NEW LIQUID HYDROCARBON COPOLYMERS COMPRISING TWO ALKOXYSILANE END GROUPS, AND PRODUCTION METHOD THEREOF

Abstract

1) Hydrocarbon copolymer P comprising 2 alkoxysilane end groups F.sup.1 and F.sup.2 of formulae: F.sup.1: (RO).sub.3-tR.sub.tSi(CH.sub.2).sub.g1- and F.sup.2: (CH.sub.2).sub.d1SiR.sub.t(OR).sub.3-t; or F.sup.1: (RO).sub.3-tR.sub.tSiRO(O)C(CH.sub.2).sub.g2 and F.sup.2: (CH.sub.2).sub.d2C(O)ORSiR.sub.t(OR).sub.3-t; wherein t is 0, 1 or 2; g1 and d1 are 1, 2 or 3; g2 and d2 are 0, 1, 2 or 3; R et R represent a C.sub.1-C.sub.4 alkyl; R is a C.sub.1-C.sub.4 alkylene radical; the main chain comprising motifs (I) and (II) in which R.sup.0 is in particular the methyl radical; and the number average molecular mass Mn thereof being between 400 and 100,000 g/mol. 2) Method for producing said copolymer, comprising: (i) a step of heating a statistical bipolymer A selected from a poly(butadiene-isoprene), a poly(butadiene-myrcene) and a poly(butadiene-farnesene); and subsequently (ii) a step of heating the formed product, in the presence of a chain transfer agent of formula (C). 3) Adhesive composition comprising said copolymer.

Claims

1. A hydrocarbon-based copolymer P comprising two alkoxysilane end groups F.sup.1 and F.sup.2 connected, respectively, to each of the two ends of the main chain, having the formulae:
F.sup.1: (RO).sub.3-tR.sub.tSi(CH.sub.2).sub.g1
and F.sup.2: (CH.sub.2).sub.d1SiR.sub.t(OR).sub.3-t; or else
F.sup.1: (RO).sub.3-tR.sub.tSiRO(O)C(CH.sub.2).sub.g2
and F.sup.2: (CH.sub.2).sub.d2C(O)ORSiR.sub.t(OR).sub.3-t; in which: t is an integer equal to 0, 1 or 2; g1 and d1, which may be identical or different, represent an integer equal to 1, 2 or 3; g2 and d2, which may be identical or different, represent an integer equal to 0, 1, 2 or 3; R and R, which may be identical or different, represent an alkyl radical comprising from 1 to 4 carbon atoms; R is an alkylene radical comprising from 1 to 4 carbon atoms; characterized in that the main chain of the copolymer P comprises: a unit (I) of formula (I) repeated p times, p being an integer other than 0: ##STR00058## a unit (II) of formula (II) repeated n times, n being an integer other than 0: ##STR00059## in which R.sup.0 represents a methyl radical or one of the three radicals having the following formula: ##STR00060## and, optionally, a unit (III) of formula (III) repeated m times, m being an integer greater than or equal to 0: ##STR00061## in which: R.sup.1, R.sup.2, R.sup.3 and R.sup.4, which may be identical or different, represent: a hydrogen or halogen atom; or a radical comprising from 1 to 22 carbon atoms which is chosen from alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy and alkylcarbonyloxyalkyl, it being possible for the hydrocarbon-based chain of said radical to be optionally interrupted with at least one oxygen atom or one sulfur atom; in addition: at least one of the groups R.sup.1 to R.sup.4 can form, with at least one other of the groups R.sup.1 to R.sup.4 and with the carbon atom or atoms to which said groups are linked, a 3- to 10-membered, optionally substituted, saturated or unsaturated hydrocarbon-based ring or heterocycle; and at least one of the pairs (R.sup.1, R.sup.2) and (R.sup.3, R.sup.4) can form, with the carbon atom to which said pair is linked, a group of two carbon atoms linked by a double bond: CC, the other carbon atom of which bears two substituents chosen from a hydrogen atom and a C.sub.1-C.sub.4 alkyl radical; and the carbon atom bearing one of the groups of the pair (R.sup.1, R.sup.2) may be linked to the carbon atom bearing one of the groups of the pair (R.sup.3, R.sup.4) by a double bond, it being understood that, in accordance with the valency rules, only one of the groups of each of these two pairs is then present; R.sup.5 represents: an oxygen or sulfur atom, or a divalent radical CH.sub.2, C(O) or NR.sup.6 in which R.sup.6 is an alkyl or alkenyl radical comprising from 1 to 22 carbon atoms; it also being pointed out that: the bond represents a single bond or a double bond; F.sup.1 and F.sup.2 are directly linked to two units (I); and n, p and m are such that the number-average molecular mass Mn of the copolymer P is within a range extending from 400 to 100 000 g/mol and its polydispersity index is within a range extending from 1.5 to 3.0.

2. The copolymer P as claimed in claim 1, characterized in that its main chain essentially consists of the repeating unit (I) of formula (I), of the repeating unit (II) of formula (II) and, optionally, of the repeating unit (III) of formula (III).

3. The copolymer P as claimed in claim 1, characterized in that the number p of units (I) and the number n of units (II) are such that: p/(n+p) is between 45% and 95%, and n/(n+p) is between 5% and 55%.

4. The copolymer P as claimed in claim 1, characterized in that its main chain is such that: the unit (I) also has the formula (I): ##STR00062## the unit (II) also has the formula (II): ##STR00063## in which R.sup.0 represents a methyl radical or one of the three radicals having the following formula: ##STR00064## and, optionally, the unit (III) also has the formula (III): ##STR00065## it being pointed out that, in the above formulae, the bond is a single bond geometrically oriented on one side or the other relative to the double bond (cis or trans).

5. The copolymer P as claimed in claim 4, characterized in that its main chain is such that: on the p units of formula (I), p also correspond to formula (I), p being an integer other than 0, less than p and such that p/p is greater than 0.8: ##STR00066## and on the n units of formula (II), n also correspond to formula (II), n being an integer other than 0, less than n and such that n/n is greater than 0.9: ##STR00067##

6. The copolymer P as claimed in claim 1, characterized in that its main chain is such that: the unit (I) also has the formula (I.sup.H): ##STR00068## the unit (II) also has the formula (II.sup.H): ##STR00069## in which R.sup.0 represents a methyl radical or one of the three radicals having the following formula: ##STR00070## and, optionally, the unit (III) has the formula (III.sup.H): ##STR00071##

7. The copolymer P as claimed in claim 1, characterized in that the radical R.sup.0 of the unit (II) represents a methyl radical.

8. The copolymer P as claimed in claim 1, characterized in that F.sup.1 is (RO).sub.3-tR.sub.tSi(CH.sub.2).sub.g1 and F.sup.2 is (CH.sub.2).sub.d1SiR.sub.t(OR).sub.3-t, with g1=d1=1.

9. Copolymer P according to claim 1, characterized in that F.sup.1 is: (RO).sub.3-tR.sub.tSiRO(O)C(CH.sub.2).sub.g2 and F.sup.2 is: (CH.sub.2).sub.d2C(O)ORSiR.sub.t(OR).sub.3-t, with g2=d2=0.

10. A process for preparing the hydrocarbon-based copolymer P as defined in claim 1, said process comprising: (i) a step of heating at a temperature ranging from 30 C. to 80 C.: (a) of a statistical bipolymer A chosen from a poly(butadiene-isoprene), a poly(butadiene-myrcene) and a poly(butadiene-farnesene); and (b) optionally a compound B of formula (B): ##STR00072## and then (ii) a step of heating the product formed in step (i) to a temperature in an interval from 20 to 60 C., in the presence of a chain-transfer agent of formula (C): ##STR00073## in which: F.sup.1 and F.sup.2 are as defined previously; the bond is a single bond geometrically oriented on one side or the other relative to the double bond (cis or trans); it also being pointed out that each of the steps (i) and (ii) is performed in the presence of a metathesis catalyst and of a solvent.

11. The process as claimed in claim 10, characterized in that step (i) leads to the formation of a macrocyclic cooligomer O comprising: the unit of formula (I) repeated p.sup.0 times, p.sup.0 being an integer other than 0; the unit of formula (II) repeated n.sup.0 times, n.sup.0 being an integer other than 0; and, optionally, the unit of formula (III) repeated m.sup.0 times, m.sup.0 being an integer greater than or equal to 0; it being pointed out that p.sup.0, n.sup.0 and m.sup.0 are such that the number-average molecular mass Mn of the cyclic cooligomer O is in a range extending from 162 to 5000 g/mol, preferably from 162 to 2000 g/mol.

12. The process as claimed in claim 10, characterized in that the bipolymer A used in step (i) is a poly-(butadiene-isoprene), preferably comprising from 45% to 95% by number of butadiene-based units and from 5% to 55% by number of isoprene-based units, said percentages being expressed on the basis of the total number of constituent units of the poly(butadiene-isoprene) chain.

13. The process as claimed in claim 12, characterized in that the chain of the poly(butadiene-isoprene) used in step (i) comprises: less than 5% by number of vinyl-1,2 butadiene units on the basis of the number of butadiene-based units, and less than 5% of the total number of vinyl-1,2 isoprene units and of vinyl-3,4 isoprene units on the basis of the number of isoprene-based units.

14. The process as claimed in claim 12, characterized in that the chain of the poly(butadiene-isoprene) used in step (i) comprises: at least 80% by number of cis-1,4 butadiene units on the basis of the number of butadiene-based units, and at least 90% by number of cis-1,4 isoprene units on the basis of the number of isoprene-based units.

15. The process as claimed in claim 10, characterized in that the molar amount of CTA to be introduced into step (ii), the molar amount of bipolymer A and, optionally, the molar amount of compound B introduced into step (i) are such that the ratio r which is equal to the ratio of the number of moles of said CTA: to the number N.sub.(A) of moles of the bipolymer A, in the case where said bipolymer A is the only reagent used in step (i), or to the sum of N.sub.(A) and of the number of moles N.sub.(B) of the compound of formula (B), in the case where the compound of formula (B) is also used in step (i), is in an interval ranging from 0.0010 to 1.0.

16. An adhesive composition comprising a copolymer P as defined in claim 1 and from 0.01% to 3% by weight of a crosslinking catalyst.

17. A process for assembling two substrates by bonding, comprising: the coating of an adhesive composition as defined in claim 16, preferably in the form of a layer with a thickness in a range from 0.3 to 5 mm, on at least one of the two surfaces which respectively belong to the two substrates to be assembled and which are intended to be brought into contact with each other along a faying surface; and then actually bringing the two substrates into contact along their faying surface.

Description

EXAMPLE 1

Depolymerization/Cyclization by Heating a Liquid poly(butadiene-isoprene), Followed by a Hot Cross-Metathesis in the Presence of CTA.SUP.1

[0237] Kuraprene LIR-390 as defined previously is used as liquid poly(butadiene-isoprene), and, as chain-transfer agent, the CTA.sup.1 having the formula:

##STR00044##

[0238] Step (i):

[0239] Poly(butadiene-isoprene) (81.00 mmol) and dry CH.sub.2Cl.sub.2 (9 ml) are introduced into a 20 ml round-bottomed flask in which was also placed a Teflon-coated magnetic stirring bar. The flask and its contents are subsequently placed under argon.

[0240] The catalyst G2 defined previously (9.6 mol) dissolved in CH.sub.2Cl.sub.2 (2 ml) is then added using a cannula.

[0241] This mixture is heated in an oil bath for 3 hours at 40 C. with stirring until the Kuraprene LIR-390 has disappeared and a mixture of macrocyclic cooligomers O has formed, as attested to by size exclusion chromatography.

[0242] Step (ii):

[0243] The compound CTA.sup.1 (0.27 mmol) is added by syringe and with stirring to the mixture contained in the flask from step (i) and heating is continued at a temperature of 40 C.

[0244] The ratio r, as defined previously, is: 0.27/81.00, i.e. 0.003

[0245] After 8 hours, with effect from the addition of the CTA.sup.1, the product present in the flask is extracted after evaporation of the solvent under vacuum. This product is then recovered in the form of a colorless liquid, after precipitating from methanol, filtering and drying at 23 C. under vacuum.

[0246] Analysis by 1H/13C NMR gives the following results:

[0247] .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): (ppm) repeating unit 2.10 (4H*n), 5.43 (2H*n), end group=1.63 (4H, m, CHCH.sub.2Si), 3.57 (18H, s, SiOCH.sub.3), 5.43 (2H, m, CHCHCH.sub.2SH, 5.48 (2H, m, CHCHCH.sub.2Si).

[0248] .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): (ppm) repeating unit 27.4, 32.7, 131.4, end group=cis 10.9 (CHCH.sub.2Si), trans 15.0 (CHCH.sub.2Si), 50.7 (SiOCH.sub.3), 122.6 (CHCHCH.sub.2SH, 131.4 (CHCHCH.sub.2Si).

[0249] These values confirm that the product obtained is a copolymer comprising two alkoxysilane end groups, the main chain of which essentially consists: [0250] of unit (I) of formula:

##STR00045##

and [0251] of unit (II) of formula:

##STR00046##

and [0252] of which two units (I) are each connected to one of the two end groups of formula:

CH.sub.2Si(OCH.sub.3).sub.3

[0253] The number-average molecular mass Mn and the polydispersity index are respectively 17 000 g/mol and 2.7.

EXAMPLE 2

Depolymerization/Cyclization by Heating a Liquid poly(butadiene-isoprene), Followed by a Hot Cross-Metathesis in the Presence of CTA.SUP.2

[0254] Example 1 is repeated, replacing, as chain-transfer agent, CTA.sup.1 with CTA.sup.2 of formula:

##STR00047##

[0255] A polymer is also recovered in the form of a colorless liquid, the .sup.1H NMR/.sup.13C NMR analysis of which gives the following values:

[0256] .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): (ppm) repeating unit 2.10 (4H*n), 5.43 (2H*n), end group=0.67 (4H, m, CH.sub.2CH.sub.2CH.sub.2Si), 1.45 (4H, m, OOCCHCHCH.sub.2CH.sub.2), 1.77 (4H, m, COOCH.sub.2CH.sub.2CH.sub.2Si), 2.19 (4H, m, OOCCHCHCH.sub.2CH.sub.2), 3.57 (18H, s, SiOCH.sub.3), 4.09 (4H, t, COOCH.sub.2CH.sub.2CH.sub.2Si), 5.81 (2H, m, CHCHCOO), 6.94 (2H, m, CH.sub.2CHCHCOO).

[0257] .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): (ppm) repeating unit 27.4, 32.7, 131.4, end group=5.5 (COOCH.sub.2CH.sub.2CH.sub.2Si), 22.2 (COOCH.sub.2CH.sub.2CH.sub.2Si), 66.2 (COOCH.sub.2CH.sub.2CH.sub.2SH, 50.7 (SiOCH.sub.3), 121.3 (CHCHCOO), 149.6 (CHCHCOO), 166.9 (COO).

[0258] These values confirm that the product obtained is a copolymer comprising two alkoxysilane end groups, the main chain of which essentially consists: [0259] of unit (I) of formula:

##STR00048##

and [0260] of unit (II) of formula:

##STR00049##

and

[0261] of which two units (I) are each connected to one of the two end groups of formula:

C(O)O(CH.sub.2).sub.3Si(OCH.sub.3).sub.3

[0262] The number-average molecular mass Mn and the polydispersity index are, respectively, 22 700 g/mol and 2.80.

EXAMPLE 3

Depolymerization/Cyclization by Heating a poly(butadiene-isoprene) in the Presence of Norbornene, Followed by Cross-Metathesis in the Presence of CTA.SUP.2

[0263] Example 2 is repeated, the 81.00 mmol of poly(butadiene-isoprene) being replaced in step (i) with a mixture of 41.00 mmol of poly(butadiene-isoprene) and of 40.00 mmol of norbornene, of formula:

##STR00050##

[0264] available from the company Sigma-Aldrich.

[0265] A polymer that is liquid at room temperature is also recovered, NMR analysis of which gives the following values:

[0266] .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): (ppm) repeating unit trans: 1.08 (2H*n), 1.39 (4H*n), 2.07 (4H*n), 2.47 (2H*n trans), 5.24-5.44 (4H*n trans), cis: 1.82-1.91 (6H*n), 2.07 (4H*n), 2.82 (2H*n cis), 5.24-5.44 (4H*n cis), end group=0.67 (4H, m, CH.sub.2CH.sub.2CH.sub.2Si), 1.45 (4H, m, OOCCHCHCH.sub.2CH.sub.2), 1.77 (4H, m, COOCH.sub.2CH.sub.2CH.sub.2Si), 2.19 (4H, m, OOCCHCHCH.sub.2CH.sub.2), 3.57 (18H, s, SiOCH.sub.3), 4.09 (4H, t, COOCH.sub.2CH.sub.2CH.sub.2Si), 5.81 (2H, m, CHCHCOO), 6.94 (2H, m, CH.sub.2CHCHCOO).

[0267] .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): (ppm) repeating unit: 27.4, 33.1, 42.1, 43.4, 130.3, 133.1, end group=5.5 (COOCH.sub.2CH.sub.2CH.sub.2Si), 22.2 (COOCH.sub.2CH.sub.2CH.sub.2Si), 66.2 (COOCH.sub.2CH.sub.2CH.sub.2Si), 50.7 (SiOCH.sub.3), 121.3 (CHCHCOO), 149.6 (CHCHCOO), 166.9 (COO)

[0268] These values confirm that the polymer obtained is a copolymer comprising two alkoxysilane end groups, the main chain of which essentially consists: [0269] of unit (I) of formula:

##STR00051## [0270] of unit (II) of formula:

##STR00052##

and [0271] of unit (III) of formula:

##STR00053##

and [0272] of which two units (I) are each connected to one of the two end groups of formula:

C(O)O(CH.sub.2).sub.3Si(OCH.sub.3).sub.3

[0273] The number-average molecular mass Mn and the polydispersity index are, respectively, 22 600 g/mol and 2.80.

EXAMPLE 4

Depolymerization/Cyclization by Heating a Liquid poly(butadiene-isoprene) in the Presence of Dicyclopentadiene, Followed by Hot Cross-Metathesis in the Presence of CTA.SUP.1

[0274] Example 3 is repeated, replacing: [0275] the norbornene with dicyclopentadiene, of formula:

##STR00054##

[0276] available from the company Sigma-Aldrich, and [0277] the CTA.sup.2 with CTA.sup.1.

[0278] A polymer that is liquid at room temperature is also recovered, NMR analysis of which gives the following values:

[0279] .sup.1H NMR (CDCl.sub.3, 500 MHz, 298 K): (ppm) repeating unit 1.24 (1H*n), 1.59 (1H*n), 2.07 (4H*n), 2.26 (2H*n), 2.62 (1H*n), 2.85 (2H*n), 3.24 (1H*n), 5.36-5.68 (4H*n), end group=1.63 (4H, m, CHCH.sub.2Si), 3.57 (18H, s, SiOCH.sub.3), 5.43 (2H, m, CHCHCH.sub.2Si), 5.48 (2H, m, CHCHCH.sub.2Si).

[0280] .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): (ppm) repeating unit 27.4, 33.1, 35.1, 38.0, 42.3, 46.0, 47.1, 55.4, 130.5, end group=cis 10.9 (CHCH.sub.2Si), trans 15.0 (CHCH.sub.2Si), 50.7 (SiOCH.sub.3), 122.6 (CHCHCH.sub.2Si), 131.4 (CHCHCH.sub.2Si).

[0281] These values confirm that the polymer obtained is a copolymer comprising two alkoxysilane end groups, the main chain of which essentially consists: [0282] of unit (I) of formula:

##STR00055## [0283] of unit (II) of formula:

##STR00056##

and [0284] of unit (III) of formula:

##STR00057##

and [0285] of which two units (I) are each connected to one of the two end groups of formula:

CH.sub.2Si(OCH.sub.3).sub.3

[0286] The number-average molecular mass Mn and the polydispersity index are, respectively, 28 300 g/mol and 2.80.

EXAMPLE 5

Preparation of an Adhesive Composition Comprising the Copolymer of Example 1

[0287] An adhesive composition consisting of 0.2% by weight of a crosslinking catalyst consisting of dioctyltin dineodecanoate (TIB KAT 223 product from the company TIB Chemicals) and 99.8% by weight of copolymer according to the invention obtained in example 1 is prepared by simple mixing.

[0288] The mixture thus obtained is left under reduced pressure (20 mbar, i.e. 2000 Pa) for 15 minutes and then packaged in an aluminum cartridge.

[0289] The measurement of the tensile strength and the elongation at break by a tensile test was performed according to the protocol described below.

[0290] The principle of the measurement consists in: [0291] drawing in a tensile testing machine, the mobile jaw of which moves at a constant speed equal to 100 mm/minute, a standard test specimen consisting of the crosslinked adhesive composition, and then [0292] recording, at the moment at which the test specimen breaks, the applied tensile stress (expressed in MPa) and also the elongation of the test specimen (expressed as a percentage).

[0293] The standard test specimen is dumbbell-shaped, 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 500 m.

[0294] To prepare the dumbbell, the conditioned composition as described previously is heated to 100 C. and the amount necessary to form, on an A4 sheet of silicone-treated paper, a film having a thickness of 300 pm is then extruded over this sheet, which film is left at 23 C. and 50% relative humidity for 7 days for crosslinking. The dumbbell is then obtained by simply cutting it out from the crosslinked film.

[0295] A tensile stress of greater than 0.7 MPa and an elongation at break of greater than 200% are thus measured for said adhesive composition.

[0296] Said adhesive composition is also subjected to tests of bonding of two wooden panels (each measuring 20 mm20 mm2 mm) to give, after crosslinking for seven days at 23 C. and formation of an adhesive seal 1 mm thick over an area of 12.5 mm20 mm, a braking stress of greater than 2 MPa in adhesive failure.