A thermoplastic elastomer composition and preparation method thereof

Abstract

The present application relates to the technical field of compositions of polymer compounds, and specifically discloses a thermoplastic elastomer composition and a preparation method thereof. The thermoplastic elastomer composition is mainly made of the following raw materials in parts by weight: 20-40 parts of SEBS elastomer, 8-20 parts of PP resin, 30-60 parts of mineral oil, 20-30 parts of ethylene-acrylic acid copolymer, 10-20 parts of activated calcium carbonate, 0.1-0.5 parts of amino-containing silane coupling agent, 0.5-1 parts of lubricant, 0.5-1 parts of anti-aging compounding agent, and 0.5-3 parts of colorant. The thermoplastic elastomer composition has the characteristics of good hardness, high tensile strength, high tear strength, high glass surface peeling residual rate, and good adhesion to glass, showing better comprehensive performance, suitable for primer-free glass injection molding bonding packaging, and meeting market demand.

Description

Technical Field

[0001] The present application relates to the technical field of polymer compound compositions, and more specifically, to a thermoplastic elastomer composition and a preparation method thereof. Background Art

[0002] Thermoplastic elastomer composition is a composition of polymer compounds with both plastic and rubber properties, and has a wide range of applications in the fields of automobiles, medical treatment, packaging, kitchens, home appliances, etc., such as glass injection molding bonding packaging, glass surface buffer layer, glass middle diaphragm layer, etc. When the thermoplastic elastomer composition is injection molded and bonded to the glass surface, the thermoplastic elastomer composition is first heated and melted to obtain a molten thermoplastic elastomer composition, and then a layer of the molten thermoplastic elastomer composition is injection molded on the glass surface, and then cured to form a rubber bonding layer. After the rubber bonding layer is peeled off from the glass surface, the glass surface peeling residue rate is basically 0, and the bonding is poor. In order to increase the bonding between the rubber bonding layer and the glass, a primer is often pre-coated on the glass surface to increase the bonding. However, the primer contains a large amount of organic solvents, which are easy to volatilize and produce harmful substances when used, posing a safety hazard to the environment and human body. Summary of the invention

[0003] In order to increase the peeling residue rate on the glass surface and enhance the adhesion, the present application provides a thermoplastic elastomer composition and a preparation method thereof.

[0004] In a first aspect, the present application provides a thermoplastic elastomer composition, which adopts the following technical solution:

[0005] A thermoplastic elastomer composition is mainly prepared from the following raw materials in parts by weight: 20-40 parts of SEBS elastomer, 8-20 parts of PP resin, 30-60 parts of mineral oil, 20-30 parts of ethylene-acrylic acid copolymer, 10-20 parts of activated calcium carbonate, 0.1-0.5 parts of amino-containing silane coupling agent, 0.5-1 parts of lubricant, 0.5-1 parts of anti-aging compounding agent and 0.5-3 parts of colorant; the activated calcium carbonate is obtained by treating calcium carbonate with 3-allyloxypropyltrimethoxysilane, hexafluoroisopropyl methacrylate and 3-(N-allylamino)propyltrimethoxysilane.

[0006] The thermoplastic elastomer composition of the present application has Shore A hardness>70, tensile strength>8MPa, tear strength>30kN / m, glass surface peeling residual rate>90% through the mutual coordination between raw materials, showing good hardness, high tensile strength, high tear strength, high glass surface peeling residual rate, good adhesion to glass, and has better comprehensive performance. It does not need to pre-coat the glass surface with a primer, avoiding the volatilization of organic solvents in the primer, reducing safety hazards to the environment and human body, and is suitable for primer-free glass injection bonding packaging to meet market demand.

[0007] The thermoplastic elastomer composition of the present application adds ethylene-acrylic acid copolymer to the raw materials, which effectively increases the bonding force and hardness. Adding an amino-containing silane coupling agent to the raw materials can not only enhance the interaction between the raw materials, reduce the internal stress concentration point, and improve the tensile strength and tear strength, but also effectively enhance the bonding ability between the thermoplastic elastomer composition and glass, and improve the glass surface peeling residual rate. Activated calcium carbonate is added to the raw materials, 3-allyloxypropyl trimethoxysilane, hexafluoroisopropyl methacrylate, 3-(N-allylamino)propyl trimethoxysilane are grafted on the surface of calcium carbonate, and active groups such as ester groups, fluorine groups, siloxy groups, and amine groups are introduced to improve the surface activity of activated calcium carbonate, increase the dispersibility, compatibility, and interfacial bonding force of activated calcium carbonate, improve the chemical bonding between it and the raw materials, reduce gaps, enhance density and cross-linked network structure stability, improve Shore hardness, tensile strength, and tear strength, and can also form chemical bonds with active groups such as hydroxyl groups on the glass surface, enhance bonding force, and improve the glass surface peeling residual rate, so that the thermoplastic elastomer composition is suitable for injection molding and bonding glass.

[0008] Optionally, the activated calcium carbonate is mainly prepared by the following method:

[0009] S1. Mix water and calcium carbonate, add 3-allyloxypropyltrimethoxysilane, stir for 2-4 hours, and filter to obtain an intermediate;

[0010] S2. Mix the organic solvent and the intermediate, add hexafluoroisopropyl methacrylate and 3-(N-allylamino)propyltrimethoxysilane, add an organic initiator, stir for 3-5 hours, filter, wash, and dry to obtain activated calcium carbonate.

[0011] Optionally, the weight ratio of calcium carbonate, 3-allyloxypropyltrimethoxysilane, hexafluoroisopropyl methacrylate, and 3-(N-allylamino)propyltrimethoxysilane is 50:(4-6):(1-3):(1-3).

[0012] By adopting the above technical scheme, 3-allyloxypropyltrimethoxysilane is first grafted on the surface of calcium carbonate, and a carbon-carbon double bond is introduced to obtain an intermediate. Then, by using a polymerization reaction, under the action of an organic initiator, hexafluoroisopropyl methacrylate and 3-(N-allylamino)propyltrimethoxysilane are grafted on the surface of the intermediate to obtain activated calcium carbonate. The preparation method of the present application ensures the stability of the grafting reaction through the mutual coordination between the various steps, and ensures the quality and use effect of the activated calcium carbonate.

[0013] Optionally, the weight ratio of calcium carbonate to organic initiator is 50:(0.1-0.5).

[0014] By adopting the above technical solution, the addition amount of the organic initiator is optimized, the stability of the grafting reaction is ensured, and the use effect of the activated calcium carbonate is enhanced.

[0015] Optionally, in the method for preparing activated calcium carbonate, in step S1, the average particle size of calcium carbonate is 1-10 μm. Preferably, the average particle size of calcium carbonate is 1-6 μm. In multiple embodiments, the average particle size of calcium carbonate is 2.6 μm, and the average particle size can also be set to 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm as needed, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0016] Optionally, in the method for preparing activated calcium carbonate, in step S1, the weight ratio of calcium carbonate to water is 5:(20-30). In multiple embodiments, the weight ratio of calcium carbonate to water is 1:5, and the weight ratio can also be set to 5:20, 5:23, 5:28, 5:30 as needed, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0017] Optionally, in the method for preparing activated calcium carbonate, in step S1, the temperature is 5-15° C. In multiple embodiments, the temperature is 10° C., and the temperature can also be set to 5° C., 8° C., 13° C., 15° C. as required, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0018] Optionally, in the method for preparing activated calcium carbonate, in step S2, the organic initiator is one or more of di-tert-butyl peroxide, tert-butyl peroxyacetate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, and didodecanoyl peroxide.

[0019] Optionally, in the method for preparing activated calcium carbonate, the weight ratio of calcium carbonate to organic solvent is 5:(30-70). In multiple embodiments, the weight ratio of calcium carbonate to organic solvent is 1:10, and the weight ratio can also be set to 5:30, 5:40, 5:60, 5:70 as required, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0020] Optionally, in the activated calcium carbonate preparation method, the organic solvent is ethanol and cyclohexanone, and the weight ratio of ethanol to cyclohexanone is (1-3): (1-3). In multiple embodiments, the weight ratio of ethanol to cyclohexanone is 1:2, and the weight ratio can also be set to 1:1, 1:3, 2:1, 2:3, 3:1, 3:2 as needed, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0021] Optionally, the amino-containing silane coupling agent is one or more of silane coupling agent KH-540, silane coupling agent KH-550, silane coupling agent KH-792, silane coupling agent NQ-62, and silane coupling agent WD-53.

[0022] By adopting the above technical solution, the amino-containing silane coupling agent is optimized, which facilitates the selection of the amino-containing silane coupling agent.

[0023] Optionally, the SEBS elastomer is one or more of SEBS elastomer YH-502T, SEBS elastomer YH-503T, and SEBS elastomer Li Changrong 7551.

[0024] Optionally, the flow rate MFR (230° C., 2.16 kg) of the PP resin is 10-100 g / 10 min.

[0025] Optionally, the mineral oil is one or more of white oil, paraffin oil, naphthenic oil, and aromatic oil;

[0026] The lubricant is one or more of stearic acid, zinc stearate, calcium stearate, oleamide, erucamide, ethylene bis stearamide, and polyethylene wax.

[0027] By adopting the above technical solution, the mineral oil and lubricant are optimized, which facilitates the selection of the mineral oil and lubricant. The mineral oil and lubricant are used to improve the fluidity and softness of the thermoplastic elastomer composition, reduce adhesion, improve production efficiency, and ensure the quality of the thermoplastic elastomer composition.

[0028] Preferably, the mineral oil is white oil, and the kinematic viscosity of the white oil at 40°C is 60-170 mm 2 / s, the flash point of the white oil is ≥260°C.

[0029] Optionally, the lubricant is erucic acid amide and zinc stearate, and the weight ratio of erucic acid amide and zinc stearate is (1-3): (1-3). In multiple embodiments, the weight ratio of erucic acid amide and zinc stearate is 1:1, and the weight ratio can also be set to 1:2, 1:3, 2:1, 2:3, 3:1, 3:2 as needed, but it is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0030] Optionally, the anti-aging compound comprises an antioxidant and an ultraviolet absorber, and the weight ratio of the antioxidant to the ultraviolet absorber is (1-3):(1-3).

[0031] By adopting the above technical solution, the anti-aging compounding agent uses antioxidants and ultraviolet absorbers, and is reasonably proportioned, so that the thermoplastic elastomer composition has good antioxidant and ultraviolet resistance, and the service life is extended. In multiple embodiments, the weight ratio of antioxidants and ultraviolet absorbers is 1:1, and the weight ratio can also be set to 1:2, 1:3, 2:1, 2:3, 3:1, 3:2 as needed, but it is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0032] Optionally, the antioxidant is one or more of antioxidant 1024, antioxidant 1010, antioxidant 264, antioxidant 168, and antioxidant B215;

[0033] The ultraviolet absorber is one or more of the ultraviolet absorber UV-531, ultraviolet absorber UV-1130, ultraviolet absorber UV-9, ultraviolet absorber UV-P, and ultraviolet absorber UV-O.

[0034] By adopting the above technical solution, antioxidants and ultraviolet absorbers are optimized, which facilitates the selection of antioxidants and ultraviolet absorbers, so that the thermoplastic elastomer composition can still maintain good stability and mechanical properties when exposed to oxygen and ultraviolet light for a long time.

[0035] Optionally, the antioxidants are two kinds of antioxidants, namely, antioxidant 1010 and antioxidant 168, and the weight ratio of antioxidant 1010 to antioxidant 168 is (1-3):(1-3). In multiple embodiments, the weight ratio of antioxidant 1010 to antioxidant 168 is 1:1, and the weight ratio can also be set to 1:2, 1:3, 2:1, 2:3, 3:1, 3:2 as needed, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0036] Optionally, the colorant is one or more of carbon black, titanium dioxide, zinc dioxide, zinc oxide, and organic pigments.

[0037] By adopting the above technical solution, the colorant is optimized and the selection of the colorant is facilitated.

[0038] In a second aspect, the present application provides a method for preparing a thermoplastic elastomer composition, which adopts the following technical solution:

[0039] A method for preparing a thermoplastic elastomer composition mainly comprises the following steps:

[0040] SEBS elastomer, PP resin, mineral oil, ethylene-acrylic acid copolymer, activated calcium carbonate, amino-containing silane coupling agent, lubricant, anti-aging compounding agent and colorant are mixed, then melt-extruded and granulated at a temperature of 160-180° C. to obtain a thermoplastic elastomer composition.

[0041] By adopting the above technical solution, the preparation of the thermoplastic elastomer composition is facilitated. In multiple embodiments, melt extrusion is performed at a temperature of 170°C, and the temperature can also be set to 160°C, 162°C, 165°C, 167°C, 172°C, 175°C, 177°C, 180°C as required, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0042] Optionally, in the preparation method of the thermoplastic elastomer composition, a twin-screw extruder is used for melt extrusion, and the screw speed is 400-600 rpm. In multiple embodiments, the screw speed is 500 rpm, and the screw speed can also be set to 400 rpm, 430 rpm, 450 rpm, 480 rpm, 530 rpm, 550 rpm, 580 rpm, 600 rpm as needed, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0043] In summary, this application has at least the following beneficial effects:

[0044] The thermoplastic elastomer composition of the present application adds ethylene-acrylic acid copolymer to the raw materials to effectively increase the bonding force and hardness. Add amino-containing silane coupling agent to enhance interaction, reduce internal stress concentration points, and improve the bonding ability between it and glass. Add activated calcium carbonate, and introduce active groups such as ester groups, fluorine groups, siloxy groups, and amine groups on the surface of calcium carbonate to improve surface activity, increase dispersibility, compatibility, and interfacial bonding, improve chemical bonding, reduce voids, increase density, and cross-linked network structure stability, and can form chemical bonds with active groups such as hydroxyl groups on the glass surface to enhance bonding. And through the mutual coordination between the raw materials, the Shore hardness A of the thermoplastic elastomer composition is > 70, tensile strength > 8MPa, tear strength > 30kN / m, and glass surface peeling residual rate > 90%, showing good hardness, high tensile strength, high tear strength, high glass surface peeling residual rate, and good adhesion to glass. It has better comprehensive performance and is suitable for primer-free glass injection molding bonding packaging to meet market demand. DETAILED DESCRIPTION

[0045] In order to make the present application easier to understand, the present application will be further described in detail below in conjunction with the examples, which are merely illustrative and are not intended to limit the scope of application of the present application. The raw materials or components used in the present application can be obtained through commercial routes or conventional methods unless otherwise specified.

[0046] Preparation Example

[0047] Preparation Example 1

[0048] An activated calcium carbonate is mainly prepared by the following method:

[0049] S1. Add 50 kg of calcium carbonate to 250 kg of water at a temperature of 10° C. and a stirring rate of 500 rpm, and stir for 3 min. Add 5 kg of 3-allyloxypropyltrimethoxysilane, and stir for 3 h. Filter to obtain an intermediate.

[0050] Among them, the average particle size of calcium carbonate is 2.6μm, and it is selected from Jiangxi Hengshengtai New Materials Co., Ltd.

[0051] S2. Add all the intermediates obtained in step S1 to 500 kg of organic solvent at a stirring rate of 500 rpm, and stir for 3 min. Add 2 kg of hexafluoroisopropyl methacrylate and 2 kg of 3-(N-allylamino)propyltrimethoxysilane, and stir for 3 min. Add 0.2 kg of organic initiator, stir for 4 h, filter, wash once with 200 kg of cyclohexanone, wash once with 200 kg of ethanol, wash once with 200 kg of water, and dry to obtain activated calcium carbonate.

[0052] Among them, the organic solvents are ethanol and cyclohexanone, and the weight ratio of ethanol to cyclohexanone is 1:2; the organic initiator is di-tert-butyl peroxide.

[0053] Preparation Example 2

[0054] An activated calcium carbonate, which is different from Preparation Example 1 in that, in the preparation method of the activated calcium carbonate, the added amounts of 3-allyloxypropyltrimethoxysilane, hexafluoroisopropyl methacrylate, and 3-(N-allylamino)propyltrimethoxysilane are different, and the added amount of 3-allyloxypropyltrimethoxysilane is 4kg; the added amount of hexafluoroisopropyl methacrylate is 1kg; and the added amount of 3-(N-allylamino)propyltrimethoxysilane is 3kg.

[0055] Preparation Example 3

[0056] An activated calcium carbonate, which is different from Preparation Example 1 in that, in the preparation method of the activated calcium carbonate, the added amounts of 3-allyloxypropyltrimethoxysilane, hexafluoroisopropyl methacrylate, and 3-(N-allylamino)propyltrimethoxysilane are different, and the added amount of 3-allyloxypropyltrimethoxysilane is 6kg; the added amount of hexafluoroisopropyl methacrylate is 3kg; and the added amount of 3-(N-allylamino)propyltrimethoxysilane is 1kg.

[0057] Example

[0058] Table 1 Amount of each raw material used in the thermoplastic elastomer composition (unit: kg)

[0059]

[0060] Example 1

[0061] A thermoplastic elastomer composition, the raw materials and raw material ratios of which are shown in Table 1.

[0062] Among them, SEBS elastomer is Yuehua SEBS elastomer YH-502T; PP resin is Formosa Plastics PP resin 1450T; mineral oil is white oil, and the white oil is No. 100 white oil; ethylene-acrylic acid copolymer is Exxon ethylene-acrylic acid copolymer Escor 5200; activated calcium carbonate is prepared by the method of Preparation Example 1; the amino-containing silane coupling agent is silane coupling agent KH-550; the lubricant is erucamide and zinc stearate, and the weight ratio of erucamide and zinc stearate is 1:1; the anti-aging compounding agent is an antioxidant and an ultraviolet absorber, and the weight ratio of the antioxidant and the ultraviolet absorber is 1:1, the antioxidant is antioxidant 1010 and antioxidant 168, and the weight ratio of antioxidant 1010 and antioxidant 168 is 1:1, and the ultraviolet absorber is ultraviolet absorber UV-531; the colorant is carbon black, the average particle size of carbon black is 18μm, and it is selected from Shandong Wanhua Tianhe New Materials Co., Ltd.

[0063] A method for preparing a thermoplastic elastomer composition mainly comprises the following steps:

[0064] Using a mixer, add mineral oil to the SEBS elastomer, stir for 5 minutes, and let stand for 12 hours. Then add PP resin, ethylene-acrylic acid copolymer, activated calcium carbonate, amino-containing silane coupling agent, lubricant, anti-aging compounding agent, and colorant, stir for 5 minutes to obtain a mixture.

[0065] The mixed material was melt-extruded and granulated using a twin-screw extruder at a temperature of 170° C. and a screw speed of 500 rpm to obtain a thermoplastic elastomer composition.

[0066] Example 2

[0067] A thermoplastic elastomer composition, which is different from Example 1 in that the raw material ratio of the thermoplastic elastomer composition is different, and the raw material ratio of the thermoplastic elastomer composition is shown in Table 1.

[0068] Example 3

[0069] A thermoplastic elastomer composition, which is different from Example 1 in that the raw material ratio of the thermoplastic elastomer composition is different, and the raw material ratio of the thermoplastic elastomer composition is shown in Table 1.

[0070] Example 4

[0071] A thermoplastic elastomer composition is different from Example 1 in that the activated calcium carbonate in the raw materials of the thermoplastic elastomer composition has a different source, and the activated calcium carbonate is prepared by the method of Preparation Example 2.

[0072] Example 5

[0073] A thermoplastic elastomer composition is different from Example 1 in that the activated calcium carbonate in the raw materials of the thermoplastic elastomer composition has a different source, and the activated calcium carbonate is prepared by the method of Preparation Example 3.

[0074] Comparative Example

[0075] Comparative Example 1

[0076] A thermoplastic elastomer composition, which is different from Example 1 in that no ethylene-acrylic acid copolymer is added to the raw materials of the thermoplastic elastomer composition.

[0077] Comparative Example 2

[0078] A thermoplastic elastomer composition, which is different from Example 1 in that the amount of ethylene-acrylic acid copolymer added in the raw materials of the thermoplastic elastomer composition is different, and the amount of ethylene-acrylic acid copolymer added is 10 kg.

[0079] Comparative Example 3

[0080] A thermoplastic elastomer composition, which is different from Example 1 in that the amount of ethylene-acrylic acid copolymer added in the raw materials of the thermoplastic elastomer composition is different, and the amount of ethylene-acrylic acid copolymer added is 40 kg.

[0081] Comparative Example 4

[0082] A thermoplastic elastomer composition, which is different from Example 1 in that no amino-containing silane coupling agent is added to the raw materials of the thermoplastic elastomer composition.

[0083] Comparative Example 5

[0084] A thermoplastic elastomer composition is different from Example 1 in that an amino-containing silane coupling agent is replaced by an equal amount of 3-allyloxypropyltrimethoxysilane in the raw materials of the thermoplastic elastomer composition.

[0085] Comparative Example 6

[0086] A thermoplastic elastomer composition, which is different from Example 1 in that no activated calcium carbonate is added to the raw materials of the thermoplastic elastomer composition.

[0087] Comparative Example 7

[0088] A thermoplastic elastomer composition, which is different from Example 1 in that an equal amount of calcium carbonate is used to replace activated calcium carbonate in the raw materials of the thermoplastic elastomer composition.

[0089] Comparative Example 8

[0090] A thermoplastic elastomer composition, which differs from Example 1 in that in the raw materials of the thermoplastic elastomer composition, in the preparation method of activated calcium carbonate, an equal amount of 3-allyloxypropyltrimethoxysilane is used to replace hexafluoroisopropyl methacrylate and 3-(N-allylamino)propyltrimethoxysilane.

[0091] Comparative Example 9

[0092] A thermoplastic elastomer composition, which differs from Example 1 in that, in the raw materials of the thermoplastic elastomer composition, in the preparation method of activated calcium carbonate, an equal amount of hexafluoroisopropyl methacrylate is used to replace 3-(N-allylamino)propyltrimethoxysilane.

[0093] Comparative Example 10

[0094] A thermoplastic elastomer composition, which differs from Example 1 in that, in the raw materials of the thermoplastic elastomer composition, in the preparation method of activated calcium carbonate, an equal amount of 3-(N-allylamino)propyltrimethoxysilane is used to replace hexafluoroisopropyl methacrylate.

[0095] Performance Testing

[0096] The thermoplastic elastomer compositions obtained in Examples 1-5 and Comparative Examples 1-10 were respectively taken, and the following performance tests were performed on the thermoplastic elastomer compositions. The test results are shown in Table 2.

[0097] Wherein, the Shore A hardness of the thermoplastic elastomer composition is tested according to ISO 868-2003.

[0098] The tensile strength of the thermoplastic elastomer composition was tested according to Type I in ISO 37-2017 at a test speed of 500 mm / min.

[0099] The tear strength of the thermoplastic elastomer composition was tested according to Type B in ISO 34-1-2015 at a test speed of 500 mm / min.

[0100] The glass surface peeling residual rate is calculated by the following method: the thermoplastic elastomer composition is heated to 200°C and melted to obtain a molten thermoplastic elastomer composition. Then a layer of molten thermoplastic elastomer composition is injection molded on a glass surface with a thickness of 3 mm. After that, the thermoplastic elastomer composition is left to stand for 6 hours at a temperature of 80°C, and the thermoplastic elastomer composition is cured on the glass surface to form a rubber bonding layer with a thickness of 1 mm. Then the temperature is lowered to 23°C, the rubber bonding layer is peeled off from the glass surface, and the glass surface peeling residual rate is calculated. Moreover, the higher the glass surface peeling residual rate, the better the bonding property of the thermoplastic elastomer composition.

[0101] Glass surface peeling residual rate / (%) = weight of rubber adhesive layer after peeling / weight of rubber adhesive layer before peeling × 100%.

[0102] Table 2 Test results

[0103]

[0104] As can be seen from Table 2, the thermoplastic elastomer composition of the present application has high Shore hardness, tensile strength and tear strength, with Shore hardness A of 73-76, tensile strength of 8.3-8.7 MPa and tear strength of 31.5-32.6 kN / m, showing the advantages of good hardness, high tensile strength and high tear strength. It also has a high glass surface peeling residual rate of 93-95%, showing the advantage of good adhesion to glass, meeting market demand.

[0105] Comparative Examples 1-3 and Example 1 are compared. In the raw materials of the thermoplastic elastomer composition of Comparative Example 1, the addition amount of ethylene-acrylic acid copolymer is 0 parts by weight; in the raw materials of the thermoplastic elastomer composition of Comparative Example 2, the addition amount of ethylene-acrylic acid copolymer is 10 parts by weight; in the raw materials of the thermoplastic elastomer composition of Example 1, the addition amount of ethylene-acrylic acid copolymer is 25 parts by weight; in the raw materials of the thermoplastic elastomer composition of Comparative Example 3, the addition amount of ethylene-acrylic acid copolymer is 40 parts by weight. It can be seen that with the increase in the addition amount of ethylene-acrylic acid copolymer, the Shore hardness and the glass surface peeling residual rate gradually increase and tend to be flat, while the tensile strength and tear strength gradually decrease, and when the addition amount of ethylene-acrylic acid copolymer is 20-30 parts by weight, the thermoplastic elastomer composition can have good Shore hardness, mechanical properties and adhesion.

[0106] Comparative Examples 4-5 and Example 1 are compared, and Comparative Example 4 is used as the basis. Compared with Comparative Example 4, 3-allyloxypropyltrimethoxysilane is added to the raw materials of the thermoplastic elastomer composition in Comparative Example 5; compared with Comparative Example 4, amino-containing silane coupling agent is added to the raw materials of the thermoplastic elastomer composition in Example 1. It can be seen that adding amino-containing silane coupling agent to the raw materials of the thermoplastic elastomer composition can increase tensile strength, tear strength and glass surface peeling residual rate.

[0107] Comparative Examples 6-7 are compared. No activated calcium carbonate was added to the raw materials of the thermoplastic elastomer composition of Comparative Example 6; calcium carbonate was added to the raw materials of the thermoplastic elastomer composition of Example 7. It can be seen that adding calcium carbonate to the raw materials of the thermoplastic elastomer composition can increase the Shore hardness, but significantly reduce the tensile strength, tear strength and adhesion. Combined with Example 1, activated calcium carbonate was added to the raw materials of the thermoplastic elastomer composition of Example 1. It can be seen that the treatment of calcium carbonate basically does not affect the Shore hardness, but greatly improves the tensile strength, tear strength and glass surface peeling residue rate.

[0108] Comparative Examples 8-10 and Example 1 are compared. The activated calcium carbonate of Comparative Example 8 is obtained by treating calcium carbonate with 3-allyloxypropyltrimethoxysilane; the activated calcium carbonate of Comparative Example 9 is obtained by treating calcium carbonate with 3-allyloxypropyltrimethoxysilane and hexafluoroisopropyl methacrylate; the activated calcium carbonate of Comparative Example 10 is obtained by treating calcium carbonate with 3-allyloxypropyltrimethoxysilane and 3-(N-allylamino)propyltrimethoxysilane; the activated calcium carbonate of Example 1 is obtained by treating calcium carbonate with 3-allyloxypropyltrimethoxysilane, hexafluoroisopropyl methacrylate, and 3-(N-allylamino)propyltrimethoxysilane. It can be seen from this that in the preparation method of activated calcium carbonate, 3-allyloxypropyltrimethoxysilane is first grafted on the surface of calcium carbonate, and then hexafluoroisopropyl methacrylate and 3-(N-allylamino)propyltrimethoxysilane are grafted simultaneously by polymerization reaction, and active groups such as ester group, fluorine group, siloxy group, and amine group are introduced. By utilizing the synergistic effect between them, the dispersibility of activated calcium carbonate and the bonding force between it and the raw materials can be improved, the tensile strength and tear strength can be improved, and the glass surface peeling residual rate can also be improved, so that the thermoplastic elastomer composition exhibits better comprehensive performance.

[0109] It should be noted that the embodiments described above are only used to explain the present application and do not constitute any limitation to the present application. The present application is described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present application may be modified as specified within the scope of the claims of the present application, and the present application may be revised without departing from the scope and spirit of the present application. Although the present application described therein relates to specific methods, materials and embodiments, it does not mean that the present application is limited to the specific examples disclosed therein. On the contrary, the present application can be extended to all other methods and applications with the same functions.

Claims

1. A thermoplastic elastomer composition, characterized in that: The thermoplastic elastomer composition is mainly made of the following raw materials in parts by weight: 20-40 parts of SEBS elastomer, 8-20 parts of PP resin, 30-60 parts of mineral oil, 20-30 parts of ethylene-acrylic acid copolymer, 10-20 parts of activated calcium carbonate, 0.1-0.5 parts of amino-containing silane coupling agent, 0.5-1 parts of lubricant, 0.5-1 parts of anti-aging compounding agent, and 0.5-3 parts of colorant; the activated calcium carbonate is obtained by treating calcium carbonate with 3-allyloxypropyltrimethoxysilane, hexafluoroisopropyl methacrylate, and 3-(N-allylamino)propyltrimethoxysilane; The activated calcium carbonate is mainly prepared by the following method: S1. Mix water and calcium carbonate, add 3-allyloxypropyltrimethoxysilane, stir for 2-4 hours, and filter to obtain an intermediate; S2. Mix the organic solvent and the intermediate, add hexafluoroisopropyl methacrylate and 3-(N-allylamino)propyltrimethoxysilane, add an organic initiator, stir for 3-5 hours, filter, wash, and dry to obtain activated calcium carbonate.

2. A thermoplastic elastomer composition according to claim 1, characterized in that: The weight ratio of calcium carbonate, 3-allyloxypropyltrimethoxysilane, hexafluoroisopropyl methacrylate, and 3-(N-allylamino)propyltrimethoxysilane is 50:(4-6):(1-3):(1-3).

3. A thermoplastic elastomer composition according to claim 1, characterized in that: The weight ratio of calcium carbonate to organic initiator is 50:(0.1-0.5).

4. A thermoplastic elastomer composition according to claim 1, characterized in that: The amino-containing silane coupling agent is one or more of silane coupling agent KH-540, silane coupling agent KH-550, silane coupling agent KH-792, silane coupling agent NQ-62, and silane coupling agent WD-53.

5. The thermoplastic elastomer composition according to claim 1, characterized in that: The mineral oil is one or more of white oil, paraffin oil, naphthenic oil, and aromatic oil; The lubricant is one or more of stearic acid, zinc stearate, calcium stearate, oleamide, erucamide, ethylene bis stearamide, and polyethylene wax.

6. A thermoplastic elastomer composition according to claim 1, characterized in that: The anti-aging compound comprises two kinds of agents, an antioxidant and an ultraviolet absorber, and the weight ratio of the antioxidant to the ultraviolet absorber is (1-3):(1-3).

7. A thermoplastic elastomer composition according to claim 6, characterized in that: The antioxidant is one or more of antioxidant 1024, antioxidant 1010, antioxidant 264, antioxidant 168, and antioxidant B215; The ultraviolet absorber is one or more of the ultraviolet absorber UV-531, ultraviolet absorber UV-1130, ultraviolet absorber UV-9, ultraviolet absorber UV-P, and ultraviolet absorber UV-O.

8. The thermoplastic elastomer composition according to claim 1, characterized in that: The colorant is one or more of carbon black, titanium dioxide, zinc white, zinc oxide, and organic pigments.

9. A method for preparing a thermoplastic elastomer composition according to any one of claims 1 to 8, characterized in that: The main steps are as follows: SEBS elastomer, PP resin, mineral oil, ethylene-acrylic acid copolymer, activated calcium carbonate, amino-containing silane coupling agent, lubricant, anti-aging compounding agent and colorant are mixed, then melt-extruded and granulated at a temperature of 160-180° C. to obtain a thermoplastic elastomer composition.

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