CN113121939A - Composite resin material, preparation method thereof and automobile part - Google Patents

Composite resin material, preparation method thereof and automobile part Download PDF

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Publication number
CN113121939A
CN113121939A CN202110343423.3A CN202110343423A CN113121939A CN 113121939 A CN113121939 A CN 113121939A CN 202110343423 A CN202110343423 A CN 202110343423A CN 113121939 A CN113121939 A CN 113121939A
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Prior art keywords
mass
resin material
composite resin
parts
black
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CN202110343423.3A
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Chinese (zh)
Inventor
郑德�
陈俊
吴波
冷海强
梁麟枝
喻海龙
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Guangdong Winner New Materials Technology Co ltd
Liuzhou Weilinna New Material Technology Co ltd
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Guangdong Winner New Materials Technology Co ltd
Liuzhou Weilinna New Material Technology Co ltd
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Priority to CN202110343423.3A priority Critical patent/CN113121939A/en
Publication of CN113121939A publication Critical patent/CN113121939A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • C08L33/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12Homopolymers or copolymers of methyl methacrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses a composite resin material, a preparation method thereof and an automobile part, wherein the composite resin material is prepared from 65-80 parts by mass of first PMMA resin, 15-30 parts by mass of ASA resin, 5-10 parts by mass of a compatilizer, 0.2-0.6 part by mass of an antioxidant, 0.2-0.5 part by mass of a processing aid, 1-2 parts by mass of a graphene oxide master batch and 0.5-1 part by mass of black toner. According to the invention, by introducing the graphene oxide master batch, the integral coloring capability of the material is improved, so that the composite resin material has a piano black mirror surface bright effect, the black and bright effect is superior to that of similar products in the market, the piano black and bright effect can be obtained by direct injection molding without spray painting, the manufacturing efficiency of automobile parts such as automobile grilles is greatly improved, the manufacturing cost is greatly saved, and the wide market application prospect is achieved.

Description

Composite resin material, preparation method thereof and automobile part
Technical Field
The invention relates to a resin material, in particular to a composite resin material, a preparation method thereof and an automobile part.
Background
With the development of economic society and the improvement of the income level of residents, automobiles become common living consumer goods and enter thousands of households, and the selection of people for purchasing the automobiles gradually changes from single travel function requirements to various considerations such as pursuing model foreward, fashion color, intelligent interconnection and the like. The automobile air inlet grille with unique modeling design and bright black color is used as the front face of an automobile and can attract the attention of consumers in the first time.
At present, the older automobile grills generally adopt ABS (acrylonitrile-butadiene-styrene plastic) spray paint or common ASA (acrylonitrile-styrene-butyl acrylate), the whole product is not black and bright enough, and the ABS contains butadiene double bonds, so the weather resistance is poor. Due to the introduction of the paint spraying process, the requirement on a workpiece is high, various problems such as pockmarks, orange peel, paint removal and the like frequently occur during paint spraying, the qualification rate is low, the production cost is greatly improved, the smell of paint is very irritant, the painted workpiece is difficult to recover to become a pain point in the industry, and the concept of green development is not met.
PMMA has excellent optical property and weather resistance, and the coloring power of the product is high. But the ASA resin is hard and brittle, the product is easy to crack, the advantages of the ASA resin and the ASA resin can be combined, an alloy material with excellent comprehensive performance and bright appearance can be obtained, and the automobile grille can be directly formed by injection molding. Similar products are also on the market, but piano black and bright effects similar to painting cannot be achieved generally, and partial products have surface fogging due to toner problems or excessive toner addition.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a composite resin material, a preparation method thereof and an automobile part, wherein the automobile part prepared from the composite resin material is high in brightness and black, and does not need to be painted.
The first aspect of the invention provides a composite resin material which is prepared from 65-80 parts by mass of a first PMMA resin, 15-30 parts by mass of an ASA resin, 5-10 parts by mass of a compatilizer, 0.2-0.6 part by mass of an antioxidant, 0.2-0.5 part by mass of a processing aid, 1-2 parts by mass of a graphene oxide master batch and 0.5-1 part by mass of a black toner.
The composite resin material provided by the embodiment of the invention has at least the following beneficial effects:
the embodiment of the invention provides a composite resin material, which simultaneously uses PMMA resin and ASA resin, so that the composite resin material has excellent mechanical properties, chemical resistance and weather resistance of PMMA and ASA, simultaneously improves the integral coloring capability of the material by introducing graphene oxide master batches, has a mirror surface brightening effect of piano black, has a black and bright effect superior to that of similar products in the market, can be directly injection-molded, can obtain the black and bright effect of piano without spraying paint, greatly improves the manufacturing efficiency of automobile parts such as automobile grilles, greatly saves the manufacturing cost, and has a wide market application prospect.
In the present application, if the first and the second are described for the purpose of distinguishing technical features, they are not to be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features or implicitly indicating the precedence of the indicated technical features.
In some embodiments of the present invention, the graphene oxide masterbatch is prepared by mixing graphene oxide, the second PMMA resin and an auxiliary agent, which is different from the auxiliary agent used for the black powder.
In some embodiments of the present invention, the graphene oxide master batch is prepared by mixing 8 to 12 parts by mass of graphene oxide, 70 to 85 parts by mass of the second PMMA resin and 5 to 10 parts by mass of an auxiliary, based on the mass of the graphene oxide master batch.
In some embodiments of the present invention, the second PMMA resin has a weight average molecular weight of 70000 to 150000. Compared with the first PMMA resin, the PMMA resin with narrower molecular weight distribution and relatively smaller molecular weight is beneficial to obtaining the graphene oxide master batch with better fluidity and dispersibility so as to ensure the stability of material performance.
In some embodiments of the present invention, the black toner powder is made by mixing carbon black and an auxiliary agent. Compared with the method of directly using carbon black, the black powder formed by adding the auxiliary agent into the carbon black can be well and uniformly mixed with PMMA resin and ASA resin (such as ASA high-rubber powder).
In further embodiments of the present invention, the carbon black is contained in an amount of 60 to 80% by mass of the black powder.
In some embodiments of the present invention, the adjuvant is selected from at least one of polyethylene wax, ethylene bis stearamide.
In some embodiments of the present invention, the first PMMA resin has a weight average molecular weight of 70000 to 200000.
In some embodiments of the invention, the ASA resin is ASA high-rubber powder, and the rubber content of the ASA high-rubber powder is 40-60%. ASA high-gum powder is an ASA resin having a high rubber content.
In some embodiments of the invention, the compatibilizing agent is selected from at least one of styrene-maleic anhydride, styrene-acrylonitrile-maleic anhydride. In further embodiments of the present invention, the content of maleic anhydride in the compatibilizer is 5 to 15%.
In some embodiments of the invention, the processing aid is selected from at least one of ethylene bis stearamide, silicone, pentaerythritol stearate.
In some embodiments of the invention, the antioxidant is selected from at least one of hindered phenolic antioxidants, such as antioxidant 1010, antioxidant 1076, and the like, phosphite antioxidants, such as triphenyl phosphite, diphenyl isooctyl phosphite, and the like.
In a second aspect of the present invention, a method for preparing the above composite resin material is provided, which comprises the following steps:
taking or preparing a graphene oxide master batch;
weighing the raw materials according to the mass parts, and adding the raw materials into a high-speed mixer for mixing to obtain a premix;
and extruding and granulating the premix.
In some embodiments of the invention, extrusion granulation is performed using a twin screw extruder having a length to diameter ratio of 40: 1, the temperature is set to 190-.
In a third aspect of the present invention, an automobile part is provided, which is made of the above composite resin material or the composite resin material obtained by the above preparation method.
In some embodiments of the invention, the automotive part is an automotive grille.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
The graphene oxide masterbatch used in the following examples was prepared according to the following steps:
mixing 10 parts by mass of graphene oxide, 80 parts by mass of PMMA resin, 5 parts by mass of polyethylene wax and 5 parts by mass of an auxiliary agent bag, and performing twin-screw extrusion, strip drawing and grain cutting to obtain the graphene oxide master batch. Wherein the weight average molecular weight of the PMMA resin is 75000.
The black toner used in the following examples was prepared by mixing 60 wt% of carbon black and 40 wt% of polyethylene wax.
The compatibilizer used was styrene-acrylonitrile-maleic anhydride, purchased from Shanghai Wen, with a maleic anhydride content of 8%.
The used processing aid is pentaerythritol stearate which plays a role of a dispersing agent.
The antioxidant used was polyphenol antioxidant 1010.
Example 1
This example provides a composite resin material, prepared according to the following steps:
weighing 65 parts by mass of PMMA resin, 25 parts by mass of ASA resin, 10 parts by mass of compatilizer, 0.3 part by mass of antioxidant, 0.4 part by mass of processing aid, 0.75 part by mass of black toner and 1.5 parts by mass of graphene oxide master batch, mixing for 8 minutes in a high-speed mixer, and taking out to obtain a premix, wherein the weight average molecular weight of the PMMA resin is 120000;
then, the premix is melted and extruded by a double-screw extruder, and is cooled and granulated, wherein the length-diameter ratio of the double-screw extruder is 40: 1, the temperature is set to be 190-245 ℃, and the rotating speed of a main engine is 300-500 rpm.
Example 2
This example provides a composite resin material, prepared according to the following steps:
weighing 63 parts by mass of PMMA resin, 27 parts by mass of ASA resin, 10 parts by mass of compatilizer, 0.3 part by mass of antioxidant, 0.4 part by mass of processing aid, 0.75 part by mass of black toner and 1.8 parts by mass of graphene oxide master batch, mixing for 8 minutes in a high-speed mixer, and taking out to obtain a premix, wherein the weight average molecular weight of the PMMA resin is 120000;
then, the premix is melted and extruded by a double-screw extruder, and is cooled and granulated, wherein the length-diameter ratio of the double-screw extruder is 40: 1, the temperature is set to be 190-245 ℃, and the rotating speed of a main engine is 300-500 rpm.
Example 3
This example provides a composite resin material, prepared according to the following steps:
weighing 74 parts by mass of PMMA resin, 20 parts by mass of ASA resin, 6 parts by mass of compatilizer, 0.3 part by mass of antioxidant, 0.4 part by mass of processing aid, 0.5 part by mass of black toner and 1.2 parts by mass of graphene oxide master batch, mixing for 8 minutes in a high-speed mixer, and taking out to obtain a premix, wherein the weight average molecular weight of the PMMA resin is 120000;
then, the premix is melted and extruded by a double-screw extruder, and is cooled and granulated, wherein the length-diameter ratio of the double-screw extruder is 40: 1, the temperature is set to be 190-245 ℃, and the rotating speed of a main engine is 300-500 rpm.
Comparative example 1
In comparative example 1, a composite resin material was provided, prepared according to the following steps:
weighing 74 parts by mass of PMMA resin, 20 parts by mass of ASA resin, 6 parts by mass of compatilizer, 0.3 part by mass of antioxidant, 0.4 part by mass of processing aid and 0.5 part by mass of black toner, mixing for 8 minutes in a high-speed mixer, and taking out to obtain a premix, wherein the weight-average molecular weight of the PMMA resin is 120000;
then, the premix is melted and extruded by a double-screw extruder, and is cooled and granulated, wherein the length-diameter ratio of the double-screw extruder is 40: 1, the temperature is set to be 190-245 ℃, and the rotating speed of a main engine is 300-500 rpm.
Comparative example 2
Comparative example 2 provides a composite resin material prepared according to the following steps:
weighing 74 parts by mass of PMMA resin, 20 parts by mass of ASA resin, 6 parts by mass of compatilizer, 0.3 part by mass of antioxidant, 0.4 part by mass of processing aid and 0.75 part by mass of black toner, mixing for 8 minutes in a high-speed mixer, and taking out to obtain a premix, wherein the weight-average molecular weight of the PMMA resin is 120000;
then, the premix is melted and extruded by a double-screw extruder, and is cooled and granulated, wherein the length-diameter ratio of the double-screw extruder is 40: 1, the temperature is set to be 190-245 ℃, and the rotating speed of a main engine is 300-500 rpm.
Comparative example 3
Comparative example 3 provides a composite resin material prepared according to the following steps:
weighing 65 parts by mass of PMMA resin, 25 parts by mass of ASA resin, 10 parts by mass of compatilizer, 0.3 part by mass of antioxidant, 0.4 part by mass of processing aid and 0.75 part by mass of black toner, mixing for 8 minutes in a high-speed mixer, and taking out to obtain a premix, wherein the weight-average molecular weight of the PMMA resin is 120000;
then, the premix is melted and extruded by a double-screw extruder, and is cooled and granulated, wherein the length-diameter ratio of the double-screw extruder is 40: 1, the temperature is set to be 190-245 ℃, and the rotating speed of a main engine is 300-500 rpm.
Effect example 1
The composite resin materials of examples 1 to 3 and comparative examples 1 to 3 were subjected to mechanical property and color difference tests, and the results of the measurements are shown in Table 1. Wherein: the impact strength of the gap of the simply supported beam is tested according to the GB/T1043.1-2008 standard, and the pendulum bob is 4J; the yield strength is tested according to the GB/T1040.2-2006 standard, the sample bar is 1A, and the tensile rate is 50 mm/min; the bending strength and the bending modulus are tested according to the GB/T9341-2008 standard, and the testing speed is 2 mm/min; the melt flow rate is tested according to the GB/T3682.1-2018 standard, and the test condition is 220 ℃/10 kg; the color difference appearance adopts a highlight sample plate with the thickness of 2mm, the Konika Meinengda CM-2500C color measuring instrument is used for testing, and whether the fog, black and bright effect occurs or not is judged by naked eyes.
TABLE 1 results of mechanical Properties and color Difference tests of composite resin materials of examples 1 to 3 and comparative examples 1 to 3
Figure BDA0002999952020000051
Figure BDA0002999952020000061
As can be seen from table 1, comparing comparative examples 1 to 3, it is understood that simply increasing the amount of the black toner or the amount of the compatibilizer in the presence of the dispersant is not effective in increasing the blackness of the material and may cause a fogging phenomenon on the surface. Comparing examples 1-3 with comparative examples 1-3, it can be seen that the embodiment of the invention can obviously improve the surface smoothness and surface fogging of the composite resin material after the graphene oxide master batch is introduced, and the prepared composite resin material has a blacker and brighter effect than the common composite resin material. The comprehensive test result shows that the black and bright effect and the non-fogging effect can not be effectively realized only by increasing the content of the black powder or adjusting the content of the compatilizer and other components in the formula, the black and bright effect of the material is greatly improved by introducing the graphene oxide master batch, paint spraying is not needed, the cost is saved, the manufacturing efficiency is improved, and the application prospect is wide.
It can be understood that, a person skilled in the art can use the composite resin material prepared by the embodiment of the invention to manufacture an automobile part, such as an automobile grille, since the composite resin prepared by the embodiment of the invention can achieve very excellent black and bright effect, and the composite resin can be manufactured into the automobile grille without painting, the manufacturing cost can be greatly saved.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.

Claims (10)

1. The composite resin material is characterized by being prepared from 65-80 parts by mass of first PMMA resin, 15-30 parts by mass of ASA resin, 5-10 parts by mass of a compatilizer, 0.2-0.6 part by mass of an antioxidant, 0.2-0.5 part by mass of a processing aid, 1-2 parts by mass of graphene oxide master batches and 0.5-1 part by mass of black powder.
2. The composite resin material according to claim 1, wherein the graphene oxide masterbatch is prepared by mixing graphene oxide, a second PMMA resin and an auxiliary agent.
3. The composite resin material according to claim 2, wherein the second PMMA resin has a weight average molecular weight of 70000 to 150000.
4. The composite resin material according to claim 1, wherein the black toner is made by mixing carbon black and an auxiliary agent; preferably, the content of the carbon black is 60 to 80% by mass of the black toner.
5. The composite resin material according to claim 2 or 4, wherein the auxiliary agent is at least one selected from polyethylene wax and ethylene bis stearamide.
6. The composite resin material according to any one of claims 1 to 4, wherein the first PMMA resin has a weight average molecular weight of 70000 to 200000.
7. The composite resin material as claimed in any one of claims 1 to 4, wherein the ASA resin is ASA high-rubber powder, and the rubber content of the ASA high-rubber powder is 40-60%.
8. The composite resin material according to any one of claims 1 to 4, wherein the compatibilizer is at least one selected from styrene-maleic anhydride, styrene-acrylonitrile-maleic anhydride; preferably, the processing aid is selected from at least one of ethylene bis stearamide, silicone, pentaerythritol stearate.
9. A method of producing a composite resin material as claimed in any one of claims 1 to 8, characterized by comprising the steps of:
taking or preparing a graphene oxide master batch;
weighing the raw materials according to the mass parts, and adding the raw materials into a high-speed mixer for mixing to obtain a premix;
and extruding and granulating the premix.
10. An automobile part characterized by being produced using the composite resin material according to any one of claims 1 to 8 or the composite resin material produced using the production method according to claim 9; preferably, the automobile part is an automobile grille.
CN202110343423.3A 2021-03-30 2021-03-30 Composite resin material, preparation method thereof and automobile part Pending CN113121939A (en)

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