Photocurable polymers, photocurable polymer compositions and lithographic processes including the same

Abstract

The present invention relates to functionalized poly(aryl ether sulfones) polymers. The invention further relates to polymer compositions including the functionalized poly(aryl ether sulfone) polymers. Still further, the invention relates to lithographic methods to form three-dimensional (3D) objects that incorporate the aforementioned polymer compositions.

1 - 15 : (canceled) 
     
     
         16 . A poly(aryl ethersulfone) (PAES) polymer comprising:
 recurring units (R PAES ) of formula (L):   
       
         
           
           
               
               
           
         
         at least one terminal group of formula (M): 
       
       
         
           
           
               
               
           
         
       
       wherein:
 each R 1  is independently selected from the group consisting of a halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; 
 each L 1  is —(CH 2 ) n —CH 2 —CH═CH 2  or a radical containing the same; 
 each i is an independently selected integer from 0 to 4; 
 n is an integer from 1 to 10; 
 T is selected from the group consisting of a bond, —CH 2 —; —O—; —SO 2 —; —S—; —C(O)—; —C(CH 3 ) 2 —; —C(CF 3 ) 2 —; —C(═CCl 2 )—; —C(CH 3 )(CH 2 CH 2 COOH)—; —N═N—; —R a C═CR b —, where each R a  and R b , independently of one another, is a hydrogen or a C1-C12-alkyl, C1-C12-alkoxy, or C6-C18-aryl group; —(CH 2 ) m — and —(CF 2 ) m — with m being an integer from 1 to 6; an aliphatic divalent group, linear or branched, of up to 6 carbon atoms; and combinations thereof. 
 
     
     
         17 . The poly(aryl ethersulfone) (PAES) polymer of  claim 16 , wherein T is selected from the group consisting of a bond, —SO 2 — and —C(CH 3 ) 2 —. 
     
     
         18 . The poly(aryl ethersulfone) (PAES) polymer of  claim 16 , wherein the poly(aryl ethersulfone) (PAES) polymer comprises at least 50 mol. % of recurring units of formula (L), based on the total number of moles in the polymer. 
     
     
         19 . The poly(aryl ethersulfone) (PAES) polymer of  claim 16 , wherein the poly(aryl ethersulfone) (PAES) polymer comprises at least 50 mol. % of recurring units selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
       based on the total number of moles in the poly(aryl ethersulfone) (PAES) polymer. 
     
     
         20 . The poly(aryl ethersulfone) (PAES) polymer of  claim 16 , wherein the poly(aryl ethersulfone) (PAES) polymer has a number average molecular weight (Mn) of less than about 20,000 g/mol, less than about 15,000 g/mol, or less than about 10,000 g/mol, as measured by gel permeation chromatography (GPC) using methylene chloride as a mobile phase, with polystyrene standards. 
     
     
         21 . The poly(aryl ethersulfone) (PAES) polymer of  claim 16 , wherein the poly(aryl ethersulfone) (PAES) polymer has a number average molecular weight (Mn) of no less than about 1,000 g/mol, as measured by gel permeation chromatography (GPC) using methylene chloride as a mobile phase, with polystyrene standards. 
     
     
         22 . A polymer composition (C) comprising:
 the poly(aryl ethersulfone) (PAES) polymer of  claim 16 , and   at least one component selected from the group consisting of reinforcing agents, photoinitiators, tougheners, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, thermal stabilizers, light stabilizers, flame retardants, nucleating agents and antioxidants.   
     
     
         23 . The polymer composition (C) of  claim 22 , wherein the component is a reinforcing agent selected from the group consisting of talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate, glass fibers, carbon fibers, synthetic polymeric fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers, and wollastonite. 
     
     
         24 . The polymer composition (C) of  claim 22  further comprising a co-reactant selected from the group consisting of 1,16-hexadecanedithiol, 1,2-benzenedimethanethiol, 1,2-ethanedithiol, 1,3-benzenedimethanethiol, 1,3-propanedithiol, 1,4-benzenedimethanethiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 2,2′-thiodiethanethiol, 2,3-dimercapto-1-propanol, 4,4′-bis(mercaptomethyl)biphenyl, and trimethylolpropane tris(3-mercaptopropionate). 
     
     
         25 . A method for making a three-dimensional (3D) article with an additive manufacturing system, the method comprising printing layers of the three-dimensional (3D) article, wherein the layers comprise the polymer composition (C) of  claim 22 . 
     
     
         26 . The method of  claim 25 , wherein the polymer composition (C) is heated to a temperature of at least 280° C. before printing. 
     
     
         27 . The method of  claim 25 , wherein the method comprises irradiating the polymer composition (C) with UV light. 
     
     
         28 . The method of  claim 27 , wherein the UV light is laser light. 
     
     
         29 . A three-dimensional (3D) article obtained, at least in part, by the method of  claim 25 . 
     
     
         30 . The poly(aryl ethersulfone) (PAES) polymer of  claim 16 , wherein the poly(aryl ethersulfone) (PAES) polymer has a number average molecular weight (Mn) of less than about 15,000 g/mol, as measured by gel permeation chromatography (GPC) using methylene chloride as a mobile phase, with polystyrene standards. 
     
     
         31 . The poly(aryl ethersulfone) (PAES) polymer of  claim 16 , wherein the poly(aryl ethersulfone) (PAES) polymer has a number average molecular weight (Mn) of less than about 10,000 g/mol, as measured by gel permeation chromatography (GPC) using methylene chloride as a mobile phase, with polystyrene standards.