An antistatic TPE material and its preparation method and application

Abstract

The present invention discloses an antistatic TPE material comprising the following components, by weight: a hydrogenated styrene elastomer, mineral oil, ABS, thermoplastic polyurethane, a styrene-maleic anhydride copolymer, and a polyether block polyamide. The antistatic TPE material not only exhibits high antistatic properties and mechanical strength but also exhibits excellent compatibility with ABS, enabling it to be used for encapsulating ABS.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to an antistatic TPE material, a preparation method thereof, and an application thereof. Background Art

[0002] Acrylonitrile-butadiene-styrene (ABS) resin is a widely used polymer that organically combines the properties of BS, SAN, and PS. BS improves toughness, impact resistance, and cold resistance; SAN imparts chemical stability, oil resistance, a certain degree of stiffness, and hardness to ABS resin; and PS imparts good dielectric properties and excellent processability. In actual use, ABS products made from ABS rubber have demonstrated dimensional stability, excellent mechanical properties with a balanced balance of toughness, hardness, and rigidity, and excellent low-temperature impact resistance. Therefore, ABS is often used in tool grips.

[0003] Thermoplastic elastomer (TPE) is a polymer composite material that combines the processing properties of thermoplastics with the physical properties of vulcanized rubber. The product combines the high elasticity, strength, and resilience of rubber with the ease and versatility of ordinary plastics. An important application of TPE is as a coating material (encapsulation), which involves encapsulating TPE soft rubber onto other materials. Because TPE has excellent anti-slip properties and a flexible feel, it can enhance the tactile feel and grip of products. TPE soft rubber can be adjusted to the appropriate hardness (hardness range Shore 25-90A) and physical properties (such as wear and scratch resistance, adhesion, melt index, etc.) based on the physical requirements of the product, providing a variety of possible material application solutions for different products. TPE is processed using encapsulation injection molding, and is commonly used in products such as handles, grips, and electronic materials. TPE materials give products a comfortable touch, improve grip, enhance product aesthetics, and increase product added value. TPE rubber is bonded to some commonly used general plastics such as PP, GPPS, HIPS, ABS and engineering plastics such as PC, PC / ABS, PA, POM and their modified materials.

[0004] However, in the prior art, the TPE material used for encapsulating ABS has the following main defects: after the antistatic agent is added to the TPE material, it will greatly affect the hydrogen bonds in the polar groups in the TPE material, resulting in the inability to encapsulate ABS. Summary of the Invention

[0005] The purpose of the present invention is to overcome the above technical defects and provide a TPE material with good ABS encapsulation, antistatic and high mechanical strength, and a preparation method and application thereof.

[0006] The present invention is achieved through the following technical solutions:

[0007] An antistatic TPE material, comprising the following components in parts by weight:

[0008] 9-31 parts of hydrogenated styrene elastomer;

[0009] 19-61 parts of mineral oil;

[0010] ABS 0.5-9 parts;

[0011] 4-16 parts of thermoplastic polyurethane;

[0012] 1-21 parts of styrene maleic anhydride copolymer;

[0013] 4-16 parts of polyether block polyamide.

[0014] As an example, the hydrogenated styrene elastomer content can be 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts.

[0015] As an example, the mineral oil content can be 19 parts, 21 parts, 23 parts, 25 parts, 27 parts, 29 parts, 31 parts, 33 parts, 35 parts, 37 parts, 39 parts, 41 parts, 43 parts, 45 parts, 47 parts, 49 parts, 51 parts, 53 parts, 55 parts, 57 parts, 59 parts, 61 parts.

[0016] As an example, the ABS content may be 0.5 parts, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, or 9 parts.

[0017] As an example, the thermoplastic polyurethane content can be 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, or 16 parts.

[0018] As an example, the content of the styrene maleic anhydride copolymer can be 1 part, 3 parts, 5 parts, 7 parts, 9 parts, 11 parts, 13 parts, 15 parts, 17 parts, 19 parts, or 21 parts.

[0019] As an example, the polyether block polyamide content can be 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, or 16 parts.

[0020] The hydrogenated styrene elastomer is at least one selected from hydrogenated styrene-butadiene block copolymer and hydrogenated styrene-isoprene block copolymer.

[0021] The present invention has no special requirements for the parameters of ABS. As an example, the MFR (230°C / 2.16kg) of ABS may be 1.2-20 g / 10min.

[0022] The mineral oil is selected from at least one of white oil, paraffin oil, cycloparaffin oil and aromatic hydrocarbon oil.

[0023] The thermoplastic polyurethane is selected from at least one of polyester polyurethane and polyether polyurethane.

[0024] Polyester polyurethane is composed of monomers mainly including 4,4'-diphenylmethane diisocyanate (MDI), 1,4-butanediol (BDO), and adipic acid (AA), wherein the content of MDI is about 35-45 wt%, AA is about 30-40 wt%, and BDO is about 20-30 wt%.

[0025] Polyether polyurethane: The main monomers are 4,4'-diphenylmethane diisocyanate (MDI), polytetramethylene glycol (PTMEG), and 1,4-butanediol (BDO). The content of MDI is about 35-45 wt%, PTMEG accounts for about 35-45 wt%, and BDO accounts for about 15-25 wt%.

[0026] The styrene maleic anhydride copolymer is selected from at least one of styrene maleic anhydride N-phenylmaleimide terpolymer and styrene-maleic anhydride copolymer.

[0027] Specifically, the styrene maleic anhydride N-phenylmaleimide terpolymer is a terpolymer composed of styrene monomer, maleic anhydride monomer, and N-phenylmaleimide monomer, and can be a random copolymer or a block copolymer.

[0028] Styrene-maleic anhydride copolymer is a copolymer of styrene monomer and maleic anhydride monomer, and can be a random copolymer or a block copolymer.

[0029] The maleic anhydride content of the styrene-maleic anhydride copolymer that can achieve the purpose of the present invention can be in the range of 8-45wt%. Preferably, the maleic anhydride content of the styrene-maleic anhydride copolymer is in the range of 12-35wt%. More preferably, the maleic anhydride content of the styrene-maleic anhydride copolymer is in the range of 18-25wt%.

[0030] Maleic anhydride content is tested using titration, using sodium hydroxide (NaOH) as the titrant. NaOH reacts with maleic anhydride to form a water-soluble sodium salt. During titration, the maleic anhydride sample is dissolved in an appropriate solvent and an indicator (such as phenolphthalein) in methanol is added. The NaOH solution in the titrant is titrated, and the endpoint of the color change is observed to determine the maleic anhydride content.

[0031] The weight average molecular weight of the styrene maleic anhydride copolymer is in the range of 3000-150000, and the weight average molecular weight is measured by gel permeation chromatography.

[0032] Polyether block polyamide is composed of regular linear hard polyamide segments embedded in soft polyether segments.

[0033] Other components may be added as needed, including 0-2 parts by weight of an auxiliary agent, selected from at least one of an antioxidant, a lubricant, and a light stabilizer. The antioxidant may be one or more of 2,6-di-tert-butyl-4-methylphenol, Antioxidant 1010, Antioxidant 1076, Antioxidant 1790, Antioxidant 168, or Antioxidant 626. The light stabilizer may be a mixture of a hindered amine light stabilizer and a triazine light stabilizer in a weight ratio of 2:1. The hindered amine light stabilizer may be 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, or Light Stabilizer 123; the triazine light stabilizer may be one or more of UV-234, UV-236, or UV-2373. The lubricant is one or more of vinyl bisstearamide, hydroxy fatty acid lubricant, erucamide, zinc stearate, magnesium stearate or polyethylene wax.

[0034] It is also possible to choose whether to add 0-50 parts of filler according to actual conditions. The filler may be white carbon black, wollastonite, calcium carbonate, glass beads, talc, kaolin, diatomaceous earth, barium sulfate, mica, etc.

[0035] The preparation method of the antistatic TPE material of the present invention comprises the following steps: first spraying a hydrogenated styrene elastomer with mineral oil to prepare a solid one-step material, then uniformly mixing it with other components, and extruding and granulating it through a twin-screw extruder at a screw temperature range of 170-250°C to obtain the antistatic TPE material.

[0036] The antistatic TPE material of the present invention is used for encapsulating ABS.

[0037] The tensile strength of the antistatic TPE material of the present invention is ≥2MPa, and the surface resistivity is greater than e*10 4 Less than e*10 11Ohm, bonding strength> 2 N / mm and reaches C and D levels.

[0038] The present invention has the following beneficial effects:

[0039] The carbamate groups in thermoplastic polyurethanes have high strength, significantly improving the material's strength and toughness. Their high polarity also makes them highly compatible with ABS, significantly enhancing the material's encapsulation properties. Furthermore, the addition of styrene-maleic anhydride copolymers not only promotes the compatibility of the three components—polyether block polyamide, hydrogenated styrene elastomer, and ABS—to enhance overall material strength, establishing better ion channels and improving material compatibility, but also increases the activity of the carbamate groups, promoting adhesion between the substrate and ABS. This results in the ABS material of the present invention not only having the advantages of high antistatic properties and mechanical strength, but also excellent compatibility with TPE materials, making it suitable for encapsulating TPE. DETAILED DESCRIPTION

[0040] The present invention will be described in detail below with reference to specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those skilled in the art, several variations and improvements can be made without departing from the scope of the present invention. These all fall within the scope of protection of the present invention.

[0041] The raw materials used in the present invention come from the following sources:

[0042] A: hydrogenated styrene-butadiene block copolymer, SEBS 7551, Lee Chang-jung, Taiwan, China;

[0043] B: cycloparaffin oil, 500N, China Southern Airlines; C: ABS, Bayblend 2253, Bayer, Germany;

[0044] D1: polyester polyurethane, Covestro Desmopan 365X;

[0045] D2: polyether polyurethane, Covestro Desmopan DP6065A;

[0046] E1: styrene maleic anhydride copolymer, maleic anhydride content 23 wt%, XIRAN® 3500, Polyscope, Netherlands;

[0047] E2: styrene maleic anhydride copolymer, maleic anhydride content 19 wt%, XIRAN® 4000, Polyscope, Netherlands;

[0048] E3: styrene maleic anhydride copolymer, maleic anhydride content 13 wt%, XIRAN® 6000, Polyscope, Netherlands;

[0049] E4: styrene maleic anhydride copolymer, maleic anhydride content is 10wt%, XIRAN®9000, Polyscope, Netherlands;

[0050] E5: styrene maleic anhydride copolymer, maleic anhydride content is 32wt%, XIRAN® 2500, Polyscope, Netherlands;

[0051] E6: styrene maleic anhydride copolymer, maleic anhydride content is 42 wt%, XIRAN®1000, Polyscope, Netherlands;

[0052] E7: styrene maleic anhydride N-phenylmaleimide terpolymer, maleic anhydride content is 10wt%, XIRAN® IZ1018M, Polyscope, Netherlands;

[0053] F1: polyether block polyamide, Pebax 7033 SP01, Arkema, France;

[0054] F2: polyether block polyamide, Pebax 5533 SP 01, Arkema, France;

[0055] F3: quaternary ammonium salt polymer, HDC-100K, Lin'an Dechang;

[0056] F4: sulfonate polymer, HDC-193K Lin'an Dechang;

[0057] G: heavy calcium carbonate, CC903, Cologne powder;

[0058] J1: antioxidant, Irganox 1010, Irgafos 168, BASF;

[0059] J2: antioxidant, Irganox 1076 BASF;

[0060] J3: Light stabilizer, Cyasorb UV-3808pps, Cytec.

[0061] In the embodiment table, J is J1:J2:J3=1:5:5.

[0062] The preparation method of the antistatic ABS material of the embodiment and comparative example is as follows: first, a hydrogenated styrene elastomer is sprayed with mineral oil to prepare a solid one-step material, and then uniformly mixed with other components. The solid material is extruded into granules through a twin-screw extruder at a screw temperature of 170°C-180°C-200°C-200°C-200°C-200°C-210°C to obtain an antistatic ABS material.

[0063] Various test methods:

[0064] (1) Adhesion strength test method: According to the requirements of GB / T 7760-2003 standard, the antistatic ABS material to be tested is injected into the ABS substrate sample on a specific mold using an injection molding machine, and the injection molding temperature is 235℃. After being placed at room temperature for 24 hours, a 90° peeling is performed to test the bonding strength between TPE and ABS substrate sample. Note: For the adhesion strength test, A: It can be peeled off easily, and the peeling surface is smooth and has no residue. B: The peeling force is large, and the peeling surface residue is as high as 50%. C: It is difficult to peel off the edges and corners, and the residue is 50%-99%. The peeling force is large. D: It is difficult to peel off the edges and corners, and the TPE is broken. The higher the adhesion strength value, the better, and the above test results meet the requirements when they reach level C or level D.

[0065] (2) Tensile strength test method: Test according to ISO527-2012 standard. After injection molding into a 2*100*100mm standard square plate, use a cutter to cut into 2 type spline strips, place it at room temperature for 24 hours, and then test it on a tensile machine. The molding cycle shall be based on the cycle of the injection molding tensile strip.

[0066] (3) Surface resistivity test method: After the sample is injection molded into a 2*100*100mm standard square plate, it is placed at room temperature for 24 hours and then its surface resistivity is tested using a surface resistivity meter. Note: For antistatic materials, the lower the surface resistivity, the better the antistatic performance, and the larger the surface resistivity, the better the insulation performance. The surface resistivity of an object is greater than or equal to e*10 14 Ohm is an insulator. Greater than e*10 4 Less than e*10 11 Ohm is antistatic material.

[0067] Table 1: Components (parts by weight) and test results of antistatic ABS materials in Examples 1-5

[0068] Example 1 Example 2 Example 3 Example 4 Example 5 A 15 25 15 30 25 B 30 25 30 60 25 C 3 3 8 1 3 D1 8 10 12 10 D2 15 E1 1 5 8 20 E2 5 F1 10 10 10 15 15 G 20 20 20 20 J 1.1 1.1 1.1 1.1 1.1 Adhesion strength, N / mm 3.8 4.2 4.8 5.8 3.9 Peeling state D D C D D Tensile strength, MPa 5.1 6.1 7.2 14 6.0 Surface resistivity (Ω) <![CDATA[e*10 8 ]]> <![CDATA[e*10 8 ]]> <![CDATA[e*10 8 ]]> <![CDATA[e*10 7 ]]> <![CDATA[e*10 9 ]]>

[0069] Table 2: Components (parts by weight) and test results of antistatic ABS materials in Examples 6-11

[0070] Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 A 25 25 25 25 25 15 B 25 25 25 25 25 30 C 3 3 3 3 3 3 D1 10 10 10 10 10 8 E1 1 E3 5 E4 5 E5 5 E6 5 E7 5 F1 15 15 15 15 15 F2 10 G 20 20 20 20 20 20 J 1.1 1.1 1.1 1.1 1.1 1.1 Adhesion strength, N / mm 3.4 2.7 3.2 2.1 2.6 3.5 Peeling state C C D D C D Tensile strength, MPa 4.8 4.2 4.1 2.5 4.7 4.6 Surface resistivity (Ω) <![CDATA[e*10 7 ]]> <![CDATA[e*10 8 ]]> <![CDATA[e*10 9 ]]> <![CDATA[e*10 11 ]]> <![CDATA[e*10 11 ]]> <![CDATA[e*10 8 ]]>

[0071] It can be seen from Examples 2 / 5-10 that when the maleic anhydride content is 18-25wt%, the bonding strength is the highest, the edge peeling is difficult, and the tensile strength is the highest; when the maleic anhydride content is 12-35wt%, the bonding strength is greater than 3.0N / mm, the peel test reaches C / D level, and the tensile strength is greater than 4MPa.

[0072] Table 4: Components (parts by weight) and test results of antistatic ABS materials in Comparative Examples 1-3

[0073] Comparative Example 1 Comparative Example 2 Comparative Example 3 A 15 15 15 B 30 30 30 C 3 3 3 D1 1.5 8 8 E1 1 0 35 F1 10 10 10 G 20 20 20 J 1.1 1.1 1.1 Adhesion strength, N / mm 2.2 0.2 1.4 Peeling state B A D Tensile strength, MPa 3.4 2.3 4.1 Surface resistivity (Ω) <![CDATA[e*10 10 ]]> <![CDATA[>e*10 12 ]]> <![CDATA[e*10 8 ]]>

[0074] It can be seen from Comparative Example 1 that when the content of thermoplastic polyurethane is too low, the bonding strength is low.

[0075] It can be seen from Comparative Example 2 that if the styrene maleic anhydride copolymer is not contained, the bonding strength is extremely poor, and the dispersion of the polyether block polyamide is poor, resulting in an excessively high surface resistivity and poor antistatic performance.

[0076] From Comparative Example 3, it can be seen that due to the excessively high content of styrene-maleic anhydride copolymer, the tensile strength of the ABS material in Comparative Example 3 is low, resulting in a low force value at break. Although it reaches D, it has no practical value.

[0077] Table 5: Components (parts by weight) and test results of antistatic ABS materials in Comparative Examples 4-7

[0078] Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 A 15 15 25 25 B 30 30 25 25 C 0 18 3 3 D1 8 8 10 10 E1 1 1 5 5 F1 10 10 F3 10 F4 10 G 20 20 20 20 J 1.1 1.1 1.1 1.1 Adhesion strength, N / mm 1.1 3.7 1.7 0.9 Peeling state A B A A Tensile strength, MPa 3.3 6.0 3.5 5.1 Surface resistivity (Ω) <![CDATA[e*10 8 ]]> <![CDATA[e*10 8 ]]> <![CDATA[e*10 10 ]]> <![CDATA[e*10 8 ]]>

[0079] It can be seen from Comparative Example 4 that if ABS is not contained, the adhesive strength is low and the tensile strength is not high.

[0080] It can be seen from Comparative Example 5 that if the ABS content is too high, the adhesion only reaches Class B, which does not meet the requirements.

[0081] It can be seen from Comparative Examples 6 / 7 that the technical effects of the present invention cannot be achieved by using the quaternary ammonium salt polymer and sulfonate polymer antistatic agents commonly used in the art.

Claims

1. An antistatic TPE material, characterized in that: Calculated by weight, it includes the following components: 15-31 parts of hydrogenated styrene elastomer; 25-61 parts of mineral oil; ABS 1-8 parts; 8-16 parts of thermoplastic polyurethane; 1-21 parts of styrene maleic anhydride copolymer; Polyether block polyamide 10-16 parts.

2. The antistatic TPE material according to claim 1, characterized in that The hydrogenated styrene elastomer is at least one selected from hydrogenated styrene-butadiene block copolymer and hydrogenated styrene-isoprene block copolymer.

3. The antistatic TPE material according to claim 1, characterized in that The mineral oil is selected from at least one of white oil, paraffin oil, cycloparaffin oil and aromatic hydrocarbon oil.

4. The antistatic TPE material according to claim 1, characterized in that The thermoplastic polyurethane is selected from at least one of polyester polyurethane and polyether polyurethane.

5. The antistatic TPE material according to claim 1, characterized in that The styrene maleic anhydride copolymer is selected from at least one of styrene maleic anhydride N-phenylmaleimide terpolymer and styrene-maleic anhydride copolymer.

6. The antistatic TPE material according to claim 1, characterized in that The maleic anhydride content of the styrene-maleic anhydride copolymer is in the range of 8-45 wt%.

7. The antistatic TPE material according to claim 6, characterized in that The maleic anhydride content of the styrene-maleic anhydride copolymer is in the range of 12-35 wt%.

8. The antistatic TPE material according to claim 7, characterized in that: The maleic anhydride content of the styrene-maleic anhydride copolymer is in the range of 18-25 wt%.

9. The antistatic TPE material according to claim 1, characterized in that The invention further comprises 0-2 parts of auxiliary agents by weight, wherein the auxiliary agents are selected from at least one of antioxidants, lubricants and light stabilizers; and further comprises 0-50 parts of fillers by weight.

10. The method for preparing the antistatic TPE material according to any one of claims 1 to 9, characterized in that: The following steps are involved: First, the hydrogenated styrene elastomer is sprayed with mineral oil to prepare a solid one-step material, and then mixed with other components. The solid material is extruded into granules through a twin-screw extruder at a screw temperature range of 170-250°C to obtain an antistatic TPE material.

11. Use of the antistatic TPE material according to any one of claims 1 to 9, characterized in that: Used for ABS coating.