Functionalized α-angelica lactone monomers and polymers obtained therefrom

Patent metadata

Field	Value
Publication number	US-12319665-B2
Application number	US-202117451170-A
Country	US
Kind code	B2
Filing date	Oct 18, 2021
Priority date	Apr 16, 2019
Publication date	Jun 3, 2025
Grant date	Jun 3, 2025

Abstract

The present invention is directed to a monomer for chain growth polymerization, in particular anionic polymerization, said monomer having the general formula (EFL)

wherein: R a is a C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 6 -C 18 aryl or C 2 -C 12 alkenyl group. The present invention is further directed to a process for the anionic polymerization of at least one compound (EFL) as defined above, wherein said anionic polymerization is conducted in the presence of an initiator selected from the group consisting of: alkali metal organyls; alkali metal alkoxides; alkali metal thiolate; alkali metal amides; and compounds of an element of group 3a of the Periodic Table of the Elements. The process of anionic polymerization yields a homo- or co-polymer (p-EFL) having pendant lactone functional groups in its repeating units.

First claim

What is claimed is:

1. A monomer for chain-growth polymerization, having the general formula:

wherein: R a is a C 3 -C 30 cycloalkyl or C 2 -C 12 alkenyl group.

2. The monomer of claim 1 , wherein R a is a C 2 -C 8 alkenyl group.

3. A method of synthesis of the monomer of claim 1 , the method comprising reacting, in the presence of an acid anhydride and an antioxidant:
at least one α-angelica lactone; and
at least one orthoester having the general formula (1):

wherein R 1 , R 2 and R 3 are independently selected from C 3 -C 30 cycloalkyl or C 2 -C 12 alkenyl groups.

4. The method of claim 3 , wherein the acid anhydride is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, and succinic anhydride.

5. The method of claim 3 , wherein the antioxidant is at least one sterically hindered phenol.

6. A method of chain growth polymerization of at least one monomer of claim 1 ,
wherein the chain growth polymerization is conducted in the presence of an initiator selected from the group consisting of alkali metal organyls, alkali metal alkoxides, alkali metal thiolate, and alkali metal amides.

7. The method of claim 6 , wherein the initiator is present in an amount of from 0.0001 to 5 wt. %, based on the total weight of the at least one monomer.

8. The method of claim 6 , wherein the initiator is an alkali metal alkoxide wherein the alkali metal alkoxide is selected from the group consisting of aliphatic alkoxides of lithium, sodium, and potassium.

9. The method of claim 6 , wherein the initiator is an alkali metal organyl, wherein the alkali metal organyl is an organolithium compound selected from the group consisting of ethyllithium, propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, diphenylhexyllithium, hexamethylenedilithium, butadienyllithium, isoprenyllithium, polystyryllithium, 1,4-dilithiobutane, 1,4-dilithio-2-butene, and 1,4-dilithiobenzene and any combination thereof.

10. The method of claim 6 , wherein the chain growth polymerization is of a monomer mixture, wherein the monomer mixture comprises:
the monomer of claim 1 in an amount of from 15 to 75 wt. %; and
at least on co-monomer in an amount of from 25 to 85 wt%, wherein the amounts are based on the total weights of the monomers in the monomer mixture.

11. The method of claim 4 , wherein the acid anhydride is present in a catalytic amount based on the total number of moles of the reactants.

12. The method of claim 5 , wherein the antioxidant is present in an amount greater than 0 and up to 10 wt %, based on the total weight of the reactants.

13. The method of claim 10 , wherein the at least one co-monomer is selected from the group consisting of (meth)acrylonitrile, alkyl (meth)acrylate esters, (meth)acrylic acids, vinyl esters, and vinyl monomers.

14. The method of claim 10 , wherein the at least one co-monomer is a vinyl monomer selected from the group consisting of 1,3-butadiene, isoprene, styrene, divinyl benzene, heterocyclic vinyl compounds, and vinyl halides.

15. A composition comprising:
the monomer of claim 1 ; and
at least one co-monomer selected from the group consisting of (meth)acrylonitrile, alkyl (meth) acrylate esters, (meth)acrylic acids, vinyl esters, and vinyl monomers.

16. A composition comprising:
a monomer having the general formula:

wherein R a is selected from the group consisting of a C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 6 -C 18 aryl, and C 2 -C 12 alkenyl group; and
at least one co-monomer.

17. The composition of claim 16 , wherein the least one co-monomer is selected from the group consisting of (meth)acrylonitrile, alkyl (meth) acrylate esters, (meth)acrylic acids, vinyl esters, and vinyl monomers.

Assignees

• Henkel Ag & Co Kgaa

Inventors

• Taden Andreas
• Beck Horst
• Brandt Adrian
• Ito Kenji
• De Vries Johannes Gerardus
• Savini Arianna
• Tin Sergey

Classifications

• C08F20/28

  containing no aromatic rings in the alcohol moiety · CPC title

• C08G63/08

  Lactones or lactides · CPC title

• C07D307/58 Primary

  One oxygen atom, e.g. butenolide · CPC title