Propargyl ether modified silicon-containing aryne resin

A technology of propargyl ether and siliaryne, which is used in the field of modified siliaryne resins, can solve the problems of high brittleness, unfavorable resin processing, poor mechanical properties of composite materials, etc., and achieves low cost and excellent processing performance. Effect

Inactive Publication Date: 2010-09-22
EAST CHINA UNIV OF SCI & TECH
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Problems solved by technology

Such as: Luneva et al. have prepared silicon-containing alkyne resins (L.K.Luneva, A.M.Sladkov, and V.V.Korshak, Vysokomolekulyarnye Soedineniya, SeriyaA, 1967, 9(4): 910-14.), its heat resistance can reach 450 ° C ~ 550 ° C; Itoh et al. used magnesium oxide as a catalyst to synthesize a silicon hydrogen aryne resin - MSP resin (a.M.Itoh, M.Mitsuzuka, K.Iwata, K.Inoue.Macromolecules, 1994, 27: 7917-7917.b.M.Itoh, K.Inoue, et al., Journal of Materials Science, 2002, 37: 3795.), has excellent thermal properties after curing, but due to the Brittleness and shrinkage during curing lead to poor mechanical properties of the composite material; Ohshita et al. successfully synthesized a series of silicon-containing polymers whose side groups are aryne groups by metal lithium method (J.Ohshita, A.Shinpo, A.Kunai.Macromolecules, 1999,32:5998-6002), this type of polymer has excellent thermal stability, and the weight loss rate at 1000°C in nitrogen is 8-10%; Buvat et al synthesized phenylacetylene-terminated containing Silahydroaryne resin (called BLJ resin) (Pierrick Buvat., et al., SAMPESymp., 2000, 46: 134-144), the cured resin does not show glass transition below 450 ° C, and decomposes at 1000 ° C under argon The residual rate is 80%; Huang Farong et al. have also prepared silicon-containing aryne resins of various structures (CN 1709928)
[0004] To sum up, although the existing silicon-containing aryne resins have their own characteristics, their common defects are: the brittleness of the silicon-containing aryne resin after curing is too high, and the adhesion to the fiber is not ideal.
However, the silicon-containing aryne resin modified by arylethynyl benzoxazine compounds has a relatively high viscosity, which is not conducive to the processing of the resin.

Method used

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preparation example Construction

[0038] (2) Preparation of silicon-containing aryne resin:

[0039] The main method for preparing the silicon-containing aryne resin of the present invention is to use Grignard reagents to react with halosilanes. The specific process is as follows: first, magnesium and halogenated alkanes are used as raw materials, and anhydrous ether reagents are used as solvents to prepare Aliphatic hydrocarbon Grignard reagent; secondly, with ethynyl arene and diethynyl arene as reactant (the preparation method is referring to CN 1680229 and CN 1680228), ether reagent is used as solvent to form alkyne lattice under the action of aliphatic Grignard reagent The third, alkyne Grignard reagent and dihalosilane (said dihalosilane is selected from one, two or more than two mixtures of compounds shown in formula IV) reaction to prepare silicon-containing aryne resin.

[0040]Wherein: the ether solvent used can be ether, propyl ether, butyl ether, dioxane, tetrahydrofuran (THF) or crown ether. The...

Embodiment 1

[0052] 1. Synthesis of bisphenol A dipropargyl ether (DPBPA)

[0053] Add 45.60 g (0.20 mol) of bisphenol A, 19.20 g (0.48 mol) of sodium hydroxide, and 0.80 g of benzyltriethylammonium chloride into a 250 ml four-necked round-bottomed flask equipped with a stirring device, a nitrogen inlet tube, and a condenser tube. g and 120ml of deionized water. The temperature of the reaction material was raised to 70°C under stirring, and 59.50 g (0.50 mol) of propyne bromide was added dropwise within 2 hours. After the reaction, the product was washed with water until neutral, and then recrystallized twice with methanol to obtain a light yellow crystal product with a yield of 75%, m.p.79-80°C.

[0054] 1 H-NMR (CDCl 3 , TMS) δ: 1.62 (s, 6H, -CH 3 ), 2.50(tr, 2H, ≡CH), 4.65(d, 4H, -CH 2 ), 6.86 (m, 4H, -O-Ar-H), 7.15 (m, 4H, -C-Ar-H); FT-IR (KBr): 3286cm -1 (≡C-H), 2110cm -1 (C≡C); elemental analysis (C 21 h 20 o 2 ) [found (calculated)] (%): C 82.19 (82.87), H 6.63 (6.62), O 1...

Embodiment 2

[0062] Resin preparation of bisphenol A dipropargyl ether modified dimethyl silicon-containing aryne resin (DPBPA-DMPSA-50)

[0063] Bisphenol A dipropargyl ether (prepared by the method described in Example 1) 5.0g, dimethyl type silicon-containing aryne resin (prepared by the method described in Example 1) 5.0g, Put it into a reactor equipped with a stirrer, a thermometer and a reflux condenser, pass an inert gas, slowly raise the temperature to 150°C, and start stirring. After the reactants are completely melted and homogeneous, continue stirring for 2 hours to obtain a reddish-brown solid resin. In the range of 75-210°C, the viscosity of the resin is less than 0.4Pa.s, and under the condition of higher than 210°C, the viscosity of the resin rises rapidly and begins to gel.

[0064] The resin was cured at 150°C for 2.0h, 170°C for 2.0h, 210°C for 2.0, and then post-treated at 250°C for 4.0h. The glass transition temperature of the cured product was 487°C. Under nitrogen at...

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Abstract

The invention relates to a propargyl ether compound modified silicon-containing aryne resin, which is prepared by stirring 5-80 weight parts of propargyl ether compound and 50-95 weight parts of silicon-containing aryne resin (of which the degree of polymerization is 2-6) to react at the temperature of 90-180 DEG C for 0.5-4.0 hours in the presence of inert gas. The modified silicon-containing arylacetylene resin of the invention has the advantages that the combined resin structure can be properly controlled by designing (molecular structure); resin has favourable processability, low softening point and low molten resin viscosity, can be dissolved in various common solvents and is convenient to use; the resin and the fiber have favourable caking property; and resin can carry out cure reaction under the action of heat and radiation, even light to form high-degree crosslinking polymer, and no micromolecules are discharged when being solidified.

Description

technical field [0001] The invention relates to a modified silicon-containing aryne resin, in particular to a silicon-containing aryne resin modified by a propargyl ether compound. Background technique [0002] Silicon-containing aryne resin is a new type of aryne-based thermosetting resin. In addition to the characteristics of aryne-based resins, it also has excellent electrical properties and high-temperature ceramic properties (that is, in this type of polymer at high temperature Can form a stable ceramic structure, such as SiC or / and SiO2, etc.). [0003] So far, silicon-containing aryne resins with various structures have been reported. Such as: Luneva et al. have prepared silicon-containing alkyne resins (L.K.Luneva, A.M.Sladkov, and V.V.Korshak, Vysokomolekulyarnye Soedineniya, SeriyaA, 1967, 9(4): 910-14.), its heat resistance can reach 450 ° C ~ 550 ° C; Itoh et al. used magnesium oxide as a catalyst to synthesize a silicon hydrogen aryne resin - MSP resin (a.M.It...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F283/00C08G77/52
Inventor 黄发荣杜磊黄健翔张玲玲张健周燕万里强齐会民扈艳红
Owner EAST CHINA UNIV OF SCI & TECH
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