CN112694636A - 一种软质pbat基生物可降解发泡材料的制备方法 - Google Patents
一种软质pbat基生物可降解发泡材料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种软质PBAT基生物可降解发泡材料的制备方法,其特征在于,包括如下步骤:1)通过硫酸酸解法制备纤维素纳米晶;2)纤维素纳米晶、聚对苯二甲酸己二酸丁二醇酯、扩链剂、发泡剂熔融共混得到熔体;3)将步骤2)中熔体减压降温挤出。本发明从原理上讲以多羟基CNC与PBAT酯基间作用引发物理交联点,将PBAT分子链交联在一起,使得分子间的作用力增加,分子的相对滑移减弱,使得本发明所制软质发泡材料比同类PBAT产品具有更好的抗蠕变性能;从工艺上大大简化了其他化学改性PBAT的工艺流程;从性能上,本发明所制软质泡沫材料与常规泡沫材料相比具有突出的生物可降解性能,环保优势明显。
Description
技术领域
本发明涉及发泡材料领域,具体涉及一种软质PBAT基生物可降解发泡材料的制备方法。
背景技术
随着电子信息技术的快速发展,网购、外卖行业飞速崛起,并在我们生活中占据越来越重要的地位,以此产生的快递物流成为其中重要的一环。为了使产品在运输过程中避免受损,防撞泡沫成为快递中必不可少的材料。目前广泛应用的发泡材料大多是由聚乙烯(PE)、聚苯乙烯(PS)、聚氨酯(PU)等制成。其中,PS发泡制品是目前使用量较大的材料,但它降解十分困难,严重破坏环境,所以有“白色污染”之称,PU泡沫片材在发泡过程中会产生对人体有害的异氰酸酯残留物,且使用之后无法进行回收再利用。这些发泡材料的大量使用且不可降解给环境带来了巨大压力,因此制备生物可降解的发泡材料成为目前全社会亟待解决的问题。
目前产业化程度最高的生物可降解材料为聚乳酸和聚对苯二甲酸己二酸丁二醇酯(PBAT),其中PBAT由于单体均可从石油衍生物中提取,因此,未来发展潜力更大。PBAT已经广泛应用于垃圾袋、食品包装袋以及薄膜包装等包装材料,并在棉签等卫生用品领域和生物医药领域等均有应用(许新华,张家星.PBAT复合材料的性能和应用[J].安徽化工,2020,225(03):14-18.)。但在当前快递物流中大量使用的泡沫材料领域尚未得到应用,其主要原因在于PBAT存在蠕变性强、熔体强度低等性能缺陷。制备聚合物发泡材料,通常要在聚合物基体中引入泡孔,常规的方法是加入发泡剂。在气泡大量形成的过程中,高聚物熔体在气泡间以间隔膜的形式存在,单位体积内气泡越多,则熔体间隔膜厚度越薄。因此,商业化泡沫材料的制备要求高分子熔体需有较高的熔体强度,以支撑极薄气泡间隔膜的形成。在专利CN108264736B中介绍了一种PBAT挤出发泡制备方法,优化了发泡的操作时间和温度窗口等,但该PBAT发泡材料的抗蠕变性能不高,材料在使用过程中容易发生塑性永久变形,实用性低。
高分子的蠕变性能一般源自分子链间的滑移,可在高聚物分子链间引入化学或物理交联点来抑制分子链间的滑移,从而有效控制高聚物的蠕变行为。对PBAT而言,由于其脂肪族聚酯的化学敏感性,化学改性容易导致其分子链的裂解,使得PBAT性能下降。因此,在PBAT体系中通过物理法引入交联点成为优选的解决方案。刘伟等将活性硅酸钙粉体加入PBAT材料中,在PBAT分子间形成临时物理交联结构,降低了分子链的运动能力,且碳酸钙粉体能促进PBAT发泡时泡孔异相成核,以此改善PBAT的可发性,制备PBAT发泡材料(刘伟,任粒,张纯,等.硅酸钙对PBAT流变性能与发泡行为的影响[J].工程塑料应用,2017(3):116-120.)。然而,由于PBAT分子链柔性显著,尽管引入成核剂,PBAT的结晶度提升幅度仍非常有限。因此,寻找其他的替代方案,在PBAT体系中引入数量可控、约束力强的物理交联点,成为PBAT泡沫材料抗蠕变改性的当务之急。
发明内容
本发明针对现有技术中PBAT熔体强度低、易蠕变的不足,提出了一种软质PBAT基生物可降解发泡材料的制备方法,本发明以CNC为物理交联剂,由于CNC表面有大量的羟基,CNC可同时与相邻的PBAT分子中酯键形成氢键,起到桥连作用,增加PBAT分子间的作用力,使得该发泡材料的抗蠕变性能得到提高,材料的回弹能力增强、使用寿命增加,因此具有更广泛的用途。
为了达到上述目的,本发明的技术方案是:
一种软质PBAT基生物可降解发泡材料的制备方法,包括如下步骤:1)通过硫酸酸解法制备纤维素纳米晶(CNC);2)纤维素纳米晶(CNC)、聚对苯二甲酸己二酸丁二醇酯(PBAT)、扩链剂、发泡剂熔融共混得到熔体;3)将步骤2)中熔体减压降温挤出。
所述的硫酸酸解法是指将纤维素微晶分散于硫酸溶液中,通过磁力搅拌机完成水解后的悬浮液反复洗涤并利用离心机离心至PH成中性,再向悬浮液中滴入浓度为0.5%的氨水并水洗,得到的纤维素纳米晶(CNC)悬浮液在去离子水中透析,在冰箱放置后彻底冷冻干燥可得到疏松的纤维素纳米晶(CNC)粉末;
所述纤维素微晶原料采用棉花、棉短绒、稻壳、松针、麻杆、橘皮中的一种或多种天然纤维素;
所述硫酸溶液的浓度为60%-70%;
所述磁力搅拌机的转速为100-120rpm,反应温度为55-65℃,反应时间为6-7h;
所述离心机的转速为10000-12000r/min,离心时间为4-7min;
所述纤维素纳米晶(CNC)悬浮液在去离子水中透析时间为12-24h。
所述的纤维素纳米晶(CNC)与聚对苯二甲酸己二酸丁二醇酯(PBAT)、扩链剂、发泡剂熔融共混,所述熔融共混各原料组分的重量份数为:聚对苯二甲酸己二酸丁二醇酯为1-100份,纤维素纳米晶为1-20份,扩链剂为1-10份,发泡剂为0.1-15份;
所述的扩链剂采用二异氰酸酯封端的长链型聚氨酯预聚体或两端由环氧基封端的长链型聚合物中的一种;
所述的发泡剂采用物理发泡剂或化学发泡剂中的一种,其中所述物理发泡剂采用超临界CO2、超临界N2、超临界丁烷中的一种;所述化学发泡剂采用偶氮类化合物、磺酰肼类化合物、碳酸钙、碳酸氢钠中的一种。
所述扩链剂优选采用甲苯-2,4二异氰酸酯(TDI),二苯甲烷二异氰酸酯(MDI)中的一种;所述偶氮类化合物的化学发泡剂优选采用偶氮二甲酰胺(AC);所述磺酰肼类化合物的化学发泡剂优选采用4,4-氧代双苯磺酰肼(OBSH)。
所述步骤2)共混步骤具体为:
(1)将聚对苯二甲酸己二酸丁二醇酯(PBAT)置于真空烘箱中80℃进行12小时干燥;
(2)取聚对苯二甲酸己二酸丁二醇酯(PBAT)、纤维素纳米晶(CNC)、扩链剂、发泡剂在双螺杆的转动下采用各自多点添加的方式充分混合并熔融得到均相体系。
所述步骤3)熔体减压降温挤出步骤具体为:将步骤2)得到的熔体在挤出模头降压降温,使泡孔成核、生长,最后冷却定型,得到软质聚对苯二甲酸己二酸丁二醇酯(PBAT)发泡材料。
本发明的有益效果为:本发明从原理上讲以多羟基CNC与PBAT酯基间作用引发物理交联点,将PBAT分子链交联在一起,使得分子间的作用力增加,分子的相对滑移减弱,使得本发明所制软质发泡材料比同类PBAT产品具有更好的抗蠕变性能;从工艺上,只需将PBAT与CNC、扩链剂、发泡剂简单熔融共混即可一步法制备,大大简化了其他化学改性PBAT的工艺流程;从性能上,本发明所制软质泡沫材料与常规泡沫材料相比具有突出的生物可降解性能,环保优势明显。
具体实施方式
实施例1
本实施例的一种软质PBAT基生物可降解发泡材料的制备方法,包括以下步骤:
1)将20.0g纤维素微晶分散与150ml浓度为60%(v/v)的硫酸溶液中,通过磁力搅拌以100rpm的速率再55℃下反应6小时完成水解。将水解后的悬浮液用去离子水反复洗涤并在10000r/min的速率下高速离心4min,直到pH为中性。向悬浮液中滴入氨水(0.5%)调节pH至7并再次水洗,将得到的CNC悬浮液在去离子水中透析12小时,在冰箱中放置成冰后彻底冷冻干燥可得到疏松的CNC粉末;
2)将PBAT置于真空烘箱中80℃进行12小时干燥后,取100份PBAT与20份的CNC,加入5份扩链剂(本实施例采用甲苯-2,4二异氰酸酯TDI),15份发泡剂(本实施例采用超临界CO2),各自多点添加,在双螺杆的转动下充分混合并熔融,控制温度为150℃;
3)将2)中熔融扩散所得的均相体系在挤出模头降压降温使泡孔成核、生长,最后冷却定型,得到软质PBAT发泡材料。
本实施例从原理上讲以多羟基CNC与PBAT酯基间作用引发物理交联点,将PBAT分子链交联在一起,使得分子间的作用力增加,分子的相对滑移减弱,使得本实施例所制软质发泡材料比同类PBAT产品具有更好的抗蠕变性能;从工艺上,只需将PBAT与CNC、扩链剂、发泡剂简单熔融共混即可一步法制备,大大简化了其他化学改性PBAT的工艺流程;从性能上,本实施例所制软质泡沫材料与常规泡沫材料相比具有突出的生物可降解性能,环保优势明显。
实施例2
本实施例的一种软质PBAT基生物可降解发泡材料的制备方法,包括以下步骤:
1)将20.0g纤维素微晶分散与150ml浓度为70%(v/v)的硫酸溶液中,通过磁力搅拌以120rpm的速率再65℃下反应7小时完成水解。将水解后的悬浮液用去离子水反复洗涤并在12000r/min的速率下高速离心7min,直到pH为中性。向悬浮液中滴入氨水(0.5%)调节pH至7并再次水洗,将得到的CNC悬浮液在去离子水中透析24小时,在冰箱中放置成冰后彻底冷冻干燥可得到疏松的CNC粉末;
2)将PBAT置于真空烘箱中80℃进行12小时干燥后,取90份PBAT与10份的CNC,加入2份扩链剂(本实施例采用甲苯-2,4二异氰酸酯TDI),4份发泡剂(本实施例采用超临界丁烷),各自多点添加,在双螺杆的转动下充分混合并熔融,控制温度为150℃;
3)将2)中熔融扩散所得的均相体系在挤出模头降压降温使泡孔成核、生长,最后冷却定型,得到PBAT发泡材料。
本实施例从原理上讲以多羟基CNC与PBAT酯基间作用引发物理交联点,将PBAT分子链交联在一起,使得分子间的作用力增加,分子的相对滑移减弱,使得本实施例所制软质发泡材料比同类PBAT产品具有更好的抗蠕变性能;从工艺上,只需将PBAT与CNC、扩链剂、发泡剂简单熔融共混即可一步法制备,大大简化了其他化学改性PBAT的工艺流程;从性能上,本实施例所制软质泡沫材料与常规泡沫材料相比具有突出的生物可降解性能,环保优势明显。
实施例3
本实施例的一种软质PBAT基生物可降解发泡材料的制备方法,包括以下步骤:
1)将20.0g纤维素微晶分散与150ml浓度为65%(v/v)的硫酸溶液中,通过磁力搅拌以110rpm的速率再60℃下反应6.5小时完成水解。将水解后的悬浮液用去离子水反复洗涤并在11000r/min的速率下高速离心5min,直到pH为中性。向悬浮液中滴入氨水(0.5%)调节pH至7并再次水洗,将得到的CNC悬浮液在去离子水中透析18小时,在冰箱中放置成冰后彻底冷冻干燥可得到疏松的CNC粉末;
2)将PBAT置于真空烘箱中80℃进行12小时干燥后,取80份PBAT与15份的CNC,加入5份扩链剂(本实施例采用二苯甲烷二异氰酸酯MDI),10份发泡剂(本实施例采用偶氮二甲酰胺AC),各自多点添加,在双螺杆的转动下充分混合并熔融,控制温度为150℃;
3)将2)中熔融扩散所得的均相体系在挤出模头降压降温使泡孔成核、生长,最后冷却定型,得到软质PBAT发泡材料。
本实施例从原理上讲以多羟基CNC与PBAT酯基间作用引发物理交联点,将PBAT分子链交联在一起,使得分子间的作用力增加,分子的相对滑移减弱,使得本实施例所制软质发泡材料比同类PBAT产品具有更好的抗蠕变性能;从工艺上,只需将PBAT与CNC、扩链剂、发泡剂简单熔融共混即可一步法制备,大大简化了其他化学改性PBAT的工艺流程;从性能上,本实施例所制软质泡沫材料与常规泡沫材料相比具有突出的生物可降解性能,环保优势明显。
实施例4
本实施例的一种软质PBAT基生物可降解发泡材料的制备方法,包括以下步骤:与实施例1相比,除了本实施例中发泡剂采用4,4-氧代双苯磺酰肼OBSH,以及各原料组分的配方改为:PBAT为50份,CNC为10份,扩链剂3份,发泡剂为5份外,其余参数与实施例1相同。
本实施例从原理上讲以多羟基CNC与PBAT酯基间作用引发物理交联点,将PBAT分子链交联在一起,使得分子间的作用力增加,分子的相对滑移减弱,使得本实施例所制软质发泡材料比同类PBAT产品具有更好的抗蠕变性能;从工艺上,只需将PBAT与CNC、扩链剂、发泡剂简单熔融共混即可一步法制备,大大简化了其他化学改性PBAT的工艺流程;从性能上,本实施例所制软质泡沫材料与常规泡沫材料相比具有突出的生物可降解性能,环保优势明显。
实施例5
本实施例的一种软质PBAT基生物可降解发泡材料的制备方法,包括以下步骤:与实施例1相比,除了本实施例中发泡剂采用碳酸钙,以及各原料组分的配方改为:PBAT为20份,CNC为5份,扩链剂2份,发泡剂为3份外,其余参数与实施例1相同。
本实施例从原理上讲以多羟基CNC与PBAT酯基间作用引发物理交联点,将PBAT分子链交联在一起,使得分子间的作用力增加,分子的相对滑移减弱,使得本实施例所制软质发泡材料比同类PBAT产品具有更好的抗蠕变性能;从工艺上,只需将PBAT与CNC、扩链剂、发泡剂简单熔融共混即可一步法制备,大大简化了其他化学改性PBAT的工艺流程;从性能上,本实施例所制软质泡沫材料与常规泡沫材料相比具有突出的生物可降解性能,环保优势明显。
实施例6
本实施例的一种软质PBAT基生物可降解发泡材料的制备方法,包括以下步骤:与实施例1相比,除了本实施例中发泡剂采用碳酸氢钠,以及各原料组分的配方改为:PBAT为1份,CNC为1份,扩链剂1份,发泡剂为0.1份外,其余参数与实施例1相同。
本实施例从原理上讲以多羟基CNC与PBAT酯基间作用引发物理交联点,将PBAT分子链交联在一起,使得分子间的作用力增加,分子的相对滑移减弱,使得本实施例所制软质发泡材料比同类PBAT产品具有更好的抗蠕变性能;从工艺上,只需将PBAT与CNC、扩链剂、发泡剂简单熔融共混即可一步法制备,大大简化了其他化学改性PBAT的工艺流程;从性能上,本实施例所制软质泡沫材料与常规泡沫材料相比具有突出的生物可降解性能,环保优势明显。
Claims (6)
1.一种软质PBAT基生物可降解发泡材料的制备方法,其特征在于,包括如下步骤:1)通过硫酸酸解法制备纤维素纳米晶;2)纤维素纳米晶、聚对苯二甲酸己二酸丁二醇酯、扩链剂、发泡剂熔融共混得到熔体;3)将步骤2)中熔体减压降温挤出。
2.如权利要求1所述的一种软质PBAT基生物可降解发泡材料的制备方法,其特征在于,所述的硫酸酸解法是指将纤维素微晶分散于硫酸溶液中,通过磁力搅拌机完成水解后的悬浮液反复洗涤并利用离心机离心至PH成中性,再向悬浮液中滴入浓度为0.5%的氨水并水洗,得到的纤维素纳米晶悬浮液在去离子水中透析,在冰箱放置后彻底冷冻干燥可得到疏松的纤维素纳米晶粉末;
所述纤维素微晶原料采用棉花、棉短绒、稻壳、松针、麻杆、橘皮中的一种或多种天然纤维素;
所述硫酸溶液的浓度为60%-70%;
所述磁力搅拌机的转速为100-120rpm,反应温度为55-65℃,反应时间为6-7h;
所述离心机的转速为10000-12000r/min,离心时间为4-7min;
所述纤维素纳米晶悬浮液在去离子水中透析时间为12-24h。
3.如权利要求1所述的一种软质PBAT基生物可降解发泡材料的制备方法,其特征在于,所述的纤维素纳米晶与聚对苯二甲酸己二酸丁二醇酯、扩链剂、发泡剂熔融共混,所述熔融共混各原料组分的重量份数为:聚对苯二甲酸己二酸丁二醇酯为1-100份,纤维素纳米晶为1-20份,扩链剂为1-10份,发泡剂为0.1-15份;
所述的扩链剂采用二异氰酸酯封端的长链型聚氨酯预聚体或两端由环氧基封端的长链型聚合物中的一种;
所述的发泡剂采用物理发泡剂或化学发泡剂中的一种,其中所述物理发泡剂采用超临界CO2、超临界N2、超临界丁烷中的一种;所述化学发泡剂采用偶氮类化合物、磺酰肼类化合物、碳酸钙、碳酸氢钠中的一种。
4.如权利要求3所述的一种软质PBAT基生物可降解发泡材料的制备方法,其特征在于,所述扩链剂采用甲苯-2,4二异氰酸酯,二苯甲烷二异氰酸酯中的一种;所述偶氮类化合物的化学发泡剂采用偶氮二甲酰胺,所述磺酰肼类化合物的化学发泡剂采用4,4-氧代双苯磺酰肼。
5.如权利要求1所述的一种软质PBAT基生物可降解发泡材料的制备方法,其特征在于,所述步骤2)共混步骤具体为:
(1)将聚对苯二甲酸己二酸丁二醇酯置于真空烘箱中80℃进行12小时干燥;
(2)取聚对苯二甲酸己二酸丁二醇酯、纤维素纳米晶、扩链剂、发泡剂在双螺杆的转动下采用各自多点添加的方式充分混合并熔融得到均相体系。
6.如权利要求1所述的一种软质PBAT基生物可降解发泡材料的制备方法,其特征在于,所述步骤3)熔体减压降温挤出步骤具体为:将步骤2)得到的熔体在挤出模头降压降温,使泡孔成核、生长,最后冷却定型,得到软质聚对苯二甲酸己二酸丁二醇酯发泡材料。
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