Bio-based spraying-free material and preparation method thereof

Abstract

The invention provides a bio-based spraying-free material and a preparation method thereof. The bio-based spraying-free material is prepared from the following raw materials in parts by weight: 30 to 65 parts of bio-based isosorbide polycarbonate, 15 to 25 parts of ASA (Acrylonitrile Styrene Acrylate) high rubber powder, 15 to 40 parts of acrylonitrile-styrene polymer, 0 to 10 parts of compatilizer, 0.1 to 0.5 part of antioxidant, 0.1 to 0.5 part of lubricant and 0.2 to 0.5 part of weather-resistant agent. The adopted bio-based isosorbide polycarbonate is non-toxic and has a rigid ester ring structure, the ASA high rubber powder and the acrylonitrile-styrene polymer provide flexibility and impact resistance, and through a rigid-flexible molecular chain structure, the impact resistance is good while the strength and hardness are maintained; besides, through the synergistic effect of all the components, while the bio-based source and environmental friendliness are maintained, the composition also has excellent heat resistance, aging resistance and weather resistance, and can meet the requirements of automobile exterior decorations.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a bio-based spray-free material and a preparation method thereof. Background Art

[0002] Polycarbonate (PC) is a type of linear high molecular polymer containing carbonate groups (-OROCO-) in the molecular chain. It not only has outstanding impact resistance and creep resistance, but also has high tensile strength, bending strength, elongation at break and rigidity. In addition, it also has high heat resistance and cold resistance. It has become one of the fastest growing thermoplastic materials in the five major general engineering plastics and has a wide range of applications in various fields. In recent years, the commonly used PC mainstream product on the market is bisphenol A polycarbonate (BPA-PC), which is widely used in bulletproof glass, food packaging, automobile transportation, aerospace, electronic and electrical boxes and construction materials. However, it is reported that BPA-PC has estrogenic effects and chronic toxic effects, which may endanger human health. Therefore, it is necessary to find a green and sustainable alternative to bisphenol A polycarbonate.

[0003] Isosorbide (ISB) is a bicyclic diol with relatively stable chemical and thermal properties. It is a renewable monomer derived from biomass and has a similar rigid structure to BPA. Isosorbide-type polycarbonate synthesized with ISB is not only green and non-toxic, but also has better optical properties, scratch resistance and weather resistance than traditional BPA-type polycarbonate. At present, isosorbide-type polycarbonate is mainly synthesized by melt polycondensation of ISB and DMC, which can effectively avoid the use of toxic monomers and solvents, does not require the recovery of catalysts, and can replace the phosgene method. However, due to the special rigid structure of ISB, the synthesized PC has the disadvantages of poor flexibility and poor processing performance. When applied to automotive exterior parts, if impact resistance, heat resistance, aging resistance and weather resistance are to be taken into account, there is still a need for improvement. Summary of the invention

[0004] 1. Technical issues to be resolved

[0005] In view of the shortcomings of the prior art, the present invention provides a bio-based spray-free material and a preparation method thereof. Through the synergistic effect of isosorbide polycarbonate, ASA high rubber powder and acrylonitrile-styrene polymer, mechanical properties, heat resistance and aging resistance can be taken into account at the same time, thereby solving the problems raised in the above background technology.

[0006] (II) Technical solution

[0007] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0008] According to a first aspect of the present invention, a bio-based spray-free material is provided. The raw materials for preparing the bio-based spray-free material include the following components in parts by weight:

[0009] 30-65 parts of bio-based isosorbide polycarbonate, 15-25 parts of ASA high rubber powder, 15-40 parts of acrylonitrile-styrene polymer, 0-10 parts of compatibilizer, 0.1-0.5 parts of antioxidant, 0.1-0.5 parts of lubricant and 0.2-0.5 parts of weathering agent.

[0010] The bio-based isosorbide polycarbonate in this application has good weather resistance, but insufficient toughness. By selecting ASA high-rubber powder that is compatible with bio-based isosorbide polycarbonate for toughening, and adding a compatibilizer to improve the compatibility of the two phases, the weather resistance and impact toughness are improved.

[0011] Since the molecular weight of bio-based isosorbide polycarbonate is lower than 10,000, the mechanical properties are poor and it is difficult to improve them with toughening agents. If the molecular weight is higher than 40,000, the viscosity is too high and it is difficult to carry out subsequent processing and molding. Preferably, the molecular weight of the bio-based isosorbide polycarbonate is 10,000 to 40,000.

[0012] Further preferably, the model of the bio-based isosorbide polycarbonate is T7450A.

[0013] Since the particle size of butyl acrylate rubber is too small, it cannot effectively absorb energy when the material is impacted, resulting in low impact strength of the material. However, if the particle size of butyl acrylate rubber is too large, the product's appearance will be poor, and large particles will have poor colorability and a negative effect on weather resistance, reducing the light aging performance of the entire material. Preferably, the particle size of butyl acrylate rubber in the ASA high rubber powder is 80-120nm, and the silicone content is 2-10%.

[0014] Further preferably, the model of the ASA high-rubber powder is Q900.

[0015] When the acrylonitrile content in the acrylonitrile-styrene polymer is lower than 20%, the compatibility with the bio-based isosorbide polycarbonate is poor, resulting in low mechanical properties of the material. When the acrylonitrile content in the acrylonitrile-styrene polymer is higher than 30%, the viscosity of the polymer is too high to be dispersed, the compatibility is reduced, and molding processing is not conducive. Preferably, the acrylonitrile content in the acrylonitrile-styrene polymer is 20 to 30%.

[0016] Preferably, the mass ratio of the ASA high rubber powder, bio-based isosorbide polycarbonate and acrylonitrile-styrene polymer is 3:11-13:3-5.

[0017] Preferably, the compatibilizer is selected from the compatibilizer SMA.

[0018] Preferably, the antioxidant comprises a primary antioxidant and a secondary antioxidant, and the mass ratio of the primary antioxidant to the secondary antioxidant is 1:2-3;

[0019] The primary antioxidant is selected from at least one of antioxidant 1010 and antioxidant 1076;

[0020] The auxiliary antioxidant is selected from at least one of antioxidant 168, antioxidant 169F, and antioxidant 412S.

[0021] Preferably, the lubricant is selected from pentaerythritol stearate;

[0022] The weathering agent is selected from at least one of UV-234, UV-328 and UV-P.

[0023] According to a second aspect of the present invention, a method for preparing a bio-based spray-free material is provided, comprising the following steps:

[0024] (1) adding bio-based isosorbide polycarbonate, ASA high rubber powder, acrylonitrile-styrene polymer, compatibilizer, antioxidant, lubricant and weathering agent into a high-speed mixer and mixing according to weight;

[0025] (2) The mixed raw materials are continuously and evenly added into a twin-screw extruder for extrusion, and the extruded material strips are cooled and pelletized to obtain the bio-based spray-free material.

[0026] Preferably, the conditions and parameters for extrusion through the twin-screw extruder are: the mixed raw materials are continuously and evenly added to the main barrel of the twin-screw extruder, the screw diameter is 35 mm, the aspect ratio L / D is 36, the temperature of zone 1 of the main barrel is 60-100°C, the temperature of zone 2 is 230-250°C, the temperature of zone 3 is 240-260°C, the temperature of zone 4 is 240-260°C, the temperature of zone 5 is 230-250°C, the temperature of zone 6 is 220-240°C, the temperature of zone 7 is 220-240°C, the temperature of zone 8 is 220-240°C, the speed of the twin screw is 300 rpm, and the extruded material strips are cooled in a water tank and then pelletized.

[0027] (III) Beneficial effects

[0028] The present invention provides a bio-based spray-free material and a preparation method thereof, which has the following beneficial effects:

[0029] This solution provides a bio-based spray-free material, which uses bio-based isosorbide polycarbonate, which is non-toxic and has a rigid ester ring structure. ASA high-rubber powder and acrylonitrile-styrene polymer provide flexibility and impact resistance. The rigid and flexible molecular chain structure maintains strength and hardness while also having good impact resistance. In addition, through the synergistic effect of each component, while maintaining bio-based origin and environmental friendliness, it also has excellent heat resistance, aging resistance and weather resistance, which can meet the needs of automotive exteriors. DETAILED DESCRIPTION

[0030] In order to explain the present invention more clearly, the present invention is further described below in conjunction with specific embodiments. It should be understood by those skilled in the art that the content described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0031] The bio-based isosorbide polycarbonate used in the embodiments of the present invention is manufactured by Mitsubishi Corporation of Japan, and the model number is T7450A;

[0032] ASA high-rubber powder, manufactured by Anqiu Donghai Plastic Industry Co., Ltd., model Q900;

[0033] Acrylonitrile-styrene polymer I, prepared by LG Yongxing Company, with an acrylonitrile content of 30%, model AS80HF;

[0034] Acrylonitrile-styrene polymer II, manufactured by Taiwan Chemical Fiber Co., Ltd., model number ASNF2200AS;

[0035] The common PC used in the comparative examples of the present invention is manufactured by Mitsubishi Chemical Corporation, and its model is S-2000F; the ASA high-rubber powder is manufactured by UMG, and its model is A600N.

[0036] Example 1

[0037] A bio-based spray-free material, wherein the raw materials for preparing the bio-based spray-free material include, by weight, 30 parts of bio-based isosorbide polycarbonate of model T7450, 25 parts of butyl acrylate rubber with a particle size of 90nm and a silicone content of 5%, ASA high rubber powder of model Q900, 40 parts of AS 80HF with an acrylonitrile content of 30%, 5 parts of a compatibilizer SMA, 0.1 parts of a primary antioxidant 1076, 0.1 parts of an auxiliary antioxidant 168, 0.3 parts of pentaerythritol stearate and 0.5 parts of UV-234.

[0038] The specific preparation method is as follows:

[0039] The prepared raw materials are added to a high-speed mixer and mixed for 5 minutes. The mixed raw materials are continuously and evenly added to a twin-screw extruder for extrusion. The screw diameter of the twin-screw extruder is controlled to be 35 mm, the aspect ratio L / D is 36, the temperature of zone 1 of the main barrel is 60-100°C, the temperature of zone 2 is 230-250°C, the temperature of zone 3 is 240-260°C, the temperature of zone 4 is 240-260°C, the temperature of zone 5 is 230-250°C, the temperature of zone 6 is 220-240°C, the temperature of zone 7 is 220-240°C, the temperature of zone 8 is 220-240°C, the speed of the twin screw is 300 rpm, the extruded material strips are cooled and pelletized to obtain a bio-based spray-free material.

[0040] Example 2

[0041] The present embodiment provides a bio-based spray-free material, wherein the raw materials for its preparation are calculated by weight and include 45 parts of bio-based isosorbide polycarbonate of model T7450, 20 parts of butyl acrylate rubber with a particle size of 90 nm and a silicone content of 5%, ASA high rubber powder of model Q900, 30 parts of AS 80HF with an acrylonitrile content of 30%, 5 parts of compatibilizer SMA, 0.1 parts of primary antioxidant 1076, 0.1 parts of auxiliary antioxidant 168, 0.3 parts of lubricant pentaerythritol stearate, and 0.5 parts of weathering agent UV-234.

[0042] Example 3

[0043] The present embodiment provides a bio-based spray-free material, wherein the raw materials for its preparation are calculated by weight and include 55 parts of bio-based isosorbide polycarbonate of model T7450, 15 parts of butyl acrylate rubber with a particle size of 90 nm and a silicone content of 5%, ASA high rubber powder of model Q900, 25 parts of AS 80HF with an acrylonitrile content of 30%, 5 parts of compatibilizer SMA, 0.1 parts of primary antioxidant 1076, 0.1 parts of auxiliary antioxidant 168, 0.3 parts of lubricant pentaerythritol stearate, and 0.5 parts of weathering agent UV-234.

[0044] Example 4

[0045] The present embodiment provides a bio-based spray-free material, wherein the raw materials for its preparation are calculated by weight and include 65 parts of bio-based isosorbide polycarbonate of model T7450, 15 parts of butyl acrylate rubber with a particle size of 90 nm and a silicone content of 5%, ASA high rubber powder of model Q900, 25 parts of AS 80HF with an acrylonitrile content of 30%, 5 parts of compatibilizer SMA, 0.1 parts of primary antioxidant 1076, 0.1 parts of auxiliary antioxidant 168, 0.3 parts of lubricant pentaerythritol stearate, and 0.2 parts of weathering agent UV-234.

[0046] Example 5

[0047] The present embodiment provides a bio-based spray-free material, wherein the raw materials for its preparation are, by weight, 65 parts of bio-based isosorbide polycarbonate of model T7450, 15 parts of butyl acrylate rubber with a particle size of 90 nm and a silicone content of 5%, ASA high rubber powder of model Q900, 15 parts of AS 80HF with an acrylonitrile content of 30%, 5 parts of compatibilizer SMA, 0.1 parts of primary antioxidant 1076, 0.1 parts of auxiliary antioxidant 168, 0.3 parts of lubricant pentaerythritol stearate, and 0.5 parts of weathering agent UV-234.

[0048] Example 6

[0049] The present embodiment provides a bio-based spray-free material, wherein the raw materials for its preparation are calculated by weight and include 65 parts of bio-based isosorbide polycarbonate of model T7450, 15 parts of butyl acrylate rubber with a particle size of 90 nm and a silicone content of 5%, ASA high rubber powder of model Q900, 25 parts of AS 80HF with an acrylonitrile content of 30%, 5 parts of compatibilizer SMA, 0.1 parts of primary antioxidant 1076, 0.1 parts of auxiliary antioxidant 168, 0.3 parts of lubricant pentaerythritol stearate, and 0.5 parts of weathering agent UV-234.

[0050] Comparative Example 7

[0051] The present embodiment provides a bio-based spray-free material, and its preparation raw materials, measured by weight, include 65 parts of bio-based isosorbide polycarbonate with model number T7450, 15 parts of butyl acrylate rubber with a particle size of 90nm and a silicone content of 5%, ASA high rubber powder with model number Q900, 20 parts of AS 80HF with an acrylonitrile content of 30%, 0.1 parts of a primary antioxidant 1076, 0.1 parts of an auxiliary antioxidant 168, 0.3 parts of a lubricant pentaerythritol stearate, and 0.5 parts of a weathering agent UV-234.

[0052] Example 8

[0053] The present embodiment provides a bio-based spray-free material, and its preparation raw materials, measured by weight, include 65 parts of bio-based isosorbide polycarbonate with model number T7450, 15 parts of butyl acrylate rubber with a particle size of 90nm and a silicone content of 5%, ASA high rubber powder with model number Q900, 10 parts of AS 80HF with an acrylonitrile content of 30%, 0.1 parts of a primary antioxidant 1076, 0.1 parts of an auxiliary antioxidant 168, 0.3 parts of a lubricant pentaerythritol stearate, and 0.5 parts of a weathering agent UV-234.

[0054] Comparative Example 1

[0055] A spray-free material, wherein the raw materials for its preparation are calculated by weight and include 45 parts of common PC, 20 parts of butyl acrylate rubber with a particle size of 90nm and a silicone content of 5%, ASA rubber powder of model A600N, 5 parts of compatibilizer SMA, 0.1 parts of primary antioxidant 1076, 0.1 parts of secondary antioxidant 168, 0.3 parts of lubricant pentaerythritol stearate and 0.5 parts of weathering agent UV-234.

[0056] Comparative Example 2

[0057] A spray-free material, wherein the raw materials for its preparation are calculated by weight and include 65 parts of common PC, 15 parts of ASA high rubber powder of model Q900 with a particle size of 90nm and a silicone content of 5%, 15 parts of AS 80HF with a content ratio of acrylonitrile to styrene of 1:3, 5 parts of compatibilizer SMA, 0.1 parts of primary antioxidant 1076, 0.1 parts of auxiliary antioxidant 168, 0.3 parts of lubricant pentaerythritol stearate and 0.5 parts of weathering agent UV-234.

[0058] Comparative Example 3

[0059] A bio-based spray-free material, wherein the raw materials for its preparation, measured by weight, include 65 parts of bio-based isosorbide polycarbonate with model number T7450, 15 parts of ASA rubber powder with model number A600N, 15 parts of AS 80HF with a content ratio of acrylonitrile to styrene of 1:3, 5 parts of compatibilizer SMA, 0.1 parts of primary antioxidant 1076, 0.1 parts of secondary antioxidant 168, 0.3 parts of lubricant pentaerythritol stearate and 0.5 parts of weathering agent UV-234.

[0060] The performance of the spray-free materials prepared in Examples 1 to 6 of the present invention and Comparative Examples 1 to 3 is tested as follows;

[0061] (1) Tensile property test: According to ISO 527-2 standard, the sample size is 170×10×4 mm, and the tensile speed is 50 mm / min;

[0062] (2) Notched impact test: performed in accordance with ISO 179-1 standard, with a specimen size of 80 × 10 × 4 mm;

[0063] (3) Bending performance test: carried out in accordance with ISO 178 standard, the sample size is 80×10×4 mm, and the bending speed is 2 mm / min;

[0064] (4) Melt flow rate test: carried out in accordance with ISO 1133-1 standard, the test conditions are 260℃ / 5kg;

[0065] (5) Density test: carried out in accordance with ISO 1183-1 standard, the sample size is 10×10×4 mm, and the test temperature is 23°C;

[0066] (6) Heat deformation temperature test: carried out in accordance with ISO 75-2 standard, the sample size is 80×10×4 mm, the conditions are 0.45 MPa, 120°C / h;

[0067] (7) Xenon lamp accelerated aging test to test weather resistance: SAE J2412 was used for light aging test. The test conditions were as follows:

[0068] Irradiance: (0.55±0.01)W / (m 2 nm)@340nm;

[0069] Lighting: 3.8h, blackboard temperature: (89±2.5)℃, relative humidity: (50±10)%;

[0070] Darkness: 1h, blackboard temperature: (38±2.5)℃, relative humidity: (95±10)%;

[0071] Filter: Quartz / Boro;

[0072] Radiation dose: 2500kJ / m 2 .

[0073] The test results are shown in Table 1:

[0074] Table 1

[0075]

[0076]

[0077] It can be seen from the data in Table 1 that the bio-based spray-free material prepared by the present invention has excellent impact toughness and heat resistance, and can meet the weather resistance requirements of automotive exterior parts. The weather resistance of comparative examples 1-3 cannot meet the requirements of ≥ level 4 and cannot be used for exterior products. It can be seen from the data in Table 1 that the mass ratio of the raw materials for preparing the bio-based spray-free material, bio-based isosorbide polycarbonate, ASA high rubber powder and SAN1 is in the range of 55-65:15-25:15, and the bio-based spray-free material has excellent effects in tensile properties, impact toughness, bending properties, heat resistance and weather resistance.

[0078] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A bio-based spray-free material, characterized in that: The raw materials for preparing the bio-based spray-free material include the following components in parts by weight: 30-65 parts of bio-based isosorbide polycarbonate, 15-25 parts of ASA high rubber powder, 15-40 parts of acrylonitrile-styrene polymer, 0-10 parts of compatibilizer, 0.1-0.5 parts of antioxidant, 0.1-0.5 parts of lubricant and 0.2-0.5 parts of weathering agent.

2. The bio-based spray-free material according to claim 1, characterized in that: The molecular weight of the bio-based isosorbide polycarbonate is 10,000-40,000.

3. The bio-based spray-free material according to claim 1, characterized in that: The particle size of the butyl acrylate rubber in the ASA high-rubber powder is 80-120 nm, and the content of organic silicon is 2-10%.

4. The bio-based spray-free material according to claim 1, characterized in that: The content of acrylonitrile in the acrylonitrile-styrene polymer is 20-30%.

5. The bio-based spray-free material according to claim 1, characterized in that: The mass ratio of the ASA high-rubber powder, the bio-based isosorbide polycarbonate and the acrylonitrile-styrene polymer is 3:11-13:3-5.

6. The bio-based spray-free material according to claim 1, characterized in that: The compatibilizer is selected from compatibilizer SMA.

7. The bio-based spray-free material according to claim 1, characterized in that: The antioxidant comprises a primary antioxidant and a secondary antioxidant, and the mass ratio of the primary antioxidant to the secondary antioxidant is 1:2-3; The primary antioxidant is selected from at least one of antioxidant 1010 and antioxidant 1076; The auxiliary antioxidant is selected from at least one of antioxidant 168, antioxidant 169F, and antioxidant 412S.

8. The bio-based spray-free material according to claim 1, characterized in that: The lubricant is selected from pentaerythritol stearate; The weathering agent is selected from at least one of UV-234, UV-328 and UV-P.

9. A method for preparing the bio-based spray-free material according to any one of claims 1 to 8, characterized in that: (1) adding bio-based isosorbide polycarbonate, ASA high rubber powder, acrylonitrile-styrene polymer, compatibilizer, antioxidant, lubricant and weathering agent into a high-speed mixer and mixing according to weight; (2) The mixed raw materials are continuously and evenly added into a twin-screw extruder for extrusion, and the extruded material strips are cooled and pelletized to obtain the bio-based spray-free material.

10. The method for preparing a bio-based spray-free material according to claim 9, characterized in that: The extrusion condition parameters of the twin-screw extruder are as follows: the screw diameter of the twin-screw extruder is 35 mm, the length-to-diameter ratio L / D is 36, the temperature of zone 1 of the main barrel is 60-100° C., the temperature of zone 2 is 230-250° C., the temperature of zone 3 is 240-260° C., the temperature of zone 4 is 240-260° C., the temperature of zone 5 is 230-250° C., the temperature of zone 6 is 220-240° C., the temperature of zone 7 is 220-240° C., the temperature of zone 8 is 220-240° C., and the rotation speed of the twin screw is 300 rpm.

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