CN106631893A - Animophenoxy phthalonitrile resin monomer and synthetic method thereof - Google Patents
Animophenoxy phthalonitrile resin monomer and synthetic method thereof Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 67
- 229920005989 resin Polymers 0.000 title claims abstract description 67
- 239000000178 monomer Substances 0.000 title claims abstract description 61
- 238000010189 synthetic method Methods 0.000 title claims description 11
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 title description 5
- 229920006391 phthalonitrile polymer Polymers 0.000 title description 5
- NEXPSTARCSTNSW-UHFFFAOYSA-N 4-amino-3-phenoxybenzene-1,2-dicarbonitrile Chemical compound NC1=CC=C(C#N)C(C#N)=C1OC1=CC=CC=C1 NEXPSTARCSTNSW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000001308 synthesis method Methods 0.000 claims abstract description 15
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- UZJZIZFCQFZDHP-UHFFFAOYSA-N 3-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=CC(C#N)=C1C#N UZJZIZFCQFZDHP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 230000009257 reactivity Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 20
- 150000002825 nitriles Chemical class 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 125000002560 nitrile group Chemical group 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WSOSWJCIAIGIEI-UHFFFAOYSA-N 3-(2-aminophenoxy)benzene-1,2-dicarbonitrile Chemical compound NC1=CC=CC=C1OC1=CC=CC(C#N)=C1C#N WSOSWJCIAIGIEI-UHFFFAOYSA-N 0.000 description 1
- NTZMSBAAHBICLE-UHFFFAOYSA-N 4-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(C#N)=C1 NTZMSBAAHBICLE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- -1 that is Chemical compound 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- 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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- Chemical Kinetics & Catalysis (AREA)
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种氨基苯氧基邻苯二甲腈树脂单体及其合成方法。该氨基苯氧基邻苯二甲腈树脂单体的分子结构式如式(Ⅰ)所示。合成方法包括(1)将邻氨基苯酚、催化剂和溶剂混合，在氮气保护下，加热至90℃～100℃并保温；(2)向保温后的溶液中加入3‑硝基邻苯二甲腈，在80℃～90℃温度下进行反应，得到氨基苯氧基邻苯二甲腈树脂单体。本发明的氨基苯氧基邻苯二甲腈树脂单体具有高反应活性、高耐热、低固化温度和短固化时间的优点，合成方法简单方便、成本低廉。
The invention discloses an aminophenoxy phthalonitrile resin monomer and a synthesis method thereof. The molecular structural formula of the aminophenoxy phthalonitrile resin monomer is shown in formula (I). The synthesis method comprises (1) mixing o-aminophenol, a catalyst and a solvent, heating to 90°C-100°C under the protection of nitrogen and keeping it warm; (2) adding 3-nitrophthalonitrile to the warmed solution , react at a temperature of 80° C. to 90° C. to obtain an aminophenoxy phthalonitrile resin monomer. The aminophenoxy phthalonitrile resin monomer of the invention has the advantages of high reactivity, high heat resistance, low curing temperature and short curing time, and the synthesis method is simple, convenient and low in cost.
Description
技术领域technical field
本发明属于有机合成高分子材料技术领域，涉及一种自催化腈基树脂单体及其合成方法，具体涉及一种氨基苯氧基邻苯二甲腈树脂单体及其合成方法。The invention belongs to the technical field of organic synthetic polymer materials, and relates to a self-catalyzed nitrile-based resin monomer and a synthesis method thereof, in particular to an aminophenoxyphthalonitrile resin monomer and a synthesis method thereof.
背景技术Background technique
航空航天、国防军事等领域对耐高温、高性能、阻燃性好的复合材料提出了新要求。邻苯二甲腈树脂以其固化物具有良好的热稳定性和机械性能，以及优异的热氧稳定性、阻燃性和较好的耐潮性，而备受青睐。目前该类树脂在航空航天、舰船、微电子及机械制造等领域已开始广泛的应用。Aerospace, national defense and military fields have put forward new requirements for composite materials with high temperature resistance, high performance and good flame retardancy. Phthalonitrile resins are favored for their cured products with good thermal stability and mechanical properties, as well as excellent thermo-oxidative stability, flame retardancy and good moisture resistance. At present, this kind of resin has been widely used in the fields of aerospace, shipbuilding, microelectronics and machinery manufacturing.
目前典型邻苯二甲腈树脂主要有联苯型双邻苯二甲腈树脂、双酚A型双邻苯二甲腈树脂、以及芳醚型邻苯二甲腈树脂。但是这类树脂单体热固化温度高、反应缓慢，需要在280℃处理近百小时才能观察到明显的凝胶现象。它们的高加工温度、低固化速率等特点是造成树脂加工性差的主要原因。At present, typical phthalonitrile resins mainly include biphenyl type bisphthalonitrile resin, bisphenol A type bisphthalonitrile resin, and aryl ether type bisphthalonitrile resin. However, this type of resin monomer has a high thermal curing temperature and slow reaction, and it needs to be treated at 280°C for nearly 100 hours to observe the obvious gel phenomenon. Their high processing temperature, low curing rate and other characteristics are the main reasons for the poor processability of the resin.
在过去的20年里，为了降低邻苯二甲腈树脂的加工温度、提升其固化速率，提高其加工性，相关人员开展了一系列的研究工作。目前主要使用的是加入催化剂和设计开发新型自催化固化单体。但是目前使用的小分子催化剂由于加入量不能太大而导致催化效果一般，同时由于其在高温下挥发而出现固化交联速度减缓。目前的自催化树脂单体有相对较好的加工性，不存在因挥发而导致固化速度降低的问题，相对传统单体固化温度和时间都有所降低。比如芳醚腈基中加入小分子催化剂的固化温度程序为(250℃保持1小时，325℃保持3小时，375℃保持8小时，425℃保持8小时，总计20小时)，固化物在氮气氛下1000℃残炭率为70-73％，而氨基自催化树脂单体可以在固化温度程序为(220℃保持1小时，250℃保持5小时，315℃保持5小时，375℃保持5小时，总计16小时)，所得固化物在氮气氛下900℃残炭率为72-74％。只是这种降低效果不太明显。In the past 20 years, in order to reduce the processing temperature of phthalonitrile resin, increase its curing rate, and improve its processability, relevant personnel have carried out a series of research work. At present, the main use is to add catalysts and design and develop new self-catalyzed curing monomers. However, the currently used small-molecule catalysts have a mediocre catalytic effect because the addition amount cannot be too large, and at the same time, the curing and cross-linking speed slows down due to its volatilization at high temperature. The current self-catalyzed resin monomers have relatively good processability, and there is no problem of slowing down the curing speed due to volatilization. Compared with traditional monomers, the curing temperature and time are reduced. For example, the curing temperature program of adding a small molecule catalyst to the aryl ether nitrile group is (250°C for 1 hour, 325°C for 3 hours, 375°C for 8 hours, 425°C for 8 hours, a total of 20 hours), and the cured product is in a nitrogen atmosphere. The carbon residue rate at 1000°C is 70-73%, and the amino autocatalytic resin monomer can be cured at a temperature program of (220°C for 1 hour, 250°C for 5 hours, 315°C for 5 hours, 375°C for 5 hours, 16 hours in total), the carbon residue rate of the obtained cured product at 900° C. under a nitrogen atmosphere is 72-74%. It's just that the reduction effect is not so obvious.
发明内容Contents of the invention
本发明要解决的技术问题是克服现有技术的不足，提供一种具有高反应活性、高耐热、低固化温度、短固化时间的氨基苯氧基邻苯二甲腈树脂单体及其合成方法。The technical problem to be solved in the present invention is to overcome the deficiencies of the prior art, to provide a kind of aminophenoxyphthalonitrile resin monomer with high reactivity, high heat resistance, low curing temperature and short curing time and its synthesis method.
为解决上述技术问题，本发明采用以下技术方案。In order to solve the above technical problems, the present invention adopts the following technical solutions.
一种氨基苯氧基邻苯二甲腈树脂单体，所述氨基苯氧基邻苯二甲腈树脂单体的分子结构式为下式(Ⅰ)：A kind of aminophenoxy phthalonitrile resin monomer, the molecular structural formula of described aminophenoxy phthalonitrile resin monomer is following formula (I):
作为一个总的技术构思，本发明还提供一种氨基苯氧基邻苯二甲腈树脂单体的合成方法，包括以下步骤：As a general technical design, the present invention also provides a kind of synthetic method of aminophenoxy phthalonitrile resin monomer, comprising the following steps:
(1)将邻氨基苯酚、催化剂和溶剂混合，在氮气保护下，加热至90℃～100℃并保温；(1) Mix o-aminophenol, catalyst and solvent, heat to 90°C-100°C under nitrogen protection and keep warm;
(2)向步骤(1)保温后的溶液中加入3-硝基邻苯二甲腈，在80℃～90℃温度下进行反应，反应后冷却，经后处理，得到氨基苯氧基邻苯二甲腈树脂单体。(2) Add 3-nitrophthalonitrile to the solution after heat preservation in step (1), react at a temperature of 80°C to 90°C, cool after the reaction, and post-process to obtain aminophenoxyphthalonitrile Dicyanonitrile resin monomer.
上述的氨基苯氧基邻苯二甲腈树脂单体的合成方法中，优选的，所述邻氨基苯酚、催化剂、溶剂、3-硝基邻苯二甲腈的比值为0.1mol～0.12mol∶0.15mol～0.18mol∶150ml～180ml∶0.08mol～0.1mol。In the synthesis method of the above-mentioned aminophenoxyphthalonitrile resin monomer, preferably, the ratio of the o-aminophenol, catalyst, solvent, and 3-nitrophthalonitrile is 0.1mol～0.12mol: 0.15mol～0.18mol: 150ml～180ml: 0.08mol～0.1mol.
上述的氨基苯氧基邻苯二甲腈树脂单体的合成方法中，优选的，所述步骤(1)中，所述保温的时间为1h～3h。In the above-mentioned synthesis method of the aminophenoxyphthalonitrile resin monomer, preferably, in the step (1), the time for keeping warm is 1 h to 3 h.
上述的氨基苯氧基邻苯二甲腈树脂单体的合成方法中，优选的，所述步骤(2)中，所述反应的时间为5h～8h。In the above synthesis method of aminophenoxyphthalonitrile resin monomer, preferably, in the step (2), the reaction time is 5h-8h.
上述的氨基苯氧基邻苯二甲腈树脂单体的合成方法中，优选的，所述步骤(1)中，所述催化剂包括无水碳酸钾、无水碳酸钠中的一种或两种。In the synthetic method of above-mentioned aminophenoxy phthalonitrile resin monomer, preferably, in described step (1), described catalyst comprises one or both in anhydrous potassium carbonate, anhydrous sodium carbonate .
上述的氨基苯氧基邻苯二甲腈树脂单体的合成方法中，优选的，所述步骤(1)中，所述溶剂包括N,N-二甲基甲酰胺、二甲亚砜、1,4-二氧六环中的一种或多种。In the synthesis method of the above-mentioned aminophenoxyphthalonitrile resin monomer, preferably, in the step (1), the solvent includes N,N-dimethylformamide, dimethyl sulfoxide, 1 , one or more of 4-dioxanes.
上述的氨基苯氧基邻苯二甲腈树脂单体的合成方法中，优选的，所述步骤(2)中，所述后处理的过程如下：向冷却后所得产物溶液中加入NaOH水溶液，析出沉淀，然后抽滤、洗涤至中性，再过滤、干燥，即得氨基苯氧基邻苯二甲腈树脂单体。In the synthesis method of the above-mentioned aminophenoxyphthalonitrile resin monomer, preferably, in the step (2), the post-treatment process is as follows: add NaOH aqueous solution to the cooled product solution, and precipitate Precipitation, then suction filtration, washing to neutrality, further filtration and drying to obtain the aminophenoxyphthalonitrile resin monomer.
上述的氨基苯氧基邻苯二甲腈树脂单体的合成方法中，优选的，所述后处理的过程中：所述NaOH水溶液的浓度为0.1mol/L～0.2mol/L，所述干燥的温度为60℃～80℃，所述干燥的时间为12h～16h。In the synthesis method of the above-mentioned aminophenoxyphthalonitrile resin monomer, preferably, in the process of the post-treatment: the concentration of the NaOH aqueous solution is 0.1mol/L～0.2mol/L, and the drying The temperature is 60°C-80°C, and the drying time is 12h-16h.
本发明的氨基苯氧基邻苯二甲腈树脂单体的合成路线图如下：The synthetic route figure of aminophenoxy phthalonitrile resin monomer of the present invention is as follows:
本发明通过改善分子空间结构，使活性氨基与不饱和腈基在空间上距离更近，从提高固化交联活性，降低固化温度、缩短固化时间，提高交联度，提高机械性能。The invention improves the molecular space structure, makes the active amino group and the unsaturated nitrile group closer in space, improves the curing crosslinking activity, reduces the curing temperature, shortens the curing time, increases the degree of crosslinking, and improves the mechanical properties.
经发明人仔细研究和比较，发现自催化固化单体中，催化活性基团与腈基的不同相对位置对催化反应有显著不同的影响。基于此，发明人设计和开发了一种新型结构的自催化单体，见式1，从空间结构上看，活性氨基与不饱和的腈基在分子内邻近，这样的距离便于活性氢转移至腈基而成环，这样的分子内转移而催化腈基聚合有利于降低固化温度和缩短固化时间。同时热重分析表明，固化后的聚合物有优良的热稳定性，在氮气氛下800℃残炭率为73％，与高温长时间固化物的热稳定性相当。这将大大改善腈基树脂的加工性能，为制备高性能复合材料提供了便利，这对于工业化生产是非常有实际意义的。After careful study and comparison by the inventors, it is found that in the self-catalytic curing monomer, different relative positions of the catalytic active group and the nitrile group have significantly different effects on the catalytic reaction. Based on this, the inventor has designed and developed a self-catalyzed monomer with a new structure, see formula 1. From the perspective of spatial structure, the active amino group and the unsaturated nitrile group are adjacent to each other in the molecule, and such a distance is convenient for the transfer of active hydrogen to The nitrile group forms a ring, and such intramolecular transfer catalyzes the polymerization of the nitrile group, which is beneficial to reduce the curing temperature and shorten the curing time. At the same time, thermogravimetric analysis shows that the cured polymer has excellent thermal stability, and the carbon residue rate is 73% at 800°C under nitrogen atmosphere, which is equivalent to the thermal stability of the high-temperature long-term cured product. This will greatly improve the processing performance of the nitrile-based resin, and provide convenience for the preparation of high-performance composite materials, which is very practical for industrial production.
与现有技术相比，本发明的优点在于：Compared with the prior art, the present invention has the advantages of:
(1)本发明提供了一种新型分子结构的自催化腈基树脂单体(即氨基苯氧基邻苯二甲腈树脂单体及其合成方法)，相比公开的自催化单体有更高的反应活性。(1) The present invention provides a kind of self-catalyzed nitrile base resin monomer (being aminophenoxy phthalonitrile resin monomer and synthetic method thereof) of a kind of novel molecular structure, has more than disclosed self-catalyzed monomer High reactivity.
(2)本发明提供的腈基树脂单体是由3-硝基邻苯二甲腈制备而来，相比传统的4-硝基邻苯二甲腈成本更低，可以降低一半，适于低成本工业化生产。(2) The nitrile-based resin monomer provided by the present invention is prepared from 3-nitrophthalonitrile, which is lower than the cost of traditional 4-nitrophthalonitrile, can be reduced by half, and is suitable for Low-cost industrial production.
(3)本发明提供的腈基树脂单体可以在相对更低的温度开始固化(200℃，1小时)，固化温度和后固化温度都有大大降低，且固化时间大大缩短。固化程序为200℃保持1小时，250℃保持30分钟，280℃保持30分钟，总时间为2小时，所得固化物在氮气氛下800℃的残炭率可以达到73％，这非常有利于低成本制备高性能复合材料。(3) The nitrile-based resin monomer provided by the present invention can be cured at a relatively lower temperature (200°C, 1 hour), the curing temperature and post-curing temperature are greatly reduced, and the curing time is greatly shortened. The curing program is 200°C for 1 hour, 250°C for 30 minutes, and 280°C for 30 minutes. The total time is 2 hours. The carbon residue rate of the obtained cured product at 800°C under nitrogen atmosphere can reach 73%, which is very beneficial for low Cost-effective preparation of high-performance composite materials.
综上，本发明提供的高活性自催化腈基树脂单体(氧基苯氧基邻苯二甲腈树脂单体)具有反应活性高、制备成本低、固化温度低、固化时间短，后固化温度低且时间短的性能，同时其固化物耐温性可以与高温、长时间腈基树脂固化物媲美。本发明的腈基树脂单体适于低成本工业化生产，可广泛应用于涂料、电子封装材料、航空航天、微电子、机械制造、船舶和树脂基复合材料等领域，具有广阔的市场前景。In summary, the highly active self-catalyzed nitrile-based resin monomer (oxyphenoxy phthalonitrile resin monomer) provided by the present invention has high reactivity, low preparation cost, low curing temperature, short curing time, and post-curing The performance of low temperature and short time, at the same time, the temperature resistance of the cured product can be compared with the cured product of nitrile resin with high temperature and long time. The nitrile-based resin monomer of the invention is suitable for low-cost industrial production, can be widely used in coatings, electronic packaging materials, aerospace, microelectronics, machinery manufacturing, ships, resin-based composite materials and other fields, and has broad market prospects.
附图说明Description of drawings
图1为本发明实施例1的氨基苯氧基邻苯二甲腈树脂单体的氢核磁谱图。Fig. 1 is the proton magnetic spectrum of the aminophenoxyphthalonitrile resin monomer of Example 1 of the present invention.
图2为本发明实施例1的氨基苯氧基邻苯二甲腈树脂单体的TGA测试图。Fig. 2 is a TGA test chart of the aminophenoxyphthalonitrile resin monomer of Example 1 of the present invention.
具体实施方式detailed description
以下结合说明书附图和具体优选的实施例对本发明作进一步描述，但并不因此而限制本发明的保护范围。The present invention will be further described below in conjunction with the accompanying drawings and specific preferred embodiments, but the protection scope of the present invention is not limited thereby.
以下实施例中所采用的材料和仪器均为市售。All materials and instruments used in the following examples are commercially available.
实施例1：Example 1:
一种本发明的氨基苯氧基邻苯二甲腈树脂单体，分子结构式为下式(Ⅰ)：A kind of aminophenoxy phthalonitrile resin monomer of the present invention, molecular structural formula is following formula (I):
一种上述本实施例的氨基苯氧基邻苯二甲腈树脂单体的合成方法，包括以下步骤：A kind of synthetic method of the above-mentioned aminophenoxy phthalonitrile resin monomer of the present embodiment, comprises the following steps:
(1)将0.1mol邻氨基苯酚、0.15mol无水碳酸钾、150ml N,N-二甲基甲酰胺DMF(溶剂)加入到干燥的反应容器(如三口瓶)中，抽真空换氮气，油浴加热至90℃，保持1小时。(1) Add 0.1mol of o-aminophenol, 0.15mol of anhydrous potassium carbonate, and 150ml of N,N-dimethylformamide DMF (solvent) into a dry reaction vessel (such as a three-necked flask), vacuumize and change nitrogen, and oil The bath was heated to 90°C for 1 hour.
(2)向上述反应容器中加入0.08mol 3-硝基邻苯二甲腈，在90℃下回流反应5小时，然后冷却至室温。(2) Add 0.08 mol of 3-nitrophthalonitrile to the above reaction vessel, reflux at 90° C. for 5 hours, and then cool to room temperature.
(3)向步骤(2)得到的产物溶液中加入0.1mol/L NaOH水溶液600ml，出现大量沉淀，抽滤，用去离子水反复洗涤至中性，过滤，将所得黄色固体粉末放置在60℃的真空干燥箱12小时，得到3-邻氨基苯氧基邻苯二甲腈，即氨基苯氧基邻苯二甲腈树脂单体。(3) Add 600ml of 0.1mol/L NaOH aqueous solution to the product solution obtained in step (2), a large amount of precipitation occurs, filter with suction, wash repeatedly with deionized water until neutral, filter, and place the resulting yellow solid powder at 60°C 12 hours in a vacuum oven to obtain 3-o-aminophenoxyphthalonitrile, that is, aminophenoxyphthalonitrile resin monomer.
本实施例制备的氨基苯氧基邻苯二甲腈树脂单体用核磁和气质联用进行了结构鉴定，如图1所示。1H NMR(400MHz,dmso)δ7.80–7.66(m,1H),7.02(t,J＝7.6Hz,1H),6.95(d,J＝7.9Hz,1H),6.91(d,J＝6.9Hz,1H),6.82(d,J＝8.0Hz,1H),6.57(t,J＝7.6Hz,1H),5.20(s,1H)。气质联用中分子离子峰为235，理论计算分子量为235，由此说明，所合成物为目标物。The structure of the aminophenoxyphthalonitrile resin monomer prepared in this example was identified by NMR and GC-MS, as shown in FIG. 1 . 1H NMR (400MHz, dmso) δ7.80–7.66(m, 1H), 7.02(t, J=7.6Hz, 1H), 6.95(d, J=7.9Hz, 1H), 6.91(d, J=6.9Hz , 1H), 6.82 (d, J=8.0Hz, 1H), 6.57 (t, J=7.6Hz, 1H), 5.20 (s, 1H). The molecular ion peak in GC-MS is 235, and the theoretically calculated molecular weight is 235, which shows that the synthesized compound is the target compound.
本实施例制备的氨基苯氧基邻苯二甲腈树脂单体经过如下固化程序(200℃保持1小时，250℃保持30分钟，280℃保持30分钟)后的TGA测试如图2所示，结果表明该树脂在氮气氛下的5％失重温度为445℃，800℃下的残炭率为73.1％。The TGA test of the aminophenoxyphthalonitrile resin monomer prepared in this example after the following curing procedure (200°C for 1 hour, 250°C for 30 minutes, and 280°C for 30 minutes) is shown in Figure 2. The results show that the 5% weight loss temperature of the resin under nitrogen atmosphere is 445°C, and the carbon residue rate at 800°C is 73.1%.
实施例2：Example 2:
一种本发明的氨基苯氧基邻苯二甲腈树脂单体，分子结构式与实施例1相同。A kind of aminophenoxy phthalonitrile resin monomer of the present invention, molecular structure formula is identical with embodiment 1.
一种本实施例的氨基苯氧基邻苯二甲腈树脂单体的合成方法，步骤与实施例1基本相同，区别仅在于：步骤(1)中，采用的溶剂为二甲亚砜DMSO。A method for synthesizing the aminophenoxyphthalonitrile resin monomer of this embodiment, the steps are basically the same as in Example 1, the only difference being that in step (1), the solvent used is dimethyl sulfoxide DMSO.
实施例3：Example 3:
一种本发明的氨基苯氧基邻苯二甲腈树脂单体，分子结构式与实施例1相同。A kind of aminophenoxy phthalonitrile resin monomer of the present invention, molecular structure formula is identical with embodiment 1.
一种本实施例的氨基苯氧基邻苯二甲腈树脂单体的合成方法，步骤与实施例1基本相同，区别仅在于：步骤(2)中，加热温度为85℃，保持5小时。A method for synthesizing the aminophenoxyphthalonitrile resin monomer of this embodiment, the steps are basically the same as in Example 1, the only difference is that in step (2), the heating temperature is 85° C. and kept for 5 hours.
实施例4：Example 4:
一种本发明的氨基苯氧基邻苯二甲腈树脂单体，分子结构式与实施例1相同。A kind of aminophenoxy phthalonitrile resin monomer of the present invention, molecular structure formula is identical with embodiment 1.
一种本实施例的氨基苯氧基邻苯二甲腈树脂单体的合成方法，步骤与实施例1基本相同，区别仅在于：步骤(1)中催化剂为无水碳酸钠。A kind of synthesis method of the aminophenoxy phthalonitrile resin monomer of the present embodiment, the steps are basically the same as in Example 1, the only difference being that the catalyst in the step (1) is anhydrous sodium carbonate.
以上所述仅是本发明的优选实施方式，本发明的保护范围并不仅局限于上述实施例。凡属于本发明思路下的技术方案均属于本发明的保护范围。应该指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下的改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above descriptions are only preferred implementations of the present invention, and the scope of protection of the present invention is not limited to the above examples. All technical solutions under the idea of the present invention belong to the protection scope of the present invention. It should be pointed out that for those skilled in the art, improvements and modifications without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903189A (en) * | 2017-10-24 | 2018-04-13 | 中国科学院化学研究所 | It is a kind of phthalonitrile-terminated containing fluorene structured poly (arylene ether nitrile) oligomer, solidfied material and preparation method thereof |
| CN108442122A (en) * | 2018-04-26 | 2018-08-24 | 湖南师范大学 | A kind of sizing agent for preparing quartz fiber/nitrile resin composite material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6590118B1 (en) * | 1999-09-29 | 2003-07-08 | Novo Nordisk A/S | Aromatic compounds |
| CN1944400A (en) * | 2006-09-14 | 2007-04-11 | 电子科技大学 | Double end group ortho-benzene dimethyl nitrile-benzo oxazine resin, solidified substance and its preparing method and use |
| CN101143928A (en) * | 2007-09-12 | 2008-03-19 | 四川大学 | A kind of polyphthalonitrile resin and preparation method thereof |
| CN102504252A (en) * | 2011-11-18 | 2012-06-20 | 电子科技大学 | Amino phenoxy phthalonitrile pre-polymer, condensate and preparation method and application thereof |
-
2015
- 2015-10-30 CN CN201510725659.8A patent/CN106631893A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6590118B1 (en) * | 1999-09-29 | 2003-07-08 | Novo Nordisk A/S | Aromatic compounds |
| CN1944400A (en) * | 2006-09-14 | 2007-04-11 | 电子科技大学 | Double end group ortho-benzene dimethyl nitrile-benzo oxazine resin, solidified substance and its preparing method and use |
| CN101143928A (en) * | 2007-09-12 | 2008-03-19 | 四川大学 | A kind of polyphthalonitrile resin and preparation method thereof |
| CN102504252A (en) * | 2011-11-18 | 2012-06-20 | 电子科技大学 | Amino phenoxy phthalonitrile pre-polymer, condensate and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王海静等: "4-苯氧基邻苯二甲腈的合成研究", 《宇航材料工艺》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903189A (en) * | 2017-10-24 | 2018-04-13 | 中国科学院化学研究所 | It is a kind of phthalonitrile-terminated containing fluorene structured poly (arylene ether nitrile) oligomer, solidfied material and preparation method thereof |
| CN108442122A (en) * | 2018-04-26 | 2018-08-24 | 湖南师范大学 | A kind of sizing agent for preparing quartz fiber/nitrile resin composite material |
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