CN113388221A - ABS composite material and preparation method thereof - Google Patents
ABS composite material and preparation method thereof Download PDFInfo
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- CN113388221A CN113388221A CN202110593447.4A CN202110593447A CN113388221A CN 113388221 A CN113388221 A CN 113388221A CN 202110593447 A CN202110593447 A CN 202110593447A CN 113388221 A CN113388221 A CN 113388221A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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Abstract
The application relates to an ABS composite material and a preparation method thereof. The ABS composite material comprises the following raw materials: 55-70 parts of ABS resin, 0.3-0.8 part of composite antioxidant, 0.3-0.8 part of composite light stabilizer, 2-10 parts of inorganic filler, 0.1-0.3 part of lubricant, 0.2-0.4 part of anti-dripping agent and 20-30 parts of flame retardant; wherein the composite antioxidant is obtained by carrying out complex reaction on an antioxidant and a polyamide-amine dendritic polymer; the composite light stabilizer is obtained by carrying out complex reaction on a light stabilizer and a polyamide-amine dendritic polymer; wherein, the parts are parts by weight. The ABS composite material provided by the scheme can solve the phenomena of yellowing and poor weather resistance of materials which often appear in the use process of the ABS material.
Description
Technical Field
The application relates to the technical field of materials, in particular to an ABS composite material and a preparation method thereof.
Background
The 5VA flame-retardant ABS has high flame-retardant and fireproof grade and excellent performance, and is widely applied to automobiles and household appliances. However, the ABS as a base material resin contains unsaturated double bonds and cyano groups in the molecule, and the ABS material is subjected to oxidation crosslinking reaction under the action of metal ions, light, oxygen and heat, so that the ABS material is yellow and has poor weather resistance.
In order to prevent the color change of the ABS resin, an antioxidant and a light stabilizer are usually added, although the additives can prevent the aging degradation of the ABS resin to a certain extent, the light stabilizer and the antioxidant belong to small molecules and are influenced by compatibility, an interface effect exists between matrix ABS resins, and the small molecules can migrate and precipitate from the matrix ABS resin after a long time, so that the surface gloss of the ABS resin is damaged. On the other hand, these adjuvant molecules are difficult to disperse in the matrix ABS resin, and complete compatibility of the adjuvant molecules with the matrix resin cannot be guaranteed. The final result is that the flame retardant ABS material often has the phenomena of yellowing and poor weather resistance during the use process.
Disclosure of Invention
In order to overcome the problems in the related art, the ABS composite material and the preparation method thereof are provided, and the problems of yellowing and poor weather resistance of the material caused by difficult precipitation and dispersion of auxiliary agent molecules in the ABS material are solved.
In a first aspect, the present application provides an ABS composite characterized in that,
the ABS composite material is prepared from the following raw materials: 55-70 parts of ABS resin, 0.3-0.8 part of composite antioxidant, 0.3-0.8 part of composite light stabilizer, 2-10 parts of inorganic filler, 0.1-0.3 part of lubricant, 0.2-0.4 part of anti-dripping agent and 20-30 parts of flame retardant;
wherein, the preparation raw materials of the composite antioxidant comprise: antioxidant and polyamidoamine dendrimer; the preparation raw materials of the composite light stabilizer comprise: light stabilizers and polyamidoamine dendrimers;
wherein, the parts are parts by weight.
In one embodiment, the antioxidant is a hindered phenolic antioxidant.
In one embodiment, the light stabilizer is a benzophenone-based light stabilizer.
In one embodiment, the polyamidoamine dendrimer is a half-generation dendrimer, the generation number of which is 1.5G to 4.5G, the terminal group species is a carboxyl group, the acid value content is 300mgKOH/G to 550mgKOH/G, and the molecular weight content is 15000-20000-.
In one embodiment, the preparation raw material of the ABS composite further comprises: at least one of a heat stabilizer and a dispersant.
In one embodiment, the inorganic filler is a combination of one or both of barium sulfate and calcium carbonate.
In one embodiment, the flame retardant is a halogenated flame retardant system flame retardant.
In a second aspect, the present application provides a method for preparing an ABS composite material, comprising:
performing a complex reaction between the polyamide-amine dendritic polymer and an antioxidant to prepare a composite antioxidant;
carrying out a complex reaction on a polyamide-amine dendritic polymer and a light stabilizer to prepare a composite light stabilizer;
adding the composite antioxidant, the composite light stabilizer, the inorganic filler, the lubricant, the anti-dripping agent and the flame retardant into ABS resin to obtain a mixed raw material;
and processing the mixed raw materials by using a granulator to obtain the ABS composite material.
In one embodiment, the complex antioxidant prepared by the complexation reaction of the polyamide-amine dendrimer and the antioxidant comprises:
and preparing the composite antioxidant based on the polyamide-amine dendritic polymer and the antioxidant by adopting a hydrothermal method.
In one embodiment, the complex light stabilizer prepared by the complexation reaction of the polyamidoamine dendrimer and the light stabilizer comprises:
and preparing the composite light stabilizer by adopting a hydrothermal method based on the polyamide-amine dendritic polymer and the light stabilizer.
In one embodiment, the polyamide-amine based dendrimer and the antioxidant are prepared by a hydrothermal method to obtain a composite antioxidant, which comprises:
dissolving the polyamide-amine dendritic polymer in dimethylformamide, and stirring at normal temperature by using a polytetrafluoroethylene stirring paddle to obtain a polyamide-amine dendritic polymer solution;
adding the antioxidant into the polyamide-amine dendritic polymer solution and uniformly stirring at normal temperature to obtain a composite antioxidant solution;
heating the composite antioxidant solution to a preset temperature, preserving heat for a preset time, cooling to room temperature, carrying out centrifugal cleaning by using alcohol until the supernatant of the composite antioxidant solution is colorless and transparent, and drying the lower-layer solid to obtain the composite antioxidant.
In one embodiment, the polyamide-amine based dendrimer and the light stabilizer are prepared by a hydrothermal method to obtain a composite light stabilizer, which comprises the following steps:
dissolving the polyamide-amine dendritic polymer in dimethylformamide, and stirring at normal temperature by using a polytetrafluoroethylene stirring paddle to obtain a polyamide-amine dendritic polymer solution;
adding the light stabilizer into the polyamide-amine dendritic polymer solution and uniformly stirring at normal temperature to obtain a composite light stabilizer solution;
heating the composite light stabilizer solution to a preset temperature, keeping the temperature for a preset time, cooling to room temperature, carrying out centrifugal cleaning by using alcohol until the supernatant of the composite light stabilizer solution is colorless and transparent, and drying the bottom precipitate to obtain the composite light stabilizer.
In one embodiment, the composite antioxidant, the composite light stabilizer, the inorganic filler, the lubricant, the anti-dripping agent and the flame retardant are added into the ABS resin to obtain a mixed raw material, which comprises:
adding the ABS resin, the flame retardant and the powder auxiliary agent into a high-speed mixer for mixing by adopting a weightlessness weighing blanking mode to obtain a mixed raw material;
the powder auxiliary agent comprises: the inorganic filler, the composite antioxidant, the composite light stabilizer, the lubricant and the anti-dripping agent.
In one embodiment, before the ABS resin is added into a high-speed mixer, the ABS resin and white mineral oil are uniformly mixed at a low speed, so that the surface of the ABS resin is coated with a layer of the white mineral oil;
the mass of the white mineral oil is 0.3 percent of the total mass of the ABS resin, the flame retardant and the powder auxiliary agent.
The technical scheme provided by the application can comprise the following beneficial effects:
in the scheme, the polyamide-amine dendrimer and the antioxidant/light stabilizer are subjected to a complex reaction, the terminal group of the polyamide-amine dendrimer and the antioxidant/light stabilizer molecule are dehydrated to form a covalent bond, thereby leading the antioxidant/light stabilizer micromolecules to be stably combined with the polyamide-amine type dendritic polymer, leading the unique three-dimensional space structure of the polyamide-amine type dendritic polymer to be capable of tightly wrapping the antioxidant/light stabilizer micromolecules, leading the polyamide-amine type dendritic polymer to be a macromolecular material, the polyamide-amine type dendritic polymer antioxidant/light stabilizer has very good compatibility with matrix ABS resin, so that the antioxidant/light stabilizer micromolecules adsorbed on the polyamide-amine type dendritic polymer can be stabilized in the matrix ABS resin for a long time without migration and precipitation; in addition, the polyamide-amine dendritic polymer wrapped with the antioxidant/light stabilizer micromolecules is in a space spherical structure, has smaller hydrodynamic radius and very low melt viscosity characteristic, and can greatly improve the problem that the antioxidant/light stabilizer is difficult to disperse in the matrix ABS resin. Therefore, the ABS composite material prepared according to the scheme solves the problems of yellowing and poor weather resistance of the material caused by difficult precipitation and dispersion of auxiliary agent molecules.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application.
Drawings
The foregoing and other objects, features and advantages of the application will be apparent from the following more particular descriptions of exemplary embodiments of the application, as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the application.
FIG. 1 is a schematic structural view of a composite light stabilizer shown in an example of the present application;
FIG. 2 is a schematic structural diagram of a complex antioxidant shown in the examples herein;
fig. 3 is a schematic flow chart of a method for preparing an ABS composite material shown in an embodiment of the present application.
Detailed Description
Preferred embodiments of the present application will be described in more detail below with reference to the accompanying drawings. While the preferred embodiments of the present application are shown in the drawings, it should be understood that the present application may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.
It should be understood that although the terms "first," "second," "third," etc. may be used herein to describe various information, these information should not be limited to these terms. These terms are only used to distinguish one type of information from another. For example, first information may also be referred to as second information, and similarly, second information may also be referred to as first information, without departing from the scope of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present application, "a plurality" means two or more unless specifically limited otherwise.
Because the light stabilizer and the antioxidant belong to small molecules and are influenced by compatibility, an interface effect exists between matrix ABS resins, and the small molecules can migrate and separate out from the matrix ABS resins after a long time, so that the surface glossiness of the ABS resins is damaged. On the other hand, these adjuvant molecules are difficult to disperse in the matrix ABS resin, and complete compatibility of the adjuvant molecules with the matrix resin cannot be guaranteed. The final result is that the flame retardant ABS material often has the phenomena of yellowing and poor weather resistance during the use process.
Example one
In view of the above problems, embodiments of the present application provide an ABS composite material, which is excellent in yellowing resistance and weather resistance.
The technical solutions of the embodiments of the present application are described in detail below.
The ABS composite material is prepared from the following raw materials: 55-70 parts of ABS resin, 0.3-0.8 part of composite antioxidant, 0.3-0.8 part of composite light stabilizer, 2-10 parts of inorganic filler, 0.1-0.3 part of lubricant, 0.2-0.4 part of anti-dripping agent and 20-30 parts of flame retardant;
wherein, the preparation raw materials of the composite antioxidant comprise: antioxidant and polyamidoamine dendrimer; the preparation raw materials of the composite light stabilizer comprise: light stabilizers and polyamidoamine dendrimers;
wherein, the parts are parts by weight.
In the examples of the present application, hindered phenol-based antioxidants are used as the antioxidants, and preferably, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], i.e., a common antioxidant 1010, can be used.
In the examples of the present application, benzophenone is used as the light stabilizer, and 2-hydroxy-4-n-octoxybenzophenone, i.e., UV531 as the light stabilizer, is preferably used.
In the examples of the present application, the polyamidoamine dendrimer is a half-generation dendrimer, the generation number of which is 1.5G to 4.5G, the terminal group species is a carboxyl group, the acid value content is 300mgKOH/G to 550mgKOH/G, and the molecular weight content is 15000-20000-.
FIG. 1 is a schematic structural diagram of a composite antioxidant and a composite light stabilizer.
Referring to fig. 1, the polyamidoamine dendrimer has high symmetry and monodispersity, the internal cavity of the polyamidoamine dendrimer can be used for wrapping other molecules, and the surface terminal group of the polyamidoamine dendrimer can be used for connecting active substances. In the embodiment of the application, the terminal group of the polyamide-amine dendrimer is dehydrated and connected with the antioxidant micromolecule to form a covalent bond, and the internal cavity of the polyamide-amine dendrimer wraps the antioxidant micromolecule to form a composite antioxidant with a polyamide-amine dendrimer/antioxidant composite structure; the end group of the polyamide-amine dendrimer is connected with the light stabilizer micromolecule in a dehydration manner to form a covalent bond, and the light stabilizer micromolecule is wrapped by the internal cavity of the polyamide-amine dendrimer to form the composite light stabilizer with the polyamide-amine dendrimer/light stabilizer composite structure.
In the embodiment of the application, the ABS resin is synthesized by a bulk polymerization method, and the polymer has the characteristics of purity, small molecular structure and less monomer residue. The notch impact strength is 25-35KJ/m2The melt index is 15-25g/10 min. Preferably, ABS-8391 may be used.
In the embodiment of the application, the inorganic filler is selected from any one of barium sulfate and calcium carbonate or a compound of the barium sulfate and the calcium carbonate. Wherein the barium sulfate can be precipitated barium sulfate produced by blind nitre method, and has mesh number of 2500. The calcium carbonate is light calcium carbonate with 1250 meshes.
In the embodiment of the application, the flame retardant is a halogen-containing flame retardant system, and specifically can be prepared by compounding decabromodiphenylethane, tetrabromobifenyl-A, bromotriazine, antimony trioxide, zinc oxide, antimony chloride, antimony bromide and the like according to a weight ratio of 3:1 to 4: 1.
In the embodiment of the application, ethylene bis stearamide is preferably used as the lubricant.
In the preparation raw materials of the ABS composite material provided by the embodiment of the application, the ABS composite material comprises a composite antioxidant and a composite light stabilizer, wherein the preparation raw materials of the composite antioxidant comprise: antioxidant and polyamidoamine dendrimer; the preparation raw materials of the composite light stabilizer comprise: light stabilizers and polyamidoamine dendrimers. The polyamide-amine dendritic polymer and the antioxidant/light stabilizer are subjected to a complex reaction, the terminal group of the polyamide-amine dendritic polymer and the antioxidant/light stabilizer molecule are dehydrated to form a covalent bond, so that the antioxidant/light stabilizer micromolecule is stably combined with the polyamide-amine dendritic polymer, the antioxidant/light stabilizer micromolecule can be tightly wrapped by the unique three-dimensional space structure of the polyamide-amine dendritic polymer, and the polyamide-amine dendritic polymer is a macromolecular material and has very good compatibility with matrix ABS resin, so that the antioxidant/light stabilizer micromolecule adsorbed on the polyamide-amine dendritic polymer can be stabilized in the matrix ABS resin for a long time without migration and precipitation; in addition, the polyamide-amine dendritic polymer wrapped with the antioxidant/light stabilizer micromolecules is in a space spherical structure, has smaller hydrodynamic radius and very low melt viscosity characteristic, and can greatly improve the problem that the antioxidant/light stabilizer is difficult to disperse in the matrix ABS resin. Therefore, the ABS composite material prepared according to the scheme solves the problems of yellowing and poor weather resistance of the material caused by difficult precipitation and dispersion of auxiliary agent molecules.
Example two
On the basis of the ABS composite material described in the first embodiment, a heat stabilizer and/or a dispersant may be added to the raw materials to improve the stability of the ABS composite material.
The embodiment of the application provides an ABS composite material, which comprises the following preparation raw materials: 55-70 parts of ABS resin, 0.3-0.8 part of composite antioxidant, 0.3-0.8 part of composite light stabilizer, 2-10 parts of inorganic filler, 0.1-0.3 part of lubricant, 0.2-0.4 part of anti-dripping agent and 20-30 parts of flame retardant, wherein the composite antioxidant is prepared from the following raw materials: antioxidant and polyamidoamine dendrimer; the preparation raw materials of the composite light stabilizer comprise: light stabilizers and polyamidoamine dendrimers; wherein, the parts are parts by weight;
the ABS composite material is prepared from the following raw materials: at least one of a heat stabilizer and a dispersant.
In the embodiment of the application, the heat stabilizer is selected from phosphite antioxidants, preferably, an antioxidant 168; the parts are 0.3 parts.
In the application example, the dispersant is selected from pentaerythritol stearate, and the part of the pentaerythritol stearate is 0.2 part.
In the embodiment of the application, in the experimental stage, the proportion of the raw materials for preparing the ABS is researched, and the specific experimental result is as follows:
in the above table, other adjuvants include: 0.2 part of lubricant, 0.3 part of anti-dripping agent, 0.3 part of heat stabilizer and 0.2 part of dispersing agent.
In the above experiment process, after each group of granulated particles is injection molded into a sample strip in an injection molding machine at 185 ℃ to 230 ℃, the sample strip comprises: color plates, tensile splines, bending splines, and impact splines; and (5) carrying out performance test on the sample strips. The bars were placed in an environment with a temperature range of 21 ℃ to 25 ℃ and a humidity range of 40% to 60% for 88h prior to testing.
In the experimental process, the method for testing the weather resistance comprises the following steps: after the tensile sample, the bending sample and the impact sample were respectively irradiated with a xenon arc lamp for 1500 hours, the tensile strength of the tensile sample, the elongation at break of the bending sample and the retention rate of physical properties of the impact strength of the impact sample were measured.
The yellowing resistance test method comprises the following steps: after the color plate was irradiated with an ultraviolet lamp for 96 hours, the change color difference value Δ E before and after irradiation was measured.
According to the analysis of the experimental results in the above table, the following results can be obtained:
according to the comparison of the experimental results of the experimental group 1 and the comparative group 1, the experimental group 2 and the comparative group 2, and the experimental group 3 and the comparative group 3, compared with the ABS material prepared by using the traditional antioxidant and the traditional light stabilizer, the ABS composite material prepared by using the composite antioxidant and the composite light stabilizer has no obvious change in tensile strength and bending strength, but the elongation at break, impact strength and melt index of the material are improved to a large extent, and in the aspects of weather resistance and yellowing resistance of the material, the color difference value delta E of the ABS composite material after being irradiated by an ultraviolet lamp for 96 hours is less than 6, and after being subjected to a 1500 lamp aging test, the retention rate of various xenon physical properties is higher than 80%, so that the ABS composite material shows excellent performances in the aspects of weather resistance and yellowing resistance.
Due to the highly branched polyamide-amine dendritic polymer and the shape of a sphere-like structure, intermolecular chains are less entangled, so that the melt viscosity is low, and the melt index of the ABS composite material is improved.
In the above experiment, an experiment group 4 for reducing the formulation is provided, and the addition amount of the flame retardant is reduced by increasing the amount of the inorganic filler, so that the formulation cost is reduced. According to the experimental result, the part of the flame retardant can be reduced by increasing the filler, but the elongation at break and the impact strength of the prepared ABS composite material are reduced to a certain degree correspondingly. But still shows more excellent performances in the aspects of weather resistance and yellowing resistance.
Furthermore, in the experiment, the research on the addition amount of the flame retardant in the comparison group 4 and the comparison group 5 is also set, and according to the experiment results of the comparison group 4 and the comparison group 5, the addition amount of the flame retardant needs to be enough to ensure that the obtained ABS composite material can pass the 5VA grade of UL 94; with the further increase of the filler part, various physical properties of the ABS composite material are sharply reduced, which indicates that in the ABS preparation process, various properties of the ABS composite material can be ensured only by controlling the filler part within a proper range.
Based on the above experimental data, in consideration of the preparation cost, preferably, the preparation raw material ratios of the ABS composite material in the embodiment of the present application are: 64-67 parts of ABS resin, 4-6 parts of inorganic filler, 26-37 parts of flame retardant, 0.5-0.7 part of composite antioxidant, 0.5-0.7 part of composite light stabilizer, 0.2 part of lubricant, 0.3 part of anti-dripping agent, 0.3 part of heat stabilizer and 0.2 part of dispersant.
The embodiment of the application provides a preparation formula of the ABS composite material added with the heat stabilizer and the dispersing agent, and experimental research is carried out on the addition proportion of each preparation raw material to obtain the preparation formula of the ABS composite material considering the material performance and the comprehensive cost. The ABS composite material shown in the embodiment of the application has excellent anti-yellowing and weather-resistant performances, meanwhile, the tensile strength, the bending strength, the elongation at break, the impact strength and the melt index of the ABS composite material can be guaranteed, and the stability of the ABS composite material is enhanced by adding the heat stabilizer and the dispersing agent.
EXAMPLE III
Corresponding to the ABS composite material, the application also provides a preparation method and corresponding embodiments of the ABS composite material.
Fig. 3 is a schematic flow chart of a method for preparing an ABS composite material shown in an embodiment of the present application.
Referring to fig. 3, the preparation method of the ABS composite material includes:
301. performing a complex reaction between the polyamide-amine dendritic polymer and an antioxidant to prepare a composite antioxidant;
in the embodiment of the application, the composite antioxidant is prepared by a hydrothermal method based on the polyamidoamine dendrimer and the antioxidant, specifically:
dissolving polyamide-amine dendritic polymer in dimethylformamide, and stirring at normal temperature by using a polytetrafluoroethylene stirring paddle to obtain a polyamide-amine dendritic polymer solution;
adding an antioxidant into the polyamide-amine dendritic polymer solution, and uniformly stirring at normal temperature to obtain a composite antioxidant solution;
heating the composite antioxidant solution to a preset temperature, preserving heat for a preset time, cooling to room temperature, carrying out centrifugal cleaning by using alcohol until the supernatant of the composite antioxidant solution is colorless and transparent, and drying the lower-layer solid to obtain the composite antioxidant.
Further, the preparation of the composite antioxidant can be carried out according to the following steps: firstly, 50g of polyamide-amine dendritic polymer is dissolved in dimethylformamide, and is stirred for 10min at normal temperature by a polytetrafluoroethylene stirring paddle, then 30g of antioxidant is respectively added into the solution in the stirring process, after stirring for 10min at normal temperature, the temperature is continuously raised to 95 ℃, the solution is cooled to room temperature after being kept for 8h, alcohol is used for centrifugal cleaning, and after the supernatant is colorless and transparent, the lower-layer precipitate is dried for standby application.
It should be noted that the above description of the preparation process of the composite antioxidant is only an example of the experimental stage given in the embodiment of the present application, and in the actual application process, the preparation parameters such as the weight of each raw material, the preset temperature, the preset duration, and the like can be adjusted according to the production requirement. That is, the description of the preparation process of the above complex antioxidant is not necessarily intended as a limitation of the present invention.
302. Carrying out a complex reaction on a polyamide-amine dendritic polymer and a light stabilizer to prepare a composite light stabilizer;
in the embodiment of the present application, the polyamide-amine dendrimer and the light stabilizer are prepared by a hydrothermal method to obtain the composite light stabilizer, specifically:
dissolving polyamide-amine dendritic polymer in dimethylformamide, and stirring at normal temperature by using a polytetrafluoroethylene stirring paddle to obtain a polyamide-amine dendritic polymer solution;
adding a light stabilizer into the polyamide-amine dendritic polymer solution, and uniformly stirring at normal temperature to obtain a composite light stabilizer solution;
heating the composite light stabilizer solution to a preset temperature, preserving the heat for a preset time, cooling to room temperature, carrying out centrifugal cleaning by using alcohol until the supernatant of the composite light stabilizer solution is colorless and transparent, and drying the lower-layer solid to obtain the composite light stabilizer.
Further, the preparation of the composite light stabilizer can be carried out according to the following steps: firstly, 50g of polyamide-amine dendritic polymer is dissolved in dimethylformamide, stirred for 10min at normal temperature by a polytetrafluoroethylene stirring paddle, then 30g of light stabilizer is respectively added into the solution in the stirring process, stirred for 10min at normal temperature, continuously heated to 95 ℃, kept warm for 8h, cooled to room temperature, centrifugally cleaned by alcohol until the supernatant is colorless and transparent, and then the lower-layer precipitate is dried for later use.
It should be noted that the above description of the preparation process of the composite light stabilizer is only an example of the experimental stage given in the embodiment of the present application, and in the practical application process, the preparation parameters such as the weight of each raw material, the preset temperature, the preset duration, and the like can be adjusted according to the production requirement. That is, the description of the above-mentioned process for preparing the composite light stabilizer is not necessarily intended as a limitation of the present invention.
303. Adding the composite antioxidant, the composite light stabilizer, the inorganic filler, the lubricant, the anti-dripping agent and the flame retardant into ABS resin to obtain a mixed raw material;
in the embodiment of the application, in order to ensure the accuracy of the blanking parts of the preparation raw materials, a weightless weighing blanking mode is adopted, and the ABS resin, the flame retardant and the powder auxiliary agent are added into a high-speed mixer for mixing to obtain a mixed raw material; the weightlessness scale is divided into 3 blanking bins for blanking, wherein the first bin is ABS resin, the second bin is a fire retardant bin, and the third bin is an auxiliary agent bin.
The powder auxiliary agent comprises: inorganic filler, composite antioxidant, composite light stabilizer, lubricant and anti-dripping agent.
Further, the powder auxiliary agent may further include at least one of a heat stabilizer and a dispersant.
Further, in order to ensure that various additives can be uniformly dispersed, before the ABS resin is added into a high-speed mixer, the ABS resin and white mineral oil are uniformly mixed at a low speed, so that a layer of white mineral oil is coated on the surface of the ABS resin;
the mass of the white mineral oil is 0.3 percent of the total mass of the ABS resin, the flame retardant and the powder auxiliary agent.
In the embodiment of the application, the rotating speed of the high-speed mixer ranges from 320r/min to 450 r/min; when the ABS resin and the white mineral oil are mixed at low speed, the rotating speed of the mixer ranges from 40r/min to 80 r/min.
It is understood that the above description of the blanking process of the mixed raw material is only one example given in the embodiments of the present application, and the specific blanking manner may be adjusted according to the actual production situation, for example, the powder auxiliary agent may also be blanked by using a vibrating screen quantitative blanking manner.
304. And processing the mixed raw materials by using a granulator to obtain the ABS composite material.
In the embodiment of the application, the mixed raw materials are granulated by a granulator, specifically, the adopted granulator is a double-screw extruder, the extrusion processing temperature is controlled to be 180-225 ℃, the vacuum degree is kept to be-0.07-0.09 MPa in the processing process, and the ABS composite material is obtained by water cooling, air drying, granulating, sieving and homogenizing after granulation.
The embodiment of the application shows a preparation method of an ABS composite material, the polyamide-amine dendritic polymer is respectively subjected to complex reaction with an antioxidant and a light stabilizer to obtain a composite antioxidant and a composite light stabilizer, the macromolecular structure, the terminal group and the internal cavity of the polyamide-amine dendritic polymer are utilized, the antioxidant and the light stabilizer are firmly wrapped in the polyamide-amine dendritic polymer to form a stable molecular system, and therefore the ABS composite material obtained by mixing ABS resin, the composite antioxidant, the composite light stabilizer, an inorganic filler, a lubricant, an anti-dripping agent and a flame retardant and then extruding and granulating the mixture through a double-screw extruder is not easy to migrate and precipitate out of matrix ABS resin to cause yellowing and poor weather resistance.
The aspects of the present application have been described in detail hereinabove with reference to the accompanying drawings. In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments. Those skilled in the art should also appreciate that the acts and modules referred to in the specification are not necessarily required in the present application. In addition, it can be understood that the steps in the method of the embodiment of the present application may be sequentially adjusted, combined, and deleted according to actual needs, and the modules in the device of the embodiment of the present application may be combined, divided, and deleted according to actual needs.
The flowchart and block diagrams in the figures illustrate the architecture, functionality, and operation of possible implementations of systems and methods according to various embodiments of the present application. It should also be noted that, in some alternative implementations, the functions noted in the block may occur out of the order noted in the figures. For example, two blocks shown in succession may, in fact, be executed substantially concurrently, or the blocks may sometimes be executed in the reverse order, depending upon the functionality involved. It will also be noted that each block of the block diagrams and/or flowchart illustration, and combinations of blocks in the block diagrams and/or flowchart illustration, can be implemented by special purpose hardware-based systems which perform the specified functions or acts, or combinations of special purpose hardware and computer instructions.
Having described embodiments of the present application, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen in order to best explain the principles of the embodiments, the practical application, or improvements made to the technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (14)
1. An ABS composite material, which is characterized in that,
the ABS composite material is prepared from the following raw materials: 55-70 parts of ABS resin, 0.3-0.8 part of composite antioxidant, 0.3-0.8 part of composite light stabilizer, 2-10 parts of inorganic filler, 0.1-0.3 part of lubricant, 0.2-0.4 part of anti-dripping agent and 20-30 parts of flame retardant;
wherein, the preparation raw materials of the composite antioxidant comprise: antioxidant and polyamidoamine dendrimer; the preparation raw materials of the composite light stabilizer comprise: light stabilizers and polyamidoamine dendrimers;
wherein, the parts are parts by weight.
2. The ABS composite according to claim 1,
the antioxidant is hindered phenol antioxidant.
3. The ABS composite according to claim 1,
the light stabilizer is a benzophenone light stabilizer.
4. The ABS composite according to claim 1,
the polyamidoamine dendrimer is a half-generation dendrimer, the generation number of the half-generation dendrimer is 1.5G-4.5G, the type of the terminal group is carboxyl, the acid value content is 300mgKOH/G-550mgKOH/G, and the molecular weight content is 15000-20000-.
5. The ABS composite according to claim 1,
the ABS composite material also comprises the following raw materials: at least one of a heat stabilizer and a dispersant.
6. The ABS composite according to claim 1,
the inorganic filler is one or two of barium sulfate and calcium carbonate.
7. The ABS composite according to claim 1,
the flame retardant is a halogen flame retardant system flame retardant.
8. A preparation method of an ABS composite material is characterized by comprising the following steps:
performing a complex reaction between the polyamide-amine dendritic polymer and an antioxidant to prepare a composite antioxidant;
carrying out a complex reaction on a polyamide-amine dendritic polymer and a light stabilizer to prepare a composite light stabilizer;
adding the composite antioxidant, the composite light stabilizer, the inorganic filler, the lubricant, the anti-dripping agent and the flame retardant into ABS resin to obtain a mixed raw material;
and processing the mixed raw materials by using a granulator to obtain the ABS composite material.
9. The preparation method of the ABS composite material according to claim 8, wherein the complex reaction of the polyamide-amine dendrimer and the antioxidant is used to prepare the composite antioxidant, and the preparation method comprises the following steps:
and preparing the composite antioxidant based on the polyamide-amine dendritic polymer and the antioxidant by adopting a hydrothermal method.
10. The preparation method of the ABS composite material according to claim 8, wherein the preparation of the composite light stabilizer by the complexation reaction of the polyamide-amine dendrimer and the light stabilizer comprises:
and preparing the composite light stabilizer by adopting a hydrothermal method based on the polyamide-amine dendritic polymer and the light stabilizer.
11. The preparation method of the ABS composite material as claimed in claim 9, wherein the polyamide-amine based dendrimer and the antioxidant are prepared by a hydrothermal method to obtain the composite antioxidant, and the preparation method comprises the following steps:
dissolving the polyamide-amine dendritic polymer in dimethylformamide, and stirring at normal temperature by using a polytetrafluoroethylene stirring paddle to obtain a polyamide-amine dendritic polymer solution;
adding the antioxidant into the polyamide-amine dendritic polymer solution and uniformly stirring at normal temperature to obtain a composite antioxidant solution;
heating the composite antioxidant solution to a preset temperature, preserving heat for a preset time, cooling to room temperature, carrying out centrifugal cleaning by using alcohol until the supernatant of the composite antioxidant solution is colorless and transparent, and drying the lower-layer solid to obtain the composite antioxidant.
12. The preparation method of the ABS composite material according to claim 10, wherein the polyamide-amine based dendrimer and the light stabilizer are prepared by a hydrothermal method to obtain the composite light stabilizer, and the preparation method comprises the following steps:
dissolving the polyamide-amine dendritic polymer in dimethylformamide, and stirring at normal temperature by using a polytetrafluoroethylene stirring paddle to obtain a polyamide-amine dendritic polymer solution;
adding the light stabilizer into the polyamide-amine dendritic polymer solution and uniformly stirring at normal temperature to obtain a composite light stabilizer solution;
heating the composite light stabilizer solution to a preset temperature, keeping the temperature for a preset time, cooling to room temperature, carrying out centrifugal cleaning by using alcohol until the supernatant of the composite light stabilizer solution is colorless and transparent, and drying the bottom precipitate to obtain the composite light stabilizer.
13. The preparation method of the ABS composite material according to claim 8, wherein the composite antioxidant, the composite light stabilizer, the inorganic filler, the lubricant, the anti-dripping agent and the flame retardant are added into the ABS resin to obtain a mixed raw material, which comprises:
adding the ABS resin, the flame retardant and the powder auxiliary agent into a high-speed mixer for mixing by adopting a weightlessness weighing blanking mode to obtain a mixed raw material;
the powder auxiliary agent comprises: the inorganic filler, the composite antioxidant, the composite light stabilizer, the lubricant and the anti-dripping agent.
14. The method for producing an ABS composite material according to claim 13,
before the ABS resin is added into a high-speed mixer, uniformly mixing the ABS resin and white mineral oil at a low speed to coat a layer of white mineral oil on the surface of the ABS resin;
the mass of the white mineral oil is 0.3 percent of the total mass of the ABS resin, the flame retardant and the powder auxiliary agent.
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