CN106810829B - Modified glass fiber reinforced PET composition and preparation method thereof - Google Patents
Modified glass fiber reinforced PET composition and preparation method thereof Download PDFInfo
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Abstract
The invention provides a modified glass fiber reinforced PET composition and a preparation method thereof, wherein the modified glass fiber reinforced PET composition is prepared by mixing, extruding and granulating 30-60 parts of PET, 0-10 parts of PBT, 25-45 parts of glass fiber, 5-15 parts of hollow glass beads, 0-5 parts of toughening agent, 5-10 parts of nucleating agent and 5-10 parts of surface improving agent. The compatibility between PET and glass fiber is enhanced by adding the hollow glass beads and the surface modifier; and similar anchoring nodes, namely cross-linking points, are formed between the glass fibers and the basic resin, so that the bonding state of the glass fibers and the resin is improved, and the separation of the glass fibers and the resin is reduced, thereby greatly reducing the exposure of the glass fibers.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and particularly relates to a modified glass fiber reinforced PET composition and a preparation method thereof.
Background
Polyethylene terephthalate (PET for short) was the earliest polyester material to be industrialized, but was almost used for synthetic fibers at the beginning; after the 80 s, PET was gradually used as engineering plastic and as thermoplastic polyester together with polybutylene terephthalate (PBT) as one of five major engineering plastics after the nucleating agent and crystallization promoter were successively developed. PET has excellent physical and mechanical properties within a wide temperature range, and the long-term use temperature can reach 120 ℃; the electric insulation property is excellent, and even under high temperature and high frequency, the electric property is still good; PET also has excellent creep resistance, fatigue resistance, rub resistance and dimensional stability; therefore, it is widely used as fiber, film, engineering plastic, polyester bottle, etc. However, PET has slow crystallization rate, difficult forming and processing, high molding temperature, long production period and poor impact property. The processability and physical properties are generally improved by reinforcing, filling, blending, etc., and among them, the reinforcing effect by glass fibers is remarkable, and the rigidity, heat resistance, chemical resistance, electrical properties and weather resistance of the resin are improved. Although the glass fiber reinforced PET product greatly improves various strengths of the product, the surface of an injection molding part has floating fibers, which not only affects the appearance, but also affects the performance of the pressure-resistant part.
Disclosure of Invention
The invention aims to provide a modified glass fiber reinforced PET composition and a preparation method thereof, which improve the condition of fiber floating on the surface of the PET composition and improve the appearance and pressure resistance of a workpiece.
The technical scheme of the invention is as follows:
the modified glass fiber reinforced PET composition is prepared from the following components in parts by weight:
30-60 parts of PET (polyethylene terephthalate),
0-10 parts of PBT (polybutylene terephthalate),
25-45 parts of glass fiber,
5-15 parts of hollow glass beads,
0-5 parts of a toughening agent,
5-10 parts of a nucleating agent,
5-10 parts of a surface improver.
Further, the intrinsic viscosity of the PET ranges from 0.6 to 1.0 dl/g.
The glass fiber is chopped glass fiber, the length of the chopped glass fiber is 2-5mm, and the diameter of the chopped glass fiber is 7-13 microns.
The average grain diameter of the hollow glass microspheres is 100 mu m, the compressive strength is 100Mpa, and the density is 0.25 g/cc.
The toughening agent is selected from one or more of maleic anhydride grafted ethylene-octene copolymer, ethylene-methyl acrylate copolymer or ethylene-methyl acrylate-glycidyl methacrylate.
The nucleating agent is sodium benzoate.
The surface improver is ethylene bis fatty acid amide (TAF) and silicone, and the mass ratio of the ethylene bis fatty acid amide (TAF) to the silicone is 1: 1, and mixing the components.
The invention also aims to provide a preparation method of the modified glass fiber reinforced PET composition, which comprises the following steps:
(1) respectively drying PET and PBT;
(2) adding the dried PET, PBT, glass fiber, hollow glass bead, toughening agent, nucleating agent and surface improver into a high-speed mixer according to the proportion and stirring for 3-5 min;
(3) and adding the uniformly mixed materials from a feed inlet of a double-screw extruder, and performing melt extrusion and granulation by the double-screw extruder to prepare the glass fiber reinforced PET composition.
Further, in the step (1), the PET is dried for 4-5h at the temperature of 110-; the PBT is dried for 4-5h at the temperature of 110-120 ℃;
in the step (3), the first zone temperature of the double-screw extruder is 220-250 ℃, the second zone temperature is 225-265 ℃, the third zone temperature is 235-275 ℃, the fourth zone temperature is 245-285 ℃, the fifth zone temperature is 240-280 ℃, the sixth zone temperature is 245-285 ℃, the head temperature is 245-285 ℃, and the rotating speed of the host is 15-35 HZ.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the invention, the hollow glass beads and the surface improver are added into the modified glass fiber reinforced PET, and because the TAF in the surface improver introduces polar groups on the basis of ethylene bis fatty acid amide, the compatibility between the PET and the glass fiber is enhanced after the TAF and the hollow glass beads are mixed; and similar anchoring nodes, namely cross-linking points, are formed between the glass fibers and the basic resin, so that the bonding state of the glass fibers and the resin is improved, and the separation of the glass fibers and the resin is reduced.
2. The hollow glass beads and the surface improver are matched with each other, so that the dispersity of the glass fibers is improved, the interface bonding strength of PET and the glass fibers is increased, and the separation of the glass fibers and resin is reduced, so that the exposure of the glass fibers is greatly reduced.
3. The modified glass fiber reinforced PET composition prepared by the invention has excellent mechanical properties.
Detailed Description
The present invention will be further described with reference to the following examples.
The mechanical property test method comprises the following steps:
the modified glass fiber reinforced PET compositions prepared in the following examples were injection molded into test specimens according to the GB standard, i.e., injection molded at 230-270 ℃ using a plastic injection molding machine. After the sample is molded, the sample is placed in a standard environment with the temperature of (23 +/-2) DEG C and the humidity of (50 +/-5)% for 16h and then tested, wherein the test environment is (23 +/-2) DEG C and the humidity is (50 +/-5)%.
The spline dimensions (length × width × thickness) are: tensile bars (dumbbell type), 170.0 × 10.0 × 4.0; curved splines, 80.0 × 10.0 × 4.0; unnotched impact specimen, 80.0 × 10.0 × 4.0; notched impact bar, 80.0X 10.0X 4.0, V notch, notch depth 1/5.
Tensile strength and elongation at break: the tensile rate was 5mm/min, as measured in GB 1040.
Flexural strength and flexural modulus: the bending speed was 1.25mm/min, measured according to GB 9341.
Impact strength of the simply supported beam notch: testing according to GB 1043.
Example 1
(1) Drying PET at 110 deg.C for 4 hr;
(2) weighing 60 parts of dried PET, 25 parts of glass fiber, 5 parts of hollow glass microsphere, 5 parts of sodium benzoate and 10 parts of surface modifier (weight ratio of TAF to silicone is 1: 1);
(3) stirring the materials weighed in the step (2) in a high-speed mixer for 3 min;
(4) then adding the uniformly mixed materials into a feed inlet of a double-screw extruder;
(5) the materials are melted, extruded and granulated by a double-screw extruder to obtain the modified glass fiber reinforced PET composition;
the processing technology of the double-screw extruder comprises the following steps: the temperature of a first zone of the double-screw extruder is 230 ℃, the temperature of a second zone is 245 ℃, the temperature of a third zone is 255 ℃, the temperature of a fourth zone is 265 ℃, the temperature of a fifth zone is 260 ℃, the temperature of a sixth zone is 265 ℃, the temperature of a machine head is 265 ℃, and the rotating speed of a main machine is 15 HZ. The results of the performance tests are shown in Table 1.
Example 2
(1) Drying PET at the temperature of 110 ℃ for 4 h; drying the PBT for 4h at the temperature of 110 ℃;
(2) weighing 40 parts of dried PET, 10 parts of PBT, 30 parts of glass fiber, 5 parts of hollow glass microsphere, 5 parts of toughening agent (maleic anhydride grafted ethylene-octene copolymer and ethylene-methyl acrylate copolymer), 10 parts of sodium benzoate and 8 parts of surface modifier (TAF: silicone weight ratio is 1: 1);
(3) stirring the materials weighed in the step (2) in a high-speed mixer for 3 min;
(4) then adding the uniformly mixed materials into a feed inlet of a double-screw extruder;
(5) the materials are melted, extruded and granulated by a double-screw extruder to obtain the modified glass fiber reinforced PET composition;
the processing technology of the double-screw extruder comprises the following steps: the temperature of a first zone of the double-screw extruder is 220 ℃, the temperature of a second zone is 225 ℃, the temperature of a third zone is 235 ℃, the temperature of a fourth zone is 245 ℃, the temperature of a fifth zone is 240 ℃, the temperature of a sixth zone is 245 ℃, the temperature of a machine head is 245 ℃, and the rotating speed of a main machine is 35 HZ. The results of the performance tests are shown in Table 1.
Example 3
(1) Drying PET at the temperature of 110 ℃ for 4 h; drying the PBT for 4h at the temperature of 110 ℃;
(2) weighing 40 parts of dried PET, 5 parts of PBT, 35 parts of glass fiber, 10 parts of hollow glass microsphere, 3 parts of toughening agent (ethylene-methyl acrylate-glycidyl methacrylate), 5 parts of sodium benzoate and 5 parts of surface modifier (TAF: silicone weight ratio is 1: 1);
(3) stirring the materials weighed in the step (2) in a high-speed mixer for 3 min;
(4) then adding the uniformly mixed materials into a feed inlet of a double-screw extruder;
(5) the materials are melted, extruded and granulated by a double-screw extruder to obtain the modified glass fiber reinforced PET composition;
the processing technology of the double-screw extruder comprises the following steps: the temperature of a first zone of the double-screw extruder is 240 ℃, the temperature of a second zone is 255 ℃, the temperature of a third zone is 265 ℃, the temperature of a fourth zone is 275 ℃, the temperature of a fifth zone is 270 ℃, the temperature of a sixth zone is 275 ℃, the temperature of a machine head is 275 ℃, and the rotating speed of a main machine is 15 HZ. The results of the performance tests are shown in Table 1.
Example 4
(1) Drying PET at 120 deg.C for 5 h; drying the PBT for 5h at the temperature of 120 ℃;
(2) weighing 30 parts of dried PET, 5 parts of PBT, 45 parts of glass fiber, 15 parts of hollow glass microsphere, 5 parts of sodium benzoate and 5 parts of surface improver (the weight ratio of TAF to silicone is 1: 1);
(3) stirring the materials weighed in the step (2) in a high-speed mixer for 5 min;
(4) then adding the uniformly mixed materials into a feed inlet of a double-screw extruder;
(5) the materials are melted, extruded and granulated by a double-screw extruder to obtain the modified glass fiber reinforced PET composition;
the processing technology of the double-screw extruder comprises the following steps: the temperature of a first zone of the double-screw extruder is 250 ℃, the temperature of a second zone is 265 ℃, the temperature of a third zone is 275 ℃, the temperature of a fourth zone is 285 ℃, the temperature of a fifth zone is 280 ℃, the temperature of a sixth zone is 285 ℃, the temperature of a machine head is 285 ℃, and the rotating speed of a main machine is 20 HZ. The results of the performance tests are shown in Table 1.
Comparative example 1
(1) Drying PET at the temperature of 110 ℃ for 4 h; drying the PBT for 4h at the temperature of 110 ℃;
(2) weighing 50 parts of dried PET, 5 parts of PBT, 35 parts of glass fiber, 5 parts of a toughening agent (ethylene-methyl acrylate-glycidyl methacrylate) and 5 parts of sodium benzoate;
(3) stirring the materials weighed in the step (2) in a high-speed mixer for 3 min;
(4) then adding the uniformly mixed materials into a feed inlet of a double-screw extruder;
(5) melting and extruding the materials by a double-screw extruder, and granulating;
the processing technology of the double-screw extruder comprises the following steps: the temperature of a first zone of the double-screw extruder is 220 ℃, the temperature of a second zone is 225 ℃, the temperature of a third zone is 235 ℃, the temperature of a fourth zone is 245 ℃, the temperature of a fifth zone is 240 ℃, the temperature of a sixth zone is 245 ℃, the temperature of a machine head is 245 ℃, and the rotating speed of a main machine is 15 HZ. The results of the performance tests are shown in Table 1.
Comparative example 2
(1) Drying PET at 140 deg.C for 4-5 h; drying the PBT for 5h at the temperature of 120 ℃;
(2) weighing 40 parts of dried PET, 5 parts of PBT, 35 parts of glass fiber, 10 parts of calcium sulfate hollow glass microspheres, 5 parts of a toughening agent (ethylene-methyl acrylate-glycidyl methacrylate) and 5 parts of sodium benzoate;
(3) stirring the materials weighed in the step (2) in a high-speed mixer for 5 min;
(4) then adding the uniformly mixed materials into a feed inlet of a double-screw extruder;
(5) melting and extruding the materials by a double-screw extruder, and granulating;
the processing technology of the double-screw extruder comprises the following steps: the temperature of a first zone of the double-screw extruder is 220 ℃, the temperature of a second zone is 225 ℃, the temperature of a third zone is 235 ℃, the temperature of a fourth zone is 245 ℃, the temperature of a fifth zone is 240 ℃, the temperature of a sixth zone is 245 ℃, the temperature of a machine head is 245 ℃, and the rotating speed of a main machine is 35 HZ. The results of the performance tests are shown in Table 1.
Comparative example 3
(1) Drying PET at 120 deg.C for 5 h; drying the PBT for 5h at the temperature of 120 ℃;
(2) weighing 40 parts of dried PET, 5 parts of PBT, 35 parts of glass fiber, 5 parts of a toughening agent (ethylene-methyl acrylate-glycidyl methacrylate) and 5 parts of sodium benzoate;
(3) stirring the materials weighed in the step (2) in a high-speed mixer for 5 min;
(4) then adding the uniformly mixed materials into a feed inlet of a double-screw extruder;
(5) melting and extruding the materials by a double-screw extruder, and granulating;
the processing technology of the double-screw extruder comprises the following steps: the temperature of a first zone of the double-screw extruder is 220 ℃, the temperature of a second zone is 225 ℃, the temperature of a third zone is 235 ℃, the temperature of a fourth zone is 245 ℃, the temperature of a fifth zone is 240 ℃, the temperature of a sixth zone is 245 ℃, the temperature of a machine head is 245 ℃, and the rotating speed of a main machine is 25 HZ. The results of the performance tests are shown in Table 1.
TABLE 1
| Performance of | Testing Method | Sheet Bit | Example 1 | Example 2 | Example 3 | Example 4 | Comparison of Example 1 | Comparison of Example 2 | Comparison of Example 3 |
| Bending strength | GB 9341 | MPa | 171 | 181 | 195 | 211 | 140 | 146 | 146 |
| Flexural modulus | GB 9341 | MPa | 6552 | 7442 | 8563 | 10224 | 5100 | 5700 | 5230 |
| Tensile strength | GB 1040 | MPa | 111 | 112 | 131 | 112 | 95 | 94 | 92 |
| Elongation at break | GB 1040 | % | 15.5 | 21.1 | 15.5 | 13.3 | 2.8 | 3.2 | 3.3 |
| Simply supported beam gap Impact strength | GB 1043 | KJ/ m2 | 21 | 22 | 20 | 21 | 9.4 | 9 | 9.2 |
| Surface of the article | Bright and no Floating fiber | Bright and no Floating fiber | Bright and no Floating fiber | Bright and no Floating fiber | With floats Fiber | With floats Fiber | With floats Fiber |
The compatibility between PET and glass fiber is enhanced by adding the hollow glass beads and the surface modifier; and similar anchoring nodes, namely cross-linking points, are formed between the glass fibers and the basic resin, so that the bonding state of the glass fibers and the resin is improved, and the separation of the glass fibers and the resin is reduced, thereby greatly reducing the exposure of the glass fibers.
As can be seen from the comparison between the examples and the comparative examples in the above Table 1, the bending strength, the bending modulus, the tensile strength, the elongation at break and the notch impact strength of the simple beam of the modified glass fiber reinforced PET composition are all obviously higher than those of the materials prepared by the comparative examples, and the surface of the product is bright and has no floating fiber.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. A modified glass fiber reinforced PET composition is characterized in that: the composition is prepared from the following components in parts by weight:
30-60 parts of PET (polyethylene terephthalate),
0-10 parts of PBT (polybutylene terephthalate),
25-45 parts of glass fiber,
5-15 parts of hollow glass beads,
0-5 parts of a toughening agent,
5-10 parts of a nucleating agent,
5-10 parts of a surface improving agent,
the surface improver is prepared from ethylene bis-fatty acid amide and silicone according to a mass ratio of 1: 1, mixing the components; the nucleating agent is sodium benzoate.
2. The modified glass fiber reinforced PET composition according to claim 1, wherein: the intrinsic viscosity of the PET ranges from 0.6 to 1.0 dl/g.
3. The modified glass fiber reinforced PET composition according to claim 1, wherein: the glass fiber is chopped glass fiber, the length of the chopped glass fiber is 2-5mm, and the diameter of the chopped glass fiber is 7-13 microns.
4. The modified glass fiber reinforced PET composition according to claim 1, wherein: the average grain diameter of the hollow glass microspheres is 100 mu m, the compressive strength is 100Mpa, and the density is 0.25 g/cc.
5. The modified glass fiber reinforced PET composition according to claim 1, wherein: the toughening agent is selected from one or more of maleic anhydride grafted ethylene-octene copolymer, ethylene-methyl acrylate copolymer or ethylene-methyl acrylate-glycidyl methacrylate.
6. A process for preparing a modified glass fiber reinforced PET composition as claimed in any one of claims 1 to 5, wherein: the method comprises the following steps:
(1) respectively drying PET and PBT;
(2) adding the dried PET, PBT, glass fiber, hollow glass bead, toughening agent, nucleating agent and surface improver into a high-speed mixer according to the proportion and stirring for 3-5 min;
(3) and adding the uniformly mixed materials from a feed inlet of a double-screw extruder, and performing melt extrusion and granulation by the double-screw extruder to prepare the modified glass fiber reinforced PET composition.
7. The method of claim 6, wherein: the PET in the step (1) is dried for 4-5h at the temperature of 110-140 ℃; the PBT is dried for 4-5h at the temperature of 110-120 ℃;
in the step (3), the first zone temperature of the double-screw extruder is 220-250 ℃, the second zone temperature is 225-265 ℃, the third zone temperature is 235-275 ℃, the fourth zone temperature is 245-285 ℃, the fifth zone temperature is 240-280 ℃, the sixth zone temperature is 245-285 ℃, the head temperature is 245-285 ℃, and the rotating speed of the host is 15-35 HZ.
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