CN113651948A - Preparation method and application of benzoxazine-based modified thiol epoxy curing agent - Google Patents

Preparation method and application of benzoxazine-based modified thiol epoxy curing agent Download PDF

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CN113651948A
CN113651948A CN202110948019.9A CN202110948019A CN113651948A CN 113651948 A CN113651948 A CN 113651948A CN 202110948019 A CN202110948019 A CN 202110948019A CN 113651948 A CN113651948 A CN 113651948A
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benzoxazine
curing agent
bisphenol
phenol
amine
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夏益青
盛玉萍
刘淋泽
王炼
颜帅
石锐
赵星宇
张雪梅
廖斌
李新跃
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Sichuan University of Science and Engineering
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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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/66—Mercaptans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/24—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/25—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • 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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Abstract

The invention relates to the technical field of curing agents, and particularly relates to a preparation method and application of a benzoxazine-based modified thiol epoxy curing agent. The method comprises the following steps: the benzoxazine is prepared by Mannich reaction of a phenol source, an amine source and aldehyde in a solvent, and the benzoxazine is subjected to ring-opening reaction with polythiol to obtain the benzoxazine-modified thiol epoxy curing agent. The invention adopts a two-step method, wherein the benzoxazine is synthesized by using phenol, amine and aldehyde through Mannich reaction, and then different polythiol compounds are modified by using benzoxazine to finally form the benzoxazine modified thiol curing agent. Due to the flexible molecular structure design of benzoxazine and the diversity of thiol compounds, different benzoxazines and thiol compounds can be adopted for regulation and control, so that a modified thiol curing agent system suitable for different use requirements is designed, a convenient and effective thiol curing agent modification method is provided, and the types of thiol curing agents are greatly enriched.

Description

Preparation method and application of benzoxazine-based modified thiol epoxy curing agent
Technical Field
The invention relates to the technical field of curing agents, and particularly relates to a preparation method and application of a benzoxazine-based modified thiol epoxy curing agent.
Background
Epoxy resin is a common thermosetting resin, and the molecular structure of the epoxy resin contains one or more active epoxy groups. But the curing agent is added to cure the epoxy resin, the curing shrinkage rate is low, and the cured product has excellent thermal stability, mechanical property, adhesion, dielectric property and processability, so the epoxy resin is widely applied to the fields of coatings, industrial molds, adhesives, aerospace, electronic materials and the like. Among them, various curing agents include thiols, amines, alkalis, and acid anhydrides. Since the network morphology and the crosslinking density of the epoxy resin are determined by the curing agent, different types of curing agents affect the physical properties of the epoxy resin, the gelation time, and other properties. In addition, compared with amine curing agents, acid anhydride curing agents and other curing agents, the thiol curing agents have the advantages of low-temperature and rapid curing, can meet the requirements of certain areas with low outdoor temperature in winter, effectively improve the efficiency of engineering construction, have higher refractive index, and have high application value in the aspect of improving the transparency of resin, so the preparation and research of the thiol curing agents become important in recent years in China.
In recent years, several domestic enterprises and research institutions have successively developed novel thiol curing agents. For example: CN 110527076A provides a preparation method of a high-quality polythiol curing agent for epoxy resin, and the prepared product is colorless and transparent, has low halogen residue, is easy to recover the catalyst, has low separation cost, and has better industrial application prospect. CN 112500554A provides a latent macromolecular polythiol curing agent, a preparation method and application thereof, and polymerization reaction can be carried out at room temperature or low temperature. CN 109880075A provides a method for preparing a high-mercapto polythiol curing agent, which comprises the preparation of chlorinated polyether polyol and the preparation of polythiol curing agent, and is characterized in that: in the preparation process of the polythiol curing agent, sodium hydrosulfide and chlorinated polyether polyol are used as raw materials to react, and the system pressure is controlled to be 0.02-4.5 MPa in the reaction process. CN 110776865A provides a preparation method of polythiol curing adhesive, which mainly reduces the exothermic temperature of the adhesive during curing by adding thioglycolic acid into the formula, reduces the thermal stress and solves the problem of rapid temperature rise and heat release during curing of the adhesive. However, there are still some disadvantages in these thiol curing agents, such as: the curing temperature and the curing time need to be adjusted by adding an accelerant, the designability of the molecular structure of the curing agent is poor, the content of free formaldehyde is high, and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method and application of a benzoxazine-based modified thiol epoxy curing agent. Through the reaction of benzoxazine and mercaptan, a tertiary amine structure is introduced into the modified mercaptan curing agent, so that the smell of the mercaptan curing agent is reduced, the defects of high free formaldehyde content and the like of the traditional Mannich base modified mercaptan curing agent can be overcome, the requirements of environmental protection are met, and the application of the coating, the adhesive, the composite material and the like is expanded.
A benzoxazine-based modified thiol epoxy curing agent has a structural formula shown in formula (1):
Figure BDA0003217514510000021
wherein R is1The corresponding phenol is selected from one or more of phenol, o-methyl phenol, M-methyl phenol, p-methyl phenol, o-allyl phenol, p-allyl phenol, guaiacol, salicylaldehyde, vanillin, eugenol, naphthol, p-halophenol, p-diphenol, resorcinol, bisphenol S, bisphenol A, bisphenol F, bisphenol E, bisphenol B, bisphenol M and bisphenol Z;
R2the corresponding amine is selected from aniline, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-xylylenediamine, naphthylamine, benzylamine, methylbenzylamine, p-aminobenzylamine, benzidine, 4 '-diaminodiphenylmethane, p-methylaniline, o-methylaniline, m-methylaniline, 4-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, 3, 5-dimethylaniline, 4' -diaminodiphenyl ether, furfurylamine, methylamine, ethylamine, propylamine, isopropylamine, butylamine, tert-butylamine, cyclohexylamine, 1,3, 5-triaminobenzene, N-bis (3-aminopropyl) methylamine, N-dimethyl-1, 3-diaminopropane, tetramethylpropylenediamine, dimethyldipropylenetriamine, 4-dimethylaminobutylamine, N-methyl-1, 3-propanediamine, N, N-tetrakis (3-aminopropyl) -1, 4-butanediamine, tris (3-aminopropyl) amine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethylenepolyamine, divinylpropylamine, 1, 6-hexanediamine, ethylenediamine, N, N-bis (2-aminoethyl) -1, 2-ethylenediamine, N-methyl-2, 2-diaminodiethylamine, trientine impurity, 4' -diaminodicyclohexylmethane, 3 ' -dimethyl-4, 4' -diaminodicyclohexylmethane, methylcyclohexanediamine, aminoethylpiperazine, methylcyclopentamine, o-diaminomethylcyclopentane, (2, 3-dimethyl) dibutylenetriamine, triaminononane, tetramethylenediamine, triaminononane, triaminetriamine, and mixtures thereof, One or more of dicyandiamide, adipic acid dihydrazide, mixed amine and hybrid amine;
R3the corresponding polythiol is selected from pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptopropionate), inositol hexakis (mercaptopropionate), tetraethyleneglycol bis (3-Mercaptopropionic acid), pentaerythritol tetrakis (3-mercaptobutanoate), cyanuric acid, dimercaptoethyl sulfide, 3, 6-dioxo-1, 8-octanedithiol, 2, 3-butanedithiol, 1, 5-pentanedithiol, 1, 4-benzenedithiol, 4-biphenyldithiol, 1, 2-benzenedimethylthiol, bis (2-mercaptoethyl) ether, 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 6-hexanedithiol, 1, 9-nonanedithiol, 1, 8-octanedithiol, 1, 16-hexadecanedithiol, 2, 3-dithio (2-mercapto) -1-propanethiol, 1, 4-benzenedimethylthiol, 1, 2-butanedithiol, 1, 10-decanedithiol, 1, 3-decanedithiol, One or more of Karenz MT NR1 trifunctional thiols;
the value range of n is that n is more than or equal to 2.
According to the second technical scheme, the preparation method of the benzoxazine-based modified thiol epoxy curing agent comprises the following steps:
performing ring-opening reaction on benzoxazine and polythiol to obtain the benzoxazine modified thiol epoxy curing agent, wherein the structural formula of the benzoxazine is shown as a formula (2):
Figure BDA0003217514510000031
the specific reaction route is as follows:
Figure BDA0003217514510000032
further, the polythiol is selected from pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptopropionate), inositol hexakis (mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), cyanuric acid, dimercaptoethyl sulfide, 3, 6-dioxo-1, 8-octanedithiol, 2, 3-butanedithiol, 1, 5-pentanethiol, 1, 4-benzenedithiol, 4-biphenyldithiol, 1, 2-benzenedimethylthiol, bis (2-mercaptoethyl) ether, 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 6-hexanedithiol, 1, 6-hexanedithiol, and mixtures thereof, 1, 9-nonanedithiol, 1, 8-octanedithiol, 1, 16-hexadecanedithiol, 2, 3-dithio (2-mercapto) -1-propanethiol, 1, 4-benzenedimethylmercaptan, 1, 2-butanedithiol, 1, 10-decanedithiol, and Karenz MT NR1 trifunctional thiol.
Further, the molar ratio of the benzoxazine to the polythiol is (1-4) to (1-20), and the ring-opening reaction specifically comprises the following steps: reacting for 2-24h at 30-140 ℃ under inert atmosphere.
Further, the benzoxazine is prepared by a Mannich reaction of a phenol source, an amine source and aldehyde in a solvent. The specific reaction route is as follows:
Figure BDA0003217514510000041
further, the phenol source is one or more of phenol, o-methyl phenol, M-methyl phenol, p-methyl phenol, o-allyl phenol, p-allyl phenol, guaiacol, salicylaldehyde, vanillin, eugenol, naphthol, p-halophenol, p-diphenol, resorcinol, bisphenol S, bisphenol a, bisphenol F, bisphenol E, bisphenol B, bisphenol M, bisphenol Z, and the aldehyde is formaldehyde or paraformaldehyde.
Further, the amine source is aniline, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-xylylenediamine, naphthylamine, benzylamine, methylbenzylamine, p-aminobenzylamine, benzidine, 4 '-diaminodiphenylmethane, p-methylaniline, o-methylaniline, m-methylaniline, 4-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, 3, 5-dimethylaniline, 4' -diaminodiphenyl ether, furfurylamine, methylamine, ethylamine, propylamine, isopropylamine, butylamine, t-butylamine, octadecylamine, cyclohexylamine, 1,3, 5-triaminobenzene, N-bis (3-aminopropyl) methylamine, N-dimethyl-1, 3-diaminopropane, tetramethylpropylenediamine, dimethyldipropylenetriamine, 4-dimethylaminobutylamine, N-methyl-1, 3-propanediamine, N, N-tetrakis (3-aminopropyl) -1, 4-butanediamine, tris (3-aminopropyl) amine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethylenepolyamine, divinylpropylamine, 1, 6-hexanediamine, ethylenediamine, N, N-bis (2-aminoethyl) -1, 2-ethylenediamine, N-methyl-2, 2-diaminodiethylamine, trientine impurity, 4' -diaminodicyclohexylmethane, 3 ' -dimethyl-4, 4' -diaminodicyclohexylmethane, methylcyclohexanediamine, aminoethylpiperazine, methylcyclopentamine, o-diaminomethylcyclopentane, (2, 3-dimethyl) dibutylenetriamine, triaminononane, tetramethylenediamine, triaminononane, triaminetriamine, and mixtures thereof, One or more of dicyandiamide, adipic acid dihydrazide, mixed amine and hybrid amine.
Further, the molar ratio of the phenol source to the amine source to the aldehyde is 1:1: 2.0-2.5; the solvent is one or more of water, toluene, 1, 4-dioxane, cyclohexanone, ethyl acetate, trichloromethane, xylene, butanone, methyl isobutyl ketone, DMF, DMAc and NMP; the total mass fraction of the phenol source, the amine source and the aldehyde in the solvent is 20-90%.
Further, the method specifically comprises the following steps: and (3) placing the phenol source and the aldehyde into a solvent, uniformly mixing, then adding the amine source in batches, heating to 80-110 ℃, stirring and reacting for 4-12 hours to obtain the product benzoxazine.
According to the third technical scheme, the benzoxazine-based modified thiol epoxy curing agent is applied to adhesives, coatings and composite materials cured at medium temperature and/or low temperature.
Further, the medium temperature range is 80-110 ℃, and the room temperature range is 20-40 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a two-step method, wherein the benzoxazine is synthesized by the Mannich reaction of phenol, amine and aldehyde, and then the benzoxazine is adopted to modify different polythiol compounds, so as to finally form the benzoxazine modified thiol curing agent. Due to the flexible molecular structure design of benzoxazine and the diversity of thiol compounds, different benzoxazines and thiol compounds can be adopted for regulation and control, so that a modified thiol curing agent system suitable for different use requirements is designed, a convenient and effective thiol curing agent modification method is provided, and the types of thiol curing agents are greatly enriched.
According to the curing agent disclosed by the invention, a tertiary amine structure is introduced into a molecular structure of the curing agent due to the access of benzoxazine, so that the reaction between an epoxy group and a thiol compound is promoted, and a tertiary amine accelerator is not required to be additionally added. Through benzoxazine modification, the molecular weight of the thiol curing agent is adjusted, so that the pungent smell of the thiol curing agent can be reduced or eliminated, and the construction conditions are improved. In addition, the use of excessive formaldehyde can be eliminated through a two-step synthesis process, so that the formaldehyde content in the mercaptan curing agent is effectively controlled, and the effect of environmental protection is achieved.
The benzoxazine modified thiol epoxy curing agent is prepared by two-step reaction: the first step is to synthesize benzoxazine, and the second step is to add polythiol to open the oxazine ring to obtain benzoxazine modified thiol curing agent. According to the invention, through the reaction of benzoxazine and mercaptan, a tertiary amine structure is introduced into the modified mercaptan curing agent, so that the curing reaction of mercaptan and epoxy resin is promoted. The structure of the tertiary amine can be divided into aliphatic and aromatic, the activity of the tertiary amine in the aliphatic is higher than that of the aromatic, namely, the curing agent containing the aliphatic tertiary amine structure has lower temperature and shorter time required by the curing of the epoxy resin in the using process; and the more the tertiary amine structures in the modified thiol curing agent are in a certain range, the shorter the time required for curing the epoxy resin is, and the lower the curing temperature is. The adjustment of curing temperature and curing time is realized by regulating and controlling the type and the content of a tertiary amine structure in the structure of the modified mercaptan curing agent, and different process conditions and performance requirements of the epoxy resin are met. The benzoxazine is introduced into the mercaptan curing agent, so that the smell of the mercaptan curing agent is reduced, the defects of high free formaldehyde content and the like of the traditional Mannich base modified mercaptan curing agent can be overcome, the requirements of environmental protection are met, and the application of the coating, the adhesive, the composite material and the like is expanded.
Drawings
FIG. 1 is an infrared spectrum of a benzoxazine prepared in example 1;
FIG. 2 is an infrared spectrum of the benzoxazine modified thiol curing agent prepared in example 2;
FIG. 3 is an infrared spectrum of the benzoxazine modified thiol curing agent prepared in example 3;
fig. 4 is an infrared spectrum of the benzoxazine modified thiol curing agent prepared in example 4.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
18.82g (0.2mol) of phenol, 13.2g (0.44mol) of paraformaldehyde and 200mL of toluene are sequentially added into a three-neck flask provided with a mechanical stirrer, a condenser and a thermometer, and the three-neck flask is placed in an oil bath to slowly raise the temperature to 55 ℃; and then adding 20.44g (0.2mol) of N, N-dimethyl-1, 3-diaminopropane at intervals of 15min in three batches, wherein the mass fraction of solute in the system is 30%, heating to 85 ℃ after the N, N-dimethyl-1, 3-diaminopropane is completely added, stirring for reacting for 4h, washing and drying after the reaction is finished to obtain light yellow liquid, namely benzoxazine P-dampa, the structure of which is shown in formula (3), and the yield is 92.7%.
Figure BDA0003217514510000061
The prepared benzoxazine was subjected to infrared spectroscopic analysis, and the results are shown in fig. 1. As can be seen from the figure, 921cm-1Is a characteristic absorption peak of the oxazine ring of 1034cm-1And stretching vibration peak of C-O-C, 1137cm-1The peak of C-N-C stretching vibration is shown. Therefore, the structure of the synthesized benzoxazine P-dampa is correct.
Example 2
4.42g (0.02mol) of benzoxazine P-dampa prepared in example 1 and 9.78g (0.02mol) of pentaerythritol tetra-3-mercaptopropionate are sequentially added into a three-necked flask provided with a magnetic stirring device, a condenser and a thermometer, and the mixture is placed in an oil bath to be slowly heated to 90 ℃ under the conditions of no solvent and nitrogen protection and stirred for reaction for 3 hours to obtain the curing agent I, wherein the structure of the curing agent I is shown as the formula (4), and the yield is 95.8%.
Figure BDA0003217514510000071
The infrared spectroscopic analysis of the obtained curing agent (i) was carried out, and the results are shown in FIG. 2. As can be seen from the figure, 921cm-1The characteristic peak of the oxazine ring disappears, 3457cm-1An absorption peak with-OH is generated, and the ring opening of the oxazine ring is indicated; and 2569cm-1is-SH stretching vibration peak, 1738cm-1Is C ═ O stretching vibration peak, 1240cm-1And 1047cm-1Is a C-O-C stretching vibration peak, 1154cm-11391cm is a C-N-C stretching vibration peak-1Is in the position of-CH3The peak of vibration of (1). This indicates that the synthesized compound has a correct structure。
Example 3
0.88g (4mmol) of benzoxazine P-dampa prepared in example 1 and 9.78g (0.02mol) of pentaerythritol tetra-3-mercaptopropionate are sequentially added into a three-necked flask provided with a magnetic stirring device, a condenser and a thermometer, and the three-necked flask is placed in an oil bath to slowly raise the temperature to 90 ℃ under the conditions of no solvent and nitrogen protection, stirred and reacted for 3 hours to obtain a curing agent, wherein the structure of the curing agent is shown as a formula (4), and the yield is 98.3%.
The infrared spectroscopic analysis was performed on the prepared curing agent (c), and the result is shown in fig. 3. As can be seen from the figure, 921cm-1The characteristic peak of the oxazine ring disappears, 3466cm-1An absorption peak with-OH is generated, and the ring opening of the oxazine ring is indicated; and 2569cm-1is-SH stretching vibration peak, 1737cm-1Is C ═ O stretching vibration peak, 1240cm-1And 1048cm-1Is a C-O-C stretching vibration peak, 1154cm-11392cm is a C-N-C stretching vibration peak-1Is in the position of-CH3The peak of vibration of (1). This indicates that the synthesized compound has a correct structure.
Example 4
0.44g (2mmol) of benzoxazine P-dampa prepared in example 1 and 9.78g (0.02mol) of pentaerythritol tetra-3-mercaptopropionate are sequentially added into a three-necked flask provided with a magnetic stirring device, a condenser and a thermometer, and the three-necked flask is placed in an oil bath to slowly raise the temperature to 90 ℃ under the conditions of no solvent and nitrogen protection, and stirred for reaction for 3 hours to obtain a curing agent (III), wherein the structure of the curing agent is shown as a formula (4) and the yield is 96.4%.
The infrared spectrum analysis of the prepared curing agent (c) is shown in fig. 4. As can be seen from the figure, 921cm-1The characteristic peak of the oxazine ring disappears, 3468cm-1An absorption peak with-OH is generated, and the ring opening of the oxazine ring is indicated; and 2569cm-1is-SH stretching vibration peak, 1738cm-1Is C ═ O stretching vibration peak, 1239cm-1And 1048cm-1Is a C-O-C stretching vibration peak, 1154cm-11391cm is a C-N-C stretching vibration peak-1Is in the position of-CH3The peak of vibration of (1). This indicates that the synthesized compound has a correct structure.
The curing agents prepared in examples 2,3 and 4 were mixed with epoxy E-44, and the gelation time thereof was measured, and the results are shown in Table 1. As can be seen from the table, the three curing agents all had a short gelation time, and low-temperature curing was achieved. As the proportion of mannich base increases, the curing time decreases dramatically, so the curing time can be adjusted by adjusting the benzoxazine ratio.
TABLE 1
Figure BDA0003217514510000081
Example 5
18.82g (0.2mol) of phenol, 35.68g (0.44mol) of 37% formaldehyde aqueous solution and 250mL of xylene are sequentially added into a three-mouth bottle provided with a mechanical stirrer, a condenser and a thermometer, and the mixture is put into an oil bath to be slowly heated to 50 ℃; and then adding 39.65g (0.2mol) of 4,4' -diaminodiphenylmethane in three batches at intervals of 15min, wherein the mass fraction of the solute in the system is 32.7%, slowly heating to 85 ℃ after the 4, 4-diaminodiphenylmethane is completely added, stirring for reaction for 5h, washing and drying after the reaction is finished to obtain a light yellow liquid, namely benzoxazine P-ddm, the structure of which is shown in the formula (5), and the yield of which is 95.3%.
Figure BDA0003217514510000082
Example 6
18.82g (0.2mol) of phenol, 35.68g (0.44mol) of 37% formaldehyde aqueous solution and 200mL of 1, 4-dioxane are sequentially added into a three-neck flask provided with a mechanical stirrer, a condenser and a thermometer, and the three-neck flask is placed in an oil bath to be slowly heated to 55 ℃; then, every 15min, adding 21.63g (0.2mol) of m-phenylenediamine in three batches, wherein the mass fraction of solute in the system is 35.8%, slowly heating to 82 ℃ after the m-phenylenediamine is completely added, stirring for reaction for 5h, washing and drying after the reaction is finished to obtain light yellow liquid, namely benzoxazine P-mpd, the structure of which is shown in formula (6), and the yield is 86.5%.
Figure BDA0003217514510000091
Example 7
18.82g (0.2mol) of phenol, 35.68g (0.44mol) of 37% formaldehyde aqueous solution and 200mL of dioxane are sequentially added into a three-neck flask provided with a mechanical stirrer, a condenser and a thermometer, and the three-neck flask is placed in an oil bath to be slowly heated to 52 ℃; and then adding 27.238g (0.2mol) of m-xylylenediamine in three batches at intervals of 15min, wherein the mass fraction of the solute in the system is 29.6%, slowly heating to 85 ℃ after the m-xylylenediamine is completely added, stirring for reaction for 5h, and washing and drying after the reaction is finished to obtain a light yellow liquid, namely the benzoxazine P-mxda, the structure of which is shown in the formula (7), and the yield of which is 88.2%.
Figure BDA0003217514510000092
Example 8
The benzoxazine P-ddm 8.69g (0.02mol) prepared in example 5 and pentaerythritol tetra-3-mercaptopropionate 9.78g (0.02mol) are sequentially added into a three-necked flask provided with a magnetic stirring device, a condenser and a thermometer, and the three-necked flask is placed in an oil bath to slowly raise the temperature to 50 ℃ under the conditions of no solvent and nitrogen protection, and is stirred for reaction for 3 hours to obtain the modified curing agent, wherein the structure of the modified curing agent is shown as the formula (8), and the yield is 97.2%.
Figure BDA0003217514510000101
Example 9
4.34g (0.01mol) of benzoxazine P-ddm prepared in example 5 and 15.66g (0.02mol) of inositol hexakis (mercaptopropionate) are sequentially added into a three-necked flask provided with a magnetic stirring device, a condenser and a thermometer, and the mixture is placed in an oil bath under the conditions of no solvent and nitrogen protection, slowly heated to 40 ℃ and stirred for reaction for 5 hours to obtain the modified curing agent, wherein the structure of the modified curing agent is shown as the formula (9), and the yield is 98.1%.
Figure BDA0003217514510000102
Example 10
3.45g (0.01mol) of benzoxazine P-mpd prepared in example 6 and 3.01g (0.02mol) of 1, 6-hexanedithiol are sequentially added into a three-necked flask provided with a magnetic stirring device, a condenser and a thermometer, and the three-necked flask is placed in an oil bath to be slowly heated to 60 ℃ under the conditions of no solvent and nitrogen protection, and stirred for reaction for 4 hours to obtain the modified curing agent, wherein the structure of the modified curing agent is shown as the formula (10), and the yield is 92.3%.
Figure BDA0003217514510000103
Example 11
The benzoxazine P-mxda 3.725g (0.01mol) prepared in example 7 and 3.01g (0.02mol) of 1, 6-hexanedithiol are sequentially added into a three-necked flask provided with a magnetic stirring device, a condenser and a thermometer, and the three-necked flask is placed in an oil bath to slowly raise the temperature to 80 ℃ under the conditions of no solvent and nitrogen protection, and stirred for 5 hours to react to obtain the modified curing agent, wherein the structure of the modified curing agent is shown in the formula (11), and the yield is 90.8%.
Figure BDA0003217514510000111
Example 12
The benzoxazine P-mxda 3.725g (0.01mol) prepared in example 7 and pentaerythritol tetra-3-mercaptopropionate 9.78g (0.02mol) are sequentially added into a three-necked flask provided with a magnetic stirring device, a condenser and a thermometer, and the three-necked flask is placed in an oil bath to slowly raise the temperature to 60 ℃ under the conditions of no solvent and nitrogen protection, and stirred for reaction for 4 hours to obtain the modified curing agent, wherein the structure of the modified curing agent is shown as the formula (12), and the yield is 94.9%.
Figure BDA0003217514510000112
Example 13
3.45g (0.01mol) of benzoxazine P-mpd prepared in example 6 and 9.78g (0.02mol) of pentaerythritol tetra-3-mercaptopropionate are sequentially added into a three-necked flask provided with a magnetic stirring device, a condenser and a thermometer, and the mixture is placed in an oil bath to be slowly heated to 50 ℃ under the conditions of no solvent and nitrogen protection, and stirred for reaction for 4 hours to obtain the modified curing agent, wherein the structure of the modified curing agent is shown as the formula (13), and the yield is 91.1%.
Figure BDA0003217514510000121
Example 14
The benzoxazine P-mxda 3.725g (0.01mol) prepared in example 7 and the inositol hexakis (mercaptopropionate) 15.66g (0.02mol) are sequentially added into a three-necked flask provided with a magnetic stirring device, a condenser and a thermometer, and placed in an oil bath under the conditions of no solvent and nitrogen protection, the temperature is slowly raised to 40 ℃, and the modified curing agent is obtained after stirring reaction for 5 hours, wherein the structure of the modified curing agent is shown as a formula (14), and the yield is 92.2%.
Figure BDA0003217514510000122
Example 15
9.41g (0.1mol) of phenol, 22.83g (0.1mol) of bisphenol A, 19.8g (0.66mol) of paraformaldehyde and 300mL of toluene are sequentially added into a three-necked bottle provided with a mechanical stirrer, a condenser and a thermometer, 29.14g (0.3mol) of furfurylamine is added, the temperature is increased to 90 ℃, stirring reaction is carried out for 5 hours, and washing and drying are carried out after the reaction is finished to obtain yellow liquid, namely benzoxazine P-BA-fa, wherein the yield is 89.2%.
Example 16
28.23g (0.3mol) of phenol, 19.8g (0.66mol) of paraformaldehyde and 300mL of toluene are sequentially added into a three-necked bottle provided with a mechanical stirrer, a condenser and a thermometer, 19.83g (0.1mol) of 4,4' -diaminodiphenylmethane and 9.31g (0.1mol) of aniline are added, the temperature is raised to 90 ℃, the stirring reaction is carried out for 5 hours, and after the reaction is finished, washing and drying are carried out to obtain light yellow liquid, namely benzoxazine P-a-ddm, wherein the yield is 86.7%.
Example 17
Benzoxazine P-BA-fa (0.02mol) prepared in example 15 and pentaerythritol tetra-3-mercaptopropionate (0.02mol) were added in sequence into a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer, and placed in an oil bath under the conditions of no solvent and nitrogen protection and slowly heated to 30 ℃ to be stirred and reacted for 15 hours to obtain the modified curing agent with the yield of 85.5%.
Example 18
Benzoxazine P-a-ddm (0.02mol) prepared in example 16 and pentaerythritol tetra-3-mercaptopropionate (0.02mol) were sequentially added into a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer, and placed in an oil bath under the conditions of no solvent and nitrogen protection to slowly raise the temperature to 40 ℃ for stirring reaction for 12 hours to obtain a modified curing agent with a yield of 81.9%.
Example 19
Benzoxazine P-ddm (0.02mol), pentaerythritol tetra-3-mercaptopropionate (0.01mol) and 1, 6-hexanedithiol (0.01mol) prepared in example 5 were added in sequence into a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer, and placed in an oil bath under the conditions of no solvent and nitrogen protection to slowly raise the temperature to 40 ℃ and stirred for reaction for 10 hours to obtain a modified curing agent with a yield of 86.3%.
Example 20
Benzoxazine P-BA-fa (0.02mol) prepared in example 15, pentaerythritol tetra-3-mercaptopropionate (0.01mol) and 1, 6-hexanedithiol (0.01mol) were added in sequence in a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer, and placed in an oil bath under the conditions of no solvent and nitrogen protection to slowly raise the temperature to 50 ℃ and stirred for reaction for 8 hours to obtain a modified curing agent with a yield of 84.3%.
Through further verification of products of examples 8-14 and 17-20, the result shows that the gelation time of the obtained benzoxazine modified amine curing agent is within the range of 15 s-100 s at 50 ℃; the gelation time is within the range of 28 s-150 s at the temperature of 40 ℃; the gelation time is in the range of 50s to 250s at 30 ℃.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A benzoxazine-based modified thiol epoxy curing agent is characterized in that the structural formula is shown as formula (1):
Figure FDA0003217514500000011
wherein R is1The corresponding phenol is selected from one or more of phenol, o-methyl phenol, M-methyl phenol, p-methyl phenol, o-allyl phenol, p-allyl phenol, guaiacol, salicylaldehyde, vanillin, eugenol, naphthol, p-halophenol, p-diphenol, resorcinol, bisphenol S, bisphenol A, bisphenol F, bisphenol E, bisphenol B, bisphenol M and bisphenol Z;
R2the corresponding amine is selected from aniline, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-xylylenediamine, naphthylamine, benzylamine, methylbenzylamine, p-aminobenzylamine, benzidine, 4 '-diaminodiphenylmethane, p-methylaniline, o-methylaniline, m-methylaniline, 4-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, 3, 5-dimethylaniline, 4' -diaminodiphenyl ether, furfurylamine, methylamine, ethylamine, propylamine, isopropylamine, butylamine, tert-butylamine, cyclohexylamine, 1,3, 5-triaminobenzene, N-bis (3-aminopropyl) methylamine, N-dimethyl-1, 3-diaminopropane, tetramethylpropylenediamine, dimethyldipropylenetriamine, 4-dimethylaminobutylamine, N-methyl-1, 3-propanediamine, N, N-tetrakis (3-aminopropyl) -1, 4-butanediamine, tris (3-aminopropyl) amine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethylenepolyamine, divinylpropylamine, 1, 6-hexanediamine, ethylenediamine, N, N-bis (2-aminoethyl) -1, 2-ethylenediamine, N-methyl-2, 2-diaminodiethylamine, trientine impurity, 4' -diaminodicyclohexylmethane, 3 ' -dimethyl-4, 4' -diaminodicyclohexylmethane, methylcyclohexanediamine, aminoethylpiperazine, methylcyclopentamine, o-diaminomethylcyclopentane, (2, 3-dimethyl) dibutylenetriamine, triaminononane, tetramethylenediamine, triaminononane, triaminetriamine, and mixtures thereof, One or more of dicyandiamide, adipic acid dihydrazide, mixed amine and hybrid amine;
R3the corresponding polythiol is selected from pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptopropionate), inositol hexakis (mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), cyanuric acid, dimercaptoethyl sulfide, 3, 6-dioxo-1, 8-octanedithiol, 2, 3-butanedithiol, 1, 5-pentanedithiol, 1, 4-benzenedithiol, 4-biphenyldithiol, 1, 2-benzenedimethylthiol, bis (2-mercaptoethyl) ether, 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 6-hexanedithiol, 1, 9-nonanedithiol, 1, 8-octanedithiol, 1, 16-hexadecanedithiol, 2, 3-dithio (2-mercapto) -1-propanethiol, 1, 4-benzenedimethylthiol, 1, 2-butanedithiol, 1, 10-decanedithiol, Karenz MT NR1 trifunctional thiol;
the value range of n is that n is more than or equal to 2.
2. The preparation method of the benzoxazine-modified thiol epoxy-based curing agent according to claim 1, comprising the following steps:
performing ring-opening reaction on benzoxazine and polythiol to obtain the benzoxazine modified thiol epoxy curing agent, wherein the structural formula of the benzoxazine is shown as a formula (2):
Figure FDA0003217514500000021
3. the method of claim 2, wherein the polythiol is selected from pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptopropionate), inositol hexakis (mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), thiocyanic acid, dimercaptoethyl sulfide, 3, 6-dioxo-1, 8-octanedithiol, 2, 3-butanedithiol, 1, 5-pentanethiol, 1, 4-benzenedithiol, 4-benzenedithiol, 1, 2-benzenedimethylthiol, bis (2-mercaptoethyl) ether, bis (3-mercaptopropionic acid), tetrakis (3-mercaptobutanoic acid) pentaerythritol ester, 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 6-hexanedithiol, 1, 9-nonanedithiol, 1, 8-octanedithiol, 1, 16-hexadecanedithiol, 2, 3-dithio (2-mercapto) -1-propanethiol, 1, 4-benzenedimethylthiol, 1, 2-butanedithiol, 1, 10-decanedithiol, and Karenz MT 1 trifunctional thiol.
4. The preparation method of the benzoxazine-modified thiol epoxy curing agent according to claim 2, wherein the molar ratio of the benzoxazine to the polythiol is 1 (1-10), and the ring-opening reaction specifically comprises the following steps: reacting for 2-24h at 30-140 ℃ under inert atmosphere.
5. The preparation method of the benzoxazine-based modified thiol epoxy curing agent according to claim 2, wherein the benzoxazine is prepared by a Mannich reaction of a phenol source, an amine source and an aldehyde in a solvent.
6. The preparation method of the benzoxazine-based modified thiol epoxy curing agent according to claim 5, wherein the phenol source is one or more of phenol, o-methylphenol, M-methylphenol, p-methylphenol, o-allylphenol, p-allylphenol, guaiacol, salicylaldehyde, vanillin, eugenol, naphthol, p-halophenol, p-diphenol, resorcinol, bisphenol S, bisphenol A, bisphenol F, bisphenol E, bisphenol B, bisphenol M, bisphenol Z, and the aldehyde is formaldehyde or paraformaldehyde.
7. The method for preparing a benzoxazine-based modified thiol epoxy curing agent according to claim 5, wherein the amine source is aniline, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-xylylenediamine, naphthylamine, benzylamine, methylbenzylamine, p-aminobenzylamine, benzidine, 4 '-diaminodiphenylmethane, p-methylaniline, o-methylaniline, m-methylaniline, 4-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, 3, 5-dimethylaniline, 4' -diaminodiphenyl ether, furfurylamine, methylamine, ethylamine, propylamine, isopropylamine, butylamine, tert-butylamine, octadecylamine, cyclohexylamine, 1,3, 5-triaminobenzene, N-bis (3-aminopropyl) methylamine, N-dimethyl-1, 3-diaminopropane, Tetramethylpropanediamine, dimethyldipropylenetriamine, 4-dimethylaminobutylamine, N-methyl-1, 3-propanediamine, N, N, N-tetrakis (3-aminopropyl) -1, 4-butanediamine, tris (3-aminopropyl) amine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethylenepolyamine, divinylpropylamine, 1, 6-hexanediamine, ethylenediamine, N, N-bis (2-aminoethyl) -1, 2-ethylenediamine, N-methyl-2, 2-diaminodiethylamine, trientine impurities, 4' -diaminodicyclohexylmethane, 3 ' -dimethyl-4, 4' -diaminodicyclohexylmethane, methylcyclohexanediamine, aminoethylpiperazine, methylcyclopentamine, One or more of o-diamine methylcyclopentane, (2, 3-dimethyl) dibutylenetriamine, triaminononane, dicyandiamide, adipic acid dihydrazide, mixed amine and hetero amine.
8. The preparation method of the benzoxazine-modified thiol epoxy curing agent according to claim 5, wherein the molar ratio of the phenol source to the amine source to the aldehyde is 1:1: 2.0-2.5; the solvent is one or more of water, toluene, 1, 4-dioxane, cyclohexanone, ethyl acetate, trichloromethane, xylene, butanone, methyl isobutyl ketone, DMF, DMAc and NMP; the mass fraction of the phenol source, the amine source and the aldehyde in the solvent is 20-90%.
9. The preparation method of the benzoxazine-modified thiol epoxy curing agent according to claim 5, which specifically comprises the following steps: and (3) placing the phenol source and the aldehyde into a solvent, uniformly mixing, then adding the amine source in batches, heating to 80-110 ℃, stirring and reacting for 4-12 hours to obtain the product benzoxazine.
10. Use of a benzoxazine-based modified thiol epoxy hardener according to claim 1 in medium and/or low temperature curing adhesives, coatings and composites.
CN202110948019.9A 2021-08-18 2021-08-18 Preparation method and application of benzoxazine-based modified thiol epoxy curing agent Pending CN113651948A (en)

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CN103748084A (en) * 2011-08-11 2014-04-23 亨斯迈先进材料美国有限责任公司 Method for producing benzoxazine compounds
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