CN106751077A - Syndiotactic polytyrene flame-proof composite material - Google Patents
Syndiotactic polytyrene flame-proof composite material Download PDFInfo
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- CN106751077A CN106751077A CN201611064855.6A CN201611064855A CN106751077A CN 106751077 A CN106751077 A CN 106751077A CN 201611064855 A CN201611064855 A CN 201611064855A CN 106751077 A CN106751077 A CN 106751077A
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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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- 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
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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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/02—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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- 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
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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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- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The present invention relates to a kind of syndiotactic polytyrene flame-proof composite material.A kind of syndiotactic polytyrene 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 glass 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 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 flame-proof 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 flame-proof composite material.
A kind of syndiotactic polytyrene 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 resin, polyacrylic acid
In pentabromo- benzyl ester, double (tribromophenoxy) ethane, double tetrabromo phthalimide ethane and tetrabromobisphenol A carbonic ester oligomer
At least one.
Above-mentioned syndiotactic polytyrene flame-proof composite material, is modified by adding glass fibre, can improve mechanical property
Can and heat resistance, add polyhexamethylene adipamide and compatilizer, do not affect the mechanical properties and heat resistance in the case of can change
Kind impact property, so that better mechanical property and heat resistance is preferable；Laser carving powder is added, the figure of needs is designed by computer software
Case and letter, local irradiation is carried out using the laser beam of high density energy to workpiece, makes material surface that physics occur with chemistry
Change, so as to obtain visible pattern, using Computer Control Technology, change mark content is very easy to, and adapts to modern production
Efficient requirement, manufacturing process is done using laser, on the surface of material can produce very fine mark and durability is non-
Chang Hao, does not have the effect of operating force with workpiece, it is ensured that the original precision of workpiece, processing mode flexibly, production efficiency it is high and
It is environmentally safe；Fire resistance is improved by compound flame retardant and fire retarding synergist, make its can be widely used in PET, PBT,
The occasion of the engineering plastics application such as 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 glass fibre is selected from short glass fiber and continuous glass fibre at least
It is a kind of.
Wherein in one embodiment, a diameter of 9 microns~15 microns of the glass fibre.
Wherein in one embodiment, the chopped length of the glass fibre is 3 millimeters~6 millimeters.
Specific embodiment
Syndiotactic polytyrene flame-proof composite material is described in further detail mainly in combination with specific embodiment below.
The syndiotactic polytyrene flame-proof composite material of one implementation method, in terms of parts by weight, including：
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 resin, polypropylene
Sour pentabromo- benzyl ester, double (tribromophenoxy) ethane, double tetrabromo phthalimide ethane and tetrabromobisphenol A carbonic ester oligomer
In 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).
Wherein in one embodiment, coupling agent is in titanate coupling agent, silane coupler and aluminate coupling agent
It is at least one.Preferably, titanate coupling agent is selected from isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, double (two pungent oxygen
Base pyrophosphoric acid ester group) ethylene titanate esters, the oleic acid acyloxy of isopropyl two (dioctyl phosphoric acid acyloxy) titanate esters and monoalkoxy
At least one in unrighted acid titanate esters.Silane coupler is selected from the VTES, (β-first of vinyl three
Epoxide ethyoxyl) in silane, gamma-aminopropyl-triethoxy-silane and 3- glycydoxy trimethoxy silanes extremely
Few one kind.Aluminate coupling agent be selected from distearyl acyl-oxygen isopropyl Aluminate, DL-411 and anti-settling Aluminate ASA in extremely
Few one kind.Certainly, it is necessary to illustrate, coupling agent is not limited to mentioned kind, the coupling of other energy reinforcing material interface performances
Agent can be used.
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, glass fibre is selected from least in short glass fiber and continuous glass fibre
Kind.Wherein in one embodiment, the length of short glass fiber is 3 millimeters~6 millimeters.
Wherein in one embodiment, a diameter of 9 microns~15 microns of glass fibre.
Wherein in one embodiment, syndiotactic polytyrene flame-proof composite material also includes the nucleator no more than 2 parts.Into
Core agent is selected from talcum powder, zinc oxide, silicate, stearate, nano imvite, carbonate, phosphate, Sodium Benzoate, unitary
At least one in carboxylate.Preferably, the particle diameter of nucleator is 0.1 micron~2 microns.Silicate is selected from alumina silicate, silicic acid
At least one in calcium, magnesium silicate and sodium metasilicate.Stearate is selected from aluminum stearate, lithium stearate, magnesium stearate, stearic acid
At least one in zinc, barium stearate and calcium stearate.Carbonate is selected from calcium carbonate, barium carbonate, zinc carbonate and magnesium carbonate
It is at least one.Phosphate is selected from least one in calcium phosphate, sodium phosphate, potassium phosphate and trbasic zinc phosphate.Unary carboxylation is selected from one
At least one in first carboxylic acid sodium, monocarboxylic acid potassium and monocarboxylic acid calcium.It should be noted that nucleator can be omitted, also may be used
Think other nucleators commonly used in the trade.
Wherein in one embodiment, syndiotactic polytyrene flame-proof composite material also includes the auxiliary agent no more than 3 parts.Auxiliary agent
Selected from least one in ultra-violet absorber, colouring agent, lubricant and releasing agent.Preferably, syndiotactic polytyrene is fire-retardant multiple
Ultra-violet absorber, 0 part~2 parts of colouring agent, 0 part~0.6 part of the lubricant and 0 that also included 0 part~0.6 part of condensation material
Part~1 part of releasing agent.Preferably, ultra-violet absorber be selected from OPS (salicylic acid is to t-octyl phenyl ester), UV-242 (2- hydroxyls-
4- (2 '-ethyl hexyl oxy) benzophenone), UV-622 (poly-succinic (4- ethoxy -2,2,6,6- tetramethyl -1- piperidines second
Alcohol) ester) and UV-326 (2'- (the 2'- hydroxyl -3'- tert-butyl group -5'- aminomethyl phenyls) -5- chlorobenzotriazoles) at least one.
Colouring agent is selected from least one in titanium dioxide, ultramarine blue, phthalocyanine green, carbon black, permanent yellow and fluorescein.Lubricant is selected from
EBS (ethylene bis-fatty acid amides), PETS (pentaerythritol stearate), SEED (two (2,2,6,6- tetramethyl -3- piperidinamines
Base)-isophtalamide) and TAF (modified ethylene bis-fatty acid amides) at least one.Releasing agent be selected from lithium stearate,
At least one in aluminum stearate, magnesium stearate and zinc stearate.Certainly, ultra-violet absorber, colouring agent, lubricant and the demoulding
Agent can be omitted, and can use other materials commonly used in the trade.
Wherein in one embodiment, syndiotactic polytyrene flame-proof composite material, in terms of parts by weight, including：
Above-mentioned syndiotactic polytyrene flame-proof composite material, is modified by adding glass fibre, can improve mechanical property
Can and heat resistance, add polyhexamethylene adipamide and compatilizer, do not affect the mechanical properties and heat resistance in the case of can change
Kind impact property, so that better mechanical property and heat resistance is preferable；Laser carving powder is added, the figure of needs is designed by computer software
Case and letter, local irradiation is carried out using the laser beam of high density energy to workpiece, makes material surface that physics occur with chemistry
Change, so as to obtain visible pattern, using Computer Control Technology, change mark content is very easy to, and adapts to modern production
Efficient requirement, manufacturing process is done using laser, on the surface of material can produce very fine mark and durability is non-
Chang Hao, does not have the effect of operating force with workpiece, it is ensured that the original precision of workpiece, processing mode flexibly, production efficiency it is high and
It is environmentally safe；Fire resistance is improved by compound flame retardant and fire retarding synergist, make its can be widely used in PET, PBT,
The occasion of the engineering plastics application such as PA, PPS.
The preparation method of above-mentioned syndiotactic polytyrene 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 glass fibre extruding pelletization are obtained into syndiotactic polytyrene flame-proof composite material.
Wherein in one embodiment, during pre-composition added into double screw extruder, then glass fibre is squeezed from twin-screw
Go out the addition of pusher side spout, through melting extrusion granulation, water-cooled, air-dry, pelletizing, be dried to obtain the fire-retardant composite wood of syndiotactic polytyrene
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~280 DEG C of area；Four 250 DEG C of areas~280 DEG C；5th area：250 DEG C~270 DEG C；Six 240 DEG C of areas~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；240 DEG C~280 DEG C of head；Screw speed be 300rpm~
600rpm。
Step S140, by syndiotactic polytyrene composite injection moulding after, by laser engraving pattern.
The preparation method of above-mentioned syndiotactic polytyrene flame-proof composite material, it is simple to operate, it is easy to industrialize.
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 glass fibre, then
Syndiotactic polytyrene flame-proof composite material is obtained after water cooled, air-dried, pelletizing, drying.
The syndiotactic polytyrene flame-proof composite material of gained after injection moulding on injection machine, the editor's need in laser engraving machine
The pattern of laser engraving, 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 glass fibre, then
Syndiotactic polytyrene flame-proof composite material is obtained after water cooled, air-dried, pelletizing, drying.
The syndiotactic polytyrene flame-proof composite material of gained after injection moulding on injection machine, the editor's need in laser engraving machine
The pattern of laser engraving, 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 glass fibre, Ran Houjing
Syndiotactic polytyrene flame-proof composite material is obtained after water-cooled, air-dried, pelletizing, drying.
The syndiotactic polytyrene flame-proof composite material of gained after injection moulding on injection machine, the editor's need in laser engraving machine
The pattern of laser engraving, 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 glass fibre, Ran Houjing
Syndiotactic polytyrene flame-proof composite material is obtained after water-cooled, air-dried, pelletizing, drying.
The syndiotactic polytyrene flame-proof composite material of gained after injection moulding on injection machine, the editor's need in laser engraving machine
The pattern of laser engraving, 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 short glass fiber, then
Syndiotactic polytyrene flame-proof composite material is obtained after water cooled, air-dried, pelletizing, drying.
The syndiotactic polytyrene flame-proof composite material of gained after injection moulding on injection machine, the editor's need in laser engraving machine
The pattern of laser engraving, 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 short glass fiber, Ran Houjing
Syndiotactic polytyrene flame-proof composite material is obtained after water-cooled, air-dried, pelletizing, drying.
The syndiotactic polytyrene flame-proof composite material of gained after injection moulding on injection machine, the editor's need in laser engraving machine
The pattern of laser engraving, it is possible to pattern needed for directly being carved on product.
Syndiotactic polytyrene flame-proof composite material prepared by embodiment 1~6 is made into test sample carries out performance test, ties
Fruit is shown in Table 1.
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 flame-proof composite material by modified, better mechanical property, fire resistance preferably and heat resistance compared with
It is good, while having excellent laser carving performance, had a good application prospect in fields such as Aero-Space, automobile, electronic apparatus.Can
It is 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 flame-proof composite material, it is characterised in that in terms of parts by weight, including：
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 flame-proof composite material according to claim 1, it is characterised in that the syndiotactic polytyrene
Weight average molecular weight be 200,000~700,000；And/or, the intrinsic viscosity 2.2dL/g~3.0dL/g of the polyhexamethylene adipamide.
3. syndiotactic polytyrene flame-proof composite material according to claim 1, it is characterised in that the fire retarding synergist choosing
From antimony oxide, sodium antimonate, antimonic acid anhydride, Firebrake ZB, metaborate, iron oxide, montmorillonite, kaolin, talcum powder, melamine
Amine, melamine salt, ammonium polyphosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, polycondensation aryl
At least one in phosphate and polytetrafluoroethylene (PTFE).
4. syndiotactic polytyrene flame-proof composite material according to claim 1, it is characterised in that the coupling agent is selected from titanium
At least one in acid esters coupling agent, silane coupler and aluminate coupling agent.
5. syndiotactic polytyrene flame-proof composite material according to claim 1, it is characterised in that the antioxidant is selected from four
[β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, N, N'- couples-(3- (3,5- di-t-butyl -4- hydroxy benzenes
Base) propiono) hexamethylene diamine, the β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, (the 3,5- bis- of 1,3,5- tri-
Tertiary butyl-4-hydroxy benzyl) isocyanuric acid, three [2.4- di-tert-butyl-phenyls] phosphite esters, double (2,4- DI-tert-butylphenol compounds)
At least one in pentaerythritol diphosphites and double (2,4- dicumylphenyl) pentaerythritol diphosphites.
6. syndiotactic polytyrene flame-proof composite material according to claim 1, it is characterised in that also including no more than 2 parts
Nucleator, the nucleator be selected from talcum powder, zinc oxide, silicate, stearate, nano imvite, carbonate, phosphoric acid
At least one in salt, Sodium Benzoate, unary carboxylation.
7. syndiotactic polytyrene flame-proof composite material according to claim 1, it is characterised in that also including no more than 3 parts
Auxiliary agent, the auxiliary agent be selected from ultra-violet absorber, colouring agent, lubricant and releasing agent at least one.
8. syndiotactic polytyrene flame-proof composite material according to claim 1, it is characterised in that the glass fibre is selected from
At least one in short glass fiber and continuous glass fibre.
9. syndiotactic polytyrene flame-proof composite material according to claim 1, it is characterised in that the glass fibre it is straight
Footpath is 9 microns~15 microns.
10. syndiotactic polytyrene flame-proof composite material according to claim 1, it is characterised in that the glass fibre
Chopped length is 3 millimeters~6 millimeters.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778317A (en) * | 2016-01-04 | 2016-07-20 | 张明威 | High-performance elastomer material |
| 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 |
| WO2022110663A1 (en) * | 2020-11-26 | 2022-06-02 | 金发科技股份有限公司 | Low-smoke-density halogen-containing flame-retardance-enhanced pbt/pet composite, preparation method therefor, and use 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105778317A (en) * | 2016-01-04 | 2016-07-20 | 张明威 | High-performance elastomer material |
| 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 |
| WO2022110663A1 (en) * | 2020-11-26 | 2022-06-02 | 金发科技股份有限公司 | Low-smoke-density halogen-containing flame-retardance-enhanced pbt/pet composite, preparation method therefor, and use thereof |
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| CN106751077B (en) | 2019-11-29 |
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