HYDROCARBON-CONTAINING POLYMERS WITH TWO ALKOXYSILANE END GROUPS

Abstract

The invention relates to a hydrocarbon polymer containing two alcoxysilane end groups having the following Formula (I). The invention also relates to a method for preparing said polymer, to an adhesive composition containing said polymer, and to the use of said adhesive composition.

Claims

1. Hydrocarbon-containing polymer comprising two alkoxysilane end groups, said hydrocarbon-containing polymer being of formula (1) below: ##STR00025## in which F.sub.1 is (R′O).sub.3-zR.sub.zSi—(CH.sub.2).sub.p1— and F.sub.2 is —(CH.sub.2).sub.q1—SiR.sub.z(OR′).sub.3-z; or F.sub.1 is (R′O).sub.3-zR.sub.zSi—R″—OOC—(CH.sub.2).sub.p2— and F.sub.2 is —(CH.sub.2).sub.q2—COO—R″—SiR.sub.z(OR′).sub.3-z; where z is an integer equal to 0, 1, 2 or 3; p1 and q1 are independently an integer equal to 1, 2 or 3; p2 and q2 are independently an integer equal to 0, 1, 2 or 3; the R and R′ groups are independently an alkyl group, preferably linear, comprising from 1 to 4, preferably from 1 to 2, carbon atoms; the R″ group is an alkylene group, preferably linear, comprising from 1 to 4 carbon atoms; and in which: each carbon-carbon bond of the chain denoted is a double bond or a single bond, in accordance with the valency rules of organic chemistry; the R1, R2, R3, R4, R5, R6, R7 and R8 groups are independently a hydrogen, a halogen atom, an alkyl group, a heteroalkyl group, an alkenyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, at least one of the R1 to R8 groups being able to form part of the same ring or heterocycle, saturated or unsaturated, with at least one other of the R1 to R8 groups, according to the valency rules of organic chemistry and at least one of the (R1,R2), (R3,R4), (R5,R6) and (R7,R8) pairs being able to be an oxo group; x and y are integers independently comprised in a range from 0 to 5, preferably from 0 to 2, even more preferably x is equal to 1 and y is equal to 1, the sum of x+y being preferably comprised in a range from 0 to 4 and even more preferably from 0 to 2; the R14, R15, R16 and R17 groups are independently a hydrogen, a halogen atom, an alkyl group, a heteroalkyl group, an alkenyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, at least one of the R14 to R17 groups being able to form part of the same ring or heterocycle, saturated or unsaturated, with at least one other of the R14 to R17 groups, according to the valency rules of organic chemistry; the R20 group is CH.sub.2, O, S, NR.sub.0 or C(═O), R.sub.0 being an alkyl group or an alkenyl group, preferably linear, comprising from 1 to 22, preferably from 1 to 14, carbon atoms; and n is an integer greater than or equal to 2 and m is an integer strictly greater than 0, the molar ratio m:n being comprised between 0 and 0.5, preferably between 0.25 and 0.5; n and m being moreover such that the number-average molecular weight Mn of the hydrocarbon-containing polymer of formula (1) is comprised in a range from 400 to 50,000 g/mol, preferably from 600 to 20,000 g/mol, and the polydispersity index (PDI) of the hydrocarbon-containing polymer of formula (1) is comprised in a range from 1.0 to 3.0, preferably from 1.0 to 2.0, even more preferably from 1.45 and 1.85.

2. Hydrocarbon-containing polymer comprising two alkoxysilane end groups according to claim 1, in which the polymer is of formula (1′) below: ##STR00026## in which x, y, m, n, F.sub.1, F.sub.2, R1, R2, R3, R4, R5, R6, R7, R8, R14, R15, R16, R17 and R20 have the meanings given in claim 1 and the bond is a geometrically oriented bond on either side with respect to the double bond (cis or trans).

3. Hydrocarbon-containing polymer comprising two alkoxysilane end groups according to claim 1, in which the polymer is of formula (1H) below: ##STR00027## in which x, y, m, n, F.sub.1, F.sub.2, R1, R2, R3, R4, R5, R6, R7, R8, R14, R15, R16, R17 and R20 have the meanings given in claim 1:

4. Hydrocarbon-containing polymer comprising two alkoxysilane end groups according to claim 1, in which F1 is (R′O).sub.3-zR.sub.zSi—(CH.sub.2).sub.p1— and F2 is —(CH.sub.2).sub.q1—SiR.sub.z(OR′).sub.3-z, with p1=1 or q1=1, preferably p1=q1=1.

5. Hydrocarbon-containing polymer comprising two alkoxysilane end groups according to claim 4, in which R′ is a methyl, z=0, p1=1 and q1=1.

6. Hydrocarbon-containing polymer comprising two alkoxysilane end groups according to claim 1, in which F1 is (R′O).sub.3-zR.sub.zSi—R″—OOC—(CH.sub.2).sub.p2— and F.sub.2 is —(CH.sub.2).sub.q2—COO—R″—SiR.sub.z(OR′).sub.3-z, with p2=0 or q2=0, preferably p2=q2=0.

7. Hydrocarbon-containing polymer comprising two alkoxysilane end groups according to claim 6, in which R′ is a methyl, R″ is the —(CH.sub.2).sub.3— group, z=0, p2=0 and q2=0.

8. Process for the preparation of at least one hydrocarbon-containing polymer comprising two alkoxysilane end groups according to claim 1, said process comprising at least one ring-opening metathesis polymerization step, in the presence of: at least one metathesis catalyst, preferably a catalyst comprising ruthenium, even more preferably a Grubbs' catalyst; at least one difunctional alkoxysilane chain transfer agent (CTA) of formula (C) below: ##STR00028## in which the bond is a geometrically oriented bond on either side with respect to the double bond (cis or trans); F.sub.1 is (R′O).sub.3-zR.sub.zSi—(CH.sub.2).sub.p1— and F.sub.2 is —(CH.sub.2).sub.q1—SiR.sub.z(OR′).sub.3-z; or F.sub.1 is (R′O).sub.3-zR.sub.zSi—R″—OOC—(CH.sub.2).sub.p2— and F.sub.2 is —(CH.sub.2).sub.q2— COO—R″—SiR.sub.z(OR′).sub.3-z; where z is an integer equal to 0, 1, 2 or 3; p1 and q1 are independently an integer equal to 1, 2 or 3; p2 and q2 are independently an integer equal to 0, 1, 2 or 3; the R and R′ groups are independently an alkyl group, preferably linear, comprising from 1 to 4, preferably from 1 to 2, carbon atoms; the R″ group is an alkylene group, preferably linear, comprising from 1 to 4 carbon atoms; at least one compound of formula (A) below: ##STR00029## in which: the R1, R2, R3, R4, R5, R6, R7 and R8 groups are independently a hydrogen, a halogen atom, an alkyl group, a heteroalkyl group, an alkenyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, at least one of the R1 to R8 groups being able to form part of the same ring or heterocycle, saturated or unsaturated, with at least one other of the R1 to R8 groups according to the valency rules of organic chemistry and at least one of the (R1,R2), (R3,R4), (R5,R6) and (R7,R8) pairs being able to be an oxo group; x and y are integers independently comprised in a range from 0 to 5, preferably from 0 to 2, even more preferably x is equal to 1 and y is equal to 1, the sum of x+y being preferably comprised in a range from 0 to 4 and even more preferably from 0 to 2; and at least one compound of formula (B): ##STR00030## in which the R14, R15, R16 and R17 groups are independently a hydrogen, a halogen atom, an alkyl group, a heteroalkyl group, an alkenyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, at least one of the R14 to R17 groups being able to form part of the same ring or heterocycle, saturated or unsaturated, with at least one other of the R14 to R17 groups, according to the valency rules of organic chemistry; and the R20 group is CH.sub.2, O, S, NR.sub.0 or C(═O), R.sub.0 being an alkyl group or an alkenyl group, preferably linear, comprising from 1 to 22, preferably from 1 to 14, carbon atoms; for a reaction time ranging from 2 to 24 hours and at a temperature comprised in a range from 20 to 60° C.

9. Preparation process according to claim 8, said process being such that the molar ratio of the CTA to the sum of the compounds of formulae (A) and (B) is comprised in a range from 0.01 to 0.10, preferably from 0.05 to 0.10.

10. Preparation process according to claim 8, said process being such that the CTA is selected from the group formed by the compounds of formula (C1) below: ##STR00031## in which z, R, R′, p1, q1 and have the meanings given in claim 8 and the compounds of formula (C2) below: ##STR00032## in which z, R, R′, R″, p2, q2 and have the meanings given in claim 8.

11. Preparation process according to claim 8, said process being such that the CTA is selected from the group formed by bis(propyltrimethoxysilyl)fumarate and trans-1,4-bis(trimethoxysilyl)but-2-ene.

12. Preparation process according to claim 8, said process moreover comprising at least one additional step of hydrogenation of double bonds.

13. Preparation process according to claim 12, such that the additional hydrogenation step is implemented by catalytic hydrogenation, under hydrogen pressure and in the presence of a hydrogenation catalyst such as a carbon-supported palladium catalyst (Pd/C).

14. Adhesive composition comprising at least one polymer according to claim 1 and from 0.01 to 3% by weight at least one cross-linking catalyst, with respect to the weight of the adhesive composition.

15. Process of bonding by assembling two substrates comprising: coating with an adhesive composition according to claim 14, in liquid form, preferably in the form of a layer with a thickness comprised in a range from 0.3 to 5 mm, preferably from 1 to 3 mm, over at least one of the two surfaces which belong respectively to the two substrates to be assembled, and which are intended to be brought into contact with each other at a tangency surface; then effectively bringing the two substrates into contact at their tangency surface.

Description

EXAMPLES

[0108] The following examples illustrate the invention without, however, limiting its scope.

[0109] The synthesis reactions of the examples were carried out in two or three steps, with a cycloolefin synthesis step, a transfer agent (CTA) of formula (C) synthesis step and a step of ring-opening metathesis polymerization of the cycoolefin of formula (A) and of the compound of formula (B) in the presence of a Grubbs' catalyst and transfer agent.

[0110] General diagram 1 of the polymerization reactions implemented in the examples is given below, and will be explained case by case in the examples.

##STR00017##

In which DCM is dichloromethane;
In which the bond is a geometrically oriented bond on either side with respect to the double bond (cis or trans); the chain transfer agent CTA is of formula (C), the cycloolefins are of formulae (A) and (B), and G2 is the metathesis catalyst of formula (9):

##STR00018##

in which Ph is phenyl and Cy is cyclohexyl; and
In which the F1 and F2 groups are symmetrical and correspond respectively to the —COO(CH.sub.2).sub.3Si(OCH.sub.3).sub.3 group (case where CTA is bis(propyltrimethoxysilyl)fumarate) and to —CH.sub.2—Si(OCH.sub.3).sub.3 (case where the CTA is trans-1,4-bis(trimethoxysilyl)but-2-ene); n is the number of moles of cycloolefins of formula (A), m is the number of moles of cycloolefins of formula (B), x is the number of moles of CTA of formula (C).

[0111] The number of monomer units in the polymer is equal to n+m.

[0112] In each of Examples 1 and 2 described below, using diagram 1, the reaction lasts 24 hours at a temperature of 40° C.

[0113] All the polymerizations were carried out in a similar way. The only differences reside in the nature and the initial concentration of the chain transfer agent (CTA). The bis(propyltrimethoxysilyl)fumarate (CTA.sup.1) and trans-1,4-bis(trimethoxysilyl)but-2-ene (CTA.sup.2) illustrating the invention, are used in Examples 1 and 2 and are of the following respective formulae:

##STR00019##

(which corresponds to the case where F.sub.1 is (R′O).sub.3-zR.sub.zSi—R″—OOC—(CH.sub.2).sub.p2— and F.sub.2 is —(CH.sub.2).sub.q2—COO—R″—SiR.sub.z(OR′).sub.3-z, with R′ methyl, R″=—(CH.sub.2).sub.3—, z=0, p2=0 and q2=0);

##STR00020##

(which corresponds to the case where F.sub.1 is (R′O).sub.3-zR.sub.zSi—(CH.sub.2).sub.p1— and F.sub.2 is —(CH.sub.2).sub.q1—SiR.sub.z(OR′).sub.3-z, with R′ methyl, z=0, p1=1 and q1=1).

Examples 1 and 2: Polymerization of a Mixture of Cycloolefins of Formulae (A) and (B)

[0114] ##STR00021##

[0115] The polymerization process described below is such that the cycloolefins of formulae (A) and (B) are respectively as follows:

##STR00022##

[0116] The cyclooctene (COE) of purity greater than 95% and the norbornene (NBN) of purity greater than 99% were commercial products from Sigma Aldrich. They were distilled over CaH.sub.2 beforehand.

[0117] The raw materials, reagents and solvents used during these syntheses were commercial products from Sigma Aldrich.

[0118] The cycloolefins of formulae (A) and (B), respectively COE (5.4 mmol) and NBN (5.4 mmol) described above, and dry CH.sub.2Cl.sub.2 (5 mL) were placed in a 100-mL flask in which a magnetic stirrer coated with Teflon® was also placed. The flask and its contents were then placed under argon. The compound of formula CTA.sup.1 or CTA.sup.2 (1.08 mmol) was then introduced into the flask by syringe. The flask was then immersed in an oil bath at 40° C. then catalyst G2 (5.4 μmol) in solution in CH.sub.2Cl.sub.2 (2 mL) was immediately added by means of a cannula. The reaction mixture then became very viscous in two minutes. The viscosity then decreased slowly over the following 10 minutes. After 24 hours starting from the addition of the catalyst, the product present in the flask was extracted after the solvent was concentrated under vacuum. A product was then recovered after precipitation from methanol, filtration and drying at 20° C. under vacuum (Yield of at least 90% in each of the cases). .sup.1H/.sup.13C NMR analysis made it possible to demonstrate that the product was indeed a polymer having the expected formula.

[0119] All the polymers prepared in the examples were recovered as solid powder or as liquid according to the NBN/COE molar ratio, colourless, easily soluble in chloroform and insoluble in methanol.

[0120] The different tests of Examples 1 and 2 are summarized in Tables 1 and 2 and detailed below.

TABLE-US-00001 TABLE 1 Test Conversion Mn.sub.DRY No. [A]/[B]/[CTA.sup.1]/[Ru] (mol/mol) (%) (g/mol) PDI 1 1,000/1,000/200/1 100 7900 1.60 Where CTA.sup.1 = bis(propyltrimethoxysilyl)fumarate

TABLE-US-00002 TABLE 2 Test Conversion Mn.sub.DRY No. [A]/[B]/[CTA.sup.2/[Ru] (mol/mol) (%) (g/mol) PDI 2 1,000/1,000/200/1 100 7800 1.58 Where CTA.sup.2 = trans-1,4-bis(trimethoxysilyl)but-2-ene

Example 1: Synthesis of a Polymer Comprising Two Alkoxysilane End Groups Starting from Cyclooctene (COE), Norbornene (NBN) and CTA.SUP.1

[0121] The reaction was implemented according to diagram 2 below, in an m:n molar ratio equal to 0.3:

##STR00023##

[0122] The polymer obtained was liquid at ambient temperature.

[0123] The NMR analyses of the polymer obtained for this test gave the following values, which confirmed the structure of the polymer:

[0124] .sup.1H NMR (CDCl.sub.3, 400 MHz, 298 K): repeat unit trans: 1.23 (12H*n), 1.72-1.89 (6H*n), 2.37 (2H*n trans), 5.31 (2H*n trans), cis:1.23 (12H*n), 1.72-1.89(6H*n), 2.72 (2H*n cis), 5.13 (2H*n cis), end group: 0.67 (4H, m, —CH.sub.2—CH.sub.2—Si—), 1.45 (4H, m, —CO—CH—CH—CH.sub.2—CH.sub.2—), 1.77 (4H, m, —O—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 2.19 (4H, m, —CO—CH—CH—CH.sub.2—CH.sub.2—), 3.57 (18H, s, —Si—O—CH.sub.3), 4.09 (4H, t, —O—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 5.81 (2H, m, —CH═CH—COO), 6.94 (2H, m, —CH═CH—COO).

[0125] .sup.13C NMR (CDCl.sub.3, 100 MHz, 298 K): repeat unit 29.17, 29.54, 29.78, 32.37, 33.10, 38.02, 38.67, 41.35, 42.77, 43.13, 43.52, 130.35, 134.89, end groups: 5.49 (—CH.sub.2—CH.sub.2—Si—), 22.24 (—O—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 50.69 (—Si—O—CH.sub.3), 66.22 (—O—CH.sub.2—CH.sub.2—CH.sub.2—Si—), 121.33 (—CH═CH—COO), 149.60 (—CH═CH—COO), 166.87 (—O—CO—).

Example 2: Synthesis of a Polymer Comprising Two Alkoxysilane End Groups Starting from Cyclooctene (COE), Norbornene (NBN) and CTA.SUP.2

[0126] The reaction was implemented according to diagram 3 below, in an m:n molar ratio equal to 0.3:

##STR00024##

[0127] The polymer obtained was liquid at ambient temperature.

[0128] The NMR analyses of the polymer obtained for this test gave the following values, which confirmed the structure of the polymer:

[0129] .sup.1H NMR (CDCl.sub.3, 400 MHz, 298 K): repeat unit trans: 1.23 (12H*n), 1.72-1.89 (6H*n), 2.37 (2H*n trans), 5.31 (2H*n trans), cis:1.23 (12H*n), 1.72-1.89 (6H*n), 2.72 (2H*n cis), 5.13 (2H*n cis), end group: 1.63 (4H, m, —CH—CH.sub.2—Si—), 3.57 (18H, s, —Si—O—CH.sub.3).

[0130] .sup.13C NMR (CDCl.sub.3, 298 K): repeat unit: 29.17, 29.54, 29.78, 32.37, 33.10, 38.02, 38.67, 41.35, 42.77, 43.13, 43.52, 130.35, 134.89, end groups: trans 15.04 (—CH—CH.sub.2Si—), cis 10.92 (—CH—CH.sub.2—Si—), 50.73 (—Si—O—CH.sub.3), 122.61 (—Si—CH.sub.2—CH═CH—), 131.39 (—Si—CH.sub.2—CH═CH—CH.sub.2—).

Example 3: Synthesis of an Adhesive Composition from a Polymer Comprising Two Alkoxysilane End Groups of Example 1

[0131] An adhesive composition comprising 0.2% by weight of a cross-linking catalyst constituted by dioctyltin dineodecanoate (product Tib kat 223 from the company Tib Chemicals), and the polymer according to the invention obtained in Example 1, is produced by mixing.

[0132] The mixture thus obtained was left under reduced stirring (20 mbar i.e. 2000 Pa) for 15 minutes before the composition thus obtained was packaged in an aluminium cartridge.

[0133] The strength and elongation at break were measured by tensile testing according to the protocol described below.

[0134] The measurement principle consists of stretching, in a tensile testing machine the movable jaw of which moves at a constant speed equal to 100 mm/min, a standard test piece constituted by the cross-linked adhesive composition, and recording, at the moment when the test piece breaks, the tensile stress applied (in MPa) as well as the elongation of the test piece (in %).

[0135] The standard test piece is in the form of a dumbbell, as illustrated in 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 μm.

[0136] In order to prepare the dumbbell, the composition packaged as described previously was heated to 100° C., followed by the extrusion onto an A4 sheet of siliconized paper, of the quantity necessary to form thereon a film having a thickness of 300 μm which was left for 7 days at 23° C. and 50% relative humidity for cross-linking. The dumbbell is then obtained by simple cutting out from the cross-linked film.

[0137] The dumbbell of the adhesive composition then has a breaking stress of 8 MPa with an elongation at break of 10%. This test is repeated twice and gives the same result.

[0138] The adhesive composition was then subjected to tests of bonding two wooden slats (each with a size of 20 mm×20 mm×2 mm) in order to lead, after cross-linking for seven days at 23° C., to a force at break of 2 MPa in adhesive rupture.