Functional molecules and other structural carbon-based molecules with rigid backbones and kinked segments

Abstract

The present disclosure relates to methods for using functional molecules and other structural carbon-based molecules with rigid backbones and kinked segments to alter the interactions between molecules, and consequently improve/modify the properties of materials. In particular, the disclosure provides methods for using functional molecules and other structural carbon-based molecules with rigid backbones and kinked segments as (1) precursors for carbon fiber, (2) “molecular agents” to separate and/or link π-π stacked aromatic systems, 3) stabilizers in composite materials to achieve better blending of matrix with fiber reinforcement, and/or (4) one of the components in carbon fibers to achieve better mechanical properties.

1 . A method of altering the interactions between molecules in a system comprising mixing functional molecules and other structural carbon-based molecules with rigid backbones and kinked segments with the molecules in the system. 
     
     
         2 . The method according to  claim 1 , wherein the system is a system for preparing carbon fibers. 
     
     
         3 . The method according to  claim 2 , further comprising:
 polymerizing functional monomers with rigid backbones and kinked segments alone or as a component to form a precursor polymer;   spinning the precursor polymer to form precursor fibers;   cross-linking the precursor polymers to stabilizer the precursor fibers; and   carbonizing or graphitizing the cross-linked precursor fibers to form carbon fibers.   
     
     
         4 . The method according to  claim 2 , further comprising:
 polymerizing functional monomers with rigid backbones and kinked segments alone or as a component to form a precursor polymer;   spinning the precursor polymer to form precursor fibers;   cross-linking the precursor polymers to stabilizer the precursor fibers through functional groups on the functional monomers; and   carbonizing or graphitizing the cross-linked precursor fibers to form carbon fibers.   
     
     
         5 . The method according to  claim 4 , wherein the precursor polymers are cross-linked through functional groups on the functional monomers by click chemistry. 
     
     
         6 . The method according to  claim 2 , further comprising:
 polymerizing functional monomers with rigid backbones and kinked segments;   blending the polymers from the polymerization step with other carbon fiber polymer precursors to form a precursor polymer mixture;   spinning the precursor polymer mixture to form precursor fibers;   cross-linking the precursor polymer mixture to stabilizer the precursor fibers; and   carbonizing or graphitizing the cross-linked precursor fibers to form carbon fibers.   
     
     
         7 . The method according to  claim 2 , wherein the functional molecules and other structural carbon-based molecules with rigid backbones and kinked segments have the following general chemical structure: 
       
         
           
           
               
               
           
         
         wherein: 
         in all structures the carbon indicated by “C” denotes a spiro carbon; 
         A 1  and A 2  are each independently selected from: 
       
       
         
           
           
               
               
           
         
         A 3  is a selected from substituted or unsubstituted C 5 -C 6  aryl, substituted or unsubstituted C 5 -C 6  heteroaryl, substituted or unsubstituted C 5 -C 6  cycloalkyl and substituted or unsubstituted C 5 -C 6  cyclic heterocycloalkyl; 
         X is —CH 2 , —C═O, —O—, or —N—R 6 ; 
         R 1 , R 2 , R 3 , and R 4  are each independently selected from H and Y—Z; 
         R 5  represents the linking point to other segments; 
         R 6  is independently at each occurrence selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl; 
         Y is independently absent or selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —NH—(C═O)—; =NO—C 1-6  alkyl-; and —(C═O)-phenyl-; 
         Z is independently selected from —N 3 , —C≡CH, —C≡C—R′, —C≡N, —(C═O)—H, —SH, —CH═CH 2 , halide, —SO 3 R 6 , —B(OR 6 ) 22 , Sn(R 6 ) 3 , and Zn(R 6 ) 2 ; 
         R′ is selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —CN, —CO 2 R 6 , —(C═O)—N(R 6 ) 2 , and —(C═O)—R 6 ; and 
         R″ is selected from R 3  and R 4 . 
       
     
     
         8 . The method according to  claim 2 , wherein the functional molecules and other structural carbon-based molecules with rigid backbones and kinked segments have one or more of the following chemical structures: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         9 . A carbon fiber produced using the method according to  claim 7 . 
     
     
         10 . The method according to  claim 1 , wherein the system is a π-π stacked aromatic system. 
     
     
         11 . The method according to  claim 10 , further comprising:
 mixing functional molecules with rigid backbones and kinked segments with a π-π stacked aromatic system.   
     
     
         12 . The method according to  claim 11 , further comprising:
 reacting with the aromatics in the π-π stacked aromatic system through additional reactive functional groups on the functional molecules.   
     
     
         13 . The method according to  claim 11 , wherein the functional molecules with rigid backbones and kinked segments have the following general chemical structure: 
       
         
           
           
               
               
           
         
         wherein: 
         in all structures the carbon indicated by “C” denotes a spiro carbon; 
         A 1  and A 2  are each independently selected from: 
       
       
         
           
           
               
               
           
         
         A 3  is a selected from substituted or unsubstituted C 5 -C 6  aryl, substituted or unsubstituted C 5 -C 6  heteroaryl, substituted or unsubstituted C 5 -C 6  cycloalkyl and substituted or unsubstituted C 5 -C 6  cyclic heterocycloalkyl; 
         X is —CH 2 , —C═O, —O—, or —N—R 6 ; 
         R 1 , R 2 , R 3 , and R 4  are each independently selected from H and Y—Z; 
         R 5  represents the linking point to other segments; 
         R 6  is independently at each occurrence selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl; 
         Y is independently absent or selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —NH—(C═O)—; =NO—C 1-6  alkyl-; and —(C═O)-phenyl-; 
         Z is independently selected from —N 3 , —C≡CH, —C≡C—R′, —C≡N, —(C═O)—H, —SH, —CH═CH 2 , halide, —SO 3 R 6 , —B(OR 6 ) 22 , Sn(R 6 ) 3 , and Zn(R 6 ) 2 ; 
         R′ is selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —CN, —CO 2 R 6 , —(C═O)—N(R 6 ) 2 , and —(C═O)—R 6 ; and 
         R″ is selected from R 3  and R 4 . 
       
     
     
         14 . The method according to  claim 11 , wherein the functional molecules with rigid backbones and kinked segments have one or more of the following chemical structures: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         15 . The method according to  claim 12 , wherein the functional molecules with rigid backbones and kinked segments have one or more of the following chemical structures: 
       
         
           
           
               
               
           
         
       
     
     
         16 . The method according to  claim 1 , wherein the system is a composite material system. 
     
     
         17 . The method according to  claim 16 , further comprising:
 mixing functional molecules with rigid backbones and kinked segments with thermoplastic or thermoset materials and filler species to form the composite materials.   
     
     
         18 . The method according to  claim 17 , wherein the functional molecules with rigid backbones and kinked segments have the following general chemical structure: 
       
         
           
           
               
               
           
         
         wherein: 
         in all structures the carbon indicated by “C” denotes a spiro carbon; 
         A 1  and A 2  are each independently selected from: 
       
       
         
           
           
               
               
           
         
         A 3  is a selected from substituted or unsubstituted C 5 -C 6  aryl, substituted or unsubstituted C 5 -C 6  heteroaryl, substituted or unsubstituted C 5 -C 6  cycloalkyl and substituted or unsubstituted C 5 -C 6  cyclic heterocycloalkyl; 
         X is —CH 2 , —C═O, —O—, or —N—R 6 ; 
         R 1 , R 2 , R 3 , and R 4  are each independently selected from H and Y—Z; 
         R 5  represents the linking point to other segments; 
         R 6  is independently at each occurrence selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl; 
         Y is independently absent or selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —NH—(C═O)—; =NO—C 1-6  alkyl-; and —(C═O)-phenyl-; 
         Z is independently selected from —N 3 , —C≡CH, —C≡C—R′, —C≡N, —(C═O)—H, —SH, —CH═CH 2 , halide, —SO 3 R 6 , —B(OR 6 ) 22 , Sn(R 6 ) 3 , and Zn(R 6 ) 2 ; 
         R′ is selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —CN, —CO 2 R 6 , —(C═O)—N(R 6 ) 2 , and —(C═O)—R 6 ; and 
         R″ is selected from R 3  and R 4 . 
       
     
     
         19 . A composite material produced using the method according to  claim 17 . 
     
     
         20 . The method according to  claim 1 , wherein the system is a hollow carbon fiber material system. 
     
     
         21 . The method according to  claim 20 , further comprising:
 mixing functional molecules with rigid backbones and kinked segments with other precursor materials to make hollow carbon fiber material.   
     
     
         22 . The method according to  claim 21 , wherein the functional molecules with rigid backbones and kinked segments have the following general chemical structure: 
       
         
           
           
               
               
           
         
         wherein: 
         in all structures the carbon indicated by “C” denotes a spiro carbon; 
         A 1  and A 2  are each independently selected from: 
       
       
         
           
           
               
               
           
         
         A 3  is a selected from substituted or unsubstituted C 5 -C 6  aryl, substituted or unsubstituted C 5 -C 6  heteroaryl, substituted or unsubstituted C 5 -C 6  cycloalkyl and substituted or unsubstituted C 5 -C 6  cyclic heterocycloalkyl; 
         X is —CH 2 , —C═O, —O—, or —N—R 6 ; 
         R 1 , R 2 , R 3 , and R 4  are each independently selected from H and Y—Z; 
         R 5  represents the linking point to other segments; 
         R 6  is independently at each occurrence selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl; 
         Y is independently absent or selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —NH—(C═O)—; =NO—C 1-6  alkyl-; and —(C═O)-phenyl-; 
         Z is independently selected from —N 3 , —C≡CH, —C≡C—R′, —C≡N, —(C═O)—H, —SH, —CH═CH 2 , halide, —SO 3 R 6 , —B(OR 6 ) 22 , Sn(R 6 ) 3 , and Zn(R 6 ) 2 ; 
         R′ is selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —CN, —CO 2 R 6 , —(C═O)—N(R 6 ) 2 , and —(C═O)—R 6 ; and 
         R″ is selected from R 3  and R 4 . 
       
     
     
         23 . A hollow carbon fiber material produced using the method according to  claim 21 .