Antibacterial hydrophilic compound

Abstract

The present disclosure provides an antibacterial hydrophilic compound. The antibacterial hydrophilic compound may react, induced by light through a hydrogen abstraction group in the structural formula thereof, with a C—H group and thus bind to a surface of a material having the C—H group (for example, chemical fibers such as polyester, chinlon, and the like; plastics, rubbers, and other similar materials), which can impart a durable antibacterial activity and hydrophilicity to the material. The antibacterial hydrophilic compound has a relatively strong binding force to the surface of the material without damaging the mechanical properties of the raw material. The present disclosure also provides a modified material that is modified by the antibacterial hydrophilic compound.

We claim: 
     
         1 . An antibacterial hydrophilic compound, wherein a general structural formula of the antibacterial hydrophilic compound is represented by L-D-Q, wherein
 at least one end of the group L is connected to the group Q through the linking group D;   the group L has a structure represented by the following formulas (L 1 ), (L 2 ), (L 3 ), (L 4 ), or (L 5 );   the group D is a single-bond, or a divalent C 1-18  hydrocarbyl group that is unsubstituted or substituted, wherein the divalent C 1-18  hydrocarbyl group includes or does not include a linking group including heteroatom(s), the heteroatom(s) being at least one of O, S, N, Si, or P atoms;   the group Q is selected from a biguanide compound residue and a polyamino compound residue represented by a formula (C 1 ), a group represented by the following formulas (D 1 ) or (D 2 ), and halamine group represented by the following formulas (B 1 ), (B 2 ), or (B 3 ), wherein the polyamino compound residue refers to a residual portion of the polyamino compound excluding —NH 2  groups or —OH groups:   
       
         
           
           
               
               
           
         
         wherein 
         when L is L 1 , r is 2; 
         when L is L 3 , r is 1 or 2; 
         Y is one of a single bond, oxygen atom, sulfur atom, selenium atom, —C(O)— group, —SO 2 — group, —NH— group, and a C 1-3  alkylene group; R 1 -R 9  and R 2 ′-R 8 ′ are independently selected from hydrogen atom, halogen atom, monovalent polar group, and monovalent C 1-18  hydrocarbyl groups that are substituted or unsubstituted; 
       
       
         
           
           
               
               
           
         
          wherein 
         c is an integer from 0 to 2, n is a positive integer from 1 to 100, R c  is selected from a monovalent C 1-18  hydrocarbyl group that is unsubstituted or substituted, and X is selected from halogen atom; 
       
       
         
           
           
               
               
           
         
         wherein
 T may be R 13  or —R 23 -A ⊖ , R 11 -R 13  are independently selected from monovalent C 1-18  hydrocarbyl groups that are unsubstituted or substituted, and R 23  is selected from divalent C 1-18  hydrocarbyl groups that are unsubstituted or substituted; R 32 -R 33  are independently selected from hydrogen atom, halogen atom, monovalent polar group, and monovalent C 1-18  hydrocarbyl groups that are substituted or unsubstituted; A is selected from —COO, —SO 3  and —OPO 2 OR e , and R e  is a monovalent C 1-6  alkyl, cycloalkyl, or aryl group, wherein R e  is unsubstituted or substituted; 
 
       
       
         
           
           
               
               
           
         
         
           wherein
 X is selected from halogen atom; and 
 an end of the group Q with “ ” is connected to the linking group D. 
 
         
       
     
     
         2 . The antibacterial hydrophilic compound of  claim 1 , wherein Y is oxygen atom, sulfur atom, or —C(O)—. 
     
     
         3 . The antibacterial hydrophilic compound of  claim 1 , wherein when the group Q is the biguanide compound residue or the polyamino compound residue represented by the formula (C1), the linking group D is a divalent C 1-18  hydrocarbyl group that is unsubstituted or substituted and includes a linking group including heteroatom(s). 
     
     
         4 . The antibacterial hydrophilic compound of  claim 3 , wherein when the group Q is the biguanide compound residue or the polyamino compound residue represented by the formula (C1), the linking group D has the following group Z, wherein the group Z is —NH—* group, —NH—C(S)—NH—* group, —NH—C(O)—NH—* group, —CO—NH—* group, —SO 2 —NH—* group, —CH(OH)—NH—* group, or —CH(OH)CH 2 —NH—* group, and an end of the group Z with “*” is connected to the side of group Q. 
     
     
         5 . The antibacterial hydrophilic compound of  claim 1 , wherein the polyamino compound is selected from one or more of chitosan, polyethyleneimine, polyamide-amine dendrimer and its derivatives, diethylenetriamine, tetraethylenepentamine, tris (4-aminophenyl) amine, tris (2-aminoethyl) amine, and N′N-bis (3-aminopropyl) methylamine. 
     
     
         6 . The antibacterial hydrophilic compound of  claim 1 , wherein in the formulas (D1) or (D2), R 23  is selected from an alkylene group having 1-18 carbon atoms; R 32 -R 33  are independently selected from hydrogen atom, halogen atom, —CN, —SCN, —NO 2 , —NO, and monovalent unsubstituted or substituted C 1-7  alkyl, cycloalkyl, or aryl. 
     
     
         7 . The antibacterial hydrophilic compound of  claim 1 , wherein when the group Q is a structure represented by the formula (D1), the linking group D is —(CH 2 ) s —*, —O—(CH 2 ) t —*, —OCO-Ph-(CH 2 ) b —*, —NH—COOCH 2 —CH 2 —*, —CH 2 —NH—COO—CH 2 —CH 2 —*, or —O—CH 2 —CH(OH)—CH 2 —NH—CH 2 —*, and an end of the group D with “*” is connected to a side of the group Q, wherein s is an integer from 0 to 10, t is an integer from 1 to 6, and b is an integer from 0 to 6. 
     
     
         8 . The antibacterial hydrophilic compound of  claim 1 , wherein when the group Q is a structure represented by the formula (D2), the linking group D has the following group Z, wherein the group Z is —NH—C(O)—NH—*, —NH—C(S)—NH—*, —NH—C(S)—O—*, or —NHCOO*—, and an end of the group Z with “*” is connected to a side of group Q. 
     
     
         9 . The antibacterial hydrophilic compound of  claim 1 , wherein when the group Q is a structural formula represented by the formula (D1) and T is R 13 , the antibacterial hydrophilic compound is obtained by a nucleophilic addition reaction of a halogenated alkane R 13 —X with a compound L 1 ′ or L 2 ′ that has a tertiary amino group and is represented by the following structural formulas; or the antibacterial hydrophilic compound is obtained by a nucleophilic addition reaction of a tertiary amine compound 
       
         
           
           
               
               
           
         
       
       with the compound L 1 ′ or L 2 ′ that has a halogenated alkyl group represented by the following structural formulas: 
       
         
           
           
               
               
           
         
       
       wherein
 r is 1 or 2; Y is one of a single bond, oxygen atom, sulfur atom, selenium atom, —C(O)—, —SO 2 —, —NH—, and a C 1-3  alkylene group; R 1 -R 10  and R 2 ′-R 9 ′ are independently selected from hydrogen atom, halogen atom, monovalent polar groups, and monovalent C 1-18  hydrocarbyl groups that are unsubstituted or substituted, and at least one of R 1 -R 10  or R 2 ′-R 9 ′ is -D-N(R 11 )(R 12 ), or -D-X, and X is halogen atom. 
 
     
     
         10 . The antibacterial hydrophilic compound of  claim 1 , wherein when the Q group has a structure represented by the formula (D 1 ), and T is R 13  or —R 23 -A ⊖ , the antibacterial hydrophilic compound is obtained by reacting a compound E with a compound L1′ or L2′ having a tertiary amino group represented by the following structural formulas: 
       
         
           
           
               
               
           
         
         wherein 
         r is 1 or 2; Y is one of a single bond, oxygen atom, sulfur atom, selenium atom, —C(O)—, —SO 2 —, —NH—, and a C 1-3  alkylene group; R 1 -R 10  and R 2 ′-R 9 ′ are independently selected from hydrogen atom, halogen atom, monovalent polar groups, and monovalent C 1-18  hydrocarbyl groups that are unsubstituted or substituted, and at least one of R 1 -R 10  or R 2 ′-R 9 ′ is -D-N(R 11 )(R 12 ); 
         the compound E is selected from sultone, carboxylic acid lactone, X(CH 2 ) w COO − M t   + , X(CH 2 ) w SO 3 -M t   + , and cyclic phosphate, wherein X is selected from Br, Cl, and I, w is an integer no less than 1, and M t   +  is selected from Li + , Na + , K + , NH 4   + , Ag + , ½ Mg 2+ , and ½ Ca 2+ ; the cyclic phosphate has a structure represented by the following formula: 
       
       
         
           
           
               
               
           
         
          Re is selected from a that is unsubstituted or substituted monovalent C 1-6  alkyl, cycloalkyl, or aryl group, and R 23  is selected from a divalent C 1-18  hydrocarbyl group that is unsubstituted or substituted. 
       
     
     
         11 . The antibacterial hydrophilic compound of  claim 8 , wherein when the group Q is a structure represented by the formula (D2), and when T is R 13  or —R 23 -A ⊖ , the antibacterial hydrophilic compound is prepared by the following method:
 (1) reacting the compound L1′ or L2′ represented by the following structural formulas with pyridine having the general formula (I) to obtain a mixture, 
 
       
         
           
           
               
               
           
         
         wherein 
         r is 1 or 2; Y is one of a single bond, oxygen atom, sulfur atom, selenium atom, —C(O)—, —SO 2 —, —NH—, and a C 1-3  alkylene group; R 1 -R 10  and R 2 ′-R 9 ′ are independently selected from hydrogen atom, halogen atom, monovalent polar groups, and monovalent C 1-18  hydrocarbyl group that is unsubstituted or substituted, and at least one of R 1 -R 10  or R 2 ′-R 9 ′ has —NCO or —NCS; 
       
       
         
           
           
               
               
           
         
          wherein 
         G′ is selected from —OH, NH 2 , or —SH, and R 31  is selected from divalent C 1-18  hydrocarbyl groups that are unsubstituted or substituted, and R 32 -R 33  are independently selected from hydrogen atom, halogen atom, monovalent polar groups, and monovalent C 1-18  hydrocarbyl groups that are unsubstituted or substituted; 
         (2) reacting the mixture with the compound E to obtain a zwitterionic type of the antibacterial hydrophilic compound: 
         the compound E is selected from sultone, carboxylic acid lactone, X(CH 2 ) w COO − M t   + , X(CH 2 ) w SO 3 -M t   + , and cyclic phosphate, wherein X is selected from Br, Cl, and I, w is an integer no less than 1, M t   +  is selected from Li + , Na + , K + , NH 4   + , Ag + , ½Mg 2+ , and ½ Ca 2+ ; cyclic phosphate has a structure represented by the following formula: 
       
       
         
           
           
               
               
           
         
          wherein Re is selected from monovalent C 1-6  alkyl that is unsubstituted or substituted, cycloalkyl, or aryl, and R 23  is selected from divalent C 1-18  hydrocarbyl groups that are unsubstituted or substituted. 
       
     
     
         12 . The antibacterial hydrophilic compound of  claim 10 , wherein the structural formula of carboxylic acid lactone is 
       
         
           
           
               
               
           
         
       
       and y is an integer from 1 to 6; the structural formula of sultone is 
       
         
           
           
               
               
           
         
       
       and x is an integer from 1 to 6. 
     
     
         13 . The antibacterial hydrophilic compound of  claim 11 , wherein the structural formula of carboxylic acid lactone is 
       
         
           
           
               
               
           
         
       
       and y is an integer from 1 to 6; the structural formula of sultone is 
       
         
           
           
               
               
           
         
       
       and x is an integer from 1 to 6. 
     
     
         14 . The antibacterial hydrophilic compound of  claim 1 , wherein when the group Q is a halamine group represented by the formula (B1), (B2), (B3) or (B4), the linking group D is an alkylene group having 1 to 10 carbon atoms. 
     
     
         15 . The antibacterial hydrophilic compound of  claim 1 , wherein when the group Q is a halamine group represented by the formula (B 1 ), (B 2 ), (B 3 ) or (B 4 ), the linking group D has the following group Z, wherein the group Z is —NH—C(O)—O—CH 2 —*, —NH—CH 2 —CH(OH)—(CH 2 ) q —*, —S—CH 2 —CH(OH)—(CH 2 ) q —*, or —O—CH 2 —CH(OH)—(CH 2 ) q *, wherein q is an integer from 1 to 6, and an end of the group Z with “*” is connected to one side of the group Q. 
     
     
         16 . The antibacterial hydrophilic compound of  claim 1 , wherein when the group Q is a halamine group represented by the formula (B 1 ), (B 2 ), (B 3 ) or (B 4 ), the linking group D has the following group Z, wherein the group Z is —NH—C(S)—O—CH 2 —*, —C(O)—O—CH 2 —*, —SO 2 —O—CH 2 —*, —O—CH 2 —*, or —CH(OH)CH 2 —O—CH 2 —*, and an end with “*” is on the side of the halamine group. 
     
     
         17 . A processing method for a surface of a material, comprising the following operations:
 providing a modification agent including an antibacterial hydrophilic compound;   spraying or brushing the modification agent on a surface of a material containing C—H groups and treating the surface with ultraviolet light to cause the antibacterial hydrophilic compound to covalently bind the surface to obtain a processed material, wherein   a general structural formula of the antibacterial hydrophilic compound is represented by L-D-Q, wherein
 at least one end of the group L is connected to the group Q through the linking group D; 
 the group L has a structure represented by the following formulas (L 2 ), (L 3 ), (L 4 ), or (L 5 ); 
 the group D is a single-bond, or a divalent C 1-18  hydrocarbyl group that is unsubstituted or substituted, wherein the divalent C 1-18  hydrocarbyl group includes or does not include a linking group including heteroatom(s), the heteroatom(s) being at least one of O, S, N, Si, or P atoms; 
 the group Q is selected from a biguanide compound residue and a polyamino compound residue represented by a formula (C 1 ), a group represented by the following formulas (D 1 ) or (D 2 ), and halamine group represented by the following formulas (B 1 ), (B 2 ), or (B 3 ), wherein the polyamino compound residue refers to a residual portion of the polyamino compound excluding —NH 2  groups or —OH groups: 
   
       
         
           
           
               
               
           
         
         
           wherein
 when L is L 1 , r=2; when L is L 2 , r is 1 or 2; Y is one of a single bond, oxygen atom, sulfur atom, selenium atom, —C(O)— group, —SO 2 — group, —NH— group, and C 1-3  alkylene groups; R 1 -R 9  and R 2 ′-R 8 ′ are independently selected from hydrogen atom, halogen atom, monovalent polar group, and monovalent C 1-18  hydrocarbyl groups that are substituted or unsubstituted; 
 
         
       
       
         
           
           
               
               
           
         
         
           
              wherein 
             c is an integer from 0 to 2, n is a positive integer from 1 to 100, R c  is selected from a monovalent C 1-18  hydrocarbyl group that is unsubstituted or substituted, and X is selected from halogen atom; 
           
         
       
       
         
           
           
               
               
           
         
         
           
             wherein
 T is R 13  or R 13  or —R 23 -A ⊖ , R 11 -R 13  are independently selected from monovalent C 1-18  hydrocarbyl groups that are unsubstituted or substituted, and R 23  is selected from divalent C 1-18  hydrocarbyl groups that are unsubstituted or substituted; R 32 -R 33  are independently selected from hydrogen atom, halogen atom, monovalent polar group, and monovalent C 1-18  hydrocarbyl groups that are substituted or unsubstituted; A is selected from —COO, —SO 3  and —OPO 2 OR e , and R e  is a monovalent C 1-6  alkyl, cycloalkyl, or aryl group, wherein R e  is unsubstituted or substituted; 
 
           
         
       
       
         
           
           
               
               
           
         
         
           
             
               wherein X is selected from halogen atom; and an end of the group Q with “ ” is connected to the linking group D. 
             
           
         
       
     
     
         18 . The processing method of  claim 17 , wherein the material containing C—H groups includes one or more of synthetic fibers, rubbers, plastics, polymer coatings, wherein the synthetic fibers include polyesters, polypropylene, acrylics, nylons, vinylon, and spandex. 
     
     
         19 . A modified material, wherein the modified material includes a surface covalently bonded with an antibacterial hydrophilic compound, the modified material having an antibacterial function, wherein
 a general structural formula of the antibacterial hydrophilic compound is represented by L-D-Q, wherein
 at least one end of the group L is connected to the group Q through the linking group D; 
 the group L has a structure represented by the following formulas (L 2 ), (L 3 ), (L 4 ), or (L 5 ); 
 the group D is a single-bond, or a divalent C 1-18  hydrocarbyl group that is unsubstituted or substituted, wherein the divalent C 1-18  hydrocarbyl group includes or does not include a linking group including heteroatom(s), the heteroatom(s) being at least one of O, S, N, Si, or P atoms; 
 the group Q is selected from a biguanide compound residue and a polyamino compound residue represented by a formula (C 1 ), a group represented by the following formulas (D 1 ) or (D 2 ), and halamine group represented by the following formulas (B 1 ), (B 2 ), or (B 3 ), wherein the polyamino compound residue refers to a residual portion of the polyamino compound excluding —NH 2  groups or —OH groups: 
   
       
         
           
           
               
               
           
         
         
           wherein
 when L is L 1 , r=2; when L is L 2 , r is 1 or 2; Y is one of a single bond, oxygen atom, sulfur atom, selenium atom, —C(O)— group, —SO 2 — group, —NH— group, and C 1-3  alkylene groups; R 1 -R 9  and R 2 ′-R 8 ′ are independently selected from hydrogen atom, halogen atom, monovalent polar group, and monovalent C 1-18  hydrocarbyl groups that are substituted or unsubstituted; 
 
         
       
       
         
           
           
               
               
           
         
         
           
              wherein 
             c is an integer from 0 to 2, n is a positive integer from 1 to 100, R c  is selected from a monovalent C 1-18  hydrocarbyl group that is unsubstituted or substituted, and X is selected from halogen atom; 
           
         
       
       
         
           
           
               
               
           
         
         
           
             wherein
 T is R 13  or R 13  or —R 23 -A ⊖ , R 11 -R 13  are independently selected from monovalent C 1-18  hydrocarbyl groups that are unsubstituted or substituted, and R 23  is selected from divalent C 1-18  hydrocarbyl groups that are unsubstituted or substituted; R 32 -R 33  are independently selected from hydrogen atom, halogen atom, monovalent polar group, and monovalent C 1-18  hydrocarbyl groups that are substituted or unsubstituted; A is selected from —COO, —SO 3  and —OPO 2 OR e , and R e  is a monovalent C 1-6  alkyl, cycloalkyl, or aryl group, wherein R e  is unsubstituted or substituted; 
 
           
         
       
       
         
           
           
               
               
           
         
         
           
             
               wherein X is selected from halogen atom; and an end of the group Q with “ ” is connected to the linking group D. 
             
           
         
       
     
     
         20 . The modified material of  claim 19 , wherein at least one mechanical property of the modified material is improved by the antibacterial hydrophilic compound.