CN1032213C - 制备结构被破坏的淀粉基组合物的方法及由此制得的组合物 - Google Patents
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Abstract
一种适用于生产生物降解塑料制品的淀粉基组合物，该组合物包含淀粉、高沸点增塑剂和结构破坏剂。该组合物可以在高于120℃的温度下进行加工，因此特别适合与较高熔点的聚合物配制聚合物混合物，并适合于在低压下与这些聚合物一起挤出，特别是，该组合物与聚乙烯醇和/或乙烯/乙烯醇混合后适合于吹塑一挤出制膜，因为它们具有所要求的机械强度和抗撕裂，耐穿孔特性，或者适合于通过注射模塑，热定型或吹塑形成最终制品。
Description
本发明涉及制备用于生产可生物降解的塑料制品的结构被破坏的淀粉基组合物的方法。
本方法特别适合于制备可与熔点较高的聚合物很容易地混合并相容的淀粉组合物，由于含有高熔点的塑料，使配制的基本上可生物降解的聚合物混合物具有机械，物理和化学性能，这些性能迄今尚不能获得。
已经知道，在一个密闭容器中，在各种水含量的条件下，于高温高压下(根据水含量而定)处理存在于植物产品中的天然淀粉，可制成一种熔融热塑材料。如果在不加压和/或不加水的条件下进行同样的热处理，将会导致材料的交联，而不能达到熔融态。尽管在高于组份玻璃化转变温度和熔点的温度下进行热处理会产生熔融的结果，但是淀粉微粒的分子结构会变得无序，从而形成所谓的“结构被破坏的淀粉”。
按照通常的方法，破坏淀粉结构的操作是在挤出机中进行的，其中加入了适量的水并保持一定的压力，该压力至少为所加入的水的蒸汽压。
已公开的欧洲专利申请EP—A—0304401叙述了由结构被破坏的淀粉生产模制品的方法，其中第一步，先在挤出机中于含水的条件下将淀粉的结构破坏，第二步，在挤出机中将由此制得的含10—20％水的组合物进行再加工，以适合于随后的注射成型。在第一步中加入到结构被破坏的淀粉中的水限制了组合物的施工性能，该组合物很难与其它聚合物相混合以制备具有所需特性的混合物，特别是对于制膜。事实上，可以仅在较低温度和高压下将该组合物挤出，从而使组合物能够仅与低熔点的聚合物形成聚合物混合物。另一方面，按该方法制得的结构被破坏的淀粉组合物不适于单独用来制膜。
为了提供能够制膜的组合物，美国专利4133784叙述了淀粉与一种可与其相容的聚合物所构成的组合物，该聚合物由乙烯/丙烯酸(EAA)形成。按照该文献中所述的制备方法，在水的存在下将淀粉加热，使其凝胶化，直到形成粘稠的分散体，在凝胶化的过程之中或之后将EAA组份加入淀粉中，由此制得的组合物，只有通过诸如展涂(铸塑)，简单挤压或压延(辊炼)、这种昂贵加工方法才能适合于制膜。
为了增加凝胶化速度，从而减少所需的用水量，在出版物Ind.En9.Chem.Res.1987，26，1659—1663页中建议于淀粉和EAA共聚物的组合物中加入尿素。由于加入尿素，使得能够挤出半干燥状态的组合物(水含量约为16％)，从而避免了必须在混合机中将淀粉和EAA与大批过量的水相混合。该文献还叙述了于淀粉和EAA共聚物混合物中加水的同时还加多元醇，通过在布拉本登混合机中预混合这些组份然后反复挤压，可以明显地减少经过该处理步骤的组合物的水含量，从而制得适合于挤压和吹塑制膜的挤出物。显然，从耗能的角度来看，所述方法是昂贵的，因为它包括加入过多的水，而随后又反复挤压进行除水。
作为本申请人进行研究的结果，发现如果在加入高沸点增塑剂和破坏结构剂的条件下，在温度低于增塑剂沸点的挤出机中将淀粉的结构破坏，可以得到被破坏结构的淀粉组合物，它能够与熔点较高的聚合物相混合，并适合在高于120℃的温度下和低压下进行挤压，而没有形成气泡的问题，并且特别适合于以后的操作如热成型和吹塑。
因此本发明的主题是制备用于生产可生物降解塑料制品的结构被破坏淀粉基组合物的方法，其特征在于它包括在加热的挤出机中将淀粉与高沸点增塑剂和破坏结构剂进行混合，破坏结构构剂从尿素，碱金属氢氧化物和碱土金属氢氧化物构成的一组化合物中选取，将该混合物混合足够长的时间，以便发生结构破坏，所采用的温度低于增塑剂的沸点，在120至170℃之间，最好在140至170℃之间。
于该方法中所使用的淀粉一般包括所有的天然淀粉或来源于植物的淀粉，这类淀粉基本上由直链淀粉和/或支链淀粉组成。可以从各种植物中提取这类淀粉，如土豆，大米，木薯，玉米和谷类如黑麦、燕麦、小麦等。玉米淀粉是优选的，也可以使用化学改性后的淀粉和不同基因型淀粉，使用这种淀粉时，不要预先干燥，也不要加任何水(其市售产品的固有结合水量为10—13重量)。在高于120℃的破坏结构处理温度下，由于所存在的水结合在淀粉上而不产生蒸汽压，以致需要高压，这构成了本发明方法的另一个优点。
用于本发明方法的增塑剂最好从甘油，聚乙二醇(分子量最好为220至4000)乙二醇，丙二醇和山梨醇构成的一组化合物中选取。通常可以使用属于沸点温度至少为150℃的一组多元醇的增塑剂。
加入到淀粉中的增塑剂用量为淀粉重量的0.05—100％，最好为淀粉重量的20—100％。
尿素和钠、钾和钙的氢氧化物特别适合于作破坏结构剂。
尿素是优选的破坏结构剂，其用量为淀粉重量的2—20％。在进行破坏结构的操作中可以于组合物中加入乙烯/丙烯酸(EAA)，其用量最多为组合物总重量的15％，使用与淀粉相容的EAA共聚物，有利于进行挤压操作。
如果使用EAA共聚物，特别是准备用于吹塑制膜的结构被破坏的淀粉组合物，最好使用一定量的氨，虽然其用量不很重要，但通常至少相当于EAA共聚物中酸基的一半。在挤压组合物过程中，加入的氨基本被除去，残余量不超过0.5％(重量)。
在破坏结构操作过程中，可以于淀粉中加入其它添加剂，无论是聚合物还是单体，只要不妨碍破坏结构处理即可。然而，这些添加剂也可以在将组合物制成预定的最终产品之前的后续混合步骤中加入。
例如，可以加入聚乙烯醇来改变模制品与水的性能；加入UV稳定剂，如碳黑，可以改进制品对日光的耐受性；如果模制品需要具有耐焰性，可以加入耐焰剂。其它添加剂包括通常结合到淀粉基模制组合物中的常用添加剂，如杀菌剂，除草剂，抗氧剂，化肥，交联剂如甲醛，多聚甲醛等。
作为该方法的结果，制得的结构被破坏的淀粉组合物可以在高于120℃的温度下进行加工，而挤压出的组合物不会产生气泡这类问题，而且在低压下也没有挥发性试剂释放出来。
该组合物特别适合与较高熔点的聚合物(如乙烯/乙烯醇)相混合，特别是与本申请同日递交的同一申请人的专利申请中所述的聚合物。
实施例1—4
在不同的挤出温度下，将表1所示的淀粉基组合物进行挤出加工。
表ICERESTAR GLOBE 03401 例1 例2 例3 例4淀粉(所结合的水量11％)％(重量) 63 63 63 63甘油 ％(重量) 25 25 25 25共聚物EAA 5981(DowChemical)(丙烯酸含量20％) 5 5 5 -％(重量)尿素 ％(重量) 7 7 7 7挤出温度 100 120 140 140
注：*为对比例
用Licoarbo DC—10送料计量器将实施例1—4的模塑组合物的各组份加入到Baker Perkins MPC/V—30挤出机中。双螺杆挤出机具有被分成两部分的螺杆直径为30mm，螺杆长度/直径比为10的螺杆单元，该挤出机与具有毛细喷嘴的单螺杆挤出机相联接，后者的螺杆直径为30mm，长度/直径比为8∶1，螺杆被分成三部分，所用的毛细喷嘴的直径为4.5mm。
将所得的挤出物制成颗粒。在140℃的温度下，将少量实施例1至4得到的颗粒进行压制模塑，制成厚度约为20微米的薄膜，采用偏振光(放大250倍)用光学显微镜分析这些薄膜，并对其进行显微照相，以确定淀粉的结构破坏情况。由对比例1的显微照片可知，挤压温度为100℃是太低了，不能使淀粉的结构破坏；其显微照片表明仍有大量完整无损的淀粉微粒存在。对实施例2(挤压温度为120℃)所得产品的分析表明，完整无损的淀粉微粒数已大大减少，虽然仍有一些存在。另一方面，按照挤出温度为140℃的实施例3，可以得到结构全部被破坏的淀粉，在对实施例3的产物所摄制的显微照片上看不到完整无损的淀粉颗粒。也可以毫无困难地将实施例3的产物制成颗粒。
实施例4与实施例3所用的挤压条件相同，但是不包括EAA—5981共聚物，对实施例4产品的分析表明在不用这种共聚物时也能获得满意结果，然而，在用这种组合物制备颗粒时会遇到一些困难。
实施例5
在同样的挤出机中，于160℃，将60％的结构被破坏的淀粉粒料和40％重量的CLARENE R 20乙烯/乙烯醇共聚物挤出。用HAAKE REOMEX 252型挤出机将最终混合物吹塑，该挤出机的L/D比为19，螺杆直径为19mm，压缩比为1∶3，螺杆转速为40rpm，并装配有吹膜机头。根据ASTM 882，由约为100微米厚的薄膜制备用于张力试验的长方形试样。将该试样在23±1℃，相对湿度为55±5％的条件下放置24小时，测得以下平均值：
杨氏模量 3.786×108帕斯卡
屈服应变 43％
屈服应力 1.61×107帕斯卡
断裂应变 207％
断裂应力 2.06×107帕斯卡
所制得的产物的特征是：熔点为135℃，玻璃化转变温度为70℃。所制得的膜特别适合用作包装材料，特别是生产一次应用包装袋。甚至老化很长时间后，增塑剂也基本上不减少，所生产的薄膜仍保持可塑性和柔韧性，基本上不受环境条件的影响。
这就是说，本发明的范围包括按本发明的方法制得的结构被破坏的淀粉组合物，同时还包括用该组合物生产的膜状制品或模制品。
Claims (9)
1.一种制备用于生产可生物降解的塑料制品的结构被破坏淀粉基组合物的方法，该方法包括如下步骤：在加热的挤出机中将淀粉与高沸点增塑剂和由尿素构成的破坏结构剂混合足够长的时间，使淀粉发生结构破坏，所用温度低于增塑剂的沸点并处于120℃-170℃之间。
2.根据权利要求1的方法，其中增塑剂选自甘油、聚乙二醇、乙二醇、丙二醇和山梨醇。
3.根据权利要求1或2的方法，其中加入到淀粉中的增塑剂用量为淀粉重量的0.05-100％。
4.根据权利要求1或2的方法，其中加入到淀粉中的增塑剂用量为淀粉重量的20-100％。
5.根据权利要求1的方法，其中在进行混合操作时加入一定量的乙烯/丙烯酸，其用量最多为混合物总重量的15％。
6.根据权利要求1或2的方法，其中所用的淀粉为天然淀粉，它没有经过预先干燥，也没有加过水。
7.根据权利要求1或2的方法，其中破坏结构剂由尿素构成，其加入量为淀粉重量的2-20％。
8.根据权利要求1或2的方法，该方法包括向淀粉中加入不妨碍破坏结构处理的添加剂，该添加剂选自UV稳定剂、耐焰剂、交联剂、杀菌剂、除草剂、抗氧剂和化肥。
9.根据权利要求1至8中任何一项的方法所制备的结构被破坏的淀粉基组合物。
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| IT67414-A/89 | 1989-05-30 | ||
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| JPH0668041B2 (ja) * | 1989-07-11 | 1994-08-31 | ワーナー・ランバート・カンパニー | 変性澱粉を含有するポリマーをベースとするブレンド組成物 |
| CA2020893A1 (en) * | 1989-07-18 | 1991-01-19 | Jean-Pierre Sachetto | Polymer base blend compositions containing destructurized starch |
| FI102480B (fi) * | 1989-07-18 | 1998-12-15 | Warner Lambert Co | Rakenteeltaan muunnettua tärkkelystä sisältävät polymeeriperustaiset s eoskoostumukset |
| BR9003322A (pt) * | 1989-07-18 | 1991-08-27 | Warner Lambert Co | Composicao de materia capaz de ser formada em artigos tendo estabilidade dimensional,produto de amido desestruturado termoplastico,artigos moldados,fundido substancialmente homogeneo de amido desestruturado termoplastico |
| CA2021119C (en) * | 1989-07-20 | 2004-05-18 | Jean-Pierre Sachetto | Polymer base blend compositions containing destructurized starch |
| NZ234495A (en) * | 1989-07-20 | 1991-08-27 | Warner Lambert Co | Polymer base-blend compositions containing destructurised starch and styrene sulphonic acid polymers |
| IT1232894B (it) * | 1989-08-03 | 1992-03-05 | Butterfly Srl | Articoli espansi di materiale plastico biodegradabile e procedimento per la loro preparazione |
| IT1232909B (it) * | 1989-08-07 | 1992-03-05 | Butterfly Srl | Composizione polimerica per la produzione di articoli di materiale plastico biodegradabile comprendente amido destrutturato e copolimero di etilene |
| 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 |
-
1989
- 1989-05-30 IT IT8967414A patent/IT1234783B/it active
-
1990
- 1990-05-23 AU AU55881/90A patent/AU623012B2/en not_active Ceased
- 1990-05-24 IL IL94494A patent/IL94494A0/xx unknown
- 1990-05-24 KR KR1019900007505A patent/KR900018239A/ko not_active Application Discontinuation
- 1990-05-28 DK DK96116081T patent/DK0758669T3/da active
- 1990-05-28 CA CA002017655A patent/CA2017655C/en not_active Expired - Fee Related
- 1990-05-28 AT AT96116081T patent/ATE205869T1/de not_active IP Right Cessation
- 1990-05-28 EP EP90110069A patent/EP0400531B1/en not_active Expired - Lifetime
- 1990-05-28 DK DK90110069.3T patent/DK0400531T3/da active
- 1990-05-28 EP EP96116081A patent/EP0758669B1/en not_active Expired - Lifetime
- 1990-05-28 NO NO902347A patent/NO306259B1/no not_active Application Discontinuation
- 1990-05-28 AT AT90110069T patent/ATE152130T1/de not_active IP Right Cessation
- 1990-05-28 ES ES90110069T patent/ES2100855T3/es not_active Expired - Lifetime
- 1990-05-28 DE DE69030527T patent/DE69030527T2/de not_active Expired - Fee Related
- 1990-05-28 ES ES96116081T patent/ES2163565T3/es not_active Expired - Lifetime
- 1990-05-28 DE DE69033806T patent/DE69033806T2/de not_active Expired - Fee Related
- 1990-05-29 CN CN90103071A patent/CN1032213C/zh not_active Expired - Fee Related
- 1990-05-29 FI FI902663A patent/FI102760B/fi not_active IP Right Cessation
- 1990-05-29 BR BR909002601A patent/BR9002601A/pt unknown
- 1990-05-29 HU HU903244A patent/HU205954B/hu not_active IP Right Cessation
- 1990-05-29 PL PL28538490A patent/PL285384A1/xx unknown
- 1990-05-29 JP JP2139544A patent/JP3040794B2/ja not_active Expired - Fee Related
- 1990-05-29 DD DD90341098A patent/DD297988A5/de not_active IP Right Cessation
-
1994
- 1994-10-28 US US08/331,338 patent/US5462982A/en not_active Expired - Fee Related
-
1995
- 1995-08-21 US US08/517,398 patent/US5569692A/en not_active Expired - Lifetime
-
1997
- 1997-06-24 GR GR970401512T patent/GR3023869T3/el unknown
-
1999
- 1999-05-10 JP JP11128682A patent/JP3076797B2/ja not_active Expired - Fee Related
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