CN114211841A - 一种可降解高阻隔复合膜及其制备方法 - Google Patents
一种可降解高阻隔复合膜及其制备方法 Download PDFInfo
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- CN114211841A CN114211841A CN202111596028.2A CN202111596028A CN114211841A CN 114211841 A CN114211841 A CN 114211841A CN 202111596028 A CN202111596028 A CN 202111596028A CN 114211841 A CN114211841 A CN 114211841A
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Classifications
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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Abstract
本发明公开了一种可降解高阻隔复合膜及其制备方法,该复合膜具有A/B、A/C、A/B/C和A/B/A/C四者之一的层结构,所述A层为改性聚对苯二甲酸‑己二酸丁二酯共聚物,包含以下质量组分:聚对苯二甲酸‑己二酸丁二酯共聚物50‑103份,热塑性淀粉20‑109份,相容剂2‑10份,增粘剂0.5‑10份,辅料1.5‑42份;所述B层为纸或纤维素膜;所述C层为复合材料,包含以下质量组分:全生物降解聚合物40‑150份,增强填料12‑60份,抗静电剂2‑16份,紫外线吸收剂0.1‑15份。本发明复合膜具有良好的阻隔性、较高层间剥离强度,可应用于液态和生鲜类食品的包装领域。
Description
技术领域
本发明涉及一种可降解高阻隔复合膜及其制备方法,属于包装薄膜领域。
背景技术
高阻隔性包装对延长食品、药品和化妆品的保质期和货架期至关重要。为了实现隔水、阻氧、直立、避光、低温热封等多重功能,通常高阻隔包装以铝箔和塑料薄膜为阻隔层,聚乙烯或聚丙烯为热封层和印刷层,纸为中间层,通过干式或挤出复合等工艺形成的复合材料。纸铝塑复合软包装的快速市场化给人们的日常生活提供了极大便捷性,但与此同时,不同材质和特性的复合软包装难以通过物理方式分离和回收,基本属于一次性包材,绝大部分作为一般生活垃圾被填埋或焚烧,给环境带来巨大压力;而用于制备复合包装材料的长纤维纸浆、聚乙烯及优质铝材在使用后仍具有较高使用价值,直接丢弃也造成大量资源浪费。因此,开发新型复合软包装材料具有深远而重要的社会意义及经济价值。
生物可降解复合软包装是将不同材质和功能的全生物降解材料结合,赋予内容物以良好保护特性和美观性的环保包装材料,这类复合软包装废弃后可直接堆埋,在特定堆肥条件下和可表明期限的降解时间内完全降解成生物质,二氧化碳和水,为减少复合塑料软包装碳足迹提供解决方案。
但由于可降解材料自身阻隔性能不够,因此很多技术方案次采用了与传统不可降解材料复合的方案,如CN113427867A公开了一种具有五层复合结构的高阻隔聚乳酸基薄膜,其中外层为高分子量聚乳酸,阻隔层为乙烯-乙烯醇共聚物(EVOH)或乙烯-醋酸乙烯共聚物(EVA),该复合薄膜将可降解材料与高阻隔的传统塑料EVOH相结合。CN112706484A公开了一种高阻隔性聚乙烯醇(PVA)复合薄膜,包括功能层和外层,功能层为多层组装的热塑性聚乙烯醇二维纳米层与EVOH二维纳米层交替结构。这些方案中的EVOH为不可降解材料,所得复合软包装废弃后仍需做分离和回收后处理,不能彻底解决复合软包装造成的塑料污染问题,也使得其中的可降解成份失去了意义。
采用全降解成份,并达到阻隔性能要求的方案也有少量公开报道,但基本都涉及到新研发的专用加工设备,辅以复杂工艺实现,现阶段难以工业化。例如CN112159544A公开了一种三层结构的环保可降解高阻隔薄膜,阻隔层位于两基层中间,阻隔层由碳酸亚丙酯、纳米介孔材料和分散剂构成,基层则由己二酸丁二醇酯-对苯二甲酸丁二醇酯共聚物、增塑剂、聚丙烯酸酯、聚碳酸亚丙酯和聚ε-己内酯/聚乙烯吡咯烷酮共混物组成,通过熔融挤出加工、双向拉伸工艺形成三层共挤出结构膜片。该工艺中为了提高薄膜的拉伸强度采用双向拉伸工艺加工生物可降解薄膜,该工艺和设备价格高昂、工艺复杂,在生物降解薄膜加工领域尚不成熟。
发明内容
本发明的目的是为解决背景技术中的一系列缺点,具体解决了目前食品复合包装领域加工过程复杂,不同材料难回收和价格高昂的问题。
为实现上述目的,第一方面,本发明提供一种可降解高阻隔复合膜,具有A/B、A/C、A/B/C和A/B/A/C四者之一的层结构,所述A层为改性聚对苯二甲酸-己二酸-丁二酯共聚物,包含以下质量组分:聚对苯二甲酸-己二酸丁二酯共聚物50-103份,热塑性淀粉20-109份,相容剂2-10份,增粘剂0.5-10份,辅料1.5-42份;所述B层为纸或纤维素膜;所述C层为复合材料,包含以下质量组分:全生物降解聚合物40-150份,增强填料12-60份,抗静电剂2-16份,紫外线吸收剂0.1-15份。
进一步地,所述热塑性淀粉的增塑剂为甘油、柠檬酸、硬脂酸、甲酰胺、尿素、山梨醇、乙二醇、乙酰柠檬酸三丁酯和环氧大豆油中的至少两种。
进一步地,所述热塑性淀粉的糊化温度为50-120℃。
进一步地,所述相容剂为琥珀酸酐、马来酸酐接枝聚对苯二甲酸-己二酸丁二酯共聚物、乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯、γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、钛酸酯偶联剂中的至少一种。
进一步地,所述增粘剂为乙烯-醋酸乙烯共聚物、乙烯-丙烯酸共聚物、木质素磺酸钠、二苯甲烷二异氰酸酯和杜邦公司的Biomax strong 120中的至少一种。
进一步地,所述全生物降解聚合物为聚羟基脂肪酸酯、聚ε-己内酯、聚丁二酸丁二醇酯、聚丁二酸-己二酸-丁二酯共聚物、聚乳酸-己内酯共聚物、癸二酸聚甘油酯、聚对苯二甲酸-共-丁二酸丁二醇酯和聚碳酸亚丙酯中的至少两种。
进一步地,所述增强填料为碳纳米管、石墨烯、白木质素、纤维素纳米晶体、纳米插层蒙脱土、高岭土、纳米碳酸钙、纤维素纳米晶须、无定形纳米级白炭黑、食品级滑石粉中的至少一种。
进一步地,所述抗静电剂为三羟乙基甲基季铵甲基硫酸盐、十八烷基二甲基季铵硝酸盐、烷基酰胺类非离子型表面活性剂、烷基磷酸酯、烷基硫酸酯、硬脂酰三甲基氯化铵和硬脂酰二甲基戊基氯化铵、(月桂酰胺丙基三甲基胺)硫酸钾酯盐、N,N-双(2-羟乙基)-N-(3’十二烷氧基-2’羟基丙基)甲胺硫酸钾酯盐、三羟乙基甲基季胺硫酸钾酯盐、N,N-十六烷基乙基吗啉硫酸乙酯盐中的至少一种。
进一步地,所述紫外线吸收剂为邻羟基苯甲酸苯酯、2,4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2-羟基-4-正辛氧基二苯甲酮、2-(2’-羟基-3’,5’-二叔苯基)-5-氯化苯并三唑、单苯甲酸间苯二酚酯、2’-2’-硫代双(4-叔辛基酚氧基)镍、三(1,2,2,6,6-五甲哌啶基)亚磷酸酯、4-苯甲酰氧基-2,2,6,6-四甲基哌啶、2,4,6-三(2’正丁氧基苯基)-1,3,5-三嗪、六甲基磷酰三胺中的至少一种。
第二方面,本发明提供一种可降解高阻隔复合膜的制备方法,包括如下步骤:
S1:将淀粉在60℃下干燥12-48h后与增塑剂按100:(10-40)比例称重并加入高速混合机搅拌2-10min,混合过程中机器内壁通冷却水进行料温冷却。将混合物料加入挤出机进行熔融、混炼、冷却和切粒,从喂料段到挤出机头的温度为80-150℃,喂料转速3-10rpm,螺杆转速50-400rpm/min,熔体压力2-10MPa,牵引和切粒速度分别为20-60rpm/min和7-20rpm/min,经切粒后得到用于改性聚对苯二甲酸己二酸丁二酯共聚物的热塑性淀粉;
S2:将S1所述热塑性淀粉颗粒、聚对苯二甲酸-己二酸丁二酯共聚物、相容剂、增粘剂和辅料混合后挤出造粒,再经挤出机吹塑成膜,吹膜机各温区操作温度为80-200℃,主机转速40-200rpm/min,并依次经过熔融、塑化、增压、冷却、牵引、切边和收卷,即得所述A层;
S3:在S2所得A层膜上方放卷B层,对A层进行加热后与B层同时经过冷却复合辊进行拉伸转移,通过压延辊压合在一起,获得A/B结构复合膜;
S4:将全生物降解聚合物、增强填料、抗静电剂和紫外线吸收剂加入多路喂料挤出系统进行熔融共混造粒,冷却后的粒料投入多层复合生产线的第一台挤出机中,使粒料熔融、塑化形成均匀流体,通过平口模形成流延薄膜作为C层;
S5:将S4所得流延膜拉伸转移,同时流延膜上方放置S2所得A层膜,两者通过压延辊压合在一起,获得A/C结构复合膜;
S6:在S4所得层流延膜上方放卷B层,两者通过压延辊压合在一起,获得B/C结构复合膜;
S7:将S2所得A层膜加热、冷却复合辊进行拉伸转移后与S6所得B/C复合膜进行二次压延复合,即得所述A/B/C结构复合膜;
S8:将S2所得A层膜放卷于B层膜两侧,其中B层膜为主放卷,对S2所得A层膜加热、拉伸转移后与B层膜压延复合,即得A/B/A结构复合膜;
S9:对S8所得A/B/A复合膜A面进行电晕处理后与S4所得材料分别拉伸转移至第二副加热和冷却复合辊,通过复合辊压延在一起即得所述A/B/A/C结构复合材料,
S10:对S3、S5、S7、S9所得材料进行电晕、收卷、分切、包装即得所述可降解高阻隔复合膜。
与现有技术相比,本发明的有益效果为:
(1)利用热塑性淀粉填充聚对苯二甲酸-己二酸丁二酯共聚物降低可降解树脂的生产成本并增加其对水蒸汽的阻隔性,并能保证其在可表明期限的自然环境中的堆肥可降解性;
(2)当复合软包装材料在使用期结束后,复合膜无需进行化学分离,直接通过堆肥处理,有助于解决目前复合软包装回收材料难回收的问题;
(3)该复合膜具有良好的阻隔性、较高层间剥离强度,可应用于液态和生鲜类食品的包装领域。
具体实施方式
现在结合实施例对本发明作进一步详细的说明,本发明的应用并不局限于下面的实施例,对本发明所做的任何形式上的变通都将落入本发明的保护范围。
实施例1-5中A、B、C各层的成分如表1所示。
表1实施例1-5中A、B、C层成分
实施例1
一种生物可降解高阻隔复合膜,该复合膜具有A/C双层结构。
所述A层厚度为50μm,由平均粒径1mm,特性黏度([η])0.9dl/g,分子量为15万的改性聚对苯二甲酸-己二酸丁二酯共聚物颗粒加工而成。所述A层包括以下重量份计的组分:聚对苯二甲酸-己二酸丁二酯共聚物50份,热塑性淀粉60份,乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯2份,乙烯-醋酸乙烯共聚物3.1份,辅料1.5份。
所述C层厚度为6μm,包含以下质量份数计的组分:癸二酸聚甘油酯23份、聚乳酸-己内酯共聚物17份、纤维素纳米晶体4份、碳纳米管9份、三羟乙基甲基季胺甲基硫酸盐12.8份、N,N-十六烷基乙基吗啉硫酸乙酯盐3.2份和三(1,2,2,6,6-五甲哌啶基)亚磷酸酯0.1份。
上述可降解高阻隔复合膜的制备方法,包括以下步骤:
S1:将直链度为20%的淀粉在60℃下干燥12h后与甘油和硬脂酸按40:15:5比例称重并加入高速混合机搅拌2min,混合过程中机器内壁通冷却水,使糊化温度保持在50℃。将混合物料加入挤出机进行熔融、混炼、冷却和切粒,从喂料段到挤出机头的温度为110-150℃,喂料转速5rpm,螺杆转速400rpm/min,熔体压力2-5MPa,牵引和切粒速度分别为20rpm/min和19rpm/min。经切粒后得到用于改性聚对苯二甲酸己二酸丁二酯共聚物的热塑性淀粉;
S2:将S1所述热塑性淀粉颗粒、聚对苯二甲酸-己二酸丁二酯共聚物,乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯、乙烯-醋酸乙烯共聚物、抗菌剂、开口剂和爽滑剂混合后挤出造粒,再经挤出机吹塑成膜,吹膜机各温区操作温度为110-160℃,主机转速200Hz,并依次经过熔融、塑化、增压、冷却、牵引、切边和收卷,即得所述A层;
S3:将癸二酸聚甘油酯、聚乳酸-己内酯共聚物、纤维素纳米晶体、碳纳米管、三羟乙基甲基季胺甲基硫酸盐、N,N-十六烷基乙基吗啉硫酸乙酯盐和三(1,2,2,6,6-五甲哌啶基)亚磷酸酯加入多路喂料挤出系统进行熔融共混造粒,冷却后的粒料投入多层复合生产线的第一台挤出机中,使粒料熔融、塑化形成均匀流体,通过平口模形成流延薄膜作为C层;
S4:所得流延膜拉伸转移,同时流延膜上方放置A层,两者通过压延辊压合在一起,获得A/C结构复合膜;
S5:对S4所得材料进行收卷、分切、包装即得所述可降解高阻隔复合膜。
实施例2
一种生物可降解高阻隔复合膜,该复合膜具有A/B/C三层结构。
所述A层厚度为55μm,由平均粒径3mm,特性黏度([η])1.2dl/g,分子量为10万的改性聚对苯二甲酸-己二酸丁二酯共聚物颗粒加工而成。所述A层包括以下重量份计的组分:聚对苯二甲酸-己二酸丁二酯共聚物103份,热塑性淀粉20份,γ-氨丙基三乙氧基硅烷3份,海藻酸钠0.5份,辅料26.3份。
所述B层厚度为400μm,材质为纤维素膜。
所述C层厚度为230μm,包含以下质量份数计的组分:聚乳酸-己内酯共聚物12份、聚羟基脂肪酸酯50份、纳米插层蒙脱土10份、碳纳米管2份、N,N-十六烷基乙基吗啉硫酸乙酯盐5.6份和三(1,2,2,6,6-五甲哌啶基)亚磷酸酯5份。
上述可降解高阻隔复合膜的制备方法,包括以下步骤:
S1:将直链度为28%的淀粉在60℃下干燥12h后与甘油和尿素按14:1:5比例称重并加入高速混合机搅拌5min,混合过程中机器内壁通冷却水,使糊化温度保持在50℃。将混合物料加入挤出机进行熔融、混炼、冷却和切粒,从喂料段到挤出机头的温度为110-130℃,喂料转速7rpm,螺杆转速300rpm/min,熔体压力3-8MPa,牵引和切粒速度分别为30rpm/min和20rpm/min。经切粒后得到用于改性聚对苯二甲酸己二酸丁二酯共聚物的热塑性淀粉;
S2:将S1所述热塑性淀粉颗粒、聚对苯二甲酸-己二酸丁二酯共聚物、γ-氨丙基三乙氧基硅烷、海藻酸钠、抗菌剂、开口剂和爽滑剂混合后挤出造粒,再经挤出机吹塑成膜,吹膜机各温区操作温度为110-140℃,主机转速400Hz,并依次经过熔融、塑化、增压、冷却、牵引、切边和收卷,即得所述A层;
S3:将聚乳酸-己内酯共聚物、聚羟基脂肪酸酯、纳米插层蒙脱土、碳纳米管、N,N-十六烷基乙基吗啉硫酸乙酯盐和三(1,2,2,6,6-五甲哌啶基)亚磷酸酯加入多路喂料挤出系统进行熔融共混造粒,冷却后的粒料投入多层复合生产线的第一台挤出机中,使粒料熔融、塑化形成均匀流体,通过平口模形成流延薄膜作为C层;
S4:在C层流延膜上方放卷B层,两者通过压延辊压合在一起,获得B/C结构复合膜;
S5:将S2所得A层膜加热、冷却复合辊进行拉伸转移后与S4所得的B/C结构复合膜进行二次压延复合,即得所述A/B/C结构复合膜。
S6:对S3所得材料进行电晕、收卷、分切、包装即得所述可降解高阻隔复合膜。
实施例3
一种生物可降解高阻隔复合膜,该复合膜具有A/B双层结构。
所述A层厚度为100μm,由平均粒径2mm,特性黏度([η])1.5dl/g,分子量为18万的改性聚对苯二甲酸-己二酸丁二酯共聚物颗粒加工而成。所述A层包括以下重量份计的组分:聚对苯二甲酸-己二酸丁二酯共聚物80份,热塑性淀粉30份,γ-氨丙基三乙氧基硅烷6份,乙烯-醋酸乙烯共聚物8.6份,辅料35.5份。
所述B层厚度为300μm,材质为纸。
上述可降解高阻隔复合膜的制备方法,包括以下步骤:
S1:将直链度为25%的淀粉在60℃下干燥48h后与硬脂酸和尿素按30:9:4比例称重并加入高速混合机搅拌8min,混合过程中机器内壁通冷却水,使糊化温度保持在120℃。将混合物料加入挤出机进行熔融、混炼、冷却和切粒,从喂料段到挤出机头的温度为110-150℃,喂料转速10rpm,螺杆转速400rpm/min,熔体压力8-10MPa,牵引和切粒速度分别为35rpm/min和20rpm/min。经切粒后得到用于改性聚对苯二甲酸己二酸丁二酯共聚物的热塑性淀粉;
S2:将S1所述热塑性淀粉颗粒、聚对苯二甲酸-己二酸丁二酯共聚物、热塑性淀粉、γ-氨丙基三乙氧基硅烷、乙烯-醋酸乙烯共聚物、抗菌剂、开口剂和爽滑剂混合后挤出造粒,再经挤出机吹塑成膜,吹膜机各温区操作温度为90-140℃,主机转速200Hz,并依次经过熔融、塑化、增压、冷却、牵引、切边和收卷,即得所述A层;
S3:在A层膜上方放卷B层,对A层进行加热后与B层同时经过冷却复合辊进行拉伸转移,通过压延辊压合在一起,获得A/B结构复合膜;
S4:对S3所得材料进行电晕、收卷、分切、包装即得所述可降解高阻隔复合膜。
实施例4
一种生物可降解高阻隔复合膜,该复合膜具有A/B/A/C四层结构。
所述A层厚度为80μm,由平均粒径4mm,特性黏度([η])1.3dl/g,分子量为12万的改性聚对苯二甲酸-己二酸丁二酯共聚物颗粒加工而成。所述A层包括以下重量份计的组分:聚对苯二甲酸-己二酸丁二酯共聚物85份,热塑性淀粉80份,乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯10份,海藻酸钠10份,辅料42份。
所述B层厚度为260μm,材质为纤维素膜。
所述C层厚度为300μm,包含以下质量份数计的组分:癸二酸聚甘油酯130份、聚羟基脂肪酸酯20份、纤维素纳米晶体5份、纳米插层蒙脱土15份、碳纳米管30份、N,N-十六烷基乙基吗啉硫酸乙酯盐2份、邻羟基苯甲酸苯酯2.9份和三(1,2,2,6,6-五甲哌啶基)亚磷酸酯12.1份。
上述可降解高阻隔复合膜的制备方法,包括以下步骤:
S1:将直链度为22%的淀粉在60℃下干燥36h后与硬脂酸和尿素按51:22:7比例称重并加入高速混合机搅拌10min,混合过程中机器内壁通冷却水,使糊化温度保持在100℃。将混合物料加入挤出机进行熔融、混炼、冷却和切粒,从喂料段到挤出机头的温度为100-140℃,喂料转速3rpm,螺杆转速200rpm/min,熔体压力2-4MPa,牵引和切粒速度分别为15rpm/min和8rpm/min。经切粒后得到用于改性聚对苯二甲酸-己二酸丁二酯共聚物的热塑性淀粉;
S2:将S1所述热塑性淀粉颗粒、聚对苯二甲酸-己二酸丁二酯共聚物、热塑性淀粉、乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯、海藻酸钠、抗菌剂、开口剂和爽滑剂混合后挤出造粒,再经挤出机吹塑成膜,吹膜机各温区操作温度为145-190℃,主机转速200Hz,并依次经过熔融、塑化、增压、冷却、牵引、切边和收卷,即得所述A层;
S3:将癸二酸聚甘油酯、聚羟基脂肪酸酯、纤维素纳米晶体、纳米插层蒙脱土、碳纳米管、N,N-十六烷基乙基吗啉硫酸乙酯盐、邻羟基苯甲酸苯酯和三(1,2,2,6,6-五甲哌啶基)亚磷酸酯加入多路喂料挤出系统进行熔融共混造粒,冷却后的粒料投入多层复合生产线的第一台挤出机中,使粒料熔融、塑化形成均匀流体,通过平口模形成流延薄膜作为C层;
S4:将S2所得A层膜放卷于B层膜两侧,其中B层膜为主放卷,对S2所得A层膜加热、拉伸转移后与B层膜压延复合,即得A/B/A结构复合膜。
S5:对S4所得A/B/A复合膜A面进行电晕处理后与S3所得材料分别拉伸转移至第二副加热和冷却复合辊,通过复合辊压延在一起即得所述A/B/A/C结构复合材料。
S6:对S5所得材料进行电晕、收卷、分切、包装即得所述可降解高阻隔复合膜。
实施例5
一种生物可降解高阻隔复合膜,该复合膜具有A/B/A/C四层结构。
所述A层厚度为95μm,由平均粒径5mm,特性黏度([η])1.5dl/g,分子量为14万的改性聚对苯二甲酸-己二酸丁二酯共聚物颗粒加工而成。所述A层包括以下重量份计的组分:聚对苯二甲酸-己二酸丁二酯共聚物80份,热塑性淀粉109份,γ-氨丙基三乙氧基硅烷7份,海藻酸钠6.4份,辅料31.2份。
所述B层厚度为50μm,材质为纤维素膜。
所述C层厚度为160μm,包含以下质量份数计的组分:癸二酸聚甘油酯45份、聚乳酸-己内酯共聚物65份、纤维素纳米晶体10份、纳米插层蒙脱土50份、三羟乙基甲基季铵甲基硫酸盐9.7份、和三(1,2,2,6,6-五甲哌啶基)亚磷酸酯8.5份。
上述可降解高阻隔复合膜的制备方法,包括以下步骤:
S1:将直链度为27%的淀粉在60℃下干燥48h后与甘油和尿素按80:11:18比例称重并加入高速混合机搅拌7min,混合过程中机器内壁通冷却水,使糊化温度保持在120℃。将混合物料加入挤出机进行熔融、混炼、冷却和切粒,从喂料段到挤出机头的温度为80-130℃,喂料转速5rpm,螺杆转速340rpm/min,熔体压力2-5MPa,牵引和切粒速度分别为7rpm/min和10rpm/min。经切粒后得到用于改性聚对苯二甲酸-己二酸丁二酯共聚物的热塑性淀粉;
S2:将S1所述热塑性淀粉颗粒、聚对苯二甲酸-己二酸丁二酯共聚物、γ-氨丙基三乙氧基硅烷、海藻酸钠、抗菌剂、开口剂和爽滑剂混合后挤出造粒,再经挤出机吹塑成膜,吹膜机各温区操作温度为80-135℃,主机转速300Hz,并依次经过熔融、塑化、增压、冷却、牵引、切边和收卷,即得所述A层;
S3:将癸二酸聚甘油酯、聚乳酸-己内酯共聚物、纤维素纳米晶体、纳米插层蒙脱土、三羟乙基甲基季铵甲基硫酸盐和三(1,2,2,6,6-五甲哌啶基)亚磷酸酯加入多路喂料挤出系统进行熔融共混造粒,冷却后的粒料投入多层复合生产线的第一台挤出机中,使粒料熔融、塑化形成均匀流体,通过平口模形成流延薄膜作为C层;
S4:将S2所得A层膜放卷于B层膜两侧,其中B层膜为主放卷,对S2所得A层膜加热、拉伸转移后与B层膜压延复合,即得A/B/A结构复合膜。
S5:对S4所得A/B/A复合膜A面进行电晕处理后与S3所得材料分别拉伸转移至第二副加热和冷却复合辊,通过复合辊压延在一起即得所述A/B/A/C结构复合材料。
S6:对S5所得材料进行电晕、收卷、分切、包装即得所述可降解高阻隔复合膜。
实验例
按本实施例方法制备A/C、A/B/C、A/B和A/B/A/C复合膜,随后将复合膜置于既定温度和湿度条件下进行阻隔性、降解性及层间剥离测试。生物降解率、水蒸气透过量、氧气透过量和剥离强度测试结果如表2所示。
表2实施例1-5中多层复合膜的生物分解率、氧气透过量、水蒸气透过量和剥离强度
实施例1-5中复合膜在6个月之内的生物分解率≥74%,符合GB/T20197-2006中关于生物可降解塑料的生物分解率应≥61%的要求。该类复合薄膜的氧气透过量和水蒸气透过量均符合GB/T 28117-2011中食品包装薄膜的要求氧气透过量和水蒸气透过量应低于20cm3/m2·24h·0.1MPa和30(g/m2·24h)的要求。食品复合包装薄膜的剥离强度一般应≥3.0N/15mm,实施例1-5的复合膜各层间剥离强度均符合要求。因此,本发明所述的可降解高阻隔复合膜有应用于对阻隔性要求较高的食品包装的潜力。
以上所述,仅是本发明的原理示意方案,并非对本发明的结构作其它形式上的限制。未表述的部分默认为采用本领域公知的方案,凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明的技术方案的范围内。
Claims (10)
1.一种可降解高阻隔复合膜,其特征在于,具有A/B、A/C、A/B/C和A/B/A/C四者之一的层结构,所述A层为改性聚对苯二甲酸-己二酸丁二酯共聚物,包含以下质量组分:聚对苯二甲酸-己二酸丁二酯共聚物50-103份,热塑性淀粉20-109份,相容剂2-10份,增粘剂0.5-10份,辅料1.5-42份;
所述B层为纸或纤维素膜;
所述C层为复合材料,包含以下质量组分:全生物降解聚合物40-150份,增强填料12-60份,抗静电剂2-16份,紫外线吸收剂0.1-15份。
2.根据权利要求1所述的可降解高阻隔复合膜,其特征在于,所述热塑性淀粉的增塑剂为甘油、柠檬酸、硬脂酸、甲酰胺、尿素、山梨醇、乙二醇、乙酰柠檬酸三丁酯和环氧大豆油中的至少两种。
3.根据权利要求1所述的可降解高阻隔复合膜,其特征在于,所述热塑性淀粉的糊化温度为50-120℃。
4.根据权利要求1所述的可降解高阻隔复合膜,其特征在于,所述相容剂为琥珀酸酐、马来酸酐接枝聚对苯二甲酸-己二酸丁二酯共聚物、乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯、γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、钛酸酯偶联剂中的至少一种。
5.根据权利要求1所述的可降解高阻隔复合膜,其特征在于,所述增粘剂为乙烯-醋酸乙烯共聚物、乙烯-丙烯酸共聚物、木质素磺酸钠、二苯甲烷二异氰酸酯和杜邦公司的Biomax strong 120中的至少一种。
6.根据权利要求1所述的可降解高阻隔复合膜,其特征在于,所述全生物降解聚合物为聚羟基脂肪酸酯、聚ε-己内酯、聚丁二酸丁二醇酯、聚丁二酸-己二酸-丁二酯共聚物、聚乳酸-己内酯共聚物、癸二酸聚甘油酯、聚对苯二甲酸-共-丁二酸丁二醇酯和聚碳酸亚丙酯中的至少两种。
7.根据权利要求1所述的可降解高阻隔复合膜,其特征在于,所述增强填料为碳纳米管、石墨烯、白木质素、纤维素纳米晶体、纳米插层蒙脱土、高岭土、纳米碳酸钙、纤维素纳米晶须、无定形纳米级白炭黑、食品级滑石粉中的至少一种。
8.根据权利要求1所述的可降解高阻隔复合膜,其特征在于,所述抗静电剂为三羟乙基甲基季铵甲基硫酸盐、十八烷基二甲基季铵硝酸盐、烷基酰胺类非离子型表面活性剂、烷基磷酸酯、烷基硫酸酯、硬脂酰三甲基氯化铵和硬脂酰二甲基戊基氯化铵、(月桂酰胺丙基三甲基胺)硫酸钾酯盐、N,N-双(2-羟乙基)-N-(3’十二烷氧基-2’羟基丙基)甲胺硫酸钾酯盐、三羟乙基甲基季胺硫酸钾酯盐、N,N-十六烷基乙基吗啉硫酸乙酯盐中的至少一种。
9.根据权利要求1所述的可降解高阻隔复合膜,其特征在于,所述紫外线吸收剂为邻羟基苯甲酸苯酯、2, 4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2-羟基-4-正辛氧基二苯甲酮、2-(2’-羟基-3’, 5’-二叔苯基)-5-氯化苯并三唑、单苯甲酸间苯二酚酯、2’-2’-硫代双(4-叔辛基酚氧基)镍、三(1, 2, 2, 6, 6-五甲哌啶基)亚磷酸酯、4-苯甲酰氧基-2,2, 6, 6-四甲基哌啶、2, 4, 6-三(2’正丁氧基苯基)-1, 3, 5-三嗪、六甲基磷酰三胺中的至少一种。
10.一种可降解高阻隔复合膜的制备方法,其特征在于,包括以下步骤:S1:将淀粉在60℃下干燥12-48h后与增塑剂按100:(10-40)比例称重并加入高速混合机搅拌2-10 min,混合过程中机器内壁通冷却水进行料温冷却。将混合物料加入挤出机进行熔融、混炼、冷却和切粒,从喂料段到挤出机头的温度为80-150℃,喂料转速3-10 rpm,螺杆转速50-400 rpm/min,熔体压力2-10 MPa,牵引和切粒速度分别为20-60 rpm/min和7-20 rpm/min,经切粒后得到用于改性聚对苯二甲酸-己二酸丁二酯共聚物的热塑性淀粉;
S2:将S1所述热塑性淀粉颗粒、聚对苯二甲酸-己二酸丁二酯共聚物、相容剂、增粘剂和辅料混合后挤出造粒,再经挤出机吹塑成膜,吹膜机各温区操作温度为80-200℃,主机转速40-200 rpm/min,并依次经过熔融、塑化、增压、冷却、牵引、切边和收卷,即得所述A层;
S3:在S2所得A层膜上方放卷B层,对A层进行加热后与B层同时经过冷却复合辊进行拉伸转移,通过压延辊压合在一起,获得A/B结构复合膜;
S4:将全生物降解聚合物、增强填料、抗静电剂和紫外线吸收剂加入多路喂料挤出系统进行熔融共混造粒,冷却后的粒料投入多层复合生产线的第一台挤出机中,使粒料熔融、塑化形成均匀流体,通过平口模形成流延薄膜作为C层;
S5: 将S4所得流延膜拉伸转移,同时流延膜上方放置S2所得A层膜,两者通过压延辊压合在一起,获得A/C结构复合膜;
S6:在S4所得层流延膜上方放卷B层,两者通过压延辊压合在一起,获得B/C结构复合膜;
S7:将S2所得A层膜加热、冷却复合辊进行拉伸转移后与S6所得B/C复合膜进行二次压延复合,即得所述A/B/C结构复合膜;
S8:将S2所得A层膜放卷于B层膜两侧,其中B层膜为主放卷,对S2所得A层膜加热、拉伸转移后与B层膜压延复合,即得A/B/A结构复合膜;
S9:对S8所得A/B/A复合膜A面进行电晕处理后与S4所得材料分别拉伸转移至第二副加热和冷却复合辊,通过复合辊压延在一起即得所述A/B/A/C结构复合材料,
S10:对S3、S5、S7、S9所得材料进行电晕、收卷、分切、包装即得所述可降解高阻隔复合膜。
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