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CN104999609B - 一种pbat淋膜的复合材料的制备方法及应用 - Google Patents

一种pbat淋膜的复合材料的制备方法及应用 Download PDF

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CN104999609B
CN104999609B CN201510337604.XA CN201510337604A CN104999609B CN 104999609 B CN104999609 B CN 104999609B CN 201510337604 A CN201510337604 A CN 201510337604A CN 104999609 B CN104999609 B CN 104999609B
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film
pbat
composite
preparation
rollers
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CN104999609A (zh
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邢鹏
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Shandong Beifute New Material Co Ltd
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Priority to CN201510337604.XA priority Critical patent/CN104999609B/zh
Priority to PCT/CN2015/084903 priority patent/WO2016127586A1/zh
Priority to US15/550,009 priority patent/US10518456B2/en
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
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    • A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
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Abstract

本发明涉及一种PBAT淋膜的复合材料的制备方法及应用，本发明通过将PBAT或者以PBAT为主，与其他可生物降解塑料或超细碳酸钙混合后的混合物通过淋膜机的逐段加温，将所述材料慢慢加热至熔融状态，然后在淋膜机淋膜的同时在滚轴通入冷水来控制滚轴的温度从而控制滚轮和淋膜的温度，使用本方法制备得到的PBAT淋膜的复合材料具有优异的力学性能，与PLA淋膜的材料相比具有同等或以上的防水、防油性能，且可以复合的厚度范围大，成本低,可以广泛应用于可降解包装领域、可降解卫生巾、纸尿裤领域。

Description

一种PBAT淋膜的复合材料的制备方法及应用
技术领域
本发明涉及一种可降解的复合材料的制备方法及应用，尤其涉及一种使用淋膜披覆技术制备复合材料的方法及应用，属于复合材料领域。
背景技术
纸质食品容器和纸质防渗漏防水防潮垃圾等容器及纸尿裤、卫生巾等为了避免液体浸渗纸材，通常会在内外表面披覆一层塑料膜，以达到防水防漏的效果，而淋膜通常使用聚乙烯(PE)或者聚丙烯(PP)为原料，这种淋膜后的纸具有了防水防漏的效果，但由于聚乙烯(PE)和聚丙烯(PP)不能生物降解，会产生大量白色垃圾，对环境造成污染。
为了解决白色污染的问题，行业内发展出一种PLA(聚乳酸)披覆的淋膜纸，PLA可自然分解，且无毒性，可达到环保效果，但PLA质脆、韧性和抗冲击性差以及热稳定性差等缺点使其应用范围大大受限，且目前的PLA淋膜技术对于淋膜的厚度具有一定的局限性，PLA的淋膜厚度不能低于22g/m2,造成PLA淋膜的成本过高，另一种可生物降解的材料PBS(聚丁二酸丁二醇酯)的加工温度低，粘性低，熔体强度差，另外，PLA、PBS是结晶聚合物，其制品往往具有一定的脆性，因此，二者在包装领域中的应用范围大大受限。
本发明中使用的PBAT是己二酸丁二醇酯和对苯二甲酸丁二醇酯的共聚物，既有良好的延展性和断裂伸长率，也具有较好的耐热性和抗冲击性，此外，PBAT还是优良的生物降解材料，因此可以用它来改善脂肪族聚酯如PLA的力学性能，肖运鹤等的“超细碳酸钙填充可降解聚酯材料的研究”(塑料，2009，38(3)：69-71)表明，PBAT与超细碳酸钙共混不仅能实现材料的完全快速降解，还能极大的节省成本，但由于PBAT本身的物理特性粘度太大，因而在淋膜的操作过程中，极易沾附于设备之上，造成不能连续生产，因此，至今未有成功使用PBAT淋膜的报道。
发明内容
本发明针对上述PBAT淋膜过程中的问题，提供一种PBAT淋膜的复合材料的制备方法及应用。
本发明解决上述技术问题的技术方案如下：
一种PBAT淋膜的复合材料的制备方法，包括以下步骤：
Ⅰ.将PBAT、PBAT 100重量份与其他可生物降解塑料5-40重量份混合后的混合物或者PBAT 100重量份与超细碳酸钙5-40重量份混合后的混合物作为基料加入搅拌桶内，通过搅拌加热干燥；
Ⅱ.将所述步骤Ⅰ中干燥后的基料通过原料输送机输送至淋膜机的储料仓；
Ⅲ.所述步骤Ⅱ中储料仓中的基料经进料口进入淋膜机螺杆加热推进，淋膜机内沿螺杆方向分为多个加热段，每个加热段的温度沿螺杆方向逐渐升高直至到达基料的熔点，熔融后的基料经输料弯头到达淋膜头；
Ⅳ.通过淋膜机台底部的前进导轮将淋膜机台推进至一定位置，使步骤Ⅲ中所述的淋膜头位于淋膜机台的两滚轮之间，再经横向气缸驱动的固定滑座进行微调，使得所述的淋膜头位于淋膜机台的两滚轮之间的正中心线位置，最后经顶推油压缸控制所述的淋膜机台上升，使得所述的两滚轮之间的淋膜中心线至淋膜头的出料口一预定的距离；
Ⅴ.基材料轴将基材输送至淋膜机台的两滚轮之间，控制淋膜机使基料淋膜披覆在基材之上，并通过横向气缸控制两滚轮间的压力来控制基料与基材之间的复合强度，所述基材为纸、无纺布或薄木纸板中的一种，同时在滚轴内通入冷却水将滚轴温度控制在20-30℃，从而保证熔融状态的薄膜披覆在基材上后能够快速冷却凝固，使薄膜复合在基材上并与滚轮相分离。
本发明的有益效果是：
本方法可以将PBAT及以PBAT为主要成分的可生物降解的混合物通过淋膜方法成功复合到基材上，所得复合材料与PLA淋膜的复合材料相比，具有优异的力学性能，可呈现同等或以上的防水、防油和耐温的效果，且PBAT可以复合的厚度范围大，最低至10g/m2,大大降低了复合材料的成本。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，所述步骤Ⅴ中滚轴内通入冷却水的同时开启滚轮上部的喷水装置喷出10-20℃的水。
采用上述进一步技术方案的有益效果是，能够使得基料膜覆在基材上后快速冷却凝固，并与滚轮相分离。
进一步，所述滚轮由防粘材料制成。
采用上述进一步技术方案的有益效果是，能够使得基料膜覆在基材上很容易的与滚轮相分离，实现连续生产。
进一步，所述防粘材料选自聚四氟乙烯、陶瓷、硅胶中的一种。
进一步，所述步骤Ⅰ中的其他可生物降解塑料是指PLA、PBS中的一种或者两种的混合物；
进一步，所述步骤Ⅲ中多个加热段为6个加热段；
进一步，所述步骤Ⅲ中6个加热段的加热温度自150℃以依次递增30-40℃、60-70℃、10-20℃、10-20℃、10-20℃的规律增加。
进一步，所述步骤Ⅳ中两滚轮之间的中心线至淋膜头出料口的预定距离为3-7cm。
进一步，所述步骤Ⅴ中两滚轮之间的压力控制在0.5-0.8Mpa。
本发明还保护一种PBAT淋膜的复合材料的制备方法在纸尿裤、卫生巾、包装领域的应用。
附图说明
图1为本发明淋膜过程整个生产线示意图；
图2为本发明中淋膜机的侧视图；
在图1和图2中，1、搅拌桶，2、原料输送机，3、储料仓，4、进料口，5、螺杆输送机，6、输送弯头，7、淋膜头，8、喷水装置，9、薄膜，10、滚轮，11、横向气缸，12、固定滑座，13、基材料轴，14、收卷机，15、淋膜机台，16、机台前进导轮，17、机台前进导轨，18、顶推油压缸
具体实施方式
以下结合实例对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1：
如附图1和2所示，一种制备PBAT淋膜的复合材料的设备，包括搅拌桶1、原料输送机2和淋膜机，搅拌桶1经原料输送机2与淋膜机的进料口4连接，淋膜机两滚轮10的上部安装有喷水装置8。
将1000g PBAT加入搅拌桶1内干燥，搅拌桶转速500r/min，干燥5min后经原料输送机2输送至淋膜机的储料仓3，PBAT由进料口4进入淋膜机的螺杆输送机5，螺杆内分为6个加热段，沿螺杆方向依次设置为150℃、190℃、260℃、275℃、285℃、305℃，熔融后的PBAT到达淋膜头7，通过淋膜机台底部的前进导轮16将淋膜机推进至一定位置，使淋膜头7位于淋膜机台的两滚轮10之间，再经淋膜机台的固定滑座12进行微调，使淋膜机膜头7位于滚轮机台的两滚轮10之间的正中心线位置，最后顶推油压缸18控制淋膜机台上升，使得两滚轮10之间的淋膜中心线至淋膜头7的出料口4cm，控制淋膜机将PBAT淋覆于40m2的纸上，控制两滚轮间的压力为0.6Mpa,同时在滚轴内通入冷却水将滚轴的温度控制在20℃，喷水装置8同时往滚轮10上喷出20℃的水，最终所得复合淋膜纸的淋膜厚度为25g/m2，所得复合淋膜纸的拉伸测试数据见表1。
实施例2：
使用与实施例1中相同的设备，将1000g PBAT和50g NatureWorks4032D型号的PLA加入搅拌桶1内干燥，搅拌桶转速500r/min，干燥5min后经原料输送机2输送至淋膜机的储料仓3，PBAT和PLA通过淋膜机的螺杆加热推进，螺杆内分为6个加热段，沿螺杆方向依次设置为160℃、190℃、260℃、280℃、290℃、315℃，熔融后的PBAT和PLA到达淋膜头7，通过淋膜机台底部的前进导轮16将淋膜机台15推进至一定位置，使淋膜机膜头7位于淋膜机台的两滚轮10之间，再经淋膜机台的滚轮滑座12进行微调，使淋膜头7于滚轮机台的两滚轮10之间的正中心线位置，最后顶推油压缸18控制淋膜机台上升，使得两滚轮10之间的淋膜中心线至淋膜头7的出料口7cm，控制淋膜机将PBAT淋覆于100m2的无纺布上，控制两滚轮间的压力为0.5Mpa,同时在滚轴内通入冷却水将滚轴的温度控制在25℃，喷水装置8同时往滚轮10上喷出10℃的水，淋膜厚度为10.5g/m2，所得复合淋膜材料的拉伸测试数据见表1。
实施例3：
使用与实施例1中结构相同的设备，滚轮由聚四氟材料制成。
将1000g PBAT和400g新疆蓝山屯河化工股份有限公司生产的TH801T型号PBS加入搅拌桶1内干燥，搅拌桶转速500r/min，干燥5min后经原料输送机2输送至淋膜机的储料仓3，PBAT和PBS通过淋膜机的螺杆加热推进，螺杆内分为6个加热段，沿螺杆方向依次设置为150℃、180℃、270℃、280℃、290℃、300℃，熔融后的PBAT和PBS到达淋膜头7，通过淋膜机台底部的前进导轮16将淋膜机台15推进至一定位置，使淋膜头7位于淋膜机台的两滚轮10之间，再经淋膜机台的滚轮滑座12进行微调，使淋膜头7于滚轮机台的两滚轮10之间的正中心线位置，最后顶推油压缸18控制淋膜机台上升，使得两滚轮10之间的淋膜中心线至淋膜头7的出料口5cm，控制淋膜机将PBAT淋覆于80m2的纸上，控制两滚轮间的压力为0.5Mpa,同时在滚轴内通入冷却水将滚轴的温度控制在25℃，淋膜厚度为17.5g/m2，所得复合淋膜材料的拉伸测试数据见表1。
实施例4：
使用与实施例1中相同的设备，滚轮由碳化硅陶瓷材料制成。
将1000g PBAT和200g超细碳酸钙加入搅拌桶1内干燥，搅拌桶转速500r/min，干燥5min后经原料输送机2输送至淋膜机的储料仓3，PBAT和超细碳酸钙通过淋膜机的螺杆加热推进，螺杆内分为6个加热段，沿螺杆方向依次设置为160℃、190℃、270℃、300℃、330℃、350℃，熔融后的PBAT和超细碳酸钙到达淋膜头7，通过淋膜机台底部的前进导轮16将淋膜机台15推进至一定位置，使淋膜头7位于淋膜机台的两滚轮10之间，再经淋膜机台的滚轮滑座12进行微调，使淋膜头7于滚轮机台的两滚轮10之间的正中心线位置，最后顶推油压缸18控制淋膜机台上升，使得两滚轮10之间的淋膜中心线至淋膜头7的出料口5cm，控制淋膜机将PBAT淋覆于50m2的薄木纸板上，控制两滚轮间的压力为0.5Mpa,同时在滚轴内通入冷却水将滚轴的温度控制在25℃，淋膜厚度为24g/m2，所得复合淋膜材料的拉伸测试数据见表1。
实施例5:
使用与实施例1中相同的设备，滚轮由硅胶制成。
将1000g PBAT和180g新疆蓝山屯河化工股份有限公司生产的TH801T型号PBS加入搅拌桶1内干燥，搅拌桶转速500r/min，干燥5min后经原料输送机2输送至淋膜机的储料仓3，PBAT和PBS通过淋膜机的螺杆加热推进，螺杆内分为6个加热段，沿螺杆方向依次设置为150℃、180℃、270℃、280℃、290℃、300℃，熔融后的PBAT和PBS到达淋膜头7，通过淋膜机台底部的前进导轮16将淋膜机台15推进至一定位置，使淋膜头7位于淋膜机台的两滚轮10之间，再经淋膜机台的滚轮滑座12进行微调，使淋膜机头7于滚轮机台的两滚轮10之间的正中心线位置，最后顶推油压缸18控制淋膜机台上升，使得两滚轮10之间的淋膜中心线至淋膜头7的出料口5cm，控制淋膜机将PBAT淋覆于100m2的纸上，控制两滚轮间的压力为0.5Mpa,同时在滚轴内通入冷却水将滚轴的温度控制在25℃，淋膜厚度为11.8g/m2，所得复合淋膜材料的拉伸测试数据见表1。
表1中拉断力测试过程实验参数如下：
试验温度：0℃，试验速度：100mm/min,夹持长度：100mm。
表1实施例1-4所得产品的拉断力测试数据
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在发明的保护范围之内。

Claims (11)

1.一种PBAT淋膜的复合材料的制备方法，包括以下步骤：
Ⅰ.将PBAT、PBAT 100重量份与其他可生物降解塑料5-40重量份混合后的混合物或者PBAT 100重量份与超细碳酸钙5-40重量份混合后的混合物作为基料加入搅拌桶(1)内，通过搅拌加热干燥；
Ⅱ.将所述步骤Ⅰ中干燥后的基料通过原料输送机(2)输送至淋膜机的储料仓(3)；
Ⅲ.所述步骤Ⅱ中储料仓(3)中的基料经进料口(4)进入淋膜机螺杆(5)加热推进，淋膜机内沿螺杆(5)方向分为多个加热段，每个加热段的温度沿螺杆(5)方向逐渐升高直至到达基料的熔点，熔融后的基料经输料弯头(6)到达淋膜头(7)；
Ⅳ.通过淋膜机台(15)底部的前进导轮(16)将淋膜机台(15)推进至一定位置，使步骤Ⅲ中所述的淋膜头(7)位于淋膜机台(15)的两滚轮(10)之间，再经横向气缸(11)驱动的固定滑座(12)进行微调，使得所述的淋膜头(7)位于淋膜机台(15)的两滚轮(10)之间的正中心线位置，最后经顶推油压缸(18)控制所述的淋膜机台(15)上升，使得所述的两滚轮(10)之间的淋膜中心线至淋膜头(7)的出料口一预定的距离；
Ⅴ.基材料轴将基材输送至淋膜机台(15)的两滚轮(10)之间，控制淋膜机使基料淋膜披覆在基材之上，并通过横向气缸(11)控制两滚轮(10)间的压力来控制基料与基材之间的复合强度，所述基材为纸、无纺布或薄木纸板中的一种，同时在滚轴内通入冷却水将滚轴温度控制在20-30℃，从而保证熔融状态的薄膜(9)披覆在基材上后能够快速冷却凝固，使薄膜(9)复合在基材上并与滚轮(10)相分离。
2.根据权利要求1所述的一种PBAT淋膜的复合材料的制备方法，其特征在于，所述步骤Ⅴ中滚轴内通入冷却水的同时开启滚轮上部的喷水装置(8)喷出10-20℃的水。
3.根据权利要求1所述的一种PBAT淋膜的复合材料的制备方法，其特征在于，所述滚轮(10)由防粘材料制成。
4.根据权利要求3所述的一种PBAT淋膜的复合材料的制备方法，其特征在于，所述防粘材料选自聚四氟乙烯、陶瓷、硅胶中的一种。
5.根据权利要求1所述的一种PBAT淋膜的复合材料的制备方法，其特征在于，所述步骤Ⅰ中其他可生物降解塑料是指PLA、PBS中的一种或者两种的混合物。
6.根据权利要求5所述的一种PBAT淋膜的复合材料的制备方法，其特征在于，所述PLA的熔点为155-170℃，PBS的熔点为110-120℃。
7.根据权利要求1-5中任一项所述的一种PBAT淋膜的复合材料的制备方法，其特征在于，所述步骤Ⅲ中的多个加热段为6个加热段。
8.根据权利要求7所述的一种PBAT淋膜的复合材料的制备方法，其特征在于，所述6个加热段的加热温度自150℃以依次递增30-40℃、60-70℃、10-20℃、10-20℃、10-20℃的规律增加。
9.根据权利要求1-5中任一项所述的一种PBAT淋膜的复合材料的制备方法，其特征在于，所述步骤Ⅳ中两滚轮(10)之间的中心线至淋膜头(7)出料口的预定距离为3-7cm。
10.根据权利要求1-5中任一项所述的一种PBAT淋膜的复合材料的制备方法，其特征在于，所述步骤Ⅴ中两滚轮(10)之间的压力控制在0.5-0.8Mpa。
11.一种如权利要求1-5中任一项所述的PBAT淋膜的复合材料的制备方法的应用，其特征在于，所述方法在可降解的纸尿裤、卫生巾、包装领域的应用。
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