FR2458562A1 - NOVEL MIXTURES OF POLYOLS AND THEIR USE IN A PROCESS FOR THE PREPARATION OF CELLULAR POLYMERS - Google Patents

Abstract

THE PRESENT INVENTION RELATES TO NEW MIXTURES OF POLYOLS. FOLLOWING THE INVENTION, THESE MIXTURES OF POLYOLS INCLUDE ABOUT 20 TO ABOUT 85 BY WEIGHT OF ONE OR MORE COMPOUNDS SELECTED FROM AMINE I DIOLS, AMID II DIOLS AND AMINE III TRIOLS AND ABOUT 15 A ABOUT 80 BY WEIGHT OF A PRIMARY HYDROXYL POLYOL IV CHARACTERIZED BY A MOLECULAR WEIGHT OF ABOUT 60 TO ABOUT 1000. THESE MIXTURES OF POLYOLS ARE PARTICULARLY INTERESTING FOR THE PREPARATION OF POLYISOCYANURATE FOAMS.

Description

"CELLULAR POLYMERS AND THEIR PREPARATION" The present invention is

  relating to cellular polymers and their intermediates, and more particularly relates to novel polyol mixtures and their use in the preparation of cellular polyisocyanurates. Cell polyisocyanurate polymers are well known in the art for use in various types of thermal insulation applications. They are also well known for their ability to resist heat and flames; see United States Patent Nos. 3,745,133, 3,986,991 and 4,003,859. Small amounts of polyols are sometimes added to the foam generating ingredients so as to modify the properties of the foam. When fluorocarbon blowing agents are used, the problem of incompatibility which may arise between the polyol, especially the primary hydroxyl polyols, and the fluorocarbon agent in premixes of resins is in general, resolved by previously mixing most, if not all, of the fluorocarbon agent with the polyisocyanate, see the United States Patents cited above. Polyisocyanurate foams are of particular use in the production of laminated foam boards which can be prepared with a variety of different materials acting as packing layers. Problems that may arise from the production of such a laminate material are 1) the lack of uniform strength of the foam core; 2) poor adhesion between the foam core and the packing layer; 3) the maintenance of good fire resistance in the foam; and 4) maintaining the friability of the foam at low levels. These problems have been overcome in the art by using small amounts of low equivalent weight polyols, especially diols, in the formulation, which is combined with the heating of the laminate formed in a microwave oven. a temperature of 71WC at 880C; see U.S. Patent No. 3,903,346. However, the low weight polyols used, particularly the preferred diols (see column 4, lines 59-61 of US Patent 3,903,346) having only hy The primary hydroxyls can not be premixed with the fluorocarbon blowing agent in a "B" type component because of the low solubility of the diol-fluorocarbon pair. This requires mixing the fluorocarbon agent with the polyisocyanate in the "A" component. In addition, because of the immiscibility of the fluorocarbon agent and diol, the above-mentioned United States patent specifies that a third component "C" is required, this third component containing the catalytic component dissolved in a low molecular weight glycol; see column 2, lines 32-33 and the examples of U.S. Patent No. 3,903,346. In addition, the laminates prepared in accordance with the aforementioned US patent, must be heated in an oven to obtain a product whose foam core has a uniform strength. Surprisingly, it has been found that high levels of fluorocarbon blowing agent are completely miscible with low molecular weight polyols containing primary hydroxyl groups when new mixtures are used which take certain types of amine or amide diols or amine triols with the primary hydroxyl based polyols. Other ingredients that may be present in the miscible mixtures are surfactants, catalysts, and the like. In addition, it has been found that the same type of mixtures containing miscible primary hydroxyls as those described above can be obtained with the exception that the fluorocarbon component is replaced by water. In addition, it has been discovered that the above-mentioned novel polyol mixtures can be used in small amounts as a Type B component to prepare polyisocyanurate foams characterized by low friability, fine cell structure, good dimensional stability. and by low flame spread, via a two-component process, i.e. a Type A and B process. The fluorocarbon component and water act as blowing agents in their process. respective foam generating formulations. In addition, the types of amino amine diols or amino amine triols discussed above may be used as sole polyol ingredients in combination with the fluorocarbon agent or the water, catalyst, surfactant and other adjuvants to obtain the polyisocyanurate foams of the present invention. . Quite unexpectedly, the pre-

  The presence of the diols of amides or amines or amine trisols in the B component gives excellent reactive compatibility between the polyisocyanate and the other ingredients. This in turn gives rise to a higher reactivity compared to the foams of the prior art and a very good reaction exotherm. The high exotherm is particularly advantageous when foam laminates are prepared because it provides excellent adhesion between the foam and the packing material, thus eliminating the need to heat the foam. laminate formed in an oven. The present invention comprises mixtures of polyols comprising (i) about 20% to about 85% by weight, based on this mixture, of a compound or a mixture of compounds selected from compounds of the following formulas: 51 1 ~~ 15 2CH2CHO - H 0 / / CH2CHO_, H R2-CN; and wherein R is an aliphatic radical having from 8 to 18 carbon atoms, and wherein R is an aliphatic radical having from 8 to 18 carbon atoms, and wherein R is an aliphatic radical having from 8 to 18 carbon atoms. inclusive, R 2 is an aliphatic radical having 7 to 17 carbon atoms inclusive, each R 1 is independently selected from hydrogen and methyl, x and y each independently has an average value of from about 4 to about 15 inclusive, x 'and y' are each independently of an average value of about 1 to 3 inclusive, x ", y" and z each independently have an average value of about 1 to about 5 inclusive, and n is 2 or 3, and (ii) about 15% to about 80% of a primary hydroxyl (IV) -containing polyol having a molecular weight of about 60 to about 1000. The invention also includes miscible mixtures from the above-mentioned polyol blends in combination with the above-mentioned polyol blends. c a fluorocarbon blowing agent or formed of water. The present invention also includes miscible blends from the aforementioned polyol blends in combination with a fluorocarbon or water blown agent and an isocyanate trimerization catalyst. The invention also includes processes for the preparation of polyisocyanurate cellular polymers which use, as a mixed component, a compound or a mixture of compounds selected from the compounds of formulas (I), (II) and (III) ci above, where the values of x and y may have independent mean values ranging from about 1 to about 15, but preferably from about 4 to about 15, x ', y', x ", y", z, n, R, R 1 and R 2 having the definitions given above, in combination with a fluorocarbon blowing agent or consisting of water and a trimerization catalyst, the mixed component preferably containing, furthermore the polyol (IV), in which case the diol (I) is as defined above with the narrowest range of x and y from about 4 to about 15, in the reaction with an organic polyisocyanate. The invention also includes the cellular polymers obtained by the aforesaid process. The invention also comprises a laminated panel having a polyisocyanurate foam core obtained according to the improved process of the present invention. By the term "aliphatic radical" is meant, with respect to R, alkyl and alkenyl radicals having from 8 to 18 carbon atoms inclusive. Examples of alkyl radicals are octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and their isomeric forms. Examples of alkenyl radicals are octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl and their isomeric forms. The term "aliphatic radical" with respect to R 2 is understood to mean alkyl and alkenyl radicals having from 7 to 17 carbon atoms inclusive Examples of alkyl and alkenyl radicals in this case are the same as above, with the exception that the range of carbon atoms is narrower, starting with heptyl or heptenyl radicals and ending with heptadecyl or heptadecenyl radicals and their isomeric forms, the polyol mixtures of the present invention can be used as the Polyurethane Ingredients in the Preparation of Polyurethane Foams Polyurethane foams are well known in the art for use in a wide range of applications involving thermal insulation and soundproofing in both industrial and commercial buildings. Polyol blends find particular use, as already mentioned, as minor constituents in the preparation of the blends. polyisocyanurate foams, especially polyisocyanurate foams prepared in foam laminates and by means of spray foam equipment. These foams are well known for their resistance to heat and

  5 fire and are used for the manufacture of laminated panels and foam mass which are both used in the construction of buildings for thermal insulation and soundproofing. The polyol blends of the present invention are prepared by simply blending together, in the aforementioned weight proportions, the amine diol (I), the amide diol (II) or the amine triol (III). and a polyol containing primary hydroxyls (IV) as defined above, in a mixing container, a storage tank or a suitable storage container, etc. Component (I), (II) or (III) is preferably used in an amount of from about 25% to about 60% by weight based on the weight of the mixture, while the polyol containing primary hydroxyls is used at about from about 40% to about 75% by weight. Preferred components (I), (II) and (III) are those of the above formulas, wherein R 1 is hydrogen in all cases. A particularly interesting diol is that which corresponds to formula (1) wherein both R 1 groups are hydrogen, and o x and y each independently have an average value of from about 5 to about 10 inclusive. A particularly useful amide diol corresponds to formula (II), wherein both R 1 groups are hydrogen and where x 'and z' are each independently an average value of from about 2 to about 3 inclusive. A particularly valuable amine triol corresponds to formula (III), in which all R 1 groups are hydrogen, and ox ", y" and z each have an average value of about 3 to about 5. inclusive, and n is 3. The amine diols (I) are prepared using ordinary reactions well known to those skilled in the art and in some cases the amine diols are available in the art. trade. Typically, the amine diols (I) can be prepared by reacting an appropriate dialkanolamine with the appropriate aliphatic halide compound (RX), or with a mixture of different RX compounds or any aliphatic group. (R) fall within the above definition, and X represents a halogen, preferably chlorine or bromine. If the desired number of alkyleneoxy groups are not already present in the dialkanolamine prior to the reaction with the aliphatic halide, they may be added thereafter by reacting the alkylated dialkanolamine with the appropriate number of moles. ethylene oxide or propylene oxide, or mixtures thereof, to obtain the amine diols of the formula (I). The amine diols (I) are preferably prepared by reacting the appropriate primary fatty amine R-NH 2 or a mixture of fatty amines where all the R groups are as defined above, with about 2 to about 30 moles, preferably about 8 to about 30 moles, and more preferably 10 to 20 moles, ethylene oxide or propylene oxide per molar proportion of amine fat; see Bulletin 1294, 2458562, entitled "Ethoxylated Fatty Amines", Ashland Chemical Company, Ashland Oil Division, Box 2219, Colum- bus, Ohio 43216, for a detailed study of the preparation of the amine diols which it contains. is question. Examples of starting fatty amines are octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine and their isomeric forms. Examples of alkenylamines are octenylamine, decenylamine, dodecenylamine, tetradecenylamine, hexadecenylamine, octadecenylamine and their isomeric forms. Other examples of such fatty amines are mixtures of alkyl and alkenyl amines, for example coconut amine which is constituted by the following mixture given in approximate weight percentages: % decylamine, 53% dodecylamine, 24% tetradecylamine, 11% hexadecylamine, 5% octadecylamine and 5% octadecenylamine; soybean amine in the following approximate proportions: 11.5% hexadecylamine, 4% octacylamine, 24.5% oleylamine, 53% linoleylamine, and 7% linolenylamine; and tallow amine in the following approximate proportions: 4% tetradecylamine, 29% hexadecylamine, 20% octadecylamine, and 47% octadecenylamine. Other examples of starting fatty amines are the halogenated fatty amines, in particular the chlorinated and brominated fatty amines, which, for example, can be obtained by the chlorination or bromination of coconut amine, soy amine, tallow amine, etc. A particularly valuable group of fatty amines includes the coconut amine mixture, the soy amine mixture and the tallow amine mixture. A preferred member of this group is coconut amine. The amide (II) diols are prepared using standard reactions well known to those skilled in the art.

  of the technique. Specifically, they can be prepared by reacting the appropriate fatty acid dialkanolamine, fatty acid ester or fatty acid chloride according to the following reaction: ACH2CHO0H R2COR3 + Wherein R 2, R 1, x 'and y' have the same definition as above and R 3 represents -OH, -OR 4 or X, where R 4 represents a compound of formula (I); any typical esterification group, such as lower alkyl, aryl, cycloalkyl, etc., and X represents a halogen, such as chlorine or bromine In the case where diethanolamine or diisopropanolamine or a mixture of these are the starting dialkanolamine, and when it is desirable to obtain amide diols in which the values of x 'and y' are greater than 1, then dialcanolamide is simply reacted. intermediate in a molar ratio with about 1 to about 4 moles of ethylene oxide or propylene oxide, or See Bulletin 1295, "Varamide Alkanolamides", Ashland Chemical Company, Division of Ashlane Oil, Inc., Box 2219, Columbus, Ohio 43216, for a detailed description of the preparation of fatty acid dialkanolamides. . The amide diols (II) are preferably prepared by converting the fatty acids to the corresponding fatty acid amides (R2CONH2) and reacting the amide with from about 2 to about 6 moles per mole of mole. amide, ethylene oxide or propylene oxide, or mixtures thereof. Examples of starting fatty acids (from which also the corresponding acid esters, acid halides and amides are derived) are the caprylic, capric, lauric, myristic, palmitic and stearic acids and their isomeric forms. Examples of unsaturated fatty acids are decylenic, dodecylenic, palmitoleic, oleic, linoleic acids and their isomeric forms. Other examples of fatty acids are mixtures, for example the fatty acid mixture derived from coconut oil which is formed from the following mixture in approximate proportions by weight percent: 8, 0% caprylic acid, 7.0% saccharic acid, 48.0% lauric acid, 17.5% myristic acid, 8.2% palmitic acid, 2.0% stearic acid, 6.0% oleic acid, and 2.5% linoleic acid, the fatty acid mixture from soybean oil: 6.5% palmitic acid, 4 2% stearic acid, 33.6% oleic acid, 52.6% linoleic acid, and 2.3% linolenic acid; and the mixture of fatty acids from tallow: 2% myristic acid, 32.5% palmitic acid, 14.5 stearic acid, 48.3% oleic acid and 2.7% linoleic acid. Other examples of starting fatty acids are the halogenated fatty acids, in particular the chlorinated and brominated fatty acids, which, for example, can be obtained by the chlorination or bromination of the fatty acid mixtures. of coconut, soy and tallow described above. A particularly preferred group of starting fatty acids and fatty acid amide intermediates are the above-described mixtures of coconut, soybean and tallow oils and mixtures thereof. coconut amide, soy amide and corresponding tallow amide. Preferred members of this group are the coconut oil blend and its cocoamide or coconut amide derivative. A preferred group of amide diols (II) are diol mixtures derived from cocoamide, soy amide and tallow amide wherein each R 1 is hydrogen and x 'and both have a value of about 3. A member of particular interest in this group of amino diols is the mixture of cocoamide diols discussed above and identified by the chemical N, N-bis (8-hydroxy-3,6-dioxaoctyl) cocoamide. Amine triols (III) are easily prepared using standard reactions well known to those skilled in the art and in some cases amine triols are commercially available. In general, the mode of preparation of the triols of amines of which n is 2 will differ slightly from that of the triols of amines of which n is equal to 3. The first triols of amines can be readily available. prepared according to the following scheme [NH3] RNH2 + CHR1-CHR1 RNHCHRCHROH - RNHCHRCHRNH2 5 V VI ethylene oxide or propylene oxide or their mixture III in which R and R are as defined above. The starting amine is reacted with an equimolar amount of ethylene oxide or propylene oxide to form the amino alcohol (V) which can easily be converted to the diamine (VI) in a characterized by reaction with ammonia, this reaction being followed by the reaction of a molar proportion of the compound (VI) with about 3 to about 15 molar proportions of ethylene oxide or propylene oxide or

  of their mixtures, so as to form the amine triol (III). The triols of amines having n equal to 3 are typically prepared by the following scheme: [HI] RNH 2 + R 1 CH = CR 1 CN - RNHCHR 1 CHR 1-CN - RNHCHR 1 CHR 1 CH 2 NH 2 VII VIII IX Ethylene oxide or ~~~~ ~ 15 ~~ propylene oxide or their mixture III <wherein R and R1 are as defined above. The starting amine is cyanoethylated with appropriately substituted acrylonitrile (VII) to form the product (VIII) which is reduced to the diamine (IX), this reaction being followed by alkoxylation with about 3 to about 15 molar proportions of ethylene oxide or propylene oxide or mixtures thereof to form the product (III). The starting fatty amines are the same as those mentioned above and those exemplified in the preparation of amine diols (I). Examples of acrylonitrile compounds which can be used in the preparation of the amine triols according to the present invention are acrylonitrile, α-methacrylonitrile, β-methacrylonitrile, α, β- dimethacrylonitrile, etc. It is preferred to use acrylonitrile. A preferred group of amine triols (III) are amine triol mixtures derived from mixtures of coconut amine, soy amine and tallow amine in which all R 1 groups represent Of hydrogen, n is 3, and x ", y" and z are each about 3 to about 5. A particularly preferred group is the amine triol mixture derived from coconut amine in wherein all R 1 groups are hydrogen, n is 3 and x ", 10 y" and z are each about 4.6. The polyol having primary hydroxyls (IV) may be any primary hydroxyl polyol having a molecular weight of from about 60 to about 1000, preferably from about 60 to 800, and more preferably from About 60 to about 600. Diols, triols and tetrols are incorporated in the polyols (IV). Preferred polyols are diols. Included in the class are primary hydroxyl-containing polyols, the various primary hydroxyl-containing diols, triols and tetrols disclosed in US Pat. No. 3,745,133, which satisfy the weight limitations of the present invention. The above-mentioned leculars and whose description with respect to these polyols is incorporated herein by reference. Preferred classes are polyester polyols prepared from dibasic carboxylic acids and polyhydric alcohols including those based on chlorendic anhydride, alkylene diols, alkoxyalkylene diols, polyalkylene ester diols, polyol Oxyalkylene ester diols, hydroxyalkylated monoamines or aliphatic diamines, resol polyols (see Methods of Polymer Chem., By WR Sorenson et al., 1961, page 293, Interscience Publishers, New York, NY) 2458562; polybutadiene resins having primary hydroxyl groups (see Poly Bd Liquid Resins, Product Bulletin BD-3, October 1974, Arco Chemical Company, Atlantic Richfield Div., New York, NY). The most preferred classes are alkylene diols, alkocyalkylene lower diols, polyalkylene ester diols, and polyoxyalkylene ester diols. Non-limiting examples of the preferred classes of polyols according to the present invention are ethylene glycol, 1,3-propanediol, 1,4-butanediol, glycerine, trimethylolpropane, pentaerythritol, diethylene glycol, polyoxyethylene glycols prepared by the addition of ethylene oxide to water, ethylene glycol or diethylene glycol, etc., which give triethylene glycol, tetraethylene glycol and higher glycols, or mixtures thereof, such that the molecular weight falls within the aforementioned range; ethoxylated glycerin, ethoxylated trimethylolpropane, ethoxylated pentaerythritol, etc. ; bis (β-hydroxyethyl) terephthalate, bis (p-hydroxyethyl) phthalate, etc. ; polyethylene succinate, polyethylene glutarate, polyethylene adipate, polybutylene succinate, polybutylene glutarate, polybutylene adipate, copolyethylene butylene succinate, copolyethylenebutylene glutarate, copolyethylenebutylene adipate, etc., hydroxy-terminated polyesters; polyoxydiethylene succinate, polyoxydiethylene glutarate, polyoxydiethylene adipate, polyoxydiethylene adipate glutarate etc., diethanolamine, triethanolamine, N, N'bis (β-hydroxyethyl) aniline, and the like. The most interesting diols are ethylene glycol diol, and polyoxydiethylene adipate glutarate polyester diols having a molecular weight of from about 400 to about 600. Particularly interesting are mixtures of about 30% about 50% by weight of diethylene glycol with about 50% to about 70% by weight

  of a polyoxydiethylene adipate glutarate polyester diol having a molecular weight of from about 400 to about 600. In the preferred polyol blends of the present invention, the fluorocarbon or water blowing agent is also present in the mixture, the fluorocarbon agent being the preferred blowing agent. When the blowing agent is a fluorocarbon agent, the unexpected advantageous characteristics of the polyol mixtures of (I), (II) or (III) with the product (IV) can be fully realized. Accordingly, miscible polyol mixtures comprising at least about 20% by weight of a fluorocarbon blowing agent and the balance being formed can be obtained. by the mixtures in the proportions mentioned above. The percentage of particular fluorocarbon agent to be dissolved in the mixture will govern the proportions of (IV) and (I), (II) or (III) to be used in any given example and its proportions, falling within the range. mentioned above, can easily be determined by one skilled in the art by successive approximation methods. Miscible polyol mixtures comprising more than 50%; By weight of fluorocarbon and even up to 90% by weight can be easily obtained with the mixtures in the aforementioned proportions of the present invention and according to the choice of mixing ingredients. In general, the amount of fluorocarbon agent which can be dissolved in the mixture for a given proportion of polyol (I), (II) or (III) is all the greater as the molecular weight of the Primary hydroxyl polyol (IV) is lower, as opposed to a mixture with a polyol (IV) of higher molecular weight taken in the same proportion. In this regard, the alkylene diols, and the lower alkoxyalkylene diols having molecular weights below 400 are interesting polyols of the formula (IV), with these lower alkoxyalkylene diols being the most interesting. The particular proportions of polyol (1), (II) or (III) with respect to the polyol (IV) to be used in any particular polyol mixture to obtain maximum miscibility with the fluorocarbon agent, can be determined by approximations - cessives. In general, when the amine diol (I) is used with the polyol (IV), mixtures of miscible polyols comprising at least 25% by weight up to at least about 65 are obtained. % by weight of a fluorocarbon blowing agent and the corresponding 75% to 35% by weight being the mixture of (I) and (IV). When one uses the amide diol (II) and the polyol (IV), target polyol mixtures are obtained comprising at least about 20% by weight up to at least about 60% by weight of a fluorocarbon blowing agent, the corresponding 80 to about 40% by weight consisting of the mixture of polyols of (II) and (IV). Finally, when the amine triol (III) and the polyol (IV) are used, miscible polyol mixtures are obtained comprising at least about 20% by weight up to at least about 5% by weight. weight of a fluorocarbon blowing agent, the corresponding 80 to about 50 wt.% being the mixture of (III) and (IV) polyols. When water is the blowing agent, it is present in the proportions of about 1% to about 6%, and preferably about 2 to about 5% by weight, 94% to 99%, and preferably the remaining 95 to 98% being product (1), (II), or (III) with product (IV). The fluorocarbon blowing agent may be any of the fluorocarbons well known to those skilled in the art and which may be used for blowing polymeric blends in the form of cellular polymers. In general, these blowing agents are halogenated aliphatic hydrocarbons which are also substituted by chlorine and / or bromine in addition to the fluorine content and are well known to those skilled in the art; see U.S. Patent 3,745,133, column 11, lines 25-38, the description of which for fluorocarbon blowing agents is incorporated herein by reference. According to a preferred embodiment of a polyol mixture of the present invention which finds particular use in the preparation of polyisocyanurate whisks, is also present in the mixture of blowing agent and components ( I), (II) or (III) and (IV), an isocyanate-trimerization catalyst. The catalytic component of isocyanate trimerization will be discussed in more detail below. The isocyanate trimerization catalyst is preferably present in the proportions of about 2 to about 20, preferably in the proportions of about 2 to about 15% by weight, the 80 to 98% by weight.

  remaining weights and preferably the remaining 85 to 98% by weight, being the above mentioned ingredients. Surprisingly, the blowing agent 10 and the polyol mixture which comprises the primary hydroxyl containing polyols are fully miscible with each other without any separation occurring during storage. this miscibility being due to the presence of the amine diol (I), the amide diol (II) or the amine triol (III). Apart from the advantages of a mixture of miscible and stable fluorochemical or fluorocarbon or water-miscible polyols, the advantageous effects of having the nitrogen-containing diol or triol present as a minor component when the Polyisocyanurate foams were prepared above. Other optional additives may be added to the polyol mixtures without affecting the miscibility and stability of the mixtures. These additives are constituted by other possible polyol components, such as secondary hydroxyl-containing polyols, dispersing agents, cell stabilizers, surfactants, flame retardants, etc. which are ordinarily used in the process of the invention. In the preparation of polyisocyanurate foams of the present invention, the amine diol, amine diol, or amine triol described above can be used as the sole polyol component in admixture with an agent. blowing agent formed from a fluorocarbon or water, and a trimerization catalyst to form a type B component for reaction with the organic polyisocyanate type A component. In this case, the values of x and y in component (I) correspond to the largest ranges as noted above, i.e., from about 1 to about 15. Percentage proportions By weight of the ingredients of the mixtures are the same as those indicated above for the proportions of catalyst to be blended with the blowing agent and the polyol component. That is, blend B is from about 2 to about 20% by weight, and preferably from about 2 to about 15% by weight of a trimerization catalyst and about 80 to about 98% by weight, and preferably about 85 to 98% by weight of component (I), (II) or (III) and a blowing agent. In the case where a fluorocarbon blowing agent is used, it is present in the proportions of from about 20 to about 80 and preferably from about 20 to about 50 wt. relative to component (I), (II) or (III), the latter component being present at a ratio of from about 20 to about 80, and preferably from about 50 to about 80% by weight. In the case where water is used as the blowing agent, it is present in an amount of from about 1 to about 6, preferably from about 2 to about 5% by weight of the component ( I), (II) or (III), which is therefore present from about 94 to about 99%, and preferably from about 95 to 98% by weight. Advantageously, the B-type mixture is used in an amount falling within the range of about 10 parts to about 120 parts, preferably in the range of about 10 to about 80 parts, and more preferably in from about 20 to about 60 parts by weight per equivalent of polyisocyanate, as long as the hydroxyl equivalents. The totals present in the mixture (B) fall in a range of about 0.05 to about 0.5 equivalents, preferably in a range of about 0.08 to about 0.4 equivalents, per equivalent of the polyisocyanate. . There is also preferably in the type B mixture a small amount of the primary hydroxyl polyol (IV) described above. This combination in the mixture not only gives rise to the stabilized miscible mixtures discussed above, but also makes it possible to obtain polyisocyanurate foams having the optimum advantageous properties discussed above, including the preparing foam laminates which do not require oven heating in order to achieve maximum foam resistance and maximum adhesion to the laminate packing layers. In this case, the values of x and y in (I) have the narrowest ranges as noted above, i.e., from about 4 to about 15. The mixture containing the diol is amine (I), amide diol (II) or amine triol (III), with the primary hydroxyl polyol (IV), the blowing agent, and the trimerization catalyst are also used. In an amount falling within the same range of isocyanate equivalent portions discussed above for the Type B mixture without component (IV); and with the same restriction mentioned above 2458562 -22

  for the range of total hydroxyl equivalents per equivalence of isocyanate. The proportions of each ingredient in the mixture by weight percent relative to the mixture are the same proportions as indicated in the description of the polyol mixtures. The amine diol (I), the amide diol (II), the amine triol (III), the primary hydroxyl polyol (IV) and the blowing agent all have the same meaning and the same range as above. The trimerization catalyst used may be any catalyst known to those skilled in the art which will catalyze the trimerization of an organic isocyanate compound to form the isocyanurate moiety. In addition, a combination of urethane generating catalyst and trimerization catalyst may be used if desired. For typical isocyanate trimerization catalysts, see The Journal of Cellular Plastics, November / December 1975, page 329, and US Patent Nos. 3,745,133, 3,896,052, 3,899,443, 3,903,018, 3,954,684 and 4,101,465, which are incorporated herein by reference. Preferred catalysts are those described in U.S. Patent Nos. 3,896,052 and 4,101,465. The first reference describes the catalytic combination (a) of an alkali metal salt of an N-substituted amide with (b) an alkali metal salt of an N- (2-hydroxyphenyl) methyl glycine and optionally ( c) a tertiary amine trimerization catalyst. The second reference describes the combination of the same components (a) and (b) discussed above with a hydroxyalkyltrialkylammonium carboxylate salt. The organic polyisocyanates which may be used in the preparation of the polyisocyanurate foams of the present invention may be any of the organic polyisocyanates ordinarily previously used in the art for this purpose. Advantageously, and in order to obtain foams having exceptionally high heat resistance and structural strength, the preferred polyisocyanates are polymethylene polyphenyl polyisocyanates, particularly those mentioned in US Pat. No. 3,745,133, the description of which for these isocyanates is given here by reference. Other useful polyisocyanates are polymethylene polyphenyl polyisocyanates treated with a small amount of an epoxy compound to reduce acidic impurities according to US Patent 3,793,362, and polymethylene polyphenyl polyisocyanates which contain high levels of the 2,4 'isomer, as is typically described in U.S. Patent 3,362,979. A particularly useful organic polyisocyanate is a mixture containing from about 30% to about 85% by weight of methylenebis (phenyl isocyanate), the remainder of this mixture being poly-methylene polyphenyl polyisocyanates having a functionality greater than 2, 0. With regard to the preparation of the polyisocyanurate foams according to the process of the invention and, in particular, polyisocyanurate foams for the preparation of foam laminates, the conventional processes and apparatus are used. known from the art (see the patents cited above); With regard to a detailed description of the method of preparation, and the use of the polyisocyanurate foam laminates, reference is made to US Pat. No. 3,896,052, which is incorporated herein by reference. incorporated by reference in the context of the present invention. The following examples describe the manner and method of manufacture and use of the invention and also specify the best mode contemplated for carrying out the invention, but the examples are in no way limiting thereto. Example 1 - The five polyisocyanurate foams (foams A to E) are prepared according to the following process. The foams are prepared in the form of hand-mixed samples by mixing together the Type A and Type B ingredients (in parts by weight) shown in Table I below, in 1.13 liter buckets. The polyisocyanate ingredient is the only component of type A whereas the ingredients of type B which are mentioned in Table I are mixed beforehand and examined before being reacted with the polyisocyanate. The mixing operation is accomplished by thorough mixing of the Type A and B ingredients in the cup with a high speed drill press motor provided with an agitator blade. The mixture is quickly poured into a cardboard boot and allowed to rise freely and harden at room temperature (about 200C). Foams B and E are according to the present invention whereas foams A, C and D are not

  not because the amine diol component has x and y values below those claimed. The type B components in all formulations are limpid without any sign of turbidity. However, in the case of foams A and C, there are secondary hydroxyl-containing polyols which are known solubilizers for fluorocarbons while in foam C the phosphate plasticizer is additionally added thereto. Foam D also contains the plasticizing ingredient. Maximum foam properties with respect to the combination of the maximum reaction exotherm with a firm, fast rate and low friability of the core and the surface are observed with the foam E. The superficial cloudiness with A foam sample removed is the point where the unreacted, glossy and moist surface of the raised or rising foam becomes cloudy or matt and indicates that an effective curing or reaction has occurred. the surface. All foam samples show a good superficial disorder. TABLE I Foams ABCDE 20 Ingredients (parts by weight) Type A: Polyisocyanate I 100 100 100 100 100 Type B: 25 Diethylene glycol 5,7 5,4 6 6 8 Varonic L-202 5,7 - 6 6 - 3 Varonic K -215 - 23.5 - - 8 4 Pluracol GP-730 5.7 - - - - PluracolDPEP-6505 - - 6 - - 30 Tris (dichloropropyl- - 7.2 18 18 - phosphate) 6 Propoxylated polyol - - 6 - L-54207 1.25 1.25 1.25 1.25 1.2 _, _ _ _ my ~ 2458562 TABLE I (cont'd) Foams ABCDE Fluorocarbon R-11B Catalyst I 5 NCO / OH Index Appearance of Component B 3 25 Approximately about 4 4 4 4 4 clear and not turbid 10 Magnesium Reaction Foam 170.5, C Fast rate or fast rate High ring friability 15 Friability of no surface Superficial disorder yes clear clear clear clear and no and no and no and no disorder disorder disorder disorder 156 145.5 148 174 slow medium fast fast low high high low au2a none none none yes yes yes yes Referrals from the table The polyisocyanate I is a polymethylene polyphenyl polyisocyanate containing about 45% by weight of methylenebis (phenyl isocyanate), the remainder of this mixture being constituted by polymethylene polyphenyl polyisocyanate having a functionality greater than 2; the equivalent of isocyanate = 133. 2 Varonic L-202 is the soy amine adduct obtained by the reaction of a 2 molar proportion of ethylene oxide with soy amine; amine equivalent weight of about 360; hydroxyl equivalents weight of about 180; issued by Chemical Products Division, Ashland Chemical Company, Columbus, Ohio. Varonic K-215 is the cocoamine adduct obtained by the reaction of a molar proportion of ethylene oxide with cocoamine; amine equivalent weight of about 885; hydroxyl equivalent weight of about 442; issued by Chemical Products Division, Ashland Chemical Company, Columbus, Ohio. Pluracol GP-730 is a propoxylated glycerin product; hydroxyl equivalents weight = 243, issued by BASF Wyandotte Chemical Corp., Wyandotte, Michigan. Pluracol PEP-650 is a propoxylated pentaerythritol product; hydroxyl equivalent weight = 148, which is issued by BASF Wyandotte Chemical Corp., Wyandotte, Michigan. 6The propoxylated polyol is the product obtained from a propoxylatiob of a mixture of sorbitol and toluene diamine up to a hydroxyl number of 360, a viscosity of 2500 centistokes at 25 C, and a specific gravity of 1.072. L-5420 is a rigid silicone foam surfactant having a hydroxyl number of about 119, issued by Union Carbide Corp., Tarrytown, N.Y. 10591; see Union Carbide Bulletin F-43565, December 1971. The R-11B fluorocarbon is an alloocene-stabilized mono-fluorofluoromethane blowing agent supplied by DuPont Chemical Corp., Wilmington, Del. Catalyst I comprises a combination in the following proportions of A) 1 part of a solution formed (a) of 45% by weight of potassium N-phenyl-2-ethyl-hexamide, (b) 27% ethylene glycol, and (c) 28% dimethylformamide; B) 3 parts of a solution of 50% by weight of sodium N- (2-hydroxy-5-nonylphenyl) methyl-N-methyl glycinate in diethylene glycol; and C) 1 part of a solution of 50% by weight of 2-hydroxypropyltrimethylammonium formate and 50% dipropylene glycol; and D) 1 part of a polyethylene glycol (molecular weight = 200). EXAMPLE 2 The following foams are prepared according to the method and apparatus described in Example 1, except as noted below. The foams of this example compare the prior art process (foams F and H) with the process of the present invention (foams G and I). Ingredients A and B are indicated

  in Table II below. The two foams F and G 2458562 contain a polyisocyanate different from the H and I foams. The type A component of the foams F and H contains the fluorocarbon blowing agent of the prior art. When the same amount of the fluorocarbon is mixed in the B component to test the miscibility, in both cases the fluorocarbon separates from the other ingredients, namely diethylene glycol, surfactant and catalyst. In the case of the G and I foams which contain the ethoxylated cocoamine in the B component, the fluorocarbon and the other ingredients are completely miscible with the diethylene glycol component. A comparison of foam emergence times between foams F and G and H and I clearly shows a much faster rate for the foams of the present invention (G and I) relative to the respective pair of foams. the prior art (F and H). The significant increases in speed clearly show the increased compatibility between components A and B which leads to a better reaction between these two, and therefore to faster emergence times compared to the formulations of the art. earlier. Although the ethoxylated amine in the G and I foams is a tertiary amine, these high molecular weight aminestertiary types are not strong bases and are used in G and I foams in very small amounts based on amine equivalents, i.e., 0.009 equivalents in each case. This low low amine content is not sufficient to account for the large lift increases of the G and I foams relative to the F and H foams, respectively, on the basis of amine-only catalysis. 2458562 TABLE II Foams FGHI Ingredients (parts by weight) Type A: Polyisocyanate I 100 Polyisocyanate II2 Fluorocarbon R-11B 21.5 Type B: Diethylene glycol 8.3 Varonicg K-215 - L-5420 1.25 Catalyst I 3.0 Fluorocarbon R-11B - NCO / OH Index 4.6 15 Foam emergence time (seconds) Cream Gel Duration without bonding 20 Exotherm (C) Core density, kg / m3 Dry thermal aging, 149 C / 24 hours% change in volume 25 Friability of core,% 3 Superficial friability Surface disorder Referred from Table II 75 104 116 172 28.16 +4.6 31 none yes 100 - 105 - 22.5 8.0 8.0 1 , 25 3.0 23 4.2 19 42 49 169 27.84 +4.1 30 none yes 105 8.3 8.0 - 8.0 1.25 1.25 3.0 3.0 - 24 4, 6 4.2 59 96 106 159 28.64 +2.9 22 none yes 21 41 47 158 28.00 +2.4 19 none yes 1 See footnote 1, Table I. 2Polyisocyanate II is a polymethylene polyphenyl polyisocyanate containing about 35% by weight of meth-methylenebis (phenyl isocyanate), the remainder of this - lange being formed polymethylene polyphenyl polyisobutylene 2458562 30 cyanate with a functionality greater than 2; the equivalent of isocyanate = 140. 3 Friability is the percentage of weight loss of the sample over a period of 10 minutes and is determined according to ASTM C-421 test method. EXAMPLE 3 The following two polyisocyanurate foams J and K of the present invention were prepared according to the process and apparatus described in Example 1, and using the ingredients in the indicated weight percentages. in Table III below. Components B are clear in both cases. Both foams have a very fine cell structure without superficial friability and a good superficial disorder is observed. Foam exotherms are good and rapid emergence profiles are evidence of rapid reactivity for both foams. It is interesting to note that the catalytic mixture used in both J and K foams contains a very small amount of the Varonic amine diol K-215 which acts as compatibilizer for the various other catalyst components. In the absence of Varonic K-215, the other catalytic components are not completely miscible. TABLE III 25 JK Foam Ingredients (parts by weight) Type A: Polyisocyanate III1 135 135 Type B: 30 Varonic K-2052 37 - Varonic K-215 - 75 DC-1933 1.5 1.5 2458562 31 Table III (continued) JK foam Fluorocarbon R-11B 22 27 Catalyst II 3 3 5 NCO / OH number 4.5 4.5 Appearance of the mixture B clear clear Foam emergence time (seconds) Cream 5 6 Gel 20 20 10 Duration without bonding 30 40 Leavening - - Exotherm, C Superficial friability none none Superficial disorder yes yes 15 Low kernel friability Appearance very fine cell cells very fine Table III references Polyisocyanate III is a polymethylene polyphenyl polyisocyanate containing about 45% by weight of methylenbis (phenyl isocyanate), the remainder of this mixture being polymethylene polyphenyl polyisocyanates having a functionality greater than 2, the equivalent of isocyanate = 135. 2 Varonic L-205 is the coconut adduct got by the reaction of a molar proportion

  ethylene oxide with cocoamine; equivalent weight of amine = about 445; weight of hydroxyl equivalents about 222; issued by Chemical Products Division, Ashland Chemical Company, Columbus, Ohio. DC-193 is a silicone surfactant supplied by Dow Corning, Midland, Michigan; see Bulletin 05- 146, February 1966. Catalyst II comprises a combination in the following proportions of: A) 1 part of a solution formed of 50% by weight of N- (2-hydroxy-5- nonylphenyl) methyl-N-methyl glycinate sodium in diethylene glycol; B) 0.50 part of potassium acetate, C) 0.30 part of water; and D) 0.50 part of Varonic K-215, which is described in reference 3 of Table I above. It will be appreciated that this catalyst mixture is quite clear and miscible. The preparation of the same catalytic mixture but without component K-215 gives a cloudy and opaque mixture. Example 4 The following two foams of water-blown polyisocyanurate L and M according to the present invention were prepared using the method and apparatus described in Example 1, and using the ingredients in the indicated weight proportions. in Table IV below. The type B component in both cases forms a clear miscible mixture. It is found that the foaming characteristics of the foams are very fast with a duration without rapid sticking despite the fact that the foams are blown with water. High foam exotherms are also observed, showing excellent conversions. The physical properties of the resulting foams are good. TABLE IV Foams LM Ingredients (parts by weight> Type A: Polyisocyanate III 135 135 Type B: Polyol blend I 23 30 L-5420 2 2 HO0 1 1 2 Catalyst II 3 3 NCO / OH index (including H 2 O) 3 2.5 Appearance of the mixture B light-clear 2458562 33 TABLE IV (cont.) Foam LM Foam emergence time (seconds) 5 Cream 15 13 Gel 31 26 Lifted 48 48 Duration without adhesive 35 30 Exothermic, C 191 195 10 Density , kg / m 42.4 44.96 Factor K 2 Joules / hr-m 2 C / m in dir 14.194 14.989 dir 14.110 14.445 15 Compressive strength, kg / cm2 Lifting 2.76 2 , 94 1 at emergence 2.1 1.4% change in volume at 70 C, 100% humidity after 24 hours -7.7 -4.7 Dry aging at 149 C, change in volume ( %) after 24 hours -2.9 +3.0 Referrals from Table IV 1 The polyol mixture I comprises a mixture in the following proportions of A) 40.8 parts of a polyester diol of a polyoxydiethylene adipate glutarate a molecular weight of 500; of B) 28.6 parts of diethylene glycol; and C) 30.6 parts of Varonic K-215. The K factor is a measure of the thermal conductivity of the materials obtained by determining the heat flux according to the ASTM C-518 test method. EXAMPLE 5 This example shows a hand-mixed N polyisocyanurate foam prepared according to the present invention, using the method and apparatus described in Example 1, and the ingredients shown in Table V. below. Component B of sample N contains a mixture of primary hydroxyl triol and diethylene glycol with a proportion of 41% by weight of fluorocarbon, the mixture being still clear without turbidity. The foam has fast emergence times with good exotherm and good friability characteristics. TABLE V 15 Foam N Ingredients (parts by weight) Type A: - Polyisocyanate III Type B: 20 TPEG-990 Diethylene glycol Varonic K-215 DC-193 Catalyst II 25 Fluorocarbon R-11B Appearance of the mixture B% of R-11B in the mix B Foam emergence time (seconds) 30 Cream Gel Duration without sticking 135 8.5 6.5 10 1.25 3.0 20 clear without turbidity 41% 13 30 35 2458562 35 TABLE V (continued) Foam N Exothermic , OC 176 Superficial friability none Superficial disorder yes Low kernel friability Table V references TPEG-990 is a trifunctional polyethylene glycol containing primary hydroxyls having a hydroxyl equivalent weight of 333, and is issued by Union Carbide Corp. , New York, N / Y. Example 6 The following polyisocyanurate foam laminates of the present invention are prepared, resistant to high temperatures and flame, using Foam O which is prepared from the ingredients shown in Table VI below. A Viking laminating machine with component temperatures "A" and "B" of 230C and 210C is used. The flow rate is 6.79 kg / minute through a low pressure contact mixing head. A low deposit technique is used instead of a spacer cylinder. The speed of the conveyor is 3.05 m / min and the temperature of the curing oven corresponds to room temperature (210 ° C to 320 ° C). Two 5.08 cm thick laminates were prepared with packing layers of 0.038 mm aluminum foil and prepared as well.

  with layers of packing formed of asphalt. The properties of the foams reported in Table VI below correspond to the foam core after removal of the gill layers. Therefore, the packing layer has no effect in itself on these results. The adhesion between the packing layer and the foam is excellent. Component B, although containing the primary hydroxyl polyester and diethylene glycol and Freon content (R-11B) of 43% by weight, is clear without any turbidity. The laminates are prepared without having to be baked at an elevated temperature because of the rapid reactivity of the formulation. The fast reactivity is also reflected in the fast emergence profile and in that it is found that the friability of the foam is extremely low despite the fact that there has been no curing step at high temperature. Good adhesion of the packing layers is also observed, as noted above. The overall physical properties of the foams are found to be good, including very low friability, good fire resistance, as well as the result of K-factor and wet aging. TABLE VI Foam O Ingredients (parts by weight) Type A: Polyisocyanate I 133 Type B Polyester diol1 9 Diethylene glycol 6,3 Varonic K-215 6,7 30 DC-193 1,25 Catalyst II 3,0 Fluorocarbon R-11B 20.0 2458562 37 Table VI (continued) 0 Appearance of the mixture B 5% of R-11B in the mixture B NCO / OH index Foam emergence time (seconds) Creaming time Gel 10 Unbleached duration Superficial friability Superficial disorder Core friability Overall density, kg / m3 Core density Compressive strength, kg / cm2 l [at emergence at emergence Closed cells2 20 K-factor 2 Joules / hr-m - C / m Wet aging (70 C, 95% relative humidity) Change in volume, after 1 day 7 days 25 days 28 days ASTM E-84 test on 5.08 cm thick samples Flame spread rate Smoke without turbidity 43% 4.9 19 40 47 none yes low 32 1.8 (6%) 2.17 1.47 94% 10.444 + 6% + 6.5% + 7.0% 38 187 30 References to Table VI 1 The polyester diol is the same diol as that described in reference 1 of Table IV under A). Foam 2458562 38 2 The closed cells are determined by the air picnometer test according to ASTM Test Method D-2856. Example 7 The following polyisocyanurate P 5 foam of the present invention was prepared using the method and apparatus described in Example 1, and using the ingredients in the weight proportions indicated in Table VII below. Component B is clear without any sign of turbidity despite the combination of the fluorocarbon with the primary hydroxides of the amide diol. The foam obtained is characterized by a very fine cell structure without any superficial friability and with a good superficial cloudiness. The exotherm of the foam is good and the rapid emergence profile shows the rapid reactivity of the foam. TABLE VII Foam P 20 Ingredients (parts by weight) Type A: Polyisocyanate III1 135 Type B: Varamide 6-CM2 49 25 DC-193 1.5 Fluorocarbon R-11B-23 Catalyst II3 3 NCO / OH number 4.5 Appearance component B clear, turbid 30 Foam emergence time (seconds) Creaming time 8 Gel 42 2458562 39 TABLE VII (continued) Foam P Time without bonding 52 Lifting 5 Exotherm, C 164.5 Superficial friability no Superficial disorder yes Friability Moderately friable core appearance Very fine cell appearance Referring to Table VII Polyisocyanate III is the same polymethylene polyphenyl polyisocyanate defined in Example 3, ref. 1 of Table III. Varamide 6-CM is the cocoamide adduct obtained by the reaction of a 6 molar proportion of ethylene oxide with a 1 molar proportion of cocoamide; amine equivalent weight = 290; hydroxyl equivalents = 193; issued by Chemical Products Div., Ashland Chemical Co., Columbus, Ohio; and further identified by the chemical name of a mixture of N, N-bis (8-hydroxy-3,6-dioxaoctyl) cocoamide. Catalyst II is the same catalytic combination as defined in Example 3, Table III, ref. 4. EXAMPLE 8 The following polyisocyanurate foams, Q.sub.R and S, are prepared according to the described method and apparatus. in Example 1, and using the ingredients shown below in Table VIII. Foams Q and R are according to the present invention while foam S is not. The B components in the case of the Q and R foams are clear without any sign of turbidity despite mixing the fluorocarbon with the primary hydroxyl containing components in both mixtures. Component A of the foam S contains the fluorocarbon blowing agent 2458562 of the prior art. When mixing the same amount of fluorocarbon

  in component B to test miscibility, the fluorocarbon separates from the other ingredients, namely diethylene glycol, surfactant and catalyst. A comparison of foam emergence times between foams Q and R on the one hand with foam S on the other hand clearly shows a much faster rate for the foams of the present invention (Q and R) compared to the foam of the prior art (S). The significant increases in speed clearly show the increased compatibility between components A and B which leads to a better reaction between these two, and therefore to faster rise times compared to the prior art formulations. TABLE VIII QRS Foams 20 Ingredients (Parts Type A: Polyisocyanate III Polyisocyanate I Flurocarbide R-11B Type B: Polyester diol2 Diethylene glycol Varamide D 6-CM L-5420 DC-193 Fluorocarbon R-11B Catalyst II Catalyst I by weight) 100 8 8 1.25 25 4.5 135 - - 100 - 21.5 9 6.3 6.7 2 22 5 8.3 1.25 3.0 2458562 41 TABLE VIII (continued) QRS foams NCO / OH number 5 Component Appearance B Foam Lift Time (seconds) Creaming Time Gel 10 Bonding Time Exotherm Exotherm, C Rate or Firm Rate Superficial Friability 15 Superficial Disorder Core Density, kg / m3 Core Friability (%) Dry Aging at 149 C,% change in volume / 24 hours 20 Referrals from Table VIII about 4 clear no cloudy 16 40 45 54 173 fast none yes 24.8 38.5 +7.4 about 4 clear not turbid about 4.6 16 75 35 104 40 116 48 - 177 172 rapid - none - yes - 32.96 28.16 32.0 31 +5.0 +4.6 1 Polyisocyanate I is polymethylene polyphenyl polyisocyte The anion defined in Example 1, Table I, ref. 1. The polyester diol: a polyester diol of polyoxydiethylene adipate glutarate with a molecular weight of 500 and a hydroxyl number of 211.5. Catalyst I is the same catalytic combination as defined in Example 1, Table I, ref. 9. EXAMPLE 9 The following polyisocyanurate T foam of the present invention is prepared according to the method and apparatus described in US Pat. Example 1, using the ingredients in the proportions by weight indicated in Table IX below. Component B is clear without any sign of turbidity despite the combination of the fluorocarbon with the primary hydroxyls of the amine triol component. The foam obtained is characterized by a very fine cellular structure without any superficial friability and with a good superficial cloudiness. The exotherm of the foam is good and the fast lifting profile is proof of the fast reactivity of the foam. TABLE IX Foam T Ingredients (parts by weight) 15 Type A: Polyisocyanate III Type B: KD-214 DC-193 20 Fluorocarbon R-11B Catalyst II NCO / OH Index Appearance of Component B 25 Foam Lift Time (seconds) Cremation time Gel Time without bonding 30 Exothermic lift, C Superficial friability Superficial disorder 135 56 1.5 23 2.5 4.5 clear, not cloudy 4 17 50 162 none light 2458562 43 TABLE IX (cont'd) T-foam Core friability 5 Very fine cell appearance Table IX references KD-124 is the ethoxylated mixture obtained by reacting ethylene oxide with a cocodiamine in the molar proportions of about 14 to 1, respectively, and in which cocodiamine by reacting cocoamine with one equivalent of acrylonitrile and reducing the cyanoethyl cocoamine mixture to cocodiamine; amine equivalent weight = 290; hydroxyl equivalent weight = 193; issued by Chemical Products Div., Ashland Chemical Co., Columbus, Ohio. EXAMPLE 10 The following U, V and W polyisocyanurate foams are prepared according to the method and apparatus described in Example 1, using the ingredients listed below in Table X. Foams U and 20 V are according to the present invention while the foam W is not. The B-type components in the U and V foams are clear without any sign of turbidity despite mixing the fluorocarbon with the primary hydroxyl components in both mixtures. The type A component of the foam W contains the fluorocarbon blowing agent of the prior art. When the same amount of the fluorocarbon is mixed in the B component to test the misibility, the fluorocarbon separates from the other ingredients, namely diethylene glycol, surfactant and catalyst. A comparison of the foam emergence times between the U and V foams on the one hand and the W foam on the other hand clearly shows a much faster rate for the foams of the present invention (U and V). compared to the foam of the prior art (W). The significant increases in speed clearly indicate the increased compatibility between components A and

  B, which leads to a better reaction between these two components, and consequently to faster emergence times compared to the formulations of the prior art. TABLE X UVW Foam Ingredients (parts in weight Type A: Polyisocyanate III Polyisocyanate I Fluorocarbon R-11B Type B: Polyester diol1 Diethylene glycol 20 KD-214 L-5420 DC-193 Fluorocarbon R-11B Catalyst II Catalyst I Catalyst NCO Ingredient aspect B 30 Foam emergence time (seconds) Creaming time Gel .s) 100 8 8 1.25 25 2.5 about 4 clear no cloudiness 16 39 135 9 6.3 6.7 2 22 2.5 approximately 4 clear no cloudiness 15 42 100 21.5 8.3 1.25 m 3.0 approximately 4.6 75 104 2458562 45 TABLE X (continued) UVW Foams Duration without bonding 46 50 116 Lifting 56 60 - 5 Exotherm, C 166 169.5 172 Rate or fast firm fast speed - Superficial friability none none - Superficial disorder yes yes - Core density, kg / m3 26.72 36.32 28.16 10 Core friability (%) 18 , 8 33.1 31 Dry aging at 149 ° C,% change in volume / 24 hours +10.8 +5.3 +4.6 Return of Table X 15 1 Polyester diol: a polyester diol of polyoxydiethylene adipate glutarate It has a molecular weight of 500, and a hydroxyl number of 211.5. Example 11 A series of fluorocarbon R-11B (monofluorotrichloromethane) mixtures were prepared with the two primary hydroxyl polyols characteristic of the present invention. The weight proportions used, including the amount of amine diol (I) when present, are varied according to the values given in Table XI below. Blends are examined for their miscibility and clarity or turbidity and for the separation of the fluorocarbon from the solution. Mixtures A to D contain diethylene glycol with fluorocarbon and in the absence of amine diol, i.e. in the presence of 100% diethylene glycol, the maximum solubility of the fluorocarbon is 15%. weight. The addition of 10% by weight of amine diol is not sufficient to impart a fluorocarbon solubility of up to 25% by weight, while an amine diol content of 20% D) does not provide a miscible solution, clear at 25% fluorocarbon. Blends E to J contain a polyester diol defined as above, wherein the pure polyester diol is capable of dissolving 20% by weight of fluorocarbon but not 25%. The stopping for the 25% fluorocarbon solubility starts at about 10 parts by weight of the amine diol (mixture G) while at the level of 20% amine diol. the fluorocarbon could dissolve up to 31% by weight. It is observed that mixtures K to M have maximum fluorocarbon levels of greater than 90% and up to 67.5% respectively for diethylene glycol and for polyester diol when a maximum of 85% is used. by weight of amine diol. It is observed that mixtures N to Q have maximum fluorocarbon solubilities of 60% and 50% respectively for diethylene glycol and polyester diol when the primary alcohol and diol mixtures are used. the amine are 50/50% by weight. TABLE XI Mixture ABCDEFGHI Ingredients (parts by weight) Diethylene glycol - Polyester diol K-2152 Fluorocarbon R-11B% by weight of primary alcohol% by weight of amine diol% by weight of fluorocarbon Aspect of the mixture 100 100 90 80 - - 10 20 17.6 25 33.3 33.3 100 100 90 80 -'H CDH I i -Fi mm oo Id me ~ OO m ~ I-. W CD tum 1. CD 'Me fCD nD H' i Cn 100 100 90 - - 10 25 33.3 33.3 100 100 90 'O 0 10 20 25 25 mnom cn 3t. ~ * Na 3 m Pi 0 0 w 0F. M` 9 0 Fi HJ P) D H mD H CD O. 80 20 40 80 20 28.5 m n J. ' H nbn -1 CD 80 20 45 80 20 31 3o n-1 CD .4 N * j ~ a Co Ln 0% N TABLE XI (cont.) Mixture JKLMN 0 PQ Ingredients (parts by weight) Diethylene glycol 1 Polyester diol K- 2152 Fluorocarbon R-11B% by weight of primary alcohols% by weight of amine diol% by weight of fluorocarbon Aspect of the mixture M 80 20 50 80 20 33.3 15 85 900 15 85 90 50 50 15 85 207.7 85,550 50, 50 60 50 175 50 50 63,6 50 50 100 50 50 50 50 50 120 50 50 55 References to Table XI 1 The same polyester diol described in US Pat. reference I of Table IV under A. 2 K-215 is the amine diol (I) defined in ref. 3 of Table I. EXAMPLE 12 A series of fluorocarbon mixtures R-11B (monofluorotrichloromethane) were prepared with three primary hydroxyl polyols characteristic of the present invention. The proportions by weight used, including the amount of cocoamide diol (II), if any, are varied according to the values given in Table XII below. The mixtures are observed for their miscibility and clarity or for their turbidity and for the separation of the fluorocarbon from the solution. Mixtures A to D contain diethylene glycol and, in the absence of amide diol, solubility

  fluorocarbon does not reach 20% by weight. The addition of 10% amide diol (mixture B) is not sufficient to impart to the fluorocarbon a solubility of 20% by weight. At least 15% of amine diol (mixture C) is required for the mixture to remain clear at 20% fluorocarbon, and obviously it is clear at the 80/20 mixes (mixture D). Mixtures E to G contain ethylene glycol and at least 20% amide diol is required to maintain solubility for fluorocarbon of 20% by weight. Mixtures H to L are prepared from a polyester diol and it is observed that although it is possible to achieve a solubility of 20% with respect to the fluorocarbon, it is not possible to reach a solubility of 25% with the pure diol. When the amide diol content is 20% (mixtures J to L), the highest level of fluorocarbon that can be achieved is about 31%. It is observed that mixtures M to O have maximum fluorocarbon levels of greater than 90% and up to 60% by weight respectively for diethylene glycol and polyester diol when using a monomer. up to 85% by weight of amide diol. It is observed that mixtures P to S have maximum fluorocarbon solubilities of 55% and 45% respectively for diethylene glycol and polyester diol when mixtures of primary alcohol and amide diol are used. are 50/50% by weight. TABLE XII Mixture ABCDEFGHIJ Ingredients (parts by weight) Diethylene glycol Ethylene glycol Polyester diol 6-CM2 Fluorocarbon R-11B% by weight of primary alcohol% by weight of amide diol% by weight of fluorocarbon Aspect of the mixture 100 90 85 80 - - - - - - 100 85 80 - - - - - - - 100 100 80 - 10 15 20 - 15 20 '- - 20 25 25 25 25 33.3 40 100 90 85 80 100 85 80 100 CDH (CDD) (CDC) CDD (CDC) CDH ish CD CDM mp Pd PJ O ## STR1 ## where: ## STR1 ## where: ## STR1 ## where: ## STR1 ## % KOHN 0 PQRS Ingredients (parts by weight) Diethylene glycol Ethylene glycol Polyester diol 6-CM2 Fluorocarbon R-11B% by weight primary alcohol% by weight of amide diol% by weight of fluorocarbon Aspect of the mixture M 80 80 20 20 45 50 80 80 2.0 20 31 33.3 No. C-FiCD CDI ## EQU1 ## 85,500 15,85,55. ## EQU1 ## 50 50 15 85 150 15 85 60 rnPJ O W H- 0 85 166.7 15 85 62.5 m (D. bD CD hi 50 125 50 50 55 HH P.IJ J. 50 150 50 50 60 CDFII 07 o (DI PJ CD hi CD References to Table XII 1 The same polyester diol described in reference 1 of Table IV above. -CM is the same cocoamide identified in reference 2 of Table VII above: ri co Ch ru 50 50 81.8 50 50 45 O PJ IQ 50 50 100 50 50 50 CD rr (D -io me M @ (DI b4 EXAMPLE 13 A series of fluorocarbon mixtures R-11B (monofluorotrichloromethane) were prepared with three primary hydroxyl polyols characteristic of the present invention, the weight proportions used, including the amount of triol of The amine (III), where present, varies according to the values given in Table XIII below: The mixtures are observed for their miscibility and clarity or for their turbidity and for the separation of the fluorocarbon from Mixtures A to D contain diethylene glycol and in the absence of amine triol the solubility of the fluorine ocarbure could not reach 20% by weight. The addition of 10% amine triol (mixture B) is not sufficient to impart a 20% solubility to the fluorocarbon. At least 15% amine triol is required for the mixture to remain clear at 20% fluorocarbon. Mixtures E to G contain ethylene glycol and at least 20% amine triol is required to maintain a solubility of 20% by weight with respect to the fluorocarbon. Mixtures H to M are prepared from a polyester diol and it is noted, although it is possible to solubilize 20% fluorocarbon, that it is not possible to solubilize 25% of fluorocarbon with pure diol and at least 15% by weight of amine triol is required to maintain the solubility of the 25% fluorocarbon (K mixture). At 20% by weight of amine triol, the maximum solubility of the fluorocarbon is about 28.6% by weight. It is observed that the N to P mixtures have maximum fluorocarbon levels of greater than 90% and up to 50% by weight respectively for diethylene glycol and polyester diol when a maximum of 85% by weight of triol is used. amine. It is observed that mixtures Q to T have maximum fluorocarbon solubilities of 50% and 40% respectively for diethylene glycol and polyester diol when the mixtures of primary alcohol and amine triol are 50/50. 50% by weight. TABLE XIII

  Mixture ABCDEFGHIJ Ingredients (parts by weight) Diethylene glycol 1 Ethylene glycol Polyester diol 2 KD-214 Fluorocarbon R-11B% by weight of primary alcohol 1% by weight of amine triol% by weight of fluorocarbon Aspect of mixture n. 90 85 80 - - - _ _ - _ _ _ _ _ _ _ _ _ _ _ _ _ - _ - _ - _ - _ - _ - _ - _ - - - - - . . - - - 100 100 90 15 20 - - 25 20 333 33.3 85 80 100 85 80 100 100 90 15 20 0 20 20 25 25 PO. p. p CD <O fiP. #####################################################################################################################. Fi F-CD o OF (DI b 'M (D ui u1 o> CDM 0 CD om m 11 ru un tJ1 nN TABLE XIII (cont.) Mixture KLMNOPQRST Ingredients (parts by weight) Diethylene glycol Ethylene glycol Polyester diol KD- 2142 Fluorocarbon R-11B% by weight of primary alcohol% by weight of amine triol% by weight of fluorocarbon Appearance of the mixture - - - 15 85 15 33.3 85 15 25 80 20 40 80 20 28.6 H- The same polyester diol described in Ref. 2 KD-214 is the above adduct. 50 50 85 85 900 100 15 15 85 85 90 50 cnt-t 'O HF 0 M PiH on P m ~ H p H, p fi CD CD 15 - 85 50, 50 50 110.5 100 122.2 66.7 15 50 50 50 85 50 50 50 52.5 50 55 40 t PO HPi C ep M eF (% O m 'H P - b "Fi CD 1 of Table IV above, of cocodiamine (III) defined in reference 1 of Table IX OB 50 50 81.8 50 50 45 on 0% 3nP H-F ep nI FI II (D F o C o 0 0 ol N U1 0o tn C0s 2458562 57.

Claims (10)

  A polyol blend, characterized in that it comprises (1) from about 20% to about 85% by weight, based on the total weight of said mixture, a representative or a mixture of representatives of the class of compounds of formulas: R1 R1 oz 10 RN ~~; R 2 -CHOH, HIY and R1 R1 I II R1 15 ~ ~ (CHR 15 "to ~~~ CHR ~ _ ± N" ~., CH 2CH0 I ;, RN RN n \ CH 2CHO * -., H 'CH Wherein R is an aliphatic radical having 8 to 18 carbon atoms, R 2 is an aliphatic radical having 7 to 17 carbon atoms, each R 1 is selected, independently, between hydrogen and a methyl group, x and y each independently have an average value of about 4 to about 15, x 'and y' each independently have an average value of about 1 to about 3, x ", y and z each independently has an average value of about 1 to about 5 and 30 n 2 or 3, and (2) about 15 to about 80 wt% of a primary hydroxyl-containing polyol characterized by molecular weight of about 60 to about 1000.   2. Mixture miscible polyols, characterized in that it comprises at least 20% by weight of a fluorocarbon blowing agent, the remainder being formed of a mixture of polyols according to claim 1.   3. - Polyol blend according to claim 1, characterized in that the component (1) is chosen between 2458562 58. between compounds of formula (I) and is a mixture of ethoxylated coconut amine diols obtained by reaction about 15 moles of ethylene oxide with the coconut amine.   4. A polyol blend according to claim 1, characterized in that the component (1) is selected from compounds of the formula (II) and consists of a mixture of N, N-bis- (8-hydroxy- 3,6-dioxa-octyl) -coco amides.   5. A polyol blend according to claim 1, characterized in that component (1) is selected from compounds of formula (III) and consists of a mixture of triols of amines derived from cocoamine and each representing the mixture at average values of x ", y" and z of 4.6 and n is equal to 3.   The polyol blend according to any one of claims 3, 4 and 5, characterized in that the primary hydroxyl-containing polyol (2) is diethylene glycol.   The polyol blend according to any one of claims 3, 4 and 5, characterized in that the primary hydroxyl-containing polyol is a polyoxydiethylene-type adipate-glutarate polyester diol having a molecular weight of between about 400 and about 600.   The polyol blend according to any of claims 3 to 5, characterized in that the primary hydroxyl-containing polyol is a mixture of about 30 to about 50% by weight of diethylene glycol and about 50 to about 70% by weight of a polyester diol of polyoxydiethylene adipateglutarate of molecular weight between about 400 and about 600.   9. An improved process for producing a cellular polymer in which the main recurring polymer unit is an isocyanurate unit, by trimerization of an organic polyisocyanate in the presence of a minor amount of a polyol, an agent pore-forming catalyst and a trimerization catalyst, characterized in that it consists in preparing the cellular polymer by bringing together: A. an organic polyisocyanate; and B. from about 10 to about 120 parts by weight, per equivalent of said polyisocyanate, of a miscible blend comprising: 2458562 59. (a) about 2 to about 20% by weight of a polyisocyanate trimerization catalyst and (b) from about 80 to about 98% by weight of a mixture comprising: 1. at least about 20% by weight of a fluorocarbon porogen, and 2. the balance consisting of a mixture of polyols according to claim 1; provided that the total number of hydroxyl equivalents present in the B mixture is in the range of about 0.05 to about 0.5 equivalents per equivalent of said polyisocyanate.   10. A process according to claim 9, characterized in that A. is a polymethylene polyphenyl polyisocyanate and B. (b) comprises: 1. at least about 20% by weight of a fluorocarbon blowing agent; the remainder consisting of a mixture of polyols according to any one of claims 6, 7 and 8.