CN1092084A - 一种与淀粉化学结合的可生物降解聚乙烯组合物及其制备方法 - Google Patents
一种与淀粉化学结合的可生物降解聚乙烯组合物及其制备方法 Download PDFInfo
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Abstract
本发明是在有机酸催化剂存在下使用偶联剂对
基质树脂和淀粉进行化学结合从而使物理性能的下
降减至最低程度,同时通过简化工艺而实现生产成本
的降低。提供一种与淀粉化学结合的可生物降解聚
乙烯组合物,包括100重量份基质树脂,5—400重量
份可生物降解掺入物质,0.01—10重量份偶联剂,
0.01—1.0重量份自由基引发剂,0.01—5重量份路易
士酸催化剂,0.01—10重量份自氧化剂和0.01—10
重量份增塑剂并提供制备该组合物的方法。由本发
明制备的聚乙烯组合物的可生物降解能力,在淀粉含
量多于10%(重量)情况下显示出极好的可生物降解
能力。
Description
本发明涉及一种使用聚乙烯是具有广泛应用的聚烯烃,各种有机酸和偶联剂,例如马来酐,甲基丙烯酸酐或马来酰亚胺,通过淀粉与聚乙烯链化学结合的可生物降解聚乙烯组合物,本发明还涉及制备该组合物的方法。
塑料由于其低价格,光学特性以及极好的物理性能而作为金属的取代材料大量生产,它作为日常生活的必需材料已确立。但是,当大批塑料产品的污染问题在世界上日趋严重时,世界各国正在制订各种各样的对策,在南朝鲜为了解决由无用的塑料废料而产生的这种污染问题已成为一件感兴趣的事情。
解决这些问题的方法包括回收,焚烧和掩埋但每种方法都有一定的限制(回收产品在使用上的限制,额外的成本和掩埋的埸地),因此近年来世界各国已怪可降解塑料作了许多研究。
可降解塑料技术可分为可光降解领域,可生物降解领域和可生物光降解领域,近年来涉及可生物光降解领域的产品作为通用塑料产品的取代物已经增加。可光降解领域技术可分为两种类型,引入光敏官能基和加入光敏试剂,前一种类型已由Dow Chemical公司,DuPont公司,Union Carbide公司和Bayer公司市售使用市售乙烯和一氧化碳的共聚物,以及Ecoplastic公司使用市售乙烯基甲酮共聚物,后一种类型由Ampacet公司和Ideamasters公司市售。由Scott-Gilead公司开发添加的金属配合物类型是主要类型。然而,当这些光可降解产品用于作通用薄膜时仍存在高成本问题而且在太阳光被遮断(当它们埋于土壤下时)的情况下可光降解产品不降解,因此,光降解领域的技术不能解决废塑料的这些通用问题于是在许多国家已进行了可生物降解领域技术另一些研究。
尽管有许多种类的可生物降解塑料,例如,衍生物形成聚合物像PHB(聚-β-羟基丁酸酯),用微生物产生生物化学的聚合物,或带有天然聚合物如几丁质或淀粉的聚合物,在本说明书中将叙述有带有淀粉的聚合物的相关现有技术所提及和改进的问题。
由GJL Griffin的美国专利4021388揭示了制备改进的可生物降解薄膜的方法,该方法用硅烷偶联剂处理淀粉的表面使之疏水性,但它在基质树脂和淀粉之间仅提高一点儿物理相互作用强度以致很难解决薄膜在掺入淀粉时物理性能的降低。
尽管由USDA(美国农业部)F.H.otey等人申请的美国专利4133784和4337181揭示了在乙烯-丙烯酸共聚物中加入α-淀粉而制备可生物降解薄膜的方法,但由于乙烯-丙烯酸共聚物价格高而很难商业化且所生产的薄膜物理性能下降。
由Seonil Glucose公司申请的南朝鲜专利公开号90-6336和91-8553揭示了一种方法,通过提高淀粉的疏水性或提高基质树脂的亲水性而提高基质树脂和淀粉之间相互作用强度以达到提高基质树脂和淀粉的相容性。
在本发明中,通过简化艺而减少生产成本,同时通过用偶联剂使基质树脂和淀粉进行化学结合而对物理性能的不利影响减少到最低程度。
本发明的一个目的是提供一种与淀粉化学结合的可生物降解聚乙烯组合物,而本发明的另一目的是提供制备此可生物降解聚乙烯组合物的方法。
本发明的组合物包括100重量份基质树脂,5-400重量份可生物降解掺入物质,0.01-10重量份偶联剂,0.01-1.0重量份自由基引发剂,0.01-5重量份路易斯酸催化剂,0.01-10重量份自氧化剂和0.01-10重量份增塑剂和可有可无的0.01-10重量份的共聚单体。
图1是根据本发明例1的可生物降解薄膜的红外线吸收光谱;和
图2是根据本发明例1的一部分可生物降解薄膜由扫描电子显微镜(X1200)所示的电子显微摄影。
基质树脂是低密度聚乙烯(LDPE),线性低密度聚乙烯(LLDPE)或高密度聚乙烯(HDPE),可生物降解掺入物质是选自由淀粉,酸处理的淀粉(稀煮沸的淀粉),酯化淀粉,醚化淀粉,阳离子淀粉,及其混合物,例如玉米淀粉,乙酸淀粉,磷酸淀粉组成的一组物质中的一个。化学结合基质树脂和淀粉的偶联剂是马来酐、甲基丙烯酸酐或马来酰亚胺,而自由基引发剂是过氧化苯甲酰、二叔丁基过氧化物,偶氮二异丁腈,叔丁基氢过氧化物,过氧化二枯基,Lupersol 101(penn walt公司)或perkadox-14(AKzo公司)。自氧化剂是选自油酸锰,硬脂酸锰油酸亚铁(Ⅱ),硬脂酸亚铁(Ⅱ)及其混合物的一组物质中的一个或多个;增塑剂是例如油酰胺,Viton或Erucamide。共聚单体是选自丙烯腈,苯乙烯和丙烯酸乙酯的一组物质中一个或多个。路易斯酸催化剂是选自油酸[CH3(CH2)7CH∶CH(CH2)7CO2H]油酸[CH3·(CH2)7·CH∶CH·(CH2)7·COOH],亚油酸,硬脂酸,乙酸,对-甲苯磺酸,癸酸,十二烷酸,十四烷酸,草酸,丙二酸,琥珀酸和己二酸。
与淀粉化学结合制备可生物降解聚乙烯组合物的方法实现了本发明的另一目的,该方法包括以一定量混合基质树脂,可生物降解掺入物质,偶联剂,自氧化剂,增塑剂,路易斯酸催化剂和自由基引发剂然后反应挤出该混合物。
采用双螺杆挤出机实施反应挤出方法通过简化工艺而降低了生产成本并在混合淀粉后将物理性能的降低减至最小程度。也就是说,将聚乙烯、自由基引发剂、偶联剂,例如马来酐,甲基丙烯酸酐或马来酰亚胺,玉米淀粉或淀粉衍生物和偶合催化剂同时引入并在150~220℃的温度和50~300rpm的螺杆转速下反应挤出从而酯化淀粉,在此期间发生偶联剂接枝到聚乙烯链上。已经发现使用0.01-10重量份偶联剂,例如马来酐、甲基丙烯酸酐或马来酰亚胺,0.01-1.0重量份自由基引发剂和0.01-5重量份路易斯酸催化剂优选各使用0.3重量份的自由基引发剂和路易斯酸催化剂,物理性能极好。
可生物降解掺入物质是,例如玉米淀粉、改性淀粉像醋酸淀粉、磷酸淀粉、氧化淀粉、阳离子淀粉等,该淀粉事先被干燥使水分含量小于3%避免在形成薄膜时产生气泡,因为工业生产的淀粉所含水分含量在12-15%的范围。
制备可降解粒料的方法是混合一定量的基质树脂,可生物降解掺入物质,偶联剂,自氧化剂,增塑剂,路易斯酸催化剂和自由基引发剂,在塑度记录仪的混合器中熔融该混合物或用配料器放置每种组分,熔融,挤出该混合物,用切粒机将其造粒。可生物降解膜的制备方法是将该粒料制成压塑薄膜或用热压机和制膜挤出机制成吹塑薄膜。压塑膜或吹塑膜也可通过将低密度聚乙烯,线性低密度聚乙烯或高密度聚乙烯加入到粒料中,然后干混并挤出该混合的粒料而制备。可生物降解树脂粒料也可模压成聚乙烯瓶。
可生物降解膜的机械性能例如拉伸强度和拉伸伸长可用Instron测定而物理性能可通过ASTM的标准仪器测定。其表面和断面也可用扫描电子显微镜来研究。可生物降解能力可通过形状变形和薄膜埋在土壤下之后物理性能依时间的变化以及用ASTM G21-70方法进行研究。
以下的例子进一步说明本发明但不限制本发明的范围。
例1
在此例中用马来酐作为偶联剂通过化学结合淀粉和聚乙烯链而制备可生物降解薄膜。
分别将50克马来酐、5克油酸、5克过氧化苯甲酰,50克油酰胺,20克油酸锰和20克油酸亚铁溶解在50ml丙酮中。将5公斤低密度聚乙烯(MI=3,密度=0.919)放入Henschel混合机中然后用上述溶液进行涂覆。
将已涂覆的聚乙烯粒料与60%(重量)的玉米淀粉(以上述低密度聚乙烯为基准)在维持在170℃且螺杆转速为250rpm的挤出机内反应挤出制备可生物降解母料料粒,在其中淀粉与聚乙烯链化学结合。将1.7公斤可生物降解母料和8.3公斤低密度聚乙烯(MI=3,密度=0.919)干混并使其通过薄膜挤出机而制备吹塑薄膜。
为测定所制备的薄膜的物理性能,用Instron测量该拉伸强度和拉伸伸长开根据ASTM G 21-70方法确定可生物降解能力。
在图1中可生物降解薄膜的红外线吸收光谱的1700-1800cm-1处显示了马来酐和淀粉上的羟基反应所产生的羧基的吸收峰,图2显示的是可生物降解薄膜由扫描电子显微镜的断面,该画面显示淀粉颗粒的断面被剖开,这进一步证实由于马来酐偶联剂的影响聚乙烯链与淀粉化学反应。
通过干混上述可生物降解母料和低密度聚乙烯(MI=3,密度=0.919)而制备的可生物降解薄膜的物理性能和可生物降解能力记录在下面表1中。
可生物降解能力根据ASTM G 21-70方法进行测定。在一定的时间(至少21天)之后,根据聚合物表面被真菌菌落覆盖的百分率对增长速率进行分类:
0%:0
少于10%:1
10-30%:2
30-60%:3
60-100%:4
例2-6
重复如例1相同的程序,不同是使用以下重量%(以聚乙烯为基准)的淀粉,用与例1相同的方法所测定的结果记录在下面的表1中。
表1
例号 | 淀粉含量(重量%) | 拉伸强度(kg/cm2) | 拉伸伸长(%) | 可生物降解能力 |
对比例1* | 0 | 180 | 400 | 0 |
1 | 10 | 169 | 346 | 3 |
2 | 20 | 153 | 315 | 4 |
3 | 30 | 127 | 230 | 4 |
4 | 40 | 102 | 155 | 4 |
5 | 50 | 65 | 80 | 4 |
6 | 60 | 43 | 50 | 4 |
*对比例1:用于如例1相同的程序测定,不同是未掺入淀粉。
例7
在此例中用苯乙烯作为偶联剂的共聚单体以增强马来酐,即偶联剂的接枝效率制备可生物降解薄膜。
分别将35克马来酐、35克苯乙烯、5克硬脂酸、20克硬脂酸亚铁、20克硬脂酸锰、50克油酰胺和5克过氧化苯甲酰溶于50ml丙酮中。将5公斤线性低密度聚乙烯(MI=1 密度=0.919)放入Henschel混合机内然后用以上的溶液涂覆。
将已涂覆的聚乙烯粒料与60%(重量)(以上述线性低密度聚乙烯为基准)的氧化淀粉在一维持在170℃且螺杆转速为230rpm的挤出机内反应挤出制备可生物降解母料粒料。
将1.7公斤可生物降解母料粒料和8.3公斤线性低密度聚乙烯(MI=1,密度=0.919)干混,使其通过薄膜挤出机而制备吹塑膜。
通过干混以上的可生物降解母料和线性低密度聚乙烯(MI=1,密度=0.919)而制备的可生物降解膜的物理性能和可生物降解能力记录在下表2中。
例8-12
重复如例7的相同程序,不同是使用以下重量%(以聚乙烯为基准)的淀粉用如例7相同的方法测定的结果记录在以下表2中。
表2
例号 | 淀粉含量(重量%) | 拉伸强度(kg/cm2) | 拉伸伸长(%) | 可生物降解能力 |
对比例2* | 0 | 330 | 600 | 0 |
7 | 10 | 298 | 530 | 3 |
8 | 20 | 254 | 495 | 4 |
9 | 30 | 194 | 435 | 4 |
10 | 40 | 126 | 258 | 4 |
11 | 50 | 95 | 120 | 4 |
12 | 60 | 75 | 75 | 4 |
*对比例2:用如例7相同的程序确定,不同是未掺入淀粉。
例13
在此例中用甲基丙烯酸酐作为偶联剂通过化学结合聚乙烯链和淀粉而制备可生物降解薄膜
分别将100克甲基丙烯酸酐,5克亚油酸,20克油酸锰,20克硬脂酸亚铁,50克油酰胺和5克过氧化苯甲酰溶于50ml丙酮中。将5公斤高密度聚乙烯(MI=0.28密度=0.945)放入Henschel混合机中然后用以上的溶液涂覆。
把该已涂覆的聚乙烯粒料与60重量%(以以上的高密度聚乙烯为基准)的玉米淀粉在维持在170℃且螺杆转速为210rpm的挤出机内进行反应挤出制备可生物降解母料粒料。
用1.7公斤的可生物降解母料和8.3公斤高密度聚乙烯(MI=0.28密度=0.945)干混并使其通过一薄膜挤出机而制备可生物降解吹塑薄膜。
通过干混以上的可生物降解母料和高密度聚乙烯(MI=0.28,密度=0.945)而制备的可生物降解薄膜的物理性能和可生物降解能力记录在下面的表3中。
例14-18
重复如例13相同的程序,不同是使以下重量%(以聚乙烯为基准)的淀粉并用如例13相同的方法进行测定,其结果记录在下面表3中。
表3
例号 | 淀粉含量(重量%) | 拉伸强度(kg/cm2) | 拉伸伸长(%) | 可生物降解能力 |
对比例3* | 0 | 640 | 600 | 0 |
13 | 10 | 585 | 540 | 3 |
14 | 20 | 547 | 505 | 4 |
15 | 30 | 325 | 425 | 4 |
16 | 40 | 216 | 237 | 4 |
17 | 50 | 134 | 115 | 4 |
18 | 60 | 90 | 68 | 4 |
*对比例3:用如例13相同的程序测定,不同是未掺入淀粉。
所制备的含有10%(重量)淀粉的可生物降解薄膜与用基本树脂制备的膜相比通过Instron测量其物理性能没有差别。已发现本发明制备可生物降解薄膜的方法是极好的方法,根据掺入淀粉而使物理性能的下降减小至最低限度,其改进之处在于通过可生物降解化学结合使基质树脂和淀粉颗粒之间的分界不清而淀粉颗粒断面切开的现像显示在用扫描电子显微镜的薄膜断面的观察图上。用10%(重量)以上的淀粉其可生物降解能力最佳。
Claims (17)
1、一种与淀粉化学结合的可生物降解聚乙烯组合物,它含有100重量份基质树脂,5-400重量份可生物降解掺入物质,0.01-10重量份偶联剂,0.01-1.0重量份自由基引发剂,0.01-5重量份路易士酸催化剂,0.01-10份量份自氧化剂和0.01-10重量份增塑剂。
2、根据权利要求1的组合物,其中还含有0.01-10重量份共聚单体。
3、根据权利要求2的组合物,其中共聚单体是选自丙烯腈,苯乙烯和丙烯酸乙酯的一组物质中的一或多个。
4、根据权利要求1的组合物,其中基质树脂是低密度聚乙烯或高密度聚乙烯。
5、根据权利要求1的组合物,其中可生物降解掺入物质是选自玉米淀粉,酸处理的淀粉,酯化淀粉,醚化淀粉,阳离子淀粉及其混合物的一组物质的一种。
6、根据权利要求1的组合物,其中偶联剂是选自马来酐,甲基丙烯酸酐和马来酰亚胺的一组物质中的一个。
7、根据权利要求1的组合物,其中自由基引发剂是过氧化苯甲酰,过氧化二-叔丁基,偶氮二异丁腈,叔丁基氢过氧化物,过氧化二枯基,Lupersol 101或Perkadox-14。
8、根据权利要求1的组合物,其中自氧化剂是选自油酸锰,硬脂酸锰,油酸亚铁(Ⅱ),硬脂酸亚铁(Ⅱ)及其混合物的一组物质中的一个或多个。
9、根据权利要求1的组合物,其中增塑剂是选自油酰胺,Viton和Erucamide的一组物质中的一个。
10、根据权利要求1的组合物,其中路易斯酸催化剂是选自油酸(CH3(CH2)7CH∶CH(CH2)7CO2H),油酸(CH3·(CH2)7·CH∶CH·(CH2)7·COOH),亚油酸,硬脂酸,乙酸,对甲苯磺酸,癸酸,十二烷酸,十四烷酸,草酸,丙二酸,琥珀酸和己二酸的一组物质中的一个或多个。
11、一种与淀粉化学结合的可生物降解聚乙烯组合物的制备方法,包括混合100重量份的基质树脂,5-400重量份的可生物降解掺入物质,0.01-10重量份偶联剂,0.01-1.0重量份自由基引发剂,0.01-5重量份路易斯酸催化剂,0.01-10重量份自氧化剂和0.01-10重量份增塑剂并反应挤出所说的混合物。
12、根据权利要求11的方法,其中还混合选自丙烯腈,苯乙烯和丙烯酸乙酯的一组物质中一个或多个共聚单体,其量为0.01-10重量份。
13、根据权利要求11的方法,其中还包括在反应挤出该混合物前干燥可生物降解掺入物质水份含量低于3%的范围。
14、根据权利要求11的方法,其中所说的混合物在150-220℃的温度以50-300rpm的螺杆速度反应挤出。
15、一种与淀粉化学结合的可生物降解聚乙烯制品包括根据权利要求1-10之一混合聚乙烯组合物,反应挤出该混合物并造粒成母料粒料。
16、根据权利要求15的可生物降解聚乙烯制品,其中还包括在母料粒料中加入低密度聚乙烯,线性低密度聚乙烯或高密度聚乙烯,干混并挤出以上的混合物。
17、根据权利要求16的可生物降解聚乙烯制品,其中可生物降解聚乙烯制品是薄膜或瓶子。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR22255/92 | 1992-11-24 | ||
KR920022255 | 1992-11-24 | ||
KR14072/93 | 1993-07-23 | ||
KR1019930014072A KR960012444B1 (ko) | 1992-11-24 | 1993-07-23 | 전분이 화학 결합된 생분해성 폴리에틸렌 조성물 및 그 제조방법 |
Publications (1)
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CN1092084A true CN1092084A (zh) | 1994-09-14 |
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CN93121454A Pending CN1092084A (zh) | 1992-11-24 | 1993-11-24 | 一种与淀粉化学结合的可生物降解聚乙烯组合物及其制备方法 |
Country Status (8)
Country | Link |
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US (1) | US5461093A (zh) |
JP (1) | JPH07126449A (zh) |
KR (1) | KR960012444B1 (zh) |
CN (1) | CN1092084A (zh) |
CA (1) | CA2109660A1 (zh) |
GB (1) | GB2272700A (zh) |
IT (1) | IT1265218B1 (zh) |
MY (1) | MY109616A (zh) |
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CN110234699A (zh) * | 2016-11-22 | 2019-09-13 | 聚合材料有限公司 | 可降解聚合物组合物及其生产方法 |
CN111073143A (zh) * | 2019-12-26 | 2020-04-28 | 苏州润佳高分子材料有限公司 | 汽车用聚丙烯-聚乙烯改性复合材料 |
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US5667574A (en) * | 1996-11-06 | 1997-09-16 | Chi May Co., Ltd. | Starch-based composition for preparing an environment degradable α-olefinic polymer molding material |
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-
1993
- 1993-07-23 KR KR1019930014072A patent/KR960012444B1/ko not_active IP Right Cessation
- 1993-11-22 CA CA002109660A patent/CA2109660A1/en not_active Abandoned
- 1993-11-23 US US08/156,369 patent/US5461093A/en not_active Expired - Lifetime
- 1993-11-23 GB GB9324071A patent/GB2272700A/en not_active Withdrawn
- 1993-11-24 JP JP5317409A patent/JPH07126449A/ja active Pending
- 1993-11-24 MY MYPI93002460A patent/MY109616A/en unknown
- 1993-11-24 CN CN93121454A patent/CN1092084A/zh active Pending
- 1993-11-24 IT IT93MI002485A patent/IT1265218B1/it active IP Right Grant
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1057580C (zh) * | 1996-01-16 | 2000-10-18 | 北京市海淀区太生新工程材料研究所 | 一种降解型组合物及用其制造仿皮料的方法 |
CN101870774A (zh) * | 2010-05-10 | 2010-10-27 | 梁雄辉 | 生物淀粉降解塑料母粒及其生产方法以及降解塑料 |
CN104448398A (zh) * | 2014-11-18 | 2015-03-25 | 东莞市方中运动制品有限公司 | 一种木薯可降解塑料及其生产工艺和生产设备 |
CN110234699A (zh) * | 2016-11-22 | 2019-09-13 | 聚合材料有限公司 | 可降解聚合物组合物及其生产方法 |
US11155702B2 (en) | 2016-11-22 | 2021-10-26 | Polymateria Limited | Degradable polymer and method of production |
CN111073143A (zh) * | 2019-12-26 | 2020-04-28 | 苏州润佳高分子材料有限公司 | 汽车用聚丙烯-聚乙烯改性复合材料 |
Also Published As
Publication number | Publication date |
---|---|
CA2109660A1 (en) | 1994-05-25 |
KR960012444B1 (ko) | 1996-09-20 |
GB2272700A (en) | 1994-05-25 |
KR940011558A (ko) | 1994-06-21 |
JPH07126449A (ja) | 1995-05-16 |
ITMI932485A1 (it) | 1995-05-24 |
ITMI932485A0 (it) | 1993-11-24 |
IT1265218B1 (it) | 1996-10-31 |
MY109616A (en) | 1997-03-31 |
US5461093A (en) | 1995-10-24 |
GB9324071D0 (en) | 1994-01-12 |
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