Isohexide-diacetal based polymers and a process thereof

Patent metadata

Field	Value
Publication number	US-9815934-B2
Application number	US-201414890060-A
Country	US
Kind code	B2
Filing date	May 9, 2014
Priority date	May 9, 2013
Publication date	Nov 14, 2017
Grant date	Nov 14, 2017

Abstract

Potentially degradable isohexide based compounds and their polymers, derived from renewable resources, are described. Degradable isohexide-based monomers and polymers obtained from renewable resources are also described. Finally, processes for synthesizing such degradable polymers via copolymerization of the isohexide-based monomers and long chain diols are disclosed.

First claim

We claim:

1. An isohexide-diacetal based polymer having a molecular weight between 3,200 and 27,600 g/mol, comprising Formula 1

wherein m ranges from 10-200.

2. The isohexide-diacetal based polymer of Formula 1 as claimed in claim 1 , wherein the Isohexide-diacetal based polymer of Formula 1 is represented by the compounds of formulae I, II, and III;

wherein R is selected from the group consisting of isomannide, isosorbide and isoidide;

wherein R is selected from the group consisting of isomannide, isosorbide and isoidide;

wherein R is selected from the group consisting of isomannide, isosorbide and isoidide and the variable m ranges from 10-200.

3. The isohexide-diacetal based polymer of Formula 1 as claimed in claim 2 is represented by the group of the following compounds:

Copolymer of isomannide-diacetal monomer and C6 to C23 linear diol,
Copolymer of isosorbide-diacetal monomer and C6 to C23 linear diol, and
Copolymer of isoidide-diacetal monomer and C6 C23 linear diol.

4. A process for the synthesis of isohexide-diacetal based polymer of formula 1 as claimed in claim 1 , wherein said process comprises the steps of:
a) suspending sodium hydride in dry tetrahydrofuran to form a sodium hydride suspension; adding slowly a THF solution of isohexide to the sodium hydride suspension over a period of 1-3 hours and stirring for 24-48 hours at room temperature ranging between 25-35° C. to form a first mixture; adding chloromethyl methyl ether to the mixture over 4-5 hours to form a second mixture and stirring the second mixture for a period ranging between 24 to 48 hours to obtain the isohexide-diacetal monomer of formula I;
b) heating isohexide-diacetal monomer of formula I as obtained in step (a) with 1-5 mol % p TSA (p-toluene sulphonic acid) at a beginning temperature ranging between 60 to 100° C. and raising the temperature to between 90 to 140° C. over a period of 1-3 hours followed by shortly evacuating the reaction vessels after every 2-3 minute during the initial 2-3 hours to obtain a polymer melt and stirring the polymer melt over 3-7 hours at 90-140° C. under reduced pressure subsequently cooling and dissolving the solid in chloroform and re-precipitating from methanol to obtain isohexide-diacetal polymer of formula II;
c) optionally heating isohexide-diacetal monomer of formula I as obtained in step (a) with 1-5 mol % p TSA (p-toluene sulphonic acid) and long chain diol at temperature ranging between 60 to 100° C. which was raising from 90 to 140° C. over a period of 1-3 hours followed by shortly evacuating the reaction vessels after every 2-3 minute during the initial 2-3 hours to obtain a polymer melt and stirring the polymer melt over 24-48 hours under reduced pressure to obtain copolymer of isohexide-diacetal with long chain diol of formula III.

5. The process as claimed in claim 4 , wherein the isohexide used in step (a) is selected from the group consisting of isomannide, isoidide and isosorbide.

6. The process as claimed in claim 4 , wherein the molecular weight of the isohexide-diacetal polymer of formula II is in the range of 3200-27600 g/mol.

7. The process as claimed in claim 4 , wherein the molecular weight of the copolymer of isohexide-diacetal with long chain diol of formula III is in the range of 10000-30000 g/mol.

8. The process as claimed in claim 4 , wherein the yield of the isohexide-diacetal polymer of formula II is in the range of 46-71%.

9. The process as claimed in claim 4 , wherein the yield of the copolymer of isohexide -diacetal with long chain diol of formula III is in the range of 97-99%.

10. An isohexide-diacetal based polymer having a molecular weight between 3,200 and 27,600 g/mol, comprising Formula 1:

wherein the isohexide-diacetal based polymer of Formula 1 is represented by the compounds of formulae II and III, with R selected from the group consisting of isomannide, isosorbide and isoidide and, with respect to formula III, the variable m ranges from 10-200:

11. The isohexide-diacetal based polymer of Formula 1 as claimed in claim 10 is represented by the group of the following compounds:

Copolymer of isomannide-diacetal monomer and C6 to C23 linear diol, Copolymer of isosorbide-diacetal monomer and C6 to C23 linear diol, and Copolymer of isoidide-diacetal monomer and C6 to C23 linear diol.

Assignees

• Council Scient Ind Res
• Council Scient Ind Res

Inventors

• Chikkali Samir Hujur
• Rajput Bhausaheb Shivaji

Classifications

• C08L59/00

  Compositions of polyacetals; Compositions of derivatives of polyacetals (of polyvinyl acetals C08L29/14) · CPC title

• C08G2/10 Primary

  Polymerisation of cyclic oligomers of formaldehyde · CPC title

• C08G2/18

  Copolymerisation of aldehydes or ketones · CPC title

• C08G2/24

  with acetals · CPC title

• C08G2261/12

  Copolymers · CPC title