CN102206385B - Fire resistant expansible polystyrene resin particle - Google Patents
Fire resistant expansible polystyrene resin particle Download PDFInfo
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- CN102206385B CN102206385B CN201010145868.2A CN201010145868A CN102206385B CN 102206385 B CN102206385 B CN 102206385B CN 201010145868 A CN201010145868 A CN 201010145868A CN 102206385 B CN102206385 B CN 102206385B
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Abstract
The invention provides a fire resistant expansible polystyrene resin particle. Even using powdered TBCO (tetrabromocyclooctane) as a fire retardant, nonuniform absorption of TBCO by resin particles and deformation of TBCO into a ball shape can be prevented, so as to realize good operability in manufacturing process. Before or during impregnation of a foaming agent by the polystyrene resin particles dispersing in an aqueous suspension, a powdered fire retardant TBCO dispersed by a silica micro powder is impregnated, and the fire resistant expansible polystyrene resin particle is obtained in the aqueous suspension, wherein, by weight, 0.45-2.0 parts of the TBCO is added into 100 parts of the polystyrene resin, and 0.3-1.5 parts of the silica powder is contained in 98.5-99.7 parts of the powdered fire retardant TBCO.
Description
Technical field
The present invention relates to fire resistant expansible polystyrene resin particle.More particularly, the present invention relates to use tetrabromo cyclooctane as the fire resistant expansible polystyrene resin particle of fire retardant.
Background technology
Expandable polystyrene resin particle is used in the purposes of broad range, is used in agriculture fishery products field, field of household appliances, building materials building field etc.Particularly, at building materials field, be used in the polystyrene type expanded moldings of the thermal insulation material on wall or floor, from saving the viewpoint of the energy, earnestly wish the expanded moldings of heat-insulating property excellence, also require it to there is flame retardant properties.
In the manufacture method of above-mentioned expandable polystyrene resin particle, adopt when polymerization the method that fire retardant and styrene monomer are added simultaneously, the method for adding fire retardant when making polystyrene resins particle impregnation whipping agent etc.As the former method, there is the method for recording in 2003-335891 communique (patent documentation 1) and JP 2002-194130 communique (patent documentation 2), as the latter's method, the method that has JP 2007-246606 communique (patent documentation 3) to record.
Patent documentation 1: TOHKEMY 2003-335891 communique
Patent documentation 2: TOHKEMY 2002-194130 communique
Patent documentation 3: TOHKEMY 2007-246606 communique
Summary of the invention
In the former method, mainly use hexabromocyclododecane (HBCD) as fire retardant.HBCD is the material of worrying to have in vivo accumulation property, wishes not use.In the latter's method, mainly use tetrabromo cyclooctane (TBCO), but there is TBCO monomer, be Powdered, due to preservation state, become TBCO and stick to each other and form the problem of ball shape.Because TBCO forms ball shape, the dispersion of fire retardant becomes inhomogeneous, and consequently resin particle becomes inhomogeneous to the absorption of powdery flame retardent, exists a part of resin particle to absorb in a large number the problem of fire retardant.In addition, because fire retardant forms ball shape, there is the poor problem of operability in manufacturing process.
The object of the invention is to, a kind of fire resistant expansible polystyrene resin particle is provided, even if this polystyrene resins particle is used pulverous tetrabromo cyclooctane (TBCO) as fire retardant, also can prevent from making resin particle become inhomogeneous to the absorption of TBCO, and can prevent from forming ball shape, thereby make the operability in manufacturing process become good.
The present inventor find by use specified quantitative in vivo not accumulation property, the good fire retardant of operability in Qie manufacturing process, can provide when making its foaming, particle thermal welding is each other excellent, and can access the foamable polystyrene resin particle of the foam molded product with excellent flame retardancy, thereby complete invention.
Flame-retardant intumescent styrene resin particle of the present invention is characterised in that: before the polystyrene resins particle impregnation whipping agent that makes to be scattered in waterborne suspension or in impregnation, the tetrabromo cyclooctane as powdery flame retardent that impregnation is disperseed by fine silica powder end, from above-mentioned waterborne suspension, take out and obtain above-mentioned fire resistant expansible polystyrene resin particle, wherein, above-mentioned polystyrene resins with respect to 100 weight parts, add the above-mentioned tetrabromo cyclooctane of 0.45～2.0 weight part, above-mentioned fire retardant is with respect to the tetrabromo cyclooctane of 98.5～99.7 weight parts, the fine silica powder end of containing 0.3～1.5 weight part.
In addition, the manufacture method of fire resistant expansible polystyrene resin particle of the present invention is characterised in that: before the polystyrene resins particle impregnation whipping agent that makes to be scattered in waterborne suspension or in impregnation, tetrabromo cyclooctane 0.45～2.0 weight part as powdery flame retardent that the impregnation of above-mentioned polystyrene resins particle is disperseed by fine silica powder end, from above-mentioned waterborne suspension, take out and obtain above-mentioned fire resistant expansible polystyrene resin particle, wherein, tetrabromo cyclooctane with respect to 98.5～99.7 weight parts, the above-mentioned fine silica powder end that above-mentioned powdery flame retardent contains 0.3～1.5 weight part.
Invention effect
Thus, flame-retardant intumescent polystyrene type particle of the present invention is characterised in that: in foamable polystyrene class particle, evenly absorb fire retardant.The fire retardant adding adds fine silica powder end in tetrabromo cyclooctane, by adding fine silica powder end, the dispersiveness of tetrabromo cyclooctane is significantly improved.Therefore, can provide the operability in manufacture very good, in expandable polystyrene resin particle, can evenly absorb fire retardant, the good fire resistant expansible polystyrene resin particle of thermal welding during moulding.
In addition, tetrabromo cyclooctane evenly and is stably disperseed by fine silica powder end, so tetrabromo cyclooctane can not produce Second Aggregation and sedimentation, the problem of pipe arrangement pipeline etc. can not occur to stop up because of tetrabromo cyclooctane.
In addition, add in the fine silica powder Mo manufacturing process in fire retardant and all in draining, flow out, in the expandable polystyrene resin particle therefore obtaining, be only absorbed with fire retardant.And, because fine silica powder end is not absorbed, so can not make the flame retardant resistance of the foam that obtained by above-mentioned flame-retardant intumescent polystyrene type particle decline.
In addition, because be the foam being obtained by the flame-retardant intumescent polystyrene resins that does not contain fire retardant HBCD, so can access in vivo not accumulation property, and can become the expandable polystyrene resin particle of the formed body of heat insulating ability and excellent in flame retardance.
Embodiment
The manufacture method of fire resistant expansible polystyrene resin particle of the present invention is characterised in that, before the polystyrene resins particle impregnation whipping agent that makes to be scattered in waterborne suspension or in impregnation, make impregnation 0.45～2.0 weight part powder flame-proof agent tetrabromo cyclooctane in above-mentioned polystyrene resins particle, thereby obtain fire resistant expansible polystyrene resin particle, the tetrabromo cyclooctane that above-mentioned fire retardant contains 98.5～99.7 weight parts, the fine silica powder of 0.3～1.5 weight part end.Wherein, if after impregnation whipping agent, add tetrabromo cyclooctane, exist the flame-retardant intumescent polystyrene resin particle obtaining that the problem of sclerosis occurs.
Below, illustrate in greater detail embodiments of the present invention.
Polystyrene resins particle in the present invention can be used the polystyrene resins particle that utilizes known method to manufacture, such as the method that can be listed below etc.:
(1) suspension polymerization is supplied with aqueous medium, styrene monomer and polymerization starter in autoclave, on the heating of autoclave inner edge, stirring limit, makes styrene monomer suspension polymerization, manufactures polystyrene resins particle;
(2) seeding polymerization method, in autoclave, supply with aqueous medium and polystyrene resins kind particle, after making polystyrene resins kind particle be scattered in aqueous medium, styrene monomer is supplied with continuously or intermittently to heating, stir limit in autoclave in limit, make polystyrene resins kind particle absorb styrene monomer, and under the existence of polymerization starter, carry out polymerization, manufacture polystyrene resins particle.Wherein, polystyrene resins kind particle can be by suspension polymerization manufacture the classification of above-mentioned (1).
Wherein, as polystyrene resins of the present invention, such as enumerating the homopolymer of the styrene monomers such as vinylbenzene, alpha-methyl styrene, Vinyl toluene, chloro-styrene, ethyl styrene, isopropyl benzene ethene, dimethyl styrene, bromstyrol or these multipolymer etc.
As above-mentioned polystyrene resins, can using above-mentioned styrene monomer as main component, above-mentioned styrene monomer with can with the multipolymer of the vinyl monomer of this styrene monomer copolymerization, as such vinyl monomer, for example can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) alkyl acrylates such as (methyl) vinylformic acid n-Hexadecane ester, (methyl) vinyl cyanide, dimethyl maleate, dimethyl fumarate, DEF, ethyl fumarate, in addition can also enumerate Vinylstyrene, two functional monomers such as aklylene glycol dimethacrylate etc.
And, from when using fire resistant expansible polystyrene resin particle to carry out in mould foaming, pre-expanded particles that fire resistant expansible polystyrene resin particle pre-frothing obtains is set out to the viewpoint of the fillibility in cavity, and the median size of polystyrene resins particle is preferably 0.3～2.0mm, 0.6～1.4mm more preferably.
In addition, if the vinylbenzene conversion weight-average molecular weight of the polystyrene resins of formation polystyrene resins particle is little, make the physical strength of the flame-proofed polystyrene resin foam formed body that fire resistant expansible polystyrene resin particle foaming obtains decline, on the other hand, if large, the foaminess of fire resistant expansible polystyrene resin particle declines, there is the tendency of the flame-proofed polystyrene resin foam formed body that can not obtain high foamability, so be preferably 200,000～500,000, more preferably 240,000～400,000.
In addition, as the polymerization starter using in above-mentioned suspension polymerization and seeding polymerization method, be not particularly limited, for example can enumerate benzoyl peroxide, lauroyl peroxide, tert butyl peroxy benzoate, tert-butyl peroxide, t-butylperoxy pivarate, tert-butyl hydroperoxide sec.-propyl carbonic ether, tert-butyl hydroperoxide-2-ethylhexyl monocarbonate, sec.-propyl carbonic ether, tert-butyl hydroperoxide acetic ester, 2, two (tert-butyl hydroperoxide) butane of 2-, tert-butyl hydroperoxide-3, 3, 5-tri-methyl hexanoic acid ester, organo-peroxide and the Diisopropyl azodicarboxylates such as di-tert-butyl peroxide six hydrogen terephthalate, the azo-compounds such as azo methyl pentane nitrile etc., these both can use separately, also can be used together more than two kinds.
And, polystyrene resins particle is scattered in aqueous medium and the waterborne suspension obtaining, can use reaction solution after the polymerization that above-mentioned suspension polymerization or seeding polymerization method carry out as waterborne suspension, or the polystyrene resins particle that can be obtained by above-mentioned suspension polymerization or seeding polymerization method from reaction solution separation, this polystyrene resins particle is suspended in the aqueous medium of other preparation, forms waterborne suspension.In addition, as aqueous medium, be not particularly limited, such as enumerating water, ethanol (alcohol) etc., preferably water.
In addition, in above-mentioned suspension polymerization or seeding polymerization method, when making styrene monomer polymerization, in order to make the drop of styrene monomer or the dispersiveness of polystyrene resins kind particle stable, can use suspension stabilizer, as such suspension stabilizer, such as enumerating the water-soluble polymers such as polyvinyl alcohol, methylcellulose gum, polyacrylamide, polyvinylpyrrolidone and the difficult water-soluble inorganic salt such as tricalcium phosphate, magnesium pyrophosphate etc., when using difficult water-soluble inorganic salt, conventionally and use anion surfactant.
As above-mentioned anion surfactant, such as enumerating the higher fatty acid salts such as the alkylbenzene sulfonates such as the alkyl-sulphates such as sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium oleate, β-tetrahydroxy naphthalenesulfonate etc., preferred alkyl benzene sulfonate.
And, in the manufacture method of fire resistant expansible polystyrene resin particle of the present invention, with known main points, make to be scattered in the polystyrene resins particle impregnation whipping agent in above-mentioned waterborne suspension.As such whipping agent, boiling point is below the softening temperature of polystyrene resins, under applicable normal pressure, be gaseous state or liquid organic compound, for example can enumerate propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, neopentane, pentamethylene, cyclopentadiene, normal hexane, the hydrocarbon such as sherwood oil, acetone, the ketones such as methylethylketone, methyl alcohol, ethanol, the alcohols such as Virahol, dme, diethyl ether, dipropyl ether, the lower boiling ether compound such as methyl ethyl ether, carbon dioxide, nitrogen, the inorganic gass such as ammonia etc., preferably boiling point is the hydrocarbon of-45～40 ℃, more preferably propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane.In addition, whipping agent both can be used separately, also can be used together more than two kinds.
In the manufacture method of fire resistant expansible polystyrene resin particle of the present invention, before the polystyrene resins particle impregnation whipping agent that makes to be scattered in waterborne suspension or in impregnation, in above-mentioned waterborne suspension, supply with powder flame-proof agent tetrabromo cyclooctane, make polystyrene resins particle impregnation powdery flame retardent adding to depress.In addition, aqueous medium, if having the aqueous medium of intermiscibility with making waterborne suspension that polystyrene resins particle disperses, is just not particularly limited, such as enumerating water, ethanol (alcohol) etc., preferably water.
In order to improve dispersiveness, above-mentioned powdery flame retardent tetrabromo cyclooctane adds fine silica powder end.As add the method at fine silica powder end to tetrabromo cyclooctane, preferably in the mixing machines such as Henschel mixer, mix certain hour.
In addition, as the fine silica powder end of adding in above-mentioned powder flame-proof agent tetrabromo cyclooctane, specific surface area is 170～330m if
2/ g, wetting ability, hydrophobicity are all good, and more preferably specific surface area is 200m
2/ g.In addition, if specific surface area is less than 170m
2/ g, just can not improve the dispersiveness of tetrabromo cyclooctane, as a result of, and tetrabromo cyclooctane generation Second Aggregation.In addition, if specific surface area is greater than 330m
2/ g, it is many that the amount of dispersing at fine silica powder end just becomes, and has the problem that upper operability worsens of manufacturing.
In addition, fine silica powder end is to the addition of tetrabromo cyclooctane, with respect to the tetrabromo cyclooctane of 98.5～99.7 weight parts, preferably adds the fine silica powder end of 0.3～1.5 weight part, as lower value, and more preferably 0.5 weight part.If be less than 0.3 weight part, just can not improve the dispersiveness of tetrabromo cyclooctane, as a result of, tetrabromo cyclooctane generation Second Aggregation.In addition, if be greater than 1.5 weight parts, the quantitative change of dispersing at fine silica powder end is many, has the problem that upper operability worsens of manufacturing.
And tetrabromo cyclooctane is with respect to the content of polystyrene resins particle, with respect to the polystyrene resins particle of 100 weight parts, be preferably adjusted into 0.45～2.0 weight part, more preferably 0.6～1.5 weight part, 0.7～1.0 weight part particularly preferably.If the flame retardant resistance of the flame-retardant intumescent polystyrene resins formed body that be less than 0.45 weight part, obtains just declines.In addition, if be greater than 2.00 weight parts, manufacturing cost improves, and on the other hand, adhesion quantitative change during pre-frothing is many, and pre-expanded particles worsens to the fillibility in die forming machine.
Make to be scattered in impregnation whipping agent and powdery flame retardent in the polystyrene resins particle in waterborne suspension, manufacture after fire resistant expansible polystyrene resin particle, from waterborne suspension, take out this fire resistant expansible polystyrene resin particle, as required, can implement to clean processing, drying treatment to fire resistant expansible polystyrene resin particle.
In addition, during from foaming in carrying out mould, pre-expanded particles that fire resistant expansible polystyrene resin particle pre-frothing obtains is set out to the viewpoint of the fillibility in cavity, and the median size of fire resistant expansible polystyrene resin particle is preferably 0.3～2.0mm, 0.6～1.4mm more preferably.
In addition, in fire resistant expansible polystyrene resin particle, except powdery flame retardent, in not damaging the scope of physical property, as required, can add the additives such as bladder regulator, weighting agent, flame retardant, lubricant, tinting material, solvent, while adding these additives in fire resistant expansible polystyrene resin particle, can in the waterborne suspension that polystyrene resins particle is disperseed, add additive.
Then,, to using above-mentioned fire resistant expansible polystyrene resin particle, the main points of manufacturing flame-proofed polystyrene resin foam formed body describe.As the main points of using fire resistant expansible polystyrene resin particle, manufacture flame-proofed polystyrene resin foam formed body, can adopt known method, specifically, can heat fire resistant expansible polystyrene resin particle, make its pre-frothing, making volume density is 0.01～0.05g/cm
3the polystyrene resins pre-expanded particles of left and right, by filling this polystyrene resins pre-expanded particles in the cavity of mould, its heating being foamed, can obtain flame-proofed polystyrene resin foam formed body.
If the density of above-mentioned flame-proofed polystyrene resin foam formed body is low, the separated foam rate of flame-proofed polystyrene resin foam formed body just declines, the heat insulating ability of flame-proofed polystyrene resin foam formed body and physical strength decline, on the other hand, if high, in mould, in expanded moldings, a needed time of circulation is elongated, and the production efficiency of flame-proofed polystyrene resin foam formed body declines, and is therefore preferably 0.01～0.05g/cm
3.
Embodiment
Below, by embodiment and comparative example explanation the present invention, but the present invention is not by these restrictions.
(embodiment 1)
(Production Example) is in the autoclave with stirrer of 100 liters of internal volumes, add tricalcium phosphate (graduation society produces greatly) 120g, Sodium dodecylbenzene sulfonate 2.4g, benzoyl peroxide (purity 75 % by weight) 140g, tert-butyl hydroperoxide-2-ethylhexyl monocarbonate 30g, ion exchanged water 40kg and styrene monomer 40kg, with 100rpm rotating speed Stirring oar, stir, form waterborne suspension.
Then, waterborne suspension, with 100rpm rotating speed Stirring oar, is stirred in limit, limit is warmed up to 90 ℃ by the temperature in autoclave, with 90 ℃ of maintenances 6 hours, then the temperature in autoclave is warmed up to 120 ℃, with 120 ℃ of maintenances 2 hours, make thus styrene monomer suspension polymerization.
Then, the temperature in autoclave is cooled to 25 ℃, in autoclave, takes out granules of polystyrene, repeatedly repeatedly clean dehydration, after drying process, by granules of polystyrene classification, obtaining particle diameter is the granules of polystyrene that 0.6～0.85mm and weight-average molecular weight are 300,000.
Then, in other 100 liters of autoclaves with stirrer, add after ion exchanged water 30kg, Sodium dodecylbenzene sulfonate 4g, magnesium pyrophosphate 100g, in autoclave, add above-mentioned granules of polystyrene 11kg as kind of a particle, stir it is evenly dispersed in water.
In addition, in 6kg ion exchanged water, disperse Sodium dodecylbenzene sulfonate 2g and magnesium pyrophosphate 20g, thereby make dispersion liquid, in addition, in 5kg styrene monomer, dissolve benzoyl peroxide (purity 75%) 88g and the tert-butyl hydroperoxide-2-ethylhexyl monocarbonate 50g as polymerization starter, make styrene monomer solution, in above-mentioned dispersion liquid, add this styrene monomer solution, use mixer for well-distribution to stir, make it emulsifying, obtain emulsion.
Then, to in autoclave, be heated to 75 ℃, and keep, in autoclave, add afterwards above-mentioned emulsion, keep 30 minutes, make to absorb smoothly styrene monomer and benzoyl peroxide in polystyrene kind particle, then, limit is warmed up to 108 ℃ by the heat-up rate with 0.2 ℃/min in autoclave from 75 ℃, limit is with dripping continuously styrene monomer 28kg in 160 minutes clockwise autoclaves, then, styrene monomer drip finish after after 20 minutes, with the heat-up rate of 1 ℃/min, be warmed up to 120 ℃, keep 90 minutes, by seeding polymerization, obtain granules of polystyrene.In addition, styrene monomer is all used to polymerization.
(embodiment 1)
At fire retardant tetrabromo cyclooctane, (the first industrial pharmacy society produces, trade(brand)name " ピ ロ ガ mono-De FR-200 ") (Japanese AEROSIL society produces in 440g, to add 2.24g silicon-dioxide, trade(brand)name " AEROSIL200 ") as flowing agent, carry out dry type mixing (for example Henschel mixer), make fire retardant A.
Then, with the cooling rate of 1 ℃/min, will in autoclave, be cooled to 90 ℃, to after adding 132g dicumyl peroxide as flame retardant in autoclave, in autoclave, add above-mentioned fire retardant A afterwards.
Then, in autoclave, add after fire retardant A, after 30 minutes, enclosed high pressure still, then by nitrogen, pressurize, to usining in autoclave, within 30 minutes, be pressed into butane (Trimethylmethane/normal butane (weight ratio)=30/70) 2640g and pentane (iso-pentane/Skellysolve A (weight ratio)=20/80) 1100g as whipping agent, keep this state 3 hours.
Then, to in autoclave, be cooled to 25 ℃, in autoclave, take out flame-retardant intumescent granules of polystyrene, repeatedly repeatedly clean, dewater, after drying process, by the classification of flame-retardant intumescent granules of polystyrene, obtaining particle diameter is that 0.85～1.2mm, median size are the flame-retardant intumescent granules of polystyrene that 1.1mm and weight-average molecular weight are 300,000.
In addition, the powdery flame retardent of fire retardant A is all by granules of polystyrene impregnation.
(embodiment 2)
In the making of fire retardant A, the amount that makes tetrabromo cyclooctane is 220g, and operation similarly to Example 1, obtains flame-retardant intumescent granules of polystyrene in addition.
(embodiment 3)
In the making of fire retardant A, the amount that makes tetrabromo cyclooctane is 660g, and operation similarly to Example 1, obtains flame-retardant intumescent granules of polystyrene in addition.
(embodiment 4)
In the making of fire retardant A, the amount that makes tetrabromo cyclooctane is 880g, and operation similarly to Example 1, obtains flame-retardant intumescent granules of polystyrene in addition.
(embodiment 5)
In the making of fire retardant A, wetting ability silicon-dioxide replaces 2.24g, uses 4.48g, and operation similarly to Example 1, obtains flame-retardant intumescent granules of polystyrene in addition.
(embodiment 6)
In the making of fire retardant A, wetting ability silicon-dioxide replaces 2.24g, uses 6.72g, and operation similarly to Example 1, obtains flame-retardant intumescent granules of polystyrene in addition.
(embodiment 7)
In the making of fire retardant A, as flowing agent, use wetting ability silicon-dioxide (Japanese AEROSIL society produces, trade(brand)name " AEROSIL300 "), operation similarly to Example 1, obtains flame-retardant intumescent granules of polystyrene in addition.
(embodiment 8)
In the making of fire retardant A, as flowing agent, use hydrophobic silica (Japanese AEROSIL society produces, trade(brand)name " AEROSILR974 "), operation similarly to Example 1, obtains flame-retardant intumescent granules of polystyrene in addition.
(comparative example 1)
In the making of fire retardant A, the amount that makes tetrabromo cyclooctane is 88g, and operation similarly to Example 1, obtains flame-retardant intumescent granules of polystyrene in addition.
(comparative example 2)
In the making of fire retardant A, the amount that makes tetrabromo cyclooctane is 1320g, and operation similarly to Example 1, obtains flame-retardant intumescent granules of polystyrene in addition.
(comparative example 3)
In the making of fire retardant A, do not use wetting ability silicon-dioxide, operation similarly to Example 1, obtains flame-retardant intumescent granules of polystyrene in addition.
(comparative example 4)
In the making of fire retardant A, wetting ability silicon-dioxide replaces 2.24g, uses 0.22g, and operation similarly to Example 1, obtains flame-retardant intumescent granules of polystyrene in addition.
(comparative example 5)
In the making of fire retardant A, wetting ability silicon-dioxide replaces 2.24g, uses 8.96g, and operation similarly to Example 1, obtains flame-retardant intumescent granules of polystyrene in addition.
(comparative example 6)
In the making of fire retardant A, as flowing agent, use wetting ability silicon-dioxide (Japanese AEROSIL society produces, trade(brand)name " AEROSIL130 "), operation similarly to Example 1, obtains flame-retardant intumescent granules of polystyrene in addition.
(comparative example 7)
In the making of fire retardant A, as flowing agent, use wetting ability silicon-dioxide (Japanese AEROSIL society produces, trade(brand)name " AEROSIL380 "), operation similarly to Example 1, obtains flame-retardant intumescent granules of polystyrene in addition.
(comparative example 8)
In the making of fire retardant A, replace wetting ability silicon-dioxide 2.24g, use tetrabromo-bisphenol-bis-(2,3-dibromopropyl ether) 88.0g, operation similarly to Example 1, obtains flame-retardant intumescent granules of polystyrene in addition.
About the various embodiments described above and each comparative example, as shown in Table 1 and Table 2, carry out following evaluation.
[measuring method of silicon-dioxide specific surface area]
The specific area measuring method at the fine silica powder end of using in the present invention is completely based on BET method.
[the adhesion evaluation of fire retardant A]
In polyethylene bag, add 100g fire retardant, be packaged into 50mm diameter cylinder, put the hammer of 1.1kg, in 40 ℃ of baking ovens, keeping, after 1 month, is taken out, and observation state, evaluates.
* ... with stone state, fire retardant solidifies, even if hold also not disintegration.
△ ... with hard state, fire retardant solidifies, if but held with regard to disintegration.
Zero ... have tight sensation, but do not solidify, be loose state.
[moulding of foamed polystyrene formed body]
In tumbler mixer, add the flame-retardant intumescent granules of polystyrene 40kg, the polyoxyethylene glycol 20g as surface treatment agent, Zinic stearas 60g, fatty acid triglycercide (production of Li Yan ビタミン society, trade(brand)name " リ ケ マ mono-Le VT-50 ") 40g and glycerine monofatty ester (production of Li Yan ビタミン society, trade(brand)name " リ ケ マ mono-Le the S-100P ") 20g that obtain, stir 30 minutes, at flame-retardant intumescent granules of polystyrene surface clad surface treatment agent.
Then, flame-retardant intumescent granules of polystyrene is taken care of after 48 hours in the refrigerator of 15 ℃, at special permission Room communique 57 (1982)-133[3347] record in the 39th page of known conventional techniques collection (foaming) until above foaming layer the volumetric quantity of analyzer be in the round tube type intermittent type pressurization pre-foaming machine of 350 liters, every 1 liter adds flame-retardant intumescent granules of polystyrene 5.8kg, by steam heating 2 minutes, obtain polystyrene pre-expanded particles.
Then, under room temperature atmosphere, above-mentioned polystyrene pre-expanded particles is placed 24 hours, on the other hand, (ShijinYuan Industrial Co., Ltd produces to prepare block forming machine, trade(brand)name " PEONY205DS "), this bulk forming machine possesses the mould of the cavity of the rectangular shape with vertical 840 * horizontal 930mm * high 530mm, filled polystyrene pre-expanded particles in the cavity of this mould, in the cavity of mould, the water vapor of 0.07MPa (gauge pressure) is pressed into 20 seconds, make polystyrene pre-expanded particles second time of foaming, then, cooling die is to become-0.01MPa of mould inner pressure, obtain the flame-proofed polystyrene expanded moldings of rectangular shape.After this, in the kiln of 70 ℃, flame-proofed polystyrene expanded moldings is taken care of 3 days.
[combination of pre-expanded particles]
Prepare W
1(g) the polystyrene pre-expanded particles obtaining with above-mentioned main points, is used the sieve that sieve aperture is 1cm to sieve to this polystyrene pre-expanded particles, is determined at the weight W of the upper residual polystyrene pre-expanded particles of sieve
2(g), based on following formula, calculate pre-expanded particles conjugation, in table 1,2, represent this result.In addition, 1 % by weight is evaluated as to " zero " below, is greater than 1 % by weight and is evaluated as " * ".
The conjugation of pre-expanded particles (% by weight)=100 * W
2/ W
1
[flammability test]
Utilize vertical cutter, from the flame-proofed polystyrene expanded moldings obtaining, cut out the test film of the rectangular shape of 5 vertical 200mm * horizontal 25mm * high 10mm, in 60 ℃ of baking ovens, place after 1 day, measuring method A according to JIS A9511-2006 measures, obtain the mean value of 5 test films, as going out the flame time, according to following standard comprehensive evaluation, using this result as going out property certainly, be illustrated in table 1,2.In addition, in above-mentioned JIS specification, the flame time of going out was necessary in 3 seconds, if within 2 seconds, take interior as preferably, if 1 second with interior for more preferably.
* ... even the flame time of going out is greater than 3 seconds or 1 test film has incompleteness or crosses the burning of knock limit indicatrix.
Zero ... the flame time of going out was greater than 1 second in 3 seconds, 5 samples are complete, there is no incompleteness, cross knock limit indicatrix and do not burn.
◎ ... the flame time of going out is in 1 second, 5 samples are complete, there is no incompleteness, cross knock limit indicatrix and do not burn.
[ocular estimate of expanded moldings]
The outward appearance of visual observations expanded moldings, evaluates based on following benchmark.
Zero ... expanded beads weld is each other level and smooth.
* ... expanded beads weld each other produces concavo-convex.
[thermal welding]
Middle body at the long side direction above lower several the 6th section product (vertical 1840mm * horizontal 980mm * thick 50mm) being obtained by kuromore cutting, along short side direction, with cutters, cut out after the line of cut of degree of depth 5mm, along this line of cut, with hand, section product are divided into 2 parts, obtain the cutting plate of vertical 920mm * horizontal 930mm * thick 50mm.
In the cutting plate cut surface obtaining, number goes out the particle (a) of expanded beads implosion and the granule number (b) breaking in the interface between expanded beads, based on following formula, calculates welding rate.In table 1,2, represent this result.In addition, 70% above welding ratio be ◎, what more than 50% be less than 70% welding ratio is zero, be less than 50% welding ratio for *.
Welding rate (%)=100 * granule number (a)/(granule number (a)+granule number (b))
By table 1, can confirm with respect to the above-mentioned polystyrene resins of 100 weight part, add the above-mentioned tetrabromo cyclooctane of 0.45～2.0 weight part, the above-mentioned tetrabromo cyclooctane as powdery flame retardent with respect to 98.5～99.7 weight parts, the embodiment at the above-mentioned fine silica powder end of containing 0.3～1.5 weight part, the combination of its adhesion evaluation, pre-expanded particles, flammability test (going out property certainly), combustion test evaluation, the ocular estimate of foam molded product, thermal welding are all good.
With respect to this, by table 2, with respect to the above-mentioned polystyrene resins of 100 weight part, the comparative example 1 that contains the above-mentioned tetrabromo cyclooctane of 0.2 weight part, its flammability test (going out property certainly) worsens, and combustion test is evaluated as *.In addition, with respect to the above-mentioned polystyrene resins of 100 weight part, the comparative example 2 that contains the above-mentioned tetrabromo cyclooctane of 3.0 weight part, its adhesion is evaluated as * and thermal welding for *.In addition, not containing the comparative example 3 of wetting ability silicon-dioxide, its adhesion is evaluated as *, the combination of pre-expanded particles is also *.At above-mentioned fine silica powder end, be in the comparative example 4 of 0.05 weight part, adhesion is evaluated as *, the combination of pre-expanded particles is also *.In addition, above-mentioned fine silica powder end is the comparative example 5 of 2 weight parts, aspect foam molded product ocular estimate, is having problem.In addition, SiO 2 powder disperses greatly.In addition, flowing agent is become to the comparative example 6 of tetrabromo-bisphenol-bis-(2,3-dibromopropyl ethers), being combined into of pre-expanded particles *, in addition, flammability test (going out property certainly) also worsens, in addition combustion test evaluation be also *.
Utilizability in industry
Flame-retardant intumescent granules of polystyrene of the present invention is used in the purposes of broad range, is used in agriculture fishery products field, field of household appliances, building materials building field etc.Particularly, at building materials field, be used in the thermal insulation material on wall or floor.
Claims (1)
1. a method of manufacturing fire resistant expansible polystyrene resin particle, it is characterized in that: before the polystyrene resins particle impregnation whipping agent that makes to be scattered in waterborne suspension or in impregnation, in above-mentioned waterborne suspension, supply with powdery flame retardent tetrabromo cyclooctane, make powdery flame retardent described in the impregnation of described polystyrene resins particle adding to depress, described powdery flame retardent is added with fine silica powder end, from described waterborne suspension, take out and obtain described fire resistant expansible polystyrene resin particle, wherein
Tetrabromo cyclooctane is with respect to the content of polystyrene resins particle, with respect to the polystyrene resins particle of 100 weight parts, is 0.45～2.0 weight part,
Described powdery flame retardent is with respect to the tetrabromo cyclooctane of 98.5～99.7 weight parts, and the described fine silica powder that contains 0.3～1.5 weight part is last,
The specific surface area being recorded by BET method at described fine silica powder end is 170～330m
2/ g.
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