A thermoplastic elastomer material and its preparation method and application

Abstract

The present invention relates to a thermoplastic elastomer material and a preparation method and application thereof. The thermoplastic elastomer material comprises a styrene elastomer, white oil, a polyamide elastomer, a compatibilizer and a filler. The present invention utilizes a styrene elastomer and a polyamide elastomer for compounding, and adds white oil to improve the processing performance of the styrene elastomer, and the compatibilizer improves the compatibility between the styrene elastomer and the polyamide elastomer. The obtained thermoplastic elastomer material has good Shore hardness and good adhesion to a PA / PP alloy material, and can be widely used as a coating material for the PA / PP alloy material.

Description

Technical Field

[0001] The invention belongs to the technical field of elastomer materials, and in particular relates to a thermoplastic elastomer material and a preparation method and application thereof. Background Art

[0002] Thermoplastic elastomer, referred to as TPE (Thermoplastic Elastomer), is a thermoplastic elastomer material produced by mixing rubber, plastic, compatibilizer and filler through a twin-screw extruder. At present, thermoplastic elastomers are widely used in many industries such as automobiles, home appliances, construction, wires and cables, etc.

[0003] Overmolding utilizes the compatibility of elastomer materials and hard plastics when softened and melted. The better the compatibility of the two materials, the easier it is to bond. A bonding layer is formed on the contact surface of the hard and soft plastics, which greatly improves the adhesion of the elastomer and plastic overmolding. The secondary overmolding process is widely used in the automotive, home appliances and consumer goods fields because it can improve the sealing, aesthetics and convenience of the product structure.

[0004] As one of the five engineering plastics with the best comprehensive performance, PA has become the material of choice for many automotive structural parts due to its excellent mechanical strength and long-term heat resistance. However, it also has the disadvantages of high water absorption and reduced performance rigidity after water absorption. The PA / PP alloy material modified by blending PP and PA can effectively improve the problem of poor rigidity of PA materials after water absorption, and can also play a good role in improving the chemical corrosion resistance of nylon materials.

[0005] At present, there have been a lot of research on PA encapsulation materials. For example, patent CN112694761A introduces a new material, maleic anhydride grafted POE, to enhance the adhesion and compatibility between polar and non-polar materials, increase the fluidity of the system and the adhesion between the material and nylon. However, compared with PA, the PA / PP alloy material has lower adhesive components, and more adhesive components need to be added to improve the compatibility with PA / PP. Secondly, in the original SEBS / olefin graft system, the high crystallinity of the olefin will affect the adhesive performance, so it is difficult for the elastomer to increase the Shore hardness.

[0006] Therefore, developing a coating material with high Shore hardness and good adhesion for PA / PP alloy materials has important research significance and application value. Summary of the invention

[0007] The object of the present invention is to overcome the defects or shortcomings of the prior art and provide a thermoplastic elastomer material. The present invention uses styrene elastomer and polyamide elastomer for compounding, and adds white oil to improve the processing performance of styrene elastomer, and a compatibilizer to improve the compatibility between styrene elastomer and polyamide elastomer. The obtained thermoplastic elastomer material has good Shore hardness and good adhesion with PA / PP alloy material, and can be widely used as a coating material for PA / PP alloy material.

[0008] Another object of the present invention is to provide a method for preparing the above-mentioned thermoplastic elastomer material.

[0009] Another object of the present invention is to provide the use of the above-mentioned thermoplastic elastomer material as a coating material in coating PA / PP alloy material.

[0010] In order to achieve the above-mentioned invention object, the present invention adopts the following technical scheme:

[0011] A thermoplastic elastomer material comprising the following components in parts by weight:

[0012] 10-40 parts of styrene elastomer,

[0013] 10-40 parts of white oil,

[0014] 5-15 parts of polyamide elastomer,

[0015] Compatibilizer 5-15 parts,

[0016] Filling 0-30 parts.

[0017] Styrene elastomers can adhere to materials such as PS, PE, PP, PC and EVA, but studies have shown that if styrene elastomers are used to coat PA / PP alloy materials, there are problems of low Shore hardness and poor adhesion. This is mainly because styrene elastomers add grafts to encapsulate PA. Increasing the content of grafts can increase the Shore hardness of the material, but the grafts have strong crystallinity, which directly affects the bonding performance. Therefore, it is difficult for traditional styrene elastomers to encapsulate PA / PP alloy materials to achieve both high Shore hardness and strong adhesion.

[0018] After repeated studies, it was found that by compounding styrene elastomer and polyamide elastomer, adding white oil to improve the processing properties of styrene elastomer, and using compatibilizer to improve the compatibility between styrene elastomer and polyamide elastomer, the obtained thermoplastic elastomer material has a more suitable Shore hardness and good adhesion to PA / PP alloy materials, and can be used for secondary overmolding of PA / PP alloy materials. Among them, polyamide elastomer and compatibilizer can provide compatibility and adhesion together, and then compound with styrene elastomer to adjust the hardness and processing properties of the material.

[0019] The dosage relationship between styrene elastomer, compatibilizer and polyamide elastomer has a great influence on the Shore hardness and the adhesion with PA / PP alloy materials. If the dosage of polyamide elastomer is too high, the Shore hardness is too high and the adhesion is low; if the dosage of polyamide elastomer is too low, the system is not easy to encapsulate.

[0020] Conventional styrene elastomers, white oils, polyamide elastomers, compatibilizers, and fillers in the art can be used in the present invention.

[0021] Preferably, the styrene elastomer is one or more of hydrogenated poly(styrene-b-isoprene), hydrogenated poly(styrene-b-butadiene-b-styrene), hydrogenated poly(styrene-b-isoprene-b-styrene) or hydrogenated poly(styrene-b-isoprene / butadiene-b-styrene).

[0022] Preferably, the kinematic viscosity of the white oil is 30 to 90 mm 2 / s.

[0023] The kinematic viscosity is measured according to standard ASTM D455-2015.

[0024] Preferably, the polyamide elastomer is TPAE.

[0025] Preferably, the polyamide type of the hard segment in the polyamide elastomer is nylon 12 series, and the Shore hardness is 20D-40D.

[0026] Shore hardness is measured according to ISO 7619-2010.

[0027] Preferably, the compatibilizer is one or more of maleic anhydride grafted styrene copolymers, maleic anhydride grafted olefin copolymers or maleic anhydride grafted polyolefins.

[0028] Preferably, the filler is one or more of calcium carbonate, talc, wollastonite, carbon black or mineral powder.

[0029] Preferably, the thermoplastic elastomer material further comprises other additives.

[0030] More preferably, the other auxiliary agent is one or more of an antioxidant or a UV resistant agent.

[0031] More preferably, the antioxidant is one or more of hindered phenol antioxidants, phosphites or diphenylamine antioxidants, and the weight portion of the antioxidant is 0.1 to 0.5 parts.

[0032] Further preferably, the UV resistant agent is one or more of a hindered amine composite UV resistant agent or a benzotriazole UV resistant agent, and the weight portion of the UV resistant agent is 0.2 to 1.0 parts.

[0033] The preparation method of the above-mentioned thermoplastic elastomer material comprises the following steps: mixing styrene elastomer and white oil; then uniformly mixing with the remaining components (polyamide elastomer, compatibilizer, filler and other additives (if any)) to obtain a mixture; and melt-extruding and granulating the mixture to obtain the thermoplastic elastomer material.

[0034] Preferably, the preparation method of the thermoplastic elastomer material comprises the following steps: adding styrene elastomer and white oil into a low-speed mixer, stirring at 50-100 rpm for 4-6 hours to obtain styrene elastomer / white oil; then stirring styrene elastomer / white oil, polyamide elastomer, compatibilizer, filler and other additives in a high-speed mixer at 300-500 rpm for 3-5 minutes to obtain a mixture; then adding the mixture into a twin-screw extruder for melt extrusion and granulation to obtain the thermoplastic elastomer material; the temperature of each section of the twin-screw extruder is 170-230°C, the aspect ratio is 40-56:1, the screw speed is 300-500 rpm, and the residence time of the entire extrusion process is approximately 50-100s.

[0035] The use of the above-mentioned thermoplastic elastomer material as a rubber encapsulating material in coating the PA / PP alloy material is also within the protection scope of the present invention.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] The present invention utilizes styrene elastomer and polyamide elastomer for compounding, and adds white oil to improve the processing performance of styrene elastomer, and a compatibilizer improves the compatibility between styrene elastomer and polyamide elastomer. The obtained thermoplastic elastomer material has good Shore hardness and good adhesion with PA / PP alloy material, and can be widely used as a coating material for PA / PP alloy material. DETAILED DESCRIPTION

[0038] The present invention is further described below in conjunction with examples. These examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples that do not specify specific conditions are usually carried out according to conventional conditions in the art or according to the conditions recommended by the manufacturer; the raw materials, reagents, etc. used, unless otherwise specified, are all raw materials and reagents that can be obtained from commercial channels such as conventional markets. Any non-substantial changes and substitutions made by those skilled in the art on the basis of the present invention belong to the scope of protection claimed by the present invention.

[0039] Some of the reagents selected in the embodiments and comparative examples of the present invention are described as follows:

[0040] Styrene elastomer 1#, Kraton, hydrogenated poly(styrene-b-butadiene-b-styrene), SEBS G1651;

[0041] Styrene elastomer 2#, Kuraray, hydrogenated poly(styrene-b-isoprene-b-styrene), SEEPS 4055;

[0042] White oil 1#: 150N, CNOOC, kinematic viscosity 30mm 2 / s;

[0043] White oil 2#: KN4006, PetroChina, kinematic viscosity 50mm 2 / s;

[0044] White oil 3#: KN4008, PetroChina, kinematic viscosity 90mm 2 / s;

[0045] White oil 4#: KN4010, kinematic viscosity is 160mm 2 / s;

[0046] Polyamide elastomer 1#, Arkema, 2533, PA12 series TPAE, Shore hardness 25D;

[0047] Polyamide elastomer 2#, Arkema, 7233, PA12 series TPAE, Shore hardness is 70D;

[0048] Polyamide elastomer 3#, Arkema, 35R53, PA11 series TPAE, Shore hardness 25D;

[0049] Polyamide elastomer 4#, Arkema, 4533, PA12 series TPAE, Shore hardness is 40D;

[0050] Polyurethane elastomer, Wanhua TPU, WHT 1180, Shore hardness 25D;

[0051] Compatibilizer 1#: Kraton Polymer, SEBS FG 1901, maleic anhydride grafted styrene copolymer;

[0052] Compatibilizer 2#: Dow Chemical, Fusabond N493, maleic anhydride grafted olefin copolymer;

[0053] Compatibilizer 3#: BONDYRAM 1001CN, maleic anhydride grafted polyolefin copolymer;

[0054] Filler: activated heavy calcium carbonate, commercially available;

[0055] Other additives: Irganox 1010 and Irgafos 168, mixed at a ratio of 1:1, both Irganox 1010 and Irgafos 168 are commercially available.

[0056] It should be understood that, unless otherwise specified, certain components (such as fillers, other additives, etc.) in the examples and comparative examples are the same commercially available products.

[0057] The preparation method of the thermoplastic elastomer material of each embodiment and comparative example of the present invention is as follows:

[0058] (1) Weigh the raw materials according to the weight ratio;

[0059] (2) mixing the white oil with styrene elastomer (SEBS) in a low-speed mixer at room temperature at 50 rpm for 4 h to obtain SEBS / white oil;

[0060] (3) Mixing the polyamide elastomer, SEBS / white oil, compatibilizer, filler and other additives in a high-speed mixer at a speed of 400 rpm for 3 min;

[0061] (4) The mixed raw materials are added into a twin-screw extruder, and after melt extrusion, they are cooled and granulated. The extrusion temperature is 210° C., the aspect ratio is 56:1, the screw speed is 400 rpm, and the residence time of the entire extrusion process is about 100 s.

[0062] The thermoplastic elastomer materials of the embodiments and comparative examples of the present invention were tested as follows:

[0063] The particle material prepared according to the above method was dried in a forced air oven at 70°C for 2 hours, and then the dried particles were made into standard specimens on an injection molding machine for testing.

[0064] Shore hardness: measured in accordance with ISO 7619-2010 standard, with a reading time of 15s; Shore hardness of 60-90A can meet the application requirements.

[0065] Lagging peel strength: The test method is in accordance with VDI 2019. The specific process is: first, the PA / PP alloy material (Kingfa, PAP2-C300) is made into a 2.0mm thick 150*40mm rectangular plate by injection molding or molding, and then the rectangular plate is placed in the lagging mold. The thermoplastic elastomer material is bonded to the surface of the PA / PP sheet by injection molding. The injection molding temperature is 250°C. Use a universal testing machine and a special fixture to peel the TPE soft glue from the lagging test plate. Measure and record the force during the peeling process. The larger the value, the greater the lagging peel strength. When the lagging peel strength reaches 2.0N / mm, it means that the application requirements can be met.

[0066] Examples 1 to 12

[0067] This embodiment provides a series of thermoplastic elastomer materials, and the formulas thereof are shown in Table 1.

[0068] Table 1 Formulas of Examples 1 to 12 (parts)

[0069]

[0070]

[0071] Comparative Examples 1 to 9

[0072] This comparative example provides a series of thermoplastic elastomer materials, and the formulas thereof are shown in Table 2.

[0073] Table 2 Formulas of Comparative Examples 1 to 9

[0074]

[0075] The test was carried out according to the above test method, and the test results are shown in Table 3.

[0076] Table 3 Performance test results of thermoplastic elastomer materials provided in the examples and comparative examples

[0077]

[0078]

[0079] It can be seen from the above test results that the thermoplastic elastomer material provided in each embodiment has a higher Shore hardness and has good adhesion to the PA / PP alloy material. The peel force is ≥3.0N / mm, which can fully meet the application requirements. Among them, the comprehensive performance of Example 1 is the best. In Comparative Example 1, no polyamide elastomer and compatibilizer for improving the compatibility between the two elastomers were added, and the non-polar SEBS had basically no adhesion to PA / PP; in Comparative Example 2, no polyamide elastomer was added, the system polarity was insufficient, and there was no adhesion to the matrix; in Comparative Example 3, no compatibilizer was added, and the non-polar SEBS and polar TPAE had poor compatibility and could not form good adhesion; in Comparative Example 4, no styrene elastomer and white oil were added, and TPAE had high crystallinity, resulting in poor adhesion; in Comparative Example 5, no styrene was added Elastomer, TPAE is plasticized by white oil and cannot form good elasticity and adhesion; in Comparative Example 6, no white oil is added, the fluidity of the system is very low and it has no processability; in Comparative Example 7, polyurethane elastomer and styrene elastomer are compounded, and the processing temperature of polyurethane is low, and it cannot form adhesion with PA / PP matrix; in Comparative Example 8, the amount of polyamide elastomer is too large, and the crystallinity is too strong, resulting in decreased adhesion; in Comparative Example 9, the amount of styrene elastomer is too large, the content of non-polar components is high, and the fluidity of the system is low, which affects the adhesion.

[0080] Those skilled in the art will appreciate that the embodiments herein are intended to help readers understand the principles of the present invention, and should be understood that the protection scope of the present invention is not limited to such specific statements and embodiments. Those skilled in the art can make various other specific variations and combinations that do not deviate from the essence of the present invention based on the technical revelations disclosed by the present invention, and these variations and combinations are still within the protection scope of the present invention.

Claims

1. A thermoplastic elastomer material, characterized in that: The composition comprises the following components in parts by weight: 30~40 parts of styrene elastomer, 10~40 parts of white oil, Polyamide elastomer 10~15 parts, Compatibilizer 5~15 parts, Filling 0~30 parts; The Shore hardness of the polyamide elastomer is 20D-40D; the Shore hardness is measured according to ISO 7619-2010 standard; The filler is one or more of calcium carbonate, talc, wollastonite or carbon black.

2. A thermoplastic elastomer material, characterized in that: The composition comprises the following components in parts by weight: 30~40 parts of styrene elastomer, 10~40 parts of white oil, Polyamide elastomer 10~15 parts, Compatibilizer 5~15 parts, Filling 0~30 parts; The Shore hardness of the polyamide elastomer is 20D-40D; the Shore hardness is measured according to ISO 7619-2010 standard; The filler is mineral powder and the amount of the filler is not zero.

3. The thermoplastic elastomer material according to claim 1 or 2, characterized in that: The styrene elastomer is one or more of hydrogenated poly(styrene-b-isoprene), hydrogenated poly(styrene-b-butadiene-b-styrene), hydrogenated poly(styrene-b-isoprene-b-styrene) or hydrogenated poly(styrene-b-isoprene / butadiene-b-styrene).

4. The thermoplastic elastomer material according to claim 1 or 2, characterized in that: The kinematic viscosity of the white oil is 30-90 mm 2 / s; the kinematic viscosity is measured according to standard ASTM D455-2015.

5. The thermoplastic elastomer material according to claim 1 or 2, characterized in that: The polyamide elastomer is TPAE.

6. The thermoplastic elastomer material according to claim 1 or 2, characterized in that: The polyamide type of the hard segment in the polyamide elastomer is nylon 12 series.

7. The thermoplastic elastomer material according to claim 1 or 2, characterized in that: The compatibilizer is one or more of maleic anhydride grafted styrene copolymers or maleic anhydride grafted polyolefins.

8. The thermoplastic elastomer material according to claim 1 or 2, characterized in that: The thermoplastic elastomer material also includes other additives; the other additives are one or more of antioxidants or UV resistant agents.

9. The method for preparing the thermoplastic elastomer material according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: mixing styrene elastomer and white oil; then uniformly mixing with the remaining components to obtain a mixture; and melting and extruding the mixture and granulating to obtain the thermoplastic elastomer material.

10. Use of the thermoplastic elastomer material according to any one of claims 1 to 8 as a coating material in coating PA / PP alloy materials.

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