CN116478442A - 一种低成本多功能化pbat发泡改性料及其制备方法 - Google Patents
一种低成本多功能化pbat发泡改性料及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种低成本多功能化PBAT发泡改性料及其制备方法,主要针对PBAT熔体强度差,生物降解材料成本高,功能化差,开发的一种多功能化低成本PBAT发泡改性料的制备技术,利用低成本的多羟基糖类,与功能化基团反应,并通过扩链剂、增容剂、功能助剂等与PBAT进行扩链功能化反应,实现了对PBAT降本增熔的同时,也赋予了其一定的功能化作用,如抗菌、阻隔、吸附等,其倍率在2~30倍可调,开闭孔可调,推进了生物降解材料在食品保鲜、电子包装、医疗、鞋材等领域的应用。
Description
技术领域
本发明涉及一种低成本多功能化PBAT发泡改性料及其制备方法,主要针对PBAT熔体强度差,生物降解材料成本高,功能化差,开发的一种多功能化低成本PBAT发泡改性料的制备技术。
背景技术
高分子材料行业对生物降解材料的研究及应用掀起了高潮,但生物降解材料的成本高,一定程度上限制了其的广泛推广,因此在保证其的生物可降解下特性下的绿色轻量化降本技术需求迫切。
目前生物降解材料主要类别为PLA、PBAT、PBS等,其中PBAT的价位最低,但目前轻量化的应用以PLA材质的为主,如挤出发泡PLA,以及低倍率的PLA吸塑泡沫产品且多用在餐盒、饮杯等低端耗品领域,低成本PBAT材质的轻量化产品应用很少,特别是低成本高倍率发泡产品,这些主要是由于PBAT的低熔体强度有关,因此急需开发一类低成本功能化PBAT发泡料,以便推进生物降解材料在高低端领域应用的低成本化。
专利CN 113549305 A公布了一种全生物降解改性PBAT发泡板材及其制备方法,其主要是采用PBAT与聚乳酸、低密度聚乙烯LDPE、聚丙烯PP其中的一种刚性聚合物,并通过与环氧基扩链剂共混完成对PBAT分子结构上的增熔、增刚作用,且其中刚性聚合物与PBAT的质量比为(5~30):100。但环氧类扩链剂主要与羟基、羧基基团反应剧烈,与聚乙烯、聚丙烯中的C-H键反应有限,且LDPE、PP属于完全不降解材料,高含量也一定程度上影响了产品的全生物降解性能,与PLA聚合物共混扩链,能一定程度上实现增刚作用,但高分子量的PLA对PBAT分子链上的反应增刚有限,且成本较高。
发明内容
本发明涉及发泡领域,主要针对PBAT熔体强度差,生物降解材料成本高,功能化差,旨在开发的一种多功能化低成本PBAT发泡改性料的制备技术,利用低成本的多羟基糖类,与功能化基团反应,并通过扩链剂、增容剂、功能助剂等与PBAT进行扩链功能化反应,实现了对PBAT降本增熔的同时,也赋予了其一定的功能化作用,如抗菌、阻隔、吸附等,其倍率在2~30倍可调,开闭孔可调,推进了生物降解材料在食品保鲜、电子包装、医疗、鞋材等领域的应用。
本发明的发泡料的制备技术如下:
1、将多羟基糖类、功能化聚合基团供体、催化剂、扩链剂按照一定比例共混后利用缩聚反应釜反应,反应得到预聚物后,通过冷冻干燥得到疏水型酯化多羟基糖Ⅰ;
2、将步骤1中所得改性多羟基糖Ⅰ按照一定比例与PBAT、扩链剂、增容剂、功能助剂通过螺杆设备加工得到功能化低成本可发PBAT改性材料Ⅱ或者PBAT改性泡沫Ⅲ;
3、将步骤2中制得的功能化低成本可发PBAT改性材料Ⅱ经过超临界气体发泡得到功能化低成本的PBAT泡沫材料Ⅳ。
其中步骤1中所述的多羟基糖为含2个及2个以上羟基基团单体的天然糖类聚聚合物,如玉米淀粉、红薯淀粉、木质纤维、竹纤维等的一种或者多种的组合;
步骤1中所述的功能化聚合基团供体为乙交酯、丙交酯、低分子量聚乳酸、低分子量聚乙醇酸、乙醇酸、醋酸酐、马来酸酐、多元酸、PPC等带有羧基、乙酰基、羟基等活性基团的多官能团物质的一种或者两种以上的共混物,与多羟基糖羟基基团摩尔比为1:1~2;
步骤1催化剂为钛酸四丁酯、醋酸锌、氧化锌、氯化亚锡、辛酸亚锡、磷酸、三氧化二锑、咪唑类、DMAP、醇铁等常用的酯化缩聚或者开环聚合的催化剂,其占多羟基糖和功能化聚合基团供体总质量的1%~5%;;
上述步骤中扩链剂为带有多个环氧基团的物质,如巴斯夫的ADR类扩链剂,联盟化学的LM-S322、环氧大豆油等,其占步骤1及步骤2中反应总体质量的0.1%~5%;
步骤2中增容剂如甘油、乙二醇、铝酸酯类、马来酸酐接枝物等,占树脂总总质量的0%~10%,根据步骤2中的功能化助剂的添加量情况添加;
步骤2中的功能化助剂,如除味剂、抗菌剂、增硬剂、抗静电剂、抗氧剂等,加入量占树脂总量的1%~30%。
步骤2中螺杆加工设备为注塑机、双螺杆挤出机,注塑发泡机、挤出发泡机等
步骤2中功能化低成本可发PBAT改性材料Ⅱ及泡沫Ⅲ形状可为粒子、板材、棒材、异型材;
步骤2中超临界气体为超临界二氧化碳、氮气中的一种或者二者的共混物;超临界气体发泡装置为珠粒发泡或者模压发泡方式。
本发明中多羟基糖类的酯化很大程度上增加了其与PBAT共混体系的相容性,也拓展了生物降解材料的加工适用领域,其中酯化多羟基糖类与PBAT质量比为1:10-1:1,优选为1:3-1:5,酯化多羟基糖类的量加入过多和过少都不能保证泡沫材料的性能。
本发明在多羟基糖类的酯化过程中加入功能化聚合基团供体,很大程度上增加了发泡体系的强度以及缓冲吸能效果,其中功能化聚合基团供体与多羟基糖羟基基团摩尔比为1:1~2,上述摩尔比范围是保证发泡条件的重要参数,功能化聚合基团供体的含量过低或过高会导致泡沫材料强度和缓冲吸能效果不能达到要求。
优选的,其中功能化聚合基团供体为低分子量聚乳酸或PPC。
有益效果
1、成分完全生物可降解;2、多羟基糖经过酯化处理,具有疏水亲油特性,可以很好的与PBAT相容,除了能提升TPS的添加量外,还拓展了发泡料加工工艺适用范围,如可以利用现有的以水为介质的EPP珠粒发泡装备,再降低成本的同时,方便更多的异型设计;3、多羟基糖结构上引入功能化基团,可以赋予材料阻隔、生物相容性,耐刺穿等特性,实现部分的功能化。
附图说明
附图1实施例1中珠粒发泡成型的PBAT泡沫。
附图2模压发泡成型的PBAT泡沫。
附图3挤出发泡成型的PBAT发泡膜材。
附图4对比例1PBAT珠粒发泡粒子形貌。
附图5a对比例2PBAT发泡的正面照。
附图5b对比例2PBAT发泡的侧面照。
附图6实施例1与对比例3中的产品应变-应力压缩曲线。
附图7实施例1与对比例3中的珠粒成型PBAT泡沫应力-缓冲系数曲线。
附图8实施例2中木质纤维酯化前后的红外谱图。
具体实施方式
应当理解,上述实施例仅为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
实施例1
将支链玉米淀粉、马来酸酐、低分子量聚乳酸(Mn≤50000)、辛酸亚锡、扩链剂LM322,环氧大豆油按照质量比75:15:10:5:1:5共混后在缩聚反应釜,150~160℃下熔融聚合1~2h后停止反应。得到预聚物,然后在冻干得到疏水型酯化淀粉。
把所得疏水型酯化淀粉与PBAT、硅烷偶联剂处理后的增硬剂碳酸钙、LM322、抗氧剂1010、按照20:60:20:0.5:0.2比例共混后加入双螺杆挤出,挤出温度为150~170℃,转速为200rpm,水下切造粒得到功能化低成本可发PBAT改性材料。
把所得的PBAT改性材料利用EPP的发泡釜进行90℃,二氧化碳6MPa发泡1h,并进行蒸汽成型(模缝15mm,压力0.5~0.7bar,成型保温10~15S),即得高强轻质的PBAT异型包材,见附图1;
实施例2
将木质纤维素、醋酸酐、PPC、醋酸锌、钛酸四丁酯、环氧氯丙烷,按照质量70:10:20:5:1共混进行反应,反应温度160~180℃。得到预聚物,然后在冻干得到疏水型酯化木质纤维素。
把所得酯化木质纤维素与PBAT、除味剂、ADR4370、抗氧剂1010、抗菌剂ZnO按照20:80:5:0.9:0.2:2比例共混后加入双螺杆挤出,挤出温度为150~180℃,转速为250rpm,制得5~6mm厚的功能化低成本可发PBAT改性板材。
把所得的PBAT改性板材放置模压发泡釜中,在100~120℃,进行二氧化碳/N2的共混12~20MPa发泡2h,即得亲肤鞋用高弹PBAT泡沫,见附图2;
实施例3
将淀粉、PPC、丙交酯、三氧化二锑、氯化亚锡,ADR4468按照质量比75:10:10:2:2:1共混进行反应,反应温度160~180℃。得到预聚物,然后在冻干得到疏水型酯化淀粉。
把所得酯化淀粉与PBAT、硅酮除味母粒、ADR4468、抗氧剂1010、多价盐类高分子抗菌剂按照30:70:5:5:0.2:5比例共混后加入超临界氮气发泡双螺杆挤出机,挤出温度为150~180℃,转速为250rpm,压力为10MPa,制得具有开孔结构的低成本抗菌PBAT发泡膜材,可用于食品或者医疗卫生耗品,见附图3。
对比例1
对比实施例1,直接用无酯化的淀粉代替酯化淀粉进行相同的操作,结构发现在EPP珠粒发泡釜中泡孔坍塌厉害,表层发粘,无法进行后期的蒸汽成型,见附图4;
对比例2
对比实施例2,直接用无酯化的木质纤维素代替酯化木质纤维素进行相同的操作,后期发泡发现泡孔坍塌,鼓泡分层严重,高倍率熔接差,见附图5a和图5b。
对比例3
对比实施例1,在步骤1中不加入低分子量聚乳酸功能基团供体,其他与实施例1一致。
对比例4
对比实施例2,在步骤1中不加入PPC类功能基团供体,其他与实施例2一致。
检测方法
1淀粉显色测试:将酯化淀粉溶于水中,滴加碘溶液,根据颜色观察淀粉的酯化情况。
2对实施例2中的酯化前后的木质纤维进行红外测试:
3发泡倍率的测定:依据标准ISO 845-2006,利用排水法测出发泡前后的密度,发泡倍率为发泡前树脂密度与泡沫体密度之比。
4力学性能测试:利用万能试验机对于实施例2及实施例3中的PBAT泡沫进行测试:
对于实施例1中珠粒成型高强轻质的PBAT异型包材泡沫压缩性能按照标GB/T4857.4-2008进行测试,以12mm/min的压缩速度对对材料的压缩及缓冲性能进行测试。其中缓冲系数根据压缩曲线通过下面算式求得:
对于实施例2中的亲肤鞋用高弹PBAT泡沫PBAT泡沫按照相应标准拉伸ISO 1798-2008、压缩永久变形GB/T6669-2008(50℃/50%/6h/30min)、直角撕裂ISO8067-2008。
5落球测试
依据标准GB/T6370-2008,对泡沫材料进行多测试,取平均值。
6硬度测试
依据标准HG/T2489-2007,利用邵氏C硬度计对泡沫材料进行测试。
结果分析
对实施例1中的酯化淀粉进行显色反应测试发现滴加碘溶液,不呈现蓝色,而呈现紫红色,说明淀粉中的羟基大部分已经和马来酸酐反应,形成酯。另外附图8中木质纤维的红外谱图中1750cm-1附近的C=O羰基峰、1250cm-1附近的C-O峰的增强及峰面积的增大及3400cm-1附近的O-H峰的削减可以表明,淀粉和木质纤维已经成功酯化,具备了疏水的特性。再根据实施例1(附图1)与对比例1(附图4)、实施例2(附图2)与对比例2(附图5)的发泡形貌可以看出,多羟基糖类的酯化很大程度上增加了其与PBAT共混体系的相容性,也拓展了生物降解材料的加工适用领域,极大程度上降低了推广成本。
从附图6中的实施例1与对比例3的压缩曲线应变—应力曲线以及附图7中根据附图6求得的实施例1与对比例3的应力—缓冲系数C曲线可以看出,泡沫材料的强度(杨氏模量越大强度越大)的先后顺序是:实施例1>EPS>对比例3,缓冲系数的结果也出现类似的规律,说明结晶性低分子量聚乳酸的加入很大程度上增加了发泡体系的强度以及缓冲吸能效果,较竞品EPS也有较大的提升。
从表1实施例2以及对比例4的PBAT泡沫产品性能列表对比可以看出,具有PPC的添加,对发泡倍率影响不大,但很大程度上提升了发泡材料的拉伸、回弹、撕裂等方面的性能,增韧、增强效果明细,用在鞋材方面,极大程度上提升了材料的耐用性,在结合抗菌、除味功能助剂的协效下,将极大程度上推动PBAT材料在高端鞋材、医疗卫生耗品等领域的应用。
表1实施例2以及对比例4的PBAT泡沫产品性能
Claims (9)
1.一种PBAT发泡改性料的制备方法,其特征在于,该方法包括以下步骤:
(1)将多羟基糖类、功能化聚合基团供体、催化剂、扩链剂按照一定比例共混后利用缩聚反应釜反应,反应得到预聚物后,通过冷冻干燥得到疏水型酯化多羟基糖Ⅰ;
(2)将步骤(1)中所得改性疏水型酯化多羟基糖Ⅰ按照一定比例与PBAT、扩链剂、增容剂、功能助剂通过螺杆设备加工得到功能化低成本可发PBAT改性材料Ⅱ或者PBAT改性泡沫Ⅲ;
(3)将步骤(2)中制得的功能化低成本可发PBAT改性材料Ⅱ经过超临界气体发泡得到功能化低成本的PBAT泡沫材料;
在多羟基糖类的酯化过程中加入功能化聚合基团供体,增加了发泡体系的强度以及缓冲吸能效果;
多羟基糖类的酯化增加了多羟基糖类与PBAT共混体系的相容性。
2.根据权利要求1所述的一种PBAT发泡改性料的制备方法,其特征在于:其中步骤1中所述的多羟基糖为含2个以上羟基基团单体的天然糖类聚合物。
3.根据权利要求2所述的一种PBAT发泡改性料的制备方法,其特征在于:所述的天然糖类聚合物为玉米淀粉、红薯淀粉、木质纤维、竹纤维中的一种或者多种的组合。
4.根据权利要求1所述的一种PBAT发泡改性料的制备方法,其特征在于:所述步骤1中所述的功能化聚合基团供体为乙交酯、丙交酯、低分子量聚乳酸、低分子量聚乙醇酸、乙醇酸、醋酸酐、马来酸酐、多元酸、PPC或带有羧基、乙酰基、羟基等活性基团的多官能团物质的一种或者两种以上的共混物,与多羟基糖羟基基团摩尔比为1:1~2。
5.根据权利要求1所述的一种PBAT发泡改性料的制备方法,其特征在于:所述步骤1催化剂为钛酸四丁酯、醋酸锌、氧化锌、氯化亚锡、辛酸亚锡、磷酸、三氧化二锑、咪唑类、DMAP或醇铁,其占多羟基糖和功能化聚合基团供体总质量的1%~5%。
6.根据权利要求1所述的一种PBAT发泡改性料的制备方法,其特征在于:所述步骤2中增容剂为甘油、乙二醇、铝酸酯类或马来酸酐接枝物,占树脂总总质量的0%~10%;所述步骤2中的功能化助剂为除味剂、抗菌剂、增硬剂、抗静电剂或抗氧化剂,加入量占树脂总量的1%~30%。
7.根据权利要求1所述的一种PBAT发泡改性料的制备方法,其特征在于:所述步骤2中PBAT改性材料Ⅱ及泡沫Ⅲ形状为粒子、板材、棒材或异型材。
8.根据权利要求1所述的一种PBAT发泡改性料的制备方法,其特征在于:所述步骤2中超临界气体为超临界二氧化碳、氮气中的一种或者二者的共混物;超临界气体发泡装置为珠粒发泡或者模压发泡。
9.根据权利要求1所述的一种PBAT发泡改性料的制备方法,其特征在于:所述功能化聚合基团供体为低分子量聚乳酸、PPC、PCL、PGA、PBS等。
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