CN104877322A - Modified fiber reinforced polycarbonate composite material and product thereof - Google Patents
Modified fiber reinforced polycarbonate composite material and product thereof Download PDFInfo
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- CN104877322A CN104877322A CN201410070375.5A CN201410070375A CN104877322A CN 104877322 A CN104877322 A CN 104877322A CN 201410070375 A CN201410070375 A CN 201410070375A CN 104877322 A CN104877322 A CN 104877322A
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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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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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses a modified fiber reinforced polycarbonate composite material, which comprises, by weight, a thermoplastic resin, a reinforcing filling material, and 5-15 parts of a flame retardant agent, wherein the thermoplastic resin comprises 45-55 parts of a PC resin and 1-10 parts of an ASA resin, and the reinforcing filling material comprises 30-40 parts of flat cross section glass fibers and 0.1-1.5 parts of a nanometer filling material. Compared with the modified fiber reinforced polycarbonate composite material and the product thereof in the prior art, the modified fiber reinforced polycarbonate composite material and the product thereof of the present invention have the following characteristics that: the flat cross section glass fibers and the fibrous filling material excluding the flat cross section glass fibers are used to reinforce the composite material adopting the polycarbonate as the matrix, the nanometer filling material is added to form the reinforced composite resin composition with characteristics of good mechanical strength, good flowability, and low warpage, and the repeated experiment results show that the purpose can be achieved through the cooperation effect of the thermoplastic resin and the nanometer particle rolling effect.
Description
[technical field]
The invention belongs to field of material technology, be specifically related to a kind of modified fibre reinforced polycarbonate matrix material and products thereof.
[background technology]
Thermoplastic resin polycarbonate by with glass fiber reinforcement after, due to the physical strength of its excellence, dimensional stability, flame retardant resistance and processing characteristics, widely use in the various fields such as mechanical part, trolley part, electrical and electronic parts, office equipment part.
But in recent years, product is lightening drives formula, to the continuous lifting that the glass fiber reinforcement thermoplastic resin of product physical strength, high heat distortion temperature, low warpage properties, low flame retardancy requires.Although by the resin combination physical strength, the excellent rigidity that coordinate glass fibre in single polycarbonate resin, because of the performance deficiency of polycarbonate resin itself, in physical strength, molding shrinkage still has shortcoming.Such as, the glass fiber reinforcement aromatic polycarbonate resin composition occurred on the market, major part exist flowing property deficiency cause ejection formation after easily buckling deformation and have the problem of stress trace.
In view of this, be in fact necessary to develop a kind of matrix material, with solve above-mentioned polycarbonate resin illiquidity cause shaping after the defect of product buckling deformation.
[summary of the invention]
Therefore, the object of this invention is to provide a kind of modified fibre reinforced polycarbonate matrix material and products thereof, adopt the product after this composite material forming to have good physical strength, mobility, low warpage properties.
In order to achieve the above object, modified fibre reinforced polycarbonate matrix material of the present invention, it represents by weight and comprises:
Thermoplastic resin, it comprises PC resin 45 ~ 55 parts and ASA resin 1 ~ 10 part;
Strengthen packing material, it comprises 30 ~ 40 parts, flat cross section glass fibre and how rice packing material 0.1 ~ 1.5 part;
Fire retardant 5 ~ 15 parts.
Alternatively, the water-intake rate of described PC resin is 0.06 ~ 0.10%, and glass transition temp is 130 ~ 170 DEG C, and viscosity-average molecular weight is 19000 ~ 22000.
Alternatively, described ASA resin is by acrylate rubber like body and vinyl cyanide, cinnamic graft copolymer.
Alternatively, the flat ratio of described flat cross section glass fibre is 0.1 ~ 0.5, and the minor axis in described flat cross section glass fibre cross section is 0.5 ~ 25 μm, and the major diameter in cross section is 1.0 ~ 250 μm.
Alternatively, the flat ratio of described flat cross section glass fibre is 0.2 ~ 0.3.
Alternatively, described how rice packing material be the calcium oxide of how meter level, calcium carbonate and carbon nanotube at least one of them.
Alternatively, described fire retardant be organic metal salt flame retardant, organic phosphorus flame retardant, organic silicon fibre retardant at least one of them.
Alternatively, described organic metal salt flame retardant comprise organic sulfonic acid alkali metal salts, borate metal salt flame retardant or stannic acid metal-salt flame retardant at least one of them, described organic phosphorus flame retardant phosplate compound, phosphoric acid ester oligomer compounds, phosphonate oligomers compound, Phosphoramido compounds at least one of them, described silicone flame retardant includes organic silicon compound.
Alternatively, described modified fibre reinforced polycarbonate matrix material also comprises fluorine-containing Antidrip agent.
Alternatively, described fluorine-containing Antidrip agent is tetrafluoroethylene or tetrafluoroethylene based copolymer.
Optionally, described modified fibre reinforced polycarbonate matrix material also comprises at least one in thermoplastic resin beyond described PC resin and ASA resin, rubber polymer, flow ability modifying agent.
Alternatively, described modified fibre reinforced polycarbonate matrix material also comprises stablizer, releasing agent, antiseptic-germicide, dispersion agent, photocatalyst system stain control agent, photochromic agent at least one.
Optionally, described stablizer is at least one in phosphorus system stablizer, hindered phenol system oxidation inhibitor, UV light absorber, photostabilizer.
In addition, the present invention also provides a kind of product, and described product is the product produced after described modified fibre reinforced polycarbonate composite material forming.
Compared to prior art, modified fibre reinforced polycarbonate matrix material of the present invention and products thereof, with the fibrous filler material beyond flat cross section glass fibre and flat cross section glass fibre, enhance the matrix material that polycarbonate is matrix, add how rice packing material, form the enhancing composite resin composition simultaneously with good physical strength, mobility, low warpage properties.Experimental result finds repeatedly, and the association undertaken by thermoplastic resin and the ball effect of nanoparticle becomes to act on, and can realize this object.
[embodiment]
Modified fibre reinforced polycarbonate matrix material of the present invention, it represents by weight and comprises:
Thermoplastic resin, it comprises PC resin 45 ~ 55 parts and ASA resin 1 ~ 10 part; The water-intake rate of described PC resin is 0.06 ~ 0.10%, and glass transition temp is 130 ~ 170 DEG C, and viscosity-average molecular weight is 19000 ~ 22000; Described ASA resin is by acrylate rubber like body and vinyl cyanide, cinnamic graft copolymer; The hydrolytic resistance of carbonate polymer self is good, and shaping after low warpage properties also especially excellent; ASA resin has excellent weathering resistance;
Strengthen packing material, it comprises 30 ~ 40 parts, flat cross section glass fibre and how rice packing material 0.1 ~ 1.5 part; Described flat cross section glass fibre has the cross section of flat pattern, flat ratio is 0.1 ~ 0.5, better flat ratio is 0.2 ~ 0.3, when particularly flat ratio is more than 0.2, the flexural strength of matrix material and shock strength can maintain extra high level, the minor axis in described flat cross section glass fibre cross section is 0.5 ~ 25 μm, and the major diameter in cross section is 1.0 ~ 250 μm; Described how rice packing material be the calcium oxide of how meter level, calcium carbonate and carbon nanotube at least one of them;
Fire retardant 5 ~ 15 parts; Described fire retardant be organic metal salt flame retardant, organic phosphorus flame retardant, organic silicon fibre retardant at least one of them; Described organic metal salt flame retardant comprise organic sulfonic acid alkali metal salts, borate metal salt flame retardant or stannic acid metal-salt flame retardant at least one of them, described organic phosphorus flame retardant phosplate compound, phosphoric acid ester oligomer compounds, phosphonate oligomers compound, Phosphoramido compounds at least one of them, described silicone flame retardant includes organic silicon compound;
Fluorine-containing Antidrip agent 1 ~ 10 part, used by this fluorine-containing Antidrip agent and above-mentioned fire retardant, better flame retardant resistance can be obtained, described fluorine-containing Antidrip agent can be tetrafluoroethylene, tetrafluoroethylene based copolymer (multipolymer of such as tetrafluoroethylene or hexafluoroethylene), this fluorine-containing Antidrip agent also can be the partially fluorinated polymkeric substance shown in United States Patent (USP) No. 4379910 publication, by fluoridize bis-phenol manufacture polycarbonate resin, but be preferably tetrafluoroethylene;
Other auxiliary agent, can for making forming process time the dispersion agent of molecular weight reduces, low key tone is stable stablizer, releasing agent, antiseptic-germicide, whiteruss and so on, photocatalyst system stain control agent, at least one in photochromic agent; Described stablizer is at least one in phosphorus system stablizer, hindered phenol system oxidation inhibitor, UV light absorber, photostabilizer; It can be at least one in the thermoplastic resin beyond described recovery PC/ recycled PET, rubber polymer, flow ability modifying agent.
For having further understanding to object of the present invention, technique means and functional effect, existing combination specifically implements to make the following instructions the present invention.
Embodiment 1:
PC resin and ASA resin is dry in dehumidifying heat pump baking oven respectively; Take dried PC resin and ASA resin and mix; Take fire retardant, tetrafluoroethylene and other auxiliary agents, then join high-speed mixer high speed premix; By mixture in above-mentioned steps and the flat cross section glass fibre taken and how rice packing material joins on twin screw extruder respectively melt extrudes granulation.
Embodiment 2:
PC resin and ASA resin is dry in dehumidifying heat pump baking oven respectively; Take dried PC resin and ASA resin and mix; Take fire retardant, tetrafluoroethylene and other auxiliary agents, then join high-speed mixer high speed premix; By mixture in above-mentioned steps and the flat cross section glass fibre taken and how rice packing material joins on twin screw extruder respectively melt extrudes granulation.
Embodiment 3:
PC resin and ASA resin is dry in dehumidifying heat pump baking oven respectively; Take dried PC resin and ASA resin and mix; Take fire retardant, tetrafluoroethylene and other auxiliary agents, then join high-speed mixer high speed premix; By mixture in above-mentioned steps and the flat cross section glass fibre taken and how rice packing material joins on twin screw extruder respectively melt extrudes granulation.
After each embodiment and comparative example melt extrude granulation above, then injection moulding ASTM standard testing batten on injection moulding machine, by the mechanical property of ASTM standard testing resulting materials, wherein test shock strength according to ASTM D256, according to ASTM D638 test tensile strength, test flexural strength and modulus in flexure according to ASTM D790, test mobility MI value according to ASTM D1238, according to UL-94 standard testing flame retardant resistance, test result is as shown in table 1:
Table 1: the test result of embodiment
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Shock strength (KJ/m 2） | 11 | 11 | 12.5 |
| Tensile strength (Mpa) | 115 | 104 | 105 |
| Flexural strength (Mpa) | 172 | 164 | 165 |
| Modulus in flexure (Mpa) | 10 | 10.4 | 11.2 |
| MI（260℃，5Kg） | 80.00 | 421.20 | 338.80 |
| Flame retardant resistance (1.0mm) | V0 | V0 | V0 |
Can be drawn by table 1: with the fibrous filler material beyond flat cross section glass fibre and flat cross section glass fibre, enhance the matrix material that polycarbonate is matrix, add how rice packing material, the association undertaken by thermoplastic resin and the ball effect of nanoparticle becomes to act on, and the enhancing composite resin composition of formation has good physical strength, mobility, low warpage properties simultaneously.
In the present invention, the matrix material that the present invention obtains also compares with the PC+35%GF resin not adding how rice packing material, and test result is as shown in table 2 below:
Table 2: test result
Can be drawn by table 2, the matrix material of gained of the present invention, add how rice packing material, the association undertaken by thermoplastic resin and the ball effect of nanoparticle becomes to act on, and has better physical strength, mobility, low warpage properties.
In addition, the present invention also provides a kind of product, and described product is the product produced after described modified fibre reinforced polycarbonate composite material forming, described product not easily warpage.
In sum, modified fibre reinforced polycarbonate matrix material of the present invention and products thereof, with the fibrous filler material beyond flat cross section glass fibre and flat cross section glass fibre, enhance the matrix material that polycarbonate is matrix, add how rice packing material, form the enhancing composite resin composition simultaneously with good physical strength, mobility, low warpage properties.Experimental result finds repeatedly, and the association undertaken by thermoplastic resin and the ball effect of nanoparticle becomes to act on, and can realize this object.Can widely use in the various fields such as mechanical part, trolley part, electrical and electronic parts, office equipment part.
Claims (14)
1. a modified fibre reinforced polycarbonate matrix material, is characterized in that, it represents by weight and comprises:
Thermoplastic resin, it comprises PC resin 45 ~ 55 parts and ASA resin 1 ~ 10 part;
Strengthen packing material, it comprises 30 ~ 40 parts, flat cross section glass fibre and how rice packing material 0.1 ~ 1.5 part;
Fire retardant 5 ~ 15 parts.
2. modified fibre reinforced polycarbonate matrix material as claimed in claim 1, it is characterized in that, the water-intake rate of described PC resin is 0.06 ~ 0.10%, and glass transition temp is 130 ~ 170 DEG C, and viscosity-average molecular weight is 19000 ~ 22000.
3. modified fibre reinforced polycarbonate matrix material as claimed in claim 1, it is characterized in that, described ASA resin is by acrylate rubber like body and vinyl cyanide, cinnamic graft copolymer.
4. modified fibre reinforced polycarbonate matrix material as claimed in claim 1, it is characterized in that, the flat ratio of described flat cross section glass fibre is 0.1 ~ 0.5, and the minor axis in described flat cross section glass fibre cross section is 0.5 ~ 25 μm, and the major diameter in cross section is 1.0 ~ 250 μm.
5. modified fibre reinforced polycarbonate matrix material as claimed in claim 4, it is characterized in that, the flat ratio of described flat cross section glass fibre is 0.2 ~ 0.3.
6. modified fibre reinforced polycarbonate matrix material as claimed in claim 1, is characterized in that, described how rice packing material be the calcium oxide of how meter level, calcium carbonate and carbon nanotube at least one of them.
7. modified fibre reinforced polycarbonate matrix material as claimed in claim 1, is characterized in that, described fire retardant be organic metal salt flame retardant, organic phosphorus flame retardant, organic silicon fibre retardant at least one of them.
8. modified fibre reinforced polycarbonate matrix material as claimed in claim 1, it is characterized in that, described organic metal salt flame retardant comprise organic sulfonic acid alkali metal salts, borate metal salt flame retardant or stannic acid metal-salt flame retardant at least one of them, described organic phosphorus flame retardant phosplate compound, phosphoric acid ester oligomer compounds, phosphonate oligomers compound, Phosphoramido compounds at least one of them, described silicone flame retardant includes organic silicon compound.
9. modified fibre reinforced polycarbonate matrix material as claimed in claim 1, it is characterized in that, described modified fibre reinforced polycarbonate matrix material also comprises fluorine-containing Antidrip agent.
10. modified fibre reinforced polycarbonate matrix material as claimed in claim 9, it is characterized in that, described fluorine-containing Antidrip agent is tetrafluoroethylene or tetrafluoroethylene based copolymer.
11. modified fibre reinforced polycarbonate matrix materials as claimed in claim 1, it is characterized in that, described modified fibre reinforced polycarbonate matrix material also comprises at least one in thermoplastic resin beyond described PC resin and ASA resin, rubber polymer, flow ability modifying agent.
12. modified fibre reinforced polycarbonate matrix materials as claimed in claim 1, it is characterized in that, described modified fibre reinforced polycarbonate matrix material also comprises stablizer, releasing agent, antiseptic-germicide, dispersion agent, photocatalyst system stain control agent, photochromic agent at least one.
13. modified fibre reinforced polycarbonate matrix materials as claimed in claim 12, is characterized in that, described stablizer is at least one in phosphorus system stablizer, hindered phenol system oxidation inhibitor, UV light absorber, photostabilizer.
14. 1 kinds of products, is characterized in that, the product of described product for producing after the modified fibre reinforced polycarbonate composite material forming according to any one of claim 1 to 13.
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| CN201410070375.5A CN104877322A (en) | 2014-02-28 | 2014-02-28 | Modified fiber reinforced polycarbonate composite material and product thereof |
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| CN201410070375.5A CN104877322A (en) | 2014-02-28 | 2014-02-28 | Modified fiber reinforced polycarbonate composite material and product thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105462222A (en) * | 2015-12-21 | 2016-04-06 | 佛山市中科院环境与安全检测认证中心有限公司 | Engineering composite material |
| CN106751652A (en) * | 2016-11-14 | 2017-05-31 | 中山市亮彩染料实业有限公司 | A kind of bloom makrolon adds fiber composite material |
| CN108424604A (en) * | 2018-04-29 | 2018-08-21 | 徐菡 | A kind of antibacterial flame-retardant HIPS composite and preparation method thereof |
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2014
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105462222A (en) * | 2015-12-21 | 2016-04-06 | 佛山市中科院环境与安全检测认证中心有限公司 | Engineering composite material |
| CN106751652A (en) * | 2016-11-14 | 2017-05-31 | 中山市亮彩染料实业有限公司 | A kind of bloom makrolon adds fiber composite material |
| CN108424604A (en) * | 2018-04-29 | 2018-08-21 | 徐菡 | A kind of antibacterial flame-retardant HIPS composite and preparation method thereof |
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