Hydrocarbon-based polymers bearing an alkoxysilane end group

Abstract

Polymer of formula (1) bearing an alkoxysilane end group: ##STR00001## in which: is a double or single bond; each of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 is H, a halo, an alkoxycarbonyl or an alkyl, m and p are each from 0 to 5, each of R and R is an alkyl, Z is an alkylene, optionally interrupted with COO, q is 0 or 1, r is 0, 1 or 2, and n is such that the number-average molar mass of the polymer (1) is from 400 to 50 000 g/mol, and the polydispersity index of the polymer (1) is from 1.0 to 2.0. Preparation by ring-opening metathesis polymerization. Use as an adhesion promoter or a reactive plasticizer.

Claims

1. A hydrocarbon-based polymer bearing an alkoxysilane end group, said hydrocarbon-based polymer being of formula (1): ##STR00016## in which: the groups R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each, independently of each other, a hydrogen, a halo group, an alkoxycarbonyl group or an alkyl group, the groups R.sub.1 to R.sub.6 possibly being linked together as members of the same ring or heterocycle comprising at least one carbon-carbon double bond, m and p are integers each within a range from 0 to 5, the sum m+p being within a range from 0 to 10, R and R, which may be identical or different, each represent a linear or branched, alkyl group comprising from 1 to 4 carbon atoms, Z is a divalent group chosen from alkylene groups interrupted with an ester function, and comprising from 1 to 22 carbon atoms, q is an integer equal to 1, r is an integer equal to 0, 1 or 2, and n is an integer such that the number-average molar mass Mn of the hydrocarbon-based polymer of formula (1) is within a range from 400 to 50,000 g/mol, and the polydispersity index (PDI) of the hydrocarbon-based polymer of formula (1) is within a range from 1.0 to 2.0.

2. The hydrocarbon-based polymer bearing an alkoxysilane end group as claimed in claim 1, such that the group of formula [Z].sub.qSi(R).sub.r(OR).sub.3-r is COO(CH.sub.2).sub.3Si(OCH.sub.3).sub.3); or COO(CH.sub.2).sub.3SiCH.sub.3(OCH.sub.3).sub.2).

3. The hydrocarbon-based polymer bearing an alkoxysilane end group as claimed in claim 1, said hydrocarbon-based polymer being of formula (2): ##STR00017## wherein each carbon-carbon bond of the chain noted as is a single bond and the bond means that the bond is geometrically oriented on one side or the other relative to the double bond, cis (Z) or trans (E).

4. The hydrocarbon-based polymer bearing an alkoxysilane end group as claimed in claim 3, wherein each of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are hydrogen.

5. The hydrocarbon-based polymer bearing an alkoxysilane end group as claimed in claim 1, wherein each of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are hydrogen.

6. A process for preparing at least one hydrocarbon-based polymer as claimed in claim 1, said process comprising at least one ring-opening metathesis polymerization in the presence of: at least one metathesis catalyst, at least one chain-transfer agent (CTA) chosen from the group formed by alkenylsilanes bearing a monosubstituted carbon-carbon double bond, and at least one compound chosen from compounds comprising at least one hydrocarbon-based ring, said ring comprising at least one carbon-carbon double bond, and substituted derivatives of this compound, said compound being of formula (7): ##STR00018## in which: each carbon-carbon bond of the chain noted as is a double bond or a single bond, in accordance with the valency rules of organic chemistry; the groups R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each, independently of the other groups or otherwise, a hydrogen, a halo group, an alkoxycarbonyl group or an alkyl group, the groups R.sub.1 to R.sub.6 possibly being linked together as members of the same saturated or unsaturated ring or heterocycle, m and p are integers each within a range from 0 to 5, the sum m+p itself being within a range from 0 to 10, said polymerization being performed for a time of less than 2 hours, when R.sub.1 and R.sub.6 are both equal to H; and said polymerization being performed for a time of less than or equal to 30 hours when at least one from among R.sub.1 and R.sub.6 is not H.

7. The preparation process as claimed in claim 6, such that the chain-transfer agent has the formula CH.sub.2CH[Z].sub.qSi(R).sub.r(OR).sub.3-r in which: R and R, which may be identical or different, each represent a linear or branched alkyl group comprising from 1 to 4 carbon atoms, Z is a divalent alkylene group interrupted with an ester function, and comprising from 1 to 22 carbon atoms, q is an integer equal to 1, and r is an integer equal to 0, 1 or 2.

8. The preparation process as claimed in claim 6, such that the chain-transfer agent is: CH.sub.2CHCOO(CH.sub.2).sub.3Si(OCH.sub.3).sub.3; or CH.sub.2CHCOO(CH.sub.2).sub.3SiCH.sub.3(OCH.sub.3).sub.2.

9. The preparation process as claimed in claim 6, said process being such that the mole ratio of the CTA to the compound comprising at least one hydrocarbon-based ring is within a range from 1 to 10 mol %.

10. The preparation process as claimed in claim 6, said process also comprising at least one additional hydrogenation of double bonds.

11. The preparation process as claimed in claim 10, such that the additional hydrogenation is performed by catalytic hydrogenation, under hydrogen pressure and in the presence of a hydrogenation catalyst.

12. In an adhesion promoter comprising a hydrocarbon-based polymer, the improvement wherein the hydrocarbon-based polymer is one according to claim 1.

13. In an adhesive composition comprising a reactive plasticizer, the improvement wherein the reactive plasticizer is a hydrocarbon-based polymer according to claim 1.

Description

EXAMPLES

(1) The examples that follow illustrate the invention without, however, limiting its scope.

(2) The synthetic reactions of the examples were performed in a single step of ring-opening polymerization of cyclooctene in the presence of a Grubbs catalyst and a transfer agent.

(3) The general reaction scheme (scheme No. 1) of the polymerizations of Examples 1 to 3 is given below, and will be explained on a case by case basis in these Examples 1 to 3.

(4) ##STR00014##

(5) Herein, CTA is the chain-transfer agent, COE is cyclooctene, 2G Grubbs is the catalyst of formula (9) and Y (equal to [Z].sub.qSi(R).sub.r(OR).sub.3-r) is chosen from Si(OCH.sub.3).sub.3 (in the case where the CTA is vinyltrimethoxysilane), CH.sub.2Si(OCH.sub.3).sub.3 (in the case where the CTA is allyltrimethoxysilane) and COO(CH.sub.2).sub.3Si(OCH.sub.3).sub.3 (in the case where the CTA is 3-(trimethoxysilyl)propyl acrylate); x is the number of moles of CTA; n is the number of moles of COE, and s is the repetition number of the monomer unit in the polymer.

(6) In any event, s is a number less than or equal to n, preferably equal to n.

(7) The reaction could last up to 2 hours.

(8) Experimental Protocol

(9) All the experiments were performed, if necessary, under an argon atmosphere.

(10) All the reagents (cyclooctene (COE), 3-hexylcyclooctene (3-H-COE), the second-generation Grubbs (or 2G Grubbs) catalyst of formula (9), vinyltrimethoxysilane, allyltrimethoxysilane and 3-(trimethoxysilyl)propyl acrylate) were products from the company Sigma-Aldrich.

(11) Cyclooctene (COE) and 3-hexylcyclooctene (3-HCOE) were degassed a first time, then dried over CaH.sub.2 and finally distilled before use.

(12) All the other products were used as received.

(13) The NMR spectra were recorded on Brker AM-500 and Brker AM-400 spectrometers, at 298 K in CDCl.sub.3. The chemical shifts were referenced relative to tetramethylsilane (TMS) using the proton (.sup.1H) or carbon (.sup.13C) resonance of the deuterated solvent. The chemical shift of .sup.29Si was referenced relative to TMS.

(14) The number-average and weight-average molar masses (M.sub.n and M.sub.w) and the polydispersity index PDI (M.sub.w/M.sub.n) of the polymers were determined by size exclusion chromatography (SEC), with polystyrene calibration, using a Polymer Laboratories PL-GPC 50 instrument. The samples were eluted with tetrahydrofuran (THF) (product from the company Sigma-Aldrich) at 30 C. and at 1.0 mL/min. The mass spectra were recorded with an AutoFlex LT high-resolution spectrometer (Brker) equipped with an N.sub.2 pulsed laser source (337 nm, 4 ns pulse width).

(15) General Polymerization Procedure of Examples 1 to 3

(16) All the polymerizations were performed in a similar manner. The only differences concerned the nature and the initial concentration of the chain-transfer agent (CTA).

(17) A typical procedure here is described below.

(18) The monomer COE (1 mmol) and dry CH.sub.2Cl.sub.2 (7 mL) were placed in a 20 mL three-necked flask into which was also placed a Teflon-coated magnetic stirring bar. The flask and its contents were then placed under argon. CTA (0.1 mmol), was then introduced into the flask by syringe. The flask was immersed in an oil bath at 40 C. immediately after the addition, via a cannula, of the G2 catalyst (5 mol) dissolved in CH.sub.2Cl.sub.2. After 5 (or 10) minutes, counting from the addition of the catalyst, the product present in the flask was extracted after concentrating the solvent under vacuum. A product was then recovered after precipitation from methanol (which made it possible to recover the catalyst), filtration and drying under vacuum. The analysis made it possible to demonstrate that the product was indeed a polymer having the expected formula.

(19) All the polymers prepared in the examples were recovered as colorless solid powders, readily soluble in chloroform and insoluble in methanol.

Example 1: Synthesis of a Polymer Comprising an Alkoxysilane End Group Starting With Cyclooctene (COE) and Vinyltrimethoxysilane

(20) The reaction was performed according to the general reaction scheme No. 1 given previously, with YSi(OCH.sub.3).sub.3.

(21) The expected polymer was synthesized. It had a melting point of 57 C.

(22) Various tests were performed according to this reaction. They are collated in Table 1 below.

(23) TABLE-US-00001 TABLE 1 Test [COE].sub.0/[CTA].sub.0/[Ru].sub.0 Conversion Mn.sub.SEC.sup.(b) No..sup.(a) (mol/mol) (%) (g/mol) PDI 1 2000:200:1 100 15 000 1.47 2 2000:100:1 100 19 000 1.51 3 2000:50:1 100 23 400 1.50 4 2000:20:1 100 34 500 1.61 in which CTA = vinyltrimethoxysilane and [X].sub.0 = initial concentration of X .sup.(a)the polymerization was performed under the following particular conditions: 5 mol of catalyst (G2), 7 mL of CH.sub.2Cl.sub.2, temperature of 40 C., time 10 minutes .sup.(b)the Mn.sub.SEC values were determined by SEC in THF at 30 C.

(24) NMR analyses of the polymer obtained in test No. 2 gave the following values, which confirmed the structural formula of the polymer:

(25) .sup.1H NMR (CDCl.sub.3, 400 MHz, 298 K).sub.ppm: 5.38; 1.97, 1.29; end groups: 2.17 (m, 4H, CH.sub.2CHCH.sub.2), 3.57 (s, 9H, (CH.sub.3OSi), 4.92-5.01 (m, 2H, CH.sub.2CHCH.sub.2), 5.80-5.82 (m, 1H, CH.sub.2CHCH.sub.2), 6.41-6.48 (m, 1H, CHCHSi).

(26) .sup.13C NMR (.sup.1H) (CDCl.sub.3, 100 MHz, 298 K).sub.ppm: 130.1 (trans) 129.9 (cis), 33.7, 32.6, 29.1, 28.2, 27.2); end groups: 154.8 (CHCHSi), 139.1 (CHCH.sub.2), 117.1 (CHCHSi), 114.1 (CH.sub.2CH), 50.5 ((CH.sub.3O).sub.3Si).

Example 2: Synthesis of a Polymer Comprising an Alkoxysilane End Group Starting With Cyclooctene (COE) and Allyltrimethoxysilane

(27) The reaction was performed according to the general reaction scheme No. 1 given previously, with YCH.sub.2Si(OCH.sub.3).sub.3.

(28) The expected polymer was synthesized. It had a melting point of 54 C.

(29) Various tests were performed according to this reaction. They are collated in Table 2 below.

(30) TABLE-US-00002 TABLE 2 Test [COE].sub.0/[CTA].sub.0/[Ru].sub.0 Conversion Mn.sub.SEC.sup.(b) No..sup.(a) (mol/mol) (%) (g/mol) PDI 5 2000:200:1 100 8500 1.28 6 2000:100:1 100 9700 1.32 7 2000:50:1 100 20 000 1.44 8 2000:20:1 100 33 800 1.55 in which CTA = allyltrimethoxysilane and [X].sub.0 = initial concentration of X .sup.(a)the polymerization was performed under the following particular conditions: 5 mol of catalyst (G2), 7 mL of CH.sub.2Cl.sub.2, temperature of 40 C., time 5 minutes .sup.(b)the Mn.sub.SEC values were determined by SEC in THF at 30 C.

(31) NMR analyses of the polymer obtained in test No. 6 gave the following values, which confirmed the structural formula of the polymer:

(32) .sup.1H NMR (CDCl.sub.3, 400 MHz, 298 K).sub.ppm: 5.37; 1.96, 1.27; end groups: 1.57 (m, 2H, CH.sub.2Si), 3.57 (s, 9H, (CH.sub.3OSi), 4.91-5.01 (m, 2H, CH.sub.2CHCH.sub.2), 5.34-5.37 (m, 2H, CHCHCH.sub.2Si), 5.79-5.84 (m, 1H, CH.sub.2CHCH.sub.2).

(33) .sup.13C NMR (.sup.1H) (CDCl.sub.3, 100 MHz, 298 K).sub.ppm: 130.3 (trans) 129.9 (cis), 33.8, 32.6, 29.6, 29.1, 28.2, 27.2; end groups: 139.2 (CHCH.sub.2), 129.9 (CHCHCH.sub.2Si), 122.6 (CHCHCH.sub.2Si), 114.1 (CH.sub.2CH), 50.7 ((CH.sub.3O).sub.3Si).

Example 3: Synthesis of a Polymer Comprising an Alkoxysilane End Group Starting With Cyclooctene (COE) and 3-(trimethoxysilyl)propyl Acrylate

(34) The reaction was performed according to the general reaction scheme No. 1 given previously, with YCOO(CH.sub.2).sub.3Si(OCH.sub.3).sub.3).

(35) The expected polymer was synthesized. It had a melting point of 59 C.

(36) Various tests were performed according to this reaction. They are collated in Table 3 below.

(37) TABLE-US-00003 TABLE 3 Test [COE].sub.0/[CTA].sub.0/[Ru].sub.0 Conversion Mn.sub.SEC.sup.(b) No..sup.(a) (mol/mol) (%) (g/mol) PDI 9 2000:200:1 100 11 300 1.82 10 2000:100:1 100 14 700 1.53 11 2000:50:1 100 26 300 1.47 12 2000:20:1 100 36 000 1.55 in which CTA = 3-(trimethoxysilyl)propyl acrylate and [X].sub.0 = initial concentration of X .sup.(a)the polymerization was performed under the following particular conditions: 5 mol of catalyst (G2), 7 mL of CH.sub.2Cl.sub.2, temperature of 40 C., time 5 minutes .sup.(b)the Mn.sub.SEC values were determined by SEC in THF at 30 C.

(38) NMR analyses of the polymer obtained in test No. 10 gave the following values, which confirmed the structural formula of the polymer:

(39) .sup.1H NMR (CDCl.sub.3, 400 MHz, 298 K).sub.ppm: 5.36; 1.97, 1.30; end groups: 0.67 (t, 2H, CH.sub.2Si), 1.76 (t, 2H, CH.sub.2CHSi), 3.58 (s, 9H, CH.sub.3OSi), 4.09 (t, 2H, CH.sub.2CH.sub.2CH.sub.2Si), 4.94 (m, 2H, CH.sub.2CHCH.sub.2), 5.38 (m, 1H, CH.sub.2CHCH.sub.2), 5.79-5.84 (m, 1H, CH.sub.2CHCO.sub.2), 6.94 (1H, CH.sub.2CHCO.sub.2).

(40) .sup.13C NMR (.sup.1H) (CDCl.sub.3, 100 MHz, 298 K).sub.ppm: 130.3 (trans) 129.9 (cis), 33.8, 32.6, 29.6, 29.1, 27.2; end groups: 166.7 (CO.sub.2CH.sub.2), 149.4 (CHCHCO.sub.2), 139.1 (CHCH.sub.2), 121.21 (CHCHCO.sub.2), 114.1 (CH.sub.2CH), 66.1 (CO.sub.2CH.sub.2), 50.6 ((CH.sub.3O).sub.3Si), 22.0 (CH.sub.2CH.sub.2Cl.sub.2), 5.20 (CH.sub.2CH.sub.2CH.sub.2).

Example 4: Synthesis of a Polymer Comprising an Alkoxysilane End Group Starting with 3-hexylcyclooctene (3-HCOE) and 3-(trimethoxysilyl)propyl Acrylate

(41) The reaction was performed according to the general reaction scheme No. 2 given below.

(42) ##STR00015##

(43) The expected polymer was synthesized.

(44) A single test was performed according to this reaction. It is collated in Table 4 below.

(45) TABLE-US-00004 TABLE 4 [3-H-COE].sub.o/[CTA].sub.o/[Ru].sub.o Conversion Mn.sub.SEC.sup.(b) (mol/mol) (%) (g/mol) PDI 2 000:100:1 100 4 300 1.56 in which CTA = 3-(trimethoxysilyl)propyl acrylate and [X].sub.0 = initial concentration of X (a) the polymerization was performed under the following particular conditions: catalyst (G2), 7 mL of CH.sub.2Cl.sub.2, temperature of 40 C., time 24 hours .sup.(b)the Mn.sub.SEC values were determined by SEC in THF at 30 C.

(46) NMR analyses of the polymer obtained gave the following values, which confirmed the structural formula of the polymer:

(47) .sup.1H NMR (CDCl.sub.3, 400 MHz, 298 K).sub.ppm: 5.33; 5.10; 1.96, 1.29; end groups: 6.93 (m, 2H, CHCHCO.sub.2), 5.83 (m, 2H, CHCHCO.sub.2), 5.50 (m, CH.sub.2CH), 5.04 (m, CH.sub.2CH), 4.08 (t, OCH.sub.2CH.sub.2CH.sub.2Si6), 3.58 (s, CH.sub.3OSi), 1.84 (m, CH(CH.sub.2).sub.5 and OCH.sub.2CH.sub.2CH.sub.2Si), 0.86 (t, (CH.sub.2).sub.5CH.sub.3), 0.67 (m, OCH.sub.2CH.sub.2CH.sub.2Si).

(48) .sup.13C NMR (.sup.1H) (CDCl.sub.3, 100 MHz, 298 K).sub.ppm: 134.8, 134.1, 129.0, 128.0, 35.9, 34.6-34.1, 31.0, 28.3-21.7; end groups: 165.6 (OCOCH), 148.3 (CHCHCO), 142.5 (CHCHCO), 120.1 (CH.sub.2CH), 112.8 (CH.sub.2CH), 65.0 (SiCH.sub.2CH.sub.2CH.sub.2OCO), 49.6 (CH.sub.3OSi), 41.9 (CHCHCH.sub.2), 31.6 (CHCH.sub.2), 13.1 (CH.sub.3(CH.sub.2).sub.5), 4.4 (SiCH.sub.2CH.sub.2CH.sub.2O).