CN111117219B - Nylon composite material, nylon product and preparation method thereof - Google Patents
Nylon composite material, nylon product and preparation method thereof Download PDFInfo
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- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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Abstract
The application relates to a nylon composite material, a nylon product and a preparation method thereof, wherein the nylon composite material comprises the following components: 33 to 66.8 percent of nylon resin, 30 to 50 percent of chopped glass fiber, 2 to 10 percent of attapulgite clay, 1 to 5 percent of compatilizer, 0.1 to 1 percent of lubricant and 0.1 to 1 percent of antioxidant. The preparation method has the advantages that the micron-sized attapulgite clay filler and a glass fiber composite reinforcing system are adopted for modification, the high-strength nylon composite material is prepared by a melt blending method, the advantages of the glass fiber reinforced nylon composite material are maintained, the strength and the heat resistance of the material are further improved, the defects of poor dimensional stability and surface floating fiber of the high-glass fiber content reinforced composite material are overcome, the nylon composite material has excellent mechanical property, good fluidity and high crystallization speed, the preparation method is simple, the cost is low, and high-strength products such as mechanical parts, automobile parts and medical sports equipment parts can be prepared by injection molding.
Description
Technical Field
The application relates to the technical field of preparation of high polymer materials, in particular to a nylon composite material, a nylon product and a preparation method thereof.
Background
Organic-inorganic nanocomposite materials have received wide attention over the last decades, and a wide variety of inorganic nanoparticles have been incorporated into polymers to improve the physical and mechanical properties of the polymer materials. The nylon engineering plastic has good comprehensive properties of high toughness, wear resistance, self lubrication, corrosion resistance and the like, is widely applied to the fields of automobiles, electronics, electrics, machinery, buildings and the like, and has higher requirements on the properties.
In recent years, nylon has been modified with a wide variety of inorganic nanoparticles. The glass fiber is added into nylon, so that the prepared nylon composite material has higher strength, but the composite material has the problems of poor dimensional stability and surface floating fiber.
Disclosure of Invention
Based on the problems, the prior glass fiber nylon composite material has poor dimensional stability and surface floating fiber, and a nylon composite material, a nylon product and a preparation method thereof are needed.
The nylon composite material comprises the following components in percentage by weight:
in one embodiment, the attapulgite clay has an average particle size of greater than 3000 mesh.
In one embodiment, the surface of the attapulgite clay is subjected to an acidification treatment or a silane coupling agent surface treatment.
In one embodiment, the compatibilizer is a maleic anhydride grafted polyethylene-octene copolymer.
In one embodiment, the chopped glass fibers have an average length of 3mm to 4.5mm and an average diameter of 10 μm to 14 μm.
In one embodiment, the nylon resin is at least one of nylon 6 or nylon 66.
In one embodiment, the lubricant is at least one of ethylene bis-stearamide, silicone powder, pentaerythritol stearate, or montanate.
In one embodiment, the antioxidant is at least one of a hindered phenolic antioxidant or a phosphorus-containing antioxidant.
The preparation method of the nylon composite material comprises the following steps:
mixing the nylon resin, the attapulgite clay, the compatilizer, the lubricant and the antioxidant according to the proportion to obtain a raw material mixture;
respectively adding the raw material mixture and the chopped glass fibers into an extruder, and carrying out melt extrusion, cooling and granulation in the extruder to obtain a modified nylon composite material;
a nylon product prepared from any one of the nylon composite materials described above.
The nylon composite material, the nylon product and the preparation method thereof adopt a micron-sized attapulgite clay filler and glass fiber composite reinforcing system for modification, and the high-strength nylon composite material is prepared by a melt blending method, so that the advantages of the glass fiber reinforced nylon composite material are maintained, the strength and the heat resistance of the material are further improved, the defects of poor dimensional stability and surface floating fiber of the high-glass fiber reinforced composite material are overcome, and the nylon composite material has the advantages of excellent mechanical property, good fluidity, high crystallization speed, simple preparation method and low cost, and can be used for preparing high-strength nylon products such as mechanical parts, automobile parts, medical sports equipment parts and the like by injection molding.
Detailed Description
In order to facilitate an understanding of the present application, a more complete description of the nylon composite, nylon articles, and methods of making the same will now be provided. Preferred examples of nylon composites, nylon articles, and methods of making the same are set forth below. However, the nylon composite, nylon article, and method of making the same may be implemented in many different forms and are not limited to the embodiments described herein. Rather, the purpose of these examples is to provide a more thorough and complete disclosure of nylon composites, nylon articles, and methods of making the same.
It will be understood that when an element is referred to as being "fixed to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like are used herein for illustrative purposes only and are not meant to be the only embodiment.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of nylon composites, nylon articles, and methods of making the same is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
An embodiment of the application is a nylon composite material comprising the following components in percentage by weight: 33 to 66.8 percent of nylon resin, 30 to 50 percent of chopped glass fiber, 2 to 10 percent of attapulgite clay, 1 to 5 percent of compatilizer, 0.1 to 1 percent of lubricant and 0.1 to 1 percent of antioxidant. The following examples are given without specific reference, and the percentages relate to mass proportions. In one embodiment, the nylon composite material comprises 40-66% of nylon resin, 30-50% of chopped glass fiber, 2-10% of attapulgite clay, 1.5-4% of compatilizer, 0.2-0.5% of lubricant and 0.2-0.4% of antioxidant. In one embodiment, the nylon composite comprises 65.4% nylon resin, 30% chopped glass fibers, 2% attapulgite clay, 2% compatibilizer, 0.3% lubricant, and 0.3% antioxidant.
In one embodiment, the nylon composite comprises 40% -66% nylon resin; in one embodiment, the nylon composite comprises the following components in weight percent: 40-66% of nylon resin, 30-50% of chopped glass fiber, 2-10% of attapulgite clay, 1-5% of compatilizer, 0.1-1% of lubricant and 0.1-1% of antioxidant. The remaining embodiments and so on. In one embodiment, the nylon composite comprises 42% -63% nylon resin; in one embodiment, the nylon composite comprises 45% -56% nylon resin; in one embodiment, the nylon composite comprises 47.2%, 52.2%, or 55.2% nylon resin; in one embodiment, the nylon resin is at least one of nylon 6 or nylon 66. In one embodiment, the nylon resin is nylon 6 (PA 6) or nylon 66 (PA 66), or the nylon resin is a mixture of both nylon 6 and nylon 66. In one embodiment, the nylon resin is a mixture of nylon 6 and nylon 66 mixed in any ratio.
In one embodiment, the nylon composite comprises 2% -8% attapulgite clay; in one embodiment, the nylon composite comprises 2% -6% attapulgite clay; in one embodiment, the nylon composite comprises 2%, 3% or 5% attapulgite clay. Attapulgite clay (ATP for short) is a natural hydrated magnesium aluminum silicate with a rod-like and needle-like crystal structure, has rich attapulgite reserves, low cost, special dispersing, high temperature resistance, salt and alkali resistance and strong adsorption decolorization capability, and has rich silicon hydroxyl groups on the surface and large polarity. In one embodiment, the average particle size of the attapulgite clay is greater than 3000 mesh, mesh being the size of the mesh size of a standard sieve. In the taylor standard sieve, the mesh size is the number of meshes in a length of 2.54 cm (1 inch), which is simply called mesh size, and the 3000 mesh size is 5 μm. The average particle size of the attapulgite clay is more than 3000 meshes, namely the average particle size of the attapulgite clay is less than 5 mu m. The larger the mesh number, the more pores per unit area, the smaller the pore size, and the finer the particles filtered by sieving. In one embodiment, the average particle size of the attapulgite clay is greater than 3200 mesh, and in one embodiment, the average particle size of the attapulgite clay is greater than 4000 mesh; in one embodiment, the surface of the attapulgite clay is subjected to an acidification treatment or a silane coupling agent surface treatment. In one embodiment, the average particle size of the attapulgite clay is greater than 3000 mesh and the surface of the attapulgite clay is acidified or surface treated with a silane coupling agent.
In one embodiment, the method of acidizing the attapulgite clay is: soaking attapulgite clay in inorganic acid, washing the attapulgite clay soaked in inorganic acid with water until the pH value is neutral, and drying the washed attapulgite clay. The surface of the attapulgite clay is acidified, so that the compatibility of the attapulgite clay and nylon resin is improved. In one embodiment, the method of acidizing the attapulgite clay is: the attapulgite clay was immersed in 37% hydrochloric acid for 24 hours. And then fishing out the soaked attapulgite clay, and washing with distilled water to remove hydrochloric acid on the surface of the attapulgite clay and impurities generated by acidification. The attapulgite clay is of a multi-surface molecular structure, so that pores are formed, impurities possibly remain in the pores of the attapulgite clay, and the impurities are dissolved by acidification, so that the pores are dredged, the specific surface area of the attapulgite clay is increased, and the adsorption capacity of the attapulgite clay is improved. After acidification, the attapulgite clay is repeatedly washed, for example, by using flowing clean water until the pH value of the surface of the attapulgite clay is 7, i.e. the attapulgite clay is adjusted to be neutral, so that hydrochloric acid is prevented from being brought into subsequent reactions to influence the subsequent reaction environment. Finally, removing the water vapor on the surface of the attapulgite clay. In one embodiment, the attapulgite clay is dried in a vacuum environment at 80 ℃ for 12 hours. Compared with a natural ventilation environment, the attapulgite clay is dried in a vacuum environment, so that the attapulgite clay is prevented from adsorbing impurities and new water vapor, and the drying efficiency is improved. The drying temperature is controlled at 80 ℃, so that the drying efficiency can be improved, and the crystal water carried by the attapulgite clay is also reserved. By setting for 12 hours to dry, it was ensured that no water vapor remained in the attapulgite clay. Based on the extremely small particle size and the strong adsorption capacity of the attapulgite clay, the vacuum constant temperature and the drying for a long time can not only remove the impurities of the attapulgite clay, but also ensure that the property of the attapulgite clay is unchanged.
In one embodiment, the nylon composite comprises 30% -50% chopped glass fibers; in one embodiment, the nylon composite comprises 30% -45% chopped glass fibers; in one embodiment, the nylon composite comprises 30%, 40% or 45% chopped glass fibers. After shearing by an extruder screw, the average length of the chopped glass fiber is changed from 3mm to 4.5mm to 0.4mm to 0.6mm, and the average diameter is 10 mu m to 14 mu m. When the average particle size of the attapulgite clay is larger than 3000 meshes, the size of the attapulgite clay in all directions is smaller than that of the chopped glass fibers, so that the attapulgite clay can be fully dispersed among the chopped glass fibers. In the nylon composite material with unit content, the chopped glass fibers and the attapulgite clay with different sizes are distributed in the matrix in a staggered way, so that the chopped glass fibers and the attapulgite clay are uniformly distributed in all directions of the matrix, thereby being beneficial to improving the mechanical properties of the matrix.
In one embodiment, the nylon composite includes 1.8% -3.7% of a compatibilizer; in one embodiment, the nylon composite includes 2% to 3.2% of a compatibilizer; in one embodiment, the nylon composite includes 2%, 2.7%, or 3.0% of a compatibilizer. In one embodiment, the compatibilizer is a maleic anhydride compatibilizer in which maleic anhydride is grafted onto the polyolefin. In one embodiment, the compatibilizer is a maleic anhydride grafted polyethylene-octene copolymer. The maleic anhydride monomer has stronger polarity, and the prepared compatilizer can improve the compatibility of inorganic filler and organic resin, improve the tensile and impact strength of the product, realize high filling, reduce the resin consumption, improve the processing rheological property and improve the surface finish by adopting maleic anhydride to graft to the polyethylene-octene copolymer.
In one embodiment, the nylon composite comprises 0.1% -0.8% of an antioxidant; in one embodiment, the nylon composite comprises 0.1% -0.5% of an antioxidant; in one embodiment, the nylon composite includes 0.1%, 0.3%, or 0.5% antioxidant. The antioxidant is a mixture of hindered phenol antioxidant and phosphorus-containing antioxidant. The hindered phenol antioxidant is not easy to oxidize due to large steric hindrance, and the addition of the hindered phenol antioxidant can play a role in eliminating free radicals and play a role in resisting thermo-oxidative aging. Not only can prevent the oxidation of the hot melt environment in the preparation of the nylon composite material, but also can prevent the aging of the nylon composite material product and prolong the service life of the product. For example, the antioxidant is obtained by mixing N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine with bis (2, 4-dicumylphenyl) pentaerythritol diphosphite in a weight ratio of 1:1.
In one embodiment, the nylon composite includes 0.1% to 0.8% lubricant; in one embodiment, the nylon composite includes 0.3% to 0.8% lubricant; in one embodiment, the nylon composite includes 0.3%, 0.5%, or 0.8% lubricant. The lubricant is at least one of ethylene bis-stearamide, silicone powder, pentaerythritol stearate or montanate or a mixture of two of the ethylene bis-stearamide, silicone powder, pentaerythritol stearate and montanate. That is, the lubricant is at least one of ethylene bis-stearamide, silicone powder, pentaerythritol stearate or montanate. Or the lubricant is a mixture of two of ethylene bis-stearamide, silicone powder, pentaerythritol stearate or montanate, and the two lubricants are mixed according to any proportion. By adding a lubricant, which is inserted between the polymer molecules in a molten state, the mutual friction between the molecules is weakened, the internal heat generation is reduced, and the melt fluidity is improved, which corresponds to the plasticizing effect, instead of adding the plasticizer additionally. Meanwhile, part of the lubricant is adhered to the surfaces of the nylon resin particles to form a molecular layer of the lubricant, so that friction between the nylon resin before and after melting and the surfaces of processing machinery is reduced, uneven dispersion of glass fibers caused by uneven surfaces of the nylon resin particles due to friction is ensured, and a fiber floating phenomenon is avoided.
The nylon composite material is modified by adopting a micron-sized attapulgite clay filler and glass fiber composite reinforcing system, and has the advantages of excellent mechanical property, good fluidity, high crystallization speed, simple preparation method and lower cost. The glass fiber reinforced nylon composite material has the advantages of maintaining the advantages of the glass fiber reinforced nylon composite material, further improving the strength and heat resistance of the material, and improving the defects of poor dimensional stability and surface floating fiber of the high glass fiber content reinforced composite material. The nylon composite material can be used for preparing nylon products such as mechanical parts, automobile parts, medical sports equipment parts and the like with high strength through injection molding.
In one embodiment, a method of making a nylon composite includes the steps of:
the nylon resin, the attapulgite clay, the compatilizer, the lubricant and the antioxidant in any embodiment are mixed according to a proportion to obtain a raw material mixture. And respectively adding the raw material mixture and the chopped glass fibers into an extruder, and carrying out melt extrusion, cooling and granulation in the extruder to obtain the modified nylon composite material.
In one embodiment, the step of mixing the components is preceded by a step of drying the nylon resin and a step of acidifying the attapulgite clay. For example, the step of drying the nylon resin is: and drying the nylon resin at 90-110 ℃ for 5-7 h to obtain the dried nylon resin. In addition, the step of acidizing the attapulgite clay comprises the following steps: soaking attapulgite clay in inorganic acid, washing the attapulgite clay soaked in inorganic acid with water until the pH value is neutral, and drying the washed attapulgite clay. Further, the step of acidifying the attapulgite clay comprises the following steps: the attapulgite clay was immersed in 37% hydrochloric acid for 24 hours. And washing the soaked attapulgite clay by distilled water until the pH value of the surface of the attapulgite clay is 7, and then drying the attapulgite clay in a vacuum environment at 80 ℃ for 12 hours.
In one embodiment, the steps of mixing the compatilizer, the lubricant, the antioxidant, the dried nylon resin and the acidified attapulgite clay according to the mass percentages are as follows: adding the components into a high-speed mixer, stirring for 3-5 min, and fully mixing to obtain a raw material mixture.
In one embodiment, the steps of adding the raw material mixture into an extruder, melt extruding, cooling and granulating, and obtaining the modified nylon composite material are as follows: the raw material mixture was fed into a twin-screw extruder, and the chopped glass fibers in the above mass percentages were fed from a side feed port of the twin-screw extruder. In one embodiment, the respective temperature zone settings for the twin screw extruder are: the temperature of the first area is 200-220 ℃, the temperature of the second area is 220-240 ℃, the temperature of the third area is 220-240 ℃, the temperature of the fourth area is 220-250 ℃, the temperature of the fifth area is 220-250 ℃, the temperature of the sixth area is 220-240 ℃, the temperature of the seventh area is 220-240 ℃, the temperature of the eighth area is 220-240 ℃, the temperature of the ninth area is 220-250 ℃, the rotating speed of the host machine is 240-400 revolutions per minute, and the yield is 200kg/h.
A nylon product prepared from the nylon composite of any of the above embodiments. The preparation method of the nylon product specifically comprises the following steps: mixing the compatilizer, the lubricant, the antioxidant, the dried nylon resin and the acidified attapulgite clay of any nylon composite material according to the mass percentage to obtain a raw material mixture. And respectively adding the raw material mixture and the chopped glass fibers into an extruder, carrying out melt extrusion in the extruder, cooling and granulating the extrudate, and finally carrying out injection molding on the granules to obtain the nylon product. The nylon product obtained by the preparation method not only maintains the advantages of the product made of the glass fiber nylon composite material, but also further improves the strength and the heat resistance of the nylon product, and overcomes the defects of poor dimensional stability and surface floating fiber of the nylon product caused by high glass fiber content. The nylon composite product has excellent mechanical property, high crystallization speed, simple preparation method and low cost, can be used for preparing nylon product parts such as high-strength machinery, automobile parts, medical or sports equipment and the like by injection molding, and has wide application.
The application will be further illustrated with reference to specific examples.
In the following composite formulations of examples and comparative examples, nylon 6 was designated PA6 BL2280, manufactured by yueya petrochemical company. The glass fiber brand is ECS11-03-568H, and is produced by a huge stone group. The attapulgite clay is provided by Anhui Boshuo technology Co., ltd. The number of the compatilizer is N416, which is produced by DuPont company. The lubricant is PETS and is manufactured by Lonza company of America. The antioxidant is 1098 and S9228 mixed according to the ratio of 1:1. Wherein the brand of the antioxidant 1098 is IRGANOX 1098, the chemical name of the antioxidant is N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, the brand of the antioxidant 1098 is Doverpho S-9228, and the chemical name of the antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, which is produced by Dover company in the United states.
The preparation method of the nylon composite material comprises the following steps:
the commercially available nylon 6 resin was dried at 100℃for 6 hours to obtain a dried nylon 6 resin. The attapulgite clay was treated with 37% hydrochloric acid for 24 hours, and then the attapulgite clay was washed with distilled water to PH 7, and then vacuum-dried at 80 ℃ for 12 hours to obtain an acidified attapulgite clay. And stirring the dried nylon 6, the acidified attapulgite clay, the compatilizer, the lubricant and the antioxidant in a high-speed mixer for 3 minutes to obtain a raw material mixture. Adding the raw material mixture into a double-screw extruder, adding chopped glass fibers at a lateral feeding port of the double-screw extruder, and carrying out melt extrusion through the double-screw extruder to obtain an extrudate. The temperature zone of the twin-screw extruder was set as: the temperature of the first area is 200-220 ℃, the temperature of the second area is 220-240 ℃, the temperature of the third area is 220-240 ℃, the temperature of the fourth area is 220-250 ℃, the temperature of the fifth area is 220-250 ℃, the temperature of the sixth area is 220-240 ℃, the temperature of the seventh area is 220-240 ℃, the temperature of the eighth area is 220-240 ℃, the temperature of the ninth area is 220-250 ℃, the rotating speed of the host machine is 240-400 rpm, and the yield is 200kg/h. And cooling, drying and granulating the extrudate to obtain the nylon composite material.
The properties of the nylon composite obtained according to the above preparation method were examined, and the examination items include tensile strength, flexural strength, notched impact strength, heat distortion temperature, melt flow rate and surface quality. The specific detection method comprises the following steps:
tensile strength was measured according to ASTM-D638, sample type I, spline size (mm): (165.+ -. 2) × (12.70.+ -. 0.2) × (3.20.+ -. 0.2), drawing speed was 50mm/min.
Flexural strength test, sample size (mm) according to ASTM-D790: (127+ -2) × (12.7+ -0.2) × (3.20+ -0.2), and the bending speed was 2mm/min.
Notched impact strength test was performed according to ASTM-D256, sample type V notched, sample size (mm): 63.5× (12.7±0.2) × (3.2±0.2); the notch type is V-shaped, and the residual thickness of the notch is 10.16mm.
Heat distortion temperature test was performed according to ASTM-D648 standard with a load of 1.82Mpa, sample size (mm): (127+ -2) x (12.7+ -0.2) x (3.20+ -0.2); the maximum deflection was 0.254mm.
Melt flow rate testing was performed in accordance with ASTM D1238.
The surface quality was visually checked, and the injection molded product was a 80mm×80mm×2mm template, and the comparison was observed.
Embodiments of the present application are specifically described below.
Example 1
The nylon composite material of the embodiment 1 comprises the following components in percentage by mass:
55.2% nylon 6, 40% chopped glass fibers, 2% attapulgite, 2% compatilizer, 0.5% lubricant and 0.3% antioxidant. The preparation method of the nylon composite material of the embodiment 1 comprises the following steps:
nylon 6 was dried and the attapulgite clay was acidified as described above. And stirring the dried nylon 6, the acidified attapulgite clay, the compatilizer, the lubricant and the antioxidant in a high-speed mixer for 3 minutes to obtain a raw material mixture. The raw material mixture is added into a double-screw extruder, chopped glass fibers are added at a lateral feeding port, and melt extrusion is performed through the double-screw extruder. The temperature zone of the twin-screw extruder was set as: the temperature of the first area is 200-220 ℃, the temperature of the second area is 220-240 ℃, the temperature of the third area is 220-240 ℃, the temperature of the fourth area is 220-250 ℃, the temperature of the fifth area is 220-250 ℃, the temperature of the sixth area is 220-240 ℃, the temperature of the seventh area is 220-240 ℃, the temperature of the eighth area is 220-240 ℃, the temperature of the ninth area is 220-250 ℃, the rotating speed of the host machine is 240-400 rpm, and the yield is 200kg/h. And cooling, granulating and drying the extrudate to obtain the nylon composite material.
Example 2
The nylon composite material of the embodiment 2 comprises the following components in percentage by mass:
52.2% nylon 6, 40% chopped glass fibers, 5% attapulgite, 2% compatilizer, 0.5% lubricant and 0.3% antioxidant.
The preparation method of the nylon composite of this embodiment 2 is the same as that of embodiment 1, and will not be described here again.
Example 3
The nylon composite material of the embodiment 3 comprises the following components in percentage by mass:
47.2% nylon 6, 40% chopped glass fiber, 10% attapulgite, 2% compatilizer, 0.5% lubricant and 0.3% antioxidant.
The preparation method of the nylon composite of this embodiment 3 is the same as that of embodiment 1, and will not be described here again.
Example 4
The nylon composite material of the embodiment 4 comprises the following components in percentage by mass:
62.2% nylon 6, 30% chopped glass fibers, 5% attapulgite, 2% compatilizer, 0.5% lubricant and 0.3% antioxidant.
The preparation method of the nylon composite of this embodiment 4 is the same as that of embodiment 1, and will not be described here again.
Example 5
The nylon composite material of the embodiment 5 comprises the following components in percentage by mass:
42.2% nylon 6, 50% chopped glass fibers, 5% attapulgite, 2% compatilizer, 0.5% lubricant and 0.3% antioxidant.
The preparation method of the nylon composite of this embodiment 5 is the same as that of embodiment 1, and will not be described here again.
Comparative example 1
The nylon composite material of the comparative example 1 comprises the following components in parts by weight:
67.2% nylon 6, 30% chopped glass fibers, 2% compatilizer, 0.5% lubricant and 0.3% antioxidant.
The preparation method of the nylon composite of comparative example 1 is the same as that of example 1 except that the comparative example 1 does not contain attapulgite clay, and a detailed description thereof is omitted.
Comparative example 2
The nylon composite material of the comparative example 2 comprises the following components in parts by weight:
47.2% nylon 6, 50% chopped glass fibers, 2% compatilizer, 0.5% lubricant and 0.3% antioxidant.
The preparation method of the nylon composite of comparative example 2 is the same as that of example 1 except that the comparative example 2 does not contain attapulgite clay, and a detailed description thereof is omitted.
Comparative example 3
The nylon composite material of the comparative example 3 comprises the following components in parts by weight:
52.2% nylon 6, 40% chopped glass fibers, 5% attapulgite clay, 2% compatibilizer, 0.5% lubricant, and 0.3% antioxidant.
In the preparation method of comparative example 3, the attapulgite clay was not acidified, and the rest of the steps of comparative example 3 are the same as those of example 1, and will not be repeated here.
The nylon composite materials prepared in each example and comparative example were subjected to performance tests, respectively, including tensile strength, flexural strength, notched impact strength, heat distortion temperature, melt flow rate and surface quality, according to the above test methods. Specific data of the respective examples and comparative examples described above are shown in table 1 below.
TABLE 1
As can be seen from the above table 1, in the nylon composite of each of the examples, as seen from examples 1 to 3, the chopped glass fibers within a certain content range, as the amount of the attapulgite clay which is acidified increases, the mechanical properties of the nylon composite are improved, wherein each component of the nylon composite of example 2 is more optimally proportioned, and in each example, the properties thereof are mostly optimal. As can be seen from example 3 and comparative example 3, comparative example 3 added attapulgite clay without surface treatment, instead, reduced the tensile strength, flexural strength and impact strength of the nylon composite, because the untreated filler had poor compatibility with the nylon resin and was easily agglomerated in the matrix, thus reducing the tensile strength, flexural strength and notched impact strength of the nylon composite. As can be seen from example 5 and comparative example 2, the nylon composite of comparative example 2, to which the surface-treated attapulgite clay was not added, had a rough surface quality and had significant fiber floats. Therefore, the addition of the attapulgite clay after the surface treatment can effectively improve the mechanical property and the surface quality of the high glass fiber nylon composite material, so that the surface of the nylon composite material is smooth and has no floating fiber. In the traditional glass fiber nylon composite material, 30% of glass fibers are added to improve the mechanical properties of the nylon composite material, but if more than 30% of glass fibers are added, the mechanical properties of the nylon composite material can be further improved, but the surface quality can be seriously affected, and the phenomena of roughness and obvious fiber floating appear. The nylon composite material of the application not only further improves the mechanical property of the nylon composite material, but also ensures that the surface quality is not affected under the condition that the proportion of glass fibers exceeds 30 percent, even 50 percent.
As can be seen from examples 4 and 5, the nylon composite system with 5% surface treated attapulgite clay and 40% -50% chopped glass fibers added has higher mechanical strength and heat resistance and maintains better fluidity than the nylon composite of comparative examples 1 and 2 without attapulgite clay. Because the attapulgite clay has lower hardness and smaller size, the attapulgite clay is well dispersed in a matrix after surface treatment, plays a role in heterogeneous nucleation, and is beneficial to improving the crystallization rate and the crystallinity of nylon resin. The attapulgite clay solves the problem that glass fibers are difficult to disperse and easy to float on the surface under the condition of high glass fiber content, thereby obtaining the high-performance reinforced nylon composite material with high mechanical strength, easy processing and good surface. The more chopped glass fibers are added, while improving the mechanical properties of the nylon composite, it is apparent that the melt flow rate is also affected.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the claims. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of the application should be assessed as that of the appended claims.
Claims (9)
1. The nylon composite material is characterized by comprising the following components in percentage by weight:
33 to 66.8 percent of nylon resin,
40 to 50 percent of chopped glass fiber,
2 to 10 percent of attapulgite clay,
1 to 5 percent of compatilizer,
0.1 to 1 percent of lubricant,
0.1 to 1 percent of antioxidant;
the average particle size of the attapulgite clay is larger than 3000 meshes, and the surface of the attapulgite clay is subjected to acidification treatment;
the compatilizer is maleic anhydride grafted polyethylene-octene copolymer;
the average length of the chopped glass fibers is 3 mm-4.5 mm, and the average diameter of the chopped glass fibers is 10 mu m-14 mu m.
2. The nylon composite of claim 1, wherein the nylon resin is at least one of nylon 6 or nylon 66.
3. The nylon composite of claim 1, wherein the lubricant is at least one of ethylene bis stearamide, silicone powder, pentaerythritol stearate, or montanate.
4. The nylon composite of claim 1, wherein the antioxidant is at least one of a hindered phenolic antioxidant or a phosphorus-containing antioxidant.
5. The nylon composite of claim 1, wherein the acidification treatment is: soaking the attapulgite clay in inorganic acid, washing the attapulgite clay soaked in the inorganic acid with water until the pH value is neutral, and drying the washed attapulgite clay.
6. The nylon composite of any one of claims 1 to 5, wherein the compatibilizing agent is 1.8% -3.7% by weight.
7. The nylon composite of any one of claims 1 to 5, wherein the antioxidant is 0.1% -0.8% by weight.
8. The preparation method of the nylon composite material is characterized by comprising the following steps of:
mixing the nylon resin, the attapulgite clay, the compatilizer, the lubricant and the antioxidant in the nylon composite material according to any one of claims 1 to 7 in proportion to obtain a raw material mixture;
and respectively adding the raw material mixture and the chopped glass fibers into an extruder, and carrying out melt extrusion, cooling and granulation in the extruder to obtain the modified nylon composite material.
9. A nylon article prepared from the nylon composite of any one of claims 1 to 7.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843911A (en) * | 2006-04-17 | 2006-10-11 | 江南大学 | Method for preparing silane coupler modified attapulgite |
| CN101613112A (en) * | 2009-07-06 | 2009-12-30 | 江南大学 | A kind of preparation of attapulgite modified by silane coupling agent |
| CN101659788A (en) * | 2009-09-14 | 2010-03-03 | 浙江工业大学 | Special material of environment-friendly flame-retardant glass-fiber reinforced nylon 6 and preparation method thereof |
| CN102504529A (en) * | 2011-11-17 | 2012-06-20 | 常州大学 | Halogen-free flame-retardant long glass fiber reinforced nylon 6 material and preparation method thereof |
| CN105504798A (en) * | 2016-01-20 | 2016-04-20 | 惠州市华聚塑化科技有限公司 | Glass fiber reinforced nylon composite material |
| CN105504799A (en) * | 2016-01-20 | 2016-04-20 | 惠州市华聚塑化科技有限公司 | Nylon composite material |
| CN108192341A (en) * | 2018-01-06 | 2018-06-22 | 泉州永聚兴塑胶原料有限公司 | It is molded the formula and preparation method of high-performance modified polyamide material |
-
2019
- 2019-12-31 CN CN201911415941.0A patent/CN111117219B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843911A (en) * | 2006-04-17 | 2006-10-11 | 江南大学 | Method for preparing silane coupler modified attapulgite |
| CN101613112A (en) * | 2009-07-06 | 2009-12-30 | 江南大学 | A kind of preparation of attapulgite modified by silane coupling agent |
| CN101659788A (en) * | 2009-09-14 | 2010-03-03 | 浙江工业大学 | Special material of environment-friendly flame-retardant glass-fiber reinforced nylon 6 and preparation method thereof |
| CN102504529A (en) * | 2011-11-17 | 2012-06-20 | 常州大学 | Halogen-free flame-retardant long glass fiber reinforced nylon 6 material and preparation method thereof |
| CN105504798A (en) * | 2016-01-20 | 2016-04-20 | 惠州市华聚塑化科技有限公司 | Glass fiber reinforced nylon composite material |
| CN105504799A (en) * | 2016-01-20 | 2016-04-20 | 惠州市华聚塑化科技有限公司 | Nylon composite material |
| CN108192341A (en) * | 2018-01-06 | 2018-06-22 | 泉州永聚兴塑胶原料有限公司 | It is molded the formula and preparation method of high-performance modified polyamide material |
Non-Patent Citations (3)
| Title |
|---|
| "凹凸棒土在塑料中的应用研究进展";李明等;《精细与专用化学品》;20180221;第26卷(第2期);第47-50页 * |
| 孔萍等主编."塑料材料".《塑料材料》.广东高等教育出版社,2017,(第1版),第261-262页. * |
| 李明等."凹凸棒土在塑料中的应用研究进展".《精细与专用化学品》.2018,第26卷(第2期),第47-50页. * |
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