CN116284137A - 一种丁香醛基本征阻燃环氧固化剂及其树脂的制备方法 - Google Patents
一种丁香醛基本征阻燃环氧固化剂及其树脂的制备方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—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
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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
本发明公开了一种丁香醛基本征阻燃环氧固化剂及其树脂的制备方法,属于生物基高分子材料技术领域。本发明以生物质丁香醛,二胺化合物,9,10‑二氢‑9‑氧杂‑10‑磷杂菲‑10‑氧化物(DOPO)为原料,首先使丁香醛和二胺合成席夫碱,然后再与DOPO反应,最终得到丁香醛基本征阻燃环氧固化剂。本发明所制备的丁香醛基本征阻燃环氧固化剂可作为环氧单体的固化剂,固化后,可赋予热固性环氧树脂阻燃性能。本发明固化过程简单,便于操作,可控性好,利用现有的化工设备即可生产,适于大规模工业化生产。
Description
技术领域
本发明属于生物基高分子材料技术领域,具体涉及一种丁香醛基本征阻燃环氧固化剂及其树脂的制备方法。
背景技术
高性能环氧树脂的制备可以通过使用新型阻燃环氧固化剂对环氧树脂基体进行性能改性。近年来,为了缓解化石资源的短缺,实现可持续发展,以生物基物质为原料,制备生物基阻燃固化剂剂越来越受到人们的关注。开发出阻燃效率高、阻燃制品综合性能优异的生物基阻燃固化剂是当前阻燃固化剂领域发展的新方向。通过不同阻燃元素(磷和氮等)的结合来构建协效阻燃固化剂体系,可以在不影响材料其它性能的前提下,提高材料的阻燃效率。因此,为了满足可持续发展和环境友好的阻燃需求,制备含不同阻燃元素的生物基阻燃固化剂是一种潜在的、可持续的方法。
发明内容
本发明的目的在于提供一种由生物质转换得到,符合绿色环保可持续发展理念、制备方法简单,易于实施的丁香醛基本征阻燃环氧固化剂的制备方法。
为了实现上述目的,本发明采用的技术方案如下:
所述丁香醛基本征阻燃环氧固化剂,结构如下:
其中,R基团为:
本发明制备具有上述结构的丁香醛基本征阻燃环氧固化剂的方法,包括以下步骤:
S1.丁香醛基双酚单体的合成:将二胺化合物溶解到无水乙醇中,再加入丁香醛无水乙醇溶液,二胺化合物与丁香醛按摩尔比1:1~4的配比加入,升温至80℃~100℃,反应3~10h,倒入蒸馏水中,有机溶剂萃取,分液,取有机层干燥,减压蒸馏,除去溶剂,乙醇洗3~6次,真空干燥,即得丁香醛基双酚单体;
S2.丁香醛基本征阻燃环氧固化剂的合成:将由S1的丁香醛基双酚单体和DOPO,按摩尔比1:0.001~10加入,升温至50℃~100℃,在氮气氛围下反应2~8h,抽滤,萃取,取有机层干燥,减压蒸馏,去除溶剂,将产物置于真空烘箱中干燥,得丁香醛基本征阻燃环氧固化剂。
本发明的另一目的在于提供一种制备阻燃环氧树脂的方法,具体为:
S3.采用上述方法得到的丁香醛基本征阻燃环氧固化剂与商用固化剂和环氧单体混合均匀,真空脱泡后,将体系浇注入模具中热固成型,即得阻燃环氧树脂产品。
优选的,S1中,二胺化合物为乙二胺、1,4-丁二胺(腐胺)、1,5-戊二胺(尸胺)、1,6-己二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、胍基丁胺、精胺、亚精胺、1,3-双(氨丙烷基)四甲基二硅醚、2-[3-(2-氨基-乙基)-1,1,3,3-四甲基-二硅氧烷基]-乙胺、间苯二胺、4-甲氧基间苯二胺、联苯二胺、3,3′-二甲氧基联苯胺(联大茴香胺)、4,4'-二氨基-3,3'-二甲基联苯基甲烷、4,4'-二氨基二苯甲烷、4,4'-二氨基二苯醚、4,4'-二氨基二硫醚或4,4'-二氨基二苯砜中的一种或两种以上的混合。
优选的,S3中,所述商业固化剂为二乙烯三胺、三乙烯四胺、四乙烯五胺、二乙氨基丙胺、乙二胺、异佛尔酮二胺、N-氨乙基哌嗪、双(4-胺基环己基)甲烷、三辛基甲胺、二氨基二苯基甲烷、二氨基二苯基砜、二氨基二苯基醚、间苯二胺、邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、十二烯基琥珀酸酐、均苯四甲酸酐、苯酮四酸二酐、乙二醇双偏苯三酸酐、甲基环己烯基四酸二酐或偏苯三甲酸酐中的一种或两种以上的混合。
优选的,S3中,将体系倒入模具中,在60℃~100℃保温1~4h,接着在100℃~130℃保温2~6h热固成型。
与现有技术相比,本发明的有益效果为:
1.本发明以生物质丁香醛,二胺化合物,9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)为原料,首先使丁香醛和二胺合成席夫碱,然后再与DOPO反应,最终得到丁香醛基本征阻燃环氧固化剂,该固化剂由生物基原料丁香醛转换得到,是一种新型的本征阻燃环氧固化剂,能够解决环氧树脂固化后易燃的问题,且符合绿色化学可持续发展原则。
2.本发明所制备的丁香醛基本征阻燃环氧固化剂可作为环氧单体的固化剂,固化后,可赋予热固性环氧树脂阻燃性能。固化过程简单,便于操作,可控性好,利用现有的化工设备即可生产,适于大规模工业化生产,可应用于高新材料技术领域。
3.本发明提供的丁香醛基本征阻燃环氧固化剂的制备方法,拓展了本征阻燃环氧固化剂的类型,对本征阻燃环氧树脂的发展具有重要的意义。
具体实施方式
下面结合具体实施例,对本发明做进一步的解释和说明。
实施例1
一种丁香醛基本征本征阻燃环氧固化剂及其树脂的制备方法,具体包括以下步骤:
HMDA-SH-DOPO的合成过程
S1.丁香醛基双酚单体(HMDA-SH)的合成:
在100mL的三口烧瓶中加入1.16g 1,6-己二胺,氮气保护,加入20mL的无水乙醇,机械搅拌至完全溶解后,再相继向其中加入3.64g丁香醛的无水乙醇溶液20mL,体系在80℃下反应6h。反应结束后,将体系倒入100mL蒸馏水中,用乙酸乙酯萃取,分液,取乙酸乙酯层用无水硫酸钠干燥过夜。随后,抽滤,滤液减压蒸馏去除溶剂,得到固体产物,将得到的产物水洗3次,真空干燥,得到HMDA-SH,产率97%。
S2.丁香醛基本征阻燃环氧固化剂(HMDA-SH-DOPO)的合成:
在装有机械搅拌,冷凝回流,氮气导入装置的500mL的三口烧瓶中,依次加入4.4g的HMDA-SH,4.3g的DOPO,在氮气氛围下,升温至80℃,反应6h。反应结束后抽滤,滤液用蒸馏水萃取,分液三次,取有机层加入无水硫酸钠干燥过夜。抽滤,取滤液通过减压蒸馏去除溶剂,产物于真空烘箱中50℃干燥,得到丁香醛基本征阻燃环氧固化剂(HMDA-SH-DOPO),产率85%。
S3.环氧树脂固化:
将固化剂(HMDA-SH-DOPO与商业固化剂DDM)和双酚A环氧树脂(按照环氧和NH一比一的摩尔比)混合均匀后,真空脱泡后,将体系倒入模具中,并于80℃保温2h,接着在110℃保温4h,得到热固性阻燃环氧树脂。
表1锥形量热实验所得各项数据
HMDA-SH-DOPO的加入会使环氧树脂的阻燃性能得到提高。锥形量热测试结果表明,在加入5%的HMDA-SH-DOPO后,峰值热释放速率、总热释放速率、总生烟量、CO生成速率和CO2生成速率与未改性的环氧固化物相比均有所下降。
实施例2
一种丁香醛基本征本征阻燃环氧固化剂及其树脂的制备方法,具体包括以下步骤:
TECH-SH-DOPO的合成过程
S1.丁香醛基双酚单体(TECH-SH)的合成:
在100mL的三口烧瓶中加入1.46g三乙烯四胺,氮气保护,加入20mL的无水乙醇,机械搅拌至完全溶解后,再相继向其中加入3.64g丁香醛的无水乙醇溶液20mL,体系在80℃下反应6h。反应结束后,将体系倒入100mL蒸馏水中,用乙酸乙酯萃取,分液,取乙酸乙酯层用无水硫酸钠干燥过夜。随后,抽滤,滤液减压蒸馏去除溶剂,得到固体产物,将得到的产物水洗3次,真空干燥,得到TECH-SH,产率96%。
S2.丁香醛基本征阻燃环氧固化剂(TECH-SH-DOPO)的合成:
在装有机械搅拌,冷凝回流,氮气导入装置的500mL的三口烧瓶中,依次加入4.7g的TECH-SH,4.3g的DOPO,在氮气氛围下,升温至80℃,反应6h。反应结束后抽滤,滤液用蒸馏水萃取,分液三次,取有机层加入无水硫酸钠干燥过夜。抽滤,取滤液通过减压蒸馏去除溶剂,产物于真空烘箱中50℃干燥,得到丁香醛基本征阻燃环氧固化剂(TECH-SH-DOPO),产率92%。
S3.环氧树脂固化:
将固化剂(TECH-SH-DOPO与商业固化剂DDM)和双酚A环氧树脂(按照环氧和NH一比一的摩尔比)混合均匀后,真空脱泡后,将体系倒入模具中,并于80℃保温2h,接着在110℃保温4h,得到热固性环氧树脂。
表2锥形量热实验所得各项数据
TECH-SH-DOPO的加入会使环氧树脂的阻燃性能得到提高。锥形量热测试结果表明,在加入5%的TECH-SH-DOPO后,峰值热释放速率、总热释放速率、总生烟量、CO生成速率和CO2生成速率与未改性的环氧固化物相比均有所下降。
实施例3
一种丁香醛基本征本征阻燃环氧固化剂及其树脂的制备方法,具体包括以下步骤:
DDE-SH-DOPO的合成过程
S1.丁香醛基双酚单体(DDE-SH)的合成:
在100mL的三口烧瓶中加入2g 4,4’二氨基二苯甲醚(DDE),氮气保护,加入20mL的无水乙醇,机械搅拌至完全溶解后,再相继向其中加入3.64g丁香醛的无水乙醇溶液20mL,体系在80℃下反应6h。反应结束后,将体系倒入100mL蒸馏水中,用乙酸乙酯萃取,分液,取乙酸乙酯层用无水硫酸钠干燥过夜。随后,抽滤,滤液减压蒸馏去除溶剂,得到固体产物,将得到的产物水洗3次,真空干燥,得到DDE-SH,产率97%。
S2.丁香醛基本征阻燃环氧固化剂(DDE-SH-DOPO)的合成:
在装有机械搅拌,冷凝回流,氮气导入装置的500mL的三口烧瓶中,依次加入5.3g的DDE-SH,4.3g的DOPO,在氮气氛围下,升温至80℃,反应6h。反应结束后抽滤,滤液用蒸馏水萃取,分液三次,取有机层加入无水硫酸钠干燥过夜。抽滤,取滤液通过减压蒸馏去除溶剂,产物于真空烘箱中50℃干燥,得到丁香醛基本征阻燃环氧固化剂(DDE-SH-DOPO),产率89%。
S3.环氧树脂固化:
将固化剂(DDE-SH-DOPO与商业固化剂DDM)和双酚A环氧树脂(按照环氧和NH一比一的摩尔比)混合均匀后,真空脱泡后,将体系倒入模具中,并于80℃保温2h,接着在110℃保温4h,得到热固性环氧树脂。
表3锥形量热实验所得各项数据
DDE-SH-DOPO的加入会使环氧树脂的阻燃性能得到提高。锥形量热测试结果表明,在加入5%的DDE-SH-DOPO后,峰值热释放速率、总热释放速率、总生烟量、CO生成速率和CO2生成速率与未改性的环氧固化物相比均有所下降。
Claims (7)
2.一种如权利要求1所述的丁香醛基本征阻燃环氧固化剂的制备方法,其特征在于,具体包括以下步骤:
S1.丁香醛基双酚单体的合成:将二胺化合物溶解到无水乙醇中,再加入丁香醛无水乙醇溶液,二胺化合物与丁香醛按摩尔比1:1~4的配比加入,升温至80℃~100℃,反应3~10h,倒入蒸馏水中,有机溶剂萃取,分液,取有机层干燥,减压蒸馏,除去溶剂,乙醇洗3~6次,真空干燥,得丁香醛基双酚单体;
S2.丁香醛基本征阻燃环氧固化剂的合成:将由S1的丁香醛基双酚单体和DOPO,按摩尔比1:0.001~10加入,升温至50℃~100℃,在氮气氛围下反应2~8h,抽滤,萃取,取有机层干燥,减压蒸馏,去除溶剂,真空干燥,得丁香醛基本征阻燃环氧固化剂。
3.根据权利要求2所述的一种丁香醛基本征阻燃环氧固化剂的制备方法,其特征在于,S1中,二胺化合物为乙二胺、1,4-丁二胺、1,5-戊二胺、1,6-己二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、胍基丁胺、精胺、亚精胺、1,3-双(氨丙烷基)四甲基二硅醚、2-[3-(2-氨基-乙基)-1,1,3,3-四甲基-二硅氧烷基]-乙胺、间苯二胺、4-甲氧基间苯二胺、联苯二胺、3,3′-二甲氧基联苯胺(联大茴香胺)、4,4'-二氨基-3,3'-二甲基联苯基甲烷、4,4'-二氨基二苯甲烷、4,4'-二氨基二苯醚、4,4'-二氨基二硫醚或4,4'-二氨基二苯砜中的一种或两种以上的组合。
4.一种采用如权利要求2或3所述方法得到的丁香醛基本征阻燃环氧固化剂制备阻燃环氧树脂的方法,其特征在于,将丁香醛基本征阻燃环氧固化剂与商用固化剂和环氧单体按照一定比例混合均匀,真空脱泡,待无气泡后,将体系浇注入模具中热固成型即得阻燃环氧树脂产品。
5.根据权利要求4所述的一种制备阻燃环氧树脂的方法,其特征在于,所述商业固化剂为二乙烯三胺、三乙烯四胺、四乙烯五胺、二乙氨基丙胺、乙二胺、异佛尔酮二胺、N-氨乙基哌嗪、双(4-胺基环己基)甲烷、三辛基甲胺、二氨基二苯基甲烷、二氨基二苯基砜、间苯二胺、邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、十二烯基琥珀酸酐、均苯四甲酸酐、苯酮四酸二酐、乙二醇双偏苯三酸酐、甲基环己烯基四酸二酐、偏苯三甲酸酐中的一种或两种以上的组合。
6.根据权利要求5所述的一种制备阻燃环氧树脂的方法,其特征在于,丁香醛基本征阻燃环氧固化剂与商用固化剂按摩尔比1:0.15~10混合。
7.根据权利要求5或6所述的一种制备阻燃环氧树脂的方法,其特征在于,将体系倒入模具中,在60℃~100℃保温1~4h,接着在100℃~130℃保温2~6h热固成型。
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