CN101910267B - Flame-retardant expandable styrene resin particle, and method for production thereof - Google Patents
Flame-retardant expandable styrene resin particle, and method for production thereof Download PDFInfo
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- CN101910267B CN101910267B CN200880123158.0A CN200880123158A CN101910267B CN 101910267 B CN101910267 B CN 101910267B CN 200880123158 A CN200880123158 A CN 200880123158A CN 101910267 B CN101910267 B CN 101910267B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0019—Use of organic additives halogenated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
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Abstract
Disclosed is a method for producing a flame-retardant expandable styrene resin particle by the suspension polymerization of a styrene monomer. The method is characterized by involving the steps of: adding 0.45 to 2.0 parts by weight of tetrabromocyclooctane to 100 parts by weight of the styrene monomer, thereby producing a styrene resin particle; and impregnating the styrene resin particle with a physical foaming agent during or after the suspension polymerization of the styrene monomer while adjusting the temperature of the impregnation to a temperature falling within the range from 80 to 110 DEG C, thereby producing the frame-retardant expandable styrene resin particle.
Description
Technical field
The present invention relates to resin particle of the foamable styrene-based of a kind of flame retardant resistance and preparation method thereof.More specifically, the present invention relates to a kind of tetrabromo cyclooctane that uses as resin particle of the foamable styrene-based of flame retardant resistance of fire retardant and preparation method thereof.
Background technology
Because the resin molded foam body of styrene-based has excellent intensity and thermal insulation, so be used as to a great extent material of construction.The preparation method of the resin molded foam body of such styrene-based comprises: make styrene monomer suspension polymerization to obtain the resin particle of styrene-based; Flood the resin particle of the styrene-based that obtains to obtain the resin particle of foamable styrene-based with pneumatogen; Make the resin particle of the foamable styrene-based that obtains foam in advance to obtain the particle of the resin pre-frothing of styrene-based; The pre-expanded beads that obtains packed into have in the mould that is used for foaming of intended shape; And the particle hot melt and the integration that under the effect of its blow(ing) pressure, make pre-frothing.
On the other hand, the resin molded foam body of above-mentioned styrene-based has inflammable problem.Especially as material of construction the time, they may cause spreading of flame when fire.Therefore, attempted by in the resin molded foam body of styrene-based, adding fire retardant to address this problem.
The example of the method for known interpolation fire retardant comprises the method that fire retardant is dissolved in styrene monomer, and the method for also flooding with fire retardant in the resin particle with pneumatogen dipping styrene-based.The example of front a kind of method comprises disclosed method in TOHKEMY 2003-335891 communique (patent document 1) and the TOHKEMY 2002-194130 communique (patent document 2), and the example of rear a kind of method comprises disclosed method in 6 (1994)-No. 18918 communiques of Japanese JP (patent document 3) and the TOHKEMY 2007-246606 communique (patent document 4).
Patent document 1: TOHKEMY 2003-335891 communique
Patent document 2: TOHKEMY 2002-194130 communique
Patent document 3: 6 (1994)-No. 18918 communiques of Japanese JP
Patent document 4: TOHKEMY 2007-246606 communique
Summary of the invention
The problem that the invention wish solves
In front a kind of method, mainly use hexabromocyclododecane (HBCD) as fire retardant.HBCD is worried the material that meeting accumulate in living organism, therefore expectation reduces the use to it.In rear a kind of method, because being resin particle at styrene-based, the dipping of fire retardant carries out, therefore its pickup is limited, thereby expectation improves the pickup of fire retardant, to improve flame retardant resistance.
In addition, also have other problem: when the pickup of fire retardant for the resin particle of styrene-based was too large, fire retardant served as nucleator, so that the size of bubble is too small in the foamed resin of resulting styrene-based.This problem especially has disadvantageous effect for rear a kind of method.That is, in rear a kind of method, there is more fire retardant in the near surface of the resin particle of styrene-based, causes in pre-expanded beads formed bubble very little in the rim surface zona.As a result, bubble possibly can't tolerate heat during producing expanded moldings by the method for forming producing fusing, the outward appearance of expanded moldings is caused detrimentally affect.In addition, there is more fire retardant at the near surface of the resin particle of styrene-based, is easy to produce so-called obturation, that is, and fusion and linking after pre-frothing between the pre-expanded beads.And in some cases, fire retardant experiences 2 reunions in the solution that floods with whipping agent, so that fire retardant disperses inequality.As a result, the resin particle of styrene-based may be uneven to the absorption of fire retardant.And absorb the uneven particle that will cause existence partly to absorb more fire retardant, and such particle thermotolerance is relatively poor.Therefore, particle may just can't tolerate in the heating of producing by the method for forming in the expanded moldings process, is shrunk to the sclerosis particle.Expanded moldings is configured as predetermined shape by the cutting of nichrome (Nichorme) line that heated usually, and nichrome wire can be upspring at the sclerosis particle in this case, produce the line with uneven shape at cut surface, thereby significantly reduce the value of the formed body that produces.In addition, have the line of uneven shape, when the applying of expanded moldings and panel is used, possibly can't produce sufficient bond strength.
And, the problem that the heat fusion between the resin pre-expanded beads of styrene-based may be very poor in addition.
The means of dealing with problems
The present inventor has been found that by with the specific fire retardant of specified quantitative and will be that specific temperature is finished the present invention with the Temperature Setting of pneumatogen dipping, a kind of resin particle of foamable styrene-based can be provided, and the resin particle of described foamable styrene-based has excellent heat fusion and allows to produce the expanded moldings with excellent flame retardancy between particle when foaming.
Therefore the present invention provides a kind of method for preparing the resin particle of the foamable styrene-based of flame retardant resistance, and the method comprises: the styrene monomer that adds in the suspension polymerization of styrene monomer with respect to 100 weight parts is that the tetrabromo cyclooctane of 0.45 weight part to 2.0 weight part is with the resin particle of acquisition styrene-based; Then, during the suspension polymerization of styrene monomer or afterwards with the resin particle of pneumatogen dipping styrene-based, simultaneously dipping temperature is adjusted to 80 to 110 ℃, to obtain the resin particle of the foamable styrene-based of flame retardant resistance.
The present invention also provides the resin particle of the foamable styrene-based of a kind of flame retardant resistance, and the resin particle of the foamable styrene-based of described sun combustion property comprises the resin particle of styrene-based and is contained in pneumatogen and tetrabromo cyclooctane in the resin particle of this styrene-based;
When the containing ratio of the contained tetrabromo cyclooctane in the rim surface zona of the resin particle of styrene-based is " a " (% by weight), when the containing ratio of contained tetrabromo cyclooctane was b (% by weight) in the integral body of the resin particle of styrene-based, contained tetrabromo cyclooctane satisfied relational expression " a "≤1.1 * " b " in the resin particle of styrene-based;
With respect to the resin particle of the styrene-based of 100 weight parts, the amount of contained tetrabromo cyclooctane is 0.45 weight part to 2.0 weight part in the integral body of the resin particle of styrene-based; And
When the resin particle of the foamable styrene-based of flame retardant resistance during with 50 times blowing ratio foaming, it is the foam of 50 μ m to 350 μ m that average bubble size is provided.
The effect of invention
Preparation method of the present invention can provide the resin particle of the foamable styrene-based of a kind of flame retardant resistance, and it does not have the thick close variation of bubble and have gratifying heat fusion when moulding in the time of can controlling bubble size, foaming.
In addition, when suspension polymerization, use tensio-active agent, can improve the dispersion stabilization of drop in suspension polymerization system of monomer mixture.
Contain flame retardant in the monomer mixture, can improve the flame retardant resistance of the resin particle of foamable styrene-based.
Regulate dipping temperature, make by the 50 times of expanded moldings that obtain of resin particle foaming with the foamable styrene-based of above-mentioned flame retardant resistance to have the average bubble size of 50 μ m to 350 μ m, so that the resin particle of the more gratifying foamable styrene-based of heat fusion to be provided.
The accompanying drawing summary
Fig. 1 is the electron photomicrograph in cross section of the pre-expanded beads of embodiment 1.
Fig. 2 is the electron photomicrograph in cross section of the pre-expanded beads of embodiment 3.
Fig. 3 is the electron photomicrograph in cross section of the pre-expanded beads of Comparative Examples 4.
Fig. 4 is the electron photomicrograph in cross section of the pre-expanded beads of Comparative Examples 5.
Fig. 5 is the electron photomicrograph in cross section of the pre-expanded beads of Comparative Examples 6.
Embodiment
In the present invention, at first carry out the suspension polymerization of styrene monomer with the resin particle of acquisition styrene-based, and in the case, in styrene monomer, add tetrabromo cyclooctane (TBCO) and polymerization starter.
The example of styrene monomer comprises vinylbenzene, alpha-methyl styrene, p-methylstyrene, t-butyl styrene, Benzene Chloride ethene etc.These monomers can use separately or it is used in combination.In these monomers, vinylbenzene particularly preferably.In addition, the ester of the acrylic or methacrylic acid such as methyl acrylate, butyl acrylate, methyl methacrylate, methacrylic acid second fat and methacrylic acid hexadecyl fat; Or the monomer such as vinyl cyanide, fumaric acid dimethyl esters and ethyl fumarate, can with the styrene monomer copolymerization.In addition, also can make difunctional monomer and styrene monomer copolymerization such as Vinylstyrene and alkylene glycol dimethacrylate.
The consumption of TBCO is 0.45 weight part to 2.00 weight part by the styrene monomer of 100 weight parts.Heat fusion when this scope can be guaranteed flame retardant resistance and moulding, and suppress the thick close variation of bubble.
Polymerization starter is not particularly limited, can selects rightly suitable polymerization starter according to polymerization temperature.The example comprises organo-peroxide, the for example special fourth fat of benzoyl peroxide, lauroyl peroxide, perbenzoic acid, t-butylperoxy pivarate, carbonic acid tert-butyl peroxy isopropyl ester, tert-butyl peroxy acetate, 2,2-two (tert-butyl hydroperoxide) butane, tert-butyl hydroperoxide-3,3,5-trimethylammonium cyclohexylpentanoic acid ester, di-tert-butyl peroxide six hydrogen terephthalate and 1,1-di-tert-butyl peroxide-3,3,5-trimethylammonium cyclohexane; And azo-compound, for example Diisopropyl azodicarboxylate and azo two (methyl pentane nitrile).These polymerization starters can use separately or it is used in combination more than 2 kinds.The consumption of polymerization starter can be 0.05 weight part to 3.0 weight part by the styrene monomer of 100 weight parts.
By TBCO is dissolved in the styrene monomer, obtain monomer mixture.This monomer mixture can comprise flame retardant.The example of flame retardant comprises cumene hydroperoxide, dicumyl peroxide, tertbutyl peroxide, 2,3-dimethyl-2,3-diphenyl butane etc.The consumption of flame retardant can be 0.1 weight part to 0.5 weight part by the styrene monomer of 100 weight parts.
Be scattered in monomer mixture in the aqueous medium and carry out suspension polymerization.
The example of aqueous medium comprises the mixture of water and water and water-soluble organic medium (for example methyl alcohol and ethanol).Aqueous medium can contain the additive of tensio-active agent and dispersion agent and so on.
The example of tensio-active agent comprises anion surfactant, cats product, zwitterionics and nonionogenic tenside.
The example of anion surfactant comprises lipid acid oils, for example sodium oleate and Viscotrol C potassium; Alkyl sulfuric ester salt, for example Sodium Lauryl Sulphate BP/USP and Texapon Special; Alkylbenzene sulfonate, for example Sodium dodecylbenzene sulfonate; Sulfonated alkyl naphathalene; Alkyl sulfonate; Dialkyl sulfosuccinates; Alkyl phosphate salt, naphthene sulfonic acid-formalin condensation product, polyoxyethylene-alkyl phenyl ether sulfuric acid, polyxyethylated sulfuric acid etc.
The example of nonionogenic tenside comprises Voranol EP 2001, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty(acid)ester, polyoxy sorbitan fatty(acid)ester, polyoxyethylene alkyl amine, glycerol fatty acid ester, oxygen ethene-oxypropylene block polymer etc.
The example of cats product comprises alkylamine salt, such as n-Laurylamine acetate and octadecylamine acetate; Quaternary ammonium salt is such as Dodecyl trimethyl ammonium chloride; Etc..
The example of zwitterionics comprises dimethyl dodecyl amine oxide and phosphoric acid ester or phosphorous acid ester tensio-active agent.
Above-mentioned tensio-active agent can use separately or it is used in combination more than 2 kinds.The consumption of tensio-active agent can be 0.002 weight part to 1.0 weight part by the aqueous medium of 100 weight parts.
The example of dispersion agent comprises water-soluble polymer, such as polyvinyl alcohol, methylcellulose gum, polyvinylpyrrolidone and polyacrylamide; With the insoluble inorganic salt, such as magnesium pyrophosphate, tricalcium phosphate and hydroxyapatite.These dispersion agents can use separately or it is used in combination more than 2 kinds.The consumption of dispersion agent can be 0.2 weight part to 10 weight part with respect to the styrene monomer of 100 weight parts.
Make styrene monomer carry out suspension polymerization.Suspension polymerization generally is to carry out under 50 ℃ to 120 ℃ 1 hour to 20 hours.As the result of suspension polymerization, obtain the resin particle of styrene-based.
In addition, during suspension polymerization or afterwards, with the resin particle of pneumatogen dipping styrene-based, thereby obtain the resin particle of the foamable styrene-based of flame retardant resistance.To be adjusted to 80 ℃ to 110 ℃ for the dipping temperature of dipping herein.Such adjusting allows to provide the resin particle of the foamable styrene-based of a kind of flame retardant resistance, and the resin particle of the foamable styrene-based of described flame retardant resistance can be controlled bubble size, not have the thick close variation of bubble and have gratifying heat fusion during in moulding in when foaming.
During suspension polymerization, the resin particle with pneumatogen dipping styrene-based can be undertaken by pneumatogen is pressed in the aqueous medium.On the other hand, when after suspension polymerization, carrying out pneumatogen to the dipping of the resin particle of styrene-based, the resin particle that can take out styrene-based from aqueous medium is used for dipping, perhaps the resin particle of styrene-based can be stayed to be used for dipping in the aqueous medium.
Pneumatogen refers to just have without decomposition the whipping agent of frothing function, i.e. so-called volatile foaming agent.The example of pneumatogen comprises aliphatic hydrocarbon, for example propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane and hexane.These pneumatogens can use separately or it is used in combination more than 2 kinds.
The median size of the resin particle of the foamable styrene-based of flame retardant resistance that obtains can be 0.3mm to 2.0mm for example.
The resin particle of the foamable styrene-based of flame retardant resistance becomes expanded moldings through known pre-frothing process and foaming-moulding process.Particularly, when 50 times of particle foaming, the mean diameter that consists of the bubble of expanded moldings is 50 μ m to 350 μ m.This scope has gratifying heat fusion so that consist of the expanded particle of expanded moldings.
A kind of resin particle of the foamable styrene-based of flame retardant resistance that is obtained by above-mentioned method side also is provided among the present invention.When the containing ratio of the contained tetrabromo cyclooctane in the rim surface zona of the resin particle of styrene-based is a (% by weight), and when the containing ratio of contained tetrabromo cyclooctane was b (% by weight) in the integral body of the resin particle of styrene-based, tetrabromo cyclooctane contained in the resin particle of styrene-based satisfied relational expression a≤1.1 * b.By satisfying this relation, then can provide the resin particle that not only satisfies flame retardant resistance but also satisfy the foamable styrene-based of flame retardant resistance of heat fusion requirement.This relation is more preferably represented by formula a≤1.05 * b.
Here, because the containing ratio " a " of tetrabromo cyclooctane in the particle rim surface zona is difficult to direct mensuration, be the value of measuring according to following methods therefore.That is, cut out the test film of thick 0.2mm from the surface of the 50 times of expanded moldings that obtain that foam by the resin particle that makes the foamable styrene-based of flame retardant resistance.Form because the surface of expanded moldings is the surface by the resin particle of the foamable styrene-based of flame retardant resistance, so test film presents the state of rim surface zona of the resin particle of the foamable styrene-based of flame retardant resistance.The amount of the tetrabromo cyclooctane in the determination experiment sheet, and calculate itself and the ratio of test film gross weight, thus obtain the containing ratio a (% by weight) of tetrabromo cyclooctane contained in each particle rim surface zona.The details of measuring method is recorded among the embodiment.
On the other hand, the containing ratio " b " of contained tetrabromo cyclooctane refers to as the ratio of raw material in order to amount with the amount of styrene monomer of the tetrabromo cyclooctane of the resin particle for preparing the foamable styrene-based of flame retardant resistance in the integral body of each particle.
Embodiment
Hereinafter will be described more specifically the present invention based on embodiment, but the present invention is not limited to these embodiment.The measuring method of the molecular weight of the resin particle of styrene-based, volume blowing ratio, blowing ratio, flame retardant resistance, average bubble size and heat fusion is as follows.
(molecular weight of the resin particle of styrene-based)
Use gel permeation chromatography (GPC) to measure weight-average molecular weight (Mw).Its measuring method is as follows.Weight-average molecular weight in the literary composition (Mw) refers to the weight-average molecular weight that illustrates as the molecular weight of polystyrene (PS).
After the sample dissolution that makes 50mg is filtered it in 10 milliliters of tetrahydrofuran (THF)s (THF) and with nonaqueous 0.45 μ m chromato-disk (chromatography disc), use chromatography to measure.Chromatographic condition is as follows.
Liquid chromatograph: trade(brand)name " gel permeation chromatograph HLC-8020 ", produced by Tosoh company
Post: trade(brand)name " TSKgel GMH-XL-L ", Φ 7.8mm * 30cm * 2 are produced by Tosoh company
Column temperature: 40 ℃
Carrier gas: tetrahydrofuran (THF) (THF)
Carrier gas flux: 1 ml/min
Injection pump temperature: 35 ℃
Detect: RI
Injection rate: 100 microlitres
The working curve polystyrene standard: commodity clear and that electrician company produces are called " shodex ", weight-average molecular weight: 1030000; Produce weight-average molecular weight: 5480000,3840000,355000,102000,37900,9100,2630,870 with Tosoh company
(volume blowing ratio)
Making after pre-expanded beads as sample freely falls into graduated cylinder, beat the bottom of graduated cylinder so that sample volume is certain, the volume of working sample and quality are according to following formula volume calculated blowing ratio.In the situation of the resin of styrene-based, the proportion of resin is 1.0.
The quality (g) of the sample volume (ml) in volume blowing ratio (multiple)=graduated cylinder/sample * numerical value proportion
(blowing ratio)
The mode that represents with 3 above significant figure is measured the test film of expanded moldings, and (size of example 50 * 50 * 25mm) and quality are calculated blowing ratio according to following formula.In the situation of resin that is styrene-based, the proportion of resin is 1.0.
Blowing ratio (multiple)=test film volume (cm
3)/test film quality (g) * resin proportion
(flame retardant resistance)
Cut the test film of 5 thick 10mm that respectively do for oneself, long 200mm, wide 25mm from expanded moldings, and provide catch fire boundary indicatrix and the knock limit indicatrix of regulation.By using candle to make each test film burning to the boundary indicatrix that catches fire as burning things which may cause a fire disaster, then leave flame, measure from the time (second) of this moment during to fray-out of flame.In 5 tests until when being no more than 3 seconds the mean time of fray-out of flame and do not have the test film burning to surpass burning circle indicatrix, then estimate formed body for passing.Be such as the candle of burning things which may cause a fire disaster, when the length of match is approximately during 10mm, its flame that provides in static combustion has length and the about width more than the 7mm more than the 50mm.
(average bubble size)
The cutting expanded moldings makes 1/10 to make a video recording with 100 times of scanning electronic microscope (S-3000N of Hitachi Ltd's production) amplifications to the inboard 9/10 or more from the face that cuts of the cut surface outside.The image of taking the photograph is printed on the A4 paper with every paper 4 sub-pictures, is calculated according to the following formula out the mean chord length (t) of bubble from the number of bubbles of (length 60mm) on any straight line.Straight line avoids bubble the drawn straight line of point of contact contact (when in certain some contact, then this bubble being counted) as much as possible arbitrarily.Measure at 6 places.
Mean chord length t=60/ (number of bubbles * photo magnification)
Then, be calculated according to the following formula bubble size D.
D＝t/0.616
(heat fusion)
After the moulding, make expanded moldings 70 ℃ of dryings 48 hours, then use nichrome wire near the center of thickness direction, to cut thick sheet as 50mm.The tabular formed body of the 350mm * 450mm that cuts * 50mm cuts away half in the central authorities of length direction.Calculating is present in all particles of section, and the particle that expanded particle itself is decided what is right and what is wrong accounts for the percentage ratio (%) of all particles.The fusion rate is 80% to be evaluated as " excellent ◎ " when above, more than 60% but be " good zero " less than 80% the time, more than 40% but be " can accept △ " less than 60% the time, is being " poor * " less than 40% the time.
Embodiment 1
In 100 liters autoclave, in containing 60g tricalcium phosphate as dispersion agent (TCP-10 that large graduation company produces) and the 40kg ion exchanged water as the 0.8g Sodium dodecylbenzene sulfonate of suspension stabilization aid (tensio-active agent), sneak into and be dissolved with 200g tetrabromo cyclooctane (the Pyrogard FR-200 that the first industrial drugmaker produces), the 120g dicumyl peroxide, then the 40kg styrene monomer of 140g benzoyl peroxide (purity 75%) and 30g peroxidized t-butyl perbenzoate under agitation makes it dissolving and disperses to form suspension.
Then, styrene monomer was carried out 6 hours and further 110 ℃ of polyreactions of carrying out 4 hours at 90 ℃.Be in the process of 90 ℃ of reactions, that is, when reaction beginning 2 hours and 3 hours, respectively 6g tricalcium phosphate (TCP-10 of large graduation company production) be appended in the suspension.Reaction makes temperature be down to room temperature (25 ℃) after finishing, and the taking-up content makes it to carry out centrifugal separation processes and dry from autoclave, thereby obtains the styrene resin particle.
The styrene resin particle that obtains is classified into the particle of 0.6mm to 0.7mm.
In 5 liters autoclave, add 2000g water, 9g magnesium pyrophosphate and 0.3g Sodium dodecylbenzene sulfonate with the preparation aqueous medium, add again the above-mentioned particle of 2000g, stir with 300rpm.
Then, be warming up to 95 ℃, keep this temperature, be pressed into simultaneously the 180g butane.Particle with butane dipping 3 hours, is cooled off thereafter and obtains foamable styrene resin particle.The foamable styrene resin particle that obtains leaves standstill 4 days in order to slaking at 15 ℃, then carries out the pre-frothing step.The pre-frothing step is carried out under a certain condition, that is, drop into the resin particle of foamable styrene-based in the pre-foaming machine and utilize steam to make it pre-frothing.The result of pre-frothing is, obtains the volume blowing ratio and be 50 times pre-expanded beads.Fig. 1 illustrates section S EM (scanning electronic microscope) photo of resulting pre-expanded beads.Fig. 1 shows obtained the pre-expanded beads that the thick close variation of bubble is suppressed in embodiment 1.
In addition, make pre-expanded beads leave standstill at normal temperatures 24 hours in order to slaking, in the die cavity of the steam molding machine that its known polystyrene foamed of packing into is used, with 0.6kg/cm
230 seconds of steam heating of G, and 20 seconds of water-cooled are with the piece shape expanded moldings of 300mm * 450mm of obtaining to foam with 50 times blowing ratio * 100mm.
Table 1 shows flame retardant resistance, average bubble size and the heat fusion of the piece shape expanded moldings that obtains.
Embodiment 2
Except the quantitative change that makes the tetrabromo cyclooctane was 400g, all the other are way and obtain expanded moldings similarly to Example 1.
Embodiment 3
Except the quantitative change that makes the tetrabromo cyclooctane was 600g, all the other are way and obtain expanded moldings similarly to Example 1.Fig. 2 illustrates the section S EM photo of resulting pre-expanded beads.Fig. 2 shows obtained the pre-expanded beads that the thick close variation of bubble is suppressed in embodiment 3.
Embodiment 4
Except the quantitative change that makes the tetrabromo cyclooctane was 800g, all the other are way and obtain expanded moldings similarly to Example 1.
Embodiment 5
Except dipping temperature is become 80 ℃, all the other are way and obtain expanded moldings similarly to Example 2.
Embodiment 6
Except dipping temperature is become 100 ℃, all the other are way and obtain expanded moldings similarly to Example 2.
Embodiment 7
Except dipping temperature is become 110 ℃, all the other are way and obtain expanded moldings similarly to Example 2.
Embodiment 8
Except not adding dicumyl peroxide, all the other are way and obtain expanded moldings similarly to Example 3.
Embodiment 9
Except the sulfonated α-olefin that uses 2.2g replaced Sodium dodecylbenzene sulfonate, all the other are way and obtain expanded moldings similarly to Example 5.
Embodiment 10
Except dipping temperature is become 110 ℃, all the other are way and obtain expanded moldings similarly to Example 9.
Embodiment 11
Except with tricalcium phosphate be become the C13-09 that Budenheim company produces from the TCP-10 that large graduation company produces, all the other are way and obtain expanded moldings similarly to Example 2.
Embodiment 12
Except not using tricalcium phosphate but use the 85g magnesium pyrophosphate, all the other are way and obtain expanded moldings similarly to Example 2.
Embodiment 13
Except not using tricalcium phosphate but use the 85g magnesium pyrophosphate, all the other are way and obtain expanded moldings similarly to Example 3.
Comparative Examples 1
Except the quantitative change that makes the tetrabromo cyclooctane was 80g, all the other are way and obtain expanded moldings similarly to Example 1.
Comparative Examples 2
Except the quantitative change that makes the tetrabromo cyclooctane was 160g, all the other are way and obtain expanded moldings similarly to Example 1.
Comparative Examples 3
Except dipping temperature is become 115 ℃, all the other are way and obtain expanded moldings similarly to Example 2.
Comparative Examples 4
Except the quantitative change that makes the tetrabromo cyclooctane was 1200g, all the other are way and obtain expanded moldings similarly to Example 1.Fig. 3 illustrates the section S EM photo of resulting pre-expanded beads.Fig. 3 shows because the consumption of fire retardant is larger in Comparative Examples 4, so bubble is less.
Comparative Examples 5
Except not adding the tetrabromo cyclooctane, all the other are way and obtain the styrene resin particle similarly to Example 1.Make resulting styrene resin particle be classified into the particle of 0.6mm to 0.7mm.
Except under the stirring of 300rpm, add in hydrotropisms's medium beyond the 10g tetrabromo cyclooctane, all the other are way and obtain expanded moldings similarly to Example 1.Fig. 4 illustrates the section S EM photo of resulting pre-expanded beads.Fig. 4 shows that so the bubble size of skin section is less, and the bubble size of central section is larger, produces the thick close variation of bubble because more fire retardant is present in the rim surface zona in Comparative Examples 5.
Comparative Examples 6
Except not adding the tetrabromo cyclooctane, all the other are way and obtain the styrene resin particle similarly to Example 1.Make resulting styrene resin particle be classified into 0.6 to 0.7mm particle.
Except under the stirring of 300rpm, add in hydrotropisms's medium beyond the 30g tetrabromo cyclooctane, all the other are way and obtain expanded moldings similarly to Example 1.Fig. 5 illustrates the section S EM photo of resulting pre-expanded beads.Fig. 5 shows that so the bubble size of skin section is less, and the bubble size of central section is larger, produces the thick close variation of bubble because more fire retardant is present in the rim surface zona in Comparative Examples 6.
Table 1 is illustrated in flame retardant resistance, average bubble size and the heat fusion of the block expanded moldings that obtains in embodiment 2 to 13 and the Comparative Examples 1 to 6.
Table 1 shows by the specific fire retardant that uses specified quantitative and will be made as specified temp with the temperature that pneumatogen floods, a kind of resin particle of foamable styrene-based can be provided, and it has excellent heat fusion and allows to produce the expanded moldings with excellent flame retardancy between particle when foaming.
Measure as follows the skin section of resin particle of the foamable styrene-based that embodiment 1 to 13 and Comparative Examples 1-6 obtain and the containing ratio of the tetrabromo cyclooctane in the integral body, the results are shown in the table 1.
(measuring method of the containing ratio of tetrabromo cyclooctane)
Cut into the sheet of thick 0.2mm, long 20cm and wide 20cm with will foam 50 times the surface of formed body of slicing machine (island worker's machine society of Fuji produce FK-4N), process again the skin section as the foamable styrene resin particle of flame retardant resistance.Measure the containing ratio of the tetrabromo cyclooctane on cropped surface.The measurement of the containing ratio of tetrabromo cyclooctane is by using fluorescent X-ray analysis instrument (RIX-2100 processed of Rigaku company) to utilize Series Analysis method (membrane process) to carry out.Particularly, the film that hot pressing prepares thick 0.1mm to 1mm, long 5cm and wide 5cm is carried out in the surface 2 to 3g that cuts in 200 to 230 ℃.Measure the weight of film and calculate basic weight, utilize C
8H
8As equilibrium composition, calculate the amount of Br from X-ray intensity meter by the Series Analysis method.In view of the percentage ratio of contained Br in the tetrabromo cyclooctane is 75%, thereby can calculate the amount of tetrabromo cyclooctane the film from the amount of resulting Br.With calculation result as the contained tetrabromo cyclooctane containing ratio of the skin section of the foamable styrene resin particle of flame retardant resistance.
Add-on when contained tetrabromo cyclooctane containing ratio floods with the tetrabromo cyclooctane in the integral body of the foamable styrene resin particle of flame retardant resistance is identical.
Fig. 2 illustrates tetrabromo cyclooctane containing ratio contained in the skin section of the foamable styrene resin particle of flame retardant resistance and the integral body, and the ratio of contained tetrabromo cyclooctane containing ratio in the contained tetrabromo cyclooctane containing ratio of skin section and the integral body.
Table 2
| TBCO containing ratio " b " in the integral body (wt%) | TBCO containing ratio " a " (wt%) in the rim surface zona | The rim surface zona of TBCO containing ratio/integral body ratio | b×1.1 | |
| Embodiment 1 | 0.50 | 0.49 | 0.98 | 0.55 |
| Embodiment 2 | 1.00 | 1.01 | 1.01 | 1.1 |
| Embodiment 3 | 1.50 | 1.52 | 1.01 | 1.65 |
| Embodiment 4 | 2.00 | 2.01 | 1.01 | 2.2 |
| Embodiment 5 | 1.00 | 0.99 | 0.99 | 1.1 |
| Embodiment 6 | 1.00 | 1.03 | 1.03 | 1.1 |
| Embodiment 7 | 1.00 | 1.01 | 1.01 | 1.1 |
| Embodiment 8 | 1.50 | 1.50 | 1.00 | 1.65 |
| Embodiment 9 | 1.00 | 1.01 | 1.01 | 1.1 |
| Embodiment 10 | 1.00 | 1.00 | 1.00 | 1.1 |
| Embodiment 11 | 1.00 | 1.00 | 1.00 | 1.1 |
| Embodiment 12 | 1.00 | 0.99 | 0.99 | 1.1 |
| Embodiment 13 | 1.50 | 1.55 | 1.03 | 1.65 |
| Comparative Examples 1 | 0.20 | 0.20 | 1.00 | 0.22 |
| Comparative Examples 2 | 0.40 | 0.41 | 1.01 | 0.44 |
| Comparative Examples 3 | 1.00 | 1.01 | 1.01 | 1.1 |
| Comparative Examples 4 | 3.00 | 2.95 | 0.98 | 3.3 |
| Comparative Examples 5 | 0.50 | 0.56 | 1.12 | 0.55 |
| Comparative Examples 6 | 1.50 | 1.71 | 1.14 | 1.65 |
Table 2 shows, a kind of resin particle that satisfies the foamable styrene-based of formula " a "≤1.1 * " b " can be provided in an embodiment, and it has excellent heat fusion and allows to produce the expanded moldings with excellent flame retardancy between particle when foaming.Table 2 also shows, on the other hand, and heat fusion and/or the poor fire of the expanded moldings that does not satisfy this formula in the Comparative Examples 5 and 6.
Claims (7)
1. method for preparing the resin particle of the foamable styrene-based of flame retardant resistance, described method comprises: the described styrene monomer that adds with respect to 100 weight parts in the suspension polymerization of styrene monomer is the tetrabromo cyclooctane of 0.45 weight part to 2.0 weight part, to obtain the resin particle of styrene-based; And then, during the suspension polymerization of described styrene monomer or flood afterwards the resin particle of described styrene-based with pneumatogen, simultaneously dipping temperature is adjusted to 80 to 110 ℃, to obtain the resin particle of the foamable styrene-based of described flame retardant resistance
Wherein said suspension polymerization is carried out in the presence of tensio-active agent.
2. the method for the resin particle of the foamable styrene-based of preparation flame retardant resistance according to claim 1, wherein said styrene monomer also contains flame retardant.
3. the method for the resin particle of the foamable styrene-based of preparation flame retardant resistance according to claim 2, wherein said flame retardant is selected from cumene hydroperoxide, dicumyl peroxide, tertbutyl peroxide and 2,3-dimethyl-2,3-diphenyl butane.
4. according to claim 2 or the method for the resin particle of the foamable styrene-based of 3 described preparation flame retardant resistances, the consumption of wherein said flame retardant is 0.1 weight part to 0.5 weight part with respect to the described styrene monomer of 100 weight parts.
5. the method for the resin particle of the foamable styrene-based of each described preparation flame retardant resistance according to claim 1～3, wherein regulate described dipping temperature, so that the resin particle by making the foamable styrene-based of described flame retardant resistance can have the average bubble size of 50 μ m to 350 μ m with 50 times the blowing ratio expanded moldings that obtains that foams.
6. the method for the resin particle of the foamable styrene-based of each described preparation flame retardant resistance according to claim 1～3, wherein said styrene monomer is selected from vinylbenzene, alpha-methyl styrene, p-methylstyrene, t-butyl styrene and Benzene Chloride ethene.
7. the resin particle of the foamable styrene-based of flame retardant resistance, it comprises: the resin particle of styrene-based, and be contained in pneumatogen and tetrabromo cyclooctane in the resin particle of described styrene-based;
When the weight percent containing ratio of the contained tetrabromo cyclooctane in the rim surface zona of the resin particle of described styrene-based is " a ", when the weight percent containing ratio of contained tetrabromo cyclooctane was " b " in the integral body of the resin particle of described styrene-based, contained tetrabromo cyclooctane satisfied relational expression " a "≤1.1 * " b " in the resin particle of described styrene-based;
The amount of contained tetrabromo cyclooctane is 0.45 weight part to 2.00 weight part with respect to the resin particle of the described styrene-based of 100 weight parts in the integral body of the resin particle of described styrene-based; And
When the resin particle of the foamable styrene-based of described flame retardant resistance foamed with 50 times blowing ratio, it was the foam of 50 μ m to 350 μ m that average bubble size is provided.
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| JP2007339903 | 2007-12-28 | ||
| PCT/JP2008/073093 WO2009084456A1 (en) | 2007-12-28 | 2008-12-18 | Flame-retardant expandable styrene resin particle, and method for production thereof |
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| JP2013076021A (en) * | 2011-09-30 | 2013-04-25 | Sekisui Plastics Co Ltd | Flame retardant foaming polystyrenic resin particle, method for manufacturing the same, foaming particle, and foam molding |
| CN110713619A (en) * | 2018-07-12 | 2020-01-21 | 第一工业制药株式会社 | Method for producing expandable styrene resin particles |
| CN109574619B (en) * | 2018-11-29 | 2021-04-02 | 中建西部建设股份有限公司 | Preparation method of magnesium phosphate foamed cement |
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| CN1675294A (en) * | 2002-08-09 | 2005-09-28 | 株式会社钟化 | Formable styrenic resin particle, and pre-formed particle and foamed moldings using the same |
| CN1747990A (en) * | 2003-04-04 | 2006-03-15 | 积水化成品工业株式会社 | Expandable styrene-modified olefin resin particle, pre-expanded particle, and process for producing molded foam |
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| JP3995516B2 (en) * | 2002-04-22 | 2007-10-24 | 積水化成品工業株式会社 | Styrenic resin pre-expanded particles having flame retardancy and method for producing the same |
| JP2005015560A (en) * | 2003-06-24 | 2005-01-20 | Jsp Corp | Regenerated expandable styrenic resin particle and its manufacturing method |
| JP4653507B2 (en) * | 2005-02-04 | 2011-03-16 | 積水化成品工業株式会社 | Expandable styrene resin particles |
| JP4937610B2 (en) * | 2005-04-12 | 2012-05-23 | 第一工業製薬株式会社 | Flame-retardant foamed polystyrene resin and molded article thereof |
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| CN1675294A (en) * | 2002-08-09 | 2005-09-28 | 株式会社钟化 | Formable styrenic resin particle, and pre-formed particle and foamed moldings using the same |
| CN1747990A (en) * | 2003-04-04 | 2006-03-15 | 积水化成品工业株式会社 | Expandable styrene-modified olefin resin particle, pre-expanded particle, and process for producing molded foam |
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| Title |
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| JP特开2003-313354A 2003.11.06 |
| JP特开2005-15560A 2005.01.20 |
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| KR20100110788A (en) | 2010-10-13 |
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| TWI428378B (en) | 2014-03-01 |
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