CA1203932A - Process for preparing polyol-catalyst mixtures useful in the preparation of rigid polyurethane cellular products - Google Patents

Abstract

PROCESS FOR PREPARING POLYOL-CATALYST
MIXTURES USEFUL IN THE PREPARATION
OF RIGID POLYURETHANE CELLULAR PRODUCTS
ABSTRACT OF THE DISCLOSURE
Polyol-catalyst mixtures, useful in the preparation of rigid polyurethane cellular products, are prepared simul-taneously by reacting a Mannich base compound, water, and an epoxide and subsequently removing the water from the reaction mixture. Also provided are new rigid polyurethane cellular products having a high content of isocyanurate linkages, superior heat distortion temperatures and improved insulating properties, which products are obtained by reacting a poly-isocyanate with the aforementioned polyol-catalyst mixture.

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Description

~3~;~32 BACKGROUND_OF THE INVENTION

1. Field of the Invention . . .. ..... . . .
This invention relates to a new process for prepar-ing polyol-catalyst mixtures. More particularly, the inven-tion relates to a new process for preparing polyol-catalyst mixtures which are useful in the preparation of improved rigid polyurethane cellular products.
Specifically, the invention provides a new process for simultaneously preparing a polyol-catalyst mixture which can be used to produce improved rigid polyurethane cellulax products, which process comprises reacting a Mannich base compound, water and an epoxide, such as ethylene oxide, together at an elevated temperature, and subsequently remov-ing the water from the reaction mixture. The invention further provides new and valuable polyurethanes, and particu-larly new rigld polyurethane cellular products having a high content of isocyanurate linkages, improved heat distortion temperatures and improved insulating properties, which prod-ucts are prepared by reacting the aforementioned polyol-0 catalyst mixture with a polyisocyanate.20 Description of the Prior Art It is known to prepare rigid polyurethane foams by the reaction of a polyisocyanate with a hydroxyl-terminated polyester, polyether or polyamine, which generally have hydroxyl numbers within the range of from about 350 to 900.
However, to date no ideal polyol has been found and, for various reasons, polyurethane foams prepared from such polyols have not been entirely satisfactory.

Still furtherr the production of a satisfactory urethane foam requires that the relative rates of the various reactions that occur be properly balanced. This balance is l 3~

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normally obtained by careful selection of a catalyst system.
The catalyst usually consists of a tertiary amine used alone or, when necessary, mixed with organic tin compounds in a manner well known to those skilled in the art. The tertiary amines so employed will normally impart an objectionable odor to the final foam product.
V. S. 3,297,597 proposes the use of certain nitrogen-containing polyols which act both as a polyol and a catalyst in the reaction with the polyisocyanates. This avoids some of the difficulties noted above, such as the odor of the amine catalyst, but still retains some of the limitations of the prior known products, such as limited heat resistance, limited compatibility and limited isocyanurate linkages retained in the cured product.
It is an object of the invention, therefore, to provide a new process for preparing polyol-catalyst mixtures useful in the preparation of polyurethane foams. It is a further object to provlde a process for preparing new polyol-catalyst mixtures which impart many improvements to the pxeparation of rlgid polyurethane cellular products. It is a further object to provide new polyol-catalyst mixtures for polyurethane foam preparation which permit the production of products having a higher number of isocyanurate linkages. It is a further object to provide new polyol-catalyst mixtures for polyurethane production which permits slower and more desirable reaction. It is a further object to provide new polyol-catalyst mixtures which give polyurethane foamed products having improved heat resistance and insulation properties. It is a further object to provide new polyol-3~ catalyst mixtures which have better compatibility with thereaction components. It is a further object to provide new ~2--~2(~3~332 polyol-catalyst mixtures which are simple and economical to prepare. These and other objects of the invention will be apparent from the following detailed description thereof SUMMARY OF TH _INVENTION
It has now been discovered that these and other objects may be accomplished by the new polyol-catalyst mix-tures of the present invention which are prepared in good yield by reacting a Mannich base compound, water and an epoxide, such as ethylene oxide, together at an elevated temperature, and then removing the water from the reaction mixture. It was surprising to find that polyol-catalyst mixtures havlng superior properties could be obtained by this straightforward economical process. It was found, or example, that the new polyol-catalyst mixtures formed it this manner had excellent compatibility with the ingredients used in the formation of polyurethane foams. In addition, the new polyol-caialyst mixtures permit better control over the rate of reaction and yielded improved products. The products Jo pre-pared, for example, haue a higher number of isocyanurate

2~ linkages and greatly improved heat resistance properties as well as excellent insulat1ng properties. The production of products having these improved properties is illustrated in the examples at the end of the specifIcation.
DETAILED DESCRIPTION OF TIE INVENTION
The process for produc1ng the new polyol-catalyst mixtures having the improved properties is made up of the following steps:
(a) mixing a Mannich base compound, water and an epoxide, such as ethylene oxide, together in a reaction cham-ber and heating the mixture to a temperature below about 150C. and, 3L2~3~3Z

(b) subsequently strippiny the water from the reaction mix ture .
The process for using the above noted polyolca-talyst mixtures in the preparation of improved rigid polyurethane cel-lular products comprises reacting the said polyol-catalyst mix-ture with the desired polyisocyanate and other components, such as blowing agent, stabilizer, fire-retardant, etc. in the desired proportions.
In order to present the inventive concept of the present invention in the greatest possible detail, the following supple-mentary disclosure is submitted.
The Mannich base used in the preparation of the new polyol-catalyst mixtures are prepared by reacting a phenolic compound with formaldehyde and an alkanolamine. Particular examples would be the reac-tion product of an alkylphenol, an alkanolamine and formaldehyde or an alkylphenol, dialkanolamine and formaldehyde. The Mannich reaction is conducted by premixing the phenolic compound with a desired amount of the alkanolamine and then slowly adding formaldehyde to the mixture at a tempera-ture below the temperature of Novolak formation (a temperaturethat will vary with the phenolic compound employed and is a temperature of less than about 35C. when phenol itself is em-ployed)~ At the end of the formaldehyde addition, the reaction mixture is slowly heated with agitation to a temperature of at least about 50C. such as a temperature within the range of about 80C. to 150C. for a period of time sufficient to reduce the formaldehyde content to at least about 1 wt percent. This will normally require from about two to about four hours reaction time at the elevated temperature.

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The pheno]ic compound to be employed in the Mannich condensation is an aromatic compound containing one or more hydroxyl groups attached directly to the aromatic nucleus and having a hydrogen atom on one or more of the ring positions 4a -~QL~5~3Z

ortho and para to the hydroxyl group and which is otherwise unsubstituted or substituted with substituents which are non-xeactive under Mannich reaction conditions. Substituent groups that may be present include alkyl, cycloalkyl, aryl, halo, nitro, carboalkoxy, haloalkyl and hydroxyalkyl. The phenolic compound is further characterized by a molecular weight within the range of from about 94 to about 500.
Examples of acceptable phenolic compounds include, among others, o- r m-, or p-cresols, ethylphenol, nonylphenol, p-phenylphenol, 2,2-bis(4~hydroxyphenyl~propane, beta-naphthol, beta-hyaroxyanthracene, p-chlorophenol, o-bxomophenol, 2,6-chlorophenol, p-nitrophenol, 4-nitro-6-phenylphenol, 3,5-dimethylphenol, p-isopropylphenol, 2-bromo-4-cyclohexyl-phenol, 2-(4-hydroxyphenyl)ethanol, and 4-chlorophenol : 15 The alkanolamine to be reacted with the phenolic compound and formaldehyde in accordance with the method of maying the Mannich bases is an alkanolamine and preferably : those of the formula H /R
H0-(C)n-N
I \

wherein R is hydrogen or an alkyl radical preferably contain-ing 1 to 4 carbon atoms, at least one Rl or R~ is hydrogen and the remaining Rl or R2 is hydrogen or a hydrocarbon or substituted hydrocarbon radical and n is an integer, ; preferably 2 to 6.
Examples of suitable alkanolamines that may be used 't'S p r~Da ~o/a n; no are monoethanolamine, diethanolamine, isvpropanolamine,~

: : bis(2-hydroxypropyl)amine, hydroxyethylmethylamine, N-hydroxy-ethylpiperazine, N-hydroxybutylamine, N-hydroxyphenyl-2,5-dimethylpiperazine, etc.

.

~Z~32 Formaldehyde may be employed in the Mannich reaction in any of its conventional forms, such as an aqueous formalin solution, an inhibited methanol solution, paraformaldehyde, or trioxane.
The proportions of reactants used in making the Mannich bases may vary over a wide range depending upon the type of product desired. For example, if phenol, diethanol-amine and formaldehyde are employed in a molar ratio of 1:3:3, the predominant product will have seven hydroxyl groups attached to a single molecule. If the molar ratio of these same reactants is changed to 1:2:2, a pentol will be obtained as the predominant product. Similarly, when the molar ratio is 1:1:1, a triol is the predominant product. If an excess of formaldehyde is used in preparing the triol or pentol, the Mannich reaction becomes complex due to the secondary conden-sation of phenol with formaldehyde.
The Mannich products possess a plurality of I.
hydroxy-terminated side chains available for further reaction with the epoxide. The preferred Mannich products may be ; 20 represented by the following formula Ox Rl--C 11 --R
C C
C
Rl wherein the Rl's represent hydrogen or a -CH2N(XOH)2 radical wherein X is an alkylene radical containing up to 8 carbon atoms. The product prepared from phenol, diethanolamine and formaldehyde in a 1:3:3 ratio may be represented by the formula 3~33Z

- CH2 - C C CH? N

C
Cl2 The exact structure of the Mannich bases will depend upon the proportion of reactants employed but they will all possess a plurality of active hydroxy terminated side chains.
A detailed description of the preparation of suitable Mannich bases may be ound in U. S. 3,297,597.
As noted in U. 5. 3,297,597, water is formed in the reaction and in that particular case, special care is taken : to remove the wa ter as notPd in col . 2, line 34 of that patent.
however, in the present process, the water is not removed but retained in the reaction to participate in the reaction with :~ the alkylene oxide. For desired results, the amount of water to be retained in the reac:tion mixture should be at least 2 by welght, and preferably between 5~ and 25~ by weight.
: As noted above, the new polyol-catalyst mixtures are obtained by reacting the above-noted Mannich bases with water and an epoxide, and preferably an alkylene oxide. The epoxide to be used include the mono- and polyepoxides, and particularly those of the formula ' `
wherein both Rs can be hydrogen or an organic radical, preferably containing up to 12 carbon atoms. Examples of ~35~3;~

the epoxides include, among others, butadiene monoepoxide, epichlorohydrin, styrene oxide, ethylene oxide, propylene oxide, butylene oxide, cyclohexeneoxide, epoxypropylbenzene, epoxypropylnapthalene, 1,2,5-triepoxypropylbenzene, and the like, and mixtures thereof. Particularly preferred are the aliphatic monoepoxides containing 2 to 8 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide.
The amount of the epoxide to be used in the prepa-ration process may vary over a wide range In general, theamount of the alkylene oxide may vary from about 1 to 10 times the amount ox the Mannich base, but should be sufficient to react with a majority of the -XOH groups in the Mannich base.
Preferably the epoxide is employed in amounts varying from about 2 to 6 moles per mole of Mannich base.
The Mannich base, water and epoxide can be combined in any order but it is generally preferred to add the epoxide to the reaction mixture containing the Mannich base and water.
Temperatures employed in the process may vary within a wide range. In general, it is desirable to maintain the tempera-ture below about 150C., and more preferably between about 90C. and 125~C. Atmospheric, superatmospheric or subatmos-pheric pressures may by utilized as desired or necessary.
The heat is continued until the desired polyol-catalyst mixture is obtained. In general, this is accomplishedwith reaçtion periods varying from about .5 hour to about 3 hours, depending upon the nature of the reactants and the temperature employed.
At the conclusion of the reaction, the water and other low molecular weight products such as excess epoxide are stripped from the reaction mixture. This is preferably accomplished by distillation under high vacuum.
The polyol-catalyst mixtures prepared by the above process may be recovered as liquids or soft solids. They will preferably have a hydroxyl number varying from about 300 to 1000, an amine content varying from 2 to 3 meg~g., color as determined by the Gardner scale of about 8 to 15 and a pH
varying from about ~0 to about 12.5.
As noted above, the new polyol-catalyst composition produced as above are particularly valuable in the reaction with isocyanates to form polyurethanes or polyisocyanurates.
They are particularly outstanding in the reaction with poly-isocyanates to form rigid cellular polyurethanes that have greatly improved properties. In this reaction they are com-lS bined with desired polyisocyanate and other componentsgenerally used in the formation of cellular products, such as blowing agents, flre retardants, stabilizers,~étc., and the reaction effected by use of known techniques.
The polyisocyanates to be used in making the foams of the present inventian include those compounds containing at least two isocyanate groups per molecule, such as, for example, tolylene diisocyanate (TDI), hexamethylenediiso-cyanate, chlorophenyldiisocyanate, bromophenyldiisocyanate, tetraisocyanatodiphenylmethane, 3,3'-dichloro-4,4'-biphenyl-diisocyanate, diphenyl diisocyanate, ethylene diisocyanate,propylene 1,2-di~isocyanate, 1,4-tetramethylene diisocyanate, p-phenylene diisocyanate, polymethylene polyphenylisocyanate 7 and mixtures thereof. Preferred polyisocyanates include the organic aromatic, aliphatic or.cycloaliphatic polyisocyanates.
Coming under special consideration are the prepolymers obtained by reacting active hydrogen containing compounds, _g_ 3~3;2 such as alcoho.ls or amines with excess polyisocyanates, which polymers contain a plurality of free isocyanate groups such as from 3 to 8 such groups.
Also of special consideration are the aromatic poly-isocyanates preferably having from 2 to 6 isocyanate groups, more preferably those such as, for example, 2,4- and 2,6-toluene diisocyanates and methylene-bridged polyphenyl polyisocyanate mixtures which have a functionallty of from about 2 to ahout 4.
These latter isocyanates compounds are generally produced by the phosgenation of corresponding methylene-bridged polyphenyl poly-amines. Yost preferred methylene-bridged polyphenyl poly-isocyanates mixtures contain about 20 to 100 weight percent methylene diphenyldiisocyanate isomer, with the remainder being polymethylene polyphenyl polyisocyanates having higher function-ality and higher molecular weights.
The most commonly used foam stabilizers are silicone oils, usually silicone-glycol copolymers such as those prepared in accordance with the disclosure of U. S. Patent No. 2,834,748.
Such materials have the formula R'Si(O-(R2SiO)n-(oxyalkylene)mR'')S

wherein R, R' and R'' are alkyl groups containing 1 to 4 carbon atoms, n is 4 to 8, m is 20 to 40, and the oxyalkylene groups are derived from ethylene and propylene oxides or mixtures there-of.
Blowing agents used to prepare rigid urethane foams are generally volatile liquids such as, for example, trichloro-fluoromethane.
Fire retardants that can be incorporated in the foam-ing mixture are of two types, those that are incorporated by mere mechanical mixing and those that become chemically bound in the polymer chains. The most commonly used of the ",~ .

~3~3Z

first type are tris(chloroethyl) phosphate and tris(chloro-propyl) phosphate. The second type of fire retardant offers another approach to the problem of fire retarding foams.
Examples of this type include chlorendic acid derivatives, terephthalate derivatlves, and various phosphorus-containlng polyols.
While the new cellular polyurethane products of the present invention are obtained by using the new polyol-catalyst mixtures produced above, it may be desirable at times to modify the product by including other types of polyols and catalysts. For example, it may be desirable to include other known catalysts for this reaction, such as, for example, polyamines, tin octoate, dibutyl tin dilaurate, n-alkyl morpholines, diazabicyclooctane, and the like. Other polyols that may be included inclose those possessing at least 2 to 6 hydroxyl groups. Suitable examples include, among others polyethylene glycol, polyesters as glycol-terephthalate, glycol-succinate, tetramethyleneglycol-adipate or other hydroxy-terminated linear esters. Other polyols may be glycerol, 1,2,6-hexanetriol, 1,3,6-octanetriol, a polyethylene ether derivative of glycerol or 1,2,6-hexanetriol, erythritol, pentaerythritol, mannitol, sorbitol, alpha-methyl glucose and sucrose. Other polyols include those prepared by reacting an alkylene oxide such as ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide, epichlorohydrin, glycidol and mixtures thereof with a polyhydric alcohol such as carbo-hydrates, glycerol, hexanetriol, petaerythritol sorbitol, methyl glucoside, sucrose, and the like In addition, alkylene oxlde adducts ox certain amines, such as, for exam-ple, any of the aforementioned oxides with amines such as ~7~ . a n ,' ethylene dlamine, aminoethylpiperazine, etc. may also be used.

~aZ~13~3;2 Hydroxy-terminated polyesters are also useful in preparing the products of the invention. These include those pxepared by reacting dibasic acids such as adipic acid, phthalic acid, terephthalic acid, and diols or triols, such as diethylene glycol, glycerol, trimethylpropane and the like Preferred polyols to be used include those obtained by reacting p~lyalkylene oxides with polyhydric alcohols, the polyols obtained by reacting the alkylene oxides with poly-amines and the polyols obtained by reacting polybasic acids with polyhydric alcohols to form hydroxy-terminated products.
The selection of the reactant components will vary depending upon the type of product desired. In general when a flexible cellular product is desired, the polyols should preferably have a functionality of from about 2 to 4 and a molecular weight of about 2000 to 6000. For rigid foams, the functionality of the polyol is preferably from about 4 to 8 and a molecular weight of about 300 to about 1200. For polyisocyanurate foams the functionality of the polyol is preferably from about 2 to 8 and the molecular weight varies from about 105 to 1000.
The amount of the polyisocyanate and the polyol-catalyst mixture to be used in making the polyurethane cellu-lar products of the present invention may nary over a wide range. In general, the amount of the polyisocyanate should be su-fficient to react with all of the OH groups present in the polyol portion of the mixture and preferably in excess thereof. More preferably there is about 1 to 8 equivalents of the isocyanate groups per equivalent of OH groups. As noted above, an unexpected advantage of the use of the new - 30 polyol-catalyst systems includes their ability to bring about the incorporation of much larger amounts of isocyanurate ~z~

linkages than possible heretofore. Coming under special consideration then would be the use o larger amounts of the isocyanates, such as, for example, from 2 to 5 equivalents of isocyanate groups per equivalent of OH.
When the polyol-catalyst mixture is added in the amount described above, the amount oE catalyst present is sufficient to effect the desired rapid reaction.
Foams may be prepared by the so-called "one-shot"
method or the "quasi-prepolymer" method. In the one-shot method, the ingredients are simultaneously intimately mixed with each other to provide a foam by a one step process. In accordance with the quasi-prepolymer method, a portion of the polyol compound is reacted in the absence of the catalyst with the polyisocyanate component. Jo prepare a foam, the lS remaining portion of the polyol is added and the two compo-nents are allowed to react in the presence of catalystic systems such as those discussed above and other appropriate additives. Usually a flexible foam is prepared by the one-shot method whereas rigid foams may be produced by that method or the quasi-pxepolymer method. Polyurethane or polyisocyan-urate elastomers, coatings, solid polymers, etc. may also be prepared by known techniques.
The polymers prepared with the new polyol-catalysts may be use for a wide~variety of end-uses. Fox example, the rigid, flexible, semi-flexible or semi-rigid type of poly-urethane or polyisocyanurate foams may be used for thermal insulation and as building materials and the like. As specific examples, the cellular products o the invention can be employed as thermal barriers in the construction of fire walls, in toe building of industrial and institutional struc-tures, and as insulating materials for high temperature ~Z~ 3;2 pipelines and ovens, in supersonic aircraft and also as missile components.
To illustrate the preparation of the new polyol-catalyst compositions and the new cellular products, the following examples are given. It is to be understood, how-ever, that the examples are given only in the way of illu5-tration and are not to be regarded as limiting the invention in any way.
E X A M P L E
10 To a 5-gallon kettle was added 10.0 lbs (0.0167 lb.
mole) of an aqueous (24% water) Mannich base condensate, which was prepared from nonylphenol, diethanolamine and aqueous 37%
formaldehyde as described in U. S. 3,297,597. The condensate solution was heated to 110C. to 115DC. and 6.0 lb (0~103 lb mole) propylene oxide was added. After divesting the reaction mixture to constant pressure a water analysis gave 14.4% water present. An additional 1.0 lb propylene oxide was added and after digestion showed a water concentration of 11.4%. The waxer and excess oxide were finally vacuum stripped to 5 mmm ; 20 Hg~llO~C. to give 14.25 lb of a dark red product, having the following analysis-~ydroxyl number, mg. KOH/g. 638 Total amine, meg./g. 2.3 Viscosity (25C.), cps 3,500 Color (Gardner) 10-11 pH (25% isopropanol:water) 10.6 E X A M P L E II
To a 15 gallon reactor kettle was added 22.0 lb tO.10 lb mole) of p-nonylphenol and 22.0 lb 10.21 lb mole) - 30 diethanolamine. Then 17.0 lb (0.21 lb mole) 37~ aqueous formalin was added slowly while the kettle temperature was ~Z~3~13;~

maintained between 30 and 40C. After all the formalin was added the kettle was heated to 110C. and the reaction mixture digested for four hours. After this period, the water concentration was 23.9~.
While heating at 110C. to 115C., 35.0 lb (0.60 lb mole) propylene oxide was slowly added. After a digestion period of two hours, the water concentration was 7.5%. Water and excess oxide were removed by vacuum stripping to 8 mm Hg/110C. The product was a dark red liquid. Yield was 82 ,10 lbs~
Analysis:
Hydrogen number, mg. KOH/g. 611 Total amine, meg./g. 2.50 Viscosity, cps (25C.) ~,450 : 15 Wt% water ~-Color (Gardner) 12 13 pH 10.7 ; E X A M P L E III
-the procedure of Example II was used; however, the : 20 aqueous Mannich condensate was prepared by admixing 11.0 lb, .p-nonylphenol, 11.0 lb dlethanolamine and 8.5 lb 37% formalin, followed by a three hour digestion period at:110C.
: The aqueous condensate was heated at 110C. while : 13.5 lb (0.307 lb mole) ethylene oxide was added After digesting for one hour at 110C. the mixture was stripped to a water concentration of 0.03%. Yield was 36.3 lb of dark red, slightly viscous liquid.
analysis:
Hydroxyl no., mg. KOH/g. 557 Total amine, meg/g. 2.84 Viscosity (2~C.), cps 7,900 P;3~3i3~

Color (Gardner) 13-.4 pH (25~ isopropanol:water) 12.1 E X A M P L E IV
_ To a 15-gallon kettle was added 14.9 lbs ~0.10 lb mole) triethanolamine ~99%) and 3.6 lb water. The resulting mixture was heated up to 110 to 115C. under nitrogen while 23.2 lbs ~0.40 lb mole) propylene oxide was slowly added.
After a two hour digestion period at 10C. to 115C. the water concentration was 6.28~.
; 10 The product was stripped in high vacuum to remove

4 to 5 lbs water and oxide. Yield was 38.0 lb of ligh`t, red-:~ brown mobile liquid.
Analysis:
I; Hydroxyl No. 580 I: 15 Total amine 5.4 : Viscosity (25~C.), cps 300 : Wt,% water 0.03 Color 6-7 pH 11.2 ; 20 : E X A M P L E V
::: : : , The procedure of Example II was repeated. However, I; the aqueous Mannlch condensate was prepared:by reacting 26.4 lbs p-nonylphenol, 26.4 lbs diethanolamine:and 20~2 lbs of 37~ aqueous formaldehyde at 95 100C. for about five hours.
:
25:~: Whlle~heating at 100C. the above condensate mix-I: . ture was reacted with 33.0 lb ethylene oxide and digesting to : : :constant pressure over a one hour period. After vacuum stripping the mixture down to S mm~g~100C. 87.3 lbs of a dark-red viscous product was:obtained.

- 30 Analysis:

, .

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Hydroxyl no. 575 Total amine 2.8 Viscosity (25C.) 7,900 Wt % water 0.16 Color (Gardner) 12-13 pH (isopropanol:water) 12.1 E X A M P L E VI
To a 15-gallon reactor kettle was added 15.0 lb (0.10 lb mole) p-tertbutylphenol and 22.0 lb diethanolamine.
Then 17.0 lb (0.21 mole) of 37% aqueous formaldehyde was added. After a four hour digestion period at 100-110~., the water concentration was 23.4%.
The aqueous condensate was heated at 110C. while 35.0 lb (0.60 lb mole) propylene oxide was added slowly.
After a one hour digestion period a 110C. the water con~en-tration was 10.6%.
The above mixture was finally vacuum stripped to 10 mm Hg/lOO~C. to give 74.6 lb of red, viscous liquid polyol.
Analysis:
Hydroxyl number 640 Total amine 2.76 Viscosity, cps (25~C.)6t800 Water, wt % 0.052 Color (Gardner) 10-11 pH (25% isopropanol:water) 10.3 E X A M P L E VII
;, :
To a one-liter stirred autoclave was added 195 g (1.0 mole) N-ben~yldiethanolamine and 72 g (4.0 mole) water.

The mixture was heated to 100-110~. and 174 gram (3.0 moles) - 30 propylene oxide was added. After a short digestion period, ~17-3~3;Z

the mixture was stripped in high vacuum to remove water and give 385 g. light yellow product.
Analysis:
Hydroxyl number 544 Total amine 2.38 Viscosity (25C.) ups 1,620 Wt. water 0.08 Color (Gardner) 9-10 pH (25~ isopropanol/water~ 10~2 E X A M P L E VIII
: The polyol-catalyst composition preparad in Example I was used to prepare a rigid foam. This was accomplished by adding 3~.S parts of the polyol to 53.5 parts of Mondur OR, : 0.5 parts silicone DC-193, 12.5 parts of fluorocarbon m e propexties of the resulting foam are shown in Table I.
: : Components used in the raaction are identified as follows:
Thanol TR-380 - an ethylene oxide adduct of aniline, see U. S.
,067,~33 Trichloroethyl phosphate : Slice DC-193 - silicone-glycol copolymer : :. Freon~R-ll-B - trifluorochloromethane Mondur MR - mixture of 50% diphenylmethane diisocyanate and : : 20 50:~ higher polymers of similar structure, has a 32~ NCO content and equivalent weight of 132 E X A MOP L E S IX to XIV
The polyol-catalyst mixtures prepared in Examples I, 3, 4, 5~ 6 and 7 were used to prepare rigid polyurethane foams. The condltions and results are shown in Table I.
: As can be seen, the use of the new polyol-catalyst mlxtures qave Products having hiqh isocyanate indices, : excellent hezt temperatures and good insulation properties.
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: In addition, there was excellent cQmpatibillty of the polyol-catalyst mixtures with the other ingredients and the rate of .
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reaction could be easily controlled. The polyol-catalyst mixtures also imparted no amine odor to the final product.

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Claims (23)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for preparing polyol-catalyst mix-tures useful in the preparation of rigid polyurethane cellular products which comprises heating a Mannich base compound with water and an epoxide and subsequently removing the water from the reaction mixture.

2. A process as in claim 1 wherein the Mannich base is a reaction product of a phenol, an alkanolamine and formaldehyde.

3. A process as in claim 1 wherein the Mannich base is a reaction product of an alkylphenol, dialkanolamine and formaldehyde.

4. A process as in claim 1 wherein the epoxide is an alkylene oxide.

5. A process as in claim 1 wherein the epoxide is an alkylene oxide of the group consisting of ethylene oxide, propylene oxide, butylene oxide and amylene oxide.

6. A process as in claim 1 wherein the Mannich base is the reaction product of a phenol, an alkanolamine and formaldehyde wherein the components are utilized in a ratio varying from 1:1:1 to 3:3:3.

7. A process as in claim 2 wherein the alkanol-amine is diisopropanolamine.

8. A process as in claim 2 wherein the phenol is nonylphenol.

9. A process for preparing a polyol-catalyst mix-ture for use in the preparation of rigid polyurethane cellular products which comprises reacting a Mannich base compound with water and alkylene oxide at a temperature between 50°C.
and 150°C. until the desired polyol-catalyst mixture has been formed and then stripping out the water.

10. A process as in claim 9 wherein the Mannich base is a reaction product of an alkylphenol, an alkanolamine and formaldehyde.

11. A polyol-catalyst mixture prepared by the process of claim 1.

12. A process for preparing cellular polyurethane products by reacting the polyol-catalyst mixture defined in claim 1 with a polyisocyanate and a volatile blowing agent.

13. A process as in claim 12 wherein the reaction mixture also contains a foam stabilizer, flame retardant and filler.

14. A process as in claim 12 wherein the polyiso-cyanate is an aromatic polyisocyanate having from 2 to 6 isocyanate groups.

15. A process as in claim 12 wherein the polyiso-cyanate equivalents to polyol equivalents vary from 1:1 to 8:1.

16. A process as in claim 12 wherein the polyiso-cyanate is a methylene-bridged polyphenyl polyisocyanate.

17. A process for preparing cellular polyurethane products by reacting (1) a polyol-catalyst mixture obtained by reacting a Mannich base compound with water and an alkylene oxide at a temperature between 50°C. and 150°C. until the desired product has been formed and then stripping off the water, with (2) a polyisocyanate and a volatile blowing agent.

18. A process as in claim 17 wherein the reaction mixture also contains a foam stabilizer, fire retardant and filler.

19. A process as in claim 17 wherein the polyiso-cyanate is an aromatic polyisocyanate.

20. A process as in claim 17 wherein -the reaction mixture also contains another dissimilar polyol.

21. A process as in claim 17 wherein the dissimilar polyol is an alkylene oxide adduct of aniline.

22. A process as in claim 17 wherein the polyiso-cyanate is a methylene-bridged polyphenyl polyisocyanate.

23. A product prepared by the process of claim 17.