CN105623192A - 改性阻燃四缩水甘油二氨基二苯基甲烷组合物的制备方法 - Google Patents
改性阻燃四缩水甘油二氨基二苯基甲烷组合物的制备方法 Download PDFInfo
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- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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Abstract
本发明涉及改性阻燃四缩水甘油二氨基二苯基甲烷组合物的制备方法，改性阻燃四缩水甘油二氨基二苯基甲烷是由[(6-氧代-6H-二苯并[c,e][1,2]氧磷杂己环-6-基)甲基]丁二酸和四缩水甘油二氨基二苯基甲烷反应制备，制得改性阻燃四缩水甘油二氨基二苯基甲烷，常温下粘度在100000～200000cps之间，环氧当量在190～300g/eq之间；用于高温预浸渍料的改性阻燃四缩水甘油二氨基二苯基甲烷的组合物配方包括：改性阻燃四缩水甘油二氨基二苯基甲烷100重量份；固化剂50～150重量份；促进剂1-5重量份；活性稀释剂5-25份，增韧剂5-40份；组合物中含磷量≥1重量％；混合后的固化物具有燃烧性能UL94？V-0，极限氧指数≥30。
Description
技术领域
本发明涉及改性阻燃四缩水甘油二氨基二苯基甲烷组合物的制备方法，更确切地说涉及四缩水甘油二氨基二苯基甲烷(TGMDA)和[(6-氧代-6H-二苯并[c,e][1,2]氧磷杂己环-6-基)甲基]丁二酸(DDP)反应制备的改性阻燃四缩水甘油二氨基二苯基甲烷组合物的制备方法。
背景技术
四官能环氧树脂的佼佼者——四缩水甘油二氨基二苯基甲烷(TGMDA)由4,4`-二氨基二苯砜固化后，拉伸模量可达到3.7GPa，可在180℃下长期使用，是耐高温复合材料首选的基体树脂，目前产品仍供不应求。为了满足高温阻燃要求，近来很多厂家都做了试制。较成功者是按照现有技术CN101157672A披露，用3,3`-二氯-4,4`-二氨基二苯基甲烷和环氧氯丙烷反应制备双[3-氯-4-双(2,3-环氧丙基)氨基苯基]甲烷，其阻燃效果好，不足之处在于产物分解毒性大。再者，单体3,3`-二氯-4,4`-二氨基二苯基甲烷制备过程需要通氯气，因此设备要求耐腐蚀性高，且氯气吸收困难，漏气对环境污染严重，所以，阻碍了它的扩大应用。因而，对阻燃四官能环氧树脂的合成路线，有必要另辟新径。
发明内容
本发明者们为了制备改性阻燃四缩水甘油二氨基二苯基甲烷(TGMDA)，采用价格较低的原料，原料制造过程毒性小，对环境友好。产品分解碎片对环境也不会造成大的危害。经过专门研究，现提出如下完整技术方案：
一种改性阻燃四缩水甘油二氨基二苯基甲烷组合物的制备方法，该改性阻燃四缩水甘油二氨基二苯基甲烷是由[(6-氧代-6H-二苯并[c,e][1,2]氧磷杂己环-6-基)甲基]丁二酸(DDP)和四缩水甘油二氨基二苯基甲烷(TGDMA)反应制备，DDP从湖北盛威化工有限公司或从鸿苇(上海)新材料科技有限公司购买使用。它的相关理化数据是：CASNo.63562-33-4，分子式C17H15O6P，m.p.191～192℃，沸点578.3℃，折光率1.641，闪点303.5℃。改性阻燃四缩水甘油二氨基二苯基甲烷制备过程的主要反应式如下：
由于DDP的加入量较少，产物分子中环氧基依然较多存在。
反应条件设定为四缩水甘油二氨基二苯基甲烷100重量份，[(6-氧代-6H-二苯并[c,e][1,2]氧磷杂己环-6-基)甲基]丁二酸30～60重量份，在0.01～0.2重量份三苯基膦存在下，於70℃～110℃，反应0.5～5小时，制得改性阻燃四缩水甘油二氨基二苯基甲烷，即[(6-氧代-6H-二苯并[c,e][1,2]氧磷杂己环-6-基)甲基]丁二酸四缩水甘油二氨基二苯基甲烷酯。常温下粘度在100000～200000cps之间，环氧当量在190～300g/eq之间；这种芳核胺化物虽然需要高温固化，但它具有较高的耐热温度，较好的热稳定性，充分发挥出多官能环氧紧密的结构特性。在最后固化产物中增加了交联密度。可以说是一种理想的环氧树脂。而且TGMDA和DDP反应历程适用于所有环氧树脂。
用于高温预浸渍料的改性阻燃四缩水甘油二氨基二苯基甲烷的组合物配方包括：改性阻燃四缩水甘油二氨基二苯基甲烷100重量份；固化剂50～150重量份；促进剂1-5重量份；活性稀释剂5-25份，增韧剂5-40份；在反应前分A、B两组份分装，A组份为改性阻燃四缩水甘油二氨基二苯基甲烷、活性稀释剂和增韧剂的混合物，B组份为固化剂和促进剂的混合物；A组分与B组分的重量配比为1.2～2.0:1；应用时，A、B两组份混合均匀即可使用，组合物中含磷量≥1重量％；A、B两组份混合后的固化物具有燃烧性能UL94V-0，极限氧指数≥30。
本发明所述的改性阻燃四缩水甘油二氨基二苯基甲烷的组合物中的固化剂是从647酸酐、甲基四氢苯酐、甲基六氢苯酐和甲基那迪克酸酐中任选一种或几种。
本发明所述的改性阻燃四缩水甘油二氨基二苯基甲烷的组合物中的促进剂是从2-乙基-4-甲基咪唑和1-甲基咪唑中任选一种或几种。
本发明所述的改性阻燃四缩水甘油二氨基二苯基甲烷的组合物中的活性稀释剂是从丁基缩水甘油醚、苯基缩水甘油醚和1,4-丁二醇二缩水甘油醚中任选一种或几种。
本发明所述的改性阻燃四缩水甘油二氨基二苯基甲烷的组合物中的增韧剂是从端羧基丁腈橡胶、端环氧基丁腈橡胶、热塑性聚醚砜树脂或其改性物中任选一种或几种。
按照本发明实施制备改性阻燃四缩水甘油二氨基二苯基甲烷组合物的浇铸标件依次于100℃下3小时、150℃下2小时、180℃下3小时固化后具有的性能：阻燃等级达到UL94V-0级别，极限氧指数≥30，玻璃化转变温度≥200℃，弯曲模量≥3.5GPa，可在180℃下长期使用。
具体实施方式
为了更好地实施本发明特举例说明之，但实施例决不是对本发明保护范围的限制。
实施例1
100g四缩水甘油二氨基二苯基甲烷(TGMDA)，40g[(6-氧代-6H-二苯并[c,e][1,2]氧磷杂己环-6-基)甲基]丁二酸(DDP)，在0.2g三苯基膦(TPP)存在下，于80℃反应3小时获得改性阻燃四缩水甘油二氨基二苯基甲烷(ITGMDA)。产品粘度为145000cps，环氧当量215g/eq。
100g上述产品ITGMDA，15g1,4-丁二醇二缩水甘油醚，15g端羧基丁腈橡胶混合均匀成A组份；80g甲基四氢苯酐，2g2-乙基-4甲基咪唑混合均匀成B组份；A、B两组份混合均匀成组合物，组合物含磷量为1.2重量％，经过100℃3h，150℃2h，180℃3h固化后，其浇铸标件阻燃级别达到UL94V-0级别，极限氧指数为34.
实施例2
100g四缩水甘油二氨基二苯基甲烷(TGMDA)，55g[(6-氧代-6H-二苯并[c,e][1,2]氧磷杂己环-6-基)甲基]丁二酸(DDP)，在0.01g三苯基膦(TPP)存在下，于110℃反应4小时，获得改性阻燃四缩水甘油二氨基二苯基甲烷(ITGMDA)；产品粘度为180000cps，环氧值为250g/eq。
使用上述获得的阻燃改性四缩水甘油二氨基二苯基甲烷(ITGMDA)100g，5g苯基缩水甘油醚、端环氧基丁腈橡胶20g混合均匀成A组份；70g甲基六氢苯酐，4g1-甲基咪唑混合均匀成B组份；A、B两组份混合均匀成组合物，组合物含磷量为1.1重量％，经过100℃3h，150℃2h，180℃3h固化后，其浇铸标件阻燃级别达到UL94V-0级别，极限氧指数为32.
实施例3
100g四缩水甘油二氨基二苯基甲烷(TGMDA)，30g[(6-氧代-6H-二苯并[c,e][1,2]氧磷杂己环-6-基)甲基]丁二酸(DDP)，在0.1g三苯基膦(TPP)存在下，于70℃下反应5小时，获得改性阻燃四缩水甘油二氨基二苯基甲烷(ITGMDA)；产品粘度为120000cps，环氧当量为176g/eq.。
使用上述获得的阻燃改性四缩水甘油二氨基二苯基甲烷(ITGMDA)100g，20g丁基缩水甘油醚，5g热塑性聚醚砜树脂混合均匀成A组份；100g甲基那迪克酸酐、2g2-乙基-4-甲基咪唑混合均匀成B组份；A、B两组份混合均匀成组合物，组合物含磷量为1重量％；经过100℃3h，150℃2h，180℃3h固化后，其浇铸标件阻燃级别达到UL94V-0级别，极限氧指数为31.1。
Claims (5)
1.改性阻燃四缩水甘油二氨基二苯基甲烷组合物的制备方法，其特征在于，改性阻燃四缩水甘油二氨基二苯基甲烷是由[(6-氧代-6H-二苯并[c,e][1,2]氧磷杂己环-6-基)甲基]丁二酸和四缩水甘油二氨基二苯基甲烷反应制备，反应条件设定为四缩水甘油二氨基二苯基甲烷100重量份，[(6-氧代-6H-二苯并[c,e][1,2]氧磷杂己环-6-基)甲基]丁二酸30～60重量份，在0.01～0.2重量份三苯基膦存在下，於70℃～110℃，反应0.5～5小时，制得改性阻燃四缩水甘油二氨基二苯基甲烷，常温下粘度在100000～200000cps之间，环氧当量在190～300g/eq之间；用于高温预浸渍料的改性阻燃四缩水甘油二氨基二苯基甲烷的组合物配方包括：改性阻燃四缩水甘油二氨基二苯基甲烷100重量份；固化剂50～150重量份；促进剂1-5重量份；活性稀释剂5-25份，增韧剂5-40份；在反应前分A、B两组份分装，A组份为改性阻燃四缩水甘油二氨基二苯基甲烷、活性稀释剂和增韧剂的混合物，B组份为固化剂和促进剂的混合物；A组分与B组分的重量配比为1.2～2.0:1；应用时，A、B两组份混合均匀即可使用，组合物中含磷量≥1重量％；A、B两组份混合后的固化物具有燃烧性能UL94V-0，极限氧指数≥30。
2.根据权利要求1所述的改性阻燃四缩水甘油二氨基二苯基甲烷组合物的制备方法，其特征在于，所述的固化剂是从647酸酐、甲基四氢苯酐、甲基六氢苯酐和甲基那迪克酸酐中任选一种或几种。
3.根据权利要求1所述的改性阻燃四缩水甘油二氨基二苯基甲烷的制备方法，其特征在于，所述的促进剂是从2-乙基-4-甲基咪唑和1-甲基咪唑中任选一种或几种。
4.根据权利要求1所述的改性阻燃四缩水甘油二氨基二苯基甲烷组合物的制备方法，其特征在于，所述的活性稀释剂是从丁基缩水甘油醚、苯基缩水甘油醚和1,4-丁二醇二缩水甘油醚中任选一种或几种。
5.根据权利要求1所述的改性阻燃四缩水甘油二氨基二苯基甲烷组合物的制备方法，其特征在于，所述的增韧剂是从端羧基丁腈橡胶、端环氧基丁腈橡胶、热塑性聚醚砜树脂或其改性物中任选一种或几种。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0680765A (ja) * | 1992-09-02 | 1994-03-22 | Nippon Ester Co Ltd | エポキシ系耐炎性熱硬化性樹脂フィルム |
| WO2003027208A1 (fr) * | 2001-09-20 | 2003-04-03 | Nof Corporation | Derives d'acide carboxylique contenant du phosphore, procede de preparation de ces derives et substances ignifugeantes |
| CN103965246A (zh) * | 2013-01-28 | 2014-08-06 | 中国科学院宁波材料技术与工程研究所 | 一种含磷生物基二酸二烯丙基酯及其制备方法和应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0680765A (ja) * | 1992-09-02 | 1994-03-22 | Nippon Ester Co Ltd | エポキシ系耐炎性熱硬化性樹脂フィルム |
| WO2003027208A1 (fr) * | 2001-09-20 | 2003-04-03 | Nof Corporation | Derives d'acide carboxylique contenant du phosphore, procede de preparation de ces derives et substances ignifugeantes |
| CN103965246A (zh) * | 2013-01-28 | 2014-08-06 | 中国科学院宁波材料技术与工程研究所 | 一种含磷生物基二酸二烯丙基酯及其制备方法和应用 |
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| CN117070051B (zh) * | 2023-10-16 | 2024-02-02 | 太原理工大学 | 适用于t800碳纤维的环氧树脂体系及其复合材料的制作方法 |
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