Process for preparing poly(arylene ethers) with pendant crosslinkable groups
View Patent ↗A process comprising: a) reacting a diphenol monomer A with a monomer B having two locations for reaction with A to form arylene ether monomer C and b) reacting arylene ether monomer C with a diphenol monomer D to form a polymer, where monomer A is HX 1 -Q 1 -X 1 H; (II) monomer B is arylene ether monomer C is and monomer D is wherein: Q 1 comprises at least one aryl or heteroaryl group; Q 2 comprises at least one aryl or heteroaryl group; X 1 is O bonded directly to an aryl carbon of Q 1 ; X 2 is O bonded directly to an aryl carbon of Q 2 ; Z is a linker comprising at least one —(C(R 2 ) 2 )— group; Y is a single bond or linker group (e.g., comprising up to about 50 carbons); R 1 is independently at each occurrence H, a halogen, an alkyl group, a heteroalkyl group, an aryl group, or a heteroaryl group; R 2 is independently at each occurrence H, an alkyl group, or a heteroalkyl group; and R 3 is H or a crosslinkable group.
1. A process, comprising a) reacting monomer A with monomer B to give arylene ether monomer C and b) reacting monomer C with another monomer D to give a polymer, wherein:
monomer A is
monomer B is
arylene ether monomer C is
monomer D is
HX 1 -Q 1 -X 1 H;
Q 1 comprises at least one aryl or heteroaryl group;
Q 2 comprises at least one aryl or heteroaryl group;
X 1 is O bonded directly to an aryl carbon of Q 1 ;
X 2 is O bonded directly to an aryl carbon of Q 2 ;
Z is a linker comprising at least one —(C(R 2 ) 2 )— group;
Y is a single bond or a linker group;
L is a nucleophilic aromatic leaving substituent;
R 1 is independently at each occurrence H, a halogen, an alkyl group, a heteroalkyl group, an aryl group, or a heteroaryl group; and
R 2 is independently at each occurrence H, an alkyl group, or a heteroalkyl group.
2. The process of claim 1 , wherein Q 1 comprises at least two aryl or heteroaryl groups.
3. The process of claim 2 , wherein Q 1 comprises a methylenediphenyl group in which the methylene carbon is bonded to at least 2 phenyl groups.
4. The process of claim 3 , wherein Q 1 is selected from the group consisting of
5. The process of claim 1 , wherein Q 1 comprises a polycyclic aromatic ring system or a polycyclic heteroaromatic ring system.
6. The process of claim 1 , wherein Y is a single bond, an alkene or an alkyne group.
7. The process of claim 1 , wherein Y is a ketone, a sulfone, or a phosphine oxide.
8. The process of claim 7 , wherein Y is selected from the group consisting of
9. The process of claim 1 , wherein Q 2 comprises a 6-membered aromatic or heteroaromatic ring, a polycyclic aromatic ring system, or a polycyclic heteroaromatic ring system.
10. The process of claim 9 , wherein Q 2 comprises
11. The process of claim 1 , wherein Z is —(CH 2 ) n — or —(CH 2 CH 2 O) n —, wherein n=1 to 10.
12. The process of claim 1 , wherein:
Q 1 comprises a methylenediphenyl group in which the methylene carbon is bonded to at least 2 phenyl groups;
Q 2 comprises a phenyl ring;
Y is a single bond;
and
Z is —CH 2 —
13. The process of claim 12 , wherein R 1 is fluorine.
14. The process of claim 12 , wherein L is a halogen, nitro group, or phenylsulfonyl group.
15. The process of claim 14 , wherein L is fluorine.
16. The process of claim 12 , wherein the methylene carbon of Q 1 is bonded to at least three phenyl groups.
17. The process of claim 1 , wherein reacting monomer A with monomer B to form monomer C comprises heating a mixture of monomer A and monomer B in a dipolar aprotic solvent to at least 110° C.
18. The process of claim 17 , further comprising cooling the reaction mixture of monomer A and monomer B after monomer C is formed and before monomer D is reacted with monomer C.
19. The process of claim 18 , wherein reacting monomer C with monomer D to form a polymer comprises heating a mixture of monomer C and monomer D in a dipolar aprotic solvent to at least 110° C. thereby providing a polymer solution.
20. The process of claim 19 , further comprising filtering the polymer solution while the temperature of the polymer solution is greater than about 80° C.