CN117384350A - Functionalized elastomer and application thereof - Google Patents

Functionalized elastomer and application thereof Download PDF

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Publication number
CN117384350A
CN117384350A CN202311380581.1A CN202311380581A CN117384350A CN 117384350 A CN117384350 A CN 117384350A CN 202311380581 A CN202311380581 A CN 202311380581A CN 117384350 A CN117384350 A CN 117384350A
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glycol
healing
elastomer
acid
bio
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Inventor
马丕明
王宏
张林曼
徐鹏武
王策勇
殷俣秀
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Jiangnan University
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Jiangnan University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67Unsaturated compounds having active hydrogen
    • C08G18/68Unsaturated polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a functional elastomer and application thereof, and belongs to the technical field of new materials. The invention introduces a multiple dynamic network composed of rich H bonds, disulfide bonds and metal coordination bonds into an elastomer, wherein the H bonds are composed of urethane bonds and U 2 The UPy segment in diol provides that the metal coordination bond is composed of a ligand provided by dimethylglyoxime and a metal ion, and the functionalized elastomer capable of self-healing at low temperature is prepared by a one-pot method. The obtained functional elastomer has good mechanical property, can realize self-healing at the low temperature of-15 ℃, and has great application prospect in the fields of low-temperature-resistant flexible wearable and the like.

Description

Functionalized elastomer and application thereof
Technical Field
The invention belongs to the technical field of new materials, and relates to a functional elastomer and application thereof.
Background
Self-healing is a biological tissue property that enables them to effectively self-repair after mechanical injury. Therefore, inspired by nature, the self-healing properties are introduced into the elastomer, greatly improving their lifetime and stability, reducing maintenance costs, and enabling novel applications. Therefore, the self-repairing material attracts great attention in many fields of automobile paint, electronic skin, soft robot, etc., and shows great prospect. Exogenous self-healing has limited ability to heal due to the reliance on self-healing agents, limiting their widespread use. Therefore, intrinsic self-healing materials based on dynamic non-covalent interactions or reversible covalent bonds are currently becoming an important research point. However, intrinsic type healing processes typically require external energy input, such as heat, light, pressure, or other agents. Since many materials in real life are damaged under ambient conditions without available external stimuli, it is highly desirable to develop elastomeric materials that can spontaneously self-heal at room temperature or even low temperatures.
Currently, developing elastomeric materials with low Wen Ziyu performance remains a significant challenge. Common methods for designing self-healing materials combine dynamic covalent bonds (disulfide bonds, imine bonds, etc.) with dynamic non-covalent bonds (H bonds, metal coordination bonds, ionic interactions, etc.). However, the materials obtained in this way are generally relatively weak. In contrast, a large number of non-covalent interactions may lead to better mechanical properties, but may impair the self-healing, stretchability and toughness of the material. Furthermore, due to their linear molecular structure, these materials may suffer from limited elasticity and potential creep. Thus, some researchers have chemically crosslinked structures based on dynamic covalent bonds such as urea bonds, boron oxygen bonds, and disulfide bonds to build relatively strong healable materials. However, the crosslinked network limits the movement of the chains and reduces the healing capacity. Overall, the self-healing ability and mechanical properties of the material are inherently mutually exclusive. Achieving both high mechanical robustness and healing efficiency remains a great challenge, especially under ambient conditions, as their requirements on molecular structure are often contradictory.
Disclosure of Invention
In order to solve the problems in the prior art, the invention adopts the following technical scheme:
the invention aims to provide a preparation method of a functionalized elastomer capable of self-healing at low temperature, which comprises the following steps:
(1) Obtaining hydroxyl end-capped bio-based aliphatic prepolymer by using bio-based diacid and dihydric alcohol to react;
(2) Mixing and reacting the hydroxyl-terminated bio-based aliphatic prepolymer with isocyanate, glycol components, glycerol, metal salt and ligand to obtain the functional elastomer.
In one embodiment of the invention, the functionalized elastomer capable of self-healing at low temperature is obtained by reacting glycol, glycerin, isocyanate and metal ions, and the topology structure of the functionalized elastomer contains a plurality of dynamic networks formed by rich hydrogen bonds, carbamate, disulfide bonds and metal coordination bonds, so that the elastomer has low Wen Ziyu bonding performance.
In one embodiment of the present invention, the bio-based glycol is one or a combination of propylene glycol, butylene glycol, rubber seed oil based glycol, palm oil based glycol, sunflower seed oil based glycol, isosorbide, pentylene glycol, ethylene glycol, and dimer alcohol.
In one embodiment of the invention, the bio-based diacid is one or a combination of itaconic acid, sebacic acid, succinic acid, azelaic acid, dimer fatty acid (DAA), dodecyl diacid, fumaric acid.
In one embodiment of the invention, the molar ratio of biobased diol to diacid is (1-2): 1.
in one embodiment of the present invention, the polymerization inhibitor in the step (1) is any one of 4-methoxyphenol and hydroquinone, and the addition amount is 0.05 to 0.5wt%.
In one embodiment of the present invention, the catalyst in the step (1) is tetrabutyl titanate, p-toluenesulfonic acid, antimony acetate, dibutyl tin laurate; the dosage is 0.05-0.5wt% of the total mass.
In one embodiment of the present invention, the reaction in step (1) is carried out at a temperature of 130 to 190℃for a period of 1 to 8 hours.
In one embodiment of the present invention, the hydroxyl terminated biobased aliphatic prepolymer in step (1) has a number average molecular weight of 1000 to 13000.
In one embodiment of the present invention, the glycol component in step (2) is U 2 -diol, or U 2 -combinations of diol with other glycol agents; the other glycol reagents are any one or more of bis (2-hydroxyethyl) disulfide, dimethylglyoxime, butanediol, propylene glycol and isosorbide.
In one embodiment of the present invention, the molar ratio of the total amount of the hydroxyl terminated biobased aliphatic prepolymer and glycol component to glycerin in step (2) is 2 to 8:1.
in one embodiment of the present invention, the molar ratio of the total amount of hydroxyl groups to isocyanate groups in the hydroxyl terminated biobased aliphatic prepolymer and diol component in step (2) is 1:1 to 2.
In one embodiment of the present invention, the isocyanate in step (2) is one or a combination of isophorone isocyanate, hexamethylene diisocyanate, toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), lysine Diisocyanate (LDI).
In one embodiment of the invention, the ligand in step (2) is dimethylglyoxime capable of forming a metal coordination bond with a metal ion.
In one embodiment of the invention, the molar ratio of ligand to glycerol in step (2) is (2-5): 1.
in one embodiment of the present invention, the metal salt in step (2) is one of copper chloride and zinc chloride.
In one embodiment of the invention, the molar ratio of metal salt to ligand in step (2) is 1:10 to 30 percent.
In one embodiment of the invention, the reaction in the step (2) is carried out by stirring at 50-80 ℃ for 1-6h, then 40-60 reacting for 12-24h under nitrogen environment, and then heating to 70-90 ℃ for continuing the reaction for 12-36 h.
In one embodiment of the present invention, the method for preparing an elastomer specifically includes:
(1) Preparing hydroxyl end capped biological aliphatic prepolymer: adding bio-based dibasic acid, dihydric alcohol, polymerization inhibitor and catalyst into a reactor, reacting at 130-190 ℃ for 1-8 h, changing an esterification system into a vacuumizing system, and reacting for 2-8 h to obtain hydroxyl end-capped bio-based aliphatic prepolymer;
(2) Vacuum dewatering the prepolymer at 90-120 deg.c for 1-3 hr, adding isocyanate, bis (2-hydroxyethyl) disulfide and U into the prepolymer at 50-80 deg.c 2 Stirring the diol, the glycerol and the metal ions for 1-6 hours, pouring the reactants into a die, putting the die into an environment with nitrogen to react for 12-24 hours at 40-60 ℃, and then reacting for 12-36 hours at 70-90 ℃.
The invention provides a low-temperature self-healing functionalized elastomer based on the preparation method.
The invention also provides application of the low-temperature self-healing functionalized elastomer in the field of self-powered friction generators and wearable equipment.
The invention also provides application of the low-temperature self-healing functionalized elastomer in the fields of automobile paint, electronic skin and soft robots.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a bio-based crosslinked elastomer containing multiple dynamic networks and a preparation method thereof, which are prepared by a one-pot method. It is characterized by that a multiple dynamic network formed from rich H bond, disulfide bond and metal coordination bond is introduced into the elastomer, in which the H bond is formed from urethane bond and U 2 The UPy section in diol provides, and the metal coordination bond is formed by a ligand provided by dimethylglyoxime and metal ions, so that a strong and weak cross-linked network is formed, and good mechanical properties are further provided for the elastomer; in addition, the bio-based prepolymer as a soft segment imparts sufficient flexibility to the elastomer and a lower glass transition temperature.
Compared with the prior reported self-healing elastomer, the low-temperature self-healing bio-based crosslinked elastomer provided by the invention has the advantages that due to abundant hydrogen bonds, metal coordination bonds and low bond energy disulfide bonds, the self-healing can be realized at the low temperature of minus 15 ℃ by matching with lower glass transition temperature. Has great application prospect in the fields of low temperature resistance, flexibility, wearing and the like.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
Example 1
(1) Into a 100ml three-necked flask, 7.8 g (0.060 mol) of itaconic acid, 8.09 g (0.040 mol) of sebacic acid, 4.18 g (0.055 mol) of 1, 3-propanediol, 4.95 g (0.055 mol) of 1, 4-butanediol and 0.05wt% of 4-methoxyphenol and 0.05wt% of tetrabutyl titanate were charged, water produced by the reaction was collected using a water separator and a condenser, the amount of nitrogen gas was set to 0.15L/min, the rotational speed at magnetic stirring was set to 380r/min, the reaction temperature was 180℃and the reaction time was 2h; then changing the reaction system into a vacuum pumping system to continue the reaction for 5 hours to obtain the light yellow hydroxyl end capped bio-based unsaturated aliphatic prepolymer, wherein the number average molecular weight is 3680g/mol.
(2) The molar ratio of the total amount of diol components and prepolymer to glycerin is 8:1 to a three-necked flask of 100ml at 50℃were charged 10mmol of prepolymer, 10mmol of dimethylglyoxime, 3mmol of bis (2-hydroxyethyl) disulfide, 1mmol of U 2 Diol, 3mmol of glycerol, in a molar ratio of total hydroxyl groups to isocyanate groups of 1:1, 28.5mmol of isophorone isocyanate, 3 drops of dibutyl tin laurate, 0.32mmol of copper chloride and 40ml of acetone are added in proportion, stirred and reacted for 2 hours, poured into a mould, dried for 24 hours at 50 ℃, then heated to 75 ℃, dried for 24 hours, and the drying process is carried out under nitrogen atmosphere, so as to obtain the cross-linked polyurethane elastomer with low Wen Ziyu synthetic property.
Example 2
(1) The corresponding pale yellow hydroxyl-terminated biobased unsaturated aliphatic prepolymer was prepared as in example 1.
(2) To 50 ℃ and 100mlInto a three-necked flask, 10mmol of prepolymer, 10mmol of dimethylglyoxime, 2mmol of bis (2-hydroxyethyl) disulfide and 2mmol of U were added 2 Diol, 3mmol glycerol, in a molar ratio of total hydroxyl groups to isocyanate of 1:1, 28.5mmol of isophorone isocyanate, 3 drops of dibutyl tin laurate, 0.32mmol of copper chloride and 40ml of acetone are added in proportion, stirred and reacted for 2 hours, poured into a mould, dried for 24 hours at 50 ℃, then heated to 75 ℃, dried for 24 hours, and the drying process is carried out under nitrogen atmosphere, so as to obtain the cross-linked polyurethane elastomer with low Wen Ziyu synthetic property.
Example 3
(1) The corresponding pale yellow hydroxyl-terminated biobased unsaturated aliphatic prepolymer was prepared as in example 1.
(2) Into a 100ml three-necked flask at 50℃were added 10mmol of prepolymer, 10mmol of dimethylglyoxime, 1mmol of bis (2-hydroxyethyl) disulfide and 3 mmole U 2 Diol, 3mmol glycerol, in a molar ratio of total hydroxyl groups to isocyanate of 1:1, 28.5mmol of isophorone isocyanate, 3 drops of dibutyl tin laurate, 0.32mmol of copper chloride and 40ml of acetone are added in proportion, stirred and reacted for 2 hours, poured into a mould, dried for 24 hours at 50 ℃, then heated to 75 ℃, dried for 24 hours, and the drying process is carried out under nitrogen atmosphere, so as to obtain the cross-linked polyurethane elastomer with low Wen Ziyu synthetic property.
Example 4
(1) The corresponding pale yellow hydroxyl-terminated biobased unsaturated aliphatic prepolymer was prepared as in example 1.
(2) 10mmol of prepolymer, 10mmol of dimethylglyoxime and 4mmol of U were put into a 100ml three-necked flask at 50℃ 2 Diol, 3mmol glycerol, in a molar ratio of total hydroxyl groups to isocyanate of 1:1, 28.5mmol of isophorone isocyanate, 3 drops of dibutyl tin laurate, 0.32mmol of copper chloride and 40ml of acetone are added in proportion, stirred and reacted for 2 hours, poured into a mould, dried for 24 hours at 50 ℃, then heated to 75 ℃, dried for 24 hours, and the drying process is carried out under nitrogen atmosphere, so as to obtain the cross-linked polyurethane elastomer with low Wen Ziyu synthetic property.
Comparative example 1
No U in the diol component 2 -diol, and no sulphur component:
(1) The corresponding pale yellow hydroxyl-terminated biobased unsaturated aliphatic prepolymer was prepared as in example 1.
(2) To a 100ml three-necked flask at 50℃were added 10mmol of prepolymer, 14mmol of dimethylglyoxime and 3mmol of glycerol in a molar ratio of the total amount of hydroxyl groups to isocyanate of 1:1, 28.5mmol of isophorone isocyanate, 3 drops of dibutyl tin laurate, 0.32mmol of copper chloride and 40ml of acetone are added in proportion, stirred and reacted for 2 hours, poured into a mould, dried for 24 hours at 50 ℃, then heated to 75 ℃, dried for 24 hours, and the drying process is carried out under nitrogen atmosphere, so as to obtain the cross-linked polyurethane elastomer with low Wen Ziyu synthetic property.
Comparative example 2
Sulfur-containing components, but no U, in glycol components 2 -diol:
(1) The corresponding pale yellow hydroxyl-terminated biobased aliphatic prepolymer was produced as in example 1.
(2) To a 100ml three-necked flask at 50℃were added 10mmol of prepolymer, 10mmol of dimethylglyoxime, 4mmol of bis (2-hydroxyethyl) disulfide and 3mmol of glycerol in a molar ratio of the total amount of hydroxyl groups to isocyanate of 1:1, 28.5mmol of isophorone isocyanate, 3 drops of dibutyl tin laurate, 0.32mmol of copper chloride and 40ml of acetone are added in proportion, stirred and reacted for 2 hours, poured into a mould, dried for 24 hours at 50 ℃, then heated to 75 ℃, dried for 24 hours, and the drying process is carried out under nitrogen atmosphere, so as to obtain the cross-linked polyurethane elastomer with low Wen Ziyu synthetic property.
The properties of the elastomers obtained in examples 1 to 4 and comparative examples 1 to 2 were measured, and the results are shown in Table 1.
TABLE 1 Performance test results
As can be seen from Table 1, the low Wen Ziyu biobased crosslinked elastomers of the present invention, due to the abundance of hydrogen bonds, metal coordination bonds, and low bond energy disulfide bonds, combine with lower glass transition temperatures to achieve self-healing at low temperatures of-10 to-15 ℃. In comparative example 2, however, U was not added 2 The diol case can only achieve self-healing at 30 c,temperatures below 30 ℃ are not effective for self-healing. In addition, disulfide bonds are bonds having a relatively low bond energy which, when incorporated into an elastomer, impart self-healing properties but reduce the strength of the elastomer. Along with U 2 An increase in diol content, a gradual increase in the tensile strength of the elastomer and a gradual decrease in the elongation at break.
Example 5
Referring to example 2, the preparation temperature of the hydroxyl terminated biobased unsaturated aliphatic prepolymer was varied, and the other was unchanged, to prepare a corresponding elastomer film. The results are shown in Table 2.
TABLE 2
As can be seen from Table 2, the low Wen Ziyu biobased crosslinked elastomer of the present invention has a gradually increasing molecular weight as the prepolymer preparation temperature increases, and thus the mechanical properties of the resulting low Wen Ziyu biobased crosslinked elastomer gradually increase, because the chain entanglement effect between crosslinking points is enhanced with the crosslinking density unchanged, resulting in an improved mechanical properties.
Example 6
Comparative optimization in different glycol components:
referring to example 2, U was changed 2 -diol is replaced by other diols, the others being unchanged, to produce the corresponding crosslinked polyurethane elastomer.
The properties of the resulting crosslinked polyurethane elastomer were measured, and the results are shown in Table 3.
TABLE 3 Table 3
The above examples are not intended to limit the scope of the invention nor the order of execution of the steps described. The present invention is obviously modified by a person skilled in the art in combination with the prior common general knowledge, and falls within the scope of protection defined by the claims of the present invention.

Claims (10)

1. The preparation method of the functionalized elastomer capable of self-healing at low temperature is characterized by comprising the following steps of:
(1) Obtaining hydroxyl end-capped bio-based aliphatic prepolymer by using bio-based diacid and dihydric alcohol to react;
(2) Mixing and reacting the hydroxyl-terminated bio-based aliphatic prepolymer with isocyanate, glycol components, glycerol, metal salt and ligand to obtain the functional elastomer.
2. The method of claim 1, wherein the bio-based glycol is one or a combination of propylene glycol, butylene glycol, rubber seed oil based glycol, palm oil based glycol, sunflower oil based glycol, isosorbide, pentylene glycol, ethylene glycol, dimer alcohol; the bio-based dibasic acid is one or a combination of itaconic acid, sebacic acid, succinic acid, azelaic acid, dimer fatty acid, dodecyl dibasic acid and fumaric acid; the mol ratio of the bio-based dihydric alcohol to the dibasic acid is (1-2): 1.
3. the method according to claim 1, wherein the polymerization inhibitor in the step (1) is any one of 4-methoxyphenol and hydroquinone, and the addition amount is 0.05 to 0.5wt%; the catalyst is tetrabutyl titanate, p-toluenesulfonic acid, antimony acetate and dibutyl tin laurate; the dosage is 0.05-0.5wt% of the total mass.
4. The process of claim 1 wherein the glycol component of step (2) is U 2 -diol, or U 2 -combinations of diol with other glycol agents; the other glycol reagents are any one or more of bis (2-hydroxyethyl) disulfide, dimethylglyoxime, butanediol, propylene glycol and isosorbide.
5. The method of claim 1, wherein the molar ratio of the total amount of hydroxyl terminated biobased aliphatic prepolymer and glycol component to glycerin in step (2) is from 2 to 8:1.
6. the method of claim 1, wherein the molar ratio of total hydroxyl groups to isocyanate groups in the hydroxyl terminated biobased aliphatic prepolymer and diol component of step (2) is 1:1 to 2; the isocyanate is one or a combination of isophorone isocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and lysine diisocyanate.
7. The method according to any one of claims 1 to 6, wherein the metal salt in step (2) is selected from one of copper chloride and zinc chloride; the molar ratio of the metal salt to the ligand is 1:10 to 30 percent; the molar ratio of the ligand to glycerol is (2-5): 1.
8. a functionalized elastomer capable of low temperature self-healing prepared by the method of any one of claims 1-7.
9. Use of the low temperature self-healing functionalized elastomer of claim 8 in the field of self-powered triboelectric generators, wearable devices.
10. Use of the low temperature self-healing functionalized elastomer according to claim 8 in the fields of automotive coatings, electronic skin and soft robotics.
CN202311380581.1A 2023-10-24 2023-10-24 Functionalized elastomer and application thereof Pending CN117384350A (en)

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Application Number Priority Date Filing Date Title
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