CN107603214B - Flame-retardant polyamide composition, and preparation method and application of flame-retardant polyamide - Google Patents
Flame-retardant polyamide composition, and preparation method and application of flame-retardant polyamide Download PDFInfo
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Abstract
The present invention relates to a flame retardant polyamide composition comprising: (A) polyamide, and (B) 5 to 40% of a flame retardant, the percentages being percentages by mass relative to the polyamide; the polyamide has a melting point of 230 ℃ or higher and a weight-average molecular weight of 25000-40000. The polyamide composition can reduce the dosage of the flame retardant, obtain the flame retardant effect equivalent to or better than that of other polyamide compositions, can not cause environmental pollution due to the decomposition of a large amount of flame retardant, and has excellent mechanical properties and wide application range.
Description
Technical Field
The invention relates to a flame-retardant polyamide composition, a preparation method and application of flame-retardant polyamide.
Background
Polyamide is a polymer composite material having excellent properties, exhibits excellent properties in terms of mechanical strength, electrical properties, abrasion resistance, and the like, and can be widely used as an engineering plastic in the fields of mechanical parts, electronics, electrical parts, and the like, and in recent years, has been further developed into various fields such as automobile interior materials and building materials. The above applications have high requirements on the flame retardant properties of polyamides.
In the prior art, for the polyamide used on a large scale, such as nylon 6 or nylon 66, the flame retardant property of the polyamide is generally improved by adding a flame retardant. Most of nylon 6 or nylon 66 is added with halogen/antimony flame retardant to realize the flame retardant effect, but the halogen/antimony flame retardant has high cost, and the halogen-containing compound released during combustion not only causes harm to human bodies, but also directly pollutes the environment. Also, with the addition of flame retardants, not only is the cost increased, but the mechanical strength of the polyamide, for example: the tensile properties, elongation at break, impact strength, etc. are gradually reduced. On the basis, the research on a polyamide product which has low addition of a flame retardant, excellent flame retardant effect and good mechanical strength has become a problem to be solved urgently in the industry.
Disclosure of Invention
According to one aspect of the present invention, there is provided a polyamide composition comprising:
(A) a polyamide, and,
(B) flame retardant 5-40%, preferably 8-30%, more preferably 15-25%;
the polyamide comprises polyamide with a melting point of 230 ℃ or above and a weight average molecular weight of 25000-40000; the percentage is a mass percentage with respect to the polyamide (component (a)).
According to one embodiment of the invention, the polyamide preferably has a limiting oxygen index of more than 30% (V/V), more preferably 31 to 36% (V/V), still more preferably 32 to 35% (V/V).
According to an embodiment of the present invention, the initial thermal decomposition temperature Td of the polyamide is preferably 280-330 ℃, more preferably 290-320 ℃, and even more preferably 300-315 ℃. The initial thermal decomposition temperature is defined as a temperature at which the polymer loses 1% weight and can be expressed as Td (1% loss).
The maximum decomposition rate of the polyamide is preferably 380-450 ℃, more preferably 390-430 ℃ and even more preferably 400-430 ℃. Thermal decomposition at maximum decomposition rateT for temperatureMaximum rate of decompositionAnd (4) showing.
According to one embodiment of the invention, the polyamide has an amino end group content of preferably 45 to 60meq/kg, more preferably 48 to 57 meq/kg.
According to one embodiment of the invention, the polyamide preferably has a glass transition temperature of 45 to 60 ℃ and more preferably 48 to 55 ℃.
According to one embodiment of the present invention, the melting point of the polyamide is preferably 240-.
Preferably, the polyamide (component (a)) comprises polypentamethyleneadipamide, i.e. polyamide 56.
In one embodiment of the present invention, the component (a) further comprises other polymers besides polyamide, and the other polymers comprise one or more of polyolefin, polyester, polycarbonate, polyacrylate, polymethacrylate, polyacrylonitrile, polyimide, epoxy resin, polyurethane, polyvinyl acetate, phenolic resin, urea resin or other polyamide.
The polyolefin comprises one or more of polyethylene, polyvinyl chloride, polypropylene, polybutylene, polystyrene, ABS, ethylene-propylene copolymer, polytetrafluoroethylene, polyvinylidene fluoride and ethylene/vinyl acetate copolymer. The polyester comprises PET and/or PBT. The other polyamides include any known polyamide, such as one or more of polyamide 6, polyamide 66, polyamide 610, polyamide 1010, and polyamide 1414.
Preferably, the weight ratio of the polyamide to the other polymer is preferably (70-99): (30-1), more preferably (80-90): (20-10).
In one embodiment of the present invention, the flame retardant comprises an organic flame retardant, preferably a phosphorus-containing flame retardant.
In one embodiment of the present invention, the phosphorus-containing flame retardant includes, but is not limited to, one or more of aryl phosphate monophosphate, aryl phosphate diphosphate, dimethyl alkyl bony phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, propylbenzene-based phosphate, butylbenzene-based phosphate, and hypophosphite; hypophosphites are preferred.
Further, the polyamide composition of the present invention may further comprise one or more of a reinforcing agent, a toughening agent, a chemical crosslinking aid, a lubricant, a heat stabilizer, an antioxidant, an ultraviolet decomposition inhibitor, a mold release agent, a colorant, a nucleating agent, and a plasticizer. The above-mentioned ingredients are present in the polyamide composition of the invention in the amounts normally used in the art.
The reinforcing agent preferably comprises any one or a combination of more of calcium carbonate, glass fiber with a circular or non-circular cross section, glass flake, glass bead, carbon fiber, talc, mica, wollastonite, calcined clay, kaolin, diatomaceous earth, magnesium sulfate, magnesium silicate, barium sulfate, titanium dioxide, sodium aluminum carbonate, barium ferrite and potassium titanate. The addition amount of the reinforcing agent is 1-20%, and the percentage is the mass percentage of the component (A).
The toughening agent preferably comprises a reactive functional group and/or a metal salt of carboxylic acid, preferably comprises a copolymer of glycidyl methacrylate and methacrylate, a copolymer of grafted unsaturated carboxylic anhydride ethylene and α -olefin, a diene copolymer of ethylene and α -olefin, a copolymer of 2-isocyanatoethyl alkene methacrylate and more than one methacrylate, and an ionomer generated by reacting 2-isocyanatoethyl alkene methacrylate with a zinc compound, a lithium compound, a magnesium compound or a manganese compound respectively.
The chemical crosslinking assistant (crosslinking agent) preferably comprises any one or a combination of more of dicumyl oxide, dibenzoyl peroxide or 2, 5-dimethyl-2, 5-bis (tert-butylperoxyhexane or di-tert-butyl peroxide). The addition amount of the chemical crosslinking assistant is 0.1-5%, and the percentage is the mass percentage of the component (A).
The lubricant preferably comprises any one or combination of several of fatty acid metal salt, fatty acid alkali metal salt, fatty acid alkaline earth metal salt, fatty acid ester and fatty acid amide, more preferably any one or combination of several of calcium stearate, calcium montanate, aluminum stearate, glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate. The fatty acid is a carboxylic acid, preferably a monocarboxylic acid or a dicarboxylic acid, more preferably a fatty acid having 10 to 44 carbon atoms, further preferably a fatty acid having 14 to 44 carbon atoms, and further preferably a fatty acid having 30 to 40 carbon atoms; for example, the fatty acid may preferably be pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, or behenic acid, and more preferably stearic acid, capric acid, and montanic acid. The metal is Al, Ca or Mg. The fatty acid ester is obtained by reacting fatty acid with fatty alcohol. The aliphatic alcohol is a monohydric alcohol to a tetrahydric alcohol, preferably n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, and further preferably glycerol and pentaerythritol. The fatty acid amide is obtained by reacting fatty acid with aliphatic amine. The aliphatic amine may be a monoamine to a triamine, preferably stearamide, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, and further preferably ethylenediamine and hexamethylenediamine. The addition amount of the reinforcing agent is 0.1-5%, and the percentage is the mass percentage of the component (A).
The heat stabilizer preferably comprises a copper compound. The copper compound is preferably cuprous halide, and more preferably any one or a combination of two of cuprous halide and alkali metal halide. The alkali metal halide is preferably KI. When the copper compound is a combination of cuprous halide and alkali metal halide, the mass ratio of cuprous halide to alkali metal halide is 1: 4. The addition amount of the heat stabilizer is 0.2-5%, and the percentage is the mass percentage of the component (A).
The antioxidant preferably comprises any one or combination of sterically hindered phenol antioxidant, sterically hindered aliphatic amine antioxidant and aromatic amine antioxidant. Sterically hindered aliphatic amine antioxidants have preferred applicability. When the antioxidant is a sterically hindered phenol antioxidant, the sterically hindered phenol antioxidant is present in an amount of 0.05 to 3%, preferably 0.1 to 1.5%, more preferably 0.1 to 1% by mass of the component (A); when the antioxidant is a steric aliphatic amine antioxidant, the steric aliphatic amine antioxidant is present in an amount of 0 to 3% by mass, preferably 0.01 to 2% by mass, more preferably 0.05 to 1.5% by mass, based on the component (a).
The ultraviolet decomposition inhibitor preferably comprises any one or combination of substituted resorcinols, salicylates, benzotriazoles and benzophenones. The amount of the ultraviolet decomposition inhibitor added is 2% or less, for example, 0.1 to 1.5%, the percentage being a mass percentage of the component (a).
The colorant preferably comprises a dye or a pigment. The pigment is an inorganic pigment or an organic pigment. The inorganic pigment is preferably titanium dioxide or ultramarine blue; the organic pigment is any one or combination of more of phthalocyanine, quinacridone and perylene. The dye is nigrosine or anthraquinone. The amount of the colorant added is 2% or less, for example, 0.1 to 1.5%, the percentage being a mass percentage based on the component (a).
The nucleating agent preferably comprises any one or a combination of several of sodium phenylphosphinate, alumina, silica and talc. The nucleating agent is added in an amount of 2% or less, for example, 0.1 to 1.5%, the percentage being a mass percentage of the component (a).
An engineering plastic whose raw material comprises the polyamide composition as described above.
The preparation method of the engineering plastic preferably comprises the following steps: the polyamide composition is melt mixed and shaped, for example injection molded, injection/blow molded, extruded or extrusion blow molded, according to methods conventional in the art to produce engineering plastics.
The invention has the beneficial effects that: the polyamide composition can reduce the dosage of the flame retardant, obtain the flame retardant effect equivalent to or better than that of other polyamide compositions, can not cause environmental pollution due to the decomposition of a large amount of flame retardant, and has excellent mechanical properties and wide application range.
Detailed Description
The invention is further illustrated by the following specific examples.
1. Determination of limiting oxygen index
The Limiting Oxygen Index (LOI) is an index which is used for representing the combustion behavior of a material and judging the difficulty of combustion of the material when the material is in contact with flame, and is used for supporting the volume fraction concentration of oxygen when the polymer is combusted in an oxygen and nitrogen mixed gas. The limiting oxygen index can be determined by burning a polymer rod downward under specified conditions using the candle test. In the invention, the limit oxygen index detection method refers to the method of ISO 4589-2 for determination.
2. Method for detecting relative viscosity η r
ISO 307.1157.1628
3. Determination of melting Point (Tm)
ISO 3146ISO 11357
4. Method for detecting tensile strength and elongation at break
ISO 527-2
5. Bending strength
ISO 527-2
6. Notched impact strength of cantilever beam
ISO 179/leA
7. UL-94 flammability rating (Underwriters Laboratory):
ISO 4589-2
the flame retardant grades of plastics include: HB. V-2, V-1 and V-0;
HB: 3-13mm sample, the burning speed is less than 40 mm/min; the burning speed of the sample is less than 70mm/min and is less than 3 mm; or extinguished before 10mm mark;
v-2: carrying out combustion test on the sample for 10s twice, and extinguishing the flame within 60 s; there may be combustion products falling.
V-1: after the sample is subjected to the combustion test for 10 seconds twice, the flame is extinguished within 60 seconds; no combustible material can fall off.
V-0: after the sample is subjected to the combustion test for 10 seconds twice, the flame is extinguished within 30 seconds; no combustible material can fall off.
8. Method for detecting content of terminal amino group
ASTM D2074
9. Glass transition temperature
ISO 11357
10. Heat generationDecomposition temperature (T)degradation)
Thermogravimetric Analysis (TGA): the relationship between the mass of the sample to be tested and the temperature change is measured at the programmed temperature so as to research the thermal stability and the components of the material. The sample was placed in an oven and dried at 80 ℃ for 12h, after which 5-10mg of the sample was placed in an alumina crucible, while using an empty crucible as a control. The sample was heated from 30 ℃ to 700 ℃ at a rate of 20 ℃/min under nitrogen.
Td (1% loss): the initial thermal decomposition temperature, defined as the temperature at which the polymer loses 1% weight.
TMaximum rate of decomposition: thermal decomposition temperature at maximum decomposition rate.
Example 1
100 parts by weight of PA56(Tm254 ℃, Mw32000), 12 parts by weight of flame retardant OP1312, 10 parts by weight of GF, 0.4 part by weight of crosslinking agent, 0.4 part by weight of lubricant, 0.6 part by weight of heat stabilizer, 0.3 part by weight of antioxidant, and 0.3 part by weight of ultraviolet decomposition inhibitor were melt-mixed at about 255 ℃ and extrusion-molded to obtain a strand for the following test.
Examples 2 to 5 and comparative examples 1 to 8
The same procedure as in example 1 was conducted except that the components and their contents were changed as shown in tables 1 to 3, and the obtained polyamide was used in the following tests. The PA6 and PA66 used in the comparative examples are both commercially available.
Wherein, OP 1312: an organic hypophosphite flame retardant;
MCA: chemical formula C6H9N9O3Melamine cyanurate flame retardants;
GF: a glass fiber reinforcement;
MBS: a methyl methacrylate-butadiene-styrene terpolymer toughening agent.
TABLE 1 Polyamide composition Components and their contents (number unit is parts by weight)
TABLE 2 Polyamide composition Components and their amounts
TABLE 3 Polyamide composition Components and their contents
The materials obtained in examples 1 to 5 and comparative examples 1 to 8 were used for tensile strength test, bending strength test, notched izod impact strength test, and UL-94 flammability rating evaluation. The results are shown in tables 4 to 6.
TABLE 4 Property parameters of the polyamide compositions of examples 1 to 6
| Group of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Tensile strengthMPa | 96 | 116 | 160 | 74 | 68 |
| Bending strength MPa | 142 | 147 | 164 | 88 | 76 |
| Notched impact strength of cantilever beam | 5.1 | 5.6 | 5.3 | 4.0 | 3.9 |
| UL-94 flammability rating (0.8mm) | V-0 | V-0 | V-0 | V-0 | V-0 |
| LOI | 36.6 | 34.1 | 35.2 | 35.3 | 34.1 |
TABLE 5 Property parameters of the polyamide compositions of comparative examples 1 to 6
| Group of | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Tensile strength | 94 | 120 | 156 | 71 | 66 |
| Bending strength | 125 | 148 | 163 | 82 | 72 |
| Notched impact strength of cantilever beam | 5.2 | 5.8 | 4.8 | 3.8 | 3.4 |
| UL-94 flammability rating (0.8mm) | V-2 | V-2 | V-2 | V-2 | V-2 |
| LOI | 26.0 | 28.1 | 25.9 | 28.5 | 27.4 |
TABLE 6 Property parameters of the polyamide compositions of comparative examples 6 to 8
| Group of | Comparative example 6 | Comparative example 7 | Comparative example 8 |
| Tensile strength | 95 | 113 | 110 |
| Bending strength | 129 | 138 | 130 |
| Notched impact strength of cantilever beam | 4.5 | 5.1 | 4.1 |
| UL-94 flammability rating (0.8mm) | V-2 | V-2 | V-2 |
| LOI | 26.0 | 27.1 | 27.1 |
Claims (12)
1. A polyamide composition, comprising:
(A) a polyamide, said polyamide comprising polyamide 56, and,
(B) 5-40% of a flame retardant; the percentages are percentages by mass relative to the polyamide;
the polyamide has a melting point of 230 ℃ or above and a weight-average molecular weight of 25500-40000; wherein the melting point of the polyamide is determined according to the method of ISO 3146;
the flame retardant is selected from one or more of triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, melamine cyanurate flame retardant MCA and organic hypophosphite flame retardant OP 1312.
2. The polyamide composition according to claim 1, wherein the flame retardant is 8 to 30% by mass.
3. The polyamide composition according to claim 1, wherein the flame retardant is 15-25% by mass.
4. The polyamide composition according to claim 1, wherein the polyamide has a limiting oxygen index of 30% or more; and/or the presence of a gas in the gas,
the initial thermal decomposition temperature of the polyamide is 280-330 ℃; and/or the presence of a gas in the gas,
the thermal decomposition temperature of the polyamide at the maximum decomposition rate is 380-450 ℃; and/or the presence of a gas in the gas,
the content of terminal amino groups of the polyamide is 45-60 meq/kg; and/or the presence of a gas in the gas,
the glass transition temperature of the polyamide is 45-60 ℃; and/or the presence of a gas in the gas,
the melting point of the polyamide is 240-270 ℃;
wherein the limiting oxygen index of the polyamide is determined according to the method of ISO 4589-2; the amino end group content of the polyamide is determined according to the method of ASTM D2074; the glass transition temperature of the polyamide is determined according to the method of ISO 11357; the initial thermal decomposition temperature is the temperature at which the weight loss of the polyamide is 1% in the thermogravimetric analysis process, and the thermal decomposition temperature at the maximum decomposition rate is the thermal decomposition temperature at the maximum decomposition rate in the thermogravimetric analysis process.
5. The polyamide composition of claim 4, wherein the polyamide has a limiting oxygen index of 31-36%; and/or the presence of a gas in the gas,
the initial thermal decomposition temperature of the polyamide is 290-320 ℃; and/or the presence of a gas in the gas,
the thermal decomposition temperature of the polyamide at the maximum decomposition rate is 390-430 ℃; and/or the presence of a gas in the gas,
the content of terminal amino groups of the polyamide is 48-57 meq/kg; and/or the presence of a gas in the gas,
the glass transition temperature of the polyamide is 48-55 ℃; and/or the presence of a gas in the gas,
the melting point of the polyamide is 250-260 ℃.
6. The polyamide composition of claim 4, wherein the polyamide has a limiting oxygen index of 32-35%; and/or the presence of a gas in the gas,
the initial thermal decomposition temperature of the polyamide is 300-315 ℃; and/or the presence of a gas in the gas,
the maximum decomposition rate of the polyamide has a thermal decomposition temperature of 400-430 ℃.
7. The polyamide composition of claim 1, further comprising other polymers including one or more of polyolefins, polyesters, polycarbonates, polyacrylates, polymethacrylates, polyacrylonitriles, polyimides, epoxy resins, polyurethanes, polyvinyl acetates, phenolic resins, urea-formaldehyde resins, and other polyamides;
the weight ratio of the polyamide to the other polymer is (70-99): (30-1).
8. The polyamide composition of claim 7 wherein the weight ratio of the polyamide to the other polymer is (80-90): (20-10).
9. The polyamide composition of claim 7, wherein the polyolefin comprises one or more of polyethylene, polyvinyl chloride, polypropylene, polybutylene, polystyrene, ABS, ethylene-propylene copolymers, polytetrafluoroethylene, polyvinylidene fluoride, and ethylene/vinyl acetate copolymers;
the polyester comprises PET and/or PBT;
the other polyamides include one or more of polyamide 6, polyamide 66, polyamide 610, polyamide 1010, and polyamide 1414.
10. The polyamide composition of claim 1, further comprising one or more of a reinforcing agent, a toughening agent, a chemical crosslinking coagent, a lubricant, a thermal stabilizer, an antioxidant, an ultraviolet decomposition inhibitor, a mold release agent, a colorant, a nucleating agent, and a plasticizer.
11. An engineering plastic whose raw material comprises the polyamide composition as claimed in any one of claims 1 to 10.
12. A preparation method of engineering plastics comprises the following steps: melt mixing the polyamide composition according to any one of claims 1 to 10 to produce an engineering plastic by injection molding, injection blow molding, extrusion or extrusion blow molding.
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| CN110903642B (en) * | 2018-09-18 | 2022-03-18 | 上海凯赛生物技术股份有限公司 | Halogen-free flame-retardant resin and preparation method thereof |
| CN109486182A (en) * | 2018-10-22 | 2019-03-19 | 滁州吉胜新材料科技有限公司 | A kind of high temperature resistant aramid fiber 56 and preparation method thereof |
| CN111117218A (en) * | 2019-12-31 | 2020-05-08 | 会通新材料(上海)有限公司 | Polyamide composition with improved color fastness after hot baking and application thereof |
| CN112694744A (en) * | 2020-12-10 | 2021-04-23 | 苏州恒坤精密电子有限公司 | Preparation method of high-temperature-resistant insulating material for power battery shell |
| CN115948050A (en) * | 2022-08-12 | 2023-04-11 | 苏州润佳高分子材料有限公司 | Anti-warping glass fiber reinforced nylon material |
| CN117887249A (en) * | 2023-12-12 | 2024-04-16 | 金发科技股份有限公司 | Flame-retardant polyamide composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793289A (en) * | 1971-10-13 | 1974-02-19 | Allied Chem | Flame retardant nylon compositions |
| CN1726258A (en) * | 2002-12-16 | 2006-01-25 | 帝斯曼知识产权资产管理有限公司 | The method for preparing the flame-retardant polymer mixture |
| CN104861648A (en) * | 2015-05-21 | 2015-08-26 | 浙江新力塑料股份有限公司 | Special halogen-free flame retardant reinforced PA (polyamide) 56 composite material for casing of low-voltage circuit breaker |
-
2016
- 2016-07-12 CN CN201610545635.9A patent/CN107603214B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793289A (en) * | 1971-10-13 | 1974-02-19 | Allied Chem | Flame retardant nylon compositions |
| CN1726258A (en) * | 2002-12-16 | 2006-01-25 | 帝斯曼知识产权资产管理有限公司 | The method for preparing the flame-retardant polymer mixture |
| CN104861648A (en) * | 2015-05-21 | 2015-08-26 | 浙江新力塑料股份有限公司 | Special halogen-free flame retardant reinforced PA (polyamide) 56 composite material for casing of low-voltage circuit breaker |
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| GR01 | Patent grant |