CN102702128A - Ether bond-containing diamine flourenyl benzoxazine - Google Patents

Abstract

Translated fromChinese

本发明是一种含醚键双胺型芴基苯并噁嗪。具有如下结构：

式中：A为含取代或未取代芳环的芴基，R₁为氢、甲基、甲氧基、三氟甲基或氰基中的一种。本发明的含醚键双胺型芴基苯并噁嗪，由于其结构中醚键的引入，可以改善苯并噁嗪树脂的韧性和加工性能，加上苯环数量的增多，聚合物的玻璃化转变温度、耐热性能和耐湿热性能不会因为柔性基团的引入而大幅下降。可用于先进复合材料基体树脂、电子封装材料、绝缘材料等领域。The invention is an ether bond-containing diamine type fluorenyl benzoxazine. has the following structure:

In the formula: A is a fluorenyl group containing a substituted or unsubstituted aromatic ring, and_R is one of hydrogen, methyl, methoxy, trifluoromethyl or cyano. The ether bond-containing diamine type fluorenyl benzoxazine of the present invention can improve the toughness and processability of the benzoxazine resin due to the introduction of the ether bond in its structure, and the increase in the number of benzene rings makes the glass of the polymer The transition temperature, heat resistance and heat and humidity resistance will not be greatly reduced due to the introduction of flexible groups. It can be used in advanced composite material matrix resin, electronic packaging material, insulating material and other fields.

Description

Translated fromChinese

含醚键双胺型芴基苯并噁嗪Diamine type fluorenyl benzoxazine containing ether bond

技术领域technical field

本发明涉及的是一种有机高分子材料，具体地说是一种含醚键双胺型芴基苯并噁嗪单体。The invention relates to an organic polymer material, in particular to an ether bond-containing diamine type fluorenyl benzoxazine monomer.

背景技术Background technique

20世纪70年代，Schreiber最早在专利中报道使用苯并噁嗪低聚物对环氧树脂进行改性(德国专利2217099，《Phenolic resin as electric insulator》)。20世纪80年代，Higginbottom在做涂覆材料的研究中首先发现了多官能度苯并噁嗪的交联反应(美国专利4501864，《Polymerizable compositions comprising polyamines and poly(dihydrobenzoxazines)》)。1994年，Ishida和Ning最先完成对聚苯并噁嗪的性能研究(Ning X，Ishida H.Phenolic materials viaring-opening polymerization-synthesis and characterization of bisphenol-A based benzoxazines andtheir polymers.J Polym Sci A Polym Chem，1994，32：1121-1129P)。通过大量的研究发现，苯并噁嗪树脂是和酚醛、环氧和马来酰亚胺一样性能优异的新型树脂材料。苯并噁嗪树脂通过灵活的分子设计性可以适应不同使用范围的力学性能、机械性能的需要。苯并噁嗪树脂还具有优异的热性能，耐化学腐蚀性及电性能。此外，对于一些特殊要求的应用，它还具有体积零收缩，高残炭，玻璃化转变温度高于固化温度，低介电常数和低吸水率等特性。苯并噁嗪原材料成本低廉，合成过程无副产物生成，固化过程中通过自身开环聚合，无需加入强酸或强碱等催化剂。而且，苯并噁嗪具有强大的分子设计性，这一特性极大拓展了苯并噁嗪树脂的应用领域。同时还可以加入到传统酚醛树脂、聚酯、环氧树脂，双马来酰亚胺树脂、聚氨酯、聚酰亚胺中作为改性材料，加速聚苯并噁嗪的商业化应用。In the 1970s, Schreiber first reported the use of benzoxazine oligomers to modify epoxy resins in patents (German patent 2217099, "Phenolic resin as electric insulator"). In the 1980s, Higginbottom first discovered the crosslinking reaction of multifunctional benzoxazines in the research of coating materials (US Patent 4501864, "Polymerizable compositions comprising polyamines and poly(dihydrobenzoxazines)"). In 1994, Ishida and Ning first completed the performance research on polybenzoxazines (Ning X, Ishida H. Phenolic materials viaring-opening polymerization-synthesis and characterization of bisphenol-A based benzoxazines and their polymers. J Polym Sci A Polym Chem , 1994, 32:1121-1129P). A large number of studies have found that benzoxazine resin is a new type of resin material with excellent performance like phenolic, epoxy and maleimide. Benzoxazine resins can adapt to the needs of mechanical properties and mechanical properties in different application ranges through flexible molecular design. Benzoxazine resins also have excellent thermal properties, chemical resistance and electrical properties. In addition, for some applications with special requirements, it also has the characteristics of zero volume shrinkage, high carbon residue, glass transition temperature higher than curing temperature, low dielectric constant and low water absorption. The raw material cost of benzoxazine is low, and no by-products are generated during the synthesis process. During the curing process, it undergoes self-ring-opening polymerization without adding catalysts such as strong acid or strong base. Moreover, benzoxazine has strong molecular design, which greatly expands the application field of benzoxazine resin. At the same time, it can also be added to traditional phenolic resin, polyester, epoxy resin, bismaleimide resin, polyurethane, and polyimide as a modified material to accelerate the commercial application of polybenzoxazine.

芴具有刚性平面联苯结构、宽能隙、高发光效率、良好的热稳定性、光稳定性、化学稳定性和易于加工等性能。通过9位引入双羟苯基和氨苯基，可制成一系列具有优良热稳定性、耐湿热性、介电性能、机械性能、耐化学品、高透明性、高折射率的聚酰亚胺树脂、聚碳酸酯、环氧树脂等。通过在芴分子中引入噁嗪环，也同样达到提高耐热性和阻燃性的作用。王军等人最早报道了芴基苯并噁嗪树脂的合成、聚合行为及热性能研究，即以双酚芴[9，9-双(4-羟苯基)芴](中国专利申请号200810137211.4，芴基双苯并噁嗪单体及其制备方法)和双胺芴[9，9-双(4-氨苯基)芴]为原料(中国专利申请号200810209638.0，芴基双苯并噁嗪单体及其制备方法)，获得一系列芴基苯并噁嗪单体。现有芴基苯并噁嗪树脂由于分子中含有悬垂的芴基，使聚苯并噁嗪树脂的脆性较大，限制了此类树脂的进一步应用。Fluorene has the properties of rigid planar biphenyl structure, wide energy gap, high luminous efficiency, good thermal stability, photostability, chemical stability and easy processing. By introducing bishydroxyphenyl and aminophenyl at the 9-position, a series of polyimides with excellent thermal stability, heat and humidity resistance, dielectric properties, mechanical properties, chemical resistance, high transparency and high refractive index can be made. Amine resin, polycarbonate, epoxy resin, etc. By introducing an oxazine ring into the fluorene molecule, the effect of improving heat resistance and flame retardancy can also be achieved. Wang Jun and others first reported the synthesis, polymerization behavior and thermal properties of fluorenyl benzoxazine resins, that is, bisphenol fluorene [9,9-bis (4-hydroxyphenyl) fluorene] (Chinese patent application number 200810137211.4 , fluorenyl bis-benzoxazine monomer and its preparation method) and bisamine fluorene [9,9-bis (4-aminophenyl) fluorene] as raw materials (Chinese Patent Application No. 200810209638.0, fluorenyl bis-benzoxazine Monomer and preparation method thereof) to obtain a series of fluorenyl benzoxazine monomers. Because the existing fluorenyl benzoxazine resins contain pendant fluorenyl groups in the molecules, the polybenzoxazine resins are relatively brittle, which limits the further application of such resins.

发明内容Contents of the invention

本发明的目的在于提供一种能够改善苯并噁嗪树脂的韧性和加工性能的含醚键双胺型芴基苯并噁嗪。The object of the present invention is to provide an ether bond-containing diamine type fluorenyl benzoxazine capable of improving the toughness and processability of the benzoxazine resin.

本发明的目的是这样实现的：The purpose of the present invention is achieved like this:

本发明的含醚键双胺型芴基苯并噁嗪具有如下结构：The ether bond-containing diamine type fluorenyl benzoxazine of the present invention has the following structure:

式中：A为含取代或未取代芳环的芴基，R₁为氢、甲基、甲氧基、三氟甲基或氰基中的一种。In the formula: A is a fluorenyl group containing a substituted or unsubstituted aromatic ring, and_R is one of hydrogen, methyl, methoxy, trifluoromethyl or cyano.

所述含取代或未取代芳环的芴基的结构式表示为：The structural formula of the fluorenyl group containing a substituted or unsubstituted aromatic ring is represented as:

式中：X为氢、甲基、甲氧基、三氟甲基或氰基中的一种。In the formula: X is one of hydrogen, methyl, methoxy, trifluoromethyl or cyano.

本发明的含醚键双胺型芴基苯并噁嗪是按照以下方式制备的：The ether bond-containing diamine type fluorenyl benzoxazine of the present invention is prepared in the following manner:

将含醚键芴二胺单体、酚类化合物和多聚甲醛加入到装有搅拌器、冷凝管、温度计的容器中，含醚键芴二胺单体、酚类化合物和多聚甲醛物质的量比为1∶2∶4，同时加入二甲苯作为溶剂，在150℃温度下反应4～15h，反应结束后冷却至室温，加入乙醇，沉淀物经洗涤、过滤、真空干燥后，将粗产物用二氯甲烷溶解，加入1mol/L氢氧化钠溶液进行碱洗，去离子水洗涤，分离，有机层加入无水硫酸钠，静置24h，过滤，滤液经旋转蒸发去除有机溶剂，真空干燥，即得到白色或淡黄色含醚键双胺型芴基苯并噁嗪单体。Add the ether bond-containing fluorene diamine monomer, phenolic compound and paraformaldehyde into a container equipped with a stirrer, a condenser tube, and a thermometer, and the ether bond-containing fluorene diamine monomer, phenol compound and paraformaldehyde The volume ratio is 1:2:4, and xylene is added as a solvent at the same time, and reacted at a temperature of 150 ° C for 4 to 15 hours. After the reaction is completed, it is cooled to room temperature, and ethanol is added. After the precipitate is washed, filtered, and vacuum-dried, the crude product is Dissolve in dichloromethane, add 1mol/L sodium hydroxide solution for alkali washing, wash with deionized water, separate, add anhydrous sodium sulfate to the organic layer, let stand for 24h, filter, remove the organic solvent by rotary evaporation of the filtrate, and vacuum dry, That is, a white or light yellow diamine fluorenyl benzoxazine monomer containing ether bonds is obtained.

所述的含醚键芴二胺单体为9，9-双(4-(4-氨基苯氧基)苯基)芴、9，9双(3-甲基4-(4-氨基苯氧基)苯基)芴、9，9-双(3-甲氧基-4-(4-氨基苯氧基)苯基)芴或9，9-双(3-三氟甲基-4-(4-氨基苯氧基)苯基)芴中的一种。The described ether bond-containing fluorene diamine monomer is 9,9-bis(4-(4-aminophenoxy)phenyl)fluorene, 9,9 bis(3-methyl 4-(4-aminophenoxy) Base) phenyl) fluorene, 9,9-bis(3-methoxy-4-(4-aminophenoxy)phenyl) fluorene or 9,9-bis(3-trifluoromethyl-4-( One of 4-aminophenoxy)phenyl)fluorene.

所述的酚类化合物为苯酚、邻甲酚、间甲酚、对甲酚、4-甲氧基苯酚、3-甲氧基苯酚、4-三氟甲基苯酚、3-三氟甲基苯酚或对腈基苯酚中的一种。Described phenolic compound is phenol, o-cresol, m-cresol, p-cresol, 4-methoxyphenol, 3-methoxyphenol, 4-trifluoromethylphenol, 3-trifluoromethylphenol Or one of p-cyanophenol.

本发明从芴二胺单体分子结构设计出发，在二元胺分子中引入柔性醚键，以改善苯并噁嗪树脂的韧性和加工性能。The invention starts from the molecular structure design of the fluorene diamine monomer and introduces flexible ether bonds into the diamine molecule to improve the toughness and processability of the benzoxazine resin.

本发明的含醚键双胺型芴基苯并噁嗪单体结构表征利用红外光谱(Spotlight 100，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，氘代氯仿(CDCl₃)作溶剂。聚合物性能测试采用差示扫描量热仪(DSC，美国TA公司)和热重分析仪(TGA，美国TA公司)，氮气氛围，升温速率为10℃/min。The structural characterization of the ether bond-containing diamine type fluorenyl benzoxazine monomer of the present invention utilizes infrared spectroscopy (Spotlight 100, PE Company of the United States) and nuclear magnetic resonance spectrometer (AVANCE-500, Swiss Bruker), and the infrared spectroscopy test adopts bromination Potassium tablet method, the sample is scanned 4 times, the resolution is 4cm^-1 , and the scanning range is 4000～500cm^-1 . The H NMR spectrum uses tetramethylsilane (TMS) as the internal standard and deuterated chloroform (CDCl₃ ) as the internal standard. solvent. Polymer properties were tested using a differential scanning calorimeter (DSC, TA Company of the United States) and a thermogravimetric analyzer (TGA, TA Company of the United States) in a nitrogen atmosphere with a heating rate of 10 °C/min.

本发明制备的含醚键双胺型芴基苯并噁嗪可用于先进复合材料基体树脂、电子封装材料、绝缘材料等领域。The ether bond-containing diamine fluorenyl benzoxazine prepared by the invention can be used in the fields of advanced composite material matrix resin, electronic packaging material, insulating material and the like.

本发明含醚键双胺型芴基苯并噁嗪及其制备方法是以含醚键芴二胺单体，与酚类化合物、多聚甲醛为原料，采用一步法合成二元胺型苯并噁嗪单体。相比传统三步法而言，不仅反应步骤、反应时间大大缩短，而且避免了反应原料从水杨醛出发，限制苯并噁嗪灵活的分子设计性的缺点。此外，由于其结构中醚键的引入，可以改善苯并噁嗪树脂的韧性和加工性能，加上苯环数量的增多，聚合物的玻璃化转变温度、耐热性能和耐湿热性能不会因为柔性基团的引入而大幅下降。The ether bond-containing diamine type fluorenyl benzoxazine and the preparation method thereof of the present invention use ether bond-containing fluorene diamine monomers, phenolic compounds, and paraformaldehyde as raw materials to synthesize dibasic amine type benzoxazines in one step. Oxazine monomer. Compared with the traditional three-step method, not only the reaction steps and reaction time are greatly shortened, but also the disadvantage of limiting the flexible molecular design of benzoxazine from starting from salicylaldehyde is avoided. In addition, due to the introduction of ether bonds in its structure, the toughness and processability of benzoxazine resin can be improved, and the number of benzene rings increases, the glass transition temperature, heat resistance and heat and humidity resistance of the polymer will not be affected by The introduction of flexible groups decreased significantly.

具体实施方式Detailed ways

下面举例对本发明做更详细的描述：The following examples describe the present invention in more detail:

实施例1Example 1

向带有磁力搅拌器、滴液漏斗及温度计的100mL三口瓶中加入5.32g(0.01mol)9，9-双-(4-(4-氨基苯氧基)苯基)芴，1.88g(0.02mol)苯酚，1.2g(0.04mol)多聚甲醛以及50mL二甲苯。加热至150℃回流反应6h，反应结束后冷却至室温，加入乙醇，沉淀物洗涤、过滤，粗产物在60℃真空烘箱中干燥24h。将粗产物用二氯甲烷溶解，加入1mol/L氢氧化钠溶液进行碱洗，用去离子水洗涤，分离，有机层加入无水硫酸钠，静置24h，过滤，滤液经旋转蒸发去除有机溶剂，真空干燥，即得到白色粉末9，9-双-(4-(4-氨基苯氧基)苯基)芴-苯酚基苯并噁嗪单体(BEF-p)，收率81.2％。Add 5.32g (0.01mol) 9,9-bis-(4-(4-aminophenoxy)phenyl)fluorene to a 100mL three-neck flask with a magnetic stirrer, dropping funnel and thermometer, 1.88g (0.02 mol) phenol, 1.2 g (0.04 mol) paraformaldehyde and 50 mL xylene. Heat to 150°C for reflux reaction for 6h, cool to room temperature after the reaction, add ethanol, wash the precipitate, filter, and dry the crude product in a vacuum oven at 60°C for 24h. Dissolve the crude product in dichloromethane, add 1mol/L sodium hydroxide solution for alkali washing, wash with deionized water, separate, add anhydrous sodium sulfate to the organic layer, let stand for 24h, filter, and remove the organic solvent by rotary evaporation of the filtrate , vacuum-dried to obtain white powder 9,9-bis-(4-(4-aminophenoxy)phenyl)fluorene-phenolyl benzoxazine monomer (BEF-p), with a yield of 81.2%.

核磁共振氢谱测试结果(500M，CDCl₃，ppm)：6.75～7.74(m，32H，ArH)，5.30(d，4H，O-CH₂-N)，4.58(d，4H，Ar-CH₂-N)；红外光谱测试结果(KBr，cm^-1)：1608、1584、1489和750(苯环的邻位二取代特征峰)，1373(噁嗪环上CH₂摇摆振动峰)，1239和1067(C-O-C不对称和对称伸缩振动)，1138(C-N-C上不对称伸缩振动)，951(C-H键面外弯曲特征)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单体。H NMR test results (500M, CDCl₃ , ppm): 6.75～7.74(m, 32H, ArH), 5.30(d, 4H, O-CH₂ -N), 4.58(d, 4H, Ar-CH₂ -N); infrared spectrum test results (KBr, cm^-1 ): 1608, 1584, 1489 and 750 (characteristic peaks of ortho disubstitution of benzene ring), 1373 (CH₂ rocking vibration peak on oxazine ring), 1239 and 1067 (COC asymmetric and symmetric stretching vibration), 1138 (asymmetric stretching vibration on CNC), 951 (CH bond out-of-plane bending feature) are the characteristic absorption peaks with oxazine ring on the benzene ring. Combined with H NMR and IR spectra, it was confirmed that the obtained product was the target monomer.

将苯并噁嗪单体BEF-p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(简写为poly-(BEF-p))，经DSC和TGA测试，得到聚苯并噁嗪树脂的玻璃化转变温度(简写为T_g，以下同)、失重5％所对应的热分解温度(简写为T₅，以下同)以及800℃下的残炭率。Put the benzoxazine monomer BEF-p into the electric blast drying oven, and use the temperature programming method to heat cure the monomer. The curing system is: 180°C/2h, 200°C/2h, 220°C/2h, 240°C °C/2h to obtain a polybenzoxazine resin (abbreviated as poly-(BEF-p)), and the glass transition temperature of the polybenzoxazine resin (abbreviated as T_g , the same below) was obtained by DSC and TGA tests , the thermal decomposition temperature corresponding to 5% weight loss (abbreviated as T₅ , the same below) and the char residue rate at 800°C.

实施例2Example 2

除原料苯酚改用邻甲苯酚，质量2.16g外，其他条件同实施例1，最后得到淡黄色9，9-双-(4-(4-氨基苯氧基)苯基)芴-邻甲苯酚基苯并噁嗪单体(BEF-o-mp)，收率71.3％。Except that the raw material phenol is replaced by o-cresol, and the quality is 2.16g, other conditions are the same as in Example 1, and finally light yellow 9,9-bis-(4-(4-aminophenoxy)phenyl)fluorene-o-cresol is obtained Benzyl benzoxazine monomer (BEF-o-mp), yield 71.3%.

核磁共振氢谱测试结果(500M，CDCl₃，ppm)：6.75～7.74(m，30H，Ar-H)，5.30(d，4H，O-CH₂-N)，4.55(d，4H，Ar-CH₂-N)，2.16(d，6H，-CH₃)；红外光谱测试结果(KBr，cm^-1)：1383、1224、1078、1159和951。Proton NMR test results (500M, CDCl₃ , ppm): 6.75～7.74(m, 30H, Ar-H), 5.30(d, 4H, O-CH₂ -N), 4.55(d, 4H, Ar- CH₂ -N), 2.16 (d, 6H, -CH₃ ); infrared spectrum test results (KBr, cm^-1 ): 1383, 1224, 1078, 1159 and 951.

固化和测试条件同实施例1，聚苯并噁嗪树脂(poly(BEF-o-mp))性能见表1。The curing and testing conditions are the same as in Example 1, and the properties of the polybenzoxazine resin (poly(BEF-o-mp)) are shown in Table 1.

实施例3Example 3

除原料苯酚改用间甲苯酚外，质量2.16g，反应时间4h外，其他条件同实施例1，最后得到淡黄色9，9-双-(4-(4-氨基苯氧基)苯基)芴-间甲苯酚基苯并噁嗪单体(BEF-m-mp)，收率62.5％。Except that the raw material phenol is changed to m-cresol, the quality is 2.16g, and the reaction time is 4h, other conditions are the same as in Example 1, and finally the light yellow 9,9-bis-(4-(4-aminophenoxy)phenyl) is obtained Fluorene-m-cresyl benzoxazine monomer (BEF-m-mp), yield 62.5%.

核磁共振氢谱测试结果(500M，CDCl3，ppm)：6.61～7.74(m，30H，Ar-H)，5.27(d，4H，O-CH₂-N)，4.45(d，4H，Ar-CH₂-N)，2.26(d，6H，-CH₃)；红外光谱测试结果(KBr，cm^-1)：1385、1259、1076、1162和956。Proton NMR test results (500M, CDCl3, ppm): 6.61～7.74(m, 30H, Ar-H), 5.27(d, 4H, O-CH₂ -N), 4.45(d, 4H, Ar-CH₂ -N), 2.26 (d, 6H, -CH₃ ); infrared spectrum test results (KBr, cm^-1 ): 1385, 1259, 1076, 1162 and 956.

固化和测试条件同实施例1，聚苯并噁嗪树脂(poly(BEF-m-mp))性能见表1。The curing and testing conditions are the same as in Example 1, and the properties of the polybenzoxazine resin (poly(BEF-m-mp)) are shown in Table 1.

实施例4Example 4

除原料苯酚改用对甲苯酚，质量2.16g，回流时间15h外，其他条件同实施例6，最后得到淡黄色9，9-双-(4-(4-氨基苯氧基)苯基)芴-对甲苯酚基苯并噁嗪单体(BEF-p-mp)，收率74.8％。Except that the raw material phenol is changed to p-cresol, the quality is 2.16g, and the reflux time is 15h, other conditions are the same as in Example 6, and finally light yellow 9,9-bis-(4-(4-aminophenoxy)phenyl)fluorene is obtained - p-cresyl benzoxazine monomer (BEF-p-mp), yield 74.8%.

核磁共振氢谱测试结果(500M，CDCl₃，ppm)：6.68～7.74(m，30H，Ar-H)，5.26(d，4H，O-CH₂-N)，4.52(d，4H，Ar-CH₂-N)，2.24(d，6H，-CH₃)；红外光谱测试结果(KBr，cm^-1)：1383、1227、1075、1162和952。Proton NMR test results (500M, CDCl₃ , ppm): 6.68～7.74(m, 30H, Ar-H), 5.26(d, 4H, O-CH₂ -N), 4.52(d, 4H, Ar- CH₂ -N), 2.24 (d, 6H, -CH₃ ); infrared spectrum test results (KBr, cm^-1 ): 1383, 1227, 1075, 1162 and 952.

固化和测试条件同实施例1，聚苯并噁嗪树脂(poly(BEF-p-mp))性能见表1。The curing and testing conditions are the same as in Example 1, and the properties of the polybenzoxazine resin (poly(BEF-p-mp)) are shown in Table 1.

实施例5Example 5

除原料苯酚改用4-甲氧基苯酚，质量2.48g，回流时间12h外，其他条件同实施例1，最后得到淡黄色9，9-双-(4-(4-氨基苯氧基)苯基)芴-对甲氧基苯酚基苯并噁嗪单体(BEF-mop)，收率71.8％。Except that the raw material phenol is changed to 4-methoxyphenol, the quality is 2.48g, and the reflux time is 12h, other conditions are the same as in Example 1, and finally the light yellow 9,9-bis-(4-(4-aminophenoxy)benzene is obtained. Base) fluorene-p-methoxyphenol-based benzoxazine monomer (BEF-mop), the yield is 71.8%.

核磁共振氢谱测试结果(500M，CDCl₃，ppm)：6.67～7.82(m，30H，ArH)，5.31(d，4H，O-CH₂-N)，4.55(d，4H，Ar-CH₂-N)，3.75(d，6H，-CH₃)；红外光谱测试结果(KBr，cm^-1)：1384、1226、1075、1177和948。H NMR test results (500M, CDCl₃ , ppm): 6.67～7.82(m, 30H, ArH), 5.31(d, 4H, O-CH₂ -N), 4.55(d, 4H, Ar-CH₂ -N), 3.75 (d, 6H, -CH₃ ); infrared spectrum test results (KBr, cm^-1 ): 1384, 1226, 1075, 1177 and 948.

固化和测试条件同实施例1，聚苯并噁嗪树脂(poly-(BEFmop))，性能见表1。The curing and testing conditions are the same as in Example 1, polybenzoxazine resin (poly-(BEFmop)), and the properties are shown in Table 1.

实施例6Example 6

除原料苯酚改用4-三氟甲基苯酚，质量为3.24g外，其他条件同实施例1，最后得到淡黄色9，9-双-(4-(4-氨基苯氧基)苯基)芴-对三氟甲基苯酚基苯并噁嗪单体(BEF-fp)，收率73.6％。Except that the raw material phenol was changed to 4-trifluoromethylphenol, and the quality was 3.24g, other conditions were the same as in Example 1, and finally obtained pale yellow 9,9-bis-(4-(4-aminophenoxy)phenyl) Fluorene-p-trifluoromethylphenol-based benzoxazine monomer (BEF-fp), yield 73.6%.

核磁共振氢谱测试结果(500M，CDCl₃，ppm)：6.65～7.87(m，30H，Ar-H)，5.31(d，4H，O-CH₂-N)，4.57(d，4H，Ar-CH₂-N)；红外光谱测试结果(KBr，cm^-1)：1383、1228、1200、1078、1175和951。Proton NMR test results (500M, CDCl₃ , ppm): 6.65～7.87(m, 30H, Ar-H), 5.31(d, 4H, O-CH₂ -N), 4.57(d, 4H, Ar- CH₂ -N); infrared spectrum test results (KBr, cm^-1 ): 1383, 1228, 1200, 1078, 1175 and 951.

固化和测试条件同实施例1，聚苯并噁嗪树脂(poly-(BEF-fp))，性能见表1。The curing and testing conditions are the same as in Example 1, polybenzoxazine resin (poly-(BEF-fp)), and the properties are shown in Table 1.

实施例7Example 7

除原料苯酚改用对氰基苯酚，质量为2.38g外，其他条件同实施例1，最后得到淡黄色9，9-双-(4-(4-氨基苯氧基)苯基)芴-对氰基苯酚基苯并噁嗪单体(BEF-cp)，收率64.8％。Except that the raw material phenol is changed to p-cyanophenol, and the quality is 2.38g, other conditions are the same as in Example 1, and finally light yellow 9,9-bis-(4-(4-aminophenoxy)phenyl)fluorene-p- Cyanophenol-based benzoxazine monomer (BEF-cp), yield 64.8%.

核磁共振氢谱测试结果(500M，CDCl₃，ppm)：6.66～7.82(m，30H，Ar-H)，5.28(d，4H，O-CH₂-N)，4.56(d，4H，Ar-CH₂-N)；红外光谱测试结果(KBr，cm^-1)：2220cm^-1(苯环上C≡N键的伸缩振动)，1383、1240、1078、1175和952。Proton NMR test results (500M, CDCl₃ , ppm): 6.66～7.82 (m, 30H, Ar-H), 5.28 (d, 4H, O-CH₂ -N), 4.56 (d, 4H, Ar- CH₂ -N); infrared spectrum test results (KBr, cm^-1 ): 2220cm^-1 (stretch vibration of C≡N bond on the benzene ring), 1383, 1240, 1078, 1175 and 952.

BEF-cp的热固化制度为：180℃/2h，200℃/2h，220℃/2h，240℃/2h，260℃/2h，测试条件同实施例1，最后得到聚苯并噁嗪树脂(poly-(BEF-cp))，性能见表1。The thermal curing system of BEF-cp is: 180 DEG C/2h, 200 DEG C/2h, 220 DEG C/2h, 240 DEG C/2h, 260 DEG C/2h, test condition is the same as embodiment 1, finally obtains polybenzoxazine resin ( poly-(BEF-cp)), the properties are shown in Table 1.

实施例8Example 8

除原料9，9-双-(4-(4-氨基苯氧基)苯基)芴改用9，9-双-(3-甲基-4-(4-氨基苯氧基)苯基)芴，质量为5.61g外，其他条件同实施例1，最后得到淡黄色9，9-双-(3-甲基-4-(4-氨基苯氧基)苯基)芴-苯酚基苯并噁嗪单体(BMEF-p)，收率65.5％。In addition to the raw material 9,9-bis-(4-(4-aminophenoxy)phenyl)fluorene is replaced by 9,9-bis-(3-methyl-4-(4-aminophenoxy)phenyl) Fluorene, quality is 5.61g, other conditions are the same as embodiment 1, finally obtain light yellow 9,9-bis-(3-methyl-4-(4-aminophenoxy) phenyl) fluorene-phenol base benzo Oxazine monomer (BMEF-p), yield 65.5%.

核磁共振氢谱测试结果(500M，CDCl₃，ppm)：6.68～7.77(m，30H，Ar-H)，5.29(d，4H，O-CH₂-N)，4.53(d，4H，Ar-CH₂-N)，2.07(d，6H，-CH₃)；红外光谱测试结果(KBr，cm^-1)：1384、1226、1078、1164和950。Proton NMR test results (500M, CDCl₃ , ppm): 6.68～7.77 (m, 30H, Ar-H), 5.29 (d, 4H, O-CH₂ -N), 4.53 (d, 4H, Ar- CH₂ -N), 2.07 (d, 6H, -CH₃ ); infrared spectrum test results (KBr, cm^-1 ): 1384, 1226, 1078, 1164 and 950.

固化和测试条件同实施例1，聚苯并噁嗪树脂(poly(BMEF-p))性能见表1。The curing and testing conditions are the same as in Example 1, and the properties of the polybenzoxazine resin (poly(BMEF-p)) are shown in Table 1.

实施例9Example 9

除原料9，9-双-(4-(4-氨基苯氧基)苯基)芴改用9，9-双-(3-甲氧基-4-(4-氨基苯氧基)苯基)芴，质量为5.93g外，其他条件同实施例1，最后得到淡黄色9，9双-(3-甲氧基4-(4-氨基苯氧基)苯基)芴-苯酚基苯并噁嗪单体(BMOEFp)，收率57.2％。In addition to the raw material 9,9-bis-(4-(4-aminophenoxy)phenyl)fluorene is replaced by 9,9-bis-(3-methoxy-4-(4-aminophenoxy)phenyl ) fluorene, quality is 5.93g, other conditions are the same as embodiment 1, finally obtain light yellow 9,9 bis-(3-methoxy 4-(4-aminophenoxy) phenyl) fluorene-phenol benzo Oxazine monomer (BMOEFp), yield 57.2%.

核磁共振氢谱测试结果(500M，CDCl₃，ppm)：6.68～7.84(m，30H，ArH)，5.32(d，4H，O-CH₂-N)，4.61(d，4H，Ar-CH₂-N)，3.81(d，6H，-CH₃)；红外光谱测试结果(KBr，cm^-1)：1381、1228、1081、1167和952。H NMR test results (500M, CDCl₃ , ppm): 6.68～7.84(m, 30H, ArH), 5.32(d, 4H, O-CH₂ -N), 4.61(d, 4H, Ar-CH₂ -N), 3.81 (d, 6H, -CH₃ ); infrared spectrum test results (KBr, cm^-1 ): 1381, 1228, 1081, 1167 and 952.

固化和测试条件同实施例1，聚苯并噁嗪树脂(poly(BMOEF-p))性能见表1。The curing and testing conditions are the same as in Example 1, and the properties of the polybenzoxazine resin (poly(BMOEF-p)) are shown in Table 1.

实施例10Example 10

除原料9，9-双-(4-(4-氨基苯氧基)苯基)芴改用9，9-双-(3-三氟-4-(4-氨基苯氧基)苯基)芴，质量为6.68g外，其他条件同实施例1，最后得到淡黄色9，9-双-(3-三氟-4-(4-氨基苯氧基)苯基)芴-苯酚基苯并噁嗪单体(BFEF-p)，收率62.3％。In addition to the raw material 9,9-bis-(4-(4-aminophenoxy)phenyl)fluorene is replaced by 9,9-bis-(3-trifluoro-4-(4-aminophenoxy)phenyl) Fluorene, quality is 6.68g, other conditions are the same as embodiment 1, finally obtain light yellow 9,9-bis-(3-trifluoro-4-(4-aminophenoxy)phenyl)fluorene-phenoxybenzo Oxazine monomer (BFEF-p), yield 62.3%.

核磁共振氢谱测试结果(500M，CDCl₃，ppm)：6.72～7.87(m，30H，Ar-H)，5.28(d，4H，O-CH₂-N)，4.57(d，4H，Ar-CH₂-N)；红外光谱测试结果(KBr，cm^-1)：1377、1228、1203、1077、1166和946。Proton NMR test results (500M, CDCl₃ , ppm): 6.72～7.87 (m, 30H, Ar-H), 5.28 (d, 4H, O-CH₂ -N), 4.57 (d, 4H, Ar- CH₂ -N); infrared spectrum test results (KBr, cm^-1 ): 1377, 1228, 1203, 1077, 1166 and 946.

固化和测试条件同实施例1，聚苯并噁嗪树脂(poly(BFEF-p))性能见表1。The curing and testing conditions are the same as in Example 1, and the properties of the polybenzoxazine resin (poly(BFEF-p)) are shown in Table 1.

表1 苯并噁嗪树脂的热性能参数Table 1 Thermal performance parameters of benzoxazine resin

从表中结果可见，结构中醚键的引入，可以改善苯并噁嗪树脂的韧性和加工性能，加上苯环数量的增多，聚合物的玻璃化转变温度、耐热性能和耐湿热性能不会因为柔性基团的引入而大幅下降，可用于先进复合材料基体树脂、电子封装材料、绝缘材料、阻燃材料、耐烧蚀材料以及层压材料等领域。It can be seen from the results in the table that the introduction of ether bonds in the structure can improve the toughness and processability of benzoxazine resins, and the increase in the number of benzene rings will lead to lower glass transition temperature, heat resistance and heat and humidity resistance of the polymer. It will be greatly reduced due to the introduction of flexible groups, and can be used in advanced composite material matrix resins, electronic packaging materials, insulating materials, flame-retardant materials, ablation-resistant materials, and laminated materials.

Claims (2)

Translated fromChinese

1.一种含醚键双胺型芴基苯并噁嗪，其特征是具有如下结构：1. A diamine type fluorenyl benzoxazine containing an ether bond, characterized in that it has the following structure:式中：A为含取代或未取代芳环的芴基，R₁为氢、甲基、甲氧基、三氟甲基或氰基中的一种。In the formula: A is a fluorenyl group containing a substituted or unsubstituted aromatic ring, and_R is one of hydrogen, methyl, methoxy, trifluoromethyl or cyano.2.根据权利要求1所述的含醚键双胺型芴基苯并噁嗪，其特征是所述含取代或未取代芳环的芴基的结构式表示为：2. The ether bond-containing diamine type fluorenyl benzoxazine according to claim 1, characterized in that the structural formula of the fluorenyl group containing substituted or unsubstituted aromatic rings is expressed as:

式中：X为氢、甲基、甲氧基、三氟甲基或氰基中的一种。In the formula: X is one of hydrogen, methyl, methoxy, trifluoromethyl or cyano.