CN111363323B - 一种缓释型抗氧化膜的制备方法与应用 - Google Patents
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Abstract
本发明是涉及食品包装领域,为解决缓释性抗氧化膜中抗氧化剂存在的问题,本发明提出了一种缓释型抗氧化膜的制备方法,基于内部可以进行离子交换的改性膨润土空间网状结构的吸附作用,以绿色的新型油脂抗氧化剂茶多酚棕榈酸酯和高效的氧清除剂抗坏血酸棕榈酸酯作为抗氧化剂,聚乳酸为膜基材,采用双辊筒炼塑法制备得到一种缓释型抗氧化膜。使用天然抗氧化剂衍生物对人体无危害,具有良好的抗氧化性能力,而且氧化膜易降解缓解环境污染问题,可以延长干果的储存时间。
Description
技术领域
本发明是涉及食品包装领域,具体涉及一种在高分子聚合物中加入抗氧化剂制备的缓释型抗氧化膜及其应用。
背景技术
缓释性抗氧化膜是将具有抗氧化能力的食品抗氧化剂分散在包装材料内,从而在一定时间或空间内阻断食品氧化过程的包装材料,常用于保存易氧化腐败食品。现阶段的缓释型抗氧化膜多使用人工合成抗氧化剂,目前市场上使用的油溶性的抗氧化剂主要为特丁基对苯二酚(TBHQ)、丁基羟基茴香醚(BHA)。虽然该类抗氧化剂抗氧化能力强,但是其安全性仍受质疑,具有一定的毒性和致癌作用。合成抗氧化剂会对慢性病患者产生不良反应,长期使用该类抗氧化剂对人体有害,可能引起退行性疾病的发生。同时一些缓释型抗氧化膜无法降解,造成环境污染。随着人们的环保意识增强,该类产品难以满足人们的需求,因此,开发一种新型绿色可降解的缓释型抗氧化膜具有重要意义。
发明内容
为解决缓释性抗氧化膜中抗氧化剂存在的问题,本发明提出了一种缓释型抗氧化膜的制备方法,使用天然抗氧化剂衍生物对人体无危害,具有良好的抗氧化性能力,而且氧化膜易降解缓解环境污染问题。
同时本发明还提出了缓释性抗氧化膜在干果储藏上的应用。
本发明通过以下技术方案实现的:一种缓释型抗氧化膜的制备方法为以下步骤:
(1)膨润土改性;
(1.1)常温下,将膨润土用乙醇配置成质量浓度为30~40%浓度的浆料,制得膨润土浆料;作为优选,用电动搅拌机搅拌18~22min;
(1.2)常温下,将硅烷偶联剂用乙醇配置成质量浓度为0.7~0.9%的溶液,制得硅烷偶联剂溶液;作为优选,用电动搅拌机搅拌15~25min。
(1.3)将(1.2)制成的硅烷偶联剂溶液加入至搅拌中的(1.1)制成的膨润土浆料中,加入后再搅拌40~50min;得到混合溶液;
(1.4)将混合溶液置于30~40℃烘箱中干燥6~8h后,过180~210目标准筛,得到改性膨润土。
上述硅烷偶联剂的使用量为膨润土质量0.8~1.0%。
所述常温为15~25℃。
(2)改性膨润土与抗氧化剂、膜原料共混;
(2.1)将茶多酚棕榈酸酯、抗坏血酸棕榈酸酯、聚乳酸、聚己二酸二乙二醇酯、改性膨润土混合后,倒入炼塑机辊筒之间,启动炼塑机;
茶多酚棕榈酸酯使用量为改性膨润土质量的0.075~0.090%,抗坏血酸棕榈酸酯使用量为改性膨润土质量的0.025~0.030%,聚乳酸使用量为改性膨润土质量的10~12%,聚己二酸二乙二醇酯使用量为改性膨润土质量的0.1~0.4%。
本发明采用的抗氧化剂茶多酚棕榈酸和抗坏血酸棕榈酸酯是天然抗氧化剂衍生物,抗氧化能力强,对人体无危害,具有良好的抗氧化性能力。
因聚乳酸具有无毒易降解的特点,本发明选择聚乳酸作为抗氧化膜的基材,所制备的抗氧化膜对人体危害小且无环境污染等问题,解决目前市场上使用的抗氧化膜大部分是无法降解,容易造成二次白色污染的问题。同时改性的膨润土与有机物聚乳酸有较好的相溶性,可最大程度发挥其缓释作用。
作为优选,所述聚乳酸的分子量为10000~11000,聚合度为130~150。
聚己二酸二乙二醇酯是由己二酸与过量乙二醇酯化生成的饱和聚酯多元醇,是配制聚氨酯涂料用的一种羟基树脂。
作为优选,炼塑机的前后辊的温度设置为100~105℃和98~102℃。
(2.2)包辊效果良好后脱辊,冷却后根据尺寸进行剪裁。
(3)缓释型抗氧化膜的制备。
(3.1)设定平板硫化机温度为105~110℃,预热金属压板,将步骤(2)产物放于两金属压板中央,在1~3MPa压力下预压2~4min;
(3.2)增大压力至10~12MPa,保压8~12min,取出后放入压力成型机中,在4~5MPa压力下保压5~8min,即得缓释型抗氧化膜。
本发明以膨润土与有机物聚乳酸和复合抗氧化剂为原料制备缓释型抗氧化膜,该方法利用改性膨润土空间网状结构的吸附作用以及聚乳酸的成膜性能,同时添加复合抗氧化剂,制备的新型抗氧化膜成膜性好,并且容易降解,对环境无污染。具有良好的抗氧化性并且缓释能力较强,可以延长干果的储存时间。因此所述的缓释型抗氧化膜的制备方法得到的缓释型抗氧化膜在干果储藏期上的应用。可以大大延长干果的贮存时间,减小在包装、运输、储存等过程中因为其被氧化而造成的经济损失。
与现有技术相比,本发明的有益效果是:
(1)缓释型抗氧化膜有良好的抗氧化能力,并且该缓释型抗氧化膜可以被降解;
(2)延长了干果的储存时间,增强了抗氧化膜的韧性,具有良好的缓释性。
附图说明
图1为本发明缓释型抗氧化膜的合成路线图;
图2为本发明的缓释机理示意图;
图3为本发明中聚乳酸的红外谱图;
图4为本发明中膨润土的红外谱图。
具体实施方式
下面通过实施例和附图对本发明作进一步详细说明,实施例中所用原料均可市购或采用常规方法制备。
实施例中聚乳酸的红外谱图如图3所示,在聚乳酸的图谱中,3000cm-1左右处的吸收峰是C-H的伸缩振动吸收峰,1454cm-1处是C-H的弯曲振动峰;1759cm-1处是C=O的伸缩振动峰,表明有羰基存在;1186cm-1、1093cm-1处的强C-O吸收峰证明聚合物中存在酯键,1363cm-1与1384cm-1处的C-H伸缩震动吸收峰证明聚合物中存在甲基;2881cm-1处的伸缩振动峰是由次甲基引起的。
实施例中膨润土的红外谱图如图4所示,膨润土的谱图中,在高频区3631cm-1附近出现Al-OH的伸缩振动吸收峰,在3502cm-1附近出现水分子的H-O-H伸缩振动吸收峰,在中频区1637cm-1附近有水分子的H-O-H弯曲振动吸收峰,这是由于膨润土层间吸附水的存在所致,在1042cm-1附近出现的强吸收峰为Si-O的弯曲振动吸收峰,在822cm-1附近出现的峰是Mg-Al-OH基团引起的振动吸收。
实施例采用如图1所示的合成路线图制备缓释型抗氧化膜。
实施例1
(1)膨润土改性
(1.1)称取50g膨润土,同时称取膨润土质量1.0%的硅烷偶联剂(KH550);
(1.2)常温下将膨润土用乙醇配置成40%质量浓度的浆料,用电动搅拌机搅拌25min。再将硅烷偶联剂用乙醇配置成质量分数为0.9%的溶液,继续搅拌25min,制得硅烷偶联剂溶液;
(1.3)将步骤(1.2)的硅烷偶联剂溶液缓慢均匀加入至膨润土浆料中,加入期间连续不断地缓慢搅拌,至完全加入后再搅拌50min;
(1.4)充分搅拌均匀后将混合溶液置于40℃烘箱中干燥8h,干燥后的填料过210目标准筛。
(2)改性膨润土与抗氧化剂、膜原料共混;
(2.1)将炼塑机的前后辊的温度设置为105℃和102℃,加入改性膨润土50g、茶多酚棕榈酸酯、抗坏血酸棕榈酸酯加入占改性膨润土总质量0.085%、0.025%,加入占改性膨润土总质量10%聚乳酸(分子量为10000,聚合度为130)和改性膨润土质量的0.4%的聚己二酸二乙二醇酯,混合均匀后将其倒入炼塑机辊筒之间,启动炼塑机。
(2.2)包辊效果良好后脱辊,冷却后剪裁合适大小尺寸,装入自封袋中,供压膜用。
(3)缓释型抗氧化膜的制备
(3.1)设定平板硫化机温度为110℃,预热金属压板,取挤出料放于两金属压板中央,3MPa压力下预压4min。
(3.2)增大压力至10MPa,保压12min,取出后放入压力成型机中,在5MPa压力下保压8min,即得缓释型抗氧化膜1。
实施例2
(1)膨润土改性
(1.1)称取55g膨润土,同时称取膨润土质量0.9%的硅烷偶联剂(KH560);
(1.2)常温下将膨润土用乙醇配置成30%质量浓度的浆料,用电动搅拌机搅拌15min。再将硅烷偶联剂用乙醇配置成质量分数为0.8%的溶液,继续搅拌15min,制得硅烷偶联剂溶液。
(1.3)将步骤(1.2)的硅烷偶联剂溶液缓慢均匀加入至膨润土浆料中,加入期间连续不断地缓慢搅拌,至完全加入后再搅拌45min。
(1.4)充分搅拌均匀后将混合溶液置于35℃烘箱中干燥6h后的填料过200目标准筛。
(2)改性膨润土与抗氧化剂、膜原料共混;
(2.1)将炼塑机的前后辊的温度设置为100℃和98℃,加入改性膨润土60g、茶多酚棕榈酸酯、抗坏血酸棕榈酸酯加入占改性膨润土总质量0.09%、0.03%,加入占改性膨润土总质量12%聚乳酸(分子量为10000,聚合度为140)和改性膨润土质量的0.2%的聚己二酸二乙二醇酯,混合均匀后将其倒入炼塑机辊筒之间,启动炼塑机。
(2.2)包辊效果良好后脱辊,冷却后剪裁合适大小尺寸,装入自封袋中,供压膜用。
(3)缓释型抗氧化膜的制备
(3.1)设定平板硫化机温度为107℃,预热金属压板,取挤出料放于两金属压板中央,2MPa压力下预压3min。
(3.2)增大压力至11MPa,保压10min,取出后放入压力成型机中,在4MPa压力下保压7min,即得缓释型抗氧化膜2。
实施例3
(1)膨润土改性
(1.1)称取50g膨润土,同时称取膨润土质量0.8%的硅烷偶联剂(KH570);
(1.2)常温下将膨润土用乙醇配置成35%质量浓度的浆料,用电动搅拌机搅拌20min。再将硅烷偶联剂用乙醇配置成质量分数为0.7%的溶液,继续搅拌20min,制得硅烷偶联剂溶液。
(1.3)将步骤(1.2)的硅烷偶联剂溶液缓慢均匀加入至膨润土浆料中,加入期间连续不断地缓慢搅拌,至完全加入后再搅拌40min。
(1.4)充分搅拌均匀后将混合溶液置于35℃烘箱中干燥7h,干燥后的填料过180目标准筛。
(2)改性膨润土与抗氧化剂、膜原料共混;
(2.1)将炼塑机的前后辊的温度设置为103℃和101℃,加入改性膨润土50g,茶多酚棕榈酸酯、抗坏血酸棕榈酸酯加入占改性膨润土总质量0.085%、0.03%,加入占改性膨润土总质量11%聚乳酸(分子量为11000,聚合度为150)和改性膨润土质量的0.3%的聚己二酸二乙二醇酯,混合均匀后将其倒入炼塑机辊筒之间,启动炼塑机。
(2.2)包辊效果良好后脱辊,冷却后剪裁合适大小尺寸,装入自封袋中,供压膜用。
(3)缓释型抗氧化膜的制备
(3.1)设定平板硫化机温度为105℃,预热金属压板,取挤出料放于两金属压板中央,1MPa压力下预压2min。
(3.2)增大压力至12MPa,保压8min,取出后放入压力成型机中,在5MPa压力下保压6min,即得缓释型抗氧化膜3。
测试例1
将实施例1~实施例3制备的缓释型抗氧化膜进行性能测试,所得数据记录如表1所示。
表1抗氧化膜的性能参数表
性能参数 | 实施例1 | 实施例2 | 实施例3 |
拉伸强度(MPa) | 7.58±0.21 | 8.23±0.14 | 7.62±0.30 |
断裂伸长率(%) | 420.36±30.74 | 453.24±29.36 | 423.39±32.24 |
透氧系数(×10<sup>-15</sup>)cm<sup>3</sup>·cm/cm<sup>2</sup>·s·Pa | 16.12±0.58 | 16.54±0.49 | 16.36±0.136 |
透湿系数(×10<sup>-15</sup>)g·cm/cm<sup>2</sup>·s·Pa | 11.06±0.28 | 10.58±0.12 | 11.65±0.36 |
通过数据分析,本方法制备的3种缓释型抗氧化膜拉伸性能较好,阻氧能力较优。
测试例2
本发明的缓释机理示意图如图2所示;以实施例1为例,对比现有市购的抗氧化膜与放置一年后的香榧各项指标观察其形态特征并测试其缓释时效,所得数据记录如表2所示。
表2抗氧化膜的效果测试
指标 | 普通抗氧化膜 | 实施例1 |
Ph值 | 4.9~5.1 | 6.0~6.2 |
酸值(KOH)/(mg/100g) | 1.23 | 0.86 |
碘值(KOH)/(mg/100g) | 118.6 | 130.2 |
保质期(year) | 0.8 | 1.2 |
抗氧化膜形态 | 棕黑色、致密性一般 | 浅棕色、致密性好 |
比较两者的Ph值、酸值和碘值,实施例1均优于市购的抗氧化膜,说明本发明的抗氧化性较市购抗氧化膜优。
测试例3
将40只体重60±5g的小白鼠随机分成4组,除了空白组对照组外,其他三组分别按0.3g/g、0.45g/g、0.6g/g的实施例1(2.1)中的抗氧化剂与聚乳酸、聚己二酸二乙二醇酯的混料进行灌胃,正常喂食,分别观察灌胃5天、10天、15天、30天小白鼠的活动情况,记录如表3所示。
表3小白鼠活动情况
由结果可知,本发明缓释型抗氧化膜中没有对小白鼠有害的成分,安全性好,无毒。
本方法利用改性膨润土空间网状结构的吸附作用以及聚乳酸的成膜性能,同时聚乳酸有易降解无毒的优点,使用抗氧性强且绿色无毒的聚乳酸和聚己二酸二乙二醇酯作为抗氧化剂,制备的新型抗氧化膜成膜性好,并且容易降解,对环境无污染。
Claims (7)
1.一种缓释型抗氧化膜的制备方法,其特征在于,所述的制备方法为以下步骤:
(1)膨润土改性;
(2)改性膨润土与抗氧化剂、膜原料共混;
(3)缓释型抗氧化膜的制备;
步骤(1)的膨润土改性过程为:将硅烷偶联剂溶液加入到膨润土浆料中混合,然后干燥;
步骤(2)中所用抗氧化剂为茶多酚棕榈酸酯、抗坏血酸棕榈酸酯,茶多酚棕榈酸酯使用量为改性膨润土质量的0.075~0.09%,抗坏血酸棕榈酸酯使用量为改性膨润土质量的0.025~0.030 %;
步骤(2)中所用膜原料为聚乳酸和聚己二酸二乙二醇酯,其中聚乳酸使用量为改性膨润土质量的10 %~12%,聚己二酸二乙二醇酯使用量为改性膨润土质量的0.1~0.4 %;
步骤(3)中缓释型抗氧化膜的制备过程为:
(3.1) 设定平板硫化机温度为 105~110 ℃,预热金属压板,将步骤(2)产物放于两金属压板中央,在1~3 MPa 压力下预压 2~4 min;
(3.2)增大压力至 10~12 MPa,保压 8~12 min,取出后放入压力成型机中,在 4~5 MPa压力下保压 5~8 min,即得缓释型抗氧化膜。
2.根据权利要求1所述的缓释型抗氧化膜的制备方法,其特征在于,所述的步骤(1)具体制备过程为:
(1.1)常温下,将膨润土用乙醇配置成质量浓度为30~40 %浓度的浆料,制得膨润土浆料;
(1.2)常温下,将硅烷偶联剂用乙醇配置成质量浓度为0.7~0.9 %的溶液,制得硅烷偶联剂溶液;
(1.3) 将(1.2)制成的硅烷偶联剂溶液加入至搅拌中的(1.1)制成的膨润土浆料中,加入后再搅拌40~50 min;得到混合溶液;
(1.4)将混合溶液置于 30~40 ℃烘箱中干燥6~8 h后,过180~210目标准筛,得到改性膨润土。
3.根据权利要求1或2所述的缓释型抗氧化膜的制备方法,其特征在于,硅烷偶联剂的使用量为膨润土质量0.8~1.0 %。
4.根据权利要求1所述的缓释型抗氧化膜的制备方法,其特征在于,步骤(2)具体步骤为:
(2.1)将茶多酚棕榈酸酯、抗坏血酸棕榈酸酯、聚乳酸、聚己二酸二乙二醇酯、改性膨润土混合后倒入炼塑机辊筒之间,启动炼塑机;
(2.2)包辊效果良好后脱辊,冷却后根据尺寸进行剪裁。
5.根据权利要求4所述的缓释型抗氧化膜的制备方法,其特征在于,炼塑机的前后辊的温度设置为100~105℃和98~102℃。
6.根据权利要求1或4所述的缓释型抗氧化膜的制备方法,其特征在于,所述聚乳酸的分子量为10000~11000,聚合度为130~150。
7.一种根据权利要求1所述的缓释型抗氧化膜的制备方法得到的缓释型抗氧化膜在干果储藏期保存上的应用。
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