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 and a log P value of greater than 3, greater than 2, or greater than 1;

b) a photoinitiator, wherein the photoinitiator is present in an amount of 0.2 wt. % to 5 wt. %; 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, wherein either the polycarbonate diol has a number average molecular weight (Mn) of greater than 1,000 grams per mole (g/mol), wherein a ratio of the diisocyanate to the polycarbonate diols present in the components has a Mn of greater than 1 , 000 g/mol, wherein a ratio of the diisocyanate to the polycarbonate diol ranges from 4 molar equivalents of the isocyanate of the diisocyanate to 1 molar equivalent of the alcohol of the polycarbonate diol, to 4 molar equivalents of the isocyanate of the diisocyanate to 3 molar equivalents of the alcohol of the polycarbonate diol; and

iv) a catalyst;

wherein the polymerization reaction product comprises a polyurethane methacrylate polymer.

2. 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 and a log P value of greater than 3, greater than 2, or greater than 1;

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, wherein either the polycarbonate diol has a Mn of greater than 1,000 grams per mole (g/mol) or a weighted average of all polycarbonate diols present in the composition has a Mn of greater than 1,000 g/mol, wherein a ratio of the diisocvanate to the polycarbonate diol ranges from 4 molar equivalents of the isocyanate of the diisocvanate to 1 molar equivalent of the alcohol of the polycarbonate diol, to 4 molar equivalents of the isocyanate of the diisocyanate to 3 molar equivalents of the alcohol of the polycarbonate diol; 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.

3. 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 Rai is the residue of a diisocyanate.

4. The photopolymerizable composition 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.

5. The photopolymerizable composition of claim 1 , wherein the monofunctional (meth)acrylate monomer is selected from the group consisting of 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, and combinations thereof.

6. The photopolymerizable composition of claim 1 , wherein in the hydroxy functional methacrylate of Formula (I), Q is an alkylene group, p is 1, and in the methacryl functional group A, R 1 is methyl.

7. The photopolymerizable composition of claim 1 , wherein the polyurethane methacrylate polymer has a weight average molecular weight (Mw) of 6,000 g/mol to 35,000 g/mol.

8. The photopolymerizable composition of claim 1 , further comprising 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.

9. The photopolymerizable composition of claim 8 , wherein the optical brightener comprises a compound of Formula (VI):

10. The photopolymerizable composition of claim 1 , wherein a cured homopolymer of the monofunctional (meth)acrylate monomer has a T g of 155° C. or greater, 170° C. or greater, or 180° C. or greater.

11. The photopolymerizable composition of claim 1 , further comprising an inhibitor in an amount of 0.001 to 1 wt. %.

12. The photopolymerizable composition of claim 1 , essentially free of any monofunctional (meth)acrylate monomer having a log of octanol/water partition coefficient (log P) value of less than 3, less than 2, or less than 1.

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

14. The article of claim 13 , 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.

15. 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 and a log P value of greater than 3, greater than 2, or greater than 1;

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, wherein either the polycarbonate diol has a Mn of greater than 1,000 grams per mole (g/mol) or a weighted average of all polycarbonate diols present in the components has a Mn of greater than 1,000 g/mol, wherein a ratio of the diisocvanate to the polycarbonate diol ranges from 4 molar equivalents of the isocvanate of the diisocvanate to 1 molar equivalent of the alcohol of the polycarbonate diol, to 4 molar equivalents of the isocvanate of the diisocvanate to 3 molar equivalents of the alcohol of the polycarbonate diol; and

iv) a catalyst;

wherein the polymerization reaction product comprises a polyurethane methacrylate polymer;

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.

16. The method of claim 15 , 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.

17. 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, wherein either the polycarbonate diol has a Mn of greater than 1,000 grams per mole (g/mol) or a weighted average of all polycarbonate diols present in the components has a Mn of greater than 1,000 g/mol; and

iv) a catalyst;

wherein the polymerization reaction product comprises a polyurethane methacrylate polymer.

18. 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, wherein either the polycarbonate diol has a Mn of greater than 1,000 grams per mole (g/mol) or a weighted average of all polycarbonate diols present in the components has a Mn of greater than 1,000 g/mol; and

iv) a catalyst;

wherein the polymerization reaction product comprises a polyurethane methacrylate polymer.

19. 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 and a log P value of greater than 3, greater than 2, or greater than 1;

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

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

i) a diisocyanate;

ii) a hydroxy functional (meth)acrylate of Formula (X):

HO-Q-(A 1 ) 2   (X)

wherein Q is a polyvalent organic linking group and A 1 is independently selected from a (meth)acryl functional group of the formula —OC(═O)C(R 4 )═CH 2 , wherein R 4 is a lower alkyl of 1 to 4 carbon atoms or H; 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, wherein either the polycarbonate diol has a number average molecular weight (Mn) of greater than 1,000 grams per mole (g/mol) or a weighted average of all polycarbonate diols present in the components has a Mn of greater than 1,000 g/mol, wherein a ratio of the diisocyanate to the polycarbonate diol ranges from 4 molar equivalents of the isocyanate of the diisocyanate to 1 molar equivalent of the alcohol of the polycarbonate diol, to 4 molar equivalents of the isocyanate of the diisocvanate to 3 molar equivalents of the alcohol of the polycarbonate diol; and

iv) a catalyst;

wherein the polymerization reaction product comprises a polyurethane methacrylate polymer.