CN113801283B - High heat-resistant Gao Cantan benzoxazine resin and preparation method thereof - Google Patents
High heat-resistant Gao Cantan benzoxazine resin and preparation method thereof Download PDFInfo
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- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229920005989 resin Polymers 0.000 title claims abstract description 35
- 239000011347 resin Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 43
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 21
- 239000011737 fluorine Substances 0.000 claims abstract description 21
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 18
- GCIUCMRUMOAHKR-UHFFFAOYSA-N 3,5-difluoropyridine-2,6-diamine Chemical compound NC1=NC(N)=C(F)C=C1F GCIUCMRUMOAHKR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000005028 tinplate Substances 0.000 claims abstract description 6
- 238000001029 thermal curing Methods 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 244000137852 Petrea volubilis Species 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- -1 benzoxazine compound Chemical class 0.000 claims 6
- 229920001568 phenolic resin Polymers 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 125000000623 heterocyclic group Chemical group 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
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- MTAODLNXWYIKSO-UHFFFAOYSA-N 2-fluoropyridine Chemical compound FC1=CC=CC=N1 MTAODLNXWYIKSO-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000005130 benzoxazines Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SNGKVNKHSAEGQZ-UHFFFAOYSA-N phenol;pyridine Chemical compound C1=CC=NC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 SNGKVNKHSAEGQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention relates to the field of resin synthesis, in particular to a high heat-resistant Gao Cantan benzoxazine resin and a preparation method thereof; 3, 5-difluoro-2, 6-diaminopyridine is used as an amine source, phenol and bisphenol A are respectively used as a phenol source to carry out condensation reaction with paraformaldehyde, two fluorine-containing pyridine type benzoxazine monomers are synthesized, and high heat resistance Gao Cantan benzoxazine resin is obtained through thermal curing; the novel benzoxazine resin prepared by the invention has high thermal stability, high carbon residue rate and good hydrophobic property, and the coating prepared by the novel benzoxazine resin has higher mechanical property, and the adhesive force to a tinplate and the pencil hardness can reach 0 grade and 6H. The resin has the advantages of easily available raw materials, simple steps, multiple choices of solvents, simplified preparation process and easy realization of industrial production.
Description
Technical Field
The invention relates to the field of resin synthesis, in particular to a high heat-resistant Gao Cantan benzoxazine resin and a preparation method thereof.
Background
The benzoxazine resin is used as a novel thermosetting resin, has the characteristics of flexible molecular design, near zero shrinkage of curing, no release of small molecules in the curing process, excellent thermal stability and flame retardant property of a cured product and the like, and has been applied to the fields of electronics, electrics, aerospace, mechanical manufacturing and the like. In recent years, due to rapid development of the electronic industry, the calculation operation speed is faster and faster, and the requirements on the performance of integrated printed circuit boards are higher and higher, resins having not only high heat resistance but also high flame retardancy are urgently needed. However, the low nitrogen content of conventional polybenzoxazine carbides can affect its application. To address this problem, an effective method has been found to dope the heteroatoms into the material, which doping process can provide more active sites and thus can significantly improve the performance of the material. Meanwhile, benzoxazines can realize the introduction of heteroatoms into a carbon skeleton due to good molecular design flexibility, which is an attractive method for preparing heteroatom-doped carbon materials. Therefore, the research carries out molecular design modification on the benzoxazine to prepare the benzoxazine with high nitrogen content and high carbon residue rate.
Pyridine has certain aromaticity because of similar structure to benzene, and chemical reaction taking the pyridine as a raw material or an intermediate is a great popularity in chemical analysis and synthesis research at present. The pyridine functional group is a six-membered heterocyclic structure containing one nitrogen heteroatom, the intramolecular and intermolecular hydrogen bonds of the resin are increased due to the existence of the electronegative nitrogen atom of the pyridine ring, and the flame retardant property of the polymer is also obviously improved due to the increase of the nitrogen element content. Meanwhile, the fluorine-containing heterocyclic structure is always a hot point developed in the resin field, and the fluorine-containing heterocyclic structure has a large proportion in a structural system and a wide application range. The fluorine-containing pyridine structure is an excellent active group, and fluorine atoms are introduced into the pyridine ring structure, so that the benzoxazine with high carbon residue and strong hydrophobicity is expected to be prepared.
Disclosure of Invention
The invention overcomes the defects of the prior art, provides the high heat-resistant Gao Cantan benzoxazine resin and the preparation method thereof, increases the carbon residue rate of the benzoxazine resin from the viewpoint of molecular design, and ensures good thermal stability.
In order to solve the technical problems, the invention adopts the following technical scheme:
the structural formula of the fluorine-containing pyridine type benzoxazine monomer comprises the following two types of monomers respectively
And->。
The structural formula of the high heat-resistant Gao Cantan benzoxazine resin comprises the following two types of resin
And->。
The preparation method of the high heat-resistant Gao Cantan benzoxazine resin comprises the steps of taking 3, 5-difluoro-2, 6-diaminopyridine as an amine source, respectively taking phenol and bisphenol A as phenol sources to carry out condensation reaction with paraformaldehyde to synthesize two fluorine-containing pyridine type benzoxazine monomers, and carrying out heat curing to obtain the high heat-resistant Gao Cantan benzoxazine resin.
Fluorine atoms are introduced into the pyridine ring structure, and the fluorine atoms and the hydrogen atoms have great approximation, and compared with the hydrogen atoms, the fluorine-containing polymer has larger electronegativity, and the formed C-F bond energy is higher, so that the fluorine-containing polymer has high structural stability, higher flame retardance and hydrophobicity, and simultaneously ensures good thermal stability and hydrophobicity.
Further, the preparation method specifically comprises the following steps:
step (1), synthesizing a fluorine-containing pyridine type benzoxazine monomer:
dissolving 3, 5-difluoro-2, 6-diaminopyridine and phenolic compound in a certain amount of organic solvent, adding into paraformaldehyde dissolved in a certain amount of organic solvent, and introducing N at 90deg.C 2 Stirring for 12h, separating out the organic solvent and water, and then vacuum drying to obtain a product, namely the fluorine-containing pyridine type benzoxazine monomer; the reaction equations are shown as (I) and (II):
(I)，
(II)；
step (2), preparing the polybenzoxazine thermosetting resin:
and dissolving the benzoxazine monomer in an organic solvent, removing the solvent from the solution in a vacuum drying oven at 50 ℃, then placing the solution in the drying oven, setting a temperature gradient for solidification, and cooling to obtain the benzoxazine thermosetting resin.
Further, in the step (1), the molar ratio of the 3, 5-difluoro-2, 6-diaminopyridine, the phenol and the paraformaldehyde is 1:3:6; the molar ratio of the 3, 5-difluoro-2, 6-diaminopyridine, bisphenol A and paraformaldehyde is 1:1:4.
Further, in the step (1), 84mL of the organic solvent is added per 0.1mol of 3, 5-difluoro-2, 6-diaminopyridine, 66mL of the organic solvent is added per 0.1mol of paraformaldehyde, and the organic solvent is a mixed solution of dioxane and ethyl acetate in a volume ratio of 2:1.
Further, in step 1, the vacuum drying is performed at 80 ℃ for 3 hours, and the yields of the products are 89% and 81%, respectively.
Preferably, in the step (2), the organic solvent is one of acetone, chloroform and dioxane.
Further, the temperature gradient in the step (2) is as follows: 130 ℃ for 1h,150 ℃ for 1h,170 ℃ for 1h,190 ℃ for 2h,210 ℃ for 2h,230 ℃ for 2h.
In addition, the invention also provides a method for preparing the polybenzoxazine coating by utilizing the benzoxazine monomer, which comprises the steps of dissolving the benzoxazine monomer in an organic solvent, spraying the solution on a pretreated tinplate, and then performing thermal curing by a temperature gradient to obtain the polybenzoxazine coating. The coating prepared from the composite material has higher mechanical property, and the adhesive force to the tinplate and the pencil hardness can reach 0 grade and 6H.
Further, the organic solvent is one of acetone, chloroform and dioxane, and the temperature gradient is as follows: 130 ℃ for 1h,150 ℃ for 1h,170 ℃ for 1h,190 ℃ for 1h.
Further, the pretreatment process of the tinplate comprises the following steps: firstly polishing by sand paper, then ultrasonically cleaning by ethanol for half an hour, and finally wiping and drying by acetone.
Compared with the prior art, the invention has the following beneficial effects:
the resin prepared by the invention introduces the fluorine-containing pyridine into the benzoxazine, increases the carbon residue rate of the benzoxazine resin, and ensures good thermal stability and hydrophobic performance of the benzoxazine resin.
The resin has the advantages of easily available raw materials, simple steps, multiple choices of solvents, simplified preparation process and easy realization of industrial production.
Drawings
FIG. 1 is an infrared spectrum of a fluorine-containing pyridine type benzoxazine monomer of example 1 of the present invention.
FIG. 2 is an infrared spectrum of a fluorine-containing pyridine type benzoxazine monomer of example 2 of the present invention.
FIG. 3 is a TGA graph of the polybenzoxazine of example 3 of this invention.
Detailed Description
The invention is further illustrated below with reference to specific examples.
Example 1
Preparation of fluoropyridine monophenol type benzoxazine: 7.25g (0.05 mol) of 3, 5-difluoro-2, 6-diaminopyridine and 14.1g (0.15 mol) of phenol are dissolved in 42mL of an organic solvent of dioxane:2:1 in ethyl acetate, the mixed solution is added in portions to 9.0g (0.30 mol) of paraformaldehyde dissolved in 198mL of an organic solvent of dioxane:2:1 in ethyl acetate, and N is introduced at 90 DEG C 2 Stirring for 12h, separating out the organic solvent and water, and then vacuum drying to obtain the product, namely the fluorine-containing pyridine type benzoxazine monomer, wherein the yield is 89%. The infrared spectrum of the prepared compound is shown in figure 1. 1483cm in FIG. 1 -1 、1608cm -1 The position is the vibration absorption peak of the benzene ring framework, 1224cm -1 Is at the position of oxazineC-N-C absorption peak at ring 1032cm -1 Is provided with a symmetrical telescopic vibration peak of C-O on an oxazine ring, 947cm -1 The structural characteristics of the fluorine-containing pyridine type benzoxazine monomer can be basically determined by an infrared spectrogram.
Example 2:
preparation of fluorine-containing pyridine bisphenol type benzoxazine: 7.25g (0.05 mol) of 3, 5-difluoro-2, 6-diaminopyridine and 11.4g (0.05 mol) of bisphenol A are dissolved in 42mL of organic solvent of dioxane:2:1 of ethyl acetate, the mixed solution is added in portions to 6.0g (0.20 mol) of paraformaldehyde dissolved in 132mL of organic solvent of dioxane:2:1 of ethyl acetate, and N is introduced at 90 DEG C 2 Stirring for 12h, separating out the organic solvent and water, and then vacuum drying to obtain the product, namely the fluorine-containing pyridine type benzoxazine monomer, wherein the yield is 81%. The infrared spectrum of the prepared compound is shown in figure 2. 1560cm in FIG. 2 -1 Is 1227 cm and 1160cm as the vibration absorption peak of benzene ring skeleton -1 Is characterized by an absorption peak of C-N-C on oxazine ring, 1039cm -1 Is provided with a symmetrical telescopic vibration peak of C-O on an oxazine ring, 946cm -1 The structural characteristics of the fluorine-containing pyridine type benzoxazine monomer can be basically determined by an infrared spectrogram.
Example 3:
preparation of polybenzoxazine: and (3) placing 0.5g of benzoxazine monomer on a glass sheet, then placing the glass sheet in a forced air drying oven, setting the temperature gradient to 130 ℃ (1 h), 150 ℃ (1 h), 170 ℃ (2 h), 190 ℃ (2 h), 210 ℃ (2 h) and 230 ℃ (2 h) for solidification, and cooling to obtain the benzoxazine thermosetting resin. The TGA profile of the resin obtained is shown in fig. 3. As can be seen from fig. 3, the temperature T5% of the weight loss of the pyridine monophenol-type benzoxazine is 332.4 ℃, the temperature T10% of the weight loss is 388.6 ℃, the carbon residue rate at 800 ℃ is 65.5%, the temperature T5% of the weight loss of the pyridine bisphenol-type benzoxazine is 348.6 ℃, the temperature T10% of the weight loss is 403.1%, and the carbon residue rate at 800 ℃ is 58.4%.
Claims (7)
1. The fluorine-containing pyridine type benzoxazine compound is characterized by comprising a monomer or a polymer, wherein the structural formula of the monomer isThe structural formula of the polymer is +.>。
2. The high heat-resistant Gao Cantan benzoxazine resin is characterized by having the structural formula of
。
3. The preparation method of the high heat-resistant Gao Cantan benzoxazine resin is characterized by comprising the following steps of:
step (1), synthesizing a fluorine-containing pyridine type benzoxazine compound:
dissolving 3, 5-difluoro-2, 6-diaminopyridine and phenolic compound in a certain amount of organic solvent, adding into paraformaldehyde dissolved in a certain amount of organic solvent, and introducing N at 90deg.C 2 Stirring for 12h, separating out the organic solvent and water, and then vacuum drying to obtain a product, namely the fluorine-containing pyridine type benzoxazine compound; when the phenolic compound is phenol, the molar ratio of the 3, 5-difluoro-2, 6-diaminopyridine, phenol and paraformaldehyde is 1:3:6; when the phenolic compound is bisphenol A, the molar ratio of the 3, 5-difluoro-2, 6-diaminopyridine, bisphenol A and paraformaldehyde is 1:1:4; the reaction equations are shown as (I) and (II):
(I)，
(II)；
step (2), preparing the polybenzoxazine thermosetting resin:
and (3) placing the benzoxazine compound in a drying oven, setting a temperature gradient for solidification, and cooling to obtain the benzoxazine thermosetting resin.
4. The method for preparing a benzoxazine resin with high heat resistance Gao Cantan according to claim 3, wherein in the step (1), 84mL of organic solvent is added to each 0.1mol of 3, 5-difluoro-2, 6-diaminopyridine, 66mL of organic solvent is added to each 0.1mol of paraformaldehyde, and the organic solvent is a mixed solution of dioxane and ethyl acetate in a volume ratio of 2:1.
5. The method for producing a benzoxazine resin with high heat resistance Gao Cantan according to claim 3, wherein the temperature gradient in the step (2) is: 130 ℃ for 1h,150 ℃ for 1h,170 ℃ for 1h,190 ℃ for 2h,210 ℃ for 2h,230 ℃ for 2h.
6. A method for preparing a polybenzoxazine coating using the benzoxazine compound according to claim 1, wherein the benzoxazine compound is dissolved in an organic solvent, the dissolved solution is sprayed on a pretreated tinplate, and then the polybenzoxazine coating is obtained by thermal curing with a temperature gradient.
7. The method for preparing a polybenzoxazine coating according to claim 6, wherein said organic solvent is one of acetone, chloroform and dioxane, and said temperature gradient is: 130 ℃ for 1h,150 ℃ for 1h,170 ℃ for 1h and 190 ℃ for 1h, wherein the pretreatment process of the tinplate comprises the following steps: firstly polishing by sand paper, then ultrasonically cleaning by ethanol for half an hour, and finally wiping and drying by acetone.
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