CN107099135B - Reinforced modified flame-retardant PA6 composition - Google Patents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- 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
- C08K2201/003—Additives being defined by their diameter
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- C08K2201/00—Specific properties of additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
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Abstract
The invention discloses a reinforced modified flame-retardant PA6 composition and a preparation method thereof, wherein the composition comprises the following components in parts by weight: PA 6: 50-80 parts; ultra-high molecular weight PE: 10-20 parts; maleic anhydride grafted PE: 1-10 parts; glass fiber: 10-30 parts; large particle size SiO 2: 5-10 parts; small particle size SiO 2: 5-10 parts; silane coupling agent: 0.5-3 parts; antioxidant: 0.5-2 parts; lubricant: 0.5-2 parts; flame retardant: 10-20 parts; products prepared from the composition have improved dimensional stability, tensile properties, impact resistance, and the like, while having enhanced flame retardant properties.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a reinforced modified flame-retardant PA6 composition.
Background
The polyamide is generally called nylon, is a general term for polymers containing amide group repeating units in a polymer macromolecular chain, is mainly obtained by polycondensation or self-polymerization of dibasic acid and diamine or amino acid lactam, and is the earliest developed and most used thermoplastic engineering plastic. Polyamide 6 has the advantages of high mechanical strength, high melting point, wear resistance, oil resistance and the like, and is widely used in the fields of automobiles, electromechanics, electronics, textiles, household appliances and the like.
The micro-nano SiO2 is one of extremely important high-tech superfine inorganic new materials, and is widely used as a filler of a resin matrix due to large specific surface area, strong surface adsorption force, large surface energy, high chemical purity and good dispersion performance.
The ultra-high molecular weight polyethylene is thermoplastic engineering plastic with excellent comprehensive performance, has an average molecular weight of about 150-800 ten thousand, and has excellent performances of impact resistance, abrasion resistance, self-lubrication, chemical corrosion resistance and the like which are incomparable with other plastics due to high molecular weight.
The polyamide 6 is easy to absorb water due to containing a large amount of polar groups, has large shrinkage rate after molding and low dimensional stability, is sensitive to gaps, and has improved flame retardant property, impact resistance and tensile property.
The currently used flame retardants for polyamides are mainly brominated polystyrene, decabromodiphenyl ether, decabromodiphenyl ethane, melamine pyrophosphate, red phosphorus and the like. However, these flame retardants are more or less expensive, difficult to process, rough in the surface of the injection molded article, and have poor color. With increasing environmental requirements, some flame retardants such as decabromodiphenyl ether may be banned and the flame retardant materials must meet the european union ROHS directive.
Therefore, the polyamide needs to be further modified so that the product has excellent flame retardant property while having good dimensional stability, impact resistance and tensile property, so as to meet the requirements of practical application.
Disclosure of Invention
The invention aims to provide a reinforced modified flame-retardant PA6 composition, which has improved dimensional stability, tensile property, impact resistance, flame retardance and the like while having heat resistance, chemical resistance, wear resistance and the like by combining a silica filler with reinforcing fibers and an inorganic halogen-free flame retardant in the composition by using a specific particle size.
The technical scheme of the invention is as follows:
a reinforced modified flame-retardant PA6 composition is composed of the following components in parts by weight: PA 6: 50-80 parts; ultra-high molecular weight PE: 10-20 parts; maleic anhydride grafted PE: 1-10 parts; glass fiber: 10-30 parts; large particle size SiO 2: 5-10 parts; small particle size SiO 2: 5-10 parts; silane coupling agent: 0.5-3 parts; antioxidant: 0.5-2 parts; lubricant: 0.5-2 parts; flame retardant: 10-20 parts; PA6 is made of polymer slice with relative viscosity of 3.0 or more, and can be made by domestic and foreign manufacturers, such as Pasteur in Germany, Mitsubishi chemical, and the product of the Japan ministry of Japan; the amount is preferably 60 to 70 parts.
The ultra-high molecular weight PE adopts a product with the weight-average molecular weight of 200-600 ten thousand, and can adopt products of Germany Hurst company, Japan three-well petrochemical and domestic Qilu petrochemical; the amount is preferably 10 to 15 parts.
The maleic anhydride grafted PE can be a commercially available product or a self-made product; the amount is preferably 5 to 8 parts.
As the glass fibers, high-strength glass fibers are used, and specific examples are S-glass fibers having a size of 910 or 995 from Owens Corning, T-glass fibers from Nittobo, HiPertex from 3B, HS 4-glass fibers from Sinomajinjingling Fiberglass, R-glass fibers from Vetrotex, and S-1 and S-2-glass fibers from AGY. The glass fibers may be in the form of short fibers, preferably chopped glass of 0.2mm to 20mm length, or in the form of continuous filament fibers; the amount is preferably 15 to 20 parts.
The SiO2 with large particle size is 10-40 μm average particle size, and the SiO2 with small particle size is 0.05-0.1 μm average particle size, with the weight ratio of 1-2:2-1, preferably 1: 1.
The silane coupling agent is a silane coupling agent having an amino group or an epoxy group, such as KH 550, KH 560, KH 602.
The antioxidant is a composite antioxidant consisting of hindered phenol antioxidant and phosphite antioxidant, wherein the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 1; the hindered phenol antioxidant is selected from one or more of 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 2, 6-di-tert-butyl-4-methyl-phenol, N '-bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionamide), 2' -bis (4-methyl-6-tert-butyl-phenol) methane and 2, 2 '-bis (4-ethyl-6-tert-butyl-phenol) methane, the phosphite antioxidant is selected from 2, 2' -ethylidene bis (4, 6-di-tert-butylphenyl) fluorophosphite and tetra (2, 4-di-tert-butylphenyl) -4, one or more of 4' -biphenyl diphosphite.
The lubricant may be calcium stearate, polyethylene wax or ethylene bis stearamide or a mixture thereof.
The flame retardant is aluminum hydroxide or magnesium hydroxide, and the size is preferably between 800-5000 meshes. The magnesium hydroxide and the aluminum hydroxide can absorb a large amount of latent heat and release moisture when being heated and decomposed, so that the actual temperature of flame on the surface of the material is reduced, the speed of degrading the polymer into low molecules is reduced, the generation of combustible substances is reduced, the concentration of oxygen on the surface is reduced by released water vapor, and the surface combustion is difficult to carry out; magnesium hydroxide and aluminum hydroxide can delay the ignition time of the material and reduce the smoke generation amount of the material and the escape speed of smoke. Meanwhile, the generated magnesium oxide or aluminum oxide can also absorb substances such as free radicals, carbon and the like, so that the flame retardant property of the flame retardant is further improved. Meanwhile, the aluminum hydroxide or the magnesium hydroxide does not contain halogen, and the product containing the aluminum hydroxide or the magnesium hydroxide does not generate toxic and harmful substances such as dioxin and the like in the combustion process, so the aluminum hydroxide or the magnesium hydroxide has good environmental protection performance.
The invention also provides a preparation method of the reinforced modified flame-retardant PA6 composition, which comprises the following steps:
(1) uniformly mixing silica particles with the same particle size, glass fibers and a silane coupling agent, performing ultrasonic dispersion for 10-30 min, adding ethanol and water, stirring in an aqueous solution at the temperature of 60-80 ℃ for 1-2 h, adjusting the pH value to 8.5-9.5 by using ammonia water, cooling, filtering, washing, and drying at the temperature of 100-120 ℃ to obtain silica particles and glass fibers with the surface modified by the silane coupling agent;
(2) PA6, the silane coupling agent surface modified silica particles obtained in the step (1), a flame retardant, ultra-high molecular weight PE, maleic anhydride grafted PE, an antioxidant and a lubricant are mixed at high speed of 1000-2000 rpm for 20-60 minutes to obtain a premix;
(3) and (3) feeding the premix obtained in the step (2) into a double-screw extruder, adding silane coupling agent surface modified glass fiber at a special glass fiber port of the double-screw extruder, wherein the temperature of a screw zone is 200-260 ℃, the rotating speed of the screw is 300-600 rpm, and extruding and granulating to obtain the reinforced modified flame-retardant PA6 particles.
In the invention, the ultra-high molecular weight polyethylene and the glass fiber are used for reinforcing together, so that the mechanical properties, such as tensile strength and the like, of the PA6 composition are greatly improved. Meanwhile, in the composition, as the filling particle silicon dioxide with different sizes and particle diameters is used, when the composition is dispersed in a polyamide resin system, large particles can form a large backbone network, and small particles have better dispersibility and can be dispersed to local areas which are difficult to reach by the large particles, such as bent parts, so that various particles can be well dispersed and filled in a matrix, and the volume shrinkage rate and the notch impact resistance of the molded product are effectively reduced. Meanwhile, the inorganic flame retardant is adopted, so that the flame retardant property of the composition is effectively improved, and the requirements of environmental protection and the like are met.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
PA6 used was a polymer chip having a relative viscosity of 3.0 or more, and a German Pasteur product, Ultramid B35, a relative viscosity of 3.3, and a number average molecular weight of 24,000.
The ultra-high molecular weight PE used RCH 1000 from Herster, Germany.
The maleic anhydride grafted PE is prepared by the following method:
to 100 parts by weight of PE-1 (LLDPE produced by Mitsui chemical Co., Ltd.), was dry-blended a solution prepared by dissolving 1 part by weight of maleic anhydride (produced by Wako pure chemical industries, Ltd., hereinafter abbreviated as MAH) and 0.06 part by weight of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane (produced by Nippon oil & fat Co., Ltd., trade name: PERHEXA 25B) in acetone. Then, the mixture was extruded at a screw rotation speed of 200rpm and an extrusion amount of 100 g/min at a resin temperature of 250 ℃ using a twin-screw kneader to obtain a maleic acid-modified polyethylene (hereinafter abbreviated as MAH-PE). The resulting MAH-PE was dissolved in xylene, and purified by reprecipitation in acetone, whereby the graft amount of maleic anhydride was measured to be 0.96 wt%.
The glass fiber adopts T-glass fiber of Nittobo and chopped fiber of 5 mm.
SiO2 particles:
particle combination 1: the average particle size of the large particles is 20 microns, the average particle size of the small particles is 0.1 micron, and the weight ratio is 1: 1;
particle combination 2: the average particle size of the large particles is 20 microns, the average particle size of the small particles is 0.1 micron, and the weight ratio is 2: 1;
particle combination 3: the average particle size of the large particles is 30 microns, the average particle size of the small particles is 0.05 microns, and the weight ratio is 1: 1;
particle combination 4: the average particle size of the large particles is 30 microns, the average particle size of the small particles is 0.1 micron, and the weight ratio is 1: 2;
particle combination 5: the average particle size of the large particles is 40 microns, the average particle size of the small particles is 0.1 micron, and the weight ratio is 1: 1;
particle combination 6: the average particle size of the large particles is 40 microns, the average particle size of the small particles is 0.05 microns, and the weight ratio is 2: 1;
particle combination 7: the average particle size of the large particles is 5 microns, the average particle size of the small particles is 1 micron, and the weight ratio is 1: 1;
particle combination 8: the average particle size of the large particles is 5 microns, the average particle size of the small particles is 0.05 microns, and the weight ratio is 1: 1;
KH 550 is used as the silane coupling agent.
The antioxidant is a mixture of 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenylyl diphosphite in a weight ratio of 1: 1.
The lubricant may be calcium stearate.
The flame retardant is magnesium hydroxide with the size of 2500 meshes.
The amounts by weight of the individual components and the properties of the products of examples 1 to 5 and comparative examples 1 to 5 are given in Table 1.
The PA6 composition particles were prepared by the following method:
accurately weighing the components, (1) uniformly mixing the silica particles with the particle sizes, the glass fibers and the silane coupling agent, ultrasonically dispersing for 30min, adding ethanol and water, stirring in an aqueous solution at 60 ℃ for 2h, adjusting the pH value to 9.5 by using ammonia water, cooling, filtering, washing, and drying at 100 ℃ to obtain the silica particles and the glass fibers with the surface modified by the silane coupling agent;
(2) PA6, the silane coupling agent surface modified silica particles obtained in the step (1), a flame retardant, ultra-high molecular weight PE, maleic anhydride grafted PE, an antioxidant and a lubricant are mixed at high speed for 60 minutes at 1000 r/min to obtain a premix;
(3) and (3) feeding the premix obtained in the step (2) into a double-screw extruder, adding silane coupling agent surface modified glass fiber at a special glass fiber port of the double-screw extruder, wherein the temperature of a screw zone is 200 ℃, 210 ℃,220 ℃,230 ℃, and 250 ℃ and the screw rotating speed is 400 rpm, and extruding and granulating to obtain the reinforced modified flame-retardant PA6 particles.
Performance testing
The impact strength of the notch of the simply supported beam is carried out according to ISO 179, and the test equipment is a Germany Zwick B5102.202 impact tester; the tensile property test is carried out according to ISO 527, the test equipment is a German Zwick Z010 electronic tensile machine, and the tensile speed is 50 mm/min; the bending performance test was performed according to ISO178, the test equipment being a Zwick Z010 electronic tensile machine, the span being 64mm and the speed being 2 mm/min. The flame retardant property test adopts UL 94 standard.
Measurement of volume shrinkage: the size of the obtained plate was injection-molded using a mold having a thickness of 3mm and sides of 130mm and the shrinkage factor was measured.
TABLE 1
It can be seen from the above examples and comparative examples that the composition of the present invention has improved tensile strength and bending strength due to the combination of ultra-high molecular weight polyethylene and glass fiber, and has reduced volume shrinkage, better dimensional stability and improved impact resistance due to the filling of silica particles with different sizes and particle diameters. The tensile strength and the bending strength of the composition without the ultra-high molecular weight polyethylene or the glass fiber are obviously reduced, and the volume shrinkage rate is larger and the impact resistance is reduced without the composition filled with the silicon dioxide with the particle size in a specific particle size range. The flame retardant property of the composition added with the flame retardant is obviously improved, and the size stabilizer, the impact resistance and the tensile property of the composition can be maintained.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (9)
1. The reinforced modified flame-retardant PA6 composition is characterized by comprising the following components in parts by weight: PA 6: 50-80 parts; ultra-high molecular weight PE: 10-20 parts; maleic anhydride grafted PE: 1-10 parts; glass fiber: 10-30 parts; SiO with large grain size2: 5-10 parts; small particle size SiO2: 5-10 parts; silane coupling agent: 0.5-3 parts; antioxidant: 0.5-2 parts; lubricant: 0.5-2 parts; flame retardant: 10-20 parts of SiO with large grain diameter2Using particles with average particle size of 10-40 μm, SiO with small particle size2The weight ratio of particles with the average particle diameter of 0.05-0.1 μm to particles with the average particle diameter of 1-2:2-1 is adopted.
2. The composition of claim 1, wherein: wherein PA6 adopts polymer chip with relative viscosity more than 3.0, and its dosage is 60-70 parts.
3. The composition of claim 1, wherein: the ultra-high molecular weight PE adopts a product with the weight-average molecular weight of 200-600 ten thousand, and the dosage of the product is 10-15 parts.
4. The composition of claim 1, wherein: the glass fibers are in the form of chopped glass of 0.2mm to 20mm length or in the form of continuous filament fibers, in an amount of 15-20 parts.
5. The composition of claim 1, wherein: the antioxidant is a composite antioxidant consisting of hindered phenol antioxidant and phosphite antioxidant, wherein the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 1.
6. The composition of claim 1, wherein: the silane coupling agent is a silane coupling agent having an amino group or an epoxy group.
7. The composition of claim 1, wherein: the lubricant is calcium stearate, polyethylene wax or ethylene bis stearamide or a mixture of the calcium stearate, the polyethylene wax and the ethylene bis stearamide.
8. The composition of claim 1, wherein: the flame retardant is aluminum hydroxide or magnesium hydroxide.
9. The process for preparing the reinforced modified flame retardant PA6 composition according to claim 1, comprising the steps of:
(1) respectively and uniformly mixing silica particles with large and small particle sizes and glass fibers with a silane coupling agent, performing ultrasonic dispersion for 10-30 min, adding ethanol and water, stirring in an aqueous solution at the temperature of 60-80 ℃ for 1-2 h, adjusting the pH value to 8.5-9.5 by using ammonia water, cooling, filtering, washing, and drying at the temperature of 100-120 ℃ to obtain silica particles and glass fibers with surface modified by the silane coupling agent;
(2) PA6, the silane coupling agent surface modified silica particles obtained in the step (1), a flame retardant, ultra-high molecular weight PE, maleic anhydride grafted PE, an antioxidant and a lubricant are mixed at high speed of 1000-2000 rpm for 20-60 minutes to obtain a premix;
(3) and (3) feeding the premix obtained in the step (2) into a double-screw extruder, adding silane coupling agent surface modified glass fiber at a special glass fiber port of the double-screw extruder, wherein the temperature of a screw zone is 200-260 ℃, the rotating speed of the screw is 300-600 rpm, and extruding and granulating to obtain the reinforced modified flame-retardant PA6 particles.
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| CN102020783A (en) * | 2010-10-25 | 2011-04-20 | 武汉大学 | Selection method of fillers for advanced encapsulating material |
| CN103160112A (en) * | 2011-12-08 | 2013-06-19 | 合肥杰事杰新材料股份有限公司 | High wear-resistant high-strength nylon 6 complex and preparation method thereof |
| CN105131536A (en) * | 2015-08-31 | 2015-12-09 | 宁波海雨新材料科技有限公司 | High-abrasion-resistant TPEE |
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| CN1858116A (en) * | 2006-05-29 | 2006-11-08 | 常熟市日之升塑胶制造厂 | Glass microfiber and super micro nano particle reinforced tenacity increased nylon composite material and its preparing method |
| CN102020783A (en) * | 2010-10-25 | 2011-04-20 | 武汉大学 | Selection method of fillers for advanced encapsulating material |
| CN103160112A (en) * | 2011-12-08 | 2013-06-19 | 合肥杰事杰新材料股份有限公司 | High wear-resistant high-strength nylon 6 complex and preparation method thereof |
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