CN1112404C - Anti-photoageing, flame-retarding, high-toughness and thermoplastic composition of styrene polymers - Google Patents
Anti-photoageing, flame-retarding, high-toughness and thermoplastic composition of styrene polymers Download PDFInfo
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- CN1112404C CN1112404C CN 00124684 CN00124684A CN1112404C CN 1112404 C CN1112404 C CN 1112404C CN 00124684 CN00124684 CN 00124684 CN 00124684 A CN00124684 A CN 00124684A CN 1112404 C CN1112404 C CN 1112404C
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Abstract
The present invention provides a composition of a photoaging resisting and flame retarding high-toughness thermoplastic styrene polymer and a preparation method thereof, and the composition can be used outdoors for a long term. The composition is prepared from 60 to 80 wt% of thermoplastic styrene polymer, 0 to 15 wt% of modified thermoplastic styrene polymer, 10 to 30 wt% of flame retardant, 2 to 10 wt% of synergist, 0.2 to 4 wt% of photostabilizer, 1 to 5 wt% of processing aid, etc. through a double-screw extrusion technology. The composition of the present invention has the advantages of long-term photoaging resisting stability, high toughness, superior flame retarding performance and outstanding process shaping performance. The composition can be widely used for meter cases of household appliances and meter cases of electronic electric appliances.
Description
The invention provides a kind of mixture and preparation method thereof of flame retardant thermoplastic styrene base polymer of life-time service out of doors.Mixture of light aging resisting high tenacity flame retardant thermoplastic styrene base polymer and preparation method thereof particularly.
High-impact polystyrene (HIPS) and acrylonitrile-butadiene-styrene copolymer (ABS) are the most frequently used styrenic polymers, owing to have good mechanical property and chemical resistance, be widely used in the shell and the junctor of home appliance, office's usefulness equipment and various electronic apparatus instrument.All these occasions all require material to have flame retardant properties preferably.Add some organic and/or inorganic fire retardant, as decabromodiphynly oxide, octabromodiphenyl ether, antimonous oxide etc. can make the mixture of styrenic polymer satisfy fire-retardant requirement.But because these fire retardants self are subjected to UV-irradiation to produce decomposition easily, cause the mixture aging rapidly decay of mechanical property of material in use of flame-retardant styrene polymer compound, product surface very easily produces colour-change, directly influences outward appearance and use.On the other hand, fire retardants such as decabromodiphynly oxide are not owing to melt in the processing temperature scope of mixture, and poor with the consistency of matrix resin, the fragility of material is very big.Therefore, life-time service, light aging resisting, high tenacity, fire-retardant thermoplastic styrene base polymer the out of doors mixture of development has important practical significance.
Adopt styrene-butadiene-styrene ternary block polymer (SBS) (referring to WO92/03499), styrene butadiene copolymer (SB) and chlorinatedpolyethylene (CPE) thermoplastic elastomers such as (referring to EP0527439A1) that the toughness of flame-proof ABS mixture is improved, but the consistency of thermoplastic elastomer such as SBS or SB and ABS matrix is very poor, and toughening effect is limited; Although CPE isopolarity thermoplastic elastomer is fine with the consistency of ABS matrix, can significantly improve the toughness of flame-proof ABS mixture, CPE is fast light, poor heat stability, very easily makes the goods variable color after the interpolation and produces the gas that is corrosive.
Add the light aging resisting property that compound light, thermo-stabilizer can improve ABS resin, but for the flame-proof ABS mixture, if the fire retardant (as decabromodiphynly oxide) that uses can not light aging resisting, then add light inlet, thermo-stabilizer after, light aging resisting property is also very poor.
Purpose of the present invention is exactly the mixture that a kind of new light aging resisting, high tenacity, thermoplastic styrene base polymer fire-retardant, life-time service out of doors are provided for the shortcoming that overcomes current material.
Mixture according to the designed light aging resisting high tenacity flame retardant thermoplastic styrene base polymer of the present invention, its feature is formed (weight %): thermoplastic styrene base polymer 60～80, modified thermoplastic styrenic polymer 0～15, fire retardant 10～30, synergistic agent 2～10, photostabilizer 0.2～4, processing aid 1～5.
The preparation method of the mixture of light aging resisting high tenacity flame retardant thermoplastic styrene base polymer of the present invention is: with the thermoplastic styrene base polymer in the mixture, modified thermoplastic styrenic polymer, fire retardant and other component step by step after high-speed stirring is mixed, send in the twin screw extruder by the feeder of delicate metering, under the conveying and shearing action of screw rod, fully fusing, compound, again through head extrude, tie rod, cooling, pelletizing and packing.
Thermoplastic styrene base polymer in the mixture of light aging resisting high tenacity flame retardant thermoplastic styrene base polymer of the present invention is to contain the multipolymer of styrene monomer and/or the mixture of these multipolymers.These multipolymers comprise high-impact polystyrene (HIPS), styrene-acrylonitrile copolymer (AS), acrylonitrile-butadiene-phenylethene grafted copolymer (ABS), acrylonitrile-styrene-acrylic terpolymer (ASA), polystyrene-poly phenyl ether blend (PS/PPO) etc., preferably HIPS and ABS, these thermoplastic styrene base polymers have constituted the basis of whole material.
Modified thermoplastic styrenic polymer in the mixture of light aging resisting high tenacity flame retardant thermoplastic styrene base polymer of the present invention is the modifier of styrene-butadiene-styrene ternary block polymer (SBS) and modifier, styrene butadiene copolymer and modifier thereof and acrylonitrile-butadiene-styrene copolymer (ABS).As maleic anhydride modified styrene-butadiene-styrene ternary block polymer, acrylic acid modified styrene-butadiene-styrene ternary block polymer, the styrene-acrylonitrile copolymer of EPDM modification etc.These modified thermoplastic styrenic polymers all have good toughness, and it is good with the consistency of matrix resin, their adding has improved the deterioration of the mechanical property of the caused body material of fire retardant significantly, has guaranteed that the mixture of light aging resisting flame retardant thermoplastic styrene base polymer of the present invention has high tenacity.
Fire retardant in the mixture of light aging resisting high tenacity flame retardant thermoplastic styrene base polymer of the present invention is novel organic halogen containing flame-retardant of energy light aging resisting, mixture as two (2, the 3-dibromopropyl) ethers of tetrabromo-bisphenol, brominated Polystyrene, bromination epoxy oligomer, tetrabromo-bisphenol and/or these compounds.These fire retardants decompose under certain high temperature and produce hydrogen bromide, and the bromize hydrogen gas proportion of generation is bigger than air, will be deposited on the combustionmaterial skin, dilute or have completely cut off replenishing of fresh air, make combustionmaterial fire smothering under the anaerobic situation.Selected these fire retardants of the present invention are all more stable to UV-light, are difficult for taking place decomposition.The molecular weight of brominated Polystyrene is preferably in 1,000～40, and between 000, the molecular weight of bromination epoxy oligomer is preferably in 1,000～100, between 000, can keep consistency preferably with body material, gives full play to fire-retardant usefulness.
Synergistic agent in the mixture of light aging resisting high tenacity flame retardant thermoplastic styrene base polymer of the present invention is those more significant other mineral-type retardant synergists of fire retardation that can make fire retardant of the present invention, mixture as oxide compound, stibnate, borate, silicon fire retardant and/or these materials of antimony specifically comprises antimonous oxide, antimony peroxide, sodium antimonate, zinc borate, SFR-100 etc.
Photostabilizer in the mixture of light aging resisting high tenacity flame retardant thermoplastic styrene base polymer of the present invention is dihydroxy benaophenonel, hydroxybenzotriazole, benzoic ether, hindered amine, phosphorous acid ester, contain the mixture of thioesters, titanium dioxide and/or these compounds.Preferably adopt the complex light stabilising system, compound as UV-531/Cyasorb UV-2908 can be brought into play the light aging resisting effect of photostabilizer to greatest extent.These photostabilizers specifically comprise UV-531, Tinuvin-P, Tinuvin-326, Tinuvin-327, Tinuvin-328, Cyasorb UV-5411, Cyasorb UV-2908, Tinuvin770, Irganox1010, Irganox168, Irganox1076, R69 etc.
Processing aid in the mixture of light aging resisting high tenacity flame retardant thermoplastic styrene base polymer of the present invention comprises lubricant and coupling agent, and these processing aids can effectively improve each component dispersiveness, reduce harmful friction when processing and moulding; Lubricant comprises the mixture of some soap, fatty acid amide and/or these compounds, specifically comprise solid paraffin, whiteruss, low molecular weight polyethylene, calcium stearate, Zinic stearas, stearic amide, methylene bis stearic amide and N, N-ethylene bis stearic acid amide (EBS) etc.Coupling agent comprises titanic acid ester and aluminic acid ester cpds, as KH-550, KH-560, A-189,101 etc.
The mixture of light aging resisting high tenacity flame retardant thermoplastic styrene base polymer of the present invention also can be according to requiring, and adds various face (look) material man-hour adding, and is made into shades of colour.
The mixture preparation method of light aging resisting high tenacity flame retardant thermoplastic styrene base polymer of the present invention adopts the twin screw expressing technique, be with the thermoplastic styrene base polymer in the mixture, modified thermoplastic styrenic polymer, fire retardant and other component step by step after high-speed stirring is mixed, send in the twin screw extruder by the feeder of delicate metering, under the conveying and shearing action of screw rod, fully fusing, compound, again through head extrude, tie rod, cooling, pelletizing and packing.This method adopts the length-to-diameter ratio of twin screw extrusion equipment to be at least 32, more preferably greater than 36; And have precise dose control and a vacuum-pumping equipment.Each section extruder temperature should be controlled between 160～230 ℃, is preferably between 170～210 ℃.Screw speed is preferably between 300～500 rev/mins between 100～600 rev/mins.The mixture of light aging resisting high tenacity flame retardant thermoplastic styrene base polymer of the present invention adopts the preparation of twin screw expressing technique, have flow process simple, continuously, the advantage of high, the constant product quality of production efficiency.
The mixture of light aging resisting high tenacity flame retardant thermoplastic styrene base polymer of the present invention is compared with the mixture of traditional flame retardant thermoplastic styrene base polymer, adopt novel light aging resisting organic compound to make fire retardant, the flame retarding efficiency height, and by adding composite light stabilizer, can guarantee the light fastness stability of the mixture of flame retardant thermoplastic styrene base polymer, simultaneously, select for use the modified thermoplastic styrenic polymer to reach toughness reinforcing effect.Owing on prescription, adopted aforesaid particular design, the mixture of light aging resisting high tenacity flame retardant thermoplastic styrene base polymer of the present invention has the characteristics on the performances such as light aging resisting, high tenacity, fire-retardant and thermoplasticity, when utilizing mixture of the present invention to make household electrical appliances and electronic apparatus meter case, moulding processability and product mechanical property are good, out of doors life-time service.
Specific embodiments of the present invention is provided by embodiment.
The preparation and the physicals thereof of the mixture of light aging resisting high tenacity flame retardant thermoplastic styrene base polymer of the present invention see attached list 1 and 2.Fire retardant decabromodiphynly oxide and tetrabromo-bisphenol as the contrast experiment adopt U.S. Albemarle Corporation product, and the trade mark is respectively FR-102E and BP-2000.Flame retardant brominated epoxy oligomer adopts the MBEO of Israel Dead Sea company, and molecular weight is about 10,000.Different ABS products has different divinyl component concentrations, and the PA-757 of Taiwan Qi Mei company and PA-747 are respectively general purpose grade and the high level ABS resin of dashing.The modified thermoplastic styrenic polymer is respectively the SBS575 of Taiwan Qi Mei company, homemade maleic anhydride modified styrene-butadiene-styrene ternary block polymer (M-SBS) and homemade acrylic acid modified styrene-butadiene-styrene ternary block polymer (A-SBS).
M-SBS and A-SBS press table 1 prescription respectively and adopt the preparation of fusion-grafting method.Press table 1 prescription, with mixing in each group material adding high-speed mixer, again compound is joined in the single screw extrusion machine respectively,, make M-SBS, the A-SBS of graft modification respectively through check rod, pelletizing.The percentage of grafting of M-SBS used in the present invention and A-SBS is respectively 0.8%, 1.0%.
Table 1
Component M-SBS A-SBS
1000 parts 1000 parts of SBS575
5 parts of maleic anhydrides
5 parts in vinylformic acid
1 part 1 part of dicumyl peroxide
1,010 3 parts 3 parts
10 parts 10 parts of white mineral oils
The concrete operations step of embodiment is basic identical, and promptly the first step mixes thermoplastic styrene base polymer, modified thermoplastic styrenic polymer, fire retardant and other component step by step through high-speed stirring; Second step was that said mixture is sent in the forcing machine through the feeder of delicate metering, under the conveying and shearing action of screw rod, fully fusing, compound, again through head extrude, tie rod, cooling, pelletizing, pack at last.
The length-to-diameter ratio that is applied to the twin screw extruder among the preparation method of the present invention is 36, and each section extruder temperature is controlled between 170～210 ℃, and screw speed is 300～500 rev/mins.
The compound of each embodiment preparation is injection molded into the standard batten of test usefulness by standard size; Physical property among each embodiment is respectively by China's national standard and U.S. UL standard testing, and is as shown in the table: quantitative measurement method hot strength GB1040 elongation at break GB1040Izod notched Izod impact strength GB1843 heat distortion temperature GB1634 bending modulus GB9341 flammability UL94 xenon lamp artificial accelerated aging performance (100hour) GB9344Izod notched Izod impact strength GB1843 value of chromatism DE GB250
Subordinate list 1 component 1234 5PA-757 100 74.4 67.4 69.4 71FR-102E 17BP-2000 12MBEO 12 22 22 antimony oxides 666 6Cyasorb UV-531 0.3 0.3 0.3Cyasorb UV-2908 0.3 0.3 0.3 titanium dioxide 111 processing aid EBS 0.5 0.5 0.5 0.5 zinc stearates 0.3 0.3 0.3 0.3KH-560 0.5 0.5 0.5 0.5 physical property hot strengths 51.3 44.8 42.6 43.5 43.8 elongation at breaks 13 10 9 11 11Izod notched Izod impact strength 14.8 4.3 8.1 5.6 5.5 heat distortion temperatures 95 85 86 88 88 bending moduluses 2,340 2,050 2,120 2,150 2170 flammability HB V-0 V-0 V-0 V-0 xenon lamp artificial accelerated aging performance (100hour) Izod notched Izod impact strength 12.6 2.3 6.5 5.2 4.7
DE 3.6 32.5 9.4 2.2 3.8
Subordinate list 2
Component 123 4PA-747 69.4 67.4 65.4 65.4M-SBS 2 4A-SBS 4MBEO 22 22 22 22 antimony oxides 666 6Cyasorb UV-531 0.3 0.3 0.3 0.3Cyasord UV-2908 0.3 0.3 0.3 0.3 titanium dioxide 1111 processing aid EBS 0.5 0.5 0.5 0.5 zinc stearates 0.3 0.3 0.3 0.3KH-560 0.5 0.5 0.5 0.5 physical property hot strengths 40.3 39.6 37.5 38.2 elongation at breaks 13 14 17 15Izod notched Izod impact strength 9.6 12.4 15.6 13.8 heat distortion temperatures 86 85 84 85 bending moduluses 1,980 1,960 1,950 1960 flammability V-0 V-0 V-0 V-0 xenon lamp artificial accelerated aging performance (100hour) Izod notched Izod impact strength 8.6 11.5 14.1 12.3
DE 2.2 2.2 2.3 2.2
Claims (6)
1. the mixture of a light aging resisting high tenacity flame retardant thermoplastic styrene base polymer, consisting of of this mixture: thermoplastic styrene base polymer 60～80 weight %, modified thermoplastic styrenic polymer 2～15 weight %, fire retardant 10～30 weight %, synergistic agent 2～10 weight %, photostabilizer 0.2～4 weight %, processing aid 1～5 weight %; Wherein said thermoplastic styrene base polymer is high-impact polystyrene or acrylonitrile-butadiene-styrene copolymer; The modifier that described modified thermoplastic styrenic polymer is the styrene-butadiene-styrene ternary block polymer, the modifier of styrene butadiene copolymer or the modifier of acrylonitrile-butadiene-styrene copolymer; Described fire retardant is the mixture of two (2, the 3-dibromopropyl) ethers of tetrabromo-bisphenol, brominated Polystyrene, bromination epoxy oligomer, tetrabromo-bisphenol and/or these compounds; Described synergistic agent is the mixture of oxide compound, stibnate, borate, silicon fire retardant and/or these materials of antimony.
2. the mixture of light aging resisting high tenacity flame retardant thermoplastic styrene base polymer according to claim 1, wherein said photostabilizer be dihydroxy benaophenonel, hydroxybenzotriazole, benzoic ether, hindered amine, phosphorous acid ester, contain the mixture of thioesters, titanium dioxide and/or these compounds.
3. the method for preparing the mixture of the described light aging resisting high tenacity of claim 1 flame retardant thermoplastic styrene base polymer, this method comprises the thermoplastic styrene base polymer in the mixture, modified thermoplastic styrenic polymer, fire retardant and other component step by step after high-speed stirring is mixed, send in the twin screw extruder by feeder, under the conveying and shearing action of screw rod, fully fusing, compound, again through head extrude, tie rod, cooling, pelletizing and packing.
4. method according to claim 3 is characterized in that the length-to-diameter ratio of described twin screw extrusion equipment is at least 32.
5, method according to claim 4, the length-to-diameter ratio that it is characterized in that described twin screw extrusion equipment is greater than 36.
6. method according to claim 5 is characterized in that described twin screw extrusion equipment has temperature control and vacuum-pumping equipment.
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| CN 00124684 CN1112404C (en) | 2000-09-28 | 2000-09-28 | Anti-photoageing, flame-retarding, high-toughness and thermoplastic composition of styrene polymers |
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| CN 00124684 CN1112404C (en) | 2000-09-28 | 2000-09-28 | Anti-photoageing, flame-retarding, high-toughness and thermoplastic composition of styrene polymers |
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| CN1298898A CN1298898A (en) | 2001-06-13 |
| CN1112404C true CN1112404C (en) | 2003-06-25 |
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| IL162449A (en) * | 2004-06-10 | 2010-05-17 | Bromine Compounds Ltd | Fire retardant formulations and styrene polymer compositions containing them |
| CN100372886C (en) * | 2006-11-24 | 2008-03-05 | 北京理工大学 | Flame-proof polystyrene composition and its preparation method |
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