CN107522831B - 一种耐高温低介电的含硅苯并噁嗪及其制备方法 - Google Patents
一种耐高温低介电的含硅苯并噁嗪及其制备方法 Download PDFInfo
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- 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0246—Polyamines containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
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Abstract
本发明公开了一种耐高温低介电的含硅苯并噁嗪及其制备方法,含硅苯并噁嗪单体以含硅二苯胺、酚类化合物和多聚甲醛为原料在溶剂回流条件下制成;含硅二苯胺由原料胺基苯酚和氯硅烷进行反应得到;含硅苯并噁嗪单体制备方法:将含硅二苯胺、酚类化合物、多聚甲醛加入到盛有有机溶剂的圆底烧瓶中,加热回流分水1~2天,然后进行分离处理,得到含硅苯并噁嗪单体。本发明的含硅苯并噁嗪单体可以单独使用或与其它苯并噁嗪单体或酚醛树脂或环氧树脂混合使用,得到的固化制品具有更好的耐热性、阻燃性、介电性和防腐性能,可以用于耐烧蚀材料、阻燃材料、防腐材料、电子封装等领域。
Description
技术领域
本发明涉及一种高温低介电的苯并噁嗪及其聚合物,具体涉及一种含硅苯并噁嗪单体、聚苯并噁嗪及相应的制备方法。
背景技术
苯并噁嗪是在传统酚醛树脂的基础上发展而来的新型树脂。它是由酚类、甲醛或多聚甲醛、伯胺通过Mannich缩合反应得到的六元杂环化合物。苯并噁嗪经高温开环聚合所生成的苯并噁嗪树脂与其他热固性树脂(如环氧树脂、酚醛树脂、双马来酰亚胺树脂等)相比,苯并噁嗪树脂不仅具有传统酚醛树脂的耐高温、阻燃、良好的介电性能和力学性能,还具有残炭率高、玻璃化转变温度高、尺寸稳定性好、固化过程不需要催化剂、无小分子放出,低吸水性及很强的分子设计性等优点,更适于作为树脂基材制备各种复合材料零部件。因此,苯并噁嗪树脂具有更广阔的应用前景。但是,现有的并噁嗪树脂的耐热性、介电性能、玻璃转化温度等有待提高,进而改善高性能结构材料、耐烧蚀材料、阻燃材料和介电材料的性能。
众所周知,含硅化合物具有高的比表面能,优异的阻燃性能、介电性能和耐烧蚀性能。所以含硅化合物在介电材料、阻燃材料、防腐材料等方面应用广泛。单把硅元素引入到苯并噁嗪中的报道还很少。目前最常见的是把苯并噁嗪与含硅化合物共混。比如,苯并噁嗪与纳米二氧化硅共混,苯并噁嗪与硅氧烷聚合物共混等。虽然共混能提高材料的阻燃、介电及表面性能,但不可避免的会降低材料的力学性能。因此,相关研究人员直接用苯胺基POSS来合成苯并噁嗪,但苯胺基POSS成本非常昂贵,不利于大规模生产。现在,人们把目光转向了胺丙基硅氧烷及其低聚物,比如用双胺丙基硅氧烷低聚物,胺丙基三甲氧基硅等来合成苯并噁嗪。所得到的苯并噁嗪具有优异的界面性能,但是由于烷基链的引入,降低了体系的热稳定性和力学性能。也有采用聚硅醚型的二酚来合成苯并噁嗪的报道,但该方法合成步骤过于繁琐,不利于实际大规模应用。
发明内容
本发明的一个目的是解决至少上述问题和/或缺陷,并提供至少后面将说明的优点。
本发明还有一个目的是解决现有的含硅苯并噁嗪存在的力学性能差、热稳定性差、阻燃性能和介电性能不够好,玻璃化转变温度不够高等技术问题,提供一种热稳定性好、高残炭率、低介电、阻燃性好和防腐性好的含硅苯并噁嗪。
本发明还有一个目的是提供一种含硅苯并噁嗪单体、及其聚合物的制备方法,工艺步骤简单,产率高,重复性好。
为了实现本发明这些目的和其它优点,本发明提供了一种耐高温低介电的含硅苯并噁嗪单体,以含硅二苯胺、酚类化合物和多聚甲醛为原料在溶剂回流条件下制成。
优选的是,所述含硅二苯胺以胺基苯酚和氯硅烷为原料,四氢呋喃为溶剂,在三乙胺存在条件下进行反应得到,含硅二苯胺的结构通式如下:
式中,R1和R2分别为甲基、乙基、苯基、乙烯基中的一种。
优选的是,所述酚类化合物为单酚类化合物,其中,含硅二苯胺、单酚类化合物、多聚甲醛的摩尔比为1:2:4.1~4.4,合成的含硅苯并噁嗪单体的结构通式如下:
式中,R3和R3分别为甲基,乙基、叔丁基、乙炔基、醛基、氰基、溴、氯、氟、乙烯基、甲氧基、硝基、羟基、胺基、羧基、磺酸基、3-(N,N-二甲基胺基)丙基中的一种。
进一步优选的是,所述单酚类化合物为苯酚,含硅二苯胺为双(对胺基苯氧基)二苯基硅,合成的苯并噁嗪单体结构式如下:
优选的是,所述酚类化合物为双酚类化合物,其中,含硅二苯胺、双酚类化合物、多聚甲醛的摩尔比为1:1:4.1~4.4,合成的含硅苯并噁嗪单体的结构通式如下:
式中,R5为亚甲基、1,1-二甲基亚甲基、亚砜基、羰基、氧中的一种。
进一步优选的是,所述双酚类化合物为双酚A,含硅二苯胺为双(对胺基苯氧基)二苯基硅,合成的苯并噁嗪单体结构式如下:
一种耐高温低介电的含硅苯并噁嗪单体的制备方法,步骤为:将含硅二苯胺、酚类化合物、多聚甲醛加入到盛有有机溶剂的圆底烧瓶中,加热回流分水1~2天,然后进行分离处理,得到含硅苯并噁嗪单体。
进一步优选的是,所述酚类化合物为单酚时,对应的耐高温低介电的含硅苯并噁嗪单体的制备方法,步骤为:将含硅二苯胺、单酚类化合物、多聚甲醛加入到盛有溶剂苯、甲苯或者氯仿的圆底烧瓶中,加热回流分水1~2天,然后用二氯甲烷萃取,饱和碳酸钾溶液洗涤,有机相旋干后柱层析得到含硅苯并噁嗪单体。
进一步优选的是,所述酚类化合物为双酚时,对应的耐高温低介电的含硅苯并噁嗪单体的制备方法,步骤为:将含硅二苯胺、双酚类化合物、多聚甲醛加入到盛有溶剂苯、甲苯或者氯仿的圆底烧瓶中,加热回流分水1~2天,然后过滤,得到含硅苯并噁嗪单体。
一种含硅苯并噁嗪单体开环聚合制备聚苯并噁嗪的方法,具体步骤:将含硅苯并噁嗪单体装入圆形铝制模具内,然后置于电热恒温干燥箱中在不同温度下分阶段固化得到开环聚合的聚苯并噁嗪,升温固化过程为:首先升温至220℃热固化2~3h,然后升温至240℃热固化2~3h,再升温至260℃热固化2~3h。
与现有技术相比,本发明的有益之处在于:
其一、以含硅二苯胺为原料制备含硅苯并噁嗪,由于含硅苯并噁嗪分子结构中不存在烷基链,具有优异的热稳定性和力学性能,同时硅原子的引入使得苯并噁嗪具有优异的介电性能、阻燃性能和防腐性能。
其二、含硅苯并噁嗪通过含硅二苯胺与酚类化合物、多聚甲醛加热回流制备,工艺简单,产率高,重复性好。
其三、含硅二胺可由羟基苯胺与氯硅烷反应制得,或由溴苯胺与氯硅烷反应制得,原料廉价易得,有效降低了经济成本。
其四、苯并噁嗪的热稳定性好、残炭率高、玻璃化转变温度高、可以作为单体单独使用或与其它苯并噁嗪单体或酚醛树脂或环氧树脂混合使用,同时苯并噁嗪中的硅有利于提高残炭率、介电性能、阻燃性能、界面性能、可应用于高性能结构材料、耐烧蚀材料、阻燃材料、电子封装材料等领域。
本发明的其它优点、目标和特征将部分通过下面的说明体现,部分还将通过对本发明的研究和时间而为本领域的技术人员所理解。
附图说明
图1.双(胺基苯氧基)二苯基硅、苯酚型含硅苯并噁嗪单体的核磁共振氢谱。
图2.双(胺基苯氧基)二苯基硅、苯酚型含硅苯并噁嗪单体的核磁共振碳谱。
图3.双(胺基苯氧基)二苯基硅、苯酚型含硅苯并噁嗪单体红外光谱图。
图4.双(胺基苯氧基)二苯基硅、苯酚型含硅苯并噁嗪单体的DSC图。
图5.双(胺基苯氧基)二苯基硅、苯酚型含硅苯并噁嗪聚合物的TGA图。
图6.双(胺基苯氧基)二苯基硅、苯酚型含硅苯并噁嗪聚合物的DSC图。
图7.双(胺基苯氧基)二苯基硅、双酚A型含硅苯并噁嗪单体的IR图。
图8.双(胺基苯氧基)二甲基硅、苯酚型含硅苯并噁嗪单体的DSC图。
具体实施方式
以下结合附图对本发明的优选实施例进行说明,应当理解,此处所描述的优选实施例仅用于说明和解释本发明,并不用于限定本发明。
实施例1
室温条件下,将2g双(胺基苯氧基)二苯基硅、0.88ml苯酚和0.62g多聚甲醛加入到盛有10ml甲苯的圆底烧瓶中,双(胺基苯氧基)二苯基硅、苯酚和多聚甲醛的摩尔比为1:2:4.1,加热回流反应2天,反应完全后,用二氯甲烷萃取,饱和碳酸钾溶液洗涤,有机相用旋转蒸发仪旋干甲苯,柱层析分离得到含硅苯并噁嗪单体。反应原理为:
将20g上述制备的含硅苯并噁嗪单体倒入圆形铝制模具内,置于电热恒温干燥箱中在不同温度下分阶段固化得到开环聚合的聚苯并噁嗪,升温固化过程为:首先升温至220℃热固化2h,然后升温至240℃热固化2h,最后升温至260℃热固化2h。
实施例2
室温条件下,将2g双(胺基苯氧基)二苯基硅、0.88ml苯酚和0.67g多聚甲醛加入到盛有10ml苯的圆底烧瓶中,双(胺基苯氧基)二苯基硅、苯酚和多聚甲醛的摩尔比为1:2:4.4,加热回流反应1天,反应完全后,用二氯甲烷萃取,饱和碳酸钾溶液洗涤,有机相用旋转蒸发仪旋干苯,柱层析分离得到含硅苯并噁嗪单体。反应原理为:
将20g上述制备的含硅苯并噁嗪单体倒入圆形铝制模具内,置于电热恒温干燥箱中在不同温度下分阶段固化得到开环聚合的聚苯并噁嗪,升温固化过程为:首先升温至220℃热固化2.5h,然后升温至240℃热固化2.5h,最后升温至260℃热固化2.5h。
实施例3
室温条件下,将2g双(胺基苯氧基)二苯基硅、0.88ml苯酚和0.64g多聚甲醛加入到盛有10ml氯仿的圆底烧瓶中,双(胺基苯氧基)二苯基硅、苯酚和多聚甲醛的摩尔比为1:2:4.2,加热回流反应1天,反应完全后,用旋转蒸发仪旋干氯仿,柱层析分离得到含硅苯并噁嗪单体。反应原理为:
将20g上述制备的含硅苯并噁嗪单体倒入圆形铝制模具内,置于电热恒温干燥箱中在不同温度下分阶段固化得到开环聚合的聚苯并噁嗪,升温固化过程为:首先升温至220℃热固化3h,然后升温至240℃热固化3h,最后升温至260℃热固化3h。
将实施例1、2和3制备的含硅苯并噁嗪单体分别进行核磁共振氢谱、核磁共振碳谱、红外光谱、DSC谱图等一系列分析,具体结果见图1~4。得出的结果是,3个实施例制备的含硅苯并噁嗪单体的同一性能表征图谱相同,具体测试结果相同,说明3个实施例制备得到的是同一种含硅苯并噁嗪单体。
图1是核磁共振氢谱测试结果1H NMR(600MHz,DMSO,ppm):7.69-7.71(m,4H,Ar-H),7.45-7.47(m,2H,Ar-H),7.39-7.42(m,4H,Ar-H),7.04-7.06(m,4H,Ar-H),6.95-6.98(m,4H,Ar-H),6.86-6.87(m,6H,Ar-H),6.84-6.85(m,2H,Ar-H),5.31(s,4H,O-CH2-N),4.52(s,4H,Ar-CH2-N)。
图2是核磁共振碳谱测试结果13C NMR(600MHz,DMSO,ppm):153.88,147.47,142.80,134.52,131.08,130.87,128.27,127.57,127.12,121.17,120.39,119.58,119.05,116.16,79.22,49.17。
图3是红外光谱测试结果(KBr,cm-1):833cm-1为O-Si键的弯曲振动峰,942cm-1为与噁嗪环直接相连的苯环的特征吸收峰,1120cm-1为Si-O键的伸缩振动峰,1233cm-1是C-Si键的伸缩振动峰,1506cm-1和1589cm-1为苯环上C=C的伸缩振动峰。
结合核磁共振氢谱和红外光谱证实所得产物为目标物含硅苯并噁嗪单体。
图4是DSC谱图(升温速率10℃/min):起始固化温度206℃,峰值固化温度227℃。
将实施例1、2和3制备的聚苯并噁嗪分别进行TGA和DSC谱图分析,具体结果见图5和图6。得出的结果是,3个实施例制备的聚苯并噁嗪的同一性能表征图谱相同,具体测试结果相同,说明3个实施例制备得到的是同一种聚苯并噁嗪。
图5是TGA谱图:聚苯并噁嗪的初始分解温度T5%为420℃(定义质量损失5%时的温度为初始分解温度),升温至463℃时质量损失10%,残炭率为74%。
图6是DSC谱图:从图中可以看到聚苯并噁嗪的玻璃化转变温度为319℃。
现有技术中,双酚A/苯胺型苯并噁嗪的初始分解温度为315℃,800℃残炭率为35%,玻璃化转变温度为160℃。从本发明的含硅苯并噁嗪聚合物的TGA和DSC谱图可以看出,该种苯并噁嗪的分解温度为420℃,比现有的双酚A/苯胺型苯并噁嗪提高了100℃,残炭率从35%提高到74%,提高了39%。玻璃化转变温度从160℃提高到319℃,提高了159℃。
实施例4
在室温条件下,将1g双(对胺基苯氧基)二苯基硅、0.57g双酚A、0.317g多聚甲醛加入到盛有10ml甲苯溶剂的圆底烧瓶中,然后油浴温度升高到130℃,回流分水反应6h,过滤,先后用甲醇、丙酮洗涤滤饼,得到含硅苯并噁嗪单体1.4g。其中双(对胺基苯氧基)二苯胺、双酚A、多聚甲醛的摩尔比为1:1:4.2.反应原理为:
将上述制备的含硅苯并噁嗪单体倒入圆形铝制模具内,置于电热恒温干燥箱中在不同温度下分阶段固化得到开环聚合的聚苯并噁嗪,升温固化过程为:首先升温至220℃热固化3h,然后升温至240℃热固化3h,最后升温至260℃热固化3h。
图7是双(胺基苯氧基)二苯基硅、双酚A型含硅苯并噁嗪单体的红外光谱图:936cm-1为噁嗪环的特征吸收峰,1227cm-1为C-Si键的伸缩振动,1117cm-1为Si-O键的伸缩振动峰,1430cm-1,1507cm-1和1612cm-1为苯环上C=C的伸缩振动峰,3461cm-1为末端羟基或胺基的伸缩振动峰。
实施例5
室温条件下,将2g双(胺基苯氧基)二甲基硅、1.28ml苯酚和0.919g多聚甲醛加入到盛有10ml氯仿的圆底烧瓶中,双(胺基苯氧基)二甲基硅、苯酚和多聚甲醛的摩尔比为1:2:4.2,加热回流反应1天,反应完全后,用旋转蒸发仪旋干氯仿,柱层析分离得到含硅苯并噁嗪单体。反应原理为:
将20g上述制备的含硅苯并噁嗪单体倒入圆形铝制模具内,置于电热恒温干燥箱中在不同温度下分阶段固化得到开环聚合的聚苯并噁嗪,升温固化过程为:首先升温至220℃热固化3h,然后升温至240℃热固化3h,最后升温至260℃热固化3h。
图8是双(对胺基苯氧基)二甲基硅、苯酚型含硅苯并噁嗪单体的DSC谱图。从图中可以看出,其起始固化温度为232℃,峰值固化温度为261℃。
综上所述,本发明制备的含硅苯并噁嗪,分子结构中不存在烷基链,具有优异的热稳定性和力学性能,同时硅原子的引入使得苯并噁嗪具有优异的介电性能、阻燃性能和防腐性能。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (9)
1.一种耐高温低介电的含硅苯并噁嗪单体,其特征在于,以含硅二苯胺、酚类化合物和多聚甲醛为原料在溶剂回流条件下制成;所述含硅二苯胺以胺基苯酚和氯硅烷为原料,四氢呋喃为溶剂,在三乙胺存在条件下进行反应得到,含硅二苯胺的结构通式如下:
式中,R1和R2分别为甲基、乙基、苯基、乙烯基中的一种。
2.如权利要求1所述的耐高温低介电的含硅苯并噁嗪单体,其特征在于,所述酚类化合物为单酚类化合物,合成的含硅苯并噁嗪单体的结构通式如下:
式中,R3和R4分别为甲基,乙基、叔丁基、乙炔基、醛基、氰基、溴、氯、氟、乙烯基、甲氧基、硝基、羟基、胺基、羧基、磺酸基、3-(N,N-二甲基胺基)丙基中的一种。
3.如权利要求1所述的耐高温低介电的含硅苯并噁嗪单体,其特征在于,所述酚类化合物为苯酚,含硅二苯胺为双(对胺基苯氧基)二苯基硅,合成的苯并噁嗪单体结构式如下:
4.如权利要求1所述的耐高温低介电的含硅苯并噁嗪单体,其特征在于,所述酚类化合物为双酚类化合物,合成的含硅苯并噁嗪单体的结构通式如下:
式中,R5为亚甲基、1,1-二甲基亚甲基、亚砜基、羰基、氧中的一种。
5.如权利要求4所述的耐高温低介电的含硅苯并噁嗪单体,其特征在于,所述双酚类化合物为双酚A,含硅二苯胺为双(对胺基苯氧基)二苯基硅,合成的苯并噁嗪单体结构式如下:
6.一种如权利要求1-5任意一项所述的耐高温低介电的含硅苯并噁嗪单体的制备方法,其特征在于,将含硅二苯胺、酚类化合物、多聚甲醛加入到盛有有机溶剂的圆底烧瓶中,加热回流分水1~2天,然后进行分离处理,得到含硅苯并噁嗪单体。
7.如权利要求6所述的耐高温低介电的含硅苯并噁嗪单体的制备方法,其特征在于,将含硅二苯胺、单酚类化合物、多聚甲醛加入到盛有溶剂苯、甲苯或者氯仿的圆底烧瓶中,加热回流分水1~2天,然后用二氯甲烷萃取,饱和碳酸钾溶液洗涤,有机相旋干后柱层析得到含硅苯并噁嗪单体。
8.如权利要求6所述的耐高温低介电的含硅苯并噁嗪单体的制备方法,其特征在于,将含硅二苯胺、双酚类化合物、多聚甲醛加入到盛有溶剂苯、甲苯或者氯仿的圆底烧瓶中,加热回流分水1~2天,然后过滤,得到含硅苯并噁嗪单体。
9.一种如权利要求6所述的含硅苯并噁嗪单体开环聚合制备聚苯并噁嗪的方法,其特征在于,将含硅苯并噁嗪单体装入圆形铝制模具内,然后置于电热恒温干燥箱中在不同温度下分阶段固化得到开环聚合的聚苯并噁嗪,升温固化过程为:首先升温至220℃热固化2~3h,升温至240℃热固化2~3h,然后升温至260℃热固化2~3h。
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