CN116640280A - Preparation method of ternary benzoxazine resin based on melamine - Google Patents
Preparation method of ternary benzoxazine resin based on melamine Download PDFInfo
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- CN116640280A CN116640280A CN202310865770.1A CN202310865770A CN116640280A CN 116640280 A CN116640280 A CN 116640280A CN 202310865770 A CN202310865770 A CN 202310865770A CN 116640280 A CN116640280 A CN 116640280A
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- melamine
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- benzoxazine resin
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- benzoxazine
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- 229920005989 resin Polymers 0.000 title claims abstract description 76
- 239000011347 resin Substances 0.000 title claims abstract description 76
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 52
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 51
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 8
- 125000003172 aldehyde group Chemical group 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 claims description 6
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 claims description 6
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 6
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 6
- 235000012141 vanillin Nutrition 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000012776 electronic material Substances 0.000 claims description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 2
- NNKQLUVBPJEUOR-UHFFFAOYSA-N 3-ethynylaniline Chemical group NC1=CC=CC(C#C)=C1 NNKQLUVBPJEUOR-UHFFFAOYSA-N 0.000 claims description 2
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical group NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 239000002262 Schiff base Substances 0.000 abstract description 3
- 150000004753 Schiff bases Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 150000005130 benzoxazines Chemical class 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 14
- 239000003292 glue Substances 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- ROBVLQBZPQQRTQ-UHFFFAOYSA-N [N].C1=CN=NN=C1 Chemical compound [N].C1=CN=NN=C1 ROBVLQBZPQQRTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- -1 heterocyclic organic compound Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
Classifications
-
- 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
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a melamine-based ternary benzoxazine resin. The method comprises the steps of firstly synthesizing ternary phenol containing Schiff base by using melamine and aldehyde phenol as raw materials through an aldehyde-amine reaction, and then reacting the ternary phenol with formaldehyde and monoamine to obtain ternary benzoxazine resin. And then polymerizing at high temperature to obtain the resin based on trisubstituted benzoxazine. The method can greatly improve the crosslinking density, heat resistance and dielectric property of the resin while reducing the curing temperature of the benzoxazine.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a melamine-based ternary benzoxazine resin.
Background
Benzoxazine is a thermosetting resin, is a compound which contains N and O six-membered oxazine rings in the structure, is widely focused because no small molecules are released in the curing process, the curing shrinkage rate is almost zero, and the benzoxazine has the advantages of high modulus, high strength, good heat resistance and the like. However, the characteristics of low crosslinking density and high brittleness limit the application scene, and the dielectric properties are not particularly excellent, and the dielectric constant is generally about 3.5, so that the dielectric material is used as a low-dielectric electronic material facing the next generation and has a certain difficulty.
Melamine is a triazine nitrogen-containing heterocyclic organic compound, which is used as a chemical raw material, is initially used for manufacturing melamine resin, and then gradually expands to the fields of adhesives, crosslinking agents, flame retardants and the like to be widely used. The method has the characteristics of low corrosion, low smoke generation, low cost, high thermal stability, good synergistic effect and the like, so that the research and development and improvement of the product are valued, and the application prospect is wide.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a preparation method of a ternary benzoxazine resin based on melamine. Firstly, synthesizing ternary phenol containing Schiff base by aldehyde-amine reaction, namely taking melamine and monohydric phenol containing aldehyde groups as raw materials, and then reacting the ternary phenol with formaldehyde and the monoamine to obtain the ternary benzoxazine resin. The method can greatly improve the crosslinking density, heat resistance and dielectric property of the resin while reducing the curing temperature of the benzoxazine, and provides reference for developing more low-cost high-performance thermosetting resin and widening the application of the high-performance thermosetting resin.
In order to achieve the purpose of the invention, the specific technical scheme of the invention is as follows:
the preparation method of the ternary benzoxazine resin based on melamine comprises the following steps:
(1) Adding melamine, a monohydric phenol containing aldehyde groups and an organic solvent to a reactor at room temperature;
(2) Heating the reaction system to a certain temperature, and stirring and reacting for a period of time to perform synthesis reaction;
(3) Dripping the solution obtained after the reaction in the step (2) into a large amount of distilled water at room temperature, uniformly stirring during dripping, and separating out white flocculent precipitate to obtain a mixture containing the white flocculent precipitate;
(4) Standing the mixture obtained in the step (3) for a period of time, filtering, changing water, precipitating, and soaking filter residues in a large amount of distilled water for a period of time;
(5) Filtering the mixture obtained in the step (4), and drying filter residues in a vacuum oven to obtain the alkylphenol; (6) Dissolving the ternary phenol obtained in the step (5) in an organic solvent, stirring and reacting with formaldehyde at a certain temperature, then dropwise adding monoamine, and stirring and reacting at a certain temperature to obtain a ternary benzoxazine resin solution; namely, the three-element benzoxazine resin solution based on melamine;
(7) And removing the solvent from the ternary benzoxazine resin solution to obtain the ternary benzoxazine resin.
The reaction formula of the preparation steps is as follows:
r1 in the reaction formula can be ether bond, etc.; r2 may be a benzene ring, phenylacetylene, methyl, ethyl, propyl, or furan group.
Further, the monohydric phenol containing aldehyde group is at least one of p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, vanillin, salicylaldehyde and aldehyde naphthol;
the monoamine is at least one of aniline, m-aminophenylacetylene, p-aminophenylacetylene, methylamine, ethylamine, propylamine and furanmethylamine.
Preferably, in the preparation method, the molar ratio of melamine to aldehyde phenol in the reaction substrate fed in step (1) is 1:3 to 1:3.5.
preferably, in the preparation method, in the reaction substrate input in the step (5), the molar ratio of the alkylphenol, the monoamine and the formaldehyde is 1:3:4 to 1:3:8.
Preferably, in the preparation method, the organic solvent in each of the step (1) and the step (5) is DMF, DMSO, DMAc or NMP, or DMF, DMSO, DMAc or NMP is a mixture of each of ethanol, butanone, acetone, toluene, dioxane and dichloromethane.
Preferably, in the preparation method, the temperature of the synthesis reaction in the step (2) is 120-130 ℃; the reaction time is 5-6 hours.
Preferably, in the preparation method, the temperature of the filter residue in the step (5) is 50-70 ℃.
Preferably, in the preparation method, the dissolution temperature of the ternary phenol and the organic solvent in the step (6) is 50+/-10 ℃, and the stirring reaction time is 0.5-1 hour; the reaction temperature after monoamine is added dropwise is 80+/-10 ℃, and the stirring reaction time is 4-6 hours.
It is a further object of the present invention to protect a melamine-based ternary benzoxazine resin prepared according to any of the above described methods.
Further, the melamine-based ternary benzoxazine resin can be used as a low-dielectric electronic material.
Preferably, the application method of the melamine-based ternary benzoxazine resin comprises the following steps: the ternary benzoxazine resin is directly used for coating film or coating.
Compared with the prior art, the invention has the following beneficial effects:
starting from the design of a molecular structure, melamine is used as a matrix to obtain the benzoxazine resin with a ternary oxazine ring structure, so that the excellent performance of the traditional benzoxazine resin is ensured, the cost is reduced, the thermal stability and the heat resistance are improved, the production cost is reduced through the introduction of melamine, the flame retardant performance is improved, and a novel preparation method is provided for producing the high-performance benzoxazine resin.
Secondly, synthesizing trifunctional phenol by using melamine and aldehyde phenol as raw materials through Schiff base synthesis reaction; and then reacting the trifunctional phenol with formaldehyde and monoamine to obtain the ternary benzoxazine resin.
The chemical structure, the reactivity and the heat resistance of the finally synthesized resin are regulated and controlled by changing the types of aldehyde phenol and amine so as to meet the requirements of different use scenes and resin types.
And (III) compared with common benzoxazine resin and benzoxazine resin containing aldehyde groups, the melamine-based ternary benzoxazine resin obtained by the method has higher crosslinking density, higher heat resistance and thermal stability and higher flame retardant capability.
(IV) the melamine-based ternary benzoxazine resin of the present invention has lower dielectric constant and dielectric loss than conventional benzoxazine resins and benzoxazine resins containing aldehyde groups.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a melamine-based ternary benzoxazine resin prepared in example 1;
FIG. 2 is an infrared spectrum of the melamine-based ternary benzoxazine resin prepared in example 2;
FIG. 3 is a DSC graph of a melamine-based ternary benzoxazine resin prepared in example 3;
fig. 4 is a TGA profile of the melamine based ternary benzoxazine resin prepared in example 4.
Detailed Description
The present invention is further illustrated by the following description of specific embodiments, which are not intended to be limiting, and various modifications or alterations can be made by those skilled in the art based on the basic idea of the invention without departing from the scope of the invention.
The reagents used in the examples below were all commercially available and were common chemicals.
Example 1:
step 1: 0.1mol of melamine and 0.35mol of p-hydroxybenzaldehyde and 150g of DMSO are added to a three-necked flask;
step 2: reflux stirring the substances in the step 1 for 5 hours at the temperature of 120 ℃, and cooling to obtain deep yellow glue solution;
step 3: standing the glue solution obtained in the step 2 at room temperature, filtering, taking brown clear filtrate, dripping the filtrate into water at room temperature, and uniformly stirring to separate out white flocculent precipitate during dripping;
step 4: standing the mixture obtained in the step 3 for a period of time, filtering, changing water, continuing to precipitate, and finally soaking the filter residue (precipitate) obtained by filtering in a large amount of distilled water for a period of time;
step 5: filtering the mixture in the step 4, and drying the precipitate in a vacuum oven at 65 ℃ to obtain brown solid resin, namely trifunctional phenol (ternary phenol);
step 6: dissolving 10g of the brown solid resin obtained in the step 5 in 10g of DMF in a three-necked flask, adding formaldehyde, and stirring and reacting for 1 hour at 50 ℃; and adding aniline into the mixture, and stirring the mixture at the temperature of 80 ℃ for reaction for 5 hours to obtain the ternary benzoxazine resin solution. Wherein, the molar ratio of the trifunctional phenol, formaldehyde and aniline is 1mol:4.5mol:3mol.
Step 7: the resulting gum solution (ternary benzoxazine resin solution) was cured in an oven at 200 ℃.
Wherein melamine is supplied by Sichuan Chemicals, paraformaldehyde, paramyxobenzaldehyde and Benzenemethylamine are purchased from the exploratory reagent platform, DMSO and DMF are purchased from Chengdu Kogyo Chemicals.
Testing to obtain cured resin with initial curing temperature of 100 ℃; the film obtained by curing at 200℃with a enthalpy of 179J/g had a CTE of 57ppm/℃and a glass transition temperature of 189℃and an initial decomposition temperature of 390℃and a dielectric constant of 3.21 at 1MHz, a dielectric loss tangent of 0.009 and a saturated water absorption of 1.1% (GB 1738-1979).
Example 2:
step 1: a mixed solvent of 0.1mol of melamine, 0.31mol of m-hydroxybenzaldehyde and 150g of DMF/ethanol (volume ratio 1:1) was added to a three-necked flask.
Step 2: and (3) refluxing and stirring the substances in the step (1) for 5 hours at the temperature of 123 ℃, and cooling to obtain the deep yellow glue solution.
Step 3: standing the glue solution obtained in the step 2 at room temperature, filtering, taking brown clear filtrate, dripping the filtrate into water at room temperature, and uniformly stirring to separate out white flocculent precipitate during dripping;
step 4: standing the mixture obtained in the step 3 for a period of time, then carrying out secondary filtration, changing water for precipitation, and finally soaking filter residues (precipitates) obtained by filtration in a large amount of distilled water for a period of time;
step 5: filtering the mixture obtained in the step 4, and drying the precipitate in a vacuum oven at 70 ℃ to obtain brown solid resin, namely trifunctional phenol (ternary phenol);
step 6: dissolving 10g of the brown solid resin obtained in the step 5 in 12g of NMP in a three-necked flask, adding formaldehyde, stirring and reacting for 0.8 hour at 50 ℃ in the three-necked flask, adding methylamine into the reacted material, stirring and reacting for 6 hours at 80 ℃ to obtain the ternary benzoxazine resin solution. Wherein, the molar ratio of the trifunctional phenol, formaldehyde and methylamine is 1mol:8mol:3mol.
Step 7: and (3) curing the obtained glue solution (ternary benzoxazine resin solution) in a baking oven at 200 ℃ to obtain the cured resin.
Wherein melamine is supplied by Sichuan Chemicals, paraformaldehyde, vanillin and methylamine are purchased from the exploratory reagent platform, and DMF, NMP and ethanol are purchased from Chengdu Kogyo chemical company.
Tested: the initial curing temperature of the obtained cured resin is 120 ℃; enthalpy of 235J/g,200 ℃ The cured film had a CTE of 65 ppm/DEG C, a glass transition temperature of 176 ℃, an initial decomposition temperature of 378 ℃, a dielectric constant of 3.40 at 1MHz, a dielectric loss tangent of 0.011, and a saturated water absorption of 1.12% (GB 1738-1979).
Example 3:
step 1: into a three-necked flask, 0.1mol of melamine, 0.3mol of salicylaldehyde and 100g of DMF were added. Melamine, salicylaldehyde, DMF were added to a three-necked flask.
Step 2: and (3) refluxing and stirring the substances in the step (1) for 4.5 hours at the temperature of 126 ℃, and cooling to obtain deep yellow glue solution.
Step 3: standing the glue solution obtained in the step 2 at room temperature, filtering, taking brown clear filtrate, dripping the filtrate into water at room temperature, and uniformly stirring to separate out white flocculent precipitate during dripping;
step 4: standing the mixture obtained in the step 3 for a period of time, then filtering again, changing water for precipitation, and soaking filter residues in a large amount of distilled water for a period of time;
step 5: filtering the mixture obtained in the step 4, and drying the precipitate in a vacuum oven at 68 ℃ to obtain the alkylphenol;
step 6: 10g of the brown solid resin obtained in the step 5 is dissolved in 14g of DMAc in a three-necked flask, formaldehyde is added at 55 ℃ and then stirred and reacted in the three-necked flask for 1 hour, and aniline is added and stirred and reacted at 80 ℃ for 6 hours to obtain a ternary benzoxazine resin solution. Wherein, the molar ratio of the trifunctional phenol, formaldehyde and aniline is 1mol:6mol:3mol.
Step 7: and (3) curing the glue solution (ternary benzoxazine resin solution) obtained in the step (6) in a drying oven at 200 ℃ to obtain the melamine-based ternary benzoxazine resin.
Wherein melamine is supplied by Sichuan Chemicals, paraformaldehyde, vanillin and aniline are purchased from exploratory reagent platforms, and DMF, DMAc are purchased from Chengdu Kogyo Chemicals.
Tested: the initial curing temperature of the obtained resin is 140 ℃; enthalpy of 132J/g,200 ℃ The cured film had a CTE of 55 ppm/DEG C, a glass transition temperature of 176 ℃, an initial decomposition temperature of 377 ℃, a dielectric constant of 3.56 at 1MHz, a dielectric loss tangent of 0.008, and a saturated water absorption of 0.9% (GB 1738-1979).
Example 4:
step 1: 0.1mol of melamine, 0.35mol of vanillin and 90g of DMAc/dioxane (volume ratio 3:1) are introduced into a three-necked flask.
Step 2: reflux stirring is carried out on the substances in the step 1 for 5 hours at 130 ℃, and the deep yellow glue solution is obtained after cooling.
Step 3: standing the glue solution obtained in the step 2 at room temperature, filtering, taking brown clear filtrate, dripping the filtrate into water at room temperature, and uniformly stirring to separate out white flocculent precipitate during dripping;
step 4: standing the mixture obtained in the step 3 for a period of time, then filtering again, changing water for precipitation, and soaking filter residues in a large amount of distilled water for a period of time;
step 5: filtering the mixture obtained in the step 4, and drying the precipitate in a vacuum oven at 69 ℃ to obtain the alkylphenol;
step 6: 10g of the brown solid resin obtained in the step 5 was dissolved in 13g of DMSO in a three-necked flask, and reacted with formaldehyde in the three-necked flask at 50℃for 1 hour with stirring, and furylmethylamine was added thereto and reacted at 80℃for 4 hours with stirring to obtain a ternary benzoxazine resin solution. Wherein, the molar ratio of the trifunctional phenol, formaldehyde and furanmethanamine is 1mol:7mol:3mol.
Step 7: and (3) curing the glue solution obtained in the step (4) in a baking oven at 200 ℃.
Wherein melamine is supplied by Sichuan Chemicals, paraformaldehyde, vanillin and furanmethanamine are purchased from exploring reagent platforms, DMSO, DMAc and dioxane are purchased from Chengdu Kogyo Chemicals.
Tested: the initial curing temperature of the obtained resin is 162 ℃; the heat enthalpy is 201J/g, the CTE of the film obtained by curing at 200 ℃ is 53 ppm/DEG C, the glass transition temperature is 173 ℃, the initial decomposition temperature is 369 ℃, the dielectric constant at 1MHz is 3.55, the dielectric loss tangent is 0.009, and the saturated water absorption is 1.13% (GB 1738-1979).
Comparative example 1:
preparation method of melamine-based ternary benzoxazine resin, the preparation method is the same as example 1, but during the development process, it was found that: because the steric effect is obvious in the melamine synthesis process, the difficulty of complete reaction of three amino groups is high, if the feeding amount of aromatic aldehyde is less than three times of the molar amount of melamine, the yield of the synthesized ternary phenol is low, and a large amount of monohydric phenol and dihydric phenol exist in the product, so that the separation and purification are difficult and the later resin performance is influenced.
When three functional groups of phenol, formaldehyde and furanmethylamine are used for synthesizing ternary benzoxazine, the mole ratio of the ternary phenol to the monoamine to the formaldehyde is 1:3:4 to 1:3:8, if the formaldehyde content is lower, the resin is difficult to polymerize, the heat resistance is poor, and if the formaldehyde content is higher, gelation is likely to occur during the synthesis.
Comparative example 2:
the preparation method of the melamine-based ternary benzoxazine resin is the same as that of example 1, and the difference is that the temperature in the step 6 is adjusted to be more than 90 ℃, and as a result, the reaction system is easy to gel out, and the target resin product cannot be obtained.
The above examples are only preferred embodiments of the present invention, but the scope of the present invention is not limited thereto. It should be noted that, for those skilled in the art, it is possible to make several improvements and modifications according to the technical solution of the present invention and the patent conception thereof without departing from the principle of the present invention, and these improvements and modifications should also be considered as the protection scope of the present invention.
Claims (10)
1. A preparation method of a melamine-based ternary benzoxazine resin is characterized by comprising the following steps: the method comprises the following steps:
(1) Adding melamine, a monohydric phenol containing aldehyde groups and an organic solvent to a reactor at room temperature;
(2) Heating the reaction system to a certain temperature, and stirring and reacting for a period of time to perform synthesis reaction;
(3) Dripping the solution obtained after the reaction in the step (2) into a large amount of distilled water at room temperature, uniformly stirring during dripping, and separating out white flocculent precipitate to obtain a mixture containing the white flocculent precipitate;
(4) Standing the mixture obtained in the step (3) for a period of time, filtering, changing water, precipitating, and soaking filter residues in a large amount of distilled water for a period of time;
(5) Filtering the mixture obtained in the step (4), and drying filter residues in a vacuum oven to obtain the alkylphenol;
(6) Dissolving the ternary phenol obtained in the step (5) in an organic solvent, stirring and reacting with formaldehyde at a certain temperature, then dropwise adding monoamine, and stirring and reacting at a certain temperature to obtain a melamine-based ternary benzoxazine resin solution;
(7) And removing the solvent from the ternary benzoxazine resin solution to obtain the ternary benzoxazine resin.
2. The method for preparing the melamine-based ternary benzoxazine resin according to claim 1, wherein the method comprises the following steps:
the monohydric phenol containing aldehyde group is at least one of p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, vanillin, salicylaldehyde and aldehyde naphthol;
the monoamine is at least one of aniline, m-aminophenylacetylene, p-aminophenylacetylene, methylamine, ethylamine, propylamine and furanmethylamine.
3. The method for preparing the melamine-based ternary benzoxazine resin according to claim 1, wherein the method comprises the following steps: in the preparation method, the mole ratio of melamine to aldehyde phenol in the reaction substrate input in the step (1) is 1:3 to 1:3.5;
in the reaction substrate input in the step (5), the mole ratio of the triphenols to the monoamines to the formaldehyde is 1:3:4 to 1:3:8.
4. the method for preparing the melamine-based ternary benzoxazine resin according to claim 1, wherein the method comprises the following steps:
the organic solvent in the step (1) and the step (5) is DMF, DMSO, DMAc or NMP or DMF, DMSO, DMAc or NMP, and the organic solvent is any one of ethanol, butanone, acetone, toluene, dioxane and dichloromethane.
5. The method for preparing the melamine-based ternary benzoxazine resin according to claim 1, wherein the method comprises the following steps: the temperature of the synthesis reaction in the step (2) is 120-130 ℃; the reaction time is 5-6 hours.
6. The method for preparing the melamine-based ternary benzoxazine resin according to claim 1, wherein the method comprises the following steps: and (3) performing vacuum drying on the filter residues in the step (5) at a temperature of 50-70 ℃.
7. The method for preparing the melamine-based ternary benzoxazine resin according to claim 1, wherein the method comprises the following steps: in the step (6), the dissolution temperature of the ternary phenol and the organic solvent is 50+/-10 ℃, and the stirring reaction time is 0.5-1 hour; the reaction temperature after monoamine is added dropwise is 80+/-10 ℃, and the stirring reaction time is 4-6 hours.
8. A melamine-based ternary benzoxazine resin prepared according to the method of any one of claims 1-7.
9. Use of the melamine-based ternary benzoxazine resin according to claim 8 in low dielectric electronic materials.
10. The method for using a melamine-based ternary benzoxazine resin according to claim 8, wherein: and directly coating or coating the obtained ternary benzoxazine resin, and then curing and forming.
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