CN106221104A - Flame retardant styrene resin compositions and preparation method thereof - Google Patents
Flame retardant styrene resin compositions and preparation method thereof Download PDFInfo
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- C08K5/00—Use of organic ingredients
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- C08K5/13—Phenols; Phenolates
- C08K5/136—Phenols containing halogens
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- C08K5/00—Use of organic ingredients
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08K5/3492—Triazines
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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- 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
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- C08L25/06—Polystyrene
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- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The present invention relates to styrene resin technical field, particularly a kind of flame retardant styrene resin compositions, including the component of following weight portion: styrene resin 84 88 weight portion；Halogenated flame retardant 7 10 weight portion；Phosphorus flame retardant 57 weight portion；Filler and auxiliary agent 0.1 10 weight portion.Compared with prior art, the present invention is by introducing cheap, less on impact strength impact phosphorus flame retardant, the Sb system fire retardant that fictitious hosts is expensive, the synergistic anti-flammability utilizing halogen phosphorus makes styrene resin reach V2 level flame retardant effect, and the impact strength of styrene resin relatively halogen sb system promotes substantially；Additionally halogen phosphorus flame-retardant system is cheap, relative usage is few, flame retarding efficiency is high, significantly reduces the production cost of V2 flame retardant styrene resin.
Description
Technical field
The present invention relates to styrene resin technical field, particularly a kind of flame retardant styrene resin compositions and system thereof
Preparation Method.
Background technology
Styrene resin is widely used in electronic apparatus, auto industry, office equipment, Communication Equipment, household electrical appliance etc.
Field, owing to styrene resin belongs to inflammable macromolecular material, when electronic apparatus etc. has the product of flame-retardancy requirements, needs
It is carried out flame-retardant modified, to meet its use requirement in terms of fire safety.In styrene resin is flame-retardant modified
Conventional flame-retardant system is halogenated flame retardant and the synergistic system of Sb system fire retardant composition, and this flame-retardant system exists the most not
Foot: halogenated flame retardant and Sb system fire retardant are expensive, and just can play the most fire-retardant when halogen antimony fire retardant addition is bigger
Effect, halogen antimony fire retardant can reduce the impact resistance of styrene resin simultaneously, especially when halogen antimony fire retardant addition relatively
Time big, the impact strength of styrene materials substantially reduces.
Summary of the invention
It is an object of the invention to halogen antimony fire retardant in the above-mentioned flame retardant styrene resin overcoming prior art to exist add
Dosage is big, causes the defect that flame retardant styrene resin production cost height, impact strength reduce, it is provided that a kind of Flameproof styrenic class
Resin combination, selects halogen system and the synergistic flame-retardant system of phosphorus flame retardant composition, and flame retarding efficiency is high, and can significantly improve
The impact strength of styrene resin.
The present invention is to use following technical scheme to realize:
A kind of styrene resin composite, it is characterised in that include the component of following weight portion:
Styrene resin 84-88 weight portion；
Halogenated flame retardant 7-10 weight portion；
Phosphorus flame retardant 5-7 weight portion；
Filler and auxiliary agent 0.1-10 weight portion.
Selecting halogen system and the synergistic flame retardant of phosphorus flame retardant composition, flame retarding efficiency is high, can significantly improve benzene second simultaneously
The impact strength of vinyl resin；Traditional halogen antimony synergistic flame-retardant system, addition is big, expensive, and halogenated flame retardant and antimony
Flame retardant is relatively big on Impact Properties of Materials impact, not only substantially increases the production cost of flame retardant styrene resin, and
Reducing the impact strength of material, current bromine antimony flame retardant styrene resin, formula relative maturity, bromine antimony number declines space
Less, it is difficult to significantly to reduce cost, introduce cheap phosphorus flame retardant and replace expensive Sb system fire retardant, solve
The problem that flame retardant styrene resin production cost of having determined is high.
Technique scheme, further, described halogenated flame retardant be chlorinated polyethylene, chlorinated paraffin, tetrabromobisphenol A,
TDE, brominated triazine, brominated epoxy, Brominated Polystyrene, bromination phenoxy resin, tribromo-benzene based phosphates, bromine
Change one or more in polycarbonate oligomer.
Technique scheme, further, described phosphorus flame retardant is bisphenol-A double (diphenyl phosphoester), resorcinol
Double (diphenyl phosphoesters), triphenyl phosphate, trimethyl phosphate, triethyl phosphate, poly aryl phosphate ester, tricresyl phosphate
In one or more.
Technique scheme, further, also includes that metal-oxide, the weight portion of described metal-oxide are 0-1 part.
Introduce metal-oxide, it is possible to improve anti-flammability further.
Technique scheme, further, described metal-oxide is magnesium, aluminum, zinc, molybdenum, nickel, copper, ferrum, potassium, sodium
One or more of oxide.
Technique scheme, further, described styrene resin is acrylonitrile-butadiene-styrene copolymer, height
Anti-impact styrene, general purpose polystyrene, MBS, acrylonitrile-chloride polyethylene-
One or more in styrol copolymer, acrylonitritrile-styrene resin, copolymer of methyl methacrylatestyrene.
Technique scheme, further, containing styrene reworked material in described styrene resin.
Technique scheme, further, described filler is inorganic filler, and described auxiliary agent is antioxidant, lubricant, impact
At least one in modifying agent.Described inorganic filler can select Pulvis Talci, barium sulfate, calcium carbonate, montmorillonite, Kaolin,
One or more in Muscovitum, glass microballoon, brucite, wollastonite.
The preparation method of a kind of styrene resin composite, claims respectively according to the proportioning described in any of the above-described claim
Component, stirs each component through high-speed mixer so that it is mix homogeneously, is then fed in double screw extruder, through twin screw
Shearing, conveying, mixing, then through head extrusion, tie rod, fetch water, pelletizing, be dried and make.
Technique scheme, further, the draw ratio of described double-screw extruder screw is 38-48, and front-end temperature is
180-200 DEG C, interrupting temperature and be 200-220 DEG C, head extrusion temperature is 220-230 DEG C, and screw speed is 300-800rpm.
Compared with prior art, the phosphorus flame retardant that the present invention is cheap by introducing, less on impact strength impact,
The Sb system fire retardant that fictitious hosts is expensive, utilizes the synergistic anti-flammability of halogen phosphorus to make styrene resin reach V2 level flame retardant effect,
And the impact strength of styrene resin relatively halogen sb system promotes substantially；Additionally halogen phosphorus flame-retardant system is cheap, relatively use
Amount less, flame retarding efficiency high, significantly reduce the production cost of V2 flame retardant styrene resin.
Detailed description of the invention
In order to be more clearly understood from the above-mentioned purpose of the present invention, feature and advantage, below in conjunction with embodiment to this
Invention is described further.
Embodiment 1
The each component of styrene resin composite and weight portion thereof:
Styrene resin 84
Halogenated flame retardant 7
Phosphorus flame retardant 6
Antioxidant 0.1
Wherein
Styrene resin is 8250 high impact grade polystyrene resins of platform；
Halogenated flame retardant is the TDE of refined treasured；
Phosphorus flame retardant is the PX-220 poly aryl phosphate ester of ten thousand Shengs；
Antioxidant is Irganox 1010.
Preparation method: weigh each component according to said ratio, will weigh up all materials and stir through high-speed mixer so that it is be mixed
Closing uniformly, mixer rotating speed is 600rpm；Said mixture is sent in extruder, in the shearing of twin screw, conveying, mixing
Under, fully melt, mixing, then through head extrusion, tie rod, fetch water, pelletizing, dry, finally pack.Double-screw extruder screw
Draw ratio is 42, and front-end temperature is 180 DEG C, and interrupting temperature is 200 DEG C, and head extrusion temperature is 220 DEG C, and screw speed is
600rpm。
Embodiment 2
The each component of styrene resin composite and weight portion thereof:
Styrene resin 86
Halogenated flame retardant 8
Phosphorus flame retardant 5
Metal-oxide 0.5
Antioxidant 0.2
Wherein
Styrene resin is 8250 resins of platform；
Halogenated flame retardant is the tetrabromobisphenol A of refined treasured；
Phosphorus flame retardant is the PX220 of ten thousand Shengs；
Metal-oxide is zinc oxide；
Antioxidant is Irganox 1010.
Preparation method: concrete steps are with reference to embodiment 1, and wherein, mixer rotating speed is 800rpm；Double-screw extruder screw
Draw ratio be 42, front-end temperature is 200 DEG C, interrupt temperature be 220 DEG C, head extrusion temperature is 220 DEG C, and screw speed is
500rpm。
Embodiment 3
The each component of styrene resin composite and weight portion thereof:
Styrene resin 85
Halogenated flame retardant 8
Phosphorus flame retardant 6
Pulvis Talci 3
Metal-oxide 1
Antioxidant 0.1
Wherein
Styrene resin is scape lake day beautiful 425TV high impact polystyrene；
Halogenated flame retardant is chlorinated paraffin；
Phosphorus flame retardant is the triphenyl phosphate of ten thousand Shengs；
Pulvis Talci is 3000 mesh；
Metal-oxide is magnesium oxide；
Antioxidant is Irganox 1076.
Preparation method: concrete steps are with reference to embodiment 1, and wherein, mixer rotating speed is 1000rpm；Double screw extruder spiral shell
The draw ratio of bar is 42, and front-end temperature is 200 DEG C, and interrupting temperature is 210 DEG C, and head extrusion temperature is 220 DEG C, and screw speed is
300rpm。
Embodiment 4
The each component of styrene resin composite and weight portion thereof:
Styrene resin 85
Halogenated flame retardant 10
Phosphorus flame retardant 5
Metal-oxide 1
Antioxidant 0.2
Lubricant 0.3
Wherein
Styrene resin is ABS121H general purpose polystyrene；
Halogenated flame retardant is brominated triazine；
Phosphorus flame retardant is the triphenyl phosphate of ten thousand Shengs；
Metal-oxide is zinc oxide；
Antioxidant is Irganox 1010；
Lubricant is fatty acid amide.
Preparation method: concrete steps are with reference to embodiment 1, and wherein, mixer rotating speed is 800rpm；Double-screw extruder screw
Draw ratio be 42, front-end temperature is 190 DEG C, interrupt temperature be 210 DEG C, head extrusion temperature is 220 DEG C, and screw speed is
600rpm。
Embodiment 5
The each component of styrene resin composite and weight portion thereof:
Styrene resin 85
Halogenated flame retardant 8
Phosphorus flame retardant 5
Barium sulfate 2
Metal-oxide 0.8
Antioxidant 0.2
Lubricant 0.5
Wherein
Styrene resin is scape lake day beautiful 425TV high impact polystyrene；
Halogenated flame retardant is the tetrabromobisphenol A of refined treasured；
Phosphorus flame retardant is the triphenyl phosphate of ten thousand Shengs；
Barium sulfate is 3000 mesh；
Metal-oxide is zinc oxide；
Antioxidant is Irganox 168；
Lubricant is fatty acid amide.
Preparation method: concrete steps are with reference to embodiment 1, and wherein, mixer rotating speed is 800rpm；Double-screw extruder screw
Draw ratio be 42, front-end temperature is 190 DEG C, interrupt temperature be 210 DEG C, head extrusion temperature is 220 DEG C, and screw speed is
500rpm。
Embodiment 6
The each component of styrene resin composite and weight portion thereof:
Styrene resin 88
Impact modifying agent 2
Halogenated flame retardant 8
Phosphorus flame retardant 6
Metal-oxide 0.1
Antioxidant 0.2
Lubricant 0.5
Wherein
Styrene resin is scape lake day beautiful 425TVL；
Impact modifying agent is SBS；
Halogenated flame retardant is brominated triazine；
Phosphorus flame retardant is that the RDP resorcinol of refined gram is double (diphenyl phosphoester)；
Metal-oxide is magnesium oxide；
Antioxidant is Irganox 1098；
Lubricant is fatty acid amide.
Preparation method: concrete steps are with reference to embodiment 1, and wherein, mixer rotating speed is 2000rpm；Double screw extruder spiral shell
The draw ratio of bar is 38, and front-end temperature is 200 DEG C, and interrupting temperature is 210 DEG C, and head extrusion temperature is 230 DEG C, and screw speed is
800rpm。
Embodiment 7
The each component of styrene resin composite and weight portion thereof:
Styrene resin 50
Styrene resin reworked material 35
Halogenated flame retardant 9
Phosphorus flame retardant 7
Antioxidant 0.2
Wherein
Styrene resin is ABS 121H；
Halogenated flame retardant is brominated triazine；
Phosphorus flame retardant is the PX220 of ten thousand Shengs；
Metal-oxide is magnesium oxide；
Antioxidant is Irganox 1010；
Preparation method: concrete steps are with reference to embodiment 1, and wherein, mixer rotating speed is 900rpm；The length of double-screw extruder screw
Footpath ratio is 42, and front-end temperature is 200 DEG C, and interrupting temperature is 210 DEG C, and head extrusion temperature is 220 DEG C, and screw speed is
500rpm。
Embodiment 8
The each component of styrene resin composite and weight portion thereof:
Styrene resin 60
Styrene resin reworked material 28
Halogenated flame retardant 8
Phosphorus flame retardant 6
Metal-oxide 1
Lubricant 0.2
Wherein
Styrene resin is the 8250 of platform；
Halogenated flame retardant is the tetrabromobisphenol A of refined treasured；
Phosphorus flame retardant is the PX220 of ten thousand Shengs；
Metal-oxide is zinc oxide；
Lubricant is fatty acid amide.
Preparation method: concrete steps are with reference to embodiment 1, and wherein, mixer rotating speed is 1000rpm；Double screw extruder spiral shell
The draw ratio of bar is 42, and front-end temperature is 180 DEG C, and interrupting temperature is 210 DEG C, and head extrusion temperature is 220 DEG C, and screw speed is
600rpm。
Comparative example 1
The each component of styrene resin composite and weight portion thereof:
Styrene resin 84
Impact modifying agent 2
Halogenated flame retardant 9
Sb system fire retardant 4
Antioxidant 0.3
Lubricant 1
Wherein
Styrene resin is 8250 resins of platform；
Impact modifying agent is SBS；
Halogenated flame retardant is the TDE of refined treasured；
Sb system fire retardant is antimony oxide；
Antioxidant is B215；
Lubricant is fatty acid amide.
Preparation method: concrete steps are with reference to embodiment 1, and wherein, mixer rotating speed is 900rpm；Double-screw extruder screw
Draw ratio be 42, front-end temperature is 180 DEG C, interrupt temperature be 220 DEG C, head extrusion temperature is 220 DEG C, and screw speed is
500rpm。
Comparative example 2
The each component of styrene resin composite and weight portion thereof:
Styrene resin 84
Impact modifying agent 2
Halogenated flame retardant 10
Sb system fire retardant 3
Antioxidant 0.2
Lubricant 0.5
Wherein
Styrene resin is 8250 resins of platform；
Impact modifying agent is SBS；
Halogenated flame retardant is tetrabromobisphenol A；
Sb system fire retardant is antimony oxide；
Antioxidant is B215；
Lubricant is calcium stearate.
Preparation method: concrete steps are with reference to embodiment 1, and wherein, mixer rotating speed is 800rpm；Double-screw extruder screw
Draw ratio be 42, front-end temperature is 160 DEG C, interrupt temperature be 210 DEG C, head extrusion temperature is 210 DEG C, and screw speed is
500rpm。
Comparative example 3
The each component of styrene resin composite and weight portion thereof:
Styrene resin 50
Styrene resin reworked material 35
Halogenated flame retardant 11
Sb system fire retardant 4
Antioxidant 0.2
Wherein
Styrene resin is 8250 resins of platform；
Impact modifying agent is SBS；
Halogenated flame retardant is tetrabromobisphenol A；
Sb system fire retardant is antimony oxide；
Antioxidant is B215.
Preparation method: concrete steps are with reference to embodiment 1, and wherein, mixer rotating speed is 1000rpm；Double screw extruder spiral shell
The draw ratio of bar is 42, and front-end temperature is 170 DEG C, and interrupting temperature is 210 DEG C, and head extrusion temperature is 210 DEG C, and screw speed is
500rpm。
To embodiment 1-8 and and the flame retardant styrene resin prepared of comparative example 1-3 carry out performance test, test index and
Method is as shown in table 1, and test result is as shown in table 2.
Table 1
| Physical property | Method of testing |
| Hot strength (50mm/min) | ASTM D638 |
| Bending strength (2mm/min) | ASTM D790 |
| Melt index (200 DEG C, 5Kg) | ASTM D1238 |
| Heat distortion temperature (1.82MPa) | ASTM D648 |
| IZOD notch impact strength (3.2mm) | ASTM D256 |
| Flammability (vertical combustion 3.0mm/1.5mm) | UL 94 |
Table 2
Embodiment 1-8 and comparative example 1-3 test result show, halogen system, the cooperative flame retardant system of phosphorus system composition have very well
Flame retarding efficiency；With the antimony based flame retardant that cheap phosphorus flame retardant fictitious hosts is expensive, production cost is greatly reduced, with
Time styrene resin composite impact strength relatively halogen sb system promote substantially；For the styrene containing phenylethylene reworked material
Resinoid, its fire resistance reaches V2 level, and impact strength also significantly improves, other every physical indexs close to styrene virgin material,
Have broad application prospects.
Embodiment described above is only to be described, the preferred embodiment of the present invention not to the scope of the present invention
Being defined, on the premise of designing spirit without departing from the present invention, those of ordinary skill in the art are to technical scheme
The various deformation made and improvement, all should fall into the protection domain of technical solution of the present invention.
Claims (10)
1. a styrene resin composite, it is characterised in that include the component of following weight portion:
Styrene resin 84-88 weight portion；
Halogenated flame retardant 7-10 weight portion；
Phosphorus flame retardant 5-7 weight portion；
Filler and auxiliary agent 0.1-10 weight portion.
Styrene resin composite the most according to claim 1, it is characterised in that described halogenated flame retardant is that chlorination gathers
Ethylene, chlorinated paraffin, tetrabromobisphenol A, TDE, brominated triazine, brominated epoxy, Brominated Polystyrene, bromination benzene oxygen
One or more in base resin, tribromo-benzene based phosphates, brominated polycarbonate oligomer.
Styrene resin composite the most according to claim 1, it is characterised in that described phosphorus flame retardant is bisphenol-A
Double (diphenyl phosphoesters), resorcinol double (diphenyl phosphoester), triphenyl phosphate, trimethyl phosphate, triethyl phosphate, many
One or more in poly-aryl phosphate ester, tricresyl phosphate.
4. according to the styrene resin composite described in any one of claim 1-3, it is characterised in that also include burning
Thing, the weight portion of described metal-oxide is 0-1 part.
Styrene resin composite the most according to claim 4, it is characterised in that described metal-oxide be magnesium,
Aluminum, zinc, molybdenum, nickel, copper, ferrum, potassium, one or more of oxide of sodium.
6. according to the styrene resin composite described in any one of claim 1-3, it is characterised in that described phenylethylene tree
Fat is acrylonitrile-butadiene-styrene copolymer, high impact styrene, general purpose polystyrene, methyl methacrylate-fourth two
Alkene-styrol copolymer, acrylonitrile-chlorianted polyethylene-styrene terpolymer, acrylonitritrile-styrene resin, methacrylic acid
One or more in methyl ester-styrol copolymer.
7. according to the styrene resin composite described in any one of claim 1-3, it is characterised in that described phenylethylene tree
Containing styrene reworked material in fat.
Styrene resin composite the most according to claim 7, it is characterised in that described filler is inorganic filler, institute
Stating auxiliary agent is at least one in antioxidant, lubricant, impact modifying agent.
9. the preparation method of a styrene resin composite, it is characterised in that described in any of the above-described claim
Proportioning weigh each component, by each component through high-speed mixer stir so that it is mix homogeneously, be then fed into double screw extruder
In, through the shearing of twin screw, conveying, mixing, then through head extrusion, tie rod, fetch water, pelletizing, dry make.
The preparation method of styrene resin composite the most according to claim 9, it is characterised in that described twin screw
The draw ratio of extruder screw is 38-48, and front-end temperature is 180-200 DEG C, interrupts temperature and is 200-220 DEG C, head extrusion temperature
Degree is for 220-230 DEG C, and screw speed is 300-800rpm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610735362.4A CN106221104A (en) | 2016-08-26 | 2016-08-26 | Flame retardant styrene resin compositions and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610735362.4A CN106221104A (en) | 2016-08-26 | 2016-08-26 | Flame retardant styrene resin compositions and preparation method thereof |
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| CN106221104A true CN106221104A (en) | 2016-12-14 |
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| CN201610735362.4A Pending CN106221104A (en) | 2016-08-26 | 2016-08-26 | Flame retardant styrene resin compositions and preparation method thereof |
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