CN106279682B - A kind of preparation method of the base of structure-biological containing isobide o-phthalonitrile resin - Google Patents

Abstract

The present invention relates to a kind of preparation methods of the base of structure-biological containing isobide o-phthalonitrile resin, this method is raw material using isobide, in polar solvent, using Anhydrous potassium carbonate as catalyst, the phthalonitrile of the structure containing isobide is synthesized with 4 nitrophthalonitriles, which can be used as monomer and prepare o-phthalonitrile resin.This kind of phthalonitrile monomer has flexible larger aliphatic heterocycle, can reduce the fusing point of monomer, simultaneously because isobide derives from reproducible biomass, meets the requirement of environmental protection and sustainable development.Under identical temperature programming condition of cure, the o-phthalonitrile resin IS Ph Resin of the structure containing isobide heat decomposition temperature T under nitrogen atmosphere_5%It is 83% up to the carbon yield at 550 DEG C, 800 DEG C, shows the hot property more excellent than petroleum base '-biphenyl diphenol type o-phthalonitrile resin BP Ph Resin.

Description

A kind of preparation method of the base of structure-biological containing isobide o-phthalonitrile resin

Technical field

The invention belongs to novel fire resistant macromolecule material preparation areas, are related to a kind of base neighbour's benzene of structure-biological containing isobide The preparation method of dimethoxy nitrile resin.

Background technology

O-phthalonitrile resin is the general name of a kind of high-performance thermosetting resin of molecular chain-end phthalonitrile structure, Its with excellent thermal stability, chemical-resistant, radioresistance, fire-retardant self-extinguishment, optical property outstanding and electric property, Excellent comprehensive performance is still kept under high temperature, is had in high-technology fields such as space flight and aviation, automobile, electronics, machineries wide Application prospect.

The Keller seminars of US Naval Research Laboratory just have been devoted to O-phthalic since late 1970s The synthesis of nitrile resin and the research of curing.They are cured using gradient increased temperature, normal pressure, are obtained by changing monomer structure A series of water absorption rates are low, heat resistance and mechanical performance are excellent o-phthalonitrile resin.Then they are also to aromatic diamines Selection, curing kinetics and the curing process of curing agent have done detailed research, have greatly pushed o-phthalonitrile resin Development [Keller T M, Griffith J R.The synthesis of highly fluorinated phthalonitrile resins and cure studies[J].Journal of Fluorine Chemistry,1979, 13:315-324；Keller T M.Phthalonitrile-based high-temperature resin[J].Journal of Polymer Science:Part A:Polymer Chemistry,1988,26:3199-3212；Laskoski M,Neal A,Keller T M,Dominguez D,Klug C A,Saab A P.Improved synthesis of oligomeric phthalonitriles and studies designed for low temperature cure[J].Journal of Polymer Science:Part A:Polymer Chemistry,2014,52:1662-1668.]。

Since the 21th century, the research of o-phthalonitrile resin enters the booming stage, in Keller et al. On the basis of the curing of development, the research direction in China mainly develops towards structure, manufacturing process and functional diversities.Herein Period, domestic Chinese Academy of Sciences Beijing chemistry institute, Sichuan University, University of Electronic Science and Technology, Jilin University, Hebei industry are big The scientific research institutions such as, Dalian University of Technology have also successively started the development work of o-phthalonitrile resin, and route is different, respectively have into Open up [Zhou H, Badashah A, Luo Z H, Liu F, Zhao T.Preparation and property comparison of ortho,meta,and para autocatalytic phthalonitrile compounds with amino group[J].Polymer Advanced Technology,2011,22:1459-1465；Zuo F,Liu X B.Synthesis and curing behavior of a novel benzoxazine-based bisphthalonitrile monomer[J].Journal of Applied Polymer Science,2010,117: 1469-1475；Zong L S,Liu C,Zhang S H,Wang J Y,Jian X G.Enhanced thermal properties of phthalonitrile networks by cooperating phenyl-s-triazine moieties in backbones[J].Polymer,2015,77:177-188.]。

Prepared phthalonitrile monomer is to cure obtained adjacent benzene two containing petroleum-based aromatic rings mostly at present Formonitrile HCN resin has preferable comprehensive performance.But shortage and environmental pollution of current conventional petroleum based raw material etc. have become can not The problem of ignorance, to meet the requirement of sustainable development, while in order to expand the diversity of o-phthalonitrile resin, we study A kind of phthalonitrile monomer of the novel structure of isobide containing biology base.Contain aliphatic heterocycle in isobide, ties Structure has certain rigidity, is introduced into phthalonitrile monomer, can not only reduce the fusing point of monomer, but also can ensure to cure The excellent comprehensive performance of o-phthalonitrile resin afterwards.And the phthalonitrile monomer and resin of this structure containing isobide are current Not disclosed report.

Invention content

The present invention is raw material using isobide, adjacent with 4- nitros using Anhydrous potassium carbonate as catalyst in polar solvent Benzene dicarbonitrile has synthesized the phthalonitrile of the structure containing isobide, which can be used as monomer and prepare o-phthalonitrile resin. This kind of phthalonitrile monomer has flexible larger aliphatic heterocycle compared with traditional petroleum base phthalonitrile monomer, The fusing point of monomer can be reduced, simultaneously because isobide derives from reproducible biomass, meets environmental protection and sustainable development Requirement.In addition the thermal stability of the o-phthalonitrile resin of the structure containing isobide is than '-biphenyl diphenol type o-phthalonitrile resin It is more excellent.

A kind of preparation method of the base of structure-biological containing isobide o-phthalonitrile resin, steps are as follows：

(1) synthesis of monomer：It is 1 in molar ratio by isobide, 4- nitrophthalonitriles and catalyst：2~3：1.5 ~3 mix successively, according still further to 10~20mL solvents are added in every gram of isobide, add the solvent dried, nitrogen protection, Under conditions of 25 DEG C, react 24~72 hours；After reaction, product is poured into cold water, is adjusted with the dilute hydrochloric acid of 1mol/L Then pH value is washed with deionized to filtrate and is in neutrality to neutrality, 70 DEG C are dried in vacuo 24 hours, obtain knot containing isobide The phthalonitrile monomer IS-Ph of structure, spare, chemical structural formula is as follows：

(2) cure：The phthalonitrile monomer and aromatic diamines curing agent for the structure containing isobide that step (1) is obtained It is 1 in mass ratio：0.02~0.15 mixing after being fully ground, is loaded into the reactor that temperature is 150~190 DEG C, heating Stirring is until then thawing completely pours into liquid mixture in mold, and to liquid mixture in 150~400 DEG C of temperature strips Cure 8 hours under part, obtains the base of structure-biological containing isobide o-phthalonitrile resin (IS-Ph Resin).

In step (1), the catalyst is Anhydrous potassium carbonate.

In step (1), the solvent is dimethyl sulfoxide (DMSO), n,N-Dimethylformamide, n,N-dimethylacetamide, N- Methyl pyrrolidone or sulfolane.

In step (2), the aromatic diamines curing agent is H₂N-Ar-NH₂；Wherein, Ar is

Beneficial effects of the present invention：The fusing point of the phthalonitrile monomer of the structure containing isobide of the present invention is 181 DEG C, Less than the fusing point (236 DEG C) of '-biphenyl diphenol type phthalonitrile monomer.It is solid with the phthalonitrile monomer of the structure containing isobide Resin heat decomposition temperature (T under nitrogen atmosphere after change_5%) up to the carbon yield at 550 DEG C, 800 DEG C it is 83%, show ratio The more excellent hot property of petroleum base '-biphenyl diphenol type o-phthalonitrile resin.Therefore, the structure of the invention containing isobide O-phthalonitrile resin has not only expanded the diversity of o-phthalonitrile resin, while having opened up biology base high-performance thermosetting tree The application range of fat.

Description of the drawings

Fig. 1 is the nuclear magnetic spectrogram of the phthalonitrile monomer (IS-Ph) of the structure containing isobide in embodiment 1.

In o-phthalonitrile resins (IS-Ph Resin) and comparative example 1 of the Fig. 2 for the structure containing isobide in embodiment 1 The thermogravimetric curve of '-biphenyl diphenol type o-phthalonitrile resin (BP-Ph Resin).

Fig. 3 is the nuclear magnetic spectrogram of '-biphenyl diphenol type phthalonitrile monomer (BP-Ph) in comparative example 1.

Specific implementation mode

Below in conjunction with attached drawing and technical solution, the specific implementation mode that further illustrates the present invention.

Embodiment 1

Monomer synthesizes：By the isobide of 0.1mol, the anhydrous carbon of the 4- nitrophthalonitriles of 0.25mol and 0.2mol Sour potassium is sequentially added into reactor, adds the dried dimethyl sulfoxide (DMSO)s of 200mL, then nitrogen protection, is reacted at 25 DEG C 72 hours.After reaction, product is poured into 3L cold water, the pH value of system is then adjusted to neutrality with the dilute hydrochloric acid of 1mol/L, Then it is washed with deionized to filtrate after being in neutrality, 70 DEG C are dried in vacuo 24 hours, obtain the neighbour of structure containing isobide benzene two Formonitrile HCN monomer (IS-Ph), it is spare.

Solidification：Weigh the phthalonitrile monomer of the dried structures containing isobide of 10g and the 4,4'- diamino of 0.5g Diphenyl sulphone (DPS) mixes.It after being fully ground, is loaded into the reactor that temperature is 180 DEG C, heating stirring until melt, then completely Liquid mixture is poured into mold, and is placed in Muffle furnace with 200 DEG C/2 hours；250 DEG C/2 hours；350 DEG C/2 hours； Temperature programming solidification in 400 DEG C/2 hours, then takes out and is cooled to room temperature, obtain the phthalonitrile tree of the structure containing isobide Fat (IS-Ph Resin).

Fig. 1 is the nucleus magnetic hydrogen spectrum spectrogram of the phthalonitrile monomer of structure containing isobide (IS-Ph).It can from figure Go out, spectrogram peak shape is clear, without other miscellaneous peaks other than remaining two solvent peaks in deuterated reagent, illustrates synthesized monomer purity It is high.By calculating, each hydrogen is all proven in nucleus magnetic hydrogen spectrum spectrogram in monomer structure, illustrates that synthesized monomer is containing different The phthalonitrile of sorbierite structure.

The thermogravimetric curve of the o-phthalonitrile resin of structure containing isobide (IS-Ph Resin) in Fig. 2, under nitrogen atmosphere Heat decomposition temperature (T_5%) be carbon yield at 550 DEG C, 800 DEG C it is 83%.

Comparative example 1

Monomer synthesizes：By the 4,4 ' of 0.1mol-'-biphenyl diphenols, the 4- nitrophthalonitriles of 0.22mol and 0.15mol Anhydrous potassium carbonate is sequentially added into reactor, adds the dried dimethyl sulfoxide (DMSO)s of 180mL, then nitrogen protection, 25 DEG C Lower reaction 72 hours.After reaction, product is poured into 3L cold water, is then adjusted to the pH value of system with the dilute hydrochloric acid of 1mol/L Then neutrality is washed with deionized to filtrate after being in neutrality, 70 DEG C are dried in vacuo 24 hours, obtain '-biphenyl diphenol type neighbour benzene two Formonitrile HCN monomer (BP-Ph), spare, chemical structural formula is as follows：

Solidification：Weigh the 4,4' diaminodiphenyl sulfone of 10g dried '-biphenyl diphenol type phthalonitrile monomer and 0.5g Mixing.It after being fully ground, is loaded into the reactor that temperature is 250 DEG C, heating stirring until melt, then by liquid completely Mixture pours into mold, and is placed in Muffle furnace with 200 DEG C/2 hours；250 DEG C/2 hours；350 DEG C/2 hours；400℃/2 The temperature programming solidification of hour, then takes out and is cooled to room temperature, obtain '-biphenyl diphenol type o-phthalonitrile resin (BP-Ph Resin)。

Fig. 3 is the nucleus magnetic hydrogen spectrum spectrogram of '-biphenyl diphenol type phthalonitrile monomer (BP-Ph).It can be seen from the figure that spectrum Figure peak shape is clear, without other miscellaneous peaks other than remaining two solvent peaks in deuterated reagent, illustrates that synthesized monomer purity is high.It is logical Calculating is crossed, each hydrogen is all proven in nucleus magnetic hydrogen spectrum spectrogram in monomer structure, illustrates that synthesized monomer is '-biphenyl diphenol Type phthalonitrile.

The thermogravimetric curve of '-biphenyl diphenol type o-phthalonitrile resin (BP-Ph Resin) in Fig. 2, heat point under nitrogen atmosphere Solve temperature (T_5%) be carbon yield at 467 DEG C, 800 DEG C it is 71%.

Claims (1)

1. a kind of preparation method of the base of structure-biological containing isobide o-phthalonitrile resin, which is characterized in that steps are as follows：

(1) synthesis of monomer：It is 1 in molar ratio by isobide, 4- nitrophthalonitriles and catalyst：2~3：1.5~3 It mixes successively, according still further to 10~20mL solvents are added in every gram of isobide, the solvent dried is added, in nitrogen protection, 25 Under conditions of DEG C, react 24~72 hours；After reaction, product is poured into cold water, pH is adjusted with the dilute hydrochloric acid of 1mol/L Then value is washed with deionized to filtrate and is in neutrality to neutrality, 70 DEG C are dried in vacuo 24 hours, obtain structure containing isobide Phthalonitrile monomer IS-Ph, spare, chemical structural formula is as follows：

(2) cure：The phthalonitrile monomer and aromatic diamines curing agent for the structure containing isobide that step (1) is obtained are by matter Amount is than being 1：0.02~0.15 mixing after being fully ground, is loaded into the reactor that temperature is 150~190 DEG C, heating stirring Until melting completely to liquid mixture, then liquid mixture is poured into mold, and under 150~400 DEG C of temperature conditions Solidification 8 hours, obtains the base o-phthalonitrile resin of structure-biological containing isobide；

In step (1), the catalyst is Anhydrous potassium carbonate；

In step (1), the solvent is dimethyl sulfoxide (DMSO), n,N-Dimethylformamide, n,N-dimethylacetamide, N- methyl Pyrrolidones or sulfolane；

In step (2), the aromatic diamines curing agent is H₂N-Ar-NH₂；Wherein, Ar is