CN111592502A - Biphenyl polyamine benzoxazine and preparation method thereof - Google Patents
Biphenyl polyamine benzoxazine and preparation method thereof Download PDFInfo
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- CN111592502A CN111592502A CN202010532458.7A CN202010532458A CN111592502A CN 111592502 A CN111592502 A CN 111592502A CN 202010532458 A CN202010532458 A CN 202010532458A CN 111592502 A CN111592502 A CN 111592502A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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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- 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
- 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
A biphenyl polyamine benzoxazine and a preparation method thereof belong to the field of materials. The biphenyl polyamine benzoxazine and the benzoxazine resin prepared from the biphenyl polyamine benzoxazine have low dielectric constant and dielectric loss through the introduction of a biphenyl polyamine structure, and the preparation method is simple and reliable.
Description
Technical Field
The application relates to the field of materials, in particular to a biphenylpolyamine benzoxazine and a preparation method thereof.
Background
The benzoxazine is a novel phenolic resin monomer containing a nitrogen-oxygen six-membered heterocyclic ring synthesized by taking a phenolic compound, aldehydes and amine compounds as raw materials. The ring-opening polymerization is carried out under the action of heating or catalyst, and a network structure which contains nitrogen and oxygen six-membered heterocyclic rings and is similar to phenolic resin is generated, namely the benzoxazine resin. And the benzoxazine does not release small molecular substances in the polymerization process, so that the polymerization shrinkage rate is low. Compared with the traditional phenolic resin, the polymerized benzoxazine resin has better flame retardant effect and chemical resistance, has the advantages of low viscosity, low dielectric constant, better molecular design and the like, and can be used in the fields of electronic packaging materials, high-performance resins, high-performance composite materials and the like.
However, how to further reduce the dielectric constant and the low dielectric loss to obtain more excellent effects is still the direction of continuous improvement for those skilled in the art.
Disclosure of Invention
An object of embodiments of the present application is to provide a biphenylpolyamine type benzoxazine and a method for preparing the same, which can improve at least one of the above-mentioned technical problems.
In a first aspect, embodiments of the present application provide a biphenyl polyamine benzoxazine, which has a structural formula as follows:
wherein R comprises H, alkyl, allyl or naphthalene ring group, and n is more than or equal to 1.
Optionally, n-1-5. .
The biphenyl polyamine benzoxazine with the structure has lower expansion coefficient, lower dielectric constant and dielectric loss through the introduction of the biphenyl structure.
In a second aspect, embodiments of the present application provide a method for preparing the above biphenyl polyamine type benzoxazine, comprising:
the compound is obtained by polymerizing a biphenyl polyamine compound, a phenolic compound and an aldehyde compound by a solvent method.
Wherein the aldehyde compound comprises formaldehyde and/or polyformaldehyde.
The phenolic compounds include monofunctional phenolic compounds.
The structure of the biphenylpolyamine compound is as follows:
wherein n is more than or equal to 1.
Optionally, n-1-5.
In the implementation process, the biphenylpolyamine benzoxazine is effectively prepared through proper raw material selection and a proper preparation mode (solvent method), the yield of the prepared biphenylpolyamine benzoxazine can reach more than 90%, and the utilization rate of the raw materials is effectively improved.
In one possible embodiment, the ratio of the amount of substance of the amino functional groups of the biphenylpolyamine compound to the phenolic hydroxyl functional groups of the phenolic compound is from 1:0.5 to 1:2.5 and the ratio of the amount of substance of the amino functional groups of the biphenylpolyamine compound to the aldehyde functional groups of the aldehyde compound is from 1:1 to 1: 5.
Through the reasonable proportion, complete reaction of the amino groups can be ensured, and the biphenyl polyamine benzoxazine shown in the application is generated.
In one possible embodiment, the polymerization comprises: heating a first mixed solution containing a phenolic compound and an aldehyde compound to 60-90 ℃, adding a diphenyl polyamine compound solution, and after the addition is finished, keeping the temperature at 70-120 ℃ for 0-360 min; or, the polymerizing comprises: heating the second mixed solution containing the phenolic compound, the aldehyde compound and the biphenylpolyamine compound to 60-120 ℃, and preserving the heat for 5-360 min.
In the implementation process, the reaction is milder and more controllable through the arrangement mode of adding the biphenyl polyamine compound solution in a first step-by-step mode, the dropwise added biphenyl polyamine compound can be ensured to be fully reacted, and in the adding process, the phenolic compound, the aldehyde compound and the biphenyl polyamine compound are subjected to polymerization reaction, so that the thermal insulation operation can be selected according to the actual situation after dropwise addition, and the biphenyl polyamine compound is fully reacted. And the polymerization reaction is carried out in a one-step mixing mode, so that the process is simpler.
Optionally, the addition time does not exceed 120 min.
Alternatively, the mode of addition is dropwise.
By means of dropwise addition, the dropwise added biphenyl polyamine compound can be fully and quickly reacted.
In one possible embodiment, the concentration of the solution of the biphenylpolyamine compound is 10 to 80% by mass.
In one possible embodiment, the solvent of the first mixed solution, the solvent of the second mixed solution, and the solvent of the solution of the biphenylpolyamine compound respectively include one or more of methanol, ethanol, isopropanol, N-butanol, dioxane, toluene, tetrahydrofuran, N-dimethylformamide, xylene, dimethyl sulfoxide, and methyl isobutyl ketone.
In one possible embodiment, the phenolic compound comprises phenol, m-cresol, p-cresol, allylphenol, p-tert-butylphenol, naphthol, o-phenol, and biphenol, with the o-phenol comprising o-cresol.
In one possible embodiment, the method for preparing the biphenyl polyamine type benzoxazine further comprises the following steps:
after the polymerization reaction is finished, cooling, filtering, and vacuum drying at 50-60 ℃.
In a third aspect, embodiments of the present application provide a benzoxazine resin obtained by ring-opening polymerization of the biphenylpolyamine-type benzoxazine provided in the first aspect.
The benzoxazine resin has low dielectric constant and dielectric loss, and can be used in the fields of electronic packaging materials, high-performance resins, high-performance composite materials and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a FT-IR test spectrum of the biphenylpolyamine-type benzoxazine obtained in example 2 and example 3 of the present application.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following description will be made specifically for the biphenylpolyamine-type benzoxazine and the preparation method thereof according to the embodiment of the present application:
a biphenyl polyamine type benzoxazine has the following structural formula:
wherein R comprises H, alkyl, allyl or naphthalene ring group, and n is more than or equal to 1.
Optionally, n is 1-5, for example n is 1, 2, 3, 4 or 5.
Among them, alkyl groups include, but are not limited to, methyl, ethyl, propyl, tert-butyl, and the like.
A preparation method of the biphenyl polyamine benzoxazine comprises the following steps:
the compound is obtained by polymerizing a biphenyl polyamine compound, a phenolic compound and an aldehyde compound by a solvent method.
Wherein, the structure of the biphenyl polyamine compound is as follows:
wherein n is more than or equal to 1.
Optionally, n is 1-5, for example n is 1, 2, 3, 4 or 5.
The aldehyde compound comprises formaldehyde and/or polyoxymethylene, for example, the aldehyde compound is formaldehyde or polyoxymethylene, and can also be a mixture of formaldehyde and polyoxymethylene.
The phenolic compound includes monofunctional phenolic compounds, wherein monofunctional phenolic compounds in this application refer to phenolic compounds containing only one phenolic hydroxyl group.
Specifically, the phenolic compound includes, but is not limited to, phenol, and may also be m-cresol, p-cresol, allyl phenol, p-tert-butyl phenol, naphthol, o-phenol, and biphenol, and the o-phenol includes o-cresol.
Wherein, in order to ensure that the amine functional group of the polymerized biphenyl polyamine compound is fully reacted, optionally, the ratio of the amount of the amine functional group of the biphenyl polyamine compound to the amount of the phenol hydroxyl functional group of the phenol compound is 1:0.5-1:2.5, for example, the ratio of the amount of the amine functional group of the biphenyl polyamine compound to the amount of the phenol hydroxyl functional group of the phenol compound is 1:0.5, 1:1, 1:1.5, 1:2 or 1:2.5, etc., and the ratio of the amine functional group of the biphenyl polyamine compound to the amount of the aldehyde functional group of the aldehyde compound is 1:1-1:5, for example, the ratio of the amine functional group of the biphenyl polyamine compound to the amount of the aldehyde functional group of the aldehyde compound is 1:1, 1:1.5, 1:2, 1:3, 1:3.5, 1:4 or 1:5, etc.
When the aldehyde compound is polyoxymethylene, the aldehyde functional group is obtained by converting polyoxymethylene into the molecular weight of formaldehyde.
Alternatively, there are two ways of polymerization via solvent process provided herein, respectively as follows:
in the first mode:
the polymerization comprises the following steps: heating the first mixed solution containing the phenolic compound and the aldehyde compound to 60-90 ℃, adding the diphenyl polyamine compound solution, and after the addition is finished, keeping the temperature at 70-120 ℃ for 0-360 min.
It should be noted that the mixed solution added with the solution of the biphenylpolyamine compound should be kept at a temperature of 60-90 ℃ during the addition process to improve the reaction efficiency.
Wherein the solvent of the first mixed solution and the solvent of the biphenylpolyamine compound solution respectively include: one or more of methanol, ethanol, isopropanol, N-butanol, dioxane, toluene, tetrahydrofuran, N-dimethylformamide, xylene, dimethyl sulfoxide and methyl isobutyl ketone.
Alternatively, the solvent of the first mixed solution and the solvent of the solution of the biphenylpolyamine compound are the same.
Wherein the first mixed solution can be prepared by the following steps: for example, the solvent, the phenolic compound and the aldehyde compound are added to a reaction vessel and stirred, or the phenolic compound solution and the aldehyde compound solution are mixed, which is not limited herein.
Optionally, the time for adding the solution of the biphenylpolyamine compound in the first mixed solution is more than zero and the adding time is not more than 120 min; the amount added per minute is set according to the actual manner of addition, the amount added and the time of addition, and optionally, the time of adding the solution of the biphenylpolyamine compound in the first mixed solution is 1 to 120min, further for example, 5 to 120 min.
Optionally, the adding mode is dropwise adding, and by the setting mode of the dropwise adding, the contact area is increased, so that the reaction is more sufficient, and meanwhile, the adding amount per minute in the dropwise adding process is kept unchanged.
Alternatively, the concentration of the solution of the biphenylpolyamine compound is 10 to 80% by mass, for example, the concentration of the solution of the biphenylpolyamine compound is 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80% by mass, etc.
In a second mode:
the polymerization comprises the following steps: heating the second mixed solution containing the phenolic compound, the aldehyde compound and the biphenylpolyamine compound to 60-120 ℃, and preserving the heat for 5-360 min.
Optionally, heating to 60-120 deg.C, and maintaining for 30-360 min to perform polymerization reaction.
Optionally, the solvent of the second mixed solution comprises: one or more of methanol, ethanol, isopropanol, N-butanol, dioxane, toluene, tetrahydrofuran, N-dimethylformamide, xylene, dimethyl sulfoxide and methyl isobutyl ketone.
The second mixed solution may be obtained by first mixing the phenolic compound, the aldehyde compound, and the biphenylpolyamine compound and then dissolving them in a solvent, or may be obtained by first dissolving the phenolic compound, the aldehyde compound, and the biphenylpolyamine compound, respectively, and then mixing the obtained phenolic compound solution, the aldehyde compound solution, and the biphenylpolyamine compound solution, wherein the mixing is performed at room temperature, and those skilled in the art can select the second mixed solution according to actual needs.
In both the first and second modes, during the polymerization reaction, the reaction atmosphere for heat preservation is an inert atmosphere or an air atmosphere, and may be an inert atmosphere, specifically, for example, nitrogen or argon atmosphere.
After the polymerization reaction is finished, the preparation methods of the biphenyl polyamine benzoxazine all further comprise the following steps: and after the polymerization reaction is finished, cooling to room temperature, carrying out suction filtration, and carrying out vacuum drying at 50-60 ℃ to obtain the biphenylpolyamine benzoxazine, wherein the obtained biphenylpolyamine benzoxazine is yellow or yellow transparent solid.
The application also provides a benzoxazine resin obtained by polymerizing the biphenyl polyamine benzoxazine provided by the application.
The polymerization mode of the biphenylpolyamine benzoxazine includes ring-opening polymerization under the action of heating or a catalyst to generate a phenolic resin-like network structure containing a nitrogen-oxygen six-membered heterocycle, and reference may be made to related technologies, which is not limited herein.
The biphenylpolyamine-type benzoxazine and the method for preparing the same according to the present application will be described in further detail with reference to examples.
The structures of the biphenylpolyamine compounds referred to in the following examples are all:
Example 1
A biphenyl polyamine type benzoxazine has the following structural formula:
the biphenyl polyamine benzoxazine is prepared by the following steps:
84g of the biphenylpolyamine compound is weighed and dissolved in dioxane to prepare a biphenylpolyamine compound solution with the mass concentration of 40%.
150g of dioxane, 24g of paraformaldehyde and 38g of phenol are sequentially added into a 500ml four-mouth bottle, stirred and heated to 75 ℃, a diphenyl polyamine compound solution is dropwise added into the bottle for 100min, and then the bottle is subjected to heat preservation reaction at 90 ℃ for 90 min. After the reaction is finished, the solvent is removed, and 119.09g of yellow solid is obtained, and the product yield of the biphenylpolyamine benzoxazine is 90.5%.
The yellow solid obtained was subjected to FT-IR testing at 943cm-1The characteristic absorption peak of the oxazine ring is shown, 1035cm-1、1111.5cm-1The absorption peak distribution corresponds to C-O-C symmetric and antisymmetric telescopic vibration peaks on the oxazine ring, which indicates that the oxazine ring is successfully prepared.
Example 2
A biphenyl polyamine type benzoxazine prepared by the following method:
170g of the biphenylpolyamine compound is weighed and dissolved in toluene to prepare a biphenylpolyamine compound solution with the mass concentration of 30%.
Adding 650g of toluene, 48g of paraformaldehyde and 76g of phenol into a 1000ml four-mouth bottle in sequence, stirring and heating to 80 ℃, beginning to dropwise add a biphenyl polyamine compound solution into the four-mouth bottle, and finishing dropwise adding for 100 min; then the reaction is carried out for 120min at 85 ℃. After the reaction, the solvent was removed to obtain 229.4g of a transparent yellow solid, and the yield of the biphenylpolyamine benzoxazine was 86.5%.
Example 3
A biphenyl polyamine type benzoxazine has the following structural formula:
the biphenyl polyamine benzoxazine is prepared by the following steps:
170g of the biphenylpolyamine compound is weighed and dissolved in toluene to prepare a biphenylpolyamine compound solution with the mass concentration of 60%.
500g of toluene, 48g of paraformaldehyde and 95.2g of 4-methylphenol are sequentially added into a 1000ml four-mouth bottle, the mixture is stirred and heated, when the temperature reaches 80 ℃, a biphenyl polyamine compound solution is dropwise added into the mixture for 90min, then the mixture is subjected to heat preservation reaction at 90 ℃ for 180min, and after the reaction is finished, the solvent is removed, so that 236.5g of transparent yellow solid is obtained, and the yield is 83.3%.
FT-IR test was carried out on the transparent yellow solids obtained in examples 2 and 3, and the results are shown in FIG. 1, with examples 2 and 3 at 943cm-1All appear characteristic absorption peak of oxazine ring, 1035cm-1、1111.5cm-1The distribution of absorption peaks corresponds to C-O-C symmetric and antisymmetric stretching vibration peaks on oxazine rings, which shows that the oxazine rings of examples 2 and 3 are successfully prepared.
Example 4
A biphenyl polyamine type benzoxazine has the following structural formula:
adding 84g of biphenylpolyamine compound, 24g of paraformaldehyde and 54.2g of allylphenol into a 500ml four-mouth bottle, uniformly stirring, adding 300g of dioxane, stirring for dissolving, heating to 90 ℃, keeping the temperature for reaction for 150min, and removing the solvent after the reaction is finished to obtain 88g of yellow solid with the yield of 73.5%.
The obtained clear yellow solid was subjected to FT-IR test at 943cm-1The characteristic absorption peak of the oxazine ring is shown, 1035cm-1、1111.5cm-1The absorption peak distribution corresponds to C-O-C symmetric and antisymmetric telescopic vibration peaks on the oxazine ring, which indicates that the oxazine ring is successfully prepared.
A biphenyl polyamine type benzoxazine resin is obtained by heating the biphenyl polyamine type benzoxazine provided in the embodiment 1 or the embodiment 3 to the temperature of 100 ℃ and 250 ℃ for ring-opening polymerization.
Test examples
With the biphenylpolyamine benzoxazine prepared in example 1 of the present application as a test group, bisphenol benzoxazine as a control group 1 and diamine benzoxazine as a control group 2, dielectric constant and dielectric loss were measured.
The synthesis method of the bisphenol benzoxazine of the control group 1 comprises the following steps:
adding 50g g of bisphenol A, 30g of paraformaldehyde and 100g of toluene into a three-neck flask in sequence, heating to 75 ℃, dropwise adding 43g of aniline solution (the solvent is toluene), and reacting for 2 hours under heat preservation. After the reaction is finished, the solvent is removed, and the temperature is reduced to room temperature to obtain yellow solid.
The synthesis method of diamine benzoxazine of control 2 was as follows:
adding 40g of 4, 4' -diaminodiphenylmethane, 27g of paraformaldehyde, 30g of phenol and 80g of toluene into a three-necked flask in sequence, heating to 90 ℃ for reaction for 3 hours, removing the solvent after the reaction is finished, and cooling to obtain a dark yellow solid.
The test conditions for the determination of the dielectric constant and the dielectric loss were:
electrical property test instrument: QBG-1A type quality factor measuring instrument, test frequency: 1MHZ, tested at 25 ℃.
The results are shown in table 1:
TABLE 1 comparison of Performance of control 1, control 2 and test groups
From table 1, it is apparent that the dielectric constant and dielectric loss of the biphenyl polyamine type benzoxazine used in the present application are effectively lower than those of the existing control group 1 and control group 2.
In conclusion, the biphenyl polyamine benzoxazine and the benzoxazine resin have low dielectric constant and dielectric loss by introducing the biphenyl structure into the biphenyl polyamine benzoxazine, and the solvent method is simple and controllable in operation, so that the prepared biphenyl polyamine benzoxazine and the benzoxazine resin have good performance.
The foregoing is illustrative of the present application and is not to be construed as limiting thereof, as numerous modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A biphenyl polyamine type benzoxazine is characterized in that the structural formula is as follows:
wherein R comprises H, alkyl, allyl or naphthalene ring base, and n is more than or equal to 1;
optionally, n-1-5.
2. A method for producing the biphenylpolyamine-type benzoxazine according to claim 1, comprising:
the biphenyl polyamine compound, the phenolic compound and the aldehyde compound are polymerized by a solvent method to obtain the compound;
the aldehyde compound comprises formaldehyde and/or polyformaldehyde;
the phenolic compound comprises a monofunctional phenolic compound;
the structure of the biphenyl polyamine compound is as follows:
wherein n is more than or equal to 1;
optionally, n-1-5.
3. The method for producing a biphenylpolyamine-type benzoxazine according to claim 2, wherein the ratio of the amount of the substance of the amino functional group of the biphenylpolyamine compound to the amount of the substance of the phenolic hydroxyl functional group of the phenolic compound is 1:0.5 to 1:2.5, and the ratio of the amount of the substance of the amino functional group of the biphenylpolyamine compound to the amount of the substance of the aldehyde functional group of the aldehyde compound is 1:1 to 1: 5.
4. The method for preparing biphenyl polyamine type benzoxazine according to claim 2, wherein the polymerization comprises: heating a first mixed solution containing the phenolic compound and the aldehyde compound to 60-90 ℃, adding a diphenyl polyamine compound solution, and after the addition is finished, keeping the temperature at 70-120 ℃ for 0-360 min;
or, the polymerizing comprises: and heating the second mixed solution containing the phenolic compound, the aldehyde compound and the biphenyl polyamine compound to 60-120 ℃, and preserving the heat for 5-360 min.
5. The method for producing biphenyl polyamine type benzoxazine according to claim 4, wherein the addition time is not more than 120 min;
alternatively, the mode of addition is dropwise.
6. The method for producing biphenyl polyamine type benzoxazine according to claim 4, wherein the mass concentration of the biphenyl polyamine compound solution is 10 to 80%.
7. The method for producing biphenyl polyamine type benzoxazine according to claim 4, wherein the solvent of the first mixed solution, the solvent of the second mixed solution and the solvent of the biphenyl polyamine compound solution each comprise: one or more of methanol, ethanol, isopropanol, N-butanol, dioxane, toluene, tetrahydrofuran, N-dimethylformamide, xylene, dimethyl sulfoxide and methyl isobutyl ketone.
8. The method for producing biphenylpolyamine-type benzoxazine according to any one of claims 2 to 7, wherein the phenolic compound comprises phenol, m-cresol, p-cresol, allyl phenol, p-tert-butyl phenol, naphthol, o-phenol and biphenol, and the o-phenol comprises o-cresol.
9. The method for producing biphenylpolyamine-type benzoxazine according to any one of claims 2 to 7, wherein the method for producing biphenylpolyamine-type benzoxazine further comprises:
after the polymerization reaction is finished, cooling, filtering, and vacuum drying at 50-60 ℃.
10. A benzoxazine resin obtained by ring-opening polymerization of the biphenylpolyamine-type benzoxazine of claim 1.
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