GB2122210A

GB2122210A - Process for the preparation of cellular polyisocyanurates

Info

Publication number: GB2122210A
Application number: GB08300969A
Authority: GB
Inventors: Charles Edwin Koehler; Thomas Roy Mcclellan
Original assignee: Upjohn Co
Current assignee: Pharmacia and Upjohn Co
Priority date: 1979-06-11
Filing date: 1983-01-14
Publication date: 1984-01-11
Also published as: MX156431A; FR2458562A1; IT8048932A0; GB2058098A; GB2122210B; FR2458562B1; GB8300969D0; AU5917780A; CH653692A5; GB2058098B; DE3020860A1; AU534921B2; BR8003394A; CA1140695A; NL8003378A; IT1143179B

Abstract

There is disclosed a process for the preparation of polyisocyanurate foams in which particular amine diols, amide diols and/or amine triols are utilised. High levels of blowing agent, particularly fluorocarbon blowing agents, are miscible with the above nitrogen containing polyols, along with trimerisation catalysts and other adjuvants. The foams are characterised by high reaction exotherms making such foams, particularly suited to the preparation of polyisocyanurate foam, laminates.

Description

1 GB 2 122 210 A 1

SPECIFICATION

Process for the preparation of cellular polyisocyanates 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 5 polyisocyanu rates.

Cellular polyisocya n u rate polymers are well known in the art for their 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 10 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 particularly 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 15 adhesion between foam core and facer material; 3) maintaining good fibre resistance in the foam; and 4) keeping foam friability at low levels. These problems have been 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 1600 to 190F; see U.S. Patent 3,903,346.

However, the low equivalent weight polyols employed, particularly the preferred diols (see column 20 4, lines 59-61 of U.S. 3,903,346) having only primary hydroxyl groups, cannot be blended beforehand with the fluorocarbon 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 25 dissolved in a low molecular weight glycol; see column 2, lines 32-33 and the examples of 3,903,346.

Furthermore, a laminate prepared in accordance with the patent noted above must be heated in an oven to provide a product having a uniform foam core strength.

Surprisingly, it has been found that high levels of fluorocarbon blowing agent are completely 30 miscible with low molecular weight polyols containing primary hydroxyl groups when novel blends comprising certain 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 35 described above, except that water replaces the fluorocarbon 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 polyisocyanu rate foams characterised 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 40 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 polyisocyan u rate 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 comoatibility 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 high 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 50 formed laminate in an oven.

This invention comprises polyol blends comprising (i) from about 20 percent to about 85 percent by weight of said blend of a member or mixture of members selected from compounds of the formulae:

2 GB 2 122 210 A 2 R, 1 (UH2UHU-+.,, H R-N (CH2C..IIC-4,-,H 1 R, R, R, (CH 2 CHO--4-iH 0 (1;t21-tlu-i-.H (CH2CHO-,-,H 1 hi 1 11 Ill (CHR ----N 1 n and R-N 1 (CH2CHOhm fl, 1 111 (CH2CH04., H 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 R, 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 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 (IV) characterised by a molecular weight of from about 60 to about 1000.

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 isocyanate trimerization catalyst.

The invention also comprises processes for the preparation of polyisocyanu rate cellular polymers which utilise, as a blended component, a member or mixture of members selected from compounds of the formulae (1), (11), or (111) above wherein the values of x and y can have independent average values of15 from about 1 to about 15 but preferably from about 4 to about 15, with x', yl, x", y", z, n, R, Rj, and R, having the definitions set forth above, in combination with a fluorocarbon or water blowing agent and a trimerisation catalyst, and, preferably, the blended component additionally containing the polyol (IV) in which case the diol (1) is defined as above with 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 polyisocyan u rate 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 25 atoms inclusive. Representative of alkyl are octyi, decyl, dodecyi, tetradecyl, hexadecyl, octadecyl, and isomeric forms thereof. Representative of alkenyl are octenyl, deceny], dodeceny], tetradecenyl, hexadecenyl, octadecenyl, and isomeric forms thereof.

The term -aliphatic radical- as it relates to R2 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 30 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 ingredients 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 35 buildings.

The polyol blends find particular utility, as set forth herein, as minor constituents in the preparation of polyisocyanu rate foams particularly those polyisocya n u rate 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 40 construction for thermal and sound insulation.

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 (1), amide diol (11), or amine triol (111) and a primary hydroxyl polyol (IV) defined above, in any suitable mixing vessel, holding tank, storage vessel, or the like. Preferably, (1), (11), or (111) is employed within a range from about 25 percent 45 to 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 (1), (11) and (111) have the formulae set forth above wherein R, is hydrogen in all cases.

A most preferred diol is that which has the formula corresponding to (1) wherein both R, groups 50 are hydrogen, and x and y each independently have an average value from about 5 to about 10 inclusive.

3 GB 2 122 210 A 3 A most preferred amide diol has the formula corresponding to (11) wherein both R, 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 (111) wherein all the IR, groups are hydrogen, and the x", y", and z each have an average value from about 3 to about 5 inclusive, and n is 3.

The amine diols (1) 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 (1) can be prepared by reacting the appropriate dialkanolamine with 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 10 groups are not already present in the dialkanolamine prior to 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 M.

Preferably, the amine diols (1) are prepared by reacting the appropriate primary fatty amine R- 15 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 octenylamine, decenylamine, dodecenylamine, tetradecenylamine, hexadecenylamine, octadecenylamine, 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% decylamine, 53% dodecylamine, 24% tetradecylamine, 11 % hexadecylamine, 5% octaclecylamine, and 5% octadecenylamine; soya amine in the following approximate proportions: 11. 5% hexaclecylamine, 4% octadecylamine, 24.5% oleylamine, 53% linoleylamine, and 7% linolenylamine; and tallow amine in the following approximate proportions: 4% tetradecylamine, 29% hexaclecylamine, 20% octaclecylamine, 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 (11) 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 R, 1 (cp12(;M"'H R2COR3+1-IN \ (CH2CHO4y-M 1 M1 -di+HR3 wherein R2, R,, x', and y' have the same definition as above and R, represents -OH, -OR4, and X 40 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 desired to obtain amide diols in which the values of x' and y' are greater than 1, then the intermediate dialkanolamide is simply reacted in a one molar proportion with from about 1 to about 4 moles of ethylene oxide or propylene oxide, or mixtures thereof. Sec. Bulletin 1295, entitled Varamide Alkanolamides, Ashland Chemical Company, Division of Ashland Oil, Inc., Box 2219, Columbus, Ohio 43216 for a detailed teaching of the preparation of fatty acid dial ka nola mides.

Preferably, the amide diols (11) are prepared by converting the fatty acids to the corresponding fatty acid amides (132CONI-12) and reacting the amide with from about 2 to about 6 moles, per mole of 50 amide, of ethylene oxide or propylene oxide, or mixtures thereof.

Illustrative of the starting fatty acids (from which the corresponding esters, acid hafides, and amides are also derived) are caprylic, capric, lauric, myristic, palmitic, stearic, and isomeric forms thereof. Illustrative 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 55 4 GB 2 122 210 A 4 acid mixture derived from coconut oil which consists of the following mixture in approximate percent proportions by,.Ajeight- 8.0% caprylic, 7.0% capric, 48.0% lauric, 17.5% myristic, 8.2% palmitic, 2.0% stearic, 6.0% oleic, and 2.5% linole1c; 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, 14511 stearic, 48.3% oleic, and 2.7% linoleic. Further illustrative of the starting fatty acids are the haingenated fatty acids, particularly the chlorinated and brominated fatty acids, which, illu'stratively, 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 10 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 (11) are the cocoamide diol, soyamide diol, and tallow amide derived diol mixtures wherein each R, 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 mixture above and identified by the 15 chemical name of N,N-bis(8-hydroxy-3,6-dioxaoctyl) cocoamide mixture.

The amine triols (111) 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 20 according to the following scheme.

[NH 31 RNH2 + CHR1- CHRI RNHCHRICHR10H RNHCHRICHR1NH2 0 1-101 v W ill --,,qsh-- E.O. or P. 0. or mixtures wherein R, and R, 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 (V1), typically by reaction with ammonia, followed by the reaction of a molar proportion of (V1) 25 with from about 3 to about 15 molar proportions of ethylene oxide or propylene oxide or mixtures thereof to form the amine triol (111).

Amine triols having n equal to 3 are typically prepared by the following scheme.

(H) RNH2+R,CH=CR,CN--+RNHCHRICHR,-CN)RNHCHR,CHR,CH2NH2 V11 Vill IX Ill E.O. or P.O. or mixture wherein R, and R, are defined above. The amine starting material is cyanoethylated with the appropriately substituted acrylonitrile (VII) to form (VIII) which is reduced to the diamine OX), followed by alkoxylation with from about 3 to about 15 molar proportions of ethylene oxide or propylene oxide or mixtures thereof to form (111).

The starting fatty amines are the same as those set forth above and exemplified in the preparation of the amine diols (1).

Illustrative of the acrylonitrile compounds which can be used in the preparation of the amine triols in accordance with the present invention are acrylonitrile, a- methacrylonitrile, P-methacrylonitrile, ctp dimethacrylonitrile, and the like. Preferred is acrylonitrile.

A preferred group of amine triols (111) are the amine triol mixtures derived from cocoamine, soya amine, and tallow amine mixtures wherein all the R, groups are hydrogen, the value of n equals 3, and 40 the value of x", y", and z each equal from about 3 to about 5. A most preferred species is the amine trio] mixture derived from cocoamine wherein all the R, 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 1000, preferably from about 60 to about 800, and most preferably from about 60 to 45 about 600. Included in the polyols (IV) are diols, triols, and tetrols. The preferred polyols are diols.

GB 2 122 210 A 5 Included in the class of primary hydroxyl containing polyols are the various primary hydroxyl containing diols, triols, and tetrols disclosed in the U.S. Patent 3,745, 133 which meet the molecular weight limitations set forth above and whose disclosure with respect to said polyols is incorporated by reference herein. The preferred classes are the polyester polyols prepared from clibasic 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 hydr6xyl 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, pentaerythritol; diethylene glycol, the polyoxyethylene glycols prepared by the addition of ethylene 15 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(A-hydroxyethyl)tereohth a I ate, bis(A- hydroxyethyl) phth a late, and the like; polyethylene succinate, polyethylene glutarate, polyethylene adipate, polybutylene succinate, 20 polybutylene glutarate, polybutylene adipate, copolyethylenebutylene succinate, copolyethylenebutylene glutarate, copolyethylenebutylene adipate, and the like hydroxy terminated polyesters; polyoxydiethylene succinate, polyoxydiethylene glutarate, polyoxydiethylene adipate, polyoxydiethylene adipate glutarate and the like; diethanolamine, triethanolamine, N,N'-bis(p hydroxyethyl) aniline, and the like.

The most preferred diols are diethylene glycol, and the polyoxydiethylene adipate glutarate polyester diols having a molecular weight from about 400 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 being the preferred blowing agent.

When the blowing agent is a fluorocarbon the unexpected and advantageous features of the polyol blends of (1), (11), or (111) with (IV) can be realised fully. Accordingly, there can be obtained miscible polyol blends comprising at least about 20 percent by weight of a fluorocarbon blowing agent 35 and the balance being the blends within the proportions set forth above. The particular percentage of fluorocarbon to be dissolved in the blend will govern the proportions of (IV) and of (1), (11) or (111) 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.

Miscible polyol blends comprising greater than 50 percent by weight of fluorocarbon and even up 40 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 (1), (11), or (111), 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 being most preferred.

The particular proportions of polyol (1), (11), or (111) to polyol (IV) to be employed in any particular polyol blend to obtain maximum miscibility with fluorocarbon can be determined by a process of trial 50 and error.

Generally speaking, when the amine diol (1) is employed 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 (1) and (IV).

When the amide diol (11) and (IV) are employed there are obtained miscible polyol blends comprising from at least about 20 percent by weight to at least about 60 percent by weight of a fluorocarbon blowing agent, the corresponding 80 percent to about 40 percent by weight being the polyol blend of (11) and (IV).

And, when the amine triol (111) and (IV) are employed there are obtained miscible polyol blends 60 comprising from at least about 20 percent by weight to at least about 50 percent by weight of a fluorocarbon blowing agent and the corresponding 80 percent to about 50 percent by weight being the polyol blend of (111) and (IV).

When water is the blowing agent it is present in the proportions of from about 1 percent to about 6 GB 2 122 210 A 6 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 (1), (11), or (111) 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 are halogenated aliphatic hydrocarbons which are also substituted by chlorine and/or bromine in addition to the fluorine content and are well known to those skilled in the art; see U.S.

Patent 3,745,133 column 11, lines 25 to 38 which disclosure relating to fluorocarbon blowing agents is incorporated by reference herein.

In a preferred embodiment of a polyol blend in accordance with the present invention which finds particular utility in the preparation of polyisocya n u rate foams, there is additionally present, in the blend 10 of blowing agent and components (1), (11), or (111) and (IV), an lsocyanate trimerization catalyst. The isocyanate trimerisation catalyst component will be discussed in detail below. The isocyanate trimerisation 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 (1), amide diol (11), or amine triol (111). 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 20 minor constituent when preparing polyisocyan u rate foams have been noted above.

Other optional additives can be added to the 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 stabilisers, surfactants, flame retardants, and the like which are commonly employed ' in the process of the invention.

In the preparation of polyisocya nu rate 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 fluorocarbon, a water blowing agent and a trimerisation catalyst to form a B side component for reaction with an A side comprised of an organic polylsocyanate. In this event the values of x and y in (1) 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 trimerisation catalyst and from about 80 to about 98, preferably about 85 to 98 percent by weight of (1), (11), or (111) 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 (1), (11), or (111), which latter, accordingly is presently in an amount from about 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 (1), (11), or 40 (111), which, accordingly, is present in an amount from about 94 to about 99, preferably 95 to 98 percent by weight.

The B side blend is advantageously employed in an amount failing within the range of from about parts to about 120 parts, preferably from about 10to about 80 parts, most preferably from about 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 stabilised miscible blends discussed above, but, additionally, provides polyisocyanurate foams having the optimum advantageous 50 properties discussed above, including the preparation of foam laminates which.require no oven heating in order to achieve maximum foam strength and adhesion to the laminate facers. In this event the values of x and y in (1) have the narrower ranges as noted above of from about 4 to about 15.

The blend containing the amine diol (1), amide diol (11), or amine triol (111), with primary hydroxyl polyol (IV), blowing agent, and trimerisation catalyst is also employed in an amount failing within the 55 same range of parts per isocyanate equivalent set forth above for the B blend without OV); and with the same proviso set forth above for the range of total hydroxyl equivalents per equivalent of isocyanate.

The proportions 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 (1), amide diol (11), amine triol (111), primary hydroxyl polyol (IV), and blowing agent, all have the same significance and scope set 60 forth above.

The trimerisation catalyst employed can be any catalyst known to those skilled in the art which will catalyse the trimerisation of an organic isocyanate compound to form the isocyanurate moiety.

Further, a combination of urethane forming catalyst and trimerisation catalyst can be employed if desired.

7 GB 2 122 210 A 7 For typical isocyanate trimerisation catalysts see The Journal 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, the disclosures of these references being hereby incorporated by reference herein.

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 metal salt of an N-substituted amide with (b) an alkali metal salt of an N-(2-hydroxyp henyl) m ethyl glycine and optionally (c) a tertiary amine trimerisation catalyst. The latter reference discloses the combination of the same (a) and (b) components above with a hydroxyalkyl-trialkylammonium carboxylate salt component.

The organic polyisocyanate which can be employed in the preparation of the polyisocyanu rate 10 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 polyisocyanates are the polymethylene polyphenyl polyisocyanates, particularly those set forth in U.S. Patent 3,745,133 whose disclosure with respect to said isocyanates is incorporated by reference herein. Also preferred are the polymethylene polyphenyl 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 3,362,979.

A most preferred organic polyisocyanate is a mixture containing from about 30 percent to about 20 percent by weight of methylenebis(phenyl isocyanate) and the remainder of said mixture comprises polymethylene polyphenyl polyisocyanates of functionality higher than 2.0.

In carrying out the preparation of polyisocyanu rate foams in accordance with the process of the invention, and, in particular, polyisocyanu rate foams for the preparation of foam laminates, the procedures and equipment conventional in the art are employed (see patents cited supra); for a detailed teaching of the mode of preparation, and utility of, polyisocyanu rate foam laminates see U.S. Patent 3,896, 052 whose disclosure relative thereto is incorporated by reference herein.

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 polyisocya nu rate foams (Foam A through E) were prepared in accordance with the following 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 1 below, in 1 qt. cups. The polylsocyanate ingredient was the sole 35 component of the A side while the B side ingredients which are listed in Table 1 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 20IC). 40 Foams B and E are in accordance with the present invention while A, C, and D are not because the amine 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 solubilisers while in C there was present additionally the phosphate plasticizer. Foam D also contained the plasticising 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 and indicates that an efficient curing or reaction has occurred at the surface. All of the foam samples showed a good surface blush.

Table 1

Foams A 8 C D E Ingredients (pts. by wt) A side:

Polyisocyanate 11 B side:

Diethylene glycol Varonic@ L-202 2 Varonic@ K-21 51 Pluracol@ GP-7304 Pluracol@ PEP-6505 100 100 100 100 55 5.7 5.4 6 5.7 5.7 6 6 6 8 23.5 - - 8 6 - - 60 8 GB 2 122 210 A 8 Table 1 (contd.) Foams A 8 c D E Tris(d ich lorop ropylphosph ate) - 7.2 18 Propoxylated poly016 L-54207 1.25 Fluorocarbon R-1 1 B" 25 Catalyst 19 3 NCO/OH index about 4 Appearance of B component clear and not turbid 339 rapid high none yes Foam reaction exotherm (OF) Firm Rate Core friability Surface friability 15 Surface blush Footnotes to Table 1 1.25 25 3 about4 clear and not turbid 313 slow low none yes 1.25 25 3 about 4 clear and not turbid 294 medium high none yes 18 6 1.25 25 3 about 4 clear and not turbid 298 rapid high none yes 1Polyisocyanate 1 is a polymethylene polyphenyl polyisocyanate containing about 45 percent by 1.25 25 3 about 4 clear and not turbid 10 345 rapid low none yes 15 weight of m ethyl enebis(phenyl isocyanate) and the remainder of said mixture consisting of polymethylene polyphenyl polyisocyanate having a functionality greater than 2; the isocyanate equivalent=133.

2 Varonic@ 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 Diviiion, Ashland Chemical Company, Columbus, Ohio.

3Varonic@ K-21 5 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.

4PI uracol@ GP-730 is a propoxylated glycerine product; hydroxyl equiv. wt.=243, and is supplied by BASF Wyandotte Chemical Corp., Wyandotte, Mich.

5PI uracol@ PEP-650 is a propoxylated pentaerythritol product; hydroxyl equiv. wt.=1 48 and is supplied by BASF Wyandotte Chemical Corp., Wyandotte, Mich.

6 Propoxylated polyol is the product obtained from propoxylating a mixture of sorbitol and toluene diamine to a hydroxyl number of 360, viscosity of 2500 centistokes at 250C, and specific gravity of 1.072.

7 L-5420: A rigid foam silicone surfactant having a hydroxyl number of about 119 supplied by Union Carbide Corp., Tarrytown, N.Y. 1059 1; see Union Carbide Bulletin F- 43565, December 197 1. 35 8FIuorocarbon R-1 1 B is a monofluorotrichloromethane blowing agent stabilised with allo ocimene and supplied by DuPont Chemical Corp., Wilmington, Del.

sCatalyst 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- ethylhexamide, (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-methyI glycinate in diethylene glycol; and C.) 1 part of a solution comprised of 50 percent by weight of 2- hydroxypropyltri m ethylammonium 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 d comparison of the prior art method (Foams F and H) versus the method in accordance with the present invention (Foams G and 1).

The ingredients of the A and B sides are set forth in Table 11 below. The F and G pair contained a different polyisocyanate from the Hand I pair. The Aside of Foams F and H contained the fluorocarbon 50 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 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 1, clearly show a much faster rate for the foams in accordance with the invention (G and 1) 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 a mine used in Foams G and I is a tertiary 60 amine, these types of high molecular weight tertiary amines are not strong bases and were used in G 9 GB 2 122 210 A 9 and 1 in very small amounts based on amine equivalents, i.e. 0.009 equivalents in each case. This low level of weak amine would not be enough to explain the dramatic rate increases of G and 1 over F and H respectively on the basis of amine catalysts alone.

Table 11

Foams F G H 1 Ingredients (pts. by wt.) A side:

Polyisocyanate 11 100 100 Polyisocyanate 112 - 105 105 Fluorocarbon R-1 1 B 21.5 - 22.5 - 10 B side:

Diethylene glycol 8.3 8.0 8.3 8.0 Varonic@ K-21 5 - 8.0 - 8.0 L-5420 1.25 1.25 1.25 1.25 Catalyst 1 3.0 3.0 3.0 3.0 15 Fluorocarbon R-1 1 B 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 20 Tack Free 116 49 106 47 Exotherm (IF) 341 336 318 316 Core density, pcf 1.76 1.74 1.79 1.75 Dry heat age 300117/24 hrs.

% A volume +4.6 +4.1 +2.9 +2.4 25 Core friability, %3 31 30 22 19 Surface friability none none none none Surface blush yes yes yes yes Footnotes to Table 11 'See Footnote 1, Table 1.

2 Polyisocyanate 11 is a polymethylene polyphenylpolyisocyanate containing about 35 percent by weight of methylene-bis(phenyl isocyanate) and the remainder of said mixture consisting of polymethylene polyphenyl polylsocyanate having a functionality greater than 2; the isocyanate equivalent=l 40.

3 The friability is the percent sample weight loss over a 10 minute period and determined in 35 accordance with ASTM Test method C-42 1.

Example 3

The following two polyisocya n u rate 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 Ill below. The B components were clear in 40 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 45 amount of the Varonic@ K-215 amine diol which acted as a compatibilising agent for the various other catalyst components. In the absence of the Varonic@ K-21 5 the other catalyst components are not completely miscible.

GB 2 122 210 A 10 Table Ill

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

Polyisoo-yanate 1111 135 135 5 B side:

Varonicg K-2052 37 - Varonic@ K-215 - 75 DC-1 93 3 1.5 1.5 Fluorocarbon R11 B 22 27 10 Catalyst 114 3 3 NCO/OH index 4.5 4.5 B mix appearance clear clear Foam rise time (seconds) 15 Cream 5 6 Gel 20 20 Tack Free 30 40 Rise - - Exotherm (OF) 328 305 20 Surface friability none none Surface blush yes yes Core friability low low Appearance very fine cell very fine cell Footnotes to Table III 'Polyisocyanate III is a polymethylene polyphenyl polyisocyanate containing 45 percent by 25 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=1 35.

2 Varonic@) L-205 is the cocoamine adduct obtained by the reaction of a 5 molar proportion of ethylene oxide with cocoa mine; a mine equivalent wt.=about 445; hydroxyl equiv. wt. about 222; 30 supplied by Chemical Products Division, Ashland Chemical Company, Columbus, Ohio.

3 DC-1 93 is a silicone surfactant supplied by Dow Corning Midland, Mich; see Bulletin 05-146, February 1966.

4Catalyst 11 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 35 in diethylene glycol; B.) 0.50 part of potassium acetate; C.) 0.30 part of water; and D.) 0.50 part of Varonic@ K-21 5 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-21 5 component yields a turbid and cloudy mixture.

Example 4

The following two water blown polyisocya n u rate 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 45 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.) 50 A side:

Polyisocyanate Ill 135 135 B side:

Polyol blend 11 23 30 L-5420 2 2 55 H20 1 1 Catalyst 11 3 3 11 GB 2 122 210 A 11 Table IV (contd.) Foams L m NCO/OH index (including H20) 3.2.5 B mix appearance clear clear Foam rise time (seconds) 5 Cream 15 13 Gel 31 26 Rise 48 48 Tack free 35 30 Exotherm (IF) 376 383 10 Density (pcf) 2.65 2.81 K-Factor 2 in BTU (ft.2) (hr) I F/in.:

in dir. 0.190 0.201 in dir. 0.189 0.193 Compressive str. (psi) 15 11 to rise 39.5 42 1 to rise 30.0 20 %A Volume at 701C, 100% relative humidity after 24 hrs. -7.7 -4.7 300cF Dry Age A Volume (%) after 24 hrs -2.9 +3.0 20 Footnotes to Table IV 'Polyol blend 1 comprises a blend in the following proportions of A.) 40.8 pts. of a polyoxydiethylene adipate glutarate polyester diol of M.M=500; B.) 28.6 pts. of diethylene glycol; and C.) 30. 6 pts. of Varonic@ K-21 5. 25 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 polyisocya nu rate foam N prepared in accordance with the present invention using the procedure and apparatus described in 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

35... F61am - N 35 Ingredients (pts. by wt.) A side:

Polyisocyanate 111 135 B side:

TPEG-9901 8.5 40 Diethylene glycol 6.5 Varonic@ K-21 5 10 DC-1 93 1.25 Catalyst 11 3.0 Fluorocarbon R-1 1 B 20 45 B mix appearance clear no turbidity % R-1 1 B in B mix 41% Foam rise time (seconds) Cream 13 Gel 30 50 Tack Free 35 Exotherm (OF) 349 Surface friability none Surface blush yes Core friability low 55 Footnote to Table V ITPEG-990 is a primary hydroxyl containing trifunctional polyethylene glycol having OH E.W.=333; and is supplied by Union Carbide Corp., New York, N.Y.

12 GB 2 122 210 A 12 Example 6

The following high temperature and flame resistant polyisocya n u rate foam laminates were prepared in accordance with the present invention using the foam 0 which was prepared from the ingredients set forth in Table M below.

A Viking laminating machine was used with "A" and -B- component temperatures of 73 OF and 5 70F respectively. Throughput was 15 lbs/min through a low pressure impingement mixing head. A pour lay down túichnique was used instead of a nip roll. The conveyor speed was 10 ft/min and the curing oven temperature was at ambient (70 to 901 F).

Two inch thick laminate was prepared with 0.001511 aluminium foil facers and also prepared with asphalt facers. The foam properties reported in Table VI below are for the foam core material after the 10 faces 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 containing the primary hydroxyl polyester and diethylene glycol and a 43% by weight content of freon (RA 1 B) was clear with no turbidity.

The laminates were prepared without the necessity of oven curing at a high temperature because15 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.

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

Table V1

Foam 0 Ingredients (pts. by wt.) A side:

Polyisocyanate 1 133 25 B side:

Polyester diol 9 Diethylene glycol 6.3 Varonic@ K-215 6.7 DC-1 93 1.25 30 Catalyst 11 3.0 Fluorocarbon R-1 1 B 20.0 B mix appearance clear no turbidity % R-1 1 B in B mix 43% NCO/OH index 4.9 35 Foam rise time (seconds) Cream 19 Gel 40 Tack Free 47 Surface friability none 40 Surface blush yes Core friability low (6%) Overall density (pcf) 2.0 Core density 1.8 Compressive str (psi) to rise 31 45 Compressive str (psi) to rise 21 Closed ceIIS2 94% K factor in BTU (ft.2) (hr) IF/in 0.14 Humid age (1 580F, 95% R.H.) A Vol., after 1 day +6% 50 7 days +6.5% 28 days +7.0% ASTM E-84 Test on 2" thick samples:

Flame spread rating 38 Smoke 187 55 Footnotes to Table V1 D-2856.

Polyester diol is the same diol described in Footnote 1 of Table IV under A. 2CIosed cells are determined by the air pycnometer test in accordance with ASTM Test method 13 GB 2 122 210 A 13 Example 7

The following polyisocyanu rate 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 V11 below.

The B side was clear without evidence of turbidity in spite of the combination of the fluorocarbon 5 with the primary hydroxyls of the amide diol.

The foam produced was characterised by a very fine cell structure with no surface 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 VIl 10

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

Polyisocyanate 1111 135 B side: 15 Varamide@ 6-CM2 49 DC-1 93 1.5 Fluorocarbon R-1 1 B 23 Catalyst 113 3 NCO/OH index 4.5 20 B side appearance clear non-turbid Foam rise time (secs) Cream 8 Gel 42 Tack free 52 25 Rise - Exotherm (IF) 328 Surface friability none Surface blush yes Core friability moderately friable 30 Appearance very fine cell Footnotes to Table VIl 1Polyisocyanate Ill is the same polymethylene polyphenyl polyisocyanate defined in Example 3, Footnote 1 of Table 111. 35 2Varamide@ 6-CM is the cocoamide adduct obtained by the reaction of a 6 molar proportion of 35 ethylene oxide- with a 1 molar proportion of cocoamide; amine eq. wt.=290; OH eq. wt.=1 93; supplied by Chemical Products Div., Ashland Chemical Co., Columbus, Ohio; and otherwise identified by the chemical name of N,N-bis(hydroxy-3, 6-dioxaoctyl)cocoamide mixture. 3Catalyst 11 is the same catalyst combination defined in Example 3, Table III, Footnote 4.

Example 8

The following polyisocyanu rate 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 0 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 45 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 0 and R on the one hand with Foam S on 50 the other, clearly shows a much faster rate for the foams in accordance with the invention (0. 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 the two hence the faster rise times over the formulations of the prior art.

14 GB 2 122 210 A 14 Table VIII

Foam 0 R S Ingredients (pts. by wt.) A side:

Polyisocyanate 111 135 5 Polylsocyanate 11 100 - 100 Fluorocarbon R-1 1 B - 21.5 B side:

Polyester dio12 - 9 - Diethylene glycol 8 6.3 8.3 10 Varamide R 6-CM 8 6.7 - L-5420 1.25 - 1.25 DC-1 93 - 2 - Fluorocarbon R-1 1 B 25 22 Catalyst 11 4.5 5 - 15 Catalyst 13 - - 3.0 NCO/OH index about4 about4 about 4.6 B side appearance clear non-turbid clear non-turbid - Foam rise time (secs) Cream 16 16 75 20 Gel 40 35 104 Tack Free 45 40 116 Rise 54 48 - Exotherm (OF) 344 351 341 Firm rate rapid rapid - 25 Surface friability none none Surface blush yes yes - Core density (pcf) T.55 2.06 1.76 Core friability (%) 38.5 32.0 31 3001F Dry Age A Volume (Y6124 hrs +7.4 +5.0 +4.6 30 Footnotes to Table VIII 1Polyisocyanate 1 is the polymethylene polyphenyl polyisocyanate defined in Example 1, Table 1 Footnote 1.

#=211.5.

2 Polyester diol: a polyoxydiethylene adipate glutarate polyester diol of MW=500, and OH 3 Catalyst 1 is the same catalyst combination defined in Example 1, Table 1, Footnote 9.

Example 9

The following polyisocya nu rate 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 40 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 exotherm was good and the rapid rise profile indicated the fast reactivity of the foam. 45 GB 2 122 210 A Table IX

Foam T Ingredients (pts. by wt.):

A side:

Polyisocyanate 111 135 6 B side:

KD-2141 56 DC-1 93 1.5 Fluorocarbon R-1 1 B 23 Catalyst 11 2.5 10 NCO/OH index 4.5 B side appearance clear non-turbid Foam rise time (secs.) Cream 4 Gel 17 15 Tack free 50 Rise Exotherm (IF) 323 Surface friability none Surface blush slight 20 Core friability low Appearance very fine cell Footnotes to Table IX 'KD-1 24 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 cocodlamine 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.=1 93; supplied by Chemical Products Div., Ashland Chemical Co., Columbus, Ohio.

Example 10

The following polyisocya nu rate Foams U, V and W were prepared in accordance with the 30 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 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 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 the Foam W on the other, clearly shows a much faster rate for the foams in accordance with the invention (U and V) 40 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 the faster rise times over the formulations of the prior art.

16 GB 2 122 210 A 16 Table X

Foam U v W Ingredients (pts. by wt.) A side:

Polyisocyanate 111 135 5 Polylsocyanate 1 100 - 100 Fluorocarbon R- 11 B 21.5 B side:

Polyesterdioll - 9 - Diethylene glycol 8 6.3 8.3 10 KD-214 8 6.7 - L-5420 1.25 - 1.25 DC-193 - 2 - Fluorocarbon R-1 1 B 25 22 Catalyst 11 2.5 2.5 15 Catalyst I - - 3.0 NCO/OH index about4 about 4 about 4.6 B side appearance clear non-turbid clear non-turbid - Foam rise time (secs) Cream 16 15 75 20 Gel 39 42 104 Tack free 46 50 116 Rise 56 60 - Exotherm (OF) 331 337 341 Firm rate rapid rapid - 25 Surface friability none none Surface blush yes yes - Core density (pcf) 1.67 2.27 1.76 Core friability (%) 18.8 33.1 31 3001F Dry Age, A %/24 hrs +10.8 +5.3 +4.6 30 Footnote to Table X Polyester diol: a polyoxydiethyiene adipate glutarate polyester diol of MW=500, and OH#--211.5.

Example 11

A series of blends of fluorocarbon R-1 1 B (monofluorotrichloromethane) with two typical primary 35 hydroxyl polyols of the present invention wereprepared. The proportions by weight employed, including the amount of amine diol (1) when present, varied according to the values set forth in Table XI below. The blends were observed for their miscibility and clearness of their turbidity and separation of the fluorocarbon from solution.

Blends A through D contained diethylene glycol with fluorocarbon and in the absence of amine 40 diol, i.e., 100% diethylene glycol, the maximum fluorocarbon solubility was 15% by weight. The addition of 10 percent by wt. amine diol was not sufficient to impart fluorocarbon solubility at the 25% by wt. level whereas a 20 percent amine diol content (blend D) did result in a clear miscible solution at percent fluorocarbon.

Blends E through J contained a polyester diol defined above wherein the pure polyester diol was 45 capable of dissolving 20 percent by weight fluorocarbon but not 25 percent. The break for 25 percent fluorocarbon solubility started at about 10 parts by weight of the amine diol (blend G) while at the 20 percent level of amine diol the fluorocarbon could reach 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 50 maximum of 85 percent by weight of amine diol was employed.

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

c Table XI

Blend A 8 c D E F G H 1 Ingredients (pts. by wt.) Diethylene glycol 100 100 90 80 Polyester diol I - - - - 100 100 90 80 80 K2152 - - 10 20 - 20 20 Fluorocarbon RA 1 B 17.6 25 33.3 33.3 25 33.3 33.3 40 45 % by wt. primary alcohol 100 100 90 80 100 100 90 so 80 % by wt. amine diol 0 0 10 20 0 0 10 20 20 % by wt. fluorocarbon 15 20 25 25 20 25 25 28.5 31 Blend appearance clear turbid turbid clear clear turbid clear clear clear miscible separates separates miscible miscible separates miscible miscible miscible Table X1 (contd.) Blend j K L m N 0 p 0 Ingredients (pts. by wt.) Diethylene glycol - 15 - - 50 50 - - Polyester dioll 80 - 15 15 50 K-2152 20 85 85 85 50 50 50 50 Fluorocarbon R-1 1 B 50 900 207.7 233.3 150 175 100 120 by wt. primary alcohol 80 15 15 15 50 50 50 50 by wt. amine diol 20 85 85 85 50 50 50 50 by wt. fluorocarbon 33.3 90 67.5 70 60 63.6 50 55 Blend appearance cloudy clear clear turbid clear turbid clear turbid miscible miscible separates miscible separates miscib;e separates Footnotes to Table XI The same polyester diol described in Footnote I of Table IV under A.

2K-215 is the amine diol (1) defined in Footnote 3 of Table 1.

N) 18 GB 2 122 210 A 18 Example 12

6 A series of blends of fluorocarbon R-1 1 B (monofluorotrichloromethane) with three typical primary hydroxyl polyols of the present invention were prepared. The proportions by weight employed, including the amount of cocoamide diol (11) 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 5 separation of the fluorocarbon from solution.

Blends A through D contained diethylene glycol and, in the absence of any amide diol, the maximum fluorocarbon 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, 10 obviously, was clear at the 80/20 blend level (blend D).

Blends E through 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 trorn a polyester diol and it was observed that while 20 percent fluorocarbon solubility was possible with the pure diol that 25 percent was not. When the 15 amide diol level was 20 percent (blends J through Q the highest fluorocarbon level attainable was about 3 1 percent.

Blends M through 0 were observed to have maximum fluorocarbon levels of greater than 90 percent and up to 60 percent by weight for diethylene glycol and the polyester 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 percent respectively for diethylene glycol and polyester diol when the primary alcohol-amide diol blends were 50/50 percent by weight.

(D Table X111

Blend A 8 c D E F G H 1 J Ingredients (pts. by wt.) Diethylene glycol 100 90 85 80 Ethylene glycol - - - - 100 85 80 Polyester dioll - - - 100 100 80 6-CM2 - 10 15 20 - 15 20 - - 20 Fluorocarbon R-1 1 B 25 25 25 25 25 25 25 25 33.3 40 % by wt. primary alcohol 100 90 85 80 100 85 80 100 100 80 by wt. amide diol 0 10 15 20 0 15 20 0 0 20 by wt. fluorocarbon 20 20 20 20 20 20 20 20 25 28.5 Blend appearance turbid turbid clear clear turbid turbid clear clear turbid clear separates separates separates separates separates Table X1111 (contd.) Blend K L m N 0 p 0 R S Ingredients (pts. by wt.) 15 Diethylene glycol 50 50 Ethylene glycol - - - - - - - - Polyester diol 1 80 80 - 15 15 - - 50 50 6-CM2 20 20 85 85 85 50 50 50 50 Fluorocarbon R- 11 B 45 50 900 150 166.7 125 150 81.8 100 by wt. primary alcohol 80 80 15 15 15 50 50 50 50 by wt. amide diol 20 20 85 85 85 50 50 50 50 by wt. fluorocarbon 31 33.3 90 60 62.5 55 60 45 50 Blend appearance just turbid clear clear turbid clear turbid clear turbid clear separates miscible miscible separates separates separates Footnotes to Table X11 The same polyester diol described in footnote 1 of Table IV above.

2 6-CM is the same cocoamide identified in footnote 2 of Table Vil above.

G) m GB 2 122 210 A 20 Example 13

A series of blends of fluorocarbon R-1 1 B (monofluorotrichloromethane) with three typical primary hydroxyl polyols of the present invention were prepared. The proportions by weight employed, including the amount of amine trio[ (111) when present, varied according to the values set forth in Table XIII below. The blends were observed for their miscibility and clearness or their turbidity and separation 5 of the fluorocarbon from solution.

Blends A tfirough 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 trio[ (blend B) was not sufficient to impart fluorocarbon solubility at the 20 percent level. It was not until at least 15 percent of amine trio[ 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 from a polyester diol and it was observed that while 20 percent fluorocarbon solubility was possible, 25 percent fluorocarbon solubility was not with the pure diol and that at least 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 the maximum fluorocarbon solubility was about 28.6 percent by weight.

Blends N through P were observed to have maximum fluorocarbon 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 percent respectively for diethylene glycol and polyester diol when the primary alcohol-amine triol blends were 50/50 percent by weight.

hi Table X11111

Blend A 8 c D E F G H 1 j Ingredients (pts. by wt.) Diethylene glycol 100 90 85 80 Ethylene glycol - - - - 100 85 80 Polyester dioll - - - 100 100 90 KD-2142 - 10 15 20 - 15 20 - - 10 Fluorocarbon RA 1 B 25 25 25 25 25 25 25 25 33.3 33.3 % by wt. primary alcohol 100 90 85 80 100 85 80 100 100 90 by wt. amine triol 0 10 15 20 0 15 20 0 0 10 by wt. fluorocarbon 20 20 20 20 20 20 20 20 25 25 Blend appearance turbid turbid clear clear turbid turbid clear clear turbid turbid separates separates miscible miscible separates separates miscible miscible separatesseparates Table X1111 (contd.) Blend K L m N 0 p 0 R S T Ingredients (pts. by wt.) Diethylene glycol 15 50 50 Ethylene glycol - - - - - - - - - - Polyester dioll 85 80 80 - 15 15 - - 50 50 KD-2142 15 20 20 85 85 85 50 50 50 50 Fluorocarbon R-1 1 B 33.3 40 45 900 100 110.5 100 122.2 66.7 81.8 by wt. primary alcohol 85 80 80 15 15 15 50 50 50 50 by wt. amine triol 15 20 20 85 85 85 50 50 50 50 by wt. fluorocarbon 25 28.6 31 90 50 52.5 50 55 40 45 Blend appearance clear clear turbid clear clear turbid clear turbid clear turbid miscible miscible separates miscible miscible separates miscible separates miscible separaLes Footnotes to Table X1111 The same polyester diol described in footnote 1 of Table IV above.

2 KD-214 is the cocodiamine (111) adduct defined in footnote 1 of Table IX above.

G) m h) N) m Ni 0 22 GB 2 122 210 A 22

Claims

Claims 1. In a process for the preparation of cellular polymer in which the major recurring polymer unit is an isocyanurate moiety said process comprising the trimerisation of an organic polyisocyanate in the presence of a minor amount of polyol, a blowing agent, and a trimerisation 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 polylsocyanate of a blend comprising (a) about 2 to about 20 percent by weight of a polyisocyanate trimerisation 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: R, R, 0 (CH2k;HU-t.' 11 R2-C-N R-N (CH2CH04,-H 1 hi 1 R-N \ R, 1 U"2Uhu-4-,,, H (CH4,-N (CH2CHO--,, H i hi 11 (CH2CH0-4.,, H 1 (CH2CHOL--H 1 M1 Ill and wherein R is an aliphatic radical having from 8 to 18 carbon atoms, inclusive, R2'S an aliphatic radical having from 7 to 17 carbon atoms, inclusive, each R, 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, 20 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. 2. A process according to claim 1 substantially as described herein with reference to any one of 25 the Examples. New claims or amendments to claims filed on 1 st Aug. 83. Superseded claim 1 New or amended claim: 1. A process for the preparation of cellular polymer in which the major recurring polymer unit is 30 an isocyanurate moiety said process comprising the trimerisation of an organic polyisocyanate in the presence of a minor amount of polyol, a blowing agent, and a trimerisation catalyst, wherein said cellular polymer is prepared 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 35 comprising (a) about 2 to about 20 percent by weight of a polyisocyanate trimerisation catalyst, and 23 GB 2 122 210 A 23 (b) about 80 to about 98 percent by weight of a mixture comprising: about 20 to about 80 percent by weight of a fluorocarbon blowing agent, the remainder of said mixture comprising: a member or mixture of members selected from compounds of the formulae: R, R, 1 1 k(;t'2Ut'O-hH 0 C H O--,-, H 11 2 X hi-C-IM \ R-N \ (CH2CHO+YH I. R, 1 k (CHR14,-N (CH2CHO+,, H 1 K1 11 R, 1 Utl2UHO+.,, H R-N \ (CH2CHO-hH 1 1.

1 hi Ill CH2C1-10+.,, H 1 and 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 R, 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' 10 It 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.

New claims or amendments to claims filed on 1 Oth June 1983.

New or amended claims:

2. A modification of the process claimed in claim 1, wherein the said component (b) comprises to 98 percent by weight of a mixture comprising:

1) 1 to 6 percent by weight of water as the blowing agent, and 2) the remainder of said mixture comprising (1), (11), or (111), or mixtures thereof.

3. A process according to claim 1 substantially as described herein with reference to any one of the Examples.

Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1984. Published by the Patent Office, 25 Southampton Buildings, London, WC2A 1 AY, from which copies may be obtained.