CN113651942A

CN113651942A - Method for modifying thermosetting polymer material by using supramolecular additive and application thereof

Info

Publication number: CN113651942A
Application number: CN202110988034.6A
Authority: CN
Inventors: 王旭; 王璐平; 郭松
Original assignee: Shandong Zhengu New Material Technology Co ltd; Shandong University
Current assignee: Shandong Zhengu New Material Technology Co ltd; Shandong University
Priority date: 2021-08-26
Filing date: 2021-08-26
Publication date: 2021-11-16
Anticipated expiration: 2041-08-26
Also published as: CN113651942B

Abstract

The invention relates to the technical field of modification of functional polymer materials, in particular to a method for modifying a thermosetting polymer material by utilizing a supramolecular additive and application thereof. The supramolecular additive is added in the pre-formation stage of the prepolymer in the synthesis process of the thermosetting polymer material, the supramolecular additive can be inserted into the main chain of the thermosetting polymer, and the crosslinked polymer network can be dissociated and recombined under proper conditions by utilizing the dynamic property of the supramolecular additive, so that network rearrangement is realized, the recoverability of the thermosetting polymer is endowed, the production cost can be controlled, and the method has high practical applicability.

Description

Method for modifying thermosetting polymer material by using supramolecular additive and application thereof

Technical Field

The invention relates to the technical field of modification of functional polymer materials, in particular to a method for modifying a thermosetting polymer material by utilizing a supramolecular additive and application thereof.

Background

The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.

Thermosetting plastics have excellent mechanical properties, dimensional stability and chemical resistance, and thus are of great interest in applications with high performance requirements such as aerospace, military and building materials. However, most thermosetting plastics are inevitably incinerated or buried, causing environmental pollution, waste of resources and economic loss. The intrinsic reason for this is that the molecular network of the thermoset is permanently cross-linked by covalent bonds and, once formed, is hardly altered. In principle, many methods are used to treat thermoset contamination, such as acid and base treatment, high voltage discharge, biodegradation, use of strong acid catalysts, and the like. However, the above methods are unsatisfactory in both effects and costs, and thus are not widely accepted in the industry.

Therefore, the recycling rate of the thermosetting plastic is improved without damaging the excellent performance of the thermosetting plastic, the problem of solving the problem is very urgent, the cyclic economy is developed, and the sustainable development goal is realized. In fact, proper molecular design can impart dynamics to the crosslinked polymer network, thereby imparting reworkability to the thermoset. This approach does not add significant cost and has become one of the most feasible methods for the reprocessing of thermosets.

The inventors have studied and found that although the prior art discloses some polymers to enhance adhesion, self-healing and recyclability of the polymers by generating new-C ═ N-bonds, the preparation process is complicated and the conditions for generating-C ═ N-bonds need to be strictly controlled. There are also some techniques for simultaneously introducing-C ═ N-bond and supramolecule into thermosetting plastics, but the inventors found that these schemes need to consider the coordination relationship between supramolecule and-C ═ N-bond to avoid the antagonism of both, which affects the strength, medium resistance and recyclability of thermosetting plastics.

Disclosure of Invention

The invention provides a method for modifying a thermosetting polymer material by utilizing a supramolecular additive and application thereof, aiming at solving the problems that the traditional thermosetting polymer material is accumulated due to overhigh recovery cost or poorer recovery effect to cause environmental pollution and how to endow the thermosetting polymer material with certain recovery capability without losing the excellent performance. The supramolecular additive is inserted into the main chain of the thermosetting polymer, and the crosslinked polymer network can be dissociated and recombined under a proper condition by utilizing the dynamic property of the supramolecular additive, so that network rearrangement is realized, the recoverability of the thermosetting polymer is endowed, the production cost can be controlled, and the application is high in practical applicability.

Specifically, the invention is realized by the following technical scheme:

in a first aspect of the present invention, there is provided a method for modifying a thermosetting polymer material with a supramolecular additive, comprising: the supermolecule additive is added in the pre-formation stage of the prepolymer in the process of synthesizing the thermosetting polymer material.

In a second aspect of the present invention, a supramolecular additive modified thermosetting polymer material prepared by the method for modifying a thermosetting polymer material with a supramolecular additive is provided.

The third aspect of the invention provides an application of the supramolecular additive modified thermosetting polymer material in the fields of high mechanical strength, high temperature resistance, solvent resistance and recyclable materials.

One or more of the technical schemes have the following beneficial effects:

1) by adopting the technical scheme, the invention introduces the supramolecular additive based on the original production process of the thermosetting polymer material, and realizes the modification of the thermosetting polymer material.

2) If the supermolecule additive is grafted to the side chain of the thermosetting polymer material, a quadruple hydrogen bond system similar to a covalent bond is formed among the side chains, so that the polymer is promoted to form a network-shaped supermolecule structure, and the material has good reworkability of the thermoplastic polymer. Therefore, according to some technical schemes, the supramolecular additive is directly grafted to the main chain of the thermosetting polymer material, and the dynamic property of the supramolecular additive enables a crosslinked polymer network to be dissociated and recombined under proper conditions, so that network rearrangement is realized, and the recoverability of the thermosetting polymer is endowed on the premise of not losing the strength and chemical tolerance of the network.

3) The method for modifying the thermosetting polymer by utilizing the supramolecular additive provided by the technical scheme of the invention is simple and feasible, easily available in raw materials, low in cost and low in requirements on reaction conditions and used equipment. The supramolecular additive selected by the technical scheme of the invention has a wider application range, and can be used for adding various types of high polymer materials.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:

FIG. 1 is a schematic drawing showing the strain cycle elongation of a UPy-OH modified thermoset polyurethane material (HMPU-U0) prepared in comparative example 1, 50% representing the maximum strain applied by the material 50%, 100% representing the maximum strain 100%, 150% representing the maximum strain 150%, 200% representing the maximum strain 200%, and 400% representing the maximum strain 400%;

FIG. 2 is a schematic drawing showing the strain cycle elongation of the UPy-OH modified thermoset polyurethane material (HMPU-U1) prepared in example 1, with 50% representing the maximum strain applied by the material at 50%, 100% representing the maximum strain at 100%, 150% representing the maximum strain at 150%, 200% representing the maximum strain at 200%, and 400% representing the maximum strain at 400%;

FIG. 3 is a schematic drawing showing the strain cycle elongation of the UPy-OH modified thermoset polyurethane material (HMPU-U2) prepared in example 2, with 50% representing the maximum strain applied by the material at 50%, 100% representing the maximum strain at 100%, 150% representing the maximum strain at 150%, 200% representing the maximum strain at 200%, and 400% representing the maximum strain at 400%;

FIG. 4 is a schematic drawing showing the strain cycle elongation of the UPy-OH modified thermoset polyurethane material (HMPU-U9) prepared in example 3, with 50% representing the maximum strain applied by the material at 50%, 100% representing the maximum strain at 100%, 150% representing the maximum strain at 150%, 200% representing the maximum strain at 200%, and 400% representing the maximum strain at 400%;

FIG. 5 is a quantitative representation of the hysteresis energy of four thermoset polyurethanes prepared in comparative example 1 and examples 1-3;

FIG. 6 is a schematic diagram of the internal dissipation factors of four thermosetting polyurethane materials prepared in comparative example 1 and examples 1-3;

FIG. 7 is a schematic representation of the storage modulus of four thermoset polyurethane materials prepared in comparative example 1 and examples 1-3;

FIG. 8 is a graph of loss modulus versus temperature for four thermoset polyurethane materials prepared in comparative example 1 and examples 1-3;

FIG. 9 is an AFM view of a thermoset polyurethane material of HMPU-U0(a), HMPU-U1(b), HMPU-U5(c), HMPU-U9(d) UPy-OH;

FIG. 10 is the mechanical properties of the UPy-OH modified thermoset polyurethane material (HMPU-U1) prepared in example 1 at different recycling times;

FIG. 11 is the mechanical properties of the UPy-OH modified thermoset polyurethane material (HMPU-U5) prepared in example 2 at different recycling times;

FIG. 12 is the mechanical properties of the UPy-OH modified thermoset polyurethane material (HMPU-U9) prepared in example 3 at different recovery times;

FIG. 13 shows a comparison of the performance of a prepolymer/crosslinker system with respect to a thermoset obtained with or without the use of a supramolecular additive.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.

The recycling rate of the thermosetting plastic is improved, and the excellent performance of the thermosetting plastic is not damaged, so that the problem is solved, the cyclic economy is developed, and the aim of sustainable development is fulfilled. In fact, proper molecular design can impart dynamics to the crosslinked polymer network, thereby imparting reworkability to the thermoset. This approach does not add significant cost and has become one of the most feasible methods for the reprocessing of thermosets.

The invention provides a method for modifying a thermosetting polymer material by utilizing a supramolecular additive and application thereof, aiming at solving the problems that the traditional thermosetting polymer material is too high in recovery cost or poor in recovery effect and accumulates to pollute the environment, and how to endow the thermosetting polymer material with certain recovery capability without losing the excellent performance. The supramolecular additive is inserted into the main chain of the thermosetting polymer, and the crosslinked polymer network can be dissociated and recombined under a proper condition by utilizing the dynamic property of the supramolecular additive, so that network rearrangement is realized, the recoverability of the thermosetting polymer is endowed, the production cost can be controlled, and the application is high in practical applicability.

Specifically, the invention is realized by the following technical scheme:

The thermosetting plastic is endowed with recoverability from the perspective of molecular design, and reversible covalent bonds or supermolecule effects are introduced to replace irreversible covalent crosslinking, so that molecular chains can flow at high temperature, and network rearrangement becomes possible. The reversible covalent bond is used for replacing irreversible covalent crosslinking, which is beneficial to maintaining high strength, but a catalyst is needed in the reaction process, and the stability of the material is worried by 'reaction species' generated in the reaction process; the use of supramolecular interactions instead of irreversible covalent cross-linking allows the network to be broken and reformed relatively easily without catalysts, due to its weak binding strength, but reduces the strength and stability of the material. The invention utilizes the supermolecule additive to modify the thermosetting polymer, and the addition of the supermolecule segment additive can balance the strength, the medium resistance and the recyclability of the material, does not greatly change the original process, and has better feasibility from the technical and cost perspectives.

In one or more embodiments of the present invention, the supramolecular additive is selected from one or more of hydroxyl-terminated ureidopyrimidinone monomers, isocyanate-terminated ureidopyrimidinone monomers, adipic acid dihydrazide, vinylidene fluoride;

preferably, the thermosetting polymer material is selected from a polyurethane material or a polyurea material.

FIG. 13 shows a comparison of the performance of a prepolymer/crosslinker system with respect to a thermoset obtained with or without the use of a supramolecular additive. As can be seen from the figure, if no supramolecular additive is used, the thermosetting polymer obtained from the prepolymer/cross-linking agent system has no recyclability, or cannot be used after being recycled, and has no recycling value. After the supermolecule additive is used, the thermosetting polymer obtained by the prepolymer/cross-linking agent/supermolecule additive system has recyclability.

Taking hydroxyl-terminated ureido pyrimidone monomer as an example to show the method and the process for modifying the thermosetting polymer material by utilizing the supramolecular additive:

in one or more embodiments of the present invention, the insertion position of the supramolecular additive is a backbone in the network of the thermoset polymeric material. As mentioned above, the modified polymer obtained by grafting onto the side chains does not have the advantage of good recyclability, and therefore in some embodiments it is chosen to insert the supramolecular additive onto the backbone of the thermoset polymeric material network.

Preferably, the supramolecular additive accounts for 0.1-20% of the mass of the raw material of the thermosetting polymer material.

Too much supramolecular additive leads to a decrease in mechanical strength and chemical resistance; too little supramolecular additive may make the material more close to thermoset properties, affecting recyclability.

In one or more embodiments of the present invention, the organic solvent of the supramolecular additive is selected from one or more of N, N-dimethylformamide, dimethylsulfoxide, toluene.

In one or more embodiments of the present invention, the supramolecular additive is dispersed in an organic solution, and then the dispersion of the supramolecular additive is added before the prepolymer of the thermosetting polymer material is formed.

The dispersion liquid of the supramolecular additive is added in the pre-formation stage of the prepolymer of the thermosetting polymer material, and the supramolecular effect is introduced into a network main chain. The step also enables a small amount of the supermolecule additive to be added, saves raw materials on the premise of realizing the modification effect, and does not change the original production route of the thermosetting polymer.

In one or more embodiments of the present invention, the supramolecular additive needs to be heated during the process of dispersing in the organic solution, the heating temperature is 100-.

In one or more embodiments of the present invention, the method specifically includes:

dispersing the supramolecular additive in an organic solution to obtain a dispersion liquid;

mixing the dispersion liquid with a thermosetting high polymer material monomer, heating for reaction, cooling and curing.

In one or more embodiments of the present invention, the heating temperature during the mixing of the dispersion and the thermosetting polymer material monomer is 70 to 90 ℃, and the heating time is 1.5 to 3 hours.

The supramolecular additive and the thermosetting material monomer can be fully mixed and fully reacted within the temperature and time range; too high a temperature may exceed the boiling point of the solvent, and too low a temperature may not ensure sufficient dissolution of the supramolecular additive and thus may not ensure a perfect reaction.

The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.

Interpretation of terms:

UPy: ureidopyrimidinones available from Shao Yuan science and technology (Shanghai) Inc.;

UPy-OH: hydroxy (-OH) terminated ureidopyrimidinone monomers;

UPy-NCO: isocyanate group (-NCO) -terminated ureidopyrimidinone monomers;

ADH adipic dihydrazide, available from Sigma Aldrich trade, Inc.;

HDI: hexamethylene diisocyanate, available from alatin Biotech, Inc.;

DMF: n, N-dimethylformamide, a common organic solvent;

DMSO, DMSO: dimethyl sulfoxide, a common organic solvent;

HMDI 4,4' -dicyclohexylmethane diisocyanate, available from Aladdin Biotechnology Ltd;

IPDI: isophorone diisocyanate, available from alatin Biotech, Inc.;

PTMEG 1000: polytetrahydrofuran (molecular weight 1000) available from alatin biochem technologies, inc;

PCL diol 2000: polycaprolactone diol (molecular weight 2000) available from sigma aldrich trade, inc;

TMPMP trimethylolpropane tris (3-mercaptopropionate) available from Sigma Aldrich trade, Inc.;

DBTDL dibutyltin dilaurate, used as a catalyst, available from carbofuran technologies, Inc.;

HDI trimer, available from Vanhua chemical Co., Ltd;

BDO 1, 4-butanediol, available from Aladdin Biotechnology GmbH;

room temperature: having a meaning well known in the art, typically 25. + -. 2 ℃.

The mechanical property testing method comprises the following steps: INSTRON 3344 electronic Universal testing machine cuts the test specimens into rectangular shapes with dimensions 25mm x 5mm x 0.6mm at room temperature and a drawing rate of 50 mm/min. At least three measurements were made for each sample and averaged.

Internal friction factor: the peak value of the ratio of storage modulus to loss modulus is generally referred to as the glass transition temperature.

Storage modulus: ability of material to store elastic deformation energy

Loss modulus: the phenomenon describing the loss (transformation) of energy to heat when a material is deformed is a measure of the energy loss.

Glass transition temperature test method: TA DiscovAn ery 850 dynamic thermomechanical analyzer, stretching a rectangular sample at a constant frequency of 1Hz at a temperature of-50-125 deg.C, and heating at a rate of 3 deg.C for min^-1。

Comparative example 1: preparation of a thermoset polyurethane with 0% hydroxy-terminated ureido pyrimidone monomer

A100 mL round bottom flask was charged with 2.63g HMDI,

5g PTMEG

1000 and 300. mu.L DBTDL and heated in an 80 ℃ oil bath for 2h with magnetic stirring. And taking out after the reaction is finished, cooling to room temperature, adding 1.4493g of THDI and 0.5828g of BDO, stirring to be uniform at room temperature, and pouring into a polytetrafluoroethylene mold for deaeration. And (3) after the polyurethane is removed until no bubbles are generated, curing the polyurethane in an oven at 90 ℃ for 12h, and demolding to obtain the target polyurethane (marked as HMPU-U0).

Example 1: preparation of a thermoset polyurethane with 1% hydroxy-terminated ureido pyrimidone monomer content

0.04883g UPy-OH and 10g DMF were first added to a 100mL round bottom flask and heated in a 120 ℃ oil bath for more than 30min with magnetic stirring until a homogeneous clear solution was formed. Then another 100mL round bottom flask was charged with 1.32g of HMDI, 2.5g of

PTMEG

1000, 200. mu.L of DBTDL and the above solution and heated in an 80 ℃ oil bath for 2h with magnetic stirring. After the reaction is finished, taking out, cooling to room temperature, adding 0.732g of THDI and 0.2867g of BDO, stirring to be uniform at room temperature, pouring into a polytetrafluoroethylene mold, and defoaming. And (3) after the polyurethane is removed until no bubbles are generated, curing the polyurethane in an oven at 90 ℃ for 12h, and demoulding to obtain the target supramolecular additive modified polyurethane (marked as HMPU-U1).

Example 2: preparation of a thermoset polyurethane with 5% hydroxy-terminated ureido pyrimidone monomer content

First, 0.225g of UPy-OH and 15g of DMF were added to a 100mL round bottom flask and heated in a 120 ℃ oil bath with magnetic stirring for more than 30min until a homogeneous clear solution was formed. Then another 100mL round bottom flask was charged with 1.32g of HMDI, 2.5g of

PTMEG

1000, 200. mu.L of DBTDL and the above solution and heated in an 80 ℃ oil bath for 2h with magnetic stirring. After the reaction is finished, taking out, cooling to room temperature, adding 0.76g of THDI and 0.2668g of BDO, stirring to be uniform at room temperature, pouring into a polytetrafluoroethylene mold, and defoaming. And (3) after the polyurethane is removed until no bubbles are generated, curing the polyurethane in an oven at 90 ℃ for 12h, and demoulding to obtain the target supramolecular additive modified polyurethane (marked as HMPU-U5).

Example 3: preparation of a thermoset polyurethane with a hydroxyl-terminated ureido pyrimidone monomer content of 9%

0.4802g UPy-OH and 20g DMF were first added to a 100mL round bottom flask and heated in a 120 ℃ oil bath for more than 30min with magnetic stirring until a homogeneous clear solution was formed. Then another 100mL round bottom flask was charged with 1.32g of HMDI, 2.5g of

PTMEG

1000, 200. mu.L of DBTDL and the above solution and heated in an 80 ℃ oil bath for 2h with magnetic stirring. After the reaction is finished, taking out, cooling to room temperature, adding 0.80g of THDI and 0.24505g of BDO, stirring to be uniform at room temperature, pouring into a polytetrafluoroethylene mold, and defoaming. And (3) after the polyurethane is removed until no bubbles are generated, curing the polyurethane in an oven at 90 ℃ for 12h, and demoulding to obtain the target supramolecular additive modified polyurethane (marked as HMPU-U9).

The results are shown in FIGS. 1-5, where the hysteresis of the material is more pronounced with increasing content of supramolecular additives, due to the fact that supramolecules cannot instantaneously recombine after dissociation due to increased supramolecular interactions; as shown in fig. 6 to 8, the glass transition temperature gradually increases and the range becomes wider, the dynamic property of the internal molecular chain is significantly enhanced, and as shown in fig. 9, the surface roughness gradually decreases and the degree of phase separation decreases. As shown in fig. 10-12, the recyclability of the material is significantly enhanced with increasing content of supramolecular additives.

Table 1 shows the data characterizing the mechanical properties of the polyurethanes described in comparative example 1 and examples 1 to 3, from which it can be seen that the toughness of the material increases and then decreases as the content of supramolecular additive increases, which indicates that the introduction of a suitable amount of supramolecular action can sufficiently dissipate energy and redistribute stress, but when the supramolecular action is excessive, the covalent cross-linked network is weakened, thus decreasing the toughness; the breaking elongation of the material shows the same trend with the toughness along with the increase of the content of the supermolecule additive; as the content of supramolecular additives increases, the young's modulus of the material increases and the glass transition temperature increases, due to the increased density of hydrogen bonds; when the content of supramolecular additives increases to a certain extent, the covalently cross-linked network is destroyed and its inherent solvent resistance is affected.

Table 1 shows the data characterizing the mechanical properties of the polyurethanes described in comparative example 1 and examples 1 to 3

Comparative example 2: preparation of a thermoset polyurethane containing 0% of isocyanate group-terminated ureidopyrimidone monomer

A100 mL round bottom flask was charged with 2.63g HMDI, 10g PCL diol 2000 and 400. mu.L DBTDL and heated in an 80 ℃ oil bath for 2h with magnetic stirring. And taking out after the reaction is finished, cooling to room temperature, adding 0.4g of TMPMP and 0.408g of BDO, stirring to be uniform at room temperature, and pouring into a polytetrafluoroethylene mold for deaeration. And (3) after the polyurethane is removed until no bubbles are generated, curing the polyurethane in a 90 ℃ oven for 12h, and demolding to obtain the target polyurethane.

Example 4: preparation of a thermoset polyurethane having an isocyanate group-terminated ureidopyrimidone monomer content of 1%

First, 0.136g UPy-NCO and 15g DMF were added to a 100mL round bottom flask and heated in a 120 ℃ oil bath with magnetic stirring for more than 30min until a homogeneous clear solution was formed. Then in another 100mL round bottom flask was added 2.63g HMDI, 10g PCL diol 2000, 400. mu.L DBTDL and the above solution and heated in an oil bath at 80 ℃ for 2h with magnetic stirring. And taking out after the reaction is finished, cooling to room temperature, adding 0.408g of TMPMP and 0.428g of BDO, stirring to be uniform at room temperature, and pouring into a polytetrafluoroethylene mold for deaeration. And (3) after the polyurethane is removed until no bubbles are generated, curing the polyurethane in a drying oven at the temperature of 90 ℃ for 12 hours, and demolding to obtain the target supramolecular additive modified polyurethane.

Example 5: preparation of a thermoset polyurethane having an isocyanate group-terminated ureidopyrimidone monomer content of 5%

First, 0.7g of UPy-NCO and 20g of DMF were added to a 100mL round bottom flask and heated in a 120 ℃ oil bath with magnetic stirring for more than 30min until a homogeneous clear solution was formed. Then in another 100mL round bottom flask was added 2.63g HMDI, 10g PCL diol 2000, 400. mu.L DBTDL and the above solution and heated in an oil bath at 80 ℃ for 2h with magnetic stirring. After the reaction is finished, taking out, cooling to room temperature, adding 0.428g of THDI and 0.5g of BDO, stirring to be uniform at room temperature, pouring into a polytetrafluoroethylene mold, and defoaming. After the polyurethane is removed until no air bubbles are generated, the polyurethane is placed in a drying oven at the temperature of 90 ℃ for curing for 12 hours, and the target supramolecular additive modified polyurethane is obtained after demoulding

Comparative example 3: preparation of a thermosetting polyurea having a monomer content of adipic acid dihydrazide of 0%

1.05175g of hexamethylenediamine and 5g of IPDI were dissolved in 50mL of toluene. In addition, 0.6306g of melamine were dissolved in 25mL of toluene. Thereafter, the above solutions were mixed and stirred in a beaker for 12 hours. The precipitate was removed and washed three times with toluene. And then drying the product for 24 hours at 70 ℃ under vacuum to obtain the target polyurea.

Example 6: preparation of a thermosetting polyurea having a monomer content of adipic acid dihydrazide of 6%

0.4355g of ADH, 0.9015g of hexamethylenediamine and 5g of IPDI were dissolved in 50mL of toluene. In addition, 0.6306g of melamine were dissolved in 25mL of toluene. Thereafter, the above solutions were mixed and stirred in a beaker for 12 hours. The precipitate was removed and washed three times with toluene. And then drying the product for 24 hours at 70 ℃ under vacuum to obtain the target supramolecular additive modified polyurea.

Example 7: preparation of a thermosetting polyurea having a monomer content of adipic acid dihydrazide of 12%

0.871g of ADH, 0.75125g of hexamethylenediamine and 5g of IPDI were dissolved in 50mL of toluene. In addition, 0.6306g of melamine were dissolved in 25mL of toluene. Thereafter, the above solutions were mixed and stirred in a beaker for 12 hours. The precipitate was removed and washed three times with toluene. And then drying the product for 24 hours at 70 ℃ under vacuum to obtain the target supramolecular additive modified polyurea.

Comparative example 4: preparation of a thermoset polyurethane having a vinylidene fluoride monomer content of 0%

A100 mL round bottom flask was charged with 2.63g HMDI,

5g PTMEG

1000 and 300. mu.L DBTDL and heated in an 80 ℃ oil bath for 2h with magnetic stirring. And taking out after the reaction is finished, cooling to room temperature, adding 1.4493g of THDI and 0.5828g of BDO, stirring to be uniform at room temperature, and pouring into a polytetrafluoroethylene mold for deaeration. And (3) after the polyurethane is removed until no bubbles are generated, curing the polyurethane in a 90 ℃ oven for 12h, and demolding to obtain the target polyurethane.

Example 8: preparation of a thermoset polyurethane having a vinylidene fluoride monomer content of 5%

A100 mL round bottom flask was charged with 0.50g of vinylidene fluoride, 2.63g of HMDI, 5g of

PTMEG

1000 and 300. mu.L of DBTDL and heated in an 80 ℃ oil bath for 2h with magnetic stirring. And taking out after the reaction is finished, cooling to room temperature, adding 1.4493g of THDI and 0.5828g of BDO, stirring to be uniform at room temperature, and pouring into a polytetrafluoroethylene mold for deaeration. And (3) after the polyurethane is removed until no bubbles are generated, curing the polyurethane in a drying oven at the temperature of 90 ℃ for 12 hours, and demolding to obtain the target supramolecular additive modified polyurethane.

Example 9: preparation of a thermoset polyurethane having a vinylidene fluoride monomer content of 10%

A100 mL round bottom flask was charged with 1.07g of vinylidene fluoride, 2.63g of HMDI, 5g of

PTMEG

Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for modifying a thermosetting polymer material by using a supramolecular additive, comprising: the supermolecule additive is added in the pre-formation stage of the prepolymer in the process of synthesizing the thermosetting polymer material.

2. A method for modifying thermosetting polymer materials with supramolecular additives as claimed in claim 1, wherein said supramolecular additives are selected from one or more of hydroxyl terminated ureidopyrimidinone monomer, isocyanate terminated ureidopyrimidinone monomer, adipic dihydrazide, vinylidene fluoride;

3. The method of claim 1, wherein the supramolecular additive is inserted into the backbone of the network of the thermoset polymer material;

4. A method for modifying thermosetting polymer materials by using supramolecular additives as claimed in claim 1, wherein the organic solvent of the supramolecular additives is selected from one or more of N, N-dimethylformamide, dimethylsulfoxide, and toluene.

5. The method of claim 1, wherein the supramolecular additive is dispersed in an organic solution before the prepolymer of the thermosetting polymer material is formed.

6. The method as claimed in claim 1, wherein the supramolecular additive is dispersed in the organic solution and is heated at 100-130 ℃ for 20-40 min.

7. The method of claim 1, wherein the method comprises the steps of:

8. The method of claim 1, wherein the dispersion is mixed with the monomer of the thermosetting polymer at a temperature of 70-90 ℃ for a time of 1.5-3 h.

9. The supramolecular additive-modified thermoset polymeric material obtained by the method for modifying a thermoset polymeric material using a supramolecular additive as claimed in any one of claims 1 to 8.

10. Use of the supramolecular additive modified thermoset high molecular material as claimed in claim 9 in the field of high mechanical strength, high temperature resistance, solvent resistance, recyclable materials.