NL8003378A - POLYOL MIXTURE. - Google Patents

Description

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"YO 517.

Title: Polyol blend.

The invention relates to cellular polymers and intermediates therefor and in particular new polyol blends and their use in the preparation of cellular polyisocyanurates.

Cellular polyisocyanurate polymers are bulky and are used for various thermal insulation purposes. They are also known for their ability to withstand heat and flame (see U.S. Pat. Nos. 3,7 ^ -5,133, 3-986 * 991 and h.003.859). Minor amounts of polyols are added sous to the foaming ingredients to modify the foaming properties. When using fluorocarbon blowing agents, an incompatibility problem may arise between the polyol, especially primary bydroxyl polyols, and fluorocarbons in resin mixtures, which are usually dissolved by first mixing most or all of the fluorocarbon with the polyisocyanate (see above patent 15). ten). Polyisocyanurate foams are especially used to make laminated foam board materials, which can be made with a wide variety of coating materials. Problems that can arise in the production of this type of lamination materials include a) lack of uniform foam core strength; B) poor adhesion between foam core and coating material; c) maintaining a good fire resistance in the foam and d) keeping the foam fragility low. These problems have hitherto been solved in the mixture by using small amounts of low equivalent weight polyols, especially diols; combined with heating the formed laminate product in an oven at 70-90 ° C (see US Patent 3,903.3½). However, the low equivalent weight polyols used, especially the preferred diols of column h4i lines 59-61 of U.S. Patent 3,903.3½, with only primary hydroxyl groups cannot be mixed with the fluorocarbon blowing agents to a B-component beforehand because of the low solubility of the diol / fluorocarbon pair.

This makes it necessary to mix the fluorocarbon with the polyisocyanate to form an A component. The patent teaches that, due to the poor miscibility of the fluorocarbon with the diol 35, a third component C is needed, which contains the catalyst, dissolved * 00 3 3 78 -2- in a low molecular weight glycol (see column 2, lines 32-33 and the illustrations of U.S. Patent No. 3,903.3½). Furthermore, a laminate made according to this patent must be heated in an oven in order to obtain a product with a uniform foam core strength.

Surprisingly, it has now been found that large amounts of fluorocarbon blowing agent are fully miscible with low molecular weight polyols having primary hydroxyl groups when new blends containing certain types of amine or amide diols or amine triols containing the primary hydroxyl polyols are used. Further ingredients which may be present in these miscible mixtures are surfactants, catalysts and the like.

Furthermore, it has been found that the same type of miscible primary hydroxyl containing mixtures as described above, except that water replaces the fluorocarbon component, can be prepared.

In addition, it has been discovered that the novel polyol compositions herein can be used in minor amounts as a B-type component for preparing polyisocyanurate foams with low friability, fine cell structure, good dimensional stability and low flame spread. a two component ie an A and a B process. The fluorocarbon and water camponents hereby act as blowing agents in their respective foam-forming preparations.

Furthermore, the said types of amide or amine diols or amine triols can be used as the sole polyol component in combination with the fluorocarbon or the water, the catalyst, the surfactant and other auxiliaries for preparing polyisocyanurate foams according to the invention.

Quite unexpectedly, amide or amine diols, or amine triols in the B-camponent, have been found to result in excellent compatibility between the polyisocyanate and the other components. This in turn leads to faster reactivity compared to older foams and a good exothermic reaction. A high exothermic heat is of particular importance when making foam laminates because it provides good adhesion between foam and coating material 800 3 3 78 L -3- making an oven treatment unnecessary.

The invention therefore includes polyol blends containing a) 20-85% by weight of a substance or a mixture of formulas 1, 2 and 3 of the formula sheet, wherein R is an aliphatic group with 8-18 carbon, R2 is an aliphatic group with 7-17 carbon atoms, each group R ^ hydrogen or methyl, x and y an average value of U to 15, x 'and y' an average value of 1 to 3, x ", y" and z each an average value of 1 to 5 and n represents 2 or 3; and b) 15-80 w / s of a primary hydroxyl polyol with a molecular weight between 60 and about 1000.

The invention also includes miscible mixtures of these polyol blends with a fluorocarbon or water blowing agent.

The invention also relates to miscible blends of these polyol blends in combination with a fluorocarbon or water blowing agent and an isocyanate trimerization catalyst.

The invention also relates to processes for preparing cellular polyisocyanurate polymers in which as a component a compound or a mixture of compounds of the formulas 1, 2 or 3 is used, in combination with a fluorocarbon or water blowing agent and a trimerization catalyst, wherein the mixed whole also contained a polyol (b, wherein the diol 1 is defined above with a smaller range for x and y from about h to 15, upon reaction with an organic polyisocyanate.

The invention also includes cellular polymers obtained by this process.

The invention further relates to a laminate with a polyisocyanyrate foam core manufactured in accordance with the improved process according to the invention.

The term "aliphatic radical" at R refers to alkyl and alkenyl groups of 8-18 carbon atoms. Typical alkyl groups are octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl or isomeric forms thereof. Typical alkenyl groups are octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl and ismers thereof.

The term "aliphatic radical" at R 1 refers to alkyl and alkenyl groups of 7-17 carbon atoms. Characteristic for these alkyl-35 and alkenyl groups are the same as shown above except that 800 3 3 78 -1 + - they start with heptyl or heptenyl and end with heptadecyl or heptadecenyl and their isaa forms.

The present polyol blends theirs are used as polyol components in the manufacture of polyurethane foams. Polyure-5 than foams are known and are widely used for thermal and sound insulation in buildings and in industry.

The polyol blends are especially used as minor ingredients in making polyisocyanurate foams off and, especially those polyisocyanurate foams off and in foam laminates made with a foam sprayer. Such slants off and are known for their good heat and flame resistance and are used especially for laminate boards. and foam interlayers in buildings for thermal and sound insulation.

The present polyol blends are prepared by simply joining and mixing the ingredients 15 in the proportions shown above. Any suitable mixing vessel, any tank and any storage tank can be used. Preferably, the compound, 1, 2 or 3 is used in an amount of 25-60% by weight while the primary hydroxyl polyol is used in an amount of 1 + 0-75% by weight.

Preferred compounds of formulas 1, 2 and 3 have the formula shown above, always being hydrogen.

A very favorable diol is that of the formula 1, in which both groups are hydrogen and x and y have an average value of 5-10.

A further very favorable amide diol corresponds to the formula 2, wherein both R 2 groups are hydrogen and x 'and y' are between about 2 and about 3.

A very favorable amine triol corresponds to the formula 3 'in which all R 2 groups represent hydrogen and x' and y 'and z have an average value of 3-5 and n is 3.

The amine diols 1 are prepared according to standard reactions and in some cases are commercially available. Typically, the amine diols 1 are prepared by reacting an appropriate dialkanolamine with an appropriate aliphatic halide compound or a mixture of several of these compounds with all groups R falling within the 800 33 78-5 I definition shown, while the halide is most preferably chlorine or bromine. is.

If the desired number of alkyleneoxy groups is not already present in the dialkolamine before the reaction, they can easily be added later by reacting the alkylated dialkamolamine with an appropriate number of moles of ethylene oxide or propylene oxide or mixtures thereof, thereby amine diols of the formula 1 are formed.

Preferably, the amine diols are prepared by reacting an appropriate primary fatty amine R-NHg a mixture of fatty amine with about 2-30 moles, most preferably 8-30 moles, especially 10-20 moles of ethylene oxide or propylene oxide per mole of fatty amines, see Bulletin 129k, entitled Ethoxylated Fatty Amines, from Ashland Chemical Company (Ashland Oil Inc.) for more details on the preparation of this type of amine diols.

Typical starting fatty amines in this case are octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecyl-15 amine and isamers thereof. Typical alkenylamines are octenylamine, decenylamine, dodecylamine, tetradecenylamine, hexadecenylamine, octadecenylamine and isamers thereof. Further characteristic fatty amines are mixtures of alkyl and alkenylamines, such as cocosamine, consisting of the following mixture: 2% decylamine, 52% dodecylamine, 20 2b% tetradecylamine, 21% hexadecylamine, 5% octadecylamine and 5% octa decenylamine; soy amine containing 11.5 hexadecylamine, b% octadeceylamine, 2b, 5% oleylamine, 53% linoleylamine and J% linolenylamine; as well as tallow amine of the composition b% tetradecylamine, 29% hexadecylamine, 20% octadecylamine and b% octadecenylamine. Further characteristic starting fatty amines are the halogenated fatty amines, especially the chlorinated and bound fatty amines, e.g. can be prepared by chlorination or coating cocosamine, soy amine, tallow amine and the like.

A preferred group of fatty amines consists of the cocosamine-30 mixture, the soy amine mixture and the tallow amine mixture. Of this group, the cocosamine is most preferred again.

The amide diol of the formula II can be prepared by reacting an appropriate dialkanolamine with an appropriate fatty acid, an appropriate fatty acid ester or a fatty acid chloride according to the equation A of the formula sheet, wherein Rgj σ 'and y' have the above meaning 800 33 78-6 and represents R ^ OH, ÖR ^ or X, wherein R ^ is an esterifying group, eg alkyl, aryl, cycloalkyl or the like and X a halogen atom, preferably chlorine or "bromine. If the starting dialkanolamine is diethanolamine or diisopropanolamine or a mixture thereof and one desires amide diols where the values for x 'and y' are greater than 1, the dialkanolamide intermediate is simply converted to a molar ratio of 1 or 1+ moles of ethylene oxide or propylene oxide or mixtures thereof See in this paper Bulletin 1295 s entitled Varamide Alkanolamides from the aforementioned Ashland Chemical Company.

Preferably, the amide diols 2 "are prepared by converting the fatty acids into the corresponding fatty acid amides RgCOHHg and reacting these amides with 2-6 moles (per mole amide) ethylene oxide or propylene axide or mixtures thereof.

Typical starting fatty acids (from which the esters, acid halides, and amides are also derived) are caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and its forms. Characteristic of the unsaturated fatty acids are decylenic acid, dodecylenic acid, palmitoleic acid, oleic acid, linoleic acid and isomeric forms thereof. Further examples of fatty acids are mixtures, e.g. obtained from coconut oil, which consist of 8l caprylic acid, 7 # capric acid, h8% lauric acid, 17.5 # myristic acid, 8.2% palmitic acid, 2.0% stearic acid, 6.0% oleic acid and 2.5% linoleic acid; the soybean oil fatty acid mixture containing 6.5 # palmitic acid, b, 2% stearic acid, 33s6 # oleic acid, 52.6% linoleic acid and 2.3% linolenic acid; as well as the fatty acid mixture of tallow oil containing 2% myristic acid, 32.5% palmitic acid, 1.5% stearic acid, 8.3% oleic acid and 2.7 # linoleic acid. Furthermore, halogenated fatty acids can also be used, in especially chlorinated and brominated fatty acids, which e.g. can be obtained by chlorination or brazing of coconut, soy and tallow fatty acid mixtures.

A preferred group of starting fatty acids or fatty acid amides consists of coconut, soy and tallow oil mixtures and the corresponding coconut amide, soy amide and tallow amide mixtures. A preferred component within this group are the coconut oil blends and the coconut amide blends.

A preferred group of amide diols of the formula II are coconut amide-diol, soy amide diol and tallow amide diol obtained from diol mixtures, wherein 800 3 3 78 -τ-each R1 represents hydrogen and both digits x 'and y' are about 3. A preferred species within this group is the cocosamide diol mixture which is chemically referred to as ϊΐ, ΐί-bis (8-bydroxy-3,6-dioxaoctyl) cocos amide mix.

The amilite triols of the formula III are also easy to prepare and their representatives are also commercially available.

Generally speaking, the method of preparation for the aminetriols with n is 2 is slightly different from that of the aminetriols with n is 3. The first amine triols can be readily prepared according to scheme 10 B of the formula sheet, wherein R and the above are represented. The starting amine material is converted with an equimolar amount of ethylene or propylene oxide to an amino alcohol 5 which can be easily converted to a diamine 6, e.g. by reaction with ammonia, followed by a reaction of a molar amount 6 with about 3-15 mol amounts of ethylene oxide and / or propylene oxide to form the amine triol of the formula III.

Amine triols with n is 3 are most preferably prepared according to scheme C, wherein R and R 2 have the above-described significance. To this end, the amine starting material is cyanoethylated with an appropriately substituted acrylonitrile 7 to form a compound of formula 8 which is reduced to diamine 9 followed by alkoxylation with 3-15 moles of ethylene oxide and / or propylene oxide to form a compound of the formula 3.

The starting fatty amines are the same as shown above in the discussion of the amine diols 1.

Characteristic of the acrylonitrile compounds which can be used in the preparation of the aminetriols are acrylonitrile,--methacrylonitrile, β-methacrylonitrile, dim-dimethacrylonitrile and the like.

Acrylonitrile itself is preferred.

A preferred group of amine triols 3 are the amine triol mixtures derived from cocosamine, soy amine and tallow amine mixtures, in which all groups R1 are hydrogen, n is 3 and the value for x, y and z is always between 3 and 5. With even more preference an amine triol mixture is used, derived from cocosamine, in which all groups R 1 are hydrogen and the value for n is equal to 3 while the value for xu, y "and 800 3 3/3 -8-z is always equal to U, 6.

The primary hydroxyl polyol k may be any primary hydroxyl polyol having a molecular weight between 60 and about 1000, most preferably between βθ and about 800, and even more preferably between βθ and about 600. The polyols b include 5 diols, triplets and tetrols. Diols are preferred.

Within the group of the primary hydroxyl-containing polyols are the various hydroxyl-containing diols, triols, and tetrols disclosed in U.S. Patent 3-7 ^ 5-133, which are within the indicated molecular weight limits while a preferred group is the polyester polyols prepared from divalent carboxylic acids and polyvalent alcohols including those based on chlorendine anhydride, alkylene diols, alkoxyalkylene diols, polyalkylene ester diols, polyoxyalkylene ester diols, hydroxyalkylated aliphatic monoamines or diamines, the resole polyols (see Prep. Methods of Polymer Chem. of Sorenson (l. ), p. 293) and the polybutadiene resins with primary hydroxyl groups (see Poly Bd Liquid Resins, Product Bulletin BD-3, October 197 from Arco Chemical Company.

The most preferred group is the alkylene diols, the lower alkoxyalkylene diols, the polyalkylene ester diols and the polyoxyalkylene ester diols.

Characteristic but not limited to these polyols: ethylene glycol, 1 ', 3-propanediol, 1, U-butanediol, glycerol, trimethylol propane, pentaerythritol, diethylene glycol, the polyoxyethylene glycols obtained by addition of ethylene oxide to water, ethylene glycol or diethylene glycol etc. to produce triethylene glycol, tetraethylene glycol and higher glycols or mixtures thereof such that the molecular weight is within the range shown above; further ethoxylated glycerol, ethoxylated trimethylol propane, ethoxylated pentaerythritol and the like; bis (β-hydroxyetbyl) terephthalate, bis (β-hydroxyethyl) phthalate, and the like; polyethylene succinate, polyethylene glutarate, polyethylene adipate, polybutylene succinate, polybutylene glutarate, polybutylene adipate, copolyethylene butylene succinate, co-polyethylene butylene glutarate, copolyethylene butylene adipate and the like hydroxyl terminated polyesters; polyoxyethylene succinate, polyoxyethylene glutarate, polyoxyethylene adipate, polyoxyethylene adipate 800 3 3 78-9 glutarate and the like; further diethanolamine, triethanolamine, N, 1P-bis (p> -hydroxyethyl) aniline and the like.

The most preferred diols are diethylene glycol and the polyoxy diethylene adipate glypole olyders with a molecular weight of between 600 and 600.

Further preferred are mixtures of about 30-50% by weight diethylene glycol with about 50-70% by weight polyoxyethylene adipate glutarate polyester diol having a molecular weight between 600 and 600.

In the preferred polyol blends of the invention, a fluorocarbon or water blowing agent is also present in the mixture, a fluorocarbon forming a preferred blowing agent.

When the blowing agent. is a fluorocarbon, the favorable properties of the polyol blends of 1,2 or 3 with k can be fully realized. Miscible polyol blends can thus be obtained containing at least 20% by weight of a fluorocarbon blowing agent, the remainder being the. present mixtures in the proportions shown. A favorable percentage of fluorocarbon to be dissolved in the mixtures controls the ratio of k to be used by 1, 2 or 3 and this ratio can be easily determined by those skilled in the art.

Miscible polyol blends containing more than 50 wt.% Fluorocarbon and even up to 90 wt.% Fluorocarbon can also be obtained with the present blends depending on the choice of blend ingredients. Generally speaking, the lower the molecular weight of the primary hydroxyl polyol k, the greater amount of fluorocarbon can be dissolved in the mixture at a given ratio of polyol 1, 2 or 3 compared to mixtures with a higher molecular weight polyol k in the same ratio. In this regard, alkene alkylene diols and lower alkoxyalkylene diols with molecular weights below 1 + 00 are preferred as polyols of the formula U, with the lower alkoxyalkylene diols being most preferred.

The specific ratios of polyol 1, 2 or 3 to polyol 1+ for maximum miscibility with fluorocarbons can easily be determined with a preview.

Generally speaking, the use of an amine diol 1 with 800 3 3 78-10- a polyol b will produce a miscible polyol mixture at least 25 parts to at least 65 parts of a fluorocarbon blowing agent with the corresponding amount of 65-35 wt. . # is formed by the mixture of 1 and b.

When the amide diol 2 with ^ is used, readily miscible polyol blends having at least about 20 parts by weight to at least 60% by weight of fluorocarbon blowing agent are obtained, while the corresponding amount of 80-0% by weight is formed by the mixture of 2 and YOU.

When a mixture of triol 3 with b is used, 10 readily miscible polyol blends are obtained with 20-50 wt.% Fluorocarbon blowing agent while the corresponding 80-50 # are blends of 3 and b.

When water is used as the blowing agent 1, it will be present in amounts of 1-6 #, preferably 2-5 #, while the remaining 9 ^ -99 # »15, preferably 95-98 # will be formed by a mixture of 1.2 or 3 with U.

The fluorocarbon blowing agent can be any conventional fluorocarbon blowing agent. Typically, these are halogenated aliphatic hydrocarbons which may also contain chlorine and bromine substituent fluids. Reference is made to US Patent 3,719,133,20 column 11, lines 25-38 where a number of examples are given.

In addition, in preferred polyol blends of the invention, an isocyanate trimerization catalyst is present. This isocyanate trimerization catalyst component will be discussed in more detail later. The isocyanate trimerization catalyst is preferably present in an amount of 2-20, most preferably 2-15 wt.%, While the remaining 80-98, most preferably 85-89 # are the components discussed above.

Surprisingly, the blowing agent and the polyol mixture containing the primary hydroxyl-containing polyols are completely miscible with one another without separation occurring during storage. This good miscibility is due to the presence of an amine diol 1, an amide diol 2 or an amine triol 3. In addition to the benefits resulting from a stable, miscible mixture of primary hydroxyl polyols and fluorocarbons or water, the nitrogen-containing diols or triols have the preparation of polyisocyanurate foams has further advantages.

Further possible additives are e.g. other polyol compounds, such as polyol-containing secondary hydroxyl groups, dispersants, cell stabilizers, surfactants, fire retardants and the like which are otherwise commonly used in foams.

In the preparation of the present polyis ocyanurate foams, the amine diol, amide diol or amine triol as single polyol components are mixed with a fluorocarbon or water as the blowing agent and a trimerization catalyst is used as the B camponate, which is then reacted with an Ac monkey onent comprising an organic polyiso-10 cyanate. In this case, the values for x and y in 1 can have the widest ranges from 1 to 15.

The weight ratios of the blend components are the same as those shown above for the ratios of catalyst to blend and blowing agent and polyol component. I.e. the B mixture 15 consists of 2-20, preferably 2-15 wt.% of a trimerization catalyst and 80-98, most preferably 85-98 wt.% of 1,2 or 3 and a blowing agent. If a fluorocarbon blowing agent is used, it is present in an amount of 20-80, preferably 20-50 wt.%, Calculated on 1, 2 or 3, the latter being then present in an amount of 20-30, preferably 50-80 wt. .%.

If water is used as the blowing agent, it is present in an amount of 1-6, preferably 2-5 wt.%, While the compound of the formula 1, 2 or 3 9 ^ -99, preferably 95-98 wt.% .

The B mixture is most preferably used in an amount of 10-120 parts, most preferably 10-80 parts, more preferably 20-60 parts by weight per equivalent of polyisocyanate; provided that the total hydroxyl equivalents in mixture B are within a range of 0.05-0.5 equivalent, most preferably 0.08 to 0.005 equivalent per equivalent of polyisocyanate.

Most preferably, a minor amount of the above-described primary hydroxyl polyol U is also present in the B mixture. This combination in the mixture not only results in the above-mentioned stabilized miscible mixtures, but also leads to polyisocyanurate soy materials with optimally favorable properties, especially for making foam laminates, which do not require oven heating for maximum foam strength and good adhesion between foam and snn 78 -12 coating. In this case, the values for x and y in 1 have the narrower ranges from 1+ to 15.

A mixture of amine diol 1, amide diol 2 or amine triol 3 with a primary hydroxyl polyol +, an blowing agent and a trimerization catalyst is also used in an amount falling within the same ranges of parts per isocyanate equivalent as shown above; and with the same proviso as shown above for the range of total hydroxyl equivalents per equivalent of isocyanate. The ratios for each component in the blend in weight percent of the blend are the same ratios as shown in the description of the polyol blends. The amine diol 1, the amide diol 2, the amine triol 3, the primary polyol 1+ and the blowing agent always have the same meaning and specifications as shown above.

The trimerization catalyst used can be any known and conventional catalyst for trimerizing an organic isocyanate into an isocyanurate. Furthermore, a combination of an urethane-forming catalyst and a trimerization catalyst can be used if desired.

For characteristic isocyanate trimerization catalysts, reference is made to The Journal of Cellular Plastics, November / December 1975, page 329; de: U.S. Patents 3,771 + 5,133, 3,896,052, 3,899. ^ 3, 3,903,018, 3-95 ^ .681 + and U.101.I + 65.

Preferred catalysts are those described in U.S. Pat. Nos. 3,896,052 and 1+. 101.1 + 65. The first of these two concerns a catalyst coordination of a) an alkali metal salt of an H-substituted amide with b) an alkali metal salt of an N- (2-hydroxy-phenyl) methylglycine as well as c) a tertiary amine trimerization catalyst. The last writing concerns the combination of the same a) and b) components with a hydroxyalkyl trialkylammoniumcarboxylate salt component. The organic polyisocyanates that can be used in the preparation of the polyisocyanurate foams can be any conventional polyisocyanate that has also been used previously. Preferably, polymethylene polyphenyl polyisocyanates are used to obtain foams with a particularly good heat resistance and structural strength, most preferably those according to US patent 3.71 + 5.133. Further favorable 800 3 3 78 -13-polyisocyanates are the polymethylene polyphenyl polyisocyanates which have been treated with a minor amount of an epoxy compound to reduce the acid-reacting impurities of U.S. Pat. No. 3,793,362 as well as the polymethylene polyphenyl polyisocyanates with a high content of 2, if - / - is ome as described in U.S. Patent 3,362,979 *

The most favorable organic polyisocyanate is a mixture containing 30-85% w / w methylene bis (phenylisocyanate), while the rest of the mixture consists of polymethylene polyphenyl polyisocyanates with a functionality greater than 2.0.

In the preparation of the present polyisocyanurate foams, in particular foam foams for making foam laminates, the usual installations and techniques are used; for more details and the use of polyisocyanurate foam laminates, reference is made to US Pat. No. 3,896,052.

The following examples further illustrate the invention.

Example I:

The following five polyisocyanurate foams (A to E) were obtained according to the following procedure.

The foam materials were prepared as hand-mixed samples by mixing together the A and B ingredients (by weight of diluent as shown in Table A). The polyisocyanate component was a single component A, while the B ingredients shown in Table A were pre-mixed before viewing with the polyisocyanate.

Mixing was performed by placing components A and B in a beaker vessel and stirring at high speed. The mixture was then poured into a cardboard box so that it could rise freely and cure at room temperature (about 20 ° C).

The foam substances B and E correspond to the invention, while A, C and D fall outside the invention because the amine diol component had values for x and y which are too low. The B ingredient was always clear without any sign of cloudiness. However, A and C contained secondary hydroxyl polyols known as fluorocarbon dissolvers, while C additionally contained a phosphate plasticizer. Foam D 35 also contained a plasticizer.

800 3 3 78 -lU-

Maximum vessel foaming properties involving maximum reaction thermo, fast curing and low core and surface crumbiness were observed with foam E.

The surface formation in a rising foam sample is the point where the glossy and damp unreacted surface of the rising foam becomes dull, indicating that a good curing reaction has occurred at the surface. All foam samples showed good surface formation.

Table A

10 _

Scfauimstoffen_A B_C_D_E_

Ingredients (parts) A: polyisocyanate 1 ^ 100 100 100 100 100 15 B: diethylene glycol 5.7 5 Λ 6 6 8

Varonic L-2022 5 »7 - 6 6

Varonic K-2153 - 23.5 - 8 h

Pluracol GP-730 5.7 - 20 Pluracol PEF-6505 - 6 - -

Iris (dichloropropyl phosphate) - 7.2 18 18 propoxylated polyol - - 6- L-5tO0T '1.25 1.25 1.25 1.25 1.25 25 fluorocarbon R-11B8 25 25 25' 25 catalyst 1 ^ 333 33 NC0 / 0H index approx. ^ Approx. U approx. K approx. K approx. K appearance B clear clear clear clear clear component -Q foam reaction 171 156 1½ lk8 17 k exotherm (° C) / hardening fast slowly moderate fast fast core crumbiness strong low strong strong low surface crumbly-none none none none none 35 surface formation yes yes yes yes yes 800 33 78 -15-

Footnotes to Table A: 1 polyisocyanate 1 is a polymethylene polyphenyl polyisocyanate containing about k-5% methylene bis (phenyl isoeyanate) and the balance polyphenyl polyisocyanate having a functionality greater than 2; the isocyanate-5 equivalent was 133.

p

Varonic L-202 is a soy amine additive obtained by reacting 2 moles of ethylene oxide with soy amine; an amine equivalent weight of about 360 °, a hydroxyl equivalent level of about 180 and marketed by Ashland Chemical Company.

-3 10 Varonic K-215 is a coconut amine additive obtained by reacting 15 moles of ethylene oxide with coconut amine; an amine equivalent weight of about 8859 a hydroxy equivalent weight of about kb-2 and marketed by Ashlartd Chemical Company.

Pluraeol GP-730 is a propoxylated glycerol product having a hydroxy-15 equivalent weight of 2k3 sold by BASF-Wyandotte Chemical Corp.

Pluraeol PEP 650 is a propoxylated pentaerythritol product with a hydroxyl equivalent weight of 1 ^ 8 sold by the same company.

r

Propoxylated polyol is a product obtained by propoxylating a mixture of sorbitol and toluene diamine to a hydroxyl number of 360, a viscosity of 2500 centistokes at 25 ° C and a s'. g. of 1,072.

7 L-5U20 is a foam silicone wetting agent with a hydroxyl number of about 119, sold by Union Carbide and listed in its bulletin 25 F-i * 3565 of December 1971.

Q

0 Fluorocarbon R-11B is a monofluorotrichloromethane blowing agent stabilized with alloocimene and is sold by DuPont Chemical Corp.

Catalyst 1 comprises a combination of the following components: A) 1 part of a solution of a) U5% by weight of potassium or phenyl-2-ethylhexamide; b) 27 # ethylene glycol and c) 28 # dimethylformamide; B) 3 parts of a solution of 50 wt.% Sodium U- (2-hydroxy-5-nonyphenyl) 1-methyl 1-N-phenyl glycinate in diethylene glycol and C) 1 part of a solution of 50 wt. # 2-hydroxypropyl trimethyl ammonium formate and 50 # dipropylene-35 glycol; and D) 1 part of a polyethylene glycol of molecular weight 200.

O Λ Λ 7 7 7Q

-16-

Example II:

The following foams were prepared in accordance with Example I with only the differences noted below. The foams of this example allow comparison between the prior art (F and H) compared to the present invention (G and i).

The ingredients of the A camponent and the B camponent are shown in Table B. Substances F and G contained polyisocyanates other than Ξ and I. The A component for F and H contained a known fluorocarbon blowing agent. When the same amount of fluorocarbon was incorporated into the B campon 10 cm. in both cases it was found that this fluorocarbon separates from the other components. In mixtures G and I, in which an ethoxylated kdkosamine was present in the B-component, the fluorocarbon was found to be completely miscible with the other constituents of this diethylene glycol caravan.

A comparison of the foam row times between F and G and H and I clearly demonstrate that the subject foams rose rapidly compared to F and H. A very marked increase in reaction rate indicates the improved compatibility between components A and B, thereby better reaction between the two occurs resulting in a faster driving time. The ethoxylated amines in the foams G and I are tertiary amines of high molecular weight but of relatively low basicity, and were used in G and I in small amounts based on their amine equivalents, i.e. 0.009 equivalents in both cases. This low weak amine content is not sufficient explanation for the sharp increase in the speed of G and I compared to F and H based on an amine catalysis alone.

Table B

Foams F G Η I

OQ

Ingredients (parts) A: polyisocyanate 1 ^ 100 100 • 2 polyisocyanate 2 - 105 105 fluorocarbon R-11B 21.5 - 22.5 300 3 3 78 35 -17-

Foams_F_G_Η_I_ B: diethylene glyeol 8.3 8.0 8.3 8.0

Varonic K-215 - 8.9 - * 8.0 5 E-5420 1.25 1.2¾. 1.25 1.25 catalyst 1 3.0 3.0 3.0 3.0 fluorocarbon R-11B - 23 24 BCO / OH index M 4.2 4.6 4.2 foam driving time in seconds 10 cream 75 19 59 21 gel 104 42 96 4l no longer adherent ll6 49 106 47 exothermia (° C) 172 169 159 158 core density, pcf, 1.76 1.7¾ 1.79 1.75 15 dry heat aging l49 ° C / 24 hours. % £ volume +4.6 +4.1 +2.9 +2.4 core chunk, 1? 31 30 22 19 surface "brittleness none no no no 20 surface formation yes yes yes yes

Footnotes to Table B

1. "

see table A.

2 polyisocyanate II is a polymethylene polyphenyl polyisocyanate with about 35 wt.% Methylene bis (phenyl isoeyanate) and the remainder "consisting of polymer by polymer polyphenyl polyisate having a functionality of more than 2 and an isocyanate equivalent of 140.

3 ....

The "friability" is the percent weight loss over a 10 minute period and "determined according to the ASTM test method C-421.

Example III:

The following two polyisocyanurate foams J and K were prepared according to the invention using the method of Example I but using the ingredients of Table C.

The B components were clear in both cases.

Both foams had fine cells and their surface was -18- not "crumbly but well formed. The foam exotherm was good all the time and the rapid rise indicated good reactivity" at "both slant off and.

It can be pointed out that the catalyst mixture used J and K contained a very minor amount of Varonic K-215 amine diol 5 which acted as a unifying agent for the various catalyst components. In the absence of Varonic K-215, the remaining cat aly s at or c cmp are inoculated and not fully miscible.

Table C

Foams J K

10 _

Ingredients (parts) A: polyisocyanate lil ”* 135 135 B: 15 Varonic K-205 ^ 37 -

Varonic K-215 - 75 DC-1933 1.5 1.5 fluorocarbon R-11B 22 27 catalyst 11 ^ 3 3.

20 ITCO / OH index ^, 5 ^, 5 B appearance clear clear foam driving time in seconds cream 5 6 gel 20 20

25 non-stick 30 kQ

rice exothermia (° C) 165 152 surface brittleness none none surface. formation yes yes 30 core fragility slight low appearance very fine cells very fine cells

Footnotes to Table C:

Polyisocyanate III is a polymethylene polyphenyl polyisocyanate with 1 + 5% by weight of methylene bis (phenyl isocyanate) and the balance polymethylene polyphenyl polyisocyanates with a functionality of more than 2 and an isocyanate equivalent of 135 · 2. Varonic L-205 is a coconut amine adduct obtained by the reaction of 800 33 78 -19-5 moles of ethylene oxide with coconut amine, an amine equivalent weight of approx.

W * 5 and a hydroxyl equivalent of about 222.

3. DC-193 is a silicone wetting agent from Dow Coming, "described in its Bulletin 05-1½ of February 1966.

Ij. .

5 · Catalyst II comprises a combination of A; 1 part of a solution of 50 wt% sodium N- (2-hydroxy-5-nonylphenyl) methyl-N-methylglycinate in diethylene glycol; B) 0.5 parts of potassium acetate; c) 0.3 parts water and D) 0.5 parts Vaxpnic K-215, pointing out that this catalyst mixture was completely clear and completely miscible. Preparation of the same catalyst component but without the K-215 component results in a cloudy appearance. mixture.

Example IV:

The following two foams -L and M obtained with water as a leavening agent were prepared according to the invention using the method and apparatus of Example I using the components according to Table D. In both cases the B-component was completely clear and miscible.

The foam rising characteristics proved very favorable despite the fact that water was inflated. High foaming exotherm indicates the particularly good conversion. The physical properties of the foams were also excellent.

Table D

Foams_L_M_

Ingredients (parts) 25 A: polyisocyanate III 135 135 B: polyohixture I 23 30 L-5 ^ 20 2 2 30 H20 1 1 catalyst II 3 3 KC0 / 0ÏÏ index (including 3 2.5 of Η ^ Ο) B appearance clear clear 35 foam driving time in (seconds) / © ηn xx 7fl -20-

continued table D

_L_M_ cream 15 13 gel 31 26 5 proof W U8 non-adhesive 35 30 exothermia i- ° C) 191 195 density (pcf) 2.65 2.81 2.

K factor in. 10 BTÜ (ft2) (h.) ° F / in .: II in direction 0.190 0.201

Jtin direction 0.189 0.193 compressive strength (psi) || with the proof 39 »5 k2 15 J. on the proof 30.0 20% L at T0 ° C, 100 $ relative humidity. after 2h hours -7.7 -U, 7 149 ° C dry aging 4 volume 20 ($) after 2h hours -2.9 +3.0

Footnotes to Table D.

1. Polyol Blend I comprises a blend of the following ingredients: A) 1 * 0.8 $ of a 500 molecular weight polyaxydiethylene adipate glutarate polyester diol; B) $ 28.6 diethylene glycol and C) $ 30.6 Varonic 25 K-215.

2 ...

. The K factor is a measure of the thermal conductivity of materials, where the heat flow is determined according to the ASTM test method C-518.

Example V: 30 This example shows a hand-mixed polyisocyanurate foam N prepared according to the invention using the method and equipment of example I. The ingredients are shown in Table E.

The B component contained a mixture of a primary hydroxyItriol and diethylene glycol with hl wt% fluorocarbon; nevertheless, the mixture remained clear without cloudiness. This foam had a fast rising time and good exotherm in addition to good friability properties.

Tahel E

Foams U

5 _ -

Ingredients (parts) A: polyisocyanate III 135 B: 10 TPEG-9901 8.5 diethylene glycol 6.5

Varonic K-215 10 DC-193 1.25 Catalyst II 3.0 15 Fluorocarbon R-HB 20 B Appearance · Clear% R-11B in B Cl% Foam Rising Time (Seconds) Cream 13 20 Gel 30 Non-Stick 35 Exotherm (° C ) IJ6 surface brittleness none.

surface formation - yes 25 core lumpiness low

Footnote to Table E; 1. TPEG-990 is a primary hydroxy-containing trifunctional polyethylene glycol having a hydroxyl equivalent weight Tan 333, sold by Union Carbide Corp.

Example VI;

The following laminates with good high temperature and flame resistance were prepared according to the invention using foam O, which was prepared from the ingredients shown in Table F.

A Viking laminator was used at the "A" and, TB "- 8 0 0 .1378 -22" component temperatures of 23 and 22 ° C respectively. Feed through 7 kg / min through a low pressure mixing head. A casting technique was used instead of a rolling technique, the transport speed was 3 m / min and the temperature in the curing oven was 22-32 ° C.

A 5 cm thick laminate was prepared with 0.0015 ”aluminum foil coatings and also prepared with asphalt coatings. The foam properties are shown in Table F for the foam core material after the surface layers were removed. The surface material therefore has no influence on these figures. The adhesion between surface material and foam was excellent.

The component B although containing a primary hydroxyl polyester and diethylene glycol and k3% by weight of freon (R-11B) remained clear without cloudiness.

The laminates were produced without the need for high temperatures in the oven, because the composition reacts quickly. This rapid reactivity is also evident from the rapid proofing profile and the fact that the foam friability was particularly low despite the fact that no curing was done at high temperatures. The surface adhesion was good.

The figures are shown in Table F below.

Table F

Sehaêmstof_0_

Ingredients (parts) A: polyisocyanate I 133 25 B: polyester diol 1 9 diethylene glycol 6.3

Varonic K-215 6.7 DC-193 1.25 30 Catalyst II 3.0 Fluorocarbon R-11B 20.0 B Appearance Clear% R-11B in B b3% NC0 / 0H Index K, 9 35 Foam Rise Time (Seconds) 800 33 78 -23- cream 19

gel kO

non-stick bj opp. "friability no 5 surface formation yes core brittleness (6%) total density (pcf) 2.0 core tight. 1,8 compressive strength 10 [I with the row 31 pressure str. (psi)} in the row 21 dense cells2 9b%

K factor in BTU

15 (ft. 2) (uj ° F / in. 0.1h moist aging (70 ° C, 95 $ RH) ^ vol. After 1 day + 6% T days + 6.5% 28 days + 7.0% 20 ASÜM E-81 test on 5 cm thick samples of flame spread 38 smoke 187

Footnotes tide table F 1. Polyester diol is the same diol as shown in Table D.

2 ♦ Dense cells were determined by air cyclometer test according to the ASTM test method D-2856.

Example VII:. ____

The following polyisocyanurate foam P was prepared according to the procedure and equipment shown in Example I using the components of Table G. The B component was clear without any sign of cloudiness despite the combination of a fluorocarbon with primary hydroxyl groups of the amide diol.

The foam material produced had very fine cells, no surface friability and a good sealing surface. The foam exotherm was good and the rise profile fast indicating a rapid 800 33 78 -2 liter activity of the sonic material.

Tahel G_.

SGhrnTn _P_

Ingredients (parts) 5 A: polyisocyanate III1 135 B: 2

Varamide 6-CM 1 + 9 DC-193 1.5 10 fluorocarbon R-11B 23 3 catalyst II 3 KCO / ΟΞ index k, 5 B appearance clear rise time (sec) 15 cream 8 gel k2 non-stick 52 proof exothermic (° C) 328 20 surface Chunkiness no surface formation yes core chunkiness rather crumbly appearance very fine cells

Footnotes bi, i Table G.

25 * Polyisocyanate III is already shown in Table C.

2. Var amide 6-CM is a coconut amide adduct obtained by reacting 6 moles of ethylene oxide with 1 mole of coconut amide; amine equivalents, 290, hydroxyl equivalent, weight 193 and sold by Ashland Chemical Co .; also referred to as N, bis (8-hydroxy-3,6-dioxaoctyl) coconut-amide mixture.

3. Catalyst II xs the same catalyst as shown in Table C. Example VIII:

The following polyisocyanurate foams Q, R and S were prepared in accordance with Example I using the constituents of Tables. According to the invention, foams Q and R are not foams S.

The B components at Q and R were clear without any haze 800 33 78 -25- despite the fact that a fluorocarbon was mixed with a primary hydroxy-containing component.

The foam A-component F contained a prior art fluorocarbon blowing agent. When the same amount of fluorocarbon was mixed into the B component to check miscibility, the fluorocarbon was found to separate from the other components.

A comparison of the foam driving times between the foams Q and R on the one hand and foam S on the other clearly shows that the present foams Q and F rise faster than the foam S. This marked difference in driving speed indicates an improved compatibility between the components A and B, achieving a better response and faster driving time.

Table Ξ 15 Foam_§_R_S_

Ingredients (parts by weight) A: 135

polyisocyanate III

polyisocyanate 1 ^ 100 - 100 20 fluorocarbon R-11B - - 21.5 B: 2 polyester diol - 9 diethylene glycol 8 6.3 8.3

Var amide. 6-CM 8 6.7 25 L-5te0 1.25 - - 1.25 DC-193 2 fluorocarbon R-11B 25 22 catalyst II U, 5 5 3 catalyst I - - 3.0 30 RCO / OH index ca. U approx. Approx. U, 6 B appearance bright clear rise time (sec.) Cream 16 l6 75

gel U0 35 IOU

35 non-stick 1 * 5 bO 116 O η Λ 7 7 7fl -26- proof .5 ^ · .U8 exothermia (° C) 1T3 ITT 1T2 foaming fast fast surfacing none none 5 surfacing yes yes core density. (pcf) 1.55 2.06 1, T6 core friability (%) 38.5 32.0 31

dry aging at 10 ° C

^ volume% / 2k ur. + T »^ +5.0 + b, 6

10 Footnotes to Table H

. Polyisocyanate I is already shown in Table A.

2. Polyester diol: a polyoxydiethylene adipate glutarate polyester diol with molecular weight 500 and bydroxyl number 211.5 · 3. Catalyst I is already shown in Table A.

Example IX;

The following polyisocyanurate foam T was prepared according to the invention using the method and equipment of Example I using the ingredients of Table I.

The B campon was clear without any haze despite the combination of the fluorocarbon with a primary hydroxy-containing amine triol.

The foam produced had a very fine cell structure, no surface friability and good surface formation.

The foam exothermic was favorable, the rising time short and the reactivity of the foam good.

Table I

Foam_T

Ingredients (parts) A: 30 Polyisocyanate III 135 B: KD-21U1 56 DC-193 1.5 Fluorocarbon R-11B 23 35 Catalyst II 2.5 800 3 3 78 -27- IICO / OH Index B-Clear driving style (sec.) cream h

5 gel IT

non-stick 50 rice exothermia (° C) 1Ö2 surf. no 10 opp. formation of slight core debris. low appearance very fine cells

Footnotes he Table I.

1. KD-12k is an ethoxylated mixture obtained by reacting ethylene oxide with a coconut diamine in a mole elevation of ca.

1h to 1, wherein the coconut diamine was obtained by reacting coconut amine with an equivalent amount of acrylonitrile and: reducing a cyanoethylated coconut amine mixture to coconut diamine; amine equivalent weight 290; hydroxyl equivalent weight 193 20 and sold by Ashland Chem. Co.

Example X:

The following polyisocyanurate foams U, V and W were prepared according to Example I using the ingredients shown in Table J. The foams U and V are according to the specifications. ...

invention, while foam ¥ is this with.

The B components in foams U and V were clear without any sign of turbidity despite the mixture of a fluorocarbon with a primary hydroxyl containing component in both blends.

The foam A-component W contained the fluorocarbon blowing agent of the prior art. When the same amount of fluorocarbon was mixed with the B component, the fluorocarbon component separated from the other ingredients.

A comparison of the driving times between the foams U and V, on the one hand, and the foam ¥, on the other hand, clearly showed the faster driving time in the foams according to the invention. The distinct 800 33 78 -28 speed increase indicates improved compatibility between components A and B, resulting in a better response and therefore shorter driving times.

Table I

5 foam fabric_U_V_W_

Ingredients (parts) A: polyisocyanate III - 135 polyisocyanate I 100 - 100 10 fluorocarbon 'R-11B - - 21; 5 B: polyester diol ^ - 9 - diethylene glycol 8 6.3 8.3 KD-21U 8 6.7 15 L-5te0 1.25 1.25 DC-193 - 2 fluorocarbon R-1U3 25 22 - Catalyst II 2.5 2.5 - Catalyst I - 3.0 20 IC0 / 0H index approx. Ü approx. V approx. U, 6 B appearance clear clear - rise time (sec.) Cream l6 15 T5 gel 39 too ÏOU- paste-free h6 50 116 proof 56 60 exothermia (° C) l66 169 172 time to firm - fast fast surface crumbling none none 30 surface formation yes yes core density (pcf) 1.67 2.27 1.76 core friability {%) 18.8 33 ', 1 31 dry aging at 1 ^ 9 ° 0 ^ volume% / 2h h. +10.8 +5.3 + k, 6

35 Footnote to Table J

800 33 78 * <-29- 1. Polyester diol: a polyoxyethylene adipate glutarate polyester diol of molecular weight 500 and hydroxy number 211.5.

Example XI:

A series of mixtures of fluorocarbon R-1IB (monofluorotrichloromethane) with two characteristic primary hydroxy polyols of the invention were prepared. The weight ratios used, including the amount of amine diol I when present, varied according to the figures shown in Table K. The blends were tested for their miscibility and clarity without cloudiness and the separation of the fluorocarbon from the solution.

Blends A-D contain diethylene glycol with fluorocarbon and no amine diol, i.e., 100% diethylene glycol; the maximum solubility for the fluorocarbon was 15% by weight. An addition of 10 wt amine diol was not sufficient to increase the fluorocarbon solubility to a level of 25 wt%, while a content of 20 wt amine diol (D) resulted in a clear solution containing 25 wt fluorocarbon.

Blends E through J contained a polyester diol as shown above, with the polyester diol found to be able to dissolve up to 20 wt% fluorocarbon, but not 25 wt. 25% fluorocarbon solubility was found to be achieved at about 10 wt.% Amine diol (G), while at the 20 wt. Level for the amine diol, the solubility for the fluorocarbon was 31 wt.

Blends K to M were found to have maximum fluorocarbon levels of over 90% and up to 61.5% diethylene glycol and polyester diol when a maximum of 85% by weight amine diol was used.

Blends R through Q had maximum fluorocarbon solubilities of $ 60 and $ 50 using diethylene glycol and a polyester diol when the primary amine diol blends were 50/50 wt.

- ✓ 800 33 78 -30- H 1 oo cu <§ cm cn clearly miscible

LON

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Hl I Η H

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Kd LA I 1Λ t- IA 1Λ VO

^ H

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ö 0 0 O 5-i S Η · <"5% 2 Η 0Η-Ρ O ft 0 <H · Η t ^

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to 9 +: HO · * 0 t JK lL

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0 a · Η O 1 Η 0 0 0 · Η £ g .HtJftMLHnaias> t-cm 800 3 3 78 -32-

Example XII:

A series of mixtures of fluorocarbon R-11B with three characteristic primary hydroxyl polyols of the invention were prepared.

The weight ratios including the amount of coconut amide diol 5 (II) when present varied according to the figures in Table L. The blends were viewed for their miscibility and clarity or turbidity and separation of the fluorocarbon from the solution.

Mixtures A to D contain diethylene glyeol and in the absence of any amide diol. the maximum fluorocarbon solubility was less than 10 wt.%. Addition of 10 # amide diol (II.) Was not sufficient to bring the fluorocarbons great solubility to a 20 # level. Only at least 15 # amide diol (c) a clear preparation was obtained with 20 # fluorocarbon and thus was clear at the 80/20 level (D).

Blends E through G contain ethylene glycol and at least 20 # of amide diol needed to maintain a 20 # of fluorocarbon solubility.

Blends H to L were prepared from a polyester diol and it was observed that while a 20 # 's fluorocarbon solubility was possible with the pure diol, a 25 #' s level was not reached. When the amide diol level reached 20 # (blends J through L), the highest attainable fluorocarbon level was about 31 #.

Blends M to 0 had maximum fluorocarbon levels of greater than 90% and up to 60% by weight for diethylene glyeol and the polyester diol, respectively, when a maximum of 85% by weight amide diol was used.

Blends P to S were found to have maximum fluorocarbon solubilities of 55 # and ^ 5 # for diethylene glyeol and polyester diol, respectively, if the primary alcohol / amide diol mixtures were 50/50 # by weight.

800 33 78 * -33-

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p ^ cloudy, separates ü o o o o o on I i co cm la co oj on h

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800 33 78 -35-

Example XIII:

A series of mixtures of fluorocarbon R-11B with three characteristic primary hydroxyl polyols of the invention were prepared.

The weight ratios including an amount of amine triol if present varied according to the figures of Table M. The blends were viewed for their miscibility and clarity or their turbidity and separation of the fluorocarbon from the solution.

Mixtures A to D contained diethylene glycol and in the absence of any aminetriol, the fluorocarbon solubility reached less than 10 wt.%. Addition of 10 # aminetriol (B) was not sufficient to bring the fluorocarbon solubility to a 20 # level. Only use at least 15 # aminetriol. a clear solution was achieved at 20 # fluorocarbon.

Blends E through G contain ethylene glycol and at least 20 # 15 amine triol needed to achieve a 20 # 's fluorocarbon solubility.

Mixtures H to M were prepared from a polyester diol and it was observed that although a 20 # crude carbon solubility was possible, a 25 # solubility of the chlorinated carbon was not achieved with the pure diol, while at 15 wt. # aminetriol this 25 # 's solubility for the fluorocarbon was reached (K). At 20 weight percent aminetriol, the maximum fluorocarbon solubility was approximately 28.6 weight percent.

Mixtures N through P had maximum fluorocarbon contents of more than 90 # (diethylene glycol), respectively. 50 wt. polyester diol 1 if a maximum of 85 # aminetriol was used.

Blends Q through T were found to be able to contain a maximum fluorocarbon content of 50 # (diethylene glycol) or ko # (polyester diol), if the primary alcohol / amine triol ratio was 50/50.

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800 3 3 78

Claims (3)

1. Polyol blend containing (l) 20-85 wt.% Based on the total weight of the mixture of a substance or mixture of the formula 1, 2 or 3 of the formula sheet, wherein R is an aliphatic group containing 8-18 carbon -atoms, Rg is an aliphatic group with 7-17 carbon atoms, each R ^ hydrogen-5 substance or methyl, x and y has an average grade of U-15, x 'and y' has an average grade of 1-3, x ", y "and z an average grade of 1-5 and n is 2 or 3; and (2) 15-80 percent by weight of a primary hydroxy-polyol having a molecular weight of 60-1000. 2. Miscible polyol blend having at least about 20 wt.% of a fluorine-10 carbon blowing agent and the remainder consisting of a polyol blend according to claim 1. 3. A polyol blend containing about 1-6 wt. water and about 9 ^ -99 wt. polyol blend according to claim A polyol mixture according to claim 1, wherein R 1 is always hydrogen and (2) is a primary hydroxyldiol 5. A polyol mixture according to claim characterized in that (1) is a compound of the formula 1 e or an ethoxylated coconut-diol mixture obtained by reacting about 15 moles of ethylene oxide with 1 mole of coconut amine. The polyol mixture according to claim k, wherein (1) is a substance of the formula II, namely R, R-bis (8-hydroxy-3,6-dioxaoctyl) coconut amide mixture. Polyol blend according to claim U, wherein (1) is a substance of the formula III, namely a mixture of amine triols derived from coconut amine, each component of the mixture having mean values for x ”, y” and z of k, 6 and n is 3. 8. Polyol mixture according to claims 5 »6 or 7, characterized in that the primary hydroxyldiol diethylene glycol is 9. Polyol mixture according to claims 5» 6 or 7, characterized in that the primary hydroxyl is a polyaxydiethylene adipate glutarate. - polyester diol with a molecular weight between 100 and 600. Polyol mixture according to claims 5-6 or 7, characterized in that the primary hydroxyldiol is a mixture of 30-50% by weight diethylene glycol and 50-70% by weight of a polyoxyethylene adipate glutarate poly - 35 ester diol with a molecular weight of U00-600. 800 3 3 78 -39- 11. A miscible polyol mixture containing at least 20 wt.% Of an in carbon dioxide blowing agent and the remainder consisting of a polyol mixture according to claims 8, 9 or 10. 12 Polyol blend containing 2-20 wt.% of an isocyanate tromerization catalyst and 80-98 wt.% of a polyol mixture according to claims 2 or 3. 13. A process for preparing a cellular polymer in which the main repeating polymeric unit is an isocyanurate The piece is characterized in that an organic polyisocyanate tromer is generated in the presence of a minor amount of a polyol, an blowing agent and a trimerization catalyst and wherein the cellular polymer is prepared by combining (A) a organic polyisocyanate; and (B) 10-120 parts by weight per equivalent of polyisocyanate of a mixture comprising: a) 2-20% by weight of a polyisocyanate trimerization catalyst and b) about 80-98% by weight of a mixture consisting of ( 1) about 20-80% by weight of a fluorocarbon coolant blowing agent and (2) about 20-80% by weight of a mixture consisting of one or more compounds of formulas 1, 2 or 3, wherein the symbols have the meanings shown above, provided that the total bydroxyl equivalent present in the mixture B is between 0.05 and 0.5 equivalent per equivalent isocyanate. l. A process for preparing a cellular polymer, wherein the main piece is an isocyanurate piece in which an organic polyisocyanate is trimerized in the presence of a minor amount of a polyol, an blowing agent and a trimerization catalyst, characterized in that this cellular polymer is prepared by combination of A) an organic polyisocyanate and B) 10-120 parts by weight per equivalent of this polyisocyanate of a miscible mixture containing a) 2-20% by weight of a polyisocyanate trimerization catalyst and b) 8Ο-98% by weight of a mixture with therein 1) at least 20% by weight of a fluorocarbon or blowing agent and 2) the residue consisting of a polyol mixture according to claim U; provided that the total hydroxy le equivalents in 800 33 7O-Mi-mixture B are between about 0.05 and 0.5 equivalent per equivalent of polyisocyanate. Process according to claim 1, characterized in that the polyisocyanate is a polymethylene polyphenyl polyisocyanate. 5 16. The method of claim 15, wherein B (b) comprises: 1. at least 20 wt.% Of a fluorocarbon blowing agent and 2. the remainder is a polyol blend according to claims 8, 9 or 10. 800 3 3 78 1 L R1 f1 (CH2CHOM 0 iCH 2cho ^ h R - * <X R2 «CN ^ ^ CH2CHO ^ - H 3 p, ^ SCH2CHOf-H ΔI y - Ri 21 yRi (ch2cho ^, h ri iCHR, fc -N ^ B- / NCH2CH0 ^ \ cH2CHO) -H Rl * I z R1 A_ ^ CH2CHO} -H R2COR3 + HN ^ fx -k 2 + HR3 ^ CH2CH0f-H ^ “I y 'Rl 1. [nh3] 2 RNH2 + CHRi— CHRj- £» RNHCHRxCHRχOH RNHCHR1CHR1NH2 E.Q. and / or PQ. 3 <c- L 2 j8_ [H] -1 RNH2 + R 1CH = CRiCN-RNHCHR 1CHRi-CN-RNHCHR-CHRiCH 2 NH 2 ED. and / or P.O. L <- The Upjohn Cojnpjiny 800 3 3 78