CN103450671B - Thermally-stabilised water-fast alcoholysis nylon master batch and preparation method thereof - Google Patents

Thermally-stabilised water-fast alcoholysis nylon master batch and preparation method thereof Download PDF

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CN103450671B
CN103450671B CN201310382550.XA CN201310382550A CN103450671B CN 103450671 B CN103450671 B CN 103450671B CN 201310382550 A CN201310382550 A CN 201310382550A CN 103450671 B CN103450671 B CN 103450671B
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thermally
master batch
nylon
alcoholysis
fast
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CN103450671A (en
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陆建华
蒋东升
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NINGBO EAGLE NEW MATERIAL Co Ltd
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NINGBO EAGLE NEW MATERIAL Co Ltd
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Abstract

A kind of thermally-stabilised water-fast alcoholysis nylon master batch, being crushed to by following raw material is blended, raw material includes according to mass fraction meter: the age resistor of the polyamide of 42.5% 67.5%, the cuprous iodide of 10% 20%, the KI of 10% 20%, the lubricant of 1% 3%, the antioxidant of 0.2% 0.5%, the interface coupling agent of 2% 4% and 5% 10%.The preparation method of a kind of thermally-stabilised water-fast alcoholysis nylon master batch, including step: S1, drying;S2, material mixture ratio;S3, batch mixing stir;S4, extrusion.The thermally-stabilised water-fast alcoholysis nylon master batch that the present invention provides, it is added in modification of nylon imparting nylon and resists chemical attack steadily in the long term, particularly high-temperature water, alcoholysis and severe chemical environment, can be widely applied in modified nylon material, make modified nylon material long-term can keep the embrittlement that stable performance and long-term opposing hydrolysis and hot alcoholic solution cause under conditions of 180 DEG C, improve the thermostability fire resistant water resistant solution of nylon, the performance of resistance to alcoholysis.

Description

Thermally-stabilised water-fast alcoholysis nylon master batch and preparation method thereof
Technical field
Dragon master batch preparing technical field of the present invention, more specifically, particularly to a kind of thermally-stabilised water-fast alcoholysis nylon master batch And preparation method thereof.
Background technology
Polyamide has impact strength and the rub resistance wear characteristic of excellence, heat resistance, the chemically-resistant property of medicine, the lubrication of excellence Property and dyeability etc., especially polyamide strengthen after its intensity after alloy modification, goods precision, dimensional stability impartial all Improve a lot, thus be used widely in the automotive industry, but the parts material requirements of automobile engine periphery Bearing engine high-temperature high heat, the pollution of vapour (diesel oil), lubricating oil, anti-icing fluid etc., for ensureing automobile engine periphery The presentation quality of its interior quality of material be not affected, the heat endurance of polyamide and hydrolysis, alcoholysis need to be improved Ability.
Summary of the invention
Object of the present invention is to provide a kind of thermally-stabilised water-fast alcoholysis nylon master batch and a kind of thermally-stabilised water-fast alcoholysis The preparation method of nylon master batch, to solve above-mentioned problem.
The invention provides a kind of thermally-stabilised water-fast alcoholysis nylon master batch, be crushed to by following raw material is blended, raw material is pressed Include according to mass fraction meter: the polyamide of 42.5%-67.5%, the cuprous iodide of 10%-20%, the KI of 10%-20%, The lubricant of 1%-3%, the antioxidant of 0.2%-0.5%, the interface coupling agent of 2%-4% and the age resistor of 5%-10%.
Preferably, described cuprous iodide is the cuprous iodide analyzing pure level, and described KI is the KI analyzing pure level.
Preferably, described lubricant is: the double oleamide of calcium stearate, zinc stearate, ethylene bis stearamide, ethylene, Any one or its most multiple combination in low-molecular-weight high polymer, silicone, ethylene-acrylic acid copolymer.
Preferably, described antioxidant is: the acid of four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrite, Three [2,4-di-tert-butyl-phenyl] phosphite ester, N, N '-bis--[3-(3,5-di-t-butyl-4 hydroxy phenyl) propionyl Base] hexamethylene diamine, in double (2,4-bis-2-methyl-2-phenylpropane base) pentaerythritol diphosphites any one or its most multiple Combination.
Preferably, described interface coupling agent is: γ-amine propyl-triethoxysilicane, γ-glycidyl ether oxygen propyl front three TMOS, γ-(methacryloxypropyl) propyl trimethoxy silicane, Research of Grafting Malaic Anhydride Onto Polyethylene, linea low density Any in Research of Grafting Malaic Anhydride Onto Polyethylene, styrene-maleic anhydride copolymer, polyolefin elastomer grafted maleic anhydride A kind of or that it is the most multiple combination.
Preferably, described age resistor is: amines antioxidants, ketone amines antioxidants, diaryl secondary amine antioxidant, to two Any one or its most multiple combination in phenylenediamine age resistor.
Present invention also offers the preparation method of a kind of thermally-stabilised water-fast alcoholysis nylon master batch, including step:
S1, drying, place nylon and be dried in the baking oven of 100 DEG C 3-4 hour;
S2, material mixture ratio, by formula in each weight percentages of components weigh respectively polyamide, cuprous iodide, KI, Lubricant, antioxidant, interface coupling agent, age resistor;
S3, batch mixing stir, and nylon, lubricant, antioxidant, interface coupling agent are joined in homogenizer and stirred all Even, render to the storage vat that the weight-loss metering at a charging aperture of homogenizer claims, then will weigh up cuprous iodide, KI, age resistor join to stir in homogenizer renders to weightlessness at another charging aperture of homogenizer The storage vat of weighing balance.The storage vat that weight-loss metering claims, then will weigh up cuprous iodide, KI, age resistor join Homogenizer stirs and renders to the storage vat that the weight-loss metering at a charging aperture of homogenizer claims;
S4, extrusion, using the mode of weight-loss metering that the material of step 3 is put into draw ratio in the ratio of formula is 40:1 Upper screw extruder in, screw rod is set and reports as 600r/min, processing temperature is set according to the kind of nylon, molten Melt mixing rear extrusion, tie rod, pelletizing, packaging.
The thermally-stabilised water-fast alcoholysis nylon master batch that the present invention provides, it is added in modification of nylon imparting nylon and supports steadily in the long term Resist chemical, particularly high-temperature water, alcoholysis and severe chemical environment, can be widely applied to modified nylon material In, make modified nylon material that stable performance and long-term opposing hydrolysis and hot alcohol long-term can be kept under conditions of 180 DEG C molten The embrittlement that liquid causes.The thermostability water-fast alcoholysis nylon master batch that the present invention provides, can apply to modified nylon field, carries The thermostability fire resistant water resistant solution of high nylon, the performance of resistance to alcoholysis, widen the field of the use of nylon, make enhancing modified Nylon66 fiber can apply to automobile engine circumferential component.
Accompanying drawing explanation
The flow chart of the preparation method of thermally-stabilised water-fast alcoholysis nylon master batch in Fig. 1 an embodiment of the present invention.
Detailed description of the invention
Below by specific embodiment and combine accompanying drawing the present invention is described in further detail.
Refer to the flow process of the preparation method of thermally-stabilised water-fast alcoholysis nylon master batch in Fig. 1, Fig. 1 an embodiment of the present invention Figure.
Embodiment 1:
Weigh 57Kg nylon 6 to be dried 2 hours at 100 DEG C, then with silicone 0.6Kg, antioxidant N, N '-bis--[3- (3,5-di-t-butyl-4 hydroxy phenyl) propiono] hexamethylene diamine 200g, antioxidant double (2,4-bis-2-methyl-2-phenylpropane base) season penta Tetrol diphosphites 200g, LDPE-g-MAH3Kg, stir 5 minutes with 1000 revs/min in high-speed stirred, wait to stir Release after mixing uniformly, the material mixed is put into weight-loss metering and claims 1# (one of them charging aperture of homogenizer Position) storage vat of feeding station, then by 15kg KI, 15kg cuprous iodide, 1.5kg zinc stearate, 300g KH560,7.5kg amines antioxidants, stirs 5 minutes with 1000 revs/min in high-speed stirred, to be mixed uniformly after put Go out, the material mixed is put into weight-loss metering and claims the storage vat of feeding station, will by the way of weightlessness claims metering Material adds in the double screw extruder that major diameter (L/D) is 40:1.
Embodiment 2:
Weigh 57Kg nylon66 fiber to be dried 2 hours at 100 DEG C, then with silicone 0.6Kg, antioxidant N, N '-bis-- [3-(3,5-di-t-butyl-4 hydroxy phenyl) propiono] hexamethylene diamine 200g, antioxidant is double (2,4-bis-2-methyl-2-phenylpropane base) Pentaerythritol diphosphites 200g, LDPE-g-MAH3Kg, stir 5 minutes with 1000 revs/min in high-speed stirred, Rear releasing to be mixed, puts into weight-loss metering the material mixed and claims the 1# storage vat of feeding station, then will 15kg KI, 15kg cuprous iodide, 1.5kg zinc stearate, 300g KH560,7.5kg amines antioxidants, Yu Gao Fast stirring is stirred 5 minutes with 1000 revs/min, rear releasing to be mixed, the material mixed is put into mistake Metering claims the storage vat of feeding station, and by the way of weightlessness metering, material being added major diameter (L/D) is called 40:1 Double screw extruder in.
Embodiment 3:
Weigh 69.5Kg nylon 6 to be dried 2 hours at 100 DEG C, then with ethylene bis stearamide 0.6Kg, antioxygen Agent N, N '-bis--[3-(3,5-di-t-butyl-4 hydroxy phenyl) propiono] hexamethylene diamine 200g, antioxidant double (2,4- Two 2-methyl-2-phenylpropane bases) pentaerythritol diphosphites 200g, SMA3Kg, with 1000 revs/min of stirrings 5 in high-speed stirred Minute, rear releasing to be mixed, the material mixed is put into weight-loss metering and claims the 1# storage vat of feeding station, Then by 10kg KI, 10kg cuprous iodide, 1.5kg zinc stearate, 300g KH560,5kg ketone amines antioxidants, Stir 5 minutes with 1000 revs/min in high-speed stirred, rear releasing to be mixed, the material mixed is put into Claim the storage vat of feeding station to weight-loss metering, by the way of weightlessness metering, material being added major diameter (L/D) is called 40: In the double screw extruder of 1.Engine speed is 600 turns/min, after extrusion after cooling, air-dries pelletizing, i.e. prepares this Thermally-stabilised hydrolysis nylon master batch described in invention.

Claims (9)

1. a thermally-stabilised water-fast alcoholysis nylon master batch, it is characterized in that, being crushed to by following raw material is blended, raw material includes according to mass fraction meter: the polyamide of 42.5%-67.5%, the cuprous iodide of 10%-20%, the KI of 10%-20%, the lubricant of 1%-3%, the antioxidant of 0.2%-0.5%, the interface coupling agent of 2%-4% and the age resistor of 5%-10%.
2., according to the thermally-stabilised water-fast alcoholysis nylon master batch described in claim 1, it is characterised in that described cuprous iodide is the cuprous iodide analyzing pure level, described KI is the KI analyzing pure level.
Thermally-stabilised water-fast alcoholysis nylon master batch the most according to claim 1, it is characterized in that, described lubricant is: any one or its most multiple combination in calcium stearate, zinc stearate, ethylene bis stearamide, ethylene double oleamide, low-molecular-weight high polymer, silicone, ethylene-acrylic acid copolymer.
Thermally-stabilised water-fast alcoholysis nylon master batch the most according to claim 1, it is characterised in that described antioxidant is: four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrite Ester, three [2; 4-di-tert-butyl-phenyl] phosphite ester, N; any one or its most multiple combination in N '-bis--[3-(3,5-di-t-butyl-4 hydroxy phenyl) propiono] hexamethylene diamine, double (2,4-bis-2-methyl-2-phenylpropane base) pentaerythritol diphosphites.
Thermally-stabilised water-fast alcoholysis nylon master batch the most according to claim 1, it is characterized in that, described interface coupling agent is: any one or its most multiple combination in gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, Research of Grafting Malaic Anhydride Onto Polyethylene, styrene-maleic anhydride copolymer, polyolefin elastomer grafted maleic anhydride.
Thermally-stabilised water-fast alcoholysis nylon master batch the most according to claim 5, it is characterised in that described Research of Grafting Malaic Anhydride Onto Polyethylene is LLDPE grafted maleic anhydride.
Thermally-stabilised water-fast alcoholysis nylon master batch the most according to claim 1, it is characterised in that described age resistor is amines antioxidants.
Thermally-stabilised water-fast alcoholysis nylon master batch the most according to claim 7, it is characterised in that described amines antioxidants is any one or its combination of two kinds in ketone amines antioxidants, diaryl secondary amine antioxidant.
9. according to the thermally-stabilised water-fast alcoholysis nylon master batch described in claim 1-8 any one, it is characterised in that preparation method includes:
Step one, polyamide is positioned in the baking oven of 100 DEG C and is dried 3-4 hour;
Step 2, by formula in each weight percentages of components weigh polyamide, cuprous iodide, KI, lubricant, antioxidant, interface coupling agent, age resistor respectively;
Step 3, polyamide, lubricant, antioxidant, interface coupling agent are joined in homogenizer and stir, render to the storage vat that the weight-loss metering at a charging aperture of homogenizer claims, then by weighing up cuprous iodide, KI, age resistor join to stir in homogenizer and render to the storage vat that the weight-loss metering at another charging aperture of homogenizer claims;
Step 4, in formula ratio use weight-loss metering mode the material of step 3 is put in the double screw extruder that draw ratio is 40: 1, screw rod is set and reports as 600r/min, processing temperature is set according to the kind of polyamide, extrusion, tie rod, pelletizing, packaging after melting mixing.
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CN107974082A (en) * 2017-11-24 2018-05-01 广东威林工程塑料股份有限公司 A kind of special polyamide compoiste material of retainer and preparation method thereof
CN112480661A (en) * 2020-10-31 2021-03-12 山东广垠新材料有限公司 High-temperature-resistant hydrolysis-resistant modified polyamide pipeline material and preparation method thereof
CN113321931A (en) * 2021-06-11 2021-08-31 上海珐工材料科技有限公司 Copper master batch with heat-resistant and stable characteristics added in PA66 continuous polymerization and preparation method thereof
CN114133730A (en) * 2021-11-16 2022-03-04 宿迁联盛科技股份有限公司 High-temperature-resistant heat-oxygen-aging-resistant polyamide heat stabilizer masterbatch and preparation method thereof
CN117777435A (en) * 2023-08-22 2024-03-29 上海北冈新材料有限公司 Semi-aromatic copolyamide, semi-aromatic polyamide composition, and preparation method and application thereof

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CN101531812B (en) * 2008-10-30 2012-10-10 上海耐特复合材料制品有限公司 Nylon 66 heat resistant hydrolysis-level thermoplastic engineering plastic
CN101613527B (en) * 2009-07-29 2011-02-09 东莞市意普万工程塑料有限公司 Alcoholysis resistance nylon composite material and preparation method thereof
CN101914288B (en) * 2010-08-30 2013-01-02 南京聚隆科技股份有限公司 Nylon 6 mineral fiber composite material for automobile engine cover lid and preparation method thereof
CN102311638B (en) * 2010-12-21 2012-12-19 深圳市科聚新材料有限公司 Hydrolysis-resistance alcoholysis-resistance glass fiber reinforced PPA (phenyl-propanolamine) material and preparation method thereof
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