CATALYTIC COMPOSITION FOR AN ADHESIVE COMPOSITION BASED ON A CROSS-LINKABLE SILYLATED POLYMER

Abstract

1) Adhesive composition comprising at least one crosslinkable silylated polymer (A) and a catalytic composition (B) comprising: a tertiary amine (C) with a pKa of greater than 11 and an organometallic compound (D) obtained by reacting a metal alkoxide (D1) with an oxime (D2).

2) Corresponding catalytic composition (B).

Claims

1. An adhesive composition comprising: at least one silylated polymer (A) comprising at least one, preferably at least two, groups of formula (I):
Si(R.sup.4).sub.p(OR.sup.5).sub.3-p(I) in which: R.sup.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.sup.4, these radicals are identical or different; R.sup.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.sup.5, these radicals are identical or different, with the possibility that two groups OR.sup.5 may be engaged in the same ring; p is an integer equal to 0, 1 or 2; and a catalytic composition (B) comprising: a tertiary amine (C) with a pKa of greater than 11; and an organometallic compound (D) obtained by reacting at least one metal alkoxide (D1) with at least one oxime (D2) chosen from an oxime of formula (V) or an oxime of formula (VI): ##STR00027## ##STR00028## in which: G.sup.1 is a hydrogen atom or a linear or branched alkyl radical comprising from 1 to 4 carbon atoms; G.sup.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 alkenylradical 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.sup.7G.sup.8) in which G.sup.7 and G.sup.8 represent, independently of each 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.sup.3 represents either a hydrogen atom, or an alkyl group containing from 1 to 4 carbon atoms, or forms the residue of an aliphatic ring containing between 4 and 14 carbon atoms with the groups G.sup.4 and/or G.sup.5 and/or G.sup.6, said aliphatic ring optionally comprising one or more heteroatoms and/or one or more double bonds and said aliphatic ring being optionally substituted with one or more alkyl groups containing from 1 to 4 carbon atoms; G.sup.4 represents either a hydrogen atom, or an alkyl group containing from 1 to 4 carbon atoms, or forms the residue of an aliphatic ring containing between 4 and 14 carbon atoms with the groups G.sup.3 and/or G.sup.5 and/or G.sup.6, said aliphatic ring optionally comprising one or more heteroatoms and/or one or more double bonds and said aliphatic ring being optionally substituted with one or more alkyl groups containing from 1 to 4 carbon atoms; it being understood that at least one of the groups G.sup.3 or G.sup.4 forms the residue of an aliphatic ring with at least one of the groups G.sup.5 or G.sup.6; G.sup.5 represents either a hydrogen atom, or an alkyl group containing from 1 to 4 carbon atoms, or forms the residue of an aliphatic ring containing between 4 and 14 carbon atoms with the groups G.sup.3 and/or G.sup.4 and/or G.sup.6, said aliphatic ring optionally comprising one or more heteroatoms and/or one or more double bonds and said aliphatic ring being optionally substituted with one or more alkyl groups containing from 1 to 4 carbon atoms; G.sup.6 represents either a hydrogen atom, or an alkyl group containing from 1 to 4 carbon atoms, or forms the residue of an aliphatic ring containing between 4 and 14 carbon atoms with the groups G.sup.3 and/or G.sup.4 and/or G.sup.5, said aliphatic ring optionally comprising one or more heteroatoms and/or one or more double bonds and said aliphatic ring being optionally substituted with one or more alkyl groups containing from 1 to 4 carbon atoms; it being understood that at least one of the groups G.sup.5 or G.sup.6 forms the residue of an aliphatic ring with at least one of the groups G.sup.3 or G.sup.4.

2. The adhesive composition as claimed in claim 1, characterized in that the silylated polymer (A) corresponds to one of the formulae (II), (Ill) or (IV): ##STR00029## in which: R.sup.4, R.sup.5 and p have the same meaning as in formula (I) described in claim 1, P represents a saturated or unsaturated, linear or branched polymeric radical optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur or silicon, R.sup.1 represents a divalent hydrocarbon-based radical comprising from 5 to 15 carbon atoms, which may be aromatic or aliphatic, linear, branched or cyclic, R.sup.3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, X represents a divalent radical chosen from NH, NR.sup.7 or S, R.sup.7 represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms and which may also comprise one or more heteroatoms, f is an integer ranging from 1 to 6.

3. The adhesive composition as claimed in claim 2, characterized in that the silylated polymer (A) corresponds to one of the formulae (II), (III) or (IV): ##STR00030## in which: R.sup.1, R.sup.3, R.sup.4, R, X, R.sup.7 and p have the same meaning as in formulae (II), (III) and (IV) described in claim 2, R.sup.2 represents a saturated or unsaturated, linear or branched divalent hydrocarbon-based radical optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur or silicon, n is an integer greater than or equal to 0.

4. The adhesive composition as claimed in claim 3, characterized in that the silylated polymer (A) is such that the radical R.sup.2 included in formulae (II), (III) and (IV) is derived from a polypropylene glycol.

5. The adhesive composition as claimed 1, characterized in that the catalytic composition (B) comprises, as tertiary amine (C), a phosphazene (C1) of formula (VII): ##STR00031## in which: J.sup.1 represents a linear or branched alkyl radical comprising from 1 to 6 carbon atoms, J.sup.2 and J.sup.3 represent, independently of each other, an alkyl radical comprising from 1 to 4 carbon atoms or together form, with the nitrogen atom to which they are attached, an aliphatic heterocycle comprising from 4 to 6 carbon atoms; J.sup.4 and J.sup.5 represent, independently of each other, an alkyl radical comprising from 1 to 4 carbon atoms or together form, with the nitrogen atom to which they are attached, an aliphatic heterocycle comprising from 3 to 4 carbon atoms; J.sup.6 and J.sup.7 represent, independently of each other, an alkyl radical comprising from 1 to 4 carbon atoms or together form, with the nitrogen atom to which they are attached, an aliphatic heterocycle comprising from 4 to 6 carbon atoms; it also being understood that J.sup.4 (or J.sup.5) may form with at least one of the groups J.sup.6 (or J.sup.7) and/or J.sup.2 (or J), and also with the two nitrogen atoms and the phosphorus atom to which they are attached, an aliphatic ring comprising 3 to 4 carbon atoms.

6. The adhesive composition as claimed 1, characterized in that the catalytic composition (B) comprises, as tertiary amine (C), a guanidine or an amidine with a pKa of greater than 11.

7. The adhesive composition as claimed in claim 1, characterized in that the catalytic composition (B) comprises an organometallic compound (D) which is obtained by reaction of a metal alkoxide (D1) in the form of formula (VIII):
M(OR).sub.y(VIII) in which: M represents a metal atom, preferably chosen from titanium, zirconium, aluminum, zinc, bismuth, silicon, hafnium, barium, cerium, cesium, rubidium and antimony, y is equal to 1, 2, 3 or 4 according to the valency of the metal atom M, and R represents an alkyl, alkenyl, carbonyl-alkyl or carbonyl-alkenyl group, said alkyl or alkenyl radical comprising from 1 to 22 carbon atoms, preferably from 1 to 15 carbon atoms.

8. The adhesive composition as claimed in claim 1, characterized in that the catalytic composition (B) comprises an organometallic compound (D) which is obtained by reacting the metal alkoxide (D1) with an oxime (D2) of formula (VI) in which: G.sup.3 and G.sup.6 each represent a hydrogen atom, and/or G.sup.4 and G.sup.5 form an aliphatic ring containing from 4 to 14 carbon atoms.

9. The adhesive composition as claimed in claim 1, characterized in that the catalytic composition (B) comprises an organometallic compound (D) which is obtained by reacting the metal alkoxide (D1) with the oxime (D2) in an alkoxide/oxime mole ratio ranging from 1:1 to 1:6.

10. The adhesive composition as claimed in claim 1, characterized in that the catalytic composition (B) comprises the tertiary amine (C) and the organometallic compound (D) in a respective amount corresponding to a ratio: number of moles of (C)/number of moles of the metal alkoxide (D1) within the range from 0.5 to 25.

11. The adhesive composition as claimed in claim 1, characterized in that the catalytic composition (B) comprises, besides the tertiary amine (C) and the organometallic compound (D), an organosilicon compound (E) chosen from: a silsesquioxane (E1); a compound (E2) of formula (IX):
K[Si(OR.sup.6).sub.3].sub.v(IX) in which: K is a saturated or unsaturated, linear or branched hydrocarbon-based radical comprising from 2 to 15 carbon atoms and one or more heteroatoms chosen from nitrogen and oxygen; R.sup.6 represents a linear or branched alkyl or alkenyl group, preferably alkyl, containing from 1 to 5 carbon atoms, preferably from 1 to 2 carbon atoms; v equal to 1, 2 or 3; and a tetraethyl orthosilicate oligomer (E3).

12. The adhesive composition as claimed in claim 1, characterized in that the catalytic composition (B) represents from 0.05% by weight to 10% by weight relative to the total weight of the adhesive composition.

13. A catalytic composition (B) comprising: a tertiary amine (C) with a pKa of greater than 11; and an organometallic compound (D) obtained by reacting at least one metal alkoxide (D1) with at least one oxime (D2) chosen from an oxime of formula (V) or an oxime of formula (VI): ##STR00032## in which: G.sup.1 is a hydrogen atom or a linear or branched alkyl radical comprising from 1 to 4 carbon atoms; G.sup.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 alkenylradical 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.sup.7G.sup.8) in which G.sup.7 and G.sup.8 represent, independently of each 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.sup.3 represents either a hydrogen atom, or an alkyl group containing from 1 to 4 carbon atoms, or forms the residue of an aliphatic ring containing between 4 and 14 carbon atoms with the groups G.sup.4 and/or G.sup.5 and/or G.sup.6, said aliphatic ring optionally comprising one or more heteroatoms and/or one or more double bonds and said aliphatic ring being optionally substituted with one or more alkyl groups containing from 1 to 4 carbon atoms; G.sup.4 represents either a hydrogen atom, or an alkyl group containing from 1 to 4 carbon atoms, or forms the residue of an aliphatic ring containing between 4 and 14 carbon atoms with the groups G.sup.3 and/or G.sup.5 and/or G.sup.6, said aliphatic ring optionally comprising one or more heteroatoms and/or one or more double bonds and said aliphatic ring being optionally substituted with one or more alkyl groups containing from 1 to 4 carbon atoms; it being understood that at least one of the groups G.sup.3 or G.sup.4 forms the residue of an aliphatic ring with at least one of the groups G.sup.5 or G.sup.6; G.sup.5 represents either a hydrogen atom, or an alkyl group containing from 1 to 4 carbon atoms, or forms the residue of an aliphatic ring containing between 4 and 14 carbon atoms with the groups G.sup.3 and/or G.sup.4 and/or G.sup.6, said aliphatic ring optionally comprising one or more heteroatoms and/or one or more double bonds and said aliphatic ring being optionally substituted with one or more alkyl groups containing from 1 to 4 carbon atoms; G.sup.6 represents either a hydrogen atom, or an alkyl group containing from 1 to 4 carbon atoms, or forms the residue of an aliphatic ring containing between 4 and 14 carbon atoms with the groups G.sup.3 and/or G.sup.4 and/or G.sup.5, said aliphatic ring optionally comprising one or more heteroatoms and/or one or more double bonds and said aliphatic ring being optionally substituted with one or more alkyl groups containing from 1 to 4 carbon atoms; it being understood that at least one of the groups G.sup.5 or G.sup.6 forms the residue of an aliphatic ring with at least one of the groups G.sup.3 or G.sup.4.

14. The catalytic composition (B) as claimed in claim 13, characterized in that the tertiary amine (C), the metal alkoxide (D1), the oxime (D2) and/or the organometallic compound (D) are as defined in one of claims 5 to 10 and/or characterized in that it also comprises the organosilicon compound (E) chosen from; a silsesquioxane (E1); a compound (E2) of formula (IX):
K[Si(OR.sup.6).sub.3].sub.v(IX) in which; K is a saturated or unsaturated, linear or branched hydrocarbon-based radical comprising from 2 to 15 carbon atoms and one or more heteroatoms chosen from nitrogen and oxygen; R.sup.6 represents a linear or branched alkyl or alkenyl group, preferably alkyl, containing from 1 to 5 carbon atoms, preferably from 1 to 2 carbon atoms; v equal to 1, 2 or 3; and a tetraethyl orthosilicate oligomer (E3).

15. A bonding process comprising the application of the adhesive composition as defined in claim 1 to a surface, followed by the crosslinking of said adhesive composition.

Description

EXAMPLE CD 1

[0268] Catalytic Composition (B):

[0269] 17.6 mmol of cyclohexanone oxime were dissolved in 16 mmol of Mesamoll in a 30 ml glass reactor, stirring for 1 hour 30 minutes at room temperature under vacuum.

[0270] Next, 17.6 mmol of Ti(OnBu).sub.4 were added to the preceding solution under nitrogen, and the mixture was stirred for 3 hours at room temperature under vacuum to give a pale yellow solution composed of titanium/oxime complexes.

[0271] Finally, 35.2 mmol of DBU were introduced into this solution. The mixture was stirred for 1 hour to obtain a catalytic composition cdl in the form of an orange solution composed of titanium/oxime complexes in equilibrium with the DBU.

[0272] Adhesive Composition:

[0273] The catalytic composition CD 1 thus obtained was incorporated into an adhesive composition prepared by simple mixing, in a rapid mixer, of the following ingredients: [0274] 41.8% by weight of MS polymer (MS S303H from Kaneka), [0275] 53% by weight of fillers of precipitated calcium carbonate type, [0276] 2.8% by weight of a moisture absorber of vinyltrimethoxysilane (VTMO) type, [0277] 1.4% by weight of an adhesion promoter of aminopropyltrimethoxysilane type and [0278] 1% by weight of the catalytic composition CD 1.

[0279] The adhesive composition thus prepared was subjected to the following tests:

[0280] Test for Measuring the Crosslinking Time

[0281] The crosslinking time (also known as the skinning time) was evaluated by touching the surface of the adhesive composition with a pointed implement every 5 minutes for 2 hours and then every 30 minutes up to 4 hours (ambient conditions: 50% relative humidity and temperature of 23 C.). The composition was considered to be non-crosslinked as long as, during touching of the surface, adhesive residues were transferred onto the pointed implement.

[0282] The result (expressed in minutes) is indicated in Table 1 below.

[0283] Stability Test

[0284] A portion of the adhesive composition prepared above is conditioned in a cartridge which is stored in an oven at 40 C.

[0285] After 21 days, the cartridge is removed from the oven and part of the composition is poured into an aluminum crucible, for the purpose of measuring the crosslinking time (in minutes) according to the above protocol.

[0286] The results are indicated in the following manner:

[0287] A 2 indicates that the adhesive composition is very stable (crosslinking time after storage for 21 days identical to the crosslinking time measured just after preparation of the adhesive composition),

[0288] A 1 indicates that the adhesive composition is stable (crosslinking time after storage for 21 days different but close to the crosslinking time measured just after preparation of the adhesive composition),

[0289] A 0 indicates that the adhesive composition is not stable (crosslinking time after storage for 21 days very different from the crosslinking time measured just after preparation of the adhesive composition),

[0290] The result (expressed in minutes) is indicated in Table 1 below.

Examples CD 2-CD 13 and Example a (Comparative)

[0291] Example CD 1 is repeated in detailed manner hereinbelow for each of these examples.

[0292] The crosslinking time results for the corresponding adhesive composition and the stability test results are indicated in Table 1 below.

EXAMPLE CD 2

[0293] Example CD 1 is repeated, replacing the DBU with the catalyst of phosphazene type P1.

EXAMPLE CD 3

[0294] Example CD 1 is repeated, replacing the DBU with the catalyst of phosphazene type BEMP.

EXAMPLE CD 4

[0295] Example CD 1 is repeated, replacing the DBU with TBD.

EXAMPLE CD 5

[0296] Example CD 1 is repeated, replacing the 16 mmol of Mesamoll with 47 mmol of xylene.

EXAMPLE CD 6

[0297] Example CD 1 is repeated, replacing the 16 mmol of Mesamoll with 10.6 mmol of pentaerythrityl tetravalerate.

EXAMPLE CD 7

[0298] Example CD 1 is repeated, replacing the 16 mmol of Mesamoll with 56.7 mmol of ethyl acetate.

EXAMPLE CD 8

[0299] Example CD 1 is repeated, replacing Ti(OnBu).sub.4 with Zn[O(CO)C.sub.9H.sub.19].sub.2.

EXAMPLE CD 9

[0300] Example CD 1 is repeated, replacing Ti(OnBu).sub.4 with Bi[O(CO)C.sub.9H.sub.19].sub.2.

EXAMPLE CD 10

[0301] Example CD 1 is repeated, replacing Ti(OnBu).sub.4 with Rb[O(CO)C.sub.9H.sub.19].

EXAMPLE CD 11

[0302] Example CD 1 is repeated, replacing Ti(OnBu).sub.4 with Cs[O(CO)C.sub.9H.sub.19].

EXAMPLE CD 12

[0303] Example CD 1 is repeated, replacing the 17.6 mmol of Ti(OnBu).sub.4 with 2.9 mmol of this same compound, and replacing the 35.2 mmol of DBU with 68.3 mmol.

EXAMPLE CD 13

[0304] Example CD 1 is repeated, replacing the 17.6 mmol of Ti(OnBu).sub.4 with 8.8 mmol of this same compound, and replacing the 35.2 mmol of DBU with 55.2 mmol.

EXAMPLE A (COMPARATIVE)

[0305] Example CD 1 is repeated, without introduction of DBU.

[0306] Example B (reference): adhesive composition with a tin catalyst The adhesive composition of Example CD1 is reproduced, replacing the 1% of catalytic composition CD1 with 0.6% of dioctyltin and adjusting the percentages of the other ingredients.

EXAMPLE C (REFERENCE): ADHESIVE COMPOSITION WITH A ZINC-BASED CATALYST

[0307] The adhesive composition of Example CD1 is reproduced, replacing the 1% of catalytic composition CD1 with 1% of zinc neodecanoate.

[0308] The crosslinking time results and the stability test results are indicated in Table 1 below.

EXAMPLE CDE 1

[0309] Catalytic Composition (B):

[0310] A catalytic composition CDE 1 is prepared by repeating the protocol for preparing the catalytic composition of Example CD 1, except that 7.7 mmol of TEOS oligomer are also introduced into the pale yellow solution composed of titanium/oxime complex and prior to the addition of the 35.2 mmol of DBU, said introduction being immediately followed by stirring of the mixture obtained for 30 minutes.

[0311] Adhesive Composition:

[0312] The protocol for preparing the adhesive composition of Example CD 1 is repeated, replacing the catalytic composition CD 1 with the catalytic composition CDE 1 thus prepared.

[0313] The adhesive composition thus obtained is subjected to the following tests: [0314] measurement of the crosslinking time in accordance with the protocol detailed in Example CD 1, [0315] measurement of the tensile stress according to the protocol described below.

[0316] Measurement of the Breaking Stress by Tensile Testing:

[0317] The principle of the measurement consists in drawing, in a tensile testing machine, the movable jaw of which is displaced at a constant speed equal to 100 mm/minute, a standard test specimen consisting of the crosslinked adhesive composition, and in recording, at the moment when the test specimen breaks, the applied tensile stress (in MPa).

[0318] The standard test specimen is dumbbell-shaped, of H2 type, as illustrated in the international standard ISO 37. The narrow part of the dumbbell used has a length of 20 mm, a width of 4 mm and a thickness of 3 mm.

[0319] To prepare the dumbbell, the adhesive composition to be tested is placed in a Teflon mold, and the composition is left to crosslink for 14 days under the standard conditions (23 C. and 50% relative humidity).

[0320] The results obtained for the crosslinking time (expressed in minutes) and the breaking stress (expressed in MPa) are indicated in Table 2 below.

Examples CDE 2 to CDE 11

[0321] Catalytic Composition (B):

[0322] For each of the examples CDE 2 to CDE 11, a catalytic composition is prepared by repeating Example CDE 1 in which the catalytic composition of Example CD 1 is replaced with, respectively, the catalytic composition of each of the examples CD 2 to CD 11.

[0323] Adhesive Composition:

[0324] The adhesive compositions corresponding to the catalytic compositions thus prepared are obtained by repeating the protocol of Example CDE 1, by simply replacing the catalytic composition CDE 1 with the appropriate catalytic composition.

[0325] The results obtained for the crosslinking time (expressed in minutes) and the breaking stress (expressed in MPa) are indicated in Table 2 below.

[0326] The results obtained for the crosslinking time and the breaking stress corresponding to Examples A, B and C (expressed in MPa) are also indicated in Table 2 below.

EXAMPLE CDE 20

[0327] Example CDE 1 is repeated, replacing the TEOS oligomer with Geniosil GF 69.

[0328] The results obtained for the crosslinking time (expressed in minutes) and the breaking stress (expressed in MPa) are indicated in Table 2 below.

EXAMPLE CDE 21

[0329] Example CDE 1 is repeated, replacing the TEOS oligomer with Dynasylan 1124.

[0330] The results obtained for the crosslinking time (expressed in minutes) and the breaking stress (expressed in MPa) are indicated in Table 2 below.

EXAMPLE CDE 22

[0331] Example CDE 1 is repeated, replacing the TEOS oligomer with Dow Corning 3074.

[0332] The results obtained for the crosslinking time (expressed in minutes) and the breaking stress (expressed in MPa) are indicated in Table 2 below.

EXAMPLE CDE 23

[0333] Example CDE 1 is repeated, replacing the TEOS oligomer with SIT8716.3.

[0334] The results obtained for the crosslinking time (expressed in minutes) and the breaking stress (expressed in MPa) are indicated in Table 2 below.

TABLE-US-00001 TABLE 1 Catalytic compositions consisting essentially of the tertiary amine (C) and of the organometallic compound (D) Crosslinking Stability on storage time in a cartridge (in Catalytic composition (B) (in mm) minutes) Example A (comp.) 80 2 Example B (ref.) 45 2 Example C (ref.) 75 2 Example CD 1 30 2 Example CD 2 45 0 Example CD 3 40 0 Example CD 4 30 1 Example CD 5 35 2 Example CD 6 30 2 Example CD 7 35 2 Example CD 8 40 2 Example CD 9 45 2 Example CD 10 40 2 Example CD 11 35 2 Example CD 12 40 2 Example CD 13 40 2

TABLE-US-00002 TABLE 2 Catalytic compositions consisting essentially of the tertiary amine (C), of the organometallic compound (D) and of the organosilicon compound (E) Crosslinking time Breaking stress Catalytic composition (B) (in min) (MPa) Example A (comp.) 80 2.3 Example B (ref.) 45 2.7 Example C (ref.) 75 2.0 Example CDE 1 30 2.8 Example CDE 2 45 1.0 Example CDE 3 40 0.4 Example CDE 4 30 2.9 Example CDE 5 35 3.2 Example CDE 6 30 2.9 Example CDE 7 35 3.2 Example CDE 8 40 3.2 Example CDE 9 45 2.9 Example CDE 10 40 2.8 Example CDE 11 35 2.8 Example CDE 20 40 2.7 Example CDE 21 40 3.1 Example CDE 22 30 3.2 Example CDE 23 45 2.7