Phenolic polymers and preparation processes thereof

The present invention concerns the use of a compound having the following formula (I), for the preparation of a polymer. The present invention also concerns the polymers obtained from polymerization of compound of formula (I), and their processes of preparation.

This application is a § 371 National Stage Application of PCT International Application No. PCT/EP2015/072958, filed Oct. 5, 2015 claiming priority of European Patent Application No. 14306563.9, filed Oct. 3, 2014, the entire contents of each are incorporated by reference.

The present invention concerns the use of specific phenolic monomers for the preparation of polymers.

The present invention also relates to new phenolic polymers, in particular polyesters, polyamides, epoxy resins and unsaturated polyesters, and preparation processes thereof.

Aromatic compounds constitute basic chemicals to manufacture everyday life items. Indeed, they play a key role in pharmaceutical, perfumes, dyestuff and polymer industries. In plastic industry, aromatic units offer rigidity, hydrophobicity and fire resistance to the derived polymers. Aromatic polyesters, such as polyalkyleneterephtalate are widely commercially used, especially in food packaging and textile field due to their good thermomechanical properties. Aromatic polyamides, such as Kevlar constitute high performance polymers thanks to their high stability and rigidity. Finally, phenolic compounds constitute a widely used raw material. For instance, Bisphenol A is an important monomer for the synthesis of polycarbonates, epoxy resins and a popular plasticizer for thermoplastic polymers. These compounds are mainly petroleum based and derived from benzene, xylene and toluene.

Phenolic polymers are difficult to prepare as it is not easy to prepare appropriate monomers with a sufficient purity. The high purity of the monomers is a pre-requisite to the synthesis of high molar mass polymer.

The aim of the present invention is to provide new phenolic thermoplastic polymers for use in numerous applications, as fibers, films, foams, composites, adhesives, coatings, etc. . . . The latter exhibit high thermal stability, high glass transition temperature and high mechanical properties. In addition, the presence of remaining phenolic functions onto the polymer skeleton also brings other properties to these materials such as anti-bacterial activity.

The present invention relates to the use of a compound having the following formula (I):

wherein:R1is H or a OR7group, R7being H, a (C1-C10)alkyl group or a (C2-C6)alkenyl group;R2is a (C1-C6)alkoxy group;R3is H or a radical of formula (II)

k being an integer varying from 1 to 6;R4is a (C1-C6)alkoxy group or a radical X chosen from the group consisting of: (C2-C6)alkenyl groups, (C1-C10)alkyl group, —CHO, —COOH, —CH2OH, and —COORa, Rabeing a (C1-C6)alkyl group or a (C2-C12)alkenyl group;

and wherein:when R1is H, then R3is a group of formula (II) and R4is a (C1-C6)alkoxy group, andwhen R1is a OR7group, then R3is H and R4is X as defined above,

for the preparation of a polymer.

The present invention is based on the fact that the compounds of formula (I) may be used as monomers suitable to be used for subsequent polymerization.

In one embodiment, the compound of formula (I) has one of the following formulae (I-1), (I-2), (I-3), (I-4), (I-5) or (I-6):

wherein:R2and k are as defined above in formula (I),R′ is a (C1-C6)alkoxy group;R6is a (C1-C6)alkyl group;R7is as defined above in formula (I), preferably H;R′7is chosen from the group consisting of: (C1-C10)alkyl groups and (C2-C6)alkenyl groups, andR9is chosen from the group consisting of: (C1-C10)alkyl groups, (C2-C6)alkenyl groups, and —COORagroups, Rabeing a (C2-C12)alkenyl group, wherein, when R′7is an alkyl group, then R9is chosen from the (C2-C6)alkenyl groups and —COORagroups, and when R′7is an alkenyl group, then R9is an alkyl group.

The present invention also relates to a polymer susceptible to be obtained by polymerization of the compound of formula (I) as defined above. Such polymer is obtained by implementing a polymerization step according to the polymerization methods well-known in the art of the compound of formula (I) as defined above.

The present invention also relates to a polymer susceptible to be obtained by polymerization of the compound of formula (I) as defined above, and of a monomer chosen from the group consisting of: diacids, diesters, diamines, and epoxy compounds.

In one embodiment, the diacids and the diesters are selected from the compounds having the following formula (V):
RbOOC-A1-COORb(V)

wherein:Rbis H or (C1-C6)alkyl group; andA1is chosen from the group consisting of:a (C2-C10)alkylene radical;a (C3-C12)cycloalkylene radical, optionally substituted by at least one (C1-C10)alkyl group;a (C2-C30)alkenylene radical;an arylene radical comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group;a heteroarylene radical comprising from 5 to 14 carbon atoms and at least one heteroatom chosen from O, S and N, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group; anda radical of formula —B1—B2—B3— wherein:B2is a (C3-C12)cycloalkylene radical, in which one or more carbon atom(s) is optionally substituted by at least one (C1-C10)alkyl group, andB1and B3, identical or different, are chosen from the (C2-C15)alkylene radicals;a radical of formula —B4—B5—, wherein B4and B5, identical or different, are chosen from the arylene radicals comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with one or several substituents chosen from the (C1-C6)alkoxy groups.

In one embodiment, the diamines are selected from the compounds having the following formula (VII):
H2N-A2-NH2(VII)
wherein A2is chosen from the group consisting of:a (C2-C10)alkylene radical;a (C3-C12)cycloalkylene radical, optionally substituted by at least one (C1-C10)alkyl group;a (C2-C30)alkenylene radical;an arylene radical comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group;a heteroarylene radical comprising from 5 to 14 carbon atoms and at least one heteroatom chosen from O, S, and N, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group; anda radical of formula —B′1—B′2—B′3— wherein:B′2is a (C1-C10)alkylene radical, andB′1and B′3, identical or different, are chosen from the arylene radicals comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group;

In another embodiment, the diamines are selected from the compounds having the following formula (X):
H2N-A3-NH2(X)
wherein A3is a radical of formula —B″1—B″2— wherein:B″1is a (C3-C12)cycloalkylene radical, in which one or more carbon atom(s) is optionally substituted by at least one (C1-C10)alkyl group, andB″2is a (C1-C10)alkylene radical.

The present invention also relates to a polymer susceptible to be obtained by polymerization of the compound of formula (I) as defined above, comprising at least one repetitive unit U, said unit U comprising a moiety having the following formula (III):

The repetitive unit U as defined above may comprise other moieties or other functional group(s) linked to the moiety of formula (III).

In one embodiment, in the formula (III) above-mentioned, R1and R2, identical or different, are chosen from the (C1-C6)alkoxy groups. In particular, R1and R2represent a methoxy group.

In one embodiment, the present invention relates to a polymer as defined above comprising at least one repetitive unit U, wherein said unit U comprises a moiety having the formula (III-a):

In one embodiment, the present invention relates to a polymer as defined above comprising at least one repetitive unit U, wherein said unit U comprises a moiety having the formula (III-b):

The present invention also relates to a compound having the following formula (IV):

wherein:A1is as defined above in formula (V);R2is a (C1-C6)alkoxy group;R6is a (C1-C6)alkyl group; and

According to a preferred embodiment, in formula (IV), n is greater than 2, preferably greater than 5, and in particular greater than 10.

The compounds of formula (IV) are compounds which are susceptible to be obtained by polymerization of a compound of formula (I) and a diacid or a diester.

In the compound having the formula (IV) as defined above, the repetitive unit U has the following formula (U-1):

wherein OR6corresponds to the R1group of the moiety of formula (III), and A1, R6and R2are as defined above.

In this compound, the repetitive units U comprise the moiety of formula (III) as defined above, which is linked on one side to a methylene radical and on the other side to a —CH2—O—C(O)-A1-C(O)—O— radical.

The compound of formula (IV) is a polymer which possesses n units U having the formula (U-1), which comprise the moiety of formula (III-1):

As used herein, the bond wherein the signis present, means that said bond is linked to another moiety, for example another functional group.

For example, the polymer having the following formula (IV) may be written as follows:

In one embodiment, in formula (IV), R2is a methoxy group.

In one embodiment, in formula (IV), R6is a methyl group.

In one embodiment, the present invention concerns a compound having the following formula (IV-1):

wherein A1and n are as defined above.

In one embodiment, in formulae (IV) and (IV-1), A1is a (C2-C10)alkylene radical, more particularly an octylene radical or an ethylene radical.

In one embodiment, in formulae (IV) and (IV-1), A1is a (C3-C12)cycloalkylene radical, optionally substituted by at least one (C1-C10)alkyl group.

In one embodiment, in formulae (IV) and (IV-1), A1is an arylene radical comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group. In particular, A1represents a phenylene radical.

In one embodiment, in formulae (IV) and (IV-1), A1is a heteroarylene radical comprising from 5 to 14 carbon atoms and at least one heteroatom chosen from O, S and N, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group.

In one embodiment, in formulae (IV) and (IV-1), A1is a radical of formula —B1—B2—B3— wherein:B2is a (C3-C12)cycloalkylene radical, in which one or more carbon atom(s) is substituted by at least one (C1-C10)alkyl group, andB1and B3, identical or different, are chosen from the (C8-C12)alkylene radicals.

In one embodiment, in formulae (IV) and (IV-1), A1is a radical of formula —B4—B5—, wherein B4and B5, identical or different, are chosen from the arylene radicals comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with one or several substituents chosen from the (C1-C6)alkoxy groups.

In one embodiment, in formulae (IV) and (IV-1), n is an integer varying from 2 to 130. According to a preferred embodiment, in formula (IV) or (IV-1), n is greater than 5, and in particular greater than 10.

The present invention also concerns a process for preparing a compound having formula (IV) or (IV-1), said process comprising at least one step of polymerization of:a compound having the following formula (I-1):

wherein R2and R6are as defined above,and a compound of formula (V) as defined above.

In one embodiment, the polymerization step is carried out in the presence of a catalyst chosen from the group consisting of: 5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), zinc acetate (ZnAc), Ti(OBu)4, dibutyl tin oxide (DBTO), and mixtures thereof.

In one embodiment, the polymerization step is carried out at a temperature comprised between 80° C. and 250° C., preferably between 120° C. and 200° C.

Typically, the catalyst may be used from 0.1% to 10% molar, preferably from 0.5% to 5% molar. Most preferably, the catalyst is Ti(OBu)4, and is used at 0.5% molar.

In one embodiment, the compound having the following formula (I-1) has the following formula (I-1-1):

In another embodiment, the compound of formula (V) has the following formula (V-1):
HOOC-A1-COOH  (V-1)
wherein A1is as defined above.

In another embodiment, the compound of formula (V) has the following formula (V-2):
RbOOC-A1-COORb(V-2)
wherein A1is as defined above, and Rbis a (C1-C6)alkyl group.

In one embodiment, preferred compounds of formula (V-1) are chosen from the following compounds:

In one embodiment, preferred compounds of formula (V-2) are chosen from the following compounds:

The present invention also relates to a compound having the following formula (IV-bis):

wherein:A4is a (C2-C10)alkylene radical;R2is a (C1-C6)alkoxy group;R6is a (C1-C6)alkyl group; andn is an integer varying from 1 to 40.

According to a preferred embodiment, in formula (IV-bis), n is greater than 2, preferably greater than 5, and in particular greater than 10.

The compounds of formula (IV-bis) are polymers which are susceptible to be obtained by polymerization of a compound of formula (I) and a diol.

In the compound having the formula (IV-bis) as defined above, the repetitive unit U has the following formula (U-2):

wherein OR6corresponds to the R1group of the moiety of formula (III), A4, R6and R2being as defined above.

According to the invention, the compound of formula (IV-bis) is a polymer which possesses n units U having the formula (U-2), which comprise the moiety of formula (III-1):

In one embodiment, in formula (IV-bis), R2is a methoxy group.

In one embodiment, in formula (IV-bis), R6is a methyl group.

In one embodiment, the present invention relates to a compound having the following formula (IV-bis-1):

wherein A4and n are as defined above.

The compound of formula (IV-bis-1) corresponds to a polymer of formula (IV-bis) wherein: R2is methoxy and R6is methyl.

In one embodiment, in formulae (IV-bis) and (IV-bis-1), A4represents a decylene radical.

The present invention also concerns a process for preparing a compound having the formula (IV-bis) or (IV-bis-1) as defined above, comprising at least one step of polymerization of:a compound having the following formula (I-2):

wherein A4is as defined above.

In one embodiment, the polymerization step is carried out in the presence of a catalyst chosen from the group consisting of: 5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), zinc acetate (ZnAc), Ti(OBu)4, dibutyl tin oxide (DBTO), and mixtures thereof.

In one embodiment, the polymerization step is carried out at a temperature comprised between 80° C. and 250° C., preferably between 120° C. and 200° C.

Typically, the catalyst may be used from 0.1% to 10% molar, preferably from 0.5% to 5% molar. Most preferably, the catalyst is Ti(OBu)4, and is used at 0.5% molar.

In one embodiment, the compound having the following formula (I-2) has the following formula (I-2-1):

The compound of formula (I-2-1) corresponds to a compound of formula (I-2) wherein R2is methoxy and R6is methyl.

In another embodiment, the compound of formula (VIII) is:

The present invention also relates to a compound having the following formula (VI):

wherein:A2is as defined above in formula (VII);R2is a (C1-C6)alkoxy group;R6is a (C1-C6)alkyl group; andn is an integer varying from 1 to 100.

According to a preferred embodiment, in formula (VI), n is greater than 2, preferably greater than 5, and in particular greater than 10.

The compounds of formula (VI) are polymers which are susceptible to be obtained by polymerization of a compound of formula (I) and a diamine.

In the polymer having the formula (VI) as defined above, the repetitive unit U has the following formula (U-3):

wherein OR6corresponds to the R1group of the moiety of formula (III), A2, R6and R2being as defined above.

According to the invention, the polymer of formula (VI) possesses n units U having the formula (U-3), which comprise the moiety of formula (III-1):

In one embodiment, in formula (VI), R2is a methoxy group.

In one embodiment, in formula (VI), R6is a methyl group.

In one embodiment, the present invention relates to a polymer having the following formula (VI-1):

wherein A2and n are as defined above.

The polymer of formula (VI-1) corresponds to a polymer of formula (VI) wherein R2is methoxy and R6is methyl.

The present invention also relates to a compound having the following formula (XII):

wherein:A2is as defined above in formula (VII);R7is as defined above in formula (I);R2is a (C1-C6)alkoxy group; andn is an integer varying from 1 to 100.

According to a preferred embodiment, in formula (XII), n is greater than 2, preferably greater than 5, and in particular greater than 10.

The compounds of formula (XII) are polymers which are susceptible to be obtained by polymerization of a compound of formula (I-6) and a diamine.

According to the invention, the polymer of formula (VI) possesses n units U having the formula (U-3-1), which comprise the moiety of formula (III-1-1):

In one embodiment, in formula (VI), R2is a methoxy group.

In one embodiment, in formula (VI), R7is H.

In one embodiment, in formulae (XII), (VI) and (VI-1), A2is a (C2-C10)alkylene radical, more particularly a hexylene radical or a decylene radical.

In one embodiment, in formulae (XII), (VI) and (VI-1), A2is a (C3-C12)cycloalkylene radical, optionally substituted by at least one (C1-C10)alkyl group.

In one embodiment, in formulae (XII), (VI) and (VI-1), A2is an arylene radical comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group, in particular a phenylene.

In one embodiment, in formulae (XII), (VI) and (VI-1), A2is a heteroarylene radical comprising from 5 to 14 carbon atoms and at least one heteroatom chosen from O, S, and N, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group.

In one embodiment, in formulae (XII), (VI) and (VI-1), A2is a radical of formula —B′1—B′2—B′3— wherein:B′2is a (C1-C10)alkylene radical, andB′1and B′3, identical or different, are chosen from the arylene radicals comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group.

The present invention also relates to a process for preparing a polymer having the formulae (VI) or (VI-1) as defined above, comprising at least one step of polymerization of:a compound having the following formula (I-3):

wherein R2and R6are as defined above,and a diamine of formula (VII) H2N-A2-NH2, A2being as defined above.

In one embodiment, the polymerization step is carried out at a temperature comprised between 60° C. and 250° C., preferably between 80° C. and 240° C.

In one embodiment, the polymerization step is carried out in presence of an equimolar quantity of the compounds of formula (I-3) and the diamine of formula (VII).

In one embodiment, the compound having the following formula (I-3), used in the above-mentioned process, has the following formula (I-3-1):

In another embodiment, the compound of formula (VII) has the following formula (VII-1):
H2N—(CH2)p—NH2(VII-1)

wherein p is an integer comprised from 1 to 20, preferably from 2 to 12.

In an embodiment, the compound of formula (VII-1) is chosen from the following compounds:

In another embodiment, the compound of formula (VII) has the following formula (VII-2):

wherein q is an integer comprised from 1 to 20, preferably from 1 to 10.

In one embodiment, the compound of formula (VII-2) is as follows:

The present invention also relates to a process for preparing a polymer having the formulae (XII) as defined above, comprising at least one step of polymerization of a compound having the formula (I-6) as defined above, and a diamine of formula (VII) H2N-A2-NH2, A2being as defined above.

The present invention also relates to a polymer having a repetitive unit comprising a moiety having the following formula (IX):

wherein:R2is as defined above,k is an integer varying from 1 to 6,R′ is a (C1-C6)alkoxy group, andA3is as defined above in formula (X).

The present invention also relates to the process for preparing a polymer comprising repetitive units containing a moiety having the formula (IX) as defined above, comprising at least one step of polymerization of:a compound having the following formula (I-4):

wherein:R2is as defined above,k is an integer varying from 1 to 6,R′ is a (C1-C6)alkoxy group;and a diamine of formula (X) H2N-A3-NH2, A3being as defined above,

A3being preferably a radical of formula —B″1—B″2— wherein:B″1is a (C3-C12)cycloalkylene radical, in which one or more carbon atom(s) is optionally substituted by at least one (C1-C10)alkyl group, andB″2is a (C1-C10)alkylene radical.

In one embodiment, the polymerization step is carried out at a temperature comprised between 60° C. and 250° C., preferably between 80° C. and 200° C.

In the process of the invention, a preferred compound of formula (I-4) has the following formula (I-4-1):

k being a defined above, such as for example the following compound:

In the process of the invention, a preferred diamine of formula (X) has the following formula:

The present invention also relates to a compound having the following formula (XI-A) or (XI-B):

wherein:R2is a (C1-C6)alkoxy group;R6is a (C1-C10)alkyl group,Y is chosen from the group consisting of: a bond, a (C1-C10)alkylene group, —C(O)O—Rc— and —Rc—O(O)C, Rcbeing a (C1-C10)alkylene radical;R8is a (C1-C6)alkoxy group or a (C1-C10)alkyl group; andn is an integer varying from 10 to 120.

In the compound having the formula (XI-A) as defined above, the repetitive unit U has the following formula (U-4):

wherein OR6corresponds to the R1group of the moiety of formula (III), Y and R2being as defined above.

According to the invention, the compound of formula (XI-A) is a polymer which possesses n units U having the formula (U-4), which comprise the moiety of formula (III-1) as defined above.

In one embodiment, in formulae (XI-A) and (XI-B), R2is a methoxy group.

In one embodiment, in formulae (XI-A) and (XI-B), R6is a methyl group.

In one embodiment, in formulae (XI-A) and (XI-B), R8is a (C1-C6)alkoxy group, in particular a methoxy group.

In one embodiment, in formulae (XI-A) and (XI-B), R8is a (C1-C10)alkyl group, in particular a methyl group.

In one embodiment, the present invention relates to a polymer having the following formula (XI-A-1) or (XI-B-1):

wherein Y, R8and n are as defined above.

In one embodiment, in formulae (XI-A) and (XI-A-1), Y is a bond.

In one embodiment, in formulae (XI-A) and (XI-A-1), Y is a (C1-C10)alkylene group, in particular a methylene group.

In one embodiment, in formulae (XI-A) and (XI-A-1), Y is a radical —COORc— or —RcOOC—, Rcbeing as defined above and being in particular a nonylene radical.

In one embodiment, in formulae (XI-B) and (XI-B-1), R8is a (C1-C10)alkyl group, in particular a methyl group.

The present invention also relates to a process for preparing a compound having the formulae (XI-A) or (XI-B), comprising at least one step of polymerization of a compound having the following formula (I-5):

wherein:R2is as defined above;R′7is chosen from the group consisting of: (C1-C10)alkyl groups and (C2-C6)alkenyl groups, andR9is chosen from the group consisting of: (C1-C10)alkyl groups, (C2-C6)alkenyl groups, and —COORagroups, Rabeing a (C2-C12)alkenyl group, wherein, when R′7is an alkyl group, then R9is chosen from the (C2-C6)alkenyl groups and —COORagroups, and when R′7is an alkenyl group, then R9is an alkyl group.

In one embodiment, the polymerization step is carried out in the presence of a Grubbs catalyst. These Grubbs catalysts are a series of transition metal carbene complexes used in particular as catalysts for olefin metathesis. The main advantage of these catalysts is their compatibility with different functional groups. The activity of these catalysts in acyclic diene metathesis polymerization (ADMET) has been widely demonstrated in a large number of publications. Such catalysts are well known from the skilled person.

Typically, the catalyst may be used from 0.1% to 10% molar, preferably from 0.5% to 5% molar. Most preferably, the catalyst is used at 2% molar.

In one embodiment, the polymerization step is carried out at a temperature comprised between 60° C. and 130° C., preferably between 80° C. and 120° C.

In one embodiment, in the formula (I-5) above-mentioned, R2is a methoxy group.

In the process of the invention, a preferred compound of formula (I-5) has the following formula (I-5-1):

In one embodiment, in formulae (I-5) and (I-5-1), R′7is a (C1-C10)alkyl group, in particular a methyl group.

In one embodiment, in formulae (I-5) and (I-5-1), R′7is a (C2-C6)alkenyl group, in particular a —CH2—CH═CH2group.

In one embodiment, in formulae (I-5) and (I-5-1), R9is a (C2-C6)alkenyl group, in particular a —CH2—CH═CH2group or a —CH═CH2group.

In one embodiment, in formulae (I-5) and (I-5-1), R9is a —COORagroup, in particular a —COO—(CH2)9—CH═CH2group.

Preferred compounds of formula (I-5) are chosen from the group consisting of:

As used herein, the term “(Cx-Cy)alkyl” means a saturated aliphatic hydrocarbon group, which may be straight or branched, having x to y carbon atoms in the chain. Preferred alkyl groups have 1 to about 12, preferably 1 to 10, and more preferably 1 to 6, 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 “(Cx-Cy)alkylene” (or “alkylidene”) refers to a divalent saturated aliphatic hydrocarbon radical, comprising from x to y carbon atoms, having preferably from 1 to 20, in particular 1 to 12 carbon atoms, and more preferably 2 to 10 carbon atoms. When said radical is linear, it may be represented by the formula (CH2)mwherein m is an integer varying from 1 to 12, and preferably from 2 to 10. The following alkylene may be cited as example: methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene.

As used herein, the term “(Cx-Cy)alkenyl” means an aliphatic hydrocarbon group containing a carbon-carbon double bond and which may be straight or branched having x to y carbon atoms in the chain. Preferred alkenyl groups have 2 to 12 carbon atoms in the chain; and more preferably about 2 to 10 or 2 to 6 carbon atoms in the chain. Exemplary alkenyl groups include for example ethenyl, propenyl, n-butenyl, i-butenyl, 3-methylbut-2-enyl, n-pentenyl, heptenyl, octenyl, nonenyl, decenyl.

As used herein, the term “alkenylene” means a hydrocarbon radical having at least one carbon-carbon double bond (straight chain or branched) wherein a hydrogen atom is removed from each of the terminal carbons such as ethenylene, propenylene, and the like.

As used herein, the term “(Cx-Cy)aryl” refers to an aromatic monocyclic or bicyclic hydrocarbon ring system having from x to y carbon atoms, preferably from 6 to 14, and more preferably 6 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 term “arylene” refers to a radical derived from arene wherein two hydrogen atoms from the cycle have been deleted. Among the arylene radicals, the phenylene radical may be cited.

As used herein, the term “cycloalkyl” represents a non-aromatic monocyclic or bicyclic ring system having in particular from 3 to 12 carbon atoms. For example, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl may be cited.

As used herein, the term “cycloalkylene” refers to a divalent, saturated or partially unsaturated, non-aromatic monocyclic, bicyclic ring system having in particular from 3 to 12 carbon atoms, such as cyclobutylene, cyclopentylene, cyclohexylene.

As used herein, the term “hereroarylene” refers to a divalent heteroaryl as defined above.

As used herein, the term “alkoxy” means an alkyl-O— group wherein the alkyl group is as herein described. Exemplary alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy and heptoxy.

As used herein, the compounds of the invention such as those having one of the formulae (IV), (IV-bis), (VI), (XI-A) or (XI-B), may also be named ‘polymers’, especially as they comprise the repetition of n repetitive units.

The invention is described in the foregoing by way of non-limiting examples.

EXAMPLES

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Example 1: Preparation of Polyesters (P1 to P8) by Esterification

General Procedure

Diol (1 equivalent) and diester (or diacid) (1 equivalent) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 0.5 mol % of titanium butoxide

The following polymers were prepared according to this procedure:

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.28 g of sebacid acid (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide 0.5 mol %.

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.75 g of Pripol (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide 0.5 mol %.

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.51 g of C22 diacid (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide 0.5 mol %.

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.16 g of succinic acid (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide 0.5 mol %.

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.16 g of maleic acid (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide 0.5 mol %.

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.23 g of terephtalic acid (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide 0.5 mol %.

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.18 g of 2,5-furandicarboxylic acid (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide 0.5 mol %.

TABLE 1Thermomechanical properties of polymers from methylated divanillyldiol and different diacidsTgTD5%DiolDiacidCatalyst(° C.)a(° C.)bPolymerTiOBu40, 5%19297P1−5284P213260P390270P497240P5113260P6140260P7aTg(glass transition temperature) determined by DSC second heating cyclebTD5%(Temperature of 5% degradation) determined by TGA.

Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from −70° C. to 200° C. at a rate of 10° C. min−1. Consecutive cooling and second heating run were also performed at 10° C. min−1. The glass transition temperatures (Tg) were calculated from the second heating run.

Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10° C. min−1under air between 20° C. and 800° C. TD5%=Temperature at which 5% of the material is degraded.

Example 2: Preparation of Polyester P1 by Transesterification

General Procedures

Methylated divanillic diol (1 equivalent) and dimethyl sebacate (1 equivalent) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2 mol % of catalyst (titanium butoxide, zinc acetate or dibutyltin oxide) or in the presence of 0.5 mol % of titanium butoxide.

According to another variant, methylated divanillic diol (1 equivalent) and dimethyl sebacate (1 equivalent) were stirred at 120° C. for 24 h in the presence of 10 mol % of TBD.

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.32 g of dimethyl sebacate (1.39 mmol) were stirred at 120° C. for 24 h in the presence of 19.3 mg of TBD −5% mol per ester function)

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.32 g of dimethyl sebacate (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.32 g of dimethyl sebacate (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 9.6 mg of Titanium butoxide (1 mol % catalyst relative per ester function).

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.32 g of dimethyl sebacate (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 6 mg of ZnAc (1 mol % catalyst relative per ester function).

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.32 g of dimethyl sebacate (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 6.9 mg of DBTO (1 mol % catalyst relative per ester function).

Size exclusion chromatography (SEC) analysis was performed at room temperature in DMF/DMSO using simultaneous UV and refraction index detections. The elution times were converted to molar mass using a calibration curve based on low dispersity (=Mn/Mw) polystyrene (PS) standards.

Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from −70° C. to 200° C. at a rate of 10° C. min−1. Consecutive cooling and second heating run were also performed at 10° C. min−1. The glass transition temperatures (Tg) were calculated from the second heating run.

Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10° C. min-1 under air between 20° C. and 800° C. TD5%=Temperature of 5% degradation.

Example 3: Preparation of Polyester P9 by Transesterification

General Procedure

Methylated dimethyl vanillate (1 equivalent) and 1,10-decanediol (1 equivalent) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2 mol % of catalyst (titanium butoxide, zinc acetate or dibutyltin oxide) or in the presence of 0.5 mol % of titanium butoxide.

According to another variant, methylated dimethyl vanillate (1 equivalent) and 1,10-decanediol (1 equivalent) were stirred at 120° C. for 24 h in the presence of 10 mol % of TBD.

Polymers Obtained from Methylated Dimethylvanillate and Decanediol Using Different Catalysts

0.5 g methylated dimethyldivanillate (1.28 mmol) and 0.23 g of 1,10-decanediol (1.28 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 8.7 mg of Titanium butoxide (1 mol % catalyst relative per ester function).

0.5 g methylated dimethyldivanillate (1.28 mmol) and 0.23 g of 1,10-decanediol (1.28 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 6.3 mg of DBTO (1 mol % catalyst relative per ester function).

0.5 g methylated dimethyldivanillate (1.28 mmol) and 0.23 g of 1,10-decanediol (1.28 mmol) (1.39 mmol) were stirred at 120° C. for 24 h in the presence of 17.8 mg of TBD −5% mol per ester function)

0.5 g methylated dimethyldivanillate (1.28 mmol) and 0.23 g of 1,10-decanediol (1.28 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 4.7 mg of ZnAc (1 mol % catalyst relative per ester function).

0.5 g methylated dimethyldivanillate (1.28 mmol) and 0.23 g of 1,10-decanediol (1.28 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.2 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from −70° C. to 200° C. at a rate of 10° C. min−1. Consecutive cooling and second heating run were also performed at 10° C. min−1. The glass transition temperatures (Tg) were calculated from the second heating run.

Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10° C. min−1under air between 20° C. and 800° C. TD5%=Temperature of 5% degradation.

Size exclusion chromatography (SEC) analysis was performed at room temperature in DMF/DMSO using simultaneous UV and refraction index detections. The elution times were converted to molar mass using a calibration curve based on low dispersity (=Mn/Mw) polystyrene (PS) standards.

Example 4: Preparation of Polyester P1 to P′8 by Transesterification

The general procedure is identical to example 1.

The polymers P′1 to P′8 possess a structure similar to the one of polymers P1 to P8, except that the value of the repetitive units (n) differs, leading to polymers with various properties.

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.32 g of dimethyl sebacate (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.79 g of Pripol ester (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.54 g of C22 diester (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.20 g of dimethyl succinate (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.27 g of dimethyl terephtalate (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.26 g of 2,5-furandicarboxylic acid (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

0.5 g of methylated divanillyl diol (1.39 mmol) and 0.54 g of methylated dimethyldivanillate (1.39 mmol) were stirred at 160° C. for 2 h under nitrogen flow and at 200° C. under vacuum for 6 h in the presence of 2.4 mg of Titanium butoxide (0.25 mol % catalyst relative per ester function).

TABLE 4Thermomechanical properties of polymers from of methylated divanillyldiol and different methyldiesters (with catalyst TiOBu40.5%)TgTD5%E′Diester(° C.)a(° C.)c(GPa)bPolymers53082.0P3′1013102.0P6′683025.1P4′−53470.1P2′1403421.4P7′383198.1P1′1023051.3P8′aDetermined by DSC second heating cyclebDetermined by DMA 3 points flexioncDetermined by TGA. Temperature of 5% degradation

Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from −70° C. to 200° C. at a rate of 10° C. min−1. Consecutive cooling and second heating run were also performed at 10° C. min−1. The glass transition temperatures (Tg) were calculated from the second heating run.

Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10° C. min−1under air between 20° C. and 800° C. TD5%=Temperature of 5% degradation.

The mechanical properties were measured with a dynamic mechanical thermal analyzer DMA RSA 3 (TA instrument). The sample temperature was modulated from −80° C. to 220° C., depending on the sample at a heating rate of 5° C./min. The measurements were performed in a 3-point bending mode at a frequency of 1 Hz, an initial static force varying between 0.1 and 0.5 N and a strain sweep of 0.1%.

Example 5: Preparation of Polyamides P10 to P12

General Procedure

Equimolar amount of diacids and diamines were dissolved in ethanol and the mixture was stirred slowly for 30 min at 80° C. to allow the formation of ammonium salt. The salt was obtained as a fine powder after elimination of the solvent and dried under vacuum. The salt was warmed at 230° C. for 4 h.

The following polyamides were synthesized:

TABLE 5Thermomechanical properties of polyamides synthesized from methylateddivanillic diacid and different diaminesTgDiacidDiamine(° C.)aName124P10136P11157P12aDetermined by DSC second heating cycle

Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from −70° C. to 200° C. at a rate of 10° C. min−1. Consecutive cooling and second heating run were also performed at 10° C. min−1. The glass transition temperatures (Tg) were calculated from the second heating run.

Example 6: Preparation of Epoxy Resin Synthesis

General Procedure

Bisepoxide and diamine were mixed together in ethanol. After evaporation of the solvent the mixture is poured into a matrix and warmed at 80° C. for 4 h.

DMA RSA 3 (TA instrument). The sample temperature was modulated from −80° C. to 220° C., depending on the sample at a heating rate of 5° C./min. The measurements were performed in a 3-point bending mode at a frequency of 1 Hz, an initial static force varying between 0.1 and 0.5 N and a strain sweep of 0.1%.

Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from −70° C. to 200° C. at a rate of 10° C. min−1. Consecutive cooling and second heating run were also performed at 10° C. min−1. The glass transition temperatures (Tg) were calculated from the second heating run.

Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10° C. min−1under air between 20° C. and 800° C. TD5%=Temperature of 5% degradation.

Example 7: Preparation of Unsaturated Polyesters

General Procedure

Unsaturated dimer (0.22 mmol) was dissolved in 1 mL of Polarclean. Grubbs catalyst (2% mol) was added to the flask. The flask was heated at 80° C. under vacuum for 18 h. Then 1 mL of ethyl vinyl ether was introduced to the flask to quench the reaction. The final polymer was diffolved into 1 mL of THF and reprecipitated in cold methanol.

The following polymers were synthesized:

The catalysts mentioned in table 7 are the following:

Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from −70° C. to 200° C. at a rate of 10° C. min−1. Consecutive cooling and second heating run were also performed at 10° C. min−1. The glass transition temperatures (Tg) were calculated from the second heating run.

Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10° C. min−1under air between 20° C. and 800° C. TD5%=Temperature of 5% degradation.

Size exclusion chromatography (SEC) analysis was performed at room temperature in DMF/DMSO using simultaneous UV and refraction index detections. The elution times were converted to molar mass using a calibration curve based on low dispersity (=Mn/Mw) polystyrene (PS) standards.

Example 8: Preparation of Polyimines

The polyimines of formula (XII) as mentioned above are prepared by reacting divanilline with a diamine.

The monomers are mixed in stoichiometric amounts in the presence of a solvent (toluene, CH3Cl) (5 mg/mL). The mixture of the monomers in the solvent is heated at reflux for 3 days in a Dean-Stark apparatus.

Then, the polymer thus obtained is washed with methanol and fractionated with a Soxhlet extractor.

The following reaction is carried out:

R being H.

The polymer thus obtained has a Mn of 3 525 g·mol−1and=1.4.

The same method could be carried out by using microwaves.