CN109942950B - Stress whitening-resistant scratch-resistant PP/PETG alloy material for vehicles and preparation method thereof - Google Patents
Stress whitening-resistant scratch-resistant PP/PETG alloy material for vehicles and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a stress whitening-resistant and scratch-resistant PP/PETG alloy material for a vehicle and a preparation method thereof. The polypropylene/polyethylene terephthalate composite material is prepared from 40-70 wt% of polypropylene, 5-20 wt% of PETG, 10-20 wt% of mineral filler, 5-15 wt% of toughening agent, 1-4 wt% of compatilizer, 0.4 wt% of antioxidant, 0.4 wt% of lubricant and 0.2 wt% of light stabilizer. Has the effects of greatly reducing stress whitening and resisting scratches.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a stress whitening resistant and scratch resistant PP/PETG alloy material for a vehicle and a preparation method thereof.
Background
With the increasing development of the automobile industry, light weight, beauty, energy conservation and environmental protection are more and more targets to be pursued by various large host products and consumers, and polypropylene (PP) with low density, high heat resistance and low performance and cost is widely applied to automobile interior and exterior decorations as a high polymer material with the largest using amount, but stress concentration and stress whitening are generated because the polypropylene is easily impacted and bent by the external force of a thimble or the material in the injection molding ejection stage. It has been found that the difference in refractive index between the silver streaks and cracks in the whitish portions is a main cause of the occurrence of the whitish portions. In addition, poor scratch resistance of polypropylene materials themselves tends to limit their further applications. The simplest method for solving the problems of stress whitening resistance and scratch resistance of PP is to add scratch-resistant auxiliary agents, such as stress whitening resistance auxiliary agents, silicone master batches, erucic acid master batches and other materials with lower molecular weight. The principle is that a protective layer is formed on the surface of a product transferred by silicone master batches with lower molecular weight before and after forming to reduce the friction coefficient so as to improve the scratch resistance coefficient, but the method can cause a series of problems of VOC (volatile organic compounds) pollution of automobile air, sticky material surface and the like, so that the development of a stress whitening resistant and scratch resistant polypropylene material for automobiles becomes a problem to be solved by experts.
PETG is known as polyethylene terephthalate-1, 4-cyclohexanedimethanol ester. The polyester is a product obtained by Polycondensation of Terephthalic Acid (PTA), Ethylene Glycol (EG) and 1, 4-Cyclohexanedimethanol (CHDM) through an ester exchange method, is a transparent and amorphous copolyester in brief, and has extremely high stress whitening resistance, high toughness, high strength and better impact resistance. At present, PETG is mainly applied to the fields of cosmetic packaging, credit cards and the like.
CN104558836A discloses a scratch-resistant and stress whitening-resistant polypropylene composite material and a preparation method thereof, wherein the stress whitening resistance and the scratch resistance of the polypropylene composite material are improved by adopting the crosslinking action of reactive siloxane and polypropylene, but the method has lower controllability and is not beneficial to large-scale production. CN105037955A discloses a polypropylene composition with low VOC, scratch resistance and stress whitening resistance and a preparation method thereof, wherein oligomeric low molecular weight polyorganosiloxane and polypropylene grafted high molecular weight polyorganosiloxane are adopted to improve the stress whitening resistance of polypropylene materials, but the phenomenon of oligomer migration and stickiness can be inevitably generated.
Disclosure of Invention
The invention aims to provide a stress whitening-resistant and scratch-resistant PP/PETG alloy material for a vehicle.
In order to achieve the aim, the invention provides a stress whitening-resistant scratch-resistant PP/PETG alloy material for vehicles, which is characterized by comprising the following components in percentage by weight: 40-70% of polypropylene, 5-20% of PETG, 10-20% of mineral filler, 5-15% of toughening agent, 1-4% of compatilizer, 0.4% of antioxidant, 0.4% of lubricant and 0.2% of light stabilizer.
Further, the polypropylene is homo-polypropylene or co-polypropylene; preferably, the melt index of the polypropylene at the temperature of 2.16/230 ℃ is 30-60 g/10 min.
Further, the melt index of the PETG at the temperature of 2.16/230 ℃ is 20-85g/10 min.
Further, the mineral filler is superfine talcum powder, wherein Si isO2The content is more than or equal to 56 percent, and the mesh number is more than or equal to 5000 meshes.
Further, the melt index of the toughening agent at the temperature of 2.16kg/190 ℃ is 5-15g/10 min; preferably, the toughening agent is one or more of ethylene-octene copolymer, ethylene propylene diene monomer, and methyl methacrylate-butadiene-styrene copolymer.
Further, the compatilizer is one or more than two of ethylene-propylene copolymer grafted maleic anhydride, ethylene-octene copolymer grafted maleic anhydride and polypropylene grafted maleic anhydride.
Further, the antioxidant is obtained by compounding a main antioxidant and an auxiliary antioxidant according to the mass ratio of 1: 1; preferably, the primary antioxidant is a hindered phenol primary antioxidant 1010 or a hindered phenol primary antioxidant 1076, and the secondary antioxidant is a phosphite secondary antioxidant 168 or a phosphite secondary antioxidant 686.
Further, the lubricant is stearate, aliphatic amide or stearic acid; preferably, the stearate is zinc stearate or calcium stearate; the aliphatic amide is amine stearate, amine erucate or N-N \ ethylene distearate; the stearic acid is stearic acid and/or hydroxystearic acid.
Further, the light stabilizer is one or a mixture of more than two of hindered amine, N-alkylated amine, ultraviolet absorbent benzotriazole and triazine benzalmalonate.
Further, the preparation method comprises the following steps:
preparing a premix: adding all the weighed materials into a high-speed stirrer, and uniformly stirring and mixing at a high speed to obtain a premix;
blending and extruding: adding the obtained premix into a parallel double-screw extruder from a main feeding hopper, and shearing, melting, blending and extruding all component materials in the parallel double-screw extruder to obtain material strips, wherein the processing temperature of each section of the double-screw extruder is 90 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 215 ℃, 220 ℃, 230 ℃, 220 ℃, 210 ℃ and a neck mold is 200 ℃;
and cooling, drying and dicing the material strips to obtain the stress whitening resistant and scratch resistant PP/PETG alloy material for the vehicle.
The inventor creatively discovers that when the weight percentages of the PP/PETG alloy material are 40-70% of polypropylene, 5-20% of PETG, 10-20% of mineral filler, 5-15% of toughening agent, 1-4% of compatilizer, 0.4% of antioxidant, 0.4% of lubricant and 0.2% of light stabilizer, the prepared PP/PETG alloy material for the vehicle has good stress whitening resistance and scratch resistance effects compared with scratch-resistant silicone master batches (silicone master batch SIC-6011P of Guangzhou silicon carbon new material Co., Ltd.), and the mechanical property of the composite material is greatly improved, and VOC pollution and the possibility of surface stickiness of a product caused by oligomer molecule migration are avoided. The PETG melt strength is relatively low, when the mixture is sheared and mixed by a screw rod, the PETG and the toughening agent form a shell-core structure similar to soft package hardness, molecular chains among the polypropylene/PETG/toughening agent are easy to entangle, and further under the action of stress, the molecular chains of the polypropylene/PETG/toughening agent can be migrated and deformed through chain segments, so that generation of silver stripes and cavities is inhibited, energy is consumed, and stress whitening is greatly reduced.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The stress whitening-resistant scratch-resistant PP/PETG alloy material for the vehicle is characterized by comprising the following components in percentage by weight: 40-70% of polypropylene, 5-20% of PETG, 10-20% of mineral filler, 5-15% of toughening agent, 1-4% of compatilizer, 0.4% of antioxidant, 0.4% of lubricant and 0.2% of light stabilizer.
Further, the polypropylene is homo-polypropylene or co-polypropylene; preferably, the melt index of the polypropylene at the temperature of 2.16/230 ℃ is 30-60 g/10 min.
Further, the melt index of the PETG at the temperature of 2.16/230 ℃ is 20-85g/10 min.
Further, the mineral filler is superfine talcum powder, wherein SiO is2The content is more than or equal to 56 percent, and the mesh number is more than or equal to 5000 meshes.
Further, the melt index of the toughening agent at the temperature of 2.16kg/190 ℃ is 5-15g/10 min; preferably, the toughening agent is one or more of ethylene-octene copolymer, ethylene propylene diene monomer, and methyl methacrylate-butadiene-styrene copolymer.
Further, the compatilizer is one or more than two of ethylene-propylene copolymer grafted maleic anhydride, ethylene-octene copolymer grafted maleic anhydride and polypropylene grafted maleic anhydride.
Further, the antioxidant is obtained by compounding a main antioxidant and an auxiliary antioxidant according to the mass ratio of 1: 1; preferably, the primary antioxidant is a hindered phenol primary antioxidant 1010 or a hindered phenol primary antioxidant 1076, and the secondary antioxidant is a phosphite secondary antioxidant 168 or a phosphite secondary antioxidant 686.
Further, the lubricant is stearate, aliphatic amide or stearic acid; preferably, the stearate is zinc stearate or calcium stearate; the aliphatic amide is amine stearate, amine erucate or N-N \ ethylene distearate; the stearic acid is stearic acid and/or hydroxystearic acid.
Further, the light stabilizer is one or a mixture of more than two of hindered amine, N-alkylated amine, ultraviolet absorbent benzotriazole and triazine benzalmalonate.
Further, the preparation method comprises the following steps:
preparing a premix: adding all the weighed materials into a high-speed stirrer, and uniformly stirring and mixing at a high speed to obtain a premix;
blending and extruding: adding the obtained premix into a parallel double-screw extruder from a main feeding hopper, and shearing, melting, blending and extruding all component materials in the parallel double-screw extruder to obtain material strips, wherein the processing temperature of each section of the double-screw extruder is 90 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 215 ℃, 220 ℃, 230 ℃, 220 ℃, 210 ℃ and a neck mold is 200 ℃;
and cooling, drying and dicing the material strips to obtain the stress whitening resistant and scratch resistant PP/PETG alloy material for the vehicle.
Example 1: preparation of stress whitening-resistant scratch-resistant PP/PETG alloy material for vehicles
Raw materials: see table 1.
The preparation method comprises the following steps:
(1) weighing PP, PETG, a toughening agent, a compatilizer, mineral filling, an antioxidant and a lubricant according to the weight percentage;
(2) adding all the materials in the step (1) into a high-speed stirrer, and uniformly stirring and mixing at a high speed to obtain a premix;
(3) adding the premix obtained in the step (2) into a parallel double-screw extruder from a main feeding hopper, and performing shearing, melting, blending and extruding on all component materials in the parallel double-screw extruder, wherein the processing temperature of the double-screw extruder is 90, 170, 180, 190, 200, 210, 215, 220, 230, 220, 210 and a neck mold is 200 ℃;
(4) and cooling, drying and granulating the material strips discharged from the die of the parallel double-screw extruder to obtain the PP/PETG alloy material for the vehicle, which is stress whitening resistant and scratch resistant.
Effect verification: see table 2.
Example 2: preparation of stress whitening-resistant scratch-resistant PP/PETG alloy material for vehicles
Raw materials: see table 1.
The preparation method comprises the following steps: see example 1.
Effect verification: see table 2.
Example 3: preparation of stress whitening-resistant scratch-resistant PP/PETG alloy material for vehicles
Raw materials: see table 1.
The preparation method comprises the following steps: see example 1.
Effect verification: see table 2.
Example 4: preparation of stress whitening-resistant scratch-resistant PP/PETG alloy material for vehicles
Raw materials: see table 1.
The preparation method comprises the following steps: see example 1.
Effect verification: see table 2.
Example 5: preparation of stress whitening-resistant scratch-resistant PP/PETG alloy material for vehicles
Raw materials: see table 1.
The preparation method comprises the following steps: see example 1.
Effect verification: see table 2.
Example 6: preparation of stress whitening-resistant scratch-resistant PP/PETG alloy material for vehicles
Raw materials: see table 1.
The preparation method comprises the following steps: see example 1.
Effect verification: see table 2.
Comparative example 1: preparation of stress whitening-resistant scratch-resistant PP/PETG alloy material for vehicles
Raw materials: see table 1.
The preparation method comprises the following steps: see example 1.
Effect verification: see table 2.
Comparative example 2: preparation of stress whitening-resistant scratch-resistant PP/PETG alloy material for vehicles
Raw materials: see table 1.
The preparation method comprises the following steps: see example 1.
Effect verification: see table 2.
TABLE 1 raw material usage tables for examples 1-6 and comparative examples 1-2
TABLE 2 summary of test results of each experimental group
As can be seen from Table 2, the mechanical properties of the stress whitening and scratch resistant PP/PETG alloy material for vehicles prepared by the technical scheme of the invention comprise tensile strength (more than 22MPa), strain elongation at break (less than 90%), bending strength (more than 28MPa), bending modulus (more than 1880MPa) and notched impact strength of a cantilever beam (more than 27 kJ/m)2) The improvement is good; the comparative examples were all less effective. The other part of the modified material is marked with stress whitening resistance and scratch resistance, and the scratch resistance and the stress whitening resistance of the modified material under stress are obtained through a ball drop test and a scratch resistance test, wherein the modified material is obtained through a cross-shaped scratch tester and a ball drop test, the Delta L represents the color difference before and after the test, and the smaller the Delta L is, the better the stress whitening resistance and the scratch resistance are. It can be seen that the stress whitening and scratch resistant PP/PETG alloy material for vehicles prepared by the technical scheme of the invention has the scratch resistance delta L less than 2, and the comparative example is much greater than 3. The falling ball whiteness Δ L was less than 3.5, while the comparative example was much more than 4. The stress whitening resistance and scratch resistance of the PP/PETG alloy material for the vehicle prepared by the technical scheme of the invention have good stress whitening resistance and scratch resistance.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (10)
1. The stress whitening-resistant scratch-resistant PP/PETG alloy material for the vehicle is characterized by comprising the following components in percentage by weight: 40-70% of polypropylene, 5-20% of PETG, 10-20% of mineral filler, 5-15% of toughening agent, 1-4% of compatilizer, 0.4% of antioxidant, 0.4% of lubricant and 0.2% of light stabilizer;
the P isThe melt index of ETG at 2.16kg/230 ℃ is 20-85g/10 min; the mineral filler is superfine pulvis Talci, wherein SiO2The content is more than or equal to 56 percent, and the mesh number is more than or equal to 5000 meshes; the toughening agent is an ethylene-octene copolymer, and the melt index is 5-15g/10min at the temperature of 2.16kg/190 ℃.
2. The stress whitening and scratch resistant PP/PETG alloy material for the vehicle as claimed in claim 1, wherein the polypropylene is homo-polypropylene or co-polypropylene.
3. The PP/PETG alloy material for the stress whitening resistance and scratch resistance vehicle as claimed in claim 2, wherein the melt index of the polypropylene at 2.16kg/230 ℃ is 30-60 g/10 min.
4. The PP/PETG alloy material for the vehicle, as recited in claim 1, wherein the compatilizer is one or more of ethylene-propylene copolymer grafted maleic anhydride, ethylene-octene copolymer grafted maleic anhydride and polypropylene grafted maleic anhydride.
5. The PP/PETG alloy material for the vehicle, which is resistant to stress whitening and scratch, as claimed in claim 1, is characterized in that the antioxidant is obtained by compounding a main antioxidant and an auxiliary antioxidant according to a mass ratio of 1: 1.
6. The PP/PETG alloy material for the vehicle, which is resistant to stress whitening and scratch according to claim 5, is characterized in that the main antioxidant is a hindered phenol main antioxidant 1010 or a hindered phenol main antioxidant 1076, and the auxiliary antioxidant is a phosphite auxiliary antioxidant 168 or a phosphite auxiliary antioxidant 686.
7. The PP/PETG alloy material for the vehicle, which is resistant to stress whitening and scratch according to claim 1, wherein the lubricant is stearate, aliphatic amide or stearic acid.
8. The PP/PETG alloy material for resisting stress whitening and scratch for the vehicle as claimed in claim 7, wherein the stearate is zinc stearate or calcium stearate; the aliphatic amide is stearic acid amide, erucic acid amide or N, N' -ethylene bisstearamide, and the stearic acid and/or hydroxystearic acid are/is stearic acid.
9. The PP/PETG alloy material for the vehicle, which is used for resisting stress whitening and scratching according to claim 1, wherein the light stabilizer is one or a mixture of any two or more of hindered amines, N-alkylated amines, ultraviolet absorbers, benzotriazoles, triazines and benzalmalonate.
10. The stress whitening-resistant scratch-resistant PP/PETG alloy material for the vehicle as claimed in any one of claims 1-9, which is prepared by the following steps:
preparing a premix: adding all the weighed materials into a high-speed stirrer, and uniformly stirring and mixing at a high speed to obtain a premix;
blending and extruding: adding the obtained premix into a parallel double-screw extruder from a main feeding hopper, and shearing, melting, blending and extruding all component materials in the parallel double-screw extruder to obtain material strips, wherein the processing temperature of each section of the double-screw extruder is 90 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 215 ℃, 220 ℃, 230 ℃, 220 ℃, 210 ℃ and a neck mold is 200 ℃;
and cooling, drying and dicing the material strips to obtain the stress whitening resistant and scratch resistant PP/PETG alloy material for the vehicle.
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