Organo-modified layered double hydroxides and composite polymer materials comprising same

Patent metadata

Field	Value
Publication number	US-10745536-B2
Application number	US-201615576459-A
Country	US
Kind code	B2
Filing date	May 19, 2016
Priority date	May 22, 2015
Publication date	Aug 18, 2020
Grant date	Aug 18, 2020

Abstract

Layered double hydroxides organo-modified by 3-(4-hydroxyphenyl)propionic acid (HPPA), by 2-(4-hydroxyphenyl)ethylsulfonic acid or by a hydroxyphenylpropenoic acid, and to composite polymer materials having same. The composite materials are advantageously made of biosourced polymers such as poly(butylene succinate). These composite materials have improved properties over the polymers that make up the composition thereof, and over the composites of the prior art.

First claim

The invention claimed is:

1. An organo-modified layered double hydroxide material corresponding to formula (I):
[M 1-x M′ x (OH) 2 ] x+ (HO-ϕ—Y—X) x. m H 2 O  (I)

wherein:
X represents a group selected from: —COO − and —SO 3 − ,
Y represents a group selected from: —CH 2 —CH 2 —and —CH═CH—,
ϕ represents a phenyl group ortho, meta or para-substituted, on the one hand with the hydroxyl group, and on the other hand with the group —Y—X,
m represents a number in the range from 0 to 2,
M represents Mg,
M′ represents Al, and
x represents a number, 0.1≤x≤0.5.

2. The material as claimed in claim 1 , wherein X represents —COO − .

3. The material as claimed in claim 1 , wherein Y represents —CH 2 —CH 2 —.

4. The material as claimed in claim 1 , which corresponds to formula (Ia):
[M 1-x M′ x (OH) 2 ] x+ (HO-ϕ-CH 2 —CH 2 —COO − ) x. m H 2 O  (Ia)

wherein ϕ is para substituted.

5. The material as claimed in claim 1 , wherein: 0.2≤x≤0.4.

6. A composite material comprising at least one polymer matrix based on poly(butylene succinate) and/or poly(propylene succinate) and at least one organo-modified layered double hydroxide material corresponding to formula (I) as claimed in claim 1 .

7. The composite material as claimed in claim 6 , comprising at least one polymer matrix based on poly(butylene succinate).

8. The composite material as claimed in claim 7 , wherein the polymer matrix comprises one or more polymers or copolymers selected from: poly(ε-caprolactone), poly(lactic acid), polyhydroxyalkanoate, poly(ethylene terephthalate), poly(butylene terephthalate), poly(ethylene naphthalate), poly(ethylene adipate), poly(ethylene succinate), poly(propylene succinate), polypropylene, polyethylene, their copolymers and the copolymers that they form with poly(butylene succinate) (PBS).

9. The composite material as claimed in claim 7 , wherein the polymer matrix consists essentially of poly(butylene succinate).

10. The composite material as claimed in claim 6 , wherein the material (I) represents from 0.1 to 10 wt % relative to the total weight of the polymer matrix.

11. The composite material as claimed in claim 6 , wherein said material is obtained by a method comprising:
supplying an organo-modified layered double hydroxide material corresponding to formula (I):
[M 1-x M′ x (OH) 2 ] x+ (HO-ϕ-Y—X) x. m H 2 O  (I)

supplying the polymer matrix,
mixing the material of formula (I) and the polymer matrix at a temperature greater than or equal to the melting point of the polymer matrix,
extruding the mixture.

12. The composite material as claimed in claim 6 , wherein said material is obtained by a method comprising:
supplying an organo-modified layered double hydroxide material corresponding to formula (I):
[M 1-x M′ x (OH) 2 ] x+ (HO-ϕ-Y—X) x. m H 2 O  (I)

supplying precursors of the polymer matrix,
mixing compound (I) and the precursors of the polymer matrix,
applying conditions to the mixture that allow polymerization of the precursors.

13. A kit for manufacturing the composite material as claimed in claim 6 , said kit comprising at least one organo-modified layered double hydroxide material corresponding to formula (I):
[M 1-x M′ x (OH) 2 ] x+ (HO-ϕ—Y—X) x. m H 2 O  (I)

wherein:
X represents a group selected from: —COO − and —SO 3 − ,
Y represents a group selected from: —CH 2 —CH 2 —and —CH═CH—,
ϕ represents a phenyl group ortho, meta or para-substituted, on the one hand with the hydroxyl group, and on the other hand with the group —Y—X,
m represents a number in the range from 0 to 2,
M represents Mg,
M′ represents Al, and
x represents a number, 0.1<x<0.5; and

at least a poly(butylene succinate) or a poly(propylene succinate) or a composition of precursors of poly(butylene succinate) or a composition of precursors of poly(propylene succinate).

Assignees

• Centre Nat Rech Scient
• Université Clermont Auvergne
• Alma Mater Studiorum—Universita di Bologna
• Ecole Nat Supérieure De Chimie De Clermont Ferrand
• Universitéblaise Pascal- Clermont Ii
• Alma Mater Studiorum- Univ Di Bologna

Inventors

• Leroux Fabrice
• Verney Vincent
• Sisti Laura
• Celli Annamaria
• Totaro Grazia

Classifications

• C01F7/784

  Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions · CPC title

• C01B13/363 Primary

  Mixtures of oxides or hydroxides by precipitation · CPC title

• C08K3/22 Primary

  of metals · CPC title

• C01P2002/08

  Intercalated structures, i.e. with atoms or molecules intercalated in their structure · CPC title

• C01G9/006

  Compounds containing zinc, with or without oxygen or hydrogen, and containing two or more other elements · CPC title