CN112538155A - 一种含磷无卤环氧树脂及其制备方法和应用 - Google Patents

一种含磷无卤环氧树脂及其制备方法和应用 Download PDF

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CN112538155A
CN112538155A CN202011201647.2A CN202011201647A CN112538155A CN 112538155 A CN112538155 A CN 112538155A CN 202011201647 A CN202011201647 A CN 202011201647A CN 112538155 A CN112538155 A CN 112538155A
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张久久
陈儒
周国荣
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Kingboard Jiangsu Chemical Co ltd
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Abstract

本发明涉及一种含磷无卤环氧树脂及其制备方法和应用，含磷无卤环氧树脂四步反应而成：反应1：由通式(1)和通式(4)在催化剂的作用下获得含有氮氧碳五元刚性杂环的环氧树脂A。反应2：由树脂A与通式(2)或通式(3)在膦系催化剂的作用下获得环氧树脂B。反应3：由多官能环氧树脂与具有一个与磷原子键联的活性氢原子的有机磷化合物发生反应获得含磷环氧树脂C。反应4：由树脂B和树脂C在磷系催化剂的作用下，树脂B的环氧基与树脂C的活性氢发生加成反应，生成环氧树脂D。利用该环氧树脂D加工而成的覆铜面板具有优良的柔韧性、高抗剥能力、高的玻璃软化点温度及良好工艺性。

Description

一种含磷无卤环氧树脂及其制备方法和应用
技术领域
本发明涉及一种含磷无卤环氧树脂及其制备方法和应用，本发明的含磷无卤环氧树脂具有优良的柔韧性、阻燃性、高玻璃软化点温度和加工性。
背景技术
目前，各种工业领域，如电子设备、电子元件都要在热或火焰中不燃烧的特性。因此，具有阻燃性能的含磷环氧树脂常用于覆铜面板中。环氧树脂生产中将卤素引入环氧树脂结构中，能够提供环氧树脂优异的阻燃性能。目前使用为广泛的就是含溴的环氧树脂，是制造生产电子设备和电子元件的主要环氧树脂。使用了含溴环氧树脂生产成的电子元件及电子设备在遇到燃烧或废弃燃烧处理时，这些含卤素的环氧树脂固化物会产生有毒有腐蚀气体，如卤代氢、卤素和二噁英，对人类健康带来极大的危害，造成环境污染。
当前市场上卤素以外阻燃环氧树脂主要是含磷阻燃环氧树脂，含磷环氧树脂生产阻燃的覆铜箔层压板，存在一个普遍问题是抗剥低，柔韧性差，加工性能差对无卤化的进程造成很大的影响。
专利号CN103627146B一种具有优良柔韧性含磷无卤素环氧树脂制备，该含磷无卤素环氧树脂不含任何卤素的阻燃环氧树脂和不使用溴阻燃，制成的覆铜面板具有优良的柔韧性、高抗剥及良好工艺性，解决了抗剥低、柔韧性差的问题。但是该含磷无卤环氧树脂存在环氧树脂固化物玻璃化温度Tg低的缺陷。
发明内容
本发明目的在于提供一种不含任何卤素的阻燃环氧树脂，属于含磷无卤环氧树脂，利用该环氧树脂加工而成的覆铜面板具有优良的柔韧性、高抗剥能力、高的玻璃软化点温度及良好工艺性。解决了现有含磷环氧树脂的抗剥低、玻璃软化温度低和柔韧性差的问题。
本发明解决上述问题所采用的技术方案为：
一种含磷无卤环氧树脂，其化学通式如下
Figure BDA0002755508190000021
式中，
A的结构式为
Figure BDA0002755508190000022
两端环氧键打开的结构式；
X的结构式为
Figure BDA0002755508190000023
Y的结构式为
Figure BDA0002755508190000024
式A中Z的结构式为
Figure BDA0002755508190000031
M的结构式为
Figure BDA0002755508190000032
W为DOPO(9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物)或DPPO(二苯基氧膦)，结构式为
W为
Figure BDA0002755508190000033
一种含磷无卤环氧树脂的制备方法，按如下四步反应而成
反应1：由通式(1)和通式(4)在催化剂的作用下获得含有氮氧碳五元刚性杂环的环氧树脂A。
反应2：由树脂A与通式(2)或通式(3)在膦系催化剂的作用下获得环氧树脂B。
反应3：由多官能环氧树脂(酚醛环氧树脂)与具有一个与磷原子键联的活性氢原子的有机磷化合物发生反应获得含磷环氧树脂C。有机磷化和物的W与酚醛环氧的反应只是和部分的环氧基反应，不是全部反应，但在树脂C的制备过程中有机磷化和物是全部反应的。
反应4：由树脂B和树脂C在磷系催化剂的作用下，树脂B的环氧基与树脂C的活性氢发生加成反应，生成环氧树脂D。即树脂D是树脂B和树脂C在催化剂催化下环氧基与酚羟基反应
反应中结构式
Figure BDA0002755508190000041
HO-X-OH (2)
H2N-Y-NH2 (3)
OCN-Z-NCO (4)，
式(1)(2)中X的结构式为
Figure BDA0002755508190000042
式(3)中Y的结构式为
Figure BDA0002755508190000051
式(4)中Z的结构式为
Figure BDA0002755508190000052
树脂A的结构式
Figure BDA0002755508190000053
树脂B的结构式
HO-X-O-A-X-OH或
Figure BDA0002755508190000054
树脂C的结构式：(反应3产物的结构简式)
Figure BDA0002755508190000055
n为自然正整数
Figure BDA0002755508190000064
W为
Figure BDA0002755508190000062
树脂D的结构式
Figure BDA0002755508190000063
优选地，反应1中的催化剂选自2-苯基咪唑，2-甲基咪唑，2-甲基-4乙基咪唑，1-甲基咪唑，4，4’-亚甲基咪唑，季鏻盐，季铵盐，叔胺中的一种或两种或多种混合物。环氧树脂A中通式(1)与通式(4)比例为100：(1-20)，更适合是100：(1-15)还更合适为100：(1-10)，如果比例太少生成的氮氧碳五元杂环比例不足，如果比例太大造成树脂分子量太大，影响后段反应。
优选地，反应2中，树脂A与通式(2)或通式(3)的摩尔比例为(0-1)：(2-5)，更适合是(0.5-1)：(2-4)还更合适为(0.75-1)：(3-4)，如果比例太小造成扩链不足，如果比例太大造成扩链太大，影响后段反应。
优选地，所述多官能环氧树脂选自苯酚醛环氧树脂，邻甲酚醛环氧树脂，双酚A酚醛环氧树脂，双酚F醛环氧树脂，双酚S醛环氧树脂，双酚AD醛环氧树脂中的一种或多种；所述有机磷化合物为DOPO(9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物)或DPPO(二苯基氧膦)。
优选地，反应4中，树脂B的摩尔比例为1-30％，优选为1-20％，更优选的选择在1-10之间，还更优选的选择在1-8％之间。
优选地，所述含磷催化剂为三苯基膦、三丁基膦、三甲氧基膦、三乙基膦、乙基或丁基三苯基磷酸盐中的任意一种或多种，用量为50-1000ppm,优选为650-800ppm，更优选为50-600ppm，还更优选为50-500ppm。含磷催化剂所用的溶剂为ACE、MEK、TOL、PM中的任意一种或多种。
作为本发明含磷无卤环氧树脂的应用之一，本发明的含磷无卤环氧树脂可以和环氧树脂常用的固化剂配伍，配成胶液。将玻璃纤维布放入胶液中浸湿，然后烘烤制成半固化片，然后再将若干半固化片叠配好在上和或下表面叠加金属箔(比如铜箔)，然后用压机升温压合固化，作为电子电器领域的PCB基板。
所述固化剂选自双氰胺、DDM、DDS中的一种或多种。
上述结构式中的n为自然正整数，取值5～50，优选10～40，更优选12～30。
与现有技术相比，本申请的特点在于：
(1)本申请是在专利CN103627146A的基础上作出的改进，增加了反应1，将通式(1)先与通式(4)发生加成反应，通过通式(4)的-OCN键和通式(1)的环氧键反应，获得含五元刚性杂环的环氧树脂A，由此显著提高玻璃软化温度。
附图说明
图1为本发明中基团X的化学结构式；
图2为本发明中基团Y的化学结构式；
图3为本发明中基团M和W的化学结构式。
具体实施方式
以下结合若干实施例对本发明作进一步详细描述，所述实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制，实施例用于对本发明的反应原理作进一步解释，不应理解为对本发明的限制。
实施例1：
反应1：向装有电动搅拌、回流冷凝管、温度计的圆底烧瓶中加入环氧当量为185g/eq双酚A型液体环氧树脂(通式(1))900g，通氮气保护，开动搅拌开启加热装置将树脂升温到155℃，抽真空到-0.095Mpa以下保持5分钟用氮气破真空，加入0.25g2-甲基咪唑溶解5分钟，用120分钟滴加100g熔融态的二苯甲烷二异氰酸酯(通式(4))，加完后升温到170-175℃保持反应60分钟，反应结束后抽真空到-0.095Mpa以下10分钟，通氮气破真空得到含五元杂环的环氧树脂A备用，环氧当量为250g/eq。
实施例2：
向装有电动搅拌、回流冷凝管、温度计的圆底烧瓶中加入180g双酚A(BPA)，通氮气保护，开启加热装置将BPA加热到熔融状态，开动搅拌，将温度保持在170℃～175℃之间。加入0.06g三苯基膦溶解10分钟，启动真空泵将四口圆底烧瓶中的空气抽走，抽到-0.095Mpa以下保持10分钟，通入氮气破真空。将120g环氧树脂A加热到熔融状态用梨形分液漏斗用60分钟滴加，加完后保持反应60分钟，反应结束后抽真空到-0.095Mpa以下10分钟，通氮气破真空得到树脂a，将物料流出置于有氮气的料槽中冷却、粉碎待用，羟基当量为278g/eq。
实施例3：
重复实施例2，其中BPA量改为200g，树脂A量为100g，其余皆同实施例2，得到树脂b，羟基当量为223g/Eq。
实施例4：
重复实施例2，其中BPA量改为220，树脂A为80g，其余皆同实施例2，到树脂c，羟基当量为186g/Eq。
实施例5：
重复实施例2，其中BPA改为BPF，量为200g，树脂A量为100g，其余步骤皆同实施例2，得到树脂d，羟基当量为188g/Eq。
实施例6：
向装有电动搅拌、回流冷凝管、温度计的圆底烧瓶中加入230.6g酚醛环氧树脂(F51)加热到100℃后启动搅拌，然后加入54.4gDOPO和0.07g三苯基膦，控制圆底烧瓶内温度为100℃搅拌5分钟后抽真空到-0.095Mpa以下，保持10分钟，通氮气破真空，升控温度到165-170℃，保持反应60分钟降温到120-130℃加入树脂a15g加入0.15g碘化乙基三苯基膦，抽真空到-0.095Mpa以下，保持10分钟，通氮气破真空，升温控温在175-180℃之间反应90分钟，抽真空到-0.095Mpa以下，用氮气破真空，用梨形分液漏斗加入100g丁酮，得到含磷环氧EP1，含磷量为2.6％，环氧当量为300g/Eq。
实施例7：
重复实施例6，其中树脂a更换为树脂b，其余步骤皆不改变，得到含磷环氧树脂EP2,含磷量为2.6％，环氧当量为305g/Eq。
实施例8：
重复实施例6，其中树脂a更换为树脂c，其余步骤皆不改变，得到含磷环氧树脂EP3,含磷量为2.6％，环氧当量为310g/Eq。
实施例9：
重复实施例6，其中树脂a更换为树脂d，其余步骤皆不改变，得到含磷环氧树脂EP4,含磷量为2.6％，环氧当量为310g/Eq。
对比例1：
向装有电动搅拌、回流冷凝管、温度计的圆底烧瓶中加入酚醛环氧环氧245.6g、DOPO54.4g、三苯基膦0.06g，启动升温控温各控在在100℃，搅拌10分钟后，启动真空泵将真空抽到-0.095Mpa以下，保持10分钟，用氮气破真空，加入100g丁酮到树脂中；得到对比例树脂，含磷量为2.6％，环氧当量为264g/Eq。
(六)环氧树脂的硬化和半固化片的制造：
为了控制上述实施例中制备的环氧树脂的性能，使用双氰胺【用量为100g环氧(100％固体)×21÷环氧树脂当量×0.55】作为硬化剂幷使用,2-甲基咪唑(为树脂的300ppm量)作为固化促进剂进行固化反应，用DMF作为溶剂，将胶液的固含量控制在60-65％之间。
将调配好的胶液均匀涂在玻璃钎维布上(7628型)，并在170℃干燥3分钟，获得半固化片。
取8张半固化片叠放好，上下各加一张1OZ铜箔，置于压机内用35kgf/㎝2压力，180℃热压120分钟，得到带铜箔层压板。
由表1的数据可以看出，使用了本发明的含磷无卤环氧树脂，层压板不但抗剥得到了很大的提升，热冲击得到了很大的提升，同时玻璃软化温度Tg也有所提升。由此可见本发明解决了以往含磷无卤环氧树脂玻璃软化温度低的缺点。
本发明的含磷无卤环氧树脂能提供优良的表面抗剥和层间粘结力，高的玻璃软化温度，板材获得良好的柔韧性，提高了PBC的加工性，提高了加工效率，减少品质的不良。
表1
Figure BDA0002755508190000091
Figure BDA0002755508190000101
上述实施例6中的DOPO(9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物)还可以用DPPO(二苯基氧膦)替换，效能相当。
实施例1中，二苯甲烷二异氰酸酯，还可以用对苯二异氰酸酯及其甲基取代物、间苯二异氰酸酯及其甲基取代物、正己烷、2-二甲基-4-甲基正己烷、联苯及其甲基取代物、环己烷及其甲基或异丙基取代物。
除上述实施例外，本发明还包括有其他实施方式，凡采用等同变换或者等效替换方式形成的技术方案，均应落入本发明权利要求的保护范围之内。

Claims (10)

1.一种含磷无卤环氧树脂，其特征在于：其化学通式如下
Figure FDA0002755508180000011
式中，
A的结构式为
Figure FDA0002755508180000012
两端环氧键打开的结构式；
X的结构式为
Figure FDA0002755508180000013
Y的结构式为
Figure FDA0002755508180000014
式A中Z的结构式为
Figure FDA0002755508180000021
M的结构式为
M为
Figure FDA0002755508180000022
A为H或
Figure FDA0002755508180000023
W为DOPO(9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物)或DPPO(二苯基氧膦)，结构式为
W为
Figure FDA0002755508180000024
2.一种含磷无卤环氧树脂的制备方法，其特征在于：按如下四步反应而成
反应1：由通式(1)和通式(4)在催化剂的作用下获得含有氮氧碳五元刚性杂环的树脂A,
反应2：由树脂A与通式(2)或通式(3)在磷系催化剂的作用下获得树脂B,
反应3：由多官能环氧树脂与具有一个与磷原子键联的活性氢原子的有机磷化合物发生反应获得含磷环氧树脂C,
反应4：由树脂B和树脂C在磷系催化剂的作用下，树脂B的环氧基与树脂C的活性氢发生加成反应，生成环氧树脂D；
反应中结构式
Figure FDA0002755508180000031
HO-X-OH (2)
H2N-Y-NH2 (3)
OCN-Z-NCO (4)，
式(1)(2)中X的结构式为
Figure FDA0002755508180000032
式(3)中Y的结构式为
Figure FDA0002755508180000033
式(4)中Z的结构式为
Figure FDA0002755508180000041
树脂A的结构式
Figure FDA0002755508180000042
树脂B的结构式
HO-X-O-A-X-OH或
Figure FDA0002755508180000043
树脂C的结构式
Figure FDA0002755508180000044
式C中M和W的结构式分别是
M为
Figure FDA0002755508180000051
A为H或
Figure FDA0002755508180000052
W为
Figure FDA0002755508180000053
；
树脂D的结构式
Figure FDA0002755508180000054
3.根据权利要求2所述的含磷无卤环氧树脂，其特征在于：反应1中，所述催化剂选自2-苯基咪唑，2-甲基咪唑，2-甲基-4乙基咪唑，1-甲基咪唑，4，4’-亚甲基咪唑，季鏻盐，季铵盐，叔胺中的一种或多种。
4.根据权利要求2所述的含磷无卤环氧树脂，其特征在于：反应1中，通式(1)与通式(4)摩尔比例为100：(1-20)。
5.根据权利要求2所述的含磷无卤环氧树脂，其特征在于：反应2中，树脂A与通式(2)或通式(3)的摩尔比例为(0-1)：(2-5)。
6.根据权利要求2所述的含磷无卤环氧树脂，其特征在于：所述多官能环氧树脂选自苯酚醛环氧树脂，邻甲酚醛环氧树脂，双酚A酚醛环氧树脂，双酚F醛环氧树脂，双酚S醛环氧树脂，双酚AD醛环氧树脂中的一种或多种；
所述有机磷化合物为DOPO(9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物)或DPPO(二苯基氧膦)。
7.根据权利要求2所述的含磷无卤环氧树脂，其特征在于：所述树脂C的磷含量为1-4％。
8.根据权利要求2所述的含磷无卤环氧树脂，其特征在于：所述含磷催化剂为三苯基膦、三丁基膦、三甲氧基膦、三乙基膦、乙基或丁基三苯基磷酸盐中的任意一种或多种，用量为50-1000ppm,含磷催化剂所用的溶剂为ACE、MEK、TOL、PM中的任意一种或多种。
9.一种含磷无卤环氧树脂的应用，其特征在于：将权利要求1的环氧树脂D或权利要求2-8之一制备的环氧树脂D，与固化剂制备成胶液，将上述无卤素含磷环氧加入固化剂和固化促进剂搅拌均匀配成胶液，然后将玻璃纤维布放入胶液中浸湿，然后烘烤制成半固化片，然后再将若干半固化片叠配好在上和或下表面叠加金属箔，然后用压机升温压合固化。
10.根据权利要求9所述的应用，其特征在于：所述固化剂选自双氰胺、DDM、DDS中的一种或多种。
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Publication number Priority date Publication date Assignee Title
CN103627146A (zh) * 2013-11-08 2014-03-12 建滔（江苏）化工有限公司 一种具有优良柔韧性含磷无卤素环氧树脂制备及应用
CN105601886A (zh) * 2016-03-08 2016-05-25 广东广山新材料有限公司 一种异氰酸酯改性环氧树脂及用途
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CN110317319A (zh) * 2018-03-30 2019-10-11 日铁化学材料株式会社 具有噁唑烷酮结构的环氧树脂、制造方法、环氧树脂组合物、纤维强化复合材料及成形体

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103627146A (zh) * 2013-11-08 2014-03-12 建滔（江苏）化工有限公司 一种具有优良柔韧性含磷无卤素环氧树脂制备及应用
CN106916282A (zh) * 2015-12-28 2017-07-04 广东生益科技股份有限公司 一种环氧树脂组合物以及使用其的预浸料和层压板
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