CN116041933A - Halogen-free high-temperature-resistant flame-retardant ABS composite PC alloy material and preparation method and application thereof - Google Patents
Halogen-free high-temperature-resistant flame-retardant ABS composite PC alloy material and preparation method and application thereof Download PDFInfo
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- CN116041933A CN116041933A CN202310060929.2A CN202310060929A CN116041933A CN 116041933 A CN116041933 A CN 116041933A CN 202310060929 A CN202310060929 A CN 202310060929A CN 116041933 A CN116041933 A CN 116041933A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to a halogen-free high-temperature-resistant flame-retardant ABS composite PC alloy material, and a preparation method and application thereof, and belongs to the technical field of high polymer materials. The ABS composite PC alloy material comprises the following components in parts by weight: 30-60 parts of PC resin, 8-25 parts of ABS resin, 20-40 parts of composite flame retardant, 4-8 parts of compatible toughening agent, 1-3 parts of stress-resistant auxiliary agent, 0.1-1 part of antioxidant and 0.1-1 part of lubricant; the composite flame retardant comprises a flame retardant BDP, a flame retardant KSS and a PTFE anti-dripping agent. According to the invention, BDP master batch, flame retardant KSS and PTFE anti-dripping agent are selected to be compounded to be used as a composite flame retardant, so that the flame retardance and high temperature resistance of the ABS composite PC alloy material are synergistically improved while the ABS composite PC alloy material has good mechanical properties.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a halogen-free high-temperature-resistant flame-retardant ABS composite PC alloy material, and a preparation method and application thereof.
Background
ABS resin is a thermoplastic high molecular material with high strength, good toughness and easy processing and forming, and is called acrylonitrile butadiene styrene terpolymer. PC resins (i.e., polycarbonates) are high molecular weight polymers containing carbonate groups in the molecular chain. The ABS composite PC alloy material combines the good heat resistance and mechanical strength of PC resin and the good processability of ABS resin, and has the advantages of chemical stability and higher cost performance. However, the existing ABS composite PC alloy material has the defects of poor flame retardant property and poor toughness, and certain potential safety hazard exists when the ABS composite PC alloy material is used for automobile interior and exterior trim.
In order to solve the problem of poor flame retardant property of the ABS composite PC alloy material, a halogen-containing flame retardant is commonly used by a person skilled in the art to modify the ABS resin so as to improve the heat resistance and the flame retardance of the ABS resin. However, a larger amount of halogen-containing flame retardant is required to achieve the ideal flame retardant effect of the ABS composite PC alloy material, but too much amount of the flame retardant can negatively affect mechanical properties such as toughness and the like of the alloy material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a halogen-free high-temperature-resistant flame-retardant ABS composite PC alloy material, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the halogen-free high-temperature-resistant flame-retardant ABS composite PC alloy material provided by the invention comprises the following components in parts by weight: 30-60 parts of PC resin, 8-25 parts of ABS resin, 20-40 parts of composite flame retardant, 4-8 parts of compatible toughening agent, 1-3 parts of stress-resistant auxiliary agent, 0.1-1 part of antioxidant and 0.1-1 part of lubricant; the composite flame retardant comprises BDP master batches, flame retardant KSS and PTFE anti-dripping agent, wherein the weight ratio of the BDP master batches to the flame retardant KSS to the PTFE anti-dripping agent is BDP master batches: flame retardant KSS: PTFE anti-drip = 90: (0.5-2): (0.5-2).
According to the invention, BDP master batch, flame retardant KSS and PTFE anti-dripping agent are selected to be compounded to be used as the composite flame retardant, so that the flame retardance and high temperature resistance of the ABS composite PC alloy material can be synergistically improved while the ABS composite PC alloy material has good mechanical properties.
As a preferred embodiment of the present invention, the PC resin has a molecular weight of not less than 2.2 ten thousand.
As a preferred embodiment of the present invention, the weight ratio of the BDP master batch, the flame retardant KSS and the PTFE anti-dripping agent is BDP master batch: flame retardant KSS: PTFE anti-drip = 90:1:1.
as a preferred embodiment of the present invention, the mass ratio of the PC resin, ABS resin and composite flame retardant is: ABS resin: composite flame retardant= (45-60): (10-15): (20-30). When the dosage of the PC resin, the ABS resin and the composite flame retardant meets the above conditions, the alloy material has good high temperature resistance and flame retardant property, and is suitable for preparing automobile plastic products.
Further preferably, the mass ratio of the PC resin to the ABS resin to the composite flame retardant is as follows: ABS resin: composite flame retardant= (55-60): 10: (20-25).
As a preferred embodiment of the present invention, the ABS resin is of the type PA-758R.
Compared with other ABS resins, the invention selects the PA-758R ABS resin, so that the prepared alloy material has better mechanical property and better acid resistance.
As a preferred embodiment of the invention, the mass ratio of the compatible toughening agent to the stress-resistant auxiliary agent is (2-3.5): 1. the invention selects the compatibility toughening agent and the stress-resistant auxiliary agent for compounding, reduces the internal stress of the material, improves the high temperature resistance and the acid resistance of the alloy material, and can also improve the toughness of the alloy material to a certain extent.
As a preferred embodiment of the present invention, the compatible toughening agent is a methyl methacrylate-butadiene-styrene copolymer.
As a preferred embodiment of the present invention, the stress-resistant auxiliary agent includes at least one of linear low density polyethylene and ethylene-methyl acrylate copolymer.
Further, the stress-resistant auxiliary agent comprises linear low-density polyethylene and ethylene-methyl acrylate copolymer, wherein the weight ratio of the linear low-density polyethylene to the ethylene-methyl acrylate copolymer is 1:2. the invention adopts the linear low-density polyethylene and the ethylene-methyl acrylate copolymer to compound, and can be used as stress-resistant auxiliary agent, thereby ensuring that the alloy material has good toughness and simultaneously cooperatively reducing the internal stress of the alloy material.
As a preferred embodiment of the present invention, the antioxidant is at least one selected from the group consisting of antioxidant 1076 and antioxidant 168.
Further, the antioxidant comprises the following components in percentage by weight: 1 and antioxidant 168.
As a preferred embodiment of the present invention, the lubricant is at least one selected from the group consisting of polyethylene wax, pentaerythritol stearate, and silicone master batch.
In a second aspect, the invention provides a preparation method of the halogen-free high-temperature-resistant flame-retardant ABS composite PC alloy material according to the first aspect, which comprises the following steps:
(1) After PC resin and flame retardant BDP are mixed, melt blending, extrusion and granulation are carried out by a double-screw extruder, so as to obtain BDP master batches;
(2) Uniformly mixing the BDP master batch obtained in the step (1), the flame retardant KSS and the PTFE anti-dripping agent to obtain a composite flame retardant;
(3) And mixing PC resin, ABS resin, a composite flame retardant, a compatible toughening agent, a stress-resistant auxiliary agent, an antioxidant and a lubricant, and performing melt blending extrusion granulation by a double-screw extruder to obtain the ABS composite PC alloy material.
As a preferred embodiment of the present invention, the weight ratio of the PC resin and the flame retardant BDP in the step (1) is 7:3.
as a preferred embodiment of the present invention, when the twin-screw extruder in the step (1) performs melt blending extrusion granulation, the temperature of a first zone of the twin-screw extruder is 180-200 ℃, the temperature of a second zone of the twin-screw extruder is 200-230 ℃, the temperature of a third zone of the twin-screw extruder is 230-240 ℃, the temperature of a fourth zone of the twin-screw extruder is 230-240 ℃, the temperature of a fifth zone of the twin-screw extruder is 230-240 ℃, the temperature of a sixth zone of the twin-screw extruder is 230-240 ℃, and the temperature of a seventh zone of the twin-screw extruder is 230-240 ℃; the rotating speed of the screw is 300-400 r/min.
As a preferred embodiment of the present invention, when the twin-screw extruder in the step (3) performs melt blending extrusion granulation, the temperature of the first region of the twin-screw extruder is 180-200 ℃, the temperature of the second region is 200-230 ℃, the temperature of the third region is 200-230 ℃, the temperature of the fourth region is 200-230 ℃, the temperature of the fifth region is 200-230 ℃, the temperature of the sixth region is 200-230 ℃, the temperature of the seventh region is 200-230 ℃, and the temperature of the eighth region is 200-230 ℃; the rotating speed of the screw is 300-400 r/min.
In a third aspect, the invention provides an application of the halogen-free high-temperature-resistant flame-retardant ABS composite PC alloy material in the preparation of automobile plastic articles.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, BDP master batch, flame retardant KSS and PTFE anti-dripping agent are selected to be compounded to be used as a composite flame retardant, so that the flame retardance and high temperature resistance of the ABS composite PC alloy material are synergistically improved while the ABS composite PC alloy material has good mechanical properties.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The materials used in the examples and comparative examples are as follows:
ABS resin 1: PA-758R, qimei corporation;
ABS resin 2: DG417, tianjin Dagu;
PC resin: weight average molecular weight is not less than 2.2 ten thousand, LG 1201-22, korean LG company;
flame retardant BDP: zhejiang Wansheng BDP;
flame retardant KSS: arichem, america;
anti-drip agent PTFE: entropy energy;
compatible toughening agents: methyl methacrylate-butadiene-styrene copolymer, core-shell MBS 2620, rohdz;
linear Low Density Polyethylene (LLDPE): LLDPE 7042;
ethylene methyl acrylate copolymer (EMA): acarma 1125AC;
antioxidant: antioxidant 1076 and antioxidant 168 are mixed according to a ratio of 1:1 weight ratio;
antioxidant 1076: basf;
antioxidant 168: basf.
Examples 1 to 9
The preparation method of the embodiment of the halogen-free high-temperature-resistant flame-retardant ABS composite PC alloy material comprises the following steps:
(1) PC resin and flame retardant BDP were mixed according to 7:3, after mixing in weight ratio, carrying out melt blending extrusion granulation by a double-screw extruder to obtain BDP master batches;
when the twin-screw extruder in the step (1) performs melt blending extrusion granulation, the temperature of a first area of the twin-screw extruder is 200 ℃, the temperature of a second area of the twin-screw extruder is 230 ℃, the temperature of a third area of the twin-screw extruder is 240 ℃, the temperature of a fourth area of the twin-screw extruder is 240 ℃, the temperature of a fifth area of the twin-screw extruder is 240 ℃, the temperature of a sixth area of the twin-screw extruder is 240 ℃, the temperature of a seventh area of the twin-screw extruder is 240 ℃, and the temperature of an eighth area of the twin-screw extruder is 240 ℃; the screw speed was 350r/min.
(2) And (3) mixing the BDP master batch obtained in the step (1), the flame retardant KSS and the PTFE anti-dripping agent according to the BDP master batch: flame retardant KSS: PTFE anti-drip = 90:1:1, uniformly mixing the components in a weight ratio to obtain a composite flame retardant;
(3) Weighing the components according to the formula shown in Table 1; after the components are mixed, the mixture is melted, blended, extruded and granulated by a double-screw extruder to obtain the ABS composite PC alloy material; the stress-resistant auxiliary agent is prepared from Linear Low Density Polyethylene (LLDPE) and ethylene-methyl acrylate copolymer (EMA) according to the following weight ratio of 1:2, mixing the materials according to the weight ratio;
when the twin-screw extruder in the step (3) performs melt blending extrusion granulation, the temperature of a first area of the twin-screw extruder is 200 ℃, the temperature of a second area of the twin-screw extruder is 230 ℃, the temperature of a third area of the twin-screw extruder is 230 ℃, the temperature of a fourth area of the twin-screw extruder is 230 ℃, the temperature of a fifth area of the twin-screw extruder is 230 ℃, the temperature of a sixth area of the twin-screw extruder is 230 ℃, the temperature of a seventh area of the twin-screw extruder is 230 ℃, and the temperature of an eighth area of the twin-screw extruder is 230 ℃; the screw speed was 400r/min.
TABLE 1
Example 10
The present embodiment provides an ABS composite PC alloy material, and the preparation method thereof is different from that of embodiment 3 in that the stress-resistant auxiliary agent in the formulation of step (3) of this embodiment is Linear Low Density Polyethylene (LLDPE).
Example 11
The preparation method of the ABS composite PC alloy material is different from that of the embodiment 3 in that the stress-resistant auxiliary agent in the formula of the step (3) of the embodiment is ethylene-methyl acrylate copolymer (EMA).
Example 12
The preparation method of the ABS composite PC alloy material is different from that of the embodiment 3 in that in the step (2) of the embodiment, the weight ratio of BDP master batch to flame retardant KSS to PTFE anti-dripping agent is BDP master batch: flame retardant KSS: PTFE anti-drip = 90:0.5:0.5.
example 13
The preparation method of the ABS composite PC alloy material is different from that of the embodiment 3 in that in the step (2) of the embodiment, the weight ratio of BDP master batch to flame retardant KSS to PTFE anti-dripping agent is BDP master batch: flame retardant KSS: PTFE anti-drip = 90:2:2.
comparative example 1
The comparative example provides an ABS composite PC alloy material, which is different from example 3 in the preparation method thereof: the ABS resin was different in type, and ABS resin 2 was used in this comparative example.
Comparative example 2
The comparative example provides an ABS composite PC alloy material, and the preparation method is different from that of the embodiment 3 in that the comparative example has no flame retardant KSS added in the composite flame retardant in the step (2), and the weight ratio of BDP master batch to PTFE anti-dripping agent is 90:1.
comparative example 3
The comparative example provides an ABS composite PC alloy material, which differs from example 3 in that no anti-dripping agent PTFE, BDP master batch and flame retardant KSS in the weight ratio of 90:1.
comparative example 4
The comparative example provides an ABS composite PC alloy material, and the preparation method is different from that of the embodiment 1 in that no stress-resistant auxiliary agent is added in the formula of the step (3), and the weight part of the compatible toughening agent is 7 parts.
The performances of examples 1 to 13 and comparative examples 1 to 5 were tested, and the test results are shown in Table 2, and the test methods are as follows:
(1) Heat distortion temperature: according to ISO 75-2;2013 standard, 0.45MPa; injection molding each product into standard sample bars for testing;
(2) Impact strength: according to ISO 179-1;2010, injection molding each product into a standard impact spline for testing, wherein the impact capacity is 4J;
(3) Flame retardant rating: injection molding each product into standard flame retardant bars (1.6 mm) according to flame retardant standard UL 94;
(4) Glacial acetic acid soaking of the insert product: and (3) injection molding each product into an insert product, soaking the insert product in a glacial acetic acid solution with the concentration of 70% in a test environment with the temperature of 22 ℃ and the humidity of 55%, and observing the appearance change of the insert product.
TABLE 2
As can be seen from Table 2, the heat distortion temperature and impact strength of the products obtained in examples 2 to 6 are significantly better than those of the other examples, the flame retardant rating reaches V0 level, and the insert product is not cracked after being soaked in glacial acetic acid for 30 minutes, which indicates that the products obtained in examples 2 to 6 have better high temperature resistance and toughness, and excellent flame retardant property and acid resistance.
The different types of ABS resins are selected in comparative example 1 and example 3, and the toughness of example 3 is obvious due to comparative example 1, which shows that compared with other types of ABS resins, the prepared alloy material has more excellent toughness by selecting the PA-758R type ABS resin.
Compared with the example 3, the formula of the comparative example 2 is not added with a flame retardant KSS, but is compounded by BDP master batch and PTFE anti-dripping agent to serve as the flame retardant, and the flame retardant property of the obtained alloy material is not obviously improved; the formula of comparative example 3 was not added with PTFE anti-dripping agent, and the flame retardant rating of the obtained alloy material was V2, which was significantly inferior to that of the alloy material of example 3.
Compared with example 3, the formula of comparative example 4 is not added with stress-resistant auxiliary agent, but correspondingly increases the weight parts of compatible toughening agent, the thermal deformation temperature of the obtained alloy material is obviously poorer, the impact strength is slightly poorer, and the insert product is cracked after being soaked in glacial acetic acid. The addition of the stress-resistant auxiliary agent can obviously improve the high temperature resistance and the acid resistance of the alloy material and improve the toughness of the alloy material to a certain extent.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The halogen-free high-temperature-resistant flame-retardant ABS composite PC alloy material is characterized by comprising the following components in parts by weight: 30-60 parts of PC resin, 8-25 parts of ABS resin, 20-40 parts of composite flame retardant, 4-8 parts of compatible toughening agent, 1-3 parts of stress-resistant auxiliary agent, 0.1-1 part of antioxidant and 0.1-1 part of lubricant; the composite flame retardant comprises a flame retardant BDP, a flame retardant KSS and a PTFE anti-dripping agent, wherein the weight ratio of the flame retardant BDP to the flame retardant KSS to the PTFE anti-dripping agent is the flame retardant BDP: flame retardant KSS: PTFE anti-drip = 90: (0.5-2): (0.5-2).
2. The halogen-free high temperature resistant flame retardant ABS composite PC alloy material according to claim 1, wherein the molecular weight of the PC resin is not less than 2.2 ten thousand.
3. The halogen-free high temperature resistant flame retardant ABS composite PC alloy material according to claim 1, wherein the mass ratio of the PC resin to the ABS resin to the composite flame retardant is: ABS resin: composite flame retardant= (45-60): (10-15): (20-30).
4. The halogen-free high temperature resistant flame retardant ABS composite PC alloy material of claim 1 wherein the compatible toughening agent is a methyl methacrylate-butadiene-styrene copolymer.
5. The halogen-free high temperature resistant flame retardant ABS composite PC alloy material of claim 1 wherein the stress resistant additive comprises at least one of linear low density polyethylene and ethylene methyl acrylate copolymer.
6. The halogen-free high temperature resistant flame retardant ABS composite PC alloy material according to claim 5, wherein the stress resistant auxiliary agent comprises linear low density polyethylene and ethylene-methyl acrylate copolymer, and the weight ratio of the linear low density polyethylene to the ethylene-methyl acrylate copolymer is 1:2.
7. the halogen-free high temperature resistant flame retardant ABS composite PC alloy material of claim 1 wherein the antioxidant is selected from at least one of antioxidant 1076, antioxidant 168.
8. The halogen-free high temperature resistant flame retardant ABS composite PC alloy material according to claim 1, wherein the lubricant is at least one selected from polyethylene wax, pentaerythritol stearate and silicone master batch.
9. A method for preparing the halogen-free high temperature resistant flame retardant ABS composite PC alloy material according to any one of claims 1 to 8, comprising the steps of:
and mixing PC resin, ABS resin, a composite flame retardant, a compatible toughening agent, a stress-resistant auxiliary agent, an antioxidant and a lubricant, and performing melt blending extrusion granulation by a double-screw extruder to obtain the ABS composite PC alloy material.
10. Use of the halogen-free high temperature resistant flame retardant ABS composite PC alloy material according to any one of claims 1-8 in the preparation of automotive plastic articles.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310060929.2A CN116041933A (en) | 2023-01-17 | 2023-01-17 | Halogen-free high-temperature-resistant flame-retardant ABS composite PC alloy material and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310060929.2A CN116041933A (en) | 2023-01-17 | 2023-01-17 | Halogen-free high-temperature-resistant flame-retardant ABS composite PC alloy material and preparation method and application thereof |
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| CN116041933A true CN116041933A (en) | 2023-05-02 |
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