IP Library Granted Patent US 10,745,536
Granted Patent B2
US 10,745,536 · App. 15/576,459 · Granted Aug 18, 2020

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

Inventors: Fabrice Leroux (Aubiere, FR); Vincent Verney (Aubiere, FR); Laura Sisti (Bologne, IT); Annamaria Celli (Bologne, IT); Grazia Totaro (Bologne, IT)
Assignees: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; UNIVERSITÉBLAISE PASCAL- CLERMONT II; ALMA MATER STUDIORUM- UNIVERSITA DI BOLOGNA; ECOLE NATIONALE SUPÉRIEURE DE CHIMIE DE CLERMONT FERRAND
C08K3/22C01B13/363C01F1/00C01F7/002C01F7/021C01G9/006C08K5/134C08L35/00C08L67/00C09C1/00C09C1/407C01P2002/08C01P2002/22C01P2004/24C01P2006/22C08K2003/2203C08K2003/2227
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Quick Facts
Patent No.
US 10,745,536
App. No.
15/576,459
Granted
Aug 18, 2020
Kind
B2
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.

Claims (44)

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).

Assignments (3)
CORRECTIVE ASSIGNMENT TO CORRECT THE EXECUTION DATES OF THE INVENTOR'S RECORDED WITH THE CHANGE OF NAME PREVIOUSLY RECORDED ON REEL 048772 FRAME 0482. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded May 8, 2019
From: LEROUX, FABRICE; VERNEY, VINCENT; SISTI, LAURA; CELLI, ANNAMARIA; TOTARO, GRAZIA
To: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; UNIVERSITÉ CLERMONT AUVERGNE; ALMA MATER STUDIORUM- UNIVERSITA DI BOLOGNA; ECOLE NATIONALE SUPERIEURE DE CHIMIE DE CLERMONT FERRAND
Reel/Frame 049122/0409 →
CHANGE OF NAME Recorded Apr 2, 2019
From: LEROUX, FABRICE; VERNEY, VINCENT; SISTI, LAURA; CELLI, ANNAMARIA; TOTARO, GRAZIA
To: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; UNIVERSITÉ CLERMONT AUVERGNE; ALMA MATER STUDIORUM- UNIVERSITA DI BOLOGNA; ECOLE NATIONALE SUPÉRIEURE DE CHIMIE DE CLERMONT FERRAND
Reel/Frame 048772/0482 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 3, 2018
From: LEROUX, FABRICE; VERNEY, VINCENT; SISTI, LAURA; CELLI, ANNAMARIA; TOTARO, GRAZIA
To: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE; UNIVERSITÉ BLAISE PASCAL- CLERMONT II; ALMA MATER STUDIORUM- UNIVERSITA DI BOLOGNA; ECOLE NATIONALE SUPÉRIEURE DE CHIMIE DE CLERMONT FERRAND
Reel/Frame 046262/0796 →
Priority Claims (1)
FR 15 54649 · May 22, 2015 · national
Continuity (1)
Related Publication 20180208739A1 · Jul 26, 2018