Polymerizable resins containing a 1,3,5-hexahydro-1,3,5-triazine moiety, methods of making, and dental compositions containing the same

1. A method of forming a hydrolytically-stable, water-soluble polymerizable resin containing a 1,3,5-hexahydro-1,3,5-triazine moiety, the method comprising:

reacting the 1,3,5-hexahydro-1,3,5-triazine moiety in the presence of a Michael donor under conditions selected to yield mono-substituted and di-substituted 1,3,5-hexahydro-1,3,5-triazine resin present in a combined amount that is greater than a combined amount of tri-substituted 1,3,5-hexahydro-1,3,5-triazine and unreacted 1,3,5-hexahydro-1,3,5-triazine moiety;

wherein the Michael donor is selected from the group consisting of a secondary amine and a thiol and the Michael donor is hydroxyl-terminated.

2. The method of claim 1 , wherein the mono- and di-substituted 1,3,5-hexahydro-1,3,5-triazine resins, respectively, have the following general formula:

wherein

X is H or CH 3 ,

R is CH 2 CH 2 —Y,

Y is —SR′, —NR′R or —NR′″;

R′ and R″ independently or the same are linear or branched linear alkyl having 1 to 18 carbon atoms with or without functional groups, and

R′″ is a cyclic alkyl having 2 to 18 carbon atoms or a heterocyclic compound.

3. The method of claim 2 , wherein R′ and R″ are of the general form R′(R″)—Z m , wherein m=1-3 and Z═—OH, —SH, —COOH, COOR′(R″)(R′″), —OPO(OH) 2 , —OPO(OR′)(OH), —PO(OH) 2 , —PO(OR′)(OH), —OSO 2 (OH), aromatics, or substituted aromatics.

4. The method of claim 1 , wherein the hydrolytically-stable, water-soluble polymerizable resin comprises at least one acrylamide group.

5. The method of claim 1 , wherein the hydrolytically-stable, water-soluble polymerizable resin comprises at least one inorganic acidic group.

6. The method of claim 1 , wherein the hydrolytically-stable, water-soluble polymerizable resin comprises at least one imidazolium group.

7. The method of claim 1 , wherein the hydrolytically-stable, water-soluble polymerizable resin comprises at least one imidazole group.

8. The method of claim 1 further comprising adding a phosphoric acid to the Michael donor of the mono- and di-substituted 1,3,5-hexahydro-1,3,5-triazine resin after the step of reacting the 1,3,5-hexahydro-1,3,5-triazine moiety with the Michael donor.

9. A method of forming a hydrolytically-stable, water-soluble polymerizable resin containing a 1,3,5-hexahydro-1,3,5-triazine moiety, the method comprising:

reacting the 1,3,5-hexahydro-1,3,5-triazine moiety in the presence of a Michael donor under conditions selected to yield mono-substituted and di-substituted 1,3,5-hexahydro-1,3,5-triazine resin present in a combined amount that is greater than a combined amount of tri-substituted 1,3,5-hexahydro-1,3,5-triazine and unreacted 1,3,5-hexahydro-1,3,5-triazine moiety;

wherein the Michael donor is imidazole.

10. The method of claim 9 further comprising converting the imidazole of the mono- and di-substituted 1,3,5-hexahydro-1,3,5-triazine resin to an imidazolium after the step of reacting the 1,3,5-hexahydro-1,3,5-triazine moiety with the Michael donor.

11. The method of claim 10 , wherein the step of converting the imidazole of the mono- and di-substituted 1,3,5-hexahydro-1,3,5-triazine resin to an imidazolium comprises reacting the mono- and di-substituted 1,3,5-hexahydro-1,3,5-triazine resin with bromohexane.

12. The method of claim 10 , wherein the step of converting the imidazole of the mono- and di-substituted 1,3,5-hexahydro-1,3,5-triazine resin to an imidazolium comprises reacting the mono- and di-substituted 1,3,5-hexahydro-1,3,5-triazine resin with bromododecane.

13. A method of forming a hydrolytically-stable, water-soluble polymerizable resin containing a 1,3,5-hexahydro-1,3,5-triazine moiety, the method comprising:

reacting the 1,3,5-hexahydro-1,3,5-triazine moiety in the presence of a Michael donor under conditions selected to yield mono-substituted and di-substituted 1,3,5-hexahydro-1,3,5-triazine resin present in a combined amount that is greater than a combined amount of tri-substituted 1,3,5-hexahydro-1,3,5-triazine and unreacted 1,3,5-hexahydro-1,3,5-triazine moiety;

wherein the Michael donor is a thiol.

14. The method of claim 13 , wherein the mono- and di-substituted 1,3,5-hexahydro-1,3,5-triazine resins, respectively, have the following general formula:

wherein

X is H or CH 3 ,

R is CH 2 CH 2 —Y,

Y is —SR′; and

R′ is a linear or branched linear alkyl having 1 to 18 carbon atoms with or without functional groups.

15. The method of claim 14 , wherein R′ is of the general form R′—Z m , wherein m=1-3 and Z═—OH, —SH, —COOH, COOR′, —OPO(OH) 2 , —OPO(OR′)(OH), —PO(OH) 2 , —PO(OR′)(OH),

—OSO 2 (OH), aromatics, or substituted aromatics.

16. The method of claim 9 , wherein the mono- and di-substituted 1,3,5-hexahydro-1,3,5-triazine resins, respectively, have the following general formula:

wherein

X is H or CH 3 ,

R is CH 2 CH 2 —Y, and

Y is imidazole.

17. The method of claim 9 , wherein the hydrolytically-stable, water-soluble polymerizable resin comprises at least one acrylamide group.