CN102643534A - Chemical corrosion resistant high impact long carbon chain nylon master batch and preparation method and application thereof - Google Patents
Chemical corrosion resistant high impact long carbon chain nylon master batch and preparation method and application thereof Download PDFInfo
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- CN102643534A CN102643534A CN2012101341004A CN201210134100A CN102643534A CN 102643534 A CN102643534 A CN 102643534A CN 2012101341004 A CN2012101341004 A CN 2012101341004A CN 201210134100 A CN201210134100 A CN 201210134100A CN 102643534 A CN102643534 A CN 102643534A
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Abstract
The invention relates to a chemical corrosion resistant high impact long carbon chain nylon master batch, which contains long carbon chain nylon, compatible toughening agents and heat stabilizers. The invention further relates to a preparation method and an application of the nylon master batch. The nylon master batch has good impact resistance, chemical corrosion resistance and low humidity absorption, and is good in compatibility with other engineering plastics and capable of improving chemical corrosion resistance, low-temperature impact resistance and dimensional stabilities of composite materials, wherein the chemical corrosion resistance includes corrosion from zinc halide, calcium halide and ethylene glycol.
Description
Technical field
The present invention relates to a kind of resistance to chemical attack high-impact long carbon chain nylon masterbatch.
Background technology
Nylon has another name called polyamide resin (PA), all contains strong polar amide group in the molecular structure, in its structure, has firm hydrogen bond, makes that the fusing point of nylon is higher, has good mechanical performance, wear resistance and self lubricity.The nylon of different carbon chain lengths has different characteristic, and carbochain is long more usually, and toughness and shock resistance are also high more.
Long carbon chain nylon mainly comprises NYLON610, nylon 1010, nylon 12, Ni Long11, nylon 612, nylon 1212, nylon 1012, nylon 1313 and nylon 1414.The long carbon chain nylon water-absorbent is little, thereby dimensional stability is good.Long carbon chain nylon is than PA6 and PA66 organic solvent-resistant (like ethylene glycol solution) more, the corrosion of more anti-chlorate.
Automobile industry lightweight at present, fuel emission standard improve, the use of biofuel to automobile component require increasingly high.Prime the fuel system component such as oil filler pipe are basically all using metallic substance or high density polyethylene(HDPE) (HDPE) to add the multi-layer co-extruded or fluoridation HDPE mono-layer tube of EVA; Multi-layer co-extruded pipe comprehensive cost is very high; Fluoridation is big for environment pollution; Use part requirement low-temperature impact-resistant (40 ℃), fire resistant oil infiltration, salt tolerant performances such as (Snow Agent contain calcium chloride, zinc chloride) such as the imperative oil filler pipe of type material.The minority vehicle has adopted nylon 6 oil filler pipes, but when run into Snow Agent winter, the oil filler pipe cracking that can be corroded.Automative air conditioning cooling system component require anti-alcoholysis like scatterer hydroecium end cap, the salt tolerant corrosion, and used modified nylon materials can not satisfy new technical requirements now.
At present, automobile-used nylon material is considered technology and economical adaptation property, needs the new higher functional master batch of performance, to improve the performance of engineering plastics commonly used, satisfies the increasingly high requirement of automobile industry.
Summary of the invention
The purpose of this invention is to provide a kind of long carbon chain nylon functional master batch, solve the difficult problem of automobile-used nylon material resistance to chemical attack that material faces (salt, terepthaloyl moietie) and low-temperature impact-resistant.
Another object of the present invention is to provide the preparation method of above-mentioned long carbon chain nylon functional master batch.
The invention provides a kind of long carbon chain nylon functional master batch, this long carbon chain nylon masterbatch contains long carbon chain nylon, compatible type toughner and thermo-stabilizer.
The present invention also provides a kind of preparation method of long carbon chain nylon functional master batch of the present invention; This method comprises: with said a kind of long carbon chain nylon, compatilizer, toughner, thermo-stabilizer pre-mixing in high-speed mixer; Extrude pelletizing through twin screw extruder, obtain said nylon functional master batch.
Long carbon chain nylon functional master batch provided by the invention has good resistance to chemical corrosion (salt, terepthaloyl moietie), low-temperature impact-resistant performance and low water absorbable, and has good and consistency general engineering plastic.
Embodiment
Long carbon chain nylon masterbatch provided by the invention contains long carbon chain nylon, compatible formulation toughner and thermo-stabilizer.
According to long carbon chain nylon masterbatch provided by the invention; Gross weight with said long carbon chain nylon masterbatch is a benchmark; The amount of said long carbon chain nylon is 50-95 weight part, preferred 60-90 weight part; The amount of said compatible type toughner is 0.01-50 weight part, preferred 1-30 weight part, and the amount of said thermo-stabilizer is 0.001-20 weight part, preferred 0.1-10 weight part.
According to long carbon chain nylon masterbatch provided by the invention, said long carbon chain nylon is at least a in NYLON610, nylon 1010, nylon 12, Ni Long11, nylon 612, nylon 1212, nylon 1012, nylon 1313 or the nylon 1414.
According to long carbon chain nylon masterbatch provided by the invention, it is at least a that said compatible type toughner is that vinylbenzene-methyl propenoic acid glycidyl alcohol copolymer (SGMA), organic-silicon-modified polyolefine, styrene-maleic anhydride copolymer (SMA), St-MAH-GMA ternary atactic copolymer, SEBS-g-MA graft copolymer, PCL-s-GMA multipolymer, nucleocapsid multilayered structure vinylformic acid imide polymer, Et-MAH-EA terpolymer, main chain are that EGMA and side chain are ethylene copolymer series and main chain in epoxy modified acrylic resin, oxazolinyl MPS, EVA, maleic anhydride graft polyolefine, acrylic acid-grafted polyolefine and the ionic polymer of acid.
According to long carbon chain nylon masterbatch provided by the invention, said thermo-stabilizer is mantoquita or contains hindered phenol and the composite antioxidant of phosphorous acid ester.Said mantoquita is the organic or inorganic copper compound, for example compound mantoquita heat-resistant agent H3336 (the thermo-stabilizer trade mark of Bruggolen company).Hindered phenol is a primary antioxidant in the said composite antioxidant, and phosphorous acid ester is an auxiliary antioxidant, and the weight ratio of primary antioxidant/auxiliary anti-oxidant is 1:1 to 1:4.The example of Hinered phenols antioxidant comprises oxidation inhibitor 1098 and 1010 (the oxidation inhibitor trade mark of Ciba company); The staple of oxidation inhibitor 1098 is N; (3-(3 for N '-two; The 5-di-tert-butyl-hydroxy phenyl) hexanediamine propionic acid amide), the staple of antioxidant 1010 are four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] tetramethylolmethane.The example of phosphite ester kind antioxidant is oxidation inhibitor 168 (the oxidation inhibitor trade mark of Ciba company), and its staple is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
According to long carbon chain nylon masterbatch provided by the invention,, can also comprise following component: one or more of inorganic filler, photostabilizer, lubricant, static inhibitor, fire retardant, nucleator and coupling agent in order to give product some properties.Gross weight with said long carbon chain nylon masterbatch is a benchmark; The amount of inorganic filler is the 0-60 weight part, and the amount of photostabilizer is the 0-5 weight part, and the amount of lubricant is the 0-10 weight part; The amount of static inhibitor is the 0-5 weight part; The amount of fire retardant is the 0-35 weight part, and the amount of coupling agent is the 0-3 weight part, and the amount of nucleator is the 0-10 weight part.
Said inorganic filler can select one or more in spun glass, mica powder, talcum powder, lime carbonate, the permanent white, and the adding of this component can improve the intensity and the flowability of nylon masterbatch.
Said lubricant can be selected one or more in ethylene bis stearic amide, modification ethylene bis stearic amide, silicone, metallic soap salt, amine hydroxybenzene, the erucicamide for use.The modification ethylene bis stearic amide is N for example, N '-ethylene bis stearic amide grafts.
According to long carbon chain nylon masterbatch provided by the invention, its preparation method comprises that mix said long carbon chain nylon, compatible formulation toughner and thermo-stabilizer (1) in high-speed mixer, obtain pre-composition; (2) above-mentioned pre-composition is extruded pelletizing through screw extrusion press, obtain described long carbon chain nylon masterbatch.
Preparing method according to long carbon chain nylon masterbatch provided by the invention; Under preferable case; Gross weight with said nylon masterbatch is a benchmark; The amount of said long carbon chain nylon is the 60-90 weight part, and the amount of said compatible type toughner is the 1-30 weight part, and the amount of said thermo-stabilizer is the 0.1-10 weight part.
The preparation method of long carbon chain nylon masterbatch is provided according to the present invention, and the major equipment of producing product has that high-speed mixer, automatic gauge are claimed, screw extrusion press.
According to long carbon chain nylon masterbatch provided by the invention; Its application comprises; With the long carbon chain nylon masterbatch with after one or more heating and meltings in nylon 6, nylon 66, polycarbonate, polyester, ppe and the acrylonitrile-butadiene-styrene terpolymer mix; Obtain plastics composite, can improve shock resistance, chemical resistance and the dimensional stability of plastics.
Embodiment 1
84.2 kilograms PA610 and 15 kilograms SEBS-g-MA graft copolymer, 0.8 kilogram H3336 behind the premix, are added in the screw extrusion press in high mixer, and heating and melting through pelletizing after the water-cooled, obtains long carbon chain nylon masterbatch of the present invention after extruding.
Embodiment 2
With 68.7 kilograms PA610,30 kilograms SEBS-g-MA graft copolymer, 0.8 kilogram H3336,0.5 kilogram of calcium stearate in high mixer behind the premix; Add in the screw extrusion press; Heating and melting through pelletizing after the water-cooled, obtains long carbon chain nylon masterbatch of the present invention after extruding.
Application examples 1
With 50 kilograms of instances, 2 gained nylon masterbatch and 20 kg nylon 6 in high mixer behind the premix; Add in the screw extrusion press; Heating and melting; Add 30 kilograms of short glass fiber T435R (the short glass fiber trade mark of Taishan glass fiber Ltd) from the side spout of screw extrusion press, through pelletizing after the water-cooled, obtain the glass reinforced composite materials after extruding.
Performance evaluation
With embodiment 1 and embodiment 2 prepared products, on injection moulding machine, to test according to iso standard injection moulding sample and by iso standard, gained is the result list in the table 1.
Can find out that from table 1 embodiment 1 and embodiment 2 have good toughness and anti-zinc chloride and terepthaloyl moietie corrosive nature.
Can find out that from table 1 application examples 1 has good comprehensive mechanical properties, anti-zinc chloride and terepthaloyl moietie corrosive nature and agent of low hygroscopicity, explain that the long carbon chain nylon masterbatch that the present invention improves has a good application prospect.
Table 1
(1) dried state (relative humidity 0)/hygrometric state (relative humidity 50) ISO1110
Claims (10)
1. long carbon chain nylon masterbatch; This long carbon chain nylon masterbatch comprises long carbon chain nylon, compatible type toughner and thermo-stabilizer; It is characterized in that, be benchmark with the gross weight of said long carbon chain nylon masterbatch, and the amount of said long carbon chain nylon is the 50-95 weight part; The amount of said compatible type toughner is the 0.01-50 weight part, and the amount of said thermo-stabilizer is the 0.001-20 weight part.
2. according to claims 1 described long carbon chain nylon masterbatch, it is characterized in that long carbon chain nylon is at least a in NYLON610, nylon 1010, nylon 12, Ni Long11, nylon 612, nylon 1212, nylon 1012, nylon 1313 or the nylon 1414.
3. according to claims 1 described long carbon chain nylon masterbatch; It is characterized in that it is at least a that said compatible type toughner is that vinylbenzene-methyl propenoic acid glycidyl alcohol copolymer (SGMA), organic-silicon-modified polyolefine, styrene-maleic anhydride copolymer (SMA), St-MAH-GMA ternary atactic copolymer, SEBS-g-MA graft copolymer, PCL-s-GMA multipolymer, nucleocapsid multilayered structure vinylformic acid imide polymer, Et-MAH-EA terpolymer, main chain are that EGMA and side chain are ethylene copolymer series and main chain in epoxy modified acrylic resin, oxazolinyl MPS, EVA, maleic anhydride graft polyolefine, acrylic acid-grafted polyolefine and the ionic polymer of acid.
4. according to claims 1 described long carbon chain nylon masterbatch; It is characterized in that; Said thermo-stabilizer is mantoquita or contains hindered phenol and the composite antioxidant of phosphorous acid ester, and said mantoquita is the organic or inorganic copper compound, and hindered phenol is a primary antioxidant in the said composite antioxidant; Phosphorous acid ester is an auxiliary antioxidant, and the weight ratio of primary antioxidant/auxiliary anti-oxidant is 1:1 to 1:4; Hinered phenols antioxidant comprise oxidation inhibitor 1098 and 1010 (the oxidation inhibitor trade mark of Ciba company); The staple of oxidation inhibitor 1098 is N; (3-(3 for N '-two; The 5-di-tert-butyl-hydroxy phenyl) hexanediamine propionic acid amide), the staple of antioxidant 1010 are four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] tetramethylolmethane; The example of phosphite ester kind antioxidant is oxidation inhibitor 168 (the oxidation inhibitor trade mark of Ciba company), and its staple is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
5. according to claims 1 described long carbon chain nylon masterbatch, it is characterized in that, can also comprise following component: one or more of inorganic filler, photostabilizer, lubricant, static inhibitor, fire retardant and coupling agent.
6. the gross weight with said long carbon chain nylon masterbatch is a benchmark; The amount of inorganic filler is the 0-60 weight part, and the amount of photostabilizer is the 0-5 weight part, and the amount of lubricant is the 0-10 weight part; The amount of static inhibitor is the 0-5 weight part; The amount of fire retardant is the 0-35 weight part, and the amount of coupling agent is the 0-3 weight part, and the amount of nucleator is the 0-10 weight part.
7. according to claims 5 described long carbon chain nylon masterbatch, it is characterized in that said inorganic filler can select one or more in spun glass, mica powder, talcum powder, lime carbonate, the permanent white.
8. according to claims 5 described long carbon chain nylon masterbatch, it is characterized in that said lubricant can be selected one or more in ethylene bis stearic amide, modification ethylene bis stearic amide, silicone, metallic soap salt, amine hydroxybenzene, the erucicamide for use.
9. resistance to chemical attack high-impact long carbon chain nylon masterbatch, its preparation method comprises that mix said long carbon chain nylon, compatible formulation toughner and thermo-stabilizer (1) in high-speed mixer, obtain pre-composition; (2) above-mentioned pre-composition is extruded pelletizing through screw extrusion press, obtain described long carbon chain nylon masterbatch.
10. resistance to chemical attack high-impact long carbon chain nylon masterbatch; Its application comprises; Said long carbon chain nylon masterbatch with after one or more engineering plastics heating and meltings in nylon 6, nylon 66, polycarbonate, polyester, ppe and the acrylonitrile-butadiene-styrene terpolymer mix, is obtained plastics composite.
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| CN103450678A (en) * | 2013-08-28 | 2013-12-18 | 宁波伊德尔新材料有限公司 | Waterproof alcoholysis high-temperature resistant renewable nylon 66 composite material and preparation method thereof |
| CN103589147A (en) * | 2013-10-29 | 2014-02-19 | 安徽安缆模具有限公司 | Impact-resistance nylon PA12 material for automobile connectors |
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| CN103613924A (en) * | 2013-11-12 | 2014-03-05 | 苏州博利迈新材料科技有限公司 | Anti-electrostatic, reinforced and toughened nylon 612 composite material and preparation method and application thereof |
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Application publication date: 20120822 |