CN105860456A - 一种可降解聚酯型防水材料及其制备方法 - Google Patents
一种可降解聚酯型防水材料及其制备方法 Download PDFInfo
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- CN105860456A CN105860456A CN201610302556.5A CN201610302556A CN105860456A CN 105860456 A CN105860456 A CN 105860456A CN 201610302556 A CN201610302556 A CN 201610302556A CN 105860456 A CN105860456 A CN 105860456A
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- acid
- waterproof material
- type waterproof
- aliphatic
- dicarboxylic acid
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Abstract
本发明涉及一种可降解聚酯型防水材料，其特征在于原料组分及各组分占原料总量的质量百分比分别为：脂肪族二羧酸‑芳香族二羧酸‑脂肪族或脂环族二元醇共聚酯：20％～89％；聚碳酸二亚丙酯1％～50％；淀粉1％～30％；偶联剂0.5％～1％；封端剂0.5％～1％；增塑剂0.5％～1％。将上述原料加入高混机中充分混合后，通过挤出机进行挤出成型，得到可降解聚酯型防水材料。所制备的材料可用于防水材料中，具备生物可降解功能。
Description
技术领域
本发明属于高分子聚合物材料合成制备领域，涉及一种可降解聚酯型防水材料及其制备方法，具体涉及一种主要由脂肪族二羧酸-芳香族二羧酸-脂肪族二元醇共聚酯/聚碳酸二亚丙酯/淀粉/其他助剂组成的可降解聚酯型防水材料及其制备方法。
背景技术
随着工业化进程的加快，人类生产和生活过程中产生的废弃物不断增多，处理废弃物的主要方法为填埋法，即将废旧塑料等污染物送到填埋场掩埋后待其自然降解。但是，废旧塑料等物质的填埋量远远大于自然降解量，导致填埋场数量不断减少，废物处理成本不断增加，环境污染日渐严重。
因而，就需要一种可直接被环境、微生物等降解的塑料，这些塑料尤其适用于一次性的快速消费品中，当这些塑料使用结束后，可在自然界微生物如细菌、霉菌、真菌及藻类作用下分解成小分子化合物，这些小分子化合物又可被植物利用，从而使材料形成了封闭的绿色循环，实现人类生产、生活与自然环境的和谐相处。
目前研究最多的生物可降解塑料是脂肪族聚酯，它在堆肥条件下可被自然界的微生物经过数月将分解成水和CO2等物质，再次参与到植物的光合作用。此外它优良的生物相容性、聚合物和降解产物无毒等优点也使其日益受到关注。然而这类聚酯较差的力学性能，较低的熔点和玻璃化转变温度(通常分别低于65℃和-30℃)难以满足实际应用中对材料性能等各方面的要求，只被应用在极少数场合。
为了充分发挥脂肪族聚酯的生物降解性并实现大规模应用，各国的科研工作者进行了很多研究工作。其中，比较成功的例子是将脂肪族聚酯和芳香族聚酯进行共聚，由此得到的这种脂肪/芳香共聚酯结合了脂肪族聚酯的可生物降解性和芳香族聚酯优异的机械及加工性能，因此在生物可降解领域中脱颖而出。BASF专利CN 1075527 C公开了一种可生物降解聚合物的制备过程，将己二酸、对苯二甲酸和1,4-丁二醇共聚得到己二酸-对苯二甲酸与1,4-丁二醇的共聚酯。杜邦专利CN 200480022043.4公开了它的共聚酯的制备过程，利用芳香族二羧酸、脂肪族二羧酸、聚(亚烷基醚)二醇和二醇共聚得到脂肪族-芳香族聚醚酯。这些共聚酯较好的结合了芳香族聚酯的力学性能和脂肪族聚酯的生物降解性能，但是它们一般都存在以下缺点：(1)生产成本偏高；(2)高度疏水的链结构、缺少活性反应点；(3)降解速率较慢，使得其进一步广泛应用受限，所以有必要对可降解聚酯进行改性研究。
聚碳酸二亚丙酯[Poly(Propylene carbonate)，缩写为PPC]是一种由环氧丙烷(PO)和二氧化碳(CO2)交替共聚而成的可完全生物降解的新型热塑性材料，可应用于食物保鲜袋、防水塑料袋、一次性纸杯等领域。
发明内容
本发明的目的在于提供一种环保、可降解、力学性能好、低成本的一种可降解聚酯型防水材料，本发明的另一目的是提供上述材料的制备方法，本发明将从根本上解决传统塑料制品或一次性纸杯对环境造成的“白色污染”，并对塑料制品和一次性纸杯的防水性能增强改进。
本发明的技术方案为：一种可降解聚酯型防水材料,其特征在于原料组分及各组分占原料总量的质量百分比分别为：脂肪族二羧酸-芳香族二羧酸-脂肪族或脂环族二元醇共聚酯：20％～89％；聚碳酸二亚丙酯1％～50％；淀粉1％～30％；偶联剂0.5％～1％；封端剂0.5％～1％；增塑剂0.5％～1％。
优选上述脂肪族二羧酸-芳香族二羧酸-脂肪族或脂环族二元醇共聚酯中所述脂肪族二羧酸为乙二酸、丙二酸、丁二酸、甲基丁二酸、戊二酸、2-甲基戊二酸、3-甲基戊二酸、1,2-环己烷二甲酸、己二酸、3-甲基己二酸、2,2,5,5-四甲基己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸或十三烷二酸中的一种或几种；所述芳香族二羧酸为间苯二甲酸、对苯二甲酸、邻苯二甲酸、2,6-萘二甲酸、1,5-萘二甲酸、2,7-萘二甲酸、4,4’-联苯二甲酸或3,4’-联苯二甲酸中的一种或几种；所述的脂肪族二元醇为乙二醇、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、1,4-丁二醇、1,2-丁二醇、1,5-戊二醇、新戊二醇、1,6-己二醇、1,4-环己二甲醇、1,3-环己二甲醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,11-十一烷二醇或1,12-十二烷二醇中的一种或几种；所述脂环族二元醇为1,2-环己烷二甲醇或1,4-环己烷二甲醇。
优选上述的聚碳酸二亚丙酯(PPC)为重均分子量为1500～3000的聚合物。优选上述的淀粉为玉米淀粉、木薯淀粉、马铃薯淀粉、酯化淀粉或醚化淀粉中的一种或多种。优选上述的偶联剂为硅烷偶联剂、钛系偶联剂、铝系偶联剂或铝钛复合偶联剂中的一种或几种。优选上述的封端剂为顺丁烯二酸酐或己内酰胺中的一种或几种。优选上述的增塑剂为乙二醇、丙三醇或山梨醇、柠檬酸三丁酯(TBC)、柠檬酸三辛酯(TOC)、乙酰柠檬酸三丁酯(ATBC)或乙酰柠檬酸三辛酯(ATOC)中的一种或几种。
本发明还提供了上述的可降解聚酯型防水材料的制备方法，其具体步骤如下：
A、脂肪族二羧酸-芳香族二羧酸-脂肪族或脂环族二元醇共聚酯的制备；
(1)将芳香族二羧酸、脂肪族二羧酸、脂肪族二元醇或脂环族二元醇与氯仿按质量百分比为1：(0.5～1.5)：(0.4～1.8)：(0.2～0.5)置于反应容器中，升温进行恒温酯化反应，然后在进行负压酯化反应，得到初步酯化产物；
(2)将上述初步酯化产物，加入占酯化产物质量百分比为0.01～0.15％脱水剂和占酯化产物质量百分比为0.1～0.5％催化剂，在高温、负压下缩聚反应得到高分子量生物可降解共聚酯；
B、可降解聚酯型防水材料的制备：将步骤A所得到的脂肪族二羧酸-芳香族二羧酸-脂肪族或脂环族二元醇共聚酯与聚碳酸二亚丙酯、淀粉、偶联剂、封端剂和增塑剂加入高混机中充分混合后，通过挤出机进行挤出成型，得到可降解聚酯型防水材料。
优选步骤(1)中升温速率为5～1010℃/min；恒温酯化反应温度为120～200℃，反应时间2～3小时；负压酯化的压力为40～100KPa，负压酯化反应时间0.5～2小时。
优选步骤(2)中缩聚反应温度控制在220～260℃；压力控制在10～50kPa内；反应时间2～5小时；升温速率为5～1010℃/min。
优选上述步骤B中所述的高混机的转速为1000～2000转/分钟；混合时间为10～30分钟；所述的挤出机为双螺杆挤出机，工艺参数为：物料温度在35-200℃之间，螺杆转速80-350转/分钟。
优选上述的脱水剂为二乙基碳二亚胺盐、二异丙基碳二亚胺盐或二环己基碳二亚胺盐中的一种；所述催化剂为钛酸四乙酯、钛酸四异丙酯、钛酸四丁酯、钛酸四异辛酯、草酸钛钾、辛酸亚锡、二丁锡二月桂酸酯、二醋酸二丁基锡、正硅酸甲酯或正硅酸乙酯中的至少一种。
有益效果：
1.本发明通过调整脂肪族二羧酸-芳香族二羧酸-脂肪族或脂环族二元醇共聚酯与PPC比例，所制备的生物可降解高分子材料能够适应各种不同条件和环境下的使用，生物可降解性能及防水性能优异，且生产成本低；
2.本发明所制备的生物可降解高分子材料降解均匀且彻底、无残留、无二次污染，在适当条件下降解速度较快；
3.本发明所制备的生物可降解高分子材料力学性能优异，且符合相关产品力学、热学性能要求。
具体实施方式
下面结合实施例对本发明做进一步详述(以下实例中未特殊说明，添加量均为质量份数)：
实施例1
首先向20份氯仿溶剂中加入100份对苯二甲酸、50份丁二酸和40份1，2-丁二醇，搅拌均匀，并以10℃/min速率迅速升温至165℃，进行酯化，恒温反应2个小时。然后在40KPa压力下进行负压酯化，时间0.5小时，再以5℃/min升温至240℃，加入0.21份钛酸四丁酯催化剂，0.021份二环己基碳二亚胺盐脱水剂，减压至45KPa进行缩聚反应4小时，即得到对苯二甲酸/丁二酸-丁二醇共聚酯。
将1份江苏中科金龙化工股份有限公司生产的重均分子量为2000的PPC、89份以上步骤得到的共聚酯产物、8.5份玉米淀粉、0.5份铝系偶联剂、0.5份顺丁烯二酸酐和0.5份乙酰柠檬酸三丁酯，初步混合后缓慢加入到高搅机中搅拌20min，高混机转速为1000转/分钟，将均匀混合料在双螺杆挤出机中挤出、造粒，挤出机温度设定为110℃，转速设定为250转/分钟。
采用本例的原料吹膜制得厚度为0.03mm的包装薄膜，在常温下土埋，根据ASTM D5338-92塑料在受控堆肥化条件下需氧生物降解的标准试验方法检测其降解性能。用所得到的粒料在烘箱中测试粒料开始发粘的温度，同时用所得到的粒料在注射机中按GB/T17037-1997的要求进行制样，然后按GB/T1040-2006和GB/T 2918-1998的要求进行拉伸性能测试，记录测试结果。采用ASTM D538-92受控堆肥化条件下测定可降解塑料需氧生物降解的试验方法测定产品降解性能。
实施例2
首先向50份氯仿溶剂中加入100份间苯二甲酸、80份1,2-环己烷二甲酸和180份乙二醇，搅拌均匀，并以10℃/min速率迅速升温至120℃，进行酯化，恒温反应2.5个小时。然后100KPa压力下进行负压酯化，时间1小时，再以5℃/min升温至220℃，加入1.23份钛酸四异辛酯催化剂，0.205份二乙基碳二亚胺盐脱水剂，减压至50KPa进行缩聚反应5小时，即得到对苯二甲酸/1,2-环己烷二甲酸-乙二醇共聚酯。
将50份江苏中科金龙化工股份有限公司生产的重均分子量为3000的PPC、20份以上步骤得到的共聚酯产物、27份木薯淀粉、1份钛系偶联剂、1份己内酰胺和1份乙二醇初步混合后缓慢加入到高搅机中搅拌20min，高混机转速2000转/分钟，将均匀混合料在双螺杆挤出机中挤出、造粒，挤出机温度设定为35℃，转速设定为100转/分钟。
按照实施例一所述方法进行性能测试，并记录数据。
实施例3
首先向30份氯仿溶剂中加入100份邻苯二甲酸、110份乙二酸和120份1，6-己二醇，搅拌均匀，并以5℃/min速率迅速升温至200℃，进行酯化，恒温反应3小时。然后60KPa压力下进行负压酯化，时间2小时，再以5℃/min升温至260℃，加入1.6份正硅酸甲酯催化剂，0.48份二异丙基碳二亚胺盐脱水剂，减压至45KPa进行缩聚反应4.5小时，即得到间苯二甲酸/丁二酸-己二醇共聚酯。
将17.9份江苏中科金龙化工股份有限公司生产的重均分子量为1500的PPC、50份以上步骤得到的共聚酯产物连同30份马铃薯淀粉、0.8份铝钛复合偶联剂、0.6份顺丁烯二酸酐和0.7份丙三醇，初步混合后缓慢加入到高搅机中搅拌20min，高混机转速为1500转/分钟，将均匀混合料在双螺杆挤出机中挤出、造粒，挤出机温度设定为200℃，转速设定为160转/分钟。
按照实施例一所述方法进行性能测试，并记录数据。
实施例4
首先向40份氯仿溶剂中加入100份2，7-萘二甲酸、150份己二酸和60份1，3-丙二醇，搅拌均匀，并以10℃/min速率迅速升温至150℃，进行酯化，恒温反应2小时。然后50KPa压力下进行负压酯化，时间1.5小时，再以10℃/min升温至235℃，加入1.4份二醋酸丁基酯催化剂，0.35份二环己基碳二亚胺盐脱水剂，减压至10KPa进行缩聚反应2小时，即得到萘二甲酸/己二酸-丙二醇共聚酯。
将40份江苏中科金龙化工股份有限公司生产的重均分子量为3000的PPC、57份以上步骤得到的共聚酯产物、1份醚化淀粉、0.6份硅烷偶联剂、0.5份己内酰胺和0.9份柠檬酸三丁酯，初步混合后缓慢加入到高搅机中搅拌30min，高混机转速为1000转/分钟，将均匀混合料在双螺杆挤出机中挤出、造粒，挤出机温度设定为90℃，转速设定为200转/分钟。
按照实施例一所述方法进行性能测试，并记录数据。
为比较本发明共混塑料防水降解改性效果，特选取市售分子量为12.4×104，玻璃化转变温度为-15.4℃的纯PBS与本发明中采用的纯PPC按照实施例一所述方法进行相同性能测试，具体测试结果如下：
表1.试验结果
通过上述实验数据可知：本发明的可降解聚酯型防水材料的降解时间较纯PPC略长，但又短于纯PBS，力学性能的实验数据中，拉伸强度比纯PPC和纯PBS提高较多；断裂伸长率处于较大的变化范围，拓宽了可降解聚酯型防水材料的应用范围。
以上公开的仅为本申请的几个具体实施例，但本申请并非局限于此，任何实质性相同的变化或其组合，都应落在本申请的保护范围内。
Claims (10)
1.一种可降解聚酯型防水材料,其特征在于其原料组分及各组分占原料总量的质量百分比分别为：脂肪族二羧酸-芳香族二羧酸-脂肪族或脂环族二元醇共聚酯：20％～89％；聚碳酸二亚丙酯1％～50％；淀粉1％～30％；偶联剂0.5％～1％；封端剂0.5％～1％；增塑剂0.5％～1％。
2.根据权利要求1所述的可降解聚酯型防水材料，其特征在于所述的脂肪族二羧酸-芳香族二羧酸-脂肪族或脂环族二元醇共聚酯中所述脂肪族二羧酸为乙二酸、丙二酸、丁二酸、甲基丁二酸、戊二酸、2-甲基戊二酸、3-甲基戊二酸、1,2-环己烷二甲酸、己二酸、3-甲基己二酸、2,2,5,5-四甲基己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸或十三烷二酸中的一种或几种；所述芳香族二羧酸为间苯二甲酸、对苯二甲酸、邻苯二甲酸、2,6-萘二甲酸、1,5-萘二甲酸、2,7-萘二甲酸、4,4’-联苯二甲酸或3,4’-联苯二甲酸中的一种或几种；所述的脂肪族二元醇为乙二醇、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、1,4-丁二醇、1,2-丁二醇、1,5-戊二醇、新戊二醇、1,6-己二醇、1,4-环己二甲醇、1,3-环己二甲醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,11-十一烷二醇或1,12-十二烷二醇中的一种或几种；所述脂环族二元醇为1,2-环己烷二甲醇或1,4-环己烷二甲醇。
3.根据权利要求1所述的可降解聚酯型防水材料，其特征在于所述的聚碳酸二亚丙酯的重均分子量为1500～3000。
4.根据权利要求1所述的可降解聚酯型防水材料，其特征在于所述的淀粉为玉米淀粉、木薯淀粉、马铃薯淀粉、酯化淀粉或醚化淀粉中的一种或多种。
5.根据权利要求1所述的可降解聚酯型防水材料，其特征在于所述的偶联剂为硅烷偶联剂、钛系偶联剂、铝系偶联剂或铝钛复合偶联剂中的一种或几种；所述的封端剂为顺丁烯二酸酐或己内酰胺中的一种或几种；所述的增塑剂为乙二醇、丙三醇或山梨醇、柠檬酸三丁酯、柠檬酸三辛酯、乙酰柠檬酸三丁酯或乙酰柠檬酸三辛酯中的一种或几种。
6.一种制备如权利要求1所述的可降解聚酯型防水材料的方法，其具体步骤如下：
A、脂肪族二羧酸-芳香族二羧酸-脂肪族或脂环族二元醇共聚酯的制备；
(1)将芳香族二羧酸、脂肪族二羧酸、脂肪族二元醇或脂环族二元醇与氯仿按质量百分比为1：(0.5～1.5)：(0.4～1.8)：(0.2～0.5)置于反应容器中，升温进行恒温酯化反应，然后在进行负压酯化反应，得到初步酯化产物；
(2)将上述初步酯化产物，加入占酯化产物质量百分比为0.01～0.15％脱水剂和占酯化产物质量百分比为0.1～0.5％催化剂，在高温、负压下缩聚反应得到高分子量生物可降解共聚酯；
B、可降解聚酯型防水材料的制备：将步骤A所得到的脂肪族二羧酸-芳香族二羧酸-脂肪族或脂环族二元醇共聚酯与聚碳酸二亚丙酯、淀粉、偶联剂、封端剂和增塑剂加入高混机中充分混合后，通过挤出机进行挤出成型，得到可降解聚酯型防水材料。
7.根据权利要求6所述的方法，其特征在于步骤(1)中的升温速率为5～1010℃/min；恒温酯化反应温度为120～200℃，反应时间2～3小时；负压酯化的压力为40～100KPa，负压酯化反应时间0.5～2小时。
8.根据权利要求6所述的方法，其特征在于步骤(2)中缩聚反应温度控制在220～260℃；压力控制在10～50kPa内；反应时间2～5小时；升温速率为5～1010℃/min。
9.根据权利要求6所述的方法，其特征在于步骤B中所述的高混机的转速为1000～2000转/分钟；混合时间为10～30分钟；所述的挤出机为双螺杆挤出机，工艺参数为：物料温度在35-200℃之间，螺杆转速80-350转/分钟。
10.根据权利要求6所述的方法，其特征在于步骤(2)中所述的脱水剂为二乙基碳二亚胺盐、二异丙基碳二亚胺盐或二环己基碳二亚胺盐中的一种；所述催化剂为钛酸四乙酯、钛酸四异丙酯、钛酸四丁酯、钛酸四异辛酯、草酸钛钾、辛酸亚锡、二丁锡二月桂酸酯、二醋酸二丁基锡、正硅酸甲酯或正硅酸乙酯中的至少一种。
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