CN113105733A - Flame-retardant polycarbonate alloy material and preparation method and application thereof - Google Patents
Flame-retardant polycarbonate alloy material and preparation method and application thereof Download PDFInfo
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- CN113105733A CN113105733A CN202110396445.6A CN202110396445A CN113105733A CN 113105733 A CN113105733 A CN 113105733A CN 202110396445 A CN202110396445 A CN 202110396445A CN 113105733 A CN113105733 A CN 113105733A
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a flame-retardant polycarbonate alloy material, which is characterized in that: the paint comprises the following components in parts by weight: 30-80 parts of PC resin, 1-20 parts of ABS resin, 5-20 parts of phosphate flame retardant, 0-5 parts of silicon flame retardant, 0-1 part of antioxidant, 0-2 parts of lubricant and 0-5 parts of anti-dripping agent; the invention relates to a preparation method and application of a flame-retardant polycarbonate alloy material. The flame-retardant polycarbonate alloy material and the polycarbonate alloy material prepared by the preparation method have the comprehensive performance of the conventional halogen-free flame-retardant PC/ABS alloy, the smoke density is lower than 60SDR, the smoke density is obviously reduced, the preparation process is simple, the cost is low, and the material can be applied to the field of automobile interior parts with more severe requirements on the smoke density.
Description
Technical Field
The invention belongs to the technical field of modification of high polymer materials, and particularly relates to a flame-retardant polycarbonate alloy material and a preparation method and application thereof.
Background
Polycarbonate (PC) is an amorphous thermoplastic engineering plastic with excellent mechanical properties, and has the advantages of high heat resistance, good transparency, high glossiness, high impact strength and the like. But the defects of poor fluidity, difficult molding processing, large residual stress of products, easy stress cracking, poor solvent resistance, notch impact sensitivity and the like limit the application of the product. Acrylonitrile-butadiene-styrene (ABS) is a versatile thermoplastic engineering plastic developed in the 40's of this century, with its internal styrene component providing good processing flow and gloss, its butadiene component providing toughness and low temperature performance, and its acrylonitrile component providing excellent chemical resistance. Therefore, ABS resin has good comprehensive properties. However, ABS resins often have unsatisfactory heat resistance and mechanical properties, and usually need to be modified for normal use.
The preparation of the polymer alloy material by blending two or more polymers is an efficient polymer material modification technology. The halogen-free flame-retardant PC/ABS alloy is a material with excellent comprehensive performance, integrates the excellent performances of PC and ABS, has the advantages of low melt viscosity, good processing performance, high impact and tensile strength and the like, has higher flame-retardant grade, and meets the requirement of environmental protection. Therefore, the halogen-free flame-retardant PC/ABS alloy can be widely applied to the fields of automobiles, household appliances, communication equipment and the like.
Although some halogen-free flame-retardant PC/ABS alloy technologies are introduced in the prior art, the Smoke Density (SDR) of the halogen-free flame-retardant PC/ABS is basically in the range of 60-80 in the disclosed technologies, and the technology of lower smoke density is not published yet.
The invention aims to develop a halogen-free flame-retardant PC/ABS alloy material with ultralow smoke density, which is applied to the field of automotive upholstery with stricter smoke density requirements.
Disclosure of Invention
The invention aims to provide a flame-retardant polycarbonate alloy material, a preparation method and application thereof, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: the flame-retardant polycarbonate alloy material comprises the following components in parts by weight: 30-80 parts of PC resin, 1-20 parts of ABS resin, 5-20 parts of phosphate flame retardant, 0-5 parts of silicon flame retardant, 0-1 part of antioxidant, 0-2 parts of lubricant and 0-5 parts of anti-dripping agent, wherein the ABS resin comprises 1 part of ABS resin, American Styron and ABS 3504; ABS resin 2, Shanghai high bridge petrochemical, brand ABS 8434; ABS resin 3, Taiwan geopetro-chemical, trade mark ABS 60P, ABS resin density 1.0-1.1g/cm3, melt index 1-20g/10min at 220 deg.C and 10KG, silicon fire retardant with core-shell structure and thermal decomposition temperature higher than 300 deg.C.
Preferably, the PC resin is bisphenol A aromatic polycarbonate, the weight-average molecular weight is 25000-45000g/mol, and the melt index is 1-35g/10min under the conditions of 300 ℃ and 1.2 KG.
In any of the above schemes, preferably, the phosphate flame retardant is one or a combination of several of triphenyl phosphate, poly bisphenol a-bis (diphenyl phosphate), and resorcinol bis (diphenyl phosphate), preferably poly bisphenol a-bis (diphenyl phosphate).
In any of the above schemes, preferably, the antioxidant is one or a combination of several hindered phenols, phosphites and thioether antioxidants, and preferably, the thioether antioxidant.
In any of the above schemes, preferably, the lubricant is one or a combination of several of an amide lubricant, an ester lubricant, a polyethylene lubricant and a stearic acid lubricant, and preferably, the ester lubricant.
In any of the above schemes, preferably, the dripping agent is one or a combination of pure polytetrafluoroethylene powder, styrene-acrylonitrile copolymer coated modified polytetrafluoroethylene powder, and polymethyl methacrylate coated modified polytetrafluoroethylene powder, and preferably, styrene-acrylonitrile copolymer coated modified polytetrafluoroethylene powder.
A preparation method of a flame-retardant polycarbonate alloy material comprises the following steps in sequence:
s1: sequentially adding PC resin, ABS resin, a silicon flame retardant, an antioxidant, a lubricant and an anti-dripping agent into a high-speed mixer to mix for 1-2min, wherein the rotating speed of the high-speed mixer is 500r/min, so as to obtain a premix;
s2: and adding the premix obtained in the step into a double-screw extruder from a main feeding port, adding the phosphate flame retardant into the double-screw extruder from a side feeding port, and carrying out melt extrusion granulation to obtain the flame-retardant polycarbonate alloy material, wherein the temperatures of a screw cylinder of the double-screw extruder from a feeding port to a machine head are respectively 140 ℃, 240 ℃, 250 ℃, 240 ℃ and 240 ℃, and the screw rotating speed is 350 r/min.
The flame-retardant polycarbonate alloy material is applied to automotive interior parts with strict requirements on smoke density.
The invention has the technical effects and advantages that: the flame-retardant polycarbonate alloy material and the polycarbonate alloy material prepared by the preparation method have the comprehensive performance of the conventional halogen-free flame-retardant PC/ABS alloy, the smoke density is lower than 60SDR, the smoke density is obviously reduced, the preparation process is simple, the cost is low, and the material can be applied to the field of automobile interior parts with more severe requirements on the smoke density.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the flame-retardant polycarbonate alloy material comprises the following components in parts by weight: 30 parts of PC resin, 1 part of ABS resin, 5 parts of phosphate flame retardant, 0.1 part of silicon flame retardant, 0.1 part of antioxidant, 0.1 part of lubricant and 0.1 part of anti-dripping agent, wherein the ABS resin comprises 1 part of ABS resin, American Styron and ABS 3504; ABS resin 2, Shanghai high bridge petrochemical, brand ABS 8434; ABS resin 3, Taiwan geopetro-chemical, trade mark ABS 60P, ABS resin density 1.0-1.1g/cm3, melt index 1-20g/10min at 220 deg.C and 10KG, silicon fire retardant with core-shell structure and thermal decomposition temperature higher than 300 deg.C.
Specifically, the PC resin is bisphenol A type aromatic polycarbonate, the weight-average molecular weight is 25000-45000g/mol, and the melt index is 1-35g/10min under the conditions of 300 ℃ and 1.2 KG.
Specifically, the phosphate flame retardant is one or a combination of more of triphenyl phosphate, poly bisphenol A-bis (diphenyl phosphate) and resorcinol bis (diphenyl phosphate), and poly bisphenol A-bis (diphenyl phosphate) is preferred.
Specifically, the antioxidant is one or a combination of more of hindered phenols, phosphites and thioether antioxidants, preferably thioether antioxidants.
Specifically, the lubricant is one or a combination of more of an amide lubricant, an ester lubricant, a polyethylene lubricant and a stearic acid lubricant, and the ester lubricant is preferred.
Specifically, the dripping agent is one or a combination of more of pure polytetrafluoroethylene powder, styrene-acrylonitrile copolymer coated modified polytetrafluoroethylene powder and polymethyl methacrylate coated modified polytetrafluoroethylene powder, and the styrene-acrylonitrile copolymer coated modified polytetrafluoroethylene powder is preferred.
Example 2:
the flame-retardant polycarbonate alloy material comprises the following components in parts by weight: 60 parts of PC resin, 10 parts of ABS resin, 15 parts of phosphate flame retardant, 3 parts of silicon flame retardant, 0.5 part of antioxidant, 1 part of lubricant and 2 parts of anti-dripping agent, wherein the ABS resin comprises 1 part of ABS resin, American Styron and a brand ABS 3504; ABS resin 2, Shanghai high bridge petrochemical, brand ABS 8434; ABS resin 3, Taiwan geopetro-chemical, trade mark ABS 60P, ABS resin density 1.0-1.1g/cm3, melt index 1-20g/10min at 220 deg.C and 10KG, silicon fire retardant with core-shell structure and thermal decomposition temperature higher than 300 deg.C.
Specifically, the PC resin is bisphenol A type aromatic polycarbonate, the weight-average molecular weight is 25000-45000g/mol, and the melt index is 1-35g/10min under the conditions of 300 ℃ and 1.2 KG.
Specifically, the phosphate flame retardant is one or a combination of more of triphenyl phosphate, poly bisphenol A-bis (diphenyl phosphate) and resorcinol bis (diphenyl phosphate), and poly bisphenol A-bis (diphenyl phosphate) is preferred.
Specifically, the antioxidant is one or a combination of more of hindered phenols, phosphites and thioether antioxidants, preferably thioether antioxidants.
Specifically, the lubricant is one or a combination of more of an amide lubricant, an ester lubricant, a polyethylene lubricant and a stearic acid lubricant, and the ester lubricant is preferred.
Specifically, the dripping agent is one or a combination of more of pure polytetrafluoroethylene powder, styrene-acrylonitrile copolymer coated modified polytetrafluoroethylene powder and polymethyl methacrylate coated modified polytetrafluoroethylene powder, and the styrene-acrylonitrile copolymer coated modified polytetrafluoroethylene powder is preferred.
Example 3:
the flame-retardant polycarbonate alloy material comprises the following components in parts by weight: 80 parts of PC resin, 20 parts of ABS resin, 20 parts of phosphate flame retardant, 5 parts of silicon flame retardant, 1 part of antioxidant, 2 parts of lubricant and 5 parts of anti-dripping agent, wherein the ABS resin comprises 1 part of ABS resin, American Styron and the trademark ABS 3504; ABS resin 2, Shanghai high bridge petrochemical, brand ABS 8434; ABS resin 3, Taiwan geopetro-chemical, trade mark ABS 60P, ABS resin density 1.0-1.1g/cm3, melt index 1-20g/10min at 220 deg.C and 10KG, silicon fire retardant with core-shell structure and thermal decomposition temperature higher than 300 deg.C.
Specifically, the PC resin is bisphenol A type aromatic polycarbonate, the weight-average molecular weight is 25000-45000g/mol, and the melt index is 1-35g/10min under the conditions of 300 ℃ and 1.2 KG.
Specifically, the phosphate flame retardant is one or a combination of more of triphenyl phosphate, poly bisphenol A-bis (diphenyl phosphate) and resorcinol bis (diphenyl phosphate), and poly bisphenol A-bis (diphenyl phosphate) is preferred.
Specifically, the antioxidant is one or a combination of more of hindered phenols, phosphites and thioether antioxidants, preferably thioether antioxidants.
Specifically, the lubricant is one or a combination of more of an amide lubricant, an ester lubricant, a polyethylene lubricant and a stearic acid lubricant, and the ester lubricant is preferred.
Specifically, the dripping agent is one or a combination of more of pure polytetrafluoroethylene powder, styrene-acrylonitrile copolymer coated modified polytetrafluoroethylene powder and polymethyl methacrylate coated modified polytetrafluoroethylene powder, and the styrene-acrylonitrile copolymer coated modified polytetrafluoroethylene powder is preferred.
Comparative example 1:
the flame-retardant polycarbonate alloy material comprises the following components in parts by weight: 29 parts of PC resin, 0.9 part of ABS resin, 4.9 parts of phosphate flame retardant, 0 part of silicon flame retardant, 0 part of antioxidant, 0 part of lubricant and 0 part of anti-dripping agent, wherein the ABS resin comprises 1 part of ABS resin, American Styron and ABS 3504; ABS resin 2, Shanghai high bridge petrochemical, brand ABS 8434; ABS resin 3, Taiwan geopetro-chemical, trade mark ABS 60P, ABS resin density 1.0-1.1g/cm3, melt index 1-20g/10min at 220 deg.C and 10KG, silicon fire retardant with core-shell structure and thermal decomposition temperature higher than 300 deg.C.
Specifically, the PC resin is bisphenol A type aromatic polycarbonate, the weight-average molecular weight is 25000-45000g/mol, and the melt index is 1-35g/10min under the conditions of 300 ℃ and 1.2 KG.
Specifically, the phosphate flame retardant is one or a combination of more of triphenyl phosphate, poly bisphenol A-bis (diphenyl phosphate) and resorcinol bis (diphenyl phosphate), and poly bisphenol A-bis (diphenyl phosphate) is preferred.
Specifically, the antioxidant is one or a combination of more of hindered phenols, phosphites and thioether antioxidants, preferably thioether antioxidants.
Specifically, the lubricant is one or a combination of more of an amide lubricant, an ester lubricant, a polyethylene lubricant and a stearic acid lubricant, and the ester lubricant is preferred.
Specifically, the dripping agent is one or a combination of more of pure polytetrafluoroethylene powder, styrene-acrylonitrile copolymer coated modified polytetrafluoroethylene powder and polymethyl methacrylate coated modified polytetrafluoroethylene powder, and the styrene-acrylonitrile copolymer coated modified polytetrafluoroethylene powder is preferred.
Comparative example 2:
the flame-retardant polycarbonate alloy material comprises the following components in parts by weight: 81 parts of PC resin, 21 parts of ABS resin, 21 parts of phosphate flame retardant, 6 parts of silicon flame retardant, 2 parts of antioxidant, 3 parts of lubricant and 6 parts of anti-dripping agent, wherein the ABS resin comprises 1 part of ABS resin, American Styron and the trademark ABS 3504; ABS resin 2, Shanghai high bridge petrochemical, brand ABS 8434; ABS resin 3, Taiwan geopetro-chemical, trade mark ABS 60P, ABS resin density 1.0-1.1g/cm3, melt index 1-20g/10min at 220 deg.C and 10KG, silicon fire retardant with core-shell structure and thermal decomposition temperature higher than 300 deg.C.
Specifically, the PC resin is bisphenol A type aromatic polycarbonate, the weight-average molecular weight is 25000-45000g/mol, and the melt index is 1-35g/10min under the conditions of 300 ℃ and 1.2 KG.
Specifically, the phosphate flame retardant is one or a combination of more of triphenyl phosphate, poly bisphenol A-bis (diphenyl phosphate) and resorcinol bis (diphenyl phosphate), and poly bisphenol A-bis (diphenyl phosphate) is preferred.
Specifically, the antioxidant is one or a combination of more of hindered phenols, phosphites and thioether antioxidants, preferably thioether antioxidants.
Specifically, the lubricant is one or a combination of more of an amide lubricant, an ester lubricant, a polyethylene lubricant and a stearic acid lubricant, and the ester lubricant is preferred.
Specifically, the dripping agent is one or a combination of more of pure polytetrafluoroethylene powder, styrene-acrylonitrile copolymer coated modified polytetrafluoroethylene powder and polymethyl methacrylate coated modified polytetrafluoroethylene powder, and the styrene-acrylonitrile copolymer coated modified polytetrafluoroethylene powder is preferred.
The invention also provides a preparation method of the flame-retardant polycarbonate alloy material, which comprises the following steps in sequence:
s1: sequentially adding PC resin, ABS resin, a silicon flame retardant, an antioxidant, a lubricant and an anti-dripping agent into a high-speed mixer to mix for 1-2min, wherein the rotating speed of the high-speed mixer is 500r/min, so as to obtain a premix;
s2: and adding the premix obtained in the step into a double-screw extruder from a main feeding port, adding the phosphate flame retardant into the double-screw extruder from a side feeding port, and carrying out melt extrusion granulation to obtain the flame-retardant polycarbonate alloy material, wherein the temperatures of a screw cylinder of the double-screw extruder from a feeding port to a machine head are respectively 140 ℃, 240 ℃, 250 ℃, 240 ℃ and 240 ℃, and the screw rotating speed is 350 r/min.
And the flame-retardant polycarbonate alloy material is applied to automotive interior parts with strict requirements on smoke density.
The compositions of the flame-retardant polycarbonate alloy materials in the examples 1, 2 and 3 and the comparative examples 1 and 2 are prepared according to the preparation method provided above to obtain a flame-retardant polycarbonate alloy material, the obtained product is placed in an oven to be dried (100 ℃, 3h) and then is subjected to injection molding to obtain a standard sample strip, the injection molding temperature is 250 ℃, the standard sample strip is subjected to performance testing after being placed for 24 hours in an environment with the relative humidity of 23 ℃ and 50%, and the performance testing results are shown in table 1:
table 1:
as can be seen from Table 1, the smoke density SDR of examples 1-3 is significantly reduced compared to comparative examples 1-2, and the tensile strength and impact strength are not affected, indicating that the mechanical properties of the material remain good and are not affected while the smoke density of the material is reduced according to the present invention.
It can be seen from examples 1-3 that the smoke density gradually decreases with increasing silicon-based flame retardant content, indicating that the silicon-based flame retardant plays an important role in the smoke density of the material.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. A flame retardant polycarbonate alloy material, characterized in that: the paint comprises the following components in parts by weight: 30-80 parts of PC resin, 1-20 parts of ABS resin, 5-20 parts of phosphate flame retardant, 0-5 parts of silicon flame retardant, 0-1 part of antioxidant, 0-2 parts of lubricant and 0-5 parts of anti-dripping agent.
2. The flame retardant polycarbonate alloy material of claim 1, wherein: the PC resin is bisphenol A aromatic polycarbonate.
3. The flame retardant polycarbonate alloy material of claim 1, wherein: the phosphate flame retardant is one or a combination of more of triphenyl phosphate, poly bisphenol A-bis (diphenyl phosphate) and resorcinol bis (diphenyl phosphate).
4. The flame retardant polycarbonate alloy material of claim 1, wherein: the antioxidant is one or a combination of more of hindered phenol, phosphite and thioether antioxidants.
5. The flame retardant polycarbonate alloy material of claim 1, wherein: the lubricant is one or a combination of more of amide lubricant, ester lubricant, polyethylene lubricant and stearic acid lubricant.
6. The flame retardant polycarbonate alloy material of claim 1, wherein: the dripping agent is one or a combination of more of pure polytetrafluoroethylene powder, styrene-acrylonitrile copolymer coated and modified polytetrafluoroethylene powder and polymethyl methacrylate coated and modified polytetrafluoroethylene powder.
7. The method for preparing the flame-retardant polycarbonate alloy material according to claim 1, wherein the method comprises the following steps: the method comprises the following steps in sequence:
s1: sequentially adding PC resin, ABS resin, a silicon flame retardant, an antioxidant, a lubricant and an anti-dripping agent into a high-speed mixer to mix for 1-2min, wherein the rotating speed of the high-speed mixer is 500r/min, so as to obtain a premix;
s2: and adding the premix obtained in the step into a double-screw extruder from a main feeding port, adding the phosphate flame retardant into the double-screw extruder from a side feeding port, and carrying out melt extrusion granulation to obtain the flame-retardant polycarbonate alloy material, wherein the temperatures of a screw cylinder of the double-screw extruder from a feeding port to a machine head are respectively 140 ℃, 240 ℃, 250 ℃, 240 ℃ and 240 ℃, and the screw rotating speed is 350 r/min.
8. Use of the flame retardant polycarbonate alloy material of any of claims 1-6 in automotive interior trim parts where smoke density is critical.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011624605X | 2020-12-31 | ||
| CN202011624605 | 2020-12-31 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260731A (en) * | 2022-08-24 | 2022-11-01 | 上海中镭新材料科技有限公司 | Polycarbonate composite material and preparation method and application thereof |
| CN115819944A (en) * | 2022-11-28 | 2023-03-21 | 江苏金发科技新材料有限公司 | Easily-demoulded flame-retardant polycarbonate composition |
-
2021
- 2021-04-13 CN CN202110396445.6A patent/CN113105733A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260731A (en) * | 2022-08-24 | 2022-11-01 | 上海中镭新材料科技有限公司 | Polycarbonate composite material and preparation method and application thereof |
| WO2024041220A1 (en) * | 2022-08-24 | 2024-02-29 | 上海中镭新材料科技有限公司 | Polycarbonate composite material, preparation method therefor, and use thereof |
| CN115819944A (en) * | 2022-11-28 | 2023-03-21 | 江苏金发科技新材料有限公司 | Easily-demoulded flame-retardant polycarbonate composition |
| CN115819944B (en) * | 2022-11-28 | 2024-03-15 | 江苏金发科技新材料有限公司 | Flame-retardant polycarbonate composition easy to demould |
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