Phthalic anhydride chain extender containing carbon-carbon triple bonds, preparation method of phthalic anhydride chain extender and preparation method of modified PET (Polyethylene Terephthalate) high polymer material
By introducing a carbon-carbon triple bond phthalic anhydride chain extender into polyimide and PET and performing high-temperature blending injection molding, the problem of insufficient processing and mechanical properties of thermoplastic polyimide materials is solved, and high mechanical strength and functionality are achieved , suitable for high load applications.
Patent Information
- Application Number
- CN202411439407.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-15
- Publication Date
- 2025-01-17
AI Technical Summary
Thermoplastic polyimide materials have difficulties in processing and mechanical properties, and their heat resistance and mechanical strength are insufficient to meet the needs of certain high load applications.
The phthalic anhydride chain extender containing carbon-carbon triple bonds was used for high-temperature blending and injection molding, and the mechanical strength and functionality of the material were improved by chain crosslinking, and the chloride catalyst without crystallization water was used for simple synthesis.
It improves the mechanical strength and functionality of the material, reduces processing difficulty and cost, enhances thermal stability and glass transition temperature, and is suitable for the industrial production of PET polyester materials.
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Figure CN119320370A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of polymer material synthesis and preparation, and in particular relates to a phthalic anhydride chain extender containing a carbon-carbon triple bond and a preparation method thereof, and a preparation method of a modified PET polymer material. Background Art
[0002] Polymers have long been used as alternatives to other materials, such as metals. Their advantage is that the material is light and relatively easy to shape. However, the mechanical strength of polymers is generally lower than that of metals. In addition, their heat resistance is low. Polyimide (PI) refers to a class of polymers containing an imide ring (-CO-NR-CO-) on the main chain, and is one of the organic polymer materials with the best comprehensive performance. It is resistant to high temperatures of more than 400°C, with a long-term use temperature range of 200-300°C. Some of them have no obvious melting point, high insulation performance, a dielectric constant of 4.0 at 103 Hz, and a dielectric loss of only 0.004-0.007. Due to its rigid aromatic heterocyclic structure, polyimide (PI) is one of the polymer materials with the best heat resistance at present, and its Tg can reach 350°C or higher. However, thermoplastic polyimide also has obvious disadvantages such as difficult processing: polyimide has a high melting point and high processing temperature, and requires special equipment and processing technology, which increases its processing difficulty and cost. Insufficient mechanical properties: The mechanical properties of polyimide, such as tensile strength, impact strength and flexural modulus, are relatively low, which limits its application in some occasions that need to withstand large loads.
[0003] Compared to thermoplastic polyimides, thermosetting polyimides have inherently good properties such as resistance to wear and friction, good electrical properties, radiation resistance, good low temperature stability and good flame retardancy. Therefore, they are used in the electronics industry for flexible cables, as insulating films on magnet wires and in medical tubing. Polyimide materials can also be used in applications exposed to high or low temperature environments, as good temperature performance of structural components is a prerequisite for functional retention. In order to improve the processability of polyimides used in aircraft and aerospace applications while maintaining their mechanical properties, cross-linking technology was introduced. When polymer chains are cross-linked, they may become shorter while maintaining or even improving mechanical properties. Shorter polymer chains have the advantage of being easier to process because the viscosity of the polymer melt or polymer solution is lower.
[0004] Based on this, it is very important to develop thermosetting polyimide containing aromatic phthalic anhydride chain extenders substituted with phenylethynyl groups acting on the reactive part. After the phthalic anhydride chain extender containing carbon-carbon triple bonds is reacted with polyimide and mixed with PET, it can not only cause chain crosslinking between polyimide molecules and PET, increase molecular weight, shorten the molecular lateral structure, increase viscosity, and increase the mechanical strength of the material after molding, but also increase the functionality of the material to meet the market demand for PET polyester materials. Summary of the invention
[0005] In view of the shortcomings of the above-mentioned prior art, the problem solved by the present invention is: to provide a phthalic anhydride chain extender containing a carbon-carbon triple bond, which is simple and quick to prepare, has good heat resistance, good mechanical properties, and excellent various properties, and a preparation method thereof, and a preparation method of a modified PET polymer material.
[0006] To solve the above problems, the technical solution adopted by the present invention is as follows:
[0007] A phthalic anhydride chain extender containing a carbon-carbon triple bond, the structural formula of which is as follows:
[0008]
[0009] A method for preparing a phthalic anhydride chain extender containing a carbon-carbon triple bond, comprising the following steps:
[0010] S1. Add 1,2,4-trimellitic anhydride chloride and organic solvent into the reaction bottle, flush with protective gas, add catalyst under mechanical stirring, and heat to 90-110°C;
[0011] S2, dissolving phenylacetylene in an organic solvent, slowly adding the mixture dropwise to the mixed solution of step S1, and maintaining the temperature to continue the reaction;
[0012] S3, separation and washing: after the raw material 1,2,4-trimellitic anhydride chloride is completely reacted, the reaction solution is cooled to 20°C, and the solid is washed several times to remove the residual solvent;
[0013] S4. Drying: Drying in a vacuum drying oven to obtain a finished carbon-carbon triple bond phthalic anhydride chain extender.
[0014] Furthermore, the organic solvent in steps S1 and S2 is one of xylene, tetrahydrofuran, chloroform, N,N-dimethylformamide, and acetonitrile.
[0015] Furthermore, in step S1, the catalyst used is a chloride without crystal water, which is one of AlCl3, ZnCl2, FeCl3, and CuCl2.
[0016] Furthermore, the molar ratio of the 1,2,4-trimellitic anhydride chloride, phenylacetylene, catalyst and organic solvent is 1:(1-1.2):(0.05-0.10):(15-25).
[0017] Furthermore, in step S1, the protective gas is one of nitrogen and helium.
[0018] A method for preparing a modified PET polymer material comprises the steps of: subjecting a phthalic anhydride chain extender containing a carbon-carbon triple bond, polyimide and PET to high temperature blending injection molding to prepare the modified PET polymer material. The polyimide is a thermosetting polyimide.
[0019] The beneficial effects of the present invention are as follows:
[0020] 1. The phthalic anhydride chain extender containing a carbon-carbon triple bond is reacted with polyimide and then mixed with PET. This can not only cause chain cross-linking between the polyimide molecules and PET, increase the molecular weight, shorten the molecular lateral structure, increase viscosity, and increase the mechanical strength of the material after molding, but also increase the functionality of the material to meet the market demand for PET polyester materials.
[0021] 2. The present invention discloses the use of chlorides without crystal water in catalyzing the electrophilic substitution reaction of 1,2,4-trimellitic anhydride chloride and phenylacetylene, providing a new choice for the synthesis of phthalic anhydride chain extenders containing carbon-carbon triple bonds. The present invention provides a simple and inexpensive synthesis preparation method. The phthalic anhydride chain extender containing carbon-carbon triple bonds prepared by a one-pot method using xylene as a solvent is blended with polyimide, which not only has a viscosity-increasing effect on polyester materials such as PET, but also has the advantages of high stability and non-toxicity.
[0022] 3. The rapid reaction of the anhydride group in the chain extender molecule of the present invention with the terminal carboxyl group of the PET material can eliminate the hydroxyl group in the molecule, so that the polyester material will not be rapidly degraded during the mixing process with the polyester resin, and no transesterification reaction will occur, which will affect its viscosity and mechanical strength after molding. The phthalic anhydride chain extender containing a carbon-carbon triple bond prepared by the chloride without crystallization water used in the present invention has a high application value for improving the viscosity, mechanical strength, crystallization temperature and glass transition temperature of thermoplastic polyester materials, and is easy to industrialize. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 This is the infrared chromatogram of the chain extender of Example 1 of the present invention.
[0024] Figure 2 This is a diagram of the liquid content of the chain extender of Example 1 of the present invention.
[0025] Figure 3 This is a data curve diagram of the Z direction of the universal testing machine test of the conventional PET specimen of the present invention.
[0026] Figure 4 This is a data curve diagram of the universal testing machine test in the Z direction when the mass ratio of the chain extender of Example 1 of the present invention to the PET material is 1:30.
[0027] Figure 5The DSC curve of the PET specimen with a mass ratio of the chain extender and the PET material of Example 1 of the present invention being 1:30.
[0028] Figure 6 The DSC curve of the PET specimen with a mass ratio of the chain extender and the PET material of Example 1 of the present invention being 2:30. DETAILED DESCRIPTION
[0029] The present invention will be further described in detail below in conjunction with the accompanying drawings.
[0030] Example 1
[0031] Add 10.5g 1,2,4-trimellitic anhydride chloride and 116.8g xylene to the reaction bottle, add 5.0g AlCl3 under nitrogen protection and mechanical stirring, raise the temperature to 100°C, slowly add 5.6g phenylacetylene, and then keep the reaction at this temperature. After the raw material 1,2,4-trimellitic anhydride chloride reacts completely, the reaction solution is cooled to 20°C and filtered. The filter cake is washed with xylene and water, and then dried in a vacuum drying oven to obtain 4-(1-keto-4-phenylynyl)phthalic anhydride, 11.7g, white solid, with a yield of 84.7%.
[0032] Example 2
[0033] Add 10.5g 1,2,4-trimellitic anhydride chloride and 116.8g xylene to the reaction bottle, add 5.1g ZnCl2 under nitrogen protection and mechanical stirring, raise the temperature to 100°C, slowly add 5.6g phenylacetylene, and then keep the reaction at this temperature. After the raw material 1,2,4-trimellitic anhydride chloride reacts completely, the reaction solution is cooled to 20°C and filtered. The filter cake is washed with xylene and water, and then dried in a vacuum drying oven to obtain 4-(1-keto-4-phenylynyl)phthalic anhydride, 10.3g, white solid, with a yield of 74.6%.
[0034] Example 3
[0035] Add 10.5g 1,2,4-trimellitic anhydride chloride and 116.8g xylene to the reaction bottle, add 6.1g FeCl3 under nitrogen protection and mechanical stirring, raise the temperature to 100°C, slowly add 5.6g phenylacetylene, and then keep the reaction at this temperature. After the raw material 1,2,4-trimellitic anhydride chloride reacts completely, the reaction solution is cooled to 20°C and filtered. The filter cake is washed with xylene and water, and then dried in a vacuum drying oven to obtain 4-(1-keto-4-phenylynyl)phthalic anhydride, 10.7g, white solid, with a yield of 77.5%.
[0036] Example 4
[0037] Add 10.5g 1,2,4-trimellitic anhydride chloride and 79.3g tetrahydrofuran to the reaction bottle, add 5.0g AlCl3 under nitrogen protection and mechanical stirring, raise the temperature to 100°C, slowly add 5.6g phenylacetylene, and then keep the reaction at this temperature. After the raw material 1,2,4-trimellitic anhydride chloride reacts completely, the reaction solution is cooled to 20°C and filtered. The filter cake is washed with xylene and water, and then dried in a vacuum drying oven to obtain 4-(1-keto-4-phenylynyl)phthalic anhydride, 9.8g, white solid, with a yield of 71.0%.
[0038] Example 5
[0039] Add 10.5g 1,2,4-trimellitic anhydride chloride and 45.2g acetonitrile to the reaction bottle, add 5.0g AlCl3 under nitrogen protection and mechanical stirring, raise the temperature to 100°C, slowly add 5.6g phenylacetylene, and then keep the reaction at this temperature. After the raw material 1,2,4-trimellitic anhydride chloride reacts completely, the reaction solution is cooled to 20°C and filtered. The filter cake is washed with xylene and water, and then dried in a vacuum drying oven to obtain 4-(1-keto-4-phenylynyl)phthalic anhydride, 8.4g, white solid, with a yield of 60.9%.
[0040] Example 6
[0041] Add 10.5g 1,2,4-trimellitic anhydride chloride and 116.8g xylene to the reaction bottle, add 5.0g AlCl3 under nitrogen protection and mechanical stirring, heat to 110°C, slowly add 5.6g phenylacetylene, and then keep the reaction at this temperature. After the raw material 1,2,4-trimellitic anhydride chloride reacts completely, the reaction solution is cooled to 20°C and filtered. The filter cake is washed with xylene and water, and then dried in a vacuum drying oven to obtain 4-(1-keto-4-phenylynyl)phthalic anhydride, 11.4g, white solid, with a yield of 82.6%.
[0042] Example 7
[0043] Add 10.5g 1,2,4-trimellitic anhydride chloride and 116.8g xylene to the reaction bottle, add 5.0g AlCl3 under helium protection and mechanical stirring, raise the temperature to 100°C, slowly add 5.6g phenylacetylene, and then keep the reaction at this temperature. After the raw material 1,2,4-trimellitic anhydride chloride reacts completely, the reaction solution is cooled to 20°C and filtered. The filter cake is washed with xylene and water, and then dried in a vacuum drying oven to obtain 4-(1-keto-4-phenylynyl)phthalic anhydride, 11.1g, white solid, with a yield of 80.4%.
[0044] Example 8
[0045] The phthalic anhydride chain extender containing a carbon-carbon triple bond of Example 1 was dissolved and diluted with acetonitrile, and injected into a liquid chromatography system (C18 reverse phase chromatography column) under the conditions of an injection volume of 1 uL, a primary alcohol detection wavelength of 273 nm, and a column temperature of 40° C., with a mobile phase of water:acetonitrile = 30:70, and a liquid content of 98.72%.
[0046] Example 9
[0047] The phthalic anhydride chain extender containing carbon-carbon triple bonds of Example 1, 5% polyimide and PET material were blended and injection molded at 265°C to prepare a modified PET polymer material, and its tensile modulus and strength were measured using a universal testing machine (model WDW). Its crystallization temperature and glass transition temperature were measured using a differential scanning calorimeter (model DSC214). When the mass ratio of the phthalic anhydride chain extender containing carbon-carbon triple bonds to the PET material was 1:30, the average tensile modulus in the Z direction was 209.41MPa, the average tensile strength in the Z direction was 2.8020MPa, the glass transition temperature was 82.42°C, and the crystallization temperature was 144.51°C. When the mass ratio of the phthalic anhydride chain extender containing carbon-carbon triple bonds to the PET material was 2:30, the average tensile modulus was 222.99MPa, the average tensile strength was 2.9590MPa, the glass transition temperature was 83.09°C, and the crystallization temperature was 148.17°C. It can be seen that the mechanical properties of the modified PET prepared by the present invention are improved, and the glass transition temperature and crystallization temperature are improved.
[0048] The test data is as follows:
[0049] Table 1 Mechanical properties (Z direction) of PET strips with a mass ratio of phthalic anhydride chain extender to PET material of 1:30
[0050]
[0051] Table 2 Mechanical properties (Z direction) of PET strips with a mass ratio of phthalic anhydride chain extender to PET material of 2:30
[0052]
[0053] Figure 1 This is the infrared chromatogram of the chain extender of Example 1 of the present invention, which can qualitatively identify the characteristics of the chain extension chain based on the infrared 1710cm characteristic peak and the benzene ring characteristic peak.
[0054] Figure 2 This is a liquid phase content diagram of the chain extender of Example 1 of the present invention, indicating that the synthesized chain extender has a high purity and is free of other impurities. The peak area percentage of the liquid chromatogram reaches 98%.
[0055] Figure 3 It is a data curve diagram of the conventional PET spline universal testing machine tested in the Z direction of the present invention; Figure 4 When the mass ratio of the chain extender of Example 1 of the present invention to the PET material is 1:30, the data curve diagram of the universal testing machine in the Z direction indicates that after adding the new chain extender, the mechanical properties of the PET material are correspondingly improved.
[0056] Figure 5 The DSC curve of the PET specimen with a mass ratio of the chain extender and the PET material of Example 1 of the present invention being 1:30; Figure 6 The DSC curve of the PET sample with a mass ratio of the chain extender and the PET material of Example 1 of the present invention of 2:30 indicates that the crystallization temperature and the glass transition temperature are increased after the addition of the new chain extender. The material with a higher crystallization temperature and glass transition temperature has good thermal stability and mechanical properties.
[0057] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims
1. A phthalic anhydride chain extender containing a carbon-carbon triple bond, characterized in that: Its structural formula is as follows:
2. A method for preparing a phthalic anhydride chain extender containing a carbon-carbon triple bond, characterized in that: Here are the steps: S1. Add 1,2,4-trimellitic anhydride chloride and organic solvent into the reaction bottle, flush with protective gas, add catalyst under mechanical stirring, and heat to 90-110°C; S2, dissolving phenylacetylene in an organic solvent, slowly adding the mixture dropwise to the mixed solution of step S1, and maintaining the temperature to continue the reaction; S3, separation and washing: after the raw material 1,2,4-trimellitic anhydride chloride is completely reacted, the reaction solution is cooled to 20°C, and the solid is washed several times to remove the residual solvent; S4. Drying: Drying in a vacuum drying oven to obtain a finished product containing a phthalic anhydride chain extender having a carbon-carbon triple bond.
3. The method for preparing a phthalic anhydride chain extender comprising a carbon-carbon triple bond according to claim 2, wherein: The organic solvent in steps S1 and S2 is one of xylene, tetrahydrofuran, chloroform, N,N-dimethylformamide and acetonitrile.
4. The method for preparing a phthalic anhydride chain extender comprising a carbon-carbon triple bond according to claim 2, wherein: In the step S1, the catalyst used is a chloride without crystal water, which is one of AlCl3, ZnCl2, FeCl3, and CuCl2.
5. The method for preparing a phthalic anhydride chain extender comprising a carbon-carbon triple bond according to claim 2, wherein: The molar ratio of the 1,2,4-trimellitic anhydride chloride, phenylacetylene, catalyst and organic solvent is 1:(1-1.2):(0.05-0.10):(15-25).
6. The method for preparing a phthalic anhydride chain extender containing a carbon-carbon triple bond according to claim 2, characterized in that: In the step S1, the protective gas is one of nitrogen and helium.
7. A method for preparing a modified PET polymer material, characterized in that: A phthalic anhydride chain extender containing a carbon-carbon triple bond, polyimide and PET are mixed and injection-molded at high temperature to prepare a modified PET polymer material.