EP3469034A1

EP3469034A1 - Cross-linkable silylated polymer-based adhesive compositions

Info

Publication number: EP3469034A1
Application number: EP17732521.4A
Authority: EP
Inventors: Boris COLIN; Guillaume Michaud; Frédéric Simon; Olivier Lavastre
Original assignee: Centre National de la Recherche Scientifique CNRS; Universite de Rennes 1; Bostik SA
Current assignee: Centre National de la Recherche Scientifique CNRS; Universite de Rennes 1; Bostik SA
Priority date: 2016-06-14
Filing date: 2017-06-05
Publication date: 2019-04-17
Also published as: FR3052457B1; JP2019523801A; JP7105702B2; US20190330503A1; CN109844053B; US10995246B2; WO2017216446A1; FR3052457A1; CN109844053A

Abstract

The present invention relates to a cross-linkable adhesive composition comprising at least one cross-linkable silylated polymer and at least one cross-linking catalyst obtained by reacting a metal alkoxide and an oxime. The invention also relates to the use of a metal compound obtained by reacting a metal alkoxide and an oxime as a catalyst for cross-linking silylated polymers.

Description

ADHESIVE COMPOSITIONS BASED ON SILYLATED POLYMERS

CROSSLINKABLE

FIELD OF THE INVENTION

The present invention relates to an adhesive composition comprising at least one crosslinkable silylated polymer and at least one metal catalyst.

BACKGROUND

The silylated polymers can be used in various types of applications, for example in adhesive compositions that can be used for all types of bonding such as bonding surface coatings, or that can be used to form a waterproofing membrane or to prepare articles. self-adhesive.

The silylated polymers may be crosslinked even at room temperature by reaction of the reactive silyl group with the moisture of the air. In order to accelerate the crosslinking of the silylated polymer, it is possible to add to the silylated polymer a crosslinking catalyst.

Generally, the crosslinking catalyst used in silylated polymer-based adhesive compositions is a tin-based catalyst, such as dibutyltin dilaurate (DBTDL), dibutyltin diacetate or dibutyltin bis (acetylacetonate).

However, the toxicity of these tin catalysts is increasingly highlighted, which leads manufacturers to avoid their use.

Tin-free catalysts have been developed for the crosslinking of silylated polymers, among which mention may be made of bismuth neodecanoate or zinc octoate. These tin-free catalysts are 2 to 3 times less effective than tin catalysts. Thus, in order to obtain crosslinking times equivalent to those obtained with the tin catalysts, it will be necessary to introduce 2 to 3 times more catalyst of the bismuth neodecanoate or zinc octoate type.

The crosslinking catalyst must make it possible to control the crosslinking kinetics of the silylated polymer during its use, but it must also remain stable during the storage of the adhesive composition before use. In addition, for optimal use of the adhesive composition, said composition must not crosslink during its storage and the catalyst must remain active to ensure its function as a catalyst during the application of the adhesive composition, at the time of crosslinking. polymer, in the presence of atmospheric moisture.

The document US 2013/0096252 describes a composition comprising a silylated polymer and an amine or organometallic type tinless crosslinking catalyst. This document describes among other catalysts of the titanium butoxide type. An adhesive composition comprising a silylated polymer and a butoxide catalyst titanium is not stable. Indeed, there is a crosslinking of the polymer, for example during storage before the use of the adhesive composition.

US 2009/275702 discloses a composition comprising a silylated polymer and a titanium-based crosslinking catalyst. This document notably discloses a catalyst based on titanium and acetylacetonate. This type of catalyst leads to long crosslinking times, in particular longer than the crosslinking times achieved with the catalysts according to the invention.

US Pat. No. 4,956,435 describes a composition comprising a polyorganosiloxane terminated by a trialkoxysilylethylene group, a titanium catalyst and an alkoxysilane crosslinking agent and optionally an oxime. Due to the presence of the crosslinking agent of the alkoxysilane type, this US Pat. No. 4,956,435 does not disclose the preparation of a catalyst, isolated beforehand, obtained by reaction of a metal alkoxide with an oxime as defined in the present invention.

The object of the present invention is to provide a crosslinkable adhesive composition, free of tin, in particular of tin alkyl, which exhibits both good stability, in particular during storage, and a satisfactory crosslinking time.

SUMMARY OF THE INVENTION

A first subject of the present invention relates to an adhesive composition comprising at least one silylated polymer (A) and at least one catalyst (B),

said at least one silylated polymer comprising at least one, preferably at least two groups of formula (I):

in which :

- R ⁴ represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, with the possibility that when there are several radicals R ⁴ , the latter are identical or different;

R ⁵ represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, with the possibility that when there are several radicals R ⁵ , the latter are identical or different, with the possibility that two OR ⁵ groups may be engaged in the same cycle;

p is an integer equal to 0, 1 or 2;

and said at least one catalyst being selected from metal compounds obtained by reaction:

at least one metal alkoxide,

with at least one oxime chosen from an oxime of formula (V) or an oxime of formula (VI): in which :

G ¹ is a hydrogen atom or a linear or branched alkyl radical comprising from 1 to 4 carbon atoms;

G ² is a hydrogen atom or a radical chosen from a linear or branched alkyl radical comprising from 1 to 10 carbon atoms, a linear or branched alkenyl radical comprising from 2 to 10 carbon atoms, a cyclic alkyl radical comprising from 3 to at 10 carbon atoms, an aryl radical or a radical -N (G ⁷ G ⁸ ) in which G ⁷ and G ⁸ represent, independently of one another, a linear or branched alkyl radical comprising from 1 to 10 atoms of carbon or a linear or branched alkenyl radical comprising from 2 to 10 carbon atoms or a benzyl radical;

G ³ represents either a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms, or forms the remainder of an aliphatic ring having between 4 and 14 carbon atoms with the groups G ⁴ and / or G ⁵ and / or G ⁶ , said aliphatic ring optionally comprising one or more heteroatoms and / or one or more double bonds and said aliphatic ring being optionally substituted by one or more alkyl groups having from 1 to 4 carbon atoms,

G ⁴ represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or forms the remainder of an aliphatic ring having 4 to 14 carbon atoms with the groups G ³ and / or G ⁵ and / or G ⁶ , said aliphatic ring optionally comprising one or more heteroatoms and / or one or more double bonds and said aliphatic ring being optionally substituted by one or more alkyl groups having from 1 to 4 carbon atoms,

it being understood that at least one of the groups G ³ or G ⁴ forms the remainder of an aliphatic ring with at least one of the groups G ⁵ or G ⁶ ;

G ⁵ represents either a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms, or forms the remainder of an aliphatic ring having between 4 and 14 carbon atoms with the groups G ³ and / or G ⁴ and / or G ⁶ , said aliphatic ring optionally comprising one or more heteroatoms and / or one or more double bonds and said aliphatic ring being optionally substituted by one or more alkyl groups having from 1 to 4 carbon atoms, G ⁶ represents either a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms, or forms the remainder of an aliphatic ring having between 4 and 14 carbon atoms with the groups G ³ and / or G ⁴ and / or G ⁵ , said aliphatic ring optionally comprising one or more heteroatoms and / or one or more double bonds and said aliphatic ring being optionally substituted by one or more alkyl groups having from 1 to 4 carbon atoms,

it being understood that at least one of the groups G ⁵ or G ⁶ forms the remainder of an aliphatic ring with at least one of the groups G ³ or G ⁴ .

According to one embodiment of the invention, the silylated polymer corresponds to one of formulas (II), (III), (IV) or (VII):

11} f

(IV>

(VII)

in which :

R ⁴ , R ⁵ and p have the same meaning as in formula (I) described in the present invention,

P represents a linear or branched, saturated or unsaturated polymeric radical optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur, silicon, and preferably having a molar mass ranging from 100 g / mol to 48600 g / mol, more particularly from 300 g / mol to 18600 g / mol or else from 500 g / mol to 12600 g / mol,

P 'represents a polysiloxane, preferably having a molar mass in number ranging from 100 g / mol to 48600 g / mol, more particularly from 300 g / mol to 18600 g / mol or else from 500 g / mol to 12600 g / mol ,

R ¹ represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms which may be aromatic or aliphatic, linear, branched or cyclic, R ³ represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms,

X represents a divalent radical chosen from -NH-, -NR ^7- or -S-,

R ⁷ represents a linear or branched alkyl radical comprising from 1 to 12 carbon atoms,

f is an integer from 1 to 6, preferably from 2 to 5, more preferably from 2 to 3.

According to one embodiment of the invention, the metal alkoxide has the formula M (OR) _y where

M represents a metal, preferably selected from titanium, zirconium, aluminum, silicon, hafnium, barium, cerium and antimony,

- y is 3 or 4, and

R represents a linear or branched alkyl group having from 1 to 5 carbon atoms, preferably from 2 to 4 carbon atoms, preferably from 3 to 4 carbon atoms, or a linear or branched alkenyl group having from 2 to 5 carbon atoms, carbon, preferably from 2 to 4 carbon atoms, preferably from 3 to 4 carbon atoms.

According to one embodiment of the invention, the oxime is an oxime of formula (V) in which:

G ¹ represents a methyl group or an ethyl group; and

G ² represents hydrogen or a linear or branched alkyl group comprising from 1 to 8 carbon atoms, or a phenyl group, or a group -N (G ⁷ G ⁸ ) where G ⁷ and G ⁸ represent a methyl, ethyl group propyl, butyl, pentyl or benzyl (-CH ₂ -C ₆ H ₅ );

or an oxime of formula (VI) in which:

G ³ and G ⁶ each represent a hydrogen atom; and

G ⁴ and G ⁵ form an aliphatic ring having from 5 to 11 carbon atoms, said ring being optionally substituted by one or more methyl, ethyl and / or propyl and said ring optionally including one or more heteroatoms chosen from a hydrogen atom, oxygen or a nitrogen atom, said nitrogen atom then not being bound to a hydrogen atom.

According to one embodiment of the invention, the catalyst (B) is obtained by reaction:

an alkoxide chosen from the following compounds: Ti (OiPr) ₄ , Ti (OnPr) ₄ , Ti (OnBu) ₄ , Zr (OiPr) ₄ , Zr (OnPr) ₄ , Zr (OnBu) ₄ ;

and an oxime chosen from the oximes of formula (V-1) and the oximes of formula (VI-

(V-1)

in which :

G ² represents H or a methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, -N (CH ₂ -C ₆ H ₅ ) 2 group;

G ⁴ and G ⁵ form a saturated aliphatic ring having from 5 to 11 carbon atoms.

According to one embodiment of the invention, the adhesive composition comprises at least 0.05% by weight, preferably from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, preferably still 1 to 3% by weight of catalyst (B) relative to the total weight of the adhesive composition.

According to one embodiment of the invention, the adhesive composition comprises at least 5% by weight, preferably at least 10% by weight, more preferably at least 15% by weight, of silylated polymer (A) relative to to the total weight of the adhesive composition.

According to one embodiment of the invention, the adhesive composition further comprises fillers, preferably in an amount of less than or equal to 80% by weight, preferably from 20 to 70% by weight, more preferably from 30 to 60% by weight, of the total weight of the adhesive composition.

According to one embodiment of the invention, the adhesive composition is characterized in that the silylated polymer (A) and the catalyst (B) are packaged in two separate compartments.

The present invention also relates to the use of a metal compound obtained by reaction:

at least one metal alkoxide,

with at least one oxime chosen from an oxime of formula (V) or an oxime of formula

in which:

G ¹ is a hydrogen atom or a linear or branched alkyl radical comprising

1 to 4 carbon atoms;

G ² is a hydrogen atom or a radical chosen from a linear or branched alkyl radical comprising from 1 to 10 carbon atoms, a linear alkenyl radical or branched radical comprising from 2 to 10 carbon atoms, a cyclic alkyl radical comprising from 3 to 10 carbon atoms, an aryl radical or a radical -N (G ⁷ G ⁸ ) in which G ⁷ and G ⁸ independently represent one of the other, a linear or branched alkyl radical comprising from 1 to 10 carbon atoms or a linear or branched alkenyl radical comprising from 2 to 10 carbon atoms or a benzyl radical;

G ⁵ represents either a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms, or forms the remainder of an aliphatic ring having between 4 and 14 carbon atoms with the groups G ³ and / or G ⁴ and / or G ⁶ , said aliphatic ring optionally comprising one or more heteroatoms and / or one or more double bonds and said aliphatic ring being optionally substituted by one or more alkyl groups having from 1 to 4 carbon atoms,

G ⁶ represents either a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms, or forms the remainder of an aliphatic ring having between 4 and 14 carbon atoms with the groups G ³ and / or G ⁴ and / or G ⁵ , said aliphatic ring optionally comprising one or more heteroatoms and / or one or more double bonds and said aliphatic ring being optionally substituted by one or more alkyl groups having from 1 to 4 carbon atoms,

it being understood that at least one of the groups G ⁵ or G ⁶ forms the remainder of an aliphatic ring with at least one of the groups G ³ or G ⁴ ; a silyl polymer crosslinking catalyst comprising at least one of at least two groups of formula (I):

which : R ⁴ represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, with the possibility that when there are several radicals R ⁴ , the latter are identical or different;

p is an integer equal to 0, 1 or 2. The invention also relates to a bonding process comprising applying the adhesive composition according to the invention to a surface followed by the crosslinking of said adhesive composition.

The adhesive composition according to the invention can be in mono- component form.

The adhesive composition according to the invention is devoid of tin.

The adhesive composition according to the invention is storage stable. The stability of the adhesive composition may have two aspects: (1) absence of crosslinking of the silylated polymer during storage or very limited crosslinking during storage and (2) stability of the alkoxide-derived catalyst.

The catalyst remains stable in the adhesive composition according to the invention during storage of said adhesive composition.

The curing time of the adhesive composition according to the invention is improved, in particular the curing time should generally not be excessive.

In addition, the curing time of the adhesive composition can be adjusted according to the metal / oxime molar ratio of the metal catalyst. Depending on the applications envisaged, it will be desirable to obtain more or less high crosslinking times.

BRIEF DESCRIPTION OF THE FIGURES

Fig. 1 represents the effectiveness of the crosslinking (quantifying the crosslinking rate) of a silylated polymer as a function of the amount of catalyst for different catalysts.

Fig. 2 represents the effectiveness of the crosslinking (quantifying the crosslinking rate) of another silylated polymer as a function of the amount of catalyst for different catalysts.

DETAILED DESCRIPTION OF THE EMBODIMENTS OF THE INVENTION

The present invention relates to an adhesive composition comprising: (A) at least one silylated polymer comprising at least one, preferably at least two groups of formula (I):

in which :

R ⁴ represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, with the possibility that when there are several radicals R ⁴ , the latter are identical or different;

p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1;

(B) at least one catalyst selected from organometallic compounds obtained by reaction:

at least one metal alkoxide,

in which :

For the purposes of the present invention, the term "adhesive composition" also refers to putty compositions or surface coating compositions.

The composition according to the invention is curable in the presence of moisture or after wetting.

Silylated polymer (A)

For the purposes of the present invention, the term "silylated polymer" means a polymer comprising at least one alkoxysilane group. Preferably, the silylated polymer comprising at least one alkoxysilane group is a polymer comprising at least one, preferably at least two groups of formula (I):

in which : R ⁴ represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, with the possibility that when there are several radicals R ⁴ , the latter are identical or different;

p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.

The silylated polymer as defined above comprises at least one crosslinkable alkoxysilyl group. The crosslinkable alkoxysilyl group is preferably positioned at the end of said polymer. Positioning in the middle of the chain is not excluded, however. The silylated polymer is not crosslinked before application of the adhesive composition. The adhesive composition is applied under conditions permitting its crosslinking.

The silylated polymer (A) is generally in the form of a more or less viscous liquid. Preferably, the silylated polymer has a viscosity ranging from 10 to 200 Pa.s, preferably ranging from 20 to 175 Pa.s, said viscosity being for example measured according to a Brookfield type method at 23 ° C. and 50% by weight. relative humidity (needle S28).

The silylated polymer (A) preferably comprises two groups of formula (I), but it may also comprise from three to six groups of formula (I).

Preferably, the silylated polymer or polymers (A) have an average molar mass ranging from 500 to 50000 g / mol, more preferably ranging from 700 to 20000 g / mol. The molar mass of the polymers can be measured by methods well known to those skilled in the art, for example by NMR and size exclusion chromatography using polystyrene type standards.

According to one embodiment of the invention, the silylated polymer (A) corresponds to one of the formulas (II), (III) or (IV):

OR- S (R ⁴ L (OR

^• o- c- c- m -n- NH - R S R ;; iP; OR ^";> _3I

i iV

in which R ⁴ , R ⁵ and p have the same meaning as in formula (I) described above, P represents a linear or branched, saturated or unsaturated polymeric radical optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur, silicon, and preferably having a molar mass in number ranging from 100 g / mol to 48600 g / mol, more particularly from 300 g / mol to 18600 g / mol or else from 500 g / mol to 12600 g / mol,

X represents a divalent radical chosen from -NH-, -NR ^7- or -S-,

Preferably, in formulas (II), (III) and / or (IV) above, P represents a polymeric radical selected in a non-limiting manner from polyethers, polycarbonates, polyesters, polyolefins, polyacrylates, polyether polyurethanes, polyester polyurethanes , polyolefin polyurethanes, polyacrylate polyurethanes, polycarbonate polyurethanes, polyether / polyester block polyurethanes.

For example, EP 2468783 discloses silylated polymers of formula (II) in which P represents a polyurethane / polyester / polyether block polymeric radical.

According to one embodiment, the silylated polymers are chosen from silylated polyurethanes, silylated polyethers, and mixtures thereof.

According to a particular embodiment, the silylated polymer corresponds to one of the formulas (ΙΓ), (ΙΙΓ) or (IV):

(IV) In formulas (ΙΓ), (ΙΙΓ) and (IV):

R ¹ , R ³ , R ⁴ , R ⁵ , X, R ⁷ and p have the same meaning as in formulas (II), (III) and (IV) described above,

R ² represents a saturated or unsaturated, linear or branched divalent hydrocarbon radical optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur, silicon, and preferably having a molar mass ranging from 100 g / mol to 48600 g / mol; mol, more particularly from 300 g / mol to 18600 g / mol or from 500 g / mol to 12600 g / mol,

n is an integer greater than or equal to 0, preferably ranging from 1 to 10.

In the silylated polymers of formulas (ΙΓ), (ΠΓ) or (IV) defined above, when the radical R ² comprises one or more heteroatoms, said one or more heteroatoms are not present at the end of the chain. In other words, the free valences of the divalent radical R ² bonded to the oxygen atoms neighboring the silylated polymer, each come from a carbon atom. Thus, the main chain of the radical R ² is terminated by a carbon atom at each of the two ends, said carbon atom then having a free valence.

According to one embodiment, the silylated polymers (A) are obtained from polyols chosen from polyether polyols, polyester polyols, polycarbonate polyols, polyacrylate polyols, polysiloxane polyols and polyolefins polyols and mixtures thereof, and preferably again from diols chosen from polyether diols, polyester diols, polycarbonate diols, polyacrylate diols, polysiloxane diols, polyolefin diols and mixtures thereof. In the case of the polymers of formulas (ΙΓ), (ΠΓ) or (IV) described above, such diols may be represented by the formula HO-R ² -OH where R ² has the same meaning as in the formulas ( ΙΓ), (ΠΓ) or (IV).

For example, among the radicals of R ² type that may be present in formulas (ΙΓ), (ΠΓ) or (IV), there may be mentioned the following divalent radicals whose formulas below show the 2 free valences: polypropylene

derived from a polyester diol

- derived from a polybutadiene diol:

- derived from a polyacrylate diol:

- derivative of a polysiloxane diol:

in which :

q represents an integer such that the molar mass in number of the radical R ² ranges from 100 g / mol to 48600 g / mol, preferably from 300 g / mol to 18600 g / mol, more preferably from 500 g / mol to 12600 g / mol g / mol,

r, s and t, represent zero or a non-zero integer such that the number-average molar mass of the radical R ² ranges from 100 g / mol to 48600 g / mol, preferably from 300 g / mol to 18600 g / mol, more preferably from 500 g / mol to 12600 g / mol, it being understood that the sum r + s + t is different from zero,

Q ¹ represents a linear or branched, saturated or unsaturated aromatic or aliphatic alkylene radical having preferably 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms,

Q ² represents a linear or branched divalent alkylene radical preferably having from 2 to 36 carbon atoms, more preferably from 1 to 8 carbon atoms,

Q ³ , Q ⁴ , Q ⁵ , Q ⁶ , Q ⁷ and Q ⁸ represent, independently of one another, a hydrogen atom or an alkyl, alkenyl or aromatic radical, preferably having from 1 to 12 carbon atoms preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms.

According to one embodiment, R ¹ is chosen from one of the following divalent radicals whose formulas below show the 2 free valences: a) the ra

e) - (CH ₂ ) ₆ - (or hexamethylene radical)

f)

The polymers of formula (II) or (ΙΓ) can be obtained according to a process described in documents EP 2336208 and WO 2009/106699. Those skilled in the art will be able to adapt the manufacturing method described in these two documents in the case of the use of different types of polyols. Among the polymers corresponding to formula (II), mention may be made of:

GENIOSIL® STP-E10 (available from Wacker): polyether comprising two groups (I) of dimethoxy type (n equal to 0, p equal to 1 and R ⁴ and R ⁵ represent a methyl group) having a number-average molar mass 8889 g / mol where R ³ represents a methyl group;

GENIOSIL® STP-E30 (available from Wacker): polyether comprising two groups (I) of dimethoxy type (n equal to 0, p equal to 1 and R ⁴ and R ⁵ represent a methyl group) having a number-average molar mass 14493 g / mol where R ³ represents a methyl group;

SPUR + ® 1050MM (available from Momentive): polyurethane comprising two groups (I) of trimethoxy type (n different from 0, p equal to 0 and R ⁵ represents a methyl group) having a number-average molar mass of 16393 g / mol where R ³ represents an n-propyl group;

SPUR + ® Y-191 16 (available from Momentive): polyurethane comprising two groups (I) of trimethoxy type (n different from 0 and R ⁵ represents a methyl group) having a number-average molecular weight ranging from 15,000 to 17,000 g / mol g / mol where R ³ represents an n-propyl group;

DESMOSEAL® XP 2636 (available from Bayer): polyurethane comprising two groups (I) of trimethoxy type (n different from 0, p equal to 0 and R ⁵ represents a methyl group) having a number average molar mass of 15038 g / mol where R ³ represents an n-propylene group. The polymers of formula (III) or (ΠΓ) can be obtained by hydrosilylation of polyether diallyl ether according to a process described for example in document EP 1829928. Among the polymers corresponding to formula (III), mention may be made of:

the MS SAX® 350 polymer (available from Kaneka) corresponding to a polyether comprising two groups (I) of dimethoxy type (p equal to 1 and R ⁴ represents a methyl group) having a number-average molar mass ranging from 14,000 to 16000 Dalton;

the MS SAX® 260 polymer (available from Kaneka) corresponding to a polyether comprising two groups (I) of dimethoxy type (p equal to 1, R ⁴ and R ⁵ represent a methyl group) having an average molecular weight in number of 16000 to 18000 g / mol g / mol where R ³ represents an ethyl group.

The polymers of formula (IV) or (IV) may for example be obtained by reaction of polyol (s) with diisocyanate (s) followed by reaction with aminosilanes or mercaptosilanes. A process for the preparation of polymers of formula (IV) or (IV) is described in document EP 2 583 988. Those skilled in the art will be able to adapt the manufacturing method described in this document in the case of the use of different types. polyols.

According to a preferred embodiment of the invention, the adhesive composition comprises at least one silylated polymer of formula (II) and / or (ΙΓ) or at least one silylated polymer of formula (III) and / or (ΙΙΓ).

According to one embodiment, the adhesive composition comprises a mixture of at least two different silylated polymers (A). For the purposes of the present invention, the term "different silylated polymers" means two polymers which differ either in their molecular mass or in their structure.

Thus, the adhesive composition may comprise a mixture of at least two different polymers of formula (II), a mixture of at least two polymers of formula (III) or a mixture of at least two polymers of formula (IV). The adhesive composition may also comprise a mixture of at least two polymers of different formula chosen from formulas (II), (III) and (IV).

According to one embodiment of the invention, the silylated polymer (A) used in the adhesive composition according to the invention corresponds to formula (VII):

where P 'represents a polysiloxane preferably having a molar mass in number ranging from 100 g / mol to 48600 g / mol, more particularly from 300 g / mol to 18600 g / mol or else from 500 g / mol to 12600 g / mol where f is an integer from 1 to 6, preferably ranging from 2 to 5, more preferably from 2 to 3, and wherein R ⁴ , R ⁵ and p have the same meaning as in formula (I) described above.

According to a particular embodiment, the silylated polymer (A) according to the invention is different from a polysiloxane-type silicone polymer, in particular is different from the polymer of formula (VII) described above where P 'is a polysiloxane.

According to one embodiment of the invention, all the silylated polymers of the adhesive composition are chosen from polymers of formula (II), (III) or (IV) as defined above, preferably from polymers of formula (ΙΓ), (ΠΓ) or (IV) as defined above.

The polymers of formulas (II), (III) and (IV) or of formula (ΙΓ), (ΠΓ) and (IV) are preferred to the polymers of formula (VII) since they make it possible to obtain a better adhesion on wood for example.

The silylated polymer (s) may be at least 5% by weight, preferably at least 10% by weight, more preferably at least 15% by weight, of the total weight of the adhesive composition. Generally, the content of silylated polymer (s) in the adhesive composition is preferably less than or equal to 90% by weight, more preferably less than or equal to 80% by weight, even more preferably less than or equal to 70% by weight. %) by weight, advantageously less than or equal to 60%> by weight, relative to the total weight of the adhesive composition.

The amount of silylated polymers (A) in the adhesive composition may depend on the use of said adhesive composition. Indeed, for a mastic composition, the adhesive composition will preferably comprise from 5 to 50% by weight of silylated polymers, preferably from 10 to 40% by weight of silylated polymers, relative to the total weight of the adhesive composition. . For an adhesive composition used for the formulation of self-adhesive pressure sensitive articles (PSA type), the adhesive composition will preferably comprise from 10 to 99.9% by weight, preferably from 15 to 90% by weight. more preferably from 20 to 80% by weight of silylated polymers, based on the total weight of the adhesive composition.

Crosslinking catalysts (B)

The catalysts (B) are intended for the crosslinking of the silylated polymer (A). The catalysts (B) defined in the present invention are stable, particularly when storing the adhesive composition. Thus, during the storage of the adhesive composition, the polymer (A) is in crosslinkable form (non-crosslinked). The crosslinking of the silylated polymer (A) takes place during the application of the adhesive composition to a surface to ensure a bonding or to form a coating or a seal. The catalyst (B) used in the present invention is a metal compound obtained by reaction:

at least one metal alkoxide,

in which :

G ⁵ represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or forms the remainder of an aliphatic ring having between 4 and 14 carbon atoms with the groups G ³ and / or G ⁴ and / or G ⁶ , said aliphatic ring optionally comprising one or more heteroatoms and / or one or more double bonds and said aliphatic ring being optionally substituted by one or more alkyl groups having from 1 to 4 carbon atoms,

The structure of the catalysts (B) according to the invention can for example be determined by X-ray diffraction.

It seems that the reaction between the metal alkoxide and the oxime can be represented by the following schematic equation:

M (OR) _y + x R'R "C = NOH → M (OR) _y _ _x (ON = CR'R") _x + x ROH where

M (OR) _is the metal alkoxide, y is 3 for the trivalent metals and y is 4 for the tetravalent metals,

R'R "C = NOH represents the oxime,

x is a number from 1 to 4 for tetravalent metals and x is a number from 1 to 3 for trivalent metals.

Without wishing to be bound by any theory, the inventors have discovered that a compound comprising at least one "MON" type bond where M represents a metal atom, O represents an oxygen atom and N represents a nitrogen atom. , exhibited excellent catalytic properties (while being stable) in a composition comprising crosslinkable silylated polymers.

For the purposes of the present invention, an "alkyl" group represents a saturated hydrocarbon chain, optionally comprising one or more heteroatoms. Preferably, the "alkyl" groups defined in the present invention consist solely of carbon and hydrogen atoms.

For the purposes of the present invention, the term "aliphatic ring" means a ring which is not aromatic. For the purposes of the present invention, the term "heteroatoms", an atom selected from oxygen, nitrogen, sulfur or silicon, preferably selected from oxygen, nitrogen, sulfur. The metal alkoxide may for example be in the form M (OR) _y where

M represents a metal atom, preferably selected from titanium, zirconium, aluminum, silicon, hafnium, barium, cerium or antimony,

- y is 3 or 4 (y is 3 for trivalent metals and y is 4 for tetravalent metals), and

- R represents an alkyl or alkenyl group, preferably alkyl, linear or branched having 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms, preferably 3 to 4 carbon atoms.

Thus, the metal alkoxide may for example be chosen from alkoxides of titanium, zirconium, aluminum, silicon, hafnium, barium, cerium or antimony.

According to one embodiment of the invention, the metal alkoxide is chosen from titanium alkoxides and zirconium alkoxides. Preferably, the titanium or zirconium alkoxide is selected from the following compounds: Ti (OiPr) 4, Ti (OnPr) ₄ , Ti (OnBu) ₄ , Zr (OiPr) ₄ , Zr (OnPr) ₄ , Zr ( OnBu) ₄ where:

"IPr" represents an iso-propyl group (-CH (CH3) ₂ ),

"NPr" represents an n-propyl group (-CH ₂ CH ₂ CH 3),

"NBu" represents an n-butyl group (-CH ₂ -CH ₂ -CH ₂ -CH 3).

According to a particular embodiment of the invention, the alkoxide is a titanium alkoxide, preferably of Ti (OiPr) ₄ , Ti (OnPr) ₄ , Ti (OnBu) ₄ , more preferably Ti (OnBu) type. ) _4.

According to one embodiment of the invention, in formula (V), G ¹ preferably represents a methyl group or an ethyl group, more preferably a methyl group.

According to one embodiment of the invention, in formula (V), G ² preferably represents hydrogen or a linear or branched alkyl group comprising from 1 to 8 carbon atoms, preferably from 1 to 6 carbon atoms more preferably 1 to 4 carbon atoms, or a phenyl group, or a group -N (G ⁷ G ⁸ ) where G ⁷ and G ⁸ preferably represent a methyl, ethyl, propyl, butyl, pentyl or benzyl group (-CH ₂ -C ₆ H 5), more preferably a methyl, ethyl, propyl or benzyl group.

The oxime of formula (VI) may be monocyclic or polycyclic, preferably monocyclic. For example, in the case of an oxime of formula (VI) polycyclic, when G ³ forms a ring with G ⁵ or G ⁶ and when G ⁴ forms a ring with G ⁵ or G ⁶ and when G ³ and G ⁴ ( and G ⁵ and G ⁶ ) are engaged in the same ring then the oxime has a tricyclic structure, for example of adamantane or norbornene type.

According to one embodiment of the invention, in the formula (VI),

G ³ and G ⁶ preferably each represent a hydrogen atom, and / or

G ⁴ and G ⁵ form an aliphatic ring, preferably saturated, having from 4 to 14 carbon atoms, preferably from 5 to 11 carbon atoms, more preferably 6 carbon atoms, said ring being optionally substituted by one or several groups methyl, ethyl and / or propyl and said ring optionally comprising one or more heteroatoms chosen from an oxygen atom, a sulfur atom or a nitrogen atom, said nitrogen atom then not being linked to a hydrogen atom.

By way of example of oximes of formula (VI), mention may be made of cyclohexanone oxime and cyclododecanone oxime.

According to a particular embodiment of the invention, the catalyst (B) is obtained by reaction:

years esque es:

- G ² represents H or a methyl, ethyl, iso-propyl, n-propyl, n-butyl, isobutyl, -N (CH ₂ -C ₆ H ₅ ) 2 group;

- G ⁴ and G ⁵ form a saturated aliphatic ring with 5 to 11 carbon atoms.

According to one particular embodiment of the invention, the catalyst (B) is chosen from the following catalysts:

product of the reaction between an alkoxide of formula Ti (OnBu) ₄ and 2-butanone oxime,

product of the reaction between an alkoxide of formula Ti (OnBu) ₄ and 4-methyl-2-pentanone oxime,

product of the reaction between an alkoxide of formula Ti (OnBu) ₄ and cyclohexanone oxime, 3-

product of the reaction between an alkoxide of formula Zr (OnPr) ₄ and cyclohexanone oxime.

According to one embodiment of the invention, the catalyst (B) is obtained by reaction of the alkoxide with the oxime according to an alkoxide: oxime molar ratio ranging from 1: 1 to 1: 4, preferably from 1: 2 to 1: 4. This embodiment is particularly preferred in the case of tetravalent metals (metal alkoxide). In the case of trivalent metals, the molar ratio of alkoxide: oxime is preferably from 1: 1 to 1: 3 and more preferably from 1: 2 to

1: 3.

The catalyst (B) may comprise at least 0.05% by weight, preferably from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, of the total weight of the adhesive composition.

The amount of catalyst in the adhesive composition can be varied to modulate the crosslinking time depending on the intended applications. Thus, for a so-called "quick setting" adhesive composition, it will be preferable to have a short curing time while for a so-called "slow setting" adhesive composition, it will be preferable to have a longer curing time.

The adhesive composition according to the invention may comprise a mixture of at least two different catalysts (B), in particular two catalysts (B) differing in the nature of the metal, in the nature of the alkoxide and / or in the nature of the oxime.

The catalyst (B) can be obtained by simply mixing the alkoxide with the oxime.

Preferably, the mixture of the alkoxide with the oxime is carried out at room temperature (about 23 ° C) at atmospheric pressure (about 1 bar).

During the preparation of the catalyst (B) according to the invention, it is possible to add a solvent in order to solubilize the oxime and the alkoxide. Such a solvent may for example be a polar solvent containing no alcohol group of R-OH type where R is a hydrocarbon group, said solvent may for example be chosen from tetrahydrofuran (THF), ethyl acetate, methyl ethyl ketone.

Of course, it will be ensured that the reaction between the metal alkoxide and the oxime takes place in the absence of any other reagent capable of disturbing, altering or competing with the said reaction, thus avoiding the use of complementary reagents. likely to lead to undesirable products or not having the advantageous properties attached to the present invention, as may be the case for example if the reaction is conducted in the presence of compounds of alkoxysilane type. Indeed, in the presence of an alkoxysilane compound such as described in US Pat. No. 4,956,435, a transalkoxylation reaction of the alkoxy functions of the alkoxysilane takes place by the hydroxyl function of the oxime. Thus, the adhesive composition, and in particular the catalyst, described herein is different from the adhesive composition, and in particular the catalyst, described in the present invention.

Thus, according to a preferred embodiment, the adhesive composition according to the invention is substantially free, preferably completely free, of free oxime. By the term "free oxime" is meant an oxime compound such as a compound of formula (V) or (VI) described in the present invention.

Alkoxide and oxime are commercially available products. Examples of preparation of catalysts (B) are given in the experimental part.

Other additives (C)

The adhesive composition according to the invention may comprise other additive (s)

(VS).

By "other additives" is meant additives which are not silylated polymers (A) or catalysts (B) as defined above.

Other additives include fillers, adhesion promoters, plasticizers, rheological agents, moisture absorbers, UV and thermal stabilizers, cocatalysts (different from the catalyst (B) defined in present invention).

The adhesive composition according to the invention may also comprise at least one co-catalyst ("crosslinker" in English), different from the catalyst (B). The co-catalyst (s) may be chosen from silicates having, for example, one or more hydrolysable groups, preferably the cocatalyst is tetraethylorthosilicate. The use of a co-catalyst may make it possible to improve the degree of crosslinking in certain cases.

The adhesive composition according to the invention may comprise fillers, said fillers possibly being inorganic fillers, organic fillers or a mixture of inorganic and organic fillers.

The inorganic fillers can be chosen from calcium carbonates, calcium polycarbonates, aluminum hydroxide, talcs, kaolins, carbon black, silica and fumed silica, quartz, glass beads.

The organic fillers may be chosen from polyvinyl chloride, polyethylene, polyamide, styrene-butadiene resins, or any other organic polymer in the form of a powder. Preferably, the fillers have a particle size ranging from 0.010 to 20 μηι, preferably ranging from 0.020 to 15 μηι, more preferably from 0.030 to 5 μηι.

The fillers present in the adhesive composition can provide different functions within the composition, for example a rheological agent function.

The fillers may comprise up to 80% by weight, preferably from 20 to 70% by weight, more preferably from 30 to 60% by weight, of the total weight of the adhesive composition.

Additives may be provided to adjust the rheology of the adhesive composition according to the application requirements. For example, a flow threshold increasing additive (rheological agent) may be added to avoid sagging during application of the composition, particularly when the surface receiving the adhesive composition layer is not horizontal.

The rheological agent (s) may represent from 0.01 to 8% by weight, preferably from 0.05 to 6% by weight, preferably from 0.1 to 5% by weight, of the total weight of the adhesive composition. .

The plasticizer may for example be chosen from benzoic acid esters, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid and maleic acid. , itaconic acid or citric acid or from derivatives of polyester, polyether, hydrocarbon mineral oil. Among phthalic acid derivatives, mention may be made of phthalates, such as dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate, diisodecyl phthalate, dibenzyl phthalate or phthalate phthalate. butyl benzyl. If the plasticizer is present, it is preferably chosen from phthalates, sebacates, adipates and benzoates.

The plasticizer must be compatible with the polymer and not demix in the adhesive composition. The plasticizer makes it possible to increase the plasticity (elongation) of the composition and to reduce its viscosity.

When a plasticizer is present in the composition, its content is preferably less than or equal to 5% by weight, preferably less than or equal to 3% by weight, expressed relative to the total weight of the adhesive composition. When present, the plasticizer is 0.1 to 5% by weight or preferably 0.5 to 3% by weight of the total weight of the adhesive composition.

The moisture absorber, if present, may be chosen from vinyltrimethoxysilane (VTMO) such as SILQUEST® Al 71 available from the company MOMENTIVE, vinyltriethoxysilane (VTEO) such as GENIOSIL® GF 56 available from from the WACKER Company or alkoxyarylsilanes such as GENIOSIL® XL 70 available from the WACKER Company.

The moisture absorber allows, in addition to the neutralization of the water possibly present in the adhesive composition, for example via the additives, to increase slightly the rate of crosslinking of the adhesive composition when it is too fast depending on the intended applications.

When a moisture absorber is present in the composition, its content is preferably less than or equal to 3% by weight, more preferably less than or equal to 2% by weight, expressed relative to the total weight of the adhesive composition. When present, the moisture absorber is present at 0.5 to 3% by weight and preferably 1 to 2% by weight of the total weight of the adhesive composition. If it is present in excessive amounts, the moisture absorber may cause the curing time of the adhesive composition to increase.

U.V and thermal stabilizers can be added to prevent (slow down or prevent) degradation of the polymer for better resistance to U.V or thermal shock. By way of examples, mention may be made of TINUVIN® 123, TINUVIN® 326 or IRGANOX® 245 available from BASF.

Examples of adhesion promoters include aminosilanes. In particular, aminosilanes make it possible to improve the crosslinking of silylated polymers of formula (II) or (ΙΓ) or (IV) or (IV). In the case of silylated polymer of formula (III) or (ΙΙΓ), it will be preferable that the adhesive composition does not comprise aminosilanes.

Adhesive composition

According to one particular embodiment of the invention, the adhesive composition comprises, as silylated polymers, silylated polymers of formulas (II) or (IV) as described above and, as catalyst, at least one compound chosen from:

the product of the reaction between an alkoxide of formula Ti (OnBu) ₄ and butanone oxime,

the product of the reaction between an alkoxide of formula Ti (OnBu) ₄ and 4-methyl-2-pentanone oxime,

the product of the reaction between an alkoxide of formula Ti (OnPr) ₄ and 3- (dibenzylamino) -2-propanone oxime of formula:

the product of the reaction between an alkoxide of formula Zr (OnPr) ₄ and cyclohexanone oxime.

According to another particular embodiment of the invention, the adhesive composition comprises, as silylated polymers, silylated polymers of formula (III) as described above and, as catalyst, at least one compound chosen from:

the product of the reaction between an alkoxide of formula Ti (OnBu) ₄ and butanone oxime, the product of the reaction between an alkoxide of formula Ti (OnBu) ₄ and 4-methyl-2-pentanone oxime,

According to one embodiment of the invention, the adhesive composition comprises: from 5 to 90% by weight, preferably from 10 to 70% by weight, more preferably from 15 to 60% by weight, of at least one silylated polymer (A),

from 0.05 to 10% by weight, preferably from 0.1 to 10% by weight, more preferably from 0.1 to 5% by weight, of at least one catalyst (B),

relative to the total weight of adhesive composition.

According to a particular embodiment of the invention, the adhesive composition comprises, in particular is constituted:

from 5 to 90% by weight, preferably from 10 to 70% by weight, more preferably from 15 to 60% by weight, of at least one silylated polymer (A),

from 0.05 to 10% by weight, preferably from 0.1 to 10% by weight, more preferably from 0.1 to 5% by weight, of at least one cocatalyst,

relative to the total weight of adhesive composition.

from 0.05 to 10%. by weight, preferably from 0.1 to 10%. by weight, more preferably from 0.1 to 5% by weight, of at least one catalyst (B),

from 10 to 80% by weight, preferably from 20 to 70% by weight. by weight, more preferably from 30 to 60% by weight, of at least one filler,

relative to the total weight of adhesive composition.

According to a particular embodiment of the invention, the adhesive composition comprises, in particular is constituted: from 5 to 90% by weight, preferably from 10 to 80% by weight, more preferably from 15 to 70% by weight, of at least one silylated polymer (A),

from 10 to 80% by weight, preferably from 20 to 70% by weight, more preferably from 30 to 60% by weight, of at least one filler,

from 0.05 to 20%, preferably from 0.1 to 15%, more preferably from 0.5 to 10% by weight of at least one other additive chosen from cocatalysts, promoters of adhesion, plasticizers, moisture absorbers, rheological agents and UV and thermal stabilizers.

relative to the total weight of adhesive composition.

Preferably, the adhesive composition according to the invention has a viscosity ranging from 10,000 to 100,000 mPa.s, measured at 23 ° C using a conventional rheometer taking a Bingham model.

The adhesive composition according to the invention is preferably packaged and stored in a sealed cartridge away from moisture.

According to one embodiment, the adhesive composition according to the invention is in two-component form in which the silylated polymer (A) and the catalyst (B) are packaged in two separate compartments. According to this embodiment, the compartment comprising the catalyst (B) may optionally comprise water, preferably in an amount ranging from 0.1% to 10% by weight relative to the total weight of the adhesive composition according to the invention. 'invention.

The adhesive composition is not crosslinked before use, for example by application to a support. The adhesive composition according to the invention is applied under conditions permitting its crosslinking. Crosslinking of the adhesive composition has the effect of creating, between the polymer chains of the silylated polymer described above and under the action of atmospheric moisture, siloxane-type bonds which lead to the formation of a polymeric network. -dimensional.

The adhesive composition according to the invention may be prepared by mixing the silylated polymer (s) (A) and the catalyst (s) at a temperature ranging from 10 ° C. to 40 ° C. and at a relative humidity ranging from 20 to 55 ° C. % (+/- 5%). When fillers are present in the adhesive composition, the catalyst (s) (B) is preferably added in a second step, after mixing the silylated polymer (s) and fillers. The other possible additives are introduced in accordance with usual practice.

The adhesive composition according to the invention may be packaged in a kit comprising at least two separate compartments and comprising the adhesion composition according to the invention. Said kit may comprise water, it being understood that in this case the water and the silylated polymer (s) are packaged in two separate compartments.

Thus, in such a kit, the adhesive composition according to the invention may be in two-component form in which the silylated polymer (A) and the catalyst (B) are packaged in two separate compartments. According to this embodiment, the kit may further comprise water, either in the compartment comprising the catalyst (B) or in a third compartment. In the case where the water is present in the compartment comprising the catalyst (B), the water may represent from 0.1% to 10% by weight relative to the total weight of the adhesive composition according to the invention.

According to another embodiment, the kit according to the present invention may comprise the adhesive composition in single-component form in a compartment and water in the second compartment. For example, according to this embodiment, the second compartment may comprise an aqueous solution of polyol.

Thus, during the application of the adhesive composition, the constituents of the compartments of the kit according to the invention are mixed in order to allow the crosslinking of the silylated polymer (s).

The present invention also relates to the use of an organometallic compound obtained by reaction:

at least one metal alkoxide,

in which G ¹ , G ² , G ³ , G ⁴ , G ⁵ and G ⁶ are as defined in the present invention, as a crosslinking catalyst for silylated polymers comprising at least one, preferably at least two groups of formula (I ):

wherein R ⁴ , R ⁵ and p are as defined in the present invention.

According to one embodiment of the use:

the catalyst is as defined above for the adhesive composition (catalyst

(B)); in particular, the catalyst (B) may have one or more of the characteristics described above for the adhesive composition; and or the silylated polymer is as defined above for the adhesive composition (silylated polymer (A)); in particular, the silylated polymer (A) may have one or more of the features described above for the adhesive composition.

The present invention also relates to a bonding process comprising the application of the adhesive composition according to the invention to a surface followed by the crosslinking of said adhesive composition.

The crosslinking of the adhesive composition is favored by moisture, in particular atmospheric moisture.

The adhesive composition according to the invention can be applied to all types of surfaces, such as concrete, tiles, metal, glass, wood and plastics.

EXAMPLES

Ex. 1: Preparation of adhesive compositions

1.1. ingredients

The following ingredients were used:

- silylated polymer (A):

o Al polymer: GENIOSIL® STP-E10 (available from Wacker), polyether of formula (II) comprising two groups (I) of dimethoxy type (mi equal to 0, p equal to 1 and R ⁴ and R ⁵ represent a methyl group) having a number average molecular weight of 8889 g / mol where R ³ represents a methyl group;

o polymer A2: SAX® 260 (available from Kaneka), polyether corresponding to formula (III) comprising two groups (I) of dimethoxy type (p equal to 1, R ⁴ and R ⁵ represent a methyl group) having a mass molar number average of 16,000 to 18,000 g / mol g / mol where R ³ represents an ethyl group;

o Polymer A3: SAX® 015 (available from Kaneka): polyether of formula (III) comprising two groups (I) of dimethoxysilane type with a molar mass of between 5000 and 7000 g / mol.

- other additives (C):

o Cl charges: precipitated calcium carbonate with particle sizes below 500 nm (Calofort® SV Chalk, available from Minerai Technologies)

o charges C2: calcium carbonate having a D50% of 1.7 μιη,

o charges C3: calcium carbonate having a D50% of 2.5 μιη,

o plasticizer C4: esters of phthalic acid and isomeric alcohols with 10 carbon atoms, o moisture absorber C5: vinyltrimethoxysilane type (VTMO).

metal alkoxide:

Zr ^IV (OnPr) ₄ available from Sigma Aldrich or Dorf Ketal under the trademark Tyzor® NPZ, in a form diluted to 70% in isopropanol; Zr (OiPr) ₄ available from Sigma Aldrich in solid form without solvent;

Zr ^IV (OnBu) ₄ available from Sigma Aldrich or Dorf Ketal under the trademark Tyzor® NBZ, in 80% diluted form in butanol;

Ti ^IV (OnPr) ₄ available from Sigma Aldrich in 98% pure form (without particular solvent);

Ti ^IV (OiPr) ₄ available from Sigma Aldrich in 97% pure form (without particular solvent);

o Ti ^IV (OnBu) ₄ available from Sigma Aldrich or Dorf Ketal under the trademark Tyzor® TnBT, in 97% pure form (without particular solvent).

1.2. Preparation of oxime ligands

1.2.1. Oxime ligands were obtained from a ketone (MIBK, acetone, 2-butanone, 2-pentanone, cyclohexanone) or from an aldehyde (salicylaldehyde) according to the following protocol:

Sodium hydroxide (100 mmol, 4 g) is dissolved in distilled water (10 mL) and a solution of ketone or aldehyde (80 mmol) is added. The mixture is cooled to 0 ° C. and a solution of hydrochloramine hydrochloride (100 mmol, 6.95 g) in distilled water is added slowly with stirring. After one night, the aqueous phase and the organic phase are separated. The aqueous phase is removed and the organic phase (containing the product of interest) is washed with distilled water (2 × 20 mL). The organic phase is dried under vacuum overnight to provide the oxime ligands from a ketone (MIBK, acetone, 2-butanone, 2-pentanone, cyclohexanone) or from an aldehyde (salicylaldehyde).

1.2.2. preparation of the oxime ligand from a TACO salt (product resulting from the addition of a triethylamine to an oxime chloroacetone - abbreviation of "Triethylamine Adduct of Chloroacetone oxime")

1.2.2.1. Preparation of the TACO salt: Hydroxylamine hydrochloride (182 mmol, 12.65 g) was dissolved in distilled water (80 mL) and a solution of chloroacetone (165.4 mmol, 13.63 mL) in diethyl ether (200 mL) is added. The mixture is cooled to 0 ° C and potassium carbonate (91 mmol, 12.57 g) is added slowly with stirring, giving off gas. After 2 hours, the aqueous and organic phases are separated and the aqueous phase is extracted with diethyl ether (60 ml). Triethylamine (172 mmol, 24 mL) diluted in acetonitrile (60 mL) is added dropwise to the organic phase and the mixture is stirred for 30 minutes to obtain a white precipitate. The solid is filtered and washed with cold acetonitrile (120 mL). A second precipitation can take place in the filtrate, which is in this case filtered and the solid thus obtained is also washed with acetonitrile (3x40 mL). The solids thus obtained are combined and dried under vacuum overnight to obtain the TACO salt as a white powder (34.42 g). 1.2.2.2. Preparation of the oxime from the salt TACO: A commercial secondary amine (dibenzylamine - 6 mmol) is added to a flask. TACO (6.6 mmol) and acetonitrile (80 mL) are successively added and the mixture is stirred at 85 ° C for 6 hours. After cooling, the acetonitrile is evaporated and ethyl acetate is added (30 mL) to precipitate the residual TACO and form an ammonium salt. The mixture is filtered and washed with ethyl acetate (2 x 14 mL). The organic phases are recovered and combined and then evaporated to provide the oxime from TACO.

1.3. Description of catalysts

Several catalysts were prepared by mixing metal alkoxide and oxime (monooxime) according to the alkoxide: oxime molar ratios given in Table 1 below. In Table 1, the oxime is designated by the name of the precursor (ketone or salt) used for the formation of said oxime.

The catalysts were prepared as follows:

The oxime ligands (from 4.5 × 10 ^-4 mol (alkoxide: oxime ratio 1: 1) to 1.8 × 10 ^-3 mol (alkoxide: oxime ratio 1: 4)) are introduced into a tube of 1 ml in 100 of solvent ( THF, methyl ethyl ketone or ethyl acetate) and stirred for 5 minutes. The metal precursors based on zirconium alkoxide and titanium (4.5 × 10 ^-4 mol) are added to the same tube and mixed for 1 hour at room temperature (25 ° C.).

A very schematic representation of the reaction between the metal alkoxide and the oxime is as follows: M (OR) ₄ + x R'R "C = NOH → M (OR) ₄ - _x (ON = CR" R ') _x + x ROH where M (OR) ₄ represents the metal alkoxide tested, R'R "C = NOH represents the oxime tested and x is a number ranging from 1 to 4.

Table 1: Description of catalysts B1 to B16 according to the invention

Molar ratio

Alkox oxime catalyst

alkox deroxime

B1 (1: 2) 1: 2 Ti ^IV (OnPr) ₄ 4-methyl-2-pentanone (MIBK)

Bl (l: 4) 1: 4 Ti ^IV (OnPr) ₄ MIBK

B2 (l: 2) 1: 2 Ti ^IV (OnPr) ₄ 2-butanone

B2 (l: 4) 1: 4 Ti ^IV (OnPr) ₄ 2-butanone

B3 (1: 2) 1: 2 Ti ^IV (OnPr) ₄ 2-pentanone

B3 (1: 4) 1: 4 Ti ^IV (OnPr) ₄ 2-pentanone

B4 (1: 2) 1: 2 Ti ^IV (OnBu) ₄ 2-butanone

B4 (1: 4) 1: 4 Ti ^IV (OnBu) ₄ 2-butanone

B5 (1: 2) 1: 2 Ti ^IV (OnBu) ₄ 2-pentanone

B5 (1: 4) 1: 4 Ti ^IV (OnBu) ₄ 2-pentanone

B6 (1: 2) 1: 2 Ti ^IV (OnBu) ₄ MIBK

B6 (1: 4) 1: 4 Ti ^IV (OnBu) ₄ MIBK

B7 (1: 2) 1: 2 Zr ^IV (OnPr) ₄ acetone

B7 (1: 4) 1: 4 Zr ^IV (OnPr) ₄ acetone

B8 (1: 2) 1: 2 Zr ^IV (OnPr) ₄ 2-butanone

B8 (1: 4) 1: 4 Zr ^IV (OnPr) ₄ 2-butanone

B9 (1: 2) 1: 2 Zr ^IV (OnPr) ₄ 2-pentanone

B9 (1: 4) 1: 4 Zr ^IV (OnPr) ₄ 2-pentanone

B10 (1: 2) 1: 2 Zr ^IV (OnPr) ₄ cyclohexanone

B10 (1: 4) 1: 4 Zr ^IV (OnPr) ₄ cyclohexanone

Bll (1: 2) 1: 2 Zr ^IV (OnBu) ₄ acetone

Bll (1: 4) 1: 4 Zr ^IV (OnBu) ₄ acetone

B12 (1: 2) 1: 2 Zr ^IV (OnBu) ₄ 2-butanone

B12 (1: 4) 1: 4 Zr ^IV (OnBu) ₄ 2-butanone

B13 (1: 2) 1: 2 Zr ^IV (OnBu) ₄ cyclohexanone

B13 (1: 4) 1: 4 Zr ^IV (OnBu) ₄ cyclohexanone

B14 (1: 2) 1: 2 Zr ^IV (OnBu) ₄ MIBK

B14 (1: 4) 1: 4 Zr ^IV (OnBu) ₄ MIBK

B15 (1: 2) 1: 2 Ti ^IV (OnPr) ₄ TACO

B15 (1: 4) 1: 4 Ti ^IV (OnPr) ₄ TACO

B16 (1: 2) 1: 2 Zr ^IV (OnPr) ₄ TACO

B16 (1: 4) 1: 4 Zr ^IV (OnPr) ₄ TACO Other catalysts, comparative, have been tested:

- Ref.1: dibutyltin dilaurate (DBTDL);

- Ref.2: Zr ^IV (OnPr) ₄

- Ref.3: Zr ^IV (OiPr) ₄

- Ref.4: Zr ^IV (OnBu) ₄

- Ref.5: Ti ^IV (OnPr) ₄

- Ref.6: Ti ^IV (OiPr) ₄

- Ref.7: Ti ^IV (OnBu) ₄

- Ref.8: 2-butanone oxime

- Ref.9: cyclohexanone oxime

- Ref.10: TACO oxime

Ref.l 1: Ti (OnPr) ₄ : salicylaldehyde oxime in a 1: 2 molar ratio

Ref.12: Ti ^IV (OnPr) ₄ : salicylaldehyde oxime in a 1: 4 molar ratio The oximes (Ref.8 to Ref.10) are those which have been described and prepared according to the protocol described above (section 1.2. 1). Catalysts Ref. 11 and Ref.12 were prepared according to the protocol described above (paragraph 1.3).

Ex. 2: Tests with Adhesive Compositions Comprising Silylated Polymer (Al)

Various adhesive compositions comprising Al silylated polymer (Geniosil® STPE-10) and various catalysts were prepared and evaluated.

In each adhesive composition, the molar amount of catalyst is 4.5 x 10 ^-4 mol, whereby the amount by weight of catalyst is adjusted according to the molar mass of each catalyst and the mass quantity of polymer Al.

Experimental protocol for each test:

The catalyst (4.5 × 10 ^-4 mol) in a solvent of the THF type, methyl ethyl ketone or ethyl acetate (100 μl) is added to a 1 ml tube and the mixture is stirred for 1 hour at room temperature. The polymer Al (10g) is introduced into a plastic container (50 mm in diameter and 30 mm in height) The catalyst is introduced into said plastic container and mixed with the polymer Al for 1 minute. The crosslinking is then measured according to the protocol described below.

Measurement of the crosslinking time

The crosslinking time (also called skinning time or "skinning time" in English) was evaluated by touching the surface with a peak every 5 minutes for 1 hour and then every 30 minutes up to 4 hours (ambient conditions : 55% humidity relative and 23 ° C). The composition was considered as uncrosslinked so that when touching the surface, glue residues were transferred to the tip.

Stability test

The adhesive compositions were prepared according to the same experimental protocol as that described above but in a glove box (without humidity). The plastic containers were left in the glove box for 7 days or 1 month before being returned to ambient conditions (55% relative humidity and 23 ° C) to measure the crosslinking time.

The results are indicated as follows:

A "2" indicates that the adhesive composition is very stable (crosslinking time after storage - 7 days or 1 month - identical to the crosslinking time measured just after preparation of the adhesive composition),

A "1" indicates that the adhesive composition is stable (time of crosslinking after storage - 7 days or 1 month - different but close to the crosslinking time measured just after preparation of the adhesive composition),

A "0" indicates that the adhesive composition is not stable (crosslinking time after storage - 7 days or 1 month - very different from the crosslinking time measured just after preparation of the adhesive composition).

Crosslinking times and stability are shown in Tables 2 and 3 below.

Table 2: Results with adhesive compositions according to the invention

Stability

Catalysts Crosslinking time

7 days 1 month

Bl (l: 2) 40 min 2 1

Bl (l: 4) 20 min 2 1

B2 (l: 2) 14 min 2 2

B2 (l: 4) 12 min 2 2

B3 (l: 2) 28 min 0 0

B3 (l: 4) 30 min 0 0

B4 (1: 2) 18 min 2 2

B4 (1: 4) 13 min 2 2

B6 (1: 2) 14 min 2 1

B6 (1: 4) 16 min 2 1

B7 (1: 2) 45 min 2 2

B7 (1: 4) 16 min 2 2

B8 (l: 2) 9 min 2 2

B8 (1: 4) 8 min 2 2

B9 (l: 2) 11 min 2 1

B9 (1: 4) 14 min 2 1

B10 (W: 2) 12 min 2 2

B10 (W: 4) 11 min 2 2

Bll (l: 2) 18 min 2 2

Bll (1: 4) 20 min 2 2

B12 (l: 2) 10 min 2 2

B12 (1: 4) 12 min 2 2

B13 (1: 2) 12 min 2 2

B13 (1: 4) 13 min 2 2

B14 (1: 2) 20 min 2 1

B14 (1: 4) 22 min 2 1

B15 (1: 2) 10 min 2 2

B15 (1: 4) 16 min 2 2

B16 (W: 2) 20min 2 2

B16 (W: 4) 25min 2 2 Table 3: Results with Comparative Adhesive Compositions

Stability was not evaluated for Comparative Examples Ref.8 to Ref.12 since no crosslinking could be obtained.

Table 3 above shows that adhesive compositions comprising a catalyst based on titanium alkoxide or zirconium (without oxime ligand) are not stable. Indeed, the compositions Ref.2 to Ref.7 show crosslinking even in its heart. Table 3 also shows that adhesive compositions comprising an oxime ligand catalyst (without titanium alkoxide or zirconium) do not crosslink.

On the contrary, Table 2 shows that the adhesive compositions according to the invention, that is to say comprising a catalyst based on titanium alkoxide or zirconium and oxime according to the invention, have both a good stability and satisfactory crosslinking times.

Thus, the examples show that the catalysts according to the invention obtained from a metal alkoxide and an oxime allow a better or identical stability to the stability of the metal alkoxide alone (without oxime) and / or a crosslinking of the same order of magnitude or even greater than that obtained with the corresponding metal alkoxide alone (without oxime). Ex. 3: Tests with adhesive compositions comprising the silylated polymer (Al) and precipitated calcium carbonate fillers (Cl)

Various adhesive compositions comprising silylated polymer Al (Geniosil® STPE-10), calcium carbonate C1 and various catalysts were prepared and evaluated.

The molar amount of catalyst in each adhesive composition is 4.5 x 10 ^-4 mol, whereby the amount by weight of catalyst is adjusted according to the molar mass of each catalyst and the mass quantity of Al polymer and fillers. Cl. Experimental protocol for each test:

The catalyst (4.5 × 10 ^-4 mol) in a solvent of the THF type, methyl ethyl ketone or ethyl acetate (100 μl) is added to a 1 ml tube and the mixture is stirred for 1 hour at room temperature. The polymer Al (5g) and the feeds Cl (5g) are introduced into a plastic container (50 mm in diameter and 30 mm in height) and mixed for 1 minute at 1800 rpm with a speed mixer. The catalyst is introduced into said plastic container and mixed with the mixture (polymer / fillers) for 1 minute The crosslinking time is then measured according to the protocol described in Example 2.

A vinyltrimethoxysilane (VTMO) moisture absorber was added to neutralize the amount of water present in the Cl charges. The amount of water present in the Cl charges was measured by Karl Fisher and the amount of VTMO was adjusted to neutralize only the water and not slow down the rate of crosslinking. The amount of VTMO can thus vary from 0 to 2000 mass ppm. Stability is evaluated in the same way as in Example 2

Crosslinking times and stability are shown in Tables 4 and 5 below.

Table 4: Results with adhesive compositions according to the invention

Stability

Catalysts Crosslinking time

7 days 1 month

Bl (l: 2) Instant reticulation 2 2

Bl (l: 4) Instant cross-linking 2 2

B2 (1: 2) Instant reticulation 2 2

B2 (1: 4) Instant cross-linking 2 2

B3 (1: 2) Instant reticulation 2 2

B3 (1: 4) Instant reticulation 2 2

B4 (l: 2) 1-2 min 2 2

B4 (1: 4) 1-2 min 2 2

B5 (1: 2) Instant reticulation - 1 min 2 2

B5 (1: 4) Instant reticulation - 1 min 2 2

B6 (1: 2) Instant reticulation - 1 min 2 2

B6 (1: 4) Instant reticulation - 1 min 2 2

B7 (l: 2) 2-3 min 2 2

B7 (l: 4) 1-2 min 2 2

B8 (l: 2) 1-2 min 2 2

B8 (l: 4) 1-2 min 2 2

B9 (l: 2) 1-2 min 2 2

B9 (l: 4) 1-2 min 2 2

B10 (l: 2) 2 min 2 2

B10 (W: 4) 3 min 2 2

Bll (l: 2) 1-2 min 2 2

Bll (l: 4) 1-2 min 2 2

B12 (l: 2) 1-2 min 2 2

B12 (1: 4) 1-2 min 2 2

B13 (1: 2) 1-2 min 2 2

B13 (1: 4) 2 min 2 2

B14 (1: 2) 1-2 min 2 2

B14 (1: 4) 1-2 min 2 2

B15 (1: 2) 4 min 2 2

B15 (1: 4) 6 min 2 2

B16 (W: 2) 14min 2 2

B16 (W: 4) 20min 2 2 Table 5: Results with Comparative Adhesive Compositions

Table 5 shows that adhesive compositions comprising an oxime ligand catalyst (without metal alkoxide) do not crosslink.

In contrast, Table 4 shows that the adhesive compositions according to the invention, that is to say comprising a catalyst based on titanium alkoxide or zirconium and oxime according to the invention, have crosslinking times. satisfactory, of the order of 1 to 2 minutes only for certain catalysts and said adhesive compositions are stable.

Ex. 4: Tests with Adhesive Compositions Comprising Silylated Polymer (A2)

Various adhesive compositions comprising silylated polymer A2 (SAX® 260) and various catalysts were prepared and evaluated.

The molar amount of catalyst in each adhesive composition is 9.5 x 10 ^-5 mol, whereby the amount by weight of catalyst is adjusted as a function of the molar mass of each catalyst and the mass quantity of polymer A2.

Experimental protocol for each test:

The catalyst (9.5 × 10 ^-5 mol) in a solvent of the THF, methyl ethyl ketone or ethyl acetate type (100 μl) is added to a 1 ml tube and the mixture is stirred for 1 hour at room temperature. The polymer A2 (10g) is introduced into a plastic container (50 mm in diameter and 30 mm in height) The catalyst is introduced into said plastic container and mixed with the polymer A2 for 1 minute. The crosslinking is then measured according to the protocol described in Example 2.

The stability is evaluated according to the protocol described in Example 2.

Crosslinking times and stability are shown in Tables 6 and 7 below. Table 6: Results with adhesive compositions according to the invention

Table 7: Results with Comparative Adhesive Compositions

It has been observed that the adhesive compositions comprising a catalyst based on titanium alkoxide or zirconium (without oxime ligand) mixed with the polymer A2 (generally valid for the polymers of formula (III) described above) are not stable. The inventors have indeed observed that in the presence of polymers of formula (III), catalysts consisting solely of alkoxide could react on themselves. Thus, after storage, the adhesive composition comprising a polymer of formula (III), such as polymer A2, and a catalyst consisting of titanium alkoxide or zirconium, can not crosslink properly because of the instability of the catalyst. himself.

In addition, Table 7 shows that adhesive compositions comprising an oxime ligand catalyst (without metal alkoxide) do not crosslink.

In contrast, Table 6 shows that the adhesive compositions according to the invention, that is to say comprising a catalyst based on titanium alkoxide or zirconium and oxime according to the invention, have both a good stability and satisfactory crosslinking times, which may be of the order of 24 or 48 hours, with a silylated polymer type A2 (difficult to crosslink).

Ex. 5: Tests with formulations comprising two silylated polymers (A2 and A3) and additives (C2 and C3 fillers, plasticizer C4 and C5 moisture absorber)

Different formulations comprising 12% by weight of a silylated polymer A2 (SAX® 260), 4% by weight of a second silylated polymer A3 (SAX® 015), 28% by weight of C2 fillers, 40% by weight of C3 fillers, 15% by weight of a C4 plasticizer and 0.8% by weight of a C5 moisture absorber.

Then, a given molar amount (9.5 x 10 ^-5 mol) of catalyst is added to each formulation described above, varying the nature of the catalyst, so that the amount by weight of catalyst is adjusted according to the molar mass of each catalyst and the mass quantity of the formulation.

Experimental protocol for each test:

The catalyst (9.5 × 10 ^-5 mol) in a solvent of the THF, methyl ethyl ketone or ethyl acetate type (100 μl) is added to a 1 ml tube and the mixture is stirred for 1 hour at room temperature. 10g of the formulation comprising the polymers A1 and A2 and the additives C2, C3, C4 and C5 are introduced into a plastic container (50 mm in diameter and 30 mm in height) .The catalyst is introduced into said container. made of plastic and mixed with the formulation (polymers + additives) for 1 minute at 1800 rpm with a speed mixer The crosslinking time is then measured according to the protocol described in Example 2.

The stability is evaluated according to the protocol described in Example 2.

Crosslinking times and stability are shown in Tables 8 and 9 below. Table 8: Results with adhesive compositions according to the invention

Table 9: Results with Comparative Adhesive Compositions

Table 9 shows that adhesive compositions comprising an oxime ligand catalyst (without titanium alkoxide or zirconium) do not crosslink.

In contrast, Table 8 shows that the adhesive compositions according to the invention, that is to say comprising a catalyst based on titanium alkoxide or zirconium and oxime according to the invention, have both a good stability and satisfactory crosslinking times. Ex. 6: Variation of the amount of catalyst

Further tests were carried out by varying the amount of catalyst from 0.05% to 5% by weight of the total weight of the adhesive composition.

6.1. An adhesive composition comprising Al silylated polymer (Geniosil® STP-E10) and from 0.05 to 5% by weight of a catalyst.

The catalysts tested are those prepared according to Example 1 above.

Fig. 1 represents the results expressed by the efficiency in min ^-1 (inverse of the crosslinking time) of the crosslinking as a function of the amount of catalyst (in weight percentage in the adhesive composition).

In this fig. 1, the curves represent different catalysts tested.

As illustrated in FIG. 1, the catalysts according to the invention are also effective at low concentration (less than 1% by weight) than the catalysts of the prior art (Ref 1 referenced DBTDL on Fig. 1) and the catalysts according to the invention are much more effective (much higher crosslinking rate) than the catalysts of the prior art at levels ranging from 1 to 5% by weight.

6.2. An adhesive composition comprising silylated polymer A2 (SAX® 260 and 0.05 to 5% by weight of a catalyst.

The catalysts tested are those prepared according to Example 1 above.

Fig. 2 represents the results expressed by the efficiency in h ^-1 (inverse of the crosslinking time) of the crosslinking as a function of the amount of catalyst (as a percentage by weight in the adhesive composition).

In this picture. 2, the curves represent different catalysts tested.

As illustrated in FIG. 2, the catalysts according to the invention are also effective at low concentration (less than 0.5% by weight) than the catalysts of the prior art (Ref 1 referenced DBTDL on Fig. 1) and the catalysts according to the invention are much more effective (much higher crosslinking rate) than the catalysts of the prior art at levels ranging from 0.5 to 5% by weight.

Claims

1. Adhesive composition comprising at least one silylated polymer (A) and at least one catalyst (B),

in which :

R ⁴ represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, with the possibility that when there are several R ⁴ radicals, the latter are identical or different;

R ⁵ represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, with the possibility that when there are several R ⁵ radicals, the latter are identical or different, with the possibility that two OR ⁵ groups can be involved in the same cycle;

- p is an integer equal to 0, 1 or 2;

and said at least one catalyst being chosen from the metal compounds obtained by reaction:

- at least one metal alkoxide,

- with at least one oxime chosen from an oxime of formula (V) or an oxime of formula (VI):

in which :

G ¹ is a hydrogen atom or a linear or branched alkyl radical comprising 1 to 4 carbon atoms;

G ² is a hydrogen atom or a radical chosen from a linear or branched alkyl radical comprising from 1 to 10 carbon atoms, a linear or branched alkenyl radical comprising from 2 to 10 carbon atoms, a cyclic alkyl radical comprising from 3 with 10 carbon atoms, an aryl radical or a radical -N(G ⁷ G ⁸ ) where G ⁷ and G ⁸ represent, independently of one another, a linear alkyl radical or branched comprising from 1 to 10 carbon atoms or a linear or branched alkenyl radical comprising from 2 to 10 carbon atoms or a benzyl radical;

G ³ represents either a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, or forms the remainder of an aliphatic cycle having between 4 and 14 carbon atoms with the G ⁴ and/or G ⁵ groups and/or G ⁶ , said aliphatic cycle optionally comprising one or more heteroatoms and/or one or more double bonds and said aliphatic cycle optionally being substituted by one or more alkyl groups having 1 to 4 carbon atoms,

G ⁴ represents either a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, or forms the remainder of an aliphatic cycle having between 4 and 14 carbon atoms with the G ³ and/or G ⁵ groups. and/or G ⁶ , said aliphatic cycle optionally comprising one or more heteroatoms and/or one or more double bonds and said aliphatic cycle optionally being substituted by one or more alkyl groups having 1 to 4 carbon atoms,

it being understood that at least one of the G ³ or G ⁴ groups forms the remainder of an aliphatic cycle with at least one of the G ⁵ or G ⁶ groups;

G ⁵ represents either a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, or forms the remainder of an aliphatic cycle having between 4 and 14 carbon atoms with the G ³ and/or G ⁴ groups and/or G ⁶ , said aliphatic cycle optionally comprising one or more heteroatoms and/or one or more double bonds and said aliphatic cycle optionally being substituted by one or more alkyl groups having 1 to 4 carbon atoms,

G ⁶ represents either a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, or forms the remainder of an aliphatic cycle having between 4 and 14 carbon atoms with the G ³ and/or G ⁴ groups and/or G ⁵ , said aliphatic cycle optionally comprising one or more heteroatoms and/or one or more double bonds and said aliphatic cycle optionally being substituted by one or more alkyl groups having 1 to 4 carbon atoms,

it being understood that at least one of the G ⁵ or G ⁶ groups forms the remainder of an aliphatic cycle with at least one of the G ³ or G ⁴ groups.

2. Composition according to claim 1, in which the silylated polymer corresponds to one of formulas (II), (III), (IV) or (VII):

(II)

(III)

O— WR— NH- -R— SifR ÏPÎO ^'

O

(IV)

(VII)

in which :

R ⁴ , R ⁵ and p have the same meaning as in formula (I) described in claim 1,

P represents a saturated or unsaturated, linear or branched polymer radical optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur, silicon, and preferably having a molar mass in number ranging from 100 g/mol to 48,600 g/mol, more particularly from 300 g/mol to 18600 g/mol or even from 500 g/mol to 12600 g/mol,

P' represents a polysiloxane, preferably having a molar mass in number ranging from 100 g/mol to 48600 g/mol, more particularly from 300 g/mol to 18600 g/mol or even from 500 g/mol to 12600 g/mol ,

R ¹ represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms which may be aromatic or aliphatic, linear, branched or cyclic, R ³ represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,

- X represents a divalent radical chosen from -NH-, -NR ⁷ - or -S-,

f is an integer ranging from 1 to 6, preferably ranging from 2 to 5, more preferably ranging from 2 to 3.

3. Composition according to claim 2, in which the silylated polymer corresponds to one of formulas (II), (III) or (IV) as defined in claim 2.

4. Composition according to claim 2 or 3, in which the silylated polymer corresponds to one of the formulas (ΙΓ), (ΠΓ) or (IV):

(IF)

(R ⁵ 0) _3.p (R ⁴ ) _p Si-R— O— R¾-0— R¾-0 R— Si(R ⁴ ) _p (OR ⁵ ) ₃ . _p

(ΙΙΓ)

(R ⁵ 0) _{3 D} (R ⁴ )„Si— R-— — NH-R-— NH-C— X— R— Si(R ⁴ )p(OR ⁵ ) ₃ „

^P II II HHJHH ' ^{3 P}

oooo ⁿ oo

(IV)

in the formulas (ΙΓ), (ΙΙΓ) and (IV):

R ¹ , R ³ , R ⁴ , R ⁵ , X, R ⁷ and p have the same meaning as in formulas (II), (III) and (IV) described in claim 2,

R ² represents a saturated or unsaturated, linear or branched divalent hydrocarbon radical optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur, silicon, and preferably having a number molar mass ranging from 100 g/mol to 48,600 g/ mol, more particularly from 300 g/mol to 18600 g/mol or even from 500 g/mol to 12600 g/mol,

- n is an integer greater than or equal to 0, preferably ranging from 1 to 10.

5. Adhesive composition according to any one of claims 1 to 4, in which the metal alkoxide corresponds to the formula M(OR) _y where

M represents a metal, preferably chosen from titanium, zirconium, aluminum, silicon, hafnium, barium, cerium and antimony,

- y is equal to 3 or 4, and

- R represents a linear or branched alkyl group having 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms, preferably 3 to 4 carbon atoms or a linear or branched alkenyl group having 2 to 5 atoms carbon, preferably 2 to 4 carbon atoms, preferably 3 to 4 carbon atoms.

6. Adhesive composition according to any one of claims 1 to 5, in which the oxime is an oxime of formula (V) in which:

G ¹ represents a methyl group or an ethyl group; And G ² represents hydrogen or a linear or branched alkyl group comprising 1 to 8 carbon atoms, or a phenyl group, or a -N(G ⁷ G ⁸ ) group where G ⁷ and G ⁸ represent a methyl, ethyl group , propyl, butyl, pentyl or benzyl (-CH ₂ -C ₆ H ₅ );

or an oxime of formula (VI) in which:

G ³ and G ⁶ each represent a hydrogen atom; And

G ⁴ and G ⁵ form an aliphatic ring having 5 to 1 1 carbon atoms, said ring optionally being substituted by one or more methyl, ethyl and/or propyl groups and said ring optionally comprising one or more heteroatoms chosen from an atom d oxygen or a nitrogen atom, said nitrogen atom then not being linked to a hydrogen atom.

7. Adhesive composition according to any one of claims 1 to 6, in which the catalyst (B) is obtained by reaction:

- an alkoxide chosen from the following compounds: Ti(OiPr) ₄ , Ti(OnPr) ₄ , Ti(OnBu) ₄ , Zr(OiPr) ₄ , Zr(OnPr) ₄ , Zr(OnBu) ₄ ;

- and an oxime chosen from the oximes of formula (V-1) and the oximes of formula (VI-

in which :

G ² represents H or a methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, -N(CH ₂ -C ₆ H ₅ ) _{2 group} ;

G ⁴ and G ⁵ form a saturated aliphatic ring having 5 to 1 1 carbon atoms.

8. Adhesive composition according to any one of claims 1 to 7, in which the catalyst (B) is obtained by reaction of the alkoxide with the oxime in an alkoxide: oxime molar ratio ranging from 1: 1 to 1:4 .

9. Adhesive composition according to any one of claims 1 to 8, comprising at least 0.05% by weight, preferably from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, of more preferably from 1 to 3% by weight of catalyst (B) relative to the total weight of the adhesive composition.

10. Adhesive composition according to any one of claims 1 to 9, comprising at least 5% by weight, preferably at least 10% by weight, more preferably at least 15% by weight, of silylated polymer (A) relative to to the total weight of the adhesive composition.

11. Adhesive composition according to any one of claims 1 to 10, further comprising fillers, preferably in an amount less than or equal to 80% by weight, preferably ranging from 20 to 70% by weight, more preferably from 30 to 60%> by weight, of the total weight of the adhesive composition.

12. Adhesive composition according to any one of claims 1 to 11, characterized in that the silylated polymer (A) and the catalyst (B) are packaged in two separate compartments.

13. Use of a metal compound obtained by reaction:

- at least one metal alkoxide,

- with at least one oxime chosen from an oxime of formula (V) or an oxime of formula

G ² is a hydrogen atom or a radical chosen from a linear or branched alkyl radical comprising from 1 to 10 carbon atoms, a linear or branched alkenyl radical comprising from 2 to 10 carbon atoms, a cyclic alkyl radical comprising from 3 with 10 carbon atoms, an aryl radical or an -N(G ⁷ G ⁸ ) radical where G ⁷ and G ⁸ represent, independently of one another, a linear or branched alkyl radical comprising from 1 to 10 atoms of carbon or a linear or branched alkenyl radical comprising from 2 to 10 carbon atoms or a benzyl radical; G ³ represents either a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, or forms the remainder of an aliphatic ring having between 4 and 14 carbon atoms with the groups G ⁴ and/or G ⁵ and/or G ⁶ , said aliphatic cycle optionally comprising one or more heteroatoms and/or one or more double bonds and said aliphatic cycle optionally being substituted by one or more alkyl groups having from 1 to 4 carbon atoms,

it being understood that at least one of the G ⁵ or G ⁶ groups forms the remainder of an aliphatic cycle with at least one of the G ³ or G ⁴ groups; as a catalyst for crosslinking silylated polymers comprising at least one, preferably at least two groups of formula (I):

in which :

R ⁵ represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, with the possibility that when there are several R ⁵ radicals, the latter are identical or different, with the possibility that two OR ⁵ groups can be involved in the same cycle; - p is an integer equal to 0, 1 or 2.

14. Use according to claim 13, in which the silylated polymer and/or the catalyst is as defined in any one of claims 2 to 11.

15. Bonding process comprising the application of the adhesive composition according to any one of claims 1 to 12 on a surface followed by the crosslinking of said adhesive composition.