CN112646337A - Spraying-free degradable composite material for automobile and preparation method thereof - Google Patents
Spraying-free degradable composite material for automobile and preparation method thereof Download PDFInfo
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
The invention discloses a spraying-free degradable composite material for automobiles and a preparation method thereof, wherein the degradable composite material mainly comprises 2-8 parts of spraying-free color master batch, 40-80 parts of polylactic acid, 5-30 parts of PBAT, 0-30 parts of filler, 0.1-1 part of antioxidant, 0.1-1 part of light stabilizer and 0.5-3 parts of processing aid. The invention has the advantages that: 1. the spraying-free degradable composite material for the automobile, which is prepared by the invention, can realize complete biodegradation, has metallic luster and pearlescent effect, does not need to be sprayed and colored again when in use, accords with the concept of environmental protection, and has the function of environmental protection. 2. The heat resistance of the degradable composite material prepared by the invention is greatly improved, and the heat resistance level of the modified polypropylene material for automobiles is reached; the impact property is greatly improved, and the problems of poor heat resistance and high brittleness of the polylactic acid material are effectively solved.
Description
Technical Field
The invention relates to the technical field of modification of high polymer materials, in particular to a spraying-free degradable composite material for automobiles and a preparation method thereof.
Background
With the increasing resource and environmental problems, degradable plastics become the hottest development direction of the current plastics industry. Polylactic acid is outstanding among degradable plastics, is prepared from bio-based raw materials, does not depend on petroleum resources, and can be completely degraded into water and carbon dioxide under composting conditions after being discarded. The polylactic acid has higher tensile strength and elastic modulus, good processing performance and great potential to replace polypropylene materials with larger consumption in automobile plastics. However, polylactic acid has limited application due to its drawbacks such as high brittleness and poor thermal stability, and it is important to improve the heat resistance and brittleness of polylactic acid by modification.
With the mature development of the automobile industry and the combination with the times, safety, comfort, environmental friendliness and individuation are all future development trends of the automobile industry. The paint is modified by adopting a spraying-free material technology, so that the use of the paint can be reduced, the environmental pollution is reduced, and meanwhile, the personalized development trend is met.
There have been some reports on degradable materials for automotive applications, and some solutions have been proposed. Patent CN102585466B relates to a biodegradable material and a molded product thereof, which is mainly prepared from polylactic acid, polybutylene succinate and polypropylene carbonate, can be used for parts such as automobile glove compartments and the like, and has complete biodegradability. Patent CN106800756B relates to a full-bio-based degradable material, a preparation method thereof, a vehicle interior and a vehicle, wherein the material mainly comprises polylactic acid, butanediol adipate-butanediol terephthalate, starch-based plastic and bamboo fiber, and can be used for automotive interior parts. At present, most of main materials of the automobile spray-free plastic adopt polypropylene and ABS, few biodegradable spray-free materials are reported, and particularly, less spray-free materials with complete biodegradability are reported, for example, patent CN102206407B relates to a biodegradable spray-free aesthetic resin and a preparation method thereof, and the main body of the composite material is polylactic acid and polymethyl methacrylate, wherein the polymethyl methacrylate is not degradable, so that the material can only realize partial biodegradability.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a spraying-free degradable composite material for automobiles and a preparation method thereof. The base material of the degradable composite material can realize complete biodegradation, is environment-friendly, and simultaneously has excellent comprehensive mechanical property, and a spraying-free metal effect and a pearlescent effect.
The purpose of the invention is realized by the following technical scheme:
the spraying-free degradable composite material for the automobile is prepared from the following raw materials in parts by weight:
polylactic acid: 40-80 parts;
PBAT: 5-30 parts of a solvent;
filling: 0-30 parts of a solvent;
antioxidant: 0.1-1 part;
light stabilizer: 0.1-1.0 part;
processing aid: 0.5-3 parts;
spraying-free color master batch: 2-8 parts;
the spraying-free color master batch is prepared from the following components in parts by weight:
l-type polylactic acid: 20-60 parts;
metallic toner: 10-40 parts;
pearl powder: 10-40 parts;
surface treating agent: 0.1-1 part;
processing aid: 0.5-3 parts.
The polylactic acid is a mixture consisting of 50-100% of L-type polylactic acid and 5-60% of D-type polylactic acid. Wherein the optical purity of the L-type polylactic acid is more than or equal to 96 percent, and the melt index is 2-30g/min under the conditions of 210 ℃ and 2.16 kg; wherein the optical purity of the D-type polylactic acid is more than or equal to 98 percent, and the melt index is 2-30g/min under the conditions of 210 ℃ and 2.16 kg.
The filler is one or a mixture of mica powder, talcum powder and glass fiber powder, the particle size range of the mica powder is 2-50 micrometers, the particle size range of the talcum powder is 1-25 micrometers, and the particle size range of the glass fiber powder is 10-200 micrometers.
The antioxidant is one or a mixture of aromatic amine, hindered phenol, phosphite ester or thioester antioxidant.
The light stabilizer is compounded by hindered amine and ultraviolet absorbent.
The processing aid is one or a mixture of more of citric acid ester, stearic acid and ethylene bis stearamide.
The metal toner is at least one of aluminum powder and silver powder, is flaky and silver element-shaped, and has a particle size range of 2-100 micrometers.
The particle size range of the pearl powder is 1-50 microns.
The surface treating agent is one or a mixture of silane coupling agent, zirconium coupling agent and titanate coupling agent.
The preparation method of the spraying-free degradable composite material for the automobile comprises the following preparation steps:
(1) preparing a spraying-free color master batch:
weighing L-type polylactic acid, metallic toner, pearl powder, a surface treating agent and a processing aid in parts by weight, then adding the L-type polylactic acid, the metallic toner, the pearl powder, the surface treating agent and the processing aid into a high-speed mixer together to mix for 2-20 minutes, then adding the mixture into a double-screw extruder, and preparing the spraying-free color master batch through melting, extruding, cooling and granulating the mixture by the double-screw extruder;
the processing temperature of the I-X area of the double-screw extruder is 80 +/-20 ℃, 175 +/-20 ℃, 180 +/-20 ℃, 185 +/-20 ℃, 195 +/-20 ℃,205 +/-20 ℃,210 +/-20 ℃ and 210 +/-20 ℃ in sequence; the rotating speed of the main screw is 500-550 r/min, and the temperature of the water tank is 20-45 ℃;
(2) the spraying-free degradable composite material for the automobile and the preparation thereof are as follows:
adding the spraying-free color master batch prepared in the step (1), polylactic acid, PBAT, a filler, an antioxidant, a light stabilizer and a processing aid into a high-speed mixer together according to parts by weight, mixing for 2-20 minutes, adding into a double-screw extruder, and preparing the spraying-free degradable composite material for the automobile by melting, extruding, cooling and granulating through the double-screw extruder;
the processing temperature of the I-X area of the double-screw extruder is 130 +/-20 ℃, 165 +/-20 ℃, 185 +/-20 ℃, 190 +/-20 ℃,200 +/-20 ℃,205 +/-20 ℃,210 +/-20 ℃ and 210 +/-20 ℃ in sequence; the rotating speed of the main screw is 500-550 r/min, and the temperature of the water tank is 20-45 ℃.
The invention has the advantages that:
1. the spraying-free degradable composite material for the automobile, which is prepared by the invention, can realize complete biodegradation, has metallic luster and pearlescent effect, does not need to be sprayed and colored again when in use, accords with the concept of environmental protection, and has the function of environmental protection.
2. The D-type polylactic acid used in the invention is in a composite material system, so that the heat resistance of the prepared degradable composite material is greatly improved, and the heat resistance level of the modified polypropylene material for automobiles is reached; the PBAT used in the invention is in a composite material system, so that the impact performance of the prepared degradable composite material is greatly improved, and the problems of poor heat resistance and high brittleness of a polylactic acid material are effectively solved.
3. The preparation method of the spraying-free degradable composite material for the automobile is simple in preparation process and low in production cost, and the preparation method of the spraying-free color master batch is beneficial to fully mixing and dispersing the metallic toner and the pearlescent toner in a composite material system, so that the prepared degradable composite material is better in metallic luster and pearlescent effect.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be emphasized that these examples are only for the purpose of further illustration of the present invention and are not to be construed as limiting the scope of the present invention. Further, it should be understood that various changes or modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the appended claims.
L-type polylactic acid of Doudaro Bien with L175 and LX530 is preferably used in the following examples, and the material flow rates at 210 deg.C and 2.16Kg are 8g/min and 24g/min, respectively. The D-type polylactic acid is preferably D120-type polylactic acid of Doudaro Bien, and the material flow rate is 24g/min under the conditions of 210 ℃ and 2.16 Kg. The PBAT is preferably based on Pasteur C1200, and the material flow rate at 210 ℃ and 2.16Kg is 6 g/min.
Example 1
(1) Preparing a spraying-free color master batch:
according to parts by weight, mixing L-type polylactic acid with the flow speed of 24 g/min: LX 53040 parts; 30 parts of aluminum powder; 30 parts of pearlescent pigment; 5500.8 parts of a silane coupling agent KH; ethylene bis stearamide EB-FF and tributyl citrate are 0.5 parts respectively; and adding the materials into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder, and carrying out melting, extrusion, cooling and grain cutting on the mixture by the double-screw extruder to prepare the spraying-free color master batch. The flow rate of the master batch was measured at 210 ℃ and 2.16Kg and was 20 g/min.
The processing temperature of the I-X area of the double-screw extruder is 85 ℃, 170 ℃, 180 ℃, 180 ℃, 195 ℃,200 ℃,200 ℃,205 ℃,210 ℃ and 210 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 35 ℃.
(2) The spraying-free degradable composite material for the automobile and the preparation thereof are as follows: 5 parts of spraying-free color master batch prepared in the step (1), 17548 parts of L-type polylactic acid L with the flow speed of 8g/min, 12 parts of D-type polylactic acid, 15 parts of PBAT and a filler in parts by weight: 20 parts of talcum powder with the particle size of 2.6 microns, 0.2 part of each of DSTP antioxidant and 168 antioxidant, 52290.2 parts of composite light stabilizer UV, 0.5 part of each of ethylene bis stearamide EB-FF and tributyl citrate are added into a high-speed mixer together and mixed uniformly, then the mixture is added into a double-screw extruder, and the mixture is melted, extruded, cooled and cut into granules by the double-screw extruder to prepare the spraying-free degradable composite material.
The processing temperature of the I-X area of the double-screw extruder is 135 ℃, 160 ℃, 180 ℃, 185 ℃, 195 ℃,200 ℃,205 ℃,210 ℃ and 215 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 36 ℃.
Example 2
(1) Preparing a spraying-free color master batch:
according to parts by weight, mixing L-type polylactic acid with the flow speed of 24 g/min: LX 53050 parts; 30 parts of aluminum powder; 20 parts of pearlescent pigment; 5500.8 parts of a silane coupling agent KH; ethylene bis stearamide EB-FF and tributyl citrate are 0.5 parts respectively; and adding the materials into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder, and carrying out melting, extrusion, cooling and grain cutting on the mixture by the double-screw extruder to prepare the spraying-free color master batch. The flow rate of the master batch was measured at 210 ℃ and 2.16Kg and found to be 22 g/min.
The processing temperature of the I-X area of the double-screw extruder is 85 ℃, 170 ℃, 180 ℃, 180 ℃, 195 ℃,200 ℃,200 ℃,205 ℃,210 ℃ and 210 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 35 ℃.
(2) The spraying-free degradable composite material for the automobile and the preparation thereof are as follows: 2 parts of spraying-free color master batch prepared in the step (1), 17536 parts of L-type polylactic acid L with the flow speed of 8g/min, 21 parts of D-type polylactic acid, 20 parts of PBAT and a filler: 20 parts of talcum powder with the particle size of 2.6 microns, 0.2 part of each of DSTP antioxidant and 168 antioxidant, 52290.2 parts of composite light stabilizer UV, 0.5 part of each of ethylene bis stearamide EB-FF and tributyl citrate are added into a high-speed mixer together and mixed uniformly, then the mixture is added into a double-screw extruder, and the mixture is melted, extruded, cooled and cut into granules by the double-screw extruder to prepare the spraying-free degradable composite material.
The processing temperature of the I-X area of the double-screw extruder is 135 ℃, 160 ℃, 180 ℃, 185 ℃, 195 ℃,200 ℃,205 ℃,210 ℃ and 215 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 36 ℃.
Example 3
(1) Preparing a spraying-free color master batch:
according to parts by weight, mixing L-type polylactic acid with the flow speed of 24 g/min: LX 53060 parts; 20 parts of aluminum powder; 20 parts of pearlescent pigment; 5500.8 parts of a silane coupling agent KH; ethylene bis stearamide EB-FF and tributyl citrate are 0.5 parts respectively; and adding the materials into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder, and carrying out melting, extrusion, cooling and grain cutting on the mixture by the double-screw extruder to prepare the spraying-free color master batch. The flow rate of the master batch was measured at 210 ℃ and 2.16Kg and found to be 22 g/min.
The processing temperature of the I-X area of the double-screw extruder is 85 ℃, 170 ℃, 180 ℃, 180 ℃, 195 ℃,200 ℃,200 ℃,205 ℃,210 ℃ and 210 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 35 ℃.
(2) The spraying-free degradable composite material for the automobile and the preparation thereof are as follows: according to parts by weight, 8 parts of spraying-free color master batch prepared in the step (1), 17537 parts of L-type polylactic acid L with the flow speed of 8g/min, 25 parts of D-type polylactic acid, 15 parts of PBAT and a filler: 15 parts of talcum powder with the particle size of 2.6 microns, 0.2 part of each of DSTP antioxidant and 168 antioxidant, 52290.2 parts of composite light stabilizer UV, 0.5 part of each of ethylene bis stearamide EB-FF and tributyl citrate are added into a high-speed mixer together and mixed uniformly, then the mixture is added into a double-screw extruder, and the mixture is melted, extruded, cooled and cut into granules by the double-screw extruder to prepare the spraying-free degradable composite material.
The processing temperature of the I-X area of the double-screw extruder is 135 ℃, 160 ℃, 180 ℃, 185 ℃, 195 ℃,200 ℃,205 ℃,210 ℃,215 ℃ and 220 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 36 ℃.
Example 4
(1) Preparing a spraying-free color master batch:
according to parts by weight, mixing L-type polylactic acid with the flow speed of 24 g/min: LX 53050 parts; 30 parts of aluminum powder; 20 parts of pearlescent pigment; 5500.8 parts of a silane coupling agent KH; ethylene bis stearamide EB-FF and tributyl citrate are 0.5 parts respectively; and adding the materials into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder, and carrying out melting, extrusion, cooling and grain cutting on the mixture by the double-screw extruder to prepare the spraying-free color master batch. The flow rate of the master batch was measured at 210 ℃ and 2.16Kg and found to be 22 g/min.
The processing temperature of the I-X area of the double-screw extruder is 85 ℃, 170 ℃, 180 ℃, 180 ℃, 195 ℃,200 ℃,200 ℃,205 ℃,210 ℃ and 210 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 35 ℃.
(2) The spraying-free degradable composite material for the automobile and the preparation thereof are as follows: 2 parts of spraying-free color master batch prepared in the step (1), 17543 parts of L-type polylactic acid L with the flow speed of 8g/min, 19 parts of D-type polylactic acid, 25 parts of PBAT and a filler: 10 parts of talcum powder with the particle size of 2.6 microns, 0.2 part of each of DSTP antioxidant and 168 antioxidant, 52290.2 parts of composite light stabilizer UV, 0.5 part of each of ethylene bis stearamide EB-FF and tributyl citrate are added into a high-speed mixer together and mixed uniformly, then the mixture is added into a double-screw extruder, and the mixture is melted, extruded, cooled and cut into granules by the double-screw extruder to prepare the spraying-free degradable composite material.
The processing temperature of the I-X area of the double-screw extruder is 135 ℃, 160 ℃, 180 ℃, 185 ℃, 195 ℃,200 ℃,205 ℃,210 ℃ and 215 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 36 ℃.
Example 5
(1) Preparing a spraying-free color master batch:
according to parts by weight, mixing L-type polylactic acid with the flow speed of 24 g/min: LX 53050 parts; 30 parts of aluminum powder; 20 parts of pearlescent pigment; 5500.8 parts of a silane coupling agent KH; ethylene bis stearamide EB-FF and tributyl citrate are 0.5 parts respectively; and adding the materials into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder, and carrying out melting, extrusion, cooling and grain cutting on the mixture by the double-screw extruder to prepare the spraying-free color master batch. The flow rate of the master batch was measured at 210 ℃ and 2.16Kg and found to be 22 g/min.
The processing temperature of the I-X area of the double-screw extruder is 85 ℃, 170 ℃, 180 ℃, 180 ℃, 195 ℃,200 ℃,200 ℃,205 ℃,210 ℃ and 210 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 35 ℃.
(2) The spraying-free degradable composite material for the automobile and the preparation thereof are as follows: adding 6 parts by weight of the spraying-free color master batch prepared in the step (1) and 0.2 part by weight of each of L-type polylactic acid L17545 parts, D-type polylactic acid 34 parts, PBAT 15 parts, DSTP antioxidant and 168 antioxidant with the flow speed of 8g/min, each of composite light stabilizer UV 52290.2 parts, ethylene bis stearamide EB-FF and tributyl citrate into a high-speed mixer together, uniformly mixing, adding into a double-screw extruder, and melting, extruding, cooling and granulating by the double-screw extruder to prepare the spraying-free degradable composite material.
The processing temperature of the I-X area of the double-screw extruder is 140 ℃, 170 ℃, 190 ℃, 195 ℃,205 ℃,210 ℃,215 ℃,220 ℃ and 225 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 37 ℃.
Example 6
(1) Preparing a spraying-free color master batch:
according to parts by weight, mixing L-type polylactic acid with the flow speed of 24 g/min: LX 53050 parts; 30 parts of aluminum powder; 20 parts of pearlescent pigment; 5500.8 parts of a silane coupling agent KH; ethylene bis stearamide EB-FF and tributyl citrate are 0.5 parts respectively; and adding the materials into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder, and carrying out melting, extrusion, cooling and grain cutting on the mixture by the double-screw extruder to prepare the spraying-free color master batch. The flow rate of the master batch was measured at 210 ℃ and 2.16Kg and found to be 22 g/min.
The processing temperature of the I-X area of the double-screw extruder is 85 ℃, 170 ℃, 180 ℃, 180 ℃, 195 ℃,200 ℃,200 ℃,205 ℃,210 ℃ and 210 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 35 ℃.
(2) The spraying-free degradable composite material for the automobile and the preparation thereof are as follows: adding 6 parts by weight of the spraying-free color master batch prepared in the step (1) and 0.2 part by weight of each of L-type polylactic acid L17532 parts, D-type polylactic acid 32 parts, PBAT 30 parts, DSTP antioxidant and 168 antioxidant with the flow speed of 8g/min, each of composite light stabilizer UV 52290.2 parts, ethylene bis stearamide EB-FF and tributyl citrate into a high-speed mixer together, uniformly mixing, adding into a double-screw extruder, and melting, extruding, cooling and granulating by the double-screw extruder to prepare the spraying-free degradable composite material.
The processing temperature of the I-X area of the double-screw extruder is 135 ℃, 160 ℃, 180 ℃, 185 ℃, 195 ℃,200 ℃,205 ℃,210 ℃ and 215 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 36 ℃.
Comparative example 1
In order to better embody the dispersibility of the spraying-free toner of the spraying-free degradable composite material for the automobile and the preparation method thereof, the comparative example is different from the example 1 in that the spraying-free degradable composite material is prepared by directly adding the aluminum powder, the pearlescent pigment and the silane coupling agent in parts by weight which are the same as those in the example 1 by adopting the conventional method for preparing the spraying-free degradable composite material, and mainly comprises the following specific implementation steps:
1.5 parts of aluminum powder, 1.5 parts of pearlescent pigment, KH 5500.04 parts of silane coupling agent, 17548 parts of L-type polylactic acid L with the flow speed of 8g/min, 12 parts of D-type polylactic acid, 15 parts of PBAT and a filler by weight: 20 parts of talcum powder with the particle size of 2.6 microns, 0.2 part of each of DSTP antioxidant and 168 antioxidant, 52290.2 parts of composite light stabilizer UV, 0.5 part of each of ethylene bis stearamide EB-FF and tributyl citrate are added into a high-speed mixer together and mixed uniformly, then the mixture is added into a double-screw extruder, and the mixture is melted, extruded, cooled and cut into granules by the double-screw extruder to prepare the spraying-free degradable composite material.
The processing temperature of the I-X area of the double-screw extruder is 135 ℃, 160 ℃, 180 ℃, 185 ℃, 195 ℃,200 ℃,205 ℃,210 ℃ and 215 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 36 ℃.
Comparative example 2
In order to better embody the thermal stability of the spraying-free degradable composite material for the automobile, the comparative example is different from the example 1 in that the D-type polylactic acid is not added, and mainly comprises the following specific implementation steps:
(1) preparing a spraying-free color master batch:
according to parts by weight, mixing L-type polylactic acid with the flow speed of 24 g/min: LX 53040 parts; 30 parts of aluminum powder; 30 parts of pearlescent pigment; 5500.8 parts of a silane coupling agent KH; ethylene bis stearamide EB-FF and tributyl citrate are 0.5 parts respectively; and adding the materials into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder, and carrying out melting, extrusion, cooling and grain cutting on the mixture by the double-screw extruder to prepare the spraying-free color master batch. The flow rate of the master batch was measured at 210 ℃ and 2.16Kg and was 20 g/min.
The processing temperature of the I-X area of the double-screw extruder is 85 ℃, 170 ℃, 180 ℃, 180 ℃, 195 ℃,200 ℃,200 ℃,205 ℃,210 ℃ and 210 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 35 ℃.
(2) The spraying-free degradable composite material for the automobile and the preparation thereof are as follows: 5 parts of spraying-free color master batch prepared in the step (1), 17560 parts of L-type polylactic acid L with the flow speed of 8g/min, 15 parts of PBAT and a filler in parts by weight: 20 parts of talcum powder with the particle size of 2.6 microns, 0.2 part of each of DSTP antioxidant and 168 antioxidant, 52290.2 parts of composite light stabilizer UV, 0.5 part of each of ethylene bis stearamide EB-FF and tributyl citrate are added into a high-speed mixer together and mixed uniformly, then the mixture is added into a double-screw extruder, and the mixture is melted, extruded, cooled and cut into granules by the double-screw extruder to prepare the spraying-free degradable composite material.
The processing temperature of the I-X area of the double-screw extruder is 135 ℃, 160 ℃, 180 ℃, 185 ℃, 195 ℃,200 ℃,205 ℃,210 ℃ and 215 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 36 ℃.
Comparative example 3
In order to better embody the impact performance of the spray-free degradable composite material for the automobile, the comparative example is different from the example 1 in that no PBAT is added, and mainly comprises the following specific implementation steps:
(1) preparing a spraying-free color master batch:
according to parts by weight, mixing L-type polylactic acid with the flow speed of 24 g/min: LX 53040 parts; 30 parts of aluminum powder; 30 parts of pearlescent pigment; 5500.8 parts of a silane coupling agent KH; ethylene bis stearamide EB-FF and tributyl citrate are 0.5 parts respectively; and adding the materials into a high-speed mixer, uniformly mixing, adding the mixture into a double-screw extruder, and carrying out melting, extrusion, cooling and grain cutting on the mixture by the double-screw extruder to prepare the spraying-free color master batch. The flow rate of the master batch was measured at 210 ℃ and 2.16Kg and was 20 g/min.
The processing temperature of the I-X area of the double-screw extruder is 85 ℃, 170 ℃, 180 ℃, 180 ℃, 195 ℃,200 ℃,200 ℃,205 ℃,210 ℃ and 210 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 35 ℃.
(2) The spraying-free degradable composite material for the automobile and the preparation thereof are as follows: 5 parts of spraying-free color master batch prepared in the step (1), 17563 parts of L-type polylactic acid with the flow speed of 8g/min, 12 parts of D-type polylactic acid and a filler in parts by weight: 20 parts of talcum powder with the particle size of 2.6 microns, 0.2 part of each of DSTP antioxidant and 168 antioxidant, 52290.2 parts of composite light stabilizer UV, 0.5 part of each of ethylene bis stearamide EB-FF and tributyl citrate are added into a high-speed mixer together and mixed uniformly, then the mixture is added into a double-screw extruder, and the mixture is melted, extruded, cooled and cut into granules by the double-screw extruder to prepare the spraying-free degradable composite material.
The processing temperature of the I-X area of the double-screw extruder is 135 ℃, 160 ℃, 180 ℃, 185 ℃, 195 ℃,200 ℃,205 ℃,210 ℃ and 215 ℃ in sequence. The rotation speed of the main screw is 550r/min, and the temperature of the water tank is 36 ℃.
Drying the particle material prepared by the method in a blast oven at 40-50 ℃ for 4-5 hours, and then carrying out injection molding on the dried particle material on an injection molding machine to prepare a sample.
TABLE 1 Performance test standards and conditions for spray-free degradable composite materials for automobiles
| Inspection index | Test method | Size of sample strip | Test conditions | Unit of |
| Tensile strength | ISO 527-2 | 170×10×4mm | 50mm/min | MPa |
| Flexural modulus | ISO 178 | 80×10×4mm | 2mm/min，64mm | MPa |
| Impact strength of simply supported beam notch | ISO 179-1 | 80×10×4mm | 23℃ | KJ/m^2 |
| Heat distortion temperature | ISO 75-2 | 80×10×4mm | 0.45MPa，120℃/h | ℃ |
| Melt flow rate | Method A | Particles | 210℃*2.16kg | g/10min |
| Appearance without spraying effect | Evaluation by manual visual inspection | 150×100×3.2mm | \ | \ |
Table 2 Performance test data of the spray-free degradable composite materials for the automobiles in examples 1-6 and comparative examples 1-3
In table 2, examples 1 to 6 according to the test results of the spray-free degradable composite material prepared according to some representative embodiments of the spray-free degradable composite material for automobile and the preparation method thereof of the present invention, in order to better embody the heat resistance, the impact resistance and the spray-free toner dispersion effect of the spray-free degradable composite material for automobile and the preparation method thereof of the present invention, the corresponding comparative example 1, comparative example 2 and comparative example 3 are used as the control of the corresponding examples. From table 2 the following conclusions can be drawn:
1. the spraying-free degradable composite material for the automobile, which is prepared by the invention, can realize complete biodegradation, has metallic luster and pearlescent effect, does not need to be sprayed and colored again when in use, accords with the concept of environmental protection, and has the function of environmental protection.
2. The D-type polylactic acid used in the invention is in a composite material system, so that the heat resistance of the prepared degradable composite material is greatly improved, and the heat resistance level of the modified polypropylene material for automobiles is reached; the PBAT used in the invention is in a composite material system, so that the impact performance of the prepared degradable composite material is greatly improved, and the problems of poor heat resistance and high brittleness of a polylactic acid material are effectively solved.
3. The preparation method of the spraying-free degradable composite material for the automobile is simple in preparation process and low in production cost, and the preparation method of the spraying-free color master batch is beneficial to fully mixing and dispersing the metallic toner and the pearlescent toner in a composite material system, so that the prepared degradable composite material is better in metallic luster and pearlescent effect.
Claims (10)
1. The spraying-free degradable composite material for the automobile is characterized in that: the composition is prepared from the following raw materials in parts by weight:
polylactic acid: 40-80 parts;
PBAT: 5-30 parts of a solvent;
filling: 0-30 parts of a solvent;
antioxidant: 0.1-1 part;
light stabilizer: 0.1-1.0 part;
processing aid: 0.5-3 parts;
spraying-free color master batch: 2-8 parts;
the spraying-free color master batch is prepared from the following components in parts by weight:
l-type polylactic acid: 20-60 parts;
metallic toner: 10-40 parts;
pearl powder: 10-40 parts;
surface treating agent: 0.1-1 part;
processing aid: 0.5-3 parts.
2. The spraying-free degradable composite material for the automobile according to claim 1, wherein: the polylactic acid is a mixture consisting of 50-100% of L-type polylactic acid and 5-60% of D-type polylactic acid.
3. The spraying-free degradable composite material for the automobile according to claim 2, wherein: the optical purity of the L-type polylactic acid is more than or equal to 96 percent, and the melt index is 2-30g/min under the conditions of 210 ℃ and 2.16 kg; the D-type polylactic acid has optical purity not less than 98% and melt index of 2-30g/min at 210 deg.c and 2.16 kg.
4. The spraying-free degradable composite material for the automobile according to claim 1, wherein: the filler is one or a mixture of mica powder, talcum powder and glass fiber powder, the particle size range of the mica powder is 2-50 micrometers, the particle size range of the talcum powder is 1-25 micrometers, and the particle size range of the glass fiber powder is 10-200 micrometers.
5. The spraying-free degradable composite material for the automobile according to claim 1, wherein: the antioxidant is one or a mixture of aromatic amine, hindered phenol, phosphite ester or thioester antioxidant.
6. The spraying-free degradable composite material for the automobile according to claim 1, wherein: the light stabilizer is compounded by hindered amine and ultraviolet absorbent.
7. The spraying-free degradable composite material for the automobile according to claim 1, wherein: the processing aid is one or a mixture of more of citric acid ester, stearic acid and ethylene bis stearamide.
8. The spraying-free degradable composite material for the automobile according to claim 1, wherein: the metal toner is at least one of aluminum powder and silver powder, is flaky and silver element-shaped, and has a particle size range of 2-100 micrometers;
the particle size range of the pearl powder is 1-50 microns.
9. The spraying-free degradable composite material for the automobile according to claim 1, wherein: the surface treating agent is one or a mixture of silane coupling agent, zirconium coupling agent and titanate coupling agent.
10. The preparation method of the spray-free degradable composite material for the automobile according to any one of claims 1 to 9, wherein the spray-free degradable composite material comprises the following steps: the preparation method comprises the following preparation steps:
(1) preparing a spraying-free color master batch:
weighing L-type polylactic acid, metallic toner, pearl powder, a surface treating agent and a processing aid in parts by weight, then adding the L-type polylactic acid, the metallic toner, the pearl powder, the surface treating agent and the processing aid into a high-speed mixer together to mix for 2-20 minutes, then adding the mixture into a double-screw extruder, and preparing the spraying-free color master batch through melting, extruding, cooling and granulating the mixture by the double-screw extruder;
the processing temperature of the I-X area of the double-screw extruder is 80 +/-20 ℃, 175 +/-20 ℃, 180 +/-20 ℃, 185 +/-20 ℃, 195 +/-20 ℃,205 +/-20 ℃,210 +/-20 ℃ and 210 +/-20 ℃ in sequence; the rotating speed of the main screw is 500-550 r/min, and the temperature of the water tank is 20-45 ℃;
(2) the spraying-free degradable composite material for the automobile and the preparation thereof are as follows:
adding the spraying-free color master batch prepared in the step (1), polylactic acid, PBAT, a filler, an antioxidant, a light stabilizer and a processing aid into a high-speed mixer together according to parts by weight, mixing for 2-20 minutes, adding into a double-screw extruder, and preparing the spraying-free degradable composite material for the automobile by melting, extruding, cooling and granulating through the double-screw extruder;
the processing temperature of the I-X area of the double-screw extruder is 130 +/-20 ℃, 165 +/-20 ℃, 185 +/-20 ℃, 190 +/-20 ℃,200 +/-20 ℃,205 +/-20 ℃,210 +/-20 ℃ and 210 +/-20 ℃ in sequence; the rotating speed of the main screw is 500-550 r/min, and the temperature of the water tank is 20-45 ℃.
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