CN119331199A - A polyurethane elastomer and its preparation method and application - Google Patents
A polyurethane elastomer and its preparation method and application Download PDFInfo
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- CN119331199A CN119331199A CN202411455456.7A CN202411455456A CN119331199A CN 119331199 A CN119331199 A CN 119331199A CN 202411455456 A CN202411455456 A CN 202411455456A CN 119331199 A CN119331199 A CN 119331199A
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Abstract
本发明涉及弹性体材料技术领域，提供了一种聚氨酯弹性体及其制备方法和应用。本发明采用聚酰胺酸作为扩链剂，将刚性的聚酰胺酸链段引入聚氨酯基体中，从而实现抗拉强度的增强，使聚氨酯弹性体具备较高的机械性能，同时在较高的温度下展现优异的形状记忆性能。进一步的，本发明还在聚氨酯弹性体中引入Eu3+，将其和聚氨酯基体中的‑COOH进行配位，利用配位键的高键能增强聚氨酯的交联密度，从而进一步提高聚氨酯弹性体的形状记忆性能，表现出更高的形状固定率和回复率；同时Eu3+的引入还使聚氨酯弹性体表现出荧光特性，在防伪涂层等领域具有广阔的应用前景。
The present invention relates to the technical field of elastomer materials, and provides a polyurethane elastomer and a preparation method and application thereof. The present invention adopts polyamic acid as a chain extender, introduces a rigid polyamic acid segment into a polyurethane matrix, thereby achieving an enhancement in tensile strength, enabling the polyurethane elastomer to have higher mechanical properties, and simultaneously exhibiting excellent shape memory performance at a higher temperature. Further, the present invention also introduces Eu 3+ into the polyurethane elastomer, coordinates it with the ‑COOH in the polyurethane matrix, and utilizes the high bond energy of the coordination bond to enhance the crosslinking density of the polyurethane, thereby further improving the shape memory performance of the polyurethane elastomer, exhibiting a higher shape fixation rate and recovery rate; at the same time, the introduction of Eu 3+ also enables the polyurethane elastomer to exhibit fluorescent properties, and has broad application prospects in the fields of anti-counterfeiting coatings and the like.
Description
Technical Field
The invention relates to the technical field of elastomer materials, in particular to a polyurethane elastomer and a preparation method and application thereof.
Background
Polyurethane is a high molecular material with excellent mechanical properties, medium resistance and self-lubricating properties, and is widely used in the fields of sealing materials, water-lubricated bearings and the like. The polyurethane is mainly prepared from isocyanate and polyalcohol through polycondensation reaction, and the molecular structure of the polyurethane comprises hard segments and soft segments, wherein the hard segments provide strength and hardness, and the soft segments endow the material with elasticity and toughness. High toughness polyurethanes generally have high flowability soft segments, which makes their glass transition temperatures low, limiting their use in thermally induced shape memory materials.
Therefore, how to increase the glass transition temperature of polyurethane while achieving high strength and high toughness remains a challenge in the art.
Disclosure of Invention
In view of this, the present invention provides a polyurethane elastomer, a preparation method and application thereof. The polyurethane elastomer provided by the invention has excellent mechanical properties, higher glass transition temperature and excellent shape memory performance, and can be used in complex environments, and furthermore, eu 3+ is introduced into polyurethane, so that the shape memory performance can be further improved, and meanwhile, the obtained polyurethane elastomer has fluorescent performance.
In order to achieve the above object, the present invention provides the following technical solutions:
The polyurethane elastomer comprises, by weight, 10-20 parts of polytetrahydrofuran, 20-30 parts of toluene diisocyanate and 1-9 parts of a chain extender, wherein the chain extender is polyamide acid, and the polyamide acid comprises 2, 2-bis (4-aminophenyl) hexafluoropropane and 4,4' - (hexafluoroisopropenyl) dipeptide anhydride.
Preferably, the weight average molecular weight of the polyamic acid is 4227 to 8120.
Preferably, the polyamic acid is used in the form of a polyamic acid-containing solution, and the preparation method of the polyamic acid-containing solution comprises the steps of mixing 2, 2-bis (4-aminophenyl) hexafluoropropane, 4'- (hexafluoroisopropenyl) dipeptide anhydride and a polar solvent for polymerization reaction to obtain the polyamic acid-containing solution, wherein the polymerization reaction temperature is 0 ℃, the reaction time is 12-24 h, and the molar ratio of the 2, 2-bis (4-aminophenyl) hexafluoropropane to the 4,4' - (hexafluoroisopropenyl) dipeptide anhydride is 1.1-1.2:1.
Preferably, the polyurethane elastomer is prepared from 1-5 parts of europium nitrate by weight.
The invention also provides a preparation method of the polyurethane elastomer, which comprises the following steps:
mixing polytetrahydrofuran, toluene diisocyanate and a polar solvent for a prepolymerization reaction to obtain an isocyanate terminated prepolymer;
And mixing the isocyanate-terminated prepolymer, polyamide acid and a catalyst for polymerization reaction, pouring the obtained polymerization reaction liquid, and removing the solvent to obtain the polyurethane elastomer.
Preferably, the temperature of the prepolymerization reaction is 70-90 ℃, the reaction time is 1-2 h, the temperature of the polymerization reaction is 70-90 ℃, and the reaction time is 3-8 h.
Preferably, when the raw materials for preparing the polyurethane elastomer further comprise europium nitrate, the preparation method further comprises the steps of mixing the polymerization reaction solution and the europium nitrate solution, and casting the obtained mixed solution.
Preferably, the temperature of the solvent is 70-90 ℃ and the time is 30-50 h.
The invention also provides an application of the polyurethane elastomer prepared by the scheme or the preparation method of the scheme (except Eu 3+) in a shape memory material.
The invention also provides an application of the polyurethane elastomer prepared by the scheme or the preparation method of the scheme (comprising Eu 3+) in a shape memory material or an anti-counterfeiting coating.
The invention provides a polyurethane elastomer, which comprises the following raw materials, by weight, 10-20 parts of polytetrahydrofuran, 20-30 parts of toluene diisocyanate and 1-9 parts of chain extender, wherein the chain extender is polyamide acid, and the raw materials for preparing the polyamide acid comprise 2, 2-bis (4-aminophenyl) hexafluoropropane and 4,4' - (hexafluoroisopropenyl) dipeptide anhydride. The rigid polyamide acid chain segment is introduced into the polyurethane matrix, the rigid chain segment and the tendency of forming pi-pi conjugation are utilized to enable the polyurethane to show higher-density hydrogen bonds, the mechanical property is enhanced, the polyurethane has excellent tensile strength and toughness, and meanwhile, the polyurethane can show excellent shape memory performance at a higher temperature by utilizing the hydrogen bond network structure of the polyurethane. In conclusion, the polyurethane elastomer provided by the invention has excellent shape memory performance, excellent mechanical property and higher glass transition temperature, can be used in complex environments, and provides a new strategy for developing high-performance shape memory polyurethane.
Furthermore, the preparation raw materials of the polyurethane elastomer provided by the invention further comprise 1-5 parts of europium nitrate. Eu 3+ is introduced to coordinate with-COOH in a polyurethane matrix, and the high bond energy of a coordination bond is utilized to enhance the crosslinking density of polyurethane, so that the shape memory performance of the polyurethane elastomer is further improved, higher shape fixation rate and recovery rate are shown, and meanwhile, the introduction of Eu 3+ also enables the polyurethane elastomer to show fluorescence characteristics, so that the shape memory process can be observed under ultraviolet rays, and the unique performance enables the material to have wide application prospect in the fields of anti-counterfeiting coatings and the like.
The invention also provides a preparation method of the polyurethane elastomer, which is easy to obtain raw materials and simple and convenient to operate. Is expected to realize commercialization.
Drawings
FIG. 1 is a stress-strain curve of polyurethane elastomers prepared in examples 1-5 and comparative example 1;
FIG. 2 is a graph showing tan delta of polyurethane elastomers prepared in examples 1 to 5;
FIG. 3 is a graph of the shape memory cycle of the polyurethane elastomer prepared in example 2;
FIG. 4 is a graph of the shape memory cycle of the polyurethane elastomer prepared in example 9;
fig. 5 is an emission spectrum of the polyurethane elastomer prepared in example 2 and example 9.
Detailed Description
The invention provides a polyurethane elastomer, which comprises the following raw materials, by weight, 10-20 parts of polytetrahydrofuran, 20-30 parts of toluene diisocyanate and 1-9 parts of chain extender, wherein the chain extender is polyamide acid, and the raw materials for preparing the polyamide acid comprise 2, 2-bis (4-aminophenyl) hexafluoropropane and 4,4' - (hexafluoroisopropenyl) dipeptide anhydride.
In the present invention, the weight average molecular weight of the polytetrahydrofuran is preferably 2000.
In the present invention, the parts by weight of the polytetrahydrofuran substance is preferably 10 parts, and the parts by weight of the toluene diisocyanate substance is preferably 20 parts.
In the present invention, the weight part of the chain extender is preferably 3 parts, and the weight average molecular weight of the polyamic acid is preferably 4227 to 8120, more preferably 5000.
In the present invention, the polyamic acid is preferably used in the form of a polyamic acid-containing solution, and the preparation method of the polyamic acid-containing solution preferably includes mixing 2, 2-bis (4-aminophenyl) hexafluoropropane, 4'- (hexafluoroisopropenyl) dipeptide anhydride and a polar solvent to perform polymerization reaction, wherein the polymerization reaction is preferably performed at a temperature of 0 ℃ for a period of time of preferably 12 to 24 hours under the protection of argon, the polymerization reaction is preferably performed under the condition of an ice bath, and the molar ratio of the 2, 2-bis (4-aminophenyl) hexafluoropropane to the 4,4' - (hexafluoroisopropenyl) dipeptide anhydride is preferably 1.1 to 1.2:1, more preferably 1.167:1, and the polar solvent is preferably one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, toluene and tetrahydrofuran, more preferably N, N-dimethylformamide is preferably anhydrous. In a specific embodiment of the present invention, it is preferable to dissolve 2, 2-bis (4-aminophenyl) hexafluoropropane and 4,4'- (hexafluoroisopropenyl) dipeptide anhydride in polar solvents separately, then drop the 4,4' - (hexafluoroisopropenyl) dipeptide anhydride solution into 2, 2-bis (4-aminophenyl) hexafluoropropane solution, and conduct polymerization under ice bath, argon protection and stirring conditions.
In the embodiment of the present invention, the polyamic acid-containing solution is obtained, and then, directly used for the synthesis of a polyurethane elastomer without any treatment, and the solid content of the polyamic acid-containing solution is preferably 15%, which will be described later.
According to the invention, the preparation raw materials of the polyurethane elastomer preferably further comprise 1-5 parts of europium nitrate, the europium nitrate is preferably europium (III) nitrate hexahydrate, the mol ratio of Eu 3+ in the europium nitrate to-COOH in the polyurethane matrix is preferably 0.25-1.25:9, and the polyurethane matrix is a polymer matrix obtained by the reaction before adding the europium nitrate.
In the invention, the polyurethane elastomer which does not comprise europium nitrate as a preparation raw material is PU-PAA, the tensile strength of the PU-PAA is more than or equal to 49MPa, the elongation at break is more than or equal to 161 percent, the toughness is more than or equal to 59MJ/m 3, the polyurethane elastomer which does not comprise europium nitrate as a preparation raw material is PU-PAA-Eu, the tensile strength of the PU-PAA-Eu is more than or equal to 50MPa, the shape fixation rate is more than or equal to 88 percent, and the shape recovery rate is more than or equal to 98 percent.
The invention also provides a preparation method of the polyurethane elastomer, which comprises the following steps:
mixing polytetrahydrofuran, toluene diisocyanate and a polar solvent for a prepolymerization reaction to obtain an isocyanate terminated prepolymer;
And mixing the isocyanate-terminated prepolymer, polyamide acid and a catalyst for polymerization reaction, pouring the obtained polymerization reaction liquid, and removing the solvent to obtain the polyurethane elastomer.
The invention mixes polytetrahydrofuran, toluene diisocyanate and polar solvent for prepolymerization reaction to obtain isocyanate terminated prepolymer. In the invention, the polar solvent is preferably one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, toluene and tetrahydrofuran, more preferably N, N-dimethylformamide, particularly anhydrous N, N-dimethylformamide, the temperature of the prepolymerization reaction is preferably 70-90 ℃, more preferably 80 ℃, and the time of the prepolymerization reaction is preferably 1-2 h. In the specific embodiment of the invention, polytetrahydrofuran is preferably melted at 70-90 ℃, toluene diisocyanate and polar solvent are added, and then the prepolymerization reaction is carried out under the protection of argon and under the stirring condition.
After the isocyanate-terminated prepolymer is obtained, the isocyanate-terminated prepolymer, the polyamide acid and the catalyst are mixed for polymerization reaction, and the obtained polymerization reaction liquid is poured for solvent removal, so that the polyurethane elastomer is obtained. In the invention, the polymerization reaction temperature is preferably 70-90 ℃, the reaction time is preferably 3-8 hours, the catalyst is preferably an organotin catalyst, more preferably dibutyltin dilaurate, the catalyst dosage is preferably 0.5-1.0% of the mass of the prepolymer, and in the specific embodiment of the invention, after the prepolymerization reaction is finished, the solution containing polyamide acid is dropwise added into the obtained prepolymer solution, and then the catalyst is added for polymerization reaction.
In the present invention, when the raw material for preparing the polyurethane elastomer further comprises europium nitrate, the polymerization reaction solution and a europium nitrate solution are preferably mixed and the obtained mixed solution is cast, the europium nitrate solution is preferably prepared from europium nitrate and a polar solvent, and the polar solvent is preferably one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, toluene and tetrahydrofuran, more preferably N, N-dimethylformamide, in particular anhydrous N, N-dimethylformamide.
In the present invention, the casting mold is preferably a teflon mold.
In the invention, the temperature of the solvent is preferably 70-90 ℃, preferably 80 ℃, the time of the solvent removal is preferably 30-50 h, more preferably 48h, and the polyurethane elastomer can be obtained after the solvent removal is completed and cooling to room temperature and demoulding.
The invention also provides an application of the polyurethane elastomer (PU-PAA) prepared by the scheme or the preparation method of the scheme in the shape memory material.
The invention also provides an application of the polyurethane elastomer (PU-PAA-Eu) prepared by the scheme or the preparation method of the scheme in a shape memory material or an anti-counterfeiting coating.
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The sources of the various materials used in the examples were bis (4-aminophenyl) hexafluoropropane from Saen chemical Co., ltd., 4' - (hexafluoroisopropenyl) dipeptide anhydride from Anhui Hill Techno, polytetrahydrofuran from Jining Hongming Chemicals Co., ltd., toluene diisocyanate from Shanghai Sanyou Chemicals Co., ltd., 1, 6-hexamethylenediamine from Saen chemical Co., shanghai, dibutyltin dilaurate from Tianjin chemical Co., ltd., N-dimethylformamide from Li Anlong Bohua pharmaceutical Co., ltd., and europium (III) nitrate hexahydrate from Anhui Hirson Chemicals Co., ltd. 10-20 parts of polytetrahydrofuran, 20-30 parts of toluene diisocyanate and 1-9 parts of chain extender
Example 1
29.17Mmol of 2, 2-bis (4-aminophenyl) hexafluoropropane was dissolved in 50mL of anhydrous N, N-dimethylformamide in a three-necked flask, 25mmol of 4,4' - (hexafluoroisopropenyl) dipeptide anhydride was then dissolved in 75mL of anhydrous N, N-dimethylformamide, and the solution was slowly dropped into the three-necked flask, followed by mechanical stirring in an ice bath under an argon atmosphere for 12 hours to obtain a polyamic acid (PAA) solution, wherein the relative molecular weight (Mw) of PAA was 5000, the PAA solution was a yellow viscous liquid with a solid content of 15%, and the PAA solution was directly used for polyurethane synthesis without any post-treatment.
2.5Mmol of polytetrahydrofuran (weight average molecular weight 2000) was melted in a three-necked flask at 80℃and then 5mmol of toluene diisocyanate and 15mL of anhydrous N, N-dimethylformamide were added, followed by mechanical stirring under an argon atmosphere at 80℃for 1 hour, and the reaction was carried out to give an isocyanate-terminated prepolymer.
A solution containing 0.5mmol of PAA was added to the prepolymer solution, and 50. Mu.L of dibutyltin dilaurate was added and the reaction was catalyzed at 80℃for 4h. After the reaction was completed, the solution was poured into a teflon mold, and placed in an oven to remove the solvent, cooled to room temperature and demolded to obtain polyurethane elastomer (PU-PAA 1).
Example 2
29.17Mmol of 2, 2-bis (4-aminophenyl) hexafluoropropane was dissolved in 50mL of anhydrous N, N-dimethylformamide in a three-necked flask, 25mmol of 4,4' - (hexafluoroisopropenyl) dipeptide anhydride was then dissolved in 75mL of anhydrous N, N-dimethylformamide, and the solution was slowly dropped into the three-necked flask, followed by mechanical stirring in an ice bath under an argon atmosphere for 12 hours to obtain a polyamic acid (PAA) solution, wherein the relative molecular weight (Mw) of PAA was 5000, the PAA solution was a yellow viscous liquid with a solid content of 15%, and the PAA solution was directly used for polyurethane synthesis without any post-treatment.
2.5Mmol of polytetrahydrofuran (weight average molecular weight 2000) was melted in a three-necked flask at 80℃and then 5mmol of toluene diisocyanate and 15mL of anhydrous N, N-dimethylformamide were added, followed by mechanical stirring under an argon atmosphere at 80℃for 1 hour, and the reaction was carried out to give an isocyanate-terminated prepolymer.
A solution containing 0.75mmol of PAA was added to the prepolymer solution, and 50. Mu.L of dibutyltin dilaurate was added and the reaction was catalyzed at 80℃for 4h. After the reaction was completed, the solution was poured into a teflon mold, and placed in an oven to remove the solvent, cooled to room temperature and demolded to obtain polyurethane elastomer (PU-PAA 2).
Example 3
29.17Mmol of 2, 2-bis (4-aminophenyl) hexafluoropropane was dissolved in 50mL of anhydrous N, N-dimethylformamide in a three-necked flask, 25mmol of 4,4' - (hexafluoroisopropenyl) dipeptide anhydride was then dissolved in 75mL of anhydrous N, N-dimethylformamide, and the solution was slowly dropped into the three-necked flask, followed by mechanical stirring in an ice bath under an argon atmosphere for 12 hours to obtain a polyamic acid (PAA) solution, wherein the relative molecular weight (Mw) of PAA was 5000, the PAA solution was a yellow viscous liquid with a solid content of 15%, and the PAA solution was directly used for polyurethane synthesis without any post-treatment.
2.5Mmol of polytetrahydrofuran (weight average molecular weight 2000) was melted in a three-necked flask at 80℃and then 5mmol of toluene diisocyanate and 15mL of anhydrous N, N-dimethylformamide were added, followed by mechanical stirring under an argon atmosphere at 80℃for 1 hour, and the reaction was carried out to give an isocyanate-terminated prepolymer.
A solution containing 1.0mmol of PAA was added to the prepolymer solution and reacted catalytically with 50. Mu.L of dibutyltin dilaurate at 80℃for 4h. After the reaction was completed, the solution was poured into a teflon mold, and placed in an oven to remove the solvent, cooled to room temperature and demolded to obtain polyurethane elastomer (PU-PAA 3).
Example 4
29.17Mmol of 2, 2-bis (4-aminophenyl) hexafluoropropane was dissolved in 50mL of anhydrous N, N-dimethylformamide in a three-necked flask, 25mmol of 4,4' - (hexafluoroisopropenyl) dipeptide anhydride was then dissolved in 75mL of anhydrous N, N-dimethylformamide, and the solution was slowly dropped into the three-necked flask, followed by mechanical stirring in an ice bath under an argon atmosphere for 12 hours to obtain a polyamic acid (PAA) solution, wherein the relative molecular weight (Mw) of PAA was 5000, the PAA solution was a yellow viscous liquid with a solid content of 15%, and the PAA solution was directly used for polyurethane synthesis without any post-treatment.
2.5Mmol of polytetrahydrofuran (weight average molecular weight 2000) was melted in a three-necked flask at 80℃and then 5mmol of toluene diisocyanate and 15mL of anhydrous N, N-dimethylformamide were added, followed by mechanical stirring under an argon atmosphere at 80℃for 1 hour, and the reaction was carried out to give an isocyanate-terminated prepolymer.
A solution containing 1.25mmol of PAA was added to the prepolymer solution, and 50. Mu.L of dibutyltin dilaurate was added and the reaction was catalyzed at 80℃for 4h. After the reaction was completed, the solution was poured into a teflon mold, and placed in an oven to remove the solvent, cooled to room temperature and demolded to obtain polyurethane elastomer (PU-PAA 4).
Example 5
29.17Mmol of 2, 2-bis (4-aminophenyl) hexafluoropropane was dissolved in 50mL of anhydrous N, N-dimethylformamide in a three-necked flask, 25mmol of 4,4' - (hexafluoroisopropenyl) dipeptide anhydride was then dissolved in 75mL of anhydrous N, N-dimethylformamide, and the solution was slowly dropped into the three-necked flask, followed by mechanical stirring in an ice bath under an argon atmosphere for 12 hours to obtain a polyamic acid (PAA) solution, wherein the relative molecular weight (Mw) of PAA was 5000, the PAA solution was a yellow viscous liquid with a solid content of 15%, and the PAA solution was directly used for polyurethane synthesis without any post-treatment.
2.5Mmol of polytetrahydrofuran (weight average molecular weight 2000) was melted in a three-necked flask at 80℃and then 5mmol of toluene diisocyanate and 15mL of anhydrous N, N-dimethylformamide were added, followed by mechanical stirring under an argon atmosphere at 80℃for 1 hour, and the reaction was carried out to give an isocyanate-terminated prepolymer.
A solution containing 1.5mmol of PAA was added to the prepolymer solution, and 50. Mu.L of dibutyltin dilaurate was added and the reaction was catalyzed at 80℃for 4h. After the reaction was completed, the solution was poured into a teflon mold, and placed in an oven to remove the solvent, cooled to room temperature and demolded to obtain polyurethane elastomer (PU-PAA 5).
Example 6
29.17Mmol of 2, 2-bis (4-aminophenyl) hexafluoropropane was dissolved in 50mL of anhydrous N, N-dimethylformamide in a three-necked flask, 25mmol of 4,4' - (hexafluoroisopropenyl) dipeptide anhydride was then dissolved in 75mL of anhydrous N, N-dimethylformamide, and the solution was slowly dropped into the three-necked flask, followed by mechanical stirring in an ice bath under an argon atmosphere for 12 hours to obtain a polyamic acid (PAA) solution, wherein the relative molecular weight (Mw) of PAA was 5000, the PAA solution was a yellow viscous liquid with a solid content of 15%, and the PAA solution was directly used for polyurethane synthesis without any post-treatment.
2.5Mmol of polytetrahydrofuran (weight average molecular weight 2000) was melted in a three-necked flask at 80℃and then 5mmol of toluene diisocyanate and 15mL of anhydrous N, N-dimethylformamide were added, followed by mechanical stirring under an argon atmosphere at 80℃for 1 hour, and the reaction was carried out to give an isocyanate-terminated prepolymer.
A solution containing 0.75mmol of PAA was added to the prepolymer solution, and 50. Mu.L of dibutyltin dilaurate was added and the reaction was catalyzed at 80℃for 4h. 0.281mmol of europium (III) nitrate hexahydrate was weighed into 10mL of anhydrous N, N-dimethylformamide, and the solution was added to a three-necked flask and stirred for 30 minutes. After completion the solution was poured into a teflon mold and placed in an oven to remove the solvent, cooled to room temperature and demolded to give a polyurethane elastomer (PU-PAA-eu0.25).
Example 7
29.17Mmol of 2, 2-bis (4-aminophenyl) hexafluoropropane was dissolved in 50mL of anhydrous N, N-dimethylformamide in a three-necked flask, 25mmol of 4,4' - (hexafluoroisopropenyl) dipeptide anhydride was then dissolved in 75mL of anhydrous N, N-dimethylformamide, and the solution was slowly dropped into the three-necked flask, followed by mechanical stirring in an ice bath under an argon atmosphere for 12 hours to obtain a polyamic acid (PAA) solution, wherein the relative molecular weight (Mw) of PAA was 5000, the PAA solution was a yellow viscous liquid with a solid content of 15%, and the PAA solution was directly used for polyurethane synthesis without any post-treatment.
2.5Mmol of polytetrahydrofuran (weight average molecular weight 2000) was melted in a three-necked flask at 80℃and then 5mmol of toluene diisocyanate and 15mL of anhydrous N, N-dimethylformamide were added, followed by mechanical stirring under an argon atmosphere at 80℃for 1 hour, and the reaction was carried out to give an isocyanate-terminated prepolymer.
A solution containing 0.75mmol of PAA was added to the prepolymer solution, and 50. Mu.L of dibutyltin dilaurate was added and the reaction was catalyzed at 80℃for 4h. 0.563mmol of europium (III) nitrate hexahydrate was dissolved in 10mL of anhydrous N, N-dimethylformamide, and the solution was added to a three-necked flask and stirred for 30 minutes. After completion the solution was poured into a teflon mold and placed in an oven to remove the solvent, cooled to room temperature and demolded to give a polyurethane elastomer (PU-PAA-eu0.5).
Example 8
29.17Mmol of 2, 2-bis (4-aminophenyl) hexafluoropropane was dissolved in 50mL of anhydrous N, N-dimethylformamide in a three-necked flask, 25mmol of 4,4' - (hexafluoroisopropenyl) dipeptide anhydride was then dissolved in 75mL of anhydrous N, N-dimethylformamide, and the solution was slowly dropped into the three-necked flask, followed by mechanical stirring in an ice bath under an argon atmosphere for 12 hours to obtain a polyamic acid (PAA) solution, wherein the relative molecular weight (Mw) of PAA was 5000, the PAA solution was a yellow viscous liquid with a solid content of 15%, and the PAA solution was directly used for polyurethane synthesis without any post-treatment.
2.5Mmol of polytetrahydrofuran (weight average molecular weight 2000) was melted in a three-necked flask at 80℃and then 5mmol of toluene diisocyanate and 15mL of anhydrous N, N-dimethylformamide were added, followed by mechanical stirring under an argon atmosphere at 80℃for 1 hour, and the reaction was carried out to give an isocyanate-terminated prepolymer.
A solution containing 0.75mmol of PAA was added to the prepolymer solution, and 50. Mu.L of dibutyltin dilaurate was added and the reaction was catalyzed at 80℃for 4h. 0.844mmol of europium (III) nitrate hexahydrate was weighed into 10mL of anhydrous N, N-dimethylformamide, and the solution was added to a three-necked flask and stirred for 30 minutes. After completion the solution was poured into a teflon mold and placed in an oven to remove the solvent, cooled to room temperature and demolded to give a polyurethane elastomer (PU-PAA-eu0.75).
Example 9
29.17Mmol of 2, 2-bis (4-aminophenyl) hexafluoropropane was dissolved in 50mL of anhydrous N, N-dimethylformamide in a three-necked flask, 25mmol of 4,4' - (hexafluoroisopropenyl) dipeptide anhydride was then dissolved in 75mL of anhydrous N, N-dimethylformamide, and the solution was slowly dropped into the three-necked flask, followed by mechanical stirring in an ice bath under an argon atmosphere for 12 hours to obtain a polyamic acid (PAA) solution, wherein the relative molecular weight (Mw) of PAA was 5000, the PAA solution was a yellow viscous liquid with a solid content of 15%, and the PAA solution was directly used for polyurethane synthesis without any post-treatment.
2.5Mmol of polytetrahydrofuran (weight average molecular weight 2000) was melted in a three-necked flask at 80℃and then 5mmol of toluene diisocyanate and 15mL of anhydrous N, N-dimethylformamide were added, followed by mechanical stirring under an argon atmosphere at 80℃for 1 hour, and the reaction was carried out to give an isocyanate-terminated prepolymer.
A solution containing 0.75mmol of PAA was added to the prepolymer solution, and 50. Mu.L of dibutyltin dilaurate was added and the reaction was catalyzed at 80℃for 4h. 1.125mmol of europium (III) nitrate hexahydrate was weighed into 10mL of anhydrous N, N-dimethylformamide, and the solution was added to a three-necked flask and stirred for 30 minutes. After completion, the solution was poured into a teflon mold, and placed in an oven to remove the solvent, cooled to room temperature and demolded to obtain polyurethane elastomer (PU-PAA-Eu 1).
Comparative example 1
2.5Mmol of polytetrahydrofuran was melted in a three-necked flask at 80℃and then 5mmol of toluene diisocyanate and 15mL of anhydrous N, N-dimethylformamide were added, followed by mechanical stirring under an argon atmosphere at 80℃for 1 hour, and the reaction was carried out to give an isocyanate-terminated prepolymer. 2.5mmol of 1, 6-hexamethylenediamine is dissolved in 10mLN, N-dimethylformamide, this solution is added to the prepolymer solution, and 50. Mu.L of dibutyltin dilaurate are added and the reaction is catalyzed at 80℃for 4h. After the reaction is completed, the solution is poured into a Teflon mold, and is put into an oven to remove the solvent, cooled to room temperature and demolded to obtain the polyurethane elastomer (PU-HMD).
Performance test:
1. Mechanical properties and glass transition temperature test
Mechanical property test is carried out on the polyurethane elastomer at room temperature by using a ShimadzuAG-X (5000N) electronic universal tester, the stretching speed is 50mm/min, the sample shape is cut into dumbbell shapes according to the international standard ISO-37 (Type 4), and the five sample bars are tested to obtain the average value. The test results are shown in Table 1.
Thermomechanical measurements performed in the stretching mode using a Netzsch 242E dynamic mechanical analyzer verify the transition temperature of the polyurethane, the oscillation frequency was 1Hz, the recording temperature range was-50 ℃ to 150 ℃, and the heating rate was 5 ℃ per minute. To ensure reliable results, more than three specimens were tested for each sample. The test results are shown in Table 1.
TABLE 1 mechanical test results
As can be seen from the data in Table 1, the polyurethane elastomer of the present invention has a higher glass transition temperature, and can maintain excellent mechanical properties, particularly, tensile strength is greatly improved as compared with comparative example 1, and 1, 6-hexamethylenediamine is used as a chain extender in comparative example 1, and the obtained polyurethane elastomer has a higher elongation at break and toughness, but has a low glass transition temperature, and cannot be used in the fields of shape memory materials and the like.
FIG. 1 is a stress-strain curve of polyurethane elastomers prepared in examples 1-5 and comparative example 1. As can be seen from FIG. 1, the polyurethane elastomers prepared in examples 1 to 5 have good mechanical properties. As can be seen from the properties of examples and comparative examples in Table 1 and FIG. 1, the polyurethane elastomer material prepared by the method of the present invention has excellent mechanical properties, particularly tensile strength, and the mechanical properties are found to be optimal when the amount of polyamic acid is 3 parts by the ratio of polyamic acid, and the glass transition temperatures of the other examples are higher than room temperature except for example 1.
FIG. 2 is a graph showing tan delta of polyurethane elastomers prepared in examples 1 to 5. As can be seen from FIG. 2, the glass transition temperature (Tg) of PU-PAA tends to increase with increasing PAA content. The substantial increase in Tg may be due to the addition of the rigid segments of PAA, the pi-pi binding is enhanced, and physical crosslinking is effected, thereby increasing the immobilization of the polymer chains.
2. Shape memory performance test
The shape memory performance was tested in a tensile mode using a Netzsch 242C dynamic mechanical analyzer with a controlled load of 2N, a shape fixation temperature of-10 ℃, a shape fixation time of 5min, a shape recovery temperature of 60 ℃, a shape recovery time of 50min, and 3 cycles.
FIG. 3 is a graph showing the shape memory cycle of the polyurethane elastomer prepared in example 2, and FIG. 4 is a graph showing the shape memory cycle of the polyurethane elastomer prepared in example 9. As can be seen from fig. 3 and 4, the polyurethane elastomers prepared in example 2 and example 9 each have excellent shape memory properties, and the shape recovery rate of the resulting polyurethane elastomer is higher due to the Eu 3+ being introduced in example 9 as compared with example 2.
3. Fluorescence Performance test
The polyurethane elastomers prepared in example 2 and example 9 were subjected to fluorescence test using an F-7000FL fluorescence spectrophotometer, and the excitation wavelength of the emission spectrum was 286nm.
Fig. 5 is an emission spectrum of the polyurethane elastomer prepared in example 2 and example 9. As can be seen from FIG. 5, the polyurethane elastomer prepared in example 9 has fluorescence characteristics due to the Eu 3+ being introduced, and can be used in the fields of anti-counterfeiting coating and the like.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
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