CN114133560B - Process for the preparation of semiaromatic polyamides with improved impact strength, semiaromatic polyamides and moulding compositions - Google Patents

Process for the preparation of semiaromatic polyamides with improved impact strength, semiaromatic polyamides and moulding compositions Download PDF

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CN114133560B
CN114133560B CN202111520456.7A CN202111520456A CN114133560B CN 114133560 B CN114133560 B CN 114133560B CN 202111520456 A CN202111520456 A CN 202111520456A CN 114133560 B CN114133560 B CN 114133560B
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acid
semi
reaction
impact strength
aromatic polyamide
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CN114133560A (en
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程圣利
李雪婷
马春林
王猛猛
贾生廷
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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
    • 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
    • C08G69/30—Solid state polycondensation
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention belongs to the technical field of polyamide, and particularly relates to a preparation method of semi-aromatic polyamide with improved impact strength, semi-aromatic polyamide and a molding composition. The preparation method of the semi-aromatic polyamide with improved impact strength comprises the steps of taking dicarboxylic acid monomers consisting of terephthalic acid, adipic acid and 1, 12-dodecanedioic acid and diamine monomers consisting of hexamethylenediamine and 1, 12-dodecanediamine as raw materials, carrying out polymerization reaction in water under the action of a catalyst and a blocking agent to obtain a prepolymer, and carrying out solid-phase tackifying or melt polycondensation reaction to obtain the semi-aromatic polyamide with improved impact strength. The invention reduces the melting point of the PA6T copolymer to a processable range, simultaneously well maintains the crystallization capability of the copolymer resin, improves the molding processability of the resin and improves the impact resistance of the copolymer resin.

Description

Process for the preparation of semiaromatic polyamides with improved impact strength, semiaromatic polyamides and moulding compositions
Technical Field
The invention belongs to the technical field of polyamide, and particularly relates to a preparation method of semi-aromatic polyamide with improved impact strength, semi-aromatic polyamide and a molding composition.
Background
Polyamides refer to a class of polymers whose backbone contains amide linkages (-CONH-). The molecular chain of the polyamide resin contains a large amount of fat structures, so that the common polyamide resin has a low melting point, and the application of the polyamide resin in the high-temperature field is limited. The melting temperature of the polyamide resin can be further increased by partially introducing an aromatic structure such as terephthalic acid, thereby increasing the use temperature of the polyamide resin. Because of the higher thermal stability and melting point than common nylon resins, such polymers are referred to as high temperature polyamides or high temperature nylons (HTPA). HTPA is often used in fields where high temperatures are required, such as automotive engine periphery and electronics, due to its better thermal stability, and in particular in soldering operations under lead-free conditions.
Semi-aromatic polyamides have a higher melting point, typically greater than 300 ℃, so semi-aromatic polyamides generally cannot be synthesized by polymerization processes like PA66 or PA 6. Conventional semi-aromatic polyamides are generally prepolymerized under high temperature and high pressure conditions by solution salification polycondensation, and the polymerization reaction is promoted to proceed in the direction of high molecular weight generation by gradual removal of water. And obtaining prepolymer after the polymerization degree reaches a certain degree, and obtaining the semi-aromatic polyamide resin with high molecular weight through further solid-phase polymerization or melt polymerization of the prepolymer. Depending on the embodiment of the finishing polymerization, the synthesis process of the semiaromatic polyamide is generally divided into a solid-phase polymerization process and a melt polycondensation process.
Since the melting point of the pure PA6T resin is up to 360 ℃ and exceeds the decomposition temperature of the resin, the pure PA6T resin has no processability and cannot be applied. To lower the melting point of PA6T resins, a copolymerization process is generally employed to introduce a low melting polyamide component, such as: PA6T/66 copolymerization, PA6T/6I, PA T/6I/66 copolymerization, and the like. However, the introduction of the comonomer also reduces the crystallization capacity of the resin, making the molding cycle time longer. In addition, the toughness of the resin is low and the impact resistance is poor due to the introduction of a PA 66-like short chain structure. To improve the above problems, a new method for improving the impact properties of semi-aromatic polyamides is desired.
Disclosure of Invention
The invention aims to solve the technical problems that: the preparation method of the semi-aromatic polyamide with improved impact strength is provided, the melting point of the PA6T copolymer is reduced to a processable range, meanwhile, the crystallization capability of the copolymer resin is well maintained, and the molding processability of the resin and the impact resistance of the copolymer resin are improved; the invention also provides the semi-aromatic polyamides prepared and molding compositions composed thereof.
First aspect:
the preparation method of the semi-aromatic polyamide with improved impact strength comprises the steps of taking dicarboxylic acid monomers consisting of terephthalic acid, adipic acid and 1, 12-dodecanedioic acid, diamine monomers consisting of hexamethylenediamine and 1, 12-dodecanediamine as raw materials, carrying out polymerization reaction in water under the action of a catalyst and a blocking agent to obtain a prepolymer, and carrying out solid-phase tackifying or melt polycondensation reaction to obtain the semi-aromatic polyamide with improved impact strength.
In the invention, the dicarboxylic acid monomer comprises the following components in mole percent: 30-100% of terephthalic acid, 0-70% of adipic acid and 0-70% of 1, 12-dodecanedioic acid.
The diamine monomer comprises the following components in mole percent: 0-100% of hexamethylenediamine and 0-100% of 1, 12-dodecanediamine.
Wherein, the content of 1, 12-dodecanedioic acid and 1, 12-dodecanediamine in the dicarboxylic acid monomer and diamine monomer is 0 when different.
The molar total number of dicarboxylic acid monomers is a, the molar total number of diamine monomers is b, and the molar ratio r=a/b of dicarboxylic acid monomers to diamine monomers, wherein the value of r ranges from 0.85 to 1.2, preferably from 0.95 to 1.1.
Since the molecular length of terephthalic acid (0.59 nm) is substantially identical to that of adipic acid (0.63 nm), when terephthalic acid is substituted for adipic acid monomer, the resulting copolyamide has a crystal structure similar to that of nylon 66, and the crystallization ability of the copolymer is not significantly affected, a phenomenon called isomorphous substitution. The invention discovers that isomorphous substitution phenomenon exists when 1, 12-dodecanedioic acid or 1, 12-dodecanediamine monomer is adopted for copolymerization, and the obtained copolymer has good crystallization capability and impact resistance.
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 thereof with monovalent or trivalent cations, and/or esters thereof, for example triphenyl phosphate, triphenyl phosphite or tris (nonylphenyl) phosphite.
Tin oxide, tin hydroxide, tin salts of monocarboxylic or polycarboxylic acids are suitable tin catalysts. Such as tin dibenzoate, tin di (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 catalyst is used in an amount of 0.0001 to 5wt%, preferably 10 to 1000ppm, most preferably 100 to 500ppm based on the total weight of the polymerized monomers.
In the present invention, a suitable end-capping agent is selected from one or more of aliphatic monocarboxylic acid compounds, alicyclic monocarboxylic acid compounds, aromatic monocarboxylic acid compounds, aliphatic monoamine compounds, alicyclic monoamine compounds and aromatic monoamine compounds.
The above monocarboxylic acids include acetic acid, propionic acid, n-butyric acid, isobutyric acid, t-butyric acid, valeric acid, pivalic acid, dimethylacetic acid, caproic acid, heptanoic acid, caprylic acid, nonanoic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, cyclopropanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, benzoic acid, p-methylbenzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-tert-butylbenzoic acid, salicylic acid, p-methoxybenzoic acid, a-naphthoic acid, β -naphthoic acid, methylnaphthalene carboxylic acid, phenylacetic acid, oleic acid, lactic acid, ricinoleic acid, linoleic acid, linolenic acid, erucic acid, various fatty acids derived from plants, acrylic acid, methacrylic acid, and mixtures thereof.
The monoamine compounds described above include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, octadecylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dicyclohexylamine, aniline, toluidine, diphenylamine, naphthylamine, and mixtures thereof.
Particularly preferred capping agents are at least one of acetic acid, propionic acid, benzoic acid.
The amount of end-capping agent is 0.01 to 10wt%, preferably 0.1 to 1wt%, most preferably 0.2 to 0.8wt% based on the total weight of the polymerized monomers.
In the invention, the reaction temperature of the polymerization reaction is 200-300 ℃ and the reaction pressure is 0.5-5MPa. The polymerization reaction is to make the nylon salt formed by the diamine monomer and the diamine monomer, deionized water, catalyst and end capping agent continuously release the water vapor in the reaction vessel under the pressure of 0.5-5MPa at the temperature of 200-300 ℃ to push the reaction to the polymerization reaction direction so as to obtain the semi-aromatic polyamide prepolymer with certain molecular weight.
In the invention, the solid-phase tackifying reaction is carried out in inert gas atmosphere or 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.
Second aspect:
the semi-aromatic polyamide with improved impact strength is prepared by the preparation method, and the melting point is 250-350 ℃ and is measured by Differential Scanning Calorimetry (DSC).
Third aspect:
the molding composition composed of the semi-aromatic polyamide with improved impact strength comprises the following raw materials in parts by weight:
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 cured 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 combinations thereof. Preferably at least one of glass fiber, carbon fiber, aramid fiber, boron fiber, metal fiber, and potassium titanate fiber.
The inorganic filler comprises fibrous, granular and nanoparticle fillers, such as glass beads, ceramic beads, kaolin, chalk, clay, alumina silica, zinc sulfide, strontium sulfide, barium sulfide, lead titanate, barium titanate, molybdenum disulfide, polytetrafluoroethylene, titanium dioxide, silicon dioxide, barium carbonate, magnesium carbonate, aluminum nitride, boron nitride, silicon carbide, potassium titanate whiskers, zinc borate, zinc phosphate, zinc oxide, titanium nitride, titanium oxide, titanium alloy, titanium calcium phosphate, aluminum borate whisker, carbon black, graphite, graphene, carbon nanotubes, nano alumina, silicate, aluminum silicate, calcium silicate, magnesium silicate, basic zinc silicate, calcium oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, zinc oxide whisker, antimony oxide, lead white, hydrated tin oxide, silver chloride, silver oxide, zinc oxide whisker, zinc oxide, 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, double hydroxide, zeolite, pyrophyllite, wollastonite, nano-layered silicate, nano-sized 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 the group consisting of isocyanate-based compounds, organosilane-based compounds, organotitanate-based compounds, organoborane-based compounds, and epoxy compounds, preferably organosilane-based compounds.
Wherein the organosilane compound is one or more selected from an alkoxysilane compound containing an epoxy group, an alkoxysilane compound containing a mercapto group, an alkoxysilane compound containing a urea group, an alkoxysilane compound containing an isocyanate group, an alkoxysilane compound containing an amino group, an alkoxysilane compound containing a hydroxyl group, an alkoxysilane compound containing a carbon-carbon unsaturated group, and an alkoxysilane compound containing an acid anhydride group; the alkoxy silane compound containing epoxy groups is selected from one or more of gamma-glycidoxypropyl trimethoxy silane, gamma-glycidoxypropyl triethoxy silane and beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane; the alkoxy silane compound containing the mercapto group is selected from gamma-mercaptopropyl trimethoxy silane and/or gamma-mercaptopropyl triethoxy silane; the alkoxy silane compound containing ureido is selected from one or more of gamma-ureidopropyl triethoxysilane, gamma-ureidopropyl trimethoxysilane and gamma- (2-ureidoethyl) amino propyl trimethoxysilane; the alkoxy silane compound containing isocyanate groups is selected from one or more of gamma-isocyanatopropyl triethoxysilane, gamma-isocyanatopropyl trimethoxysilane, gamma-isocyanatopropyl methyl dimethoxy silane, gamma-isocyanatopropyl methyl diethoxysilane, gamma-isocyanatopropyl ethyl dimethoxy silane, gamma-isocyanatopropyl ethyl diethoxysilane and gamma-isocyanatopropyl trichlorosilane; the amino-containing alkoxysilane compound is selected from one or more of gamma- (2-aminoethyl) aminopropyl methyl dimethoxy silane, gamma- (2-aminoethyl) aminopropyl trimethoxy silane and gamma-aminopropyl trimethoxy silane; the alkoxy silane compound containing hydroxyl is selected from gamma-hydroxypropyl trimethoxysilane and/or gamma-hydroxypropyl triethoxysilane; the alkoxy silane compound containing carbon-carbon unsaturated groups is selected from one or more of gamma-methacryloxypropyl trimethoxy silane, vinyl trimethoxy silane and N-beta- (N-vinylbenzyl amino ethyl) -gamma-amino propyl trimethoxy silane hydrochloride; the alkoxysilane compound containing an acid anhydride group is selected from 3-trimethoxysilylpropyl succinic anhydride; the organosilane compound is preferably gamma-methacryloxypropyl trimethoxysilane, gamma- (2-aminoethyl) aminopropyl methyl dimethoxy silane, gamma- (2-aminoethyl) aminopropyl trimethoxysilane, gamma-aminopropyl trimethoxysilane or 3-trimethoxysilylpropyl succinic anhydride.
The coupling agent is used in an amount of 0.05 to 10wt%, preferably 0.15wt% based on the weight of the inorganic filler; when the amount of the coupling agent is less than 0.05wt%, the inorganic filler is liable to be coagulated and there is a risk of poor dispersion in the polyamide resin, eventually leading to a decrease in mechanical properties.
In the present invention, the additive includes one or more of an antioxidant, a flame retardant, a lubricant, a mold release agent, a nucleating agent, a colorant, a plasticizer, a toughening agent, an antistatic agent, a solubilizer, a dispersant, a stabilizer, a flow modifier, or other polymer resins. The additives are all common assistants in the field and are added according to the performance requirements of the composition.
In the invention, the antioxidant comprises amine antioxidants, phenolic antioxidants and ester antioxidants.
Amine antioxidants include, but are not limited to, p-isopropoxydiphenyl amine; 4, 4-bis (α, α -dimethylbenzyl) diphenylamine, N-bis (1, 4-dimethylpentyl) p-phenylenediamine, N-di- β -naphthylp-phenylenediamine, N- (1, 3-dimethylbutyl) -N-phenyl-p-phenylenediamine, 2, 4-trimethyl-1, 2 dihydroquinoline polymer, and the like.
Phenolic antioxidants include, but are not limited to, 1-hydroxy-3-methyl-4-isopropylbenzene, 2,4, 6-tri-tert-butylphenol, n-stearyl β - (4-hydroxy-3, 5-di-tert-butylphenyl) propionate, pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and the like.
Esters antioxidants include, but are not limited to, n-stearyl β - (4-hydroxy-3, 5-di-t-butylphenyl) propionate, dilauryl thiodipropionate, stearyl β, β -thiodibutyrate, triphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, and the like.
In the present invention, the flame retardant includes halogen flame retardants 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 (tetrabromophthaloyl) imine, ethylenebis pentabromodiphenyl, tris (tribromophenoxy) triazine, bis (dibromopropyl) tetrabromobisphenol a, bis (dibromopropyl) tetrabromobisphenol S, brominated polyphenylene oxides (including poly (di) bromophenyl ether, etc.), brominated polystyrene (including polydibromostyrene, polytriabromostyrene, crosslinked brominated polystyrene, etc.), brominated crosslinked aromatic polymer brominated epoxy resin, brominated phenoxy resin, brominated styrene-maleic anhydride copolymer, tetrabromobisphenol S, tris (tribromoneopentyl) phosphate, polybromotrimethylphenylindane, tris (dibromopropyl) isocyanurate, etc. The halogen flame retardant is preferably a brominated polyphenylene ether (including poly (di) bromophenyl ether) and the like) and a brominated polystyrene (including poly (dibromostyrene), poly (tribromostyrene), crosslinked brominated polystyrene and the like), more preferably a brominated polystyrene, from the viewpoints of low generation of corrosive gas during melt processing such as extrusion or molding, and mechanical properties such as flame retardancy, toughness and rigidity. Wherein the bromine content in the brominated polystyrene is preferably 55wt% to 75wt%.
The halogen-free flame retardant is one or more selected from nitrogen-containing flame retardants, phosphine-containing flame retardants or flame retardants containing nitrogen and phosphine; phosphine-containing flame retardants are preferred. The phosphorus-containing flame retardant comprises one or more of red phosphorus, aryl phosphate monophosphate, aryl phosphate bisphosphonate, dimethyl alkyl phosphonate, triphenyl phosphonate, tricresyl phosphonate, tri (xylene) phosphonate, propylbenzene phosphonate, butylbenzene phosphonate or phosphinate; preferably phosphinates; the phosphinate is represented by a compound represented by the following formula (I) and/or (II).
In the formula (I) and the formula (II), R and R may be the same or different and each represents a linear or branched C 1 ～C 6 -alkyl, aryl or phenyl. R is R 3 Represents C in a linear or branched form 1 ～C 10 Alkylene, C 6 ～C 10 Arylene, C 6 ～C 10 -alkylarylenes, or C 6 ～C 10 Aryl alkylene. 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 methylphosphinate, magnesium methylphosphinate, aluminum methylphosphinate, zinc methylphosphinate, calcium methylphosphinate, magnesium methane-bis (methylphosphinate), aluminum methane-bis (methylphosphinate), zinc methane-bis (methylphosphinate), benzene-1, 4- (dimethylphosphinate) calcium benzene-1, 4- (dimethylphosphinate) magnesium, benzene-1, 4- (dimethylphosphinate) aluminum, benzene-1, 4- (dimethylphosphinate) zinc, phenylphosphinate, calcium phenylphosphinate, magnesium phenylphosphinate, zinc dimethylphosphinate, zinc phenylphosphinate, and the like, preferably calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, ethylmethylphosphinate beggar, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, and more preferably aluminum diethylphosphinate.
Phosphinate compounds as flame retardants are readily available from the market. Examples of phosphinate compounds available from the market include EXOLIT OP11230, 0P1311, 0P1312, 0P930, P935, etc. manufactured by Clariant, clariant.
Among them, when phosphinate or diphosphine oxide is used, melamine polyphosphate is preferably used as the phosphorus flame retardant. By using melamine polyphosphate in combination, carbonization of polyamide can be promoted and the burning time can be shortened in the flame retardancy test. If an excessive amount of melamine polyphosphate is used, there is a tendency that a problem such as mold contamination occurs when the polyamide composition is injection molded, and therefore, the amount of melamine polyphosphate is preferably less than 1 part by mass relative to 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, and polymeric melamine phosphate, ammonium polyphosphate, trishydroxyethyl isocyanurate (optionally also ammonium polyphosphate in the form of a mixture with trishydroxyethyl 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 agent can be selected to be used as the flame retardant auxiliary agent, wherein the flame retardant auxiliary agent comprises antimony trioxide, antimony tetraoxide, antimony pentoxide, antimony iso-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, silica (silica), and the like. They may be used alone or in combination of 2 or more. These flame retardant aids may be treated with coupling agents such as silane coupling agents, titanium coupling agents, and the like. Among them, zinc stannate, sodium antimonate and/or zinc borate are preferable.
The additive component in the polyamide composition of the polyamide resin according to the invention may also comprise up to 50wt% 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 prepared by grafting or copolymerizing 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 homo-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 homo-or copolymer obtained by grafting or copolymerizing with an anhydride, (meth) acrylic acid or an ester thereof; the impact modifiers may also be carboxylic acid functionalized copolymers such as poly (ethylene-co- (methacrylic acid) or poly (ethylene-1-olefin-co (meth) acrylic acid) in which the 1-olefin is an alkene or an unsaturated (meth) acrylate having more than 4 atoms, including those copolymers in which the acid groups are neutralized to some extent by metal ions.
Impact modifiers based on styrene monomers (styrene and styrene derivatives) and other vinylaromatic 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 the styrene or in the form of mixtures with styrene are vinylaromatic monomers substituted on the aromatic ring and/or on the c=c double bond by C1-C20 hydrocarbon groups or by halogen atoms. Examples of alkenyl aromatic monomers are styrene, p-methylstyrene, alpha-methylstyrene, ethylstyrene, t-butylstyrene, vinyltoluene, 1, 2-diphenylethylene, 1-diphenylethylene, vinylxylene, vinyltoluene, vinylnaphthalene, divinylbenzene, bromostyrene, and chlorostyrenes, and combinations thereof. Styrene, p-methylstyrene, alpha-methylstyrene, vinylnaphthalene tert-butylstyrene, vinyltoluene, 1, 2-diphenylethylene, 1-diphenylethylene or mixtures of these substances are preferred.
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. Preference is given to 1, 3-butadiene and isoprene, in particular 1, 3-butadiene (hereinafter referred to by the abbreviation 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 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.
Copolymers of maleic anhydride grafted functionalized butadiene with styrene, non-polar or polar olefin homopolymers and copolymers made 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, are particularly preferred. Examples of commercially available impact modifiers that may be used in the additive component are:
TAFMER MC201: blend of g-MA (0.6%) 67% EP copolymer (20 mo1% propylene) +33% EB copolymer (15 mo1% 1-butene): mitsui Chemicals, japan.
TAFMER MH5010: g-MA (0.6%) ethylene-butene copolymer: mitsui.
TAFMER MH7010: g-MA (0.6%) ethylene-butene copolymer: mitsui.
TAFMER MH7020: g-MA (0.7%) EP copolymer: mitsui.
EXXELOR VA1801: g-MA (0.7%) EP copolymer: exxon Mobile Chemicals, US.
EXXELOR VA1803: g-MA (0.5-0.9%) EP copolymer, amorphous, exxon.
EXXELOR VA1810: g-MA (0.5%) EP copolymer, exxon.
EXXELOR MDEX 9411：g-MA(0.7％)EPDM，Exxon。
Fusebond MN4930: g-MA (0.5%) ethylene-octene copolymer, duPont, US.
FUSABOND EB560D: g-MA ethylene-n-butyl acrylate copolymer, duPont ELVALOY, duPont.
In addition to conjugated dienes, the hydrogenated block copolymers, if appropriate, contain lower hydrocarbon moieties, such as ethylene, propylene, 1-butene, dicyclopentadiene or nonconjugated dienes. 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, for example (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-polyisoprene, 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 available on the market are the various products under the trade names (Phillips), (Shell), (Dexco) and (Kuraray).
Examples of crystalline olefin polymers are low density, medium density 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 foregoing.
Preferably, the above impact modifiers comprise components having groups which are introduced by thermal reaction or free radical reaction of the backbone polymer with an unsaturated dicarboxylic anhydride, 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 here it is preferred to use an agent selected from the group consisting of:
maleic acid, maleic anhydride, monobutyl maleate, fumaric acid, aconitic acid and/or itaconic anhydride. Preferably 0.1 to 4.0% by weight of unsaturated anhydrides are grafted onto the impact-resistant component as component C, or unsaturated dianhydrides or precursors thereof are applied by grafting together with other unsaturated monomers. The grafting degree is usually preferably from 0.1 to 1.0%, particularly preferably from 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, other resins used such as polyolefin-based resins such as 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, polyarylate, and liquid crystal polyester; 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 polyether ether ketone and polyallylether ketone; a polynitrile-based resin such as polyacrylonitrile, polymethacrylonitrile, acrylonitrile/styrene copolymer, acrylonitrile/butadiene/styrene copolymer, and methacrylonitrile/butadiene/styrene copolymer; a polymethacrylate resin such as polymethyl methacrylate and polyethyl methacrylate; polyvinyl ester resins such as polyvinyl acetate; polyvinyl chloride resins such as polyvinylidene chloride, polyvinyl chloride-vinyl 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/vinylidene fluoride copolymer; polycarbonate resins such as polycarbonate; polyimide-based resins such as thermoplastic polyimide, polyamideimide, and polyether imide; thermoplastic polyurethane resin.
The polyamide composition of the polyamide resin of the invention is used for multicolor molding or polymer alloy, and the polymer material also comprises aliphatic polyamide and/or semi-aromatic polyamide, such as one or more of aliphatic diacid and aliphatic diamine which are derived from 4-20 carbon atoms, lactam of 4-20 carbon atoms, or polymer of aliphatic diacid, aliphatic diamine and lactam of 4-20 carbon atoms. Including, but not limited to, polyhexamethylene adipamide (PA 66), polylactam (PA 6), polyhexamethylene sebacamide (PA 610), polyamide 612, polyhexamethylene sebacamide (PA 1010), monohexamethylenediamine-caprolactam copolymer (PA 66/6), polyhexamethylene undecalamide (PA 11), polylactam (PA 12), and mixtures of two or more thereof. Semi-aromatic polyamides such as poly (m-xylylene adipamide) (MXD 6), poly (hexamethylene terephthalamide) (PA 6T), poly (nonylene terephthalamide) (PA 9T), poly (decylene terephthalamide) (PA 10T), poly (dodecylmethylene terephthalamide) (PA 12T), poly (4-aminocyclo) methane dodecanamide (PACM 12), polyamide-based resins such as polyamide raw material monomers for forming them and/or copolymers obtained using a plurality of the above polyamide raw material monomers. In addition to the polyamides described above, amorphous polyamides including, but not limited to, polycondensates of isophthalic acid/terephthalic acid/1, 6-hexamethylenediamine/bis (3-methyl-4-aminocyclohexyl) methane, polycondensates of terephthalic acid/2, 4-trimethyl-1, 6-hexamethylenediamine/2, 4-trimethyl-1, 6-hexamethylenediamine, polycondensates of isophthalic acid/bis (-methyl-4-aminocyclohexyl) methane/-dodecalactam, polycondensates of isophthalic acid/terephthalic acid/1, 6 hexamethylenediamine, polycondensates of isophthalic acid/2, 4-trimethyl-1, 6-hexamethylenediamine/2, 4-trimethyl-1, 6-hexamethylenediamine, polycondensates of isophthalic acid/terephthalic acid/2, 4-trimethyl-1, 6-hexamethylenediamine, polycondensates of isophthalic acid/terephthalic acid/other diamine components, or a polyamide resin such as a polyamide raw material monomer for forming the polyamide raw material monomer 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 further comprises polyphenyl 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 comprising 2,3, 6-trimethylphenol, and mixtures of polymers. Poly (2, 6-dimethyl-1, 4-phenylene) ether optionally in combination with 2,3, 6-trimethylphenol units is preferred. 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, the polyamide or both. The interaction may be chemical (e.g. by grafting) and/or physical (e.g. by influence on the surface properties of the dispersed phase).
To improve the compatibility of the resin and/or impact modifier with the polyamide resin, no more than 15% by mass of a solubilizer may be added in the present invention, which may be a polyfunctional compound containing at least one carboxylic acid group, carboxylic anhydride group, ester group, amide group or imide group. Such as maleic acid, maleic anhydride, 2-methyl maleic anhydride, 2-chloromaleic anhydride, 2, 3-diylmaleic anhydride, bicyclo [2, 1] -5-heptene-2, 3-dicarboxylic anhydride, 4-methyl-4-cyclohexan-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-dione spiro (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, mesaconic acid, acrylic acid, methacrylic acid, ethacrylic acid, methyl maleic anhydride, itaconic acid itaconic anhydride, butenylsuccinic acid, butenylsuccinic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, N-phenylmaleimide, 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-hydroxy-nonadecane-1, 2, 3-tricarboxylic acid and mono-or diesters of the above acids with C1 to C12 alcohols (e.g. methanol or ethanol), mono-or diamides of the above acids (if appropriate, alkyl or aryl groups having up to 12 carbon atoms may be substituted on N, and salts with alkali metals or alkaline earth metals (e.g., calcium and potassium). Among them, maleic acid, fumaric acid, maleic anhydride and citric acid are preferable.
The additive component in the polyamide composition of the polyamide resin of the present invention may further comprise 0 to 20 parts by weight of a polyol. The polyol comprises at least one of dihydric alcohol, trihydric alcohol, polyhydric alcohol with hydroxyl number more than or equal to four and polyhydric alcohol. The dihydric alcohol comprises at least one of 1, 2-ethylene glycol, 1, 3-propylene glycol, 2, 3-butanediol, 1, 5-pentanediol, 2-dimethyl-1, 3-propanediol and polyether glycol; the triols include, but are not limited to, glycerol, trimethylol propane, 2, 3-bis (2 '-hydroxyethyl) cyclohexane-1-ol, 1,2, 6-hexanetriol, 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 '-propoxyl) hexane-1, 2-diol 1, 1-tris [ (2' -hydroxyethoxy) methyl ] ethane, 1-tris [ (2 '-hydroxypropoxy) methyl ] propane 1, 1-tris (4' -hydroxyphenyl) ethane, 1-tris (hydroxyphenyl) propane at least one of 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-tetrakis (methoxy) propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and polyvinyl alcohol having a degree of polymerization, ethylene vinyl alcohol copolymers, dendritic hyperbranched polyesters, and combinations of the foregoing polyols.
The polyamide composition of the polyamide resin of the present invention may further comprise a lubricant including, but not limited to, calcium stearate, sodium stearate, zinc stearate, lithium stearate, calcium montanate, glyceryl monostearate, glyceryl tristearate, ethylene bis-stearamide, ethylene bis-lauramide, ethylene bis-oleamide, low molecular weight ionomer, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, polyethylene wax, oxidized polyethylene, fatty acid amide, pentaerythritol tetrastearate, and combinations thereof.
In the polyamide composition of the polyamide resin of the present invention, the additive component may further comprise a heat stabilizer comprising a copper-based stabilizer, a phenol-based stabilizer, a phosphite-based stabilizer, a hindered amine-based stabilizer, a sulfur-containing stabilizer, an inorganic phosphorus-containing stabilizer, an oxalic acid aniline-based stabilizer, an aromatic secondary amine-based stabilizer, carbon black, metal powder, and combinations thereof.
The additive component in the polyamide composition of the polyamide resin of the present invention may further comprise a copper compound including, but not limited to, organic or inorganic acids, monovalent or divalent copper salts of mono-or dihydric phenols, copper phosphate, copper pyrophosphate, copper sulfate and copper nitrate, copper oxide or copper oxide, copper salt complexes with amines, amides, lactams, cyanides or phosphines, monovalent or divalent copper halides, monovalent or divalent copper fatty acid copper salts. Particularly preferred are monovalent copper compounds, cuprous iodide, cuprous chloride, cuprous bromide, cupric acetate, cupric fatty acid, cuprous oxide, cupric chloride, cupric bromide, cupric iodide, cupric sulfate, 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 may be given: hindered phenol compounds. Hindered phenolic compounds include, but are not limited to, N '-hexane-1, 6-diylbis [3- (3, 5-di-t-butyl-4-hydroxyphenyl propionamide) ], pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], N' -hexamethylenebis (3, 5-di-t-butyl-4-hydroxy hydrocinnamamide), 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-t-butyl-4-hydroxybenzylphosphonate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3, 5-tris (4-t-butyl-3, 6-dimethylbenzyl) isocyanurate, 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, without particular limitation, and examples thereof include: trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, diphenyl octyl phosphite, triisodecyl phosphite, monodiisodecyl phosphite, monodiphenyl ditridecyl phosphite, diisodecyl diphenyl phosphite, diphenyl tridecyl 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 tetrakis (tridecyl) diphosphite, tetrakis (C12-C15 mixed alkyl) -4,4' -isopropylidenediphenyl diphosphite, 4' -isopropylidenebis (2-tert-butylphenyl) di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetrakis (tridecyl) -1, 3-tris (2-di-tert-butylphenyl) tris (2, 4-di-tert-butyl-5-methylphenyl) phosphite, tris (3-di-tert-butylphenyl) 4' -butylphenyl) 4,4' -di-tert-butylphenyl-4-propylidene-4-diphenyl phosphite, mixed 4-di-tert-butylphenyl-4-propylidene phosphite, 4-di-tert-butylphenyl-4-butylidene-4-3-di-tert-butylphenyl phosphite, 4-propylidene phosphite, mixed 4-di-tert-butylphenyl phosphite, 4,4' -isopropylidene bis (2-tert-butylphenyl) di (nonylphenyl) phosphite, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3, 5-di-tert-butyl-4-hydroxyphenyl) phosphite, hydrogenated 4,4' -isopropylidene diphenyl phosphite, bis (octylphenyl) bis (4, 4' -butylidenebis (3-methyl-6-tert-butylphenyl)) -1, 6-hexanol bisphosphite, hexa (tridecyl) -1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tris (4, 4' -isopropylidene bis (2-tert-butylphenyl) phosphite, tris (1, 3-stearoyloxyisopropyl) phosphite, 2-methylenebis (4, 6-di-tert-butylphenyl) octyl phosphite, 2-methylenebis (3-methyl-4, 6-di-tert-butylphenyl) -2-ethyl phosphite, tetrakis (2, 4-di-tert-butylphenyl) -4,4' -biphenylene phosphite and the like can be used as the stabilizer, two or more kinds may be used in combination.
The phosphite stabilizer may be a pentaerythritol-based phosphite compound. Examples of the pentaerythritol phosphite compound include: 2, 6-di-tert-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl-methyl-pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl isodecyl-pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl-Gui Ji-pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl isotridecyl-pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl-stearyl-pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl-cyclohexyl-pentaerythritol diphosphite, and 2, 6-Di-tert-butyl-4-methylphenyl benzyl pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl ethyl cellosolve pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl butyl carbitol pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl octyl phenyl pentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl nonylphenyl pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 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-methylphenyl-pentaerythritol diphosphite, bis (2, 6-di-tert-amyl-4-methylphenyl) pentaerythritol diphosphite, bis 2, 6-di-tert-octyl-4-methylphenyl) pentaerythritol diphosphite, and the like.
These pentaerythritol-based phosphite stabilizers may be used singly or in combination. 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-amyl-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) pentatetrol diphosphite is more preferable.
In the polyamide composition of the polyamide resin according to the invention, the additive component may also comprise suitable sterically hindered amine stabilizers, for example selected from the group consisting of bis (2, 6-tetramethyl-4-piperidinyl) sebacate, bis (2, 6-tetramethyl-4-piperidinyl) succinate, bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, bis (2, 6-tetramethyl-4-piperidinyl) succinate, bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, linear or cyclic condensates of N, N' -bis (2, 6-tetramethyl-4-piperidyl hexamethylenediamine and 1-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine, tri (2, 6-tetramethyl-4-piperidinyl) nitrilotriacetic acid ester, tetra (2, 6-tetramethyl-4-piperidinyl) 1,2,3, 4-butanetetracarboxylic acid ester, tri (2, 6-tetramethyl-4-piperidinyl) nitrilotriacetic acid ester, tetra (2, 6-tetramethyl-4-piperidinyl) 1,2,3, 4-butanetetracarboxylate, bis (2, 6-tetramethyl-4-piperidinyl) oxalate, bis (2, 6-tetramethyl-4-piperidinyl) malonate, bis (2, 6-tetramethyl-4-piperidinyl) sebacate, bis (2, 6-tetramethyl-4-piperidinyl) adipate, bis (2, 6-tetramethyl-4-piperidinyl) sebacate, bis (2, 6-tetramethyl-4-piperidinyl) adipate, tris (2, 6-tetramethyl-4-piperidinyl) -benzene-1, 3, 5-tricarboxylic acid ester, tris (2, 6-tetramethyl-4-piperidinyl) -benzene-1, 3, 4-tricarboxylic acid ester, 1, 2-bis (2, 6-tetramethyl-4-piperidyloxy) -ethane, alpha-bis (2, 6-tetramethyl-4-piperidyloxy) -p-xylene, 1, 2-bis (2, 6-tetramethyl-4-picolyl) -ethane, alpha, alpha-bis (2, 6-tetramethyl-4-piperidyloxy) p-xylene, malonic acid bis (1, 2, 6-pentamethylpiperidinyl) -2-N-butyl-2- (2-hydroxy-3, 5-di-tert-butylbenzyl) ester, 3-N-octyl-7, 9-tetramethyl-1, 3, 8-triazaspiro [4.5] decane-2, 4-dione, bis (1-octyloxy-2, 6-tetramethylpiperidinyl) sebacate, linear or cyclic condensates of bis (1-octyloxy-2, 6-tetramethylpiperidinyl) succinate, N, N' -bis (2, 6-tetramethyl-4-piperidinyl) hexamethylenediamine and 4-morpholino-2, 6-dichloro-1, 3, 5-triazine, 4-methoxy-2, 6-tetramethylpiperidine, 4-acetoxy-2, 6-tetramethylpiperidine, condensate of 2-chloro-4, 6-bis (4-N-butylamino-2, 6-tetramethylpiperidinyl-1, 3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane, condensate of 2-chloro-4, 6-bis (4-N-ylamino-1, 2, 6-pentamethylpiperidinyl) -1,3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7, 9-tetramethyl-1, 3, 8-triazaspiro [4.5] decane-2, 4-dione, 4-benzyloxy-2, 6-tetramethylpiperidine, 4-phenoxy-2, 6-tetramethylpiperidine, N, condensate of N '-bis (2, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1, 3, 5-triazine, a condensate of 4-benzyloxy-2, 6-tetramethylpiperidine, 4-phenoxy-2, 6-tetramethylpiperidine, N, N' -bis (2, 6-tetramethyl-4-piperidinyl) hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1, 3, 5-triazine, condensate of 1, 2-bis (3-aminopropylamino) ethane, 2,4, 6-trichloro-1, 3, 5-triazine and 4-butylamino-2, 6-tetramethylpiperidine (CAS number: 136504-96-6), 1, 6-hexamethylenediamine, 2,4, 6-trichloro-1, 3, 5-triazine, condensate of N, N-dibutylamine and 4-butylamino-2, 6-tetramethylpiperidine (CAS No.: 192268-61-7), N- (2, 6-tetramethyl-4-piperidinyl) -N-dodecylsuccinimide, n '-bis (2, 6-tetramethyl-4-piperidinyl) hexamethylenediamine, poly [ methylpropyl-3-oxy- (2, 6-tetramethyl-4-piperidinyl) ] siloxane, 2, 4-bis [ - (1-cyclohexyloxy-2, 6-tetramethylpiperidin-4-yl) -N-butylamino ] -6- (2-hydroxyethyl) amino-1, 3, 5-triazine, N' -bis (2, 6-tetramethyl-4-piperidinyl) hexamethylenediamine, poly [ methylpropyl-3-oxy- (2, 6-tetramethyl-4-piperidinyl) ] siloxane, 2, 4-bis [ - (1-cyclohexyloxy-2, 6-tetramethylpiperidin-4-yl) -N-butylamino ] -6- (2-hydroxyethyl) amino-1, 3, 5-triazine, 1- (2-hydroxy-2-methylpropyloxy) -4-octadecanoyloxy-2, 6-tetramethylpiperidine, 5- (2-ethylhexanoyl) oxymethyl-3, 5-trimethyl-2-inone, sanduvor (Clariant CAS No.: 106917-31-1), the reaction product of 5- (2-ethylhexanoyl) oxymethyl-3, 5-trimethyl-2-morpholone, 2, 4-bis [ (1-cyclohexyloxy-2, 6-piperidin-4-yl) butylamino ] -6-chloro-s-triazine with N, N '-bis (3-aminopropyl) ethylenediamine, 1,3, 5-tris (N-cyclohexyl-N- (2, 6-tetramethylpiperazin-3-one-4-yl) amino) -s-triazine, 1,3, 5-tris (N-cyclohexyl-N- (1, 2, 6-pentamethylpiperazin-3-one-4-yl) amino) -s-triazine, 2,4, 6-tris (2' -hydroxy-4 '-octoxyphenyl) -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 '-propyloxyphenyl) -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.
In the polyamide composition of the polyamide resin according to 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 thio compounds such as didodecyl thiodipropionate, ditetradecyl thiodipropionate, dioctadecyl thiodipropionate, pentaerythritol tetrakis (3-dodecyl thiopropionate), and thiobis (N-phenyl-beta-naphthylamine); mercaptobenzimidazole compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and metal salts of 2-mercaptobenzimidazole; dithiocarbamic acid compounds such as metal salts of diethyl dithiocarbamic acid and metal salts of dibutyl dithiocarbamic acid, and thiourea compounds such as 1, 3-bis (dimethylaminopropyl) -2-thiourea and tributylthiourea; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthate, trilaurylthiophosphite, and the like. Among these, mercaptobenzimidazole compounds, dithiocarbamate compounds, thiourea compounds and organic thio compounds are preferable, and mercaptobenzimidazole compounds and organic thio compounds are more preferable. In particular, a thioether compound having a thioether structure is reduced by taking oxygen from an oxidized substance, and thus can be suitably used. Specifically, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, ditetradecyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-dodecyl thiopropionate) are more preferable, ditetradecyl thiodipropionate, pentaerythritol tetrakis (3-dodecyl thiopropionate) and 2-mercaptomethylbenzimidazole are more preferable, and pentaerythritol tetrakis (3-dodecyl thiopropionate) is particularly preferable. These sulfur-containing stabilizers may be used singly or in combination.
In the polyamide composition of the polyamide resin according to 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 acid, phosphorous acid, hypophosphorous acid, metal phosphate, metal phosphite, metal hypophosphite, and the like; examples of the phosphoric acid, phosphorous acid and hypophosphorous acid include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphorous acid and diphosphorous acid; examples of the metal phosphate, metal phosphite and metal hypophosphite include salts of a compound such as phosphoric acid and a metal of group 1 of the periodic table; as inorganic phosphorus-containing stabilizers, preference is given to the solubilityExamples of the compound include sodium phosphate, sodium phosphite and sodium hypophosphite, more preferably sodium phosphite and sodium hypophosphite, and still more preferably sodium hypophosphite; the inorganic phosphorus-containing stabilizer may be, for example, a hydrate thereof (preferably sodium hypophosphite hydrate (NaH) 2 PO 2 ·nH 2 O)). One kind of these inorganic phosphorus-containing stabilizers may be used, and two or more kinds may be used in combination.
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 acid anilide stabilizer, 4' -dioctyloxyoxanilide, 2' -diethoxyoxanilide, 2' -dioctyloxy-5, 5' -di-t-butoxyoxanilide, 2' -didodecyloxy-5, 5' -di-t-butoxyoxanilide, 2-ethoxy-2 ' -ethyloxanilide, N ' -bis (3-dimethylaminopropyl) oxanilide, 2-ethoxy-5-t-butyl-2 ' -ethoxyoxanilide (ethoxanilide) and its mixture with 2-ethoxy-2 ' -ethyl-5, 4' -di-t-butoxyoxanilide, mixture of o-methoxy-disubstituted oxanilide with p-methoxy-disubstituted oxanilide, mixture of o-ethoxy-disubstituted oxanilide with p-ethoxy-disubstituted oxanilide, and the like are preferable.
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 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. Specifically, compounds having a diphenylamine skeleton such as p, p '-dialkyldiphenylamine (the number of carbon atoms of the alkyl group is 8 to 14), octylated diphenylamine, 4' -bis (. Alpha.,. Alpha. -dimethyl) diphenylamine, p (p-toluenesulfonamide) diphenylamine, N '-diphenylp-phenylenediamine, N-phenyl-N' -isopropylp-phenylenediamine, N-phenyl-N '- (1, 3-dimethylbutyl) p-phenylenediamine, and N-phenyl-N' - (3-methacryloyloxy-2-hydroxypropyl) p-phenylenediamine; compounds having a phenyl amine skeleton such as N-phenyl-1-naphthylamine and N, N' -di-2-naphthylp-phenylenediamine; and compounds having a dinaphthyl amine skeleton such as 2, 2-dinaphthyl amine, 1, 2-bis Cai Jian and 1, 1-dinaphthyl amine. Of these, 4' -bis (α, α -dimethylbenzyl) diphenylamine, N ' -di-2-naphthylp-phenylenediamine and N, N ' -diphenylp-phenylenediamine are more preferable, and N, N ' -di-2-naphthylp-phenylenediamine and 4,4' -bis (α, α -dimethylbenzyl) diphenylamine are particularly preferable.
In the polyamide composition of the polyamide resin according to 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 salt or calcium salt of montanic acid and hyperbranched polymer.
In the polyamide composition of the polyamide resin according to 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 a plurality of benzophenone compounds, salicylate compounds or benzotriazole compounds. 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 granulating, dicing or pelletising 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 wire-type pelletizer.
In order to obtain the molded article of the present invention, the polyamide resin or the composition of the present invention may be molded by any molding method such as injection molding, extrusion molding, blow molding, vacuum molding, melt spinning, film molding, etc. The semiaromatic polyamide resin composition of the present invention can be applied to various articles in the fields of electronic appliances, automobiles, aviation, aerospace, ships, household appliances, building materials, cleaning articles, sports articles, daily necessities, etc. For example, cooling water system components of an automobile engine, particularly radiator tank components such as the top and bottom of a radiator tank, coolant storage tanks, water pipes, water pump housings, water pump impellers, water pump components such as valves, and the like, which are used in contact with cooling water in an automobile engine room; an engine air inlet pipeline, an air inlet manifold, a booster 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 is applicable to active or passive components or parts of molded articles, printed circuit boards, housing parts, films, wires, switches, plugs, bushings, relays, resistors, capacitors, sockets, fuse holders, relays, wire reel frames, housings for LC or LED, windings, transistors, connectors, regulators, integrated circuits, processors, heat sinks, controllers, memories, inductors, transformer insulation, adapter housings, cell phone computer structural members, insulators, display backplanes, mouse housings, motor backshells, electronic and electrical safety elements, spacers, fillets, staples, fixing pins, sliding rails, guides, screws, nuts, isolating films; and switches, ultra-small slide switches, DIP switches, switch housings, lamp sockets, strapping, connectors, connector housings, IC sockets, bobbins, spool covers, relays, relay boxes, capacitor housings, motor internals, small motor housings, gear cams, balance wheels, gaskets, insulators, fasteners, buckles, wire clamps, bicycle wheels, small footprint wheels, helmets, terminal blocks, insulating parts of the housing starter of an electric tool, spoilers, cans, radiator tanks, cavity cans, liquid reservoirs, fuse boxes, air cleaner housings, housings of air conditioning fan terminals, covers, suction and exhaust pipes, bearing holders, cylinder head covers, water pipe impellers, clutch release levers, speaker diaphragms, heat resistant containers, microwave oven components, electric cooker components, printer ribbon guides; connectors adapted to SMT, sockets, connectors, sockets, power supply components, switches, sensors, capacitor sockets, relays, resistors, fuse holders, coil bobbins, housings for LCs or LEDs, and the like, automotive/vehicle-related components, home appliance/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:
according to the invention, 1, 12-dodecanedioic acid, 1, 12-dodecanediamine and other isomorphous substitution monomers are introduced, so that the melting point of the PA6T copolymer is reduced to a processable range, the crystallization capability of the copolymer resin is well maintained, and the molding processability of the resin is improved; in addition, the introduction of the long chain structure diacid or diamine monomer improves the impact resistance of the copolymer resin.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The test methods used in the examples are as follows:
(1) Polyamide resin melting point and melting enthalpy:
melting Point (T) of Polyamide resin m ) As determined by differential scanning calorimetry DSC (Perkin Elmer Diamond). In DSC test of sample, T m The results of (2) are derived from a secondary temperature rising DSC curve. In DSC test, the heating and cooling rates are 10 ℃/min, the purge gas and the protective gas are nitrogen in the test process, and the purge gas rate is 20mL/min. Melting Point (T) m ) The peak temperature of the melting peak in the secondary temperature rise curve is selected. The melting enthalpy Δh is calculated from the integrated area of the melting peak in the quadratic temperature rise curve.
(2) Intrinsic viscosity:
the logarithmic intrinsic viscosity eta of polyamides having concentrations of 0.5, 0.1, 0.3 and 1g/dl is measured in concentrated sulfuric acid at 25 DEG C inh 。
η inh ＝[ln(t 1 /t 0 )]/C
Wherein ηinh represents logarithmic specific viscosity (dl/g), t 0 Indicating the flow time (sec) of the solvent, t 1 The flow-through time (sec) of the sample solution is represented, and C represents the concentration (g/dl) of the sample solution.
Extrapolation of the data for ηinh to a concentration of 0 gives the intrinsic viscosity of the sample, [ η ].
(3) Tensile strength:
the test conditions were 23℃and 10mm/min, determined according to 1S 0527-2. Wherein the injection spline is obtained by staying for 10min or less in the cavity of the injection molding machine at a temperature 20 ℃ higher than the melting point.
(4) Elongation at break:
the test conditions were 23℃and 10mm/min, determined according to 1S 0527-2.
(5) Notched impact strength:
the test conditions were 23℃and the notch type was type A, determined according to 1S 0180/1A.
(6) Mechanical properties, tensile strength and elongation at break:
the prepared semiaromatic polyamide was injection molded into dumbbell-shaped bars, which were tested for tensile strength and elongation at break according to ASTM standards.
Example 1
A heating jacket is arranged outside the 10L stainless steel high-pressure polymerization reaction kettle, a mechanical stirring and thermocouple for measuring the temperature in the kettle, which is sealed by magnetic force, is arranged in the kettle, and a charging hole, an air inlet and outlet, a rupture disk and a pressure gauge are arranged on the kettle cover. 1.162kg (10 mol) of hexamethylenediamine, 0.997kg (6 mol) of terephthalic acid, 0.921kg (4 mol) of 1, 12-dodecanedioic acid, 24.5g (0.05 mol) of benzoic acid, 1g of sodium hypophosphite and 3kg of deionized water are added into the reaction kettle, after the materials are added, a charging valve is closed, nitrogen is charged 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 was continuously raised to 220℃with stirring. The reaction was continued for 2 hours at 220℃and 2MPa by removing part of the water. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried in vacuo at 80℃for 24 hours, and then subjected to solid-phase polymerization under a nitrogen gas stream at 250℃for 10 hours to obtain the final semiaromatic polyamide resin.
Example 2
A heating jacket is arranged outside the 10L stainless steel high-pressure polymerization reaction kettle, a mechanical stirring and thermocouple for measuring the temperature in the kettle, which is sealed by magnetic force, is arranged in the kettle, and a charging hole, an air inlet and outlet, a rupture disk and a pressure gauge are arranged on the kettle cover. To the reaction vessel were added 0.581kg (5 mol) of hexamethylenediamine, 1.002kg (5 mol) of 1, 12-dodecanediamine, 1.163kg (7 mol) of terephthalic acid, 0.691kg (3 mol) of 1, 12-dodecanedioic acid, 24.5g (0.05 mol) of benzoic acid, 1g of sodium hypophosphite and 3kg of deionized water, and after the addition of the materials, the charging valve was closed, nitrogen was charged and discharged three times, and the air in the reaction vessel was discharged. Heating is started, and when the temperature in the reaction kettle reaches 95 ℃, mechanical stirring is started. The temperature was continuously raised to 220℃with stirring. The reaction was continued for 2 hours at 220℃and 2MPa by removing part of the water. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried in vacuo at 80℃for 24 hours, and then subjected to solid-phase polymerization under a nitrogen gas stream at 250℃for 10 hours to obtain the final semiaromatic polyamide resin.
Example 3
A heating jacket is arranged outside the 10L stainless steel high-pressure polymerization reaction kettle, a mechanical stirring and thermocouple for measuring the temperature in the kettle, which is sealed by magnetic force, is arranged in the kettle, and a charging hole, an air inlet and outlet, a rupture disk and a pressure gauge are arranged on the kettle cover. To the reaction vessel were added 0.581kg (5 mol) of hexamethylenediamine, 1.002kg (5 mol) of 1, 12-dodecanediamine, 1.163kg (7 mol) of terephthalic acid, 0.438kg (3 mol) of adipic acid, 24.5g (0.05 mol) of benzoic acid, 1g of sodium hypophosphite and 3kg of deionized water, after the addition of the materials was completed, the addition valve was closed, nitrogen was charged and discharged three times, and the air in the reaction vessel was discharged. Heating is started, and when the temperature in the reaction kettle reaches 95 ℃, mechanical stirring is started. The temperature was continuously raised to 220℃with stirring. The reaction was continued for 2 hours at 220℃and 2MPa by removing part of the water. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried in vacuo at 80℃for 24 hours, and then subjected to solid-phase polymerization under a nitrogen gas stream at 250℃for 10 hours to obtain the final semiaromatic polyamide resin.
Example 4
A heating jacket is arranged outside the 10L stainless steel high-pressure polymerization reaction kettle, a mechanical stirring and thermocouple for measuring the temperature in the kettle, which is sealed by magnetic force, is arranged in the kettle, and a charging hole, an air inlet and outlet, a rupture disk and a pressure gauge are arranged on the kettle cover. To the reaction vessel were added 0.349kg (3 mol) of hexamethylenediamine, 1.403kg (7 mol) of 1, 12-dodecanediamine, 1.329kg (8 mol) of terephthalic acid, 0.146kg (1 mol) of adipic acid, 0.230kg (1 mol) of 1, 12-dodecanedioic acid, 24.5g (0.05 mol) of benzoic acid, 1g of sodium hypophosphite and 3kg of deionized water, and after the addition of the materials, the addition valve was closed, nitrogen was charged three times, and the air in the reaction vessel was discharged. Heating is started, and when the temperature in the reaction kettle reaches 95 ℃, mechanical stirring is started. The temperature was continuously raised to 220℃with stirring. The reaction was continued for 2 hours at 220℃and 2MPa by removing part of the water. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried in vacuo at 80℃for 24 hours, and then subjected to solid-phase polymerization under a nitrogen gas stream at 250℃for 10 hours to obtain the final semiaromatic polyamide resin.
Example 5
A heating jacket is arranged outside the 10L stainless steel high-pressure polymerization reaction kettle, a mechanical stirring and thermocouple for measuring the temperature in the kettle, which is sealed by magnetic force, is arranged in the kettle, and a charging hole, an air inlet and outlet, a rupture disk and a pressure gauge are arranged on the kettle cover. 2.004kg (10 mol) of 1, 12-dodecanediamine, 1.661kg (10 mol) of terephthalic acid, 24.5g (0.05 mol) of benzoic acid, 1g of sodium hypophosphite and 3kg of deionized water are added into the reaction kettle, after the materials are added, a 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 was continuously raised to 220℃with stirring. The reaction was continued for 2 hours at 220℃and 2MPa by removing part of the water. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried in vacuo at 80℃for 24 hours, and then subjected to solid-phase polymerization under a nitrogen gas stream at 250℃for 10 hours to obtain the final semiaromatic polyamide resin.
The results of the tests of examples 1-5 and the material ratios are shown in Table 1.
Table 1 examples 1-5 feeding conditions and experimental results
Comparative example 1
A heating jacket is arranged outside the 10L stainless steel high-pressure polymerization reaction kettle, a mechanical stirring and thermocouple for measuring the temperature in the kettle, which is sealed by magnetic force, is arranged in the kettle, and a charging hole, an air inlet and outlet, a rupture disk and a pressure gauge are arranged on the kettle cover. 1.162kg (10 mol) of hexamethylenediamine, 0.708kg (3.5 mol) of sebacic acid, 1.080kg (6.5 mol) of terephthalic acid, 24.5g (0.2 mol) of benzoic acid, 1g of sodium hypophosphite and 3kg of deionized water are added into the reaction kettle, after the materials are added, a charging valve is closed, nitrogen is charged and discharged 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 continuously raised to 220℃with stirring. The reaction was continued for 2 hours at 220℃and 2MPa by removing part of the water. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried in vacuo at 80℃for 24 hours, and then subjected to solid-phase polymerization under a nitrogen gas stream at 250℃for 10 hours to obtain the final semiaromatic polyamide resin.
Comparative example 2
A heating jacket is arranged outside the 10L stainless steel high-pressure polymerization reaction kettle, a mechanical stirring and thermocouple for measuring the temperature in the kettle, which is sealed by magnetic force, is arranged in the kettle, and a charging hole, an air inlet and outlet, a rupture disk and a pressure gauge are arranged on the kettle cover. 1.583kg (10 mol) of trimethylhexamethylenediamine, 0.708kg (3.5 mol) of sebacic acid, 1.080kg (6.5 mol) of terephthalic acid, 24.5g (0.2 mol) of benzoic acid, 1g of sodium hypophosphite and 3kg of deionized water are added into the reaction kettle, after the addition of the materials, a charging valve is closed, nitrogen is charged and discharged 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 was continuously raised to 220℃with stirring. The reaction was continued for 2 hours at 220℃and 2MPa by removing part of the water. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried in vacuo at 80℃for 24 hours, and then subjected to solid-phase polymerization under a nitrogen gas stream at 250℃for 10 hours to obtain the final semiaromatic polyamide resin.
Comparative example 3
A heating jacket is arranged outside the 10L stainless steel high-pressure polymerization reaction kettle, a mechanical stirring and thermocouple for measuring the temperature in the kettle, which is sealed by magnetic force, is arranged in the kettle, and a charging hole, an air inlet and outlet, a rupture disk and a pressure gauge are arranged on the kettle cover. 1.162kg (10 mol) of hexamethylenediamine, 0.498kg (3 mol) of isophthalic acid, 1.163kg (7 mol) of terephthalic acid, 24.5g (0.2 mol) of benzoic acid, 1g of sodium hypophosphite and 3kg of deionized water are added into the reaction kettle, after the materials are added, a 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 was continuously raised to 220℃with stirring. The reaction was continued for 2 hours at 220℃and 2MPa by removing part of the water. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried in vacuo at 80℃for 24 hours, and then subjected to solid-phase polymerization under a nitrogen gas stream at 250℃for 10 hours to obtain the final semiaromatic polyamide resin.
Comparative example 4
A heating jacket is arranged outside the 10L stainless steel high-pressure polymerization reaction kettle, a mechanical stirring and thermocouple for measuring the temperature in the kettle, which is sealed by magnetic force, is arranged in the kettle, and a charging hole, an air inlet and outlet, a rupture disk and a pressure gauge are arranged on the kettle cover. To the reaction vessel were added 0.581kg (5 mol) of hexamethylenediamine, 0.791kg (3 mol) of nonylenediamine, 0.498kg (3 mol) of isophthalic acid, 1.163kg (7 mol) of terephthalic acid, 24.5g (0.2 mol) of benzoic acid, 1g of sodium hypophosphite and 3kg of deionized water, after the addition of the materials was completed, the feed valve was closed, nitrogen was purged three times, and the air in the reaction vessel was discharged. Heating is started, and when the temperature in the reaction kettle reaches 95 ℃, mechanical stirring is started. The temperature was continuously raised to 220℃with stirring. The reaction was continued for 2 hours at 220℃and 2MPa by removing part of the water. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried in vacuo at 80℃for 24 hours, and then subjected to solid-phase polymerization under a nitrogen gas stream at 250℃for 10 hours to obtain the final semiaromatic polyamide resin.
Comparative example 5
A heating jacket is arranged outside the 10L stainless steel high-pressure polymerization reaction kettle, a mechanical stirring and thermocouple for measuring the temperature in the kettle, which is sealed by magnetic force, is arranged in the kettle, and a charging hole, an air inlet and outlet, a rupture disk and a pressure gauge are arranged on the kettle cover. 1.162kg (10 mol) of hexamethylenediamine, 0.657kg (4.5 mol) of adipic acid, 0.914kg (5.5 mol) of terephthalic acid, 24.5g (0.2 mol) of benzoic acid, 1g of sodium hypophosphite and 3kg of deionized water are added into the reaction kettle, after the materials are added, a charging valve is closed, nitrogen is charged and discharged 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 was continuously raised to 220℃with stirring. The reaction was continued for 2 hours at 220℃and 2MPa by removing part of the water. Discharging after the reaction is finished, thereby obtaining the prepolymer. The prepolymer was dried in vacuo at 80℃for 24 hours, and then subjected to solid-phase polymerization under a nitrogen gas stream at 250℃for 10 hours to obtain the final semiaromatic polyamide resin.
Comparative examples 1-5 the results and material ratios are shown in Table 2.
Table 2 comparative examples 1-5 feeding conditions and experimental results
From the results of the invention, the isomorphous substitution monomers such as hexamethylenediamine, adipic acid, terephthalic acid, 1, 12-dodecanedioic acid and 1, 12-dodecanediamine can well maintain the crystallization capability of the copolymer resin while reducing the melting point of the PA6T copolymer to a processable range; in addition, the introduction of the long chain structure diacid or diamine monomer improves the impact resistance of the copolymer resin.
Examples 6 to 9
The semiaromatic polyamide resins prepared in examples 1 to 4 were used, respectively, for preparing molding compositions whose raw material compositions are shown in Table 3. Wherein examples 6-9 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 1-4, antioxidant and talcum powder with the formula amount are uniformly mixed through a V-shaped rotary drum, and then are extruded and modified through a double screw extruder, wherein glass fiber with the formula amount is added through a side feeding hole of the double screw extruder, so that the modified semi-aromatic polyamide resin is obtained.
The modified semiaromatic polyamide resin was injection molded into dumbbell-shaped bars by an injection molding machine, and the bars were tested for tensile strength and elongation at break by a tensile machine according to ASTM standards. The test results are shown in Table 3.
TABLE 3 raw material composition compositions and mechanical test results for examples 6-9
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Claims (7)

1. A process for preparing a semi-aromatic polyamide having improved impact strength, characterized by: taking dicarboxylic acid monomers consisting of terephthalic acid, adipic acid and 1, 12-dodecanedioic acid and diamine monomers consisting of hexamethylenediamine and 1, 12-dodecanediamine as raw materials, carrying out polymerization reaction in water under the action of a catalyst and a blocking agent to obtain prepolymer, and carrying out solid-phase tackifying or melt polycondensation reaction to obtain semi-aromatic polyamide with improved impact strength;
Wherein, the mole percentages of the components of the dicarboxylic acid monomer are: 70% of terephthalic acid and 30% of 1, 12-dodecanedioic acid; the diamine monomer comprises the following components in mole percent: 50% of hexamethylenediamine and 50% of 1, 12-dodecanediamine;
alternatively, the dicarboxylic acid monomer may comprise the following components in mole percent: 10% of adipic acid, 80% of terephthalic acid and 10% of 1, 12-dodecanedioic acid; the diamine monomer comprises the following components in mole percent: 30% of hexamethylenediamine and 70% of 1, 12-dodecanediamine;
the molar ratio of dicarboxylic acid monomer to diamine monomer was 1.
2. The method for producing an impact strength-improving semi-aromatic polyamide according to claim 1, wherein: the catalyst is selected from inorganic and/or organic phosphorus, tin or lead compounds and mixtures thereof; the catalyst is used in an amount of 0.0001 to 5wt% based on the total weight of the polymerized monomers.
3. The method for producing an impact strength-improving semi-aromatic polyamide according to claim 1, wherein: the end capping agent is selected from one or more of aliphatic monocarboxylic acid compounds, alicyclic monocarboxylic acid compounds, aromatic monocarboxylic acid compounds, aliphatic monoamine compounds, alicyclic monoamine compounds and aromatic monoamine compounds; the amount of the end-capping agent is 0.01 to 10wt% based on the total weight of the polymerized monomers.
4. The method for producing an impact strength-improving semi-aromatic polyamide according to claim 1, wherein: the reaction temperature of the polymerization reaction is 200-300 ℃ and the reaction pressure is 0.5-5MPa.
5. The method for producing an impact strength-improving semi-aromatic polyamide according to claim 1, wherein: the solid-phase tackifying reaction is carried out in inert gas atmosphere or 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.
6. A semiaromatic polyamide characterized in that: the process according to any one of claims 1 to 5, having a melting point of 250 to 350 ℃.
7. A molding composition of the semiaromatic polyamide according to claim 6, characterized in that: the material comprises the following raw materials in parts by weight:
30-100 parts of semi-aromatic polyamide,
0-70 parts of reinforcing material,
0-70 parts of inorganic filler,
0-60 parts of additive;
the additives include one or more of antioxidants, flame retardants, lubricants, mold release agents, nucleating agents, colorants, plasticizers, toughening agents, antistatic agents, solubilizing agents, dispersants, stabilizers, flow modifiers, or other polymeric resins.
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