CN1050391A - 用于生产生物降解塑料制品的聚合物组合物及其制备方法 - Google Patents
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Abstract
一种用于生产生物降解塑料制品的聚合物组合
物,它包括一种乙烯/乙烯醇共聚物和解体的淀粉。
此组合物尤其用于生产具有良好耐打孔性和抗扯性
的薄膜和具有改进的机械强度的成型制品。用这种
组合物制成的产品还是良好的氧气和二氧化碳隔离
层。
Description
本发明涉及用来生产生物降解塑料制品的聚合物组合物以及其制备方法。
近年来,人们已作了许多努力来寻找一种生物降解聚合物来取代传统的以石油为基础的塑料材料(其在环境中的效果不佳)。已经进行的研究一方面提供了这样的组合物,将该组合物按传统的方法可加工成包装膜和铺地膜,另一方面也提供了一类组合物,将其用于生产成型制品可具有良好的机械强度。
作为生产薄膜的组合物,美国专利4133784介绍了由淀粉和乙烯-丙烯酸共聚物(EAA)构成的组合物,因此组合物可制成柔软的,抗水的,可热焊接的并可生物降解的薄膜。
通过浇铸(涂布),简单挤出或压延(辊炼)技术可将组合物制成薄膜。然而这些方法既慢又很贵。此外,用一定量的淀粉成分(用其来实现所需的机械性能)会使产品的生物降解度和紫外线稳定程度大受影响。
美国专利4337181建议在EAA共聚物-淀粉组合物中加入一定量的中和剂,例如:氨或胺,其量要足以中和EAA的部分或全部酸基,然后将由此获得的组成物(水分为2至10%)进行吹塑成型。
在Ind.Eng.Chem.Res.1987,26,第1659-1663页上也从经济性和质量的观点建议在EAA共聚物/淀粉组合物中加入脲和/或多元醇以便简化生产并改进所得的薄膜。脲的存在可有效地改进淀粉与少量水的胶凝作用,因而可以从半干组合物(水含量约为16%)直接生产均匀的薄膜并且可以避免在进行挤出之前所必须进行的在混合器中将大量水与EAA共聚物-淀粉混合物所进行的混合。
然而总的来说由上述技术文件中所述方法生产的薄膜其抗扯性低,这就使得它们完全不适于用来生产包装制品,如袋子等等。
因此本发明的第一个目的是提供一种组合物,使用传统的制膜技术可将此组合物制成薄膜并进而生产片材,此种片材除了具有柔韧性,抗水性,热焊接性和生物降解性以外还具有良好的机械强度特性以及良好的抗撕性和打孔性。
关于成型制品的生产,这个词是指壁厚大于0.2毫米的制品,美国专利4591475叙述了一种注射成型方法,该方法用尚未被解体的淀粉作原料。
在这种情况下已经发现这种方法是很易变的,因为产品在熔融态的粘度取决于切断形变的速率,此速率使成型方法极大地依赖于螺杆的速度,温度和压力条件和/或水含量,并降低所生产制品的质量。
在欧州专利申请公开件304401中叙述了一种从已被解体的淀粉而注射成型膜片的方法。在这种情况中,由这种方法所得到的制品其机械性能很差,而且在水中极易溶解。
按照上述观点,本发明更进一步的目的是提供一种组合物,用该组合物生产成型制品可具有良好的物理和机械性能。
按照所拟定的目的,本发明的第一主题是用来生产可生物降解的塑料制品的聚合物组合物,它包括乙烯/乙烯醇共聚物和已被解体的淀粉。
根据本发明组合物中乙烯/乙烯醇共聚物的作用是提供所需要的机械,物理和化学性能,典型的共聚物其乙烯含量从10~90%(重量),优选10-40%(重量)(15-50%摩尔),更优选30-45%(摩尔),其熔融指数(230℃,2.16公斤)在2和50之间,优选6和20之间。
乙烯/乙烯醇共聚物的进一步优选特性如下:
特性粘度,〔η〕 0.50-0.9
(在30℃时于DMSO中测试) 优选0.65-0.80
分子量分布 Mw/Mn 1.3-4
(在四氢呋喃中,用凝胶渗透色谱测量)
熔点温度 <180℃
优选160-170℃
水解度*90-99.9%
*碱性水解,残余的碱用酸滴定。
可以使用由Solvay生产的,商业名称为Clarene(注册商标)的共聚物。
在本说明书及权利要求中所用的“淀粉”一词通常包括基本上由直链淀粉和/或支链淀粉组成的所有天然的或来源于植物的淀粉。这些淀粉可以从各种植物中提取,如:土豆,大米,木薯,玉米和谷类如黑类,燕麦和小麦。优选玉米淀粉。淀粉一词还包括酸度指数已降低到3和6之间的改性淀粉,以及土豆淀粉,其中与磷酸根缔合的阳离子的类型及浓度均已改变。在本发明的方法中可以使用淀粉的乙氧基衍生物,淀粉的乙酸盐类,阳离子淀粉,氧化淀粉,交联淀粉等等。
已被解体的淀粉一词是指淀粉已用高于其组分的玻璃化转变温度和熔点温度进行了热处理,因此其组分经受了吸热转变,从而使淀粉颗粒的分子结构形成了无序状态。
下面将更全面地叙述本发明的解体淀粉方法和制备组合物的方法。
根据本发明的组合物中,已解体的淀粉和乙烯/乙烯醇共聚的重量比从1∶19至19∶1,优选1∶4至4∶1。
此组合物最好包括一种沸点高于150℃的高沸点增塑剂,其数量为淀粉重量的0.05~100%,优选0.05~40%。
所使用的增塑剂为多元醇,如分子量为200~4000的聚乙二醇、1,2-亚乙基二醇,丙二醇,山梨醇,优选甘油。
此组合物还可包括一定量的脲,其量为淀粉组分重量的2~20%。虽然不是必须使用脲,但根据制备组合物的方法用脲作为淀粉一解体剂比较好,通过下文即可对这一点更全面地了解。
此组合物还可包含其它低熔点聚合物,尤其是改性乙烯聚合物,特别是乙烯/丙烯酸(EAA)共聚物,或者甚至是聚乙烯醇,聚合物的含量最多为组合物总重量的15%,对于EAA共聚物,要使用水分散共聚物,如美国专利4133784中所叙述的那些聚合物,该专利的内容已作为结果包括在本说明书内。
组合物中还可以有交联剂如:甲醛,仲甲醛,仲乙醛和表氯醇。
人们还希望此组合物中还包括能赋予制品(用组合物制备)特殊性质的其它添加剂。例如加入紫外线稳定剂,如碳黑,可改进制品耐日光性,如果制品需要有耐火性,则可加入耐火剂。其它的添加剂包括在淀粉基的成型或吹塑挤出组合物中通常加入的那些添加剂,如:杀菌剂,除草剂,抗氧化剂,肥料,遮光剂,稳定剂和增塑剂。所有这些添加剂的用量可以是本专业领域内行所知道的常规用量,或者用常规试验来简单确定,添加剂的用量最高为最终组合物重量的20%。
组合物中的水来自所用淀粉固有的水分或在制备方法过程中所加入的适量水,全部水量不大于组合物重量的6%。
此组合物是在加热的挤出机中经混合而制备的,由此而生产出挤出物,可将挤出物造粒随后用于常规的塑料加工。
制备此组合物的方法(它构成本发明更进一步的主题),以其最常见的形式来说包括以下步骤,将乙烯/乙烯醇共聚物和淀粉以1∶19至19∶1,优选1∶4至4∶1的重量比,加上数量为淀粉重量的0.05~100%的高沸点增塑剂,还可以加入解体剂,此解体剂选自由脲,碱土金属或碱金属的氢氧化物组成的一组化合物,在一台被加热的挤出机中进行混合,挤出机的加热温度和加热时间要足以使淀粉解体。
可以在单独的混合阶段制备组合物,在这种情况下,所用解体剂的量为淀粉重量的2-20%并加入适量的水,其数量为淀粉重量的0.05~100%,用钠,钾和钙的氢氧化物可以组成其它有用的解体剂。在挤出机中还可加入氨,所用的氨其重量通过在挤出过程中或在这之后的干燥阶段处理而减少为不大于组合物重量的0.5%。
根据所用淀粉的种类以及它的水含量,挤出机内的温度在120℃和170℃之间,优选130℃至160℃的范围。
根据优选的实施例,本发明组合物的制备方法包括混合步骤,即在一加热的挤出机中,将乙烯/乙烯醇共聚物与解体淀粉基组分进行混合。解体淀粉基组分是预先制备的,即在一台挤出机中将淀粉与一定量(淀粉重量的0.05~100%)的高沸点增塑剂,在有一定量解体剂(解体剂选自由脲,碱的氢氧化物,碱土的氢氧化物组成的一组化合物)的存在下进行混合而成的,该解体剂在低于增塑剂沸点及120℃和170℃之间,优选130℃-160℃之间的温度可有效地引起淀粉的解体。
解体淀粉是预先在没有加入水的条件下制备的,也就是在仅有淀粉固有的水份存在下进行的,此水含量通常为10-13%(重量),在制备解体淀粉组分的过程中,可在淀粉中加入低熔点共聚物,尤其是EAA
已经发现在有高沸点增塑剂存在而不加水情况下预先制备解体淀粉组分时,所产生的组合物可在高于120℃的温度进行加工而不会产生气泡,该组合物可在低压下进行挤出而不会有易挥发物所带来的问题。此组合物尤其适于接下来与乙烯醇共聚物组分在挤出机中进行混合。
此组合物是本发明的主题,它通常被制成粒料的形式,接下来用注模吹塑,热成型技术等制成薄膜或成型产品。
使用此组合物通过常规的塑料加工工艺而获得的成型产品和薄膜也在本发明的范围之内。尤其是对于薄膜或片状材料,此组合物可使通过挤一吹方法生产的薄膜具有良好的机械强度特性,尤其是耐截断和耐打孔性,并且还可使薄膜用作氧和二氧化碳的不渗透膜,还可用于包装和覆盖。
通过下面的例子可对本发明的进一步特性和优点了解得更清楚,这些例子仅用来说明本发明。
例1
将乙烯/乙烯醇共聚物,Clarene R20(注册商标),和为共聚物重量15%的甘油在140℃由HAAKE Reomex挤出机进行挤出,挤出机的型号是252,长径比(L/D)为19,螺杆直径为19mm,压缩比为1∶3,螺杆转速为40rpm。
将由此获得的50份产品与70份GLOBE03401 CERESTAR(注册商标)的淀粉,50份的水和15份的脲进行混合,然后用相同的挤出机在120℃进行挤出,把由此得到的挤出物制成粒料。
把此粒料供入带有吹膜机头的相同挤出机。从约为100微米厚的薄膜作出长方形测试件用于ASTM882的拉伸试验。
测试条件为23±1℃,55±5%相对湿度,24小时。
机械强度测试得到下列结果(用平均值表示):
杨氏模量 5285Kg/cm2
屈服应变 17%
断裂应变 52.8%
屈服应力 186Kg/cm2
断裂应力 178Kg/cm2
例2
制备一种组合物,它含有:
-63%重量的未干燥GLOBE03401 CERESTAR(商标)淀粉(带有11%的水分);
-25%重量的甘油;
-7%重量的脲;
-5%重量的Dow化学公司的共聚物EAA5981(含有20%的丙烯酸)。
用Licoarbo DC-10送料计量器将组合物供入Baker Perkins MPC/v-30挤出机。挤出机由分为两个区域的双螺杆单元构成,螺杆直径为30mm,螺杆长径比(L/D)为10∶1,将此挤出机与一台单螺杆挤出机相连接,该挤出机带有毛细管机头,螺杆直径为30mm,长径比(L/D)为8∶1,螺杆分为三段,所用毛细管喷嘴的直径为4.5mm。
挤出温度为140℃。
所获得的挤出物进行造粒不会有问题。
用相同的挤出机在160℃挤出60%的解体淀粉颗粒和40%(重量)的ClareneR20乙烯/乙烯醇共聚物。最终的掺混料于160℃在例1所述的HAAKE挤出机中吹膜。
所获产品的特性为熔点135℃,玻璃转化温度为70℃。
按照例1所述的长方形测试件的制备及条件测量机械弯曲性能,得到下列平均值:
杨氏模量 3861Kg/cm2
屈服应变 43%
屈服应力 164kg/cm2
断裂应变 207%
断裂应力 210kg/cm2
按照ASTM标准D1004在所获得的测试件上测定的抗扯性为540g/100μm。耐打孔性和断裂能分别为3.3Kg/μm和0.13焦耳/100μm。
例3~8
制备一种组合物,它含有:
-39%重量的未干燥的GLOBE 03401 CERESTAR(商标)淀粉(与例2相同)
-37%重量的乙烯/乙烯醇共聚物,此共聚物的性能列于表1
-12.8%重量的甘油
-3.2%重量的水
-3%重量的EAA 5981共聚物(DOW Chemical)
-5%的脲。
用重量送料计量器将组合物供入例2中所使用的那种Baker Perkins MPC/V-30挤出机。
在进行测试的3-8过程中,挤出机双螺杆区域的挤出加工温度在120-179℃范围内变化,而在单螺杆区域,挤出加工温度在170-140℃范围内变化。
将所获得的挤出物造粒,然后在大约160℃按例1所述挤出吹膜。
膜的拉伸机械性能列于表2。
表1、例3-8中所用乙烯/乙烯醇聚合物的性能。
例3 例4 例5 例6 例7 例8
乙烯含量 42 38 38 38 44 44
(摩尔%)
特性粘度 0.79 0.67 0.67 0.67 0.77 0.77
(DMSO,30℃)
Mw/Mn 3.6 1.7 1.7 1.7 1.7 1.7
熔融温度(℃) 164 179 169 176 166 162
水解度 99.3 99.6 98.5 99.6 99.6 99.7
熔融流动指数 20 - - - - -
(230℃,
2.16公斤)
熔融流动指数 - 25 25 8 12 3
(210℃,
2.16公斤)
表2 根据例3-8所得的薄膜的机械性能
拉伸试样性能 例3 例4 例5 例6 例7 例8
δb(MPa) 17.6 10.9 10.4 17.0 18.0 22.0
εb(%) 238 206 312 333 334 333
E(MPa) 149 88 64.5 109 110 285
eb(KJ/m2) 1550 914 1462 1936 1966 2508
Claims (19)
1、一种用于生产生物降解塑料制品的聚合物组合物,它包括一种乙烯/乙烯醇共聚物和一种解体的淀粉,其中所说的乙烯/乙烯醇共聚物中乙烯含量从10~90%(重量),共聚物的熔融流动指数从2~50。
2、根据权利要求1的聚合物组合物,其中共聚物和淀粉的重量比从1∶19至19∶1。
3、根据权利要求1的聚合物组合物,其中共聚物和淀粉的重量比从1∶4至4∶1。
4、根据权利要求1的聚合物组合物,还包括高沸点增塑剂,其浓度为淀粉组分重量的0.05至100%。
5、根据权利要求4的聚合物组合物,其中高沸点增塑剂的浓度为淀粉组分重量的20%至100%。
6、根据权利要求4或权利要求5的组合物,其中高沸点增塑剂选自由甘油、聚乙二醇、1,2亚乙基二醇、丙二醇、山梨醇组成的一组化合物以及它们的混合物。
7、根据权利要求1至6中任一项的组合物,还包括为淀粉组分重量的2~20%的脲。
8、根据权利要求1至7中任一项的组合物,还包括含量最高为组合物总重量的6%的水。
9、根据权利要求1至8中任一项的组合物,还包括一定量的聚合物,它选自改性的乙烯共聚物,尤其是乙烯/丙烯酸和它们的混合物,聚合物的用量最多为组合物重量的15%。
10、根据权利要求1至9中任一项的组合物,还包括聚乙烯醇。
11、根据权利要求1至10中任一项的组合物,还包括最多为组合物重量0.5%的氨。
12、根据权利要求1至11的组合物,其中乙烯/乙烯醇共聚物中乙烯含量从10~40%(重量),共聚物熔融流动指数从6至20。
13、根据权利要求1至12中任一项的聚合物组合物所制成的薄膜形式的制品。
14、根据权利要求1至12中任一项的聚合物组合物所制成的成型制品。
15、一种制备聚合物组合物的方法,此组合物用于生产可生物降解的塑料制品,该方法包括的步骤。
-将乙烯/乙烯醇共聚物和淀粉以1∶19至19∶1的重量比,以及为淀粉重量的0.05~100%的高沸点增塑剂进行混合,并且还可以存在一种解体剂,此解体剂选自由脲,碱土金属或碱金属的氢氧化物组成的一组化合物,混合是在一台挤出机中进行,挤出机被加热至一定温度,此温度和混合的时间要足以使淀粉解体。
16、根据权利要求15的方法,包括下列步骤:即在一台加热的(120℃至170℃之间)挤出机中将一种乙烯/乙烯醇共聚物与一种解体淀粉基组分进行混合,解体淀粉基组分是预先制备的,即在一台挤出机中将淀粉与一定量(淀粉重量的0.05至100%)的高沸点增塑剂在有一定量解体剂的存在下进行混合而制备的,该解体剂选自由脲,碱或碱土金属氢氧化物组成的一组化合物,在低于增塑剂沸点及120和170℃之间的温度下,该解体剂可有效地使淀粉解体。
17、根据权利要求15或16的方法,其中高沸点增塑剂选自由甘油,聚乙二醇、1,2亚乙基二醇、丙二醇、山梨醇组成的组以及它们的混合物。
18、根据权利要求15的方法,其中加入为淀粉组分重量的2至20%的解体剂,其中进行混合操作时,加入为淀粉重量的0.05至100%的水,其中水的浓度被减至不大于组合物总重量的6%的值。
19、根据权利要求16至18中任一项的方法,还包括加入氨。
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- 1990-05-28 NO NO902348A patent/NO179213C/no unknown
- 1990-05-28 ES ES90110070T patent/ES2062177T3/es not_active Expired - Lifetime
- 1990-05-28 DK DK90110070.1T patent/DK0400532T3/da active
- 1990-05-28 AT AT90110070T patent/ATE99719T1/de not_active IP Right Cessation
- 1990-05-28 CA CA002017654A patent/CA2017654C/en not_active Expired - Lifetime
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- 1990-05-28 DE DE69005702T patent/DE69005702T2/de not_active Expired - Lifetime
- 1990-05-29 JP JP2139543A patent/JPH0331333A/ja active Granted
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- 1990-05-29 RU SU904830150A patent/RU2073037C1/ru active
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CN1037515C (zh) * | 1993-08-24 | 1998-02-25 | 北京市星辰现代控制工程研究所 | 一种可生物降解的含淀粉的高分子组合物及其制备方法 |
CN1107585C (zh) * | 1998-04-21 | 2003-05-07 | 吴新国 | 一种薄膜及其生产方法 |
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