Curable Polymeric Compositions

Abstract

Compounds and compositions are provided which are useful in additive printing, particularly additive printing techniques such as stereolithography (SLA), wherein a composition of one or more photocurable compounds, such as a compound with multiple ethylenically unsaturated groups and a compound with multiple thiol groups, is photopolymerized, optionally in the presence of two or more thermocurable compounds which are reactive with one another and are subjected to thermopolymerization, to form a manufactured article in solid form.

1 - 54 . (canceled) 
     
     
         55 . A composition comprising a first organic compound (polySH) having multiple thiol groups (SH), a second organic compound (polyEU) having multiple ethylenically unsaturated groups (EU), and a photoinitiator; and optionally a stabilizer;
 wherein the composition has an SH to EU equivalents ratio of X:Y, where X ranges from 25-75 and Y ranges from 75-25 and the sum of X and Y is 100.   
     
     
         56 . The composition of  claim 55  wherein polySH is a water soluble, bioabsorbable macromere having a molecular weight of greater than 1,000 g/mol. 
     
     
         57 . The composition of  claim 55  wherein polyEU is a water soluble, bioabsorbable methacrylate. 
     
     
         58 . The composition of  claim 55  wherein EU of polyEU is norbornenyl. 
     
     
         59 . The composition of  claim 55  wherein at least one polyEU and polySH further has multiple ester groups and multiple carbonate groups, where optionally polyEU has both multiple ester groups and multiple carbonate groups, or where optionally both of polySH and polyEU further have both multiple ester groups and multiple carbonate groups. 
     
     
         60 . The composition of  claim 55  wherein at least one of polySH and polyEU further has multiple carbonate groups and multiple urethane groups, where optionally polyEU has both multiple carbonate groups and multiple urethane groups, or where optionally both of polySH and polyEU further have both multiple carbonate groups and multiple urethane groups. 
     
     
         61 . The composition of  claim 55  which is free of volatile materials having a boiling point of less than 110° C. 
     
     
         62 . A composition comprising a photochemically cured reaction product of the composition of  claim 55 . 
     
     
         63 . An additive manufacturing process comprising:
 (a) providing a vat containing a composition of  claim 55 ;   (b) directing actinic radiation from a light source into the first composition in the vat, where the actinic radiation is effective to induce polymerization of components of the composition so as to form a second composition; and   (c) forming a solid article.   
     
     
         64 . A composition comprising a first organic compound (polyhv) having multiple photopolymerizable groups (hv), a photoinitiator, a second organic compound (polyΔ1) having multiple reactive groups Δ1, and a third organic compound (polyΔ2) having multiple reactive groups Δ2, where Δ1 reacts with Δ2 upon contact and exposure to a temperature of greater than 50° C., wherein the polyhv is a bioabsorbable macromere having a molecular weight of greater than 1,000 g/mol. 
     
     
         65 . The composition of  claim 64  wherein polyhv is polyEU acrylate or methyacrylate. 
     
     
         66 . The composition of  claim 64  wherein hv of polyhv is norbornenyl. 
     
     
         67 . The composition of  claim 64  wherein at least one polyhv, polyΔ1 and polyΔ2 further has multiple ester groups and multiple carbonate groups, where optionally polyhv has both multiple ester groups and multiple carbonate groups, or where optionally polyhv and at least one of polyΔ1 and polyΔ2 has both multiple ester groups and multiple carbonate groups. 
     
     
         68 . The composition of  claim 64  wherein at least one of polyhv, polyΔ1 and polyΔ2 further has multiple carbonate groups and multiple urethane groups, where optionally polyhv has both multiple carbonate groups and multiple urethane groups, or where optionally polyhv and at least one of polyΔ1 and polyΔ2 has both multiple carbonate groups and multiple urethane groups. 
     
     
         69 . The composition of  claim 64  wherein the multiple Δ1 of polyΔ1 is 2, 3 or 4; or the multiple Δ2 of polyΔ2 is 2, 3 or 4, or both the multiple Δ1 of polyΔ1 is 2, 3 or 4 and the multiple Δ2 of polyΔ2 is 2, 3 or 4. 
     
     
         70 . The composition of  claim 64  which is free of volatile materials having a boiling point of less than 110° C. 
     
     
         71 . The composition of  claim 64  which is bioabsorbable. 
     
     
         72 . An additive manufacturing process comprising:
 (a) providing a vat containing a first composition of  claim 64 ;   (b) directing actinic radiation from a light source into the first composition in the vat, where the actinic radiation is effective to induce polymerization of components of the first composition so as to form a second composition comprising photochemically cured composition; and   (c) applying thermal energy to the second composition comprising the photochemically cured composition so as to form a third composition comprising photochemically cured and thermally cured composition.   
     
     
         73 . An article comprising a photochemically cured and thermally cured reaction product of the method of  claim 72 .