CN110551274B - Intrinsic self-repairing and recyclable polythiourea polymer and preparation method and application thereof - Google Patents

Intrinsic self-repairing and recyclable polythiourea polymer and preparation method and application thereof Download PDF

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CN110551274B
CN110551274B CN201910723064.7A CN201910723064A CN110551274B CN 110551274 B CN110551274 B CN 110551274B CN 201910723064 A CN201910723064 A CN 201910723064A CN 110551274 B CN110551274 B CN 110551274B
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张泽平
李艳梅
容敏智
章明秋
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National Sun Yat Sen University
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Abstract

The invention relates to an intrinsic self-repairing and recyclable polythiourea polymer, and a preparation method and application thereof. The polythiourea polymer comprises the following components in parts by weight: 1.9-24.5 parts of diamine monomer, 3.7-5.9 parts of diisothiocyanate monomer and 0.07-2.2 parts of amine monomer cross-linking agent; the amine monomer crosslinker has a functionality greater than 2. The polythiourea polymer provided by the invention contains a characteristic dynamic reversible thiourea bond unit, and endows the polythiourea polymer material with the properties of thermoreversible self-repairing and solid crushing or solvent degradation recovery, thereby enhancing the service stability of the material and prolonging the service life. The preparation method provided by the invention is simple in process, the thermoreversible temperature range of the thiourea bond is wide (35-120 ℃), and no catalyst is required to be added.

Description

Intrinsic self-repairing and recyclable polythiourea polymer and preparation method and application thereof
Technical Field
The invention belongs to the technical field of intelligent polymer materials, and particularly relates to an intrinsic self-repairing and recyclable polythiourea polymer, and a preparation method and application thereof.
Background
The polymer material, the metal material and the inorganic material are arranged in parallel as three pillars in a material structure, and the polymer material has wide application prospect. However, in the processing and using processes of the polymer material, the performance of the polymer material is often reduced due to internal microcracks and local damage, the service life of the polymer material is shortened, and even potential safety hazards are caused. The self-repairing high polymer material simulates the principle of organism injury healing, self-heals through a certain mechanism, and is a high polymer intelligent material with the greatest prospect for solving the key problems.
The self-repairing high polymer material comprises intrinsic self-repairing and external self-repairing. The external self-repairing system is repaired by embedding a micro-container for encapsulating a repairing agent or a catalyst, but has the problem that the same part is difficult to repair repeatedly. The intrinsic self-repairing high polymer material is generally repaired by utilizing a dynamic reversible bond, and the problem of repeated repair of the same part can be well solved. The dynamic reversible bonds used for constructing self-repairing polymer materials are generally classified into dynamic reversible noncovalent bonds and covalent bonds. At present, reported non-covalent bond systems mainly comprise hydrogen bonds, host-guest interactions, pi-pi stacking interactions, electrostatic interactions and the like; the covalent bond system mainly comprises Diels-Alder bond, C-ON bond, disulfide bond, acylhydrazone bond, carbamate bond, urea bond and the like. Among them, the self-repairing polymer material based on the dynamic reversible covalent bond has higher structural stability and mechanical strength, and is receiving wide attention.
In recent years, people utilize the reversible characteristics of urethane bonds and urea bonds to prepare a series of intrinsic self-repairing materials. However, the following disadvantages, for example: the thermoreversible temperature of the common urethane bond is higher, even a high content of toxic catalyst is needed; on the other hand, in order to reduce the temperature of the thermoreversible reaction, a special electronegativity (such as an oxime bond) and a large steric hindrance (such as tert-butyl) group are introduced into a reversible bond molecular structure, which generally needs to synthesize a specific monomer, so that the use of the commercialized conventional monomer is limited, and the popularization and application of the conventional polyurethane and polyurea are not facilitated. From the viewpoint of bond energy, the bond energy of thiourea bond is lower than that of urea bond of the same type, and dynamic reversibility can be exhibited over a wide temperature range without the need for a catalyst and without the need for introduction of a specific electronegative group or a large steric hindrance substituent. Therefore, it is necessary to develop a self-repairing chemistry based on a dynamic thermoreversible thiourea bond to prepare a self-repairing material with higher mechanical strength and repairing efficiency.
Disclosure of Invention
The invention aims to overcome the defects or shortcomings that the intrinsic self-repairing material in the prior art has higher thermoreversible temperature, needs to use high-content toxic catalyst and synthesize specific monomer, and limits the use of commercial conventional monomer; an intrinsically self-healing and recyclable polythiourea polymer is provided. The polythiourea polymer provided by the invention contains a characteristic dynamic reversible thiourea bond unit, and endows the polythiourea polymer material with the properties of thermoreversible self-repairing and solid crushing or solvent degradation recovery, thereby enhancing the service stability of the material and prolonging the service life.
Another object of the present invention is to provide a process for the preparation of polythiourea polymers as described above.
Another object of the present invention is to provide the use of the polythiourea polymer described above for the preparation of self-healing and recyclable polymeric materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
an intrinsic self-repairing and recoverable polythiourea polymer comprises the following components in parts by weight:
1.9 to 24.5 portions of diamine monomer,
3.7 to 5.9 parts of diisothiocyanate monomer,
0.07-2.2 parts of amine monomer crosslinking agent;
the amine monomer crosslinker has a functionality greater than 2.
In the polythiourea polymer provided by the invention, diamine monomer reacts with diisothiocyanate to obtain a linear polymer containing a characteristic dynamic reversible thiourea bond unit, and then the linear polymer reacts with an amine monomer crosslinking agent to obtain the polythiourea polymer.
The structural formula of the dynamic reversible thiourea bond unit is shown as the formula (I):
Figure BDA0002157920040000021
wherein R is1Is methylene or phenyl; r2Hydrogen, phenyl, alkyl; r3Methylene and phenyl.
In the thiourea bond unit structure, because the number of electron layers of the sulfur atom is large, the capability of attracting electrons is weaker than that of oxygen atoms, and the p-pi conjugation effect of lone-pair electrons on the N atom and C ═ S double bonds is reduced, so that the bond energy of C-N bonds is lower, and finally, the thiourea bond has dynamic reversibility. The repair mechanism of the polythiourea polymer with the thiourea bond-containing structure is that C-N bonds connected with thiocarbonyl carbons and a fatty chain on a polymer molecular chain are broken to cause the formation of reaction end groups, and reactive groups are contacted with each other along with the full movement or diffusion of chain segments, so that exchange and recombination reactions of macromolecular chains among damaged surfaces or broken particles of the polymer occur, and the repair and the recycling of a polymer network are realized.
The process of polymer self-repair by using dynamic reversible covalent bonds has the core that the breakage-recombination of the covalent bonds is realized, and even if the related polymer materials are broken in a fragment mode, new covalent bonds can be formed among the fragments to recover the mechanical property, which actually means that the reversible reaction based on the covalent bonds can realize the solid recovery and the recycling of the polymer materials. In actual operation, the abandoned polymer products can be crushed and then the block polymer with (or close to) the original mechanical property can be prepared again by adopting the compression molding or solid phase extrusion molding technology and through the exchange recombination of macromolecular chains among polymer particles at the temperature of the thermal reversible reaction and under certain pressure. The recovery process is carried out under the condition of all solid state, so the method is simple to operate, low in energy consumption and promising in development prospect. On the other hand, the general thermosetting material cannot be dissolved, but can be controllably degraded to obtain a uniform solution by utilizing the dissociation of a thermal reversible bond under the assistance of a small amount of micromolecule monomers forming a reversible unit, and the solution method is utilized to degrade and recover the thermosetting material, so that the original molecular structure of the material is more favorably kept.
According to the invention, a thiourea structure with a dynamic reversible carbon-nitrogen bond is introduced into the polymer material, so that the polymer material is endowed with the properties of thermoreversible self-repairing and solid-state crushing or solvent degradation and recovery, thereby enhancing the use stability of the material and prolonging the service life.
Preferably, the polythiourea polymer consists of the following components in parts by weight:
2.6 to 20.7 portions of diamine monomer,
3.7 to 5.9 parts of diisothiocyanate monomer,
0.07-2.2 parts of amine monomer crosslinking agent.
Preferably, the polythiourea polymer contains dynamic reversible thiourea bond units characterized by formula I:
Figure BDA0002157920040000031
wherein R is1Is methylene or phenyl; r2Is hydrogen, phenyl or alkyl; r3Is methylene or phenyl.
More preferably, the alkyl group is methyl, methylene, isopropyl, tert-butyl or cyclohexyl.
Preferably, the polythiourea polymer consists of the following components in parts by weight:
1.9 to 24.5 portions of diamine monomer,
3.7 to 5.9 parts of diisothiocyanate monomer,
0.07-2.2 parts of amine monomer crosslinking agent;
preferably, the diamine monomer is one or more of the following diamines containing primary amine or secondary amine structures:
Figure BDA0002157920040000041
wherein n is 2-5, and m is 30-32.
More preferably, the diamine monomer is one or more of 1, 2-bis (2-aminoethoxy) ethane, diethylene glycol bis (3-aminopropyl) ether, polyether amine, bis (3-aminopropyl) terminated polyethylene glycol or 1, 6-hexamethylene diamine, 4 '-methylene bis (cyclohexylamine) or N, N' -diethyl ethylene diamine.
Most preferably, M of said polyetheraminen230 or Mn＝400。
Most preferably, M of the bis (3-aminopropyl) terminated polyethylene glycoln＝1500。
Preferably, the diisothiocyanate monomer is one or more of the following substances:
Figure BDA0002157920040000042
more preferably, the diisothiocyanate monomer is terephthalocyanate.
Preferably, the amine monomer crosslinking agent is one or more of the substances shown in the following structural formula:
Figure BDA0002157920040000051
r is H or dimer acid.
More preferably, the amine monomer crosslinking agent is one or more of pentaethylenehexamine, polyamide curing agent or tri (2-aminoethyl) amine.
The preparation method of the polythiourea polymer comprises the following steps: dissolving diisothiocyanate monomers, adding diamine monomers for polycondensation, adding an amine monomer cross-linking agent for continuous reaction, and curing to obtain the polythiourea polymer.
The preparation method provided by the invention has the advantages of simple process, low temperature of thermal reversibility of the thiourea bond and no need of additional catalyst. The obtained polythiourea polymer has high mechanical strength.
Preferably, the reaction time after the diamine monomer is added is 16-24 h.
Preferably, the curing process is as follows: pouring the mixture into a mold, and curing at 60-80 ℃ for 12-24 h.
The application of the polythiourea polymer in the preparation of self-repairing and recyclable polymer materials is also within the protection scope of the invention.
The polythiourea polymer provided by the invention has the advantages of short repair time and high repair efficiency; the recovery efficiency is high.
Preferably, the self-healing method of the polythiourea polymer is as follows: the polythiourea polymer which is broken by mechanical damage is butted with the broken surface and is placed at 35-120 ℃ until recovery.
More preferably, the standing time is 0.5-24 h.
Preferably, the polythiourea polymer is recoverable by a process comprising: crushing the polythiourea polymer, and then carrying out hot press molding;
more preferably, the hot press forming process comprises the following steps: and carrying out hot press molding on the polythiourea polymer powder for 5-12 h at 35-120 ℃ and under the pressure of 3-10 MPa.
The invention herein provides another recoverable process for polythiourea polymers.
Preferably, the polythiourea polymer is recoverable by a process comprising: with the assistance of diamine monomer, the polythiourea polymer is degraded in polar solvent, and diisothiocyanate with the same molar ratio as the diamine monomer is added for reaction and then is cast into a film.
After casting into a film, a block material similar to the tensile strength of the original sample can be obtained.
Preferably, the diamine monomer is one or more of N, N '-diethyl ethylenediamine, diethylene glycol di (3-aminopropyl) ether or 4,4' -methylene bis (cyclohexylamine).
Preferably, the diisothiocyanate is terephthalocyanate.
More preferably, the polar solvent is one or more of DMF or DMSO.
Compared with the prior art, the invention has the following beneficial effects:
the polythiourea polymer provided by the invention contains a characteristic dynamic reversible thiourea bond unit, and endows the polythiourea polymer material with the properties of thermoreversible self-repairing and solid crushing or solvent degradation recovery, thereby enhancing the service stability of the material and prolonging the service life.
The preparation method provided by the invention has simple process, wide thermoreversible temperature range (35-120 ℃) of thiourea bonds, and no additional catalyst.
Drawings
FIG. 1 is a photograph of a crack repair of a self-healing polythiourea prepared in example 6 (a, c are the original cracks, respectively; b, d are micrographs of a treatment at 80 ℃ for 2.5h and 5h, respectively);
FIG. 2 is an infrared spectrum of a polythiourea polymer prepared by example 6.
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 invention, the repairing effect of the material is qualitatively evaluated by adopting microcrack repairing (as shown in figure 1); in addition, the polymer sample bars are made into dumbbell-type sample bars (l is 25mm, b is 2mm, h is 0.5mm) and subjected to a repair test, i.e., after the sample bars are cut from the middle, the cross sections of the sample bars are butted and heat-treated at 35 to 120 ℃ to test the tensile strength of the polymer, and the tensile strength is calculated as follows:
σ＝F/(b·l)
in the formula: f, the maximum load of the tensile failure of the sample; b, the width of the butt joint surface of the sample; l, sample butt joint face length. The repair efficiency is defined as the ratio of the tensile strength or elongation at break or elastic modulus of the repair sample to the original sample:
η＝σrecycled/σvirginor η ═ epsilonrecycled/εvirginOr η ═ Erecycled/Evirgin
The recovery efficiency of the material was evaluated by a tensile test method: polythiourea materials prepared in examples 1 to 11 were subjected to a tensile test to obtain an original mechanical strength, and then a polymer material was pulverized under liquid nitrogen quenching, and the obtained polymer powder was hot-pressed at 35 to 120 ℃ and 5MPa for a certain period of time to obtain a recovered sample (a rectangular film of 20X 40 mm) and subjected to a tensile test. Recovery efficiency is defined as the ratio of the tensile strength or elongation at break or elastic modulus of the recovered sample to the original sample.
Similarly, a tensile test is adopted to evaluate the solvent degradation recovery effect, after the polythiourea material prepared in examples 1 to 11 is subjected to a tensile test to obtain original mechanical strength, the polymer is dissolved in a DMF solvent containing a certain amount of diamine monomer (N, N '-diethylethylenediamine in examples 1 to 9, diethylene glycol di (3-aminopropyl) ether in example 10, and 4,4' -methylenebis (cyclohexylamine) in example 11) at 35 to 120 ℃, diisothiocyanate (p-phenylene diisothiocyanate in each example) in a corresponding proportion is added for reaction for 24 hours, then casting molding is carried out again to prepare a polythiourea bulk material, and the recovery efficiency is defined as the tensile strength, or the ratio of the elongation at break, or the elastic modulus of the recovered sample to the original sample.
Example 1
This example provides a polythiourea polymer (referred to as crosslinked polythiourea, the same applies below) prepared as follows.
Adding 5.0 parts of terephthal-isothiocyanate into a 250mL three-necked flask with mechanical stirring in a nitrogen atmosphere, adding 100.0 parts of DMF solvent, heating to 50 ℃ to dissolve the terephthal-isothiocyanate, adding 1.1 parts of N, N' -diethylethylenediamine and 1.9 parts of 1, 2-bis (2-aminoethoxy) ethane, reacting for 16h at 50 ℃, adding 0.1 part of pentaethylenehexamine, continuing to react for 8h, pouring into a mold, continuing to cure for 16h at 60 ℃ to obtain cross-linked polythiourea, and connecting a fracture surface in the air at 35-120 ℃ to repair for 0.5-24 h after the material is scratched or fractured, thus repairing. The polymer is crushed, hot pressed or degraded and cast to form new sample, and partial mechanical strength can be recovered. The results of the tensile testing before and after repair or recycling of the polymeric material are shown in tables 1,2 and 3, respectively.
Example 2
This example provides a polythiourea polymer prepared as follows.
Adding 5.0 parts of terephthal-isothiocyanate into a 250mL three-necked flask with mechanical stirring in a nitrogen atmosphere, adding 100.0 parts of DMF solvent, heating to 50 ℃ to dissolve the terephthal-isothiocyanate, adding 1.1 parts of N, N' -diethylethylenediamine and 2.9 parts of diethylene glycol bis (3-aminopropyl) ether, reacting for 16 hours at 50 ℃, adding 0.1 part of pentaethylenehexamine, continuing to react for 8 hours, pouring into a mold, continuing to cure for 16 hours at 60 ℃ to obtain crosslinked polythiourea, and after the material is scratched or broken, connecting the broken surface in the air at 35-120 ℃ for repairing for 0.5-24 hours, thus repairing. The polymer is crushed, hot pressed or degraded and cast to form new sample, and partial mechanical strength can be recovered. The results of the tensile testing before and after repair or recycling of the polymeric material are shown in tables 1,2 and 3, respectively.
Example 3
This example provides a polythiourea polymer prepared as follows.
Adding 5.0 parts of terephthal-isothiocyanate into a 250mL three-necked flask with mechanical stirring in a nitrogen atmosphere, adding 100.0 parts of DMF solvent, heating to 50 ℃ to dissolve the terephthal-isothiocyanate, adding 1.1 parts of N, N' -diethyl ethylenediamine and 3.0 parts of polyetheramine PEA230 (with the number average molecular weight of 230), reacting for 16 hours at 50 ℃, adding 0.1 part of pentaethylene hexamine, continuing to react for 8 hours, pouring into a mold, continuing to cure for 16 hours at 60 ℃ to obtain cross-linked polythiourea, and after the material is scratched or broken, connecting the broken surface in the air at 35-120 ℃ to repair for 0.5-24 hours, thus repairing. The polymer is crushed, hot pressed or degraded and cast to form new sample, and partial mechanical strength can be recovered. The results of the tensile testing before and after repair or recycling of the polymeric material are shown in tables 1,2 and 3, respectively.
Example 4
This example provides a polythiourea polymer prepared as follows.
Adding 5.0 parts of terephthal-isothiocyanate into a 250mL three-necked flask with mechanical stirring in a nitrogen atmosphere, adding 100.0 parts of DMF solvent, heating to 50 ℃ to dissolve the terephthal-isothiocyanate, adding 1.1 parts of N, N' -diethyl ethylenediamine and 5.2 parts of polyetheramine PEA400 (with the number average molecular weight of 400), reacting for 16 hours at 50 ℃, adding 0.1 part of pentaethylene hexamine, continuing to react for 8 hours, pouring into a mold, continuing to cure for 16 hours at 60 ℃ to obtain cross-linked polythiourea, and after the material is scratched or broken, connecting the broken surface in the air at 35-120 ℃ to repair for 0.5-24 hours, thus repairing. The polymer is crushed, hot pressed or degraded and cast to form new sample, and partial mechanical strength can be recovered. The results of the tensile testing before and after repair or recycling of the polymeric material are shown in tables 1,2 and 3, respectively.
Example 5
This example provides a polythiourea polymer prepared as follows.
Adding 5.0 parts of terephthal-isothiocyanate into a 250mL three-necked flask with mechanical stirring in a nitrogen atmosphere, adding 100.0 parts of DMF solvent, heating to 50 ℃ to dissolve the terephthal-isothiocyanate, adding 1.1 parts of N, N' -diethylethylenediamine and 19.6 parts of bis (3-aminopropyl) terminated polyethylene glycol (number average molecular weight 1500), reacting for 16 hours at 50 ℃, adding 0.1 part of pentaethylenehexamine, continuing to react for 8 hours, pouring into a mold, continuing to cure for 16 hours at 60 ℃ to obtain cross-linked polythiourea, and connecting a fracture surface in the air at 35-120 ℃ to repair for 0.5-24 hours after the material is scratched or fractured, thus repairing. The polymer is crushed, hot pressed or degraded and cast to form new sample, and partial mechanical strength can be recovered. The results of the tensile testing before and after repair or recycling of the polymeric material are shown in tables 1,2 and 3, respectively.
Example 6
This example provides a polythiourea polymer prepared as follows.
Adding 5.0 parts of terephthal-isothiocyanate into a 250mL three-necked flask with mechanical stirring in a nitrogen atmosphere, adding 100.0 parts of DMF solvent, heating to 50 ℃ to dissolve the terephthal-isothiocyanate, adding 1.1 parts of N, N' -diethyl ethylenediamine and 1.5 parts of 1, 6-hexanediamine, reacting at 50 ℃ for 16h, adding 0.1 part of pentaethylene hexamine, continuing to react for 8h, pouring into a mold, continuing to cure for 16h at 60 ℃ to obtain cross-linked polythiourea, and repairing the material after scratching or breaking, wherein the broken surface is connected in the air at 35-120 ℃ for 0.5-24 h. The polymer is crushed, hot pressed or degraded and cast to form new sample, and partial mechanical strength can be recovered. The results of the tensile testing before and after repair or recycling of the polymeric material are shown in tables 1,2 and 3, respectively.
The obtained polythiourea polymer has an infrared spectrum as shown in FIG. 2, and a stretching vibration peak of-NCS group of raw diisothiocyanate of 2100cm-1Disappearance and appearance of characteristic peak vN-C＝S(I)(1513cm-1)、νN-C＝S(II)(1338cm-1)、νN-C＝S(III)(1088cm-1) And N-H (3237 cm)-1) And (3) verifying that the isothiocyanate group has reacted with the amine group to generate a corresponding thiourea structure.
The pictures before and after repair are shown in figure 1. As shown in fig. 1a and 1c, the initial crack picture is shown; FIGS. 1b and 1d are micrographs after a repair treatment at 80 ℃ for 2.5h and 5 h. As can be seen from the figure, the cross-linked polythiourea achieves significant crack repair upon thermal stimulation.
Example 7
This example provides a polythiourea polymer prepared as follows.
Adding 5.0 parts of p-phenylene diisothiocyanate into a 250mL three-necked flask with mechanical stirring in a nitrogen atmosphere, adding 100.0 parts of DMF solvent, heating to 50 ℃ to dissolve the p-phenylene diisothiocyanate, adding 1.1 parts of N, N '-diethyl ethylenediamine and 2.7 parts of 4,4' -methylenebis (cyclohexylamine), reacting for 16h at 60 ℃, adding 0.1 part of pentaethylenehexamine, continuing to react for 8h, pouring into a mold, continuing to cure for 16h at 60 ℃ to obtain crosslinked polythiourea, and after the material is scratched or broken, connecting the broken surface in the air at 35-120 ℃ to repair for 0.5-24 h, thus repairing. The polymer is crushed, hot pressed or degraded and cast to form new sample, and partial mechanical strength can be recovered. The results of the tensile testing before and after repair or recycling of the polymeric material are shown in tables 1,2 and 3, respectively.
Example 8
This example provides a polythiourea polymer prepared as follows.
Adding 5.0 parts of terephthal-isothiocyanate into a 250ml three-neck flask with mechanical stirring in a nitrogen atmosphere, adding 100.0 parts of DMF solvent, heating to 50 ℃ to dissolve the terephthal-isothiocyanate, adding 1.1 parts of N, N' -diethyl ethylenediamine and 1.5 parts of 1, 6-hexanediamine, reacting for 16h at 50 ℃, adding 1.2 parts of polyamide curing agent 125 (amine value of 295mgKOH/g) to continue reacting for 8h, pouring into a mold to continue curing for 16h at 60 ℃ to obtain cross-linked polythiourea, and connecting a fracture surface in the air at 35-120 ℃ to repair for 0.5-24 h after the material is scratched or fractured, thus repairing. The polymer is crushed, hot pressed or degraded and cast to form new sample, and partial mechanical strength can be recovered. The results of the tensile testing before and after repair or recycling of the polymeric material are shown in tables 1,2 and 3, respectively.
Example 9
This example provides a polythiourea polymer prepared as follows.
Adding 5.0 parts of terephthal-isothiocyanate into a 250mL three-necked flask with mechanical stirring in a nitrogen atmosphere, adding 100.0 parts of DMF solvent, heating to 50 ℃ to dissolve the terephthal-isothiocyanate, adding 1.1 parts of N, N' -diethyl ethylenediamine and 1.5 parts of 1, 6-hexanediamine, reacting for 16 hours at 50 ℃, adding 1.8 parts of polyamide curing agent 115 (with an amine value of 190mgKOH/g) to continue reacting for 8 hours, pouring into a mold to continue curing for 16 hours at 60 ℃ to obtain cross-linked polythiourea, and connecting a fracture surface in the air at 35-120 ℃ to repair for 0.5-24 hours after the material is scratched or fractured, thus repairing. The polymer is crushed, hot pressed or degraded and cast to form new sample, and partial mechanical strength can be recovered. The results of the tensile testing before and after repair or recycling of the polymeric material are shown in tables 1,2 and 3, respectively.
Example 10
This example provides a polythiourea polymer prepared as follows.
Adding 5.0 parts of terephthal-isothiocyanate into a 250mL three-necked flask with mechanical stirring in a nitrogen atmosphere, adding 100.0 parts of DMF solvent, heating to 50 ℃ to dissolve the terephthal-isothiocyanate, adding 4.5 parts of diethylene glycol bis (3-aminopropyl) ether, reacting at 50 ℃ for 16h, adding 0.2 part of tris (2-aminoethyl) amine, continuing to react for 8h, pouring into a mold, continuing to cure at 60 ℃ for 16h to obtain cross-linked polythiourea, and repairing the material after scratching or breaking, wherein the breaking surface is connected in the air at 35-120 ℃ for 0.5-24 h, thus repairing. The polymer is crushed, hot pressed or degraded and cast to form new sample, and partial mechanical strength can be recovered. The results of the tensile testing before and after repair or recycling of the polymeric material are shown in tables 1,2 and 3, respectively.
Example 11
This example provides a polythiourea polymer prepared as follows.
Adding 5.0 parts of terephthalocyanum isothiocyanate into a 250mL three-necked flask with mechanical stirring in a nitrogen atmosphere, adding 100.0 parts of DMF solvent, heating to 50 ℃ to dissolve the terephthalocyanum isothiocyanate, adding 4.3 parts of 4,4' -methylenebis (cyclohexylamine), reacting at 50 ℃ for 16h, adding 0.2 part of tris (2-aminoethyl) amine, continuing to react for 8h, pouring into a mold, continuing to cure at 60 ℃ for 16h to obtain cross-linked polythiourea, and repairing the broken surface of the material at 35-120 ℃ in the air for 0.5-24 h after the material is scratched or broken. The polymer is crushed, hot pressed or degraded and cast to form new sample, and partial mechanical strength can be recovered. The results of the tensile testing before and after repair or recycling of the polymeric material are shown in tables 1,2 and 3, respectively.
Comparative example 1
This comparative example provides a polymer material having a urea linkage structure, which was prepared as follows.
Under nitrogen atmosphere, 4.2 parts of 1, 6-hexamethylene diisocyanate are added into a 250mL three-necked flask with mechanical stirring, 100.0 parts of DMF solvent is added to mix 1, 6-hexamethylene diisocyanate and the solvent uniformly, 8.7 parts of polyetheramine PEA400 (number average molecular weight 400) is added, after reaction for 5 hours at 60 ℃, 0.3 part of tris (2-aminoethyl) amine is added to continue the reaction for 8 hours, the mixture is poured into a mold and is continued to be cured for 16 hours at 60 ℃ to obtain cross-linked polyurea which is used as a comparative sample of example 3 (the amount of the substance with the number of thiourea bond units in example 3 is equal to the amount of the substance with the number of urea bond units in the comparative example). The results of the tensile testing before and after repair and recycling of the polymeric material are shown in tables 1,2 and 3, respectively. The molecular structural formula of the 1, 6-hexamethylene diisocyanate is as follows:
Figure BDA0002157920040000121
comparative example 2
This comparative example provides a polymeric material prepared as follows.
Under nitrogen atmosphere, 4.8 parts of m-xylylene diisocyanate was added to a 250mL three-necked flask with mechanical stirring, 100.0 parts of DMF solvent was added, the temperature was raised to 50 ℃ to dissolve the m-xylylene diisocyanate, 9.0 parts of polyetheramine PEA400 (number average molecular weight 400) was added, after reaction at 60 ℃ for 5 hours, a crosslinking agent obtained by reacting 0.6 part of 1, 6-hexamethylene diisocyanate trimer with 0.6 part of tris (2-aminoethyl) amine was added to continue the reaction for 8 hours, and the resulting mixture was poured into a mold and cured at 60 ℃ for 16 hours to obtain crosslinked polyurea, which was used as a comparative sample of example 6 (the amount of the substance having the same number of thiourea bond units as that of the urea bond units in this comparative example 6). The results of the tensile testing before and after repair and recycling of the polymeric material are shown in tables 1,2 and 3, respectively. The molecular structural formulas of the m-xylylene diisocyanate, the 1, 6-hexamethylene diisocyanate trimer and the cross-linking agent obtained by reacting the 1, 6-hexamethylene diisocyanate trimer with the tri (2-aminoethyl) amine are respectively as follows:
Figure BDA0002157920040000122
comparative example 3
This comparative example provides a polymeric material prepared as follows.
Under nitrogen atmosphere, 4.8 parts of m-xylylene diisocyanate was added to a 250mL three-necked flask with mechanical stirring, 100.0 parts of DMF solvent was added, the temperature was raised to 50 ℃ to dissolve the m-xylylene diisocyanate, 9.0 parts of polyetheramine PEA400 (number average molecular weight 400) was added, after reaction at 50 ℃ for 5 hours, 0.4 part of tris (2-aminoethyl) amine was added to continue the reaction for 8 hours, and the mixture was poured into a mold and cured at 60 ℃ for 16 hours to obtain crosslinked polyurea as a comparative sample of example 10 (the amount of the substance having the same number of thiourea bond units as that of the present comparative example in example 10). The results of the tensile testing before and after repair and recycling of the polymeric material are shown in tables 1,2 and 3, respectively.
Table 1 comparison of the effects of the polymer material butt-joint repair test
Figure BDA0002157920040000131
As is clear from table 1, the polymers having a thiourea structure (examples 1 to 11) were recovered in terms of the breaking strength, the elongation at break and the elastic modulus after being cut by heat treatment for a certain period of time, and both the breaking strength and the elastic modulus recovery rate were more than 82%. And even though the polymers containing the urea bond structures (comparative examples 1-3) are subjected to the same repairing conditions, the breaking strength, the breaking elongation and the elastic modulus can be repaired only rarely, and the repairing efficiency is lower than 56%. Among these, the mechanical strength recovery of the control was partly due to the large number of hydrogen bonds in the urea bond structure.
Table 2 comparison of solid state recovery effects of tensile testing of polymeric materials
Figure BDA0002157920040000132
Figure BDA0002157920040000141
As is clear from Table 2, the polymers having a thiourea structure (examples 1 to 11) were all reshaped by crushing and hot pressing, and had mechanical strength equivalent to that of the starting material and high recovery efficiency. The polymers containing urea bond structures (comparative examples 1 to 3) can be reshaped by crushing and hot pressing due to a large number of hydrogen bonds in the urea bond structures, but the recovery efficiency of the breaking strength, the breaking elongation and the elastic modulus is lower than 50%.
TABLE 3 comparison of solvent degradation recovery effects of tensile testing of Polymer materials
Figure BDA0002157920040000142
Figure BDA0002157920040000151
Remarking: table 3 "-" represents that the materials prepared in comparative examples 1,2 and 3 could not give a uniform solution due to degradation.
As shown in Table 3, the polymers containing thiourea structure (examples 1 to 11) can be reshaped by solution degradation-casting, the mechanical strength of the obtained material is equivalent to that of the original material, the integrity of the molecular structure of the polymer can be better preserved by solution degradation, and the recovery efficiency is high. The polymers containing urea bond structures (comparative examples 1 to 3) could not be degraded in DMF solution containing diamine monomers to give a homogeneous solution.
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 (10)

1. An intrinsic self-repairing and recyclable polythiourea polymer is characterized by comprising the following components in parts by weight:
1.9 to 24.5 portions of diamine monomer,
3.7 to 5.9 parts of diisothiocyanate monomer,
0.07-2.2 parts of amine monomer crosslinking agent;
the amine monomer crosslinker has a functionality greater than 2.
2. The polythiourea polymer of claim 1 which is comprised of the following components in parts by weight:
2.6 to 20.7 portions of diamine monomer,
5.0 parts of diisothiocyanate monomer,
0.1-1.8 parts of amine monomer crosslinking agent.
3. The polythiourea polymer of claim 1 wherein the polythiourea polymer comprises dynamically reversible thiourea linkage units having the characteristics shown in formula I:
Figure FDA0002453811340000011
wherein R is1Is methylene or phenyl; r2Is hydrogen, phenyl or alkyl; r3Is methylene or phenyl.
4. The polythiourea polymer of claim 1 wherein the diamine monomer is a diamine containing a primary or secondary amine structure.
5. The polythiourea polymer of claim 4 wherein the diamine monomer is one or more of the following structures:
Figure FDA0002453811340000021
wherein n is 2-5; m is 30 to 32.
6. The polythiourea polymer of claim 1 wherein the diisothiocyanate monomer is one or more of the following structures:
Figure FDA0002453811340000022
7. the polythiourea polymer of claim 1 wherein the amine monomer crosslinker is one or more of the following structures:
Figure FDA0002453811340000031
r is H or dimer acid.
8. A process for preparing a polythiourea polymer of any of claims 1 to 7 comprising the steps of: dissolving diisothiocyanate monomers, adding diamine monomers for polycondensation, adding an amine monomer cross-linking agent for continuous reaction, and curing to obtain the polythiourea polymer.
9. Use of the polythiourea polymer of any of claims 1 to 7 in the preparation of self-healing and recyclable polymeric materials.
10. The use of claim 9, wherein the polythiourea polymer is self-healing by: butting the fracture surfaces of polythiourea polymers fractured by mechanical damage and placing the polythiourea polymers at 35-120 ℃ until the polythiourea polymers are recovered; the recoverable method comprises crushing the polythiourea polymer and then carrying out hot press molding; or with the assistance of diamine monomer, degrading polythiourea polymer in polar solvent, adding diisothiocyanate with the same molar ratio as diamine monomer, and casting to form film.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021230241A1 (en) * 2020-05-11 2021-11-18 国立大学法人 東京大学 Self-healing polymer material
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CN115073688A (en) * 2021-08-25 2022-09-20 南京理工大学 Super-ductility room-temperature intrinsic self-repairing elastomer material and preparation method thereof
CN115434073B (en) * 2022-09-13 2023-06-02 上海迅江科技有限公司 Polyurethane nanofiber waterproof and moisture-permeable membrane and preparation method and application thereof

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB534699A (en) * 1938-09-15 1941-03-14 Du Pont Polymeric compounds suitable for filaments, films, coating compositions, plastics and the like
GB1039371A (en) * 1961-12-01 1966-08-17 Courtaulds Ltd Polythioureas
WO2002092558A1 (en) * 2001-05-14 2002-11-21 Gencell S.A. Polythiourea lipid derivatives
CN1602322A (en) * 2001-11-14 2005-03-30 埃西勒国际通用光学公司 High refractive index and high impact resistant polythiourethane/urea material, method of manufacturing same and its use in the optical field
CN1705694A (en) * 2002-12-20 2005-12-07 Ppg工业俄亥俄公司 High impact poly (urethane urea) polysulfides
CN1837261A (en) * 2005-03-23 2006-09-27 中南大学 Process for preparing polyester-base thiourea resin
CN101460535A (en) * 2005-12-16 2009-06-17 Ppg工业俄亥俄公司 Polyurethanes, polyurethane(ureas) sulfur-containing polyurethanes and sulfur-containing polyurethane(ureas) and methods of preparation
CN105582020A (en) * 2014-10-21 2016-05-18 浙江大学 Application of linear polythiourea and hyperbranched polythiourea in preparation of anti-tumor medicines and anti-virus or anti-bacterial medicines
CN108884209A (en) * 2016-03-30 2018-11-23 三井化学株式会社 Polymerizable composition for optical material, the optical material and plastic lens obtained by the composition
CN109265636A (en) * 2018-08-10 2019-01-25 四川大学 Novel high-performance THERMALLY REVERSIBLE COVALENT polymer based on amide groups urea bond and preparation method thereof
CN109666166A (en) * 2017-10-17 2019-04-23 翁秋梅 A kind of energy-absorbing method based on dynamic crosslinking polymer
CN109666160A (en) * 2017-10-17 2019-04-23 翁秋梅 A kind of dynamic aggregation object with hybrid cross-linked network
CN110041491A (en) * 2019-04-30 2019-07-23 郑州大学 A kind of high-intensity and high-tenacity selfreparing thermoplastic polyurethane urea elastomer and preparation method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150344613A1 (en) * 2014-05-30 2015-12-03 Empire Technology Development Llc Polythiourea compositions and methods of use

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB534699A (en) * 1938-09-15 1941-03-14 Du Pont Polymeric compounds suitable for filaments, films, coating compositions, plastics and the like
GB1039371A (en) * 1961-12-01 1966-08-17 Courtaulds Ltd Polythioureas
WO2002092558A1 (en) * 2001-05-14 2002-11-21 Gencell S.A. Polythiourea lipid derivatives
CN1602322A (en) * 2001-11-14 2005-03-30 埃西勒国际通用光学公司 High refractive index and high impact resistant polythiourethane/urea material, method of manufacturing same and its use in the optical field
CN1705694A (en) * 2002-12-20 2005-12-07 Ppg工业俄亥俄公司 High impact poly (urethane urea) polysulfides
CN1837261A (en) * 2005-03-23 2006-09-27 中南大学 Process for preparing polyester-base thiourea resin
CN101460535A (en) * 2005-12-16 2009-06-17 Ppg工业俄亥俄公司 Polyurethanes, polyurethane(ureas) sulfur-containing polyurethanes and sulfur-containing polyurethane(ureas) and methods of preparation
CN105582020A (en) * 2014-10-21 2016-05-18 浙江大学 Application of linear polythiourea and hyperbranched polythiourea in preparation of anti-tumor medicines and anti-virus or anti-bacterial medicines
CN108884209A (en) * 2016-03-30 2018-11-23 三井化学株式会社 Polymerizable composition for optical material, the optical material and plastic lens obtained by the composition
CN109666166A (en) * 2017-10-17 2019-04-23 翁秋梅 A kind of energy-absorbing method based on dynamic crosslinking polymer
CN109666160A (en) * 2017-10-17 2019-04-23 翁秋梅 A kind of dynamic aggregation object with hybrid cross-linked network
CN109265636A (en) * 2018-08-10 2019-01-25 四川大学 Novel high-performance THERMALLY REVERSIBLE COVALENT polymer based on amide groups urea bond and preparation method thereof
CN110041491A (en) * 2019-04-30 2019-07-23 郑州大学 A kind of high-intensity and high-tenacity selfreparing thermoplastic polyurethane urea elastomer and preparation method

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Mechanically robust, readily repairable polymers via tailored noncovalent cross-linking;Yanagisawa Yu et al.;《SCIENCE》;20180105;第359卷(第6371期);第72-76页 *
Research Progress of Processing of Crosslinked Polymers Based on Reversible Covalent Chemistry: a New Challenge to the Development of Polymer Engineering;Zhang ZePing et al.;《ACTA POLYMERICA SINICA》;20180731(第7期);第829-852页 *
Rigid Urea and Self-Healing Thiourea Ethanlamine Monolayers;Stefaniu Cristina et al.;《LANGMUIR》;20150203;第31卷(第4期);第1296-1302页 *
聚硫脲缓释微胶囊的制备及其性能表征;张文灵 等;《石油化工》;20071015;第36卷(第10期);第1021-1024页 *

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