CN104403129A - Double-component crosslinking agent, preparation method and applications thereof - Google Patents

Abstract

The invention discloses a two-component cross-linking agent and its preparation method and application; Silane compounds with azide groups: The two-component cross-linking agent of the present invention introduces the ring-forming reaction of azide-alkyne under heating conditions as a cross-linking method, and realizes the preparation of cross-linked polymer insulation at a lower temperature, without metal catalysts and by-products Layer material, the preparation process is simple, suitable for various polymer materials (polystyrene, polymethylmethacrylate and polyvinylphenol, etc.), the obtained material is a potential organic field effect transistor gate insulating layer material, It can be used in the solution method to prepare various OFETs devices, and the application prospect is very wide.

Description

Two-component crosslinking agent and its preparation method and use

technical field

The invention relates to a two-component crosslinking agent and its preparation method and application.

Background technique

Organic field-effect transistors (OFETs) are transistor devices with organic semiconductor materials as the active layer, and are one of the important organic semiconductor devices. Compared with non-field effect transistors, organic field effect transistors have many advantages: 1. They are mechanically flexible, compatible with plastic substrates, and can be used in foldable products; 2. The manufacturing process is simple and does not require high temperature and high vacuum and complex lithography technology; 3. The preparation process is simple and the cost is low; 4. The organic matter is easy to obtain, and the performance of the field effect transistor can be easily adjusted through the chemical modification of the organic molecule; 5. It can realize large-scale, large-scale scale bending etc. The characteristics that these inorganic devices do not have make them have potential application prospects in large-area, low-cost, and flexible organic electronics (such as driving circuits for flexible display devices, radio frequency identification tags, and sensors). (see literature: Klauk, H., Organicthin-film transistors, Chem.Soc.Rev., 2010,39, 2643-2666; Facchetti, A., π-Conjugated polymers for organic electronics and photovoltaic cell applications, Chem.Mater., 2011, 23, 733-758; Wang, C., Dong, H., Hu, W., Liu, Y., Zhu, D., Semiconductoringπ-conjugated systems in field-effect transistors: a material odyssey of organic electronics, Chem. Rev., 2012, 112, 2208-2267; Arias, A.C., MacKenzie, J.D., McCulloch, I., Rivnay, J., Salleo, A., Materials and applications for large area electronics: solution-based approaches, Chem. Rev. ,2010,110,3–24)

In an organic field effect transistor, the material of the insulating layer is an important component, mainly because the charge of the organic field effect transistor is mainly transmitted in the organic semiconductor layer (2-6 molecular layers) on the side adjacent to the insulating layer. The organic insulating layer materials currently used in the research of organic thin film transistors mainly include the following categories: polymethyl methacrylate, polyimide, polyvinyl phenol, polystyrene, polyvinyl alcohol, etc. Compared with inorganic insulating layer materials, they have the following advantages: rich material types; low surface roughness; low surface trap density; low impurity concentration; good compatibility with organic semiconductors and flexible substrates; can be applied to low-cost The low-temperature, solution processing technology, which has good compatibility with the flexible concept of organic thin film transistors. These advantages make organic insulating layer materials show great potential in flexible electronic applications.

In order to realize the multilayer structure of the device, orthogonal solvents or cross-linked insulating layer materials are required. The choice of orthogonal solvents limits the application of many materials. At present, most of the cross-linked insulating layers are applied to organic field effect transistors. preparation. The cross-linking process can be achieved by light and heat. However, most photocrosslinking also requires some photoinitiators and catalysts, some of which are strong acids and bases, which will greatly affect device performance. In addition, most of the thermally crosslinked insulating layer materials currently used have relatively high curing temperatures (greater than 150°C). High crosslinking temperatures will cause a series of problems for some flexible substrates, and the crosslinking process will also affect device performance. by-products.

Contents of the invention

The object of the present invention is to overcome the defects in the above-mentioned prior art, and provide a novel two-component crosslinking agent and its preparation method and application. The cross-linking agent prepared by the invention can realize an effective cross-linking process at a relatively low temperature without the need of a catalyst and without generating by-products.

The purpose of the present invention is achieved through the following technical solutions:

In a first aspect, the present invention relates to a two-component cross-linking agent, the two-component cross-linking agent comprising an acetylenic bond-containing silane compound represented by formula (I) and an azide group-containing compound represented by formula (II) Group of silane compounds:

In a second aspect, the present invention relates to the use of the two-component crosslinking agent of the present invention in the preparation of crosslinked polymer materials.

As a preferred solution, after the two-component crosslinking agent of the present invention is blended and dissolved with the polymer, it is spin-coated to form a film, and the crosslinked polymer material is formed under low-temperature heating conditions.

As a preferred solution, the polymer is selected from polystyrene, polymethyl methacrylate and poly-p-vinylphenol.

As a preferred version, when the two-component crosslinking agent is blended and dissolved with a polymer selected from polystyrene and polymethyl methacrylate, the solvent used is selected from dichloromethane, chloroform, tetrahydrofuran, ethyl acetate, Toluene or chlorobenzene; when the two-component cross-linking agent is blended and dissolved with poly-p-vinylphenol, the solvent used is tetrahydrofuran.

As a preferred solution, the weight ratio of the polymer, the silane compound containing acetylene bond, and the silane compound containing azide group is 20:10:10-15.

As a preferred solution, the low-temperature heating conditions are specifically: the temperature is 80-100° C., and the heating time is 10-30 minutes. This temperature range meets the low temperature standard, and the temperature of the traditional thermally crosslinked insulating layer is above 150 degrees.

In a third aspect, the present invention relates to a method for preparing the two-component crosslinking agent of the present invention, the preparation method comprising:

A. Dissolve propynyl alcohol and organic base in anhydrous ether, add 1,2-bis(trichloromethyl)ethane dropwise under ice bath, and react to obtain the silane compound containing acetylenic bond;

B. Dissolving 3-azidopropanol and an organic base in anhydrous ether, and adding 1,2-bis(trichloromethyl)ethane dropwise under ice-cooling to react to obtain the azide group-containing silane compound.

The preparation route is as follows:

As a preferred solution, the molar ratio of 1,2-bis(trichloromethyl)ethane to propynol is 1:6 to 1:8; when the molar ratio is lower than 1:6, 1,2-bis (Trichloromethyl) ethane reaction is incomplete, can not obtain pure target product; When molar ratio is greater than 1; 8, cause the waste of propynyl alcohol and the residue of propynyl alcohol in target product; Said 1, The molar ratio of 2-bis(trichloromethyl)ethane to 3-azidopropanol is 1:6~1:8; similarly, when the molar ratio is lower than 1:6, 1,2-bis(tri Chloromethyl) ethane reaction is incomplete, can not obtain pure target product; When mol ratio is greater than 1:8, cause the waste of 3-azidopropanol and the residue of 3-azidopropanol in target product.

As a preferred solution, the reaction conditions are: stirring at room temperature for 12-24 hours, if the reaction time is less than 12 hours, the reaction is incomplete and the pure target product cannot be obtained.

As a preferred option, the preparation method also includes post-processing; the post-processing specifically includes: after the reaction is completed, the generated salt is removed by filtration, washed six times with deionized water, dried over anhydrous magnesium sulfate, spinned to remove the solvent, and vacuum-dried .

As a preferred embodiment, the organic base is pyridine, and the molar ratio of pyridine to propynyl alcohol or 3-azidopropanol is 1:1.

In a fourth aspect, the present invention relates to a silane compound containing an alkyne bond represented by formula (I),

In a fifth aspect, the present invention relates to a method for preparing an alkyne bond-containing silane compound represented by formula (I), comprising dissolving propynyl alcohol and an organic base in an organic solvent, and adding 1,2-bis( Trichloromethyl) ethane, react to obtain silane compounds containing alkyne bonds.

As a preferred solution, the reaction condition is stirring at room temperature for 12 to 24 hours, and the best effect is 16 hours.

As a preferred solution, the molar ratio of 1,2-bis(trichloromethyl)ethane to propynyl alcohol is 1:6-1:8, and the molar ratio with the best effect is 1:7.

As a preferred version, the organic solvent is anhydrous ether.

As a preferred embodiment, the organic base is pyridine.

As a preferred solution, the preparation method also includes post-processing, specifically: after the reaction is completed, the formed salt is removed by filtration, washed six times with deionized water, dried with anhydrous magnesium sulfate, spinned to remove the solvent, and vacuum-dried.

In the sixth aspect, the present invention also relates to the use of an acetylenic bond-containing silane compound represented by formula (I) in the preparation of crosslinked polymer materials.

In the seventh aspect, the present invention also relates to an azide group-containing silane compound represented by formula (II):

In the eighth aspect, the present invention also relates to a method for preparing an azide-group-containing silane compound represented by formula (II), comprising the following steps: dissolving 3-azidopropanol and an organic base in an organic solvent, placing the mixture in an ice bath Add 1,2-bis(trichloromethyl)ethane dropwise, and react to obtain a silane compound containing an azide group.

As a preferred solution, the reaction condition is stirring at room temperature for 12 to 24 hours, and the best effect is 16 hours.

As a preferred solution, the molar ratio of 1,2-bis(trichloromethyl)ethane to propynyl alcohol is 1:6-1:8, and the molar ratio with the best effect is 1:7.

As a preferred version, the organic solvent is anhydrous ether.

As a preferred embodiment, the organic base is pyridine.

As a preferred solution, the preparation method also includes post-processing, specifically: after the reaction is completed, the formed salt is removed by filtration, washed six times with deionized water, dried with anhydrous magnesium sulfate, spinned to remove the solvent, and vacuum-dried.

In the ninth aspect, the present invention also relates to the use of an azide group-containing silane compound represented by formula (II) in the preparation of crosslinked polymer materials.

Compared with the prior art, the present invention has the following beneficial effects:

(1) The method of the present invention is simple and effective, the raw materials are easy to synthesize and prepare, the cost is low, and the target product obtained has high purity;

(2) The present invention adopts a novel cross-linking agent, introduces the ring-forming reaction of azide-alkyne as a cross-linking method under heating conditions, and realizes the preparation of cross-linking under the conditions of lower temperature, no metal catalyst and no by-products polymer film material.

Description of drawings

Other characteristics, objects and advantages of the present invention will become more apparent by reading the detailed description of non-limiting embodiments made with reference to the following drawings:

Fig. 1 is the synthetic route figure of embodiment 1 novel linking agent;

Fig. 2 is the hydrogen nuclear magnetic resonance spectrum ( ¹ H-NMR) of the silane compound A containing acetylenic bond;

Fig. 3 is the carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR) of silane compound A containing acetylenic bond;

Fig. 4 is the infrared absorption spectrum (FT-IR) of the silane compound A containing alkyne bond;

Fig. 5 is the hydrogen nuclear magnetic resonance spectrum ( ¹ H-NMR) of the silane compound B containing an azide group;

Fig. 6 is the carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR) of the silane compound B containing an azide group;

Fig. 7 is the infrared absorption spectrum (FT-IR) of the silane compound B containing azide group;

Fig. 8 is the infrared absorption spectrum (FT-IR) of polystyrene and novel crosslinking agent blend material;

Fig. 9 is the differential calorimetry scanning curve (DSC) of polystyrene and novel crosslinking agent blend material;

Fig. 10 is the thermogravimetric analysis curve (TGA) of polystyrene and novel crosslinking agent blend material;

Figure 11 is the infrared absorption spectrum (FT-IR) of polymethyl methacrylate and novel crosslinking agent blend material;

Fig. 12 is the differential calorimetry scanning curve (DSC) of polymethyl methacrylate and novel crosslinking agent blend material;

Fig. 13 is the thermogravimetric analysis curve (TGA) of polymethyl methacrylate and novel crosslinking agent blend material;

Figure 14 is the infrared absorption spectrum (FT-IR) of poly-p-vinylphenol and novel crosslinking agent blend material;

Fig. 15 is the differential calorimetry scanning curve (DSC) of poly-p-vinylphenol and novel crosslinking agent blend material;

Fig. 16 is the thermogravimetric analysis curve (TGA) of poly-p-vinylphenol and the new crosslinking agent blend material.

Detailed ways

The present invention will be described in detail below in conjunction with specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

Embodiment 1, the preparation method of novel linking agent

This example provides a preparation method for a new type of crosslinking agent. The crosslinking agent includes silane compounds containing acetylenic bonds and silane compounds containing azide groups. Its structure is shown in the following formula (I), and its synthetic route is shown in Fig. 1.

1.1. Preparation of acetylenic bond-containing silane compound (A)

The structural formula of the silane compound A containing an acetylenic bond is as follows, and its preparation method is as follows:

See Figure 2 for the hydrogen nuclear magnetic resonance spectrum ( ¹ H-NMR) of the silane compound A containing the alkyne bond; Figure 3 is the carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR) for the silane compound A containing the alkyne bond; The infrared absorption spectrum (FT-IR) of the bonded silane compound A.

Its preparation method is: add propynyl alcohol (1.12g, 21.0mmol) and pyridine (1.60mL, 21.0mmol) into 25mL of anhydrous ether, slowly drop 1,2-bis(trichloromethyl) under ice bath Ethane (0.90g, 3.0mmol), after the dropwise addition, gradually returned to room temperature and stirred for 16h. After the reaction was finished, remove the generated pyridinium hydrochloride by suction filtration, wash the filtrate six times with deionized water, dry the organic phase over anhydrous magnesium sulfate, evaporate the solvent after suction filtration, and dry in vacuo to obtain 1.1g of a light yellow oily liquid. The yield is 83%.

Proton NMR: ¹ H NMR (δ, CDCl ₃ ): 4.45 (d, J = 3.2Hz, 2H), 2.45 (t, J = 3.2Hz, 1H), 0.84ppm (s, 0.7H). Carbon NMR : ¹³ C NMR (δ, CDCl ₃ ): 81.36, 73.90, 51.55, 1.86.

Infrared spectrum: FTIR 3285, 2931, 2865, 2125, 1689, 1458, 1367, 1260, 1153, 1055, 923, 783, 660, ^{627cm -1}

1.2, preparation of silane compound (B) containing azide group

The structural formula of the azide group-containing silane compound B is as follows. Its preparation method is as follows steps:

See Fig. 5 is the hydrogen nuclear magnetic resonance spectrum ( ^1H -NMR) of the silane compound B containing the azide group; Fig. 6 is the carbon nuclear magnetic resonance spectrum ( ^13C -NMR) of the silane compound B containing the azide group; Fig. 7 is the infrared absorption spectrum (FT-IR) of the silane compound B containing an azide group.

Its preparation method is: add 3-azidopropanol (2.02g, 21.0mmol) and pyridine (1.60mL, 21.0mmol) into 25mL of anhydrous ether, slowly add 1,2-bis(trichloro Methyl)ethane (0.90g, 3.0mmol), after the dropwise addition, gradually returned to room temperature, and stirred for 16h. After the reaction was finished, remove the pyridinium hydrochloride generated by suction filtration, wash the filtrate six times with deionized water, dry the organic phase over anhydrous magnesium sulfate, evaporate the solvent after suction filtration, and dry in vacuo to obtain 1.9g light yellow oily liquid. The yield is 93%.

Proton NMR spectrum: ¹ H NMR (δ, CDCl ₃ ): 3.87(t, J=6.0Hz, 1H), 3.45(t, J=6.5Hz, 1H), 1.86(dd, J=6.5, 6.0Hz, 1H ),0.68ppm(s,0.32H). C NMR spectrum: ¹³ CNMR(δ,CDCl ₃ ):59.75,48.13,31.63,1.28

Infrared spectrum: FTIR 2931, 2882, 2092, 1458, 1318, 1252, 1087, 989, 825, 742cm ^-1 .

In the examples, the copolymer silane compound A containing acetylenic bond and silane compound B containing azide group is soluble in common organic solvents, such as chloroform, toluene, chlorobenzene, tetrahydrofuran, dichloromethane, ethyl acetate, etc. .

Embodiment 2, infrared absorption spectrum, differential calorimetry scanning analysis and thermogravimetric analysis of cross-linked polystyrene material

The cross-linking agent used in this embodiment is the novel cross-linking agent prepared in Example 1, which is blended with polystyrene; the weight ratio of polystyrene, acetylenic bond-containing silane compound, and azide group-containing silane compound is 20:10:10, the solvent is dichloromethane) after spin coating on the silicon wafer, the characterization of infrared absorption spectrum is carried out; the solid obtained after the mixed solution is dried in vacuum is used for differential calorimetry scanning analysis and thermogravimetric analysis.

Figure 8 shows the infrared absorption spectrum of the thermally crosslinked polystyrene material after spin-coating to form a film. The absorption peaks at 2100cm ^-1 and 3290cm ^-1 in the spectrum are the characteristic absorption peaks of the azide group and the alkyne bond respectively, indicating that The prepared polystyrene film contains azide group and alkyne bond. After heating the sample at 80°C for 10 minutes, it can be seen that the absorption intensity of the characteristic peak of the azide group and the alkyne bond is obviously weakened, indicating that the azide-alkyne ring formation reaction has occurred; after heating for 20 minutes, the azide group and the The absorption intensity of the characteristic peak of the acetylene bond is not significantly weakened, indicating that the reaction has reached equilibrium. Figure 9 shows that polystyrene has no obvious heat change below 350 °C; while the polystyrene material with crosslinking agent has an obvious exothermic peak in the range of 80-200 °C, indicating that an azide-alkyne ring formation reaction has occurred ; The exothermic peak at 270°C is caused by the decomposition of the azide groups not involved in the crosslinking reaction. Figure 10 shows that the polystyrene material with cross-linking agent has a smaller weight loss than polystyrene due to the cross-linking reaction during the heating process.

Infrared absorption spectrum, differential calorimetry scanning analysis and thermal analysis of the polymethyl methacrylate material of embodiment 3, crosslinking reanalysis

The cross-linking agent used in this example is the novel cross-linking agent prepared in Example 1, which is blended with polymethyl methacrylate; polymethyl methacrylate, silane compounds containing alkyne bonds, The weight ratio of the silane compound is 20:10:10, and the solvent is dichloromethane) to carry out the characterization of the infrared absorption spectrum after spin-coating on the silicon wafer; The solid obtained after the mixed solution is dried in vacuum is used for differential calorimetry scanning analysis and thermal reanalysis.

Figure 11 shows the infrared absorption spectrum of the thermally crosslinked polymethyl methacrylate material after spin-coating and forming a film. The absorption peaks at 2100cm ^-1 and 3290cm ^-1 in the spectrum are characteristic absorptions of azide groups and alkyne bonds, respectively. peak, indicating that the prepared polymethyl methacrylate film contains azido and acetylenic bonds. After heating the sample at 80°C for 10 minutes, it can be seen that the absorption intensity of the characteristic peak of the azide group and the alkyne bond is obviously weakened, indicating that the azide-alkyne ring formation reaction has occurred; after heating for 20 minutes, the azide group and the The absorption intensity of the characteristic peak of the acetylene bond was not significantly weakened, indicating that the reaction reached equilibrium. Figure 12 shows that polymethyl methacrylate has an obvious endothermic peak in the range of 275-350°C, which is caused by the decomposition of polymethyl methacrylate. However, the polystyrene material with cross-linking agent has an obvious exothermic peak in the range of 80-200 ° C, indicating that the azide-alkyne ring formation reaction has occurred; the exothermic peak at 260 ° C is not involved in the cross-linking reaction. Caused by decomposition of the azide group. Figure 13 shows that the polymethyl methacrylate material added with a cross-linking agent has a higher decomposition temperature and a smaller weight loss than polystyrene due to the cross-linking reaction occurring during the heating process.

Infrared absorption spectrum, differential calorimetry scanning analysis and thermogravimetry of embodiment 4, cross-linked polyvinylphenol material analyze

The cross-linking agent used in this example is the novel cross-linking agent prepared in Example 1, which is blended with poly-p-vinylphenol; poly-p-vinylphenol, silane compounds containing acetylenic bonds, and silane compounds containing azide groups The weight ratio is 20:10:10, the solvent is tetrahydrofuran) and the infrared absorption spectrum is characterized after spin-coating on the silicon wafer; the solid obtained after the mixed solution is vacuum-dried is used for differential calorimetry scanning analysis and thermogravimetric analysis.

Figure 14 shows the infrared absorption spectrum of thermally crosslinked poly-p-vinylphenol material after spin-coating to form a film. The absorption peaks at 2100cm ^-1 and 3290cm ^-1 in the spectrum are the characteristic absorption peaks of azide group and acetylenic bond respectively , indicating that the prepared poly(p-vinylphenol) film contains azido and alkyne linkages. After heating the sample at 80°C for 10 minutes, it can be seen that the absorption intensity of the characteristic peak of the azide group and the alkyne bond is obviously weakened, indicating that the azide-alkyne ring formation reaction has occurred; after heating for 20 minutes, the azide group and the The absorption intensity of the characteristic peak of the acetylene bond was not significantly weakened, indicating that the reaction reached equilibrium. Figure 15 shows that poly-p-vinylphenol has an obvious endothermic peak in the range of 160-200 °C, which is caused by the endothermic dehydration of poly-p-vinylphenol; There is an obvious exothermic peak in the range of ~200 °C, indicating that the azide-alkyne ring formation reaction has occurred. Figure 16 shows that the poly-p-vinylphenol material with cross-linking agent has a smaller weight loss than poly-p-vinyl phenol due to the cross-linking reaction during the heating process.

In summary, the novel cross-linking agent of the present invention introduces the ring-forming reaction of azide-alkyne under heating conditions as a cross-linking method, and realizes the preparation of cross-linked products at lower temperatures, without metal catalysts and by-products. Polystyrene, polymethylmethacrylate and polyvinylphenol materials, the resulting material is a potential organic field effect transistor gate insulating layer material, which can be used to prepare various OFETs devices by solution method, and has a wide application prospect .

Specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art may make various changes or modifications within the scope of the claims, which do not affect the essence of the present invention.

Claims (10)

1. A two-component cross-linking agent, characterized in that, said two-component cross-linking agent comprises a silane compound containing an acetylenic bond shown in formula (I) and an azide-containing group shown in formula (II) Silane compounds: 2. A use of a two-component crosslinking agent as claimed in claim 1 in the preparation of crosslinked polymer materials. 3. The use according to claim 2, characterized in that, after the two-component cross-linking agent and the polymer are blended and dissolved, spin-coated to form a film, and heated at 80-100°C to form the cross-linked polymer material. 4. The use according to claim 3, characterized in that the polymer is selected from polystyrene, polymethyl methacrylate, poly-p-vinylphenol. 5. purposes according to claim 4, is characterized in that, when described two-component cross-linking agent is mixed with the polymer that is selected from polystyrene, polymethyl methacrylate and dissolves, the solvent that adopts is selected from two Chloromethane, chloroform, tetrahydrofuran, ethyl acetate, toluene or chlorobenzene; when the two-component crosslinking agent is blended and dissolved with poly-p-vinylphenol, the solvent used is tetrahydrofuran. 6 . The use according to claim 3 , wherein the weight ratio of the polymer, the silane compound containing an acetylene bond, and the silane compound containing an azide group is 20:10:10˜15. 7. a preparation method of two-component cross-linking agent as claimed in claim 1, is characterized in that, described preparation method comprises: A. Dissolve propynyl alcohol and organic base in anhydrous ether, add 1,2-bis(trichloromethyl)ethane dropwise under ice bath, and react to obtain the silane compound containing acetylenic bond; B. Dissolving 3-azidopropanol and an organic base in anhydrous ether, and adding 1,2-bis(trichloromethyl)ethane dropwise under ice-cooling to react to obtain the azide group-containing silane compound. 8. The preparation method of the two-component crosslinking agent according to claim 7, characterized in that, the molar ratio of the 1,2-bis(trichloromethyl)ethane and propynyl alcohol is 1:6～ 1:8; the molar ratio of 1,2-bis(trichloromethyl)ethane to 3-azidopropanol is 1:6-1:8. 9. The preparation method of the two-component cross-linking agent according to claim 7, characterized in that, the reaction condition is: stirring at room temperature for 12-24 hours. 10. the preparation method of two-component linking agent according to claim 7, is characterized in that, described organic base is pyridine, and the mol ratio of described pyridine and propynyl alcohol or 3-azidopropanol is 1: 1.