CN113136088B - Method for preparing high-performance matrix resin based on quadruple hydrogen bond toughened polybenzoxazine - Google Patents

Method for preparing high-performance matrix resin based on quadruple hydrogen bond toughened polybenzoxazine Download PDF

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CN113136088B
CN113136088B CN202110385067.1A CN202110385067A CN113136088B CN 113136088 B CN113136088 B CN 113136088B CN 202110385067 A CN202110385067 A CN 202110385067A CN 113136088 B CN113136088 B CN 113136088B
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benzoxazine
hydrogen bond
upy
matrix resin
nco
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CN113136088A (en
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王智
王维维
赵思培
乔子贺
杜杰
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North University of China
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

The invention discloses a method for preparing high-performance matrix resin based on quadruple hydrogen bond toughened polybenzoxazine. Namely, a quadruple hydrogen bond self-assembly molecule 2-ureido-4 [1H ] pyrimidone (UPy-NCO) with an isocyanate group at the end is introduced into a benzoxazine monomer. The terminal isocyanate group can react with phenolic hydroxyl generated by ring opening of benzoxazine, so that a quadruple hydrogen bond dynamic crosslinking network based on UPy group is introduced into a resin system. When the resin is impacted by the outside, the hydrogen bonds can be broken and recombined to realize energy dissipation and absorb part of impact energy, so that the toughness of the resin is improved. And due to the existence of the dynamic cross-linked network, the resin system can still keep higher mechanical property level after being repeatedly damaged.

Description

Method for preparing high-performance matrix resin based on quadruple hydrogen bond toughened polybenzoxazine
Technical Field
The invention relates to the field of resin modification, in particular to a method for preparing high-performance matrix resin based on quadruple hydrogen bond toughened polybenzoxazine.
Background
Benzoxazines are benzo-six-membered heterocyclic compounds synthesized from phenols, primary amines and aldehydes. The benzoxazine resin not only maintains the advantages of good mechanical property, heat resistance, dielectric property and the like of the traditional phenolic resin, but also has volume change close to zero during curing, and no micromolecule substance is discharged during curing, so that the cured product of the benzoxazine resin has low porosity and high precision. Strong acid catalysis is not needed during benzoxazine curing, and the benzoxazine curing agent has the characteristics of flexible molecular design, high carbon residue, low water absorption and the like. Although benzoxazine has the unique excellent properties, like other thermosetting resins, benzoxazine also has the disadvantages of large brittleness, low impact strength and poor toughness of cured products. The defects greatly limit the popularization and the application of the high-performance structural material in high and new technical fields such as aerospace and the like.
In recent decades, a large number of researchers have been engaged in toughening and modifying benzoxazine resins, and the methods adopted can be summarized as the following two methods. One method is to utilize the flexible molecular design of benzoxazine and introduce flexible groups into monomers to realize the improvement of toughness. This method is often costly and time consuming and difficult to achieve in an industrial process. The other method is to realize the improvement of the toughness of the resin by copolymerizing or blending two or more different materials, for example, adding small particles (rubber particles, inorganic nanoparticles and the like) with certain shapes and sizes into a resin system to form a two-phase or multi-phase structure. Or thermoplastic plastics or other thermosetting resins are introduced into the benzoxazine resin, and phase separation reaction occurs in the curing process, so that the sea-island structure, the bicontinuous phase structure and the reverse transformation structure are formed, and the toughness of the system can be effectively improved. However, in the above modification method, the crosslinked network is destroyed after the resin is damaged, it is difficult to withstand the secondary damage, and the improvement of the toughness of the resin system is accompanied by the sacrifice of the thermal properties or the processability. On the premise of keeping the balance of the toughness, the thermal property and the processability of the resin, the resin system can still keep a higher mechanical property level after being repeatedly damaged, which is still a challenging problem.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a method for preparing high-performance matrix resin based on quadruple hydrogen bond toughened polybenzoxazine; reversible hydrogen bonds are introduced into the benzoxazine resin, so that the toughness of the benzoxazine resin is improved, and the benzoxazine resin can still keep a higher mechanical property level after being repeatedly damaged.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for preparing high-performance matrix resin based on quadruple hydrogen bond toughened polybenzoxazine is characterized in that quadruple hydrogen bond self-assembly molecules 2-ureido-4 [1H ] pyrimidone (UPy-NCO) with the tail end containing isocyanate groups are introduced into benzoxazine monomers, and the high-performance benzoxazine matrix resin is obtained after thermocuring, so that the high mechanical property level can be still maintained after repeated damage.
The terminal isocyanate group of UPy-NCO can react with phenolic hydroxyl generated by ring opening of benzoxazine, so that a quadruple hydrogen bond dynamic crosslinking network based on UPy group is introduced into a resin system. On one hand, when the resin is impacted by the outside, the energy dissipation is realized through the breakage and recombination of the hydrogen bonds, and part of impact energy is absorbed, so that the toughness of the resin is improved. On the other hand, nitrogen atoms in UPy molecules can form new-OH … N hydrogen bonds with benzoxazine, and the type and the number of the system hydrogen bonds are adjusted, so that the crosslinking density of the system is improved, and the toughness of the resin is improved. The original crosslinking state can be recovered under certain conditions after the dynamic crosslinking network is damaged, and the resin can still keep higher mechanical property level after being repeatedly damaged.
Further, the method for preparing the high-performance matrix resin based on the quadruple hydrogen bond toughened polybenzoxazine specifically comprises the following steps:
step (1): benzoxazine monomers were blended with 2-ureido-4 [1H ] pyrimidinone (UPy-NCO) in an organic solvent and sonicated to complete dissolution.
Step (2): and (3) removing the solvent from the dissolved solution in a vacuum drying oven at 140 ℃, then placing the dissolved solution in a blast drying oven, setting a temperature gradient for solidification, and cooling to obtain the high-performance benzoxazine matrix resin.
Further, the addition amount of UPy-NCO is 1-5 wt% of the total amount of benzoxazine monomers.
Further, the benzoxazine is one or more of bisphenol A type benzoxazine, MDA type benzoxazine, bisphenol F type benzoxazine and monocyclic benzoxazine.
Further, the organic solvent in the step (1) is one of DMF, DMSO and ethanol.
Further, the temperature gradient in the step (2) is as follows: the temperature is kept at 160 ℃ for 2h, 180 ℃ for 2h and 200 ℃ for 2 h.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention utilizes quadruple hydrogen bond self-assembly molecule 2-ureido-4 [1H ] pyrimidone (UPy-NCO) with the tail end containing isocyanate group to carry out toughening modification on benzoxazine resin, and can greatly improve the toughness of the benzoxazine resin.
2. The invention utilizes quadruple hydrogen bond self-assembly molecule 2-ureido-4 [1H ] pyrimidone (UPy-NCO) with the tail end containing isocyanate group to toughen and modify the benzoxazine resin, and the resin system can still keep higher mechanical property level after being repeatedly damaged.
3. The invention utilizes quadruple hydrogen bond self-assembly molecule 2-ureido-4 [1H ] pyrimidone (UPy-NCO) with the tail end containing isocyanate group to toughen and modify the benzoxazine resin, realizes the balance of toughness, thermal property and processability of the resin and has wide application prospect.
And 4, the synthesis method of UPy-NCO is simple, and the blending modification mode is easy to realize industrial production.
Drawings
FIG. 1 is a diagram of quadruple hydrogen bonds in UPy-NCO. The quadruple hydrogen bonds have stronger dynamic property than common hydrogen bonds, a quadruple hydrogen bond dynamic cross-linking network is introduced into a resin system, when the resin is impacted by the outside, the hydrogen bonds are broken and recombined to realize energy dissipation, and part of impact energy is absorbed, so that the toughness of the resin is improved.
FIG. 2 is a graph showing the impact strength of modified resins at different amounts of UPy-NCO added in examples and comparative examples of the present invention.
FIG. 3 is a graph showing the loss tangent (tan. delta.) of the modified resin as a function of temperature for various amounts of UPy-NCO added in examples and comparative examples of the present invention.
FIG. 4 is a graph showing the temperature dependence of the complex viscosity of the modified resin at different UPy-NCO addition levels in example 3 of the present invention and in comparative examples.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
The method for preparing high-performance matrix resin from 2-ureido-4 [1H ] pyrimidinone (UPy-NCO) toughened polybenzoxazine comprises the following steps:
step one, blending bisphenol A benzoxazine and UPy-NCO into DMF (solvent) according to the mass ratio of 99:1, and performing ultrasonic treatment until complete dissolution.
Step two: the preparation of UPy-NCO/bisphenol A benzoxazine modified resin comprises,
the dissolved solution was poured into an aluminum mold preheated in advance and coated with a release agent, and then placed in a vacuum oven at 140 ℃ to remove the solvent until no significant bubbles were generated. And then placing the mixture in a blast oven, setting the temperature gradient to be 160 ℃/2h +180 ℃/2h +200 ℃/2h for curing, and cooling to obtain the UPy-NCO modified benzoxazine resin.
Example 2
The method for preparing high-performance matrix resin from 2-ureido-4 [1H ] pyrimidone (UPy-NCO) toughened polybenzoxazine comprises the following steps:
step one, blending bisphenol A benzoxazine and UPy-NCO in DMF (solvent) according to the mass ratio of 97:3, and performing ultrasonic treatment until complete dissolution.
Step two: the preparation of UPy-NCO/bisphenol A benzoxazine modified resin comprises,
the dissolved solution was poured into an aluminum mold preheated in advance and coated with a release agent, and then placed in a vacuum oven at 140 ℃ to remove the solvent until no significant bubbles were generated. And then placing the mixture in a blast oven, setting the temperature gradient to be 160 ℃/2h +180 ℃/2h +200 ℃/2h for curing, and cooling to obtain the UPy-NCO modified benzoxazine resin.
Example 3
The method for preparing high-performance matrix resin from 2-ureido-4 [1H ] pyrimidone (UPy-NCO) toughening polybenzoxazine comprises the following steps:
step one, blending BA-a and UPy-NCO in DMF (solvent) according to the mass ratio of 95:5, and carrying out ultrasonic treatment until the BA-a and the UPy-NCO are completely dissolved.
Step two: the preparation of UPy-NCO/bisphenol A benzoxazine modified resin comprises,
the solution was poured into an aluminum mold preheated in advance and coated with a release agent, and then placed in a vacuum drying oven at 140 ℃ to remove the solvent until no significant air bubbles were generated. And then placing the mixture in a blast oven, setting the temperature gradient to be 160 ℃/2h +180 ℃/2h +200 ℃/2h for curing, and cooling to obtain the UPy-NCO modified benzoxazine resin.
Comparative example one: the preparation of the unmodified bisphenol A benzoxazine resin comprises,
bisphenol a benzoxazine was added to DMF (solvent) and sonicated to complete dissolution. The dissolved solution was poured into an aluminum mold preheated in advance and coated with a release agent, and then placed in a vacuum oven at 140 ℃ to remove the solvent until no significant bubbles were generated. Then placing the mixture in a blast oven, setting the temperature gradient to be 160 ℃/2h +180 ℃/2h +200 ℃/2h for curing, and cooling to obtain the benzoxazine resin.
The impact strength test, the determination of the relationship between the loss tangent (tan delta) of the modified resin and the temperature change, and the determination of the relationship between the composite viscosity of the modified resin and the temperature change were carried out on the unmodified bisphenol a type benzoxazine resins of examples one to three UPy-NCO and comparative example one, and the determination results are shown in table 1 and fig. 2 to 3.
TABLE 1 impact Strength of UPy-NCO-modified benzoxazine resins prepared in examples one to three
Item UPy-NCO content Impact Strength (kJ/m)2)
Comparative example 1 0 6.03
Example one 1wt％ 12.39
Example two 3wt％ 14.11
EXAMPLE III 5wt％ 11.06
As can be seen from the table, the toughness of the benzoxazine resin can be obviously improved by adding UPy-NCO, and when the UPy-NCO content is 3 wt%, the impact strength of the blended resin system reaches 14.11kJ/m2The content of the benzoxazine resin is improved by 134 percent compared with that of the unmodified benzoxazine resin.
As can be seen from FIG. 2, the impact strength of the cured unmodified bisphenol A benzoxazine resin was 6.03 kJ. m-2. The impact strength of the UPy-NCO/BA-a blending system shows a tendency of increasing and then decreasing with the increasing UPy-NCO content. When the UPy-NCO content is 1 wt%, 3 wt% and 5 wt%, the impact strength of the blended system is respectively increased by 105%, 134% and 83% compared with that of the pure benzoxazine resin, and the values reach 12.39, 14.11 and 11.06 kJ.m-2。
As can be seen from FIG. 3, the blending system has only one peak value at 200 ℃, which shows that the UPy-NCO/bisphenol A benzoxazine blending system has only one glass transition temperature (T)g) No phase separation structure is formed in the blend. It can also be seen that the T of the UPy-NCO/bisphenol A benzoxazine blendgHigher than pure benzoxazine and increases with the UPy-NCO content, when the UPy-NCO addition is only 3 wt%, the blend has a TgUp to 206 ℃ which is 31 ℃ higher than that of pure benzoxazine, indicating that only a small amount of addition was madeThe UPy-NCO can obviously improve the heat resistance of the benzoxazine resin.
As can be seen from FIG. 4, in order to compare the rheological properties of the pure bisphenol A benzoxazine and UPy-NCO/BA-a blend systems, the processing window was determined at a viscosity of 1000 pas. It can be found by calculation that the processing window of a 5 wt% UPy-NCO/bisphenol a type benzoxazine blending system is about 120 ℃, which provides a sufficient temperature range for the preparation of modified benzoxazine resin based composite materials.

Claims (6)

1. A method for preparing high-performance matrix resin based on quadruple hydrogen bond toughened polybenzoxazine is characterized in that quadruple hydrogen bond self-assembly molecules UPy-NCO with isocyanate groups at the tail ends are introduced into benzoxazine monomers, and the high-performance benzoxazine matrix resin is obtained after thermocuring, so that the high mechanical property level can be maintained after repeated damage.
2. The method for preparing the high-performance matrix resin based on the quadruple hydrogen bond toughened polybenzoxazine as claimed in claim 1, which is characterized by comprising the following steps:
step (1): blending benzoxazine monomer and UPy-NCO in an organic solvent, and performing ultrasonic treatment until the benzoxazine monomer and UPy-NCO are completely dissolved;
step (2): and (3) removing the solvent from the dissolved solution in a vacuum drying oven at 140 ℃, then placing the dissolved solution in a blast oven, setting a temperature gradient for solidification, and cooling to obtain the high-performance benzoxazine matrix resin.
3. The method for preparing the high-performance matrix resin based on the quadruple hydrogen bond toughened polybenzoxazine as claimed in claim 1 or 2, wherein the UPy-NCO is added in an amount of 1-5 wt% based on the total amount of benzoxazine monomers.
4. The method for preparing the high-performance matrix resin based on the quadruple hydrogen bond toughened polybenzoxazine according to the claim 1 or the claim 2, wherein the benzoxazine is one or more of bisphenol A benzoxazine, MDA benzoxazine, bisphenol F benzoxazine and monocyclic benzoxazine.
5. The method for preparing the high-performance matrix resin based on the quadruple hydrogen bond toughened polybenzoxazine as claimed in claim 2, wherein the organic solvent in the step (1) is one of DMF, DMSO and ethanol.
6. The method for preparing the high-performance matrix resin based on the quadruple hydrogen bond toughened polybenzoxazine as claimed in claim 2, wherein the temperature gradient in the step (2) is as follows: the temperature is kept at 160 ℃ for 2h, 180 ℃ for 2h and 200 ℃ for 2 h.
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