Photopolymerizable compositions including a polyurethane methacrylate polymer prepared using a polycarbonate diol, articles, and methods

1. A photopolymerizable composition comprising:

a) 40-60 parts by weight of a monofunctional (meth)acrylate monomer, per 100 parts of the total photopolymerizable composition, wherein a cured homopolymer of the monofunctional (meth)acrylate monomer has a T g of 125° C. or greater;

b) a photoinitiator; and

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

i) a diisocyanate;

ii) a hydroxy functional methacrylate of Formula (I):

HO-Q-(A) p   (I)

wherein Q is a polyvalent organic linking group, A is a methacryl functional group of the formula —OC(═O)C(R 1 )═CH 2 , wherein R 1 is a lower alkyl of 1 to 4 carbon atoms, and wherein p is 1 or 2; and

iii) a polycarbonate diol of Formula (II):

H(O—R 2 —O—C(═O)) m —O—R 3 —OH  (II)

wherein each of R 2 in each (O—R 2 —O—C(═O)) repeat unit, and R 3 are independently an aliphatic, cycloaliphatic, or aliphatic/cycloaliphatic alkylene group and an average number of carbon atoms in a combination of all the R 2 and R 3 groups is 4 to 10, and m is 2 to 23; and

iv) a catalyst;

wherein the polymerization reaction product comprises a polyurethane methacrylate polymer having a weight average molecular weight (Mw) of 8,000 g/mol or greater and wherein the photopolymerizable composition contains 11% by weight or less of any monofunctional (meth)acrylate monomer having a log P value of less than 3, less than 2, or less than 1, based on the total weight of the photopolymerizable composition.

2. The photopolymerizable composition of claim 1 , further comprising a compound of Formula (III):

(H 2 C═C(R 1 )C(═O)—O) p -Q-OC(═O)NH—R di —NHC(═O)O-Q-(O—C(═O)C(R 1 )═CH 2 ) p   (III)

wherein Q and R 1 are as defined for Formula (I), and R di is the residue of a diisocyanate.

3. The photopolymerizable composition of claim 2 , wherein the compound of Formula (III) is present in an amount of 5 to 20 wt. %, based on the weight of the polymerizable composition.

4. The photopolymerizable composition of claim 2 , wherein the compound of Formula (III) is added to the photopolymerizable composition.

5. The photopolymerizable composition of claim 1 , wherein the diisocyanate comprises an aliphatic isocyanate.

6. The photopolymerizable composition of claim 1 , exhibiting a dynamic viscosity of 1 to 10 Pa·s at 40 degrees Celsius.

7. The photopolymerizable composition 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.

8. The photopolymerizable composition of claim 1 , further comprising a UV absorber in an amount of 0.001 to 5% by weight, based on the total weight of the photopolymerizable composition.

9. The photopolymerizable composition of claim 1 , further comprising an inhibitor in an amount of 0.001 to 2% by weight, based on the total weight of the photopolymerizable composition.

10. The photopolymerizable composition of claim 1 , wherein the catalyst is free of tin.

11. The photopolymerizable composition of claim 1 , wherein a ratio of the diisocyanate to the polycarbonate diol is 4 molar equivalents of the isocyanate of the diisocyanate to 2 molar equivalents of the alcohol of the polycarbonate diol.

12. An article comprising a photopolymerization reaction product of the photopolymerizable composition of claim 1 .

13. The article of claim 12 , exhibiting at least two properties selected from the group consisting of an initial relaxation modulus of 100 megapascals (MPa) or greater 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 article of claim 12 , exhibiting an elongation at break of a printed article of 70% or greater.

15. The article of claim 12 , comprising 1 wt. % or less extractable components.

16. A method of making an article, the method comprising:

a) obtaining a photopolymerizable composition comprising:

1) 40-60 parts by weight of a monofunctional (meth)acrylate monomer, per 100 parts of the total photopolymerizable composition, wherein a cured homopolymer of the monofunctional (meth)acrylate monomer has a T g of 125° C. or greater;

2) A photoinitiator, wherein the photoinitiator is present in an amount of 0.2 wt. % to 5 wt. %; and

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

i) a diisocyanate;

ii) a hydroxy functional methacrylate of Formula (I):

HO-Q-(A) p   (I)

wherein Q is a polyvalent organic linking group, A is a methacryl functional group of the formula —OC(═O)C(R 1 )═CH 2 , wherein R 1 is a lower alkyl of 1 to 4 carbon atoms, and wherein p is 1 or 2;

iii) a polycarbonate diol of Formula (II):

H(O—R 2 —O—C(═O)) m —O—R 3 —OH  (II)

wherein each of R 2 in each (O—R 3 —O—C(═O)) repeat unit, and R 3 are independently an aliphatic, cycloaliphatic, or aliphatic/cycloaliphatic alkylene group and an average number of carbon atoms in a combination of all the R 2 and R 3 groups is 4 to 10, and m is 2 to 23; and

iv) a catalyst;

wherein the polymerization reaction product comprises a polyurethane methacrylate polymer having a weight average molecular weight (Mw) of 8,000 g/mol or greater and 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;

b) selectively curing the photopolymerizable composition to form the article; and

c) repeating steps a) and b) to form multiple layers and create the article comprising a three-dimensional structure.

17. The method of claim 16 , wherein the photopolymerizable composition is cured using actinic radiation including UV radiation, e-beam radiation, visible radiation, or a combination thereof, and 90% or greater of the actinic radiation is absorbed over a distance of 150 micrometers of the photopolymerizable composition.

18. The method of claim 16 , further comprising post curing the article using actinic radiation.

19. The method of claim 16 , wherein the method comprises vat polymerization of the photopolymerizable composition.

20. The method of claim 16 , further comprising subjecting the article to a heat treatment.

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

1) 40-60 parts by weight of a monofunctional (meth)acrylate monomer, per 100 parts of the total photopolymerizable composition, wherein a cured homopolymer of the monofunctional (meth)acrylate monomer has a T g of 125° C. or greater;

2) A photoinitiator, wherein the photoinitiator is present in an amount of 0.2 wt. % to 5 wt. %; and

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

i) a diisocyanate;

ii) a hydroxy functional methacrylate of Formula (I):

HO-Q-(A) p   (I)

wherein Q is a polyvalent organic linking group, A is a methacryl functional group of the formula —OC(═O)C(R 1 )═CH 2 , wherein R 1 is a lower alkyl of 1 to 4 carbon atoms, and wherein p is 1 or 2;

iii) a polycarbonate diol of Formula (II):

H(O—R 2 —O—C(═O)) m —O—R 3 —OH  (II)

wherein each of R 2 in each (O—R 2 —O—C(═O)) repeat unit, and R 3 are independently an aliphatic, cycloaliphatic, or aliphatic/cycloaliphatic alkylene group and an average number of carbon atoms in a combination of all the R 2 and R 3 groups is 4 to 10, and m is 2 to 23; and

iv) a catalyst;

wherein the polymerization reaction product comprises a polyurethane methacrylate polymer having a weight average molecular weight (Mw) of 8,000 g/mol or greater and 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.

22. 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 article; and

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

1) 40-60 parts by weight of a monofunctional (meth)acrylate monomer, per 100 parts of the total photopolymerizable composition, wherein a cured homopolymer of the monofunctional (meth)acrylate monomer has a T g of 125° C. or greater;

2) A photoinitiator, wherein the photoinitiator is present in an amount of 0.2 wt. % to 5 wt. %; and

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

i) a diisocyanate;

ii) a hydroxy functional methacrylate of Formula (I):

HO-Q-(A) p   (I)

wherein Q is a polyvalent organic linking group, A is a methacryl functional group of the formula —OC(═O)C(R 1 )═CH 2 , wherein R 1 is a lower alkyl of 1 to 4 carbon atoms, and wherein p is 1 or 2;

iii) a polycarbonate diol of Formula (II):

H(O—R 2 —O—C(═O)) m —O—R 3 —OH  (II)

wherein each of R 2 in each (O—R 2 —O—C(═O)) repeat unit, and R 3 are independently an aliphatic, cycloaliphatic, or aliphatic/cycloaliphatic alkylene group and a number of carbon atoms in a combination of all the R 2 and R 3 groups is 4 to 10, and m is 2 to 23; and

iv) a catalyst;

wherein the polymerization reaction product comprises a polyurethane methacrylate polymer having a weight average molecular weight (Mw) of 8,000 g/mol or greater and 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.