阅读说明：本技术 一种含有螺环结构的邻苯二甲腈单体及其树脂 (Phthalonitrile monomer containing spiro structure and resin thereof ) 是由 白胜楠 于晓燕 张庆新 于 2020-07-17 设计创作，主要内容包括：本发明为一种含有螺环结构的邻苯二甲腈单体及其树脂。该单体的结构式如下。制备方法中,利用3,3,3’,3’-四甲基-6,6’-二羟基-1,1’-螺旋双茚满和4-硝基邻苯二甲腈为原料,首次制备了一种含有螺环结构的邻苯二甲腈单体及其树脂。本发明扩大了聚苯腈树脂的应用范围,在航空航天、发动机外壳、微电子封装等领域具有广阔的应用前景。<Image he="229" wi="700" file="DDA0002589653800000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention relates to a phthalonitrile monomer containing a spiro structure and resin thereof. The structural formula of the monomer is shown as follows. In the preparation method, 3,3,3',3' -tetramethyl-6, 6 '-dihydroxy-1, 1' -spiral biindane and 4-nitrophthalonitrile are used as raw materials, and the phthalonitrile monomer containing the spiro structure and the resin thereof are prepared for the first time. The invention enlarges the application range of the polybenzonitrile resin and has wide application prospect in the fields of aerospace, engine shells, microelectronic packaging and the like.)

1. A phthalonitrile monomer containing a spiro structure is characterized in that the structural formula of the monomer is as follows:

2. the process for producing a spiro-phthalonitrile-containing monomer according to claim 1, which comprises the steps of:

adding 3,3,3',3' -tetramethyl-6, 6 '-dihydroxy-1, 1' -spiral biindane and a catalyst into a reactor under the atmosphere of protective gas, then adding a polar organic solvent, stirring for 1-2 hours at 80-90 ℃, then adding 4-nitrophthalonitrile, and continuing to stir and react for 6-8 hours at 80-90 ℃; after the reaction liquid is cooled to room temperature, pouring the reaction liquid into deionized water, separating out a product, and then carrying out reduced pressure suction filtration, deionized water washing and vacuum drying to obtain a phthalonitrile monomer containing a spiro structure;

wherein, the molar ratio is 3,3,3',3' -tetramethyl-6, 6 '-dihydroxy-1, 1' -spiral double indane: catalyst 1:2-1: 2.5; 1800ml of organic solvent is added into each mole of 3,3,3',3' -tetramethyl-6, 6 '-dihydroxy-1, 1' -spiral bis-indane; the molar ratio of 3,3,3',3' -tetramethyl-6, 6 '-dihydroxy-1, 1' -helical bisindane: 4-nitrophthalonitrile ═ 1:2.

3. The process for producing a spiro-phthalonitrile-containing monomer according to claim 2, wherein the catalyst is anhydrous potassium carbonate or anhydrous sodium carbonate.

4. The process for producing a spiro-phthalonitrile-containing monomer according to claim 2, wherein the polar organic solvent is N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide or N-methylpyrrolidone.

5. The method for producing a spiro phthalonitrile-containing monomer according to claim 2, wherein the protective gas is nitrogen or argon.

6. The phthalonitrile resin with a spiro structure is characterized by being prepared by the following method, and comprising the following steps:

mixing phthalonitrile monomer containing spiro structure with aromatic amine curing agent, grinding for 0.5-1 h, putting into a mold, melting at 260-280 ℃, vacuum degassing for 10-20min, transferring to a muffle furnace while hot, and carrying out temperature programming curing at 260-410 ℃ to finally obtain phthalonitrile resin containing spiro structure;

wherein, the mass ratio is that phthalonitrile monomer: aromatic amine curing agent 1: 0.05-0.1;

the aromatic amine curing agent is 4,4 '-diaminodiphenyl ether, 4' -bis (4-aminophenoxy) diphenyl sulfone, 3,4 '-diaminodiphenyl ether or 4,4' -diaminodiphenyl sulfone.

7. The phthalonitrile resin having a spiro structure according to claim 6, wherein the temperature-programmed step comprises: the temperature is maintained at each temperature segment of 260-.

Technical Field

The invention belongs to the field of preparation of novel high-temperature-resistant high polymer materials, and relates to a preparation method of a high-temperature-resistant phthalonitrile monomer containing a spiro structure and resin thereof.

Background

The phthalonitrile resin is obtained by the bulk addition polymerization of phthalonitrile monomer under the condition that aromatic amine containing active hydrogen atoms is used as a curing agent, and is called as the polyphenylacrylonitrile resin for short. As a novel high-temperature-resistant thermosetting resin, the high-temperature-resistant thermosetting resin has excellent thermal stability and thermal oxidation stability, excellent thermal mechanical property, low water absorption rate and excellent chemical corrosion resistance, so that the high-temperature-resistant thermosetting resin has great application potential in the fields of aerospace, ship warships, electronic packaging and the like.

Polybenzonitrile resins developed to date by the Keller group in the 80's of the 20 th century, a variety of phthalonitrile monomers with different structures and functions were developed. These include oligomeric monomers containing bisphenol A (R.Du, W.Li, X.Liu, Synthesis and thermal properties of bisphenol A. they contain inorganic monomers and organic monomers, M.Laskoski, M.B.Schear, A.New, D.D.Dominguez, H.L.Rickskoski, J.Hervey, T.M.Keller, Improved Synthesis and properties of organic monomers and inorganic monomers, Polymer-basic polymeric resins and polymers, Polymer, 67, 185: 191, Synthesis and 9. J.S.P.Y.Y.Q.P.Y.P.Y.P.Y.P.Y.P.Y.P.Y.Q.P.Y.P.Y.Q.P.P.Y.P.Y.Q.P.Y.P.Y.N.P.P.P.P.Y.N.P.P.P.Y.P.P.Y.P.P.Y.K.P.P.P.P.G.Y.P.G.Y.K.P.P.Y.Y.K.P.M.Y.M.K.K.K.P.P.H.M.M.Y.Y.N.Y.Y.K.K.K.K.K.K.N.P.K.H.M.M.K.K.P.K.P.P.H.M.P.K.Y.M.K.K.K.K.K.K.K.K.K.K.K.P.P.P.K.P.K.K.M.P.K.K.P.K.K.K.P.K.K.P.K.K.K.K.K.K.P.P.P.P.K.K.P.P.K.K.P.K.K.P.K.K.K.P.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.P.P.K.K.K.K.K.P.P.K.K.P.K.K.K.K.K.P.P.K.K.K.K.K.P.K.K.K.K.K.K.K.. The oligomeric monomer lowers the melting point of the monomer due to the introduction of a flexible ether bond, but the polymer lowers the thermal stability due to the long molecular chain and the high content of ether bond.

Disclosure of Invention

The invention aims to provide a spiro phthalonitrile-containing monomer and a resin thereof aiming at the defects in the prior art. The monomers and resins have a twisted spiro structure. In the preparation method, 3,3' -tetramethyl-6, 6' -dihydroxy-1, 1' -spiral biindane and 4-nitrophthalonitrile are used as raw materials, and the phthalonitrile monomer containing the spiro structure and the resin thereof are prepared for the first time. The invention enlarges the application range of the polybenzonitrile resin and has wide application prospect in the fields of aerospace, engine shells, microelectronic packaging and the like.

The technical scheme of the invention is as follows:

a phthalonitrile monomer containing a spiro structure has the following structural formula:

a preparation method of a spiro phthalonitrile-containing monomer comprises the following steps:

adding 3,3,3',3' -tetramethyl-6, 6 '-dihydroxy-1, 1' -spiral biindane and a catalyst into a reactor under the atmosphere of protective gas, then adding a polar organic solvent, stirring for 1-2 hours at 80-90 ℃, then adding 4-nitrophthalonitrile, and continuing to stir and react for 6-8 hours at 80-90 ℃; after the reaction liquid is cooled to room temperature, pouring the reaction liquid into deionized water, separating out a product, and then carrying out reduced pressure suction filtration, deionized water washing and vacuum drying to obtain a phthalonitrile monomer containing a spiro structure;

wherein, the molar ratio is 3,3,3',3' -tetramethyl-6, 6 '-dihydroxy-1, 1' -spiral double indane: the catalyst is 1:2-1: 2.5; 1800ml of organic solvent is added into each mole of 3,3,3',3' -tetramethyl-6, 6 '-dihydroxy-1, 1' -spiral bis-indane; the molar ratio of 3,3,3',3' -tetramethyl-6, 6 '-dihydroxy-1, 1' -helical bisindane: 4-nitrophthalonitrile is 1: 2;

the catalyst is anhydrous potassium carbonate or anhydrous sodium carbonate.

The polar organic solvent is N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone.

The protective gas is nitrogen or argon.

The phthalonitrile resin containing the spiro structure is prepared by the following method, and comprises the following steps:

mixing phthalonitrile monomer containing spiro structure with aromatic amine curing agent, grinding for 0.5-1 h, putting into a mold, melting at 260-280 ℃, vacuum degassing for 10-20min, transferring to a muffle furnace while hot, and carrying out temperature programming curing at 260-410 ℃ to finally obtain phthalonitrile resin containing spiro structure;

wherein, the mass ratio is that phthalonitrile monomer: aromatic amine curing agent is 1: 0.05-0.1;

the aromatic amine curing agent is 4,4 '-diaminodiphenyl ether, 4' -bis (4-aminophenoxy) diphenyl sulfone, 3,4 '-diaminodiphenyl ether or 4,4' -diaminodiphenyl sulfone;

the temperature programming step comprises the following steps: the temperature is raised and cured at a rate of 3-5 ℃/min in each temperature segment of 260-.

The chemical reagents are all commercially available.

The invention has the beneficial effects that:

the invention firstly introduces a twisted rigid spiro structure into phthalonitrile monomer molecules to prepare the novel phthalonitrile resin containing the spiro structure. The variety of the polybenzonitrile resin is enriched. The twisted spiro structure can impart better solubility to the monomer. The improved solubility is beneficial to further processing of the monomer and preparation of the composite material. Meanwhile, due to the existence of the twisted structure, the steric hindrance between molecular chains is larger, the stacking density of the polymer can be reduced, and the dielectric constant of the material is reduced. By controlling the curing temperature and time, the temperature at which the resin loses 5% by weight can reach more than 500 ℃. The application range of the polybenzonitrile resin is expanded, and the polybenzonitrile resin is expected to be applied to the fields of aerospace, engine housings, microelectronic packaging and the like.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of phthalonitrile monomer containing spiro structure obtained in example 1.

FIG. 2 is an infrared spectrum of the phthalonitrile monomer having a spiro structure obtained in example 1 and a raw material.

Detailed Description