CN108359069B - Method for modifying benzoxazine resin through maleimide internal chain extension - Google Patents
Method for modifying benzoxazine resin through maleimide internal chain extension Download PDFInfo
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- CN108359069B CN108359069B CN201810258836.XA CN201810258836A CN108359069B CN 108359069 B CN108359069 B CN 108359069B CN 201810258836 A CN201810258836 A CN 201810258836A CN 108359069 B CN108359069 B CN 108359069B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
Abstract
The invention discloses a method for modifying benzoxazine resin by extending chain in maleimide, which adopts diamine chain-extended bismaleimide to synthesize a prepolymer taking amino as an end group as an amine source, and carries out Mannich polycondensation reaction with a phenolic compound and formaldehyde (or paraformaldehyde) to prepare a corresponding benzoxazine oligomer. The synthesized prepolymer of maleimide and diamine contains a primary amine end group and a reactive secondary amine group in a molecular structure, so that the ring-opening reaction of benzoxazine can be promoted and the curing reaction temperature can be reduced; on the other hand, the reactive sites are reactive with epoxy resins or isocyanates, and the polymer can be further improved in performance.
Description
Technical Field
The invention belongs to the field of thermosetting resin preparation, and particularly relates to a method for modifying benzoxazine resin through maleimide internal chain extension.
Background
Bismaleimide (BMI) is a thermosetting resin with excellent heat resistance, has good heat resistance, radiation resistance, damp and heat resistance, aging resistance and electrical insulation, and has an increasingly wide application range. However, bismaleimide resins themselves have high melting points, poor solubility, and poor toughness of cured products, and unmodified bismaleimide resins have no practical application value. Aiming at the defects of maleimide resin, the domestic and foreign researches mainly adopt diamine compounds, allyl bisphenol A and derivatives thereof to modify the maleimide resin to obtain a prepolymer taking maleimide functional groups as end groups, so that the melting point of a BMI monomer can be reduced, the solubility of BMI is improved, and the toughness of a corresponding cured product is greatly improved. The reaction of diamine chain extension modification BMI is as follows:
nowadays, a novel high-performance resin, namely benzoxazine resin, is developed on the basis of the traditional phenolic resin, and is a six-membered heterocyclic compound prepared by a phenolic compound, an amine compound and formaldehyde (or paraformaldehyde) through a Mannich shrinkage reaction. Under the action of heat or catalyst, the benzoxazine intermediate undergoes ring-opening polymerization to form a nitrogen-containing network structure similar to phenolic resin. The novel thermosetting resin not only has the high temperature resistance, corrosion resistance, aging resistance, flame retardance and good mechanical properties which are equivalent to those of the traditional phenolic resin, but also has the characteristics of no micromolecule release, zero shrinkage or micro expansion of a system in the curing process, low surface energy, lower low dielectric constant and the like of a corresponding polymer, so that the novel thermosetting resin is widely concerned by academia and the business industry at home and abroad.
However, the benzoxazine resin still has the defects of high curing temperature, poor toughness of a corresponding cured product and the like. Based on the molecular design flexibility of benzoxazine, Chinese patents invented in 'a preparation method of bisphenol A type benzoxazine containing maleimide' (application number is 201310296947.7), 'an ortho-maleimide monofunctional benzoxazine monomer and its preparation method' (application number is 201610762806.3) 'a maleimide group-terminated benzoxazine oligomer and its preparation method' (201611180419.5), etc. maleimide functional groups are introduced into the structure of benzoxazine molecules as substituents corresponding to amine sources or phenol sources, and through the reaction of maleimide functional groups, the crosslinking density of corresponding polymers is further increased, the heat resistance is improved, but the toughness of the polymers is not obviously improved, even decreased.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention aims to synthesize an oligomer with primary amine functional group as an end group by adopting the chain extension reaction of diamine and bismaleimide as the basis, and then prepare a benzoxazine oligomer by reacting with a phenolic compound and formaldehyde (or paraformaldehyde).
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for modifying benzoxazine resin by maleimide internal chain extension comprises the following steps:
(1) synthesis of chain extension product of bismaleimide containing terminal amino and diamine
Adding a high-boiling-point polar solvent and Nmol diamine into a three-necked bottle provided with a stirrer, a condenser and a thermometer, stirring and dissolving the diamine under the protection of nitrogen, heating to 90-130 ℃, adding Mmol bismaleimide, wherein M is less than N, and carrying out heat preservation reaction for 0.5-4.0 h to obtain a solution of the bismaleimide containing terminal amino and a diamine chain extension product;
the chain extension reaction equation of diamine and bismaleimide is as follows:
in the formula, bridging the substrate R1、R2Respectively one of the following:
(2) synthesis of benzoxazine oligomers
Adding a low-polarity solvent, 2(N-M) mol of phenolic compound and 4.0(N-M) -4.8 (N-M) mol of formaldehyde or paraformaldehyde into a four-mouth bottle provided with a stirrer, a condenser and a constant-pressure funnel, heating to 45-75 ℃, then dropwise adding the solution of the amino-terminated bismaleimide obtained in the step (1) and the diamine chain extension product into the system, heating to 80-130 ℃ after dropwise adding, and reacting for 4-12 hours to obtain a benzoxazine oligomer-containing reaction liquid;
the reaction equation for synthesizing the benzoxazine oligomer is as follows:
in the formula
Is one of the following structures:
(3) product separation and purification
And (3) adding deionized water and ethanol into the benzoxazine oligomer-containing reaction liquid obtained in the step (2), washing an organic phase, separating liquid to obtain an organic phase, and distilling the organic phase under reduced pressure to obtain the deep red benzoxazine oligomer.
Based on the flexible molecular design of the benzoxazine compound and the chain extension reaction of the diamine compound and the bismaleimide, the invention adopts diamine chain extension bismaleimide to synthesize a prepolymer taking amino as an end group as an amine source, and carries out Mannich polycondensation reaction with the phenolic compound and formaldehyde (or paraformaldehyde) to prepare the corresponding benzoxazine oligomer, thereby realizing the purposes of reducing the polymerization reaction temperature of benzoxazine and improving the toughness of the corresponding polymer.
In the step (1), in order to better dissolve the diamine and prevent the diamine from being oxidized, the temperature can be increased to 50-70 ℃ for dissolution, and the temperature is increased for reaction after the diamine is fully dissolved. After the reaction is finished, the obtained solution of the bismaleimide containing the terminal amino and the diamine chain extension product can be cooled to 30-40 ℃ to prevent the amino from being oxidized at high temperature.
In the step (2), the temperature is increased to 45-75 ℃, so that the synthesis of the benzoxazine structure can be ensured, and the side reaction can be increased when the temperature is too low. After the reaction is finished, the obtained reaction liquid containing the benzoxazine oligomer can be cooled to 40-60 ℃ so as to facilitate subsequent separation and purification and avoid volatilization of the organic solvent caused by overhigh temperature.
In the step (3), deionized water and ethanol are used for washing the organic phase, so that part of high-boiling polar solvent, byproducts and the like in the organic phase can be removed, and the organic phase can be washed for 2-3 times as required.
Preferably, the high-boiling polar solvent used in step (1) is at least one of N, N '-dimethylformamide, N' -dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone. In the step (1), the solid content (mass percent) of the reactant can be 20-60%, the solid content is too low, the solvent consumption is large, and the solid content can be preferably 40-60%.
Preferably, the ratio M/N of the amount of bismaleimide to diamine in step (1) is 0.1 to 0.8. The ratio of M/N is more preferably 0.3 to 0.5. The molecular weight of the synthesized product is too large due to the overlarge M/N ratio, and the subsequent processing and application of the product are not facilitated.
Preferably, in the step (1), the reaction temperature of the diamine and the bismaleimide chain extension is 90-100 ℃, and the reaction time is 1-1.5 h. The condition can ensure that the oxidation of the terminal amino group is reduced as much as possible under the condition of complete reaction of diamine and bismaleimide, and the equivalent shortage of the amino group in the next synthetic process is avoided.
Preferably, the amount of the substance of formaldehyde or paraformaldehyde in step (2) is 4.4(N-M) to 4.6(N-M) mol. The excessive formaldehyde or paraformaldehyde in the condensation reaction can ensure the ring-closing rate of the benzoxazine.
Preferably, the low-polar solvent in the step (2) is at least one of chloroform, toluene, xylene, dichlorobenzene and dioxane. The dosage of the low-polarity solvent is 2-6 times of the mass of the phenolic compound.
Preferably, after the dropwise adding in the step (2) is finished, the temperature is raised to 90-100 ℃, and the reaction is carried out for 6-8 h.
Preferably, the bismaleimide in the step (1) is added within 20-50 min. The bismaleimide can be added for multiple times in 20-50 min in batches to prevent violent reaction and sudden polymerization.
Preferably, the solution of the bismaleimide containing terminal amino groups and the diamine chain extension product in the step (2) is dripped off within 30-120 min. The dripping is too fast, the side reaction is too much, the yield of the product is influenced, and the dripping is too slow, so that the economical efficiency is not facilitated.
Preferably, the reduced pressure distillation temperature in the step (3) is 80-120 ℃.
The benzoxazine oligomer-containing reaction liquid obtained in the step (2) can be directly used for dipping or coating without separation and purification according to the use requirement.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts diamine and bismaleimide chain extension reaction to synthesize oligomer taking primary amine functional group as an end group as an amine source of the benzoxazine, and the molecular designability of the benzoxazine oligomer is further increased due to the rich varieties of the bismaleimide and the diamine, and the structure and the performance of the benzoxazine polymer can be regulated and controlled by selecting the diamine and the bismaleimide with different structures.
(2 the synthesized prepolymer of maleimide and diamine contains a primary amine end group and a reactive secondary amine group in a molecular structure, so that the ring-opening reaction of benzoxazine can be promoted and the polymerization temperature can be reduced, and the reactive active site can react with epoxy resin or isocyanate, so that the high performance of a polymer is further realized and the toughness of the polymer of the benzoxazine resin is improved.
Drawings
FIG. 1 is an infrared spectrum of the product prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
500ml of DMF was taken in a three-necked flask equipped with stirrer, condenser and thermometer, slowly warmed to 65 ℃ and 1mol (198g) of 4, 4' -diaminodiphenylmethane was added thereto, and nitrogen was introduced for protection, to dissolve the diamine completely with stirring. Then slowly heating to 90 ℃, adding 0.5mol (179g) of diphenylmethane bismaleimide in batches within 30min, reacting for 1.5h under heat preservation, then slowly cooling to 30-40 ℃ to obtain bismaleimide with an amino end group and diamine chain extension product solution, and preserving heat for later use.
1mol (134g) of 2-allylphenol, 2.3mol (69g) of paraformaldehyde and 400ml of toluene were put into a four-necked flask equipped with a stirrer, a condenser, a thermometer and a constant pressure funnel, and the temperature was slowly raised to 55 to 60 ℃. Gradually dropwise adding the obtained bismaleimide containing terminal amino and diamine chain extension product solution into the system, slowly heating to 95 ℃ within 40min, and reacting at constant temperature for 6 h. After the reaction is finished, cooling the reaction system to 50 ℃.
And adding deionized water and a proper amount of ethanol into the reaction solution, washing the organic phase for 2-3 times, and removing part of the high-boiling-point polar solvent, the byproducts and the like. And (3) obtaining an organic phase by liquid separation, heating the organic phase to 120 ℃, carrying out reduced pressure distillation, and removing residual solvent in the system to obtain a dark red benzoxazine oligomer solid with the yield of 97.6%. The infrared spectrum of the product prepared in this example is shown in FIG. 1, wherein 3030cm-1A characteristic peak corresponding to-NH in the structure; 2900cm-1Corresponding structure of-CH2-a characteristic peak; 1716 and 1668cm-1Characteristic peak corresponding to-C ═ O in the structure; 941cm-1Corresponding to the characteristic peak of the oxazine ring structure in the structure.
Example 2
300ml of DMAc is added into a three-neck flask provided with a stirrer, a condenser and a thermometer, the temperature is slowly raised to 60 ℃, 1.4mol (151.2g) of p-phenylenediamine is added, nitrogen is introduced for protection, and the diamine is completely dissolved under the condition of stirring. And then slowly heating to 90 ℃, adding 0.5mol (179g) of diphenylmethane bismaleimide in batches within 40min, reacting for 1.0h under heat preservation, then slowly cooling to 30-40 ℃ to obtain bismaleimide with an amino end group and diamine chain extension product solution, and preserving heat for later use.
1.8mol (169.2g) of phenol, 4.1mol (123g) of paraformaldehyde and 600ml of xylene are added into a four-neck flask provided with a stirrer, a condenser, a thermometer and a constant pressure funnel, and the temperature is slowly raised to 55-60 ℃. Gradually dropwise adding the obtained bismaleimide containing terminal amino and diamine chain extension product solution into the system, slowly heating to 100 ℃ within 60min, and reacting at constant temperature for 6 h. After the reaction is finished, cooling the reaction system to 50 ℃.
And adding deionized water and a proper amount of ethanol into the reaction solution, washing the organic phase for 2-3 times, and removing part of the high-boiling-point polar solvent, the byproducts and the like. And (3) obtaining an organic phase by liquid separation, heating the organic phase to 120 ℃, carrying out reduced pressure distillation, and removing residual solvent in the system to obtain a dark red benzoxazine oligomer solid with the yield of 96.9%. The infrared spectrogram result of the product obtained in this example is the same as that of example 1.
Best mode for carrying out the invention
300ml of NMP was added to a three-necked flask equipped with a stirrer, condenser and thermometer, the temperature was slowly raised to 65 ℃ and 1mol (198g) of 4, 4' -diaminodiphenylmethane was added thereto, and nitrogen was introduced for protection, to completely dissolve the diamine while stirring. Then slowly heating to 90 ℃, adding 0.5mol (134g) of p-benzene bismaleimide in batches within 50min, reacting for 2.0h under heat preservation, then slowly cooling to 35-40 ℃ to obtain bismaleimide with an amino end group and diamine chain extension product solution, and preserving heat for later use.
1mol (94g) of phenol, 2.2mol (66g) of paraformaldehyde and 400ml of toluene are added into a four-neck flask provided with a stirrer, a condenser, a thermometer and a constant pressure funnel, and the temperature is slowly increased to 55-60 ℃. Gradually dropwise adding the obtained bismaleimide containing terminal amino and diamine chain extension product solution into the system, slowly heating to 85 ℃ within 60min, and reacting at constant temperature for 6 h. After the reaction is finished, cooling the reaction system to 50 ℃.
And adding deionized water and a proper amount of ethanol into the reaction solution, washing the organic phase for 2-3 times, and removing part of the high-boiling-point polar solvent, the byproducts and the like. And (3) obtaining an organic phase by liquid separation, heating the organic phase to 90 ℃, carrying out reduced pressure distillation, and removing residual solvent in the system to obtain a dark red benzoxazine oligomer solid with the yield of 95.1%. The infrared spectrogram result of the product obtained in this example is the same as that of example 1.
The above examples of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Variations and modifications in other variations will occur to those skilled in the art upon reading the foregoing description. Not all embodiments are exhaustive. All obvious changes and modifications of the present invention are within the scope of the present invention.
Claims (10)
1. A method for modifying benzoxazine resin through maleimide internal chain extension is characterized by comprising the following steps:
(1) synthesis of chain extension product of bismaleimide containing terminal amino and diamine
Adding a high-boiling-point polar solvent and Nmol diamine into a three-necked bottle provided with a stirrer, a condenser and a thermometer, stirring and dissolving the diamine under the protection of nitrogen, heating to 90-130 ℃, adding Mmol bismaleimide, wherein M is less than N, and carrying out heat preservation reaction for 0.5-4.0 h to obtain a solution of the bismaleimide containing terminal amino and a diamine chain extension product;
the chain extension reaction equation of diamine and bismaleimide is as follows:
in the formula, bridging the substrate R1、R2Respectively one of the following:
(2) synthesis of benzoxazine oligomers
Adding a low-polarity solvent, 2(N-M) mol of phenolic compound and 4.0(N-M) -4.8 (N-M) mol of formaldehyde or paraformaldehyde into a four-mouth bottle provided with a stirrer, a condenser and a constant-pressure funnel, heating to 45-75 ℃, then dropwise adding the solution of the amino-terminated bismaleimide obtained in the step (1) and the diamine chain extension product into the system, heating to 80-130 ℃ after dropwise adding, and reacting for 4-12 hours to obtain a benzoxazine oligomer-containing reaction liquid;
the reaction equation for synthesizing the benzoxazine oligomer is as follows:
in the formula
Is one of the following structures:
(3) product separation and purification
And (3) adding deionized water and ethanol into the benzoxazine oligomer-containing reaction liquid obtained in the step (2), washing an organic phase, separating liquid to obtain an organic phase, and distilling the organic phase under reduced pressure to obtain the deep red benzoxazine oligomer.
2. The method for preparing a maleimide internally chain-extended modified benzoxazine resin according to claim 1, wherein the high boiling polar solvent in step (1) is at least one of N, N '-dimethylformamide, N' -dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone.
3. The method for preparing a maleimide internally chain-extended modified benzoxazine resin according to claim 1, wherein the ratio M/N of the amount of bismaleimide to diamine substance in the step (1) is 0.1-0.8.
4. The method for preparing the maleimide internal chain extension modified benzoxazine resin according to claim 1, wherein the diamine and bismaleimide chain extension reaction temperature in the step (1) is 90-100 ℃, and the reaction time is 1-1.5 h.
5. The method for preparing a maleimide internally chain-extended modified benzoxazine resin according to claim 1, wherein the amount of formaldehyde or paraformaldehyde substance in step (2) is 4.4(N-M) to 4.6(N-M) mol.
6. The method for preparing a maleimide internally chain-extended modified benzoxazine resin according to claim 1, wherein the low-polar solvent in the step (2) is at least one of chloroform, toluene, xylene, dichlorobenzene and dioxane.
7. The method for preparing the maleimide internal chain extension modified benzoxazine resin according to claim 1, wherein after the dropwise addition in the step (2), the temperature is raised to 90-100 ℃ for reaction for 6-8 hours.
8. The method for preparing the maleimide internal-chain-extension modified benzoxazine resin according to claim 1, wherein the bismaleimide is added in 20-50 min in the step (1).
9. The method for preparing the maleimide internal chain extension modified benzoxazine resin according to claim 1, wherein the solution of the amine-terminated bismaleimide and diamine chain extension product obtained in the step (2) is dripped out within 30-120 min.
10. The method for preparing the maleimide internal chain extension modified benzoxazine resin according to claim 1, wherein the reduced pressure distillation temperature in the step (3) is 80-120 ℃.
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| JP2728515B2 (en) * | 1989-09-07 | 1998-03-18 | 昭和高分子株式会社 | Curable resin composition |
| JP2010100802A (en) * | 2008-09-24 | 2010-05-06 | Sekisui Chem Co Ltd | Epoxy-based resin composition, sheet-like molded product, prepreg, cured product, laminated plate, and multilayer laminated plate |
| CN107129493A (en) * | 2017-04-10 | 2017-09-05 | 江苏大学 | A kind of two amine type bi-benzoxazines of the imide containing alicyclic and preparation method thereof |
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| US4296219A (en) * | 1978-03-31 | 1981-10-20 | Hitachi, Ltd. | Bismide-ether compounds, compositions thereof, and method of producing same |
| JP2728515B2 (en) * | 1989-09-07 | 1998-03-18 | 昭和高分子株式会社 | Curable resin composition |
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| JP2010100802A (en) * | 2008-09-24 | 2010-05-06 | Sekisui Chem Co Ltd | Epoxy-based resin composition, sheet-like molded product, prepreg, cured product, laminated plate, and multilayer laminated plate |
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