CN106349489B - Polymethacrylate material and preparation method and application thereof - Google Patents
Polymethacrylate material and preparation method and application thereof Download PDFInfo
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- CN106349489B CN106349489B CN201610705578.6A CN201610705578A CN106349489B CN 106349489 B CN106349489 B CN 106349489B CN 201610705578 A CN201610705578 A CN 201610705578A CN 106349489 B CN106349489 B CN 106349489B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Manufacturing & Machinery (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a polymethacrylic acid material and a preparation method and application thereof; the polymethacrylic material comprises polymethacrylate and a photosensitive initiating cross-linking agent; the mass ratio of the polymethacrylate to the photosensitive initiation cross-linking agent is 20-10: 1. The material adopts a novel crosslinking mode, only simple mixing is needed, the film generates free radicals by photosensitive initiation crosslinking agent under ultraviolet radiation, the free radicals extract hydrogen from the alkyl of the macromolecule to form new free radicals, and then the crosslinking network is formed by free radical coupling, thus obtaining the crosslinking material with solvent resistance. The crosslinking mode does not need to functionalize the macromolecule in advance, realizes the preparation of the crosslinked polymethacrylate material under the conditions of normal temperature, no metal catalyst and no by-product, has simple preparation process, excellent insulating property of the obtained material, is suitable for preparing various OFETs devices by a solution method, and has wide application prospect.
Description
Technical Field
The invention relates to a polymethacrylate material, a preparation method and application thereof, in particular to a preparation method of mixed-photocrosslinking, a crosslinked polymethacrylate film material obtained by the preparation method and application thereof.
Background
Organic field-effect transistors (OFETs) are triode devices that use organic conjugated molecules as the active semiconductor layer, inorganic or high molecular substances as the insulating layer, and are switched by gate voltage regulation. Advantages of organic field effect transistors: firstly, the organic material has wide sources, and the performance of the material can be changed by adjusting the molecular structures of the organic small molecules and the polymer so as to meet the actual requirement; secondly, the processing technology of OFETs is relatively simple, and the requirements on production equipment, processing conditions and processing environment are low, so that the production cost is low; thirdly, OFETs can be processed by adopting a low-temperature deposition method or a solution film forming method, so that the processing speed is high, and a large-area device can be prepared. The characteristics make the organic electronic product have potential application prospect in the aspects of large area, low cost and flexible organic electronic products.
In organic field effect transistors, the insulating layer material is an important component. Due to the fact that interaction force between organic molecules is weak, carrier is in hopping transmission instead of energy band transmission when being transmitted on the organic semiconductor, and due to the fact that the carrier is in a special transmission mode of organic small molecules and polymer semiconductors, the effect of the insulating layer on the semiconductor layer is wider. Through a large number of researches, the ideal insulating layer has the following characteristics: the leakage current is lower and the chemical and physical stability is better; the surface trap density and defects are as low as possible to obtain the maximum mobility; the material has better compatibility to p-type and n-type organic semiconductor materials; has a dielectric constant large enough to lower the threshold voltage and turn-on voltage of the device; the processing can be carried out by the technologies of solution spin coating, printing, stamping and the like; can be compatible with a flexible substrate, and can meet the commercial requirements of low energy consumption and low cost.
The organic field effect transistor is of a multilayer film structure, a solvent used in the following step is required to be avoided from dissolving a processed film in the previous step in layer-by-layer processing, an orthogonal solvent or a cross-linked insulating layer is required to realize the solvent resistance of the material, the selection of the orthogonal solvent limits the application of a plurality of materials, and most of the organic field effect transistors are prepared by applying the cross-linked insulating layer to the organic field effect transistor at present. The currently applied crosslinking method is thermal crosslinking, and most of thermally crosslinked insulating layer materials have relatively high curing temperature (more than 150 ℃) which is higher than the use temperature of some flexible substrates. Some byproducts are also generated during the crosslinking process, which affects the performance of the device.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a polymethacrylate material and a preparation method and application thereof. The polymer does not need to be functionalized in advance, the cross-linked polymethacrylate material is prepared at normal temperature under the conditions of no metal catalyst and no by-product by simply mixing the polymer with a cross-linking agent and using the free radical reaction of active carbonyl and active hydrogen as a cross-linking mode, the preparation process is simple, the obtained material has excellent insulating property, and the cross-linked polymethacrylate material is suitable for preparing various OFETs devices by a solution method and has wide application prospect.
The purpose of the invention is realized by the following technical scheme:
the invention provides a polymethacrylate material, which comprises polymethacrylate and a photosensitive initiation cross-linking agent; the mass ratio of the polymethacrylate to the photosensitive initiation cross-linking agent is 20-10: 1. If the mass ratio is too much, the polymethacrylate can cause insufficient crosslinking, and can be dissolved by a solvent used in a subsequent process in the process of preparing the organic field effect transistor by a continuous solution method, so that the performance of the obtained device is poor; too little polymethacrylate can result in small molecule residues of the cross-linking agent, non-uniformity of the obtained insulating layer film and poor device performance.
Preferably, the mass ratio of the polymethacrylate to the photosensitive initiating crosslinking agent is 20: 1.
Preferably, the polymethacrylate is at least one of polymethyl methacrylate and isobutyl polymethacrylate.
Preferably, the photosensitive cross-linking agent has the following structural formula (I):
wherein: r ═ CnH2nN is a natural number, and n is not less than 2.
Preferably, the preparation method of the photosensitive initiation crosslinking agent comprises the following steps:
s1, adding 3-benzoylbenzoic acid into a mixed solution formed by dichloromethane and diethyl ether, adding a dichloromethane solution containing 4-pyrrolidinyl pyridine and N, N-dicycloethyl carbodiimide under the protection of nitrogen, and uniformly stirring to obtain a mixed solution a;
s2, mixing R (OH)2Adding the mixed solution a into the mixed solution a, stirring, and fully reacting to obtain a suspension b;
s3, carrying out suction filtration, cleaning and drying on the suspension b to obtain a crude product;
s4, separating and drying the crude product through a silica gel column to obtain the photosensitive initiation cross-linking agent;
the R (OH)2In which R is CnH2nN is a natural number, and n is not less than 2.
Preferably, in step S1, the stirring time is 15-20 min; in step S2, the stirring time is 12-15 h.
Preferably, in step S4, the ratio of 3-benzoylbenzoic acid: n, N-dicycloethylcarbodiimide: r (OH)2In a molar ratio of 2: 2: 1.
the invention also provides a preparation method of the polymethacrylate material, which comprises the following steps: the photosensitive initiation cross-linking agent and the polymethacrylate are blended, added into a solvent for dissolving, spin-coated on a substrate to form a film, and then the polymethacrylate material is formed under ultraviolet radiation.
Preferably, the solvent is selected from at least one of dichloromethane, chloroform, ethyl acetate, toluene, N-dimethylformamide or chlorobenzene.
Preferably, the ultraviolet radiation specifically employs the following steps: the adopted wavelength is 365nm, and the power is 7000-7100 mW/cm2The ultraviolet light is irradiated for 10-30 min.
The invention also provides an application of the polymethacrylate material in an organic field effect transistor.
It should be noted that the hybrid radical crosslinking method provided by the present invention can also be applied to other polymer systems, and these polymer materials can be simply mixed with the photosensitive initiation crosslinking agent as long as they have active hydrogen, such as tertiary hydrogen or secondary hydrogen, so that the active hydrogen of these polymer materials can be abstracted to form carbon radicals, and the radicals can be coupled to form a crosslinked network, thereby preparing other crosslinked polymer materials suitable for organic field effect transistors.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts a novel photo-crosslinking method, and the cross-linked polymethacrylate material can be prepared by simply mixing the cross-linking agent and the matrix material (polymethacrylate) and then carrying out ultraviolet radiation;
2. the material adopts a novel crosslinking mode, only simple mixing is needed, the film generates free radicals by photosensitive initiation crosslinking agent under ultraviolet radiation, the free radicals extract hydrogen from the alkyl of the macromolecule to form new free radicals, and then a crosslinking network is formed by free radical coupling, thus obtaining the crosslinking material with solvent resistance;
3. the invention adopts a photosensitive initiation cross-linking agent, and under the condition of introducing ultraviolet radiation, the free radical reaction of active carbonyl and active hydrogen is taken as a cross-linking mode, so that the cross-linked polymethacrylate material is prepared under the conditions of normal temperature, no metal catalyst and no by-product;
4. the cross-linked polymethacrylate material obtained by the invention is suitable for preparing various organic field effect transistor devices by a solution method, and is a cross-linked polymer insulating layer material with excellent performance.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic diagram of the synthesis scheme of polymethacrylate materials of the present invention;
FIG. 2 is a schematic diagram of a synthetic route for the photo-labile initiated cross-linker of the present invention;
FIG. 3 is a diagram of the crosslinking mechanism of a photosensitive initiated crosslinker for crosslinking polymethacrylates;
FIG. 4 is a hydrogen nuclear magnetic resonance (1H-NMR) spectrum of the two-carbon light sensitive initiating crosslinker prepared in example 1;
FIG. 5 is a hydrogen nuclear magnetic resonance spectrum (1H-NMR) of the four-carbon light sensitive initiating crosslinker prepared in example 2;
FIG. 6 is an infrared absorption spectrum (FT-IR) of the two-carbon photo-sensitive initiation cross-linker prepared in example 1;
FIG. 7 is an infrared absorption spectrum (FT-IR) of the four-carbon photo-sensitive initiation cross-linker prepared in example 2;
FIG. 8 shows an infrared absorption spectrum (FT-IR) of a polymethacrylate material prepared from a dicarbo photosensitization initiation cross-linking agent and polymethyl methacrylate;
FIG. 9 shows an infrared absorption spectrum (FT-IR) of a polymethacrylate material prepared from a dicarbo photosensitization-initiated cross-linking agent and polyisobutyl methacrylate;
FIG. 10 shows an infrared absorption spectrum (FT-IR) of a polymethacrylate material prepared from a four-carbon photosensitization-initiated cross-linking agent and polymethyl methacrylate;
FIG. 11 is an infrared absorption spectrum (FT-IR) of a polymethacrylate material prepared from a four-carbon photosensitized initiation cross-linking agent and polyisobutyl methacrylate;
FIG. 12 is a thermogravimetric analysis (TGA) of a solid thick film made of a two carbon photo sensitive initiating crosslinker and polymethylmethacrylate;
FIG. 13 is a Differential Scanning Calorimetry (DSC) curve of a thick solid film made from a four carbon photo-labile initiating crosslinker and polymethylmethacrylate;
FIG. 14 is a thermogravimetric plot (TGA) of a thick solid film prepared from a dicarbo-photosensitive initiating crosslinker and polyisobutyl methacrylate
FIG. 15 is a Differential Scanning Calorimetry (DSC) curve of a thick solid film made from a four carbon photo-sensitive initiating crosslinker and polyisobutyl methacrylate;
FIG. 16 is a schematic view of a metal-insulator-metal (MIM) structure;
fig. 17 is a capacitance curve for a MIM device prepared using solution 1 in example 5;
fig. 18 is a capacitance curve for the MIM device prepared using solution 2 in example 5;
fig. 19 is a leakage current density curve for a MIM device.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
EXAMPLE 1 preparation of two-carbon photo-initiated crosslinker
This example provides a method for preparing a photo-sensitive cross-linking agent, the synthetic route of which is shown in FIG. 2, and the cross-linking mechanism of which is shown in FIG. 3. The structural formula of the two-carbon photosensitive initiation crosslinking agent containing activated carbonyl is as follows, and the preparation method comprises the following steps:
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum (1H-NMR) of the two-carbon activated carbonyl group-containing photo-labile initiated cross-linking agent prepared in this example; FIG. 6 shows an infrared absorption spectrum (FT-IR) of the two-carbon activated carbonyl group-containing crosslinking agent obtained in this example.
The preparation method comprises the steps of adding 3-benzoylbenzoic acid (1.3400g, 6mmol) into a mixed solution of dichloromethane and ether (50m L), adding a dichloromethane (10m L) solution containing 4-pyrrolidinyl pyridine (0.0830g, 0.6mmol) and N, N-dicycloethyl carbodiimide (1.2207g, 6mmol) under the protection of nitrogen, stirring for 15 minutes, slowly dropwise adding ethylene glycol (0.1860g, 3mmol) into a reaction system, stirring for 12 hours, carrying out suction filtration on a reaction product, washing a filtrate for 3 times with deionized water, washing a dilute acetic acid solution for 3 times, washing a saturated sodium chloride solution for 1 time, finally drying with anhydrous magnesium sulfate, carrying out suction filtration, evaporating a solvent to obtain light yellow powder, taking a mixed solution of ethyl acetate and petroleum ether (1:3 volume ratio) as an eluent, separating a product through a silica gel column, and carrying out vacuum drying to obtain 401mg of white powder with the yield of 81%.
Nuclear magnetic hydrogen spectrum: 1H NMR (400MHz, Chloroform-d)8.47(s,1H),8.27(dd, J ═ 7.8,1.2Hz,1H),8.03(dd, J ═ 7.7,1.3Hz,1H),7.81(d, J ═ 7.8Hz,2H),7.61(td, J ═ 7.9,3.2Hz,2H),7.49(t, J ═ 7.8Hz,2H),4.71(s,2H).
Infrared spectrum: FTIR 172716491239713 cm-1.
In this example, the photo-labile initiation cross-linker, when blended with a polymer, is soluble in many common organic solvents, such as methylene chloride, chloroform, ethyl acetate, toluene, N-dimethylformamide, or chlorobenzene, among others.
EXAMPLE 2 preparation of a novel four-carbon activated carbonyl-containing photo-initiated Cross-linker
This example provides a method for preparing a photo-initiated cross-linking agent, the synthetic route of which is shown in FIG. 2, and the mechanism of which is shown in FIG. 3. The structural formula of the four-carbon photosensitive initiation crosslinking agent containing activated carbonyl is as follows, and the preparation method comprises the following steps:
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum (1H-NMR) of the four-carbon activated carbonyl group-containing photo-labile initiated cross-linking agent prepared in this example; FIG. 7 shows an infrared absorption spectrum (FT-IR) of the four-carbon reactive carbonyl group-containing crosslinking agent obtained in this example.
The preparation method comprises the steps of adding 3-benzoylbenzoic acid (1.0212g, 4.50mmol) into a mixed solution of dichloromethane and ether (40m L), adding a dichloromethane (5m L) solution containing 4-pyrrolidinylpyridine (0.0669g, 0.45mmol) and N, N-dicycloethylcarbodiimide (0.9313g, 4.50mmol) under the protection of nitrogen, stirring for 15 minutes, slowly dropwise adding 1, 4-butanediol (0.2034g, 2.26mmol) into a reaction system, stirring for 12 hours, carrying out suction filtration on a reaction product, washing a filtrate for 3 times with deionized water, washing for 3 times with a dilute acetic acid solution and 1 time with a saturated sodium chloride solution, finally drying with anhydrous magnesium sulfate, carrying out suction filtration, evaporating to remove a solvent to obtain light yellow powder, taking a mixed solution of ethyl acetate and petroleum ether (1:3 volume ratio) as an eluent, separating a pure product through a silica gel column, and carrying out vacuum drying to obtain 357mg of white powder with the yield of 82%.
Nuclear magnetic hydrogen spectrum: 1H NMR (400MHz, Chloroform-d)8.46(s,1H),8.28(dd, J ═ 7.8,1.3Hz,1H),8.02(dd, J ═ 7.7,1.2Hz,1H), 7.86-7.78 (m,2H),7.56(dt, J ═ 35.0,7.9Hz,4H),4.44(s,2H).
Infrared spectrum: FTIR 172116551267708 cm-1.
In the examples, the photo-labile initiating crosslinker, when blended with a polymer, is soluble in many common organic solvents such as methylene chloride, chloroform, ethyl acetate, toluene, N-dimethylformamide, or chlorobenzene, among others.
Example 3 Cross-Linked polymethyl methacrylate Material
The crosslinking agent used in this example is the two-carbon photosensitive initiated crosslinking agent prepared in example 1 or the four-carbon photosensitive self-initiated crosslinking agent prepared in example 2, and is blended with polymethacrylate, and the preparation method is shown in fig. 1, and specifically includes the following steps:
60mg of polymethyl methacrylate was mixed with 3mg of a photo-sensitive initiating crosslinker in methylene chloride. Spin-coating on silicon substrate, and crosslinking under irradiation with an ultraviolet lamp having a wavelength of 365nm and a radiant energy of 7000mW/cm2 for a variable irradiation time, sampling every ten minutes of irradiation, and performing infrared spectroscopy until the irradiation time reaches 40 minutes. Obtaining the polymethacrylate material.
FIG. 8 shows an infrared absorption spectrum (FT-IR) of a polymethacrylate material prepared from a two-carbon photosensitization initiation cross-linking agent and polymethyl methacrylate in this example, and FIG. 10 shows an infrared absorption spectrum (FT-IR) of a mixture material of a four-carbon cross-linking agent and polymethyl methacrylate. 3000cm in the map-1Left and right sum 1700cm-1Left and rightThe absorption peaks of (a) are respectively characteristic absorption peaks of active carbon-hydrogen bonds in the polymethacrylate and active carbonyl groups in the photosensitive initiating crosslinking agent. Radiating the sample at 365nm with the radiant energy of 7000mW/cm2After the ultraviolet lamp is irradiated for 10 minutes, the absorption intensity of the characteristic peak of the active carbon-hydrogen bond and the active carbonyl group is obviously weakened, which indicates that the active carbonyl and the active carbon-hydrogen bond are subjected to free radical reaction under the photo-crosslinking condition; after 20 minutes of crosslinking, the tendency to decrease the characteristic peaks of the radicals is slowed down, or even insignificant, indicating that the reaction is in equilibrium. Therefore, 20 minutes is the optimum crosslinking time for the insulating film material.
In order to meet the quality requirement of thermal analysis, a cross-linked membrane with a micron-sized membrane thickness is designed, 60mg of polymethyl methacrylate and 3mg of photosensitive initiation cross-linking agent are mixed, and the solvent is dichloromethane. The mixed solution was dried under vacuum for 36 hours to obtain a thick solid film. For sufficient crosslinking, the thick film was exposed to a radiation energy of 7000mW/cm at a wavelength of 365nm2Irradiating for 1h under an ultraviolet lamp to obtain the cross-linked solid thick film. This sample was used for differential scanning calorimetry and thermogravimetric analysis only.
FIG. 12 is a thermogravimetric analysis (TGA) of a solid thick film made of the dicarbo-photosensitive initiating crosslinker and polymethylmethacrylate of this example. FIG. 13 is a Differential Scanning Calorimetry (DSC) curve of a thick solid film made from the four-carbon photo-sensitive initiating crosslinker and poly (methyl methacrylate) of this example. FIG. 12 shows that the thermal weight loss curve of the polymethyl methacrylate material does not change much after the addition of the photo-sensitive initiation cross-linking agent. Firstly, the amount of the crosslinking agent is small in order to ensure the value of the surface roughness of the insulating layer. The resulting cross-linked material is less cross-linked and therefore does not significantly alter the thermal properties of the matrix material. In addition, no weight loss occurs in the low-temperature region, which indicates that the mixed material has no small molecular crosslinking agent residue basically, i.e. the added crosslinking agent and the matrix material polymethyl methacrylate have a crosslinking reaction. The differential scanning calorimetry analysis of FIG. 13 also shows that the addition of the photo-sensitive initiating crosslinker has little effect on the thermal properties of the substrate. In the differential scanning calorimetry analysis chart of the blank sample and the sample added with the photosensitive initiating crosslinking agent, only one exothermic peak of glass transition temperature is shown.
Example 4 Cross-Linked polyisobutyl methacrylate Material
The cross-linking agent used in this example is the four-carbon photosensitive initiation cross-linking agent prepared in example 2, and is blended with polymethacrylate, and the preparation method is shown in fig. 1, and specifically includes the following steps:
60mg of polymethacrylate was mixed with 3mg of a photo-sensitive initiating cross-linking agent in dichloromethane. Spin-coating on a silicon substrate, followed by irradiating with radiation energy of 7000mW/cm at a wavelength of 365nm2The cross-linking is carried out by the irradiation of an ultraviolet lamp, the irradiation time is variable, sampling is carried out once every ten minutes of irradiation, and the infrared spectrogram analysis is carried out until the irradiation is carried out for 40 minutes, thus obtaining the polymethacrylate material.
FIG. 9 shows an infrared absorption spectrum (FT-IR) of a polymethacrylate material prepared from a dicarbo photosensitization-initiated cross-linking agent and polyisobutyl methacrylate; FIG. 11 shows an infrared absorption spectrum (FT-IR) of a polymethacrylate material prepared from a four-carbon photosensitized initiation cross-linking agent and polyisobutyl methacrylate. 3000cm in the map-1Left and right sum 1700cm-1The left and right absorption peaks are respectively the characteristic absorption peaks of the active carbon-hydrogen bond in the polymethacrylate and the active carbonyl in the photosensitive initiating cross-linking agent. Radiating the sample at 365nm with the radiant energy of 7000mW/cm2After the ultraviolet lamp is irradiated for 10 minutes, the absorption intensity of the characteristic peak of the active carbon-hydrogen bond and the active carbonyl group is obviously weakened, which indicates that the active carbonyl and the active carbon-hydrogen bond are subjected to free radical reaction under the photo-crosslinking condition; after 20 minutes of crosslinking, the tendency to decrease the characteristic peaks of the radicals is slowed down, or even insignificant, indicating that the reaction is in equilibrium. Therefore, 20 minutes is the optimum crosslinking time for the insulating film material.
In order to meet the quality requirement of thermal analysis, a crosslinked film with micron-sized film thickness is designed, 60mg of polyisobutyl methacrylate and 3mg of photosensitive initiation crosslinking agent are mixed, and the solvent is dichloromethane. The mixed solution was dried under vacuum for 36 hours to obtain a thick solid film. For sufficient crosslinking, the thick film was exposed to a radiation energy of 7000mW/cm at a wavelength of 365nm2Under ultraviolet lamp for 1h to obtain cross-linkingSolid thick film. This sample was used for differential scanning calorimetry and thermogravimetric analysis only.
FIG. 14 is a thermogravimetric plot (TGA) of a thick solid film prepared from the dicarbo-photosensitive initiating crosslinker and polyisobutyl methacrylate of this example. FIG. 15 is a Differential Scanning Calorimetry (DSC) curve of a thick solid film prepared from the four-carbon photosensitive initiating crosslinker and polyisobutyl methacrylate of this example. FIG. 14 shows that the thermal weight loss curve of the polyisobutyl methacrylate material is not changed much after the photosensitive initiation cross-linking agent is added. Firstly, the amount of the crosslinking agent is small in order to ensure the value of the surface roughness of the insulating layer. The resulting cross-linked material is less cross-linked and therefore does not significantly alter the thermal properties of the matrix material. In addition, no weight loss occurs in the low-temperature region, which indicates that the mixed material has no small-molecule cross-linking agent residue basically, i.e. the added cross-linking agent and the matrix material of the polyisobutyl methacrylate have a cross-linking reaction. The differential scanning calorimetry analysis of FIG. 15 also shows that the addition of the photo-sensitive initiating crosslinker has little effect on the thermal properties of the substrate. In the differential scanning calorimetry analysis chart of the blank sample and the sample added with the photosensitive initiating crosslinking agent, only one exothermic peak of glass transition temperature is shown.
EXAMPLE 5 MIM Properties of novel crosslinked polymethacrylate blend Material as insulating layer
The novel cross-linked polyisobutyl methacrylate mixture material used in this example was prepared by blending polyisobutyl methacrylate with the photosensitive self-initiating photo-cross-linking agent prepared in example 2 and then cross-linking the blend under UV irradiation. Solution 1: 60mg of polymethyl methacrylate and 3mg of novel photosensitive self-initiated photocrosslinking agent are blended and dissolved in 2ml of chlorobenzene; solution 2: 60mg of polyisobutyl methacrylate and 3mg of the novel photosensitive self-initiating photocrosslinker were dissolved in 2ml of chlorobenzene in a blend.
Fig. 16 is a schematic view of a metal-insulator-metal (MIM) structure of a cross-linked polymethacrylate mixture material. As shown in fig. 16, the MIM device is prepared by: evaporating and plating a 40 nm-thick aluminum metal layer on a glass substrate to serve as an electrode, and blending polymethacrylate and photosensitive self-initiated photocrosslinking agent with chlorobenzeneThe solution (solution 1 or solution 2) was stirred at room temperature for 12 hours and spin-coated on a silicon substrate. Subsequently, the energy of radiation with the wavelength of 365nm is 7000mW/cm2The UV lamp is used for crosslinking, and the crosslinking time is 20 minutes. After crosslinking was complete, the coupons were annealed at a temperature of 100 ℃ to volatilize the residual solvent. Then, a silver electrode having a thickness of 40nm was deposited on the insulating layer by evaporation.
Fig. 17 is a capacitance curve of an MIM device fabricated using solution 1 according to this example, wherein sample 1, sample 2, and sample 3 are parallel samples. When the frequency increases from 20Hz to 105At Hz, the dielectric constant and the phase angle value of the crosslinked polymethyl methacrylate film material show stability, which indicates that the crosslinked insulating layer film has stable property. Fig. 18 is a graph of capacitance curves for MIM devices prepared using solution 2 of this example, where sample 1, sample 2, and sample 3 are parallel samples. When the frequency increases from 20Hz to 105At Hz, the dielectric constant and the phase angle value of the cross-linked polyisobutyl methacrylate film material are not obviously changed, which shows that the dielectric property of the cross-linked insulating layer film is stable.
This example also discusses the leakage current density of the MIM device insulating layer made of polymethacrylates with different cross-linking agents and different ratios, as shown in fig. 19. It can be seen that the four-carbon crosslinker crosslinked polymeric material exhibits a smaller and more stable leakage current density than the two-carbon crosslinker crosslinked polymeric material under the same electric field. This is because the more the carbon content is, the more flexible the molecules are, the more free the movement of the polymer, the better the crosslinking, the less the leakage defects of the prepared crosslinking agent, and thus the less and more stable leakage current density is exhibited.
In conclusion, the photocrosslinking polymethacrylate material provided by the invention adopts a crosslinking mode of radical reaction of active carbonyl and active hydrogen under the condition of ultraviolet radiation, so that the preparation of the crosslinked polymethacrylate material under the conditions of normal temperature, no metal catalyst and no by-product is realized, and the obtained material is suitable for OFETs devices prepared by a solution method as an insulating layer material. The main contribution of the invention lies in that the potential insulating material is solidified by a simple photo-crosslinking mode, thereby being widely applied to the work of preparing devices by a solution method. The preparation process is simple, the obtained material has excellent insulating property, is suitable for preparing various OFETs devices by a solution method, and has wide application prospect.
The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.
Claims (6)
1. A polymethacrylate material is characterized by comprising polymethacrylate and a photosensitive initiation cross-linking agent; the mass ratio of the polymethacrylate to the photosensitive initiation cross-linking agent is 20-10: 1;
the structural formula of the photosensitive initiation crosslinking agent is shown as the following formula (I):
wherein: r ═ C4H8。
2. The polymethacrylate material as claimed in claim 1 wherein the mass ratio of polymethacrylate to the photo-sensitive initiating cross-linking agent is 20: 1.
3. A method for preparing a polymethacrylate material as claimed in any one of claims 1-2, comprising the steps of: the photosensitive initiation cross-linking agent and the polymethacrylate are blended, added into a solvent for dissolving, spin-coated on a substrate to form a film, and then the polymethacrylate material is formed under ultraviolet radiation.
4. The method according to claim 3, wherein the solvent is at least one selected from dichloromethane, chloroform, ethyl acetate, toluene, N-dimethylformamide, and chlorobenzene.
5. The method for preparing the polymethacrylate material as claimed in claim 3, wherein the ultraviolet radiation specifically adopts the following steps: the adopted wavelength is 365nm, and the power is 7000-7100 mW/cm2The ultraviolet light is irradiated for 10-30 min.
6. Use of a polymethacrylate material as claimed in any one of claims 1-2 in an organic field effect transistor.
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| CN105336860A (en) * | 2015-11-09 | 2016-02-17 | 南京邮电大学 | Flexible low-voltage organic field effect transistor and manufacturing method thereof |
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