CN1049671A - 生物降解塑料发泡制品及其制造方法 - Google Patents
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Abstract
生物降解塑料发泡制品是由包括有淀粉,与淀粉
相溶的聚合物,特别是以乙烯-丙烯酸共聚物和/或
乙烯-乙烯醇共聚物和发泡剂的组合物进行挤出而
制造出来的,优选的发泡剂是由碳酸氢钠在聚合酸存
在下而制成的。
Description
本发明涉及生物降解塑料的发泡制品及这种制品的制造方法。
最近几年,人们做了许多制造生物降解模制件的试验。为了制造这种制品,在所提出的各种原料之中,由于淀粉价格便宜,又是自然界中最丰富的天然产物和可以完全降解,所以淀粉是最理想的原料。
已公开的欧洲专利申请EP-A-304,401描述了从变性淀粉来注模胶囊的方法。可是,用这种方法制造的制品,不但具有不良的机械性能,而且非常能溶于水。
未公开的意大利专利申请号41002-A/89及相应的国际申请PCT/EP90/00375(也是未公开的)描述了一种能够使机械性能改进的模制件的制造方法。在这种方法中,将淀粉用乙烯-丙烯酸共聚物混合而成的,还要尽可能地把尿素和/或氨加入到挤出机中,并使温度加热到90~150℃。用这种方法,挤出时带入少于6%重量,优选小于2%重量的水份,然后将此结果组合物在130到160℃之间的温度进行挤出。
EP-A-087,847描述了一种用淀粉制造发泡凝胶化制品的方法,它是在挤压机于温度为60~220℃时的压力下,在含水量为10~30%重量和在能产生气体或形成气体的发泡剂存在下来加热粒状或粉状淀粉的,所得的发泡物是具有开孔及高的水溶性,适用于易脆制品的包装材料,或作为吸声或绝热材料或用于食品工业。
本发明的目的是提供一种生物可完全降解的发泡制品。它是不溶于水的,而且能够通过一般的工艺技术就可获得热塑性塑料,例如挤出或注模法,还具有良好的机械性能,例如其弯曲强度及伸长都可与通普发泡塑料相匹敌。
鉴于上述目的,本发明发泡制品的首要目的是其原料的制造,它包括淀粉和选自乙烯-丙烯酸和乙烯-乙烯醇共聚物及其混合物的制备。其制造是具有闭孔结构,和其密度为0.1~0.3克/立方厘米。
在发泡制品的制造中,所用的乙烯-乙烯醇共聚物中乙烯含量最好为10~40%重量份(15~50%摩尔)优选为30~35%摩尔,其熔融指数(230℃、2.16公斤)为2~50之间,优选为6~20之间。
另外,乙烯-乙烯醇共聚物还具有下列最佳特征:
特性粘度 0.50~0.9(30℃时用二甲基亚砜),优选为0.65~0.80
分子量分布(MW/MN) 1.3~4(在四氢呋喃中用凝胶渗透色谱)
熔点(温度) 180℃,优选为160~170℃
水解度★90~99.9%
★碱性水解及残余的碱用酸滴定。
所选用的乙烯-丙烯酸共聚物(EAA)是通过混合物的共聚合作而制造的,所含丙烯酸量为3~30%重量,优选为20%重量,相应地乙烯含量为97-70%重量,优选为80%重量。
所用的淀粉包括自然界所有的普通的淀粉或植物源淀粉,实质上是由直链淀粉和/或支链淀粉组成的。它们都是从各种植物中提取的。例如土豆、大米、木薯、玉米以及谷类(如黑麦、燕麦和小麦)、优选的是玉米淀粉。用化学方法改性的淀粉也能够作为淀粉类来使用。
淀粉对聚合物所用的比率为9∶1~1∶9,优选的比率为4∶1~1∶4,然而,本发明尤其与制品种类有关,合成聚合物的组份优选从20到40%重量(以淀粉和聚合物总量计)。
根据本发明的发泡制品可以通过使用物理发泡剂来制得,例如,二氧化碳及正戊烷或其化学发泡剂,例如碳酸盐,它是与淀粉和聚合物一起送入挤出机桶内的。
根据优选的方法,是使用碳酸氢钠配合能与淀粉相溶的聚合酸而制成的。
本发明的中一个目的是提供一种生物降解塑料发泡制品的制造方法,其特征在于包括挤出步骤,其组份包括淀粉和合成聚合物,它是选自含有乙烯-乙烯醇和乙烯-丙烯酸共聚物及其混合物,在聚合酸和碳酸氢钠作为发泡剂的存在下进行的方法。
在普通合成塑料发泡制品的制造中,使用碳酸氢钠作为化学发泡剂是众所周知的。但是仅仅使用此发泡剂来制造发泡塑料,通过挤出会有不良的性能。因此,在实际中,例如在制造发泡聚苯乙烯板材时,碳酸氢钠仅作为成核剂与物理发泡剂相配合是有利的。如在上述的EP-A-0087,847中它是用作发泡剂的,结果产生开孔的结构,它是不适用于本发明的目的。
故此,根据本发明的范围内,人们可以发现上述的聚合酸、碳酸氢钠相配合是很有效的发泡作用,它能制造出具有密度下降到0.1,一般为0.1到0.3的发泡制品。
根据本发明,有可能无需希望进行物-化发泡,此发泡不会引起碳酸氢钠的热分解而是在聚合物的羧基和碳酸氢钠之间进行化学反应而释放二氧化碳和水。
所用的聚合酸,优选采用具有侧基羧基的聚合物,例如聚丙烯酸、乙烯-丙烯酸共聚物(EAA)和乙烯-乙烯醇-丙烯酸共聚物。上述所定义的同样EAA聚合物也可以采用。
挤出温度为从100到180℃范围,是根据所选用的与淀粉混合的共聚物的种类而定。
在实施例中与淀粉共混合的共聚物和聚合酸,这两者都是EAA共聚物。挤压温度可以低到100到120℃,优选为100到110℃之间,即低于碳酸氢钠的热分解温度。事实上,根据这实施例挤出的最佳结果是当进行挤压时,挤压机的加热温度是低于碳酸氢钠的热分解温度,这是在挤出时由于聚合酸的羧基和碳酸氢钠之间的化学反应结果而产生二氧化碳和水而得以证实。
加入碳酸氢钠的量是在聚合酸中每当量的自由羧基至少为0.3个碳酸氢钠当量。
为了易于进行发泡,成核剂,例如二氧化硅可以包括在聚合物组份中。
如希望进一步降低发泡(挤出)制品的密度时,把作为填料的热解发泡淀粉(成颗粒状)加入到挤出机内的聚合组份中是有利的,如上述EP-A-0087847的方法,或加入中空玻璃微珠,其量可占总组份的高达30%重量,优选为5到20%重量。
挤出方法基本上是以改性淀粉和淀粉相与共聚物相互相渗透的进行的。
为了促进淀粉的改性,而淀粉本身的原有水含量为10到13%重量,可以把水加到干淀粉中接近25%的重量。不过,最终产品的含水量应小于6%,优选为0到2%重量之间。
挤出的组合物也可含有高达30%的尿素(以组份和高沸点增塑剂总量计)。此增塑剂如甘油、乙二醇等。
根据产生发泡制品所期望的特性及其用途,可进一步考虑加入添加剂,此类添加剂可包括聚合物,例如聚乙烯醇,在塑料的制备上,通用的添加剂如紫外线稳定剂、阻焰剂、杀菌剂、除草剂、抗氧剂、肥料、不透明剂、防粘剂、润滑剂和增塑剂。
发泡制品也可按PCT/EP90/00375的方法将碳酸氢(钠加入到淀粉的粒子中和预先制好的可相淀的聚合物中,其量在本发明说明书中加以参考。
例1
组合物的制备,含有:
带有水量为11%的淀粉GLOBE 3401CERESTAR为36%重量;
道化学的共聚物EAA5981为36%重量(带有20%的丙烯酸);
6%重量的水
14%的尿素,和
8%重量的碳酸氢钠。
此产物预先混合,然后加入挤出机中,在膨胀管中挤出。在挤出机内的温度保持在100到110℃的范围内。
此发泡制品的密度接近0.15克/立方厘米,其闭孔大小为0.3毫米到2毫米之间,伸长高于10%。
例2
组合物的制备,含有:
36%重量的淀粉(GLOBE 3401CERESTAR)
18%重量的EAA共聚物Dow5981
6%重量的水
9%重量的甘油
5%重量的尿素
18%的乙烯-乙烯醇(含乙烯共聚单体30%摩尔)
8%重量的碳酸氢钠
将此组合物于挤出机的桶内在17℃下混合,注射模塑成尺寸为3×120×20毫米的样片。
此发泡制品具有密度为约0.3克/立方厘米,闭孔尺寸在0.5到2.5毫米之间。
Claims (16)
1、生物降解塑料的发泡制品,其特征在于所使用的原料包括淀粉和选自乙烯-乙烯醇和乙烯-丙烯酸及其混合物的合成聚合物,所述制品具有闭孔结构和密度为0.1~0.3克/立方厘米。
2、根据权利要求1所述的发泡制品,其中乙烯-乙烯醇共聚物中乙烯的含量为10~40%重量和其熔体流动指数为6~20。
3、根据权利要求1所述的发泡制品,其中乙烯-丙烯酸共聚物是通过从含有丙烯酸为3~30%重量和乙烯为97~70%重量的混合物中进行共聚合作用而制造出来的。
4、根据权利要求1所述的发泡制品,其中所述的淀粉和共聚物的重量比为1∶4~4∶1。
5、根据权利要求1所述的发泡制品,进一步还包括尿素和/或高沸点增塑剂。
6、根据权利要求1所述的发泡制品,进一步还包括有选自乙烯-丙烯酸、聚丙烯酸和乙烯-丙烯酸-乙烯醇共聚物组的聚合酸。
7、根据权利要求1所述的发泡制品,包括由粒状热解发泡淀粉或中空玻璃微珠的填料。
8、一种生物降解塑料发泡制品的制造方法,其特征在于挤出包括有淀粉和选自乙烯-乙烯醇和乙烯-丙烯酸的合成聚合物的组份,在聚合酸和碳酸氢钠作为发泡剂的存在进行挤出的方法。
9、根据权利要求8所述的方法,其中聚合酸是选自含有聚丙烯酸、乙烯-丙烯酸和乙烯-丙烯酸-乙烯醇共聚物基团的聚合酸。
10、根据权利要求8所述的方法,其中共聚物是包括含有3到30%重量的丙烯酸和97到70%重量的乙烯混合物共聚合所制造的。
11、根据权利要求8所述的方法,其中乙烯-乙烯醇共聚物含有乙烯量从10到40%重量和其熔体流动指数为从6到20。
12、根据权利要求8所述的方法,其中加入碳酸氢钠的量,是对于在聚合酸上每当量的自由羧基至少是0.3当量的碳酸氢钠。
13、根据权利要求8所述的方法,其中淀粉和共聚物的比率是从4∶1到1∶4。
14、根据权利要求8所述的方法,组合物包括尿素的量高达30%重量(以组合物和高沸点增塑剂的总重量计)。
15、根据权利要求8所述的方法,其中共聚物和聚合酸都是乙烯-丙烯酸和其中此组合物是在挤出机的桶内加热到100℃至碳酸钠热分解温度之间的温度进行混合的。
16、根据权利要求8所述的方法,其中此组合物包括的水量从10到25%重量(以干淀粉计)。
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IT67667-A/89 | 1989-08-03 | ||
IT8967667A IT1232894B (it) | 1989-08-03 | 1989-08-03 | Articoli espansi di materiale plastico biodegradabile e procedimento per la loro preparazione |
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EP (1) | EP0436689B1 (zh) |
JP (1) | JP2958347B2 (zh) |
CN (1) | CN1049671A (zh) |
AT (1) | ATE120781T1 (zh) |
AU (1) | AU629022B2 (zh) |
BR (1) | BR9006875A (zh) |
CA (1) | CA2037913C (zh) |
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GR (1) | GR1002606B (zh) |
HU (1) | HUT57245A (zh) |
IL (1) | IL95261A (zh) |
IT (1) | IT1232894B (zh) |
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CN112029153A (zh) * | 2019-06-04 | 2020-12-04 | 湖南工业大学 | 一种环保型淀粉基发泡材料及其制备方法 |
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IT1234783B (it) * | 1989-05-30 | 1992-05-27 | Butterfly Srl | Procedimento per la produzione di composizioni a base di amido destrutturato e composizioni cosi ottenute |
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IT1232910B (it) * | 1989-08-07 | 1992-03-05 | Butterfly Srl | Composizioni polimeriche per la produzione di articoli di materiale plastico biodegradabile e procedimenti per la loro preparazione |
US5409973A (en) * | 1989-08-07 | 1995-04-25 | Butterfly S.R.L. | Polymer composition including destructured starch and an ethylene copolymer |
JPH03199245A (ja) * | 1989-12-27 | 1991-08-30 | Agency Of Ind Science & Technol | 微生物崩壊性熱可塑性樹脂発泡体及びその製造方法 |
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-
1989
- 1989-08-03 IT IT8967667A patent/IT1232894B/it active
-
1990
- 1990-08-01 RU SU904895478A patent/RU2066332C1/ru active
- 1990-08-01 CA CA002037913A patent/CA2037913C/en not_active Expired - Fee Related
- 1990-08-01 AT AT90910652T patent/ATE120781T1/de not_active IP Right Cessation
- 1990-08-01 ES ES90910652T patent/ES2071103T3/es not_active Expired - Lifetime
- 1990-08-01 HU HU906103A patent/HUT57245A/hu unknown
- 1990-08-01 BR BR909006875A patent/BR9006875A/pt not_active Application Discontinuation
- 1990-08-01 WO PCT/EP1990/001252 patent/WO1991002023A1/en active IP Right Grant
- 1990-08-01 DE DE69018426T patent/DE69018426T2/de not_active Expired - Fee Related
- 1990-08-01 JP JP2510419A patent/JP2958347B2/ja not_active Expired - Fee Related
- 1990-08-01 AU AU60552/90A patent/AU629022B2/en not_active Ceased
- 1990-08-01 IL IL9526190A patent/IL95261A/en not_active IP Right Cessation
- 1990-08-01 EP EP90910652A patent/EP0436689B1/en not_active Expired - Lifetime
- 1990-08-01 DK DK90910652.8T patent/DK0436689T3/da active
- 1990-08-02 CN CN90107256A patent/CN1049671A/zh active Pending
- 1990-08-02 PL PL28632890A patent/PL286328A1/xx unknown
- 1990-08-02 GR GR900100585A patent/GR1002606B/el unknown
-
1991
- 1991-04-02 FI FI911582A patent/FI98305C/fi not_active IP Right Cessation
- 1991-04-02 NO NO911288A patent/NO180236C/no unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102264824A (zh) * | 2009-01-06 | 2011-11-30 | 昭和电工株式会社 | 发泡性树脂组合物以及发泡体 |
CN112029153A (zh) * | 2019-06-04 | 2020-12-04 | 湖南工业大学 | 一种环保型淀粉基发泡材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
DK0436689T3 (da) | 1995-06-19 |
HUT57245A (en) | 1991-11-28 |
ES2071103T3 (es) | 1995-06-16 |
NO911288L (no) | 1991-05-27 |
FI98305C (fi) | 1997-05-26 |
PL286328A1 (en) | 1991-12-02 |
ATE120781T1 (de) | 1995-04-15 |
NO180236C (no) | 1997-03-12 |
IT8967667A0 (it) | 1989-08-03 |
NO180236B (no) | 1996-12-02 |
CA2037913C (en) | 2001-12-18 |
IT1232894B (it) | 1992-03-05 |
AU629022B2 (en) | 1992-09-24 |
GR900100585A (el) | 1991-12-30 |
WO1991002023A1 (en) | 1991-02-21 |
BR9006875A (pt) | 1991-08-27 |
CA2037913A1 (en) | 1991-02-04 |
IL95261A (en) | 1994-04-12 |
JP2958347B2 (ja) | 1999-10-06 |
EP0436689A1 (en) | 1991-07-17 |
HU906103D0 (en) | 1991-10-28 |
IL95261A0 (en) | 1991-06-30 |
DE69018426D1 (de) | 1995-05-11 |
GR1002606B (el) | 1997-02-18 |
DE69018426T2 (de) | 1995-09-14 |
JPH04500833A (ja) | 1992-02-13 |
AU6055290A (en) | 1991-03-11 |
FI98305B (fi) | 1997-02-14 |
EP0436689B1 (en) | 1995-04-05 |
FI911582A0 (fi) | 1991-04-02 |
RU2066332C1 (ru) | 1996-09-10 |
NO911288D0 (no) | 1991-04-02 |
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