CN114940740B - High-performance transparent room-temperature self-repairing polyurethane elastomer based on multiple reversible actions and preparation method thereof - Google Patents
High-performance transparent room-temperature self-repairing polyurethane elastomer based on multiple reversible actions and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of self-repairing polyurethane elastomers, and discloses a high-performance transparent room-temperature self-repairing polyurethane elastomer based on multiple reversible actions and a preparation method thereof. The method comprises the following steps: 1) Reacting polyether polyol with diisocyanate to obtain polyurethane prepolymer; 2) Sequentially carrying out chain extension reaction on the polyurethane prepolymer and chain extender boric acid and dimethylglyoxime to obtain polyurethane reaction liquid; adding metal salt solution for reaction, and curing and forming to obtain the polyurethane elastomer. The elastomer of the invention has good mechanical property and self-repairing property and keeps higher transparency. The room temperature self-repairing efficiency of the invention is higher than 90%, the mechanical property is excellent (the tensile strength can reach 15.3MPa, the elongation at break is over 1200%), and the light transmittance in the visible light range is higher than 80%.
Description
Technical Field
The invention belongs to the technical field of functional polyurethane materials, and particularly relates to a high-performance transparent room-temperature self-repairing polyurethane elastomer based on multiple reversible actions and a preparation method thereof.
Background
The self-repairing material is an intelligent material developed in more than ten years, and can repair the damaged material spontaneously or under the stimulation of certain external conditions, and recover the performance of the material, so that the service life of the material is prolonged, the resource waste is reduced, and the sustainable development of the resource is realized. Intrinsic self-healing materials rely on reversible fragmentation-recombination of dynamic effects to effect self-healing of the material by introducing dynamic covalent bonds or dynamic non-covalent bonds into the polymer. However, the bond energy of dynamic bonds is often lower than that of covalent bonds, and the introduction of dynamic bonds often leads to a great reduction in the mechanical properties of the material. For room temperature self-repairing materials, the materials need to have better molecular chain movement capability under room temperature conditions, which is disadvantageous for mechanical properties, and how to maintain the balance between the self-repairing properties and the mechanical strength is always a great challenge for researchers. Furthermore, the maintenance of transparency also requires that the polymer have an amorphous or amorphous structure, which is clearly detrimental to the improvement of strength.
Polysiloxane elastomers which exhibit excellent light transmittance (greater than 90%) but have tensile strength of only 0.17MPa (Xingyue Lei, yawen Huang, shai Liang, et al preparation of highly transparent, room-temperature self-healing and recyclable silicon elastomers based on dynamic imine bond and their ion responsive properties, materials Letters,2020, 268:127598) have been reported to undergo room temperature self-repair back through imine bonds. Chinese patent No. CN 110684175A discloses a super-tough room temperature self-repairing elastomer material with high light transmittance, the elastomer realizes self-repairing through abundant hydrogen bonding between molecules, and has light transmittance of more than 90% in the visible light region, however, the mechanical strength of the elastomer can only reach 4.83MPa at maximum. The Chinese patent application CN 110105534A discloses a transparent high-strength high-toughness room temperature self-repairing elastomer material, wherein the elastomer obtains excellent room temperature self-repairing capability and better mechanical strength through the synergistic effect of hydrogen bond, disulfide bond and coordination effect, and the light transmittance can reach more than 90 percent. By adjusting the molecular chain structure of the elastomer, the mechanical strength of the elastomer can reach more than 8MPa, but the elastomer still needs to be further improved to meet the requirements of practical application. The transparent self-repairing elastomer prepared by the prior art often cannot achieve the transparency, the self-repairing performance and the mechanical performance of the elastomer, and the preparation of the transparent room-temperature self-repairing elastomer with high performance is an extremely serious challenge in the current research.
According to the invention, the dynamic covalent bond boric acid ester bond and the oxime urethane bond are simultaneously introduced to the polyurethane main chain to endow the polyurethane main chain with self-repairing capability, dynamic covalent bonds with different strengths form coordination, namely, weak dynamic bonds (oxime urethane bonds) can be reversibly broken under mild conditions so that the elastomer keeps higher molecular chain movement capability, and strong dynamic bonds (boric acid ester bonds) can keep certain strength; and then, metal ions are further introduced to form dynamic coordination crosslinking to enhance the action force between molecular chains, weaker hydrogen bonds and coordination bonds in the polyurethane can be sequentially broken when the elastomer is acted by external force, the effect of dissipating energy is achieved in a multi-level manner, and the strength and toughness of the elastomer are improved. The invention utilizes the synergistic effect of multiple reversible bonds to regulate and control the interaction force between molecular chains and the movement capacity of polymer chain segments, and prepares the transparent room temperature self-repairing elastomer material with high performance.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a high-performance transparent room-temperature self-repairing polyurethane elastomer based on multiple reversible actions and a preparation method thereof. According to the invention, polyurethane prepolymer is obtained by reacting polyether polyol with diisocyanate, then boric acid chain extender and oxime chain extender are used for chain extension of the prepolymer, so that reversible covalent bonds (boric acid ester and oxime urethane bonds) are introduced into polyurethane molecular chains, finally, metal salt and oxime urethane bonds are added to form coordination, multiple dynamic actions are introduced into polyurethane, and the molecular chain structure of the polymer is reasonably regulated, so that the transparent high-performance room-temperature self-repairing elastomer is obtained. The mechanical strength of the polyurethane elastomer prepared by the method can reach 15.3+/-0.7 MPa, meanwhile, the high elongation at break (1232+/-68%) is maintained, the self-repairing efficiency can reach more than 90% after being repaired for 24 hours under the room temperature condition, the light transmittance in the visible light range is more than 80%, and the transparency, the self-repairing performance and the mechanical performance are simultaneously realized.
The aim of the invention is achieved by the following technical scheme:
the preparation method of the high-performance transparent room-temperature self-repairing polyurethane elastomer based on the multiple reversible actions comprises the following steps:
1) Polyether polyol and diisocyanate react under the action of a catalyst to obtain polyurethane prepolymer;
2) The polyurethane prepolymer is subjected to chain extension reaction with boric acid serving as a chain extender and dimethylglyoxime serving as a chain extender in sequence to obtain polyurethane reaction liquid; and mixing the metal salt solution with polyurethane reaction liquid for reaction, and finally curing and forming to obtain the polyurethane elastomer.
The polyurethane prepolymer is obtained by reacting polyether polyol with diisocyanate under the action of a catalyst; in the polyurethane prepolymer, the mol ratio of diisocyanate to polyether polyol is 2-2.1: 1.
the diisocyanate is one or more of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, 4' -diphenylmethane diisocyanate and toluene diisocyanate, preferably one or more of 1, 6-hexamethylene diisocyanate and isophorone diisocyanate.
The polyether polyol of step 1) is preferably a polyether diol, which is dehydrated prior to use, such as: and (5) vacuum dehydration treatment.
The polyether polyol is one or more of polytetrahydrofuran glycol, polypropylene glycol and polysiloxane glycol.
The molecular weight of the polyether polyol is 800-1500.
The polyether polyol in the step 1) is more preferably one or more of polytetrahydrofuran glycol 1000, polypropylene glycol 1000 and polysiloxane glycol 1000.
The reaction temperature in the step 1) is 80-85 ℃, and the reaction time is 3-4 h.
The catalyst in the step 1) is more than one of dibutyl tin dilaurate, stannous octoate, zinc iso-octoate and zinc neodecanoate.
The addition amount of the catalyst is 0.1-2% of the mass of the polyether polyol.
Adding an organic solvent in the reaction process of the step 1) to adjust the reaction viscosity, wherein the organic solvent is one or more of N, N '-dimethylformamide, N' -dimethylacetamide, toluene and tetrahydrofuran.
The addition amount of the organic solvent satisfies the reactant concentration of 2-3 g/ml. The reactant concentration refers to the concentration of the total mass of the reactants (referring to the total mass of polyether polyol and diisocyanate) in the organic solvent.
The metal salt in the step 2) is more than one of zinc chloride and aluminum chloride.
The mole ratio of the chain extender boric acid to the polyether polyol in the step 2) is 0.3-0.7: 1, a step of; the mole ratio of the chain extender dimethylglyoxime to the polyether polyol is 0.3-0.5: 1, preferably 0.4:1, a step of; the molar ratio of the metal salt to the chain extender dimethylglyoxime is 0-0.6: 1, preferably 0.4 to 0.6:1.
the chain extension reaction condition of the chain extender boric acid in the step 2) is that the reaction is carried out for 4 to 10 hours at the temperature of 70 to 80 ℃; the chain extender dimethylglyoxime reacts for 1-3 hours at the temperature of 60-70 ℃; the reaction condition of the metal salt is that the metal salt reacts for 30min to 1h at the temperature of 60 to 70 ℃. The reaction is carried out with stirring.
In the step 2), the chain extender boric acid is dissolved by adopting an organic solvent before the reaction, and the chain extender dimethylglyoxime is dissolved by adopting the organic solvent before the reaction;
such as: the molar ratio of boric acid to organic solvent in the boric acid solution is (1-7): 100; the mole ratio of the dimethylglyoxime in the dimethylglyoxime solution to the organic solvent is (3-5): 100.
an organic solvent is added in the chain extension reaction process of the chain extender boric acid to control the viscosity of the reaction liquid, so that the gel is prevented;
each organic solvent is more than one of N, N '-dimethylformamide, N' -dimethylacetamide, toluene and tetrahydrofuran.
The addition amount of the organic solvent satisfies the following conditions: the concentration of the reaction solution is controlled to be 0.5-0.8 g/ml. The concentration of the reaction liquid here means the concentration of the prepolymer and the chain extender in the organic solvent.
The metal salt solution in the step 2) is a solution obtained by dissolving metal salt in an organic solvent; the organic solvent is more than one of tetrahydrofuran, N '-dimethylformamide and N, N' -dimethylacetamide.
The concentration of the metal salt solution is 0.4-0.6 mol/L.
And 2) the solidification forming process is heated and formed under vacuum condition, namely, the solidification forming process is kept stand for 12 to 24 hours at the temperature of 60 to 80 ℃ under vacuum condition.
The repairing method of the high-performance transparent room-temperature self-repairing polyurethane elastomer based on multiple reversible actions comprises the following steps: the sample is cut into a standard dumbbell-shaped sample, the sample is cut from the middle by a cutter, two sections are butted together, the sample is extruded for 10 seconds and then repaired for 24 hours in a room temperature environment, and then the tensile strength of the repaired sample is measured. The self-healing efficiency (η) is defined as follows:
in the method, in the process of the invention,
σ healed -tensile strength in MPa for the repair sample;
σ pristine the tensile strength is the original tensile strength, and the unit is MPa.
The tensile strength of the high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions can reach 15.3MPa, the elongation at break can reach 1200%, and the 24-hour self-repairing efficiency can reach more than 90%.
The repairing mechanism of the high-performance transparent room-temperature self-repairing polyurethane elastomer based on multiple reversible actions is as follows: the existence of the boric acid ester bond and the oxime ammonia ester bond in the molecular chain enables the molecular chain segment to decompose the movement of the whole chain into the movement of multiple chain segments, improves the movement capacity of the molecular chain segment, and enables the elastomer to show excellent self-repairing performance. The hydrogen bond and the coordination bond can be sequentially disconnected as sacrificial bonds under the action of external force, so that the effect of dissipating energy is achieved in a multi-level manner, and the strength and the toughness of the elastomer are improved. The mechanical property and the self-repairing property of the material are simultaneously realized through the synergistic effect of multiple dynamic bonds. In addition, the micro-region size of the polyurethane is controlled by adjusting the molecular chain structure, so that the light transmittance of the polyurethane elastomer in the visible light range can be kept above 80%.
Compared with the prior art, the invention has the following advantages:
1) The invention simultaneously takes into account the mechanical property, self-repairing property and transparency of the polyurethane elastomer, the tensile strength of the prepared room temperature self-repairing elastomer can reach 15.3MPa, the elongation at break can reach 1200%, the self-repairing efficiency of repairing for 24 hours under room temperature condition can reach more than 90%, and meanwhile, the light transmittance of the elastomer in the visible light range is kept at more than 80%.
2) Polyether glycol with high flexibility is selected as a soft segment, and the intermolecular force of the polyether glycol is weak, so that hydrogen bond action is not easy to form, and the elastomer keeps better molecular chain movement capability; the introduction of the reversible borate ester bond and the reversible oxime urethane bond can decompose the movement of the whole chain of the molecular chain into the movement of a plurality of chain segments, so that the self-repairing capability of the elastomer is enhanced; the introduction of coordination action enhances the interaction force among molecular chains in the polyurethane hard segment phase, and meanwhile, the coordination action and hydrogen bonds can be reversibly broken and dissipate energy in the stretching process of the elastomer, so that the mechanical strength of the elastomer is greatly improved.
3) The synthesis reaction condition of the invention is mild, the preparation process is simple, and the raw materials are easy to obtain.
Drawings
Fig. 1 is a graph of light transmittance in the visible wavelength range of the polyurethane elastomers prepared in example 1, example 2, example 3 and example 6.
Detailed Description
The invention will be further illustrated with reference to specific examples and figures, to which the scope of protection is not limited. The following parts are molar parts unless specified.
Example 1
A high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions comprises the following synthesis steps:
(1) 10 parts of polytetrahydrofuran (PTMEG 1000) with a molecular weight of 1000 (number average molecular weight) are vacuumized at 110 ℃, and after water removal for 1h, heating is turned off; after the temperature was reduced to 80 ℃,20 parts of 3-isocyanatomethylene-3, 5-trimethylcyclohexyl isocyanate (IPDI) was added, 0.3 part of dibutyltin dilaurate (DBTDL) as a catalyst and 100 parts of toluene were added to adjust the viscosity of the reactants, and the prepolymer was obtained after reaction for 4 hours at 80 ℃.
(2) 6 parts of boric acid (H) 3 BO 3 ) After 100 parts of DMF was completely dissolved, the mixture was added to the prepolymer obtained in the step (1) to react at 80℃while 200 parts of toluene was added to dilute the mixture to prevent gelation, and after 10 hours, the heating was stopped to obtain a preliminary chain extension product.
(3) Weighing 4 parts of Dimethylglyoxime (DMG), adding 100 parts of DMF (dimethyl formamide) into the product obtained in the step (2) after complete dissolution, reacting for 2 hours at 60 ℃, adding 2 parts of zinc chloride into the reaction solution after complete dissolution by 40 parts of tetrahydrofuran, reacting for 30 minutes at 60 ℃, pouring into a polytetrafluoroethylene mould to form a plate, and preserving heat for 12 hours at 60 ℃ under vacuum condition to obtain the polyurethane elastomer.
Example 2
A high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions comprises the following synthesis steps:
(1) 10 parts of polytetrahydrofuran (PTMEG 1000) with a molecular weight of 1000 (number average molecular weight) are vacuumized at 110 ℃, and after water removal for 1h, heating is turned off; after the temperature was reduced to 80 ℃,20 parts of 3-isocyanatomethylene-3, 5-trimethylcyclohexyl isocyanate (IPDI) was added, 0.3 part of dibutyltin dilaurate (DBTDL) as a catalyst and 100 parts of toluene were added to adjust the viscosity of the reactants, and the prepolymer was obtained after reaction for 4 hours at 80 ℃.
(2) 6 parts of boric acid (H) 3 BO 3 ) After 100 parts of DMF was completely dissolved, the mixture was added to the prepolymer obtained in the step (1) to react at 80℃while 200 parts of toluene was added to dilute the mixture to prevent gelation, and after 10 hours, the heating was stopped to obtain a preliminary chain extension product.
(3) Weighing 4 parts of Dimethylglyoxime (DMG), adding 100 parts of DMF (dimethyl formamide) into the product obtained in the step (2) after complete dissolution, reacting for 2 hours at 60 ℃, adding 1 part of zinc chloride into the reaction solution after complete dissolution by 100 parts of tetrahydrofuran, reacting for 30 minutes at 60 ℃, pouring into a polytetrafluoroethylene mould to form a plate, and preserving heat for 12 hours at 60 ℃ under vacuum condition to obtain the polyurethane elastomer.
Example 3
A high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions comprises the following synthesis steps:
(1) 10 parts of polytetrahydrofuran (PTMEG 1000) with a molecular weight of 1000 (number average molecular weight) are vacuumized at 110 ℃, and after water removal for 1h, heating is turned off; after the temperature was reduced to 80 ℃,20 parts of 3-isocyanatomethylene-3, 5-trimethylcyclohexyl isocyanate (IPDI) was added, 0.3 part of dibutyltin dilaurate (DBTDL) as a catalyst and 100 parts of toluene were added to adjust the viscosity of the reactants, and the prepolymer was obtained after reaction for 4 hours at 80 ℃.
(2) 6 parts of boric acid (H) 3 BO 3 )，After 100 parts of DMF was completely dissolved, the mixture was added to the prepolymer obtained in the step (1) to react at 80℃while 200 parts of toluene was added to dilute the mixture to prevent gelation, and after 10 hours, the heating was stopped to obtain a preliminary chain extension product.
(3) Weighing 4 parts of Dimethylglyoxime (DMG), adding 100 parts of DMF (dimethyl formamide) into the product obtained in the step (2) after complete dissolution, reacting for 2 hours at 60 ℃, adding 0.5 part of zinc chloride into the reaction solution after complete dissolution by 50 parts of tetrahydrofuran, reacting for 30 minutes at 60 ℃, pouring into a polytetrafluoroethylene mould to form a plate, and preserving heat for 12 hours at 60 ℃ under vacuum condition to obtain the polyurethane elastomer.
Example 4
A high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions comprises the following synthesis steps:
(1) 10 parts of polytetrahydrofuran (PTMEG 1000) with a molecular weight of 1000 (number average molecular weight) are vacuumized at 110 ℃, and after water removal for 1h, heating is turned off; after the temperature is reduced to 80 ℃,20 parts of 4,4' -diphenylmethane diisocyanate (MDI) is added, 0.3 part of catalyst dibutyl tin dilaurate (DBTDL) and 100 parts of toluene are added to regulate the viscosity of the reactant, and the prepolymer is obtained after the reaction is carried out for 4 hours at 80 ℃.
(2) 6 parts of boric acid (H) 3 BO 3 ) After 100 parts of DMF was completely dissolved, the mixture was added to the prepolymer obtained in the step (1) to react at 80℃while 200 parts of toluene was added to dilute the mixture to prevent gelation, and after 10 hours, the heating was stopped to obtain a preliminary chain extension product.
(3) Weighing 4 parts of Dimethylglyoxime (DMG), adding 100 parts of DMF (dimethyl formamide) into the product obtained in the step (2) after complete dissolution, reacting for 2 hours at 60 ℃, adding 2 parts of zinc chloride into the reaction solution after complete dissolution by 200 parts of tetrahydrofuran, reacting for 30 minutes at 60 ℃, pouring into a polytetrafluoroethylene mould to form a plate, and preserving heat for 12 hours at 60 ℃ under vacuum condition to obtain the polyurethane elastomer.
Example 5
A high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions comprises the following synthesis steps:
(1) 10 parts of polytetrahydrofuran (PTMEG 1000) with a molecular weight of 1000 (number average molecular weight) are vacuumized at 110 ℃, and after water removal for 1h, heating is turned off; after the temperature is reduced to 80 ℃,20 parts of Toluene Diisocyanate (TDI) is added, 0.3 part of catalyst dibutyl tin dilaurate (DBTDL) and 100 parts of toluene are added to regulate the viscosity of the reactant, and the prepolymer is obtained after the reaction is carried out for 4 hours at 80 ℃.
(2) 6 parts of boric acid (H) 3 BO 3 ) After 100 parts of DMF was completely dissolved, the mixture was added to the prepolymer obtained in the step (1) to react at 80℃while 200 parts of toluene was added to dilute the mixture to prevent gelation, and after 10 hours, the heating was stopped to obtain a preliminary chain extension product.
(3) Weighing 4 parts of Dimethylglyoxime (DMG), adding 100 parts of DMF (dimethyl formamide) into the product obtained in the step (2) after complete dissolution, reacting for 2 hours at 60 ℃, adding 2 parts of zinc chloride into the reaction solution after complete dissolution by 200 parts of tetrahydrofuran, reacting for 30 minutes at 60 ℃, pouring into a polytetrafluoroethylene mould to form a plate, and preserving heat for 12 hours at 60 ℃ under vacuum condition to obtain the polyurethane elastomer.
Example 6
A high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions comprises the following synthesis steps:
(1) 10 parts of polytetrahydrofuran (PTMEG 1000) with a molecular weight of 1000 (number average molecular weight) are vacuumized at 110 ℃, and after water removal for 1h, heating is turned off; after the temperature was reduced to 80 ℃,20 parts of 3-isocyanatomethylene-3, 5-trimethylcyclohexyl isocyanate (IPDI) was added, 0.3 part of dibutyltin dilaurate (DBTDL) as a catalyst and 100 parts of toluene were added to adjust the viscosity of the reactants, and the prepolymer was obtained after reaction for 4 hours at 80 ℃.
(2) 6 parts of boric acid (H) 3 BO 3 ) After 100 parts of DMF was completely dissolved, the mixture was added to the prepolymer obtained in the step (1) to react at 80℃while 200 parts of toluene was added to dilute the mixture to prevent gelation, and after 10 hours, the heating was stopped to obtain a preliminary chain extension product.
(3) Weighing 4 parts of Dimethylglyoxime (DMG), adding 100 parts of DMF (dimethyl formamide) into the product obtained in the step (2) after complete dissolution, reacting for 2 hours at 60 ℃, pouring into a polytetrafluoroethylene mould to form a plate, and preserving heat for 12 hours at 60 ℃ under vacuum condition for forming and curing to obtain the polyurethane elastomer.
Comparative example 1
A high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions comprises the following synthesis steps:
(1) 10 parts of polytetrahydrofuran (PTMEG 1000) with a molecular weight of 1000 (number average molecular weight) are vacuumized at 110 ℃, and after water removal for 1h, heating is turned off; after the temperature was reduced to 80 ℃,20 parts of 3-isocyanatomethylene-3, 5-trimethylcyclohexyl isocyanate (IPDI) was added, 0.3 part of dibutyltin dilaurate (DBTDL) as a catalyst and 100 parts of toluene were added to adjust the viscosity of the reactants, and the prepolymer was obtained after reaction for 4 hours at 80 ℃.
(2) 6 parts of 1, 4-Butanediol (BDO) is weighed, 100 parts of DMF is added into the prepolymer obtained in the step (1) after complete dissolution, reaction is carried out at 80 ℃, 200 parts of toluene is added during the reaction to prevent gel, heating is stopped after 10 hours, and a preliminary chain extension product is obtained.
(3) Weighing 4 parts of Dimethylglyoxime (DMG), adding 100 parts of DMF (dimethyl formamide) into the product obtained in the step (2) after complete dissolution, reacting for 2 hours at 60 ℃, adding 2 parts of zinc chloride into the reaction solution after complete dissolution by 200 parts of tetrahydrofuran, reacting for 30 minutes at 60 ℃, pouring into a polytetrafluoroethylene mould to form a plate, and preserving heat for 12 hours at 60 ℃ under vacuum condition to obtain the polyurethane elastomer.
Comparative example 2
A high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions comprises the following synthesis steps:
(1) 10 parts of polytetrahydrofuran (PTMEG 1000) with a molecular weight of 1000 (number average molecular weight) are vacuumized at 110 ℃, and after water removal for 1h, heating is turned off; after the temperature was reduced to 80 ℃,20 parts of 3-isocyanatomethylene-3, 5-trimethylcyclohexyl isocyanate (IPDI) was added, 0.3 part of dibutyltin dilaurate (DBTDL) as a catalyst and 100 parts of toluene were added to adjust the viscosity of the reactants, and the prepolymer was obtained after reaction for 4 hours at 80 ℃.
(2) 6 parts of boric acid (H) 3 BO 3 ) After 100 parts of DMF was completely dissolved, the mixture was added to the prepolymer obtained in the step (1) to react at 80℃while 200 parts of toluene was added to dilute the mixture to prevent gelation, and after 10 hours, the heating was stopped to obtain a preliminary chain extension product.
(3) Weighing 4 parts of 1, 4-Butanediol (BDO), adding 100 parts of DMF (dimethyl formamide) into the product obtained in the step (2) after complete dissolution, reacting for 2 hours at 60 ℃, adding 2 parts of zinc chloride into the reaction liquid after complete dissolution by 200 parts of tetrahydrofuran, reacting for 30 minutes at 60 ℃, pouring into a polytetrafluoroethylene mould to form a plate, and preserving heat for 12 hours at 60 ℃ under vacuum condition to obtain the polyurethane elastomer.
Comparative example 3
A high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions comprises the following synthesis steps:
(1) 10 parts of polytetrahydrofuran (PTMEG 1000) with a molecular weight of 1000 (number average molecular weight) are vacuumized at 110 ℃, and after water removal for 1h, heating is turned off; after the temperature was reduced to 80 ℃,20 parts of 3-isocyanatomethylene-3, 5-trimethylcyclohexyl isocyanate (IPDI) was added, 0.3 part of dibutyltin dilaurate (DBTDL) as a catalyst and 100 parts of toluene were added to adjust the viscosity of the reactants, and the prepolymer was obtained after reaction for 4 hours at 80 ℃.
(2) 10 parts of 1, 4-Butanediol (BDO) is weighed, 100 parts of DMF is added into the prepolymer obtained in the step (1) after complete dissolution, reaction is carried out at 80 ℃, 200 parts of toluene is added during the reaction to prevent gel, and heating is stopped after 2 hours, so that a chain extension product is obtained.
(3) And (3) adding 2 parts of zinc chloride into the reaction liquid after being completely dissolved by 200 parts of tetrahydrofuran, reacting for 30min at 60 ℃, pouring into a polytetrafluoroethylene die to form a plate, and preserving heat for 12h at 60 ℃ under vacuum condition to form and cure to obtain the polyurethane elastomer.
Comparative example 1 is a polyurethane elastomer having no borate bond introduced into the main chain and containing only oxime urethane bonds and coordinate bonds, comparative example 2 is a polyurethane elastomer having no oxime urethane bonds introduced into the main chain and containing only borate bonds and coordinate bonds, and comparative example 3 is a polyurethane elastomer having no borate bonds and oxime urethane bonds introduced into the main chain and containing only metal salts. The mechanical tensile strength test and the self-repairing test were performed on the above examples and comparative examples, respectively, and the results are shown in table 1.
Example 1 is a high performance transparent room temperature self-healing polyurethane elastomer based on multiple reversible actions prepared according to the present invention. Examples 2 and 3 changed the concentration of coordinated zinc ions based only on example 1, and example 6 was a polyurethane elastomer containing no coordination bonds. By comparing examples 1, 2, 3 and 6, the tensile strength of the elastomer is greatly improved with the increase of the molar amount of zinc ions, and the self-repairing efficiency is only slightly reduced, which indicates that the introduction of the metal coordination bond enhances the mechanical strength of the elastomer, and meanwhile, the elastomer can still maintain higher room temperature self-repairing efficiency due to the dynamic nature of the coordination bond. Example 4 and example 5 are polyurethane elastomers with MDI and TDI forming hard segment phases respectively, which have higher mechanical strength than example 1, but hardly have room temperature self-repairing ability, which means that the hard segment aggregation degree of the elastomers in the two systems is high, and the molecular chain movement is limited under room temperature condition, so that self-repairing is difficult to perform; in the embodiment 1, IPDI is adopted to form a hard segment phase, and the asymmetric structure of the IPDI leads the structure of the hard segment to be irregular, thereby being beneficial to the realization of the self-repairing function.
Table 1 mechanical properties and room temperature self-healing efficiency of each example and comparative example
Fig. 1 shows the transmittance of the elastomer prepared in examples 1, 2, 3 and 6 in the visible light range, and it can be seen that the transmittance of the elastomer (thickness of 1 mm) slightly decreases with the increase of the zinc ion concentration, but the transmittance of 80% can be maintained in the visible light wavelength range, so as to meet the demands of daily use.
The above examples are examples of the present invention for preparing the transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions, but the present invention is not limited to the above examples, and the implementation of the present invention is not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be equivalent substitution, and are included in the scope of the present invention.
Claims (10)
1. A preparation method of a high-performance transparent room-temperature self-repairing polyurethane elastomer based on multiple reversible actions is characterized by comprising the following steps: the method comprises the following steps:
1) Polyether polyol and diisocyanate react under the action of a catalyst to obtain polyurethane prepolymer;
2) The polyurethane prepolymer is subjected to chain extension reaction with boric acid serving as a chain extender and dimethylglyoxime serving as a chain extender in sequence to obtain polyurethane reaction liquid; then mixing metal salt with polyurethane reaction liquid for reaction, and finally curing and forming to obtain a polyurethane elastomer;
step 1) the polyether polyol is polyether glycol; the diisocyanate is more than one of 1, 6-hexamethylene diisocyanate and isophorone diisocyanate;
the metal salt in the step 2) is more than one of zinc chloride and aluminum chloride.
2. The method for preparing the high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions according to claim 1, which is characterized in that: the molar ratio of the chain extender boric acid to the polyether polyol in the step 2) is 0.3-0.7: 1, a step of; the mole ratio of the chain extender dimethylglyoxime to the polyether polyol is 0.3-0.5: 1, a step of; the molar ratio of the metal salt to the chain extender dimethylglyoxime is 0-0.6: 1, a step of;
the chain extension reaction condition of the chain extender boric acid in the step 2) is that the reaction is carried out for 4 to 10 hours at the temperature of 70 to 80 ℃; the chain extender dimethylglyoxime reacts for 1-3 hours at the temperature of 60-70 ℃; the reaction condition of the metal salt is that the metal salt reacts for 30min to 1h at the temperature of 60 to 70 ℃.
3. The method for preparing the high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions according to claim 2, which is characterized in that: the mole ratio of the chain extender dimethylglyoxime to the polyether polyol is 0.4:1, a step of; the molar ratio of the metal salt to the chain extender dimethylglyoxime is 0.4-0.6: 1.
4. the method for preparing the high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions according to claim 1, which is characterized in that:
the molar ratio of diisocyanate to polyether polyol in the step 1) is 2-2.1: 1, a step of;
the diisocyanate is more than one of 1, 6-hexamethylene diisocyanate and isophorone diisocyanate;
the polyether polyol in the step 1) is more than one of polytetrahydrofuran glycol and polypropylene glycol;
the molecular weight of the polyether polyol is 800-1500;
the reaction temperature in the step 1) is 80-85 ℃, and the reaction time is 3-4 hours.
5. The method for preparing the high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions according to claim 4, which is characterized in that:
the polyether polyol in the step 1) is one or a mixture of a plurality of polytetrahydrofuran glycol 1000 and polypropylene glycol 1000.
6. The method for preparing the high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions according to claim 1, which is characterized in that:
the catalyst in the step 1) is more than one of dibutyl tin dilaurate, stannous octoate, zinc iso-octoate and zinc neodecanoate;
the addition amount of the catalyst is 0.1% -2% of the mass of the polyether polyol;
the polyether polyol is dehydrated prior to use.
7. The method for preparing the high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions according to claim 1, which is characterized in that: adding an organic solvent in the reaction process of the step 1) to adjust the reaction viscosity, wherein the organic solvent is more than one of N, N '-dimethylformamide, N' -dimethylacetamide, toluene and tetrahydrofuran;
in the step 2), the chain extender boric acid is dissolved by adopting an organic solvent before the reaction, and the chain extender dimethylglyoxime is dissolved by adopting the organic solvent before the reaction;
an organic solvent is added in the chain extension reaction process of the chain extender boric acid to control the viscosity of the reaction liquid, so that the gel is prevented;
each organic solvent is more than one of N, N '-dimethylformamide, N' -dimethylacetamide, toluene and tetrahydrofuran.
8. The method for preparing the high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions according to claim 1, which is characterized in that: the metal salt is used in the form of a solution in the step 2), and is obtained by dissolving the metal salt in an organic solvent; the organic solvent is more than one of tetrahydrofuran, N '-dimethylformamide and N, N' -dimethylacetamide;
the concentration of the metal salt solution is 0.4-0.6 mol/L;
and 2) performing heating forming in the curing forming process under vacuum condition, namely standing for 12-24 hours at 60-80 ℃ under vacuum condition.
9. A high performance transparent room temperature self-healing polyurethane elastomer based on multiple reversible actions obtained by the preparation method of any one of claims 1 to 8.
10. The method for repairing the high-performance transparent room temperature self-repairing polyurethane elastomer based on multiple reversible actions according to claim 9, wherein the method comprises the following steps: and (3) attaching the sections of the formed polyurethane elastomer together, and repairing the extruded polyurethane elastomer in a room temperature environment.
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| CN116903823A (en) * | 2023-08-17 | 2023-10-20 | 广州境好新材料有限公司 | Bio-based self-repairing polyurethane resin and preparation method thereof |
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