SE202425C1

SE202425C1 -

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Publication number: SE202425C1
Authority: SE
Publication date: 1965-01-01

Description

Uppfinnare: J E Jones, P T Garner och A V Mercer Prioritet begdrd fran den 21 mars 1963 och 5 februari 1964 (Storbritannien) Polyuretaner kunna framstallas genorn att omsatta en forening, som i sin molekylstruktur innehailer ett flertal hydroxylgrupper (en sadan forening benamnes i det foljande »hydroxylforening» eller »hydroxylgrupphaltigt medel») med en Mrening, som i sin molekylstruktur innehaller ett flertal isocyanat- eller isotiocyanatgrupper (i det foljande benamnd »organiskt polyisocyanat» eller »organiskt polyisotiocyanat)). For att Oka reaktionshastigheten Indian det organiska polyisocyanatet (eller det organiska polyisotiocyanatet) och hydroxylforeningen genomfores reaktionen normalt i narvaro av en katalysator, sarskilt en tertiar amin sasom trietylendiamin. En polyuretan med skumstruktur eller ett polyuretanskum erhalles som resultat av in situ-utveckling av en gas vid den kemiska reaktion, som leder till polyuretanbildningen, eller genom fi5rangning av ett flyktigt vatskeformigt skummedel infort i reaktionsblandningen eller genom en kombination av hada forfarandena. En skumstabilisator, t. ex. en silikonolja, inforlivas ofta med reaktionsblandningen. Om ekvivalentvikten has hydroxylforeningen Egger mellan c:a 70 och 250, kunna stela polyuretanskum erhallas, medan om ekvivalentvikten hos hydroxylforeningen Egger mellan c:a 250 och 2000 bojliga polyuretanskum kunna erhallas. Med uttrycket »ekvivalentvikt» avses fOrhallandet genomsnittlig molekylvikt Enligt uppfinningen erhalles en polyuretan, som innehaller bade halogenatomer och fosforatomer i sin molekylstruktur. En sadan polyuretan kan uppvisa goda brandfordrojande egenskaper. Inventors: JE Jones, PT Garner and AV Mercer Priority requested from 21 March 1963 and 5 February 1964 (Great Britain) Polyurethanes can be produced by the gene to react an compound which in its molecular structure contains several hydroxyl groups (such an association is hereinafter referred to as » hydroxyl compound "or" hydroxyl group-containing agent ") having a purification which in its molecular structure contains a plurality of isocyanate or isothiocyanate groups (hereinafter referred to as" organic polyisocyanate "or" organic polyisothiocyanate)). In order to increase the reaction rate of Indian organic polyisocyanate (or the organic polyisothiocyanate) and the hydroxyl compound, the reaction is normally carried out in the presence of a catalyst, especially a tertiary amine such as triethylenediamine. A polyurethane having a foam structure or a polyurethane foam is obtained as a result of in situ evolution of a gas in the chemical reaction leading to the formation of polyurethane, or by trapping a volatile liquid foaming agent introduced into the reaction mixture or by a combination of the methods. A foam stabilizer, e.g. a silicone oil, is often incorporated into the reaction mixture. If the equivalent weight of the hydroxyl compound Egger is between about 70 and 250, rigid polyurethane foams can be obtained, while if the equivalent weight of the hydroxyl compound Egger between about 250 and 2000 flexible polyurethane foams can be obtained. By the term "equivalent weight" is meant the ratio of average molecular weight. According to the invention, a polyurethane is obtained which contains both halogen atoms and phosphorus atoms in its molecular structure. Such a polyurethane can exhibit good fire-retardant properties.

Sattet enligt uppfinningen for framstallning av en polyuretan kannetecknas i huvudsak darav, att ett organiskt polyisocyanat eller ett organiskt polyisotiocyanat omsattes med en polyhaloeter och en fosfonitrilpolyolester. Uppfinningen avser aver' de enligt forfarandet erhallna polyuretanerna. The process according to the invention for the preparation of a polyurethane is mainly characterized in that an organic polyisocyanate or an organic polyisothiocyanate is reacted with a polyhaloether and a phosphonitrile polyol ester. The invention also relates to the polyurethanes obtained according to the process.

Fosfonitrilpolyolestern innefattar en fosfonitrilglykolester, men anvandandet av en fosfonitrilester av en alkohol som i sin molekylstruktur innehailer mer an tva alkoholgrupper, är ej uteslutet. Exempel pa fosfonitrilglykolestern aro fosfonitrilmonoetylenglykolestrar, fosfonitrilmonopropylenglykolestrar, fosfonitrildipropylenglykoles tzar, fosfonitriltripropylenglykolestrar och fosfonitriltetrapropylenglykolestrar. Den vid utforande av forfarandet enligt uppfinningen anvanda fosfonitrilpolyolestern kan harledas frail en fosfonitrilhalid med den allmanna formeln (PNC12). eller (PNBr2). dar n är ett heltal stone an eller lika med 3. Foretradesvis harleder sig fosfonitrilglykolestem frail en fosfonitrilhalid med den allmanna formeln (PNClOn eller (PNBr2)n, dar n ar ett heltal minst 3 och hogst 20, och annu hellre harleder sig fosfonitrilglykolestern fran 2,2,4,4,6,6-hexaklorcyklotrifosfazen och 2,2,4,4,6,6,8,8-oktaklorcyklotetrafosfazen. Speciella exempel pa fosfonitrilglykolestrarna aro mono- och dipropylenglykolestrar av 2,2,4, 4,6,6-hexaklorcyklotrifosfazen och 2,2,4,4,6,6,8,8- ekvivalentvikt = genomsn. antal OH-grupper per molekyl Om ej annat angives, skall uttrycket >>polyuretan» har innefatta liven »polyuretanskum 2202 4 oktaklorcyklotetrafosfazen. Om onskvart kan fosfonitrilglykolestern -agoras av en blandning av fosfonitrilglykolestrar. The phosphonitrile polyol ester comprises a phosphonitrile glycol ester, but the use of a phosphonitrile ester of an alcohol which in its molecular structure contains more than two alcohol groups is not excluded. Examples of the phosphonitrile glycol ester are phosphonitrile monoethylene glycol esters, phosphonitrile monopropylene glycol esters, phosphonitrile dipropylene glycol esters, phosphonitrile tripropylene glycol esters and phosphonitrile tetrapropylene glycol esters. The phosphonitrile polyol ester used in carrying out the process according to the invention can be derived from a phosphonitrile halide of the general formula (PNC12). or (PNBr2). where n is an integer of stone equal to or equal to 3. Preferably the phosphonitrile glycol ester derives from a phosphonitrile halide of the general formula (PNClOn or (PNBr2) n, where n is an integer of at least 3 and at most 20, and more preferably phosphonitrile glycol ester leads to 2 , 2,4,4,6,6-hexachlorocyclotriphosphazene and 2,2,4,4,6,6,8,8-octachlorocyclotetraphosphazene Special examples of the phosphonitrile glycol esters are mono- and dipropylene glycol esters of 2,2,4, 4,6 , 6-hexachlorocyclotrifosphazene and 2,2,4,4,6,6,8,8- equivalent weight = average number of OH groups per molecule Unless otherwise stated, the term "polyurethane" shall include the life "polyurethane foam 2202 4 octachlorocyclotetraphosphazene If desired, the phosphonitrile glycol ester can be agarized by a mixture of phosphonitrile glycol esters.

Fosfonitrilliolyolestern kan lampligen framstallas genom att omsatta en flervard alkohol med en fosfonitrilhalid i narvaro av ett alkalimetallkarbonat. Med fordel utgores fosfonitrilhaliden av en blandning av fosfonitrilhalider. Exempel pa glykoler, som kunna anvandas vid framstallningen av namnda fosfonitrilglykolestrar, aro etylenglykol, dietylenglykol, trietylenglykol och monopropylenglykol, men de foredragna glykolerna aro di-, trioch tetrapropylenglykol. Foretradesvis Mr den vid genomforande av forfarandet anvanda mangden flervard alkohol yam lika med eller i huvudsak lika med den mangd flervard alkohol, som erfordras for fullstandig omvandling av fosfonitrilhaliden till motsvarande fosfonitrilpolyolester. The phosphonitrilliolyl ester can be conveniently prepared by reacting a polyhydric alcohol with a phosphonitrile halide in the presence of an alkali metal carbonate. Advantageously, the phosphonitrile halide is a mixture of phosphonitrile halides. Examples of glycols which can be used in the preparation of said phosphonitrile glycol esters are ethylene glycol, diethylene glycol, triethylene glycol and monopropylene glycol, but the preferred glycols are di-, trio and tetrapropylene glycol. Preferably, the amount of polyhydric alcohol used in carrying out the process is equal to or substantially equal to the amount of polyhydric alcohol required for the complete conversion of the phosphonitrile halide to the corresponding phosphonitrile polyol ester.

De polyhaloetrar, som kunna anvandas vid forfarandet enligt uppfinningen aro foretradesvis addukter, som i sin molekylstruktur innehalla ett flertal aktiva vateatomer i stand att reagera med isocyanat- eller isotiocyanat-radikaler, vilka addukter framstallas genom aft omsatta en halosubstituerad alkylenoxid, eventuellt tillsammans med en alkylenoxid, med en forening som i sin molekylstruktur innehaller minst tva aktiva vateatomer. En polyhaloeter innehaller i sin molekylstruktur hydroxi-avslutade polymera kedjor innehallande caialkylen- eller halo-sub stituerade mdalkylenradikaler. Bland alkylenoxiderna kunna namnas etylenoxid, propylenoxid och 1-butenoxid, och bland de halo-substituerade alkylenoxiderna epiklorhydrin, epibromhydrin och 2- metylepiklorhydrin. Exempel pa foreningar innehallande minst tvã aktiva vateatomer aro vatten, monopropylenglykol, glycerol och sorbitol. Medan de vid forfarandet anvandbara polyhaloetrarna kunna vara dioler, exempelvis polyepiklorhydrin eller en monopropylenglykol-epibromhydrin-addukt, är det att foredraga att anvanda trioler, sasom glycerol-epiklorhydrin- och glycerol-epibromhydrin-addukter, tetroler, sasom pentaerytritolepiklorhydrin-addukter, och hexoler, sasom sorbitol-epiklorhydrin-addukter. Exempel pa polyhaloetrar, som aro sampolymerer, aro glycerolepiklorhydrin-propylenoxid-addukter och sorbitol-epiklorhydrin-propylenoxid-addukter. The polyhaloethers which can be used in the process according to the invention are preferably adducts which in their molecular structure contain a plurality of active hydrogen atoms capable of reacting with isocyanate or isothiocyanate radicals, which adducts are prepared by reacting a halo-substituted alkylene oxide, optionally together with oxide , with an association which in its molecular structure contains at least two active hydrogen atoms. A polyhaloether contains in its molecular structure hydroxy-terminated polymeric chains containing calcium alkylene or halo-substituted methylene radicals. Among the alkylene oxides may be mentioned ethylene oxide, propylene oxide and 1-butene oxide, and among the halo-substituted alkylene oxides epichlorohydrin, epibromohydrin and 2-methylpichlorohydrin. Examples of compounds containing at least two active hydrogen atoms are water, monopropylene glycol, glycerol and sorbitol. While the polyhaloethers useful in the process may be diols, for example polyepichlorohydrin or a monopropylene glycol-epibromohydrin adduct, it is preferable to use triols, such as glycerol-epichlorohydrin and glycerol-epibromohydrin adducts, tetrols and hydrolytes, tetrols and hexolithrices such as sorbitol-epichlorohydrin adducts. Examples of polyhaloethers are copolymers, glycerol epichlorohydrin-propylene oxide adducts and sorbitol-epichlorohydrin-propylene oxide adducts.

Valfritt anvandbara polyetrar vid forfarandet enligt uppfinningen aro addukter, som i sin molekylstruktur innehalla ett flertal aktiva vateatomer, med formaga aft reagera med isocyanat- eller isotiocyanat-radikaler, vilka addukter framstallas genom att omsatta en alkylenoxid med en forening innehallande aktiva vateatomer. I addukten ersattas de aktiva vateatomerna med hydroxi-avslutade oxialkylenkedjor. Anvandbara polyetrar aro bl. a. polyoxialkylenglykoler, sasom polyetylenglykol och polypropylenglykol samt addukter mellan alkylenoxider och flervarda alkoholer, exempelvis en monopropylenglykol-propylenoxidaddukt och en pentaerytrito1-1-butenoxid-addukt. De Lir narvarande fiiredragna valfritt anvandbara polyetrarna aro glycerol-propylenoxid-addukter. Optionally useful polyethers in the process of the invention are adducts which in their molecular structure contain a plurality of active hydrogen atoms, capable of reacting with isocyanate or isothiocyanate radicals, which adducts are prepared by reacting an alkylene oxide with a compound containing active hydrogen atoms. In the adduct, the active hydrogen atoms are replaced by hydroxy-terminated oxyalkylene chains. Usable polyethers include a. polyoxyalkylene glycols, such as polyethylene glycol and polypropylene glycol and adducts between alkylene oxides and polyhydric alcohols, for example a monopropylene glycol-propylene oxide adduct and a pentaerythritol-1-butene oxide adduct. The presently optionally preferred polyethers are glycerol-propylene oxide adducts.

For framstallning av stela polyuretanskum bOr ekvivalentvikten hos hydroxylforeningen lampligen ligga mellan 100 och 130. Ett tillfredsstallande sten polyuretanskum kan med fordel framstallas med an-vandande sasom hydroxylforening av dipropylenglykoles tern av blandade fosfonitrilklorider med den allmanna formeln (PNC12)., en glycerol-propylenoxid-addukt med en genomsnittlig molekylvikt mellan 275 och 325 och en glycerolepiklorhydrin-addukt med en genomsnittlig molekylvikt mellan 375 och 425. For the production of rigid polyurethane foams, the equivalent weight of the hydroxyl compound should suitably be between 100 and 130. A satisfactory stone polyurethane foam can be advantageously prepared using such as hydroxyl compound of dipropylene glycols tern of mixed phosphonitrile chlorides of the general formula (PNC12-propyl). adduct with an average molecular weight between 275 and 325 and a glycerol epichlorohydrin adduct with an average molecular weight between 375 and 425.

Polyuretanerna enligt uppfinningen ha brandfordrOjande egenskaper. Brandfordrojande polyuretaner kunna framstallas av fosfonitrilpolyolestrar och polyhaloetrar i enlighet med uppfinningen, cla proportionerna mellan namnda estrar och namnda polyhaloetrar aro sadana, att hydroxylforeningen lamnar c:a 0,5-3 vikt-% fosfor och c:a 5-30 vikt-% halogen. Sarskilt namnvarda aro hydroxylfOreningar, som lamna 1-2 vikt-% fosfor och 10-20 vikt-% klor. Polyuretaner framstallda enligt uppfinningen kunna aven uppvisa god dimensionsstabilitet under fuktiga fOrhallanden. The polyurethanes according to the invention have flame retardant properties. Fire-retardant polyurethanes can be prepared from phosphonitrile polyol esters and polyhaloethers in accordance with the invention, the proportions between said esters and said polyhaloethers are such that the hydroxyl compound leaves about 0.5-3% by weight of phosphorus and about 5-30% by weight of halogen. . Particularly named are hydroxyl compounds which leave 1-2% by weight of phosphorus and 10-20% by weight of chlorine. Polyurethanes made according to the invention can also show good dimensional stability under humid conditions.

Uppfinningen fortydligas i det Raj ande genom exempel, vid vilka polyuretanskum erhollos genom omsattning av en hydroxylforening med tekniskt p,p'-difenylmetan-diisocyanat, som salufores under benamningen »Caradate 30», och skumstrukturen erholls antingen genom utveckling av koldioxid vid den reaktion, som ledde till polyuretanbildningen, eller genom forangning av triklorfluormetan (saluford under benamningen »Isceon 11»). Receptet for framstallningen av polyuretanskum_ menvar foljande: Hydroxylforening 100 viktdelar Trie tylendiamin 0,» Trietylamin 1,» Silikonolja L 1,0 »Caradate 30» samt % molart overskott Vatten eller 4,0 » »Isceon 11» 35-» Det 10 %-iga molara overskottet av »Caradate 30» baserades pa totala antalet aktiva vateatomer i receptet istand att reagera med det organiska polyisocyanatet. Den brandfordrojande verkan faststalldes i exempel 1-12 enligt ASTM-prov D-1692-59T. Betingelserna vid framstallningen av polyuretanskummen och de erhallna resultaten framga av tabell 1 nedan Exempel 1-4. Dessa exempel askadliggOra verkan av franvaron av klor och/eller fosfor pa de brandfordrojande egenskaperna has polyuretan- 20243 skum. I exempel 1 och 2 utgjordes hydroxylforeningen av en glycerol-propylenoxid-addukt med den genomsnittliga molekylvikten 300, och i exempel 3 och 4 utgjordes hydroxylforeningen av en glycerol-epiklorhydrin-propylenwrid-addukt med den genomsnittliga molekylvikten 400. The invention is further illustrated by examples in which polyurethane foams are recovered by reacting a hydroxyl compound with technical p, p'-diphenylmethane diisocyanate, which is marketed under the name "Caradate 30", and the foam structure is obtained either by evolution of carbon dioxide in that reaction, which led to the formation of polyurethane, or by evaporation of trichlorofluoromethane (marketed under the name «Isceon 11»). The recipe for the production of polyurethane foam is as follows: Hydroxyl compound 100 parts by weight Trie tylenediamine 0, »Triethylamine 1,» Silicone oil L 1.0 »Caradate 30» and% molar excess Water or 4.0 »» Isceon 11 »35-» It 10% - The molar excess of "Caradate 30" was based on the total number of active hydrogen atoms in the recipe capable of reacting with the organic polyisocyanate. The fire retardant effect was determined in Examples 1-12 according to ASTM test D-1692-59T. The conditions for the preparation of the polyurethane foam and the results obtained are shown in Table 1 below Examples 1-4. These examples are detrimental to the effect of the absence of chlorine and / or phosphorus on the fire retardant properties of polyurethane foam. In Examples 1 and 2, the hydroxyl compound was a glycerol-propylene oxide adduct having an average molecular weight of 300, and in Examples 3 and 4, the hydroxyl compound was a glycerol-epichlorohydrin-propylene oxide adduct having an average molecular weight of 400.

Exempel 5-11. I dessa exempel utgjordes hydroxylforeningen av en fosfonitrilglykolester, -en glycerol-epiklorhydrin-addukt med molekylvikt c:a 400 och en glycerol-propylenoxid-addukt med molekylvikt c:a 300. I exempel 5 och 6 utgjordes fosfonitrilglykolestern av dipropylenglykolestrar av blandade cykliska fosfonitrilklorider med den allmanna formeln (PNC12)„, vilka fosfonitrilklorider innehollo 50-60 vikt-% 2,2,4,4, 6,6-hexaklorcyklotrifosfazen, 10-15 vikt-°,/, 2,2, 4,4,6,6,8,8-oktaklorcyklotrifosfazen, 1-3 vikt-% lineara fosfonitrilklorider och aterstoden cykliska fosfonitrilklorider med den allmanna formeln (PNCI,)y, ddr y är ett heltal stone an 4. Namnda blandning av fosfonitrilklorider benamnes i det foljande fosfonitrilkloridblandning A. I exempel 7-10 utgjordes fosfonitrilestern av dipropylenglykolestrar av 2,2,4,4,6,6-hexaklorcyklotrifosfazen och 2,2,4,4,6,6,8,8-oktaklorcyklotetrafosfazen medan i exempel 11 fosfonitrilglykolestern utgjordes av dietylenglykolestrar av 2,2,4,4,6,6-hexaklor cyklotrifosfazen och 2,2,4,4,6,6,8,8-oktaklorcyklotetrafosfazen. Examples 5-11. In these examples, the hydroxyl compound was a phosphonitrile glycol ester, a glycerol-epichlorohydrin adduct having a molecular weight of about 400 and a glycerol-propylene oxide adduct having a molecular weight of about 300. In Examples 5 and 6, the phosphonitrile glycol ester sulfocyl esters of dipole the general formula (PNC12) 2, which phosphonitrile chlorides contained 50-60% by weight of 2,2,4,4, 6,6-hexachlorocyclotrifosphazene, 10-15% by weight, 2,2, 4,4,6, 6,8,8-octachlorocyclotriphosphazene, 1-3% by weight of linear phosphonitrile chlorides and the residue cyclic phosphonitrile chlorides of the general formula (PNCI,) y, ddr y are an integer of stone an 4. The said mixture of phosphonitrile chlorides is named in the following A. chlorophyllone In Examples 7-10 the phosphonitrile ester of dipropylene glycol esters consisted of 2,2,4,4,6,6-hexachlorocyclotrifosphazene and 2,2,4,4,6,6,8,8-octachlorocyclotetraphosphazene while in Example 11 the phosphonitrile glycol ester consisted of diethylene glycol esters of 2,2,4,4,6,6-hexachlorocycle otrifosphazene and 2,2,4,4,6,6,8,8-octachlorocyclotetraphosphazene.

Exempel 12-15. I dessa exempel inneholl hydroxylthreningen en fosfonitrilglykolester, en glycerol-epildorhydrin-propylenoxid-addukt och en sorbitol-epiklorhydrin-propylenoxid-addukt. exempel 12 utgjordes fosfonitrilglykolestern av tripropylenglykolestrar av fosfonitrilkloridblandning A. I exempel 13 och 14 utgjordes fosfonitrilglykolestern av tripropylenglykolestrar av en blandning av fosfonitrilklorider innehallande 3035 vikt-% 2,2,4,4,6,6-hexaklorcyklotrifosfazen, 10-15 vikt-% 2,2,4,4,6,6,8,8-oktaklorcyklotetrafosfazen, 20-25 vikt-% lineara fosfonitrilklorider och Aterstoden cykliska fosfonitrilklorider med den allmanna formeln (PNC1,)y, vilken blandning av fosfonitrilklorider i det foljande benamnes fosfonitrilkloridblandning B. I exempel 15 utgjordes fosfonitrilkloridestern av tetrapropylenglykolestrar av fosfonitrilkloridblandning B. Examples 12-15. In these examples, the hydroxylthrenate contained a phosphonitrile glycol ester, a glycerol-epildorhydrin-propylene oxide adduct and a sorbitol-epichlorohydrin-propylene oxide adduct. Example 12, the phosphonitrile glycol ester consisted of tripropylene glycol esters of phosphonitrile chloride mixture A. In Examples 13 and 14, the phosphonitrile glycol ester of tripropylene glycol esters consisted of a mixture of phosphonitrile chlorides containing 3035% by weight of 2,2,4,4,6,6-hexafloro , 2,4,4,6,6,8,8-octachlorocyclotetraphosphazene, 20-25% by weight of linear phosphonitrile chlorides and Aterstoden cyclic phosphonitrile chlorides of the general formula (PNC1,) y, which mixture of phosphonitrile chlorides in the phosphonitrile mixture of the following name B. In Example 15, the phosphonitrile chloride ester consisted of tetrapropylene glycol esters of phosphonitrile chloride mixture B.

Exempel 16 och 17. I dessa exempel utgjordes hydroxylfOreningen av en blandning av dipropylenglykolestrar av 2,2,4,4,6,6-hexaklorcyklotrifosfazen och 2,2,4,4,6,6,8,8-oktaklorcyklotetrafosfazen, en glycerol-epiklorhydrin-addukt med molekylvikt c:a 400 och en glycerol-propylenoxidaddukt med molekylvikt c:a 300. Examples 16 and 17. In these examples, the hydroxyl compound consisted of a mixture of dipropylene glycol esters of 2,2,4,4,6,6-hexachlorocyclotriphosphazene and 2,2,4,4,6,6,8,8-octachlorocyclotetraphosphazene, a glycerol -epichlorohydrin adduct with a molecular weight of about 400 and a glycerol-propylene oxide adduct with a molecular weight of about 300.

Tabell 1. Table 1.

Exempel 1 2 Fosforhalt I vikt-%* Klorhalt i vikt-%* Blasmedel Vatten »Isceon 11» ASTM-prov Klassifieering Helt uppbrunnen Brannen langd, cm Helt uppbrunnen 3 Vatten S.S. 9,7 4 »Isceon 11» Brunnen 15,2 1,4 Vatten S.S. 6,4 6 1,4 »Isceon 111 S.S. 5,1 7 1,4 Vatten S.S. 7,9 8 1,4 »Isceon 11» S.S. 5,3 9 1,4 Vatten S.S. 4,1 1,4 »Isceon 11» S.S. 3,3 11 1,4 »Isceon 11» I.B. 12 1,»Isceon 111 S.S. 3,2 13 1,Vatten S.S. 3,2 14 1,»Isceon 1S.S. 3,2 1,»Isceon 11» S.S. _3,2 16 2,0 Vatten S.S. 7,1 17 2,0 »Isceon 1S.S. 5,1 S.S. = sjalvslocknande 1.B. icke brinnande * raknat pa totala vikten av hydroxylforeningen. Example 1 2 Phosphorus content In weight -% * Chlorine content in weight -% * Blowing agent Water »Isceon 11» ASTM test Classification Fully burnt Fire length, cm Fully burnt 3 Water S.S. 9.7 4 »Isceon 11» Well 15.2 1.4 Water S.S. 6.4 6 1.4 »Isceon 111 S.S. 5.1 7 1.4 Water S.S. 7.9 8 1.4 »Isceon 11» S.S. 5.3 9 1.4 Water S.S. 4.1 1.4 »Isceon 11» S.S. 3.3 11 1.4 »Isceon 11» I.B. 12 1, »Isceon 111 S.S. 3.2 13 1, Water S.S. 3.2 14 1, »Isceon 1S.S. 3.2 1, »Isceon 11» S.S. _3.2 16 2.0 Water S.S. 7.1 17 2.0 »Isceon 1S.S. 5.1 S.S. = self-extinguishing 1.B. non-burning * based on the total weight of the hydroxyl compound.

Exempel 18-32. I dessa exempel faststalldes dimensionsstabiliteten lies polyuretanskum under fuktiga forhallanden genom att utsatta ett prov av skummet med dimensionerna 15,24 x 2,54 x 2,54 cm for en relativ fuktighet av 100 % och en temperatur av 37,8° C under 168 timmar samt mata langdOkningen hos provet. Resultaten aro sammanfattade i tabell 2 nedan. I exempel 18 och 19 utgjordes hydroxylforeningen av en glycerolepiklorhydrin-propylencodd-addukt med molekylvikt c:a 400. I exempel 20-32 utgjordes hydroxylforeningen av de blandningar, som anvandes i exempel 5-17. 4 Exem- Fosfor- Klor- pelhalt ihalt i vikt-vikt- Tabell 2. Examples 18-32. In these examples, the dimensional stability of polyurethane foam under humid conditions was determined by subjecting a sample of the foam measuring 15.24 x 2.54 x 2.54 cm to a relative humidity of 100% and a temperature of 37.8 ° C for 168 hours. and feed the length increase of the sample. The results are summarized in Table 2 below. In Examples 18 and 19, the hydroxyl compound was a glycerol epichlorohydrin-propylene codd adduct having a molecular weight of about 400. In Examples 20-32, the hydroxyl compound was the mixtures used in Examples 5-17. 4 Example- Phosphorus- Chlorine content in weight-weight- Table 2.

Blasmedel 202 % Langdiikning %* %* 18 0 Vatten —0,8 19 0 »Isceon 11» Noll 1,4 Vatten +0,4 21 1,4 »Isceon 11» + 0,8 22 1,4 Vatten —0,4 23 1,1 »Isceon 11» + 1,1 24 1,4 Vatten —0,4 1,4 »Isceon 11» + 1,1 26 1,4 »Isceon 11» + 0,4 27 1,»Isceon 11» + 0,4 28 1,Vatten —0,8 29 1,»Isceon 11» + 1,2 1,»Isceon lb 1,2 31 2,0 Vatten —0,8 32 2,0 »Isceon lb + 1,1 * ranat pt totala vikten av hydroxylforeningen Blowing agent 202% Long thickness% *% * 18 0 Water —0.8 19 0 »Isceon 11» Zero 1.4 Water +0.4 21 1.4 »Isceon 11» + 0.8 22 1.4 Water —0, 4 23 1,1 »Isceon 11» + 1,1 24 1,4 Water —0,4 1,4 »Isceon 11» + 1,1 26 1,4 »Isceon 11» + 0,4 27 1, »Isceon 11 »+ 0.4 28 1, Water —0.8 29 1,» Isceon 11 »+ 1.2 1,» Isceon lb 1.2 31 2.0 Water —0.8 32 2.0 »Isceon lb + 1.1 * plotted on the total weight of the hydroxyl compound

Claims

Patent claim:

A process for producing a polyurethane, characterized in that an organic polyisocyanate or an organic polyisothiocyanate is reacted with a hydroxyl group-containing agent comprising a phosphonitrile polyol ester and a polyhaloether.

2. A kit according to claim 1, characterized in that the polyhaloether consists of a glycerol epichlorohydrin adduct.

3. A kit according to claim 1 or 2, characterized in that the hydroxyl group-containing agent also comprises a polyether.

4. A kit according to claim 3, characterized in that the polyether consists of a glycerol-propylene oxide adduct.

Modification of the kit according to claim 1, characterized in that the hydroxyl group-containing agent comprises a phosphonitrile polyol ester, a glycerol-epichlorohydrin adduct and a glycerol-propylene oxide adduct. 4

Claimed as claimed in one of the preceding claims, ddray may be that the phosphonitrile polyol ester is or comprises a phosphonitrile glycol ester.

Claim 6 according to claim 6, characterized in that the phosphonitrile glycol ester consists of the dipropylene glycol ester of a phosphonitrile halide.

8. According to claim 6, it is claimed that the phosphonitrile glycol ester consists of the tripropylene glycol ester of a phosphonitrile halide.

9. A kit according to claim 6, characterized in that the phosphonitrile glycol ester consists of the tetrapropylene glycol ester of a phosphonitrile halide.

10. According to one of claims 7-9, it is claimed that the phosphonitrile halide is of the general formula (PNC12). or (PNBr2). ddr n is an integer greater than or equal to 3.

11. A kit according to claim 10, characterized in that the phosphonitrile halide is of the general formula (PNC12) „or (PNBr2)„, where n is an integer of at least 3 and at most 20.

12. A kit according to claim 11, characterized in that the phosphonitrile halide consists of 2,2,4,4, 6,6-hexachlorocyclotriphosphazene and / or 2,2,4,4,6,6,8,8-octachlorocyclotetraphosphazene.

13. According to some of the foregoing patent claims, characterized in that the equivalent weight of the hydroxyl group-containing agent Egger is between 100 and 130.

14. According to one of the preceding claims, characterized in that the hydroxyl group-containing agent leaves 0.5-3% by weight of phosphorus and 5-30% by weight of halogen.

15. A kit according to claim 14, characterized in that the hydroxyl group-containing agent leaves 1-2% by weight of phosphorus and 10-20% by weight of chlorine.

16. Polyurethane prepared from the salt of any of the foregoing patent claims. Request publications: