United States Patent [19] [11] Patent Number: 4,518,778 Cuscurida [45] Date of Patent: May 21, 1985

United States Patent [19] [11] Patent Number: 4,518,778 Cuscurida [45] Date of Patent: May 21, 1985 [54] POLYMER POLYOLS FROM ALKYLENE 4,089,835 5/1978 Konig et a1. ...................... .. 252/308 OXIDE ADDUCTS OF ALKANOLAMINES guscul'iga -- 222; . , , USCUrl a ............ .. [75] Inventor: Michael Cuscurida, Austin, Tex‘ 4,309,532 l/l982 Cuscurida ........ .. .. 544/398 [73] Assigneez Texaco Inc" White Plains, N_Y_ 4,374,209 2/1983 Rowlands ......................... .. 521/166 2 A . N .: 135 Primary Examiner-Donald G. Daus [ 1] pp! 0 5 ’ 99 Assistant Examiner—Cecilia Shen [22] Filed! Jlll- 14, 1983 Attorney, Agent, or Firm-Jack H. Park; Kenneth R. [51] Int. (:1.3 .................. .. c071) 241/04; CO8G 18/28; Pr‘em; Dav'd L- Mossma“ CO7C 125/06 [57] ABSTRACT [52] US. Cl. .................................. .. 544/398; 252/182; _ 521/164; 521/166; 528/73; 528/76; 560/26; A polymer polyol made by the reactlon of an alkylene 560/115; 560/158 oxide adduct of a hydroxyl-containing amine, a poly [58] Field of Search .................. .. 544/398; 528/73, 76; ether polyol of about 3000 to 8000 molecular weight 560/26, 115, 158; 252/182; 521/164, 166 and an organic polyisocyanate 1s disclosed. This poly R C_ d mer polyol may be used in the manufacture of ?exible [56] eferences "8 polyurethane foams. The polymer polyols are more US. PATENT DOCUMENTS stable than those made by other procedures. 3,294,751 12/1966 Beitchman .......................... .. 528/77 3,325,421 6/1967 Muller ............................... .. 252/308 16 Claims, N0 Drawings 4,518,778 1 2 isocyanates in a polyol solvent are U.S. Pat. Nos. POLYMER POLYOLS FROM ALKYLENE OXIDE 4,374,209 and 4,296,213. Particularly, the present inven ADDUCTS OF ALKANOLAMINES tion is an improvement on the latter method in that alkoxylated alkanolamines are used to produce polymer BACKGROUND OF THE INVENTION 5 polyols more stable than (no phase separation) those of 1. Field of the _Invention U.S. Pat. No. 4,296,213. ' This invention pertains to the ?eld of polyurethane plastics. The invention'more particularly relates to pol SUMMARY OF THE INVENTION ymer polyols made from alkanolamines, polyether poly The invention is a method for producing a polymer ols and polyisocyanates. polyol by reacting an alkylene oxide adduct of a hy 2. Description of the Prior Art droxyl-containing amine, a polyether polyol and an The use of a polyol in the preparation of polyure organic polyisocyanate. thanes by reaction of the polyol with a polyisocyanate in the presence of a catalyst and perhaps other ingredi DESCRIPTION OF THE PREFERRED ents is well known. Conventional polyols for ?exible EMBODIMENTS polyurethane foams are usually made by the reaction of The polymer polyol is made by the reaction of an a polyhydric alcohol with an alkylene oxide, usually alkylene oxide adduct of a hydroxyl-containing amine, a ethylene oxide and/or propylene oxide, to a molecular polyether polyol and an organic polyisocyanate. The weight of about 2000 to 3000 and above. These polyols hydroxyl containing amine should range in molecular are then reacted with polyisocyanate in the presence of weight range from about 60 to about 200 and preferably water or other blowing agents such as fluorocarbons to from about 60 to about 150. Preferably, the alkanola obtain polyurethane foams (see, for example, U.S. Pat. mine is a trifunctional monoamine, a difunctional mono No. 2,929,800). The prior art describes modi?ed polyols amine, an aromatic amine or a diamine. Suitable com in which vinyl monomers such as styrene or acryloni pounds include monoethanolamine, diethanolamine, trile or other materials such as the reaction products of triethanolamine, 2-(2-arninoethoxyethanol), hydroxye toluene diisocyanate and hydrazine hydrate have been thylpiperazine, N-rnethylethanolamine Z-hydroxyethyl included to improve the properties of the polyol and ethylenediamine, ethylenediamine, aniline and toluene thus, the properties of the resulting foam. However, diamine. some of these prior art materials are highly toxic and The alkylene oxides used to react with the alkanola require in addition, stripping of unreacted vinyl mono mine are preferably ethylene oxide, propylene oxide, mers or water of hydration. U.S. Pat. No. 4,107,102 butylene oxide and mixtures thereof. It is well known to describes the manufacture of polyurethane foam using a polyol containing hydrazine and its 'adducts. react alkylene oxides with amines, particularly those Ureido-polyols for polyurethanes are known to be containing hydroxyl groups, typically in the presence of made simply by reacting an alkanolamine with an or an alkaline catalyst, such as sodium hydroxide. For ganic isocyanate according to U.S. Pat. No. 3,294,751. example, see the methods described in U.S. Pat. Nos. No solvent polyol seems to be used. 3,393,243; 3,535,307; 3,706,714 and 4,166,172, incorpo German Offenlegungsschrift No. 2,110,055 discloses rated by reference herein. a process for making a polyurethane product whereby a The polyether polyol which is used has a hydroxyl hydroxyl-containing amine is included in the formula number preferably between about 20 and 60. The polyol tion in a one-shot process. That is, the hydroxyl-con is generally an alkylene oxide adduct of a polyhydric taining amine is simply included initially with the polyol alcohol with a functionality of from about 2 to about 4. and the polyisocyanate and a polyurethane product The alkylene oxide may suitably be ethylene oxide, results. The German process does not use a polyurea propylene oxide, or 1,2-butylene oxide or a mixture of polymer polyol which is then reacted with a polyisocy 45 some or all of these. The polyol will preferably have a anate. molecular weight within the range of from about 2,000 U.S. Pat. No. 3,325,421 discloses the method of mak to about 8,000 and more preferably, from about 3,000 to ing a stable dispersion of a urea in a composition com about 7,000. The alkylene oxide is preferably propylene prising an organic polyisocyanate and a compound oxide or a mixture of propylene oxide and ethylene having at least two alcoholic hydroxyl groups. oxide. Stable dispersions of polyureas can be prepared from Most preferably, the polyether polyol solvent is a mixtures consisting of hydroxyl-group containing mate mixed alkylene oxide/diepoxide adduct of a polyhydric rials, polyamines and polyisocyanates as taught by U.S. initiator, such as those described in U.S. Pat. Nos. Pat. No. 4,089,835. The dispersing media may be a poly 4,316,991; 4,309,532 and 4,323,658, incorporated by ether, a polyester, a polyester amide or a polycarbonate, 55 reference herein. while the polyamine should contain primary or second The polyisocyanate used herein may be any aromatic ary amine groups. or aliphatic polyisocyanate. Typical aromatic polyiso British Pat. No. 2,098,229 discloses that polymer. cyanates include m-phenylene diisocyanate, p-pheny polyols for use in urethane foams may be made by react lene diisocyanate, polymethylene polyphenyl polyiso ing triethanolamine with a polyisocyanate in the pres 60 cyanates, 2,4-toluene diisocyanate, 2,6-tolulene diisocy ence of a polyol solvent. Polyurea polymer polyols anate, dianisidine diisocyanate, bitolylene diisocyanate, made by the reaction of alkanolamines with polyisocya naphthalene-1,4-diisocyanate, xylylene- l ,4-diisocya nates in the presence of polyether polyols and absence nate, xylylene-1,3-diisocyanate, bis(4-isocyanato of a catalyst, may be stabilized by quenching with a phenyl)methane, bis(3-methyl-4-isocyanatophenyl)me secondary amine as described in U.S. Pat. No. 65 thane, and 4,4’-diphenylpropane diisocyanate and mix 4,293,470. tures thereof. Other disclosures concerning the production of poly Greatly preferred aromatic polyisocyanates used in mer polyols by the reaction of alkanolamines with poly the practice of the invention are 2,4- and 2,6-toluene 4,518,778 3 4 diisocyanates and methylene-bridged polyphenyl poly than those of US. Pat. No. 4,296,213; that is, they do isocyanate mixtures which have a functionality of from not separate as readily into two phases. about 2 to about 4. These latter isocyanate compounds In order to form the polyurethane foam, a catalyst are generally produced by the phosgenation of corre useful in preparing foams of this type is employed in the sponding methylene bridged polyphenyl polyamines, usual manner. Such catalyst may include one or more of which are conventionally produced by the reaction of the following: formaldehyde and primary aromatic amines, such as (a) Tertiary amines such as trimethylamine, triethyl aniline, in the presence of hydrochloric acid and/or amine, N-methylmorpholine, N-ethylmorpholine, N,N other acidic catalysts. Known processes for preparing dimethylbenzylamine, N,N-dimethylethanolamine, polyamines and corresponding methylene-bridged O N,N,N'N’-tetramethyl-1,3-butanediamine, N,N-dime polyphenyl polyisocyanates therefrom are described in thylpiperazine, 1,4-diazabicyclo[2.2.2]octane and the the literature and in many patents; for example, US. like; Pat. Nos. 2,683,730; 2,950,263; 3,012,008; 3,344,162 and (b) Tertiary phosphines such as trialkylphosphines, 3,362,979. dialkylbenzylphosphines, and the like; Most preferred methylene-bridged polyphenyl poly (0) Strong bases such as alkali and alkaline earth isocyanate mixtures used here contain about 20 to about metal hydroxides, alkoxides, and phenoxides; 100 weight percent methylene diphenyldiisocyanate (d) Acidic metal salts of strong acids such as ferric isomers, with

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