Unsaturated deoxybenzoin compounds and polymers prepared therefrom

Patent metadata

Field	Value
Publication number	US-10065913-B2
Application number	US-201615286768-A
Country	US
Kind code	B2
Filing date	Oct 6, 2016
Priority date	Oct 7, 2015
Publication date	Sep 4, 2018
Grant date	Sep 4, 2018

Abstract

Deoxybenzoin compounds including unsaturation are disclosed. The unsaturated deoxybenxoin compounds have the structure (I), (II), or (III)

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and n are defined herein. Also disclosed are polyesters including repeating units having the structure (IV), (V), or a combination thereof

wherein Ar 1 , R 7 , and m are defined herein. The polyesters can be further functionalized, for example by various phosphorous-containing compounds. The polyesters described herein can be useful for the preparation of various articles having reduced flammability.

First claim

The invention claimed is:

1. An unsaturated deoxybenzoin compound having the structure (I), (II), or (III)

wherein
R 1 and R 2 are independently at each occurrence hydrogen, a halogen, a nitrile group, a C 1-6 alkyl group, or a C 6-20 aryl group;
R 3 , R 4 , R 5 , and R 6 are independently at each occurrence hydrogen, a halogen, a hydroxyl group, a nitrile group, a C 1-6 alkyl group, a C 1-6 alkoxy group, or a C 6-20 aryl group; and
n is independently at each occurrence an integer from 1 to 12.

2. The deoxybenzoin compound of claim 1 , wherein each occurrence of R 1 and R 2 is hydrogen.

3. The deoxybenzoin compound of claim 1 , wherein each occurrence of n is 1.

4. The deoxybenzoin compound of claim 1 , wherein each occurrence of R 3 , R 4 , R 5 , and R 6 is hydrogen.

5. The deoxybenzoin compound of claim 1 ,
wherein
the deoxybenzoin compound has the structure (I)

each occurrence of R 1 and R 2 is hydrogen; and
each occurrence of R 3 , R 4 , and R 5 is hydrogen.

6. The deoxybenzoin compound of claim 1 ,
wherein
the deoxybenzoin compound has the structure (II)

each occurrence of R 1 and R 2 is hydrogen; and
each occurrence of R 3 , R 4 , R 5 , and R 6 is hydrogen.

7. The deoxybenzoin compound of claim 1 , wherein
the deoxybenzoin compound has the structure (III)

each occurrence of R 1 and R 2 is hydrogen;
each occurrence of n is 1; and
each occurrence of R 3 , R 4 , R 5 , and R 6 is hydrogen.

8. A polyester comprising repeating units having the structure (IV), (V), or a combination thereof

wherein
Ar 1 is a divalent substituted or unsubstituted C 6-20 arylene group;
R 7 is independently at each occurrence a halogen, a hydroxyl group, a nitrile group, a C 1-6 alkyl group, a C 1-6 alkoxy group, or a C 6-20 aryl group; and
m is independently at each occurrence 0, 1, 2, 3, or 4.

9. The polyester of claim 8 , wherein Ar 1 is a phenylene group.

10. The polyester of claim 8 , wherein m is 0.

11. The polyester of claim 8 , wherein the polyester is a copolyester further comprising repeating units derived from a dihydroxy compound of the formula

wherein
R a and R b are each independently a halogen atom or a C 1-6 alkyl group;
p and each occurrence of q are each independently 0, 1, 2, 3, or 4;
c is 0, 1, 2, 3, or 4; and
X a is a single bond, —O—, —S—, —S(O)—, —SO 2 —, —C(O)—, or a C 1-18 hydrocarbylene group.

12. The polyester of claim 8 , wherein the polyester is a copolyester further comprising repeating units derived from bisphenol A.

13. The polyester of claim 8 , wherein the polyester has a number average molecular weight of 1,000 to 100,000 Daltons.

14. The polyester of claim 8 , wherein
the polyester has repeating units of formula (VI)

Ar 1 is a phenylene group; and
the polyester has a molecular weight of 10,000 to 100,000 Daltons.

15. The polyester of claim 8 , wherein
the polyester is a copolyester comprising repeating units of formulas (VI) and (VII)

Ar 1 is phenylene;
Ar 2 is 4,4′-diphenylene isopropylidene; and
the polyester has a molecular weight of 10,000 to 100,000 Daltons.

16. The polyester of claim 8 , wherein
the polyester has repeating units of formula (VIII)

Ar 1 is a phenylene group; and
the polyester has a molecular weight of 10,000 to 100,000 Daltons.

17. The polyester of claim 8 , wherein
the polyester is a copolyester comprising repeating units of formulas (VIII) and (VII)

Ar 1 is phenylene;
Ar 2 is 4,4′-diphenylene isopropylidene; and
the polyester has a molecular weight of 10,000 to 100,000 Daltons.

18. The polyester of claim 8 , wherein the polyester exhibits one or more of the following properties:
a five percent weight loss temperature of greater than or equal to 350° C., as determined using thermogravimetric analysis;
a char yield of at least 35 percent after 60 minutes at 750° C., as determined by thermogravimetric analysis;
a heat release capacity of less than or equal to 150 joules per gram-Kelvin determined using a pyrolysis combustion flow calorimeter; and
a total heat release of less than 15 kilojoules per gram determined using a pyrolysis combustion flow calorimeter.

19. A polyester comprising repeating units having the structure (IX), (X), or a combination thereof

wherein
Ar 1 is a divalent substituted or unsubstituted C 6-20 arylene group;
R 7 is independently at each occurrence a halogen, a hydroxyl group, a nitrile group, a C 1-6 alkyl group, a C 1-6 alkoxy group, or a C 6-20 aryl group;
m is independently at each occurrence 0, 1, 2, 3, or 4; and
R 8 is a phosphorous-containing group.

20. The polyester of claim 19 , wherein R 8 is independently at each occurrence

or a combination thereof.

Assignees

• Univ Massachusetts

Inventors

• Mir Aabid A
• Emrick Todd
• Choudhary Umesh

Classifications

• C08G63/181

  Acids containing aromatic rings · CPC title

• C08G63/6926

  Dicarboxylic acids and dihydroxy compounds · CPC title

• C07C49/84

  containing ether groups, [IMAGE cpc-sch-C07C-0958.gif] groups,[IMAGE cpc-sch-C07C-0959.gif] groups, or[IMAGE cpc-sch-C07C-0960.gif] groups · CPC title

• C08G63/91

  Polymers modified by chemical after-treatment · CPC title

• C08G63/00

  Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule (polyester-amides C08G69/44; polyester-imides C08G73/16) · CPC title