US 12,168,720 B2
Synthesis of functionalized polymers through devulcanization from waste containing elastomers
Isabelle Dez, Caen (FR); Annie-Claude Gaumont, Caen (FR); and Jean-Nicolas Noël, Pont-Saint-Martin (FR)
Assigned to CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE, Paris (FR); UNIVERSITE DE CAEN NORMANDIE, Caen (FR); and ECOLE NATIONALE SUPERIEURE D'INGENIEURS DE CAEN, Caen (FR)
Appl. No. 17/310,653
Filed by CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE, Paris (FR); UNIVERSITE DE CAEN NORMANDIE, Caen (FR); and ECOLE NATIONALE SUPERIEURE D'INGENIEURS DE CAEN, Caen (FR)
PCT Filed Feb. 18, 2020, PCT No. PCT/EP2020/054215
§ 371(c)(1), (2) Date Aug. 16, 2021,
PCT Pub. No. WO2020/169589, PCT Pub. Date Aug. 27, 2020.
Claims priority of application No. 1901667 (FR), filed on Feb. 19, 2019.
Prior Publication US 2021/0388174 A1, Dec. 16, 2021
Int. Cl. C08J 11/26 (2006.01); C08L 17/00 (2006.01)
CPC C08J 11/26 (2013.01) [C08L 17/00 (2013.01); C08J 2321/00 (2013.01); C08L 2203/02 (2013.01); C08L 2207/04 (2013.01)] 10 Claims
 
1. A method for synthesizing polymers by devulcanization from waste containing elastomers, said method comprising:
a) contacting said waste containing elastomers with a solvent in the presence of an agent for devulcanization of cross-linking points that comprise a sulphur atom bound to another sulphur atom or to a carbon atom;
b) heating the mixture obtained in step a) at a temperature comprised between 20° C. and 250° C. for a time comprised between 15 minutes and 24 hours; and said method including:
the devulcanizing agent is a compound according to formula (1)

OG Complex Work Unit Chemistry
in which R and R′ are identical or different and each represent, independently of one another, a substituent exerting a donor mesomeric effect or an attractor mesomeric effect or a donor inductive effect or an attractor inductive effect, R and R′ are selected independently of one another from the group comprising hydrogen (—H), the halogen atoms selected from iodine, bromine, fluorine and chlorine, the group of (C1-18)alkyls, primary amines (—NH2), secondary amines (—NHRa1, Ra1 being selected from (C1-C5)alkyl groups and aromatic rings) or tertiary amines (—NRa1Ra2, where Ra1 and Ra2, which are identical or different, may each independently of one another be a (C1-C5)alkyl group or an aromatic ring), hydroxyl (—OH), the alcoholates (or a salt) (Ra1—O, Ra1 being selected from (C1-C5)alkyl groups and aromatic rings), the (C1-C5)alkoxy groups, a thiol (—SH), the thioethers (—SRa1, Ra1 being selected from (C1-C5)alkyl groups and aromatic rings), a thiolate (or a salt) (Ra1—S), Ra1 being selected from (C1-C5)alkyl groups and aromatic rings), an aromatic ring, a conjugated base of a carboxylic acid (—COO), a carboxyl group (—COOH), the esters (—CO2 Ra1, Ra1 being selected from (C1-C5)alkyl groups and heterocycles), an aldehyde group (—CHO), a carbonyl (—COR), a nitro group (—NO2), a nitrile group (—CN), a sulphonyl group (—SO2—), a sulphonate group (salt or acid)(—SO3), a sulphone (—SO2R), a phosphate group —O—PO(ORa1)(ORa2) where Ra1 and Ra2, which are identical or different, may each independently of one another be a hydrogen or (C1-C5)alkyl group or an aromatic ring), a primary amide group (—CONH2), secondary amide group (—CONHRa1, Ra1 being selected from (C1-C5)alkyl groups and aromatic rings) or tertiary amide group (—CONRa1Ra2, Ra1 and Ra2, which are identical or different, may each independently of one another be a (C1-C5)alkyl group or an aromatic ring)) and R, R′ or both are different from a hydrogen atom and wherein said synthesized polymers are functionalized elastomer according to formula 3 or 3′,

OG Complex Work Unit Chemistry
in which x is an integer comprised between 0 and 6, n is an integer comprised between 6 and 600, m is an integer comprised between 6 and 600, Y is a hydrogen atom or a methyl group, and
R and R′, which are identical or different for each unit, are selected from the group comprising halogen atoms selected from iodine, bromine, fluorine and chlorine, the group of (C1-18) alkyls, the primary amines (—NH2), secondary amines (—NHRa1, Ra1 being selected from (C1-C5) alkyl groups and aromatic rings) or tertiary amines (—NRa1Ra2, where Ra1 and Ra2, which are identical or different, may each independently of one another be a (C1-C5) alkyl group or an aromatic ring), hydroxyl (—OH), the alcoholates (or a salt) (Ra1—O—, Ra1 being selected from (C1-C5) alkyl groups and aromatic rings), the (C1-C5) alkoxy groups, a thiol (—SH), the thioethers (—SRa1, Ra1 being selected from (C1-C5) alkyl groups and aromatic rings), a thiolate (or a salt)(Ra1 —S—, Raj being selected from (C1-C5) alkyl groups and aromatic rings), an aromatic ring, a conjugated base of a carboxylic acid (—COO—), a carboxyl group (—COOH), the esters (—CO2 Ra1, Ra1 being selected from (C1-C5) alkyl groups and heterocycles), an aldehyde group (—CHO), a carbonyl (—COR), a nitro group (—NO2), a nitrile group (—CN), a sulphonyl group (—SO2—), a sulphonate group (salt or acid)(—SO3), a sulphone (—SO2R), a phosphate group —O—PO (ORa1) (ORa2) where Ra1 and Ra2, which are identical or different, may each independently of one another be a hydrogen or (C1-C5) alkyl group or an aromatic ring), a primary amide group (—CONH2), secondary amide group (—CONHRa1, Raj being selected from (C1-C5) alkyl groups and aromatic rings) or tertiary amide group (—CONRa1Ra2, Ra1 and Ra2, which are identical or different, may each independently of one another be a (C1-C5) alkyl group or an aromatic ring).