DK142548B - Process for the production of rigid polyisocyanurate foams and a homogeneous liquid mixture for use in the process. - Google Patents
Process for the production of rigid polyisocyanurate foams and a homogeneous liquid mixture for use in the process. Download PDFInfo
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- DK142548B DK142548B DK629572AA DK629572A DK142548B DK 142548 B DK142548 B DK 142548B DK 629572A A DK629572A A DK 629572AA DK 629572 A DK629572 A DK 629572A DK 142548 B DK142548 B DK 142548B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
(½^ \Ra) (11) fremlæggelsessmrift 1^2548 DANMARK <·» Im.CI.* C 08 8 18/22 «(21) Ansøgning nr. 6295/72 (22) Indleveret den 15· dec. 1972 (24) Løbedag 15· deC. 1972 (44) Ansøgningen fremlagt og fremlæggelsesskriftet offentliggjort den 17· HOV· 1 98Ο(½ ^ \ Ra) (11) Petition 1 ^ 2548 DENMARK <· »Im.CI. * C 08 8 18/22 '(21) Application No 6295/72 (22) Filed on 15 · Dec. 1972 (24) Race day 15 · deC. 1972 (44) The application presented and the petition published on 17 · HOV · 1 98Ο
DIREKTORATET FORDIRECTORATE OF
PATENT- OG VAREMÆRKEVÆSENET (30) Prioritet begæret fra denPATENT AND TRADEMARKET SYSTEM (30) Priority requested from it
15. Jan. 1972, 1685/72, GB15. Jan. 1972, 1685/72, GB
(71) SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ N. V., Car el van Byland t=(71) SHELL INTERNATIONAL RESEARCH COMPANY N. V., Car el van Byland t =
Taan 50, Haag, NL.Taan 50, The Hague, NL.
i72) Opfinder: Michael Anthony Haas, Lillian Road 51» Barnes, London S.W. 15, GB: Reinhart Schiffauer, Gresham Road 55# Staines, Middlesex, GB.i72) Inventor: Michael Anthony Haas, 51 Lillian Road »Barnes, London S.W. 15, GB: Reinhart Schiffauer, Gresham Road 55 # Staines, Middlesex, GB.
(74) Fuldmægtig under sagens behandling:(74) Plenipotentiary in the proceedings:
Plougmann & Vingtoft Patentbureau.Plougmann & Vingtoft Patent Office.
(54) Fremgangsmåde til fremstilling af stive polyisocyanuratskumstoffer samt en homogen væskeformig blanding til anvendelse ved fremgangsmåden.(54) Process for the production of rigid polyisocyanurate foams and a homogeneous liquid mixture for use in the process.
Den foreliggende opfindelse angår en fremgangsmåde til fremstilling af stive polyisocyanuratskumstoffer ved under skumdannende betingelser at omsatte et organisk polyisocyanat med en væskeformig blanding, der udover eventuelle tilsætningsstoffer består af kaliumacetat i en katalytisk mængde, trichlorfluormethan og en polyol, idet der anvendes overskud af isocyanatgrupper i forhold til aktive hydrogenatomer, kendetegnet ved, at den væskeformige blanding er homogen, at en del af polyolen i den væskeformige blanding udgøres af en diol, b, som er en alkandiol eller en polyetherdiol med en gennemsnitlig molekylvægt på 100 - 500 og med mindst én sekundær hydroxygruppe i molekylet, og at den resterende del af polyolen udgøres af en polyetherpolyol, c, med en gennemsnitlig molekylvægt på 200 - 10.000, med det forbehold, at hvis den gennem- 2 142548 snitlige molekylvægt af polyetherpolyolen, c, er 20Q - 500, da er c ikke en diol med mindst én sekundær hydroxygruppe i molekylet, samt at opløseligheden af kaliumacetat i polyetherpolyolen, c, er mindst 10 g/liter ved 25°C, hvorhos vægtforholdet mellem diolen b og polyetherpolyolen c er mellem 5:1 og 1:5.The present invention relates to a process for preparing rigid polyisocyanurate foams by reacting under foam-forming conditions an organic polyisocyanate with a liquid mixture which, in addition to any additives, consists of potassium acetate in a catalytic amount, trichlorofluoromethane and a polyol using excess isocyanate ratio. to active hydrogen atoms, characterized in that the liquid mixture is homogeneous, that a portion of the polyol in the liquid mixture is constituted by a diol, b, which is an alkanediol or a polyether diol having an average molecular weight of 100-500 and having at least one secondary hydroxy group in the molecule and that the remaining portion of the polyol is constituted by a polyether polyol, c, having an average molecular weight of 200 - 10,000, provided that if the average molecular weight of the polyether polyol, c is 20Q - 500, then c is not a diol with at least one secondary hydroxy group in the molecule, as well as solute the content of potassium acetate in the polyether polyol, c, is at least 10 g / liter at 25 ° C, the weight ratio of the diol b to the polyether polyol c being between 5: 1 and 1: 5.
Det er kendt at fremstille isocyanuratskumstoffer ved at omsætte et organisk polyisocyanat med en polyol i nærværelse af en katalysator, som er i stand til at trimerisere isocyanatgrupper til isocyanurat-ringe, og et opskumningsmiddel. Det er også kendt at anvende kaliumacetat opløst i visse polyoler som trimeriseringskatalysator og at anvende trichlorfluoxmethan som opskumningsmiddel.It is known to prepare isocyanurate foams by reacting an organic polyisocyanate with a polyol in the presence of a catalyst capable of trimerizing isocyanate groups to isocyanurate rings and a foaming agent. It is also known to use potassium acetate dissolved in certain polyols as a trimerization catalyst and to use trichlorofluoxmethane as a foaming agent.
Et praktisk problem, som man støder på under anvendelse af den kendte teknik, er, at det er vanskeligt at danne en opløsning indeholdende polyol, trichlorfluormethan og kaliumacetat. Det er muligt at opløse kaliumacetat i visse polyoler, men ved tilsætning af trichlorf luormethan bliver sådanne blandinger heterogene. Sådanne heterogene blandinger giver ikke et homogent skum. En måde, på hvilken disse ulemper kan overvindes, går ud på at blande trichlorfluormethan med det organiske polyisocyanat og kun bringe de ublandbare komponenter i forbindelse med hinanden umiddelbart før der fremstilles isocyanuratskumstoffer. Imidlertid medfører denne løsning en uønsket begrænsning af udførelsen af fremgangsmåden.A practical problem encountered using the prior art is that it is difficult to form a solution containing polyol, trichlorofluoromethane and potassium acetate. It is possible to dissolve potassium acetate in certain polyols, but by the addition of trichlorofluoromethane such mixtures become heterogeneous. Such heterogeneous mixtures do not give a homogeneous foam. One way in which these drawbacks can be overcome is to mix trichlorofluoromethane with the organic polyisocyanate and bring only the immiscible components into contact with each other immediately before producing isocyanurate foams. However, this solution causes an undesirable restriction on the performance of the method.
Det har nu overraskende vist sig, at der kan dannes en homogen blanding af kaliumacetat og trichlorfluormethan i mindst én polyol ved nærværelse af en diol, som indeholder mindst én sekundær hydroxygruppe.It has now surprisingly been found that a homogeneous mixture of potassium acetate and trichlorofluoromethane can be formed in at least one polyol in the presence of a diol containing at least one secondary hydroxy group.
Ifølge den foreliggende opfindelse er en væskeformig blanding, til anvendelse sammen med et organisk polyisocyanat ved udøvelse af fremgangsmåden ifølge opfindelsen, ejendommelig ved, at blandingen er homogen, og at den udover eventuelle tilsætningsstoffer består af a) kaliumacetat i en katalytisk mængde, b) en diol, som er en alkandiol eller en polyetherdiol med en gennemsnitlig molekylvægt på 100 - 500 og med mindst én sekundær hydroxygruppe i molekylet, 3 142548 c) en polyetherpolyol med en gennemsnitlig molekylvægt på 200 -10.000, med det forbehold, at hvis den gennemsnitlige molekylvægt af polyetherpolyolen er 200 - 500, da er polyetherpolyolen ikke en diol med mindst én sekundær hydroxygruppe i molekylet, og d) trichlorfluormethan, med det forbehold, at kaliumacetat har en opløselighed i polyetherpolyolen c på mindst 10 g/liter ved 25°C, hvorhos vægtforholdet mellem diolen b og polyetherpolyolen c er mellem 5:1 og 1:5.According to the present invention, a liquid mixture for use with an organic polyisocyanate in the practice of the invention is characterized in that the mixture is homogeneous and that, in addition to any additives, it consists of a) potassium acetate in a catalytic amount, b) a diol which is an alkanediol or a polyether diol having an average molecular weight of 100-500 and having at least one secondary hydroxy group in the molecule; c) a polyether polyol having an average molecular weight of 200-10,000, provided that if the average molecular weight of the polyether polyol is 200-500, then the polyether polyol is not a diol with at least one secondary hydroxy group in the molecule, and d) trichlorofluoromethane, with the proviso that potassium acetate has a solubility in the polyether polyol c of at least 10 g / liter at 25 ° C. the weight ratio of the diol b to the polyether polyol c is between 5: 1 and 1: 5.
Egnede alkandioler eller polyetherdioler (hvilke dioler i det følgende betegnes "sekundære dioler") er f.eks. polyoxypropylenglyco-ler med forskellige molekylvægte såsom dipropylenglycol, tripropylen-glycol og tetrapropylenglycol, 1,3-butandiol, 1,3-pentandiol, 1,4--pentandiol, 2,4-pentandiol, 2-methyl-2,4-pentandiol (hexylenglycol), 1,2-hexandiol, 1,4-hexandiol, 1,5-hexandiol, 2,3-hexandiol, 2,4--hexandiol, 2,5-hexandiol og 3,4-hexandiol og blandinger deraf. Foretrukne dioler har én sekundær hydroxygruppe og én primær hydroxygruppe.Suitable alkanediols or polyetherdiols (hereinafter referred to as "secondary diols") are e.g. polyoxypropylene glycols having different molecular weights such as dipropylene glycol, tripropylene glycol and tetrapropylene glycol, 1,3-butanediol, 1,3-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol ( hexylene glycol), 1,2-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 2,3-hexanediol, 2,4-hexanediol, 2,5-hexanediol and 3,4-hexanediol and mixtures thereof. Preferred diols have one secondary hydroxy group and one primary hydroxy group.
Kaliumacetat skal have en opløselighed i polyetherpolyolen på mindst 10 g/liter ved 25°C. Foretrukne polyetherpolyoler, der i det følgende betegnes "polyoler", er de polyetherpolyoler, som kan fremstilles ved omsætning af ét eller flere alkylenoxider, f.eks. ethylenoxid, propylenoxid, styrenoxid eller epichlorhydrin, med en alkanpolyol, f.eks. en alkylendiol, med det forbehold, at polyoler, ifald de er dioler og fremstillet ved denne omsætning, har en gennemsnitlig molekylvægt på over 500, eller alkylenpolyol såsom ethylengly-col, glycerol, pentaerythritol, saccharose eller sorbitol eller en al-kylenoxidpolymer eller -copolymer såsom en blokcopolymer eller en copolymer med tilfældigt fordelte repetitionsenheder. Andre egnede polyoler kan fremstilles ved omsætning af én eller flere af de ovenfor angivne polyoler med mindre end den støkiometriske 4 142548 mængde organisk polyisocyanat. Særligt foretrukne polyoler er sådanne, dér fremstilles ved omsætning af en triol såsom glycerol med propylenoxid.Potassium acetate must have a solubility in the polyether polyol of at least 10 g / liter at 25 ° C. Preferred polyether polyols, hereinafter referred to as "polyols", are those polyether polyols which can be prepared by reacting one or more alkylene oxides, e.g. ethylene oxide, propylene oxide, styrene oxide or epichlorohydrin, with an alkane polyol, e.g. an alkylene diol, provided that polyols, if they are diols and prepared by this reaction, have an average molecular weight of more than 500, or alkylene polyol such as ethylene glycol, glycerol, pentaerythritol, sucrose or sorbitol or an alkylene oxide polymer or copolymer such as a block copolymer or a copolymer with randomly distributed repeating units. Other suitable polyols may be prepared by reacting one or more of the above polyols with less than the stoichiometric amount of organic polyisocyanate. Particularly preferred polyols are those prepared there by reacting a triol such as glycerol with propylene oxide.
Vægtforholdet mellem den sekundære diol og polyolen i den væskeformige homogene blanding kan variere inden for vide grænser, men ligger mellem 5:1 og 1:5, fortrinsvis 1:2 - 1:5.The weight ratio of the secondary diol to the polyol in the liquid homogeneous mixture may vary within wide limits, but is between 5: 1 and 1: 5, preferably 1: 2 - 1: 5.
Mængden af kaliumacetat kan også variere inden for vide grænser og kan f.eks. være 0,5 - 20, fortrinsvis 2,5 - 7,5, vægtdele, beregnet på 100 vægtdele total sekundær diol og polyol. Den maksimale mængde kaliumacetat, som kan være til stede i den væskeformige blanding, vil være begrænset af opløselighedsgraden i diolen, polyolen og tri-chlorfluormethanet. Fortrinsvis opløses kaliumacetatet i polyolen, om nødvendigt under opvarmning. Eventuelt tilstedeværende uopløst kaliumacetat fjernes fra blandingen, før den sekundære diol og tri-chlorfluormethanet tilsættes for at danne den væskeformige blanding.The amount of potassium acetate may also vary within wide limits and may e.g. be 0.5-20, preferably 2.5 - 7.5, parts by weight based on 100 parts by weight of total secondary diol and polyol. The maximum amount of potassium acetate that may be present in the liquid mixture will be limited by the solubility degree of the diol, polyol and trichlorofluoromethane. Preferably, the potassium acetate is dissolved in the polyol, if necessary under heating. Any unsolved potassium acetate present is removed from the mixture before the secondary diol and the trichlorofluoromethane are added to form the liquid mixture.
Trichlorfluormethanmængden i den væskeformige blanding kan variere betydeligt og kan f.eks. være 50 - 300 vægtdele, beregnet på 100 vægtdele af den totale mængde sekundær diol og polyol.The amount of trichlorofluoromethane in the liquid mixture can vary considerably and may e.g. be 50 to 300 parts by weight, calculated on 100 parts by weight of the total amount of secondary diol and polyol.
Egnede organiske polyisocyanater er f.eks. monoarylpolyisocyanater og polyarylpolyisocyanater såsom polyarylpolyalkylenpolyisocyanater. Eksempler på monoarylpolyisocyanater er tolylen-2,4-diisocyanat og tolylen-2,6-diisocyanat og blandinger deraf såsom 80:20 eller 65:35, beregnet på vægtdele, m-phenylendiisocyanat og p-phenylendiisocya-nat. Eksempler på polyarylpolyisocyanater er naphthalen-1,5-diiso-cyanat, diphenylmethyl-4,4'-diisocyanat, 3-methyldiphenylmethan--4,4'-diisocyanat og diphenyl-4,4'-diisocyanat.Suitable organic polyisocyanates are e.g. monoaryl polyisocyanates and polyaryl polyisocyanates such as polyaryl polyalkylene polyisocyanates. Examples of monoaryl polyisocyanates are tolylene-2,4-diisocyanate and tolylene-2,6-diisocyanate and mixtures thereof such as 80:20 or 65:35 by weight, m-phenylene diisocyanate and p-phenylene diisocyanate. Examples of polyaryl polyisocyanates are naphthalene-1,5-diisocyanate, diphenylmethyl-4,4'-diisocyanate, 3-methyldiphenylmethane-4,4'-diisocyanate and diphenyl-4,4'-diisocyanate.
Et særlig egnet polyarylpolyisocyanat er råt diphenylmethandiisocya-nat, som fremstilles med phosgenering af rå diphenylmethandiaminer, som kan fremstilles ved omsætning af aromatiske aminer såsom anilin, o-chloranilin eller o-toluidin med formaldehyd og saltsyre. Når der som aromatisk amin anvendes anilin, er produktet en blanding af diphenyl-4, 4'-diisocyanat, diphenyl-2,4'-diisocyanat og tilsvarende polyisocyanater med højere molekylvægt og funktionalitet såsom tri-og tetraisocyanater. Mængden af sådanne komponenter i blandingen vil c 142548 5 variere afhængigt af den mængde formaldehyd og anilin, der er anvendt til fremstilling af de rå diphenylmethanpolyaminer. Egnede vægtforhold mellem anilin og formaldehyd er 4:1 - 4:1,5.A particularly suitable polyaryl polyisocyanate is crude diphenylmethane diisocyanate, which is prepared by phosgenation of crude diphenylmethanediamines which can be prepared by reacting aromatic amines such as aniline, o-chloroaniline or o-toluidine with formaldehyde and hydrochloric acid. When aniline is used as an aromatic amine, the product is a mixture of diphenyl-4,4'-diisocyanate, diphenyl-2,4'-diisocyanate and corresponding higher molecular weight polyisocyanates and functionality such as tri and tetraisocyanates. The amount of such components in the mixture will vary depending on the amount of formaldehyde and aniline used to prepare the crude diphenylmethane polyamines. Suitable weight ratios of aniline to formaldehyde are 4: 1 - 4: 1.5.
Egnede rå diphenylmethandiisocyanater indeholder 30-90 vægtprocent, fortrinsvis 40 - 65 vægtprocent, beregnet i forhold til polyisocyanat med en funktionalitet større end 2. De difunktionelle forbindelser indeholder væsentlige mængder af diphenylmethan-4,4'--diisocyanat. Mængderne af de ovenfor angivne forbindelser kan også varieres ved at fjerne noget diphenyl-4,4'-diamin fra det rå diphe-nylmethandiaminudgangsmateriale eller noget diphenylmethan-4,4’-diisocyanat fra det rå diphenylmethandiisocyanatprodukt.Suitable crude diphenylmethane diisocyanates contain 30-90% by weight, preferably 40-65% by weight, calculated relative to polyisocyanate having a functionality greater than 2. The difunctional compounds contain substantial amounts of diphenylmethane-4,4 'diisocyanate. The amounts of the above compounds may also be varied by removing some diphenyl-4,4'-diamine from the crude diphenylmethane diamine starting material or some diphenylmethane-4,4'-diisocyanate from the crude diphenylmethane diisocyanate product.
Den mængde organisk polyisocyanat, der lades reagere med den væskeformige blanding, kan variere inden for vide grænser, men er sædvanligvis 2-10, fortrinsvis 3-7, ækvivalenter isocyanatgrupper i det organiske polyisocyanat pr. ækvivalent aktiv hydroxygruppe i polyolen.The amount of organic polyisocyanate which is allowed to react with the liquid mixture may vary within wide limits, but is usually 2-10, preferably 3-7, equivalent isocyanate groups in the organic polyisocyanate per minute. equivalent active hydroxy group in the polyol.
Den væskeformige blanding og/eller det organiske polyisocyanat, som omsættes med hinanden til dannelse af stive polyisocyanurat-skumstoffer, kan yderligere indeholde additiver.The liquid mixture and / or the organic polyisocyanate which react with each other to form rigid polyisocyanurate foams may further contain additives.
Egnede additiver er f.eks. fyldstoffer såsom kridt og ler, antioxi-danter, flammeretarderende midler såsom trichlorethylphosphat og siliconolier såsom siloxan-oxyalkylencopolymere. Sædvanlige poly- : urethankatalysatorer såsom aminer, f.eks. triethylendiamin og tri-ethylamin, som katalyserer omsætningen mellem hydroxy- og isocyanat-grupperne, kan også være til stede.Suitable additives are e.g. fillers such as chalk and clay, antioxidants, flame retardants such as trichloroethyl phosphate, and silicone oils such as siloxane oxyalkylene copolymers. Conventional polyurethane catalysts such as amines, e.g. triethylenediamine and triethylamine which catalyze the reaction between the hydroxy and isocyanate groups may also be present.
Den væskeformige blanding og det organiske polyisocyanat kan omsættes med hinanden under skumstofdannende betingelser under dannelse af støbte emner, plader eller blokke af skumstof eller laminater.The liquid mixture and the organic polyisocyanate may react with each other under foam-forming conditions to form molded blanks, sheets or blocks of foam or laminates.
Den væskeformige blandings trichlorfluormethanbestanddel bringes til at fordampe, og derved skummer reaktionsblandingen. Reaktionsvarmen kan være tilstrækkelig til fordampning af trichlorfluormetha-net, eller der må yderligere føres varme til reaktionsblandingen.The trichlorofluoromethane component of the liquid mixture is evaporated, thereby foaming the reaction mixture. The heat of reaction may be sufficient to evaporate the trichlorofluoromethane or heat may be added further to the reaction mixture.
6 1425486 142548
De ved fremgangsmåden ifølge den foreliggende opfindelse fremstillede stive isocyanuratskumstoffer har gode egenskaber ved høj temperatur såsom modstandsdygtighed over for ild og er især egnede til anvendelse som isoleringsmaterialer og bygningselementer.The rigid isocyanurate foams prepared by the process of the present invention have good high temperature properties such as fire resistance and are particularly suitable for use as insulating materials and building elements.
Opfindelsen belyses ved de følgende eksempler, hvor polyol A betegner et glycerolinitieret propylenoxidaddukt med over 80% sek.hydro-xygrupper, som er fremstillet ved basisk katalyse, og som har en gennemsnitlig molekylvægt på ca. 300, polyol B betegner et glycerolinitieret propylenoxidaddukt med lidt under 80% sek.hy-droxygrupper og indeholdende ca. 5 vægtprocent af tilfældigt mellem enderne fordelte repetitionse'nheder hidrørende fra ethylenoxid og ca. 10 vægtprocent af endegrupper hidrørende fra ethylenoxid, hvor de angivne vægtprocent er beregnet på den totale vægt af ethylen- og propylenoxidreaktanterne, hvilket propylenoxidaddukt har en gennemsnitlig molekylvægt på ca. 4500, og polyol C betegner et glycerolinitieret propylenoxidaddukt med næsten alle hydroxygrupper sekundært placeret, som er fremstillet ved basisk katalyse, og som har en gennemsnitlig molekylvægt på ca. 3000 og. en hydroxyværdi på ca. 56 mg KOH/g. Opløseligheden af kaliumacetat i polyolerne A, B og C er større end 10 g/liter ved 25°C.The invention is illustrated by the following examples in which polyol A represents a glycerol-initiated propylene oxide adduct having more than 80% sec hydroxy groups prepared by basic catalysis and having an average molecular weight of approx. 300, polyol B represents a glycerol-initiated propylene oxide adduct having slightly less than 80% sec-hydroxy groups and containing ca. 5% by weight of repetition units randomly distributed between the ends from ethylene oxide and approx. 10% by weight of end groups derived from ethylene oxide, the weight percent indicated being based on the total weight of the ethylene and propylene oxide reactants, which propylene oxide adduct has an average molecular weight of approx. 4500, and polyol C represents a glycerol-initiated propylene oxide adduct with almost all hydroxy groups secondarily prepared by basic catalysis and having an average molecular weight of about 3000 and. a hydroxy value of approx. 56 mg KOH / g. The solubility of potassium acetate in polyols A, B and C is greater than 10 g / liter at 25 ° C.
Eksempel A.Example A.
En sammensætning (type A) bestående af følgende bestanddele fremstilles ved stuetemperatur.A composition (type A) consisting of the following ingredients is prepared at room temperature.
Bestanddel VægtdeleComponent Weight parts
Polyol A 20Polyol A 20
Kaliumacetat 0,25Potassium acetate 0.25
Trichlorfluormethan 17.Trichlorofluoromethane 17.
Sammensætningen er heterogen.The composition is heterogeneous.
Ved stuetemperatur fremstilles yderligere 4 sammensætninger ved i sammensætninger af typen A yderligere at anvende dioler med mindst én sekundær hydroxygruppe. Sammensætningerne fremgår af tabel I.At room temperature, an additional 4 compositions are prepared by using, in type A compositions, diols having at least one secondary hydroxy group. The compositions are shown in Table I.
142548 7142548 7
Tabel ITable I
Bestanddel Samraensætning/vægtdele 12 3 4Component Co-composition / parts by weight 12 3 4
Polyol A 10 18 10 20Polyol A 10 18 10 20
Tripropylenglycol 5---Tripropylene Glycol 5 ---
Polypropylenglycol (MW 250) 10 4Polypropylene Glycol (MW 250) 10 4
Hexylenglycol 4Hexylene glycol 4
Kaliumacetat 0,25 0,5 0,25 0,5Potassium acetate 0.25 0.5 0.25 0.5
Trichlorfluormethan 21 17 11 21Trichlorofluoromethane 21 17 11 21
Alle fire sammensætninger er homogene blandinger. Der iagttages ingen heterogenitet.All four compositions are homogeneous mixtures. No heterogeneity is observed.
Til sammenligning fremstilles yderligere ved stuetemperatur tre sammensætninger ved i sammensætninger af typen A yderligere at anvende en triol og dioler, som ikke har en sekundær hydroxygruppe. Sammensætningerne fremgår af tabel II.In comparison, three compositions are further prepared at room temperature by further using in a type A compositions a triol and diols which do not have a secondary hydroxy group. The compositions are shown in Table II.
Tabel IITable II
Bestanddel Sammensætning/vægtdele .Component Composition / parts by weight.
5 6,16.1
Polyol A 15 20 20Polyol A 15 20 20
Monoethylenglycol 7 “ I ~ 1,4-Butandiol - 10Monoethylene Glycol 7 "I ~ 1,4-Butanediol - 10
Glycerol 8Glycerol 8
Kaliumacetat 0,4 0,5 0,5Potassium acetate 0.4 0.5 0.5
Trichlorfluormethan 15 20 20Trichlorofluoromethane 15 20 20
Alle tre sammensætninger er heterogene.All three compositions are heterogeneous.
8 1425488 142548
Eksempel B.Example B.
En. sammensætning (type B) bestående af følgende bestanddele fremstilles ved stuetemperatur.One. composition (type B) consisting of the following ingredients is prepared at room temperature.
Bestanddel VægtdeleComponent Weight parts
Polyol A 20Polyol A 20
Polyol B 10Polyol B 10
Kaliumacetat 0,25Potassium acetate 0.25
Trichlorfluormethan 22.Trichlorofluoromethane 22.
Sammensætningen er heterogen.The composition is heterogeneous.
Ved stuetemperatur fremstilles yderligere to sammensætninger ved i sammensætninger af type B yderligere at anvende dioler med mindst én sekundær hydroxygruppe. Sammensætningerne fremgår af tabel III.At room temperature, two further compositions are prepared by further using diols having at least one secondary hydroxy group in type B compositions. The compositions are shown in Table III.
Tabel IIITable III
Bestanddel Sammensætning/vægtdele 8 9Component Composition / parts by weight 8 9
Polyol A 20 15Polyol A 20 15
Polyol B 9 10Polyol B 9 10
Tripropylenglycol 8Tripropylene glycol 8
Polypropylenglycol (MW 250) - 10Polypropylene Glycol (MW 250) - 10
Kaliumacetat 0,5 0,25Potassium acetate 0.5 0.25
Trichlorfluormethan 24 17Trichlorofluoromethane 24 17
Begge sammensætninger er homogene blandinger. Der iagttages ingen heterogenitet.Both compositions are homogeneous mixtures. No heterogeneity is observed.
9 1425489 142548
Til sammenligning fremstilles ved stuetemperatur yderligere tre sammensætninger ved i sammensætninger af type B yderligere at anvende en triol og dioler, som ikke har en sekundær hydroxygruppe. Sammensætningerne fremgår af tabel IV.In comparison, at room temperature, a further three compositions are prepared by further using in a type B compositions a triol and diols which do not have a secondary hydroxy group. The compositions are shown in Table IV.
Tabel IVTable IV
iin
Bestanddel Sammensætning/vægtdele 10 ! 11 12 iComponent Composition / parts by weight 10! 11 12 i
Polyol A 10 10 20Polyol A 10 10 20
Polyol B 10 10 20Polyol B 10 10 20
Monoethylenglycol 5 1,4-Butandiol - 4Monoethylene Glycol 5 1,4-Butanediol - 4
Glycerol - - 9Glycerol - - 9
Kaliumacetat 0,25 0,25 0,5Potassium acetate 0.25 0.25 0.5
Trichlorfluormethan 10 11 19 iTrichlorofluoromethane 10 11 19 i
Alle tre sammensætninger er heterogene.All three compositions are heterogeneous.
Eksempel C.Example C.
Ved stuetemperatur fremstilles to sammensætninger bestående af de i tabel V angivne bestanddele.At room temperature, two compositions are made up of the ingredients listed in Table V.
Tabel VTable V
Bestanddel Sammensætning/vaegtdele 13 14Component Composition / weight parts 13 14
Polyol C 18 20Polyol C 18 20
Diethylenglycol 8 2,5Diethylene glycol 8 2.5
Hexylenglycol - 8Hexylene Glycol - 8
Kaliumacetat 0,25 0,5Potassium acetate 0.25 0.5
Trichlorfluormethan 20 20 jTrichlorofluoromethane 20 20 j
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB168372 | 1972-01-13 | ||
| GB168372 | 1972-01-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DK142548B true DK142548B (en) | 1980-11-17 |
| DK142548C DK142548C (en) | 1981-07-06 |
Family
ID=9726210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK629572AA DK142548B (en) | 1972-01-13 | 1972-12-15 | Process for the production of rigid polyisocyanurate foams and a homogeneous liquid mixture for use in the process. |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS4881996A (en) |
| BE (1) | BE792706A (en) |
| DE (1) | DE2261545A1 (en) |
| DK (1) | DK142548B (en) |
| FR (1) | FR2167532B1 (en) |
| GB (1) | GB1343581A (en) |
| IT (1) | IT971959B (en) |
| NL (1) | NL7216883A (en) |
| ZA (1) | ZA728863B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3836424A (en) * | 1972-07-18 | 1974-09-17 | R Grieve | Polyisocyanurate foam articles |
| DE2607380C3 (en) * | 1976-02-24 | 1981-07-23 | Bayer Ag, 5090 Leverkusen | Process for the production of thermoformable polyisocyanurate foams |
| JPS55151021A (en) * | 1979-05-14 | 1980-11-25 | Achilles Corp | Production of urethane-modified isocyanurate foam with high water and moisture resistance |
| JPS55155015A (en) * | 1979-05-23 | 1980-12-03 | Achilles Corp | Preparation of flame-retardant, low-smoke generating rigid foam |
| DE3230771A1 (en) * | 1982-08-19 | 1984-02-23 | Th. Goldschmidt Ag, 4300 Essen | METHOD FOR PRODUCING POLYMERISATS WITH LONG-CHAIN ALKYL RESIDUES AND / OR ARYL RESIDES BONDED IN SIDES |
| DE3347574A1 (en) * | 1983-12-30 | 1985-07-11 | Bayer Ag, 5090 Leverkusen | SINGLE-PHASE, STABLE, SALTY MIXTURES AND THEIR USE FOR THE PRODUCTION OF POLYURETHANES |
| US6660782B1 (en) * | 1998-04-22 | 2003-12-09 | Essex Specialty Products, Inc. | Rigid polyurethane foams and method to form said foams using low molecular weight diols and triols |
-
0
- BE BE792706D patent/BE792706A/en not_active IP Right Cessation
-
1972
- 1972-01-13 GB GB168372A patent/GB1343581A/en not_active Expired
- 1972-12-13 NL NL7216883A patent/NL7216883A/xx not_active Application Discontinuation
- 1972-12-15 DE DE19722261545 patent/DE2261545A1/en active Pending
- 1972-12-15 DK DK629572AA patent/DK142548B/en not_active IP Right Cessation
- 1972-12-15 ZA ZA728863A patent/ZA728863B/en unknown
- 1972-12-15 JP JP47125324A patent/JPS4881996A/ja active Pending
- 1972-12-15 FR FR7244739A patent/FR2167532B1/fr not_active Expired
- 1972-12-15 IT IT33010/72A patent/IT971959B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| JPS4881996A (en) | 1973-11-01 |
| BE792706A (en) | 1973-06-14 |
| DK142548C (en) | 1981-07-06 |
| DE2261545A1 (en) | 1973-07-19 |
| ZA728863B (en) | 1973-09-26 |
| NL7216883A (en) | 1973-07-17 |
| FR2167532B1 (en) | 1975-09-12 |
| IT971959B (en) | 1974-05-10 |
| GB1343581A (en) | 1974-01-10 |
| FR2167532A1 (en) | 1973-08-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AHB | Application shelved due to non-payment | ||
| PBP | Patent lapsed |