CN105062062A - Halogen-free flame-retardant nylon composite material and preparation method thereof - Google Patents

Halogen-free flame-retardant nylon composite material and preparation method thereof Download PDF

Info

Publication number
CN105062062A
CN105062062A CN201510588777.9A CN201510588777A CN105062062A CN 105062062 A CN105062062 A CN 105062062A CN 201510588777 A CN201510588777 A CN 201510588777A CN 105062062 A CN105062062 A CN 105062062A
Authority
CN
China
Prior art keywords
halogen
matrix material
resin
mixture
fusing point
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510588777.9A
Other languages
Chinese (zh)
Inventor
王研石
王代军
李卫明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongguan Wofu Engineering Plastic Science & Technology Co Ltd
Original Assignee
Dongguan Wofu Engineering Plastic Science & Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongguan Wofu Engineering Plastic Science & Technology Co Ltd filed Critical Dongguan Wofu Engineering Plastic Science & Technology Co Ltd
Priority to CN201510588777.9A priority Critical patent/CN105062062A/en
Publication of CN105062062A publication Critical patent/CN105062062A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92514—Pressure
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/017—Additives being an antistatic agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids

Abstract

The invention relates to the technical field of high molecular materials, in particular to a halogen-free flame-retardant nylon composite material and a preparation method thereof. The flame-retardant nylon composite material and preparation method thereof comprises the following raw materials in parts by weight: 70-90 parts of PA66 resin, 5-15 parts of PA6 resin, 5-15 parts of halogen-free flame retardant, 0.1-0.5 part of a stabilizing agent and 0.1-0.5 part of a nucleating agent. The nylon composite material utilizes a special nucleating technology, the crystallization speed is high, performances at high temperature are stable, the nylon composite material is not easy to age, the comprehensive performance is good, the rigidity is high, and the appearance of a product is very bright; furthermore, the flame retardance level is up to the UL94V0 level, and the fireproofness is good; the nylon composite material is low in precipitation and dripping-resistant and has high electrical performance and excellent heat resistance; a CTI value is high, the electrical performance is good, the impact strength is high, and environmental-friendliness is achieved.

Description

A kind of halogen-free reinforced nylon matrix material and preparation method thereof
Technical field
The present invention relates to technical field of polymer materials, be specifically related to a kind of halogen-free reinforced nylon matrix material and preparation method thereof.
Background technology
Nylon resin, i.e. polymeric amide, there is excellent mechanical strength, wear resistance, self lubricity, erosion resistance and good machine-shaping property, at present oneself become that output in five large general engineering plastic is maximum, kind at most, purposes the most extensively, the base resin of high comprehensive performance.
Along with developing rapidly of electric industry and other special industries, its flame retardant properties of the nylon of non-modified is poor, and its vertical combustion can only reach UL94V-2 level, and oxygen index is about 24, and produces drippage in combustion, belongs to inflammable material.In use very easily initiation fire, especially at electronics field, Yin Nilong and the fire caused is countless, causes damage larger.
The fire retardant kind used in current nylon66 fiber is more, comprising: bromide fire retardant is as decabromodiphenyl oxide, decabromodiphenyl ethane etc.; Phosphorus flame retardant is as red phosphorus; Nitrogenated flame retardant is as trimeric cyanamide, cyanurate (MCA), and solid flame retardant is as antimonous oxide, zinc borate, silicon-dioxide etc.What halogen-free flame-retardant system application was wider is red phosphorus and trimeric cyanamide salt, but red phosphorus band look itself, can only black products be used for, and general only in nylon 6, range of application is narrower.In addition be then trimeric cyanamide salt, mainly trimeric cyanamide urea hydrochlorate and phosphoric acid salt, but its flame retardant effect is not good, and the flame retardant effect extremely unstable formed, general addition is large and can not reach higher flame retardant rating, also can only be applicable to the not high occasion of flame-retardancy requirements.
The patent No. is that the Chinese invention patent of ZL201110117041.5 discloses a kind of flame-retardant nylon resin composition, the fire retardant of employing be selected from TDE, three-(tribromophenoxy)-triazine, brominated Polystyrene, brominated epoxy resin and melamine cyanurate at least one; Fire retarding synergist is selected from least one in the oxide compound of antimony, stibnate and V race metallic element compound.
The patent No. is that the Chinese invention patent of ZL201110117041.5 discloses a kind of flame-retardant nylon resin composition, by adding fire retardant modification, makes the excellent fireproof performance of whole resin combination; Simultaneously, in formula, the consistency of each component is better, the synergy of lubricant and oxidation inhibitor, the processing flowability of nylon resin can be improved, improve fire retardant dispersing property in the composition, obtained flame-retardant nylon resin composition outdoor weatherability can be good, and high, the fire-retardant degree of shock strength, bending strength and tensile strength well, mobility is high.But be not difficult to find out from its formula, its fire-retardant employing be halogen containing flame-retardant, simultaneously in order to the flame retardant effect promoting halogen containing flame-retardant has also coordinated the oxide compound of antimony, stibnate or V race metallic element compound to be used as fire retarding synergist.Halogen containing flame-retardant refers to the fire retardant containing elements such as Cl, Br, F, halogen containing flame-retardant is the flame retardant products that in current plastic, rubber material, fire-retardant application is maximum, mainly it is organic fire-retardant, chemical property is inertia, relatively good with the consistency of plastics, good flame retardation effect, use cost are low, and all multiple features are all that other fire retardant is irreplaceable, but Halogen fire retardant material can produce a large amount of smog and poisonous corrosive hydrogen halides gas, causes secondary to endanger.Now forbid completely in some developed countries, obvious prior art has the necessity improved further.
Summary of the invention
In order to overcome the shortcoming and defect existed in prior art, the object of the present invention is to provide a kind of halogen-free reinforced nylon matrix material, this nylon composite materials adopts special one-tenth nuclear technique, crystallization velocity is fast, and stable performance is under the high temperature conditions not easily aging, over-all properties is better, have higher rigidity, products appearance is very bright, and fire-retardant rank reaches UL94V0 level, fire line is good, have low precipitation, anti-drippage, high electrical property and excellent heat resistance, CTI value is high, good electric property, shock strength is high, good to environment, environmental protection.
Another object of the present invention is to the preparation method providing a kind of halogen-free reinforced nylon matrix material, this preparation method's technique is simple, and convenient operation and control, steady quality, production efficiency is high, and production cost is low, can large-scale industrial production.
Object of the present invention is achieved through the following technical solutions: a kind of halogen-free reinforced nylon matrix material, and described nylon composite materials comprises the raw material of following weight part:
PA66 resin 70-90 part
PA6 resin 5-15 part
Halogen-free flame retardants 5-15 part
Stablizer 0.1-0.5 part
Nucleator 0.1-0.5 part.
Nylon composite materials of the present invention adopts special one-tenth nuclear technique, and crystallization velocity is fast, stable performance under the high temperature conditions, not easily aging, over-all properties is better, has higher rigidity, products appearance is very bright, and fire-retardant rank reaches UL94V0 level, and fire line is good, have low precipitation, anti-drippage, high electrical property and excellent heat resistance, CTI value is high, good electric property, shock strength is high, good to environment, environmental protection.
Preferably, described PA66 resin is that density is at 1.10-1.14g/cm 3, fusing point 250-254 DEG C, molecular-weight average at 10,000-100, the PA 66 of 000.
The present invention is by adopting density at 1.10-1.14g/cm 3, fusing point 250-254 DEG C, molecular-weight average at 10,000-100, the PA 66 of 000, makes nylon composite materials have excellent tensile strength, resistance to tough, shock-resistance and wear resistance good.
Preferably, described PA6 resin is that density is at 1.14-1.18g/cm 3, fusing point 215-225 DEG C, molecular-weight average at 10,000-100, the polycaprolactam of 000.
The present invention is by adopting density at 1.14-1.18g/cm 3, fusing point 215-225 DEG C, molecular-weight average at 10,000-100, the polycaprolactam of 000, as PA6 resin, makes nylon composite materials have excellent thermoplasticity, toughness and good endurance.
Preferably, described halogen-free flame retardants be fusing point 348-352 DEG C, density is at 1.5-1.7g/cm 3melamine cyanurate.
The present invention by adopt fusing point 348-352 DEG C, density is at 1.5-1.7g/cm 3melamine cyanurate as halogen-free flame retardants, make the fire-retardant rank of nylon composite materials reach UL94V0 level, fire line is good, has low precipitation, anti-drippage, high electrical property and excellent heat resistance
Preferably, described stablizer is fusing point at the N of 270-274 DEG C, N '-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzenedicarboxamide.
The present invention is by the N of employing fusing point at 270-274 DEG C, N '-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzenedicarboxamide is as stablizer, compatible with nylon with interlinkage amidation by " molecular recognition ", improve the melt stability of nylon composite materials, thus improve nylon composite materials processibility, reduce fiber wire broken rate, improve the quality of products; To the light, heat, oxidation etc. of nylon composite materials, there is long-acting stabilization; Filler and the dispersiveness of pigment in nylon composite materials can be improved.
Preferably, the mixture that described nucleator is made up of with weight ratio 0.8-1.2:1 inorganic nucleator and organic nucleating agent, the particle diameter of nucleator is 0.1-1 μm.
The present invention is by adopting inorganic nucleator and the composite use of organic nucleating agent, and to control its weight ratio be 0.8-1.2:1, and crystallization velocity is fast, make nylon composite materials stable performance under the high temperature conditions, not easily aging, over-all properties is better, have higher rigidity, products appearance is very bright.
Preferably, described inorganic nucleator comprises at least one in superfine talcum powder, polynite and calcium carbonate.More preferred, the mixture that described inorganic nucleator is made up of with weight ratio 1:1.5-2.5:2-4 superfine talcum powder, polynite and calcium carbonate.
The present invention is by adopting superfine talcum powder, polynite and calcium carbonate as the composite use of inorganic nucleator, and to control its weight ratio be 1:1.5-2.5:2-4, crystallization velocity is fast, makes nylon composite materials stable performance under the high temperature conditions, not easily aging, over-all properties is better.
Described organic nucleating agent comprises at least one in Sodium Benzoate, sorbyl alcohol dibenzyl ester and long-chain linear saturated carboxylic acid sodium salt.More preferred, the mixture that described organic nucleating agent is made up of with weight ratio 0.8-1.2:1:1.4-2.2 Sodium Benzoate, sorbyl alcohol dibenzyl ester and long-chain linear saturated carboxylic acid sodium salt.
The present invention is by adopting Sodium Benzoate, sorbyl alcohol dibenzyl ester and long-chain linear saturated carboxylic acid sodium salt as the composite use of organic nucleating agent, and to control its weight ratio be 0.8-1.2:1:1.4-2.2, crystallization velocity is fast, make nylon composite materials stable performance under the high temperature conditions, not easily aging, over-all properties is better, and have higher rigidity, products appearance is very bright
Preferably, described nylon composite materials also comprises lubricant 0.5-1.5 part, and described lubricant comprises at least one in modified vinyl bis-stearamides, pentaerythritol stearate and oxidized polyethlene wax.More preferred, the mixture that described lubricant is made up of with weight ratio 0.8-1.2:1.6-2.4:1 modified vinyl bis-stearamides, pentaerythritol stearate and oxidized polyethlene wax.
The present invention is by adopting modified vinyl bis-stearamides, pentaerythritol stearate and oxidized polyethlene wax as the composite use of lubricant, and to control its weight ratio be 0.8-1.2:1.6-2.4:1, oxidized polyethlene wax is external lubricant, can reduce the friction of nylon resin melt and mould, machine barrel; Modified vinyl bis-stearamides and pentaerythritol stearate are internal lubricants, can reduce the intermolecular friction of nylon resin melt; Three kinds of mix lubricant use can improve the mobility of nylon composite materials in the course of processing and the release property of goods.
Preferably, the mixture that is made up of with weight ratio 2-3:1 at the pentaerythritol tetrastearate of 55-65 DEG C at 25-35mgKOH/g, fusing point in the tetramethylolmethane tristearate of 50-60 DEG C and hydroxyl value at 55-65mgKOH/g, fusing point hydroxyl value of described pentaerythritol stearate.
The present invention by adopt hydroxyl value at 55-65mgKOH/g, fusing point in the tetramethylolmethane tristearate of 50-60 DEG C and hydroxyl value at 25-35mgKOH/g, fusing point at the pentaerythritol tetrastearate of 55-65 DEG C as the composite use of pentaerythritol stearate, and to control its weight ratio be 2-3:1, there is good thermostability and low volatility, the good demoulding and flowing property, significantly can improve the processing characteristics of nylon composite materials when high temperature, improve transparency and the surface smoothness of goods.
Described nylon composite materials also comprises modification POE resin 3-7 part, static inhibitor 1-5 part, oxidation inhibitor 0.5-1.5 part, intensity modifier 1-5 part, plasticized modifier 1-5 part, impact modifier 1-5 part.
Described modification POE resin is polypropylene/ethylene-octene copolymer that polypropylene and POE resin blending and modifying obtain; Described ethylene-octene copolymer is the ethylene-octene copolymer of octene monomers content at 20%-30%.
The present invention as modification POE resin, significantly can improve normal temperature and the low-temperature impact toughness of material by polypropylene/ethylene-octene copolymer of adopting polypropylene and POE resin blending and modifying and obtaining.The present invention, by adopting octene monomers content at the ethylene-octene copolymer of 20%-30%, can significantly improve resistance to impact shock and the resistance toheat of material, and the Main Mechanical such as tensile strength, tear strength all has significant improvement.
The mixture that described polypropylene is made up of with weight ratio 1.4-2.2:1 Co-polypropylene and homo-polypropylene; Described Co-polypropylene is the Co-polypropylene of melting index at 10-50g/10min; Described homo-polypropylene is the homo-polypropylene of melting index at 60-100g/10min.
The present invention by adopt melting index in the Co-polypropylene of 10-50g/10min and melting index in the homo-polypropylene of 60-100g/10min as the composite use of polypropylene, and to control its weight ratio be 1.4-2.2:1, resistance to impact shock and the heat-drawn wire of material can be significantly improved.
The mixture that described static inhibitor is made up of with weight ratio 1:1.4-2.2 carbon black and carbon fiber.
The present invention is by adopting carbon black and carbon fiber as the composite use of static inhibitor, and to control its weight ratio be 1:1.4-2.2, make material modified surface resistivity reach 5-7 the order of magnitude, on the basis keeping material shock resistance, the antistatic property of material can be significantly improved.
Described carbon black is that specific surface area is at 80-140m 3/ g, particle diameter are at the carbon black of 8-12nm; Described carbon fiber is the carbon fiber of length-to-diameter ratio at 400-600.
The present invention is by adopting specific surface area at 80-140m 3/ g, particle diameter, at the carbon black of 8-12nm, can significantly improve the antistatic property of material.The present invention, by adopting length-to-diameter ratio at the carbon fiber of 400-600, can significantly improve the antistatic property of material.
The mixture that described oxidation inhibitor is made up of with weight ratio 1:1-2 antioxidant 1010 and irgasfos 168.
The present invention is by adopting antioxidant 1010 and irgasfos 168 as the composite use of oxidation inhibitor, and to control its weight ratio be 1:1-2, two kinds of oxidation inhibitor are environmental protection oxidation inhibitor and have certain synergy, can delay or suppress the carrying out of material oxidation process, thus stop the aging of material and extend its work-ing life.
The mixture that described intensity modifier is made up of with weight ratio 1.6-2.4:1 at the magnesium salt whisker of 6-10 μm at the basalt fibre of 4-8 μm and filament diameter filament diameter.
Basalt fibre, be basalt building stones after 1450 DEG C ~ 1500 DEG C meltings, by the continuous fibre of platinum rhodium bushing high speed pulling.Be similar to glass fibre, its performance is between high strength S glass fibre and alkali-free E glass fibre, and basalt continuous fiber is good stability not only, but also has electrical insulating property, anticorrosive, flame resistant, the multiple excellent properties such as high temperature resistant.Adopt basalt building stones as intensity modifier, compared with glass fibre, there is the advantages such as intensity is high, shock strength is high, temperature tolerance is excellent.
Magnesium salt whisker is single palpus fibrous texture, and diameter is in nano-scale range, and magnesium salt whisker has very high physical and mechanical properties, the intensity of energy Reinforced Nylon material after adding; And magnesium salt whisker easily disperses, good with the consistency of resin, obtained nylon product surface scratch resistance capability is strong, dimensional stabilizing not easily buckling deformation, and can improve the ageing resistance of nylon product.
The present invention is by adopting basalt fibre and magnesium salt whisker as the composite use of intensity modifier, and to control its weight ratio be 1.6-2.4:1, significantly can mention the intensity of nylon material.
Described plasticized modifier is the vinyl elastomerics of maleic anhydride and methyl methacrylate dual graft.
The present invention, by adopting the vinyl elastomerics of maleic anhydride and methyl methacrylate dual graft as plasticized modifier, can significantly improve toughness and the resistance to impact shock of material.
Described impact modifier is the polyester type Polyurethane Thermoplastic Elastomer of molecular weight at 40000-80000.
Polyester type Polyurethane Thermoplastic Elastomer has excellent in abrasion resistance, ozone resistance is fabulous, hardness is large, intensity is high, good springiness, low temperature resistant, have the advantages such as good oil resistant, chemical-resistant resistance and environmental resistance.
The present invention is by adopting molecular weight in the polyester type Polyurethane Thermoplastic Elastomer of 40000-80000 as impact modifier, the shock resistance of material can be improved, the processing characteristics that can also reduce the melt viscosity of material, improve mobility, improve plastics, improves the erosion resistance of material, rigidity, flame retardant resistance, electrical insulating property, thermotolerance and molding processibility.
Another object of the present invention is achieved through the following technical solutions: a kind of preparation method of halogen-free reinforced nylon matrix material, comprises the steps:
(1) take above-mentioned raw materials by weight ratio, join blended 5-10min in high speed mixer, obtain mixture;
(2) blended for step (1) mixture obtained is extruded through forcing machine, cooling, pelletizing and screening, obtained nylon composite materials;
In described step (2), the processing parameter of forcing machine is: a district temperature 210-250 DEG C, two district temperature 210-250 DEG C, three district temperature 210-250 DEG C, four district temperature 210-250 DEG C, five district temperature 210-250 DEG C, six district temperature 210-250 DEG C, seven district temperature 210-240 DEG C, eight district temperature 210-240 DEG C, nine district temperature 210-240 DEG C, die head temperature 210-230 DEG C, pressure 18-23Mpa, screw speed 350-450r/min.
Preparation method's technique of the present invention is simple, and convenient operation and control, steady quality, production efficiency is high, and production cost is low, can large-scale industrial production.
Beneficial effect of the present invention is: nylon composite materials of the present invention adopts special one-tenth nuclear technique, and crystallization velocity is fast, stable performance under the high temperature conditions, not easily aging, over-all properties is better, has higher rigidity, products appearance is very bright, and fire-retardant rank reaches UL94V0 level, and fire line is good, have low precipitation, anti-drippage, high electrical property and excellent heat resistance, CTI value is high, good electric property, shock strength is high, good to environment, environmental protection.
Preparation method's technique of the present invention is simple, and convenient operation and control, steady quality, production efficiency is high, and production cost is low, can large-scale industrial production.
Embodiment
For the ease of the understanding of those skilled in the art, below in conjunction with embodiment, the present invention is further illustrated, and the content that embodiment is mentioned not is limitation of the invention.
Embodiment 1
A kind of halogen-free reinforced nylon matrix material, described nylon composite materials comprises the raw material of following weight part:
PA66 resin 70 parts
PA6 resin 5 parts
Halogen-free flame retardants 5 parts
Stablizer 0.1 part
Nucleator 0.1 part.
Described PA66 resin is that density is at 1.10g/cm 3, fusing point 250 DEG C, molecular-weight average 10, the PA 66 of 000.
Described PA6 resin is that density is at 1.14g/cm 3, fusing point 215 DEG C, molecular-weight average 10, the polycaprolactam of 000.
Described halogen-free flame retardants be fusing point 348 DEG C, density is at 1.5g/cm 3melamine cyanurate.
Described stablizer is fusing point at the N of 270 DEG C, N '-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzenedicarboxamide.
The mixture that described nucleator is made up of with weight ratio 0.8:1 inorganic nucleator and organic nucleating agent, the particle diameter of nucleator is 0.1 μm.
The mixture that described inorganic nucleator is made up of with weight ratio 1:1.5:2 superfine talcum powder, polynite and calcium carbonate; The mixture that described organic nucleating agent is made up of with weight ratio 0.8:1:1.4 Sodium Benzoate, sorbyl alcohol dibenzyl ester and long-chain linear saturated carboxylic acid sodium salt.
Described nylon composite materials also comprises lubricant 0.5 part, the mixture that described lubricant is made up of with weight ratio 0.8:1.6:1 modified vinyl bis-stearamides, pentaerythritol stearate and oxidized polyethlene wax.
The mixture that described pentaerythritol stearate is made up of with weight ratio 2:1 at the pentaerythritol tetrastearate of 55 DEG C at 25mgKOH/g, fusing point in the tetramethylolmethane tristearate of 50 DEG C and hydroxyl value at 55mgKOH/g, fusing point hydroxyl value.
A preparation method for halogen-free reinforced nylon matrix material, comprises the steps:
(1) take above-mentioned raw materials by weight ratio, join blended 5min in high speed mixer, obtain mixture;
(2) blended for step (1) mixture obtained is extruded through forcing machine, cooling, pelletizing and screening, obtained nylon composite materials;
In described step (2), the processing parameter of twin screw extruder is: district's temperature 210 DEG C, two district's temperature 210 DEG C, three district's temperature 210 DEG C, four district's temperature 210 DEG C, five district's temperature 210 DEG C, six district's temperature 210 DEG C, seven district's temperature 210 DEG C, eight district's temperature 210 DEG C, nine district's temperature 210 DEG C, die head temperature 210 DEG C, pressure 18Mpa, screw speed 350r/min.
Embodiment 2
A kind of halogen-free reinforced nylon matrix material, described nylon composite materials comprises the raw material of following weight part:
PA66 resin 75 parts
PA6 resin 8 parts
Halogen-free flame retardants 8 parts
Stablizer 0.2 part
Nucleator 0.2 part.
Described PA66 resin is that density is at 1.11g/cm 3, fusing point 251 DEG C, molecular-weight average 30, the PA 66 of 000.
Described PA6 resin is that density is at 1.15g/cm 3, fusing point 218 DEG C, molecular-weight average 30, the polycaprolactam of 000.
Described halogen-free flame retardants be fusing point 349 DEG C, density is at 1.55g/cm 3melamine cyanurate.
Described stablizer is fusing point at the N of 271 DEG C, N '-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzenedicarboxamide.
The mixture that described nucleator is made up of with weight ratio 0.9:1 inorganic nucleator and organic nucleating agent, the particle diameter of nucleator is 0.3 μm.
The mixture that described inorganic nucleator is made up of with weight ratio 1:1.8:2.5 superfine talcum powder, polynite and calcium carbonate; The mixture that described organic nucleating agent is made up of with weight ratio 0.9:1:1.6 Sodium Benzoate, sorbyl alcohol dibenzyl ester and long-chain linear saturated carboxylic acid sodium salt.
Described nylon composite materials also comprises lubricant 0.8 part, the mixture that described lubricant is made up of with weight ratio 0.9:1.8:1 modified vinyl bis-stearamides, pentaerythritol stearate and oxidized polyethlene wax.
The mixture that described pentaerythritol stearate is made up of with weight ratio 2.2:1 at the pentaerythritol tetrastearate of 58 DEG C at 28mgKOH/g, fusing point in the tetramethylolmethane tristearate of 52 DEG C and hydroxyl value at 58mgKOH/g, fusing point hydroxyl value.
A preparation method for halogen-free reinforced nylon matrix material, comprises the steps:
(1) take above-mentioned raw materials by weight ratio, join blended 6min in high speed mixer, obtain mixture;
(2) blended for step (1) mixture obtained is extruded through forcing machine, cooling, pelletizing and screening, obtained nylon composite materials;
In described step (2), the processing parameter of twin screw extruder is: district's temperature 220 DEG C, two district's temperature 220 DEG C, three district's temperature 220 DEG C, four district's temperature 220 DEG C, five district's temperature 220 DEG C, six district's temperature 220 DEG C, seven district's temperature 218 DEG C, eight district's temperature 218 DEG C, nine district's temperature 218 DEG C, die head temperature 215 DEG C, pressure 20Mpa, screw speed 380r/min.
Embodiment 3
A kind of halogen-free reinforced nylon matrix material, described nylon composite materials comprises the raw material of following weight part:
PA66 resin 80 parts
PA6 resin 10 parts
Halogen-free flame retardants 10 parts
Stablizer 0.3 part
Nucleator 0.3 part.
Described PA66 resin is that density is at 1.12g/cm 3, fusing point 252 DEG C, molecular-weight average 50, the PA 66 of 000.
Described PA6 resin is that density is at 1.16g/cm 3, fusing point 220 DEG C, molecular-weight average 50, the polycaprolactam of 000.
Described halogen-free flame retardants be fusing point 350 DEG C, density is at 1.6g/cm 3melamine cyanurate.
Described stablizer is fusing point at the N of 272 DEG C, N '-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzenedicarboxamide.
The mixture that described nucleator is made up of with weight ratio 1:1 inorganic nucleator and organic nucleating agent, the particle diameter of nucleator is 0.5 μm.
The mixture that described inorganic nucleator is made up of with weight ratio 1:2:3 superfine talcum powder, polynite and calcium carbonate; The mixture that described organic nucleating agent is made up of with weight ratio 1:1:1.8 Sodium Benzoate, sorbyl alcohol dibenzyl ester and long-chain linear saturated carboxylic acid sodium salt.
Described nylon composite materials also comprises lubricant 1 part, the mixture that described lubricant is made up of with weight ratio 1:2:1 modified vinyl bis-stearamides, pentaerythritol stearate and oxidized polyethlene wax.
The mixture that described pentaerythritol stearate is made up of with weight ratio 2.5:1 at the pentaerythritol tetrastearate of 60 DEG C at 30mgKOH/g, fusing point in the tetramethylolmethane tristearate of 55 DEG C and hydroxyl value at 60mgKOH/g, fusing point hydroxyl value.
A preparation method for halogen-free reinforced nylon matrix material, comprises the steps:
(1) take above-mentioned raw materials by weight ratio, join blended 8min in high speed mixer, obtain mixture;
(2) blended for step (1) mixture obtained is extruded through forcing machine, cooling, pelletizing and screening, obtained nylon composite materials;
In described step (2), the processing parameter of twin screw extruder is: district's temperature 230 DEG C, two district's temperature 230 DEG C, three district's temperature 230 DEG C, four district's temperature 230 DEG C, five district's temperature 230 DEG C, six district's temperature 230 DEG C, seven district's temperature 225 DEG C, eight district's temperature 225 DEG C, nine district's temperature 225 DEG C, die head temperature 2120 DEG C, pressure 20Mpa, screw speed 400r/min.
Embodiment 4
A kind of halogen-free reinforced nylon matrix material, described nylon composite materials comprises the raw material of following weight part:
PA66 resin 85 parts
PA6 resin 12 parts
Halogen-free flame retardants 12 parts
Stablizer 0.4 part
Nucleator 0.4 part.
Described PA66 resin is that density is at 1.13g/cm 3, fusing point 253 DEG C, molecular-weight average 80, the PA 66 of 000.
Described PA6 resin is that density is at 1.17g/cm 3, fusing point 222 DEG C, molecular-weight average 80, the polycaprolactam of 000.
Described halogen-free flame retardants be fusing point 351 DEG C, density is at 1.65g/cm 3melamine cyanurate.
Described stablizer is fusing point at the N of 273 DEG C, N '-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzenedicarboxamide.
The mixture that described nucleator is made up of with weight ratio 1.1:1 inorganic nucleator and organic nucleating agent, the particle diameter of nucleator is 0.8 μm.
The mixture that described inorganic nucleator is made up of with weight ratio 1:2.2:3.5 superfine talcum powder, polynite and calcium carbonate; The mixture that described organic nucleating agent is made up of with weight ratio 1.1:1:2 Sodium Benzoate, sorbyl alcohol dibenzyl ester and long-chain linear saturated carboxylic acid sodium salt.
Described nylon composite materials also comprises lubricant 1.2 parts, the mixture that described lubricant is made up of with weight ratio 1.1:2.2:1 modified vinyl bis-stearamides, pentaerythritol stearate and oxidized polyethlene wax.
The mixture that described pentaerythritol stearate is made up of with weight ratio 2.8:1 at the pentaerythritol tetrastearate of 62 DEG C at 32mgKOH/g, fusing point in the tetramethylolmethane tristearate of 58 DEG C and hydroxyl value at 62mgKOH/g, fusing point hydroxyl value.
A preparation method for halogen-free reinforced nylon matrix material, comprises the steps:
(1) take above-mentioned raw materials by weight ratio, join blended 9min in high speed mixer, obtain mixture;
(2) blended for step (1) mixture obtained is extruded through forcing machine, cooling, pelletizing and screening, obtained nylon composite materials;
In described step (2), the processing parameter of twin screw extruder is: district's temperature 240 DEG C, two district's temperature 240 DEG C, three district's temperature 240 DEG C, four district's temperature 240 DEG C, five district's temperature 240 DEG C, six district's temperature 240 DEG C, seven district's temperature 232 DEG C, eight district's temperature 232 DEG C, nine district's temperature 232 DEG C, die head temperature 225 DEG C, pressure 22Mpa, screw speed 420r/min.
Embodiment 5
A kind of halogen-free reinforced nylon matrix material, described nylon composite materials comprises the raw material of following weight part:
PA66 resin 90 parts
PA6 resin 15 parts
Halogen-free flame retardants 15 parts
Stablizer 0.5 part
Nucleator 0.5 part.
Described PA66 resin is that density is at 1.14g/cm 3, fusing point 254 DEG C, molecular-weight average 100, the PA 66 of 000.
Described PA6 resin is that density is at 1.18g/cm 3, fusing point 225 DEG C, molecular-weight average 100, the polycaprolactam of 000.
Described halogen-free flame retardants be fusing point 352 DEG C, density is at 1.7g/cm 3melamine cyanurate.
Described stablizer is fusing point at the N of 274 DEG C, N '-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzenedicarboxamide.
The mixture that described nucleator is made up of with weight ratio 1.2:1 inorganic nucleator and organic nucleating agent, the particle diameter of nucleator is 1 μm.
The mixture that described inorganic nucleator is made up of with weight ratio 1:2.5:4 superfine talcum powder, polynite and calcium carbonate; The mixture that described organic nucleating agent is made up of with weight ratio 1.2:1:2.2 Sodium Benzoate, sorbyl alcohol dibenzyl ester and long-chain linear saturated carboxylic acid sodium salt.
Described nylon composite materials also comprises lubricant 1.5 parts, the mixture that described lubricant is made up of with weight ratio 1.2:2.4:1 modified vinyl bis-stearamides, pentaerythritol stearate and oxidized polyethlene wax.
The mixture that described pentaerythritol stearate is made up of with weight ratio 3:1 at the pentaerythritol tetrastearate of 65 DEG C at 35mgKOH/g, fusing point in the tetramethylolmethane tristearate of 60 DEG C and hydroxyl value at 65mgKOH/g, fusing point hydroxyl value.
A preparation method for halogen-free reinforced nylon matrix material, comprises the steps:
(1) take above-mentioned raw materials by weight ratio, join blended 10min in high speed mixer, obtain mixture;
(2) blended for step (1) mixture obtained is extruded through forcing machine, cooling, pelletizing and screening, obtained nylon composite materials;
In described step (2), the processing parameter of twin screw extruder is: district's temperature 250 DEG C, two district's temperature 250 DEG C, three district's temperature 250 DEG C, four district's temperature 250 DEG C, five district's temperature 250 DEG C, six district's temperature 250 DEG C, seven district's temperature 240 DEG C, eight district's temperature 240 DEG C, nine district's temperature 240 DEG C, die head temperature 230 DEG C, pressure 23Mpa, screw speed 450r/min.
Embodiment 6
The present embodiment is in the difference of above-described embodiment 1:
Described nylon composite materials also comprises modification POE resin 3 parts, 1 part, static inhibitor, 0.5 part, oxidation inhibitor, intensity modifier 1 part, plasticized modifier 1 part, impact modifier 1 part.
Described modification POE resin is polypropylene/ethylene-octene copolymer that polypropylene and POE resin blending and modifying obtain; Described ethylene-octene copolymer be octene monomers content 20% ethylene-octene copolymer.
The mixture that described polypropylene is made up of with weight ratio 1.4:1 Co-polypropylene and homo-polypropylene; Described Co-polypropylene is the Co-polypropylene of melting index at 10g/10min; Described homo-polypropylene is the homo-polypropylene of melting index at 60g/10min.
The mixture that described static inhibitor is made up of with weight ratio 1:1.4 carbon black and carbon fiber.
Described carbon black is that specific surface area is at 800m 3/ g, particle diameter are at the carbon black of 8nm; Described carbon fiber be length-to-diameter ratio 400 carbon fiber.
The mixture that described oxidation inhibitor is made up of with weight ratio 1:1 antioxidant 1010 and irgasfos 168.
The mixture that described intensity modifier is made up of with weight ratio 1.6:1 at the magnesium salt whisker of 6 μm at the basalt fibre of 4 μm and filament diameter filament diameter.
Described plasticized modifier is the vinyl elastomerics of maleic anhydride and methyl methacrylate dual graft.
Described impact modifier be molecular weight 40000 polyester type Polyurethane Thermoplastic Elastomer.
Embodiment 7
The present embodiment is in the difference of above-described embodiment 2:
Described nylon composite materials also comprises modification POE resin 4 parts, 2 parts, static inhibitor, 0.8 part, oxidation inhibitor, intensity modifier 2 parts, plasticized modifier 2 parts, impact modifier 2 parts.
Described modification POE resin is polypropylene/ethylene-octene copolymer that polypropylene and POE resin blending and modifying obtain; Described ethylene-octene copolymer be octene monomers content 22% ethylene-octene copolymer.
The mixture that described polypropylene is made up of with weight ratio 1.6:1 Co-polypropylene and homo-polypropylene; Described Co-polypropylene is the Co-polypropylene of melting index at 20g/10min; Described homo-polypropylene is the homo-polypropylene of melting index at 70g/10min.
The mixture that described static inhibitor is made up of with weight ratio 1:1.6 carbon black and carbon fiber.
Described carbon black is that specific surface area is at 100m 3/ g, particle diameter are at the carbon black of 9nm; Described carbon fiber be length-to-diameter ratio 450 carbon fiber.
The mixture that described oxidation inhibitor is made up of with weight ratio 1:1.2 antioxidant 1010 and irgasfos 168.
The mixture that described intensity modifier is made up of with weight ratio 1.8:1 at the magnesium salt whisker of 7 μm at the basalt fibre of 4 ~ 8 μm and filament diameter filament diameter.
Described plasticized modifier is the vinyl elastomerics of maleic anhydride and methyl methacrylate dual graft.
Described impact modifier be molecular weight 50000 polyester type Polyurethane Thermoplastic Elastomer.
Embodiment 8
The present embodiment is in the difference of above-described embodiment 3:
Described nylon composite materials also comprises modification POE resin 5 parts, 3 parts, static inhibitor, 1 part, oxidation inhibitor, intensity modifier 3 parts, plasticized modifier 3 parts, impact modifier 3 parts.
Described modification POE resin is polypropylene/ethylene-octene copolymer that polypropylene and POE resin blending and modifying obtain; Described ethylene-octene copolymer be octene monomers content 25% ethylene-octene copolymer.
The mixture that described polypropylene is made up of with weight ratio 1.8:1 Co-polypropylene and homo-polypropylene; Described Co-polypropylene is the Co-polypropylene of melting index at 30g/10min; Described homo-polypropylene is the homo-polypropylene of melting index at 80g/10min.
The mixture that described static inhibitor is made up of with weight ratio 1:1.8 carbon black and carbon fiber.
Described carbon black is that specific surface area is at 110m 3/ g, particle diameter are at the carbon black of 10nm; Described carbon fiber be length-to-diameter ratio 500 carbon fiber.
The mixture that described oxidation inhibitor is made up of with weight ratio 1:1.5 antioxidant 1010 and irgasfos 168.
The mixture that described intensity modifier is made up of with weight ratio 2:1 at the magnesium salt whisker of 8 μm at the basalt fibre of 6 μm and filament diameter filament diameter.
Described plasticized modifier is the vinyl elastomerics of maleic anhydride and methyl methacrylate dual graft.
Described impact modifier be molecular weight 60000 polyester type Polyurethane Thermoplastic Elastomer.
Embodiment 9
The present embodiment is in the difference of above-described embodiment 4:
Described nylon composite materials also comprises modification POE resin 6 parts, 4 parts, static inhibitor, 1.2 parts, oxidation inhibitor, intensity modifier 4 parts, plasticized modifier 4 parts, impact modifier 4 parts.
Described modification POE resin is polypropylene/ethylene-octene copolymer that polypropylene and POE resin blending and modifying obtain; Described ethylene-octene copolymer be octene monomers content 28% ethylene-octene copolymer.
The mixture that described polypropylene is made up of with weight ratio 2:1 Co-polypropylene and homo-polypropylene; Described Co-polypropylene is the Co-polypropylene of melting index at 40g/10min; Described homo-polypropylene is the homo-polypropylene of melting index at 90g/10min.
The mixture that described static inhibitor is made up of with weight ratio 1:2 carbon black and carbon fiber.
Described carbon black is that specific surface area is at 120m 3/ g, particle diameter are at the carbon black of 11nm; Described carbon fiber be length-to-diameter ratio 550 carbon fiber.
The mixture that described oxidation inhibitor is made up of with weight ratio 1:1.8 antioxidant 1010 and irgasfos 168.
The mixture that described intensity modifier is made up of with weight ratio 2.2:1 at the magnesium salt whisker of 9 μm at the basalt fibre of 7 μm and filament diameter filament diameter.
Described plasticized modifier is the vinyl elastomerics of maleic anhydride and methyl methacrylate dual graft.
Described impact modifier be molecular weight 70000 polyester type Polyurethane Thermoplastic Elastomer.
Embodiment 10
The present embodiment is in the difference of above-described embodiment 5:
Described nylon composite materials also comprises modification POE resin 7 parts, 5 parts, static inhibitor, 1.5 parts, oxidation inhibitor, intensity modifier 5 parts, plasticized modifier 5 parts, impact modifier 5 parts.
Described modification POE resin is polypropylene/ethylene-octene copolymer that polypropylene and POE resin blending and modifying obtain; Described ethylene-octene copolymer be octene monomers content 30% ethylene-octene copolymer.
The mixture that described polypropylene is made up of with weight ratio 2.2:1 Co-polypropylene and homo-polypropylene; Described Co-polypropylene is the Co-polypropylene of melting index at 50g/10min; Described homo-polypropylene is the homo-polypropylene of melting index at 100g/10min.
The mixture that described static inhibitor is made up of with weight ratio 1:2.2 carbon black and carbon fiber.
Described carbon black is that specific surface area is at 140m 3/ g, particle diameter are at the carbon black of 12nm; Described carbon fiber be length-to-diameter ratio 600 carbon fiber.
The mixture that described oxidation inhibitor is made up of with weight ratio 1:2 antioxidant 1010 and irgasfos 168.
The mixture that described intensity modifier is made up of with weight ratio 2.4:1 at the magnesium salt whisker of 10 μm at the basalt fibre of 8 μm and filament diameter filament diameter.
Described plasticized modifier is the vinyl elastomerics of maleic anhydride and methyl methacrylate dual graft.
Described impact modifier be molecular weight 80000 polyester type Polyurethane Thermoplastic Elastomer.
The mechanical and physical performance of the nylon composite materials that embodiment 1-10 obtains is as shown in table 1.
Table 1
Test event Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Notched Izod impact strength (KJ/m 2） 5.5 5.8 6 5.9 5.7
Elongation at break % 12 11 10 10 9
Tensile strength (MPa) 80 82 85 84 81
Flexural strength (MPa) 115 118 120 119 116
Modulus in flexure (MPa) 2600 2650 2700 2680 2620
UL94 flame retardant rating V0 V0 V0 V0 V0
Test event Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10
Notched Izod impact strength (KJ/m 2） 6.1 6.4 6.6 6.5 6.3
Elongation at break % 13 12 11 11 10
Tensile strength (MPa) 88 90 93 92 89
Flexural strength (MPa) 126 129 132 130 127
Modulus in flexure (MPa) 2860 2915 2970 2948 2882
UL94 flame retardant rating V0 V0 V0 V0 V0
As can be seen from Table 1, the nylon composite materials that the present invention obtains adopts special one-tenth nuclear technique, and crystallization velocity is fast, stable performance under the high temperature conditions, not easily aging, over-all properties is better, have higher rigidity, products appearance is very bright, and fire-retardant rank reaches UL94V0 level, fire line is good, has low precipitation, anti-drippage, high electrical property and excellent heat resistance, CTI value is high, good electric property, and shock strength is high, good to environment, environmental protection.Above-described embodiment is the present invention's preferably implementation, and in addition, the present invention can also realize by alternate manner, and any apparent replacement is all within protection scope of the present invention without departing from the inventive concept of the premise.

Claims (10)

1. a halogen-free reinforced nylon matrix material, is characterized in that: described nylon composite materials comprises the raw material of following weight part:
PA66 resin 70-90 part
PA6 resin 5-15 part
Halogen-free flame retardants 5-15 part
Stablizer 0.1-0.5 part
Nucleator 0.1-0.5 part.
2. a kind of halogen-free reinforced nylon matrix material according to claim 1, is characterized in that: described PA66 resin be density 1.10-1.14g/cm3, fusing point 250-254 DEG C, molecular-weight average at 10,000-100, the PA 66 of 000.
3. a kind of halogen-free reinforced nylon matrix material according to claim 1, is characterized in that: described PA6 resin be density 1.14-1.18g/cm3, fusing point 215-225 DEG C, molecular-weight average at 10,000-100, the polycaprolactam of 000.
4. a kind of halogen-free reinforced nylon matrix material according to claim 1, is characterized in that: described halogen-free flame retardants be fusing point 348-352 DEG C, density is at the melamine cyanurate of 1.5-1.7g/cm3.
5. a kind of halogen-free reinforced nylon matrix material according to claim 1, is characterized in that: described stablizer is fusing point at the N of 270-274 DEG C, N '-bis-(2,2,6,6-tetramethyl--4-piperidyl)-1,3-benzenedicarboxamide.
6. a kind of halogen-free reinforced nylon matrix material according to claim 1, is characterized in that: the mixture that described nucleator is made up of with weight ratio 0.8-1.2:1 inorganic nucleator and organic nucleating agent, the particle diameter of nucleator is 0.1-1 μm.
7. a kind of halogen-free reinforced nylon matrix material according to claim 6, is characterized in that: described inorganic nucleator comprises at least one in superfine talcum powder, polynite and calcium carbonate; Described organic nucleating agent comprises at least one in Sodium Benzoate, sorbyl alcohol dibenzyl ester and long-chain linear saturated carboxylic acid sodium salt.
8. a kind of halogen-free reinforced nylon matrix material according to claim 1, it is characterized in that: described nylon composite materials also comprises lubricant 0.5-1.5 part, and described lubricant comprises at least one in modified vinyl bis-stearamides, pentaerythritol stearate and oxidized polyethlene wax.
9. a kind of halogen-free reinforced nylon matrix material according to claim 8, is characterized in that: the mixture that described pentaerythritol stearate is made up of with weight ratio 2-3:1 at the pentaerythritol tetrastearate of 55-65 DEG C at 25-35mgKOH/g, fusing point in the tetramethylolmethane tristearate of 50-60 DEG C and hydroxyl value at 55-65mgKOH/g, fusing point hydroxyl value.
10. the preparation method of a kind of halogen-free reinforced nylon matrix material as described in any one of claim 1-9, is characterized in that: comprise the steps:
(1) take above-mentioned raw materials by weight ratio, join blended 5-10min in high speed mixer, obtain mixture;
(2) blended for step (1) mixture obtained is extruded through forcing machine, cooling, pelletizing and screening, obtained nylon composite materials;
In described step (2), the processing parameter of forcing machine is: a district temperature 210-250 DEG C, two district temperature 210-250 DEG C, three district temperature 210-250 DEG C, four district temperature 210-250 DEG C, five district temperature 210-250 DEG C, six district temperature 210-250 DEG C, seven district temperature 210-240 DEG C, eight district temperature 210-240 DEG C, nine district temperature 210-240 DEG C, die head temperature 210-230 DEG C, pressure 18-23Mpa, screw speed 350-450r/min.
CN201510588777.9A 2015-09-16 2015-09-16 Halogen-free flame-retardant nylon composite material and preparation method thereof Pending CN105062062A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510588777.9A CN105062062A (en) 2015-09-16 2015-09-16 Halogen-free flame-retardant nylon composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510588777.9A CN105062062A (en) 2015-09-16 2015-09-16 Halogen-free flame-retardant nylon composite material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN105062062A true CN105062062A (en) 2015-11-18

Family

ID=54491598

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510588777.9A Pending CN105062062A (en) 2015-09-16 2015-09-16 Halogen-free flame-retardant nylon composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105062062A (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105754142A (en) * 2016-02-29 2016-07-13 广州呈和科技有限公司 Hydrotalcite-containing stiffening nucleating agent composition
CN105924956A (en) * 2016-05-24 2016-09-07 桐城市中汇塑业有限公司 Halogen-free flame-retardant nylon composite material
CN106589931A (en) * 2016-11-16 2017-04-26 马鞍山市华能电力线路器材有限责任公司 High-toughness flame-retardant nylon composite for electric power fitting and preparation method of nylon composite
CN108795037A (en) * 2018-06-21 2018-11-13 广东聚石化学股份有限公司 A kind of uvioresistant halogen-free reinforced nylon composition and preparation method thereof for fastener
CN109423043A (en) * 2017-08-24 2019-03-05 尤尼吉可株式会社 Foaming Amilan polyamide resin composition, foaming polyamide granulate mixture and expanded moldings
CN109535706A (en) * 2018-10-18 2019-03-29 金旸（厦门）新材料科技有限公司 A kind of Weather resistant halogen-free flame retardant enhancing nylon material and preparation method
CN110016226A (en) * 2019-04-04 2019-07-16 安徽联科水基材料科技有限公司 The fire-retardant nylon composite material and preparation method and application of a kind of resistance to ultralow temperature impact and high fluidity
CN111040445A (en) * 2019-12-31 2020-04-21 苏州旭光聚合物有限公司 Flame-retardant nylon 66/nylon 6 composite material with high mechanical property
CN112940494A (en) * 2020-12-29 2021-06-11 浙江普利特新材料有限公司 Precipitation-resistant polyamide composite material and preparation method thereof
CN116751450A (en) * 2023-06-02 2023-09-15 南京利华工程塑料有限公司 Flame-retardant nylon and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101085864A (en) * 2007-05-30 2007-12-12 深圳市科聚新材料有限公司 Halogen-free phosphor-free environmental protection inflaming retarding polyamide resin and preparation method thereof
CN101760005A (en) * 2008-12-26 2010-06-30 上海杰事杰新材料股份有限公司 High-viscosity halogen-free flame-retardant polyamide composition
CN102321361A (en) * 2011-08-04 2012-01-18 金发科技股份有限公司 Low-warpage halogen-free flame retardant reinforced polyamide composite material
KR101333587B1 (en) * 2010-12-21 2013-11-28 제일모직주식회사 Polyamide-based Resin Composition with Low Thermal Expansion Coefficient

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101085864A (en) * 2007-05-30 2007-12-12 深圳市科聚新材料有限公司 Halogen-free phosphor-free environmental protection inflaming retarding polyamide resin and preparation method thereof
CN101760005A (en) * 2008-12-26 2010-06-30 上海杰事杰新材料股份有限公司 High-viscosity halogen-free flame-retardant polyamide composition
KR101333587B1 (en) * 2010-12-21 2013-11-28 제일모직주식회사 Polyamide-based Resin Composition with Low Thermal Expansion Coefficient
CN102321361A (en) * 2011-08-04 2012-01-18 金发科技股份有限公司 Low-warpage halogen-free flame retardant reinforced polyamide composite material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
于文杰 等: "《塑料助剂与配方设计技术 第三版》", 31 July 2010, 化学工业出版社 *
刘志坚: "《聚合物成核剂》", 29 February 2012, 中国石化出版社 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105754142A (en) * 2016-02-29 2016-07-13 广州呈和科技有限公司 Hydrotalcite-containing stiffening nucleating agent composition
WO2017148302A1 (en) * 2016-02-29 2017-09-08 呈和科技股份有限公司 Rigidity-enhancing nucleating agent composition containing hydrotalcite
CN105754142B (en) * 2016-02-29 2018-06-01 呈和科技股份有限公司 A kind of reinforcement nucleating agent composition containing hydrotalcite
CN105924956A (en) * 2016-05-24 2016-09-07 桐城市中汇塑业有限公司 Halogen-free flame-retardant nylon composite material
CN106589931A (en) * 2016-11-16 2017-04-26 马鞍山市华能电力线路器材有限责任公司 High-toughness flame-retardant nylon composite for electric power fitting and preparation method of nylon composite
CN109423043A (en) * 2017-08-24 2019-03-05 尤尼吉可株式会社 Foaming Amilan polyamide resin composition, foaming polyamide granulate mixture and expanded moldings
CN108795037A (en) * 2018-06-21 2018-11-13 广东聚石化学股份有限公司 A kind of uvioresistant halogen-free reinforced nylon composition and preparation method thereof for fastener
CN108795037B (en) * 2018-06-21 2020-11-17 广东聚石化学股份有限公司 Ultraviolet-resistant halogen-free flame-retardant nylon composition for fasteners and preparation method thereof
CN109535706A (en) * 2018-10-18 2019-03-29 金旸（厦门）新材料科技有限公司 A kind of Weather resistant halogen-free flame retardant enhancing nylon material and preparation method
CN110016226A (en) * 2019-04-04 2019-07-16 安徽联科水基材料科技有限公司 The fire-retardant nylon composite material and preparation method and application of a kind of resistance to ultralow temperature impact and high fluidity
CN111040445A (en) * 2019-12-31 2020-04-21 苏州旭光聚合物有限公司 Flame-retardant nylon 66/nylon 6 composite material with high mechanical property
CN112940494A (en) * 2020-12-29 2021-06-11 浙江普利特新材料有限公司 Precipitation-resistant polyamide composite material and preparation method thereof
CN116751450A (en) * 2023-06-02 2023-09-15 南京利华工程塑料有限公司 Flame-retardant nylon and preparation method thereof

Similar Documents

Publication Publication Date Title
CN105062062A (en) Halogen-free flame-retardant nylon composite material and preparation method thereof
CN103059470B (en) High-abrasion-resistant and environment-friendly polyvinyl chloride (PVC) modified materials and preparation method thereof
CN102181108B (en) Crosslinked high flame-retardant foamed polyvinyl chloride modified material
CN101280097A (en) Nanometer flame-proof polyethylene glycol terephthalate engineering plastics and preparation thereof
CN109897303B (en) Radio frequency wire polyvinyl chloride cable material and preparation method thereof
CN102911463A (en) High-temperature resistant flame-retardant environment-friendly PVC (polyvinyl chloride) modified material and preparation method thereof
CN101469119A (en) Flame-retardant reinforced polycarbonate composition
CN104341709B (en) Crow steel charcoal modified polyacetal/polyurethane alloys marine cable protective cover material and production method thereof
CN101503570A (en) Glass fiber reinforced environment-friendly flame-retardant nylon alloy for thin-walled products and preparation method thereof
CN102093629A (en) High-luster flame retardant polypropylene complex without precipitates on surface and preparation method thereof
CN101891953A (en) Halogen-free flame retardant reinforced polyamide composition and molded product thereof
CN101899192A (en) Low-smoke fireproof polyvinyl chloride/acrylonitrile butadiene styrene (PVC/ABS) alloy and preparation method thereof
CN110079021B (en) High-temperature-aging-resistant flame-retardant polypropylene material for corrugated pipe and preparation method thereof
CN110105738B (en) Flame-retardant PC/ABS material and preparation method and application thereof
CN104927229A (en) Low-temperature-resistant, oil-resistant and flame-retardant soft polyvinyl chloride cable material and preparation method thereof
CN105462157A (en) High-fluidity, scratch-resistant and low-temperature-resistant brominated flame-retardant ABS (acrylonitrile-butadiene-styrene)/TPU (thermoplastic polyurethane) alloy material as well as preparation method and application thereof
CN104448574A (en) Environment-friendly weather-resistant flame-retardant PP material and preparation method thereof
CN102002199A (en) Polyethylene sheath material with high flame resistance at 90 DEG C
CN104277454A (en) Preparation method of high-impact weather-resistant flame-retardant reinforced nylon 6 for high glow-wire
CN103333478A (en) Halogen-free flame-retardant polycarbonate and preparation method thereof
CN110713657A (en) Polypropylene composite flame-retardant material for vehicle interior trim and preparation method and application thereof
CN103881181A (en) Flame-retardant antistatic polyethylene plastic and its preparation method
CN102816405B (en) Low-smoke halogen-free flame-retardant thermoplastic elastomer and preparation method thereof
CN103242614B (en) Halogen-free flame-retarding HIPS plastic modified material and preparation method thereof
CN102120881A (en) Inflaming retarding reinforced polyamide/polyformaldehyde composition and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20151118

RJ01 Rejection of invention patent application after publication