CN117327388A - 一种淀粉改性可降解塑料及其制备方法 - Google Patents
一种淀粉改性可降解塑料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种淀粉改性可降解塑料及其制备方法,以对硝基苯甲酸和二乙醇胺为原料在DCC的作用下,对硝基苯甲酸上的羧基和二乙醇胺上的仲胺脱水反应,制得中间体1,将中间体1和己内酯为原料,在辛酸亚锡的作用下,形成嵌段共聚物,制得改性聚己内酯,将改性聚己内酯用钯碳还原,使得改性聚己内酯侧链上的硝基转变为氨基,再与改性单体挤出造粒,该改性淀粉上含有长链烷基和有机硅链段,能够降低可降解塑料的吸水性,同时含有弹性聚氨酯链段和有机硅链段,能够增加可降解塑料的机械性能,进而避免了淀粉使可降解塑料变脆的问题,该可降解塑料为改性聚己内酯分子链和改性淀粉分子链交叉的网格状,使得机械性能相较单一的链状分子塑料更强。
Description
技术领域
本发明涉及可降解塑料制备技术领域,具体涉及一种淀粉改性可降解塑料及其制备方法。
背景技术
近年来,随着塑料制品的不断发展,高分子材料由于其耐腐蚀、质量轻、廉价、容易加工成型等优点,已经在许多领域代替了传统材料。但随着高分子材料的使用越来越广泛,高分子材料之间的共价键键能较高,较好的耐腐蚀特性也使得废弃的高分子塑料在自然环境中难以自然降解而形成的“白色污染”对环境造成了极大的影响。目前对塑料制品的处理方法主要还集中在:掩埋,焚烧,回收再利用这三种方法,但其中掩埋和焚烧对环境仍然会造成一定的影响,而回收再利用的整体成本较高,这三种方法都不是处理白色污染的理想方法。此外,由于传统塑料的主要来源不油是一种不可再生资源,而不油资源的枯竭危机也对塑料产业的发展产生了极大的影响。因此,为了解决日益严重的环境污染问题,摆脱对石油资源的依赖,天然可降解高分子以及合成可降解的高分子材料是近期研究的热点。
发明内容
本发明的目的在于提供一种淀粉改性可降解塑料及其制备方法,解决了现阶段淀粉改性的可降解塑料会变脆的问题。
本发明的目的可以通过以下技术方案实现:
一种淀粉改性可降解塑料的制备方法,具体包括如下步骤:
步骤A1:将对硝基苯甲酸、二乙醇胺、DCC和甲苯混合均匀,在转速为200-300r/min,温度为30-40℃的条件下,进行反应3-5h,制得中间体1,将中间体1、己内酯和DMF混合均匀,通入氮气保护,在转速为150-200r/min,温度为140-145℃的条件下,搅拌并加入辛酸亚锡,进行反应5-7h,制得改性聚己内酯;
步骤A2:将改性聚己内酯、二氯甲烷和钯碳混合均匀,通入氮气置换空气,再通入氢气置换空气,在温度为50-55℃,压强为1MPa的条件下,进行反应至氢气不再被吸收,过滤去除滤渣,将滤液蒸馏去除二氯甲烷,将底物和改性淀粉加入双螺杆挤出机中,在转速为30-60r/min,温度为150-160℃的条件下,挤出造粒,制得可降解塑料。
进一步,步骤A1所述的对硝基苯甲酸、二乙醇胺和DCC的摩尔比为1:1:1.1,中间体1、己内酯和辛酸亚锡的用量比为10mmol:15mL:0.4mmol。
进一步,步骤A2所述的改性聚己内酯、二氯甲烷和钯碳的用量比为0.2g:100mL:1g,底物和改性淀粉的质量比为1:1.5。
进一步,所述的改性淀粉由如下步骤制成:
步骤B1:将二苯二氯硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅和去离子水混合,在转速为200-300r/min,温度为60-70℃的条件下,搅拌10-15min后,加入浓硫酸和1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷,进行反应4-6h后,调节pH至中性,制得中间体2,将氯苯和光气、异氰酸苯酯混合,在转速为150-200r/min,温度为0℃的条件下,搅拌并加入中间体2,升温至70-80℃,保温2-3h,升温至130-135℃,保温5-7h,制得改性单体;
步骤B2:将玉米淀粉加入去离子水中,在转速为200-300r/min,温度为85-90℃的条件下,搅拌并加入硬脂酸和盐酸,升温至95℃,进行反应40-50min,制得预处理淀粉,将改性单体和聚四氢呋喃醚二醇混合,在转速为200-300r/min,温度为80-85℃的条件下,进行反应3-5h后,加入1,4-丁二醇、二月桂酸二丁基锡和N,N-二甲基乙酰胺,继续反应10-15min,加入预处理淀粉,继续反应1-1.5h,制得改性淀粉。
进一步,步骤B1所述的二苯二氯硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅、去离子水和1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷的用量比为1mmol:2mmol:20mL:2mmol,浓硫酸的用量为二苯二氯硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅和1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷质量和的1-1.5%,氯苯、光气、异氰酸苯酯和中间体2的用量比为250mL:3mol:0.5mol:1mol。
进一步,步骤B2所述的玉米淀粉、去离子水、硬脂酸和盐酸的用量比为8g:150mL:0.3g:0.1mL,改性单体、聚四氢呋喃醚二醇、1,4-丁二醇和预处理淀粉的质量比为52:35:2.5:200,二月桂酸二丁基锡的用量比为改性单体、聚四氢呋喃醚二醇和1,4-丁二醇质量和的0.01%,聚四氢呋喃醚二醇的分子量为1000。
本发明的有益效果:本发明制备的一种淀粉改性可降解塑料以对硝基苯甲酸和二乙醇胺为原料在DCC的作用下,对硝基苯甲酸上的羧基和二乙醇胺上的仲胺脱水反应,制得中间体1,将中间体1和己内酯为原料,在辛酸亚锡的作用下,形成嵌段共聚物,制得改性聚己内酯,将改性聚己内酯用钯碳还原,使得改性聚己内酯侧链上的硝基转变为氨基,再与改性单体挤出造粒,改性淀粉侧链上含有环氧基能够与氨基反应,使得改性淀粉分子链与改性聚己内酯分子链连接,起到架桥作用,达到分子链穿插效果,进而增强可降解塑料的韧性,改性淀粉以二苯二氯硅烷和3-缩水甘油醚氧基丙基甲基二乙氧基硅为原料,先水解,再与1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷聚合,形成双胺封端的聚硅氧烷,制得中间体2,将中间体2和光气,在异氰酸苯酯的作用下,使得氨基转变异氰酸酯基,制得改性单体,将玉米淀粉用硬脂酸处理,使得玉米淀粉分子链上接枝长链烷基,制得预处理淀粉,将改性单体、聚四氢呋喃醚二醇和1,4-丁二醇反应,形成聚氨酯预聚体,再与预处理淀粉上的羟基反应,制得改性淀粉,该改性淀粉上含有长链烷基和有机硅链段,能够降低可降解塑料的吸水性,同时含有弹性聚氨酯链段和有机硅链段,能够增加可降解塑料的机械性能,进而避免了淀粉使可降解塑料变脆的问题,该可降解塑料为改性聚己内酯分子链和改性淀粉分子链交叉的网格状,使得机械性能相较单一的链状分子塑料更强。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
一种淀粉改性可降解塑料的制备方法,具体包括如下步骤:
步骤A1:将对硝基苯甲酸、二乙醇胺、DCC和甲苯混合均匀,在转速为200r/min,温度为30℃的条件下,进行反应3h,制得中间体1,将中间体1、己内酯和DMF混合均匀,通入氮气保护,在转速为150r/min,温度为140℃的条件下,搅拌并加入辛酸亚锡,进行反应5h,制得改性聚己内酯;
步骤A2:将改性聚己内酯、二氯甲烷和钯碳混合均匀,通入氮气置换空气,再通入氢气置换空气,在温度为50℃,压强为1MPa的条件下,进行反应至氢气不再被吸收,过滤去除滤渣,将滤液蒸馏去除二氯甲烷,将底物和改性淀粉加入双螺杆挤出机中,在转速为30r/min,温度为150℃的条件下,挤出造粒,制得可降解塑料。
步骤A1所述的对硝基苯甲酸、二乙醇胺和DCC的摩尔比为1:1:1.1,中间体1、己内酯和辛酸亚锡的用量比为10mmol:15mL:0.4mmol。
步骤A2所述的改性聚己内酯、二氯甲烷和钯碳的用量比为0.2g:100mL:1g,底物和改性淀粉的质量比为1:1.5。
所述的改性淀粉由如下步骤制成:
步骤B1:将二苯二氯硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅和去离子水混合,在转速为200r/min,温度为60℃的条件下,搅拌10min后,加入浓硫酸和1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷,进行反应4h后,调节pH至中性,制得中间体2,将氯苯和光气、异氰酸苯酯混合,在转速为150r/min,温度为0℃的条件下,搅拌并加入中间体1,升温至70℃,保温2h,升温至130℃,保温5h,制得改性单体;
步骤B2:将玉米淀粉加入去离子水中,在转速为200r/min,温度为85℃的条件下,搅拌并加入硬脂酸和盐酸,升温至95℃,进行反应40min,制得预处理淀粉,将改性单体和聚四氢呋喃醚二醇混合,在转速为200r/min,温度为80℃的条件下,进行反应3h后,加入1,4-丁二醇、二月桂酸二丁基锡和N,N-二甲基乙酰胺,继续反应10min,加入预处理淀粉,继续反应1h,制得改性淀粉。
步骤B1所述的二苯二氯硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅、去离子水和1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷的用量比为1mmol:2mmol:20mL:2mmol,浓硫酸的用量为二苯二氯硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅和1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷质量和的1%,氯苯、光气、异氰酸苯酯和中间体2的用量比为250mL:3mol:0.5mol:1mol。
步骤B2所述的玉米淀粉、去离子水、硬脂酸和盐酸的用量比为8g:150mL:0.3g:0.1mL,改性单体、聚四氢呋喃醚二醇、1,4-丁二醇和预处理淀粉的质量比为52:35:2.5:200,二月桂酸二丁基锡的用量比为改性单体、聚四氢呋喃醚二醇和1,4-丁二醇质量和的0.01%,聚四氢呋喃醚二醇的分子量为1000。
实施例2
一种淀粉改性可降解塑料的制备方法,具体包括如下步骤:
步骤A1:将对硝基苯甲酸、二乙醇胺、DCC和甲苯混合均匀,在转速为200r/min,温度为35℃的条件下,进行反应4h,制得中间体1,将中间体1、己内酯和DMF混合均匀,通入氮气保护,在转速为150r/min,温度为145℃的条件下,搅拌并加入辛酸亚锡,进行反应6h,制得改性聚己内酯;
步骤A2:将改性聚己内酯、二氯甲烷和钯碳混合均匀,通入氮气置换空气,再通入氢气置换空气,在温度为55℃,压强为1MPa的条件下,进行反应至氢气不再被吸收,过滤去除滤渣,将滤液蒸馏去除二氯甲烷,将底物和改性淀粉加入双螺杆挤出机中,在转速为30r/min,温度为155℃的条件下,挤出造粒,制得可降解塑料。
步骤A1所述的对硝基苯甲酸、二乙醇胺和DCC的摩尔比为1:1:1.1,中间体1、己内酯和辛酸亚锡的用量比为10mmol:15mL:0.4mmol。
步骤A2所述的改性聚己内酯、二氯甲烷和钯碳的用量比为0.2g:100mL:1g,底物和改性淀粉的质量比为1:1.5。
所述的改性淀粉由如下步骤制成:
步骤B1:将二苯二氯硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅和去离子水混合,在转速为200r/min,温度为65℃的条件下,搅拌15min后,加入浓硫酸和1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷,进行反应5h后,调节pH至中性,制得中间体2,将氯苯和光气、异氰酸苯酯混合,在转速为150r/min,温度为0℃的条件下,搅拌并加入中间体1,升温至75℃,保温2.5h,升温至130℃,保温6h,制得改性单体;
步骤B2:将玉米淀粉加入去离子水中,在转速为300r/min,温度为88℃的条件下,搅拌并加入硬脂酸和盐酸,升温至95℃,进行反应45min,制得预处理淀粉,将改性单体和聚四氢呋喃醚二醇混合,在转速为200r/min,温度为83℃的条件下,进行反应4h后,加入1,4-丁二醇、二月桂酸二丁基锡和N,N-二甲基乙酰胺,继续反应10min,加入预处理淀粉,继续反应1.3h,制得改性淀粉。
步骤B1所述的二苯二氯硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅、去离子水和1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷的用量比为1mmol:2mmol:20mL:2mmol,浓硫酸的用量为二苯二氯硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅和1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷质量和的1.3%,氯苯、光气、异氰酸苯酯和中间体2的用量比为250mL:3mol:0.5mol:1mol。
步骤B2所述的玉米淀粉、去离子水、硬脂酸和盐酸的用量比为8g:150mL:0.3g:0.1mL,改性单体、聚四氢呋喃醚二醇、1,4-丁二醇和预处理淀粉的质量比为52:35:2.5:200,二月桂酸二丁基锡的用量比为改性单体、聚四氢呋喃醚二醇和1,4-丁二醇质量和的0.01%,聚四氢呋喃醚二醇的分子量为1000。
实施例3
一种淀粉改性可降解塑料的制备方法,具体包括如下步骤:
步骤A1:将对硝基苯甲酸、二乙醇胺、DCC和甲苯混合均匀,在转速为300r/min,温度为40℃的条件下,进行反应5h,制得中间体1,将中间体1、己内酯和DMF混合均匀,通入氮气保护,在转速为200r/min,温度为145℃的条件下,搅拌并加入辛酸亚锡,进行反应7h,制得改性聚己内酯;
步骤A2:将改性聚己内酯、二氯甲烷和钯碳混合均匀,通入氮气置换空气,再通入氢气置换空气,在温度为55℃,压强为1MPa的条件下,进行反应至氢气不再被吸收,过滤去除滤渣,将滤液蒸馏去除二氯甲烷,将底物和改性淀粉加入双螺杆挤出机中,在转速为60r/min,温度为160℃的条件下,挤出造粒,制得可降解塑料。
步骤A1所述的对硝基苯甲酸、二乙醇胺和DCC的摩尔比为1:1:1.1,中间体1、己内酯和辛酸亚锡的用量比为10mmol:15mL:0.4mmol。
步骤A2所述的改性聚己内酯、二氯甲烷和钯碳的用量比为0.2g:100mL:1g,底物和改性淀粉的质量比为1:1.5。
所述的改性淀粉由如下步骤制成:
步骤B1:将二苯二氯硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅和去离子水混合,在转速为300r/min,温度为70℃的条件下,搅拌15min后,加入浓硫酸和1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷,进行反应6h后,调节pH至中性,制得中间体2,将氯苯和光气、异氰酸苯酯混合,在转速为200r/min,温度为0℃的条件下,搅拌并加入中间体1,升温至80℃,保温3h,升温至135℃,保温7h,制得改性单体;
步骤B2:将玉米淀粉加入去离子水中,在转速为300r/min,温度为90℃的条件下,搅拌并加入硬脂酸和盐酸,升温至95℃,进行反应50min,制得预处理淀粉,将改性单体和聚四氢呋喃醚二醇混合,在转速为300r/min,温度为85℃的条件下,进行反应5h后,加入1,4-丁二醇、二月桂酸二丁基锡和N,N-二甲基乙酰胺,继续反应15min,加入预处理淀粉,继续反应1.5h,制得改性淀粉。
步骤B1所述的二苯二氯硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅、去离子水和1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷的用量比为1mmol:2mmol:20mL:2mmol,浓硫酸的用量为二苯二氯硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅和1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷质量和的1.5%,氯苯、光气、异氰酸苯酯和中间体2的用量比为250mL:3mol:0.5mol:1mol。
步骤B2所述的玉米淀粉、去离子水、硬脂酸和盐酸的用量比为8g:150mL:0.3g:0.1mL,改性单体、聚四氢呋喃醚二醇、1,4-丁二醇和预处理淀粉的质量比为52:35:2.5:200,二月桂酸二丁基锡的用量比为改性单体、聚四氢呋喃醚二醇和1,4-丁二醇质量和的0.01%,聚四氢呋喃醚二醇的分子量为1000。
对比例1
本对比例与实施例1相比用玉米淀粉代替预处理玉米淀粉,其余步骤相同。
对比例2
本对比例与实施例1相比用玉米淀粉代替改性淀粉,其余步骤相同。
对比例3
本对比例与实施例1相比未加入3-缩水甘油醚氧基丙基甲基二乙氧基硅,其余步骤相同。
将实施例1-3和对比例1-3制得的可降解塑料,依照GB/T1040-92的标准,制成长度为50mm,窄截面长度为16mm,窄截面宽度为4mm的标准哑铃型,拉伸速度为200mm/min,检测拉伸强度和断裂伸长率,依照GB/T1043-79的标准检测缺口冲击强度,依照GB/T1042-79的方法,进行弯曲强度测试,检测结果如下表所示。
由上表可知本申请具有很好的机械性能。
以上内容仅仅是对本发明的构思所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明的构思或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
Claims (7)
1.一种淀粉改性可降解塑料的制备方法,其特征在于:具体包括如下步骤:
步骤A1:将对硝基苯甲酸、二乙醇胺、DCC和甲苯混合反应,制得中间体1,将中间体1、己内酯和DMF混合均匀,通入氮气保护,搅拌并加入辛酸亚锡,进行反应,制得改性聚己内酯;
步骤A2:将改性聚己内酯、二氯甲烷和钯碳混合均匀,通入氮气置换空气,再通入氢气置换空气,进行反应至氢气不再被吸收,过滤去除滤渣,将滤液蒸馏去除二氯甲烷,将底物和改性淀粉加入双螺杆挤出机中,挤出造粒,制得可降解塑料。
2.根据权利要求1所述的一种淀粉改性可降解塑料的制备方法,其特征在于:步骤A1所述的对硝基苯甲酸、二乙醇胺和DCC的摩尔比为1:1:1.1,中间体1、己内酯和辛酸亚锡的用量比为10mmol:15mL:0.4mmol。
3.根据权利要求1所述的一种淀粉改性可降解塑料的制备方法,其特征在于:步骤A2所述的改性聚己内酯、二氯甲烷和钯碳的用量比为0.2g:100mL:1g,底物和改性淀粉的质量比为1:1.5。
4.根据权利要求1所述的一种淀粉改性可降解塑料的制备方法,其特征在于:所述的改性淀粉由如下步骤制成:
步骤B1:将二苯二氯硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅和去离子水混合搅拌后,加入浓硫酸和1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷,进行反应后,调节pH至中性,制得中间体2,将氯苯和光气、异氰酸苯酯混合,搅拌并加入中间体2,升温保温,制得改性单体;
步骤B2:将玉米淀粉加入去离子水中,搅拌并加入硬脂酸和盐酸,升温反应,制得预处理淀粉,将改性单体和聚四氢呋喃醚二醇混合反应后,加入1,4-丁二醇、二月桂酸二丁基锡和N,N-二甲基乙酰胺,继续反应,再加入预处理淀粉,继续反应,制得改性淀粉。
5.根据权利要求4所述的一种淀粉改性可降解塑料的制备方法,其特征在于:步骤B1所述的二苯二氯硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅、去离子水和1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷的用量比为1mmol:2mmol:20mL:2mmol,浓硫酸的用量为二苯二氯硅烷、3-缩水甘油醚氧基丙基甲基二乙氧基硅和1,3-双(3-氨基丙基)-1,1,3,3-四甲基二硅氧烷质量和的1-1.5%,氯苯、光气、异氰酸苯酯和中间体2的用量比为250mL:3mol:0.5mol:1mol。
6.根据权利要求4所述的一种淀粉改性可降解塑料的制备方法,其特征在于:步骤B2所述的玉米淀粉、去离子水、硬脂酸和盐酸的用量比为8g:150mL:0.3g:0.1mL,改性单体、聚四氢呋喃醚二醇、1,4-丁二醇和预处理淀粉的质量比为52:35:2.5:200,二月桂酸二丁基锡的用量比为改性单体、聚四氢呋喃醚二醇和1,4-丁二醇质量和的0.01%。
7.一种淀粉改性可降解塑料,其特征在于:根据权利要求1-6任一所述的制备方法制备而成。
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