CN112759923A - Glass fiber reinforced semi-aromatic polyamide molding composition with specific glass fiber length and molded product - Google Patents
Glass fiber reinforced semi-aromatic polyamide molding composition with specific glass fiber length and molded product Download PDFInfo
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- CN112759923A CN112759923A CN202011568037.6A CN202011568037A CN112759923A CN 112759923 A CN112759923 A CN 112759923A CN 202011568037 A CN202011568037 A CN 202011568037A CN 112759923 A CN112759923 A CN 112759923A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- 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
Abstract
The invention discloses a glass fiber reinforced semi-aromatic polyamide molding composition with specific glass fiber length and a molding product, wherein the glass fiber reinforced semi-aromatic polyamide molding composition with specific glass fiber length comprises the following components in parts by weight: (A)25 to 90 parts of at least one semi-aromatic polyamide resin, (B)5 to 70 parts of glass fibers having an arithmetic mean length of 200 to 450 μm, (C)0 to 2 parts of an additive. The glass fiber-reinforced semi-aromatic polyamide molding composition having a specific glass fiber length of the present invention achieves a balance of water absorption properties and flowability as compared with molding compositions having a glass fiber length other than an arithmetic mean length of 230 μm to 400 μm, so that moldings made from the molding composition of the present invention can be used for sliding parts and engine peripheral parts.
Description
Technical Field
The invention relates to a shooting polymer blend modification, to a glass fiber-reinforced polyamide molding composition, and also to the use of this composition.
Background
The polyamide has good comprehensive properties including mechanical property, heat resistance, abrasion resistance, chemical resistance and self-lubricity, low friction coefficient, certain flame retardance, easy processing and the like, and is widely suitable for being filled, reinforced and modified by glass fibers and other fillers, so that the performance is improved and the application range is expanded. Semi-aromatic polyamides have been developed in recent years with great emphasis on their superior heat resistance and mechanical properties.
The high-temperature resistant nylon has good wear resistance, heat resistance, oil resistance and chemical resistance, greatly reduces the water absorption rate and shrinkage rate of raw materials, has excellent dimensional stability and mechanical strength, can bear high strength and high load, resists high temperature and works in severe environment, is particularly suitable for being used as sliding parts such as manufacturing transmission parts such as gears, turbines and cams, as well as wear-resistant and antifriction parts such as bearings, bushes, guide rails and pistons, general structural parts and related functional parts of an engine area, and is an excellent polymer material for replacing metal materials around automobile engines. The above application areas often require the achievement of high performance under various severe working conditions by the introduction of glass fiber reinforcement.
CN104046000A discloses an alkali-free chopped glass fiber reinforced 6T/610 material, and compared with a glass fiber reinforced material, the tensile strength, impact strength, bending strength, heat distortion temperature and the like of the alkali-free chopped glass fiber reinforced 6T/610 material are all obviously and greatly improved.
CN104210113A discloses a high-performance long glass fiber reinforced nylon 10T composite material and a preparation method thereof, which can improve the strength and rigidity of the glass fiber reinforced nylon 10T composite material, greatly improve the toughness thereof, improve the processing performance thereof and expand the applicable processing mode thereof. Because the long glass fiber is used, the common double-screw extruder is difficult to be applied, and a long glass fiber special device is required to be used, so that the cost is higher; the adding amount of the glass fiber can not be conveniently controlled, and the glass fiber is not beneficial to uniformly dispersing in the nylon.
CN104284771 discloses an engine cover made of glass fiber reinforced material derived from PA4T, which has good sealing performance in a wide temperature range and a wide pressure range, and the sealing function of the engine cover can be maintained in a long service life when the engine cover is in contact with various fluids.
CN105017763A discloses a rare earth modified glass fiber reinforced high-temperature resistant nylon composite material, and the obtained composite material has better mechanical and wear-resisting properties compared with glass fiber reinforced high-temperature resistant nylon which is not subjected to rare earth surface treatment. However, the preparation method of the rare earth modified glass fiber is complicated, and the preparation process needs organic solvents such as ethanol and the like, so that the preparation method does not meet the requirements of environmental protection.
CN108165003A discloses a high-glass-fiber-content reinforced high-temperature nylon composite material and a preparation method thereof, and compared with a low-glass-fiber-content reinforced high-temperature nylon composite material, the material has greatly improved properties such as tensile strength, tensile modulus, impact strength and the like.
However, the above prior arts have focused on the influence of polyamide matrix resin, glass fiber content and surface treatment, additive composition, etc. on the material performance, and neglect the influence of glass fiber length on the material.
Disclosure of Invention
The invention aims to provide a glass fiber reinforced semi-aromatic polyamide molding composition with specific glass fiber length, a glass fiber reinforced semi-aromatic polyamide molding product with specific glass fiber length and a preparation method of the glass fiber reinforced semi-aromatic polyamide molding composition. The glass fiber reinforced semi-aromatic polyamide molding composition having a specific glass fiber length of the present invention achieves a balance of water absorption properties and flowability as compared to molding compositions having glass fibers having a length other than an arithmetic average length of 230 to 400 μm.
1. The glass fiber reinforced semi-aromatic polyamide molding composition with specific glass fiber length is characterized by comprising the following components in parts by weight:
(A)25 to 90 parts of at least one semi-aromatic polyamide resin;
(B)5 to 70 parts of glass fibers having an arithmetic mean length of 200 to 450 μm;
(C)0 to 2 parts of an additive.
Preferably, the glass fibers have an arithmetic mean length of 230 to 400 μm.
For the purposes of the present invention, the expression "average length" used for the glass fibers means the average length according to ISO 22314: a part of 2006(E) determined average length (arithmetic mean) with the tolerances mentioned in the description about the standard. Thus, according to the method described in this detailed description, the arithmetic mean length of the glass fiber lengths in the molding composition is determined by starting from a sample of the glass fiber reinforced semi-aromatic polyamide molding composition having a specific glass fiber length. Here, this value is the average length of the glass fibers present in the glass fiber reinforced semi-aromatic polyamide molding composition having a specific glass fiber length, not necessarily the average length of the glass fiber starting material. That is, one of the other aspects essential to the invention is that such molding compositions can also be produced by starting from the initially longer glass fibers; the processing method, in particular the extrusion method, is adjusted in such a way that in the resulting glass fiber-reinforced semi-aromatic polyamide molding composition having a specific glass fiber length and in the polymer moldings produced therefrom, the average fiber length is respectively from 200 μm to 450 μm of the protection required, in particular the average fiber length is respectively from 200 μm to 500 μm of the protection to be protected.
Preferably, the semi-aromatic polyamide resin comprises the following repeating units and derivatives derived from the following repeating units:
(i) terephthalic acid or a derivative thereof, and optionally one or more aromatic or aliphatic diacids or derivatives thereof other than terephthalic acid;
(ii) one or more aliphatic diamines having from 4 to 20 carbon atoms, and/or optionally one or more additional diamines;
(iii) and optionally one or more aminocarboxylic acids and/or lactams;
wherein terephthalic acid or a derivative thereof is present in an amount of 40 to 100 mole percent of (i), one or more aliphatic diamines having 4 to 20 carbon atoms are present in an amount of 40 to 100 mole percent of (ii), and one or more aminocarboxylic acids or lactams are present in an amount of 0 to 25 mole percent of the total amount of (i) + (ii) + (iii), the mole percentages of component (i) and component (ii) being equal, and the sum of component (i) and component (ii) being present in an amount of 0 to 25 mole percent of the total amount of (i) + (ii) + (iii).
Further, the aliphatic diamine having 4 to 20 carbon atoms is at least one selected from straight-chain aliphatic diamines such as 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, 14-tetradecanediamine, 1, 16-hexadecanediamine, 1, 18-octadecanediamine and the like, and/or 1-butyl-1, 2-ethylenediamine, 1-dimethyl-1, 4-butanediamine, 1-ethyl-1, 4-butanediamine, 1, 2-dimethyl-1, 4-butanediamine, 1, 3-dimethyl-1, 4-butanediamine, 1, 4-dimethyl-1, 4-butanediamine, 2, 3-dimethyl-1, 4-butanediamine, 2-methyl-1, 5-pentanediamine, 3-methyl-1, 5-pentanediamine, 2, 5-dimethyl-1, 6-hexanediamine, 2, 4-dimethyl-1, 6-hexanediamine, 3-dimethyl-1, 6-hexanediamine, 2, 4-trimethyl-1, 6-hexanediamine, 2, 4-diethyl-1, 6-hexanediamine, hexane diamine, hexane, 2, 2-dimethyl-1, 7-heptanediamine, 2, 3-dimethyl-1, 7-heptanediamine, 2, 4-dimethyl-1, 7-heptanediamine, 2, 5-dimethyl-1, 7-heptanediamine, 2-methyl-1, 8-octanediamine, 3-methyl-1, 8-octanediamine, 4-methyl-1, 8-octanediamine, 1, 3-dimethyl-1, 8-octanediamine, 1, 4-dimethyl-1, 8-octanediamine, 2, 4-dimethyl-1, 8-octanediamine, 3, 4-dimethyl-1, 8-octanediamine, 4, 5-dimethyl-1, 8-octanediamine, 2, at least one branched aliphatic diamine such as 2-dimethyl-1, 8-octanediamine, 3-dimethyl-1, 8-octanediamine, 4-dimethyl-1, 8-octanediamine, 5-methyl-1, 9-nonanediamine, etc.
Preferably, the diamine is one or the combination of any two selected from 1, 6-hexamethylene diamine, 1, 10-decamethylene diamine and 1, 12-dodecane diamine.
The amount of the semi-aromatic polyamide (a) present in the composition of the invention is from 25 to 90 parts, preferably from 35 to 80 parts, and particularly preferably from 45 to 75 parts.
The glass fibers (B) have a circular and/or non-circular cross section, wherein in the case of flat glass fibers the dimensional ratio of the large cross-sectional axis to the small cross-sectional axis is in particular > 2: 1, preferably 2: 1 to 5: 1, and particularly preferably 3: 1 to 4.5: 1. In a preferred embodiment, the cross-section of the glass fiber is only circular.
For the reinforcement of the molding compositions according to the invention, it is also possible to use mixtures of the glass fibers (B) having a circular and a non-circular cross section, the content of the glass fibers having a circular cross section preferably representing more than 50% by weight of the total composition of the glass fibers.
Irrespective of the cross-sectional shape and the fiber length, the glass fibers (B) themselves may be selected from E glass fibers, a glass fibers, C glass fibers, D glass fibers, M glass fibers, S glass fibers or R glass fibers, preferably E glass fibers, R glass fibers or S glass fibers.
In order to obtain more excellent mechanical properties of the glass fiber reinforced semi-aromatic polyamide molding composition having a specific glass fiber length, the glass fibers (B) may be functionally treated with a coupling agent.
Wherein the coupling agent includes but is not limited to isocyanate compound, organic silane compound, organic titanate compound, organic borane compound, epoxy compound; preferably an organic silane compound;
wherein the organic silane compound includes, but is not limited to, one or more of an epoxy group-containing alkoxysilane compound, a mercapto group-containing alkoxysilane compound, a urea group-containing alkoxysilane compound, an isocyanate group-containing alkoxysilane compound, an amine 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 comprises one or more of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane and beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane;
the mercapto group-containing alkoxysilane compound includes, but is not limited to, gamma-mercaptopropyltrimethoxysilane and/or gamma-mercaptopropyltriethoxysilane;
the ureido-containing alkoxy silane compound comprises one or more of gamma-ureidopropyltriethoxysilane, gamma-ureidopropyltrimethoxysilane and gamma- (2-ureidoethyl) amino-terminated propyltrimethoxysilane;
the alkoxy silane compound containing the isocyanate group comprises one or more of gamma-isocyanatopropyl triethoxysilane, gamma-isocyanatopropyl trimethoxysilane, gamma-isocyanatopropyl methyldimethoxysilane, gamma-isocyanatopropyl methyldiethoxysilane, gamma-isocyanatopropyl ethyldimethoxysilane, gamma-isocyanatopropyl ethyldiethoxysilane and gamma-isocyanatopropyl trichlorosilane;
the alkoxy silane compound containing terminal amino comprises one or more of gamma- (2-terminal amino ethyl) terminal amino propyl methyl dimethoxy silane, gamma- (2-terminal amino ethyl) terminal amino propyl trimethoxy silane and gamma-terminal amino propyl trimethoxy silane;
the hydroxyl group-containing alkoxysilane compound includes, but is not limited to, gamma-hydroxypropyltrimethoxysilane and/or gamma-hydroxypropyltriethoxysilane;
the alkoxy silane compound containing the carbon-carbon unsaturated group comprises one or more of gamma-methacryloxypropyltrimethoxysilane, vinyl trimethoxysilane and N-beta- (N-vinyl benzyl terminal aminoethyl) -gamma-terminal aminopropyltrimethoxysilane hydrochloride;
the alkoxysilane compound having an acid anhydride group includes, but is not limited to, 3-trimethoxysilylpropyl succinic anhydride;
the organic silane compound is preferably gamma-methacryloxypropyltrimethoxysilane, gamma- (2-terminal aminoethyl) terminal aminopropylmethyldimethoxysilane, gamma- (2-terminal aminoethyl) terminal aminopropyltrimethoxysilane, gamma-terminal aminopropyltrimethoxysilane or 3-trimethoxysilylpropyl succinic anhydride.
The glass fiber-reinforced semi-aromatic polyamide molding composition having a specific glass fiber length may be prepared by subjecting the glass fiber (B) to a surface treatment with the organic silane-based compound according to a conventional method and then melt-kneading the same with the semi-aromatic polyamide resin.
The organic silane compound may be added to the glass fiber (B) and the semi-aromatic polyamide resin directly at the same time of melt-kneading, and the mixture may be blended in situ.
The additive (C) comprises one or more of an impact modifier, other polymers and processing aids.
The stabilizer used in the present embodiment includes, but is not limited to, at least one of a phenol stabilizer, a phosphite stabilizer, a hindered amine stabilizer, a triazine stabilizer, a sulfur-containing stabilizer, and an inorganic phosphorus-containing stabilizer.
One or more of the stabilizers may be used in combination.
The phenolic stabilizer is not particularly limited, and examples thereof include: a hindered phenolic compound.
Examples of the hindered phenol compound include: n, 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-hydroxyhydrocinnamamide), 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, a salt thereof, a hydrate thereof, a salt thereof, and a pharmaceutically acceptable salt thereof, Diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, and 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanuric acid, and the like. These may be used alone or in combination of two or more.
When the phenolic heat stabilizer is used, the content of the phenolic heat stabilizer in the glass fiber reinforced semi-aromatic polyamide molding composition with the specific glass fiber length is preferably 0.01 to 1 part by weight, and more preferably 0.1 to 1 part by weight, relative to 100 parts by weight of the glass fiber reinforced semi-aromatic polyamide molding composition with the specific glass fiber length. When the content of the phenolic heat stabilizer is within the above range, the heat aging resistance of the glass fiber-reinforced semi-aromatic polyamide molding composition having a specific glass fiber length can be further improved, and the amount of gas generation can be further reduced.
The phosphite-based stabilizer is not particularly limited, and examples thereof include: trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, diphenyloctyl phosphite, triisodecyl phosphite, diisodecyl monobenzene phosphite, ditridecyl phosphite, diisooctyl diphenyl phosphite, diisodecyl diphenyl phosphite, ditridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tris (2, 4-di-tert-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4 '-butylidene-bis (3-methyl-6-tert-butylphenyl tetra (tridecyl)) diphosphite, tetrakis (C12-C15 mixed alkyl) -4, 4' -isopropylidene diphenyl diphosphite, 4,4 '-isopropylidenebis (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' -butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetrakis (C1-C15 mixed alkyl) -4, 4 '-isopropylidenediphenyl diphosphite, tris (mono-, di-mixed nonylphenyl) phosphite, 4' -isopropylidenebis (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-ethylhexyl phosphite, 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.
The phosphite stabilizer may be used alone or in combination of two or more.
The phosphite stabilizer may be a pentaerythritol phosphite compound.
The pentaerythritol-type phosphite compound may be exemplified by: 2, 6-di-tert-butyl-4-methylphenylphenylpentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenylmethylpentaerythritol diphosphite, 2, 6-di-tert-butyl-4-methylphenyl2-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-, 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, 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-pentyl-4-methylphenyl pentaerythritol diphosphite, bis (2, 6-di-tert-pentyl-4-methylphenyl) pentaerythritol diphosphite and bis (2, 6-di-tert-pentyl-4-methylphenyl) pentaerythritol diphosphite 2, 6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite, and the like.
The pentaerythritol type phosphite ester stabilizer can be used in one kind, and can also be used in combination of two or more kinds.
The pentaerythritol-type phosphite compound is preferably 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 or the like, and more preferably bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite.
The hindered amine-based stabilizer is not particularly limited, and examples thereof include: 4-acetoxy-2, 2,6, 6-tetramethylpiperidine, 4-stearoyloxy-2, 2,6, 6-tetramethylpiperidine, 4-acryloyloxy-2, 2,6, 6-tetramethylpiperidine, 4- (phenylacetoxy) -2, 2,6, 6-tetramethylpiperidine, 4-benzoyloxy-2, 2,6, 6-tetramethylpiperidine, 4-methoxy-2, 2,6, 6-tetramethylpiperidine, 4-stearyloxy-2, 2,6, 6-tetramethylpiperidine, 4-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidine, 4-benzyloxy-2, 2,6, 6-tetramethylpiperidine, 4-phenoxy-2, 2,6, 6-tetramethylpiperidine, 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, 1, 2-bis (2, 2,6, 6-tetramethyl-4-piperidyloxy) -ethane, α' -bis (2, 2,6, 6-tetramethyl-4-piperidyloxy) p-xylene, bis (2, 2,6, 6-tetramethyl-4-piperidyl) -toluene-2, 4-dicarbamate, bis (2, 2,6, 6-tetramethyl-4-piperidyl) -hexamethylene-1, 6-dicarbamate, tris (2, 2,6, 6-tetramethyl-4-piperidyl) -benzene-1, 3, 5-tricarbamate, tris (2, 2,6, 6-tetramethyl-4-piperidyl) -benzene-1, 3, 4-tricarboxylate, 1- [2- {3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy } butyl ] -4- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ] -2, 2,6, 6-tetramethylpiperidine, and condensates of 1,2, 3, 4-butanetetracarboxylic acid, 1,2, 2,6, 6-pentamethyl-4-piperidinol and β, β, β ', β' -tetramethyl-3, 9- [2, 4,8, 10-tetraoxaspiro (5.5) undecane ] diethanol, and the like.
One or more of the hindered amine stabilizers may be used.
The triazine-based stabilizer is not particularly limited, and examples thereof include: hydroxyphenyl triazines, and the like.
Examples of the hydroxyphenyl triazine include: 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 ' -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 and 2,4, 6-tris (2 '-hydroxy-4' -ethoxycarbonylmethoxyphenyl) -1, 3, 5-triazine, and the like.
One or more triazine-based stabilizers may be used in combination.
The sulfur-containing stabilizer is not particularly limited, and examples thereof include: pentaerythritol tetrakis (3-laurylthiopropionate), dilauryl 3,3 ' -thiodipropionate, dimyristyl 3,3 ' -thiodipropionate, distearyl 3,3 ' -thiodipropionate, and the like.
The sulfur-containing stabilizer may be used alone or in combination of two or more.
The inorganic phosphorus-containing stabilizer may be, for example, a hydrate thereof (preferably, a hydrate of sodium hypophosphite (NaH)2PO2·nH2O))。
The inorganic phosphorus-containing stabilizer may be used alone or in combination of two or more.
Wherein the impact modifier may be natural rubber, polybutadiene, polyisoprene, polyisobutylene, copolymers of butadiene and/or isoprene with styrene or with styrene derivatives and with other comonomers, hydrogenated copolymers, and/or copolymers obtained by grafting, or copolymers obtained by copolymerization with anhydrides, (meth) acrylic acid or esters thereof; the impact modifier may also 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 copolymerization with an anhydride, (meth) acrylic acid or an ester thereof; the impact modifier may also be a carboxylic acid functionalized copolymer, such as a poly (ethylene-co- (meth) acrylic acid) or a poly (ethylene-1-olefin-co- (meth) acrylic acid), wherein the 1-olefin is an alkene or an unsaturated (meth) acrylate having more than 4 atoms.
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. The block copolymer comprises at least one block a derived from an alkenyl aromatic compound and at least one block b derived from a conjugated diene. In the case of hydrogenated block copolymers, the proportion of aliphatic unsaturated carbon-carbon double bonds is reduced by hydrogenation. Suitable block copolymers are di-, tri-, tetra-and multiblock copolymers having a linear structure. However, branched and star structures may also be used according to the invention. Branched block copolymers are obtained in a known manner, for example by grafting of polymer "side branches" to the polymer backbone.
Other alkenyl aromatic compounds which may be used together with styrene or in the form of mixtures with styrene are vinyl aromatic monomers which are substituted on the aromatic ring and/or on the C ═ C double bond by C1-20 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, chlorostyrene, and combinations thereof. Styrene, p-methylstyrene, alpha-methylstyrene, and vinylnaphthalene are preferred.
Styrene, alpha-methylstyrene, p-methylstyrene, ethylstyrene, tert-butylstyrene, vinyltoluene, 1, 2-diphenylethylene, 1-diphenylethylene or mixtures of these substances are preferably used. It is particularly preferred to use styrene. Also, alkenylnaphthalenes may be used.
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, especially 1, 3-butadiene (hereinafter referred to as butadiene in abbreviated form), are preferred.
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. The block copolymers are generally prepared by anionic polymerization in a manner known per se.
In addition to the styrene monomer and the diene monomer, other additional monomers may also be used simultaneously. The proportion of comonomers, based on the total amount of alkenyl aromatic monomers used, is preferably from 0 to 50% by weight, particularly preferably from 0 to 30% by weight, and particularly preferably from 0 to 15% by weight. Examples of suitable comonomers are acrylates, in particular C1-C12 alkyl acrylates, for example n-butyl acrylate or 2-ethylhexyl acrylate, and methacrylates, in particular C1-C12 alkyl methacrylates, for example Methyl Methacrylate (MMA). Other possible comonomers are (meth) acrylonitrile, glycidyl (meth) acrylate, vinyl methyl ether, diallyl and divinyl ethers of dihydric alcohols, divinyl benzene and vinyl acetate.
In addition to the conjugated diene, the hydrogenated block copolymer also contains a lower hydrocarbon moiety, such as ethylene, propylene, 1-butene, dicyclopentadiene, or a non-conjugated diene. The proportion of unreduced aliphatic unsaturation originating from block b in the hydrogenated block copolymer is less than 50%, preferably less than 25%, more preferably less than 10%. The aromatic moieties derived from block a are reduced to a degree of up to 25%. Hydrogenated block copolymers, i.e., styrene- (ethylene-butylene) diblock copolymers and styrene- (ethylene-butylene) -styrene triblock copolymers, were obtained by hydrogenation of styrene-butadiene copolymers and hydrogenation of styrene-butadiene-styrene copolymers.
The block copolymers have a molar mass of from 5000g/mol to 500000g/mol, preferably from 20000g/mol to 300000g/mol, in particular from 40000g/mol to 200000 g/mol.
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-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 any combination of the foregoing.
Suitable non-hydrogenated block copolymers are commercially available under the trade names (Phillips), (Shell), (Dexco) and (Kuraray).
The polyamide composition of the present invention comprising the above polyamide resin, the additive component may further comprise other polymers including, but not limited to, aliphatic polyamide, amorphous polyamide, polyolefin homopolymer or ethylene- α -olefin copolymer, ethylene-acrylate copolymer.
The aliphatic polyamide comprises but is not limited to 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), polycaprolactam (PA6), polyhexamethylene sebacamide (PA610), polyhexamethylene sebacamide (PA1010), adipic acid-hexamethylenediamine-caprolactam copolymer (PA66/6), polyundecanolactam (PA11), polydodecanolactam (PA12), and mixtures of two or more of the foregoing.
The amorphous polyamide includes, but is not limited to, a polycondensate of isophthalic acid/terephthalic acid/1, 6-hexamethylenediamine/bis (3-methyl-4-aminocyclohexyl) methane, a polycondensate of terephthalic acid/2, 2, 4-trimethyl-1, 6-hexamethylenediamine/2, 4, 4-trimethyl-1, 6-hexamethylenediamine, a polycondensate of isophthalic acid/bis (3-methyl-4-aminocyclohexyl) methane/ω -dodecalactam, a polycondensate of isophthalic acid/terephthalic acid/1, 6-hexamethylenediamine, isophthalic acid/2, 2, 4-trimethyl-1, 6-hexamethylenediamine/2, 4, 4-trimethyl-1, 6-hexamethylenediamine polycondensate, isophthalic acid/terephthalic acid/2, 2, 4-trimethyl-1, 6-hexamethylenediamine/2, 4, 4-trimethyl-1, 6-hexamethylenediamine polycondensate, isophthalic acid/terephthalic acid/other diamine component polycondensate. By adding the amorphous polyamide, the surface gloss and the like can be improved.
Examples of the (co) polymer include a vinyl copolymer, a conjugated diene polymer, and a conjugated diene-aromatic vinyl hydrocarbon copolymer. The ethylene copolymer herein refers to a copolymer or a multipolymer of ethylene and another monomer. The other monomer to be copolymerized with ethylene may be selected from α -olefins having 3 or more carbon atoms, non-conjugated dienes, vinyl acetate, vinyl alcohol, α, β -unsaturated carboxylic acids and derivatives thereof, and the like.
The above-mentioned alpha-olefin having 3 or more carbon atoms includes propylene, butene-1, pentene-1, 3-methylpentene-1, octene-1 and the like, and propylene and butene-1 can be preferably used. Examples of the non-conjugated diene include norbornene compounds such as 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-crotyl-2-norbornene, 5- (2-methyl-2-butenyl) -2-norbornene, 5- (2-ethyl-2-butenyl) -2-norbornene and 5-methyl-5-vinylnorbornene; dicyclopentadiene, methyltetrahydroindene, 4,7,8, 9-tetrahydroindene, 1, 5-cyclooctadiene, 1, 4-hexadiene, isoprene, 6-methyl-1, 5-heptadiene, 11-tridecadiene, and the like. Preferred examples thereof include 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene and 1, 4-hexadiene. Examples of the α, β -unsaturated carboxylic acid include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and butenedicarboxylic acid, and derivatives thereof, such as alkyl esters, aryl esters, glycidyl esters, acid anhydrides, and imides, which are formed by the reaction of the above compounds.
The conjugated diene polymer is a polymer containing at least 1 or more kinds of conjugated dienes as a constituent component, and examples thereof include a homopolymer such as 1, 3-butadiene, and a copolymer of 1 or more kinds of monomers selected from 1, 3-butadiene, isoprene (2-methyl-1, 3-butadiene), 2, 3-dimethyl-1, 3-butadiene, and 1, 3-pentadiene. It is also preferable to use a substance in which a part or all of unsaturated bonds of these polymers are reduced by hydrogenation.
The conjugated diene-aromatic vinyl hydrocarbon copolymer is a block copolymer or a random copolymer comprising a conjugated diene and an aromatic vinyl hydrocarbon. Examples of the conjugated diene constituting the conjugated diene-aromatic vinyl hydrocarbon copolymer include the above-mentioned monomers, and 1, 3-butadiene and isoprene are particularly preferable. Examples of the aromatic vinyl hydrocarbon include styrene, α -methylstyrene, o-methylstyrene, p-methylstyrene, 1, 3-dimethylstyrene, vinylnaphthalene, and the like, and among them, styrene can be preferably used. In addition, as the conjugated diene-aromatic vinyl hydrocarbon copolymer, it is also possible to preferably use one in which a part or all of unsaturated bonds other than double bonds of aromatic rings of the conjugated diene-aromatic vinyl hydrocarbon copolymer are reduced by hydrogenation.
The granule modifier can also be used in combination of more than 2 kinds.
Specific examples of the agent for modifying the impact modifier of the (co) polymer include ethylene/propylene copolymer, ethylene/butene-1 copolymer, ethylene/hexene-1 copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene/5-ethylidene-2-norbornene copolymer, unhydrogenated or hydrogenated styrene/isoprene/styrene triblock copolymer, unhydrogenated or hydrogenated styrene/butadiene/styrene triblock copolymer, ethylene/methacrylic acid copolymer, and a material obtained by salt-forming a part or all of the carboxylic acid moiety in these copolymers with sodium, lithium, potassium, zinc or calcium, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/methyl methacrylate copolymer, ethylene/butene-1 copolymer, ethylene/hexene-1 copolymer, ethylene/propylene/5-ethylidene-2-norbornene copolymer, unhydrogenated or hydrogenated styrene/isoprene/, Ethylene/ethyl methacrylate copolymer, ethylene/ethyl acrylate-g-maleic anhydride copolymer ("g" means graft, the same applies hereinafter), ethylene/methyl methacrylate-g-maleic anhydride copolymer, ethylene/ethyl acrylate-g-maleimide copolymer, ethylene/ethyl acrylate-g-N-phenylmaleimide copolymer and partially saponified products of these copolymers, ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, ethylene/methyl methacrylate/glycidyl methacrylate copolymer, ethylene/glycidyl acrylate copolymer, ethylene/vinyl acetate/glycidyl acrylate copolymer, ethylene/methyl methacrylate/glycidyl methacrylate copolymer, ethylene/vinyl acetate/acrylic acid copolymer, ethylene/methyl methacrylate copolymer, ethylene/vinyl acetate/acrylic acid copolymer, ethylene/vinyl acetate/glycidyl acrylate copolymer, ethylene/vinyl acetate/acrylic acid copolymer, ethylene, Ethylene/glycidyl ether copolymer, ethylene/propylene-g-maleic anhydride copolymer, ethylene/butene-1-g-maleic anhydride copolymer, ethylene/propylene/1, 4-hexadiene-g-maleic anhydride copolymer, ethylene/propylene/dicyclopentadiene-g-maleic anhydride copolymer, ethylene/propylene/2, 5-norbornadiene-g-maleic anhydride copolymer, ethylene/propylene-g-N-phenylmaleimide copolymer, ethylene/butene-1-g-N-phenylmaleimide copolymer, hydrogenated styrene/butadiene/styrene-g-maleic anhydride copolymer, hydrogenated styrene/isoprene/styrene-g-maleic anhydride copolymer, ethylene/propylene-g-glycidyl methacrylate copolymer, ethylene/propylene-g-maleic anhydride copolymer, ethylene/propylene-b-isoprene/styrene-g-maleic anhydride copolymer, ethylene/propylene-b-isoprene/, Ethylene/butene-1-g-glycidyl methacrylate copolymer, ethylene/propylene/1, 4-hexadiene-g-glycidyl methacrylate copolymer, ethylene/propylene/dicyclopentadiene-g-glycidyl methacrylate copolymer, hydrogenated styrene/butadiene/styrene-g-glycidyl methacrylate copolymer, nylon 12/polybutylene glycol copolymer, nylon 12/polypropylene glycol copolymer, polybutylene terephthalate/polybutylene glycol copolymer, polybutylene terephthalate/polypropylene glycol copolymer and the like. Among them, ethylene/methacrylic acid copolymers and materials obtained by salt-forming part or all of carboxylic acid moieties in these copolymers with sodium, lithium, potassium, zinc, calcium, ethylene/propylene-g-maleic anhydride copolymers, ethylene/butene-1-g-maleic anhydride copolymers, and hydrogenated styrene/butadiene/styrene-g-maleic anhydride copolymers are more preferable. Among these, ethylene/methacrylic acid copolymers and materials obtained by salt-forming part or all of the carboxylic acid moieties in these copolymers with sodium, lithium, potassium, zinc, calcium, ethylene/propylene-g-maleic anhydride copolymers and ethylene/butene-1-g-maleic anhydride copolymers are particularly preferable. Preferably, the other polymer comprises a component having anhydride groups, these being reacted by thermal or free radical reaction of the backbone polymer with an unsaturated dianhydride, with an unsaturated dicarboxylic acid, or with a monoalkyl ester of an unsaturated dicarboxylic acid, the ester being present in excess to ensure that the reaction is complete and that a polyamide of the appropriate concentration is produced.
Examples of the polymer containing an α, β -unsaturated dicarboxylic acid anhydride include: polymers containing an α, β unsaturated dicarboxylic acid anhydride as a copolymerization component, polymers modified with an α, β unsaturated dicarboxylic acid anhydride, and the like.
The α, β unsaturated dicarboxylic acid anhydride includes, for example: a compound represented by the following formula I.
In the formula I, R1 and R2 are respectively and independently hydrogen or alkyl with 1-3 carbon atoms.
Examples of the α, β unsaturated dicarboxylic acid anhydride include maleic anhydride and methyl maleic anhydride, and maleic anhydride is preferable.
The polymer containing an α, β -unsaturated dicarboxylic acid anhydride as a copolymerization component includes, for example: copolymers of aromatic vinyl compounds and α, β unsaturated dicarboxylic acid anhydrides, and the like.
The polymers modified with α, β unsaturated dicarboxylic acid anhydrides include, for example: polyphenylene ether resins or polypropylene resins modified with α, β unsaturated dicarboxylic acid anhydrides.
The polymer containing an α, β -unsaturated dicarboxylic acid anhydride is preferably a copolymer of an aromatic vinyl compound and an α, β -unsaturated dicarboxylic acid anhydride.
Examples of the aromatic vinyl compound used in the present embodiment include compounds represented by the following formula II.
In the formula II, R3 and R4 are each independently hydrogen or alkyl having 1 to 3 carbon atoms, and k is an integer of 1 to 5.
Examples of the aromatic vinyl compound include: styrene, α -methylstyrene, p-methylstyrene, etc., with styrene being preferred.
The proportions of the aromatic vinyl compound component and the α, β unsaturated dicarboxylic acid anhydride component in the copolymer of the aromatic vinyl compound and the α, β unsaturated dicarboxylic acid anhydride are preferably 50 to 99 wt% of the aromatic vinyl compound component and 1 to 50 wt% of the α, β unsaturated dicarboxylic acid anhydride component, from the viewpoint of fluidity, thermal decomposition resistance, and the like. More preferably, the proportion of the α, β unsaturated dicarboxylic acid anhydride component is 5 wt% to 20 wt%, still more preferably 8 wt% to 15 wt%.
By setting the proportion of the α, β unsaturated dicarboxylic acid anhydride component to 1 wt% or more, a polyamide composition excellent in mechanical properties such as toughness and rigidity can be obtained. Further, by setting the proportion of the α, β -unsaturated dicarboxylic acid anhydride component to 50 wt% or less, deterioration of the polyamide composition due to the α, β -unsaturated dicarboxylic acid anhydride can be prevented.
Further, the additive component may comprise a component having functional groups such as carboxylic acid groups, ester groups, epoxy groups, oxazoline groups, carbodiimide groups, isocyanate groups, silanol groups, and carboxylate groups, or the additive component may comprise a combination of two or more of the foregoing functional groups. The monomers having said functional groups may be incorporated by copolymerization or grafting onto the elastomeric polyolefin.
Further, the impact modifier based on an olefin polymer may also be modified by grafting with an unsaturated silane compound such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetylsilane, methacryloxypropyltrimethoxysilane, or propenyl trimethoxysilane.
The elastomeric polyolefins are random, alternating or block copolymers having a linear, branched or core-shell structure and contain functional groups that can react with the end groups of the polyamide, thereby providing sufficient compatibility between the polyamide and the impact modifier.
Thus, the impact modifier of the invention includes homopolymers or copolymers of olefins (e.g., ethylene, propylene, 1-butene), or copolymers of olefins and copolymerizable monomers (e.g., vinyl acetate, (meth) acrylates, and methylhexadiene).
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 polymers.
Examples of commercially available impact modifiers that can be used in the additive component are:
TAFMERMC 201: g-MA (-0.6%) blend of 67% EP copolymer (20 mol% propylene) + 33% EB copolymer (15 mol% 1-butene)): mitsui chemicals, japan.
TAFMERMH 5010: g-MA (-0.6%) ethylene-butene copolymer; mitsui.
TAFMERMH 7010: g-MA (-0.7%) ethylene-butene copolymer; mitsui.
TAFMERMH 7020: g-MA (-0.7%) EP copolymer; mitsui.
EXXELORVA 1801: g-MA (-0.7%) EP copolymer; ExxonMobileChemicals, US.
EXXELORVA 1803: g-MA (0.5-0.9%) EP copolymer, amorphous, Exxon.
Exxelova 1810: g-MA (-0.5%) EP copolymer, Exxon.
EXXELORMDEX941l：g-MA(0.7％)EPDM，Exxon。
Fusebondmn 493D: g-MA (-0.5%) ethylene-octene copolymer, DuPont, US.
Fusabondeab 560D: (g-MA) ethylene-n-butyl acrylate copolymer, DuPont ELVALOY, DuPont.
Also preferred are ionic polymers in which the polymer-bound carboxyl groups are all bound to each other or to some extent by metal ions.
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.
The amount of the additive (C) present in the composition of the invention is preferably from 0.001 to 18 parts, particularly preferably from 0.01 to 10 parts, and particularly preferably from 0.1 to 5 parts.
The invention also provides a sliding part and an engine peripheral part which are made of the glass fiber reinforced semi-aromatic polyamide molding composition with the specific glass fiber length. The components are used in the electrical/electronic industry, in particular in the form of large-surface-area components for components of circuit boards, housings, foils, wires, switches, distributors, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, connectors, controllers, storage devices and sensors, in particular in the form of components of complex design with a fine structure for housing components of switch cabinets.
Has the advantages that:
the glass fiber reinforced semi-aromatic polyamide molding composition with the specific glass fiber length is added with the glass fiber with the arithmetic mean length of 200-450 mu m to form the blocking effect on water molecules, so that the composition product has higher fusing index and good water absorption and dimensional stability.
The invention also provides a sliding part and an engine peripheral part which are made of the glass fiber reinforced semi-aromatic polyamide molding composition with the specific glass fiber length, and the parts have good water absorption and dimensional stability.
Detailed Description
Various embodiments of the present disclosure will be described more fully hereinafter. The present disclosure is capable of various embodiments and of modifications and variations therein. However, it should be understood that: there is no intention to limit the various embodiments of the disclosure to the specific embodiments disclosed herein, but rather, the disclosure is to cover all modifications, equivalents, and/or alternatives falling within the spirit and scope of the various embodiments of the disclosure.
Hereinafter, the terms "includes" or "may include" used in various embodiments of the present disclosure indicate the presence of the disclosed functions, operations, or elements, and do not limit the addition of one or more functions, operations, or elements. Furthermore, as used in various embodiments of the present disclosure, the terms "comprising," "having," and their derivatives, are intended to be only representative of the particular feature, number, step, operation, element, component, or combination of the foregoing, and should not be construed as first excluding the possibility of one or more other features, numbers, steps, operations, elements, components, or combinations of the foregoing, or adding one or more features, numbers, steps, operations, elements, components, or combinations of the foregoing.
In various embodiments of the disclosure, the expression "or" at least one of a or/and B "includes any or all combinations of the words listed simultaneously. For example, the expression "a or B" or "at least one of a or/and B" may include a, may include B, or may include both a and B.
Expressions (such as "first", "second", and the like) used in various embodiments of the present disclosure may modify various constituent elements in the various embodiments, but may not limit the respective constituent elements. For example, the above description does not limit the order and/or importance of the elements described. The foregoing description is for the purpose of distinguishing one element from another. For example, the first user device and the second user device indicate different user devices, although both are user devices. For example, a first element could be termed a second element, and, similarly, a second element could be termed a first element, without departing from the scope of various embodiments of the present disclosure.
It should be noted that: if it is described that one constituent element is "connected" to another constituent element, the first constituent element may be directly connected to the second constituent element, and a third constituent element may be "connected" between the first constituent element and the second constituent element. In contrast, when one constituent element is "directly connected" to another constituent element, it is understood that there is no third constituent element between the first constituent element and the second constituent element.
The term "user" used in various embodiments of the present disclosure may indicate a person using an electronic device or a device using an electronic device (e.g., an artificial intelligence electronic device).
The terminology used in the various embodiments of the present disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of the various embodiments of the present disclosure. As used herein, the singular is intended to include the plural as well, unless the context clearly indicates otherwise. Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the various embodiments of the present disclosure belong. The terms (such as those defined in commonly used dictionaries) should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein in various embodiments of the disclosure.
Materials:
PA10T, brand No.: vicnyl 700, melting point: the relative viscosity is 2.15 at 316 ℃, the proportion of terephthalic acid in diacid is 100mol percent, and the method is provided by special engineering plastics company Limited of Zhuhaiwantong;
PA10T/10I, brand: vicnyl 6100, melting point: 293 ℃, relative viscosity of 2.12, proportion of terephthalic acid in diacid of 85mol percent, provided by Zhuhaiwantong special engineering plastics company Limited;
PA6T/66, brand: vicnyl 400, melting point: 308 ℃, the relative viscosity is 2.22, the proportion of terephthalic acid in diacid is 54mol percent, and the method is provided by special engineering plastics company of Zhuhaiwantong;
PA66, brand No.: EP1106, melting point: 265 ℃ and relative viscosity of 2.28, supplied by Huafeng group Limited company;
glass fibers ECS10-03-568H, available from Jushi group, Inc.;
antioxidant S-EED, available from Claine corporation.
The test method comprises the following steps:
method for testing melting point of semi-aromatic polyamide resin: see ISO11357 (2009). The specific test method comprises the following steps: the melting point and the melting enthalpy of the sample are tested by a Perkin Elmer Diamond DSC analyzer; the heating rate is 10 ℃/min.
Method for testing relative viscosity of semi-aromatic polyamide resin: reference GB12006.1-2009, polyamide viscosity number determination method; the specific test method comprises the following steps: the relative viscosity r of a polyamide at a concentration of 10mg/ml is measured in 98% concentrated sulfuric acid at 25 ℃. + -. 0.01 ℃.
Testing the average length of the glass fiber: 1.5g of the sample was added to 25ml of hexafluoroisopropanol, allowed to stand at 22 ℃ for 14 hours, and then sonicated for 30 minutes. The soluble components were removed together with the solvent by filtration through a G2 frit (glass frit). The dried residue in the frit was transferred to a microscope slide. According to ISO 22314: sections 6.2 to 6.4 of 2006(E), the length distribution of the glass fibers was determined at 125 times magnification. Measurements were made on three pictures, 200 fibres in each case, to find the average length of the glass fibres.
Water absorption: and (3) performing injection molding according to the ISO178-2010 requirement to obtain a bent sample strip, comparing the weight change rate of the bent sample strip before and after boiling in water at 80 ℃ for 24h, and calculating the formula as water absorption rate (the weight of the sample after boiling in water-the weight of the sample before boiling in water)/the weight of the sample before boiling in water.
Dimensional stability: the dimensional stability before and after water absorption is characterized by using the dimensional change rate, a curved sample strip is obtained by injection molding according to the ISO178 requirement, and the length change rate of the curved sample strip before and after boiling in water at 80 ℃ for 24 hours is compared, wherein the calculation formula is as follows: the dimensional change rate is (length after boiling sample-length before boiling sample)/length before boiling sample.
And (3) determination of melt index: referring to ISO 1873-2007, the test was performed under the condition that the weight is 2.16kg at 15 ℃ above the melting point. The samples were oven dried at 120 ℃ for 4h before testing.
TABLE 1
TABLE 2
The glass fibers of comparative examples 1 to 4 have a length of less than 230 μm, an excessively small size, difficulty in forming a barrier effect against water molecules, and high water absorption and dimensional change rates; however, the glass fiber having a length of more than 400 μm as described in comparative example 6 resulted in a decrease in melt index and poor flowability.
As can be seen from tables 1 and 2, the glass fiber-reinforced semi-aromatic polyamide molding composition having a specific glass fiber length of the present invention has a balance between water absorption properties and fluidity as compared with the molding composition having the glass fibers with an arithmetic mean length of 230 μm to 400 μm or more, so that a molded article made from the molding composition of the present invention can be used for sliding parts and engine peripheral parts, and also has a balance between water absorption properties and fluidity. It is applicable in the electrical/electronics industry, in particular in the form of large surface area components for components of circuit boards, housings, foils, wires, switches, distributors, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, connectors, controllers, storage devices and sensors, in particular in the form of components of complex design with a precise structure for housing parts of switch cabinets.
Those skilled in the art will appreciate that the modules in the devices in the implementation scenario may be distributed in the devices in the implementation scenario according to the description of the implementation scenario, or may be located in one or more devices different from the present implementation scenario with corresponding changes. The modules of the implementation scenario may be combined into one module, or may be further split into a plurality of sub-modules.
The above-mentioned invention numbers are merely for description and do not represent the merits of the implementation scenarios.
The above disclosure is only a few specific implementation scenarios of the present invention, however, the present invention is not limited thereto, and any variations that can be made by those skilled in the art are intended to fall within the scope of the present invention.
Claims (12)
1. The glass fiber reinforced semi-aromatic polyamide molding composition with specific glass fiber length is characterized by comprising the following components in parts by weight:
(A)25 to 90 parts of at least one semi-aromatic polyamide resin;
(B)5 to 70 parts of glass fibers having an arithmetic mean length of 200 to 450 μm;
(C)0 to 2 parts of an additive.
2. Glass fiber reinforced semi-aromatic polyamide molding composition having a specific glass fiber length according to claim 1, characterized in that the glass fibers have an arithmetic mean length of 230 to 400 μ ι η.
3. The glass fiber reinforced semi-aromatic polyamide molding composition having a specific glass fiber length according to claim 1, characterized in that the semi-aromatic polyamide resin comprises the following repeating units and derivatives derived from the following repeating units:
(i) terephthalic acid or a derivative thereof, and optionally one or more aromatic or aliphatic diacids or derivatives thereof other than terephthalic acid;
(ii) one or more aliphatic diamines having from 4 to 20 carbon atoms, and/or optionally one or more additional diamines;
(iii) and optionally one or more aminocarboxylic acids and/or lactams;
wherein terephthalic acid or a derivative thereof is present in an amount of 40 to 100 mole percent of (i), one or more aliphatic diamines having 4 to 20 carbon atoms are present in an amount of 40 to 100 mole percent of (ii), and one or more aminocarboxylic acids or lactams are present in an amount of 0 to 25 mole percent of the total amount of (i) + (ii) + (iii), wherein component (i) and component (ii) are equal in mole percent and the sum of component (i) and component (ii) is present in an amount of 0 to 25 mole percent of the total amount of (i) + (ii) + (iii).
4. Glass fiber reinforced semi-aromatic polyamide molding composition having a specific glass fiber length according to claim 3, characterized in that the component (ii) contains at least one aliphatic diamine ii-1 having 8-12 carbon atoms, and ii-1 is present in 40 to 100 mole percent, preferably 100 mole percent, of ii.
5. The glass fiber reinforced semi-aromatic polyamide molding composition having a specific glass fiber length of claim 3, wherein the aliphatic diamine having 4 to 20 carbon atoms is selected from at least one of linear aliphatic diamines such as 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, 14-tetradecanediamine, 1, 16-hexadecanediamine, 1, 18-octadecanediamine, and/or 1-butyl-1, 2-ethylenediamine, 1-dimethyl-1, 4-butanediamine, 1-ethyl-1, 4-butanediamine, 1, 2-dimethyl-1, 4-butanediamine, 1, 3-dimethyl-1, 4-butanediamine, 1, 4-dimethyl-1, 4-butanediamine, 2, 3-dimethyl-1, 4-butanediamine, 2-methyl-1, 5-pentanediamine, 3-methyl-1, 5-pentanediamine, 2, 5-dimethyl-1, 6-hexanediamine, 2, 4-dimethyl-1, 6-hexanediamine, 3-dimethyl-1, 6-hexanediamine, 2, 4-trimethyl-1, 6-hexanediamine, 2,4, 4-trimethyl-1, 6-hexanediamine, 2, 4-diethyl-1, 6-hexanediamine, 2-dimethyl-1, 7-heptanediamine, 2, 3-dimethyl-1, 7-heptanediamine, 2, 4-dimethyl-1, 7-heptanediamine, 2, 5-dimethyl-1, 7-heptanediamine, 2-methyl-1, 8-octanediamine, 3-methyl-1, 8-octanediamine, 4-methyl-1, 8-octanediamine, 1, 3-dimethyl-1, 8-octanediamine, 1, 4-dimethyl-1, 8-octanediamine, 2, 4-dimethyl-1, 8-octanediamine, 3, 4-dimethyl-1, 8-octanediamine, At least one of branched aliphatic diamines such as 4, 5-dimethyl-1, 8-octanediamine, 2-dimethyl-1, 8-octanediamine, 3-dimethyl-1, 8-octanediamine, 4-dimethyl-1, 8-octanediamine and 5-methyl-1, 9-nonanediamine.
6. Glass fiber reinforced semi-aromatic polyamide molding composition having a specific glass fiber length according to claim 5, characterized in that one or a combination of any two of 1, 6-hexanediamine, 1, 10-decanediamine and 1, 12-dodecanediamine is preferred.
7. Glass fiber reinforced semi-aromatic polyamide molding composition having a specific glass fiber length according to any one of claims 1 to 4, characterized in that the concentration of concentrated sulfuric acid is 10mg/ml measured in 98% concentrated sulfuric acid at 25 ℃ ± 0.01 ℃, and the relative viscosity of the semi-aromatic polyamide resin is 1.7 to 2.8, preferably 1.85 to 2.45, more preferably 2.0 to 2.3.
8. The glass fiber reinforced semi-aromatic polyamide molding composition with a specific glass fiber length according to any one of claims 1 to 4, characterized in that the semi-aromatic polyamide resin has a melting point of 280-.
9. Glass fiber reinforced semi-aromatic polyamide molding composition having a specific glass fiber length according to any one of claims 1 to 4, characterized in that the glass fiber is present in a fraction of 5 to 55 parts, preferably 10 to 50 parts, and particularly preferably 15 to 40 parts.
10. Glass fiber reinforced semi-aromatic polyamide molding composition having a specific glass fiber length according to any one of claims 1 to 4, characterized in that the at least one additive is present in a fraction of 0.001 to 18 parts, preferably 0.01 to 10 parts, and particularly preferably 0.1 to 5 parts.
11. Glass fiber reinforced semi-aromatic polyamide molding composition having a specific glass fiber length according to any one of claims 1 to 4, characterized in that the cross section of the glass fiber is circular.
12. Moulding of a glass fiber reinforced semi-aromatic polyamide moulding composition with specific glass fiber length according to claim 1, characterized in that the moulding contains at least partially the glass fiber reinforced semi-aromatic polyamide moulding composition with specific glass fiber length of claim 1, which is preferably used in the form of an assembly for the electrical/electronics industry, in particular in the form of a large surface area assembly for components of circuit boards, housings, foils, wires, switches, dispensers, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, connectors, controllers, storage devices and sensors, in particular in the form of a complex designed assembly with a fine structure for housing parts of switch cabinets.
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| CN114605820A (en) * | 2022-03-09 | 2022-06-10 | 珠海万通特种工程塑料有限公司 | Reinforced semi-aromatic polyamide composition and preparation method and application thereof |
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