# US 11,999,816 B2 · Thermoplastic polyurethane from recycled raw materials

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- Number: US 11,999,816 B2
- Document ID: US11999816B2
- Status: Granted
- Kind: B2
- Application number: 16/980,084
- Filed: 2019-03-12
- Published: 2021-01-21
- Granted: 2024-06-04
- Earliest claimed: 2018-03-13
- Assignees: BASF SE
- Applicants: BASF SE
- Inventors: Frank Prissok; Elmar Poeselt; Dirk Kempfert; Lionel Gehringer; Juergen Weiser; Matthias Goldbeck
- Web page: https://patentgrep.com/patent/US11999816B2

## CPC

- C08G 18/5045: {containing urethane groups}
- C08F 4/80: selected from iron group metals or platinum group metals
- C08G 18/3206: {aliphatic}
- C08G 18/4238: {derived from dicarboxylic acids and dialcohols}
- C08G 18/4615: {containing nitrogen}
- C08G 18/4854: {Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group}
- C08G 18/6607: {with compounds of group C08G18/3203}
- C08G 18/7671: {containing only one alkylene bisphenyl group}
- C08J 11/04: of polymers
- C08J 2375/04: Polyurethanes
- Y02P 20/143: the feedstock being recycled material, e.g. plastics
- Y02W 30/62: Plastics recycling; Rubber recycling
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02W: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT

## Abstract

The present invention relates to a process for producing a thermoplastic polyurethane reacting at least one thermoplastic polyurethane (TPU-1) or a polyurethane mixture comprising a thermoplastic polyurethane (TPU-1) with at least one compound (V1) comprising two hydroxyl groups to obtain a mixture (G-a) comprising a thermoplastic polyurethane (TPU-2) and the reaction of the mixture (G-a) with a mixture (G-b) comprising an isocyanate composition (ZI) comprising at least one diisocyanate and optionally and a polyol composition (ZP) comprising at least one polyol (P2) to obtain a thermoplastic polyurethane (TPU target), wherein the proportion of the employed components (ZI) and (ZP) is matched to the hard segment content of the employed thermoplastic polyurethane (TPU-1), (V1) and the hard segment content of the thermoplastic polyurethane (TPU target). The invention further relates to a thermoplastic polyurethane obtained or obtainable by such a process and to the use thereof for producing extruded, injection molded and pressed articles as well as foams, cable sheathings, hoses, profiles, drive belts, fibers, nonwovens, films, moldings, soles, sporting goods, shoes, plugs, housings, damping elements for the electricals industry, automotive industry, mechanical engineering, 3D printing, medicine and consumer goods.

## Claims

### Claim 1

A process for producing a thermoplastic polyurethane, the process comprising:
(a) reacting a thermoplastic polyurethane (TPU-1) or a polyurethane mixture comprising TPU-1 with a compound (V1) having two hydroxyl groups to obtain a mixture (G-a) comprising a thermoplastic polyurethane (TPU-2), wherein an average molecular weight of TPU-2 is less than an average molecular weight of TPU-1; and
(b) reacting G-a with a mixture (G-b) comprising an isocyanate composition (ZI) comprising a diisocyanate and optionally a polyol composition (ZP) comprising a polyol (P2) to obtain a thermoplastic polyurethane (TPU-target),
wherein a proportion of ZI and ZP is matched to a hard segment content of TPU-1, V1 and a hard segment content of TPU-target, and
a proportion of ZI, ZP and V1 is matched to the hard segment content of TPU-1 via formula (1):
HSCG-c=(HSCTPU-target−wTPU-1*HSCTPU-1)/(1−wTPU-1) (1),
where
HSCG-c=a hard segment content of a mixture (G-c), wherein G-c=G-b+V1,
HSCTPU-target=a hard segment content of the obtained TPU-target,
wTPU-1=a mass fraction of TPU-1, based on a total mass of TPU-1 and G-c, and
HSCTPU-1=the hard segment content of TPU-1.

### Claim 2 (depends on 1)

The process of claim 1, wherein V1 is selected from the group consisting of diols (D1) having a number-average molecular weight <500 g/mol and polyols (P1) having a number-average molecular weight ≥500 g/mol, and
in formula (1), HSCG-c=the hard segment content of G-c, wherein G-c=G-b+V1=G-b+D1+P1.

### Claim 3 (depends on 1)

The process of claim 1, wherein the average molecular weight of TPU-2 is less than 50% of the average molecular weight of TPU-1.

### Claim 4 (depends on 1)

The process of claim 1, wherein TPU-2 is OH-terminated and the average molecular weight of TPU-2 is less than 50,000.

### Claim 5 (depends on 1)

The process of claim 1, wherein the reaction in (a) is carried out at a temperature in a range of from 200° C. to 360° C.

### Claim 6 (depends on 1)

The process of claim 1, wherein the reaction in (b) is carried out at a temperature in a range of from 170° C. to 260° C.

### Claim 7 (depends on 1)

The process of claim 1, wherein the reaction in (a) and the reaction in (b) are carried out continuously in an extruder.

### Claim 8 (depends on 1)

The process of claim 1, wherein a catalyst that accelerates cleavage of TPU-1 is added to the reaction in (a).

### Claim 9 (depends on 8)

The process of claim 8, wherein the catalyst is selected from the group consisting of metal catalysts based on tin, zinc, titanium, bismuth or iron.

### Claim 10 (depends on 2)

The process of claim 2, wherein D1 is selected from the group consisting of 1,2-ethylene glycol, propane-1,3-diol, butane-1,4-diol and hexane-1,6-diol.

### Claim 11 (depends on 2)

The process of claim 2, wherein P1 and/or P2 are selected from the group consisting of polyetherols, polyesterols, polycarbonate alcohols and hybrid polyols.

### Claim 12 (depends on 1)

The process of claim 1, wherein the diisocyanate is selected from the group consisting of diphenylmethane 2,2′-, 2,4′- and/or 4,4′-diisocyanate (MDI), tolylene 2,4- and/or 2,6-diisocyanate (TDI), methylene dicyclohexyl 4,4′-, 2,4′- and/or 2,2′-diisocyanate (H12MDI), hexamethylene diisocyanate (HDI) and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI).

### Claim 13 (depends on 1)

The process of claim 1, wherein TPU-1 or the polyurethane mixture comprising TPU-1 derives from a recycling process.

### Claim 14 (depends on 13)

The process of claim 13, wherein the recycling process comprises:
(i) providing a shaped article that consists substantially of a thermoplastic polyurethane;
(ii) comminuting the shaped article; and
(iii) agglomerating the comminuted shaped article to afford an intermediate product (TPU-ZP).

### Claim 15 (depends on 14)

The process of claim 14, wherein the shaped article is a shoe or a part of a shoe.

### Claim 16 (depends on 14)

The process of claim 14, wherein the shaped article comprises a pure or welded expanded thermoplastic polyurethane.

### Claim 17 (depends on 14)

The process of claim 14, wherein the shaped article comprises at least 85% by weight of a thermoplastic polyurethane.

### Claim 18 (depends on 14)

The process of claim 14, wherein the shaped article comprises at least 95% by weight of a thermoplastic polyurethane.

### Claim 19 (depends on 14)

The process of claim 14, wherein, in the agglomeration of (iii), a temperature is below 200° C.

### Claim 20 (depends on 15)

The process of claim 15, wherein, for the agglomeration of (iii), said process employs an apparatus comprising a conveying screw having a feed and an annular compression space, wherein the conveying screw passes feed material axially into the compression space.

### Claim 21 (depends on 1)

A thermoplastic polyurethane obtained or obtainable by the process of claim 1.

### Claim 22

A process for producing a component, the process comprising:
obtaining a thermoplastic polyurethane by a process comprising:
(a) reacting a thermoplastic polyurethane (TPU-1) or a polyurethane mixture comprising TPU-1 with a compound (V1) having two hydroxyl groups to obtain a mixture (G-a) comprising a thermoplastic polyurethane (TPU-2), wherein an average molecular weight of TPU-2 is less than an average molecular weight of TPU-1; and
(b) reacting G-a with a mixture (G-b) comprising an isocyanate composition (ZI) comprising a diisocyanate and optionally a polyol composition (ZP) comprising a polyol (P2) to obtain a thermoplastic polyurethane (TPU-target),
wherein a proportion of ZI and ZP is matched to a hard segment content of TPU-1, V1 and a hard segment content of TPU-target, and
a proportion of ZI, ZP and V1 is matched to the hard segment content of TPU-1 via formula (1):
HSCG-c=(HSCTPU-target−wTPU-1*HSCTPU-1)/(1−wTPU-1) (1),
where
HSCG-c=a hard segment content of a mixture (G-c), wherein G-c=G-b+V1,
HSCTPU-target=a hard segment content of the obtained TPU-target,
wTPU-1=a mass fraction of TPU-1, based on a total mass of TPU-1 and G-c, and
HSCTPU-1=the hard segment content of TPU-1; and
processing said thermoplastic polyurethane thereby obtaining said component;
wherein said component is an extruded, injection molded or pressed article, a foam, a cable sheathing, a hose, a profile, a drive belt, a fiber, a nonwoven, a film, a molding, a sole, a sporting good, a shoe, a plug, a housing, or a damping element.