High-performance TPR modifier as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of preparation of TPR (Thermoplastic Rubber), and provides a high-performance TPR modifier as well as a preparation method and application thereof. Comprising the following components in parts by mass: 100 parts of SBS (Styrene Butadiene Styrene), 40-60 parts of naphthenic oil, 10-20 parts of an auxiliary agent, 5-15 parts of a styrene-butadiene copolymer, 10-20 parts of super white calcium carbonate, 0.4-0.8 part of an antioxidant and 0.6-1 part of zinc stearate, the preparation method comprises the following steps: mixing SBS and naphthenic oil to obtain oil-filled SBS; the preparation method comprises the following steps: mixing oil-extended SBS, an auxiliary agent, a styrene-butadiene copolymer, ultra-white calcium carbonate, an antioxidant and zinc stearate, and granulating to obtain the high-performance TPR modifier. The high-performance TPR modifier provided by the invention has excellent fluidity, resilience and mechanical properties, can effectively improve the flexibility and elasticity of EVA after being added into a formula of an EVA shoe material, and perfectly combines the excellent wear resistance of rubber and the low specific gravity characteristic of EVA.

Description

Technical Field

[0001] The present invention relates to the technical field of TPR preparation, and in particular to a high-performance TPR modifier and a preparation method and application thereof. Background Art

[0002] EVA is an ethylene-vinyl acetate copolymer material, which is a non-toxic, odorless, transparent thermoplastic. Shoe materials are the main application field of EVA resin in my country. In the EVA resin used in shoe materials, the vinyl acetate content is generally 15% to 22%. Because EVA resin blended foam products are light, have good colorability and are resistant to chemical corrosion, they are widely used in the soles and interior materials of mid-to-high-end tourist shoes, mountaineering shoes, slippers, and sandals. Shunde and Zhongshan in Guangdong, Jinjiang and Quanzhou in Fujian, and Wenzhou in Zhejiang are the main production bases of my country's footwear industry, consuming a large amount of EVA resin products every year. EVA shoe materials have good shockproof, cushioning, heat insulation, heat preservation and cold protection and low temperature performance, can withstand severe cold and exposure, have closed cells, and have good sound insulation. Among them, the closed cell structure makes EVA shoe materials non-absorbent, moisture-proof, and have good water resistance. It can also withstand corrosion from chemicals such as seawater, grease, acid, and alkali, and has the characteristics of antibacterial, non-toxic, odorless, and pollution-free. However, since EVA itself has poor properties in terms of softness, compression resistance, anti-slip properties, elasticity and material stretchability, elastomers are needed as modifiers.

[0003] The foaming system of TPR foaming material is the same as that of general EVA foaming system, which is to use peroxide as bridge and then use chemical foaming agent to foam to form independent foaming material. TPR foaming material has good compatibility with EVA, and has a better hardness range, soft touch and lower compression resistance.

[0004] In summary, how to provide a high-performance TPR modifier for improving the softness and resilience of EVA shoe materials is an urgent problem to be solved in this field. Summary of the invention

[0005] In view of this, the present invention provides a high-performance TPR modifier and a preparation method and application thereof to solve the problem of poor softness and resilience of existing EVA shoe materials.

[0006] In order to achieve the above object, the present invention adopts the following technical solution:

[0007] The present invention provides a high-performance TPR modifier, comprising the following components in parts by weight:

[0008] 100 parts of SBS, 40-60 parts of cyclohexane oil, 10-20 parts of additives, 5-15 parts of styrene-butadiene copolymer, 10-20 parts of ultra-white calcium carbonate, 0.4-0.8 parts of antioxidant, and 0.6-1 parts of zinc stearate.

[0009] Preferably, the antioxidant includes antioxidant 1076 and / or antioxidant 168.

[0010] Preferably, the auxiliary agent includes one or more of polystyrene, polyvinyl chloride and ethylene-vinyl acetate copolymer.

[0011] The present invention also provides a method for preparing the above-mentioned high-performance TPR modifier, comprising the following steps:

[0012] (1) SBS and naphthenic oil are mixed to obtain oil-extended SBS;

[0013] (2) The oil-extended SBS, the additive, the styrene-butadiene copolymer, the ultra-white calcium carbonate, the antioxidant and the zinc stearate are mixed and granulated to obtain a high-performance TPR modifier.

[0014] Preferably, the mixing temperature in step (1) is 15 to 60° C., and the mixing time is 30 to 120 minutes.

[0015] Preferably, the granulation process in step (2) includes 10 temperature control zones and 1 die zone arranged in sequence, wherein the temperature of zone 1 of the temperature control zone is 155-165°C, the temperature of zones 2-5 is independently 190-210°C, the temperature of zones 6-7 is independently 185-195°C, the temperature of zones 8-10 is independently 140-160°C, and the temperature of the die zone is 140-160°C.

[0016] Preferably, the main engine speed of the granulation is 180-240 r / min, and the feeding speed is 12-20 r / min.

[0017] The present invention also provides an application of a high-performance TPR modifier prepared by the preparation method of the high-performance TPR modifier in EVA shoe materials.

[0018] It can be seen from the above technical solution that compared with the prior art, the present invention has the following beneficial effects:

[0019] 1. The oil-extended SBS of the present invention is obtained by mixing SBS and naphthenic oil. SBS has good compatibility with naphthenic oil and absorbs less light such as ultraviolet rays, which can increase the fluidity of the high-performance TPR modifier of the present invention, improve its processing performance, and maintain its good mechanical properties. In addition, an auxiliary agent is added to the raw material of the high-performance TPR modifier of the present invention, which is beneficial to improve the fluidity and viscosity of the high-performance TPR modifier. Among them, the polystyrene auxiliary agent can not only improve the fluidity of the TPR modifier, but also improve the hardness of the TPR modifier and improve its processing performance.

[0020] 2. The high-performance TPR modifier prepared by the present invention has excellent fluidity, resilience and mechanical properties. At the same time, after the high-performance TPR modifier of the present invention is applied to EVA shoe materials, it can reduce the force between EVA molecular chains, play a plasticizing role, and can also improve the flexibility of the foaming material, promote the foaming of the EVA material, and make the pores grow more fully and more evenly. DETAILED DESCRIPTION

[0021] The invention provides a high-performance TPR modifier, which comprises the following components in parts by weight: 100 parts of SBS, 40-60 parts of cyclohexane oil, 10-20 parts of an auxiliary agent, 5-15 parts of a styrene-butadiene copolymer, 10-20 parts of ultra-white calcium carbonate, 0.4-0.8 parts of an antioxidant, and 0.6-1 parts of zinc stearate.

[0022] In the present invention, the cyclohexane oil is preferably 42 to 58 parts, more preferably 45 to 55 parts, and more preferably 48 to 50 parts; the auxiliary agent is preferably 12 to 18 parts, more preferably 13 to 16 parts, and more preferably 15 parts; the styrene-butadiene copolymer is preferably 7 to 14 parts, more preferably 9 to 12 parts, and more preferably 10 parts; the ultra-white calcium carbonate is preferably 12 to 18 parts, more preferably 14 to 17 parts, and more preferably 15 parts; the antioxidant is preferably 0.45 to 0.7 parts, more preferably 0.5 to 0.65 parts, and more preferably 0.6 parts; the zinc stearate is preferably 0.65 to 0.9 parts, more preferably 0.7 to 0.85 parts, and more preferably 0.8 parts.

[0023] In the present invention, the auxiliary agent preferably includes one or more of polystyrene, polyvinyl chloride and ethylene-vinyl acetate copolymer, and more preferably polystyrene GPPS; polystyrene GPPS can improve the fluidity and hardness of the high-performance TPR modifier and improve its processing performance. Crystalline polystyrene GPPS with a low softening point can more easily enter SBS and enhance the effect of PS cross-linking points.

[0024] In the present invention, the antioxidant preferably includes antioxidant 1076 and / or antioxidant 168.

[0025] The present invention also provides a method for preparing the above-mentioned high-performance TPR modifier, comprising the following steps:

[0026] (1) SBS and naphthenic oil are mixed to obtain oil-extended SBS;

[0027] (2) The oil-extended SBS, the additive, the styrene-butadiene copolymer, the ultra-white calcium carbonate, the antioxidant and the zinc stearate are mixed and granulated to obtain a high-performance TPR modifier.

[0028] In the present invention, the step (1) further comprises stirring the SBS in a high-speed stirrer.

[0029] In the present invention, the stirring time is preferably 2 to 5 minutes, more preferably 2.5 to 4 minutes, and even more preferably 3 minutes.

[0030] In the present invention, the mixing temperature in step (1) is preferably 15 to 60° C., more preferably 25 to 40° C., and more preferably 30° C.; the mixing time is preferably 30 to 120 minutes, more preferably 35 to 100 minutes, and more preferably 40 to 60 minutes.

[0031] In the present invention, the granulation process in step (2) includes 10 temperature control zones and 1 die zone arranged in sequence, wherein the temperature of zone 1 of the temperature control zone is preferably 155-165°C, more preferably 158-162°C, and more preferably 160°C; the temperature of zones 2-5 is independently preferably 190-210°C, more preferably 195-205°C, and more preferably 200°C; the temperature of zones 6-7 is independently preferably 185-195°C, more preferably 188-192°C, and more preferably 190°C; the temperature of zones 8-10 is independently preferably 140-160°C, more preferably 145-155°C, and more preferably 150°C; the temperature of the die zone is preferably 140-160°C, more preferably 145-155°C, and more preferably 150°C.

[0032] In the present invention, the main engine speed of the granulation is preferably 180-240 r / min, more preferably 200-230 r / min, more preferably 220 r / min; the feeding speed is preferably 12-20 r / min, more preferably 14-18 r / min, more preferably 16 r / min.

[0033] In the present invention, the twin-screw extruder is preferably a 65-grade screw machine.

[0034] In the present invention, the granulation operation is preferably to add the mixed material into a twin-screw extruder for extrusion, underwater stranding, and pelletizing with a pelletizer. Meanwhile, air drying is performed with an air dryer between stranding and pelletizing to reduce the moisture content of the material.

[0035] In the present invention, the process further comprises drying the cut particles after the granulation is completed.

[0036] In the present invention, the drying operation is preferably to feed the cut particles into a horizontal mixer for stirring, and to heat the particles at the same time, so that the moisture content of the particles is ≤0.15%, and finally to package the dried finished product.

[0037] In the present invention, the moisture content of the particles is preferably 0.10% to 0.15%, more preferably 0.11% to 0.14%, and even more preferably 0.12% to 0.13%.

[0038] In the present invention, the heating temperature is preferably 40-60°C, more preferably 45-55°C, and more preferably 50°C; the heating time is preferably 50-70 min, more preferably 55-65 min, and more preferably 60 min.

[0039] The present invention also provides an application of the high-performance TPR modifier prepared by the preparation method in EVA shoe materials.

[0040] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0041] Example 1

[0042] 100 parts of SBS (model 3546) were placed in a high-speed mixer and stirred for 3 minutes until they were dispersed, and then 40 parts of KN4006 naphthenic oil were added, and the mixture was fully stirred at a temperature of 30°C for 30 minutes, and then allowed to stand for 1 hour to obtain oil-extended SBS; 10 parts of polystyrene, 10 parts of styrene-butadiene copolymer, 20 parts of ultra-white calcium carbonate (316A), 0.4 parts of antioxidant 1076 and 0.6 parts of zinc stearate were added to the oil-extended SBS and stirred for 20 minutes to obtain a mixed material; then the mixed material was added to 65 grade screw The products were extruded in a screw machine, with the temperature of zone 1 in the temperature control zone controlled at 160°C, the temperatures of zones 2 to 5 at 200°C, the temperatures of zones 6 to 7 at 190°C, the temperatures of zones 8 to 10 at 150°C, the temperature of the die zone at 150°C, the main engine speed at 220r / min, the feed speed at 16r / min, and after extrusion by a screw machine, they were stretched underwater, air-dried in an air dryer, and pelletized by a pelletizer; the cut particles were then sent to a horizontal mixer for stirring, and the particles were heated at 50°C for 60 minutes to obtain a high-performance TPR modifier.

[0043] Example 2

[0044] 100 parts of SBS (model 3546) were placed in a high-speed mixer and stirred for 3 minutes until they were dispersed, and then 50 parts of KN4006 naphthenic oil were added, and the mixture was fully stirred at a temperature of 30°C for 30 minutes, and then allowed to stand for 1 hour to obtain oil-extended SBS; 10 parts of polystyrene, 10 parts of styrene-butadiene copolymer, 20 parts of ultra-white calcium carbonate (316A), 0.4 parts of antioxidant 1076 and 0.6 parts of zinc stearate were added to the oil-extended SBS and stirred for 20 minutes to obtain a mixed material; then the mixed material was added to 65 grade screw The products were extruded in a screw machine, with the temperature of zone 1 in the temperature control zone controlled at 160°C, the temperatures of zones 2 to 5 at 200°C, the temperatures of zones 6 to 7 at 190°C, the temperatures of zones 8 to 10 at 150°C, the temperature of the die zone at 150°C, the main engine speed at 220r / min, the feed speed at 16r / min, and after extrusion by a screw machine, they were stretched underwater, air-dried in an air dryer, and pelletized by a pelletizer; the cut particles were then sent to a horizontal mixer for stirring, and the particles were heated at 50°C for 60 minutes to obtain a high-performance TPR modifier.

[0045] Example 3

[0046] 100 parts of SBS (model 3546) were placed in a high-speed mixer and stirred for 3 minutes until they were dispersed, and then 60 parts of KN4006 naphthenic oil were added, and the mixture was fully stirred at a temperature of 30°C for 30 minutes, and then allowed to stand for 1 hour to obtain oil-extended SBS; 10 parts of polystyrene, 10 parts of styrene-butadiene copolymer, 20 parts of ultra-white calcium carbonate (316A), 0.4 parts of antioxidant 1076 and 0.6 parts of zinc stearate were added to the oil-extended SBS and stirred for 20 minutes to obtain a mixed material; then the mixed material was added to 65 grade screw The products were extruded in a screw machine, with the temperature of zone 1 in the temperature control zone controlled at 160°C, the temperatures of zones 2 to 5 at 200°C, the temperatures of zones 6 to 7 at 190°C, the temperatures of zones 8 to 10 at 150°C, the temperature of the die zone at 150°C, the main engine speed at 220r / min, the feed speed at 16r / min, and after extrusion by a screw machine, they were stretched underwater, air-dried in an air dryer, and pelletized by a pelletizer; the cut particles were then sent to a horizontal mixer for stirring, and the particles were heated at 50°C for 60 minutes to obtain a high-performance TPR modifier.

[0047] Example 4

[0048] 100 parts of SBS (model 3546) were placed in a high-speed mixer and stirred for 2 minutes until dispersed, and then 50 parts of KN4006 naphthenic oil were added, and the mixture was fully stirred at a temperature of 15°C for 120 minutes, and then allowed to stand for 1 hour to obtain oil-extended SBS; 15 parts of polyvinyl chloride, 5 parts of styrene-butadiene copolymer, 10 parts of ultra-white calcium carbonate (316A), 0.6 parts of antioxidant 168 and 0.8 parts of zinc stearate were added to the oil-extended SBS and stirred for 20 minutes to obtain a mixed material; then the mixed material was added to 65 grade screw The temperature of zone 1 in the temperature control zone is controlled to be 155°C, the temperature of zones 2 to 5 is 190°C, the temperature of zones 6 to 7 is 185°C, the temperature of zones 8 to 10 is 140°C, the temperature of the die zone is 140°C, the main engine speed is 180r / min, the feeding speed is 12r / min, after being extruded by the screw machine, underwater drawing, air drying in an air dryer, and pelletizing in a pelletizer; the cut particles are then sent to a horizontal mixer for stirring, and the particles are heated at 50°C for 60 minutes to obtain a high-performance TPR modifier.

[0049] Example 5

[0050] 100 parts of SBS (model 3546) were placed in a high-speed mixer and stirred for 5 minutes until it was dispersed, and then 50 parts of KN4006 naphthenic oil were added, and the mixture was fully stirred at a temperature of 60°C for 60 minutes, and then allowed to stand for 1 hour to obtain oil-extended SBS; 20 parts of ethylene-vinyl acetate copolymer, 15 parts of styrene-butadiene copolymer, 15 parts of ultra-white calcium carbonate (316A), 0.8 parts of antioxidant 168 and 1 part of zinc stearate were added to the oil-extended SBS and stirred for 20 minutes to obtain a mixed material; then the mixed material was added to 65 The product was extruded in a screw machine, with the temperature of zone 1 in the temperature control zone controlled at 165°C, the temperatures of zones 2 to 5 at 210°C, the temperatures of zones 6 to 7 at 195°C, the temperatures of zones 8 to 10 at 160°C, the temperature of the die zone at 160°C, the main engine speed at 240r / min, the feed speed at 20r / min, and after extrusion by the screw machine, the product was underwater stretched, air-dried in an air dryer, and pelletized in a pelletizer; the cut particles were then sent to a horizontal mixer for stirring, and the particles were heated at 50°C for 60 minutes to obtain a high-performance TPR modifier.

[0051] Experimental Example 1

[0052] The performance tests were performed on the high performance TPR modifiers prepared in Examples 1 to 3. The results are shown in Table 1.

[0053] Table 1 Performance test results of high performance TPR modifiers prepared in Examples 1 to 3

[0054]

[0055]

[0056] It can be seen from Table 1 that the TPR modifiers prepared in Examples 1 to 3 of the present invention have excellent fluidity, resilience and mechanical properties.

[0057] Application Example 1

[0058] The high-performance TPR modifier prepared in Example 2 was added to the EVA shoe material formula system, as shown in Table 2.

[0059] Table 2 EVA shoe material formula

[0060] raw material Recipe 1 Recipe 2 Recipe 3 Recipe 4 TPR 0 10 20 30 EVA 100 100 100 100 AC foaming agent 6 6 6 6 Zinc Oxide 0.5 0.5 0.5 0.5 Zinc stearate 1 1 1 1 DCP crosslinking aid 0.9 0.9 0.9 0.9 talcum powder 15 15 15 15

[0061] After weighing various raw materials according to the formula in Table 2, they were mixed on a double-roll mill at a temperature of 120°C. First, TPR and EVA were mixed evenly, and then zinc oxide and zinc stearate were added, and they were fully mixed in the form of triangle packages. After being uniform, talcum powder, AC foaming agent and DCP cross-linking agent were added, and the mixing was continued for 10 minutes. Finally, the mixture was mixed 8 times in the form of triangle packages, and the mixture was removed from the machine and placed in a flat vulcanizer. It was pressed at 170°C for 600 seconds and taken out to obtain EVA shoe materials. The hardness and resilience properties of EVA shoe materials were tested, and the results are shown in Table 3.

[0062] Table 3 Test results of hardness and resilience of EVA shoe materials

[0063] Test items Recipe 1 Recipe 2 Recipe 3 Recipe 4 Hardness(Shore A) 63 60 58 56 Rebound(%) 40 43 44.2 45.4

[0064] It can be seen from Table 3 that after the high-performance TPR modifier prepared in Example 2 is added to the EVA shoe material formula system, the performance of EVA in terms of softness and elasticity is effectively improved. The EVA modified by the TPR material has better dynamic viscoelastic properties, which can perfectly combine the excellent wear resistance of rubber and the low specific gravity characteristics of EVA.

[0065] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A high performance TPR modifier, characterized in that: The composition includes the following components in parts by weight: 100 parts of SBS, 40-60 parts of cyclohexane oil, 10-20 parts of additives, 5-15 parts of styrene-butadiene copolymer, 10-20 parts of ultra-white calcium carbonate, 0.4-0.8 parts of antioxidant, and 0.6-1 parts of zinc stearate.

2. A high performance TPR modifier according to claim 1, characterized in that: The auxiliary agent includes one or more of polystyrene, polyvinyl chloride and ethylene-vinyl acetate copolymer.

3. A high performance TPR modifier according to claim 2, characterized in that: The antioxidant includes antioxidant 1076 and / or antioxidant 168.

4. The method for preparing a high-performance TPR modifier according to any one of claims 1 to 3, characterized in that: The steps include: (1) SBS and naphthenic oil are mixed to obtain oil-extended SBS; (2) The oil-extended SBS, the additive, the styrene-butadiene copolymer, the ultra-white calcium carbonate, the antioxidant and the zinc stearate are mixed and granulated to obtain a high-performance TPR modifier.

5. The method for preparing a high-performance TPR modifier according to claim 4, characterized in that: The mixing temperature in step (1) is 15 to 60° C., and the mixing time is 30 to 120 minutes.

6. The method for preparing a high-performance TPR modifier according to claim 5, characterized in that: The granulation process in step (2) includes 10 temperature control zones and 1 die zone arranged in sequence, wherein the temperature of zone 1 of the temperature control zone is 155-165°C, the temperature of zones 2-5 is independently 190-210°C, the temperature of zones 6-7 is independently 185-195°C, the temperature of zones 8-10 is independently 140-160°C, and the temperature of the die zone is 140-160°C.

7. The method for preparing a high-performance TPR modifier according to claim 6, characterized in that: The main machine speed of the granulation is 180-240 r / min, and the feeding speed is 12-20 r / min.

8. Use of the high-performance TPR modifier prepared by the method for preparing a high-performance TPR modifier according to any one of claims 4 to 7 in EVA shoe materials.

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