Cross-linkable silylated polymer-based adhesive compositions

Patent metadata

Field	Value
Publication number	US-10995246-B2
Application number	US-201716310054-A
Country	US
Kind code	B2
Filing date	Jun 5, 2017
Priority date	Jun 14, 2016
Publication date	May 4, 2021
Grant date	May 4, 2021

Abstract

The present invention provides a curable adhesive composition comprising at least one curable silylated polymer and at least one curing catalyst obtained by reaction of a metal alkoxide and an oxime. The present invention also provides the use of a metal compound obtained by reaction of a metal alkoxide and an oxime as curing catalyst for silylated polymers.

First claim

The invention claimed is:

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 aliph

Assignees

• Bostik Sa
• Centre Nat Rech Scient
• Univ Rennes

Inventors

• Colin Boris
• Michaud Guillaume
• Simon Frederic
• Lavastre Olivier

Classifications

• C08G18/222

  metal compounds not provided for in groups C08G18/225 - C08G18/26 · CPC title

• C08G18/4825

  Polyethers containing two hydroxy groups (C08G18/4833 - C08G18/5096 take precedence) · CPC title

• C09J175/08 Primary

  from polyethers · CPC title

• C09J183/04 Primary

  Polysiloxanes · CPC title

• C09J201/10

  containing hydrolysable silane groups · CPC title