CN1252412A - 一种酚醛型环氧树脂固化剂及其制造方法 - Google Patents
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Abstract
本发明公开了一种酚醛型环氧树脂固化剂及其制造方法,固化剂是以双醛A及甲醛为原料,按摩尔比1∶0.2～3.2的比例加入总量25%～400%的溶剂中,在含0.5%～2.5%酸性催化剂和45～120℃的温度下反应2～10小时制得,产品的平均分子量为400～2000,其中含双酚A残留量10%～20%,解决了固化剂树脂耐热性差、固化不充分及树脂清漆稳定性差等问题,具有与环氧树脂相溶性好、易混合、固化物耐热性好及强度高等优点,广泛适用于环氧树脂固化剂尤其是环氧敷铜箔层压板使用。
Description
本发明涉及一种酚醛型环氧树脂固化剂及其制造方法，尤其是一种用于环氧敷铜箔层压板及其它材质层压板用环氧树脂固化剂及其制造方法。
在现有技术中，很少有关于BPA型环氧树脂固化剂(BPA-novolak)合成方法的报导，仅在日本专利JP61072018中提到用苯酚、BPA、37％福尔马林合成的环氧固化剂，用于固化溴化BPA环氧树脂制造敷铜箔多层层压板，在日本专利JP61069828中报导了用BPA37％HCHO在碱性条件下合成四羟甲基化BPA，再在酸性条件下与苯酚缩合制造环氧固化剂。环氧敷铜箔层压板及其它材质层压板用环氧树脂固化剂多为双氰胺及苯酚线性酚醛，在层压板制造时，通常用环氧树脂及其固化剂溶解于丁酮等有机溶剂中，加入固化促进剂，成为环氧树脂清漆，然后，将此树脂清漆浸渍于玻璃布，再用干燥器蒸发令溶剂挥发，成为半固化浸胶物，将此半固化浸胶物加到一定层数，最后叠上铜箔，在加压条件下，加热使之固化，这样得到的叠层层压板再进行机钻加工制成印刷电路板。在层压板制造技术领域，要求树脂固化性(即固化反应活性)固化树脂耐热性，层压板的钻孔加工性、耐湿性、电气特性及其色相稳定性、树脂清漆的稳定性等均优良。当用双氰胺为固化剂时，对于层压板的机钻加工性、色相稳定性及电气特性不存在问题，但固化树脂耐热性差、树脂清漆的稳定性欠佳(可使时间短)，因环氧树脂与双氰胺相溶性差，半固化浸胶物有泛白现象，固化不能充分等缺陷。使用苯酚novolak为固化剂时，也由于游离苯酚的原因造成色相稳定性极差，并直接影响产品质量，不能得到性能优良的固化物，从而造成电路板的报废或影响使用寿命。
本发明的目的在于制造一种酚醛型环氧树脂固化剂，其与环氧树脂具有良好的相溶性，与树脂混合易均匀并不会有固化剂析出现象，同时提高树脂交联密度，以改善固化物的性能，特别是改善耐热性和耐湿性。
为了达到上述目的，本发明采用了如下的技术方法：按双酚A与甲醛的摩尔比为1∶0.2～3.2的比例，加入重量为二者总量的25％～400％的溶剂中，加入双酚A重量的0.5％～2.5％酸性催化剂，催化剂为有机酸、无机酸、路易斯酸、强酸性阳离子交换树脂或固体酸的一种或其任何几种任意比例的混合物，在45～120℃的温度下反应2～10小时，静置，分层，取上层轻液，中和、水洗，在PH为6～7时升温、脱除溶剂，得平均分子量为400～2000，含残留双酚A重量10％～20％的固化剂产品。
在本发明实施过程中，较好的技术方案可以是：甲醛可以是多聚甲醛、三聚甲醛或37％的福尔马林溶液。溶剂可以是甲酸、乙酸、丙酸等低级羧酸类；甲醇、乙醇、异丙醇等低级醇类；甲苯、乙苯、二甲苯等芳香族烃类；甲酮、丁酮、甲基异丁基酮等酮类；二烷、二异丙醚等醚类；氯仿、氯苯、二氯乙烯等卤代烃类等等这些化合物的一种或几种以任意比例的混合物溶剂的使用量相对于BPA约为1/3-10倍，理想的使用量为1/2-5倍。
在实施本发明的过程中，较好的技术方案还可以是：1摩尔BPA结合0.2～3.2摩尔甲醛较好，超出此范围时，树脂清漆稳定性差，且当F/P＞3.2时，平均分子量过高，与环氧树脂相溶性下降；当F/P＜0.2时，产物中未反应BPA含量过高，且平均分子量过低，造成固化物耐热性降低。催化剂用量相对于BPA使用量为0.5％～2.5％，若催化剂用量低于0.5％，反应速度较慢，造成分子量偏低，未反应BPA含量偏高；若催化剂用量高于2.5％，反应速度过快，造成分子量偏高，产物与环氧树脂相溶性差。
本发明制造的固化剂(BPA-novolak)平均分子量Mu＝400-2000，当Mu＜400时，与环氧树脂固化后耐热性能较差，当Mu＞2000时，与环氧树脂的相溶性变差。本发明制造的BPA-novolak中未反应的BPA含量低于20％，若高于此范围，则固化物的耐热性能下降，且其它诸如电气性能和强度均有影响。在实际制造过程中，反应时间为2～10小时，反应中利用凝胶色谱分析仪测分子量来控制反应终点，分子量达400以上时即可终止反应，分子量在400～2000时，产品中的残留双酚A相应地在10％20％的范围以内。
本发明较好的技术方案又可以是：酸性催化剂为草酸、水杨酸、甲酸、乙酸和甲苯磺酸等有机酸；盐酸、稀硝酸、稀硫酸、磷酸等无机物；三氯化铝、氯化锡、三氟化硼等路易斯酸；由聚苯乙烯、二乙烯丙基的强酸性阳离子交换树脂SK1-B、RCP1SOH等；丝光沸石、硅酸铝等固体酸这些化合物中的一种或任何几种以任意比例的混合物。实际上，本发明可用的催化剂甚多，只要是酸性的，一般均可以采用。
与现有技术相比，本发明具有以下明显的优点：
1、本发明产品与环氧树脂有很好的相溶性，故与树脂混合易均匀并不会有固化剂析出现象；
2、本发明产品的分子中苯环密度高，增加了其分子刚性，使用后使固化物的耐热性及强度增加；
3、该发明产品分子含有大量羟基可与环氧基反应，从而提高树脂固化的交联密度，使环氧树脂固化物各项性能尤其是物理机械性能具有明显改善。
以下通过具体的实施例对本发明进行更加详细的描述：
实施例1
将BPA228.3g(1mol)、50％甲醛60g(0.9mol)加入圆底四口烧瓶中，并在烧瓶上装上搅拌器、温度计、回流冷凝器，再向体系中加入甲苯65g，升温搅拌使反应物均匀分散并溶解半小时，温度维持在80℃，然后加入1.1415g甲苯磺酸，维持在80℃反应1小时，再加入1.1415g甲苯磺酸维持80℃反应1h，第三次加入1.1415g甲苯磺酸并维持80℃反应1h后，向体系中加入甲苯325g，纯水200g，充分搅拌20分钟后停止搅拌，静置30分钟，除去下层重液，将轻液中加入纯水200g，NaOH适量，搅匀后测其PH值，当PH＝7时，静止30分钟，分去重液，轻液升温脱溶剂，温度达到200℃，压力达到-0.1MPa时卸除压力，将产品从釜中倒出，自然冷却，得到237g浅黄色固体产品。
实施例2～12
操作方法同例1，工艺条件、原材料配比及测试结果见表1。
表1实施例 F/P 催化剂种类及用量(％) 反应时间(小时) 反应温度(℃) Mu BPA％1 0.9 E 1.5 3 80 717 17.682 0.7 J 1.0 3 60 502 10.793 0.4 F 0.5 10 80 615 15.064 0.85 M 0.5 5 90 832 16.925 1.20 A 0.5+N 0.5 8 75 1015 13.026 0.65 O 0.5+I 1.0 3 100 934 17.087 0.25 A 0.5+P 1.0 4 110 410 18.728 3.0 E 1.5+P 1.0 2 115 854 13.689 0.2 B 1.3+L 0.8 4 118 440 18.5910 1.8 C 1.0+G 1.2 6 95 890 17.4211 3.2 D 1.0+H 1.0 7 85 997 18.9612 2.4 K 1.2+B 1.2 3 48 405 19.32
注：1、表中A草酸、B水杨酸、C甲酸、D乙酸、E甲苯磺酸、F盐酸、G稀硝酸、H稀硫酸、I磷酸、J三氯化铝、K三氟化硼、L氯化锡、MSK1-B、NRCP1SOH、O丝光沸石、P硅酸铝
2、表中催化剂用量，其百分含量以双酚A用量为基数。
Claims (7)
1、一种酚醛型环氧树脂固化剂的制造方法，以苯酚及甲醛为原料，在催化剂作用下，于溶剂中加热反应，脱除溶剂，本发明的特征在于：按双酚A与甲醛的摩尔比为1∶0.2～3.2的比例，加入重量为二者总量的25％～400％的溶剂中，加入双酚A重量的0.5％～2.5％酸性催化剂，催化剂为有机酸、无机酸、路易斯酸、强酸性阳离子交换树脂或固体酸的一种或其任何几种任意比例的混合物，在45～120℃的温度下反应2～10小时，静置，分层，取上层轻液，中和、水洗，在PH为6～7时升温、脱除溶剂，得平均分子量为400～2000，含残留双酚A重量10％～20％的固化剂产品。
2、根据权利要求1所述的制造方法，其特征在于有机酸催化剂为草酸、水杨酸、甲酸、乙酸和甲苯磺酸。
3、根据权利要求1所述的制造方法，其特征在于无机酸催化剂为盐酸、稀硝酸、稀硫酸和磷酸。
4、根据权利要求1所述的制造方法，其特征在于路易斯酸催化剂为三氯化铝、三氟化硼和氯化锡。
5、根据权利要求1所述的制造方法，其特征在于阳离子交换树脂催化剂是聚苯乙烯、二乙烯丙基的强酸性阳离子交换树脂SK1-B及RCPISOH。
6、根据权利要求1所述的制造方法，其特征在于固体酸催化剂是丝光沸石和硅酸铝。
7、按照权利要求1方法所制造的产品。
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| US3862260A (en) * | 1973-05-07 | 1975-01-21 | Union Carbide Corp | Epoxy curing system |
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| JPS61243821A (ja) * | 1985-04-23 | 1986-10-30 | Hitachi Chem Co Ltd | 半導体封止用エポキシ樹脂組成物 |
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| JPH08283656A (ja) * | 1995-04-13 | 1996-10-29 | Mitsui Petrochem Ind Ltd | 速硬化性粉体塗料用固形エポキシ樹脂組成物 |
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| CN103506171B (zh) * | 2012-06-15 | 2015-11-25 | 华东理工大学 | 改性酸性阳离子交换树脂及其用途 |
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