WO2018167201A1 - New branched polymers, their preparation process, and uses thereof - Google Patents

New branched polymers, their preparation process, and uses thereof Download PDF

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Publication number
WO2018167201A1
WO2018167201A1 PCT/EP2018/056500 EP2018056500W WO2018167201A1 WO 2018167201 A1 WO2018167201 A1 WO 2018167201A1 EP 2018056500 W EP2018056500 W EP 2018056500W WO 2018167201 A1 WO2018167201 A1 WO 2018167201A1
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formula
repetitive unit
carbon atoms
polymer
linear
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PCT/EP2018/056500
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French (fr)
Inventor
Didier Pintori
Ludivine DECOENE
Blandine Testud
Etienne GRAU
Henri Cramail
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Pivert
Université De Bordeaux
Iterg
Centre National De La Recherche Scientifique
Institut Polytechnique De Bordeaux
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Priority to EP18709642.5A priority Critical patent/EP3596152A1/en
Publication of WO2018167201A1 publication Critical patent/WO2018167201A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids

Definitions

  • the present invention concerns new branched polymers, and in particular branched polyesters, and their process of preparation.
  • the present invention also concerns new branched polymers susceptible to be obtained according to the process of the invention, as well as uses thereof.
  • Branched polymers belong to a class of synthetic tree-like macromolecules called dendritic polymers (Gao and Yan, 2004). They are polymers with densely branched structure and a large number of end groups. Dendritic polymers include dendrimers which have completely branched star-like topologies and branched polymers which have imperfectly branched or irregular structures.
  • Branched polymers have a wide range of applications. Branched polymers can be used as additives, such as tougheners for thermosets, cross-linking or adhesive agents, dispersers, compatibilizers or rheology modifiers....
  • the aim of the present invention is to provide new branched polymers, and more particularly new renewable branched polymers.
  • the aim of the present invention is also to provide a process of preparation of branched polymers, easy to be implemented.
  • Another aim of the present invention is to provide new branched polymers which are more fluid than those of prior art.
  • Another aim of the present invention is to provide a process of preparation of branched polymers with a control of the functionality of the resulting polymer.
  • the present invention relates to a polymer comprising:
  • - Ai represents H or a linear or branched divalent alkyl group comprising from 1 to 20 carbon atoms, preferably from 2 to 12, and more preferably from 5 to 10;
  • a 2 represents a bond or a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 1 to 10, and more preferably from 1 to 5;
  • a 3 represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 1 to 10, and more preferably from 1 to 5;
  • a 4 represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 2 to 12, and more preferably from 4 to 10;
  • R 1 ; R 2 , R 3 and R 4 are — j or H; at least one of them being H and at least one of them being— j ;
  • - j is 0 or 1 ;
  • i is 0 when j is 1 and j is 0 when i is 1 or 2;
  • a 2 is a bond, when is H and i is 0, and ii) at least one repetitive unit (U) having one of the following formulae (S) or
  • - A-i ' represents H or a linear or branched divalent alkyl group comprising from 1 to 20 carbon atoms, preferably from 2 to 12, and more preferably from 5 to 10;
  • a 2 ' represents a bond or a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 1 to 10, and more preferably from 1 to 5, wherein said alkylene radical may also be interrupted by one or two double bonds;
  • a 3 ' represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 1 to 10, and more preferably from 1 to 5, wherein said alkylene radical may also be interrupted by one or two double bonds, or A 3 ' is a bond;
  • a 4 ' represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 2 to 12, and more preferably from 4 to 10, or A 4 ' is a bond;
  • - k is 0, 1 or 2 and I is 0 or 1 ; k+l being 1 , 2 or 3; and
  • - m is 0 or 1 ; and n is 0 or 1 ; m+n being 1 or 2.
  • the polymers of the invention thus comprise at least one repetitive unit (V) and at least one repetitive unit (U) as defined above.
  • Such polymers may also be named “copolymers” as they comprise at least two distinct repetitive units.
  • the polymer of the invention comprises at least one repetitive unit (V) of formula (T) and at least one repetitive unit (U) of formula (S).
  • V repetitive unit
  • U repetitive unit
  • the inventors advantageously synthesized new renewable branched polymers, more particularly copolymers, from renewable monomers, having interesting properties.
  • the inventors notably developed a facile and efficient process to yield new branched renewable polymers, more particularly copolymers.
  • the polymer or copolymer of the invention comprises at least one repetitive unit (V) having one of the formulae (T), (T) or (T").
  • the polymer of the invention comprises at least one repetitive unit (V) of formula (T) as defined above.
  • V repetitive unit having the following formula (T1 ):
  • a 1 ; A 2 , A 3 and A 4 are as defined above.
  • the polymer according to the invention comprises at least one unit (V) having the following formula (T2):
  • a 1 ; A 2 , A 3 , and A 4 are as defined above;
  • R 2 and R 3 are— j or H, only one of R 2 and R 3 being H.
  • the polymer according to the invention comprises:
  • a 1 ; A 2 , A 3 and A 4 are as defined above.
  • AAccccoorrddiinngg ttoo aann eemmbbooddiimmeenntt,, tthhee ppoollyymmeerr ooff tthhee iinnvveennttiioonn ccoommpprriis seess aatt lleeaasstt oonnee rreeppeettiittiivvee uunniitt ((VV)) hhaavviinngg tthhee ffoorrmmuullaa ((TT33)) aass ddeeffiinneedd aabboovvee..
  • AAccccoorrddiinngg ttoo aann eemmbbooddiimmeenntt,, tthhee ppoollyymmeerr ooff tthhee iinnvveennttiioonn ccoommpprriis seess aatt lleeaasstt oonnee rreeppeettiittiivvee uunniitt ((VV)) hhaavviinngg tthhee ffoorrmmuullaa ((TT44)) aass ddeeffiinneedd aabboovvee..
  • AAccccoorrddiinngg ttoo aann eemmbbooddiimmeenntt,, tthhee ppoollyymmeerr ooff tthhee iinnvveennttiioonn ccoommpprriis seess aatt lleeaasstt oonnee rreeppeettiittiivvee uunniitt ((VV)) hhaavviinngg tthhee ffoorrmmuullaa ((TT33)) aass ddeeffiinneedd aabboovvee aanndd aatt lleeaasstt oonnee rreeppeettiittiivvee ((VV)) hhaavviinngg tthhee foorrmmuullaa ((TT44))
  • the polymer according to the invention comprises at least one unit (V) having the following formula (T5):
  • a 1 ; A 2 , A 3 , and A 4 are as defined above.
  • the repetitive unit (V) has one of the above- mentioned formulae (T1 ), (T2) or (T5).
  • the polymer of the invention further comprises at least repetitive unit (Z) havin the formula (I)
  • a 1 ; A 2 , A 3 , and A 4 are as defined above;
  • R a being selected from the group consisting of: H, a linear or branched alkyl group comprising from 1 to 20 carbon atoms, and an aryl group comprising from 6 to 22 carbon atoms, R a being preferably H or Me.
  • the repetitive unit (Z) has the formula (I) wherein Y is -OMe.
  • the repetitive unit (Z) has the formula (I) wherein Y is -OH.
  • the polymer comprises at least one repetitive unit ( ⁇ ') having the formula (II):
  • a 2 , A 3 , and A 4 are as defined above, and being identical or different;
  • - Y represents -OR a , R a being selected from the group consisting of: H, a linear or branched alkyl group comprising from 1 to 20 carbon atoms, and an aryl group comprising from 6 to 22 carbon atoms.
  • the repetitive unit (Z) has the formula (I) as mentioned above wherein the radical A A 2 - is an alkyl group comprising 8 carbon atoms.
  • the repetitive unit (Z) has the formula (I) as mentioned above wherein the radical A A 2 - is H (A 2 being a bond and being H).
  • the repetitive unit (Z) has the formula (I) as mentioned above wherein the radical -A 3 -A 4 - is an alkylene radical comprising 1 1 carbon atoms.
  • the repetitive unit (Z) has the formula (I) as mentioned above wherein the radical -A 3 -A 4 - is an alkylene radical comprising 8 carbon atoms.
  • the repetitive unit ( ⁇ ') has the formula (II) as mentioned above wherein the radical A A 2 - is an alkyl group comprising 8 carbon atoms.
  • the repetitive unit ( ⁇ ') has the formula (II) as mentioned above wherein the radical A A 2 - is H (A 2 being a bond and being H).
  • the repetitive unit ( ⁇ ') has the formula (II) as mentioned above wherein the radical -A 3 -A 4 - is an alkylene radical comprising 1 1 carbon atoms.
  • the repetitive unit ( ⁇ ') has the formula (II) as mentioned above wherein the radical -A 3 -A 4 - is an alkylene radical comprising 8 carbon atoms.
  • the above-mentioned repetitive unit ( ⁇ ') has the following formula (11-1 ):
  • the repetitive unit ( ⁇ ') has the formula (11-2):
  • repetitive unit ( ⁇ ') has the formula (II-3):
  • the polymer of the invention comprises:
  • the polymer according to the invention comprises:
  • the polymer or copolymer of the invention comprises at least one repetitive unit (U) having one of the formulae (S) or (S').
  • the polymer of the invention comprises at least one repetitive unit (U) of formula (S) as defined above.
  • a ⁇ , ⁇ 2 ', A 3 ' and A 4 ' are as defined above, and wherein the double bond can be cis or trans, preferably cis.
  • the polymer according to the invention comprises at least one unit (U) having the following formula (S2): wherein ⁇ ⁇ 2 ', A 3 ' and A 4 ' are as defined above, and wherein the double bond can be cis or trans, preferably cis.
  • the polymer according to the invention comprises at least one unit (U) having the following formula (S3):
  • a ⁇ , ⁇ 2 ', A 3 ' and A 4 ' are as defined above, and wherein the double bond can be cis or trans, preferably cis.
  • the polymer according to the invention comprises at least one unit (U) having the following formula (S4):
  • ⁇ ⁇ 2 ', A 3 ' and A 4 ' are as defined above, and wherein the double bond can be cis or trans, preferably cis.
  • the polymer according to the invention comprises at least one unit (U) having the following formula (S5): wherein A ⁇ , ⁇ 2 ', A 3 ' and A 4 ' are as defined above, and wherein the double bond can be cis or trans, preferably cis.
  • the polymer according to the invention comprises at least one unit (U) having the following formula (S6): wherein A ⁇ , ⁇ 2 ', A 3 ' and A 4 ' are as defined above, and wherein the double bond can be cis or trans, preferably cis.
  • the polymer of the invention comprises at least one repetitive unit (U) having one of the formulae (S1 ), (S2), (S3), (S4), (S5) or (S6).
  • the polymer of the invention comprises at least one repetitive unit (U) of formula (S2) as defined above.
  • the radical -A' 3 -A' 4 - is an alkylene radical comprising 7 carbon atoms.
  • the radical -A' 2 - is an alkylene radical comprising 1 carbon atom.
  • the radical A' is an alkyl group comprising 6 carbon atoms.
  • the polymer of the invention comprises a repetitive unit having the following formula:
  • the polymer of the invention comprises at least one re etitive unit (W) having one of the following formulae (III) or (IV):
  • a ⁇ , ⁇ 2 ', A 3 ' and A 4 ' are as defined above, and wherein the double bond can be cis or trans, preferably cis.
  • the polymer of the invention comprises:
  • alkyl means a saturated aliphatic hydrocarbon group, which may be straight or branched, having about 1 to about 20 carbon atoms in the chain. Preferred alkyl groups have 1 to about 10 carbon atoms in the chain. The following alkyl groups may be cited as example: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl.
  • alkylene refers to a divalent radical comprising from 1 to 20 carbon atoms, and preferably from 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • radical When said radical is linear, it may be represented by the formula (CH 2 ) k wherein k is an integer varying from 1 to 12, and preferably from 1 to 6.
  • alkylene may be cited as example: methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene.
  • aryl refers to an aromatic monocyclic or bicyclic hydrocarbon ring system having from 6 to 22, preferably 5 to 10, carbons atoms, wherein any ring atom capable of substitution may be substituted by a substituent.
  • aryl moieties include, but are not limited to, phenyl, naphthyl, and anthracenyl.
  • the polymer according to the invention is a branched polymer, in particular a branched polyester, comprising notably a combination of unit(s) (V) and linear unit(s) (U), said units (V) and (U) being as defined above.
  • the branched polymer or copolymer of the invention comprises several polymeric chains corresponding notably to the succession of (V) and (U) units.
  • the different units (V) and (U) are linked to each other through ⁇ which is present on each unit.
  • ⁇ represents a bond which is a link between the different repetitive units of the polymer of the invention.
  • repetitive units of the polymer of the invention comprise -O- moiety(ies) and/or -C(O)- moiety(ies) which are linked together to form ester bonds.
  • one unit (V) may be linked to one unit (U) as follows, through a bond being present on the unit (V) and another which is present on the unit (U), as follows:
  • a 1 ; A 2 , A 3 , A 4 , ⁇ ⁇ 2 ', A 3 ' and A 4 ' are as defined above, and wherein the double bond can be cis or trans, preferably cis.
  • one unit (V) may be linked to two units (U) as follows, through a bond being present on the unit (V) and another which is present on each unit (U), as follows:
  • one unit (V) may be linked to three units (U) as follows, through a bond being present on the unit (V) and another which is present on each unit (U), as follows:
  • the unit (V) is preferably derived from methyl 9,10-dihydroxystearate, and has thus the following formula:
  • the unit (U) is preferably derived from methyl ricinoleate, and has thus the following formula:
  • the polymer according to the invention is a polyester comprising at least one (V) unit as defined above and least one (U) unit as defined above.
  • the present invention also relates to a process for preparing a polymer as defined above, comprising a step of polymerization of at least one monomer of formula (P):
  • R 5 represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms or an aryl radical comprising from 6 to 22 carbon atoms; and at least one monomer of formula (Q):
  • R 6 represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms or an aryl radical comprising from 6 to 22 carbon atoms;
  • a catalyst selected from the group consisting of: Zn(OAc) 2 (anhydrous zinc acetate), Ti(OBu) 4 (titanium butoxide), Ti(OiPr) 4 (titanium isopropoxide), Sb 2 0 3 (antimony (III) oxide), stannous octoate, dibutyltin oxide (DBTO), 7-methyl-1 ,5,7- triazabicyclo(4.4.0)dec-5-ene (m-TBD), and 1 ,5,7-triazabicyclo[4.4.0]dec-5- ene (TBD);
  • a catalyst selected from the group consisting of: Zn(OAc) 2 (anhydrous zinc acetate), Ti(OBu) 4 (titanium butoxide), Ti(OiPr) 4 (titanium isopropoxide), Sb 2 0 3 (antimony (III) oxide), stannous octoate, dibutyltin oxide (DBTO), 7-methyl-1
  • said process optionally comprising a step of recovering said polymer.
  • the catalyst is Zn(OAc) 2 , 1 ,5,7- triazabicyclo[4.4.0]dec-5-ene or stannous octoate.
  • the catalyst is 1 ,5,7-triazabicyclo[4.4.0]dec-5-ene.
  • the catalyst is Zn(OAc) 2 .
  • the amount of catalyst is comprised from 0.05% to 10%, preferably from 0.5% to 5%, more preferably from 1 % to 2%, and even more preferably from 1 .2% to 1 .8%, by weight relative to the weight of the monomer of formula (P) as defined above.
  • the monomer of formula (P) has the formula (P-1 ):
  • a 1 ; A 2 , A 3 , A 4 , and R 5 are as defined above.
  • the monomer of formula (P) is preferably methyl 9,10-dihydroxystearate.
  • the monomer of formula (Q) has the formula (Q-1 ):
  • ⁇ ⁇ 2 ', ⁇ 3 ', A 4 ', and R 6 are as defined above.
  • the monomer of formula (Q) is preferably methyl ricinoleate.
  • the polymerization of the monomers is a bulk polymerization.
  • bulk polymerization also known as “mass polymerization” means a polymerization carried out in the absence of solvent or dispersant.
  • the polymerization step is carried out by heating the monomers of formulae (P) and (Q) as defined above, in the presence of the catalyst, at a temperature ⁇ comprised from 90°C to 130°C for 1 hour to 48 hours, then by heating further at a temperature T 2 comprised from 90°C, preferably from 140°C, to 180°C for 1 hour to 48 hours.
  • the temperatures ⁇ and T 2 are different.
  • the polymerization step is carried out by heating the monomers as defined above in the presence of the catalyst, at a temperature ⁇ comprised from 90°C, preferably from 100°C, to 120°C for 1 hour to 48 hours, preferably for 1 to 10 hours, then by heating further at a temperature T 2 comprised from 90°C, preferably from 160°C to 170°C for 1 hour to 48 hours, preferably for 10 to 20 hours.
  • the polymerization step is carried out by heating the monomers as defined above in the presence of the catalyst, at a temperature ⁇ comprised from 90°C, preferably from 100°C, to 120°C for 1 hour to 3 hours, then by heating further at a temperature T 2 comprised from 90°C, preferably from 160°C, to 170°C for about 13 hours.
  • the polymerization step is carried out under nitrogen at a temperature ⁇ comprised from 90°C to 130°C.
  • the polymerization step is further heated at a temperature T 2 comprised from 90°C, preferably from 140°C, to 180°C under dynamic vacuum.
  • the process of the invention comprises two heating steps, a first step being carried out at a temperature ⁇ comprised from 90°C, preferably from 100°C, to 120°C for 1 hour to 48 hours, and then a second step being carried out at a temperature T 2 comprised from 90°C, preferably from 160°C, to 170°C for 1 hour to 48 hours.
  • an intermediate oligomer is obtained which is then further heated in order to obtain the polymer of the invention.
  • the process is a one-pot process, and in particular a two- steps one-pot process.
  • the term "one-pot process” means a process wherein two or more reactions are conducted in a single reaction vessel without isolating or purifying the resulting intermediate(s).
  • the intermediate oligomer is obtained after the first heating step of the monomers at a temperature ⁇ comprised from 90°C to 130°C and the second heating step at a temperature T 2 comprised from 90°C, preferably from 140°C, to 180°C.
  • the present invention also relates to a polymer susceptible to be obtained according to the process as defined above.
  • Example 1 Preparation of a copolymer from monomers methyl 9,10- dihydroxystearate and methyl ricinoleate (50/50)
  • Methyl 9,10-dihydroxystearate (AB2)(15 g, 45.4 mmol) and methyl ricinoleate (AB)(14.2 g, 45.4 mmol) were introduced into a 250 mL three-necked flask equipped with a thermocouple, a condenser and connected to a vacuum pump. The mixture is magnetically stirred under vacuum (2 mbar) at 90°C for 1 hour.
  • the flask is then heated gradually to 120°C under nitrogen for 2 hours, then 160°C for 2 hours, gradually decreasing the vacuum to 1 mbar.
  • the reaction medium is then heated at 180°C for further 2 hours under a vacuum of 1 mbar.
  • the reactor After reacting for 6 hours, the reactor is cooled to below 100°C and 200 ml of toluene are added to the reaction medium in order to fluidize it.
  • the mixture is cooled to ambient temperature and the organic phase is washed with water until the neutrality of the washings is reached.
  • Toluene and traces of water are removed by vacuum distillation of toluene (toluene / water azeotrope).
  • the obtained polymer has a highly viscous appearance at room temperature.
  • the yield is greater than 90%.
  • IOH being the hydroxyl value which is defined as the number of milligrams of potassium hydroxide required to neutralize the acetic acid taken up on acetylation of one gram of a chemical substance that contains free hydroxyl groups,
  • IA being the acid value (or "neutralization number” or “acid number” or “acidity”) which is the mass of potassium hydroxide (KOH) in milligrams that is required to neutralize one gram of chemical substance, and
  • D being the density of the substance, which is its mass per unit volume.

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Abstract

The present invention relates to a polymer comprising: i) at least one repetitive unit (V) having one of the following formulae (T) and ii) at least one repetitive unit (U) having one of the following formulae (S).

Description

NEW BRANCHED POLYMERS, THEIR PREPARATION PROCESS, AND USES THEREOF
The present invention concerns new branched polymers, and in particular branched polyesters, and their process of preparation.
The present invention also concerns new branched polymers susceptible to be obtained according to the process of the invention, as well as uses thereof.
Over the last decades, branched polymers have attracted a growing interest because of their unique architecture.
Branched polymers belong to a class of synthetic tree-like macromolecules called dendritic polymers (Gao and Yan, 2004). They are polymers with densely branched structure and a large number of end groups. Dendritic polymers include dendrimers which have completely branched star-like topologies and branched polymers which have imperfectly branched or irregular structures.
Branched polymers have a wide range of applications. Branched polymers can be used as additives, such as tougheners for thermosets, cross-linking or adhesive agents, dispersers, compatibilizers or rheology modifiers....
There is a need for new branched polymers, and more particularly for new renewable branched polymers.
The aim of the present invention is to provide new branched polymers, and more particularly new renewable branched polymers.
The aim of the present invention is also to provide a process of preparation of branched polymers, easy to be implemented.
Another aim of the present invention is to provide new branched polymers which are more fluid than those of prior art.
Another aim of the present invention is to provide a process of preparation of branched polymers with a control of the functionality of the resulting polymer. Thus, the present invention relates to a polymer comprising:
i) at least one repetitive unit (V) having one of the following formulae (T), (T)):
Figure imgf000003_0001
wherein:
- Ai represents H or a linear or branched divalent alkyl group comprising from 1 to 20 carbon atoms, preferably from 2 to 12, and more preferably from 5 to 10;
- A2 represents a bond or a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 1 to 10, and more preferably from 1 to 5;
- A3 represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 1 to 10, and more preferably from 1 to 5;
- A4 represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 2 to 12, and more preferably from 4 to 10;
- R1 ; R2, R3 and R4 are — j or H; at least one of them being H and at least one of them being— j ;
- i is 0, 1 or 2;
- j is 0 or 1 ;
wherein i is 0 when j is 1 and j is 0 when i is 1 or 2;
and wherein A2 is a bond, when is H and i is 0, and ii) at least one repetitive unit (U) having one of the following formulae (S) or
(S') :
Figure imgf000004_0001
the double bond -CH=CH- in formulae (S) and (S') being either cis or trans, wherein:
- A-i ' represents H or a linear or branched divalent alkyl group comprising from 1 to 20 carbon atoms, preferably from 2 to 12, and more preferably from 5 to 10;
- A2' represents a bond or a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 1 to 10, and more preferably from 1 to 5, wherein said alkylene radical may also be interrupted by one or two double bonds;
- A3' represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 1 to 10, and more preferably from 1 to 5, wherein said alkylene radical may also be interrupted by one or two double bonds, or A3' is a bond;
- A4' represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 2 to 12, and more preferably from 4 to 10, or A4' is a bond;
- k is 0, 1 or 2 and I is 0 or 1 ; k+l being 1 , 2 or 3; and
- m is 0 or 1 ; and n is 0 or 1 ; m+n being 1 or 2.
The polymers of the invention thus comprise at least one repetitive unit (V) and at least one repetitive unit (U) as defined above. Such polymers may also be named "copolymers" as they comprise at least two distinct repetitive units.
According to a preferred embodiment, the polymer of the invention comprises at least one repetitive unit (V) of formula (T) and at least one repetitive unit (U) of formula (S). The inventors advantageously synthesized new renewable branched polymers, more particularly copolymers, from renewable monomers, having interesting properties. The inventors notably developed a facile and efficient process to yield new branched renewable polymers, more particularly copolymers.
Repetitive unit (V)
As mentioned above, the polymer or copolymer of the invention comprises at least one repetitive unit (V) having one of the formulae (T), (T) or (T").
According to an embodiment, the polymer of the invention comprises at least one repetitive unit (V) of formula (T) as defined above.
Preferably, it comprises a repetitive unit (V) having the following formula (T1 ):
Figure imgf000005_0001
wherein A1 ; A2, A3 and A4 are as defined above.
A unit having formula (T1 ) corresponds to a unit having formula (T) as mentioned above, wherein i=j=0.
In one embodiment, the polymer according to the invention comprises at least one unit (V) having the following formula (T2):
Figure imgf000005_0002
wherein:
- A1 ; A2, A3, and A4 are as defined above; and
- R2 and R3 are— j or H, only one of R2 and R3 being H.
A unit having formula (T2) corresponds to a unit having formula (T) as mentioned above, wherein i=j=0.
In one embodiment, the polymer according to the invention comprises:
- at least one repetitive unit (V) having the following formula (T3):
Figure imgf000005_0003
(T3) and/or
at least one repetitive unit (V) having the following formula (T4)
Figure imgf000006_0001
wherein A1 ; A2, A3 and A4 are as defined above.
AAccccoorrddiinngg ttoo aann eemmbbooddiimmeenntt,, tthhee ppoollyymmeerr ooff tthhee iinnvveennttiioonn ccoommpprriisseess aatt lleeaasstt oonnee rreeppeettiittiivvee uunniitt ((VV)) hhaavviinngg tthhee ffoorrmmuullaa ((TT33)) aass ddeeffiinneedd aabboovvee..
AAccccoorrddiinngg ttoo aann eemmbbooddiimmeenntt,, tthhee ppoollyymmeerr ooff tthhee iinnvveennttiioonn ccoommpprriisseess aatt lleeaasstt oonnee rreeppeettiittiivvee uunniitt ((VV)) hhaavviinngg tthhee ffoorrmmuullaa ((TT44)) aass ddeeffiinneedd aabboovvee..
AAccccoorrddiinngg ttoo aann eemmbbooddiimmeenntt,, tthhee ppoollyymmeerr ooff tthhee iinnvveennttiioonn ccoommpprriisseess aatt lleeaasstt oonnee rreeppeettiittiivvee uunniitt ((VV)) hhaavviinngg tthhee ffoorrmmuullaa ((TT33)) aass ddeeffiinneedd aabboovvee aanndd aatt lleeaasstt oonnee rreeppeettiittiivvee ((VV)) hhaavviinngg tthhee ffoorrmmuullaa ((TT44)) aass ddeeffiinneedd aabboovvee..
AA uunniitt hhaavviinngg ffoorrmmuullaa ((TT33)) ccoorrrreessppoonnddss ttoo aa uunniitt hhaavviinngg ffoorrmmuullaa ((TT22)) aass mmeennttiioonneedd aabboovvee,, wwhheerreeiinn RR33==HH aanndd RR22==
A unit having formula (T4) corres ds to a unit having formula (T2) as mentioned above, wherein R2=H and R3= .
Figure imgf000006_0002
In one embodiment, the polymer according to the invention comprises at least one unit (V) having the following formula (T5):
Figure imgf000006_0003
wherein A1 ; A2, A3, and A4 are as defined above.
According to an embodiment, the repetitive unit (V) has one of the above- mentioned formulae (T1 ), (T2) or (T5). In one embodiment, the polymer of the invention further comprises at least repetitive unit (Z) havin the formula (I)
Figure imgf000007_0001
wherein:
- A1 ; A2, A3, and A4 are as defined above; and
- Y represents -ORa, Ra being selected from the group consisting of: H, a linear or branched alkyl group comprising from 1 to 20 carbon atoms, and an aryl group comprising from 6 to 22 carbon atoms, Ra being preferably H or Me.
In one embodiment, in the polymer according to the invention, the repetitive unit (Z) has the formula (I) wherein Y is -OMe.
In one embodiment, in the polymer according to the invention, the repetitive unit (Z) has the formula (I) wherein Y is -OH.
According to an embodiment, the polymer comprises at least one repetitive unit (Ζ') having the formula (II):
Figure imgf000007_0002
wherein:
- A1 ; A2, A3, and A4 are as defined above, and being identical or different; and
- Y represents -ORa, Ra being selected from the group consisting of: H, a linear or branched alkyl group comprising from 1 to 20 carbon atoms, and an aryl group comprising from 6 to 22 carbon atoms. In one embodiment, the repetitive unit (Z) has the formula (I) as mentioned above wherein the radical A A2- is an alkyl group comprising 8 carbon atoms.
In one embodiment, the repetitive unit (Z) has the formula (I) as mentioned above wherein the radical A A2- is H (A2 being a bond and being H).
In one embodiment, the repetitive unit (Z) has the formula (I) as mentioned above wherein the radical -A3-A4- is an alkylene radical comprising 1 1 carbon atoms.
In one embodiment, the repetitive unit (Z) has the formula (I) as mentioned above wherein the radical -A3-A4- is an alkylene radical comprising 8 carbon atoms.
In one embodiment, the repetitive unit (Ζ') has the formula (II) as mentioned above wherein the radical A A2- is an alkyl group comprising 8 carbon atoms.
In one embodiment, the repetitive unit (Ζ') has the formula (II) as mentioned above wherein the radical A A2- is H (A2 being a bond and being H).
In one embodiment, the repetitive unit (Ζ') has the formula (II) as mentioned above wherein the radical -A3-A4- is an alkylene radical comprising 1 1 carbon atoms.
In one embodiment, the repetitive unit (Ζ') has the formula (II) as mentioned above wherein the radical -A3-A4- is an alkylene radical comprising 8 carbon atoms.
In one embodiment, the above-mentioned repetitive unit (Ζ') has the following formula (11-1 ):
Figure imgf000008_0001
(11-1 )
Such repetitive unit corresponds to a repetitive unit of formula (II) as defined above wherein Y=OMe, the radical -A3-A4- is an alkylene radical comprising 7 carbon atoms, and the radical A A2- is an alkyl group comprising 8 carbon atoms. In one embodiment the repetitive unit (Ζ') has the formula (11-2):
Figure imgf000009_0001
Such repetitive unit corresponds to a repetitive unit of formula (II) as defined above wherein Y=OMe, the radical -A3-A4- is an alkylene radical comprising 1 1 carbon atoms, and the radical A A2- is an alkyl group comprising 8 carbon atoms.
In one embodiment the repetitive unit (Ζ') has the formula (II-3):
Figure imgf000009_0002
Such repetitive unit corresponds to a repetitive unit of formula (II) as defined above wherein Y=OMe, the radical -A3-A4- is an alkylene radical comprising 8 carbon atoms, and the radical A A2- is H.
According to an embodiment, the polymer of the invention comprises:
- at least one repetitive unit (V) having the formula (T1 ) as defined above;
- at least one repetitive unit (V) having the formula (T2) as defined above;
- at least one repetitive unit (V) having the formula (T5) as defined above; and
- optionally at least one repetitive unit (Ζ') having the formula (II) as defined above. In one embodiment, the polymer according to the invention comprises:
- at least one repetitive unit (V) having the formula (T1 ) as defined above;
- at least one repetitive unit (V) having the formula (T2) as defined above;
- at least one repetitive unit (V) having the formula (T3) as defined above;
- at least one repetitive unit (V) having the formula (T4) as defined above;
- at least one repetitive unit (V) having the formula (T5) as defined above; and
- optionally at least one repetitive unit (Ζ') having the formula (II) as defined above, in particular having the formula (11-1 ), (II-2) or (II-3).
Repetitive unit (U)
As mentioned above, the polymer or copolymer of the invention comprises at least one repetitive unit (U) having one of the formulae (S) or (S').
According to an embodiment, the polymer of the invention comprises at least one repetitive unit (U) of formula (S) as defined above.
Preferably, it comprises a repetitive unit (U) having the following formula (S1 ):
Figure imgf000010_0001
wherein A^, Α2', A3' and A4' are as defined above, and wherein the double bond can be cis or trans, preferably cis.
A unit having formula (S1 ) corresponds to a unit having formula (S) as mentioned above, wherein k=1 and l=0.
In one embodiment, the polymer according to the invention comprises at least one unit (U) having the following formula (S2):
Figure imgf000010_0002
wherein Α Α2', A3' and A4' are as defined above, and wherein the double bond can be cis or trans, preferably cis.
A unit having formula (S2) corresponds to a unit having formula (S') as mentioned above, wherein m=1 and n=0. In one embodiment, the polymer according to the invention comprises at least one unit (U) having the following formula (S3):
Figure imgf000011_0001
wherein A^, Α2', A3' and A4' are as defined above, and wherein the double bond can be cis or trans, preferably cis.
A unit having formula (S3) corresponds to a unit having formula (S) as mentioned above, wherein k=l=1 .
In one embodiment, the polymer according to the invention comprises at least one unit (U) having the following formula (S4):
Figure imgf000011_0002
wherein Α Α2', A3' and A4' are as defined above, and wherein the double bond can be cis or trans, preferably cis.
A unit having formula (S4) corresponds to a unit having formula (S) as mentioned above, wherein k=0 and 1=1 .
In one embodiment, the polymer according to the invention comprises at least one unit (U) having the following formula (S5):
Figure imgf000011_0003
wherein A^, Α2', A3' and A4' are as defined above, and wherein the double bond can be cis or trans, preferably cis.
A unit having formula (S5) corresponds to a unit having formula (S') as mentioned above, wherein m=0 and n=1 . In one embodiment, the polymer according to the invention comprises at least one unit (U) having the following formula (S6):
Figure imgf000012_0001
wherein A^, Α2', A3' and A4' are as defined above, and wherein the double bond can be cis or trans, preferably cis.
A unit having formula (S6) corresponds to a unit having formula (S') as mentioned above, wherein m=n=1 .
According to an embodiment, the polymer of the invention comprises at least one repetitive unit (U) having one of the formulae (S1 ), (S2), (S3), (S4), (S5) or (S6).
In the above formulae (S), (S'), (S1 ), (S2), (S3), (S4), (S5), and (S6), the double bond (group -CH=CH-) may be cis or trans, and is preferably cis.
According to an embodiment, the polymer of the invention comprises at least one repetitive unit (U) of formula (S2) as defined above.
Preferably, in formula (S2), the radical -A'3-A'4- is an alkylene radical comprising 7 carbon atoms.
Preferably, in formula (S2), the radical -A'2- is an alkylene radical comprising 1 carbon atom.
Preferably, in formula (S2), the radical A' is an alkyl group comprising 6 carbon atoms.
According to an embodiment, the polymer of the invention comprises a repetitive unit having the following formula:
Figure imgf000012_0002
According to an embodiment, the polymer of the invention comprises at least one re etitive unit (W) having one of the following formulae (III) or (IV):
Figure imgf000013_0001
wherein A^, Α2', A3' and A4' are as defined above, and wherein the double bond can be cis or trans, preferably cis.
According to an embodiment, the polymer of the invention comprises:
at least one repetitive unit U) having the formula (S1 ) as defined above; at least one repetitive unit U) having the formula (S2) as defined above; at least one repetitive unit U) having the formula (S3) as defined above; at least one repetitive unit U) having the formula (S4) as defined above; at least one repetitive unit U) having the formula (S5) as defined above; at least one repetitive unit (U) having the formula (S6) as defined above; and - optionally at least one repetitive unit (W) having the formula (III) or (IV) as defined above.
As used herein, the term "alkyl" means a saturated aliphatic hydrocarbon group, which may be straight or branched, having about 1 to about 20 carbon atoms in the chain. Preferred alkyl groups have 1 to about 10 carbon atoms in the chain. The following alkyl groups may be cited as example: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl.
As used herein, the term "alkylene" (or "alkylidene") refers to a divalent radical comprising from 1 to 20 carbon atoms, and preferably from 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms. When said radical is linear, it may be represented by the formula (CH2)k wherein k is an integer varying from 1 to 12, and preferably from 1 to 6. The following alkylene may be cited as example: methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene. As used herein, the term "aryl" refers to an aromatic monocyclic or bicyclic hydrocarbon ring system having from 6 to 22, preferably 5 to 10, carbons atoms, wherein any ring atom capable of substitution may be substituted by a substituent. Examples of aryl moieties include, but are not limited to, phenyl, naphthyl, and anthracenyl.
As used herein, the polymer according to the invention is a branched polymer, in particular a branched polyester, comprising notably a combination of unit(s) (V) and linear unit(s) (U), said units (V) and (U) being as defined above.
The branched polymer or copolymer of the invention comprises several polymeric chains corresponding notably to the succession of (V) and (U) units.
In particular, in the polymer according to the invention, the different units (V) and (U) are linked to each other through \ which is present on each unit.
In the present invention, ^ represents a bond which is a link between the different repetitive units of the polymer of the invention.
In particular, the repetitive units of the polymer of the invention comprise -O- moiety(ies) and/or -C(O)- moiety(ies) which are linked together to form ester bonds.
In particular, the— o-j moiety in one unit (V) or (U) is linked to a-c-^ moiety in another unit. °
For example, one unit (V) may be linked to one unit (U) as follows, through a bond being present on the unit (V) and another which is present on the unit (U), as follows:
Figure imgf000014_0001
Figure imgf000015_0001
wherein A1 ; A2, A3, A4, Α Α2', A3' and A4' are as defined above, and wherein the double bond can be cis or trans, preferably cis.
For example, one unit (V) may be linked to two units (U) as follows, through a bond being present on the unit (V) and another which is present on each unit (U), as follows:
Figure imgf000015_0002
For example, one unit (V) may be linked to three units (U) as follows, through a bond being present on the unit (V) and another which is present on each unit (U), as follows:
Figure imgf000016_0001
In one preferred embodiment of the invention, the unit (V) is preferably derived from methyl 9,10-dihydroxystearate, and has thus the following formula:
Figure imgf000016_0002
Figure imgf000016_0003
Figure imgf000017_0001
In one preferred embodiment of the invention, the unit (U) is preferably derived from methyl ricinoleate, and has thus the following formula:
Figure imgf000017_0002
In one preferred embodiment of the invention, the polymer according to the invention is a polyester comprising at least one (V) unit as defined above and least one (U) unit as defined above.
Figure imgf000018_0001
Figure imgf000019_0001
The present invention also relates to a process for preparing a polymer as defined above, comprising a step of polymerization of at least one monomer of formula (P):
Figure imgf000019_0002
wherein:
- i, j, A1 ; A2, A3, and A4 are as defined above; and
- R5 represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms or an aryl radical comprising from 6 to 22 carbon atoms; and at least one monomer of formula (Q):
Figure imgf000019_0003
wherein:
- k, I, Α Α2', A3', and A4' are as defined above; and
- R6 represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms or an aryl radical comprising from 6 to 22 carbon atoms;
said step being carried out in the presence of a catalyst selected from the group consisting of: Zn(OAc)2 (anhydrous zinc acetate), Ti(OBu)4 (titanium butoxide), Ti(OiPr)4 (titanium isopropoxide), Sb203 (antimony (III) oxide), stannous octoate, dibutyltin oxide (DBTO), 7-methyl-1 ,5,7- triazabicyclo(4.4.0)dec-5-ene (m-TBD), and 1 ,5,7-triazabicyclo[4.4.0]dec-5- ene (TBD);
said process optionally comprising a step of recovering said polymer.
According to a preferred embodiment, the catalyst is Zn(OAc)2, 1 ,5,7- triazabicyclo[4.4.0]dec-5-ene or stannous octoate.
In one embodiment, in the process according to the invention, the catalyst is 1 ,5,7-triazabicyclo[4.4.0]dec-5-ene.
In one embodiment, in the process according to the invention, the catalyst is Zn(OAc)2.
In one embodiment, the amount of catalyst is comprised from 0.05% to 10%, preferably from 0.5% to 5%, more preferably from 1 % to 2%, and even more preferably from 1 .2% to 1 .8%, by weight relative to the weight of the monomer of formula (P) as defined above.
In one embodiment, the monomer of formula (P) has the formula (P-1 ):
Figure imgf000020_0001
wherein A1 ; A2, A3, A4, and R5 are as defined above.
The monomer of formula (P) is preferably methyl 9,10-dihydroxystearate.
In one embodiment, the monomer of formula (Q) has the formula (Q-1 ):
Figure imgf000020_0002
wherein Α Α2', Α3', A4', and R6 are as defined above.
The monomer of formula (Q) is preferably methyl ricinoleate.
In one embodiment, the polymerization of the monomers is a bulk polymerization. As used herein, the term "bulk polymerization" also known as "mass polymerization" means a polymerization carried out in the absence of solvent or dispersant.
In one embodiment, the polymerization step is carried out by heating the monomers of formulae (P) and (Q) as defined above, in the presence of the catalyst, at a temperature ΤΊ comprised from 90°C to 130°C for 1 hour to 48 hours, then by heating further at a temperature T2 comprised from 90°C, preferably from 140°C, to 180°C for 1 hour to 48 hours.
Preferably, the temperatures ΤΊ and T2 are different.
In one embodiment, the polymerization step is carried out by heating the monomers as defined above in the presence of the catalyst, at a temperature ΤΊ comprised from 90°C, preferably from 100°C, to 120°C for 1 hour to 48 hours, preferably for 1 to 10 hours, then by heating further at a temperature T2 comprised from 90°C, preferably from 160°C to 170°C for 1 hour to 48 hours, preferably for 10 to 20 hours.
In one embodiment, the polymerization step is carried out by heating the monomers as defined above in the presence of the catalyst, at a temperature ΤΊ comprised from 90°C, preferably from 100°C, to 120°C for 1 hour to 3 hours, then by heating further at a temperature T2 comprised from 90°C, preferably from 160°C, to 170°C for about 13 hours.
In one embodiment, the polymerization step is carried out under nitrogen at a temperature ΤΊ comprised from 90°C to 130°C.
In one embodiment, the polymerization step is further heated at a temperature T2 comprised from 90°C, preferably from 140°C, to 180°C under dynamic vacuum.
In a preferred embodiment, the process of the invention comprises two heating steps, a first step being carried out at a temperature ΤΊ comprised from 90°C, preferably from 100°C, to 120°C for 1 hour to 48 hours, and then a second step being carried out at a temperature T2 comprised from 90°C, preferably from 160°C, to 170°C for 1 hour to 48 hours.
At the end of the first heating step, an intermediate oligomer is obtained which is then further heated in order to obtain the polymer of the invention. In one embodiment, the process is a one-pot process, and in particular a two- steps one-pot process.
As used herein, the term "one-pot process" means a process wherein two or more reactions are conducted in a single reaction vessel without isolating or purifying the resulting intermediate(s). For example, the intermediate oligomer is obtained after the first heating step of the monomers at a temperature ΤΊ comprised from 90°C to 130°C and the second heating step at a temperature T2 comprised from 90°C, preferably from 140°C, to 180°C.
The present invention also relates to a polymer susceptible to be obtained according to the process as defined above.
EXAMPLES
Example 1 : Preparation of a copolymer from monomers methyl 9,10- dihydroxystearate and methyl ricinoleate (50/50)
Methyl 9,10-dihydroxystearate (AB2)(15 g, 45.4 mmol) and methyl ricinoleate (AB)(14.2 g, 45.4 mmol) were introduced into a 250 mL three-necked flask equipped with a thermocouple, a condenser and connected to a vacuum pump. The mixture is magnetically stirred under vacuum (2 mbar) at 90°C for 1 hour.
Under nitrogen, sodium methanolate (0.3 g, 1 %, 5.5 mmol) is added to the reaction mixture and the flask is made inert.
The flask is then heated gradually to 120°C under nitrogen for 2 hours, then 160°C for 2 hours, gradually decreasing the vacuum to 1 mbar. The reaction medium is then heated at 180°C for further 2 hours under a vacuum of 1 mbar.
After reacting for 6 hours, the reactor is cooled to below 100°C and 200 ml of toluene are added to the reaction medium in order to fluidize it.
The mixture is cooled to ambient temperature and the organic phase is washed with water until the neutrality of the washings is reached.
Toluene and traces of water are removed by vacuum distillation of toluene (toluene / water azeotrope).
The obtained polymer has a highly viscous appearance at room temperature.
The yield is greater than 90%.
The above protocol is applied with different amounts and ratios of both monomers.
AB2 AB Mn Mw IOH IA
D Tg(°C)
(%mol) (%mol) (g/mol) (g/mol) (mgKOH/g) (mgKOH/g)
10 90 4,365 14,442 3.3 -71 .0 22.2 4.67
20 80 4,312 18,099 4.2 -69.0 66.1 1 .91
30 70 5,632 24,191 4.3 -64.8 82.5 3.95
50 50 7,246 36,075 5.0 -54.9 1 13.4 1 .87
90 10 7,665 39,248 5.1 -33.0 165 5.45 Tg being the glass transition temperature,
IOH being the hydroxyl value which is defined as the number of milligrams of potassium hydroxide required to neutralize the acetic acid taken up on acetylation of one gram of a chemical substance that contains free hydroxyl groups,
IA being the acid value (or "neutralization number" or "acid number" or "acidity") which is the mass of potassium hydroxide (KOH) in milligrams that is required to neutralize one gram of chemical substance, and
D being the density of the substance, which is its mass per unit volume.

Claims

1. A polymer comprising:
i) at least one repetitive unit (V) having one of the following formulae (T), (T) or (T-):
Figure imgf000025_0001
wherein:
- Ai represents H or a linear or branched divalent alkyl group comprising from 1 to 20 carbon atoms;
- A2 represents a bond or a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms;
- A3 represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms;
- A4 represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms;
- R1 ; R2, R3 and R4 are — j or H; at least one of them being H and at least one of them being— j;
- i is 0, 1 or 2;
- j is 0 or 1 ;
wherein i is 0 when j is 1 and j is 0 when i is 1 or 2;
and wherein A2 is a bond, when is H and i is 0, and least one repetitive unit (U) having one of the following formulae (S)
(S') :
Figure imgf000026_0001
the double bond -CH=CH- in formulae (S) and (S') being either c/'s or trans, wherein:
- A-i ' represents H or a linear or branched divalent alkyl group comprising from 1 to 20 carbon atoms, preferably from 2 to 12, and more preferably from 5 to 10;
- A2' represents a bond or a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 1 to 10, and more preferably from 1 to 5, wherein said alkylene radical may also be interrupted by one or two double bonds;
- A3' represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 1 to 10, and more preferably from 1 to 5, wherein said alkylene radical may also be interrupted by one or two double bonds, or A3' is a bond;
- A4' represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 2 to 12, and more preferably from 4 to 10, or A4' is a bond;
- k is 0, 1 or 2 and I is 0 or 1 ; k+l being 1 , 2 or 3; and
- m is 0 or 1 ; and n is 0 or 1 ; m+n being 1 or 2.
2. The polymer of claim 1 , comprising at least one repetitive unit (V) of formula (T) and at least one repetitive unit (U) of formula (S).
3. The polymer of claim 1 or 2, wherein the repetitive unit (V) has one of the following formulae (T1 ), (T2) or (T5):
Figure imgf000027_0001
wherein A1 ; A2, A3, A4, R2, and R3 are as defined in claim 1 .
4. The polymer of any one of claims 1 to 3, wherein the repetitive unit (U) has the one of the following formulae (S1 ), (S2), (S3), (S4), (S5) or (S6):
Figure imgf000027_0002
(S5)
Figure imgf000028_0001
wherein A^, A2\ A3' and A4' are as defined in claim 1 .
5. The polymer of any one of claims 1 to 4, further comprising at least one repetitive unit (Z) havin the formula (I):
Figure imgf000028_0002
wherein:
- A1 ; A2, A3, and A4 are as defined in claim 1 ; and
- Y represents -0Ra, Ra being selected from the group consisting of: H, a linear or branched alkyl group comprising from 1 to 20 carbon atoms, and an aryl group comprising from 6 to 22 carbon atoms.
6. The polymer of any one of claims 1 to 5, further comprising at least one repetitive unit (Ζ') having the formula (II):
Figure imgf000028_0003
wherein:
- A1 ; A2, A3, and A4 are as defined in claim 1 ; and
- Y represents -ORa, Ra being selected from the group consisting of: H, a linear or branched alkyl group comprising from 1 to 20 carbon atoms, and an aryl group comprising from 6 to 22 carbon atoms.
7. The polymer of any one of claims 1 to 6, comprising:
- at least one repetitive unit (V) having the formula (T1 ) as defined in claim 3;
- at least one repetitive unit (V) having the formula (T2) as defined in claim 3;
- at least one repetitive unit (V) having the formula (T5) as defined in claim 3;
- and optionally at least one repetitive unit (Ζ') having the formula (II) as defined in claim 6.
8. The polymer of any one of claims 1 to 7, further comprising at least one re etitive unit (W) having one of the following formulae (III) or (IV):
Figure imgf000029_0001
wherein Α Α2', A3' and A4' are as defined in claim 1.
9. The polymer of any one of claims 1 to 8, comprising:
at least one repetitive unit (U) having the formula (S1 ) as defined in claim 4; at least one repetitive unit (U) having the formula (S2) as defined in claim 4; at least one repetitive unit (U) having the formula (S3) as defined in claim 4; at least one repetitive unit (U) having the formula (S4) as defined in claim 4; at least one repetitive unit (U) having the formula (S5) as defined in claim 4; at least one repetitive unit (U) having the formula (S6) as defined in claim 4; - and optionally at least one repetitive unit (W) having the formula (III) or (IV) as defined in claim 8.
10. A process for preparing a polymer of any one of claims comprising a step of polymerization of at least one monomer of formula (P)
Figure imgf000029_0002
wherein: - i, j, A1 ; A2, A3, and A4 are as defined in claim 1 ; and
- R5 represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms or an aryl radical comprising from 6 to 22 carbon atoms; and at least one monomer of formula (Q):
Figure imgf000030_0001
wherein:
- k, I, Α-ι ', Α2', A3' and A4' are as defined in claim 1 ; and
- R6 represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms or an aryl radical comprising from 6 to 22 carbon atoms; said step being carried out in the presence of a catalyst selected from the group consisting of: Zn(OAc)2, Ti(OBu)4, Ti(OiPr)4, Sb203, stannous octoate, dibutyltin oxide, 7-methyl-1 ,5,7-triazabicyclo(4.4.0)dec-5-ene, and 1 ,5,7- triazabicyclo[4.4.0]dec-5-ene;
said process optionally comprising a step of recovering said polymer.
11. The process of claim 10, wherein the catalyst is Zn(OAc)2, 1 ,5,7- triazabicyclo[4.4.0]dec-5-ene or stannous octoate.
12. The process according to claim 10 or 1 1 , wherein the amount of catalyst is comprised from 0.05% to 10% by weight relative to the weight of the monomer of formula (IV).
13. The process according to any one of claims 10 to 12, wherein the polymerization step is carried out by heating the monomers of formulae (V) and (VI) as defined in claim 10, in the presence of the catalyst, at a temperature
Figure imgf000030_0002
comprised from 90°C to 130°C for 1 hour to 48 hours, then by heating further at a temperature T2 comprised from 90°C to 180°C for 1 hour to 48 hours.
14. A polymer susceptible to be obtained according to the process according to any one of claims 10 to 13.
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EP2213694A1 (en) * 2007-09-04 2010-08-04 Keio University 12-hydroxystearic acid copolymer and method for producing the same
WO2016059230A1 (en) * 2014-10-16 2016-04-21 Pivert New branched polymers, their preparation process, and uses thereof

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