CN109852056B - Wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition and preparation method thereof - Google Patents
Wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition and a preparation method thereof, wherein the composition comprises the following raw materials in parts by weight: 40-90 parts of PPS resin, 10-30 parts of carbon fiber, 10-30 parts of glass microsphere, 1-5 parts of low-density polyethylene and 0.1-1 part of antioxidant; the preparation method comprises the following steps: PPS resin, low-density polyethylene and an antioxidant are mixed and then fed from a main feeding port of an extruder; respectively feeding carbon fibers and glass beads from a side feeding port of an extruder; and blending and granulating through an extruder to obtain the wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition. Compared with the prior art, the invention has the advantages of high bending modulus, good toughness, flame retardance, no obvious scratch after the surface is scratched, good wear resistance and the like.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition and a preparation method thereof.
Background
Polyphenylene sulfide is widely used in the automotive and electronics industries due to its excellent heat resistance, flowability, flame retardancy, and electrical properties. But the mechanical property of the single polyphenylene sulfide material is not ideal enough, so that the application range of the polyphenylene sulfide material is limited. Carbon fiber is an organic fiber material, which can be usually made into a composite material with resin, can greatly enhance the mechanical properties of the resin, and can greatly reduce the weight of the composite material. The carbon fiber reinforced polyphenylene sulfide has ultrahigh rigidity, can replace metal, and has low density, strong rigidity and convenient processing. After the carbon fiber is added with the polyphenylene sulfide, the surface wear resistance is improved; however, the carbon fiber reinforced polyphenylene sulfide composition has a low retention length of carbon fibers, and if the retention length of carbon fibers is reduced, the strength and the surface wear resistance of the material are affected, which is not favorable for improving the tensile strength, the bending strength and the impact strength of the carbon fiber reinforced polyphenylene sulfide composition.
Chinese patent CN108373591A discloses a polyphenylene sulfide composite material with high carbon fiber content, which is characterized by comprising the following components in percentage by weight: 20 to 30 percent of polyphenylene sulfide, 70 to 85 percent of carbon fiber and 0.1 to 2 percent of coupling agent; the carbon fiber reinforced polyphenylene sulfide composite material is prepared by taking polyphenylene sulfide non-woven fabrics as raw materials and adopting a hot pressing method, the method can effectively reduce the adverse effect of carbon fiber deformation caused by polyphenylene sulfide melt flow, and can effectively prevent crack propagation, so that the tensile strength, the bending strength and the impact strength of the carbon fiber reinforced polyphenylene sulfide composite material are greatly improved. The carbon fiber reinforced polyphenylene sulfide composite material obtained by the patent technology has the tensile strength of 1250Mpa, the bending strength of 1130Mpa and the impact strength of 230KJ/m2Further improvements are desired.
Chinese patent CN102391648A discloses a polyphenylene sulfide composite material and a preparation method thereof, and a process for preparing a corrosion-resistant pump overflowing component by using the composite material, belonging to the technical field of corrosion-resistant materials and application. The composite material comprises the following main components in parts by mass: 100 parts of polyphenylene sulfide, 40-100 parts of reinforcing fiber, 18-35 parts of hollow glass microsphere and 25-60 parts of polyamide. The invention adopts a melt cladding method to prepare the composite material. The composite material is used for preparing the anti-corrosion pump overflowing component by adopting a compression molding process or an injection molding process. According to the method, the hollow glass beads are adopted to improve the wear resistance and the impact resistance of the carbon fiber reinforced polyphenylene sulfide composite material, the impact strength of the polyamide is further extremely high, but the problem of breakage of the hollow glass beads can influence the improvement of the performance of the carbon fiber reinforced polyphenylene sulfide composite material, and the content of the glass beads of the material is low, so that the improvement of the performance of the carbon fiber reinforced polyphenylene sulfide composite material can also be influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition comprises the following components in parts by weight:
the melt index of the PPS resin at 316 ℃ is not lower than 300g/10 min.
The carbon fiber is T700 carbon fiber.
The glass beads are solid beads with the particle size of 2 um.
Solid glass beads with small particle size are selected, the solid glass beads are hard and wear-resistant and are not easy to break, and the spherical glass beads with uniform and completely regular size can effectively improve the friction performance of the composite material; the glass beads are spherical fillers, and the addition of the glass beads can improve the flowability of the material and promote the carbon fibers to flow along the flowing direction, so that the mutual abrasion among the carbon fibers is reduced, and the high carbon fiber retention length is obtained, thereby improving the tensile strength, the bending strength and the impact strength of the composite material; the cenospheres are brittle when extruded, so solid cenospheres are selected. Too large glass beads reduce the improvement of fluidity, have too great physical influence, are too small and are difficult to disperse.
The Low Density Polyethylene (LDPE) has a number average molecular weight of 2000 to 10000,
the LDPE is added to promote the carbon fibers to be arranged along the flowing direction, so that the remaining length of the carbon fibers is increased, and the rigidity of the wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition is further improved.
The antioxidant is selected from one or more of antioxidant 245, antioxidant 1076 and antioxidant 168.
The invention also provides a preparation method of the wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition, which comprises the following steps:
PPS resin, LDPE and an antioxidant are mixed and then fed from a main feeding port of an extruder; respectively feeding carbon fibers and glass beads from a side feeding port of an extruder; and blending and granulating through an extruder to obtain the wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition.
The extruder is a double-screw extruder, the control temperature of the extruder is 280-310 ℃, the rotating speed of the double-screw extruder is 450-550 rpm, preferably 500rpm, and the pressure is 1.8-2.2 MPa, preferably 2 MPa.
The key principle for preparing the wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition is that low-density polyethylene (LDPE) and glass beads are added, the particle size of the glass beads is very important, and the hollow beads are fragile during extrusion, so solid beads are selected. The too big glass bead reduces the mobility improvement, and the rerum natura influence is too big, and glass bead is too little, and dispersion difficulty, the glass bead dispersion inequality that the particle size is less leads to promoting carbon fiber to flow direction and arranges the effect not good.
Compared with the prior art, the wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition has the advantages of high bending modulus, good toughness, flame retardance and no obvious scratch after the surface is scratched. By adding the LDPE and the glass beads, the carbon fibers are distributed along the flowing direction, so that the retention length of the carbon fibers is increased, the rigidity is improved, and the wear resistance of the material is improved by the glass beads.
Detailed Description
The present invention will be described in detail with reference to specific 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 variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The PPS1 in the following examples and comparative examples was PPS having an MI (316 ℃ C. by 5kg) of 300g/10 min; PPS2 is PPS having an MI (316 ℃ 5kg) of 200g/10 min; the carbon fiber is Dongli T700, the particle diameter of the glass bead is 2um, the weight average molecular weight of the LDPE is 3000, and the antioxidant is antioxidant 1010 and antioxidant 168 produced by CIBA company.
Comparative example 1
A wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition and a preparation method thereof are disclosed, the method comprises the following steps:
(1) weighing the following components in parts by weight: PPS 2: 90, carbon fiber: 10, 0.1-1 of antioxidant, wherein the PPS2 is PPS with MI (316 ℃ C. 5kg) of 200g/10 min; the carbon fiber is Dongli T700, and the antioxidant is antioxidant 1010 and antioxidant 168 produced by CIBA company.
(2) PPS and an antioxidant are added into a mixer, mixed and fed from a main feeding port of an extruder, carbon fibers are fed from a side feeding port, melted and extruded at the temperature of 280-310 ℃, the rotating speed of a screw extruder is 500rpm, the pressure is 2MPa, and the product is obtained through melting, extruding and granulating.
Comparative example 2
A wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition and a preparation method thereof are disclosed, the method comprises the following steps:
(1) weighing the following components in parts by weight: PPS 1: 40, carbon fiber: 30, glass beads: 30, 0.1-1% of antioxidant; wherein PPS1 is PPS having an MI (316 ℃ C. 5kg) of 300g/10 min; the carbon fiber is Dongli T700, the glass bead has a particle size of 2um, and the antioxidant is antioxidant 1010 and antioxidant 168 produced by CIBA company.
(2) PPS1 and an antioxidant are added into a mixer, mixed and fed from a main feeding port of an extruder, carbon fibers and glass microspheres are fed from a side feeding port, melted and extruded at the temperature of 280-310 ℃, the rotating speed of a screw extruder is 500rpm, the pressure is 2MPa, and the product is obtained through melting, extrusion and granulation.
Example 1
A wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition and a preparation method thereof are disclosed, the method comprises the following steps:
(1) weighing the following components in parts by weight: PPS 1: 45, carbon fiber: 30, glass beads: 30, LDPE 5, antioxidant, 0.5; wherein PPS1 is PPS having an MI (316 ℃ C. 5kg) of 300g/10 min; the carbon fiber is Dongli T700, the particle diameter of the glass bead is 2um, the weight average molecular weight of the LDPE is 3000, and the antioxidant is antioxidant 1010 and antioxidant 168 produced by CIBA company.
(2) PPS1 and an antioxidant are mixed and then fed from a main feeding port of an extruder, carbon fibers and glass microspheres are fed from a side feeding port, and are melted and extruded at the temperature of 280-310 ℃, the rotating speed of a screw extruder is 500rpm, the pressure is 2MPa, and the product is obtained through melting, extrusion and granulation.
Example 2
A wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition and a preparation method thereof are disclosed, the method comprises the following steps:
(1) weighing the following components in parts by weight: PPS 1: 55, carbon fiber: 30, glass beads: 10, 5 of LDPE and 0.3 of antioxidant; wherein PPS1 is PPS having an MI (316 ℃ C. 5kg) of 300g/10 min; the carbon fiber is Dongli T700, the particle diameter of the glass bead is 2um, the weight average molecular weight of the LDPE is 3000, and the antioxidant is antioxidant 1010 and antioxidant 168 produced by CIBA company.
(2) PPS1 and an antioxidant are mixed and then fed from a main feeding port of an extruder, carbon fibers and glass microspheres are fed from a side feeding port, and are melted and extruded at the temperature of 280-310 ℃, the rotating speed of a screw extruder is 500rpm, the pressure is 2MPa, and the product is obtained through melting, extrusion and granulation.
Example 3
A wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition and a preparation method thereof are disclosed, the method comprises the following steps:
(1) weighing the following components in parts by weight: PPS 1: 47, carbon fiber: 20, glass beads: 20, 3 parts of LDPE and 0.1-1 part of antioxidant; wherein PPS1 is PPS having an MI (316 ℃ C. 5kg) of 300g/10 min; the carbon fiber is Dongli T700, the particle diameter of the glass bead is 2um, the weight average molecular weight of the LDPE is 3000, and the antioxidant is antioxidant 1010 and antioxidant 168 produced by CIBA company.
(2) PPS1 and an antioxidant are mixed and then fed from a main feeding port of an extruder, carbon fibers and glass microspheres are fed from a side feeding port, and are melted and extruded at the temperature of 280-310 ℃, the rotating speed of a screw extruder is 500rpm, the pressure is 2MPa, and the product is obtained through melting, extrusion and granulation.
Example 4
The wear-resistant and flame-retardant carbon fiber reinforced polyphenylene sulfide compositions obtained in comparative examples 1-2 and examples 1-3 were subjected to performance tests, and the test results are shown in table 1. Flexural modulus was performed according to ASTM D790; unnotched impact strength was tested according to ASTM D256 with a bar thickness of 1/8 "; notched impact strength was measured according to ASTM D256 with a bar thickness of 1/8 "; the flame resistance was measured according to UL94 standard, and the specimens had a thickness of 1.6 mm. The test condition of the surface wear resistance of the material is that the material is molded into a high-gloss surface, the material is rubbed 5000 times by non-woven fabrics under the 50N load condition, and the surface state is observed.
TABLE 1 Performance testing of compositions of comparative examples 1-2 and examples 1-3
The more ≧ in the form, the more serious the scratch.
As can be seen from Table 1, example 2 has high flexural modulus, good toughness, flame retardance, and no significant scratch after the surface was scratched. By adding the LDPE and the glass beads, the carbon fibers are distributed along the flowing direction, so that the retention length of the carbon fibers is increased, the rigidity is improved, and the wear resistance of the material is improved by the glass beads.
Example 5
A wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition and a preparation method thereof are disclosed, the method comprises the following steps:
(1) weighing the following components in parts by weight: PPS 1: 40, carbon fiber: 10, glass beads: 10, LDPE: 1, 0.1 of antioxidant; wherein PPS1 is PPS having an MI (316 ℃ C. 5kg) of 300g/10 min; the carbon fiber is Dongli T700, the particle diameter of the glass bead is 2um, the weight average molecular weight of the LDPE is 10000, and the antioxidant is a mixture of antioxidant 245, antioxidant 1076 and antioxidant 168 produced by CIBA company.
(2) PPS1 and an antioxidant are mixed and then fed from a main feeding port of an extruder, carbon fibers and glass microspheres are fed from a side feeding port, and are melted and extruded at 280 ℃, the rotating speed of a screw extruder is 450rpm, the pressure is 1.8MPa, and the product is obtained through melting, extruding and granulating.
Example 5
A wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition and a preparation method thereof are disclosed, the method comprises the following steps:
(1) weighing the following components in parts by weight: PPS 1: 90, carbon fiber: 30, glass beads: 30, LDPE:5, antioxidant 1; wherein PPS1 is PPS having an MI (316 ℃ C. 5kg) of 300g/10 min; the carbon fiber is Dongli T700, the particle diameter of the glass bead is 2um, the weight average molecular weight of the LDPE is 2000, and the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 produced by CIBA company.
(2) PPS1 and an antioxidant are mixed and then fed from a main feeding port of an extruder, carbon fibers and glass microspheres are fed from a side feeding port, and are melted and extruded at the temperature of 310 ℃, the rotating speed of a screw extruder is 550rpm, the pressure is 2.2MPa, and the product is obtained through melting, extruding and granulating.
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 (2)
1. The wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition is characterized by comprising the following components in parts by weight:
PPS resin 55;
carbon fibers 30;
glass beads 10;
low density polyethylene LDPE 5;
0.3 of antioxidant;
the PPS resin is PPS with MI316 ℃ of 5kg of 300g/10 min;
the carbon fiber is T700 carbon fiber;
the glass beads are solid beads with the particle size of 2um, are used for improving the flowability of the material and simultaneously promote the carbon fibers to flow along the flowing direction;
the weight average molecular weight of the low-density polyethylene LDPE is 3000, and the LDPE is used for promoting the carbon fibers to be arranged along the flowing direction and improving the retention length of the carbon fibers;
the antioxidant adopts antioxidant 1010 and antioxidant 168 produced by CIBA company;
the preparation method of the wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition comprises the following steps:
PPS resin, low-density polyethylene LDPE and an antioxidant are mixed and then fed from a main feeding port of an extruder; respectively feeding carbon fibers and glass beads from a side feeding port of an extruder; and (2) performing melt extrusion at 280-310 ℃, wherein the rotating speed of a screw extruder is 500rpm, the pressure is 2MPa, and performing melt extrusion and granulation to obtain the wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition.
2. A method for preparing the abrasion resistant and fire retardant carbon fiber reinforced polyphenylene sulfide composition according to claim 1, comprising the steps of:
PPS resin, low-density polyethylene LDPE and an antioxidant are mixed and then fed from a main feeding port of an extruder; respectively feeding carbon fibers and glass beads from a side feeding port of an extruder; and (2) performing melt extrusion at 280-310 ℃, wherein the rotating speed of a screw extruder is 500rpm, the pressure is 2MPa, and performing melt extrusion and granulation to obtain the wear-resistant flame-retardant carbon fiber reinforced polyphenylene sulfide composition.
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