NO138212B - PROCEDURE FOR MANUFACTURE OF SELF-EXTINGUABLE, EXPANDABLE POLYSTYRENE PARTICLES - Google Patents
PROCEDURE FOR MANUFACTURE OF SELF-EXTINGUABLE, EXPANDABLE POLYSTYRENE PARTICLES Download PDFInfo
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- NO138212B NO138212B NO742492A NO742492A NO138212B NO 138212 B NO138212 B NO 138212B NO 742492 A NO742492 A NO 742492A NO 742492 A NO742492 A NO 742492A NO 138212 B NO138212 B NO 138212B
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- Prior art keywords
- pentabromochlorocyclohexane
- styrene
- polymerization
- polymer
- self
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- 238000000034 method Methods 0.000 title claims description 18
- 239000002245 particle Substances 0.000 title claims description 10
- 229920006248 expandable polystyrene Polymers 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 22
- UZOSVZSBPTTWIG-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-chlorocyclohexane Chemical compound ClC1C(Br)C(Br)C(Br)C(Br)C1Br UZOSVZSBPTTWIG-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 150000003254 radicals Chemical class 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 239000007900 aqueous suspension Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 15
- 239000004793 Polystyrene Substances 0.000 description 12
- 229920002223 polystyrene Polymers 0.000 description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 10
- -1 bromine compound Chemical class 0.000 description 10
- 229910052794 bromium Inorganic materials 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000002366 halogen compounds Chemical class 0.000 description 6
- 239000000375 suspending agent Substances 0.000 description 6
- 239000004604 Blowing Agent Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000001506 calcium phosphate Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 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 description 4
- 229940078499 tricalcium phosphate Drugs 0.000 description 4
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 4
- 235000019731 tricalcium phosphate Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- 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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 239000013068 control sample Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002102 polyvinyl toluene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polymerisation Methods In General (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Description
Oppfinnelsen vedrører en'fremgangsmåte for fremstilling The invention relates to a method of production
av selvslukkende, ekspanderbare polystyrenpartikler. of self-extinguishing, expandable polystyrene particles.
Det er kjent, f.eks. fra US-patenter nr. 3 058 926 og It is known, e.g. from US Patents Nos. 3,058,926 and
3 2 74 133, å gjøre polystyren selvslukkende ved tilsetning av organiske halogenholdige forbindelser. Når pentabromklorcykloheksan innlemmes i polymeren, f.eks. ved tilsetning av halogenforbindelsen under "hard-bead~."-impregneringen med et esemiddel, blir polystyrenet varmefølsomt. Tilsetning av pentabromklorcykloheksanet til monomerblandingen før polymerisasjonen i f.eks. en vandig suspensjonspolymerisasjon, interfererer med polymerisasjonen av styrenet og resulterer i dannelse av et lavmolekylært polystyren. 3 2 74 133, to make polystyrene self-extinguishing by adding organic halogen-containing compounds. When pentabromochlorocyclohexane is incorporated into the polymer, e.g. by adding the halogen compound during the "hard-bead~" impregnation with a foaming agent, the polystyrene becomes heat sensitive. Addition of the pentabromochlorocyclohexane to the monomer mixture prior to polymerization in e.g. an aqueous suspension polymerization, interferes with the polymerization of the styrene and results in the formation of a low molecular weight polystyrene.
Det har nå vist seg at det kan fremstilles et varmesta-bilt , selvslukkende, ekspanderbart polystyren ved polymerisering av styren i vandig suspensjon til mellom 92 og 98 % av monomeren er overført til polymer, tilsetning av pentabromklorcykloheksan, esemiddel og ytterligere friradikal-initiator til suspensjonen, hvoretter polymerisasjonen fortsettes til fullført omdannelse. Halogenforbindelsen innlemmes øyensynlig i polystyrenkjedene ved It has now been shown that a heat-stable, self-extinguishing, expandable polystyrene can be produced by polymerization of styrene in aqueous suspension until between 92 and 98% of the monomer has been transferred to polymer, addition of pentabromochlorocyclohexane, blowing agent and additional free radical initiator to the suspension , after which the polymerization is continued until complete conversion. The halogen compound is apparently incorporated into the polystyrene chains by
en kjedeoverføringsreaksjon. a chain transfer reaction.
I henhold til oppfinnelsen tilveiebringes en fremgangsmåte for fremstilling av selvslukkende, ekspanderbare polystyrenpartikler ved polymerisering av styren i en vandig suspensjon i nærvær av en katalytisk mengde av en friradikal-initiator, et esemiddel og pentabromklorcykloheksan, og fremgangsmåten er karakterisert ved at styren polymeriseres i nærvær av friradikal-initiatoren til 92-98 % omdannelse av monomer til polymer, at det ved et punkt mellom 92 og 98 % omdannelse tilsettes en blanding av 0,5-5,0 vekt%, basert på styren,av pentabromklorcykloheksan, According to the invention, a method is provided for the production of self-extinguishing, expandable polystyrene particles by polymerizing styrene in an aqueous suspension in the presence of a catalytic amount of a free radical initiator, a blowing agent and pentabromochlorocyclohexane, and the method is characterized in that the styrene is polymerized in the presence of the free radical initiator to 92-98% conversion of monomer to polymer, that at a point between 92 and 98% conversion a mixture of 0.5-5.0% by weight, based on styrene, of pentabromochlorocyclohexane is added,
5-15 % av et esemiddel og ytterligere 0,3-0,5 % friradikal-initiator, og at pentabromklorcykloheksanet inkorporeres kjemisk i de 5-15% of a blowing agent and a further 0.3-0.5% free radical initiator, and that the pentabromochlorocyclohexane is chemically incorporated into the
voksende polymerkjeder ved fullførelse av polymerisasjonen i vandig suspensjon ved oppvarming av suspensjonen under temperatur- growing polymer chains upon completion of the polymerization in aqueous suspension by heating the suspension below temperature
og tidsbetingelser som er tilstrekkelige til å polymerisere den gjenværende monomer fullstendig, og at polymerpartiklene utvinnes. and time conditions sufficient to completely polymerize the remaining monomer and recover the polymer particles.
Polymerisering av styren i vandig suspensjon er en vel-kjent operasjon. Styrenet og en friradikal-initiator i form av en oljefase blandes med vann og oppvarmes. Blandingen røres eller agiteres slik at oljefasen er i form av små, individuelle dråper. Etter at polymerisasjonen er kommet til et visst punkt, har dråpene tendens til å bli klebrige, slik at røring alene er utilstrekkelig til å holde dråpene fra koalescering. Det er derfor nødvendig å anvende et suspenderingsmiddel i polymerisasjonsblandingen. Eksempler på egnede suspenderingsmidler er polyvinylalkohol, hydroksy-etylcellulose og en blanding av trikalsiumfosfat og et anionisk overflateaktivt middel. Polymerization of styrene in aqueous suspension is a well-known operation. The styrene and a free radical initiator in the form of an oil phase are mixed with water and heated. The mixture is stirred or agitated so that the oil phase is in the form of small, individual droplets. After the polymerization has reached a certain point, the droplets tend to become sticky, so that stirring alone is insufficient to keep the droplets from coalescing. It is therefore necessary to use a suspending agent in the polymerization mixture. Examples of suitable suspending agents are polyvinyl alcohol, hydroxyethyl cellulose and a mixture of tricalcium phosphate and an anionic surfactant.
Temperaturen for polymerisasjonen må være høy nok til at polymerisasjonen finner sted med rimelig hastighet, og det foretrukne temperaturområde ligger mellom 70 og 120°C. The temperature for the polymerization must be high enough for the polymerization to take place at a reasonable rate, and the preferred temperature range is between 70 and 120°C.
Typiske radikal-initiatorer er de oljeløselige peroksy-der, f.eks. benzoylperoksyd, lauroylperoksyd og t-butylperbenzoat, samt azobisisobutyronitril. Typical radical initiators are the oil-soluble peroxides, e.g. benzoyl peroxide, lauroyl peroxide and t-butyl perbenzoate, as well as azobisisobutyronitrile.
I overensstemmelse med oppfinnelsen, når polymerisasjonen har nådd et punkt mellom 92 og 98 % omdannelse av styrenet til polystyren, tilsettes en blanding av pentabromklorcykloheksan, esemiddel og ytterligere initiator til suspensjonen, og polymeri-sas jonen fortsettes så til fullstendig omdannelse. In accordance with the invention, when the polymerization has reached a point between 92 and 98% conversion of the styrene to polystyrene, a mixture of pentabromochlorocyclohexane, blowing agent and additional initiator is added to the suspension, and the polymerization is then continued until complete conversion.
Pentabromklorcykloheksanet anvendes i mengder mellom 0,5 og 5,0 vekt% basert på styrenmonomeren. Mindre enn 0,5 % av halogenforbindelsen gir ikke en selvslukkende polymer. Mer enn 5,0 % er ikke nødvendig for at polymeren skal få selvslukkende egenskaper. The pentabromochlorocyclohexane is used in amounts between 0.5 and 5.0% by weight based on the styrene monomer. Less than 0.5% of the halogen compound does not give a self-extinguishing polymer. More than 5.0% is not necessary for the polymer to acquire self-extinguishing properties.
Esemidlene er forbindelser som er gasser eller normalt flytende, men som vil gi gasser ved oppvarmning. Foretrukne esemidler omfatter alifatiske hydrokarboner som inneholder 1-7 karbonatomer i molekylet, f.eks. petroleter eller metan, etan, propan, butan, pentan, heksan, heptan, cykloheksan, isopentan og deres halogenerte derivater som koker ved en temperatur under poly-merens mykningspunkt. Midlene anvendes i mengder mellom 5 og 15 vekt% regnet på polymerpartiklene. The evaporating agents are compounds which are gases or normally liquid, but which will give off gases when heated. Preferred emulsifiers include aliphatic hydrocarbons containing 1-7 carbon atoms in the molecule, e.g. petroleum ether or methane, ethane, propane, butane, pentane, hexane, heptane, cyclohexane, isopentane and their halogenated derivatives which boil at a temperature below the softening point of the polymer. The agents are used in amounts between 5 and 15% by weight calculated on the polymer particles.
Oppfinnelsen skal i det følgende illustreres ved hjelp In the following, the invention will be illustrated with help
av eksempler. of examples.
Eksempel I Example I
Til en egnet reaktor utstyrt med rører ble tilsatt 100 deler vann, 0,64 del trikalsiumfosfat og 0,0048 del natriumdode-cylbenzensulfonat. Systemet ble spylt med nitrogen. Det ble så tilsatt 100 deler styren som inneholdt 0,37 del benzoylperoksyd og 0,10 del t-butylperbenzoat. Blandingen ble oppvarmet til 90°C i løpet av ca. 1 time, under agitering, og ble holdt ved 90°C i tilnærmet 5 timer eller inntil tilnærmet 92-95 % omdannelse, hvilket ble bestemt ved prøvetagning. Det ble så tilsatt 0,5 del pentabromklorcykloheksan, 0,35 del 2,5-dimetyl-2,5-di(tert.-butyl-peroksy)heksan og 9,0 deler n-pentan. Temperaturen til blandingen ble så hevet til 110°C og holdt ved denne temperatur i 6 timer for fullstendig å polymerisere den gjenværende monomer. Polymerpartiklene ble utvunnet fra polymerisasjonsblandingen, vasket og tørket. To a suitable reactor equipped with stirrers were added 100 parts of water, 0.64 part of tricalcium phosphate and 0.0048 part of sodium dodecylbenzene sulphonate. The system was flushed with nitrogen. 100 parts of styrene containing 0.37 parts of benzoyl peroxide and 0.10 parts of t-butyl perbenzoate were then added. The mixture was heated to 90°C during approx. 1 hour, with agitation, and was held at 90°C for approximately 5 hours or until approximately 92-95% conversion as determined by sampling. 0.5 parts of pentabromochlorocyclohexane, 0.35 parts of 2,5-dimethyl-2,5-di(tert-butyl-peroxy)hexane and 9.0 parts of n-pentane were then added. The temperature of the mixture was then raised to 110°C and held at this temperature for 6 hours to completely polymerize the remaining monomer. The polymer particles were recovered from the polymerization mixture, washed and dried.
En kontrollprøve ble utført ved den identiske prosess, mens man utelot halogenforbindelsen fra impregnerings- og fullfø-relsestrinnet. A control sample was carried out by the identical process, while omitting the halogen compound from the impregnation and finishing step.
Polystyrenet fra kontrollprøven og det som ble fremstilt ved fremgangsmåten i henhold til oppfinnelsen, var i alt vesentlig like med hensyn til molekylvekt. The polystyrene from the control sample and that produced by the method according to the invention were essentially the same in terms of molecular weight.
Skumstrimler med tetthet ca. 20 kg/m3 ble støpt av de to prøver av ekspanderbare kuler og ble testet med hensyn på selvslukkende egenskaper ved at strimlene ble holdt i vertikal posisjon og ved påføring av en flamme i nedre ende. Ved fjerning av flammen fortsatte strimlene fra kontrollprøven å brenne, mens på strimlen av prøven som inneholdt halogenforbindelsen, flammen sluknet i løpet av mindre enn to sekunder. Foam strips with a density of approx. 20 kg/m3 were cast from the two samples of expandable balls and were tested for self-extinguishing properties by holding the strips in a vertical position and by applying a flame at the lower end. On removal of the flame, the strips from the control sample continued to burn, while on the strip of the sample containing the halogen compound, the flame went out in less than two seconds.
Pentabromklorcykloheksanet kunne ikke utlutes fra poly-styrenprøven - hvilket indikerer at forbindelsen var kjemisk in-korporert i polymerkjedene„ The pentabromochlorocyclohexane could not be leached from the polystyrene sample - indicating that the compound was chemically incorporated into the polymer chains.
Eksempel II Example II
Fremgangsmåten fra eksempel I ble gjentatt under anvendel-se av 0,10, 0,20, 0,30, 0,50, 1,0, 3,0 og 5,0 deler pentabromklorcykloheksan i impregneringstrinnet. De resulterende ekspanderbare perler ble støpt til skumstrimler med tettheter på mindre enn 24 kg/m<3>. The procedure from Example I was repeated using 0.10, 0.20, 0.30, 0.50, 1.0, 3.0 and 5.0 parts of pentabromochlorocyclohexane in the impregnation step. The resulting expandable beads were molded into foam strips with densities of less than 24 kg/m<3>.
Skum som inneholdt mindre enn 0,5 del av halogenforbindelsen pr. Foam that contained less than 0.5 part of the halogen compound per
100 deler polystyren, ble fullstendig brent ved testing i verti-kalstrimmeltesten. De skum som inneholdt 0,5 eller mer av halo-genf orbindelsen , var selvslukkende. 100 parts polystyrene was completely burned when tested in the vertical strip test. The foams which contained 0.5 or more of the halo-regen compound were self-extinguishing.
Eksempel III Example III
I den hensikt å vise at fremgangsmåten i henhold til oppfinnelsen avviker fra fremgangsmåten i henhold til US-patent nr. 3 058 926 ble fremgangsmåten fra eksempel 8 i henhold til patentet utført som følger: En sats bestående av 100 g styren, 0,225 vekt% benzoylperoksyd og 6,4% pentan av kommersiell kvalitet ble anbragt i et trykkresistent kar i blanding med samme vektmengde av en vandig løsning av 1% polyvinylalkohol som suspenderingsmiddel. Blandingen ble omrørt og ble oppvarmet i det lukkede kar for polymerisering av monomeren under tids- og temperaturbetingelser som følger: 16 timer ved 82°C, 2 timer ved 98°C og 6 timer ved 120°C. Deretter ble blandingen avkjølt til 95°C. En løsning av 10 ml vann inneholdende 1 vekt% metylcellulose og en løsning av 3,0% av pentanet, 1,1% pentabromklorcykloheksan og 0,4% dikumylperoksyd ble tilsatt til karet. Den resulterende blanding ble omrørt og opprettholdt ved en temperatur på 9 5°C i 2 timer og ble deretter avkjølt til 20°C. Polymerperlene ble separert fra den vandige væske og ble vasket og tørket. Den tørkede polymer ble ekstrahert med en blanding av metanol og n-pentan og ekstrakten analysert med hensyn på bromforbindelse. Bromforbindelsen ble funnet å være i stor grad til stede i ekstrakten, hvilket indikerer at bromforbindelsen ikke blir kjemisk forbundet med polystyrenet, og hvilket videre indikerer at styrenet ble polymerisert til mer enn 98% omdannelse ved den innledende polymerisasjonsplan. Siden fremgangsmåten i hen- In order to show that the method according to the invention deviates from the method according to US patent no. 3,058,926, the method from example 8 according to the patent was carried out as follows: A batch consisting of 100 g styrene, 0.225% by weight benzoyl peroxide and 6.4% commercial grade pentane was placed in a pressure-resistant vessel in admixture with an equal amount by weight of an aqueous solution of 1% polyvinyl alcohol as suspending agent. The mixture was stirred and was heated in the closed vessel to polymerize the monomer under time and temperature conditions as follows: 16 hours at 82°C, 2 hours at 98°C and 6 hours at 120°C. The mixture was then cooled to 95°C. A solution of 10 ml of water containing 1% by weight of methylcellulose and a solution of 3.0% of the pentane, 1.1% of pentabromochlorocyclohexane and 0.4% of dicumyl peroxide was added to the vessel. The resulting mixture was stirred and maintained at a temperature of 95°C for 2 hours and was then cooled to 20°C. The polymer beads were separated from the aqueous liquid and were washed and dried. The dried polymer was extracted with a mixture of methanol and n-pentane and the extract analyzed for bromine compound. The bromine compound was found to be largely present in the extract, indicating that the bromine compound does not become chemically associated with the polystyrene, and further indicating that the styrene was polymerized to greater than 98% conversion at the initial polymerization schedule. Since the procedure in
hold til oppfinnelsen ga et polystyren som har bromforbindelsen kjemisk bundet i polymeren, er de to fremgangsmåter ikke like. unless the invention produced a polystyrene which has the bromine compound chemically bound in the polymer, the two methods are not the same.
Gjentagelse av ovennevnte fremgangsmåte, under anven-delse av 0,4 g trikalsiumfosfat og 32 ml av en .0,01% vandig løs-ning av natriumbisulfitt,istedenfor polyvinylalkoholen som suspenderingsmiddel, ga de samme resultater. Bromforbindelsen viste seg i vesentlig grad i ekstrakten. Repetition of the above procedure, using 0.4 g of tricalcium phosphate and 32 ml of a 0.01% aqueous solution of sodium bisulphite, instead of the polyvinyl alcohol as suspending agent, gave the same results. The bromine compound appeared to a significant extent in the extract.
Natriumsaltet av sulfonert polyvinyltoluen anvendt The sodium salt of sulfonated polyvinyltoluene used
som suspenderingsmiddel i fremgangsmåten i henhold til US-patent as suspending agent in the method according to the US patent
nr. 3 058 926 kunne ikke fåes fra kommersielle kilder. Det er ingen grunn til å anta at naturen av suspenderingsmidlet ville påvirke resultatene. No. 3,058,926 could not be obtained from commercial sources. There is no reason to suppose that the nature of the suspending agent would affect the results.
Eksempel IV Example IV
For å illustrere det faktura at impregneringen av polystyren som var polymerisert til minst 99,7% omdannelse, som vist i US-patentskrift nr. 3 274 133, ikke tillater kjemisk binding av bromforbindelsen til polystyrenet, ble følgende forsøk utført: In order to illustrate the fact that the impregnation of polystyrene that had been polymerized to at least 99.7% conversion, as shown in US Patent No. 3,274,133, does not allow chemical binding of the bromine compound to the polystyrene, the following experiment was carried out:
Det blegjort et første forsøk som kopierte eksempel I A first attempt was made that copied example I
i foreliggende søknad. -Bromforbindelsen kunne ikke finnes i ekstrakten. in the present application. - The bromine compound could not be found in the extract.
I et annet forsøk ble styren polymerisert i suspensjon til minst 99,7% omdannelse, som angitt i eksempel I i henhold til US-patent nr. 3 274 133. Polymerkulene som således dannet seg, ble suspendert i vann som inneholdt trikalsiumfosfat og natriumbenzensulfonat, som suspensjonsstabilisatorer. Etter tilsetning av en blanding av 8,0% n-pentan som esemiddel og 1,1% pentabromklorcykloheksan -ble suspensjonen oppvarmet til 90°C In another experiment, the styrene was polymerized in suspension to at least 99.7% conversion, as indicated in Example I according to US Patent No. 3,274,133. The polymer spheres thus formed were suspended in water containing tricalcium phosphate and sodium benzenesulfonate, as suspension stabilizers. After adding a mixture of 8.0% n-pentane as blowing agent and 1.1% pentabromochlorocyclohexane - the suspension was heated to 90°C
i 5 timer for å sikre impregnering av polymerpartiklene. Ekstrak-sjon av de resulterende polymerpartikler med en metanol/pentan-blanding viste at i alt vesentlig all bromforbindelse var til stede i ekstrakten. for 5 hours to ensure impregnation of the polymer particles. Extraction of the resulting polymer particles with a methanol/pentane mixture showed that essentially all the bromine compound was present in the extract.
Av dette kan man se at den fremgangsmåte som er be-skrevet i US-patentskrift nr. 3 274 133, ikke inkorporerer bromforbindelsen i polymeren i uekstraherbar form. Siden fremgangsmåten i henhold til foreliggende søknad inkorporerer bromforbindelsen i polymeren på en måte som gjør den uekstraherbar, sees det at de to fremgangsmåter er fundamentalt forskjellige. From this it can be seen that the method described in US Patent No. 3,274,133 does not incorporate the bromine compound into the polymer in an unextractable form. Since the method according to the present application incorporates the bromine compound into the polymer in a way that makes it unextractable, it can be seen that the two methods are fundamentally different.
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US37774873A | 1973-07-09 | 1973-07-09 |
Publications (3)
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NO742492L NO742492L (en) | 1975-02-03 |
NO138212B true NO138212B (en) | 1978-04-17 |
NO138212C NO138212C (en) | 1978-07-26 |
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NO742492A NO138212C (en) | 1973-07-09 | 1974-07-08 | PROCEDURE FOR MANUFACTURE OF SELF-EXTINGUABLE, EXPANDABLE POLYSTYRENE PARTICLES |
Country Status (11)
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JP (1) | JPS5039380A (en) |
AR (1) | AR200524A1 (en) |
BE (1) | BE817428A (en) |
BR (1) | BR7405619D0 (en) |
CA (1) | CA1019500A (en) |
DE (1) | DE2431337B2 (en) |
FR (1) | FR2236883B1 (en) |
GB (1) | GB1463378A (en) |
NL (1) | NL7409051A (en) |
NO (1) | NO138212C (en) |
SE (1) | SE395904B (en) |
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JPH0653193U (en) * | 1992-12-29 | 1994-07-19 | 株式会社ユメディア | Ballpoint pen |
PL2105457T5 (en) * | 2008-03-27 | 2019-05-31 | Arkema France | Process for the preparation of expandable polystyrene |
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US3058929A (en) * | 1958-07-24 | 1962-10-16 | Dow Chemical Co | Method of polymerizing a vinyl aromatic monomer in the presence of an organic bromide and an organic peroxide and a self-extinguishing vinyl aromatic polymer containing same |
BE729746A (en) * | 1968-08-15 | 1969-08-18 |
-
1974
- 1974-06-28 GB GB2894774A patent/GB1463378A/en not_active Expired
- 1974-06-29 DE DE19742431337 patent/DE2431337B2/en not_active Withdrawn
- 1974-07-04 JP JP49076876A patent/JPS5039380A/ja active Pending
- 1974-07-04 NL NL7409051A patent/NL7409051A/en not_active Application Discontinuation
- 1974-07-05 CA CA204,214A patent/CA1019500A/en not_active Expired
- 1974-07-05 SE SE7408874A patent/SE395904B/en unknown
- 1974-07-08 FR FR7423724A patent/FR2236883B1/fr not_active Expired
- 1974-07-08 AR AR254589A patent/AR200524A1/en active
- 1974-07-08 NO NO742492A patent/NO138212C/en unknown
- 1974-07-08 BR BR5619/74A patent/BR7405619D0/en unknown
- 1974-07-09 BE BE146366A patent/BE817428A/en unknown
Also Published As
Publication number | Publication date |
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SE395904B (en) | 1977-08-29 |
DE2431337B2 (en) | 1977-12-01 |
NO138212C (en) | 1978-07-26 |
FR2236883A1 (en) | 1975-02-07 |
NO742492L (en) | 1975-02-03 |
JPS5039380A (en) | 1975-04-11 |
AR200524A1 (en) | 1974-11-15 |
SE7408874L (en) | 1975-01-10 |
DE2431337A1 (en) | 1975-01-30 |
NL7409051A (en) | 1975-01-13 |
CA1019500A (en) | 1977-10-18 |
BR7405619D0 (en) | 1975-05-13 |
GB1463378A (en) | 1977-02-02 |
BE817428A (en) | 1974-11-04 |
FR2236883B1 (en) | 1978-11-24 |
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