(poly)ester and (poly)amide compositions, method for modifying (poly)esters or (poly)amides and catalyst therefor

Patent metadata

Field	Value
Publication number	US-2025179263-A1
Application number	US-202218840724-A
Country	US
Kind code	A1
Filing date	Feb 23, 2022
Priority date	Feb 23, 2022
Publication date	Jun 5, 2025
Grant date	—

Abstract

Disclosed are transesterification and transamidation reactions and depolymerization reactions of polyesters and polyamides using catalysts comprising a structural unit of formula (I). Therein, o is a positive integer of at least 1, R 3 is selected from the group of hydrogen, halogen, or optionally substituted C 1 -C 18 alkyl, Z is a group-BG-Cat + M, BG is a covalent bond or a divalent bridge group, Cat + is a selected cationic residue, preferably an imidazolinium group, covalently attached to BG, M is an i-times charged anion An i− for charge-compensation, and i is an integer from 1 to 4. The invention provides a method for (trans)esterification or (trans)amidation reactions to produce biodiesel, to depolymerize polyesters/polyamides using reusable polymer catalysts, wherein the polymer catalysts not only provide a homogeneous and high catalytic activity for degradation or transformation reactions but allow also a heterogeneous separation of the catalysts and/or impurities, such as additives, colorants (pigments or dyes), from the reaction products.

First claim

1 . A composition comprising
A) at least one (poly)ester or (poly)amide or combinations thereof, and B) at least one polymer comprising a structural unit of formula (I)
—(CH 2 —CR 3 Z) o —  (I)

wherein o is a positive integer of at least 1, R 3 is selected from the group of hydrogen, halogen, C 1 -C 18 alkyl or C 1 -C 18 alkyl substituted with one or more substituents independently selected from the group of hydroxy, carboxy, acyloxy, OR′, O 2 CR′, and CO 2 R′, R′ is selected from the group of optionally substituted C 1 -C 18 alkyl, optionally substituted C 2 -C 18 alkenyl, optionally substituted aryl, substituted heterocyclyl, optionally substituted aralkyl, optionally substituted alkaryl, wherein said optional substituents are selected from the group consisting of epoxy, alkoxycarbonyl, aryloxycarbonyl, isocyanato, cyano, silyl, halo and dialkylamino, Z is a group -BG-Cat + M, BG is a covalent bond or a divalent bridge group, Cat + is a one-time positively charged cationic residue selected from the group of one-time positively charged heterocyclic residues having one, two or three ring nitrogen atoms and optionally one ring oxygen atom, one ring sulfur atom, one ring phosphorus atom, one ring arsenic atom or one ring antimony atom, ammonium cations, phosphonium cations, arsonium cations or antimonium cations covalently attached to BG, M is a negatively i-charged counter-ion of type An i− which is selected from the group of organic or inorganic anions, wherein An i− will interact with one or more cationic residues Cat + for charge-compensation in polymer B), and i is an integer from 1 to 4.

2 . The composition according to claim 1 , wherein component A) is a solid polyester or polyamide which is provided in a carrier liquid C) that is a suitable solvent for the monomer(s) resulting from degradation of said polyester or polyamide.

3 . The composition according to claim 1 , wherein component A) is a (poly)ester.

4 . The composition according to claim 3 , wherein the polyester is a poly carboxylic ester which is selected from polyethylene terephthalate (PET), polyethylene furanoate (PEF), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyglycolic acid (PGA), polylactic acid (PLA), polycaprolactone (PCL), polyethylene adipate (PEA), polyhydroxyalkanoate (PHA), polyhydroxy-butyrate (PHB), polyethylene naphthalate (PEN), Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), and a polycondensate of 4-hydroxybenzoic acid and 6-hydroxynaphthalene-2-carboxylic acid (VECTRAN).

5 . The composition according to claim 1 , wherein component B) is a copolymer comprising recurring units of formulae (I) and (II) and optionally (III),
—(CH 2 —CR 1 W) m —  (II)
—(CH 2 —CR 2 Y) n —  (III)
wherein formula (I) is as defined in claim 1 , m and n independently of one another are positive integers of at least 1, R 1 and R 2 independently of one another are selected from the group of hydrogen, halogen, C 1 -C 18 alkyl or C 1 -C 18 alkyl substituted with one or more substituents independently selected from the group of hydroxy, carboxy, acyloxy, OR′, O 2 CR′, and CO 2 R′, W and Y independently or one another are selected from the group of hydrogen, halogen, C 1 -C 18 alkyl, cycloalkyl, alkoxy, alkylamino, and aryl, CO 2 H, CO 2 R′, COR′, CN, CONH 2 , CONHR′, CONR′ 2 , O 2 CR′ and OR′.

6 . The composition according to claim 5 , wherein component B) is a block-copolymer or a quasi-block copolymer comprising at least one block of recurring units of formula (II) and at least one block of recurring units of formula (IIIa)
[—(CH 2 —CR 1 W—) m ]  (II),
[—(CH 2 —CR 2 Y—) n . . . —(CH 2 —CR 3 Z—) o ]  (IIIa),
wherein the two recurring units in formula (IIIa) are arranged in a statistical manner or in the form of blocks.

7 . The composition according to claim 1 , wherein BG is a covalent bond, an alkylene group of 1-10 carbon atoms, a phenylene group, an aralkylene group —C 6 H 4 —(CH 2 ) p —, wherein p is an integer between 1 and 100, or groups selected from —COO—(CH 2 ) t — or —CONH—(CH 2 ) t —, wherein t is an integer from 1 to 100, and the carbon atom in the —COO— group or in the —CH—NH— group is attached to the polymer backbone and one carbon atom in the —(CH 2 ) p — group is attached to Cat + .

8 . The composition according to claim 1 , wherein Cat + is selected from monovalent quaternary ammonium residues, monovalent quaternary phosphonium residues, one-times positively charged monovalent heterocyclic groups with one to three ring nitrogen atoms and optionally one oxygen or one sulfur ring atom, said heterocyclic groups having 5 or 6 ring atoms.

9 . The composition according to claim 8 , wherein Cat + is selected from pyrimidine, imidazole, piperidine, pyrrolidine, pyridine, pyrazol, oxazol, triazol, thiazol, methimazol, benzotriazol, isoquinol and viologen-type compounds.

10 . The composition according to claim 1 , wherein the anions An i− are selected from the group consisting of BRF 3 − , BRR′F 2 − , BR 4 − , CF 3 SO 3 − , CF 3 CO 2 − , HCO 2 − , RCO 2 − , RNH 2 CO 2 − , N(CF 3 SO 2 ) 2 − , N(RSO 2 ) 2 − , N(CF 2 S 2 O 4 ) − , RSO 3 − , and RR′PO 4 − , wherein R and R′ are independently selected from the group consisting of alkyl, alkenyl, alkynyl, haloalkyl, alkoxyalkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, and heteroarylalkyl.

11 . The composition according to claim 1 , wherein the anions An i− are selected from anions having the formula [Me q Hal r ] i− , in which Me is selected from the group consisting of B, P, As, Sb, Al, Au, Nb, Cd, Cu, Mn, Fe, Ga, Hf, Co, Ni, Ga, Pb, Sn, Ti, Zn and Zr, preferably selected from the group consisting of Zn, Fe and Co, Hal is a halogen atom, preferably selected from Fluoride, Chloride and Bromide, q is an integer between 1 and 6, r is an integer between 3 and 14, and i is an integer between 1 and 4.

12 . The composition according to claim 11 , wherein the anions An i− are selected from the group consisting of [ZnCl 4 ] 2− , [Zn 2 Cl 6 ] 2− , [Zn 3 Cl 8 ] 2− , [Zn 4 Cl 10 ] 2− , [FeCl 4 ] − , [FeCl 4 ] 2− , [Fe 2 Cl 7 ] − , [CoCl 4 ] 2− , [CoCl 2 (CoCl 4 ) 2 ] 4− , [CoCl 2 (Co 2 Cl 4 ) 3 ] 4− and the any mixtures thereof.

13 . The composition according to claim 1 , wherein the catalyst B) is a polymer or a copolymer comprising structural units of one or more of the formulae listed below:

wherein
p is an integer and ranges from 1 to 100,
R 3 , R 4 , R 5 and R 6 are independently selected from the group of hydrogen, halogen, C 1 -C 18 alkyl optionally substituted with one or more substituents independently selected from the group of hydroxy, carboxy, acyloxy, OR′, O 2 CR′, and CO 2 R′, optionally substituted aryl, optionally substituted heterocyclic rings, optionally substituted aralkyl, optionally substituted alkaryl; optionally substituted alkylthio, optionally substituted arylthiol, optionally substituted alkoxy, wherein said optional substituents are selected from the group consisting of epoxy, alkoxycarbonyl, aryloxycarbonyl, isocyanato, cyano, silyl, halo and dialkylamino,
X is selected from the group of N, P, As or Sb, and
wherein the anions An i− are selected from anions having the formula [Me q Hal r ] i− , in which Me is selected from the group consisting of B, P, As, Sb, Al, Au, Nb, Cd, Cu, Mn, Fe, Ga, Hf, Co, Ni, Ga, Pb, Sn, Ti, Zn and Zr, preferably selected from the group consisting of Zn, Fe and Co, Hal is a halogen atom, pre

Assignees

• Univ Jena Friedrich Schiller
• Centro De Investigacion En Quim Aplicada

Inventors

• Guerrero Sanchez Carlos
• Lechuga Islas Victor Daniel
• Guerrero Santos Ramiro
• Schubert Ulrich S

Classifications

• C08L67/02

  Polyesters derived from dicarboxylic acids and dihydroxy compounds (C08L67/06 takes precedence) · CPC title

• C08J2453/00

  Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers · CPC title

• C08J2425/18

  Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen · CPC title

• C08J2367/02

  Polyesters derived from dicarboxylic acids and dihydroxy compounds; (C08J2367/06 takes precedence) · CPC title

• C08F297/026

  polymerising acrylic acid, methacrylic acid or derivatives thereof · CPC title