CN106751075A - Syndiotactic polytyrene polyhexamethylene adipamide flame-proof composite material - Google Patents
Syndiotactic polytyrene polyhexamethylene adipamide flame-proof composite material Download PDFInfo
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- CN106751075A CN106751075A CN201611064051.6A CN201611064051A CN106751075A CN 106751075 A CN106751075 A CN 106751075A CN 201611064051 A CN201611064051 A CN 201611064051A CN 106751075 A CN106751075 A CN 106751075A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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Abstract
The present invention relates to a kind of syndiotactic polytyrene polyhexamethylene adipamide flame-proof composite material.A kind of syndiotactic polytyrene polyhexamethylene adipamide flame-proof composite material, in terms of parts by weight, including：15~40 parts of syndiotactic polytyrene；5.7~20 parts of polyhexamethylene adipamide；16~20 parts of fire retardant；4~6 parts of fire retarding synergist；3.5~6 parts of compatilizer；1~5 part of laser carving powder；0.3~0.6 part of coupling agent；0.4~0.7 part of antioxidant；And 10~50 parts of basalt fibre；Wherein, the laser carving powder is selected from least one in silica, titanium dioxide, zinc sulphide, chrome green, neodymia, bismuth oxide, tin oxide, zinc molybdate, ammonium molybdate, alkali formula cupric phosphate, cupric oxide, copper-chrome black, copper carbonate, copper sulphate, copper chloride, copper chromite and carbon black.The processing of above-mentioned syndiotactic polytyrene polyhexamethylene adipamide flame-proof composite material is relatively easy to, better mechanical property, fire resistance is preferable and heat resistance is preferable.
Description
Technical field
The present invention relates to polymeric material field, more particularly to a kind of syndiotactic polytyrene-polyhexamethylene adipamide resistance
Retardant composite material.
Background technology
Syndiotactic polytyrene (sPS) is a kind of new engineering plastics, with low-gravity, low-k, bending die high
Amount, excellent heat resistance, good stiffness, high-melting-point (about 270 DEG C of Tm) and excellent solvent resistance, it is resistance to vapor permeability the characteristics of.SPS has
Fabulous development prospect, potential market is boundless, however, the fragility that sPS is present is big, mechanics, heat resistance and anti-flammability be not high
Etc. defect, its range of application is greatly limit, it is necessary to which it is modified, with the application of commensurate structure material.
Upgrading with the industry such as electronic apparatus and automobile develops, requirement more and more higher of the people to outward appearance and false proof
Need, the processing mode that traditional frosting obtains pattern is essentially ink printing, this technique not only tedious process, efficiency is low
Under, and substantial amounts of organic solvent pollution can be caused, Long Term Contact will also result in harm to human body, be difficult to meet reality
Need.
The content of the invention
Based on this, there is provided between one kind processing is relatively easy to, better mechanical property, fire resistance are preferable and heat resistance is preferable
Stereospecific polymerized styrene-polyhexamethylene adipamide flame-proof composite material.
A kind of syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material, in terms of parts by weight, including：
Wherein, the laser carving powder be selected from silica, titanium dioxide, zinc sulphide, chrome green, neodymia, bismuth oxide,
Tin oxide, zinc molybdate, ammonium molybdate, alkali formula cupric phosphate, cupric oxide, copper-chrome black, copper carbonate, copper sulphate, copper chloride, copper chromite,
Cupric thiocyanate, spinelle, tin ash, tin ash, sodium stannate, potassium stannate, zinc sulfate, antimony oxide, antimony pentoxide, metaantimmonic acid
At least one in sodium, potassium carbonate, barium sulfate and carbon black；The compatilizer is selected from maleic anhydride stem grafting polyolefin elastomer, third
Olefin(e) acid ester-ethylene oxidic ester-ethylene-dien terpolymer, methacrylate-butadiene-styrene rubber-styrene copolymer, ethene-
Acrylate copolymer, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene terpolymer, acrylonitrile-second
In alkene-styrene copolymer, hydrogenated styrene-butadiene-styrene block copolymers grafted maleic anhydride at least one
Kind；The fire retardant is selected from TDE, brominated Polystyrene, polydibromstyrol, brominated epoxy, polyacrylic acid pentabromo-
In benzyl ester, double (tribromophenoxy) ethane, double tetrabromo phthalimide ethane and tetrabromobisphenol A carbonic ester oligomer extremely
Few one kind.
Above-mentioned syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material, is changed by adding basalt fibre
Property, can improve mechanical property and heat resistance, polyhexamethylene adipamide and compatilizer are added, do not affecting the mechanical properties and heat-resisting
Impact property can be improved in the case of property, so that better mechanical property and heat resistance is preferable；Laser carving powder is added, it is soft by computer
Part designs the pattern and letter of needs, and local irradiation is carried out to workpiece using the laser beam of high density energy, makes material surface
There is the change of physics and chemistry, so as to obtain visible pattern, using Computer Control Technology, change mark content is held very much
Easily, the efficient requirement of modern production is adapted to, manufacturing process is done using laser, can produced on the surface of material very fine
Mark and durability is very good, there is no the effect of operating force with workpiece, it is ensured that the original precision of workpiece, processing mode spirit
Living, production efficiency is high and environmentally safe；Fire resistance is improved by compound flame retardant and fire retarding synergist, makes it extensive
Apply the occasion in the engineering plastics application such as PET, PBT, PA, PPS.
Wherein in one embodiment, the weight average molecular weight of the syndiotactic polytyrene is 200,000~700,000；And/or, institute
State the intrinsic viscosity 2.2dL/g~3.0dL/g of polyhexamethylene adipamide.
Wherein in one embodiment, the fire retarding synergist be selected from antimony oxide, sodium antimonate, antimonic acid anhydride, Firebrake ZB,
Metaborate, iron oxide, montmorillonite, kaolin, talcum powder, melamine, melamine salt, ammonium polyphosphate, phosphoric acid triphen
At least one in ester, tricresyl phosphate, cresyl diphenyl phosphate, polycondensation aryl phosphate ester and polytetrafluoroethylene (PTFE).
Wherein in one embodiment, the coupling agent is selected from the coupling of titanate coupling agent, silane coupler and Aluminate
At least one in agent.
Wherein in one embodiment, the antioxidant is selected from four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid]
Pentaerythritol ester, N, N'- is double-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine, β-(3,5- di-t-butyls-
4- hydroxy phenyls) the positive octadecanol ester of propionic acid, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanuric acid, three [2.4-
Di-tert-butyl-phenyl] phosphite ester, double (2,4-DTBP) pentaerythritol diphosphites and double (2,4- dicumyl benzene
Base) at least one in pentaerythritol diphosphites.
Wherein in one embodiment, also including the nucleator no more than 2 parts, the nucleator is selected from talcum powder, oxidation
At least one in zinc, silicate, stearate, nano imvite, carbonate, phosphate, Sodium Benzoate, unary carboxylation.
Wherein in one embodiment, also including the auxiliary agent no more than 3 parts, the auxiliary agent be selected from ultra-violet absorber, into
At least one in core agent, colouring agent, lubricant and releasing agent.
Wherein in one embodiment, the basalt fibre is selected from and is chopped in basalt fibre and continuous basalt fiber
At least one.
Wherein in one embodiment, a diameter of 9 microns~15 microns of the basalt fibre.
Wherein in one embodiment, the chopped length of the basalt fibre is 3 millimeters~6 millimeters.
Specific embodiment
Syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material is made into one mainly in combination with specific embodiment below
Step detailed description.
The syndiotactic polytyrene of one implementation method-polyhexamethylene adipamide flame-proof composite material, in terms of parts by weight, bag
Include：
Laser carving powder is selected from silica, titanium dioxide, zinc sulphide, chrome green, neodymia, bismuth oxide, tin oxide, molybdenum
Sour zinc, ammonium molybdate, alkali formula cupric phosphate, cupric oxide, copper-chrome black, copper carbonate, copper sulphate, copper chloride, copper chromite, cupric thiocyanate,
Spinelle, tin ash, tin ash, sodium stannate, potassium stannate, zinc sulfate, antimony oxide, antimony pentoxide, sodium antimonate, carbonic acid
At least one in potassium, barium sulfate and carbon black.Wherein in one embodiment, the particle diameter of laser carving powder is 0.3 micron~2.6 micro-
Rice.
Compatilizer is selected from maleic anhydride stem grafting polyolefin elastomer, acrylate-ethylene oxidic ester-ethene ternary polymerization
Thing, methacrylate-butadiene-styrene rubber-styrene copolymer, vinyl-acrylate copolymer, ethylene-vinyl acetate
Copolymer, acrylonitrile-butadiene-styrene terpolymer, acrylonitrile-vinyl-styrene copolymer, hydrogenation of benzene second
At least one in alkene-butadiene-styrene block copolymer grafted maleic anhydride.Preferably, maleic anhydride stem grafting polyolefin
Elastomer is selected from maleic anhydride grafted polyethylene elastomer, maleic anhydride grafting poly 1-butene elastomer, maleic anhydride and is grafted and gathers
At least one in ethylene-acrylic acid copolymer elastomer and maleic anhydride grafted polyethylene-vinyl acetate copolymer elastomer.
Fire retardant is selected from TDE, brominated Polystyrene, polydibromstyrol, brominated epoxy, polyacrylic acid five
In bromobenzyl ester, double (tribromophenoxy) ethane, double tetrabromo phthalimide ethane and tetrabromobisphenol A carbonic ester oligomer
It is at least one.
Wherein in one embodiment, fire retarding synergist is selected from antimony oxide, sodium antimonate, antimonic acid anhydride, Firebrake ZB, oxidation
Iron, montmorillonite, kaolin, talcum powder, melamine, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate,
At least one in polycondensation aryl phosphate ester and polytetrafluoroethylene (PTFE).
Wherein in one embodiment, the weight average molecular weight of syndiotactic polytyrene (sPS) is 200,000~700,000.Preferably,
Normality is more than or equal to 97% between syndiotactic polytyrene.
Wherein in one embodiment, the intrinsic viscosity 2.2dL/g~3.0dL/g of polyhexamethylene adipamide (PA66).
In one of embodiment, coupling agent is at least one in titanate coupling agent, silane coupler and aluminate coupling agent.It is excellent
Choosing, titanate coupling agent is selected from isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, double (two octyloxy pyrophosphates
Base) ethylene titanate esters, the oleic acid acyloxy of isopropyl two (dioctyl phosphoric acid acyloxy) titanate esters and monoalkoxy unsaturated fat
At least one in sour titanate esters.Silane coupler is selected from VTES, (the 'beta '-methoxy ethoxy of vinyl three
Base) at least one in silane, gamma-aminopropyl-triethoxy-silane and 3- glycydoxy trimethoxy silanes.
Aluminate coupling agent is selected from least one in distearyl acyl-oxygen isopropyl Aluminate, DL-411 and anti-settling Aluminate ASA.
Certainly, it is necessary to explanation, coupling agent is not limited to mentioned kind, other can the coupling agent of reinforcing material interface performances can be with
Use.
Wherein in one embodiment, antioxidant is selected from antioxidant 1010 (four [β-(3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid] pentaerythritol ester), antioxidant 1098 (N, N'- be double-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) oneself
Diamines), antioxidant 1076 (β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid), antioxidant 3114 (1,3,
5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanuric acid), irgasfos 168 (three [2.4- di-tert-butyl-phenyls] phosphorous acid
Ester), (double (2,4- bis- is withered for antioxidant 626 (double (2,4- DI-tert-butylphenol compounds) pentaerythritol diphosphites) and antioxidant 9228
Base phenyl) pentaerythritol diphosphites) at least one.Certainly, antioxidant is not limited to above-mentioned material, and other can be prevented
Material aging, organized polymerization thing thermal oxidative degradation and the antioxidant for increasing the service life can be used.
Wherein in one embodiment, basalt fibre is selected from be chopped basalt fibre and continuous basalt fiber extremely
Few one kind.Wherein in one embodiment, the length of the basalt fibre that is chopped is 3 millimeters~6 millimeters.
Wherein in one embodiment, a diameter of 9 microns~15 microns of basalt fibre.
Wherein in one embodiment, syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material also includes not surpassing
Cross 2 parts of nucleator.Nucleator is selected from talcum powder, zinc oxide, silicate, stearate, nano imvite, carbonate, phosphoric acid
At least one in salt, Sodium Benzoate, unary carboxylation.Preferably, the particle diameter of nucleator is 0.1 micron~2 microns.Silicate
Selected from least one in alumina silicate, calcium silicates, magnesium silicate and sodium metasilicate.Stearate is selected from aluminum stearate, lithium stearate, hard
At least one in fatty acid magnesium, zinc stearate, barium stearate and calcium stearate.Carbonate is selected from calcium carbonate, barium carbonate, zinc carbonate
And at least one in magnesium carbonate.Phosphate is selected from least one in calcium phosphate, sodium phosphate, potassium phosphate and trbasic zinc phosphate.Unitary
Carboxylate is selected from least one in monocarboxylic acid sodium, monocarboxylic acid potassium and monocarboxylic acid calcium.It should be noted that nucleator can
To omit, or other nucleators commonly used in the trade.
Wherein in one embodiment, syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material also includes not surpassing
Cross 3 parts of auxiliary agent.Auxiliary agent is selected from least one in ultra-violet absorber, colouring agent, lubricant and releasing agent.Preferably,
The ultra-violet absorber that also included 0 part~0.6 part of stereospecific polymerized styrene flame-proof composite material, 0 part~2 parts of colouring agent, 0 part~
0.6 part of lubricant and 0 part~1 part of releasing agent.Preferably, (salicylic acid is to t-octyl benzene selected from OPS for ultra-violet absorber
Ester), UV-242 (2- hydroxyls -4- (2 '-ethyl hexyl oxy) benzophenone), UV-622 (poly-succinic (4- ethoxy -2,2,6,
6- tetramethyl -1- piperidine ethanols) ester) and UV-326 (2'- (the 2'- hydroxyl -3'- tert-butyl group -5'- aminomethyl phenyls) -5- chlorobenzenes and three
Azoles) at least one.Colouring agent be selected from titanium dioxide, ultramarine blue, phthalocyanine green, carbon black, permanent yellow and fluorescein at least
It is a kind of.Lubricant is selected from EBS (ethylene bis-fatty acid amides), PETS (pentaerythritol stearate), SEED (two (2,2,6,6-
Tetramethyl -3- piperidines amido)-isophtalamide) and TAF (modified ethylene bis-fatty acid amides) at least one.The demoulding
Agent is selected from least one in lithium stearate, aluminum stearate, magnesium stearate and zinc stearate.Certainly, ultra-violet absorber, coloring
Agent, lubricant and releasing agent can be omitted, and can use other materials commonly used in the trade.
Wherein in one embodiment, syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material, with parts by weight
Meter, including：
Above-mentioned syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material, is changed by adding basalt fibre
Property, can improve mechanical property and heat resistance, polyhexamethylene adipamide and compatilizer are added, do not affecting the mechanical properties and heat-resisting
Impact property can be improved in the case of property, so that better mechanical property and heat resistance is preferable；Laser carving powder is added, it is soft by computer
Part designs the pattern and letter of needs, and local irradiation is carried out to workpiece using the laser beam of high density energy, makes material surface
There is the change of physics and chemistry, so as to obtain visible pattern, using Computer Control Technology, change mark content is held very much
Easily, the efficient requirement of modern production is adapted to, manufacturing process is done using laser, can produced on the surface of material very fine
Mark and durability is very good, there is no the effect of operating force with workpiece, it is ensured that the original precision of workpiece, processing mode spirit
Living, production efficiency is high and environmentally safe；Fire resistance is improved by compound flame retardant and fire retarding synergist, makes it extensive
Apply the occasion in the engineering plastics application such as PET, PBT, PA, PPS.
The preparation method of above-mentioned syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material, comprises the following steps：
Step S110, sPS and PA66 are dried treatment.
Wherein in one embodiment, by sPS and PA66 respectively in 100 DEG C~120 DEG C forced air dryings 1 hour~4 hours.
Certainly, when sPS and PA66 are more dried in itself, then treatment need not be dried, step S110 can be omitted.
Step S120, dried sPS and PA66 and compatilizer and coupling agent are uniformly mixed after, sequentially add radium
Carving powder, antioxidant, nucleator and auxiliary agent are well mixed and obtain pre-composition.
Wherein in one embodiment, during dried sPS and PA66 and compatilizer and coupling agent added into mixer,
Mixing 1 minute~3 minutes is stirred under 200 revs/min~500 revs/min of rotating speed, after machine to be mixed stops, being sequentially added fire-retardant
Agent, fire retarding synergist, laser carving powder, antioxidant, nucleator and auxiliary agent, stir mixing under 200 revs/min~500 revs/min of rotating speed
2 minutes~5 minutes.
Step S130, pre-composition and basalt fibre extruding pelletization are obtained into syndiotactic polytyrene-polyhexamethylene adipamide
Flame-proof composite material.
Wherein in one embodiment, during pre-composition added into double screw extruder, then by basalt fibre from twin-screw
Extruder side spout add, through melting extrusion granulation, water-cooled, air-dry, pelletizing, be dried to obtain syndiotactic polytyrene-gather oneself two
Acyl hexamethylene diamine flame-proof composite material.Preferably, the fabrication process condition of double screw extruder is as follows：One 180 DEG C of area~220 DEG C；
Two 240 DEG C of areas~260 DEG C；Three 250 DEG C of areas~280 DEG C；Four 250 DEG C of areas~280 DEG C；5th area：250 DEG C~270 DEG C；Six areas 240
DEG C~260 DEG C；Seven 220 DEG C of areas~260 DEG C；Eight 220 DEG C of areas~260 DEG C；Nine 220 DEG C of areas~250 DEG C；Head 240 DEG C~280
℃；Screw speed is 300rpm~600rpm.
Step S140, by syndiotactic polytyrene composite injection moulding after, by laser engraving pattern.
The preparation method of above-mentioned syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material, it is simple to operate, it is easy to work
Industry.
It is below specific embodiment part：
Part in following examples is parts by weight.
Embodiment 1
It is 97% from a normality, weight average molecular weight is 300,000 sPS resins, is 3.0dl/g's from intrinsic viscosity
PA66 resins, respectively at after forced air drying at 120 DEG C 3 hours, by 40 parts of dried sPS, 20 parts of PA66,4.2 parts of hydrogenation of benzene
Ethylene-butadiene-styrene block copolymer grafted maleic anhydride, 0.4 part of KH550 (silane coupler) sequentially add mixer
In, stirred under 200 revs/min of rotating speed after mixing 3 minutes, after machine to be mixed stops, sequentially adding 12.1 part of ten bromine
Diphenylethane, 6 parts of brominated Polystyrenes, 3 parts of antimony oxides (average grain diameter is 0.9 micron), 2 parts of kaolin (average grain diameters
Be 1.2 microns), 0.3 part of titanium dioxide (average grain diameter is 0.3 micron), 0.2 part of neodymia (average grain diameter is 0.5 micron),
0.2 part of bismuth oxide (average grain diameter is 0.5 micron), 0.3 part of alkali formula cupric phosphate (average grain diameter is 1.3 microns), 0.2 part of antioxidant
1010th, 0.4 part of antioxidant, 626,0.3 part of nucleator monocarboxylic acid calcium, 0.4 part of lubricant PETS be in mixer, 200 turns/
Mixing 3 minutes is stirred under the rotating speed for dividing, well mixed pre-composition is obtained；
Well mixed pre-composition is placed in double screw extruder by following condition melting extrusion：One 200 DEG C of area；2nd area
250℃；Three 270 DEG C of areas；Four 270 DEG C of areas；5th area：260℃；Six 250 DEG C of areas；Seven 250 DEG C of areas；Eight 240 DEG C of areas；Nine 240 DEG C of areas；
270 DEG C of head；Screw speed is 350rpm；Side feeding 10 parts of filament diameters of addition are 13 microns of continuous basalt fiber, so
By water-cooled, air-dry, pelletizing, obtain syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material after drying.
The syndiotactic polytyrene of gained-polyhexamethylene adipamide flame-proof composite material after injection moulding on injection machine,
The pattern of editor's need laser engraving in laser engraving machine, it is possible to pattern needed for directly being carved on product.
Embodiment 2
It is 97.5% from a normality, weight average molecular weight is 400,000 sPS resins, is 2.7dl/g's from intrinsic viscosity
PA66 resins, respectively at after forced air drying at 120 DEG C 3 hours, by 35 parts of dried sPS, 11.5 parts of PA66,5 parts of compatilizers
Acrylate-ethylene oxidic ester-ethylene copolymer, 0.3 part of isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate coupling agent
Sequentially add in mixer, stirred under 250 revs/min of rotating speed after mixing 2 minutes, after machine to be mixed stops, then successively
Add 16 parts of TDEs, 3 parts of antimony oxides (average grain diameter is 0.9 micron), (average grain diameter is 0.5 for 3 parts of montmorillonites
Micron), 3 parts of barium sulfate (average grain diameter is 2.6 microns), 1 part of tin oxide (average grain diameter is 0.7 micron), 1 part of copper chromite
(average grain diameter is 0.5 micron), 0.3 part of antioxidant 1076,0.4 part of irgasfos 168,0.2 part of nucleator sodium phosphate, 0.3 part of profit
Lubrication prescription SEED stirs mixing 4 minutes in mixer under 300 revs/min of rotating speed, obtains well mixed pre-composition；
Well mixed pre-composition is placed in double screw extruder by following condition melting extrusion：One 210 DEG C of area；2nd area
260℃；Three 275 DEG C of areas；Four 275 DEG C of areas；5th area：265℃；Six 255 DEG C of areas；Seven 250 DEG C of areas；Eight 240 DEG C of areas；Nine 240 DEG C of areas；
270 DEG C of head；Screw speed is 400rpm；Side feeding 20 parts of filament diameters of addition are 11 microns of continuous basalt fiber, so
By water-cooled, air-dry, pelletizing, obtain syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material after drying.
The syndiotactic polytyrene of gained-polyhexamethylene adipamide flame-proof composite material after injection moulding on injection machine,
The pattern of editor's need laser engraving in laser engraving machine, it is possible to pattern needed for directly being carved on product.
Embodiment 3
It is 98% from a normality, weight average molecular weight is 500,000 sPS resins, is 2.7dl/g's from intrinsic viscosity
PA66 resins, respectively at after forced air drying at 120 DEG C 2 hours, by 24.5 parts of dried sPS, 10 parts of PA66,6 parts of compatilizers
Ethylene vinyl acetate copolymer, 0.6 part of distearyl acyl-oxygen isopropyl aluminate coupling agent are sequentially added in mixer, 300
Rev/min rotating speed under stir and mix 1 minute after, after machine to be mixed stops, sequentially adding 20 parts of brominated Polystyrenes,
4.5 parts of antimony oxides (average grain diameter is 0.9 micron), 1.3 parts of tin oxide (average grain diameter is 0.5 micron), 0.6 part of zinc molybdate
(average grain diameter is 0.3 micron), 0.6 part of zinc sulphide (average grain diameter is 0.4 micron), 0.3 part of antioxidant, 1098,0.3 part of antioxygen
9228,0.2 part of nucleator Sodium Benzoate of agent, 0.8 part of carbon black, 0.3 part of lithium stearate releasing agent in mixer, at 450 revs/min
Rotating speed under stir mixing 3 minutes, obtain well mixed pre-composition；
Well mixed pre-composition is placed in double screw extruder by following condition melting extrusion：One 210 DEG C of area；2nd area
255℃；Three 275 DEG C of areas；Four 275 DEG C of areas；5th area：260℃；Six 250 DEG C of areas；Seven 250 DEG C of areas；Eight 240 DEG C of areas；Nine 240 DEG C of areas；
275 DEG C of head；Screw speed is 450rpm；Side feeding 30 parts of filament diameters of addition are 9 microns of continuous basalt fiber, then
Syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material is obtained after water cooled, air-dried, pelletizing, drying.
The syndiotactic polytyrene of gained-polyhexamethylene adipamide flame-proof composite material after injection moulding on injection machine,
The pattern of editor's need laser engraving in laser engraving machine, it is possible to pattern needed for directly being carved on product.
Embodiment 4
It is 98% from a normality, weight average molecular weight is 500,000 sPS resins, is 2.7dl/g's from intrinsic viscosity
PA66 resins, respectively at after forced air drying at 120 DEG C 2 hours, by 24.5 parts of dried sPS, 10 parts of PA66,6 parts of compatilizers
Ethylene vinyl acetate copolymer, 0.6 part of distearyl acyl-oxygen isopropyl aluminate coupling agent are sequentially added in mixer, 300
Rev/min rotating speed under stir and mix 1 minute after, after machine to be mixed stops, sequentially adding 20 parts of brominated Polystyrenes,
4.5 parts of antimony oxides (average grain diameter is 0.9 micron), 0.3 part of 1098,0.3 part of antioxidant, 9228,0.2 part of antioxidant nucleation
Agent Sodium Benzoate, 0.8 part of carbon black, 0.3 part of lithium stearate releasing agent stir mixing in mixer under 450 revs/min of rotating speed
3 minutes, obtain well mixed pre-composition；
Well mixed pre-composition is placed in double screw extruder by following condition melting extrusion：One 210 DEG C of area；2nd area
255℃；Three 275 DEG C of areas；Four 275 DEG C of areas；5th area：260℃；Six 250 DEG C of areas；Seven 250 DEG C of areas；Eight 240 DEG C of areas；Nine 240 DEG C of areas；
275 DEG C of head；Screw speed is 450rpm；Side feeding 30 parts of filament diameters of addition are 9 microns of continuous basalt fiber, then
Syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material is obtained after water cooled, air-dried, pelletizing, drying.
The syndiotactic polytyrene of gained-polyhexamethylene adipamide flame-proof composite material after injection moulding on injection machine,
The pattern of editor's need laser engraving in laser engraving machine, fails to carve required pattern on product.
Embodiment 5
It is 98.5% from a normality, weight average molecular weight is 700,000 sPS resins, is 2.5dl/g's from intrinsic viscosity
PA66 resins, respectively at after forced air drying at 110 DEG C 3 hours, by weight, by 17.5 parts of dried sPS, 10 parts of PA66,2
Part compatilizer hydrogenated styrene-butadiene-styrene block copolymers grafted maleic anhydride, 1.5 parts of acrylate-glycidols
Ester-ethylene copolymer, 0.3 part of KH560 silane couplers, 0.2 part of oleic acid acyloxy of isopropyl two (dioctyl phosphoric acid acyloxy)
Titanate esters are sequentially added in mixer, are stirred under 380 revs/min of rotating speed after mixing 1 minute, after machine to be mixed stops,
Sequentially add 8 parts of brominated Polystyrenes, 10 parts of brominated epoxy resins, 4 parts of antimony oxides (average grain diameter is 0.9 micron), 1
Part silica (average grain diameter is 0.5 micron), 1 part of cupric oxide (average grain diameter is 0.8 micron), 1 part of potassium stannate (average grain diameter
Be 0.5 micron), 0.3 part of antioxidant 3114,0.4 part of antioxidant, 9228,0.4 part of lubricant TAF, 0.3 part of EBS, 0.2 part of UV-
326th, 0.3 part of UV-242,0.3 part of ultramarine blue, 0.3 part of permanent yellow, 1 part of zinc stearate is in mixer, in 280 revs/min turn
The lower stirring mixing of speed 5 minutes, obtains well mixed pre-composition；
Well mixed pre-composition is placed in double screw extruder by following condition melting extrusion：One 220 DEG C of area；2nd area
260℃；Three 280 DEG C of areas；Four 275 DEG C of areas；5th area：270℃；Six 260 DEG C of areas；Seven 255 DEG C of areas；Eight 245 DEG C of areas；Nine 240 DEG C of areas；
275 DEG C of head；Screw speed is 500rpm；Side feeding 40 parts of filament diameters of addition are 13 microns of chopped basalt fibre, so
By water-cooled, air-dry, pelletizing, obtain syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material after drying.
The syndiotactic polytyrene of gained-polyhexamethylene adipamide flame-proof composite material after injection moulding on injection machine,
The pattern of editor's need laser engraving in laser engraving machine, it is possible to pattern needed for directly being carved on product.
Embodiment 6
It is 99% from a normality, weight average molecular weight is 200,000 sPS resins, is 2.2dl/g's from intrinsic viscosity
PA66 resins, respectively at after forced air drying at 115 DEG C 3 hours, by weight, by 15 parts of dried sPS, 5.7 parts of PA66,
3.5 parts of compatilizer hydrogenated styrene-butadiene-styrene block copolymers grafted maleic anhydrides, 0.5 part of KH560 are silane coupled
Agent is sequentially added in mixer, is stirred under 380 revs/min of rotating speed after mixing 1 minute, after machine to be mixed stops, then according to
It is secondary to add 18 parts of brominated epoxy resins, 4 parts of antimony oxides (average grain diameter is 0.9 micron), 2 parts of cupric thiocyanate (average grain diameters
Be 0.5 micron), 0.5 part of zinc molybdate (average grain diameter is 0.5 micron), 0.2 part of antioxidant 1010,0.2 part of irgasfos 168,0.4
Part lubricant TAF stirs mixing 5 minutes in mixer under 280 revs/min of rotating speed, obtains well mixed pre-composition；
Well mixed pre-composition is placed in double screw extruder by following condition melting extrusion：One 220 DEG C of area；2nd area
260℃；Three 280 DEG C of areas；Four 275 DEG C of areas；5th area：270℃；Six 260 DEG C of areas；Seven 255 DEG C of areas；Eight 245 DEG C of areas；Nine 240 DEG C of areas；
275 DEG C of head；Screw speed is 500rpm；Side feeding 50 parts of filament diameters of addition are 9 microns of chopped basalt fibre, then
Syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material is obtained after water cooled, air-dried, pelletizing, drying.
The syndiotactic polytyrene of gained-polyhexamethylene adipamide flame-proof composite material after injection moulding on injection machine,
The pattern of editor's need laser engraving in laser engraving machine, it is possible to pattern needed for directly being carved on product.
Syndiotactic polytyrene prepared by embodiment 1~5 and comparative example 1-polyhexamethylene adipamide flame-proof composite material system
Performance test is carried out into test sample, 1 is the results are shown in Table.
Table 1
As it can be seen from table 1 adding laser carving powder and compatilizer in embodiment 1~3 and embodiment 5~6, compatilizer is selected from horse
Maleic anhydride grafted polyolefin elastomer, acrylate-ethylene oxidic ester-ethylene-dien terpolymer, methacrylate-butylbenzene rubber
Glue-styrene copolymer, vinyl-acrylate copolymer, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-
Styrene copolymer, acrylonitrile-vinyl-styrene copolymer, hydrogenated styrene-butadiene-styrene block are total to
At least one in polymers grafted maleic anhydride, so as to while with excellent laser carving performance, maintain preferable mechanics
Performance.
Syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material is by modified, better mechanical property, fire resistance
Preferable and heat resistance preferably, while having excellent laser carving performance, has good in fields such as Aero-Space, automobile, electronic apparatus
Good application prospect.Can be widely used in the occasion of the engineering plastics application such as PET, PBT, PA, PPS.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of syndiotactic polytyrene-polyhexamethylene adipamide flame-proof composite material, it is characterised in that in terms of parts by weight, bag
Include：
Wherein, the laser carving powder is selected from silica, titanium dioxide, zinc sulphide, chrome green, neodymia, bismuth oxide, oxidation
Tin, zinc molybdate, ammonium molybdate, alkali formula cupric phosphate, cupric oxide, copper-chrome black, copper carbonate, copper sulphate, copper chloride, copper chromite, sulphur cyanogen
Sour copper, spinelle, tin ash, tin ash, sodium stannate, potassium stannate, zinc sulfate, antimony oxide, antimony pentoxide, sodium antimonate,
At least one in potassium carbonate, barium sulfate and carbon black；The compatilizer is selected from maleic anhydride stem grafting polyolefin elastomer, acrylic acid
Ester-ethylene oxidic ester-ethylene-dien terpolymer, methacrylate-butadiene-styrene rubber-styrene copolymer, ethylene-propylene
Acid ester copolymer, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene terpolymer, acrylonitrile-vinyl-
At least one in styrene copolymer, hydrogenated styrene-butadiene-styrene block copolymers grafted maleic anhydride；
The fire retardant is selected from TDE, brominated Polystyrene, polydibromstyrol, brominated epoxy resin, polyacrylic acid five
In bromobenzyl ester, double (tribromophenoxy) ethane, double tetrabromo phthalimide ethane and tetrabromobisphenol A carbonic ester oligomer
It is at least one.
2. syndiotactic polytyrene according to claim 1-polyhexamethylene adipamide flame-proof composite material, it is characterised in that
The weight average molecular weight of the syndiotactic polytyrene is 200,000~700,000；And/or, the intrinsic viscosity of the polyhexamethylene adipamide
2.2dL/g~3.0dL/g.
3. syndiotactic polytyrene according to claim 1-polyhexamethylene adipamide flame-proof composite material, it is characterised in that
The fire retarding synergist is selected from antimony oxide, sodium antimonate, antimonic acid anhydride, Firebrake ZB, metaborate, iron oxide, montmorillonite, kaolinite
Soil, talcum powder, melamine, melamine salt, ammonium polyphosphate, triphenyl phosphate, tricresyl phosphate, tolyl diphenyl
At least one in phosphate, polycondensation aryl phosphate ester and polytetrafluoroethylene (PTFE).
4. syndiotactic polytyrene according to claim 1-polyhexamethylene adipamide flame-proof composite material, it is characterised in that
The coupling agent is selected from least one in titanate coupling agent, silane coupler and aluminate coupling agent.
5. syndiotactic polytyrene according to claim 1-polyhexamethylene adipamide flame-proof composite material, it is characterised in that
The antioxidant is selected from four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, N, N'- couples-(3- (3,5-
Di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, β-(3,5- di-tert-butyl-hydroxy phenyls) positive octadecanol of propionic acid
It is ester, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanuric acid, three [2.4- di-tert-butyl-phenyls] phosphite esters, double
In (2,4-DTBP) pentaerythritol diphosphites and double (2,4- dicumylphenyl) pentaerythritol diphosphites
At least one.
6. syndiotactic polytyrene according to claim 1-polyhexamethylene adipamide flame-proof composite material, it is characterised in that
Also include the nucleator no more than 2 parts, the nucleator is selected from talcum powder, zinc oxide, silicate, stearate, nanometer and covers de-
At least one in soil, carbonate, phosphate, Sodium Benzoate, unary carboxylation.
7. syndiotactic polytyrene according to claim 1-polyhexamethylene adipamide flame-proof composite material, it is characterised in that
Also include no more than 3 parts of auxiliary agent, the auxiliary agent is selected from ultra-violet absorber, colouring agent, lubricant and releasing agent at least
It is a kind of.
8. syndiotactic polytyrene according to claim 1-polyhexamethylene adipamide flame-proof composite material, it is characterised in that
The basalt fibre is selected from least one in be chopped basalt fibre and continuous basalt fiber.
9. syndiotactic polytyrene according to claim 1-polyhexamethylene adipamide flame-proof composite material, it is characterised in that
A diameter of 9 microns~15 microns of the basalt fibre.
10. syndiotactic polytyrene according to claim 1-polyhexamethylene adipamide flame-proof composite material, it is characterised in that
The chopped length of the basalt fibre is 3 millimeters~6 millimeters.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175290A (en) * | 2020-10-02 | 2021-01-05 | 东莞市烁康新材料科技有限公司 | Laser etching powder applied to laser marking and preparation process thereof |
| CN115011084A (en) * | 2022-07-15 | 2022-09-06 | 中钢集团马鞍山矿山研究总院股份有限公司 | High-toughness heat-resistant flame-retardant PC/PBT alloy material and preparation method thereof |
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| US20040054082A1 (en) * | 2001-12-03 | 2004-03-18 | Bank David H | Toughened polymer blends with improved surface properties |
| CN102702669A (en) * | 2012-06-15 | 2012-10-03 | 昆山聚威工程塑料有限公司 | PC /ABS (poly carbonate/acrylonitrile butadiene styrene) laser etching electroplating material |
| CN105524461A (en) * | 2016-01-05 | 2016-04-27 | 广州市聚赛龙工程塑料有限公司 | Gasoline-resistant glass-fiber-reinforced halogen-free flame-retardant sPS composite material and preparation method thereof |
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| US20040054082A1 (en) * | 2001-12-03 | 2004-03-18 | Bank David H | Toughened polymer blends with improved surface properties |
| CN102702669A (en) * | 2012-06-15 | 2012-10-03 | 昆山聚威工程塑料有限公司 | PC /ABS (poly carbonate/acrylonitrile butadiene styrene) laser etching electroplating material |
| CN105524461A (en) * | 2016-01-05 | 2016-04-27 | 广州市聚赛龙工程塑料有限公司 | Gasoline-resistant glass-fiber-reinforced halogen-free flame-retardant sPS composite material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112175290A (en) * | 2020-10-02 | 2021-01-05 | 东莞市烁康新材料科技有限公司 | Laser etching powder applied to laser marking and preparation process thereof |
| CN115011084A (en) * | 2022-07-15 | 2022-09-06 | 中钢集团马鞍山矿山研究总院股份有限公司 | High-toughness heat-resistant flame-retardant PC/PBT alloy material and preparation method thereof |
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