Elastomer material capable of synchronously enhancing mechanical property and fluorescence property as well as preparation method and application of elastomer material
The preparation of fluorescent elastomers through molecular integration methods has solved the problems of poor compatibility with the elastomer matrix and insufficient mechanical properties, and achieved synchronous improvement of fluorescent performance and mechanical properties.
Patent Information
- Application Number
- CN202510434368.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-08
- Publication Date
- 2025-07-08
AI Technical Summary
In the prior art, the fluorescent elastomers prepared by physical mixing method have poor interface compatibility with the elastomer matrix, resulting in uneven fluorescence and reduced mechanical strength. Chemical grafting methods cannot improve the mechanical properties, but may weaken the mechanical properties of the elastomer.
Through molecular integration methods, elastomer materials that synchronize mechanical and fluorescent properties are prepared using specific proportions of diols, diisocyanates, catalysts, mechanical chain extenders and fluorescent chain extenders. The specific steps include dissolution, heating reaction, and defoaming and drying.
The fluorescence and mechanical properties of fluorescent elastomers have been significantly improved, with good tensile properties and enhanced fluorescence intensity, which solves the problem of poor mechanical properties of fluorescent elastomers in traditional methods.
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Figure CN120271786A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of the preparation of fluorescent elastomer materials, and particularly relates to an elastomer material with simultaneously enhanced mechanical properties and fluorescent properties, and a preparation method and application thereof. Background Technique
[0002] Disclosing the information of this background technical part is only intended to increase the understanding of the overall background of the present invention, and is not necessarily regarded as an admission or any form of implication that this information constitutes the prior art already known to those of ordinary skill in the art.
[0003] Fluorescent elastomers have received increasing attention and extensive research in sensors, information encryption, crack monitoring, displays, etc. due to their excellent flexibility, high stability, and specific responsiveness. Incorporating various fluorescent molecules into the elastomer matrix is a simple method for preparing fluorescent elastomers, such as introducing rare earth ions, quantum dots, or luminescent dyes into the elastomer.
[0004] However, the elastomers prepared by this physical mixing method have the problem of poor interfacial compatibility between the fluorescent molecules and the elastomer matrix, resulting in the aggregation of fluorescent molecules, uneven fluorescence intensity, and possible reduction of the mechanical strength of the material. In the prior art, the problem of interfacial compatibility of fluorescent molecules is solved by chemically grafting chromophores into the elastomer network. However, the chemical grafting method usually does not increase the mechanical properties of the material, and even weakens the mechanical properties of the elastomer, making the chemically grafted fluorescent elastomers generally have poor mechanical properties at the present stage. Summary of the Invention
[0005] In order to solve the above problems, the present invention provides an elastomer material with simultaneously enhanced mechanical properties and fluorescent properties, and a preparation method and application thereof. The present invention realizes the preparation of a fluorescent elastomer with significantly improved mechanical properties and fluorescent properties through molecular integration, thereby preparing a high-performance fluorescent elastomer with high practical applicability.
[0006] Specifically, the technical solution of the present invention is as follows:
[0007] In the first aspect of the present invention, an elastomer material with simultaneously enhanced mechanical properties and fluorescent properties is provided. The raw materials of the elastomer material, by mass percentage, are: 60-75% of diol, 12-15% of diisocyanate, 0.1-0.3% of catalyst, and 10-28% of chain extender, wherein the chain extender includes a mechanical chain extender and a fluorescent chain extender;
[0008] The molar ratio of the chain extender to the diisocyanate is 0.5-2:1; the molar ratio of the diisocyanate to the diol is 1.5-3:1; the molar ratio of the mechanical chain extender to the fluorescent chain extender is 0.5-1.5:1.
[0009] Preferably, the diol is selected from one or more of polytetrahydrofuran (PTMEG), polycaprolactone (PCL), polyethylene glycol (PEG), and polypropylene glycol (PPG), and has an average molecular weight of 1000 - 2000 g / mol.
[0010] Preferably, the diisocyanate is selected from one or more of 4,4'-dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and 1,5-naphthalene diisocyanate (NDI).
[0011] Preferably, the catalyst is selected from one or more of dibutyltin dilaurate (DBTDL), bismuth laurate, stannous octoate, and bismuth isooctoate.
[0012] Preferably, the mechanical chain extender is selected from one or more of 1,4-butanediamine (BDA), isophorone diamine (IPDA), 1,3-propanediamine (DAP), and isophthalic dihydrazide (IPDH).
[0013] Preferably, the fluorescent chain extender is selected from one or more of 5-amino-2-(4-aminophenyl)benzimidazole (PABZ), 1,5-naphthalenediamine (NDA), 1,6-diaminopyrene (PyDA), and 2,6-diaminoanthraquinone (ADAQ).
[0014] In a second aspect of the present invention, there is provided a method for preparing an elastomeric material that simultaneously enhances mechanical properties and fluorescent properties as described above, comprising the following steps:
[0015] S1. Dissolve the diol in an organic solvent to obtain phase A;
[0016] S2. Add the diisocyanate and the catalyst to phase A, and carry out a heating reaction to obtain a prepolymer B;
[0017] S3. Add the chain extender dissolved in an organic solvent to phase B, carry out a heating reaction, and perform post-treatment to obtain the elastomeric material.
[0018] Preferably, in step S1, the organic solvent is selected from one or more of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), tetrahydrofuran (THF), and carbon tetrachloride (CTC).
[0019] Preferably, in step S2, the temperature of the heating reaction is 60 - 80 °C, and the reaction time is 1 - 3 h.
[0020] Preferably, in step S3, the organic solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, and carbon tetrachloride.
[0021] Preferably, in step S3, the temperature of the heating reaction is 25-60°C, and the reaction time is 4-8 h.
[0022] Preferably, in step S3, the product after the heating reaction also needs to be degassed and dried to obtain the elastomeric material.
[0023] In the third aspect of the present invention, there is provided an application of the elastomeric material for synchronously enhancing mechanical properties and fluorescence properties described in the first aspect and / or the elastomeric material for synchronously enhancing mechanical properties and fluorescence properties prepared by the preparation method described in the second aspect in flexible electronic devices and biomedical materials.
[0024] One or more embodiments of the present invention have at least the following beneficial effects:
[0025] (1) The traditional preparation method of fluorescent elastomers is to chemically graft fluorescent chromophores onto the elastomer network. This method often weakens the mechanical properties of the original elastomer. The present invention designs and manufactures fluorescent elastomers by controllably assembling two kinds of molecules. Compared with the fluorescent elastomers synthesized by the traditional chemical grafting method using only a single fluorescent molecule, it has the characteristics of simple and controllable synthesis method, solves the problem of poor mechanical properties of the fluorescent elastomers synthesized by the traditional chemical grafting method, and can additionally enhance the fluorescence properties of the material.
[0026] (2) The fluorescent elastomers prepared by the present invention have good tensile properties and fluorescence properties. Description of the Drawings
[0027] The specification drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention.
[0028] Figure 1 It is the Fourier transform infrared spectrum (FTIR) of the elastomeric material prepared in Example 1 of the present invention;
[0029] Figure 2 It is the Fourier transform infrared spectrum of the elastomeric material prepared in Example 3 of the present invention;
[0030] Figure 3 It is a comparison chart of the toughness of the elastomeric materials prepared in Example 5 and Comparative Example 1;
[0031] Figure 4 It is a comparison chart of the stress-strain test of the elastomeric materials prepared in Example 3 and Comparative Example 2;
[0032] Figure 5 It is a comparison chart of the toughness of the elastomeric materials prepared in Example 3 and Comparative Example 2;
[0033] Figure 6 Fluorescence intensity comparison chart of the elastomeric materials prepared in Example 3 and Comparative Example 2. Detailed implementation manners
[0034] It should be noted that the following detailed descriptions are all exemplary and are intended to provide further explanations of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meanings as those commonly understood by those of ordinary skill in the technical field to which the present invention belongs.
[0035] The present invention will be further described in detail below in conjunction with specific examples. It should be noted that the specific examples are interpretations rather than limitations of the present invention.
[0036] Example 1 : This example provides an elastomeric material for simultaneously enhancing mechanical properties and fluorescence properties and a preparation method thereof, including the following steps:
[0037] (1) Add 10 g of solvent DMF and 10 g of diol PCL to a 250 mL flask to obtain Phase A;
[0038] (2) Add 2.63 g of diisocyanate HMDI and 50 μL of catalyst DBTDL to Phase A, heat to 80 °C, and stir and react for 2 h to obtain prepolymer B;
[0039] (3) Dissolve 0.1806 g of DAP and 0.5606 g of PABZ in 40 g of DMF and add it to Phase B, heat to 60 °C, stir and react for 4 h, defoam and dry to obtain a fluorescent elastomer;
[0040] The FTIR diagram of the fluorescent elastomer prepared in this example is as Figure 1 shown:
[0041] As can be seen from Figure 1 the fluorescent elastomer prepared in this example has a C=O peak at 1715 cm -1 and no N=C=O peak is found at 2260 cm -1 , proving the successful synthesis of the fluorescent elastomer.
[0042] Example 2 : This example provides an elastomeric material for simultaneously enhancing mechanical properties and fluorescence properties and a preparation method thereof, including the following steps:
[0043] (1) Add 10 g of solvent DMF and 10 g of diol PCL to a 250 mL flask to obtain Phase A;
[0044] (2) Add 2.22 g of diisocyanate IPDI and 80 μL of catalyst DBTDL to Phase A, heat to 80 °C, and stir and react for 3 h to obtain prepolymer B;
[0045] (3) Dissolve 0.1806 g of DAP and 0.3955 g of NDA in 40 g of DMF, add it to Phase B, heat to 55 °C, stir and react for 5 h, defoam and dry to obtain the fluorescent elastomer.
[0046] Example 3 : This example provides an elastomer material that simultaneously enhances mechanical properties and fluorescence properties and its preparation method, including the following steps:
[0047] (1) Add 10 g of DMF as the solvent and 10 g of PTMEG as the diol to a 250 mL flask to obtain Phase A;
[0048] (2) Add 2.83 g of HMDI as the diisocyanate and 40 μL of DBTDL as the catalyst to Phase A, heat to 80 °C, stir and react for 3 h to obtain the prepolymer B;
[0049] (3) Dissolve 0.4257 g of IPDA and 0.5606 g of PABZ in 40 g of DMF, add it to Phase B, heat to 55 °C, stir and react for 3 h, defoam and dry to obtain the fluorescent elastomer.
[0050] The FTIR diagram of the fluorescent elastomer prepared in this example is as Figure 2 shown. The fluorescent elastomer prepared in this example has a C=O peak at 1724 cm -1 and no N=C=O peak is found at 2260 cm -1 , proving the successful synthesis of the fluorescent elastomer.
[0051] Example 4 : This example provides an elastomer material that simultaneously enhances mechanical properties and fluorescence properties and its preparation method, including the following steps:
[0052] (1) Add 10 g of DMF as the solvent and 10 g of PPG as the diol to a 250 mL flask to obtain Phase A;
[0053] (2) Add 1.68 g of HDI as the diisocyanate and 80 μL of DBTDL as the catalyst to Phase A, heat to 70 °C, stir and react for 3 h to obtain the prepolymer B;
[0054] (3) Dissolve 0.2203 g of BDA and 0.5807 g of PyDA in 40 g of DMF, add it to Phase B, heat to 35 °C, stir and react for 5 h, defoam and dry to obtain the fluorescent elastomer.
[0055] Example 5 : This example provides an elastomer material that simultaneously enhances mechanical properties and fluorescence properties and its preparation method, including the following steps:
[0056] (1) Add 10 g of the solvent DMF and 10 g of the diol PCL to a 250 mL flask to obtain Phase A;
[0057] (2) Add 2.83 g of the diisocyanate HMDI and 40 μL of the catalyst DBTDL to Phase A, heat to 80 °C, and stir and react for 1 h to obtain the prepolymer B;
[0058] (3) Dissolve 0.4855 g of IPDH and 0.5606 g of PABZ in 40 g of DMF, add it to Phase B, heat to 60 °C, stir and react for 4 h, and remove bubbles and dry to obtain the fluorescent elastomer.
[0059] Example 6 : This example provides an elastomer material that simultaneously enhances mechanical properties and fluorescence properties and its preparation method, including the following steps:
[0060] (1) Add 10 g of the solvent DMF and 10 g of the diol PPG to a 250 mL flask to obtain Phase A;
[0061] (2) Add 2.1 g of the diisocyanate NDI and 40 μL of the catalyst DBTDL to Phase A, heat to 80 °C, and stir and react for 1 h to obtain the prepolymer B;
[0062] (3) Dissolve 0.4855 g of IPDH and 0.5956 g of ADAQ in 40 g of DMF, add it to Phase B, heat to 30 °C, stir and react for 4 h, and remove bubbles and dry to obtain the fluorescent elastomer.
[0063] Comparative Example 1 : This comparative example provides an elastomer material with fluorescence properties and its preparation method, including the following steps:
[0064] (1) Add 10 g of the solvent DMF and 10 g of the diol PCL to a 250 mL flask to obtain Phase A;
[0065] (2) Add 2.83 g of the diisocyanate HMDI and 40 μL of the catalyst DBTDL to Phase A, heat to 80 °C, and stir and react for 3 h to obtain the prepolymer B;
[0066] (3) Dissolve 1.1212 g of PABZ in 40 g of DMF, add it to Phase B, heat to 55 °C, stir and react for 3 h, and remove bubbles and dry to obtain the fluorescent elastomer.
[0067] Comparative Example 2 : This comparative example provides an elastomer material with fluorescence properties and its preparation method, including the following steps:
[0068] (1) Add 10 g of the solvent DMF and 10 g of the diol PTMEG into a 250 mL flask to obtain Phase A;
[0069] (2) Add 2.83 g of the diisocyanate HMDI and 40 μL of the catalyst DBTDL into Phase A, heat to 80 °C, and stir and react for 3 h to obtain the prepolymer B;
[0070] (3) Dissolve 1.1212 g of PABZ in 40 g of DMF, add it into Phase B, heat to 55 °C, stir and react for 3 h, and then defoam and dry to obtain the fluorescent elastomer.
[0071] Comparative Example 3 : This comparative example provides an elastomer material and its preparation method, including the following steps:
[0072] (1) Add 10 g of the solvent DMF and 10 g of the diol PTMEG into a 250 mL flask to obtain Phase A;
[0073] (2) Add 2.83 g of the diisocyanate HMDI and 40 μL of the catalyst DBTDL into Phase A, heat to 80 °C, and stir and react for 3 h to obtain the prepolymer B;
[0074] (3) Dissolve 0.9304 g of IPDA in 40 g of DMF, add it into Phase B, heat to 55 °C, stir and react for 3 h, and then defoam and dry to obtain the elastomer.
[0075] Comparative Example 4 : This comparative example provides an elastomer material and its preparation method, including the following steps:
[0076] (1) Add 10 g of the solvent DMF and 10 g of the diol PTMEG into a 250 mL flask to obtain Phase A;
[0077] (2) Add 2.83 g of the diisocyanate HMDI and 40 μL of the catalyst DBTDL into Phase A, heat to 80 °C, and stir and react for 3 h to obtain the prepolymer B;
[0078] (3) Dissolve 0.6385 g of IPDA and 0.2803 g of PABZ in 40 g of DMF, add it into Phase B, heat to 55 °C, stir and react for 3 h, and then defoam and dry to obtain the fluorescent elastomer.
[0079] Comparative Example 5 : This comparative example provides an elastomer material and its preparation method, including the following steps:
[0080] (1) Add 10 g of the solvent DMF and 10 g of the diol PTMEG into a 250 mL flask to obtain Phase A;
[0081] (2) 2.83 g of diisocyanate HMDI and 40 μL of catalyst DBTDL were added to phase A, heated to 80 °C, and stirred for 3 h to obtain prepolymer B;
[0082] (3) 0.2326 g of IPDA and 0.8409 g of PABZ were dissolved in 40 g of DMF and added to phase B, heated to 55 °C, and stirred for 3 h. After defoaming and drying, a fluorescent elastomer was obtained.
[0083] Test Example 1 :
[0084] In this example, a universal tensile machine was used to test the mechanical properties and fluorescence properties of the elastomer materials prepared in Examples 1-5 and Comparative Examples 1-5; a fluorescence spectrometer was used to test the fluorescence properties. The specific data are shown in Tables 1-2:
[0085] Table 1
[0086]
[0087] Table 2
[0088]
[0089]
[0090] It can be seen from the test results that in Comparative Examples 1-2, only the fluorescent chain extender was added. Although the fluorescence properties of the prepared elastomer materials were improved, their mechanical properties and fluorescence properties were lower than those of the elastomer materials prepared in the examples of the present invention (as Figures 3 to 6 shown). This is because the commonly used polyurethane chain extender was used as an accompanying fragment to form a mismatched supramolecular fragment with the fluorescent fragment in the original elastomer. The mismatched supramolecule can greatly enhance the dissipation ability of the material, enhance the toughness of the material, and the accompanying fragment can hinder the aggregation of the fluorescent group and enhance the fluorescence properties of the material.
[0091] In Comparative Example 3, only the mechanical chain extender was added. The mechanical properties and fluorescence properties of the prepared elastomer material were lower than those of the elastomer materials prepared in the examples of the present invention. This is because there are four molecular configurations for the double chain extender, including a strong binding configuration and a weak binding configuration. The less stable configuration will preferentially slide under the action of stretching, resulting in energy dissipation, thereby endowing the matrix material with high extensibility and toughness.
[0092] Compared with Comparative Examples 4-5, in the examples of the present invention, by controlling the addition amounts of the fluorescent chain extender and the mechanical chain extender, the mechanical properties of the fluorescent elastomer and the fluorescence intensity under 365 nm excitation were successfully enhanced simultaneously.
[0093] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
Claims
1. An elastomeric material that simultaneously enhances mechanical and fluorescence properties, characterized in that, The raw materials of the elastomeric material, by mass percentage, are: diol 60-75%, diisocyanate 12-15%, catalyst 0.1-0.3%, chain extender 10-28%, wherein the chain extender includes a mechanical chain extender and a fluorescent chain extender; The molar ratio of the chain extender to the diisocyanate is 0.5-2:1; the molar ratio of the diisocyanate to the diol is 1.5-3:1; the molar ratio of the mechanical chain extender to the fluorescent chain extender is 0.5-1.5:
1.
2. The elastomeric material with enhanced mechanical and fluorescence properties simultaneously as claimed in claim 1, characterized in that, The diol is selected from one or more of polytetrahydrofuran, polycaprolactone, polyethylene glycol and polypropylene glycol, and the average molecular weight is 1000-2000 g / mol.
3. The elastomeric material with enhanced mechanical and fluorescence properties as claimed in claim 1, wherein The diisocyanate is selected from one or more of 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and 1,5-naphthalene diisocyanate.
4. The elastomeric material with enhanced mechanical and fluorescence properties as claimed in claim 1, wherein The catalyst is selected from one or more of dibutyltin dilaurate, bismuth laurate, stannous octoate or bismuth isooctoate.
5. The elastomeric material with enhanced mechanical and fluorescence properties simultaneously as claimed in claim 1, wherein, The mechanical chain extender is selected from one or more of 1,4-butanediamine, isophorone diamine, 1,3-propanediamine and 1,6-hexanediamine.
6. The elastomeric material for synchronously enhancing mechanical properties and fluorescence properties as described in claim 1, characterized in that, The fluorescent chain extender is selected from one or more of 5-amino-2-(4-aminophenyl)benzimidazole, 1,5-naphthalenediamine, 1,6-diamino pyrene and 2,6-diamino anthraquinone.
7. A method for preparing an elastomeric material that simultaneously enhances mechanical properties and fluorescence properties as described in any one of claims 1 to 6, characterized in that, It includes the following steps: S1. Dissolve the diol in an organic solvent to obtain phase A; S2. Add the diisocyanate and the catalyst to phase A, and carry out a heating reaction to obtain prepolymer B; S3. Add the chain extender dissolved in the organic solvent to phase B, carry out a heating reaction, and perform post-treatment to obtain the elastomeric material.
8. The preparation method according to claim 7, characterized in that, In step S1, the organic solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran and carbon tetrachloride.
9. The preparation method according to claim 7, characterized in that, In step S2, the temperature of the heating reaction is 60-80 °C and the reaction time is 1-3 h; Preferably, in step S3, the organic solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, carbon tetrachloride; the temperature of the heating reaction is 25-60 °C, and the reaction time is 4-8 h.
10. Application of the elastomeric material simultaneously having strong mechanical and fluorescent properties according to any one of claims 1-6 and / or the elastomeric material simultaneously having strong mechanical and fluorescent properties prepared by the preparation method according to any one of claims 7-9 in flexible electronic devices and biomedical materials.