Synthesis of polyurethane polymers in flow reactors

Patent metadata

Field	Value
Publication number	US-12540212-B2
Application number	US-202117318004-A
Country	US
Kind code	B2
Filing date	May 12, 2021
Priority date	May 12, 2021
Publication date	Feb 3, 2026
Grant date	Feb 3, 2026

Abstract

Techniques regarding the polymerization of polyurethanes are provided. For example, one or more embodiments described herein can comprise synthesizing, via a polymerization reaction performed within a flow reactor, a polyurethane. The polymerization reaction can polymerize a diol with a diisocyanate.

First claim

What is claimed is:

1 . A method, comprising:
synthesizing, via a polymerization reaction performed within a flow reactor comprising a plurality of reactor loops, a polyurethane, wherein the polymerization reaction polymerizes a diol with a diisocyanate monomer; wherein the synthesizing further comprises supplying the diol to the flow reactor through a first inlet, supplying the diisocyanate monomer to the flow reactor through a second inlet, and supplying an organic catalyst to the flow reactor through a third inlet; introducing anhydrous tetrahydrofuran (THF) into the flow reactor at a point downstream of one or more reactor loops of the plurality of reactor loops via a fourth inlet.

2 . The method of claim 1 , wherein the polymerization reaction further includes polymerizing a second diol with the diisocyanate monomer, wherein the diol has a melting temperature above ambient conditions, and wherein the second diol has a glass transition temperature below the ambient conditions.

3 . The method of claim 2 , wherein the diol is selected from the group consisting of 1,6-hexanediol, 1,8-octanediol, and diethylene glycol, wherein the diisocyanate monomer is selected from the group consisting of 4,4′-methylene diphenyl diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate, wherein the polymerization reaction includes a catalyst selected from the group consisting of, 8-diazabiciclo[5.4.0]undeca-7-ene, dibutyltin dilaurate, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and yttrium (III) isopropoxide oxide, and wherein the second diol is selected from the group consisting of polyethylene glycol, polycaprolactone diol, polylactide diol, poly (carbo) siloxane diol and polyvalerolactone diol.

4 . The method of claim 2 , wherein the second diol is synthesized via a second polymerization reaction performed within the flow reactor.

5 . The method of claim 4 , wherein the second polymerization reaction is a ring-opening polymerization of a cyclic monomer in the presence of an initiator and a urea catalyst.

6 . The method of claim 5 , wherein the cyclic monomer is selected from the group consisting of ε-caprolactone, lactide, valerolactones, cyclic carbonates and cyclic (carbo) siloxanes, wherein the initiator is selected from the group consisting of 1,8-octanediol, 1,6-hexanediol, and diethylene glycol, and wherein the urea catalyst is selected from the group consisting of 1,3-Bis[3,5-bis(trifluoromethyl) phenyl]urea, 1-[3,5-Bis (trifluoromethyl) phenyl]-3-[4-(trifluoromethyl) phenyl]urea, N-[3,5-bis (trifluoromethyl)-phenyl]-N′-phenylurea, N-[3,5-bis(trifluoromethyl)phenyl]-N′-cyclohexylurea, 1-phenyl-3-(3-(trifluoromethyl) phenyl) urea, 1,3-Diphenylurea, 1-cyclohexyl-3-phenylurea, and the respective thioureas.

7 . The method of claim 1 , wherein the polymerization reaction further includes polymerizing the diol and the diisocyanate monomer with 2-hydroxyethyl methacrylate, wherein an end-cap group derived from the 2-hydroxyethyl methacrylate is positioned at an end of a polymer backbone of the polyurethane as a result of the synthesizing.

8 . The method of claim 1 , further comprising:
generating a reactant conversion value based on a fourier-transform infrared spectra generated by a measurement device that is in fluid communication with the flow reactor.

9 . The method of claim 8 , further comprising:
employing, by a processor, a computer model to identify a target residence time associated with the polymerization reaction based on the reactant conversion value.

10 . The method of claim 9 , further comprising:
modifying the synthesizing by adjusting a flow rate within the flow reactor via a proportional-integral-derivative controller based on the target residence time.

11 . A computer-implemented method, comprising:
controlling, by a system operatively coupled to a processor, a set of proportional-integral derivative (PID) controllers to supply diol to a flow reactor, comprising a plurality of reactor loops, through a first inlet, the diisocyanate monomer to the flow reactor through a second inlet, and the organic catalyst to the flow reactor through a third inlet; measuring, by the system, a reactant conversion of a polyurethane polymerization reaction within the flow reactor; wherein the polymerization reaction polymerizes the diol with the diisocyanate monomer; and adjusting, by the system, a flow rate of a chemical reactant within the flow reactor based on the measuring to achieve a target polyurethane structure, wherein the adjusting the flow rate comprises introducing anhydrous tetrahydrofuran (THF) into the flow reactor at a point downstream of one or more reactor loops of the plurality of reactor loops via a fourth inlet.

12 . The computer-implemented method of claim 11 , further comprising:
employing, by the system, a computer model to determine a target residence time associated with the polyurethane polymerization reaction based on the reactant conversion, wherein the adjusting the flow rate results in the target residence time.

13 . The computer-implemented method of claim 12 , wherein the measuring the reactant conversion is performed by at least one analysis technique selected from the group consisting of fourier-transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, inline viscometry, gas chromatography, and ultraviolet-visible absorption spectroscopy.

14 . The computer-implemented method of claim 11 , wherein the introducing is associated with a variable time delay corresponding to flow rate changes within the flow reactor, and wherein the computer-implemented method further comprises:
predicting, by the system, based on accuracy of one or more historical predictions of time delay, the variable time delay prior to occurrence of the variable time delay; and in response to the predicting, operating, by the system, another PID controller, other than the PID controllers, controlling a fourth inlet to introduce the THF, thereby minimizing or eliminating the time delay.

Assignees

• IBM

Inventors

• Erdmann Tim
• Park Nathaniel H
• Hedrick James L
• Arrechea Pedro

Classifications

• B01J2208/00548

  Flow · CPC title

• C08G18/72

  Polyisocyanates or polyisothiocyanates · CPC title

• C08G18/1858

  having carbon-to-nitrogen double bonds · CPC title

• B01J8/0278

  Feeding reactive fluids (for solid material B01J8/0015) · CPC title

• C08G18/3203 Primary

  Polyhydroxy compounds · CPC title