High-temperature-resistant TPE material and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, and particularly discloses a high-temperature-resistant TPE material and a preparation method thereof. The high-temperature-resistant TPE material comprises the following components in parts by mass: 73.6-76.6 parts of a polyolefin elastomer; 21 to 23 parts of polypropylene; 1.6 to 3.4 parts of an auxiliary agent; the auxiliary agent at least comprises a compound of N-dodecyl succinic anhydride, dibutyl maleate and didodecyl thiodipropionate. The TPE material has the advantages that the heat resistance of the TPE material is improved, and the influence on the mechanical property is less.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials, and particularly to a high-temperature resistant TPE material and a preparation method thereof. Background Art

[0002] Currently, polymer materials are widely used in many fields due to their light weight, strong plasticity and other characteristics. However, traditional TPE materials are prone to softening, deformation and even decomposition in high-temperature environments, which limits their applications in high-temperature environments. Conventional TPE materials generally can only withstand temperatures of about 100 °C. Therefore, the heat resistance of TPE materials is insufficient, resulting in a decline in the mechanical properties of the materials under high-temperature conditions, affecting the scope of use and service life of the materials.

[0003] Existing improvement schemes mostly improve heat resistance by adding inorganic fillers or special modifiers, but these schemes often lead to a decline in the mechanical properties of the materials and an increase in cost. Therefore, there is still room for improvement. Summary of the Invention

[0004] In order to improve the heat resistance of TPE materials and have less impact on mechanical properties, the present application provides a high-temperature resistant TPE material and a preparation method thereof.

[0005] In a first aspect, the present application provides a high-temperature resistant TPE material, adopting the following technical solution: A high-temperature resistant TPE material, comprising the following components in parts by mass: 73.6 - 76.6 parts of polyolefin elastomer; 21 - 23 parts of polypropylene; 1.6 - 3.4 parts of additives; The additives at least include a compound of N-dodecyl succinic anhydride, dibutyl maleate and dilauryl thiodipropionate.

[0006] By adopting the above technical solution, through the compounding of polyolefin elastomer and polypropylene and then adding N-dodecyl succinic anhydride, dibutyl maleate and dilauryl thiodipropionate, the TPE material can have better heat resistance and better mechanical properties.

[0007] Preferably, the mass ratio of N-dodecyl succinic anhydride, dibutyl maleate and dilauryl thiodipropionate is 0.8 - 1:0.2 - 0.4:0.6 - 0.8.

[0008] By adopting the above technical solution, by specifically selecting the mass ratio of N-dodecyl succinic anhydride, dibutyl maleate and dilauryl thiodipropionate, the effect of improving heat resistance is better, and the mechanical properties of the TPE material can be better improved.

[0009] Preferably, the auxiliary agent further includes an antioxidant and a light stabilizer.

[0010] By adopting the above technical solution, by adding an antioxidant and a light stabilizer, the processing quality of the TPE material is better, the material is more stable, and the service life is longer.

[0011] Preferably, the mass ratio of the N-dodecyl succinic anhydride, dibutyl maleate, dilauryl thiodipropionate, antioxidant, and light stabilizer is 0.8-1:0.2-0.4:0.6-0.8:0.4-0.6:0.4-0.6.

[0012] By adopting the above technical solution, by specifically selecting the mass ratio of the N-dodecyl succinic anhydride, dibutyl maleate, dilauryl thiodipropionate, antioxidant, and light stabilizer, the performance of the TPE material is more stable.

[0013] Preferably, the antioxidant is antioxidant 1010 and the light stabilizer is light stabilizer 770.

[0014] By adopting the above technical solution, by specifically selecting antioxidant 1010 and light stabilizer 770, the performance of the TPE material is more stable and the quality is better.

[0015] Preferably, the polyolefin elastomer is an ethylene-octene copolymer.

[0016] By adopting the above technical solution, by specifically selecting the polyolefin elastomer as an ethylene-octene copolymer, the effect of blending with polypropylene is better, and the heat resistance and mechanical properties of the TPE material are better.

[0017] In a second aspect, the present application provides a method for preparing a high-temperature resistant TPE material, adopting the following technical solution: A method for preparing the above high-temperature resistant TPE material, comprising the following steps: Step 1), mixing the N-dodecyl succinic anhydride, dibutyl maleate, and dilauryl thiodipropionate evenly to obtain an auxiliary agent premix; Step 2), mixing the auxiliary agent premix and other raw materials evenly to obtain a premix; Step 3), extruding the premix through an extruder and pelletizing to obtain a high-temperature resistant TPE material.

[0018] By adopting the above technical solution, by first mixing the N-dodecyl succinic anhydride, dibutyl maleate, and dilauryl thiodipropionate evenly, the auxiliary agent premix can better exert its modification effect, and the prepared TPE material has better heat resistance and better performance.

[0019] Preferably, in step 1), N-dodecyl succinic anhydride, dibutyl maleate, and dilauryl thiodipropionate are stirred at 90-100 °C for 60-90 min to obtain a premixed additive.

[0020] By adopting the above technical solution, by stirring and mixing at 90-100 °C, N-dodecyl succinic anhydride, dibutyl maleate, and dilauryl thiodipropionate are all in a liquid state, and can be fully mixed, and the modification effect of the prepared additive is better.

[0021] Preferably, in step 1), under a nitrogen atmosphere, N-dodecyl succinic anhydride, dibutyl maleate, and dilauryl thiodipropionate are heated to 90-100 °C and stirred.

[0022] By adopting the above technical solution, by adding a nitrogen atmosphere, the oxidation under high temperature is reduced, the modification effect of the premixed additive is better, and the heat resistance and mechanical properties of the TPE material are better improved.

[0023] In summary, the present application has the following beneficial effects: 1. Since the present application uses a blend of polyolefin elastomer and polypropylene and then adds N-dodecyl succinic anhydride, dibutyl maleate, and dilauryl thiodipropionate, the TPE material can have better heat resistance and better mechanical properties.

[0024] 2. In the present application, preferably by specifically selecting the mass ratio of N-dodecyl succinic anhydride, dibutyl maleate, and dilauryl thiodipropionate, the effect of improving heat resistance is better, and the mechanical properties of the TPE material can be better improved.

[0025] 3. In the present application, preferably by adding an antioxidant and a light stabilizer, the processing quality of the TPE material is better, the material is more stable, and the service life is longer. Specific Embodiments

[0026] The following further describes the present application in detail with reference to examples.

[0027] Example 1 A high-temperature resistant TPE material and a preparation method thereof, including the following steps: Step 1), 0.8 kg of N-dodecyl succinic anhydride, 0.2 kg of dibutyl maleate, and 0.6 kg of dilauryl thiodipropionate are put into a stirring kettle, nitrogen is introduced, air is discharged, and under a nitrogen atmosphere, it is heated to 90 °C, the rotation speed is 60 r / min, and stirred for 60 min to be mixed evenly to obtain a premixed additive.

[0028] Step 2), add 76.6 kg of ethylene octene copolymer, 21 kg of polypropylene, 0.4 kg of antioxidant 1010, and 0.4 kg of light stabilizer 770 to the auxiliary premix. Keep the temperature at 90 °C, the rotation speed at 120 r / min, and stir for 10 min until evenly mixed to obtain the premix.

[0029] Step 3), inject the premix into a twin-screw extruder, extrude and pelletize to obtain a high-temperature resistant TPE material. The temperatures of zones 1-14 of the twin-screw extruder are 100 °C, 180 °C, 180 °C, 180 °C, 180 °C, 180 °C, 120 °C, 120 °C, 120 °C, 120 °C, 120 °C, 120 °C, 120 °C, 120 °C in sequence, the head temperature of the twin-screw extruder is 130 °C, and the main engine rotation speed of the twin-screw extruder is 260 r / min.

[0030] N-dodecyl succinic anhydride was purchased from Hubei Weishi Chemical Reagent Co., Ltd.

[0031] Dibutyl maleate was purchased from Shandong Xuchen Chemical Technology Co., Ltd.

[0032] Dilauryl thiodipropionate was purchased from Wuhan Chengtian Fine Chemical Co., Ltd.

[0033] The ethylene octene copolymer was purchased from Exxon in the United States, product name: POE, model: 3980FL.

[0034] The polypropylene was purchased from Sinopec, grade: YPJ-1215C.

[0035] Antioxidant 1010 was purchased from Henan Wanshan New Material Technology Co., Ltd.

[0036] Light stabilizer 770 was purchased from Fujian Disheng Technology Co., Ltd.

[0037] Example 2 A high-temperature resistant TPE material and a preparation method thereof, including the following steps: Step 1), put 0.9 kg of N-dodecyl succinic anhydride, 0.3 kg of dibutyl maleate, and 0.7 kg of dilauryl thiodipropionate into a stirring kettle, introduce nitrogen, discharge air, and under a nitrogen atmosphere, heat to 95 °C, with a rotation speed of 60 r / min, and stir for 75 min until evenly mixed to obtain the auxiliary premix.

[0038] Step 2), add 75.1 kg of ethylene octene copolymer, 22 kg of polypropylene, 0.5 kg of antioxidant 1010, and 0.5 kg of light stabilizer 770 to the auxiliary premix. Keep the temperature at 95 °C, the rotation speed at 120 r / min, and stir for 10 min until evenly mixed to obtain the premix.

[0039] Step 3), inject the premix into a twin-screw extruder, extrude and pelletize to obtain a heat-resistant TPE material. The temperatures of zones 1 - 14 of the twin-screw extruder are 130°C, 205°C, 205°C, 205°C, 205°C, 205°C, 150°C, 150°C, 150°C, 150°C, 150°C, 150°C, 150°C, 150°C in sequence. The temperature of the head of the twin-screw extruder is 165°C, and the main machine speed of the twin-screw extruder is 430 r / min.

[0040] N-Dodecenyl succinic anhydride was purchased from Hubei Weishi Chemical Reagent Co., Ltd.

[0041] Dibutyl maleate was purchased from Shandong Xuchen Chemical Technology Co., Ltd.

[0042] Dilauryl thiodipropionate was purchased from Wuhan Chengtian Fine Chemical Co., Ltd.

[0043] Ethylene octene copolymer was purchased from Exxon in the United States, product name: POE, model: 3980FL.

[0044] Polypropylene was purchased from Sinopec, grade: YPJ-1215C.

[0045] Antioxidant 1010 was purchased from Henan Wanshan New Material Technology Co., Ltd.

[0046] Light stabilizer 770 was purchased from Fujian Disheng Technology Co., Ltd.

[0047] Example 3 A heat-resistant TPE material and a preparation method of the heat-resistant TPE material, comprising the following steps: Step 1), put 1 kg of N-dodecenyl succinic anhydride, 0.4 kg of dibutyl maleate, and 0.8 kg of dilauryl thiodipropionate into a stirring kettle, introduce nitrogen, discharge air, and under a nitrogen atmosphere, heat to 100°C, rotate at 60 r / min, and stir for 90 min to mix evenly to obtain an auxiliary premix.

[0048] Step 2), add 73.6 kg of ethylene octene copolymer, 23 kg of polypropylene, 0.6 kg of antioxidant 1010, and 0.6 kg of light stabilizer 770 to the auxiliary premix, keep the temperature at 100°C, rotate at 120 r / min, and stir for 10 min to mix evenly to obtain a premix.

[0049] Step 3): Inject the premix into a twin-screw extruder, extrude and pelletize to obtain a high-temperature resistant TPE material. The temperatures of zones 1-14 of the twin-screw extruder are 160 °C, 230 °C, 230 °C, 230 °C, 230 °C, 230 °C, 180 °C, 180 °C, 180 °C, 180 °C, 180 °C, 180 °C, 180 °C, 180 °C in sequence. The head temperature of the twin-screw extruder is 200 °C, and the main machine speed of the twin-screw extruder is 600 r / min.

[0050] N-dodecyl succinic anhydride was purchased from Hubei Weishi Chemical Reagent Co., Ltd.

[0051] Dibutyl maleate was purchased from Shandong Xuchen Chemical Technology Co., Ltd.

[0052] Dilauryl thiodipropionate was purchased from Wuhan Chengtian Fine Chemical Co., Ltd.

[0053] Ethylene-octene copolymer was purchased from ExxonMobil in the United States, product name: POE, model: 3980FL.

[0054] Polypropylene was purchased from Sinopec, grade: YPJ-1215C.

[0055] Antioxidant 1010 was purchased from Henan Wanshan New Material Technology Co., Ltd.

[0056] Light stabilizer 770 was purchased from Fujian Disheng Technology Co., Ltd.

[0057] Comparative Example 1 A high-temperature resistant TPE material and a preparation method thereof, comprising the following steps: Step 1): Put 0.9 kg of potassium titanate whiskers, 0.3 kg of dibutyl maleate, and 0.7 kg of dilauryl thiodipropionate into a stirring kettle, introduce nitrogen, discharge air, heat to 95 °C under a nitrogen atmosphere, stir at a speed of 60 r / min for 75 min, and mix evenly to obtain an additive premix.

[0058] Step 2): Add 75.1 kg of ethylene-octene copolymer, 22 kg of polypropylene, 0.5 kg of antioxidant 1010, and 0.5 kg of light stabilizer 770 to the additive premix, keep the temperature at 95 °C, stir at a speed of 120 r / min for 10 min, and mix evenly to obtain a premix.

[0059] Step 3), inject the premix into a twin-screw extruder, extrude and pelletize to obtain a heat-resistant TPE material. The temperatures of zones 1 - 14 of the twin-screw extruder are 130 °C, 205 °C, 205 °C, 205 °C, 205 °C, 205 °C, 150 °C, 150 °C, 150 °C, 150 °C, 150 °C, 150 °C, 150 °C, 150 °C in sequence. The head temperature of the twin-screw extruder is 165 °C, and the main machine speed of the twin-screw extruder is 430 r / min.

[0060] Potassium titanate whiskers were purchased from Wuhan Kemike Biopharmaceutical Technology Co., Ltd.

[0061] Dibutyl maleate was purchased from Shandong Xuchen Chemical Technology Co., Ltd.

[0062] Dilauryl thiodipropionate was purchased from Wuhan Chengtian Fine Chemical Co., Ltd.

[0063] Ethylene-octene copolymer was purchased from Exxon in the United States, product name: POE, model: 3980FL.

[0064] Polypropylene was purchased from Sinopec, grade: YPJ-1215C.

[0065] Antioxidant 1010 was purchased from Henan Wanshan New Material Technology Co., Ltd.

[0066] Light stabilizer 770 was purchased from Fujian Disheng Technology Co., Ltd.

[0067] Comparative Example 2 A heat-resistant TPE material and a preparation method thereof, comprising the following steps: Step 1), put 0.9 kg of N-dodecyl succinic anhydride, 0.3 kg of magnesium oxide, and 0.7 kg of dilauryl thiodipropionate into a stirring kettle, introduce nitrogen, discharge air, heat to 95 °C under a nitrogen atmosphere, stir at a speed of 60 r / min for 75 min, and mix evenly to obtain an additive premix.

[0068] Step 2), add 75.1 kg of ethylene-octene copolymer, 22 kg of polypropylene, 0.5 kg of antioxidant 1010, and 0.5 kg of light stabilizer 770 to the additive premix, keep the temperature at 95 °C, stir at a speed of 120 r / min for 10 min, and mix evenly to obtain a premix.

[0069] Step 3), inject the premix into a twin-screw extruder, extrude and pelletize to obtain a high-temperature resistant TPE material. The temperatures of zones 1 - 14 of the twin-screw extruder are 130°C, 205°C, 205°C, 205°C, 205°C, 205°C, 150°C, 150°C, 150°C, 150°C, 150°C, 150°C, 150°C, 150°C in sequence. The head temperature of the twin-screw extruder is 165°C, and the main machine speed of the twin-screw extruder is 430 r / min.

[0070] N-Dodecenyl succinic anhydride was purchased from Hubei Weishi Chemical Reagent Co., Ltd.

[0071] Magnesium oxide was purchased from Hebei Yuechao Wear-resistant Materials Co., Ltd., with a particle size of 50 μm.

[0072] Dilauryl thiodipropionate was purchased from Wuhan Chengtian Fine Chemical Co., Ltd.

[0073] Ethylene octene copolymer was purchased from Exxon in the United States, product name: POE, model: 3980FL.

[0074] Polypropylene was purchased from Sinopec, grade: YPJ-1215C.

[0075] Antioxidant 1010 was purchased from Henan Wanshan New Material Technology Co., Ltd.

[0076] Light stabilizer 770 was purchased from Fujian Disheng Technology Co., Ltd.

[0077] Comparative Example 3 A high-temperature resistant TPE material and a preparation method thereof, comprising the following steps: Step 1), put 0.9 kg of N-dodecenyl succinic anhydride, 0.3 kg of dibutyl maleate, and 0.7 kg of zinc borate into a stirring kettle, introduce nitrogen, discharge air, heat to 95°C under a nitrogen atmosphere, with a rotation speed of 60 r / min, and stir for 75 min to mix evenly to obtain an auxiliary premix.

[0078] Step 2), add 75.1 kg of ethylene octene copolymer, 22 kg of polypropylene, 0.5 kg of antioxidant 1010, and 0.5 kg of light stabilizer 770 to the auxiliary premix, keep the temperature at 95°C, with a rotation speed of 120 r / min, and stir for 10 min to mix evenly to obtain a premix.

[0079] Step 3), inject the premix into a twin-screw extruder, extrude and pelletize to obtain a high-temperature resistant TPE material. The temperatures of zones 1-14 of the twin-screw extruder are 130 °C, 205 °C, 205 °C, 205 °C, 205 °C, 205 °C, 150 °C, 150 °C, 150 °C, 150 °C, 150 °C, 150 °C, 150 °C, 150 °C in sequence. The temperature of the head of the twin-screw extruder is 165 °C, and the main machine speed of the twin-screw extruder is 430 r / min.

[0080] N-Dodecyl succinic anhydride was purchased from Hubei Weishi Chemical Reagent Co., Ltd.

[0081] Dibutyl maleate was purchased from Shandong Xuchen Chemical Technology Co., Ltd.

[0082] Zinc borate was purchased from Shandong Huibang New Material Technology Co., Ltd.

[0083] Ethylene octene copolymer was purchased from ExxonMobil in the United States, product name: POE, model: 3980FL.

[0084] Polypropylene was purchased from Sinopec, grade: YPJ-1215C.

[0085] Antioxidant 1010 was purchased from Henan Wanshan New Material Technology Co., Ltd.

[0086] Light stabilizer 770 was purchased from Fujian Disheng Technology Co., Ltd.

[0087] Comparative Example 4 A high-temperature resistant TPE material and a preparation method thereof, comprising the following steps: Step 1), put 0.9 kg of potassium titanate whiskers, 0.3 kg of magnesium oxide, and 0.7 kg of zinc borate into a stirring kettle, introduce nitrogen, discharge air, heat to 95 °C under a nitrogen atmosphere, rotate at 60 r / min, and stir for 75 min to mix evenly to obtain an additive premix.

[0088] Step 2), add 75.1 kg of ethylene octene copolymer, 22 kg of polypropylene, 0.5 kg of antioxidant 1010, and 0.5 kg of light stabilizer 770 to the additive premix, keep the temperature at 95 °C, rotate at 120 r / min, and stir for 10 min to mix evenly to obtain a premix.

[0089] Step 3), injecting the premix into a twin-screw extruder, extruding, and granulating to obtain a high temperature resistant TPE material, the temperatures of zones 1-14 of the twin-screw extruder are 130°C, 205°C, 205°C, 205°C, 205°C, 150°C, 150°C, 150°C, 150°C, 150°C, 150°C, 150°C, 150°C, 150°C, the head temperature of the twin-screw extruder is 165°C, and the main engine speed of the twin-screw extruder is 430r / min.

[0090] Potassium titanate whiskers were purchased from Wuhan Kemik Biopharmaceutical Technology Co., Ltd.

[0091] Magnesium oxide was purchased from Hebei Yuechao Wear Resistant Materials Co., Ltd. with a particle size of 50 μm.

[0092] Zinc borate was purchased from Shandong Huibang New Material Technology Co., Ltd.

[0093] Ethylene octene copolymer was purchased from Exxon in the United States, product name: POE, model: 3980FL.

[0094] Polypropylene was purchased from Sinopec, brand: YPJ-1215C.

[0095] Antioxidant 1010 was purchased from Henan Wanshan New Material Technology Co., Ltd.

[0096] Light stabilizer 770 was purchased from Fujian Disheng Technology Co., Ltd.

[0097] Experiment 1 According to GB / T1633-2000 "Determination of Vicat Softening Temperature (VST) of Thermoplastic Plastics", the Vicat softening temperature of the test samples made of high temperature resistant TPE materials in each embodiment and comparative example was tested.

[0098] Experiment 2 According to GB / T1040.2-2022 "Determination of Tensile Properties of Plastics Part 2: Test Conditions for Molded and Extruded Plastics", the tensile strength of the specimens made of high temperature resistant TPE materials in each embodiment and comparative example was tested. Type 1A specimens were selected for testing, and the test speed was 50 mm / min.

[0099] The specific experimental data of Experiments 1 and 2 are shown in Table 1.

[0100] Table 1 Vicat softening temperature (°C) Tensile strength (MPa) Example 1 138 9.35 Example 2 142 9.49 Example 3 141 9.24 Comparative Example 1 123 5.67 Comparative Example 2 119 5.84 Comparative Example 3 126 6.12 Comparative Example 4 114 5.26 According to the data comparison of each embodiment and the comparative example in Table 1, it can be obtained that the Vicat softening temperature of each embodiment is higher than that of each comparative example. It can be seen that after adding the additive formed by compounding N-dodecyl succinic anhydride, dibutyl maleate and didodecyl thiodipropionate, the effect of improving the heat resistance of the TPE material is better than the effect of traditional addition of inorganic fillers.

[0101] The tensile strength of each embodiment is significantly higher than that of each comparative example. It can be seen that by adding the auxiliary agent prepared by compounding N-dodecyl succinic anhydride, dibutyl maleate, and didodecyl thiodipropionate, not only the heat resistance of the TPE material can be improved, but also the mechanical properties of the TPE material can be improved, thereby improving the quality of the TPE material.

[0102] 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 heat-resistant TPE material, characterized in that: Comprising the following components in parts by mass: 73.6 - 76.6 parts of polyolefin elastomer; 21 - 23 parts of polypropylene; 1.6 - 3.4 parts of additives; The additives at least include the compounding of N-dodecyl succinic anhydride, dibutyl maleate, and dilauryl thiodipropionate.

2. The heat-resistant TPE material according to claim 1, wherein: The mass ratio of N-dodecyl succinic anhydride, dibutyl maleate, and dilauryl thiodipropionate is 0.8 - 1:0.2 - 0.4:0.6 - 0.

8.

3. The heat-resistant TPE material according to claim 2, characterized in that: The additives further include antioxidant and light stabilizer.

4. The heat-resistant TPE material according to claim 3, wherein: The mass ratio of N-dodecyl succinic anhydride, dibutyl maleate, dilauryl thiodipropionate, antioxidant, and light stabilizer is 0.8 - 1:0.2 - 0.4:0.6 - 0.8:0.4 - 0.6:0.4 - 0.

6.

5. A heat-resistant TPE material according to claim 4, characterized in that: The antioxidant is antioxidant 1010, and the light stabilizer is light stabilizer 770.

6. A heat-resistant TPE material according to any one of claims 1-5, characterized in that: The polyolefin elastomer is ethylene-octene copolymer.

7. A preparation method of the high-temperature resistant TPE material according to any one of claims 1-6, characterized in that: Comprising the following steps: Step 1), mixing N-dodecyl succinic anhydride, dibutyl maleate, and dilauryl thiodipropionate uniformly to obtain an additive premix; Step 2), mixing the additive premix and other raw materials uniformly to obtain a premix; Step 3), extruding the premix through an extruder and pelletizing to obtain a high-temperature resistant TPE material.

8. The preparation method of a heat-resistant TPE material according to claim 7, characterized in that: In the said Step 1), N-dodecyl succinic anhydride, dibutyl maleate, and dilauryl thiodipropionate are stirred at 90 - 100 °C for 60 - 90 min to obtain an additive premix.

9. The preparation method of a heat-resistant TPE material according to claim 8, characterized in that: In the said Step 1), under a nitrogen atmosphere, N-dodecyl succinic anhydride, dibutyl maleate, and dilauryl thiodipropionate are heated to 90 - 100 °C for stirring.