CN112322034A - Anti-yellowing nylon composite material and preparation method thereof - Google Patents
Anti-yellowing nylon composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a yellowing-resistant nylon composite material and a preparation method thereof, wherein during preparation, 20-98 parts of dry nylon resin, 0.2-10 parts of organic solvent, 0-40 parts of filler, 0.05-0.4 part of antioxidant and 0.1-0.8 part of lubricant are added into a main feed, and the organic solvent reduces the viscosity of a blending system; 0-60 parts of reinforced fiber and 0.02-10 parts of end capping agent are added into the side feeding material, and the organic solvent is favorable for the uniform dispersion and the activity capability of the end capping agent in the system, so that the end capping rate of the end group of the nylon molecular chain is increased, and the amino and carboxyl at the tail end of the nylon molecular chain in the blending system are greatly reduced; in the process of vaporizing and discharging the added organic solvent, oxygen, monomers and oligomers in the blending system are taken away, so that the materials are prevented from being oxidized, decomposed and yellowed due to long-time contact with oxygen in the high-temperature melting and blending processes, and the product with yellowing resistance, heat resistance and thermal stability obviously improved is obtained.
Description
Technical Field
The invention belongs to the technical field of high polymer material processing, and particularly relates to a yellowing-resistant nylon composite material and a preparation method thereof.
Background
Polyamide, commonly known as nylon and known by the English name Polyamide, is a generic name for polymers containing amide groups in the repeating units of the macromolecular main chain. The polyamide can be prepared by ring-opening polymerization of lactam or polycondensation of diamine and dibasic acid. The raw material for manufacturing the fiber is firstly used, and then is suitable for being filled, reinforced and modified by glass fiber and other fillers due to good comprehensive properties including mechanical property, heat resistance, abrasion resistance, chemical resistance and self-lubricity, low friction coefficient, certain flame retardance and easy processing, so that the performance of the resin is greatly improved, and the fiber is widely applied to the fields of machinery, automobiles, electric appliances, textile equipment, chemical equipment, aviation, metallurgy and the like. The polyamides are various in variety, such as PA6, PA66, PA11, PA12, PA46, PA610, PA612 and PA PAl010, and new varieties such as semi-aromatic nylon and special nylon developed in recent years, and are the varieties with the largest yield, the largest variety and the widest application from five general engineering plastics.
The amido bond in the polyamide endows the nylon with excellent mechanical property, and simultaneously, in the processing and using processes, the amido bond is aged and decomposed due to the influence of factors such as heat, ultraviolet rays, oxygen, moisture in the atmosphere and the like, and the color gradually turns yellow. Yellowing is more pronounced if the product formulation as a whole is alkaline. Because the nylon product is obtained by polymerizing lactam or dibasic acid and diamine, the tail end of a molecular chain still has unreacted amino and carboxyl after the reaction is finished, although an end-blocking measure can be adopted in the polymerization process, all the amino and carboxyl on the molecular chain of the polyamide can not be blocked due to low content of an end-blocking agent, the yellowing effect of the polyamide can be further aggravated by the amino and new amino generated by molecular chain breakage in the later processing and modification process of the polyamide, and the use of the polyamide in light-color application occasions, such as LED lamp brackets and other fields, is influenced.
The conventional solution is to add various hindered phenols, hindered amines, phosphoric acid antioxidants and heat stabilizers to inhibit the breakage of amide molecular chains and the occurrence of side reactions. However, these small-molecule assistants first act to protect the polyamide matrix by themselves, by oxidative decomposition, which is increasingly weaker or even eliminated as the number of processing and service cycles increases. And in the later processing and using process, the small molecular aids are slowly separated out, so that the appearance of the finished piece is influenced. Furthermore, the price of such additives is often several times that of the polyamide matrix, and the addition of large amounts will undoubtedly increase the production costs and reduce the market competitiveness of the final product. More importantly, the addition of the heat stabilizer can only prevent molecular chain from being broken to generate new amino and carboxyl, and the original terminal group in the resin cannot be reduced or eliminated.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a yellowing-resistant nylon composite material and a preparation method thereof, and solves the problem of yellowing effect in the background technology.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: the preparation method of the yellowing-resistant nylon composite material comprises the following steps:
(1) uniformly mixing 20-98 parts by mass of dried nylon resin, 0.2-10 parts by mass of organic solvent, 0-40 parts by mass of filler, 0.05-0.4 part by mass of antioxidant and 0.1-0.8 part by mass of lubricant to obtain a mixture;
(2) adding the mixture into a double-screw extruder from a main feeding port of the double-screw extruder, adding 0-60 parts of reinforcing fiber and 0.02-10 parts of end-capping reagent into the double-screw extruder from a side feeding port or a liquid feeding port of the double-screw extruder, and obtaining the yellowing-resistant nylon composite material after bracing, cooling, granulating and drying;
wherein the processing temperature of each area of the double-screw extruder is 260 +/-80 ℃, the head temperature is 265 +/-80 ℃, and the boiling point of the organic solvent is higher than 150 ℃ and lower than 300 ℃.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the anti-yellowing nylon composite material prepared by the preparation method comprises the following components in parts by mass:
compared with the background technology, the technical scheme has the following advantages:
1. according to the invention, the organic solvent is added into the main feeding port, so that the viscosity of the system is reduced under the condition of not increasing the processing temperature, and the thermal decomposition of the system at high temperature is reduced, so that the product has better quality;
2. according to the invention, after the viscosity of the system is reduced by adding the organic solvent, the end-capping reagent is added from the side feeding, so that the uniform dispersion and the activity capability of the end-capping reagent in the system are facilitated, and the end-capping reagent can freely react with molecular chain end groups, thereby increasing the end-capping rate of the end groups, solving the problem that all amino groups and carboxyl groups on the polyamide molecular chain cannot be sealed due to low content of the end-capping reagent in the prior art, and obtaining a product with obviously improved heat resistance and heat stability;
3. the boiling point of the added organic solvent is controlled to be higher than 150 ℃ but lower than 300 ℃, and a large amount of organic solvent can be vaporized and discharged from the system at the processing temperature of the double-screw extruder, so that air carried in the material can be taken out, the material is prevented from being oxidized, decomposed and yellowed due to long-time contact with oxygen in the processes of high-temperature melting and blending, and the color of the product is white;
4. the invention adopts a double-screw extruder with a vacuum port, and accelerates the taking away of organic solvent and a small amount of monomers and oligomers existing in a blending system by a vacuumizing mode, thereby reducing the monomers and oligomers in the final product; the gas content in the injection molding process is reduced, the phenomena of corrosion of monomers and oligomers to a mold, precipitation adhesion on the surface of a manufactured part, blockage of an exhaust hole of the mold and scorching of the manufactured part far away from a glue port end caused by poor exhaust due to blockage of the mold hole are avoided, and the manufactured part has better surface gloss, excellent mechanical property and heat resistance;
5. the invention reduces the addition of small molecular additives such as an antioxidant, a heat stabilizer and the like, can reduce the production cost, improve the market competitiveness of products, reduce the addition of powder additives in the modification process and improve the production environment of workshops.
Detailed Description
It should be noted that, in the examples or comparative examples provided below, the following detection methods were employed:
and (3) testing the content of the terminal amino group: titrating the content of terminal amino groups of the product by using a full-automatic potentiometric titrator, taking 0.8g of nylon product, adding 50mL of m-cresol, heating and stirring at 65 ℃, adding 33mL of isopropanol after the sample is observed to be completely dissolved, continuing stirring for 15min, and titrating the content of the terminal amino groups by using a calibrated perchloric acid-ethanol standard solution.
And (3) testing the content of terminal carboxyl groups: titrating the content of terminal carboxyl of the product by a full-automatic potentiometric titrator, taking 0.5g of nylon product, adding 50mL of o-cresol, heating and refluxing, observing that the sample is completely dissolved, rapidly adding 400uL of formaldehyde solution after cooling, and titrating the content of terminal carboxyl by using a calibrated KOH-ethanol solution.
Monomer and oligomer content testing: adding 20-30 g of nylon product (vacuum drying at 110 ℃ for 24h) and 200mL of distilled water into a 300mL conical flask, and stirring for 24h in boiling water at 100 ℃; the filtrate after filtration and the particle cleaning solution (50mL water and 50mL isopropyl alcohol) were distilled under reduced pressure to remove the solvent to obtain a dried extract component, and the weight was measured to calculate the content of extractables as follows:
the calculation formula is as follows:
in the formula:
m0-mass of polymer product, g;
m1-mass of extracted component, g;
the monomer and oligomer content of the w-nylon product.
And (3) yellowing resistance test: drying the nylon product to be tested in a forced air oven at 180 ℃ for 2h, and then comparing the b values before and after the test by using a yellowness index color difference meter.
The following examples were prepared as follows:
(1) uniformly mixing nylon resin, an organic solvent, a filler (if contained), an antioxidant and a lubricant according to the proportion in the table 1 to obtain a mixture;
(2) adding the mixture into a double-screw extruder from a main feeding port of the double-screw extruder, adding the reinforced fiber (if contained) and the end-capping reagent into the double-screw extruder from a side feeding port or a liquid feeding port of the double-screw extruder, and carrying out bracing, cooling, granulating and drying to obtain the yellowing-resistant nylon composite material;
wherein, in the step (1), the dried nylon resin is obtained by blowing and drying the nylon resin at 60-140 ℃ for 4-12 hours, the rotating speed of the high-speed mixer is 300-800r/min, and the mixing time is 2-10 min.
In step (2), the length to diameter ratio of the twin-screw extruder is selected from 32:1 to 72:1, preferably from 44:1 to 60: 1;
the double-screw extruder is selected from all double-screw extruders with heating and blending functions, preferably a double-screw extruder with double vacuum ports, can be used, and only needs to ensure good suction effect;
the screw rotating speed of the double-screw extruder is selected from 50-900r/min, preferably 100-300r/min, and the slower screw rotating speed is helpful for prolonging the retention time of materials in a screw barrel and improving the end capping effect.
If the end-capping reagent is liquid, the end-capping reagent needs to be quantitatively added into the blending system at a constant speed through a liquid charging port by using a peristaltic pump. If the end-capping reagent is a solid, it may be fed into the blending system by a conventional side-feed screw.
Comparative example 1
(1) Adding 99.4 parts of dried nylon resin polyhexamethylene adipamide (PA66), 0.1 part of antioxidant N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 0.1 part of antioxidant tris [ 2.4-di-tert-butylphenyl ] phosphite and 0.4 part of lubricant zinc stearate into a high-speed mixer, and uniformly mixing to obtain a mixture;
(2) and drawing strips, cooling, cutting into granules and drying to obtain the nylon PA66 material.
Wherein, in the step (1), the dried nylon resin PA66 is obtained by drying the nylon resin PA66 for 6 hours by blowing at 100 ℃; the rotating speed of the high-speed mixer is 600r/min, and the mixing time is 4 min.
In the step (2), the length-diameter ratio of the double-screw extruder is 48, the double-vacuum port is arranged, the processing temperature is 270 ℃, the head temperature is 265 ℃, and the rotating speed of the double-screw extruder is 250 r/min.
The resulting product was tested for amino end group content, carboxyl end group content, monomer and oligomer content, and yellowing resistance, and the results are shown in table 1 below.
Comparative example 2
The production process of the product is basically the same as that of the comparative example 1, except that 4 parts of organic solvent N-methyl pyrrolidone is added, and the N-methyl pyrrolidone and other raw materials are blended in a high-speed mixer and then are blended and extruded by a double-screw extruder to obtain the product.
The resulting product was tested for amino end group content, carboxyl end group content, monomer and oligomer content, and yellowing resistance, and the results are shown in table 1 below.
Comparative example 3
The production process of the product is basically the same as that of the comparative example 1, except that 2 parts of the end-capping agent of the m-toluene isocyanate is added, the end-capping agent is quantitatively added into a blending system at a constant speed through a liquid charging opening by using a peristaltic pump, and the mixture is blended and extruded by a double-screw extruder to obtain the product.
The resulting product was tested for amino end group content, carboxyl end group content, monomer and oligomer content, and yellowing resistance, and the results are shown in table 1 below.
Example 1
In the embodiment 1, 4 parts of organic solvent N-methyl pyrrolidone is added, the organic solvent N-methyl pyrrolidone and other raw materials are blended in a high-speed mixer, 2 parts of end capping agent m-toluene isocyanate is added, the end capping agent is quantitatively added into a blending system at a constant speed through a liquid feeding port by using a peristaltic pump, and the mixture is blended and extruded by a double-screw extruder to obtain a product.
The resulting product was tested for amino end group content, carboxyl end group content, monomer and oligomer content, and yellowing resistance, and the results are shown in table 1 below.
TABLE 1 COMPARATIVE EXAMPLES 1-3 AND EXAMPLE 1 FORMULATIONS AND PERFORMANCE TESTS
As can be seen from the comparison of the formulas and the performance test tables of the comparative examples 1 to 3 and the example 1, the content of the monomer and the oligomer in the product is obviously reduced by adding the organic solvent into the blending system in the comparative example 2, because the organic solvent brings out part of the monomer and the oligomer in the process of massive gasification, the content of the monomer and the oligomer in the system is obviously reduced. Comparative example 3 the content of the terminal amino group and the terminal carboxyl group of the product is obviously reduced by adding the end capping agent into the blending system, because the end capping agent reacts with the terminal amino group and the terminal carboxyl group at the tail end of the nylon molecular chain to play the role of end capping in the blending process, the content of the terminal amino group and the content of the terminal carboxyl group in the system are obviously reduced. In the embodiment 1, the organic solvent and the end capping agent are added simultaneously, so that the content of the terminal amino group and the content of the terminal carboxyl group of the product are further reduced on the basis of the comparative example 3, and the content of the monomer and the oligomer in the system is also obviously reduced, because the viscosity of the system is reduced by adding the organic solvent, the mobility of the end capping agent in the blending system is enhanced, the end capping agent can better react with the terminal amino group and the terminal carboxyl group at the tail end of a nylon molecular chain, so that the content of the terminal amino group and the terminal carboxyl group in the system is further reduced, and simultaneously, a large amount of the monomer and the oligomer are taken away by the organic solvent in the gasification process, so that the monomer. The b value is closely related to the content of the terminal amino group and the terminal carboxyl group in the system, and the content of the terminal amino group and the terminal carboxyl group is the least in example 1, so that the b value is also the smallest, and the best yellowing resistance is shown.
Examples 2 to 7
The formulations and properties of examples 2 to 7 are shown in table 2 below, the production process is basically the same as that of example 1, except that the type and amount of the nylon resin, the type and amount of the organic solvent, and the type and amount of the end-capping agent are changed, fillers and reinforcing fibers are added in examples 6 and 7, the fillers, the resin and the additives are blended in a high-speed mixer and then are blended and extruded through a double-screw extruder, and the reinforcing fibers can be fed into the extruder from a side feeding screw to be blended and extruded. The processing temperature is properly adjusted according to the different types of nylon resin, and the general rule is that the processing temperature is about 5 ℃ higher than the melting point of a product without adding fibers, and the processing temperature is about 15 ℃ higher than the melting point of the product with fibers.
Table 2 examples 2-7 formulations and performance test tables
By comparing the formula of the above examples 2 to 7 and the performance test table, it can be seen that the content of the terminal amino group and the terminal carboxyl group of the product is related to the content of the organic solvent and the end-capping reagent in the blending system. Generally, the higher the content of the blocking agent, the lower the content of the terminal amino groups and the terminal carboxyl groups, and the more the amount of the organic solvent used is increased, the further enhancement of the effect is attained. In addition, the use amount of the organic solvent is increased, and the obvious effect of reducing the content of the monomer and the oligomer in the system is also achieved. The reduction of the content of the terminal amino groups and the terminal carboxyl groups can be realized by the method of the invention for different nylon resin matrixes. Meanwhile, the added filler or reinforcing fiber can realize the effect of improving the mechanical property and the heat resistance of the product.
It will be appreciated by those skilled in the art that the same or similar technical effects as those of the above embodiments can be expected when the technical parameters of the present invention are changed within the following ranges:
the nylon resin is prepared from a diacid unit and a diamine unit or an aminocarboxylic acid unit through polycondensation reaction, and can also be obtained through ring-opening polymerization of a lactam monomer.
The dibasic acid unit is selected from aliphatic dibasic acid of C4-C36, alicyclic dibasic acid of C4-C36, aromatic dibasic acid of C8-C18 or a mixture thereof;
the aliphatic dibasic acid is preferably selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, octadecenedioic acid, eicosanedioic acid, docosanedioic acid or mixtures thereof, and further preferably from succinic acid, adipic acid, sebacic acid, dodecanedioic acid or mixtures thereof.
The cycloaliphatic diacid is preferably selected from the group consisting of cyclohexanedicarboxylic acid, cyclohexanediacetic acid, or mixtures thereof.
The aromatic dibasic acid is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid or a mixture thereof.
The diamine unit is selected from C4-C36 aliphatic diamine, C4-C36 alicyclic diamine, C8-C18 aromatic diamine or a mixture thereof;
the aliphatic diamine is preferably selected from ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, decylenediamine, undecylenediamine, dodecyldiamine, tridecylenediamine, tetradecylenediamine, pentadecylenediamine, hexadecylenediamine, heptadecylenediamine, octadecylenediamine, nonadecylenediamine, eicosanediamine, docosanediamine, 2,2, 4-trimethyl-1, 6-hexanediamine, 2,4, 4-trimethyl-1, 6-hexanediamine, 1, 3-diaminopentane, 2-methyl-1, 5-pentanediamine, 2-methyl-1, 8-octanediamine or a mixture thereof, further preferably selected from butylenediamine, pentylenediamine, hexylenediamine, nonylenediamine, decylenediamine, 2-methyl-1, 5-pentanediamine, 2-methyl-1, 8-octanediamine, or a mixture thereof.
The alicyclic diamine is preferably selected from the group consisting of cyclohexyldiamine, bis (3, 5-dialkyl-4-aminocyclohexyl) methane, bis (3, 5-dialkyl-4-aminocyclohexyl) ethane, bis (3, 5-dialkyl-4-aminocyclohexyl) propane, bis (3, 5-dialkyl-4-aminocyclohexyl) butane, bis (3-methyl-4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) methane, isopropylidene bis (cyclohexylamine), 1-amino-3-aminomethyl-3, 5, 5-trimethylcyclohexane, bis (aminoethyl) piperazine, bis (aminopropyl) piperazine or a mixture thereof.
The aminocarboxylic acid is selected from C4-C18 aminocarboxylic acid units or mixtures thereof, preferably 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminocaprylic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, p-aminobenzoic acid or mixtures thereof.
The lactam is selected from C4-C18 lactam units or a mixture thereof, preferably pyrrolidone, 2-piperidone, caprolactam, enantholactam, caprylolactam, nonanolactam, decanolactam, undecanolactam, dodecanolactam or a mixture thereof.
Further, the nylon resin is preferably selected from polycaprolactam (PA6), polytetramethyleneadipamide (PA46), polypentylglycol adipamide (PA56), polyhexamethyleneadipamide (PA66), polyhexamethylenesebacamide (PA610), polydecamethylenesebacamide (PA1010), polyhexamethylenedodecadicarboxamide (PA612), polydecamethylenedodecamide (PA1012), polyundecanolactam (PA11), polydodecanolactam (PA12), polydodecanoyldodecadiamine (PA1212), copolymerized nylon of polyhexamethyleneterephthalamide/hexamethylene isophthalamide (PA6T/6I), copolymerized nylon of polyhexamethyleneterephthalamide/hexamethylene adipamide (PA6T/66), copolymerized nylon of polyhexamethyleneterephthalamide/hexamethylene isophthalamide (PA6T/6I/66), copolymerized nylon of polyhexamethyleneterephthalamide/caprolactam (PA6T/6), Poly (hexamethylene terephthalamide)/2-methylpentamethylene terephthalamide copolymer nylons (PA6T/M-5T), poly (nonane terephthalamide) (PA9T), poly (decamethylene terephthalamide) (PA10T) or mixtures thereof.
The organic solvent is selected from organic solvents with certain solubility (solubility is more than 1g) for nylon products, and is preferably selected from N, N-dimethylformamide, N-methylpyrrolidone, phenol, m-cresol, o-cresol, toluene, xylene, dichloromethane, trichloromethane, carbon tetrachloride or 1, 2-dichloroethane or a mixture thereof.
The organic solvent is further preferably an organic solvent having a boiling point of less than 300 ℃, preferably N, N-dimethylformamide, N-methylpyrrolidone, phenol, m-cresol, o-cresol, toluene, xylene, dichloromethane, carbon tetrachloride, 1, 2-dichloroethane or a mixture thereof.
Further, the organic solvent is preferably selected from organic solvents having a boiling point higher than 150 ℃ and lower than 300 ℃, preferably N, N-dimethylformamide, N-methylpyrrolidone, phenol, m-cresol, o-cresol or a mixture thereof.
The filler is selected from wollastonite, zeolite, talc, pyrophyllite, dolomite, feldspar, clay, kaolin, bentonite, montmorillonite, hectorite, diatomaceous earth, sericite, mica, synthetic mica, alumina, silica, magnesia, iron oxide, zinc oxide, zirconia, titanium dioxide, silica, permanent/magnetizable metal compounds/alloys, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide, quartz, lime, gypsum, asbestos, aluminosilicate, chalk or mixtures thereof. Further preferred is selected from wollastonite, talc, kaolin, montmorillonite, magnesium oxide, zinc oxide, titanium dioxide, silica, calcium carbonate, barium sulfate, magnesium hydroxide, aluminum hydroxide or a mixture thereof.
The blocking agent is selected from compounds containing epoxy groups, isocyanate groups and the like, which can react with terminal amino groups and carboxyl groups and do not contain polar groups after the reaction.
Further, the epoxy group-containing compound is preferably one or a mixture of several selected from the group consisting of ethylene oxide, propylene oxide, epichlorohydrin, 1, 2-epoxycyclopentane, 1, 2-epoxypentane and 1, 2-epoxyhexane, and further preferably ethylene oxide, propylene oxide, epichlorohydrin or a mixture thereof.
Further, the isocyanate group-containing compound is preferably selected from the group consisting of propane isocyanate, butane isocyanate, pentane isocyanate, hexane isocyanate, octane isocyanate, decane isocyanate, benzene isocyanate, p-toluene isocyanate, m-toluene isocyanate, o-toluene isocyanate, or a mixture thereof.
The reinforcing fibers are selected from glass fibers, potassium titanate fibers, metal clad glass fibers, ceramic fibers, wollastonite fibers, carbon fibers, metal carbide fibers, metal cured fibers, asbestos fibers, alumina fibers, silicon carbide fibers, gypsum fibers, boron fibers, aramid fibers, or mixtures thereof. Further preferred are glass fibers, carbon fibers, aramid fibers or mixtures thereof.
The antioxidant is selected from copper salt, amine antioxidant, phenol antioxidant, sulfur antioxidant and phosphorus antioxidant. These antioxidants may be used alone or in combination, and any antioxidant or combination thereof which does not adversely affect the experimental effects of the present invention can be used in the present invention. Further preferred is a compound selected from cuprous chloride, N '-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione, tris [2, 4-di-tert-butylphenyl ] phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, tetrakis (2, 4-di-tert-butylphenyl) 4,4' -diphenyl diphosphite or a mixture thereof.
The lubricant is selected from long carbon chain carboxylic acids, amide waxes, carboxylic acid esters, carboxylic acid metal salts, polyols, olefin waxes, silicones. These lubricants may be used alone or in combination, and may be used in the present invention as long as the properties of the product are not affected. Further selected from stearic acid, palmitic acid, montanic acid, ethylene bis stearamide, erucamide, pentaerythritol stearate, montanic acid esters, zinc stearate, calcium stearate, sodium montanate, calcium montanate, pentaerythritol, dipentaerythritol, polyethylene waxes, oxidized polyethylene waxes, silicones, or mixtures thereof.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a yellowing-resistant nylon composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly mixing 20-98 parts by mass of dried nylon resin, 0.2-10 parts by mass of organic solvent, 0-40 parts by mass of filler, 0.05-0.4 part by mass of antioxidant and 0.1-0.8 part by mass of lubricant to obtain a mixture;
(2) adding the mixture into a double-screw extruder from a main feeding port of the double-screw extruder, adding 0-60 parts of reinforcing fiber and 0.02-10 parts of end-capping reagent into the double-screw extruder from a side feeding port or a liquid feeding port of the double-screw extruder, and obtaining the yellowing-resistant nylon composite material after bracing, cooling, granulating and drying;
wherein the processing temperature of each area of the double-screw extruder is 260 +/-80 ℃, the head temperature is 265 +/-80 ℃, and the boiling point of the organic solvent is higher than 150 ℃ and lower than 300 ℃.
2. The preparation method of the yellowing-resistant nylon composite material as claimed in claim 1, wherein the preparation method comprises the following steps: the double-screw extruder has a heating blending function and is provided with a vacuum port, and the organic solvent takes away oxygen, monomers and oligomers in a blending system in the processing process and is discharged out of the double-screw extruder from the vacuum port.
3. The preparation method of the yellowing-resistant nylon composite material as claimed in claim 1, wherein the preparation method comprises the following steps: the organic solvent comprises at least one of N, N-dimethylformamide, N-methylpyrrolidone, phenol, m-cresol, o-cresol, toluene, xylene, dichloromethane, carbon tetrachloride and 1, 2-dichloroethane.
4. The preparation method of the yellowing-resistant nylon composite material as claimed in claim 1, wherein the preparation method comprises the following steps: the blocking agent is used for reacting with amino and carboxyl at the tail end of a nylon molecular chain, does not have a polar group after reaction, and comprises a compound containing an epoxy group or an isocyanate group.
5. The preparation method of the yellowing-resistant nylon composite material as claimed in claim 1, wherein the preparation method comprises the following steps: the blocking agent comprises at least one of ethylene oxide, propylene oxide, epichlorohydrin, 1, 2-epoxycyclopentane, 1, 2-epoxypentane, 1, 2-epoxyhexane, propylene isocyanate, butyl isocyanate, amyl isocyanate, hexamethylene isocyanate, octyl isocyanate, decyl isocyanate, phenyl isocyanate, p-toluene isocyanate, m-toluene isocyanate and o-toluene isocyanate.
6. The preparation method of the yellowing-resistant nylon composite material as claimed in claim 1, wherein the preparation method comprises the following steps: the screw rotating speed of the double-screw extruder is 50-900r/min, and the length-diameter ratio of the screw is 32:1-72: 1.
7. The preparation method of the yellowing-resistant nylon composite material as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (1), the nylon resin is dried by blowing air at 60-140 ℃ for 4-12 hours to obtain the dried nylon resin, and the dried nylon resin is uniformly mixed with other components by adopting a high-speed mixer with the rotating speed of 300-800 r/min.
8. The yellowing-resistant nylon composite material prepared by the method of any one of claims 1 to 7, which is characterized in that: the adhesive comprises the following components in parts by mass:
9. the yellowing-resistant nylon composite material of claim 8, wherein: the adhesive comprises the following components in parts by mass:
10. the yellowing-resistant nylon composite material of claim 8, wherein: the content of terminal carboxyl groups of the composite material is not higher than 57mmol/kg, the content of terminal amino groups is not higher than 19mmol/kg, and the content of monomers and oligomers is not higher than 0.32 wt%.
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| CN115851113A (en) * | 2022-12-09 | 2023-03-28 | 万华化学集团股份有限公司 | Nylon powder coating and preparation method and application thereof |
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| CN102918080A (en) * | 2010-07-27 | 2013-02-06 | 三菱瓦斯化学株式会社 | Polyamide resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115851113A (en) * | 2022-12-09 | 2023-03-28 | 万华化学集团股份有限公司 | Nylon powder coating and preparation method and application thereof |
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