CN112029073A - 环氧树脂固化剂、反应方法以及固化性环氧树脂组合物 - Google Patents
环氧树脂固化剂、反应方法以及固化性环氧树脂组合物 Download PDFInfo
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- CN112029073A CN112029073A CN202010926152.XA CN202010926152A CN112029073A CN 112029073 A CN112029073 A CN 112029073A CN 202010926152 A CN202010926152 A CN 202010926152A CN 112029073 A CN112029073 A CN 112029073A
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- epoxy resin
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- phosphorus
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Abstract
本发明提供通过与缩水甘油基具有反应性、从而能够提供可以期待阻燃化、低介电常数化等的固化性环氧树脂组合物的新型含磷化合物,具体而言,提供由下述通式(I)表示的含磷化合物。式(I)中,m表示1~10的数,R1、R2、R3以及R4彼此独立地表示氢原子、烷基或芳基,R5表示烷基、链烷二基、链烷三基、链烷四基或芳香族基团,X表示氧原子或硫原子,Y表示氧原子、硫原子或=NR',R'表示氢原子、烷基或芳基。
Description
本申请是申请日为2014年9月10日且发明名称为“含磷化合物以及含有该化合物的固化性环氧树脂组合物”的PCT/JP2014/073994进入中国国家阶段的中国专利申请No.201480049257.4的分案申请。
技术领域
本发明涉及含磷化合物,详细而言,涉及具有反应性、能够提供通过与环氧化合物并用而可以期待阻燃化、低介电常数化等的固化性环氧树脂组合物的含磷化合物。
背景技术
近年来,随着对于世界环境问题、对人体的安全性的关注提高,关于电气/电子制品,除了阻燃性之外,更少的有害性、更高的安全性这样的要求也增大。即,要求有害性气体和烟雾的产生少。
溴系阻燃剂虽然具有良好的阻燃性,但在燃烧时产生有害的卤化氢(溴化氢)气体,因此逐渐抑制其使用。因此,正在开发在通常的环氧树脂中配合有非卤素系阻燃剂、例如氮化合物、磷化合物或无机化合物等的组合物。但是,这些赋予阻燃性添加剂存在下述问题:阻燃化效果不充分,或者对环氧树脂的固化带来不良影响,或者使固化组合物的玻璃化转变温度等物性降低等。
例如,作为磷系阻燃剂,磷酸三苯脂广泛应用于各种树脂,在专利文献1中提出了将由高分子量类型的二元酚和苯酚构成的磷系阻燃剂用于环氧树脂。
但是,为了用这些阻燃剂赋予充分的阻燃性,需要大量地配合,如果大量地配合来满足阻燃性,则玻璃化转变温度降低,相反,如果为了提高玻璃化转变温度而使阻燃剂的配合量变少量,则阻燃性不足。另外,在专利文献2中提出了使用反应性的磷酸酯化合物,但由于磷酸酯在加入到树脂中时容易吸湿,或者一部分变成三维结构,环氧树脂的粘度增大,从而作业性大幅降低,因此不实用。
现有技术文献
专利文献
专利文献1:日本特开平8-337709号公报
专利文献2:日本特开平10-195178号公报
发明内容
发明所要解决的问题
本发明的目的在于,提供与缩水甘油基具有反应性的含磷化合物,具体而言,提供通过与缩水甘油基具有反应性从而能够提供可以期待阻燃化、低介电常数化等的固化性环氧树脂组合物的含磷化合物。
用于解决问题的手段
本发明者们为了实现上述目的进行了深入的研究,结果发现,具有特定结构的含磷化合物是能够实现上述目的的化合物,从而完成了本发明。
即,本发明提供由下述通式(I)表示的含磷化合物。
(式中,m表示1~10的数,R1、R2、R3以及R4彼此独立地表示氢原子、烷基或芳基,R5表示烷基、链烷二基、链烷三基、链烷四基或芳香族基团,X表示氧原子或硫原子,Y表示氧原子、硫原子或=NR',R'表示氢原子、烷基或芳基。)
另外,本发明提供一种反应方法,其特征在于,上述含磷化合物通过下述反应机理与环氧化合物反应。
(式中,m表示1~10的数,R1、R2、R3以及R4彼此独立地表示氢原子、烷基或芳基;R5表示烷基、链烷二基、链烷三基、链烷四基或芳香族基团;X表示氧原子或硫原子;Y表示氧原子、硫原子或=NR',其中,R'表示氢原子、烷基或芳基;Ar表示芳香族基团。)
另外,本发明提供一种环氧树脂固化剂,其含有上述含磷化合物。
另外,本发明提供一种固化性环氧树脂组合物,其含有上述环氧树脂固化剂。
发明效果
根据本发明,能够提供与环氧树脂的反应性优良的含磷化合物,通过配合该化合物,可以期待环氧树脂的阻燃化、低介电常数化等。
附图说明
图1是表示实施例1中得到的含磷化合物(I-1)的1H-NMR图谱的图。
图2是表示实施例1中得到的含磷化合物(I-1)的31P-NMR图谱的图。
图3是表示实施例1中得到的含磷化合物(I-1)的GC-MS图谱的图。
图4是表示实施例2中得到的含磷化合物(I-2)的1H-NMR图谱的图。
图5是表示实施例2中得到的含磷化合物(I-2)的31P-NMR图谱的图。
图6是表示实施例2中得到的含磷化合物(I-2)的GC-MS图谱的图。
图7是表示实施例3中得到的含磷化合物(I-3)的1H-NMR图谱的图。
图8是表示实施例3中得到的含磷化合物(I-3)的31P-NMR图谱的图。
图9是表示实施例3中得到的含磷化合物(I-3)的GC-MS图谱的图。
图10是表示实施例4中得到的含磷化合物(I-9)的1H-NMR图谱的图。
图11是表示实施例4中得到的含磷化合物(I-9)的31P-NMR图谱的图。
图12是表示实施例5中得到的S4的1H-NMR图谱的图。
图13是表示实施例5中得到的S4的31P-NMR图谱的图。
图14是表示实施例5中得到的S4的GC-MS图谱的图。
图15是表示实施例6中得到的S5的1H-NMR图谱的图。
图16是表示实施例6中得到的S5的31P-NMR图谱的图。
图17是表示实施例6中得到的S5的GC-MS图谱的图。
具体实施方式
以下,基于优选的实施方式对本发明进行详细地说明。
本发明的含磷化合物为由通式(I)表示的新型化合物,在其结构中,含有与缩水甘油基具有反应性的基团。
通式(I)中,作为R1、R2、R3、R4以及Y为=NR'时由R'表示的烷基,例如可以列举出:甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基、异戊基、叔戊基、己基、异己基、辛基、2-乙基己基、叔辛基、壬基、癸基等碳原子数为1~10的烷基;作为R1、R2、R3、R4以及Y为=NR'时由R'表示的芳基,例如可以列举出:苯基、萘基等碳原子数为6~12的芳基等;作为R1、R2、R3、R4,优选为碳原子数为1~5的烷基。
作为由R5表示的烷基,例如可以列举出:甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基、异戊基、叔戊基、己基、异己基、辛基、2-乙基己基、叔辛基、壬基、癸基等碳原子数为1~10的烷基等;作为由R5表示的链烷二基,例如可以列举出:亚甲基、亚乙基、亚丙基、亚丁基、亚辛基等碳原子数为1~10的链烷二基;作为由R5表示的链烷三基,例如可以列举出:甲烷三基、1,1,3-乙烷三基等碳原子数为1~6的链烷三基;作为链烷四基,可以列举出:1,1,2,2-乙烷四基等碳原子数为2~6的链烷四基。
作为由R5表示的芳香族基团,例如可以列举出:对苯二酚、间苯二酚、邻苯二酚、间苯三酚等单核多元酚化合物的残基;二羟基萘、联苯基双酚、亚甲基双酚(双酚F)、亚甲基双(邻甲酚)、亚乙基双酚、异亚丙基双酚(双酚A)、异亚丙基双(邻甲酚)、四溴双酚A、1,3-双(4-羟基枯基苯)、1,4-双(4-羟基枯基苯)、1,1,3-三(4-羟基苯基)丁烷、1,1,2,2-四(4-羟基苯基)乙烷、硫代双酚、磺酰基双酚、羟基双酚、苯酚酚醛清漆、甲酚酚醛清漆、乙基苯酚酚醛清漆、丁基苯酚酚醛清漆、辛基苯酚酚醛清漆、间苯二酚酚醛清漆、萜烯酚等多核多元酚化合物的残基等,其中,优选为由下述式(1)~(9)表示的基团。
式(1)中,n表示1~4的整数。
式(7)中,R6表示氢原子或碳原子数为1~4的烷基,o表示1~3的整数,p表示0~50的整数。
式(8)中,q表示0~50的整数。
式(9)中,r表示0~25的整数,s表示0~25的整数,r+s表示5~50的整数。
式(7)~(9)中,Z表示:
其中,式(iii)中,R8和R9为氢原子、CH3或CF3。
式(x)中,t为4~12的整数。
式(xii)中,R10为氢原子或CH3,R1~R4、X和Y与所述通式(I)中的含义相同。
作为本发明的含磷化合物,例如可以列举出由下述式(I-1)~(I-9)表示的化合物。
从含磷化合物中的磷含量和原料获得的容易性的观点出发,本发明的含磷化合物之中,特别优选上述通式(I)中R1、R2、R3以及R4彼此独立地表示碳原子数为1~5的烷基、R5表示由上述式(1)~(9)表示的芳香族基团、X以及Y表示氧原子的化合物。
本发明的含磷化合物的制造方法可以通过下述所示的式(A)或式(B)的方法来制造。
(式(A)中,R1~R5、X以及Y与上述通式(I)中的含义相同。)
(式(B)中,R1~R5、X以及Y与上述通式(I)相同含义。)
作为此处使用的碱(base),例如可以列举出:三乙胺、三丁胺、二氮杂双环十一碳烯、二氮杂双环壬烯、1,4-二氮杂双环[2.2.2]辛烷等叔胺、呲啶、N,N-二甲基氨基呲啶等呲啶类、1-甲基咪唑等咪唑类、三苯基膦、三丁基膦、三环己基膦等膦类等。
作为此处使用的溶剂(solv),例如可以列举出:甲基乙基酮、甲基戊基酮、二乙基酮、丙酮、甲基异丙基酮、丙二醇单甲基醚乙酸酯、环己酮等酮类;四氢呋喃、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、丙二醇单甲基醚等醚类;乙酸乙酯、乙酸正丁酯等酯类;苯、甲苯、二甲苯等芳香族烃;四氯甲烷、氯仿、三氯乙烷、二氯甲烷等卤代脂肪族烃;氯苯等卤代芳香族烃等。
这些反应可以在-80~100℃下、优选在室温~50℃下用0.5小时~72小时、优选用1小时~24小时实施。
本发明的含磷化合物由于可以通过下述反应机理与环氧化合物(环氧树脂)效率良好地反应,因而优选用作环氧树脂固化剂。
(式中,m表示1~10的数;R1、R2、R3以及R4彼此独立地表示氢原子、烷基或芳基;R5表示烷基、链烷二基、链烷三基、链烷四基或芳香族基团;X表示氧原子或硫原子;Y表示氧原子、硫原子或=NR',其中,R'表示氢原子、烷基或芳基;Ar表示芳香族基团。)
上述反应式中,作为由Ar表示的芳香族基团,可以列举出在对通式(I)所进行的说明中作为由R1等表示的芳基、由R5表示的芳香族基团例示出的基团等。
本发明的环氧树脂固化剂含有本发明的含磷化合物至少一种即可,可以单独使用或组合多种使用。另外,除了本发明的含磷化合物以外,也可以使用公知的环氧树脂固化剂。作为公知的固化剂,可以列举出在后述的本发明的固化性环氧树脂组合物中例示出的通用的环氧树脂固化剂。它们也可以混合使用多种。
本发明的环氧树脂固化剂中,本发明的含磷化合物的含量优选为5~100质量%,更优选为20~100质量%。
本发明的固化性环氧树脂组合物是将含有本发明的含磷化合物而成的环氧树脂固化剂与环氧化合物(环氧树脂)组合而得到的。
作为用于本发明的固化性环氧树脂组合物的环氧化合物,例如可以列举出:对苯二酚、间苯二酚、邻苯二酚、间苯三酚等单核多元酚化合物的聚缩水甘油基醚化合物;二羟基萘、联苯基双酚、亚甲基双酚(双酚F)、亚甲基双(邻甲酚)、亚乙基双酚、异亚丙基双酚(双酚A)、异亚丙基双(邻甲酚)、四溴双酚A、1,3-双(4-羟基枯基苯)、1,4-双(4-羟基枯基苯)、1,1,3-三(4-羟基苯基)丁烷、1,1,2,2-四(4-羟基苯基)乙烷、硫代双酚、磺酰基双酚、羟基双酚、苯酚酚醛清漆、甲酚酚醛清漆、乙基苯酚酚醛清漆、丁基苯酚酚醛清漆、辛基苯酚酚醛清漆、间苯二酚酚醛清漆、萜烯酚等多核多元酚化合物的聚缩水甘油基醚化合物;乙二醇、丙二醇、丁二醇、己二醇、聚乙二醇、硫代二甘醇、甘油、三羟甲基丙烷、季戊四醇、山梨糖醇、双酚A-环氧乙烷加成物等多元醇类的聚缩水甘油基醚;马来酸、富马酸、衣康酸、琥珀酸、戊二酸、辛二酸、己二酸、壬二酸、癸二酸、二聚酸、三聚酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、偏苯三酸、均苯三酸、均苯四酸、四氢邻苯二甲酸、六氢邻苯二甲酸、内亚甲基四氢邻苯二甲酸等脂肪族、芳香族或脂环族多元酸的缩水甘油酯类以及甲基丙烯酸缩水甘油酯的均聚物或共聚物;N,N-二缩水甘油基苯胺、双(4-(N-甲基-N-缩水甘油基氨基)苯基)甲烷、二缩水甘油基邻甲苯胺等具有缩水甘油基氨基的环氧化合物;乙烯基环己烯二环氧化物、二环戊二烯二环氧化物、3,4-环氧环己基甲基-3,4-环氧环己烷羧酸酯、3,4-环氧-6-甲基环己基甲基-6-甲基环己烷羧酸酯、双(3,4-环氧-6-甲基环己基甲基)已二酸酯等环状烯烃化合物的环氧化物;环氧化聚丁二烯、环氧化苯乙烯-丁二烯共聚物等环氧化共轭二烯聚合物;三缩水甘油基异氰脲酸酯等杂环化合物。另外,这些环氧化合物可以是通过末端异氰酸酯的预聚物进行内部交联而成的化合物或者用多元的活性氢化合物(多元酚、多胺、含羰基的化合物、聚磷酸酯等)进行高分子量化而成的化合物。
作为上述环氧化合物,优选环氧当量为70~3000、进一步优选环氧当量为90~2000的环氧化合物。当该环氧当量小于70时,固化物的物性有可能降低;当该环氧当量大于3000时,有可能得不到充分的固化性,因此不优选。
本发明的固化性环氧树脂组合物中,关于含有本发明的含磷化合物而成的环氧树脂固化剂与环氧化合物的使用量,相对于本发明的含磷化合物1当量,优选环氧化合物为0.1~5当量,更优选为1~3当量。
本发明的固化性环氧树脂组合物中优选使用固化催化剂。作为这样的固化性催化剂,使用对二甲基氨基呲啶、三苯基膦、咪唑、叔胺、膦、季铵盐、季鏻盐。
在本发明的固化性环氧树脂组合物中可以使用通用的环氧树脂固化剂。作为该环氧树脂固化剂,例如可以列举出:2-乙基-4-甲基咪唑、1,2-二甲基咪唑、1-(2-甲基咪唑-1-基甲基)萘-2-醇等咪唑类;二乙三胺、三乙三胺、四乙五胺等聚烷基多胺类;1,2-二氨基环己烷、1,4-二氨基-3,6-二乙基环己烷、异佛尔酮二胺等脂环式多胺类;间二甲苯二胺、二氨基二苯基甲烷、二氨基二苯基砜等芳香族多胺类等。另外,还可以列举出:使这些多胺类与苯基缩水甘油基醚、丁基缩水甘油基醚、双酚A-二缩水甘油基醚、双酚F-二缩水甘油基醚等缩水甘油基醚类或羧酸的缩水甘油酯类等各种环氧树脂通过常规方法反应而制造的聚环氧加成改性物;使这些有机多胺类与邻苯二甲酸、间苯二甲酸、二聚酸等羧酸类通过常规方法反应而制造的酰胺化改性物;使这些多胺类与甲醛等醛类以及苯酚、甲酚、二甲苯酚、叔丁基苯酚、间苯二酚等在核中具有至少一个醛化反应性部位的酚类通过常规方法反应而制造的曼尼希化改性物等。另外,也可以使用双氰胺、酸酐、咪唑类等潜在性固化剂。
另外,本发明的固化性环氧树脂组合物中,根据需要,还可以含有单缩水甘油基醚类、邻苯二甲酸二辛酯、邻苯二甲酸二丁酯、苯甲醇、煤焦油等反应性或非反应性的稀释剂(增塑剂);玻璃纤维、碳纤维、纤维素、硅砂、水泥、高岭土、粘土、氢氧化铝、膨润土、滑石、二氧化硅、微粉末二氧化硅、二氧化钛、炭黑、石墨、氧化铁、沥青物质等填充剂或颜料;γ-氨基丙基三乙氧基硅烷、N-β-(氨基乙基)-γ-氨基丙基三乙氧基硅烷、N-β-(氨基乙基)-N’-β-(氨基乙基)-γ-氨基丙基三乙氧基硅烷、γ-苯胺基丙基三乙氧基硅烷、γ-环氧丙氧基丙基三乙氧基硅烷、β-(3,4-环氧环己基)乙基三乙氧基硅烷、乙烯基三乙氧基硅烷、N-β-(N-乙烯基苄基氨基乙基)-γ-氨基丙基三乙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-氯丙基三甲氧基硅烷、γ-巯基丙基三甲氧基硅烷等硅烷偶合剂;小烛树蜡、巴西棕榈蜡、木蜡、虫蜡、蜂蜡、羊毛脂、鲸蜡、褐煤蜡、石油蜡、脂肪族蜡、脂肪族酯、脂肪族醚、芳香族酯、芳香族醚等润滑剂;增稠剂;触变剂;抗氧化剂;光稳定剂;紫外线吸收剂;阻燃剂;消泡剂;防锈剂;胶体二氧化硅、胶体氧化铝等常用的添加物,还可以进一步并用二甲苯树脂、石油树脂等粘合性的树脂类。
本发明的固化性环氧树脂组合物可以用于例如针对混凝土、水泥灰浆、各种金属、皮革、玻璃、橡胶、塑料、木、布、纸等的涂料或粘接剂;包装用粘合带、粘合标签、冷冻食品标签、可剥离标签、POS标签、粘合壁纸、粘合地板的粘合剂;铜版纸、低定量涂布纸、铸涂纸、涂装纸板、无碳复印纸、浸渍纸等加工纸;天然纤维、合成纤维、玻璃纤维、碳纤维、金属纤维等的收敛剂、防开线剂、加工剂等纤维处理剂;密封材料、水泥混和剂、防水材料等建筑材料;电子/电气设备用密封剂等广泛的用途。
实施例
接着,通过实施例对本发明进行更加详细地说明,但本发明不受这些实施例的任何限定。
[实施例1]含磷化合物[I-1]的合成
在具备转子、回流管以及隔膜的100mL三口烧瓶中装入4-二甲基氨基呲啶(DMAP)0.1g(1mmol)。充分地干燥,进行氮气置换,用注射器注入苯酚0.9g(10mmol)、超脱水四氢呋喃10mL。在使反应温度不超过30℃的状态下用注射器滴加双(二甲基氨基)磷酰氯2.0g(12mmol)。滴加结束后,搅拌10分钟,在使反应温度不超过40℃的状态下用注射器滴加三乙胺1.2g(12mmol)。滴加结束后,搅拌一夜。在反应溶液中加入饱和氯化铵水溶液5mL以及水5mL,充分进行搅拌。将反应溶液转移至分液漏斗中,用10mL***提取3次,得到有机层。将有机层用10mL水清洗,用无水硫酸镁干燥,用蒸发器除去溶剂,得到淡黄色液体(粗收率为93.3%、GC纯度为70.5%)。将粗产物通过柱色谱法(固定相:硅胶、流动相:乙酸乙酯(2体积)/己烷(1体积)、Rf=0.20)进行精制,由此,得到目标含磷化合物[I-1](无色液体、总收率:44.0%、GC纯度:>99%、31P-NMR:15.94ppm)。将鉴定结果示于图1(1H-NMR)、图2(31P-NMR)以及图3(GC-MS)。
[实施例2]含磷化合物[I-2]的合成
将具备转子、回流管以及隔膜的100mL三口烧瓶充分地干燥,进行氮气置换。在用食盐/冰水浴冷却的同时,装入乙胺四氢呋喃溶液9.5g(21mmol)、三乙胺2.1g(21mmol)以及超脱水四氢呋喃5mL。搅拌5分钟后,在使反应温度不超过0℃的状态下用注射器滴加磷酸苯基二氯化物2.1g(10mmol)。滴加结束后,再搅拌1小时。除去食盐/冰水浴,在室温下搅拌一夜。在反应溶液中加入饱和氯化铵水溶液5mL、水5mL,充分地搅拌。将溶液转移至分液漏斗,用乙酸乙酯10mL提取3次,得到有机层。将有机层用水10mL清洗,用无水硫酸镁干燥,用蒸发器除去溶剂,得到淡黄色液体(粗收率为92.9%、GC纯度为98.5%)。将粗产物通过柱色谱法(固定相:硅胶、流动相:乙酸乙酯、Rf=0.23)进行精制,由此,得到目标含磷化合物[I-2](无色液体、总收率:73.8%、GC纯度:>99%、31P-NMR:12.01ppm)。将鉴定结果示于图4(1H-NMR)、图5(31P-NMR)以及图6(GC-MS)。
[实施例3]含磷化合物[I-3]的合成
将具备转子、回流管以及隔膜的100mL三口烧瓶充分地干燥,进行氮气置换。在用食盐/冰水浴冷却的同时,装入甲基胺四氢呋喃溶液9.0g(21mmol)三乙胺2.1g(21mmol)以及超脱水四氢呋喃5mL。搅拌5分钟后,在使反应温度不超过0℃的状态下用注射器滴加磷酸苯基二氯化物2.1g(10mmol)。滴加结束后,再搅拌1小时。除去食盐/冰水浴,室温下搅拌一夜。在反应溶液中加入丙酮10mL,充分地搅拌,通过过滤分离成固体成分和滤液。在所得到的固体成分中加入丙酮10mL,充分地搅拌,再次分离成固体成分和滤液。以同样的顺序再次用丙酮清洗固体成分。回收全部滤液,用蒸发器除去溶剂,得到淡黄色晶体(粗收率为110.3%、GC纯度为95.5%)。将粗产物通过柱色谱法(固定相:硅胶、流动相:乙酸乙酯(6体积)/甲醇(1体积)、Rf=0.46)进行精制,由此,得到目标含磷化合物[I-3](白色晶体、总收率:56.5%、GC纯度:97.4%、31P-NMR:15.27ppm)。将鉴定结果示于图7(1H-NMR)、图8(31P-NMR)以及图9(GC-MS)。
[实施例4]含磷化合物[I-9]的合成
在具备转子、回流管以及N2导入口的30mL二口烧瓶中装入氯化镁0.03g(0.3mmol)、4,4'-亚甲基二苯酚2.00g(10mmol)以及磷酰氯30.67g(200mmol)。在导入N2的同时进行加热直至反应溶液回流,在该温度下搅拌一夜。导入的N2由回流管上部排出,排出的气体全部在氢氧化钠水溶液中起泡,将通过反应产生的氯化氢进行捕集。反应后,通过蒸发器除去过量的磷酰氯,得到黄色的液体(中间体)。所得到的中间体用脱水四氢呋喃10mL溶解,制备中间体的THF溶液。接着,将具备转子、回流管以及隔膜的100mL三口烧瓶充分地干燥,进行氮气置换。在用食盐/冰水浴冷却的同时,装入甲基胺四氢呋喃溶液18.08g(42mmol)、三乙胺4.25g(42mmol)。搅拌5分钟后,在使反应温度不超过20℃的状态下用注射器滴加中间体的THF溶液。滴加结束后,再搅拌1小时。除去食盐/冰水浴,室温下搅拌一夜。反应后,通过蒸发器除去溶剂以及过量的原料,得到淡黄色固体。将粗产物通过柱色谱法(固定相:硅胶、流动相:乙酸乙酯(5体积)/甲醇(1体积)、Rf=0.29)进行精制,得到目标含磷化合物[I-9](白色固体、总收率:35.2%)。将鉴定结果示于图10(1H-NMR)以及图11(31P-NMR)。
[实施例5]
根据下述反应式,在DMAP 2.3mg(7.5mol%)催化剂存在下,使实施例2中得到的含磷化合物[I-2]57.1mg(0.25mmol)与Adeka Glycirol ED-509S51.6mg(0.25mmol)在氮气流下、在140℃下反应2小时。由1H-NMR(图12)、31P-NMR(图13)以及GC-MS(图14)确认得到了作为主产物的S4。
[实施例6]
根据下述反应式,在DMAP 2.3mg(7.5mol%)催化剂存在下,使实施例3中得到的含磷化合物[I-3]50.0mg(0.25mmol)与Adeka Glycirol ED-509S51.6mg(0.25mmol)在氮气流下、在130℃下反应2小时。由1H-NMR(图15)、31P-NMR(图16)以及GC-MS(图17)确认得到了作为主产物的S5。
[实施例7]
将Adeka Resin EP-4100L 1.02g(100.0重量份)、本发明的含磷化合物[I-9]0.16g(15.7重量份)以及2-乙基-4-甲基咪唑0.03g(3.0重量份)混合,在恒温槽中在150℃下加热3小时,接着在180℃下加热3小时,得到无粘性的褐色的固化物。用DSC测量该固化物的Tg,结果为140℃。
前文由本发明的实施例示出了本发明的含磷化合物与缩水甘油基具有反应性。通过在环氧树脂组合物中配合本发明的磷酸酯,固化物物性的降低得以抑制,能够提供可以期待具有阻燃性、低介电常数的环氧树脂固化物。
Claims (5)
2.根据权利要求1所述的环氧树脂固化剂,其特征在于,所述通式(I)中,X以及Y表示氧原子。
4.根据权利要求3所述的反应方法,其特征在于,所述通式(I)中,X以及Y表示氧原子。
5.一种固化性环氧树脂组合物,其含有权利要求1或2所述的环氧树脂固化剂。
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TWI679242B (zh) | 2015-03-23 | 2019-12-11 | 日商Adeka股份有限公司 | 環氧樹脂組成物 |
JP7066268B2 (ja) * | 2017-08-23 | 2022-05-13 | 株式会社Adeka | 難燃性エポキシ樹脂組成物 |
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JPH10265487A (ja) * | 1997-03-21 | 1998-10-06 | Kanagawa Univ | ホスホン酸エステル類並びにポリホスホネートの 製造方法と硬化性組成物 |
CN102617637A (zh) * | 2012-02-23 | 2012-08-01 | 四川大学 | 以对苯二酚磷酸酯为骨架的有机磷氮系阻燃剂的制备方法 |
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US1333276A (en) * | 1919-10-25 | 1920-03-09 | Thomas E Murray | Seal-fastening |
US1494774A (en) * | 1923-05-29 | 1924-05-20 | Eugene H Davis | Cake-cutting machine |
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NL131206C (zh) * | 1965-09-03 | |||
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FR2102301A1 (zh) * | 1970-08-17 | 1972-04-07 | Monsanto Co | |
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DE2505326A1 (de) * | 1974-02-18 | 1975-08-21 | Sandoz Ag | Flammfest ausgeruestete regenerierte cellulose |
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2014
- 2014-09-10 EP EP14850484.8A patent/EP3053928A4/en not_active Withdrawn
- 2014-09-10 WO PCT/JP2014/073994 patent/WO2015049965A1/ja active Application Filing
- 2014-09-10 BR BR112016005231-5A patent/BR112016005231B1/pt active IP Right Grant
- 2014-09-10 CN CN202010926152.XA patent/CN112029073A/zh active Pending
- 2014-09-10 JP JP2015540441A patent/JP6499968B2/ja active Active
- 2014-09-10 CN CN201480049257.4A patent/CN105764910A/zh active Pending
- 2014-09-10 KR KR1020167005774A patent/KR102320939B1/ko active IP Right Grant
- 2014-09-19 TW TW103132525A patent/TWI623547B/zh active
- 2014-11-10 US US14/915,766 patent/US9738667B2/en active Active
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US4086302A (en) * | 1975-07-28 | 1978-04-25 | Monsanto Company | Phosphoroamidates |
JPH10265487A (ja) * | 1997-03-21 | 1998-10-06 | Kanagawa Univ | ホスホン酸エステル類並びにポリホスホネートの 製造方法と硬化性組成物 |
CN102617637A (zh) * | 2012-02-23 | 2012-08-01 | 四川大学 | 以对苯二酚磷酸酯为骨架的有机磷氮系阻燃剂的制备方法 |
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EP3053928A1 (en) | 2016-08-10 |
EP3053928A4 (en) | 2017-03-01 |
KR102320939B1 (ko) | 2021-11-03 |
CN105764910A (zh) | 2016-07-13 |
WO2015049965A1 (ja) | 2015-04-09 |
JPWO2015049965A1 (ja) | 2017-03-09 |
JP6499968B2 (ja) | 2019-04-10 |
US9738667B2 (en) | 2017-08-22 |
US20160200747A1 (en) | 2016-07-14 |
BR112016005231B1 (pt) | 2021-04-13 |
TWI623547B (zh) | 2018-05-11 |
KR20160065814A (ko) | 2016-06-09 |
TW201518312A (zh) | 2015-05-16 |
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