Photopolymerizable Compositions Including a Polyurethane Methacrylate Polymer Prepared Using a Polycarbonate Diol, Articles, and Methods

Abstract

The present disclosure provides a photopolymerizable composition. The photopolymerizable composition includes a) 40-60 parts by weight of a monofunctional (meth)acrylate monomer, per 100 parts of the total photopolymerizable composition; b) a photoinitiator; and c) a polymerization reaction product of components. A cured homopolymer of the monofunctional (meth)acrylate monomer has a glass transition temperature of 125 degrees Celsius or greater. The polymerization reaction product of components includes i) a diisocyanate; ii) a hydroxy functional methacrylate; iii) a polycarbonate diol; and iv) a catalyst. The polymerization reaction product includes a polyurethane methacrylate polymer. Often, the polycarbonate diol has a number average molecular weight 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; alternatively, the polyurethane methacrylate polymer has a weight average molecular weight of 8,000 g/mol or greater. An article is also provided including the photopolymerizable composition reaction product. Further, the present disclosure provides articles and methods of making articles. Methods are additionally provided, including receiving, by a manufacturing device having one or more processors, a digital object comprising data specifying an article; and generating, with the manufacturing device by an additive manufacturing process, the article based on the digital object. A system is also provided, including a display that displays a 3D model of an article; and 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 article.

1 . An article comprising a photopolymerization reaction product of 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 article exhibits a peak loss modulus below 20° C. and a tan delta peak>80° C.   
     
     
         2 . The article of  claim 1 , exhibiting a peak loss modulus below 15° C. or below 10° C. 
     
     
         3 . The article of  claim 1 , exhibiting a tan delta peak>100° C. or >110° C. 
     
     
         4 . The 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 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. 
     
     
         5 . The article of  claim 4 , exhibiting each of an initial relaxation modulus of 100 megapascals (MPa) or greater at 2% strain at 37° C., an elongation at break of a printed article of 20% or greater, and a tensile strength at yield of 14 MPa or greater. 
     
     
         6 . The article of  claim 1 , exhibiting an elongation at break of a printed article of 70% or greater. 
     
     
         7 . The article of  claim 1 , comprising 1 wt. % or less extractable components. 
     
     
         8 . The article of  claim 1 , 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. 
     
     
         9 . The article of  claim 1 , wherein the polymerization reaction product comprises a polyurethane methacrylate polymer having a weight average molecular weight (Mw) of 8,000 g/mol or greater. 
     
     
         10 . An article comprising a photopolymerization reaction product of 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 article exhibits a 30 minute relaxation modulus of 100 MPa or greater.   
     
     
         11 . The article of  claim 10 , exhibiting an initial relaxation modulus of 100 megapascals (MPa) or greater measured at 2% strain at 37° C. 
     
     
         12 . The article of  claim 10 , exhibiting a percent loss of relaxation modulus of 70% or less. 
     
     
         13 . The article of  claim 10 , exhibiting an elongation at break of a printed article of 20% or greater. 
     
     
         14 . The article of  claim 10 , exhibiting a tensile strength at yield of 14 MPa or greater. 
     
     
         15 . The article of  claim 10 , comprising 1 wt. % or less extractable components. 
     
     
         16 . The article of  claim 10 , exhibiting two glass transition temperatures (T g ), wherein the first T g  is 20° C. or less and the second T g  is 80° C. or more. 
     
     
         17 . The article of  claim 10 , exhibiting each of an initial relaxation modulus of 100 megapascals (MPa) or greater at 2% strain at 37° C., an elongation at break of a printed article of 20% or greater, and a tensile strength at yield of 14 MPa or greater. 
     
     
         18 . The article of  claim 10 , exhibiting an elongation at break of a printed article of 70% or greater. 
     
     
         19 . The article of  claim 10 , 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. 
     
     
         20 . The article of  claim 10 , wherein the polymerization reaction product comprises a polyurethane methacrylate polymer having a weight average molecular weight (Mw) of 8,000 g/mol or greater.