CN1157625A - 磷改性的环氧树脂，其制造方法和用途 - Google Patents

磷改性的环氧树脂，其制造方法和用途 Download PDF

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CN1157625A
CN1157625A CN95195033A CN95195033A CN1157625A CN 1157625 A CN1157625 A CN 1157625A CN 95195033 A CN95195033 A CN 95195033A CN 95195033 A CN95195033 A CN 95195033A CN 1157625 A CN1157625 A CN 1157625A
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J·修比尔
H·卡皮特兹
H-J·克勒尔
W·罗格尔
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Abstract

本发明有关化学式(I)和/或(II)的磷改性的环氧树脂。此外本发明的对象是这种磷改性的环氧树脂的制造方法和它用于制造模制体，涂层或层压制品的应用。

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磷改性的环氧树脂，其制造方法和用途
本发明涉及新的磷改性的环氧树脂，它的制造方法和用途。新的磷改性的环氧树脂以其作为具有极好的可加工性的阻燃添加剂为著称。
当今环氧树脂广泛地应用于制造具有高水平的热、机械和电性能的反应性树脂模制材料和涂层和制造层压制品。低分子量或低聚体的原料可使用不同的硬化剂，例如羧酸酐、胺、酚或异氰酸酯等，或通过离子型聚合转化成高质量的热固性塑料。环氧树脂的另一优点是它的可加工性能。在原始状态它们是低分子或低聚物和在加工温度显示低粘度，因此它们特别适用于浇铸复杂的电子和电气元件以及用于浸渍和浸轧工艺过程。在适用的反应加速剂存在下它显示足够的使用寿命。用普通的无机惰性填料它具有高度可填充性。
为了在火灾和事故中保护有关人员以及确保电气或电子仪器的功能维持一定时间，目前在电工技术中对环氧树脂模制材料(固化的环氧树脂)常常提出阻燃的要求。亦即环氧树脂模制材料必须能自灭和不使火灾继续漫延。详细的要求在各个有关产品的标准中有说明。在电子学和电工技术采用的环氧树脂模制材料的可燃性测试主要按照UL94V。
环氧树脂的阻燃标定的可能方法归纳在文献中(例如Troitzsch，J.，“International Plastics Flamanability Handbook”，2nd edition，CarlHamser Verlag，München，1990；Yehaskel，4.，“Fire and Flame RetardantPolymer”，Noyes Data Corporation，New Jersey，USA，1979)。
目前环氧树脂模制材料一般采用含卤，特别是含溴的芳族组分进行阻燃整理。大多是含有夹层组分的例如含填充材料的或含玻璃织物的模制材料，它往往含有三氧化二锑作为协同剂。这里的问题是，在事故中由于阴燃和燃烧生成腐蚀性分解产物和在不合适的条件下生成生态上和毒物学上不可接受的分解产物。对于无害的通过燃烧处理这些产物在技术上要投入可观的费用。
因此对环氧树脂有很大需求，这些树脂不添加含卤组分可达到标准所要求的难燃性。
作为使树脂状的基质达到阻燃性的有效方式，提出了应用有机磷化合物。曾经试验过的有，环氧树脂用以磷酸酯为基础的添加剂，例如三苯基磷酸酯进行改性(DE 1 287 312)。然而在升高的温度时这些化合物会从模制材料迁移至表面和导致影响介电性能和造成E-腐蚀。
因此本发明的任务是，提供用于环氧树脂新的含磷添加剂，它除了阻燃性外还具有很好的存放稳定性，允许改变磷含量，生产简单和成本合适和尤其是也适用于高填充材料含量普通的电子学和电工技术。
本发明涉及化学式(I)和/或化学式(II)新的磷改性环氧树脂：
Figure A9519503300062
其中：
R1，R2和R3是表示相互独立的含有1至20个碳原子，优选1至10个碳原子的烃基；
R4是表示含缩水甘油基的聚环氧化合物，优选为二环氧化合物减去缩水甘油基后的基团；
m表示2至6，优选2至4和尤其是2的整数。
此外本发明还涉及这种磷改性环氧树脂的制造方法以及涉及用于制造模制体，涂层和层压制品(复合材料)的用途和这些物体本身。
按本发明磷改性的环氧树脂一般具有平均分子量 Mn(数均，用凝胶色谱法测定；聚苯乙烯为标准物)至约10,000，优选是从约200至5000和特别是约从400至2000。
在上式(I)或(II)中R1、R2和R3优选是代表烃基，它具有脂肪族和/或芳族的特性和它可被杂原子或杂基团间隔，特别是代表饱和的或不饱和的，直链的或支链的脂肪族基，如烷基，链烯基，环烷基，优选是具有1至8个碳原子，尤其是1至4个碳原子，如甲基，乙基，正-或异-丙基，正-，异-或叔-丁基。此外这些基也可代表芳基或芳烷基，如不取代的或优选是被1-3个具有1至6个碳原子的烷基取代的苯基或萘基或如在烷基中带有1至6个碳原子的苯基烷基，例如苄基。
R4在化学式(I)/(II)中优选是代表减去缩水甘油基的
-聚醚，聚醚多醇，聚酯或聚酯多醇；
-烃基，它具有饱和的或不饱和的脂肪族特性和/或芳烃特性和此烃基被杂原子如氧和氮，以及被杂基团，如-NR1CO-(R1如同上述意义)间隔和/或可含有这些杂原子或杂基团，在此这些烃基一般至少有6个，优选至少含有12-30个碳原子；优选是芳基，特别是苯基，它可以是取代的，但优选是不取代的；或
-环氧化合物与多胺，多醇，聚己内酯多醇，含羟基的聚酯，聚醚，聚二醇，羟基-，羧基-和氨基功能的聚合物油，聚羧酸，羟基-或氨基功能的聚四氢呋喃的反应产物。R4也可代表这些不同的基。
R4特别是表示双酚-A-二缩水甘油醚，双酚-F-缩水甘油醚或它们的低聚物相应的基，或四氢化苯二酸，邻苯二酸，间苯二酸或对苯二酸的二缩水甘油酯相应的基以及这些基的混合物。
R4也可表示苯酚/甲醛-以及间苯二酚/甲醛-酚醛清漆的聚缩水甘油醚。
下面是用化学式表示这些R4基：
Figure A9519503300082
Figure A9519503300084
在其中指数m意义如上述，q是0至40的整数，优选是代表0至10，指数p表示0或1和R5是氢和/或为C1至C10-烷基。
R4完全特别是表示(IIIa)，亦即特别优选的磷改性环氧树脂具有化学式(I’)和(II’)
Figure A9519503300091
按本发明磷改性的环氧树脂各按制造方法和加入的膦酸酐/次膦酸酐的纯度还含有一定量的，最多不超过30％(重量)，优选是不超过20％(重量)的其它结构单元，以总的混合料为基础。这种副产物以上面给定的量对本发明产品的外观没有实质性影响，通常它甚至对阻燃作用还有贡献。
按本发明的磷改性的环氧树脂，如上面已叙述过，特征是特别有良好的存放稳定性。
用在室温中和在相对空气湿度最大为50％在96小时后环氧值的变化来表达存放稳定性。以起始值100％为基础，一般环氧值不会低于90％，优选在约95％至100％范围内变化。对一些按本发明磷改性的树脂，这个值只有通过混入下式(VI)的无磷的环氧树脂达到，优选是用于制造按本发明化合物的同样树脂。
按本发明磷改性的环氧树脂的制造可适当的通过化学式(IV)的膦酸酐和/或化学式(V)的次膦酸酐与化学式(VI)的聚环氧化合物在一惰性溶剂(稀释剂)或使用适宜的反应程序时也可在本体中进行反应来完成，
Figure A9519503300101
其中R1，R2和R3的意义如同上述和z代表至少3，优选是3至10和尤其是3，
Figure A9519503300102
其中R4以及指数m同样与上述意义相同。
作为化学式(IV)的膦酸酐例如可考虑：甲烷膦酸酐，乙烷膦酸酐，正-和/或异-丙烷膦酸酐，己烷膦酸酐，苯膦酸酐和甲苯基膦酸酐或相应的混合物。
这种膦酸酐的制备例如在EP公开说明书0004323中有叙述。此外在有机化学((1993)第XII/1卷612页上(Heuben-Weyl，Meth.d.Organ.Chem.(1963).Bd XII/1.Seit612)以及在DE公开说明书2758580和4126235中均有介绍。
化学式(IV)的次膦酸酐这里有：二甲基次膦酸酐，乙基甲基次膦酸酐，二乙基次膦酸酐，二丙基次膦酸酐，甲基苯基次膦酸酐，二苯基次膦酸酐，二-对甲苯基次膦酸酐和二-对甲氧基苯基次膦酸酐。
次膦酸酐的制造例如在DE公开说明书2129583中有叙述。
按本发明采用的酸酐各按其制造方法可含一定量的游离酸，但一般不超过20％(重量)，优选不超过15％(重量)，和尤其不超过10％(重量)。
优选采用的聚环氧化合物如化学式(VI)是以双酚A，双酚F和双酚S为基础的双-脱水甘油醚(为这种双酚和环氧氯(卤)丙烷的反应产物)或它们的低聚物和邻苯二酸，间苯二酸，对苯二酸，四氢邻苯二酸和/或六氢邻苯二酸的二缩水甘油酯。其它适用的聚环氧化合物在“环氧树脂手册”(“Handbook of Epoxy Resins”von Henry lee und Kris Neville，McGraw-Hill Book Company，1967)和在“环氧树脂”单行本(dieMonographie von Henry Lee“Epoxy Resins”，American Chemical Society1970)“人造油漆树脂”(Wagner/Sarx，“Lackkunstharze”，Carl HamserVerlag(1971)S，174ff，“应用高分子化学”(“Angew，Makromol.Chemie”Bd.44(1975)seite151-163)，DE公开说明书2757733，EP公开说明书0384939以及在德国专利申请p4308185.1中均有介绍；引入这些文献可供参考。
如果在本发明的方法中采用溶剂(稀释剂)，则它是质子惰性的和优选具有极性。例如这些溶剂是：N-甲基吡咯烷酮；二甲基甲酰胺；醚，如二乙醚，四氢呋喃，二氧六环，必要时带有1至6个碳原子的支化烷基的一元醇形成的乙二醇单-或二醚，丙二醇单-或二醚，丁二醇单-或二醚；酮，如丙酮，甲乙酮，甲基异丙基酮，甲基异丁基酮，环己酮和类似物质；酯，如乙酸乙酯，乙酸丁酯，乙酸乙二醇酯，乙酸甲氧基丙基酯；卤代烃；脂(环)族和/或芳香族烃，如己烷，庚烷，环己烷，甲苯，各种二甲苯以及沸点范围从约150-180℃的芳烃溶剂(较高沸点的矿物油馏分，如solvesso)。在此溶剂可单独或混合使用。
通式为(V)的缩水甘油醚与酸酐的反应通常在温度从-20℃至170℃，特别在20-130℃进行。
按本发明的磷改性的环氧树脂可有利的作为阻燃添加剂在许多应用领域用于制造模制体、预浸渍体、涂层或层压制品(复合材料)，特别是在电子工程用作绝缘目的。在此这种磷改性树脂中混入含量至80％(重量)、优选至50％(重量)的无磷环氧树脂。作为固化剂可采用已知的环氧树脂固化剂，如在DE公开说明书2743680或在EP公开说明书274646中已有叙述。例如这些材料适用于作电子元件的复盖层，涂层和包封，用于电线圈的绝缘，用于制造绝缘元件和与纤维状的填充组分制造复合材料，特别是制造层压制品用于印刷电路板技术。
以下实施例进一步解释本发明：实施例1
将250g环氧树脂，它是通过2摩尔环氧氯丙烷与含有环氧当量从180至192的1摩尔2，2-双(4-羟苯基)-丙烷(双酚A)反应制造的(Beckopox EP140，Epoxidharz von Hoechst)，加热至40℃，将281g(1.32摩尔)的丙烷膦酸酐(在乙酸乙酯中的50％的溶液)在90分钟内滴加入。此反应是放热的。然后搅拌1小时和接着回流16个小时。
折射率：nD 20：1.4950
粘度：(用Hoppler-粘度计测试)：2566mPa·S[25℃]。实施例2
50g环氧树脂，它是通过2摩尔环氧氯丙烷与1摩尔2，2-双(4-羟苯基)-丙烷(双酚A；环氧树脂D、E、R332 Dow环氧树脂)进行反应制造的，和31.5g(0.159摩尔)乙基甲基次膦酸酐在150℃搅拌6小时；然后继续加入20g(0.1摩尔)乙基甲基次膦酸酐和继续在150℃搅拌16小时。冷却后与乙酸乙酯制成75％的溶液。
折射率：nD 22：1.4870
粘度(用Hppler-粘度计测试)：80mPa·S[25℃]。实施例3
预浸渍体的制备
a)由150g实施例1的反应产物制成的溶液与195g环氧化的酚醛树脂(环氧值：0.56摩尔/100g)，65g具有胺含量为9.35％的多胺，0.7g 2-甲基咪唑在140g甲乙酮和40g二甲基甲酰胺中进行混合(树脂基质的磷含量为3.1％)。此多胺通过由甲苯-2，4-二异氰酸酯和甲苯-2，6-二异氰酸酯混合物的三聚反应和随后水解(得到NH2值为9.35％的产物)制得。
b)用按a)得到的溶液将玻璃布(玻璃布型号7628，单位面积重197g/m2)借助于实验室浸渍装置连续进行浸渍和在一垂直干燥装置中在温度为50-160℃下进行干燥。这样制得的预浸渍体具有的剩余胶凝时间为123秒和此预浸渍体不粘，在室温(最高为21℃和最大相对空气湿度为50％)具有存放稳定性。实施例4
层压制品的制造和测试
将8个按例3制成的预浸渍体放在一个层压机中在175℃和35巴进行冲压。在40分钟后从层压机中取出厚度为1.6mm的层压制品，随后在200℃恒温2小时。用此方法得到的层压制品的Tg为180℃(DMTA)和按UL94V测得的平均燃烧时间为3.8秒，它相当于V-O等级。
用于电工技术的热固性塑料必须是难燃的。对这种材料的阻燃要求大多是按照UL 94V-O。对这种材料的测试是将测试物体垂直靠在下边缘上用一规定的火焰燃烧。10次测试的燃烧的时间总数不能超过50秒。

Claims (9)

1.化学式(I)和/或化学式(II)的磷改性的环氧树脂
Figure A9519503300021
Figure A9519503300022
其中：
R1、R2和R3是相互独立为带有1至20个碳原子，优选是1至10个碳原子的烃基。
R4是表示含缩水甘油基的聚环氧化合物减去缩水甘油基后的基团，
m表示2-6的整数，优选是2-4的整数。
2.按权利要求1磷改性的环氧树脂，其特征是，R1、R2和R3各代表一个带有1至8个碳原子，优选1至4个碳原子的脂肪族基。
3.按权利要求1或2的磷改性的环氧树脂，其特征是，R4代表含有两个缩水甘油基的聚醚，聚醚多醇，聚酯和/或聚酯多醇减去二个缩水甘油基后的基团。
4.按权利要求1至3的一项或多项的磷改性的环氧树脂，其特征是，R4是代表下式基团，在其中q表示0-40的整数，优选表示0-10的整数。
5.按权利要求1至4的一项或多项的磷改性的环氧树脂，其特征是，它的平均分子量 Mn在200和5000之间。
6.按权利要求1至5的一项或多项的磷改性环氧树脂的制造方法，其特征是，将化学式(IV)的膦酸酐和/或化学式(V)的次膦酸酐
Figure A9519503300032
在其中R1，R2和R3意义同上述和z代表至少3，优选是3至10，与化学式(VI)的聚环氧化合物在其中R4及指数m同样如同上述意义，在一惰性溶剂或按照适当的反应程序在本体中反应。
7.按权利要求6的方法，其特征是，反应是在温度为-20℃至170℃进行。
8.按权利要求1至5的一项或多项的磷改性环氧树脂或按权利要求6或7的一项得到的磷改性的环氧树脂的应用，必要时与无磷环氧树脂混合，用于制造模制体，涂层和层压制品，优选是应用在电子技术上。
9.使用按权利要求1至5的一项和多项或按权利要求6或7的一项得到的磷改性的环氧树脂制造的模制体，涂层或层压制品。
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