CN105153144B - 主链双胺型喹喔啉基苯并噁嗪及其制备方法 - Google Patents
主链双胺型喹喔啉基苯并噁嗪及其制备方法 Download PDFInfo
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- 150000004985 diamines Chemical class 0.000 title claims abstract description 22
- ZHTXFOFNOCKVRR-UHFFFAOYSA-N 3-quinoxalin-2-yl-2H-1,2-benzoxazine Chemical compound N1=C(C=NC2=CC=CC=C12)C=1NOC2=C(C=1)C=CC=C2 ZHTXFOFNOCKVRR-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 19
- ZYMCBJWUWHHVRX-UHFFFAOYSA-N (4-nitrophenyl)-phenylmethanone Chemical compound C1=CC([N+](=O)[O-])=CC=C1C(=O)C1=CC=CC=C1 ZYMCBJWUWHHVRX-UHFFFAOYSA-N 0.000 claims abstract description 10
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 14
- -1 methoxyl group Chemical group 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
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- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 5
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- ZYYNLLHFNBENFK-UHFFFAOYSA-N 2-nitroquinoxaline Chemical compound C1=CC=CC2=NC([N+](=O)[O-])=CN=C21 ZYYNLLHFNBENFK-UHFFFAOYSA-N 0.000 abstract 2
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 abstract 2
- WSDQIHATCCOMLH-UHFFFAOYSA-N phenyl n-(3,5-dichlorophenyl)carbamate Chemical compound ClC1=CC(Cl)=CC(NC(=O)OC=2C=CC=CC=2)=C1 WSDQIHATCCOMLH-UHFFFAOYSA-N 0.000 abstract 2
- YOWAEZWWQFSEJD-UHFFFAOYSA-N quinoxalin-2-amine Chemical compound C1=CC=CC2=NC(N)=CN=C21 YOWAEZWWQFSEJD-UHFFFAOYSA-N 0.000 abstract 2
- FYTRVVJHEWUARG-UHFFFAOYSA-N n-(2-aminophenyl)nitramide Chemical class NC1=CC=CC=C1N[N+]([O-])=O FYTRVVJHEWUARG-UHFFFAOYSA-N 0.000 abstract 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract 1
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 14
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- 238000013461 design Methods 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- CRBUJVZQLUDCSZ-UHFFFAOYSA-N 4-nitrosobenzene-1,2-diamine Chemical compound NC1=CC=C(N=O)C=C1N CRBUJVZQLUDCSZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
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- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
-
- 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
- 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
本发明提供的是一种主链双胺型型喹喔啉基苯并噁嗪及其制备方法。以4‑硝基苯偶酰和4‑硝基邻苯二胺为原料,得到2‑(4‑硝基苯基)‑3‑苯基‑6‑硝基喹喔啉和2‑苯基‑3‑(4‑硝基苯基)‑6‑硝基喹喔啉混合物,经催化还原得到2‑(4‑氨苯基)‑3‑苯基‑6‑氨基喹喔啉和2‑苯基‑3‑(4‑氨苯基)‑6‑氨基喹喔啉混合物,再与酚类化合物、多聚甲醛经一步法Mannich缩合,得到一种喹喔啉环位于主链的双胺型喹喔啉基苯并噁嗪混合单体;本发明合成的主链双胺型喹喔啉基聚苯并噁嗪具有优良的热性能及力学性能,可广泛用于高性能结构材料、电子封装材料、耐腐蚀材料和阻燃材料等领域。
Description
技术领域
本发明涉及的是一种有机高分子材料,本发明也涉及一种有机高分子材料的制备方法。具体地说是一种主链双胺型喹喔啉基苯并噁嗪及其制备方法。
背景技术
苯并噁嗪树脂是一种新型的酚醛树脂,它能够自催化开环聚合成三维网络结构,其聚合物具有热稳定性和机械性能优异、耐潮湿性、阻燃性、低吸水性及绝缘性好等优点。在固化过程中,无小分子释放、低膨胀系数、低粘度、接近零收缩,并且具有很强的分子设计性,且用于合成苯并噁嗪的主要原料价格低廉、来源广泛。苯并噁嗪在先进复合材料基体树脂、耐烧蚀材料方面存在应用价值,可应用在航空航天、电子封装、建筑等行业。
喹喔啉是一种杂环化合物,它由一个苯环与一个吡嗪环稠合而成,其2、3、6位可引入多种活性基团,具有非常灵活的分子设计性,可用于合成聚苯基喹喔啉、喹喔啉基聚酰亚胺、聚醚、聚酯等聚合物。与此同时,这种喹喔啉结构具有较高的键能、庞大的摩尔体积以及较弱的极性,赋予了以其制得的聚合物优良的耐热及热氧化稳定性、耐环境稳定性、低介电常数与介电损耗、在有机溶剂中良好的溶解性以及良好的力学加工性能。
发明内容
本发明的目的在于提供一种具有优良的热性能及力学性能的主链双胺型喹喔啉基苯并噁嗪。本发明的目的还在于提供一种主链双胺型喹喔啉基苯并噁嗪的制备方法。
本发明的目的是这样实现的:
本发明的主链双胺型喹喔啉基苯并噁嗪单体的结构式为:
式中,R为氢、甲基、甲氧基、乙基、乙氧基、三氟甲基、三氟甲氧基或腈基中的一种。
本发明的主链双胺型喹喔啉基苯并噁嗪是按照以下方式制备的:
(1)以冰乙酸为溶剂,向容器中加入摩尔比为1:1~1.2的4-硝基苯偶酰和4-硝基邻苯二胺,混合物回流5~12h,然后冷却至室温,过滤,滤饼烘干,所得粗产物用冰乙酸重结晶1~3次,得到2-(4-硝基苯基)-3-苯基-6-硝基喹喔啉和2-苯基-3-(4-硝基苯基)-6-硝基喹喔啉混合物、简写为M1;
(2)将质量比为1:0.03~0.05的M1与钯碳加入乙醇中,逐滴加入质量比浓度为80%的水合肼,其中,水合肼同M1的摩尔比为3.2~4:1,在回流温度下反应8~12h,趁热过滤,冷却至室温,再经过滤、水洗、真空干燥,得到2-(4-氨苯基)-3-苯基-6-氨基喹喔啉和2-苯基-3-(4-氨苯基)-6-氨基喹喔啉混合物、简写为M2;
(3)将M2、酚类化合物、多聚甲醛以及甲苯或二甲苯依次加入到容器中,M2、酚类化合物和多聚甲醛的摩尔比为1:2:4,在100~160℃下反应4~8h,将所得产物加入到正己烷中,沉淀物用正己烷洗涤数次,真空干燥,最终得到主链双胺型喹喔啉基苯并噁嗪单体。
步骤(3)中所述的酚类化合物为苯酚、间甲酚、对甲酚、3-乙基苯酚、4-乙基苯酚、3-甲氧基苯酚、2-乙氧基苯酚、3-三氟甲基苯酚、3-三氟甲氧基苯酚或对腈基苯酚中的一种。
本发明的主链双胺型喹喔啉基苯并噁嗪单体结构表征利用红外光谱(Spotlight100,美国PE公司)和核磁共振谱仪(AVANCE-500,瑞士Bruker),红外光谱测试采用溴化钾压片法,样品扫描4次,分辨率4cm-1,扫描范围到4000~500cm-1,核磁共振氢谱是以四甲基硅烷(TMS)作内标,氘代二甲基亚砜(DMSO)作溶剂。聚合物性能测试采用热重分析仪(TGA,美国TA公司)和示差扫描量热仪(DSC,美国TA公司)。其中TGA和DSC均使用氮气氛围,升温速率为20℃/min。
本发明从分子设计的角度出发,利用喹喔啉中2、3、6位具有较高的活性,合成了一种喹喔啉二胺,由于喹喔啉特殊的分子结构,这种喹喔啉二胺是一种空间结构不同的互变异构体(如图2),即含有两种分子结构:2-(4-氨苯基)-3-苯基-5-氨基喹喔啉和2-苯基-3-(4-氨苯基)-5-氨基喹喔啉的混合物,以其为原料合成出一类具有不同空间构型,且喹喔啉环位于主链的双胺型喹喔啉基苯并噁嗪混合物。
本发明以4-硝基苯偶酰和4-硝基邻苯二胺为原料,得到2-(4-硝基苯基)-3-苯基-6-硝基喹喔啉和2-苯基-3-(4-硝基苯基)-6-硝基喹喔啉混合物,经催化还原得到2-(4-氨苯基)-3-苯基-6-氨基喹喔啉和2-苯基-3-(4-氨苯基)-6-氨基喹喔啉混合物,再与酚类化合物、多聚甲醛经一步法Mannich缩合,得到一种喹喔啉环位于主链的双胺型喹喔啉基苯并噁嗪混合单体;本发明合成的主链双胺型喹喔啉基聚苯并噁嗪具有优良的热性能及力学性能,可广泛用于高性能结构材料、电子封装材料、耐腐蚀材料和阻燃材料等领域。
附图说明
图1是本发明的主链双胺型喹喔啉基苯并噁嗪的结构示意图。
图2是喹喔啉二胺空间结构不同的互变异构体示意图。
具体实施方式
下面通过实施例对本发明进行具体描述,有必要在此指出的是,本发明实施例只用于对本发明进行进一步说明,但不能理解为对本发明保护范围的限制,该领域的技术熟练人员根据上述本发明的内容作出一些非本质的改进和调整。
实施例1
(1)向三口烧瓶中分别加入4-硝基苯偶酰(25.5g,0.1mol)、4-硝基邻苯二胺(16.8g,0.11mol)和250mL冰乙酸,混合物回流反应6h,然后冷却至室温后,过滤收集形成的沉淀,烘干,所得粗产物用冰乙酸重结晶,得到2-(4-硝基苯基)-3-苯基-6-硝基喹喔啉和2-苯基-3-(4-硝基苯基)-6-硝基喹喔啉混合物(M1,30.3g),收率81.5%;
(2)将M1(18.6g,0.05mol)和钯碳催化剂(0.56g)加入到500mL乙醇中,逐滴加入80%水合肼(2.25g),在回流温度下反应10h,趁热过滤,除去钯碳催化剂,滤液冷却至室温,析出晶体,过滤,再用蒸馏水水洗3~4次,最后经真空干燥,得到2-(4-氨苯基)-3-苯基-6-氨基喹喔啉和2-苯基-3-(4-氨苯基)-6-氨基喹喔啉混合物(M2,14.1g),收率90.4%;
(3)向带有磁力搅拌器、冷凝管以及温度计的三口烧瓶中分别加入的M2(3.12g,0.01mol)、苯酚(1.88g,0.02mol)、多聚甲醛(1.2g,0.04mol)和10mL二甲苯,在140℃下反应6h,反应结束后冷却至室温,加入正己烷,沉淀物用正己烷洗涤,再经过滤、真空干燥,最终得到苯酚-双胺型喹喔啉基苯并噁嗪单体,收率79.9%。
核磁共振氢谱测试结果(500M,DMSO,ppm):8.33~6.68(m,20H,Ar-H),5.47(s,2H,O-CH2-N),5.34(s,2H,O-CH2-N),4.69(s,2H,Ar-CH2-N),4.47(s,2H,Ar-CH2-N);红外光谱测试结果(KBr,cm-1):1322(噁嗪环上CH2摇摆振动),1225和1069(C-O-C不对称和对称伸缩振动),1156(C-N-C不对称伸缩振动),949(C-H键面外弯曲振动,也是苯环上带有噁嗪环的特征吸收峰),结合核磁共振氢谱和红外光谱证实所得产物为目标产物。
将所得的苯并噁嗪单体放入电热鼓风干燥箱内,采用程序升温法对单体进行热固化,固化制度为:180℃/2h,200℃/2h,220℃/2h,240℃/2h,得到聚苯并噁嗪树脂,经DSC和TGA测试,得到聚苯并噁嗪树脂的玻璃化转变温度Tg为262℃,失重5%和10%所对应的热分解温度(简写为T5和T10)分别为393和418℃,800℃下的残炭率Yc为57.2%。
实施例2
除步骤(3)中苯酚改为间甲酚(2.16g,0.02mol),二甲苯改为甲苯,反应温度改为110℃外,其他条件同实施例1,最后得到间甲酚-双胺型苯并噁嗪单体,收率82.1%。
核磁共振氢谱测试结果(500M,DMSO,ppm):8.34~6.62(m,18H,Ar-H),5.40(s,2H,O-CH2-N),5.32(s,2H,O-CH2-N),4.64(s,2H,Ar-CH2-N),4.44(s,2H,Ar-CH2-N),2.26(s,6H,-CH3);红外光谱测试结果(KBr,cm-1):1323,1230,1073,1173和947。
固化和测试条件同实施例1,聚苯并噁嗪树脂的Tg、T5、T10和Yc值分别为253℃、384℃、408℃和54.5%。
实施例3
除步骤(3)中苯酚改为邻甲酚(2.16g,0.02mol),反应温度改为100℃,反应时间改为8h外,其他条件同实施例1,最后得到邻甲酚-双胺型苯并噁嗪单体,收率79.7%。
核磁共振氢谱测试结果(500M,DMSO,ppm):8.34~6.62(m,18H,Ar-H),5.47(s,2H,O-CH2-N),5.32(s,2H,O-CH2-N),4.69(s,2H,Ar-CH2-N),4.43(s,2H,Ar-CH2-N),2.16(s,6H,-CH3);红外光谱测试结果(KBr,cm-1):1322,1230,1073,1173和950。
固化和测试条件同实施例1,聚苯并噁嗪树脂的Tg、T5、T10和Yc值分别为208℃、377℃、402℃和42.8%。
实施例4
除步骤(1)中回流反应时间由6h改为10h,步骤(3)中的苯酚改为4-甲氧基苯酚(2.48g)外,其他条件同实施例1,最后得到4-甲氧基苯酚-双胺型苯并噁嗪单体,收率70.8%。
核磁共振氢谱测试结果(500M,DMSO,ppm):8.38~6.61(m,18H,Ar-H),5.40(s,2H,O-CH2-N),5.31(s,2H,O-CH2-N),4.65(s,2H,Ar-CH2-N),4.41(s,2H,Ar-CH2-N),3.72(s,6H,-OCH3);红外光谱测试结果(KBr,cm-1):1323,1229,1073,1172和948。
固化和测试条件同实施例1,聚苯并噁嗪树脂的Tg、T5、T10和Yc值分别为227℃、378℃、403℃和50.5%。
实施例5
除步骤(3)中苯酚改为3-三氟甲基苯酚(3.24g,0.02mol)外,其他条件同实施例1,最后得到3-三氟甲基苯酚-双胺型苯并噁嗪单体,收率72.7%。
核磁共振氢谱测试结果(500M,DMSO,ppm):8.43~6.59(m,18H,Ar-H),5.38(s,2H,O-CH2-N),5.32(s,2H,O-CH2-N),4.65(s,2H,Ar-CH2-N),4.40(s,2H,Ar-CH2-N);红外光谱测试结果(KBr,cm-1):1322,1229,1200,1073,1173和953。
固化和测试条件同实施例1,聚苯并噁嗪树脂的Tg、T5、T10和Yc值分别为255℃、390℃、423℃和59.6%。
实施例6
除将步骤(3)中苯酚改为对腈基苯酚(2.38g,0.02mol)外,其他条件同实施例1,最后得到对腈基苯酚-双胺型苯并噁嗪单体,收率64.6%。
核磁共振氢谱测试结果(500M,DMSO,ppm):8.38~6.60(m,20H,Ar-H),5.37(s,2H,O-CH2-N),5.29(s,2H,O-CH2-N),4.64(s,2H,Ar-CH2-N),4.39(s,2H,Ar-CH2-N);红外光谱测试结果(KBr,cm-1):2231(-CN伸缩振动),1322,1240,1073,1173和954。
除后固化温度增加了280℃/2h外,前期固化制度和测试条件同实施例1,聚苯并噁嗪树脂的Tg、T5、T10和Yc值分别为289℃、380℃、425℃和60.8%。
由上述实施例可以看出,本发明利用喹喔啉中2、3、6位具有较高的活性,合成了一种主链双胺型喹喔啉基苯并噁嗪混合单体,由于喹喔啉环位于聚合物主链之中,混合单体分子的空间构型不同,聚合物链段的空间位阻降低,聚合物网络的自由体积下降,聚合物链段的堆积更加致密,加上更多的分子内和分子间氢键的存在,因而主链双胺型喹喔啉基聚苯并噁嗪树脂具有更优良的热稳定性、阻燃性能、耐湿热性能以及机械性能,可用于制造高性能结构材料、电子封装材料、耐腐蚀材料和阻燃材料等。
Claims (3)
1.一种主链双胺型喹喔啉基苯并噁嗪单体,其特征是结构式为:
式中,R为氢、甲基、甲氧基、乙基、乙氧基、三氟甲基、三氟甲氧基或腈基中的一种。
2.一种权利要求1所述的主链双胺型喹喔啉基苯并噁嗪单体的制备方法,其特征是包括如下步骤:
(1)以冰乙酸为溶剂,向容器中加入摩尔比为1:1~1.2的4-硝基苯偶酰和4-硝基邻苯二胺,混合物回流5~12h,然后冷却至室温,过滤,滤饼烘干,所得粗产物用冰乙酸重结晶1~3次,得到2-(4-硝基苯基)-3-苯基-6-硝基喹喔啉和2-苯基-3-(4-硝基苯基)-6-硝基喹喔啉混合物、简写为M1;
(2)将质量比为1:0.03~0.05的M1与钯碳加入乙醇中,逐滴加入质量比浓度为80%的水合肼,其中,水合肼同M1的摩尔比为3.2~4:1,在回流温度下反应8~12h,趁热过滤,冷却至室温,再经过滤、水洗、真空干燥,得到2-(4-氨苯基)-3-苯基-6-氨基喹喔啉和2-苯基-3-(4-氨苯基)-6-氨基喹喔啉混合物、简写为M2;
(3)将M2、酚类化合物、多聚甲醛以及甲苯或二甲苯依次加入到容器中,M2、酚类化合物和多聚甲醛的摩尔比为1:2:4,在100~160℃下反应4~8h,将所得产物加入到正己烷中,沉淀物用正己烷洗涤数次,真空干燥,最终得到主链双胺型喹喔啉基苯并噁嗪单体。
3.根据权利要求2所述的主链双胺型喹喔啉基苯并噁嗪单体的制备方法,其特征是:所述的酚类化合物为苯酚、间甲酚、对甲酚、3-乙基苯酚、4-乙基苯酚、3-甲氧基苯酚、2-乙氧基苯酚、3-三氟甲基苯酚、3-三氟甲氧基苯酚或对腈基苯酚中的一种。
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