CN109553551B - Modified bismaleimide monomer, repairable resin and preparation and repair methods - Google Patents

Modified bismaleimide monomer, repairable resin and preparation and repair methods Download PDF

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CN109553551B
CN109553551B CN201811337554.5A CN201811337554A CN109553551B CN 109553551 B CN109553551 B CN 109553551B CN 201811337554 A CN201811337554 A CN 201811337554A CN 109553551 B CN109553551 B CN 109553551B
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diamine
repairable
bismaleimide resin
bismaleimide
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汪东
李丽英
柯红军
卢山
田正刚
王国勇
李永民
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Aerospace Research Institute of Materials and Processing Technology
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
    • C07C317/36—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms
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    • C07D—HETEROCYCLIC COMPOUNDS
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    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
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    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract

The invention provides a modified bismaleimide monomer, a repairable resin and preparation and repair methods thereof, wherein each repeating unit contains a dynamic imine bond. The modified bismaleimide monomer contains dynamic imine cross-linking bonds, and the heat exchange reaction of the dynamic imine cross-linking bonds is remarkably accelerated when the dynamic imine cross-linking bonds are heated, so that the movement rearrangement of a polymer chain is induced; the bismaleimide resin has dynamic imine bridging bonds, the heat exchange reaction of the imine bridging bonds is remarkably accelerated when the imine bridging bonds are heated, so that the kinematic rearrangement of a high molecular chain is induced, and the damaged bismaleimide resin can be fused by the dynamic exchange of the imine bonds and the rearrangement of the high molecular chain, so that the bismaleimide resin has repairability.

Description

Modified bismaleimide monomer, repairable resin and preparation and repair methods
Technical Field
The invention relates to a modified bismaleimide monomer, a repairable resin, and preparation and repair methods thereof, and belongs to the technical field of functional composite materials.
Background
The resin-based composite material occupies an important position in the application of aerospace aircrafts due to the advantages of high specific strength and weight reduction. With the continuous improvement of the Mach number of the current high-performance aircraft, higher and higher requirements are put forward on the temperature resistance of resin-based materials. The bismaleimide resin condensate has good high temperature resistance, radiation resistance, moisture resistance and low water absorption rate, and is increasingly widely applied to various industries such as aerospace industry, electronic and electrical industry, transportation industry and the like. However, the traditional bismaleimide resin is insoluble and infusible after being cured and molded due to the irreversible chemical crosslinking network structure, and is difficult to repair an in-situ body like a thermoplastic polymer when the bismaleimide resin is damaged in the using process of a material, so that great potential safety hazard is brought to the whole structure. Therefore, it is important to develop bismaleimide resin materials with repairable performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a bimaleimide monomer with a repairable function, a bimaleimide resin and preparation and repair methods thereof.
The technical solution of the invention is as follows: a modified bismaleimide monomer, each repeat unit comprising the following segments:
Figure BDA0001861624430000011
wherein the radical R 1 And R 2 At least one of which is an aromatic group.
A repairable bismaleimide resin is obtained by reacting a modified bismaleimide monomer, an allyl compound and a catalyst, wherein each repeating unit of the modified bismaleimide monomer comprises the following segments:
Figure BDA0001861624430000021
wherein the radical R 1 And R 2 At least one of which is an aromatic group.
A preparation method of a modified bismaleimide monomer is realized by the following steps:
the first step, preparing modified diamine,
a1.1, dissolving diamine and a dialdehyde monomer in an organic solvent respectively to obtain a solution 1 and a solution 2 respectively, wherein the diamine and/or the dialdehyde is aromatic;
A1dropwise adding the solution 2 into the solution 1 according to the proportion, fully reacting, and drying to obtain a product containing each repeating unit
Figure BDA0001861624430000022
A modified diamine of a segment in which the radical R 1 And R 2 At least one of them is an aromatic group;
secondly, reacting the modified diamine prepared in the first step with dianhydride to obtain a diamine containing each repeating unit
Figure BDA0001861624430000023
Segmented bismaleimide monomers.
A preparation method of repairable bismaleimide resin is realized by the following steps:
the first step, preparing modified diamine,
a1.1, dissolving diamine and a dialdehyde monomer in an organic solvent respectively to obtain a solution 1 and a solution 2 respectively, wherein the diamine and/or the dialdehyde is aromatic;
a1.2, dropwise adding the solution 2 into the solution 1 according to the proportion, fully reacting, and drying to obtain a product containing each repeating unit
Figure BDA0001861624430000024
A modified diamine of a segment in which the radical R 1 And R 2 At least one of them is an aromatic group;
secondly, reacting the modified diamine prepared in the first step with dianhydride to obtain a diamine containing each repeating unit
Figure BDA0001861624430000025
A modified bismaleimide monomer of a fragment;
step three, reacting the modified bismaleimide monomer obtained in the step two with an allyl compound according to a proportion, adding a proper amount of catalyst, and fully reacting to obtain a compound containing each repeating unit
Figure BDA0001861624430000031
Segmented bismaleimide resin system.
A repairable bismaleimide resin repairing method is realized by the following steps:
firstly, preparing diamine restoration solution,
the diamine restoration solution is an organic diamine solution with a certain concentration;
secondly, coating the diamine repairing liquid prepared in the first step on the damaged position of the repairable bismaleimide resin, and heating and preserving heat until the surface of the repairable bismaleimide resin is dissolved;
and thirdly, continuously heating to the temperature not higher than the oxidation temperature of the repairable bismaleimide resin, and volatilizing the diamine repair liquid to finish the repair of the bismaleimide resin.
Compared with the prior art, the invention has the beneficial effects that:
(1) the modified bismaleimide monomer contains dynamic imine cross-linking bonds, and the heat exchange reaction of the dynamic imine cross-linking bonds is remarkably accelerated when the dynamic imine cross-linking bonds are heated, so that the movement rearrangement of a polymer chain is induced;
(2) the bismaleimide resin has dynamic imine bridging bonds, the heat exchange reaction of the imine bridging bonds is remarkably accelerated when the imine bridging bonds are heated, so that the movement rearrangement of a high molecular chain is induced, and the damaged bismaleimide resin can be fused with the rearrangement of the high molecular chain through the dynamic exchange of the imine bonds, so that the bismaleimide resin has repairability;
(3) the preparation method has universality, mild reaction conditions and simple preparation process;
(4) the bismaleimide resin prepared by the invention overcomes the problem that the bismaleimide resin cannot be repaired after being damaged in the prior art, and can realize better repair under the assistance of diamine micromolecule solution based on the heat exchange reaction of imine bonds;
(5) the bismaleimide resin prepared by the invention has excellent heat resistance, mechanical property and repairability, and has potential application prospect in the field of future intelligent high polymer materials.
Detailed Description
The invention provides a modified bismaleimide monomer, wherein each repeating unit contains the following segments:
Figure BDA0001861624430000032
wherein the radical R 1 And R 2 At least one of which is an aromatic group.
The modified bismaleimide monomer is prepared by reacting modified diamine with dianhydride, and each repeating unit of the diamine at least comprises the following segments:
Figure BDA0001861624430000041
the modified bismaleimide monomer adopts modified diamine with dynamic imine bridging bonds, the dynamic imine bridging bonds are introduced into the bismaleimide monomer, and the heat exchange reaction of the dynamic imine bridging bonds is remarkably accelerated when the dynamic imine bridging bonds are heated, so that the movement rearrangement of a high molecular chain is induced.
The modified bismaleimide monomer can be prepared by adopting a preparation method known in the field, and only by adopting modified diamine with dynamic imine bridging bonds and introducing the dynamic imine bridging bonds into the bismaleimide monomer. For example, modified diamine with dynamic imine bridging bond is reacted with dianhydride to prepare modified bismaleimide monomer.
The method is realized by the following steps:
1. preparing modified diamine containing dynamic imine bonds;
the modified diamine is diamine containing dynamic imine bridging bond, and the group R adjacent to the imine bond 1 And R 2 At least one of the groups is an aromatic group, so that the dynamic property of the imine bond is ensured. The dynamic imine cross-linking bond can remarkably accelerate the heat exchange reaction when being heated, thereby inducing the movement rearrangement of the polymer chain.
The modified diamine can be prepared by the preparation method known in the art, as long as the prepared modified diamine can contain the dynamic imine bridging bond. If the aromatic diamine is prepared by condensation reaction of organic diamine and organic dialdehyde, the types of the organic diamine monomer and the organic dialdehyde are not limited, and the organic diamine monomer and/or the organic dialdehyde are aromatic. The organic diamine can be aliphatic diamine or aromatic diamine, such as one or more of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, m-phenylenediamine, tri (2-aminoethyl) amine, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl ether, and diaminodiphenyl ketone. The organic dialdehyde monomer can be aliphatic dialdehyde or aromatic dialdehyde, preferably terephthalaldehyde, m-phthalaldehyde and other one or mixture thereof.
The method is realized by the following steps:
(1) dissolving diamine and dialdehyde monomers in organic solvents respectively to obtain a solution 1 and a solution 2 respectively, wherein the diamine and/or the dialdehyde is aromatic;
(2) and dropwise adding the solution 2 into the solution 1 according to the proportion, fully reacting, and drying to obtain the modified diamine containing dynamic imine bonds.
The molar ratio of the organic diamine to the dialdehyde monomer is 2: 1, are well known in the art. And dropwise adding the solution 2 into the solution 1 slowly under rapid stirring, preferably fully reacting for 6-24 h at 25-80 ℃, and drying in vacuum to ensure that the imine condensation reaction is fully carried out.
2. Reacting modified diamine containing dynamic imine bonds with dianhydride to prepare the modified bismaleimide monomer.
The reaction of diamine and dianhydride to obtain bismaleimide monomer is well known in the art, for example, maleic anhydride can be used as dianhydride, and the specific process and ratio of the reaction of diamine and dianhydride can be found in the well-known art. Preferably, the modified diamine containing dynamic imine bonds and maleic anhydride are dissolved in glacial acetic acid, reflux reaction is carried out for 5-8 h at the temperature of 110-130 ℃, and the modified Bismaleimide Monomer (BMI) is obtained after purification and drying.
The invention also provides a repairable bismaleimide resin which is obtained by reacting a modified bismaleimide monomer, an allyl compound and a catalyst, wherein each repeating unit of the modified bismaleimide monomer contains the following segments:
Figure BDA0001861624430000051
wherein the radical R 1 And R 2 At least one of which is an aromatic group.
The allyl compound is used as the toughening agent, the type is not limited, and the allyl compound can play a toughening role and has no adverse effect on a bismaleimide resin system. One or more of O, O ' -diallyl bisphenol A, 4, 4 ' -bis (O-propenyl phenoxy) diphenyl sulfone, 4, 4 ' -bis (O-propenyl phenoxy) benzophenone and the like which are commonly used can be adopted. The amount of allyl compound added is well known in the art and is selected according to the requirements of the resin to be prepared.
The catalyst adopted by the invention is a catalyst type commonly used in a bismaleimide resin system, is not limited by a special type, and can be one or a mixture of more of commonly used copper acetylacetonate, zirconium acetylacetonate, chromium acetylacetonate, triphenylphosphine, 2-methyl-4 ethylimidazole and the like. The amount of catalyst to be added is known in the art and is selected by the person skilled in the art according to the preparation.
The repairable resin is prepared by reacting a modified bismaleimide monomer, an allyl compound and a catalyst, wherein the modified bismaleimide monomer is prepared by reacting modified diamine and dianhydride, the modified diamine is prepared by condensation reaction of diamine and dialdehyde, and the diamine and/or the dialdehyde is aromatic.
The method is realized by the following steps:
1. preparing a modified bismaleimide monomer containing a dynamic imine bond by adopting the method;
2. reacting the modified bismaleimide resin containing dynamic imine bonds with an allyl compound according to a proportion, adding a proper amount of catalyst, and fully reacting to obtain the bismaleimide resin system containing dynamic imine bonds.
The specific preparation ratio and the process parameters can be selected from known techniques, and the following preferred ratio can also be adopted.
The compounding ratio of the repairable bismaleimide resin is preferably as follows: 75-85% of modified bismaleimide monomer, 15-25% of allyl compound and 100% of bismaleimide monomer and allyl compound; the proper amount of the catalyst is preferably 0.01-0.05% of the total mass of the resin.
Preferably, the modified bismaleimide monomer and the allyl compound react for 0.5-1 hour at 100-120 ℃, the temperature is reduced to 60-80 ℃, a proper amount of catalyst is added, and the mixture is stirred for 10-30min at 60-80 ℃ to obtain the repairable bismaleimide resin.
The principle is as follows: the modified diamine containing imine bonds is prepared, dynamic imine bonds are ingeniously introduced into a bismaleimide resin cross-linked network through imidization reaction of diamine and anhydride, the heat exchange reaction of the imine cross-linked bonds is remarkably accelerated when the imine cross-linked bonds are heated, and therefore movement rearrangement of high molecular chains is induced, and accordingly, damaged bismaleimide resins can be fused through dynamic exchange of the imine bonds and rearrangement of the high molecular chains under certain conditions, and recovery and repair of the resins are achieved.
The invention also provides a repairing method for the repairable bismaleimide resin, which is realized by the following steps:
1. preparing diamine restoration solution;
dissolving organic diamine in an organic solvent to prepare an organic diamine solution with a certain concentration;
the organic diamine used for preparing the diamine restoration solution is not particularly limited, and may be one or a mixture of several of aliphatic diamine and aromatic diamine.
The concentration of the diamine repairing solution is not suitable to be too high, and if the concentration is too high, the movement rearrangement of a high molecular chain at a damaged part can be influenced, and the repairing effect can be influenced, so that the concentration is generally not higher than 15 mg/mL; theoretically, the lower the concentration of the diamine restoration solution, the more favorable the restoration, but the slower the imine bond exchange reaction is induced and the longer the restoration time, so the concentration of the diamine restoration solution is preferably 8mg/mL to 15 mg/mL.
The organic solvent is not limited in kind, and may be any solvent which can dissolve the diamine in a desired concentration range in principle and does not adversely affect the resin or the diamine itself, for example, a solvent of DMF/acetone (v/v ═ 1:1) may be used.
2. And (3) coating the diamine repairing liquid on the damaged position of the repairable bismaleimide resin, and heating and insulating until the surface of the repairable bismaleimide resin is dissolved.
In the step, the exchange reaction of imine bonds in the excitation of the bismaleimide resin can be repaired, the bismaleimide resin reacts with low-molecular diamine to release the imine bonds, and the long chain recombination of the bismaleimide resin can be repaired to repair defects.
The lower limit of the heating temperature range is the initial temperature for exciting the imine bond exchange reaction in the repairable bismaleimide resin, the upper limit is lower than the oxidation temperature of the repairable bismaleimide resin, the higher the heating temperature is, the shorter the required time is, and the optimal temperature can be selected by a person skilled in the art in the heating temperature range. In general, in a common bismaleimide resin system, the lower limit of the heating temperature range is more than or equal to 90 ℃, and the upper limit is less than or equal to 160 ℃.
3. And continuously heating to volatilize the repairing liquid to finish repairing.
The upper heating limit of the step is lower than the repairable bismaleimide resin oxidation temperature, the higher the heating temperature is, the shorter the time required for volatilization is, and the optimal heating temperature can be selected by a person skilled in the art according to specific situations. Generally, in a common bismaleimide resin system, the lower limit of the heating temperature is more than or equal to 160 ℃, and the upper limit is not higher than 180 ℃.
The mechanism of the repair is that organic diamine molecules in the repair liquid perform exchange reaction with dynamic imine bonds in the repairable resin at a certain temperature, so that a macromolecular chain at a damaged interface is induced to perform kinematic rearrangement, and the repair is completed.
The present invention will be described in detail with reference to specific examples.
Example 1
Weighing 15.0g of ethylenediamine, dissolving the ethylenediamine in 30ml of methanol, and stirring for 10min at room temperature to obtain a clear solution 1; 16.5g of terephthalaldehyde was weighed and dissolved in 15ml of methanol, and treated with ultrasound at room temperature for 5min to obtain a clear solution 2. Heating the solution 1 to 40 ℃, dropwise and slowly adding the solution 2 into the rapidly stirred solution 1 by using a constant-pressure dropping funnel, fully reacting for 12 hours, and performing vacuum drying to obtain the modified diamine containing the dynamic imine bond structure, wherein the structural formula is as follows:
Figure BDA0001861624430000081
example 2
Weighing 50g of diaminodiphenylmethane (DDM) and dissolving in 60ml of methanol, and stirring at room temperature for 10min to obtain a clear solution 1; 16.7g of terephthalaldehyde was weighed and dissolved in 15ml of methanol, and treated with ultrasound at room temperature for 5min to obtain a clear solution 2. Heating the solution 1 to 40 ℃, dropwise and slowly adding the solution 2 into the rapidly stirred solution 1 by using a constant-pressure dropping funnel, fully reacting for 12 hours, and performing vacuum drying to obtain the modified diamine containing an imine bond structure, wherein the structural formula is as follows:
Figure BDA0001861624430000082
example 3
Weighing 50g of Diamino Diphenyl Sulfone (DDS) and dissolving in 60ml of methanol, and stirring for 10min at room temperature to obtain a clear solution 1; 13.5g of terephthalaldehyde was weighed and dissolved in 15ml of methanol, and treated with ultrasound at room temperature for 5min to obtain a clear solution 2. Heating the solution 1 to 40 ℃, dropwise and slowly adding the solution 2 into the rapidly stirred solution 1 by using a constant-pressure dropping funnel, fully reacting for 12 hours, and performing vacuum drying to obtain the modified diamine containing an imine bond structure, wherein the structural formula is as follows:
Figure BDA0001861624430000091
example 4
30g of maleic anhydride and 33.4g of the modified diamine prepared in example 1 were dissolved in 150mL of glacial acetic acid, and the mixture was refluxed at 120 ℃ for 6 hours, purified and dried to obtain modified Bismaleimide (BMI) having the following structural formula:
Figure BDA0001861624430000092
example 5
30g of maleic anhydride and 76g of the modified diamine prepared in example 2 were dissolved in 200mL of glacial acetic acid, reacted at 120 ℃ under reflux for 6h, purified and dried to give modified Bismaleimide (BMI) of the formula:
Figure BDA0001861624430000093
example 6
Dissolving 30g of maleic anhydride and 91g of modified diamine of example 3 in 200mL of glacial acetic acid, carrying out reflux reaction at 120 ℃ for 6h, purifying and drying to obtain modified Bismaleimide (BMI), wherein the structural formula is as follows:
Figure BDA0001861624430000101
example 7
75g of the modified bismaleimide prepared in the embodiment 4 is weighed, 25g of diallyl bisphenol A is added to react for 1 hour at the temperature of 115 ℃, the temperature is reduced to 80 ℃, a catalyst accounting for 0.012 percent of the total amount of the reactants is added, and the stirring is continued for 30 minutes at the temperature of 80 ℃ to obtain the needed bismaleimide resin.
The glass transition temperature, tensile strength and repair efficiency of the bismaleimide resin cured product are shown in table 1.
Example 8
Weighing 80g of the modified bismaleimide prepared in the embodiment 5, adding 20g of diallyl bisphenol A, reacting at 115 ℃ for 1h, cooling to 80 ℃, adding a catalyst accounting for 0.012 percent of the total amount of the reactants, and continuously stirring at 80 ℃ for 30min to obtain the needed bismaleimide resin.
The glass transition temperature, tensile strength and repair efficiency of the cured resin are shown in Table 1.
Example 9
85g of the modified bismaleimide prepared in example 6 was weighed, 15g of diallyl bisphenol A was added, the reaction was carried out at 115 ℃ for 1h, the temperature was reduced to 80 ℃, a catalyst in an amount of 0.012% of the total amount of the reactants was added, and the mixture was stirred at 80 ℃ for 30min to obtain the desired bismaleimide resin.
The glass transition temperature, tensile strength and repair efficiency of the cured resin are shown in Table 1.
Comparative example 1
Step 1: dissolving 30g of maleic anhydride and 30.3g of diaminodiphenylmethane (DDM) in mL of glacial acetic acid, carrying out reflux reaction at 120 ℃ for 6h, purifying, and drying to obtain Bismaleimide (BMI);
step 2: weighing 60g of bismaleimide, adding 25g of diallyl bisphenol A, reacting at 115 ℃ for 1h, cooling to 80 ℃, adding a catalyst accounting for 0.012 percent of the total amount of the reactants, and continuously stirring at 80 ℃ for 30min to obtain the needed bismaleimide resin.
The glass transition temperature, tensile strength and repair efficiency of the cured resin are shown in Table 1.
TABLE 1
Figure BDA0001861624430000111
Example 10
The bismaleimide resin repair performance provided in table 1 was verified as follows:
1) the resin samples of examples 7 to 9 and comparative example 1 were prepared into rectangular specimens of 100X 10X 1mm in size, and a notch of 0.3mm in depth and 0.5mm in width was formed at the center in the longitudinal direction of the specimen, extending across the entire width to obtain damaged specimens.
2) Ethylenediamine was dissolved in a solvent of DMF/acetone (v/v ═ 1:1) to prepare a diamine restoration solution with a concentration of 10 mg/mL.
3) And (3) coating the damaged part of the damaged sample strip prepared by the resin in the step 1) by using the prepared diamine repairing liquid, heating to 100 ℃, and keeping the temperature until the surface of the damaged sample strip prepared by the resin in the examples 7-9 is dissolved, wherein the surface of the damaged sample strip prepared by the resin in the comparative example 1 cannot be dissolved.
4) The damaged sample strips prepared by the resin in the embodiments 7-9 are continuously heated to 160 ℃, so that the repairing liquid is volatilized to finish repairing.
5) For the damaged sample strips prepared from the resin of examples 7-9 after the repair is completed, the tensile strength of the sample before and after the repair is tested (see table 1 for specific data), and the repair efficiency is calculated according to the following formula:
repair efficiency (%) — tensile strength after repair of damaged sample/tensile strength of undamaged sample × 100%.
Examples 11 to 12
The damaged sample strips prepared by the resin in example 7 are subjected to a repair test by the method in example 10, wherein the concentration of the diamine repair solution in example 11 is 8mg/mL, the concentration of the diamine repair solution in example 12 is 15mg/mL, and the rest is consistent with that in example 10, and the tensile strength retention rate after repair is 93% and 90%.
The invention has not been described in detail and is in part known to those of skill in the art.

Claims (6)

1. A repairable bismaleimide resin restoration method is characterized by comprising the following steps:
firstly, preparing diamine restoration solution,
the diamine restoration solution is an organic diamine solution with a certain concentration;
secondly, coating the diamine repairing liquid prepared in the first step on the damaged part of the repairable bismaleimide resin, heating and insulating until the surface of the repairable bismaleimide resin is dissolved, wherein the lower limit of the heating temperature range is the initial temperature for exciting the imine bond exchange reaction in the repairable bismaleimide resin;
the repairable bismaleimide resin is obtained by reacting a modified bismaleimide monomer, an allyl compound and a catalyst, and the repairable bismaleimide resin is prepared by the following steps,
step 1, preparing modified diamine,
a1.1, dissolving diamine and a dialdehyde monomer in an organic solvent respectively to obtain a solution 1 and a solution 2 respectively, wherein the diamine and/or the dialdehyde is aromatic;
a1.2, dropwise adding the solution 2 into the solution 1 according to the proportion, fully reacting, and drying to obtain a product containing each repeating unit
Figure FDA0003524131770000011
A modified diamine of a segment in which the radical R 1 And R 2 At least one of them is an aromatic group;
step 2, reacting the modified diamine prepared in the step 1 with dianhydride to obtain a diamine containing each repeating unit
Figure FDA0003524131770000012
A modified bismaleimide monomer of a fragment;
step 3, reacting the modified bismaleimide monomer obtained in the step 2 with an allyl compound according to a proportion, adding a proper amount of catalyst, and fully reacting to obtain a product containing each repeating unit
Figure FDA0003524131770000013
A segmented bismaleimide resin system;
and thirdly, continuously heating to the temperature not higher than the oxidation temperature of the repairable bismaleimide resin, and volatilizing the diamine repair liquid to finish the repair of the bismaleimide resin.
2. The method for repairing repairable bismaleimide resin as claimed in claim 1, wherein: the concentration of the diamine restoration solution in the first step is not higher than 15 mg/mL.
3. The method for repairing repairable bismaleimide resin as claimed in claim 1, wherein: the concentration of the diamine restoration solution in the first step is 8 mg/mL-15 mg/mL.
4. The method for repairing repairable bismaleimide resin as claimed in claim 1, wherein: the upper limit of the heating temperature range in the second step is lower than the repairable bismaleimide resin oxidation temperature.
5. The method for repairing repairable bismaleimide resin as claimed in claim 1, wherein: the upper heating limit in the third step is lower than the repairable bismaleimide resin oxidation temperature.
6. The method for repairing repairable bismaleimide resin as claimed in claim 5, wherein: and in the third step, the heating temperature is 160-180 ℃.
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CN108129639A (en) * 2016-12-01 2018-06-08 航天特种材料及工艺技术研究所 A kind of epoxy curing agent and preparation method

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