GB2049716A - Method for making nitrogen- containing polyols - Google Patents

Abstract

Polyols are prepared by (a) reacting ammonia, formaldehyde and a phenol having the formula: <IMAGE> wherein at least one of the positions ortho- and para- to the hydroxy group is unsubstituted, and each R is hydrogen, halogen, nitro or a C1-C12 alkyl, cycloalkyl, aryl, haloalkyl or hydroxyalkyl group, at a temperature of 20 to 100 DEG C, and (b) combining the resulting aminomethylphenol having the formula: <IMAGE> sequentially with first ethylene oxide and then propylene oxide, wherein the ethylene oxide/propylene oxide molar ratio is larger than 0.5, at a temperature of 30 to 200 DEG C. Polyurethanes produced by reacting the polyols with polyisocyanates have low friability. The polyols themselves have a viscosity low enough for convenient handling.

Description

SPECIFICATION Method for making nitrogen-containing polyols This invention concerns the preparation of polyols for use in preparing polyurethane foams.

U.S. Patent 4,137,265 discloses and claims a polyol prepared by the reaction of propylene oxide with a condensation product of phenol, formaldehyde and an alkanolamine. Canadian Patent 922,323 discloses a nitrogen-containing polyol obtained by the reaction of propylene oxide with a condensation product of phenol, formaldehyde and ammonia. Foams prepared from the polyol of the Canadian Patent have many excellent properties but are too friable to be useful. Also, the polyol of the Canadian Patent has a very high viscosity making it difficult to handle.

This invention provides a method for preparing polyol by the sequential reaction of ethylene and propylene oxide with a condensation product of phenol, formaldehyde and ammonia. The resulting polyol is similar in structure to the polyol of U.S. Patent 4,137,265 and has superior properties to the polyol of Canadian Patent 922,323.

More specifically this invention provides a method for preparing a nitrogen-containing polyol which comprises combining an aminomethyl phenol represented by the formula:

sequentially with first ethylene oxide and then propylene oxide wherein the ethylene oxide/propylene oxide molar ratio is larger than about 0.5 at a temperature within the range of about 300 to about 2000 C., said aminomethylphenol having been prepared at a temperature within the range of about 200 to about 1000C. by the reaction of ammonia, formaldehyde and phenol having the formula:

wherein at least one of the positions ortho- and para- to the hydroxy group is unsubstituted and each R is selected from the group consisting of hydrogen, halo, nitro and C1-C12 alkyl, cycloalkyl, aryl, haloalkyl and hydroxyalkyl.

The invention also provides a method for preparing a polyurethane foam using the polyol resulting from the method above.

The present polyols are obtained from a phenol, formaldehyde, ammonia and sequential addition of ethylene oxide and propylene oxide, all readily available and inexpensive starting materials, by a stepwise process. The phenol formaldehyde and ammonia are first reacted at a temperature below about 1 000C. to prepare an aminomethylphenol. The crude aminomethylphenol is then alkoxylated by reaction with an alkylene oxide at a temperature between about 300 and 2000 C.

The phenol to be employed in the present reaction is one that is unsubstituted in at least one of the positions ortho and para to the phenolic hydroxyl group. The other positions may be unsubstituted or substituted with substituent groups which are non-reactive under the conditions employed in the formation of the aminomethylphenol. Substituent groups that may be present include alkyl, cycloalkyl, aryl, halo, nitro, haloalkyl and hydroxyalkyl. Thus, acceptable phenols are those having the formula:

wherein each R is selected from the group consisting of hydrogen, halo, nitro and C1-C12 alkyl, cycloalkyl, aryl, haloalkyl and hydroxyalkyl and at least one of the positions ortho and para to the phenolic hydroxyl group is unsubstituted. The reactivity of the phenol is reduced by the presence of many substituents or bulky substituents.Examples of acceptable phenolic compounds include phenol, o-, m- arid p-cresols, ethylphenol, o-bromophenol, o-chlorophenol, p-phenylphenol, o-chloromethylphenol, 2,6-dichlorophenol, 2-nitrophenol, p-cyclohexylphenol, 3,5-dimethylphenol, nonylphenol and 2-(2-hydroxypropyl)phenol. The preferred starting materials are phenol and p-nonylphenol.

The formaldehyde employed is preferably in the form of paraformaldehyde. Formaldehyde containing water, such as formalin solution, may be used but is preferably avoided. Any water introduced with the reactants is present during the first alkoxylation step and increases the likelihood that some of the alkylene oxide will react with water to form polyglycols. For the same reason anhydrous ammonia is preferred over aqueous solutions of ammonia.

The aminomethylphenols are prepared by mixing the phenol and formaldehyde at a temperature between about 200 and 1000C., preferably 40-600C., and then adding anhydrous ammonia to the mixture at a rate to maintain the reaction temperature. The molar ratio of phenol to formaldehyde is about 1:1, while an excess of about 1.1 to about 2 mols of ammonia is employed to insure complete reaction. The use of an excess of formaldehyde generally results in the formulation of a resinous polymer.

The product from the reaction of the phenol, formaldehyde and ammonia is a complex mixture, the exact composition of which is unknown. The predominant component of this mixture is an aminomethylphenol; so for purposes of this application, the mixture will be referred to as an aminomethylphenol and will be represented by the formula:

wherein each R is selected from the group consisting of hydrogen, halo, nitro and C1-C12 alkyl, cycloalkyl, aryl, haloalkyl and hydroxyalkyl.

Attempts to remove the unreacted ammonia and water formed during the reaction from the crude reaction product by vacuum stripping may lead to decomposition. Accordingiy, the product is preferably alkoxylated using a two-step process. First, the ethylene oxide is added non-catalytically to the crude reaction product. In this first partial alkoxylation as much as one mol of alkylene oxide is added per mol of aminomethylphenol. More alkylene oxide can be added in this first step, but more is not necessary.

This addition is conducted at a temperature of about 30 to about 2000 C. Water and other volatile materials are removed by stripping at a temperature of up to about 1 250C. under partial vacuum, and additional alkylene oxide is then added to the stripped product noncatalyticaily at a temperature of about 300 to about 2000C. to produce a product having a hydroxyl number within the desired range of about 300 to about 675. Surprisingly, we found there is substantially no reaction of the alkylene oxide with the free ammonia or water in the first alkoxylation step.Generally, if all the oxide that will react in a reasonable time is added in the second alkoxylation step, a product having the desired hydroxyl number will result All the oxide may be added in one step prior to removing the ammonia and water, but this procedure increases the likelihood that some of the oxide will react with the ammonia or water.

The alkylene oxide to be employed in the process are ethylene oxide, propylene oxide added sequentially to the above described condensation product of a phenol formaldehyde and ammonia. First, ethylene oxide is added and then propylene oxide is added. The molar ratio of ethylene oxide to propylene oxide should be at least about 0.5. The condensation with ethylene oxide and propylene oxide may be carried out by merely introducing the respective oxide, under pressure if desired, into a vessel containing the Mannich reaction product of a phenol, formaldehyde and ammonia. No catalyst need be added since the basic nitrogen in the product provides sufficient catalytic activity to promote the reaction.Temperatures between about 300C and about 2000C may be employed but the preferred temperatures are in the range of about 90 to 1 1 OOC. The final condensation products are purified from unreacted and partially reacted materials by vacuum stripping and have hydroxyl numbers in the range of from 300 to 675 and viscosities between about 5,000 and 50,000 centipoises at 250C.

As pointed out above, the polyols made by the method of the present invention offer many advantages over polyols prepared by the method of Canadian Patent 922,323. The addition of the required amount of ethylene oxide to the product will be shown to impart excellent friability properties two rigid foam prepared from the polyol.

The polyols of the present invention may be used as the sole polyol component in the preparation of a polyurethane foam or may be employed with up to 70 6 of a conventional polyol. Many examples of conventional polyols are known to those skilled in the art and may include those prepared by the reaction of an alkylene oxide with a polyhydric compound selected from the group consisting of carbohydrates and aliphatic and aromatic compounds containing from about three to about eight hydroxyl groups, such as hexanetriol, pentaerythritol, sorbitol, methylglucoside, sucrose, 1 ,3,3-tris(hydroxypropoxyphenyl)propane, etc. In addition, alkylene oxide adducts of certain amines, such as, for example, ethylenediamine, aminoethylpiperazine, triethanolamine, etc., may be used.Hydroxy-terminated polyesters are also sometimes employed to prepare rigid polyurethane foams. Such polyesters are usually prepared from dibasic acids such as phthalic and adipic acids and diols or triols such as diethylene glycol, glycerine, trimethylolpropane, etc.

In preparing foams from the instant polyols, conventional foam preparation procedures are used with the exception that no extraneous catalyst is needed. Polyisocyanates, blowing agents, foam stabilizers and fire retardants useful in the preparation of rigid polyurethane foams are well known to those skilled in the art. Both one-shot and quasi-prepolymer processes may be employed.

If the quasi-prepolymer method is used to prepare rigid urethane foam in accordance with the present invention, it is preferred that the quasi-prepolymer be prepared by reacting a conventional polyol of the type above-described with an amount of polyisocyanate sufficient to provide from about 20-40 wt.% of free isocyanato groups (based on the total amount of polyisocyanate used) in the quasi-prepolymer reaction product. An amount of the polyol of the present invention sufficient to provide about one hydroxyl group per free isocyanato group in the quasi-prepolymer is then added to the quasi-prepolymer in the presence of a foam stabilizer, a blowing agent and, if desired, a fire retardant.

The most commonly used foam stabilizers are organic silanes or siloxanes, usually silicone-glycol copolymers. Such a material might be one having the formula: R' Si [0-(R2Si O), -(Oxyalkylene),R"], wherein R, R' and R" are alkyl groups containing 1-4 carbon atoms, n is 4-8, m is 20-40 and the oxyalkylene groups are derived from ethylene or propylene oxides.

Blowing agents used in the preparation of urethane foams are described, for example, in United States Patent No. 3,072,582. Blowing agents are generally volatile liquids, such as fluorocarbons.

Blowing of foams is sometimes accomplished by using a small amount of water and an excess of polyisocyanate. The water reacts with the isocyanate, generating carbon dioxide which acts as the blowing agent.

Fire retardants that can be incorporated in the foaming mixture are of two types. The first of these comprises those that are incorporated by mere mechanical mixing and include, for example, tris(chloroethyl)phosphate, tris(2,3-dibromopropyl)phosphate, diammonium phosphate, various halogenated compounds and antimony oxide. The second type of fire retardant comprises those that become chemically bound in the polymer chain. Examples of this type include chlorendic acid derivatives and various phosphorous-containing polyols.

Although normally an amine catalyst such as triethylenediamine, triethylamine, dimethylpiperazine, N-methylmorpholine, N-ethylmorpholine or N,N,N',N'-tetramethylbutanediamine is used in the preparation of a polyurethane foam, such a catalys is not necessary when the polyols of the present invention are used. If a faster rise time or tack-free time is desired, one of the above-desired amine catalysts and/or a metallo organic catalyst may be added. Metallo organic catalysts that may be used are well known to those skilled in the art. The most common of such catalysts are organic tin compounds such as stannous octoate, stannous laurate, dibutyltin dilaurate, dibutyltin oxide, etc.

Polyisocyanates useful in the preparation of polyurethane foams are well known to those skilled in the art. Such a polyisocyanate is suitably an organic aromatic or aliphatic polyisocyanate such as, for example, diphenyl-4,6,4'-triisocyanate, 3,3'-dichloro-4,4'-biphenyl diisocyanate, diphenyl diisocyanate, ethylene dissocyanate, propylene-l ,2-diisocyanate, octamethylene diisocyanate, 1,4-tetramethylene diisocyanate, m-and p-phenylene diisocyanates, xylene- 1 ,4-diisocynate, xylene- 1, 3-diisocyanate, naphthylene-1 ,4-diisocyanate, 2,4- and 2,6-toluene diisocyanates, o,o'-, o,p'- and p,p'diphenylmethane diisocyanates, p-isocyanatobenzyl isocyanate, polymethylene polyphenylisocyanate, and mixtures thereof.

The use of the polyols of the present invention in the preparation of polyurethane foams will be further illustrated by the following specific examples of foams prepared by the one-shot method. All of the foams were prepared by mixing all the components except the polyisocyanate. The polyisocyanate was then added, the mixture was stirred and was then poured into an open mold where it was allowed to rise. The formulations, processing details and foam properties are shown in the following table. The polyisocyanate used was a polymethylene polyphenylisocyanate.

EXAMPLE 1 To a 15 gallon kettle was added 18.8 Ib. (0.20 lb. mole) of melted phenol, which was heated and stirred under a nitrogen pad at 400C while 17.0 Ib. (0.21 lb. mole) of 37% aqueous formaldehyde was added slowly so as to keep the temperature below 400C. Then, 3.6 lb. (0.21 lb. mole) of anhydrous ammonia was pressured in from the bottom of the kettle at a rate to maintain the temperature between 4o-600C (Exotherm to 50-600C at first). This mixture was digested at 50-600C for one hour.

Then, 17.6 Ib. (0.40 Ib. mole) of ethylene oxide was added slowly over a 1 1/2 hour period holding the temperature at 50-550C. The mixture was then heated up to 950C where it was digested for one hour I before cooling overnight (7 hours).

The mixture was heated to 1000C and the condensate was stripped of water down to 5-7 mm Hg. A total of 13.55 lb. H20 was removed.

The condensate was heated at 95-1 000C while 34.8 Ib. (0.60 lb. mole) of propylene oxide was added over a two hour period. The mixture was digested for another hour and the excess oxide was vented. The mixture was then stripped down to 57 mm Hg and 4.6 lb. oxide and water was removed.

Yield was 70.40 lb of dark yellow, clear viscous liquid.

Molar ratio of ethylene oxide/propylene oxide in reaction mixture = 0.67.

Product Analysis Hydroxyl No. 501 Total Amine (meg/g.) 2.83 Viscosity (250C) 15,300 cp Color (Gardner) 6 Wt. % H20 0.059 pH 10.7 EXAMPLE 2 To a 15 gallon kettle was added 22.0 lb (0.10 lib. mole) of p-nonyl phenol which was stirred under nitrogen at about 300C while 17.0 Ib. (0.21 lb. mole) of 37% aqueous formaldehyde was added slowly so as to keep the temperature below 400 C. Then, 3.6 Ib. (0.21 Ib. mole) of anhydrous ammonia was pressured in from the bottom of the kettle at a rate so as to maintain the temperature between 40--600C. The resulting mixture was then digested at 50-600C for one hour and cooled overnight under N2. (About 5 hours.) The above mixture was heated up to 500C and the addition of 1 7.6 lb. (0.40 lb. mole) ethylene oxide was started at a rate so as to maintain a temperature between 50--600C (1 1/2 hours). The mixture was heated up to 1000C and digested there for one hour. Then the mixture was stripped under vacuum to remove 14.76 Ib. water and volatiles. A sample of the condensate was taken (golden yellow and very viscous). Then 29.0 lb. (0.50 Ib. mole) propylene oxide was added slowly over a 2 1/2 hour period ending up with a pressure of 55 psi. A digestion period of 2 1/2 hour lowered the total pressure to 46 psi before cooling overnight.

The above reaction mixture was heated up to 100-1 050C and the excess oxide was vented (-4.35 Ib.). The mixture was then stripped down in high vacuum to 6 mm Hg/1 050C. Yield-was 66.4 Ib.

of clear, red viscous liquid.

Molar ratio of ethylene oxide/propylene oxide in reaction mixture = 0.80.

Product Analysis Hydroxyl No. 423 Total Amine 2.97 Vis. (250C) 17,750 cp Wt. % H20 0.020 Color 7.0 EXAMPLE 3 To a 5 gallon kettle was added 8.0 Ib. (0.085 lb. mole) of melted phenol, which was heaed and stirred under a nitrogen pad at 400C while 7.3 lb.(0.90 Ib. mole) of 37% aqueous formaldehyde was added so as to keep the temperature to less than 450C. Then, 1.60 lb. (0.94 Ib. mole) of anhydrous ammonia gas was pressured in from the bottom of the kettle at a rate so as to maintain the temperature between 40--500C. After the addition the mixture was digested at 50-600C for one hour.

The above reaction was heated at 500C while 6.6 lb. (0.150 lb. mole) ethylene oxide was added at a rate so as to keep the temperature at 50-600C. Then, 2.32 (0.40 lb. mole) propylene oxide was added while keeping the temperature to less than 600 C. After this addition, the mixture was heated up to 95-1 000C where it was digested for one hour. Vacuum was then applied to strip off 6.45 lb. water and yield the Mannich condensate.

To the Mannich condensate (4711-30-1) whch was stirred and heated at 11 O0C, was added 11 .E Ibs. (0.200 Ib. mole) propylene oxide while keeping the temperature to less than 11 50C. After the addition, the mixture was digested for one hour before venting any excess PO (1.0 lb.) The product was finally stripped in high vacuum down to 5 mm Hg/i 050C to yield about 30 Ibs (28.40 Ib) of a golden yellow product.

Molar ratio of ethylene oxide/propylene oxide in reaction mixture = 0.25.

Product Analysis Hydroxy No. 512 Viscosity (250C) 15,000 cp Total Amine 2.94 Wt. % H20 0.02 EXAMPLE 4 To a 5 gallon (Buflovac) kettle was added 11.0 Ib. (0.05 Ib. mole) of p-nonyl phenol which was stirred under N2 at about 300C while 8.1 Ib (0.10 lib. mole) of 37% aqueous formaldehyde was added while keeping the temperature to less than 400 C. Then, 1.80 Ib. (0.106 lb. mole) of anhydrous ammonia was pressured in through the oxide feed line while maintaining the reaction temperature between 40-500C. The resulting mixture was heated up slowly to 90-1 000C and digested there for 2 hours.

The above mixture was cooled to 500C and 8.8 Ib. (0.20 Ib. mole) of ethylene oxide was added in slowly while keeping the temperature to less than 600 C. After the EO addition the reaction mixture was heated up to 100--1 100C and digested there for one hour. High vacuum was then applied down to 5 mm Hg/1050C to remove about 7.0 Ib. water.

The condensate mixture was heated at 100-1 050C and 11.0 Ib. (0.190 Ib. mole) propylene oxide was added while keeping the reaction temperature to less than 11 00C. After completing the addition, the mixture was digested at 1 1 OOC for one hour or until constant pressure was reached. Then, the product was stripped in high vacuum down to 5 mm Hg/i 1 00C.

Yield was 25.95 lb.

Molar ratio of ethylene oxide/propylene oxide in reaction mixture = 1.0.

Product Analysis Hydroxyl No. 469 Viscosity (250C) 36,000 cp Total Amine 3.20 Wt.%H20 0.01 Color 7 pH 10.7 EXAMPLE 5 POLYURETHANE FOAMS PREPARED FROM ABOVE POLYOLS Formulation, pbw. Example 1 Example 2 Example 3 Example 4 Polyol from Ex. 1 38.5 Polyol from Ex. 2 41.5 Polyol from Ex. 3 38.1 Polyol from Ex. 4 39.9 Silicone DC-193 0.5 0.5 0.5 0.5 EXAMPLE 5 (Continued) POLYURETHANE FOAMS PREPARED FROM ABOVE POLYOLS Formulation, pbw. Example 1 Example 2 Example 3 Example 4 FreonR-11-B 13.0 14.0 13.0 13.0 Thanate P-270 (1.05=lndex) 48.0 44.0 48.4 46.6 Mixing Time (Sec.) 15 10 15 13 Cream Time (Sec.) 26 12 33 17 Tack Free Time (Sec.) 120 90 130 60 Rise Time (Sec.) 170 160 200 120 Initial Surface Friability V.Slight None Yes None Foam Appearance Good Good Good Density (Ib/ft.3) 2.01 1.98 1.97 2.06 K-Factor 0.119 0.123 0.122 0.117 Impressive Strength With Rise (psi) 45.81 35.96 44.24 41.96 X Rise 16.08 14.25 10.65 16.24 Heat Distortion (OC) 143 142 136 161 % Closed Cells 93.02 93.78 93.79 93.86 ASTM 1692 Burn (BHA) in/sec 1.72/52/3 3.8"/min 3.8"/min 3.8"/min ASTM 1692 Burn in/min (AHA) 2.15/54.3 *Friability (% Wt.Loss) 2.7 0.6 0 3.6 Dimentional Stability AV AW AL AV AW AL AV AW AL AV AW AL 580F, 100% RH, 1 week +3.6 +0.7 +2.0+14.6-0.8 +8.2 +1.2 -1.0 +1.0 +4.8 -0.4 +3.0 800F,Dry, 1 week +2.2 +0.2 +1.8 +6.8 - +4.0 +2.6 +0.7 +1.3 +3.1 -0.4 +1.7 -200F, Dry, 1 week -3.6 +0.4 -1.8 -3.8 - -2.2 -2.2 +0.5 -1.3 -3.0 +0.4 -1.7 * Small cube of foam about 1/2"x1/2"x1/2" is tumbled for 10 minutes in cylindrical screen cage.

Wt. loss is measured. % wt. loss recorded.

Examples 6,.7 and 8 directly compare the friability of rigid foam made with a polyol prepared according to the invention (Example 7) compared to one prepared according to the method in Canadian Patent 922,323 (Example 6). Foams made from the two polyols are shown in Example 8 where a hand measurement comparison of friability is shown. Example 9 shows foam made from the polyols of Examples 6 and 7 and Example 10 compares their friability characteristics using a mechanical testing device.

EXAMPLE 6 PREPARATION OF A POLYOL ACCORDING TO CANADIAN PATENT 922,323 Raw Materials Ibs. Ib.-mole mole ratio Phenol 8.0 .085 1.00 37% Formaldehyde 7.6 .093 1.10 Ammonia, anhydrous 1.74 .102 1.20 Oxide (Propylene) 9.9 .170 2.0 Propylene oxide, st addn. 2.5 .043 0.5 Propylene oxide, 2nd addn. 12.0 .207 2.43 To a 5-gallon kettle was added the melted phenol, which was heated and stirred under a nitrogen pad at 400C while the aqueous formaldehyde was added slowly so as to keep the reaction temperature at less than 450C. Then, anhydrous ammonia was pressured in from the bottom of the kettle while maintaining the temperature between 40-500C. After the addition, the resulting mixture was digested at 50-600C for one hour.

While the reaction mixture was heated at 500C, the propylene oxide was added so as to keep the reaction temperature at less than 600C. Then, the propylene oxide addition was carried out (C600C).

After these oxide additions, the mixture was heated up to 95-1 000C where it was digested for one hour. Vacuum was applied and 6.5 Ib. water stripped off leaving the Mannich condensate mixture.

While heating the condensate at 11 00C, the second propylene oxide addition was carried out while keeping the kettle temperature at less than 115 C. The mixture was then digested for one hour before any excess oxide was vented. The product was finally vacuum stripped down to 5 mm Hg/i 050C. The golden-yellow, viscous polyol was obtained in the amount of 31.15 Ib. Cycle time was 12 hours.

Product Analysis Method Result Hydroxyl number, mg KOH/g ST-31.13-7 566 Total amines, meg/g ST-5.22 3.40 Viscosity, cps at 250C Brookfield 121,000 Color, Gardner 3-4 Water, wt 9/0 ST-31.53 0.17 EXAMPLE 7 PREPARATION OF POLYOL ACCORDING TO THE PRESENT INVENTION Raw Materials Ibs. Ib.-mole mole ratio Phenol 8.0 .085 1.00 37% Formaldehyde 7.6 .093 1.10 Ammonia, anhydrous 1.74 .102 1.20 Ethylene oxide 7.5 .170 2.0 Propylene oxide, st addn. 2.5 .043 0.5 Propylene oxide, 2nd addn. 12.0 .207 2.43 To a 5-gallon kettle was added the melted phenol, which was heated and stirred under a nitrogen pad at 400C while the aqueous formaldehyde was added slowly so as to keep the reaction temperature at less than 450C.Then, anhydrous ammonia was pressured in from the bottom of the kettle while maintaining the temperature between 40-500C. After the addition, the resulting mixture was digested at 50-600C for one hour.

While the reaction mixture was heated at 500 C, the ethylene oxide was added so as to keep the reaction temperature at less than 600 C. Then, the first propylene oxide was carried out ( < 600C). After these oxide additions, the mixture was heated up to 95-1 000C where it was digested for one hour.

Vacuum was applied and 6.5 Ib water stripped off leaving the Mannich condensate mixture.

While heating the condensate at 11 00C, the second propylene oxide addition was carried out while keeping the kettle temperature at less than 11 SOC. The mixture was then digested for one hour before any excess oxide was vented. The product was finally vacuum stripped down to 5 mm Hg/1 050C. The golden-yellow, viscous polyol was obtained in the amount of 31.15 Ib. Cycle time was 12 hours.

Product Analysis Method Result Hydroxyl number, mg KdH/g ST-31.13-7 547 Total amines, meg/g ST-5.22 3.19 Viscosity, cps at 250C Brookfield 16,000 Color, Gardner 4 Water, wt % ST-31.53 0.03 EXAMPLE 8 FOAMS MADE FROM POLYOLS OF EXAMPLES 6 s 7 Formulation, pbw. Example 6 Example 7 Polyol from Example 6 35.7 Polyol from Example 7 36.9 Silicone DC-193 0.5 0.5 Freon R-1 1-B 13.0 13.0 EXAMPLE 8 (Continued) FOAMS MADE FROM POLYOLS OF EXAMPLES 6 a 7 Formulation, pbw.Example 6 Example 7 Mondur MR 50.8 49.6 Isocyanate Index 1.05 1.05 Mixing Time (Sec.) 1 5 1 5 Cream Time (Sec.) 83 29 Tack Free Time (Sec.) 300 105 Rise Time (Sec.) 420 1 50 Initial Surface Friability Very** Slight* Foam Appearance Good Good Density (lb./ft.3) 1.91 1.89 K-Factor 0.130 0.118 Compressive Str. (psi) With Rise 38.45 41.58 Perpendicularto Rise 17.08 16.75 Heat Distortion (OC) 178 155 % Closed Cells 90.97 92.86 Friability (Int.) % Wt.Loss 25.3 7.4 Dimentional Stability AV AW AL AV AW AL 58 F,100% RH,1 Week +1.0-0.4 +1.2 +1.4-0.2 +1.3 800F, Dry, 1 Week +2.4 +0.3 +1.8 +1.4 -0.1 +1.2 -200F,Dry, 1 Week -3.3 +0.1 -1.8 -3.5 +0.4 -1.8 *No friability after 1 5 minutes.

**Very friable even after 24 hours.

EXAMPLE 9 FOAMS MADE FROM POLYOLS OF EXAMPLES 6 & 7 The following foams were made from the polyols of Examples 6 and 7 rhe resulting foams were tested in Example 10 following.

Formulation, pbw. Example 6 Example 7 Polyol from Example 6 35.7 Polyol from Example 7 36.9 Silicone DC-193 0.5 0.5 Freon R-1 1-B 13.0 13.0 Mondur MR 50.8 49.6 Isocyanate Index 1.05 1.05 Mixing Time, Sec. 15 15 Cream Time, Sec. 85 25 Tack Free Time, Sec. 300 100 Rise Time, Sec. 400 150 r EXAMPLE 10 SURFACE ABRASION TEST Instrument: Crockmeter (Model CM-5) Manufacturer: Atlas Electric Drives Description of Test The foams made in Example 9 were tested as follows: The top of each foam was cut off at about one inch below the top surface. Each of the two pieces of foam was cut into three 4" x 4" squares.The surface of each square was subjected to 200 abrasion strokes (100 cycles) by a one inch wide metal arm, which was covered with a carborundum emery cloth (Course-J-1 35R). Each stroke was 2" in length. The initial height and weight of each sample was recorded. After the testing was completed, the final height and weight of each sample was recorded.

From this data as shown in the attached table, the % weight loss and % height loss of each sample could be calculated. The average of the three samples of each foam is also shown.

RESULTS FROM SURFACE ABRASION TEST Initial Final Initial Final Weight Thickness Percent Percent Weight Weight Thickness Thickness Loss Loss Weight Thickness Foam (See Ex. 8) grams Grams inches inches grams inches loss loss Example 7 8.02 7.88 1.000 0.878 0.14 0.122 1.7 12.2 Example 7 8.17 8.11 0.989 0.908 0.06 0.081 0.7 8.2 Example 7 7.15 7.03 0.930 0.895 0.12 0.035 1.7 3.8 Average - - - - - - 1.4 8.1 Example 6 9.41 8.75 0.922 0.880 0.66 0.11 7.0 11.1 Example 6 10.68 9.93 1.045 0.950 0.75 0.295 7.0 23.7 Example 6 8.42 7.52 0.988 0.700 0.90 0.288 10.7 29.1 Average - - - - - - 8.2 21.3

Claims (13)

1. A method for preparing a nitrogen-containing polyol which compnses (a) reacting ammonia, formaldehyde and a phenol having the formula:

wherein at least one of the positions ortho- and para- to the hydroxy group is unsubstituted, and each R is hydrogen, halogen, nitro or a C1-C12 alkyl, cycloalkyl, aryl, haioalkyl or hydroxyalkyl group, at a temperature of 20 to 1000C, and (b) combining the resulting aminomethylphenol having the formula

sequentially with first ethylene oxide and then propylene oxide, wherein the ethylene oxide/propylene oxide molar ratio is larger than 0.5, at a temperature of 30 to 2000C.

2. A method as claimed in Claim 1 wherein the phenol is phenol or nonyl phenol.

3. A method as claimed in Claim 1 or 2 wherein the formaldehyde is employed in the form of paraformaldehyde.

4. A method as claimed in any preceding Claim wherein the temperature in step (a) is from 40 to 600C.

5. A method as claimed in any preceding Claim wherein from 1.1 to 2 moles of ammonia are employed in step (a).

6. A method as claimed in any preceding Claim wherein the temperature in step (b) is from 90 to 1 100C.

7. A method as claimed in any preceding Claim wherein step (b) is conducted by adding ethylene oxide to the aminomethylphenol at a temperature of 30 to 2000C, stripping water and any other volatiles under reduced pressure of up to 1 250C, and adding the propylene oxide at a temperature of 30 to 2000 C.

8. A method for preparing a polyurethane which comprises reacting an organic polyisocyanate with a nitrogen-containing polyol as claimed in any of the preceding Claims.

9. A method as claimed in Claim 8 wherein the nitrogen-containing polyol is employed with up to 70% of a conventional polyol.

10. A method as claimed in Claim 1 and substantially as hereinbefore described with reference to any of Examples 1,2,4and7.

11. A nitrogen-containing polyol prepared by a method as claimed in any of Claims 1 to 7 and 10.

12. A method as claimed in Claim 8 and substantially as hereinbefore described with reference to any of Examples 5, 8 and 9.

13. A polyurethane when prepared by a method as claimed in any of Claims 8, 9 and 12.