CN107915817B - Main chain type benzoxazine containing amide structure and preparation method thereof - Google Patents
Main chain type benzoxazine containing amide structure and preparation method thereof Download PDFInfo
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- CN107915817B CN107915817B CN201711298437.8A CN201711298437A CN107915817B CN 107915817 B CN107915817 B CN 107915817B CN 201711298437 A CN201711298437 A CN 201711298437A CN 107915817 B CN107915817 B CN 107915817B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
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Abstract
The invention provides a main chain type benzoxazine containing an amide structure and a preparation method thereof, and the main chain type benzoxazine has the following structural formula:
wherein, -R1-is one of the following structures:
‑R2-is one of the following structures:
. According to the invention, an amide structure is introduced into benzoxazine molecules, so that the ring-opening curing temperature of benzoxazine is effectively reduced, and the ring-opening curing of benzoxazine can be promoted because hydrogen in an amide group and oxygen on an oxazine ring form an intermolecular hydrogen bond. Therefore, the initial curing temperature of the benzoxazine is lower than 150 ℃, the production energy consumption is obviously reduced, and the processing cost is reduced.
Description
Technical Field
The invention relates to a thermosetting resin and a preparation method thereof, in particular to a main chain type benzoxazine containing an amide structure and a preparation method thereof.
Background
The traditional phenolic resin is widely applied with good heat resistance, mechanical property, corrosion resistance and insulating property, but the application is limited because of the defects of harsh curing conditions and small molecule release during curing. The benzoxazine resin for overcoming the defects is produced at the same time, has the advantages of the traditional phenolic resin, has low shrinkage rate of a finished product during curing, and has excellent flame retardance and moisture resistance. The benzoxazine resin has wide application prospect in the aspects of high-performance novel paint, adhesive, high-temperature-resistant insulating material and the like.
The patent application published at present relates to improvement and preparation of benzoxazine, for example, application No. 200610020858.X, the heat-resistant benzoxazine resin compound, the preparation method and the application thereof, discloses that a low molecular weight curing agent containing aldehyde group activated group is introduced into a resin system, so that the crosslinking density of a cured product is further improved, the thermal stability is improved, but the preparation process is more complicated; for example, as disclosed in 'a benzoxazine containing maleic amide and allyl ether and its preparation method' with application number 200610020900.8, the benzoxazine containing maleic amide and allyl ether has the advantages of greatly improved thermal stability, greatly widened processing temperature window, easy molding, but higher preparation cost and by-product existence.
The main chain type benzoxazine is an oligomer or polymer which introduces benzoxazine groups into a high molecular chain as a repeating unit, and the structural general formula of the main chain type benzoxazine is as follows:
the precursor of the benzoxazine resin with high molecular weight can be prepared to effectively improve the thermodynamic property of the resin. However, no report has been made so far on the synthesis and application of main chain type benzoxazine containing amide structure, and the initial curing temperature of the material is reduced.
In view of the above-mentioned shortcomings of the existing benzoxazine monomer, the present inventors have made active research and innovation based on practical experience and professional knowledge that are abundant for many years in the design and manufacture of such products, and together with the application of theory, in order to create a main chain type benzoxazine containing an amide structure and a preparation method thereof, so that the benzoxazine has more practicability. After continuous research and design and repeated trial production and improvement, the invention with practical value is finally created.
Disclosure of Invention
The invention provides a main chain type benzoxazine containing an amide structure and a preparation method thereof, which can reduce the initial curing temperature.
The invention is realized by adopting the following scheme:
the main chain type benzoxazine containing an amide structure provided by the invention has the following structural formula:
wherein, -R1-is one of the following structures:
-R2-is one of the following structures:
Preferably, the glass transition temperature of the main chain type benzoxazine containing the amide structure is 360-400 ℃, and the glass transition temperature is higher than that of the conventional benzoxazine, so that the benzoxazine can be better applied to high-temperature occasions or places with higher requirements on environment, and the application range of the benzoxazine is expanded.
The preparation method of the main chain type benzoxazine containing the amide structure comprises the following operation steps:
(1) the reaction of diacyl chloride compound and p-aminophenol to prepare diphenol with amide structure includes the following reaction equation:
(2) the method is characterized in that diphenol containing an amide structure, diamine compounds and paraformaldehyde are reacted to prepare the main chain type benzoxazine containing the amide structure, and the reaction equation is as follows:
preferably, in the preparation method of the main chain type benzoxazine containing the amide structure, the molar ratio of the diacid chloride compound to the p-aminophenol in the first step is 1: 2-3, which is beneficial to the synthesis of diphenol containing the amide structure, and glacial acetic acid is used as a solvent in the reaction.
Preferably, in the preparation method of the main chain type benzoxazine containing the amide structure, the reaction temperature in the first step is 90-100 ℃, the temperature can ensure that the reaction is smoothly carried out, meanwhile, the temperature is not too high, the energy is saved, and the reaction time is 3-5 hours.
Preferably, in the preparation method of the main chain type benzoxazine containing the amide structure, the molar ratio of diphenol containing the amide structure to the diamine compound to the paraformaldehyde is 1:1: 4-5, the ratio can effectively improve the ring formation rate of benzoxazine rings, and the excessive paraformaldehyde is easy to remove.
Preferably, in the preparation method of the main chain type benzoxazine containing the amide structure, the reaction temperature in the second step is 110-130 ℃, preferably 120 ℃, the high cyclization rate of the benzoxazine can be ensured, and the reaction time is 12-14 hours.
Preferably, the second step reaction is carried out in a solvent, and the solvent is one of toluene or xylene. The toluene and the xylene have good solubility to products, and the system is a homogeneous reaction system, which is beneficial to controlling the reaction. Meanwhile, the toluene and the xylene are cheap and easy to obtain.
Preferably, the preparation method of the main chain type benzoxazine containing an amide structure comprises the following steps:
wherein, -R1-is one of the following structures:
preferably, the diamine compound is one of the following structures:
wherein, -R2-is one of the following structures:
the invention has the beneficial effects that:
(1) according to the invention, an amide structure is introduced into benzoxazine molecules, so that the ring-opening curing temperature of benzoxazine is effectively reduced, and the ring-opening curing of benzoxazine can be promoted because hydrogen in an amide group and oxygen on an oxazine ring form an intermolecular hydrogen bond. Therefore, the initial curing temperature of the benzoxazine is lower than 150 ℃, the production energy consumption is obviously reduced, and the processing cost is reduced.
(2) The amide group has good high thermal stability, so that the high temperature resistance of the polymer obtained after curing of the main chain type benzoxazine is more than 450 ℃, and the carbon residue rate at 800 ℃ is more than 70%; the preparation method is simple in preparation process, low in equipment requirement and suitable for large-scale production.
Drawings
FIG. 1 is an infrared spectrum of a main chain benzoxazine obtained in example 1;
FIG. 2 DSC of main chain benzoxazines obtained in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The method comprises the following specific operation steps:
1. mixing a diacid chloride compound and p-aminophenol, adding the mixture into a glacial acetic acid solvent system, filling inert protective gas into the reaction system, heating the system from room temperature to 100 ℃, reacting for 3-5 hours, and pouring reaction liquid into deionized water after the reaction is finished to perform precipitation, filtration, water washing and drying to obtain diphenol with an amide structure; wherein the inert protective gas is nitrogen or argon, etc.; the molar ratio of the diacid chloride compound to the p-aminophenol is 1:2-1: 3; preferably 1: 2.2.
2. Mixing diphenol containing an amide structure, a diamine compound and paraformaldehyde, adding into a xylene solvent, heating the system to 120 ℃, reacting for 12-14 hours, and settling, filtering and drying reaction liquid after the reaction is finished to obtain a product. Wherein the molar ratio of diphenol containing amide structure, diamine compound and paraformaldehyde is 1:1:4-1:1:5, and the preferred molar ratio is 1:1: 4.4.
Example 1
The preparation method of the main chain type benzoxazine containing the amide structure comprises the following specific steps:
(1) 20g of m-phthaloyl chloride, 21.6g of p-aminophenol and 70ml of glacial acetic acid are added into a reaction bottle containing a stirrer, a thermometer and a condenser tube, the reaction device is vacuumized by a vacuum pump, and then nitrogen is filled into the reaction bottle, and the steps are repeated for three times. Heating to 100 ℃ at the speed of 10 ℃/h for reaction for 3 hours under the condition of introducing nitrogen for protection. Then 200ml of deionized water was added to obtain a large amount of precipitate. After suction filtration, washing with a large amount of deionized water for three times, and drying in a vacuum box at 50 ℃ to obtain 28.3g of diphenol containing an amide structure with the yield of 82%. The reaction equation is as follows:
(2) 20g of the amide structure-containing diphenol compound obtained in the previous step, 11.4g of 4, 4-diaminodiphenylmethane, 6.9g of paraformaldehyde and 80ml of xylene are weighed and respectively added into a reaction bottle provided with a stirrer, a thermometer and a condenser tube, and the mixture is heated to 120 ℃ for reaction for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was allowed to stand for precipitation, and the precipitate was washed with water, filtered, and dried under vacuum for 12 hours to obtain 27.7g of a product with a yield of 81%. The reaction equation is as follows:
in this example, the structure of the obtained main chain benzoxazine product is:
the Fourier infrared transform spectrogram and differential scanning calorimetry characterization result of the product are shown in the attached figures 1 and 2. FIG. 1 is an infrared spectrum at 1667cm-1Characteristic absorption peak at amide group, 939cm-1The characteristic absorption peak of the oxazine ring is shown. FIG. 2 is a DSC chart obtained by differential scanning calorimetry, and it can be seen that the initial ring-opening curing temperature of the main chain type benzoxazine is 137 ℃ and the maximum curing peak temperature is 176 ℃.
After the ring-opening curing of the main-chain benzoxazine obtained in this example, the polymer weight loss 5% temperature was 540 ℃, and the carbon residue rate at 800 ℃ was 72%.
Example 2
The preparation method of the main chain type benzoxazine containing the amide structure comprises the following specific steps:
(1) 20g of m-phthaloyl chloride, 21.6g of p-aminophenol and 70ml of glacial acetic acid are added into a reaction bottle containing a stirrer, a thermometer and a condenser tube, the reaction device is vacuumized by a vacuum pump, and then nitrogen is filled into the reaction bottle, and the steps are repeated for three times. Heating to 100 ℃ at the speed of 10 ℃/h for reaction for 3 hours under the condition of introducing nitrogen for protection. Then 200ml of deionized water was added to obtain a large amount of precipitate. After suction filtration, washing with a large amount of deionized water for three times, and drying in a vacuum box at 50 ℃ to obtain 28.3g of diphenol containing an amide structure with the yield of 82%. The reaction equation is as follows:
(2) 20g of the amide structure-containing diphenol compound obtained in the previous step, 12.2g of 4, 4' -diaminobenzophenone, 6.9g of paraformaldehyde and 80ml of xylene are weighed and respectively added into a reaction bottle provided with a stirrer, a thermometer and a condenser tube, and the mixture is heated to 120 ℃ for reaction for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was allowed to stand for precipitation, and the precipitate was washed with water, filtered, and dried under vacuum for 12 hours to obtain 29.4g of a product in 84% yield. The reaction equation is as follows:
in this example, the structure of the obtained main chain benzoxazine product is:
after the ring-opening curing of the main chain type benzoxazine obtained in this example, the 5% weight loss temperature of the polymer was 554 ℃ and the carbon residue rate at 800 ℃ was 75%.
Example 3
The preparation method of the main chain type benzoxazine containing the amide structure comprises the following specific steps:
(1) 21.6g of terephthaloyl chloride, 21.6g of p-aminophenol and 70ml of glacial acetic acid are added into a reaction bottle containing a stirrer, a thermometer and a condenser tube, a reaction device is vacuumized by a vacuum pump, and then nitrogen is filled into the reaction bottle for three times. Heating to 100 ℃ at the speed of 10 ℃/h for reaction for 3 hours under the condition of introducing nitrogen for protection. Then 200ml of deionized water was added to obtain a large amount of precipitate. After suction filtration, washing with a large amount of deionized water for three times, and drying in a vacuum box at 50 ℃ to obtain 29.3g of diphenol containing an amide structure with a yield of 85%.
(2) 20g of the amide structure-containing diphenol compound obtained in the previous step, 11.4g of 4, 4-diaminodiphenylmethane, 6.9g of paraformaldehyde and 80ml of xylene are weighed and respectively added into a reaction bottle provided with a stirrer, a thermometer and a condenser tube, and the mixture is heated to 120 ℃ for reaction for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was allowed to stand for precipitation, and the precipitate was washed with water, filtered, and dried under vacuum for 12 hours to obtain 29.0g of a product in 85% yield. The reaction equation is as follows:
in this example, the structure of the obtained main chain benzoxazine product is:
after the main chain type benzoxazine obtained in the embodiment is subjected to ring opening curing, the 5% weight loss temperature of the polymer is 537 ℃, and the carbon residue rate at 800 ℃ is 73%
Example 4
The preparation method of the main chain type benzoxazine containing the amide structure comprises the following specific steps:
(1) 21.6g of terephthaloyl chloride, 21.6g of p-aminophenol and 70ml of glacial acetic acid are added into a reaction bottle containing a stirrer, a thermometer and a condenser tube, a reaction device is vacuumized by a vacuum pump, and then nitrogen is filled into the reaction bottle for three times. Heating to 100 ℃ at the speed of 10 ℃/h for reaction for 3 hours under the condition of introducing nitrogen for protection. Then 200ml of deionized water was added to obtain a large amount of precipitate. After suction filtration, washing with a large amount of deionized water for three times, and drying in a vacuum box at 50 ℃ to obtain 29.3g of diphenol containing an amide structure with a yield of 85%.
(2) 20g of the amide structure-containing diphenol compound obtained in the previous step, 12.2g of 4, 4' -diaminobenzophenone, 6.9g of paraformaldehyde and 80ml of xylene are weighed and respectively added into a reaction bottle provided with a stirrer, a thermometer and a condenser tube, and the mixture is heated to 120 ℃ for reaction for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was allowed to stand for precipitation, and the precipitate was washed with water, filtered, and dried under vacuum for 12 hours to obtain 30.1g of a product with a yield of 86%. The reaction equation is as follows:
in this example, the structure of the obtained main chain benzoxazine product is:
after the ring-opening curing of the main-chain benzoxazine obtained in the example, the 5% weight loss temperature of the polymer was 542 ℃, and the carbon residue rate at 800 ℃ was 74%.
The invention has the advantages that an amide structure is introduced into the main chain type benzoxazine as a repeating unit, the cured polymer can resist the high temperature of 450-550 ℃, the carbon residue rate is more than 70% at 800 ℃, and the polymer has very good mechanical property. The method has simple preparation process and low requirement on equipment, and is suitable for large-scale production.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. A main chain type benzoxazine containing an amide structure is characterized in that: a molecular formula having the structure:
wherein, -R1-is one of the following structures:
-R2-is one of the following structures:
2. the amide structure-containing main chain benzoxazine according to claim 1, wherein: the glass transition temperature is 360-400 ℃.
3. The method for producing a main chain type benzoxazine containing an amide structure according to claim 1 or 2, wherein: the method comprises the following operation steps:
(1) the reaction of diacyl chloride compound and p-aminophenol to prepare diphenol with amide structure includes the following reaction equation:
wherein, -R1-is one of the following structures:
(2) the method is characterized in that diphenol containing an amide structure, diamine compounds and paraformaldehyde are reacted to prepare the main chain type benzoxazine containing the amide structure, and the reaction equation is as follows:
wherein, -R1-is one of the following structures:
-R2-is one of the following structures:
4. the method for producing a main chain type benzoxazine containing an amide structure according to claim 3, wherein: the molar ratio of the diacyl chloride compound to the p-aminophenol in the step (1) is 1: 2-3, and glacial acetic acid is used as a solvent in the reaction.
5. The method for producing a main chain type benzoxazine containing an amide structure according to claim 3, wherein: the reaction temperature of the step (1) is 90-100 ℃, and the reaction time is 3-5 hours.
6. The method for producing a main chain type benzoxazine containing an amide structure according to claim 3, wherein: the molar ratio of diphenol containing an amide structure in the step (2) to diamine compound to paraformaldehyde is 1:1: 4-5.
7. The method for producing main chain type benzoxazine containing an amide structure according to claim 6, wherein: the reaction temperature in the step (2) is 110-130 ℃, and the reaction time is 12-14 hours.
8. The method for producing a main chain type benzoxazine containing an amide structure according to claim 6 or 7, wherein: the step (2) reaction is carried out in a solvent, and the solvent is one of toluene or xylene.
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