Bio-based thermoplastic resin composite material and preparation method thereof

Abstract

The invention discloses a bio-based thermoplastic resin composite material and a preparation method thereof, and the bio-based thermoplastic resin composite material comprises the following components in parts by weight: 90-110 parts of thermoplastic resin, 2-4 parts of bio-based fibers, 8-12 parts of an organosilicon composite material, and 0.1-0.5 part of an antioxidant. The bio-based thermoplastic resin composite material prepared by the invention has excellent heat resistance, radiation resistance and wear resistance, also has recoverability and light weight performance, can be used as an automobile part material, and can be applied to the field of automobile parts. The problems that the compatibility between a bio-based material and macromolecular resin is poor, and the application range of a thermoplastic resin composite material is limited can be solved.

Description

Technical Field

[0001] The invention relates to the technical field of composites, and in particular to a bio-based thermoplastic resin composite material and a preparation method thereof. Background Art

[0002] With the continuous development and update of automotive materials, thermoplastic resin composites, with their lightweight, impact resistance, low expansion coefficient, corrosion resistance and other characteristics, make up for the shortcomings of traditional metal materials, meet special process and special design requirements, and have become a very important component of automotive composite materials. Compared with thermosetting resin materials, thermoplastic resin composites have the great advantages of simple molding process and recyclability, so the prospect of their application in automobiles is more extensive.

[0003] In order to improve the weather resistance, light aging resistance and friction resistance of currently commonly used thermoplastic resin materials, most of them adopt the addition of various compatibilizers, coupling agents, light stabilizers, etc. Although it can work to a certain extent, these additives will migrate to the surface after long-term light radiation or long-term use, resulting in the deterioration of the surface appearance quality of the resin material or affecting the mechanical properties of the finished product. At the same time, it will cause serious pollution and safety hazards to the production environment, and it is impossible to achieve the purpose of environmental protection and carbon reduction from the source.

[0004] Although aging can be improved by selecting the appropriate type and amount of plasticizers and stabilizers, reducing shear heat generation in the molding process, shortening the time the rubber is in a molten state, lowering the molding temperature, and using nitrogen to clean the hydraulic cylinder of the molding machine, etc., there are still some effects. It is impossible to control the migration of various additives to the surface to cause aging phenomena such as stickiness from the source. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a bio-based thermoplastic resin composite material and a preparation method thereof, which has excellent heat resistance, radiation resistance and wear resistance, and at the same time has both recyclability and lightweight performance. It can be used for automotive parts materials and can solve the problems of poor compatibility between bio-based materials and polymer resins and limited application range of thermoplastic resin composite materials.

[0006] The technical problem to be solved by the present invention is achieved through the following technical solutions:

[0007] A bio-based thermoplastic resin composite material comprises the following components in parts by weight: 90-110 parts of thermoplastic resin, 2-4 parts of bio-based fiber, 8-12 parts of organic silicon composite material, and 0.1-0.5 parts of antioxidant.

[0008] Preferably, the above technical solution includes the following components in parts by weight: 100 parts of thermoplastic resin, 3 parts of bio-based fiber, 10 parts of organosilicon composite material, and 0.3 parts of antioxidant.

[0009] Preferably, in the above technical solution, the thermoplastic resin is polyethylene, polypropylene, nylon 6, polybutylene terephthalate or polystyrene.

[0010] Preferably, in the above technical solution, the bio-based fiber is kenaf fiber, flax fiber, bamboo fiber, wood fiber or cotton fiber.

[0011] Preferably, in the above technical solution, the organic silicon composite material is a composite of modified organic silicon resin and modified aluminum oxide at a mass ratio of 1:0.1-1:7. The modified organic silicon and modified aluminum oxide particles play a synergistic role in the same system. In addition to stabilizing the structure, the modified aluminum oxide can reduce the amount of modified organic silicon and provide excellent performance.

[0012] Preferably, in the above technical solution, the modified silicone resin is prepared by the following method:

[0013] (1) Add the following raw materials into a flask: 2 g sodium dodecyl sulfate (SDS), 1 g octylphenol polyoxyethylene ether (OP-10), 0.35 g potassium persulfate (KPS), 0.75 g sodium bicarbonate (NaHCO3), and 100 g deionized water, stir and heat to 80°C;

[0014] (2) adding 1 / 10 of the core monomer dropwise for 15 minutes to obtain a seed emulsion; wherein the core monomer comprises: 25 g of butyl acrylate (BA) and 50 g of methyl acrylate (BMA);

[0015] (3) After keeping warm for 20 minutes, the remaining core monomer and initiator solution are added dropwise in parallel for 2 hours. After the addition is completed, the mixture is kept warm for 30 minutes to obtain a core emulsion; wherein the initiator solution comprises: 1 g SDS, 0.5 g OP-10, 0.2 g KPS, and 25 g deionized water;

[0016] (3) After the insulation is completed, the shell monomer and the initiator solution are added dropwise in parallel. After 2 / 3 of the shell monomer is added dropwise, vinyl triisopropoxy silane (AC-76) is added to the remaining shell monomer. The total dropping time is 3 hours; wherein the shell monomer includes: 52.5g isooctyl methacrylate (iBOA), 15g BA, 7.5g acrylic acid (AA), and the initiator solution includes: 0.2g KPS, 25g deionized water;

[0017] (4) After the dripping is completed, keep the temperature for 1 hour, cool it to below 40°C, discharge the material, and filter it to obtain the modified silicone.

[0018] Preferably, in the above technical solution, the antioxidant is one or a mixture of tris(2,4-di-tert-butyl)phenyl phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate or 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene produced by BASF.

[0019] A method for preparing a bio-based thermoplastic resin composite material comprises the following steps:

[0020] (1) Weigh 90-110 parts of thermoplastic resin, 2-4 parts of bio-based fiber, 8-12 parts of organosilicon composite material, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture;

[0021] (2) Extruding the mixed material obtained in step (1) from an extruder and granulating it to obtain a thermoplastic resin composite material.

[0022] Preferably, in the above technical scheme, the extruder includes six temperature zones arranged in sequence, the temperature of the first temperature zone is 170℃-260℃, the temperature of the second temperature zone is 220℃-260℃, the temperature of the third temperature zone is 230℃-260℃, the temperature of the fourth temperature zone is 240℃-260℃, the temperature of the fifth temperature zone is 240℃-260℃, the temperature of the sixth temperature zone is 240℃-260℃, the head temperature of the twin-screw extruder is 230℃-260℃, and the screw speed is 220r / min-300r / min.

[0023] Application of a bio-based thermoplastic resin composite material in public transportation cabin interiors.

[0024] The present invention introduces bio-based ingredients and silicone components, which effectively controls the stability of the material, enhances the heat resistance, radiation resistance and wear resistance of the resin substrate, and has excellent dimensional stability. It also gives full play to its cross-linking interaction, greatly improves the performance of the resin material, can achieve renewable resource utilization, and the product is compatible with the environment. It conforms to the industry trend of economic development in the automotive industry and has broad development space.

[0025] The modified silicone composite material and bio-based fiber are blended and modified to prepare a thermoplastic resin composite material mixture, and then the mixture is extruded from an extruder for granulation to obtain a thermoplastic resin composite material, wherein the modified silicone resin is synthesized by semi-continuous seed emulsion polymerization using vinyl triisopropoxysilane. The modified silicone composite material has the properties of both inorganic and organic materials. Due to the difference in bond energy, the vinyl in the silicone can promote the migration of the silicon carbon layer material surface, prevent the internal polymer material from contacting with oxygen in the air or undergoing oxidation chain scission reaction under light radiation, and can maintain the initial physical properties in a wide temperature range, showing good resistance to high and low temperatures, radiation, and weathering. The composite material is entangled with the thermoplastic resin, so that the composite material and the thermoplastic resin form physical crosslinking points, which increases the interface compatibility, can effectively increase the heat resistance, radiation resistance and wear resistance of the thermoplastic resin composite material, and can be recycled, so that the utilization rate of the thermoplastic composite material is greatly improved and the production cost is reduced.

[0026] The above technical solution of the present invention has the following beneficial effects:

[0027] (1) The preparation process is simple, the raw materials are environmentally friendly and low-carbon, and the natural fiber materials help reduce weight. At the same time, the production and preparation process meets the low-carbon goals of automobiles and is conducive to promoting carbon reduction throughout the life cycle of automobiles;

[0028] (2) It has good heat resistance, radiation resistance, weather resistance, flame retardancy, low emission, and no odor. It can effectively reduce material waste, improve component assembly tolerances, and improve component quality without generating harmful emissions. DETAILED DESCRIPTION

[0029] Various exemplary embodiments of the present invention will now be described in detail. It should be noted that the relative arrangement of components and steps, numerical expressions and numerical values ​​set forth in these embodiments do not limit the scope of the present invention unless otherwise specifically stated.

[0030] Example 1

[0031] A method for preparing a bio-based thermoplastic resin composite material comprises the following steps:

[0032] (1) Weigh 90 parts of polypropylene (PP), 2 parts of flax fiber, 8 parts of silicone composite material, and 0.1 part of Irganox 1010, mix and stir evenly to obtain a mixture.

[0033] (2) The mixed material is extruded from an extruder and granulated to obtain a composite material example 1.

[0034] The organic silicon composite material in the above step (1) is a composite of modified organic silicon resin and modified aluminum oxide in a mass ratio of 1:0.1.

[0035] Modified alumina is commercially available, and the modified silicone resin is prepared by the following preparation method:

[0036] In a 500mL four-necked flask equipped with a stirring paddle, a condenser, a thermometer and a constant pressure dropping funnel, add 2g SDS, 1g OP-10, 0.35g KPS, 0.75g NaHCO3 and 100g deionized water, stir and heat to 80°C at the same time; add 1 / 10 of the core monomer (25g BA, 50g BMA) dropwise, and finish dropping within 15 minutes to obtain a seed emulsion; after keeping warm for 20 minutes, add the remaining core monomer and initiator solution (1g SDS, 0.5g OP-10, 0.2g KPS, 25g deionized water) dropwise in parallel, the dropping time is 2h, and keep warm for 30 minutes after dropping to obtain a core emulsion. After the insulation is completed, shell monomer (52.5g BOA, 15g BA, 7.5g AA) and initiator solution (0.2g KPS, 25g deionized water) are added dropwise in parallel; after 2 / 3 of the shell monomer is added dropwise, AC-76 is added to the remaining shell monomer, and the total dropping time is 3h; after the dropping is completed, the mixture is kept warm for 1h, cooled to below 40°C, discharged, and filtered to obtain the modified silicone resin.

[0037] In the above step (2), the twin-screw extruder includes six temperature zones arranged in sequence, the temperature of the first temperature zone is 170°C, the temperature of the second temperature zone is 220°C, the temperature of the third temperature zone is 230°C, the temperature of the fourth temperature zone is 240°C, the temperature of the fifth temperature zone is 240°C, the temperature of the sixth temperature zone is 240°C, the head temperature of the twin-screw extruder is 230°C, and the screw speed is 220r / min.

[0038] Example 2

[0039] A method for preparing a bio-based thermoplastic resin composite material comprises the following steps:

[0040] (1) 110 parts of polybutylene terephthalate (PBT), 4 parts of bamboo fiber, 12 parts of silicone composite material, 0.1 parts of Irganox 1010, 0.2 parts of Irganox 168, and 0.3 parts of Irganox 1330 were weighed and mixed and stirred to obtain a mixture.

[0041] (2) Extruding the mixed material from the extruder and granulating it to obtain Composite Material Example 2.

[0042] The organic silicon composite material in the above step (1) is a composite of modified organic silicon resin and modified aluminum oxide in a mass ratio of 1:7.

[0043] The modified alumina is commercially available, and the modified silicone resin is prepared by the preparation method of Example 1.

[0044] In the above step (2), the twin-screw extruder includes six temperature zones arranged in sequence, the temperature of the first temperature zone is 200°C, the temperature of the second temperature zone is 260°C, the temperature of the third temperature zone is 260°C, the temperature of the fourth temperature zone is 260°C, the temperature of the fifth temperature zone is 260°C, the temperature of the sixth temperature zone is 260°C, the head temperature of the twin-screw extruder is 260°C, and the screw speed is 300r / min.

[0045] Example 3

[0046] A method for preparing a bio-based thermoplastic resin composite material comprises the following steps:

[0047] (1) Weigh 100 parts of polyethylene (PE), 3 parts of kenaf fiber, 10 parts of modified silicone resin material N3, 0.2 parts of Irganox 1330, and 0.1 parts of Irganox 168, mix and stir evenly to obtain a mixture.

[0048] (2) The mixed material is extruded from an extruder and granulated to obtain PE composite material example 3.

[0049] The organic silicon composite material in the above step (1) is a composite of modified organic silicon resin and modified aluminum oxide in a mass ratio of 1:5.

[0050] The modified alumina is commercially available, and the modified silicone resin is prepared by the preparation method of the present application.

[0051] In the above step (2), the twin-screw extruder includes six temperature zones arranged in sequence, the temperature of the first temperature zone is 120°C, the temperature of the second temperature zone is 180°C, the temperature of the third temperature zone is 180°C, the temperature of the fourth temperature zone is 180°C, the temperature of the fifth temperature zone is 180°C, the temperature of the sixth temperature zone is 180°C, the head temperature of the twin-screw extruder is 180°C, and the screw speed is 300r / min.

[0052] Comparative Example 1

[0053] A method for preparing a bio-based thermoplastic resin composite material comprises the following steps:

[0054] (1) Weigh 100 parts of polyethylene (PE), 3 parts of flax fiber, 0.2 parts of Irganox 1330, and 0.1 parts of Irganox 168, mix and stir evenly to obtain a mixture.

[0055] (2) The mixed material is extruded from an extruder and granulated to obtain a PE composite material comparison 1.

[0056] In the above step (2), the twin-screw extruder includes six temperature zones arranged in sequence, the temperature of the first temperature zone is 170°C, the temperature of the second temperature zone is 220°C, the temperature of the third temperature zone is 230°C, the temperature of the fourth temperature zone is 240°C, the temperature of the fifth temperature zone is 240°C, the temperature of the sixth temperature zone is 240°C, the head temperature of the twin-screw extruder is 230°C, and the screw speed is 220r / min.

[0057] Performance test of Examples 1-3 and Comparative Example 1:

[0058] (1) Abrasion resistance test: The scratch resistance test is conducted with a scratch resistance tester, the cross grid size is greater than or equal to 40mm*40mm, the test load is 10N, the speed is 1000mm / min, and the cutter diameter is 1mm. After scratching, the color difference ΔL before and after the scratching area is measured under D65 light source in the cross grid area. ΔL ≤ 2.0 is in compliance with the standard, where the larger the level, the worse the effect.

[0059] (2) Light aging test: Place the sample in a xenon light instrument with the following light requirements: black standard temperature (100±3)℃; sample room temperature (65±3)℃; sample room relative air humidity (20±10)%; irradiation intensity (420nm) 1.2W / m2. The following irradiation is considered as one light cycle, such as Ci4000 xenon light instrument = 280KJ / m2 (420nm). Perform 5 cycles of chlorine lamp aging test and observe the surface grayscale level. The larger the level, the worse the effect. Grayscale ≥4 is qualified. Observe whether there are bubbles, cracks, powdering and other problems on the surface.

[0060] (3) Environmental alternation test: The test has 8 cycles in total, one cycle includes 60 minutes of heating to 80°C and 80% humidity; 240 minutes of maintaining 80°C and 80% humidity; 120 minutes of cooling to -40°C and 30% humidity; 240 minutes of maintaining -40°C; 60 minutes of temperature rising to 23°C and 30% humidity. The samples are tested using the DIN EN ISO 2049 standard of the 100-grid test to obtain the grade results, and the larger the grade, the worse the effect. A 10N Newton pen with a 0.75mm head (model 318S) is used for the scratch resistance test.

[0061] (4) Odor test: No water is added to the 1L container, stored at (80±2)℃, storage time (2h±10min): The test is completed by more than 5 judges, and the evaluation value is the average. The scoring criteria are as follows: 1. There is an unbearable odor; 2. There is a strong interfering odor; 3. There is an interfering odor; 4. There is a clear odor, but not interfering; 5. There is an odor, but not interfering; 6. No odor.

[0062] The experimental results are shown in Table 1.

[0063] Table 1 Performance test

[0064] project Example 1 Example 2 Example 3 Comparative Example Friction resistance test 1.5 1.6 1.8 0.8 Light aging test 4 4 4 3 Environmental alternation test 0.7 0.8 0.9 0.2 Odor test 4 4 4 3

[0065] The modified organosilicon bio-based composite thermoplastic resin of the present application integrates the organosilicon composite material with the bio-based fiber and the thermoplastic resin block, which can ensure that the composite thermoplastic resin composite material is resistant to high and low temperatures, corrosion-resistant, non-toxic and odorless, and has good weather resistance. Compared with ordinary thermoplastic resin materials, it is not easily decomposed by ultraviolet light and ozone oxidation, has better radiation resistance and weather resistance, and has a longer service life. It is economical, environmentally friendly, non-toxic, pollution-free, and has no residual toxicity. It also meets the requirements of the low-carbon strategy in the automobile production process.

[0066] The silicone / bio-based composite thermoplastic resin proposed in the present invention has excellent light resistance and weather resistance, as well as extremely good safety in use. It can be used not only in automobile cabin interiors, but also in other public transportation scenarios (buses, subways, airplanes, etc.), effectively eliminating the adverse effects of pollution or bumps and scratches on the interior surface during use, thereby improving cabin comfort and reducing maintenance requirements.

[0067] Although the present invention has been disclosed as above by the embodiments, it is not intended to limit the present invention. Any person skilled in the art may make various choices and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention is limited by the claims and their equivalents.

Claims

1. A bio-based thermoplastic resin composite material, characterized in that: The invention comprises the following components in parts by weight: 90-110 parts of thermoplastic resin, 2-4 parts of bio-based fiber, 8-12 parts of organic silicon composite material and 0.1-0.5 parts of antioxidant.

2. The bio-based thermoplastic resin composite material according to claim 1, characterized in that: The invention comprises the following components in parts by weight: 100 parts of thermoplastic resin, 3 parts of bio-based fiber, 10 parts of organic silicon composite material and 0.3 parts of antioxidant.

3. The bio-based thermoplastic resin composite material according to claim 1, characterized in that: The thermoplastic resin is polyethylene, polypropylene, nylon 6, polybutylene terephthalate or polystyrene.

4. The bio-based thermoplastic resin composite material according to claim 1, characterized in that: The bio-based fiber is kenaf fiber, flax fiber, bamboo fiber, wood fiber or cotton fiber.

5. The bio-based thermoplastic resin composite material according to claim 1, characterized in that: The organic silicon composite material is a composite of modified organic silicon resin and modified aluminum oxide in a mass ratio of 1:0.1-1:

7.

6. The bio-based thermoplastic resin composite material according to claim 5, characterized in that: The modified silicone resin is prepared by the following method: (1) Add the following raw materials into a flask: 2 g sodium dodecyl sulfate (SDS), 1 g octylphenol polyoxyethylene ether (OP-10), 0.35 g potassium persulfate (KPS), 0.75 g sodium bicarbonate (NaHCO3), and 100 g deionized water, stir and heat to 80°C; (2) adding 1 / 10 of the core monomer dropwise for 15 minutes to obtain a seed emulsion; wherein the core monomer comprises: 25 g of butyl acrylate (BA) and 50 g of methyl acrylate (BMA); (3) After keeping warm for 20 minutes, the remaining core monomer and initiator solution are added dropwise in parallel for 2 hours. After the addition is completed, the mixture is kept warm for 30 minutes to obtain a core emulsion; wherein the initiator solution comprises: 1 g SDS, 0.5 g OP-10, 0.2 g KPS, and 25 g deionized water; (3) After the insulation is completed, the shell monomer and the initiator solution are added dropwise in parallel. After 2 / 3 of the shell monomer is added dropwise, vinyl triisopropoxy silane (AC-76) is added to the remaining shell monomer. The total dropping time is 3 hours; wherein the shell monomer includes: 52.5g isooctyl methacrylate (iBOA), 15g BA, 7.5g acrylic acid (AA), and the initiator solution includes: 0.2g KPS, 25g deionized water; (4) After the dripping is completed, keep the temperature for 1 hour, cool it to below 40°C, discharge the material, and filter it to obtain the modified silicone.

7. The bio-based thermoplastic resin composite material according to claim 1, characterized in that: The antioxidant is one of tris(2,4-di-tert-butyl)phenyl phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate or 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene or a mixture of several thereof.

8. The method for preparing a bio-based thermoplastic resin composite material according to any one of claims 1 to 7, characterized in that: The following steps are involved: (1) Weigh 90-110 parts of thermoplastic resin, 2-4 parts of bio-based fiber, 8-12 parts of organosilicon composite material, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture; (2) Extruding the mixed material obtained in step (1) from an extruder and granulating it to obtain a thermoplastic resin composite material.

9. The method for preparing a bio-based thermoplastic resin composite material according to claim 8, characterized in that: The extruder includes six temperature zones arranged in sequence, the temperature of the first temperature zone is 170℃-260℃, the temperature of the second temperature zone is 220℃-260℃, the temperature of the third temperature zone is 230℃-260℃, the temperature of the fourth temperature zone is 240℃-260℃, the temperature of the fifth temperature zone is 240℃-260℃, the temperature of the sixth temperature zone is 240℃-260℃, the head temperature of the twin-screw extruder is 230℃-260℃, and the screw speed is 220r / min-300r / min.

10. Use of the bio-based thermoplastic resin composite material according to claims 1-7 in public transportation cabin interiors.