CN1161407C - 一种用于粘合、密封和涂层的组合物 - Google Patents
一种用于粘合、密封和涂层的组合物 Download PDFInfo
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Abstract
基于苯乙烯共聚物的用于粘结、密封与涂敷组合物,其特征是,上述苯乙烯共聚物主要含有苯乙烯,并含有非芳族的聚亚烷基氧化物和/或其脂肪衍生物,这些无毒性增塑剂具有良好相容性,而且能增强粘性、弹性与延展性。这种组合物适用于在制备粘合、涂层和密封组合物中用作粘结剂。
Description
本发明涉及一种基于苯乙烯共聚物的用于粘合、密封与涂层的物料,其中至少含有一种其它共聚用单体和作为增塑剂的聚亚烷基氧化物。
上述这种物质是众所共知的,美国专利文献US 4,869,934描述了一种用于地板的磨光、洗净与涂敷的组合物,其中含有以下组成:31.2份重量的由甲基丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸甲酯和苯乙烯,以10∶18∶52∶20比例所组成的共聚物,1.6份重量的永久性增塑剂(BuOCH2CH2O)3PO,7.0份重量的挥发性增塑剂Me(OC3H6)2OH,以及约48份重量的水。然而,上述已知组合物存在缺点,至少是上述挥发性增塑剂对环境不利,或者是有毒的。
在BASF的1984年一月的T1/ED 115d-1技术信息中描述了一种“Plastilit 3060”的产品,它涉及聚丙二醇-烷基苯基醚,它可用作聚合物分散体的增塑剂,特别用于聚丙烯酸酯。作为具体的聚合物,可以是由苯乙烯和丙烯酸丁酯所组成的共聚物,以及由丙烯酸乙酯,丙烯酸乙己酯和丙烯腈所组成的共聚物,这种组合物可用作密封物质,它在使用后迅速成膜,具有很小的后硬化作用,并在低温使用时具有良好的拉伸性能。此外,它与填料可形成糊状的流动性粘合剂,后者具有良好的粘合强度并高弹性。该增塑剂可增强共聚物的弹性作用,不会因膜层吸水而导致明显的减弱。所以当加入9%的增塑剂时,该膜层的线性延展几乎由300%升至4000%。按已有的报导,该增塑剂的生物学作用表明,它们对人体健康没有损害作用。然而,在长期的接触下可能会对皮肤与粘膜有刺激作用。另外的缺点还包括,分散体的粘度会因Plastilit 3060的加入而明显地增高,因此,应严格限制加入的填料量。此外,几乎不能再加入其它的增塑剂。
下面两篇文献也存在同样的上述缺点。例如波兰专利说明书PL 119091描述了一种用于陶瓷与塑料的无毒的和不易燃的粘合剂,它除了含丙烯酸酯-苯乙烯分散体外,还含有聚丙二醇-烷基苯基醚,填料和有机溶剂,以及水。
德国专利DE 3638224描述了一种弹性的密封料,它含有一种苯乙烯-丁二烯橡胶,α-甲基苯乙烯聚合物,诸如烃和芳香烃的溶剂,以及聚丙二醇烷基苯基醚。
捷克专利CS 259825描述了一种用于标签和胶带的粘合剂,它主要含有一种由丙烯酸酯,不饱和羧酸,以及必要时的苯乙烯、烷基苯乙烯或乙烯醋酸酯所组成的共聚物,其它组分还包括有机溶剂,以及诸如聚乙二醇和聚丙二醇的增塑剂。
根据上述现有技术,本发明提出制备一种由苯乙烯共聚物和一种非芳族增塑剂所组成的没有毒性的组合物。它适用于作为粘合剂,而且具有令人满意的胶粘性。
根据本发明的权利要求,可以解决上述发明任务,其特征在于,上述苯乙烯共聚物主要含有苯乙烯,而上述增塑剂是非芳族的聚烷基二醇和/或其油脂化学衍生物。
上述苯乙烯共聚物主要含有苯乙烯或甲基苯乙烯,其含量优选为单体总量的30%(重量),特别是60%(重量)以上,但不超过98%,特别是不超过85%(重量)。苯乙烯或甲基苯乙烯的共聚单体可以是其醇组分中含有1-12个碳原子,尤其是2-8个碳原子的丙烯酸酯或甲基丙烯酸酯。上述丙烯酸酯也可以含有用于进行后交联的反应基,其它的共聚单体可以包括,乙烯酯,马来酸酯,乙烯,丙烯酰胺,丙烯酸,丁二烯,丙烯腈,它们可以以单一物质,也可以是以混合物形式使用,最好是由上述的单体制备的其分子量为100000克/摩尔以上(按凝胶色谱法)的统计共聚物,市售的苯乙烯共聚物有,Acronal 290D,Scopacryl D 343,Ubatol VAF 1539,Acronal S 360 D,Scopacryl PAA D 8875,Acronal S 400,Acronal S 401,Styrofan A 900,Rhodopas DS 913,Joncryl 678,Vinnapas LL 6010与SAF 54,Neocryl A621(由苯乙烯、丙烯酸酯所组成的共聚物),Pliotec LS 1(由苯乙烯、丙烯酸丁酯,甲基丙烯酸所组成的三元共聚物),Mowilith DM 611,Mowilith DM680,Styropor P 555(纯苯乙烯),Buna EM 2116,Styrolux 684 D,Rhodopas SB 012(由苯乙烯、丁二烯组成的共聚物),Novodur P2M,Synthomer VL 10286(由苯乙烯,丁二烯和丙烯腈组成的三元共聚物)。
上述苯乙烯共聚物可根据现有已知方法制备,特别是采用乳液聚合法或珠状聚合法(Perl polymerization)。由此,形成浓度约40-70%(重量)苯乙烯共聚物的含水分散体。当然,也可同样以本体聚合或溶液聚合进行制备。
聚亚烷基氧化物是指具有X(R-O-)nH化学式的聚醚。其中,R表示一个或多个,并以一个为宜的以下基团:亚乙基,亚丙基,或四亚甲基;n是1-50,优选为2-30,尤其是4-20的数值;x是具有1-12,或1-6功能基的非芳族的起动分子。上述优选的聚亚烷基氧化物是聚乙二醇和聚丙二醇,也可以是聚丁二醇,它还可以使用由聚乙二醇与聚丙二醇所组成的嵌段共聚物。终端OH基可以完全地或部分地酯化(例如与脂肪酸或二元羧酸)或者醚化。其分子量(渗透平均值)是低于5000,尤其是低于2500,并以低于1500为宜。市售的聚亚烷基氧化物有聚丙二醇420,620与2020(Huls公司产品),Pluronic型(BASF公司产品),Voranole(Dow公司产品),以及聚乙二醇(Hoechst公司产品)。
上述的聚亚烷基氧化物通常是通过环氧乙烯和/或环氧丙烷在水,乙二醇,丙二醇,多元醇,如丙三醇,聚丙三醇,三羟甲基丙烷,季戊四醇,山梨糖醇,葡萄糖,多糖,氨水,三乙醇胺,或羧酸等的加聚而制备的。
适用于上述加聚的起动分子也可以是具有和环氧乙烷或环氧乙烷进行反应的功能基的脂肪物质。上述脂肪物质平均含有1-10,优选1.5-6.0的,至少下列一个官能基,-OH,-SH,-NH2,-COOH或酸酐基或在有水情况下的氧化物基。
也可以采用无官能基的脂肪的化合物,这时必须加入反应的催化剂量的水,醇或羧酸。
具有官能基的脂肪衍生物,如环氧化的大豆油或甘油三酸脂/MSA加成物和聚亚烷基氧化物进行转化反应而形成本发明的产物。
上述“脂肪化合物”是指脂肪酸,脂肪醇或其衍生物,其中至少含有一个上述的官能基。通常,其分子量大于100,优选的大于200,但不超过20,000,优选为300-1500。聚醚与由环氧乙烯或环氧丙烯和脂肪物质的反应产物的重量比是1∶0.01~3,优选为1∶0.1~2。
上述“脂肪酸”是指具有1个或多个羧基(-COOH)的酸,该羧基可以和饱和、不饱和,直链或支链的具有8个,优选为12个以上的碳原子的烷基相结合。它除了含有上述的-OH,-SH,-C=C-,-COOH,氨基,酸酐基或环氧基外,还可以含有其它基团,如醚基,酯基,卤基,酰胺基,氨基,和氨基甲酸乙酯基和脲基。然而,上述羧酸最好是天然脂肪酸或脂肪酸混合物,二聚脂肪酸和三聚脂肪酸。脂肪酸的具体实例除了饱和的以外,特别可以是一元或多元不饱和的酸,棕榈油酸,油酸,反油酸,岩芹酸,芥酸,蓖麻油酸,羟基甲氧基硬脂酸,12-羟基硬脂酸,亚油酸,亚麻酸,和顺-9-二十碳烯酸。
除了天然存在的脂肪酸外,还可以使用多羟基脂肪酸,它们可以通过对不饱和脂肪和油,或者脂肪酸和醇组成的酯,用H活性化合物,例如醇,胺,以及羧酸的开环作用及随后的皂(碱)化反应而制备。这些用作反应原料必要的脂肪或油脂可以来自植物源,也可来自动物源,或者可以根据石油化学的合成方式而制得的。
上述脂肪酸也可以由油基和脂基的原料制得,例如通过En-反应,狄尔斯-阿德耳反应,酯基转移作用,缩合反应,接枝反应(例如和马来酸酐或丙烯酸等),以及环氧化反应而制得的。作为实例,可以是a)不饱和脂肪酸,如棕榈油酸,油酸,反油酸,岩芹酸,芥酸,亚油酸,亚麻酸,顺-9-二十碳烯酸的环氧化物,b)不饱和脂肪酸和马来酸,马来酸酐,甲基丙烯酸或丙烯酸的反应产物,c)羟基羧酸,如蓖麻油酸或12-羟基硬脂酸和多羟基羧酸的缩合产物。
不是所有的上述脂肪酸在室温中都稳性。因此,如果需要,本发明可以使用上述脂肪酸的衍生物,例如其酯或酰胺。
本发明的优选实施方案,采用了由上述脂肪酸和一元醇或多元醇所组成的酯或偏酯。这里所说的“醇”,是指脂族与脂环族的,饱和与不饱和的,支链或直链烃的羟基衍生物。除了一元醇外,它们也可以是在聚氨基甲酸乙酯化学中所熟知的具有羟基的低分子的链增长剂或交联剂。上述的所谓低分子范围的实例是甲醇,乙醇,丙醇,丁醇,戊醇,癸醇,辛醇,2-乙己醇,2-辛醇,乙二醇,丙二醇,三亚甲基二醇,四亚甲基二醇,2,3-丁二醇,六亚甲基二醇,八亚甲基二醇,新戊二醇,1,4-双羟基甲基环己烷,格尔伯特醇,2-甲基-1,3-丙二醇,(1,2,6)-己三醇,丙三醇,三羟甲基丙烷,三羟甲基乙烷,季戊四醇,山梨糖醇,甲酸酯,甲基糖苷,丁二醇,以及由二聚脂肪酸和三聚脂肪酸还原的醇。由松香树脂衍生的醇,如松香醇也可用于酯化。
也可以用含OH基的叔胺,聚丙三醇或部分水解的聚乙烯酯代替上述的醇。
此外,对低聚化也可以使用聚羧酸或羟基羧酸。例如,草酸,丙二酸,琥珀酸,马来酸,富马酸,戊二酸,己二酸,辛二酸,癸二酸,1,11-十一烷基酸,1,12-十二烷基酸,苯二甲酸,间苯二甲酸,对苯二甲酸,六氢苯二甲酸,四氢苯二甲酸或二聚脂肪酸,三聚脂肪酸,柠檬酸,乳酸,洒石酸,蓖麻油酸,12-羟基硬脂酸,优选是使用己二醇。
上述适用的酯类,除了部分皂化的脂肪外,例如甘油单硬脂酸酯,优选的是来自菜籽(新),向日葵,大豆,亚麻,蓖麻仁,椰仁,油棕榈,油棕榈仁与油橄榄的天然脂肪和油,以及其甲基酯。优选的脂肪和油包括牛油脂,它含67%油酸,2%硬脂酸,1%的十七烷基酸,10%C12-C16的饱和酸,12%亚油酸,以及2%具有>C18碳原子的饱和酸,或者如新向日葵(NSb)制得的油,它含有约80%油酸,5%硬脂酸,8%亚油酸与约7%棕榈酸。当然,也可以使用其相应的环氧化物和与马来酸酐的反应产物。其它还可以是经部分脱水与完全脱水的蓖麻油,经部分乙酰化的蓖麻仁油,以及具有二聚脂肪酸的环氧化的大豆油的开环化物。
此外,还可以使用脂肪酸酯,以及其可得到的环氧化衍生物,这种酯的实例例如,大豆油脂肪酸甲酯,亚麻油脂肪酸甲酯、蓖麻酸甲酯、环氧硬脂酸甲酯,环氧硬脂酸-2-乙己酯。上述的甘油脂中优选的是三甘油酯,例如菜籽油,亚麻油,大豆油,蓖麻仁油,部分或完全脱水的蓖麻仁油,部分乙酰化的蓖麻仁油,大豆油的环氧化物,亚麻油的环氧化物,菜籽油的环氧化物,环氧化的向日葵油。
优选使用环氧化的亲核、开环的,不饱和脂肪酸的三甘油酯。上述的亲核是指醇,例如甲醇,乙醇,乙二醇,丙三醇或三羟甲基丙烷,胺,例如乙醇胺,二乙醇胺,三乙醇胺,乙二胺或六亚甲基二胺,或羧酸,例如醋酸,二聚脂肪酸,马来酸,苯二甲酸或是有C6-C36脂肪酸的混合物。
上述的脂肪和油(三甘油酯)可以是天然状态的,也可以是经热处理和/或氧化处理的,或者环氧化反应或经马来酸酐或丙烯酸的加成反应所得的衍生物。具体实例如,棕榈油,花生油,菜籽油,棉籽油,大豆油,蓖麻仁油,部分或完全脱水的蓖麻仁油,部分乙酰基化的蓖麻仁油,向日葵油,亚麻油,聚合油,吹制油(blown oils),环氧化的大豆油,环氧化的亚麻油,菜籽油,椰子油,棕榈仁油与牛脂油。
上述衍生物也可以是上述脂肪酸的酰胺,它们可以通过和伯胺和仲胺或聚胺反应而制得的,例如,和单乙醇胺,二乙醇胺,乙二胺,六亚甲基二胺,氨水。然而,其中还必须含有亲核基团,以与亚烷基氧化物反应。
上述的“脂肪醇”是指含有一个或多个羟基的化合物。该羟基可以和饱和的或不饱和的、直链的或支链的、具有8个以上,尤其是12个以上碳原子的烷基相结合。它们除了含有以后与亚烷基氧化物进行反应所必要的-SH,-C=C-,-COOH,氨基,酸酐基或环氧化物基外,还可以含有其它的基团,例如,醚基,酯基,卤基,酰胺基,氨基,脲基,以及氨基甲酸乙酯基。用于本发明的脂肪醇的具体实例是蓖麻醇,12-羟基硬脂醇,油醇,瓢儿菜醇,亚麻醇,花生醇,顺-9-二十碳烯醇,瓢儿菜醇,顺芜醇,二聚二醇(即二聚脂肪酸甲酯的加氢产物)。
上述脂肪醇的衍生物可以是对称和不对称的、具有一元羧酸或多元羧酸的醚与酯。上述的一元羧酸包括,蚁酸,醋酸,丙酸,丁酸,戊酸,己酸,庚酸,辛酸,壬酸,癸酸,十一烷基酸,月桂酸,十三烷基酸,肉豆蔻酸,十五烷基酸,棕榈酸,十七烷基酸,硬脂酸,十九烷基酸,花生酸、山萮酸、二十四烷基酸,蜡酸与蜂花酸。上述的多元(聚)羧酸包括如草酸,己二酸,马来酸,酒石酸与柠檬酸。同时,也可以将上述的脂肪酸用作羧酸,例如油酸油酯。
上述脂肪醇也可以进行醚化,特别是多元醇,例如烷基聚糖苷,二聚二醇醚。当然,上述脂肪物质的混合物也可以用作与亚烷基氧化物进行反应时的起始分子。
苯乙烯共聚合物对起增塑作用的,非芳属聚亚烷基二醇或其油脂化学衍生物的重量比是100∶0.5~50,优选为100∶2.5~40,并以100∶7.5~15或100∶20~40为宜。
本发明的物质除了含有上述两个基本组分外,还含有其它成分,例如抗氧化剂、颜料、填料、增塑剂、防腐剂、消泡剂、成膜助剂、香料、水、粘合介质、溶剂、色料、防火剂、流动助剂、树脂、增粘剂、粘度调节剂、分散助剂(例如聚丙烯酸的钠盐或铵盐)、乳化剂(例如烷基醚磷酸酯和磺基琥珀酸酯)、以及增稠剂(例如MC,HEG)。
作为树脂可以是,聚异丁烯或聚丁烯(例如BP的Hyvis 10),松香树脂及其衍生物(酯,加氢产物,松香醇),丙烯酸酯树脂,苯酚树脂,萜烯-苯酚树脂,聚萜烯,环氧化物树脂,烃树脂,茚-香豆酮树脂,以及密胺树脂。
作为抗氧化剂可以是:磷酸及其盐,次磷酸及其盐,抗坏血酸及其衍生物(特别是抗坏血酸基棕榈酸酯),生育酚及其衍生物,抗坏血酸衍生物与生育酚衍生物的混合物,位阻苯酚衍生物,特别是BHA(叔丁基-4-甲氧基苯酚)与BHT(2,6-二-叔-丁基-4-甲基苯酚),五倍子酸及其衍生物,特别是五倍酸烷基酯,芳香胺,例如二苯胺,萘胺与1,4-苯二胺,二氢基喹啉,有机的硫化物及多硫化物,二硫氨基甲酸酯,以及巯基苯并咪唑。
作为粘度调节剂可以是:纤维素醚,氢化的蓖麻仁油,以及高分散性的硅酸。
作为填料或颜料可以是:白垩,重晶石,高岭土,炭黑,石膏,气溶胶,硅胶,滑石粉,石墨,或者铝,铁,锌,钛,铬,钴,镍,锰等的金属氧化物或者混合氧化物,还有铬酸盐,钼酸盐,碳酸盐,硅酸盐,铝酸盐,硫酸盐,天然纤维,纤维素,木屑,酞花青以及石英粉。
除了本发明的增塑剂以外的另外的增塑剂可以是:不含聚亚烷基氧化物成分的油脂化学的增塑剂,特别是脂肪酸甲基脂,脂肪酸与其它醇所组成的酯,三甘油脂。根据所使用目的,确定添加剂的加入量。
通常,可以把相同的脂肪化合物用作另外的增塑剂,如上面所述的在制备聚亚烷基氧化物的油脂化学衍生物时用作原料的化合物。当然,并不再需要反应性基团,它可以通过和C1-C4单元醇或羧酸进行转化反应而去活化。
本发明物质是按以下由原料制备,可以在聚合过程中,之前或之后,向共聚物或向共聚物分散体中添加本发明的增塑剂。通常,其配方是这样构成的,即首先加入聚合物或聚合物分散体。然后,在搅拌下再加入其它组分(必要时提高温度),最好是使用共聚物-分散体。
通常,本发明的增塑剂可以对苯乙烯共聚物产生以下变化:
-其玻璃转化温度降低
-共聚物成为粘性
-其粘度部分提高,部分降低
-其断裂伸长明显提高
-在施加最大力时,其延伸性会剧烈提高,它以橡胶弹性表示。
具有特别意义的是,这些作用是持久性的,也就是说,在60℃下,三周之内不会观察到该增塑剂的变化。为此,进行如下的试验:在60℃下,把膜层置于硅酮纸之间持续3周,而且每间隔3天,评价该纸的斑点情况。
当聚丙二醇具有约600克/摩尔的分子量时,就特别有效。当其加入量为15%(重量)时,苯乙烯/丙烯酸丁酯共聚物的粘性由7500降到1700。该条件是,在60℃下在烧杯中将100重量份的Acronal 290 D和15份重量的聚丙二醇629(Huls公司制备),混合30分钟,直至均匀分散为止。其断裂延伸性也提高12000%以上。TG降到-35℃。其它的本发明的特别重要的增塑剂有,如戊丙三醇×20EO×50PO,TMP×12PO,以及环氧化大豆油和由20%(重量)的环氧乙烷进行反应的初馏份脂肪酸所生成的产物。它们具有如下的作用,在一定浓度下,该分散体的粘性和玻璃转变温度都降低。此外,它们也使聚合物膜层有橡胶弹性性质。
根据上述特性,本发明的组合物适合于在制备粘合剂,密封结合物,以及涂层组合物中用作粘结剂。
作为粘合剂具体的有:热熔化粘合剂,溶剂粘合剂,分散粘合剂,装配用粘合剂,粘附性粘合剂,接触粘合剂,以及再分散粉剂,万能胶及胶粘捧。可以粘附的是纸张,纸板,木材,纺织物,墙壁覆层,瓷砖,标签,皮革,橡皮,塑料,玻璃,陶瓷以及金属。上述的涂层剂可以包括:塑料溶胶,分散涂料,以及屋顶的绝缘涂层。上述的密封剂既可以用于建筑工业也可用于汽车领域。本发明的组合物也可以加入到水性凝结剂中,如水泥或石膏。
根据所用增塑剂的种类及用量,以及取决于通用的组合物,粘合剂具有不同的特性,如不同的粘性,特别是不同的粘附力。由80%(重量)的Acronal290 D和20%(重量)的聚丙二醇600所组成的组合物可以防止地板覆层,特别是具有纺织物底衬的地毯,或者有沥青,PVC或不规则的聚丙烯背衬的地毯对通常底基上的滑动。上述底基可以是灰泥地面。例如水泥,硬石膏地面,或者木板,压合木屑板,或金属制底基。它们可以是未经处理的,或是用基于水泥,聚氨基甲酸乙酯,环氧树脂或分散体的调平料或涂层进行预处理的。
下列组合物不单具有防滑效果,而且可使地板覆层在上述底基上具有更高的但有限的强度,以便易于再除去。
-30%(重量)Acronal 290 D
-5%(重量)聚丙二醇600
-5%(重量)分散助剂,乳化剂,消泡剂,增稠剂,
-15%(重量)松香甲基酯,
-15%(重量)水,
-30%(重量)白垩。
上述地板覆层可以是成片或面砖并可以由PVC或纺织物料组成,特别是CV覆层(缓冲乙烯)和纺织物覆层,该覆层具有乳胶或PUR泡沫背面,有纺织物底衬或稳定涂层。
这两种组合物是在15-50℃,特别是15-30℃温度下,在分散体中按一定的顺序搅拌加入其它的原料而制得的。
下列组合物可以使地板覆层牢固地粘合在上述的底基上。
35%(重量),Acronal 290 D
37%(重量),白垩
20%(重量),一种80%的香脂树脂的二乙二醇单丁醚溶液
5%(重量),聚丙二醇600
3%(重量),分散助剂,乳化剂,消泡剂,增稠剂。
该要粘贴的地板覆层可以是PVC,CV,亚麻或纺织品覆层,它具有不同的背衬,或是具有纺织品或PVC底面的不均匀覆层。
据下列步骤制备组合物:在15-30℃温度下,向分散体中搅拌加入聚丙二醇600分散助剂,乳化剂,消泡剂和增稠剂。然后在50-90℃,优选70-80℃温度下,连续不断加入香脂树脂,并继续搅拌,使混合物均匀混合,接着在搅拌下加入填料,并继续搅拌混合,直至该混合物均匀混合,并且不含结块状物。
为了制备封缝混合物,必须使苯乙烯共聚物中的TG在-10℃以下的温度优选为-20℃以下。此外,尽管含有较高的填料,但该分散体必须形成平坦的膜层。可应用的密封组合物可以具有下列组成:34%(重量)的Acronal290 D,1%的菜籽油甲基酯,5%的聚丙二醇600,以及60%的白垩,该分散体呈膏状,而且宜于铺展。由此制成的膜层具有弹性,而且具有强的回弹性。这种组合物适于用作封缝物质。
实施例
I.原料
1.Acronal 290 D=50%的苯乙烯/丙烯酸丁酯共聚物(阴离子型)的含水分散体,
2.PPG 620=分子量为约600的聚丙二醇,
3.PPG 2020=分子量为约2000的聚丙二醇,
4.A=脂肪醇(C12-C14)和环氧乙烷,以摩尔比为1∶3的反应产物,
5.B=蓖麻油和环氧乙烷,以摩尔比为1∶20的反应产物,
6.C=聚丙醇-烷基苯基醚(Plastilit 3060),
7.D=环氧化的大豆油和由20%(重量)环氧乙烷反应初馏脂肪酸的反应产物,例如按下列步骤制备的。
在压热器中将4000克的大豆多元醇85(Sojapolyol 85)和12.5克的50%KOH水溶液混合,在90℃与<40mbar条件下,抽真空20分钟,以除去其中的水份。然后,再加入1000克的环氧乙烷,并在160℃下反应,反应时间进行30分钟后。冷却至90℃,并再加入11.1克的90%乳酸,测得的OHZ(OH值)是94,SZ(酸值)是04。
II.物质的制备
在60℃温度下,在烧杯中混合100份重量的Acronal 290 D和表中所列量的聚丙二醇30分钟,直至该分散体达到均匀为止。
III.对该物质的检测
按下列步骤制备试验用样品:改性分散体置入模中并在40℃的培养箱中制成膜。将膜在标准状态下(23℃,50%LF)放置7天,然后进行检测。
按下进行固体浓度(FK)的测定:将5-10克的上述试样放在铝盘中,并在120-130℃温度下加热2小时,然后再次称量。
按下进行粘度的测定:Brookfield RVT(20℃)。
按下列条件测定断裂延伸(延伸率):lnstrom 4302,自动的物料测试装置Serie IX,试样宽度为5mm,试样厚度为1mm,试样长度为15mm,牵引速度是200mm/分钟。
按下测定组分的相容性(渗漏):使膜在60℃时夹在硅酮纸中间。经3周后,评判纸上的斑点。
按下测定玻璃转变温度(TG):具有Dupont 2100的测量池的DSC 910,有盖的Al-坩埚,3升/小时的N2气,20K/分。
按下测定粘附性(RK):将一个钢珠(直径20nn,重32.25克)在本发明组合物的膜的斜面上(高26mm,斜长115mm)向下滚动。然后测定在聚合物膜上的滚动距离。(以mm计)。
上述试验结果列于表中,其中,
-脂族的增塑剂是与芳香族的共聚物相容(无渗漏),
-玻璃转变温度强烈降低,可达到-10℃,甚至-20℃以下,
-添加约10%后,该物质就变成粘性,
-通常粘度是剧烈增高,然而它可以保持不变,或甚至降低,
-断裂延伸率提高,有时很强。
表1:根据本发明物质的组成与特性(实例2、3、4与5)
实例 添加物 % FK 粘度 延伸率% 渗漏 TG RK
(mPas)
1 - 0 51,25 7500 1598 不 21
2a PPG 600 2,5 53,70 15500 4471 不 >130(32)
2b ″ 7,5 57,60 6000 3470 不 -6 >130(32)
2c ″ 15 59,10 1700 >12000 不 -35 16(32)
3a PPG 2020 2,5 51,80 36000 4544 不
3b ″ 7,5 54,30 38000 5642 不 -2 >130(32)
3c ″ 15 58,30 122000 6214 不 -17 14(32)
4a A 2,5 50,80 18500 4159 不
4b ″ 7,5 51,93 64000 5875 不 -12
4c ″ 15 52,50 1100000 是
5a B 2,5 54,00 10500 4312 不
5b ″ 7,5 56,30 7400 6819 不 9
5c ″ 15 56,70 11000 4983 不
6a C 2,5 11000 4779 >130
6b ″ 7,5 28000 4274 52
6c ″ 15,0 70000 9000 10
续(表1)
实例 添加物 % FK 粘度 延伸率% 渗漏 TG
(mPas)
7a D 2,5 56,40 32000 4318 不
7b ″ 7,5 55,60 20000 6206 不 6
7c ″ 15,0 62,20 32000 9021 不 -7
Claims (9)
1.基于苯乙烯和至少一种其它共聚物用单体的共聚物和一种聚亚烷基氧化物的组合物在制备粘合剂、密封和涂料组合物中的用途,其中该苯乙烯共聚物中苯乙烯的含量高于30%重量,而作为增塑剂的聚亚烷基氧化物是一种非芳族的聚亚烷基氧化物和/或其油脂化学的衍生物,且该组合物不含任何潜在的由甲醛与苯酚、脲或三嗪缩合而形成的可热固化树脂。
2.根据权利要求1的用途,其特征是,该组合物还含有一种不和烯化氧反应的油脂化学的增塑剂。
3.根据权利要求1的用途,其特征是,所述聚亚烷基氧化物是环氧乙烷,环氧丙烷或环氧丁烷的均聚物或共聚物,且该聚亚烷基氧化物的油脂化学衍生物是脂肪物质和环氧乙烷,环氧丙烷或环氧丁烷的反应产物。
4.根据权利要求1-3中任一项的用途,其特征是,上述聚亚烷基氧化物和/或其油脂化学的衍生物的分子量高于400。
5.根据权利要求1-3中任一项的用途,其特征是,在每100份重量的苯乙烯共聚物中有0.5-50份重量的油脂化学的衍生物。
6.根据权利要求1-5中任一项的组合物的制备方法,其特征是,把该增塑剂混入苯乙烯共聚物的含水分散体。
7.根据权利要求1-3中任一项的组合物的用途,其中,用于制备粘合剂,密封剂和涂料组合物。
8.根据权利要求7的用途,其特征是,该粘合剂可用于粘贴地板覆层。
9.根据权利要求7的用途,其特征是,该密封剂可用作封缝剂。
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JP4765048B2 (ja) * | 2004-02-13 | 2011-09-07 | ローター・インコーポレイテツド | 粘着付与剤分散体 |
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US8468770B2 (en) | 2009-09-23 | 2013-06-25 | Textile Rubber & Chemical Company, Inc. | Floor covering product and method of using same |
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GR3036960T3 (en) | 2002-01-31 |
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HUP9901624A2 (hu) | 1999-08-30 |
EP0833864A1 (de) | 1998-04-08 |
CZ294142B6 (cs) | 2004-10-13 |
NO974858D0 (no) | 1997-10-21 |
KR19990028304A (ko) | 1999-04-15 |
NO974858L (no) | 1997-10-21 |
ATE204315T1 (de) | 2001-09-15 |
WO1997000912A1 (de) | 1997-01-09 |
BR9608955A (pt) | 1999-03-02 |
ES2162077T3 (es) | 2001-12-16 |
CZ416497A3 (cs) | 1998-06-17 |
PL184685B1 (pl) | 2002-11-29 |
US6800682B1 (en) | 2004-10-05 |
KR100418108B1 (ko) | 2004-05-20 |
PL322875A1 (en) | 1998-03-02 |
JPH11507974A (ja) | 1999-07-13 |
DE19624148A1 (de) | 1997-01-02 |
HU225429B1 (en) | 2006-11-28 |
EP0833864B2 (de) | 2005-08-10 |
HUP9901624A3 (en) | 2000-04-28 |
AU6224996A (en) | 1997-01-22 |
DK0833864T3 (da) | 2001-11-12 |
RU2235746C2 (ru) | 2004-09-10 |
DK0833864T4 (da) | 2005-12-19 |
CA2225423A1 (en) | 1997-01-09 |
PT833864E (pt) | 2002-02-28 |
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