WO2022036983A1 - 抗老化tpu-abs合金材料及其制备方法 - Google Patents

抗老化tpu-abs合金材料及其制备方法 Download PDF

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WO2022036983A1
WO2022036983A1 PCT/CN2020/140457 CN2020140457W WO2022036983A1 WO 2022036983 A1 WO2022036983 A1 WO 2022036983A1 CN 2020140457 W CN2020140457 W CN 2020140457W WO 2022036983 A1 WO2022036983 A1 WO 2022036983A1
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parts
tpu
aging
abs
alloy material
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PCT/CN2020/140457
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French (fr)
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何建雄
杨博
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何建雄
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention relates to the technical field of alloy materials, in particular to an anti-aging TPU-ABS alloy material and a preparation method thereof.
  • ABS (Acrylonitrile butadiene Styrene copolymers), acrylonitrile-butadiene-styrene copolymer, is a thermoplastic polymer material structure with high strength, good toughness and easy processing. ABS can perform normally in the environment of -25 ⁇ 60 °C, and has good formability. The surface of the processed product is smooth, easy to dye and electroplating, and can be mixed with various resins to form a blend. Now it is mainly used for Alloy, plastic. However, the existing ABS materials have the disadvantages of poor solvent resistance, low dielectric strength, and low elongation at the same time.
  • TPU thermoplastic polyurethanes
  • thermoplastic polyurethane elastomer rubber is a linear block copolymer. With the increase or decrease of temperature, the intermolecular hydrogen bond crosslinking or the light intermolecular crosslinking is reversible, so TPU Not only has the elasticity of rubber, excellent processing performance, but also excellent scratch resistance, low temperature bending and printing.
  • ABS/TPU Alloy Properties and Microstructure "Modern Plastics Processing and Application” and “Research on Blending and Modification of Thermoplastic Polyurethane to ABS” "Synthetic Resins and Plastics” pointed out that TPU has good compatibility with ABS, and the addition of TPU It can improve the toughness and fluidity of ABS at the same time. However, the anti-aging properties of ABS/TPU alloy materials need to be further improved during use.
  • the ABS/TPU alloy material includes the following components by mass percentage: 50-75% of ABS; 24.8-49.9% of TPU; and 0.1-0.2% of antioxidant.
  • the preparation method includes the following steps: respectively weighing each component raw material according to the components contained in the above-mentioned ABS/TPU alloy material and their contents; after drying the ABS and the TPU, they are mixed with the antioxidant to obtain a Mixed material; put the mixed material into a twin-screw extruder, knead, extrude and granulate.
  • the ABS/TPU alloy material has balanced strength, excellent wear resistance and low temperature bending resistance, solvent resistance and high fluidity, and the overall comprehensive performance is the best. It can be widely used in artificial nails, medical equipment, and computer keys. and other fields. However, the anti-aging performance of the ABS/TPU alloy material prepared by the invention needs to be improved.
  • CN103360718B discloses an anti-aging ABS-TPU plastic alloy, which is composed of the following components by weight: 100 parts of ABS, 15-25 parts of TPU, and 0.5-1.5 parts of anti-aging agent.
  • the anti-aging ABS-TPU plastic alloy of the invention can significantly improve the stress cracking resistance of TPU, and can improve its stability to oxygen, ozone and ultraviolet rays, and can improve the impact resistance, wear resistance, and molding processing of ABS. sex. It can be used in the production of auto parts, pulleys, low-load gears and washers, and has excellent thermal aging properties, suitable for use in extreme high temperature environments, but the anti-aging properties under low temperature conditions need to be improved.
  • the obtained anti-aging TPU-ABS alloy material has good anti-aging performance, and has good comprehensive performance at low temperature of 0 °C and high temperature of 90 °C. necessary.
  • the purpose of the present invention is to provide an anti-aging TPU-ABS alloy material and a preparation method thereof. , especially under the conditions of low temperature of 0 °C and high temperature of 90 °C, it has good tensile strength and notched impact strength.
  • One of the objects of the present invention is to provide a kind of anti-aging TPU-ABS alloy material, in order to achieve this purpose, the present invention adopts the following technical scheme:
  • An anti-aging TPU-ABS alloy material in parts by weight, the anti-aging TPU-ABS alloy material includes the following components:
  • the composite antiaging agent is composed of dibutylhydroxytoluene, 2-hydroxy-4-n-octyloxybenzophenone and 2,6-di-tert-butyl-4-methylphenol.
  • the TPU and ABS of the present invention can form hydrogen bonds through blending, and have good compatibility.
  • -Composite anti-aging agent composed of di-tert-butyl-4-methylphenol, the synergistic effect of each component makes the anti-aging TPU-ABS alloy material prepared has good anti-aging performance under high temperature and low temperature conditions, It has good low temperature folding resistance, good processability and mechanical properties, especially good tensile strength and notched impact strength under low temperature below 10 °C and high temperature above 90 °C.
  • the anti-aging TPU-ABS alloy material includes the following components:
  • 50-80 parts of ABS for example, the weight parts of ABS are 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79 or 80 servings etc.
  • 40-60 parts of TPU for example, the weight parts of TPU are 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53, 54, 55, 56, 57, 58, 59, or 60, etc.
  • the weight part of composite anti-aging agent is 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part, etc.
  • ABS plastic is a terpolymer of three monomers, acrylonitrile (A), butadiene (B) and styrene (S).
  • A acrylonitrile
  • B butadiene
  • S styrene
  • A makes it resistant to chemical corrosion, heat resistance, and has a certain surface hardness
  • B makes it have high elasticity and toughness
  • S makes it have the processing and molding characteristics of thermoplastics and improve electrical properties . Therefore, ABS plastic is a kind of "tough, hard and rigid" material with easily available raw materials, good comprehensive performance, low price and wide application. ABS plastic has been widely used in machinery, electrical, textile, automobile, aircraft, ship and other manufacturing industries and chemical industry.
  • ABS has excellent comprehensive physical and mechanical properties, good low temperature impact resistance, dimensional stability, electrical properties, abrasion resistance, chemical resistance, dyeing, finished product processing and mechanical processing.
  • ABS resin is resistant to water, inorganic salts, alkalis and acids, insoluble in most alcohols and hydrocarbon solvents, but easily soluble in aldehydes, ketones, esters and some chlorinated hydrocarbons.
  • ABS resin has a low heat distortion temperature and is flammable, and has poor heat resistance.
  • TPU is a material between rubber and plastic, which is seen from its rigidity.
  • the rigidity of TPU can be measured by elastic modulus.
  • the elastic modulus of rubber is usually 1 ⁇ 10Mpa
  • TPU is 10 ⁇ 1000Mpa
  • plastic nylon, ABS, PC, POM
  • the hardness range of TPU is quite wide, from Shore A 60 to Shore D 80 and has high elasticity throughout the hardness range;
  • TPU is flexible in a wide temperature range of -40 to 120 °C without the need for plasticizers;
  • TPU It has good resistance to oils (mineral oils, animal and vegetable oils and lubricating oils) and many solvents; TPU also has good weather resistance and excellent resistance to high-energy rays. It is well known that wear resistance, tear resistance and flexural strength are excellent; high tensile strength, high elongation, and low long-term compression set are all significant advantages of TPU.
  • the weight part of the dibutylhydroxytoluene is 10-30 parts
  • the weight part of the 2-hydroxy-4-n-octyloxybenzophenone is 30-50 parts by weight parts
  • the weight part of the 2,6-di-tert-butyl-4-methylphenol is 30-40 parts.
  • the composite anti-aging agent made of the above proportions and materials can achieve better anti-aging effect only by adding a small amount of the composite anti-aging agent.
  • the weight parts of the dibutyl hydroxytoluene are 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 or 30 parts, etc.;
  • the weight parts of benzophenone are 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts or 50 parts, etc.
  • the weight parts of the 2,6-di-tert-butyl-4-methylphenol are 30 parts, 31 parts, 32 parts, 33, 34, 35, 36, 37, 38, 39, or 40, etc.
  • the anti-aging TPU-ABS alloy material includes the following components:
  • the composite anti-aging agent is composed of 10-20 parts of dibutylhydroxytoluene, 40-50 parts of 2-hydroxy-4-n-octyloxybenzophenone and 2,6 parts of - Composition of 30-40 parts of di-tert-butyl-4-methylphenol.
  • the anti-aging TPU-ABS alloy material further includes 1-2 parts of a light stabilizer.
  • the light stabilizer can act synergistically with the composite anti-aging agent to further improve the anti-aging properties of the alloy material.
  • the light stabilizer is an ultraviolet absorber.
  • the ultraviolet absorber is a benzophenone type ultraviolet absorber and/or a benzotriazole type ultraviolet absorber
  • the ABS is transparent grade ABS and/or heat resistant grade ABS.
  • the A-type Shore hardness of the TPU is 60-65A.
  • the second purpose of the present invention is to provide the preparation method of the anti-aging TPU-ABS alloy material described in one of the purposes, which is simple in technology, convenient in operation, suitable for industrialized production, and comprises the following steps:
  • step 1) mixing the pretreated ABS and TPU in step 1) according to the proportioning ratio, adding the composite anti-aging agent prepared in step 2), and mixing uniformly to obtain a mixture;
  • step 4) Adding the mixture obtained in step 3) into a twin-screw extruder for extrusion and granulation, and drying to obtain the anti-aging TPU-ABS alloy material.
  • the drying temperature is 90-100°C, for example, the drying temperature is 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C or 100°C, etc.; the drying time is 1-2h, for example, the drying time is 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h Wait.
  • the extrusion temperature of the twin-screw extruder is 180-220° C., for example, the length-diameter ratio is 25-40, and the screw speed is 200-800 rpm.
  • the temperature of the screw barrel is set to: a zone temperature of 80 °C, the temperature of the second zone is 190°C, the temperature of the third zone is 200°C, the temperature of the fourth zone is 210°C, the temperature of the fifth zone is 220°C, the temperature of the sixth zone is 220°C, the temperature of the seventh zone is 220°C, the temperature of the eighth zone is 220°C, and the temperature of the nine zone is 220°C.
  • the tenth zone temperature is 220°C, the head temperature is 220°C; the screw speed is 200-800 rpm. Under the shearing, mixing and conveying of the screw, the material can be fully melted and compounded.
  • the TPU-ABS alloy material of the present invention has good anti-aging properties, and has good tensile strength and notched impact strength under low temperature and high temperature conditions, especially under 0°C low temperature and 90°C high temperature conditions. Specifically, after the TPU-ABS alloy material prepared by the present invention is subjected to 90° C., 500h thermal oxidation aging test, the tensile strength retention rate is 82.7-88.7%, and the notched impact strength retention rate is 82.6-89.1%, 0° C., 500h After the low temperature experiment, the retention rate of tensile strength is 80.1-84.5%, and the retention rate of notched impact strength is 80.4-85.7%.
  • An anti-aging TPU-ABS alloy material of the present embodiment includes the following components:
  • ABS is transparent grade ABS (Japan Electric Chemicals (ABS TH-21)), TPU (BASF)
  • A-type Shore hardness is 60A;
  • the composite anti-aging agent is composed of dibutylhydroxytoluene, 2-hydroxy-4-n-octyloxybenzophenone and 2,6-di-tert-butyl-4-methylphenol; according to the weight of the composite anti-aging agent 100
  • the parts by weight of dibutylhydroxytoluene are 20 parts
  • the parts by weight of 2-hydroxy-4-n-octyloxybenzophenone are 50 parts
  • the parts by weight of 2,6-di-tert-butyl-4-methylphenol are The weight part is 30 parts.
  • ABS and TPU were dried and pretreated at 100°C for 1h respectively;
  • step 1) mixing the pretreated ABS and TPU in step 1) according to the proportioning ratio, adding the composite anti-aging agent prepared in step 2), and mixing uniformly to obtain a mixture;
  • the extrusion temperature of the twin-screw extruder is 180-220° C.
  • An anti-aging TPU-ABS alloy material of the present embodiment includes the following components:
  • ABS is transparent grade ABS (Japan Electric Chemical (ABS TH-21)), and the A-type Shore hardness of TPU (BASF) is 63A;
  • the composite anti-aging agent is composed of dibutylhydroxytoluene, 2-hydroxy-4-n-octyloxybenzophenone and 2,6-di-tert-butyl-4-methylphenol; according to the weight of the composite anti-aging agent 100
  • the parts by weight of dibutylhydroxytoluene are 30 parts
  • the parts by weight of 2-hydroxy-4-n-octyloxybenzophenone are 40 parts
  • the parts by weight of 2,6-di-tert-butyl-4-methylphenol are The weight part is 30 parts.
  • ABS and TPU were dried and pretreated at 95°C for 1.5h respectively;
  • step 3 mixing the pretreated ABS and TPU of step 1) by proportioning, adding the composite antiaging agent obtained in step 2), and mixing to obtain a mixture;
  • the extrusion temperature of the twin-screw extruder is 180-220° C.
  • An anti-aging TPU-ABS alloy material of the present embodiment includes the following components:
  • ABS is transparent grade ABS (Japan Electric Chemicals (ABS TH-21)), TPU (BASF)
  • A-type Shore hardness is 60A;
  • the composite anti-aging agent is composed of dibutylhydroxytoluene, 2-hydroxy-4-n-octyloxybenzophenone and 2,6-di-tert-butyl-4-methylphenol; according to the weight of the composite anti-aging agent 100
  • the parts by weight of dibutylhydroxytoluene are 20 parts
  • the parts by weight of 2-hydroxy-4-n-octyloxybenzophenone are 40 parts
  • the parts by weight of 2,6-di-tert-butyl-4-methylphenol are The weight part is 40 parts.
  • ABS and TPU were dried and pretreated at 98°C for 1.2h respectively;
  • step 1) mixing the pretreated ABS and TPU in step 1) according to the proportioning ratio, adding the composite anti-aging agent prepared in step 2), and mixing uniformly to obtain a mixture;
  • the extrusion temperature of the twin-screw extruder is 180-220° C.
  • An anti-aging TPU-ABS alloy material of the present embodiment includes the following components:
  • ABS is transparent grade ABS (Japan Electric Chemical (ABS TH-21)), and the A-type Shore hardness of TPU (BASF) is 65A;
  • the composite anti-aging agent is composed of dibutylhydroxytoluene, 2-hydroxy-4-n-octyloxybenzophenone and 2,6-di-tert-butyl-4-methylphenol; according to the weight of the composite anti-aging agent 100 In parts, the weight part of dibutylhydroxytoluene is 30 parts, the weight part of 2-hydroxy-4-n-octyloxybenzophenone is 30 parts, and the weight part of 2,6-di-tert-butyl-4-methylphenol is 30 parts by weight. The weight part is 40 parts.
  • ABS and TPU were dried and pretreated at 100°C for 1h respectively;
  • step 1) mixing the pretreated ABS and TPU in step 1) according to the proportioning ratio, adding the composite anti-aging agent prepared in step 2), and mixing uniformly to obtain a mixture;
  • the extrusion temperature of the twin-screw extruder is 180-220° C.
  • An anti-aging TPU-ABS alloy material of the present embodiment includes the following components:
  • ABS is transparent grade ABS (Japan Electric Chemicals (ABS TH-21)), TPU (BASF)
  • A-type Shore hardness is 60A;
  • the composite anti-aging agent is composed of dibutylhydroxytoluene, 2-hydroxy-4-n-octyloxybenzophenone and 2,6-di-tert-butyl-4-methylphenol; according to the weight of the composite anti-aging agent 100
  • the parts by weight of dibutylhydroxytoluene are 20 parts
  • the parts by weight of 2-hydroxy-4-n-octyloxybenzophenone are 50 parts
  • the parts by weight of 2,6-di-tert-butyl-4-methylphenol are The weight part is 30 parts.
  • ABS and TPU were dried and pretreated at 92°C for 1.6h respectively;
  • step 1) mixing the pretreated ABS and TPU in step 1) according to the proportioning ratio, adding the composite anti-aging agent prepared in step 2), and mixing uniformly to obtain a mixture;
  • the extrusion temperature of the twin-screw extruder is 180-220° C.
  • An anti-aging TPU-ABS alloy material of the present embodiment includes the following components:
  • ABS is transparent grade ABS (Japan Electric Chemicals (ABS TH-21)), TPU (BASF)
  • A-type Shore hardness is 60A;
  • the composite anti-aging agent is composed of dibutylhydroxytoluene, 2-hydroxy-4-n-octyloxybenzophenone and 2,6-di-tert-butyl-4-methylphenol; according to the weight of the composite anti-aging agent 100
  • the parts by weight of dibutylhydroxytoluene are 20 parts
  • the parts by weight of 2-hydroxy-4-n-octyloxybenzophenone are 50 parts
  • the parts by weight of 2,6-di-tert-butyl-4-methylphenol are The weight part is 30 parts.
  • ABS and TPU were dried and pretreated at 100°C for 1h respectively;
  • step 1) Mix the pretreated ABS and TPU in step 1) according to the ratio, and add the composite anti-aging agent, 2,4-dihydroxybenzophenone and 2-(2'-hydroxy-3' obtained in step 2), 5'-di-tert-phenyl)-5-benzotriazole chloride, mix well to obtain a mixture;
  • the extrusion temperature of the twin-screw extruder is 180-220° C.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the A-type Shore hardness of the TPU is 30A, and the others are the same as those of Embodiment 1.
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the A-type Shore hardness of the TPU is 80A, and the others are the same as those of Embodiment 1.
  • Example 1 The difference between this comparative example and Example 1 is that, based on 100 parts by weight of the composite anti-aging agent, the composite anti-aging agent is composed of 35 parts of dibutylhydroxytoluene and 65 parts of 2-hydroxy-4-n-octyloxydibenzyl
  • the ketone composition is the same as in Example 1.
  • Example 1 The difference between this comparative example and Example 1 is that, based on 100 parts by weight of the composite anti-aging agent, the composite anti-aging agent is composed of 45 parts of dibutylhydroxytoluene and 55 parts of 2,6-di-tert-butyl-4-methyl.
  • the composition of the base phenol is the same as that of Example 1.
  • Example 1 The difference between this comparative example and Example 1 is that, based on 100 parts by weight of the composite anti-aging agent, the composite anti-aging agent is composed of 60 parts of 2-hydroxy-4-n-octyloxybenzophenone and 40 parts of 2,6- The composition of di-tert-butyl-4-methylphenol is the same as in Example 1.
  • Example 1 The difference between this comparative example and Example 1 is that the anti-aging agent is only dibutylhydroxytoluene, and the others are the same as those of Example 1.
  • Example 1 The difference between this comparative example and Example 1 is that the anti-aging agent is only 2-hydroxy-4-n-octyloxybenzophenone, and the others are the same as those of Example 1.
  • Example 1 The difference between this comparative example and Example 1 is that the anti-aging agent is only 2,6-di-tert-butyl-4-methylphenol, and the others are the same as those of Example 1.
  • the TPU-ABS alloy materials prepared in Examples 1-8 and Comparative Examples 1-6 were tested for performance. According to the thermal-oxidative aging test standard GB/T7141-2008, artificial accelerated aging experiments (90° C.) were performed on the prepared alloy materials. , 500h), and measure the tensile strength and Izod impact strength of the plastic before and after artificially accelerated aging, and test the notched impact strength of the TPU-ABS alloy material at 0°C with reference to the ASTM D256 standard. The test results are shown in Table 1. .
  • Tensile strength retention rate (tensile strength after artificial accelerated aging-tensile strength before artificial accelerated aging) ⁇ tensile strength before artificial accelerated aging ⁇ 100%.
  • Impact strength retention rate (Izod notched impact strength after artificial accelerated aging-Izod notched impact strength before artificial accelerated aging) ⁇ Izod notched impact strength before artificial accelerated aging ⁇ 100%.
  • the TPU-ABS alloy material of the invention has good anti-aging performance, and has good tensile strength and notch impact strength under low temperature and high temperature conditions, especially under the low temperature conditions of 0°C and high temperature conditions of 90°C.
  • Example 6 After adding the light stabilizer in Example 6, it cooperates with the composite anti-aging agent to further improve the anti-aging performance of the TPU-ABS alloy material.
  • the A-type Shore hardness of the TPU of Example 7 and Example 8 is too low or too high, and neither can achieve better low-temperature and high-temperature aging resistance.
  • Comparative Examples 1-6 lack of one or two components in the composite anti-aging agent, can not achieve better low-temperature and high-temperature anti-aging properties.
  • the present invention illustrates the detailed process equipment and process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process equipment and process flow to be implemented. .
  • Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Abstract

一种抗老化TPU-ABS合金材料及其制备方法。抗老化TPU-ABS合金材料，按重量份计，包括如下组分：ABS50-80份、TPU40-60份和复合抗老化剂0.1-1份；所述复合抗老化剂由二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚组成。制得的抗老化TPU-ABS合金材料抗老化性能好，0℃低温及90℃的高温条件下均有较好的拉伸强度、缺口冲击强度。

Description

[根据细则37.2由ISA制定的发明名称]　抗老化TPU-ABS合金材料及其制备方法
本公开基于申请号为202010849946.0，申请日为2020年08月21日的中国专利申请提出，并要求该中国专利申请的优先权，该中国专利申请的全部内容在此引入本申请作为参考。
技术领域
本发明涉及合金材料技术领域，尤其涉及一种抗老化TPU-ABS合金材料及其制备方法。
背景技术
ABS(Acrylonitrile butadiene Styrene copolymers)，丙烯腈-丁二烯-苯乙烯共聚物，是一种强度高、韧性好、易于加工成型的热塑型高分子材料结构。ABS可以在-25～60℃的环境下表现正常，而且有很好的成型性，加工出的产品表面光洁，易于染色和电镀，而且可与多种树脂配混成共混物，现在主要用于合金、塑料。但现有ABS材料同时具有耐溶剂性差、低介电强度，以及低拉伸率的缺点。
TPU(Thermoplastic polyurethanes)，热塑性聚氨酯弹性体橡胶，是一种线性嵌段共聚物，随着温度的升高或降低，分子间氢键交联或大分子间轻度交联具有可逆性，因此TPU不仅具有橡胶的弹性、优异的加工性能，更具有优异的耐划伤性、低温弯折性和印刷性。
“ABS/TPU合金性能与微观结构”《现代塑料加工应用》及“热塑性聚氨酯对ABS的共混改性研究”《合成树脂及塑料》中指出TPU与ABS有良好的相容性，TPU的加入可以同时改善ABS的韧性和流动性。但是，ABS/TPU合 金材料在使用过程中，抗老化性能需要进一步提高。
CN107141697A公开了一种ABS/TPU合金材料及其制备方法与应用。该ABS/TPU合金材料包括如下质量百分含量的成分：ABS50～75％；TPU24.8～49.9％；抗氧剂0.1～0.2％。该制备方法包括如下步骤：按照上述ABS/TPU合金材料所含的成分及其含量分别称取各成分原料；将所述ABS和所述TPU进行干燥处理后与所述抗氧剂混合处理，得混合物料；将所述混合物料投入双螺杆挤出机中，经混炼挤出造粒。该ABS/TPU合金材料具有均衡的强度、优异的耐磨性和低温弯折性、耐溶剂性和高流动性，总体综合性能达到最佳，可广泛应用于人造指甲、医疗器材，以及电脑按键等领域。但是，该发明制得的ABS/TPU合金材料抗老化性能有待提高。
CN103360718B公开了一种抗老化ABS-TPU塑料合金，由下述组分按重量份组成：100份ABS、15-25份TPU、0.5-1.5份抗老化剂。该发明的抗老化ABS-TPU塑料合金可以显著提高TPU的耐应力开裂性，并能提高其对氧、臭氧、紫外线的稳定性，并能改善ABS的耐冲击性、耐磨损性、成型加工性。可用于生产汽车零部件、皮带轮、低载荷齿轮和垫圈，且具有优秀的热老化性能，适合在极端高温环境下使用，但是，低温条件下的抗老化性能有待提高。
因此，开发一种抗老化TPU-ABS合金材料及其制备方法，是制得的抗老化TPU-ABS合金材料抗老化性能好，0℃低温及90℃的高温条件下均有较好的综合性能很有必要。
发明内容
针对现有技术的不足，本发明的目的在于提供一种抗老化TPU-ABS合金材料及其制备方法，本发明制得的抗老化TPU-ABS合金材料的抗老化性能好，低温和高温条件下，尤其是0℃低温及90℃的高温条件下均有较好的拉伸强度、 缺口冲击强度。
本发明的目的之一在于提供一种抗老化TPU-ABS合金材料，为达此目的，本发明采用以下技术方案：
一种抗老化TPU-ABS合金材料，按重量份计，所述抗老化TPU-ABS合金材料包括如下组分：
ABS           50-80份
TPU           40-60份
复合抗老化剂  0.1-1份；
其中，所述复合抗老化剂由二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚组成。
本发明的TPU与ABS通过共混可形成氢键，并且具有良好的相容性，通过加入少量的由二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚组成的复合抗老化剂，各组分之间协同作用使制得的抗老化TPU-ABS合金材料在高温和低温条件下均具有良好的抗老化性能，具有良好的低温耐折性，良好的加工性能和力学性能，尤其是10℃以下低温及90℃以上的高温条件下均有较好的拉伸强度、缺口冲击强度。
具体地，按重量份计，所述抗老化TPU-ABS合金材料包括如下组分：
ABS50-80份，例如ABS的重量份为50份、51份、52份、53份、54份、55份、56份、57份、58份、59份、60份、61份、62份、63份、64份、65份、66份、67份、68份、69份、70份、71份、72份、73份、74份、75份、76份、77份、78份、79份或80份等。
TPU40-60份，例如TPU的重量份为40份、41份、42份、43份、44份、45份、46份、47份、48份、49份、50份、51份、52份、53份、54份、55 份、56份、57份、58份、59份或60份等。
复合抗老化剂0.1-1份，例如复合抗老化剂的重量份为0.1份、0.2份、0.3份、0.4份、0.5份、0.6份、0.7份、0.8份、0.9份或1份等。
ABS塑料是丙烯腈(A)、丁二烯(B)、苯乙烯(S)三种单体的三元共聚物，三种单体相对含量可任意变化，制成各种树脂。ABS兼有三种组元的共同性能，A使其耐化学腐蚀、耐热，并有一定的表面硬度，B使其具有高弹性和韧性，S使其具有热塑性塑料的加工成型特性并改善电性能。因此ABS塑料是一种原料易得、综合性能良好、价格便宜、用途广泛的“坚韧、质硬、刚性”材料。ABS塑料在机械、电气、纺织、汽车、飞机、轮船等制造工业及化工中获得了广泛的应用。ABS具有优良的综合物理和机械性能，较好的低温抗冲击性能、尺寸稳定性，电性能、耐磨性、抗化学药品性、染色性、成品加工和机械加工较好。ABS树脂耐水、无机盐、碱和酸类，不溶于大部分醇类和烃类溶剂，而容易溶于醛、酮、酯和某些氯代烃中。ABS树脂热变形温度低可燃，耐热性较差。
TPU作为弹性体是介于橡胶和塑料之间的一种材料，这从它的刚性看出来，TPU的刚性可由弹性模量来度量。橡胶的弹性模量通常在1～10Mpa，TPU在10～1000Mpa，塑料(尼龙，ABS，PC，POM)在1000～10000Mpa。TPU的硬度范围相当宽，从Shore A 60～Shore D 80并且在整个硬度范围内具有高弹性；TPU在很宽的温度范围内-40～120℃，具有柔性，而不需要增塑剂；TPU对油类(矿物油，动植物油脂和润滑油)和许多溶剂有良好的抵抗能力；TPU还有良好的耐天候性，极优的耐高能射线性能。众所周知的耐磨性、抗撕裂性、屈扰强度都是优良的；拉伸强度高，伸长率大，长期压缩永久变形率低等都是TPU的显著优点。
其中，按复合抗老化剂100重量份计，所述二丁基羟基甲苯的重量份为10-30 份，所述2-羟基-4正辛氧基二苯甲酮的重量份为30-50份，所述2，6-二叔丁基-4-甲基苯酚的重量份为30-40份。采用上述配比和材料制成的复合抗老化剂，只需添加少量的复合抗老化剂就能取得较好的抗老化效果。
具体地，按复合抗老化剂100重量份计，所述二丁基羟基甲苯的重量份为10份、11份、12份、13份、14份、15份、16份、17份、18份、19份、20份、21份、22份、23份、24份、25份、26份、27份、28份、29份或30份等；所述2-羟基-4正辛氧基二苯甲酮的重量份为30份、31份、32份、33份、34份、35份、36份、37份、38份、39份、40份、41份、42份、43份、44份、45份、46份、47份、48份、49份或50份等；所述2，6-二叔丁基-4-甲基苯酚的重量份为30份、31份、32份、33份、34份、35份、36份、37份、38份、39份或40份等。
优选地，按重量份计，所述抗老化TPU-ABS合金材料包括如下组分：
ABS           60-70份
TPU           40-50份
复合抗老化剂  0.1-0.5份；
其中，按复合抗老化剂100重量份计，所述复合抗老化剂由二丁基羟基甲苯10-20份、2-羟基-4正辛氧基二苯甲酮40-50份和2，6-二叔丁基-4-甲基苯酚30-40份组成。
按重量份计，所述抗老化TPU-ABS合金材料还包括1-2份的光稳定剂。光稳定剂可以与复合抗老化剂协同作用，进一步改善合金材料的抗老化性能。
所述光稳定剂为紫外线吸收剂。
优选地，所述紫外线吸收剂为二苯甲酮类紫外线吸收剂和/或苯并三唑类紫外线吸收剂
所述ABS为透明级ABS和/或耐热级ABS。
所述TPU的A型邵氏硬度为60-65A。
本发明的目的之二在于提供一种目的之一所述的抗老化TPU-ABS合金材料的制备方法，工艺简单，操作方便，适合于工业化生产，包括如下步骤：
1)将ABS、TPU分别进行干燥预处理；
2)以二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚为原料制备复合抗老化剂；
3)按配比将步骤1)预处理的ABS、TPU混合，加入步骤2)制得的复合抗老化剂，混合均匀得到混合物；
4)将步骤3)得到的混合物加入双螺杆挤出机中挤出造粒，干燥后得到所述抗老化TPU-ABS合金材料。
步骤1)中，所述干燥的温度为90-100℃，例如干燥的温度为90℃、91℃、92℃、93℃、94℃、95℃、96℃、97℃、98℃、99℃或100℃等；所述干燥的时间为1-2h，例如干燥的时间为1h、1.1h、1.2h、1.3h、1.4h、1.5h、1.6h、1.7h、1.8h、1.9h或2h等。
步骤4)中，所述双螺杆挤出机的挤出温度为180-220℃，例如长径比为25-40，螺杆转速为200-800rpm，例如螺筒温度设定为：一区温度80℃，二区温度190℃，三区温度200℃，四区温度210℃，五区温度220℃，六区温度220℃，七区温度220℃，八区温度220℃，九区温度220℃，十区温度220℃，机头温度220℃；螺杆转速为200-800转/分钟。在螺杆的剪切、混炼及输送下，物料得以充分熔化、复合。
与现有技术相比，本发明的有益效果为：
本发明的TPU-ABS合金材料的抗老化性能好，在低温和高温条件下，尤其 是0℃低温及90℃的高温条件下均有较好的拉伸强度、缺口冲击强度。具体的，本发明制得的TPU-ABS合金材料经90℃，500h热氧老化实验后，拉伸强度保持率为82.7-88.7％，缺口冲击强度保持率为82.6-89.1％，0℃，500h低温实验后，拉伸强度保持率80.1-84.5％，缺口冲击强度保持率为80.4-85.7％。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
如无具体说明，本发明的各种原料均可市售购得，或根据本领域的常规方法制备得到。
实施例1
本实施例的一种抗老化TPU-ABS合金材料，按重量份计，包括如下组分：
ABS           60份
TPU           50份
复合抗老化剂  0.3份；
其中，ABS为透明级ABS(日本电气化学(ABS TH-21))，TPU(巴斯夫)的A型邵氏硬度为60A；
其中，复合抗老化剂由二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚组成；按复合抗老化剂100重量份计，二丁基羟基甲苯的重量份为20份，2-羟基-4正辛氧基二苯甲酮的重量份为50份，2，6-二叔丁基-4-甲基苯酚的重量份为30份。
本实施例的抗老化TPU-ABS合金材料的制备方法，包括如下步骤：
1)将ABS、TPU分别进行100℃干燥预处理1h；
2)以二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚为原料制备复合抗老化剂；
3)按配比将步骤1)预处理的ABS、TPU混合，加入步骤2)制得的复合抗老化剂，混合均匀得到混合物；
4)将步骤3)得到的混合物加入双螺杆挤出机中挤出造粒，双螺杆挤出机的挤出温度为180-220℃，螺筒温度设定为：一区温度80℃，二区温度190℃，三区温度200℃，四区温度210℃，五区温度220℃，六区温度220℃，七区温度220℃，八区温度220℃，九区温度220℃，十区温度220℃，机头温度220℃；长径比为30，螺杆转速为700rpm，干燥后得到所述抗老化TPU-ABS合金材料。
实施例2
本实施例的一种抗老化TPU-ABS合金材料，按重量份计，包括如下组分：
ABS           70份
TPU           60份
复合抗老化剂  0.5份；
其中，ABS为透明级ABS(日本电气化学(ABS TH-21))，TPU(巴斯夫)的A型邵氏硬度为63A；
其中，复合抗老化剂由二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚组成；按复合抗老化剂100重量份计，二丁基羟基甲苯的重量份为30份，2-羟基-4正辛氧基二苯甲酮的重量份为40份，2，6-二叔丁基-4-甲基苯酚的重量份为30份。
本实施例的抗老化TPU-ABS合金材料的制备方法，包括如下步骤：
1)将ABS、TPU分别进行95℃干燥预处理1.5h；
2)以二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚为原料制备复合抗老化剂；
3)按配比将步骤1)预处理的ABS、TPU混合，加入步骤2)制得的复合 抗老化剂，混合均匀得到混合物；
4)将步骤3)得到的混合物加入双螺杆挤出机中挤出造粒，双螺杆挤出机的挤出温度为180-220℃，螺筒温度设定为：一区温度80℃，二区温度190℃，三区温度200℃，四区温度210℃，五区温度220℃，六区温度220℃，七区温度220℃，八区温度220℃，九区温度220℃，十区温度220℃，机头温度220℃；长径比为30，螺杆转速为600rpm，干燥后得到所述抗老化TPU-ABS合金材料。
实施例3
本实施例的一种抗老化TPU-ABS合金材料，按重量份计，包括如下组分：
ABS           50份
TPU           60份
复合抗老化剂  0.8份；
其中，ABS为透明级ABS(日本电气化学(ABS TH-21))，TPU(巴斯夫)的A型邵氏硬度为60A；
其中，复合抗老化剂由二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚组成；按复合抗老化剂100重量份计，二丁基羟基甲苯的重量份为20份，2-羟基-4正辛氧基二苯甲酮的重量份为40份，2，6-二叔丁基-4-甲基苯酚的重量份为40份。
本实施例的抗老化TPU-ABS合金材料的制备方法，包括如下步骤：
1)将ABS、TPU分别进行98℃干燥预处理1.2h；
2)以二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚为原料制备复合抗老化剂；
3)按配比将步骤1)预处理的ABS、TPU混合，加入步骤2)制得的复合抗老化剂，混合均匀得到混合物；
4)将步骤3)得到的混合物加入双螺杆挤出机中挤出造粒，双螺杆挤出机的挤出温度为180-220℃，螺筒温度设定为：一区温度80℃，二区温度190℃，三区温度200℃，四区温度210℃，五区温度220℃，六区温度220℃，七区温度220℃，八区温度220℃，九区温度220℃，十区温度220℃，机头温度220℃；长径比为40，螺杆转速为800rpm，干燥后得到所述抗老化TPU-ABS合金材料。
实施例4
本实施例的一种抗老化TPU-ABS合金材料，按重量份计，包括如下组分：
ABS           80份
TPU           60份
复合抗老化剂  1份；
其中，ABS为透明级ABS(日本电气化学(ABS TH-21))，TPU(巴斯夫)的A型邵氏硬度为65A；
其中，复合抗老化剂由二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚组成；按复合抗老化剂100重量份计，二丁基羟基甲苯的重量份为30份，2-羟基-4正辛氧基二苯甲酮的重量份为30份，2，6-二叔丁基-4-甲基苯酚的重量份为40份。
本实施例的抗老化TPU-ABS合金材料的制备方法，包括如下步骤：
1)将ABS、TPU分别进行100℃干燥预处理1h；
2)以二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚为原料制备复合抗老化剂；
3)按配比将步骤1)预处理的ABS、TPU混合，加入步骤2)制得的复合抗老化剂，混合均匀得到混合物；
4)将步骤3)得到的混合物加入双螺杆挤出机中挤出造粒，双螺杆挤出机 的挤出温度为180-220℃，螺筒温度设定为：一区温度80℃，二区温度190℃，三区温度200℃，四区温度210℃，五区温度220℃，六区温度220℃，七区温度220℃，八区温度220℃，九区温度220℃，十区温度220℃，机头温度220℃；长径比为30，螺杆转速为400rpm，干燥后得到所述抗老化TPU-ABS合金材料。
实施例5
本实施例的一种抗老化TPU-ABS合金材料，按重量份计，包括如下组分：
ABS           70份
TPU           60份
复合抗老化剂  0.2份；
其中，ABS为透明级ABS(日本电气化学(ABS TH-21))，TPU(巴斯夫)的A型邵氏硬度为60A；
其中，复合抗老化剂由二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚组成；按复合抗老化剂100重量份计，二丁基羟基甲苯的重量份为20份，2-羟基-4正辛氧基二苯甲酮的重量份为50份，2，6-二叔丁基-4-甲基苯酚的重量份为30份。
本实施例的抗老化TPU-ABS合金材料的制备方法，包括如下步骤：
1)将ABS、TPU分别进行92℃干燥预处理1.6h；
2)以二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚为原料制备复合抗老化剂；
3)按配比将步骤1)预处理的ABS、TPU混合，加入步骤2)制得的复合抗老化剂，混合均匀得到混合物；
4)将步骤3)得到的混合物加入双螺杆挤出机中挤出造粒，双螺杆挤出机的挤出温度为180-220℃，螺筒温度设定为：一区温度80℃，二区温度190℃， 三区温度200℃，四区温度210℃，五区温度220℃，六区温度220℃，七区温度220℃，八区温度220℃，九区温度220℃，十区温度220℃，机头温度220℃；长径比为35，螺杆转速为500rpm，干燥后得到所述抗老化TPU-ABS合金材料。
实施例6
本实施例的一种抗老化TPU-ABS合金材料，按重量份计，包括如下组分：
Figure PCTCN2020140457-appb-000001
其中，ABS为透明级ABS(日本电气化学(ABS TH-21))，TPU(巴斯夫)的A型邵氏硬度为60A；
其中，复合抗老化剂由二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚组成；按复合抗老化剂100重量份计，二丁基羟基甲苯的重量份为20份，2-羟基-4正辛氧基二苯甲酮的重量份为50份，2，6-二叔丁基-4-甲基苯酚的重量份为30份。
本实施例的抗老化TPU-ABS合金材料的制备方法，包括如下步骤：
1)将ABS、TPU分别进行100℃干燥预处理1h；
2)以二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚为原料制备复合抗老化剂；
3)按配比将步骤1)预处理的ABS、TPU混合，加入步骤2)制得的复合抗老化剂、2，4-二羟基二苯甲酮和2-(2’-羟基-3’，5’-二叔苯基)-5-氯化苯并三唑，混合均匀得到混合物；
4)将步骤3)得到的混合物加入双螺杆挤出机中挤出造粒，双螺杆挤出机的挤出温度为180-220℃，螺筒温度设定为：一区温度80℃，二区温度190℃，三区温度200℃，四区温度210℃，五区温度220℃，六区温度220℃，七区温度220℃，八区温度220℃，九区温度220℃，十区温度220℃，机头温度220℃；长径比为30，螺杆转速为700rpm，干燥后得到所述抗老化TPU-ABS合金材料。
实施例7
本实施例与实施例1的区别之处在于，TPU的A型邵氏硬度为30A，其他的与实施例1的均相同。
实施例8
本实施例与实施例1的区别之处在于，TPU的A型邵氏硬度为80A，其他的与实施例1的均相同。
对比例1
本对比例与实施例1的区别之处在于，按复合抗老化剂100重量份计，复合抗老化剂由35份二丁基羟基甲苯和65份2-羟基-4正辛氧基二苯甲酮组成，其他的与实施例1的均相同。
对比例2
本对比例与实施例1的区别之处在于，按复合抗老化剂100重量份计，复合抗老化剂由45份二丁基羟基甲苯和55份2，6-二叔丁基-4-甲基苯酚组成，其他的与实施例1的均相同。
对比例3
本对比例与实施例1的区别之处在于，按复合抗老化剂100重量份计，复合抗老化剂由60份2-羟基-4正辛氧基二苯甲酮和40份2，6-二叔丁基-4-甲基苯酚组成，其他的与实施例1的均相同。
对比例4
本对比例与实施例1的区别之处在于，抗老化剂只有二丁基羟基甲苯，其他的与实施例1的均相同。
对比例5
本对比例与实施例1的区别之处在于，抗老化剂只有2-羟基-4正辛氧基二苯甲酮，其他的与实施例1的均相同。
对比例6
本对比例与实施例1的区别之处在于，抗老化剂只有2，6-二叔丁基-4-甲基苯酚，其他的与实施例1的均相同。
将实施例1-8与对比例1-6制得的TPU-ABS合金材料进行性能测试，根据热氧老化实验标准GB/T7141-2008，对制得的合金材料进行人工加速老化实验(90℃，500h)，并分别测定该塑料人工加速老化前后的拉伸强度、悬臂梁缺口冲击强度，参照ASTM D256标准测试0℃下的TPU-ABS合金材料的缺口冲击强度，测试结果如表1所示。
拉伸强度保持率＝(人工加速老化后的拉伸强度-人工加速老化前的拉伸强度)÷人工加速老化前的拉伸强度×100％。
冲击强度保持率＝(人工加速老化后的悬臂梁缺口冲击强度-人工加速老化前的悬臂梁缺口冲击强度)÷人工加速老化前的悬臂梁缺口冲击强度×100％。
表1
Figure PCTCN2020140457-appb-000002
Figure PCTCN2020140457-appb-000003
本发明的TPU-ABS合金材料的抗老化性能好，在低温和高温条件下，尤其是0℃低温及90℃的高温条件下均有较好的拉伸强度、缺口冲击强度。
实施例6中添加了光稳定剂后，与复合抗老化剂协同作用，进一步改善了TPU-ABS合金材料的抗老化性能。
实施例7、实施例8TPU的A型邵氏硬度太低或者太高，均不能达到较佳的低温和高温抗老化性能。
对比例1-6，复合抗老化剂中缺少一种或缺少两种组分，均不能达到较佳的低温和高温抗老化性能。
本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述 详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。

Claims (10)

  1. 一种抗老化TPU-ABS合金材料，其特征在于，按重量份计，所述抗老化TPU-ABS合金材料包括如下组分：
    ABS                 50-80份
    TPU                 40-60份
    复合抗老化剂        0.1-1份；
    其中，所述复合抗老化剂由二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚组成。
  2. 根据权利要求1所述的抗老化TPU-ABS合金材料，其特征在于，按复合抗老化剂100重量份计，所述二丁基羟基甲苯的重量份为10-30份，所述2-羟基-4正辛氧基二苯甲酮的重量份为30-50份，所述2，6-二叔丁基-4-甲基苯酚的重量份为30-40份。
  3. 根据权利要求1或2所述的抗老化TPU-ABS合金材料，其特征在于，按重量份计，所述抗老化TPU-ABS合金材料包括如下组分：
    ABS                 60-70份
    TPU                 40-50份
    复合抗老化剂        0.1-0.5份；
    其中，按复合抗老化剂100重量份计，所述复合抗老化剂由二丁基羟基甲苯10-20份、2-羟基-4正辛氧基二苯甲酮40-50份和2，6-二叔丁基-4-甲基苯酚30-40份组成。
  4. 根据权利要求1-3之一所述的抗老化TPU-ABS合金材料，其特征在于，按重量份计，所述抗老化TPU-ABS合金材料还包括1-2份的光稳定剂。
  5. 根据权利要求4所述的抗老化TPU-ABS合金材料，其特征在于，所述 光稳定剂为紫外线吸收剂；
    优选地，所述紫外线吸收剂为二苯甲酮类紫外线吸收剂和/或苯并三唑类紫外线吸收剂。
  6. 根据权利要求1-5之一所述的抗老化TPU-ABS合金材料，其特征在于，所述ABS为透明级ABS和/或耐热级ABS。
  7. 根据权利要求1-6之一所述的抗老化TPU-ABS合金材料，其特征在于，所述TPU的A型邵氏硬度为60-65A。
  8. 一种如权利要求1-7之一所述的抗老化TPU-ABS合金材料的制备方法，其特征在于，所述制备方法包括如下步骤：
    1)将ABS、TPU分别进行干燥预处理；
    2)以二丁基羟基甲苯、2-羟基-4正辛氧基二苯甲酮和2，6-二叔丁基-4-甲基苯酚为原料制备复合抗老化剂；
    3)按配比将步骤1)预处理的ABS、TPU混合，加入步骤2)制得的复合抗老化剂，混合均匀得到混合物；
    4)将步骤3)得到的混合物加入双螺杆挤出机中挤出造粒，干燥后得到所述抗老化TPU-ABS合金材料。
  9. 根据权利要求8所述的制备方法，其特征在于，步骤1)中，所述干燥的温度为90-100℃，所述干燥的时间为1-2h。
  10. 根据权利要求8或9所述的制备方法，其特征在于，步骤4)中，所述双螺杆挤出机的挤出温度为180-220℃，长径比为25-40，螺杆转速为200-800rpm。
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