24%。综上所述,P4复合膜具有高气体阻隔性和水蒸气透过率,膜内容易形成低氧、高二氧化碳及低湿度的环境,为果蔬保鲜膜的研发提供理论基础。

, authors=陈道业, 戴凡炜, 潘颖斌, 陈飞平, 王玲, 陈于陇*, authorsList=陈道业, 戴凡炜, 潘颖斌, 陈飞平, 王玲, 陈于陇, authorCompany=null, correspAuthors=陈于陇, authorNote=

陈道业(1989−),男,硕士,实习研究员,研究方向:农产品贮藏与加工,E-mail:

, correspAuthorsNote=
陈于陇(1968−),男,博士,研究员,研究方向:农产品保鲜与物流,E-mail:。
, copyrightStatement=版权所有 © 2026《食品工业科技》编辑部, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=04QuwMbvPtNvMzqdFnNktg==, magXml=DqgaQistHCtdIQW9kH+2Dw==, pdfUrl=null, pdf=xRBUC3R1eRZS/SXvDv3IRg==, pdfFileSize=1800714, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=QRUBTOXE4C6VjuhJAXK7aA==, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=UXydvQlrdmn0ZaylmlqXMg==, mapNumber=null, fund=null)}, authors=[Author(id=1320881571096277646, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881091876073548, orderNo=0, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=1169989884@qq.com, emailSecond=null, emailThird=null, correspondingAuthor=0, authorType=1, ext={EN=AuthorExt(id=1320881571180163728, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881091876073548, authorId=1320881571096277646, language=EN, stringName=Daoye CHEN, firstName=Daoye, middleName=null, lastName=CHEN, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=null, address=Sericultural & Agri-Food Research Institute Guangdong Academy of Agricultural Sciences, Key Laboratory of Functional Foods, Ministry of Agriculture and Rural Affairs, Guangdong Key Laboratory of Agricultural Products Processing, Guangzhou 510610, China, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1320881571247272593, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881091876073548, authorId=1320881571096277646, language=CN, stringName=陈道业, firstName=null, middleName=null, lastName=null, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=null, address=广东省农业科学院蚕业与农产品加工研究所/农业农村部功能食品重点实验室/广东省农产品加工重点实验室,广东广州 510610, bio={"content":"

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注:a~e分别代表P0、P2、P4、P6、P8膜的SEM图。

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注:图中小写字母表示处理组间差异显著(P<0.05),图5~图7同。

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Melting temperatures and relative crystallinities of different composite films

, figureFileSmall=null, figureFileBig=null, tableContent=
样品名熔融温度Tm(℃)相对结晶度XC(%)
P0114.540.96
P2114.242.66
P4113.944.36
P6113.646.08
P8113.347.78
), ArticleFig(id=1320881576158802629, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320881091876073548, language=CN, label=表1, caption=

不同复合膜的熔融温度及相对结晶度

, figureFileSmall=null, figureFileBig=null, tableContent=
样品名熔融温度Tm(℃)相对结晶度XC(%)
P0114.540.96
P2114.242.66
P4113.944.36
P6113.646.08
P8113.347.78
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不同多羟基聚合物含量对聚乙烯自发气调包装膜性能的影响
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陈道业 , 戴凡炜 , 潘颖斌 , 陈飞平 , 王玲 , 陈于陇 *
食品工业科技 | 研究与探讨 2026,47(17): 159-165
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食品工业科技 |研究与探讨 2026 , 47 (17) : 159 -165
不同多羟基聚合物含量对聚乙烯自发气调包装膜性能的影响
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陈道业(1989−),男,硕士,实习研究员,研究方向:农产品贮藏与加工,E-mail:

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陈道业 , 戴凡炜, 潘颖斌, 陈飞平, 王玲, 陈于陇*
作者信息
  • 广东省农业科学院蚕业与农产品加工研究所/农业农村部功能食品重点实验室/广东省农产品加工重点实验室,广东广州 510610
通讯作者:
陈于陇(1968−),男,博士,研究员,研究方向:农产品保鲜与物流,E-mail:。
作者简介:

陈道业(1989−),男,硕士,实习研究员,研究方向:农产品贮藏与加工,E-mail:

Influence of Different Contents of Polyhydroxy Polymers on the Performance of Polyethylene Spontaneous Modified Atmosphere Packaging Films
Daoye CHEN , Fanwei DAI, Yingbin PAN, Feiping CHEN, Ling WANG, Yulong CHEN*
Affiliations
  • Sericultural & Agri-Food Research Institute Guangdong Academy of Agricultural Sciences, Key Laboratory of Functional Foods, Ministry of Agriculture and Rural Affairs, Guangdong Key Laboratory of Agricultural Products Processing, Guangzhou 510610, China
出版时间: 2026-09-01 doi: 10.13386/j.issn1002-0306.2025080246
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聚乙烯(Polyethylene,PE)包装膜的气体阻隔性和水蒸气透过率低,不利于调节果蔬的呼吸代谢及内包装环境的湿度,容易加速果蔬的衰老、长霉。为了提高PE袋的气体阻隔性、水蒸气透过率,本研究以PE为基材,添加不同量的多羟基聚合物,采用熔融共混合造粒吹膜工艺得到P0、P2、P4、P6、P8复合膜,对其结构、结晶度、光学、力学及阻隔性能进行测试,得到自发气调包装膜的最佳配方。结果表明,P4复合膜的断裂伸长率(横向)、水蒸气透过量较PE膜分别提升82.38%、222.84%,接触角、二氧化碳透过量、氧气透过量分别下降21.46%、10.59%、34.24%。综上所述,P4复合膜具有高气体阻隔性和水蒸气透过率,膜内容易形成低氧、高二氧化碳及低湿度的环境,为果蔬保鲜膜的研发提供理论基础。

聚乙烯  /  自发气调  /  包装膜  /  透气性  /  透水性

The low gas barrier and water vapor permeability of polyethylene (PE) packaging film limit the regulation of respiratory metabolism and humidity within the packaging environment. Consequently, this can accelerate the aging and mold growth of fruits and vegetables. To enhance the gas barrier properties and water vapor transmission rate of PE bags, in this study, PE served as the base material, with varying amounts of polyhydroxy polymers incorporated. The composite films (P0, P2, P4, P6, P8) were prepared via melt blending and granulation blow film processes. Their structure, crystallinity, optical properties, mechanical properties, and barrier performance were characterized to identify the optimal formulation for spontaneous modified atmosphere packaging films. The results indicated that the P4 composite film exhibited increases of 82.38% and 222.84% in elongation at break (transverse direction) and water vapor permeability, respectively, compared to the PE film. Its contact angle, carbon dioxide and oxygen permeability decreased by 21.46%, 10.59% and 34.24%, respectively. In summary, the P4 composite film demonstrates excellent gas barrier properties and water vapor permeability. Its composition can readily create an environment characterized by low oxygen, high carbon dioxide, and low humidity, providing a theoretical basis for developing fruit and vegetable preservation films.

polyethylene  /  modified atmosphere  /  packaging film  /  air permeability  /  water permeability
陈道业, 戴凡炜, 潘颖斌, 陈飞平, 王玲, 陈于陇. 不同多羟基聚合物含量对聚乙烯自发气调包装膜性能的影响. 食品工业科技, 2026 , 47 (17) : 159 -165 . DOI: 10.13386/j.issn1002-0306.2025080246
Daoye CHEN, Fanwei DAI, Yingbin PAN, Feiping CHEN, Ling WANG, Yulong CHEN. Influence of Different Contents of Polyhydroxy Polymers on the Performance of Polyethylene Spontaneous Modified Atmosphere Packaging Films[J]. Science and Technology of Food Industry, 2026 , 47 (17) : 159 -165 . DOI: 10.13386/j.issn1002-0306.2025080246
食品包装是新鲜农产品加工的最后一道工序,可以保护产品,提高其商品价值。包装与冷链管理相结合,可以保持新鲜产品的质量并延长其保质期[1]。气调包装是一种常用的保鲜方法,而自发气调因操作简单、安全性高、成本低等优势受到广泛关注。自发气调的关键在于选择合适的包装保鲜袋,使包装材料的气体渗透性与产品的呼吸速度相适应,自动调节包装内部的湿度、气体成分及比例,从而达到保鲜的效果[2]。
气调包装袋的材料、厚度直接影响其透气性和透湿性,从而影响果蔬保鲜效果。聚乙烯(Polyethylene,PE)化学性质稳定,无色无味、成本低、加工性能优良、轻便且柔韧、容易回收再利用,是重要的气调包装膜材料[3]。但PE的低氧气阻隔性不利于果蔬的自发气调呼吸,高水蒸气阻隔性容易引起果蔬腐烂,限制了其在食品包装材料中的应用。因此,提高PE膜氧气阻隔性及水蒸气透过量有利于保持果蔬的贮藏品质。研究表明,气体小分子在聚合物中的渗透行为是物理吸附过程,其与聚合物的链结构、结晶度、链的取向和堆砌直接相关[4],可通过聚合物共混、涂布技术等增加基质中的结晶区域,形成气体无法直接渗透的屏障,减缓氧气在基体中的渗透速率,提高材料的氧气阻隔性能[5]。李娟华等[6]将纳米CaCO3、纳米SiO2添加到PE中制备CaCO3/SiO2/PE复合膜,以提高PE膜的气体阻隔性,延长鲜海带的保鲜期。付宇杰[7]用1.0wt%衣康酸(IA)对聚乙烯醇(PVA)涂布液进行改性,制备了PVA-IA/PE涂布膜,有效提高了PE膜的氧气阻隔性,形成低O2、高CO2的环境,调节果蔬的呼吸强度。PE膜不含极性基团,其表面亲水性差,不利于水蒸气的渗透,可通过亲水改性提高水蒸气透过量。Praveen等[8]将沸石添加至低密度聚乙烯(LDPE)中得到LDPE-沸石复合膜,其可以主动改变包装内气体的湿度和成分,从而抑制微生物的呼吸和生长,延长果蔬的贮藏期。郑丽霞[9]通过空气等离子体引发聚乙烯薄膜表面接枝丙烯酸单体进行改性,引入亲水性自由基,提高PE的亲水性。因此,加入增加PE结晶区域且含有极性基团的材料对PE进行改性能同时提高其氧气阻隔性及水蒸气透过量。
多羟基聚合物是一种由丙三醇、聚乙烯醇等组成的可降解复合材料,无毒无味,适用于食品包装领域,其分子链中含有大量亲水基团,且是重要的氧气阻隔材料。王文涛[10]在PE膜中添加淀粉和聚乙烯醇改善淀粉基纳米复合膜的阻水、阻气和亲水性能。鲍慧娟[11]研究壳聚糖-PE双层抑菌保鲜膜发现,添加0.94%壳聚糖能将保鲜膜的水蒸气透过率提升至38.45 g/(m2·24 h),氧气透过率降至6767.63 cm3/(m2·24 h·atm),有助于形成低O2、高CO2的环境,延长果蔬的货架期。然而,也有研究指出,多羟基聚合物容易吸水发生溶胀,阻塞通道,反而削弱复合膜透水性能[12]。多羟基聚合物在PE膜中呈现复杂的双重效应,其调控机理尚需进一步研究。本文以PE为基材,分别添加0、2%、4%、6%、8%多羟基聚合物对PE膜进行改性,研究复合膜的微观结构、傅里叶红外光谱图、力学性能、透水透气性能等的变化规律,为改善PE膜的透水性,提高其气体阻隔性提供理论依据。
DFDA-7042线型聚乙烯(LLDPE)、2426K低密度聚乙烯(LDPE) 中国石油化工股份有限公司茂名分公司;丙三醇 天津市富宇精细化工有限公司;聚乙烯醇1788 上海影佳实业发展有限公司。
TDS-20同向双螺杆挤出机 南京鸿铭挤出设备有限公司;JYC-28小型吹膜实验机 佛山市金中河机械有限公司;Merlin场发射扫描电子显微镜 德国蔡司公司;VERTEX 70型傅里叶变换红外光谱仪 德国布鲁克公司;BSG-11A气体透过率测试仪、W-B-31E水蒸气透过率测试仪(杯式法)、STR-300A智能电子拉力试验机 广州西唐机电科技有限公司;UV-1900i紫外分光光度计 日本岛津公司;DSA100接触角测试仪 德国克吕士公司;DSC 21400A-0318-L差示扫描量热仪 德国耐驰公司。
PE复合膜的制备参考王文涛[10]的方法并作修改。将LLDPE与LDPE按1:1混合均匀得到PE胶粒,再分别将0、2%、4%、6%、8%多羟基聚合物材料加入到PE胶粒中,混合均匀,分别通过双螺杆挤出机(一区~六区机头温度分别为175、185、195、195、195、200、200 ℃,主机频率为28 Hz)造粒,小型吹膜实验机吹膜(一区~五区温度分别为195、195、200、200、200 ℃),得到的PE复合膜(复合膜的厚度约为0.025 mm)分别命名为P0、P2、P4、P6、P8。
用扫描电镜(SEM)对复合膜的截面形貌进行表征。将PE复合膜用液氮脆断,喷金,在15 kV工作电压下对样品形貌进行表征。
利用差示扫描热量仪对复合膜的结晶和熔融行为进行表征[13]。称取5 mg试样,密封于标准铝制坩埚。温度程序设置分为两个阶段:初始阶段以10 ℃/min的升温速率将体系从25 ℃加热至250 ℃后恒温5 min;第二阶段以相同速率程序降温至25 ℃后恒温5 min,完成材料再结晶过程,记录DSC曲线。测试过程均在氮气气氛中进行。薄膜材料的相对结晶度根据以下公式进行计算。
$\rm \text{Xc}(\text{%})=\frac{{\Delta{H}}_{\text{f}}}{{\Delta H}_{\text{f}}^{0}}\times 100 $
式中,Xc表示相对结晶度,%;∆Hf表示测得的熔融焓,J/g;$ \Delta \mathrm{H}_{\mathrm{f}}^{0} $聚乙烯全结晶参照基准值(293 J/g)。
利用傅里叶变换红外光谱仪进行测试,将样品干燥24 h后,溴化钾压片,以4 cm−1的分辨率和4000~400 cm−1的波数范围对复合膜表面官能团进行表征。
复合膜的透光性能依据GB/T 2410-2008[14],使用紫外-可见分光光度计在475 nm处测得复合膜的吸光度(A),按以下公式计算透光率(T):
$ \text{T}={0.1}^{\text{A}} $
复合膜的力学性能通过智能电子拉力试验机,参照GB/T 1040.1-2018[15]进行测定。复合膜测试条的尺寸为2×10 cm,拉伸间距为5 cm,拉伸速率1000 mm/min。
复合包装膜的透气性能通过BSG-11A气体透过率测定仪,参照GB/ T 1038-2000[16],采用压差法进行测定。复合膜测试样品的直径为95 mm,测试条件为23 ℃、相对湿度(RH)90%。
复合膜亲水性的测试参考GB/T 30693-2014[17],测定膜与水的接触角。将复合膜平整地置于测试仪观测台上,从针头处挤出约2 μL去离子水于复合膜表面,静置3 s后记录分析复合膜的接触角。
复合膜的透湿性能测试通过W-B-31E水蒸气透过率测定仪,参照国家标准 GB/T 1037-2021[18],采用杯式法进行测定。复合膜测试样品的直径为77 mm,测试条件为38 ℃、相对湿度(RH)90%。
所描述的所有实验均为三次重复。数据统计使用Microsoft Excel 2010完成,图表绘制使用Origin 2025完成,处理组间显著性分析借助SPSS 25.0软件完成。图中不同小写字母表示处理组间差异显著(P<0.05)。
图1(a~e)显示出PE复合膜的颗粒感随着多羟基聚合物添加量的增加而增强。图1(a)显示出纯PE膜表面相对平整光滑,有明显的拉伸纹理,整体结构致密,颗粒性较弱。表明纯PE膜具有较强的延展性,有利于其力学性能;但其表面粗糙度较低,缺乏微观孔洞结构,对水蒸气阻隔性能较强。当加入2%多羟基聚合物后,复合膜表面纹理变粗糙,开始出现细微颗粒状突起,改变了膜的微观结构(图1(b));随着多羟基聚合物添加量的增加,复合膜表面由平滑逐渐变得粗糙,颗粒明显增多,形成微孔结构,对改善水汽阻隔性等有积极作用,但会降低部分力学强度[19]。这种变化表明多羟基聚合物对复合膜微观结构有明显的调控作用,尤其对膜的亲水性、透湿性、透气性、机械强度有重要影响。
多羟基聚合物的引入改变PE原有的结构,从而影响复合膜的熔融与结晶行为。不同多羟基聚合物含量复合膜的DSC曲线与数据分别如图2和表1所示。P0的相对结晶度、熔融温度分别为40.96%、114.5 ℃,随着多羟基聚合物添加量的增加,复合膜的相对结晶度呈上升的变化趋势,而熔融温度则呈下降的变化规律。这是由于均匀分散的多羟基聚合物可作为异相成核剂,大幅增加PE的成核位点,形成更多的小晶核,提高结晶速率。但小晶体的表面自由能较高,热力学稳定性较差,熔化所需的能量减少,界面能降低,熔融温度下降[20]。且多羟基聚合物与PE存在极性差异,界面相容性差,晶体内部有序性下降,引起链折叠缺陷,熔融温度下降。
不同PE复合膜的傅里叶红外光谱图如图3所示,所有处理组均在2922.3 cm−1和2850.8 cm−1处显示出强吸收峰,分别属于-CH2的不对称伸缩振动和对称伸缩振动,这是PE典型的官能团特征。五个处理组在此区域的峰位基本一致,说明PE链结构稳定,复合过程中主链并未发生降解或交联。吸收峰强度随多羟基聚合物添加量的增加略有下降,可能是引入的极性基团(-OH)与PE的非极性链段发生物理缠结或分散[21],降低了链段的自由度和伸缩活性,使得该处的吸收强度下降,说明材料内部结构由单一的晶态向更复杂的非晶-晶态混合结构转变,增强复合膜的抗疲劳能力。
所有处理组均在1463.3 cm−1处显示出强吸收峰,该吸收峰是PE碳链弯曲振动的重要信号,与聚合物链段的密集堆积和局部结构相关联,表明PE的主要链结构在引入多羟基聚合物后没有被破坏。但该处峰形随多羟基聚合物添加量的增加而出现展宽和波动,这可能是多羟基聚合物的引入稀释了PE亚甲基的密度,通过链间相互作用调节链段柔顺性,从而影响其弯曲振动,增强材料的柔性。
1379.8 cm−1处的吸收峰主要反映-CH3或-CH(OH)弯曲振动,P0在此处的吸收峰较弱(主要由PE末端CH3引起),但其他处理组的吸收峰随着多羟基聚合物添加量的增加逐渐增强,表明该峰主要源自多羟基聚合物结构中含氧官能团的基团振动。
719.4 cm−1波段是PE结晶区最典型的吸收特征之一,被广泛用于表征PE材料的结晶度。P0在此处的吸收峰清晰、强烈。随着多羟基聚合物添加比例上升,该处吸收峰呈先减弱后增强的变化规律,这是由于PE与多羟基聚合物之间的非共融性造成链段规整度下降,晶区尺寸降低。多羟基聚合物的引入破坏了原本高度有序的晶体结构,使材料逐渐转变为非晶相主导或半晶态结构,从而增加材料的韧性及可塑性[22]。
不同复合膜的透光率如图4所示。P0的透光率为91.70%,随着多羟基聚合物的含量增加,复合膜的透光率呈下降的变化趋势,P8的透光率降至84.86%,各处理组间差异显著(P<0.05)。这种现象由多羟基聚合物与PE基材的折射率差异致光散射引起,且散射效应随多羟基聚合物含量的增加而增强,透光率则相应降低[23]。多羟基聚合物含量增加,其聚集成大颗粒或团簇加剧光散射,同时也增加膜的粗糙程度。多羟基聚合物粒子聚集程度越高,复合膜表面越粗糙,越不利于光线穿透,其透光率越低[24]。这一研究结果与李海朝等[25]对甲壳素/明胶复合膜的研究结论相一致,多羟基聚合物与基底的相互作用减少膜有序排列的网络结构,增加对光的散射,降低光的透过率[26]。
不同多羟基聚合物含量PE复合膜的力学性能如图5所示。复合膜的纵向、横向拉伸强度均呈下降的变化趋势(图5A)。P0膜的纵向、横向拉伸强度分别为17.84、14.59 MPa,而P8膜的纵向、横向拉伸强度分别降至13.01、10.83 MPa,这可能与相界面结合力有关。PE与多羟基聚合物为不同极性的物质,两者相容性差,直接共混时容易形成宏观相分离,界面结合力弱,外力作用下界面处容易开裂,导致拉伸强度下降[27−28]。图5A中P2、P4的纵向拉伸强度差异不显著,P0、P2、P4的横向拉伸强度差异不显著。因此,加入4%多羟基聚合物对PE膜拉伸强度的下降趋势影响并不显著。
复合膜的纵向、横向断裂伸长率呈上升的变化趋势(图5B)。P0膜的纵向、横向断裂伸长率分别为296.36%、274.46%,而P8膜的纵向、横向断裂伸长率分别升至637.54%、595.27%。这与多羟基聚合物的化学性质有关,多羟基聚合物分子链含有大量羟基,其亲水性和柔性起到增塑剂的作用,降低PE分子链间的内摩擦,使链段更容易滑移,从而提升延展性。多羟基聚合物与PE也能通过氢键或界面偶联形成部分相容的相态作为应力集中点的能量耗散中心,吸收能量,提升复合膜的韧性。复合膜韧性的提升与结晶度也有关,加入多羟基聚合物会影响纯PE膜的分子链紧密排列,非晶区比例增加,分子链自由体积更大,链段活动性增强。拉伸时,非晶区的分子链通过解缠结、取向、滑移吸收能量,提升塑性变形能力[28]。如图5B所示,加入多羟基聚合物后,复合膜纵向、横向断裂伸长率均快速上升,P4与P0的断裂伸长率差异显著(P<0.05)。但复合膜纵向、横向拉伸强度却随着多羟基聚合物的含量增加而下降, 添加量大于4%时其下降速率明显增大。综上所述,P4复合膜同时兼具出色的拉伸强度和断裂伸长率,4%多羟基聚合物添加量为最优用量。
不同多羟基聚合物含量 PE复合膜的气体阻隔性能如图6所示,复合膜的CO2透过量和O2透过量均呈先下降后上升的变化趋势。P0膜的CO2透过量为47386.24 cm3/(m2·24 h·0.1 MPa),P6降至36868.62 cm3/(m2·24 h·0.1 MPa),P8升至36913.46 cm3/(m2·24 h·0.1 MPa);而P0膜的O2透过量为13504.32 cm3/(m2·24 h·0.1 MPa),P4膜降至最低8880.64 cm3/(m2·24 h·0.1 MPa)后上升。这现象与多羟基聚合物的化学性质有关,多羟基聚合物是极性材料,分子链含有大量羟基,能形成氢键网络,对CO2、O2等极性气体具有很好的阻隔性[29],加入多羟基聚合物能显著降低复合膜的透气性。但多羟基聚合物含量超过某一临界比例后,其亲水性可能导致膜吸水溶胀,反而增加CO2、O2的扩散通道,降低复合膜的气体阻隔性[30]。不同复合膜气体阻隔性能先升后降现象与结晶区域密切相关,PE的结晶区对气体有阻隔作用,多羟基聚合物的加入干扰PE的结晶行为,初期多羟基聚合物自身的高阻隔性占优,复合膜气体透过量降低,但过量多羟基聚合物导致非晶区增多,同时也易发生相分离,产生界面缺陷,反而促进气体渗透[31]。作为一款新型的果蔬自发气调包装袋应具备较高的气体阻隔性,更有利于包装袋内形成低O2、高CO2的环境,抑制果蔬呼吸速率,延长贮藏期[32]。如图6B所示,复合膜P4的氧气透过量最小,显著小于P0、P2(P<0.05),能有效阻隔包装袋内外氧气的交换;其二氧化碳透过量较P0显著降低(P<0.05)(图6A),有利于袋内二氧化碳含量的提高,形成低O2、高CO2的环境。综上所述,P4复合膜兼具出色的CO2和O2阻隔性,是一款理想的自发气调包装膜。
接触角是衡量材料表面润湿性的重要指标,不同多羟基聚合物含量 PE复合膜的接触角如图7A所示,复合膜的接触角呈先下降后上升的变化趋势。P0膜的接触角为100.11°,P4降至78.63°后上升。这是由于多羟基聚合物富含羟基,极性较强,可与水分子形成氢键网络,降低表面能,增强亲水性[33];当多羟基聚合物均匀分散在PE基体中时,表面羟基暴露,复合膜接触角显著降低。但当多羟基聚合物的添加量超过某一临界比例后,多羟基聚合物与PE容易发生相分离,形成微米级岛状结构或界面缺陷,复合膜表面粗糙度增加,引发Cassie-Baxter效应[34],导致接触角上升;也有可能是高浓度的多羟基聚合物促进分子链形成更多结晶区,表面羟基被包裹,暴露的极性基团减少,接触角上升。
图7B中复合膜的水蒸气透过量呈先上升后下降的变化趋势。P0膜的水蒸气透过量为11.47 g/(m2·24 h),P4升至37.03 g/(m2·24 h)后下降。这是由于多羟基聚合物的极性基团能吸附水分子,形成氢键网络,促进传输[35],且少量的多羟基聚合物可在复合膜表面偏析,直接暴露羟基,进一步增强膜表面的吸附能力。但当多羟基聚合物的添加量超过某一临界比例后,分子链间氢键增强,形成更多结晶区,导致结晶区包裹部分羟基,减少有效亲水位点[36];过量的多羟基聚合物也会吸湿而过度溶胀,导致结构塌陷,阻塞通道,阻碍水蒸气透过。包装袋内的高湿环境会导致霉菌的繁殖,引起果蔬腐烂。因此,水蒸气透过量高的包装袋更有利于保持袋内干爽的环境,抑制霉菌的生长,延长果蔬的贮藏期。图7A中P4的接触角显著小于其他组分(P<0.05),最有利于水蒸气的吸附;而其水蒸气透过量显著大于其他组分(P<0.05),则最有利于水蒸气的透过。综上所述,P4复合膜兼具出色的亲水性和水蒸气透过能力,是理想的自发气调包装膜。
本文通过研究不同多羟基聚合物含量对PE膜结构、光学、力学及阻隔性能的影响,表明多羟基聚合物的加入使复合膜表面纹理变粗糙,颗粒增多,形成微孔结构,改变了复合膜的微观结构、结晶度、水汽阻隔性等。4%多羟基聚合物复合膜(P4膜)的表面颗粒性增强,透光率、拉伸强度、接触角下降,但其断裂伸长率(横向:500.57%)、CO2阻隔性(42370.02 cm3/(m2·24 h·0.1 MPa))、O2阻隔性(8880.64 cm3/(m2·24 h·0.1 MPa))、水蒸气透过量(37.03 g/(m2·24 h))分别较纯PE膜提升82.38%、10.59%、34.24%、222.84%,对改善水蒸气透过性能、气体阻隔性能等有积极作用。然而,该保鲜膜实际的自发气调效果及透水性能仍需进一步验证。总体而言,该研究为自发气调包装袋的开发、生产制造提供理论基础。

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LI Q Q. Preparation and research on hydrophilic polypropylene microporous membrane[D]. Shanghai: Donghua University, 2021.
2026年第47卷第17期
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doi: 10.13386/j.issn1002-0306.2025080246
  • 接收时间:2025-08-25
  • 首发时间:2026-10-24
  • 出版时间:2026-09-01
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  • 收稿日期:2025-08-25
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    广东省农业科学院蚕业与农产品加工研究所/农业农村部功能食品重点实验室/广东省农产品加工重点实验室,广东广州 510610

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陈于陇(1968−),男,博士,研究员,研究方向:农产品保鲜与物流,E-mail:。
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2种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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