CN103172795B - Silicon containing hybrid resin and preparation method thereof - Google Patents

Abstract

The invention discloses a novel silicon containing hybrid resin and a preparation method of the hybrid resin. The silicon containing hybrid resin is prepared by the method comprising the following steps of: mixing and stirring an organosilicon polymer, N-vinyl pyrrolidone and a curing agent to obtain a uniform mixture, and heating, curing and molding the obtained uniform mixture to obtain a gel solid, namely the silicon containing hybrid resin, wherein the organosilicon polymer is the polyborosilazane (PSNB) as shown in formula (I), and n is 2-100. The hybrid resin prepared by the method disclosed by the invention is pretty high in temperature resistance and good in light transmittance, the temperature resistance can be as high as more than 400 DEG C, and the light transmittance is more than 80% (600nm).

Description

A kind of silicon-containing hybrid resin and preparation method thereof

technical field

The invention relates to a silicon-containing hybrid resin and a preparation method thereof.

Background technique

Organic-inorganic hybrid materials have shown broad application prospects in the development of new functional materials, and became a hot research field in chemistry and materials science in the late 1990s. Organic-inorganic hybrid material is a uniformly dispersed multi-phase material, which is characterized by large interface area and strong interfacial interaction between the organic phase and the inorganic phase. There is an essential difference.

There are many classification methods for organic-inorganic hybrid materials. According to the interface properties and material composition between the two phases, they can be divided into three categories: (I) inorganic embedded organic phase; (II) organic filled inorganic phase; (III) chemically bonded organic phase with the inorganic phase. Among the preparation methods of organic-inorganic hybrid materials, the most reported in the literature are: sol-gel method, physical blending method and in-situ polymerization method and so on. Among them, the sol-gel method is an earlier and more widely used method. This method has mild reaction conditions, room temperature or slightly higher than room temperature; good uniformity, chemical composition can be selectively doped, design precursors and synthesis The route makes the organic phase and the inorganic phase reach the level of "molecular composite". The physical blending method is easy to operate and simple in process. Similar to the blending modification of polymers, the blending of organic matter (polymers) and inorganic nanoparticles. The prepared hybrid material is simply blended, and the organic phase and the inorganic phase are connected to each other through weak bonds, such as van der Waals force, hydrogen bond or interionic force, and there is no chemical bond. The in-situ polymerization method is in-situ filling to make the nanoparticles uniformly dispersed in the monomer, and then in-situ polymerization under certain conditions. The filled particles of the hybrid material prepared by this method are evenly dispersed, the particles are not easy to agglomerate, and the size characteristics of the particles are better maintained.

In general, organic-inorganic hybrid materials have the characteristics of both organic polymers and inorganic materials, and exhibit superior performance in terms of optical transparency, adjustable refractive index, mechanical properties, and temperature resistance. Therefore, organic-inorganic hybrid materials have broad application prospects in the fields of coatings, thin films, nanocomposites, and organic ceramics.

Contents of the invention

The object of the present invention is to provide a novel silicon-containing hybrid resin and a preparation method thereof.

The present invention provides that the provided silicon-containing hybrid resin is prepared according to a method comprising the following steps: mixing and stirring the organosilicon polymer, N-vinylpyrrolidone and a curing agent to obtain a homogeneous mixture, and preparing the homogeneous mixture Carrying out heating and curing molding to obtain a gel solid, which is the silicon-containing hybrid resin;

Wherein, the organosilicon polymer is polyborosilazane (PSNB) represented by formula (I), n=2-100;

The structural formula of the N-vinylpyrrolidone (NVP) is shown in formula (II);

In the above method, the curing agent can be at least one of the free radical initiators that initiate vinyl group polymerization; specifically, it can be dicumyl peroxide (DCP), benzoyl peroxide (BPO) or azo Diisobutyronitrile (AIBN). The addition amount of the curing agent is 0-0.5% of the mass of the mixture, but not 0; further it can be 0.2-0.5%; specifically 0.2%, 0.3%, 0.4% or 0.5%.

In the above method, the addition amount of the organosilicon polymer and N-vinylpyrrolidone can have different ratios, so as to further improve and compare the temperature resistance and light transmittance of the hybrid resin.

In the above method, the amount of the silicone polymer added can be 0-100% (but not including 0%, 100%) of the mass of the mixture, and can further be 20-80% of the mass of the mixture, specifically 20% , 40%, 60%, 80%. The amount of N-vinylpyrrolidone added is 0-100% (but not including 0%, 100%) of the mass of the mixture, and can further be 20-80% of the mass of the mixture, specifically 20%, 40%, 60%, 80%.

In the above method, the curing molding procedure is: curing at 100°C for 4 hours, curing at 120°C for 2 hours, curing at 140°C for 2 hours, and curing at 180°C for 2 hours.

In the above method, the rate of heating the mixture to the curing and molding temperature is 0.5°C-2°C/min, specifically 0.5°C/min, 1°C/min or 2°C/min.

The silicon-containing hybrid resin prepared by the above method provided by the present invention has a thermal decomposition temperature above 400°C, specifically 410°C, 406°C, 408°C, 403°C, 415°C or 490°C; the light transmittance is 80°C %, specifically 80.8%, 93.7%, 92.5%, 91.8%, 89.2% or 87.1% (600nm).

Hybrid resin of the present invention and preparation method thereof have the following advantages:

(1) The prepared hybrid resin has the characteristics of high temperature resistance and good light transmittance, the temperature resistance can reach above 400°C, and the light transmittance is above 80% (600nm); Toxic, cheap, high boiling point, low melting point, high flash point, easy free radical polymerization of N-vinylpyrrolidone, the process is simple, safe and economical. The cost of hybrid resin is significantly lower than that of polyborosilazane resin.

Description of drawings

Fig. 1 is the appearance photograph of the transparent yellow cylindrical sample prepared in embodiment 2.

Fig. 2 is a picture of the light transmittance of the hybrid resin prepared in Examples 1-4.

Detailed ways

The present invention will be described below through specific examples, but the present invention is not limited thereto.

The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials and reagents used in the following examples can be obtained from commercial sources unless otherwise specified.

The polyborosilazane shown in the formula (I) used in the following examples of the present invention is prepared according to the method of the document [J.Mater.Sci.2011,46,5940], specifically as follows: methyl vinyl dichlorosilane , methylhydrogendichlorosilane, boron trichloride, and hexamethyldisilazane are ammonolytically polymerized under an ammonia atmosphere to obtain the polymer shown in formula (I); the polymerization reaction temperature can be 0-200°C; The molar ratio of methylvinyldichlorosilane, methylhydrogendichlorosilane, boron trichloride and hexamethyldisilazane is 1:1:1:6. The molecular weight of the obtained polyborosilazane is 470-2400 (ie n=2-100).

Embodiment 1, preparation of silicon-containing hybrid resin

With polyborosilazane 3g shown in formula (I) and N-vinylpyrrolidone 12g, and the curing agent dicumyl peroxide (DCP) of 30mg, its add-on is 0.2% of mixture quality, mix and stir, Pour into a steel mold, then raise the temperature to 100°C at a heating rate of 1°C/min and hold for 4 hours, then raise the temperature to 120°C at a heating rate of 0.5°C/min and hold for 2 hours, then heat at a heating rate of 0.5°C/min Raise to 140°C and hold for 2 hours, then raise the temperature to 180°C at a rate of 0.5°C/min and hold for 2 hours. After cooling down to room temperature, release the mold to obtain a transparent yellow cylindrical gel solid sample, which is the silicon-containing hybrid resin. Its thermal decomposition temperature is 406°C, and its light transmittance is 93.7%.

Embodiment 2, preparation of silicon-containing hybrid resin

With polyborosilazane 6g shown in formula (I) and N-vinylpyrrolidone 9g, and the curing agent dicumyl peroxide (DCP) of 30mg, its add-on is 0.2% of mixture quality, mix uniformly, pour Put it into a steel mold, then raise the temperature to 100°C at a heating rate of 1°C/min and hold it for 4 hours, then raise the temperature to 120°C at a heating rate of 0.5°C/min and hold it for 2 hours, then raise the temperature at a heating rate of 0.5°C/min Heat to 140°C and hold for 2 hours, then raise the temperature to 180°C at a rate of 0.5°C/min and hold for 2 hours. After cooling down to room temperature, release the mold to obtain a transparent yellow cylindrical gel solid sample, which is a silicon-containing hybrid resin. Its thermal decomposition temperature is 408°C, and its light transmittance is 92.5%.

Embodiment 3, preparation of silicon-containing hybrid resin

With polyborosilazane 9g shown in formula (I) and N-vinylpyrrolidone 6g, and the curing agent dicumyl peroxide (DCP) of 30mg, its add-on is 0.2% of mixture quality, mix uniformly, pour Put it into a steel mold, then raise the temperature to 100°C at a heating rate of 1°C/min and hold it for 4 hours, then raise the temperature to 120°C at a heating rate of 0.5°C/min and hold it for 2 hours, then raise the temperature at a heating rate of 0.5°C/min to 140°C and keep it warm for 2 hours, then raise it to 180°C at a rate of 0.5°C/min and hold it for 2 hours, and then release it from the mold after cooling down to room temperature to get a transparent yellow cylindrical gel solid sample, which is a new silicon-containing hybrid resin. The decomposition temperature is 403°C, and the light transmittance is 91.8%.

Embodiment 4, preparation of silicon-containing hybrid resin

With polyborosilazane 12g shown in formula (I) and N-vinylpyrrolidone 3g, and the curing agent dicumyl peroxide (DCP) of 30mg, its add-on is 0.2% of mixture quality, mix uniformly, pour Put it into a steel mold, then raise the temperature to 100°C at a heating rate of 1°C/min and hold it for 4 hours, then raise the temperature to 120°C at a heating rate of 0.5°C/min and hold it for 2 hours, then raise the temperature at a heating rate of 0.5°C/min Heat to 140°C and hold for 2 hours, then raise the temperature to 180°C at a rate of 0.5°C/min and hold for 2 hours. After cooling down to room temperature, release the mold to obtain a transparent yellow cylindrical gel solid sample, which is a silicon-containing hybrid resin. Its thermal decomposition temperature is 415°C, and its light transmittance is 89.2%.

Claims (5)

1. prepare a method for siliceous hybrid resin, comprise the steps: organosilicon polymer and NVP to mix with solidifying agent, obtain mixture, obtain gel solids by shaping for described mixture solidified, be described siliceous hybrid resin;

Wherein, described organosilicon polymer is the PVDF hollow fiber membrane shown in formula I, n=2 ~ 100;

Described solidifying agent is at least one in the radical initiator of initiation vinyl groups polymerization;

The add-on of described organosilicon polymer is the 20-80% of the quality of mixture; The add-on of described NVP is the 20-80% of the quality of mixture; The add-on of described solidifying agent is the 0.2-0.5% of described mixture quality;

The temperature of described curing molding is 20 DEG C-180 DEG C, and the time is 1h-20h.

2. method according to claim 1, is characterized in that: described solidifying agent is selected from following one: dicumyl peroxide, benzoyl peroxide and Diisopropyl azodicarboxylate.

3. method according to claim 1, is characterized in that: the temperature rise rate described mixture being heated to the temperature of described curing molding is 0.5 DEG C-2 DEG C/min.

4. the siliceous hybrid resin for preparing of method according to any one of claim 1-3.

5. siliceous hybrid resin according to claim 4, is characterized in that: the heat decomposition temperature of described resin is more than 400 DEG C; The transmittance at 600nm place is more than 80%.