Betapropiolactone and functionalized betapropiolactone based polymer systems

Patent metadata

Field	Value
Publication number	US-11780958-B2
Application number	US-202118020722-A
Country	US
Kind code	B2
Filing date	Aug 13, 2021
Priority date	Aug 17, 2020
Publication date	Oct 10, 2023
Grant date	Oct 10, 2023

Abstract

Disclosed herein are polymers, copolymers and polymer systems based on polypropiolactones which can be biodegradable and can enhance the recyclability of polymer systems, which can be functionalized to introduce desired functionality into the polymers and/or which may optionally be prepared from renewable raw materials. Disclosed are novel functionalized beta propiolactones. Some of the novel functionalized beta propiolactones have functional groups bound to the ring structure of the lactone that provide improved polymer systems. Disclosed are novel homopolymers of the functionalized beta propiolactones. Disclosed are novel copolymers based on the functionalized beta propiolactones with beta propiolactone or other monomers which copolymerize with the functionalized beta propiolactones.

First claim

What is claimed is:

1. A composition comprising a polymeric layer disposed on a layer of a homopolymer of one or more functionalized beta-propiolactones or copolymer containing one or more functionalized beta-propiolactones and beta-propiolactone; wherein the homopolymers and copolymers are polypropiolactones and the functionalized beta-propiolactones correspond to the formula:

wherein independently in each occurrence R 1 , R 2 , R 3 , R 4 are separately in each occurrence hydrogen, a hydrocarbyl moiety or a fluorocarbyl moiety; the hydrocarbyl moiety or fluorocarbyl moiety may optionally contain at least one heteroatom or at least one substituent, wherein at least one R 1 , R 2 , R 3 , R 4 are present as the hydrocarbyl moiety or fluorocarbyl moiety.

2. The composition according to claim 1 wherein one or more functional groups of the functionalized beta-propiolactones form a covalent bond or ionic bond with the polymeric layer.

3. The composition according to claim 1 , wherein at least one R 1 , R 2 , R 3 , R 4 are present as the hydrocarbyl or fluorocarbyl moiety that enhances function of the functionalized beta-propiolactones incorporated into polymer chains useful in coatings or films.

4. The composition according to claim 1 , comprising one or more functionalized beta-propiolactone wherein at least one R 1 , R 2 , R 3 , R 4 are hydrocarbyl or fluorocarbyl groups that contain one or more of unsaturated groups, electrophilic groups, nucleophilic groups, anionic groups, cationic groups, zwitterions, hydrophobic groups, hydrophilic groups, halogen atoms, natural minerals, synthetic minerals, carbon based particles, an ultraviolet active group, a polymer having surfactant properties, and polymerization initiators.

5. The composition according to claim 1 , comprising one or more functionalized beta-propiolactone wherein R 1 , R 2 , R 3 , R 4 are separately in each occurrence hydrogen, fluorocarbyl moiety, aryl, substituted aryl, cycloaliphatic, substituted cycloaliphatic, aliphatic or substituted aliphatic moiety.

6. The composition according to claim 1 , comprising one or more functionalized beta-propiolactone wherein R 1 , R 2 , R 3 , R 4 are separately in each occurrence hydrogen, alkyl, alkenyl, cycloalkyl, heterocyclyl, alkyl heterocyclyl, aryl, aralkyl, alkaryl, heteroaryl, alkyl heteroaryl, or polyoxyalkylene; or two of R 1 , R 2 , R 3 , R 4 may form a 5-20 membered cyclic, heterocyclic ring; or R 1 , R 2 , R 3 , R 4 may be separately in each occurrence C 1 -C 15 alkyl, C 2 -C 15 alkenyl, C 3 -C 15 cycloalkyl, C 2 -C 20 heterocyclyl, C 3 -C 20 alkyl heterocyclyl, C 6 -C 18 aryl, C 7 -C 18 alkaryl, C 7 -C 25 aralkyl, C 5 -C 18 heteroaryl, C 6 -C 25 alkyl heteroaryl, or polyoxyalkylene; or a linking group (L) which functions to link the functional portion of the groups to a cyclic ring.

7. The composition according to claim 1 , comprising one or more functionalized beta-propiolactones wherein the substituent is halo, a poly tetrafluoro alkene, alkylthio, alkoxy, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, ester, polyalkylene oxide, unsaturated groups, natural mineral, synthetic mineral, or a carbon-based structure.

8. The composition according to claim 1 , comprising one or more functionalized beta-propiolactones wherein one or more of R 1 , R 2 , R 3 , R 4 is a halogen substituted alkyl group, a sulfonic acid substituted alkyloxy group, an alkyl sulfonate alkyloxy group, an alkyl ether substituted alkyl group, a polyalkylene oxide substituted alkyl group, an alkyl ester substituted alkyl group, an alkenyloxy substituted alkyl group, an aryl ester substituted alkyl group, an alkenyl group, a cyano substituted alkyl group, an alkenyl ester substituted alkyl group, a cycloalkyl substituted alkyl group, an aryl group, a heteroatom containing cycloalkenyl alkyl ether substituted alkyl group, a hydroxyl substituted alkyl group, a cycloaliphatic substituted alkenyl group, an aryl substituted alkyl group, a haloaryl substituted alkyl group, an aryloxy substituted alkyl group, an alkyl ether substituted alkaryl group, a hetero atom containing cycloaliphatic group substituted alkyl group, an alkyl amide substituted alkyl group, an alkenyl substituted cycloaliphatic group; two of R 1 or R 2 and R 3 or R 4 form a cyclic ring, which may optionally contain one or more unsaturated groups, an alkyl group substituted with a beta propiolactone group which may optionally be contain one or more ether groups and/or one or more hydroxyl groups, a glycidyl ether group, or a benzocyclobutene substituted alkyl group, optionally substituted with one or more ether groups, and optionally a linking group (L) which functions to link the functional portion of the groups to the cyclic ring.

9. The composition according to claim 1 , comprising one or more functionalized beta-propiolactone wherein R 1 is a heterocycle that is polymerizable, such as an oxazoline, or corresponds to one of the formulas;

wherein m and n are independently integers of 1 or more, with the proviso that where m, n or both are greater than 1 and the units in parenthesis may be arranged in any manner;
R 5 is hydrogen or an alkyl group; and
L is a linking group.

10. The composition according to claim 1 , comprising a polymer having pendant electrophilic, nucleophilic, or ionic groups bonded to the homopolymer of one or more functionalized beta-propiolactones or copolymer containing one or more functionalized beta-propiolactones having pendant electrophilic, nucleophilic, or ionic groups bonded to the polymer through the pendant electrophilic, nucleophilic, or ionic groups.

11. The composition according to claim 1 , wherein the functionalized beta-propiolactones have one or more pendant groups which are polymerizable by anionic polymerization, cationic polymerization, condensation polymerization, radical polymerization, ring opening metathesis, zwitterions, and a layer of a polymer that polymerizes by anionic polymerization, cationic polymerization, condensation polymerization, or addition polymerization, wherein the one or more of the pendant groups polymerize with the polymer that polymerizes by anionic polymerization, cationic polymerization, condensation polymerization, radical polymerization, or ring opening metathesis, and covalently bond the two layers together.

12. A multilayer polymeric structure comprising separate layers of two incompatible polymers with one or more of beta-propiolactones, functionalized beta-propiolactones or a polymer containing one or more of beta-priopiolactones and functionalized beta-propiolactones disposed between the layers; wherein the polymer containing the one or more functionalized beta-propiolactones is a polypropiolactone and the functionalized beta-propiolactones correspond to the formula:

wherein independently in each occurrence R 1 , R 2 , R 3 , R 4 are separately in each occurrence hydrogen, a hydrocarbyl moiety or a fluorocarbyl moiety; the hydrocarbyl moiety or fluorocarbyl moiety may optionally contain at least one heteroatom or at least one substituent, wherein at least one R 1 , R 2 , R 3 , R 4 are present as the hydrocarbyl or fluorocarbyl moiety.

13. A composition comprising a substrate, a layer of one or more of beta-propiolactones and functionalized beta-propiolactones or a polymer containing one or more o

Assignees

• Novomer Inc

Inventors

• Coates Geoffrey W
• Uhrig Jeffrey K
• Stoutenburg Eric

Classifications

• C08G63/08 Primary

  Lactones or lactides · CPC title

• B32B27/08

  of synthetic resin · CPC title

• B32B27/36

  comprising polyesters · CPC title

• C09D167/04

  Polyesters derived from hydroxycarboxylic acids, e.g. lactones (C09D167/06 takes precedence) · CPC title

• B32B2250/02

  2 layers · CPC title