CN110628026A - Method for continuously synthesizing polyimide precursor by using microreactor - Google Patents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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Abstract
The application relates to a method for continuously synthesizing a polyimide precursor by utilizing a microreactor, which comprises the following steps: under the protection of nitrogen or inert gas, diamine with preset solid content is dissolved in a polar aprotic solvent to obtain a diamine solution; under the protection of nitrogen or inert gas, dissolving anhydride with preset solid content in a polar aprotic solvent to obtain an anhydride solution; conveying the anhydride solution and the diamine solution into a microreactor with a channel with a preset size at a preset flow rate through a metering device, mixing two phases, and reacting for a preset time at a preset reaction temperature to obtain a polyamic acid solution; the obtained polyamic acid solution was imidized to obtain polyimide. The method has the advantages of short reaction time, accurate and controllable reaction temperature and concentration, narrow polyimide molecular weight distribution and continuous reaction.
Description
Technical Field
The application relates to the technical field of organic synthesis, in particular to a method for continuously synthesizing a polyimide precursor by using a microreactor.
Background
Polyimide is a polymer containing a five-membered imide ring in the main molecular chain, and has a large number of aromatic heterocyclic structures, so that the polyimide has excellent comprehensive properties, such as good mechanical properties, excellent thermal stability, controllable thermal expansion properties, excellent electrical/insulating properties and the like. Polyimides have been used in a variety of fields such as aerospace and microelectronics. Polyimide synthesis methods can be divided into two main categories: the first is to prepare polyimide by forming an imide ring in a reaction; the second type is a polyimide obtained by condensation polymerization of a monomer having an imide ring. At present, the polycondensation reaction of the dicarboxylic anhydride and the diamine is the most common and most important method for preparing the polyimide, and the polymerization reaction can be divided into a 'one-step method' and a 'two-step method' from the reaction mechanism.
The one-step method is that the binary anhydride and diamine monomer are heated in a high boiling point solvent to a certain temperature or are directly polymerized in a molten state to obtain the polyimide with high molecular weight. The one-step process has a limited range of applications due to the high polymerization temperature and the requirement of a certain solubility of the polymer in the organic solvent. The first step of the "two-step" process comprises dissolving dianhydride and diamine in an aprotic polar solvent, polymerizing for a certain time to obtain a polyimide precursor-polyamic acid solution; the second step comprises the chemical imidization of the polyamic acid solution under the action of acetic anhydride and catalyst to form polyimide, or the high temperature dehydration to form polyimide product. The two-step method has the advantage that the precursor polyamic acid (PAA) of polyimide can be obtained at room temperature or lower temperature, so that the subsequent coating and other processing are simple and convenient. The two-step process is suitable for the preparation of virtually all polyimides. However, the conventional polyimide preparation is generally more than 6 hours, the reaction time is long, the reaction temperature and the reaction concentration are not uniformly distributed, and the batch reaction is adopted.
The micro-reactor technology originated in the nineties of the last century and belongs to a front-edge development technology. Microreactors are three-dimensional structural elements that can be used for chemical reactions and are manufactured by precision machining techniques. The fluid channel of the micro-reactor is in the micron or millimeter grade, and the small size enables the specific surface area, the temperature, the pressure and the like of the fluid in the micro-reactor to be effectively improved, so that the heat transfer, mass transfer and flow characteristics of the fluid are changed, and the aim of strengthening the reaction is fulfilled. Meanwhile, the microreactor can contain a plurality of microchannels, and fluids can be mixed and flow in the reactor in a specific state, so that high yield can be realized and the microreactor is easy to amplify. Compared with the conventional reactor, the micro-reactor equipment has the advantages that the small occupied space can realize an efficient process, and the economic, safety and ecological benefits are realized. Therefore, the microreactor technology has attracted great attention in organic synthesis, polymerization reaction, nano-particle reaction and photochemical reaction, and is primarily applied to the fields of material preparation, water treatment and the like.
Disclosure of Invention
Although microreactor technology has received much attention in organic synthesis and polymerization reactions, there is no report of continuous synthesis of polyimide through microreactors. Whether the polyimide is synthesized by the "one-step" or "two-step" method as described above, they are batch reactions and require a long polymerization time. It is generally believed that existing microreactors have difficulty providing the mixing length required for polyimide synthesis. Therefore, no scholars focused on the study of the continuous synthesis of polyimides in microreactors.
The present application aims to provide a method for continuously synthesizing a polyimide precursor by using a microreactor, thereby solving the technical problems in the prior art. Specifically, the application provides a method for preparing a polyimide precursor by using a continuous flow microreactor technology, aiming at the defects of wide molecular weight, unfavorable continuous production due to the fact that the traditional polyimide preparation time is long, and the reaction temperature and concentration distribution are uneven, and the like.
In order to solve the above technical problems, the present application provides the following technical solutions.
In a first aspect, the present application provides a method for continuously synthesizing a polyimide precursor using a microreactor, characterized in that the method comprises the steps of:
s1: under the protection of nitrogen or inert gas, diamine with preset solid content is dissolved in a polar aprotic solvent to obtain a diamine solution;
s2: under the protection of nitrogen or inert gas, dissolving anhydride with preset solid content in a polar aprotic solvent to obtain an anhydride solution;
s3: and (2) conveying the anhydride solution and the diamine solution into a microreactor with a channel with a preset size at a preset flow rate through a metering device, mixing the two phases, and reacting at a preset reaction temperature for a preset time to obtain the polyimide precursor.
In one embodiment of the first aspect, the diamine is one or more of 4,4 '-diaminodiphenyl ether, 2,2' -bis (trifluoromethyl) -4,4 '-diaminophenyl ether, 2,2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 1, 4-phenylenediamine, 1, 3-phenylenediamine, 3, 3' -dialkyl-4, 4 '-diaminodiphenylmethane, 3, 4' -diaminodiphenyl ether, 4 '-diaminobenzophenone, 3, 3', 5,5 '-tetramethyl-4, 4' -diaminodiphenylmethane.
In one embodiment of the first aspect, the acid anhydride is 1,2,4, 5-pyromellitic dianhydride, 3,3 ', 4,4' -benzophenone tetracarboxylic dianhydride, 4,4 '-diphenyl ether dianhydride, 3,3,4, 4-biphenyl dianhydride, 4, 4-hexafluoroisopropyl phthalic anhydride, 4,4' - (acetylene-1, 2, -diyl) diphthalic anhydride, Benzophenone Tetracarboxylic Dianhydride (BTDA), anisole tetracarboxylic dianhydride (ODPA), thiodipropionic anhydride (TDPA), diphenylsulfone tetracarboxylic dianhydride (DSDA), hexafluoro dianhydride (6FDA), triphendiether tetracarboxylic dianhydride (HQDPA), bisphenol a dianhydride (BPADA), bis- (3, 4-phthalic anhydride) -dimethylsilane (SiDA), cyclobutane tetracarboxylic dianhydride (CBDA), cyclopentyltetracarboxylic dianhydride (CPDA), 1,2,3, 4-cyclohexane tetracarboxylic dianhydride (CHDA), bicyclo [2.2.2] octane-2, 3,5, 6-tetracarboxylic dianhydride (BOTDA), and bicyclo [2.2.1] hexane-2, 3,5, 6-tetracarboxylic dianhydride (BHTDA).
In one embodiment of the first aspect, the polar aprotic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, or dimethylsulfoxide.
In one embodiment of the first aspect, the predetermined solids content in step S1 and the predetermined solids content in step S2 are each independently from 1% to 50% by weight.
In one embodiment of the first aspect, in step S3, the molar ratio of the diamine to the anhydride is 1: 1 to 1.1.
In an embodiment of the first aspect, in step S3, the metering device is one or more of an injection pump, a peristaltic pump, or a constant flow pump.
In one embodiment of the first aspect, the predetermined flow rate is 0.05ml/min to 100ml/min in step S3.
In one embodiment of the first aspect, in step S3, the predetermined size of the channel of the microreactor is 0.2mm to 10 mm.
In one embodiment of the first aspect, in step S3, the predetermined reaction time is 10min to 24 h.
In one embodiment of the first aspect, in step S3, the predetermined reaction temperature is 0 to 80 ℃.
In one embodiment of the first aspect, the polyimide has a molecular weight distribution coefficient of 1.5 to 5 in step S4.
Compared with the prior art, the method has the advantages that the reaction time is short, the reaction temperature and the concentration are accurate and controllable, the molecular weight distribution of the polyimide is narrow, and the reaction can be continuously carried out.
Drawings
Fig. 1 shows a schematic view of an apparatus according to an embodiment of the present application.
In fig. 1, reference numeral 1 denotes a metering apparatus; reference numeral 2 denotes an acid anhydride solution, and reference numeral 3 denotes a diamine solution; and reference numeral 4 denotes a microreactor.
FIG. 2 is an infrared spectrum of a polyimide prepared according to one embodiment of the present application.
FIG. 3 is a GPC chart of a polyimide prepared according to one example of the present application.
Detailed Description
The synthesis method of polyimide comprises a 'one-step method' or a 'two-step method', but the synthesis methods belong to batch reaction and both require long polymerization reaction time. Furthermore, existing microreactors are generally considered to be difficult to provide the mixing length required for the synthesis of polyimides. Therefore, no one has focused on a technique for continuously synthesizing polyimide in a microreactor.
The present application aims to provide a method for continuously synthesizing a polyimide precursor by using a microreactor, thereby solving the technical problems in the prior art. Specifically, aiming at the defects of long time, uneven reaction temperature and concentration distribution, intermittent reaction and the like of the traditional polyimide preparation, the application provides a method for preparing a polyimide precursor by using a continuous flow microreactor technology.
In a specific embodiment, the present application provides a method for synthesizing a polyimide precursor, which includes respectively placing diamine and anhydride with a certain solid content in a polar aprotic solvent protected by nitrogen or inert gas, controlling a certain molar ratio of the diamine to the anhydride, stirring to completely dissolve the diamine, mixing a dianhydride solution and a diamine solution at a certain flow rate and a certain flow rate into a microreactor with a certain size, and reacting at a certain reaction temperature for a certain time to obtain the polyimide precursor.
In one embodiment, the polyimide precursor is a polyamic acid solution. In one embodiment, the polyamic acid solution is imidized to provide a polyimide. The polyimide prepared by the method has the advantages of short time, continuity and narrow molecular weight distribution.
In one embodiment, the present application relates to a method for preparing a polyimide precursor by a continuous flow microreactor technique, characterized by the steps of:
diamine and anhydride with certain solid content are respectively put in a polar aprotic solvent protected by nitrogen or inert gas, the molar ratio of the diamine to the anhydride is controlled, after the diamine and the anhydride are completely dissolved by stirring, a dianhydride solution and a diamine solution are mixed into a microreactor with a certain size at a certain flow rate and a certain phase through a metering device, and the polyimide precursor is obtained after a reaction for a certain time at a certain reaction temperature.
In one embodiment, the method for preparing the polyimide precursor by the continuous-flow microreactor technology is characterized in that: the certain solid content in the step is 1 to 50 percent
In one embodiment, the method for preparing the polyimide precursor by the continuous-flow microreactor technology is characterized in that: the diamine in the step (a) is one or more of 4,4 '-diaminodiphenyl ether, 2,2' -bis (trifluoromethyl) -4,4 '-diaminophenyl ether, 2,2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 1, 4-phenylenediamine, 1, 3-phenylenediamine, 3, 3' -dialkyl-4, 4 '-diaminodiphenylmethane, 3, 4' -diaminodiphenyl ether, 4 '-diaminobenzophenone, and 3, 3', 5,5 '-tetramethyl-4, 4' -diaminodiphenylmethane.
In one embodiment, the method for preparing the polyimide precursor by the continuous-flow microreactor technology is characterized in that: the acid anhydride in step (a) is 1,2,4, 5-pyromellitic dianhydride, 3,3 ', 4,4' -benzophenone tetracarboxylic dianhydride, 4,4 '-diphenyl ether dianhydride, 3,3,4, 4-biphenyl dianhydride, 4, 4-hexafluoroisopropyl phthalic anhydride, 4,4' - (acetylene-1, 2, -diyl) diphthalic anhydride, Benzophenone Tetracarboxylic Dianhydride (BTDA), anisole tetracarboxylic dianhydride (ODPA), thiodipropionic anhydride (TDPA), diphenylsulfone tetracarboxylic dianhydride (DSDA), hexafluoro dianhydride (6FDA), triphendiether tetracarboxylic dianhydride (dphqa), bisphenol a dianhydride (BPADA), bis- (3, 4-phthalic anhydride) -dimethylsilane (SiDA), cyclobutane tetracarboxylic dianhydride (CBDA), cyclopentanetetracarboxylic dianhydride (CPDA), 1,2,3, 4-cyclohexane tetracarboxylic dianhydride (CHDA), bicyclo [2.2.2] octane-2, 3,5, 6-tetracarboxylic dianhydride (BOTDA) and bicyclo [2.2.1] hexane-2, 3,5, 6-tetracarboxylic dianhydride (BHTDA).
In one embodiment, the method for preparing the polyimide precursor by the continuous-flow microreactor technology is characterized in that: the certain molar ratio in the step (a) is 1: 1 to 1.1.
In one embodiment, the method for preparing the polyimide precursor by the continuous-flow microreactor technology is characterized in that: the polar aprotic solvent in step (a) is: n, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone.
In one embodiment, the method for preparing the polyimide precursor by the continuous-flow microreactor technology is characterized in that: the metering equipment in the step is as follows: one or more of an injection pump, a peristaltic pump and a constant flow pump.
In one embodiment, the method for preparing the polyimide precursor by the continuous-flow microreactor technology is characterized in that: the certain flow rate in the step is 0.05 ml/min-100 ml/min.
In one embodiment, the method for preparing the polyimide precursor by the continuous-flow microreactor technology is characterized in that: the reactor with a certain size in the step is a microreactor with the diameter of 0.2 mm-10 mm.
In one embodiment, the length of the microreactor can be customized according to actual needs, for example, a length of 2m, 3m, 5m or more.
In one embodiment, the method for preparing the polyimide precursor by the continuous-flow microreactor technology is characterized in that: the certain reaction time in the step is 10 min-24 h.
In one embodiment, the method for preparing the polyimide precursor by the continuous-flow microreactor technology is characterized in that: the certain reaction temperature in the step is 0-80 ℃.
Examples
The present application will now be described and illustrated in further detail with reference to the following examples. All chemical raw materials can be purchased from the market unless otherwise specified. Those skilled in the art will appreciate that the following embodiments are exemplary only.
In the following examples, the infrared spectrometer used was a Spectrum 100 FT-IR spectrometer (Perkin Elmer, Inc., United States).
In the following examples, the GPC chromatograph used was a Perkin-Elmer Series 200, with the following specific test conditions: the calibration standard for GPC analysis was polystyrene containing 0.03mol/L LiBr and 0.03mol/L H in Dimethylformamide (DMF) eluent3PO4The elution rate was 0.6 mL/min. The temperature was 40 ℃.
Example 1
This example relates to the continuous synthesis of polyimide using a microreactor. The specific experimental procedure of this example will be described below with reference to fig. 1.
4,4' -diaminodiphenyl ether and 4, 4-hexafluoroisopropyl phthalic anhydride with solid content of 15% are respectively dissolved in N, N-dimethylacetamide solvent protected by nitrogen, and the molar ratio of diamine to anhydride is controlled to be 1: 1, after stirring to completely dissolve the two solutions, the acid anhydride solution 2 and the diamine solution 3 were fed into a microreactor having an inner diameter of 1mm and a length of 8.9m at a flow rate of 0.1ml/min by means of a syringe pump 1, and the two solutions were subjected to a two-phase mixing reaction in the microreactor. Then, the resultant mixture was reacted at a reaction temperature of 20 ℃ for 15min to obtain a polyamic acid solution.
Next, the obtained polyamic acid solution was imidized (80 ℃/1h, 120 ℃/1h, 150 ℃/1h, 180 ℃/1h, 220 ℃/1h and 250 ℃/4h, heating rate 5 ℃) to obtain polyimide.
The polyimide prepared in this example was subjected to infrared spectroscopy, and the results are shown in FIG. 2. 719cm, as shown in FIG. 2-1Is C ═ O flexural vibration absorption peak, 1246cm-1Is C-O stretching vibration absorption peak, 1373cm-1Is C-N stretching vibration absorption peak, 1728cm-1、1787cm-1C ═ O telescopic absorptions.
GPC measurement was carried out on the polyimide prepared in this example, and the results are shown in FIG. 3. As can be seen from FIG. 3, the number average molecular weight of the polyimide according to this example was 11.6X 103g/mol, molecular weight distribution coefficient of 2.49.
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (10)
1. A method for continuously synthesizing a polyimide precursor by using a microreactor, comprising the steps of:
s1: under the protection of nitrogen or inert gas, diamine with preset solid content is dissolved in a polar aprotic solvent to obtain a diamine solution;
s2: under the protection of nitrogen or inert gas, dissolving anhydride with preset solid content in a polar aprotic solvent to obtain an anhydride solution;
s3: and (2) conveying the anhydride solution and the diamine solution into a microreactor with a channel with a preset size at a preset flow rate through a metering device, mixing the two phases, and reacting at a preset reaction temperature for a preset time to obtain the polyimide precursor.
2. The method for continuously synthesizing a polyimide precursor using a microreactor as claimed in claim 1, wherein the diamine is one or more selected from the group consisting of 4,4 '-diaminodiphenyl ether, 2,2' -bis (trifluoromethyl) -4,4 '-diaminophenyl ether, 2,2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 1, 4-phenylenediamine, 1, 3-phenylenediamine, 3, 3' -dialkyl-4, 4 '-diaminodiphenylmethane, 3, 4' -diaminodiphenyl ether, 4 '-diaminobenzophenone, 3, 3', 5,5 '-tetramethyl-4, 4' -diaminodiphenylmethane;
and/or the acid anhydride is: 1,2,4, 5-pyromellitic dianhydride, 3,3 ', 4,4' -benzophenone tetracarboxylic dianhydride, 4,4 '-diphenyl ether dianhydride, 3,3,4, 4-biphenyl dianhydride, 4, 4-hexafluoroisopropyl phthalic anhydride, 4,4' - (acetylene-1, 2, -diyl) diphthalic anhydride, Benzophenone Tetracarboxylic Dianhydride (BTDA), diphenylmethyl ether tetracarboxylic dianhydride (ODPA), thiodipropionic anhydride (TDPA), diphenylsulfone tetracarboxylic dianhydride (DSDA), hexafluoro dianhydride (6FDA), triphendiether tetracarboxylic dianhydride (HQDPA), bisphenol A dianhydride (BPADA), bis- (3, 4-phthalic anhydride) -dimethylsilane (SiDA), cyclobutane tetracarboxylic dianhydride (CBDA), cyclopentanetetracarboxylic dianhydride (CPDA), 1,2,3, 4-cyclohexanetetracarboxylic dianhydride (CHDA), One or more of bicyclo [2.2.2] octane-2, 3,5, 6-tetracarboxylic dianhydride (BOTDA) and bicyclo [2.2.1] hexane-2, 3,5, 6-tetracarboxylic dianhydride (BHTDA);
and/or the polar aprotic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone or dimethylsulfoxide.
3. The method for continuously synthesizing a polyimide precursor using a microreactor as claimed in claim 1, wherein the predetermined solid content in the step S1 and the predetermined solid content in the step S2 are each independently 1% to 50% by weight.
4. The method for continuously synthesizing a polyimide precursor using a microreactor as claimed in claim 1, wherein in step S3, the molar ratio of the diamine to the acid anhydride is 1: 1 to 1.1.
5. The method for continuously synthesizing the polyimide precursor by using the microreactor as claimed in claim 1, wherein in step S3, the metering device is one or more of an injection pump, a peristaltic pump or a constant flow pump.
6. The method for continuously synthesizing a polyimide precursor using a microreactor as claimed in claim 1, wherein the predetermined flow rate is 0.05ml/min to 100ml/min in step S3.
7. The method for continuously synthesizing a polyimide precursor using a microreactor as claimed in claim 1, wherein the predetermined size of the channel of the microreactor in step S3 is 0.2mm to 10 mm.
8. The method for continuously synthesizing a polyimide precursor using a microreactor as claimed in claim 1, wherein the predetermined reaction time is 10min to 24 hours in step S3.
9. The method for continuously synthesizing a polyimide precursor using a microreactor as claimed in claim 1, wherein the predetermined reaction temperature is 0 to 80 ℃ in step S3.
10. The method for continuously synthesizing a polyimide precursor using a microreactor as claimed in claim 1, wherein the polyimide precursor has a molecular weight distribution coefficient of 1.5 to 5 in step S4.
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| CN114573811A (en) * | 2021-12-29 | 2022-06-03 | 宁波博雅聚力新材料科技有限公司 | Imide slurry, synthesis method thereof and composition containing imide slurry |
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