CN103709431A - Polystyrene with high flame retardant property and preparation method thereof - Google Patents
Polystyrene with high flame retardant property and preparation method thereof Download PDFInfo
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- CN103709431A CN103709431A CN201310695725.2A CN201310695725A CN103709431A CN 103709431 A CN103709431 A CN 103709431A CN 201310695725 A CN201310695725 A CN 201310695725A CN 103709431 A CN103709431 A CN 103709431A
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- polystyrene
- flame retardant
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- high flame
- flame resistance
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 78
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 71
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 70
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 20
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical class OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 claims description 20
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 18
- 239000004411 aluminium Substances 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000011324 bead Substances 0.000 claims description 17
- 239000001506 calcium phosphate Substances 0.000 claims description 17
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 17
- 235000011010 calcium phosphates Nutrition 0.000 claims description 17
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- GFMYEVPBEJFZHH-UHFFFAOYSA-N CP(O)(O)O Chemical group CP(O)(O)O GFMYEVPBEJFZHH-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 230000009466 transformation Effects 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 239000006260 foam Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- -1 aminomethyl phenyl Chemical group 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 150000004702 methyl esters Chemical class 0.000 claims description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 5
- 238000005502 peroxidation Methods 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000012874 anionic emulsifier Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 239000012875 nonionic emulsifier Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005187 foaming Methods 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000004088 foaming agent Substances 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- XXVACRIMKRHRHA-UHFFFAOYSA-N oxido(phenoxy)phosphanium Chemical class O=[PH2]Oc1ccccc1 XXVACRIMKRHRHA-UHFFFAOYSA-N 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 7
- 229920006248 expandable polystyrene Polymers 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 1
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method for polystyrene with high flame retardant property and a prepared polystyrene material. Hypophosphite and phenyl phosphinates which serve as halogen-free environment-friendly solid flame retardants and a halogen-free liquid flame retardant are adopted to prepare a composite flame retardant which works on the polystyrene material. The preparation method for the polystyrene material comprises the steps of feeding a dispersing agent, an emulsifier, an initiator and styrene into a high-pressure polymerization kettle to generate reaction, and adding the composite flame retardant after a certain conversion rate is achieved; adding a foaming agent after particles are hardened; closing the reaction kettle, heating the reaction kettle, preserving the temperature, and washing and drying to obtain material ball particles; foaming the material ball particles, curing foamed balls under room temperature, and putting the foamed balls into a mold to obtain the polystyrene material with high flame retardant property. According to the preparation method and the polystyrene material, the halogen-free environment-friendly solid flame retardants and the halogen-free liquid flame retardant are mixed; the solid phase flame retardants are uniformly dispersed in the liquid phase flame retardant to achieve a synergistic flame retardant effect; the flame retardant performance of the polystyrene material is realized, and various excellent properties of the polystyrene are kept.
Description
Technical field
The present invention relates to a kind of polystyrene material and preparation method thereof, particularly relate to a kind of high flame resistance polystyrene and preparation method thereof, comprise high flame resistance polystyrene foamed (EPS) material and high flame resistance extruded polystyrene (XPS) material.
Background technology
Polystyrene (PS) is thermoplastic resin, because of its cheap and easy machine-shaping, is therefore able to widespread use.At present widespread use be Expandable Polystyrene (EPS) material (EPS) and extruded polystyrene material (XPS).Especially EPS material, due to its good use properties, the production moulding processing unit of cheap cost, simple possible and can be made into the different products that require, thereby obtain swift and violent development.At present, China has become the maximum EPS producing country in the whole world, and its production and consumption total amount all ranks first in the world.Due to the superior heat preservation and insulation of polystyrene material, be widely used in external-wall heat-insulation material, and its annual requirement still increasing progressively fast, market potential is very huge.
But regrettably, this polystyrene material is with C, H element is main polymer materials, in addition it is again a kind of rigid foam of unicellular structure, the state that presents thin-walled porous after foaming, thereby become one of material that in all polymer materialss, limiting oxygen index(LOI) is minimum, very easily burning, not only can light at a lower temperature, once and catch fire and can acutely burn, flame spreads at a high speed and diffuses to whole surface, make the melting of base material high shrinkage, do not become charcoal, produce a large amount of black smog simultaneously, toxic gas and with the molten drop of naked light, cause development of combustion more serious.
Because polystyrene material has the feature of special molecular chain structure, degraded and combustioncharacteristics and foamy structure, the polystyrene foamed material that its flame-retardant modified quite difficulty, especially preparation are had to excellent flame retardancy energy and mechanical property still belongs to global problem.
At present, few for research and the coverage of the polystyrene material of high flame resistance, the fire retardant relating to has halogen system, phosphorus system, nitrogen-phosphorus is compound and inorganic combustion inhibitor etc.
Chinese patent (CN11796114A) discloses and has used fire retardant and the caking agent that the particle diameter of 10-60wt% is 1-50 μ m, expandable polystyrene bead and one step foaming bubble grain are carried out to surface-coated, improved insulativity and the flame retardant resistance of expanded polystyrene foam, fire retardant used is one or more of metal or nonmetal oxide, metal or nonmetal oxyhydroxide, silicate, borate and carbonate.The fire retardant that this method is used and polystyrene bubble grain consistency are poor, and the mechanical property of the polystyrene material of gained is difficult to reach service requirements.
U.S. Albemarle Corporation (CN101087819A) and Oohara (USPatent 6569912) all disclose and have used bromide fire retardant or nitrogenous phosphorus flame retardant and HBCD compound flame retardant, all make polystyrene material obtain the flame retardant properties of higher level.But along with the enhancing of environmental consciousness and awareness of safety, halogen is that a series of safety issues and the environmental problem that flame-retardant system brings will cause more concern day by day.
Find the trend that novel, efficient fire retardant is the flame-retardant modified development of polystyrene material.
Summary of the invention
The object of the invention is the deficiency existing for prior art, the high flame resistance polystyrene material that a kind of preparation method of high flame resistance polystyrene is provided and makes, this material not only flame retardant properties is good, and mechanical property is also all good.
For realizing the object of the invention and solving its technical problem, by the following technical solutions:
A preparation method for high flame resistance polystyrene, is characterized in that, described method comprises the following steps:
A) deionized water is added in high pressure polymerisation reactor, drop into dispersion agent, emulsifying agent and initiator and stir, drop into vinylbenzene, be warming up to 85-90 ℃ and keep the constant lower reaction of still temperature;
B) when reaction reaches after certain transformation efficiency, add fire retardant; Described fire retardant is the compound flame retardant that hypophosphite, phenyl phosphinic acid salt, dimethyl methyl phosphonate and annular phosphonate form;
C) after particle hardening, add appropriate active calcium phosphate, add whipping agent simultaneously;
D) closed reactor, is warming up to 105-125 ℃ and insulation, cooling discharge; Washing, dry, obtains material bead;
E) resulting materials bead is foamed in foam maker; By the at room temperature slaking of the alveolar sphere of pre-frothing, enter mould and obtain described high flame resistance polystyrene.
The fire retardant that the present invention adopts is the compound flame retardant of halogen-free environment-friendly type solid flame retardant hypophosphite, phenyl phosphinic acid salt and Halogen liquid flame retardant.The preferred hypo-aluminum orthophosphate of described hypophosphite, the preferred phenyl phosphinic acid aluminium of phenyl phosphinic acid salt, aminomethyl phenyl hypo-aluminum orthophosphate, diethyl phospho acid aluminium, hydroxymethyl phenyl phospho acid aluminium, annular phosphonate is as methyl-phosphorous acid two (2-methyl-5-ethyl-2-oxo-1,3,2-dioxa phospha cyclohexyl-5-methylene radical) ester, methyl-phosphorous acid (2-methyl-5-ethyl-2-oxo-1,3,2-dioxa phosphorus heterocycle cyclohexyl-5-methylene radical) methyl ester etc.
Described compound flame retardant, the compound flame retardant of recommendation hypo-aluminum orthophosphate of the present invention, phenyl phosphinic acid aluminium, dimethyl methyl phosphonate (DMMP) and annular phosphonate, mass ratio is respectively 1～2:1～1.5:1～2:1～1.5.
The consumption of described compound flame retardant, counts 1.0-15wt% based on polystyrene material.
The dispersion agent of abovementioned steps in a) can be active calcium phosphate, Natvosol, gelatin etc.Recommendation active calcium phosphate of the present invention.The usage quantity of dispersion agent is the 1.0-2.0% of polystyrene material quality.
The emulsifying agent of abovementioned steps in a) can be nonionic emulsifier (as Emcol PO-50, Aldo 28, Tegin etc.) and anionic emulsifier (as alkylsulfonate, alkyl-sulphate etc.).Recommendation Sodium dodecylbenzene sulfonate of the present invention.The usage quantity of emulsifying agent is the 0.5-2% of polystyrene material quality.
The initiator of abovementioned steps in a) can be peroxidation two alkane, peroxyester, peroxidation two acyls.Recommendation dibenzoyl peroxide of the present invention or peroxidized t-butyl perbenzoate.The usage quantity of initiator is the 0.5-2% of polystyrene material quality.
Abovementioned steps c) whipping agent in can be pneumatogen (as pentane, Freon11, Freon114 etc.) or chemical foaming agent (calcium carbonate etc.).Recommendation pentane of the present invention.The usage quantity of whipping agent is 5% of polystyrene material quality.
In described method, in step b), the present invention recommends when transformation efficiency >=85%, then adds described fire retardant.
In described method, after in step d), the present invention recommends closed reactor, holding temperature is at 115 ℃.
In described method, the alveolar sphere that in step e), the present invention recommends pre-frothing is slaking 24h at normal temperatures.
The invention still further relates to high flame resistance polystyrene material prepared by described method.
The polystyrene material that prior art prepares is because flame retardant properties is poor, so be limited by very large in actual applications.The fire retardant that the present invention adopts is environmentally friendly fire retardant, is the compound flame retardant of halogen-free environment-friendly type solid flame retardant hypophosphite, phenyl phosphinic acid salt and Halogen liquid flame retardant, and by dispersion agent, solid phase fire retardant is dispersed in liquid phase fire retardant.The compound flame retardant that the present invention recommends is specially: hypo-aluminum orthophosphate, phenyl phosphinic acid aluminium, DMMP and annular phosphonate compound flame retardant.Wherein hypo-aluminum orthophosphate is inorganic phosphorus flame retardant, its phosphorus content high (41.89%), and aluminium element has certain cigarette effect that presses down, and can obviously reduce smoke density; Phenyl phosphinic acid aluminium is organic secondary phosphine acid salt fire retardant, and the dispersiveness in organic phase is splendid; DMMP and annular phosphonate are organic phosphorus flame retardant, by with hypo-aluminum orthophosphate, the composite rear synergistic of phenyl phosphinic acid aluminium, can make polystyrene material reach A level flame retardant properties.
The present invention adopts halogen-free environment-friendly type solid flame retardant hypophosphite, phenyl phosphinic acid salt and Halogen liquid flame retardant complex role in polystyrene material, solid phase fire retardant is dispersed in liquid phase fire retardant and reaches the fire-retardant effect of efficient synergistic, has solved poor this problem of polystyrene material flame retardant properties.The prepared high flame resistance polystyrene material of the inventive method, keeping under the prerequisite of the original various premium propertiess of polystyrene (as: physical and mechanical properties, acid-fast alkali-proof performance etc.), greatly improved its flame retardant resistance, met the fire-resistant requirement of polystyrene material, and preparation process is simple, processing condition are easy to control, environmentally friendly, raw materials cost is cheap, is more suitable for suitability for industrialized production.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to be more well understood to technique means of the present invention, and can be implemented according to specification sheets, and be below preferred embodiment of the present invention.Protection scope of the present invention is not limited to described specific examples, but be limited by claim.All object of the present invention and main ideas of not departing from, any combination and change formed similar other embodiment and all belong to scope involved in the present invention within the scope of claims.
Embodiment
Embodiment 1
By formula, take 100g deionized water in polymermaking autoclave, drop into active calcium phosphate 2g, Sodium dodecylbenzene sulfonate 2g, dibenzoyl peroxide 2g stirring, drop into 200g vinylbenzene, heat up and make the constant reaction at 85 ℃ of still temperature; After reach >=85% transformation efficiency, add 7.5g hypo-aluminum orthophosphate, 7.5g phenyl phosphinic acid aluminium, 7.5g dimethyl methyl phosphonate and 7.5g methyl-phosphorous acid two (2-methyl-5-ethyl-2-oxo-1,3,2-dioxa phospha cyclohexyl-5-methylene radical) ester compound flame retardant; After particle hardening, add appropriate active calcium phosphate, add 10g pentane simultaneously; Closed reactor, be warming up to 115 ℃ and be incubated for some time after be cooled to 38 ℃ of dischargings; Washing, dry, obtains material bead; Resulting materials bead is foamed in foam maker; By the alveolar sphere of pre-frothing slaking 24h at room temperature, enter mould and obtain high flame resistance polystyrene material.
Flame retardant properties, the mechanical experimental results of this polystyrene material show: oxygen index 32, vertical combustion grade UL-94 V-0 level, water-intake rate 1.6%, flexural strength 0.3Mpa, compressive strength 0.15Mpa, thermal conductivity 0.035w/m
.k.
Embodiment 2
By formula, take 100g deionized water in polymermaking autoclave, drop into active calcium phosphate 2.5g, Sodium dodecylbenzene sulfonate 2.5g, dibenzoyl peroxide 2.5g stirring, drop into 200g vinylbenzene, heat up and make the constant reaction at 85 ℃ of still temperature; After reach >=85% transformation efficiency, hypo-aluminum orthophosphate, 7.5g phenyl phosphinic acid aluminium, the dimethyl methyl phosphonate of 7.5g and the methyl-phosphorous acid of 7.5g two (2-methyl-5-ethyl-2-oxo-1 that adds 7.5g, 3,2-dioxa phospha cyclohexyl-5-methylene radical) ester compound flame retardant; After particle hardening, add appropriate active calcium phosphate, add 10g pentane simultaneously; Closed reactor, be warming up to 115 ℃ and be incubated for some time after be cooled to 38 ℃ of dischargings; Washing, dry, obtains material bead; Resulting materials bead is foamed in foam maker; By the alveolar sphere of pre-frothing slaking 24h at room temperature, enter mould and obtain high flame resistance polystyrene material.
Flame retardant properties, the mechanical experimental results of this polystyrene material show: oxygen index 33, vertical combustion grade UL-94 V-0 level, water-intake rate 1.5%, flexural strength 0.3Mpa, compressive strength 0.17Mpa, thermal conductivity 0.037w/m
.k.
Embodiment 3
By formula, take 100g deionized water in polymermaking autoclave, drop into active calcium phosphate 4g, Sodium dodecylbenzene sulfonate 4g, peroxidized t-butyl perbenzoate 2.5g stirring, drop into 200g vinylbenzene, heat up and make the constant reaction at 90 ℃ of still temperature; After reach >=85% transformation efficiency, add hypo-aluminum orthophosphate, 5g phenyl phosphinic acid aluminium, the dimethyl methyl phosphonate of 5g and the methyl-phosphorous acid of 5g two (2-methyl-5-ethyl-2-oxo-1,3,2-dioxa phospha cyclohexyl-5-methylene radical) the ester compound flame retardant of 5g; After particle hardening, add appropriate active calcium phosphate, add 10g pentane simultaneously; Closed reactor, be warming up to 115 ℃ and be incubated for some time after be cooled to 38 ℃ of dischargings; Washing, dry, obtains material bead; Resulting materials bead is foamed in foam maker; By the alveolar sphere of pre-frothing slaking 24h at room temperature, enter mould and obtain high flame resistance polystyrene material.
Flame retardant properties, the mechanical experimental results of this polystyrene material show: oxygen index 33, vertical combustion grade UL-94 V-0 level, water-intake rate 1.5%, flexural strength 0.3Mpa, compressive strength 0.17Mpa, thermal conductivity 0.037w/m
.k.
Embodiment 4
By formula, take 100g deionized water in polymermaking autoclave, drop into active calcium phosphate 4g, Sodium dodecylbenzene sulfonate 4g, peroxidized t-butyl perbenzoate 2.5g stirring, drop into 200g vinylbenzene, heat up and make the constant reaction at 85 ℃ of still temperature; After reach >=85% transformation efficiency, hypo-aluminum orthophosphate, 7.5g phenyl phosphinic acid aluminium, the dimethyl methyl phosphonate of 7.5g and the methyl-phosphorous acid of 5g (2-methyl-5-ethyl-2-oxo-1 that adds 10g, 3,2-dioxa phosphorus heterocycle cyclohexyl-5-methylene radical) methyl ester) compound flame retardant; After particle hardening, add appropriate active calcium phosphate, add 10g pentane simultaneously; Closed reactor, be warming up to 115 ℃ and be incubated for some time after be cooled to 38 ℃ of dischargings; Washing, dry, obtains material bead; Resulting materials bead is foamed in foam maker; By the alveolar sphere of pre-frothing slaking 24h at room temperature, enter mould and obtain high flame resistance polystyrene material.
Flame retardant properties, the mechanical experimental results of this polystyrene material show: oxygen index 32, vertical combustion grade UL-94 V-0 level, water-intake rate 1.5%, flexural strength 0.3Mpa, compressive strength 0.15Mpa, thermal conductivity 0.040w/m
.k.
Embodiment 5
By formula, take 100g deionized water in polymermaking autoclave, drop into active calcium phosphate 3g, Sodium dodecylbenzene sulfonate 2.5g, peroxidized t-butyl perbenzoate 3g stirring, drop into 200g vinylbenzene, heat up and make the constant reaction at 87 ℃ of still temperature; After reach >=85% transformation efficiency, hypo-aluminum orthophosphate, 7.5g phenyl phosphinic acid aluminium, the dimethyl methyl phosphonate of 7.5g and the methyl-phosphorous acid of 5g (2-methyl-5-ethyl-2-oxo-1 that adds 10g, 3,2-dioxa phosphorus heterocycle cyclohexyl-5-methylene radical) methyl ester) compound flame retardant; After particle hardening, add appropriate active calcium phosphate, add 10g pentane simultaneously; Closed reactor, be warming up to 110 ℃ and be incubated for some time after be cooled to 38 ℃ of dischargings; Washing, dry, obtains material bead; Resulting materials bead is foamed in foam maker; By the alveolar sphere of pre-frothing slaking 24h at room temperature, enter mould and obtain high flame resistance polystyrene material.
Flame retardant properties, the mechanical experimental results of this polystyrene material show: oxygen index 32, vertical combustion grade UL-94 V-0 level, water-intake rate 1.3%, flexural strength 0.3Mpa, compressive strength 0.17Mpa, thermal conductivity 0.040w/m
.k.
Embodiment 6
By formula, take 100g deionized water in polymermaking autoclave, drop into active calcium phosphate 3.5g, Sodium dodecylbenzene sulfonate 3.5g, peroxidized t-butyl perbenzoate 2.5g stirring, drop into 200g vinylbenzene, heat up and make the constant reaction at 85 ℃ of still temperature; After reach >=85% transformation efficiency, add hypo-aluminum orthophosphate, the 10g phenyl phosphinic acid aluminium of 7.5g, dimethyl methyl phosphonate and 5g methyl-phosphorous acid (2-methyl-5-ethyl-2-oxo-1 of 7.55g, 3,2-dioxa phosphorus heterocycle cyclohexyl-5-methylene radical) methyl ester) compound flame retardant; After particle hardening, add appropriate active calcium phosphate, add 10g pentane simultaneously; Closed reactor, be warming up to 110 ℃ and be incubated for some time after be cooled to 38 ℃ of dischargings; Washing, dry, obtains material bead; Resulting materials bead is foamed in foam maker; By the alveolar sphere of pre-frothing slaking 24h at room temperature, enter mould and obtain high flame resistance polystyrene material.
Flame retardant properties, the mechanical experimental results of this polystyrene material show: oxygen index 33, vertical combustion grade UL-94 V-0 level, water-intake rate 1.3%, flexural strength 0.3Mpa, compressive strength 0.16Mpa, thermal conductivity 0.039w/m
.k.
Claims (10)
1. a preparation method for high flame resistance polystyrene, is characterized in that, described method comprises the following steps:
A) deionized water is added in high pressure polymerisation reactor, drop into dispersion agent, emulsifying agent and initiator and stir, drop into vinylbenzene, be warming up to 85-90 ℃ and keep the constant lower reaction of still temperature;
B) when reaction reaches after certain transformation efficiency, add fire retardant; Described fire retardant is the compound flame retardant that hypophosphite, phenyl phosphinic acid salt, dimethyl methyl phosphonate and annular phosphonate form;
C) after particle hardening, add appropriate active calcium phosphate, add whipping agent simultaneously;
D) closed reactor, is warming up to 105-125 ℃ and insulation, cooling discharge; Washing, dry, obtains material bead;
E) resulting materials bead is foamed in foam maker; By the at room temperature slaking of the alveolar sphere of pre-frothing, enter mould and obtain described high flame resistance polystyrene.
2. the preparation method of high flame resistance polystyrene according to claim 1, it is characterized in that, described hypophosphite is selected from hypo-aluminum orthophosphate, phenyl phosphinic acid salt is selected from phenyl phosphinic acid aluminium, aminomethyl phenyl hypo-aluminum orthophosphate, diethyl phospho acid aluminium, hydroxymethyl phenyl phospho acid aluminium, annular phosphonate is selected from methyl-phosphorous acid two (2-methyl-5-ethyl-2-oxo-1,3,2-dioxa phospha cyclohexyl-5-methylene radical) ester, methyl-phosphorous acid (2-methyl-5-ethyl-2-oxo-1,3,2-dioxa phosphorus heterocycle cyclohexyl-5-methylene radical) methyl ester.
3. the preparation method of high flame resistance polystyrene according to claim 2, it is characterized in that, described compound flame retardant is the compound flame retardant that hypo-aluminum orthophosphate, phenyl phosphinic acid aluminium, dimethyl methyl phosphonate and annular phosphonate form, and mass ratio is respectively 1～2:1～1.5:1～2:1～1.5.
4. according to the preparation method of the arbitrary described high flame resistance polystyrene of claim 1-3, it is characterized in that the 1.0-15wt% that the consumption of described compound flame retardant is polystyrene material.
5. the preparation method of high flame resistance polystyrene according to claim 1, is characterized in that, the dispersion agent described in step a) is active calcium phosphate, Natvosol or gelatin, and usage quantity is the 1.0-2.0% of polystyrene material quality.
6. the preparation method of high flame resistance polystyrene according to claim 1, is characterized in that, the emulsifying agent described in step a) is nonionic emulsifier or anionic emulsifier, and usage quantity is the 0.5-2% of polystyrene material quality.
7. the preparation method of high flame resistance polystyrene according to claim 1, is characterized in that, the initiator described in step a) is peroxidation two alkane, peroxyester or peroxidation two acyls, the 0.5-2% of usage quantity polystyrene material quality.
8. the preparation method of high flame resistance polystyrene according to claim 1, is characterized in that, the whipping agent described in step c) is used pentane, and usage quantity is 5% of polystyrene material quality.
9. the preparation method of high flame resistance polystyrene according to claim 1, is characterized in that, in described method, adds described fire retardant in step b) when transformation efficiency >=85%.
10. the polystyrene material making according to the preparation method of the arbitrary high flame resistance polystyrene described in claim 1 to 9.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN104558316A (en) * | 2014-12-23 | 2015-04-29 | 安徽助成信息科技有限公司 | Method for synthesizing polystyrene microspheres based on emulsion method |
| CN104917115A (en) * | 2015-06-23 | 2015-09-16 | 国网山东省电力公司济南供电公司 | Fire protection method for cable intermediate connector on cable bridge |
| CN105906965A (en) * | 2016-06-01 | 2016-08-31 | 望江县精美欣钢构有限公司 | Flame retardant thermal insulation polystyrene material and preparation method thereof |
| CN105968352A (en) * | 2016-06-29 | 2016-09-28 | 广州大学 | Preparation methods of amino triazine derivative macromolecular char forming agent and polypropylene flame retardant |
| CN114940719A (en) * | 2022-05-12 | 2022-08-26 | 洪湖市一泰科技有限公司 | Flame-retardant polystyrene and preparation method thereof |
| CN115433385A (en) * | 2022-09-19 | 2022-12-06 | 安徽裕河新材料有限公司 | Preparation method of expanded polystyrene |
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| CN101230274A (en) * | 2007-12-27 | 2008-07-30 | 南京师范大学 | Method for preparing annular phosphonate or annular phosphate flame retardant |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN104558316A (en) * | 2014-12-23 | 2015-04-29 | 安徽助成信息科技有限公司 | Method for synthesizing polystyrene microspheres based on emulsion method |
| CN104917115A (en) * | 2015-06-23 | 2015-09-16 | 国网山东省电力公司济南供电公司 | Fire protection method for cable intermediate connector on cable bridge |
| CN105906965A (en) * | 2016-06-01 | 2016-08-31 | 望江县精美欣钢构有限公司 | Flame retardant thermal insulation polystyrene material and preparation method thereof |
| CN105968352A (en) * | 2016-06-29 | 2016-09-28 | 广州大学 | Preparation methods of amino triazine derivative macromolecular char forming agent and polypropylene flame retardant |
| CN114940719A (en) * | 2022-05-12 | 2022-08-26 | 洪湖市一泰科技有限公司 | Flame-retardant polystyrene and preparation method thereof |
| CN114940719B (en) * | 2022-05-12 | 2023-11-24 | 洪湖市一泰科技有限公司 | Flame-retardant polystyrene and preparation method thereof |
| CN115433385A (en) * | 2022-09-19 | 2022-12-06 | 安徽裕河新材料有限公司 | Preparation method of expanded polystyrene |
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