A low-cost and highly wear-resistant TPE modified material and preparation method thereof

Abstract

The invention relates to the technical field of TPE, and in particular to a low-cost and highly wear-resistant TPE modified material and a preparation method thereof. The invention adds recycled old tire rubber particles which can reduce cost and improve wear resistance on the basis of SEBS, and then adds POE and metallocene polyethylene to improve processing performance and mechanical properties, so as to finally prepare a low-cost and highly wear-resistant TPE modified material. In order to improve the compatibility and dispersibility of the recycled old tire rubber particles in the system, the invention performs a separate surface modification treatment on the recycled old tire rubber particles, and adds a specific compatibilizer in the final preparation process link. After the selection of the above-mentioned specific raw materials and the specific preparation process, the TPE modified material prepared by the invention not only has effectively reduced cost, but also has greatly improved wear resistance, and has excellent mechanical properties in other aspects.

Description

Technical Field

[0001] The invention relates to the technical field of TPE, and in particular to a low-cost and highly wear-resistant TPE modified material and a preparation method thereof. Background Art

[0002] Thermoplastic Elastomer (TPE) is a material that has the characteristics of high elasticity, high strength, high resilience of rubber and can be processed by injection molding. It is widely used because of its environmental protection, non-toxicity, safety, wide hardness range, excellent colorability, soft touch, weather resistance, fatigue resistance and temperature resistance, and excellent processing performance.

[0003] In actual production, the price of TPE materials is relatively high, and the wear resistance of TPE materials during use is not high, which also limits its application. The "A Wear-Resistant SEBS Thermoplastic Elastomer Material and Its Preparation Method" disclosed in the Chinese patent document with announcement number CN105566924A is prepared from the following raw materials by weight: 100 parts of SEBS resin; 100-150 parts of white oil; 100-400 parts of polypropylene; 200-400 parts of filler; 1-3 parts of lubricant; 0.2-1 parts of antioxidant additive; 25-50 parts of wear-resistant additive, but the wear resistance of the material is not enhanced. On the contrary, due to the presence of more fillers and additives, the mechanical properties of the material are reduced. Summary of the invention

[0004] The object of the present invention is to provide a low-cost and highly wear-resistant TPE modified material and a preparation method thereof in view of the deficiencies in the prior art.

[0005] The purpose of the present invention is achieved through the following technical solution: a low-cost and highly wear-resistant TPE modified material, which includes the following substances in parts by weight:

[0006] SEBS 40-50 parts by weight

[0007] Recycled tire rubber particles 10-20 parts by weight

[0008] POE 10-20 parts by weight

[0009] Metallocene polyethylene 5-10 parts by weight

[0010] Compatibilizer 1-5 parts by weight

[0011] 0.5-2 parts by weight of triethoxyvinylsilane

[0012] Calcium carbonate 1-5 parts by weight

[0013] 1-5 parts by weight of graphene oxide,

[0014] The recycled tire rubber particles are obtained through surface modification treatment, and the recycled tire rubber particles of the present invention mainly contain natural rubber and synthetic rubber as main components.

[0015] Preferably, the SEBS is oil-extended SEBS, which is specifically obtained by stirring SEBS and cyclohexane oil at a weight ratio of (3-2):1 at a low speed for 3-6 hours and leaving for 2-3 days.

[0016] Preferably, the compatibilizer is a SEBS maleic acid graft copolymer and a POE maleic acid graft copolymer in a mass ratio of (2-3):1.

[0017] Preferably, the mass content of the styrene segments in the SEBS is 32-34wt%.

[0018] Preferably, the melt flow rate of the POE is 4-10 g / 10 min (190° C., 2.16 kg).

[0019] Preferably, SEBS is a linear triblock copolymer with polystyrene as the terminal segment and ethylene-butene copolymer obtained by hydrogenating polybutadiene as the middle elastic block.

[0020] Preferably, the POE is Dow POE 7447. The SEBS elastomer is SEBS YH-503T from Baling Petrochemical.

[0021] Preferably, the melt flow rate of the metallocene polyethylene is 2.5-3.5 g / 10 min (190° C., 2.16 kg). The metallocene polyethylene has good toughness and tensile strength during processing, and the processed product has good impact resistance and puncture resistance, which helps to improve the wear resistance and mechanical properties of the TPE of the present invention.

[0022] The above-mentioned method for preparing a low-cost and highly wear-resistant TPE modified material comprises the following steps:

[0023] Step 1: Add 10-20 parts by weight of recycled tire rubber particles to 50-80 parts by weight of water, add 1-5 parts by weight of potassium hydroxide, heat to 80-90°C under stirring, then add 0.5-1 parts by weight of lauric acid and 0.5-1 parts by weight of glyceryl monostearate, continue stirring for 2-5 hours, cool, wash and dry;

[0024] Step 2: adding 0.5-2 parts by weight of triethoxyvinylsilane, 1-5 parts by weight of calcium carbonate, and 1-5 parts by weight of graphene oxide to 10-20 parts by weight of dried recycled tire rubber particles and grinding them into rubber powder;

[0025] Step 3: Add the rubber powder obtained in step 2, 40-50 parts by weight of SEBS, 10-20 parts by weight of POE, 5-10 parts by weight of metallocene polyethylene, and 1-5 parts by weight of a compatibilizer into a twin-screw extruder for melt extrusion to obtain a low-cost and highly wear-resistant TPE modified material.

[0026] Preferably, the temperature of the twin-screw extruder in step three is 170-230°C.

[0027] The beneficial effects of the present invention are as follows: on the basis of SEBS, the present invention adds recycled old tire rubber particles which can reduce costs and improve wear resistance, and then adds POE and metallocene polyethylene to improve processing performance and mechanical properties, and finally prepares a low-cost and high-wear-resistant TPE modified material. In order to improve the compatibility and dispersibility of the recycled old tire rubber particles in the system, the present invention performs a separate surface modification treatment on the recycled old tire rubber particles, and adds a specific compatibilizer in the final preparation process. After the selection of the above-mentioned specific raw materials and the specific preparation process, the TPE modified material prepared by the present invention not only effectively reduces costs, but also greatly improves wear resistance, and has excellent mechanical properties in other aspects. DETAILED DESCRIPTION

[0028] The present invention is further described in conjunction with the following examples.

[0029] Example 1

[0030] A low-cost and highly wear-resistant TPE modified material comprises the following substances in parts by weight: SEBS, recycled tire rubber particles, POE, metallocene polyethylene, a compatibilizer, triethoxyvinylsilane, calcium carbonate, and graphene oxide, wherein the recycled tire rubber particles are obtained through surface modification treatment.

[0031] The SEBS is oil-extended SEBS, which is specifically obtained by stirring SEBS and naphthenic oil at a weight ratio of 3:1 at a low speed for 3 hours and leaving them for 3 days.

[0032] The compatibilizer is a SEBS maleic acid graft copolymer and a POE maleic acid graft copolymer in a mass ratio of 3:1.

[0033] The mass content of the styrene segments in the SEBS is 32 wt %.

[0034] The melt flow rate of the POE is 4 g / 10 min (190° C., 2.16 kg).

[0035] The melt flow rate of the metallocene polyethylene is 2.5 g / 10 min (190° C., 2.16 kg).

[0036] The above-mentioned method for preparing a low-cost and highly wear-resistant TPE modified material comprises the following steps:

[0037] Step 1: Add 10 parts by weight of recycled tire rubber particles to 50 parts by weight of water, add 1 part by weight of potassium hydroxide, heat to 80°C under stirring, then add 0.5 parts by weight of lauric acid and 0.5 parts by weight of glyceryl monostearate, continue stirring for 2 hours, cool, wash and dry;

[0038] Step 2: Add 0.5 parts by weight of triethoxyvinylsilane, 1 part by weight of calcium carbonate, and 1 part by weight of graphene oxide to 10 parts by weight of the dried recycled tire rubber particles and grind them into rubber powder;

[0039] Step 3: Add the rubber powder obtained in step 2, 40 parts by weight of SEBS, 10 parts by weight of POE, 5 parts by weight of metallocene polyethylene and 1 part by weight of a compatibilizer into a twin-screw extruder for melt extrusion to obtain a low-cost and highly wear-resistant TPE modified material.

[0040] The temperature of the twin-screw extruder in step 3 is 170-230°C.

[0041] Example 2

[0042] A low-cost and highly wear-resistant TPE modified material comprises the following substances in parts by weight: SEBS, recycled tire rubber particles, POE, metallocene polyethylene, a compatibilizer, triethoxyvinylsilane, calcium carbonate, and graphene oxide, wherein the recycled tire rubber particles are obtained through surface modification treatment.

[0043] The SEBS is oil-extended SEBS, which is specifically obtained by stirring SEBS and naphthenic oil at a weight ratio of 2:1 at a low speed for 5 hours and leaving them for 3 days.

[0044] The compatibilizer is a SEBS maleic acid graft copolymer and a POE maleic acid graft copolymer in a mass ratio of 2:1.

[0045] The mass content of the styrene segments in the SEBS is 33 wt %.

[0046] The melt flow rate of the POE is 6 g / 10 min (190° C., 2.16 kg).

[0047] The melt flow rate of the metallocene polyethylene is 3.0 g / 10 min (190° C., 2.16 kg).

[0048] The above-mentioned method for preparing a low-cost and highly wear-resistant TPE modified material comprises the following steps:

[0049] Step 1: Add 15 parts by weight of recycled tire rubber particles to 60 parts by weight of water, add 4 parts by weight of potassium hydroxide, heat to 85° C. under stirring, then add 0.8 parts by weight of lauric acid and 0.8 parts by weight of glyceryl monostearate, continue stirring for 3 hours, cool, wash and dry;

[0050] Step 2: Add 1 part by weight of triethoxyvinylsilane, 3 parts by weight of calcium carbonate, and 3 parts by weight of graphene oxide to 15 parts by weight of the dried recycled tire rubber particles and grind them into rubber powder;

[0051] Step 3: Add the rubber powder obtained in step 2, 45 parts by weight of SEBS, 15 parts by weight of POE, 8 parts by weight of metallocene polyethylene, and 3 parts by weight of a compatibilizer into a twin-screw extruder for melt extrusion to obtain a low-cost and highly wear-resistant TPE modified material.

[0052] The temperature of the twin-screw extruder in step 3 is 170-230°C.

[0053] Example 3

[0054] A low-cost and highly wear-resistant TPE modified material comprises the following substances in parts by weight: SEBS, recycled tire rubber particles, POE, metallocene polyethylene, a compatibilizer, triethoxyvinylsilane, calcium carbonate, and graphene oxide, wherein the recycled tire rubber particles are obtained through surface modification treatment.

[0055] The SEBS is oil-extended SEBS, which is specifically obtained by stirring SEBS and naphthenic oil at a weight ratio of 2:1 at a low speed for 6 hours and leaving them for 3 days.

[0056] The compatibilizer is a SEBS maleic acid graft copolymer and a POE maleic acid graft copolymer in a mass ratio of 3:1.

[0057] The mass content of the styrene segments in the SEBS is 33 wt %.

[0058] The melt flow rate of the POE is 7 g / 10 min (190° C., 2.16 kg).

[0059] The melt flow rate of the metallocene polyethylene is 3.5 g / 10 min (190° C., 2.16 kg).

[0060] The method for preparing the above-mentioned low-cost and highly wear-resistant TPE modified material comprises the following steps:

[0061] Step 1: Add 20 parts by weight of recycled tire rubber particles to 80 parts by weight of water, add 5 parts by weight of potassium hydroxide, heat to 90° C. under stirring, then add 1 part by weight of lauric acid and 1 part by weight of glyceryl monostearate, continue stirring for 5 hours, cool, wash and dry;

[0062] Step 2: Add 2 parts by weight of triethoxyvinylsilane, 5 parts by weight of calcium carbonate and 5 parts by weight of graphene oxide to 20 parts by weight of the dried recycled tire rubber particles and grind them into rubber powder;

[0063] Step 3: Add the rubber powder obtained in step 2, 50 parts by weight of SEBS, 20 parts by weight of POE, 10 parts by weight of metallocene polyethylene, and 5 parts by weight of a compatibilizer into a twin-screw extruder for melt extrusion to obtain a low-cost and highly wear-resistant TPE modified material.

[0064] The temperature of the twin-screw extruder in step 3 is 170-230°C.

[0065] Example 4

[0066] A low-cost and highly wear-resistant TPE modified material comprises the following substances in parts by weight: SEBS, recycled tire rubber particles, POE, metallocene polyethylene, a compatibilizer, triethoxyvinylsilane, calcium carbonate, and graphene oxide, wherein the recycled tire rubber particles are obtained through surface modification treatment.

[0067] The SEBS is oil-extended SEBS, which is specifically obtained by stirring SEBS and naphthenic oil at a weight ratio of 2:1 at a low speed for 5 hours and leaving them for 3 days.

[0068] The compatibilizer is a SEBS maleic acid graft copolymer and a POE maleic acid graft copolymer in a mass ratio of 2:1.

[0069] The mass content of the styrene segments in the SEBS is 33 wt %.

[0070] The melt flow rate of the POE is 6 g / 10 min (190° C., 2.16 kg).

[0071] The melt flow rate of the metallocene polyethylene is 3.0 g / 10 min (190° C., 2.16 kg).

[0072] The method for preparing the above-mentioned low-cost and highly wear-resistant TPE modified material comprises the following steps:

[0073] Step 1: Add 15 parts by weight of recycled tire rubber particles to 60 parts by weight of water, add 4 parts by weight of potassium hydroxide, heat to 85° C. under stirring, then add 0.8 parts by weight of lauric acid and 0.8 parts by weight of glyceryl monostearate, continue stirring for 3 hours, cool, wash and dry;

[0074] Step 2: 15 parts by weight of dried recycled tire rubber particles are added with 1 part by weight of triethoxyvinylsilane, 3 parts by weight of calcium carbonate, and 3 parts by weight of graphene oxide to grind into rubber powder. The graphene oxide of the embodiment of the present invention is treated as follows before use: 30 mg of graphene oxide is dissolved in 30 ml of distilled water, subjected to low-temperature ultrasound for 3 hours, and then 0.3 ml of pyrrole monomer and 0.3 g of sodium p-hydroxybenzenesulfonate are added, stirred in a water bath for 30 minutes, 1.021 g of ammonium persulfate is added dropwise, reacted for 26 hours, and washed and vacuum dried to obtain; the calcium carbonate of the embodiment of the present invention includes nano calcium carbonate powder and large-particle calcium carbonate powder, the weight ratio of nano calcium carbonate powder to large-particle calcium carbonate powder is 15:1, and the particle size of the large-particle calcium carbonate powder is less than 2500 mesh;

[0075] Step 3: Add the rubber powder obtained in step 2, 45 parts by weight of SEBS, 15 parts by weight of POE, 8 parts by weight of metallocene polyethylene, and 3 parts by weight of a compatibilizer into a twin-screw extruder for melt extrusion to obtain a low-cost and highly wear-resistant TPE modified material.

[0076] The temperature of the twin-screw extruder in step 3 is 170-230°C.

[0077] Comparative Example 1

[0078] The difference between the present invention and Example 2 is that: this comparative example does not adopt step one, and directly adds 1 weight part of triethoxyvinylsilane, 3 weight parts of calcium carbonate, and 3 weight parts of graphene oxide to 15 weight parts of recycled old tire rubber particles and grinds them into rubber powder. The rest is the same as Example 2.

[0079] Comparative Example 2

[0080] The difference between the present invention and Example 2 is that in step 2 of this comparative example, 15 parts by weight of the dried recycled tire rubber particles are directly ground into rubber powder, and the rest is the same as Example 2.

[0081] The thermoplastic elastomer flame retardant materials of Examples 1-4 and Comparative Examples 1-2 were subjected to performance tests, and the performance is shown in the following table:

[0082] .

[0083] It can be seen from the above data that the TPE modified materials of Examples 1-4 of the present invention have lower wear rates and better mechanical properties than those of Comparative Examples 1-2, among which Example 4 has the best performance.

[0084] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A low-cost and highly wear-resistant TPE modified material, characterized by: The invention comprises the following materials in parts by weight: SEBS, recycled tire rubber particles, POE, metallocene polyethylene, a compatibilizer, triethoxyvinylsilane, calcium carbonate, and graphene oxide, wherein the recycled tire rubber particles are obtained by surface modification treatment. The SEBS is oil-extended SEBS, which is specifically obtained by stirring SEBS and naphthenic oil at a weight ratio of 2:1 at a low speed for 5 hours and placing them for 3 days.

3. The compatibilizer is a SEBS maleic acid graft copolymer and a POE maleic acid graft copolymer at a weight ratio of 2:

1. The mass content of the styrene chain segment in the SEBS is 33wt%, and the melt flow rate of the POE is 6g / 10min at 190°C and 2.16kg. The melt flow rate of the metallocene polyethylene is 3.0 g / 10 min at 190° C. and 2.16 kg. The method for preparing the above-mentioned low-cost and highly wear-resistant TPE modified material comprises the following steps: Step 1: Add 15 parts by weight of recycled tire rubber particles to 60 parts by weight of water, add 4 parts by weight of potassium hydroxide, heat to 85° C. under stirring, then add 0.8 parts by weight of lauric acid and 0.8 parts by weight of glyceryl monostearate, continue stirring for 3 hours, cool, wash and dry; Step 2: 15 parts by weight of dried recycled tire rubber particles are added with 1 part by weight of triethoxyvinylsilane, 3 parts by weight of calcium carbonate, and 3 parts by weight of graphene oxide to grind into rubber powder. The graphene oxide of the embodiment of the present invention is treated as follows before use: 30 mg of graphene oxide is dissolved in 30 ml of distilled water, subjected to low-temperature ultrasound for 3 hours, and then 0.3 ml of pyrrole monomer and 0.3 g of sodium p-hydroxybenzenesulfonate are added, stirred in a water bath for 30 minutes, 1.021 g of ammonium persulfate is added dropwise, reacted for 26 hours, and washed and vacuum dried to obtain; the calcium carbonate includes nano calcium carbonate powder and large-particle calcium carbonate powder, the weight ratio of the nano calcium carbonate powder to the large-particle calcium carbonate powder is 15:1, and the particle size of the large-particle calcium carbonate powder is less than 2500 mesh; Step 3: Add the rubber powder obtained in step 2, 45 parts by weight of SEBS, 15 parts by weight of POE, 8 parts by weight of metallocene polyethylene, and 3 parts by weight of a compatibilizer into a twin-screw extruder for melt extrusion to obtain a low-cost and highly wear-resistant TPE modified material. The temperature of the twin-screw extruder in step 3 is 170-230°C.