Novel polyimide
The new type of fatty polypelide prepared through the green synthesis method solves the lack of processing performance, cost and environmental protection of the aromatic polyamide, realized efficient and environmentally friendly polypelide preparation, and expanded its place in it Application in the field of environmentally friendly materials.
Patent Information
- Application Number
- CN202411692646.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-25
- Publication Date
- 2025-01-24
AI Technical Summary
Aromatic polyimides have disadvantages in processing properties, color and transmittance, production costs and environmental sustainability, resulting in limited application.
Through a green, environmentally friendly, simple, and efficient synthesis method, a new type of completely biological derived fatty polypenamide is prepared, using biomolecules of macaronic acid or pomaceic acid di -aggregated CBTA and fat The athletes are perimed at thermal agglomeration to form a salt monomer and eventually get polyimide.
The low -cost and efficient preparation of polytamide is realized, and the material can be effectively degraded in seawater, and has the potential for the application of environmentally friendly materials.
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Abstract
Description
Technical Field
[0001] The invention belongs to the field of chemical industry and relates to a novel polyimide. Technical Background
[0002] As a special engineering material, polyimide has outstanding characteristics in performance and synthesis. Whether as a structural material or as a functional material, its huge application prospects have been fully recognized and has been widely used in aviation, aerospace, microelectronics, nano, liquid crystal, separation membrane, laser and other fields.
[0003] As a high-performance polymer material, aromatic polyimide has shown excellent performance and broad application prospects in many fields, but it also has some disadvantages.
[0004] 1. Poor processing performance
[0005] Difficult to process: Aromatic polyimide exhibits poor processing performance during processing due to the rigidity and high crystallinity of its molecular chain. Specifically, aromatic polyimide can only be melt molded at high temperatures and is difficult to dissolve in commonly used organic solvents, which makes its processing and molding more difficult.
[0006] High melting temperature: To improve processing performance, researchers have worked to lower the melt plasticization temperature of polyimide, but this challenge still exists.
[0007] 2. Color and transmittance issues
[0008] Darker color: Due to the presence of conjugated large π bonds in aromatic polyimide molecules, polyimide films tend to be darker in color and have lower transmittance. This feature limits its application in fields that require high transmittance materials, such as optical films.
[0009] 3. Cost Issues
[0010] High production cost: The production process of aromatic polyimide is relatively complicated and requires high-quality raw materials and precise processing technology, which leads to relatively high production cost. The high cost may limit its application in some cost-sensitive fields.
[0011] 4. Environmental protection and sustainability
[0012] Environmental challenges: Aromatic polyimide may cause certain environmental pollution problems during production and use. With the improvement of environmental awareness, how to reduce the environmental impact during its production and use has become an urgent problem to be solved.
[0013] Sustainability: Waste disposal of aromatic polyimides is also a challenge given their durability and difficulty in degradation. Summary of the invention
[0014] In order to overcome the above-mentioned deficiencies of the prior art, the present invention prepares a new type of polyimide through a green, environmentally friendly, simple and efficient synthesis method, which can be effectively photodegraded in seawater and can be effectively used for environmental protection.
[0015] CBTA is derived by photodimerization of the biomolecules maleic acid or fumaric acid. Among the aliphatic diamines, pentamethylenediamine can be obtained as a biomonomer under fermentation conditions. Then the polyimide from CBTA and pentamethylenediamine is a completely bio-derived aliphatic polyimide.
[0016] A new type of polyimide, the structure of which is as follows:
[0017]
[0018] In formula 1:
[0019] R is NH2(CH2)n1NH2, where n1 is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20;
[0020] or NH2(CH2)n2O(CH2)n2O(CH2)n2NH2, wherein n2 is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12;
[0021] or NH2CHR`(CH2)n3NH2, wherein n3 is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19); x is a positive integer, wherein R` is CH3 or –CH2CH3 or -CH2CH2CH3 or -CH2CH2CH2CH3;
[0022] or NH2CH2CHR``(CH2)n4NH2, wherein n4 is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18); x is a positive integer, wherein R`` is CH3 or –CH2CH3 or -CH2CH2CH3 or -CH2CH2CH2CH3;
[0023] or NH2CH2CH2CHR```(CH2)n5NH2, where n5 is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17), and x is a positive integer; where R``` is CH3 or –CH2CH3 or -CH2CH2CH3 or -CH2CH2CH2CH3.
[0024] The second object of the present invention is to provide a method for preparing a novel polyimide, the method comprising: obtaining corresponding salt monomer crystals based on cyclobutanetetracarboxylic acid and aliphatic diamine molecules, the two raw materials reacting by thermal polymerization at a molar ratio of 1:1, and the salt monomer will not form a diamide bond during the thermal polymerization process, thereby finally forming the corresponding aliphatic polyimide.
[0025] The polyimide of the present invention is based on the thermal polymerization reaction of the salt monomer method, which is the key factor for the formation of aliphatic polyimide.
[0026] In one embodiment, the specific steps are as follows:
[0027] Step 1, dissolving cyclobutanetetracarboxylic acid and aliphatic diamine in organic solvents respectively, and stirring to obtain corresponding solutions;
[0028] Step 2, mixing the two cyclobutane tetracarboxylic acid solutions and the aliphatic diamine solution, stirring, and obtaining corresponding salt monomers;
[0029] Step 3, obtaining the novel polyimide molecule by thermal polymerization of the salt monomers in step 2.
[0030] In one embodiment, the organic solvent in step 1 comprises one or a mixed solvent of methanol, ethanol, isopropanol, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide.
[0031] In one embodiment, the aliphatic diamine in step 1 includes one or more of ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, nonanediamine or decanediamine.
[0032] In one embodiment, the solvent used in the solution in step 2 includes water, an organic solvent or a mixture of water and an organic solvent, and the organic solvent includes one or more mixed solvents of methanol, ethanol, isopropanol, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide, and a highly crystalline salt monomer is obtained by recrystallizing the salt monomer powder.
[0033] In one embodiment, the salt monomers may be recrystallized.
[0034] In one embodiment, the thermal polymerization temperature in step 3 is 50-400°C.
[0035] Beneficial effects:
[0036] The present invention provides a novel polyimide, wherein cyclobutane tetracarboxylic acid (CBTA) and NH2(CH2)nNH2 (n=2,3,4...20) are dissolved in an organic solvent respectively, and a solution is obtained after stirring; then the two different solutions are mixed, and ions are precipitated to obtain corresponding crystals; and then aliphatic polyimide is obtained by thermal polymerization of salt monomers. The synthesis process is green, environmentally friendly, simple, and efficient, and it further enriches the types of existing polyimides. It is also the first fully aliphatic polyimide in the world, expanding the performance and application field of polyimide. Its excellent degradation performance can be used for environmentally friendly materials. BRIEF DESCRIPTION OF THE DRAWINGS
[0037] Figure 1 It is the hydrogen nuclear magnetic resonance spectrum of the polyimide [CBTA+Cx] prepared in the example of the present invention.
[0038] Figure 2 It is the infrared absorption spectrum of the polyimide [CBTA+Cx] prepared in the example of the present invention.
[0039] Figure 3 It is a statistical diagram of thermodynamic properties data of the polyimide [CBTA+Cx] prepared in the examples of the present invention.
[0040] Figure 4 It is a stress-strain curve diagram of the polyimide [CBTA+Cx] prepared in the example of the present invention.
[0041] Figure 5 It is the infrared absorption spectrum of the photodegradation product of the polyimide [CBTA+C5] prepared in Example 1 of the present invention.
[0042] Figure 6 It is a sample photo of the polyimide [CBTA+C5] prepared in Example 1 of the present invention before and after photodegradation and its microscopic morphology.
[0043] Figure 7 It is the insulation performance test of the polyimide [CBTA+Cx] prepared in the example of the present invention, and the dependence of its dielectric constant and dielectric loss on frequency. DETAILED DESCRIPTION
[0044] It is worth noting that the raw materials used in the present invention are all common commercially available products, and their sources are not specifically limited.
[0045] The present invention is further described below in conjunction with examples. The following examples are only used as illustrations of the present invention and are not intended to limit the scope of the present invention.
[0046] Embodiment 1:
[0047] A polyimide was designed based on cyclobutane tetracarboxylic acid (CBTA) and NH2(CH2)5NH2 molecular compounds. 2.32g and 1.02g of the two monomers were taken respectively, dissolved in ethanol, stirred evenly, and after stirring was completed, the two solvents were mixed, and stirring was continued. Salt monomers were precipitated, filtered and dried to obtain salt monomers. The obtained salt monomers were polymerized at 300°C using a thermal polymerization method to form a polyimide (CBTA+C5-PI).
[0048] Polyimide (CBTA+C5-PI) was subjected to a photodegradation experiment under strong fluorescent light. The product was sampled at 3 and 10 days after photodegradation, its infrared absorption spectrum was measured, and its microscopic morphology was observed under a microscope. The actual pictures of the samples before and after photodegradation and their microscopic morphology are shown in the figure below. Figure 6 shown.
[0049] The H NMR spectrum of polyimide (CBTA+C5-PI) is as follows: Figure 1 shown.
[0050] The infrared spectrum of polyimide (CBTA+C5-PI) is as follows Figure 2 shown.
[0051] The thermodynamic properties of polyimide (CBTA+C5-PI) are as follows: Figure 3 shown.
[0052] The mechanical properties of polyimide (CBTA+C5-PI) are as follows: Figure 4 shown.
[0053] The infrared absorption spectrum of the photodegradation product of polyimide (CBTA+C5-PI) is shown in Figure 5 shown.
[0054] The insulation performance data of polyimide (CBTA+C5-PI) are as follows: Figure 7 shown.
[0055] Embodiment 2:
[0056] A polyimide was designed based on cyclobutane tetracarboxylic acid (CBTA) and NH2(CH2)6NH2 molecular compounds. 2.32g and 1.16g of the two monomers were taken respectively, dissolved in ethanol, stirred evenly, and after stirring was completed, the two solvents were mixed, and stirring was continued. Salt monomers were precipitated, filtered and dried to obtain salt monomers. The obtained salt monomers were polymerized at 300°C using a thermal polymerization method to form a polyimide (CBTA+C6-PI).
[0057] The H NMR spectrum of polyimide (CBTA+C6-PI) is as follows: Figure 1 shown.
[0058] The infrared spectrum of polyimide (CBTA+C6-PI) is as follows Figure 2 shown.
[0059] The thermodynamic properties of polyimide (CBTA+C6-PI) are as follows: Figure 3 shown.
[0060] The mechanical properties of polyimide (CBTA+C6-PI) are as follows: Figure 4 shown.
[0061] The insulation performance data of polyimide (CBTA+C6-PI) are as follows: Figure 7 shown.
[0062] Embodiment 3:
[0063] A polyimide was designed based on cyclobutane tetracarboxylic acid (CBTA) and NH2(CH2)7NH2 molecular compounds. 2.32g and 1.30g of the two monomers were taken respectively, dissolved in ethanol, stirred evenly, and after stirring was completed, the two solvents were mixed, and stirring was continued. Salt monomers were precipitated, filtered and dried to obtain salt monomers. The obtained salt monomers were polymerized at 300°C using a thermal polymerization method to form a polyimide (CBTA+C7-PI).
[0064] The nuclear magnetic resonance hydrogen spectrum of polyimide (CBTA+C7-PI) is as follows Figure 1 shown.
[0065] The infrared spectrum of polyimide (CBTA+C7-PI) is as follows Figure 2 shown.
[0066] The thermodynamic properties of polyimide (CBTA+C7-PI) are as follows: Figure 3 shown.
[0067] The mechanical properties of polyimide (CBTA+C7-PI) are as follows: Figure 4 shown.
[0068] The insulation performance data of polyimide (CBTA+C7-PI) are as follows: Figure 7 shown.
[0069] Embodiment 4:
[0070] A polyimide was designed based on cyclobutane tetracarboxylic acid (CBTA) and NH2(CH2)8NH2 molecular compounds. 2.32g and 1.44g of the two monomers were taken respectively, dissolved in ethanol, stirred evenly, and after stirring was completed, the two solvents were mixed, and stirring was continued. Salt monomers were precipitated, filtered and dried to obtain salt monomers. The obtained salt monomers were polymerized at 300°C using a thermal polymerization method to form a polyimide (CBTA+C8-PI).
[0071] The H NMR spectrum of polyimide (CBTA+C8-PI) is as follows: Figure 1 shown.
[0072] The infrared spectrum of polyimide (CBTA+C8-PI) is as follows Figure 2 shown.
[0073] The thermodynamic properties of polyimide (CBTA+C8-PI) are as follows: Figure 3 shown.
[0074] The mechanical properties of polyimide (CBTA+C8-PI) are as follows: Figure 4 shown.
[0075] The insulation performance data of polyimide (CBTA+C8-PI) are as follows: Figure 7 shown.
[0076] Embodiment 5:
[0077] A polyimide was designed based on cyclobutane tetracarboxylic acid (CBTA) and NH2(CH2)9NH2 molecular compounds. 2.32g and 1.58g of the two monomers were taken respectively, dissolved in ethanol, stirred evenly, and after stirring was completed, the two solvents were mixed, and stirring was continued. Salt monomers were precipitated, filtered and dried to obtain salt monomers. The obtained salt monomers were polymerized at 300°C using a thermal polymerization method to form a polyimide (CBTA+C9-PI).
[0078] The nuclear magnetic resonance hydrogen spectrum of polyimide (CBTA+C9-PI) is as follows Figure 1 shown.
[0079] The infrared spectrum of polyimide (CBTA+C9-PI) is as follows Figure 2 shown.
[0080] The thermodynamic properties of polyimide (CBTA+C9-PI) are as follows: Figure 3 shown.
[0081] The mechanical properties of polyimide (CBTA+C9-PI) are as follows: Figure 4 shown.
[0082] The insulation performance data of polyimide (CBTA+C9-PI) are as follows: Figure 7 shown.
[0083] Embodiment 6:
[0084] Design of a polyimide based on cyclobutanetetracarboxylic acid (CBTA) and NH2(CH2) 10NH2 molecular compound, 2.32g and 1.72g of the two monomers are taken respectively, dissolved in ethanol, stirred evenly, and after stirring is completed, the two solvents are mixed, and stirring is continued, the salt monomer is precipitated, filtered and dried to obtain the salt monomer. The obtained salt monomer is polymerized at 300°C by thermal polymerization to form polyimide (CBTA+C10-PI).
[0085] The H NMR spectrum of polyimide (CBTA+C10-PI) is as follows: Figure 1 shown.
[0086] The infrared spectrum of polyimide (CBTA+C10-PI) is as follows Figure 2 shown.
[0087] The thermodynamic properties of polyimide (CBTA+C10-PI) are as follows: Figure 3 shown.
[0088] The mechanical properties of polyimide (CBTA+C10-PI) are as follows: Figure 4 shown.
[0089] The insulation performance data of polyimide (CBTA+C10-PI) are as follows: Figure 7 shown.
[0090] Embodiment 7:
[0091] Design of a polyimide based on cyclobutanetetracarboxylic acid (CBTA) and NH2(CH2) 11 NH2 molecular compound, 2.32g and 1.86g of the two monomers are taken respectively, dissolved in ethanol, stirred evenly, and after stirring is completed, the two solvents are mixed, and stirring is continued, the salt monomer is precipitated, filtered and dried to obtain the salt monomer. The obtained salt monomer is polymerized at 300°C by thermal polymerization to form polyimide (CBTA+C11-PI).
[0092] The H NMR spectrum of polyimide (CBTA+C11-PI) is as follows: Figure 1 shown.
[0093] The infrared spectrum of polyimide (CBTA+C11-PI) is as follows Figure 2 shown.
[0094] Thermodynamic properties of polyimide (CBTA+C11-PI) are as follows: Figure 3 shown.
[0095] The mechanical properties of polyimide (CBTA+C11-PI) are as follows: Figure 4 shown.
[0096] The insulation performance data of polyimide (CBTA+C11-PI) are as follows: Figure 7 shown.
[0097] Embodiment 8:
[0098] Design of a polyimide based on cyclobutanetetracarboxylic acid (CBTA) and NH2(CH2) 12 NH2 molecular compound, 2.32g and 2.00g of the two monomers are taken respectively, dissolved in ethanol, stirred evenly, and after stirring is completed, the two solvents are mixed, and stirring is continued, the salt monomer is precipitated, filtered and dried to obtain the salt monomer. The obtained salt monomer is polymerized at 300°C by thermal polymerization to form polyimide (CBTA+C12-PI).
[0099] The H NMR spectrum of polyimide (CBTA+C12-PI) is as follows: Figure 1 shown.
[0100] The infrared spectrum of polyimide (CBTA+C12-PI) is as follows Figure 2 shown.
[0101] The thermodynamic properties of polyimide (CBTA+C12-PI) are as follows: Figure 3 shown.
[0102] The mechanical properties of polyimide (CBTA+C12-PI) are as follows: Figure 4 shown.
[0103] The insulation performance data of polyimide (CBTA+C12-PI) are as follows: Figure 7 shown.
[0104] Polyimide [CBTA + Cx-PI] H NMR spectrum Figure 1 As shown, through the results of H NMR spectrum, it can be seen that polyimide [CBTA+C5-PI, CBTA+C6-PI, CBTA+C7-PI, CBTA+C8-PI, CBTA+C9-PI, CBTA+C10-PI, CBTA+C11PI, CBTA+C12-PI,] was successfully synthesized.
[0105] Infrared spectrum of polyimide [CBTA+Cx-PI] Figure 2As shown, through the infrared spectrum results, it can be seen that all PIs show the absorption of asymmetric and symmetric stretching of the C=O of the imide group at 1785 and 1725 cm-1, respectively, as well as the absorption caused by the stretching of the imide CN at 1365 cm-1, and the two peaks between 2800 and 3000 cm-1 are aromatic C-Hx stretching. The results of FTIR can confirm the successful synthesis of polyimide [CBTA+C5-PI, CBTA+C6-PI, CBTA+C7-PI, CBTA+C8-PI, CBTA+C9-PI, CBTA+C10-PI, CBTA+C11PI, CBTA+C12-PI,].
[0106] Thermodynamic properties of polyimide [CBTA+Cx-PI] Figure 3 As shown in Table 1, the thermal degradation temperature of polyimide [CBTA+Cx-PI] is more than 440℃, and the melting points of polyimide [CBTA+C5-PI, CBTA+C7-PI, CBTA+C9-PI, CBTA+C11-PI] and polyimide [CBTA+C10-PI, CBTA+C12-PI] are decreasing. The data of thermodynamic properties are shown in Table 1.
[0107] Table 1. Relevant data of thermodynamic properties.
[0108]
[0109] “--” represents not determined; “a” measured on cooling; “b” measured onheating
[0110] Mechanical properties of polyimide [CBTA+Cx-PI] Figure 4 As shown in Table 2, the stress is between 18 and 35 MPa, and the elongation is maintained between 19 and 86%.
[0111] Table 2. Mechanical properties related data
[0112]
[0113] The infrared absorption spectrum of the photodegradation product of polyimide [CBTA+C5] in Example 1 is as follows Figure 5 As shown, after light degradation, a new infrared peak appears between 1500 and 1600 cm-1, which is the characteristic peak of the carbon-carbon double bond. This proves that the four-membered ring is opened by light and the polyimide is degraded.
[0114] Polyimide [CBTA+Cx-PI] insulation properties such as Figure 7As shown, the dielectric constants of all polyimide films are maintained at about 3, and the dielectric losses of all polyimide films are maintained at an extremely low level.
[0115] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the purpose and scope of the technical solution of the present invention, which should be included in the scope of the claims of the present invention.
Claims
1. A novel polyimide, characterized in that: Its structure is as follows: In formula 1: R is NH2(CH2)n1NH2, where n1 is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20; or NH2(CH2)n2O(CH2)n2O(CH2)n2NH2, wherein n2 is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; or NH2CHR`(CH2)n3NH2, wherein n3 is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19); x is a positive integer, wherein R` is CH3 or –CH2CH3 or -CH2CH2CH3 or -CH2CH2CH2CH3; or NH2CH2CHR``(CH2)n4NH2, wherein n4 is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18); x is a positive integer, wherein R`` is CH3 or –CH2CH3 or -CH2CH2CH3 or -CH2CH2CH2CH3; or NH2CH2CH2CHR```(CH2)n5NH2, where n5 is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17), and x is a positive integer; where R``` is CH3 or –CH2CH3 or -CH2CH2CH3 or -CH2CH2CH2CH3.
2. The method for preparing a novel polyimide according to claim 1, characterized in that: Based on cyclobutanetetracarboxylic acid and aliphatic diamine molecules, corresponding salt monomer crystals are obtained, the two raw materials react through thermal polymerization at a molar ratio of 1:1, and the salt monomer will not form a diamide bond during the thermal polymerization process, thereby finally forming the corresponding aliphatic polyimide.
3. The method for preparing a novel polyimide according to claim 2, characterized in that: The specific steps are as follows: Step 1, dissolving cyclobutanetetracarboxylic acid and aliphatic diamine in organic solvents respectively, and stirring to obtain corresponding solutions; Step 2, mixing the two cyclobutane tetracarboxylic acid solutions and the aliphatic diamine solution, stirring, and obtaining the corresponding salt monomer; Step 3, obtaining the novel polyimide molecule by thermal polymerization of the salt monomers in step 2.
4. The method for preparing a novel polyimide according to claim 3, characterized in that: The organic solvent in step 1 includes one or a mixed solvent of methanol, ethanol, isopropanol, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide.
5. The method for preparing a novel polyimide according to claim 3, characterized in that: The solvent used in the solution in step 2 includes water, an organic solvent or a mixture of water and an organic solvent. The organic solvent includes one or more mixed solvents of methanol, ethanol, isopropanol, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide. The highly crystalline salt monomer is obtained by recrystallizing the salt monomer powder.
6. A novel polyimide according to claim 3, characterized in that: The aliphatic diamine in step 1 includes one or more of ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, nonanediamine or decanediamine.
7. A novel polyimide according to claim 3, characterized in that: The thermal polymerization temperature in step 3 is 50-400°C.
Citation Information
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