CN114058008A - Process for preparing semi-aromatic polyamides end-capped with monocarboxylic acids, semi-aromatic polyamides and molding compositions - Google Patents

Process for preparing semi-aromatic polyamides end-capped with monocarboxylic acids, semi-aromatic polyamides and molding compositions Download PDF

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CN114058008A
CN114058008A CN202111520458.6A CN202111520458A CN114058008A CN 114058008 A CN114058008 A CN 114058008A CN 202111520458 A CN202111520458 A CN 202111520458A CN 114058008 A CN114058008 A CN 114058008A
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acid
semi
lactam
monomer
aromatic
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程圣利
李雪婷
刘慧敏
田华
刘建明
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Shandong Guangyin New Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

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  • Polymers & Plastics (AREA)
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  • Polyamides (AREA)

Abstract

The invention belongs to the technical field of polyamide, and particularly relates to a preparation method of semi-aromatic polyamide terminated by monocarboxylic acid, semi-aromatic polyamide and a molding composition. The preparation method of the semi-aromatic polyamide terminated by the monocarboxylic acid comprises the following steps: (1) polymerizing a dicarboxylic acid monomer, a diamine monomer, a monocarboxylic acid compound, a catalyst and water in a pressure reaction vessel to obtain a prepolymer; (2) and (3) performing solid-phase tackifying or melt polycondensation reaction on the prepolymer to obtain the semi-aromatic polyamide. The invention reduces the concentration of free diamine monomer in the polymerization system by adding the monocarboxylic acid compound, thereby reducing the loss of the diamine monomer in the polymerization process.

Description

Process for preparing semi-aromatic polyamides end-capped with monocarboxylic acids, semi-aromatic polyamides and molding compositions
Technical Field
The invention belongs to the technical field of polyamide, and particularly relates to a preparation method of semi-aromatic polyamide terminated by monocarboxylic acid, semi-aromatic polyamide and a molding composition.
Background
Polyamide is a polymer whose main chain contains amido bond (-CONH-). Due to the existence of amido bonds, stronger hydrogen bond action exists among polyamide molecular chains, the crystallization of the polyamide resin is promoted by the existence of the hydrogen bonds, and the interaction among the polyamide molecular chains is enhanced, so that the polyamide resin has good mechanical property, wear resistance, chemical resistance and the like. Polyamide resins are generally used in various fields such as automobiles, electronic and electronic appliances, building materials, lighting, aerospace fields, and the like in the form of pipes, profiles, articles, films, fibers, or the like.
The conventional polyamide resin has a low melting point due to a large amount of fatty structures, and thus the application of the polyamide resin in the high-temperature field is limited. By partially introducing an aromatic structure such as terephthalic acid, the melting temperature of the polyamide resin can be further increased, thereby increasing the use temperature of the polyamide resin. Because of its higher thermal stability and melting point than ordinary nylon resins, this class of polymers is called high temperature polyamides or high temperature nylons (HTPA). Due to its better thermal stability, HTPA is often used in areas where high temperature resistance is required, such as automotive engine surroundings and in the field of electronics, especially in soldering operations under lead-free conditions.
Semi-aromatic polyamides generally cannot be synthesized by polymerization processes like PA66 or PA6, since they have higher melting points, typically greater than 300 ℃. The traditional semi-aromatic polyamide is usually prepared by a solution salifying polycondensation process, prepolymerization is carried out under the conditions of high temperature and high pressure, and the polymerization reaction is promoted to be carried out towards the direction of generating high molecular weight by gradually removing water. When the degree of polymerization reaches a certain degree, a prepolymer is obtained, and the prepolymer is further subjected to solid-phase polymerization or melt polymerization to obtain a semiaromatic polyamide resin having a high molecular weight. The synthesis process of semi-aromatic polyamides is generally divided into a solid phase polymerization process and a melt polycondensation process, depending on the implementation of the post-polycondensation.
In the polymerization process, in order to ensure the smooth progress of the polymerization reaction, the water in the polymerization system needs to be gradually discharged out of the reaction system. As the diamine monomer has higher volatility, a small amount of the diamine monomer is inevitably discharged out of a polymerization system along with water vapor in the system drainage process. The discharge of a small amount of diamine monomer causes material unbalance in a polymerization system, and for polycondensation reaction, the material monomer ratio unbalance causes that a high molecular weight polymer cannot be obtained in the later polymerization stage, and the final product performance is influenced. Commercially, it is common to employ high temperature, high pressure polymerization processes while keeping the diamine monomer added in a slight excess to compensate for the loss of diamine monomer. However, an excess of diamine monomer results in an excess portion of diamine monomer not being available to salt with diacid monomer, and the free diamine monomer is more volatile, resulting in loss of diamine monomer during polymerization. In addition, because a small amount of diamine monomer is contained in the discharged water vapor in the polymerization process, a large amount of wastewater containing the diamine monomer is generated, and the expansion and operation of production are not facilitated from the economic and environmental aspects.
Since only the diamine monomer in a free state is volatile, the loss of the diamine monomer during the polymerization process can be reduced by reducing the content of the free diamine monomer.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method of the semi-aromatic polyamide terminated by the monocarboxylic acid is provided, the loss of the diamine monomer in the polymerization process is greatly reduced by reducing the content of the free diamine monomer, and the method has good economic value and environmental protection value; the invention also provides a preparation method thereof and a molding composition comprising the same.
In a first aspect:
the preparation method of the semi-aromatic polyamide terminated by the monocarboxylic acid comprises the following steps:
(1) polymerizing a dicarboxylic acid monomer, a diamine monomer, a monocarboxylic acid compound, a catalyst and water in a pressure reaction vessel to obtain a prepolymer;
(2) and (3) performing solid-phase tackifying or melt polycondensation reaction on the prepolymer to obtain the semi-aromatic polyamide.
In the invention, the dicarboxylic acid monomer is a dicarboxylic acid monomer containing 4-36 carbon atoms, and comprises an aliphatic dicarboxylic acid monomer, an alicyclic dicarboxylic acid monomer and/or an aromatic dicarboxylic acid monomer, and an aliphatic or alicyclic dicarboxylic acid monomer. Such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, heptadecanedicarboxylic acid, octadecanedicarboxylic acid, nonadecanedicarboxylic acid, eicosanedicarboxylic acid, 2-methyladipic acid, 2-dimethylglutaric acid, 3-diethylsuccinic acid, maleic acid, fumaric acid, itaconic acid, dimer acid, cis-and/or trans-cyclohexane-1, 2-dicarboxylic acid, cis-and/or trans-cyclohexane-1, 3-dicarboxylic acid, cis-and/or trans-cyclohexane-1, 4-dicarboxylic acid, cis-and/or trans-cyclopentane-1, 2-dicarboxylic acid, isophthalic acid, maleic acid, fumaric acid, maleic acid, and/or trans-cyclohexane-1, 2-dicarboxylic acid, One or more of cis-and/or trans-cyclopentane-1, 3-dicarboxylic acid and 2-methylglutaric acid; aromatic structural dicarboxylic acid monomers such as terephthalic acid, isophthalic acid, phthalic acid, 2, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 1, 4-phenylenedioxydiacetic acid, 1, 3-phenylenedioxydiacetic acid, 2 ' -biphenyldicarboxylic acid, 4 ' -oxybis (benzoic acid), diphenylmethane-4, 4 ' -dicarboxylic acid, diphenylsulfone-4, 4 ' -dicarboxylic acid, 4 ' -biphenyldicarboxylic acid, furandicarboxylic acid, and combinations thereof.
In the invention, the diamine monomer is a diamine monomer containing 2-36 carbon atoms, and comprises an aliphatic structure diamine monomer, an alicyclic structure diamine monomer and/or an aromatic structure diamine monomer, and an aliphatic structure diamine monomer or an alicyclic structure diamine monomer. Such as ethylenediamine, 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-undecanediamine, 1, 12-dodecanediamine, 1, 13-tridecanediamine, 1, 14-tetradecanediamine, 1, 15-pentadecanediamine, 1, 16-hexadecanediamine, 1, 17-heptadecanediamine, 1, 18-octadecanediamine, 1, 19-nonadecanediamine, 1, 20-eicosanediamine, 2-methyl-1, 5-pentanediamine, 3-methyl-1, 5-pentanediamine, 2-butyl-2-ethyl-1, 5-pentamethylenediamine, 2, 4-dimethyl-1, 6-hexamethylenediamine, 2, 4-trimethyl-1, 6-hexamethylenediamine, 2,4, 4-trimethyl-1, 6-hexamethylenediamine, 2-methyl-1, 8-octanediamine, 5-methyl-1, 9-nonanediamine, 2, 4-dimethyl-octanediamine, 1, 3-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 3 '-dimethyl-4, 4' -diaminodicyclohexylmethane, isophorone diamine, norbornane dimethylamine, cis-1, 4-cyclohexane diamine, trans-1, 4-cyclohexane diamine, methylcyclohexane diamine, bis (aminopropyl) piperazine, ethylene diamine, propylene diamine, and propylene diamine, and propylene diamine, propylene diamine, One or more of aminoethylpiperazine; aromatic structural diamine monomers such as one or more of m-xylylenediamine, p-phenylenediamine, m-phenylenediamine, bis (4-aminophenyl) methane, 3-methylbenzidine, 2-bis (4-aminophenyl) propane, 1-bis (4-aminophenyl) cyclohexane, 1, 4-diaminonaphthalene, 1, 5-diaminonaphthalene, 2, 6-diaminonaphthalene, 1, 3-diaminotoluene, N '-dimethyl-4, 4' -biphenyldiamine, bis (4-methylaminophenyl) methane, 2-bis (4-methylaminophenyl) propane.
In the present invention, the monocarboxylic acid compound is one or more selected from the group consisting of an aliphatic monocarboxylic acid compound, an alicyclic monocarboxylic acid compound, and an aromatic monocarboxylic acid compound.
The monocarboxylic acid compound includes acetic acid, propionic acid, n-butyric acid, isobutyric acid, t-butyric acid, valeric acid, pivalic acid, dimethylacetic acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, cyclopropanecarboxylic acid, cyclopentanecarboxylic acid, cyclopentaneacetic acid, cyclohexanecarboxylic acid, benzoic acid, p-methylbenzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-tert-butylbenzoic acid, salicylic acid, p-methoxybenzoic acid, α -naphthoic acid, β -naphthoic acid, methylnaphthoic acid, phenylacetic acid, oleic acid, lactic acid, ricinoleic acid, linoleic acid, linolenic acid, erucic acid, various plant-derived fatty acids, acrylic acid, methacrylic acid, and mixtures thereof.
Particularly preferred monocarboxylic acid compounds are at least one of acetic acid, propionic acid, and benzoic acid.
Wherein, the total mole number of dicarboxylic acid monomers a, the total mole number of diamine monomers b, the total mole number of monocarboxylic acid compounds c, wherein c/a is 0.01-0.03, and the defined parameter r:
Figure BDA0003407338960000031
the value range of r is 1-1.1.
In the present invention, at the beginning of the polymerization reaction in step (1), lactam and/or amino acid may be added, and the lactam and/or amino acid may be selected from propane-3-lactam (. beta. -lactam.; beta. -propiolactam), butane-4-lactam (. gamma. -lactam.; gamma. -butyrolactam), 2-piperidone (. delta. -lactam.; delta. -valerolactam), caprolactam (. epsilon. -lactam.; epsilon. -caprolactam.; alpha.,. omega. -aminocaproic acid, heptan-7-lactam (. zeta. -lactam.; zeta. -heptanolactam.), alpha.,. omega. -aminononanoic acid, nonane-9-lactam (. theta. -lactam.; theta. -nonanolactam), decan 10-lactam (. omega. -decanolactam), Alpha, omega-aminoundecanoic acid, laurolactam, omega-aminododecanoic acid, eta-octanolactam (eta-lactam; eta-octanolactam), or a combination thereof; the addition amount of the lactam and/or the amino acid is 0-90% of the total mole number of the polymerization monomers.
In the present invention, suitable catalysts are selected from inorganic and/or organic phosphorus, tin or lead compounds and mixtures thereof.
Suitable phosphorus-containing compounds are phosphoric acid, phosphorous acid, hypophosphorous acid, phenylphosphoric acid, phenylphosphinic acid and/or salts with monovalent or trivalent cations thereof, and/or esters thereof, for example triphenyl phosphate, triphenyl phosphite or tris (nonylphenyl) phosphite.
Suitable tin catalysts are tin oxide, tin hydroxide, tin salts of monocarboxylic or polycarboxylic acids. Such as tin dibenzoate, tin bis (2-ethylhexanoate), tin oxalate, dibutyltin oxide, butylstannoic acid, tin dilaurate, and the like.
Suitable lead compounds include lead oxide, lead hydroxide, lead acetate, basic lead acetate, lead carbonate, and the like.
Particularly preferred catalysts are hypophosphorous acid and its salts, such as sodium or potassium hypophosphite.
The amount of the catalyst is 0.0001 to 5% by weight, preferably 10 to 1000ppm, most preferably 100 to 500ppm, based on the total weight of the polymerization monomers.
In the invention, the reaction temperature of the polymerization reaction is 200-300 ℃, and the reaction pressure is 0.5-5 MPa. The polymerization reaction refers to that under the temperature of 200-300 ℃ and the pressure of 0.5-5MPa, the nylon salt formed by the diacid monomer and the diamine monomer, deionized water, a catalyst and an end-capping reagent continuously release water vapor in a reaction container, and the reaction is propelled to the polymerization reaction direction, so that the semi-aromatic polyamide prepolymer with a certain molecular weight is obtained.
In the invention, the solid-phase tackifying reaction is carried out in an inert gas atmosphere or under a vacuum condition, the reaction temperature is 220-280 ℃, and the reaction time is 2-24 hours; the melt polycondensation is carried out in an extrusion device with a vent, the reaction temperature is 280-350 ℃, and the reaction time is within 0.5 hour.
In a second aspect:
the semi-aromatic polyamide is prepared by the preparation method, the melting point of the semi-aromatic polyamide is 250-350 ℃, and the melting point is measured by Differential Scanning Calorimetry (DSC).
In a third aspect:
the molding composition composed of the semi-aromatic polyamide comprises the following raw materials in parts by weight:
Figure BDA0003407338960000041
wherein the reinforcing material is selected from one of glass fiber, potassium titanate whisker, metal clad glass fiber, carbon fiber, ceramic fiber, wollastonite fiber, mullite fiber, silica fiber, quartz fiber, ceramic fiber, basalt fiber, metal carbide fiber, metal solidified fiber, asbestos fiber, alumina fiber, silicon carbide fiber, boron fiber, calcium carbonate whisker, aluminum borate whisker, zinc oxide whisker, aramid fiber, liquid crystal polyester fiber, nylon fiber, ultra-high molecular weight polyethylene fiber, polyimide fiber, polyphenylene sulfide fiber, polybenzimidazole fiber, polybenzoxazole fiber, polyaryletherketone fiber, wood fiber, flax fiber, hemp fiber and sisal fiber, natural fiber and combination thereof. Preferably at least one of glass fiber, carbon fiber, aramid fiber, boron fiber, metal fiber, and potassium titanate fiber.
Inorganic fillers include fibrous, particulate, nanoparticulate fillers such as glass microbeads, ceramic microbeads, kaolin, chalk, clay, alumino-silica, zinc sulfide, strontium sulfide, barium sulfide, lead titanate, barium titanate, molybdenum disulfide, polytetrafluoroethylene, titanium dioxide, silica, barium carbonate, magnesium carbonate, aluminum nitride, boron nitride, silicon carbide, potassium titanate whiskers, zinc borate, zinc phosphate, calcium phosphate, aluminum borate whiskers, carbon black, graphite, graphene, carbon nanotubes, nano-alumina, silicates, aluminum silicate, calcium silicate, magnesium silicate, zinc basic silicate, calcium oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, zinc oxide whiskers, antimony oxide, white lead, hydrated tin oxide, silver chloride, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, Zinc hydroxide, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, calcium stearate, zinc stearate, magnesium stearate, potassium palmitate, magnesium behenate, talc, asbestos, carbon nanotubes, silicon carbide, hydrotalcite, metal microspheres, sericite, mica, vermiculite, illite, smectite, montmorillonite, hectorite, dihydroxide, zeolite, pyrophyllite, wollastonite, nano-layered silicate, nano-alumina, boehmite, serpentine, hydrocalumite, sepiolite, dolomite, xonotlite, silica-alumina, bentonite, montmorillonite, hectorite, synthetic mica, and related modified treatment products.
In the present invention, in order to provide the polyamide composition with more excellent mechanical properties, the inorganic filler may be functionally treated with a coupling agent selected from isocyanate-based compounds, organic silane-based compounds, organic titanate-based compounds, organic borane-based compounds, and epoxy compounds, preferably organic silane-based compounds.
Wherein the organic silane compound is selected from one or more of an epoxy group-containing alkoxysilane compound, a mercapto group-containing alkoxysilane compound, a ureido group-containing alkoxysilane compound, an isocyanate group-containing alkoxysilane compound, an amino group-containing alkoxysilane compound, a hydroxyl group-containing alkoxysilane compound, a carbon-carbon unsaturated group-containing alkoxysilane compound, and an acid anhydride group-containing alkoxysilane compound; the alkoxy silane compound containing the epoxy group is selected from one or more of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane and beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane; the alkoxy silane compound containing the sulfydryl is selected from gamma-mercaptopropyltrimethoxysilane and/or gamma-mercaptopropyltriethoxysilane; the ureido-containing alkoxy silane compound is selected from one or more of gamma-ureidopropyl triethoxy silane, gamma-ureidopropyl trimethoxy silane and gamma- (2-ureidoethyl) aminopropyl trimethoxy silane; the alkoxy silane compound containing the isocyanate group is selected from one or more of gamma-isocyanate propyl triethoxysilane, gamma-isocyanate propyl trimethoxysilane, gamma-isocyanate propyl methyldimethoxysilane, gamma-isocyanate propyl methyldiethoxysilane, gamma-isocyanate propyl ethyldimethoxysilane, gamma-isocyanate propyl ethyldiethoxysilane and gamma-isocyanate propyl trichlorosilane; the alkoxy silane compound containing amino is selected from one or more of gamma- (2-aminoethyl) aminopropylmethyldimethoxysilane, gamma- (2-aminoethyl) aminopropyltrimethoxysilane and gamma-aminopropyltrimethoxysilane; the alkoxy silane compound containing hydroxyl is selected from gamma-hydroxypropyl trimethoxy silane and/or gamma-hydroxypropyl triethoxy silane; the alkoxy silane compound containing carbon-carbon unsaturated group is selected from one or more of gamma-methacryloxypropyltrimethoxysilane, vinyl trimethoxy silane and N-beta- (N-vinyl benzyl aminoethyl) -gamma-aminopropyl trimethoxy silane hydrochloride; the alkoxysilane compound containing an acid anhydride group is selected from 3-trimethoxysilylpropyl succinic anhydride; the organic silane compound is preferably gamma-methacryloxypropyltrimethoxysilane, gamma- (2-aminoethyl) aminopropylmethyldimethoxysilane, gamma- (2-aminoethyl) aminopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane or 3-trimethoxysilylpropylsuccinic anhydride.
The amount of the coupling agent is 0.05-10 wt% of the weight of the inorganic filler, and preferably 0.15 wt%; when the amount of the coupling agent is less than 0.05 wt%, the inorganic filler is easily aggregated and is poorly dispersed in the polyamide resin, eventually resulting in a decrease in mechanical properties.
In the present invention, the additives include one or more of antioxidants, flame retardants, lubricants, mold release agents, nucleating agents, colorants, plasticizers, toughening agents, antistatic agents, solubilizing agents, dispersing agents, stabilizers, flow modifiers, or other polymer resins. The additives are all commonly used auxiliary agents in the field and are added according to the performance requirements of the composition.
In the invention, the antioxidant comprises amine antioxidant, phenol antioxidant and ester antioxidant.
Amine antioxidants include, but are not limited to, p-isopropoxydiphenylamine; 4,4- (bis α, α -dimethylbenzyl) diphenylamine, N-bis (1, 4-dimethylpentyl) p-phenylenediamine, N-di- β -naphthylp-phenylenediamine, N (1, 3-dimethylbutyl) -N-phenylphenylenediamine, 2, 4-trimethyl-1, 2-dihydroquinoline polymer, and the like.
The phenolic antioxidant includes, but is not limited to, 1-hydroxy-3-methyl-4-isopropylbenzene, 2,4, 6-tri-tert-butylphenol, n-octadecyl beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionate, pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and the like.
The ester antioxidant includes, but is not limited to, n-octadecyl beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionate, dilauryl thiodipropionate, octadecyl beta, beta-thiodibutyrate, triphenyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, and the like.
In the present invention, the flame retardant includes a halogen-based flame retardant including, but not limited to, hexabromocyclododecane, decabromodiphenyl ether, octabromodiphenyl ether, tetrabromobisphenol A, bis (tribromophenoxy) ethane, bis (pentabromophenoxy) ethane, tetrabromobisphenol A epoxy resin, tetrabromobisphenol A carbonate, ethylenebis (tetrabromophthalimide), ethylenebis-pentabromobiphenyl, tris (tribromophenoxy) triazine, bis (dibromopropyl) tetrabromobisphenol A, bis (dibromopropyl) tetrabromobisphenol S, brominated polyphenylene ethers (including poly (di) bromophenyl ether and the like), brominated polystyrenes (including polydibromostyrene, polytribromostyrene, crosslinked brominated polystyrenes and the like), brominated crosslinked aromatic polymer brominated epoxy resin, brominated phenoxy resin, brominated styrene-maleic anhydride copolymer, and halogen-free flame retardant, Tetrabromobisphenol S, tris (tribromoneopentyl) phosphate, polybromotrimethylphenylindane, tris (dibromopropyl) isocyanurate, and the like. As the halogen-based flame retardant, brominated polyphenylene ethers (including poly (di) bromophenyl ether) and the like), brominated polystyrenes (including polydibromostyrene, polytribromostyrene, crosslinked brominated polystyrenes and the like) are preferable, and brominated polystyrenes are more preferable, from the viewpoints of low generation of corrosive gas during melt processing such as extrusion or molding and the expression of mechanical properties such as flame retardancy, toughness and rigidity. Wherein, the bromine content in the brominated polystyrene is preferably 55 wt% to 75 wt%.
The halogen-free flame retardant is selected from one or more of nitrogen-containing flame retardant, phosphine-containing flame retardant or nitrogen and phosphine-containing flame retardant; phosphine containing flame retardants are preferred. The phosphorus-containing flame retardant comprises one or more of red phosphorus, aryl phosphate monophosphate, aryl phosphate diphosphonate, dimethyl alkyl phosphonate, triphenyl phosphonate, tricresyl phosphonate, trixylene phosphonate, propyl benzene phosphonate, butyl benzene phosphonate or phosphinate; preferably a phosphinate; the phosphinate is represented by a compound represented by the following formula (I) and/or (II).
Figure BDA0003407338960000071
In the formula (I) and the formula (II), R and R may be the same or different,each represents a straight chain or branched C1～C6-alkyl, aryl or phenyl. R3Represents a straight chain or branched C1～C10Alkylene radical, C6～C10Arylene radical, C6～C10An alkylarylene radical, or C6～C10An arylalkylene group. M represents a calcium atom, a magnesium atom, an aluminum atom and/or a zinc atom. m is 2 or 3, n is 1 or 3, and x is 1 or 2.
More specific examples of phosphinate compounds include, but are not limited to, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl n-propylphosphinate, magnesium methyl n-propylphosphinate, aluminum methyl n-propylphosphinate, zinc methyl n-propylphosphinate, calcium methylphosphinate, magnesium methanedi (methylphosphinate), aluminum methanedi (methylphosphinate), zinc methanedi (methylphosphinate), calcium benzene-1, 4- (dimethylphosphinate) magnesium benzene-1, 4- (dimethylphosphinic acid) aluminum, benzene-1, 4- (dimethylphosphinic acid) zinc, phenylphosphinic acid calcium, phenylphosphinic acid magnesium, phenylphosphinic acid aluminum, phenylphosphinic acid zinc, diphenylphosphinic acid calcium, diphenylphosphinic acid magnesium, diphenylphosphinic acid aluminum, diphenylphosphinic acid zinc, etc., with dimethylphosphinic acid calcium, dimethylphosphinic acid aluminum, dimethylphosphinic acid zinc, ethylmethylphosphinic acid beggar, ethylmethylphosphinic acid aluminum, ethylmethylphosphinic acid zinc, diethylphosphinic acid calcium, diethylphosphinic acid aluminum, diethylphosphinic acid zinc, more preferably diethylphosphinic acid aluminum.
Phosphinate compounds as flame retardants are readily available from the market. Examples of commercially available phosphinate compounds include EXOLIT OP11230, 0P1311, 0P1312, 0P930, P935, and the like, manufactured by Clariant.
Among them, when a phosphinate or diphosphine oxide is used, it is preferable to use a polyphosphoric acid melamine as the phosphorus-based flame retardant in combination. By using polyphosphoric acid melamine in combination, carbonization of polyamide can be promoted and combustion time can be shortened in a flame retardancy test. When the melamine polyphosphate is used in an excessive amount, there is a tendency that a problem such as mold contamination is caused when the polyamide composition is injection-molded, and therefore, the amount of the melamine polyphosphate is preferably less than 1 part by mass based on 100 parts by mass of the polyamide.
The nitrogen-containing flame retardants include, but are not limited to, melamine cyanurate, melamine sulfate, melamine borate, melamine oxalate, melamine phosphate (melamine dihydrogen phosphate, melamine hydrogen phosphate) or melamine dihydrogen pyrophosphate, neopentyl glycol melamine borate, guanidine, and derivatives thereof known to those skilled in the art, as well as polymerized melamine phosphate, ammonium polyphosphate, trihydroxyethyl isocyanurate (optionally also ammonium polyphosphate in a mixture with trihydroxyethyl isocyanurate).
In order to further improve the flame retardant effect of the flame retardant, the composition of the flame retardant and the flame retardant auxiliary can be selected in the invention, and the flame retardant auxiliary comprises antimony trioxide, antimony tetraoxide, antimony pentoxide and other antimony oxides; iron oxides such as iron oxide and gamma-iron oxide; metal oxides such as sodium oxide, tin dioxide, zinc oxide, aluminum oxide (alumina), aluminum oxide (boehmite), titanium oxide, calcium oxide, zirconium oxide, manganese oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, nickel oxide, copper oxide, and tungsten oxide; metal powders of aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, tin, antimony, nickel, copper, tungsten, and the like; metal carbonates such as zinc carbonate, calcium carbonate, magnesium carbonate, and barium carbonate; metal borates such as zinc borate, magnesium borate, calcium borate, and aluminum borate; magnesium hydroxide, calcium hydroxide, aluminum hydroxide, kaolin, clay, zinc stannate, sodium antimonate, silicon dioxide (silica), and the like. They may be used alone or in combination of 2 or more. These flame retardant aids may be treated with a coupling agent such as a silane coupling agent, a titanium coupling agent, or the like. Among them, zinc stannate, sodium antimonate and/or zinc borate are preferable.
In the polyamide composition of the polyamide resin according to the invention, the additive component may also comprise up to 50% by weight of one or more impact modifiers. Such impact modifiers include, but are not limited to, crystalline olefin polymers, natural rubber, ethylene-alpha-olefin copolymers, ethylene-acrylate copolymers, polybutadiene, polyisoprene, polyisobutylene, copolymers of butadiene and/or isoprene with styrene or with styrene derivatives and/or with other comonomers, hydrogenated copolymers, and/or copolymers made by grafting or copolymerization with anhydrides, (meth) acrylic acid or esters thereof. The impact modifier may be a grafted rubber having a crosslinked elastomeric core composed of butadiene, isoprene or alkyl acrylate and having a grafted shell composed of polystyrene, or may be a non-polar or polar olefin homopolymer or copolymer, such as ethylene-propylene rubber, ethylene-propylene diene rubber, or ethylene-octene rubber, or ethylene-vinyl acetate rubber, or a non-polar or polar olefin homopolymer or copolymer obtained by grafting or copolymerization with an anhydride, (meth) acrylic acid or an ester thereof; the impact modifier may also be a carboxylic acid functionalized copolymer, such as poly (ethylene-co- (methacrylic acid) or poly (ethylene-1-olefin-co (meth) acrylic acid), where the 1-olefin is an alkene or an unsaturated (meth) acrylate having more than 4 atoms, including those copolymers where the acid groups are neutralized to some extent by metal ions.
Impact modifiers based on styrene monomers (styrene and styrene derivatives) and other vinyl aromatic monomers are block copolymers composed of alkenyl aromatic compounds and conjugated dienes, and hydrogenated block copolymers composed of alkenyl aromatic compounds and conjugated dienes, and combinations of these types of impact modifiers. Other alkenyl aromatic compounds which may be used together with styrene or in the form of mixtures with styrene are vinylaromatic monomers which are substituted on the aromatic ring and/or on the C ═ C double bond by C1 to C20 hydrocarbon radicals or by halogen atoms. Examples of alkenyl aromatic monomers are styrene, p-methylstyrene, alpha-methylstyrene, ethylstyrene, tert-butylstyrene, vinyltoluene, 1, 2-diphenylethylene, 1-diphenylethylene, vinylxylene, vinyltoluene, vinylnaphthalene, divinylbenzene, bromostyrene, and chlorostyrene, and combinations thereof. Preference is given to styrene, p-methylstyrene, alpha-methylstyrene, vinylnaphthalene tert-butylstyrene, vinyltoluene, 1, 2-diphenylethylene, 1-diphenylethylene or mixtures of these substances.
Examples of diene monomers which may be used are 1, 3-butadiene, 2-methyl-1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, 1, 3-hexadiene, isoprene, chloroprene and piperylene. 1, 3-butadiene and isoprene are preferred, with 1, 3-butadiene being particularly preferred (hereinafter referred to in abbreviated form as butadiene). The alkenyl aromatic monomer used preferably comprises styrene and the diene monomer used preferably comprises butadiene, which means that styrene-butadiene block copolymers are preferred.
In addition to the styrene monomer and the diene monomer, other additional monomers may also be used simultaneously. Examples of suitable comonomers are acrylic esters, in particular C1-C12 alkyl acrylates, for example n-butyl acrylate or 2-ethylhexyl acrylate, and methacrylic esters, in particular C1-C12 alkyl methacrylates, for example Methyl Methacrylate (MMA), respectively. Other possible comonomers are (meth) acrylonitrile, glycidyl (meth) acrylate, vinyl methyl ether, diallyl and divinyl ethers of dihydric alcohols, divinylbenzene and vinyl acetate.
Particularly preferred are maleic anhydride graft-functionalized copolymers of butadiene and styrene, nonpolar or polar olefin homo-and copolymers prepared by grafting with maleic anhydride, and carboxylic acid-functionalized copolymers, such as poly (ethylene-co (meth) acrylic acid) or poly (ethylene-co-1-olefin-co (meth) acrylic acid), in which the acid groups have been neutralized to some extent by metal ions. Examples of commercially available impact modifiers that can be used in the additive component are:
TAFMER MC 201: g-MA (0.6%) blend of 67% EP copolymer (20mo 1% propylene) + 33% EB copolymer (15mo 1% 1-butene): mitsui Chemicals, japan.
TAFMER MH 5010: g-MA (0.6%) ethylene-butene copolymer: mitsui.
TAFMER MH 7010: g-MA (0.6%) ethylene-butene copolymer: mitsui.
TAFMER MH 7020: g-MA (0.7%) EP copolymer: mitsui.
EXXELOR VA 1801: g-MA (0.7%) EP copolymer: exxon Mobile Chemicals, US.
EXXELOR VA 1803: g-MA (0.5-0.9%) EP copolymer, amorphous, Exxon.
EXXELOR VA 1810: g-MA (0.5%) EP copolymer, Exxon.
EXXELOR MDEX 9411：g-MA(0.7％)EPDM，Exxon。
FUSABOND MN 4930: g-MA (0.5%) ethylene-octene copolymer, DuPont, US.
FUSABOND EB 560D: g-MA ethylene-n-butyl acrylate copolymer, DuPont ELVALOY, DuPont.
In addition to the conjugated diene, the hydrogenated block copolymer may, if appropriate, also contain a lower hydrocarbon moiety, such as ethylene, propylene, 1-butene, dicyclopentadiene or a non-conjugated diene. The hydrogenated block copolymers include, but are not limited to, hydrogenated block copolymers obtained by hydrogenation of styrene-butadiene copolymers and hydrogenation of styrene-butadiene-styrene copolymers, i.e., styrene- (ethylene-butylene) diblock copolymers and styrene- (ethylene-butylene) -styrene triblock copolymers. Suitable hydrogenated block copolymers are commercially available products such as (Kraton polymers) G1650, G1651, and G1652, and (Asahi Chemicals) H1041, H1043, H1052, H1062, H1141, and H1272.
Examples of non-hydrogenated block copolymers are polystyrene-polybutadiene, polystyrene-poly (ethylene-propylene) polystyrene-polyisopentadiene, poly (alpha-methylstyrene) -polybutadiene, polystyrene-polybutadiene-polystyrene (SBS), polystyrene-poly (ethylene-propylene) -polystyrene, polystyrene-polyisoprene-polystyrene, and poly (alpha-methylstyrene) polybutadiene-poly (alpha-methylstyrene), and combinations thereof. Suitable non-hydrogenated block copolymers are commercially available under the trade names (Phillips), (Shell), (Dexco) and (Kuraray).
Examples of crystalline olefin polymers are low, medium and high density polyethylene, polypropylene, polybutadiene, poly-4-methylpentene, ethylene-propylene block copolymers, or ethylene-propylene random copolymers, ethylene-methylhexadiene copolymers, propylene-methylhexadiene copolymers, ethylene-propylene butene copolymers, ethylene propylene hexene copolymers, ethylene-propylene-methylhexadiene copolymers, poly (ethylene-vinyl acetate) (EVA), poly (ethylene-ethyl acrylate) (EEA), ethylene octene copolymers, ethylene-butene copolymers, ethylene hexene copolymers, ethylene propylene diene terpolymers, and combinations of the above.
Preferably, the above-mentioned impact modifiers comprise a component having groups introduced by thermal or radical reaction of the main chain polymer with an unsaturated dianhydride, with an unsaturated dicarboxylic acid, or with a monoalkyl ester of an unsaturated dicarboxylic acid, in a concentration sufficient for good bonding with the polyamide, and it is preferred here to use an agent selected from:
maleic acid, maleic anhydride, monobutyl maleate, fumaric acid, aconitic acid and/or itaconic anhydride. Preferably 0.1 to 4.0 wt% of an unsaturated anhydride is grafted onto the impact resistant component as a constituent of C, or an unsaturated dianhydride or precursor thereof is applied by grafting together with other unsaturated monomers. The degree of grafting is generally preferably 0.1 to 1.0%, particularly preferably 0.3 to 0.7%.
In the polyamide composition of the polyamide resin of the present invention, the additive component may further contain other materials used in multicolor molding or polymer alloy, and other resins used such as polyolefin-based resins of low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, ethylene/propylene copolymer, ethylene/butene copolymer, ethylene/vinyl acetate copolymer, saponified product of ethylene/vinyl acetate copolymer, ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/methyl acrylate copolymer, ethylene/methyl methacrylate copolymer, ethylene/ethyl acrylate copolymer, polybutadiene, ethylene/propylene/diene copolymer, polystyrene, etc.; polyester resins such as polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polyarylates, and liquid crystal polyesters; polyether resins such as polyacetal and polyphenylene ether; polysulfone resins such as polysulfone and polyethersulfone; polythioether resins such as polyphenylene sulfide and polythioether sulfone; polyketone resins such as polyetheretherketone and polyallylether; polyacrylonitrile, polymethacrylonitrile, acrylonitrile/styrene copolymer, acrylonitrile/butadiene/styrene copolymer, methacrylonitrile/butadiene/styrene copolymer, and the like; polymethacrylate-based resins such as polymethyl methacrylate and polyethyl methacrylate; polyvinyl ester resins such as polyvinyl acetate; polyvinyl chloride resins such as polyvinylidene chloride, polyvinyl chloride/vinylidene chloride copolymer, and vinylidene chloride/methyl acrylate copolymer; cellulose resins such as cellulose acetate and cellulose butyrate; fluorine-based resins such as polyvinylidene fluoride, polyvinyl fluoride, ethylene/tetrafluoroethylene copolymer, polychlorotrifluoroethylene, ethylene/chlorotrifluoroethylene copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, and tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride copolymer; polycarbonate resins such as polycarbonate; polyimide resins such as thermoplastic polyimide, polyimide imide, and polyetherimide; a thermoplastic polyurethane resin.
In the polyamide composition of the polyamide resin, the polymer material applied to multicolor molding or polymer alloy further comprises aliphatic polyamide and/or semi-aromatic polyamide, such as one or more polymers derived from aliphatic diacid and aliphatic diamine with 4-20 carbon atoms, or lactam with 4-20 carbon atoms, or aliphatic diacid, aliphatic diamine and lactam with 4-20 carbon atoms. Including, but not limited to, polyhexamethylene adipamide (PA66), polylactam (PA6), polyhexamethylene sebacamide (PA610), polyamide 612, polyhexamethylene sebacamide (PA1010), polyhexamethylene adipamide-caprolactam copolymer (PA66/6), polyundecanolactam (PA11), polydodecanolactam (PA12), and mixtures of two or more thereof. Examples of the semi-aromatic polyamide include polyamide resins such as poly (m-xylylene adipamide) (MXD6), polyhexamethylene terephthalamide (PA6T), polynonylene terephthalamide (PA9T), polydecylene terephthalamide (PA10T), polydodecamethylene terephthalamide (PA12T), poly (4-aminocyclyl) methane dodecamide (PACM12), polyamide raw material monomers for forming these, and/or copolymers obtained using a plurality of the above polyamide raw material monomers. In addition to the polyamides described above, amorphous polyamides are also included, which include, but are not limited to, condensates of isophthalic acid/terephthalic acid/1, 6-hexanediamine/bis (3-methyl-4-aminocyclohexyl) methane, condensates of terephthalic acid/2, 2, 4-trimethyl-1, 6-hexanediamine/2, 4, 4-trimethyl-1, 6-hexanediamine, condensates of isophthalic acid/bis (-methyl-4-aminocyclohexyl) methane/-dodecalactam, condensates of isophthalic acid/terephthalic acid/1, 6-hexanediamine, condensates of isophthalic acid/2, 2, 4-trimethyl-1, 6-hexanediamine/2, examples of the polyamide resin include a polycondensate of 4, 4-trimethyl-1, 6-hexamethylenediamine, a polycondensate of isophthalic acid/terephthalic acid/2, 2, 4-trimethyl-1, 6-hexamethylenediamine/2, 4, 4-trimethyl-1, 6-hexamethylenediamine, a polycondensate of isophthalic acid/terephthalic acid/another diamine component, a polyamide raw material monomer for forming the same, and/or a copolymer obtained by using a plurality of the polyamide raw material monomers. By adding the amorphous polyamide, the surface gloss and the like can be improved.
In the polyamide composition of the polyamide resin, the polymer material applied to multicolor molding or polymer alloy also comprises polyphenylene ether (PPE). Suitable polyphenylene ethers include, but are not limited to, poly (2, 6-diethyl-1, 4-phenylene) ether, poly (2-methyl-6-ethyl-1, 4-phenylene) ether, poly (2-methyl-6-propyl-1, 4-phenylene) ether, poly (2, 6-dipropyl-1, 4-phenylene) ether, poly (2-ethyl-6-propyl-1, 4-phenylene) ether, or copolymers such as those containing 2,3, 6-trimethylphenol, and mixtures of polymers. Preference is given to poly (2, 6-dimethyl-1, 4-phenylene) ether optionally in combination with 2,3, 6-trimethylphenol units. The polyphenylene ether may be used in the form of a homopolymer, copolymer, graft copolymer, block copolymer or ionomer. For better compatibility, compatibilizers in the form of polyfunctional compounds are used which interact with the polyphenylene ether, polyamide or both. The interaction may be chemical (e.g. by grafting) and/or physical (e.g. by effect on the surface properties of the dispersed phase).
In order to improve the compatibility of the resin and/or impact modifier with the polyamide resin, up to 15% by mass of a solubilizing agent, which may be a polyfunctional compound containing at least one carboxylic acid group, carboxylic anhydride group, ester group, amide group or imide group, may be added in the present invention. Such as maleic acid, maleic anhydride, 2-methylmaleic anhydride, 2-chloromaleic anhydride, 2, 3-diylmaleic anhydride, bicyclo [2,2,1] -5-heptene-2, 3-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1, 2-dicarboxylic anhydride, bicyclo (2.2.2) oct-5-ene-2, 3-dicarboxylic anhydride, 1,2,3,4,5,8,9, 10-octahydronaphthalene-2, 3-dicarboxylic anhydride, 2-oxo-1, 3-diketospiro (4.4) non-7-ene, bicyclo (2.2.1) hept-5-ene-2, 3-dicarboxylic anhydride, maleopimaric anhydride, phthalic anhydride, citraconic anhydride, fumaric acid, crotonic acid, maleic anhydride, citraconic anhydride, fumaric acid, maleic anhydride, crotonic acid, maleic anhydride, maleic, Mesaconic acid, acrylic acid, methacrylic acid, ethacrylic acid, methyl maleic anhydride, itaconic acid, itaconic anhydride, butenyl succinic acid, butenyl succinic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, N-phenyl maleimide, citric acid, malic acid, norborn-5-ene-2, 3-dicarboxylic anhydride, nadic anhydride (nadic anhydride), methylnadic anhydride, nadic anhydride (himic anhydride), methylnadic anhydride, and x-methyl-bicyclo (2.2.1) hept-5-ene 2, 3-dicarboxylic anhydride (XMNA), 2-hydroxynonadecane-1, 2, 3-tricarboxylic acid and mono-or diesters of the above acids with C1 to C12 alcohols (e.g., methanol or ethanol), monoamides or diamides of the above acids (if appropriate, alkyl or aryl groups having up to 12 carbon atoms which may be substituted on the N) and salts with alkali or alkaline earth metals, such as calcium and potassium. Among them, maleic acid, fumaric acid, maleic anhydride and citric acid are preferable.
In the polyamide composition of the polyamide resin of the present invention, the additive component may further comprise 0 to 20 parts by weight of a polyol. The polyol comprises at least one of dihydric alcohol, trihydric alcohol, polyol with the hydroxyl number being more than or equal to four, and polymeric polyol. The dihydric alcohol comprises at least one of 1, 2-ethanediol, 1, 3-propanediol, 2, 3-butanediol, 1, 5-pentanediol, 2-dimethyl-1, 3-propanediol and polyether glycol; the trihydric alcohols include, but are not limited to, glycerol, trimethylolpropane, 2, 3-bis (2 '-hydroxyethyl) cyclohexan-1-ol, 1,2, 6-hexanetriol, 1,1, 1-tris- (hydroxymethyl) ethane, 3- (2' -hydroxyethoxy) propane-1, 2-diol, 3- (2 '-hydroxypropoxy) propane-1, 2-diol, 2- (2' -hydroxyethoxy) alkane-1, 2-diol, 6- (2 '-propoxy) hexane-1, 2-diol, 1,1, 1-tris [ (2' -hydroxyethoxy) methyl ] ethane, 1,1, 1-tris [ (2 '-hydroxypropoxy) methyl ] propane, 1,1, 1-tris (4' -hydroxyphenyl) ethane, glycerol, 2 '-hydroxyethoxy) propane, 1, 2-diol, 2-hydroxypropoxy, 1, 1-tris (2' -hydroxypropoxy) propane, 2-diol, 1,1, 1-tris (2-hydroxy-ethoxy) ethane, 1,1, 1-hydroxy-1, 1-hydroxy-1, 1-hydroxy-ethoxy) propane, 1-hydroxy-1-hydroxy-2-hydroxy-ethoxy) propane, 1-hydroxy-2-hydroxy-ethoxy) propane, 1-2-hydroxy-1-hydroxy-2-hydroxy-2-hydroxy-ethoxy) propane, 1-hydroxy-2-hydroxy-2, 1,1, 1-hydroxy-2, 1, 1-hydroxy-2, 1,1,1, at least one of 1,1, 1-tris (hydroxyphenyl) propane, 1,1, 5-tris (hydroxyphenyl) -3-methylpentane, trimethylolpropane ethoxylate, trimethylolpropane propoxylate and trihydroxy polyether compounds (e.g. diethylene glycol, triethylene glycol); the polyols and/or polymers having a hydroxyl number of four or more include, but are not limited to, 1, 3-tris (dihydroxy-3-methylphenyl) propane, 1, 4-tris (dihydroxyphenyl) butane, di (trimethylolpropane), 1,3, 3-tetrakis (methoxy) propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and polyvinyl alcohols having a certain degree of polymerization, ethylene vinyl alcohol copolymers, dendritic hyperbranched polyesters, and combinations thereof.
In the polyamide composition of the polyamide resin of the present invention, the additive component may further comprise a lubricant, and the lubricant includes, but is not limited to, calcium stearate, sodium stearate, zinc stearate, lithium stearate, calcium montanate, glycerol monostearate, glycerol tristearate, ethylene bis-stearamide, ethylene bis-lauramide, ethylene bis-oleamide, low molecular weight ionomers, ethylene-acrylic acid copolymers, ethylene-vinyl acetate copolymers, polyethylene wax, oxidized polyethylene, fatty acid amides, pentaerythritol tetrastearate, and combinations thereof.
In the polyamide composition of the polyamide resin of the present invention, the additive component may further include a thermal stabilizer comprising a copper-based stabilizer, a phenol-based stabilizer, a phosphite-based stabilizer, a hindered amine-based stabilizer, a sulfur-based stabilizer, an inorganic phosphorus-containing stabilizer, an oxalic acid aniline-based stabilizer, an aromatic secondary amine-based stabilizer, carbon black, a metal powder, and a combination thereof.
In the polyamide composition of the polyamide resin of the present invention, the additive component may further comprise a copper compound including, but not limited to, monovalent or divalent copper salts of organic or inorganic acids, monohydric or dihydric phenols, copper phosphates, copper pyrophosphates, copper sulfates and nitrates, copper oxides or cuprous oxides, complexes of copper salts with amines, amides, lactams, cyanides or phosphines, halides of monovalent or divalent copper, and fatty acid copper salts of monovalent or divalent copper. Particularly preferred are monovalent copper compounds, cuprous iodide, cuprous chloride, cuprous bromide, cupric acetate, cupric fatty acid, cuprous oxide, and divalent copper compounds, cupric chloride, cupric bromide, cupric iodide, cupric sulfate, and cupric oxide.
The polyamide composition of the invention may preferably comprise an alkali metal halide in an amount of 1 to 20 times the weight of the copper compound. Alkali metal halides include, but are not limited to, lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, and potassium iodide. Among them, potassium iodide is preferable.
In the polyamide composition of the polyamide resin of the present invention, the additive component may further include a phenolic stabilizer, and as the phenolic stabilizer, there is no particular limitation, and examples thereof include: a hindered phenolic compound. The hindered phenol compound includes, but is not limited to, N '-hexane-1, 6-diylbis [3- (3, 5-di-t-butyl-4-hydroxyphenylpropionamide) ], pentaerythrityl tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], N' -hexamethylenebis (3, 5-di-t-butyl-4-hydroxyhydrocinnamide), triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate ], 3, 9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propynyloxy ] -1, 1-dimethylethyl } -2,4,8, 10-tetraoxaspiro [5.5] undecane, diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanuric acid and the like.
These phenolic stabilizers may be used singly or in combination.
In the polyamide composition of the polyamide resin of the present invention, the additive component may further include a phosphite stabilizer, which is not particularly limited, and examples thereof include: trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, diphenyloctyl phosphite, triisodecyl phosphite, diisodecyl monobenzylphosphite, ditridecyl phosphite, diisooctyl diphenylphosphite, diisodecyl diphenylphosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tris (2, 4-di-tert-butyl-5-methylphenyl) phosphite, tris (oxyethyl) phosphite, 4 '-butylidene-bis (3-methyl-6-tert-butylphenyl tetra (tridecyl)) diphosphite, tetrakis (C12-C15 mixed alkyl) -4, 4' -isopropylidene diphenyl diphosphite, 4,4 '-isopropylidene-bis (2-tert-butylphenyl) -bis (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetrakis (tridecyl) -1,1, 3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane diphosphite, tetrakis (tridecyl) -4, 4' -butylidene-bis (3-methyl-6-tert-butylphenyl) diphosphite, (C1-C15 mixed alkyl) -4,4 '-isopropylidene diphenyl diphosphite, tris (mono-, di-mixed nonylphenyl) phosphite, 4' -isopropylidene-bis (2-tert-butylphenyl) -bis (nonylphenyl) phosphite, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, Tris (3, 5-di-tert-butyl-4-hydroxyphenyl) phosphite, hydrogenated 4,4 ' -isopropylidenediphenyl phosphite, bis (octylphenyl) bis (4,4 ' -butylidenebis (3-methyl-6-tert-butylphenyl)). 1, 6-hexanol diphosphite, hexa (tridecyl) -1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tris (4,4 ' -isopropylidenebis (2-tert-butylphenyl) phosphite, tris (1, 3-stearoyloxyisopropyl) phosphite, 2-methylenebis (4, 6-di-tert-butylphenyl) octylphosphite, 2-methylenebis (3-methyl-4, 6-di-tert-butylphenyl) -2-ethylphosphite, tetrakis (2, 4-di-tert-butyl-5-methylphenyl) -4,4 '-biphenylene diphosphite, tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenylene diphosphite, and the like. These phosphite stabilizers may be used singly or in combination of two or more.
The phosphite stabilizer may be a pentaerythritol phosphite compound. Examples of the pentaerythritol type phosphite compound include: 2, 6-di-tert-butyl-4-methylphenylphenylpentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenylphenylmethylpentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl-2-ethylhexyl pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenylisodecyl pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyllauryl pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenylisotridecyl pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenylstearyl pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenylpentaerythritol diphosphite, 2, 6-tert-butyl-4-methyl-phenyl-pentaerythritol-phosphite, 2, 6-di-tert-butyl-4-methylphenylcyclohexylpentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenylbenzyl pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenylethylcellulose pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenylcarbinol pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyloctylphenyl pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenylnonylphenyl pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methyl-phenyl-pentaerythritol diphosphite, 2, 6-butyl-4-methyl-butyl-4-methyl-butyl-ethyl-butyl-4-methyl-ethyl-butyl-4-methyl-butyl-4-methyl-butyl-ethyl-butyl-4-butyl-methyl-ethyl-butyl-4-butyl-methyl-butyl-pentaerythritol-4-butyl-4-butyl-methyl-butyl-4-butyl-pentaerythritol-butyl-methyl-butyl-4-butyl-ethyl-butyl-ethyl-butyl-pentaerythritol-butyl-ethyl-butyl-phosphite ester, 2, 6-butyl-, Bis (2, 6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl 2, 6-di-tert-butylphenyl pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl 2, 4-di-tert-octylphenyl pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl 2-cyclohexylphenyl pentaerythritol diphosphite, 2, 6-di-tert-amyl-4-methylphenylphenyl pentaerythritol diphosphite, bis (2, 6-di-tert-amyl-4-methylphenyl) pentaerythritol diphosphite and bis 2, 6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite, and the like.
These pentaerythritol type phosphite stabilizers may be used singly or in combination of two or more kinds. As the pentaerythritol type phosphite compound, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2, 6-di-t-pentyl-4-methylphenyl) pentaerythritol diphosphite, bis (2, 6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite and the like are preferable, and bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is more preferable.
In the polyamide composition of the polyamide resin of the present invention, the additive component may further comprise a suitable hindered amine-based stabilizer selected from, for example, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6, 6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) n-butyl-3, 5-di-t-butyl-4-hydroxymalonate, 1- (2-hydroxyethyl) -2, condensation products of 2,6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidylhexamethylenediamine and 1-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine, tris (2,2,6, 6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6, 6-tetramethyl-4-piperidyl) 1,2,3, 4-butanetetracarboxylic acid, 4- (ethylcarbamoyloxy) -2,2,6, 6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6, 6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6, 6-tetramethylpiperidine, bis (2,2,6, 6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6, 6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6, 6-tetramethyl-4-piperidyl) malonate, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6, 6-tetramethyl-4-piperidyl) adipate, bis (2,2,6, 6-tetramethyl-4-piperidyl) terephthalate, bis (2,2,6, 6-tetramethyl-piperidyl) -toluene-2, 4-diaminoformate, bis (2,2,6, 6-tetramethyl-4-piperidyl) -hexamethylene-1, 6-dicarbamate, tris (2,2,6, 6-tetramethyl-4-piperidyl) -benzene-1, 3, 5-tricarboxylate, tris (2,2,6, 6-tetramethyl-4-piperidyl) -benzene-1, 3, 4-tricarboxylate, 1, 2-bis (2,2,6, 6-tetramethyl-4-piperidinyloxy) -ethane, α, α -bis (2,2,6, 6-tetramethyl-4-piperidinyloxy) p-xylene, 1, 1' - (1, 2-ethylene) bis (3,3,5, 5-tetramethylpiperazinone), 4-benzoyl-2, 2,6, 6-tetramethylpiperidine, 4- (phenylacetyloxy) -2,2,6, 6-tetramethylpiperidine, 4-stearyloxy-2, 2,6, 6-tetramethylpiperidine, malonic acid bis (1,2,2,6, 6-pentamethylpiperidyl) -2-n-butyl-2- (2 hydroxy-3, 5-di-tert-butylbenzyl) ester, 3-n-octyl-7, 7,9, 9-tetramethyl-1, 3, 8-triazaspiro [4.5] decane-2, 4-dione, sebacic acid bis (1-octyloxy-2, 2,6, 6-tetramethylpiperidyl) ester, succinic acid bis (1-octyloxy-2, 2,6, 6-tetramethylpiperidyl) ester, a linear or cyclic condensate of N, N' -bis (2,2,6, 6-tetramethylpiperidyl) hexamethylenediamine and 4-morpholino-2, 6-dichloro-1, 3, 5-triazine, a condensate of 4-methoxy-2, 2,6, 6-tetramethylpiperidine, 4-acetoxy-2, 2,6, 6-tetramethylpiperidine, 2-chloro-4, 6-bis (4-N-butylamino-2, 2,6, 6-tetramethylpiperidyl-1, 3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane, a condensate of 2-chloro-4, 6-bis (4-N-butylamino-1, a condensate of 2,2,6, 6-pentamethylpiperidyl) -1,3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7, 7,9, 9-tetramethyl-1, 3, 8-triazaspiro [4.5] decane-2, 4-dione, 3-dodecyl-1- (2,2,6, 6-tetramethyl-4-piperidyl) pyrrolidine-2, 5-dione, 3-dodecyl-1- (1,2,2,6, 6-pentamethyl-4-piperidyl) pyrrolidine-2, 5-dione, 4-stearoyloxy-2, 2,6, 6-tetramethylpiperidine, 4-acryloyloxy-2, 2,6, 6-tetramethylpiperidine, a mixture of 4-hexadecyloxy-and 4-stearyloxy-2, 2,6, 6-tetramethylpiperidine, 4-epoxy-2, 2,6, 6-tetramethylpiperidine, 4-benzyloxy-2, 2,6, 6-tetramethylpiperidine, 4-phenoxy-2, 2,6, 6-tetramethylpiperidine, a condensate of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1, 3, 5-triazine, 1, 2-bis (3-aminopropylamino) ethane, 2,4, 6-trichloro-1, a condensate of 3, 5-triazine and 4-butylamino-2, 2,6, 6-tetramethylpiperidine (CAS number: 136504-96-6), a condensate of 1, 6-hexamethylenediamine, 2,4, 6-trichloro-1, 3, 5-triazine, N-dibutylamine and 4-butylamino-2, 2,6, 6-tetramethylpiperidine (CAS number: 192268-61-7), N- (2,2,6, 6-tetramethyl-4-piperidyl) -N-dodecylsuccinimide, N- (1,2,2,6, 6-pentamethyl-4-piperidyl) -N-dodecylsuccinimide, 2-undecyl-7, 7,9, 9-tetramethyl-1-oxa-3, 8-diaza-4-oxospiro [4,5] decane, the reaction product of 7,7,9, 9-tetramethyl-2-cycloundecanyl-1-oxo-3, 8-diaza-4-oxospiro [4,5] decane and epichlorohydrin, 1, 1-bis (1,2,2,6, 6-pentamethyl-4-piperidinyloxycarbonyl) -2- (4-methoxyphenyl) ene, N, N '-diformyl-N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) hexamethylenediamine, poly [ methylpropyl-3-oxy- (2,2,6, 6-tetramethyl-4-piperidyl) ] siloxane, 2, 4-bis [ - (1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) -N-butylamino ] -6- (2-hydroxyethyl) amino-1, 3, 5-triazine, 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2, 2,6, 6-tetramethylpiperidine, 5- (2-ethylhexanoyl) oxymethyl-3, 3, 5-trimethyl-2-quinolinone, Sanduvor (Clariant CAS No.: 106917-31-1), 5- (2-ethylhexanoyl) oxymethyl-3, 3, 5-trimethyl-2-morpholinone, 2, 4-bis [ (1-cyclohexyloxy-2, 2,6, 6-piperidin-4-yl) butylamino ] -6-chloro-s-triazine reaction product with N, N ' -bis (3-aminopropyl) ethylenediamine, 1,3, 5-tris (N-cyclohexyl-N- (2,2,6, 6-tetramethylpiperazin-3-on-4-yl) amino) -s-triazine, 1,3, 5-tris (N-cyclohexyl-N- (1,2,2,6, 6-pentamethylpiperazin-3-on-4-yl) amino) -s-triazine, 2,4, 6-tris (2 ' -hydroxy-4 ' -octyloxyphenyl) -1,3, 5-triazine, 2- (2 '-hydroxy-4' -hexyloxyphenyl) -4, 6-diphenyl-1, 3, 5-triazine, 2- (2 '-hydroxy-4' -octyloxyphenyl) -4, 6-bis (2 ', 4' -dimethylphenyl) -1,3, 5-triazine, 2- (2 ', 4' -dihydroxyphenyl) -4, 6-bis (2 ', 4' -dimethylphenyl) -1,3, 5-triazine, 2, 4-bis (2 '-hydroxy-4' -propoxyphenyl) -6- (2 ', 4' -dimethylphenyl) -1,3, 5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (4 ' -methylphenyl) -1,3, 5-triazine, 2- (2 ' -hydroxy-4 ' -dodecyloxyphenyl) -4, 6-bis (2 ', 4 ' -dimethylphenyl) -1,3, 5-triazine, 2,4, 6-tris (2 ' -hydroxy-4 ' -isopropoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2 ' -hydroxy-4 ' -n-hexyloxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2 ' -hydroxy-4 ' -ethoxycarbonylmethoxyphenyl) -1,3, 5-triazine. These stabilizers may be used singly or in combination of two or more.
In the polyamide composition of the polyamide resin of the present invention, the additive component may further include a sulfur-containing stabilizer. The sulfur-containing stabilizer is not particularly limited, and examples thereof include: organic thioacid compounds such as didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate) and thiobis (N-phenyl-. beta. -naphthylamine); mercaptobenzimidazole compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole and metal salts of 2-mercaptobenzimidazole; dithiocarbamate compounds such as metal salts of diethyldithiocarbamate and metal salts of dibutyldithiocarbamate, and thiourea compounds such as 1, 3-bis (dimethylaminopropyl) -2-thiourea and tributylthiourea; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropyl xanthate, trilauryltrithiophosphite and the like. Among these, mercaptobenzimidazole compounds, dithiocarbamic acid compounds, thiourea compounds, and organic thioacid compounds are preferable, and mercaptobenzimidazole compounds and organic thioacid compounds are more preferable. In particular, a thioether-based compound having a thioether structure can be suitably used because it takes oxygen from an oxidized substance and reduces it. Specifically, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, ditetradecylthiodipropionate, dioctadecylthiodipropionate, and pentaerythritol tetrakis (3-dodecylthiopropionate) are more preferable, ditetradecylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate), and 2-mercaptomethylbenzimidazole are further more preferable, and pentaerythritol tetrakis (3-dodecylthiopropionate) is particularly preferable. These sulfur-containing stabilizers may be used singly or in combination.
In the polyamide composition of the polyamide resin of the present invention, the additive component may further include an inorganic phosphorus-containing stabilizer. The inorganic phosphorus-containing stabilizer is not particularly limited, and examples thereof include phosphoric acids, phosphorous acids, hypophosphorous acids, metal salts of phosphoric acid, metal salts of phosphorous acid, and hypophosphorous acidsMetal phosphate salts, etc.; the phosphoric acids, phosphorous acids and hypophosphorous acids include, for example, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphorous acid, diphosphorous acid, and the like; examples of the metal salts of phosphoric acid, phosphorous acid and hypophosphorous acid include salts of the above-mentioned compounds such as phosphoric acid with a metal of group 1 of the periodic Table of the elements; the inorganic phosphorus-containing stabilizer is preferably a soluble compound, and examples thereof include sodium phosphate, sodium phosphite and sodium hypophosphite, more preferably sodium hypophosphite and sodium hypophosphite, and still more preferably sodium hypophosphite; as the inorganic phosphorus-containing stabilizer, for example, a hydrate thereof (preferably, a hydrate of sodium hypophosphite (NaH) may be mentioned2PO2·nH2O)). These inorganic phosphorus-containing stabilizers may be used singly or in combination of two or more kinds.
In the polyamide composition of the polyamide resin of the present invention, the additive component may further include an oxalic acid aniline stabilizer. As the oxalic anilide-based stabilizer, 4 ' -dioctyloxyoxanilide, 2 ' -diethoxyoxanilide, 2 ' -dioctyloxy-5, 5 ' -di-tert-butoxanilide, 2 ' -didodecyloxy-5, 5 ' -di-tert-butoxanilide, 2-ethoxy-2 ' -ethyloxanilide, N ' -bis (3-dimethylaminopropyl) oxalanilide, 2-ethoxy-5-tert-butyl-2 ' -ethoxyoxanilide (ethoxanilide) and a mixture thereof with 2-ethoxy-2 ' -ethyl-5, 4 ' -di-tert-butoxanilide, a mixture of o-methoxy-di-substituted oxanilide and p-methoxy-di-substituted oxanilide, a mixture of o-ethoxy-2 ' -ethyl-5, 4 ' -di-tert-butoxanilide, a mixture of o-methoxy-di-substituted oxanilide and p-N, Mixtures of o-ethoxy disubstituted oxanilides and p-ethoxy disubstituted oxanilides, and the like.
In the polyamide composition of the polyamide resin of the present invention, the additive component may further include an aromatic secondary amine-based stabilizer. The aromatic secondary amine-based stabilizer is preferably a compound having a diphenylamine skeleton, a compound having a phenylnaphthylamine skeleton, or a compound having a dinaphthylamine skeleton, and more preferably a compound having a diphenylamine skeleton or a compound having a phenylnaphthylamine skeleton. Specific examples thereof include compounds having a diphenylamine skeleton such as p, p '-dialkyldiphenylamine (having 8 to 14 carbon atoms in the alkyl group), octylated diphenylamine, 4' -bis (. alpha.,. alpha. -dimethyl) diphenylamine, p (p-toluenesulfonamide) diphenylamine, N '-diphenylp-phenylenediamine, N-phenyl-N' -isopropyl-p-phenylenediamine, N-phenyl-N '- (1, 3-dimethylbutyl) p-phenylenediamine and N-phenyl-N' - (3-methacryloyloxy-2-hydroxypropyl) p-phenylenediamine; compounds having a phenylamine skeleton such as N-phenyl-1-naphthylamine and N, N' -di-2-naphthyl-p-phenylenediamine; and compounds having a dinaphthylamine skeleton such as 2, 2-dinaphthylamine, 1, 2-dinaphthylamine, and 1, 1-dinaphthylamine. Among these, 4 ' -bis (. alpha.,. alpha. -dimethylbenzyl) diphenylamine, N ' -di-2-naphthyl-p-phenylenediamine and N, N ' -diphenyl-p-phenylenediamine are more preferable, and N, N ' -di-2-naphthyl-p-phenylenediamine and 4,4 ' -bis (. alpha.,. alpha. -dimethylbenzyl) diphenylamine are particularly preferable.
In the polyamide composition of the polyamide resin of the present invention, the additive component may further include a flow modifier. The flow modifier is one or a mixture of more of fluorine-containing polymer, PE wax, EBS, sodium or calcium montanate and hyperbranched polymer.
In the polyamide composition of the polyamide resin of the present invention, the additive component may further include a light stabilizer. In the heat-resistant polyamide composition, the light stabilizer is preferably one or a mixture of more of a benzophenone compound, a salicylate compound or a benzotriazole compound. The compounding step of the composition of the present invention may be performed by any method known in the art including, but not limited to, direct extrusion, ribbon extrusion, reactive injection molding, vertical mixing, horizontal mixing, feed mixing, and combinations thereof. The method may further comprise the step of pelletizing, dicing or granulating the heat resistant polyamide material once it has been compounded. For example, the heat resistant polyamide material may be pelletized using an underwater pelletizer or a linear pelletizer.
The polyamide resin or the composition of the present invention can be molded by any molding method such as injection molding, extrusion molding, blow molding, vacuum molding, melt spinning, and film molding to obtain the molded article of the present invention. The semi-aromatic polyamide resin composition can be applied to various products in the fields of electronic appliances, automobiles, aviation, aerospace, ships, household electrical appliances, building materials, cleaning products, sports products, daily necessities and the like. For example, components of an automobile engine coolant system, particularly components of radiator tanks such as the top and bottom of the radiator tank, water pump components such as a coolant reservoir tank, a water pipe, a water pump housing, a water pump impeller, and a valve, and the like, which are used in an automobile engine room in contact with coolant; the engine comprises an engine air inlet pipeline, an air inlet manifold, a supercharger component, a gear, a fan wheel, an engine cover, an engine guard plate, a heat exchanger shell, a refrigerator shell, a fastener and a gasket; in the field of electronics, the invention can be applied to active or passive components or parts of molded parts, printed circuit boards, housing parts, films, wires, switches, plugs, bushings, relays, resistors, capacitors, sockets, fuse holders, relays, wire-wound frameworks, housings for LC or LED, windings, transistors, connectors, regulators, integrated circuits, processors, heat sinks, controllers, memories, inductors, transformer insulators, adapter housings, mobile computer components, insulators, display backplanes, mouse housings, motor rear covers, electronic and electrical safety elements, partitions, molding, fastening pins, slide rails, guides, screws, nuts, isolating films; and switches, subminiature slide switches, DIP switches, switch cases, lamp holders, straps, connectors, connector cases, IC sockets, bobbins, bobbin covers, relays, relay boxes, capacitor cases, internal parts of motors, small-sized motor cases, gear cams, balance wheels, spacers, insulators, fasteners, clasps, wire clips, bicycle wheel, small foot print wheel, safety helmet, terminal platform, insulation part of shell starter of electric tool, spoiler, tank, radiator water tank, cavity tank, liquid storage tank, fuse box, air purifier shell, shell of air conditioner fan terminal, wheel cover, air suction and exhaust pipe, bearing, cylinder head cover, water pipe impeller, clutch separating rod, loudspeaker vibrating plate, heat-resisting container, microwave oven component, electric cooker component, printer ribbon guider; SMT-compliant connectors, sockets, plug-ins, sockets, power supply components, switches, sensors, capacitor sockets, relays, resistors, fuse holders, wire bobbins, housings for LC or LED, and other electrical/electronic-related components, automobile/vehicle-related components, home/office electrical components, computer-related components, facsimile/copier-related components, mechanical-related components, and other various uses.
Compared with the prior art, the invention has the following beneficial effects:
the invention reduces the concentration of free diamine monomer in a polymerization system by adding a certain amount of monocarboxylic acid compound, thereby reducing the loss of diamine monomer in the polymerization process.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Description of terms:
the proportionality coefficient r:
the mole total number a of dicarboxylic acid monomers, the mole total number b of diamine monomers, the mole total number c of monocarboxylic acid compounds, and a calculation formula for defining a proportion coefficient r:
Figure BDA0003407338960000191
the test methods used in the examples are as follows:
(1) melting point of polyamide resin:
melting Point (T) of Polyamide resinm) Determined by differential scanning calorimetry, DSC, (Perkin Elmer Diamond). DSC measurement of the sample, TmResults of (2) are from the secondary temperature rise DSC curve. In DSC test, the heating and cooling rates are both 10 ℃/min, the purge gas and the protective gas are both nitrogen in the test process, and the purge gas rate is 20 mL/min. Melting Point (T)m) Selected from the peak temperatures of the melting peaks in the quadratic heating curve.
(2) Intrinsic viscosity:
logarithmic viscosity eta of polyamides at concentrations of 0.5, 0.1, 0.3 and 1g/dl measured in concentrated sulfuric acid at 25 deg.Cinh。
ηinh＝[ln(t1/t0)]/C
Wherein η inh represents logarithmic viscosity (dl/g), t0Represents the flow time (sec), t, of the solvent1Represents the flow-through time (sec) of the sample solution, and C represents the concentration (g/dl) of the sample solution.
Extrapolating the data for η inh to a concentration of 0 to obtain the intrinsic viscosity of the sample.
(3) Diamine content in the effluent:
and titrating by using a dilute hydrochloric acid solution with standard concentration by using methyl red as an indicator, and converting the mass fraction of the diamine by using materials.
(4) Mechanical properties, tensile strength and elongation at break:
the prepared semi-aromatic polyamide was injection molded into dumbbell-shaped specimens, and the tensile strength and elongation at break thereof were tested according to the ASTM standard.
Example 1: PA 6T/66-50: 50
A10L stainless steel high-pressure polymerization reaction kettle is externally provided with a heating jacket, a magnetic-seal mechanical stirring and thermocouple for measuring the temperature in the kettle are arranged in the kettle, and a kettle cover is provided with a feeding port, an air inlet and outlet, a rupture disc and a pressure gauge for feeding materials. 1.162kg (10mol) of hexamethylene diamine, 0.731kg (5mol) of adipic acid, 0.831kg (5mol) of terephthalic acid, 12.21g of benzoic acid, 1g of sodium hypophosphite and 3kg of deionized water are added into a reaction kettle, after the materials are added, a feeding valve is closed, nitrogen is filled for three times, and air in the reaction kettle is discharged. Heating is started, and when the temperature in the reaction kettle reaches 95 ℃, mechanical stirring is started. The temperature is increased continuously until the temperature in the kettle rises to 220 ℃ under stirring. The reaction was continued for 2 hours at 220 ℃ under 2MPa by removing part of the water. Collecting the water vapor and diamine monomer discharged in the polymerization process through a coil cooling device. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried under vacuum at 80 ℃ for 24 hours and then subjected to solid-phase polymerization at 250 ℃ for 10 hours under a nitrogen gas stream to obtain a final semi-aromatic polyamide resin.
The content of the diamine monomer in the discharged water vapor in the polymerization process can be measured by titration of a dilute hydrochloric acid solution, and the mass fraction of the diamine monomer in the discharged water vapor can be calculated by conversion.
Example 2: PA 6T/66-50: 50
The polymerization process conditions and the feeding conditions in this example were the same as in example 1 except that the amount of benzoic acid added was changed to 24.42g (0.2 mol).
Example 3: PA 6T/66-50: 50
The polymerization conditions and the addition of the solution in this example were the same as those in example 1 except that the amount of benzoic acid added was changed to 36.64g (0.3 mol).
Example 4: PA6T/6I 65:35
A10L stainless steel high-pressure polymerization reaction kettle is externally provided with a heating jacket, a magnetic-seal mechanical stirring and thermocouple for measuring the temperature in the kettle are arranged in the kettle, and a kettle cover is provided with a feeding port, an air inlet and outlet, a rupture disc and a pressure gauge for feeding materials. 1.162kg (10mol) of hexamethylene diamine, 1.080kg (6.5mol) of terephthalic acid, 0.581kg (3.5mol) of isophthalic acid, 36.64g of benzoic acid, 1g of sodium hypophosphite and 3kg of deionized water are added into a reaction kettle, a charging valve is closed after the materials are added, nitrogen is filled and discharged for three times, and air in the reaction kettle is discharged. Heating is started, and when the temperature in the reaction kettle reaches 95 ℃, mechanical stirring is started. The temperature is increased continuously until the temperature in the kettle rises to 220 ℃ under stirring. The reaction was continued for 2 hours at 220 ℃ under 2MPa by removing part of the water. And collecting the water vapor and diamine monomers discharged in the polymerization process through a coil cooling device. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried under vacuum at 80 ℃ for 24 hours and then subjected to solid-phase polymerization at 250 ℃ for 10 hours under a nitrogen gas stream to obtain a final semi-aromatic polyamide resin.
The content of the diamine monomer in the discharged water vapor in the polymerization process can be measured by titration of a dilute hydrochloric acid solution, and the mass fraction of the diamine monomer in the discharged water vapor can be calculated by conversion.
Example 5: PA6T/6I/66 ═ 65:25:10
A10L stainless steel high-pressure polymerization reaction kettle is externally provided with a heating jacket, a magnetic-seal mechanical stirring and thermocouple for measuring the temperature in the kettle are arranged in the kettle, and a kettle cover is provided with a feeding port, an air inlet and outlet, a rupture disc and a pressure gauge for feeding materials. 1.162kg (10mol) of hexamethylene diamine, 1.080kg (6.5mol) of terephthalic acid, 0.415kg (2.5mol) of isophthalic acid, 0.146kg (1mol) of adipic acid, 36.64g of benzoic acid, 1g of sodium hypophosphite and 3kg of deionized water are added into a reaction kettle, a feeding valve is closed after the materials are completely added, nitrogen is filled for three times, and air in the reaction kettle is discharged. Heating is started, and when the temperature in the reaction kettle reaches 95 ℃, mechanical stirring is started. The temperature is increased continuously until the temperature in the kettle rises to 220 ℃ under stirring. The reaction was continued for 2 hours at 220 ℃ under 2MPa by removing part of the water. And collecting the water vapor and diamine monomers discharged in the polymerization process through a coil cooling device. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried under vacuum at 80 ℃ for 24 hours and then subjected to solid-phase polymerization at 250 ℃ for 10 hours under a nitrogen gas stream to obtain a final semi-aromatic polyamide resin.
The content of the diamine monomer in the discharged water vapor in the polymerization process can be measured by titration of a dilute hydrochloric acid solution, and the mass fraction of the diamine monomer in the discharged water vapor can be calculated by conversion.
Example 6: PA10T
A10L stainless steel high-pressure polymerization reaction kettle is externally provided with a heating jacket, a magnetic-seal mechanical stirring and thermocouple for measuring the temperature in the kettle are arranged in the kettle, and a kettle cover is provided with a feeding port, an air inlet and outlet, a rupture disc and a pressure gauge for feeding materials. Adding 1.723kg (10mol) of decamethylene diamine, 1.661kg (10mol) of terephthalic acid, 36.64g of benzoic acid, 1g of sodium hypophosphite and 3kg of deionized water into a reaction kettle, closing a charging valve after the materials are added, filling nitrogen for three times, and discharging air in the reaction kettle. Heating is started, and when the temperature in the reaction kettle reaches 95 ℃, mechanical stirring is started. The temperature is increased continuously until the temperature in the kettle rises to 220 ℃ under stirring. The reaction was continued for 2 hours at 220 ℃ under 2MPa by removing part of the water. And collecting the water vapor and diamine monomers discharged in the polymerization process through a coil cooling device. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was vacuum-dried at 80 ℃ for 24 hours and then subjected to solid-phase polymerization at 250 ℃ for 10 hours under a nitrogen gas stream to obtain a final semi-aromatic polyamide resin.
The content of the diamine monomer in the discharged water vapor in the polymerization process can be measured by titration of a dilute hydrochloric acid solution, and the mass fraction of the diamine monomer in the discharged water vapor can be calculated by conversion.
The test results and the material ratios of examples 1 to 6 are shown in Table 1.
Table 1 examples 1-6 addition and experimental results
Item Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
Hexamethylenediamine per mole 10 10 10 10 10 -
Decamethylenediamine/mol - - - - - 10
Adipic acid/mol 5 5 5 - 1.0 -
Terephthalic acid/mol 5 5 5 6.5 6.5 10
Isophthalic acid/mol - - - 3.5 2.5 -
Benzoic acid/mol 0.1 0.2 0.3 0.3 0.3 0.3
Sodium hypophosphite/g 1 1 1 1 1 1
Coefficient of proportionality r 1.005 1.010 1.015 1.015 1.015 1.015
Intrinsic viscosity (dl/g) of prepolymer 0.167 0.172 0.169 0.175 0.174 0.156
Intrinsic viscosity (dl/g) of semi-aromatic polyamide 1.45 1.43 1.38 1.46 1.51 1.54
Semi-aromatic polyamide melting point/. degree.C 307 306 307 302 310 315
Diamine content in the effluent water/wt% 0.26 0.15 0.07 0.05 0.06 0.03
Comparative example 1: PA 6T/66-50: 50
A10L stainless steel high-pressure polymerization reaction kettle is externally provided with a heating jacket, a magnetic-seal mechanical stirring and thermocouple for measuring the temperature in the kettle are arranged in the kettle, and a kettle cover is provided with a feeding port, an air inlet and outlet, a rupture disc and a pressure gauge for feeding materials. 1.185kg (10.2mol) of hexamethylene diamine, 0.731kg (5mol) of adipic acid, 0.831kg (5mol) of terephthalic acid, 1g of sodium hypophosphite and 3kg of deionized water are added into a reaction kettle, a feeding valve is closed after the materials are added, nitrogen is filled for three times, and air in the reaction kettle is discharged. Starting heating, and starting mechanical stirring when the temperature in the reaction kettle reaches 95 ℃. The temperature is increased continuously until the temperature in the kettle rises to 220 ℃ under stirring. The reaction was continued for 2 hours at 220 ℃ under 2MPa by removing part of the water. And collecting the water vapor and diamine monomers discharged in the polymerization process through a coil cooling device. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried under vacuum at 80 ℃ for 24 hours and then subjected to solid phase polymerization at 250 ℃ for 10 hours under a nitrogen gas stream to obtain the final semi-aromatic polyamide resin.
The content of the diamine monomer in the discharged water vapor in the polymerization process can be measured by titration of a dilute hydrochloric acid solution, and the mass fraction of the diamine monomer in the discharged water vapor can be calculated by conversion.
Comparative example 2: PA6T/6I 65:35
A10L stainless steel high-pressure polymerization reaction kettle is externally provided with a heating jacket, a magnetic-seal mechanical stirring and thermocouple for measuring the temperature in the kettle are arranged in the kettle, and a kettle cover is provided with a feeding port, an air inlet and outlet, a rupture disc and a pressure gauge for feeding materials. 1.185kg (10.2mol) of hexamethylene diamine, 1.080kg (6.5mol) of terephthalic acid, 0.581kg (3.5mol) of m-benzoic acid, 1g of sodium hypophosphite and 3kg of deionized water are added into a reaction kettle, a charging valve is closed after the materials are added, nitrogen is charged for three times, and air in the reaction kettle is discharged. Heating is started, and when the temperature in the reaction kettle reaches 95 ℃, mechanical stirring is started. The temperature was further raised to 220 ℃ under stirring. The reaction was continued for 2 hours at 220 ℃ under 2MPa by removing part of the water. And collecting the water vapor and diamine monomers discharged in the polymerization process through a coil cooling device. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried under vacuum at 80 ℃ for 24 hours and then subjected to solid-phase polymerization at 250 ℃ for 10 hours under a nitrogen gas stream to obtain a final semi-aromatic polyamide resin.
The content of the diamine monomer in the discharged water vapor in the polymerization process can be measured by titration of a dilute hydrochloric acid solution, and the mass fraction of the diamine monomer in the discharged water vapor can be calculated by conversion.
Comparative example 3: PA6T/6I/66 ═ 65:25:10
A10L stainless steel high-pressure polymerization reaction kettle is externally provided with a heating jacket, a magnetic-seal mechanical stirring and thermocouple for measuring the temperature in the kettle are arranged in the kettle, and a kettle cover is provided with a feeding port, an air inlet and outlet, a rupture disc and a pressure gauge for feeding materials. 1.185kg (10.2mol) of hexamethylene diamine, 1.080kg (6.5mol) of terephthalic acid, 0.415kg (2.5mol) of isophthalic acid, 0.146kg (1mol) of adipic acid, 1g of sodium hypophosphite and 3kg of deionized water are added into a reaction kettle, a feeding valve is closed after the materials are added, nitrogen is filled and exhausted for three times, and air in the reaction kettle is exhausted. Heating is started, and when the temperature in the reaction kettle reaches 95 ℃, mechanical stirring is started. The temperature was further raised to 220 ℃ by stirring. The reaction was continued for 2 hours at 220 ℃ under 2MPa by removing part of the water. And collecting the water vapor and diamine monomers discharged in the polymerization process through a coil cooling device. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried under vacuum at 80 ℃ for 24 hours and then subjected to solid phase polymerization at 250 ℃ for 10 hours under a nitrogen gas stream to obtain a final semi-aromatic polyamide resin.
The content of the diamine monomer in the discharged water vapor in the polymerization process can be measured by titration of a dilute hydrochloric acid solution, and the mass fraction of the diamine monomer in the discharged water vapor can be calculated by conversion.
Comparative example 4: PA10T
A10L stainless steel high-pressure polymerization reaction kettle is externally provided with a heating jacket, a magnetic-seal mechanical stirring and thermocouple for measuring the temperature in the kettle are arranged in the kettle, and a kettle cover is provided with a feeding port, an air inlet and outlet, a rupture disc and a pressure gauge for feeding materials. 1.758kg (10mol) decamethylene diamine, 1.661kg (10mol) terephthalic acid, 1g sodium hypophosphite and 3kg deionized water are added into the reaction kettle, after the materials are added, the charging valve is closed, nitrogen is charged and discharged for three times, and the air in the reaction kettle is discharged. Heating is started, and when the temperature in the reaction kettle reaches 95 ℃, mechanical stirring is started. The temperature is increased continuously until the temperature in the kettle rises to 220 ℃ under stirring. The reaction was continued for 2 hours at 220 ℃ under 2MPa by removing part of the water. And collecting water vapor and diamine monomer exhausted in the polymerization process through a coil cooling device. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried under vacuum at 80 ℃ for 24 hours and then subjected to solid-phase polymerization at 250 ℃ for 10 hours under a nitrogen gas stream to obtain a final semi-aromatic polyamide resin.
The content of the diamine monomer in the discharged water vapor in the polymerization process can be measured by titration of a dilute hydrochloric acid solution, and the mass fraction of the diamine monomer in the discharged water vapor can be calculated by conversion.
The test results and material ratios of comparative examples 1 to 4 are shown in Table 2.
TABLE 2 comparative examples 1-4 addition and experimental results
Item Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
Hexamethylenediamine per mole 10.2 10.2 10.2 -
Decamethylenediamine/mol - - - 10.2
Adipic acid/mol 5 - 1.0 -
Terephthalic acid/mol 5 6.5 6.5 10
Isophthalic acid/mol - 3.5 2.5 -
Sodium hypophosphite/g 1 1 1 1
Intrinsic viscosity (dl/g) of prepolymer 0.158 0.165 0.181 0.167
Intrinsic viscosity (dl/g) of semi-aromatic polyamide 1.51 1.56 1.58 1.61
Semi-aromatic polyamide melting point/. degree.C 306 301 309 314
Diamine content in the effluent water/wt% 1.50 1.43 1.62 0.98
As can be seen from tables 1-2, the present invention can greatly reduce the content of diamine monomer in the discharged water vapor during the polymerization process by adding the monocarboxylic acid compound and adjusting the proportionality coefficient r.
Examples 7 to 10
The semi-aromatic polyamide resins prepared in examples 1 to 4 were used for the preparation of molding compositions, respectively, whose raw material compositions are shown in Table 3. Wherein examples 7-10 correspond in sequence to the semi-aromatic polyamide resins of examples 1-4.
The preparation method comprises the following steps:
the semi-aromatic polyamide resin obtained in examples 1 to 4 was uniformly mixed with the antioxidant and talc in the amounts of the formula by means of a V-drum, and then subjected to extrusion modification by means of a twin-screw extruder, wherein the glass fiber in the amount of the formula was fed through a side feed port of the twin-screw extruder, to thereby obtain a modified semi-aromatic polyamide resin.
The modified semi-aromatic polyamide resin is injection-molded into dumbbell-shaped sample strips by an injection molding machine, and the tensile strength and the elongation at break of the sample strips are tested by a tensile machine according to the ASTM standard. The test results are shown in table 3.
TABLE 3 compositions of the raw materials of the compositions of examples 7-10 and mechanical test results
Figure BDA0003407338960000241

Claims (10)

1. A process for preparing a semi-aromatic polyamide terminated with a monocarboxylic acid, characterized in that: the method comprises the following steps:
(1) polymerizing a dicarboxylic acid monomer, a diamine monomer, a monocarboxylic acid compound, a catalyst and water in a pressure reaction vessel to obtain a prepolymer;
(2) and (3) performing solid-phase tackifying or melt polycondensation reaction on the prepolymer to obtain the semi-aromatic polyamide.
2. The process for the preparation of semi-aromatic polyamides end-capped with monocarboxylic acids according to claim 1, characterized in that: the dicarboxylic acid monomer A is a dicarboxylic acid monomer containing 4-36 carbon atoms, and comprises an aliphatic dicarboxylic acid monomer, an alicyclic dicarboxylic acid monomer and/or an aromatic dicarboxylic acid monomer, and an aliphatic or alicyclic dicarboxylic acid monomer;
the diamine monomer B is a diamine monomer containing 2-36 carbon atoms, and comprises an aliphatic diamine monomer, an alicyclic diamine monomer and/or an aromatic diamine monomer, and an aliphatic diamine monomer or an alicyclic diamine monomer.
3. The process for the preparation of semi-aromatic polyamides end-capped with monocarboxylic acids according to claim 1, characterized in that: the monocarboxylic acid compound is selected from one or more of aliphatic structure monocarboxylic acid compounds, alicyclic structure monocarboxylic acid compounds and aromatic structure monocarboxylic acid compounds.
4. The process for the preparation of semi-aromatic polyamides end-capped with monocarboxylic acids according to claim 1, characterized in that: the total mole number a of dicarboxylic acid monomers, the total mole number b of diamine monomers, and the total mole number c of monocarboxylic acid compounds, wherein c/a is 0.01-0.03, and the defined parameter r:
Figure FDA0003407338950000011
the value range of r is 1-1.1.
5. The process for the preparation of semi-aromatic polyamides end-capped with monocarboxylic acids according to claim 1, characterized in that: at the beginning of the polymerization reaction in step (1), lactams and/or amino acids selected from the group consisting of propane-3-lactam (. beta. -lactam; beta. -propiolactam), butane-4-lactam (. gamma. -lactam; gamma. -butyrolactam), 2-piperidone (. delta. -lactam; delta. -valerolactam), caprolactam (. epsilon. -lactam; epsilon. -caprolactam), alpha, omega-aminocaproic acid, hepta-7-lactam (. zeta. -lactam; zeta. -heptanolactam), alpha, omega-aminononanoic acid, nonane-9-lactam (. theta. -lactam; theta-nonanolactam), decan-10-lactam (. omega. -decanolactam) and the like may also be added, Alpha, omega-aminoundecanoic acid, laurolactam, omega-aminododecanoic acid, eta-octanolactam (eta-lactam; eta-octanolactam) or a combination thereof, the lactam and/or the amino acid being added in an amount of 0 to 90% of the total molar amount of the monomers.
6. The process for the preparation of semi-aromatic polyamides end-capped with monocarboxylic acids according to claim 1, characterized in that: the catalyst is selected from inorganic and/or organic phosphorus, tin or lead compounds and mixtures thereof; the amount of the catalyst is 0.0001-5 wt% of the total weight of the polymerization monomers.
7. The process for the preparation of semi-aromatic polyamides end-capped with monocarboxylic acids according to claim 1, characterized in that: in the step (1), the reaction temperature of the polymerization reaction is 200-300 ℃, and the reaction pressure is 0.5-5 MPa.
8. The process for the preparation of semi-aromatic polyamides end-capped with monocarboxylic acids according to claim 1, characterized in that: in the step (2), the solid-phase tackifying reaction is carried out in an inert gas atmosphere or under a vacuum condition, the reaction temperature is 220-280 ℃, and the reaction time is 2-24 hours; the melt polycondensation is carried out in an extrusion device with an exhaust port, the reaction temperature is 280-350 ℃, and the reaction time is within 0.5 hour.
9. A semi-aromatic polyamide characterized by: prepared by the preparation method as described in any one of claims 1-8, and has a melting point of 250-350 ℃.
10. A molding composition consisting of a semi-aromatic polyamide according to claim 9, characterized in that: the composite material comprises the following raw materials in parts by weight:
Figure FDA0003407338950000021
the additives include one or more of antioxidants, flame retardants, lubricants, mold release agents, nucleating agents, colorants, plasticizers, toughening agents, antistatic agents, solubilizers, dispersants, stabilizers, flow modifiers, or other polymeric resins.
CN202111520458.6A 2021-12-13 2021-12-13 Process for preparing semi-aromatic polyamides end-capped with monocarboxylic acids, semi-aromatic polyamides and molding compositions Pending CN114058008A (en)

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CN101463130A (en) * 2008-07-10 2009-06-24 金发科技股份有限公司 Semi-aromatic polyamide and low wastewater discharge preparation thereof
CN101759853A (en) * 2008-12-26 2010-06-30 金发科技股份有限公司 Method for preparing semi-aromatic polyamide
CN106243347A (en) * 2016-08-24 2016-12-21 江门市德众泰工程塑胶科技有限公司 A kind of preparation method of environmental protection polyamide
CN112661955A (en) * 2020-12-25 2021-04-16 江门市德众泰工程塑胶科技有限公司 Preparation method of semi-aromatic copolyamide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101463130A (en) * 2008-07-10 2009-06-24 金发科技股份有限公司 Semi-aromatic polyamide and low wastewater discharge preparation thereof
CN101759853A (en) * 2008-12-26 2010-06-30 金发科技股份有限公司 Method for preparing semi-aromatic polyamide
CN106243347A (en) * 2016-08-24 2016-12-21 江门市德众泰工程塑胶科技有限公司 A kind of preparation method of environmental protection polyamide
CN112661955A (en) * 2020-12-25 2021-04-16 江门市德众泰工程塑胶科技有限公司 Preparation method of semi-aromatic copolyamide

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