CN113831717A - Flame-retardant high-gloss high-hardness polycarbonate composite material and preparation method thereof - Google Patents
Flame-retardant high-gloss high-hardness polycarbonate composite material and preparation method thereof Download PDFInfo
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- CN113831717A CN113831717A CN202111208987.2A CN202111208987A CN113831717A CN 113831717 A CN113831717 A CN 113831717A CN 202111208987 A CN202111208987 A CN 202111208987A CN 113831717 A CN113831717 A CN 113831717A
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- polycarbonate
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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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
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Abstract
The invention discloses a flame-retardant high-gloss high-hardness polycarbonate composite material and a preparation method thereof, wherein the composite material is prepared by mixing polycarbonate, a reinforcing agent, a halogen-free flame retardant and an auxiliary agent in proportion; the preparation method of the material comprises the steps of mixing raw materials; melting and extruding; cooling; and pelletizing, drying and the like. The flame-retardant polycarbonate composite material with high gloss and high hardness provided by the invention has the flame retardant grade of UL-94V-0 grade, has metallic luster, has the scratch resistance grade of 1H, and is excellent in mechanical property, remarkable in flame retardant effect, good in thermal stability, high in efficiency and low in toxicity; the addition amount of the self-made halogen-free flame retardant is less than that of other flame retardants, the preparation process flow is simple, the equipment investment is low, and the income is large; the preparation method has simple flow, low equipment investment and great benefit.
Description
Technical Field
The invention belongs to the field of fireproof materials and preparation methods thereof, and particularly relates to a flame-retardant high-gloss high-hardness polycarbonate composite material and a preparation method thereof.
Background
As a polycarbonate material for engineering plastics, the polycarbonate material has the advantages of high mechanical strength, high impact strength, high transparency, high weather resistance and the like. However, the polycarbonate material has a flame retardant rating of UL-94V-2 and an oxygen index of about 25, and is a combustible substance which drops during combustion; the polycarbonate material has low surface hardness and scratch resistance grade of 2B, scratches are generated after the polycarbonate material is scratched by hard objects, and when the polycarbonate material is applied to the field of electronics and electricity, flame retardant modification and wear resistance modification are required.
Meanwhile, with the promulgation and implementation of a series of environmental protection laws and regulations at home and abroad, safe, environment-friendly and high-performance materials are increasingly concerned by people, and the market also puts higher requirements on the mechanical properties, flame retardance and fireproof performance of the materials.
In the prior art, the polycarbonate material which takes alkyl phosphate as a main flame retardant is generally used, and can meet the flame retardant grade UL-94V-0, but with the increase of the addition amount of the flame retardant, the mechanical property of the polycarbonate is reduced, so that the mechanical property of the polycarbonate must be improved while the polycarbonate is flame-retardant and fireproof. The sulfonate flame retardant, the phosphorus flame retardant and the nitrogen-phosphorus flame retardant belong to halogen-free flame retardants, and compared with the phosphorus flame retardant and the nitrogen-phosphorus flame retardant, the sulfonate flame retardant has the advantages of being small in addition amount, high in flame retardant efficiency, low in influence on mechanical properties of materials, small in toxic and corrosive gas generated in a combustion process and the like, and becomes one of trends of polycarbonate flame retardants.
Disclosure of Invention
The invention is provided for overcoming the defects of scraping resistance, poor flame-retardant and fireproof performance and the like of polycarbonate in the prior art, and aims to provide a flame-retardant high-gloss high-hardness polycarbonate composite material and a preparation method thereof.
The invention is realized by the following technical scheme:
the flame-retardant high-gloss high-hardness polycarbonate composite material comprises the following components in percentage by weight:
50% -80% of polycarbonate;
5% -30% of a reinforcing agent;
0.1% -30% of halogen-free flame retardant;
1% -15% of an auxiliary agent.
In the above technical solution, the reinforcing agent includes any one or more of polymethyl methacrylate or polystyrene.
In the technical scheme, the halogen-free flame retardant is prepared by adding any one or more of ammonium polyphosphate, melamine, potassium perfluorobutylsulfonate, KKS, MPP, MCA and zinc borate into a mixer for compounding.
In the technical scheme, the auxiliary agent comprises any one or more of a toughening agent, a compatilizer, an anti-dripping agent, an antioxidant and a lubricant.
In the technical scheme, the toughening agent is MBS or POE; the compatilizer is MAH graft or GMA graft; the anti-dripping agent is polytetrafluoroethylene; the antioxidant is any one of an antioxidant 1098, an antioxidant 1076 or an antioxidant 168; the lubricant is calcium stearate.
A preparation method of a flame-retardant high-gloss high-hardness polycarbonate composite material comprises the following steps:
mixing the raw materials
Adding the polycarbonate, the reinforcing agent, the halogen-free flame retardant and the auxiliary agent into a mixer for mixing to obtain a uniformly mixed blend of polycarbonate and the like;
(ii) melting and extrusion
Adding the blend obtained in the step (i) from a main feeding port of a double-screw extruder, and melting and extruding the blend in the double-screw extruder to obtain a blend melt;
(iii) Cooling
Putting the blend melt which is melted and extruded in the double-screw extruder into a cooling machine for cooling;
(iv) dicing
Step (iii), after cooling, putting the product into a granulator for granulation;
(v) drying
And (4) putting the product after being cut into granules into a dryer for full drying, thus obtaining the flame-retardant high-gloss high-hardness polycarbonate composite material product.
In the technical scheme, the temperature for mixing the raw materials in the step (i) is 70-160 ℃; the melting temperature of the step (ii) is 210-280 ℃; cooling the melt of the blend to 40-60 ℃ while cooling in the step (iii); and (v) controlling the drying temperature in the step (v) to be 90-110 ℃.
In the technical scheme, in the dicing in the step (iv), the particle size is controlled to be 2-3 mm after dicing.
The invention has the beneficial effects that:
the invention provides a flame-retardant high-gloss high-hardness polycarbonate composite material and a preparation method thereof, wherein the flame-retardant grade of the composite material is UL-94V-0 grade, the composite material has metallic luster, the scratch-resistant grade reaches 1H, the mechanical property is excellent, the flame-retardant effect is obvious, the thermal stability is good, and the polycarbonate composite material is efficient and low-toxic; the addition amount of the self-made halogen-free flame retardant is less than that of other flame retardants, the preparation process flow is simple, the equipment investment is low, and the income is large; the preparation method has simple flow, low equipment investment and great benefit.
The invention adopts the self-made sulfonate flame retardant as the main flame retardant, and the sulfonate flame retardant is less in addition amount than alkyl phosphate in a polycarbonate system, so that the flame retardant effect is better, and the quality of the prepared polycarbonate is better. The scratch resistance of the polycarbonate composite material is improved by polymethyl methacrylate or polystyrene, the scratch resistance grades of the surfaces of the polymethyl methacrylate and the polystyrene are both 3H, the two materials have better light transmittance, and the composite material after being blended and modified with the polycarbonate has metallic luster.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention is further described below by the specific embodiments.
The flame-retardant high-gloss high-hardness polycarbonate composite material comprises the following components in percentage by weight:
50% -80% of polycarbonate;
5% -50% of a reinforcing agent;
0.1% -30% of halogen-free flame retardant;
1% -15% of an auxiliary agent;
the reinforcing agent comprises one or more of polymethyl methacrylate or polystyrene.
The halogen-free flame retardant is any one or more of ammonium polyphosphate, melamine, potassium perfluorobutylsulfonate, KKS, MPP, MCA or zinc borate.
The auxiliary agent comprises any one or more of a toughening agent, a compatilizer, an anti-dripping agent, an antioxidant and a lubricant, and is added into a mixer for compounding.
The toughening agent is MBS or POE; the compatilizer is MAH graft or GMA graft; the anti-dripping agent is polytetrafluoroethylene; the antioxidant is any one of an antioxidant 1098, an antioxidant 1076 or an antioxidant 168; the lubricant is calcium stearate.
A preparation method of a flame-retardant high-gloss high-hardness polycarbonate composite material comprises the following steps:
mixing the raw materials
Adding the raw materials such as polycarbonate, a reinforcing agent, a self-made halogen-free flame retardant, a powder additive and the like into a mixer at the temperature of 70-160 ℃ for mixing to obtain a uniformly mixed polycarbonate blend;
(ii) melting and extrusion
Adding the obtained blend from a main feeding port of a double-screw extruder, and melting and extruding the blend in the double-screw extruder to obtain a polycarbonate blend melt, wherein the melting temperature is 210-280 ℃;
(iii) Cooling
Putting the polycarbonate blend melt subjected to melt extrusion in a double-screw extruder into a cooling machine to be cooled to 40-60 DEG C
(iv) dicing
After cooling, putting the mixture into a granulator for granulating, wherein the particle size is 2-3 mm;
(v) drying
And (4) cutting into particles, and then putting the particles into a dryer for full drying, wherein the temperature is controlled to be 90-110 ℃, and then the high-fire-resistance polycarbonate composite material product is obtained.
Example 1
Mixing the raw materials
Adding 80Kg of polycarbonate, 15Kg of polymethyl methacrylate, 2Kg of flame retardant and 3Kg of auxiliary agent into a mixer at 70 ℃ for mixing to obtain a polycarbonate blend with uniformly coated powder;
the 3Kg of auxiliary agent consists of 1Kg of toughening agent, 1Kg of compatilizer, 0.3Kg of anti-dripping agent, 0.4Kg of antioxidant and 0.3Kg of lubricant;
(ii) melting and extrusion
Adding the polycarbonate blend from a main feeding port of a double-screw extruder, properly adjusting the feeding speed and the screw rotating speed, and melting and extruding the polycarbonate blend and the double-screw extruder to obtain a polycarbonate blend melt, wherein the melting temperature is 210 ℃;
(iii) Cooling
Putting the polycarbonate blend melt which is melt extruded in a double-screw extruder into a cooler to be cooled to 40 ℃;
(iv) dicing
After cooling, putting the mixture into a granulator for granulating, wherein the particle size is 2 mm;
(v) drying
And (4) cutting into particles, and then putting the particles into a dryer for full drying to obtain the polycarbonate reinforced flame-retardant composite material product.
The flame retardant grade of the obtained product reaches UL-94V-1 grade, and the scratch resistance grade is 1H.
Example 2
Mixing the raw materials
Adding 60Kg of polycarbonate, 35Kg of reinforcing agent, 2Kg of flame retardant and 3Kg of auxiliary agent into a mixer at 110 ℃ for mixing to obtain a polycarbonate blend with uniformly wrapped powder;
the 35Kg reinforcing agent consists of 30Kg polymethyl methacrylate and 5Kg polystyrene;
the 3Kg of auxiliary agent consists of 1Kg of toughening agent, 1Kg of compatilizer, 0.3Kg of anti-dripping agent, 0.4Kg of antioxidant and 0.3Kg of lubricant;
(ii) melting and extrusion
Adding the polycarbonate blend from a main feeding port of a double-screw extruder, properly adjusting the feeding speed and the screw rotating speed, and melting and extruding the polycarbonate blend and the double-screw extruder to obtain a polycarbonate blend melt, wherein the melting temperature is 250 ℃;
(iii) Cooling
Putting the polycarbonate blend melt which is melted and extruded in a double-screw extruder into a cooler to be cooled to 50 ℃;
(iv) dicing
After cooling, putting the mixture into a granulator for granulating, wherein the particle size is 2 mm;
(v) drying
And (4) cutting into particles, and then putting the particles into a dryer for full drying to obtain the polycarbonate reinforced flame-retardant composite material product.
The flame retardant grade of the obtained product reaches UL-94V-0 grade, the scratch resistance grade is 1H, and the use requirements of mechanical and flame retardant fireproof performances of electronic and electric appliances are met.
Example 3
Mixing the raw materials
Adding 50Kg of polycarbonate, 45Kg of reinforcing agent, 2Kg of flame retardant and 3Kg of auxiliary agent into a mixer at 150 ℃ for mixing to obtain a polycarbonate blend with uniformly wrapped powder;
the 45Kg reinforcing agent consists of 35Kg polymethyl methacrylate and 10Kg polystyrene;
the 3Kg of auxiliary agent consists of 1Kg of toughening agent, 1Kg of compatilizer, 0.3Kg of anti-dripping agent, 0.4Kg of antioxidant and 0.3Kg of lubricant;
(ii) melting and extrusion
Adding the polycarbonate blend from a main feeding port of a double-screw extruder, properly adjusting the feeding speed and the screw rotating speed, and melting and extruding the polycarbonate blend and the double-screw extruder to obtain a polycarbonate blend melt, wherein the melting temperature is 280 ℃;
(iii) Cooling
Putting the polycarbonate blend melt which is melted and extruded in a double-screw extruder into a cooler to be cooled to 60 ℃;
(iv) dicing
After cooling, putting the mixture into a granulator for granulating, wherein the particle size is 3 mm;
(v) drying
And (4) cutting into particles, and then putting the particles into a dryer for full drying to obtain the polycarbonate reinforced flame-retardant composite material product.
The flame retardant grade of the obtained product reaches UL-94V-0 grade, and the scratch resistance grade is 1H.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (8)
1. The flame-retardant high-gloss high-hardness polycarbonate composite material is characterized in that: the composite material comprises the following components in percentage by weight:
50% -80% of polycarbonate;
5% -30% of a reinforcing agent;
0.1% -30% of halogen-free flame retardant;
1% -15% of an auxiliary agent.
2. The flame retardant high gloss high stiffness polycarbonate composite of claim 1, wherein: the reinforcing agent is any one or more of polymethyl methacrylate or polystyrene.
3. The flame retardant high gloss high stiffness polycarbonate composite of claim 1, wherein: the halogen-free flame retardant is prepared by adding any one or more of ammonium polyphosphate, melamine, potassium perfluorobutylsulfonate, KKS, MPP, MCA or zinc borate into a mixer for compounding.
4. The flame retardant high gloss high stiffness polycarbonate composite of claim 1, wherein: the auxiliary agent comprises any one or more of a toughening agent, a compatilizer, an anti-dripping agent, an antioxidant and a lubricant.
5. The flame retardant high gloss high stiffness polycarbonate composite of claim 4, wherein: the toughening agent is MBS or POE;
the compatilizer is MAH graft or GMA graft;
the anti-dripping agent is polytetrafluoroethylene;
the antioxidant is any one of an antioxidant 1098, an antioxidant 1076 or an antioxidant 168;
the lubricant is calcium stearate.
6. The preparation method of the flame-retardant high-gloss high-hardness polycarbonate composite material applied to any one of claims 1 to 5 is characterized by comprising the following steps: the method comprises the following steps:
mixing the raw materials
Adding the polycarbonate, the reinforcing agent, the halogen-free flame retardant and the auxiliary agent into a mixer for mixing to obtain a uniformly mixed blend of polycarbonate and the like;
(ii) melting and extrusion
Adding the blend obtained in the step (i) from a main feeding port of a double-screw extruder, and melting and extruding the blend in the double-screw extruder to obtain a blend melt;
(iii) Cooling
Putting the blend melt which is melted and extruded in the double-screw extruder into a cooling machine for cooling;
(iv) dicing
Step (iii), after cooling, putting the product into a granulator for granulation;
(v) drying
And (4) putting the product after being cut into granules into a dryer for full drying, thus obtaining the flame-retardant high-gloss high-hardness polycarbonate composite material product.
7. The flame retardant high gloss high stiffness polycarbonate composite of claim 6, wherein: the temperature for mixing the raw materials in the step (i) is 70-160 ℃; the melting temperature of the step (ii) is 210-280 ℃; cooling the melt of the blend to 40-60 ℃ while cooling in the step (iii); and (v) controlling the drying temperature in the step (v) to be 90-110 ℃.
8. The flame retardant high gloss high stiffness polycarbonate composite of claim 1, wherein: and (iv) in the granulating in the step (iv), controlling the particle size after the granulating to be 2-3 mm.
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| CN202111208987.2A CN113831717A (en) | 2021-10-18 | 2021-10-18 | Flame-retardant high-gloss high-hardness polycarbonate composite material and preparation method thereof |
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| CN202111208987.2A CN113831717A (en) | 2021-10-18 | 2021-10-18 | Flame-retardant high-gloss high-hardness polycarbonate composite material and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475739A (en) * | 2008-11-28 | 2009-07-08 | 上海锦湖日丽塑料有限公司 | High gloss, scratch-resistant, halogen-free and flame-retardant polycarbonate resin composition |
| CN103467953A (en) * | 2012-06-06 | 2013-12-25 | 合肥杰事杰新材料股份有限公司 | Modified scratch-resistant polycarbonate composition and preparation method thereof |
| CN104086969A (en) * | 2014-07-11 | 2014-10-08 | 上海锦湖日丽塑料有限公司 | Transparent scratch-resistant PC/PMMA (Poly Carbonate/Polymethyl Methacrylate) alloy material and preparation method thereof |
| CN106751661A (en) * | 2016-12-12 | 2017-05-31 | 广东威林工程塑料股份有限公司 | A kind of low cost, HI high impact, high glaze and halogen-free and flame-retardant polycarbonate material and preparation method thereof |
-
2021
- 2021-10-18 CN CN202111208987.2A patent/CN113831717A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475739A (en) * | 2008-11-28 | 2009-07-08 | 上海锦湖日丽塑料有限公司 | High gloss, scratch-resistant, halogen-free and flame-retardant polycarbonate resin composition |
| CN103467953A (en) * | 2012-06-06 | 2013-12-25 | 合肥杰事杰新材料股份有限公司 | Modified scratch-resistant polycarbonate composition and preparation method thereof |
| CN104086969A (en) * | 2014-07-11 | 2014-10-08 | 上海锦湖日丽塑料有限公司 | Transparent scratch-resistant PC/PMMA (Poly Carbonate/Polymethyl Methacrylate) alloy material and preparation method thereof |
| CN106751661A (en) * | 2016-12-12 | 2017-05-31 | 广东威林工程塑料股份有限公司 | A kind of low cost, HI high impact, high glaze and halogen-free and flame-retardant polycarbonate material and preparation method thereof |
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