CN106243562A - 一种淀粉基生物可降解塑料的制备方法 - Google Patents
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Abstract
本发明涉及一种淀粉基生物可降解塑料的制备方法,属于塑料制备技术领域。该方法通过高压萃取法提取得橙皮精油,用其和微生物复配对淀粉进行发酵改性,增加淀粉表面的酯基官能团,提高淀粉的疏水性,再将疏水改性后的淀粉和聚氯乙烯共混后即可制得可降解塑料。本发明通过增加淀粉表面疏水基团数量来提高其疏水性,从而改善淀粉与塑料之间的相容性,解决了常见的淀粉基生物可降解塑料由于淀粉分子中含有大量羟基与塑料进行混炼时两者相容性差导致塑料产品的力学性能和产品稳定性差的问题,具有优异的生物降解性。
Description
技术领域
本发明涉及一种淀粉基生物可降解塑料的制备方法,属于塑料制备技术领域。
背景技术
塑料比强度高、质量轻、难锈蚀、有一定的绝热和绝缘性以及具有与金属材料某些相似性能,因而20世纪80年代以来,塑料工业突飞猛进,塑料生产技术有了很大的发展,塑料己经渗透到工业,农业,国防及人们生产和生活的各个领域,与混凝土、钢铁和木材并称四大工业材料。由于塑料本身具有质量轻,耐腐蚀,绝缘性和易于成型加工等优点,使其成为人们不可或缺的材料。
然而现在塑料的使用却面临巨大的挑战。在自然界中塑料很难降解,使用后产生大量固体废弃物,对环境造成严重的污染。当前全球塑料产量增长速度惊人,使得这一问题的解决显得更加迫切。现在处理这些塑料垃圾时大部分采用焚烧和掩埋的方法,但都未能真正解决问题。
淀粉是一种多糖类化合物,广泛存在玉米,小麦,马铃薯等植物中,具有来源广的材料,成本低,可生物降解等优点,因此很早就有人将其作为生物降解研究。但是,天然淀粉本身在结构和性能上存在的缺陷,如淀粉的热稳定性差,加工温度不能过高;淀粉的亲水性较强与聚烯烃类树脂进行混炼时,两者不易均匀分散和互容直接影响塑料产品的力学性能和产品的稳定性。所以,淀粉直接填充到聚烯烃类树脂中的含量不能大于15%。然而,淀粉基生物降解塑料的降解能力主要取决于淀粉在塑料中的添加量,会直接影响塑料的可降解时间和程度。当淀粉的填充量>50%时,经一定时间才可能达到完全降解的程度。为此,就必须对淀粉进行疏水化改性处理。
发明内容
本发明主要解决的技术问题:针对目前常见的淀粉基生物可降解塑料由于淀粉分子中含有大量羟基与塑料进行混炼时两者相容性差,导致制品对湿度变化相当敏感,吸水后制品的力学性能明显降低,因此应用范围受到了限制的缺陷,提供了一种淀粉基生物可降解塑料的制备方法。该方法通过高压萃取法提取得橙皮精油,用其和微生物复配对淀粉进行发酵改性,增加淀粉表面的酯基官能团,提高淀粉的疏水性,再将疏水改性后的淀粉和聚氯乙烯共混后即可制得可降解塑料。本发明通过增加淀粉表面疏水基团数量来提高其疏水性,从而改善淀粉与塑料之间的相容性,解决了常见的淀粉基生物可降解塑料由于淀粉分子中含有大量羟基与塑料进行混炼时两者相容性差导致塑料产品的力学性能和产品稳定性差的问题,具有优异的生物降解性。
为了解决上述技术问题,本发明所采用的技术方案是:
(1)称取4~5kg橙皮放入气流粉碎机中粉碎后过60目标准筛,将过筛后的橙皮粉末和正丁烷按固液比为1:5混合后放入高压萃取釜中,在压力为0.4~0.6MPa,温度为50~60℃条件下萃取1~2h,分离得到萃取液,蒸馏回收正丁烷后得到粗橙皮油;
(2)按体积比为1:3将上述得到的粗橙皮油和质量浓度为90%的乙醇溶液混合后倒入超声萃取仪中,在50~60℃下以200~300W功率超声萃取40~60min后静置分层得到油相,再将油相移入蒸馏装置,在70~80℃下蒸馏回收乙醇后即得橙皮精油;
(3)按固液比为1:5将玉米淀粉和橙皮精油混合并放入高剪切乳化机中,以3000~4000r/min转速高速分散20~30min得淀粉分散液,将分散液转入陶瓷发酵罐中,再按接种量为8~10%向陶瓷罐中接入绿脓杆菌,用搅拌棒搅拌均匀后将发酵罐移入35~37℃温室中保温发酵改性10~15h;
(4)待改性结束后将改性产物放入高速离心机,以7000~8000r/min转速离心处理15~20min,分离得到下层沉淀,将沉淀转入布氏漏斗,用无水乙醇抽滤洗涤3~5遍后将滤渣放入烘箱在70~75℃下干燥2~3h后即得疏水改性淀粉;
(5)按质量比为3:5将上述疏水改性淀粉和聚氯乙烯混合均匀得混合单体,再加入混合单体总质量15~20%邻苯二甲酸二辛脂和5~10%聚乙二醇,一起放入双滚筒开炼机在80~90℃下混炼15~20min后转放于平板硫化机中在100~105℃以10~12MPa压力热压8~10min,再以5~7MPa压力常温压制4~6min后即可得到淀粉基生物可降解塑料。
本发明的具体应用方法:将本发明制得的淀粉基生物可降解塑料加热熔融后加入流延机料斗中,调节刮刀刀具为0.6~0.8mm,使热糊状液在流道上形成薄膜,调节冷却辊温度至15~25℃,使流道上薄膜迅速冷却成型,调节收卷张力为8~10kg,使冷却后的薄膜成卷,即得淀粉基生物可降解保鲜膜。经检测,本发明制得的可降解塑料在7~10天后降解率可达50~70%,15~20天后降解率达到90%以上,具有极佳的可降解性。
本发明的有益效果是:
(1)本发明制得的淀粉基生物可降解塑料原材料来源广泛,制备过程简单易操作,成本低廉;
(2)本发明制得的淀粉基生物可降解塑料具有极佳的生物降解性,在7~10天后降解率可达50~70%,15~20天后降解率达到90%以上,是一种绿色环保的新型材料。
具体实施方式
称取4~5kg橙皮放入气流粉碎机中粉碎后过60目标准筛,将过筛后的橙皮粉末和正丁烷按固液比为1:5混合后放入高压萃取釜中,在压力为0.4~0.6MPa,温度为50~60℃条件下萃取1~2h,分离得到萃取液,蒸馏回收正丁烷后得到粗橙皮油;按体积比为1:3将上述得到的粗橙皮油和质量浓度为90%的乙醇溶液混合后倒入超声萃取仪中,在50~60℃下以200~300W功率超声萃取40~60min后静置分层得到油相,再将油相移入蒸馏装置,在70~80℃下蒸馏回收乙醇后即得橙皮精油;按固液比为1:5将玉米淀粉和橙皮精油混合并放入高剪切乳化机中,以3000~4000r/min转速高速分散20~30min得淀粉分散液,将分散液转入陶瓷发酵罐中,再按接种量为8~10%向陶瓷罐中接入绿脓杆菌,用搅拌棒搅拌均匀后将发酵罐移入35~37℃温室中保温发酵改性10~15h;待改性结束后将改性产物放入高速离心机,以7000~8000r/min转速离心处理15~20min,分离得到下层沉淀,将沉淀转入布氏漏斗,用无水乙醇抽滤洗涤3~5遍后将滤渣放入烘箱在70~75℃下干燥2~3h后即得疏水改性淀粉;按质量比为3:5将上述疏水改性淀粉和聚氯乙烯混合均匀得混合单体,再加入混合单体总质量15~20%邻苯二甲酸二辛脂和5~10%聚乙二醇,一起放入双滚筒开炼机在80~90℃下混炼15~20min后转放于平板硫化机中在100~105℃以10~12MPa压力热压8~10min,再以5~7MPa压力常温压制4~6min后即可得到淀粉基生物可降解塑料。
实例1
称取4kg橙皮放入气流粉碎机中粉碎后过60目标准筛,将过筛后的橙皮粉末和正丁烷按固液比为1:5混合后放入高压萃取釜中,在压力为0.4MPa,温度为50℃条件下萃取1h,分离得到萃取液,蒸馏回收正丁烷后得到粗橙皮油;按体积比为1:3将上述得到的粗橙皮油和质量浓度为90%的乙醇溶液混合后倒入超声萃取仪中,在50℃下以200W功率超声萃取40min后静置分层得到油相,再将油相移入蒸馏装置,在70℃下蒸馏回收乙醇后即得橙皮精油;按固液比为1:5将玉米淀粉和橙皮精油混合并放入高剪切乳化机中,以3000r/min转速高速分散20min得淀粉分散液,将分散液转入陶瓷发酵罐中,再按接种量为8%向陶瓷罐中接入绿脓杆菌,用搅拌棒搅拌均匀后将发酵罐移入35℃温室中保温发酵改性10h;待改性结束后将改性产物放入高速离心机,以7000r/min转速离心处理15min,分离得到下层沉淀,将沉淀转入布氏漏斗,用无水乙醇抽滤洗涤3遍后将滤渣放入烘箱在70℃下干燥2h后即得疏水改性淀粉;按质量比为3:5将上述疏水改性淀粉和聚氯乙烯混合均匀得混合单体,再加入混合单体总质量15%邻苯二甲酸二辛脂和5%聚乙二醇,一起放入双滚筒开炼机在80℃下混炼15min后转放于平板硫化机中在100℃以10MPa压力热压8min,再以5MPa压力常温压制4min后即可得到淀粉基生物可降解塑料。
本发明的具体应用方法:将本发明制得的淀粉基生物可降解塑料加热熔融后加入流延机料斗中,调节刮刀刀具为0.6mm,使热糊状液在流道上形成薄膜,调节冷却辊温度至15℃,使流道上薄膜迅速冷却成型,调节收卷张力为8kg,使冷却后的薄膜成卷,即得淀粉基生物可降解保鲜膜。经检测,本发明制得的可降解塑料在7天后降解率可达50%,15天后降解率达到93%,具有极佳的可降解性。
实例2
称取5kg橙皮放入气流粉碎机中粉碎后过60目标准筛,将过筛后的橙皮粉末和正丁烷按固液比为1:5混合后放入高压萃取釜中,在压力为0.5MPa,温度为55℃条件下萃取2h,分离得到萃取液,蒸馏回收正丁烷后得到粗橙皮油;按体积比为1:3将上述得到的粗橙皮油和质量浓度为90%的乙醇溶液混合后倒入超声萃取仪中,在55℃下以250W功率超声萃取50min后静置分层得到油相,再将油相移入蒸馏装置,在75℃下蒸馏回收乙醇后即得橙皮精油;按固液比为1:5将玉米淀粉和橙皮精油混合并放入高剪切乳化机中,以3500r/min转速高速分散25min得淀粉分散液,将分散液转入陶瓷发酵罐中,再按接种量为9%向陶瓷罐中接入绿脓杆菌,用搅拌棒搅拌均匀后将发酵罐移入36℃温室中保温发酵改性13h;待改性结束后将改性产物放入高速离心机,以7500r/min转速离心处理18min,分离得到下层沉淀,将沉淀转入布氏漏斗,用无水乙醇抽滤洗涤4遍后将滤渣放入烘箱在73℃下干燥3h后即得疏水改性淀粉;按质量比为3:5将上述疏水改性淀粉和聚氯乙烯混合均匀得混合单体,再加入混合单体总质量18%邻苯二甲酸二辛脂和8%聚乙二醇,一起放入双滚筒开炼机在85℃下混炼18min后转放于平板硫化机中在103℃以11MPa压力热压9min,再以6MPa压力常温压制5min后即可得到淀粉基生物可降解塑料。
本发明的具体应用方法:将本发明制得的淀粉基生物可降解塑料加热熔融后加入流延机料斗中,调节刮刀刀具为0.7mm,使热糊状液在流道上形成薄膜,调节冷却辊温度至20℃,使流道上薄膜迅速冷却成型,调节收卷张力为9kg,使冷却后的薄膜成卷,即得淀粉基生物可降解保鲜膜。经检测,本发明制得的可降解塑料在9天后降解率可达60%,18天后降解率达到95%,具有极佳的可降解性。
实例3
称取5kg橙皮放入气流粉碎机中粉碎后过60目标准筛,将过筛后的橙皮粉末和正丁烷按固液比为1:5混合后放入高压萃取釜中,在压力为0.6MPa,温度为60℃条件下萃取2h,分离得到萃取液,蒸馏回收正丁烷后得到粗橙皮油;按体积比为1:3将上述得到的粗橙皮油和质量浓度为90%的乙醇溶液混合后倒入超声萃取仪中,在60℃下以300W功率超声萃取60min后静置分层得到油相,再将油相移入蒸馏装置,在80℃下蒸馏回收乙醇后即得橙皮精油;按固液比为1:5将玉米淀粉和橙皮精油混合并放入高剪切乳化机中,以4000r/min转速高速分散30min得淀粉分散液,将分散液转入陶瓷发酵罐中,再按接种量为10%向陶瓷罐中接入绿脓杆菌,用搅拌棒搅拌均匀后将发酵罐移入37℃温室中保温发酵改性15h;待改性结束后将改性产物放入高速离心机,以8000r/min转速离心处理20min,分离得到下层沉淀,将沉淀转入布氏漏斗,用无水乙醇抽滤洗涤5遍后将滤渣放入烘箱在75℃下干燥3h后即得疏水改性淀粉;按质量比为3:5将上述疏水改性淀粉和聚氯乙烯混合均匀得混合单体,再加入混合单体总质量20%邻苯二甲酸二辛脂和10%聚乙二醇,一起放入双滚筒开炼机在90℃下混炼20min后转放于平板硫化机中在105℃以12MPa压力热压10min,再以7MPa压力常温压制6min后即可得到淀粉基生物可降解塑料。
本发明的具体应用方法:将本发明制得的淀粉基生物可降解塑料加热熔融后加入流延机料斗中,调节刮刀刀具为0.8mm,使热糊状液在流道上形成薄膜,调节冷却辊温度至25℃,使流道上薄膜迅速冷却成型,调节收卷张力为10kg,使冷却后的薄膜成卷,即得淀粉基生物可降解保鲜膜。经检测,本发明制得的可降解塑料在10天后降解率可达70%, 20天后降解率达到95%,具有极佳的可降解性。
Claims (1)
1.一种淀粉基生物可降解塑料的制备方法,其特征在于具体制备步骤为:
(1)称取4~5kg橙皮放入气流粉碎机中粉碎后过60目标准筛,将过筛后的橙皮粉末和正丁烷按固液比为1:5混合后放入高压萃取釜中,在压力为0.4~0.6MPa,温度为50~60℃条件下萃取1~2h,分离得到萃取液,蒸馏回收正丁烷后得到粗橙皮油;
(2)按体积比为1:3将上述得到的粗橙皮油和质量浓度为90%的乙醇溶液混合后倒入超声萃取仪中,在50~60℃下以200~300W功率超声萃取40~60min后静置分层得到油相,再将油相移入蒸馏装置,在70~80℃下蒸馏回收乙醇后即得橙皮精油;
(3)按固液比为1:5将玉米淀粉和橙皮精油混合并放入高剪切乳化机中,以3000~4000r/min转速高速分散20~30min得淀粉分散液,将分散液转入陶瓷发酵罐中,再按接种量为8~10%向陶瓷罐中接入绿脓杆菌,用搅拌棒搅拌均匀后将发酵罐移入35~37℃温室中保温发酵改性10~15h;
(4)待改性结束后将改性产物放入高速离心机,以7000~8000r/min转速离心处理15~20min,分离得到下层沉淀,将沉淀转入布氏漏斗,用无水乙醇抽滤洗涤3~5遍后将滤渣放入烘箱在70~75℃下干燥2~3h后即得疏水改性淀粉;
(5)按质量比为3:5将上述疏水改性淀粉和聚氯乙烯混合均匀得混合单体,再加入混合单体总质量15~20%邻苯二甲酸二辛脂和5~10%聚乙二醇,一起放入双滚筒开炼机在80~90℃下混炼15~20min后转放于平板硫化机中在100~105℃下以10~12MPa压力热压8~10min,再以5~7MPa压力常温压制4~6min后即可得到淀粉基生物可降解塑料。
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