Method for preparing polythiols

Patent metadata

Field	Value
Publication number	US-11999682-B2
Application number	US-201816483298-A
Country	US
Kind code	B2
Filing date	Feb 6, 2018
Priority date	Feb 13, 2017
Publication date	Jun 4, 2024
Grant date	Jun 4, 2024

Abstract

Provided is a process for preparing polythiols by preparing a sulfhydration reaction medium, simultaneously carrying out radical sulfhydration reaction of at least one polyene and acid-catalyzed sulfhydration reaction of the polyene and recovering a mixture including at least two polythiols. Also provided is a mixture of polythiols obtained from the process described herein.

First claim

The invention claimed is:

1. A process for controlling regioselectivity of
prepared polythiols comprising:
preparing a sulfhydration reaction medium comprising bringing into contact in a reactor:
at least one polyene;
at least one radical initiator that includes a photochemical radical initiator;
at least one heterogeneous acid catalyst that is a resin;
at least one sulfhydryl group donor compound;

optionally, at least one solvent;
simultaneously carrying out the radical sulfhydration reaction of said at least one polyene and the acid-catalyzed sulfhydration reaction of said at least one polyene which includes irradiation of the reaction medium at wavelengths sufficient to obtain radical initiation; and
recovering a mixture comprising least substituted polythiols and most substituted polythiols, wherein for the least substituted polythiols, the sulhydryl group of the sulfhydryl group donor is predominantly attached to the least substituted carbon atoms of the polythiol when the sulfhydration reaction is radical initiated, and wherein for the most substituted polythiol, the sulhydryl group of the sulfhydryl group donor is predominantly attached to the most substituted carbon atoms of the polythiol when the sulfhydration reaction is acid-catalyzed, and where the ratio between the least substituted polythiol formed and the most substituted polythiol formed is controlled by adjusting the radical initiated and the acid-catalyzed reaction conditions,
wherein said at least one sulfhydryl group donor compound is chosen from hydrogen sulfide, thiocarboxylic acids and dialkyl di- and poly-sulfides, taken alone or as a combination of two or more thereof.

2. The process according to claim 1 , wherein said at least one polyene is a compound with a hydrocarbon chain that comprises at least two unsaturations in double bond form, it being possible for said chain to be linear or cyclic, saturated or unsaturated, and to optionally comprise one or more heteroatoms chosen from columns 15, 16 and 17 of the Periodic Table of the Elements, and to be interrupted or substituted by one or more aromatic groups.

3. The process according to claim 1 , wherein said at least one polyene is a hydrocarbon compound comprising from 2 to 20 double bonds, limits included.

4. The process according to claim 1 , wherein said at least one polyene is chosen from triallyisocyanurate and derivatives thereof, terpenes and derivatives thereof, comprising at least two double bonds.

5. The process according to claim 1 , wherein said at least one radical initiator also includes a thermal initiator.

6. The process according to claim 5 , wherein said at least one radical initiator is chosen from peroxides, hydroperoxides, azobisisobutyronitrile, 2,2-dimethoxy-1,2-diphenylethan-1-one, alkyl phosphites and xanthene derivatives, taken alone or as a combination of two or more thereof.

7. The process according to claim 1 , carried out in the absence of solvent.

8. The process according to claim 1 , wherein said at least one sulfhydryl group donor compound is a disulfide oil.

9. The process according to claim 1 , wherein the irradiation is ultraviolet radiation.

10. The process according to claim 9 , wherein the ultraviolet radiation has a wavelength of between 180 nm and 400 nm.

Assignees

• Arkema France

Inventors

• Saint-Louis-Augustin Pascal
• Fremy Georges
• Monguillon Bernard
• Corbel Louis

Classifications

• C07C319/04 Primary

  by addition of hydrogen sulfide or its salts to unsaturated compounds · CPC title

• C07C321/04

  of an acyclic saturated carbon skeleton · CPC title