CN103408755A - Low-viscosity cyano resin monomer and polymer, and preparation method thereof - Google Patents
Low-viscosity cyano resin monomer and polymer, and preparation method thereof Download PDFInfo
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- CN103408755A CN103408755A CN2013102862817A CN201310286281A CN103408755A CN 103408755 A CN103408755 A CN 103408755A CN 2013102862817 A CN2013102862817 A CN 2013102862817A CN 201310286281 A CN201310286281 A CN 201310286281A CN 103408755 A CN103408755 A CN 103408755A
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Abstract
The invention relates to a low-viscosity cyano resin and a preparation method thereof, belonging to the technical field of organic high polymer materials. The low-viscosity cyano resin is prepared by proportionally mixing benzoxazine-ring-containing tetra-ortho-phthalonitrile resin monomer and diluter with para-nonyl phenol-type phthalonitrile monomer. The benzoxazine-ring-containing tetra-ortho-phthalonitrile resin monomer and nonyl phenol-type phthalonitrile monomer can be blended within a wider proportion range; and the mixture has the advantages of lower and adjustable viscosity at low temperature, favorable flowability, low-temperature curing and other processing properties. Meanwhile, the addition of the para-nonyl phenol-type phthalonitrile monomer has small influence on the heat stability of the benzoxazine-ring-containing tetra-ortho-phthalonitrile resin. The mixed resin has favorable processability of the benzoxazine resin and excellent temperature tolerance of the cyano resin, has the advantages of low-temperature processing, medium-temperature molding and high-temperature application, and can be used in the fields of space navigation and ship structural materials, paints, adhesives, electronic packaging materials and the like. The preparation method is easy to control, has the advantages of low reaction temperature and energy saving, and is suitable for continuous industrial production.
Description
Technical field
The invention belongs to the organic polymer material technical field, relate in particular to a kind of low viscosity itrile group resin monomer and polymkeric substance and preparation method thereof.
Background technology
O-phthalonitrile resin is the Keller synthetic acquisition first by US Naval Research Laboratory (NRL) the eighties in 20th century.Although the O-phthalic nitrile polymer shows excellent thermostability, mechanical property, thermo-oxidative stability and flame retardant resistance, this resinoid processing temperature window narrows, curing reaction is very slow, and concentrated heat release is obvious.Therefore, these shortcomings have seriously limited processibility and the overall application of this kind resin.
Benzoxazine colophony was found by Holly and Cope first the forties in 20th century in synthetic Mannich reaction product.Although it has overcome traditional resol, in the shaping solidification process, discharge micromolecular shortcoming, have lower viscosity and good processibility.Yet, due to benzoxazine, there is chelating hydrogen bond in a large amount of molecules in polymerization process, cause cross-linking density lower, so its thermotolerance and flame retardant resistance are difficult to meet the performance requriements of the extreme field such as aerospace industry to material.
The people such as Chinese patent Liu CN944400 filial piety ripple have synthesized a kind of double-terminal phthalonitrile resin that contains the benzoxazine ring, this patent provides a kind of 4-amino-benzene oxygen phthalonitrile monomer, and take its double-terminal phthalonitrile resin that contains the benzoxazine ring prepared as raw material.This resin has activity of curing reaction preferably, has both had the performance of benzoxazine colophony low-temperature curing, has again the resistant to elevated temperatures performance of o-phthalonitrile resin, and this resin solidification starting temperature is at 120 ℃-180 ℃.After Procuring, can obtain cured article at 320 ℃ of-370 ℃ of post curing treatment.
Summary of the invention
The objective of the invention is low viscosity and low-temperature curing performance in conjunction with the benzoxazine resinoid, and the thermostability of the excellence of o-phthalonitrile resin, flame retardant resistance and mechanical property preferably, a kind of low viscosity itrile group resin monomer and polymkeric substance are provided.
Two other purpose of the present invention is to provide the preparation method of a kind of low viscosity itrile group resin monomer and polymkeric substance thereof.
To achieve these goals, the technical solution adopted in the present invention is: a kind of low viscosity itrile group resin monomer, be to be formed by a kind of neighbours' phthalonitrile resin monomer and a kind of n nonylphenol type phthalonitrile monomer interworking that contains the benzoxazine ring, it contains neighbours' phthalonitrile resin monomer of benzoxazine ring and the structural formula of n nonylphenol type phthalonitrile monomer is respectively:
With
.
A kind of preparation method of low viscosity itrile group resin monomer comprises the following steps:
N nonylphenol type phthalonitrile monomer is added in reaction vessel, be heated to 60 ℃, then add the neighbours' benzene dicarbonitrile monomer that contains the benzoxazine ring to stir 30 minutes; Then be cooled to room temperature;
Wherein, n nonylphenol type phthalonitrile monomer content is between 1% ~ 30%.
A kind of low viscosity itrile group resinous polymer, be a kind of polymkeric substance of low viscosity itrile group resin monomer, and its structure is the reticulated structure of the Polybenzoxazine, π-pi-conjugated phthalocyanine ring and the triazine ring that comprise nitrogenous Mannich bridge construction;
The Polybenzoxazine structural formula of described nitrogenous Mannich bridge construction is:
The structural formula of described triazine ring is:
The structural formula of described phthalocyanine ring is:
Wherein, described low viscosity itrile group resin monomer, be to be obtained by a kind of neighbours' phthalonitrile resin monomer and n nonylphenol type phthalonitrile monomer interworking that contains the benzoxazine ring, its neighbours' phthalonitrile resin monomer and n nonylphenol type phthalonitrile monomer structural formula that contains the benzoxazine ring is respectively:
A kind of preparation method of low viscosity itrile group resinous polymer, be that described low viscosity itrile group resin monomer is heated to reaction 1-5 hour under 100 ~ 180 ℃, then, 240 ℃ of lower thermal treatments 3 ~ 5 hours, obtain low viscosity itrile group resinous polymer.
Owing to having adopted technique scheme, the present invention has following beneficial effect:
Reaction mechanism of the present invention can be described below:
The neighbours' phthalonitrile resin monomer that contains the benzoxazine ring in low viscosity itrile group resin interworking monomer provided by the present invention, at first ring-opening polymerization occurs under catalyzer or heat effect, form nitrogenous Mannich bridge construction, have simultaneously a large amount of active hydrogens to produce.The researchist finds the effectively itrile group polymerization in catalysis o-phthalonitrile resin monomer of a large amount of active hydrogens that the ring-opening polymerization of: benzoxazine ring produces.In addition, the people such as Burchill study discovery, and the cyano group polymerisate is mainly to take triazine ring and phthalocyanine ring as main.
The structure of polymkeric substance provided by the invention is through Fourier infrared (FTIR) spectrograph characterization test.The thermal characteristics of itrile group resinous polymer provided by the invention adopts differential scanning calorimeter MQ100 (DSC) and the thermal gravimetric analyzer Q50 of U.S. TA company to analyze.Wherein, the fusing point of low viscosity itrile group resin interworking monomer and curing summit temperature adopt DSC10 ℃/min to test; The carbon yield when temperature when the itrile group resinous polymer decomposes 5% and 800 ℃ adopts 20 ℃/min of TGA to test.
Low viscosity itrile group resin interworking monomer provided by the invention and polymkeric substance, adopt Fourier infrared (FTIR) spectrograph to carry out characterization test to its structure.Wherein the charateristic avsorption band of itrile group resinous polymer exists: 1010 cm
-1(phthalocyanine ring); 1360 cm
-1With 1520 cm
-1(triazine ring); 1246,1208 cm
-1(ehter bond); 832,782,729 cm
-1(charateristic avsorption band of phenyl ring), this test result show that described itrile group resinous polymer is the neighbours' phthalonitrile resin polymkeric substance (having occurred above charateristic avsorption band on the infared spectrum because of resin cured matter) that contains part benzoxazine ring.
The performance perameter of low viscosity itrile group resin provided by the invention is:
DSC solidifies peak temperature: 220 ~ 240 ℃; The temperature of decomposition 5%: 410 ~ 470 ℃; The carbon yield of 800 ℃: 65-75%.
Low viscosity itrile group resin interworking monomer provided by the invention, to adopt two kinds of phthalonitrile monomer interworkings to obtain, wherein contain in neighbours' benzene dicarbonitrile monomer of benzoxazine ring, after introducing benzoxazine structure, it has excellent shaping performance and good Molecular Structure Design.Under n nonylphenol type phthalonitrile monomer room temperature, exist with liquid form, have excellent mobility and low viscosity.Low viscosity itrile group resin interworking monomer provided by the invention has than low viscosity and melting viscosity, and the mobility had under lesser temps has been improved the processibility of resin greatly.Low viscosity itrile group resinous polymer provided by the invention has excellent activity of curing reaction, lower water-absorbent.Reaction process of the present invention is simply controlled, and product has good market outlook.
In sum, beneficial effect of the present invention is embodied in:
Described low viscosity itrile group resin is that the neighbours' phthalonitrile resin monomer and the n nonylphenol type phthalonitrile monomer interworking that contain the benzoxazine ring form, it has good mobility and low viscosity, make this resin better than traditional benzoxazine resinoid temperature tolerance and flame retardant resistance, better than traditional O-phthalic nitrile resin processibility.Described itrile group resinous polymer is formed by described itrile group resin polymerization, has the characteristics of machining at low temperature, middle temperature moulding, applied at elevated temperature, can be used for the fields such as coating, caking agent, electronic package material, Aeronautics and Astronautics, boats and ships and polymer matrix composites.
Raw materials used by regulating (the neighbours' benzene dicarbonitrile monomer and the n nonylphenol type phthalonitrile monomer that contain the benzoxazine ring) and formula, can obtain and possess the mobility that the benzoxazine resinoid is good, low viscosity and viscosity are adjustable, the serial low viscosity itrile group resin interworking monomer of the characteristics such as low-temperature curing.
In addition, by serial low viscosity itrile group resin interworking Unit heating polymerization gained series low viscosity itrile group resinous polymer, contain Polybenzoxazine structure and π-pi-conjugated phthalocyanine ring structure and the triazine ring structure of nitrogenous Mannich bridge, thereby give the thermal stability that material is higher.
The accompanying drawing explanation
Fig. 1 is the structural formula that contains neighbours' benzene dicarbonitrile monomer of benzoxazine ring provided by the invention.
Fig. 2 is the structural formula of n nonylphenol type phthalonitrile monomer provided by the invention.
Fig. 3 is three kinds of structures that comprise in low viscosity itrile group resinous polymer provided by the invention, and wherein (a) is the Polybenzoxazine structural formula of nitrogenous Mannich bridge construction, (b) is the structural formula of triazine ring, is (c) structural formula of phthalocyanine ring.
Embodiment
Below the present invention will be further described for the description by embodiment, but this is not limitation of the present invention, those skilled in the art, according to basic thought of the present invention, can make various modification or modification, only otherwise break away from basic thought of the present invention, all within the scope of the present invention.
Embodiment mono-
(1) preparation of low viscosity itrile group resin monomer:
1g n nonylphenol type phthalonitrile monomer is added in reaction vessel, be heated to 60 ℃, then the neighbours' benzene dicarbonitrile monomer that adds 9g to contain the benzoxazine ring stirred 30 minutes; Then be cooled to room temperature.
Under the low viscosity itrile group resin monomer viscosity at ambient temperature made thus, be 20 Pa.s, curing summit temperature is 223 ℃.
(2) preparation of low viscosity itrile group resinous polymer:
The low viscosity itrile group resin monomer prepared previously is heated to reaction 1-5 hour under 100 ~ 180 ℃, then, 240 ℃ of lower thermal treatments 3 ~ 5 hours, obtains the itrile group resinous polymer.
This itrile group resinous polymer 1010 cm
-1(phthalocyanine ring); 1360 cm
-1With 1520 cm
-1(triazine ring); 1246,1208 cm
-1(Ar-O-Ar); 832,782,729 cm
-1(phenyl ring) locates all to have occurred charateristic avsorption band.240 ℃ of low viscosity itrile group resinous polymers prepared according to the method were processed after 3 hours, and the temperature while decomposing 5% is 455 ℃; Carbon yield under the nitrogen atmosphere of 800 ℃ is 70%.
Embodiment bis-
(2) preparation of low viscosity itrile group resin monomer:
3g n nonylphenol type phthalonitrile monomer is added in reaction vessel, be heated to 60 ℃, then the neighbours' benzene dicarbonitrile monomer that adds 7g to contain the benzoxazine ring stirred 30 minutes; Then be cooled to room temperature.
Under the low viscosity itrile group resin monomer viscosity at ambient temperature made thus, be 10 Pa.s, curing summit temperature is 228 ℃.
(2) preparation of low viscosity itrile group resinous polymer:
The low viscosity itrile group resin monomer prepared previously is heated to reaction 1-5 hour under 100 ~ 180 ℃, then, 240 ℃ of lower thermal treatments 3 ~ 5 hours, obtains low viscosity itrile group resinous polymer.
This low viscosity itrile group resinous polymer 1010 cm
-1(phthalocyanine ring); 1360 cm
-1With 1520 cm
-1(triazine ring); 1246,1208 cm
-1(Ar-O-Ar); 832,782,729 cm
-1(phenyl ring) locates all to have occurred charateristic avsorption band.240 ℃ of low viscosity itrile group resinous polymers prepared according to the method were processed after 3 hours, and the temperature while decomposing 5% is 420 ℃; Carbon yield under the nitrogen atmosphere of 800 ℃ is 68%.
By above-mentioned embodiment, can be found out: low viscosity itrile group resin monomer provided by the invention and polymkeric substance have low viscosity, wider processing temperature window, and on the DSC spectrogram, curing exothermic peak appears at 220 ~ 240 ℃.The temperature 410 of decomposition 5% under the nitrogen atmosphere of 800 ℃ ~-470 ℃; The thermolysis carbon yield surpasses 60%.Thereby low viscosity itrile group resin monomer provided by the invention and polymkeric substance have significantly improved its processibility.The low viscosity itrile group resinous polymer obtained has by this method greatly improved traditional narrow shortcoming of bi-phthalonitrile process window, and thermotolerance is also kept simultaneously, can be for high-tech areas such as aerospace, naval vessels.
Claims (4)
1. low viscosity itrile group resin monomer, it is characterized in that: be to be formed by a kind of neighbours' phthalonitrile resin monomer and a kind of n nonylphenol type phthalonitrile monomer interworking that contains the benzoxazine ring, it contains neighbours' phthalonitrile resin monomer of benzoxazine ring and the structural formula of n nonylphenol type phthalonitrile monomer is respectively:
With
.
2. the preparation method of a low viscosity itrile group resin monomer as claimed in claim 1 is characterized in that: comprise the following steps:
N nonylphenol type phthalonitrile monomer is added in reaction vessel, be heated to 60 ℃, then add the neighbours' benzene dicarbonitrile monomer that contains the benzoxazine ring to stir 30 minutes; Then be cooled to room temperature;
Wherein, n nonylphenol type phthalonitrile monomer content is between 1% ~ 30%.
3. low viscosity itrile group resinous polymer is characterized in that: be a kind of polymkeric substance of low viscosity itrile group resin monomer, its structure is the reticulated structure of the Polybenzoxazine, π-pi-conjugated phthalocyanine ring and the triazine ring that comprise nitrogenous Mannich bridge construction;
The Polybenzoxazine structural formula of described nitrogenous Mannich bridge construction is:
The structural formula of described triazine ring is:
The structural formula of described phthalocyanine ring is:
Wherein, described low viscosity itrile group resin monomer, be to be obtained by a kind of neighbours' phthalonitrile resin monomer and n nonylphenol type phthalonitrile monomer interworking that contains the benzoxazine ring, its neighbours' phthalonitrile resin monomer and n nonylphenol type phthalonitrile monomer structural formula that contains the benzoxazine ring is respectively:
4. the preparation method of a low viscosity itrile group resinous polymer as claimed in claim 3, it is characterized in that: described low viscosity itrile group resin monomer is heated to reaction 1-5 hour under 100 ~ 180 ℃, 240 ℃ of lower thermal treatments 3 ~ 5 hours, obtain low viscosity itrile group resinous polymer again.
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Cited By (8)
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| CN103709746A (en) * | 2013-12-19 | 2014-04-09 | 成都德美精英化工有限公司 | Nitrile resin composite material and preparation method thereof |
| CN103739519A (en) * | 2013-12-10 | 2014-04-23 | 电子科技大学 | Low-viscosity nitrile resin monomer, copolymer, cured material and preparation method thereof |
| CN103756312A (en) * | 2013-12-19 | 2014-04-30 | 成都德美精英化工有限公司 | Low-density high temperature resistant cyano resin composite material and preparation method thereof |
| KR20160063685A (en) * | 2014-11-27 | 2016-06-07 | 주식회사 엘지화학 | Phthalonitrile compound |
| KR20160064714A (en) * | 2014-11-28 | 2016-06-08 | 주식회사 엘지화학 | Phthalonitrile compound |
| WO2017105890A1 (en) | 2015-12-15 | 2017-06-22 | 3M Innovative Properties Company | Benzoxazine and phthalonitrile resin blends |
| WO2018084465A1 (en) * | 2016-11-04 | 2018-05-11 | 주식회사 엘지화학 | Polymerizable composition |
| CN114478971A (en) * | 2022-03-09 | 2022-05-13 | 电子科技大学 | Nitrile-group functionalized benzoxazine resin and preparation method of polymer and composite material thereof |
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| CN103739519A (en) * | 2013-12-10 | 2014-04-23 | 电子科技大学 | Low-viscosity nitrile resin monomer, copolymer, cured material and preparation method thereof |
| CN103709746A (en) * | 2013-12-19 | 2014-04-09 | 成都德美精英化工有限公司 | Nitrile resin composite material and preparation method thereof |
| CN103756312A (en) * | 2013-12-19 | 2014-04-30 | 成都德美精英化工有限公司 | Low-density high temperature resistant cyano resin composite material and preparation method thereof |
| CN103709746B (en) * | 2013-12-19 | 2016-04-20 | 成都德美精英化工有限公司 | A kind of Nitrile resin composite material and preparation method thereof |
| CN103756312B (en) * | 2013-12-19 | 2017-02-01 | 成都德美精英化工有限公司 | Low-density high temperature resistant cyano resin composite material and preparation method thereof |
| KR20160063685A (en) * | 2014-11-27 | 2016-06-07 | 주식회사 엘지화학 | Phthalonitrile compound |
| KR101985800B1 (en) | 2014-11-27 | 2019-06-04 | 주식회사 엘지화학 | Phthalonitrile compound |
| KR101901128B1 (en) | 2014-11-28 | 2018-09-27 | 주식회사 엘지화학 | Phthalonitrile compound |
| KR20160064714A (en) * | 2014-11-28 | 2016-06-08 | 주식회사 엘지화학 | Phthalonitrile compound |
| CN108431134A (en) * | 2015-12-15 | 2018-08-21 | 3M创新有限公司 | Benzoxazine and phthalonitrile resin blend |
| WO2017105890A1 (en) | 2015-12-15 | 2017-06-22 | 3M Innovative Properties Company | Benzoxazine and phthalonitrile resin blends |
| JP2018537574A (en) * | 2015-12-15 | 2018-12-20 | スリーエム イノベイティブ プロパティズ カンパニー | Benzoxazine and phthalonitrile resin blends |
| EP3390539A4 (en) * | 2015-12-15 | 2019-09-04 | 3M Innovative Properties Company | Benzoxazine and phthalonitrile resin blends |
| US10556991B2 (en) | 2015-12-15 | 2020-02-11 | 3M Innovative Properties Company | Benzoxazine and phthalonitrile resin blends |
| CN108431134B (en) * | 2015-12-15 | 2021-03-09 | 3M创新有限公司 | Benzoxazine and phthalonitrile resin blends |
| WO2018084465A1 (en) * | 2016-11-04 | 2018-05-11 | 주식회사 엘지화학 | Polymerizable composition |
| CN109923149A (en) * | 2016-11-04 | 2019-06-21 | 株式会社Lg化学 | Polymerisable compound |
| US11091592B2 (en) | 2016-11-04 | 2021-08-17 | Lg Chem, Ltd. | Polymerizable composition |
| CN109923149B (en) * | 2016-11-04 | 2021-08-17 | 株式会社Lg化学 | Polymerizable composition |
| CN114478971A (en) * | 2022-03-09 | 2022-05-13 | 电子科技大学 | Nitrile-group functionalized benzoxazine resin and preparation method of polymer and composite material thereof |
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Application publication date: 20131127 |