CN1171804A - 冷藏室中使用的阻挡层 - Google Patents
冷藏室中使用的阻挡层 Download PDFInfo
- Publication number
- CN1171804A CN1171804A CN95197184A CN95197184A CN1171804A CN 1171804 A CN1171804 A CN 1171804A CN 95197184 A CN95197184 A CN 95197184A CN 95197184 A CN95197184 A CN 95197184A CN 1171804 A CN1171804 A CN 1171804A
- Authority
- CN
- China
- Prior art keywords
- styrene
- composition
- blocking layer
- barrier layer
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
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Abstract
公开了用于绝热壁室结构的、特别是诸如冰箱、洗碟机之类的家用电器绝热壁室结构的阻挡层组合物。阻挡层组合物是抗聚氨酯泡沫体发泡剂作用的,并有(i)有效量的改性聚烯烃,最优选的是用选自马来酐、马来酸、马来酐衍生物、马来酸衍生物和它们的混合物的化合物改性的聚乙烯,和(ii)有效量的橡胶。阻挡层组合物可选择性地和最优选地进一步含(iii)选自聚乙烯、聚丙烯、聚丁烯和它们的共聚物的有效量聚烯烃。本发明进一步提供了掺有上述阻挡层的可热成型的复合材料以及加有可成型的复合材料的绝热壁室结构。最后,本发明还提供加有本发明阻挡层的可热成型的复合材料的制备方法。
Description
本发明提供抗聚氨酯泡沫体发泡剂作用的组合物、由所说组合物组成的阻挡层、掺有所说阻挡层的可热成型的复合材料、生产所说可热成型的复合材料的方法以及加有所说可热成型的复合材料的绝缘室壁结构,此结构用于家用电器的构造,特别是冰箱和洗碟机。
一般的家用电器冷藏室是由金属外壳、塑料内衬(典型的是用ABS(丙烯腈-丁二烯-苯乙烯)或HIPS(高抗冲性聚苯乙烯)制成)和绝缘泡沫体芯(一般是用聚氨酯泡沫体)组成,泡沫体有聚氨酯泡沫体发泡剂封闭于其中。目前工业上使用的发泡剂是氟利昂或一氟三氯甲烷(一种全卤代甲烷)。但是增加的环境保护条例强烈要求(并在某些情况下托管)使用氟利昂代用品。氟利昂最有希望的代用品是至少含一个氢原子的卤代烃。
聚氨酯的发泡剂,诸如氟利昂和氟利昂代用品如2-氟-2,2-二氯乙烷和2,2-二氯-1,1,1-三氟乙烷能使内衬起泡、产生灾害性龟裂、细小裂纹并损失抗冲性(使脆化),以及产生应力泛白和/或溶解现象。这些氟利昂代用品在化学上对内衬的攻击似乎比氟利昂更加剧烈。普遍认为,发泡剂对内衬的攻击是在冷却时并在发泡剂凝聚成液体时发生的。这种循环的有利条件是在运输和贮存过程中出现的。在生产过程中可将冷藏室进行热-冷交替使发泡剂蒸发和冷凝的循环过程来模拟输送条件。
先有技术试图解决的此问题包括了阻挡层的使用。阻挡层的主要功能是阻止发泡剂攻击塑料内衬。但是除了要提供抗聚氨酯泡沫发泡剂的优良溶剂外,阻挡层组合物还必须有一定的加工特性,特别是用作家用电器冷藏室构造的阻挡层组合物必须是可挤塑、可热成型和可重复使用的。
本文所用的可挤塑性意指组合物可同时或相继与包括塑料内衬的材料一起进行挤塑以形成热塑性复合材料。因此,阻挡层组合物必须能粘附在常用以制造塑料内衬的基于苯乙烯的聚合物上。基于苯乙烯的聚合物说明性实例是ABS、HIPS和它们的混合物。阻挡层与一个或多个内衬层共挤塑的能力提供了很大的成本和效率上的优点。
此外,阻挡层组合物必须是可热塑成型的,特别是必须不能损害掺有这种阻挡层的复合结构的热成型能力。如果得到的复合材料不能热成型成要求的内衬形状,则制造商将会有成本和生产优点上的重大损失。本领域中的技术熟练者将会认识到,热成型性因此是在家用电器冷藏室构造中用作阻挡层组合物不可缺少的。
最后,阻挡层组合物必须对可热成型复合材料的重复使用性或再循环性不起负作用。在制造家用电器冷藏室时,热成型的冷藏室内衬一般要经修整,去掉多余的复合材料。修整掉的或碎屑材料常被加到原始内衬材料中,即以苯乙烯为基础的聚合物中。作为结果,阻挡层组合物与内衬材料的相容性是特别重要的。内衬材料的性质必须是不被负作用影响的。本领域的技术熟练者会认识到,多余的可热成型的复合材料的再使用的能力节省了大量的成本。
因此,极希望提供一种能呈现(a)优良的抗聚氨酯泡沫发泡剂的溶剂、(b)对内衬和复合结构制造的可挤塑性和粘附性、(c)一经阻挡层掺入复合结构后的热成型性和(d)碎屑材料掺入原始内衬材料的重复使用性的阻挡层组合物。
虽然先有技术对解决此问题已做过数次尝试,但没有能提供所要求的平衡性能。
例如,US 5,118,174(Benford等人)公开了一种用于绝热的家用电器冷藏室结构的多组分叠层结构。此多组分叠层结构含有阻挡层,但它提供的抗溶剂性和重复使用能力都是不够的。
US 5,227,245(Brands等人)公开了一种用以阻止绝热室壁结构中的溶剂攻击的阻挡层,它主要是由无定形热塑性聚酯树脂(是芳族二羧酸和含活泼氢的原料的加合共聚物)组成的。但此聚酯与苯乙烯型树脂具有的相容性能很差,因此阻挡层缺乏所要求的重复使用能力。
最后,US 5,221,136和5,340,208(Hauck等人)公开了一种由聚烯烃和可用马来酐官能化的嵌段共聚橡胶组成的阻挡层。但已发现用这类阻挡层制备的一些可热成型的复合材料的热成型性不是最好。特别是发现这种阻挡层能粘结在热成型过程使用的阴膜中。此外,还发现这类阻挡层组合物与基于苯乙烯的内衬材料一起使用时具有有限的重复使用能力。
因此,本发明的一个目的是提供能抵抗聚氨酯泡沫体发泡剂的作用和呈现诸如挤塑性、热成型性和重复使用性之类的加工特性的阻挡层组合物。
本发明的另一目的是提供能粘附在一个或多个内衬层上以形成可热成型的复合材料的阻挡层。
本发明的更特别的目的是提供能与一个或多个内衬层一起挤塑以形成可热成型的复合材料的阻挡层。
本发明的又一目的是提供含有保护一个或多个内衬层不受聚氨酯泡沫体发泡剂作用而且还具有与包括所说内衬层的材料有要求的重复使用相容性的可热成型的复合材料。
本发明最后的一个目的是提供包括含有保护内衬层不受聚氨酯泡沫体发泡剂作用的阻挡层的可热成型的复合材料的绝热室壁结构。
本发明的各种目的都是以特殊的阻挡层组合物(A)提供的。阻挡层组合物(A)能抵抗聚氨酯泡沫体发泡剂的作用,它包括(i)有效量的改性聚烯烃,最好是用选自马来酐、马来酸、马来酐衍生物、马来酸衍生物的化合物和它们的混合物改性的;(ii)有效量的一种橡胶。选择性的并且最优选的阻挡层组合物(A)将进一步含有效量的一种聚烯烃(iii),聚烯烃选自聚乙烯、聚丙烯、聚丁烯和它们的共聚物;还可选择性地含有基于苯乙烯的聚合物(iv)。
本发明进一步提供了具有包括一个或多个基于苯乙烯的一种或多种聚合物的次层的官能层(I)和粘附于官能层(I)的至少一个表面上的阻挡层(II),其中阻挡层(II)包括阻挡层组合物(A)。
本发明也提供了可热成型的复合材料与外部结构壁(III)组合并有聚氨酯泡沫绝热体(IV)粘附于阻挡层(II)和外部结构壁(III)以将其置于二者之间的绝热室壁结构。
最后,本发明提供了制备可热成型的复合材料的方法,它要求提供一官能层(I)和粘附在官能层(I)上的阻挡层(II)。
图1为冷藏室示意图。
图2为作为图1的冷藏室塑料内壁的内室示意图。
图3为形成图2内室的可热成型的复合材料部分横截面图。
现参见附图,图1说明本发明的一个特别合意的终用途的应用。该冷藏装置1有一绝热的壁室结构E,它是由金属外壳2、内室3和在其间就地发泡的绝热体4组成的,内室3用可热成型的复合材料5(见图2)形成。
参见图3,可热成型的复合材料5是由官能层6和阻挡层7组成。
官能层6用作冷藏装置1内部的视觉愉快部分。官能层6一般由一个或多个基于苯乙烯的一种或多种聚合物的次层(8,9)组成。基于苯乙烯的聚合物的适合例子包括ABS、HIPS和它们的混合物。
一特别优选的实例说明于图3,其中的官能层6由次层8和9组成。一般说来,次层8通常是提供一视觉愉快的高光泽外观,而次层9一般是提供合意的性能特征,诸如好的抗食物污染和正常的磨损和撕裂性能。特别适于用作次层8的例证性材料包括HIPS。用作次层8的特别合意的材料是高光泽中抗冲聚苯乙烯(例如PS-7800由BASF公司商品供应,Wyandotte,Michigan)。
适合用作次层9的例证性材料包括本体HIPS(例如,一特别合意的材料是以标称熔体流动速率2.6g/10min(按ASTMS条件G测定)和维卡软化点102℃为特征的高抗冲聚苯乙烯PS-7100,也有BASF的商品供应)或ABS。
一般说来,次层8和9包括官能层6。但应认识到,用现今供应的许多聚合物组合物,官能层6也可用单层或两层以上的多层组成。
在上述特别优选的具体实施方案中,次层8一般占官能层6总重的1-10重量%,而次层9一般占官能层6总重的99-90重量%,更特别的是次层8占官能层6总重的1-5重量%,而次层9占99-95重量%。
阻挡层7可由下述的(i)-(iv)组成:
(i)有效量的改性聚烯烃,
(ii)有效量的橡胶;
(iii)聚乙烯、聚丙烯、聚丁烯和它们的共聚物和/或
(iv)基于苯乙烯的聚合物。
阻挡层组合物(A)含有改性聚烯烃(i)。本发明所用术语“改性聚烯烃”意欲描述由不饱和羧酸或其官能衍生物或另一含乙烯官能基的单体在下述涉及组分(iii)的任何烯烃聚合物上的接枝聚合衍生物的聚烯烃接枝共聚物。但要如此改性的聚烯烃最好是聚乙烯(HDPE,LDPE,LLDPE)。
要在上述烯烃聚合物上接枝的不饱和羧酸或其官能衍生物或另外的含乙烯官能基的单体包括,例如诸如丙烯酸、甲基丙烯酸、马来酸、富马酸、衣康酸和山梨酸之类的羧酸;诸如马来酐和衣康酐之类的酸酐;诸如丙烯酰胺和甲基丙烯酰胺之类的酰胺,诸如丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯之类的含环氧基的化合物;诸如甲基丙烯酸(2-羟乙基)酯和聚乙二醇单丙烯酸酯之类的含羟乙基的酯;以及诸如丙烯酸钠、甲基丙烯酸钠和丙烯酸锌之类的金属盐。这些接枝单体可以单独使用或结合使用。在这些酸和酸酐中,特别优选的是马来酸和马来酐以及它们的衍生物。
所说接枝单体的比例最好是在基于组分(i)的0.005-5摩尔%范围。这种聚合物类型的最佳具体实施方案包括马来酸或马来酐在HDPE上接枝的产物。不饱和羧酸或其官能衍生物或另外的含乙烯官能基的单体在烯烃聚合物上的接枝共聚合能用多种方法进行。例如将烯烃聚合物、接枝单体和自由基引发剂混合在一起,并以熔融态捏合;另一方法是将接枝单体加入烯烃聚合物在适合溶剂中的溶液或悬浮液。
用作改性聚烯烃(i)的最优选的材料是以熔体指数1.2g/10min(按ASTM D 1238测定)和密度0.961g/cm3(按ASTM D 1505测定)为特征的改性聚烯烃(例如PlexarPX 209,由Quantum公司商品提供,Cincinnati,Ohio)。
阻挡层组合物(A)将进一步包括橡胶(ii)。适合的橡胶一般是合成的嵌段共聚物橡胶。说明性实例包括苯乙烯嵌段二嵌段、苯乙烯-乙烯/丁烯-苯乙烯三嵌段、用马来酐、马来酸或它们的混合物官能化的苯乙烯-乙烯/丁烯-苯乙烯三嵌段共聚物或上述的任何共聚物的组合。特别适合的橡胶(ii)是线型苯乙烯-丁二烯-苯乙烯橡胶(例如Stereon840A,一种苯乙烯含量为43重量%的线型苯乙烯-丁二烯-苯乙烯橡胶,Mw为94000,Mw/Mn值为1.40,Firestone Tire&Rubber Co.提供商品;和Finaclear520,一种苯乙烯含量为43重量%的线型苯乙烯-丁二烯-苯乙烯橡胶,Mw为85000,Mw/Mn值为1.10,Fina公司提供商品,Houston,Texas)。
阻挡层组合物(A)也选择性地并最优选地含有聚烯烃(iii)。虽然含组分(i)和(ii)的组合物能够提供所希望的特性性能,但聚烯烃(iii)的加入提供了重要的成本优势而对本发明的组合物或阻挡层的特性或加工性能没有任何的减低。
广义地说,聚烯烃组分(iii)的定义包括了聚乙烯、聚丙烯和聚丁烯的各种类型以及悉知的它们的共聚物。虽然聚乙烯以外的聚烯烃能按本发明提供共混物,但各种聚乙烯则是优先选择的,包括在聚乙烯中的是以所谓的齐格勒-纳塔(Ziegler-Natta)配位催化剂进行乙烯的聚聚制备的线型(非支化的)高密度聚乙烯HDPE材料(密度=0.940-0.970g/ml)、以自由基催化剂在高温高压下进行乙烯的聚合以提供支化的聚乙烯制备的LLPE材料(密度=0.910-0.934g/ml)、在齐格勒-纳塔条件下由乙烯和少量α,β-烯属不饱和C3~C12烯烃提供基本上是线型的但有得自α-烯烃组分的烷基侧链的低密度聚乙烯制备的LLDPE材料(密度=0.88-0.935g/ml)。在这组聚乙烯中,优选选择的是上面述及的高密度聚乙烯。
另外,适合的聚烯烃(iii)也需有1-10之间的熔体流动指数(MFI),最优选的是1-3之间。特别优选的聚烯烃是以密度0.96g/ml(按ASTM D 1505测定)和熔体指数1.15g/10min(按ASTM D 1238测定)为特征的高密度聚乙烯(例如,由Quantum公司商品供应的LM-6187 HDPE, Cincinnati,Ohio)。
最后,阻挡层组合物(A)可进一步选择性地含有基于苯乙烯的聚合物(iv)。本发明的基于苯乙烯的聚合物组分(iv)是聚苯乙烯树脂或ABS(丙烯腈-丁二烯-苯乙烯)共聚物。聚苯乙烯树脂包括苯乙烯均聚物(结晶聚苯乙烯)或橡胶改性的聚苯乙烯(高抗冲聚苯乙烯(HIPS))。聚苯乙烯是高分子量聚合物,其重均分子量最好大于150,000g/mol左右。橡胶改性的聚苯乙烯是最优先选择的,它是用诸如聚丁二烯或苯乙烯-丁二烯共聚物的弹性体改性的聚苯乙烯,是众所周知的材料。此材料叙述于例如“现代塑料大全”(Modern PlasticsEncyclopedia),Mc Graw-Hill,P72(1983-1984)。其制备方法是在聚丁二烯或苯乙烯-丁二烯共聚物存在下聚合苯乙烯单体。能在本发明中使用的ABS共聚物树脂是本领域中技术熟练者悉知的。这种材料的制备叙述于例如US 3,563,845,US 3,565,746和US 3,509,237中,均在此提出供参考。
总的说来,阻挡层组合物(A)一般可有:
(i)1-70重量份改性聚烯烃,
(ii)1-40重量份橡胶,
(iii)0-90重量份聚烯烃,
(iv)0-50重量份基于苯乙烯的聚合物,组分(i)-(iv)相加即为阻挡层组合物(A)总量。
优选的阻挡层组合物具有:
(i)5-40重量份改性聚烯烃,
(ii)5-30重量份橡胶,
(iii)20-80重量份聚烯烃和
(iv)0-48重量份基于苯乙烯的聚合物,组分(i)-(iv)相加即为阻挡层组合物(A)的总重。
最优选的本发明阻挡层组合物具有:
(i)5-30重量份改性聚合物,
(ii)5-20重量份橡胶,
(iii)30-70重量份聚烯烃和
(iv)0-30重量份基于苯乙烯的聚合物,组合(i)-(iv)相加即为阻挡层组合物的总重。
现将两个特别优选的阻挡层组合物(A)的具体实施方案叙述于下:
具体实施方案1(重量份) | 具体实施方案2(重量份) | |
改性聚烯烃(i) | 15-25 | 15-25 |
橡胶(ii) | 10-20 | 10-20 |
聚烯烃(iii) | 60-70 | 35-45 |
基于苯乙烯的聚合物(iv) | - | 20-40 |
用熟知的加工方法将阻挡层组合物(A)的组分(i)-(iv)加工以形成均匀的混合物。混合物可用熟知的聚合物加工技术按需要切粒或立即将其形成层。
现参见可热成型的复合材料5,阻挡层7一般为复合材料5总重的1-50重量%,而官能层6是基于复合材料重量计算的50-99重量%。更具体的是,官能层6和阻挡层7分别占复合材料5总重的70-99重量%和30-1重量%。如果复合材料5有80-95重量%的官能层6和5-20重量%的阻挡层7,则是最优先选择的。
更优选的是将阻挡层7直接在次层9上同时共挤塑形成可热成型的复合材料5。在此优选的具体实施方案中,次层9将与次层8共同扩展并附着于次层8。另外的方法是,可将先制成的阻挡层7相继叠层在官能层6上,更优选次层9上。本领域技术熟练者会知道,应用包括增热和/或增压的众所周知的叠层技术是足以形成可热成型的复合材料5的。
可热成型的复合材料5一般是热成型成为装置的室结构的,诸如图2中所示的作为内室3。本领域技术熟练者知道,这种加工技术在本技术领域中是熟知的,并且一般包括利用阴阳模具共同操作的冲压方法。大家知道,在大多数模塑操作中,阻挡层7的一个表面是向外的,远离内室3的内部,因而与阴模保持接触。因此,在热成型过程中阻挡层7不与阴模粘合是热成型性的一个方面的要求。
然后将热成型的内室3与外壳进行装置,因而其间存在空隙。将聚氨酯泡沫体组合物置于其中并在内室3和外壳2之间现场成泡以形成就地成泡的绝热体4。内室3、外壳2和其间的就地成泡的绝热体4所得到的绝热结构在此被定义为绝热壁室结构E。
外壳2可由适合用作装置构造的外表面的熟知材料构成。硬质塑料是适合的,金属是最优选的。
在本发明中,优选的就地成泡绝热体4是聚氨酯泡沫体。聚氨酯泡沫体的制备是将有机聚异氰酸酯在反应条件下与能和异氰酸酯反应的含活泼氢的化合物(诸如多元醇)在发泡剂存在下紧密混合,然后将此成泡混合物导入冷藏室的内室3和外壳2之间的空隙处。
制备聚氨酯采用的发泡剂一般是在大气压下沸点为约50℃至约+100℃的有机化合物。一般说来,为此目的选择的化合物是卤代有机化合物,特别是那些含氟和/或氯的化合物,因为它们还有助于给予泡沫体好的绝热性质。
在本发明中,制备聚氨酯泡沫体4的优选发泡剂是那些包括氢卤碳的化合物。氢卤碳化合物由于它们一般的较低的耗臭氧潜力,它们优选于全卤碳化合物,虽然本发明不排除使用小量的全卤代碳化合物(诸如三氯一氟甲烷和二氯二氟甲烷)。
适合的氢卤碳化合物包括氢氯氟碳、氢氟碳和氢氯碳化合物,特别是那些具有1-3个碳原子的化合物,因为它们有适合的沸点。
由于可用性、处理容易和制备的聚氨酯泡沫体要求的物理性能,制备本发明中使用的绝热聚氨酯泡沫体的优选发泡剂包括二氯一氟乙烷和其异构体、一氯二氟乙烯和其异构体,四氟乙烷和其异构体以及1,1,1-三氯乙烷。但是,本领域技术熟练者会意识到,使用其它聚氨酯泡沫体发泡剂是在本发明范围之内的。
发泡剂的使用量应足以提供总堆积密度为约10-约200kg/m3的泡沫体,优选的堆积密度为约15-约100kg/m3,更优选约18-约60kg/m3。
制备聚氨酯泡沫体的有用的含活泼氢的化合物包括那些具有两个或多个含能与异氰酸酯反应的活泼氢的基团的材料。这类化合物合称为polyahl。在这类polyahl化合物中,优选的是那些每分子具有至少两个羟基、伯或仲胺、羧酸,或硫醇基的化合物。多元醇(即每分子至少有两个羟基的化合物)是特别优选的,因为它们与聚异氰酸酯有所要求的反应性。
制备硬质聚氨酯的适合异氰酸酯反应性材料,包括那些具有约50-约700、优选约70-约300、更优选约70-约150当量重量(equivalent weight)的材料。这类异氰酸酯反应性材料每分子最好也有至少2个、优选约3个至约16个、优选约达8个活泼氢原子的官能度。
适合的其它异氰酸酯反应性材料包括聚醚型多元醇、聚酯型多元醇、多羟基封端的缩醛树脂、羟基封端的胺和聚胺等。基于性能、可用性和成本考虑,制备硬质泡沫体最优选的是聚醚型多元醇,它是将氧化烯烃加入具有约2-8个、优选约3-8个活泼氢原子的引发剂制备的。
制备聚氨酯的有用的聚异氰酸酯包括芳族、脂族和环脂族聚异氰酸酯以及它们的组合。这些类型的代表是二异氰酸酯,诸如间-或对-亚苯基二异氰酸酯、甲苯-2,4-二异氰酸酯、甲苯-2,6-二异氰酸酯、六亚甲基-1,5-二异氰酸酯、四亚甲基-1,4-二异氰酸酯、环己烷-1,4-二异氰酸酯、六氢甲苯二异氰酸酯(以及异构体)、萘-1,5-二异氰酸酯、1-甲苯基-2,4-苯基二异氰酸酯、二苯甲烷-4,4’-二异氰酸酯、二苯甲烷-2,4’-二异氰酸酯、亚联苯基-4,4’-二异氰酸酯、3,3’-二甲氧基-4,4’-亚联苯基二异氰酸酯和3,3’-二甲基二苯丙烷-4,4’-二异氰酸酯;三异氰酸酯,诸如甲苯-2,4,6-三异氰酸酯;以及聚异氰酸酯,诸如4,4’-二甲基二苯甲烷-2,2’,5,5’-四异氰酸酯和各种多亚甲基多苯基聚异氰酸酯。
粗品聚异氰酸酯也可在本发明实践中使用,诸如由粗甲苯二胺混合物进行光气化作用得到的粗甲苯二异氰酸酯,或由粗二苯甲烷二胺进行光气化作用得到的粗二苯甲烷二异氰酸酯。
特别优选的是桥亚甲基多苯基聚异氰酸酯,这是由于它们交联聚氨酯的能力。异氰酸酯指数(异氰酸酯当量与含活泼氢的基团当量之比)最好是约0.9-约5.0、优选约0.9-约3.0。最优选约1.0-约1.5。
除上述关键组分外,经常需要在制备多孔聚氨酯时采用某些其它的组分。这些附加的组分是水、催化剂、表面活性剂、阻燃剂、防腐剂、着色剂、抗氧化剂、增强剂、填充剂等。
水是常被采用的,以起发泡剂前体和加工助剂的作用。水能与异氰酸酯反应导致二氧化碳气的产生,在形成泡沫体的反应中后者起着发泡剂的功能。使用水时,其量最好是每100重量份总的含活泼氢的化合物不超过约7、优选约6、更优选约5重量份。在每100重量份总的含活泼氢的化合物中存在有至少约0.5、优选至少约1重量份水时,可以见到好的效果。水量超过这些范围是可以的,但得到的泡沫体的物理性能可能是不理想的,诸如较差的尺寸稳定性和绝热性。
在制取聚氨酯泡沫体时,一般是高度优选少量的表面活性剂以稳定起泡的反应混合物,直至固化。这种表面活性剂最好包括一液体或固体有机硅氧烷表面活性剂。其它的较少优选的表面活性剂包括长链醇的聚乙二醇醚、长链烷基酸酸硫酯的叔胺盐或链烷醇胺盐、烷基磺酸酯和烷基芳基磺酸。这样的表面活性剂的使用量应足以稳定发泡的反应混合物,而不产生溃陷和形成大的不均匀的孔隙。一般,为达到此目的在每100重量份总的含活泼氢的化合物中有约0.2-约5份表面活性剂是足够的。
含活泼氢的化合物与聚异氰酸酯的反应最好使用一种或多种催化剂。任何包括的聚氨酯催化剂都是可以使用的,它们包括叔胺化合物和有机金属化合物。叔胺化合物之例包括三亚乙基二胺、N-甲基吗啉、五甲基二亚乙基三胺、四甲基亚乙基二胺、1-甲基-4-二甲氨基乙基哌嗪、3-甲氧基-N-二乙基丙胺、N-乙基吗啉、二乙基乙醇胺、N,N-二甲基-N’,N’-二甲基异丙基亚丙邻二胺、N,N-二乙基-3-二乙氨基丙胺、二甲基苄胺等。有机金属催化剂之例包括有机汞、有机铅、有机铁和有机锡催化剂。其中有机锡催化剂是优先选择的。适合的锡催化剂包括氯化亚锡;羧酸的锡盐,诸如二(2-乙基己酸)二丁基锡盐以及其它有机金属化合物。三聚聚异氰酸酯的催化剂,诸如碱金属醇盐,也是可以选择性使用的。这种催化剂的用量是显著增加聚异氰酸酯反应速率的量。典型的用量是每100重量份存在的总的含活泼氢的化合物约0.001至约1份催化剂。
在制取聚氨酯泡沫体时,是将含活泼氢的化合物、聚异氰酸酯和其它组分互相接触,彻底混合,并让其反应、膨胀并固化成为多孔聚合物。具体的混合设备不是关键问题,可方便地使用各种类型的混合头和喷雾设备。在将聚异氰酸酯与含活泼氢的组分进行反应之前将某些原料进行预混合物常常是方便的,但不是必须的。例如,除了聚异氰酸酯,将含活泼氢的化合物、发泡剂、表面活性剂、催化剂和其它组分混合,然后再将此混合物与聚异氰酸酯接触,常常是有用的。另外也可将所有的组分分别导入聚异氰酸酯和多元醇接触的混合区。将所有的或部分的含活泼氢化合物与聚异氰酸酯进行预反应以形成预聚物也是可以的,虽然这不是优先选择的。
实施例
下面的实施例是对本发明的说明,无论如何不应被解释为限制本发明。所有的份数和百分数是指重量百分数,除非另外指出。
实施例1
二氯二氟乙烷起泡研究
以标称熔体流动速率2.6g/10min(按ASTM D 1238,条件G测定)为特征的高冲击聚苯乙烯,PS-7100/保护阻挡层结构的板通过将样品板封于瓶口而暴露于35℃下的液态二氯二氟乙烷(HCFC 141-6)蒸气。样品板的制备是将保护层加压层叠在PS-7100上,使在28密耳(mil)的PS-7100上有2密耳的保护层。表1所述的各种组合物阻挡层是在200℃用单螺杆挤塑机混合制备的。二氯二氟乙烷通过样品扩散,监测其化学攻击。出现起泡时记录时间,其结果叙述于表1中。保护阻挡层/PS-7100的粘附性用手拉剥离试验进行评定。粘附性试验的结果包括在表1中。表1:二氯二氟乙烷起泡试验(35℃下的二氯二氟乙烷蒸汽)
板结构:28密耳PS 7100本体层,2密耳保护层
材料Plexar PX 209:Quantum公司的马来酐改性HDPE(改性聚烯烃
样品号 | 保护层组合物 | 保护层厚度(密耳) | 起泡时间(小时) | 粘合试验 |
1 | 无(只用30密耳PS-7100) | 0 | 2-3 | |
2 | LM-6187 HDPE | 2 | 48-50 | 差 |
3 | Plexar PX 209 | 2 | 150-160 | 差 |
4 | 85%LM-6178 HDPE15%Stereon 840A | 21 | 16-18 | 很好 |
5 | 85%Plexar PX20915%Stereon 840A | 21 | 94-96 | 很好 |
6 | 43%LM-6187 HDPE42%PS5350 HIPS15%Stereon 840A | 2 | 6-8 | 好 |
7 | 43%Plexar PX20942%PS5350 HIPS15%Stereon 840A | 2 | 16-18 | 好 |
8 | 43%Plexar PX20942%PS 5350 HIPS15%FinaClear 520 | 2 | 16-18 | 好 |
9 | 50%Plexar PX20935%Ps5350 HIPS15%Stereon 840A | 2 | 22-26 | 好 |
(i))LM-6187:Quantum公司的HDPE,d=0.96,MPI=1.15
(聚烯烃(iii))PS-5350:BASF公司的高抗冲聚苯乙烯(基于苯乙烯的聚合物
(iv))Stereon 840A:Firestone的S-B-S三嵌段共聚物(橡胶(ii))FinaClear 520:Fina的S-B-S三嵌段共聚物(橡胶(ii))
实施例2
重复使用相容性
保护层重复使用相容性是用测试含15%保护层、83.5%PS-7100和1.5%PS-7800的混合物的注射模塑样品的性能评定的。表2中总结的结果说明保护层组合物提供了极好的重复使用相容性。当下面讨论的样品呈现最佳可重复使用性时,预料可在表1中其余的样品中能掺入0.3-3%附加的橡胶(iii)以提高它们的重复使用相容性。
表2:重量使用相容性研究结果
材料PS-7100:BASF的高抗冲聚苯乙烯PS-7800:BASF的高抗冲聚苯乙烯
A | B | C | D | E | F | G | |
PS7100 | 98 | 83.5 | 83.5 | 83.5 | 83.5 | 83.5 | 83.5 |
PS7800 | 2 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
样品7 | - | 15 | - | - | - | - | - |
样品8 | - | - | 1.5 | - | - | - | - |
样品9 | - | - | - | 15 | - | - | - |
样品10 | - | - | - | - | 15 | 15 | - |
样品15 | - | - | - | - | - | - | - |
样品16 | - | - | - | - | - | - | 15 |
MFR(200.0℃,5.Okg)Vicat(℃) | 2.9101 | 3.1102 | 2.9102 | 3.1102 | 3.1102 | 3.3102 | 3.7102 |
拉伸屈服强度(磅/英寸2) | 2485 | 2632 | 2689 | 2630 | 2694 | 2952 | 2946 |
拉伸断裂强度(磅/英寸2) | 3721 | 3773 | 3945 | 3738 | 3925 | 4024 | 3960 |
拉伸伸长(%) | 54 | 75 | 77 | 74 | 68 | 68 | 63 |
拉伸模量(千磅/英寸2) | 181 | 179 | 176 | 169 | 176 | 177 | 175 |
悬壁梁冲击强度(英尺-磅/英寸)加德纳冲击强度(英寸-磅) | 2.1299 | 2.8203 | 2.7>320 | 2.5204 | 2.6312 | 2.4243 | 2.4210 |
须知,在此所示和叙述的本发明构成了本发明的最佳具体实施方案,但不包括所有的可能形式,任何人或本领域一般技术人员都能创造公开于此的本发明的各种具体实施方案而不脱离公开的和要求保护的本发明精神和范围。
Claims (10)
1.一种抗聚氨酯泡沫体发泡剂作用的组合物,该组合物包括:
(i)有效量的改性聚烯烃和
(ii)有效量的橡胶。
2.权利要求1的组合物,该组合物包括:
(i)1-70重量份改性聚烯烃,
(ii)1-40重量份橡胶,
(iii)0-90重量份选自聚乙烯、聚丙烯、聚丁烯和它们的共聚物的聚烯烃和
(iv)0-50重量份基于苯乙烯的聚合物,其中所有重量份相加等于组合物的总重。
3.权利要求1或2的组合物,其中改性聚烯烃(i)是用选自马来酐、马来酸、马来酐衍生物、马来酸衍生物以及它们的混合物的化合物改性的聚乙烯。
4.权利要求1-3任一项的组合物,其中橡胶(ii)是选自苯乙烯-丁二烯二嵌段、苯乙烯-丁烯-苯乙烯三嵌段、苯乙烯-乙烯/丁烯-苯乙烯、以马来酐、马来酸或它们的混合物官能化的苯乙烯-乙烯/丁烯-苯乙烯三嵌段;或其混合物的合成嵌段共聚物橡胶。
5.权利要求1-4任一项的组合物,其中聚烯烃(iii)是密度为0.940-0.970之间、熔体指数为1.00-1.30的HDPE。
6.权利要求1-5任一项的组合物,其中基于苯乙烯的聚合物(iv)是HIPS。
7.一种能够保护一个或多个第一层不受聚氨酸泡沫体发泡剂作用的阻挡层,该阻挡层包括权利要求1-6任一项的组合物。
8.一种可热成型的复合材料,该材料包括:
(I)包含由一种或多种基于苯乙烯的聚合物组成的一个或多个次层的官能层,和
(II)粘附于官能层的至少一个表面上的权利要求7的阻挡层。
9.权利要求8的可热成型的复合材料,它包括50-99重量份的官能层(I)和1-50重量份的阻挡层(II),其中所有的重量份相加等于可热成型的复合材料的总重。
10.一种绝热的室壁结构,它包括:
(I)包含由一种或多种基于苯乙烯的聚合物组成的一个或多个次层的官能层,
(II)粘附在官能层的至少一个表面上的权利要求7的阻挡层,
(III)外结构壁,和
(IV)粘附于阻挡层(II)和外结构壁(III)上以将其置于二者之间的绝热体。
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US36671194A | 1994-12-30 | 1994-12-30 | |
US08/366,711 | 1994-12-30 |
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CN1171804A true CN1171804A (zh) | 1998-01-28 |
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CN95197184A Pending CN1171804A (zh) | 1994-12-30 | 1995-12-19 | 冷藏室中使用的阻挡层 |
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US (1) | US5834126A (zh) |
EP (1) | EP0800553B1 (zh) |
JP (1) | JPH11500758A (zh) |
CN (1) | CN1171804A (zh) |
AU (1) | AU698503B2 (zh) |
BG (1) | BG62858B1 (zh) |
BR (1) | BR9510682A (zh) |
CA (2) | CA2164487A1 (zh) |
CZ (1) | CZ197897A3 (zh) |
DE (1) | DE69502510T2 (zh) |
ES (1) | ES2116786T3 (zh) |
FI (1) | FI972721A (zh) |
HU (1) | HU215774B (zh) |
NO (1) | NO973002L (zh) |
NZ (1) | NZ298399A (zh) |
PL (1) | PL321017A1 (zh) |
SK (1) | SK77497A3 (zh) |
WO (1) | WO1996020977A1 (zh) |
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- 1995-12-05 CA CA002164487A patent/CA2164487A1/en not_active Abandoned
- 1995-12-19 CN CN95197184A patent/CN1171804A/zh active Pending
- 1995-12-19 WO PCT/EP1995/005023 patent/WO1996020977A1/en not_active Application Discontinuation
- 1995-12-19 NZ NZ298399A patent/NZ298399A/en unknown
- 1995-12-19 ES ES95942698T patent/ES2116786T3/es not_active Expired - Lifetime
- 1995-12-19 AU AU43877/96A patent/AU698503B2/en not_active Ceased
- 1995-12-19 JP JP8520703A patent/JPH11500758A/ja active Pending
- 1995-12-19 PL PL95321017A patent/PL321017A1/xx unknown
- 1995-12-19 SK SK774-97A patent/SK77497A3/sk unknown
- 1995-12-19 HU HU9800404A patent/HU215774B/hu not_active IP Right Cessation
- 1995-12-19 DE DE69502510T patent/DE69502510T2/de not_active Expired - Fee Related
- 1995-12-19 CA CA002209192A patent/CA2209192A1/en not_active Abandoned
- 1995-12-19 BR BR9510682A patent/BR9510682A/pt not_active Application Discontinuation
- 1995-12-19 EP EP95942698A patent/EP0800553B1/en not_active Expired - Lifetime
- 1995-12-19 CZ CZ971978A patent/CZ197897A3/cs unknown
-
1997
- 1997-06-17 BG BG101630A patent/BG62858B1/bg unknown
- 1997-06-24 FI FI972721A patent/FI972721A/fi unknown
- 1997-06-27 NO NO973002A patent/NO973002L/no not_active Application Discontinuation
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1328040C (zh) * | 2000-11-30 | 2007-07-25 | 住友化学工业株式会社 | 泡沫聚烯烃树脂板材 |
CN102472559A (zh) * | 2009-07-07 | 2012-05-23 | 阿塞里克股份有限公司 | 包含塑料内衬的冰箱 |
CN102472559B (zh) * | 2009-07-07 | 2014-07-30 | 阿塞里克股份有限公司 | 包含塑料内衬的冰箱 |
CN107208956A (zh) * | 2014-12-12 | 2017-09-26 | 霍尼韦尔国际公司 | 改善的abs衬垫和包含其的冷却柜 |
Also Published As
Publication number | Publication date |
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SK77497A3 (en) | 1998-07-08 |
CZ197897A3 (cs) | 1998-06-17 |
DE69502510D1 (de) | 1998-06-18 |
NO973002D0 (no) | 1997-06-27 |
DE69502510T2 (de) | 1998-09-10 |
BR9510682A (pt) | 1999-03-30 |
CA2209192A1 (en) | 1996-07-11 |
JPH11500758A (ja) | 1999-01-19 |
PL321017A1 (en) | 1997-11-24 |
NO973002L (no) | 1997-08-27 |
HU215774B (hu) | 1999-02-01 |
WO1996020977A1 (en) | 1996-07-11 |
MX9704623A (es) | 1997-09-30 |
AU4387796A (en) | 1996-07-24 |
FI972721A0 (fi) | 1997-06-24 |
BG62858B1 (bg) | 2000-09-29 |
AU698503B2 (en) | 1998-10-29 |
EP0800553B1 (en) | 1998-05-13 |
ES2116786T3 (es) | 1998-07-16 |
US5834126A (en) | 1998-11-10 |
FI972721A (fi) | 1997-06-24 |
EP0800553A1 (en) | 1997-10-15 |
BG101630A (en) | 1998-02-27 |
HUT77570A (hu) | 1998-06-29 |
NZ298399A (en) | 1998-11-25 |
CA2164487A1 (en) | 1996-07-01 |
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