CN107254164A - One kind enhancing modified Pa 6 composition - Google Patents

One kind enhancing modified Pa 6 composition Download PDF

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Publication number
CN107254164A
CN107254164A CN201710541671.2A CN201710541671A CN107254164A CN 107254164 A CN107254164 A CN 107254164A CN 201710541671 A CN201710541671 A CN 201710541671A CN 107254164 A CN107254164 A CN 107254164A
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Prior art keywords
parts
composition
antioxidant
silane coupler
particle
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CN201710541671.2A
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Chinese (zh)
Inventor
毛秋娣
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Ningbo Best Plastic Technology Co Ltd
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Ningbo Best Plastic Technology Co Ltd
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Priority to CN201710541671.2A priority Critical patent/CN107254164A/en
Publication of CN107254164A publication Critical patent/CN107254164A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/004Additives being defined by their length
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/068Ultra high molecular weight polyethylene

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses one kind enhancing modified Pa 6 composition and preparation method thereof, 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;The product prepared by said composition has improved dimensional stability, tensile property, impact resistance etc..

Description

One kind enhancing modified Pa 6 composition
Technical field
The invention belongs to technical field of polymer materials, and in particular to one kind enhancing modified Pa 6 composition.
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.
SiO2 is one of ultra tiny New Inorganic Materials of extremely important high-tech, because its specific surface area is big, superficial attractive forces By force, surface can be big, and chemical purity is high, dispersive property is good, has special performance in terms of thermal resistance, resistance, 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, easily Warpage is produced, dimensional stability is not high, and to notch sensitive, shock resistance and tensile property are to be improved.Accordingly, it would be desirable to right It is further modified, to meet application request.
The content of the invention
Strengthen modified Pa 6 composition it is an object of the invention to provide one kind, by using specified particle diameter group in composition Close silica filler so that composition is while with the performance such as heat-resisting, chemicals-resistant, wear-resisting, with improved size Stability, tensile property, impact resistance etc..
Technical scheme is as follows:
One kind enhancing modified Pa 6 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;PA6 uses relative viscosity For more than 3.0 polymer chips, the equal of domestic and international producer is used, such as German BASF, Mitsubishi chemistry, Japanese space The Products such as the emerging production in portion;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.
The present invention also provides a kind of preparation method of enhancing modified Pa 6 composition, 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 of the silane coupler surface obtained in PA6, step (1) modification, super high molecular weight PE, maleic anhydride grafting PE, antioxidant, lubricant were premixed in 1000~2000 revs/min of lower mixed at high speed 20~60 minutes Material;
(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 PA6 particles 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.
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.
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 of the silane coupler surface obtained in PA6, step (1) modification, super high 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 PA6 particles.
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.
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.
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 (8)

1. one kind enhancing modified Pa 6 composition, it is characterised in that be made up of the component of following parts by weight:PA6:50-80 parts;It is super HMW 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, wherein, big grain Footpath 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, and two The part by weight of person is 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. a kind of preparation method of enhancing modified Pa 6 composition 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) by the silicon dioxide granule, super high molecular weight PE, horse of the silane coupler surface obtained in PA6, step (1) modification Maleic anhydride grafted PE, antioxidant, lubricant obtained premix in 1000~2000 revs/min of lower mixed at high speed 20~60 minutes;
(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 PA6 particles must be strengthened.
CN201710541671.2A 2017-07-05 2017-07-05 One kind enhancing modified Pa 6 composition Pending CN107254164A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107815746A (en) * 2017-11-14 2018-03-20 天津长芦海晶集团有限公司 The preparation method of high-hydroscopicity easy dyeing modified polyamine fibre
CN110964312A (en) * 2018-09-28 2020-04-07 句容市飞达箱包有限公司 Composite material with high wear resistance and application thereof
CN110964313A (en) * 2018-09-28 2020-04-07 句容市飞达箱包有限公司 Preparation method of composite material with high wear resistance
CN115651396A (en) * 2022-10-13 2023-01-31 金发科技股份有限公司 Polyamide resin composite material and preparation method and application thereof
CN116514436A (en) * 2023-04-28 2023-08-01 深圳市砼科院有限公司 Crack resistance reinforcing agent for concrete and preparation method thereof

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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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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107815746A (en) * 2017-11-14 2018-03-20 天津长芦海晶集团有限公司 The preparation method of high-hydroscopicity easy dyeing modified polyamine fibre
CN110964312A (en) * 2018-09-28 2020-04-07 句容市飞达箱包有限公司 Composite material with high wear resistance and application thereof
CN110964313A (en) * 2018-09-28 2020-04-07 句容市飞达箱包有限公司 Preparation method of composite material with high wear resistance
CN115651396A (en) * 2022-10-13 2023-01-31 金发科技股份有限公司 Polyamide resin composite material and preparation method and application thereof
CN115651396B (en) * 2022-10-13 2023-09-26 金发科技股份有限公司 Polyamide resin composite material and preparation method and application thereof
CN116514436A (en) * 2023-04-28 2023-08-01 深圳市砼科院有限公司 Crack resistance reinforcing agent for concrete and preparation method thereof

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Application publication date: 20171017