CN113549323B - High-strength high-fluidity low-warpage long glass fiber reinforced polyamide composite material and preparation method and application thereof - Google Patents
High-strength high-fluidity low-warpage long glass fiber reinforced polyamide composite material and preparation method and application thereof Download PDFInfo
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- 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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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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Abstract
The invention provides a glass fiber reinforced polyamide composite material granule, which comprises flat glass fibers; the length direction of the flat glass fibers is distributed in the same direction as the length direction of the polyamide composite material granules. The invention also provides the high-strength flat continuous long glass fiber reinforced PA66 composite material, which not only increases the mechanical property of the PA66 composite material, but also improves the fluidity and the appearance of a product, reduces the buckling deformation of a composite material product, can obviously improve the mechanical property, the length of a runner and the surface quality of the long glass fiber reinforced PA66 composite material, ensures that the prepared industrial fan blade is not easy to buckle deformation, is stable to use under the condition of high-speed rotation, and meets the development new requirements of the industrial fan blade material on high mechanical property, high dimensional stability, high surface quality and low water absorption.
Description
Technical Field
The invention belongs to the technical field of glass fiber modified polyamide composite materials, relates to a glass fiber reinforced polyamide composite material granule, a glass fiber reinforced polyamide composite material, a preparation method and application thereof, and particularly relates to a high-strength high-fluidity low-warpage long glass fiber reinforced polyamide (PA 66) composite material, a preparation method and application thereof.
Background
Polyamide resin, named polyamide, PA for short. Commonly known as Nylon (Nylon), which is a generic term for polymers containing amide groups in the repeat units of the macromolecular backbone. Is the variety with the largest yield, the largest variety and the largest application in the five engineering plastics. PA66, also known as polyamide 66 or nylon 66, is more widely used in the automotive industry, instrument housings and other products requiring impact resistance and high strength, and is widely used in the manufacture of parts for mechanical, automotive, chemical and electrical devices, such as gears, rollers, pulleys, rollers, impellers in pump bodies, fan blades, high pressure seals, valve seats, gaskets, bushings, various handles, support frames, wire wrap inner layers, and the like.
Compared with the short glass fiber reinforced PA66 composite material, the long glass fiber reinforced PA66 composite material has better mechanical property, thermal stability and dimensional stability due to longer fiber retention length, and is widely applied to the fields of construction, automobiles, household appliances and the like. With the improvement of the living standard of people, especially the rapid development of the building industry, the industrial fan is widely applied to industrial plants, logistics storage, waiting rooms, exhibition halls, gymnasiums, super-equal-altitude spaces, and is a common industrial machine for ventilation of spaces and cooling of personnel. Industrial fans place higher demands on the performance of the blade material. In the existing long glass fiber PA66 fan blade material, the fiber retention length is longer, the fluidity is poor, the processing performance is poor in the injection molding process due to the fact that the product is larger, the surface quality of the product is poor, the requirements on the injection molding process and the injection molding machine are high, and the water absorption of the material is serious. And the fan blade is easy to warp and deform, has low mechanical property, and is unfavorable for the stability of the fan blade in high-speed rotation.
Thus, how to find a more suitable glass fiber reinforced polyamide composite material, and to reasonably solve the existing problems of the glass fiber reinforced polyamide composite material, is also one of the focuses of attention of many researchers with prospective properties in the field.
Disclosure of Invention
In view of the above, the technical problems to be solved by the invention are a glass fiber reinforced polyamide composite material granule, a glass fiber reinforced polyamide composite material, a preparation method and application thereof, in particular to a high-strength high-flow low-warpage long glass fiber reinforced polyamide (PA 66) composite material, which can remarkably improve the mechanical property, the runner length and the surface quality of the long glass fiber reinforced PA66 composite material, and the prepared industrial fan blade is not easy to warp and deform, is stable to use under the condition of high-speed rotation, and meets the new development requirement of the industrial fan blade material.
The invention provides a glass fiber reinforced polyamide composite material granule, which comprises flat glass fibers;
the length direction of the flat glass fibers is distributed in the same direction as the length direction of the polyamide composite material granules.
Preferably, the flat glass fiber is specifically a glass fiber with a flat section;
the section length of the flat glass fiber is 9.75-11.5 mu m;
the cross-sectional width of the flat glass fiber is 1.4-3.25 mu m;
the cross-section width-to-thickness ratio of the flat glass fiber is (3-8): 1, a step of;
the length of the polyamide composite material granules is 8-15 mm.
Preferably, the length of the flat glass fibers is equal to the length of the polyamide composite pellets;
the single polyamide composite material granule contains 4000-4800 flat glass fibers;
the mass content of the flat glass fiber in the polyamide composite material granules is 20% -60%;
the polyamide composite material is a flat long glass fiber continuous distribution polyamide composite material;
the polyamide composite material granules are resin raw materials for preparing fan blades.
The invention provides a glass fiber reinforced polyamide composite material, which comprises the following raw materials in parts by mass:
preferably, the PA66 resin comprises a low viscosity polyamide resin;
the relative viscosity of the PA66 resin is 2.42-2.48;
the semi-aromatic nylon is obtained by polycondensation synthesis of m-xylylenediamine and adipic acid;
the melt index of the semi-aromatic nylon is 41.8g/10min;
the flat glass fibers include long flat glass fibers.
Preferably, the length of the flat glass fiber is 6500-9000 m;
the flat glass fiber is specifically a flat glass fiber with an auxiliary agent compounded on the surface;
the auxiliary agent comprises one or more of a sizing agent, a film forming agent, a coupling agent, a lubricant, a defoaming agent and acid;
the mass ratio of the auxiliary agent to the flat glass fiber is 0.15-1.2%.
Preferably, the lubricant comprises an ethylene acrylic acid copolymer and/or an amide wax;
the nucleating agent comprises a P22 nucleating agent;
the antioxidant comprises hindered phenol antioxidants and/or phosphite antioxidants;
the color master batch comprises one or more of nylon 66 carrier carbon black master batch, PP carrier carbon black master batch and nylon 66 aniline black master batch;
after the glass fiber reinforced polyamide composite material is pelletized, the glass fiber reinforced polyamide composite material pellet in any one of the technical schemes is obtained.
The invention provides a preparation method of a glass fiber reinforced polyamide composite material, which comprises the following steps:
1) Mixing PA66 resin, semi-aromatic nylon resin, lubricant, nucleating agent and antioxidant to obtain premix;
2) And (3) feeding the molten material obtained by the premix obtained by the steps after double-screw melting extrusion into a dipping mold in which the flat glass fibers are placed, taking out the mold after the molten material is dipped into the flat glass fibers, and cooling to obtain the glass fiber reinforced polyamide composite material.
Preferably, the twin-screw melt extrusion has a twin-screw aspect ratio of (30 to 60): 1, a step of;
the temperature of the double-screw melt extrusion is 250-280 ℃;
the vacuum pressure of the double-screw melt extrusion is less than or equal to 0.02Mpa;
the flat glass fiber is specifically a flat glass fiber with a surface composited with an impregnating compound;
the temperature in the impregnation die is 260-280 ℃;
the cooling mode comprises water cooling;
and (3) granulating after cooling to obtain glass fiber reinforced polyamide composite material granules.
The invention also provides glass fiber reinforced polyamide composite material granules according to any one of the technical schemes, glass fiber reinforced polyamide composite material according to any one of the technical schemes or application of the glass fiber reinforced polyamide composite material prepared by the preparation method according to any one of the technical schemes in fan blade aspect.
The invention provides a glass fiber reinforced polyamide composite material granule, which comprises flat glass fibers; the length direction of the flat glass fibers is distributed in the same direction as the length direction of the polyamide composite material granules. Compared with the prior art, the invention aims at the problems of the existing long glass fiber PA66 fan blade material, and researches prove that the fiber has longer retention length, poor fluidity, poor processing performance in the injection molding process due to larger product, poor product surface quality, higher requirements on the injection molding process and the injection molding machine, and serious water absorption of the material. The cylindrical glass fiber is highly oriented in the pellet injection molding process, and the PA66 is also a crystalline material, so that the shrinkage rate of the long glass fiber reinforced PA66 composite material in each direction is large, and finally, the fan blade is extremely easy to warp and deform. The mechanical property of the PA66 composite material fan blade prepared by adopting the cylindrical glass fiber with common strength and modulus is lower, which is not beneficial to the stability of the fan blade in high-speed rotation.
The invention particularly relates to a polyamide composite material granule containing flat glass fibers, which contains oriented flat glass fibers, so that a corresponding high-strength high-flow low-warpage long glass fiber reinforced polyamide composite material is obtained. The high-strength flat continuous long glass fiber reinforced PA66 composite material provided by the invention utilizes the high-strength continuous flat glass fiber to replace common cylindrical glass fiber, so that the mechanical property of the glass fiber reinforced PA66 composite material is improved, the fluidity and the appearance of a product of the glass fiber reinforced PA66 composite material are improved, and the buckling deformation of a product of the flat long glass fiber reinforced PA66 composite material is reduced. Meanwhile, the high fluidity and the special chemical structure of the semi-aromatic nylon are utilized, and the water absorption of the long glass fiber reinforced PA66 composite material is reduced on the premise of further improving the wettability, fluidity and mechanical property of the nylon resin to glass fibers. Meets the development requirements of high mechanical property, high dimensional stability, high surface quality and low water absorption of the industrial fan blade material.
The high-strength high-fluidity low-warpage long glass fiber reinforced PA66 composite material and the preparation method thereof provided by the invention can overcome the defects of low mechanical property, poor fluidity, easiness in buckling deformation, poor surface quality and high water absorption rate of the conventional long glass fiber reinforced PA66 composite material, can remarkably improve the mechanical property, runner length and surface quality of the long glass fiber reinforced PA66 composite material, and can ensure that the prepared industrial fan blade is not easy to buckle deformation, is stable in use under the condition of high-speed rotation, and meets the new development requirement of the industrial fan blade material.
Experimental results show that the high-strength flat continuous long glass fiber reinforced PA66 composite material provided by the invention utilizes the high-strength continuous flat glass fiber to replace common cylindrical glass fiber, so that the mechanical property of the PA66 composite material is enhanced, the fluidity of the PA66 composite material and the appearance of a product are improved, and the buckling deformation and the water absorption of the product are reduced.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further the features and advantages of the invention and are not limiting of the patent claims of the invention.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs analytically pure or conventional purity used in the field of polyamide production.
The invention provides a glass fiber reinforced polyamide composite material granule, which comprises flat glass fibers;
the length direction of the flat glass fibers is distributed in the same direction as the length direction of the polyamide composite material granules.
In the present invention, the homeotropic distribution is preferably such that the length direction of the flat glass fibers is parallel or slightly angled to the length direction of the polyamide composite pellets. The length direction of the flat glass fibers is consistent with the length direction of the polyamide composite material pellets as a whole.
In the present invention, the flat glass fiber is preferably a glass fiber having a flat cross section.
In the present invention, the flat glass fiber preferably has a cross-sectional length of 9.75 to 11.5. Mu.m, more preferably 10.05 to 11.2. Mu.m, still more preferably 10.35 to 10.9. Mu.m.
In the present invention, the flat glass fiber preferably has a cross-sectional width of 1.4 to 3.25. Mu.m, more preferably 1.7 to 3.0. Mu.m, still more preferably 2.0 to 2.7. Mu.m, still more preferably 2.3 to 2.4. Mu.m.
In the present invention, the flat glass fiber preferably has a cross-sectional aspect ratio of (3 to 8): 1, more preferably (4 to 7): 1, more preferably (5 to 6): 1.
in the present invention, the length of the polyamide composite material pellet is preferably 8 to 15mm, more preferably 9 to 14mm, still more preferably 10 to 13mm, and still more preferably 11 to 12mm.
In the present invention, the length of the flat glass fibers is preferably equal to the pellet length of the polyamide composite material.
In the present invention, the polyamide composite material pellets preferably contain 4000 to 4800 flat glass fibers, more preferably 4100 to 4700, still more preferably 4200 to 4600, still more preferably 4300 to 4500.
In the present invention, the mass content of the flat glass fibers in the polyamide composite material pellet is preferably 20% to 60%, more preferably 25% to 55%, still more preferably 30% to 50%, still more preferably 35% to 45%.
In the present invention, the polyamide composite material is preferably a flat long glass fiber continuous distribution polyamide composite material.
In the present invention, the polyamide composite material pellet is preferably a resin raw material for producing fan blades.
The invention provides a glass fiber reinforced polyamide composite material, which comprises the following raw materials in parts by mass:
in the present invention, the amount of the PA66 resin added is preferably 30 to 60 parts by weight, more preferably 35 to 55 parts by weight, and still more preferably 40 to 50 parts by weight.
In the present invention, the PA66 resin preferably includes a low viscosity polyamide resin. The relative viscosity of the PA66 resin is preferably 2.42 to 2.48, more preferably 2.43 to 2.47, and still more preferably 2.44 to 2.46. Specifically, the PA66 resin brand may be EPR24 type resin of the godet company.
In the present invention, the amount of the semiaromatic nylon to be added is preferably 5 to 20 parts by weight, more preferably 8 to 17 parts by weight, and still more preferably 11 to 14 parts by weight.
In the present invention, the semiaromatic nylon is preferably synthesized by polycondensation of m-xylylenediamine and adipic acid, and is a crystalline polyamide resin. Specifically, the melt index of the semi-aromatic nylon is preferably 41.8g/10min, wherein the melt index is 41.8g/10min under the test condition of 275 ℃/2.16 kg.
In the present invention, the amount of the flat glass fiber to be added is preferably 30 to 50 parts by weight, more preferably 34 to 46 parts by weight, still more preferably 38 to 42 parts by weight.
In the present invention, the flat glass fibers preferably include flat long glass fibers, more preferably continuous flat long glass fibers. The length of the flat glass fiber is preferably 6500 to 9000m, more preferably 7000 to 8500m, and still more preferably 7500 to 8000m.
In the present invention, the flat glass fiber is preferably a flat glass fiber having an auxiliary agent compounded on the surface thereof.
In the present invention, the auxiliary agent preferably includes one or more of a sizing agent, a film-forming agent, a coupling agent, a lubricant, an antifoaming agent, and an acid, and more preferably a sizing agent, a film-forming agent, a coupling agent, a lubricant, an antifoaming agent, or an acid.
In the present invention, the mass ratio of the auxiliary agent to the flat glass fiber is preferably 0.15% to 1.2%, more preferably 0.35% to 1.0%, and still more preferably 0.55% to 0.8%.
In the present invention, the amount of the lubricant to be added is preferably 0.1 to 1 part by weight, more preferably 0.3 to 0.8 part by weight, and still more preferably 0.5 to 0.6 part by weight. The lubricant preferably comprises an ethylene acrylic acid copolymer and/or an amide wax, more preferably an ethylene acrylic acid copolymer or an amide wax.
In the present invention, the nucleating agent is preferably added in an amount of 0.05 to 0.5 part by weight, more preferably 0.15 to 0.4 part by weight, still more preferably 0.25 to 0.3 part by weight. The nucleating agent preferably comprises a P22 nucleating agent. Specifically, the nucleating agent may be P22, which is a bougueman brand.
In the present invention, the antioxidant is preferably added in an amount of 0.2 to 3 parts by weight, more preferably 0.7 to 2.5 parts by weight, and still more preferably 1.2 to 2.2 parts by weight.
In the present invention, the antioxidant preferably includes a hindered phenol-based antioxidant and/or a phosphite-based antioxidant, more preferably a hindered phenol-based antioxidant or a phosphite-based antioxidant.
In the present invention, the amount of the masterbatch to be added is preferably 0 to 2 parts by weight, more preferably 0.4 to 1.6 parts by weight, still more preferably 0.8 to 1.2 parts by weight.
In the present invention, the color master batch preferably includes one or more of nylon 66 carrier carbon black master batch, PP carrier carbon black master batch and nylon 66 aniline black master batch, more preferably nylon 66 carrier carbon black master batch, PP carrier carbon black master batch or nylon 66 aniline black master batch.
In the invention, after the glass fiber reinforced polyamide composite material is pelletized, the glass fiber reinforced polyamide composite material pellet in any one of the technical schemes is obtained.
The invention provides a preparation method of a glass fiber reinforced polyamide composite material, which comprises the following steps:
1) Mixing PA66 resin, semi-aromatic nylon resin, lubricant, nucleating agent and antioxidant to obtain premix;
2) And (3) feeding the molten material obtained by the premix obtained by the steps after double-screw melting extrusion into a dipping mold in which the flat glass fibers are placed, taking out the mold after the molten material is dipped into the flat glass fibers, and cooling to obtain the glass fiber reinforced polyamide composite material.
Firstly, mixing PA66 resin, semi-aromatic nylon resin, a lubricant, a nucleating agent and an antioxidant to obtain a premix.
The invention further comprises the steps of feeding the molten material obtained by the steps of carrying out double-screw melting extrusion on the premix into a dipping mold in which the flat glass fibers are placed, taking out the mold after the molten material is dipped in the flat glass fibers, and cooling to obtain the glass fiber reinforced polyamide composite material.
In the present invention, the twin-screw melt extrusion preferably has a twin-screw aspect ratio of (30 to 60): 1, more preferably (35 to 55): 1, more preferably (40 to 50): 1.
in the present invention, the temperature of the twin-screw melt extrusion is preferably 250 to 280 ℃, more preferably 255 to 275 ℃, and still more preferably 260 to 270 ℃.
In the present invention, the vacuum pressure of the twin-screw melt extrusion is preferably 0.02Mpa or less, more preferably 0.01Mpa or less, more preferably 0.001Mpa or less, more preferably 0.0001Mpa or less.
In the present invention, the flat glass fiber is preferably flat in cross section, and may be a high-strength continuous flat long glass fiber, specifically, the glass formulation of the high-strength continuous flat long glass fiber may be a high-strength high-modulus glass fiber produced by Chongqing International composite material Co., ltd, and more specifically, a commercially available continuous flat long glass fiber ER5301T-2000 is preferred.
In the present invention, the flat glass fiber is preferably a flat glass fiber having a surface compounded with a sizing agent.
In the present invention, the temperature in the impregnation die is preferably 260 to 280 ℃, more preferably 264 to 276 ℃, and still more preferably 268 to 272 ℃.
In the present invention, the infiltration is preferably cladding.
In the present invention, the cooling means preferably includes water cooling.
In the present invention, the cooled and pelletized polyamide composite material pellets are preferably obtained.
The invention relates to a complete and refined integral preparation process, which better ensures the performance of a glass fiber reinforced polyamide composite material, better reduces the buckling deformation degree and the water absorption of a flat long glass fiber reinforced PA66 composite material product, improves the mechanical property, the dimensional stability and the surface quality, and the preparation method of the glass fiber reinforced polyamide composite material specifically comprises the following steps:
step 1: the section of the high-strength continuous flat long glass fiber is flat, the glass formula of the high-strength continuous flat long glass fiber is preferably Chongqing international high-strength high-modulus glass fiber, and the surface of the high-strength continuous flat long glass fiber is coated with an impregnating compound with good compatibility with PA66 resin.
Step 2: uniformly mixing PA66 resin, semi-aromatic nylon resin, lubricant, nucleating agent, antioxidant and black master batch in a high-speed mixer according to a proportion to obtain premix;
step 3: adding the premix obtained in the step 2 into a mixture with the length-diameter ratio of (30-60): and 1, simultaneously penetrating the 16 rolls of high-strength continuous flat glass fibers in the step 1 through a melting dipping die, melting and extruding the premix through the double-screw extruder, then entering the dipping die, fully dipping the high-strength continuous flat glass fibers in the dipping die, cooling and forming in a cooling water tank, and granulating to obtain the high-strength high-flow low-warpage long glass fiber reinforced PA66 composite material.
Wherein, the processing temperature of each section of the double-screw extruder is preferably controlled between 250 and 280 ℃, the vacuum degree is preferably-0.1 MPa, and the temperature of the impregnating mold is preferably 280 ℃. More specifically, the twin screw extruder had an aspect ratio of 48:1. in step 3, the premix is fed into the twin-screw extruder at a rate of 60 kg/hr for melt dispersion while passing the high-strength continuous flat glass fiber through a dipping mold, and the drawing speed thereof may be 20m/min.
The invention also provides glass fiber reinforced polyamide composite material granules according to any one of the technical schemes, glass fiber reinforced polyamide composite material according to any one of the technical schemes or application of the glass fiber reinforced polyamide composite material prepared by the preparation method according to any one of the technical schemes in fan blade aspect.
The invention provides a high-strength high-fluidity low-warpage long glass fiber reinforced polyamide (PA 66) composite material, and a preparation method and application thereof. The polyamide composite material granules containing the flat glass fibers provided by the invention contain oriented flat glass fibers, so that the corresponding high-strength high-flow low-warpage long glass fiber reinforced polyamide composite material is obtained. The high-strength flat continuous long glass fiber reinforced PA66 composite material utilizes the high-strength continuous flat glass fiber to replace common cylindrical glass fiber, so that the mechanical property of the glass fiber reinforced PA66 composite material is improved, the fluidity and the appearance of a product of the glass fiber reinforced PA66 composite material are improved, and the buckling deformation of the product of the flat long glass fiber reinforced PA66 composite material is reduced. Meanwhile, the high fluidity and the special chemical structure of the semi-aromatic nylon are utilized, and the water absorption of the long glass fiber reinforced PA66 composite material is reduced on the premise of further improving the wettability, fluidity and mechanical property of the nylon resin to glass fibers. Meets the development requirements of high mechanical property, high dimensional stability, high surface quality and low water absorption of the industrial fan blade material.
The high-strength high-fluidity low-warpage long glass fiber reinforced PA66 composite material and the preparation method thereof provided by the invention can overcome the defects of low mechanical property, poor fluidity, easiness in buckling deformation, poor surface quality and high water absorption rate of the conventional long glass fiber reinforced PA66 composite material, can remarkably improve the mechanical property, runner length and surface quality of the long glass fiber reinforced PA66 composite material, and can ensure that the prepared industrial fan blade is not easy to buckle deformation, is stable in use under the condition of high-speed rotation, and meets the new development requirement of the industrial fan blade material.
Experimental results show that the high-strength flat continuous long glass fiber reinforced PA66 composite material provided by the invention utilizes the high-strength continuous flat glass fiber to replace common cylindrical glass fiber, so that the mechanical property of the PA66 composite material is enhanced, the fluidity of the PA66 composite material and the appearance of a product are improved, and the buckling deformation and the water absorption of the product are reduced.
For further explanation of the present invention, the following describes in detail a glass fiber reinforced polyamide composite pellet, a glass fiber reinforced polyamide composite, a preparation method and an application thereof with reference to examples, but it should be understood that these examples are implemented on the premise of the technical scheme of the present invention, and detailed embodiments and specific operation procedures are given only for further explanation of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the examples described below.
Example 1
The high-strength continuous flat long glass fiber reinforced PA66 composite material 1 comprises the following raw materials:
49.2 kg of PA66 (polyamide) resin, model PA66-EPR24;
16 rolls (4800 rolls each) of high-strength continuous flat long glass fibers, the model is ER5301T-2000, the cross section of the glass fibers is flat, the width-to-thickness ratio of the cross section is 4:1, and the surfaces of the glass fibers are coated with impregnating compound which has good compatibility with PA66 resin;
0.15 kg of lubricant is ethylene-acrylic acid copolymer lubricant;
10 kg of semi-aromatic nylon resin MXD6 with a special chemical structure: is synthesized by polycondensation of m-xylylenediamine and adipic acid;
0.15 kg of hindered phenol type main antioxidant, the model number of which is Irganox 1098, and 0.15 kg of phosphite type antioxidant, the model number of which is Irganox 168;
0.3 kg of black master batch, the model is CABOT-PA3785;
0.05 kg of nucleating agent, and the model is P22.
A preparation method of a high-strength continuous flat long glass fiber reinforced PA66 composite material 1, which is prepared by the following raw materials by weight,
step 1: high strength continuous flat glass fiber model ER 5301T-2000;
step 2: 49.2 kg of PA66 resin of the type PA66-EPR24, 10 kg of semiaromatic nylon MXD6, 0.15 kg of hindered phenol antioxidant of the type Irganox 1098, 0.15 kg of phosphite antioxidant of the type Irganox 168, 0.3 kg of black master batch of the type CABOT-PA3785, 0.15 kg of polyethylene-acrylic acid copolymer lubricant and 0.05 kg of nucleating agent P22 are mixed. Fully and uniformly mixing in a high-speed mixer to obtain a premix 1;
step 3: and (3) feeding the premix 1 obtained in the step (2) from a main feeding port of a double-screw extruder with the length-diameter ratio of 48:1 at the rate of 60 kg/h, simultaneously feeding the 16 rolls of high-strength continuous flat glass fibers in the step (1) through a melting dipping mold, feeding the premix into the dipping mold after being melted and extruded by the double-screw extruder, fully dipping the high-strength continuous flat glass fibers in the dipping mold, cooling and forming in a cooling water tank, and granulating into 12mm long granules to obtain the high-strength continuous flat long glass fiber reinforced PA66 composite material 1 with the glass fiber content of 40%. Wherein the processing temperature of each section of the double-screw extruder is controlled to be 250-280 ℃, the vacuum degree is minus 0.1MPa, and the temperature of the impregnating mold is 280 ℃.
The properties of the high strength continuous flat long glass fiber reinforced PA66 composite 1 with 40% glass fiber content were tested as follows: the injection molding machine condition is 280 ℃, the length of the spiral flow channel of the granules is 750mm (the width is 20mm, the thickness is 2 mm), the shrinkage rate in the flowing direction is 0.12%, the shrinkage rate in the vertical flowing direction is 0.2%, and the water absorption rate (23 ℃ for 24 h) is 0.4%.
The result shows that the high-strength continuous flat long glass fiber reinforced PA66 composite material 1 prepared by the invention has high fluidity, high mechanical property, high dimensional stability and low water absorption. Meets the new development requirement of the industrial fan blade material.
Example 2
The high-strength continuous flat long glass fiber reinforced PA66 composite material 2 comprises the following raw materials:
59.2 kg of PA66 (polyamide) resin, model PA66-EPR24;
16 rolls of high-strength flat long glass fiber, the model is ER5301T-2000, the section of the fiber is flat, and the width-to-thickness ratio of the section is 4:1;
0.15 kg of lubricant is ethylene-acrylic acid copolymer lubricant;
0.15 kg of hindered phenol type main antioxidant, the model number of which is Irganox 1098, and 0.15 kg of phosphite type antioxidant, the model number of which is Irganox 168;
0.3 kg of black master batch, and the model is CABOT-PA3785.
0.05 kg of nucleating agent, and the model is P22.
The preparation method of the high-strength continuous flat long glass fiber reinforced PA66 composite material 2 comprises the steps of preparing raw materials according to the weight;
step 1: high strength continuous flat glass fiber model ER 5301T-2000;
step 2: 59.2 kg of PA66 (polyamide) resin of type PA66-EPR24, 0.15 kg of phenolic antioxidant of type Irganox 1098 and 0.15 kg of phosphite antioxidant of type Irganox 168, 0.3 kg of black masterbatch of type CABOT-PA3785 and 0.15 kg of polyethylene-acrylic acid copolymer lubricant and 0.05 kg of nucleating agent of type P22 were mixed. Fully and uniformly mixing in a high-speed mixer to obtain a premix 2;
step 3: and (2) feeding the premix 2 obtained in the step (2) from a main feeding port of a double-screw extruder with the length-diameter ratio of 48:1 at the rate of 60 kg/h, simultaneously feeding the 16 rolls of high-strength continuous flat glass fibers in the step (1) through a melting and dipping die, feeding the premix into the dipping die after being melted and extruded by the double-screw extruder, fully dipping the high-strength continuous flat glass fibers in the dipping die, cooling and forming in a cooling water tank, and granulating into 12mm long granules to obtain the 40% high-strength continuous flat long glass fiber reinforced PA66 composite material 2. Wherein, the processing temperature of each section of the double-screw extruder is controlled between 250 ℃ and 280 ℃ and the vacuum degree is-0.1 MPa. The impregnation die temperature was 280 ℃.
The properties of the high strength continuous flat long glass fiber reinforced PA66 composite 2 with 40% glass fiber content were tested as follows: under the test condition of the injection molding machine at 280 ℃ and 60Mpa injection pressure, the length of the spiral flow channel of the granules is 720mm (the width is 20mm and the thickness is 2 mm), the shrinkage rate in the flowing direction is 0.15%, the shrinkage rate in the vertical flowing direction is 0.25%, and the water absorption rate (23 ℃ for 24 h) is 0.65%.
The results show that the high-strength continuous flat long glass fiber reinforced PA66 composite material 2 has certain high fluidity, high mechanical property, high dimensional stability, but increased water absorption.
Comparative example 1
The raw materials are taken according to the following components:
59.2 kg of PA66 (polyamide) resin, model PA66-EPR24;
16 rolls of common cylindrical glass fiber, model ER4301R-2400;
0.15 kg of lubricant is ethylene-acrylic acid copolymer lubricant;
0.15 kg of hindered phenol type main antioxidant, the model number of which is Irganox 1098, and 0.15 kg of phosphite type antioxidant, the model number of which is Irganox 168;
0.3 kg of black master batch, and the model is CABOT-PA3785.
0.05 kg of nucleating agent, and the model is P22.
A common long glass fiber reinforced PA66 composite of the comparative example was prepared in the same manner as in step 2 and step 3 of example 1: 59.2 kg of PA66 (polyamide) resin with the model of PA66-EPR24, 0.15 kg of hindered phenol antioxidant with the model of Irganox 1098, 0.15 kg of phosphite antioxidant with the model of Irganox 168, 0.3 kg of black master batch with the model of CABOT-PA3785, 0.15 kg of ethylene-acrylic acid copolymer lubricant and 0.05 kg of nucleating agent P22 are fully and uniformly mixed in a high-speed mixer to obtain a premix of a comparative example;
and (2) simultaneously penetrating the 16 rolls of common cylindrical glass fibers ER4301R-2400 in the step (1) through a melting dipping mold, melting and extruding the premix through the double-screw extruder, then entering the dipping mold, fully dipping the common long glass fibers in the dipping mold, cooling and forming in a cooling water tank, and granulating into 12mm long granules to obtain the 40% common long glass fiber reinforced PA66 composite material. Wherein, the processing temperature of each section of the double-screw extruder is controlled between 250 ℃ and 280 ℃ and the vacuum degree is-0.1 Mpa. The impregnation die temperature was 280 ℃.
Test results show that the performance of the comparative flat long glass fiber reinforced polypropylene composite material with 40% glass fiber content is as follows: under the test condition of the injection molding machine at 280 ℃ and 60Mpa injection pressure, the length of the spiral flow channel of the granules is 700mm (the width is 20mm and the thickness is 2 mm), the shrinkage rate in the flowing direction is 0.2%, the shrinkage rate in the vertical flowing direction is 0.28%, and the water absorption rate (23 ℃ and 24 h) is 1.1%.
The present invention provides a high strength, high flow, low warp, long glass fiber reinforced polyamide (PA 66) composite material, and methods of making and using the same, and specific examples of which are provided herein to illustrate the principles and embodiments of the invention and to assist in understanding the methods of the invention and its core ideas, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems, and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. A glass fiber reinforced polyamide composite pellet, wherein the polyamide composite pellet comprises flat glass fibers;
the length direction of the flat glass fiber is distributed in the same direction as the length direction of the polyamide composite material granules;
the polyamide composite material granules are flat long glass fiber continuous distribution polyamide composite material granules;
the section length of the flat glass fiber is 9.75-11.5 mu m;
the section width of the flat glass fiber is 1.4-3.25 mu m;
the length of the flat glass fiber is equal to the length of the polyamide composite material granules;
the preparation method of the glass fiber reinforced polyamide composite material granule comprises the following steps:
1) Mixing PA66 resin, semi-aromatic nylon resin, lubricant, nucleating agent and antioxidant to obtain premix;
2) And (3) feeding the molten material obtained by the steps after the premix is subjected to double-screw melt extrusion into a dipping mold in which the flat glass fibers are placed, taking out the mold after the molten material is dipped into the flat glass fibers, cooling to obtain a glass fiber reinforced polyamide composite material, and granulating to obtain glass fiber reinforced polyamide composite material granules.
2. Polyamide composite pellet according to claim 1, characterized in that the flat glass fibers are in particular glass fibers with a flat cross section;
the cross-section width-to-thickness ratio of the flat glass fiber is (3-8): 1, a step of;
the length of the polyamide composite material granules is 8-15 mm.
3. The polyamide composite pellet according to claim 1, wherein 4000 to 4800 flat glass fibers are contained in a single polyamide composite pellet;
the mass content of the flat glass fiber in the polyamide composite material granules is 20% -60%.
4. The polyamide composite pellet of claim 1 wherein the twin screw melt extrusion has a twin screw aspect ratio of (30-60): 1, a step of;
the temperature of the double-screw melt extrusion is 250-280 ℃;
the vacuum pressure of the double-screw melt extrusion is less than or equal to 0.02Mpa.
5. The polyamide composite pellet of claim 1 wherein the flat glass fibers are specifically flat glass fibers having a sizing agent compounded on the surface;
the temperature in the impregnation die is 260-280 ℃;
the cooling mode comprises water cooling.
6. A glass fiber reinforced polyamide composite material as claimed in any one of claims 1 to 5, comprising, in parts by mass:
30-60 parts of PA66 resin;
5-20 parts of semi-aromatic nylon;
30-50 parts by weight of flat glass fiber;
0.1-1 parts by weight of a lubricant;
0.05-0.5 parts by weight of a nucleating agent;
0.2-3 parts of an antioxidant;
0-2 parts of color master batch.
7. The polyamide composite material of claim 6 wherein said PA66 resin comprises a low viscosity polyamide resin;
the relative viscosity of the PA66 resin is 2.42-2.48;
the semi-aromatic nylon is obtained by polycondensation synthesis of m-xylylenediamine and adipic acid;
the melt index of the semi-aromatic nylon is 41.8g/10min;
the flat glass fibers include long flat glass fibers.
8. The polyamide composite material of claim 6 wherein said flat glass fibers have a length of 6500 to 9000m;
the flat glass fiber is specifically a flat glass fiber with an auxiliary agent compounded on the surface;
the auxiliary agent comprises one or more of a sizing agent, a film forming agent, a coupling agent, a lubricant, a defoaming agent and acid;
the mass ratio of the auxiliary agent to the flat glass fiber is 0.15% -1.2%.
9. The polyamide composite material of claim 6 wherein said lubricant comprises an ethylene acrylic acid copolymer and/or an amide wax;
the nucleating agent comprises a P22 nucleating agent;
the antioxidant comprises hindered phenol antioxidants and/or phosphite antioxidants;
the color master batch comprises one or more of nylon 66 carrier carbon black master batch, PP carrier carbon black master batch and nylon 66 aniline black master batch;
and granulating the glass fiber reinforced polyamide composite material to obtain glass fiber reinforced polyamide composite material granules.
10. Use of the glass fiber reinforced polyamide composite pellets of any of claims 1 to 5 or the glass fiber reinforced polyamide composite of any of claims 6 to 9 in fan blades.
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| CN115433457B (en) * | 2022-10-09 | 2023-08-22 | 山东龙腾新材料有限公司 | Nylon composite material with stable and compatible glass fibers and preparation method thereof |
| CN116003999A (en) * | 2022-12-12 | 2023-04-25 | 金旸（厦门）新材料科技有限公司 | Low-warpage and easy-to-weld nylon composite material and preparation method thereof |
| CN116239885A (en) * | 2023-02-27 | 2023-06-09 | 山西泰宝密封技术有限公司 | Low-warpage polyamide modified material, mine truck oil cylinder guide ring and preparation process thereof |
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