CN1346383A - 可减少形成放射斑趋向的聚碳酸酯组合物 - Google Patents
可减少形成放射斑趋向的聚碳酸酯组合物 Download PDFInfo
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Abstract
公开了一种透明的具有良好的脱模性质的热塑性模塑组合物。该组合物不包含磁性成分,其包含一种聚碳酸酯树酯和占0.01-0.3wt%的一种脱模剂。该脱模剂是由式(I)代表的化合物(其中R1表示C1-30烷基)与选自式(i)(其中R2和R3独立地表示C1-30烷基或者芳基)和式(ii)(其中n是1-7)中的至少一种化合物进行反应的产物。
Description
发明领域
本发明涉及透明的热塑性模塑组合物,尤其是具有良好的脱模性质的聚碳酸酯模塑组合物。
发明概述
这里R1表示C1-30-烷基,
其中R2和R3独立地表示C1-30-烷基或者芳基,
其中n是1-7。
发明背景
单硬脂酸甘油酯(GMS)作为一种脱模剂用于热塑性聚碳酸酯模塑组合物其效果是众所周知的。然而本领域技术人员已观察到:作为与单硬脂酸甘油酯酯交换的结果,聚碳酸酯分子量的降解显示出使用这种脱模剂的缺点。在模塑期间因主要处于受热状态下,酯交换的产物,单硬脂酸甘油酯-碳酸酯,分解产生二氧化碳,它导致了被称为放射斑(splay)的模塑缺陷。这一缺陷是光存储器部件例如光盘的生产者所主要关心的,这不仅因为其美观方面的问题而且也考虑到储存信息的复制问题。本发明解决了上述问题。
一种在结构上符合本发明的脱模剂的化合物已经公开在美国专利5,145,751中。该′751文献公开了一种磁记录介质,它包括一种无磁性的基质和一种涂在该基质上的磁性记录层。该层包括一种包裹本发明脱模剂的化合物。
发明详述
本发明的热塑性组合物的特点在于:其中没有磁性成分,并且包含一种聚碳酸酯树酯和一种相对于聚碳酸酯重量为准计,大约0.01-0.3%,优选0.03-0.1%的脱模剂。
制备本发明的共聚物的适用聚碳酸酯树酯是均聚碳酸酯和共聚碳酸酯及其混合物。
该聚碳酸酯通常有重均分子量10,000-200,000,优选15,000-22,000,其熔体流动速率,按照ASTM D-1238方法,在300℃是约1-约95g/10min,优选大约60-90g/10min。其可以由例如已知的两相界面方法,由一种碳酸衍生物例如光气和二羟基化合物经过缩聚反应而制得(见德国公开文本2,063,050;2,063,052;1,570,703;2,211,956;2,211,957和2,248,817;法国专利1,561,518;和由H.Schnell编著“聚碳酸酯的化学和物理(Chemistry and Physics ofPolycarbonates)”,Interscience Publishers,New York,N.Y.,1964中的专论,全部的文献在这此引入作为参考)。
在本文中,适于制备本发明的聚碳酸酯的二羟基化合物应符合结构式(1)或者(2)。
e和g都表示0-1的数;
Z表示F、Cl、Br,或者C1-C4-烷基,并且如果几个Z基团都是一个芳基的取代基时,它们可以彼此相同或者不同;
d表示0-4的整数;
f表示0-3的整数。
在实施本发明中采用的二羟基化合物包括:对苯二酚、间苯二酚、双-(羟苯基)-链烷、双-(羟苯基)-醚、双-(羟苯基)-酮、双-(羟苯基)-亚砜、双-(羟苯基)-硫化物、双-(羟苯基)-砜、二羟基二苯基环烷烃和α,α-双-(羟苯基)-二异丙基-苯以及它们的环结构上烷基化的化合物。这些和其他合适的芳族二羟基化合物描述在,例如美国专利:5,227,458;5,105,004;5,126,428;5,109,076;5,104,723;5,086,157;3,028,356;2,999,835;3,148,172;2,991,273;3,271,367和2,999,846中,全部文献在此引入作为参考。
其它适合的双酚实例是2,2-双-(4-羟苯基)-丙烷(双酚A)、2,4-双-(4-羟苯基)-2-甲基丁烷、1,1-双-(4-羟苯基)-环己烷、α,α’-双-(4-羟苯基)-对-二异丙苯、2,2-双-(3-甲基-4-羟苯基)-丙烷、2,2-双-(3-氯基-4-羟苯基)-丙烷、双-(3,5-二甲基-4-羟苯基)-甲烷、2,2-双-(3,5二甲基-4-羟苯基)-丙烷、双-(3,5-二甲基-4-羟苯基)-硫化物、双-(3,5二甲基-4-羟苯基)-亚砜、双-(3,5-二甲基-4-羟苯基)-砜,二羟基-二苯甲酮、2,4-双-(3,5-二甲基-4-羟苯基)-环己烷、α,α’-双-(3,5-二甲基-4-羟苯基)-对-二异丙苯与4,4’-磺酰联苯酚。
特别优选的芳族双酚的实例是:2,2-双-(4-羟苯基)-丙烷、2,2-双-(3,5-二甲基-4-羟苯基)-丙烷、1,1-双-(4-羟苯基)-环己烷与1,1-双-(4-羟苯基)-3,3,5-三甲基环己烷。
最优选的双酚是2,2-双-(4-羟苯基)-丙烷(双酚A)。
本发明的聚碳酸酯可要求它们的结构单元衍生于一个或多个合适的双酚。
在实施本发明中合适的树脂包括:以苯酚-酞为基础的聚碳酸酯,共聚碳酸酯与三聚碳酸酯,例如在美国专利3,036,036与4,210,741中所描述的,两个文献在此引入作为参考。
本发明的聚碳酸酯也可以通过与其中少量的,例如相对于双酚为准计,0.05-2.0摩尔%的多羟基化合物缩合而被支化。
这一类型的聚碳酸酯已经在,例如德国公开文本1,570,533;2,116,974与2,113,374;英国专利885,442与1,079,821和美国专利3,544,514中描述。以下是一些可以被用于此目的的多羟基化合物的一些实例:间苯三酚;4,6-二甲基-2,4,6-三-(4-羟苯基)-庚烷;1,3,5-三-(4-羟苯基)-苯;1,1,1-三-(4-羟苯基)-乙烷;三-(4-羟苯基)-苯基甲烷;2,2-双-[4,4-(4,4’-二羟基二苯基)]-环己基-丙烷;2,4-双-(4-羟基-1-异亚丙基)-苯酚;2,6-双-(2-二羟基-5’-甲苯基)-4-甲酚;2,4-二羟基苯甲酸;2-(4-羟苯基)-2-(2,4-二羟苯基)-丙烷和1,4-双-(4,4-二羟基三苯基甲基)-苯。其他一些多官能化合物是2,4-二羟基苯甲酸、苯均三酸、氰尿酰氯和3,3-双-(4-羟苯基)-2-氧代-2,3-二氢吲哚。
除上述的缩聚反应方法之外,其他制备本发明的聚碳酸酯的方法是在均相中的缩聚反应和酯交换。这些合适的方法都已经公开并且在此引入作为参考,例如美国专利3,028,365;2,999,846;3,153,008;和2,991,273。
制备聚碳酸酯的优选方法是界面缩聚方法。
可以使用其他的制成本发明的聚碳酸酯的合成方法,例如公开在美国专利3,912,688中的方法,该文献在此引入作为参考。
合适的聚碳酸酯树酯是市售的,例如Makrolon FCR、Makrolon 2600Makrolon 2800和Makrolon 3100,所有这些产品都是以双酚为基础的各自的分子量不同的均聚碳酸酯树脂,其特性在于它们的熔体流动指数(MFR),按照ASTM D-1238方法,大约分别为:16.5-24,13-16,7.5-13.0和3.5-6.5g/10min。特别合适的产品是Makrolon CD 2005和Makrolon DP1-1265,其分别具有MFR值为60-70和70-90g/10min.。这些是拜耳公司(Pittsburgh,Pennsylvania)的产品。
一种在实施本发明中合适的聚碳酸酯树酯是已知的并且它的结构和制备方法已经公开,例如美国专利3,030,331;3,169,121;3,395,119;3,729,447;4,255,556;4,260,731;4,369,303和4,714,746,所有这些文献在此引入作为参考。
其中R1表示C1-30烷基,优选C4-25烷基,更优选C14-20烷基,
其中R2和R3独立地表示C1-30烷基,优选C4-25烷基,更优选C14-20烷基或者芳基,
其中n是1-7,优选2-5。
其中R1、R2和R3独立地是C4-25烷基和n是2-5。
对此合适的反应和催化剂描述于Org.Synth.III,502(1955),该文献在此引入作为参考。
本发明的组合物可包含常规的添加剂,这些添加剂因具有该领域承认的功能而众所周知。这些添加剂包括染料,阻燃剂和水解稳定剂,紫外稳定剂,增塑剂和脱模剂。在一个优选实施方案中,该组合物适于制造非常透明的光存储器部件。用于这些部件的模塑制品其特性在于按照ASTM D-1003方法对100mils厚的样品测量得出的透明度至少为88%。
本发明的稳定的组合物的制备方法是常规的。
实施例
已经制备了一种符合本发明的脱模剂并且测定了其效果。
一种结构符合上面结构式(IV)的脱模剂的制备方法描述如下,其中R1是C17烷基并且n=3:
向一个装备有迪安-斯达克分水器和冷凝器的250毫升圆底烧瓶中加入10.22克单硬脂酸甘油酯,75毫升的干甲苯,0.09克的对甲苯磺酸一水合物和4.0毫升的环己酮。在搅拌下进行回流反应,直至经迪安-斯达克分水器收集的水达到理论值(大约0.5毫升)。一旦该反应完成,加入2.0毫升的三乙胺并且通过蒸馏除去甲苯。向残留的熔融物料中加入280毫升的甲醇并且缓慢地使其冷却至室温以沉淀出反应产物。为了保证该物料已经全部沉淀,慢慢地加入70毫升的去离子水。该沉淀物通过真空过滤被收集并在减压下干燥,得到10.994克的白色粉末。
制备本发明的组合物:
将按照如上所述的步骤制备的试剂加入到一种以双酚-A为基础的具有重均分子量约18,000的均聚碳酸酯树脂中,加入量为300ppm,得到的制品按通常方法进行模塑。该试剂显示出的脱模性质相当于单硬脂酸甘油酯。由本发明的组合物制备的光盘上统计出的放射斑数量显著小于使用等量单硬脂酸甘油酯的光盘。
虽然在上文中为了说明的目的已经详细描述了本发明,但是应该理解这些细节仅用于说明的目的。除可被本权利要求书所限定之外,本领域的技术人员能够在其中做出变化而不会脱离本发明的实质和范围。
Claims (10)
2.按照权利要求1中的组合物,其中相对于聚碳酸酯的重量,所述的脱模剂的存在量为0.03-0.1%。
3.按照权利要求1的模塑组合物,其中所述的一员化合物是式(i)并且R1表示C4-25烷基。
4.按照权利要求1的模塑组合物,其中所述的一员化合物是式(i)并且R2与R3独立地表示C4-25烷基。
5.按照权利要求1的模塑组合物,其中所述的一员化合物是式(i)并且R1、R2与R3独立地表示C14-20烷基。
8.按照权利要求1的模塑组合物,其中所述的脱模剂符合下式其中R1表示C4-25烷基并且n是2-5。
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US09/290,906 US6046301A (en) | 1999-04-12 | 1999-04-12 | Polycarbonate compositions having reduced tendency to splay |
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AU2017330346A1 (en) | 2016-09-21 | 2019-02-21 | Nextcure, Inc. | Antibodies for Siglec-15 and methods of use thereof |
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ES2206223T3 (es) | 2004-05-16 |
AU4225900A (en) | 2000-11-14 |
WO2000061671A1 (en) | 2000-10-19 |
US6046301A (en) | 2000-04-04 |
DE60005169D1 (de) | 2003-10-16 |
CA2370029A1 (en) | 2000-10-19 |
DE60005169T2 (de) | 2004-07-01 |
CN1142970C (zh) | 2004-03-24 |
TWI230177B (en) | 2005-04-01 |
HK1045853B (zh) | 2005-01-14 |
EP1173509B1 (en) | 2003-09-10 |
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