Environmentally-friendly flexible conductive polyurethane (PU) and preparation method thereof

Abstract

An environmentally-friendly flexible conductive polyurethane (PU) and a preparation method thereof are disclosed. The environmentally-friendly flexible conductive PU is prepared by subjecting a mixture of a component A and a component B in a specified mass ratio to in-situ solvent-free polymerization, where the component A is prepared from a polyol, a T-type chain extender, a diselenide diol, high-conductivity carbon black, a dispersing agent, a catalyst, and a leveling agent, and the component B is prepared from a polyisocyanate, a polyol, a multi-walled carbon nanotube (MWCNT), and a dispersing agent. The PU has a reliable electrically-conductive function, and shows a self-healing function under room temperature or light conditions when damaged, wherein a microphase separation value HBI (0.5 to 3.0) of soft and hard segment molecules can be adjusted to achieve different hand touches and different mechanical properties, and an organic pollutant emission (volatile organic compound (VOC)) is less than 50 mg/kg.

Claims

1. A preparation method of an environmentally-friendly flexible conductive polyurethane (PU), comprising the following steps: 1) Preparation of a first component, comprising: heating at least one reagent selected from the group consisting of a polyol, a diselenide diol, and a T-type chain extender to 50? C. to 130? C., adding high-conductivity carbon black and a dispersing agent, ultrasonically stirring, and adding a catalyst and a leveling agent to obtain a hydroxyl-terminated polymer as the first component; 2) Preparation of a second component, comprising: heating a polyisocyanate or the polyol to 50? C. to 130? C., adding a multi-walled carbon nanotube (MWCNT) and the dispersing agent, ultrasonically stirring, adding remaining materials, and stirring at a predetermined temperature to obtain an isocyanate-terminated prepolymer as the second component; and 3) Preparation of the environmentally-friendly flexible conductive PU: adding the first component and the second component to a reactor according to a specified weight ratio, stirring at a high speed of 1,500 r/min to 2,000 r/min for 4 min to 10 min, and aging at 100? C. to 120? C. for 1 hour to 2 hours to obtain the environmentally-friendly flexible conductive PU.

2. The preparation method of the environmentally-friendly flexible conductive PU according to claim 1, wherein in step 1, the first component is prepared from the following components, in parts by weight: 60 to 90 parts of the polyol, 50 to 80 parts of the diselenide diol, 30 to 60 parts of the T-type chain extender, 0.1 to 2 parts of the high-conductivity carbon black, 0.01 to 0.2 parts of the dispersing agent, 0.1 to 1 part of the catalyst, and 0.1 to 1 part of the leveling agent.

3. The preparation method of the environmentally-friendly flexible conductive PU according to claim 2, wherein in step 2, the second component is prepared from the following components, in parts by weight: 100 to 250 parts of the polyisocyanate, 30 to 100 parts of the polyol, 0.05 to 0.4 parts of the MWCNT, and 0 to 0.1 parts of the dispersing agent.

4. The preparation method of the environmentally-friendly flexible conductive PU according to claim 3, wherein in step 3, the specified weight ratio of the first component to the second component is 1:(1-1.1).

5. The preparation method of the environmentally-friendly flexible conductive PU according to claim 2, wherein in step 3, the specified weight ratio of the first component to the second component is 1:(1-1.1).

6. The preparation method of the environmentally-friendly flexible conductive PU according to claim 1, wherein in step 3, the specified weight ratio of the first component to the second component is 1:(1-1.1).

7. The preparation method of the environmentally-friendly flexible conductive PU according to claim 6, wherein in step 1, a dynamic diselenide bond is present in a molecular chain of the diselenide diol; and the T-type chain extender has a structure comprising a diolamine molecular chain with a side chain and a diamido group on the side chain.

8. The preparation method of the environmentally-friendly flexible conductive PU according to claim 7, wherein the dispersing agent is at least one selected from the group consisting of N-methylpyrrolidone (NMP), sodium dodecyl sulfate (SDS), and dodecylbenzene sulfonic acid (DBSA); and the catalyst is dibutyltin dilaurate or stannous octoate.

9. The preparation method of the environmentally-friendly flexible conductive PU according to claim 8, wherein the high-conductivity carbon black is a spherical powder, and has a particle size of 20 nm to 100 nm and a specific surface area (SSA) of 60 m.sup.2.Math.g.sup.?1 to 1,000 m.sup.2.Math.g.sup.?1; and the MWCNT is rod-shaped or tubular, and has a length of 0.5 ?m to 40 ?m and a diameter of 10 nm to 30 nm.

10. The preparation method of the environmentally-friendly flexible conductive PU according to claim 8, wherein the diselenide diol has a structure of: ##STR00003## the structure of the T-type chain extender is: ##STR00004##

11. The preparation method of the environmentally-friendly flexible conductive PU according to claim 7, wherein the high-conductivity carbon black is a spherical powder, and has a particle size of 20 nm to 100 nm and a specific surface area (SSA) of 60 m.sup.2.Math.g.sup.?1 to 1,000 m.sup.2.Math.g.sup.?1; and the MWCNT is rod-shaped or tubular, and has a length of 0.5 ?m to 40 ?m and a diameter of 10 nm to 30 nm.

12. The preparation method of the environmentally-friendly flexible conductive PU according to claim 7, wherein the diselenide diol has a structure of: ##STR00005## the structure of the T-type chain extender is: ##STR00006##

13. The preparation method of the environmentally-friendly flexible conductive PU according to claim 6, wherein the polyisocyanate is at least one selected from the group consisting of isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and diphenylmethane diisocyanate (MDI); and the polyol is at least one selected from the group consisting of polytetrahydrofuran ether glycol, polycaprolactone glycol, polypropylene glycol (PPG), polycarbonate diol, and polyethylene adipate glycol, and the polyol has a relative molecular mass of 1,000 to 2,000 Da.

14. The preparation method of the environmentally-friendly flexible conductive PU according to claim 13, wherein the high-conductivity carbon black is a spherical powder, and has a particle size of 20 nm to 100 nm and a specific surface area (SSA) of 60 m.sup.2.Math.g.sup.?1 to 1,000 m.sup.2.Math.g.sup.?1; and the MWCNT is rod-shaped or tubular, and has a length of 0.5 ?m to 40 ?m and a diameter of 10 nm to 30 nm.

15. The preparation method of the environmentally-friendly flexible conductive PU according to claim 13, wherein the diselenide diol has a structure of: ##STR00007## the T-type chain extender has a structure of: ##STR00008##

16. An environmentally-friendly flexible conductive PU prepared by the preparation method according to claim 1.

17. The environmentally-friendly flexible conductive PU according to claim 16, wherein in step 1, the first component is prepared from the following components, in parts by weight: 60 to 90 parts of the polyol, 50 to 80 parts of the diselenide diol, 30 to 60 parts of the T-type chain extender, 0.1 to 2 parts of the high-conductivity carbon black, 0.01 to 0.2 parts of the dispersing agent, 0.1 to 1 part of the catalyst, and 0.1 to 1 part of the leveling agent.

18. The environmentally-friendly flexible conductive PU according to claim 17, wherein in step 2, the second component is prepared from the following components, in parts by weight: 100 to 250 parts of the polyisocyanate, 30 to 100 parts of the polyol, 0.05 to 0.4 parts of the MWCNT, and 0 to 0.1 parts of the dispersing agent.

19. The environmentally-friendly flexible conductive PU according to claim 16, wherein in step 3, the specified weight ratio of the first component to the second component is 1:(1-1.1).

20. The environmentally-friendly flexible conductive PU according to claim 19, wherein in step 1, a dynamic diselenide bond is present in a molecular chain of the diselenide diol; and the T-type chain extender has a structure comprising a diolamine molecular chain with a side chain and a diamido group on the side chain.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) In order to more clearly illustrate the technical solutions in the embodiments of the present disclosure or related technologies, a brief introduction of the accompanying drawings used in the description of the embodiments or related technologies is given. Obviously, the drawings in the following description are some embodiments of the present disclosure, for those of ordinary skill in the art, other drawings can also be obtained according to these drawings without any creative effort.

(2) FIG. 1A shows the morphology of SFPU before the healing;

(3) FIG. 1B shows the morphology of SFPU after the healing; and

(4) FIG. 2 is a schematic diagram illustrating the formation of a conductive network inside the SFPU film.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(5) It should be noted that the examples in the present disclosure or features in the examples may be combined in a non-conflicting manner.

(6) The technical solutions in the examples of the present disclosure are clearly and completely described below with reference to the accompanying drawings in the examples of the present disclosure. Apparently, the described examples are merely a part rather than all of the examples of the present disclosure. All other examples obtained by a person of ordinary skill in the art based on the examples of the present disclosure without creative efforts shall fall within the protection scope of the present disclosure.

(7) Specific implementation steps are as follows (1) preparation of a component A: in parts by weight, 60 to 90 parts of a polyol, 50 to 80 parts of a diselenide diol, 30 to 60 parts of a T-type chain extender, 0.1 to 2 parts of high-conductivity carbon black, 0 to 0.2 part of a dispersing agent, 0.1 to 1 part of a catalyst, and 0.1 to 1 part of a leveling agent are taken; one or more selected from the group consisting of the polyol, the diselenide diol, and the T-type chain extender are heated to 50? C. to 130? C., then the high-conductivity carbon black and the dispersing agent are added, and a resulting mixture is ultrasonically stirred; and the remaining materials are added to obtain a hydroxyl-terminated polymer, which is the component A; (2) preparation of a component B: in parts by weight, 100 to 250 parts of a polyisocyanate, 30 to 100 parts of a polyol, 0.05 to 0.4 part of an MWCNT, and 0 to 0.1 part of a dispersing agent are taken; the polyisocyanate or the polyol is heated to 50? C. to 130? C., the MWCNT and the dispersing agent are added, and a resulting mixture is ultrasonically stirred; and the remaining materials are added, and a resulting mixture is stirred at a high temperature to obtain an isocyanate-terminated prepolymer, which is the component B; and (3) the component A and the component B are added to a reactor according to a weight ratio of 1:(1-1.1), and a resulting mixture is stirred at a high speed of 1,500 r/min to 2,000 r/min for 4 min to 10 min and then aged at 100? C. to 120? C. for 1 hour to 2 hours to obtain the environmentally-friendly flexible conductive PU.

Example 1

(8) An environmentally-friendly flexible conductive PU was prepared. The following raw materials in parts by weight were prepared: raw materials for a component A: 85 parts of PPG, 30 parts of a T-type chain extender, 80 parts of a diselenide diol, 1 part of dibutyltin dilaurate, 1 part of high-conductivity carbon black, 0.1 part of DBSA, 0.1 part of dibutyltin dilaurate, and 0.1 part of a leveling agent BYK-UV3510; and raw materials for a component B: 100 parts of IPDI, 75 parts of PPG, 0.4 part of an MWCNT, and 0.1 part of DBSA.

(9) Then, according to the above method, the 100 parts of IPDI were heated to 80? C., the 0.4 part of MWCNT and 0.1 part of DBSA were added, and a resulting mixture was ultrasonically stirred for 1 hour at a high temperature, cooled, then mixed with 75 parts of PPG, and stirred at a high speed for 20 min to obtain the component B; the 85 parts of PPG were heated to 90? C., the 1 part of high-conductivity carbon black and 0.1 part of DB SA were added, and a resulting mixture was ultrasonically stirred for 1 hour at a high temperature; and the 30 parts of T-type chain extender, 80 parts of diselenide diol, 0.1 part of dibutyltin dilaurate, and 0.1 part of leveling agent BYK-UV3510 were gradually added, and a resulting mixture was stirred for 10 min to obtain the component A.

(10) The component B was added to the component A to allow a reaction at 1,500 r/min for 5 min, and a resulting material was poured into a mold, coated for film formation, and cured in a 100? C. oven for 1 hour to obtain a film, which was the environmentally-friendly flexible conductive PU.

Example 2

(11) An environmentally-friendly flexible conductive PU was prepared. The following raw materials in parts by weight were prepared: raw materials for a component A: 45 parts of polytetrahydrofuran ether glycol, 40 parts of polycaprolactone glycol, 40 parts of a T-type chain extender, 60 parts of a diselenide diol, 0.1 part of dibutyltin dilaurate, 0.1 part of a leveling agent BYK-UV3510, 1 part of high-conductivity carbon black, and 0.1 part of NMP; and raw materials for a component B: 78 parts of TDI, 40 parts of polytetrahydrofuran ether glycol, 35 parts of polycaprolactone glycol, 0.3 part of an MWCNT, and 0.1 part of NMP.

(12) The 78 parts of TDI were heated to 100? C., the 0.3 part of MWCNT and 0.1 part of NMP were added, and a resulting mixture was ultrasonically stirred for 40 min at a high temperature, cooled, mixed with the 40 parts of polytetrahydrofuran ether glycol and 35 parts of polycaprolactone glycol, and stirred at a high speed for 20 min to obtain the component B; the 40 parts of T-type chain extender were heated to 60? C., the 1 part of high-conductivity carbon black and 0.1 part of NMP were added, and a resulting mixture was ultrasonically stirred for 1 hour at a high temperature and then cooled; and the 45 parts of polytetrahydrofuran ether glycol, 40 parts of polycaprolactone glycol, 60 parts of diselenide diol, 1 part of dibutyltin dilaurate, and 0.1 part of leveling agent were simultaneously added, and a resulting mixture was stirred at a high speed for 20 min to obtain the component A.

(13) The component B was added to the component A to allow a reaction at 1,500 r/min for 10 min, and a resulting material was poured into a mold, coated for film formation, and cured in a 100? C. oven for 1 hour to obtain a film, which was the environmentally-friendly flexible conductive PU.

(14) FIGS. 1A and 1B respectively shows optical microscopy images of the sample cut with a knife before and after healing at room temperature under light for 12 hours, and an obvious healing effect can be observed.

Example 3

(15) An environmentally-friendly flexible conductive PU was prepared. The following raw materials in parts by weight were prepared: raw materials for a component A: 85 parts of PPG, 45 parts of a T-type chain extender, 65 parts of a diselenide diol, 0.1 part of dibutyltin dilaurate, 0.1 part of a leveling agent BYK-UV3510, and 2 parts of high-conductivity carbon black; and raw materials for a component B: 78 parts of TDI, 75 parts of PPG, and 0.2 part of an MWCNT.

(16) The 78 parts of TDI were heated to 80? C., the 0.2 part of MWCNT was added, and a resulting mixture was ultrasonically stirred for 1.5 hours at a high temperature, cooled, mixed with the 75 parts of PPG, and stirred at a high speed for 20 min to obtain the component B; the 85 parts of PPG were heated to 120? C., the 2 parts of high-conductivity carbon black were added, a resulting mixture was ultrasonically stirred for 1 hour at a high temperature and then cooled, and the 45 parts of T-type chain extender, 65 parts of diselenide diol, 0.1 part of dibutyltin dilaurate, and 0.1 part of leveling agent were gradually added to obtain the component A.

(17) The component B was added to the component A to allow a reaction at 2,000 r/min for 5 min, and a resulting material was poured into a mold, coated for film formation, and cured in a 100? C. oven for 1.5 hours to obtain a film, which was the environmentally-friendly flexible conductive PU.

Example 4

(18) An environmentally-friendly flexible conductive PU was prepared. The following raw materials in parts by weight were prepared: raw materials for a component A: 85 parts of polytetrahydrofuran ether glycol, 50 parts of a T-type chain extender, 60 parts of a diselenide diol, 0.1 part of dibutyltin dilaurate, 0.1 part of a leveling agent BYK-UV3510, and 2 parts of high-conductivity carbon black; and raw materials for a component B: 100 parts of IPDI, 75 parts of polytetrahydrofuran ether glycol, and 0.1 part of an MWCNT.

(19) The 100 parts of IPDI were heated to 60? C., the 0.1 part of MWCNT was added, and a resulting mixture was ultrasonically stirred for 30 min at a high temperature, cooled, mixed with the 75 parts of polytetrahydrofuran ether glycol, and stirred at a high speed for 15 min to obtain the component B; the 85 parts of polytetrahydrofuran ether glycol were heated to 100? C., the 2 parts of high-conductivity carbon black were added, and a resulting mixture was ultrasonically stirred for 1 hour at a high temperature and then cooled, and the 50 parts of T-type chain extender, 60 parts of diselenide diol, 0.1 part of dibutyltin dilaurate, and 0.1 part of leveling agent BYK-UV3510 were gradually added to obtain the component A.

(20) The component B was added to the component A to allow a reaction at 2,000 r/min for 8 min, and a resulting material was poured into a mold, coated for film formation, and cured in a 120? C. oven for 1 hour to obtain a film, which was the environmentally-friendly flexible conductive PU.

(21) The performance of Examples 1 to 4 was tested:

(22) TABLE-US-00001 TABLE 1 Example Example Example Example 1 2 3 4 Electric 1.6 ? 10.sup.4 1.8 ? 10.sup.4 1.7 ? 10.sup.4 1.8 ? 10.sup.4 conductivity/ ? .Math. cm ? .Math. cm ? .Math. cm ? .Math. cm volume resistivity Healing Room Room Room Room conditions temperature, temperature, temperature, temperature, light, 12 h light, 12 h light, 12 h light, 12 h Healing 90% 85% 86% 85% efficiency

(23) A variety of performance data tested according to national standards can be obtained from Table 1.

Comparative Example

(24) The test performances of various conductive PUs currently available are shown in Table 2 (data sources).

(25) TABLE-US-00002 TABLE 2 Conductive Silver T-ZnO/ Silver MWCNT.sup.[4] material nanowire.sup.[1] Ag nanowire.sup.[3] nanofiller.sup.[2] Preparation Solvent- Waterborne Solvent- WPU conditions based PU polyurethane based PU (WPU) Electric Resistance: Conductivity: Con- Con- conductivity 0.23 M? to 6.35 ? 10.sup.4 ductivity: ductivity: 2.86 M? S/m, and 353 S/cm 500 S/cm resistance: 0.52 ? Self-healing Thermally- No healing No healing No healing conditions reversible performance performance performance DA reaction .sup.[1]CN111825872A Self-healing transparent polyurethane composite material with electric conductivity and thermal reversibility, and preparation method thereof. .sup.[2]Xu, Y, Yang Y, Yan D X, et al. Flexible and conductive polyurethane composites for electromagnetic shielding and printable circuit[J]. Chemical Engineering Journal, 2019, 360: 1427-1436. .sup.[3]Al-Attabi N Y, Adhikari R, Cass P, et al. Silver nanowire as an efficient filler for high conductive polyurethane composites[J]. Materials and Technology, 2019, 35(4): 462-468. .sup.[4]Andreoli E, Liao K S, Cricini A, et al. Carbon black instead of mutiwall carbon nanotubes for achieving comparable high electrical conductivities in polyurethane-based coatings[J]. Thin Solid Films, 2014, 550: 558-563.

(26) FIGS. 1A and 1B respectively shows optical microscopy images of the sample in the example cut with a knife before and after healing at room temperature under light for 12 hours, and an obvious healing effect can be observed. FIG. 2 is a schematic diagram illustrating a conductive network of the film.

(27) Through performance comparison of the environmentally-friendly flexible conductive PU prepared by the present disclosure with a flexible conductive PU prepared by an existing solution, it can be seen that the PU synthesized by the present disclosure has prominent electric conductivity, with a volume resistivity of 1.8?10.sup.4 ?.Math.cm; and the PU can be healed at room temperature under light for 12 hours when damaged, and the healed PU shows prominent performance, with a healing efficiency up to 90%, which can guarantee the safety and reliability of the conductive material.

(28) The self-healing conductive PU synthesized by the present disclosure can achieve an electric conduction effect and a low percolation threshold at a low addition level, and the PU prepared by this solution does not require a solvent, is healthy and environmentally friendly, and involves simple self-healing conditions.

(29) The environmentally-friendly self-healing PU flexible conductive films prepared in the examples of the present disclosure have prominent self-healing performance, electric conductivity, and mechanical performance, and involves simple healing conditions. In the conductive film, an MWCNT and high-conductivity nano-carbon black are introduced into PU to form a Go network-like structure inside the PU, and the two conductive fillers cooperate to achieve electric conduction, such that excellent electrical conductivity can be achieved at a small amount of the conductive fillers. The PU resin adopts diselenide bonds and hydrogen bonds, and the self-healing is achieved through the breaking and recombining of the diselenide bonds and hydrogen bonds, where the diselenide bonds can be triggered under visible light conditions, and the hydrogen bonds can be triggered under room temperature. The combination of the two solutions enables an excellent self-healing effect under room temperature and light conditions, and the required healing conditions are simple, which has promising application prospects. Moreover, the PU does not require a solvent, which solves the problem of organic pollutant emission during the production and use of solvent-based PU. As the MWCNT and carbon black are used as conductive fillers, the low addition level, low cost, and electric conductivity can all be considered.

(30) In summary, the conductive PU obtained by the technical solution of the present disclosure has promising application prospects.

(31) Finally, it should be noted that the above are only preferred examples of the present disclosure and are not intended to limit the present disclosure. Although the present disclosure has been described in detail with reference to the above examples, those skilled in the art can still modify the technical solutions described in the above examples, or equivalently substitute some of the technical features of the examples. Any modifications, equivalent substitutions, improvements, and the like within the spirit and principle of the present disclosure should fall within the protection scope of the present disclosure.