CN105315469A - Silicon-nitrile-based hybrid resin and synthesizing method thereof - Google Patents
Silicon-nitrile-based hybrid resin and synthesizing method thereof Download PDFInfo
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- CN105315469A CN105315469A CN201510642188.4A CN201510642188A CN105315469A CN 105315469 A CN105315469 A CN 105315469A CN 201510642188 A CN201510642188 A CN 201510642188A CN 105315469 A CN105315469 A CN 105315469A
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Abstract
The invention discloses silicon-nitrile-based hybrid resin and a synthesizing method thereof. The molecular structural formula of the silicon-nitrile-based hybrid resin is shown as a formula (I). The synthesizing method comprises the following steps that reacting is performed by taking sulfydryl propyl methylsiloxane and 4-nitrophthalonitrile as main raw materials, and then the silicon-nitrile-based hybrid resin is obtained. The silicon-nitrile-based hybrid resin has the advantages of being low in melting point, capable of resisting high temperature, not prone to hydrolysis, excellent in heat stability and curing performance and the like; the synthesizing method is simple and easy to control, lower in reaction temperature, shorter in time and suitable for industrialized production.
Description
Technical field
The invention belongs to organic synthesis technical field of polymer materials, relate to a kind of silica-based itrile group hybrid resin and synthetic method thereof, particularly relate to the resistant to elevated temperatures silica-based itrile group hybrid resin of a kind of low melting point and synthetic method thereof.
Background technology
The rapid advances of aerospace industry, has higher requirement to the high temperature resistant of material and antioxidant property, and silicon-containing polymer, owing to having excellent fire-resistant oxidation resistant performance, thus meets this requirement well.Simultaneously, o-phthalonitrile resin is a kind of novel fire resistant thermosetting resin, with its cured article, there is good thermostability and mechanical property, and the thermo-oxidative stability of excellence, flame retardant resistance and good moisture resistivity, have in fields such as aerospace, naval vessel, microelectronics and machinofacture and apply more and more widely.
Therefore, numerous investigator attempt study a kind of novel resin can in conjunction with both advantage, the people such as such as Zhou Quan have synthesized several different silicon-based hybrid resin linking phenylacetylene with Si-N key, and have suitable viscosity under this several resin normal temperature, the mechanical property of its polymkeric substance is also excellent simultaneously.But this kind of monomer has a unavoidable shortcoming, the facile hydrolysis because Si-N key exists, thus must store by strict water-less environment, and needs the low temperature environment of liquid nitrogen, cause application to have numerous difficulty.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, provides a kind of low melting point, high temperature resistant, not facile hydrolysis and have silica-based itrile group hybrid resin and the synthetic method thereof of excellent thermostability and curing performance.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A kind of silica-based itrile group hybrid resin, the molecular structural formula of described silica-based itrile group hybrid resin is lower formula I:
The number-average molecular weight of described silica-based itrile group hybrid resin is 7000 ~ 13000.In this molecular weight ranges, m: n generally in the scope of 7 ~ 11.
As a total inventive concept, the present invention also provides a kind of synthetic method of silica-based itrile group hybrid resin, comprises the following steps:
React for main raw material with mercaptopropyi methylsiloxane and 4-nitrophthalonitrile, obtain silica-based itrile group hybrid resin.
The synthetic method of above-mentioned silica-based itrile group hybrid resin, preferably, described synthetic method specifically comprises the following steps:
(1) under nitrogen protection, mercaptopropyi methylsiloxane and acid binding agent are dissolved in solvent, obtain the solution of silicone-containing sulfydryl salt;
(2) joined by 4-nitrophthalonitrile in the solution of the silicone-containing sulfydryl salt that described step (1) obtains and react, products therefrom solution, through aftertreatment, obtains silica-based itrile group hybrid resin.
The synthetic method of above-mentioned silica-based itrile group hybrid resin, preferably, the ratio of described mercaptopropyi methylsiloxane, acid binding agent, solvent and 4-nitrophthalonitrile is: 0.0075mol ~ 0.01mol: 0.01125mol ~ 0.015mol: 20ml ~ 30ml: 0.0075mol ~ 0.01mol.
The synthetic method of above-mentioned silica-based itrile group hybrid resin, preferably, in described step (1), the number-average molecular weight of described mercaptopropyi methylsiloxane is 4000 ~ 7000, and kinematic viscosity is 75cSt ~ 150cSt.
The synthetic method of above-mentioned silica-based itrile group hybrid resin, preferably, in described step (1), described acid binding agent comprise in Anhydrous potassium carbonate, anhydrous sodium carbonate, sodium bicarbonate, potassium hydroxide, sodium hydroxide, pyridine, imidazoles, triethylamine and Tetramethyl Ethylene Diamine one or more.
The synthetic method of above-mentioned silica-based itrile group hybrid resin, preferably, in described step (1), described solvent comprise in toluene, DMF, methyl-sulphoxide, Isosorbide-5-Nitrae-dioxane and pyridine one or more.
The synthetic method of above-mentioned silica-based itrile group hybrid resin, preferably, in described step (1), adopt the mode of stirring at normal temperature to dissolve, the time of described stirring at normal temperature is 1h ~ 4h; In described step (2), described temperature of reaction is normal temperature, Keep agitation in reaction process, and described churning time is 12h ~ 24h.
The synthetic method of above-mentioned silica-based itrile group hybrid resin, preferably, in described step (2), the process of described aftertreatment is: add water in products therefrom solution, stirs, and adopts extraction agent extraction, then revolve and steam to remove extraction agent, obtain silica-based itrile group hybrid resin.
The synthetic method of above-mentioned silica-based itrile group hybrid resin, preferably, described extraction agent comprises toluene, methylene dichloride or ethyl acetate.
The synthetic route of silica-based itrile group hybrid resin of the present invention is as follows:
The present invention, by improving molecular structure, polysiloxane backbone is introduced the phthalonitrile side chain of Heat stability is good, mechanical property excellence, thus improves thermostability further, simultaneously can with the suitable advantage of viscosity under low melting point, normal temperature.
Compared with prior art, the invention has the advantages that:
(1) silica-based itrile group hybrid resin of the present invention, be a kind of with polysiloxane (Si-O-Si) for main chain, take phthalonitrile as the new polymers of side chain, not only effectively combine high temperature resistant, the advantage such as mechanical property is excellent of silica-based and itrile group, and owing to there is not Si-N key, the hydrolysis problem that effectively to avoid with silicon nitrogen be main chain.
(2) silica-based itrile group hybrid resin of the present invention, has the advantage that viscosity under low melting point, normal temperature is suitable simultaneously, is applicable to that liquid phase is shaping waits novel low-cost technique, has good processing performance.
(3) silica-based itrile group hybrid resin of the present invention, heated polymerizable resulting polymers contains grips phthalocyanine ring structure and triazine ring structure altogether, can give the thermal stability that material is high.
(4) synthetic method of silica-based itrile group hybrid resin of the present invention, by improving molecular structure, polysiloxane backbone is introduced the phthalonitrile side chain of Heat stability is good, mechanical property excellence, synthesized silica-based itrile group hybrid resin has the thermostability higher compared with phthalonitrile, simultaneously with the advantage that viscosity under low melting point, normal temperature is suitable.And this synthetic method is simple and easy to control, temperature of reaction is lower, the time is shorter, is suitable for suitability for industrialized production.
To sum up, silica-based itrile group hybrid resin provided by the invention has low fusing point, suitable viscosity, good processing performance, and better resistance to elevated temperatures.Synthetic method of the present invention is simply effective, and reaction process is simply controlled, can be widely used in the fields such as coating, electronic package material, aerospace, microelectronics, machinofacture, boats and ships and polymer matrix composites, have wide market outlook.
Accompanying drawing explanation
Fig. 1 is the silica-based itrile group hybrid resin close shot photo at normal temperatures of the embodiment of the present invention 1.
Fig. 2 is the hydrogen nuclear magnetic spectrogram of the silica-based itrile group hybrid resin of the embodiment of the present invention 1.
Embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
The material adopted in following examples and instrument are commercially available.
Embodiment 1:
A kind of silica-based itrile group hybrid resin of the present invention, molecular structural formula is lower formula I:
The number-average molecular weight of this silica-based itrile group hybrid resin is 7000 ~ 13000.
A synthetic method for the silica-based itrile group hybrid resin of above-mentioned the present embodiment, comprises the following steps:
(1) under nitrogen protection; by the mercaptopropyi methylsiloxane of 0.0075mol, (number-average molecular weight is 4000-7000; kinematic viscosity is 75cSt ~ 150cSt); the Anhydrous potassium carbonate mixed dissolution of 0.01125mol is in 20ml methyl-sulphoxide DMSO (solvent); under normal temperature, (35 DEG C) stir 1 hour, obtain the solution of silicone-containing sulfydryl sylvite.
(2) joined by the 4-nitrophthalonitrile of 0.0075mol in the solution of above-mentioned silicone-containing sulfydryl sylvite, under normal temperature, (35 DEG C) stir 24 hours, obtain reaction mixture.
(3) stop stirring, in above-mentioned reaction mixture, add 100ml pure water, stir, use 20ml extraction into ethyl acetate, repeatedly extract 5 times, merge the extraction liquid of 5 times, revolving and steam removing extraction agent, is the silica-based itrile group hybrid resin of viscous state under namely obtaining normal temperature, as shown in Figure 1.
Adopt nuclear-magnetism to carry out Structural Identification to silica-based itrile group hybrid resin prepared by above-mentioned the present embodiment, as shown in Figure 2, proton shift value is as follows:
1hNMR (400MHz, cdcl
3) δ 7.60 (d, J=8.3Hz, 1.08H), 7.49 (s, 0.99H), 7.45 (dd, J=8.4,1.8Hz, 0.98H), 2.97 (dd, J=13.6,6.4Hz, 2.25H), 2.09 (s, 1H), 1.69 (dd, J=15.2,7.6Hz, 2.34H), 0.78 – 0.52 (m, 2.41H), 0.14 –-0.03 (m, 3.26H).Each H-shift value marks in the drawings, all coincide with target compound.Detect through GPC, this target compound number-average molecular weight is 7000-13000.
Embodiment 2:
A kind of silica-based itrile group hybrid resin of the present invention is identical with embodiment 1.
A synthetic method for the silica-based itrile group hybrid resin of the present embodiment, step is substantially the same manner as Example 1, and difference is only: in step (1), the solvent of employing is DMF DMF, and churning time is 2 hours; In step (2), churning time is 16 hours.
Embodiment 3:
A kind of silica-based itrile group hybrid resin of the present invention is identical with embodiment 1.
A synthetic method for the silica-based itrile group hybrid resin of the present embodiment, step is substantially the same manner as Example 1, and difference is only: in step (1), the solvent of employing is Isosorbide-5-Nitrae-dioxane, and churning time is 3 hours; In step (2), churning time is 22 hours.
Embodiment 4:
A kind of silica-based itrile group hybrid resin of the present invention is identical with embodiment 1.
A synthetic method for the silica-based itrile group hybrid resin of the present embodiment, step is substantially the same manner as Example 1, and difference is only: in step (1), the acid binding agent of employing is anhydrous sodium carbonate, obtains the solution of silicone-containing sulfydryl sodium salt.
Embodiment 5:
A kind of silica-based itrile group hybrid resin of the present invention is identical with embodiment 1.
A synthetic method for the silica-based itrile group hybrid resin of the present embodiment, step is substantially the same manner as Example 1, and difference is only: in step (1), the acid binding agent of employing is triethylamine, obtains the solution of silicone-containing sulfydryl salt.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is also not only confined to above-described embodiment.All technical schemes belonged under thinking of the present invention all belong to protection scope of the present invention.It is noted that for those skilled in the art, improvements and modifications under the premise without departing from the principles of the invention, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a silica-based itrile group hybrid resin, is characterized in that, the molecular structural formula of described silica-based itrile group hybrid resin is lower formula I:
The number-average molecular weight of described silica-based itrile group hybrid resin is 7000 ~ 13000.
2. a synthetic method for silica-based itrile group hybrid resin, comprises the following steps:
React for main raw material with mercaptopropyi methylsiloxane and 4-nitrophthalonitrile, obtain silica-based itrile group hybrid resin.
3. the synthetic method of silica-based itrile group hybrid resin according to claim 2, it is characterized in that, described synthetic method specifically comprises the following steps:
(1) under nitrogen protection, mercaptopropyi methylsiloxane and acid binding agent are dissolved in solvent, obtain the solution of silicone-containing sulfydryl salt;
(2) joined by 4-nitrophthalonitrile in the solution of the silicone-containing sulfydryl salt that described step (1) obtains and react, products therefrom solution, through aftertreatment, obtains silica-based itrile group hybrid resin.
4. the synthetic method of silica-based itrile group hybrid resin according to claim 3, it is characterized in that, the ratio of described mercaptopropyi methylsiloxane, acid binding agent, solvent and 4-nitrophthalonitrile is: 0.0075mol ~ 0.01mol: 0.01125mol ~ 0.015mol: 20ml ~ 30ml: 0.0075mol ~ 0.01mol.
5. the synthetic method of silica-based itrile group hybrid resin according to claim 3, is characterized in that, in described step (1), the number-average molecular weight of described mercaptopropyi methylsiloxane is 4000 ~ 7000, and kinematic viscosity is 75cSt ~ 150cSt.
6. the synthetic method of silica-based itrile group hybrid resin according to claim 3, it is characterized in that, in described step (1), described acid binding agent comprise in Anhydrous potassium carbonate, anhydrous sodium carbonate, sodium bicarbonate, potassium hydroxide, sodium hydroxide, pyridine, imidazoles, triethylamine and Tetramethyl Ethylene Diamine one or more.
7. the synthetic method of silica-based itrile group hybrid resin according to claim 3, it is characterized in that, in described step (1), described solvent comprises toluene, N, one or more in dinethylformamide, methyl-sulphoxide, Isosorbide-5-Nitrae-dioxane and pyridine.
8. the synthetic method of the silica-based itrile group hybrid resin according to any one of claim 3 ~ 7, is characterized in that, in described step (1), adopt the mode of stirring at normal temperature to dissolve, the time of described stirring at normal temperature is 1h ~ 4h; In described step (2), described temperature of reaction is normal temperature, Keep agitation in reaction process, and described churning time is 12h ~ 24h.
9. the synthetic method of the silica-based itrile group hybrid resin according to any one of claim 3 ~ 7, it is characterized in that, in described step (2), the process of described aftertreatment is: add water in products therefrom solution, stir, employing extraction agent extracts, and then revolves and steams to remove extraction agent, obtain silica-based itrile group hybrid resin.
10. the synthetic method of silica-based itrile group hybrid resin according to claim 9, it is characterized in that, described extraction agent comprises toluene, methylene dichloride or ethyl acetate.
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| CN108442122A (en) * | 2018-04-26 | 2018-08-24 | 湖南师范大学 | Sizing agent for preparing quartz fiber/nitrile resin composite material |
| CN108484917A (en) * | 2018-04-28 | 2018-09-04 | 哈尔滨玻璃钢研究院有限公司 | A kind of preparation method of the bi-phthalonitrile polymer of the structures of POSS containing silsesquioxane |
| CN112778525A (en) * | 2020-12-31 | 2021-05-11 | 中硅艾德(厦门)新材料科技有限公司 | Phthalonitrile monomer liquid at normal temperature and synthesis method thereof |
| WO2022121328A1 (en) * | 2020-12-09 | 2022-06-16 | 山东大学 | Hydrophilic silicone rubber serving as medical catheter, preparation method therefor and application thereof |
| CN115141373A (en) * | 2022-08-04 | 2022-10-04 | 齐鲁工业大学 | Preparation method of epoxy phthalonitrile/polysiloxane copolymer resin |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108442122A (en) * | 2018-04-26 | 2018-08-24 | 湖南师范大学 | Sizing agent for preparing quartz fiber/nitrile resin composite material |
| CN108484917A (en) * | 2018-04-28 | 2018-09-04 | 哈尔滨玻璃钢研究院有限公司 | A kind of preparation method of the bi-phthalonitrile polymer of the structures of POSS containing silsesquioxane |
| WO2022121328A1 (en) * | 2020-12-09 | 2022-06-16 | 山东大学 | Hydrophilic silicone rubber serving as medical catheter, preparation method therefor and application thereof |
| CN112778525A (en) * | 2020-12-31 | 2021-05-11 | 中硅艾德(厦门)新材料科技有限公司 | Phthalonitrile monomer liquid at normal temperature and synthesis method thereof |
| CN115141373A (en) * | 2022-08-04 | 2022-10-04 | 齐鲁工业大学 | Preparation method of epoxy phthalonitrile/polysiloxane copolymer resin |
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