CN113549323A - High-strength high-flow low-warpage long glass fiber reinforced polyamide composite material, and preparation method and application thereof - Google Patents
High-strength high-flow low-warpage long glass fiber reinforced polyamide composite material, and preparation method and application thereof Download PDFInfo
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- CN113549323A CN113549323A CN202110902102.2A CN202110902102A CN113549323A CN 113549323 A CN113549323 A CN 113549323A CN 202110902102 A CN202110902102 A CN 202110902102A CN 113549323 A CN113549323 A CN 113549323A
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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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The invention provides a glass fiber reinforced polyamide composite material pellet, which comprises flat glass fibers; the flat glass fibers are distributed in the longitudinal direction in the same direction as the polyamide composite pellets. The invention also provides a 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 finished piece, reduces the buckling deformation of a composite material product, and can obviously improve the mechanical property, the flow channel length and the surface quality of the long glass fiber reinforced PA66 composite material.
Description
Technical Field
The invention belongs to the technical field of glass fiber modified polyamide composite materials, and relates to glass fiber reinforced polyamide composite material granules, 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 (PA66) composite material, a preparation method and application thereof.
Background
Polyamide resin, known by the English name of polyamine, abbreviated as PA. Commonly known as Nylon (Nylon), which is a generic name for polymers containing amide groups in the repeat units of the macromolecular backbone. The variety has the maximum yield, the maximum variety and the widest application in five engineering plastics. PA66 is also called polyamide 66 or nylon 66, and is widely used in the automobile industry, instrument housings and other products requiring impact resistance and high strength, and widely used in manufacturing parts of machinery, automobiles, chemical and electrical devices, such as gears, rollers, pulleys, rollers, impellers in pump bodies, fan blades, high-pressure sealing rings, valve seats, gaskets, bushings, various handles, support frames, inner layers of wire bags, and the like.
Compared with the short glass fiber reinforced PA66 composite material, the long glass fiber reinforced PA66 composite material has longer fiber retention length, so that the composite material has better mechanical property, thermal stability and size stability, and is widely applied to the fields of buildings, automobiles, household appliances and the like. Along with the improvement of the living standard of people, especially the rapid development of the building industry, the industrial fan is widely applied to high and large spaces such as industrial factory buildings, logistics storage, waiting rooms, exhibition halls, gymnasiums and business supermarkets, and is used as a common industrial machine for space ventilation and personnel cooling. Industrial fans place higher demands on the performance of the fan 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 in the injection molding process is poor due to the larger part, the surface quality of the part is poor, the requirements on the injection molding process and the injection molding machine are higher, and the water absorption of the material is also serious. But also has the problems that the fan blade is easy to warp and deform, has lower mechanical property, is not beneficial to the stability of the fan blade in high-speed rotation, and the like.
Therefore, how to find a more suitable glass fiber reinforced polyamide composite material and reasonably solve the existing problems of the glass fiber reinforced polyamide composite material is one of the focuses of great concern of many prospective researchers in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is a glass fiber reinforced polyamide composite material pellet, a glass fiber reinforced polyamide composite material, a preparation method and an application thereof, and particularly relates to a high-strength, high-flow and low-warpage long glass fiber reinforced polyamide (PA66) composite material, which can significantly improve the mechanical properties, the length of a flow channel and the surface quality of a long glass fiber reinforced PA66 composite material, and the prepared industrial fan blade is not easy to warp and deform, is stable in use under a high-speed rotation condition, and meets the new development requirements of industrial fan blade materials.
The invention provides a glass fiber reinforced polyamide composite material pellet, which comprises flat glass fibers;
the flat glass fibers are distributed in the longitudinal direction in the same direction as the polyamide composite pellets.
Preferably, the flat glass fiber is a glass fiber with a flat section;
the length of the cross section 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 μm;
the cross-section width-thickness ratio of the flat glass fiber is (3-8): 1;
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;
each 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 polyamide composite material with flat long glass fibers continuously distributed;
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 weight:
preferably, the PA66 resin includes a low viscosity polyamide resin;
the relative viscosity of the PA66 resin is 2.42-2.48;
the semi-aromatic nylon is prepared by condensation polymerization of m-xylylenediamine and adipic acid;
the melt index of the semi-aromatic nylon is 41.8g/10 min;
the flat glass fibers comprise flat long 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 the surface compounded with an auxiliary agent;
the auxiliary agent comprises one or more of a wetting 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 antioxidant and/or phosphite antioxidant;
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 the glass fiber reinforced polyamide composite material granules in any one of the technical schemes.
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, a lubricant, a nucleating agent and an antioxidant to obtain a premix;
2) and (3) feeding the melt material obtained by melting and extruding the premix material through the double screws into an impregnation die with flat glass fibers, infiltrating the flat glass fibers with the melt material, demolding, and cooling to obtain the glass fiber reinforced polyamide composite material.
Preferably, the length-diameter ratio of the twin-screw in the twin-screw melt extrusion is (30-60): 1;
the temperature of the twin-screw melt extrusion is 250-280 ℃;
the vacuum pressure of the twin-screw melt extrusion is less than or equal to 0.02 Mpa;
the flat glass fiber is specifically a flat glass fiber with a surface compounded with a sizing agent;
the temperature in the dipping die is 260-280 ℃;
the cooling mode comprises water cooling;
and pelletizing after cooling to obtain the glass fiber reinforced polyamide composite material granules.
The invention also provides the glass fiber reinforced polyamide composite material pellet of any one of the above technical schemes, the glass fiber reinforced polyamide composite material of any one of the above technical schemes or the application of the glass fiber reinforced polyamide composite material prepared by the preparation method of any one of the above technical schemes in the fan blade aspect.
The invention provides a glass fiber reinforced polyamide composite material pellet, which comprises flat glass fibers; the flat glass fibers are distributed in the longitudinal direction in the same direction as the polyamide composite pellets. 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 retention length is longer, the fluidity is not good, the processing performance is poorer in the injection molding process due to larger parts, the surface quality of the parts is not good, the requirements on the injection molding process and the injection molding machine are higher, and the water absorption of the material is also serious. Cylindrical glass fiber is highly oriented in the process of pellet injection molding, and PA66 is a crystalline material, so that the shrinkage rate of the long glass fiber reinforced PA66 composite material is greatly different in all directions, and finally, the fan blade is extremely easy to warp and deform. The PA66 composite material fan blade prepared by the cylindrical glass fiber with common strength and modulus has lower mechanical property, which is not beneficial to the stability of the fan blade in high-speed rotation.
The invention particularly relates to a polyamide composite pellet containing flat glass fibers, which contains oriented flat glass fibers, and further obtains a corresponding long glass fiber reinforced polyamide composite material with high strength, high fluidity and low warpage. According to the high-strength flat continuous long glass fiber reinforced PA66 composite material provided by the invention, the high-strength continuous flat glass fiber is used for replacing common cylindrical glass fiber, so that the mechanical property of the glass fiber reinforced PA66 composite material is increased, the flowability and the appearance of a workpiece of the glass fiber reinforced PA66 composite material are improved, and the warping deformation of a flat long glass fiber reinforced PA66 composite material product 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 the glass fiber. The development requirements of high mechanical property, high dimensional stability, high surface quality and low water absorption of the industrial fan blade material are met.
The high-strength high-flow 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, easy warpage and deformation, poor surface quality and high water absorption rate of the conventional long glass fiber reinforced PA66 composite material, can obviously improve the mechanical property, the length of a flow channel and the surface quality of a long glass fiber reinforced PA66 composite material, and can ensure that 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 requirements 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 high-strength continuous flat glass fibers to replace common cylindrical glass fibers, so that the mechanical property of the PA66 composite material is enhanced, the flowability and the appearance of a workpiece of the PA66 composite material are improved, and the warping deformation and the water absorption of the product are reduced.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially 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 their purity, and the present invention preferably employs analytical purification or conventional purity used in the field of polyamide production.
The invention provides a glass fiber reinforced polyamide composite material pellet, which comprises flat glass fibers;
the flat glass fibers are distributed in the longitudinal direction in the same direction as the polyamide composite pellets.
In the present invention, the homeotropic distribution is preferably such that the lengthwise direction of the flat glass fibers is parallel to or slightly angled with respect to the lengthwise direction of the polyamide composite pellets. Overall, the length direction of the flat glass fibers coincides with the length direction of the polyamide composite pellets.
In the present invention, the flat glass fiber is particularly preferably a glass fiber having a flat cross section.
In the present invention, the cross-sectional length of the flat glass fiber is preferably 9.75 to 11.5 μm, more preferably 10.05 to 11.2 μm, and still more preferably 10.35 to 10.9 μm.
In the present invention, the cross-sectional width of the flat glass fiber is preferably 1.4 to 3.25. mu.m, more preferably 1.7 to 3.0. mu.m, more preferably 2.0 to 2.7. mu.m, and more preferably 2.3 to 2.4. mu.m.
In the invention, the cross-sectional width-thickness ratio of the flat glass fiber is preferably (3-8): 1, more preferably (4-7): 1, more preferably (5-6): 1.
in the present invention, the length of the polyamide composite pellet is preferably 8 to 15mm, more preferably 9 to 14mm, more preferably 10 to 13mm, and more preferably 11 to 12 mm.
In the present invention, the length of the flat glass fiber is preferably equal to the length of the polyamide composite pellets.
In the present invention, the single polyamide composite pellet preferably contains 4000 to 4800 flat glass fibers, more preferably 4100 to 4700 flat glass fibers, more preferably 4200 to 4600 flat glass fibers, and more preferably 4300 to 4500 flat glass fibers.
In the present invention, the mass content of the flat glass fiber in the polyamide composite pellet is preferably 20% to 60%, more preferably 25% to 55%, more preferably 30% to 50%, 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 pellets are preferably a raw material for a resin used for the production of fan blades.
The invention provides a glass fiber reinforced polyamide composite material, which comprises the following raw materials in parts by weight:
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 polyamide resin having low viscosity. The relative viscosity of the PA66 resin is preferably 2.42-2.48, more preferably 2.43-2.47, and more preferably 2.44-2.46. Specifically, the PA66 resin brand may be EPR24 type resin from suma limited.
In the present invention, the semi-aromatic nylon is preferably added in an amount of 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 semi-aromatic nylon is preferably a crystalline polyamide resin obtained by polycondensation of m-xylylenediamine and adipic acid. Specifically, the semi-aromatic nylon preferably has a melt index of 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 flat glass fiber is preferably added in an amount of 30 to 50 parts by weight, more preferably 34 to 46 parts by weight, and still more preferably 38 to 42 parts by weight.
In the present invention, the flat glass fiber preferably includes a flat long glass fiber, more preferably a continuous flat long glass fiber. The length of the flat glass fiber is preferably 6500-9000 m, more preferably 7000-8500 m, and more preferably 7500-8000 m.
In the present invention, the flat glass fiber is particularly preferably a flat glass fiber having an auxiliary compounded on the surface thereof.
In the present invention, the auxiliary agent preferably includes one or more of an impregnating agent, a film-forming agent, a coupling agent, a lubricant, an antifoaming agent, and an acid, and more preferably an impregnating 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 to the flat glass fibers 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 lubricant is preferably added in an amount of 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 parts by weight, more preferably 0.15 to 0.4 parts by weight, and still more preferably 0.25 to 0.3 parts by weight. The nucleating agent preferably comprises a P22 nucleating agent. Specifically, the nucleating agent may be available under the brand name of P22 from brongman.
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, and more preferably a hindered phenol-based antioxidant or a phosphite-based antioxidant.
In the invention, the addition amount of the color master batch is preferably 0 to 2 parts by weight, more preferably 0.4 to 1.6 parts by weight, and more preferably 0.8 to 1.2 parts by weight.
In the present invention, the color masterbatch preferably comprises one or more of nylon 66 carrier carbon black masterbatch, PP carrier carbon black masterbatch and nylon 66 nigrosine black masterbatch, and more preferably nylon 66 carrier carbon black masterbatch, PP carrier carbon black masterbatch or nylon 66 nigrosine black masterbatch.
In the invention, the glass fiber reinforced polyamide composite material is granulated to obtain the glass fiber reinforced polyamide composite material granule in any one of the above technical schemes.
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, a lubricant, a nucleating agent and an antioxidant to obtain a premix;
2) and (3) feeding the melt material obtained by melting and extruding the premix material through the double screws into an impregnation die with flat glass fibers, infiltrating the flat glass fibers with the melt material, demolding, and cooling to obtain the glass fiber reinforced polyamide composite material.
The invention firstly mixes PA66 resin, semi-aromatic nylon resin, lubricant, nucleating agent and antioxidant to obtain the premix.
The melt material obtained by melting and extruding the premix through the double screws is fed into an impregnation die with flat glass fibers, the melt material is used for infiltrating the flat glass fibers and then is discharged from the die, and the glass fiber reinforced polyamide composite material is obtained after cooling.
In the invention, the length-diameter ratio of the twin-screw in the twin-screw melt extrusion is preferably (30-60): 1, more preferably (35-55): 1, more preferably (40 to 50): 1.
in the invention, the temperature of the twin-screw melt extrusion is preferably 250-280 ℃, more preferably 255-275 ℃, and more preferably 260-270 ℃.
In the present invention, the vacuum pressure in the twin-screw melt extrusion is preferably 0.02MPa or less, more preferably 0.01MPa or less, still more preferably 0.001MPa or less, still more preferably 0.0001MPa or less.
In the present invention, the flat glass fiber preferably has a flat 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 materials Co., Ltd, and more specifically, a commercially available continuous flat long glass fiber ER5301T-2000 is preferred.
In the present invention, the flat glass fibers are preferably flat glass fibers having a surface compounded with a sizing agent.
In the invention, the temperature in the dipping die is preferably 260-280 ℃, more preferably 264-276 ℃ and more preferably 268-272 ℃.
In the present invention, the impregnation is preferably a coating.
In the present invention, the cooling means preferably includes water cooling.
In the present invention, the cooled polyamide composite material is preferably pelletized to obtain glass fiber-reinforced polyamide composite material pellets.
The invention is a complete and refined integral preparation process, better ensures the performance of the 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, and improves the mechanical property, the dimensional stability and the surface quality, and the preparation method of the glass fiber reinforced polyamide composite material can specifically comprise 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 a wetting agent which is well compatible with PA66 resin.
Step 2: uniformly mixing PA66 resin, semi-aromatic nylon resin, a lubricant, a nucleating agent, an antioxidant and black master batch in a high-speed mixer according to a proportion to obtain a premix;
and step 3: adding the premix obtained in the step 2 into a premix with the length-diameter ratio of (30-60): 1, simultaneously threading the 16 rolls of high-strength continuous flat glass fibers obtained in the step 1 through a melting and dipping die, melting and extruding the premix through the twin-screw extruder, then feeding the obtained mixture into the dipping die, fully soaking the high-strength continuous flat glass fibers in the dipping die, cooling and molding the obtained product in a cooling water tank, and pelletizing the obtained product to obtain the high-strength high-flow low-warpage long glass fiber reinforced PA66 composite material.
The processing temperature of each section of the double-screw extruder is preferably controlled to be 250-280 ℃, the vacuum degree is preferably-0.1 MPa, and the temperature of the dipping die is preferably 280 ℃. More specifically, the twin-screw extruder has a length to diameter 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 an impregnation die, and the drawing speed thereof may be 20 m/min.
The invention also provides the glass fiber reinforced polyamide composite material pellet of any one of the above technical schemes, the glass fiber reinforced polyamide composite material of any one of the above technical schemes or the application of the glass fiber reinforced polyamide composite material prepared by the preparation method of any one of the above technical schemes in the fan blade aspect.
The invention provides a high-strength high-flow low-warpage long glass fiber reinforced polyamide (PA66) composite material, a preparation method and application. The invention provides a polyamide composite material pellet containing flat glass fibers, which contains oriented flat glass fibers, and further obtains a corresponding long glass fiber reinforced polyamide composite material with high strength, high fluidity and low warpage. According to the high-strength flat continuous long glass fiber reinforced PA66 composite material, the high-strength continuous flat glass fiber is used for replacing common cylindrical glass fiber, so that the mechanical property of the glass fiber reinforced PA66 composite material is improved, the flowability and the appearance of a workpiece of the glass fiber reinforced PA66 composite material are improved, and the warping deformation of a flat long glass fiber reinforced PA66 composite material product 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 the glass fiber. The development requirements of high mechanical property, high dimensional stability, high surface quality and low water absorption of the industrial fan blade material are met.
The high-strength high-flow 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, easy warpage and deformation, poor surface quality and high water absorption rate of the conventional long glass fiber reinforced PA66 composite material, can obviously improve the mechanical property, the length of a flow channel and the surface quality of a long glass fiber reinforced PA66 composite material, and can ensure that 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 requirements 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 high-strength continuous flat glass fibers to replace common cylindrical glass fibers, so that the mechanical property of the PA66 composite material is enhanced, the flowability and the appearance of a workpiece of the PA66 composite material are improved, and the warping deformation and the water absorption of the product are reduced.
In order to further illustrate the present invention, the following examples are provided to describe the glass fiber reinforced polyamide composite pellets, the glass fiber reinforced polyamide composite, the preparation method and the application in detail, but it should be understood that the examples are carried out on the premise of the technical scheme of the present invention, the detailed embodiments and the specific operation procedures are given only for further illustration of the features and advantages of the present invention, and the scope of the present invention is not limited to the following examples.
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, type PA66-EPR 24;
16 rolls (4800 rolls each) of high-strength continuous flat long glass fiber, the model number of the glass fiber is ER5301T-2000, the section of the glass fiber is flat, the width-thickness ratio of the cross section is 4:1, and the surface of the glass fiber is coated with a wetting agent which is well compatible with PA66 resin;
0.15 kg of lubricant is an ethylene-acrylic acid copolymer lubricant;
10 kg of semi-aromatic nylon resin MXD6 with a special chemical structure: is synthesized by condensation polymerization of m-xylylenediamine and adipic acid;
0.15 kg of hindered phenol type primary antioxidant, type Irganox 1098, and 0.15 kg of phosphite type antioxidant, type Irganox 168;
0.3 kg of black master batch, the model number of which is CABOT-PA 3785;
0.05 kg of nucleating agent, model P22.
The preparation method of the high-strength continuous flat long glass fiber reinforced PA66 composite material 1 comprises the steps of preparing raw materials according to the weight,
step 1: high strength continuous flat glass fibers of type ER 5301T-2000;
step 2: 49.2 kg of PA66 resin with the model of PA66-EPR24, 10 kg of semi-aromatic nylon MXD6, 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 polyethylene-acrylic acid copolymer lubricant and 0.05 kg of nucleating agent P22 were added. Fully and uniformly mixing in a high-speed mixer to obtain premix 1;
and step 3: and (2) 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 speed of 60 kg/h, simultaneously threading the 16 rolls of high-strength continuous flat glass fibers in the step (1) through a melting and dipping die, melting and extruding the premix by the double-screw extruder, feeding the premix into the dipping die, fully soaking the high-strength continuous flat glass fibers in the dipping die, cooling and molding the mixture in a cooling water tank, and pelletizing the mixture into 12mm long pellets 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-0.1 MPa, and the temperature of the dipping die is 280 ℃.
The high strength continuous flat long glass fiber reinforced PA66 composite 1 with a glass fiber content of 40% was tested to perform as follows: the injection molding machine conditions are 280 ℃, 60MPa injection pressure conditions, the pellet spiral runner length is 750mm (width 20mm, thickness 2mm), the shrinkage rate in the flow direction is 0.12%, the shrinkage rate in the vertical flow direction is 0.2%, and the water absorption rate (23 ℃, 24h) 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, type PA66-EPR 24;
16 rolls of high-strength flat long glass fiber, the model number of the high-strength flat long glass fiber is ER5301T-2000, the section of the high-strength flat long glass fiber is flat, and the width-thickness ratio of the cross section is 4: 1;
0.15 kg of lubricant is an ethylene-acrylic acid copolymer lubricant;
0.15 kg of hindered phenol type primary antioxidant, type Irganox 1098, and 0.15 kg of phosphite type antioxidant, type Irganox 168;
0.3 kg of black master batch, the model of which is CABOT-PA 3785.
0.05 kg of nucleating agent, model 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 fibers of type ER 5301T-2000;
step 2: 59.2 kg of PA66 (polyamide) resin with the model of PA66-EPR24, 0.15 kg of phenolic 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 polyethylene-acrylic acid copolymer lubricant and 0.05 kg of nucleating agent with the model of P22 are added. Fully and uniformly mixing in a high-speed mixer to obtain premix 2;
and 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 speed of 60 kg/h, simultaneously threading the 16 rolls of high-strength continuous flat glass fibers in the step (1) through a melting and dipping die, melting and extruding the premix by the double-screw extruder, feeding the premix into the dipping die, fully soaking the high-strength continuous flat glass fibers in the dipping die, cooling and molding the mixture in a cooling water tank, and pelletizing the mixture into 12mm long pellets 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 at 250 ℃ and 280 ℃, and the vacuum degree is-0.1 MPa. The dip mold temperature was 280 ℃.
The high strength continuous flat long glass fiber reinforced PA66 composite 2 with a glass fiber content of 40% was tested to perform as follows: the injection molding machine conditions are 280 ℃, under the test conditions of 60Mpa injection pressure, the spiral flow channel length of the granules is 720mm (the width is 20mm, the thickness is 2mm), the shrinkage rate in the flow direction is 0.15%, the shrinkage rate in the vertical flow direction is 0.25%, and the water absorption rate (23 ℃, 24h) is 0.65%.
The result shows that the high-strength continuous flat long glass fiber reinforced PA66 composite material 2 has certain high fluidity, high mechanical property and high dimensional stability, but the water absorption rate is increased.
Comparative example 1
Taking the following raw materials:
59.2 kg of PA66 (polyamide) resin, type PA66-EPR 24;
16 rolls of common cylindrical glass fiber with the model number of ER 4301R-2400;
0.15 kg of lubricant is an ethylene-acrylic acid copolymer lubricant;
0.15 kg of hindered phenol type primary antioxidant, type Irganox 1098, and 0.15 kg of phosphite type antioxidant, type Irganox 168;
0.3 kg of black master batch, the model of which is CABOT-PA 3785.
0.05 kg of nucleating agent, model P22.
A comparative example of a conventional long glass fiber reinforced PA66 composite 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 compound for a comparative example;
and meanwhile, threading the 16 rolls of ordinary cylindrical glass fibers ER4301R-2400 obtained in the step 1 through a melting and dipping die, melting and extruding the premix through the double-screw extruder, then feeding the premix into the dipping die, fully soaking the ordinary long glass fibers in the dipping die, cooling and molding the mixture in a cooling water tank, and cutting the mixture into 12mm long granules to obtain the 40% ordinary long glass fiber reinforced PA66 composite material. Wherein, the processing temperature of each section of the double-screw extruder is controlled at 250 ℃ and 280 ℃, and the vacuum degree is-0.1 Mpa. The dip mold temperature was 280 ℃.
The test results show that the comparative flat long glass fiber reinforced polypropylene composite with 40% glass fiber content has the following properties: the injection molding machine conditions are 280 ℃, under the test conditions of 60Mpa injection pressure, the spiral flow channel length of the granules is 700mm (the width is 20mm, the thickness is 2mm), the shrinkage rate in the flow direction is 0.2%, the shrinkage rate in the vertical flow direction is 0.28%, and the water absorption rate (23 ℃, 24h) is 1.1%.
The foregoing detailed description of a high strength, high flow, low warpage long glass fiber reinforced polyamide (PA66) composite material and method of making and using the same provided by the present invention is presented herein using specific examples to illustrate the principles and embodiments of the present invention, the above examples are provided only to aid in the understanding of the method and its core ideas, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any combination of the methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention 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 languages of the claims.
Claims (10)
1. A glass fiber reinforced polyamide composite pellet, characterized in that the polyamide composite pellet comprises flat glass fibers;
the flat glass fibers are distributed in the longitudinal direction in the same direction as the polyamide composite pellets.
2. Polyamide composite pellets according to claim 1, characterized in that the flat glass fibers are in particular glass fibers with a flat cross section;
the length of the cross section 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 μm;
the cross-section width-thickness ratio of the flat glass fiber is (3-8): 1;
the length of the polyamide composite material granules is 8-15 mm.
3. Polyamide composite pellets according to claim 1, characterized in that the length of the flat glass fibers is equal to the length of the polyamide composite pellets;
each 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 polyamide composite material with flat long glass fibers continuously distributed;
the polyamide composite material granules are resin raw materials for preparing fan blades.
4. The glass fiber reinforced polyamide composite material is characterized by comprising the following raw materials in parts by weight:
5. the polyamide composite material of claim 4, wherein 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 prepared by condensation polymerization of m-xylylenediamine and adipic acid;
the melt index of the semi-aromatic nylon is 41.8g/10 min;
the flat glass fibers comprise flat long glass fibers.
6. The polyamide composite material according to claim 4, characterized in that the flat glass fibers have a length of 6500 to 9000 m;
the flat glass fiber is specifically a flat glass fiber with the surface compounded with an auxiliary agent;
the auxiliary agent comprises one or more of a wetting 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%.
7. The polyamide composite of claim 4, wherein 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 antioxidant and/or phosphite antioxidant;
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;
the glass fiber reinforced polyamide composite material is pelletized to obtain the glass fiber reinforced polyamide composite material pellet as claimed in any one of claims 1 to 3.
8. A preparation method of a glass fiber reinforced polyamide composite material is characterized by comprising the following steps:
1) mixing PA66 resin, semi-aromatic nylon resin, a lubricant, a nucleating agent and an antioxidant to obtain a premix;
2) and (3) feeding the melt material obtained by melting and extruding the premix material through the double screws into an impregnation die with flat glass fibers, infiltrating the flat glass fibers with the melt material, demolding, and cooling to obtain the glass fiber reinforced polyamide composite material.
9. The preparation method of claim 8, wherein the twin-screw melt extrusion has a twin-screw length-diameter ratio of (30-60): 1;
the temperature of the twin-screw melt extrusion is 250-280 ℃;
the vacuum pressure of the twin-screw melt extrusion is less than or equal to 0.02 Mpa;
the flat glass fiber is specifically a flat glass fiber with a surface compounded with a sizing agent;
the temperature in the dipping die is 260-280 ℃;
the cooling mode comprises water cooling;
and pelletizing after cooling to obtain the glass fiber reinforced polyamide composite material granules.
10. Use of the glass fiber reinforced polyamide composite pellets according to any one of claims 1 to 3, the glass fiber reinforced polyamide composite according to any one of claims 4 to 7 or the glass fiber reinforced polyamide composite produced by the production method according to any one of claims 8 to 9 in fan blades.
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