Phosphinated poly(2,6-dimethyl phenylene oxide) oligomers and thermosets thereof

Patent metadata

Field	Value
Publication number	US-10544261-B2
Application number	US-201615287962-A
Country	US
Kind code	B2
Filing date	Oct 7, 2016
Priority date	Oct 8, 2015
Publication date	Jan 28, 2020
Grant date	Jan 28, 2020

Abstract

The present invention relates to a phosphinated poly(2,6-dimethy phenylene oxide)oligomer, specifically an unsaturated group-containing phosphinated poly(2,6-dimethy phenylene oxide)oligomer, and processes for producing the same. A thermoset produced from the unsaturated group-containing phosphinated poly(2,6-dimethy phenylene oxide)oligomers according to the present invention exhibits flame retardancy and has a low dielectric constant and dissipation factor and a high glass transition temperature.

First claim

What is claimed is:

1. A phosphinated poly(2,6-dimethyl phenylene oxide) oligomer of formula (2):

wherein each group has the following meaning:
P 1 denotes

P 2 denotes

R 1 , R 3 each independently denotes H or a straight chain or branched chain alkyl having 1 to 6 C-atoms;
R 2 each independently denotes H, or a straight chain or branched chain alkyl having 1 to 6 C-atoms, and at least one R 2 is H;
R 4 denotes H, alkenyl or aryl having 1 to 10 C-atoms and comprising 0 to 3 oxygen atoms, or the combination thereof; and
m, n each independently denotes an integer from 0 to 30.

2. The oligomer according to claim 1 , wherein at least the oligomer of formula (2) comprises a phosphinated poly(2,6-dimethyl phenylene oxide) bisphenol oligomer of formula (3):

wherein P 1 , P 2 , R 1 , R 2 , R 3 , m, and n are as defined in claim 1 .

3. The oligomer according to claim 2 , wherein at least the oligomer of formula (3) comprises a phosphinated poly(2,6-dimethyl phenylene oxide) bisphenol oligomer of formula (IIc):

wherein R 1 , and R 3 are each independently H, or a straight chain or branched chain alkyl having 1 to 6 C-atoms;
R 2 is each independently H, or a straight chain or branched chain alkyl having 1 to 6 C-atoms, and at least one R 2 is H; and
m, and n are each independently an integer from 0 to 30.

4. The oligomer according to claim 1 , wherein R 4 is alkenyl or aryl having 1 to 10 C-atoms and comprising 0 to 3 oxygen atoms, or the combination thereof.

5. The oligomer according to claim 1 , wherein R 4 denotes

6. The oligomer according to claim 1 , wherein at least the oligomer of formula (2) comprises an unsaturated group-containing phosphinated poly(2,6-dimethyl phenylene oxide) oligomer of formula (IIIc),

wherein R 1 , and R 3 are each independently H, or a straight chain or branched chain alkyl having 1 to 6 C-atoms;
R 2 each independently is H, or a straight chain or branched chain alkyl having 1 to 6 C-atoms, and at least one R 2 is H;
m, and n are each independently an integer from 0 to 30; and
R 4 denotes

7. The oligomer according to claim 1 , wherein R 1 , and R 3 each independently denote H, CH 3 , or C 2 H 5 , one R 2 denotes H, the other R 2 denotes CH 3 or C 2 H 5 , and m and n each independently denote an integer from 0 to 20.

8. The oligomer according to claim 1 , wherein at least the oligomer of formula (2) comprises an unsaturated group-containing phosphinated poly(2,6-dimethyl phenylene oxide) oligomer of formula (IIIc-M), (IIIc-A) or (IIIc-VB):

wherein m and n are each independently an integer from 0 to 30.

9. A process for producing the oligomer of formula (3) set forth in claim 2 , comprising a reaction of compound of formula (I):

with poly(2,6-dimethyl phenylene oxide) under the catalysis of CuCl and an amine compound to produce a phosphinated poly(2,6-dimethyl phenylene oxide) bisphenol oligomer of formula (3), wherein R 1 , and R 3 are each independently H, or a straight chain or branched chain alkyl having 1 to 6 C-atoms; R 2 is each independently H, or a straight chain or branched chain alkyl having 1 to 6 C-atoms, and at least one R 2 is H.

10. The process according to claim 9 , wherein the amine compound comprises dibutylamine or 4-dimethylaminopyridine.

11. A process for preparing the oligomer of formula (3) set forth in claim 2 , comprising conducting a redistribution reaction for a compound of formula (I):

wherein R 1 , and R 3 are each independently H, or a straight chain or branched chain alkyl having 1 to 6 C-atoms; R 2 is each independently H, or a straight chain or branched chain alkyl having 1 to 6 C-atoms, and at least one R 2 is H;
and a poly(2,6-dimethyl phenylene oxide) oligomer of formula (5):

wherein
Y denotes

and
p, q each independently denotes an integer from 0 to 50;
under the catalysis of a benzoyl peroxide to produce a phosphinated poly(2,6-dimethyl phenylene oxide) bisphenol oligomer of formula (3).

12. The process according to claim 11 , wherein the produced phosphinated poly(2,6-dimethyl phenylene oxide) bisphenol oligomer of formula (3) comprises at least an oligomer of formula (IIc)

wherein R 1 , and R 3 are each independently H, or a straight chain or branched chain alkyl having 1 to 6 C-atoms; R 2 is each independently H, or a straight chain or branched chain alkyl having 1 to 6 C-atoms, and at least one R 2 is H; and m, and n are each independently an integer from 0 to 30.

13. A process for producing the compound of formula (2) set forth in claim 1 , comprising reacting a phosphinated poly(2,6-dimethyl phenylene oxide) bisphenol oligomer of formula (3)

wherein:
P 1 is

P 2 is

R 1 , and R 3 are each independently H, or a straight chain or branched chain alkyl having 1 to 6 C-atoms;
R 2 each independently is H, or a straight chain or branched chain alkyl having 1 to 6 C-atoms, and at least one R 2 is H; and
m, and n are each independently an integer from 0 to 30,
with methacrylic anhydride, allyl bromine, or 4-chloromethylstyrene under the catalysis of a alkali catalyst to produce an unsaturated group-containing phosphinated poly(2,6-dimethyl phenylene oxide) oligomer of formula (2).

14. The process according to claim 13 , wherein the phosphinated poly(2,6-dimethyl phenylene oxide) bisphenol oligomer of formula (3) comprises an oligomer of formula (IIc)

wherein R 1 , and R 3 are each independently H, or a straight chain or branched chain alkyl having 1 to 6 C-atoms; R 2 is each independently H, or a straight

Assignees

• Chang Chun Plastics Co Ltd

Inventors

• Lin Ching Hsuan
• Wang Ping-Chieh
• Tu An-Pang
• Hwang Kuen-Yuan
• Tseng Chun Yu

Classifications

• C08G65/4006 Primary

  (I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X) · CPC title

• C07F9/65744

  condensed with carbocyclic or heterocyclic rings or ring systems · CPC title

• C08J7/08

  Heat treatment · CPC title

• C08G65/485

  Polyphenylene oxides · CPC title

• C07F9/657172

  the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: [IMAGE cpc-sch-C07F-1008.gif] (X = O, S) · CPC title