Bonding PP antistatic TPE material and preparation method and application thereof

Abstract

The invention belongs to the technical field of thermoplastic elastomer materials, and particularly relates to a PP-bonded antistatic TPE material as well as a preparation method and application thereof. The ethylene-propylene copolymer elastomer has good compatibility with PP and hydrogenated styrene elastomers, and the bonding capacity of the material and PP can be remarkably improved; pOE has the characteristics of less crystallization and slow cooling, and can not only increase the toughness of the material, but also prolong the temperature holding time of the material during injection molding after being added into the material, so that the bonding capacity of the obtained TPE and PP is improved; the polyether block amide can form an ion channel in the TPE material, so that the antistatic capacity of the material is effectively improved, and the bonding capacity of PP is basically not reduced. Through the synergistic effect of the components, the TPE material which is good in PP encapsulation property, high in antistatic property and excellent in mechanical property is obtained.

Description

Technical Field

[0001] The present invention belongs to the technical field of thermoplastic elastomer materials, and more specifically, relates to a bonding PP antistatic TPE material and a preparation method and application thereof. Background Art

[0002] Thermoplastic Elastomer (TPE) is a material that has the characteristics of high elasticity, high strength and high resilience of rubber and can be processed by injection molding. TPE has many advantages, such as environmental protection, non-toxicity and safety, wide hardness range, excellent colorability, soft touch, weather resistance, fatigue resistance, temperature resistance, excellent processing performance and no need for vulcanization. Therefore, as a new type of multifunctional environmentally friendly material, TPE has a very broad application market.

[0003] With the popularization of intelligent robots, the application of antistatic casters has gradually increased. Casters are mainly PP casters. In order to make the casters more shock-absorbing and silent, a rubber coating is usually set on the surface of the casters, which plays a certain shock-absorbing role and helps the casters to roll smoothly. At present, most of the TPE materials used to make rubber coatings on the market use carbon black as an antistatic agent. Carbon black is difficult to disperse and has a great impact on the physical properties of low-hardness TPE. If TPE with added carbon black is applied to the rubber coating of polypropylene (PP) casters, it is easy to have a weak adhesion of the rubber coating layer. The rubber layer is easy to loosen and fall off during the rolling and vibration of the casters, resulting in the problem that the casters cannot operate normally. In the related art, there are also cases where organic polymer siloxane materials are used as antistatic agents, and the antistatic effect is very good, but the rubber coating effect for PP casters is not ideal. Therefore, the existing TPE materials cannot meet the requirements of PP caster rubber coating, and there is an urgent need for a TPE material with good PP rubber coating, good antistatic effect and high mechanical strength. Summary of the invention

[0004] The technical problem to be solved by the present invention is to overcome the defects and shortcomings of existing TPE materials that it is difficult to have good encapsulation performance, strong antistatic ability and excellent mechanical properties, and to provide a bonding PP antistatic TPE material.

[0005] The purpose of the present invention is to provide a method for preparing the bonded PP antistatic TPE material.

[0006] Another object of the present invention is to provide the application of the bonded PP antistatic TPE material.

[0007] Another object of the present invention is to provide a rubber-coated PP product.

[0008] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0009] The present invention protects a bonding PP antistatic TPE material, which comprises the following components by weight: 9 to 32 parts of hydrogenated styrene elastomer; 18 to 61 parts of mineral oil; 4 to 16 parts of polypropylene; 4 to 17 parts of POE; 1 to 16 parts of ethylene-propylene copolymer elastomer; 3 to 18 parts of polyether block amide; 0 to 40 parts of filler; and 0 to 3 parts of auxiliary agent.

[0010] The polypropylene end (i.e., PP end) of the ethylene-propylene copolymer elastomer shows a high degree of compatibility with polypropylene, while the other end contains vinyl groups, which show good affinity with hydrogenated styrene elastomers, making them closely compatible with such elastomers. This feature significantly enhances the bonding ability between TPE materials and PP materials, achieving a more solid bond. There are two types of POE, one is a polymer of ethylene and butene, and the other is a polymer of ethylene and octene, which has the characteristics of less crystallization and slow cooling. Adding it to the material can not only increase the toughness of the material, but also increase the material temperature holding time during injection molding, thereby improving the bonding ability of TPE and PP. Polyether block amide belongs to a polymer material, which is obtained by block copolymerization of polyether and polyamide, and can form ion channels in TPE, effectively improving the antistatic ability of the material without reducing the bonding ability to PP. The above components work synergistically to obtain a TPE material with good PP encapsulation, strong antistatic properties, and excellent mechanical properties.

[0011] Specifically, the hydrogenated styrene elastomer can be 9 parts, 10 parts, 12 parts, 15 parts, 20 parts, 30 parts, 32 parts, etc., or an interval range formed by any of the above values, such as 9-12 parts, 10-15 parts, 10-30 parts, etc., but is not limited thereto.

[0012] Specifically, the mineral oil can be 18 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 50 parts, 55 parts, 60 parts, 61 parts, etc., or an interval range formed by any of the above values, such as 20-60 parts, 18-50 parts, 20-40 parts, etc., but is not limited to these.

[0013] Specifically, the polypropylene can be 4 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 16 parts, etc., or an interval range formed by any of the above values, such as 4-8 parts, 5-15 parts, 8-16 parts, etc., but is not limited thereto.

[0014] Specifically, POE can be 4 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 17 parts, etc., or an interval range formed by any of the above values, such as 4-8 parts, 5-10 parts, 8-17 parts, etc., but is not limited thereto.

[0015] Specifically, the ethylene-propylene copolymer elastomer can be 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 16 parts, etc., or an interval range formed by any of the above values, such as 1-8 parts, 2-15 parts, 8-16 parts, etc., but is not limited thereto.

[0016] Specifically, the polyether block amide can be 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, etc., or an interval range formed by any of the above values, such as 3-8 parts, 5-15 parts, 3-18 parts, etc., but is not limited thereto.

[0017] Furthermore, the total weight percentage of the hydrogenated styrene elastomer and the mineral oil in the bonded PP antistatic TPE material is not less than 19%.

[0018] Furthermore, the total weight percentage of the hydrogenated styrene elastomer and the mineral oil in the bonded PP antistatic TPE material is not less than 40%.

[0019] Preferably, the bonding PP antistatic TPE material comprises the following components by weight: 10 to 30 parts of the hydrogenated styrene elastomer; 20 to 60 parts of mineral oil; 5 to 15 parts of polypropylene; 5 to 15 parts of POE; 2 to 15 parts of ethylene-propylene copolymer elastomer; 5 to 15 parts of polyether block amide; 10 to 30 parts of filler; and 1 to 2 parts of additives.

[0020] More preferably, the bonding PP antistatic TPE material comprises the following components by weight: 15 to 25 parts of the hydrogenated styrene elastomer; 30 to 50 parts of mineral oil; 8 to 12 parts of polypropylene; 7 to 13 parts of POE; 6 to 12 parts of ethylene-propylene copolymer elastomer; 8 to 12 parts of polyether block amide; 18 to 25 parts of filler; and 1.5 to 2 parts of additives.

[0021] Specifically, in the present invention, the ethylene content in the ethylene-propylene copolymer elastomer can be 2wt%, 5wt%, 8wt%, 9wt%, 11wt%, 13wt%, 16wt%, 20wt%, etc., or an interval range formed by any of the above values, such as 2-8wt%, 5-16wt%, 9-13wt%, 16-20wt%, etc., but not limited to this.

[0022] Preferably, the ethylene content in the ethylene-propylene copolymer elastomer is 2-20 wt %. Within this range, the ethylene-propylene copolymer elastomer can improve the bonding ability between the TPE material and the PP material.

[0023] More preferably, the ethylene content in the ethylene-propylene copolymer elastomer is 9 to 13 wt %. When the ethylene content is within this range, the compatibility between polypropylene and TPE material reaches a better state, which can further improve the bonding ability between TPE material and PP material.

[0024] Furthermore, the testing standard for the ethylene content in the ethylene-propylene copolymer elastomer is Q / SYDS0240.118-2004.

[0025] Preferably, the hydrogenated styrene-based elastomer includes at least one of a hydrogenated styrene-butadiene block copolymer and a hydrogenated styrene-isoprene block copolymer.

[0026] Preferably, the POE is selected from at least one of ethylene-butene polymer and ethylene-octene polymer.

[0027] Furthermore, the polypropylene is at least one of homopolymer polypropylene, block copolymer polypropylene and random copolymer polypropylene, preferably random copolymer polypropylene. Random copolymer polypropylene has a small crystallinity and a slow cooling rate, which enables the material to have a better temperature retention rate and less crystallization when coated on PP, and less damage to the bonding group.

[0028] Furthermore, the block copolymer polypropylene is obtained by copolymerizing propylene and part of ethylene.

[0029] Random copolymer polypropylene (PP random copolymer) is obtained by copolymerizing propylene monomer and a small amount of ethylene monomer, and the ethylene monomer is randomly distributed in the long chain of propylene.

[0030] Furthermore, the ethylene-propylene copolymer elastomer is mainly composed of repeating monomers of isotactic propylene and randomly distributed ethylene, forming an elastomeric material similar to POE.

[0031] Preferably, the mineral oil comprises at least one of cycloparaffin oil, white oil, paraffin oil and aromatic oil, and more preferably cycloparaffin oil. All of the above mineral oils can achieve the purpose of the present invention, and cycloparaffin oil has better compatibility with hydrogenated styrene elastomers.

[0032] Preferably, the filler includes at least one of calcium carbonate, white carbon black, wollastonite, glass microspheres, talc, kaolin, diatomaceous earth, barium sulfate and mica.

[0033] Preferably, the auxiliary agent includes at least one of an antioxidant, a lubricant, and a light stabilizer. The auxiliary agent can be added according to actual needs.

[0034] Furthermore, the antioxidant includes one or more of 2,6-di-tert-butyl-4-methylphenol, antioxidant 1010, antioxidant 1076, antioxidant 1790, antioxidant 168, and antioxidant 626.

[0035] Furthermore, the light stabilizer is a hindered amine light stabilizer and / or a triazine light stabilizer.

[0036] Preferably, the light stabilizer is a mixture of a hindered amine light stabilizer and a triazine light stabilizer in a weight ratio of 2:1.

[0037] Furthermore, the hindered amine light stabilizer includes one or more of light stabilizer 622, light stabilizer 770, light stabilizer 944, light stabilizer 783, light stabilizer 791, light stabilizer 3853, light stabilizer 292, and light stabilizer 123.

[0038] Furthermore, the triazine light stabilizer is one or more of UV-234, UV-236, and UV-2373.

[0039] Furthermore, the lubricant includes one or more of vinyl bisstearamide, hydroxy fatty acid lubricant, erucic acid amide, zinc stearate, magnesium stearate or polyethylene wax.

[0040] The present invention also protects a method for preparing the bonded PP antistatic TPE material, comprising the following steps:

[0041] S1. The hydrogenated styrene elastomer is mixed with mineral oil to form a solid one-step material;

[0042] S2. The solid first-step material obtained in step S1 is mixed with other components and then melt-extruded at 170-250° C. to obtain the adhesive PP antistatic TPE material.

[0043] The present invention also protects the use of the bonded PP antistatic TPE material in the preparation of TPE products coated with PP.

[0044] The present invention protects a rubber-coated PP product, which includes a PP substrate and a coating agent coated on the surface of the PP substrate, wherein the coating agent is the bonding PP antistatic TPE material.

[0045] Compared with the prior art, the present invention has the following beneficial effects: the ethylene-propylene copolymer elastomer of the present invention has good compatibility with both PP and hydrogenated styrene elastomer, and can significantly improve the bonding ability between the material and PP; POE has the characteristics of less crystallization and slow cooling, and adding it to the material can not only increase the toughness of the material, but also increase the material temperature holding time during injection molding, thereby improving the bonding ability between the obtained TPE and PP; polyether block amide can form ion channels in the TPE material, effectively improve the antistatic ability of the material, and basically do not reduce the bonding ability of PP. The above components work synergistically to obtain a TPE material with good PP encapsulation, strong antistatic properties, and excellent mechanical properties. DETAILED DESCRIPTION

[0046] The present invention is further described below with reference to specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0047] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0048] (1) Hydrogenated styrene elastomer

[0049] A1: hydrogenated styrene-butadiene block copolymer, SEBS 7551, Lee Chang-jung, Taiwan Province;

[0050] A2: hydrogenated styrene-isoprene block copolymer, SEPS YH-4051, Baling Petrochemical;

[0051] (2) Mineral oil

[0052] B: cycloparaffin oil, 500N;

[0053] (3) Polypropylene

[0054] C1: Random copolymer polypropylene, brand PP RJ766MO, manufacturer Borouge Chemical;

[0055] C2: block copolymer polypropylene, brand BX3800, manufacturer SK, South Korea;

[0056] C3: homopolymer polypropylene, brand PP HP-500N, manufacturer Basel;

[0057] (4) POE

[0058] D1: Ethylene-butene polymer, ExxonMobil POE (Exact) POE 9061;

[0059] D2: Ethylene-octene polymer, Affinity TM PF 1146G;

[0060] (5) Ethylene-propylene copolymer elastomer

[0061] E1: Ethylene-propylene copolymer elastomer, Vistamaxx 3020FL; ethylene content 11wt%

[0062] E2: Ethylene-propylene copolymer elastomer, Vistamaxx 3588FL; ethylene content 4wt%

[0063] E3: Ethylene-propylene copolymer elastomer, Vistamaxx 6102FL; ethylene content 16wt%

[0064] (6) EPDM

[0065] F: EPDM, Vistalon 2504N ExxonMobil;

[0066] (7) Antistatic agent

[0067] G1: polyether block amide, Pebax7033SP01, Arkema, France;

[0068] G2: polyether block amide, Pebax3533 SP 01, Arkema, France;

[0069] G3: Alkyl dimethyl hydroxyethyl quaternary ammonium nitrate HDC-109 Lin'an Dechang;

[0070] G4: PP-based carbon black masterbatch, PP-03, Yunpeng New Materials;

[0071] (8) Filling

[0072] H: calcium carbonate, WN503, Changzhou calcium carbonate;

[0073] (9) Additives

[0074] J: Antioxidant, Irganox 1010, Irgafos 168, BASF;

[0075] K1: Light stabilizer, light stabilizer 622, Jadejia;

[0076] K2: Light stabilizer, UV-234, Jadejia;

[0077] L: Lubricant, vinyl bisstearamide, E1818, Kraton.

[0078] Preparation and performance testing of antistatic TPE materials of Examples 1 to 10 and Comparative Examples 1 to 5

[0079] 1. Preparation of antistatic TPE materials

[0080] Preparation method of antistatic TPE material of embodiment and comparative example: According to the formula of Table 1 or Table 2, the hydrogenated styrene elastomer is first sprayed with mineral oil to prepare a solid one-step material, and then mixed with other components evenly, and granulated by extrusion through a twin-screw extruder, and the screw temperature range is 170-250°C to obtain a bonded PP antistatic TPE material.

[0081] 2. Performance Testing

[0082] (1) Adhesion strength test

[0083] According to the requirements of GB / T 7760-2003 standard, the antistatic TPE material to be tested is injected onto the PP substrate sample strip using an injection molding machine on a specific mold, and the injection molding temperature is 200°C. After being placed at room temperature for 24 hours, a 90° peeling is performed to test the bonding strength between the coated TPE and the PP substrate sample strip.

[0084] For the adhesive strength test, A: can be easily peeled off, the peeling surface is smooth and has no residue. B: The peeling force is large, and the residue on the peeling surface is as high as 50%. C: It is difficult to peel off the edges and corners, the residue is 50%-99%, and the peeling force is large. D: It is difficult to peel off the edges and corners, the TPE is broken, and the peeling force is large.

[0085] (2) Tensile strength test

[0086] According to the ISO527-2012 standard test, the antistatic TPE materials obtained in the examples and comparative examples were injection molded into 2*100*100mm standard square plates, cut into 2-type strips using a cutter, and placed at room temperature for 24 hours before being tested by a stretching machine. The molding cycle was based on the cycle of the injection molding and stretching strips.

[0087] (3) Hardness test

[0088] According to the ISO 7619-1 standard test, the antistatic TPE materials obtained in the examples and comparative examples were injection molded into 2*100*100mm standard square plates, left for 24 hours, and then pressed with a Shore A hardness tester for 15 seconds and the readings were taken.

[0089] Hardness is a basic property of materials. There is no good or bad distinction between high and low hardness. You can choose materials of different hardness according to your needs.

[0090] (4) Surface resistivity test

[0091] The antistatic TPE materials obtained in the examples and comparative examples were injection molded into 2*100*100 mm standard square plates, and then placed at room temperature for 24 hours before using a surface resistance meter to test their surface resistivity.

[0092] For antistatic materials, the lower the surface resistivity, the better the antistatic performance, and the larger the surface resistivity, the better the insulation performance. 12 Ω is an insulator. Greater than 10 4 Less than 10 11 Ω is antistatic material. Antistatic ability <10 9 It means it has excellent antistatic ability.

[0093] 3. Test results

[0094] Table 1 Raw materials used in Examples 1 to 10, their weight fractions and performance results

[0095]

[0096]

[0097] Table 2 Raw materials used in Comparative Examples 1 to 5 and their weight fractions and performance results

[0098]

[0099] The results are shown in Table 1 and Table 2. From the above data, we can see that:

[0100] The comparison results of Comparative Example 1 and Example 1 show that the addition of POE elastomer significantly enhances the bonding ability of TPE to PP;

[0101] The comparison results of Comparative Example 2 and Example 1 show that the addition of ethylene-propylene copolymer elastomer can provide sites compatible with hydrogenated styrene elastomer and PP, significantly enhance the adhesion of TPE to PP, and improve the dispersion performance of the material.

[0102] The comparison results of Comparative Example 3 and Example 1 show that the ethylene-propylene copolymer elastomer of the present application can significantly enhance the adhesion of TPE to PP, and the bonding grade reaches C to D levels. Other similar substances such as EPDM rubber have certain cross-linking properties and are not compatible with PP during injection molding, and cannot effectively enhance the adhesion.

[0103] The comparison results of Comparative Examples 4 to 5 with Example 1 show that among various antistatic agents, only polyether block amide has good antistatic performance without reducing the adhesion performance of the system.

[0104] The results of Examples 1 to 10 show that the ethylene-propylene copolymer elastomer of the present invention has good compatibility with both PP and hydrogenated styrene elastomers, and can significantly improve the bonding ability between the material and PP; POE has the characteristics of less crystallization and slow cooling. Adding it to the material can not only increase the toughness of the material, but also increase the material temperature holding time during injection molding, thereby improving the bonding ability between the obtained TPE and PP; polyether block amide can form ion channels in the TPE material, effectively improve the antistatic ability of the material, and basically do not reduce the bonding ability of PP. The above components work synergistically to obtain a TPE material with good PP encapsulation, strong antistatic properties, and excellent mechanical properties.

[0105] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A bonding PP antistatic TPE material, characterized in that: The composition comprises the following components by weight: 9 to 32 parts of hydrogenated styrene elastomer, 18 to 61 parts of mineral oil, 4 to 16 parts of polypropylene, 4 to 17 parts of POE, 1 to 16 parts of ethylene-propylene copolymer elastomer, 3 to 18 parts of polyether block amide, 0 to 40 parts of filler and 0 to 3 parts of auxiliary agent.

2. The bonding PP antistatic TPE material according to claim 1, characterized in that: The ethylene content of the ethylene-propylene copolymer elastomer is 2-20 wt %, preferably 9-13 wt %.

3. The bonding PP antistatic TPE material according to claim 1, characterized in that: The hydrogenated styrene-based elastomer includes at least one of a hydrogenated styrene-butadiene block copolymer and a hydrogenated styrene-isoprene block copolymer.

4. The bonding PP antistatic TPE material according to claim 1, characterized in that: The POE is selected from at least one of ethylene-butene polymer and ethylene-octene polymer.

5. The bonding PP antistatic TPE material according to claim 1, characterized in that: The polypropylene is selected from at least one of homopolymer polypropylene, block copolymer polypropylene and random copolymer polypropylene, and preferably includes random copolymer polypropylene.

6. The bonding PP antistatic TPE material according to claim 1, characterized in that: The mineral oil includes at least one of cycloparaffin oil, white oil, paraffin oil and aromatic hydrocarbon oil.

7. The bonding PP antistatic TPE material according to claim 1, characterized in that: The auxiliary agent includes at least one of an antioxidant, a lubricant, and a light stabilizer.

8. The method for preparing the bonded PP antistatic TPE material according to any one of claims 1 to 7, characterized in that: The steps include: S1. The hydrogenated styrene elastomer is mixed with mineral oil to form a solid one-step material; S2. The solid first-step material obtained in step S1 is mixed with other components and then melt-extruded at 170-250° C. to obtain the adhesive PP antistatic TPE material.

9. Use of the bonded PP antistatic TPE material according to any one of claims 1 to 7 in the preparation of TPE products coated with PP.

10. A plastic-coated PP product, characterized in that: It comprises a PP matrix and a coating agent coated on the surface of the PP matrix, wherein the coating agent is the bonding PP antistatic TPE material according to any one of claims 1 to 7.

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