Telechelic poly(imide) oligomers, methods of manufacture, and uses thereof

Patent metadata

Field	Value
Publication number	US-10696792-B2
Application number	US-201716347105-A
Country	US
Kind code	B2
Filing date	Nov 16, 2017
Priority date	Nov 16, 2016
Publication date	Jun 30, 2020
Grant date	Jun 30, 2020

Abstract

A ureido-pyrimidinone oligomer having the formula (I) wherein each Z′ is independently the same or different, and is a substituted or unsubstituted straight or branched chain C 1-10 alkyl, each R 1 is independently the same or different, and is a substituted or unsubstituted straight or branched chain C 1-20 alkylene, substituted or unsubstituted C 2-20 alkenylene, substituted or unsubstituted C 3-8 cycloalkylene, or substituted or unsubstituted C 6-18 arylene, each V is independently the same or different, and is a substituted or unsubstituted tetravalent C 4-40 hydrocarbon group, each R is independently the same or different, and is a substituted or unsubstituted C 1-24 divalent hydrocarbon group; and n has an average value of 2 to 50, preferably 3 to 40, more preferably 5 to 30.

First claim

What is claimed is:

1. A ureido-pyrimidinone oligomer having the formula

wherein
each Z′ is independently the same or different, and is a substituted or unsubstituted straight or branched chain C 1-10 alkyl,
each R 1 is independently the same or different, and is a substituted or unsubstituted straight or branched chain C 1-20 alkylene, substituted or unsubstituted C 2-20 alkenylene, substituted or unsubstituted C 3-8 cycloalkylene, or substituted or unsubstituted C 6-18 arylene,
each V is independently the same or different, and is a substituted or unsubstituted tetravalent C 4-40 hydrocarbon group,
each R is independently the same or different, and is a substituted or unsubstituted C 1-24 divalent hydrocarbon group, and
n has an average value of 2 to 50.

2. The oligomer of claim 1 , wherein Z′ is an unsubstituted C 1-3 alkyl, and R 1 is a straight chain C 3-10 alkylene.

3. The oligomer of claim 2 , wherein Z′ is methyl and R 1 is n-hexylene.

4. The oligomer of claim 1 , wherein V is a substituted or unsubstituted C 6-20 aromatic hydrocarbon group.

5. The oligomer of claim 1 , wherein V is

wherein W is —O—, —S—, —C(O)—, —SO 2 —, —SO—, —P(R a )(═O)— wherein R a is a C 1-8 alkyl or C 6-12 aryl, —C y H 2y — wherein y is an integer from 1 to 5 or a halogenated derivative thereof, or a group of the formula —O—Z—O— wherein Z is a substituted or unsubstituted aromatic C 6-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6 C 1-8 alkyl groups, 1 to 8 halogen atoms, or a combination thereof, provided that the valence of Z is not exceeded.

6. The oligomer of claim 1 , being a poly(etherimide) of the formula

wherein each Z is independently a substituted or unsubstituted aromatic C 6-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6 C 1-8 alkyl groups, 1 to 8 halogen atoms, or a combination thereof, provided that the valence of Z is not exceeded.

7. The oligomer of claim 6 , wherein Z is a divalent group of the formula

wherein
each R a and R b is independently the same or different, and is a halogen atom or a monovalent C 1-6 alkyl group,
p and q are each 0 to 4;
c is 0 to 4; and
each X a is independently the same or different, and is a single bond, —O—, —S—, —S(O)—, —S(O) 2 —, —C(O)—, or a C 1-18 hydrocarbon group.

8. The oligomer of claim 7 , wherein Z is a divalent group of the formula

wherein Q is —O—, —S—, —C(O)—, —SO 2 —, —SO—, or —C y H 2y — wherein y is an integer from 1 to 5 or a halogenated derivative thereof.

9. The oligomer of claim 1 , wherein R is a substituted or unsubstituted C 6-24 arylene group, a substituted or unsubstituted straight or branched chain C 1-20 alkylene group, or a substituted or unsubstituted C 3-8 cycloalkylene group.

10. The oligomer of claim 9 , wherein R is divalent group of the formula

wherein Q 1 is —O—, —S—, —C(O)—, —SO 2 —, —SO—, —P(R a )(O)— wherein W is a C 1-8 alkyl or C 6-12 aryl, —C y H 2y — wherein y is an integer from 1 to 5 or a halogenated derivative thereof, or —(C 6 H 10 ) z — wherein z is an integer from 1 to 4.

11. The oligomer of claim 10 , wherein R is m-phenylene, p-phenylene, bis(4,4′-phenylene)sulfone, bis(3,4′-phenylene)sulfone, or bis(3,3′-phenylene)sulfone.

12. A method for producing the ureido-pyrimidinone oligomer of claim 1 , the method comprising: reacting an amino-terminated oligomer of the formula

with an isocytosine of the formula

in the presence of a catalyst, under conditions effective to produce the ureido-pyrimidinone oligomer.

13. The method of claim 12 , wherein the amino-terminated oligomer and the isocytosine are reacted at a mole ratio of 1:3 to 1:1.1.

14. The method of claim 12 , wherein the reacting comprises
reacting the amino-terminated oligomer and the isocytosine in a solvent at a first temperature for a first period of time to form a first intermediate mixture;
adding the catalyst to the first intermediate mixture to form a second intermediate mixture; and
heating the second intermediate mixture at a second temperature to provide the ureido-pyrimidinone oligomer.

15. The method of claim 12 , wherein the amino-terminated oligomer is of the formula

16. The oligomer of claim 1 , wherein the oligomer has at least one of
an intrinsic glass transition temperature of greater than or equal to 180° C.,
a number average molecular weight of the ureido-pyrimidinone oligomer is 4,000 to 40,000 grams per mole, or
a Young's modulus greater than or equal to a Young's modulus of the same polyetherimide without the ureido-pyrimidinone groups, and having a molar mass of greater than 16,000 grams per mole.

17. An article comprising the oligomer of claim 1 .

18. The article of claim 17 , wherein the article is a film, a fiber, a foam, or a molded part.

19. The article of claim 17 , wherein the article is a film prepared by solution-casting the oligomer.

20. The article of claim 18 , wherein the article is a film prepared by melt processing the oligomer.

Assignees

• Sabic Global Technologies Bv

Inventors

• Odle Roy Ray
• Liu Guoliang
• Cao Ke
• Long Timothy Edward
• Dennis Joseph Michael

Classifications

• C08G2115/06

  to carbodiimide or uretone-imine groups · CPC title

• C07D239/47

  One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine · CPC title

• C08G73/1053 Primary

  with oxygen only in the tetracarboxylic moiety · CPC title

• C08G73/10

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title

• C08L2203/12

  used for fibers · CPC title