CN1127264A - 新环氧树脂及其制备和应用 - Google Patents

新环氧树脂及其制备和应用 Download PDF

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CN1127264A
CN1127264A CN95108104A CN95108104A CN1127264A CN 1127264 A CN1127264 A CN 1127264A CN 95108104 A CN95108104 A CN 95108104A CN 95108104 A CN95108104 A CN 95108104A CN 1127264 A CN1127264 A CN 1127264A
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resins
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U·诺伊曼
M·霍内尔
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Hoechst AG
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Abstract

包含双酚化合物的环氧树脂，其双酚的至少一个芳环，通过一个直链或支链，取代或未取代的亚烷基与至少一个芳基相接。

Description

新环氧树脂及其制备和应用
本发明涉及由芳烷基化的二酚和二环氧化合物构成，或由芳烷基化的二酚和表氯醇构成的环氧树脂，及其制备方法和应用。
含有环氧化物基的树脂一般是众所周知的(H.Lee，K.Neville in“Handbook of Epoxy Resins”，Reissue 1982，Mc Graw Hill Book Compa-ny，New York；C.A May in“Epoxy Resins”，Marcel Dekker，Inc.NewYork and Basel，1988)。例如可通过多羟酚与表氯醇在氢氧化钠溶液存在下反应，或把双酚化合物加成到双环氧化合物中反应，而制备出环氧树脂。由于可通过环氧与酚基本结构改性而导致产生各式各样的性质，这种相对低分子量活性树脂在各种材料中应用是非常广泛的。
已知的工业制取的环氧树脂要么不溶，要么不完全溶于芳族溶剂中，而只溶于(相当昂贵的)脂族酯类和醚类，如醋酸丁酯，甲氧丙醇、乙二醇单丁醚和二甘醇二甲醚等。
因此，本发明的目的是提供能溶于如二甲苯或甲苯这样的芳族溶剂的环氧树脂，且使该已知环氧树脂性能突出。
根据本发明，可以用芳烷基化双酚类取代至少一部分通常采用的双酚化合物来制取环氧树脂，以达到此目的。
因此，本发明提供了这样的环氧树脂，它包含的双酚化合物其双酚的至少一个芳环通过一个直链或支链，取代或未取代的亚烷基，与至少一个芳基相接。根据本发明，这些芳基化的双酚化合物的比例为10％至90％，20％至80％则更佳，而用来制备环氧树脂的最佳比例为占全部双酚化合物总量的30％至70％。其余比例的双酚化合物是常规使用的非芳烷基化双酚类。在本发明范围内同样可用脂族二元醇代替未取代双酚，与上述比例的芳烷基化双酚化合物结合使用。在本发明范围内，也可用分子中由含3个或3个以上羟基的多元酚和/或分子中含3个或3个以上环氧基的多环氧化合物来代替小比例的(至多占原料量的5％)的双酚化合物和/或二环氧化合物。同样，一元酚和/或单环氧化合物可代替小比例的双酚化合物和/或二环氧化合物(至多占原料量的5％)。
本发明尤其提供了其中一些双酚化合物平均带有一个芳烷基的环氧树脂，根据本发明制备环氧树脂所用双酚化合物总量中，这些单取代双酚化合物的比例为10％至90％，而20％至80％则更佳，30％至70％为最佳。
根据本发明用于制备环氧树脂的双酚化合物的合成工艺在同时提交的德国专利申请P4436097.5中有所说明。
适用于本发明的双酚化合物为二羟基芳族化合物与带有一个链烯基的芳族化合物的反应产物。在这些化合物中，链烯基也可以是含有一个环内或环外双键的稠合环脂族环的一部分。在这种情况下，优选进行烷基化反应，以在反应后所用双酚化合物平均携带一个芳烷基。适用的双酚的实例为双酚A，双酚F，异构的二羟基苯和二羟基萘的反应产物，以及二羟二苯醚，二羟二苯甲酮和二羟二苯砜的反应生成物。适用的链烯基芳烃化合物有8至15个碳原子并含有至少一个芳环和单一的链烯基。其实例有苯乙烯及其同系物，异丙烯基苯，茚和二苯基乙烯。
可采用多种本技术领域的普通技术人员已知的方式让制备相应环氧树脂的芳烷基化双酚化合物组分，或按需要与未改性双酚类的混合物参与反应：
1)与作为环氧化物组分的表氯醇的增链加成反应(Taffy法)，其中可用过量的表氯醇控制反应产物的平均分子量。根据需要，可利用连续加入双酚化合物进一步构成该产物。
2)所谓“高级”反应：与作为环氧化物组分的双环氧化物(二环氧甘油醚)，也可与不同种二环氧甘油醚的混合物的反应(此时双环氧化合物的分子量优选平均每环氧基为100至525g/mol)。
以上所有反应中，其目的是使树脂中有剩余环氧基，相当于环氧当量(分子量除以环氧基数)为180至5000g/mol，而230至2000g/mol为更佳。
适用于本发明的二环氧甘油醚的数均分子量(Mn)为约300至7000g/mol，且一环氧当量为150—3500g/mol。其实例有表氯醇或甲基表氯醇与二(羟苯基)甲烷(双酚F)或2，2—二(4—羟苯基)丙烷(双酚A)，1，4—丁二醇，1，6—己二醇，二(羟甲基)环己烷，聚丙二醇(平均分子量为200至4000g/mol)的反应产物，及与二羟基二苯酮，二羟基萘，及间苯二酚反应的反应产物。制取适当分子量的双环氧化合物既要选择适当比例的双酚化合物和表氯醇，也要在加入催化剂(如路易斯酸，路易斯碱或鏻盐)的时候，将单体二环氧甘油基化合物与其他双酚化合物反应。据此发明，在该二环氧甘油基化合物合成中也可采用上述芳烷基化双酚化合物。
详细例举的适用环氧化合物可在手册“Epoxidverbindungen undHarze”(环氧化合物与树脂)A.M.Paquin，Sringer Verlag，Berlin 1958，第四章及上面提及的手册中找到。
根据本发明，可分两阶段制备该改性环氧树脂，第一阶段，一种非芳烷基化双酚组分与链烯基芳族化合物组分在弱酸存在下反应，温度为100℃至160℃(最好为120℃至155℃)。第二阶段，将上述反应产物与环氧化合物组分反应，此时，前述的两种工艺衍生物都可使用。
一步法制备改性环氧树脂的方法是将一种芳烷基化和未芳烷基化的双酚组分的混合物与一种环氧化合物组分反应。
上述双酚类化合物作为双酚组分可单独或以混合物的形式使用。本发明中的术语“双酚组分”也包括在双酚化合物中加入少量的三元或多元酚及一元酚。每次加入量基于双酚组分原料总量计，为少于5％，而少于2％为更佳。
本发明的改性环氧树脂可用于生产例如铸塑树脂，粘合剂和注模，特别是用作结构树脂，可按需要与常规惰性填充剂结合，如：白垩，高岭土，锯末，云母或玻璃珠，或与含纤维的增强剂结合，如：玻璃，芳族聚酰胺，碳纤维或金属纤维。
在下列实施例中，除特别说明外，所有含量，份数和百分比均以质量计。
实施例1：A.双酚F              200g(1.0mol)B.二水合草酸         2.2gC.硼酸               1.15gD.苯乙烯              104g(1.0mol)E.Beckopox EP 140#   613.5g(3.35eq)F.三苯膦              2.1g
Beckopox Ep 140是Hoechst AG基于双酚A制备的一种液体树脂
于氮气氛下120℃的温度下，将B、C加入A中。然后在最初温度为120℃的情况下，以滴加速度能确保滴入时该放热反应的温度保持在120℃至最高温度160℃之间的方式加入D。加完D后，该反应混合物在160℃下保持2小时。此时，可根据确定固体含量来检测反应程度(2g生成物/2g二甲苯；在一循环空气烘箱中在160℃下一小时)。将混合物温度冷却至120℃时，加入E，随后加入F。为确保完全反应，升温到160℃—170℃。保持160℃的反应温度，直至达到理论环氧当量。
环氧当量          670—690g/mol
25℃在丁基二甘醇中浓度为40％时的粘度为
                  480—510mpa.s
实施例2：
A.双酚A           228g(1.0mol)
B.草酸二水合物           4.2g
C.硼酸                  1.15g
D.苯乙烯          208g(2.0mol)
E.表氯醇                 650g
F.四甲基氯化铵           2.1g
G.去离子水             2.1g
H.去离子水             10g
I.去离子水             460g
J.二甲苯               500g
K.10％磷酸             见本文
于氮气氛下在160℃时将B、C加入A。然后在初温为160℃下以滴加速度能确保该升温反应的温度保持在155℃至165℃之间的方式加入D。加完D后，在160℃下保持该反应混合物2小时，此时，根据确定固含量来检测反应程度(2g生成物/2g二甲苯；在循环空气烘箱中160℃的温度下一小时)。加入更多剂量的草酸可能是必要的。将温度冷却至100℃，将熔体溶于E中，再将G溶于F中，在60℃下加入。在70℃的温度下搅拌该混合物60分钟，然后在80℃的温度和约500百帕压力下用120分钟加入H，其加入方式以能同时进行共沸脱水。然后减压蒸除表氯醇，且温度升高(最高温度120℃，压力降至50百帕)。将反应物在120℃，50百帕压力下，放置30分钟。并在同样条件下用30分钟加入H。冷却混合物，温度降至100℃以下，将减压条件移除，然后加入I，95℃下，剧烈搅拌混合物15分钟。分离水相，基于测定的可水解的氯含量，在搅拌条件下加入为需要量1.5倍的浓度为4％的氢氧化钠溶液，在90℃下连续搅拌90分钟。将该混合物溶于J中，分离水相。加入K后，PH值为6.0至7.2之间，在共沸条件下脱水，汽提出约50ml二甲苯，并过滤该混合物。在最高温度为150℃和减压条件下(至多50百帕)脱除溶剂。
环氧当量                        290—295g/mol
氯总含量                                 ＜0.4％
可水解氯含量                             ＜0.1％
25℃时粘度为                         55,000mpa.s
实施例3
A.间苯二酚                           110g(1.0mol)
B.草酸二水合物                               2.2g
C.硼酸                                      1.15g
D.苯乙烯                             130g(1.25mol)
E.Beckopox EP 140#                  580g(3.17eq)
F.三苯膦                                     1.5g
Beckopox R EP 140是由Hoechst AG基于双酚A制备的液体树脂。
将B、C在120℃于氮气氛下加入A中。在初温为120℃时加入D，以滴加速度能确保该放热反应温度保持在120℃与最高温度130℃之间的方式加入D。D完全加入后，反应混合物在160℃下保持2小时。其间，可根据确定固含量来测定反应程度(2g生成物/2g二甲苯；于160℃下在循环空气烘箱内1小时)。将该混合物冷却至120℃，加入E，随后加入F。为确保反应完全，加热至160℃与170之间。反应混合物温度保持在160℃直到达到理论环氧当量。
环氧当量：                           715—745g/mol
25℃下在丁基二甘醇中浓度
        为40％时的粘度为             720—750mPa.s
实施例4：
A.双酚A                              228g(1.0mol)
 B.草酸二水合物                              2.2g
 C.硼酸                                     1.15g
 D.苯乙烯                             104g(1.0mol)
 E.例2制备的树脂                      744g(2.54eq)
 F.三苯膦                                    5.0g
在160℃下于氮气氛中将B、C加入A。在初温为160℃的情况下滴入D，以滴加速度能确保该放热反应温度介于155℃至165℃(最高温度)间的方式加入D。当完全滴入D后，反应混合物在160℃下保持2小时。其间，根据确定固含量来检测反应程度(2g反应生成物/2g二甲苯；160℃下在循环空气烘箱中一小时)。随后加入草酸，可能是必要的。将该混合物冷却至120℃，加入E，随后分二批或多批加入F，为确保反应完全，将温度升高达160℃至170℃。将反应混合物保持在160℃，直至达到理论环氧当量。
环氧当量                                     2000—2400g/mol
25℃下在丁基二甘醇中浓度为                  2100—3000mPa.s
             40％时的粘度
实施例5：
A.双酚F                                      200g(1.0mol)
B.草酸二水合物                                      2.2g
C.硼酸                                             1.15g
D.茚                                         116g(1.0mol)
E.Beckopox EP 140#                           608g(3.32eq)
F.三苯膦                                            4.1g
# Beckopox EP 140是Hoechst AG用双酚A制备的一种液体树脂。
在120℃下，于氮气氛中将B、C加入A。在初温度为120℃情况下，滴入D，以滴加速度能确保该放热反应温度介于120℃至160℃(最高温度)之间的方式加入D。当完全加入D后，在160℃温度下保持该反应混合物2小时，其间，根据确定固含量来测定反应程度(2g生成物/2g二甲苯；在160℃下于循环空气烘箱中1小时)。将该混合物冷却至120℃，加入E，随后加入F。为确保完全反应，将温度升高达160℃—170℃，保持反应混合物的温度为160℃，直至达到理论环氧当量。
环氧当量                            705—735g/mol
25℃下浓度为40％在丁基二甘醇        550—580mPa.s
                  中的粘度

Claims (8)

1.一种环氧树脂，包含双酚化合物，其双酚的至少一个芳环通过一个直链或支链，取代或未取代的亚烷基，与至少一个芳基相接。
2.权利要求1中所述环氧树脂，含有一种芳烷基化的双酚化合物，其比例为制备此环氧树脂所用双酚化合物总质量的10—90％。
3.权利要求1中所述环氧树脂，含有其中平均每摩尔双酚化合物具有一个芳烷基取代基的芳烷基化双酚化合物。
4.权利要求1中所述环氧树脂，其中芳烷基取代基选自含有8至15个碳原子的芳烷基。
5.两步法制备改性环氧树脂的方法，该方法包括在第一阶段在弱酸存在的情况下将双酚组分与链烯基芳族组分反应；其后，如需要，在加入更多的同种或不同种双酚组分后，将该产物与一种环氧组分反应。
6.一步法制备改性环氧树脂的方法，包括将芳烷基化双酚组分和非芳烷基化的双酚组分的混合物与一种环氧化合物组分反应。
7.如权利要求5或6所述的方法制备的改性环氧树脂。
8.权利要求1，2和7任一项所述改性环氧树脂用于制造铸塑树脂，粘合剂，注模料，填料及(纤维)增强的结构树脂的应用。
CN95108104A 1994-06-30 1995-06-28 新环氧树脂及其制备和应用 Pending CN1127264A (zh)

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DE19944436095 DE4436095A1 (de) 1994-10-10 1994-10-10 Neuartige Epoxidharze, ihre Herstellung und Verwendung

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