CN1051273C - 用植物原料制造生物降解膜的方法 - Google Patents

用植物原料制造生物降解膜的方法 Download PDF

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CN1051273C
CN1051273C CN93109726A CN93109726A CN1051273C CN 1051273 C CN1051273 C CN 1051273C CN 93109726 A CN93109726 A CN 93109726A CN 93109726 A CN93109726 A CN 93109726A CN 1051273 C CN1051273 C CN 1051273C
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additive
film
template
melt
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CN1084117A (zh
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J·洛克
W·波默雷茨
J·霍耶尔
K·克伦克
H·施米特
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Biotechnology biochemistry natural packing Research Development Co.,Ltd.
EUL Gense Taili Co.,Ltd. Parkinson
BioTec Biologische Naturverpackungen GmbH and Co KG
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Abstract

本发明提出用碳水化合物形态的植物原料一步连续制造生物降解膜的方法，其中植物原料得到改性，塑化后一步不间断成膜。本发明的优点在于淀粉分子剪切应力降低，因此提高了膜性能并且制造成本少，耗时短，能耗低，节省空间。

Description

用植物原料制造生物降解膜的方法
本发明涉及用植物原料制造生物降解膜的方法。在制造例如符合环保要求的包装材料方面，该方法显得越来越重要，其目的是制成具有足够强度并易分解或溶解成其原始天然成分的膜。
用淀粉制造热塑性颗粒的方法已见于US-A-4133784，US-A-4021388和DE-A-1322440，这些颗粒可经第二步加工成膜，其中淀粉在合成聚合物中作填料，而制造和改进结构受损的热塑性淀粉的方法也已见于EP-4-378646和EP-A-397819。
WO90/05161A1也公开了可热塑性加工的淀粉及其制备方法，其中将骨料及必要时的其它添加剂加入淀粉原料中以使其熔点降到低于其分解点的水平，其目的是改善淀粉熔体的结构，从而在热塑性淀粉的制造和加工时容易进行处理。
EP-A1-0474095公开了用植物原料如淀粉作初始物料制造可生物降解制品如盘，杯和纸箱等的方法，其中原料中补充添加剂，塑化后在第一挤出机中转化成呈胶粒或颗粒的中间体，然后在第二挤出机中将该中间体模制成要求制品。
同样，用植物原料成膜的常见方法分成完全独立的两步进行，其中结构受损并在挤出工艺中塑化的生物聚合物熔体在第一步结束时冷却后高压下强制通过模具并进行造粒。为了避免生物聚合物发泡，要求对熔体进行冷却，其中造成的高剪切应力会使淀粉分子结构受损，同时又会撕下各种分子片段，使淀粉聚合物链缩短并使分子量降低。所得淀粉颗粒然后在进一步挤出工艺中于相似条件下加工成膜，其中生物聚合物会再分解，因为分子量降低并且链缩短。这种对分子结构的双重损害，尤其是使直链淀粉链缩短会导致所得膜的性能(抗拉强度和弹性等)激剧下降，而且这种双重挤出费时，能耗和投资大。
相比之下，本发明目的是提出用植物原料制造可生物降解膜的低投资方法，其中可避免现有技术的缺陷，同时又可提高所得膜的质量并达到例如高抗拉强度和弹性。
这一目的可通过下述技术特征而达到。
在达到这一目的的过程中，本发明基于这样一种概念，即在连续的一步工艺中必要时分解并改性植物原料如碳水化合物原料，其中不涉及中间产物并且不中断操作，塑化后压制成膜。螺杆挤出机中适宜于传送膜料的构型和合适的温度条件可保证生物聚合物的仔细加工。
植物原料可包括碳水化合物如面粉或天然淀粉，为天然或杂化物形式，可用例如马铃薯，木薯，豌豆，蚕豆，玉米，wax corn，直链淀粉含量高的玉米，谷物如小麦及其部分制品，大麦或高粱，由物理和/或化学改性淀粉组成的淀粉衍生物，纤维素衍生物，天然橡胶(碳水化合物聚合物)，半纤维素，多糖，水解胶体或这些原料中的一种或多种的混合物制成。
本发明具有以下优点。
本发明方法降低了生物聚合物的剪切强度，分解和分子量损失，结果使其制备方法更容易进行，因为进行反应的挤出机和成膜过程构成一个工艺操作单元。不需要将吸湿颗粒贮存在真空铝化合物中，而且混料和成膜一步完成。生产成本更低，因为不需要包装和运输颗粒并且人力和设备投资减少。另外，还可节省运送和熔化颗粒所需能源。与现有技术比较起来，所得膜性能得以提高。
以下参照附图说明本发明。
图1a为本发明吹塑膜生产线侧视图。
图1b为本发明图1a生产线顶视图。
图2a为本发明平面膜生产线侧视图。
图2b为本发明图2a生产线顶视图。
图3a为示出包括双管模板的螺杆挤出机端部的本发明方案示意图。
图3b为示出包括单管模板的螺杆挤出机端部的本发明方案示意图。
图3c为示出包括平面模板的螺杆挤出机端部的本发明方案示意图。
图1a和1b为本发明吹塑膜生产线的两种视图，其中示出了由运送和混合或捏和膜料的螺杆挤出机(未示出)连接的生产段1-6和模板7。固态植物原料和必要时的添加剂的混合物用计量装置17(仅示于图1a中)测量并经过第一段1的第一入口11加入，同时液态添加剂经过第二入口12加入。添加剂例子包括乳化剂，增塑剂，防腐剂和水。在第2段中，混合物加热并捏和。液态添加剂也可经第三入口13加入。在第3段中，温度进一步升高并让植物原料与添加剂反应而形成熔体。在第4段中，熔体在真空装置14中抽空，其中让水从熔体中蒸发而使熔体冷却，而且熔体在第5段中进一步冷却。在第6段中，熔体受压而在模板内造成压力累积，然后经管模板7吹塑形成膜15。类似生产线示于图2a和2b中(计量装置17仅示于图2a中)。图2a，2b和图1a，1b之间的差别在于平面膜16由平面模板9模制成。
图3a为本发明方案之一示意图，其中用双管模板8制造吹塑膜15，在双导向螺杆10之后设有两根单导向螺杆19以将熔体送达模板8。
在图3b中，用单管模板7制造吹塑膜15，其中模板由设在双导向螺杆10后的齿轮泵18供给熔体。
在图3c所示包括生产平面膜16的平面模板9的方案中，双导向螺杆10将熔体直接送达模板9。
螺杆挤出机10优选形状为双导向螺杆并且1-6段中每一段优选具有以下构型：第1和2段中为右手导向；第3段中为右和左手导向并必要时交替几次；第4和5段中为激剧右手导向；而第6段中为平缓右手导向。这些不同的构型保证控制并达到不同的传送速度，在每一段中进行捏和和混料并因此使生物聚合物达到要求的仔细处理。
第1-6段和模板7，8或9显示出可控制温度分布，其中温度条件包括：第1段10-80℃，优选50℃；第2段10-150℃，优选80-100℃；第3段70-200℃，优选120-160℃；第4段70-200℃，优选120-160℃；第5段70-200℃，优选80-120℃；第6段40-200℃，优选40-60℃；而模板7，8或9处40-150℃，优选50-70℃。
本发明方法得到的干状态膜含40-100wt％、优选75-95wt％碳水化合物。
在本发明方法中，可以加入甘油单硬脂酸酯添加剂作乳化剂，优选在第一段(1)中加入；可以加入甘油添加剂作增塑剂，优选在第二段(2)中加入；可以加入水添加剂作溶剂，优选在第二段(2)中加入；可以加入山梨酸钾添加剂作防腐剂，优选在第一段(1)中加入。上述添加剂的用量使得本发明方法得到的干状态膜含有0-25wt％、优选0.1-2.5wt％甘油单硬脂酸酯，0-40wt％、优选10-28wt％甘油以及0-5wt％、优选0.1-0.5wt％山梨酸钾。此外，本发明方法得到的薄膜可以含有0-35wt％、优选10-20wt％水。
本发明方法实施方案如以下所述，其中应用德国Werner undPfleiderer公司制造的双螺杆挤出机(ZSK40)。
实施例1
将包括马铃薯淀粉和乳化剂(甘油单-二酯)的固态混合物以及液态成分水和甘油连续加入双螺杆挤出机中。
固体：
马铃薯淀粉                   99％
乳化剂                       1％
                             100％
液态添加剂：
水                           14％
甘油                         86％
工艺中混合比：
固体                         75％
液体                         25％
温度分布：
第1段                        50℃
第2段                        80℃
第3段                        120℃
第4段                        120℃
第5段                        80℃
第6段                        60℃
模板                         60℃
RPM                          170分钟-1
转矩                         30％
压力                         80巴
吹塑比                       1∶4
得到透明膜，其性能如下：
膜厚：                       35μm
长度方向上抗拉强度           12.1N/mm2
宽度方向上抗拉强度           11.8N/mm2
10g膜在100g水中20℃溶解时间  15分钟
实施例2
将包括马铃薯淀粉和乳化剂(甘油单-二酯)的固态混合物以及液态成分水和甘油连续加入双螺杆挤出机中。
固体
马铃薯淀粉                   99％
乳化剂                       1％
                             100％
液态添加剂：
水                           20％
甘油                         80％
                             100％工艺中混合比：固体                          75％液体                          25％温度分布：第1段                         50℃第2段                         80℃第3段                         140℃第4段                         140℃第5段                         100℃第6段                         60℃模板                          60℃RPM                           170分钟-1转矩                          20％压力                          60巴吹塑比                        1∶4得到透明膜，其性能如下：膜厚：                        30μm长度方向上抗拉强度            10.2N/mm2宽度方向上抗拉强度            9.4N/mm210g膜在100g水中20℃溶解时间   11分钟实施例3
将包括马铃薯淀粉和乳化剂(甘油单-二酯)的固态混合物以及液态成分水和甘油连续加入双螺杆挤出机中。固体马铃薯淀粉                   99％乳化剂                       1％
                            100％液态添加剂：水                           10％甘油                         90％
                            100％工艺中混合比：固体                         75％液体                         25％温度分布：第1段                        50℃第2段                        80℃第3段                        160℃第4段                        160℃第5段                        120℃第6段                        60℃模板                         60℃
RPM                            230分钟-1
转矩                           15％
压力                           52巴
吹塑比                         1∶4
得到透明膜，其性能如下：
膜厚：                         33μm
长度方向上抗拉强度             9.4N/mm2
宽度方向上抗拉强度             8.2N/mm2
10g膜在100g水中20℃溶解时间    8分钟
实施例4
将包括玉米淀粉和乳化剂(甘油单-二酯)的固态混合物以及液态成分水和甘油连续加入双螺杆挤出机中。
固体
玉米淀粉                       98％
乳化剂                         2％
                               100％
液态添加剂：
水                             14％
甘油                           86％
                               100％
工艺中混合比：固体                             70％液体                             30％温度分布：第1段                            50℃第2段                            80℃第3段                            140℃第4段                            140℃第5段                            100℃第6段                            60℃模板                             60℃RPM                              200分钟-1转矩                             18％压力                             45巴吹塑比                           1∶3得到不透明膜，其性能如下：膜厚：                           42μm长度方向上抗拉强度               8.2N/mm2宽度方向上抗拉强度               6.8N/mm210g膜在100g水中20℃溶解时间     24分钟实施例5将包括小麦面粉和乳化剂(甘油单-二酯)的固态混合物以及液态成分水和甘油连续加入双螺杆挤出机中。
固体
Type405小麦面粉               98％
乳化剂                        2％
                              100％
液态添加剂：
水                            25％
甘油                          75％
                              100％
工艺中混合比：
固体                          70％
液体                          30％
温度分布：
第1段                         50℃
第2段                         80℃
第3段                         140℃
第4段                         140℃
第5段                         100℃
第6段                         60℃
模板                          60℃
RPM                           200分钟-1
转矩                          20％
压力                          55
该材料用平面狭缝模板模制并拉成膜。
得到不透明膜，其性能如下：
膜厚：                        94μm
长度方向上抗拉强度            9.6N/mm2
宽度方向上抗拉强度            9.0N/mm2
10g膜在100g水中20℃溶解时间   64分钟
实施例6
将包括马铃薯淀粉和乳化剂(甘油单-二酯)的固态混合物以及液态成分水和甘油连续加入双螺杆挤出机中。在双螺杆段结束时，该材料经过齿轮泵送达单管模板。
固体
马铃薯淀粉                     99％
乳化剂                         1％
                               100％
液态添加剂：
水                             14％
甘油                           86％
                               100％
工艺中混合比：固体                           80％液体                           20％温度分布：第1段                          50℃第2段                          100℃第3段                          140℃第4段                          140℃第5段                          80℃第6段                          40℃模板                           50℃RPM                            200分钟-1转矩                           62％泵入口压力                     80巴泵出口压力                     210巴吹塑比                         1∶4得到透明膜，其性能如下：膜厚：                         29μm长度方向上抗拉强度             14.1N/mm2宽度方向上抗拉强度             12.6N/mm210g膜在100g水中20℃溶解时间    10分钟实施例7
将包括马铃薯淀粉和乳化剂(甘油单-二酯)的固态混合物以及液态成分水和甘油连续加入双螺杆挤出机中。在双螺杆段结束时，该材料继续送到两根单导向螺杆，然后再继续送到双管模板8。在螺杆中，用两股产品物流形成两根同心管后立即相互层叠并一起吹塑成膜。
固体
马铃薯淀粉                       99％
乳化剂                           1％
                                 100％
液态添加剂：
水                               20％
甘油                             80％
                                 100％
工艺中混合比：
固体                             75％
液体                             25％
温度分布：
第1段                            50℃
第2段                            100℃
第3段                            120℃
第4段                            120℃第5段                          80℃第6段                          60℃模板                           70℃RPM                            160分钟-1转矩                           44％压力                           50吹塑比                         1∶4得到透明膜，其性能如下：膜厚：                         38μm长度方向上抗拉强度             11.4N/mm2宽度方向上抗拉强度             9.4N/mm210g膜在100g水中20℃溶解时间    31分钟

Claims (33)

1.用植物原料制造生物降解膜的方法，其中植物原料的塑化和随后的成膜过程一步连续进行，其中包括以下步骤：
a.在第一段(1)中经第一入口(11)连续加入已测定的植物原料，并将它们混合，
b.在第二段(2)中将混合物加热和捏和，
c.在第三段(3)中将植物原料加热并使其反应形成熔体，
d.在第四段(4)的真空装置(14)中将所说熔体抽空，其中让水从熔体蒸发并抽出，从而使熔体冷却，
e.第五段(5)中使熔体进一步冷却，
f.在第六段(6)中使熔体受压，
g.熔体经模板(7；8；9)挤出成膜(15；16)。
2.权利要求1的方法，其中植物原料为碳水化合物形式的植物原料。
3.权利要求1的方法，其中原料在工艺中改性和/或分解。
4.权利要求1或2或3的方法，其中植物原料包括面粉或天然淀粉，为天然或杂化物形式，可用马铃薯，木薯，豌豆，蚕豆，玉米，waxcorn，直链淀粉含量高的玉米，谷物，由物理和/或化学改性淀粉组成的淀粉衍生物，纤维素衍生物，天然橡胶，半纤维素，多糖，水解胶体或这些原料中的一种或多种的混合物制成。
5.权利要求1的方法，其中在步骤a中经第一入口(11)加入固态添加剂。
6.权利要求1的方法，其中在步骤a中在第一段(1)中经第二入口(12)加入液态添加剂。
7.权利要求1的方法，其中在步骤b中在第二段(2)中经第三入口(13)连续加入液态添加剂。
8.权利要求5-7中任一项的方法，其中在步骤c中添加剂与植物原料在第三段中反应形成熔体。
9.权利要求1的方法，其中在第一至第六段(1-6)中用螺杆挤出机(10)并根据(1-6)每一段中螺杆部件的构型和螺杆的转速将混合物或熔体传送，混合以及压制。
10.权利要求1的方法，其中第一至第六段中温度可选调。
11.权利要求1的方法，其中模板为单管模板(7)并制成吹塑膜(15)。
12.权利要求1的方法，其中模板为双管模板(8)并制成吹塑膜(15)。
13.权利要求1的方法，其中模板为平面模板(9)并制成平面膜(16)。
14.权利要求1的方法，其中在第一入口(11)前设置植物原料和添加剂的计量装置(17)。
15.权利要求9的方法，其中在螺杆挤出机(10)和模板(7，8，9)之间设置齿轮泵(18)或至少一根单导向螺杆(19)。
16.权利要求9的方法，其中螺杆挤出机(10)为双螺杆挤出机。
17.权利要求16的方法，其中双螺杆挤出机(10)具有以下构型：
a.在第一和第二段(分别为1和2)中为右手导向，
b.在第三段(3)中为右和左手导向并可交替一或几次，
c.在第四和第五段(分别为4和5)中为激剧右手导向，
d.在第六段(6)中为平缓右手导向。
18.权利要求10的方法，其中各段及模板温度条件如下：第一段(1)为10-80℃；第二段(2)为10-150℃；第三段(3)为70-200℃；第四段(4)为70-200℃；第五段(5)为70-200℃；第六段(6)为40-200℃；模板(7，8，9)处为40-150℃。
19.权利要求18的方法，其中各段及模板温度条件如下：第一段(1)为50℃；第二段(2)为80-100℃；第三段(3)为120-160℃；第四段(4)为120-160℃；第五段(5)为80-120℃；第六段(6)为40-60℃；模板(7，8，9)处为50-70℃。
20.权利要求1的方法，其中干状态膜含40-100wt％碳水化合物。
21.权利要求20的方法，其中干状态膜含75-95wt％碳水化合物。
22.权利要求1的方法，其中加入甘油单硬脂酸酯添加剂作乳化剂。
23.权利要求22的方法，其中在第一段(1)中加入甘油单硬脂酸酯添加剂。
24.权利要求1的方法，其中加入甘油添加剂作增塑剂。
25.权利要求24的方法，其中在第二段(2)中加入甘油添加剂。
26.权利要求1的方法，其中加入水添加剂作溶剂。
27.权利要求26的方法，其中在第二段(2)中加入水添加剂。
28.权利要求10的方法，其中加入山梨酸钾添加剂作防腐剂。
29.权利要求28的方法，其中在第一段(1)中加入山梨酸钾添加剂。
30.权利要求1的方法，其中干状态膜(15；16)含0-25wt％甘油单硬脂酸酯，0-40wt％甘油以及0-5wt％山梨酸钾。
31.权利要求30的方法，其中干状态膜(15；16)含0.1-2.5wt％甘油单硬脂酸酯，10-28wt％甘油以及0.1-0.5wt％山梨酸钾。
32.权利要求1的方法，其中膜(15；16)含0-35wt％水。
33.权利要求32的方法，其中膜(15；16)含10-20wt％水。
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NO950679L (no) 1995-02-23
CA2143291A1 (en) 1994-03-03
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GR3030189T3 (en) 1999-08-31
JPH08500380A (ja) 1996-01-16
AU4952193A (en) 1994-03-15
PL307610A1 (en) 1995-06-12
AU677964B2 (en) 1997-05-15
FI950835A0 (fi) 1995-02-23
EP0656032A1 (de) 1995-06-07
CA2143291C (en) 1999-02-02
ES2131117T3 (es) 1999-07-16
EP0656032B1 (de) 1999-04-07
DK0656032T3 (da) 1999-10-18
DE4228016C1 (de) 1994-03-31
NO950679D0 (no) 1995-02-23
ATE178625T1 (de) 1999-04-15
TW303378B (zh) 1997-04-21
JP3398731B2 (ja) 2003-04-21
US5525281A (en) 1996-06-11
WO1994004600A1 (de) 1994-03-03
FI950835A (fi) 1995-02-23
MY109052A (en) 1996-11-30
CZ48395A3 (en) 1995-09-13
BR9306957A (pt) 1999-01-12

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