ORGANO-MODIFIED LAYERED DOUBLE HYDROXIDES AND COMPOSITE POLYMER MATERIALS COMPRISING SAME

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

1-15. (canceled)

16. An organo-modified layered double hydroxide material corresponding to formula (I):
[M.sub.1-xM.sub.x(OH).sub.2].sup.x+(HO--YX).sub.x.mH.sub.2O(I) wherein: X represents a group selected from: COO.sup. and SO.sub.3.sup., Y represents a group selected from: CH.sub.2CH.sub.2 and CHCH, 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 YX, m represents a number in the range from 0 to 2, and either: M represents one or more cations selected from: Mg, Zn, Co, Ni, Ca, Cu, M represents one or more cations selected from: Al, Ga, Fe, Cr, and x represents a number, 0.1x0.5, or: M represents Li, M represents Al, and x=2/3.

17. The material as claimed in claim 16, wherein the compound X represents COO.sup..

18. The material as claimed in claim 16, wherein the compound Y represents CH.sub.2CH.sub.2.

19. The material as claimed in claim 16, which corresponds to formula (Ia):
[M.sub.1-xM.sub.x(OH).sub.2].sup.x+(HO--CH.sub.2CH.sub.2COO.sup.).sub.x.mH.sub.2O(Ia) wherein is para substituted.

20. The material as claimed in claim 16, wherein: 0.2x0.4.

21. The material as claimed in claim 16, wherein M represents one or more cations selected from Mg and Zn, and M represents one or more cations selected from Al and Fe.

22. The material as claimed in claim 21, wherein Mg represents at least 50% of the cations M; the percentages being expressed in moles, relative to the total number of moles of cation M.

23. The material as claimed in claim 22, wherein Mg represents at least 75% of the cations M; the percentages being expressed in moles, relative to the total number of moles of cation M.

24. The material as claimed in claim 23, wherein Mg represents 100% of the cations M; the percentages being expressed in moles, relative to the total number of moles of cation M.

25. The material as claimed in claim 21, wherein Al represents at least 50% of the cations M; the percentages being expressed in moles, relative to the total number of moles of cation M.

26. The material as claimed in claim 25, wherein Al represents at least 75% of the cations M; the percentages being expressed in moles, relative to the total number of moles of cation M.

27. The material as claimed in claim 26, wherein Al represents 100% of the cations M, the percentages being expressed in moles, relative to the total number of moles of cation M.

28. 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 16.

29. The composite material as claimed in claim 28, comprising at least one polymer matrix based on poly(butylene succinate).

30. The composite material as claimed in claim 29, wherein the polymer matrix comprises one or more polymers or copolymers selected from: poly(-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).

31. The composite material as claimed in claim 29, wherein the polymer matrix consists essentially of poly(butylene succinate).

32. The composite material as claimed in claim 28, wherein the material (I) represents from 0.1 to 10 wt % relative to the total weight of the polymer matrix.

33. The composite material as claimed in claim 28, wherein said material is obtained by a method comprising: supplying an organo-modified layered double hydroxide material corresponding to formula (I):
[M.sub.1-xM.sub.x(OH).sub.2].sup.x+(HO--YX).sub.x.mH.sub.2O(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.

34. The composite material as claimed in claim 28, wherein said material is obtained by a method comprising: supplying an organo-modified layered double hydroxide material corresponding to formula (I):
[M.sub.1-xM.sub.x(OH).sub.2].sup.x+(HO--YX).sub.x.mH.sub.2O(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.

35. A kit for manufacturing a composite material as claimed in claim 28, said kit comprising at least one organo-modified layered double hydroxide material corresponding to formula (I):
[M.sub.1-xM.sub.x(OH).sub.2].sup.x+(HO--YX).sub.x.mH.sub.2O(I) wherein: X represents a group selected from: COO.sup. and SO.sub.3.sup., Y represents a group selected from: CH.sub.2CH.sub.2 and CHCH, 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 YX, m represents a number in the range from 0 to 2, and either: M represents one or more cations selected from: Mg, Zn, Co, Ni, Ca, Cu, M represents one or more cations selected from: Al, Ga, Fe, Cr, and x represents a number, 0.1x0.5, or: M represents Li, M represents Al, and x=2/3; 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).

Description

FIGURES

[0185] FIGS. 1, 2a, 2b, 3a, 3b: Graphical representation of the melt viscoelasticity of various composites PBS/(Mg or Zn: HPPA-modified Al) Cole-Cole diagram with abscissa: real component of complex viscosity; ordinate: imaginary component of complex viscosity.

[0186] FIGS. 4a, 4b, 5a, 5b: Graphical representation of the melt viscoelasticity of various composites PBS/(Mg: Al modified with HPPA or various surfactants) Cole-Cole diagram with abscissa: real component of complex viscosity; ordinate: imaginary component of complex viscosity.

[0187] FIG. 6: Graphical representation of the melt viscoelasticity of various composites PPS/(Mg: HPPA-modified Al) Cole-Cole diagram with abscissa: real component of complex viscosity; ordinate: imaginary component of complex viscosity.

[0188] FIG. 7: Graphical representation of the melt viscoelasticity of various composites PBSA/(Mg: HPPA-modified Al) Cole-Cole diagram with abscissa: real component of complex viscosity; ordinate: imaginary component of complex viscosity.

[0189] FIG. 1: PBS-LDH.sub.ZnAl-HPPA in situ (protocol 3) () PBS NaturePlast; () PBS-LDH.sub.ZnAl-HPPA 1 wt %; () PBS-LDH.sub.ZnAl-HPPA 3 wt %; () PBS-LDH.sub.ZnAl-HPPA 5 wt %; () PBS-LDH.sub.ZnAl-HPPA 10 wt %.

[0190] FIG. 2a: PBS-LDH.sub.MgAl-HPPA in situ (protocol 3) () PBS NaturePlast; () PBS-LDH.sub.MgAl-HPPA 1 wt %; () PBS-LDH.sub.MgAl-HPPA 3 wt %; () PBS-LDH.sub.MgAl-HPPA 5 wt %; () PBS-LDH.sub.MgAl-HPPA 10 wt %.

[0191] FIG. 2b: Enlargement of FIG. 2a between 0 and 400 Pa.Math.s PBS-LDH.sub.MgAl-HPPA in situ () PBS NaturePlast; () PBS-LDH.sub.MgAl-HPPA 1 wt %; () PBS-LDH.sub.MgAl-HPPA 3 wt %; () PBS-LDH.sub.MgAl-HPPA 5 wt %; () PBS-LDH.sub.MgAl-HPPA 10 wt %.

[0192] FIG. 3a: PBS-LDH.sub.ZnAl-HPPA ex-situ (protocol 2) () PBS Enpol IRE G4560; () PBS-LDH.sub.ZnAl-HPPA 1 wt %; (x) PBS-LDH.sub.ZnAl-HPPA 2.5 wt %; () PBS-LDH.sub.ZnAl-HPPA 5 wt %; (*) PBS-LDH.sub.ZnAl-HPPA 7.5 wt %; () PBS-LDH.sub.ZnAl-HPPA 10 wt %.

[0193] FIG. 3b: Enlargement of FIG. 3a between 0 and 1000 Pa.Math.s PBS-LDH.sub.ZnAl-HPPA ex situ () PBS Enpol IRE G4560; () PBS-LDH.sub.ZnAl-HPPA 1 wt %; (x) PBS-LDH.sub.ZnAl-HPPA 2.5 wt %; () PBS-LDH.sub.ZnAl-HPPA 5 wt %; (*) PBS-LDH.sub.ZnAl-HPPA 7.5 wt %; () PBS-LDH.sub.ZnAl-HPPA 10 wt %.

[0194] FIG. 4a: PBS-LDH.sub.MgAl-HPPA in situ (protocol 3) (*) PBS prepared by polycondensation (protocol 3); (x) PBS-LDH.sub.MgAl-HPPA 3 wt %; () PBS-LDH.sub.MgAl-citrate 3 wt %; (.diamond-solid.) PBS-LDH.sub.MgAl-succinate 3 wt %; (.circle-solid.) PBS-LDH A-sebacate 3 wt %; () PBS-LDH.sub.MgAl-adipate 3 wt %; () PBS-LDH.sub.MgAl-ricinoleate 3 wt %.

[0195] FIG. 4b: Enlargement of FIG. 4a between 0 and 150 Pa.Math.s PBS-LDH.sub.MgAl-HPPA in situ (protocol 3) (*) PBS prepared by polycondensation (protocol 3); (x) PBS-LDH.sub.MgAl-HPPA 3 wt %; () PBS-LDH.sub.MgAl-citrate 3 wt %; (.diamond-solid.) PBS-LDH.sub.MgAl-succinate 3 wt %; (.circle-solid.) PBS-LDH.sub.MgAl-sebacate 3 wt %; () PBS-LDH.sub.MgAl-adipate 3 wt %; () PBS-LDH.sub.MgAl-ricinoleate 3 wt %.

[0196] FIG. 5a: PBS-LDH.sub.MgAl-HPPA ex-situ (protocol 2) (*) PBS Enpol IRE G4560; (x) PBS-LDH.sub.MgAl-HPPA 2.5 wt %; (.diamond-solid.) PBS-LDH.sub.MgAl-succinate 3 wt %; (.circle-solid.) PBS-LDH.sub.MgAl-sebacate 3 wt %; () PBS-LDH.sub.MgAl-adipate 3 wt %.

[0197] FIG. 5b: Enlargement of FIG. 5a between 0 and 250 Pa.Math.s PBS-LDH.sub.MgAl-HPPA ex-situ (protocol 2) (*) PBS Enpol IRE G4560; (x) PBS-LDH.sub.MgAl-HPPA 2.5 wt %; (.diamond-solid.) PBS-LDH.sub.MgAl-succinate 3 wt %; (.circle-solid.) PBS-LDH.sub.MgAl-sebacate 3 wt %; () PBS-LDH.sub.MgAl-adipate 3 wt %.

[0198] FIG. 6: PPS-LDH.sub.MgAl-HPPA ex-situ (protocol 2) (*) PPS (protocol 4); (.circle-solid.) PPS-LDH.sub.MgAl-HPPA 1 wt %; () PPS-LDH.sub.MgAl-HPPA 5 wt %; (.diamond-solid.) PPS-LDH.sub.MgAl-HPPA 10 wt %.

[0199] FIG. 7: PBSA-LDH.sub.MgAl-HPPA ex-situ (protocol 2) (*); PBSA (protocol 5); (.circle-solid.) PBSA-LDH.sub.MgAl-HPPA 1 wt %; () PBSA-LDH.sub.MgAl-HPPA 5 wt %; (.diamond-solid.) PBSA-LDH.sub.MgAl-HPPA 10 wt %.

EXPERIMENTAL SECTION

[0200] IMaterials and Methods:

[0201] Raw Materials:

[0202] PBS: A Type of PBS was Used for the Reactive Mixing: [0203] PBS1: Enpol IRE G4560injection fluid grade, marketed by the company Ire Chemical Ltd. [0204] PBS2: PBE003 Nature Plastextrusion grade, marketed by the company NaturePlast

[0205] PPS (poly(propylene)succinate): Prepared according to protocol 4

[0206] PBSA (poly(butylene succinate-co-adipate): Prepared according to protocol 5

[0207] Methods of Processing:

[0208] Preparation of Organo-Modified LDH (Protocol 1):

[0209] This is carried out as a one pot synthesis to obtain the hybrid assembly either in the form of powder, or in the form of paste.

[0210] A quantity of M(NO.sub.3).sub.2(M=Mg, Zn, Co, Ni, Ca, Cu) and of M(NO.sub.3).sub.3(M=Al, Ga, Fe, Co) is added to a reactor containing an amount of organic molecule of the carboxylic acid type or ester of carboxylic acid (HPPA). The pH of the mixture is controlled to pH=90.1 by adding soda, the whole being placed under nitrogen. Coprecipitation of the salts at basic pH is effected at room temperature. The paste formed is then centrifuged and washed with deionized water 3 times to remove the excess HPPA and unreacted reactants. The yield is high: in the region of 95% taking into account the theoretical empirical formula (calculation based on thermogravimetry and elemental chemical analysis).

[0211] Extrusion (Protocol 2):

[0212] The mixtures were prepared in the molten state in co-rotating twin-screw extrusion using a THERMO Instrument micro-compounder. The total amount of material introduced is about 6 g (polymer+organo-modified LDH), with 1, 2.5, 5, 7.5, and 10 wt % of the organo-modified LDH relative to the weight of polymer, the rotary speed of the screws is 100 rev/min for kneading times of 2 to 3 min maximum at 140 C. A control (T1) is prepared without filler.

[0213] Polycondensation In Situ (Protocol 3):

[0214] A concave-bottomed wide-neck glass reactor (250 ml capacity) was charged with 1, 3, 5, 10% of the organo-modified LDH (for example 1.4 g, which corresponds to 3 wt % relative to the theoretical yield of the polymer), butanediol (30 g, 0.33 mol) and titanium tetrabutoxide (0.06 g, 1.7 10.sup.4 mol).

[0215] The reactor was closed with a three-neck cover equipped with a mechanical stirrer and a torquemeter. The system is connected to a water-cooled condenser and is immersed in an oil bath with thermostatic control to 190 C., stirring vigorously. After one hour the oil bath was cooled to 180 C. and dimethyl succinate (40 g, 0.27 mol) was added, the temperature was then raised to 190 C. and was kept at this value until the methanol had distilled (about 1 hour). The distillate recovered during this first step in the condenser was collected and analyzed by FT-IR. The temperature was then increased to 230 C., the cover was heated to a temperature of 110 C. with a strip heater and the reactor is connected to a condenser cooled with liquid nitrogen. Dynamic vacuum was then applied for 60 minutes to reach 0.1 mbar. After a variable time depending on the cation composition (about 90 min for the Mg.sub.2Al series), a very viscous product, transparent and with a light brownish color in the molten state was removed from the reactor. The molecular structure of PBS was confirmed by .sup.1H NMR.

[0216] Polycondensation (Protocol 4):

[0217] A concave-bottomed wide-neck glass reactor (250 ml capacity) was charged with 1,3-propanediol (34 g, 0.45 mol) and dimethyl succinate (51 g, 0.35 mol) and titanium tetrabutoxide (0.07 g, 2.0 10.sup.4 mol). The reactor was closed with a three-neck cover equipped with a mechanical stirrer and a torquemeter. The system is connected to a water-cooled condenser and is immersed in an oil bath with thermostatic control to 200 C., with stirring at 340 rev/min. The cover was heated to a temperature of 80 C. with a strip heater. The oil bath was maintained at 200 C. until the methanol had distilled (about 1 hour). The distillate recovered during this first step in the condenser was collected and analyzed by FT-IR. The cover was heated to a temperature of 90 C., and the reactor is connected to a condenser cooled with liquid nitrogen. The temperature ramp up to 230 C. and dynamic vacuum to 0.9 mbar were then applied for about 60 minutes. After about 240 min, a very viscous product, transparent and with a light yellow color, and in the molten state, was removed from the reactor. The molecular structure of PPS was confirmed by .sup.1H NMR.

[0218] Polycondensation (Protocol 5):

[0219] A concave-bottomed wide-neck glass reactor (250 ml capacity) was charged with 1,4-butanediol (40 g, 0.44 mol) and dimethyl succinate (43 g, 0.30 mol), dimethyl adipate (13 g, 0.074 mol) and titanium tetrabutoxide (0.05 g, 1.6 10.sup.4 mol). The reactor was closed with a three-neck cover equipped with a mechanical stirrer and a torquemeter. The system is connected to a water-cooled condenser and immersed in an oil bath with thermostatic control to 190 C., with stirring at 200 rev/min. The cover was heated to a temperature of 80 C. with a strip heater. The oil bath was maintained at 190 C. until the methanol had distilled (about 1 hour 30 minutes). The distillate recovered during this first step in the condenser was collected and analyzed by FT-IR. The cover was heated to a temperature of 110 C. and the reactor is connected to a condenser cooled with liquid nitrogen. The temperature ramp up to 230 C. and dynamic vacuum to 0.4 mbar were then applied for about 40 minutes. After about 300 min, a very viscous product, transparent and with a light yellow color, and in the molten state, was removed from the reactor. The molecular structure of PBSA was confirmed by .sup.1H NMR.

[0220] Methods of Characterization:

[0221] X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), thermogravimetric analysis (TGA), Differential Scanning Calorimetry (DSC), Dynamic Mechanical Thermal Analysis (DMTA).

[0222] Rheology Testing:

[0223] The rheological measurements were performed in parallel plane-plane geometry and in oscillating mode using an ARESTA Instrument mechanical spectrometer at stressing frequencies between 0.1 and 100 rad/s.

[0224] IISynthesis:

[0225] Organo-Modified LDH:

[0226] The following materials were prepared from 3-(4-hydroxyphenyl)propionic acid following protocol 1 given above:

TABLE-US-00001 TABLE 1 HPPA-modified LDH materials Material M M Formula Characterization M1 Mg Al [Mg.sub.2/3 Al.sub.1/3(OH).sub.2].sup.1/3+ (HOCH.sub.2CH.sub.2COO.sup.).sub.1/3m H.sub.2O XRD, FTIR, TGA M2 Zn Al [Zn.sub.2/3 Al.sub.1/3(OH).sub.2].sup.1/3+ (HOCH.sub.2CH.sub.2COO.sup.).sub.1/3m H.sub.2O XRD, FTIR, TGA

[0227] The following materials were prepared from sodium dodecylsulfate (SDS), sodium succinate (SU), sodium sebacate (SE), sodium adipate (AD), citric acid (CA), and ricinoleic acid (RA) following protocol 1 given above:

TABLE-US-00002 TABLE 2 LDH materials modified with sodium dodecylsulfate (SDS), sodium succinate (SU), sodium sebacate (SE), sodium adipate (AD), citric acid (CA), and ricinoleic acid (RA) (comparative) Material Organic No. M M anion Formula Characterization M1 Mg Al SDS [Mg.sub.2/3 Al.sub.1/3(OH).sub.2].sup.1/3+ (SDS.sup.).sub.1/3m H.sub.2O XRD, FTIR, TGA M2 Zn Al SDS [Zn.sub.2/3 Al.sub.1/3(OH).sub.2].sup.1/3+ (SDS.sup.).sub.1/3m H.sub.2O XRD, FTIR, TGA M3 Mg Al SU [Mg.sub.2/3 Al.sub.1/3(OH).sub.2].sup.1/3+ (SU.sup.2).sub.0.16 m H.sub.2O XRD, FTIR, TGA M4 Mg Al SE [Mg.sub.2/3 Al.sub.1/3(OH).sub.2].sup.1/3+ (SE.sup.2).sub.0.16 m H.sub.2O XRD, FTIR, TGA M5 Mg Al AD [Mg.sub.2/3 Al.sub.1/3(OH).sub.2].sup.1/3+ (AD.sup.2).sub.0.16 m H.sub.2O XRD, FTIR, TGA M6 Mg Al CA [Mg.sub.2/3 Al.sub.1/3(OH).sub.2].sup.1/3+ (CA.sup.3).sub.0.11 m H.sub.2O XRD, FTIR, TGA M7 Mg Al RA [Mg.sub.2/3 Al.sub.1/3(OH).sub.2].sup.1/3+ (RA.sup.).sub.0.33 m H.sub.2O XRD, FTIR, TGA

[0228] PBS/Organo-Modified LDH Composite:

[0229] The following materials were prepared following protocol 2 above:

TABLE-US-00003 TABLE 3 PBS/organo-modified LDH materials according to the invention (C1 to C5), according to the prior art (C1 to C5) and controls (T1 to T2) wt % Com- Organo- organo- posite modified modified No. LDH PBS LDH/PBS Characterization FIGS. C1 M2 PBS1 1 XRD, TGA, rheology, 3 C2 M2 PBS1 2.5 XRD, TGA, rheology, 3 C3 M2 PBS1 5 XRD, TGA, rheology, 3 C4 M2 PBS1 7.5 XRD, TGA, rheology, 3 C5 M2 PBS1 10 XRD, TGA, rheology, 3 C1 M1 PBS1 5 XRD, TGA, rheology C2 M2 PBS1 5 XRD, TGA, rheology C3 M3 PBS2 3 XRD, TGA, rheology 5 C4 M4 PBS2 3 XRD, TGA, rheology 5 C5 M5 PBS2 3 XRD, TGA, rheology 5 T1 PBS1 XRD, TGA, rheology 1, 2a, 2b, 5a, 5b T2 PBS2 XRD, TGA, rheology 3a, 3b

[0230] The following materials were prepared following protocol 3 above:

TABLE-US-00004 TABLE 4 PBS/organo-modified LDH materials according to the invention (C6 to C13), and according to the prior art (C6 to C10) Organo- wt % organo- Composite modified modified No. LDH LDH/PBS Characterization FIGS. C6 M1 1 XRD, DSC, TGA, rheology, DMTA 2 C7 M1 3 XRD, DSC, TGA, rheology, DMTA 2 C8 M1 5 XRD, DSC, TGA, rheology, DMTA 2 C9 M1 10 XRD, DSC, TGA, rheology, DMTA 2 C10 M2 1 XRD, DSC, TGA, rheology, DMTA 1 C11 M2 3 XRD, DSC, TGA, rheology, DMTA 1 C12 M2 5 XRD, DSC, TGA, rheology, DMTA 1 C13 M2 10 XRD, DSC, TGA, rheology, DMTA 1 C6 M6 3 XRD, DSC, TGA, rheology, DMTA 4 C7 M3 3 XRD, DSC, TGA, rheology, DMTA 4 C8 M4 3 XRD, DSC, TGA, rheology, DMTA 4 C9 M5 3 XRD, DSC, TGA, rheology, DMTA 4 C10 M7 3 XRD, DSC, TGA, rheology, DMTA 4

[0231] PPS/Organo-Modified LDH Composite:

[0232] The following materials were prepared following protocol 2. The control was prepared following protocol 4P

TABLE-US-00005 TABLE 5 PPS/organo-modified LDH materials according to the invention (C14 to C16) and control (T3) wt % Organo- organo- Composite modified modified No. LDH PPS LDH/PBS Characterization FIGS. C14 M1 PPS 1 XRD, DSC, 6 TGA, rheology C15 M1 PPS 5 XRD, DSC, 6 TGA, rheology C16 M1 PPS 10 XRD, DSC, 6 TGA, rheology T3 PPS XRD, DSC, 6 TGA, rheology

[0233] PBSA/Organo-Modified LDH Composite:

[0234] The following materials were prepared following protocol 2. The control was prepared following protocol 5.

TABLE-US-00006 TABLE 6 PBSA/organo-modified LDH materials according to the invention (C17 to C19) and control (T4) wt % Com- Organo- organo- posite modified modified No. LDH PBSA LDH/PPS Characterization FIGS. C17 M1 PBSA 1 XRD, DSC, TGA, 7 rheology C18 M1 PBSA 5 XRD, DSC, TGA, 7 rheology C19 M1 PBSA 10 XRD, DSC, TGA, 7 rheology T4 PBSA XRD, DSC, TGA, 7 rheology

[0235] IIIResults:

[0236] FIGS. 1, 2 and 3 illustrate the effect of introducing filler M1 (Mg: HPPA-modified Al) and M2 (Zn: HPPA-modified Al) in variable amounts relative to PBS. The composite is the result from protocols 2 and 3. A very strong effect was found on the elastic and viscous components of the complex viscosity, which is reflected in the Cole-Cole diagram by a large increase in Newtonian viscosity .sub.0 (extrapolation of the circular arc on the real-number axis). As this Newtonian viscosity is directly proportional to the molecular weight, this translates into an indisputable chain extender effect. Note that for a level of 10%, a threshold of behavior of the gel type is reached by the method of preparation in situ, and independently of the nature of M.

[0237] An LDH material organo-modified with the dodecylsulfate surfactant serves as reference filler for the counter-examples C1, C2 (protocol ex-situ 1&2). The controls T1 and T2 are commercially available PBSs used without filler.

[0238] The LDH/SDS fillers M1 and M2 are used for comparison and are representative of the LDH fillers known from the prior art.

[0239] The mechanical properties (Newtonian viscosity) obtained for a dispersion of 5 wt % of LDH/SDS (comparative examples C1, C2) are equivalent to those obtained without filler (control T2) or else far lower (control T1). The Newtonian viscosity .sub.0 (extrapolation of the circular arc on the real-number axis) is in fact almost equal to that of T2, showing no effect of the addition of fillers on the viscoelasticity of the chains. For the ex-situ protocol, the dispersion has a slightly plasticizing effect with a decrease in Newtonian viscosity .sub.0 relative to the control T1.

[0240] Quantitatively:

[0241] T1 (control): .sub.0=150 Pa.Math.s (at 140 C.),

[0242] C1 (comparative): .sub.0=120 Pa.Math.s (at 140 C.)

[0243] C3 (according to the invention): .sub.0>1000 Pa.Math.s (at 140 C.)

[0244] FIGS. 4 and 5 illustrate the effect of introducing HPPA relative to surfactants such as citric acid (CA), sodium succinate (SU), sodium sebacate (SE), sodium adipate (AD) and ricinoleic acid (RA) in the PBS-LDH.sub.MgAl material. The composites obtained are the result from protocols 2 and 3. It is found that introduction of HPPA is reflected in the Cole-Cole diagram by a large increase in Newtonian viscosity .sub.0 (extrapolation of the circular arc on the real-number axis) relative to the other surfactants.

[0245] The examples illustrate aliphatic polyesters such as poly(butylene succinate), poly(propylene)succinate and poly(butylene succinate-co-adipate). FIGS. 6 and 7 present composite materials comprising an LDH.sub.MgAl organo-modified with variable amounts of HPPA and a polymer matrix such as poly(propylene)succinate or poly(butylene succinate-co-adipate). A very strong effect is found on the elastic and viscous components of the complex viscosity, which is reflected in the Cole-Cole diagram by a large increase in Newtonian viscosity .sub.0 (extrapolation of the circular arc on the real-number axis).