CN1221608C - Halogen-free fire-resistant high anti-impact polystyrene/ polyphenyl ether complex containing modified polyphenyl ether and method for production thereof - Google Patents
Halogen-free fire-resistant high anti-impact polystyrene/ polyphenyl ether complex containing modified polyphenyl ether and method for production thereof Download PDFInfo
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- CN1221608C CN1221608C CN 03113673 CN03113673A CN1221608C CN 1221608 C CN1221608 C CN 1221608C CN 03113673 CN03113673 CN 03113673 CN 03113673 A CN03113673 A CN 03113673A CN 1221608 C CN1221608 C CN 1221608C
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Abstract
The present invention relates to a halogen-free, flame retarding and high impact polystyrene/polyphenyl ether composition containing modified polyphenyl ether and a preparation method thereof. The composition belongs to the field of a high molecular material. The composition comprises 40 to 65 wt% of high impact polystyrene resin, 8 to 40 wt% of polyphenyl ether, 5 to 25 wt% of flame retardant and 0.5 to 5 wt% of processing aid. The composition is prepared by adopting a secondary extrusion technology by high-speed premixing dispersion. The composition of the present invention solves the problems of mechanical property reduction, poor stability, environment incompatibility, etc. occurring in the fire retardation of high impact polystyrene resin in the prior art. The composition has a series of outstanding advantages of fire retardancy, environmental protection, weatherability, thermal stability, good mechanical performance, easy processing forming, etc. The composition is very suitable for the light-colored household appliance industrial fields of displayers, video recorders, copying machines, facsimile machines, printers, air conditioners, electric refrigerators, etc. having very great development prospects at present.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of halogen-free flameproof mixture and preparation method thereof.
Background technology
Polystyrene (PS) is to realize industrialization by German I.G method our company (predecessor of BASF AG) in nineteen thirty.As one of five big general-purpose plastics, it has, and formability is good, matter is hard, transparent, rigidity, electrical insulating property, agent of low hygroscopicity, dyeing and advantage such as cheap easily.Generate high-impact polystyrene (HIPS) mixes a small amount of elastomerics in PS after, it has overcome the crisp shortcoming of polystyrene, thereby is widely used in industries such as electronics, automobile, household electrical appliances, instrument, daily necessities, toy.But HIPS burns easily, and weathering resistance is poor, and mobile difference can not be fit to make shortcomings such as surface requirements height and large thin-wall goods after the modification, has limited it and has further promoted the use of.Particularly enter the very promising light household electric appliances field of tool at present such as indicating meter, video recorder, duplicating machine, facsimile recorder, printer, conditioner, refrigerator.(Plastics Technology，1995，41(1)：36～40)
What occur at present much aiming at such use and the halogen-containing flame-retarding HIPS kind ubiquity some shortcomings developed.As adopt the fire-retardant polystyrene mechanical property of halogen-containing compound decabromodiphenyl oxide (being DBDPO), tetrabromo-bisphenol good, flame retarding efficiency height, but weathering resistance is poor, goods in use be subjected to ultraviolet influence easily and produce variable color, problem such as become fragile.And studies show that among the DBDPO in recent years exists and may limit use in several European countries to cancer De dioxin/two furans problems.Therefore in fire-retardant development from now on, must consider the compatibility problem of material and environment.
Adopt effectively flame-retarding HIPS of clorafin, do not have dioxin/two furans problems simultaneously, but its poor stability, its decomposition temperature has only 170 ℃, is lower than the processing temperature of HIPS, and its degradation production hydrogenchloride has serious corrosive nature to mould simultaneously.
Adopt the fire-retardant HIPS of phosphorus system not have dioxin/two furans problems, compliance with environmental protection requirements, but the mechanical property reduction is more.
Summary of the invention
The object of the present invention is to provide a kind of premium properties that keeps the HIPS resin, flame retardant rating reaches the UL94V-0 level, with the no dioxin of good of Environmental compatibility/two furans problems, ultraviolet light and thermal ageing are strong, Heat stability is good, mobile high, product surface gloss, the halogen-free flame-proof highly anti-flush polyphenylacetylene/polyphenyl ether composite that contains Noryl that practical value is high.
Another object of the present invention is to provide the preparation method of above-mentioned mixture.
Noryl halogen-free flame-proof highly anti-flush polyphenylacetylene/the polyphenyl ether composite that contains of the present invention, comprise following component: high-impact polystyrene resin resin 40～65 weight %, polyphenylene oxide 8～40 weight %, fire retardant 5～25 weight %, processing aid 0.5～5 weight % can also contain retardant synergist 1～6 weight %, impact modifying agent 1～15 weight %, oxidation inhibitor 0.1～0.6 weight %, coupling agent 0.2～1 weight %.
Wherein fire retardant is that micro encapsulation multilayer encapsulated red phosphorus, titanium dioxide multilayer coat one or more the mixture in grey red phosphorus, phosphorous acid lipid, the phosphoric acid lipid, more than several based flame retardants very high thermostability and not halogen-containing is all arranged, can obtain very good fire-retardant and processing effect.
Retardant synergist is one or more the mixture in melamine salt, zinc borate, the magnesium hydroxide, adopts multiple retardant synergist recombination energy to make flame retardant effect more remarkable.
The adding of impact modifying agent mainly is to prevent that the adding of fire retardant from making material mechanical performance descend.The selection of impact modifying agent must consider that itself and resin should have good consistency, and impact modifying agent will form suitable phase structure and could more effectively improve toughening effect in material matrix simultaneously.The impact modifying agent that uses among the present invention is one or more the mixture in styrene isoprene styrene block copolymer (SIS) (SIS), styrene-butadiene-styrene block copolymer (SBS), Hydrogenated SBS, the styrene-acrylonitrile copolymer acid butyl ester binary graft modification ethylene-propylene rubber(EPR) (EPDM-g-St/BA).
Oxidation inhibitor is phenols, phosphorous acid esters, contain one or more the mixture in thioesters class, the metal passivator, the phenolic antioxidant that wherein is suitable for body series has 2,4,6-BHT, E-330,2246,1010, phosphorous acid esters have TNP, 168, containing the thioesters class is DLTP, DSTP, and metal passivator has GI-09-367, MD1025, OABH.Because phosphorous acid esters can be eliminated equally by ultraviolet ray and produce the peroxidation group, thereby also play the effect that prevents photoaging.
Coupling agent is one or more the mixture in silane coupling agent, titanate coupling agent, the aluminate coupling agent, as KH550, KH570, A-143, A-186, sulfonyl azide silane, NDZ-101, OL-1618.Coupling agent has improved the consistency between fire retardant and resin, the plasticized modifier, strengthens the bounding force at interface between them, improves the mechanical property of material.
Processing aid is one or more the mixture in fatty acid amide, fatty acid mixture, paraffin, white mineral oil, organic silicone oil, the alpha-methyl styrene, add the dispersiveness that effectively to improve each component man-hour, reduce plastic melt and the bonding strength of metallic surface and the internal friction of plastic melt, the weld mark that occurs in the product when helping solving injection moulding, surface luster is poor, problems such as demoulding difficulty.
Its preparation method in the halogen-free flame-proof highly anti-flush polyphenylacetylene/polyphenyl ether composite that contains Noryl of the present invention is to adopt high speed pre-mixing and dispersing secondary expressing technique.Earlier polyphenylene oxide is mixed after twin screw is extruded by 1: 1～3 weight ratios with high-impact polystyrene resin and be processed as Noryl (MPPO), under high-speed stirring behind the thorough mixing by the twin screw extruder fusion, mixing, extrude, cool off, dry, pelletizing and packing, each subregion temperature of barrel should remain between 220 ℃～260 ℃; Again with all the other high-impact polystyrene resins, MPPO, fire retardant, retardant synergist, impact modifying agent, oxidation inhibitor, coupling agent and and processing aid after the high-speed mixer dispersing and mixing, by the twin screw extruder fusion, mixing, extrude, cool off, dry, pelletizing and packing, each subregion temperature of barrel should remain between 160 ℃～250 ℃.
Preparation method's of the present invention twin screw extruder length-to-diameter ratio is 32～40, and screw speed is 300～500 rev/mins.
The benefit of such secondary expressing technique is to make PPO obtain well to disperse, and the constant product quality of gained.After in mixture, adding MPPO, can reduce the consumption of fire retardant, improve mechanical performance of products.
Compare with traditional flame-proof highly anti-flush polyphenylacetylene resin complexes, halogen-free flame-proof highly anti-flush polyphenylacetylene/the polyphenyl ether composite that contains Noryl of the present invention, owing in composite body system, added polyphenylene oxide, both reduced the consumption of fire retardant, improved mechanical performance of products again.That the high-impact polystyrene/polyphenyl ether composite of the halogen-free flameproof of gained has is fire-retardant, environmental protection, weather-proof, thermally-stabilised, a series of outstanding advantages such as mechanical property is good, easy machine-shaping, is very suitable for the very promising light household electric appliances field of tool at present such as indicating meter, video recorder, duplicating machine, facsimile recorder, printer, conditioner, refrigerator.
Embodiment
Preparation and the physicals thereof that contains the halogen-free flame-proof highly anti-flush polyphenylacetylene/polyphenyl ether composite of Noryl of the present invention sees Table 1.HIPS is adopted in this test, and fire retardant is a micro encapsulation red phosphorus, and impact modifying agent is styrene/acrylic butyl ester binary graft modification EPDM (EPDM-g-St/BA).
Because partial cross-linked EPDM has very low second-order transition temperature, higher intensity.Styrene/acrylic butyl ester multipolymer in the grafting not only has good consistency with HIPS, and because the existence of butyl acrylate makes grafted chain have good kindliness.These characteristics make EPDM-g-St/BA that HIPS is had good toughening effect, can keep the rigidity of HIPS again.
The concrete operation steps of halogen-free flame-proof highly anti-flush polyphenylacetylene/polyphenyl ether composite embodiment that contains Noryl of the present invention is:
1.MPPO the preparation method
With polyphenylene oxide and high-impact polystyrene resin by 40: 60 weight ratios, under high-speed stirring behind the thorough mixing by the twin screw extruder fusion, mixing, extrude, cool off, dry, pelletizing and packing.Each subregion temperature of barrel should remain on 240 ℃.
2. the preparation method of the high-impact polystyrene/polyphenyl ether composite of halogen-free flameproof
To remain high-impact polystyrene resin, MPPO, plasticized modifier, fire retardant, retardant synergist, coupling agent oxidation inhibitor and processing aid under high-speed stirring behind the thorough mixing by the twin screw extruder fusion, mixing, extrude, cool off, dry, pelletizing and packing.Each subregion temperature of barrel should remain on 200 ℃.
Wherein the twin screw extruder length-to-diameter ratio is 38, and screw speed is 400 rev/mins.
The mixture of embodiment preparation is injection molded into the standard batten of testing usefulness by standard size, and physicals by China's national standard and U.S. UL standard testing, sees Table 2 respectively.
Table 1
| Component | 1 | 2 | 3 | 4 | 5* |
| Resin HIPS | 100 | 59.1 | 55.1 | 57.1 | 55.1 |
| 1010 dose of 168 processing of the impact modified EPDM-g-St/BA agent of MPPO MPPO flame retardant microcapsule red phosphorus (phosphorous 85%) agent titanium dioxide multilayer coating structure grey red phosphorus (phosphorous 33%) triphenyl phosphate fire-resistant synergistic hydroxide magnesia mixture coupling organo-silicon coupling agent agent KH550 antioxygen stearmide auxiliary agent calcium stearate butyl stearate | 20 10 6 3 0.5 0.2 0.2 0.5 0.25 0.25 | 15 16 2 7 3 0.5 0.2 0.2 0.5 0.25 0.25 | 15 8 8 7 3 0.5 0.2 0.2 0.5 0.25 0.25 | 15 22 7 3 0.5 0.2 0.2 0.5 0.25 0.25 | |
| Physical property melt index hot strength elongation at break Izod notched Izod impact strength heat distortion temperature bending modulus bending strength flammability (1.6mm) | 2.7 27 40 11 85 2300 39 HB | 5.0 27 30 8.2 86 2100 35 V-0 | 4.0 25 27 8.5 87 2100 32 V-1 | 6.0 25 26 8.2 80 2100 31 V-2 | 3.8 25 27 7.8 87 2100 32 V-0 |
Table 2
| Physicals | Unit | Testing method |
| Melt index hot strength elongation at break Izod notched Izod impact strength heat distortion temperature bending modulus bending strength flammability Izod notched Izod impact strength | g/10min MPa ％ KJ/m 2 ℃ MPa MPa / KJ/m 2 | GB3682 GB1040 GB1040 GB1843 GB1634 GB9341 GB9341 UL94 GB1843 |
Claims (10)
1, a kind of halogen-free flame-proof highly anti-flush polyphenylacetylene/polyphenyl ether composite that contains Noryl, comprise following component: high-impact polystyrene resin 40～65 weight %, polyphenylene oxide 8～40 weight %, fire retardant 5～25 weight %, processing aid 0.5～5 weight %; Earlier polyphenylene oxide is mixed after twin screw is extruded being processed as Noryl with high-impact polystyrene resin by 1: 1～3 weight ratios, again all the other high-impact polystyrene resins, Noryl, fire retardant, processing aid are mixed; Wherein said fire retardant is that micro encapsulation multilayer encapsulated red phosphorus, titanium dioxide multilayer coat one or more the mixture in grey red phosphorus, phosphorous acid lipid, the phosphoric acid lipid, and described processing aid is one or more the mixture in fatty acid amide, fatty acid mixture, paraffin, white mineral oil, organic silicone oil, the alpha-methyl styrene.
2, the halogen-free flame-proof highly anti-flush polyphenylacetylene/polyphenyl ether composite that contains Noryl according to claim 1 is characterized in that containing retardant synergist 1～6 weight %.
3, the halogen-free flame-proof highly anti-flush polyphenylacetylene/polyphenyl ether composite that contains Noryl according to claim 1 and 2 is characterized in that containing impact modifying agent 1～15 weight %.
4, the halogen-free flame-proof highly anti-flush polyphenylacetylene/polyphenyl ether composite that contains Noryl according to claim 3 is characterized in that containing oxidation inhibitor 0.1～0.6 weight %.
5, the halogen-free flame-proof highly anti-flush polyphenylacetylene/polyphenyl ether composite that contains Noryl according to claim 4 is characterized in that containing coupling agent 0.2～1 weight %.
6, the halogen-free flame-proof highly anti-flush polyphenylacetylene/polyphenyl ether composite that contains Noryl according to claim 2, wherein said retardant synergist are one or more the mixture in melamine salt, zinc borate, the magnesium hydroxide.
7, the halogen-free flame-proof highly anti-flush polyphenylacetylene/polyphenyl ether composite that contains Noryl according to claim 3, wherein said impact modifying agent are one or more the mixture in styrene isoprene styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymers, the styrene-acrylonitrile copolymer acid butyl ester binary graft modification ethylene-propylene rubber(EPR).
8, the halogen-free flame-proof highly anti-flush polyphenylacetylene/polyphenyl ether composite that contains Noryl according to claim 4, wherein oxidation inhibitor is phenols, phosphorous acid esters, contains one or more the mixture in thioesters class, the metal passivator.
9, the halogen-free flame-proof highly anti-flush polyphenylacetylene/polyphenyl ether composite that contains Noryl according to claim 5, wherein said coupling agent are one or more the mixture in silane coupling agent, titanate coupling agent, the aluminate coupling agent.
10, the Noryl halogen-free flame-proof highly anti-flush polyphenylacetylene/polyphenyl ether composite that contains according to claim 5, its preparation method are to adopt high speed pre-mixing and dispersing secondary expressing technique; Earlier polyphenylene oxide is mixed after twin screw is extruded by 1: 1～3 weight ratios with high-impact polystyrene resin and be processed as Noryl, again with all the other high-impact polystyrene resins, Noryl, fire retardant, retardant synergist, impact modifying agent, oxidation inhibitor, coupling agent and processing aid after the high-speed mixer dispersing and mixing, by the twin screw extruder fusion, mixing, extrude, cool off, dry, pelletizing and packing.
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| CN101358028B (en) * | 2008-09-02 | 2011-05-11 | 宁波一舟塑胶有限公司 | Halogen-free flame-retardant thermoplastic elastomer electrical cable material using polyphenylene ether as base material and preparation method thereof |
| CN101570631B (en) * | 2009-06-01 | 2011-11-02 | 南京聚隆科技股份有限公司 | High-heat resistance halogen-free fire-retarding polyphenylether and polystyrene composite and preparation method thereof |
| CN101880451B (en) * | 2010-07-23 | 2012-05-09 | 北京化工大学 | Halogen-free fire-retardant polyphenyl ether compound and method for preparing same |
| CN102051037B (en) * | 2010-12-30 | 2012-07-18 | 金发科技股份有限公司 | Halogen-free flame-proof polyenyl ether composition |
| CN102382387B (en) * | 2011-11-02 | 2013-05-29 | 深圳职业技术学院 | Composition of halogen-free flame-retardant polystyrene plastic and preparation method thereof |
| CN102504429A (en) * | 2011-12-02 | 2012-06-20 | 太原理工大学 | Flame-retardant polystyrene nano-composite material and preparation method thereof |
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| CN103242614B (en) * | 2013-05-31 | 2016-01-13 | 广东国立科技股份有限公司 | Halogen-free flame-retarding HIPS plastic modified material and preparation method thereof |
| CN105504639A (en) * | 2013-07-30 | 2016-04-20 | 江苏理工学院 | Preparation method for halogen-free flame-retardant high-impact polystyrene |
| CN105199364B (en) * | 2015-10-28 | 2017-10-24 | 沈阳化工大学 | A kind of fire-retardant ageing-resistant PPO HIPS high polymer alloys and preparation method thereof |
| CN107880421A (en) * | 2017-11-21 | 2018-04-06 | 丁妙严 | Heat resistant type PS, PPO blending formula |
| CN110615937B (en) * | 2019-10-09 | 2023-04-14 | 江苏万纳普新材料科技有限公司 | Special halogen-free flame-retardant synergistic functional master batch for modifying polyphenyl ether and preparation method thereof |
| CN112745592B (en) * | 2020-12-29 | 2023-12-12 | 成都金发科技新材料有限公司 | Styrene composition and application and preparation method thereof |
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