CN107312304B - Two-dimensional reinforced polycarbonate composite material and preparation method thereof - Google Patents
Two-dimensional reinforced polycarbonate composite material and preparation method thereof Download PDFInfo
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- CN107312304B CN107312304B CN201710519205.4A CN201710519205A CN107312304B CN 107312304 B CN107312304 B CN 107312304B CN 201710519205 A CN201710519205 A CN 201710519205A CN 107312304 B CN107312304 B CN 107312304B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/04—Antistatic
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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
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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
Abstract
The invention discloses a two-dimensional reinforced polycarbonate composite material and a preparation method thereof; the composition comprises the following components in parts by weight: polycarbonate resin PC: 70-80, acrylonitrile-styrene copolymer resin SAN: 10-20 parts of nano clay, 1-5 parts of nano clay, 5-10 parts of toughening agent, 0.1-1 part of antioxidant and 0.1-1 part of lubricant. When in preparation, the PC resin, the SAN resin, the toughening agent, the antioxidant and the lubricant are added into a mixing stirrer for mixing; and mixing and granulating the obtained mixture through a double-screw extruder, adding nano clay into a side feeding port, adding an ultrasonic device outside a seventh zone of the extruder, and performing melt extrusion and granulation to obtain the product, namely the two-dimensional reinforced PC alloy material. Compared with the prior art, the polycarbonate composition provided by the invention has the advantages that the ultrasonic device is additionally arranged in the side feeding area to disperse nano clay particles, the compatibility of PC and SAN is increased, and the properties of enhancing the surface, blocking and the like of a material are improved.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a two-dimensional reinforced polycarbonate composite material and a preparation method thereof.
Background
The polycarbonate alloy has excellent properties such as high impact toughness, high temperature resistance and the like, and is widely applied to the fields of automobiles, household appliances, office supplies and the like, but due to brittleness and insufficient strength, cracking can occur, the product is unstable, falling resistance is not achieved, and the like, so that the use is limited.
The common fiber reinforced system is modified by adding mineral modified polycarbonate, but the obtained material has insufficient surface gloss or risks of mineral precipitation. And anisotropy may exist for fiber reinforcement as a one-dimensional reinforcement.
The prior reinforcing material has the defects of uneven dispersion of reinforcing components, low reinforcing effect caused by agglomeration of additives with excessively fine particle sizes and the like.
Disclosure of Invention
The present invention aims to overcome the defects of the prior art and provide a two-dimensionally reinforced polycarbonate composite material and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
the invention relates to a two-dimensional reinforced polycarbonate composite material composition, which comprises the following components in parts by weight:
polycarbonate (C): 70-80 parts;
acrylonitrile-styrene copolymer: 10-20 parts;
nano clay: 1-5 parts;
a toughening agent: 5-10 parts;
antioxidant: 0.1-1 part;
lubricant: 0.1 to 1 portion.
Preferably, the polycarbonate is an aromatic polycarbonate produced by a transesterification method.
Preferably, the weight average molecular weight of the polycarbonate is 30000-54000.
Preferably, the weight-average molecular weight of the acrylonitrile-styrene copolymer is 120000-160000, and the acrylonitrile-styrene copolymer comprises 25-38% of acrylonitrile and 62-75% of styrene by mass percentage.
Preferably, the nano clay is a layered montmorillonite mineral with the particle size of 60-75nm, and comprises long-chain quaternary ammonium salt grafted montmorillonite. The long-chain quaternary ammonium salt grafted montmorillonite is a mineral grafted on a montmorillonite main chain by quaternary ammonium salt with the chain segment length of 10-30 chain segments.
Preferably, the toughening agent comprises one or two of methyl methacrylate/acrylic acid polymer, acrylic acid-silicon rubber toughening agent, methacrylate toughening agent, ethylene-acrylate copolymerization toughening agent, ethylene-acrylate-glycidyl methacrylate terpolymer or ethylene-vinyl acetate copolymer-maleic anhydride.
Preferably, the antioxidant comprises one or more of an antioxidant 245, an antioxidant 1076 and an antioxidant 168.
Preferably, the lubricant comprises one or more of silicone powder, pentaerythritol ester, ethylene bisstearamide and butyl stearate.
The present invention also relates to a method for preparing the two-dimensionally reinforced polycarbonate composite composition of the present invention, comprising the steps of:
s1, adding the polycarbonate, the acrylonitrile-styrene copolymer, the toughening agent, the antioxidant and the lubricant into a mixing stirrer for mixing;
and S2, blending and granulating the obtained mixture through a double-screw extruder, adding the nano clay into a side feeding port, adding an ultrasonic device into a seventh area of the extruder, wherein the rotating speed of the screw extruder is 500-900 rpm, the pressure is 2-3 MPa, and performing melt extrusion and granulation to obtain the two-dimensional reinforced polycarbonate composite material composition.
Preferably, the screw diameter of the double-screw extruder is 46mm, and the length-diameter ratio is 50.
The principle of the invention is as follows: the PC adopting the ester exchange method can react with the functional groups on the surface of the nano clay through hydroxyl, so that the compatibility with SAN is increased, and the appearance of the PC alloy is improved. The nano clay with the particle size of 60-75nm is fully dispersed in a PC alloy system, so that the strength of the PC alloy material can be enhanced, and the layered montmorillonite structure enables the material to have excellent barrier property, antistatic property and flame retardance. The filler has small grain diameter, so that the surface of the product is smooth and the phenomenon of mineral precipitation does not occur. The nano clay is added through side feeding to prevent the phenomena of uneven dispersion and agglomeration of the nano particles.
Compared with the prior art, the invention has the beneficial effects that:
1. the polycarbonate composition of the invention selects ester exchange PC, has more hydroxyl groups than PC prepared by other methods, and increases the compatibility with SAN through the reaction of the hydroxyl groups and the functional groups on the surface of nano clay, thereby improving the appearance of PC alloy.
2. The nano clay with the particle size of 60-75nm is fully dispersed in a PC alloy system, the strength of the PC alloy material can be enhanced,
3. in order to enable the nano clay to react with the ester exchange PC better, an extruder with a large length-diameter ratio is used, the nano clay is fed laterally, and an ultrasonic device is additionally arranged in the seven zones, so that the nano clay is uniformly dispersed; the PC alloy material with two-dimensional reinforcement and excellent surface is obtained.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
In the following examples and comparative examples, bisphenol A type polycarbonate with molecular weight of 30000-54000, specifically L-1250Y formed by Asahi, was selected, and tested to have melt index of 10g/10min at 300 ℃ according to ASTM D1234 standard; the SAN has the molecular weight of 120000-160000 and comprises 25-38% by mass of acrylonitrile, SAN320 and SAN326 of Korean Jinhu lake; the nano clay is a layered montmorillonite mineral with the particle size of 60-75 nm; the antioxidant is 1010 and 168 produced by CIBA company.
Comparative example 1
A two-dimensional reinforced polycarbonate composite material and a preparation method thereof, wherein the method comprises the following steps:
(1) weighing the following components in parts by weight: PC is L1250Y: 70, SAN is SAN 320: 20, toughening agent EXL-2691A: 10, an antioxidant 10100.1, an antioxidant 1680.1 and a lubricant PETS 1.
(2) And (2) feeding the raw materials mainly, adding 1 part of nano clay and a side feed port, performing melt extrusion at 200-270 ℃, performing melt extrusion at the rotating speed of 700rpm and the pressure of 2MPa of a screw extruder, and performing melt extrusion and granulation to obtain the product.
(3) The diameter of the screw of the extruder is 46mm, and the length-diameter ratio is 50.
Contrast ratio 2
A two-dimensional reinforced polycarbonate composite material and a preparation method thereof, wherein the method comprises the following steps:
(1) weighing the following components in parts by weight: PC is L1250Y: 70, SAN is SAN 320: 20, toughening agent EXL-2691A: 10, 10100.1, 1680.1, 1 part of PETS 1 serving as a lubricant and 1 part of nano clay.
(2) The raw materials are fed in a main feeding mode, melt extrusion is carried out at the temperature of 200-270 ℃, the rotating speed of a screw extruder is 700rpm, the pressure is 2MPa, and the product is obtained through melt extrusion and granulation.
(3) The diameter of the screw of the extruder is 46mm, and the length-diameter ratio is 50.
Comparative example 3
A two-dimensional reinforced polycarbonate composite material and a preparation method thereof, wherein the method comprises the following steps:
(1) weighing the following components in parts by weight: PC is L1250Y: 70, SAN is SAN 320: 20, toughening agent EXL-2691A: 10, an antioxidant 10100.1, an antioxidant 1680.1 and a lubricant PETS 1.
(2) The raw materials are fed in a main feeding mode, melt extrusion is carried out at the temperature of 200-270 ℃, an ultrasonic device is additionally arranged in a seventh area of an extruder for ultrasonic treatment, the rotating speed of a screw extruder is 700rpm, the pressure is 2MPa, and the product is obtained through melt extrusion and granulation.
(3) The diameter of the screw of the extruder is 46mm, and the length-diameter ratio is 50.
Comparative example 4
A two-dimensional reinforced polycarbonate composite material and a preparation method thereof, wherein the method comprises the following steps:
(1) weighing the following components in parts by weight: PC is L1250Y: 70, SAN is SAN 320: 20, a toughening agent: 10 parts of polyester type thermoplastic polyurethane elastomer, an antioxidant 10100.1, an antioxidant 1680.1 and a lubricant PETS 1.
(2) The raw materials are fed in through main feeding, 1 part of nano clay is added through a side feeding port, an ultrasonic device is additionally arranged in a seventh area of an extruder, the raw materials are melted and extruded at the temperature of 200-270 ℃, the rotating speed of a screw extruder is 700rpm, the pressure is 2MPa, and the product is obtained through melting, extruding and granulating.
(3) The diameter of the screw of the extruder is 46mm, and the length-diameter ratio is 50.
Comparative example 5
A two-dimensional reinforced polycarbonate composite material and a preparation method thereof, wherein the method comprises the following steps:
(1) weighing the following components in parts by weight: PC is L1250Y: 70, SAN is SAN 320: 20, toughening agent EXL-2691A: 10, 10100.1 parts of antioxidant, 1680.1 parts of antioxidant, PETS 1 parts of lubricant and 3 parts of compatilizer styrene-acrylate copolymer.
(2) The raw materials are fed in through main feeding, 1 part of nano clay is added through a side feeding port, an ultrasonic device is additionally arranged in a seventh area of an extruder, the raw materials are melted and extruded at the temperature of 200-270 ℃, the rotating speed of a screw extruder is 700rpm, the pressure is 2MPa, and the product is obtained through melting, extruding and granulating.
(3) The diameter of the screw of the extruder is 46mm, and the length-diameter ratio is 50.
Example 1
(1) Weighing the following components in parts by weight: PC is L1250Y: 70, SAN is SAN 320: 20, toughening agent EXL-2691A: 10, an antioxidant 10100.1, an antioxidant 1680.1 and a lubricant PETS 1.
(2) The raw materials are fed in through main feeding, 1 part of nano clay is added through a side feeding port, an ultrasonic device is additionally arranged in a seventh area of an extruder, the raw materials are melted and extruded at the temperature of 200-270 ℃, the rotating speed of a screw extruder is 700rpm, the pressure is 2MPa, and the product is obtained through melting, extruding and granulating.
(3) The diameter of the screw of the extruder is 46mm, and the length-diameter ratio is 50.
Example 2
(1) Weighing the following components in parts by weight: PC is L1250Y: 80, SAN is SAN 320: 10, toughening agent EXL-2691A: 5, 0.1 part of antioxidant 1010, and the weight ratio of antioxidant: 1680.5, lubricant PETS: 0.3.
(2) feeding the raw materials mainly, wherein the nano clay comprises the following components: 5 parts of the raw materials are added through a side feeding port, an ultrasonic device is additionally arranged in a seventh area of the extruder, the raw materials are melted and extruded at the temperature of 200-280 ℃, the rotating speed of the screw extruder is 500rpm, the pressure is 2MPa, and the product is obtained through melting, extruding and granulating.
(3) The diameter of the screw of the extruder is 46mm, and the length-diameter ratio is 50.
Example 3
(1) Weighing the following components in parts by weight: PC is L1250Y: 75, SAN is SAN 320: 15, toughening agent EXL-2691A: 8, antioxidant 10100.2, antioxidant 168: 0.8, lubricant PETS: 0.5.
(2) feeding the raw materials mainly, wherein the nano clay comprises the following components: 3 parts of the raw materials are added through a side feeding port, an ultrasonic device is additionally arranged in a seventh area of the extruder, the raw materials are melted and extruded at the temperature of 200-280 ℃, the rotating speed of the screw extruder is 900rpm, the pressure is 3MPa, and the product is obtained through melting, extruding and granulating.
(3) The diameter of the screw of the extruder is 46mm, and the length-diameter ratio is 50.
Example 4
(1) Weighing the following components in parts by weight: PC is L1250Y: 78, SAN is SAN 320: 18, toughening agent EXL-2691A: 6, antioxidant 1010: 0.3, antioxidant 168: 0.3, lubricant PETS: 1.
(2) and (3) feeding the raw materials mainly, adding 4 parts of nano clay and a side feeding port, adding an ultrasonic device in a seventh area of an extruder, performing melt extrusion at 200-280 ℃, performing melt extrusion at the rotating speed of 600rpm and the pressure of 2MPa by using a screw extruder, and performing melt extrusion and granulation to obtain the product.
(3) The diameter of the screw of the extruder is 46mm, and the length-diameter ratio is 50.
The test results of the respective comparative examples and examples are shown in table 1. Tensile strength was measured according to ASTM D638, and flexural strength was measured according to ASTM D790.
TABLE 1
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (6)
1. The two-dimensional reinforced polycarbonate composite material composition is characterized by comprising the following components in parts by weight:
polycarbonate (C): 70-80 parts;
acrylonitrile-styrene copolymer: 10-20 parts;
nano clay: 1-5 parts;
a toughening agent: 5-10 parts;
antioxidant: 0.1-1 part;
lubricant: 0.1-1 part;
the polycarbonate is ester exchange aromatic polycarbonate;
the nano clay is long-chain quaternary ammonium salt grafted montmorillonite with the particle size of 60-75nm, wherein quaternary ammonium salt with chain segment length of 10-30 chain segments is grafted on the main chain of the montmorillonite;
the toughening agent comprises one or two of an acrylic acid-silicon rubber toughening agent, a methacrylate toughening agent, an ethylene-acrylate copolymer toughening agent or an ethylene-vinyl acetate copolymer-maleic anhydride;
the two-dimensionally reinforced polycarbonate composite composition is prepared by a method comprising the steps of:
s1, adding the polycarbonate, the acrylonitrile-styrene copolymer, the toughening agent, the antioxidant and the lubricant into a mixing stirrer for mixing;
and S2, blending and granulating the obtained mixture through a double-screw extruder, adding the nano clay into a side feeding port, adding an ultrasonic device into a seventh area of the extruder, wherein the rotating speed of the screw extruder is 500-900 rpm, the pressure is 2-3 MPa, and performing melt extrusion and granulation to obtain the two-dimensional reinforced polycarbonate composite material composition.
2. The two-dimensionally reinforced polycarbonate composite composition of claim 1, wherein the polycarbonate has a weight average molecular weight of 30000-54000.
3. The two-dimensionally reinforced polycarbonate composite composition according to claim 1, wherein the acrylonitrile-styrene copolymer has a weight average molecular weight of 120000-160000, and comprises 25-38% by mass of acrylonitrile and 62-75% by mass of styrene.
4. The two-dimensionally reinforced polycarbonate composite composition of claim 1, wherein the antioxidant comprises one or more of antioxidant 245, antioxidant 1076, and antioxidant 168.
5. The two-dimensionally reinforced polycarbonate composite composition of claim 1, wherein the lubricant comprises one or more of silicone powder, pentaerythritol ester, ethylene bisstearamide, butyl stearate.
6. The two-dimensional reinforced polycarbonate composite composition of claim 1, wherein the twin screw extruder has a screw diameter of 46mm and an aspect ratio of 50.
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| CN112063147A (en) * | 2020-09-10 | 2020-12-11 | 安庆会通新材料有限公司 | Two-dimensional organic metal framework MOF modified PC material |
| CN112795162A (en) * | 2020-12-30 | 2021-05-14 | 会通新材料股份有限公司 | Easily-sprayed high-rigidity alloy material and preparation method thereof |
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| WO2005071012A1 (en) * | 2004-01-13 | 2005-08-04 | Polyone Corporation | Use of a thermoplastic vulcanizate as an impact modifier in blends of polyester and polycarbonate |
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| US6262162B1 (en) * | 1999-03-19 | 2001-07-17 | Amcol International Corporation | Layered compositions with multi-charged onium ions as exchange cations, and their application to prepare monomer, oligomer, and polymer intercalates and nanocomposites prepared with the layered compositions of the intercalates |
| CN100427545C (en) * | 2006-07-27 | 2008-10-22 | 上海交通大学 | Process for preparing polycarbonate /acrylonitirle-ternary ethyl propylene rubber-styrene resin / laminated silicate nano composite material |
| CN103709709B (en) * | 2013-12-20 | 2016-01-06 | 上海锦湖日丽塑料有限公司 | Polycarbonate compositions of a kind of high tenacity and preparation method thereof |
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| WO2005071012A1 (en) * | 2004-01-13 | 2005-08-04 | Polyone Corporation | Use of a thermoplastic vulcanizate as an impact modifier in blends of polyester and polycarbonate |
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