High-weather-resistance environment-friendly EVA composite material and preparation method thereof

Abstract

The invention relates to the technical field of EVA materials, and particularly discloses a high-weather-resistance environment-friendly EVA composite material and a preparation method thereof. The high-weather-resistance environment-friendly EVA composite material comprises the following components in parts by mass: 40-50 parts of EVA resin; 20 to 30 parts of LDPE resin; 5-10 parts of a heat stabilizer; 5-10 parts of a plasticizer; 3-4.5 parts of compound oil; the compound oil is formed by compounding nigella esculenta seed oil, sacha inchi oil and eucommia ulmoides seed oil. The weather-resistant EVA composite material has the advantages that the weather resistance of the EVA composite material is improved, and relatively high physical properties are kept.

Description

Technical Field

[0001] The present invention relates to the field of EVA materials, and in particular to a highly weather-resistant and environmentally friendly EVA composite material and a preparation method thereof. Background Art

[0002] In recent years, with the increasing awareness of environmental protection and the improvement of product quality requirements, the development of high-performance, low-pollution new materials has become an important topic in the field of materials science. EVA has been widely used in many industrial sectors due to its good flexibility, impact resistance and adhesion. However, traditional EVA materials are prone to aging under long-term exposure to natural conditions such as ultraviolet light, high temperature, and humidity changes, resulting in performance degradation, which limits its further application in some fields.

[0003] At present, the common methods to improve the weather resistance of EVA materials include adding UV absorbers, antioxidants, anti-aging agents and other additives. Although these additives can slow down the aging rate of EVA to a certain extent, if these additives are to significantly improve the weather resistance of EVA, they usually need to be added in large quantities. The large addition of UV absorbers, antioxidants, anti-aging agents and other additives will lead to a significant decrease in the physical properties of EVA materials. Therefore, there is still room for improvement. Summary of the invention

[0004] In order to improve the weather resistance of EVA composite materials and maintain high physical properties, the present application provides a highly weather-resistant and environmentally friendly EVA composite material and a preparation method thereof.

[0005] In the first aspect, the present application provides a highly weather-resistant and environmentally friendly EVA composite material, which adopts the following technical solution: A highly weather-resistant and environmentally friendly EVA composite material comprises the following components in parts by weight: 40-50 parts of EVA resin; 20-30 parts of LDPE resin; Heat stabilizer 5-10 parts; 5-10 parts of plasticizer; 3-4.5 parts of compound oil; The compound oil is a compound of black cumin seed oil, sacha inchi oil and eucommia ulmoides seed oil.

[0006] By adopting the above technical scheme, a composite oil prepared by adding black cumin seed oil, sacha inchi oil and eucommia seed oil into EVA resin, the black cumin seed oil, sacha inchi oil and eucommia seed oil can effectively protect the EVA resin under the mutual cooperation of the black cumin seed oil, sacha inchi oil and eucommia seed oil, so that the weather resistance of the composite material is significantly improved, and at the same time, the physical properties of the composite material can be enhanced, so that the application range of the composite material is wider.

[0007] By compounding EVA resin and LDPE resin, the composite material has higher flexibility, higher tensile strength and elongation at break, further improving the application range of the composite material.

[0008] The use of heat stabilizers can reduce thermal oxidative aging during the extrusion process of composite materials, reduce process difficulty, and improve product quality.

[0009] Plasticizers can improve the physical properties of composite materials, enhance the tensile strength of composite materials, and better meet various usage requirements.

[0010] Preferably, the mass ratio of the black cumin seed oil, sacha inchi oil and eucommia seed oil is 1.5-2:0.5-1:1-1.5.

[0011] By adopting the above technical scheme and specifically selecting the mass ratio of black cumin seed oil, sacha inchi oil and eucommia seed oil, the black cumin seed oil, sacha inchi oil and eucommia seed oil can cooperate with each other better, and the weather resistance of the composite material can be better improved.

[0012] Preferably, the heat stabilizer is a compound of methyl tin mercaptan, stearic acid and zinc laurate.

[0013] By adopting the above technical solution and specifically selecting methyltin mercaptan, stearic acid and zinc laurate, the effect of reducing the thermal oxidation aging phenomenon during the processing of the composite material is better.

[0014] Preferably, the mass ratio of the methyl tin mercaptan, stearic acid and zinc laurate is 1-2:3-5:1-3.

[0015] By adopting the above technical solution and specifically selecting the mass ratio of methyltin mercaptan, stearic acid and zinc laurate, the effect of resisting thermal oxidative aging is further improved, so that the performance of the composite material after high-temperature extrusion is better.

[0016] Preferably, the plasticizer is a compound of n-octanol, dioctyl adipate and dibutyl maleate.

[0017] By adopting the above technical solution and specifically selecting n-octanol, dioctyl adipate and dibutyl maleate, the physical properties of the composite material can be better improved.

[0018] Preferably, the mass ratio of n-octanol, dioctyl adipate and dibutyl maleate is 2-4:1-2:2-4.

[0019] By adopting the above technical solution and specifically selecting the mass ratio of n-octanol, dioctyl adipate and dibutyl maleate, the effect of improving the tensile strength of the composite material is better.

[0020] In a second aspect, the present application provides a method for preparing a highly weather-resistant and environmentally friendly EVA composite material, using the following technical solution: A method for preparing the above-mentioned highly weather-resistant and environmentally friendly EVA composite material comprises the following steps: Step 1), EVA resin, LDPE resin, heat stabilizer, plasticizer, and composite oil are uniformly stirred to obtain a premix; Step 2), extruding and granulating the premix to obtain a highly weather-resistant and environmentally friendly EVA composite material.

[0021] By adopting the above technical scheme, the obtained high weather resistance and environmentally friendly EVA composite material has good weather resistance, better physical properties, a wide range of applications, and high economic value.

[0022] Preferably, in step 2), the extrusion temperature is 200-220°C.

[0023] By adopting the above technical solution and specifically selecting the extrusion temperature to be 200-220° C., the components are fully mixed, the modification effect on the composite material is better, and the weather resistance of the composite material is more significantly improved.

[0024] In summary, this application has the following beneficial effects: 1. Since the composite oil prepared by adding black cumin seed oil, sacha inchi oil and eucommia seed oil to EVA resin can effectively protect the EVA resin under the cooperation of black cumin seed oil, sacha inchi oil and eucommia seed oil, the weather resistance of the composite material can be significantly improved, and the physical properties of the composite material can be enhanced, so that the application range of the composite material is wider.

[0025] 2. In the present application, it is preferred to specifically select the mass ratio of black cumin seed oil, sacha inchi oil and eucommia seed oil so that the black cumin seed oil, sacha inchi oil and eucommia seed oil cooperate with each other better, which can better improve the weather resistance of the composite material.

[0026] 3. In the present application, it is preferred to compound EVA resin and LDPE resin to make the composite material more flexible, and the composite material has higher tensile strength and elongation at break, further improving the application range of the composite material, and reducing the thermal oxidative aging phenomenon during the extrusion process of the composite material by using a heat stabilizer, reducing the process difficulty and improving the product quality, and then using a plasticizer to improve the physical properties of the composite material, better improve the tensile strength of the composite material, and better meet the needs of various use requirements. DETAILED DESCRIPTION

[0027] The present application is further described in detail below in conjunction with embodiments.

[0028] Example 1 A highly weather-resistant and environmentally friendly EVA composite material comprises the following components: EVA resin, LDPE resin, heat stabilizer, plasticizer, compound oil.

[0029] The heat stabilizer is a compound of methyl tin mercaptan, stearic acid and zinc laurate.

[0030] The plasticizer is a compound of n-octanol, dioctyl adipate and dibutyl maleate.

[0031] The compound oil is a compound of black cumin seed oil, sacha inchi oil and eucommia ulmoides seed oil.

[0032] The EVA resin was purchased from Mitsui Chemicals of Japan, with a grade of 220.

[0033] LDPE resin was purchased from Sinopec with the brand name 1C7AS.

[0034] Methyltin mercaptan was purchased from Shandong Yueyang New Materials Co., Ltd., CAS No.: 451-65-34.

[0035] Stearic acid was purchased from Hubei Xinghengye Technology Co., Ltd., CAS No.: 57-11-4.

[0036] Zinc laurate was purchased from Wuhan Smack Biotechnology Co., Ltd., CAS number: 2452-01-9.

[0037] n-Octanol was purchased from Shandong Langcheng Chemical Co., Ltd., CAS No.: 111-87-5.

[0038] Dioctyl adipate was purchased from Shandong Yueyang New Materials Co., Ltd., CAS No.: 103-23-1.

[0039] Dibutyl maleate was purchased from Hubei Shineng Chemical Technology Co., Ltd., CAS No.: 105-76-0.

[0040] Black cumin seed oil was purchased from Jiangxi Xuesong Natural Medicinal Oil Co., Ltd.

[0041] Sacha Inchi oil was purchased from the Hongxing Natural Medicinal Spice Oil Factory in Jishui County.

[0042] Eucommia seed oil was purchased from Xi'an Shilin Biotechnology Co., Ltd.

[0043] The preparation method of the highly weather-resistant and environmentally friendly EVA composite material comprises the following steps: Step 1), 40kg EVA resin, 20kg LDPE resin, 1kg methyl tin mercaptan, 3kg stearic acid, 1kg zinc laurate, 2kg n-octanol, 1kg dioctyl adipate, 2kg dibutyl maleate, 1.5kg black cumin seed oil, 0.5kg sacha inchi oil, 1kg eucommia seed oil are put into a stirred tank, 240r / min, stirred for 20min, stirred evenly to obtain a premix.

[0044] Step 2), the premix is ​​put into a twin-screw extruder for extrusion and underwater granulation to obtain a highly weather-resistant and environmentally friendly EVA composite material. The processing temperatures of the twin-screw extruder zones I-XI are set to: 165°C, 165°C, 175°C, 185°C, 195°C, 195°C, 195°C, 200°C, 200°C, 200°C, and the screw speed is 40r / min.

[0045] Example 2 A highly weather-resistant and environmentally friendly EVA composite material comprises the following components: EVA resin, LDPE resin, heat stabilizer, plasticizer, compound oil.

[0046] The heat stabilizer is a compound of methyl tin mercaptan, stearic acid and zinc laurate.

[0047] The plasticizer is a compound of n-octanol, dioctyl adipate and dibutyl maleate.

[0048] The compound oil is a compound of black cumin seed oil, sacha inchi oil and eucommia ulmoides seed oil.

[0049] The EVA resin was purchased from Mitsui Chemicals of Japan, with a grade of 220.

[0050] LDPE resin was purchased from Sinopec with the brand name 1C7AS.

[0051] Methyltin mercaptan was purchased from Shandong Yueyang New Materials Co., Ltd., CAS No.: 451-65-34.

[0052] Stearic acid was purchased from Hubei Xinghengye Technology Co., Ltd., CAS No.: 57-11-4.

[0053] Zinc laurate was purchased from Wuhan Smack Biotechnology Co., Ltd., CAS number: 2452-01-9.

[0054] n-Octanol was purchased from Shandong Langcheng Chemical Co., Ltd., CAS No.: 111-87-5.

[0055] Dioctyl adipate was purchased from Shandong Yueyang New Materials Co., Ltd., CAS No.: 103-23-1.

[0056] Dibutyl maleate was purchased from Hubei Shineng Chemical Technology Co., Ltd., CAS No.: 105-76-0.

[0057] Black cumin seed oil was purchased from Jiangxi Xuesong Natural Medicinal Oil Co., Ltd.

[0058] Sacha Inchi oil was purchased from the Hongxing Natural Medicinal Spice Oil Factory in Jishui County.

[0059] Eucommia seed oil was purchased from Xi'an Shilin Biotechnology Co., Ltd.

[0060] The preparation method of the highly weather-resistant and environmentally friendly EVA composite material comprises the following steps: Step 1), 45kg EVA resin, 25kg LDPE resin, 1.5kg methyl tin mercaptan, 4kg stearic acid, 2kg zinc laurate, 3kg n-octanol, 1.5kg dioctyl adipate, 3kg dibutyl maleate, 1.8kg black cumin seed oil, 0.7kg sacha inchi oil, 1.2kg eucommia seed oil are put into a stirred tank, 240r / min, stirred for 20min, stirred evenly to obtain a premix.

[0061] Step 2), the premix is ​​put into a twin-screw extruder for extrusion and underwater granulation to obtain a highly weather-resistant and environmentally friendly EVA composite material. The processing temperatures of the twin-screw extruder zones I-XI are set to: 175°C, 175°C, 185°C, 195°C, 205°C, 205°C, 205°C, 210°C, 210°C, 210°C, and the screw speed is 40r / min.

[0062] Example 3 A highly weather-resistant and environmentally friendly EVA composite material comprises the following components: EVA resin, LDPE resin, heat stabilizer, plasticizer, compound oil.

[0063] The heat stabilizer is a compound of methyl tin mercaptan, stearic acid and zinc laurate.

[0064] The plasticizer is a compound of n-octanol, dioctyl adipate and dibutyl maleate.

[0065] The compound oil is a compound of black cumin seed oil, sacha inchi oil and eucommia ulmoides seed oil.

[0066] The EVA resin was purchased from Mitsui Chemicals of Japan, with a grade of 220.

[0067] LDPE resin was purchased from Sinopec with the brand name 1C7AS.

[0068] Methyltin mercaptan was purchased from Shandong Yueyang New Materials Co., Ltd., CAS No.: 451-65-34.

[0069] Stearic acid was purchased from Hubei Xinghengye Technology Co., Ltd., CAS No.: 57-11-4.

[0070] Zinc laurate was purchased from Wuhan Smack Biotechnology Co., Ltd., CAS number: 2452-01-9.

[0071] n-Octanol was purchased from Shandong Langcheng Chemical Co., Ltd., CAS No.: 111-87-5.

[0072] Dioctyl adipate was purchased from Shandong Yueyang New Materials Co., Ltd., CAS No.: 103-23-1.

[0073] Dibutyl maleate was purchased from Hubei Shineng Chemical Technology Co., Ltd., CAS No.: 105-76-0.

[0074] Black cumin seed oil was purchased from Jiangxi Xuesong Natural Medicinal Oil Co., Ltd.

[0075] Sacha Inchi oil was purchased from the Hongxing Natural Medicinal Spice Oil Factory in Jishui County.

[0076] Eucommia seed oil was purchased from Xi'an Shilin Biotechnology Co., Ltd.

[0077] The preparation method of the highly weather-resistant and environmentally friendly EVA composite material comprises the following steps: Step 1), 50kg EVA resin, 30kg LDPE resin, 2kg methyl tin mercaptan, 5kg stearic acid, 3kg zinc laurate, 4kg n-octanol, 2kg dioctyl adipate, 4kg dibutyl maleate, 2kg black cumin seed oil, 1kg sacha inchi oil, 1.5kg eucommia seed oil are put into a stirred tank, 240r / min, stirred for 20min, stirred evenly to obtain a premix.

[0078] Step 2), the premix is ​​put into a twin-screw extruder for extrusion and underwater granulation to obtain a highly weather-resistant and environmentally friendly EVA composite material. The processing temperatures of the twin-screw extruder zones I-XI are set to: 185°C, 185°C, 195°C, 205°C, 215°C, 215°C, 215°C, 220°C, 220°C, 220°C, and the screw speed is 40r / min.

[0079] Comparative Example 1 A highly weather-resistant and environmentally friendly EVA composite material, compared with Example 2, the only difference is: Replace the black cumin seed oil with an equal amount of flaxseed oil.

[0080] The flaxseed oil was purchased from Jiangxi Xuesong Natural Medicinal Oil Co., Ltd.

[0081] Comparative Example 2 A highly weather-resistant and environmentally friendly EVA composite material, compared with Example 2, the only difference is: Replace sacha inchi oil with an equal amount of neem seed oil.

[0082] Neem seed oil was purchased from Hubei Yuanmeng Biotechnology Co., Ltd.

[0083] Comparative Example 3 A highly weather-resistant and environmentally friendly EVA composite material, compared with Example 2, the only difference is: Use apple seed oil to replace eucommia seed oil in equal amounts.

[0084] Apple seed oil Jiangxi Yuanshangcao Spice Co., Ltd.

[0085] Comparative Example 4 A highly weather-resistant and environmentally friendly EVA composite material, compared with Example 2, the only difference is: Use flaxseed oil to replace black cumin seed oil in an equal amount, use neem seed oil to replace sacha inchi oil in an equal amount, and use apple seed oil to replace eucommia seed oil in an equal amount.

[0086] The flaxseed oil was purchased from Jiangxi Xuesong Natural Medicinal Oil Co., Ltd.

[0087] Neem seed oil was purchased from Hubei Yuanmeng Biotechnology Co., Ltd.

[0088] Apple seed oil Jiangxi Yuanshangcao Spice Co., Ltd.

[0089] Comparative Example 5 A highly weather-resistant and environmentally friendly EVA composite material, compared with Example 2, the only difference is: Use antioxidant 2246 to replace black cumin seed oil in equal amounts.

[0090] Antioxidant 2246 was purchased from Nanjing Milan Chemical Co., Ltd.

[0091] Comparative Example 6 A highly weather-resistant and environmentally friendly EVA composite material, compared with Example 2, the only difference is: An equal amount of antioxidant 1076 was used to replace sacha inchi oil.

[0092] Antioxidant 1076 was purchased from Dongguan Zhenming Chemical Co., Ltd.

[0093] Comparative Example 7 A highly weather-resistant and environmentally friendly EVA composite material, compared with Example 2, the only difference is: An equal amount of antioxidant 1010 was used to replace eucommia seed oil.

[0094] Antioxidant 1010 was purchased from Jinan Junteng Chemical Co., Ltd.

[0095] Comparative Example 8 A highly weather-resistant and environmentally friendly EVA composite material, compared with Example 2, the only difference is: Antioxidant 2246 was used to replace black cumin seed oil in equal amounts, antioxidant 1076 was used to replace sacha inchi oil in equal amounts, and antioxidant 1010 was used to replace eucommia seed oil in equal amounts.

[0096] Antioxidant 2246 was purchased from Nanjing Milan Chemical Co., Ltd.

[0097] Antioxidant 1076 was purchased from Dongguan Zhenming Chemical Co., Ltd.

[0098] Antioxidant 1010 was purchased from Jinan Junteng Chemical Co., Ltd.

[0099] Experiment 1 According to GB / T13642-2015 "Dynamic tensile test for ozone cracking resistance of vulcanized rubber or thermoplastic rubber", the ozone aging resistance (ozone concentration 800pphm, elongation 20%, 40°C) of the samples prepared from the high weather-resistant and environmentally friendly EVA composite materials of each embodiment and comparative example was tested, and the time required for cracking was tested.

[0100] 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 samples made of high weather-resistant and environmentally friendly EVA composite materials in each embodiment and comparative example was tested using Type 1A samples.

[0101] The specific test data of Experiments 1 and 2 are shown in Table 1.

[0102] Table 1 Ozone cracking time (h) Tensile strength(MPa) Example 1 42 23.4 Example 2 43 23.7 Example 3 45 24.1 Comparative Example 1 29 22.8 Comparative Example 2 31 22.6 Comparative Example 3 27 23.1 Comparative Example 4 26 22.5 Comparative Example 5 40 14.3 Comparative Example 6 38 15.7 Comparative Example 7 41 14.6 Comparative Example 8 43 14.1 According to the data comparison of each embodiment and comparative example in Table 1, the weather resistance of each embodiment is significantly better than that of comparative examples 1-4, and the physical performance is slightly better than that of comparative examples 1-4. It can be seen that only the composite oil formed by adding black cumin seed oil, sacha inchi oil and eucommia seed oil can significantly improve the weather resistance. Although the use of other oils also helps to maintain the physical properties of the EVA composite material, the effect of improving the weather resistance is relatively general.

[0103] The weather resistance of each embodiment is slightly better than that of comparative examples 5-8. At the same time, the tensile strength of each embodiment is significantly better than that of comparative examples 5-8. It can be seen that the composite oil formed by adding black cumin seed oil, sacha inchi oil and eucommia seed oil to the EVA composite material can make the weather resistance of the EVA composite material reach the level when a large amount of antioxidant is added. At the same time, only adding black cumin seed oil, sacha inchi oil and eucommia seed oil without adding antioxidant can keep the tensile strength of the EVA composite material at a high level, and will not cause a significant decrease in the tensile strength of the EVA resin as in comparative examples 5-8.

[0104] 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 highly weather-resistant and environmentally friendly EVA composite material, characterized by: The composition includes the following components in parts by weight: 40-50 parts of EVA resin; 20-30 parts of LDPE resin; Heat stabilizer 5-10 parts; 5-10 parts of plasticizer; 3-4.5 parts of compound oil; The compound oil is a compound of black cumin seed oil, sacha inchi oil and eucommia ulmoides seed oil.

2. The highly weather-resistant and environmentally friendly EVA composite material according to claim 1, characterized in that: The mass ratio of the black cumin seed oil, sacha inchi oil and eucommia ulmoides seed oil is 1.5-2:0.5-1:1-1.

5.

3. The highly weather-resistant and environmentally friendly EVA composite material according to claim 1, characterized in that: The heat stabilizer is a compound of methyltin mercaptan, stearic acid and zinc laurate.

4. The highly weather-resistant and environmentally friendly EVA composite material according to claim 3, characterized in that: The mass ratio of the methyl tin mercaptan, stearic acid and zinc laurate is 1-2:3-5:1-3.

5. The highly weather-resistant and environmentally friendly EVA composite material according to claim 1, characterized in that: The plasticizer is a compound of n-octanol, dioctyl adipate and dibutyl maleate.

6. The highly weather-resistant and environmentally friendly EVA composite material according to claim 5, characterized in that: The mass ratio of n-octanol, dioctyl adipate and dibutyl maleate is 2-4:1-2:2-4.

7. A method for preparing a highly weather-resistant and environmentally friendly EVA composite material according to any one of claims 1 to 6, characterized in that: The following steps are involved: Step 1), EVA resin, LDPE resin, heat stabilizer, plasticizer and compound oil are uniformly stirred to obtain a premix; Step 2), the premix is ​​extruded and granulated to obtain a highly weather-resistant and environmentally friendly EVA composite material.

8. The method for preparing a highly weather-resistant and environmentally friendly EVA composite material according to claim 7, characterized in that: In the step 2), the extrusion temperature is 200-220°C.