CN1325424A - 包含淀粉和多糖酯的可生物降解组合物 - Google Patents
包含淀粉和多糖酯的可生物降解组合物 Download PDFInfo
- Publication number
- CN1325424A CN1325424A CN99812908A CN99812908A CN1325424A CN 1325424 A CN1325424 A CN 1325424A CN 99812908 A CN99812908 A CN 99812908A CN 99812908 A CN99812908 A CN 99812908A CN 1325424 A CN1325424 A CN 1325424A
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- Prior art keywords
- starch
- ester
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- acid
- additive
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- 239000005017 polysaccharide Substances 0.000 title claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 21
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- 229960003656 ricinoleic acid Drugs 0.000 claims description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 2
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- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims 1
- 239000001095 magnesium carbonate Substances 0.000 claims 1
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- PCMORTLOPMLEFB-ONEGZZNKSA-N sinapic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-ONEGZZNKSA-N 0.000 claims 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
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- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
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Abstract
可生物降解的异相组合物包括部分或完全变构和/或复合的淀粉、多糖酯及多糖酯的增塑剂。在这些组合物中多糖酯构成基体而淀粉以至少80%颗粒的数均尺寸小于1μm且优选小于0.5μm的颗粒或微区形式构成分散相。该组合物还包含能将溶液pH值提高并保持在4或更大的添加剂,所述溶液是通过使用1∶10的粒料∶水重量比在环境温度下使粒料形式的组合物与水接触1小时而获得的。
Description
本发明涉及包含淀粉和多糖酯、适于生产能在堆肥期间快速分解的模塑制品的可生物降解组合物。
据文献报道薄纤维素乙酸酯膜可快速降解；但是，厚膜或具有厚壁的制品进行生物降解所需的时间极长。例如，少于60％的厚膜降解需要2个月。
这一问题在包含淀粉和纤维素酯的组合物由具有良好可生物降解性的组合物供应组成的情况下可得到解决，所述组合物适于生产在堆肥期间具有适当分解能力的成型制品。
在专利文献中描述了聚合物组分间相容性改进了的但不具备适当生物降解性的包含淀粉和纤维素酯的组合物。
例如，EP-A-0722980描述的组合物中通过使用选自各种类聚合物物质的特殊相增容剂而赋予淀粉和纤维素酯彼此间更大的相容性，并且所述增容剂除了改进相容性外还由于在纤维素酯基体中的淀粉上赋予了高水平的分散性而具有改进生物降解性的效果。
但是，由该组合物生产的制品在堆肥期间的分解速率仍太低。
现在已令人惊讶地发现可以显著提高由部分或全部包含变构和/或复合淀粉和多糖酯，优选纤维素酯的组合物生产的制品的生物降解性，并由此提高其在堆肥期间的分解能力。
在标准堆肥条件下所生产制品的分解时间可缩短为小于2个月。
本发明的包含淀粉和多糖酯优选纤维素酯或淀粉酯的组合物以下述微结构为特征：其中酯构成基体而变构和/或分散的淀粉构成分散相，微区或分散颗粒的数均尺寸小于1μm，优选小于0.5μm，并且特征还在于它们包含能将溶液pH值提高并保持在4或更大的添加剂，所述溶液是通过使水∶颗粒重量比为10∶1在环境温度下将组合物颗粒浸没在水中1小时而获得的。
可以存在一部分天然结晶淀粉，相对起始淀粉含量最多为30％。
具有上述控制pH能力的添加剂具有通过中和在分解条件下水解纤维素酯所产生酸而显著提高组合物生物降解性的效力。任何不溶于水并具有上述能力的物质均为适宜的添加剂。
添加剂的实例为碱土金属的碳酸盐和氢氧化物如CaCO3,MgCO3,Mg(OH)2。CaCO3是优选的添加剂。
组合物包括重量比为1∶0.6-1∶18，优选为1∶2-1∶3的淀粉和被10-40wt％量增塑剂增塑的多糖酯。
添加剂以相对淀粉和增塑多糖酯重量0.5-30wt％，优选5-20wt％的量存在。
可以使用大于30wt％的量但不会带来任何有意义的进一步改进。
添加剂的量太大会对组合物的机械性能有不利影响。
除了多糖酯相的增塑剂外，组合物还可包括用量相对淀粉重量为0.5-50wt％的淀粉相增塑剂。
为了生产如上述的精细分散微结构，使用属于下列种类的添加剂：
a)与多糖酯和/或淀粉相容的聚合物，其上接枝含有4-40个碳原子的脂族或多羟基化链，
b)含有2-24个碳原子的羟基酸和/或二胺与脂族或芳族二异氰酸酯或与环氧化合物或酸酐的共聚物，
c)脂族聚酯、聚酰胺、聚脲或聚亚烷基二醇与脂族或芳族二异氰酸酯的共聚物，
d)与多糖酯和/或淀粉相容的聚合物，其上接枝有溶于淀粉的多元醇或能复合淀粉的聚合物，及
e)能够复合淀粉的聚合物，如乙烯/乙烯醇或乙烯/丙烯酸共聚物、脂族聚酯和聚酰胺。
a)型添加剂优选通过接枝脂族链而获得，该脂族链衍生自带有可使链接枝更容易的诸如羧基基团、酯或盐端基的植物或动物脂肪的如油酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、亚油酸和蓖麻油酸。
与纤维素酯相容的聚合物的实例为：
-各种取代度(DS)的纤维素酯，
-各种DS值的淀粉酯，如乙酸酯，
-各种DS值的淀粉酯，如淀粉与乙二醇或丙二醇的反应产物，
-部分水解的聚乙酸乙烯酯，
-脂族聚酯和脂族/芳族共聚酯。
接枝链的数目为聚合链中每100个单体单元有0.1-100，优选0.2-50，更优选0.3-20个接枝链。
b)型和c)型添加剂的实例为可由脂族聚酯如聚己内酯和聚丁二酸二乙酯生产的共聚物。
由Goodrich以Estane商标54351级出售的己内酯-氨基甲酸乙酯共聚物为b)类共聚物的代表。
添加剂以相对淀粉和增塑多糖酯重量和0.1-20wt％，优选0.5-10wt％的量存在。
除了上述组分，本发明的组合物还可包含用量最多为30wt％，优选少于10wt％的聚乙烯醇、聚乙酸乙烯酯、热塑性聚酯合成聚合物如聚己内酯、己内酯与异氰酸酯的共聚物、乳酸聚合物、聚乙烯或聚丁烯及一般的聚亚烷基己二酸酯、癸二酸酯和壬二酸酯。
用于制备组合物的淀粉为从各种植物如玉米、小麦、马铃薯、木薯和谷类淀粉中提取的天然淀粉。术语淀粉还包括高支链淀粉含量的淀粉(“蜡状”淀粉)、高直链淀粉含量的淀粉、化学和物理改性淀粉、与磷酸酯基团相连的阳离子的类型和浓度被改进的淀粉、淀粉乙氧基化物、淀粉乙酸酯、阳离子型淀粉、水解淀粉、氧化和交联淀粉。
最终组合物包含部分或全部变构和/或复合的淀粉。变构淀粉是指失去其颗粒结构的淀粉(这意谓着不存在在250-700倍放大倍数范围内可由光学显微镜在极化光下可见的马尔他十字形)。
复合淀粉是指在氯仿中除去纤维素或淀粉酯后在946-947cm-1附近的第二派生FTIR中显示吸收带(在高淀粉浓度时不用抽提纤维素或淀粉酯)或在X-射线衍射实验中在2θ为12-13和20附近也显示峰的淀粉。
代表性纤维素和淀粉酯包括各种取代度的纤维素乙酸酯、丙酸酯和/或丁酸酯。DS为1.5-2.5的纤维素乙酸酯是优选的。
用于纤维素酯的增塑剂优选选自下列化合物：
-与最多含有6个碳原子的脂族酸的甘油酯，特别是二醋精和三醋精，
-柠檬酸酯，特别是柠檬酸三甲酯或三乙酯，以及乙酰基-三乙基柠檬酸酯，
-酒石酸二烷基酯，
-脂族酸酯、内酯和交酯，
-脂族酸二烷基酯如由乙二酸、戊二酸、己二酸、癸二酸、辛二酸、壬二酸得到者，优选己二酸二丁酯和癸二酸二丁酯，
-烷基基团含有1-10个碳原子的芳香酸二烷基酯，特别是邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、甲氧基乙基邻苯二甲酸酯和乙氧基乙基邻苯二甲酸酯，
-聚乙二醇己二酸酯、戊二酸酯或癸二酸酯，
-烷基和芳基磷酸酯，特别是三乙基和三甲苯基磷酸酯，
-脂肪酸烷基酯如油酸丁酯，
-聚合物增塑剂如由Rohm and Haas以商标Paraplex、Arche DanielsMidland以Admex和Union Carbide以Flexol出售的产品，
-三羟甲基丙烷和季戊四醇、带有烷基磷酸酯端基的聚乙二醇的混合脂族-芳族酯。
优选增塑剂为同时用作淀粉相和纤维素酯相增塑剂者。醋精属于该优选种类。
淀粉增塑剂包括水、甘油、甘油乙氧基化物、乙二醇或丙二醇、聚乙二醇、聚丙二醇、1,2-丙二醇、1,3-丙二醇、1,2-,1,3-,1,4-丁二醇、1,6-,1,5-己二醇、山梨糖醇二乙氧基化物和三羟甲基丙烷一乙氧基化物。
淀粉通常在与所有其它组分混合物混合阶段被直接增塑。但是，也可以使用淀粉相和纤维素相被分别增塑的两段法。
本发明组合物的制备包括在加热挤塑机中或在从流变学观点看可保证使淀粉和纤维素酯组分彼此相容的适当温度和剪切应力条件的任何封闭容器中混合各组分，在水和增塑剂存在下于80-210℃下进行。
制备组合物的优选方法包括：
-第一步，包括让各组分从挤塑机中通过，在挤塑机中所耗时间为2-50秒，在此期间使淀粉和纤维素酯在增塑剂及可能加入的水作用下经历膨胀，在80-180℃进行，
-混合步，在此期间使上述步骤的混合物经历特别适于使熔融纤维素酯和淀粉粘度相似(如果起始粘度不同)的剪切应力条件，
-选择性脱气步骤，得到水含量少于6wt％的熔体，它同时可保证在挤塑产品中不形成气泡。如果要生产发泡材料，水含量可高于6wt％且可达到18-20wt％。
挤塑所得熔融材料形成粒料，利用任何常规技术由此生产制品，或者组合物可直接被挤塑生产模塑或注塑制品。
本发明组合物适于生产泡沫塑料、发泡挤塑容器、发泡挤塑板、模塑泡沫塑料、注塑制品如玩具和一次性餐具及一般要求在堆肥期间分解时间不超过2个月的任何用途的制品。提供下列实施例是出于说明的目的而非要限制本发明范围。
实施例
实施例1-4为对比例；实施例5-7为根据本发明的。
(A)混合
实施例的组合物是使用直径为30mm且L∶D=25的2030型双螺杆APV挤塑机制备的。16个控温区的温度分布如下：
60℃×1-100℃×1-180℃×14。
螺杆旋转速率为120rpm。
(B)注塑
将由挤塑机生产的粒料供给Sandretto系列60注压机以生产成型试验样品。通过光学显微镜或通过SEM电子显微镜检测样品的表面质量。
还试验了样品的生物降解性。
试验结果在表1和2中给出。
表1
| 实施例1实施例2实施例3实施例4实施例5实施例6实施例7 | |
| Aceplast LSCAB二醋精环氧化豆油玉米淀粉DS=1.3的乙酰化淀粉Sorbilene(山梨糖醇乙氧基化物)芥酰胺SAC DS 1.3/月桂酸酯4.6SAC DS 1.1/月桂酸酯3.2碳酸钙氢氧化镁粘土 | 75 44 44 44 38 38 384425 16 14 14 1416 1632 32 27 25 25 2557.8 7.8 7.8 7.8 7.8 7.80.2 0.2 0.2 0.2 0.2 0.2555 1010 |
| 脚注 | a B c a,d a,d a,d a,d |
(a)试验材料的生物降解性(结果在表2中给出)
(b)试验样品发生严重分层
(c)试验样品倾向于分层
(d)样品表面外观均匀无剥落。
根据SEM，所有具有表面特性(d)的样品均具有这样的微观结构：其中分散的淀粉相为微区形式，至少80％的微区的数均尺寸小于0.3μm。
表符号说明
1)Aceplast LS为由意大利Verbania的Societa Acetati S.p.A出售的取代度为2.5的纤维素乙酸酯。
2)CAB为由Eastman Chemicals以商标CAB831-20出售的纤维素丁酸酯/乙酸酯。
3)DS=1.3的乙酰化淀粉是由National Starch生产的并称作“78-0403GDS-1233”。
4)表中所指添加剂是由DS为1.3和2.1的淀粉乙酸酯(SAC)通过接枝上每100单体单元SAC基团含量为4.2和3.2的月桂基基团而生产的。
接枝是使用月桂酰氯在二甲基乙酰胺中进行的。
用吡啶中和后，用乙醚沉淀出增容剂。
组合物的生物降解性
生物降解性是通过记录样品的重量损失而进行试验的，样品被装入聚丙烯网(网眼1mm)中并放入到湿度为55％且被加热到55℃的培养箱中的老化堆肥基底中。装入许多样品，即每个网一个样品以便在降解时间内过程连续。对于每个样品，使用50g堆肥。结构在表2中给出。
表2样品经过15,60和150天后重量损失百分比
| 实施例 | 15天 | 60天 | 150天 |
| 1 | 18.6 | 23.1 | 26.3 |
| 4 | 29.8 | 39.1 | 51.7 |
| 6 | 40.0 | ＞90.0 | 完全降解 |
| 7 | 50.0 | ＞90.0 | 完全降解 |
| 8 | 35.0 | ＞80.0 | 完全降解 |
Claims (16)
1．可生物降解的异相组合物，包括部分或完全变构和/或复合的淀粉、多糖酯及多糖酯的增塑剂，其中多糖酯构成基体而淀粉以至少80％颗粒的数均尺寸小于1μm的颗粒或微区形式构成分散相，该组合物包含能将溶液pH值提高并保持在4或更大的添加剂，所述溶液是通过使用1∶10的粒料：水重量比在环境温度下使粒料形式的组合物与水接触1小时而获得的。
2．根据权利要求1的可生物降解组合物，其中多糖酯为纤维素或淀粉酯。
3．根据权利要求1或2的可生物降解组合物，其中分散相颗粒或微区的尺寸小于0.5μm。
4．根据任意上述权利要求的可生物降解组合物，其中添加剂选自碱土金属的碳酸盐和氢氧化物。
5．根据权利要求4的可生物降解组合物，其中添加剂选自碳酸钙和碳酸镁。
6．根据权利要求1-5任意一项的可生物降解组合物，其中多糖酯为取代度大于2，优选大于2.4的纤维素乙酸酯。
7．根据权利要求1-6任意一项的可生物降解组合物，其中多糖酯的增塑剂以相对多糖酯重量15-50wt％的量存在。
8．根据权利要求1-7任意一项的可生物降解组合物，其中调节pH的添加剂以相对淀粉和增塑纤维素酯重量0.5-30wt％的量存在。
9．根据权利要求8的可生物降解组合物，其中添加剂以5-15wt％的量存在。
10．根据权利要求1-9任意一项的可生物降解组合物，包括选自下列化合物的添加剂：
-与多糖酯相容的聚合物或共聚物，其上接枝含有4-40个碳原子的脂族或多羟基化链，
-由含有2-24个碳原子的羟基酸和二胺、脂族聚酯、聚酰胺、聚脲和聚亚烷基二醇与脂族或芳族二异氰酸酯获得的共聚物，
-通过接枝溶于淀粉的多元醇由与多糖酯相容的聚合物制备的共聚物。
11．根据权利要求10的可生物降解组合物，其中添加剂以相对淀粉和增塑纤维素酯重量0.1-20wt％的量使用。
12．根据权利要求1-9任意一项的可生物降解组合物，其中添加剂选自与用脂肪酸接枝的纤维素酯相容的聚合物或共聚物及聚己内酯和脂族或芳族二异氰酸酯间的嵌段共聚物，所述脂肪酸选自油酸、月桂酸、棕榈酸、硬脂酸、芥子酸、亚油酸和蓖麻油酸。
13．根据权利要求1-12任意一项的可生物降解组合物，包括用于淀粉相的增塑剂，用量相对淀粉重量为1-50wt％。
14．根据权利要求1-13任意一项的可生物降解组合物，其中增塑纤维素酯∶淀粉的重量比为1∶1-18∶1。
15．由权利要求1-14的组合物生产的制品。
16．根据权利要求15的制品，适于生产泡沫塑料、发泡挤塑容器、发泡挤塑板、模塑泡沫塑料。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT1998TO000735A IT1303553B1 (it) | 1998-09-01 | 1998-09-01 | Composizioni biodegradabili comprendenti amido ed esteri di cellulosa. |
| ITTO98A000735 | 1998-09-01 |
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| Publication Number | Publication Date |
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| CN1325424A true CN1325424A (zh) | 2001-12-05 |
| CN1225494C CN1225494C (zh) | 2005-11-02 |
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| CNB998129089A Expired - Fee Related CN1225494C (zh) | 1998-09-01 | 1999-08-31 | 包含淀粉和多糖酯的可生物降解组合物 |
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| EP (1) | EP1109858B1 (zh) |
| JP (1) | JP4303890B2 (zh) |
| KR (1) | KR20010073073A (zh) |
| CN (1) | CN1225494C (zh) |
| AT (1) | ATE238386T1 (zh) |
| AU (1) | AU755074B2 (zh) |
| BR (1) | BR9913491A (zh) |
| CA (1) | CA2342174C (zh) |
| DE (1) | DE69907224T2 (zh) |
| DK (1) | DK1109858T3 (zh) |
| ES (1) | ES2195611T3 (zh) |
| HR (1) | HRP20010241A2 (zh) |
| IL (1) | IL141664A0 (zh) |
| IT (1) | IT1303553B1 (zh) |
| MX (1) | MXPA01002196A (zh) |
| NO (1) | NO328637B1 (zh) |
| WO (1) | WO2000012616A1 (zh) |
| ZA (1) | ZA200102222B (zh) |
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| CN100497452C (zh) * | 2002-01-16 | 2009-06-10 | 伊士曼化工公司 | 用作聚合物的增塑剂的新型糖酯和多元醇酯、包含所述增塑剂的组合物和制品以及所述增塑剂的使用方法 |
| CN103044714A (zh) * | 2011-10-11 | 2013-04-17 | 陈镜荣 | 一种塑料制作方法 |
| CN112375259A (zh) * | 2014-12-11 | 2021-02-19 | 索尔维阿塞托有限公司 | 包含碱性添加剂的聚合物组合物，方法以及包含所述聚合物组合物的物品 |
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| EP0947559B1 (en) * | 1996-11-05 | 2004-10-27 | NOVAMONT S.p.A. | Biodegradable polymeric compositions comprising starch and a thermoplastic polymer |
| US20030220466A1 (en) * | 2001-12-04 | 2003-11-27 | Ministero Dell'universita' E Della Ricerca Scientifica E Tecnologica | Simplified method of producing biodegradable aliphatic polyesters |
| JP4646355B2 (ja) * | 2000-05-08 | 2011-03-09 | 日本コーンスターチ株式会社 | 生分解性樹脂発泡体の製造方法 |
| DE102004007941B4 (de) * | 2004-02-18 | 2006-04-27 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Biologisch abbaubares Compound, das sich für Spritzguss, Folienextrusion und zum Blasformen eignet, Verfahren zu seiner Herstellung und seine Verwendung, insbesondere im Lebensmittelbereich |
| EP1580228A1 (en) * | 2004-03-24 | 2005-09-28 | Nederlandse Organisatie voor toegepast-natuurwetenschappelijk onderzoek TNO | Process for gelatinising starch using a biodegradable polymer material bearing aldehyde groups |
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| US8802754B2 (en) * | 2005-01-25 | 2014-08-12 | Mgpi Processing, Inc. | Starch-plastic composite resins and profiles made by extrusion |
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| US8435354B2 (en) * | 2005-10-11 | 2013-05-07 | The Procter & Gamble Company | Water stable compositions and articles comprising starch and methods of making the same |
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| CN101784596B (zh) * | 2007-06-01 | 2012-09-05 | 普朗蒂克科技有限公司 | 淀粉纳米复合材料 |
| DE102007050770A1 (de) * | 2007-10-22 | 2009-04-23 | Biotec Biologische Naturverpackungen Gmbh & Co. Kg | Polymeres Material und Verfahren zu dessen Herstellung |
| FR2927088B1 (fr) * | 2008-02-01 | 2011-02-25 | Roquette Freres | Compositions thermoplastiques a base d'amidon plastifie et procede de preparation de telles compositions. |
| FR2927084B1 (fr) * | 2008-02-01 | 2011-02-25 | Roquette Freres | Procede de preparation de compositions thermoplastiques a base d'amidon plastifie et compositions ainsi obtenues. |
| CA2723192A1 (en) | 2008-05-07 | 2009-11-12 | Surmodics, Inc. | Delivery of nucleic acid complexes from particles |
| DE102008051579A1 (de) * | 2008-10-14 | 2010-04-15 | Rhodia Acetow Gmbh | Biologisch abbaubarer Kunststoff und Verwendung desselben |
| BR112012010007B1 (pt) | 2009-10-30 | 2021-04-06 | Stichting Kennis Exploitatie Rb. | Composição biodegradável, artigo biodegradável e processo para fabricação de uma composição biodegradável |
| US8901092B2 (en) | 2010-12-29 | 2014-12-02 | Surmodics, Inc. | Functionalized polysaccharides for active agent delivery |
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| WO2023059853A1 (en) * | 2021-10-08 | 2023-04-13 | Eastman Chemical Company | Articles containing melt processable cellulose ester compositions comprising amorphous biofiller |
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| WO2023059849A1 (en) * | 2021-10-08 | 2023-04-13 | Eastman Chemical Company | Process for making melt processable cellulose ester compositions comprising amorphous biofiller |
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| DE4237535C2 (de) | 1992-11-06 | 2000-05-25 | Biotec Biolog Naturverpack | Biologisch abbaubare Polymermischung, ein Verfahren und eine Folie |
| JPH07102114A (ja) * | 1993-10-04 | 1995-04-18 | Teijin Ltd | 生分解性組成物 |
| IT1272871B (it) | 1995-01-10 | 1997-07-01 | Novamont Spa | Composizioni termoplastiche compredenti amido ed altre componenti di origine naturale |
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1998
- 1998-09-01 IT IT1998TO000735A patent/IT1303553B1/it active IP Right Grant
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- 1999-08-31 WO PCT/EP1999/006390 patent/WO2000012616A1/en not_active Application Discontinuation
- 1999-08-31 MX MXPA01002196A patent/MXPA01002196A/es not_active Application Discontinuation
- 1999-08-31 KR KR1020017002633A patent/KR20010073073A/ko not_active Application Discontinuation
- 1999-08-31 DE DE69907224T patent/DE69907224T2/de not_active Expired - Lifetime
- 1999-08-31 US US09/786,189 patent/US6730724B1/en not_active Expired - Lifetime
- 1999-08-31 EP EP99946073A patent/EP1109858B1/en not_active Expired - Lifetime
- 1999-08-31 AT AT99946073T patent/ATE238386T1/de active
- 1999-08-31 ZA ZA200102222A patent/ZA200102222B/en unknown
- 1999-08-31 BR BR9913491-8A patent/BR9913491A/pt not_active IP Right Cessation
- 1999-08-31 JP JP2000567622A patent/JP4303890B2/ja not_active Expired - Fee Related
- 1999-08-31 CN CNB998129089A patent/CN1225494C/zh not_active Expired - Fee Related
- 1999-08-31 IL IL14166499A patent/IL141664A0/xx unknown
- 1999-08-31 ES ES99946073T patent/ES2195611T3/es not_active Expired - Lifetime
- 1999-08-31 DK DK99946073T patent/DK1109858T3/da active
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497452C (zh) * | 2002-01-16 | 2009-06-10 | 伊士曼化工公司 | 用作聚合物的增塑剂的新型糖酯和多元醇酯、包含所述增塑剂的组合物和制品以及所述增塑剂的使用方法 |
| CN103044714A (zh) * | 2011-10-11 | 2013-04-17 | 陈镜荣 | 一种塑料制作方法 |
| CN112375259A (zh) * | 2014-12-11 | 2021-02-19 | 索尔维阿塞托有限公司 | 包含碱性添加剂的聚合物组合物，方法以及包含所述聚合物组合物的物品 |
| CN115716938A (zh) * | 2014-12-11 | 2023-02-28 | 索尔维阿塞托有限公司 | 包含碱性添加剂的聚合物组合物，方法以及包含所述聚合物组合物的物品 |
| CN112375259B (zh) * | 2014-12-11 | 2023-10-03 | 索尔维阿塞托有限公司 | 包含碱性添加剂的聚合物组合物，方法以及包含所述聚合物组合物的物品 |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE238386T1 (de) | 2003-05-15 |
| DE69907224D1 (de) | 2003-05-28 |
| NO328637B1 (no) | 2010-04-12 |
| WO2000012616A1 (en) | 2000-03-09 |
| MXPA01002196A (es) | 2003-03-27 |
| KR20010073073A (ko) | 2001-07-31 |
| CN1225494C (zh) | 2005-11-02 |
| NO20011039L (no) | 2001-02-28 |
| AU5857099A (en) | 2000-03-21 |
| US6730724B1 (en) | 2004-05-04 |
| DE69907224T2 (de) | 2003-12-11 |
| HRP20010241A2 (en) | 2002-04-30 |
| ITTO980735A1 (it) | 2000-03-01 |
| JP4303890B2 (ja) | 2009-07-29 |
| ES2195611T3 (es) | 2003-12-01 |
| IL141664A0 (en) | 2002-03-10 |
| AU755074B2 (en) | 2002-12-05 |
| BR9913491A (pt) | 2001-05-22 |
| CA2342174A1 (en) | 2000-03-09 |
| NO20011039D0 (no) | 2001-02-28 |
| IT1303553B1 (it) | 2000-11-14 |
| JP2002523598A (ja) | 2002-07-30 |
| ZA200102222B (en) | 2001-09-18 |
| ITTO980735A0 (it) | 1998-09-01 |
| DK1109858T3 (da) | 2003-08-04 |
| EP1109858A1 (en) | 2001-06-27 |
| CA2342174C (en) | 2008-12-09 |
| EP1109858B1 (en) | 2003-04-23 |
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