Compositions including a photolatent amine, camphorquinone, and coumarin and related methods

Patent metadata

Field	Value
Publication number	US-11198757-B2
Application number	US-201716347426-A
Country	US
Kind code	B2
Filing date	Nov 2, 2017
Priority date	Nov 3, 2016
Publication date	Dec 14, 2021
Grant date	Dec 14, 2021

Abstract

A composition includes a photolatent amine, camphorquinone, and a coumarin sensitizer. The coumarin sensitizer is triplet photosensitizer and has an absorbance with a wavelength of maximum absorbance in a range from 390 nanometers to 510 nanometers. Compositions that further include a polymerizable material are also disclosed. Polymer networks preparable from such compositions and methods for making the polymer networks are also disclosed.

First claim

What is claimed is:

1. A composition comprising a photolatent amine, camphorquinone, and a coumarin sensitizer, wherein the coumarin sensitizer comprises at least one of 3,3′-carbonylbis(5,7-dimethoxycoumarin), 3-benzoyl-7-diethylaminocoumarin, 7-diethylamino-3-thenoylcoumarin, 3-(2-benzofuroyl)-7-diethylaminocoumarin, 7-diethylamino-5′,7′-dimethoxy-3,3′-carbonylbiscoumarin, 3,3′-carbonylbis(7-diethylaminocoumarin), 9-(7-diethylamino-3-coumarinoyl)-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one, and 9,9′-carbonylbis(1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one).

2. The composition of claim 1 , wherein the coumarin sensitizer comprises at least one of 3,3′-carbonylbis(7-diethylaminocoumarin), 7-diethylamino-3-thenoylcoumarin, 3-(2-benzofuroyl)-7-diethylaminocoumarin, and 9,9′-carbonylbis(1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one).

3. A composition comprising a photolatent amine, camphorquinone, and a coumarin sensitizer, wherein the coumarin sensitizer is a triplet photosensitizer and has an absorbance with a wavelength of maximum absorbance in a range from 390 nanometers to 510 nanometers, and wherein the photolatent amine is represented by formula:
N(R 7 )(R 6 )—CH(R 5 )—N(R 4 )—C(R 1 )(R 2 )(R 3 ),

wherein
R 1 is selected from the group consisting of phenyl, naphthyl, phenanthryl, anthracenyl, pyrenyl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, anthraquinonyl, dibenzofuryl, chromenyl, xanthenyl, thioxanthyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, terphenyl, stilbenyl, fluorenyl, phenoxazinyl, and combinations thereof, wherein any of these are unsubstituted or substituted by one or more alkyl, alkenyl, alkynyl, haloalkyl, —NO 2 , —NR 10 R 11 , —CN, —OR 12 , —SR 12 , —C(O)R 13 , —C(O)OR 14 , or halogen groups, a radical of the formula N(R 7 )(R 6 )—CH(R 5 )—N(R 4 )—C(R 1 )(R 2 )(R 3 )—, or a combination thereof;
R 2 and R 3 each are independently selected from the group consisting of hydrogen, alkyl, and phenyl that is unsubstituted or is substituted by one or more times by alkyl, CN, —OR 12 , —SR 12 , halogen, or haloalkyl;
R 5 is alkyl or —NR 8 R 9 ;
R 4 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are each independently hydrogen or alkyl; or
R 4 and R 6 together form a C 2 -C 6 alkylene bridge that is unsubstituted or substituted by one or more alkyl groups having up to four carbon atoms; or
R 5 and R 7 , independently of R 4 and R 6 , together form a C 2 -C 6 alkylene bridge that is unsubstituted or is substituted by one or more alkyl groups having up to four carbon atoms; or

if R 5 is —NR 8 R 9 , R 7 and R 9 together form a C 2 -C 6 alkylene bridge that is unsubstituted or substituted by one or more alkyl groups having up to four carbon atoms.

4. The composition of claim 3 , wherein the photolatent amine comprises at least one compound represented by formula

wherein R 1 is phenyl, naphthyl, or anthracenyl, each of which is unsubstituted or substituted by at least one substituent selected from the group consisting of methyl, cyano, nitro, ethenyl, and chloro.

5. The composition of claim 3 , wherein photolatent amine photochemically generates at least one of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1,5-diazabicyclo[4.3.0]non-5-ene (DBN).

6. The composition of claim 3 , further comprising at least one polymerizable material.

7. The composition of claim 3 , further comprising a polythiol comprising more than one thiol group and a polyepoxide comprising more than one epoxide group.

8. The composition of claim 7 , wherein the polythiol is monomeric.

9. The composition of claim 7 , wherein the polythiol is an oligomeric or polymeric polythioether or polysulfide.

10. The composition of claim 7 , further comprising a second amine, wherein the second amine comprises at least one of triethylamine, dimethylethanolamine, benzyldimethylamine, dimethylaniline, tribenzylamine, triphenylamine, tetramethylguanidine (TMG), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), quinuclidine, diphenylguanidine (DPG), dimethylaminomethyl phenol, or tris(dimethylaminomethyl)phenol.

11. A polymer network preparable from the composition of claim 7 , wherein at least some of the thiol groups and epoxide groups have reacted to form thioether groups and hydroxyl groups.

12. The polymer network of claim 11 , wherein the polymer network is a sealant disposed on an aircraft.

13. A method of making a polymer network, the method comprising:
combining the composition of claim 3 with a curable material; and
exposing the curable material to light having a wavelength in a range from 400 nanometers to 510 nanometers to at least partially cure the curable material.

14. The method of claim 13 , wherein the curable material comprises a polythiol comprising more than one thiol group and a polyepoxide comprising more than one epoxide group.

15. The composition of claim 1 , wherein a weight ratio of the photolatent amine to a combined weight of camphorquinone and the coumarin sensitizer is in a range from 1:1 to 5:1.

16. The composition of claim 1 , wherein a weight ratio of camphorquinone to the coumarin sensitizer is in range from 1:1 to 10:1.

17. The composition of claim 1 , further comprising at least one polymerizable material.

18. The composition of claim 1 , further comprising a polythiol comprising more than one thiol group and a polyepoxide comprising more than one epoxide group.

19. The composition of claim 18 , wherein the polythiol is an oligomeric or polymeric polythioether or polysulfide.

20. The composition of claim 3 , wherein the coumarin sensitizer comprises at least one of 3,3′-carbonylbis(5,7-dimethoxycoumarin), 3-benzoyl-7-diethylaminocoumarin, 7-diethylamino-3-thenoylcoumarin, 3-(2-benzofuroyl)-7-diethylaminocoumarin, 7-diethylamino-5′,7′-dimethoxy-3,3-carbonylbiscoumarin, 3,3′-carbonylbis(7-diethylaminocoumarin), 9-(7-diethylamino-3-coumarinoyl)-1,2,4,5-tetrahydro-3H, 6H,10H[1]benzopyrano [9,9a, 1-gh]quinolazine-10-one, and 9,9′-carbonylbis(1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one).

Assignees

• 3M Innovative Properties Co

Inventors

• Clough Robert S
• Ye Sheng
• Gong Tao
• Zook Jonathan D
• Demoss Susan E
• Blackwell Charlie P

Classifications

• G03F7/038

  Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021) · CPC title

• C08G59/56 Primary

  together with other curing agents · CPC title

• G03F7/0045 Primary

  with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors · CPC title

• C09J181/02

  Polythioethers; Polythioether-ethers · CPC title

• C09J163/00

  Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins · CPC title