CN1103674C - 能生物降解的膨化淀粉制品和其制备方法 - Google Patents

能生物降解的膨化淀粉制品和其制备方法 Download PDF

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CN1103674C
CN1103674C CN99108477A CN99108477A CN1103674C CN 1103674 C CN1103674 C CN 1103674C CN 99108477 A CN99108477 A CN 99108477A CN 99108477 A CN99108477 A CN 99108477A CN 1103674 C CN1103674 C CN 1103674C
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D·S·勒瑟
J·内弗林
R·L·比尔默斯
D·C·劳林斯
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Abstract

本发明公开了一种能生物降解的膨化淀粉制品，在10%的相对湿度和23℃下具有小于0.451b/ft3的低堆积密度和小于1.0%的低含尘量，包括：a)改性淀粉，具有约10-30wt%的直链淀粉并用约2-6wt%的具有2-4个碳原子的结合烯化氧改性，和b)以淀粉重量计，约8-15wt%的水解聚乙烯醇并具有约88-99%的水解度。

Description

能生物降解的膨化淀粉制品和其制备方法
本发明涉及能生物降解的膨化或起泡淀粉制品，包括具有低堆积密度和低含尘量性能的包装制品，本发明还涉及这类制品的制备方法。
淀粉，作为一种容易得到的能生物降解原料，已被用来制成起泡的膜和其它用于不同目的的成形制品。一些这类淀粉制品和它们的用途分别公开在1991年7月30日和1991年8月27日授予N.Lacourse等人的专利US5035930和US5043196中，该专利指出将含至少45wt％高直链淀粉的淀粉挤压成膨化包装制品。在1992年3月10日授予G.Lay等人的专利US5095054公开了包括具有不同热塑性聚合材料的破坏性(destructurized)淀粉的热塑性聚合组合物。这些组合物包括例如聚烯烃、乙烯基聚合物、聚缩醛、聚酯、聚碳酸酯、聚醚等的聚合物和改性和未经改性淀粉。该专利还公开了将这类组合物形成为成形产品的方法。
近年来，由于淀粉容易获得和对环保有益的特性，人们已采取例如上述的各种方法将淀粉和其衍生物形成为不同制品。其它公开的文献有1995年2月28日授予E.George等人的专利US5393804，其中指出了使用包括分子量低的转化或降解淀粉、增塑剂和链烯醇聚合物的能生物降解的组合物产品的成形方法。另一公开的专利，1996年5月22日公开的EP 0 712883，显示了使用具有特定粒径的淀粉的成形制品的成形方法。尽管这些方法提供了它们所公开的特定产品的适宜性能，但是它们一般不适宜既要求堆积密度低又要求弹性好或脆性低的场合。由于这类产品一般随着堆积密度降低而变得更脆，因此这通常发生在制得的淀粉产品的堆积密度低的时候。在将产品用于例如需要堆积密度低且弹性好或脆性低的松散充填料的包装用途时，上述情况特别明显，特别是在相对湿度低的地方，该问题更明显。
现已发现，当使用经选择的烯氧化改性的淀粉和水解聚乙烯醇的组合时，可以得到堆积密度低且粉尘少或脆性低的淀粉基料产品。
更确切地说，本发明涉及一种在10％的相对湿度和23℃下具有小于0.45lb./ft.3的低堆积密度和小于1.0％的低含尘量的能生物降解的膨化制品，包括；
a)改性淀粉，具有约10-30wt％的直链淀粉并用约2-6wt％结合量的具有2-4个碳原子的烯化氧改性，和
b)以淀粉重量计，约8-15wt％的水解聚乙烯醇并具有约88-99％的水解度。
本发明还涉及上述膨化制品的制备方法，其中在17-25％的总水分含量下挤压包括改性淀粉和水解聚乙烯醇的组合物。
根据本发明，将选择的改性淀粉和水解聚乙烯醇一起膨化以制备堆积密度低、含尘量低或脆性低的能生物降解的制品。
本发明中使用的淀粉原料可以是任意几种天然的或改性的且具有约10-30wt％的直链淀粉的淀粉。包括从例如玉米、马铃薯、木薯、小麦、大米、西谷米和高粱的植物源获得的淀粉，优选玉米和木薯淀粉。
本发明中使用的淀粉原料通过与烯化氧的醚化来改性，尤其是含有2-4个碳原子的烯化氧，并优选含3个碳原子的烯化氧或氧化丙烯。改性量是很重要的，特别的使用约2-6wt％结合量的烯化氧，优选使用约3-5％结合量的烯化氧。
本发明中使用的聚乙烯醇组分经过水解，特别是部分到完全水解。聚乙烯醇为公知的通过水解聚乙酸乙烯酯制备的可商购得到的产品。一般可以得到定义为部分水解到完全或超水解的具有约88-99％的水解度。优选聚乙烯醇经过完全水解，且具有约97.5-98.9％的水解度。聚乙烯醇的粘度随分子量而变化，并以20℃下4％的水溶液的厘泊数计量。有效的粘度范围为约2-50厘泊，优选在约25-50厘泊的较高范围。该较高范围一般涉及每摩尔约130000-180000克的重均分子量。以淀粉重量计，所用聚乙烯醇的量为约8-15wt％，优选约10-12wt％。
堆积密度低且含尘量低或脆性低的本发明的膨化或起泡制品通过挤压本发明定义的改性淀粉和水解聚乙烯醇的选择组合物来制备。在进行挤压过程中重要的是，在挤压机中的淀粉原料的总水分含量以淀粉原料的干重计在约17-25wt％和优选约18-22wt％。总水分含量或含水量定义为包括干燥淀粉的残余水分、从大气中吸收的水分和向挤压机中加入的水。在加工过程中挤压机内的温度一般在约100-250℃，尤其是约150-200℃。在制备本发明的膨化松散充填料制品过程中，可以在接近挤压机出料端使用一模具并在约400-2000和优选750-1200psi的模具压力下进行挤出。
为了更方便加工淀粉组合物和制备具有堆积密度低和脆性低的希望特性的成形产品，可以向进料中根据需要加入成核剂。成核剂的使用有利于改善膨化制品的细孔组织和其它希望的特性。在制备本发明的膨化淀粉制品过程中可以使用多种成核剂。这类成核剂包括任意无机盐或其混合物，特别是例如硫酸钠、氯化钠和硅酸镁(滑石粉)的碱金属或碱土金属盐。这类金属的氧化物也是有用的，例如氧化镁和氧化钡。也可以使用在粘土中发现的例如矾土和硅酸铝的含铝制品和二氧化硅，以及例如二氧化钛的钛制品。优选成核剂是硫酸钠和滑石粉。以淀粉重量计，成核剂的使用量可以在约0.05-1.5wt％，优选约0.1-0.5wt％。使用的是除了可能存在于淀粉中的任意残余盐的成核剂。这包括例如硫酸钠和氯化钠的残余盐。以淀粉重量计，淀粉原料中残余盐与成核剂的和为约0.5-1.5wt％，优选约0.75-1.25wt％。
可能对挤压过程和膨化产品的最终特性有帮助的原材料的另一特性是淀粉原料的粒径。已发现约400-1600微米，尤其是约600-1200微米的淀粉原料粒径有助于加工并提供均匀的闭合细孔组织。为了获得具有这种粒径的淀粉原料，可以使用所谓压型造粒(campactgranulating)的方法，一般称为chilsonating。
包括选择的改性淀粉和水解聚乙烯醇的组合的本发明的膨化制品的弹性和强度特性良好。在成形的制品中特别希望的特性是脆性非常低，表现在低的相对湿度(10％)下小于1.0％的低含尘量。另一希望和令人吃惊的特性是形成的制品呈现出非常低的堆积密度(＜0.45lb./ft.3)。这些复合特性加上膨化制品拥有的均匀闭合细孔组织使它们利用在不同领域，特别是在包装领域很有用例如松散填充料。松散填充料为包装材料、填料、衬垫或包装元件，其目的在于提供回弹性或能吸收冲击负载或振动能。松散填充料应自由流动并填充到任意孔隙，以便包装的内含物被固定并被缓冲。
通过下面的实施例对本发明进行进一步的说明，除非另有说明，所有份数和百分比都以重量计，所有温度都是摄氏度。
下面的步骤用来测定按照整个说明书和权利要求书说明评价的物料的特性。
                      堆积密度试验
本发明膨化松散填充料制品的堆积密度测定如下。将膨化松散填充料放在不锈钢烧杯(Ohauss系列800)中。然后使用三梁式天平(Ohauss系列800)对装有物料的烧杯称重，直接用lbs/ft3计量。
                        粉尘试验
在特定条件下对膨化松散填充料的粉尘量测定如下：
1.将将要试验的膨压松散填充料放在固定在10％的相对湿度(RH)和23℃的恒湿室中调节48小时；
2.将约15.0g调节过的松散填充料加入到1加仑钢制涂料罐中。该罐经过改进，以使罐的顶部和底部具有金属丝网筛1.5”。网孔为宽5mm、长10mm的菱形。罐在中间分开以便于添加膨化或松散填充料并通过垫圈固定在一起；
3.将该涂料罐放在涂料罐震动器(Red Devil 5400涂料混合器)上震动30分钟；
4.将膨化物料与粉尘分离，然后称重，使用下式计算粉尘百分比(％)：
[(Wi-Wf)/Wi]×100＝％粉尘重
其中：
Wi为震动前膨化物料的最初重量，
Wf为震动后膨化物料的最终重量。
                         实施例1
用3wt％结合量的氧化丙烯(PO)改性的并含有约9.9％的经完全水解的聚乙烯醇(PVA)(从Air Products and Chemicals Inc.获得的Airvol325)的玉米淀粉样品在直径为65mm的APV Baker双螺杆挤压机中挤压。向挤压机中加入水分以使淀粉的总水分含量达到约2 0％，此外添加约0.29wt％的滑石粉作为成核剂(淀粉原料含约0.98％的残余硫酸钠)。在10％相对湿度和23℃下使用前述的步骤测定膨化制品的堆积密度和含尘百分数，列于下表。使用玉米淀粉作对比样品，一个样品没有聚乙烯醇，另一个样品没有用氧化丙烯改性，测定堆积密度和含尘百分数，也列于下表中。
                        表样品  原料        改性        PVA量   堆积密度    含尘量
                 ％PO        ％       lb/ft 3     ％A    玉米淀粉        5            9.9       0.38         0.73B    玉米淀粉        ---          5         0.74         67.00C    玉米淀粉        5            ---       0.92         67.00D    Hylon VII1     5.5          ---       0.62         0.47E    Hylon VII1     5.5          5         0.56         0.61F    小麦淀粉        ---          20        0.55         0.51含70％直链淀粉的高直链玉米淀粉
结果显示：当使用根据本发明的用氧化丙烯改性过的玉米淀粉和经完全水解的聚丙烯醇(样品A)时，形成的膨化泡沫制品好，并且令人吃惊地呈现出低的堆积密度和含尘量或脆性。相反，当使用玉米淀粉的对比样品时，一个没有用氧化丙烯改性(样品B)，一个没有聚乙烯醇(样品C)，两个的堆积密度和含尘量都很高，并且不具备使用根据本发明的组合物制得的制品的吸引人的特性。对比样品(D和E)使用含约70％直链淀粉的高直链玉米淀粉Hylon VII(National Starch andChemical Company的产品)制成。两个样品都用氧化丙烯(PO)改性，样品D不含聚乙烯醇(PVA)，样品E含聚乙烯醇。然而两个样品都含有比较低的粉尘，但是与本发明的制品相比，两个样品都具有相当高的堆积密度。另一个对比样品，用小麦淀粉和20％的聚乙烯醇制成样品F，结果制品的含尘量特性良好，但是堆积密度高。

Claims (10)

1.一种能生物降解的膨化制品，在10％的相对湿度和23℃下具有小于0.45lb/ft3的低堆积密度和小于1.0％的低含尘量，包括；
a)改性淀粉，具有约10-30wt％的直链淀粉并用约2-6wt％结合量的具有2-4个碳原子的烯化氧改性，和
b)以淀粉重量计，约8-15wt％的水解聚乙烯醇并具有约88-99％的水解度。
2.如权利要求1的制品，其中淀粉选自玉米和木薯淀粉。
3.如权利要求2的制品，其中淀粉用约3-5％的烯化氧改性，并使用约10-12％的聚乙烯醇。
4.如权利要求3的制品，其中烯化氧具有3个碳原子，聚乙烯醇经完全水解并具有约97.5-98.9％的水解度，淀粉为玉米淀粉。
5.如权利要求4的制品，其为松散填充包装料。
6.一种能生物降解的膨化成形制品的制备方法，该膨化制品在10％的相对湿度和23℃下具有小于0.45lb/ft3的低堆积密度和小于1.0％的低含尘量，并包括：
a)改性淀粉，具有约10-30wt％的直链淀粉并用约2-6wt％结合量的具有2-4个碳原子的烯化氧改性，和
b)以淀粉重量计，约8-15wt％的水解聚乙烯醇，具有约88-99％的水解度；
在约17-25％的总水分含量和约100-250℃的温度下进行挤压。
7.如权利要求6的方法，其中淀粉选自玉米和木薯淀粉。
8.如权利要求7的方法，其中以淀粉重量计使用约0.05-1.5wt％的成核剂，并且淀粉用约3-5％的烯化氧改性，以及使用约10-12％的聚乙烯醇。
9.如权利要求8的方法，其中淀粉为玉米淀粉，成核剂选自碱金属和碱土金属的盐和氧化物、矾土、硅酸铝、二氧化硅和二氧化钛，聚乙烯醇经完全水解并具有约97.5-98.9％的水解度。
10.如权利要求9的方法，其中制品为松散填充包装料。
CN99108477A 1998-06-16 1999-06-15 能生物降解的膨化淀粉制品和其制备方法 Expired - Fee Related CN1103674C (zh)

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