CN100378138C - 改进二氧化碳-环氧丙烷共聚物脆性和冷流性的方法 - Google Patents
改进二氧化碳-环氧丙烷共聚物脆性和冷流性的方法 Download PDFInfo
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Abstract
本发明属于一种改进二氧化碳-环氧丙烷共聚物的脆性和冷流性的方法。按重量比取PPC50～98份，最佳60～95份，PBS2～50份，最佳为5～40份，顺丁烯二酸酐1份， SiO2 0.5～3.0份，最佳为1～2份。在高搅机中混合均匀后在40℃下真空干燥10小时，在Haake密炼机中以30r/min的速度在140℃下密炼得到PPC/PBS(或PBSA)共混物。共混物具有完全生物降解的性能，与PPC相比，共混物的拉伸强度保持在30MPa以上，断裂伸长率提高3-15倍，大幅度改善了PPC的脆性；PPC/PBS共混物在70℃下可保持尺寸稳定，PPC/PBSA共混物在55℃下可保持尺寸稳定，均没有粘流现象发生，大幅度提高了PPC的耐热性能。
Description
技术领域：
本发明属于一种改进二氧化碳-环氧丙烷共聚物的脆性和冷流性的方法。
背景技术：
PPC是由二氧化碳和环氧丙烷共聚合成的可完全生物降解的一种脂肪族聚碳酸酯，中国专利CN1116332C和中国专利申请03105023.9提供了高分子量PPC的合成方法。由于PPC的链柔性较大，为无定型态，分子链间相互作用力较小，其玻璃化转变温度较低(37-40℃)加上PPC链端为羟基，因此PPC存在室温粘流及低温脆性较大等缺陷。对PPC进行封端可防止其从末端发生解拉链反应，提高PPC的热稳定性。对PPC与不同高分子材料共混可提高PPC的热学和力学性能。陈立班指出PPC与聚丙烯酸甲酯或乙酯、硝基纤维素、醋酸纤维素、丙基纤维素、聚己内酯、聚偏二氟乙烯、乙烯-醋酸乙烯共聚物等具有相容性(高分子通报，3，128-133，1999)。Robenson指出PPC和聚乙酸乙烯酯(PVAc)(80∶20)共混，所获得的共混物的强度是原聚合物的倍数(US 4,912,149(1990))。Dixon指出PPC与聚氯乙烯(PVC)共混可以改善聚氯乙烯的熔融流动性及隔氧性能(US 4,137,280(1979))。叶晓光等指出PPC与聚碳酸酯(PC)共混做为热电转换材料的基体，其断裂伸长率由7％提高到20％，而断裂强度无明显降低，所得的共混物具有良好的加工性能，并可制造模塑料；此外，PPC与聚乙烯醇(PVA)共混体系具有良好的相容性并可增加韧性，可用于制造膜、乳液、黏合剂等(化学通报，10，29-34(1997))。
聚丁二酸丁二醇酯和聚丁二酸/己二酸丁二醇酯(PBS和PBSA)是半结晶聚合物，具有可完全生物降解性能，其玻璃化转变温度可在-32-45℃之间调节，但生产成本较高。
发明内容：
为了解决PPC脆性和冷流性技术问题，发明人提出的技术方案是PPC与PBS(或PBSA)共混，既能保持其各自的完全生物降解性，又能改善PPC的热学力学性能，和脆性冷流性的方法。
本发明的目的是提供一种改进二氧化碳一环氧丙烷共聚物的脆性和冷流性的方法。
本发明主要采用可生物降解的主链含长烷基链的脂肪族聚碳酸酯改进二氧化碳-环氧丙烷共聚物的脆性和室温粘流问题。
本发明所用的PPC按中国专利CN1116332C和中国专利申请03105023.9提供的方法制备。PPC数均分子量Mn为45000～120000g/mol，最佳数均分子量为55000～90000；分子量分布指数Mw/Mn为2.5～6.5，最佳为3.0～5.0，玻璃化温度为35-39℃。PBS和PBSA(Bionolle)由ShowaHighpolymer CO，LTD.提供。PBS的密度为1.26g/cm3，变形温度97℃，结晶度35-45％，玻璃化转变温度-32℃，熔点114-115℃。PBSA的密度为1.23g/cm3，变形温度69℃，结晶度20-35％，玻璃化转变温度-45℃，熔点93-95℃。防止PPC在共混过程中发生“解拉链”反应的封端剂为市售顺丁二烯二酸酐(1级品)。
本发明提供的改进二氧化碳-环氧丙烷共聚物脆性和冷流性的方法如下：
按重量比取PPC 50～98份，最佳60～95份；PBS(或PBSA)2～50份，最佳为5～40份；顺丁烯二酸酐(MAH)1份；SiO2 0.5～3.0份，最佳为1～2份。将它们在高搅机中混合均匀。混合物40℃下真空干燥10小时后，在haake密炼机中以30r/mim的速度在140℃下密炼得到PPC/PBS(或PPC/PBSA)共混物。
本发明的PPC的封端剂为顺丁烯二酸酐。为防止在热加工过程中PPC发生解拉链讲解反应，通常在加工过程中用封端剂对PPC进行封端。
顺丁烯二酸酐作为封端剂不仅有利于共混加工过程，而且原料易得，价格适中。
上述的共混物在140℃下压制成1毫米厚板材，测试力学性能。测试结果表明：本发明提供的改进二氧化碳-环氧丙烷共聚物脆性和冷流性的方法，改进二氧化碳-环氧丙烷共聚物的脆性和室温粘流问题。所得到的PPC共混物与纯PPC相比，共混物的拉伸强度保持在30MPa以上，断裂伸长率提高3-15倍，PPC/PBS共混物在70℃下可保持尺寸稳定，没有粘流现象发生，而PPC/PBSA共混物在55℃下可保持尺寸稳定，没有粘流现象发生，大幅度提高了PPC的耐热性能。
具体实施方式
实施例1
取数均分子量为60000g/mol，分子量分布指数为4.3的PPC 92.5份，PBS 5份，MAH 1份，SiO2 1.5份在高搅机中混合均匀。混合物在真空烘箱中，40℃下真空干燥10小时后，于haake密炼机中以30r/min的速度在140℃下密炼至扭距曲线平稳，得到PPC/PBS共混物。
上述得到PPC/PBS共混物用平板硫化机，在140℃下压制成1毫米厚的板材，杨氏模量为639.5MPa；屈服强度为32.48MPa；拉伸强度为32.48MPa；
断裂伸长率为190.9％；断裂功为0.58J/mm2，70℃下没有粘流现象。
实施例2
取数均分子量为56000g/mol，分子量分布指数为3.5的PPC 87.5份，PBS 10份，MAH 1份，SiO2 1.5份在高搅机中混合均匀。混合物在真空烘箱中，40℃下真空干燥10小时后，于haake密炼机中以30r/min的速度在140℃下密炼至扭距曲线平稳，得到PPC/PBS共混物。
得到PPC/PBS共混物用平板硫化机在140℃下压制成1毫米厚的板材，杨氏模量为566.3MPa；屈服强度为 27.33MPa；拉伸强度为27.33MPa；断裂伸长率为463.7％；断裂功为1.26J/mm2，在70℃下可保持尺寸稳定，没有粘流现象发生。
实施例3
取数均分子量为71000g/mol，分子量分布指数为3.5的PPC 58.5份，PBS39份，MAH 1份，SiO2 1.5份在高搅机中混合均匀。混合物在真空烘箱中，40℃下真空干燥10小时后，于haake密炼机中以30r/min的速度在140℃下密炼至扭距曲线平稳，得到PPC/PBS共混物。
得到PPC/PBS共混物用平板硫化机在140℃下压制成1毫米厚的板材，杨氏模量为598.2MPa；屈服强度为34.71MPa；拉伸强度为34.71MPa；断裂伸长率为444.8％；断裂功为1.90J/mm2，在70℃下可保持尺寸稳定，没有粘流现象发生。
实施例4
取数均分子量为85000g/mol，分子量分布指数为5.0的PPC 77.5份，PBS
20份，MAH 1份，SiO2 2份在高搅机中混合均匀。混合物在真空烘箱中，40℃下真空干燥10小时后，于haake密炼机中以30r/min的速度在140℃下密炼至扭距曲线平稳，得到PPC/PBS共混物。
得到PPC/PBS共混物用平板硫化机在140℃下压制成1毫米厚的板材，杨式模量为722.6MPa；屈服强度为39.43MPa；拉伸强度为39.43MPa；断裂伸长率为126.5％；断裂功为0.54J/mm2，在70℃下可保持尺寸稳定，没有粘流现象发生。
实施例5
取数均分子量为56000g/mol，分子量分布指数为3.5的PPC 87.5份，PBSA 10份，MAH 1份，SiO2 1.5份在高搅机中混合均匀。混合物在真空烘箱中，40℃下真空干燥10小时后，于haake密炼机中以30r/min的速度在140℃下密炼至扭距曲线平稳，得到PPC/PBS共混物。
得到PPC/PBSA共混物用平板硫化机在140℃下压制成1毫米厚的板材，杨氏模量为612.5MPa；屈服强度为30.42MPa；拉伸强度为35.24MPa；断裂伸长率为440.8％；断裂功为1.71J/mm2，在70℃下可保持尺寸稳定，没有粘流现象发生。
比较例
取数均分子量为56000g/mol，分子量分布指数为3.5的PPC 97.5份，MAH 1份，SiO2 1.5份在高搅机中混合均匀。混合物在真空烘箱中，40℃下真空干燥10小时后，于haake密炼机中以30r/min的速度在140℃下密炼至扭距曲线平稳得到PPC。
得到PPC的样品用平板硫化机在140℃下压制成1毫米厚的板材，杨氏模量为717.6MPa；屈服强度为42.6MPa；拉伸强度为42.6MPa；断裂伸长率为34.73％；断裂功为0.17J/mm2。在室温下(25-30℃)存在粘流现象，35℃以上温度时粘流现象十分严重，造成粒料团聚。
Claims (4)
1.一种改进二氧化碳—环氧丙烷共聚物的脆性和冷流性的方法，其特征在于，按重量比取PPC 50～98份；PBS或PBSA 2～50份；顺丁烯二酸酐(MAH)1份；SiO2 0.5～3.0份；将它们在高搅机中混合均匀；混合物真空干燥，在haake密炼机中密炼得到共混物，从而使二氧化碳—环氧丙烷共聚物(PPC)的脆性和冷流性得到改进。
2.按权利要求1所述的一种改进二氧化碳—环氧丙烷共聚物的脆性和冷流性的方法，其特征在于：按重量比取PPC 50～98份；PBS或PBSA2～50份；顺丁烯二酸酐(MAH)1份；SiO2 0.5～3.0份；将它们在高搅机中混合均匀；混合物真空干燥，在haake密炼机中密炼得到共混物，从而使二氧化碳—环氧丙烷共聚物(PPC)的脆性和冷流性得到改进。
3.按权利要求1所述的一种改进二氧化碳—环氧丙烷共聚物的脆性和冷流性的方法，其特征在于：按重量比取PPC 60～95份；PBS或PBSA 5～40份；顺丁烯二酸酐(MAH)1份；SiO2为1～2份；将它们在高搅机中混合均匀；混合物40℃下真空干燥10小时，在haake密炼机中以30r/min的速度在140℃下密炼得到共混物，从而使二氧化碳—环氧丙烷共聚物(PPC)的脆性和冷流性得到改进。
4.按权利要求2所述的一种改进二氧化碳—环氧丙烷共聚物的脆性和冷流性的方法，其特征在于：按重量比取PPC 60～95份；PBS或PBSA 5～40份；顺丁烯二酸酐(MAH)1份；SiO2为1～2份；将它们在高搅机中混合均匀；混合物40℃下真空干燥10小时，在haake密炼机中以30r/min的速度在140℃下密炼得到共混物，从而使二氧化碳—环氧丙烷共聚物(PPC)的脆性和冷流性得到改进。
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| CNB2005100173001A CN100378138C (zh) | 2005-11-21 | 2005-11-21 | 改进二氧化碳-环氧丙烷共聚物脆性和冷流性的方法 |
| US11/589,940 US20070117908A1 (en) | 2005-11-21 | 2006-10-31 | Blend for improving the brittleness and cold flowability of a carbon dioxide-propylene oxide copolymer and method for producing the same |
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| CN100586971C (zh) * | 2008-07-18 | 2010-02-03 | 中国科学院长春应用化学研究所 | 一种交联的二氧化碳-环氧丙烷共聚物的制备方法 |
| CN101857668B (zh) * | 2010-07-02 | 2012-12-12 | 中国科学院长春应用化学研究所 | 一种可生物降解聚合物及其制备方法 |
| US8906488B2 (en) | 2010-07-14 | 2014-12-09 | Kimberly-Clark Worldwide, Inc. | Biodegradable blends and films having nano-structural features |
| EP2426174A1 (en) * | 2010-09-03 | 2012-03-07 | SK Innovation Co. Ltd. | Resin composition for sheet products |
| CN101914277B (zh) * | 2010-09-15 | 2012-02-01 | 中国科学院长春应用化学研究所 | 完全生物降解高韧性聚丙撑碳酸酯组合物及其制备方法 |
| CN101935445B (zh) * | 2010-09-21 | 2012-05-23 | 中国科学院长春应用化学研究所 | 一种二氧化碳-环氧丙烷共聚物组合物 |
| KR101406989B1 (ko) * | 2011-01-18 | 2014-06-13 | 에스케이이노베이션 주식회사 | 다층필름 |
| JP6007009B2 (ja) * | 2012-07-13 | 2016-10-12 | 住友精化株式会社 | 脂肪族ポリカーボネート樹脂組成物 |
| CN103965603B (zh) * | 2014-05-06 | 2016-01-20 | 宁波家塑生物材料科技有限公司 | 聚碳酸亚丙酯/聚丁二酸丁二醇酯/淀粉全生物降解复合材料及其制备方法 |
| CN104479081B (zh) * | 2015-01-14 | 2017-03-29 | 河北工业大学 | 一种通过反应挤出改性聚丙撑碳酸酯的方法 |
| CN105061971A (zh) * | 2015-06-16 | 2015-11-18 | 华南理工大学 | 酸酐和微晶纤维素协同改性聚甲基乙撑碳酸酯制备全降解复合材料的方法 |
| CN106009600B (zh) * | 2016-07-29 | 2019-07-23 | 菏泽学院 | 改善聚环氧乙烷/聚丁二酸丁二醇酯共混物力学性能的方法 |
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| US4912149A (en) * | 1989-02-22 | 1990-03-27 | Air Products And Chemicals, Inc. | Blends of poly(vinyl acetate) and poly(propylene carbonate) |
| US4946884A (en) * | 1989-03-22 | 1990-08-07 | Air Products And Chemicals, Inc. | Blends of poly(propylene carbonate) and poly(methyl methacrylate) and their use in decomposition molding |
| CN1371942A (zh) * | 2002-03-04 | 2002-10-02 | 中国科学院长春应用化学研究所 | 二氧化碳－环氧丙烷共聚物与聚3－羟基烷酸酯共混物的制备方法 |
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| US4066630A (en) * | 1977-01-10 | 1978-01-03 | Air Products And Chemicals, Inc. | End capped polyalkylene carbonates having improved thermal stability |
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| US4145525A (en) * | 1977-10-03 | 1979-03-20 | Air Products And Chemicals, Inc. | End capped polyalkylene carbonates |
| US4137280A (en) * | 1978-04-19 | 1979-01-30 | Air Products And Chemicals, Inc. | Polyalkylene carbonates as processing aids for polyvinyl chloride |
| US5763513A (en) * | 1994-05-19 | 1998-06-09 | Mitsui Toatsu Chemicals, Inc. | L-lactic acid polymer composition, molded product and film |
| US6573340B1 (en) * | 2000-08-23 | 2003-06-03 | Biotec Biologische Naturverpackungen Gmbh & Co. Kg | Biodegradable polymer films and sheets suitable for use as laminate coatings as well as wraps and other packaging materials |
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| US4912149A (en) * | 1989-02-22 | 1990-03-27 | Air Products And Chemicals, Inc. | Blends of poly(vinyl acetate) and poly(propylene carbonate) |
| US4946884A (en) * | 1989-03-22 | 1990-08-07 | Air Products And Chemicals, Inc. | Blends of poly(propylene carbonate) and poly(methyl methacrylate) and their use in decomposition molding |
| CN1371942A (zh) * | 2002-03-04 | 2002-10-02 | 中国科学院长春应用化学研究所 | 二氧化碳－环氧丙烷共聚物与聚3－羟基烷酸酯共混物的制备方法 |
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