CN107099135A - It is a kind of to strengthen modified flame-proof PA 6 composition - Google Patents
It is a kind of to strengthen modified flame-proof PA 6 composition Download PDFInfo
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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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- C—CHEMISTRY; METALLURGY
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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
Strengthen modified flame-proof PA 6 composition and preparation method thereof the invention discloses a kind of, composition is made up of the component of following parts by weight：PA6：50 80 parts；Super high molecular weight PE：10 20 parts；Maleic anhydride is grafted PE：1 10 parts；Glass fibre：10 30 parts；Big particle diameter SiO2：5 10 parts；Small particle SiO2：5 10 parts；Silane coupler：0.5 3 parts；Antioxidant：0.5 2 parts；Lubricant：0.5 2 parts；Fire retardant：10 20 parts；The product prepared by said composition has an improved dimensional stability, tensile property, impact resistance etc., while having the fire resistance of lifting.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to the flame-proof PA 6 composition that a kind of enhancing is modified.
Background technology
Polyamide is commonly referred to as nylon, and it is the polymer containing amide group repeat unit in polymer macromolecule chain
General name, is mainly obtained by binary acid and diamine or amino acid lactams through polycondensation or autohemagglutination, is to develop earliest, usage amount maximum
Thermoplastic engineering plastic.Polyamide 6 has the advantages that mechanical strength is high, fusing point is high, wear-resistance and oil-resistance, be widely used in automobile,
The fields such as electromechanics, electronics, weaving, household electrical appliances.
Micro-nano SiO2 is one of ultra tiny New Inorganic Materials of extremely important high-tech, because its specific surface area is big, surface
Absorption affinity is strong, and surface can be big, and chemical purity is high, dispersive property is good, is widely used as the filler of resin matrix.
Ultra-high molecular weight polyethylene is a kind of thermoplastic engineering plastic with Good All-around Property, and mean molecule quantity is about
1500000~8,000,000, because molecular weight is high and have the unrivaled excellent impact resistance of other plastics, wear-resistant, self lubricity,
The performance such as resistant to chemical etching.
Polyamide 6 is due to containing substantial amounts of polar group, causing its hygroscopic, while shaping post-shrinkage ratio is larger, size
Stability is not high, and to notch sensitive, fire resistance, shock resistance and tensile property are to be improved.
The fire retardant that polyamide is commonly used at present mainly has brominated Polystyrene, deca-BDE, TDE, burnt phosphorus
Sour melamine, red phosphorus etc..But these fire retardants more or less have expensive, processing difficulties, injection-molded item surface is thick
It is rough, the shortcomings of color is not good.With environmental requirement more and more higher, some fire retardants such as deca-BDE may be disabled, resistance
Combustible material has to comply with the ROHS instructions of European Union.
Accordingly, it would be desirable to be further modified to polyamide, so as to make its product with good dimensional stability,
While impact resistance, tensile property, with excellent fire resistance, to meet application request.
The content of the invention
Strengthen modified flame-proof PA 6 composition it is an object of the invention to provide a kind of, it is specific by being used in composition
Mechanical fraction silica filler and reinforcing fiber and inorganic no-halogen fire retardant so that composition is with heat-resisting, chemically-resistant
While the performance such as product, wear-resisting, with improved dimensional stability, tensile property, impact resistance and anti-flammability etc..
Technical scheme is as follows：
It is a kind of to strengthen modified flame-proof PA 6 composition, it is made up of the component of following parts by weight：PA6：50-80 parts；Superelevation point
Son amount PE：10-20 parts；Maleic anhydride is grafted PE：1-10 parts；Glass fibre：10-30 parts；Big particle diameter SiO2：5-10 parts；Granule
Footpath SiO2：5-10 parts；Silane coupler：0.5-3 parts；Antioxidant：0.5-2 parts；Lubricant：0.5-2 parts；Fire retardant：10-20
Part；PA6 uses relative viscosity for more than 3.0 polymer chips, and the equal of domestic and international producer use, such as German BASF,
The Products such as Mitsubishi chemistry, Ube Industries Ltd.；Its consumption is preferably 60-70 parts.
Super high molecular weight PE uses weight average molecular weight for 200-600 ten thousand product, can be using German Hirst company, Japan
The product of three well petrochemistry, domestic Qilu Petrochemical；Its consumption is preferably 10-15 parts.
Maleic anhydride grafting PE can use commercially available prod or self-control；Its consumption is preferably 5-8 parts.
Glass fibre uses high strength glass fiber, and instantiation is to have 910 or 995 chis from OwensCorning
Very little S- glass fibres, the T- glass fibres from Nittobo, the HiPertex from 3B, come from
SinomaJinjingFiberglass HS4- glass fibres, the R- glass fibres from Vetrotex and the S- from AGY
1 and S-2- glass fibres.Glass fibre can be in the form of chopped fiber, preferably with 0.2mm to the staple glass of 20mm length shape
Formula, or in the form of continuous filament fiber；Its consumption is preferably 15-20 parts.
Big particle diameter SiO2 uses average grain diameter for 10-40 μm of particle, and small particle SiO2 uses average grain diameter for 0.05-
0.1 μm of particle, both part by weight are 1-2:2-1, preferably 1:1.
Silane coupler uses the silane coupler with amino or epoxy radicals, such as KH 550, KH 560, KH 602.
Antioxidant is the composite antioxidant that Hinered phenols antioxidant is constituted with phosphite ester kind antioxidant, wherein Hinered phenols
The mass ratio of antioxidant and phosphite ester kind antioxidant is 1: 1；The Hinered phenols antioxidant is selected from 1,3,5- trimethyls -2,4,
6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene, 2,6- di-t-butyl -4- methyl-phenols, N, (3, the 5- bis- tertiary fourths of N '-two
Base -4- hydroxy phenylpropionyls amine), 2,2 '-bis- (4- methyl-6-terts butyl-phenol) methane, 2,2 '-bis- (tertiary fourths of 4- ethyls -6-
Base-phenol) one or more in methane, the phosphite ester kind antioxidant is selected from 2,2 '-ethylenebis (4,6- di-t-butyls
Phenyl) fluorophosphite, four (2,4- di-tert-butyl-phenyls) -4, the one or more in 4 '-xenyl bis-phosphite.
Lubricant can be using calcium stearate, Tissuemat E or ethylene bis stearamide or the mixture being made up of them.
Fire retardant uses aluminium hydroxide or magnesium hydroxide, is preferably sized between 800-5000 mesh.Due to magnesium hydroxide, hydrogen
Aluminum oxide can absorb a large amount of latent heat when being thermally decomposed, and discharge moisture, reduce the actual temperature of material surface flame,
It is that depolymerization slows down for low molecular speed, reduces the generation of combustible, the steam discharged reduces surface
Oxygen concentration, is difficult to surface combustion；Magnesium hydroxide, aluminium hydroxide can also postpone the ignitor firing time of material, and reduce material
The effusion speed of the raw smoke of material and flue gas.The magnesia or aluminum oxide of generation simultaneously can also absorb the material such as free radical, carbon,
Further increase its fire resistance.Meanwhile, aluminium hydroxide or magnesium hydroxide do not contain halogen, and the product containing it is burned
Also the poisonous and harmful substances such as dioxin will not be produced in journey, therefore it has good environmental-protecting performance.
The present invention also provides a kind of preparation method for the flame-proof PA 6 composition for strengthening modification, comprises the following steps：
(1) silicon dioxide granule, glass fibre, silane coupler of big small particle are well mixed, through ultrasonic disperse 10
Second alcohol and water is added after~30min, 1~2h is stirred in 60~80 DEG C of the aqueous solution, then with ammoniacal liquor adjust pH value to 8.5~
9.5, cooling, filtering, washing after 100~120 DEG C of dryings, obtain the silicon dioxide granule and glass of silane coupler surface modification
Glass fiber；
(2) by the silicon dioxide granule, fire retardant, superelevation of the silane coupler surface obtained in PA6, step (1) modification
Molecular weight PE, maleic anhydride grafting PE, antioxidant, lubricant were obtained in 1000~2000 revs/min of lower mixed at high speed 20~60 minutes
To premix；
(3) premix for obtaining step (2) is fed in double screw extruder, fine in the special glass of double screw extruder
The glass fibre that silane coupler surface is modified is added at Wei Kou, the wherein temperature in screw rod area is 200~260 DEG C, screw speed
For 300~600 revs/min, extruding pelletization, you can modified flame-proof PA 6 particle must be strengthened.
In the present invention, strengthen jointly with glass fibre by using ultra-high molecular weight polyethylene, PA6 combinations greatly improved
The mechanical property of thing, such as tensile strength.Simultaneously in the composition of the present invention, due to having used the different filling of big small particle
Particle silica, when being dispersed in polyamide resin resin system, big particle can form big backbone network, and small particles then have
Preferably dispersiveness, can be distributed to the regional area that some big particles are difficult to reach, such as crooked position, and then cause various
Particle can dispersed filler well in the base, effectively reduce the cubical contraction after formed product and anti-notch shock
Performance.Inorganic combustion inhibitor is used simultaneously, the fire resistance of composition is effectively increased, and meets the requirement such as environmental protection.
Embodiment
Technical scheme is further detailed and described below by way of embodiment.
PA6 use relative viscosity for more than 3.0 polymer chips, using German BASF product, Ultramid B
35, relative viscosity 3.3, number-average molecular weight 24,000.
Super high molecular weight PE uses the RCH 1000 of German Hirst company.
Maleic anhydride is grafted PE, adopts and is made with the following method：
Into the 100 parts by weight PE-1 LLDPE of production (Mitsui Chemicals society), it is dry-mixed add by 1 parts by weight maleic anhydride (and
Guang Chun medicines society produces, hereinafter simply referred to as MAH) and 0.06 parts by weight 2,5- dimethyl -2,5- bis(t-butylperoxy) hexane (days
This grease society produces, trade name PERHEXA 25B) it is dissolved in the solution of acetone.Then using twin screw compounder in resin temperature
At 250 DEG C of degree, extruded within 100g/ minutes with screw speed 200rpm, extrusion capacity, obtain maleic acid modified polyethylene (below
Referred to as MAH-PE).Obtained MAH-PE is dissolved in dimethylbenzene, reprecipitation is refined in acetone, determines Malaysia
The grafting amount of acid anhydrides is 0.96 weight %.
Glass fibre uses Nittobo T- glass fibres, 5mm chopped strand.
SiO2 particles：
Particle combinations 1：The average grain diameter of big particle is 20 microns, and the average grain diameter of small particles is 0.1 micron, part by weight
For 1：1；
Particle combinations 2：The average grain diameter of big particle is 20 microns, and the average grain diameter of small particles is 0.1 micron, part by weight
For 2：1；
Particle combinations 3：The average grain diameter of big particle is 30 microns, and the average grain diameter of small particles is 0.05 micron, weight ratio
Example is 1：1；
Particle combinations 4：The average grain diameter of big particle is 30 microns, and the average grain diameter of small particles is 0.1 micron, part by weight
For 1：2；
Particle combinations 5：The average grain diameter of big particle is 40 microns, and the average grain diameter of small particles is 0.1 micron, part by weight
For 1：1；
Particle combinations 6：The average grain diameter of big particle is 40 microns, and the average grain diameter of small particles is 0.05 micron, weight ratio
Example is 2：1；
Particle combinations 7：The average grain diameter of big particle is 5 microns, and the average grain diameter of small particles is 1 micron, and part by weight is
1：1；
Particle combinations 8：The average grain diameter of big particle is 5 microns, and the average grain diameter of small particles is 0.05 micron, part by weight
For 1：1；
Silane coupler uses KH 550.
Antioxidant uses 1,3,5- trimethyls -2,4, (3, the 5- di-tert-butyl-4-hydroxyl benzyl) benzene of 6- tri- and four (2,4- bis-
Tert-butyl-phenyl) -4,4 '-xenyl bis-phosphite is with 1:Mixture of 1 weight than formation.
Lubricant can use calcium stearate.
Fire retardant uses magnesium hydroxide, and size is 2500 mesh.
Embodiment 1-5 and comparative example 1-5 each components weight consumption and properties of product are shown in Table 1.
PA6 composition particles are adopted to be prepared with the following method：
Accurately weigh after each component, (1) mixes the silicon dioxide granule, glass fibre, silane coupler of big small particle
Uniformly, second alcohol and water is added after ultrasonic disperse 30min, 2h is stirred in 60 DEG C of the aqueous solution, then arrived with ammoniacal liquor regulation pH value
9.5, cooling, filtering, washing after 100 DEG C of dryings, obtain the silicon dioxide granule and glass fibers of silane coupler surface modification
Dimension；
(2) by the silicon dioxide granule, fire retardant, superelevation of the silane coupler surface obtained in PA6, step (1) modification
Molecular weight PE, maleic anhydride grafting PE, antioxidant, lubricant obtained premix in 1000 revs/min of lower mixed at high speed 60 minutes；
(3) premix for obtaining step (2) is fed in double screw extruder, fine in the special glass of double screw extruder
The glass fibre that silane coupler surface is modified is added at Wei Kou, the temperature in wherein screw rod area is respectively 200 DEG C, 210 DEG C, 220
DEG C, 230 DEG C, 250 DEG C of screw speeds are 400 revs/min, extruding pelletization, you can must strengthen modified flame-proof PA 6 particle.
Performance test
Simply supported beam notch impact strength is performed by ISO 179, and test equipment is Germany's Zwick B5102.202 impact tests
Machine；Tensile property test is performed by ISO 527, and test equipment is Germany's Zwick Z010 electronic tensile machines, and draw speed is
50mm/min；The test of bending property is performed by ISO178, and test equipment is Zwick Z010 electronic tensile machines, and span is
64mm, speed is 2mm/min.Fire resistance test uses the standards of UL 94.
Cubical contraction is measured：Using the flat board obtained with 3mm thickness and the mold injection of 130mm sides size simultaneously
Determine shrinkage factor.
Table 1
By above-described embodiment and comparative example, composition of the invention as a result of ultra-high molecular weight polyethylene with
The combination of glass fibre so that its product has the tensile strength and bending strength improved, and as a result of big small particle
Different silicon dioxide granules are filled so that product, which has, reduces cubical contraction, more preferable dimensional stability, raising
Shock resistance.Without ultra-high molecular weight polyethylene or the composition of glass fibre, its tensile strength and bending strength are obvious
Reduction, without the silica-filled composition of the big small particle of specified particle diameter scope, its cubical contraction is larger, impact resistance
Can reduction.Composition for the addition of fire retardant, its fire resistance is significantly improved, while its dimensionally stable agent, anti-impact
Hitting property and tensile property can be maintained.
The foregoing is only a preferred embodiment of the present invention, therefore can not limit the scope that the present invention is implemented according to this, i.e.,
The equivalent changes and modifications made according to the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.
Claims (9)
1. a kind of strengthen modified flame-proof PA 6 composition, it is characterised in that is made up of the component of following parts by weight：PA6：50-80
Part；Super high molecular weight PE：10-20 parts；Maleic anhydride is grafted PE：1-10 parts；Glass fibre：10-30 parts；Big particle diameter SiO2：5-
10 parts；Small particle SiO2：5-10 parts；Silane coupler：0.5-3 parts；Antioxidant：0.5-2 parts；Lubricant：0.5-2 parts；It is fire-retardant
Agent：10-20 parts, wherein, big particle diameter SiO2 uses average grain diameter for 10-40 μm of particle, and small particle SiO2 uses average grain diameter
For 0.05-0.1 μm of particle, both part by weight are 1-2:2-1.
2. composition as claimed in claim 1, it is characterised in that：Wherein PA6 use relative viscosity for more than 3.0 polymer
Section, its consumption is preferably 60-70 parts.
3. composition as claimed in claim 1, it is characterised in that：Super high molecular weight PE uses weight average molecular weight for 200-600
Ten thousand product, its consumption is preferably 10-15 parts.
4. composition as claimed in claim 1, it is characterised in that：Glass fibre can in the form of chopped fiber, preferably with
0.2mm to the staple glass of 20mm length form, or in the form of continuous filament fiber；Its consumption is preferably 15-20 parts.
5. composition as claimed in claim 1, it is characterised in that：Antioxidant is that Hinered phenols antioxidant resists with phosphorous acid esters
The composite antioxidant of oxygen agent composition, the wherein mass ratio of Hinered phenols antioxidant and phosphite ester kind antioxidant are 1: 1.
6. composition as claimed in claim 1, it is characterised in that：Silane coupler uses the silane with amino or epoxy radicals
Coupling agent.
7. composition as claimed in claim 1, it is characterised in that：Lubricant is double using calcium stearate, Tissuemat E or ethylene
Stearmide or the mixture being made up of them.
8. composition as claimed in claim 1, it is characterised in that：Fire retardant uses aluminium hydroxide or magnesium hydroxide.
9. a kind of preparation method of flame-proof PA 6 composition for strengthening modification as claimed in claim 1, comprises the following steps：
(1) silicon dioxide granule, glass fibre, silane coupler of big small particle are well mixed, through ultrasonic disperse 10~
Second alcohol and water is added after 30min, 1~2h is stirred in 60~80 DEG C of the aqueous solution, then pH value is adjusted to 8.5~9.5 with ammoniacal liquor,
Cooling, filtering, washing, after 100~120 DEG C of dryings, obtain the silicon dioxide granule and glass fibers of silane coupler surface modification
Dimension；
(2) silicon dioxide granule, fire retardant, the supra polymer being modified the silane coupler surface obtained in PA6, step (1)
PE, maleic anhydride grafting PE, antioxidant, lubricant are measured in 1000~2000 revs/min of lower mixed at high speed 20~60 minutes, obtains pre-
Batch mixing；
(3) premix for obtaining step (2) is fed in double screw extruder, in the special glass fiber mouthful of double screw extruder
The glass fibre that place addition silane coupler surface is modified, the wherein temperature in screw rod area is 200~260 DEG C, and screw speed is 300
~600 revs/min, extruding pelletization, you can modified fire retardant PA6 particles must be strengthened.
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Cited By (1)
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| CN115141482A (en) * | 2022-06-10 | 2022-10-04 | 昆山纳诺新材料科技有限公司 | Preparation method of low-cost environment-friendly heat-conducting plastic particles |
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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 |
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