Method of preparing benzoxazine-thiol polymers films

Patent metadata

Field	Value
Publication number	US-9840591-B2
Application number	US-201113813306-A
Country	US
Kind code	B2
Filing date	Aug 2, 2011
Priority date	Aug 4, 2010
Publication date	Dec 12, 2017
Grant date	Dec 12, 2017

Abstract

A process for preparing benzoxazine-thiol polymer film is described comprising forming a rolling bank of a curable composition comprising a polybenzoxazine and a polythiol, wherein the rolling bank contacts first and second carrier substrates; passing the first and second substrates with the curable composition therebetween through a nip; and at least partially curing the curable composition to provide the corresponding polymeric layer. The compositions are useful in coating, sealants, adhesive and many other applications.

First claim

What is claimed is:

1. A method of preparing a benzoxazine-thiol polymer film comprising forming a rolling bank of a curable composition comprising a polybenzoxazine and a non-polymeric polythiol, wherein the rolling bank contacts first and second carrier substrates; passing the first and second substrates with the curable composition therebetween through a nip forming a thin reactive film with a thickness of less than or equal to 15 mils (381 micrometers); and at least partially curing the curable composition to provide the corresponding polymeric film, wherein the polythiol is of the formula R 4 —(S—H) n , where R 4 is an (hetero)hydrocarbyl having a valance of n, and n is 2 to 6.

2. The method of claim 1 , wherein the first and second carrier substrates with the curable composition therebetween are passed through the nip under conditions sufficient to provide a layer of the curable composition.

3. The method of claim 1 , wherein the curable composition is solvent-free.

4. The method of claim 1 , wherein at least one of said first and second carrier substrates is a release liner.

5. The method of claim 1 , comprising:
providing a first metering element and a second metering element defining a nip gap therebetween;
providing a first carrier substrate having a first width and a second carrier substrate having a second width;
disposing the first and second carrier substrates between the first and second metering elements;
forming the rolling bank between the first and second carrier substrates, wherein the rolling bank is medially disposed with respect to at least one of the first and second widths, comprises the curable composition, and has a first temperature;
independently heating at least a portion, at least partially proximate the rolling bank, of at least one of the first and second metering elements to a second temperature;
continuously passing, while disposed between the first and second carrier substrates, at least a portion of the curable composition of the rolling bank through the nip gap to form the thin reactive film sandwiched between the first and second carrier substrates; and
at least partially curing the thin reactive film to provide the thin film sandwiched between the first and second carrier substrates.

6. The method of claim 5 , wherein said at least one of the first and second metering elements is substantially uniformly heated.

7. The method of claim 1 , wherein, contemporaneously, the second temperature is greater than or equal to the first temperature.

8. The method of claim 1 , wherein at least one of the first and second metering elements comprises a rotatable roll.

9. The method of claim 5 , wherein at least one of the first and second metering elements comprises a fixed bar.

10. The method of claim 1 , wherein at least one of the first and second carrier substrates comprises a release coating thereon adjacent to the thin film.

11. The method of claim 1 , further comprising separating the first carrier substrate from the thin film.

12. The method of claim 11 , further comprising separating the second carrier substrate from the thin film.

13. The method of claim 1 , wherein the polybenzoxazine is of the formula:

wherein
each of R 1 is H or an alkyl group;
R 2 is H, a covalent bond, or a polyvalent (hetero)hydrocarbyl group;
R 5 is the (hetero)hydrocarbyl residue of a primary amino compound having a valence of x, and
x is at least 1.

14. The method of claim 1 , wherein the polybenzoxazine is of the formula:

wherein
each of R 1 is H or an alkyl group;
R 2 is H, a covalent bond, or a divalent (hetero)hydrocarbyl group;
R 5 is the divalent (hetero)hydrocarbyl group.

15. The method of claim 14 , wherein R 5 is a poly(alkyleneoxy) group.

16. The method of claim 1 , wherein the polybenzoxazine is of the formula:

each of R 1 is H or an alkyl group;
R 2 is H, a covalent bond, or a divalent (hetero)hydrocarbyl group;
R 5 is the (hetero)hydrocarbyl group.

17. The method of claim 1 , wherein the polybenzoxazine is of the formula:

wherein,
each of R 1 is H or an alkyl group;
R 2 is H, a covalent bond, or a divalent (hetero)hydrocarbyl group;
R 5 is the divalent (hetero)hydrocarbyl residue of a primary diamino compound.

18. The method of claim 1 , wherein R 4 is a non-polymeric aliphatic, cycloaliphatic, aromatic or alkyl-substituted aromatic moiety having from 1 to 30 carbon atoms and optionally 1 to four catenary heteroatoms of oxygen, nitrogen or sulfur.

19. The method of claim 1 , where the benzoxazine is derived from the reaction product of a phenol, an aldehyde and a primary amine.

20. The method of claim 1 , where the benzoxazine is derived from the reaction product of a bisphenol, an aldehyde and a primary amine.

21. The method of claim 1 , where the benzoxazine is derived from the reaction product of phenol, an aldehyde and a polyamine.

22. The method of claim 21 , wherein the polyamine is a poly(ethyleneoxy) diamine.

23. The method of claim 5 , wherein the partially cured curable composition comprises a polymer of the formula:

wherein
R 1 is H or an alkyl group;
R 2 is H, a covalent bond, or a divalent (hetero)hydrocarbyl group;
R 4 is (hetero)hydrocarbyl group of valence n and n is 2 to 6;
R 5 is a (hetero)hydrocarbyl group, and y is at least 2.

24. The method of claim 5 , wherein the polybenzoxazine compound comprises a mixture of an N-aromatic polybenzoxazine compounds and an N-aliphatic polybenzoxazine compounds.

25. The method of claim 24 , wherein the benzoxazine comprises
a. 30 to 90 mole % of said N-aryl benzoxazine
b. 10 to 70 mole % of said N-alkyl benzoxazine; and
c. a stoichiometric equivalent of said thiol compound±15%.

26. The method of claim 24 , wherein the first temperature is sufficient to initiate the curing of the N-aliphatic polybenzoxazine compounds with the polythiol.

Assignees

• Gorodisher Ilya
• Johnson Michael A
• 3M Innovative Properties Co

Inventors

• Gorodisher Ilya
• Johnson Michael A

Classifications

• B29K2105/243

  Partially cured · CPC title

• C08G75/14 Primary

  Polysulfides · CPC title

• B29K2081/00

  Use of polymers having sulfur, with or without nitrogen, oxygen or carbon only, in the main chain, as moulding material · CPC title

• C08J5/18 Primary

  Manufacture of films or sheets · CPC title

• C08J2379/02

  Polyamines · CPC title