METHOD FOR PREPARING COMPOUNDS WITH AN ALKOXYSILYL GROUP

Abstract

Method for preparing a compound having an alkoxysilyl group of formula (I), wherein X represents —O— or —NR.sup.4— with R.sup.4═H or C.sub.1-C.sub.4alkyl; R.sup.1 is a radical having from 1 to 20 carbon atoms; R.sup.2 and R.sup.3 are a C.sub.1-C.sub.4 alkyl radical; p is an integer equal to 0, 1 or 2; comprising a cross metathesis reaction in the presence (i) of a compound having a group of acrylate type and of formula: —X(C═O)—CH═CH.sub.2, (ii) of an α-olefinic silane of formula (II): and (iii) of a metathesis catalyst chosen from GRUBBS catalysts and 2nd generation HOVEYDA-GRUBBS (HG2) catalysts. 2) Compound having said alkoxysilyl group, obtained by the method 1).

Claims

1. A process for preparing a compound (A) comprising at least one alkoxysilyl group F of formula (I): ##STR00044## wherein: X represents —O— or the group —NR.sup.4— wherein R.sup.4 represents a hydrogen atom or an alkyl radical comprising from 1 to 20 carbon atoms, preferably from 1 to 4 carbon atoms; R.sup.1 is a linear or branched, saturated or unsaturated hydrocarbon-based radical comprising from 1 to 20 carbon atoms, preferably from 1 to 9 carbon atoms and even more preferentially from 1 to 2 carbon atoms; R.sup.2 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.2, these radicals are identical or different; R.sup.3 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.3, these radicals are identical or different, and with the possibility, in addition, that two groups OR.sup.3 may be engaged in the same ring; p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1; said process comprising a cross-metathesis reaction in the presence of: (i) a compound (B) comprising at least one acrylate or acrylamide group F′ of formula (I′):
—X(C═O)—CH═CH.sub.2   (I′) wherein X is as defined above; (ii) an α-olefinic silane (C) of formula (II):
H.sub.2C═CH—R.sup.1—Si(R.sup.2).sub.p(OR.sup.3).sub.(3-p)   (II); wherein R.sup.1, R.sup.2 and R.sup.3 are as defined above; and (iii) a metathesis catalyst (D) chosen from the 2.sup.nd-generation Grubbs catalyst (G2) of formula: ##STR00045## and the 2.sup.nd-generation Hoveyda-Grubbs catalyst (HG2) of formula: ##STR00046##

2. The preparation process as claimed in claim 1, characterized in that the compound (A) is a polymer of which the main chain is chosen: when X is —O—, from a polyether, a polyester, a polyene, a poly(meth)acrylate or a polyurethane; and when X is the group —NR.sup.4—, from a polyether, a polyene, a poly(meth)acrylate or a polyurethane; which is obtained from a polymer (B) of which the main chain is identical to that of the polymer (A).

3. The preparation process as claimed in claim 2, characterized in that the polymer (A) comprises 2 end groups F of formula (I) and in that the polymer (B) comprises 2 end groups F′ of formula (I′).

4. The preparation process as claimed in claim 2, characterized in that the main chain of the polymers (A) and (B) is a polyurethane chosen from a polyether-polyurethane, a polyester-polyurethane, a polyether-polyester-polyurethane, a polyene-polyurethane, a polyether-polyene-polyurethane or a poly(meth)acrylate-polyurethane.

5. The preparation process as claimed in claim 2, characterized in that the polymer (A) and the precursor polymer (B) have a polyurethane as their main chain and comprise 2 end groups, respectively F of formula (I) and F′ of formula (I′), wherein X represents —O—.

6. The preparation process as claimed in claim 5, characterized in that the polyurethane (A) corresponds to one of the formulae (VII) and (VIII): ##STR00047## and the precursor polyurethane (B) corresponds, respectively, to one of the following formulae (VII′) and (VIII′): ##STR00048## wherein: F is the alkoxysilyl group of formula (I)-1: ##STR00049## F′ is the acrylate group; R.sup.5 represents a divalent hydrocarbon-based radical comprising from 5 to 15 carbon atoms which can be aromatic or aliphatic and linear, branched or cyclic; R.sup.6 represents a saturated or unsaturated, linear or branched divalent hydrocarbon-based radical optionally comprising one or more oxygen atoms; R′.sup.O represents a linear or branched, aliphatic or cyclic, saturated or unsaturated divalent BOSTIK-0060 alkylene radical comprising from 2 to 6 carbon atoms; r is an integer greater than or equal to 0; s is an integer strictly greater than 0.

7. The preparation process as claimed in claim 1, characterized in that the compound (A) has a molar mass of between 170 and 1000 g/mol and corresponds to formula (VI):
M[(X—(C═O)—CH═CH—R.sup.1—Si(R.sup.2).sub.p(OR.sup.3).sub.(3-p)].sub.f  (VI) wherein: M is a linear, branched or cyclic, saturated or unsaturated hydrocarbon-based radical comprising from 1 to 6 free valences and optionally having one or more heteroatoms or an ester function or a urethane function or a urea function; and f is an integer ranging from 1 to 6; and the compound (B) corresponds to formula (VI′):
M[(X—(C═O)—CH═CH.sub.2].sub.f  (VI′) wherein M is as defined in formula (VI).

8. The preparation process as claimed in claim 1, characterized in that the metathesis catalyst (D) is the catalyst (HG2).

9. A compound (A) comprising at least one alkoxysilyl group F of formula (I): ##STR00050## wherein: X represents —O— or the group —NR.sup.4— wherein R.sup.4 represents a hydrogen atom or an alkyl radical comprising from 1 to 20 carbon atoms, preferably from 1 to 4 carbon atoms; R.sup.1 is a linear or branched, saturated or unsaturated hydrocarbon-based radical comprising from 1 to 20 carbon atoms, preferably from 1 to 9 carbon atoms and even more preferentially from 1 to 2 carbon atoms; R.sup.2 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.2, these radicals are identical or different; R.sup.3 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.3, these radicals are identical or different, and with the possibility, in addition, that two groups OR.sup.3 may be engaged in the same ring; p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.

10. The compound (A) as claimed in claim 9, produced by a process comprising a cross-metathesis reaction in the presence of: (i) a compound (B) comprising at least one acrylate or acrylamide group F′ of formula (I′):
—X(C═O)—CH═CH.sub.2   (I′) wherein X is as defined above; (ii) an α-olefinic silane (C) of formula (II):
H.sub.2C═CH—R.sup.1—Si(R.sup.2).sub.p(OR.sup.3.sub.(3-p)   (II): wherein R.sup.1, R.sup.2 and R.sup.3 are as defined above; and (iii) a methathesis catalyst (D) chosen from the 2.sup.nd-generation Grubbs catalyst (G2) of formula: ##STR00051## and the 2.sup.nd-generation Hoveyda-Grubbs catalyst (HG2) of formula: ##STR00052##

11. The compound (A) as claimed in claim 9, characterized in that it is a polymer of which the main chain is chosen: when X is —O—, from a polyether, a polyester, a polyene, a poly(meth)acrylate or a polyurethane; and when X is the group —NR.sup.4—, from a polyether, a polyene, a poly(meth)acrylate or a polyurethane; and which comprises 2 end groups F.

12. The polymer (A) as claimed in claim 11, characterized in that R.sup.1 is a hydrocarbon-based radical comprising from 1 to 2 carbon atoms.

13. The polymer (A) as claimed in claim 11, characterized in that it is a polyurethane which comprises 2 end groups F corresponding to one of the following formulae:
—O(C═O)—CH═CH—R.sup.1—Si(R.sup.2).sub.p(OR.sup.3).sub.(3-p)  (I)-1
—O(C═O)—NH—R.sup.O—O(C═O)—CH═CH—R.sup.1—Si(R.sup.2).sub.p(OR.sup.3).sub.(3-p)  (I)-2
—NH(C═O)—O—R′.sup.O—O(C═O)—CH═CH—R.sup.1—Si(R.sup.2).sub.p(OR.sup.3).sub.(3-p)  (I)-3
—NH(C═O)—O—R.sup.N—NR.sup.4—(C═O)—CH═CH—R.sup.1—Si(R.sup.2).sub.p(OR.sup.3).sub.(3-p)  (I)-5. wherein R.sup.O, R′.sup.O and R.sup.N are identical or different and represent a linear or branched, aliphatic or cyclic, saturated or unsaturated divalent hydrocarbon-based radical, preferably comprising from 2 to 24 carbon atoms, and being optionally interrupted by one or more heteroatoms.

14. The polymer (A) as claimed in claim 13, characterized in that it corresponds to one of formulae (VII) and (VIII): ##STR00053## wherein: F is the alkoxysilyl group of formula (I)-1: ##STR00054## R.sup.5 represents a divalent hydrocarbon-based radical comprising from 5 to 15 carbon atoms which can be aromatic or aliphatic and linear, branched or cyclic; R.sup.6 represents a saturated or unsaturated, linear or branched divalent hydrocarbon-based radical optionally comprising one or more oxygen atoms; r is an integer greater than or equal to 0; s is an integer strictly greater than 0.

Description

EXAMPLE 1: CROSS-METATHESIS OF TRIPROPYLENE GLYCOL DIACRYLATE (COMPOUND (B)) IN THE PRESENCE OF ALLYL TRIMETHOXYSILANE (COMPOUND (C)) AND OF THE HG2 CATALYST (COMPOUND (D))

[0330] Use is made of tripropylene glycol diacrylate (molar mass 300 g/mol, commercially available under the name SR 306 from Sartomer), and, as compound (C), allyl trimethoxysilane having the following formula:

##STR00031##

[0331] The tripropylene glycol diacrylate (1.7 mmol), purified beforehand on neutral silica, is introduced into a 10 ml round-bottomed flask in which a Teflon®-coated magnetic stirring bar has been placed.

[0332] Allyl trimethoxysilane (4.0 mmol) is then added with stirring to the round-bottomed flask by means of a syringe under an argon atmosphere. The ratio r.sup.6 of the reagents, as defined previously, is equal to 4.0 mmol divided by (2×1.7 mmol), i.e. 1.17. [0333] Then, a solution of Hoveyda-Grubbs (HG2) catalyst (0.57 μmol or 0.57×10−3 mmol) in dry CH.sub.2Cl.sub.2 (3 ml) is then added in 3 batches at 40 minute intervals. The ratio r.sup.7, as defined above, is equal to (2×1.7 mmol) divided by (0.57×10−3 mmol) i.e. 5965.

[0334] The round-bottomed flask and its contents are placed under argon and then immersed in an oil bath at 40° C. for 2 hours in order to remove from the reaction medium the ethylene which is generated by the cross-metathesis reaction. The round-bottomed flask and its contents are then brought to 80° C. under reduced pressure for 1 hour in order to remove the excess unreacted allyl trimethoxysilane.

[0335] After 3 hours, counting from the addition of the catalyst, the product present in the round-bottomed flask is extracted after evaporation of the solvent under vacuum. The product is then recovered in the form of a colorless liquid without any purification, with a yield of 99% of isolated product (corresponding to the mixture of disilylated and monosilylated compounds) and a degree of conversion of the acrylate functions of 92%. [0336] Analysis by .sup.1H/.sup.13C NMR gives the following results:

[0337] .sup.1H NMR (400 MHz, CDCl.sub.3, 293 K) δ (ppm)=7.00 (dt, J=15, 10 Hz, CH.sub.2CH═CH, 1H), 5.79 (d, J=15 Hz, CH.sub.2CH═CH, 1H), 5.05 (bm, CH(CH.sub.3)O(C═O), 1H), 4.06; 3.67 (bm, CH(CH.sub.3)OCH.sub.2CH(CH.sub.3)O(C═O), 1H) overlapping with 4.06 (s, CH.sub.2O(C═O), 2H), 4.00; 3.80 (bm, CH(CH.sub.3)CH.sub.2O(C═O), 1H), 3.55 (s, CH.sub.3OSi, 18H), 3.53 (s, CH.sub.2OCH(CH.sub.3)CH.sub.2O(C═O), 2H), 3.39 (m, CH.sub.2CH(CH.sub.3)O(C═O), 2H), 1.81 (dd, J=8, 5 Hz, CH.sub.2CH═CH, 2H), 1.22 (d, J=6 Hz, CH(CH.sub.3)O(C═O), 3H), 1.14 (bm, CH(CH.sub.3)CH.sub.2O(C═O), 3H), 1.09 (bm, CH(CH.sub.3)OCH.sub.2CH(CH.sub.3)O(C═O), 3H).

[0338] .sup.13C{.sup.1H} NMR (100 MHz, CDCl.sub.3, 293 K) δ (ppm)=166.3, 166.0, 144.8, 144.5, 121.7, 120.8, 76.0, 75.2, 73.6, 72.2, 69.5, 67.2, 53.6, 51.2, 21.2, 17.8, 16.9. FT-IR v (cm.sup.−1)=2970 (C═C—H stretch, alkene), 1710 (C═O stretch, ester), 1640 (C═C stretch, alkene), 1070 (C—O stretch), 810 (═C—H bend, alkene), 770 (═C—H bend, alkene). ESI-MS [M.sup.+Na.sup.−] (C.sub.23H.sub.44O.sub.12NaSi.sub.2), z=1, m/z.sub.calculated=591.22635, m/z.sub.experimental=591.2267.

[0339] These values confirm the majority presence of the disilylated compound (A) of the following structure:

##STR00032##

and the minority presence of the monosilylated compound of the following structure:

##STR00033##

EXAMPLE 2: CROSS-METATHESIS OF TRIPROPYLENE GLYCOL DIACRYLATE (COMPOUND (B)) IN THE PRESENCE OF ALLYL TRIMETHOXYSILANE (COMPOUND (C)) AND OF THE G2 CATALYST (COMPOUND (D))

[0340] Example 1 is repeated, replacing the HG2 catalyst with the G2 catalyst.

[0341] The same product is obtained, with a yield of 95% of isolated product and a degree of conversion of the acrylate functions of 70%.

EXAMPLE 3: CROSS-METATHESIS OF A POLYURETHANE DIACRYLATE (POLYMER (B)) IN THE PRESENCE OF ALLYL TRIMETHOXYSILANE (COMPOUND (C)) AND OF THE HG2 CATALYST (COMPOUND (D))

[0342] Step 1: Synthesis of Polyurethane Diacrylate:

[0343] A polyurethane diacrylate is synthesized in 2 steps according to the following procedure:

##STR00034##

[0344] 1163 g of polypropylene glycol (0.58 mol) having a number-average molecular weight (Mn) equal to 1800 g/mol, 201 g of 2,4-toluene diisocyanate (1.15 mol), and 1.4 g of Borchi® Kat 315 catalyst (commercially available from Borchers) are successively introduced into a 2-liter reactor.

[0345] The mixture is heated at 80° C. until total consumption of the —OH functions corresponding to the obtaining of a polyurethane comprising —NCO end groups, having an NCO % of 3.2% by weight. 1.4 g of hydroquinone monomethyl ether (MEHQ-polymerization inhibitor) then 132 g of 2-hydroxyethyl acrylate (1.02 mol) are then introduced into the reaction medium in a stoichiometric mole ratio relative to the —NCO functions of the polyurethane comprising —NCO end groups, previously obtained. The mixture is maintained at 80° C. with stirring until complete disappearance of the —NCO functions by infrared.

[0346] Step 2: Cross-Metathesis of Polyurethane Diacrylate:

[0347] Use is made of the polyurethane diacrylate from step 1, and, as compound (C), allyl trimethoxysilane having the following formula:

##STR00035##

[0348] Polyurethane diacrylate (10.0 mmol) and dry CH.sub.2Cl.sub.2 (17 ml) are introduced into a 50 ml round-bottomed flask in which a Teflon®-coated magnetic stirring bar has also been placed.

[0349] Allyl trimethoxysilane (21.0 mmol) is then added with stirring to the round-bottomed flask by means of a syringe under an argon atmosphere. The ratio r.sup.6 of the reagents, as defined above, is equal to 21.0 mmol divided by (2×10.0 mmol), i.e. 1.05.

[0350] Then a solution of Hoveyda-Grubbs (HG2) catalyst (0.05 mmol) in dry CH.sub.2Cl.sub.2 (3 ml) is subsequently added in 3 batches at 40 minute intervals. The ratio r.sup.7, as defined above, is equal to 20.0 mmol divided by 0.05 mmol, i.e. 400.

[0351] The round-bottomed flask and its contents are placed under argon and then immersed in an oil bath at 40° C. for 2 hours in order to remove from the reaction medium the ethylene generated by the cross-metathesis. The round-bottomed flask and its contents are then brought to 80° C. under reduced pressure for 1 hour in order to remove the excess unreacted allyl trimethoxysilane.

[0352] After 3 hours, counting from the addition of the catalyst, the product present in the round-bottomed flask is extracted after evaporation of the solvent under vacuum. The product is then recovered in the form of a colorless liquid without any purification, with a yield of 99% of isolated product and a degree of conversion of the acrylate functions of 96%.

[0353] Analysis by 1H/.sup.13C NMR gives the following results:

[0354] .sup.1H NMR (400 MHz, CDCl.sub.3, 293 K) δ (ppm)=7.67 (bs, C(NH)═CH═C(NH), 1H), 7.41-7.22 (bs, NH, 1H), 7.13 (bd, CH═CH═C(NH), 1H), 6.95 (bd, CH═CH═C(NH), 1H), 6.95 (bd, CH═CHCH.sub.2Si(OCH.sub.3).sub.3, 1H), 6.64 (bs, NH, 1H), 5.74 (bdd, CH═CHCH.sub.2Si(OCH.sub.3).sub.3, 1H), 4.90 (bm, CH(CH.sub.3)O(C═O)), 4.27 (bs, OCH.sub.2CH.sub.2O, 4H), 3.60-3.37 (bm, CH(CH.sub.3)O(C═O)), 3.47 (s, Si(OCH.sub.3).sub.3), 3.31 (bd, CH.sub.2CH(CH.sub.3)O(C═O), 2.09 (s, C(CH.sub.3)CH═CH═C(NH), 3H), 1.74 (bd, CH═CHCH.sub.2Si(OCH.sub.3).sub.3, 2H), 1.19 (bs, CH(CH.sub.3)O(C═O)), 1.03 (bs, CH(CH.sub.3)O(C═O)).

[0355] .sup.13C{.sup.1H} NMR (100 MHz, CDCl.sub.3, 293 K) δ (ppm)=166.0, 153.1, 145.3, 137.0, 135.9, 130.5, 120.5, 114.5, 111.9, 175.0, 73.2, 70.3, 63.0, 62.1, 50.7, 17.1, 16.9. FT-IR v (cm.sup.−1)=3300 (N—H stretch, amide), 2970 (C═C stretch), 1720 (C═O stretch, ester), 1080 (C—O stretch).

[0356] These values confirm the majority presence of the disilylated compound of the following structure:

##STR00036##

and the minority presence of the monosilylated compound of the following structure:

##STR00037##

EXAMPLE 4: CROSS-METATHESIS OF A POLYPROPYLENE GLYCOL DIACRYLATE (POLYMER (B)) IN THE PRESENCE OF ALLYL TRIMETHOXYSILANE (COMPOUND (C)) AND OF THE HG2 CATALYST (COMPOUND (D))

[0357] Step 1: Synthesis of Polypropylene Glycol Diacrylate:

[0358] A polyurethane diacrylate is synthesized in one step according to the following procedure:

##STR00038##

[0359] 1163 g of polypropylene glycol (0.58 mol) having a number-average molecular weight (Mn) equal to 1800 g/mol, 164 g of 2-isocyanatoethyl acrylate (1.16 mol), 1.4 g of hydroquinone monomethyl ether (MEHQ-polymerization inhibitor), then 1.4 g of Borchi® Kat 315 catalyst (commercially available from Borchers) are successively introduced into a 2-liter reactor, and the mixture is heated at 80° C. until complete disappearance of the —NCO functions by infrared.

[0360] Step 2: Cross-Metathesis of Polypropylene Glycol Diacrylate:

[0361] Step 2 of example 3 is repeated, replacing the polyurethane diacrylate with the polypropylene glycol diacrylate obtained in step 1.

[0362] A product is obtained which is recovered in the form of a colorless liquid without any purification, with a yield of 99% of isolated product and a degree of conversion of the acrylate functions of 98%.

[0363] .sup.1H/.sup.13C NMR analysis confirms the majority presence of the disilylated compound of the following structure:

##STR00039##

and the minority presence of the monosilylated product of the following structure:

##STR00040##

EXAMPLE 5: CROSS-METATHESIS OF A POLYISOPRENE DIOL DIACRYLATE (POLYMER (B)) IN THE PRESENCE OF ALLYL TRIMETHOXYSILANE (COMPOUND (C)) AND OF THE HG2 CATALYST (COMPOUND (D))

[0364] Saturated polyisoprene diol diacrylate (PIPA available from San Esters) is used, and allyl trimethoxysilane of the following formula is used as transfer agent:

##STR00041##

[0365] The saturated polyisoprene diol diacrylate (10.0 mmol) having a number-average molecular weight (Mn) equal to 2700 g/mol and dry CH.sub.2Cl.sub.2 (17 ml) are introduced into a 50 ml round-bottomed flask in which a Teflon®-coated magnetic stirring bar has been placed.

[0366] Allyl trimethoxysilane (21.0 mmol) is then added with stirring to the round-bottomed flask by means of a syringe under an argon atmosphere. The ratio r.sup.6 of the reagents, as defined above, is equal to 21 mmol divided by (2×10.0 mmol), i.e. 1.05.

[0367] Then a solution of Hoveyda-Grubbs (HG2) catalyst (0.05 mmol) in dry CH.sub.2Cl.sub.2 (3 ml) is subsequently added in 3 batches at 40 minute intervals. The ratio r.sup.7, as defined above, is equal to 20.0 mmol divided by 0.05 mmol, i.e. 400.

[0368] The round-bottomed flask and its contents are placed under argon and then immersed in an oil bath at 40° C. for 2 hours in order to remove from the reaction medium the ethylene generated by the cross-metathesis. The round-bottomed flask and its contents are then brought to 80° C. under reduced pressure for 1 hour in order to remove the excess unreacted allyl trimethoxysilane.

[0369] After 3 hours, counting from the addition of the catalyst, the product present in the round-bottomed flask is extracted after evaporation of the solvent under vacuum. The product is then recovered in the form of a colorless liquid without any purification, with a yield of 99% of isolated product and a degree of conversion of the acrylate functions of 96%.

[0370] As for the previous examples, the .sup.1H/.sup.13C MR analysis confirms the majority presence of the disilylated compound of the following structure:

##STR00042##

and the minority presence of the compound product of the following structure:

##STR00043##