Cross-linkable silylated polymer-based adhesive compositions

1. 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 group of formula (I):

—Si(R 4 ) p (OR 5 ) 3-p   (I)

wherein:

R 4 represents a linear or branched alkyl radical having from 1 to 4 carbon atoms, it being possible that when there are more than one radicals R 4 , the latter are identical or different;

R 5 represents a linear or branched alkyl radical having from 1 to 4 carbon atoms, it being possible that when there are more than one radicals R 5 , the latter are identical or different, it being possible that two groups OR 5 may be engaged in the same ring;

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

and said at least one catalyst being selected from the metal compounds obtained by reaction, in the absence of any other reagent in said reaction:

of at least one metal alkoxide,

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

wherein:

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

G 2 is a hydrogen atom or a radical selected from a linear or branched alkyl radical having from 1 to 10 carbon atoms, a linear or branched alkenyl radical having from 2 to 10 carbon atoms, a cyclic alkyl radical having from 3 to 10 carbon atoms, an aryl radical or a radical —N(G 7 G 8 ) where G 7 and G 8 independently represent a linear or branched alkyl radical having from 1 to 10 carbon atoms or a linear or branched alkenyl radical having 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 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 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 ,

and wherein the adhesive composition is substantially free of free oxime.

2. The composition according to claim 1 , wherein the silylated polymer corresponds to one of the formulae (II), (III), (IV) or (VII):

wherein:

R 4 , R 5 and p have the same meaning as in the 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, sulphur, silicon, and

P′ represents a polysiloxane,

R 1 represents a divalent hydrocarbon radical having 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 having from 1 to 6 carbon atoms,

X represents a divalent radical selected from —NH—, —NR 7 — or —S—,

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

f is an integer ranging from 1 to 6.

3. The composition according to claim 2 , wherein the silylated polymer corresponds to one of the formulae (II), (III) or (IV) as defined in claim 2 .

4. The composition according to claim 3 , wherein the silylated polymer corresponds to one of the formulae (II′), (III′) or (IV′):

wherein in the formulae (II′), (III′) and (IV′)

R 1 represents a divalent hydrocarbon radical having 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 having from 1 to 6 carbon atoms,

R 4 represents a linear or branched alkyl radical having from 1 to 4 carbon atoms, it being possible that when there are more than one radicals R 4 , the latter are identical or different;

R 5 represents a linear or branched alkyl radical having from 1 to 4 carbon atoms, it being possible that when there are more than one radicals R 5 , the latter are identical or different, it being possible that two groups OR 5 may be engaged in the same ring;

X represents a divalent radical selected from —NH—, —NR 7 — or —S—,

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

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

R 2 represents a saturated or unsaturated, linear or branched divalent hydrocarbon radical optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulphur, or silicon,

n is an integer greater than or equal to 0.

5. The composition according to claim 2 , wherein the silylated polymer corresponds to one of the formulae (II′), (III′) or (IV′):

in the formulae (II′), (III′) and (IV′)

R 1 , R 3 , R 4 , R 5 , X, R 7 and p have the same meaning as in the formulae (II), (Ill) 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, sulphur, silicon,

n is an integer greater than or equal to 0.

6. The adhesive composition according to claim 1 , wherein the metal alkoxide corresponds to the formula M(OR) y where

M represents a metal,

y is equal to 3 or 4, and

R represents a linear or branched alkyl group having from 1 to 5 carbon atoms.

7. The adhesive composition according to claim 1 , wherein the oxime is an oxime of formula (V) wherein:

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

G 2 represents hydrogen or a linear or branched alkyl group having 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, propyl, butyl, pentyl or benzyl (—CH 2 —C 6 H 5 ) group;

or an oxime of formula (VI) wherein:

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 groups and said ring optionally comprising one or more heteroatoms selected from an oxygen atom or a nitrogen atom, said nitrogen atom then not being bonded to a hydrogen atom.

8. The adhesive composition according to claim 1 , wherein the catalyst (B) is obtained by reaction:

of an alkoxide selected 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 selected from the oximes of formula (V-1) and the oximes of formula (VI-1):

wherein:

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.

9. The adhesive composition according to claim 1 , wherein 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.

10. The adhesive composition according to claim 1 , comprising at least 0.05% by weight, of catalyst (B) based on the total weight of the adhesive composition.

11. The adhesive composition according to claim 1 , comprising at least 5% by weight, of silylated polymer (A) based on the total weight of the adhesive composition.

12. The adhesive composition according to claim 1 , further comprising fillers.

13. The adhesive composition according to claim 1 , characterized in that the silylated polymer (A) and the catalyst (B) are packaged in two separate compartments.

14. A bonding method comprising applying the adhesive composition according to claim 1 to a surface and then curing said adhesive composition.

15. An adhesive composition of claim 1 comprising

an amount of catalyst B in a range selected from 0.1 to 10% by weight, 0.5 to 5% by weight, or 1 to 3% by weight,

an amount of silylated polymer (A) selected from at least 10% by weight or at least 15% by weight, and

an amount of filler within a range selected from 20 to 70% by weight or 30 to 60% by weight, each based on the total weight of the adhesive composition.

16. The composition according to claim 1 , wherein the reaction between the metal alkoxide and the oxime is represented by the following schematic equation:

M(OR) y +xR′R″C═NOH→M(OR) y-x (ON═CR′R″) x +xROH   

where

M(OR) y represents the metal alkoxide,

y is equal to 3 for trivalent metals and y is equal to 4 for tetravalent metals,

M represents a metal atom,

R represents a linear or branched alkyl or alkenyl group having from 1 to 5 carbon atoms,

R′R″C═NOH represents the oxime of formula (V) or (VI), and x is a number ranging from 1 to 4 for tetravalent metals and x is a number ranging from 1 to 3 for trivalent metals.

17. The composition according to claim 1 , wherein the adhesive composition is completely free of free oxime.

18. A method comprising using a metal compound as curing catalyst for silylated polymers, wherein said metal compound is obtained by reaction:

of at least one metal alkoxide,

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

wherein:

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

G 2 is a hydrogen atom or a radical selected from a linear or branched alkyl radical having from 1 to 10 carbon atoms, a linear or branched alkenyl radical having from 2 to 10 carbon atoms, a cyclic alkyl radical having from 3 to 10 carbon atoms, an aryl radical or a radical—N(G 7 G 8 ) where G 7 and G 8 independently represent a linear or branched alkyl radical having from 1 to 10 carbon atoms or a linear or branched alkenyl radical having 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 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 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 ;

said silylated polymers comprising at least one group of formula (I):

—Si(R 4 ) p (OR 5 ) 3-p   (I)

wherein:

R 4 represents a linear or branched alkyl radical having from 1 to 4 carbon atoms, it being possible that when there are more than one radicals R 4 , the latter are identical or different;

R 5 represents a linear or branched alkyl radical having from 1 to 4 carbon atoms, it being possible that when there are more than one radicals R 5 , the latter are identical or different, it being possible that two groups OR 5 may be engaged in the same ring;

p is an integer equal to 0, 1 or 2, such that the obtained metal compound is substantially free of free oxime.

19. A method according to claim 18 , wherein the silylated polymer corresponds to one of the formulae (II), (III), (IV) or (VII):

wherein:

R 4 represents a linear or branched alkyl radical having from 1 to 4 carbon atoms, it being possible that when there are more than one radicals R 4 , the latter are identical or different;

R 5 represents a linear or branched alkyl radical having from 1 to 4 carbon atoms, it being possible that when there are more than one radicals R 5 , the latter are identical or different, it being possible that two groups OR 5 may be engaged in the same ring;

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

P represents a saturated or unsaturated, linear or branched polymer radical optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulphur, silicon, and

P′ represents a polysiloxane,

R 1 represents a divalent hydrocarbon radical having 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 having from 1 to 6 carbon atoms,

X represents a divalent radical selected from —NH—, —NR 7 — or —S—,

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

f is an integer ranging from 1 to 6 .

20. A method according to claim 19 , wherein the silylated polymer corresponds to one of the formulae (II′), (III′) or (IV′):

wherein in the formulae (II′), (III′) and (IV′)

R 1 represents a divalent hydrocarbon radical having 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 having from 1 to 6 carbon atoms,

R 4 represents a linear or branched alkyl radical having from 1 to 4 carbon atoms, it being possible that when there are more than one radicals R 4 , the latter are identical or different;

R 5 represents a linear or branched alkyl radical having from 1 to 4 carbon atoms, it being possible that when there are more than one radicals R 5 , the latter are identical or different, it being possible that two groups OR 5 may be engaged in the same ring;

X represents a divalent radical selected from —NH—, —NR 7 — or —S—,

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

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

R 2 represents a saturated or unsaturated, linear or branched divalent hydrocarbon radical optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulphur, silicon, and

n is an integer greater than or equal to 0.