CN109370131B

CN109370131B - Dynamic topological interlocking dual network and preparation method and application thereof

Info

Publication number: CN109370131B
Application number: CN201810866569.4A
Authority: CN
Inventors: 容敏智; 彭伟黎; 章明秋
Original assignee: Sun Yat Sen University
Current assignee: Sun Yat Sen University
Priority date: 2018-08-01
Filing date: 2018-08-01
Publication date: 2021-01-22
Anticipated expiration: 2038-08-01
Also published as: CN109370131A

Abstract

The invention relates to a dynamic topological interlocking dual network and a preparation method and application thereof. The dynamic topological interlocking double network comprises the following components in parts by weight: 20-80 parts of a polyurethane dynamic reversible crosslinking network; 20-80 parts of a polyacrylate dynamic reversible crosslinking network; the polyurethane dynamic reversible crosslinking network is polyurethane containing reversible bonds, the polyacrylate dynamic reversible crosslinking network is polyacrylate containing reversible bonds, and the reversible bonds contained in the polyurethane and the polyacrylate are different and do not influence each other. The dynamic topological interlocking double network provided by the invention has the capability of multiple unlocking and secondary interlocking, shows stronger mechanical property than the initial single network, has good multiple self-repairing capability and solid recycling performance, and has wide application prospect.

Description

Dynamic topological interlocking dual network and preparation method and application thereof

Technical Field

The invention belongs to the field of intelligent polymer materials, and particularly relates to a dynamic topological interlocking dual network, and a preparation method and application thereof.

Background

Polymer materials have many advantages such as light weight, easy processing, excellent mechanical properties, and the like, and thus are widely used in various fields. With the progress of society and the improvement of living standard, people have higher and higher requirements on the performance of high polymer materials. The high polymer material not only has excellent mechanical property, but also can be self-repaired and recycled for many times so as to ensure the stability of the material and prolong the service life. However, the mechanical properties and the self-repairing properties of the polymer materials are often contradictory, because the mobility of molecular chains and the rapid chemical bond dynamic exchange reaction are necessary conditions required by intrinsic polymer self-repairing, but these characteristics often cause the reduction of the mechanical properties of the materials.

The mechanical property of the high polymer material has a great relationship with the physical and chemical structure thereof, and although the mechanical property of the high polymer material can be improved by changing the crosslinking density, the rigidity degree of a molecular chain and the like of the high polymer material, the self-repairing of the high polymer material can be greatly hindered. Changing the topological structure of the high molecular material can also effectively change the mechanical properties of the material, such as the traditional interpenetrating network polymer and double-network polymer, and forming a special topological structure by mixing and interpenetrating two different networks, so that the two networks generate a synergistic effect, the functions of each network are fully exerted, and the mechanical properties of the final product are improved. However, no matter interpenetrating networks or double networks exist, the related polymer networks are mainly crosslinked by irreversible covalent bonds, and the polymer networks have no self-repairing performance and can not be recycled.

Therefore, the development of a polymer material which has strong mechanical property, self-repairing property and can be recycled has important research significance and application value.

Disclosure of Invention

The invention aims to overcome the defects that the high molecular material in the prior art has no self-repairing function and cannot be recycled, and provides a dynamic topological interlocking double network. The dynamic topological interlocking double network provided by the invention is crosslinked through the dynamic covalent bonds of the polyurethane dynamic reversible crosslinked network and the polyacrylate dynamic reversible crosslinked network, so that the crosslinked network dynamic exchange tends to be in a dissociation state in the network compounding process, the networks are fully mixed, and then the dynamic covalent bonds of the networks are recombined to obtain the dynamic topological interlocking double network. The double network has the capability of multiple unlocking and secondary interlocking, shows stronger mechanical property than the original single network, and simultaneously has good multiple self-repairing capability and solid-state recycling performance.

The invention also aims to provide a preparation method of the dynamic topological interlocking dual network.

The invention also aims to provide the method for unlocking and re-interlocking the dynamic topological interlocking dual network.

The invention also aims to provide application of the dynamic topological interlocking double network in preparing high-performance self-repairing or recyclable polymer materials.

Another object of the present invention is to provide a self-repairing method of the above dynamic topology interlocking dual network.

Another object of the present invention is to provide a method for recovering the dynamic topology interlocking dual network.

In order to achieve the purpose, the invention adopts the following technical scheme:

a dynamic topological interlocking dual network comprises the following components in parts by weight:

20-80 parts of polyurethane dynamic reversible crosslinked network

20-80 parts of a polyacrylate dynamic reversible crosslinking network;

the polyurethane dynamic reversible crosslinking network is polyurethane containing reversible bonds, the polyacrylate dynamic reversible crosslinking network is polyacrylate containing reversible bonds, and the reversible bonds contained in the polyurethane network and the polyacrylate network are different and do not affect each other.

The dynamic topological interlocking double network provided by the invention is crosslinked through the dynamic covalent bonds of the polyurethane dynamic reversible crosslinked network and the polyacrylate dynamic reversible crosslinked network, so that the crosslinked network dynamic exchange tends to be in a dissociation state in the network compounding process, the networks are fully mixed, and then the dynamic covalent bonds of the networks are recombined to obtain the dynamic topological interlocking double network. The double network has the capability of multiple unlocking and secondary interlocking, shows stronger mechanical property than the original single network, and simultaneously has good multiple self-repairing capability and solid-state recycling performance.

Preferably, the reversible bond is a disulfide bond, a schiff base, a borate bond, a C-ON bond, a host-guest reversible bond, or a metal ion coordination bond.

Preferably, the dynamic topological interlocking dual network consists of the following components in parts by weight:

50 parts of polyurethane dynamic reversible crosslinked network

50 parts of polyacrylate dynamic reversible crosslinking network.

The invention provides a dynamic reversible crosslinking network of polyurethane containing disulfide bond reversible bonds.

Preferably, the polyurethane dynamic reversible crosslinked network is prepared by the following method:

s11: under the catalytic action of a catalyst, carrying out prepolymerization reaction on dihydric alcohol and diisocyanate to obtain a polyurethane prepolymer;

s12: adding a chain extender containing a disulfide bond into the polyurethane prepolymer obtained in the step S11 for chain extension;

s13: and adding trifunctional alcohol or trifunctional ammonia crosslinking agent into the chain extension product obtained in the step S12 for crosslinking reaction to obtain the polyurethane dynamic reversible crosslinked network.

The disulfide bond-containing polyurethane dynamic reversible crosslinked network can be crosslinked with a polyacrylate dynamic reversible crosslinked network containing dynamic reversible bonds (such as borate bonds, Schiff base bonds and the like), and topological interlocking among network molecules is generated to obtain a dynamic topological interlocking double network.

Preferably, the mass ratio of the catalyst, the dihydric alcohol and the diisocyanate in the S11 is 0.01-0.1: 2-20: 1-5; the prepolymerization reaction is carried out at the temperature of 50-70 ℃ for 4-12 h.

Preferably, in the chain extension reaction system in S12, the mass fraction of the disulfide chain extender is 0.5-2%; the reaction temperature of the chain extension is 50-70 ℃, and the reaction time is 6-12 h.

Preferably, the mass fraction of the trifunctional alcohol or trifunctional ammonia crosslinking agent in the crosslinking reaction system in S13 is 0.25-1%; the temperature of the crosslinking reaction is 50-70 ℃, and the time is 6-12 h.

More specifically, the preparation method of the polyurethane dynamic reversible crosslinked network comprises the following steps:

s11: dissolving 2-20 parts of diol subjected to vacuum drying at 100-120 ℃ for 12-24 hours by using 30-60 parts of anhydrous solvent, placing the diol into a 100mL three-neck flask, dissolving 1-5 parts of diisocyanate in 2-10 parts of anhydrous solvent, dropwise adding the diisocyanate into the three-neck flask under the protection of high-purity nitrogen under the conditions of reflux condensation and magnetic stirring, controlling the reaction temperature to be 40-70 ℃, adding 0.01-0.1 part of catalyst into a reaction system, and reacting for 4-12 hours to obtain the polyurethane prepolymer PU.

S12: dissolving 0.5-2 parts of a disulfide chain extender into 2-5 parts of an anhydrous solvent, adding the solution into a reaction system, and performing chain extension reaction at 50-70 ℃ for 6-12 hours to obtain the disulfide bond-containing linear polyurethane.

S13: and then dissolving 0.1-1 part of trifunctional alcohol or trifunctional ammonia crosslinking agent in 2-5 parts of anhydrous solvent, adding the solution into a reaction system, and reacting at 50-70 ℃ for 6-12 h to obtain disulfide bond-containing crosslinked polyurethane PU-SS viscous gel, namely the polyurethane dynamic reversible crosslinked network.

More preferably, the anhydrous solvent in S11-S13 is one or more of anhydrous dichloromethane, anhydrous tetrahydrofuran, anhydrous acetone or anhydrous NN dimethylformamide.

More preferably, the diol in S11 is one or more of polyester diol and polyether diol; the diisocyanate is one or more of isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), 4' -dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI) or Lysine Diisocyanate (LDI); the catalyst is DBTDL.

More preferably, the disulfide chain extender in S12 is one or more of 2,2' -diaminodiphenyl disulfide, 4' -diaminodiphenyl disulfide, bis (2-hydroxyethyl) disulfide or 4,4' -dihydroxydiphenyl disulfide.

More preferably, the trifunctional crosslinker in S13 is one or more of triethanolamine, trimethylolpropane, castor oil, and pentaerythritol.

The invention provides a polyacrylate dynamic reversible crosslinked network containing borate bonds or Schiff base bond reversible bonds.

Preferably, the polyacrylate dynamic reversible crosslinked network is prepared by the following method:

s21: uniformly mixing an acrylate monomer and an allyl diol monomer or an acrylate monomer and allyl aromatic aldehyde, and adding a free radical initiator to initiate monomer polymerization to obtain a polymerization product;

s22: adding a boric acid crosslinking agent and diol or a polyamine crosslinking agent and aldehyde groups into the polymerization product obtained in the step S21, and carrying out crosslinking reaction to obtain a polyacrylate network;

or S23: and (2) uniformly mixing an acrylate monomer and a diene cross-linking agent containing borate, or uniformly mixing the acrylate monomer and the diene cross-linking agent containing Schiff base, and adding a free radical initiator to initiate monomer polymerization to obtain the polyacrylate network.

Preferably, the mass ratio of the radical initiator, the acrylate monomer and the allyl diol monomer/allyl aromatic aldehyde in S21 is 0.1-0.5: 5-20: 1-5; the polymerization temperature of the monomer is 60-80 ℃, and the reaction time is 10-24 h.

Preferably, the molar ratio of hydroxyl groups in the boric acid crosslinking agent to allyl diol monomers in the crosslinking reaction system in S22 is 1:2 or the molar ratio of amino groups to allyl aromatic aldehyde in the polyamine crosslinking agent is 1: 2; the temperature of the crosslinking reaction is 30-70 ℃, and the time is 1-3 h.

Preferably, the mass ratio of the free radical initiator, the acrylate monomer and the diene cross-linking agent containing borate to the diene cross-linking agent containing Schiff base in S23 is 0.1-0.5: 5-20: 1-5; the polymerization temperature of the monomer is 60-80 ℃, and the reaction time is 10-24 h.

More specifically, the preparation method of the polyacrylate dynamic reversible crosslinked network comprises the following steps:

s21: weighing 5-20 parts of acrylate monomer, 1-5 parts of allyl diol monomer or allyl aromatic aldehyde in 30-60 parts of organic solvent, and adding N₂And (2) magnetically stirring for 0.5-1 h under protection, controlling the reaction temperature to be 60-80 ℃, then gradually dripping 5-20 parts of organic solution containing 0.1-0.5 part of free radical initiator by using a constant-pressure dropping funnel, and continuing to mechanically stir and react for 10-24 h after dripping.

S22: and (3) adding 0.5-2 parts of a boric acid crosslinking agent or a polyamine crosslinking agent into the linear polymerization product obtained in the step S21 for crosslinking, reacting for 1-3 hours at 30-70 ℃ to crosslink diol or aldehyde groups, and casting to form a film, thus obtaining the polyacrylate dynamic reversible crosslinking network viscous gel, namely the polyacrylate dynamic reversible crosslinking network.

Or S23: weighing 5-20 parts of acrylate monomer and 1-5 parts of diene cross-linking containing boric acid esterDiene cross-linking agent containing Schiff base in 30-60 parts of organic solvent, and N₂And (2) magnetically stirring for 0.5-1 h under protection, controlling the reaction temperature to be 60-80 ℃, then gradually dripping 5-20 parts of organic solution containing 0.1-0.5 part of free radical initiator by using a constant-pressure dropping funnel, and continuing to mechanically stir and react for 10-24 h after dripping.

Preferably, the acrylate monomers in S21 and S23 are one or more of acrylic acid, methyl acrylate, tert-butyl acrylate, methyl methacrylate and tert-butyl methacrylate; the allyl diol is 3-allyloxy-1, 2-propanediol; the allyl aromatic aldehyde is polyethylene glycol p-benzaldehyde ester methacrylate; the organic solvent is one or more of dioxane and NN dimethylformamide; the free radical initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate initiator, benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide.

Preferably, the diboronic acid crosslinking agent in S22 is one or more of 1, 4-phenyl diboronic acid and boric acid; the polyamine crosslinking agent is one or more of ethylenediamine, hexamethylenediamine, p-phenylenediamine and triaminoethylamine.

Preferably, the diene crosslinking agent containing borate in S23 is one or more of p-allyloxybenzene borate or diallyl borate; the diene cross-linking agent containing Schiff base is one or more of diallyl Schiff base or diallyl aromatic Schiff base.

The preparation method of the dynamic topological interlocking dual network comprises the following steps:

s31: mixing the polyurethane dynamic reversible crosslinking network and the polyacrylate dynamic reversible crosslinking network, stirring and carrying out ultrasonic treatment to obtain a mixture;

s32: treating the mixture obtained in the step S31 at a high temperature of 60-100 ℃ or under the irradiation of ultraviolet light to obtain a yellow transparent sticky polymer;

s33: and (4) pouring the yellow transparent viscous polymer obtained in the step S32, standing and drying to obtain the dynamic interlocking double network.

According to the invention, by utilizing the dynamic reversibility of reversible bonds, the polyurethane dynamic reversible crosslinked network containing the reversible bonds and the polyacrylate dynamic reversible crosslinked network are subjected to topological interlocking between network molecules in the processes of light and heat treatment to obtain the dynamic topological interlocking double network. The topological interlocking double network provided by the invention can be unlocked into the initial single network again under certain acidic solvent treatment, and the initial raw material single network is obtained again. The recovered single network can be interlocked again to obtain the dynamic topological interlocking double network, the process can be repeated for many times, and the dynamic topological interlocking multiple network can be prepared theoretically. The topological interlocking double network provided by the invention has stronger mechanical property than the initial single network, has good repeated self-repairing capability and solid recycling performance, and has wide application prospect.

Preferably, the stirring time in S31 is 0.5-2 h; the ultrasonic time is 0.5-2 h.

Preferably, the treatment time under the high-temperature condition in S32 is 3-12 h; in S32, the irradiation power under the ultraviolet light is 100-3000 w, and the time is 1-12 h.

More specifically, the method for unlocking and re-interlocking the dynamic topology interlocking dual network comprises the following steps:

s31: taking the polyurethane dynamic reversible crosslinking network and the polyacrylate dynamic reversible crosslinking network, stirring the mixture by a homogenizer for 0.5 to 2 hours to mix the mixture evenly, and then heating the mixture by ultrasonic for 0.5 to 2 hours to further mix the mixture to obtain a mixture;

s32: and (3) treating the mixture obtained in the step S31 at 60-100 ℃ for 3-12 h, or illuminating for 1-12 h by adopting an ultraviolet lamp with the power of 100-3000 w, further completely interpenetrating the mixture to obtain a yellow transparent sticky polymer, pouring the yellow transparent sticky polymer into a mold, standing for 0.5-1 h to remove bubbles, standing at room temperature for 12-24 h, and then placing in a vacuum drying oven at 50-80 ℃ for 1-3 days to obtain a yellow transparent dynamic interlocking double network DILDN, namely the dynamic topological interlocking double network.

The method for unlocking and interlocking again by the dynamic topological interlocking double networks comprises the following steps:

s41: crushing the dynamic topological interlocking double network at a low temperature of not higher than-60 ℃, and stirring and crushing for 2-3 times at a high speed to obtain a powder sample;

s42: dispersing the powder sample obtained in the step S41 in a mixed solution soaked in an acidic solvent with the pH value of 2-4.5;

s43: filtering the mixed solution obtained in the step S42 to obtain filtrate and residual solid; pouring the obtained filtrate into a film and drying to obtain an unlocked polyacrylate dynamic reversible crosslinked network; the obtained residual solid is molded into a film to obtain an unlocked polyurethane dynamic reversible crosslinked network;

s44: and (3) crushing the unlocked polyacrylate network and the unlocked polyurethane network obtained in the step (S43) at a low temperature, uniformly mixing, placing in a solvent, treating at a high temperature of 60-150 ℃ or under ultraviolet irradiation, casting to form a film, standing and drying to obtain the secondary interlocking dynamic topological interlocking double network.

Preferably, NN dimethylformamide and dimethyl sulfoxide are selected as a solvent in S44.

The dynamic topological interlocking double network is soaked in an acid solution for a long time so as to unlock a polyacrylate network and a polyurethane network in the dynamic topological interlocking double network, the two unlocked networks are interlocked again under light or heat treatment to obtain the dynamic topological interlocking double network, and the process can be repeated for many times.

Preferably, in S41, cryogenic pulverization is performed using liquid nitrogen as a cryogenic coolant.

Preferably, the mass ratio of the powder sample to the acidic solvent in S42 is 5-20: 40-200.

Preferably, the drying temperature in S43 is 60-80 ℃; the temperature of the die pressing is 50-150 ℃, the pressure of the die pressing is 1-15 MPa, and the time of the die pressing is 1-12 h.

Preferably, repeating S41-S44 can obtain a polyacrylate dynamic reversible crosslinked network unlocked for multiple times, an unlocked polyurethane dynamic reversible crosslinked network unlocked for multiple times, and a dynamic topological interlocking double network interlocked again.

s41: rapidly freezing the dynamic topological interlocking network by using liquid nitrogen, and crushing for 2-3 times to obtain a powder sample;

s42: soaking 5-20 parts of the powder sample obtained in the step S41 in 40-200 parts of an acidic solvent with the pH value of 2-4.5 for 1-7 days to enable reversible bonds in polyacrylate dynamic reversible crosslinked network components in the dynamic topological interlocking network to tend to be unlocked, so that the polyurethane dynamic reversible crosslinked network components still keep complete, and enabling the polyacrylate linear polymer to be unlocked from the dynamic topological interlocking network and dissolved in the solution after long-time soaking;

s43: and (3) filtering the mixed solution obtained in the step (S42) by using a Buchner funnel, collecting filtrate and residual solids, pouring the filtrate into a film, drying the film in a drying oven at the temperature of 60-80 ℃ to obtain an unlocked polyacrylate dynamic reversible crosslinked network, and molding the residual solids into a film to obtain an unlocked polyurethane dynamic reversible crosslinked network, wherein the molding temperature is 50-150 ℃, the molding pressure is 1-15 MPa, and the molding time is 1-12 h.

S44: and (3) smashing the unlocked polyacrylate network and the unlocked polyurethane network obtained in the step (S43) for 2-3 times at low temperature by using liquid nitrogen, uniformly mixing, placing in a solvent, treating under a high-temperature condition or under ultraviolet irradiation, casting to form a film, standing and drying to obtain the secondary interlocked dynamic topological interlocking double network. The high temperature range is 50-150 ℃, and the high temperature treatment time is 3-12 h; the power of the ultraviolet light irradiation is 100-3000 w, and the time is 1-12 h.

S45: and the unlocked polyacrylate dynamic reversible crosslinked network, the unlocked polyurethane dynamic reversible crosslinked network and the re-interlocked dynamic topological interlocking double network can be obtained for multiple times after the steps from S41 to S44 are repeated for multiple times.

Preferably, the acidic solvent in S42 is one or more of acidic dioxane or acidic NN dimethylformamide.

The application of the dynamic topological interlocking double network in the preparation of high-performance self-repairing or recyclable polymer materials is also within the protection scope of the invention.

The invention also requests to protect the self-repairing method of the dynamic topology interlocking double network, which comprises the following steps: and carrying out butt joint fixing on the dynamic topological interlocking double-network fracture surface at the temperature of 25-80 ℃ for repairing, wherein the repairing time is 1-30 h.

The invention also requests to protect the recovery method of the dynamic topology interlocking dual network, which comprises the following steps: and crushing the dynamic topological interlocking dual network, and then carrying out die pressing for 2-40 h at 50-120 ℃ and 1-15 MPa.

Compared with the prior art, the invention has the following beneficial effects:

the dynamic topological interlocking double network provided by the invention is crosslinked through the dynamic covalent bonds of the polyurethane dynamic reversible crosslinked network and the polyacrylate dynamic reversible crosslinked network, so that the crosslinked network dynamic exchange tends to be in a dissociation state in the network compounding process, the networks are fully mixed, and then the dynamic covalent bonds of the networks are recombined to obtain the dynamic topological interlocking double network. The double network has the capability of multiple unlocking and secondary interlocking, shows stronger mechanical property than the original single network, has good multiple self-repairing capability and solid recycling performance, and has wide application prospect.

Drawings

FIG. 1 is a picture of a polyacrylate dynamic reversible crosslinked network (a) provided in example 10, a polyurethane dynamic reversible crosslinked network (b) provided in example 5, a dynamic topological interlocking double network (c) provided in example 16, and an interlocking incomplete network (d) provided in comparative example 1;

FIG. 2 is the example 10-polyacrylate dynamic reversible crosslinked network; example 5-polyurethane dynamic reversible crosslinked network; example 16-dynamic topology interlocking dual network; comparative example 1-comparison of interlocking incomplete network tensile properties;

fig. 3 is a schematic structural diagram of a dynamic topology interlocking dual network (c).

Detailed Description

The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.

In the embodiment of the invention, the repairing performance of the dynamic topology interlocking double-network cured material is quantitatively analyzed and characterized by adopting a tensile test: and (3) performing tensile test by using a universal testing machine, wherein the tensile rate is 50mm/min, butting the sections of the two materials after the sample is broken or cut off, processing the sample at 25-100 ℃ for 1-30 h, and performing tensile test on the repaired sample again to obtain the tensile breaking stress. The above process is repeated to carry out a plurality of repair experiments. The repairing efficiency of the hot-pressed recycled sample is tested by the same method, and the repairing efficiency (eta) is the tensile strength (sigma) after repairing_healed) And original tensile strength (sigma)_virgin) The ratio of (A) to (B) is as follows:

η＝σ_Healed/σ_Virgin

in the formula sigma_Healed-post-repair tensile strength;

σ_Virgin-initial tensile strength.

The tensile strength σ/MPa is calculated as follows:

σ＝F/A

in the formula: f-maximum tensile breaking force of specimen (N)

A-cross-sectional area of tensile specimen (mm)²)。

EXAMPLE 1 preparation of p-allyloxybenzeneborate ester

The preparation method of the VPBE of the p-allyloxybenzene borate comprises the following steps:

5 parts by weight of 4-vinylphenylboronic acid and 4 parts by weight of 3-allyloxy-1, 2-propanediol are dissolved in 40 parts by weight of dry dichloromethane at room temperature N₂The reaction was magnetically stirred for 24h under protection, centrifuged to remove residual solids, the supernatant was collected and the solvent was removed by rotary evaporation to give a very pale yellow liquid with 95% yield.

EXAMPLE 2 preparation of polyethylene glycol p-benzaldehyde ester methacrylate

The preparation method of polyethylene glycol p-benzaldehyde ester methacrylate PEG-FD is as follows:

weighing 14 parts by weight of polyethylene glycol methacrylate and 8 parts by weight of p-carboxybenzaldehyde, dissolving in 150 parts by weight of anhydrous tetrahydrofuran, pouring the mixture into a three-neck flask with magnetons, introducing nitrogen for 30min, dropwise adding 20 parts by weight of DCC and 1.5 parts by weight of DMAP dissolved in 30 parts by weight of anhydrous THF at-20 ℃, slowly heating the temperature to 30 ℃, reacting for 24h, filtering to remove solid precipitates, performing rotary evaporation to remove most of THF, performing suction filtration to remove precipitated solids, dropwise adding the rest concentrated solution into 100 parts by weight of diethyl ether to generate a large amount of precipitates, filtering to remove the precipitates, repeating for 3 times, performing rotary drying on the solvent to obtain a pale yellow liquid, putting the pale yellow liquid into a refrigerator overnight to generate a small amount of precipitates, performing centrifugal removal, and storing the pale yellow liquid at the temperature of-4 ℃ in a refrigerator, wherein the yield is 92%.

Example 3 preparation of a polyurethane dynamic reversible crosslinked network 1

Dissolving 5 parts by weight of polytetrahydrofuran 2000 dried at 100 ℃ in vacuum in 50 parts by weight of dichloromethane, placing the mixture in a three-neck flask, dissolving 2.3 parts by weight of IPDI in 10 parts by weight of dichloromethane, dropwise adding the IPDI into the three-neck flask under the conditions of reflux condensation and magnetic stirring under the protection of high-purity nitrogen, controlling the reaction temperature to be 50 ℃, adding 0.2 part by weight of catalyst DBTDL into the reaction system, and reacting for 12 hours to obtain the polyurethane prepolymer PU. Adding 1 part by weight of 2,2' -diaminodiphenyl disulfide into a reaction system, and carrying out chain extension reaction for 4 hours at 50 ℃ to obtain the disulfide bond-containing linear polyurethane. Subsequently, 0.25 part by weight of triethanolamine TEOA was added to the reaction system and reacted overnight to obtain a crosslinked polyurethane PU-SS-1 containing disulfide bonds. After the casting film is formed, the mixture is placed at room temperature for 24 hours, then is placed at 80 ℃ for solidification for 48 hours, and then is cooled to the room temperature, and the test results of the tensile properties are shown in table 1.

Example 4 preparation of a polyurethane dynamically reversible crosslinked network 2

Dissolving 2.5 parts by weight of polyethylene glycol 2000 and 2.5 parts by weight of polytetrahydrofuran 2000 which are dried at 100 ℃ in vacuum in 50 parts by weight of dichloromethane, placing the mixture into a three-neck flask, dissolving 2.3 parts by weight of IPDI in 10 parts by weight of dichloromethane, dropwise adding the mixture into the three-neck flask under the conditions of reflux condensation and magnetic stirring under the protection of high-purity nitrogen, controlling the reaction temperature to be 50 ℃, adding 0.2 part by weight of catalyst DBTDL into the reaction system, and reacting for 12 hours to obtain the polyurethane prepolymer PU. Adding 1 part by weight of 2,2' -diaminodiphenyl disulfide into a reaction system, and carrying out chain extension reaction for 4 hours at 50 ℃ to obtain the disulfide bond-containing linear polyurethane. Subsequently, 0.25 part by weight of triethanolamine TEOA was added to the reaction system and reacted overnight to obtain a disulfide bond-containing crosslinked polyurethane PU-SS-2. After the casting film is formed, the mixture is placed at room temperature for 24 hours, then is placed at 80 ℃ for solidification for 48 hours, and then is cooled to the room temperature, and the test results of the tensile properties are shown in table 1.

Example 5 preparation of a polyurethane dynamic reversible crosslinked network 3

Dissolving 10 parts by weight of polyethylene glycol 2000 dried at 100 ℃ in vacuum in 50 parts by weight of dichloromethane, dissolving, placing in a three-neck flask, dissolving 2.3 parts by weight of IPDI in 10 parts by weight of dichloromethane, dropwise adding into the three-neck flask under the conditions of reflux condensation and magnetic stirring under the protection of high-purity nitrogen, controlling the reaction temperature to be 60 ℃, then adding 0.2 part by weight of catalyst DBTDL into the reaction system, and reacting for 12 hours to obtain the polyurethane prepolymer PU. Adding 0.5 weight part of 2,2' -diaminodiphenyl disulfide into a reaction system, and carrying out chain extension reaction for 4 hours at the temperature of 60 ℃ to obtain the disulfide bond-containing linear polyurethane. Subsequently, 0.25 part by weight of triethanolamine TEOA was added to the reaction system and reacted overnight to obtain a disulfide bond-containing crosslinked polyurethane PU-SS-3. After the film is cast and formed, the film is placed at room temperature for 24h, then the film is placed at 80 ℃ for solidification for 48h, then the film is cooled to the room temperature, the appearance of the film is shown as figure 1(b), the test result of the tensile property is shown in table 1, and the specific tensile curve is shown in figure 2.

Example 6 preparation of a polyurethane dynamic reversible crosslinked network 4

Dissolving 10 parts by weight of polyethylene glycol 2000 dried at 100 ℃ in vacuum in 50 parts by weight of dichloromethane, dissolving, placing in a three-neck flask, dissolving 4.5 parts by weight of IPDI in 10 parts by weight of dichloromethane, dropwise adding into the three-neck flask under the conditions of reflux condensation and magnetic stirring under the protection of high-purity nitrogen, controlling the reaction temperature to be 60 ℃, then adding 0.2 part by weight of catalyst DBTDL into the reaction system, and reacting for 12 hours to obtain the polyurethane prepolymer PU. Adding 0.5 weight part of 2,2' -diaminodiphenyl disulfide into a reaction system, and carrying out chain extension reaction for 4 hours at the temperature of 60 ℃ to obtain the disulfide bond-containing linear polyurethane. Subsequently, 0.5 part by weight of triethanolamine TEOA was added to the reaction system and reacted overnight to obtain a disulfide bond-containing crosslinked polyurethane PU-SS-4. After the casting film is formed, the mixture is placed at room temperature for 24 hours, then is placed at 80 ℃ for solidification for 48 hours, and then is cooled to the room temperature, and the test results of the tensile properties are shown in table 1.

Example 7 preparation of a polyurethane dynamic reversible crosslinked network 5

Dissolving 10 parts by weight of poly-epsilon-caprolactone 2000 dried at 100 ℃ in vacuum in 50 parts by weight of dichloromethane, placing the dissolved poly-epsilon-caprolactone in a three-neck flask, dissolving 2.3 parts by weight of IPDI in 10 parts by weight of dichloromethane, adding the IPDI into the three-neck flask dropwise under the conditions of reflux condensation and magnetic stirring under the protection of high-purity nitrogen, controlling the reaction temperature to be 60 ℃, adding 0.2 part by weight of catalyst DBTDL into the reaction system, and reacting for 12 hours to obtain the polyurethane prepolymer PU. Adding 0.5 weight part of bis (2-hydroxyethyl) disulfide into a reaction system, and carrying out chain extension reaction for 4 hours at the temperature of 60 ℃ to obtain the disulfide bond-containing linear polyurethane. Subsequently, 0.25 part by weight of triethanolamine TEOA was added to the reaction system and reacted overnight to obtain a crosslinked polyurethane PU-SS-5 containing disulfide bonds. After the casting film is formed, the mixture is placed at room temperature for 24 hours, then is placed at 80 ℃ for solidification for 48 hours, and then is cooled to the room temperature, and the test results of the tensile properties are shown in table 1.

Example 8 preparation of a polyurethane dynamic reversible crosslinked network 6

Dissolving 10 parts by weight of polyethylene glycol 2000 dried at 100 ℃ in vacuum in 50 parts by weight of dichloromethane, dissolving, placing in a three-neck flask, dissolving 2.5 parts by weight of MDI in 10 parts by weight of dichloromethane, dropwise adding into the three-neck flask under the conditions of reflux condensation and magnetic stirring under the protection of high-purity nitrogen, controlling the reaction temperature to be 60 ℃, adding 0.2 part by weight of catalyst DBTDL into the reaction system, and reacting for 12 hours to obtain the polyurethane prepolymer PU. Adding 0.5 weight part of 2,2' -diaminodiphenyl disulfide into a reaction system, and carrying out chain extension reaction for 4 hours at the temperature of 60 ℃ to obtain the disulfide bond-containing linear polyurethane. Subsequently, 0.25 part by weight of triethanolamine TEOA was added to the reaction system and reacted overnight to obtain a disulfide bond-containing crosslinked polyurethane PU-SS-6. After the casting film is formed, the mixture is placed at room temperature for 24 hours, then is placed at 80 ℃ for solidification for 48 hours, is cooled to room temperature, and the test results of the tensile properties are shown in table 1.

Example 9 preparation of a polyurethane dynamic reversible crosslinked network 7

Dissolving 10 parts by weight of polyethylene glycol 2000 dried at 100 ℃ in vacuum in 50 parts by weight of dichloromethane, placing the mixture in a three-neck flask, dissolving 1.7 parts by weight of HDI in 10 parts by weight of dichloromethane, dropwise adding the mixture into the three-neck flask under the conditions of reflux condensation and magnetic stirring under the protection of high-purity nitrogen, controlling the reaction temperature to be 60 ℃, adding 0.2 part by weight of catalyst DBTDL into the reaction system, and reacting for 12 hours to obtain the polyurethane prepolymer PU. Adding 0.5 weight part of 2,2' -diaminodiphenyl disulfide into a reaction system, and carrying out chain extension reaction for 4 hours at the temperature of 60 ℃ to obtain the disulfide bond-containing linear polyurethane. Subsequently, 0.25 part by weight of triethanolamine TEOA was added to the reaction system and reacted overnight to obtain a disulfide bond-containing crosslinked polyurethane PU-SS-7. After the casting film is formed, the mixture is placed at room temperature for 24 hours, then is placed at 80 ℃ for solidification for 48 hours, is cooled to room temperature, and the test results of the tensile properties are shown in table 1.

Example 10 preparation of polyacrylate dynamically reversible crosslinked network 1

Weighing 10 parts by weight of methyl acrylate, 5 parts by weight of acrylic acid and 1.5 parts by weight of 3-allyloxy-1, 2-propanediol, and dissolving in 50 parts by weight of N, N-dimethylformamide₂And magnetically stirring for 0.5h under protection, controlling the reaction temperature to be 60 ℃, then gradually dropwise adding 20 parts by weight of N, N dimethylformamide solution containing 0.4 part by weight of AIBN by using a constant-pressure dropping funnel, continuously mechanically stirring and reacting for 24h after dropwise adding, and cooling to room temperature to remove the N, N dimethylformamide by rotary evaporation to obtain the linear PA. Adding 0.8 weight part of 1, 4-phenyl diboronic acid, uniformly mixing, casting to form a film, standing at room temperature for 24 hours, and curing at 80 ℃ for 48And h, cooling to room temperature to obtain the polyacrylate dynamic reversible crosslinked network PA-1, wherein the appearance of the photo is shown as figure 1(a), the test result of the tensile property is shown in table 1, and the specific tensile curve is shown in figure 2.

EXAMPLE 11 preparation of polyacrylate dynamically reversible crosslinked network 2

Weighing 15 parts by weight of methyl acrylate, 3 parts by weight of acrylic acid and 4 parts by weight of p-allyloxybenzoborate, dissolving in 50 parts by weight of N, N-dimethylformamide₂And (2) magnetically stirring for 0.5h under protection, controlling the reaction temperature to be 60 ℃, then gradually dropwise adding 20 parts by weight of N, N dimethylformamide solution containing 0.4 part by weight of AIBN by using a constant-pressure dropping funnel, and continuously mechanically stirring and reacting for 24h after dropwise adding is finished to obtain the polyacrylate dynamic reversible crosslinked network. And (3) casting to form a film, standing at room temperature for 24h, curing at 80 ℃ for 48h, and cooling to room temperature to obtain the polyacrylate dynamic reversible crosslinked network PA-2, wherein the tensile property test results are shown in Table 1.

EXAMPLE 12 preparation of polyacrylate dynamically reversible crosslinked network 3

Weighing 10 parts by weight of methyl acrylate and 6 parts by weight of polyethylene glycol p-benzaldehyde ester methacrylate in 50 parts by weight of N, N-dimethylformamide₂And magnetically stirring for 0.5h under protection, controlling the reaction temperature to be 60 ℃, then gradually dropwise adding 20 parts by weight of N, N dimethylformamide solution containing 0.4 part by weight of AIBN by using a constant-pressure dropping funnel, continuously mechanically stirring and reacting for 24h after dropwise adding, and cooling to room temperature to remove the N, N dimethylformamide by rotary evaporation to obtain the linear PA. Adding 0.3 part by weight of ethylenediamine, uniformly mixing, casting to form a film, standing at room temperature for 24h, standing at 80 ℃ for curing for 48h, and cooling to room temperature to obtain the polyacrylate dynamic reversible crosslinked network PA-3, wherein the tensile property test results are shown in Table 1.

Example 13 preparation of polyacrylate dynamically reversible crosslinked network 4

Weighing 10 parts by weight of methyl acrylate and 12 parts by weight of polyethylene glycol p-benzaldehyde ester methacrylate, dissolving in 50 parts by weight of N, N-dimethylformamide₂Magnetically stirring for 0.5 hr under protection, controlling reaction temperature to 60 deg.C, and gradually adding 0.4 weight of solution into the solution via a constant pressure dropping funnelAnd (3) adding 20 parts by weight of N, N dimethylformamide solution of AIBN, continuously mechanically stirring and reacting for 24 hours after dropwise addition, cooling to room temperature, and removing the N, N dimethylformamide by rotary evaporation to obtain the linear PA. Adding 0.6 part by weight of ethylenediamine, uniformly mixing, casting to form a film, standing at room temperature for 24h, standing at 80 ℃ for curing for 48h, and cooling to room temperature to obtain the polyacrylate dynamic reversible crosslinked network PA-4, wherein the tensile property test results are shown in Table 1.

Example 14 preparation of polyacrylate dynamic reversible crosslinked network 5

Weighing 15 parts by weight of methyl acrylate and 12 parts by weight of polyethylene glycol p-benzaldehyde ester methacrylate, dissolving in 50 parts by weight of N, N-dimethylformamide₂And magnetically stirring for 0.5h under protection, controlling the reaction temperature to be 60 ℃, then gradually dropwise adding 20 parts by weight of N, N dimethylformamide solution containing 0.4 part by weight of AIBN by using a constant-pressure dropping funnel, continuously mechanically stirring and reacting for 24h after dropwise adding, and cooling to room temperature to remove the N, N dimethylformamide by rotary evaporation to obtain the linear PA. Adding 0.58 part by weight of hexamethylene diamine, uniformly mixing, casting to form a film, standing at room temperature for 24 hours, standing at 80 ℃ for curing for 48 hours, and cooling to room temperature to obtain the polyacrylate dynamic reversible crosslinked network PA-5, wherein the test results of the tensile property are shown in Table 1.

Example 15 preparation of polyacrylate dynamically reversible crosslinked network 6

15 parts by weight of methyl methacrylate, 5 parts by weight of tert-butyl acrylate and 1.5 parts by weight of 3-allyloxy-1, 2-propanediol were weighed out and dissolved in 50 parts by weight of N, N-dimethylformamide₂And magnetically stirring for 0.5h under protection, controlling the reaction temperature to be 60 ℃, then gradually dropwise adding 20 parts by weight of N, N dimethylformamide solution containing 0.4 part by weight of AIBN by using a constant-pressure dropping funnel, continuously mechanically stirring and reacting for 24h after dropwise adding, and cooling to room temperature to remove the N, N dimethylformamide by rotary evaporation to obtain the linear PA. Adding 0.8 part by weight of 1, 4-phenyl diboronic acid, uniformly mixing, casting to form a film, standing at room temperature for 24 hours, standing at 80 ℃ for curing for 48 hours, and cooling to room temperature to obtain the polyacrylate dynamic reversible crosslinked network PA-6, wherein the tensile property test results are shown in table 1.

Example 16 preparation of dynamic topology interlocking Dual network 1

Weighing 25 parts by weight of the polyurethane crosslinked network gel obtained in the example 5 and 75 parts by weight of the polyacrylate crosslinked network gel obtained in the example 10, stirring the materials by a strong machine to mix, then carrying out ultrasonic heating for 1h, then placing the materials in an oven at 80 ℃, further enabling the materials to be completely interpenetrated to obtain a yellow transparent sticky polymer, pouring the yellow transparent sticky polymer into a mold, placing the mold at room temperature for 24h, placing the mold at 80 ℃ for curing for 48h, and cooling the mold to room temperature to obtain a dynamic topological interlocking double-network 1, wherein an appearance photo is shown in a figure 1(c), the test results of the tensile properties are shown in a table 1, the specific tensile curve is shown in a table 2, after the material is tensile fractured, the sections of the material are butted, and after placing the material at 60 ℃ for 10h, the tensile properties of the material are tested, and the test results of the multiple self-repairing. And crushing the dynamic topological interlocking double network, pressing for 26 hours at 60 ℃ and 15MPa to obtain a recovered sample, and performing tensile test, wherein the mechanical property test results of the multiple recovered materials are shown in Table 3.

Example 17 preparation of dynamic topologically interlocking Dual network 2

Weighing 50 parts by weight of the polyurethane crosslinked network gel obtained in the example 5 and 50 parts by weight of the polyacrylate crosslinked network gel obtained in the example 10, stirring the materials strongly and mechanically to mix the materials, then carrying out ultrasonic heating for 1h, then placing the materials in an oven at 80 ℃, further completely interlocking the materials to obtain a yellow transparent sticky polymer, pouring the yellow transparent sticky polymer into a mold, placing the mold at room temperature for 24h, placing the mold at 80 ℃ for curing for 48h, cooling the mold to room temperature to obtain a dynamic topological interlocking double-network 2, testing the tensile property test result of the dynamic topological interlocking double-network 2 shown in the table 1, after the material is stretched and broken, butting the section of the material, placing the material at 80 ℃ for 10h for self-repairing, testing the tensile property of the material, and testing the multiple self-repairing property test result of the material shown. And crushing the dynamic topological interlocking double network, pressing for 26 hours at 80 ℃ under 10MPa to obtain a recovered sample, and performing tensile test, wherein the mechanical property test results of the multiple recovered materials are shown in Table 3.

Example 18 preparation of dynamic topologically interlocking Dual network 3

Weighing 75 parts by weight of the polyurethane crosslinked network gel obtained in the example 5 and 25 parts by weight of the polyacrylate crosslinked network gel obtained in the example 10, stirring the materials by a strong machine to mix the materials, then carrying out ultrasonic heating for 1h, then placing the materials in an oven at 80 ℃, further completely interlocking the materials to obtain a yellow transparent sticky polymer, pouring the yellow transparent sticky polymer into a mold, placing the mold at room temperature for 24h, placing the mold at 80 ℃ for curing for 48h, cooling the mold to room temperature to obtain a dynamic topological interlocking double-network 3, testing the tensile property test result of the dynamic topological interlocking double-network 3 shown in table 1, after the material is stretched and broken, butting the section of the material, placing the material at 80 ℃ for 10h for self-repairing, testing the tensile property of the material, and testing the multiple self-repairing property test result of the. And crushing the dynamic topological interlocking double network, pressing for 26 hours at 100 ℃ and 5MPa to obtain a recovered sample, and performing tensile test, wherein the mechanical property test results of the multiple recovered materials are shown in Table 3.

Example 19 preparation of dynamic topologically interlocking Dual network 4

Weighing 50 parts by weight of the polyurethane crosslinked network gel obtained in example 5 and 50 parts by weight of the polyacrylate crosslinked network gel obtained in example 12, stirring the materials strongly and mechanically to mix the materials, then carrying out ultrasonic heating for 1h, then placing the materials in an oven at 80 ℃, further enabling the materials to be completely interpenetrated to obtain a yellow and transparent viscous polymer, pouring the viscous polymer into a mold, placing the viscous polymer at room temperature for 24h, then placing the viscous polymer at 80 ℃ for curing for 48h, and cooling the viscous polymer to the room temperature to obtain a dynamic topological interlocking double-network 4, wherein the test results of the tensile properties of the dynamic topological interlocking double-network 4 are shown in table 1. After the material is stretched and broken, the sections of the material are butted, and after the material is placed at 80 ℃ for 10 hours for self-repairing, the tensile property of the material is tested, and the results of multiple self-repairing performance tests are shown in table 2. Crushing the dynamic topological interlocking double-network cured material, then pressing for 26h at 80 ℃ and 10MPa to obtain a recovered sample, and then performing tensile test, wherein the mechanical property test results of the multiple recovered materials are shown in Table 3.

Example 20 preparation of dynamic topologically interlocking Dual network 5

Weighing 50 parts by weight of the polyurethane crosslinked network gel obtained in example 7 and 50 parts by weight of the polyacrylate crosslinked network gel obtained in example 10, stirring the materials strongly and mechanically to mix, then heating the materials ultrasonically for 1h, then placing the materials under the condition of ultraviolet lamp illumination with the power of 1000w for 4h, further completely interlocking the materials to obtain a yellow transparent viscous polymer, pouring the viscous polymer into a mold, placing the viscous polymer at room temperature for 24h, then placing the viscous polymer at 80 ℃ for curing for 48h, and cooling the viscous polymer to the room temperature to obtain a dynamic topological interlocking double-network 5, wherein the test results of the tensile properties of the dynamic topological interlocking double-network 5 are shown in table 1. After the material is stretched and broken, the sections of the material are butted, and after the material is placed at 80 ℃ for 10 hours for self-repairing, the tensile property of the material is tested, and the results of multiple self-repairing performance tests are shown in table 2. And crushing the dynamic topological interlocking double network, pressing for 26 hours at 80 ℃ under 10MPa to obtain a recovered sample, and performing tensile test, wherein the mechanical property test results of the multiple recovered materials are shown in Table 3.

Example 21 preparation of dynamic topologically interlocking Dual network 6

Weighing 50 parts by weight of the polyurethane crosslinked network gel obtained in example 7 and 50 parts by weight of the polyacrylate crosslinked network gel obtained in example 12, stirring the materials strongly and mechanically to mix, then heating the materials ultrasonically for 1h, then placing the materials under the condition of ultraviolet lamp illumination with the power of 1000w for 4h, further completely interlocking the materials to obtain a yellow transparent viscous polymer, pouring the viscous polymer into a mold, placing the viscous polymer at room temperature for 24h, then placing the viscous polymer at 80 ℃ for curing for 48h, and cooling the viscous polymer to the room temperature to obtain a dynamic topological interlocking double-network 6, wherein the test results of the tensile properties of the dynamic topological interlocking double-network 6 are shown in table 1. After the material is stretched and broken, the sections of the material are butted, and after the material is placed at 80 ℃ for 10 hours for self-repairing, the tensile property of the material is tested, and the results of multiple self-repairing performance tests are shown in table 2. And crushing the dynamic topological interlocking double network, pressing for 26 hours at 80 ℃ under 10MPa to obtain a recovered sample, and performing tensile test, wherein the mechanical property test results of the multiple recovered materials are shown in Table 3.

Embodiment 22 unlocking of dynamic topology interlocking Dual networks 1

The dynamic topological interlocking double network obtained in example 17 was rapidly frozen, pulverized and dispersed with a large amount of dioxane, followed by addition of an acid to adjust the pH to 4, immersion in an acidic solution for 7 days, filtration to obtain a residual solid component, drying and compression molding into tablets at a molding temperature of 80 ℃ and a molding pressure of 10MPa for 2 hours. The unlocked polyurethane dynamic reversible crosslinked network (PU) is obtained, and the tensile property test results of the PU after being cooled to room temperature are shown in Table 1. Collecting filtrate, performing rotary evaporation to remove volatile acid HCl, pouring the filtrate into a film, and drying the film in an oven at 80 ℃ for 48 hours to obtain an unlocked polyacrylate dynamic reversible crosslinked network (PA), wherein the test results of the tensile properties are shown in Table 1.

Example 23 unlocking of dynamic topology interlocking Dual networks 2

The dynamic topological interlocking double network obtained in example 17 was frozen rapidly, crushed and dispersed with a large amount of DMF, followed by addition of an acid to adjust pH to 2, immersion in an acidic solution for 7 days, filtration to obtain a residual solid component, drying and compression molding into tablets at a molding temperature of 80 ℃ and a molding pressure of 10MPa for 2 h. The unlocked polyurethane dynamic reversible crosslinked network (PU) is obtained, and the tensile property test results of the PU after being cooled to room temperature are shown in Table 1. Collecting filtrate, performing rotary evaporation to remove volatile acid HCl, pouring the filtrate into a film, and drying the film in an oven at 80 ℃ for 48 hours to obtain an unlocked polyacrylate dynamic reversible crosslinked network (PA), wherein the test results of the tensile properties are shown in Table 1.

Embodiment 24 unlocking of dynamic topology interlocking Dual networks 3

The dynamic topological interlocking double network obtained in example 17 was frozen rapidly, crushed and dispersed with a large amount of DMF, followed by addition of an acid to adjust pH to 3, and after long-term immersion in an acidic solution for 7 days, filtration was carried out to obtain a residual solid component, and the mold pressing temperature was 80 ℃ and the mold pressing pressure was 10MPa and the mold pressing was 2 h. The unlocked polyurethane dynamic reversible crosslinked network is obtained, and the tensile property test result of the network is shown in table 1 after the network is cooled to room temperature. Collecting filtrate, performing rotary evaporation to remove volatile acid HCl, pouring the filtrate into a film, and drying the film in an oven at the temperature of 80 ℃ for 48 hours to obtain an unlocked polyacrylate dynamic reversible crosslinked network, wherein the test results of the tensile properties are shown in Table 1.

Example 25 unlocking of dynamic topology interlocking Dual network 4

The dynamic topological interlocking double network obtained in example 19 was frozen rapidly, crushed and dispersed with a large amount of DMF, followed by addition of an acid to adjust pH to 2, immersion in an acidic solution for 7 days, filtration to obtain a residual solid component, drying and compression molding into tablets at a molding temperature of 80 ℃ and a molding pressure of 10MPa for 2 h. The unlocked polyurethane dynamic reversible crosslinked network (PU) is obtained, and the tensile property test results of the PU after being cooled to room temperature are shown in Table 1. Collecting filtrate, performing rotary evaporation to remove volatile acid HC, pouring the filtrate into a film, and drying the film in an oven at 80 ℃ for 48 hours to obtain an unlocked polyacrylate dynamic reversible crosslinked network (PA), wherein the test results of the tensile properties are shown in Table 1.

Example 26 unlocking of dynamic topology interlocking Dual networks 5

The dynamic topological interlocking double network obtained in the embodiment 20 is frozen rapidly, crushed and dispersed by a large amount of DMF, then acid is added to adjust the pH value to 2, the obtained product is soaked in an acid solution for 7 days, the residual solid component is obtained by filtering, the obtained product is crushed at low temperature after drying, dispersed in DMF, placed in an ultraviolet lamp with the power of 1000w for 12 hours, the obtained solution is cast into a film and placed in an oven with the temperature of 80 ℃, the obtained film is dried for 48 hours to obtain the unlocked polyurethane dynamic reversible crosslinking network (PU), and the test result of the tensile property is tested after the PU is cooled to room temperature, and is shown in Table 1. Collecting filtrate, performing rotary evaporation to remove volatile acid HCl, pouring the filtrate into a film, and drying the film in an oven at 80 ℃ for 48 hours to obtain an unlocked polyacrylate dynamic reversible crosslinked network (PA), wherein the test results of the tensile properties are shown in Table 1.

Example 27 unlocking of dynamic topology interlocking Dual networks 6

The dynamic topological interlocking double network obtained in the example 21 is frozen rapidly, crushed and dispersed by a large amount of DMF, then acid is added to adjust the pH value to 2, the obtained product is soaked in an acid solution for 7 days, the residual solid component is obtained by filtration, the obtained product is crushed at low temperature after drying, dispersed in DMF, placed in an ultraviolet lamp with the power of 1000w for 12 hours, the solution is cast into a film and dried in an oven with the temperature of 80 ℃ for 48 hours to obtain the unlocked polyurethane dynamic reversible crosslinking network (PU), and the test result of the tensile property is tested after the PU is cooled to room temperature, and is shown in Table 1. Collecting filtrate, performing rotary evaporation to remove volatile acid HCl, pouring the filtrate into a film, and drying the film in an oven at 80 ℃ for 48 hours to obtain an unlocked polyacrylate dynamic reversible crosslinked network (PA), wherein the test results of the tensile properties are shown in Table 1.

Example 28 Re-interlocking of dynamic topology interlocking Dual networks 1

25 parts by weight of the unlocked polyacrylate dynamic reversible crosslinked network obtained in the embodiment 22 and 75 parts by weight of the unlocked polyurethane dynamic reversible crosslinked network are ground in liquid nitrogen at a low temperature for 2-3 times, the obtained powder is uniformly mixed and placed in DMF, the mixture is treated for 2 hours at a high temperature of 150 ℃, a film is cast, the mixture is stood and dried to obtain a re-interlocked dynamic topological interlocking double network, a re-dynamic topological interlocking double network 1 is obtained, the mixture is cooled to room temperature, and the test results of the tensile properties of the mixture are shown in Table 1.

Example 29 Re-interlocking of dynamic topology interlocking Dual networks 2

And (2) crushing 50 parts by weight of the unlocked polyacrylate dynamic reversible crosslinked network obtained in the embodiment 22 and 50 parts by weight of the unlocked polyurethane dynamic reversible crosslinked network in liquid nitrogen at a low temperature for 2-3 times, uniformly mixing the obtained powder, placing the mixture in DMF, treating the mixture for 5 hours at a high temperature of 100 ℃, casting the mixture to form a film, standing and drying the film to obtain a re-interlocked dynamic topological interlocking double network, obtaining a re-dynamic topological interlocking double network 2, cooling the re-interlocked dynamic topological interlocking double network to room temperature, and testing the tensile property of the re-interlocked dynamic topological interlocking double network, wherein the test results are shown in table 1.

Example 30 Re-interlocking of dynamic topology interlocking Dual networks 3

75 parts by weight of the unlocked polyacrylate dynamic reversible crosslinked network obtained in the example 22 and 25 parts by weight of the unlocked polyurethane dynamic reversible crosslinked network are ground in liquid nitrogen at low temperature for 2-3 times, the obtained powder is uniformly mixed and placed in DMF, the mixture is treated for 12 hours at the high temperature of 80 ℃, a film is cast, the mixture is stood and dried to obtain a re-interlocked dynamic topological interlocking double network, a re-dynamic topological interlocking double network 3 is obtained, the mixture is cooled to room temperature, and the test results of the tensile properties of the mixture are shown in Table 1.

Example 31 Re-interlocking of dynamic topology interlocking Dual networks 4

The method comprises the following steps of crushing 50 parts by weight of the unlocked polyacrylate dynamic reversible crosslinked network obtained in the embodiment 25 and 50 parts by weight of the unlocked polyurethane dynamic reversible crosslinked network in liquid nitrogen at a low temperature for 2-3 times, uniformly mixing the obtained powder, placing the obtained powder in DMSO, treating the obtained mixture for 2 hours at a high temperature of 150 ℃, casting the obtained mixture to form a film, standing and drying the obtained film to obtain a re-interlocked dynamic topological interlocking double network, obtaining a re-dynamic topological interlocking double network 4, cooling the obtained product to room temperature, and testing the tensile property of the obtained product, wherein the test results are shown in table 1.

Example 32 Re-interlocking of dynamic topology interlocking Dual networks 5

50 parts by weight of the unlocked polyacrylate dynamic reversible crosslinked network obtained in example 26 and 50 parts by weight of the unlocked polyurethane dynamic reversible crosslinked network are ground in liquid nitrogen at low temperature for 2-3 times, the obtained powder is dispersed in DMF and placed in an ultraviolet lamp with the power of 1000w for 12h, then a film is cast and dried in an oven at 80 ℃ for 48h to obtain a new dynamic topological interlocking double network, the new dynamic topological interlocking double network is cooled to room temperature, and the test results of the tensile properties are shown in Table 1.

Example 33 Re-interlocking of dynamic topology interlocking Dual networks 6

50 parts by weight of the unlocked polyacrylate dynamic reversible crosslinked network obtained in example 27 and 50 parts by weight of the unlocked polyurethane dynamic reversible crosslinked network are pulverized at low temperature by liquid nitrogen for 2-3 times, the obtained powder is dispersed in DMF and placed in an ultraviolet lamp with the power of 1000w for 12 hours, then a film is cast and dried in an oven at 80 ℃ for 48 hours to obtain a new dynamic topological interlocking double network, the new dynamic topological interlocking double network is cooled to room temperature, and the test results of the tensile properties are shown in Table 1.

Comparative example 1 preparation of interlocking incomplete network 1

50 parts by weight of the polyurethane crosslinked network gel obtained in example 5 and 50 parts by weight of the polyacrylate crosslinked network gel obtained in example 10 are weighed and mixed by strong mechanical stirring, quickly poured into a mold, placed at room temperature for 24 hours, cured at 80 ℃ for 48 hours, and cooled to room temperature to obtain an interlocking incomplete network 1, the appearance of which is shown in fig. 1(d), and the test results of the tensile properties are shown in table 1, and the specific tensile curve is shown in fig. 2.

Comparative example 2 preparation of interlocking incomplete network 2

50 parts by weight of the polyurethane crosslinked network gel obtained in example 5 and 50 parts by weight of the polyacrylate crosslinked network gel obtained in example 12 were weighed and mixed by strong mechanical stirring, and the mixture was rapidly poured into a mold, and after being left at room temperature for 24 hours, the mold was left at 80 ℃ to cure for 48 hours, and the mixture was cooled to room temperature to obtain an incomplete interlocking network 2, and the tensile properties of the incomplete interlocking network 2 were measured and the results are shown in table 1.

Comparative example 3 preparation of interlocking incomplete network 3

50 parts by weight of the polyurethane crosslinked network gel obtained in example 7 and 50 parts by weight of the polyacrylate crosslinked network gel obtained in example 10 were weighed and mixed by strong mechanical stirring, and the mixture was rapidly poured into a mold, and after being left at room temperature for 24 hours, the mold was left at 80 ℃ to cure for 48 hours, and the mixture was cooled to room temperature to obtain an incomplete interlocking network 3, and the tensile properties of the incomplete interlocking network 3 were measured and the results are shown in table 1.

Comparative example 4 interlocking incomplete network preparation 4

50 parts by weight of the polyurethane crosslinked network gel obtained in example 7 and 50 parts by weight of the polyacrylate crosslinked network gel obtained in example 12 were weighed and mixed by strong mechanical stirring, and the mixture was rapidly poured into a mold, left at room temperature for 24 hours, cured at 80 ℃ for 48 hours, and cooled to room temperature to obtain an incomplete interlocking network 4, and the tensile properties of the incomplete interlocking network 4 were measured and shown in table 1.

TABLE 1 comparison of tensile Properties of different examples and comparative examples

。

TABLE 2 comparison of multiple self-healing repair Performance for different examples

。

TABLE 3 comparison of tensile Strength of recycled samples of various examples with Properties of the original Material

。

It can be seen from the results of table 1, table 2 and table 3 that the topology interlocking dual network provided by the present invention can be unlocked into the initial single network again under a certain process, and the single network obtained by unlocking can be interlocked again under light and heat treatment to obtain the dynamic topology interlocking dual network, and this process can be repeated many times. The topological interlocking double network provided by the invention has stronger mechanical property than the initial single network, and simultaneously has good self-repairing and solid-state hot-pressing recovery properties, the recovery efficiency is high, the mechanical property of the recovered material can be kept good, and no obvious attenuation is caused.

The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims

1. A dynamic topological interlocking dual network is characterized by comprising the following components in parts by weight:

20-80 parts of polyurethane network

20-80 parts of a polyacrylate network;

the polyurethane network is crosslinked polyurethane containing reversible bonds, the polyacrylate network is crosslinked polyacrylate containing reversible bonds, and the reversible bonds contained in the polyurethane network and the polyacrylate network are different and do not influence each other.

2. The dynamic topological interlocking twin network of claim 1, wherein said reversible bond is a disulfide bond, a schiff base, a borate bond, a C-ON bond, a host-guest reversible bond, or a metal ion coordination bond.

3. The dynamic topological interlocking dual network as claimed in claim 1, characterized by comprising the following components in parts by weight:

50 portions of polyurethane network

50 parts of polyacrylate network.

4. The dynamic topological interlocking dual network according to claim 1, wherein said polyurethane network is prepared by the following method:

s13: and adding trifunctional alcohol or trifunctional ammonia crosslinking agent into the chain extension product obtained in the step S12 for crosslinking reaction to obtain the polyurethane network.

5. The dynamic topological interlocking dual network of claim 1, wherein said polyacrylate network is prepared by the following method:

6. A method for preparing a dynamic topological interlocking dual network as claimed in any one of claims 1 to 5, characterized by comprising the following steps:

s31: mixing the polyurethane network and the polyacrylate network, stirring and carrying out ultrasonic treatment to obtain a mixture;

s32: treating the mixture obtained in the step S31 at a high temperature of 60-150 ℃ or under the irradiation of ultraviolet light to obtain a yellow transparent sticky polymer;

s33: and (4) pouring the yellow transparent viscous polymer obtained in the step S32, standing and drying to obtain the dynamic topological interlocking double network.

7. The method for unlocking and re-interlocking the dynamic topological interlocking dual network as claimed in any one of claims 1 to 5, comprising the following steps:

s41: crushing the dynamic topological interlocking double network at a low temperature of not higher than-60 ℃, and crushing for 2-3 times by high-speed rotation impact to obtain a powder sample;

s43: filtering the mixed solution obtained in the step S42 to obtain filtrate and residual solid; pouring the obtained filtrate into a film and drying to obtain an unlocked polyacrylate network; the obtained residual solid is molded into a film to obtain an unlocked polyurethane network;

8. Use of the dynamic topological interlocking double network of any one of claims 1 to 5 in the preparation of high-performance self-healing or recyclable polymer materials.

9. The self-repairing method of the dynamic topological interlocking double network, which is characterized by comprising the following steps: and carrying out butt joint fixing on the dynamic topological interlocking double-network fracture surface at the temperature of 25-80 ℃ for repairing, wherein the repairing time is 1-30 h.

10. The recovery method of the dynamic topological interlocking dual network as claimed in any one of claims 1 to 5, characterized by comprising the following steps: and crushing the dynamic topological interlocking dual network, and then carrying out die pressing for 2-40 h at 50-120 ℃ and 1-15 MPa.