# US 10,767,026 B2 · Process for degrading plastic products

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- Number: US 10,767,026 B2
- Document ID: US10767026B2
- Status: Granted
- Kind: B2
- Application number: 16/302,107
- Filed: 2017-05-18
- Published: 2019-07-18
- Granted: 2020-09-08
- Earliest claimed: 2016-05-19
- Assignees: Carbios
- Applicants: Carbios
- Inventors: Marie-Laure Desrousseaux; Helene Texier; Sophie Duquesne; Alain Marty; Mediha Aloui Dalibey; Michel Chateau
- Web page: https://patentgrep.com/patent/US10767026B2

## CPC

- C08J 11/105: {by treatment with enzymes}
- C08J 11/14: by treatment with steam or water
- C08J 2367/02: Polyesters derived from dicarboxylic acids and dihydroxy compounds; (C08J2367/06 takes precedence)
- C08J 2367/04: Polyesters derived from hydroxy carboxylic acids, e.g. lactones (C08J2367/06 takes precedence)
- Y02W 30/62: Plastics recycling; Rubber recycling
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- Y02W: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT

## Abstract

The present invention relates to processes for degrading plastic products and the uses thereof. The processes of the invention particularly comprise a step of amorphizing a plastic product prior to a step of depolymerization. The processes of the invention are particularly useful for degrading a plastic product comprising polyethylene terephthalate and/or polylactic acid. The invention also relates to a method of producing monomers and/or oligomers from a plastic product comprising at least one polyester, particularly polyethylene terephthalate and/or polylactic acid, comprising submitting the plastic product both to an amorphization step and to a depolymerization step.

## Claims

### Claim 1

A process for degrading a plastic product comprising at least one semi-crystalline thermoplastic polyester comprising the steps of:
a) amorphizing at least partially said at least one semi-crystalline thermoplastic polyester of the plastic product by heating the plastic product at a temperature above the melting temperature (Tm) of said semi-crystalline thermoplastic polyester, and further cooling the plastic product at a temperature below the crystallization temperature (Tc) of said semi-crystalline thermoplastic polyester, and
b) depolymerizing said at least partially amorphized polyester of the plastic product by contacting the plastic product with a depolymerase able to depolymerize said at least partially amorphized polyester into monomers and/or oligomers.

### Claim 2 (depends on 1)

The process of claim 1, wherein the cooling of said plastic product comprises cooling the plastic product to a temperature below the glass transition temperature (Tg) of said semi-crystalline thermoplastic polyester of the plastic product.

### Claim 3 (depends on 1)

The process of claim 1, wherein the step of amorphizing further comprises adding at least one degrading agent.

### Claim 4 (depends on 3)

The process of claim 3, wherein the degrading agent is selected from the group consisting of water, monomers of a polyester of the plastic product, metal alkoxides, alcohol and plasticizers.

### Claim 5 (depends on 1)

The process of claim 1, wherein the step of amorphizing is performed by use of an extruder.

### Claim 6 (depends on 1)

The process of claim 1, wherein the step of amorphizing leads to at least partially amorphized polyester with at most 30% of crystallinity.

### Claim 7 (depends on 1)

The process of claim 1, wherein the depolymerising step comprises contacting the plastic product with at least one microorganism expressing and excreting a depolymerase able to depolymerize said at least partially amorphized polyester into monomers and/or oligomers.

### Claim 8 (depends on 1)

The process of claim 1, further comprising recovering oligomers and/or monomers resulting from depolymerisation of said at least partially amorphized polyester of the plastic product.

### Claim 9 (depends on 8)

The process of claim 8, wherein the recovered oligomers and/or monomers are further purified.

### Claim 10 (depends on 1)

The process of claim 1, further comprising a preliminary depolymerising step performed prior to the amorphizing step.

### Claim 11 (depends on 1)

The process of claim 1, comprising a pretreatment step to modify the plastic product mechanically and/or physically and/or chemically and/or biologically.

### Claim 12 (depends on 11)

The process of claim 11, wherein said pretreatment step is performed before the amorphizing step and/or before the depolymerising step.

### Claim 13 (depends on 1)

The process of claim 1, wherein the plastic product comprises semi-crystalline polyesters, selected from polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylen terephthalate (PBT), polyethylene isosorbide terephthalate (PEIT), polylactic acid (PLA), polyhydroxy alkanoate (PHA), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polyethylene furanoate (PEF), polycaprolactone (PCL), poly(ethylene adipate) (PEA), polybutylene succinate terephthalate (PBST), polyethylene succinate (PES), poly(butylene succinate/terephthalate/isophthalate)-co-(lactate) (PBSTIL) and blends/mixtures of these materials.

### Claim 14 (depends on 1)

The process of claim 1, wherein the plastic product comprises semi-crystalline polyethylene terephthalate and/or semi-crystalline polylactic acid.

### Claim 15 (depends on 13)

The process of claim 13, wherein the depolymerizing step is performed by contacting the plastic product with a depolymerase selected from the group consisting of cutinases, proteases, lipases, carboxylesterases and esterases.

### Claim 16 (depends on 1)

The process of claim 1, wherein the plastic product comprises at least PET, and the amorphizing step comprises heating the plastic product to a temperature above 245° C., then cooling the plastic product to a temperature between 5° C. and 65° C.

### Claim 17 (depends on 1)

The process of claim 1, wherein the plastic product comprises at least PET, and the depolymerizing step comprises submitting the plastic product to a cutinase.

### Claim 18 (depends on 1)

The process of claim 1, wherein the plastic product comprises at least PET, and the amorphizing step comprises exposing the plastic product to a temperature above 245° C., then exposing the plastic product to a temperature comprised between 5° C. and 65° C., and the depolymerising step comprises contacting the plastic product to a cutinase.

### Claim 19

A method of producing monomers and/or oligomers from a plastic product containing at least one semi-crystalline thermoplastic polyester, comprising submitting the plastic product to an amorphization step to amorphize at least partially said semi-crystalline thermoplastic polyester of the plastic product, wherein the amorphization step comprises heating the plastic product to a temperature above the melting temperature (Tm) of said semi-crystalline thermoplastic polyester and further cooling the product to a temperature below the crystallization temperature (Tc) of said semi-crystalline thermoplastic polyester, and to a depolymerising step to depolymerise said at least partially amorphized polyester of the plastic product, wherein the depolymerizing step comprises contacting the plastic product with a depolymerase able to degrade said at least partially amorphized polyester.

### Claim 20 (depends on 19)

The method of claim 19, wherein the plastic product comprises polyethylene terephthalate, the depolymerizing step comprising exposing the plastic product to a cutinase.

### Claim 21

A process for degrading a plastic product comprising at least one semi-crystalline thermoplastic polyester that has been previously amorphized by heating the plastic product to a temperature above the melting temperature (Tm) of said semi-crystalline thermoplastic polyester and further cooling the plastic product to a temperature below the crystallization temperature (Tc) of said semi-crystalline thermoplastic polyester comprising contacting said amorphized plastic product with a depolymerase able to degrade said previously amorphized polyester.
