Polyurethane catalysts from sulfur based salts
This invention discloses the use of sulfite salts as catalysts to make polyurethane polymers. In particular, this invention discloses the use of metal salts such as alkali metal salts as well as alkyl ammonium salts such as tetralkyl ammonium salts as catalysts to make polyurethane polymers. The sulfite salts are useful to make a wide variety of polyurethane polymers and polyurethane foam polymer products such as flexible polyurethane foam polymers, rigid foam polyurethane polymers, semi-rigid polyurethane polymer, microcellular polyurethane polymer, and spray foam polyurethane polymer as well as any polymeric material that requires the assistance of catalysts to promote the formation of urethane and urea bonds such as those found in polyurethane emusions for paints, coatings, protective coatings, lacquer, etc as well as other polyurethane or polyurethane containing materials such as thermoplastic polymers, thermoplastic polyurethane polymers, elastomers, adhesives, sealants, etc. Examples of catalysts comprising the invention include sodium sulfite, potassium sulfite, lithium sulfite, tetramethylammonium sulfite and the like.
1. A process for producing polyurethane consisting of contacting at least one polyester polyol and at least one isocyanate while in the presence of A) a catalyst consisting of at least one sulfite, and B) at least one optional component selected from the group consisting of at least one cell stabilizer, at least one blowing agent, at least one crosslinking agent, at least one chain extender, at least one pigment, at least one filler, at least one flame retardant, at least one auxiliary urethane gelling catalyst, at least one auxiliary urethane blowing catalyst, at least one transition metal catalyst, at least one alkali carboxylate salt, at least one alkali earth carboxylate salt, or any combination thereof; wherein the sulfite consists of at least one member selected from the group consisting of sodium sulfite (Na 2 SO 3 ), potassium sulfite (K 2 SO 3 ), lithium sulfite (Li 2 SO 3 ), cesium sulfite (Cs 2 SO 3 ), calcium sulfite (CaSO 3 ), magnesium sulfite (MgSO 3 ), tetramethylammonium sulfite [(Me 4 N) 2 SO 3 ], tetraethylammonium sulfite [(Et 4 N) 2 SO 3 ], tetrabutylammonium sulfite [(Bu 4 N) 2 SO 3 ], trimethylbenzyl ammonium sulfite [(Me 3 N—CH 2 —C 6 H 5 ) 2 SO 3 ], cetyltrimethylammonium sulfite [(Me 3 N—(CH 2 ) 14 —CH 3 ) 2 SO 3 ], N-methyl-pyridinium sulfite [(Me-C 5 NH 5 ) 2 SO 3 ], and di-alkylimidazolium sulfite salts [(R 2 C 3 N 2 H 3 ) 2 SO 3 ], and wherein the amount of the at least one sulfite is about 0.1 to about 20 parts by weight per hundred parts by weight of the at least one polyol.
2. A process for producing polyurethane consisting of contacting at least one polyester polyol and at least one isocyanate while in the presence of A) a gelling catalyst consisting of at least one sulfite and at least one blowing catalyst selected from the group consisting of 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, N,N,N′-trimethyl-N′-3-aminopropyl-bis(aminoethyl) ether, bis(dimethylaminoethyl)ether, pentamethyldiethylene triamine, and hexamethyltriethylenetetraamine, and B) at least one optional component selected from the group consisting of at least one cell stabilizer, at least one blowing agent, at least one crosslinking agent, at least one chain extender, at least one pigment, at least one filler, at least one flame retardant, at least one auxiliary urethane gelling catalyst, at least one auxiliary urethane blowing catalyst, at least one transition metal catalyst, at least one alkali carboxylate salt, at least one alkali earth carboxylate salt, or any combination thereof; wherein the sulfite has a structural formula of at least one of: i) M 2 SO 3 where M is an alkali metal selected from the group of Na, K, Li, Cs, ii) MSO 3 where M is an alkali earth metal selected from the group of Ca, Mg, Sr, Ba; and iii) M 2 SO 3 where M is a quaternary ammonium ion of general formula R 1 R 2 R 3 R 4 N where R 1 , R 2 , R 3 , R 4 are C 1 -C 18 alkyl, alkenyl, aryl, alkylaryl, substituted alkyl, alkenyl or alkylaryl linear, branched with or without heterocyclic containing groups, and wherein the amount of the at least one sulfite is about 0.1 to about 20 parts by weight per hundred parts by weight of the at least one polyol.
3. A process for producing polyurethane consisting of contacting at least one polyester polyol and at least one isocyanate while in the presence of A) a catalyst composition consisting of i) a gelling catalyst consisting of at least one sulfite and ii) at least one tetralkylammonium phase transfer catalyst selected from the group consisting of carboxylates, sulfonates, halide ions, and sulfates of tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, benzyltrimethylammonium, dibenzyldimethylammonium, tribenzylmethylammonium, tetrabenzylammonium, phenyltrimethylammonium, diphenyldimethylammonium, triphenylmethylammonium, tetraphenylammonium, dialkylimidazolium, and N-methyl-triethylenediammonium, and B) at least one optional component selected from the group consisting of at least one cell stabilizer, at least one blowing agent, at least one crosslinking agent, at least one chain extender, at least one pigment, at least one filler, at least one flame retardant, at least one auxiliary urethane gelling catalyst, at least one auxiliary urethane blowing catalyst, at least one transition metal catalyst, at least one alkali carboxylate salt, at least one alkali earth carboxylate salt, or any combination thereof; wherein the sulfite has a structural formula of at least one of: i) M 2 SO 3 where M is an alkali metal selected from the group of Na, K, Li, Cs, ii) M 2 SO 3 where M is an alkali earth metal selected from the group of Ca, Mg, Sr, Ba; and iii) M 2 SO 3 where M is a quaternary ammonium ion of general formula R 1 R 2 R 3 R 4 N where R 1 , R 2 , R 3 , R 4 are C 1 -C 18 alkyl, alkenyl, aryl, alkylaryl, substituted alkyl, alkenyl or alkylaryl linear, branched with or without heterocyclic containing groups, and wherein the amount of the at least one sulfite is about 0.1 to about 20 parts by weight per hundred parts by weight of the at least one polyol.
4. A process for producing polyurethane consisting of contacting at least one polyester polyol and at least one isocyanate while in the presence of A) a catalyst composition consisting of i) a gelling catalyst consisting of at least one sulfite, ii) at least one blowing catalyst, and iii) at least one tetralkylammonium phase transfer catalyst, and B) at least one optional component selected from the group consisting of at least one cell stabilizer, at least one blowing agent, at least one crosslinking agent, at least one chain extender, at least one pigment, at least one filler, at least one flame retardant, at least one auxiliary urethane gelling catalyst, at least one auxiliary urethane blowing catalyst, at least one transition metal catalyst, at least one alkali carboxylate salt, at least one alkali earth carboxylate salt, or any combination thereof; wherein the sulfite has a structural formula of at least one of: i) M 2 SO 3 where M is an alkali metal selected from the group of Na, K, Li, Cs, ii) M 2 SO 3 where M is an alkali earth metal selected from the group of Ca, Mg, Sr, Ba; and iii) M 2 SO 3 where M is a quaternary ammonium ion of general formula R 1 R 2 R 3 R 4 N where R 1 , R 2 , R 3 , R 4 are C 1 -C 18 alkyl, alkenyl, aryl, alkylaryl, substituted alkyl, alkenyl or alkylaryl linear, branched with or without heterocyclic containing groups; wherein the at least one blowing catalyst is selected from the group consisting of 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, N,N,N′-trimethyl-N′-3-aminopropyl-bis(aminoethyl) ether, bis(dimethylaminoethyl)ether, pentamethyldiethylene triamine, and hexamethyltriethylenetetraamine; wherein the at least one tetralkylammonium phase transfer catalyst is selected from the group consisting of carboxylates, sulfonates, halide ions, and sulfates of tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, benzyltrimethylammonium, dibenzyldimethylammonium, tribenzylmethylammonium, tetrabenzylammonium, phenyltrimethylammonium, diphenyldimethylammonium, triphenylmethylammonium, tetraphenylammonium, dialkylimidazolium, and N-methyl-triethylenediammonium; and wherein the amount of the at least one sulfite is about 0.1 to about 20 parts by weight per hundred parts by weight of the at least one polyol.