Orthodontic articles prepared using a polycarbonate diol, and methods of making same

1. An orthodontic article comprising:

a) a polymerized reaction product of a photopolymerizable composition comprising:

i) a monofunctional (meth)acrylate monomer whose cured homopolymer has a T g of 90° C. or greater;

ii) a photoinitiator; and

iii) a polymerization reaction product of components, the components comprising:

1) an isocyanate;

2) a (meth)acrylate mono-ol;

3) a polycarbonate diol of Formula (I):

H(O—R 1 —O—C(═O)) m —O—R 2 —OH  (I)

wherein each of R 1 in each (O—R 1 —O—C(═O)) repeat unit and each R 2 are independently an aliphatic, cycloaliphatic, or aliphatic/cycloaliphatic alkylene group and an average number of carbon atoms in a combination of all the R 1 and R 2 groups is 4 to 10, and m is 2 to 23; and

4) a catalyst;

wherein the polymerized reaction product of the photopolymerizable composition has a shape of the orthodontic article.

2. The orthodontic article of claim 1 , wherein the (meth)acrylate mono-ol is of Formula (II):

HO-Q-(A) p   (II)

wherein Q is a polyvalent organic linking group, A is a (meth)acryl functional group of the formula —XC(═O)C(R 3 )═CH 2 , wherein X is O, S, or NR 4 , R 4 is H or an alkyl of 1 to 4 carbon atoms, R 3 is a lower alkyl of 1 to 4 carbon atoms or H, and wherein p is 1 or 2.

3. The orthodontic article of claim 1 , wherein the photopolymerizable composition further comprises a compound of Formula (III):

(H 2 C═C(R 3 )C(═O)—X) p -Q-OC(═O)NH—R di —NHC(═O)O-Q-(X—C(═O)(R 3 )C═CH 2 ) p   (III),

wherein X, Q, p, and R 3 are as defined for Formula (II), and R di is the residue of a diisocyanate.

4. The orthodontic article of claim 3 , wherein the compound of Formula (III) is added to the photopolymerizable composition.

5. The orthodontic article of claim 3 , wherein the compound of Formula (III) is present in an amount of 5 to 20 wt. %, based on the weight of the polymerizable composition.

6. The orthodontic article of claim 3 , wherein the compound of Formula (III) is of Formula (IV):

(IV).

7. The orthodontic article of claim 1 , wherein the monofunctional (meth)acrylate monomer is selected from the group consisting of dicyclopentadienyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dimethyl-1-adamantyl acrylate, cyclohexyl methacrylate, tert-butyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, cis-4-tert-butyl-cyclohexylmethacrylate, 2-decahydronapthyl methacrylate, 1-adamantyl acrylate, 73/27 trans/cis-4-tert-butylcyclohexylmethacrylate, dicyclopentadienyl methacrylate, dicyclopentanyl methacrylate, trans-4-tert-butylcyclohexyl methacrylate, d,l-isobornyl methacrylate, dimethyl-1-adamantyl methacrylate, d,l-bornyl methacrylate, 3-tetracyclo[4.4.0.1.1]dodecyl methacrylate, 1-adamantyl methacrylate, or combinations thereof.

8. The orthodontic article of claim 1 , wherein the polycarbonate diol has a molecular weight of 800 g/mol to 2,200 g/mol, or 1,800 g/mol to 2,200 g/mol.

9. The orthodontic article of claim 1 , wherein the photopolymerizable composition further comprises a UV absorber comprising an optical brightener in an amount of 0.001 to 5% by weight, based on the total weight of the photopolymerizable composition.

10. The orthodontic article of claim 9 , wherein the optical brightener comprises a compound of Formula (V):

(V).

11. The orthodontic article of claim 1 , wherein the polyurethane (meth)acrylate polymer has a molecular weight of 6,000 g/mol to 35,000 g/mol.

12. The orthodontic article of claim 1 , wherein a cured homopolymer of the monofunctional (meth)acrylate monomer has a T g of 100° C. or greater, 170° C. or greater, or 180° C. or greater.

13. The orthodontic article of claim 1 , exhibiting at least two properties selected from the group consisting of an initial relaxation modulus of 100 megapascals (MPa) or greater measured at 2% strain at 37° C., a percent loss of relaxation modulus of 70% or less, a 30 minute relaxation modulus of 100 MPa or greater, an elongation at break of a printed article of 20% or greater, and a tensile strength at yield of 14 MPa or greater.

14. The orthodontic article of claim 1 , exhibiting a peak in loss modulus of 20° C. or less and a tan delta peak of 80° C. or greater.

15. The orthodontic article of claim 1 , further comprising an inhibitor in an amount of 0.001 to 1 wt. %, based on the total weight of the photopolymerizable composition.

16. The orthodontic article of claim 1 , wherein the photoinitiator is present in an amount of 0.2 wt. % to 5 wt. %.

17. The orthodontic article of claim 1 , wherein the monofunctional (meth)acrylate monomer has a log of octanol/water partition coefficient (log P) value of greater than 3, greater than 2, or greater than 1.

18. A method of making an orthodontic article, the method comprising:

a) obtaining a photopolymerizable composition comprising:

i) a monofunctional (meth)acrylate monomer whose cured homopolymer has a T g of 90° C. or greater;

ii) a photoinitiator; and

iii) a polymerization reaction product of components, the components comprising:

1) an isocyanate;

2) a (meth)acrylate mono-ol;

3) a polycarbonate diol of Formula (I):

H(O—R 1 —O—C(═O)) m —O—R 2 —OH  (I)

wherein each of R 1 in each (O—R 1 —O—C(═O)) repeat unit and each R 2 are independently an aliphatic, cycloaliphatic, or aliphatic/cycloaliphatic alkylene group and an average number of carbon atoms in a combination of all the R 1 and R 2 groups is 4 to 10, and m is 2 to 23; and

4) a catalyst;

b) selectively curing the photopolymerizable composition; and

c) repeating steps a) and b) to form multiple layers and create the orthodontic article.

19. The method of claim 18 , wherein the photopolymerizable composition is cured using actinic radiation comprising UV radiation, e-beam radiation, visible radiation, or a combination thereof.

20. The method of claim 18 , further comprising subjecting the orthodontic article to a heat treatment.

21. A non-transitory machine readable medium comprising data representing a three-dimensional model of an orthodontic article, when accessed by one or more processors interfacing with a 3D printer, causes the 3D printer to create an orthodontic article comprising a reaction product of a photopolymerizable composition comprising a blend of:

a) a monofunctional (meth)acrylate monomer whose cured homopolymer has a T g of 90° C. or greater;

b) a photoinitiator; and

c) a polymerization reaction product of components, the components comprising:

i) an isocyanate;

ii) a (meth)acrylate mono-ol;

iii) a polycarbonate diol of Formula (I):

H(O—R 1 —O—C(═O)) m —O—R 2 —OH  (I)

wherein each of R 1 in each (O—R 1 —O—C(═O)) repeat unit and each R 2 are independently an aliphatic, cycloaliphatic, or aliphatic/cycloaliphatic alkylene group and an average number of carbon atoms in a combination of all the R 1 and R 2 groups is 4 to 10, and m is 2 to 23; and

iv) a catalyst.

22. A method comprising:

a) retrieving, from a non-transitory machine readable medium, data representing a 3D model of an article;

b) executing, by one or more processors, a 3D printing application interfacing with a manufacturing device using the data; and

c) generating, by the manufacturing device, a physical object of the orthodontic article, the orthodontic article comprising a reaction product of a photopolymerizable composition, the photopolymerizable composition comprising a blend of:

i) a monofunctional (meth)acrylate monomer whose cured homopolymer has a T g of 90° C. or greater;

ii) a photoinitiator; and

iii) a polymerization reaction product of components, the components comprising:

1) an isocyanate;

2) a (meth)acrylate mono-ol;

3) a polycarbonate diol of Formula (I):

H(O—R 1 —O—C(═O)) m —O—R 2 —OH  (I)

wherein each of R 1 in each (O—R 1 —O—C(═O)) repeat unit and each R 2 are independently an aliphatic, cycloaliphatic, or aliphatic/cycloaliphatic alkylene group and an average number of carbon atoms in a combination of all the R 1 and R 2 groups is 4 to 10, and m is 2 to 23; and

4) a catalyst.

23. A method comprising:

a) receiving, by a manufacturing device having one or more processors, a digital object comprising data specifying a plurality of layers of an orthodontic article; and

b) generating, with the manufacturing device by an additive manufacturing process, the orthodontic article based on the digital object, the orthodontic article comprising a reaction product of a photopolymerizable composition, the photopolymerizable composition comprising a blend of:

i) a monofunctional (meth)acrylate monomer whose cured homopolymer has a T g of 90° C. or greater;

ii) a photoinitiator; and

iii) a polymerization reaction product of components, the components comprising:

1) an isocyanate;

2) a (meth)acrylate mono-ol;

3) a polycarbonate diol of Formula (I):

H(O—R 1 —O—C(═O)) m —O—R 2 —OH  (I)

 wherein each of R 1 in each (O—R 1 —O—C(═O)) repeat unit and each R 2 are independently an aliphatic, cycloaliphatic, or aliphatic/cycloaliphatic alkylene group and an average number of carbon atoms in a combination of all the R 1 and R 2 groups is 4 to 10, and m is 2 to 23; and

4) a catalyst.

24. A system comprising:

a) a display that displays a 3D model of an orthodontic article; and

b) one or more processors that, in response to the 3D model selected by a user, cause a 3D printer to create a physical object of an orthodontic article, the orthodontic article comprising a reaction product of a photopolymerizable composition, the photopolymerizable composition comprising a blend of:

i) a monofunctional (meth)acrylate monomer whose cured homopolymer has a T g of 90° C. or greater;

ii) a photoinitiator; and

iii) a polymerization reaction product of components, the components comprising:

1) an isocyanate;

2) a (meth)acrylate mono-ol;

3) a polycarbonate diol of Formula (I):

H(O—R 1 —O—C(═O)) m —O—R 2 —OH  (I)

wherein each of R 1 in each (O—R 1 —O—C(═O)) repeat unit and each R 2 are independently an aliphatic, cycloaliphatic, or aliphatic/cycloaliphatic alkylene group and an average number of carbon atoms in a combination of all the R 1 and R 2 groups is 4 to 10, and m is 2 to 23; and

4) a catalyst.

25. The orthodontic article of claim 1 , wherein the photopolymerizable composition is essentially free of any monofunctional (meth)acrylate monomer having a log P value of less than 3, less than 2, or less than 1.

26. The orthodontic article of claim 1 , wherein the diisocyanate comprises an aliphatic isocyanate.

27. The orthodontic article of claim 1 , wherein the photopolymerizable composition exhibits a dynamic viscosity of 1 to 10 Pa·s at 40 degrees Celsius.

28. The orthodontic article of claim 1 , wherein the polycarbonate diol has a number average molecular weight (Mn) of 450 grams per mole (g/mol) to 3,200 g/mol.

29. The orthodontic article of claim 1 , wherein the photopolymerizable composition further comprises a UV absorber in an amount of 0.001 to 5% by weight, based on the total weight of the photopolymerizable composition.

30. The orthodontic article of claim 1 , wherein the catalyst is free of tin.

31. The orthodontic article of claim 1 , wherein a ratio of the diisocyanate to the polycarbonate diol is 4 molar equivalents of the isocyanate to 2 molar equivalents of the alcohol of the polycarbonate diol.

32. The orthodontic article of claim 1 , wherein the photopolymerizable composition further comprises a difunctional monomer in an amount of up to 15 wt. %, based on the total weight of the photopolymerizable composition, and wherein the difunctional monomer comprises a compound of Formula (X) or Formula (XI):

H 2 C═C(R 3 )C(═O)X-Q-O—C(═O)NH—R di —NHC(═O)—O-Q-XC(═O)C(R 3 )═CH 2   (X),

wherein R di is the residue of a diisocyanate, Q, X, and R 3 are as defined for Formula (II);

H 2 C═C(R 3 )C(═O)—O-Q-NH—C(═O)—(O—R 1 —O—C(═O)) m —O—R 2 —O—C(═O)NH-Q-O—C(═O)C(R 3 )═CH 2   (XI),

wherein Q and R 3 are as defined for Formula (II) and R 1 and R 2 are as defined for Formula (I).

33. The orthodontic article of claim 1 , wherein the photopolymerizable composition further comprises a second polymerization reaction product of components, wherein the components comprise:

1) an isocyanate functional (meth)acrylate compound of Formula (VII):

(A) p -Q-NCO  (VII),

wherein A, p, and Q are as defined for Formula (II);

2) a polycarbonate diol of Formula (I):

H(O—R 1 —O—C(═O)) m —O—R 2 —OH  (I); and

3) a catalyst,

wherein each of R 1 in each (O—R 1 —O—C(═O)) repeat unit and each R 2 are independently an aliphatic, cycloaliphatic, or aliphatic/cycloaliphatic alkylene group and an average number of carbon atoms in a combination of all the R 1 and R 2 groups is 4 to 10, and m is 2 to 23.

34. The orthodontic article of claim 1 , wherein the photopolymerizable composition further comprises a second polymerization reaction product comprising a compound of Formula (VIII):

(H 2 C═C(R 3 )C(═O)—O) p -Q-NH—C(═O)—(O—R 1 —O—C(═O)) m —O—R 2 —O—C(═O)NH-Q-(O—C(═O)(R 3 )C═CH 2 ) p   (VIII),

wherein Q, p, and R 3 are as defined for Formula and R 1 and R 2 are as defined for Formula (I).

35. The orthodontic article of claim 1 , wherein the monofunctional acrylate monomer comprises a cycloaliphatic monofunctional (meth)acrylate.

36. The orthodontic article of claim 1 , exhibiting an elongation at break of a printed article of 70% or greater.

37. The orthodontic article of claim 1 , comprising 1 wt. % or less extractable components.

38. The method of claim 18 , further comprising post curing the article using actinic radiation.

39. The method of claim 18 , wherein the method comprises vat polymerization of the photopolymerizable composition.