CN103160036B - A kind of flame-retardant high-impact modified polystyrene resin and preparation method thereof - Google Patents
A kind of flame-retardant high-impact modified polystyrene resin and preparation method thereof Download PDFInfo
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- CN103160036B CN103160036B CN201110424173.2A CN201110424173A CN103160036B CN 103160036 B CN103160036 B CN 103160036B CN 201110424173 A CN201110424173 A CN 201110424173A CN 103160036 B CN103160036 B CN 103160036B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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Abstract
The invention belongs to technical field of polymer materials, relate to a kind of modified polystyrene composition and preparation method thereof.Said composition is made up of the component comprising following weight portion: high-impact polystyrene resin 70 80 parts；Bromide fire retardant 12 15 parts；Chlorinated polyethylene 2 10 parts；Antimony oxide 15 parts；0.1 1 parts of antioxidant；Lubricant 0.1 0.5 parts.The present invention makes high impact polystyrene keep equivalence even preferably fire retardation while reducing antimony consumption, and it is less to the Effect on Mechanical Properties of high impact polystyrene, high impact polystyrene is made still to keep the highest impact resilience, it is adaptable to have household appliances and electronic product such as casing of domestic electrical equipment, electrical appliance, the instrument and meter accessory etc. of fire-retardant demand.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of modified polystyrene composition and preparation method thereof.
Background technology
High impact polystyrene (HIPS) is a kind of common resins for universal use, the processing good, easy of HIPS combination property and valency
Lattice relative moderate, be widely used in casing of domestic electrical equipment, electrical appliance, instrument and meter accessory, television set telephone case,
Refrigerator linings etc., under most of situations, these fields of employment are required to HIPS and have high flame retardant, except some small members are big
Majority requires that it can reach the V-0 level flame-retardant standard of UL94-.
High impact polystyrene self property determines that it is inflammability plastics, poor fire, pure high impact polystyrene
Vertical combustion is only the HB level of UL94 standard, and poor fire constrains the development of HIPS, because the damage of plastics inflammable initiation injures and deaths
Accident can be found everywhere, and therefore the research and development of flame-retarding HIPS become a big study hotspot.Through development for many years, flame-retarding HIPS system
Having reached its maturity, modal fire retardant systems has halogen based compound, halogen based compound jointly to improve with auxiliary flame retardant
Flame retardant effect.Auxiliary flame retardant is presently mainly mineral-type auxiliary flame retardant, mainly sb oxide, generally antimony oxide
(Sb2O3) and antimony pentoxide (Sb2O5), be most commonly that antimony oxide, antimony from a kind of non-renewable mineral resources,
Along with the continuous increase of yield, its storage capacity constantly reduces, and it is special that antimony ore is classified as protective mining by Ministry of Land and Resources
Determining mineral, control total quantity, protection antimony resource and price, therefore the market price also improves constantly, the cost of antimony oxide
Also the 10-20% of flame-retarding HIPS cost has been accounted for.From the point of view of current market supply and achievement in research, halogen-free flame-retarding HIPS short-term
Inside being still unlikely to quickly develop, what major part market still selected is to have halogen fire retardant, therefore suitable in the urgent need to finding
Compound replace antimonide as the synergist of halogen system flame-retardant system to reduce cost.
Based on problem above, the invention provides a kind of new flame-retardant system, make while reducing antimony oxide consumption
HIPS keeps equivalence even preferably fire retardation, accreditation to reach the FV-0 standard of UL94 standard, and the mechanical property to HIPS
Can affect less.
Summary of the invention
It is an object of the invention to overcome the defect of above-mentioned prior art and provide a kind of modified polystyrene resin and
Preparation method.
Modified to the flame-retarding HIPS using antimony oxide to be auxiliary flame retardant, it is intended to high impact polystyrene is made
Substitute fire resistance in the case of antimony oxide still be able to reach FV-by cheaper widely fire retardant part of originating
0 grade, simultaneously little to the Effect on Mechanical Properties of HIPS.
Object of the present invention is to provide a kind of flame-retarding HIPS combination with high flame resistance and good impact property
Thing, the bromide fire retardant that this flame-retarding HIPS resin is used does not produces the harmful gass such as two English when burning, can pass through
ROHS testing standard, on the other hand this flame-retarding HIPS still uses halogen antimony synergistic system, therefore can guarantee that fire-retardant effect.Additionally,
This flame-retarding HIPS also uses inorganic mineral salt and inorganic matter composition synergistic system part to substitute Sb2O3, still ensure that good fire-retardant
Effect, reduces cost simultaneously.
For achieving the above object, the technical scheme that the present invention uses is as follows:
A kind of MPS, is made up of the component comprising following weight portion:
High-impact polystyrene resin 70-80 part；
Bromide fire retardant 12-15 part；
Chlorinated polyethylene 2-10 part；
Antimony oxide 1-5 part；
Antioxidant 0.1-1 part；
Lubricant 0.1-0.5 part.
Described MPS also includes 0.1-4 weight portion auxiliary flame retardant, preferably 1-4 part auxiliary flame retardant.
Described high-impact polystyrene resin preferred 73-77 weight portion.
Described bromide fire retardant preferred 13-14 weight portion.
Described chlorinated polyethylene preferred 4-8 weight portion；
Described antimony oxide preferred 1-4 weight portion；
Described antioxidant preferred 0.1-1 weight portion；
Described lubricant preferred 0.1-0.5 weight portion.
Described high-impact polystyrene resin includes various types of high impact polystyrene trees disclosed in prior art
Fat, is preferred for the injection grade high-impact polystyrene resin of household electric appliances.
Described bromide fire retardant includes brominated epoxy resin, brominated Polystyrene, tetrabromobisphenol A, tribromphenol, tetrabromo
One or more in ethane, brominated triazine or tribromophenol isocyanates.
Described antimony oxide is 300-12500 mesh.
Described auxiliary flame retardant is the mixture of silicon dioxide, magnesium oxide and montmorillonite, and mixed proportion is any.
The antioxidant used is Hinered phenols or phosphite ester kind antioxidant, preferably 2,6-di-t-butyl-4-methylbenzene
Phenol, 2,4,6-tri-butyl-phenols, β-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) acrylic acid octadecyl ester (antioxidant
1076), 2,2 '-thiobis (4-methyl-6-tert-butylphenol), triphenyl phosphite, trisnonylphenyl phosphite, three (2,
4-tert-butyl-phenyl) phosphite ester (irgasfos 168) or four [methylene-3 ,-3 ', 5-(di-t-butyl-4-hydroxy-pheny) third
Olefin(e) acid] one or more in methane.
The lubricant used is selected from stearic acid, calcium stearate, zinc stearate, fatty acid complex, N, N '-ethylene pair
One or more in stearmide (EBS), Tissuemat E or methyl-silicone oil.
A kind of preparation method of above-mentioned MPS, the method comprises the following steps:
(1) each raw material is weighed the most according to the above ratio, by high-impact polystyrene resin, bromide fire retardant, chlorinated polyethylene
Alkene, antimony oxide, auxiliary flame retardant, antioxidant and lubricant mix 5-by high-speed mixer under the conditions of 60 DEG C-90 DEG C
20 minutes；
(2) by pay-off, the above-mentioned material mixed is sent in double screw extruder, material cutting at screw rod
Cut, the mixing and lower sufficiently fusion of conveying, after eventually passing extrusion, tie rod, cooling, make pellet.
In described step (2), the temperature in each district of double screw extruder is set to: 160 DEG C～180 DEG C of I district, 160 DEG C of II district
～180 DEG C, 165 DEG C～190 DEG C of III district, 165 DEG C～190 DEG C of IV district, 165 DEG C～200 DEG C of V district, 165 DEG C～200 DEG C of VI district,
175 DEG C～215 DEG C of VII district, 175 DEG C～220 DEG C of VIII district, 185 DEG C～225 DEG C of VIIII district, 185 DEG C～230 DEG C of X district, head
Temperature 200 DEG C～230 DEG C.
Beneficial effect:
Compared with prior art, the present invention can be tested by ROHS, solves some and is instructed the restriction brought by ROHS.This
Outward, utilize the mixture part of inorganic mineral and inorganic matter to instead of antimony oxide, both ensure that flame retardant effect and mechanical property
Can, reduce again the cost of production.This low antimony content flame-retarding HIPS good fluidity, is applicable to extrusion and injection, existing
On the basis of flame retarding process, a small amount of production technology is only needed to adjust and can put into production.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, and its purpose is only that and is best understood from the object of the invention, and
Unrestricted protection scope of the present invention.
The percent of the following stated, in addition to particularly pointing out, is mass percent.
By the formula proportion in table 1, HIPS resinoid, various fire retardant, antioxidant and lubricant are put into high-speed mixer
In 70 DEG C of mixing within 10 minutes, be sufficiently mixed uniformly
By pay-off, material is sent in double screw extruder, material screw rod shearing, mixing and conveying under fill
The fusion divided, after eventually passing extrusion, tie rod, cooling, makes pellet.
The temperature in each district of screw rod is set to: 160 DEG C of I district, 162 DEG C of II district, 171 DEG C of III district, 170 DEG C of IV district, V district 175
DEG C, 179 DEG C of VI district, 180 DEG C of VII district, 181 DEG C of VIII district, 190 DEG C of VIIII district, 191 DEG C of X district, head temperature 200 DEG C.Pellet
Make standard batten through screw rod injection moulding, carry out every Mechanics Performance Testing and fire resistance test.Testing standard and result are shown in
Table 2.
The thermoplastic resin used in specific embodiment is HIPS (Shanghai match section, 622), and the bromide fire retardant of use is four
Bromine bisphenol-A (Jin Hu, tetrabromobisphenol A), the chlorinated polyethylene of use be the antimony oxide that CPE2135 (AsiaSat) uses be 600
Mesh, the auxiliary flame retardant of use is the complex being made up of silicon dioxide 50%, magnesium oxide 40%, montmorillonite 10%, use
Rush flowable is calcium stearate, and primary antioxidant is 1076, and auxiliary anti-oxidant is 168.
Table 1
Table 2
As can be seen from Table 2, comparative example uses antimony oxide and auxiliary flame retardant ratio to be 4: 0, and its fire-retardant rank is
UL94-96FV-0.When by shown in embodiment 1,2,3, auxiliary flame retardant substitutes antimony oxide with the replacement amount less than 60%
When, keeping its fire-retardant rank is FV-0, simultaneously little to Effect on Mechanical Properties.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and apply this
Bright.These embodiments obviously easily can be made various amendment by person skilled in the art, and described herein
General Principle is applied in other embodiments without through performing creative labour.Therefore, the invention is not restricted to enforcement here
Example, those skilled in the art are according to the announcement of the present invention, and the improvement made without departing from scope and amendment all should be
Within protection scope of the present invention.
Claims (13)
1. a MPS, it is characterised in that: it is made up of the component of following weight portion:
Described auxiliary flame retardant is only the mixture of silicon dioxide, magnesium oxide and montmorillonite.
MPS the most according to claim 1, it is characterised in that: auxiliary flame retardant is 1-4 weight portion.
MPS the most according to claim 1, it is characterised in that: described high-impact polystyrene resin is
73-77 weight portion.
MPS the most according to claim 1, it is characterised in that: described bromide fire retardant is 13-14 weight
Part.
MPS the most according to claim 1, it is characterised in that: described chlorinated polyethylene is 4-8 weight portion.
MPS the most according to claim 1, it is characterised in that: described high-impact polystyrene resin is for using
Injection grade high-impact polystyrene resin in household electric appliances.
MPS the most according to claim 1, it is characterised in that: described bromide fire retardant includes brominated epoxy
In resin, brominated Polystyrene, tetrabromobisphenol A, tribromphenol, tetrabromoethane, brominated triazine or tribromophenol isocyanates one
More than Zhong.
MPS the most according to claim 1, it is characterised in that: described antimony oxide is 300-12500
Mesh.
MPS the most according to claim 1, it is characterised in that: the antioxidant used is Hinered phenols or Asia
Phosphoric acid ester antioxidant.
MPS the most according to claim 1, it is characterised in that: the antioxidant used is selected from 2,6-bis-uncle
Butyl-4-methylphenol, 2,4,6-tri-butyl-phenol, β-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) acrylic acid octadecyl
Ester, 2,2'-thiobis (4-methyl-6-tert-butylphenol), triphenyl phosphite, trisnonylphenyl phosphite, three (uncles 2,4-
Butyl phenyl) in phosphite ester or four [methylene-3 ,-3 ', 5-(di-t-butyl-4-hydroxy-pheny) acrylic acid] methane one
More than Zhong.
11. MPSs according to claim 1, it is characterised in that: the lubricant used is selected from stearic acid, hard
One in fat acid calcium, zinc stearate, fatty acid complex, N, N '-ethylene bis stearamide, Tissuemat E or methyl-silicone oil
Above.
The preparation method of 12. 1 kinds of arbitrary described MPSs of the claims 1-11, it is characterised in that: the method
Comprise the following steps:
(1) first ratio according to claim 1 weighs each raw material, high-impact polystyrene resin, bromide fire retardant, chlorination is gathered
Ethylene, antimony oxide, auxiliary flame retardant, antioxidant and lubricant are mixed under the conditions of 60 DEG C-90 DEG C by high-speed mixer
5-20 minute；
(2) by pay-off, being sent into by the above-mentioned material mixed in double screw extruder, material is in the shearing, mixed of screw rod
Refining and the lower sufficiently fusion of conveying, after eventually passing extrusion, tie rod, cooling, make pellet.
13. preparation methoies according to claim 12, it is characterised in that: in described step (2), double screw extruder is each
The temperature in district is set to: 160 DEG C～180 DEG C of I district, 160 DEG C～180 DEG C of II district, 165 DEG C～190 DEG C of III district, 165 DEG C of IV district～
190 DEG C, 165 DEG C～200 DEG C of V district, 165 DEG C～200 DEG C of VI district, 175 DEG C～215 DEG C of VII district, 175 DEG C～220 DEG C of VIII district,
185 DEG C～225 DEG C of VIIII district, 185 DEG C～230 DEG C of X district, head temperature 200 DEG C～230 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110424173.2A CN103160036B (en) | 2011-12-16 | 2011-12-16 | A kind of flame-retardant high-impact modified polystyrene resin and preparation method thereof |
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| CN201110424173.2A CN103160036B (en) | 2011-12-16 | 2011-12-16 | A kind of flame-retardant high-impact modified polystyrene resin and preparation method thereof |
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| CN103160036A CN103160036A (en) | 2013-06-19 |
| CN103160036B true CN103160036B (en) | 2016-11-23 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104059185A (en) * | 2014-06-18 | 2014-09-24 | 安徽圣源橡塑科技有限公司 | Flame-retardant polystyrene composite material and preparation method thereof |
| CN104744837B (en) * | 2015-04-13 | 2017-04-26 | 刘新智 | Brominated flame retardant yellowing inhibitor and application thereof |
| CN106117947A (en) * | 2016-08-18 | 2016-11-16 | 东莞市宇豪塑胶科技有限公司 | Black household appliances modification HIPS plastic |
| CN106280189A (en) * | 2016-08-18 | 2017-01-04 | 刘世超 | Aging resistance HIPS plastic |
| CN106380711B (en) * | 2016-08-26 | 2019-03-26 | 青岛海尔新材料研发有限公司 | A kind of fiberglass reinforced fire retardant polystyrene resin composite and preparation method thereof |
| CN106633580A (en) * | 2016-10-17 | 2017-05-10 | 珠海格力电器股份有限公司 | Impact-resistant polystyrene composite material with high heat resistance and high flame-retardant rating, and preparation method and application thereof |
| CN112341743A (en) * | 2020-10-27 | 2021-02-09 | 青岛海尔新材料研发有限公司 | Chemical-resistant flame-retardant HIPS material and preparation method thereof |
| CN113372676B (en) * | 2021-05-25 | 2022-12-02 | 会通新材料股份有限公司 | Flame-retardant high impact polystyrene composition and preparation method thereof |
| CN113402836B (en) * | 2021-07-14 | 2022-10-21 | 上海葛蓝化工科技有限公司 | Macromolecular phosphorus-halogen flame retardant modified high impact polystyrene resin composition and preparation method thereof |
| CN113444334B (en) * | 2021-07-14 | 2022-10-21 | 上海葛蓝化工科技有限公司 | Preparation method of high-impact polystyrene modified by high-molecular composite flame retardant |
| CN116496620B (en) * | 2023-05-26 | 2024-08-30 | 金旸（厦门）新材料科技有限公司 | Low-temperature-resistant high-impact-resistant high-flame-retardant polyamide composite material and preparation method thereof |
Citations (2)
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| CN101845153A (en) * | 2010-06-04 | 2010-09-29 | 深圳市联合鑫科技有限公司 | Inorganic powder additive-type flame retardant and preparation method thereof |
| CN102181118A (en) * | 2011-01-27 | 2011-09-14 | 佛山市南海东方塑料制品有限公司 | Processing technology of low-cost high-performance bromine-containing flame-retardant HIPS material |
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- 2011-12-16 CN CN201110424173.2A patent/CN103160036B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845153A (en) * | 2010-06-04 | 2010-09-29 | 深圳市联合鑫科技有限公司 | Inorganic powder additive-type flame retardant and preparation method thereof |
| CN102181118A (en) * | 2011-01-27 | 2011-09-14 | 佛山市南海东方塑料制品有限公司 | Processing technology of low-cost high-performance bromine-containing flame-retardant HIPS material |
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