US 12,077,644 B2
Amide acid oligomer process for molding polyimide composites
Masahiko Miyauchi, Pasadena, TX (US)
Assigned to Kaneka Americas Holding, Inc., Pasadena, TX (US)
Appl. No. 17/282,256
Filed by Kaneka Americas Holding, Inc., Pasadena, TX (US)
PCT Filed Oct. 2, 2019, PCT No. PCT/US2019/054286
§ 371(c)(1), (2) Date Apr. 1, 2021,
PCT Pub. No. WO2020/072639, PCT Pub. Date Apr. 9, 2020.
Claims priority of provisional application 62/740,149, filed on Oct. 2, 2018.
Prior Publication US 2021/0340344 A1, Nov. 4, 2021
Int. Cl. C08J 5/04 (2006.01); B32B 5/26 (2006.01); B32B 27/28 (2006.01); C08G 73/10 (2006.01); C08G 73/12 (2006.01); C08J 5/24 (2006.01)
CPC C08J 5/243 (2021.05) [B32B 5/26 (2013.01); B32B 27/281 (2013.01); C08G 73/1032 (2013.01); C08G 73/1071 (2013.01); C08G 73/122 (2013.01); C08J 5/042 (2013.01); B32B 2260/023 (2013.01); B32B 2260/046 (2013.01); B32B 2262/106 (2013.01); B32B 2305/076 (2013.01); B32B 2307/542 (2013.01); B32B 2307/558 (2013.01); C08J 2379/08 (2013.01)] 15 Claims
OG exemplary drawing
 
1. A method of making an amide acid oligomer solution, comprising:
dissolving an aromatic diamine and an aromatic tetracarboxylic compound in a solvent to form a mixture, wherein the solvent has a boiling point of less than 150° C.;
stirring the mixture at a temperature ranging from about 5° C. to about 60° C. for about 1 hour to about 24 hours to form a reaction solution;
adding unsaturated acid anhydride to the reaction solution; and
stirring the reaction solution at a temperature ranging from about 5° C. to about 60° C. for about 1 minute to about 180 minutes to form an amide acid oligomer solution, the amide acid oligomer solution having the amide acid oligomer in the solvent,
wherein the amide acid oligomer is represented by at least one of the following General Formulae (1)-(4):

OG Complex Work Unit Chemistry
wherein in the General Formula (1):
each R1 and R2 represents a bivalent aromatic diamine residue;
each R3 and R4 represents a tetravalent aromatic tetracarboxylic acid residue;
the two amide groups attached to R3 and R4 exist at either trans- or cis-position;
each R5 and R6 represents a hydrogen atom or a phenyl group, where at least one of R5 or R6 is a phenyl group;
m and n satisfy the following relations: m≥1, n≥0, 1≤m+n≤20, and 0.05≤m/(m+n)≤1;
the repeating units formed by m and n are arranged in blocks or randomly; and
the two amide linkages attached to the tetravalent aromatic tetracarboxylic acid residue represented by R3 and R4 are oriented such that the two amide linkages on either side of the residue are located at the meta-position of the residue relative to each other, and/or at the para-position of the residue relative to each other;

OG Complex Work Unit Chemistry
wherein in the General Formula (2):
each R1 and R2 represents a bivalent aromatic diamine residue;
each R3 and R4 represents a tetravalent aromatic tetracarboxylic acid residue;
the two amide groups attached to R3 and R4 exist at either trans- or cis-position;
each R5 and R6 represents a hydrogen atom or a phenyl group, where at least one of R5 or R6 is a phenyl group;
m and n satisfy the following relations: m≥1, n≥0, l≤m+n≤20, and 0.05≤m/(m+n)≤1; and
the repeating units formed by m and n are arranged in blocks or randomly; and
the two amide linkages attached to the tetravalent aromatic tetracarboxylic acid residue represented by R3 and R4 are oriented such that the two amide linkages on either side of the residue are located at the meta-position of the residue relative to each other, and/or at the para-position of the residue relative to each other;

OG Complex Work Unit Chemistry
wherein in the General Formula (3), each R1 and R2 represents bivalent aromatic diamine residue; each R5 and R6 represents a hydrogen atom or a phenyl group, where at least one of R5 or R6 is a phenyl group; m and n satisfy the following relations: m≥1, n≥0, l≤m+n≤20, and 0.05≤m/(m+n)≤1; and the repeating units formed by m and n are arranged in blocks or randomly; and

OG Complex Work Unit Chemistry
wherein in the General Formula (4):
each R1 and R2 represents a bivalent aromatic diamine residue;
each R3 and R4 represents a tetravalent aromatic tetracarboxylic acid residue;
the two amide groups attached to R3 and R4 exist at either trans- or cis-position;
each R5 and R6 represents a hydrogen atom or a phenyl group, where at least one of R5 or R6 is a phenyl group;
m and n satisfy the following relations: m≥1, n≥0, 1≤m+n≤20, and 0.05≤m/(m+n)≤1; and
the repeating units formed by m and n are arranged in blocks or randomly; and
the two amide linkages attached to the tetravalent aromatic tetracarboxylic acid residue represented by R3 and R4 are oriented such that the two amide linkages on either side of the residue are located at the meta-position of the residue relative to each other, and/or at the para-position of the residue relative to each other.
 
12. An amide acid oligomer powder having a complex viscosity higher than 104 Pa·s over a temperature range of about 25° C. to about 250° C.