CN108003312B - Main chain type polybenzoxazine containing amide and imide structures and preparation method thereof - Google Patents
Main chain type polybenzoxazine containing amide and imide structures and preparation method thereof Download PDFInfo
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- CN108003312B CN108003312B CN201711295507.4A CN201711295507A CN108003312B CN 108003312 B CN108003312 B CN 108003312B CN 201711295507 A CN201711295507 A CN 201711295507A CN 108003312 B CN108003312 B CN 108003312B
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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
Abstract
The invention providesProvides a main chain type polybenzoxazine containing an amide structure and an imide structure, which is characterized in that: a molecular formula having the structure:
Description
Technical Field
The invention relates to a thermosetting resin and a preparation method thereof, in particular to a main chain type polybenzoxazine containing an amide and imide structure and a preparation method thereof.
Background
The benzoxazine resin has good environmental effect, zero shrinkage rate in the curing reaction process, good flame retardant property, good low-humidity property, wider molecular structure design range, lower dielectric constant and other excellent properties, and domestic and foreign scholars research the synthesis, structure and application of benzoxazine, and related scientific research work promotes the continuous forward development of the benzoxazine field.
The chinese patent of the present application No. 201010152884.4, "a method for producing a bisphenol a novolac benzoxazine resin", discloses a method for producing a bisphenol a novolac benzoxazine resin; the chinese patent "preparation method of diphenyl ether supported benzoxazine resin" of application No. 201010152859.6 discloses a preparation method of diphenyl ether supported benzoxazine resin; the chinese patent application No. 200910097549.6, "bis-benzoxazine containing imide structure and preparation method thereof" discloses a preparation method of bis-benzoxazine containing imide structure. The preparation method of benzoxazine resin disclosed in the prior art prepares benzoxazine with different structures and different performances by using different amine sources and phenol sources for combination. However, the prepared benzoxazine monomer has the defect of brittleness, so that the benzoxazine monomer is difficult to process into a film material, and the application range of the benzoxazine monomer is limited. In addition, no relevant report relates to a preparation method of the main chain type polybenzoxazine resin containing an amide structure and an imide structure.
In view of the above-mentioned shortcomings of the existing benzoxazine monomer, the present inventors have made extensive research and innovation based on practical experience and professional knowledge for many years in designing and manufacturing such products, and by using the theory, in order to create a main chain type polybenzoxazine containing amide and imide structures and a preparation method thereof, so that the polybenzoxazine 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 novel main chain type polybenzoxazine containing an amide and imide structure and a preparation method thereof, which can reduce the brittleness of materials.
The invention is realized by adopting the following scheme:
the main chain type polybenzoxazine containing the amide and imide structures has the following molecular formula:
n is a positive integer.
Preferably, the glass transition temperature of the main chain type polybenzoxazine containing amide and imide structures is 270-390 ℃.
The main chain type polybenzoxazine containing an amide structure and an imide structure comprises the following operation steps:
the first step is as follows: trimellitic anhydride and m/p-aminophenol are adopted to prepare diphenol containing amido and imido groups by condensation reaction under the condition of using glacial acetic acid as a solvent, and the chemical reaction equation is as follows:
the second step is that: the method comprises the following steps of taking diphenol containing acylamino and imido group prepared in the first step as a phenol source, taking diamine containing R group as an amine source, and reacting with paraformaldehyde to prepare the main chain type polybenzoxazine containing acylamino and imido group, wherein the chemical reaction equation is as follows:
wherein NH2-R-NH2Is one of the following:
the third step: and (3) dissolving the main chain type polybenzoxazine obtained in the second step in a DMSO organic solvent to prepare a solution with the mass concentration of 40-80%, and curing to obtain a target product.
Preferably, the main chain type polybenzoxazine containing amide and imide structures has a molar ratio of trimellitic anhydride to m/p-aminophenol of 1: 2-1: 2.02, preferably 1: 2.02, the ratio is favorable for the synthesis of phenol containing amide and imide structures, and the excessive m/p-aminophenol is easy to remove.
Preferably, the reaction in the first step is carried out in a glacial acetic acid solvent system, the temperature of the reaction is increased from room temperature to 120 ℃ in a step mode, the bumping of the system is prevented, the reaction time is 4-12 hours, after the reaction is stopped, the solution system is precipitated by deionized water, and then alkali washing, filtering and drying are carried out to obtain the diphenol containing the amide group and the imide group.
Preferably, the main chain type polybenzoxazine containing amide and imide structures, the diphenol containing amide groups and imide groups, different diamines and paraformaldehyde in the second step have a molar ratio of 1: 1: 4-1: 1: 4.02, preferably 1: 1: 4.02, the ratio is favorable for improving the ring forming rate of the benzoxazine, and the excessive paraformaldehyde is easy to remove.
Preferably, the reaction in the second step is carried out at 80-110 ℃ for 30-120 minutes.
Preferably, the main chain type polybenzoxazine containing the amide and imide structures is washed by low-concentration (5% -10%) sodium hydroxide after the reaction of the second step is stopped, the low-concentration sodium hydroxide solution can remove impurities in a reaction system and can not cause ring opening polymerization of benzoxazine monomers, then the polybenzoxazine is washed by deionized water, then the water is removed, the polybenzoxazine is precipitated by an organic solvent, and then the polybenzoxazine is filtered and dried to finally obtain the main chain type polybenzoxazine containing the amide and imide structures.
Preferably, the main chain type polybenzoxazine containing amide and imide structures is prepared into a solution in the third step, then the solution is poured into a mold coated with a release agent, firstly, the solution is slowly thermally treated at 100 ℃ for 24 hours to remove the solvent, and then, the solution is cured at 180-240 ℃ for 1-5 hours to obtain a target product.
The invention has the beneficial effects that:
1. the main chain type polybenzoxazine resin prepared by the invention has good toughness, improves the weakness that benzoxazine monomers have brittleness, and widens the application range of the benzoxazine resin;
2. the amide structure with strong polarity is introduced into a high-molecular main chain as a repeating unit, so that the crystallinity, melting point and strength of the polymer are greatly improved, and the resin has more excellent comprehensive performance;
3. the benzoxazine is subjected to ring-opening polymerization by adopting a thermosetting treatment mode, so that the polymerization degree of the resin is further improved, and the benzoxazine resin with higher polymerization degree, more compactness and high performance is prepared.
The preparation method of the main chain type polybenzoxazine containing the amide and imide structures, provided by the invention, comprises three steps. The first step is as follows: trimellitic anhydride and m/p-aminophenol are subjected to condensation reaction under the condition of using glacial acetic acid as a solvent to prepare diphenol containing acylamino and imido; the second step is that: using diphenol containing acylamino and imido as a phenol source, using diamine containing R group as an amine source to react with paraformaldehyde to prepare main chain type polybenzoxazine containing acylamino and imido; the third step: dissolving the main chain type polybenzoxazine obtained in the second step in an organic solvent to prepare a solution with a certain concentration, pouring the solution in a mold coated with a release agent, and curing at a high temperature to obtain a benzoxazine resin with higher polymerization degree, compactness and high performance; the operation steps are simple, and the requirements on the preparation conditions are not strict.
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 trimellitic anhydride and m/p-aminophenol according to a molar ratio, adding the mixture into a glacial acetic acid solvent system, carrying out reaction, heating the temperature from room temperature to 120 ℃ in a step mode, and removing moisture in time by using a water knockout instrument in the reaction process, wherein the reaction time is 4-12 hours. And after the reaction is stopped, precipitating the solution system by using deionized water, and then carrying out alkaline washing, filtering and drying to obtain the diphenol containing the amide group and the imide group.
2) Mixing the diphenol containing the acylamino and the imido prepared in the first step with different diamines and paraformaldehyde according to a molar ratio, and then heating to react at 80-110 ℃ for 30-120 minutes. After the reaction is stopped, washing with low-concentration (5% -10%) sodium hydroxide, then washing with deionized water, removing water, precipitating with an organic solvent, filtering, and drying to finally obtain the main chain type polybenzoxazine containing amide and imide structures.
3) And (3) dissolving the main chain type polybenzoxazine obtained in the second step in a DMSO organic solvent to prepare a solution with a certain concentration, and pouring the solution into a mold coated with a release agent. Firstly, slowly carrying out heat treatment at 100 ℃ for 24 hours to remove the solvent, and then curing at 200 ℃ for two hours to obtain the benzoxazine resin with higher polymerization degree, compactness and high performance.
Example 1
(1) 7.685g of trimellitic anhydride, 8.730g of p-aminophenol and 110mL of glacial acetic acid are added into a reaction bottle provided with a water separator and a condenser tube, the reaction is heated to 120 ℃ from room temperature, and the reaction is finished after 4-12 hours. And precipitating the solution system by using deionized water, then performing alkali washing, filtering and drying to obtain 9.538g of diphenol containing amide groups and imide groups, wherein the yield is 63.7%.
The reaction equation is as follows:
(2) 7.487g (0.02mol) of diphenol containing amide groups and imide groups obtained by the reaction in the previous step, 2.163g (0.02mol) of p-phenylenediamine and 2.403g (0.08mol) of paraformaldehyde are weighed, respectively added into a reaction bottle provided with a stirrer, a thermometer and a condenser tube, heated to 80 ℃, stirred for 0.5h, and then heated to 110 ℃ for reaction for 0.5 h. After the reaction is finished, washing with low-concentration (5% -10%) sodium hydroxide, then washing with deionized water, removing water, precipitating with an organic solvent, filtering, and drying to finally obtain the main chain type polybenzoxazine containing the amide and imide structures.
The chemical reaction equation is as follows:
(3) and (3) dissolving the main chain type polybenzoxazine obtained in the second step in a DMSO organic solvent to prepare a solution with a certain concentration, and pouring the solution into a mold coated with a release agent. The solvent was first removed by slow heat treatment at 100 ℃ for 24 hours, followed by curing at 200 ℃ for two hours to give 9.228g of the desired product in 82.3% yield.
The structural formula of the main chain type polybenzoxazine containing the amide and imide structures obtained in the embodiment is as follows:
after the main chain type benzoxazine containing amide and imide structures obtained in the example is subjected to ring opening curing, the measured weight loss temperature of the polymer at 5% is 530 ℃, and the carbon residue rate at 800 ℃ is 73%.
Example 2
(1) 7.685g of trimellitic anhydride, 8.730g of p-aminophenol and 110mL of glacial acetic acid are added into a reaction bottle provided with a water separator and a condenser tube, the reaction is heated to 120 ℃ from room temperature, and the reaction is finished after 4-12 hours. And precipitating the solution system by using deionized water, then performing alkali washing, filtering and drying to obtain 9.538g of diphenol containing amide groups and imide groups, wherein the yield is 63.7%. The reaction equation is as follows:
(2) 7.487g (0.02mol) of diphenol containing amide groups and imide groups obtained by the reaction in the previous step, 2.724g (0.02mol) of 2, 5-dimethyl-1, 4-phenylenediamine and 2.403g (0.08mol) of paraformaldehyde are respectively added into a reaction bottle provided with a stirrer, a thermometer and a condenser tube, heated to 80 ℃, stirred for 0.5h and then heated to 110 ℃ for reaction for 0.5 h. After the reaction is finished, washing with low-concentration (5% -10%) sodium hydroxide, then washing with deionized water, removing water, precipitating with an organic solvent, filtering, and drying to finally obtain the main chain type polybenzoxazine containing the amide and imide structures.
(3) And (3) dissolving the main chain type polybenzoxazine obtained in the second step in a DMSO organic solvent to prepare a solution with a certain concentration, and pouring the solution into a mold coated with a release agent. The solvent was removed by first slow heat treatment at 100 ℃ for 24 hours, followed by curing at 200 ℃ for two hours to give 9.442g of the target product in 80.2% yield.
The structural formula of the main chain type polybenzoxazine containing the amide and imide structures obtained in the embodiment is as follows:
after the main chain type benzoxazine containing amide and imide structures obtained in the example is subjected to ring opening curing, the measured weight loss temperature of the polymer at 5% is 523 ℃, and the carbon residue rate at 800 ℃ is 68%.
Example 3
(1) 7.685g of trimellitic anhydride, 8.730g of p-aminophenol and 110mL of glacial acetic acid are added into a reaction bottle provided with a water separator and a condenser tube, the reaction is heated to 120 ℃ from room temperature, and the reaction is finished after 4-12 hours. And precipitating the solution system by using deionized water, then performing alkali washing, filtering and drying to obtain 9.538g of diphenol containing amide groups and imide groups, wherein the yield is 63.7%. The reaction equation is as follows:
(2) 7.487g (0.02mol) of diphenol containing amide groups and imide groups obtained by the reaction in the previous step, 3.965g (0.02mol) of 4,4' -diaminodiphenylmethane and 2.403g (0.08mol) of paraformaldehyde are weighed, respectively added into a reaction bottle provided with a stirrer, a thermometer and a condenser tube, heated to 80 ℃, stirred for 0.5h, and then heated to 110 ℃ for reaction for 0.5 h. After the reaction is finished, washing with low-concentration (5% -10%) sodium hydroxide, then washing with deionized water, removing water, precipitating with an organic solvent, filtering, and drying to finally obtain the main chain type polybenzoxazine containing the amide and imide structures.
The chemical reaction equation is as follows:
(3) and (3) dissolving the main chain type polybenzoxazine obtained in the second step in a DMSO organic solvent to prepare a solution with a certain concentration, and pouring the solution into a mold coated with a release agent. The solvent was first removed by slow heat treatment at 100 ℃ for 24 hours, followed by curing at 200 ℃ for two hours to give 10.633g of the desired product in 81.7% yield.
The structural formula of the main chain type polybenzoxazine containing the amide and imide structures obtained in the embodiment is as follows:
after the main chain type benzoxazine containing amide and imide structures obtained in the embodiment is subjected to ring opening curing, the measured weight loss temperature of the polymer at 5% is 562 ℃, and the carbon residue rate of the polymer at 800 ℃ is 75%.
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 (9)
1. A main chain type polybenzoxazine containing an amide structure and an imide structure is characterized in that: a molecular formula having the structure:
wherein n is a positive integer, R is:
any one of them.
2. The main chain type polybenzoxazine containing an amide and an imide structure according to claim 1, wherein: the glass transition temperature is 270-390 ℃.
3. The main chain type polybenzoxazine containing an amide or imide structure according to claim 1 or 2, wherein: the method comprises the following operation steps:
the first step is as follows: trimellitic anhydride and m/p-aminophenol are adopted to prepare diphenol containing amido and imido groups by condensation reaction under the condition of using glacial acetic acid as a solvent, and the chemical reaction equation is as follows:
the second step is that: the method comprises the following steps of taking diphenol containing acylamino and imido group prepared in the first step as a phenol source, taking diamine containing R group as an amine source, and reacting with paraformaldehyde to prepare the main chain type polybenzoxazine containing acylamino and imido group, wherein the chemical reaction equation is as follows:
wherein NH2-R-NH2Is one of the following:
the third step: and (3) dissolving the main chain type polybenzoxazine obtained in the second step in a DMSO organic solvent to prepare a solution with the concentration of 40-80%, and curing to obtain a target product.
4. The main chain type polybenzoxazine containing an amide and an imide structure according to claim 3, wherein: in the first step, the molar ratio of trimellitic anhydride to m/p-aminophenol is 1: 2-1: 2.02.
5. the main chain type polybenzoxazine containing an amide and an imide structure according to claim 3, wherein: and the reaction in the first step is carried out in a glacial acetic acid solvent system, the temperature of the reaction is increased from room temperature to 120 ℃ in a step mode, the reaction time is 4-12 hours, the solution system is precipitated by deionized water after the reaction is stopped, and then alkali washing, filtering and drying are carried out to obtain the diphenol containing the amide group and the imide group.
6. The main chain type polybenzoxazine containing an amide and an imide structure according to claim 3, wherein: in the second step, diphenol containing acylamino and imido, diamine containing R group and paraformaldehyde are mixed according to a molar ratio of 1: 1: 4-1: 1: 4.02.
7. the main chain type polybenzoxazine containing an amide and an imide structure according to claim 3, wherein: the reaction in the second step is carried out at the temperature of 80-110 ℃, and the reaction time is 30-120 minutes.
8. The main chain type polybenzoxazine containing an amide or imide structure according to claim 6 or 7, wherein: and after the reaction in the second step is stopped, washing with sodium hydroxide, washing with deionized water, removing water, precipitating with an organic solvent, filtering, and drying to finally obtain the main chain type polybenzoxazine containing the amide and imide structures.
9. The main chain type polybenzoxazine containing an amide and an imide structure according to claim 3, wherein: after the solution is prepared in the third step, the solution is poured into a mold coated with a release agent, the solution is slowly thermally treated at 100 ℃ for 24 hours to remove the solvent, and then the solution is cured at 180-240 ℃ for 1-5 hours to obtain a target product.
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