METHOD FOR THE MANUFACTURE OF URETHANE-MODIFIED ISOCYANURATE FOAMS

Abstract: A method for the manufacture of urethane-modified polyisocyanurate foams in which an isocyanate is blended with a "B" side comprising a polyol blend, a surfactant, a blowing agent, and catalyst. The polyol blend comprises a mixture of a polyalkoxylated amine and a polyalkoxylated quaternary ammonium borate ester, and a resin polyol, with any remainder being a polyether or polyester polyol. All com­ ponents of the "B" side will remain a homogeneous liquid without phase separation and without the need for agitation for at least 7 days after blending.

Description: Method for the manufacture of urethane-modified isocyanurate foams This invention pertains to the formation of urethane-modified isocyanurate foams using mixtures of polyalkoxylated amines and polyalkoxylated quaternary ammonium borate esters as copolyols. More particularly this invention relates to the use of such copolyols to form foams having NCO/ OH ratios of 1.5 to 3.5, using very inexpensive, commercially available resin polyols. A blend of these polyalkoxylated amines and polyalkoxylated quaternary ammonium borate esters with the aforesaid resin polyol and, optionally, a polyether or polyester polyol is very stable and will remain a homogeneous liquid without phase separation and without the need for agitation for at least 7 days after blending. Urethane and polyisocyanate foams are manufactured using a blend of an isocyanate and a polyol. The molar ratio of isocyanate to polyol, that is, the ratio of NCO functional groups to OH functional groups, is known as "the index" or "NCO/OH ratio". Foams are manufactured with both isocyanates and polyols and when the molar ratio of isocyanate to polyol is between 1.05 to 1.15, a urethane foam is formed according to the reaction: EMI1.1 The urethane product shown above is the monomeric structural unit that combines to form the polyurethane foam. At an index between 1.5 and 3.5, a urethane-modified isocyanurate foam is formed. At indices above 4.1, an isocyanurate foam is formed having the monomeric unit: EMI1.2 which may have a minority of urethane linkages. Herein, the terms isocyanurate and polyisocyanurate and the terms urethane and polyurethane in reference to foams will be used interchangably. Currently, urethane-modified polyisocyanurate foams are manufactured u sing polyether or polyester polyols, as for example the Vorano 0 group of polyols available from Dow Chemical Company, Midland, Michigan. When combined with a catalyst, a surfactant, and a blowing agent, and then with an isocyanate in the known manner, these polyether or polyester polyols form a foam having good qualities. Certain resin polyols, such as the Terate resin polyol available from Hercules, Incorporated, Wilmington, Delaware, the D 400 Polyol resin polyol available from Dixie Chemical Company, 10701 Bay Area Boulevard, Pasadena, Texas, and the Foamol 250 resin polyols available from Jim Walter Research Corporation, 10301 9th St. North, St. Petersburg, Florida, are of a hydroxyl number sufficient so as to theoretically permit their use in foam manufacture. In practice, however, these polyols have proved to be unacceptable at concentrations in excess of 40% (wt.) of the total polyol blend for use in manufacturing high quality urethane-modified polyisocyanurate foams. Because the resin polyols are about one-third less costly than the currently used conventional polyether or polyester polyols, it is desirable that a polyol blend be found that may be used with larger quantities of such resin polyols to result in a polyisocyanurate foam having acceptable properties and at a lower cost. The present invention is a method for the manufacture of urethane -modified polyisocyanurate foams, comprising blending an isocyanate with a "B" side, the "B" side comprising a polyol blend, -a surfactant, a blowing agent, and a catalyst. The polyol blend comprises: a. at least 5% (wt.) of a mixture of a polyalkoxylated amine and a poly alkoxylated quaternary ammonium borate ester b. at least 40% (wt.) of a resin polyol, said resin polyol comprising at least 70% (wt.) of a combination of polymers and monomers having the general formula EMI3.1 wherein n is between 0 and 50, R11 is either H- or CH3- , and p and q are each integers between 1 and 10; or at least 45% (wt.) of a resin polyol, said resin polyol either having the general formula EMI3.2 wherein n' is either 1 or 2 and x' is an integer between 1 and 20, inclusive; or having the general formula EMI3.3 wherein n is an integer between 1 and 4 inclusive and x and y are in tegers each having a value of between 2 and 20, inclusive; c. the remainder of said polyol blend being a polyether or polyester polyol. All of the components of the "B" side may be blended and will thereafter remain a homogeneous liquid without phase separation and without the need for agitation for at least seven days. In one embodiment of the invention the weight ratio of polyalkoxylated amine to polyalkoxylated quaternary ammonium borate ester is between 1:0.15 and 1:12.0 when use is made of resin polyol comprising at least 70% (wt.) of a compound having the general formula (I). In another embodiment of the invention the weight ratio of polyalkoxylated amine to polyalkoxylated quaternary ammonium borate ester is between 1:0.15 and 1:4.1 when use is made of resin polyol having the general formula (II) or (III). In yet another embodiment of the invention, the polyalkoxylated amine is selected from the group consisting of: EMI4.1 wherein R is selected from the group of alkyl radicals having between 1 and 18 carbon atoms, x and y are integers each having a value of at least one and wherein the sum of x and y does not exceed 50 and wherein R and R2 may be the same or different and may be selected from the groups consisting of H-, CH3-, C1-C10 straight- or branched-chain alkyl or alkenyl radicals, a phenyl group, a benzyl group or halogenated alkyl group. In a most preferred polyalkoxylated amine, R corresponds to the tallow alkyl group, R1 and R2 are each H-, and x plus y equal 5. Hence, the preferred polyalkoxylated amine is a tallow penta-ethoxylated amine. In a still further embodiment of the invention, the polyalkoxylated quaternary ammonium borate esters are of the general formula: EMI5.1 wherein R3 is a straight- or branched-chain alkyl or alkenyl radical having from 1 to 30 carbon atoms, inclusive, or a phenyl or benzyl radical; R4 is H-, a C1 to C10 straight- or branched-chain alkyl or alkenyl radical, a phenyl group, a benzyl group, or a halogenated alkyl group; R5 and R6 are different or the same and are selected from the group including H-, or a C1 to C10 straight- or branchedchain alkyl or alkenyl radical, a phenyl group, or a benzyl group; and wherein m is an integer between 0 to 30, inclusive. Preferably, the polyalkoxylated quaternary ammonium borate ester will include an R3 that is a straight- or branched-chain alkyl or alkenyl radical having from 8 to 18 carbon atoms, and R4, R5, R6 will be H-. The borate ester anion may alternatively include a CH3- at the R6 position. A most preferred quaternary ammonium borate ester has an m equal to 0 and an R3 corresponding to the tallowalkyl (C18H37) radical. In yet another embodiment of the present invention, the polyalkoxylated amine is selected from the group consisting of: EMI5.2 wherein R7 is selected from the group of C1-C20 alkyl groups and R8 is a C2 to C alkyl group; R1 and R2 are the same or diffe 2 5 rent and may be selected from the groups consisting of H-, CH3-, C1 to C10 straight- or branched-chain alkyl or alkenyl radicals, a phenyl group, a benzyl group, or a halogenated alkyl group; and x and y are integers each having a value of at least 1 and having a sum not exceeding 50. The isocyanates may be selected from the groups including the organic polyisocyanates which are disclosed herein as useful in the production of conventionally manufactured polyisocyanurate foams. A preferred polyisocyanate is Mondu MR, a polycyclic aromatic polyisocyanate available from the Mobay Chemical Corporation, Pittsburgh, Pennsylvania. Present urethane-modified polyisocyanurate foams may be manufactured according to methods known in the art. These methods comprise blending two components, stirring, and allowing the blend to rise in an open container so as to form the desired foam. The two components are known as the "A" and "B° components, with the "AW component comprising the isocyanate and the "B" component comprising a blend of polyol, catalyst, surfactant, and blowing agent. Catalysts may be selected from those conventionally used in the art, including metal salts, alkali metal salts, and tertiary amine trimerization catalysts. A preferred catalyst is potassium octanoate or potassium-2ethylhexanoate. The present preferred catalyst is M & T - T 45 catalyst, which is 45% active potassium 2-ethylhexanoate and 55% polyethylene glycol having a molecular weight of 200, and which is available from M & T Chemicals Inc., Rahway, N.J., 07065. The amount of catalyst to be used will range from 0.01% to 2% of the total polyol blend weight. The blo wiflg agent may be selected from the group including water, methylene chloride, or any of the fluorocarbons known to those skilled in the art which can be used for blowing polymer mixtures into cellular polymers. Generally speaking, such fluorocarbon blowing agents are fluorinated aliphatic hydrocarbons which may also be substituted by chlorine and/or bromine. A most preferred blowing agent is Freon llA, a trifluorochloromethane produced by E.I. Du Pont de Nemours & Company, Wilmington, Delaware. Surfactants may likewise be chosen from among those known to the skilled in the art; a preferred surfactant is DC-193, a surfactant having silicon glycol copolymers with a direct silicon-carbon bonds, and sold by the Dow Corning Corporation, Midland, Michigan. The present polyol blends may be obtained by mixing in a container the polyalkoxylated amine, polyalkoxylated quaternary ammonium borate ester, resin polyol, and optionally, the polyether or polyester polyol. The polyalkoxylated amines may include polyethoxylated or polvpropoxylated amines, wherein the amines are tertiary amines having one fatty alkyl group derived from various fatty sources and two or more polyoxyethylene or polyoxypropylene groups attached to the nitrogen. Typical of these polyethoxylated or polypropoxylated amines are the Ethomeene polyethoxylated amines available from the Armak Company, 300 S. Wacker Drive, Chicago, Illinois, 60606, preferably being of the general formula: EMI7.1 wherein R is selected from the group of alkyl radicals having between 1 and 18 carbon atoms, x and y are integers each having a value of one or more, the sum of x and y not exceeding 50; and wherein R1 and R2 may be the same or different, and may be selected from the groups consisting of H-, CH3-, Cl-Cl0 straight- or branched-chain alkyl or alkenyl radicals, a phenyl group, a benzyl group or halogenated alkyl group. Another preferred polyalkoxylated amine includes the compound Ethomeen EA-80 polyethoxylated ether amine, which is manufactured by the combination of a C8 and C10 branched-chain alcohol and which is also available from the Armak Company, Chicago, Illinois. These preferred ether amines are selected from the group consisting of: EMI7.2 wherein R7 is selected from the group of C1-C20 alkyl groups, and R8 is a C2 to C5 alkyl group; R1 and R2 are the same or different and may be selected from the groups consisting of H-, CH3-, C1 to C10 straight- or branched-chain alkyl or alkenyl radicals, a phenyl group, a benzyl group, or a halogenated alkyl group; and x and y are in tegers each having a value of at least 1 and having a sum not exceeding 50. Also required for the polyol blend are polyalkoxylated quaternary ammonium borate esters. These compounds are of the general formula: EMI8.1 wherein R3 is a straight- or branched-chain alkyl or alkenyl radical having from 1 to 30 carbon atoms, inclusive, or a phenyl or benzyl radical; R4 is H-, a C1 to C10 straight- or branched-chain alkyl or alkenyl radical, a phenyl group, a benzyl group, or a halogenated alkyl group; R5 and R6 are different or the same and are selected from the group including H-, or a C1 to C10 straight- or branched-chain alkyl or alkenyl radical, a phenyl group, or a benzyl group; and wherein m is an integer between 0 to 30, inclusive. The cationic portion of the polyalkoxylated quaternary ammonium borate ester may also be selected from the group described by the general formula: EMI8.2 wherein m and R4 are as defined hereinabove, Rg is a C1-C20 alkyl or alkoxy group, and R10 is a C2 to C5 alkyl group. Preferably, R10 is a -C3H6- and R9 is a combination of approximately equal amounts of C12-C15 alkyl groups. In this specification, the cationic portion of the polyalkoxylated quaternary ammonium borate esters may be selected from either of the above two general formulae. The polyol blend will comprise one of the resin polyols corresponding to either formula (I), (II) or (III) above. With respect to the resin polyol of which at least 70% by weight will be a compound having the general formula (I), at least 40% by weight of the polyol blend will comprise this resin polyol. Examples of these resin polyols include the Te rate 200 series resin polyols for rigid and semi-rigid polyurethane foam described in Bulletin OR-255 of Hercules, Inc., Wilmington, Delaware 19899, and the above formula (I) is believed to be an accurate structural representation of about 70% of the weight of the Terates resin polyols. The Terates resin polyols are general purpose, moderate viscosity, aro matic polyester polyols derived from polycarbomethoxy-substituted di phenyls, polyphenyls, and benzyl esters of the toluate family. The Terate z polyols are dark colored, highly polar liquids that are insolu ble in aliphatic hydrocarbon solvents and water. Product grades and typical properties are as follows: TABLE 1 Product Grade Viscosity at Hydroxy Acid Number as Water, Average 25 C, cps Number Carboxylic Acid Percent Equivalent Weight Terate" 202 1,900 440 4.5 0.1 127.5 Terate 203 19,000 315 5.1 0.1 i78 Terate 204 13,000 # 275 6 0.1 204 Terate# 211 18,000 540 3 0.1 104 Teratet 2i3 30,000 315 3 0.1 178 (alat 40 C A most preferred Terate 0 resin polyol for use in the present invention is Terates 203 resin polyol. With respect to the resin polyols corresponding to either formula (II) or (III), at least 45%, and preferably up to 80%, by weight of the polyol blend will comprise one of them. Examples of these resin polyols are the D-400 Polyol and the Foamol 250 polyol mentioned hereinabove. The D-400 and the Foamol 250 resin polyols are dark colored, highly polar liquids that are insoluble in aliphatic hydrocarbon solvents and water. The remainder of the polyol blend, if the total polyol blend will not be limited to the polyalkoxylated amine, polyalkoxylated quaternary ammonium borate ester, and resin polyol, will be a conventional polyether or poly ester polyol. These polyether or polyester polyols are well known in the art of polyurethane and polyisocyanurate foam manufacture, as for example the Voranol polyether polyols manufactured by the Dow Chemical Company, Midland, Michigan. A most preferred polyether or polyester polyol is Voranolt 575. The particular polyol blend in accordance with this invention is advantageous in that all of the components of the "B" side may be blended together with a polyol blend and the "BX side will thereafter remain a homogeneous liquid without phase separation and without the need for agitation for at least 7 days, and may still be used to manufacture a foam having excellent physical properties. There are several criteria to be noted in determining whether a foam is of an acceptable quality. Of lesser importance is the tack free time, which is preferably about 60 seconds or less. Dimensional stability is more important, and the foam should not exceed 115% of its original dimensions after seven days. Dimensional stability is tested at two conditions: 700C and 100t relative humidity; and 930C and ambient humidity. Another important criterion is the percentage of closed cells in the foam itself, with a minimum of 85% required. Finally, a percent friability, the loss of weight of the polyisocyanurate foam due to crumbling, is determined by the ASTM C 421 test. The friability of a foam is good if under 20% and excellent if under 10%. The following examples will demonstrate the use of the present polyol blend in the manufacture of polyisocyanurate foams using low cost resin polyols. The first four examples pertain to the manufacture of the particular mixture of a polyalkoxylated amine and a polyalkoxylated quaternary ammonium borate ester. These mixtures are used in this invention in an amount comprising at least 5% (wt.) of the polyol blend. ExamPle 1 304 grass of 1,2-propanediol (4.0 gram moles) are added to 124 grams of boric acid (2.0 gram moles) in a one-liter, three neck flask equipped with a heating mantle, a Dean-Stark trap, and a condenser. The mixture is heated to 1280C at atmospheric pressure, and retained at that temperature and pressure for about 3 1/2 hours, during which time 44.5 grams of water was stripped from the mixture. A water aspirator is then started to create a slight vacuum at the condenser, and another 65.0 grams of water is stripped from the mixture during the next 5 3/4 hours. The total water removed (109.5 grams) corresponds to the stoichiometric amount, but analysis of the borate ester adduct remaining in the flask showed that it contained 3.48 water. 40 grams (0.25 gram moles) of the borate ester formed are added to 262 grams (1.0 gram mole) of Armeen TM 97 aliphatic amine, so as to obtain a 1:0.25 ratio of amine to borate ester, and 58.1 grams diethylene glycol, a solvent. After heating the reaction mixture to 750C, 121.0 grams (2.75 gram moles) of ethylene oxide are added thereto over the next 2 1/2 hours. Analysis of the resulting mixture showed a blend containing 45.4% free amine and 36.7% of a quaternary ammonium propylene glycol borate ester having the formula: EMI11.1 This formula corresponds to Armol l0lB-3 polyethoxylated amine/ammonium borate ester blend. Example 2 A 100 gallon Monel reactor was charged with 84 kg (0.71 mole) of Armeen# TM 97 aliphatic amine and 13.6 kg of diethylene glycol, and the mixture was heated to 650C. Over a two hour period, 38.5 kg (0.53 mole) of the bis-propylene glycol borate ester described in Example 1 was pumped into the reactor, causing the temperature to rise to 80"C. After cooling to 750C, 60 kg (3.02 mole) of ethylene oxide was added over a period of two hours and 42 minutes. During this time the total reactor pressure was not allowed to exceed 3.6 bar and the temperature was maintained at 950C. The mixture was allowed to digest for another 2 hours and 40 minutes, where upon analysis showed 1.317 meq/g of quat and 0.307 meq/g of free amine and 0.3% H2O. The reactor was purged with a stream of nitrogen at 75-850C for 4 hours and an additional 6 hours at 1000C. Analysis showed 0.11% H2O. This is Armol 101B-1. 12.6 kg of the 101B-1 and 48.6 kgs. Ethomeene T/15 were mixed in a 30 gallon Pfaudler reactor at 700C. Water was removed from the blend by sparging with a stream of nitrogen at 700C at 27" Hg vacuum over a 5 1/2 hour period. Analysis after this time showed; quat 0.238 meq/g, free amines 1.779 meg/g, pH (10% in H2O) 10.9, H2O < 0.1% and OH value 318. This product corresponds to ArmolTM 201B-155 ArmolTM 201B-175 amine/ammonium blend. Example 3 17.7 kg or ArmolTh l0lB-l amine/ammonium borate ester blend and 43.5 kg of Ethomeens T/15 ethoxylated amines was blended at 700C in a 30 gallon Pfaudler reactor. Water was removed by sparging with a stream of nitrogen at 70 C, 27" Hg vacuum over 5 hours. Analysis showed; quat 0.331 meq/g, free amine 1.650 meq/g, pH (10% in water) 10.9, H2O < 0.l%, OH value Th 332. This product corresponds to Armol 201B-135 amine/ammonium borate ester blend. ArmolTM 201B-145, ArmolTM 201B-155 and ArmolTM 201-175 amine/ammonium borate ester blend are manufactured in the manner described above using ArmolTM 101B-1: Ethomeen T/15 ratios of 4.8:8.2, 5.9:7.1 and 9.3:5.7, respectively. Example 4 304 grams of 1,2-propane diol (4.0 gram moles) are added to 124 grams of boric acid (2.0 gram moles) in a one-liter, three neck flask equipped with a heating mantle, a Dean Stark trap, and a condenser. The mixture is heated to 1280C at atmospheric pressure, and retained there for about 3 1/2 hours, during which time about 44.5 grams of water are stripped from the mixture. A water aspirator is then started so as to create a slight vacuum at the condenser, and another 65.0 grams of water is stripped from the mixture during the next 5 3/4 hours. The total water removed of 109.5 grams corresponds to the stoichiometric amount, but analysis of the adduct remaining in the flask showed that it contained 3.4% water. 160 grams (1.0 gram mole) of this propylene glycol borate ester are added to 262 grams (1.0 gram mole) of Armeens TMD aliphatic amine and 134 grams (1.0 gram mole) of dipropylene glycol, a solvent. The reactor in which these reactants are blended is communicative with an ethylene oxide reservoir through a stainless steel tube. Four moles of ethylene oxide, pressurized in its reservoir by nitrogen, are slowly added to the reactor over the next 8 1/2 hours, and the resulting quaternary is represented by the formula: EMI13.1 The product formed in the above ethoxylation comprises 48.6% of the ethoxylated quaternary ammonium borate ester shown above and 10.3% free amine, and corresponds to ArmolTM 101B-4 amine/quaternary ammonium borate ester. ArmolTM 101B-2 amine/quaternary ammonium borate ester may be manufactured by adding 75 grams (0.469 gram moles) of the propylene glycol borate ester described in the first paragraph of this example to 246 grams (0.939 gram moles) Armeen TM-97, and 35 grams of diethylene glycol, and then ethoxylating this blend with 144 grams (4.0 gram moles) of ethylene oxide in the manner described in the second paragraph of this example. The ratios of free amine to quaternary in the presently used amine /quaternary ammonium borate ester blend are as follows: Amine/quaternary ammonium Ratio, free amines: borate ester blend quat ArmolTM 101B-1 1:4.06 101B-2 1:1.51 101B-3 1:0.54 101B-4 1:11.6 TM Armol 201B-125 1:0.15 201B-135 1:0.23 201B-145 1:0.35 201B-155 1:0.49 201B-175 1:0.86 Example 5 A urethane-modified polyisocyanurate foam was manufactured by blending 170.3 grams of Mondur BR with a "B" side comprising 20 grams of Armo r 201B-125, 67.5 grams Terate 203, 12.5 grams Voranol 575, 2.5 grams Dow Corning DC-l93, and 41 grams Freon llA. The resulting foam had a cream time of 24 seconds, a gel time of 46 seconds, a tack free time of 69 seconds, a density of 0.033 gram per cc., a 1.21% friability, 88.3% closed cells, was at 109.41% of its original dimensions after seven days at 700C and 100% relative humidity, and was at 106.81% of its original dimensions after seven days at 930C and the ambient relative humidity. Examples 6-9 Urethane-modified diisocyanurate foams were manufactured in substantially the same manner set forth in Example 5, except that instead of Armof 2015-125, other amine/guaternary ammonium borate ester blends were used in accordance with the data in Table 2 below. The reaction profile, densities, percent closed cells, and percent friability are also shown in Table 2. Example 10 E 11 Urethane-modified polyisocyanurate foams were prepared by blending 20 grams of a amine/ammonium borate ester blend with Terate 203. The particular amine/quaternary ammonium borate ester blend used and the reaction profiles and physical properties of the foams manufactured are disclosed in Table 3 below. Examples 12-14 In the following examples, the "B" side, comprising the polyol blend, a surfactant, a blowing agent, and a catalyst were blended and allowed to stand without agitation for seven days. At the end of the seven days, the blends were observed to determine whether they had remained homoge neous. Non-homogeneity, or phase separation of the "B" sides, which were stored in a sealed one-pint jar on a shelf, could be easily determined by viewing the blend. Upon phase separation, the "Bw side would be seen to contain separate and distinct layers. The results are listed in Table 4; those samples showing homogeneity are indicated by the word "yes" in the row entitled "One Week Stability". Example 15 This example is substantially similar to Examples 12-14, except that here the "B" side contain no polyether polyol and no catalyst. Instead, the "B" side contained 20 grams of ArmolTM 201B-125 and 80 &commat; grams of Terate 203 as the polyol blend, and 38.5 grams of Freon llA. The blend remained in a stable and homogeneous form for seven days without agitation. Examples 16 & 17 Urethane-modified polyisocyanurate foams were manufactured in substantially the same manner as set forth in Example 5, except that instead of ArmolTM 201B-125, ArmolTM 101B-1 and ArmolTM 201B-135 were used in accordance with the data in Table 5 below. The reaction profile, densities, percent closed cells and percent friability are also shown in Table 5. The "B" sides used in the manufacture of Examples 16 and 17, like the "B" sides used in the manufacture of all of the previous foams in Examples 5-15, pass the seven day stability test. TABLE 2 Example 6 Example 7 Example 8 Example 9 Armol 210B-135 17.5 - - Armol 210B-145 - 15 - Armol 210B-155 - - 15.0 Armol 210B-175 - - - 15 Terate 203 67.5 67.5 67.5 67.5 Voranol 575 15 17.5 17. 17.5 DC-193 2.5 2.5 2.5 2.5 Freon 11A 42 43 43 41.5 Mondur MR 175.2 180.6 182.6 182.6 NCO/OH Ratio 2.0 2.0 2.0 2.0 Reaction Profile (Min:Sec) Cream Time 0:25 0:29 0:27 0:19 Gel Time 0:43 0:49 0:43 0:29 Track Free Time 1:03 1:18 0:58 0: :33 Density (gram per cc.) 0.032 0.032 0.032 0.032 Humind Aging, 70 C/100% RH, 1 day 5.73 8.25 5.66 6.30 % change in volume 7 days 7.06 10.05 6.70 6.71 Dry Aging, 93 C/ambient RH, 1 day 1.69 1.71 0.72 1.89 % change in volume 7 days 3.39 3.50 2.01 3.23 % Closed Cells 93.3 90.4 90.9 92.8 % Friability 0.9 1.95 0.62 0 TABLE 4 EMI17.1 <tb> <SEP> Example <SEP> 10 <SEP> Example <SEP> 11 <tb> Armol <SEP> 201B-125 <SEP> 20 <SEP> - <tb> Armol <SEP> 201B-135 <SEP> -- <SEP> 20 <tb> Terate <SEP> 203 <SEP> 80 <SEP> 80 <tb> DC-193 <SEP> 2.5 <SEP> 2.5 <tb> Freon <SEP> llA <SEP> 38.5 <SEP> 38.5 <tb> ondur <SEP> MR <SEP> 151.3 <tb> <SEP> 152.6 <tb> NCO/OH <SEP> Ratio <SEP> 2.0 <SEP> 2.0 <tb> Reaction <SEP> Profile <SEP> (Min:Sec) <tb> Cream <SEP> Time <SEP> 0:24 <SEP> 0:19 <tb> Gel <SEP> Time <SEP> 0:50 <SEP> 0:34 <tb> Tack <SEP> Free <SEP> Time <SEP> 1:23 <SEP> 0: :53 <tb> Density <SEP> (grm <SEP> per <SEP> cc.) <SEP> e.o3.3 <SEP> 0.033 <tb> Humid <SEP> Aging, <SEP> 70 <SEP> 0C/100% <SEP> RH, <SEP> 1 <SEP> day <SEP> 16.77 <SEP> 6.99 <tb> <SEP> % <SEP> change <SEP> in <SEP> volume <SEP> 7 <SEP> days <SEP> 18.27 <SEP> 8.54 <tb> Dry <SEP> Aging, <SEP> 93 <SEP> 0ambient <SEP> RH, <SEP> 1 <SEP> day <SEP> 3.84 <SEP> 3.44 <tb> <SEP> % <SEP> change <SEP> in <SEP> volume <SEP> 7 <SEP> days <SEP> 6.72 <SEP> 5.73 <tb> % <SEP> Closed <SEP> Cells <SEP> 92.7 <SEP> 92.7 <tb> % <SEP> Friability <SEP> . <SEP> 1.1 <SEP> 0.1 <tb> Example 12 Example 13 Example 14 Armol 101B-1 10 - Armol 101B-2 - 10 Armol 101B-125 - - 10 Terate 203 45 45 45 Voranol 575 45 45 45 DC-193 2.5 2.5 2.5 T-45 0.5 0.5 0.5 Freon 11A 50.5 48 48 One Week Stability YES YES YES TABLE 5 EMI19.1 <tb> <SEP> Example <SEP> 16 <SEP> Example <SEP> 17 <tb> Armol <SEP> 10113-1 <SEP> -- <SEP> 15.0 <tb> Armol <SEP> 201B-135 <SEP> 10.0 <SEP> - <tb> Terate <SEP> 203 <SEP> 45.0 <SEP> 67.5 <tb> Voranol <SEP> 575 <SEP> 45.0 <SEP> 17.5 <tb> T-45 <SEP> 0.5 <SEP> 0.5 <tb> DC-193 <SEP> 2.5 <SEP> 2.5 <tb> Freon <SEP> llA <SEP> 57 <SEP> 60.0 <tb> Mondur <SEP> MR <SEP> 275 <SEP> 293.6 <tb> NCO/OH <SEP> Ratio <SEP> 2.50 <SEP> 3.0 <tb> Reaction <SEP> Profile <SEP> (Min:Sec) <tb> Cream <SEP> Time <SEP> 0:36 <SEP> 0:17 <tb> Gel <SEP> Time <SEP> 1:13 <SEP> 0:21 <tb> Tack <SEP> Free <SEP> Time <SEP> 1: :48 <SEP> 0:25 <tb> Density <SEP> ( <SEP> gram <SEP> per <SEP> cc.) <SEP> o.o2E <SEP> 0.031 <tb> Humid <SEP> Aging, <SEP> 7c <SEP> 0C/100% <SEP> RH, <SEP> 1 <SEP> day <SEP> 5.1 <SEP> 4.9 <tb> <SEP> % <SEP> change <SEP> in <SEP> volume <SEP> 7 <SEP> days <SEP> 4.9 <SEP> 5.7 <tb> Dry <SEP> Aging, <SEP> 3 <SEP> OC/ambient <SEP> RH, <SEP> 1 <SEP> day <SEP> 1.2 <SEP> 1.7 <tb> <SEP> % <SEP> change <SEP> in <SEP> volume <SEP> 7 <SEP> days <SEP> 1.5 <SEP> 3.7 <tb> : :% <SEP> Closed <SEP> Cells <SEP> 85.0 <SEP> 90.7 <tb> % <SEP> Friability <SEP> 5.2 <SEP> 1.7 <tb> Example 18 A urethane-modified polyisocyanurate foam with an index of 3.0 was manufactured by blending 302 grams of Mondur MR with a Bw side comprising 17.5 grams of Armol 201B-135, 67.5 grams Foamol 250, 15.0 grams Voranol 575r 2.5 grams Dow Corning DC-193, and 61.0 grams Freon llA. The resulting foam had a cream time of 24 seconds, a gel time of 41 seconds, a tack free time of 85 seconds, a density of 0.029 gram per cc., a 3.2% friability, 92.8% closed cells, was at 105.75% of its original dimensions after seven days at 709C and 100% relative humidity, and was at 104.96% of its original dimensions after seven days at 930C and the ambient relative humidity. Example 19-23 Urethane-modified polyisocyanurate foams were manufactured in substantially the same manner set forth in Example 18, but at different indexes and frequently using Armol 201B-125 instead of Armol 201B-135. The reaction profiles, densities, percent closed cells, and percent friabilities are shown in Table 6. Examples 24-27 Urethane-modified polyisocyanurate foams were prepared in substantially the same manner set forth in Examples 18-23 but using the aforementioned D-400 resin polyol instead of Foamol 250. The particular amine/quaternary ammonium borate ester blend used and the reaction profiles and physical properties of the foams manufactured are disclosed in Table 7 below. TABLE 6 Example 19 Example 20 Example 21 Example 22 Example 23 Armol 201B-135 - - - - 17.5 Armol 201B-125 17.5 20.0 20.0 17.5 Foamol 250 67.5 80.0 80.0 67.5 67.5 Voranol 575 15 - - 15.0 15.0 DC-193 2.5 2.5 2.5 2.5 2.5 T-45 2.0 0.7 0.5 0.6 0.9 Freon 11A 68.5 63.5 56.5 61.0 68.5 Mondur MR 350.2 318.9 273.3 300.2 352.3 NCO/OH Ratio 3.5 3.5 3.0 3.0 3.5 Reaction Profile (Min:Sec) Cream Time 0:20 0:15 0:15 0:29 0:23 Gel Time 0:36 0:31 0:29 0:51 0:43 Track Free Time 1:08 2:15 1: :10 1:38 2:00 Density (gram per cc.) 0.029 0.030 0.030 0.028 0.029 Humid Aging, 70 C/ambient RH, 1 day 3.79 7.42 6.39 5.83 3.57 % change in volume 7 days 6.77 8.86 8.00 7.38 4.82 Dry Aging, 93 C/ambient RH, 1 day 2.98 2.36 2.05 1.37 3.13 % change in volume 7 days 4.75 3.28 3.04 3.51 4.23 % Closed Cells 87.3 91.7 92.3 85.0 90.1 % Friability 25.5 2.6 3.2 13.3 18.9 TABLE 7 EMI22.1 <tb> <SEP> Example <SEP> 24 <SEP> Example <SEP> 25 <tb> Armol <SEP> 201B-125 <SEP> 17.5 <SEP> - <tb> Armol <SEP> 201B-135 <SEP> -- <SEP> 17.5 <tb> .D-400 <SEP> resin <SEP> polyol <SEP> 67.5 <SEP> 67.5 <tb> iVoranol <SEP> 575 <SEP> 15.0 <SEP> 15.0 <tb> DC-193 <SEP> 2.5 <tb> T-45 <SEP> 0.7 <SEP> 0.7 <tb> Freon <SEP> 11A <SEP> 51.5 <SEP> 51.5 <tb> Mondur <SEP> MR <SEP> 237.1 <SEP> 238.9 <tb> C/ <SEP> Ratio <SEP> 3.0 <SEP> 3.0 <tb> Reaction <SEP> Profile <SEP> (in: :Sec) <tb> Cream <SEP> Time <SEP> 0:15 <SEP> 0=15 <tb> Gel <SEP> Time <SEP> 0:29 <SEP> 0:29 <tb> Tack <SEP> Free <SEP> Time <SEP> 0:38 <SEP> 0:35 <tb> Density <SEP> ( <SEP> gram <SEP> per <SEP> cc) <SEP> 0.02g <SEP> ,o31 <tb> tumid <SEP> Aging, <SEP> Jo <SEP> oc/100% <SEP> RH, <SEP> 1 <SEP> day <SEP> 5.23 <SEP> 5.11 <tb> <SEP> z <SEP> change <SEP> in <SEP> volume <SEP> 7 <SEP> days <SEP> 6.52 <SEP> 6.24 <tb> Dry <SEP> Aging, <SEP> 53 <SEP> C/ambient <SEP> RH, <SEP> 1 <SEP> day <SEP> 3.09 <SEP> 5,07 <tb> <SEP> t <SEP> change <SEP> in <SEP> volume <SEP> 7 <SEP> days <SEP> 5.33 <SEP> 6.72 <tb> t <SEP> Closed <SEP> Cells <SEP> 86.2 <SEP> 86.76 <tb> % <SEP> Friability <SEP> 9.4 <SEP> 6.5 <tb> TABLE 7 (cont.) EMI23.1 <tb> <SEP> Example <SEP> 2 <SEP> Example <SEP> Zi <tb> Armol <SEP> 201B-125 <SEP> -- <SEP> 17.5 <tb> Armol <SEP> 201B-135 <SEP> 17.5 <SEP> - <tb> D-400 <SEP> resin <SEP> polyol <SEP> 67.5 <SEP> 67.5 <tb> Voranol <SEP> 575 <SEP> 15.0 <SEP> 15.0 <tb> DC-193 <SEP> 2.5 <SEP> z., <tb> T-45 <SEP> 0.9 <SEP> 1.5 <tb> Freon <SEP> llA <SEP> 57.5 <SEP> 57.5 <tb> Mondur <SEP> MR <SEP> 278.7 <SEP> 276.6 <tb> NCO/OH <SEP> Ratio <SEP> 3.5 <tb> Reaction <SEP> Profile <SEP> (blin:Sec) <tb> Cream <SEP> Time <SEP> 0:25 <SEP> 0:26 <tb> Gel <SEP> Time <SEP> 0:43 <SEP> 0:54 <tb> Tack <SEP> Free <SEP> Time <SEP> 1:15 <SEP> 2: :30 <tb> Density <SEP> (gram <SEP> per <SEP> cc) <SEP> o.os3 <SEP> 0.023 <tb> Humid <SEP> Aging, <SEP> ?O <SEP> C/100% <SEP> RH, <SEP> 1 <SEP> day <SEP> 6.85 <SEP> 5.50 <tb> <SEP> % <SEP> change <SEP> in <SEP> volume <SEP> 7 <SEP> days <SEP> 8.94 <SEP> 5.92 <tb> Dry <SEP> Aging, <SEP> 93 <SEP> OC/ambient <SEP> RH, <SEP> 1 <SEP> day <SEP> 3.61 <SEP> 2.01 <tb> <SEP> % <SEP> change <SEP> in <SEP> volume <SEP> 7 <SEP> days <SEP> 5.29 <SEP> 4.44 <tb> % <SEP> Closed <SEP> Cells <SEP> 90.6 <SEP> 84.5 <tb> % <SEP> Friability <SEP> 3.5 <SEP> 19.1 <tb>

Claims: Claims 1. A method for the manufacture of urethane-modified polyisocyanurate foams, comprising blending an isocyanate with a "B" side, said "B" side comprising a polyol blend, a surfactant, a blowing agent, and a catalyst, said polyol blend comprising: a. at least 5% (wt.) of a mixture of a polyalkoxylated amine and a polyalkoxylated quaternary ammonium borate ester b. -at least 40% (wt.) of a resin polyol, said resin polyol compri sing at least 70% (wt.) of a combination of polymers and monomers having the general formula: EMI24.1 wherein n is between 0 and 50, R11 is either H- or CH3-, and p and q are each integers between 1 and 10; or at least 45% (wt.) of a resin polyol, said resin polyol either having the general formula EMI24.2 wherein n' is either 1 or 2 and x' is an integer between 1 and 20, inclusive or having the general formula EMI24.3 wherein n is an integer between 1 and 4 inclusive and x and y are integers each having a value of between 2 and 20, inclusive; c. the remainder of said polyol blend being a polyether or polyester polyol. 2. Method as set forth in claim 1 wherein the weight ratio of polyalko xylated amine to polyalkoxylated quaternary ammonium borate ester is between 1:0.15 and 1:12.0 when use is made of a resin polyol compri sing at least 70% (wt.) of a compound having the general formula (I). 3. Method as set forth in claim 1 wherein the weight ratio of polyalko xylated amine to polyalkoxylated quaternary ammonium borate ester is between 1:0.15 and 1:4.1 when use is made of a resin polyol having the general formula (II) or (III). 4. The method as set forth in claim 1, 2 or 3, wherein said polyalkoxy lated amine is selected from the group consisting of EMI25.1 wherein R is selected from the group of alkyl radicals having between 1 and 18 carbon atoms, x and y are integers each having a value of at least one and wherein the sum of x and y does not exceed 50 and wherein R1 and R2 may be the same or different and may be selec ted from the groups consisting of H-, CH3-, C1-C10 straight- or branched-chain alkyl or alkenyl radicals, a phenyl group, a benzyl group or halogenated alkyl group. 5. The method as set forth in claim 4, wherein R is the tallow alkyl group, R1 and R2 are each H-, and wherein x plus y equal 5. 6. The method as set forth in any of the foregoing claims, wherein said polyaloxylated quaternary ammonium borate ester is of the general formula: EMI26.1 wherein R3 is a straight- or branched-chain alkyl or alkenyl radi cal having from 1 to 30 carbon atoms, inclusive, or a phenyl or benzyl radical; R4 is H-, a C1 to C10 straight- or branched chain alkyl or alkenyl radical, a phenyl group, a benzyl group, or a halogenated alkyl group; R5 and R6 are different or the same and are selected from the group including H-, or a C1 to C10 straight or branched-chain -alkyl or alkenyl radical, a phenyl group, or a benzyl group; and wherein m is an integer between 0 to 30, inclusive. 7. The compound as set forth in claim 6, wherein R3 is a straight- or branched-chain alkyl or alkenyl radical having from 8 to 18 carbon atoms, and R4 is H-. 8. The compound as set forth in claim 6, wherein R5 and R6 are H-. 9. The compound as set forth in claim 6, wherein R5 is H- and R6 is CH3-. 10. The compound as set forth in claim 8 or 9, wherein m is O. 11. The compound as set forth in claim 10, wherein R3 is C18H37-. 12. The method as set forth in claim 1, 2 or 3, wherein said polyalkoxy lated amine is selected from the group consisting of EMI26.2 wherein R7 is selected from the group of C1-C20 alkyl groups and R8 is a C2 to C5 alkyl group; R1 and R2 are the same or different and may be selected from the groups consisting of H-, CH3-, C1 to C10 straight- or branched-chain alkyl or alkenyl radicals, a phenyl group, a benzyl group, or a halogenated alkyl group; and x and y are integers each having a value of at least 1 and a sum not exceeding 50. 13. The method as set forth in claim 1, 2 or 3, wherein said polyalkoxy lated quaternary ammonium borate ester is of the general formula: EMI27.1 wherein R4 is H-, a C1 to C10 straight- or branched-chain alkyl or alkenyl radical, a phenyl group, a benzyl group, or a halogenated alkyl group; R5 and R6 are different or the same and are selected from the group including H-, or a C1 to C10 straight- or branched-chain alkyl or alkenyl radical, a phenyl group, or a benzyl group, m is an integer between 0 and 30, inclusive, Rg is a C1-C20 alkyl group, and R10 is a C2 to C5 alkyl group.

Inventors: WHITE, KENNETH B.
Applicants: AKZO N.V.
Application year: 1984
Main classification: C08G18
IPC codes: C08G18