Compositions and methods of additive manufacturing of aromatic thermoplastics and articles made therefrom

Abstract

Polymer resins for the vat photopolymerization of thermoplastics are provided, in particular for the vat photopolymerization of thermoplastics with exception thermal stability and mechanical properties. In some aspects, the polymer resins are prepared by ring opening of an aromatic dianhydride with an alcohol containing an acrylate or methacrylate to produce a photocrosslinkable diacid monomer; conversion of the photocrosslinkable diacid monomer to a photocrosslinkable diacyl chloride; and polymerization of the photocrosslinkable diacyl chloride with an aromatic diamine to produce a photocrosslinkable precursor polymer. Upon crosslinking and drying, a thermal imidization can yield aromatic polyimide polymers with high yield and with micron-scale structural resolution.

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         41 . A method of making a polymer resin for vat photopolymerization, the method comprising:
 ring opening of an aromatic dianhydride with an alcohol containing an acrylate or methacrylate to produce a photocrosslinkable diacid monomer;   conversion of the photocrosslinkable diacid monomer to a photocrosslinkable diacyl chloride;   polymerization of the photocrosslinkable diacyl chloride with an aromatic diamine to produce a photocrosslinkable precursor polymer; and   dissolving a photointiator and the photocrosslinkable precursor polymer in a suitable organic solvent.   
     
     
         42 . The method according to  claim 41 , wherein the aromatic dianhydride is selected from the group consisting of 
       
         
           
           
               
               
           
         
         where Y is selected from the group consisting of O, S, C═O, C(CF 3 ) 2 , C(CH 3 ) 2 , SO 2 , and C≡C. 
       
     
     
         43 . The method according to  claim 41 , wherein the alcohol has a structure according to the following formula 
       
         
           
           
               
               
           
         
         wherein each occurrence of R 2  is independently a linear or branched alkyl group having from 1 to 6 carbon atoms, 
         wherein each occurrence of R 3  is independently a hydrogen or a methyl, and 
         wherein each occurrence of R 4  is independently a hydrogen, a linear alkyl group, or a branched alkyl group having from 1 to 12, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 1, or 2 to 5 carbon atoms; 
       
     
     
         44 . The method according to  claim 41 , wherein the diamine is selected from the group consisting of aromatic groups selected from the group consisting of 
       
         
           
           
               
               
           
         
         where the aromatic group comprises two amine substituents attached thereto, 
         where each occurrence of Z is independently O, CH 2 , CH 2 CH 2 , SO 2 , C(CF 3 ) 2 , C(CH 3 ) 2 , S, S—S, CH═CH, C═O, C≡C, or NH; 
         where each occurrence of Z 1  is independently H, Cl, OH, OCH 3 , CH 3 , or CH 2 CH 3 ; 
         where each occurrence of Z 2  is independently H, CH 3 , CF 3 , or SO 3 H; and where each occurrence of n is independently 0, 1, 2, or 3. 
       
     
     
         45 . A method of making an article, the method comprising:
 (a) applying an effective amount of a light to a solution comprising a photocrosslinkable precursor polymer to crosslink the photocrosslinkable precursor polymer to form a layer of a precursor article,   wherein the photocrosslinkable precursor polymer comprises repeat units having a structure according to the following formula   
       
         
           
           
               
               
           
         
         wherein R has a structure according to the following formula 
       
       
         
           
           
               
               
           
         
         wherein each occurrence of R 2  is independently a linear or branched alkyl group having from 1 to 6 carbon atoms, 
         wherein each occurrence of R 3  is independently a hydrogen or a methyl, 
         wherein each occurrence of X is a substituted or unsubstituted aromatic group, 
         wherein each occurrence of A is a substituted or unsubstituted aromatic group, and 
         wherein each occurrence of R 4  is independently a hydrogen, a linear alkyl group, or a branched alkyl group having from 1 to 12, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 1, or 2 to 5 carbon atoms; 
         (b) repeating step (a) a number of times to form the precursor article in a layer-by-layer fashion; and 
         (c) heating the precursor article to a first elevated temperature for a period of time to form the article comprising polyimide repeat units having a structure according to the following formula 
       
       
         
           
           
               
               
           
         
       
     
     
         46 . A method of making an article, the method comprising:
 (a) applying an effective amount of a light to a solution comprising a photocrosslinkable precursor polymer to crosslink the photocrosslinkable precursor polymer to form a layer of a precursor article,   wherein the photocrosslinkable precursor polymer comprises repeat units having a structure according to the following formula   
       
         
           
           
               
               
           
         
         wherein R has a structure according to the following formula 
         wherein each occurrence of R 2  is independently a linear or branched alkyl group having from 1 to 6 carbon atoms, 
         wherein each occurrence of R 3  is independently a hydrogen or a methyl, 
         wherein each occurrence of X is a substituted or unsubstituted aromatic group, 
         wherein each occurrence of A is a substituted or unsubstituted aromatic group, and 
         wherein each occurrence of R 4  is independently a Hydrogen or a linear or branched alkyl group having from 1 to 6 carbon atoms; 
         (b) repeating step (a) to form the precursor article in a layer-by-layer fashion; and 
         (c) heating the precursor article to a first elevated temperature for a period of time to form the article comprising polyimide repeat units having a structure according to the following 
       
       
         
           
           
               
               
           
         
       
     
     
         47 . A method of making an article, the method comprising:
 (a) applying an effective amount of a light to a solution comprising a photocrosslinkable precursor polymer to crosslink the photocrosslinkable precursor polymer to form a layer of a precursor article,   wherein the photocrosslinkable precursor polymer comprises repeat units having a structure according to the following formula   
       
         
           
           
               
               
           
         
         wherein R has a structure according to the following formula 
       
       
         
           
           
               
               
           
         
         wherein each occurrence of R 2  is independently a linear or branched alkyl group having from 1 to 6 carbon atoms, 
         wherein each occurrence of R 3  is independently a hydrogen or a methyl, 
         wherein each occurrence of X is an aromatic diamine, and 
         wherein each occurrence of A is a dianhydride; 
         (b) repeating step (a) a number of times to form the precursor article in a layer-by-layer fashion; and 
         (c) heating the precursor article to a first elevated temperature for a period of time to form the article comprising polyimide repeat units having a structure according to the following formula 
       
       
         
           
           
               
               
           
         
       
     
     
         48 . The method according to  claim 45 , wherein X is an aromatic group having one or more hydroxy or methoxy substituents adjacent to the amine substituent, and wherein the method further comprises
 (d) heating the article to a second elevated temperature for a second period of time to convert at least some of the polyimide repeat units into polybenzoxazole repeat units having a structure according to the following formula   
       
         
           
           
               
               
           
         
       
     
     
         49 . The method according to  claim 45 , the method further comprising drying the precursor article to remove the solvent prior to forming the polyimide repeat units. 
     
     
         50 . The method according to  claim 49 , wherein the drying is performed by drying the precursor article in a vacuum oven for about 1 h. at one or more temperatures between 25° C. and 150° C. 
     
     
         51 . The method according to  claim 45 , wherein the article does not comprise a layered structure. 
     
     
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         53 . An article prepared by the method according to  claim 45 . 
     
     
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         55 . A 3D printed article comprising a polyimide polymer comprising repeat units having a structure according to the following formula 
       
         
           
           
               
               
           
         
         wherein each occurrence of X is a substituted or unsubstituted aromatic group, and 
         wherein each occurrence of A is a substituted or unsubstituted aromatic group. 
       
     
     
         56 . A 3D printed article comprising a polybenzoxazole polymer comprising repeat units having a structure according to the following formula 
       
         
           
           
               
               
           
         
       
     
     
         57 . The article according to  claim 55 , wherein A is independently selected from the group consisting of substituted and unsubstituted phenyl, substituted and unsubstituted biphenyl, substituted and unsubstituted diphenyl ether, substituted and unsubstituted benzophenone, substituted and unsubstituted (perfluoropropane-2,2-diyl)phenyl, substituted and unsubstituted propane-2,2-diylphenyl, sulfonyldiphenyl, and substituted and unsubstituted diphenylacetylene. 
     
     
         58 . The article according to  claim 55  wherein each occurrence is independently selected from the group consisting of 
       
         
           
           
               
               
           
         
         where Y is selected from the group consisting of O, S, C═O, C(CF 3 ) 2 , C(CH 3 ) 2 , SO 2 , and C≡C. 
       
     
     
         59 . The article according to  claim 55 , wherein X is selected from the group consisting of substituted and unsubstituted phenyl, substituted and unsubstituted biphenyl, substituted and unsubstituted, substituted and unsubstituted diphenyl ether, substituted and unsubstituted benzophenone, substituted and unsubstituted (perfluoropropane-2,2-diyl)phenyl, substituted and unsubstituted propane-2,2-diylphenyl, sulfonyldiphenyl, substituted and unsubstituted fluorene, substituted and unsubstituted naphthyl, and substituted and unsubstituted pyrene. 
     
     
         60 . The article according to  claim 55 , wherein X is selected from the group consisting of 
       
         
           
           
               
               
           
         
         where each occurrence of Z is independently O, CH 2 , CH 2 CH 2 , SO 2 , C(CF 3 ) 2 , C(CH 3 ) 2 , S, S—S, CH═CH, C═O, C≡C, or NH; 
         where each occurrence of Z 1  is independently H, Cl, OH, OCH 3 , CH 3 , or CH 2 CH 3 ; 
         where each occurrence of Z 2  is independently H, CH 3 , CF 3 , or SO 3 H; and where each occurrence of n is independently 0, 1, 2, or 3.