CN112322034B - Yellowing-resistant nylon composite material and preparation method thereof - Google Patents
Yellowing-resistant nylon composite material and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a yellowing-resistant nylon composite material and a preparation method thereof, wherein 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 through a main feed, and the viscosity of a blending system is reduced by the organic solvent; adding 0-60 parts of reinforcing fiber and 0.02-10 parts of end capping agent into the side feed, wherein the organic solvent is favorable for uniform dispersion and activity 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 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 yellowing after contacting with oxygen for a long time in the high-temperature melting and blending process, and the products with obviously improved yellowing resistance, heat resistance and thermal stability are obtained.
Description
Technical Field
The invention belongs to the technical field of polymer material processing, and particularly relates to a yellowing-resistant nylon composite material and a preparation method thereof.
Background
Polyamide, commonly known as nylon, is called Polyamide in english, which is a generic name for polymers containing amide groups in the repeat units of the macromolecular backbone. The polyamide can be prepared by ring-opening polymerization of lactam or polycondensation of diamine and diacid. The raw materials for manufacturing the fiber are low in friction coefficient, flame retardant and easy to process due to good comprehensive properties including mechanical properties, heat resistance, abrasion resistance, chemical resistance and self-lubricating property, are suitable for filling, reinforcing and modifying with glass fibers and other fillers, greatly improve the properties of the resin, and are widely applied to the fields of machinery, automobiles, electrical appliances, textile equipment, chemical equipment, aviation, metallurgy and the like. The polyamides have various varieties including PA6, PA66, PA11, PA12, PA46, PA610, PA612, PAl010, and new varieties of semi-aromatic nylon, special nylon, and the like developed in recent years, and are the varieties with the largest yield, the largest variety and the largest application among five general engineering plastics.
The amide bond in the polyamide gives excellent mechanical properties to nylon, and meanwhile, the amide bond is aged and decomposed due to the influence of factors such as heat, ultraviolet rays, oxygen, moisture in the atmosphere and the like in the processing and using processes, so that the color of the polyamide becomes yellow gradually. At this time, if the product formulation is entirely alkaline, yellowing is more pronounced. The nylon product is obtained by polymerizing lactam or dibasic acid and diamine, and after the reaction is finished, the tail end of a molecular chain still has unreacted amino groups and carboxyl groups, and although end capping measures are adopted in the polymerization process, all the amino groups and the carboxyl groups on a polyamide molecular chain cannot be capped due to low content of an end capping agent, and the yellowing effect of the polyamide is further aggravated by the amino groups at the moment and new amino groups generated by molecular chain breakage of the polyamide in the later processing and modification process, so that the nylon product is influenced in light-color application occasions such as the application of LED lamp brackets and other fields.
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 auxiliaries act to protect the polyamide matrix by itself first undergoing oxidative decomposition, which is weaker and even vanishes with increasing processing times and service cycle. In addition, the micromolecular auxiliary agents can slowly separate out in the later processing and using processes, so that the appearance of the finished product is affected. In addition, the price of the additive is usually several times that of the polyamide matrix, and the addition of large dosage can certainly increase the production cost and reduce the market competitiveness of the final product. More importantly, the addition of the heat stabilizer can only prevent the breakage of molecular chains to generate new amino groups and carboxyl groups, and the original end groups 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 art.
One of the technical schemes adopted 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 dry 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 fibers and 0.02-10 parts of end capping agent 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 region of the double-screw extruder is 260+/-80 ℃, the temperature of a machine head 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 yellowing-resistant nylon composite material prepared by the preparation method comprises the following components in parts by mass:
compared with the background technology, the technical proposal 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 blocking agent is added from the side feeding, so that the uniform dispersion and the activity capability of the blocking agent in the system are facilitated, the blocking agent can react with the end groups of the molecular chain freely, the blocking rate of the end groups is increased, the problems that the blocking agent content is low and all amino groups and carboxyl groups on the molecular chain of polyamide cannot be blocked in the prior art are solved, and the product with obviously improved heat resistance and thermal stability is obtained;
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 entrained in materials is brought out, oxidative decomposition and yellowing of the materials in the high-temperature melting and blending processes due to long-time contact with oxygen are avoided, and the color of the product is white;
4. the invention adopts a double-screw extruder with a vacuum port, and takes away a small amount of monomers and oligomers existing in the organic solvent and the blending system in an accelerating way by utilizing a vacuumizing way, thereby reducing the monomers and oligomers in the final product; the gas content in the injection molding process is reduced, and the phenomena of corrosion of monomers and oligomers to a die, precipitation adhesion on the surface of a manufactured part, blocking of an exhaust hole of the die, and scorching of a glue inlet end of the manufactured part caused by poor exhaust due to blocking of the die hole are avoided, so that the manufactured part has better surface gloss, excellent mechanical property and heat resistance;
5. the invention reduces the addition of small molecule auxiliary agents such as antioxidant, heat stabilizer and the like, can reduce the production cost, improves the market competitiveness of the product, reduces the addition of powder auxiliary agents in the modification process and improves the production environment of workshops.
Detailed Description
In the examples or comparative examples provided below, the following detection methods were employed:
end amino content test: titrating the amino content 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 ℃, observing that the sample is completely dissolved, adding 33mL of isopropanol, continuously stirring for 15min, and titrating the amino content of the product by using a calibrated perchloric acid-ethanol standard solution.
And (3) terminal carboxyl content test: titration of the carboxyl end group content of the product by a full-automatic potentiometric titrator, taking 0.5g of nylon product, adding 50mL of o-cresol for heating reflux, observing that the sample is completely dissolved, rapidly adding 400uL of formaldehyde solution after cooling, and titration of the carboxyl end group content by using a calibrated KOH-ethanol solution.
Monomer and oligomer content testing: adding 20-30 g nylon product (vacuum dried at 110 ℃ for 24 h) and 200mL distilled water into a 300mL conical flask, and stirring with boiling water at 100 ℃ for 24h; the filtered filtrate and the particulate washings (50 mL of water and 50mL of isopropanol) were distilled under reduced pressure to remove the solvent and obtain dry extract components, which were weighed and the extractables content calculated as follows:
the calculation formula is as follows:
wherein:
m 0 -the mass of the polymer product, g;
m 1 -mass of extracted components, g;
monomer and oligomer content in the w-nylon product.
Yellowing resistance test: the nylon product to be tested is dried in a forced air oven at 180 ℃ for 2 hours, and then the b values before and after the test are compared by using a yellowness index color difference meter.
The following examples were prepared using the following methods:
(1) Uniformly mixing nylon resin, an organic solvent, a filler (such as a filler), an antioxidant and a lubricant according to the proportion shown 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 reinforcing fibers (such as containing) and a blocking agent 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 in the step (1), the dried nylon resin is obtained by air drying the nylon resin at 60-140 ℃ for 4-12 hours, the rotating speed of a high-speed mixer is 300-800r/min, and the mixing time is 2-10min.
In step (2), the aspect ratio of the twin screw extruder is selected from 32:1 to 72:1, preferably 44:1 to 60:1;
the double-screw extruder is selected from all double-screw extruders with heating and blending functions, preferably double-screw extruders with double vacuum ports, and double-screw extruders with single vacuum ports can be used, and only good suction effect is ensured;
the screw speed of the double-screw extruder is selected from 50-900r/min, preferably 100-300r/min, and the slower screw speed is beneficial to prolonging the residence time of materials in the screw machine barrel and improving the end-capping effect.
If the end-capping agent is liquid, the end-capping agent needs to be quantitatively added into the blending system at a constant speed through a liquid charging port by utilizing a peristaltic pump. The endcapping agent, if solid, may be fed into the blending system by a conventional side feed screw.
Comparative example 1
(1) 99.4 parts of dried nylon resin polyhexamethylene adipamide (PA 66), 0.1 part of antioxidant N, N' -bis- (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 are added into a high-speed mixer to be uniformly mixed to obtain a mixture;
(2) And drawing, cooling, granulating and drying to obtain the nylon PA66 material.
Wherein, in the step (1), the dried nylon resin PA66 is obtained by air-drying the nylon resin PA66 at 100 ℃ for 6 hours; the rotation speed of the high-speed mixer is 600r/min, and the mixing time is 4min.
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 temperature of a machine head is 265 ℃, and the rotating speed of the double-screw extruder is 250r/min.
The resulting product was tested for terminal amino content, terminal carboxyl 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 comparative example 1, except that 4 parts of organic solvent N-methyl pyrrolidone is added, and the product is obtained by blending and extruding the mixture with other raw materials in a high-speed mixer through a double-screw extruder.
The resulting product was tested for terminal amino content, terminal carboxyl 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 comparative example 1, except that 2 parts of m-toluene isocyanate serving as a blocking agent is added, the blocking agent is quantitatively added into a blending system at a constant speed through a liquid feed inlet by using a peristaltic pump, and the product is obtained through blending extrusion by a double-screw extruder.
The resulting product was tested for terminal amino content, terminal carboxyl 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 blocking agent m-toluene isocyanate is added, the blocking agent is quantitatively added into a blending system at a constant speed through a liquid feed inlet by a peristaltic pump, and the blending extrusion is carried out through a double-screw extruder, so that the product is obtained.
The resulting product was tested for terminal amino content, terminal carboxyl content, monomer and oligomer content, and yellowing resistance, and the results are shown in Table 1 below.
Table 1 comparative examples 1 to 3 and example 1 formulations and performance test tables
As can be seen from comparing the formulations and performance test tables of comparative examples 1 to 3 and example 1, comparative example 2 adds an organic solvent to the blending system, the monomer and oligomer contents of the product are significantly reduced, because the organic solvent brings out a part of the monomer and oligomer during the process of massive vaporization, thereby significantly reducing the monomer and oligomer contents in the system. Comparative example 3 the end-capping reagent was added to the blend system and the end-amino and end-carboxyl content of the product was significantly reduced, since the end-capping reagent reacted with the end-amino and end-carboxyl at the end of the nylon molecular chain during blending to effect end-capping, and thus the end-amino and end-carboxyl content in the system was significantly reduced. In the embodiment 1, the organic solvent and the end capping agent are added at the same time, the content of the end amino and the end carboxyl of the product is further reduced on the basis of the comparative example 3, and the content of monomers and oligomers in the system is also obviously reduced, because the addition of the organic solvent reduces the viscosity of the system, so that the activity of the end capping agent in the blending system is enhanced, the end amino and the end carboxyl of the end of a nylon molecular chain can better react, the content of the end amino and the end carboxyl in the system is further reduced, and meanwhile, the organic solvent takes away a large amount of monomers and oligomers in the gasification process, so that the monomers and oligomers in the system are also obviously reduced. The b value is closely related to the content of the terminal amino groups and the terminal carboxyl groups in the system, and the content of the terminal amino groups and the terminal carboxyl groups in the embodiment 1 is the least, so that the b value is also the least, 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, and the production process is substantially the same as that of example 1, except that the type and amount of nylon resin, the type and amount of organic solvent, and the type and amount of capping agent are changed, and examples 6 and 7 are also added with filler and reinforcing fiber, and the filler, resin and additive are blended in a high-speed mixer and then extruded through a twin-screw extruder, and the reinforcing fiber is extruded from a side-feed screw-fed extruder. The processing temperature is properly adjusted according to the types of nylon resin, and the general rule is that the processing temperature is about 5 ℃ higher than the melting point for a non-fiber-added product and about 15 ℃ higher than the melting point for a fiber-added product.
Table 2 examples 2-7 formulations and performance test tables
As can be seen by comparing the formulations of examples 2-7 and the performance test tables, the amino and carboxyl terminal groups content of the product was related to the content of the organic solvent and the end-capping agent in the blend system. In general, the higher the content of the blocking agent, the lower the content of the terminal amino groups and the content of the terminal carboxyl groups, and the more the amount of the organic solvent is added on the basis, the effect is further enhanced. In addition, the use level of the organic solvent is increased, and the method has obvious effect on reducing the content of monomers and oligomers in the system. For different nylon resin matrixes, the reduction of the content of terminal amino groups and terminal carboxyl groups can be realized by the method. Meanwhile, the added filler or reinforcing fiber can realize the effect of improving the mechanical property and heat resistance of the product.
Those skilled in the art will recognize 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 dibasic acid unit and a diamine unit or an aminocarboxylic acid unit through a polycondensation reaction, and can also be prepared from lactam monomers through ring-opening polymerization.
The diacid unit is selected from C4-C36 aliphatic diacid, C4-C36 alicyclic diacid, C8-C18 aromatic diacid 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, eicosanedioic acid, docosanedioic acid or a mixture thereof, more preferably from succinic acid, adipic acid, sebacic acid, dodecanedioic acid or a mixture thereof.
The cycloaliphatic diacid is preferably selected from cyclohexanedicarboxylic acid, cyclohexanediacetic acid, or mixtures thereof.
The aromatic diacid is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, or mixtures 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, pentylene diamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, decylenediamine, undecylenediamine, dodecylenediamine, tridecyldiamine, tetradecylenediamine, pentadecylenediamine, hexadecylenediamine, heptadecylenediamine, octadecyl diamine, nonadecylenediamine, eicosylenediamine, docosyylenediamine, 2, 4-trimethyl-1, 6-hexamethylenediamine, 2, 4-trimethyl-1, 6-hexamethylenediamine, 1, 3-diaminopentane, 2-methyl-1, 5-pentylene diamine, 2-methyl-1, 8-octylenediamine or a mixture thereof, further preferably selected from butanediamine, pentylene diamine, hexylenediamine, nonylenediamine, decylenediamine, 2-methyl-1, 5-pentylene diamine, 2-methyl-1, 8-octyldiamine or a mixture thereof.
The cycloaliphatic diamine is preferably selected from the group consisting of cyclohexanediamine, 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, isopropylidenedi (cyclohexylamine), 1-amino-3-aminomethyl-3, 5-trimethylcyclohexane, bis (aminoethyl) piperazine, bis (aminopropyl) piperazine, and mixtures thereof.
The aminocarboxylic acid is selected from a C4-C18 aminocarboxylic acid unit or a mixture 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 a mixture thereof.
The lactam is selected from C4-C18 lactam units or mixtures thereof, preferably pyrrolidone, 2-piperidone, caprolactam, heptanolactam, octalactam, nonanolactam, decalactam, undecanolactam, dodecalactam or mixtures thereof.
Further, the nylon resin is preferably selected from polycaprolactam (PA 6), polybutylene adipamide (PA 46), polybutylene adipamide (PA 56), polyhexamethylene adipamide (PA 66), polyhexamethylene sebacamide (PA 610), polyhexamethylene sebacamide (PA 1010), polyhexamethylene dodecanoamide (PA 612), polyhexamethylene dodecanoamide (PA 1012), polyhexamethylene undecanolactam (PA 11), polydodecanoamide (PA 12), polyhexamethylene dodecanoamide (PA 1212), a copolymer nylon of polyhexamethylene terephthalamide/hexamethylene isophthalamide (PA 6T/6I), a copolymer nylon of polyhexamethylene terephthalamide/hexamethylene adipamide (PA 6T/66), a copolymer nylon of polyhexamethylene terephthalamide/hexamethylene isophthalamide (PA 6T/6I/66), a copolymer nylon of polyhexamethylene terephthalamide/caprolactam (PA 6T/6), a copolymer nylon of polyhexamethylene terephthalamide/hexamethylene terephthalamide/2-methylpentanamide (PA 6T/6), a copolymer nylon of hexamethylene terephthalamide/M-p-phenylene terephthalamide/M (PA 10), or a mixture thereof.
The organic solvent is selected from organic solvents having a certain solubility (solubility greater than 1 g) to the nylon product, preferably selected from N, N-dimethylformamide, N-methylpyrrolidone, phenol, m-cresol, o-cresol, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride or 1, 2-dichloroethane or mixtures thereof.
The organic solvent is further preferably selected from organic solvents having a boiling point below 300 ℃, preferably N, N-dimethylformamide, N-methylpyrrolidone, phenol, m-cresol, o-cresol, toluene, xylene, methylene chloride, carbon tetrachloride, 1, 2-dichloroethane or mixtures thereof.
Further, the organic solvent is preferably an organic solvent having a boiling point above 150 ℃ and below 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, titania, 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 are materials selected from wollastonite, talc, kaolin, montmorillonite, magnesium oxide, zinc oxide, titanium dioxide, silica, calcium carbonate, barium sulfate, magnesium hydroxide, aluminum hydroxide or mixtures 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 have polar groups after the reaction.
Further, the epoxy group-containing compound is preferably one or a mixture of several selected from ethylene oxide, propylene oxide, epichlorohydrin, 1, 2-cyclopentane, 1, 2-pentane oxide, 1, 2-hexane oxide, and more preferably ethylene oxide, propylene oxide, epichlorohydrin or a mixture thereof.
Further, the isocyanate group-containing compound is preferably selected from the group consisting of propyl isocyanate, butyl isocyanate, pentyl isocyanate, hexyl isocyanate, octyl isocyanate, decyl isocyanate, phenyl isocyanate, p-toluene isocyanate, m-toluene isocyanate, o-toluene isocyanate, and mixtures 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 fibers from glass, carbon, aramid or mixtures thereof.
The antioxidant is selected from copper salt, amine antioxidant, phenol antioxidant, sulfur antioxidant and phosphorus-containing antioxidant. These antioxidants may be used alone or in combination, as long as the antioxidants and combinations thereof which do not adversely affect the experimental effect of the present invention are applicable to the present invention. Further preferred are those selected from cuprous chloride, N '-bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 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 mixtures thereof.
The lubricant is selected from long carbon chain carboxylic acids, amide waxes, carboxylic acid esters, metal salts of carboxylic acids, polyols, olefin waxes, silicones. These lubricants may be used alone or in combination, and may be used in the present invention as long as they do not affect the properties of the product. Further selected from stearic acid, palmitic acid, montanic acid, ethylenebisstearamide, erucamide, pentaerythritol stearate, montanic acid esters, zinc stearate, calcium stearate, sodium montanate, calcium montanate, pentaerythritol, dipentaerythritol, polyethylene wax, oxidized polyethylene wax, silicone or mixtures thereof.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (5)
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 dry 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 fibers and 0.02-10 parts of end capping agent 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;
the processing temperature of each region of the double-screw extruder is 260+/-80 ℃, the temperature of a machine head is 265+/-80 ℃, and the boiling point of the organic solvent is higher than 150 ℃ and lower than 300 ℃;
the double-screw extruder is provided with a vacuum port and has a heating and blending function, 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 through the vacuum port;
the organic solvent comprises at least one of N, N-dimethylformamide, phenol, m-cresol and o-cresol;
the blocking agent comprises at least one of ethylene oxide, propylene oxide, epichlorohydrin, 1, 2-cyclopentane, 1, 2-pentane, 1, 2-hexane, propyl isocyanate, butyl isocyanate, pentyl isocyanate, hexyl isocyanate, octyl isocyanate, decyl isocyanate, phenyl isocyanate, p-toluene isocyanate, m-toluene isocyanate and o-toluene isocyanate.
2. The method for preparing the yellowing-resistant nylon composite material according to claim 1, which is characterized in that: 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.
3. The method for preparing the yellowing-resistant nylon composite material according to claim 1, which is characterized in that: in the step (1), the nylon resin is dried by blowing 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.
4. The method for preparing the yellowing-resistant nylon composite material according to claim 1, which is characterized in that: the prepared yellowing-resistant nylon composite material comprises the following components in parts by mass:
35-95 parts of nylon resin,
5-30 parts of filler,
5-50 parts of reinforcing fiber,
0.1 to 0.3 part of antioxidant,
0.2-0.5 parts of lubricant.
5. The method for preparing the yellowing-resistant nylon composite material according to claim 4, which is characterized in that: the yellowing-resistant nylon composite material has a carboxyl end group content of not higher than 57mmol/kg, an amino end group content of not higher than 19mmol/kg, and monomer and oligomer contents of not higher than 0.32wt%.
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| CN101208390A (en) * | 2005-07-22 | 2008-06-25 | 三菱瓦斯化学株式会社 | Polyamide resin composition |
| CN102918080A (en) * | 2010-07-27 | 2013-02-06 | 三菱瓦斯化学株式会社 | Polyamide resin |
| CN110845721A (en) * | 2019-11-04 | 2020-02-28 | 江门市德众泰工程塑胶科技有限公司 | Preparation method of semi-aromatic polyamide |
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| CN101208390A (en) * | 2005-07-22 | 2008-06-25 | 三菱瓦斯化学株式会社 | Polyamide resin composition |
| CN102918080A (en) * | 2010-07-27 | 2013-02-06 | 三菱瓦斯化学株式会社 | Polyamide resin |
| CN110845721A (en) * | 2019-11-04 | 2020-02-28 | 江门市德众泰工程塑胶科技有限公司 | Preparation method of semi-aromatic polyamide |
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