CN1119447A - 磷改性的环氧树脂及其制备方法和应用 - Google Patents
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Abstract
本发明涉及具有环氧值为0至1摩尔/100克的磷改性环氧树脂,包括由下列化合物衍生的结构单元:(A)每分子具有至少两个环氧基的聚环氧化物,和(B)焦膦酸和/或膦酸单酯。本发明还提供了制备这种磷改性环氧树脂的方法并提供了这些树脂在生产模压件、涂料或层压制件方面的应用。
Description
本发明涉及新型的含磷环氧树脂及其制备方法和应用。该新型的含磷环氧树脂除了具有抗燃性之外,还特别易于加工,因为它们尤其具有非常好的储藏稳定性。
目前,环氧树脂大规模地应用于制备具有高质量的热、机械以及电气特性的模压件和涂料,而且还可以生产层压制件。利用各种硬化剂例如羧酸酐、胺、酚或异氰酸酯,可以使低分子量的或低聚的起始组分反应生成高级的热固性材料。环氧树脂的另一个优点是它们的加工性能。在起始状态,它们是低分子量的或低聚的,且在加工温度下具有低粘度。因此,它们非常适宜于密封复杂的电气或电子元件,而且还适用于饱和和浸渍法。在适宜的反应加速剂存在下它们具有令人满意的适用期。它们还可以用常规的无机填料充填。
为了在万一失火或事故情况下人员能得到保护,连续运转的电气或电子装置能安全地保持一定时间,在电气工程中常常需要固化的环氧树脂材料具有抗燃性能。这意味着,固化的环氧树脂材料必须具有自熄性,而且必须不使火势蔓延。详细的要求在应用于有关产品的标准中均作了规定。用于电子或电气工程的固化的环氧树脂必须首先符合UL94V的燃烧性试验要求。
关于使环氧树脂具有抗燃性的可能的方法的综述,可以在文献中查到(例如,Troitzsch,J.,“International Plastics FlammabilityHandbook”,2nd edition,Carl Hanser Verlag,Munich,1990;Yehaskel,A.,“Fire and Flame Retardant Polymers”,Noyes DataCorporation,New Jersey,USA,1979)。
目前,通常采用含卤素的,特别是含溴的芳族组分使环氧树脂具有抗燃性。上述树脂通常含有填料或玻璃纤维且通常含有作为增效剂的三氧化锑。这种树脂的问题在于,万一偶然发烟或燃烧会产生腐蚀,且在不利的条件下会产生生态学或毒物学上不安全的分解产物。因此,大量技术工作的精力都花费在采用焚化的安全处置上。
因此,非常需要一种能达到标准中要求的抗燃性而又不添加卤化组分的环氧树脂。
已发现了一种在树脂类基材中使用有机磷化合物实现抗燃性的有效方法。因此,已试验了采用基于磷酸脂类例如磷酸三苯酯的添加剂使环氧树脂改性(DE 1,287,312)。然而,这些化合物特别是在高温下往往从固化材料中迁移到表面上,影响介电性且导致电腐蚀。
具有化学键合磷的环氧树脂可以通过将工业环氧树脂与各种磷酸的P—OH基团反应而制得,P—OH基团被加成到环氧乙烷环上且同时引起部分环氧聚合。这样,就产生磷改性的环氧树脂,它仍然具有活性并且在固化时结合到网络中。
用磷酸、磷酸脂和焦磷酸二酯作为酸性交联剂交联环氧树脂的实例在美国专利US 2,541,027中作了叙述。这里,首先制备了部分相应的反应产物,这些反应产物随后进行交联。这些反应产物的储藏性能不稳定。类似的产物事实上按催化剂的量用作环氧树脂固化的加速剂(法国专利FR 2,008,402)。
用膦酸交联环氧树脂的研究也已公开(ZA专利6805283)。
美国专利US 4,613,661还公开了磷酸单酯和环氧树脂的反应产物,它仍含有自由环氧基且能用常规的交联剂固化。这些产物对某些油漆和涂料系统是很重要。
因此,本发明的目的是提供磷改性的环氧树脂,该环氧树脂除了具有抗燃性之外,还具有高度的储藏稳定性,可以改变磷含量,其制备方法简单、便宜,而且还特别适用于通常要求填料含量高的电子和电气工程。
本发明提供了具有环氧值为0至约1摩尔/100克的磷改性环氧树脂,它包括由下列化合物衍生的结构单元(A)每分子具有至少两个环氧基,优选末端环氧基的聚环氧化物,和(B)焦膦酸和/或膦酸单酯。
本发明还提供了制备这类磷改性环氧树脂的方法以及它们在生产模塑件、涂层和层压制件(复合材料)中的应用,以及这些制件本身。
本发明的磷改性环氧树脂,根据环氧树脂的不同,以该树脂为基准,一般具有约0.5—13%(以重量计)的磷含量,这种磷含量可以按聚环氧化物与焦膦酸/膦酸单酯的摩尔比的需要确定。此外,采用的环氧树脂的官能度应符合每分子磷改性环氧树脂平均有至少一个环氧基、优选1—3个环氧基的要求。
本发明的磷改性环氧树脂优选的磷含量以树脂为基准为约1—8%(以重量计),特别优选约2—5%(以重量计)。它们优选为可固化的。它们优选每分子平均含至少一个环氧基,特别优选1—3个环氧基;因此,平均官能度优选至少为1,特别优选1—3。环氧值优选为约0.02—1摩尔/100克,特别优选约0.02—0.6摩尔/100克。此外,本发明的磷改性环氧树脂通常具有平均分子量
Mn(数均分子量;采用凝胶色谱法测定;聚苯乙烯标准)至多为约10,000,优选约200—5000,且特别优选约400—2000。
结构单元(A)的平均分子量
Mn(数均分子量;同样采用凝胶色谱法测定;聚苯乙烯标准)通常至多约为9000,且优选约150—4000,特别优选约300—1800;它们最好是由每分子平均具有2—6环氧基(官能度2—6)的聚环氧化物衍生的。这些聚环氧化物优选基于芳族胺的聚缩水甘油醚、多元酚、这些酚和/或酚醛清漆的氢化产物(参阅下文)。
结构单元(B)最好是式(I)的焦膦酸衍生的式中R1为具有1—10个碳原子的烃基,优选1—6个碳原子,它们可以具有脂族和/或芳族特性且可以被杂原子或杂原子基团间隔,优选饱和的或不饱和的、直链或支链的脂族基团,例如烷基、链烯基、环烷基,优选具有1—8个碳原子,特别优选1—6个碳原子,例如甲基、乙基、正和异丙基、正、异和叔丁基、各种戊基和己基,或芳基或芳烷基,例如未取代的苯基或优选被具有1—6个碳原子的1—3个烷基取代的苯基,或例如在烷基中具有1—6个碳原子苯烷基,例如苄基。
最好,结构单元(B)可由式(II)的膦酸单酯衍生:其中R1定义同式(I),R2是具有1—6个碳原子的烷基,优选C1—C4烷基、尤其是C1或C2烷基。
本发明磷改性的环氧树脂除了抗燃性之外,还特别具有良好的储藏稳定性。
以在室温和大气相对湿度至多50%的情况下,96小时后环氧值的变化表示的储藏稳定性,以起始值100%为基准通常不低于90%,优选变化范围在95—100%之间。
本发明磷改性环氧树脂的制备可以按如下进行,例如将聚环氧化物(A)与焦膦酸和/或膦酸单酯(B)反应,优选在惰性溶剂(稀释剂)中或,采用改进的反应方法,以及不用溶剂/稀释剂。
根据本发明所用的优选不合卤素的聚环氧化物可以是饱和的或不饱和的,且可以是脂族、环脂族、芳族和/或杂环的。此外,它们可以含有在混合或反应条件下不造成任何干扰副反应的取代基,例如烷基或芳基取代基,醚基或类似的基团。也可以使用各种聚环氧化物的混合物。这些聚环氧化物的平均分子量
Mn至多约9,000,但一般为150—4,000,优选300—1,800。
这些聚环氧化物优选具有式(III)结构:其中:n=1—5的整数,优选1—3;m=1—5的整数,优选1—3,n+m之和必须为2—6的整数,优选2—4。R2是以下(n+m)价基团—聚醚、聚醚多醇、聚酯或聚酯多醇;—烃基,它们可以具有饱和的或不饱和的脂族特性和/或芳族特性,且可以被杂原子间隔和/或含杂原子,例如氧和氮,以及杂原子基团例如—NR1CO—(R1的定义同上),这些烃基通常含至少6个碳原子,优选至少12—30个碳原子,优选含芳基,特别优选苯基,它们可以是被取代的,但优选未取代的;—环氧化合物与多胺、多醇、聚己酸内酯多醇、含OH—的聚酯、聚醚、聚二醇、羟基—、羧基—和氨基官能的聚合物油、聚羧酸、羟基—或氨基官能的聚四氢呋喃的反应产物。R2也可是一些上述的基团。R2优选下列相应的基团:双酚—A—二环氧甘油醚、双酚—F二醛清甘油醚或其低聚物、酚/甲醛或甲酚/甲醛酚醛清漆的聚缩水甘油醚、四氢化邻苯二甲酸、邻苯二甲酸、间苯二酸或对苯二环氧甲酸的二环氧甘油酯以及这些基团的混合物。
—CH2—R5—CH2—(R5=(CH2)r,或亚环己基(IIIg)其中R4是氢和/或C1—C10烷基,n和m定义如上,p是0或1,q是整数0—40、优选0—10,r是整数4—8。
例如,这些聚环氧化物是基于多羟基的优选二羟基的醇、酚、这些酚的氢化产物和/或酚醛清漆(一元酚或多元酚例如酚和/或甲酚与醛特别是甲醛在酸性催化剂存在下的反应产物)的聚缩水甘油醚,它们是按已知的方法,例如通过相应的多元醇与表氯醇反应制得的。
可以在此提及的多元酚的实例是:间苯二酚、氢醌、2,2—双(4—羟基苯基)丙烷(双酚A)、二羟基二苯基甲烷的异构体混合物(双酚F)、4,4′—二羟基二苯基环己烷、4,4′—二羟基—3,3′—二甲基二苯基丙烷、4,4′—二羟基二苯基、4,4′—二羟基二苯甲酮、双(4—羟基苯基)—1,1—乙烷、双(4—羟基苯基)—1,1′—异丁烷、双(4—羟基—叔丁基—苯基)—2,2—丙烷、双(2—羟基萘基)甲烷、1,5—二羟基亚萘基、三(4—羟基苯基)甲烷、1,1′—氧双(4—羟基苯基)。双酚A和双酚F是本发明优选的。
多元脂族醇的聚缩水甘油醚也适宜于作为聚环氧化物。这些可以提及的多元醇的实例是1,4—丁二醇、1,6—己二醇、聚亚烷基二醇、丙三醇、三羟甲基丙烷、双(4—羟基环己基)—2,2—丙烷和季戊四醇。
另一些适宜的聚环氧化物是(聚)缩水甘油酯,它们是通过表氯醇或类似的环氧化合物与脂族的、环脂族的或芳族的多羧酸例如草酸、己二酸、戊二酸、邻苯二甲酸、间苯二酸、对苯二甲酸、四氢化邻苯二甲酸或六氢化邻苯二甲酸、2,6—萘二甲酸和二聚脂肪酸的反应制得的。这些酯的实例是对苯二甲酸二环氧丙酯和六氢化邻苯二甲酸二环氧丙酯。
在某些情况下采用下述聚环氧化物也是有利的,在该聚环氧化物中,环氧基无规地分布在分子链上;且该聚环氧化物可用含有这些环氧基的烯属不饱和化合物例如丙烯酸或甲基丙烯酸的缩水甘油酯通过乳液聚合进行制备。
另一些可以采用的聚环氧化物是,例如基于杂环系的聚环氧化物,例如海因环氧树脂、异氰脲酸三缩水甘油酯和/或它的低聚物、三缩水甘油基—p—氨基苯酚、三缩水甘油基—p—氨基二苯醚、四缩水甘油基二氨基二苯甲烷、四缩水甘油基二氨基二苯醚、四(4—缩水甘油氧苯基)乙烷、尿唑环氧化物、尿嘧啶环氧化物、噁唑烷酮—改性的环氧树脂。此外,基于芳族胺例如苯胺的聚环氧化物,例如N,N—缩水甘油苯胺、二氨基二苯甲烷和N,N′—二甲基氨基二苯甲烷或—二苯基I砜。另一些适宜的聚环氧化物叙述于“Handbook ofEpoxy Resins”by Henry Lee and Kris Neville,McGraw—HillBook Company,1967,in the monograph by Henry Lee“EpoxyResins”,American Chemical Society,1970,in Wagner/Sarx,“Lackkunstharze”,Carl Hanser Verlag(1971),pp.174 ff,in“Angew.,Makromol.Chemie”,Volume 44(1975),PP.151—163,in DE—A 2,757,733 and in EP—A 0,384,939,这些文献在此并入本文作为参考。
优选采用的聚环氧化物是基于双酚A、双酚F和双酚S(这些双酚和表氯(卤)醇的反应产物)的二环氧甘油醚或其低聚物、酚/甲醛和/或甲酚/甲醛酚醛清漆的聚缩水甘油醚以及邻苯二甲酸、间苯二酸、对苯二甲酸、四氢化邻苯二甲酸和/或六氢化邻苯二甲酸以及偏苯三酸的环氧甘油酯、芳胺和杂环氮碱的N—缩水甘油基化合物如N,N—二缩水甘油基苯胺、N,N,O—三缩水甘油基—p—氨基苯酚、三缩水甘油基异氢脲酸酯和N,N,N′,N′—四缩水甘油基双(对氨基苯基)甲烷,海因环氧树脂和尿嘧啶环氧树脂以及多元脂族醇(如丁二醇,三羟甲基丙烷和聚亚烷基二醇)的二—和多缩水甘油化合物。此外,噁唑烷二酮—改性的环氧树脂也合适。这类化合物是已知的(见:“Angew.Makromol.Chem”,44卷(1975),第151—163页,及美国专利3334110);这里可提到的一个例子是双酚A二环氧甘油醚与二异氰酸二苯基甲烷在合适的加速剂存在下的反应产物。在制备磷改性的环氧树脂中,聚环氧树脂可单独存在,也可以呈混合物的形式。所用的聚环氧树脂优选是环氧化酚醛清漆。
用于与聚环氧化物反应的焦膦酸最好具有式I结构。代表例是甲基焦膦酸,丙基焦膦酸,丁基焦膦酸和苯基焦膦酸。
优选具有式(II)结构的合适的膦酸单酯的例子是:甲基膦酸单甲酯,乙基膦酸单乙酯,丙基膦酸单乙酯和苯基膦酸单甲酯。
举例来说,通过已知方法(例如参见Houben—Weyl,Methodender organischen Chemie,第4版,XII/1(1963),606页)使膦酸脱水来制备式(I)的焦膦酸酐。通过部分水解相应的膦酸二酯、尤其是用氢氧化钠溶液(见:“J.Organometallic Chem.”12卷(1960),459页)或用相应的醇部分酯化游离的膦酸制备膦酸单酯。
变化聚环氧化物与焦磷酸或磷酸单酯的当量比可调节本发明磷改性的环氧树脂的磷含量。通常,聚环氧化物和焦膦酸和/或膦酸单酯的当量比为1∶0.1—1∶1,优选1∶0.1—1∶0.8,特别是1∶0.1—1∶0.4。
如果在本发明的方法中使用溶剂(稀释剂),则它们是质子惰性的,最好具有极性。其例子有N—甲基吡咯烷酮;二甲基甲酰胺;醚,如乙醚,四氢呋喃,二恶烷,具有支链或非支链C1—C6烷基的单醇的乙二醇一或二醚、丙二醇一或二醚、丁二醇一或二醚;酮,如丙酮,甲乙酮,甲基异丙基酮,甲基异丁基酮,环己酮和类似的酮;酯,例如乙酸乙酯、乙酸丁酯、乙酸乙二醇酯、乙酸甲氧基丙酯;卤代烃类;(环)脂族和/或芳族烃例如己烷、庚烷、环己烷、甲苯、各种二甲苯以及沸程为约150—180℃的芳族溶剂(高沸点矿物油的馏分例如Solvesso)。这些溶剂可以单独使用或以混合物形式使用。
聚环氧化物与焦膦酸和/或膦酸单酯的反应通常发生于温度-20至130℃,优选20—90℃。
本发明的磷改性的环氧树脂具有良好的抗燃性和高的储藏稳定性;它们允许改变磷含量,并可简单廉价地制备。它们可有利地用于许多应用领域制备模塑件、半固化片、涂层或层合体(复合材料),尤其是用于电气工程绝缘。例如,它们适用于覆盖、涂覆和屏蔽电子部件,适用于电绕组绝缘,适用于生产绝缘元件以及掺入纤维成分的复合材料,特别是用于印刷线路板的层压件。
以下用实施例更具体地介绍本发明的实施方案。
实施例
通过使溶于甲乙酮中的环氧化酚醛清漆(环氧值:0.56mol/100g,平均官能度:3.6)与焦膦酸和两种不同的膦酸单酯反应来制备磷改性的环氧树脂。在该反应中,溶液在100℃油浴温度回流搅拌90分钟。
溶液的组成如下:a)440pbm(质量份)酚醛清漆,170pbm甲乙酮和60pbm丙基焦膦酸;b)400pbm酚醛清漆,170pbm甲乙酮和70pbm丙基膦酸单乙酯;c)400pbm酚醛清漆,156pbm甲乙酮和56pbm甲基膦酸单甲酯。
反应产物号a),b),c)的性质如下:a)环氧值(0小时和96小时后):0.35/0.34mol/100g,磷含量3.3%;b)环氧值(0小时和96小时后):0.36/0.34mol/100g,磷含量3.4%;c)环氧值(0小时和96小时后):0.38/0.37mol/100g,磷含量3.4%。
Claims (17)
1.一种具有环氧值为0至1摩尔/100克的磷改性环氧树脂,包括由下列化合物衍生的结构单元(A)每分子具有至少两个环氧基的聚环氧化物,和(B)焦膦酸和/或膦酸单酯。
2.根据权利要求1的磷改性环氧树脂,其中以该树脂为基准,磷含量为0.5—13%(以重量计)。
3.根据权利要求1或2的磷改性环氧树脂,其中环氧值为0.02—1摩尔/100克。
4.根据权利要求1—3中任一项或多项的磷改性环氧树脂,该树脂每分子平均含至少一个环氧基。
5.根据权利要求1—4中任一项或多项的磷改性环氧树脂,其中该树脂的平均分子量
Mn为200—5000。
6.根据权利要求1—5中任一项或多项的磷改性环氧树脂,其中结构单元(A)平均分子量
Mn为150—4000。
7.根据权利要求1—6中任一项或多项的磷改性环氧树脂,其中结构单元(A)由每分子具有2—6环氧基的聚环氧化物衍生。
8.根据权利要求1—7中任一项或多项的磷改性环氧树脂,其中结构单元(A)由基于多元酚、这些酚的氢化产物和/或酚醛清漆的聚缩水甘油醚衍生。
10.根据权利要求9的磷改性环氧树脂,其中R1是C1—C10、优选C1—C6烷基、芳基、优选苯基或芳烷基。
12.根据权利要求11的磷改性环氧树脂,其中R1是C1—C10烷基、优选C1—C6烷基,芳基,优选苯基或芳烷基。
13.一种制备如权利要求1—12中一项或多项的磷改性环氧树脂的方法,该方法包括在情性稀释剂中或在不存在稀释剂/溶剂的条件下,使聚环氧化物(A)和焦膦酸和/或膦酸单酯(B)相互反应。
14.根据权利要求13的方法,其中该反应在温度-20至130℃下进行。
15.根据权利要求13或14的方法,其中聚环氧化物与焦膦酸和/或膦酸单酯的当量比为1∶0.1至1∶0.8。
16.权利要求1—12中一项或多项磷改性环氧树脂或权利要求13—15中一项或多项获得的磷改性环氧树脂用于生产模塑件、涂层或层压件、优选用于电气工程的用途。
17.使用权利要求1—12中一项或多项的磷改性环氧树脂或按照权利要求13—15中一项或多项获得的膦改性环氧树脂制得的模塑件、涂层或层压件。
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-
1993
- 1993-03-15 DE DE4340834A patent/DE4340834A1/de not_active Withdrawn
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1994
- 1994-03-10 KR KR1019950703868A patent/KR100304600B1/ko not_active IP Right Cessation
- 1994-03-10 KR KR1019950703897A patent/KR960701118A/ko not_active Application Discontinuation
- 1994-03-10 PL PL94310629A patent/PL175777B1/pl unknown
- 1994-03-10 AT AT94911149T patent/ATE154369T1/de not_active IP Right Cessation
- 1994-03-10 PL PL94310630A patent/PL176714B1/pl unknown
- 1994-03-10 JP JP6520606A patent/JPH08507813A/ja active Pending
- 1994-03-10 EP EP94911149A patent/EP0689559B1/de not_active Expired - Lifetime
- 1994-03-10 JP JP6520607A patent/JPH08507814A/ja not_active Ceased
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- 1994-03-10 HU HU9502639A patent/HU214671B/hu not_active IP Right Cessation
- 1994-03-10 EP EP94911874A patent/EP0689560A1/de not_active Withdrawn
- 1994-03-10 CN CN94191463A patent/CN1046949C/zh not_active Expired - Fee Related
- 1994-03-10 WO PCT/EP1994/000750 patent/WO1994021706A1/de active IP Right Grant
- 1994-03-10 RU RU95121947A patent/RU2126426C1/ru active
- 1994-03-10 CA CA002158366A patent/CA2158366A1/en not_active Abandoned
- 1994-03-10 CZ CZ952400A patent/CZ240095A3/cs unknown
- 1994-03-10 RU RU95121641A patent/RU2116323C1/ru active
- 1994-03-10 HU HU9502671A patent/HU213902B/hu not_active IP Right Cessation
- 1994-03-10 DE DE59403119T patent/DE59403119D1/de not_active Expired - Fee Related
- 1994-03-10 CA CA002158362A patent/CA2158362A1/en not_active Abandoned
- 1994-03-10 CZ CZ19952246A patent/CZ287737B6/cs not_active IP Right Cessation
- 1994-03-10 CN CN94191474A patent/CN1119447A/zh active Pending
- 1994-03-10 WO PCT/EP1994/000749 patent/WO1994021705A1/de not_active Application Discontinuation
- 1994-04-21 TW TW083103561A patent/TW261623B/zh active
- 1994-04-21 TW TW083103560A patent/TW261622B/zh active
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101880507A (zh) * | 2010-07-02 | 2010-11-10 | 石家庄市金达特种涂料有限公司 | 一种膨胀型水性防火清漆及制备方法 |
CN101880507B (zh) * | 2010-07-02 | 2013-03-13 | 石家庄市金达特种涂料有限公司 | 一种膨胀型水性防火清漆及制备方法 |
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