Polyimide-based block copolymers and polyimide-based film comprising the same

1. A polyimide-based block copolymer comprising

a first repeating unit represented by Chemical Formula 1, and

a second repeating unit represented by Chemical Formula 2:

wherein, in Chemical Formulae 1 and 2,

each R 1 is the same as or different from each other in each repeating unit, and each is independently a single bond, —O—, —S—, —C(═O)—, —CH(OH)—, —S(═O) 2 —, —Si(CH 3 ) 2 —, —(CH 2 ) p —(wherein 1≤p≤10), —(CF 2 ) q — (wherein 1≤q≤10), —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —C(═O)NH—, or a C6 to C30 aromatic organic group;

each R 2 is independently —H, —F, —Cl, —Br, —I, —CF 3 , —CCl 3 , —CBr 3 , —CI 3 , —NO 2 , —CN, —COCH 3 , —CO 2 C 2 H 5 , a silyl group containing three C1 to C10 aliphatic organic groups, a C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group;

n1 and n2 are independently 0 to 3;

Ar 1 and Ar 2 are the same as or different from each other in each repeating unit, and each is independently a C6 to C30 aromatic organic group, at least one of Ar 1 and Ar 2 comprises a C6 to C30 aromatic organic group substituted with —COOH, acrylate, or methacrylate, and the aromatic organic group exists alone, or two or more aromatic organic groups are bonded to each other to form a condensed ring, or two or more aromatic organic groups are linked by a single bond, —O—, —S—, —C(═O)—, —CH(OH)—, —S(═O) 2 —, —Si(CH 3 ) 2 —, —(CH 2 ) p —(wherein 1≤p≤10), —(CF 2 ) q — (wherein 1≤q≤10), —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, or —C(═O)NH—;

E 1 to E 6 are independently a single bond, —NH—, or —C(═O)—;

each Z 1 is the same as or different from each other in each repeating unit, and each is independently a trivalent linking group derived from at least one compound selected from the group consisting of triacyl halide, triamine, and tricarboxylic acid; and

each Z 2 is the same as or different from each other in each repeating unit, and each is independently a divalent linking group derived from at least one compound selected from the group consisting of diacyl halide, diamine, and dicarboxylic acid.

2. The polyimide-based block copolymer of claim 1 ,

wherein Ar 1 and Ar 2 are independently a group represented by Chemical Formula Ar(A) or Ar(B):

wherein, in Chemical Formulae Ar(A) and Ar(B),

each R 3 is independently —COOH, acrylate, or methacrylate;

n3 to n5 are independently 0 to 4, and at least one of n3 to n5 included in Ar 1 and Ar 2 is more than 1; and

each R 4 is independently a single bond, —O—, —S—, —C(═O)—, —CH(OH)—, —S(═O) 2 —, —Si(CH 3 ) 2 —, —(CH 2 ) p — (wherein 1≤p≤10), —(CF 2 ) q — (wherein 1≤q≤10), —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, or —C(═O)NH—.

3. The polyimide-based block copolymer of claim 1 ,

wherein Z 1 is a trivalent linking group derived from at least one compound selected from the group consisting of benzene-1,3,5-tricarbonyl trichloride, benzene-1,3,5-tricarboxylic acid, benzene-1,3,5-triamine, benzene-1,2,4-triamine, cyclohexane-1,3,5-triamine, cyclohexane-1,2,4-triamine, and pyrimidine-2,4,6-triamine; and

Z 2 is a divalent linking group derived from at least one compound selected from the group consisting of isophthaloyl dichloride, terephthaloyl chloride, isophthalic acid, terephthalic acid, benzene-1,3-diamine, benzene-1,4-diamine, pyrimidine-2,5-diamine, pyrimidine-2,4-diamine, cyclohexane-1,3-diamine, and cyclohexane-1,4-diamine.

4. The polyimide-based block copolymer of claim 1 ,

wherein Z 1 is selected from the group represented by Chemical Formula Z1, and

Z 2 is selected from the group represented by Chemical Formula Z2:

5. The polyimide-based block copolymer of claim 1 ,

wherein the first repeating unit comprises a repeating unit represented by Chemical Formula 1A, and the second repeating unit comprises a repeating unit represented by Chemical Formula 2A:

wherein, in Chemical Formulae 1A and 2A,

each R 2 is independently —H, —F, —Cl, —Br, —I, —CF 3 , —CCl 3 , —CBr 3 , —CI 3 , —NO 2 , —CN, —COCH 3 , —CO 2 C 2 H 5 , a silyl group containing three C1 to C10 aliphatic organic groups, a C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group;

n1 and n2 are independently 0 to 3; and

Ar 1 and Ar 2 are the same as or different from each other in each repeating unit, and each is independently a C6 to C30 aromatic organic group, at least one of Ar 1 and Ar 2 comprises a C6 to C30 aromatic organic group substituted with —COOH, acrylate, or methacrylate, and the aromatic organic group exists alone, or two or more aromatic organic groups are bonded to each other to form a condensed ring, or two or more aromatic organic groups are linked by a single bond, —O—, —S—, —C(═O)—, —CH(OH)—, —S(═O) 2 —, —Si(CH 3 ) 2 —, —(CH 2 ) p —(wherein 1≤p≤10), —(CF 2 ) q — (wherein 1≤q≤10), —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, or —C(═O)NH—.

6. The polyimide-based block copolymer of claim 1 ,

wherein the first repeating unit comprises a repeating unit represented by Chemical Formula 1B, and the second repeating unit comprises a repeating unit represented by Chemical Formula 2B:

wherein, in Chemical Formulae 1B and 2B,

each R 2 is independently —H, —F, —Cl, —Br, —I, —CF 3 , —CCl 3 , —CBr 3 , —CI 3 , —NO 2 , —CN, —COCH 3 , —CO 2 C 2 H 5 , a silyl group containing three C1 to C10 aliphatic organic groups, a C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group;

n1 and n2 are independently 0 to 3;

each R 3 is independently —COOH, acrylate, or methacrylate;

n3 to n5 are independently 0 to 4, and at least one of n3 to n5 is more than 1; and

each R 4 is independently a single bond, —O—, —S—, —C(═O)—, —CH(OH)—, —S(═O) 2 —, —Si(CH 3 ) 2 —, —(CH 2 ) p — (wherein 1≤p≤10), —(CF 2 ) q — (wherein 1≤q≤10), —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, or —C(═O)NH—.

7. The polyimide-based block copolymer of claim 1 , wherein a weight ratio of the first repeating unit to the second repeating unit is 1:1 to 3:1.

8. The polyimide-based block copolymer of claim 1 , wherein a weight average molecular weight thereof is 100,000 to 5,000,000 g/mol.

9. A polyimide-based film comprising the polyimide-based block copolymer according to claim 1 .

10. The polyimide-based film of claim 9 , wherein pencil hardness is at least 1H, as measured in accordance with ASTM D3363.