Polyurethane Catalysts from Sulfur Based Salts

Patent metadata

Field	Value
Publication number	US-2016102169-A1
Application number	US-201514881544-A
Country	US
Kind code	A1
Filing date	Oct 13, 2015
Priority date	Oct 13, 2014
Publication date	Apr 14, 2016
Grant date	—

Abstract

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.

First claim

1 . A catalyst composition comprising at least one sulfite and at least one tertiary amine.

2 . The catalyst composition of claim 1 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, alkelnyl, aryl, alkylaryl, substituted alkyl, alkenyl or alkylaryl linear, branched with or without heterocyclic containing groups.

3 . The catalyst composition of claim 2 wherein the sulfite comprises 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 3 NH 3 ) 2 SO 3 ], and di-alkylimidazolium sulfite salts [(R 2 C 3 N 2 H 3 ) 2 SO 3 ].

4 . The catalyst composition of claim 2 wherein the sulfite has a formula (X n ) m (Y m ) n [SO 3 ] (m.n+n.m/2) where X is a metal cation with charge n, Y is an alkylammonium or polyalkylammonium ion with charge m, X is selected from the group of Li + , Na + , K + , Cs + , Be 2+ , Mg 2+ , Ca 2+ , and Zn 2+ , n is an integer from 1 to 4; preferentially from 1 to 3, and m is an integer from 1 to 6.

5 . The catalyst composition of claim 4 wherein Y comprises at least one ammonium cation of general formula R 1 R 2 R 3 R 4 N.

6 . The catalyst composition of claim 5 wherein Y comprises at least one member selected from the group consisting of tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, benzyltrimethylammonium, dibenzyldimethylammonium, tribenzylmethylammonium, tetrabenzylammonium, phenyltrimethylammonium, diphenyldimethylammonium, triphenylmethylammonium, tetraphenylammonium, and dialkylimidazolium, triethylenediamine based quaternary ammonium.

7 . The catalyst composition of claim 2 wherein the sulfite has a general formula [(X n ) m.w ][(Y m ) n.z ][SO 3 ] (m.n+n.m/2) where X is a metal cation with charge n, Y is an alkylammonium or polyalkylammonium ion with charge m, and w and z are any integer defined such that w+z=2, and n and m range from 1 to 4.

8 . The catalyst composition of claim 7 wherein X cations are Li + , Na + , K + , Cs + , Be 2+ , Mg 2+ , Ca 2+ , and Zn 2+ ; and Y cations are ammonium cations of general formula R 1 R 2 R 3 R 4 N.

9 . The catalyst composition of claim 8 wherein Y comprise at least one member selected from the group consisting of tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, benzyltrimethylammonium, dibenzyldimethylammonium, tribenzylmethylammonium, tetrabenzylammonium, phenyltrimethylammonium, diphenyldimethylammonium, triphenylmethylammonium, tetraphenylammonium, dialkylimidazolium, and triethylenediamine based quaternary ammonium.

10 . The catalyst composition of claim 1 wherein the composition is substantially free of amines.

11 . The catalyst composition of claim 1 wherein the composition is substantially free of metal compounds based on Sn, Hg, Pb, Bi, and Zn.

13 . A composition comprising at least one sulfite catalyst, water, at least one polyol and at least one member selected from phase transfer catalysts, at least one tertiary amine catalyst, and at least one metal catalyst.

14 . A process for producing polyurethane comprising contacting at least one polyol and at least one isocyante while in the presence of a catalyst comprising at least one sulfite.

15 . The process of claim 14 wherein the catalyst comprises the catalyst composition of claim 2 .

16 . The process of claim 14 wherein the polyurethane comprises a foam.

17 . A polyurethane foam made by the process of claim 14 .

18 . The polyurethane foam of claim 17 wherein the foam comprises about 0.02 to about 0.6 wt. % sulfur.

19 . The polyurethane foam of claim 17 wherein the foam has no amine emissions when measured in accordance with VDA-278.

20 . The polyurethane foam of claim 17 wherein the foam has no aldehyde emissions.

21 . A catalyst composition comprising at least one member selected from the group consisting of i) 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, alkelnyl, aryl, alkylaryl, substituted alkyl, alkenyl or alkylaryl linear, branched with or without heterocyclic containing groups, ii) a sulfite having a formula (X n ) m (Y m ) n [SO 3 ] (m.n+n.m/2) where X is a metal cation with charge n, Y is an alkylammonium or polyalkylammonium ion with charge m, X is selected from the group of Li + , Na + , K + , Cs + , Be 2+ , Mg 2+ , Ca 2+ , and Zn 2+ , n is an integer from 1 to 4; preferentially from 1 to 3, and m is an integer from 1 to 6, and iii) a sulfite having a general formula [(X n ) m.w ][(Y m ) n.z ][SO 3 ] (m.n+n.m/2) where X is a metal cation with charge n, Y is an alkylammonium or polyalkylammonium ion with charge m, and w and z are any integer defined such that w+z=2, and n and m range from 1 to 4.

Assignees

• Air Prod & Chem

Inventors

• Burdeniuc Juan Jesus

Classifications

• B01J31/0238

  with a primary amino group · CPC title

• C08G18/1875

  containing ammonium salts or mixtures of secondary of tertiary amines and acids · CPC title

• C08G18/18

  containing secondary or tertiary amines or salts thereof · CPC title

• C08G18/1825

  having hydroxy or primary amino groups · CPC title

• C08G18/7621 Primary

  being toluene diisocyanate including isomer mixtures · CPC title