Photolatent catalysts based on organometallic compounds

• US 8,318,830 B2
• Filed: 10/10/2008
• Issued: 11/27/2012
• Est. Priority Date: 10/17/2007
• Status: Active Grant

• Current Assignee: BASF SE
• Original Assignee: BASF SE
• Inventors: Kohli Steck, Rachel, Lordelot, Caroline, Vogel, Thomas, Baudin, Gisele, Brown, Paul, Dietliker, Kurt, Huesler, Rinaldo, Jung, Tunja, Simmendinger, Peter, Studer, Katia, Carroy, Antoine
• Primary Examiner(s): Berman, Susan W
• Application Number:
  US12/738,362
• Publication Number:
  US 20100234485A1
• Time in Patent Office: 1,509 Days
• Field of Search: 522/29, 522/66, 522/146, 522/174, 522/134, 522/33, 522/37, 522/39, 522/42, 522/44, 522/46, 522/53, 522/63, 528/56, 528/58, 528/65, 556/83, 556/88, 556/94, 556/90, 556/89, 556/87, 556/37, 556/77, 556/78, 556/54, 556/55, 556/56, 556/182, 556/51, 556/70, 556/81, 556/170
• US Class Current: 522/33
• CPC Class Codes: C08G 18/222 metal compounds not provided for in groups C08G18/225 - C08G18/26
• CPC Class Codes: C08G 18/227 of antimony, bismuth or arsenic
• CPC Class Codes: C08G 18/24 of tin
• CPC Class Codes: C08G 18/42 Polycondensates having carboxylic or carbonic ester groups in the main chain
• CPC Class Codes: C08G 18/6216 Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
• CPC Class Codes: C08G 18/792 formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• CPC Class Codes: C08G 18/80 Masked polyisocyanates
• CPC Class Codes: C09D 175/04 Polyurethanes

Abstract

The present invention provides organometallic latent catalyst compounds, which are suitable as catalysts in polyaddition or polycondensation reactions which are catalysed by a Lewis acid type catalyst, in particular for the crosslinking of a blocked or unblocked isocyanate or isothiocyanate component with a polyol or polythiolto form a polyurethane (PU).

Claims

1. A polymerizable composition comprising

(a) at least one blocked or unblocked isocyanate or isothiocyanate component,

(b) at least one polyol;

and

(c) at least one latent catalyst compound comprising

a photoactive moiety (PI) bound to a metal and capable of initiating a polyaddition or a polycondensation reaction by exposure to electromagnetic radiation of a wavelength range of 200-800 nm,

wherein the latent catalyst is a compound of the formula I or II,

Me(PI)_(m-x)A_x 

 

(I)

A_x(PI)_(m-1-x)Me-O-Me(PI)_(m-1-x)A_x 

 

(II), wherein

Me is Sn, Bi, Al, Zr or Ti;

m denotes an integer from 1 up to the coordination number of Me;

x is an integer from 0 to (m−

1);

A is C₁-C₂₀alkyl, halogen, C₇-C₃₀arylalkyl, C₁-C₂₀alkoxy, C₂-C₂₀alkanoyloxy, C₆-C₁₈aryl or C₆-C₁₈aryl which is substituted by one or more C₁-C₂₀ alkyl; and

provided that in case x is greater than one, the A are identical or different; and

PI independently of each other is selected from the group consisting of formulas (Z), (B), (C), (D), (E), (F), (G), (H), (J), (K), (L) and (M)

2. The polymerizable composition according to claim 1, wherein the latent catalyst compound of formula I or II

Me is Sn, Bi, Al, Zr or Ti;

m denotes an integer from 1 up to the coordination number of Me;

x is an integer from 0 to (m−

1);

A is C₁-C₂₀ alkyl, halogen, C₁-C₂₀ alkoxy, C₂-C₂₀ alkanoyloxy or C₆-C₁₈aryl;

PI independently of each other is selected from the group consisting of formulas (Z), (B), (C), (D), (E), (F), (G), (L) and (M);

y is 0 or 1;

R₁, R₂ and R₃ independently of one another are hydrogen or C₁-C₆-alkyl;

R₄ is hydrogen, or R₃ and R₄ together are S;

R₅ is hydrogen;

R₆ is hydrogen;

Y₁ and Y₃ independently of one another are O, (CO)O, C₁-C₂₀alkylene, C₁-C₂₀alkylene-O—

or C₁-C₂₀alkylene-(CO)O—

;

Y₂ is a direct bond;

R₇ and R₈ independently of one another are C₁-C₆-alkyl;

or R₇ and R₈ together with the carbon atom to which they are attached form a cyclohexyl ring;

R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ are hydrogen;

R₁₆ is phenyl;

R₁₇ is CN;

R₁₉ and R₂₀ together with the N-atom to which they are attached, are

3. A polymerizable composition according to claim 1, comprising in addition to components (a), (b) and (c) a further additive (d).

4. A polymerizable composition according to claim 3, wherein the further additive (d) is a photosensitizer compound.

5. A polymerizable composition according to claim 1, which comprises 0.001 to 15% by weight of the latent catalyst compound based on the total composition.

6. The polymerizable composition according to claim 1, wherein Me is Sn.

7. The polymerizable composition according to claim 1, wherein Me is Bi.

8. The polymerizable composition according to claim 1, wherein Me is Al.

9. The polymerizable composition according to claim 1, wherein Me is Zr.

10. The polymerizable composition according to claim 1, wherein Me is Ti.

11. A coated substrate, comprising:

on at least one surface, the polymerized or crosslinked composition according to claim 1.

12. A polymerized or crosslinked composition obtained by a process comprising curing a polymerizable composition according to claim 1.

13. A latent catalyst compound, which is of the formula I or II,

Me(PI)_(m-x)A_x 

 

(I)

A_x(PI)_(m-1-x)Me-O-Me(PI)_(m-1-x)A_x 

 

(II), wherein

Me is Sn, Bi, Al, Zr or Ti;

m denotes an integer from 1 up to the coordination number of Me;

x is an integer from 0 to (m−

1);

A is C₁-C₂₀ alkyl, C₇-C₃₀ arylalkyl, C₁-C₂₀alkoxy, C₂-C₂₀alkanoyloxy, C₆-C₁₈aryl or C₆-C₁₈aryl which is substituted by one or more C₁-C₂₀alkyl;

or, if x is 1, A additionally is halogen;

provided that in case x is greater than one, the A are identical or different.

PI independently of each other is selected from the group of formulas (Z), (B), (C), (D), (F), (G), (H), (J), (K) and (M)

14. A process for polymerizing compounds, which are capable to crosslink in the presence of a Lewis acid, wherein a latent catalyst compound as defined in claim 13 is added to said compounds and the resulting mixture is irradiated with electromagnetic radiation of a wavelength range of 200-800 nm.

15. A process according to claim 14, wherein the component which is capable to crosslink in the presence of a Lewis acid is a mixture of (a) a blocked or unblocked isocyanate or isothiocyanate component and (b) a polyol.

16. A process for polymerizing compounds, which are capable to crosslink in the presence of a Lewis acid, wherein a latent catalyst composition as defined in claim 13 is added to said compounds and the resulting mixture is subjected to a heat treatment, or the mixture is irradiated with electromagnetic radiation and simultaneously with or after the irradiation subjected to a heat treatment.

17. A process according to claim 14 for the preparation of adhesives, sealings, coatings, potting components, printing inks, printing plates, foams, moulding compounds, or photostructured layers.