CN104356640B - The preparation method of polyacrylate compound particle for nylon 6 low temperature toughening modifyings - Google Patents

The preparation method of polyacrylate compound particle for nylon 6 low temperature toughening modifyings Download PDF

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CN104356640B
CN104356640B CN201410631588.0A CN201410631588A CN104356640B CN 104356640 B CN104356640 B CN 104356640B CN 201410631588 A CN201410631588 A CN 201410631588A CN 104356640 B CN104356640 B CN 104356640B
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emulsion
nylon
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CN104356640A (en
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李国华
马静
张广林
姚艳梅
何连岐
瞿雄伟
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HEBEI EURASIAN TUBE INDUSTRY CO., LTD.
Hebei University of Technology
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HEBEI EURASIAN TUBE INDUSTRY Co Ltd
Hebei University of Technology
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/76—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Mechanical Engineering (AREA)
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  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The present invention is a kind of preparation method of nylon 6 low temperature toughening modifyings polyacrylate compound particle, and the method comprises the following steps: a, the surface modification of nano silicon; B, the preparation of seed emulsion; C, nuclear layer monomer pre-emulsification; D, shell monomers pre-emulsification; E, the preparation of initiator solution; F, the preparation of polyacrylate compound particle: obtain polyacrylate dispersion, freezing breakdown of emulsion, by washing, suction filtration, after vacuum drying, obtains the powder of polyacrylate compound particle. The seed using in the present invention is the nano silicon of surface through silane coupler modified mistake, in the time reacting with the acrylate monomer of stratum nucleare, graft reaction easily occurs, thereby makes the interface binding power between inorganic-organic firm; The soft monomer polymer using is the different monooctyl ester of polyacrylic acid, and its glass transition temperature, far below room temperature, can keep good elasticity at low temperatures, thereby improves the low-temperature flexibility of nylon 6.

Description

The preparation method of polyacrylate compound particle for nylon 6 low temperature toughening modifyings
Technical field
The invention belongs to engineering plastic modification field, relate to the preparation of nylon 6 low temperature toughening modifyings polyacrylate compound particleMethod.
Background introduction
Nylon 6 is the very regular linear molecules of structure, contains amido link in macromolecular chain, can form hydrogen bond. It hasWear-resisting, the good characteristic such as intensity good, corrosion-resistant, self-lubricating, be widely used in machinery, electronic apparatus, automobile and chemical building materialEtc. industry. But nylon 6 also exists some shortcomings, as lower in notched Izod impact strength, dry state and low temperature impact properties are poor etc., toughProperty deficiency makes it apply and be restricted as engineering plastics. Therefore, improve the cryomechanics of nylon 6 engineering plasticCan, expand its application tool and be of great significance. The flat just grade in Shandong is by three of nylon 6, calcium carbonate, maleic anhydride graftUnit EP rubbers and compatilizer etc. join melting in double screw extruder, then the side that glass fibre is placed in double screw extruder is fedMaterial mouthful, compound with above-mentioned material melting, last extruding pelletization obtains material modified. Result shows: the breach of nylon 6 after modificationImpact strength improved 1 times [Lu Pingcai, Zhao Yinzhu. a kind of modified nylon 6 material and preparation method thereof [P]. China invention is speciallyProfit, CN102850784.2013-01-02]. Although this method increases the toughness of nylon 6, does not improve Buddhist nunThe low-temperature flexibility of dragon 6. Yang Guisheng etc. first utilize high-speed mixer to prepare cross-linked ethylene/alpha olefin copolymer, then by itself and Buddhist nunDragon 6, through double screw extruder melt blending, obtains nylon 6 toughening materials after last extruding pelletization. Result shows: at-30 DEG C,The notched Izod impact strength of nylon 6 improved 1 times [Yang Guisheng, Yu Fei. a kind of polyamide toughening material and preparation method thereof [P]. inState's patent of invention, CN103951969.2014-07-30]. The drawback of this method is the preparation process that is not easy to control flexibilizerAnd dispersed in matrix resin of flexibilizer, the stability of modified effect is restricted. Compound particle be taking inorganic particulate asSeed, crosslinked elastomer (soft monomer polymer) is stratum nucleare, have polymer (the hard monomer polymerization of higher glass transition temperatureThing) be the polymer of shell. Adopt shell surface-functionalized compound particle, because itself and nylon-6 matrix body have good chemistry increasingCapacitive, seed adopts inorganic particulate nano silica, and stratum nucleare adopts the different monooctyl ester elastomer of polyacrylic acid, its glass transition temperatureDegree is far below room temperature, and shell is the copolymer of polymethyl methacrylate and function monomer. By this compound particle and nylon 6 worksAfter engineering plastics melt blending, can significantly improve the low-temperature impact toughness of nylon 6, keep the suitable hot strength of blend simultaneously.
Summary of the invention
The technical problem to be solved in the present invention is: the system that a kind of nylon 6 low temperature toughening modifyings polyacrylate compound particle is providedPreparation Method. First adopt seeded emulsion polymerization technology, the inorganic particulate taking after surface treatment: nano silicon is seed, withPolyacrylate monomer is stratum nucleare, taking polyacrylate monomer and acrylic acid series function monomer copolymer as shell, at relevant breastUnder the effect of agent and crosslinking agent, prepare complex emulsions, then by this complex emulsions through freezing breakdown of emulsion, washing and vacuum dryingAfter, obtain nylon 6 low temperature toughening modifying polyacrylate compound particles. By this compound particle and nylon 6 melt blendings, canThe low temperature notched impact strength of nylon 6 is improved to 6.82 times at-30 DEG C.
Technical scheme of the present invention is:
A preparation method for polyacrylate compound particle for nylon 6 low temperature toughening modifyings, comprises the following steps:
A, the surface modification of nano silicon: nano grade silica particles is scattered in absolute ethyl alcohol, is mixed with mass fractionBe 50% nano silicon absolute ethyl alcohol dispersion liquid, ultrasonic processing 20～40min; Taking quality is SiO 2 powder quality5% silane coupler, is scattered in absolute ethyl alcohol, is mixed with mass fraction and is 10% coupling agent absolute ethyl alcohol dispersion liquid, stirsMix lower to watery hydrochloric acid adjusting pH value to 4; Above-mentioned whole nano silicon absolute ethyl alcohol dispersion liquids are added to logical condensed water and nitrogenReactor in, and 50 DEG C of stirred in water bath, then drip above-mentioned whole coupling agent absolute ethyl alcohol dispersion liquid, 60～120minDrip off, continue after insulation reaction 20～30h centrifugation; Wash centrifugal go out lower floor's paste, vacuum drying at 60 DEG C,Obtain the nano silica powder of surface modification;
B, the preparation of seed emulsion: the surface-treated nano silica powder that emulsifying agent, above-mentioned a step are obtained and go fromSub-water mixes, and stirs and ultrasonic 60min, obtains seed emulsion; Wherein, mass ratio is emulsifying agent: above-mentioned a step obtainsSurface-treated nano silica powder: deionized water=1:20:280;
C, nuclear layer monomer pre-emulsification: by crosslinking agent, stir after emulsifying agent and acrylate monomer mix, obtain nuclear layer monomer pre-Emulsion; Wherein, mass ratio is crosslinking agent: emulsifying agent: acrylate monomer=8～18:25:2000;
D, shell monomers pre-emulsification: emulsifying agent, acrylic ester monomer are mixed and the rear stirring of acrylic acid series function monomer mixing,Obtain shell monomers pre-emulsion; Wherein, quality is than emulsifying agent: acrylic ester monomer=1:50, acrylic acid series function listWeight is 0.5% of monomer gross mass, described monomer gross mass refer to the modified manometer silicon dioxide adding in b step quality,Acrylic ester monomer quality sum in acrylate monomer quality and d step in c step;
E, the preparation of initiator solution: stir after initator is mixed with mass ratio 11:1000 with deionized water, obtain initatorSolution I; After initator is mixed with mass ratio 4.3:1000 with deionized water, stir, obtain a initiator solution II, join altogetherMake 3 parts of identical initiator solution II, for subsequent use; Wherein, in initiator solution I and every part of initiator solution II, use go fromSub-water quality is identical;
F, the preparation of polyacrylate compound particle: to the logical nitrogen of the reactor that seed emulsion is housed in b step, and in returned coldUnder coagulating, stirring, be warming up to 75 ± 1 DEG C, after temperature constant, add initiator solution I, after 5min, start to drip c step and obtainThe nuclear layer monomer pre-emulsion arriving, and at the uniform velocity drip off in 100～150min; Then drip the shell pre-emulsification that d step obtainsLiquid, and at the uniform velocity drip off in 80～30min; In the time dripping nuclear layer monomer pre-emulsion and shell monomers pre-emulsion, every 60minAdd a initiator solution II, the initiator solution II of equivalent adds 3 times, and wherein initiator solution is disposable adding; ItRear insulation reaction 60min, then be down to room temperature, obtain polyacrylate dispersion; By the freezing breakdown of emulsion of the above-mentioned emulsion making; AfterThrough washing, suction filtration, after vacuum drying, obtain the powder of polyacrylate compound particle;
The wherein quality of modified manometer silicon dioxide in b step: acrylate monomer quality in c step: acrylate in d stepClass monomer mass=1:11～16:8～3, the gross mass of deionized water: monomer gross mass=9:10, the gross mass of described deionized water isRefer in b step in deionized water and e step the gross mass of whole deionized waters in initiator solution; Described monomer gross mass isRefer in the quality, c step of the modified manometer silicon dioxide adding in b step acrylic acid in acrylate monomer quality and d stepEsters monomer quality sum;
Described silane coupler is acryloxy propyl trimethoxy silicane;
Described b, c, the emulsifying agent in d step is dodecyl biphenyl sodium sulfonate;
In described c step, acrylate monomer is Isooctyl acrylate monomer, and in described d step, acrylic ester monomer is methylMethyl acrylate, acrylic acid series function monomer is methacrylic acid;
Described crosslinking agent is 1,6 hexanediyl ester;
Described initator is potassium peroxydisulfate;
The average grain diameter of described SiO 2 powder is 20～40nm.
A preparation method for polyacrylate compound particle/nylon 6 Blends, comprises the following steps:
Polyacrylate compound particle powder obtained above and nylon 6 are total to mass ratio 1:5 melting on double screw extruderMixed, extrude after pelletizing, vacuum drying injection mo(u)lding on injection machine.
The invention has the beneficial effects as follows: in the present invention taking the nano silicon inorganic particulate after surface treatment as seed, to gather thirdAlkene acid ester monomer is stratum nucleare, taking polyacrylate monomer and acrylic acid series function monomer copolymer as shell, passes through seed emulsionPolymerization is prepared complex emulsions, and this complex emulsions, after freezing breakdown of emulsion, washing and vacuum drying, is obtained to compound particle, logicalCrossing this compound particle modification of nylon 6 tools has the following advantages:
The glass transition temperature of the different monooctyl ester of 1 polyacrylic acid, far below room temperature, can keep good elasticity, at low temperatures to gatherIsooctyl acrylate monomer is composite emulsion particle prepared by stratum nucleare, can improve the low-temperature impact toughness of nylon 6;
The seed using in 2 the present invention is the nano silicon of surface through silane coupler modified mistake, because its surface exists band edge, in the time reacting with the acrylate monomer of stratum nucleare, easily there is graft reaction, thereby make inorganic-organic in the graft reaction point of two keysBetween interface binding power firm;
3 because nano silicon inorganic particulate has higher-strength and the feature such as thermally-stabilised, with surface through silane coupler modifiedThe nano silicon of crossing is seed, and by itself and polyacrylate is compound and and nylon 6 mixing, can make preparation modification Buddhist nunDragon 6 blends are in having higher low-temperature flexibility, and hot strength keeps high value;
The coated appropriately crosslinked elastomer stratum nucleare of polymethyl methacrylate shells layer of 4 rigidity, can promote compound particle at nylonDispersed in 6, keeps the stable of nylon 6 mixing physical performance;
5 at the surface and copolymerized methacrylic acid of compound particle, the amine in the carboxyl (COOH) in monomer structure and nylon-6 matrix body main chainBase (NH2) react, compound particle is bonded in nylon-6 matrix body effectively;
6 when stratum nucleare dosage of crosslinking agent be 0.5%, each constituent mass than (inorganic particulate: soft monomer polymer: hard monomer polymer) isWhen 1:15:4, the notched Izod impact strength of nylon 6 under-30 DEG C of low temperature improves at most, the notched Izod impact strength of nylon 6 Blends(30 DEG C) peak is 6.82 times of pure nylon 6.
Brief description of the drawings
Fig. 1 is that the conversion ratio of poly acrylate composite emulsion of embodiment 11 is with the change curve in reaction time.
Fig. 2 is that the latex particle size of poly acrylate composite emulsion of embodiment 11 is with the change curve in reaction time.
Fig. 3 is polyacrylate compound particle/nylon 6 Blends mechanical curves of different stratum nucleare dosage of crosslinking agent.
Fig. 4 is polyacrylate compound particle/nylon 6 Blends mechanical curves of different each constituent mass ratios.
Fig. 5 is the impact fracture surface SEM picture of pure nylon 6.
Fig. 6 is the impact fracture surface SEM photo of polyacrylate compound particle/nylon 6 Blends of embodiment 11.
Detailed description of the invention
Embodiment 1
A, the surface modification of nano silicon: the nano grade silica particles that is 20nm by 20g average grain diameter is scattered in 40gIn absolute ethyl alcohol, ultrasonic processing 30min. Take 1g acryloxy propyl trimethoxy silicane, and join fill 10g withoutIn the beaker of water-ethanol, be mixed with coupling agent absolute ethyl alcohol dispersion liquid, under stirring, reconcile pH value to 4 with watery hydrochloric acid. By nanometer twoSilica absolute ethyl alcohol dispersion liquid adds in the four-hole boiling flask of 500ml of the logical condensed water of reflux condenser and nitrogen, and at 50 DEG C of waterIn bath, stir, then drip coupling agent absolute ethyl alcohol dispersion liquid, 1.5h drips off, and continues after insulation reaction 24h centrifugal pointFrom. Lower floor's paste that centrifugation is gone out, with absolute ethanol washing, vacuum drying 24h at 60 DEG C, obtains surface and changesThe nano silica powder of property;
B, the preparation of seed emulsion: the surface that 0.5g emulsifying agent dodecyl biphenyl sodium sulfonate, 10g are obtained by a step changesProperty nano silica powder and 140g deionized water join in 500mL four-hole boiling flask, stir and ultrasonic 60min, make itBe uniformly dispersed, obtain seed emulsion;
C, nuclear layer monomer pre-emulsification: by 0.52g crosslinking agent 1,6 hexanediyl ester, 1.625g emulsifying agent dodecylBiphenyl sodium sulfonate, 130g Isooctyl acrylate monomer join in beaker, on magnetic stirring apparatus, stir, and obtain nuclear layer monomerPre-emulsion.
D, shell monomers pre-emulsification: by 1.2g emulsifying agent dodecyl biphenyl sodium sulfonate, 1g methacrylic acid, 60g methyl-propOlefin(e) acid methyl esters joins in beaker, on magnetic stirring apparatus, stirs, and obtains shell monomers pre-emulsion.
E, the preparation of initiator solution: 0.11g initator and 10g deionized water are joined in beaker, on magnetic stirring apparatusBe stirred to abundant dissolving, obtain initiator solution I; 0.043g initator and 10g deionized water are joined in beaker, at magneticOn power agitator, be stirred to abundant dissolving, obtain a initiator solution II, prepare 3 parts of identical initiator solution II, for subsequent use.
F, the preparation of polyacrylate compound particle: to the logical nitrogen of the 500ml four-hole boiling flask that seed emulsion is housed in b step, returnFlow condenser leads to condensed water, is warming up to 75 ± 1 DEG C under the state of opening stirring, after temperature constant, adds initiator solution I,After 5min, start to drip nuclear layer monomer pre-emulsion, and at the uniform velocity drip off in 120min; Then drip shell pre-emulsion, andIn 60min, at the uniform velocity drip off; In the time dripping nuclear layer monomer pre-emulsion and shell monomers pre-emulsion, add and draw every 60minSend out agent solution II, the initiator solution II of equivalent adds 3 times, and wherein initiator solution is disposable adding; Insulation reaction afterwards60min, then be down to room temperature, obtain polyacrylate dispersion. Finally, emulsion obtained above is freezing in-15 DEG C of refrigerator-freezers24h carries out breakdown of emulsion; By washing, suction filtration, 60 DEG C of vacuum drying, after 24 hours, obtain the powder of polyacrylate compound particleEnd.
G, the preparation of polyacrylate compound particle/nylon 6 Blends: by polyacrylate compound particle obtained above 100gPowder and 500g nylon 6 melt blending on twin-screw mixer extruder, extrudes pelletizing, and the temperature in the each district of extruder is respectively217 DEG C, 225 DEG C, 233 DEG C, 235 DEG C, 235 DEG C, 228 DEG C, 215 DEG C, screw speed is 315r/min, through vacuum dryingAfter, injection mo(u)lding on injection machine, each section of temperature of injection machine is 225 DEG C, 230 DEG C, 235 DEG C, 230 DEG C, screw speed is 45r/min。
Nylon 6 low temperature toughening modifyings prepared by the inventive method are as follows with the performance test methods of polyacrylate compound particle:
(1) adopt dynamic light scattering method at 25 DEG C, to measure the equal particle diameter of z and the dispersion of distribution index (Particle of emulsion particleDistributionIndex, PDI), instrument is the ZetasizerZS90 type dynamic light scattering analysis of Malvern company of BritainInstrument. Probe temperature is 25 DEG C.
(2) adopt gravimetric method to calculate Theoretical Grain Size, monomer conversion and the agglomerated thing content of poly acrylate composite emulsion. CalculateMethod is as follows:
The performance test methods of polyacrylate compound particle and nylon 6 Blends for the inventive method nylon 6 low temperature toughening modifyingsAs follows:
(1) impact strength test, computing formula is:
α t = 1000 A b × d
In formula: αtFor notched Izod impact strength, kJ/m2; The merit that A consumes for thrusting sample, J; B is the width of indentation, there sample,Mm; D is the remaining thickness of indentation, there sample, mm.
By by the injection molded standard notch shock batten of injection machine, be of a size of 80mm × 10mm × 2.7mm, for eliminating in sampleStress need to be placed 24 hours at-30 DEG C, then tests its notched Izod impact strength (kJ/m2), instrument is that Shenzhen is newly thought carefully limitedThe ZBC-4 type impact tester for simple supported beam that company produces.
(1) hot strength test, computing formula is:
σ t = P b × d
In formula: σtFor the hot strength of polymer; P is the maximum load of sample before fracture; B is specimen width, mm; D is examinationSample thickness, mm.
By the dumbbell shape tensile bars being obtained by injection machine injection moulding, at 23 DEG C ± 1 DEG C, place 24 hours to eliminate sample internal stress,With newly thinking carefully in Shenzhen afterwards that the CMF6104 type microcomputer controlled electronic universal tester that Co., Ltd produces carries out extension test, surveysObtain the tensile property of intermingling material, probe temperature: 23 DEG C ± 1 DEG C; Draw speed: 10mm/min.
Other steps of embodiment 2～6 are identical with embodiment 1, but dosage of crosslinking agent difference in c step, embodiment's 2～6Dosage of crosslinking agent in c step is respectively 0.65g, 0.78g, 0.91g, 1.04g, 1.17g.
Other steps of embodiment 7～12 are identical with embodiment 1, and difference is listed in table 1.
The difference summary sheet of the each embodiment of table 1
Nylon 6 low temperature toughening modifyings prepared in above-described embodiment are listed in by the emulsion polymerisation parameter of polyacrylate compound particleIn table 2, the mechanical property of polyacrylate compound particle/nylon 6 Blends of preparing in above-described embodiment is listed in table 3.
The parameter summary sheet of polyacrylate compound particle for table 2 nylon 6 low temperature toughening modifyings
The mechanical property summary sheet of table 3 polyacrylate compound particle/nylon 6 Blends
As seen from Figure 1, the instantaneous conversion rate of polymerisation is very high, and all higher than 95%, total conversion is along with the prolongation of timeAnd constantly increase, finally up to 99%, this explanation monomer adds speed to be less than the polymerization rate of monomer, the monomer newly addingAt former emulsion particle surface polymerization reaction take place; By seeing in Fig. 2, along with the continuous dropping of monomer, latex particle constantly becomesGreatly, actual measurement particle diameter and Theoretical Grain Size are basically identical, illustrate that the latex particle size forming is controlled. And can see from table 2, hand overThe consumption of connection agent does not affect substantially on the size of ultimate size, and particle diameter profile exponent is very little. As can be seen from Figure 3, along withThe increase of dosage of crosslinking agent, the low temperature notched impact strength (30 DEG C) of modification of nylon 6 presents the Changing Pattern of first increases and then decreases.In the time that dosage of crosslinking agent is 0.5%, it is maximum that the low temperature notched impact strength of blend (30 DEG C) value reaches. Can from Fig. 4Arrive, make adding of polyacrylate compound particle the low temperature notched impact strength (30 DEG C) of nylon 6 increase, and under hot strengthFall few. In the time that each constituent mass ratio is 1:15:4, the low temperature notched impact strength (30 DEG C) of nylon 6 improves at most. By showing3 can draw, when dosage of crosslinking agent is 0.5%, each constituent mass when for 1:15:4, the low temperature notched of modification of nylon 6 is impactedIntensity (30 DEG C) is 6.82 times of pure nylon 6. From Fig. 5, can clearly find out: the smooth nothing of break surface of pure nylon 6Stress whitening phenomenon, presents brittle fracture feature; And modification of nylon 6 break surfaces are very coarse, there is wire drawing phenomenon, occurTypical shear yielding, is obvious ductile rupture, and this is consistent with mechanical experimental results.

Claims (3)

1. a preparation method for polyacrylate compound particle for nylon 6 low temperature toughening modifyings, is characterized by the method and comprises the following steps:
A, the surface modification of nano silicon: nano grade silica particles is scattered in absolute ethyl alcohol, is mixed with mass fraction and is 50% nano silicon absolute ethyl alcohol dispersion liquid, ultrasonic processing 20～40min; Take the silane coupler that quality is SiO 2 powder quality 5%, be scattered in absolute ethyl alcohol, be mixed with mass fraction and be 10% coupling agent absolute ethyl alcohol dispersion liquid, under stirring, regulate pH value to 4 with watery hydrochloric acid; Above-mentioned whole nano silicon absolute ethyl alcohol dispersion liquids are added in the reactor of logical condensed water and nitrogen, and 50 DEG C of stirred in water bath, then dripping above-mentioned whole coupling agent absolute ethyl alcohol dispersion liquid, 60～120min drips off, continue after insulation reaction 20～30h centrifugation; Wash centrifugal go out lower floor's paste, vacuum drying at 60 DEG C, obtains the nano silica powder of surface modification;
B, the preparation of seed emulsion: the nano silica powder of the surface modification that emulsifying agent, above-mentioned a step are obtained and deionized water are mixed, stirs and ultrasonic 60min, obtains seed emulsion; Wherein, mass ratio is emulsifying agent: the nano silica powder of the surface modification that above-mentioned a step obtains: deionized water=1:20:280;
C, nuclear layer monomer pre-emulsification: by crosslinking agent, stir after emulsifying agent and acrylate monomer mix, obtain nuclear layer monomer pre-emulsion; Wherein, mass ratio is crosslinking agent: emulsifying agent: acrylate monomer=8～18:25:2000;
D, shell monomers pre-emulsification: stir after emulsifying agent, acrylic ester monomer and acrylic acid series function monomer are mixed, obtain shell monomers pre-emulsion; Wherein, quality is than emulsifying agent: acrylic ester monomer=1:50, acrylic acid series function monomer quality is 0.5% of monomer gross mass, and described monomer gross mass refers in the quality, c step of the modified manometer silicon dioxide adding in b step acrylic ester monomer quality sum in acrylate monomer quality and d step;
E, the preparation of initiator solution: stir after initator is mixed with mass ratio 11:1000 with deionized water, obtain initiator solution I; After initator is mixed with mass ratio 4.3:1000 with deionized water, stir, obtain a initiator solution II, prepare altogether 3 parts of identical initiator solution II, for subsequent use; Wherein, initiator solution I is identical with the deionized water quality of using in every part of initiator solution II;
F, the preparation of polyacrylate compound particle: to the logical nitrogen of the reactor that seed emulsion is housed in b step, and be warming up to 75 ± 1 DEG C under reflux condensation mode, stirring, after temperature constant, add initiator solution I, after 5min, start to drip the nuclear layer monomer pre-emulsion that c step obtains, and at the uniform velocity drip off in 100～150min; Then drip the shell monomers pre-emulsion that d step obtains, and at the uniform velocity drip off in 80～30min; In the time dripping nuclear layer monomer pre-emulsion and shell monomers pre-emulsion, add a initiator solution II every 60min, the initiator solution II of equivalent adds 3 times, and wherein initiator solution is disposable adding; Insulation reaction 60min afterwards, then be down to room temperature, obtain polyacrylate dispersion; By the freezing breakdown of emulsion of the above-mentioned emulsion making; By washing, suction filtration, after vacuum drying, obtain the powder of polyacrylate compound particle;
The wherein quality of modified manometer silicon dioxide in b step: acrylate monomer quality in c step: acrylic ester monomer quality=1:11 ~ 16:8 ~ 3 in d step, the gross mass of deionized water: monomer gross mass=9:10, the gross mass of described deionized water refers in b step in deionized water and e step the gross mass of whole deionized waters in initiator solution; Described monomer gross mass refers in the quality, c step of the modified manometer silicon dioxide adding in b step acrylic ester monomer quality sum in acrylate monomer quality and d step;
Described silane coupler is acryloxy propyl trimethoxy silicane;
Described b, c, the emulsifying agent in d step is dodecyl biphenyl sodium sulfonate;
In described c step, acrylate monomer is Isooctyl acrylate monomer, and in described d step, acrylic ester monomer is methyl methacrylate, and acrylic acid series function monomer is methacrylic acid;
Described crosslinking agent is 1,6-hexanediyl ester;
Described initator is potassium peroxydisulfate.
2. the preparation method of polyacrylate compound particle for nylon 6 low temperature toughening modifyings as claimed in claim 1, the average grain diameter that it is characterized by described SiO 2 powder is 20～40nm.
3. a preparation method for polyacrylate compound particle/nylon 6 Blends, comprises the following steps:
The polyacrylate compound particle powder that claim 1 is obtained and nylon 6, with mass ratio 1:5 melt blending on double screw extruder, are extruded after pelletizing, vacuum drying injection mo(u)lding on injection machine.
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CN105418836B (en) * 2016-01-12 2017-08-29 河北工业大学 The preparation method of makrolon toughness reinforcing acrylate polymer/nano silicon compound particle
CN105524210B (en) * 2016-01-12 2017-07-11 河北工业大学 The makrolon toughness reinforcing preparation method of multi-layered acrylic ester polymer particle
CN114292478A (en) * 2022-02-26 2022-04-08 常州市五洲环保科技有限公司 Preparation method of modified material for PVC
CN114479194A (en) * 2022-03-01 2022-05-13 常州市五洲环保科技有限公司 Preparation method of functional material for polyvinyl chloride
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