IONIC POLYMERS AND THEIR USE AS WET-ADHESIVES AND COATINGS

Abstract

The present application discloses an adhesive composition comprising a polymer of the formulae A, B and C:

##STR00001##

and methods for using the adhesive composition.

##STR00002##

Claims

1. An adhesive composition comprising a polymer of the formulae A, B and C: ##STR00048## wherein: each m, n and o is independently 100 to 1,000,000; each a, b, s, t, x and y is independently 0, 1 or 2; each L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5 and L.sup.6 is independently absent or is independently selected from the group consisting of —CH.sub.2—, —O—, —S—, —(CH.sub.2).sub.1,2—, —CH(CH.sub.2-).sub.2—, —C(O)O—, —C(O)OCH.sub.2—, —CH.sub.2C(O)O—, —CH.sub.2C(O)NH—, —C(O)NHCH.sub.2—, —C(O)NH— and —NR′— where R′ is selected from H, —CH.sub.3, —CH.sub.2CH.sub.3 and —CH.sub.2C.sub.6H.sub.5 or substituted benzyl, or a bond; each A, B, M, N, X and Y is independently absent or selected from the group consisting of an aryl, substituted aryl, aryl ammonium, heteroaryl, substituted heteroaryl, heteroarylammonium X.sup.−and substituted heteroarylammonium X.sup.−, wherein each X.sup.− is independently a counter anion selected from the group consisting of Cl.sup.−, Br.sup.−, I.sup.−, —SO.sub.4.sup.−2 and —PO.sub.4.sup.−3; provided that not all of L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5 and L.sup.6, and A, B, M, N, X and Y are absent; provided that for Formula A, only one of A, B is a heteroarylammonium X.sup.−or a substituted heteroarylammonium X.sup.−; and provided that when L.sup.1 is −(CH.sub.2).sub.1,2— or a bond, then the group -(A).sub.a-L.sup.2-(B).sub.b is not a group selected from -heteroarylammonium(X)-L.sup.2-dihydroxy-phenyl, a substituted or unsubstituted imidazole and a substituted or unsubstituted imidazolinium (X.sup.−).

2. The adhesive of claim 1, wherein each A, B, M, N, X and Y is independently selected from the group consisting of: ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055## wherein: each L.sup.1, L.sup.2, L.sup.3 and L.sup.4 is independently H, —CH.sub.3, —CH.sub.2-, —O—, —S—, —(CH.sub.2).sub.1,2—, —CH(CH.sub.2—).sub.2, —C(O)O—, —C(O)OCH.sub.2—, —CH.sub.2C(O)O—, —CH.sub.2C(O)NH—, —C(O)NHCH.sub.2—, —C(O)NH— and —NR′— where R′ is selected from H, —CH.sub.3, —CH.sub.2CH.sub.3 and —CH.sub.2C.sub.6H.sub.5, a bond and —NR'- where R′ is selected from H, —CH.sub.3, —CH.sub.2CH.sub.3and —CH.sub.2C.sub.6H.sub.5 or substituted benzyl; each R, R.sup.1 and R.sup.2 is independently H or is selected from the group consisting of F, Cl, Br, I, —OH, —SiH.sub.2OH, —NO.sub.2, —CH.sub.3, —CF.sub.3, a substituted aryl group, —CO.sub.2H, —SO.sub.4H, —SO.sub.3H, —PO.sub.4H.sub.2, —PO.sub.3H.sub.2, —NH.sub.3.sup.+, —CH.sub.2C.sub.6H.sub.5, -3,4-dihydroxyphenyl, —CH.sub.2-3,4-dihydroxyphenyl, N-succinimidyl, —NR′R″ where R′ and R″ are each independently selected from H, —CH.sub.3, —CH.sub.2CH.sub.3 and —CH.sub.2C.sub.6H.sub.5 or substituted benzyl, and a curable group; each R.sup.3 is independently H or is selected from the group consisting of —CH.sub.3, —CH.sub.2CH.sub.3, a substituted aryl group, —CO.sub.2H, —SO.sub.4H, —SO.sub.3H, —PO.sub.4H.sub.2, —PO.sub.3H.sub.2, —NH.sub.3.sup.+ and —CH.sub.2C.sub.6H.sub.5 or substituted benzyl, and a curable group; and Z is —(CH.sub.2).sub.t— or —(NH)— where t is 0 or 1.

3. The adhesive of claim 1, wherein each of B, N and Y independently comprises an amine, glycidyl, acrylate, methacrylate or a vinyl derivative of the formulae: ##STR00056##

4. The adhesive of claim 1, wherein at least one of A, B, M, N, X and Y is independently selected from the group consisting of the formulae: -L.sup.1-COOH, -L.sup.1-SO.sub.4H, -L.sup.1-SO.sub.3H, -L.sup.1-PO.sub.4H.sub.2, -L.sup.1-PO.sub.3H.sub.2 and L.sup.1-NH.sub.3.sup.+; -L.sup.3-COOH, -L.sup.3-SO.sub.4H, -L.sup.3-SO.sub.3H, -L.sup.3-PO.sub.4H.sub.2, -L.sup.3-PO.sub.3H.sub.2 and L.sup.3-NH.sub.3.sup.+; and -L.sup.5-COOH, -L.sup.5-SO.sub.4H, -L.sup.5-SO.sub.3H, -L.sup.5-PO.sub.4H.sub.2, -L.sup.5-PO.sub.3H.sub.2 and L.sup.5-NH.sub.3.sup.+; wherein each L.sup.1, L.sup.3 and L.sup.5 is independently selected from a bond, —CH.sub.2—, —O—, —S—, —C(O)OCH.sub.2—, —C(O)NHCH.sub.2— and —NR′— where R′ is selected from H, —CH.sub.3, —CH.sub.2CH.sub.3 and —CH.sub.2C.sub.6H.sub.5 or a substituted benzyl;

5. The adhesive of claim 1, wherein each of B, N and Y is independently selected from the group consisting of the formulae: ##STR00057##

6.-8. (canceled)

9. The adhesive of claim 1, wherein the substituted aryl group is selected from the group consisting of: ##STR00058## ##STR00059## ##STR00060## and b, n and y is 1 or 2.

10. The adhesive of claim 1, comprising the formulae B.sup.1, B.sup.2, B.sup.3, B.sup.4 and B.sup.5: ##STR00061## wherein: each m and n is independently 100 to 1,000,000; each L.sup.1 and L.sup.3 is independently selected from a bond, —CH.sub.2—, —O—, —S—, —C(O)O—, —C(O)OCH.sub.2—, —CH.sub.2C(O)O—, —CH.sub.2C(O)NH—, —C(O)NHCH.sub.2—, —C(O)NH— and —NR′— where R′ is selected from H, —CH.sub.3, —CH.sub.2CH.sub.3 and —CH.sub.2C.sub.6H.sub.5 or substituted benzyl; each R and R.sup.1 is independently H or is selected from the group consisting of F, Cl, Br, I, —OH, —SiH.sub.2OH, —NO.sub.2, —CH.sub.3, —CO.sub.2H, —SO.sub.4H, —SO.sub.3H, —PO.sub.4H.sub.2, —PO.sub.3H.sub.2, —NH.sub.3.sup.+, —CH.sub.2C.sub.6H.sub.5, -3,4- dihydroxyphenyl, —CH.sub.2-3,4-dihydroxyphenyl, —NR′R″ where R′ and R″ are each independently selected from H, —CH.sub.3, —CH.sub.2CH.sub.3, —CH.sub.2C.sub.6H.sub.5 or substituted benzyl, and a curable group; each R.sup.3 is independently H or is selected from the group consisting of —CH.sub.3, —CH.sub.2CH.sub.3, —CO.sub.2H, —SO.sub.4H, —SO.sub.3H, —PO.sub.4H.sub.2, —PO.sub.3H.sub.2, —NH.sub.3.sup.+, —CH.sub.2C.sub.6H.sub.5 or substituted benzyl and a curable group; and each X.sup.− is independently a counter anion selected from the group consisting of Cl.sup.−, Br.sup.−, I.sup.−, —SO.sub.4 .sup.2, —PO.sub.4 .sup.3 and CH.sub.3CO.sub.2.

11. The adhesive of claim 1, comprising the formulae C.sup.1, C.sup.2,C.sup.3, C.sup.4, C.sup.5 and C.sup.6: ##STR00062## wherein: each m, n and y is independently 100 to 1,000,000; each L.sup.1, L.sup.3 and L.sup.5 is independently selected from —CH.sub.2—, —O—, —S—, —(CH.sub.2).sub.1,2—, —CH(CH.sub.2—).sub.2, —C(O)O—, —C(O)OCH.sub.2—, —CH.sub.2C(O)O—, —CH.sub.2C(O)NH—, —C(O)NHCH.sub.2—, —C(O)NH— and —NR′— where R′ is selected from H, —CH.sub.3, —CH.sub.2CH.sub.3 and —CH.sub.2C.sub.6H.sub.5 or substituted benzyl, or a bond; each R and R.sup.1 is independently H or is selected from the group consisting of F, Cl, Br, I, —OH, —SiH.sub.2OH, —NO.sub.2, —CH.sub.3, —CO.sub.2H, —SO.sub.4H, —SO.sub.3H, —PO.sub.4H.sub.2, —PO.sub.3H.sub.2, —NH.sub.3.sup.+, —CH.sub.2C.sub.6H.sub.5 or substituted benzyl, -3,4-dihydroxyphenyl, —CH.sub.2-3,4-dihydroxyphenyl and —NR′R″ where R′ and R″ are each independently selected from H, —CH.sub.3, —CH.sub.2CH.sub.3 and —CH.sub.2C.sub.6H.sub.5 or substituted benzyl; each R.sup.3 is independently H or is selected from the group consisting of —CH.sub.3, —CH.sub.2CH.sub.3, —CO.sub.2H, —SO.sub.4H, —SO.sub.3H, —PO.sub.4H.sub.2, —PO.sub.3H.sub.2, —NH.sub.3.sup.+ and —CH.sub.2C.sub.6H.sub.5; and each X.sup.− is independently a counter anion selected from the group consisting of Cl.sup.−, Br.sup.−, I.sup.−, —SO.sub.4.sup.−2 and —PO.sub.4.sup.−3.

12.-13. (canceled)

14. The adhesive of claim 1, wherein the curable group is a photocurable group, a photopolymerizable group, a thermal curable group and a solvent curable group.

15. A method for sealing a first object having a surface to a second object having surface, the method comprising: 1) applying an adhesive to the surface of the first object; 2) contacting the surface of the first object comprising the adhesive with the surface of the second object for a sufficient period of time until the first and second object forms a seal; wherein the adhesive is an adhesive composition comprising a polymer of the formula A, B or C: ##STR00063## wherein: each m, n and o is independently 100 to 1,000,000; each a, b, s, t, x and y is independently 0, 1 or 2; each L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5 and L.sup.6 is independently absent or is independently selected from —CH.sub.2—, —O—, —S—, (CH.sub.2).sub.1,2—, —CH(CH.sub.2—).sub.2, —C(O)O—, —C(O)OCH.sub.2—, —CH.sub.2C(O)O—, —CH.sub.2C(O)NH—, —C(O)NHCH.sub.2—, —C(O)NH— and —NR′— where R′ is selected from H, —CH.sub.3, —CH.sub.2CH.sub.3 and —CH.sub.2C.sub.6H.sub.5 or substituted benzyl, or a bond; each A, B, M, N, X and Y is independently absent or is independently selected from the group consisting of an aryl, substituted aryl, heteroaryl, substituted heteroaryl, heteroarylammonium X.sup.− and substituted heteroarylammonium X.sup.−, wherein each X.sup.− is independently a counter anion selected from the group consisting of Cl.sup.−, Br.sup.−, I.sup.−, —SO.sub.4.sup.−2 and —PO.sub.4.sup.−3; provided that not all of L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5 and L.sup.6 and A, B, M, N, X and Y are absent.

16. The method of claim 15, wherein the adhesive comprises of the formulae A.sup.1, A.sup.2, A.sup.3, A.sup.4, A.sup.5, A.sup.6, A.sup.7, A.sup.8, A.sup.9, A.sup.10, A.sup.11, A.sup.11, A.sup.12, A.sup.13 and A.sup.14: ##STR00064## ##STR00065## ##STR00066## wherein: each n is independently 100 to 1,000,000; each L.sup.1 and L.sup.3 is independently selected from a bond, —CH.sub.2—, —O—, —S—, —C(O)O—, —C(O)OCH.sub.2—, —CH.sub.2C(O)O—, —CH.sub.2C(O)NH—, —C(O)NHCH.sub.2—, —C(O)NH— and —NR′— where R′ is selected from H, —CH.sub.3, —CH.sub.2CH.sub.3 and —CH.sub.2C.sub.6H.sub.5 or substituted benzyl; each R and R.sup.1 is independently H or is selected from the group consisting of F, Cl, Br, I, —OH, —SiH.sub.2OH, —NO.sub.2, —CH.sub.3, —CO.sub.2H, —SO.sub.4H, —SO.sub.3H, —PO.sub.4H.sub.2, —PO.sub.3H.sub.2, —NH.sub.3.sup.+, —CH.sub.2C.sub.6H.sub.5, —3,4-dihydroxyphenyl, a curable group, —CH.sub.2-3,4-dihydroxyphenyl, —NR′R″ where R′ and R″ are each independently selected from H, —CH.sub.3, —CH.sub.2CH.sub.3 and —CH.sub.2C.sub.6H.sub.5 or substituted benzyl; each R.sup.3 is independently H or is selected from the group consisting of —CH.sub.3, —CH.sub.2CH.sub.3, a curable group and —CH.sub.2C.sub.6H.sub.5 where the C.sub.6H.sub.5 group is optionally substituted with 1 substituent selected from the group consisting of halogen (—F, —Cl, —Br— or —I), —OH, —SH, —SiH.sub.2OH, —NH.sub.2, —NO.sub.2, —CO.sub.2H, —SO.sub.4H, —SO.sub.3H, —PO.sub.4H.sub.2, —PO.sub.3H.sub.2, —N.sub.3.sup.+, —CH.sub.3, —CF.sub.3, —OCH.sub.3 and —OCF.sub.3; and each X.sup.−is independently a counter anion selected from Cl.sup.−, Br.sup.−, I.sup.−, —SO.sub.4.sup.−2, —PO.sub.4.sup.−3 and CH.sub.3CO.sub.2.sup.−, each X.sup.− is independently a counter anion selected from the group consisting of Cl.sup.−, Br.sup.−, I.sup.−, —SO.sub.4.sup.−2 and —PO.sub.4.sup.−3.

17. The method of claim 15, wherein the adhesive comprises of the formulae B.sup.1, B.sup.2, B.sup.3, B.sup.4, B.sup.5 and B.sup.6: ##STR00067## wherein: each m and n is independently 100 to 1,000,000; each L.sup.1 and L.sup.3 is independently selected from a bond, —CH.sub.2—, —O—, —S—, —C(O)O—, —C(O)OCH.sub.2—, —CH.sub.2C(O)O—, —CH.sub.2C(O)NH—, —C(O)NHCH.sub.2—, —C(O)NH— and —NR′— where R′ is selected from H, —CH.sub.3, —CH.sub.2CH.sub.3 and —CH.sub.2C.sub.6H.sub.5 or substituted benzyl; each R and R.sup.1 is independently H or is selected from the group consisting of F, Cl, Br, I, —CF.sub.3, —OH, —SiH.sub.2OH, —NO.sub.2, —CO.sub.2H, —SO.sub.4H, —SO.sub.3H, —PO.sub.4H.sub.2, —PO.sub.3H.sub.2, —NH.sub.3.sup.+, —CH.sub.3, —CH.sub.2C.sub.6H.sub.5, -3,4-dihydroxyphenyl, —CH.sub.2-3,4-dihydroxyphenyl, a curable group, —NR′R″ where R′ and R″ are each independently selected from H, —CH.sub.3, —CH.sub.2CH.sub.3 and —CH.sub.2C.sub.6H.sub.5 or substituted benzyl; each R.sup.3 is independently H or is selected from the group consisting of —CO.sub.2H, —SO.sub.4H, —SO.sub.3H, —PO.sub.4H.sub.2, —PO.sub.3H.sub.2, —NH.sub.3.sup.+, —CH.sub.3, —CH.sub.2CH.sub.3, —CH.sub.2C.sub.6H.sub.5 or substituted benzyl, and a curable group; and each X.sup.− is independently a counter anion selected from the group consisting of Cl.sup.−, Br.sup.−, I.sup.−, —SO.sub.4.sup.−2 and —PO.sub.4.sup.−3.

18. The method of claim 15, wherein the adhesive comprises the formulae C.sup.1, C.sup.2, C.sup.3, C.sup.4, C.sup.5 and C.sup.6: ##STR00068## wherein: each m, n and y is independently 100 to 1,000,000; each L.sup.1, L.sup.3 and L.sup.5 is independently selected from a bond, —CH.sub.2—, —O—, —S—, —C(O)O—, —C(O)OCH.sub.2—, —CH.sub.2C(O)O—, —CH.sub.2C(O)NH—, —C(O)NHCH.sub.2—, —C(O)NH— and —NR′— where R′ is selected from H, —CH.sub.3, —CH.sub.2CH.sub.3 and —CH.sub.2C.sub.6H.sub.5 or substituted benzyl; each R and R.sup.1 is independently H or is selected from the group consisting of F, Cl, Br, I, —OH, —SiH.sub.2OH, —NO.sub.2, —CO.sub.2H, —SO.sub.4H, —SO.sub.3H, —PO.sub.4H.sub.2, —PO.sub.3H.sub.2, —NH.sub.3.sup.+, —CH.sub.3, —CF.sub.3, —CH.sub.2C.sub.6H.sub.5, -3,4-dihydroxyphenyl, a curable group, —CH.sub.2-3,4-dihydroxyphenyl, —NR′R″ where R′ and R″ are each independently selected from H, —CH.sub.3, —CH.sub.2CH.sub.3 and —CH.sub.2C.sub.6H.sub.5 or substituted benzyl; each R.sup.3 is independently H or is selected from the group consisting of —CO.sub.2H, —SO.sub.4H, —SO.sub.3H, —PO.sub.4H.sub.2, —PO.sub.3H.sub.2, —NH.sub.3.sup.+, —CH.sub.3, —CH.sub.2CH.sub.3, —CH.sub.2C.sub.6H.sub.5 and a curable group; and each X.sup.− is independently a counter anion selected from the group consisting of Cl.sup.−, Br.sup.−, I.sup.−, —SO.sub.4.sup.−2 and —PO.sub.4.sup.−3.

19.-20. (canceled)

21. The method of claim 15, wherein at least one of A, B, M, N, X and Y is independently selected from the group consisting of the formulae: -L.sup.1—COOH, -L.sup.1-SO.sub.4H, -L.sup.1-SO.sub.3H, -L.sup.1-PO.sub.4H.sub.2, -L.sup.1—PO.sub.3H.sub.2 and L.sup.1-NH.sub.3.sup.+; -L.sup.3—COOH, -L.sup.3-SO.sub.4H, -L.sup.3-SO.sub.3H, -L.sup.3-PO.sub.4H.sub.2, -L.sup.3—PO.sub.3H.sub.2 and L.sup.3-NH.sub.3.sup.+; and -L.sup.5—COOH, -L.sup.5-SO.sub.4H, -L.sup.5-SO.sub.3H, -L.sup.5-PO.sub.4H.sub.2, -L.sup.5—PO.sub.3H.sub.2 and L.sup.5-NH.sub.3.sup.+; wherein each L.sup.1, L.sup.3 and L.sup.5 is independently selected from a bond, —CH.sub.2—, —O—, —S— and —NR′— where R′ is selected from H, —CH.sub.3, —CH.sub.2CH.sub.3 and —CH.sub.2C.sub.6H.sub.5.

22. The method of claim 15, wherein each of B, N and Y independently comprises a derivative of the formulae: ##STR00069##

23. The method of claim 15, wherein each of B, N and Y is independently selected from the group consisting of the formulae: ##STR00070##

24. The method of claim 15, wherein at least one of A, M and X is independently selected from the group consisting of the formulae: ##STR00071##

25. The method of claim 15, wherein the adhesive is further cured.

26. The method of claim 15, wherein the first object is independently selected from the group consisting of a dermis, metal, a metal oxide, a mineral, mica, silicon, glass, calcium, enamel, bone, steel, tooth enamel, tooth dentin, hydroxylapatite, kaolin and zirconia; and the second object is selected from the group consisting of a tissue, dermis, metal, a metal oxide, a mineral, mica, silicon, glass, calcium, enamel, bone, steel, tooth enamel, tooth dentin, hydroxylapatite, kaolin and zirconia.

27. (canceled)

28. The method of claim 15, wherein the first object is dermis and the second object is selected from the group consisting of a metal, a metal oxide, a mineral, mica, silicon, glass, calcium, enamel, bone, steel, tooth enamel, tooth dentin, hydroxylapatite, kaolin and zirconia.

29.-31. (canceled)

Description

DETAILED DESCRIPTION OF THE INVENTION

[0086] Definition:

[0087] The term “copolymer” means a polymer that is made from two or more different monomers. Examples of such monomers may include ethylene, styrene and acrylonitrile, and their substituted derivatives. For example, two different monomers may be allowed to polymerize in a reaction medium such that a copolymer is formed that contains both residues of the two different monomeric units. In one aspect, the copolymer may be a random copolymer having no definitive sequence of the monomer units. In another aspect, the copolymer may be a regular copolymer with regular alternating sequence of two monomer units. In another aspect, the copolymer may be a block copolymer containing a block of one monomer connected to a block of another monomer.

[0088] The total number average molecular weight (Mn.sub.t or Mn) of the polymers or block polymers or copolymers of the present invention is typically provided in various ranges, of from about 5,000 to 6,000, 6,000 to 8,000, 8,000 to 10,000, 10,000 to 12,000, 28,000 to 30,000, 43,000 to 45,000, 53,000 to 55,000, 58,000 to 60,000, 78,000 to 80,000, 88,000 to 90,000, 97,000 to 100,000, 115,000 to 120,000, 125,000 to 130,000, 135,000 to 140,000, 145,000 to 150,000, 200,000 to 400,000, 400,000 to 500,000, 500,000 to 600,000, 600,000 to 700,000 or about 700,000 to about 1,000,000. The Mn may be determined standard methods employed in the an, such as by using chromatography such as gel permeation chromatography (GPC). The molecular weight of the block copolymer and properties obtained are dependent upon the molecular weight of each of the polymers or polymeric blocks.

[0089] The term “cure” or “curing” refers to the hardening or toughening of a polymer material by cross-linking of the polymer chains in the polymer. Such process may be performed by various methods, including by heat, light (UV or visible), radiation, electron beams or by adding certain chemical additives. In certain curing procedures, the additive may be activated with UV radiation resulting in a UV curing process.

[0090] The term “homopolymer” means a polymer that are formed by the reaction starting with the same monomer. Homopolymers may include addition polymers that are polymers or macromolecules that are formed by the addition reaction of olefins, acetylenes, aldehydes or other compounds having an unsaturated bond or functional group. Representative homopolymers from monomers include polyethylene from ethylene, poly(vinyl chloride) from vinyl chloride, polyacrylonitrile from acrylonitrile, polystyrene from styrene etc.

[0091] The term “monomer” means any substance or molecule that can be converted or made into a polymer. Examples of such monomers may include ethylene, styrene and acrylonitrile. Monomers may also refer to dimers or trimers, if for example, the dimers or trimers can also undergo further polymerization.

[0092] “Optionally substituted” means a group, such as an alkyl group, an aryl group, a heteroaryl group, as disclosed herein, may be substituted by one or more substituents selected from halogen (—F, —Cl, —Br— or —I), —OH, —SH, —SiH.sub.2OH, —NH.sub.2, —NO.sub.2, —CH.sub.3, —CF.sub.3, —OCH.sub.3 and —OCF.sub.3. For example, an optionally substituted or substituted benzyl group substituted with 1 substituent selected from the group consisting of halogen (—F, —Cl, —Br— or —I), —OH, —SH, —SiH.sub.2OH, —NH.sub.2, —NO.sub.2, —CO.sub.2H, —SO.sub.4H, —SO.sub.3H, —PO.sub.4H.sub.2, —NH.sub.3.sup.+, —CH.sub.3, —CF.sub.3, —OCH.sub.3 and —OCF.sub.3.

[0093] The term “polymer” means a molecule having a structure that is composed of multiple repeating units, and may refer to a substance or molecule with high molecular weight. Representative of such polymers may include linear polymers comprising a long chain of skeletal atoms to which are attached substituents or substituent groups; branched polymers that may be linear polymers with branches of the same or similar basic structure as the main chain; or cross-linked. or network polymers where chemical linkages are present between the chains of the polymers. The polymers or copolymers may be random copolymers, alternating copolymers (e.g., regular alternating A and B monomers), periodic copolymers, statistical copolymers or block copolymers.

[0094] The term “random” polymers or copolymers are polymers in which the monomer units are incorporated into the chain wherein there can exist various combinations of ordering including block polymer units where, for example, either the first monomeric unit or second monomeric unit (or third unit, fourth unit etc . . . , as provided herein) or both units may be repeated and are adjacent to one another. “Alternating” first monomeric and second monomeric copolymers are those in which the first monomeric and second monomeric units occur in repeating alternate sequences on the polymer chain in atactic structures (such as isotactic or syndiotactic) or in combinations of the general formula as described herein, wherein x and y are integers from 1 to 10,000. The term “substantially random” as used herein in reference to the first and second monomeric units form a copolymer where the distribution of the monomers or monomeric units of the copolymer may be described by the Bernoulli statistical model or by a first or second order Markovian statistical model, as described by J. C. Randall in Polymer Sequence Determination, Carbon-13 NMR Method. Academic Press NY, 1977, pp. 71-78. The composition (of monomer) distribution of the copolymer can also be determined using .sup.13C NMR analysis using the methods described in U.S. Pat. No. 5,292,845; U.S. Pat. No. 5,089,321, and by J. C. Randall, Rev. Macromol. Chem. Phys. C29, pp. 201-317 (1989).

[0095] In one embodiment, the present application disclosescationic or amphilic ionic copolymer-containing heterocycles and heterocyclic salts such as pyridines and substituted pyridines, pyridinium salts, substituted pyridinium salts, imidazoles and substituted imidazoles, imidazolium salts and substituted imidazolium salts, epoxides, glycidol derivatives, hydroxy aromatics, hydroxy phenols, polyhydroxy phenols, catechol and substituted catechol monomers which can undergo multiple continuous phase inversion in saline water and may be solidified into an adhesive such as a wet adhesive or wet glue. In another embodiment, there is provided the heterocyclic salts in combination with imidazoles and substituted imidazoles, imidazolium salts and substituted imidazolium salts, epoxides, glycidol derivatives, hydroxy aromatics, hydroxy phenols, polyhydroxy phenols, catechol and substituted catechol monomers. These ionic polymer glues can adhere and adsorb onto surfaces of biological tissues, bones, hydrogels, plastics, metals, ceramics and/or the interfaces between them through a combination of electrostatic, hydrophobic, chelating interactions and hydrogen bonding. Lee, B. P.; Messersmith, P. B.; Israelachvili, J. N.; Waite, J. H., Mussel-Inspired Adhesives and Coatings. Annu Rev Mater Res, 2011, 41, 99-132. The bonding strength of these ionic polymer glue can be further enhanced through secondary crosslinking with another functional group, for example, by oxidative crosslinking of a functional group, such as catechol, cationic/anionic/radical polymerization of epoxides, acrylates, methacrylates; coupling/crosslinking of epoxides, arylates, methacrylates, aldehydes, N-succinimidyl group, etc., and at different pH, such as at pH>6 conditions.

[0096] Some embodiments of the current invention are discussed in detail below. In describing embodiments, specific terminology is employed for the sake of clarity. However, the invention is not intended to be limited to the specific terminology so selected. A person skilled in the relevant art will recognize that other equivalent components can be employed and other methods developed without departing from the broad concepts of the current invention. All references cited in this specification, including the Background, Detailed Description sections and Examples, are incorporated by reference into this disclosure as if each had been individually incorporated.

[0097] Some embodiments in the present application are directed to polymers, such as ionic polymers, that may be used under moist or wet conditions, such as an underwater glue. In one embodiment, the underwater adhesive (wet or bio-glue) is based anionic copolymers containing(1) nitrogen-containing heterocyclic cationic functional residues such as imidazolium groups and pyridinium groups, that are selected from the group consisting of an ammonium, quinolinium, isoquinolinium, phenathridinium, phenanthrolinium, pyrimidinium, benzothoazolinium, benzothiadiazolinium, purinium, pyrazinium or acridinium and (2) coupling residues such as di, tri-, tetra- and penta-hydroxy benzene, polycyclic hydrocarbons (e.g., naphthalene, anthracene, etc.), aryls, heteroaryl, N-succinimidyl, indole and imidazole moieties and their derivatives, that may form bonds, such as hydrogen bonds, covalent bonds and/or attachments on to a material surface and/or form crosslinked networks such as aldehydes, mono-, di- or poly-acrylates and methacrylates, di, tri-, tetra- and penta-hydroxy benzene, polycyclic hydrocarbons (e.g., naphthalene, anthracene, etc.), aryls, heteroaryl, N-succinimidyl, indole and imidazole moieties and their derivatives.

[0098] In one variation, the ionic copolymer may be based on any polymer backbones such as polystyrene, polyacrylate, polymethacrylate, polyester, polyether from any vinyl, acrylate and/or methacrylate co-monomers.

[0099] In one embodiment, the disclosed polymer contains aryl derivatives, such as benzyl or phenyl derivatives, attached to the pyridine and imidazolium groups through methylene spacer groups. The polymer glue is soluble in water and forms stable aqueous solution. When the aqueous solution of ionic polymer glue is applied to substrates submerged in saline water (salt concentration: 0.1-2 M, pH 1-12 or isotonic), the polymer can undergo liquid-to-solid phase inversions and self-assemble into viscoelastic underwater glue. The glue may coat surfaces (e.g. biological tissues, hydrogel, plastics, metal, glass, ceramics) in saline water, or glue two surfaces or objects together. The strength of the glue can be further enhanced through the oxidative crosslinking of monomers, such as catechol monomers, at pH above 5, 6, 7 or pH 8-9.

[0100] In one aspect, x, z are monomer molar ratio of the imidazolium and catechol monomers in the ionic polymer. In some embodiments, the polymer disclosed in the present application may be used as underwater glue or adhesive coating in saline water. The ionic polymer glue of the present application have strong adhesion/cohesion in saline water. The ionic polymer glue may adhere to diverse surfaces and self-assembles into a primer, a coating, a glue or an adhesive layer. In some embodiments, the ionic polymer glue of the present application may be applied onto biological tissues, such as human tissues, including teeth, bones and medical and dental implants, and other materials, including plastics, ceramics and metals.

[0101] In some embodiments, the adhesive polymer or ionic polymer glue of the present application may be crosslinked or further cured, as disclosed herein. In one variation, the polymer may be crosslinked with aqueous oxidizing agents, or in an environment or condition where the pH>6.

[0102] In some embodiments, the ionic polymer glue of the present application may be used as an adhesive or a bio-glue for surgical intervention, plastic surgery, dental adhesive, bone adhesive, wet glue for tissue-tissue adhesion and bone-tissue adhesion or joints, underwater glue for bone-tissue joints, adhesive coatings for dental and medical implants, or surface primers for mineral fillers used for polymer composites including dental and bone cements, adhesives, composites or electronic devices.

[0103] General Scheme for The Preparation of Representative polymers:

##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042##

[0104] Experimental:

[0105] The procedures for the preparation of the homopolymers or copolymers are based on a related process for the preparation of highly conductive, mesoporous, graphitic nanostructures as described in J. Yuan et al., Chem. Mater. 2010, 22, 5003-5012.

General Procedure:

[0106] The co-monomers (for example protected catechol acrylate and 2-diethylaminoethyl acrylate) are mixed in accordance with the desired molar ratios for each application, along with a catalyst (for example, 0.01 equiv of a radical photoinitiator, e.g., acrylic acid and azobisisobutyronitrile (AIBN)) dissolved in desired solvent such as toluene/THF for non-polar co-monomers or DMF/diglyme/water for polar co-monomers.

[0107] In one particular process of using the copolymers, such as polymers comprising catechol cationic copolymers, the copolymers are prepared from a protected catechol acrylate due to the spontaneous autoxidation of the catechol functional group, or the reactions are carried in acidic conditions to generate a reducing environment (pH<5.5) for catechols. In one method, where the protecting groups are present, the silyl-protecting groups are later cleaved in an aqueous pH<3 solution at room temperature.

[0108] Visible or UV light curing system: For further crosslinking of acrylate side groups of non-acrylate copolymers (e.g., polyester with acrylate side chains) to enhance cohesion of glues, visible or UV radical polymerization are carried out.

[0109] Hand peel test: Once each adhesive film is prepared on PET backing and tested by hand. The stickiness or adhesive property of the tapes in water is stronger than stickiness of 3M Scotch packing tapes in dry ambient condition.

[0110] 1-Vinyl 3-benzylimidazolium chloride:

##STR00043##

[0111] The title compound was prepared as follows: 30 ml of N-vinylimidazole (331 mmol, 1 equiv.) was added to a dry round bottom flask fitted with a rubber septa, stir bar, and argon needle. 100 ml of anhydrous MeCN was added to the flask via syringe, and stirred. Once completely dissolved, 30 ml of benzyl chloride (339 mmol, 1.02 equiv.) was added and the mixture was stirred at 65° C. for 18-24 hours under argon. The mixture was then cooled to ambient temperature, and volatiles were removed by rotary evaporation under reduced pressure to obtain a viscous oil. Traces of MeCN and excess benzyl chloride were removed by addition of diethyl ether to the flask, which was then vigorously swirled then let settle, and the ether layer was decanted off from the oil. This process of swirling with ether, settling, then decantation, was repeated several times with fresh ether until no further odor of benzyl chloride could be detected. The last traces of solvent were then removed on high vacuum to obtain the desired compound as a tan froth of bubbles in quantitative yield (73 grams, 100%).

[0112] Poly (1-vinyl 3-benzylimidazolium chloride, HP-1)

##STR00044##

[0113] The title compound was prepared as follows: To a dry round bottom flask fitted with a stir bar, rubber septa, and argon needle was added 43.7 grams of the preceding imidazolium salt dissolved in 150 ml of anhydrous DMF. 164 mg of AIBN (azabisisobutryonitrile, 1 mmol, 0.005 equiv.) was added as a solid, and the solution was sparged with argon for 10 minutes. Once fully sparged, the flask was heated at 85° C. for 3 days, with stiffing. The flask was cooled to ambient temperature, and DMF was removed by 3 rounds of coevaporation with toluene on a rotary evaporator. The polymer was purified by dissolving the crude residue in a minimum amount of methanol, and reprecipitation from THF (volume MeOH:THF=1:10), where the solid was let settle and supernatant discarded. This process of reprecipitation was repeated once more. Traces of methanol were removed by stiffing the solids with THF, letting settle then decanting off the THF. This process was repeated, substituting hexanes for THF, where after decantation the solids were transferred by spatula to a round bottom flask, and traces of solvent were removed under high-vacuum to afford pure polymer.

Synthesis of Homopolymer (HP-2):

[0114] ##STR00045##

[0115] Into a 50 mL flask equipped with a magnetic stir bar under nitrogen is added the monomer 4-vinyl-1-benzylpyridinium chloride (M3, 5 g). The monomer is dissolved in 50 mL of DMF. Azobisisobutyronitrile (AIBN) initiator (100 mg) was added into the solution. The solution is then stirred at 90° C. for 20 h. The mixture is cooled to room temperature. Polymer is then precipitated and dried as described in the above procedure. About 5 g of HP-2 is obtained after the purification.

Synthesis of Copolymer, P2:

[0116] Both monomers M1 and M2 are prepared according to literature methods. See for example, J. Yuan et al., Chem. Mater. 2010, 22, 5003-5012. 1-Vinyl-3-benzyl imidazolium chloride (monomer M1, 1 g) and silyl protected catechol acrylate derivative (monomer M2, 0.3 g) are added to a 250 mL 3—N RBF with a magnetic stir bar under nitrogen. The monomers are dissolved in N,N-dimethylformamide (DMF, 10 mL) and stirred at room temperature for about 15 minutes. Azobisisobutyronitrile (AIBN) initiator (13 mg) is added into the solution mixture, and the reaction mixture is stirred and heated to 80° C. for 24 h (FIG. 1). After the reaction is completed, the solution is transferred to a 500 mL RBF. Diethyl ether (150 mL) is added to the stirred reaction mixture to precipitate out the crude polymer product, P1.

[0117] The resulting mixture with the solid precipitate is stirred at room temperature for 15 mins. and DMF (10 mL) is added to re-dissolve the solids. To the stirred mixture is slowly added diethyl ether (150 mL) to re-precipitate the polymer. Unreacted monomers are dissolved in the diethyl ether and are removed from the product.

[0118] The precipitated polymer is filtered with a Buchi filter funnel using Whatman paper, and the solid polymer is washed with 30 mL diethyl ether and air dried for about 1 hour. The dried polymer is transferred to a 250 mL RBF and water (10 mL) is added with stiffing to dissolve the polymer. To the stirred aqueous solution of the polymer at room temperature is added 50 mL of aqueous HC1 (pH=2, 0.01 M HCl prepared by dissolving 1 mL 0.5 M HCl (Sigma Aldrich) in 49 mL DI water) and stirred for 2 h, and dialyzed thoroughly as follows. The P1 polymer solution is added into dialysis tube (molecular weight cutoff: 1000), and is dialyzed against DI water (1 L) for 72 h, during which the water is exchanged with fresh DI water for 5 times. The purified polymer P1 is obtained after freeze drying as follows. P1 polymer solution is freezed at −30° C. and subsequently dried under vacuum (300 Pa pressure) for 24 h. Synthesis of Copolymer P3 and Epoxy Curing to Form Copolymer P4:

##STR00046## ##STR00047##

wherein: x and y define the block polymer and are integer greater than 1; and R and R′ are each independently H, C.sub.1-C.sub.6alkyl, —CH.sub.2C.sub.6H.sub.5 wherein the alkyl and the C.sub.6H.sub.5 are optionally substituted by 1 or 2 substituents selected from the group consisting of halogen (—F, —Cl, —Br— or —I), —OH, —SH, —SiH.sub.2OH, —NH.sub.2, —NO.sub.2, —CH.sub.3, —CF.sub.3, —OCH.sub.3 and —OCF.sub.3.

[0119] FIG. 2. Synthesis of copolymer P3 and epoxy curing to form P4. Synthesis of Copolymer P3:

[0120] Both monomers M1 and M3 are prepared according to literature methods. See J. Yuan et al., Chem. Mater. 2010, 22, 5003-5012. 1-Vinyl-3-benzyl imidazolium chloride (monomer M1, 1 g) and glycidyl vinyl acetate (monomer M3, 0.2 g) are added to a 250 mL 3—N RBF with a magnetic stir bar under nitrogen. The monomers are dissolved in N,N-dimethylformamide DMF, 10 mL) and stirred at room temperature for about 15 minutes. Azobisisobutyronitrile (AIBN) initiator (13 mg) is added into the solution mixture, and the reaction mixture is stirred and heated to 80° C. for 24 h (FIG. 2). After the reaction is complete, the solution is transferred to a 500 mL RBF. Diethyl ether (150 mL) is added to the stirred reaction mixture to precipitate out the crude polymer product, P3. The resulting mixture with the solid precipitate is stirred at room temperature for 15 mins and DMF (10 mL) is added to re-dissolve the solids. To the stirred mixture is slowly added diethyl ether (150 mL) to re-precipitate the polymer. Unreacted monomers are dissolved in the diethyl ether and removed from product.

[0121] The precipitated polymer is filtered with a Buchi filter funnel using Whatman paper, and the solid polymer is washed with 30 mL diethyl ether and air dried for about 1 hour. The purified polymer P3 is obtained after freeze drying as follows. P3 polymer solution is freezed at -30° C. and subsequently dried under vacuum (300 Pa pressure) for 24 h.

General Process:

[0122] A process for further crosslinking or curing process between the polymer or copolymer functional groups in the polymer chain can also effected when the polymer comprises certain crosslinkable or curable functional groups or residues. The crosslinking or curing process may provide a significantly stronger adhesive when compared to the similar polymeric adhesive composition without the additional crosslinking or curing step (e.g., P3 to P4). Such crosslinkable or curable functional group includes, for example, a vinyl group, an acrylate, an epoxide, a glycidyl, a hydroxy aryl, polyhydroxy aryl such as a catechol group.

[0123] In one embodiment, when the curable group is a hydroxy aryl group, such as a catechol group, curing of the polymer may be performed by changing the pH of the aqueous formulation comprising the polymer to a different pH, such as a more basic pH. For example, the polymer formulation may be contacted with water or an aqueous solution at a pH of about pH of 5, pH>5, pH>5.5, pH>6, pH>6.5, pH>7, pH>7.5, pH>8, pH>8.5, pH>9 or higher.

[0124] In another embodiment of the process, the materials or the surface of the materials comprising the adhesive may be first contacted or immersed in water or in an aqueous solution, and then the pH of the resulting mixture or composition may be increased to the desired pH, depending on the nature of the polymer, the functional group and the nature of the materials being glued together. Without being bound by the proposed mechanism of action disclosed herein, it is believed that the polymer or the functional groups, such as a hydroxy aryl group, undergo a curing or crosslinking process by way of an auto-oxidative crosslinking process or may be initiated by a metal ion(s) via coordination chemistry; to form a significantly stronger adhesive when compared to the use of the adhesive without a curing step. In another embodiment where the polymer comprises a functional group or residue such as an acrylate, a methacrylate or a substituted acrylate, the polymer may be crosslinked via visible light or UV light via photoinitiated polymerization.

[0125] In another embodiment, when the polymer comprises an epoxy group, such as an epoxide or a glycidyl group, the curing step may be performed using an a reagent, such as an amine. Such an amine may be a di- or tri-amine based epoxy curing agent Amines that may be used for amine-based epoxy curing includes aliphatic amines such as diethylamine (DEA), methylamine (MA), dimethylamine (DMA), cycloaliphatic amines such as cyclohexylamine (CHA) and cyclohexylmethylamine (CHMA), and aromatic amines such as aniline (AA) and methylaniline (MAA). Such a curing process is similar to that of the method for curing epoxy resin, where the adhesive maybe prepared or mixed and cured immediately before applying the adhesive to attach two surfaces. In one method, the dried polymer is transferred to a 250 mL RBF and water (10 mL) is added with stiffing to dissolve the polymer. To the stirred aqueous solution of the polymer at room temperature is added diethylamine (DEA) and allowed to cure. Performance of Adhesive Compositions with Different Materials:

Preparation of the Adhesive Composition:

[0126] 1 g of the homopolymer or the copolymer was added into a 50 mL RBF with a magnetic stirrer. 10 mL of water was added to the homopolymer or copolymer and the resulting mixture was stirred for 15 minutes to form a milky white, relatively viscous adhesive composition. The adhesion experiments described below may employ the polymer adhesive composition.

[0127] For the copolymers that are functionalized with extra crosslinkable residues, optionally, there is a second step of curing of the adhesive composition that may be performed to increase or enhance the bonding performance For example, in the case of the preparation of copolymers with catechol functional groups (i.e., 3,4-dihydroxyphenyl-), a catechol-mediated auto-oxidation process may be performed.

[0128] Accordingly, in addition to joining two test strips of the same or different material composition, the strips (or materials) may be immersed in water, at a pH of about 5, pH >5, pH>5.5, pH>6, pH>7, pH>8, pH>9, or pH range of 8-9, the polymer undergoes further curing or crosslinking to form a stronger adhesive. Under certain conditions, the catechol or other hydroxy benzyl or hydroxy aryl groups may undergo auto-oxidative crosslinking above neutral pH, such as pH>7.

[0129] Depending on the type or the nature of the functional groups of the polymers as described herein, the curing step may also be performed by crosslinking mechanism or chemistry. For example, where the polymer comprises a hydroxyphenyl group or dihydroxyphenyl group such as a catechol group, the crosslinking process may be initiated by a metal ion(s) by way of coordination chemistry. The pH of the solution may be lower than pH 5.5, the concentration should be considered with respect to solubility, stoichiometry, and the nature of the metal ion may affect the crosslinking process.

[0130] The adhesive may also be soluble in pure water or in the presence of saline or a saline solution. For example, the salt solution may comprise of a single salt or a mixture of salts, including NaBr, NaCl, NaI, LiBr, LiCl and LiI. In one particular aspect, the higher salt concentration (body fluid or sea water) in the applied media will cause a drying effect of the polymer when polymer solution in pure water or aqueous salt solution at low concentration is applied to surfaces in aqueous salt solution at higher concentration such as body fluid, salt water or sea water.

[0131] Two strips of pork tissues of about 1 inch long, half inch wide and about ⅛ inch thick are immersed in a saline solution for about 10 seconds. While leaving the dermises immersed in the saline solution, approximately 1 mL of the adhesive composition is drawn up into a pipette and injected or delivered onto one surface of the first of the two tissues to form a milky white layer of adhesive of about 2-3 square centimeters on the surface. While still immersed in the saline solution, one surface of the second tissue surface is brought into contact with the first tissue surface with the layer of adhesive and the two tissues are lightly pressed together for about 2 seconds, and then released. The resulting tissues are then glued together in the saline solution.

[0132] Two strips of plastics (made of PVC, polyethylene or polyurethane) of about 1 inch long, half inch wide and about ¼ inch thick are immersed in a saline solution for about 10 seconds. While leaving the plastic strips immersed in the saline solution, approximately 1 mL of the adhesive composition is drawn up into a pipette and injected or delivered onto one surface of the first of the two plastic strips to form a milky white layer of adhesive of about 2-3 square centimeters on the surface. While still immersed in the saline solution, one surface of the second plastic strip is brought into contact with the first plastic strip with the layer of adhesive and the two plastic strips are pressed together with a thumb and index finger for about 2 seconds, and then released. The resulting two plastic strips are then sealed or glued together.

[0133] The glues adhere all the different type of materials and surfaces including tissue to tissue, tissue to metal, tissue to plastic, tissue to mineral, mineral to metal, mineral to plastic, metal to metal, metal to plastic, plastic to plastic, mineral to mineral, and among other materials in wet conditions including under water. Such materials include tissues, such as human tissues, animal tissues, skin, tooth enamel, dentine, metals such as aluminum, stainless steel, copper, brass, glass, plastic, and combinations of these materials.

[0134] This solution can also be used as a low tack reusable adhesive (such as Post-it® notes). Such low tack or pressure sensitive adhesives may exhibit a low level of adhesion when first applied and may remove cleanly from a surface. In one aspect, the solution comprise of water, ethanol, NaCl, and the adhesive compound. As an example for preparing the resuable and sprayable low-tack pressure-sensitive adhesive solution, the adhesive compound is dissolved in water at 1-30 w/v % concentration, then the solution is diluted with ethanol to 10% to 90%. Saturated NaCl aqueous solution (1-30%) is then added. This solution can be sprayed on or applied to any surfaces that need to be low tack or anti-slippery under moist or wet conditions.

[0135] As another example, M2 can be replaced with vinyl alcohol. After copolymerization, the alcohol side group may be modified to acrylate or methacrylate by reaction with acryloyl chloride or methacryloyl chloride via acryl chloride esterification by nucleophilic addition-elimination with alcohol. The substituted acrylate or methacrylate residues can be crosslinked via radical polymerizations.

[0136] While the foregoing description describes specific embodiments, those with ordinary skill in the art will appreciate that various modifications and alternatives can be developed. Accordingly, the particular embodiments described above are meant to be illustrative only, and not to limit the scope of the invention, which is to be given the full breadth of the appended claims, and any and all equivalents thereof.