High-temperature-resistant polyamide adhesive tape and preparation method thereof
By adding halogen-doped ZnO2 powder to the polyamide strip, the problem of thermal deformation and aging of the polyamide strip in high-temperature environments is solved, and its high-temperature resistance is significantly improved.
Patent Information
- Application Number
- CN202411426868.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-12
- Publication Date
- 2025-01-14
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Polyamide strips exhibit thermal deformation, degradation of dimensional stability and accelerated aging in high temperature environments, and cannot meet the long-term stable performance requirements.
By adding halogen-doped ZnO2 powder as a thermal stabilizer to the polyamide strip, the energy band structure of ZnO2 is changed, its thermal stability is increased, and its crystal structure is improved to remain stable at high temperatures.
It significantly improves the high-temperature resistance of the polyamide strip, delays thermal oxidative degradation, and maintains better crystal morphology and stability, thus improving the processing performance and finished product quality of the strip.
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of rubber strips, and more specifically, to a high temperature resistant polyamide rubber strip and a preparation method thereof. Background Art
[0002] Polyamide rubber strips, also known as nylon rubber strips, are an engineering material with excellent performance and broad application prospects. Polyamide rubber strips are products made from polyamide resins, which have the characteristics of toughness, wear resistance, and self-lubrication. Polyamide rubber strips are widely used in the industrial field, such as sealing, shockproofing, anti-skid and protection of mechanical equipment. Its wear resistance and self-lubrication make it an ideal choice for mechanical parts and transmission components. In the electronics and electrical industry, polyamide rubber strips are often used for insulation, protection and fixation of circuit boards. In the field of automobile manufacturing, polyamide rubber strips are used for sealing and sound insulation of doors, windows, sunroofs and other parts. Its excellent wear resistance and weather resistance ensure the durability and reliability of automotive parts.
[0003] Although polyamide strips have demonstrated excellent performance in multiple industrial fields, in certain application scenarios, especially those involving high-temperature environments, the high-temperature resistance of polyamide strips seems to be somewhat inadequate. In high-temperature environments, polyamide materials may undergo thermal deformation, resulting in decreased dimensional stability, which in turn affects their sealing, sound insulation or protective functions. In addition, long-term exposure to high temperatures may also accelerate the aging process of the material and weaken its mechanical strength and durability. Therefore, for equipment or components with high working environment temperatures, such as sealing strips of certain industrial furnaces, electronic equipment housing seals in high-temperature environments, or seals in automobile engine compartments, polyamide strips cannot meet long-term stable performance requirements. Summary of the invention
[0004] In order to improve the high temperature resistance of a polyamide rubber strip, the present application provides a high temperature resistant polyamide rubber strip and a preparation method thereof.
[0005] The application provides a high temperature resistant polyamide rubber strip adopts the following technical solution:
[0006] A high temperature resistant polyamide rubber strip, comprising the following raw materials in parts by weight:
[0007] 80-100 parts of dimer acid type polyamide;
[0008] 10-15 parts of silicone resin;
[0009] 3-6 parts of benzoyl peroxide;
[0010] Halogen-doped ZnO 2 8-15 parts of flour;
[0011] 5-10 parts of filler;
[0012] 2-5 parts of antioxidant;
[0013] 2-5 parts of defoaming agent.
[0014] By adopting the above technical solution, by adding halogen-doped ZnO 2 The high temperature resistance of polyamide strips is significantly improved. Halogen atom doping can change the ZnO 2 The energy band structure of ZnO increases its thermal stability. At high temperatures, halogen atoms can capture free radicals on the polyamide molecular chain, thereby preventing the occurrence of chain reactions and delaying the thermal oxidative degradation of polyamide. In addition, the doping of halogen atoms can improve the thermal stability of ZnO. 2 The crystal structure of halogen-doped ZnO is more stable. 2 The powder can maintain a good crystal morphology and stability, thus playing the role of thermal stabilizer more effectively. 2 The powder also has good dispersibility and compatibility, and can be fully mixed with raw materials such as polyamide to improve the processing performance of the rubber strip and the quality of the finished product.
[0015] In summary, halogen-doped ZnO 2 Powder plays an important role as a heat stabilizer in high-temperature resistant polyamide rubber strips. It significantly improves the high-temperature resistance of polyamide rubber strips by improving thermal stability and improving crystal structure.
[0016] Optionally, the halogen-doped ZnO 2 The powder is prepared by the following method:
[0017] (1) dissolving a Zn precursor in a hydrochloric acid aqueous solution to obtain a zinc salt solution, adding an ammonium halide salt to the tin salt solution under stirring, and then magnetically stirring for 2-8 hours to obtain a precursor solution;
[0018] (2) The precursor solution is kept at 150-200°C for 12-24 hours and then filtered. The precipitate is washed and dried to obtain halogen-doped ZnO 2 pink.
[0019] Optionally, the Zn precursor in step (1) includes Zn(OH) 2 、ZnCO 3 and ZnSO 4 Any one of .
[0020] Optionally, the mass concentration of the hydrochloric acid aqueous solution used in step (1) is 65%; based on 1g of Zn, the amount of the hydrochloric acid aqueous solution used is 3-7mL.
[0021] Optionally, the ammonium halide salt in step (1) is NH 4 F or NH 4 Br; the amount of ammonium halide added is 1-5% of the mass of the Zn precursor.
[0022] Optionally, the filler is titanium dioxide.
[0023] In a first aspect, the present application provides a method for preparing a high temperature resistant polyamide rubber strip, using the following technical solution:
[0024] A method for preparing a high temperature resistant polyamide rubber strip comprises the following steps:
[0025] S1, heating the dimer acid type polyamide to a viscous flow state, adding the silicone resin and benzoyl peroxide, stirring and mixing, and gradually heating, heating to a preset temperature, and then reacting at a constant temperature for a period of time; adding a defoaming agent and stirring during the constant temperature reaction, and obtaining a premix after the constant temperature reaction is completed;
[0026] S2, adding halogen-doped ZnO to the premix 2 The powder, filler and antioxidant are mixed together to obtain a mixed material, and the mixed material is extruded, granulated and dried to obtain the high-temperature resistant polyamide rubber strip.
[0027] Optionally, the preset temperature in step S1 is 205-220° C., and the constant temperature reaction time is 1 hour.
[0028] In summary, this application has the following beneficial effects:
[0029] 1. The polyamide adhesive strip of the present application is added with halogen-doped ZnO 2 Powder acts as a thermal stabilizer, and the doping of halogen atoms can change the ZnO 2 The energy band structure of ZnO increases its thermal stability. At high temperatures, halogen atoms can capture free radicals on the polyamide molecular chain, thereby preventing the occurrence of chain reactions and delaying the thermal oxidative degradation of polyamide. In addition, the doping of halogen atoms can improve the thermal stability of ZnO. 2 The crystal structure of halogen-doped ZnO is more stable. 2 The powder can maintain a good crystal morphology and stability, so as to more effectively play the role of heat stabilizer, thereby significantly improving the high temperature resistance of polyamide rubber strips.
[0030] 2. The preparation method of the high-temperature resistant polyamide rubber strip of the present application has the advantages of mature technology, high raw material utilization rate, environmental protection, low energy consumption and excellent product performance. The application of the rubber strip brings the beneficial effects of broadening the application field, improving product reliability and reducing maintenance costs. DETAILED DESCRIPTION
[0031] The present application is further described in detail below with reference to the embodiments.
[0032] Halogen-doped ZnO 2 Preparation example of powder
[0033] Preparation Example 1
[0034] A fluorine-doped ZnO 2 Powder is prepared by the following method:
[0035] (1) 10g Zn(OH) 2 Dissolve in 40 mL of 65% hydrochloric acid aqueous solution to obtain a zinc salt solution. Add 0.5 g of NH 4 F, and then magnetic stirring was performed for 4 h to obtain a precursor solution.
[0036] (2) The precursor solution was kept at 180°C for 16 hours. After the heat preservation, it was filtered, and the precipitate was washed several times with deionized water and then dried to obtain fluorine-doped ZnO 2 pink.
[0037] Preparation Example 2
[0038] A Bromine-doped ZnO 2 Powder is prepared by the following method:
[0039] (1) 15 g ZnCO 3 Dissolve in 60 mL of 65% hydrochloric acid aqueous solution to obtain a zinc salt solution. Add 0.45 g of NH 4 Br, and then magnetically stirred for 8 h to obtain a precursor solution.
[0040] (2) The precursor solution was kept at 150°C for 24 hours. After the heat preservation, it was filtered, and the precipitate was washed several times with deionized water and then dried to obtain bromine-doped ZnO. 2 pink.
[0041] Preparation Example 3
[0042] A Bromine-doped ZnO 2 Powder is prepared by the following method:
[0043] (1) 8 g ZnSO 4 Dissolve in 32 mL of 65% hydrochloric acid to obtain a zinc salt solution. Add 0.1 g NH 4 Br, and then magnetically stirred for 2 h to obtain a precursor solution.
[0044] (2) The precursor solution was kept at 200°C for 12 hours. After the heat preservation, it was filtered, and the precipitate was washed several times with deionized water and then dried to obtain bromine-doped ZnO 2 pink.
[0045] Example
[0046] Example 1
[0047] A high temperature resistant polyamide rubber strip, the raw material dosage of which is shown in Table 1, wherein: the dimer acid type polyamide is ethylenediamine amide; the halogen-doped ZnO 2 The powder was prepared from fluorine-doped ZnO 2 powder; the filler is titanium dioxide; the antioxidant is DNP; the defoaming agent is polyether defoaming agent.
[0048] A high temperature resistant polyamide rubber strip is prepared by the following method:
[0049] S1. Heat the dimer acid type polyamide to a viscous flow state, add silicone resin and benzoyl peroxide, stir and mix, and gradually heat to 205°C, and react at a constant temperature for 1 hour. During the constant temperature reaction, add a defoaming agent and stir, and obtain a premix after the reaction is completed.
[0050] S2, adding halogen-doped ZnO to the premix 2 The powder, filler and antioxidant are mixed together to obtain a mixed material, and the mixed material is extruded, granulated and dried to obtain the high-temperature resistant polyamide rubber strip.
[0051] Example 2
[0052] A high temperature resistant polyamide rubber strip, the raw material dosage of which is shown in Table 1, wherein: the dimer acid type polyamide is propylene diamine amide; the halogen-doped ZnO 2 The powder was prepared from bromine-doped ZnO 2 powder; the filler is titanium dioxide; the antioxidant is DNP; the defoaming agent is polyether defoaming agent.
[0053] A high temperature resistant polyamide rubber strip is prepared by the following method:
[0054] S1. Heat the dimer acid type polyamide to a viscous flow state, add silicone resin and benzoyl peroxide, stir and mix, and gradually heat to 210°C, and react at a constant temperature for 1 hour. During the constant temperature reaction, add a defoaming agent and stir, and obtain a premix after the reaction is completed.
[0055] S2, adding halogen-doped ZnO to the premix 2 The powder, filler and antioxidant are mixed together to obtain a mixed material, and the mixed material is extruded, granulated and dried to obtain the high-temperature resistant polyamide rubber strip.
[0056] Example 3
[0057] A high temperature resistant polyamide rubber strip, the raw material dosage of which is shown in Table 1, wherein: the dimer acid type polyamide is selected from butanediamine amide; the halogen-doped ZnO 2 The powder was prepared from bromine-doped ZnO 2 powder; the filler is titanium dioxide; the antioxidant is DNP; the defoaming agent is polyether defoaming agent.
[0058] A high temperature resistant polyamide rubber strip is prepared by the following method:
[0059] S1. Heat the dimer acid type polyamide to a viscous flow state, add silicone resin and benzoyl peroxide, stir and mix, and gradually heat to 220°C, and react at a constant temperature for 1 hour. During the constant temperature reaction, add a defoaming agent and stir, and obtain a premix after the reaction is completed.
[0060] S2, adding halogen-doped ZnO to the premix 2 The powder, filler and antioxidant are mixed together to obtain a mixed material, and the mixed material is extruded, granulated and dried to obtain the high-temperature resistant polyamide rubber strip.
[0061] Table 1 Amount of each raw material used in Examples 1-3 (g)
[0062] raw material Example 1 Example 2 Example 3 Dimer acid type polyamide 80 90 100 Silicone resin 10 12 15 Benzoyl peroxide 3 5 6 <![CDATA[Halogen-doped ZnO 2 powder]]> 8 12 15 filler 5 8 10 Antioxidants 2 3 5 Defoaming agent 2 3 5
[0063] Comparative Example
[0064] Comparative Example 1
[0065] A polyamide rubber strip, which is different from Example 1 in that an equal amount of ZnO is used in this comparative example. 2 Powder instead of fluorine-doped ZnO 2 pink.
[0066] Comparative Example 2
[0067] A polyamide rubber strip, which is different from Example 1 in that the halogen-doped ZnO 2 The dosage of powder is 5g.
[0068] Comparative Example 3
[0069] A polyamide rubber strip, which is different from Example 1 in that an equal amount of ethylenediamine amide is used instead of silicone resin in this comparative example.
[0070] Performance testing
[0071] The samples in Examples 1-3 and Comparative Examples 1-3 were tested for tensile strength according to GB / T7753 and softening point according to the test method in GB / T4507-2014. The results are shown in Table 2.
[0072] Table 2 Test results of Examples 1-3 and Comparative Examples 1-3
[0073] project Tensile strength(N / mm) Softening point(℃) Example 1 46.5 254 Example 2 47.2 257 Example 3 46.0 252 Comparative Example 1 45.3 112 Comparative Example 2 43.2 168 Comparative Example 3 31.5 231
[0074] The softening points in Examples 1-3 are 254°C, 257°C and 252°C, respectively, which are much higher than the softening point of conventional polyamide strips, indicating that halogen-doped ZnO 2 The powder significantly improves the high temperature resistance of the rubber strip.
[0075] In Comparative Example 1, the softening point dropped sharply to 112°C, indicating that the undoped ZnO 2 The high temperature resistance of ZnO powder is far inferior to that of halogen-doped ZnO 2 pink.
[0076] In Comparative Example 2, when halogen-doped ZnO 2 When the amount of powder is reduced, the softening point is also reduced to 168℃, but it is still higher than that of undoped ZnO. 2 Powder Comparative Example 1, halogen-doped ZnO 2 Powder can provide a certain degree of high temperature resistance even at lower dosages.
[0077] In Comparative Example 3, although the tensile strength dropped significantly, the softening point remained at 231°C, indicating that although the silicone resin has an important influence on the tensile strength, its contribution to high temperature resistance is not as good as that of halogen-doped ZnO 2 The powder is noticeable.
[0078] In summary, halogen-doped ZnO 2 Powder plays an important role as a heat stabilizer in high-temperature resistant polyamide rubber strips. It significantly improves the high-temperature resistance of polyamide rubber strips by improving thermal stability and improving crystal structure.
[0079] The tensile strengths in Examples 1-3 were 46.5 N / mm, 47.2 N / mm and 46.0 N / mm, respectively, all remaining at a high level, indicating that the halogen-doped ZnO 2 The powder did not negatively affect the tensile strength of the strips, but may have helped maintain the tensile strength due to its stabilizing effect at high temperatures.
[0080] In Comparative Example 1, undoped ZnO 2 Powder replaces halogen-doped ZnO 2 After powdering, the tensile strength decreased slightly (45.3N / mm), but not significantly. However, the more significant effect was on the softening point.
[0081] In Comparative Example 3, since ethylenediamine amide was used to replace the silicone resin, the tensile strength dropped significantly to 31.5 N / mm, indicating that the silicone resin played an important role in improving the tensile strength.
[0082] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.
Claims
1. A high temperature resistant polyamide rubber strip, characterized in that: The invention comprises the following raw materials in parts by weight: 80-100 parts of dimer acid type polyamide; 10-15 parts of silicone resin; 3-6 parts of benzoyl peroxide; 8-15 parts of halogen-doped ZnO2 powder; 5-10 parts of filler; 2-5 parts of antioxidant; 2-5 parts of defoaming agent.
2. The high temperature resistant polyamide rubber strip according to claim 1, characterized in that: The halogen-doped ZnO2 powder is prepared by the following method: (1) dissolving a Zn precursor in a hydrochloric acid aqueous solution to obtain a zinc salt solution, adding an ammonium halide salt to the tin salt solution under stirring, and then magnetically stirring for 2-8 hours to obtain a precursor solution; (2) The precursor solution is kept at 150-200°C for 12-24 hours and then filtered. The precipitate is washed and dried to obtain halogen-doped ZnO2 powder.
3. The high temperature resistant polyamide rubber strip according to claim 2, characterized in that: The Zn precursor in step (1) includes any one of Zn(OH)2, ZnCO3 and ZnSO4.
4. The high temperature resistant polyamide rubber strip according to claim 2, characterized in that: The mass concentration of the hydrochloric acid aqueous solution used in step (1) is 65%; based on 1g of Zn, the amount of the hydrochloric acid aqueous solution used is 3-7mL.
5. The high temperature resistant polyamide rubber strip according to claim 2, characterized in that: The ammonium halide salt in step (1) is selected from NH4F or NH4Br; the amount of the ammonium halide salt added is 1-5% of the mass of the Zn precursor.
6. The high temperature resistant polyamide rubber strip according to claim 1, characterized in that: The filler is titanium dioxide.
7. A method for preparing a high temperature resistant polyamide rubber strip according to any one of claims 1 to 6, characterized in that: The steps include: S1. Heat the dimer acid type polyamide to a viscous flow state, add the silicone resin and benzoyl peroxide, stir and mix, and gradually increase the temperature. After the temperature reaches a preset temperature, keep the temperature constant for a period of time; During the isothermal reaction, a defoaming agent is added and stirred, and a premix is obtained after the isothermal reaction is completed; S2. Add halogen-doped ZnO2 powder, filler and antioxidant to the premix and mix together to obtain a mixture. The mixture is extruded, granulated and dried to obtain the high-temperature resistant polyamide rubber strip.
8. The method for preparing a high temperature resistant polyamide rubber strip according to claim 7, characterized in that: The preset temperature in step S1 is 205-220° C., and the constant temperature reaction time is 1 hour.