CA1140695A - Miscible fluorocarbon-polyol blends - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Disclosed are novel polyol blends comprising from about 20 percent to about 85 percent by weight of said blend of a member or mixture of members selected from particular types of amine diols (I), amide diols (II), and amine triols (III), and from about 15 percent to about 80 percent by weight of a primary hydroxyl polyol (IV) characterized by a molecular weight of from about 60 to about 1000.
The polyol blends are miscible with fluorocarbon blowing agents and water and other adjuvants including trimerization catalysts.
The novel blends are particularly useful in an improved process for the preparation of polyisocyanurate foams. The foams are characterized by high reaction exotherma making such foams particularly suited to the preparation of polyisocyanurate foam laminates.

Description

BA~KGROU~D OF THE INVENTION
1. Field of the In~ention This invention relates to cellular polymers and intermediates therefor and is more particularly concerned with novel polyol blends and their use in a process for the preparation of cellular polyiso-cyanurates.

2. Description of the Prior Art Cellular polyisocyanurate polymers are well known in the art for tneir use in various types of thermal insulating applications. They are also well known for their ability to withstand heat and flame; see U. S.
Patents 3,745,133, 3,986,991, and 4,003,859. Minor amounts of polyols are sometimes added to the foam forming ingredients to modify the foam properties. When fluorocarbon blowing agents are employed the problem of the incompatibility that may arise between the polyol, particularly primary hydroxyl polyols, and fluorocarbon in resin premixes is generally solved by premixing most, if not all, the fluorocarbon with the polyisocyanate; see the patents cited supra.
Polyisocyanurate foams find particular utility in the production of laminated foam board stock material which can be prepared with a variety of different facer materials. Problems which can arise in the production of such laminate material include 1.) lack of uniform foam core strength; 2.) poor adhesion between foam core and facer material; 3.) màintaining good fire resistance in the foam; and 4.) keeping foam friability at low levels. These problems have been 1$'~

overcome in the art by employing minor amounts of low equivalent weight polyols, particularly diols, in the formulation, combined with the heating of the formed laminate product in an oven at 160 to 190F.; see U.S.
Patent 3,903,346.
However, the low equivalent weight polyols employed, particularly the preferred diols (see column 4, lines 59-61 of U. S. 3,903,346) having only primary hydroxyl groups, cannot be blended beforehand with the fluoro-carbon blowing agent in a "B" side component because of the low solubility of the diol-fluorocarbon pair.
This necessitates the blending of the fluorocarbon with the polyisocyanate in the "A" side component. Further, because of the fluorocarbon diol immiscibility, the above patent teaches that a third component "C" is required which contains the catalyst constituent dissolved in a low molecular weight glycol; see column 2, lines 32-33 and the examples of 3,903,346.
Furthermore, a laminate preparad in accordance with the patent noted above must be heated in an oven to provide a product having a uniform foam core strength.
Surprisinglyj it has been found that high levels of fluorocarbon blowing agent are completely miscible with low molecular weight polyols containing primary 2S hydroxyl groups when novel blends comprisiny certai~ types of amine or amide diols or amine triols with the primary hydroxyl polyols are employed, Additional ingredients which can be present in the miscible blends are surfactants, catalysts, and the like.
Further, it has been found that the same type of ~'`

miscible primary hydroxyl containing blends as described above, except that water replaces the fluoro-carbon component, can be obtained.
Furthermore, it has been discovered that the novel polyol blends above can be employed in minor amounts as a B type component to prepare polyisocyanurate foams characterized by low friability, fine cell structure, good dimensional stability, and low flame spread, via a two-component, i.e., an A, and a B side, process.
The fluorocarbon and water components act as the blowing agents in their respective foam forming formulations.
Further, the certain types of amide or amine diols or amine triols referred to above can be employed as the sole polyol ingredient in combination with the fluorocarbon or water, catalyst, surfactant, and other adjuvants to provide polyisocyanurate foams in accordance with the present invention.
Quite unexpectedly, the presence of the amide or amine diols or amine triols in the B side gives rise to excellent reactant compatibility between the polyisocyanate and the other ingredients. This gives rise in turn to faster reactivity compared to prior art foams and very good reaction exotherm. The hlgh exotherm is of particular advantage when foam laminates are being prepared because it results in excellent adhesion between foam and facer material thereby eliminating the need of heating the formed laminate in an oven.
SUMMARY OF THE INVENTION
This invention comprises polyol blends comprising (i) from about 20 percent to about 85 percent by weight of sa~ blend of a member or mixture of members selected from compounds of the formulae:

f CH2CHOt-H 1 ~ CH2CHO ~,H
R-N ~ ; R2-C-N ~ ; and Rl R
I II
Rl f CH2CHO~

R-~ ~ CH 2 ~HO~
CH 2CHO~H

III

wherein R is an aliphatic radical having from 8 to 18 carbon atoms, inclusive, R2 is an aliphatic radical having from 7 to 17 carbon atoms, inclusive, each Rl is independently selected from the group consisting of hydrogen or methyl, x and y each independently have an average value from about 4 to about 15 inclusive, x~
and y' each independently have an average value from about l to about 3, inclusive, x" , y" , and z each ~ independently have an average value from about l to about 5, inclusive, and n is 2 or 3; and (ii) from about 15 percent to about 80 percent by weight of a primary hydroxyl polyol (IV) characterized by a molecular weight of from about 60 to about lO00.
This invention also comprises miscible blends arising from the above polyol blends in combination with a fluorocarbon or water blowing agent.
This invention also comprises miscible blends arising from the above polyol blends in combination with a fluorocarbon or water blowing agent and an 35~5F

isocyarlate trimerization catalyst.
The invention also comprises processes for the preparation of polyisocyanurate cellular polymers which utilize, as a blended component, a member or mixture of members selected from compounds of the formulae (I~, (II), or (III) above wherein the values of x and y can have independent average values of from about 1 to about 15 but preferably from about 4 to about 15, with x', y', x", y", z, n, R, Rl, and R2 having the definitions set forth abovel in combination with a fluorocarbon or water blowing agent and a trimerization catalyst, and, preferably, the blended component additionally containing the polyol (IV) in which case the diol (I) is defined as above witll the narrower range of x and y of about 4 to about 15, in the reaction with an organic polyisocyanate.
The invention also comprises the cellular polymers produced in accordance with the above process.
The invention also comprises a laminate panel having a polyisocyanurate foam core made in accordance with the improved process in accordance with the present invention.
The term "aliphatic radical" as it relates to R means alkyl and alkenyl having from 8 to 18 carbon atoms inclusive.
Representative of alkyl are octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and isomeric forms thereof. Representative of alkenyl are octenyl, decenyl, dodecenyl, -tetradecenyl, hexadecenyl, octa-decenyl, and isomeric forrns thereof.
The term "aliphatic radical" as it relates to Rz 35~5~
11~0~;~5 means alkyl and alkenyl having from 7 to 17 carbon atoms inclusive. Representative of alkyl and alkenyl in this case are the same as above except for the lower carbon atom range beginning at heptyl or heptenyl and ending at heptadecyl or heptadecenyl and isomeric forms thereof.
The polyol blends in accordance with the present invention can be used as the polyol ingxedients in the preparation of polyurethane foams. Polyurethane foams are well known in the art for their use in a wide variety of applications including thermal and sound insulation for both industrial and residential buildings.
The polyol blends find particular utility, as set forth herein, as minor constituents in the preparation of polyisocyanurate foams particularly those polyiso-cyanurate foams prepared in foam laminate machinery and by spray foam equipment. Such foams are well known for their heat and fire resistance and are used in making laminate boards and foam bun stock which are both used in building construction for thermal and sound insulation, DET~ILED DESCRIPTION OF THE INVENTION
The polyol blends in accordance with the present invention are prepared simply by mixing together, in the proportions by weight set forth above, the amine diol (I), amide diol (II), or aminé triol (III? and a primary hydroxyl polyol (IV) defined above, in any suitable mixing vessel, holding tank/ storage vessel, or the like. Preferably, (I), (II), or (III) is employed within a range of from about 25 percent to ~7-about 60 percent by weight of the blend while the primary hydroxyl polyol is employed within a range of from about 40 percent to about 75 percent by weight.
Preferred members of (I), (II), and (III) have the formulae set forth above wherein Rl is hydrogen in all cases.

A most preferred diol is that which has the formula corresponding to (I) wherein both Rl groups are hydrogen, and x and y each independently have an average value from abo~t 5 to about 10 inclusive.
10A most preferred amide diol has the formula corresponding to (II) wherein both Rl groups are ~ ;
hydrogen and x' and y' each independently have an average value from about 2 to about 3 inclusive.

A most preferred amine triol has the formula corresponding to (III) wherein all the Rl groups are hydrogen, and the x", y", and z each have an average value from abo~t 3 to about 5 inclusive, and n is 3.
The amine diols (I) are prepared using standard reactions known to those skilled in the art and in ` some instances the amine diols are commercially available. Typically, the amine diols (I) can be prepared by reacting the appropriate dialkanolamine ~ith the appropriate aliphatic halide (R-X) compound, or mixture of different R-X compounds where all the aliphatic groups (R) fall within the definition above and X is halogen preferably chlorine or bromine. If the desired number of alkyleneoxy groups are not already present in the dialkanolamine prior to ~14~5 reaction with the aliphatic halide they can be readily added afterward by reacting the alkylated dialkanolamine with the appropriate number of moles of ethylene oxide or propylene oxide, or mixtures thereof, to provide the amine diols of formula (I).
Preferably, the amine diols (I) are prepared ~y reacting the appropriate primary fatty amine R-NH2 or mixture of fatty amines wherein all the R groups are defined as above, with from about 2 to about 30 moles, preferably from about 8 to about 30 moles, most preferably 10 to 20 moles, of ethylene oxide or propylene oxide per molar proportion of fatty amine;
see Bulletin 1294, entitled Ethoxylated Fatty Amines, Ashland Chemical Company, Division of Ashland Oil Inc., Box 2219, Columbus, Ohio 43216 for a detailed teaching of the preparation of the subject amine diols.
Illustrative of the starting fatty amines are octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, and isomeric forms thereof. Illustrative of the alkenylamines are octenyl-amine, decenylamine, dodecenylamine, tetradecenylamine, hexadecenylamine, octadecenylaminej and isomeric forms thereof. Further illustrative of said fatty amines are mixtures of alkyl- and alkenylamines, for example, cocoamine which consists of the following mixture in approximate percent proportions by weight: 2% decyl-amine, 53% dodecylamine, 24% tetradecylamine, 11% hexa-decylamine, 5% octadecylamine, and 5% octadecenylamine;
soya amine in the following approximate proportions:
11.5% hexadecylamine, 4% octadecylamine, 24.5% oleyl-amine, 53% linoleylamine, and 7% linolenylamine; and tallow amine in the following approximate proportions:
4~ tetradecylamine, 29~ hexadecylamine, 20~ octadecyl-amine, and 47~ octadecenylamine. Further illustrative of the starting fatty amines are the halogenated fatty amines, particularly the chlorinated and brominated fatty amines, which, illustratively, can be made by the chlorination or bromination of cocoamine, soya amine, tallow amine, and the like.
A particularly preferred group of fatty amines consists of cocoamine mixture, soya amine mixture, and tallow amine mixture. A preferred member of this group is cocoamine.
The amide diols (II) are prepared using standard reactions known to those skilled in the art. Typically, they can be prepared by reacting the appropriate dialkanolamine with the appropriate fatty acid, fatty acid ester, or fatty acid chloride according to the following equation ll ~CH2CHO~-~H
R2COR3 + H ~ x ~ II + HR3 yCH2CHot-~H
Rl wherein R2 , Rl, x', and y' have the same definition as above and R3 represents -OH, -OR4, and X wherein R4 represents any typical esterifying group such as lower alkyl, aryl, cycloalkyl, and the like, and X is halogen preferably chlorine or bromine. In the event that diethanolamine or diisopropanolamine or a mixture thereof is the starting dialkanolamine, and it is 6~

desired to obtain amide diols in which the values of x'and y'are greater than 1, then the intermedia~e dialkanolamide is simply reacted in a one molar propor-tion with from about 1 to al~out 4 molcs of ethylcne oxide or ~ropylene oxide, or mixtures thereof. Sec sulletin 1295, entitled Varamiclc ~lkal~olamiclcs, Ashland Chemical Company, Division of Ashland Oil, Inc., Box 2219, Columbus, Ohio 43216 for a detailed teaching oE tl~e preparation of fatty acid dialkanolamides.
Preferably, the amide diols (IIjare 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 amide, of ethylene oxide or propylene oxide, or mixtures tl~ereof.
Illustrative of the starting fatty acids (from wllicll the corresponding esters, acid halides, and amides are also derived) are caprylic, capric, lauric, myristic, palmitic, stearic, and isomeric forms thereof. Illustra-tive of the unsaturated fatty acids are decylenic, dodecylenic, palmitoleic, oleic, linoleic, and isomeric forms thereof. Further illustrative of said fatty acids are mixtures, for example, the fatty aci~ mixture derived from coconut oil which consists of the following mixture in approximate percent proportions by weight: 8.0~ caprylic,7.0~ capric, 48.0% lauric, 17.5% myristic, 8.2% palmitic, 2.0% stearic, 6.0%
oleic, and 2.5~ linoleic; the fatty acid mixture from soybean oil: 6.5% palmitic, 4.2% stearic, 33.6%

oleic, 52.6~ linoleic, and 2.3% linolenic; and the fatty acid mixture from tallow: 2% myristic, 32.5%

palmitic, 14.5~ stearic, 48.3~ oleic, and 2.7% linoleic.
Further i~lustrative of the starting fatty acids are the halogenated fatty acids, particularly the chlori-nated and brominated fatty acids, which, illustratively, can be made by the chlorination or bromination of the coconut, soybean, and tallow fatty acid mixtures described above.
A particularly preferred group of starting fatty acids and fatty acid amide intermediates consists of the coconut, soybean, and tallow oil mixtures described above and the corresponding cocoamide~ soyamide, and tallow amide mixtures. Preferred members of this group are the coconut oil mixture and its cocoamide mixture derivative.
A preferred group of amide diols (II)are the cocoamide diol, soyamide diol, and tallow amide derived diol mixtures wherein each Rl is H and both x'and y' have a value of about 3. A preferred species within this group of amide diols is the cocoamide diol mi~ture above and identified by the chemical name of N,N-bis(8-hydroxy-3,6-dioxaoctyl)cocoamide mixture.
The amine triols (III) are easily prepared using standard reactions known to those skilled in the art and in some instances the amine triols are commercially available.
Generally speaking, the mode of preparation of the amine triols having n equal to 2 will differ slightly from those amine triols having n equal to 3. The former amine triols can be easily prepared according to the following scheme.

[NH3]
RNH2 ~ C ~ - CHRl - ~ RNHCHRlCHRlOH ~ RNHCHRlCHRlNH2 V VI
E.O. or P.o. or mixtures ~II ~
wherein R, and Rl are defined above. The amine starting material is reacted with an equimolar amount of ethylene or propylene oxide to form the aminoalcohol (V) which can be easily transformed into the diamine (VI~, typically by reaction with ammonia, followed by the reaction of a molar proportion of (VI) with from about

3 to about 15 molar proportions of ethylene oxide or propylene oxide or mixtures thereof to form the amine triol (III).
Amine triols ha~ing n equal to 3 are typically prepared by the following scheme.
[H]
RNH2+ RlCH=CRlCN ~ RNHCHRlCHRl-CN--e RNHCHRlCHRlCH2NH2 VII VIII IX

E.O. or P.O.
or mixture wherein R, and Rl are defined above. The amine starting material is cyanoethylated with the appropriately substituted acrylonitrile (VII)to form (VIII) which is reduced to the diamine (IX) , followed by alkoxylation with from about 3 to about 15 molar proportions of ethylene oxide or propylene oxide or mixtures thereof to form (III).
The starting fatty amines are the same as those set forth above and exemplified in the preparation of the amine diols (I).

` -9~i Illustrative of the acrylonitrile compounds which can be used in the preparation of the amine triols in accordance with the present invention are acrylonitrile, ~-methacrylonitrile, ~-methacrylonitrile, ~,~-dimeth-acrylonitrile, and the like. Preferred is acrylonitrile.
A preferred group of amine triols (III) are the amine triol mixtures derived from cocoamine, soya amine, and tallow amine mixtures wherein all the Rl groups are hydrogen, the value of n equals 3, and the value of x", y", and z each equal from about 3 to about 5. A most pre~erred species is the amine triol mixture derived from cocoamine wherein all the Rl groups are hydrogen, the value of n equals 3, and the value of x", y", and z each equal about 4.6.
The primary hydroxyl polyol (IV) can be any primary hydroxyl polyol having a molecular weight of from about 60 to about 1000, preferably from about 60 to about ~00, and most preferably from about 60 to about 600. Included in the polyols (IV) are diols, triols, and tetrols. The preferred polyols are diols.
Included in the class of primary hydroxyl contain-ing polyols are the various primary hydroxyl containing diols, triols, and tetrols disclosed in U. S. Patent 3,745,133 which meet the molecular weight limitations set forth above. The preferred ~5 classes are the polyester polyols prepared from dibasic carboxylic acids and polyhydric alcohols including those based on chlorendic 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. by W. R. Sorenson et al., 1961, page 293, Interscience Publishers, New York, N.Y.), and polybutadiene resins having primary hydroxyl groups, (see Poly Bd Liquid Resins, Product Bulletin BD-3, October 1974, Arco Chemical Company, Div. of Atlantic Richfield, New York, N. Y.).
The most preferred classes are the alkylene diols, lower alkoxyalkylene diols, polyalkylene ester diols, and polyoxyalkylene ester diols.
Illustrative, but not limiting, of the preferred classes of polyols in accordance with the present invention are ethylene glycol, 1,3-propanediol, 1,4-butanediol, glycerine, trimethylolpropane, pentaery-thritol; diethylene glycol, the polyoxyethylene glycolsprepared by the addition of ethylene oxide to water, ethylene glycol, or diethylene glycol, etc., which provide triethylene glycol, tetraethylene glycol, and higher glycols, or mixtures thereof such that the molecular weight falls within the range set forth above;
ethoxylated glycerine, ethoxylated trimethylolpropane, ethoxylated pentaerythritol, and the like; bis(~-hydroxyethyl)terephthalate, bis(~-hydroxyethyl)phthalate, and the like; polyethylene succinate, polyethylene glutarate, polyethylene adipate, polybutylene succinate, polybutylene glutarate, polybutylene adipate, copoly-ethylenebutylene succinate, copolyethylenebutylene glutarate, copolyethylenebutylene adipate, and the like hydroxy terminated polyesters; polyoxydiethylene succinate, polyoxydiethylene glutarate, polyoxy-. -15 6~i dietllylerle adipate, polyoxydiethylene adipate glutarate and the like; diethanolamine, triethanolamine, N,N' bis(~-hydroxyethyl)anilin~, and the like.
The most preferred diols are diethylene glycol, and the polyoxydiethylene adipate glutarate polyester diols having a molecular weight from about ~00 to about 600.
Particularly preferred are blends of from about 30 percent to about 50 percent by weight of diethylene glycol with from about 50 percent to about 70 percent by weight of a polyoxydiethylene adipate glutarate polyester diol having a molecular weight from about 400 to about 600.
In the preferred polyol blends in accordance with the present invention a fluorocarbon or water blowing agent is also present in the blend with the fluorocarbon beiny the preferred blowing agent.
When the blowing agent is a fluorocarbon the unexpected and advantageous features of the polyol blends Of (I), (II), or (III) with (IV) can be realized fully Accordingly, there can be obtained miscible polyol blends comprising at least about 20 percent by weight of a fluorocarbon blowing agent and the balance being the blends within the proportions set forth above.
The particular percentage of fluorocarbon to be dissolved in the bl~nd will govern the proportions of (IV) and of (I), (II), or tIII) to be employed in any given instance and these proportions, falling within the range set forth above, can be easily determined by one skilled in the art by trial and error methods.

~4~

Miscible polyol blends comprising greater than 50 percent by weight of fluorocarbon and even up to 90 percent by weight can be readily obtained with the blends within the proportions set forth above in accordance with the present invention and depending on the choice of blend ingredients. Generally speaking, the lower the molecular weight of the primary hydroxyl polyol (IV) the greater is the amount of fluorocarbon which can be dissolved in the blend at a given proportion of polyol (I), (II), or (III), as opposed to a blend with a polyol (IV) of higher molecular weight at the same proportion. In this connection, the alkylene diols, and lower alkoxyalkylene diols having molecular weights of less than 400 are preferred polyols of formula (IV) with the latter lower alkoxyalkylene diols heing most preferred.
The particular proportions of polyol (I),(II), or (III) to polyol (IV) to be employed in any particular polyol blend to obtain maximum miscibility with fluoro-carbon can be determined by a process of trial and error.
Generally speaking, when the amine diol (I) isemployed with (IV) there are obtained miscible polyol blends comprising from at least about 25 percent by weight to at least about 65 percent by weight of a fluorocarbon blowing agent and the corresponding 75 percent to about 35 percent by weight being the blend ` of (I) and (IV).
When the amide diol (II) and (IV) are employed there are obtained miscible polyol blends comprising from at least about 20 percent by weight to at least .

about 60 perc~nt by weight of a fluorocarbon blowing agent, the corresponding 80 percent to about 40 percent by weight being the polyol blend of (II) and (IV).
Andr when the amine triol (III) and (IV) are employed there are obtained miscible polyol blends comprising from at least about 20 percent by weight to at least about 50 percent by weight of a fluoro-carbon blowing agent and the corresponding 80 percent to about 50 percent by weight being the polyol blend of (III) and (IV).
When water is the blowing agent it is present in the proportions of from about 1 percent to about 6 percent, preferably from about 2 to about 5 percent by weight with the balance of 94 percent to 99 percent and preferably 95 to 98 percent comprising (I), (II), or (III) with (IV).
The fluorocarbon blowing agent can be any of the fluorocarbons known to those skilled in the art and which can be used for blowing polymer mixtures into cellular polymers. Generally speaking, such blowing agents ar~e 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 to 38.

In a preferred embodiment of a polyol blend in accordance with the present invention which finds particular utility in the preparation of polyisocyanurate foams, there is additionally present, in the blend of blowing agent and components (I), (II), or (III) and (IV), an isocyanate trimerization catalyst. The isocyanate trimerization catalyst component will be discussed in detail below. The isocyanate trimerization catalyst is advantageously present in the proportions of from about 2 to about 20, preferably from about 2 to about 15 weight percent, with the balance of about 80 to about 98, preferably about 85 to 98 percent, comprising the ingredients set forth above.
Surprisingly, the blowing agent and the polyol blend which includes the primary hydroxyl containing polyols are completely miscible in each other with no separation occurring upon storage, which miscibility is due to the presence of the amine diol (I), amide diol (II), or amine triol (III). Aside from the advantages arising from having a stable, miscible blend of primary hydroxyl polyol and fluorocarbon or water, the beneficial effects of having the nitrogen containing diol or triol present as a minor constituent when preparing polyisocyanurate foams have been noted above.
Other optional additives can be added to the ~ji 3 5 2 5F

,. .

polyol blends without detracting from the miscibility and stability of the blends. Such additives include other optional polyol components such as secondary hydroxyl containing polyols, dispersing agents, cell stabilizers, surfactants, flame retardants, and the like which are commonly employed in the process of the invention.
In the preparation of polyisocyanurate foams in accordance with the present invention, the amine diol, amide diol or amine triol described above can be employed as the sole polyol component in admixture with a fluoro-carbon or water blowing agent and a trimerization catalyst to form a B side component for reaction with an A side comprised of an organic polyiso-cyanate. In this event the values of x and y in (I) can have the broader ranges as noted above of from about 1 to about 15.
The percent by weight proportions of the blend ingredients are the same as those set forth above for the proportions of catalyst to be blended with blowing agent and polyol component.
That is to say the B blend is comprised of from about 2 to about 20, preferably from about 2 to about 15 percent by weight of a trimer-ization catalyst and from about 80 to about 98, preferably about 85 to 98 percent by weight of ~I), (II), or (III) and blowing agent~ In the event that a fluorocarbon blowing agent is employed it is present in the proportions of about 20 to about 80, preferably from about 20 to about 50 percent by weight in respect of the (I), (II),or (III), which latter, accordingly is present in an amount from about 20 to about 80, preferably from about 50 to about 80 percent by weight.
In the event that water is employed as the blowing agent it is present in the proportions of from about 1 to about 6, preferably from about 2 to about 5 percent by weight in respect of the (I), (II), or(III), which, accordingly, is present in an amount from about 94 to about 99, preferably 95 to 9~ percent by weight.
The B side blend is advantageously employed in an amount falling within the range of from about 10 parts to about 120 parts, preferably ~rom about 10 to about 80 parts, most preferably from about 20 parts to about 60 parts by weight per equivalent of polyisocyanate;
provided the total hydroxyl equivalents present in said blend (B) are within a range of from about 0.05 to about 0.5 equivalent, preferably about 0.08 to about 0.4 equivalent, per equivalent of said polyisocyanate.
Preferably there is also present in the B side blend a minor amount of the primary hydroxyl polyol (IV) described above. This combination in the blend not only gives rise to the stabilized miscible blends discussed above, but, additionally,provides polyiso-cyanurate foams having the optimum advantageous proper-t1es discussed above, including the preparation of foam laminates which require no oven heating in order ~o achieve maximum foam strength and adhesion to the laminate facers. In this event the values of x and y S

in (I) have the narrower ranges as noted above of from about 4 to about 15.
The blend containing the amine diol (I), amide diol (II), or amine triol (III), with primary hydroxyl polyol (IV), blowing agent, and trimerization catalyst is also employed in an amount falling within the same range of parts per isocyanate equivalent set forth above for the B blend with-out (IV); and with the same proviso set forth above for the range of total hydroxyl equivalents per equivalent of isocyanate. The pro~ortions of each ingredient in the blend in percent by weight of the blend are the same proportions set forth in the description of the polyol blends. The amine diol (I), ami~e diol (II), amine triol (III), primary hydroxyl polyol (IV), and blowing agent, all have the same significance and scope set forth above.
The trimerization catalyst employed can be any catalyst known to those skilled in the art which will catalyze the trimerization of an organic isoc~anate compound to form the isocyanurate moiety. Further, a combination of urethane forming catalyst and trimeriza-tion catalyst can be employed if desired.
For typical isocyanate trimerization catalysts see ~he ~ournal of Cellular Plastics, November/December 1975, page 329; U. S. Patents 3,745,133, 3,896,052, 3,899,443, 3,903,018, 3,954,684, and 4,101,465.

Preferred as catalysts are the ones disclosed in U. S. 3,896,052, and 4,101,465. The former reference discloses the catalyst combination of (a) an alkali ~ ~4(~6~i metal salt of an N-substituted amide with (b) an alkali metal salt of an N-(2-hydroxyphenyl)methyl glycine ana optionally (c) a tertiary amine trimerization catalyst.
The latter reference discloses the combination sf the same (a) and (b) components above with a hydroxyalkyl-trialkylammonium carboxylate salt component.
The organic polyisocyanates which can be employed in the preparation of the polyisocyanurate foams in accordance with the present invention can be any of the organic polyisocyanates conventionally employed in the art for this purpose previously. Advantageously, and in order to obtain foams having exceptionally high heat resistance and structural strength, the preferred poly-isocyanates are the polymethylene polyphenyl polyiso-lS cyanates, particularly those set forth in U. S. Patent3,745,133. Also preferred are the polymethylene poly-phenyl polyisocyanates treated with a minor amount of an epoxy compound to reduce acidic impurities in accordance with U. S. 3,793,362; and the polymethylene polyphenyl polyisocyanates which contain high levels of the 2,4'-isomer as typically disclosed in U. S. Patent 3,36~,979.
A most preferred organic polyisocyanate is a mixture containing from about 30 percent to about 85 percent by weight of methylenebistphenyl isocyanate) and the remainder of said mixture comprises polymethylene polyphenyl polyisocyanates of functionality higher than 2Ø
In carrying out the preparation of polyisocyanurate 6~5 foams in accordance with the process of the invention, and, in particular, polyi60cyanurate foams for the preparation of ~oam laminates, the procedures and aquipment conventional in the art are employed (see patents cited supra); for a detailed teaching of the mode of preparation, and utility o~, polyisocyanurate foam laminates see U. S. Patent 3,896,052.

The following examples describe the manner and process of making and using the invention and set forth the best mode contemplated by the inventors of carrying out the invention but are not to be construed as limiting.
Example 1 The following five polyisocyanurate foams (Foam A
through E) were prepared in accordance with the followlng procedure.
The foams were prepared as hand-mix samples by blending together the A and the B side ingredients (in parts by weight) set forth in Table I below, in 1 qt.
cups. The polyisocyanate ingredient was the sole component of the A side while the B side ingredients which are listed in Table I were premixed and observed prior to being reacted with the polyisocyanate. The blending operation was carried out by thoroughly mixing the A and B sides in the cup with a high speed drill press motor equipped with a stirrer blade. The mixture was rapidly poured into a cardboard box and allowed to rise freely and cure at room temperature (circa 20C).
Foams B and E are in accordance with the present invention while A, C, and D are not because the amine B

diol component had values of x and y below that called for. The B sides in all of the formulations were clear with no evidence of turbidity. However, in the case of A and C, secondary hydroxyl polyols were present which are known fluorocarbon solubilizers while in C there was present additionally the phosphate plasticizer.
Foam D also contained the plasticizing ingredient.
Maximum foam properties with respect to the combination of maximum reaction exotherm with rapid firm rate and low core and surface friability were observed with Foam E.
The surface blush in respect of a rising foam sample is the point when the shiny and moist unreacted surface of the rising foam becomes dulled or blushed lS and indicates that an efficient curing or reaction has occurred at the surface. All of the foam samples showed a good surface blush.
TABLE I

.
Foams A B C D E
~0 Ingredients(pts.by wt.) A side:

Polyisocyanate I100 100 100 100 100 B side:

Diethylene glycol 5.7 5.4 6 6 8 Varonic~ L-202 5.7 - 6 6 Varonic~ K-2153 - 23.5 - - 8 Pluracol~ GP-73045.7 Pluracol~ PEP-6505 - - 6 Tris(dichloropropyl- 7.2 18 18 phosphate) TABLE I ( continued) Foams A B C D E
Propoxylated polyol6 _ _ _ 6 L-54207 1.25 1025 1.25 1.25 1.25 Fluorocarbon R-llB25 25 25 25 25 Catalyst I 3 3 3 3 3 NCO/OH index- about about about about about

4 4 4 4 Appearance of B clear clear clear clear clear component and and and and and not not not not not turbid turbid turbid turbid turbid Foam reaction exotherm (F) 339 313 294 298 345 Firm rate rapid slow medium rapid rapid Core friability high low high high low Surface friability none none none none none Surface blush yes yes yes yes yes Footnotes to Table I
lPolyisocyanate I is a polymethylene polyphenyl polyiso-cyanate containing about 45 percent by weight of methylenebis(phenyl isocyanate) and the remainder of said mixture consisting of polymethylene polyphenyl polyisocyanate having a functionality greater than 2;
the isocyanate equivalent = 133.
2Varonic~ L-202 is the soya amine adduct obtained by the reaction of a 2 molar proportion of ethylene oxide with soya amine; amine equivalent wt. about 360; hydroxyl equiv. wt. about 180; supplied by Chemical Products Division, Ashland Chemical Company, Columbus, Ohio.
3Varonic~ K-215 is the cocoamine adduct obtained by the reaction of a 15 molar proportion of ethylene oxide with cocoamine; amine equivalent wt. about 885; hydroxyl equiv.
wt. about 442; supplied by Chemical Products Division, Ashland Chemical Company, Columbus, Ohio.
4Pluracol~ GP-730 is a propoxylated glycerine product;
hydroxyl equiv. wt. = 243, and is supplied by BASF
Wyandotte Chemical Corp., Wyandotte, Mich.

S

Footnotes to Table I (cont'd.) 5Pluracol~ PEP-650 is a propoxylated pentaerythritol product; hydroxyl equiv. wt. = 148 and is supplied by BASF Wyandotte Chemical Corp., Wyandotte, Mich.
6Propoxylated polyol is the product obtained from propoxylating a mixture of sorbitol and toluene diamine to a hydroxyl number of 360, viscosity of 2500 centi-stokes at ~5C, and specific gravity of 1.072.
7L-5420: A rigid foam silicone surfactant having a hydroxyl number of about 119 supplied by Union Carbide Corp., Tarrytown, N.Y. 10591; see Union Carbide Bulletin F-43565, December 1971.
Fluorocarbon R-llB is monofluorotrichloromethane blowing agent stabilized with allo-ocimene and supplied by DuPont Chemical Corp., Wilmington, Del.
9Catalyst I comprises a combination in the following proportions of A.) 1 part of a solution comprised of (a) 45 percent by weight of potassium N-phenyl-2-ethyl-hexamide, (b) 27 percent ethylene glycol, and (c) 28 percent dimethylformamide; B.) 3 parts of a solution comprised of 50 percent by weight of sodium N-(2-hydroxy-5-nonylphenyl)methyl-N-methyl glycinate in diethylene glycol; and C.) 1 part of a solution comprised of 50 percent by weight of 2-hydroxypropyltrimethyl-ammonium formate and 50 percent dipropylene glycol; and D.) 1 part of a polyethyleneglycol (MW = 200).
Example 2 The following foams were prepared in accordance with the procedure and apparatus described in Example 1 except as noted below. The foams of this example set forth a comparison of the prior art method (Foams F
and H) versus the method in accordance with the present invention (Foams G and I).
The ingredients of the A and B sides are set forth in Table II below. The F and G pair contained a different polyisocyanate from the H and I pair. ~he A side of Foams F and H contained the fluorocarbon blowing agent in accordance with the prior art. When the same amount of the fluorocarbon was mixed into the B side to test miscibility, in both cases, the ~ 3525F

fluorocarbon separated from the other ingredients, namely, diethylene glycol, surfactant, and catalyst.
In the case of Foams G and I which contained the ethoxylated cocoamine in the B side, the fluorocarbon and other ingredients were completely miscible with the diethylene glycol component.
A comparison of the foam rise times between F and G, and H and I, clearly show a much faster rate for the foams in accordance with the invention (G and I) over the respective pair in accordance with the prior art (F and H). The dramatic rate increase clearly indicates the increased compatibility between the A and B sides which leads to better reaction between the two hence the faster rise times over the formulations of the prior art. While the ethoxylated amine used in Foams G and I is a tertiary amine, these types of high molecular weight tertiary amines are not strong bases and were used in G and I in very small amounts based on amine equivalents, iOe. 0.009 equivalents in each case.
l`hi~ low level of weak amine would not be enough to explain the dramatic rate increases of G and I over F
and H respectively on the basis of amine catalysis alone.
TAB~E II

Foams F G H
Ingredients (pts. by wt.) A side:

Polyisocyanate I 100 100 - -Polyisocyanate II - - 105 105 Fluorocarbon R-llB21.5 - 22.5 .~ , , TA~LE II (continued) Foams F G ~ I

B side:
Diethylene glycol8.3 8.0 8.3 8.0 Varonic~ K-215 - 8.0 - 8.0 L-5420 1.25 1.25 1.251.25 Catalyst I 3.0 3.0 3.0 3.0 Fluorocarbon R-llB - 23 - 24 NCO/OH index 4.6 4.2 4.6 4.2 Foam rise time(seconds) Cream 75 19 59 21 Gel 104 42 96 41 Tack free 116 49 106 47 Exotherm (F) 341 336 318 316 Core density, pcf1.76 1.74 1.791.75 Dry heat age 300F/24 hrs.
% ~ volume +4.6 +4.1 +2.9~2.4 Core friability, % 31 30 22 19 Surface friabilitynone none nonenone Surface blush yes yes yes yes Footnotes to Table II
See Footnote 1, Table 1.
Polyisocyanate II is a polymethylene polyphenylpolyiso cyanate containing about 35 percent by weight of methylene-bis(phenyl isocyanate) and the remainder of said mixture consisting of polymethylene polyphenyl polyisocyanate having a functionality greater than 2; the isocyanate equivalent = 140.
3The friability is the percent sample weight loss over a 10 minute period and determined in accordance with ASTM Test method C-421.

~4~

Example 3 The following two polyisocyanurate foams J and K in accordance with the present invention were prepared in accordance with the procedure and apparatus described in Example 1 and using the ingredients in the proportions by weight set forth in Table III below. The B components were clear in both cases.
Both foams were very fine celled in structure with no surface friability and a good surface blush was observed. The foam exotherms were good and the rapid rise profiles indicated the fast reactivity for both foams.
It is noteworthy that the catalyst mixture employed in both J and K contained a very minor amount of the lS Varonic~ K-215 amine diol which acted as a compatibiliz-ing agent for the various other catalyst components. In the absence of the Varonic~ K-215 the other catalyst components are not completely miscible.
TABLE III

-Foam J K

Ingredients (pts. by wt.) A side:

Polyisocyanate IIIl 135 135 B side:

Varonic~ K-2052 37 Varonic~ K-215 - 75 DC-1933 1.5 1.5 Fluorocarbon R-llB22 27 Catalyst II4 3 3 NCO/OH index 4.5 4.5 - 3525E' i ~

TABLE III (continued) Foam J K
B mix appearance clear clear Foam rise tirne(seconds) Cream 5 6 Gel 20 20 Tack free 30 40 Rise - -Exotherm (F) 328 305 Surface friabilitynone none Surface blush yes yes Core friability low low Appearance very fine very fine cell cell Footnotes to Table III
lPolyisocyanate III is a polymethylene polyphenyl poly-isocyanate containing about 45 percent by weight of methylenebis(phenyl isocyanate) and the remainder of said mixture consisting of polymethylene polyphenyl polyisocyanates having a functionality greater than 2, the isocyanate equivalent = 135.
2Varonic~ L-205 is the cocoamine adduct obtained by the reaction of a 5 molar proportion of ethylene oxide with cocoamine; amine equivalent wt. = about 445; hydroxyl equiv. wt. about 222; supplied by Chemical Products L)ivision, Ashland Chemical Company, Columbus, Ohio.
3DC-193 is a silicone surfactant supplied by Dow Corning, Midland, Mich.; see Bulletin 05-146, February 1966.
Catalyst II comprises a combination in the following proportions of: A.) 1 part of a solution comprised of 50 percent by weight of sodium N-(2-hydroxy-5-nonyl phenyl)methyl-N-methyl glycinate in diethylene ylycol;
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 Footnote 3 of Table I above. It should be noted that this catalyst blend is completely clear and miscible. Preparation of the same catalyst blend but without the K-215 component yields a turbid and cloudy mixture.

Example 4 The following two water blown polyisocyanurate foams L and M were prepared in accordance with the present invention using the procedure and apparatus described in Example 1 and using the ingredients in the proportions by weight set forth in Table IV below.
The B side in both cases formed a clear miscible blend.
The foam rise characteristics were found to be very rapid with a quick tack free time in spite of the foams being water blown. High foam exotherms were also observed attesting to the excellent conversions. The resulting foam physical properties were good.
TABLE IV

Foams L M
-Ingredients (pts.by wt.) A side:

Polyisocyanate III 135 135 B side:

Polyol blend I 23 30 Catalyst II 3 3 NCO/OH index (includiny ~l2O) 3 2.5 B mix appearance clear clear Foam rise time(seconds) Cream 15 13 Gel 31 26 Rise 48 48 Tack free 35 30 ~ 6~ 3525F

TABLE IV (continued) Foams L M

Exotherm (F) 376 3 83 Density (pcf) 2.65 2.81 K-Factor in BTU( ft.2)(hr.)F/in.:
in 1I dir. 0.190 0.201 in 1 dir. 0.189 '0.193 Compressive str.(psi) ¦I to rise 39. 5 42 1 to rise 30.0 20 % ~ Volume at 70C, 100 relative humidity after 24 hrs. -7.7 ~4-7 300F Dry Age~Volume(%) after 24 hrs. -2.9 +3.0 Footnotes _ Table I

~olyol blend I comprises a blend in the following pro-portions of A.) 40.8 pts. of a polyoxydiethylene adipate glutarate polyester diol of M.W. = 500; B.) 28.6 pts. of diethylene glycol; and C.) 30. 6 pts. of Varonic~ K-215.
2K-Factor is a measure of thermal conductivity of materials by determining heat flow in accordance with ASTM Test method C-518.
Example 5 This example sets forth a hand-mix polyiso-cyanurate foam N prepared in accordance with the present invention using the procedure and apparatus described ;n Example 1 and the ingredients set forth in Table V below.
The B side of sample N contained a mixture of primary hydroxyl triol and diethylene glycol with a 41~ by weight proportion of fluorocarbon yet the blend stayed clear with no turbidity.

-The foam had fast rise times with a good exotherm and good friability characteristics.
TABLE V
Foam N

Ingredients (pts. by wt.) A side:
Polyisocyanate III 135 B side:
TPEG-990 8.5 Diethylene glycol 6.5 Varonic~ K-215 10 DC-193 1.25 Catalyst II 3.0 Fluorocarbon R-ilB 20 B mix appearance clear no turbidity ~ R-llB in B mix 41 Foam rise time (seconds) Cream 13 Gel 30 Tack free 35 Exotherm (F) 349 Surface friability none Surface blush yes Core friability low Footnote to Table V
TPEG-990 is a primary hydroxyl containing trifunctional polyethylene glycol having an OH E.W. a 333; and is supplied by Union Carbide Corp., New York, N.Y.
Example 6 The following high temperature and flame resistant ~34-polyisocyanurate foam laminates were prepared in accordance with the present invention using the foam O
which was prepared from the ingredients set forth in Table VI below.
A Viking laminating machine was used with "A" and "B" component temperatures of 73F and 70F respectively.
Throughput was 15 lbs.~min. through a low pressure impingement mixing head. A pour lay down technique was used instead of a nip roll. The conveyor speed was 10 ft./min. and the curing oven temperature was at ambient (70 to 90~F).
Two inch thick laminate was prepared with 0.0015"
aluminum foil facers and also prepared with asphalt facers. The foam properties reported in Table VI below are for the foam core material after the facers had been removed. Therefore, the facer material itself has no affect on this data. The adhesion between facer material and foam was excellent.
The component B, although containiny the primary hydroxyl polyester and diethylene glycol and a 43% by weight content of freon (R-llB~ was clear with no turbidity.
Tlle laminates were prepared without the necessity of oven curing at a high temperature because of the rapid reactivity of the formulation. The rapid reactivity also was reflected in the rapid rise profile and the fact that foam friability was found to be very low in spite of the lack of a high temperature cure step. Good facer adhesion, as noted above, was also observed.

6~i;

The overall foam physical properties were found to be good including the very low friability, good fire resistance, K factor, and h~nid age data.
TABLE VI

Foam O
-Ingredients (pts. by wt.) A side:

Polyisocyanate I 133 B side:
Polyester dioll 9 Diethylene glycol 6.3 Varonic~ K-215 6.7 DC-193 1.25 Catalyst II 3.0 Fluorocarbon R-llB 20.0 B mix appearance clear no turbldlty % R-llB in B mix 4 NCO/OH index 4.9 Foam rise time (seconds) Cream 19 Gel 40 Tack free 47 Surface friability none Surface blush yes Core friability low (6~) Overall density (pcf) 2.0 Core density 1.8 Compressive str.(psi) ll to rise 31 6~

TABLE VI (continued3 Foam -Compressive str. (psi) 1 to rise 21 Cloced cells 94%

K Factor in BTU (ft.2)(hr.)F/in. 0.14 Humid age (15BF, 95~ R.H.) ~ Vol., after 1 day +6%
7 days +6.5%
28 days +7.0%

ASTM E-84 Test on 2" thick samples:
Flame spread rating 38 Smoke 187 Footnotes to Table VI

lPolyester diol is the same diol described in Foot-note 1 of Table IV under A.).
2Closed cells are determined by the air pycnometer test in accordance with ASTM Test method D-2856.

~xample 7 The following polyisocyanurate foam P was prepared in accordance with the present invention in accordance with the procedure and apparatus described in Example 1 using the ingredients in the proportions by weight set forth in Table VII below.
The B side was clear without evidence of turbidity in spite of the combination of the fluorocarbon with the primary hydroxyls of the amide diol.
The foam produced was characterized by a very fine cell structure with no surface friability and with a good surface blush.

6~

The foam exotherm was good and the rapid rise profile indicated the fast reactivity of the foam.
TABLE VII
Foam p Ingredients (pts. by wt.) A side:
Polyisocyanate III 135 B side:
Varamide~ 6-CM 49 DC-193 1.5 Fluorocarbon R-llB 23 Catalyst II 3 NCO/OH index 4.5 B side appearance clear non-turbid Foam rise time (secs.) Cream 8 Gel 42 Tack free 52 Rise Exotherm (F) 328 Surface friability none Surface blush yas Core friabilitymoderately fxiable Appearance ~ery fine cell Footnotes to Table VII
Polylsocyanate III is the same polymethylene polyphenyl poly-isocyanate defined in Example 3j Footnote 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 eq. wt.= 290~ OH eq.
wt.=193; supplied by Chemical Products Div.,Ashland Chemical Co.,Columbus,Ohio.; and otherwise identified by the chemical name of N,N-bis(8-hydroxy-3,6-dioxaoctyl)cocoamide mixture.

3Catalyst II is the same catalyst combination defined in Example 3, Table III, Footnote 4.

~L4(~
Example 8 The following polyisocyanurate Foams Q, R, and S
were prepared in accordance with the procedure and apparatus described in Example 1 and using the ingredients set forth below in Table VIII. Foams Q
and R are in accordance with the present invention while Foam S is not.
The B side components in the case of Foams Q and R
were clear with no evidence of turbidity in spite of the mixture of the fluorocarbon with the primary hydroxyl containing components in both blends.
The A side of Foam S contained the fluorocarbon blowing agent in accordance with the prior art. When the same amount of the fluorocarbon was mixed into the B side to test miscibility the fluorocarbon separated from the other ingredients, namely, diethylene glycol, surfactant, and catalyst.
A comparison of the foam rise times between Foams Q and R on the one hand with Foam S on the other, clearly shows a much faster rate for the foams in accordance with the invention(Q and R) over the prior art (S) . The dramatic rate increase clearly indicates the increased compatibility between the A and B sides which leads to better reaction between the two hence the faster rise times over the formulations of the prior art.

TABLE VIII
.
Foam Q R S

.
Ingredients (pts. by wt.) A side:

Polyisocyanate III - 135 , TABLE VIII (continued) Foam Q R S
Polylsocyanate Iloo - loo Fluorocarbon R-llB - - 21.5 B side:
Polyester diol2 9 Diethylene ~lycol 8 6.3 8.3 Varamide~ 6-CM 8 6.7 ~ -L-5420 1.25 - 1.25 Fluorocarbon R-llB 25 22 Catalyst II 4.5 5 Catalyst I3 - _ 3.0 NCO/OH indexabout 4 about 4 about 4.6 B side appearanceclear clear non-turbid non-turbid Foam rise ti~e(secs.~
Cream 16 lÇ 75 Gel 40 35 104 Tack free 45 4Q 116 Rise 54 48 Exotherm (F? 344 351 341 Firm rate rapid rapid Surface friabllity none no~e 25 Surface blus~ yes yes Core densi-ty(pcf)1.55 2.06 1.76 Core friability(~) 38.5 32.0 31 300F Dry Age, ~ Volume ~/24 hrs. +7.4 +5.0 +4.6 Footnotes to Table VIII
_ lPolyisocyanate T iS the polymethylene polyphenyl poly-isocyanate defined in Example 1, Table I, Footnote 1.
Polyester diol: a polyoxydiethylene adipate glutarate polyester diol of MW = 500, and OH # = 211.5.
S Catalyst I is the same catalyst combination defined in Example 1, Table 1, Footnote 9.
Example 9 The following polyisocyanurate Foam T was prepared in accordance with the present invention in accordance with the procedure and apparatus described in Example 1 using the ingredients in the proportions by weight set forth in Table IX below.
The B side was clear without evidence of turbidity in spite of the combination of the fluorocarbon with the primary hydroxyls of the amine triol constituent.
The foam produced was characterized by a very fine cell structure with no sur~ace friability and with a good surface blush.
The foam exotherm was good and the rapid rise profile indicated the fast reactivity of the foam.
TABLE IX

Foam T

Ingredients (pts. by wt.) A side:
Polyisocyanate I~I; 135 B side DC-193 1.5 Fluorocarbon R-llB 23 CatalySt II 2.5 ~ 3525E' ~l~LOff95i TABLE IX (continued) Foam T

NCO/OH index 4.5 B side appearance clear non-turbid Foam rise time (secs.) Cream 4 Gel 17 Tack free 50 Rise Exotherm (F) 323 Surface friabilitynone Surface blush slight Core friability low Appearance very fine cell Footnotes to Table IX
~ D-124 is the ethoxylated mixture obtained by reacting ethylene oxide with a cocodiamine in the molar proportions of about 14 to 1 respectively, and wherein the cocodiamine is obtained by reacting cocoamine with an equivalent of acrylonitrile and reducing the cyanoethylated cocoamine mixture to the cocodiamine; amine eq. wt. = 290; OH eq. wt. =
193; supplied by Chemical Products Div., Ashland Chemical Co., Columbus, Ohio.

; , . ;

Example _ The following polyisocyanurate Foams U, V, and W
were prepared in accordance with the procedure and apparatus described in Example 1 and using the ingredients set forth below in Table X. Foams U and V are in accordance with the present invention while Foam W is not.
The B side components in the case of Foam U and V
were clear witll no evidence of turbidity in spite of the mixture of the fluorocarbon with the primary hydroxyl containing components in both blends.
The A side of Foam W contained the fluorocarbon blowing agent in accordance with the prior art. When the same amount of the fluorocarbon was mixed into the B side to test miscibility the fluorocarbon separated from the other ingredients, namely, diethylene glycol, surfactant, and catalyst.
A comparison of the foam rise times between Foams U and V on the one hand with Foa~ W on the other, ~0 clearly shows a much faster rate for the foams in accordance with the invention(U and V) over the prior art(W) . The dramatic rate increase clearly indicates the increased compatibility between the A and B sides which leads to better reaction between the two hence 25 the faster rise times over the formulations of the prior artO
``` ` ` T~BI,E X
` Foam U V W

Ingredients (pts. by wt.) A side:
Polyisocyanate III 135 TABLE X (continued) Foam U V W
Polyisocyanate I 100 - 100 Fluorocarbon R-llB - - 21.5 B side:
Polyester dioll - 9 Diethylene glycol 8 6.3 8.3 KD-214 8 6.7 L-5420 1.25 - 1.25 Fluorocarbon R-llB 25 22 Catalyst II 2.5 2.5 Catalyst I - - 3.0 NCO/OH index about 4 about 4 about 4.6 15 B side appearance clear clear non-turbid non-turbid Foam rise time (secs.) Cream 16 15 75 Gel 39 42 104 Tack free 46 50 116 Rise 56 60 Exotherm (F) 331 337 341 Firm rate rapid rapid Surface friabilitynone none Surface blush yes yes Core density (pcf)1.67 2.27 1.76 Core friability(%)18.8 33.1 31 300F Dry Age, ~Volume %/24 hrs.+10.8 +5.3 +4.6 Footnote to Table X

lPolyester diol: a polyoxydiethylene adipate glutarate polyester diol of MW = 500, and OE~ # = 211.5.

, :.
LO~

Example _ A series of blends of fluorocarbon R-llB (monfluoro-trichloromethane) with two typical primary hydroxyl polyols of the present invention were prepared. The proportions by weight employed, including the amount of amine diol(I) when present, varied according to the values set forth in Table ~I below. The blends were observed for their miscibility and clearness or their turbidity,and separation of the fluorocarbon from solution.
Blends A through D contained diethylene glycol with fluorocarbon and in the absence of amine diol, i.e., 100% diethylene glycol, the maximum fluorocarbon solubility was 15~ by weight. The addition of 10 per-cent by wt. amine diol was not sufficient to impartfluorocarbon solubility at the 25% by wt. level whereas a 20 percent amine diol content (blend D) did result in a clear miscible solution at 25 percent fluorocarbon.
Blends E through J contained a polyester diol defined above wherein the pure polyester diol was capable of dissolving 20 percent by weight fluorocarbon but not 25 percent. The break for 25 percent fluoro carbon solubility started at about 10 parts by weight of the amine diol (blend G) while at the 20 percent level of amlne diol the fluorocarbon could xeach up to 31 percent by wt.
Blends K through M were observed to have maximum fluorocarbon levels of greater than 90 percent and up to 67.5 percent for diethylene glycol and the polyester diol respectively when a maximum of 85 percent by -~5-63~1$

weight of amine diol was employed.
Blends N throu~h Q were observed to have maximum fluorocarbon solubilities of 60 percent and 50 percent respectively for diethylene glycol and polyester diol when the primary alcohol-amine diol blends were 50/50 percent by weight.

~0 H I ~ ~ ~ ~ ~ ~ miscible :~: I ~ ~0 ~o ~) ~o u) misecarible o o ~ o o ~ clear miscible r~
o ~ o o ~ turbid ~ ~ ~ ~ ~ separates o ~ o o o clear ~ I o I ~ ~ ~ miscible x a ~ ~ ~ ~ ~ ~ mlisecarible o o ~ o o ~ turbid E~ O a~ I ~1 o~ ~ ~
~ separates o ~ o o o turbid m ~ I I ~ ~ ~ separates o ~ o o ~ clear miscible ~ ~ ~d O ~ ' o :~ ~I P:; 0 0 h Q. ~1 0 ~ O
-- ~ ' O h Ei ~I h ~Q o Q Q~ 0 ~ (d h aJ
~ ~ ~ 0 O ~1 3 ~ 3 aJ ~ ~ ~1 o ~ ~ ~ ~
R ~ .4 ~:
m ~ a ~ 0 0~O 0~O

~7-~SZ5 -O O O O O ~ turbid separates o o o o o o clear ~ I u~ In o ~ miscible o o ~ o o ~ turbid o ~ I ~ ~ ~ ~ ~ separates 4 _ ~9 ~
~ z ~ ~ clear ~ H
~I misclble H
~ a O ~1 ~ ~ o turbid separates H ~`I ~1 X O ~
clear ~ $
~ ~ ~ ~ ~ ~0 ~ ~ ~ miscible E~ ~ ~ ~o ~
o ~o ~o clear ~
a~ mlsclble ~1 .,~
o o o o o ~ 1 d 1~ I ~ c ou y ,~

al H
~ ,~
O
3 ~ H ¦ 3 3 m ~ 'o~
rl (d a ~ 1 ~ r~
U~ ~ ~1 I h O a) .4 U~ E3 a) 1 Ql ~1 0 ~3 ~ O ~ E~ ~
~ O S lE~ i O O rS
u~ 5 ~ tL~
~ a) u~
a~ E~
o 3 3 3 a) U s~ o u~ u~
~ ~ ~ ~ ~ o ,~ ~ ~ a m ~ ~1 o I ,~ a~ o ~ a ~ ~0~ ~ O E~
H m ~48-~ZSE

~ . ~, Example ~
A series of blends of fluorocarbon R-lls (monfluoro-trichloromethane) with three typical primary hydroxyl polyols of the present invention were prepared. The proportions by weight employed, including the amount of cocoamide diol (II) when present, varied according to the values set forth in Table XII below. The blends were observed for their miscibility and clearness or their turbidity and separation of the fluorocarbon from solution.
Blends A through D contained diethylene glycol and, in the absence of any amide diol, the maximum fluoro-carbon solubility did not reach 20 percent by weight.
The addition of 10 percent amide diol (blend B) was not sufficient to impart fluorocarbon solubility at the 20 percent level. It was not until at least 15 percent of amide diol (blend C) did the blend remain clear at 20 percent fluorocarbon, and, obviously, was clear at the 80/20 blend level (blend D).
Blends E througll G contained ethylene glycol and at least 20 percent of amide diol was required to maintain a 20 percent fluorocarbon solubility.
Blends H through L were prepared from a polyester diol and it was observed that while 20 percent fluoro-carbon solubility was possible with the pure diol that 25 percent was not. ~hen the amide diol level was 20 percent (blends J through L) the highest fluorocarbon level attainable was about 31 percent ~lends M through O were observed to have maximum fluorocarbon levels of greater than 90 percent and up 06~

to 60 percent by weight for diethy~ene glycol and the polyestex diol respectively when a maximum of 85 percent by weight of amide diol was employed.
Blends P through S were observed to have maximum fluorocarbon solubilities of 55 percent and 45 percent respectively for diethylene glycol and polyester diol when the primary alcohol-amide diol blends were 50/50 percent by weight.

~ 36~ii o o o o o U~ 1 , c ear oo ~ o o `~ ~urbid HI I ~ I ~ ~ ~ separates o~ o o o clear $ I I oI ~ o ~
~1 ~

~ o o o clear I o~ I ~ ~ a:) ~ ~

o turbid separates o ~ o o o turbid separates H

H o O ~ clear X ~ oo I I ~

E~ Il~ n o 1 _ ~
c~e~_ o o ~ o o o turbid m ~ separates o ~ o o o turbid separates ~o 3 8 o m ~ ~o o ~ ~ ~c~
u~ V ~ ~ Is~ o a~
O ,1 ~ 1~a~ h Q~ _I V 0 ~3 ~ O ~::
u~ a~ ~/ ~,Q h 1~3 S~
Q) ~ a) ~ . . .
~1 ~ ~ O
.~ o 3 3 Q~ ~ O
-l m ~ o I ~ a~
~ a ~ O d~ 0~O
H

~3: SZS~

I I u~ u, o u~ ul ui turbid ~ separates o o ~ o o u, clear ~; I I u, u, u, u, ~

o o o o o o turbid Oi L~ I I U~ U U) U) ~ separateS
~='.

~ O O u~ u~ ui clear ci r-l . H

_ o u ~ ~ u, u, u, turbid separates ui u o u, u, o clear o~ ~ miscible " ~
H ~ Ci X ~ ~ I I ~ O ~ ~ ~ clear ai O
mlscible O O
o o o o o o ~ turbid separates ~
.~ .~
o ~ o o ~ just R
~4 I Io~ ~ ~ ~ ~ ~ 1 c ear ~ ~

3 ~ H¦ ~ o ~i X ~ c ui ~, O ~ ai ~ ul u., ai ~ h Q ~ ~ ai ~ ¦ Q~ a s ~ ai ~, . , , ~ ul a ~i r~ i V ~ ~ U~
~i ~i ~ r~ N 3 3 3 ~ 0 U,i ~ a) l~ o ,-i h a~ 1 ~ R Q ~ ~ ~ a m ~ O I ,~ o o ~ I

~ a ~ a ~9 E4 o\ o\o~ r-i O
H al ~4 r l ~`I

~SZS~ _5~

Example 13 A series of blends of fluorocarbon R-llB (mon-fluorotrichloromethane) with three typical primary hydroxyl polyols of the present invention were prepared.
S The proportions by weight employed, including the amount of amine triol (III) when present, varied according to the values set forth in Table ~III below. The blends were observed for their miscibility and clearness or their turbidity and separation of the fluorocarbon from solution.
Blends A through D contained diethylene glycol and in the absence of any amine triol the fluorocarbon solubility could not reach 20 percent by weight. The addition of 10 percent amine triol (blend B) was not sufficient to impart fluorocarbon solubility at the 20 percent level. It was not until at least 15 percent of amine triol did the blend remain clear at 20 percent fluorocarbon.
Blends E through G contained ethylene glycol and at least 20 percent amine triol was required to maintain 20 percent fluorocarbon solubility.
Blends H through M were prepared ~rom a polyester diol and it was observed that while 20 percent fluorocarbon solubility was possible, 25 percent fluoro~arbon solubility was not with the pure diol and thàt at leas~
15 percent by weight~amine triol was required to maintain 25 percent fluorocarbon solubility (blend K).
At a 20 percent by weight content of amine triol t~e maximum fluorocarbon solubility was about 28.6 percent by weight.

~L3L4~6~;

Blends N through P were observed to have maximum flurocarbon levels of greater than 90 percent and up to 50 percent by weight for diethylene glycol and the polyester diol respectively when a maximum of 85 percent-by weight of amine triol was employed.
Blends Q through T were observed to have maximum fluorocarbon solubilities of 50 percent and 40 percent respectively for diethylene glycol and polyester diol when the primary alcohol-amine triol blends were 50/50 percent by weight.

6~

O O ~ O O ~ turbid ~ I I ~ ~ ~ ~ ~ ~ separates H I ~ o I ~ o ~ turbid ~ ~ ~ separates r~ .
o ~ o o o clear I I O I ~ ~ N miscible o o ~ o o o clear miscible I ~ ~ ~ ~ o turbid separates ~ o o o turbid w I ~ I I ~ ~ separates H
HH ~ clear x a ~ ~ ~ ~ ~ ~ ~ ~ miscible o clear miscible O O ~ O O O turbid m ~ I ~ ~ ~ ~ ~ ~ separates O ~ o o o turbid separates o ~1 o :~ O O R
~ ~ m R O r-l ~ O a) ~ U ,1 ~1 1 ~ o C) u~ ` ~ O ~I P~ h O ~ O '~
~
~o 0 ~) R h ~: ~ a) a) ,~ . . .
~ ~ ~ ~ ~ U J~
ra .~ ~ o 3 3 3 ~a ~ ra a~ ~ ~ ~ ~ ~ o R
m ~ o ~
H ~ m ~5 ~S Z S ~

O O ~ O O ~ turbid separates o o o clear miscible ~ .
o o ~ o o ~ turbid separates o x o o o o o clear H
a ~ ~ ~ ~ ~ ~ ~ ~ miscible ~ ~ . turbid ~ ~ ~ separates ~ Q

~ ~ o ~ ~ o clear _ o ~ ~ ~ ~ ~ ~ ~ ~ miscible ~ o' o ~ ~ o clear ~
o z ~ ~ miscible _ ~ a~
H O O ~ O O ~ turbid H ~ I I ~ ~ ~ ~ ~ ~ separates ~D
o o o ~ ~o ~ clear .

clear miscible ~ od ~ O HX¦ ~ ~
~ O ~ , ~~ o a~
Q",~ ~ 8 ~ ~ ~~ ~ $1 ~ ~
."
''~ r g 3 ~ 3 d ~ td Q .4 .~ ~ ~: K
S C~ K

~SZ5 .

Claims (2)

A polyol blend comprising (i) from about 20 percent by weight to about 85 percent by weight based on the total weight of said blend, of a member or mixture of members selected from compounds of the formulae:

; ; and I II

III
wherein R is an aliphatic radical having from 8 to 18 carbon atoms, inclusive, R2 is an aliphatic radical having from 7 to 17 carbon atoms, inclusive, each R1 is independently selected from the group consisting of hydrogen and methyl, x and y each independently have an average value from about 4 to about 15, inclusive, x' and y' each independently have an average value from about 1 to about 3, inclusive, x", y", and z each independently have an average value from about 1 to about 5, inclusive, and n is 2 or 3; and (ii) from about 15 percent to about 80 percent by weight of a primary hydroxyl polyol characterized by a molecular weight of from about 60 to about 1000.

A miscible polyol blend comprising at least about 20 percent by weight of a fluorocarbon blowing agent and the balance being a polyol blend set forth in claim l.

A polyol blend comprising from about 1 percent to about 6 percent by weight of water and from about 94 percent to about 99 percent by weight of the polyol blend set forth in
1. claim 1.
   
   A polyol blend according to claim 1 wherein R1 represents hydrogen in all cases and (ii) is a primary hydroxyl diol.
   
   A polyol blend according to claim 4 wherein (i) is selected from the formula I and is an ethoxylated cocoamine diol mixture obtained from the reaction of about 15 moles of ethylene oxide with cocoamine.
   
   A polyol blend according to claim 4 wherein (i) is selected from the formula II and is an N,N-bis(8-hydroxy-3,6-dioxaoctyl)cocoamide mixture.
   
   A polyol blend according to claim 4 wherein (i) is selected from the formula III comprising a mixture of amine triols derived from cocoamine and each member of the mixture has x", y", and z average values of 4.6, and n is 3.
   
   A polyol blend according to claim 5 wherein the primary hydroxyl diol (ii) is selected from (a) diethylene glycol, (b) a polyoxydiethylene adipate glutarate polyester diol having a molecular weight from about 400 to about 600, and (c) mixtures of from about 30 percent to about 50 percent by weight of said (a) and from about 50 percent to about 70 percent of said (b).
   
   A polyol blend according to claim 6 wherein the primary hydroxy diol (ii) is selected from (a) diethylene glycol, (b) a polyoxydiethylene adipate glutarate polyester diol having a molecular weight from about 400 to about 600, and (c) mixtures of from about 30 percent to about 50 percent by weight of said (a) and from about 50 percent to about 70 percent of said (b).
   
   A polyol blend according to claim 7 wherein the primary hydroxyl diol (ii) is selected from (a) diethylene glycol, (b) a polyoxydiethylene adipate glutarate polyester diol having a molecular weight from about 400 to about 600, and (c) mixtures of from about 30 percent to about 50 percent by weight of said (a) and from about 50 percent to about 70 percent of said (b).
   
   A miscible polyol blend comprising at least about 20 percent by weight of a fluorocarbon blowing agent and the balance being a polyol blend set forth in any one of claims 8, 9, or 10.
   
   A polyol blend comprising from about 2 to about 20 percent by weight of an isocyanate trimerization catalyst and from about 80 to about 98 percent by weight of the polyol blend according to claim 2 or 3.
   
   In a process for the preparation of a cellular polymer in which the major recurring polymer unit is an isocyanurate moiety said process comprising the trimer-ization of an organic polyisocyanate in the presence of a minor amount of a polyol, a blowing agent, and a trimerization catalyst, the improvement which comprises preparing said cellular polymer by bringing together:
   A. an organic polyisocyanate; and B. from about 10 to about 120 parts by weight per equivalent of polyisocyanate of a blend comprising:
   (a) about 2 to about 20 percent by weight of a polyisocyanate trimerization catalyst, and (b) about 80 to about 98 percent by weight of a mixture comprising:
   1. about 20 to about 80 percent by weight of a fluorocarbon blowing agent, and 2. about 20 to about 80 percent by weight of a member or mixture of members selected from compounds of the formulae:
   
   ; ; and I II
   
   III
   wherein R is an aliphatic radical having from 8 to 18 carbon atoms, inclusive, R2 is an aliphatic radical having from 7 to 17 carbon atoms, inclusive, each R1 is independently selected from the group consisting of hydrogen and methyl, x and y each independently have an average value from about 1 to about 15 inclusive, x' and y' each independently have an average value from about 1 to about 3, inclusive, x", y", and z each independently have an average value from about 1 to about 5, inclusive, and n is 2 or 3; and provided the total hydroxyl equivalents present in said blend (B) are within a range of from about 0.05 to about 0.5 equivalent per equivalent of isocyanate.
   
   In a process for the preparation of a cellular polymer in which the major recurring polymer unit is an isocyanurate moiety said process comprising the trimerization of an organic polyisocyanate in the presence of a minor amount of a polyol, a blowing agent, and a trimerization catalyst, the improvement which comprises preparing said 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:
   (a) about 2 to about 20 percent by weight of a polyisocyanate trimerization catalyst, and (b) about 80 to about 98 percent by weight of a mixture comprising:
   1. at least about 20 percent by weight of a fluorocarbon blowing agent, and 2. the balance being a polyol mixture according to claim 4; and provided the total hydroxyl equivalents present in said blend (B) are within the range of from about 0.05 to about 0.5 equivalent per equivalent of said polyisocyanate.
   
   A process according to claim 14 wherein said poly-isocyanate is a polymethylene polyphenyl polyisocyanate.
   
   A process according to claim 15 wherein B(b) comprises:
   1. at least about 20 percent by weight of a fluorocarbon blowing agent, and 2. the balance being a polyol mixture in accordance with claim 8 or 10.
   
   A process according to claim 15 wherein B(b) comprises:
   1. at least about 20 percent by weight of a fluorocarbon blowing agent, and
2. 2. the balance being a polyol mixture in according with claim 9.
   
   Page 62 of 62 Pages