CN105838065A - Antistatic polyamide mold material and preparing method thereof - Google Patents

Antistatic polyamide mold material and preparing method thereof Download PDF

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Publication number
CN105838065A
CN105838065A CN201610275885.5A CN201610275885A CN105838065A CN 105838065 A CN105838065 A CN 105838065A CN 201610275885 A CN201610275885 A CN 201610275885A CN 105838065 A CN105838065 A CN 105838065A
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詹金珠
王玉宝
张如宏
陈士坤
崔伟东
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ANHUI ANLAN MOULD Co Ltd
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ANHUI ANLAN MOULD Co Ltd
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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
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/04Antistatic
    • 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
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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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)
  • Organic Insulating Materials (AREA)

Abstract

The invention discloses an antistatic polyamide mold material .The antistatic polyamide mold material is prepared from, by weight, 2-4 parts of expanded perlite, 100-130 parts of polyamide 66, 120-140 parts of dimethyl formamide, 4-6 parts of molybdenum disulfide, 0.7-1 part of hexadecyl trimethyl ammonium bromide, 0.3-1 part of chitosan, 2-3 parts of polystyrene, 1-2 parts of dodecyl dimethyl betaine, 20-30 parts of glass fibers, 2-3 parts of fatty acid polyglycol ester, 2-4 parts of tributyl citrate, 0.7-1 part of dodecylthiol, 0.2-0.6 part of triisopropanolamine, 1-3 parts of anhydrous calcium chloride, 1-2 parts of p-aminobenzene sulfonic acid, 1-2 parts of hydroxypropyl methylcellulose and 2-3 parts of sodium potassium silicate .According to the antistatic polyamide mold material, added modified molybdenum disulfide can be dispersed in a polymer matrix, and the thermal stability of the material is effectively improved; meanwhile, molybdenum disulfide can release non-ignitable gas sulfur dioxide in the thermal degradation process, and the flame-retardant performance of the material can be improved through the diluting effect of sulfur dioxide .

Description

A kind of antistatic nylon mold materials and preparation method thereof
Technical field
The present invention relates to mold materials technical field, particularly relate to a kind of antistatic nylon mold materials and preparation method thereof.
Background technology
Mould produces indispensable frock as modern industry, play conclusive effect aborning, current mould uses metal material mostly, quality and the life-span of metal die are the highest, but its cost of manufacture is expensive, especially some complex contours, the difficult metal die shaped, manufacturing process is extremely complex, a lot of metal materials there is also processing difficulties simultaneously, and the process-cycle is long, and the defect that after die wear, repair time is longer;
Along with developing rapidly of industry, improving constantly of the aspects such as polymer composites intensity and precision, the range of application making its goods is also constantly expanding, for metal material, polymer composites cost of manufacture is cheap, easy-formation, and the process-cycle is short, repair time is short, and these advantages make it have huge potentiality in mould applications;
Molybdenum disulfide nano sheet layer has relatively low heat conductivity, plays lamella blocking effect for molybdenum bisuphide and provide safeguard in polymeric material pyrolysis and combustion process;Meanwhile, the existence of transition metal molybdenum can promote that polymeric matrix forms fine and close solid layer of charcoal, it is possible to effectively stops the exchanges of mass and energy between flame and polymeric matrix, the degraded of suppression polymer, the final fire resistance improving polymeric material.Additionally, molybdate compound is as multiple polymers such as PA, PVC, PS, HIPS, ABS, polyolefin and the smoke suppressant of Halogen polyester, polymeric material burning cigarette and the growing amount of CO can be reduced, reduce the fire risk of material, win the quality time for fire rescue;
The most domestic and international document report for molybdenum bisuphide with polymer composites is concentrated mainly on the aspects such as electric conductivity and the frictional behaviour of composite, seldom relate to hot property and the fire safety evaluating performance of material, therefore, system carry out molybdenum bisuphide and derivant thereof the applied research in terms of flame retardance of polymer material, to exploitation BACN, enrich and improve flame retardance of polymer system, being of great immediate significance.
But, there is a most thorny difficult problem in the research of current molybdenum-disulfide radical polymer nanocomposites.The dispersion in polymeric matrix of efficiently the peeling off of such as molybdenum bisuphide, molybdenum disulfide nano sheet layer and single molybdenum disulfide nano sheet layer there may be the problems such as flame retarding efficiency is the highest;
Therefore, in order to solve the problems referred to above, the present invention explores, designs efficient molybdenum bisuphide stripping means;Utilize organic molecule modified molybdenum disulfide nanoscale twins to improve its dispersibility in polymeric matrix;From the angle of MOLECULE DESIGN, at molybdenum bisuphide sheet surfaces grafting organic fire-retardant and carrying inorganic metal compound nanoparticles, complex functionality molybdenum bisuphide material.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of antistatic nylon mold materials and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of antistatic nylon mold materials, it is made up of the raw material of following weight parts:
Expanded perlite 2-4, nylon66 fiber 100-130, dimethylformamide 120-140, molybdenum bisuphide 4-6, cetyl trimethylammonium bromide 0.7-1, chitosan 0.3-1, polystyrene 2-3, dodecyldimethylammonium hydroxide inner salt 1-2, glass fibre 20-30, fatty acid polyethylene glycol ester 2-3, tributyl citrate 2-4, lauryl mercaptan 0.7-1, triisopropanolamine 0.2-0.6, anhydrous calcium chloride 1-3, p-aminobenzene sulfonic acid 1-2, hydroxypropyl methyl cellulose 1-2, sodium potassium silicate 2-3.
The preparation method of a kind of described nylon mold materials, comprises the following steps:
(1) above-mentioned lithium chloride is taken, join in the deionized water of its weight 800-1000 times, stirring and dissolving, add above-mentioned molybdenum bisuphide, supersound process 1-2 hour, ultrasonic power is 300-400w, stands 40-52 hour, filters, take the 30-40% of above-mentioned dimethylformamide weight, add the above-mentioned precipitation being filtrated to get, disperse 5-7 minute under the rotating speed that 1500-1600/ divides, molybdenum bisuphide suspension must be peeled off;
(2) above-mentioned sodium potassium silicate is joined in the deionized water of its weight 10-13 times, stir, add hydroxypropyl methyl cellulose, rise high-temperature and be 70-75 DEG C, insulated and stirred 4-7 minute, obtain fiber dispersion;
(3) by above-mentioned cetyl trimethylammonium bromide, chitosan mixing, join in the deionized water of compound weight 100-120 times, stir, obtain lysate;
(4) above-mentioned stripping molybdenum bisuphide suspension is heated to 30-40 DEG C, drip above-mentioned lysate, insulation reaction 7-8 hour after dropping, 4000-5000 rev/min is stirred 7-10 minute, adds above-mentioned fiber dispersion, rise high-temperature and be 70-75 DEG C, insulated and stirred 10-15 minute, filters, and precipitation is used the acetum of 15-20%, absolute ethanol washing 3-4 time respectively, it is dried 20-26 hour at 60-65 DEG C, obtains organically-modified molybdenum bisuphide;
(5) take the 30-40% of residue dimethylformamide weight, add polystyrene, stir;
(6) take above-mentioned organically-modified molybdenum bisuphide, join in remaining dimethylformamide, ultrasonic disperse 3-4 hour, add the dimethyl formamide solution of above-mentioned polystyrene, stirring mixing 10-15 hour, adds above-mentioned anhydrous calcium chloride, pours in polytetrafluoroethylcontainer container, send in the baking oven of 100-105 DEG C and be dried 20-25 hour, raise oven temperature and be 130-135 DEG C, continue to be dried 10-13 hour, discharging, the solid content obtained is pulverized, obtains modified composite material;
(7) by above-mentioned p-aminobenzene sulfonic acid, lauryl mercaptan mixing, rise high-temperature and be 80-90 DEG C, add the 20-26% of above-mentioned nylon66 fiber weight, heat-insulation preheating 10-14 minute, mix with above-mentioned modified composite material, triisopropanolamine, rise high-temperature and be 110-120 DEG C, continue insulation 6-10 minute, obtain premix material;
(8) above-mentioned premix material is mixed with remaining each raw material, stir, send in injection machine, adding heat fusing, be injected in mould by nozzle by the fluid after melted, the initial temperature of mould is maintained at 130-150 DEG C, after injection molding under 80-90MPa pressurize 1-2s, cooling, the demoulding, obtain described nylon mold materials.
nullThe invention have the advantage that the machine modified molybdenum disulfide that the present invention adds can well be dispersed in polymeric matrix,And define uniform network structure between polymer molecular chain,Effectively limit the motion of polymer molecular chain,Delay the thermal degradation of polymer molecular chain,The two-dimensional nano lamellar structure adding molybdenum bisuphide self can reduce conduction of heat,Therefore the heat stability of finished-product material is effectively raised,Molybdenum bisuphide can discharge non-flammable gases sulfur dioxide in thermal degradation process simultaneously,Good diluting effect can be played,Thus improve fire resistance,And finished product burning during molybdenum bisuphide to pyrolysis and combustion process in breeze be formed with facilitation,Combustion heat release amount and thermal decomposition product are equally played good iris action by thick and heavy and closely knit layer of charcoal,Therefore the finished-product material of the present invention has good heat stability and fire resistance,The material of the present invention adds dodecyldimethylammonium hydroxide inner salt etc.,Effectively raise the antistatic property of finished product.
Detailed description of the invention
A kind of antistatic nylon mold materials, it is made up of the raw material of following weight parts:
Expanded perlite 2, nylon66 fiber 100, dimethylformamide 120, molybdenum bisuphide 4, cetyl trimethylammonium bromide 0.7, chitosan 0.3, polystyrene 2, dodecyldimethylammonium hydroxide inner salt 1, glass fibre 20, fatty acid polyethylene glycol ester 2, tributyl citrate 2, lauryl mercaptan 0.7, triisopropanolamine 0.2, anhydrous calcium chloride 1, p-aminobenzene sulfonic acid 1, hydroxypropyl methyl cellulose 1, sodium potassium silicate 2.
The preparation method of a kind of described nylon mold materials, comprises the following steps:
(1) above-mentioned lithium chloride is taken, join in the deionized water of its weight 800 times, stirring and dissolving, add above-mentioned molybdenum bisuphide, supersound process 1 hour, ultrasonic power is 300w, stands 40 hours, filters, take the 30% of above-mentioned dimethylformamide weight, add the above-mentioned precipitation being filtrated to get, disperse 5 minutes under the rotating speed of 1500/ point, molybdenum bisuphide suspension must be peeled off;
(2) being joined by above-mentioned sodium potassium silicate in the deionized water of its weight 10 times, stir, add hydroxypropyl methyl cellulose, rising high-temperature is 70 DEG C, and insulated and stirred 4 minutes obtains fiber dispersion;
(3) by above-mentioned cetyl trimethylammonium bromide, chitosan mixing, join in the deionized water of compound weight 100 times, stir, obtain lysate;
(4) above-mentioned stripping molybdenum bisuphide suspension is heated to 30 DEG C, drip above-mentioned lysate, insulation reaction 7 hours after dropping, 4000 revs/min are stirred 7 minutes, add above-mentioned fiber dispersion, rising high-temperature is 70 DEG C, insulated and stirred 10 minutes, filters, by precipitation respectively with 15% acetum, absolute ethanol washing 3 times, it is dried 20 hours at 60 DEG C, obtains organically-modified molybdenum bisuphide;
(5) take the 30% of residue dimethylformamide weight, add polystyrene, stir;
(6) take above-mentioned organically-modified molybdenum bisuphide, join in remaining dimethylformamide, ultrasonic disperse 3 hours, add the dimethyl formamide solution of above-mentioned polystyrene, stirring mixing 10 hours, adds above-mentioned anhydrous calcium chloride, pours in polytetrafluoroethylcontainer container, send in the baking oven of 100 DEG C and be dried 20 hours, raising oven temperature is 130 DEG C, continues to be dried 10 hours, discharging, the solid content obtained is pulverized, obtains modified composite material;
(7) by above-mentioned p-aminobenzene sulfonic acid, lauryl mercaptan mixing, rising high-temperature is 80 DEG C, adds the 20% of above-mentioned nylon66 fiber weight, heat-insulation preheating 10 minutes, mixes with above-mentioned modified composite material, triisopropanolamine, and rising high-temperature is 110 DEG C, continue insulation 6 minutes, obtain premix material;
(8) above-mentioned premix material is mixed with remaining each raw material, stir, send in injection machine, add heat fusing, will melted after fluid be injected in mould by nozzle, the initial temperature of mould is maintained at 130 DEG C, after injection molding under 80MPa pressurize 1s, cooling, the demoulding, obtain described nylon mold materials.
The performance detection of the mould prepared with material of the present invention:
Appearance test:
The defects such as bubble-free, shrinkage cavity, surface indentation and wall unevenness are even, solid colour;
Ballistic work/J 23-40 DEG C: crack-free.

Claims (2)

1. an antistatic nylon mold materials, it is characterised in that it is made up of the raw material of following weight parts:
Expanded perlite 2-4, nylon66 fiber 100-130, dimethylformamide 120-140, molybdenum bisuphide 4-6, cetyl trimethylammonium bromide 0.7-1, chitosan 0.3-1, polystyrene 2-3, dodecyldimethylammonium hydroxide inner salt 1-2, glass fibre 20-30, fatty acid polyethylene glycol ester 2-3, tributyl citrate 2-4, lauryl mercaptan 0.7-1, triisopropanolamine 0.2-0.6, anhydrous calcium chloride 1-3, p-aminobenzene sulfonic acid 1-2, hydroxypropyl methyl cellulose 1-2, sodium potassium silicate 2-3.
2. the preparation method of a nylon mold materials as claimed in claim 1, it is characterised in that comprise the following steps:
(1) above-mentioned lithium chloride is taken, join in the deionized water of its weight 800-1000 times, stirring and dissolving, add above-mentioned molybdenum bisuphide, supersound process 1-2 hour, ultrasonic power is 300-400w, stands 40-52 hour, filters, take the 30-40% of above-mentioned dimethylformamide weight, add the above-mentioned precipitation being filtrated to get, disperse 5-7 minute under the rotating speed that 1500-1600/ divides, molybdenum bisuphide suspension must be peeled off;
(2) above-mentioned sodium potassium silicate is joined in the deionized water of its weight 10-13 times, stir, add hydroxypropyl methyl cellulose, rise high-temperature and be 70-75 DEG C, insulated and stirred 4-7 minute, obtain fiber dispersion;
(3) by above-mentioned cetyl trimethylammonium bromide, chitosan mixing, join in the deionized water of compound weight 100-120 times, stir, obtain lysate;
(4) above-mentioned stripping molybdenum bisuphide suspension is heated to 30-40 DEG C, drip above-mentioned lysate, insulation reaction 7-8 hour after dropping, 4000-5000 rev/min is stirred 7-10 minute, adds above-mentioned fiber dispersion, rise high-temperature and be 70-75 DEG C, insulated and stirred 10-15 minute, filters, and precipitation is used the acetum of 15-20%, absolute ethanol washing 3-4 time respectively, it is dried 20-26 hour at 60-65 DEG C, obtains organically-modified molybdenum bisuphide;
(5) take the 30-40% of residue dimethylformamide weight, add polystyrene, stir;
(6) take above-mentioned organically-modified molybdenum bisuphide, join in remaining dimethylformamide, ultrasonic disperse 3-4 hour, add the dimethyl formamide solution of above-mentioned polystyrene, stirring mixing 10-15 hour, adds above-mentioned anhydrous calcium chloride, pours in polytetrafluoroethylcontainer container, send in the baking oven of 100-105 DEG C and be dried 20-25 hour, raise oven temperature and be 130-135 DEG C, continue to be dried 10-13 hour, discharging, the solid content obtained is pulverized, obtains modified composite material;
(7) by above-mentioned p-aminobenzene sulfonic acid, lauryl mercaptan mixing, rise high-temperature and be 80-90 DEG C, add the 20-26% of above-mentioned nylon66 fiber weight, heat-insulation preheating 10-14 minute, mix with above-mentioned modified composite material, triisopropanolamine, rise high-temperature and be 110-120 DEG C, continue insulation 6-10 minute, obtain premix material;
(8) above-mentioned premix material is mixed with remaining each raw material, stir, send in injection machine, adding heat fusing, be injected in mould by nozzle by the fluid after melted, the initial temperature of mould is maintained at 130-150 DEG C, after injection molding under 80-90MPa pressurize 1-2s, cooling, the demoulding, obtain described nylon mold materials.
CN201610275885.5A 2016-04-29 2016-04-29 Antistatic polyamide mold material and preparing method thereof Withdrawn CN105838065A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107629445A (en) * 2017-09-13 2018-01-26 苏州聚慧邦新材料科技有限公司 A kind of fire-retardant nylon material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
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CN103483808A (en) * 2012-06-11 2014-01-01 辽宁辽杰科技有限公司 Composite thermoplastic resin mould material, preparation method thereof, mould and manufacturing method thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107629445A (en) * 2017-09-13 2018-01-26 苏州聚慧邦新材料科技有限公司 A kind of fire-retardant nylon material and preparation method thereof

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Application publication date: 20160810