DK154776B - PROCEDURE FOR THE PREPARATION OF AN EXTENSIVE FOAM BODY OF A THERMOPLASTIC, SYNTHETIC, ALKENYLAROMATIC POLYMER - Google Patents
PROCEDURE FOR THE PREPARATION OF AN EXTENSIVE FOAM BODY OF A THERMOPLASTIC, SYNTHETIC, ALKENYLAROMATIC POLYMER Download PDFInfo
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- DK154776B DK154776B DK044477AA DK44477A DK154776B DK 154776 B DK154776 B DK 154776B DK 044477A A DK044477A A DK 044477AA DK 44477 A DK44477 A DK 44477A DK 154776 B DK154776 B DK 154776B
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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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
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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
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Description
Opfindelsen angår en fremgangsmåde til fremstilling af et af langt skumstof legeme af en termoplastisk, syntetisk, alkenyl- aromatisk polymer ifølge den indledende del af patentkravet.The invention relates to a process for producing a long foamed body of a thermoplastic, synthetic, alkenyl aromatic polymer according to the preamble of the claim.
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5 En af hovedanvendelserne for styrenpolymerskumstoffer er varmeisoleringsområdet. Et styrenpolymerskumstof til varmeisolering har gerne små celler og fremragende dimensionsstabilitet.5 One of the main uses for styrene polymer foams is the thermal insulation area. A styrene polymer foam for thermal insulation preferably has small cells and excellent dimensional stability.
Det er også særdeles ønskværdigt, at skumstoffets isoleringsværdi opretholdes i et så langt tidsrum som muligt. Fra et 10 fremsti 11ingsmæssigt synspunkt har visse halogenholdige for bindelser, såsom dichlordifluormethan været velegnede i forbindelse med fremstillingen af ekstruderede styrenpolymerskum-stoffer. For tiden antages det, at sådanne forbindelser, når de frigives i atmosfæren, kan reducere ozonlagets effektivitet 15 som solskjold, og det er derfor ønskeligt, at fluorerede og/eller chlorerede forbindelser, der kan reducere ozonlagets effektivitet, generelt kan elimineres fra anvendelser, hvor de til sidst frigives til atmosfæren.It is also highly desirable that the insulating value of the foam be maintained for as long as possible. From a manufacturing standpoint, certain halogen-containing compounds such as dichlorodifluoromethane have been well suited for the preparation of extruded styrene polymer foams. Currently, it is believed that such compounds, when released into the atmosphere, can reduce the efficiency of the ozone layer 15 as a sun shield, and it is therefore desirable that fluorinated and / or chlorinated compounds which can reduce the ozone layer's effectiveness can generally be eliminated from applications where they are eventually released into the atmosphere.
20 Fra US patentskrift nr. 3.287.477 og fransk patentskrift nr. 1.215.410 kendes polystyrenskumstoffer, der f.eks. kan indeholde l-chlor-l,l,2,2,2-pentafluorethan, eventuelt i blanding med andre fluorerede og/eller chlorerede forbindelser eller hydrocarboner. I US patentskrift nr. 3.287.477 beskrives såle-25 des en ekstruderingsfremgangsmåde og en dertil egnet indretning, hvormed man udover skumbare polymerer også kan fremstille opskummede termoplastiske polymerer, hvortil der kan anvendes flydende eller gasformige produkter som skummiddel. Fransk patentskrift nr. 1.215.410 angår ligeledes en fremgangsmåde 30 til fremstilling af skumbare polymermasser på grundlag af termopl astiske, al kyl alkenyl aromatiske polymerer, de derved opnåede skumbare masser samt de heraf dannede skumlegemer, der har en massefylde på 20 til 25 g/1.From U.S. Patent No. 3,287,477 and French Patent No. 1,215,410, polystyrene foams are known which, e.g. may contain 1-chloro-1,1,2,2,2-pentafluoroethane, optionally in admixture with other fluorinated and / or chlorinated compounds or hydrocarbons. Thus, US Patent No. 3,287,477 discloses an extrusion process and a suitable device which, in addition to foamable polymers, can also produce foamed thermoplastic polymers for which liquid or gaseous products can be used as foaming agents. French Patent No. 1,215,410 also relates to a process 30 for the production of foamable polymer masses based on thermoplastic, all-cooled alkenyl aromatic polymers, the foamable masses thus obtained and the foamed bodies having a density of 20 to 25 g / m first
35 Formålet med opfindelsen er derfor at tilvejebringe en fremgangsmåde til fremstilling af et aflangt skumstof legeme af en termoplastisk, syntetisk, alkenylaromatisk polymer, der har en høj dimensionsstabilitet og en god varmeisoleringsevne med 2The object of the invention is therefore to provide a process for producing an elongated foam body of a thermoplastic, synthetic, alkenyl aromatic polymer having a high dimensional stability and good thermal insulation ability with 2
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gunstig ældningsbestandighed, hvorved der ved udvælgelsen af skummiddelblandingen forhindres, at der er fare for ozonlaget.favorable aging resistance, thereby preventing the danger of the ozone layer in selecting the foaming agent mixture.
a Opfindelsen angår en fremgangsmåde til fremstilling af et af- 5 langt skumstoflegeme af en termoplastisk, syntetisk, alkenyl- aromatisk polymer med en maskinretning og en tværretning, idet legemet afgrænser et stort antal lukkede, ikke indbyrdes forbundne gasholdige celler, cellerne har en gennemsnitlig cellestørrelse fra 0,1 til 1,2 mm, skumstof legemet har en overve-10 jende ensartet cellestruktur og er uden diskontinuiteter, le gemet er uden væsentlig variation i gennemsnitlig cellestørrelse, når cellestørrelsen måles ved at tage gennemsnitet af cellediameteren tværs over legemets mindste tværsnitsdimension (måles f.eks. ved hjælp af ASTM-metode D 2842-69), har et 15 tværsnitsareal på mindst 51,6 cm2 og en mindste tværsnitsdi mension på mindst 6,35 mm, idet skumstof legemet har en vand-damppermeabi1itet, som ikke er større end 2,27 g»cm/dm2 mbar og målt ved hjælp af ASTM metode C 355-64 Procedures for Desiccant Method, en massefylde fra 16 til 80 g/1, hvilken frem-20 gangsmåde er ejendommelig ved, at der anvendes et skummiddel eller en skummiddelblanding af a) 30 til 100 vægt% 1,1-dif1uor-l-chlorethan og eventuelt mindst én anden forbindelse med formlen: 25 Ri - CF2 - R2 hvori Ri er en methyl-, ethyl-, chlormethyl-, dif1uormethyl-, chlorf1uormethy1 -, fluormethyl- eller trif1uormethylgruppe, og r2 er hydrogen, chlor, fluor eller en trif1uormethy1- eller methylgruppe, og at forbindelsen indeholder højst 3 carbonato-30 mer, og hvis forbindelsen som halogen kun indeholder 2 fluoratomer, skal forbindelsen have 3 carbonatomer, og b) fra 0 til 30 vægt% af mindst én forbindelse valgt blandt f luorchlormethan, methylchlorid, ethylchlorid, chlordifluor- 35 methan eller 1,1-difluorethan.The invention relates to a method for producing a long foam body of a thermoplastic, synthetic, alkenyl aromatic polymer having a machine direction and a transverse direction, the body defining a large number of closed, unrelated gaseous cells, the cells having an average cell size from 0.1 to 1.2 mm, the foam body has a predominantly uniform cell structure and is free of discontinuities, the store is without significant variation in average cell size when measuring cell size by taking average cell diameter across the smallest cross-sectional dimension of the body ( is measured, for example, by ASTM method D 2842-69), has a cross-sectional area of at least 51.6 cm 2 and a minimum cross-sectional dimension of at least 6.35 mm, the foam body having a water vapor permeability which is not is greater than 2.27 g »cm / dm2 mbar and measured by ASTM Method C 355-64 Procedures for Desiccant Method, a density of 16 to 80 g / l, which method is characterized by using a foaming agent or a foaming mixture of a) 30 to 100% by weight of 1,1-difluoro-1-chloroethane and optionally at least one other compound of the formula: R 1 - CF 2 - R 2 wherein R 1 is a methyl, ethyl, chloromethyl, difluoromethyl, chlorofluoromethyl, fluoromethyl or trifluoromethyl group, and r 2 is hydrogen, chloro, fluoro or a trifluoromethyl or methyl group and the compound contains no more than 3 carbon atoms and if the compound contains only halogen 2 fluorine atoms, the compound must have 3 carbon atoms, and b) from 0 to 30% by weight of at least one compound selected from fluorochloromethane, methyl chloride, ethyl chloride, chlorodifluoromethane or 1,1-difluoroethane.
Flygtige flydende opskumningsmidler, som anvendes til at fremstille skumstoffer i overensstemmelse med fremgangsmåden iføl-Volatile liquid foaming agents used to make foams in accordance with the method of
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3 ge den foreliggende opfindelse, kan være blandinger af et skummiddel med høj permeabilitet og et skummiddel med lav permeabilitet. Enten skummidlet med høj permeabilitet og/eller skummidlet med lav permeabilitet kan være en blanding af et 5 eller flere egnede skummidler. Skummidlet med lav permeabilitet i blandingen af skummidler, som kan anvendes til at fremstille skumstoffer i overensstemmelse med den foreliggende opfindelse, udgør hensigtsmæssigt fra 30 til 70 vægt% af skummi dde Ibland i ngen .3 according to the present invention may be mixtures of a high permeability foam agent and a low permeability foam agent. Either the high permeability foam agent and / or the low permeability foam agent may be a mixture of one or more suitable foaming agents. The low permeability foaming agent in the mixture of foaming agents which can be used to make foams in accordance with the present invention is conveniently from 30 to 70% by weight of foam sometimes at any one time.
1010
Skummidler med lav permeabilitet er: 1,1,1-trifluorpropan, 2.2- di f1uorpropan, 1,1,2,2-tetrafl uorethan, 1,1,1,2-tetraflu- or-2-chlorethan, 1,1,1-trif1uor-2-chlorethan, pentafluorethan, 1.1.2- trif1uorethan, 1,1,1-trifluorethan, octaf1uorpropan og 15 1,1-difluor-lchlorethan og blandinger deraf. Alle de foregå ende forbindelser har den krævede permeabi1 itetsværdi og var-meledni ngsevne.Low permeability foams are: 1,1,1-trifluoropropane, 2.2-di fluoropropane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoro-2-chloroethane, 1.1, 1-trifluoro-2-chloroethane, pentafluoroethane, 1.1.2-trifluoroethane, 1,1,1-trifluoroethane, octafluoropropane and 1,1-difluoro-chloroethane and mixtures thereof. All the preceding compounds have the required permeability value and thermal conductivity.
Sekundære skummidler eller skummidler med høj permeabilitet, 20 som er velegnede ved fremstillingen af skumstof i overensstemmelse med den foreliggende opfindelse, omfatter: fluorchlor-methan, methylchlorid, ethylchlorid, chlordif1uormethan og 1,1-dif1uorethan og blandinger deraf.Secondary or high permeability foams suitable for the preparation of foams in accordance with the present invention include: fluorochloromethane, methyl chloride, ethyl chloride, chlorodifluoromethane and 1,1-difluoroethane and mixtures thereof.
25 Udtrykket "alkenylaromatisk, thermoplastisk, syntetisk poly mer" betegner en fast polymer ud fra en eller flere polymeri-serbare alkenylaromatiske forbindelser. Polymeren eller copo-lymeren omfatter i kemisk bundet form mindst 70 vægt% af mindst én alkenylaromatisk forbindelse med den almene formel 30The term "alkenyl aromatic, thermoplastic, synthetic polymer" refers to a solid polymer from one or more polymerizable alkenyl aromatic compounds. The polymer or copolymer comprises in chemically bonded form at least 70% by weight of at least one alkenyl aromatic compound of the general formula
RR
Ar-C=CH2 hvori Ar betegner en aromatisk hydrocarbongruppe eller en aro-matisk halogen-hydrocarbongruppe af benzenrækken, og R er hy-drogen eller methylgruppen. Eksempler på alkenylaromatiske harpikser er de faste homopolymerer af styren, a-methylstyren, o-methylstyren, m-methylstyren, p-methylstyren, ar-ethylsty- 4Ar-C = CH 2 wherein Ar represents an aromatic hydrocarbon group or an aromatic halohydrocarbon group of the benzene series and R is the hydrogen or methyl group. Examples of alkenyl aromatic resins are the solid homopolymers of styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ar-ethylstyrene.
DK 15 4 7 7 6 BDK 15 4 7 7 6 B
ren, ar-vinylxylen, ar-chlorstyren eller ar-bromstyren og de faste copolymerer af to eller flere af sådanne alkenylaroma-tiske forbindelser med mindre mængder af andre let polymeri-serbare olefiniske forbindelser, såsom f.eks. methylmethacry-5 lat, acrylonitril, maleinsyreanhydrid, citraconsyreanhydrid, itaconsyreanhydrid, acrylsyre og gummi forstærkede (enten naturlige eller syntetiske) styrenpolymerer.pure, arvinylxylene, archlorostyrene or arbromostyrene and the solid copolymers of two or more of such alkenyl aromatic compounds with minor amounts of other readily polymerizable olefinic compounds such as e.g. methyl methacrylate, acrylonitrile, maleic anhydride, citraconic anhydride, itaconic anhydride, acrylic acid and rubber reinforced (either natural or synthetic) styrene polymers.
Fremstillingen af alkenylaromatiske, termoplastiske polymer-10 skumstoffer sker på kendt måde, hvorhos det flygtige flydende opskumningsmiddel indsprøjtes i en varmeplastificeret polymerstrøm i en ekstruder. Fra ekstruderen ledes den varme plasti-ficerede gel til et blandeapparat, idet blandeapparatet er et roterende blandeapparat, hvori en med tænder forsynet rotor er 15 anbragt i et hus, hvis indervæg har tænder, der er i indgreb med tænderne på rotoren. Den varme plastificerede gel fra ekstruderen fødes til blandeapparatets indgangsende og fjernes fra udgangsenden, idet strømmen løber i en overvejende aksial retning. Fra blandeapparatet passerer gelen gennem kølere og 20 fra kølerne til en dyse, som ekstruderer en i alt væsentligt rektangulær plade.The preparation of alkenyl aromatic thermoplastic polymer foams occurs in a known manner in which the volatile liquid foaming agent is injected into a heat-plasticized polymer stream in an extruder. From the extruder, the hot plasticized gel is passed to a mixer, the mixer being a rotary mixer in which a toothed rotor is housed in a housing whose inner wall has teeth which engage the teeth of the rotor. The hot plasticized gel from the extruder is fed to the input end of the mixer and removed from the output end as the current flows in a predominantly axial direction. From the mixer, the gel passes through coolers and from the coolers to a nozzle which extrudes a substantially rectangular plate.
Ved fremstillingen af skumstof legemer ifølge den foreliggende opfindelse er det ofte ønskeligt at tilsætte et kernedannende 25 middel såsom f.eks. talkum, calciumsilikat eller indigo til at reducere cellestørrelsen.In the preparation of foam bodies of the present invention, it is often desirable to add a nucleating agent such as e.g. talc, calcium silicate or indigo to reduce cell size.
Der blev fremstillet et stort antal skumstoffer ved at iblande polystyren med indhold af flammehæmmende middel, som er en 30 monochlorpentabromcyklohexan af kommerciel renhed, bariumstea-rat, magnesiumoxid og et kernedannende middel. Blandingen blev født til en ekstruder, og et skummiddel blev indsprøjtet kontinuerligt i ekstruderens cylinder, polystyrenskumstof blev ekstruderet som en rektangulær plade med en tværsnitsdimension 35 på ca. 2,54 x 25,4 cm. Opskumningstemperaturerne var fra 112 til 118°C. Alle koncentrationer, der er angivet som dele eller dele pr. hundrede (pph), er vægtdele pr. 100 dele polystyrenharpiks. Fødehastighederne, skummiddel sammensætningen og fy-A large number of foams were prepared by admixing polystyrene containing flame retardant, which is a commercial purity monochloropentabromocyclohexane, barium stearate, magnesium oxide and a nucleating agent. The mixture was born to an extruder, and a foam agent was continuously injected into the extruder's cylinder. Polystyrene foam was extruded as a rectangular plate having a cross-sectional dimension 35 of approx. 2.54 x 25.4 cm. The foaming temperatures were from 112 to 118 ° C. All concentrations indicated as parts or parts per hundred (pph), are parts by weight per hour. 100 parts polystyrene resin. The feed rates, the foam composition and the
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5 siske egenskaber er angivet i de følgende tabeller. Massefylden er angivet i g/Ί, cellestørrelsen i mm; under skummidel er vist vægtprocenten og komponenten i skummidlet.Five properties are listed in the following tables. Density is given in g / Ί, cell size in mm; below the foam part is shown the weight percent and component of the foam agent.
5 De fremstillede og i tabellerne anførte skumstoffer indeholdt 3 dele pr. 100 af det flammehammende middel, 0,075 dele pr.5 The foams manufactured and listed in the tables contained 3 parts per 100 of the flame retardant, 0.075 parts per
100 bar iumstearat, 0,03 dele pr. 100 magnesiumoxid. Enhederne for den målte K-faktor er J/sek. · cm ♦ °C og er bestemt på prøver afskåret fra det ekstruderede stof på en sådan måde, at 10 alle overfladerne på den rektangulære prøve er blevet afskåret fra den oprindeligt ekstruderede bjælke til opnåelse af udskårne celler fra hver af overfladerne. Ældning af prøverne skete ved stuetemperatur på ca. 20-25'C. I kolonnen "beregnet K-faktor" findes værdier beregnet for K-faktoren for skummet 15 efter 5 år ved omgivelsernes temperatur i luft og K-faktoren for absolut ældning. Når man kender massefylden, cellestørrel-sen, skummiddelkoncentrationen, skummiddel sammensætningen, K-faktoren, skummidlets permeabilitet, K-faktoren når skumstoffet netop er blevt ekstruderet, kan K-faktoren på ethvert se-20 nere tidspunkt let beregnes med stor nøjagtighed. K-faktoren efter absolut ældning er den K-faktor, skumstoffet ville have, hvis skummidlet i cellerne fuldstændigt var erstattet med luft. Ekstrusionerne vist i forsøgene 7 og 8 i tabellen tilvejebringer ikke et skumstof i overensstemmelse med den fore-25 liggende opfindelse, men tjener udelukkende til sammenligning. Hvis cellestørrelsen og K-faktoren vurderes, er det indlysende, at for et hvilket som helst af skummiddelsystemerne giver den mindste cellestørrelse den laveste K-faktor. Det bør også bemærkes, at fra tabellens første seks linier forbedres lang-30 tidsisoleringsværdien væsentligt ved anvendelsen af et skum- middel med lav permeabilitet i forbindelse med et skummiddel med høj permeabilitet. Permeabi1 i teten er cm3/0,025 mm/645 cm2/dag/atm. Methylchlorids permeabilitet = 980, 1,1-difluor-ethans permeabilitet = 8,4, chlordif1uormethans permeabilitet 35 s 19, ethylchlorids permeabilitet = 84, luftpermeabi1itet * 110, chlorfluormethans permeabilitet = 329, og 1,1-difluor-1-chlorethans permeabilitet * 0,07.100 bar ium stearate, 0.03 parts per 100 magnesium oxide. The units of the measured K-factor are J / sec. And are determined on samples cut from the extruded fabric in such a way that all the surfaces of the rectangular sample have been cut off from the initially extruded beam to obtain cut cells from each of the surfaces. Aging of the samples occurred at room temperature of approx. 20-25 ° C. In the column "calculated K-factor", values calculated for the K-factor of foam 15 after 5 years at ambient temperature in air and the K-factor for absolute aging are found. Knowing the density, cell size, foam concentration, foam composition, K factor, foam permeability, K factor when the foam has just been extruded, the K factor can easily be calculated with great accuracy at any later time. The K-factor after absolute aging is the K-factor that the foam would have if the foam agent in the cells had been completely replaced by air. The extrusions shown in experiments 7 and 8 of the table do not provide a foam in accordance with the present invention, but serve for comparison purposes only. If the cell size and the K factor are assessed, it is obvious that for any of the foaming systems, the smallest cell size gives the lowest K factor. It should also be noted that from the first six lines of the table, the long-term insulation value is significantly improved by the use of a low permeability foaming agent in conjunction with a high permeability foaming agent. The permeability of the density is cm3 / 0.025 mm / 645 cm2 / day / atm. Methyl chloride permeability = 980, 1,1-difluoro-ethane permeability = 8.4, chlorodifluoromethane permeability 35 s 19, ethyl chloride permeability = 84, air permeability * 110, chlorofluoromethane permeability = 329, and 1,1-difluoro-1 * chloroethane permeability 0.07.
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Tabel 2 viser dimensionsstabi11 teten af forskellige skumstoffer fra tabel 1.Table 2 shows the dimensional stability of various foams from Table 1.
Tabel 2 5Table 2 5
Virkningen af skummiddel type på skumstoffets dimensionsstabi1 itetThe effect of foam type on the dimensional stability of the foam
Dimensionsstabilitet ved 60°C og en relativ fugtighed på 100% (% ændring på 1 uge)Dimensional stability at 60 ° C and a relative humidity of 100% (% change in 1 week)
Eks. Skummiddel_vertikalt horisontalt Ext.Ex. Foam_ Vertical Horizontal Ext.
10 2 50/50 chlorfluormethan/ -0,23 -0,05 +0,24 1.1- di fluor-1-chlorethan 5 50/50 methylchlorid/ -0,17 +0,19 +0,32 1.1- difluor-1-chlorethan 15 8 chlorfluormethan -0,41 -0,18 -0,10 (sammenligningseksempel) 9 40/60 chlorfluormethan/ -1,37 +0,35 +0,22 1.1- difluor-l-chlorethan 10 30/70 chlorfluormethan/ -0,95 -0,23 +2,33 1.1- difluor-l-chlorethan 20 11 60/40 chlorf1uormethan/ -0,80 -0,12 +0,48 1.1- di fluor-1-chlorethan 12 70/30 chlorf1uormethan/ -1,40 -0,32 +0,13 1.1- difluor-l-chlorethan 13 40/60 methylchlorid/ -0,43 +0,14 +0,33 1.1- difluor-l-chlorethan 15 40/60 1,1-dif1uorethan/ -0,67 +0,57 +1,00 1.1- difluor-1-chlorethan 16 1,1-difluor-l-chlorethan -0,45 -0,41 +5,07 30 17 40/50/10 ch1orf1 uorme- -0,21 +0,05 +0,88 than/1,1-dif1uor-1-chlorethan/chlordifluormethan 18 39/48,7/12,3 chlor- -0,21 +0,02 +0,32 fluormethan/1,1-diflu-35 or-l-chlorethan/1,1- di fluorethan2 50/50 chlorofluoromethane / -0.23 -0.05 +0.24 1.1-di fluoro-1-chloroethane 50/50 methyl chloride / -0.17 +0.19 +0.32 1.1-difluoro-1 -chloroethane 8 8 chlorofluoromethane -0.41 -0.18 -0.10 (comparative example) 9 40/60 chlorofluoromethane / -1.37 +0.35 +0.22 1.1- difluoro-1-chloroethane 10 30/70 chlorofluoromethane / -0.95 -0.23 +2.33 1.1- Difluoro-1-chloroethane 20/60 60/40 Chlorofluoromethane / -0.80 -0.12 +0.48 1.1- Difluoro-1-chloroethane 12 70 / Chlorofluoromethane / -1.40 -0.32 +0.13 1.1-difluoro-1-chloroethane 13 40/60 methyl chloride / -0.43 +0.14 +0.33 1.1-difluoro-1-chloroethane 40 / 60 1,1-difluoroethane / -0.67 +0.57 +1.00 1.1-difluoro-1-chloroethane 16 1,1-difluoro-1-chloroethane -0.45 -0.41 +5.07 30 17 40/50/10 chlorophenyl--0.21 +0.05 +0.88 than / 1,1-difluoro-1-chloroethane / chlorodifluoromethane 18 39 / 48.7 / 12.3 chloro--0.21 + 0.02 + 0.32 fluoromethane / 1,1-difluoro-1-chloroethane / 1,1-di fluoroethane
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK338277A DK160508C (en) | 1976-02-03 | 1977-07-27 | PROCEDURE FOR THE PREPARATION OF AN EXTENSIVE FOAM BODY OF A THERMOPLASTIC SYNTHETIC ALKENYLAROMATIC POLYMER |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US65469076A | 1976-02-03 | 1976-02-03 | |
US65469076 | 1976-02-03 |
Publications (3)
Publication Number | Publication Date |
---|---|
DK44477A DK44477A (en) | 1977-08-04 |
DK154776B true DK154776B (en) | 1988-12-19 |
DK154776C DK154776C (en) | 1989-05-16 |
Family
ID=24625864
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DK044477A DK154776C (en) | 1976-02-03 | 1977-02-02 | PROCEDURE FOR PREPARING AN EXTENSIVE FOAM BODY OF A THERMOPLASTIC, SYNTHETIC, ALKENYLAROMATIC POLYMER |
Country Status (15)
Country | Link |
---|---|
JP (1) | JPS5295773A (en) |
AU (1) | AU507080B2 (en) |
BE (1) | BE850971A (en) |
BR (1) | BR7700611A (en) |
CA (1) | CA1086450A (en) |
CH (1) | CH633816A5 (en) |
DE (1) | DE2704278C2 (en) |
DK (1) | DK154776C (en) |
ES (1) | ES455332A1 (en) |
FR (1) | FR2340342A1 (en) |
GB (1) | GB1537421A (en) |
IT (1) | IT1112146B (en) |
NL (1) | NL170297C (en) |
NO (1) | NO147989C (en) |
SE (1) | SE426072B (en) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2738719A1 (en) * | 1977-08-27 | 1979-03-08 | Bayer Ag | Process for the production of foamed plastics |
GB2125796B (en) * | 1982-08-23 | 1986-03-19 | Cosden Technology | Flame retarding extruded plastics foam compositions |
US4528300A (en) * | 1984-01-31 | 1985-07-09 | The Dow Chemical Company | Process for producing dimensionally stable polyolefin foams using environmentally acceptable blowing agent systems |
BR8807460A (en) * | 1987-04-15 | 1990-04-10 | Dow Chemical Co | METHOD OF EXTRUSION OF A SYNTHETIC AROMATIC RESIN FOAM BODY WITH ALKENYLES WITH CLOSED CELLS |
JPH01247434A (en) * | 1988-03-30 | 1989-10-03 | Sekisui Plastics Co Ltd | Production of flame-retarding styrene resin foam |
JP2835726B2 (en) * | 1988-05-16 | 1998-12-14 | 株式会社 ジェイエスピー | Method for producing plate-like polystyrene resin foam |
DE3829633A1 (en) * | 1988-09-01 | 1990-03-15 | Basf Ag | METHOD FOR PRODUCING FOAM PANELS WITH HIGH PRESSURE RESISTANCE AND HIGH THERMAL INSULATION |
US4912140A (en) * | 1988-09-21 | 1990-03-27 | The Dow Chemical Company | Expandable and expanded alkenyl aromatic polymer particles |
JP2922953B2 (en) * | 1988-10-17 | 1999-07-26 | ザ ダウ ケミカル カンパニー | Insulated alkenyl aromatic polymer foam |
US4916166A (en) * | 1988-10-17 | 1990-04-10 | The Dow Chemical Company | Insulating alkenyl aromatic polymer foam |
ES2083978T3 (en) * | 1989-02-01 | 1996-05-01 | Asahi Glass Co Ltd | AZEOTROPIC MIXTURE OR SIMILAR TO AN AZEOTROPIC MIXTURE BASED ON HYDROGENATED, CHLORINATED AND FLUORATED HYDROCARBONS. |
US5320683A (en) * | 1989-02-06 | 1994-06-14 | Asahi Glass Company Ltd. | Azeotropic or azeotropic-like composition of hydrochlorofluoropropane |
US5120481A (en) * | 1989-02-28 | 1992-06-09 | U.C. Industries, Inc. | Process for preparing extruded foam bodies |
DE3930594A1 (en) * | 1989-09-13 | 1991-03-14 | Gefinex Jackon Gmbh | Moulded foam prods., esp. of polystyrene foam - by extrusion, using mixt. of above 30 wt. per cent 1,1-di:fluoro-1-chloro-ethane and water and-or nitrogen as blowing agent |
US5011866A (en) * | 1989-11-08 | 1991-04-30 | The Dow Chemical Company | Insulating alkenyl aromatic polymer foam |
DE3939986A1 (en) * | 1989-12-02 | 1991-06-06 | Gefinex Gmbh | Prodn. of foams of polystyrene or polyethylene - using chloro:di:fluoro:methane contg. ammonium bi:carbonate or other ammonium cpd. as blowing agent |
US4956395A (en) * | 1990-01-18 | 1990-09-11 | Amoco Corporation | Styrenic foam blowing agent composition |
US6121337A (en) * | 1990-03-23 | 2000-09-19 | E. I. Du Pont De Nemours And Company | Compositions containing 1,1,2,2-tetrafluoroethane (HFC-134) for closed-cell polymer foam production |
US5106882A (en) * | 1991-05-28 | 1992-04-21 | The Dow Chemical Company | Insulating alkenyl aromatic polymer foam |
JPH0553140U (en) * | 1991-12-20 | 1993-07-13 | 星和電機株式会社 | Waterproof retainer for cable connection |
KR20010033292A (en) | 1997-12-18 | 2001-04-25 | 그래햄 이. 테일러 | Foams comprising HFC-134 and a low solubility co-blowing agent and a process for making |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1215410A (en) * | 1957-11-29 | 1960-04-19 | Dow Chemical Co | A method of making a latently foaming polymerized composition |
US3287477A (en) * | 1964-11-12 | 1966-11-22 | Koppers Co Inc | Process and apparatus for extruding a foamed plastic |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA975500A (en) | 1969-02-06 | 1975-09-30 | Joseph G. Spitzer | Structures such as applicator pads for cleaning and other purposes, propellant compositions for forming the same, and process |
CH572269A5 (en) * | 1972-07-20 | 1976-01-30 | Bbc Brown Boveri & Cie |
-
1977
- 1977-01-14 CA CA269,739A patent/CA1086450A/en not_active Expired
- 1977-01-25 ES ES455332A patent/ES455332A1/en not_active Expired
- 1977-01-27 NL NLAANVRAGE7700842,A patent/NL170297C/en not_active IP Right Cessation
- 1977-01-31 IT IT47858/77A patent/IT1112146B/en active
- 1977-01-31 GB GB3907/77A patent/GB1537421A/en not_active Expired
- 1977-02-01 BE BE174560A patent/BE850971A/en not_active IP Right Cessation
- 1977-02-01 CH CH120377A patent/CH633816A5/en not_active IP Right Cessation
- 1977-02-01 BR BR7700611A patent/BR7700611A/en unknown
- 1977-02-02 DE DE2704278A patent/DE2704278C2/en not_active Expired
- 1977-02-02 SE SE7701144A patent/SE426072B/en not_active IP Right Cessation
- 1977-02-02 JP JP1058877A patent/JPS5295773A/en active Granted
- 1977-02-02 NO NO770347A patent/NO147989C/en unknown
- 1977-02-02 DK DK044477A patent/DK154776C/en active
- 1977-02-02 AU AU21876/77A patent/AU507080B2/en not_active Expired
- 1977-02-02 FR FR7702924A patent/FR2340342A1/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1215410A (en) * | 1957-11-29 | 1960-04-19 | Dow Chemical Co | A method of making a latently foaming polymerized composition |
US3287477A (en) * | 1964-11-12 | 1966-11-22 | Koppers Co Inc | Process and apparatus for extruding a foamed plastic |
Also Published As
Publication number | Publication date |
---|---|
FR2340342B1 (en) | 1983-07-01 |
BR7700611A (en) | 1977-08-16 |
BE850971A (en) | 1977-08-01 |
NL7700842A (en) | 1977-08-05 |
DE2704278A1 (en) | 1977-08-04 |
GB1537421A (en) | 1978-12-29 |
SE7701144L (en) | 1977-08-04 |
DK154776C (en) | 1989-05-16 |
CA1086450A (en) | 1980-09-23 |
NL170297C (en) | 1982-10-18 |
FR2340342A1 (en) | 1977-09-02 |
NO770347L (en) | 1977-08-04 |
IT1112146B (en) | 1986-01-13 |
NO147989B (en) | 1983-04-11 |
NL170297B (en) | 1982-05-17 |
ES455332A1 (en) | 1978-05-16 |
CH633816A5 (en) | 1982-12-31 |
DK44477A (en) | 1977-08-04 |
NO147989C (en) | 1983-07-20 |
JPS5295773A (en) | 1977-08-11 |
SE426072B (en) | 1982-12-06 |
DE2704278C2 (en) | 1983-08-04 |
AU2187677A (en) | 1978-08-10 |
JPS577175B2 (en) | 1982-02-09 |
AU507080B2 (en) | 1980-01-31 |
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