EP3512898A1

EP3512898A1 - Hydrocarbon polymers with two 2-oxo-1,3-dioxolan-4-carboxylate end groups

Info

Publication number: EP3512898A1
Application number: EP17780795.5A
Authority: EP
Inventors: Guillaume Michaud; Frédéric Simon; Stéphane Fouquay
Original assignee: Bostik SA
Current assignee: Bostik SA
Priority date: 2016-09-15
Filing date: 2017-09-11
Publication date: 2019-07-24
Also published as: FR3055900A1; WO2018050993A1; US20190241700A1; FR3055900B1

Abstract

1) Hydrocarbon polymer comprising two 2-oxo-1,3-dioxolan-4-carboxylate end groups of formula (I): - F¹ represents a radical of formula (Ma) and F² represents a radical of formula (IIb): wherein g and d, identical or different, represent a whole number equal to 1, 2 or 3; -R¹ to R¹² represent a hydrogen atom or an alkyl radical comprising from 1 to 22 carbon atoms; - x and y are whole numbers such that the sum x + y is in a range from 0 to 2; - R¹³ is an oxygen or sulphur atom, or a divalent radical -Chb; - n1, n2, m, p1 and p2 are a whole number or equal to 0 and such that the molecular mass Mn of the polymer of formula (I) is between 400 and 100,000 g/mol. 2) Method for preparing said polymer by ring-opening polymerisation through metathesis. 3) Use as an adhesive mixed with an amino compound comprising at least two amino groups.

Description

Hydrocarbon polymers with two terminal groups 2-oxo-1,3-dioxol

4-carboxylate

The present invention relates to hydrocarbon polymers comprising two end groups 2-oxo-1,3-dioxolan-4-carboxylate (also called cyclocarbonate carboxylates), their preparation and their use as an adhesive.

Polyurethanes are widely used in the field of adhesives, because of the versatility of their properties, made possible by their very high number of structural shapes.

The synthesis of polyurethanes is traditionally done by reaction between a diol and a diisocyanate. Diisocyanates are toxic compounds as such, and are generally obtained from phosgene, itself very toxic by inhalation or contact. The manufacturing process used in the industry generally involves the reaction of an amine with an excess of phosgene to form an isocyanate.

The search for alternatives to the synthesis of polyurethanes without using isocyanate (or NIPU for "Non Isocyanate PolyUrethane" in English, ie "polyurethane without isocyanate"), represents a major challenge for industry adhesives.

This research has been the subject of numerous studies. The most studied approaches relate to the use of polymers capable of reacting with amines or oligomers of amines to form polyurethanes or derivatives structurally close to polyurethanes.

An example of such an approach is the patent application WO 2014/091 173 in the name of Bostik and the CNRS, which describes hydrocarbon polymers comprising two end-terminal groups (2-oxo-1,3-dioxolan-4). -yl) capable of being obtained by metathesis ring opening polymerization, from at least one cyclic cycloolefin, at least one unsaturated chain transfer agent comprising a terminal group (2-oxo-1,3-dioxolan - 4-yl) methyl, and at least one metathesis catalyst. These polymers can then reacting with a (poly) amine to form polyurethanes, without the use of isocyanate, which can be advantageously used to formulate coating, putty or adhesive compositions. However, this reaction is relatively long and remains to be improved.

The object of the present invention is to provide novel polyurethane-type polymer synthesis intermediates for the manufacture of coating compositions, putties or adhesives, and all or part of the disadvantages of the prior art.

In particular, the object of the present invention is to provide novel intermediates whose synthesis does not use isocyanates and is capable of reacting more rapidly with a (poly) amine, compared with hydrocarbon polymers with terminal (2-oxo) 1, 3-dioxolan-4-yl) of the application WO 2014/091 173.

Thus, the present invention relates to a hydrocarbon polymer comprising two end groups 2-oxo-1,3-dioxolan-4-carboxylate (also called cyclocarbonate carboxylates), said hydrocarbon polymer having the formula (I):

(I)

in which :

F ¹ represents a radical of formula (IIa) and F ² represents a radical of formula (Mb):

in which g and d, which are identical or different, represent an integer equal to 1, 2 or 3; each carbon-carbon bond of the main chain of the polymer, denoted == represents a double bond or a single bond, in accordance with the valence rules of organic chemistry; - R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ , identical or different, represent:

a hydrogen or halogen atom; or

a radical comprising from 1 to 22 carbon atoms chosen from alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy and alkenylcarbonyloxy, the hydrocarbon chain of said radical possibly being interrupted by at least one oxygen atom or one sulfur atom; in addition:

at least one of the groups R ¹ to R ⁸ may form, with at least one other group R ¹ to R ⁸ and with the carbon atom or atoms to which the said groups are connected, a saturated or unsaturated hydrocarbon ring or heterocycle, optionally substituted, and comprising from 3 to 10 members; and

at least one of the pairs (R ¹ , R ² ), (R ³ , R ⁴ ), (R ⁵ , R ⁶ ) and (R ⁷ , R ⁸ ) can form, with the carbon atom to which said pair is bonded, a carbonyl group C = O or a group of 2 carbon atoms connected by a double bond: C = C, the other carbon atom carries 2 substituents chosen from a hydrogen atom or a Ci-C radical ₄ alkyl;

x and y are integers, identical or different, in a range from 0 to 6, the sum x + y being in the range 0 to 6;

- R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , identical or different, represent:

a hydrogen or halogen atom; or

a radical comprising from 1 to 22 carbon atoms and chosen from alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy and alkylcarbonyloxyalkyl, the hydrocarbon chain of said radical possibly being interrupted by at least one oxygen atom or one sulfur atom; ; in addition:

at least one of the groups R ⁹ to R ¹² may form, with at least one other group R ⁹ to R ^12, and with the carbon atom or atoms to which said groups are connected, a saturated or unsaturated hydrocarbon ring or heterocycle, optionally substituted, and comprising from 3 to 10 members; and

at least one of the pairs (R ⁹ , R ¹⁰ ) and (R ^{1 1} , R ¹² ) can form with the carbon atom to which said pair is linked a group of 2 carbon atoms connected by a double bond: C = C, the other carbon atom has two substituents selected from a hydrogen atom or a Ci-C ₄ alkyl; and

the carbon atom carrying one of the groups of the pair (R ⁹ , R ¹⁰ ) can be connected to the carbon atom carrying one of the groups of the pair (R ^{1 1} , R ¹² ) by a double bond, it being understood that, according to the valence rules, only one of the groups of each of these 2 pairs is then present;

R ¹³ represents:

an oxygen or sulfur atom, or

a divalent radical -Ch -, -C (= O) - or -NR ° - in which R ° is an alkyl or alkenyl radical comprising from 1 to 22 carbon atoms;

n1 and n2, identical or different, are each an integer or equal to 0, the sum of which is denoted by n;

m is an integer or equal to 0;

p1 and p2, which are identical or different, are each an integer or equal to 0 whose sum p1 + p2 satisfies the equation: p1 + p2 = q x (z + 1)

in which :

q is an integer or equal to 0; and

z is an integer ranging from 1 to 5; and

n1, n2, m, p1 and p2 being further such that the number-average molecular weight Mn of the polymer of formula (I) is in the range of 400 to 100,000 g / mol and its polymolecularity index is included in a range from 1.0 to 3.0.

The various groups, radicals and letters which are included in the formula (I) and which are defined above, retain throughout the present text, and, in the absence of indication to the contrary, the same definition. The following variants of the polymer of formula (I), taken individually or in combination, are particularly preferred:

- g and d included in the definition of F ¹ and F ² are identical and preferably equal to 1;

- R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom or an alkyl radical comprising from 1 to 14 carbon atoms, and even more preferably from 1 to 8;

the integers x and y are in a range from 0 to 2, the sum x + y being in a range from 0 to 2;

x is 1 and y is 1;

- R ⁹ , R ¹⁰ , R ^{1 1} and R ¹² represent a hydrogen atom or a radical whose hydrocarbon portion comprises from 1 to 14 carbon atoms, and even more preferably from 1 to 8;

- R ¹³ represents the divalent radical -Ch -,

z is an integer equal to 1 or 2; and or

the number-average molecular mass Mn lies in a range of from 3,000 to 50,000 g / mol, more particularly from 5,000 to 30,000 g / mol, and the polymolecularity index is in a range of from 1 to 4; at 2.0.

The main chain of the polymer of formula (I) may therefore comprise a single repeating unit chosen from:

the repeated repetition pattern p1 + p2 times, or

- the repeated repetition pattern n1 + n2 times; or

- the repetition pattern repeated once;

it may also comprise 2 motifs chosen from any two of the 3 patterns identified above, it may also include these 3 motifs. When the main chain of the polymer of formula (I) comprises several units, it is understood that the distribution of said units on said main chain is statistical, and that the polymer of formula (I) is then a random polymer.

Preferably, the main chain of the polymer of formula (I) necessarily comprises the repeated repetition pattern p1 + p2 times, corresponding to a meaning of q different from 0, and even more preferably said pattern as well as that repeated m times. As it appears above, the terminal groups F ¹ and F ² are generally symmetrical with respect to the main chain, that is to say that they correspond substantially, with the exception of the indices g and d. .

By "terminal group" is meant a group located at one of the two ends of the main chain of the polymer, which is constituted by one or more repeating units.

Polymolecularity index (also called polydispersity index or PDI) is defined as the ratio Mw / Mn, that is to say the ratio of the weight average molecular weight to the number average molecular weight of the polymer.

In the present text, the two average molecular weights Mn and Mw are measured by Size Exclusion Chromatography (SEC), which is also referred to as gel permeation chromatography (or the term "Size Exclusion Chromatography"). by the corresponding English acronym GPC). The calibration implemented is usually a PEG (PolyEthyleneGlycol) or PS (Polystyrene) calibration, preferably PS.

When one of the indices n1, n2, p1, p2, m, x or y that applies to a set of two brackets equals zero, this means that there is no group between the brackets at which this index apply. For example, the grouping:

represents a simple connection:

represents a double bond:

The polymers of formula (I) according to the invention are particularly homogeneous and temperature-stable.

They can form, after a polyaddition reaction at a temperature below 80 ° C with a primary and / or secondary polyamine and at the end of a reaction time advantageously reduced, a polyurethane that can form an adhesive seal. The adhesive seal thus formed has high cohesion values, in particular greater than 2 MPa. Such cohesive values allow a use of said polymer as an adhesive, for example as a seal on a usual support (concrete, glass, marble), in the field of building, or for gluing glazing in the automotive industry and naval.

The polymers of formula (I) according to the invention are solid or liquid at room temperature (i.e. about 20 ° C.).

According to a preferred variant of the polymer according to the invention, when m is non-zero, that p1 and p2 are non-zero and that n1 and n2 are each equal to 0 (corresponding to the presence in the main chain of the polymer of the only 2 units of repetition repeated respectively p1 + p2 times and m times), then the ratio:

m / (p1 + p2 + m)

is in the range of 30 to 70%, and more preferably is about 50%.

According to a second alternative of this same preferred variant, when m is equal to 0, that p1 and p2 are non-zero and the sum n1 + n2 is non-zero (corresponding to the presence in the main chain of the polymer of the only 2 units of repetition repeated p1 + p2 times and n1 + n2 times respectively), then at least one of the groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is other than an atom of hydrogen, and the ratio:

(n1 + n2) / (p1 + p2 + n1 + n2)

is in the range of 30 to 70%, and more preferably is about 50%.

According to a third alternative of this same preferred variant, when m is different from 0, that p1 and p2 are each equal to 0, the sum n1 + n2 is non-zero (corresponding to the presence in the main chain of the polymer of only 2 repetition patterns repeated respectively m times and n1 + n2 times), and that each of the groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a hydrogen atom, then The report :

m / (m + n1 + n2)

is in the range of 30 to 70%, and more preferably is about 50%. According to a fourth alternative of said preferred variant, when m is non-zero, and p1 and p2 are non-zero, the sum n1 + n2 is non-zero (corresponding to the presence in the main chain of the polymer of the 3 repeating units) and that each of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a hydrogen atom, then the ratio:

m / (p1 + p2 + n1 + n2 + m)

is in the range of 30 to 70%, and more preferably is about 50%.

According to another fifth alternative of said preferred variant, when m is non-zero, that p1 and p2 are non-zero, the sum n1 + n2 is non-zero (corresponding to the presence in the main chain of the polymer of the 3 repeating units) and that at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is other than a hydrogen atom, then the ratio:

(m + n1 + n2) / (p1 + p2 + n1 + n2 + m)

is in the range of 30 to 70%, and more preferably is about 50%.

According to the alternatives of said preferred variant, the polymer of formula (I) is generally in the form of a viscous liquid, and is characterized by a Brookfield viscosity at 23 ° C ranging from 1 mPa.s to 500 Pa.s, preferably from 1 to 150 Pa.s and even more preferably from 1 to 50 Pa.s. It is then advantageously easy to implement and can be combined with an additional component such as a tackifying resin or a filler, to form an adhesive composition.

When the polymer according to the invention is solid at ambient temperature, it is thermoplastic, that is to say deformable and heat fusible (i.e. at a temperature above ambient temperature). It can therefore be used, mixed with a polyamine at the time of use, as a two-component adhesive applied to the interface of substrates to be assembled at their tangency surface.

According to one embodiment of the invention, all the bonds of formula (I) are carbon-carbon double bonds, and formula (I) then becomes the following formula (Γ):

(Ι ')

wherein x, y, n 1, n 2, m, p 1, p 2, F ¹ , F ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ^{1 1} , R ¹² and R ¹³ have the meanings given above and the bond is a geometrically oriented bond on one side or the other with respect to the double bond (cis or trans).

Each of the double bonds of the polymer of formula (Γ) is oriented geometrically cis or trans, preferably is of cis orientation. The geometric isomers of the polymer of formula (Γ) are generally present in variable proportions, with most often a majority of cis (Z) oriented double bonds, and preferably all cis (Z) oriented. It is also possible according to the invention to obtain only one of the geometric isomers, according to the reaction conditions and in particular according to the nature of the catalyst used.

According to another embodiment of the invention, all the bonds of formula (I) are carbon-carbon single bonds, and formula (I) then becomes formula III) below:

(IH)

wherein x, y, n 1, n 2, m, p 1, p 2, F ¹ , F ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ^{1 1} , R ¹² and R ¹³ have the meanings given above.

The formula (IH) illustrates the case where the main chain of the polymer of formula (I) is saturated, that is to say contains only saturated bonds.

In this case, preferably, x is 1 and y is 1. The polymer of formula (IH) may for example be derived from the hydrogenation of the unsaturated polymer of formula (Γ).

According to one embodiment of the polymer of formula (I) according to the invention, m, p1 and p2 are each equal to 0, the polymer having the following formula (II):

(II)

in which x, y, n 1, n 2, F ¹ , F ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ have the meanings given above.

In a particularly preferred manner, x is equal to 1 and y is 1.

According to a particularly preferred form of this embodiment, all the bonds of formula (II) are carbon-carbon double bonds, and formula (II) then becomes the following formula ΙΓ):

Formulas (II) and (ΙΓ) illustrate the case where the main chain of the polymer of formula (I) comprises a single repeating unit, corresponding to that which is repeated n1 + n2 times.

According to another embodiment of the polymer of formula (I) according to the invention, n1 and n2 are each equal to 0, the polymer having the following formula (III):

in which m, p1, p2 F ¹ , F ² , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ have the meanings given above. According to a particularly preferred form of this embodiment, all the bonds of formula (III) are carbon-carbon double bonds, and formula (III) then becomes the following formula (ΙΙΓ):

(ΙΙΓ)

The formulas (III) and (ΙΙΓ) illustrate the case where the main chain of the polymer of formula (I) comprises two repeating units, corresponding to those which are repeated respectively (p1 + p2) times and m times.

With regard to the 2-oxo-1, 3-dioxolan-4-carboxylate end groups of the polymer according to the invention, preferably - (Ch 1 - and - (Ch 2) - each represent a divalent methylene radical. F ¹ and F ² are identical and represent, respectively, the radicals:

The invention also relates to a method for preparing a hydrocarbon polymer comprising two end groups 2-oxo-1,3-dioxolan-4-carboxylate of formula (I) according to the invention, said process comprising at least one polymerization reaction by ring opening by metathesis (also called "Ring-Opening Metathesis Polymerization" or ROMP in English), in the presence:

(a) a metathesis catalyst;

(b) a chain transfer agent (hereinafter also referred to as CTA for "Chain Transfer Agent") comprising 2 2-oxo-1,3-dioxolan-4-carboxylate groups, of formula (B ) next :

(B) in which :

- F ¹ and F ² are as defined above;

the bond is a geometrically oriented bond on one side or the other with respect to the double bond (cis or trans); and (c) at least one compound C selected from:

the compound of formula C1):

wherein z is as previously defined;

the compound of formula (C2):

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , x and y are as previously defined; and

the formula component (C3):

wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are as previously defined;

said polymerization reaction being further implemented:

for a period ranging from 2 to 24 hours and at a temperature in a range of 20 to 70 ° C: and with a ratio r, equal to the ratio of the number of moles of said CTA to the total number of moles of compound C, in a range from 0.0010 to 1.0.

In the definition of the preparation method given above, it is understood that the indefinite article "a", as it relates to a reagent or to the catalyst used, must be interpreted as meaning "at least a ", that is," one or more ". In particular, said method may implement one or more compound (s) C having either the same formula or a different formula, preferably of different formula. When the process uses several compound (s) C, the denominator of the ratio r defined above is the sum of the total number of moles of the compounds C used.

According to a preferred variant of said method, a single compound C is used, corresponding to formula (C2).

According to another preferred variant of said method, at least one compound C is used, corresponding to formula (C1). According to a more particularly preferred embodiment of this latter variant, two compounds C are used, one of the formula (C1) and the other of the formula (C3).

The duration and the temperature of the reaction generally depend on its operating conditions, in particular the nature of the solvent used, and in particular the catalytic loading rate. The skilled person is able to adapt them depending on the circumstances.

Thus, preferably, the duration of the polymerization reaction is from 2 to 10 hours, and the ratio r defined above is in the range of 0.0010 to 0.3.

(a) Metathesis catalyst:

The metathesis catalyst is preferably a catalyst comprising ruthenium, and even more preferably a Grubbs catalyst,

Such a catalyst is generally a commercial product.

The metathesis catalyst is most often a transition metal catalyst including a catalyst comprising ruthenium most often in the form of complex (s) of ruthenium such as a ruthenium-carbene complex. By Grubbs catalyst is generally defined according to the invention a Grubbs catalyst 1 ^st or 2 ^nd generation, but also any other Grubbs catalyst (such as ruthenium carbene) or Hoveyda-Grubbs accessible to the skilled person , such as for example the substituted Grubbs catalysts described in US Pat. No. 5,849,851.

A Grubbs catalyst 1 ^st generation is generally of the formula (G1):

wherein Ph is phenyl, Cy is cyclohexyl, and P (Cy) 3 is a tricyclohexylphosphine group.

The IUPAC name for this compound is: benzylidene-bis (tricyclohexylphosphine) dichlororuthenium (CAS number 172222-30-9). Such a catalyst is available in particular from Aldrich.

A ^2nd generation Grubbs (or G2) catalyst is generally of formula (G

wherein Ph is phenyl and Cy is cyclohexyl.

The IUPAC name of the second generation of this catalyst is benzylidene [1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (tricyclohexylphosphine) ruthenium (CAS number 246047-72-3). This catalyst is also available from Aldrich.

(b) CTA of formula (B):

CTA of formula (B) can be prepared from unsaturated linear diol

(for example 2-butene-1,4-diol available from ALDRICH) and 2-oxo-1,3-dioxolan-4-carboxylic acid according to the 3-step procedure described below adapted from the WO application. 2014/206636:

Step 1: Gentle oxidation of glycerol carbonate to 2-oxo-1,3-dioxolan-4-carboxylic acid acid (according to the protocol of Example 2 of WO 2014/206636):

Step 2: Synthesis of 2-oxo-1,3-dioxolan-4-acyl chloride (according to the protocol of Example 3 of WO 2014/206636):

Step 3: Synthesis of CTA of formula (B)

According to a preferred variant of the invention, the groups - (Ch 1 - and - (CH 2) d - included in the formula (B) of the CTA each represent a divalent methylene radical, in which case F ¹ and F ² are identical and the CTA of formula (B) is advantageously the compound of formula:

hereinafter referred to as CTA;

(c) compound C of formula (CD

The cyclic compound of formula (C1) generally comprises from 8 to 32 carbon atoms. Preferably, it is chosen from the group formed by:

1,5-cyclooctadiene (hereinafter referred to as COD) of formula:

(corresponding to z = 1)

and 1,5,9-cyclododecatriene (hereinafter referred to as CDT) composed of 12 carbon atoms of formula

(corresponding to z = 2)

these 2 compounds being commercially available from Evonik Degussa and Arkema France.

(d) compound C of formula (C2):

The compound of formula (C2) generally comprises from 6 to 30, preferably from 6 to 22, carbon atoms.

Preferably:

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom or an alkyl radical comprising from 1 to 14 carbon atoms, and even more preferably from 1 at 8 ; the integers x and y are in a range from 0 to 2, the sum x + y being in a range from 0 to 2.

According to an even more preferred variant:

x is equal to 1 and y is 1 and / or

at most one of the groups (R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ ) is a C 1 -C 6 alkyl radical and all the others represent a hydrogen atom .

The compound of formula (C2) is in particular chosen from:

cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene and cyclododecene.

5-epoxy-cyclooctene, of formula:

(available from Aldrich),

5-oxocyclooctene, of formula:

or from a 5-alkyl-cyclooctene, of formula:

wherein R is an alkyl radical having 1 to 22 carbon atoms, preferably 1 to 14; R being for example the n-hexyl radical.

Among these compounds, cyclooctene is particularly preferred.

(e) compound C of formula (C3)

The compound of formula (C3) generally comprises from 6 to 30, preferably from 6 to 22, carbon atoms.

Preferably:

R ⁹ , R ¹⁰ , R ¹¹ and R ¹² represent a hydrogen atom or an alkyl or alkoxycarbonyl radical comprising from 1 to 14 carbon atoms, and even more preferably from 1 to 8;

the radical R °, included in the group -NR ° which is one of the meanings of R ¹³ , is a linear radical comprising from 1 to 14 carbon atoms.

According to an even more preferred variant:

at most one of the groups selected from (R ⁹ , R ¹⁰ , R ¹¹ and R ¹² ) is a C 1-6 alkoxycarbonyl radical and all the others represent a hydrogen atom; and or

R ¹³ represents a radical -CH 2 - or an oxygen atom.

The compound of formula (E) is especially chosen from:

norbornene, of the following formula:

norbornadiene, of the following formula:

dic clopentadiene, of the following formula:

7-oxanorbornene, of the following formula:

7-oxanorbornadiene, of the following formula:

5-ethylidene-2-norbornene, of the following formula:

or else 5-norbonene-2-methylacetate, of the following formula:

The compound of formula (C3) may also be chosen from compounds of the following formulas:

in which R is as defined above for the compound of formula (C2). The compound of formula (C3) may also be chosen from the group formed by the addition products (or adducts in English) resulting from the Diels-Alder reaction using cyclopentadiene or furan as starting material, as well as the compounds norbornene derivatives such as branched norbornenes as described in WO 2001/04173 (such as: isobornyl norbornene carboxylate, phenyl norbornene carboxylate, ethylhexyl norbornene carboxylate, phenoxyethyl norbornene carboxylate and alkyl dicarboxymide norbornene, the alkyl having the more often 3 to 8 carbon atoms) and branched norbornenes as described in WO 201 1/038057 (norbornene dicarboxylic anhydrides and optionally 7-oxanorbornene dicarboxylic anhydrides).

Among the various compounds of formula (C3) mentioned, methyl norbornene, 7-oxanorbornene, 5-norbornene-2-carboxylate, of formula:

methyl 5-oxanorbornene-2-carboxylate, of formula:

or else dicyclopentadiene.

The step of polymerization by ring opening metathesis (or ROMP for "Ring-Opening Metathesis Polymerization" in English) is implemented most often in the presence of at least one solvent, generally chosen from the group formed by the solvents aqueous or organic compounds typically used in polymerization reactions and which are inert under the conditions of the polymerization, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water or mixtures thereof. A preferred solvent is selected from the group consisting of benzene, toluene, para-xylene, methylene chloride, dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, hexane heptane, a mixture liquid isoparaffins (eg Isopar®), methanol, ethanol, water or mixtures thereof. Even more preferably, the solvent is selected from the group consisting of benzene, toluene, paraxylene, methylene chloride, 1,2-dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, hexane, heptane, methanol, ethanol or mixtures thereof. Even more particularly preferably, the solvent is dichloromethane, 1,2-dicholoroethane, toluene, heptane or a mixture of toluene and 1,2-dichloroethane. The solubility of the polymer formed during the polymerization reaction depends generally and mainly on the choice of solvent, the nature and the proportion of comonomers and the number average molecular weight of the polymer obtained. It is also possible that the reaction is carried out without solvent.

The method for preparing a hydrocarbon polymer according to the invention may further comprise at least one additional step of hydrogenation of double bonds.

This step is generally carried out by catalytic hydrogenation, most often under hydrogen pressure and in the presence of a hydrogenation catalyst such as a palladium catalyst supported by carbon (Pd / C). It more particularly makes it possible to form a saturated compound of formula (IH) from an unsaturated compound of formula (Γ), and in particular the saturated compounds corresponding to the compounds of formula (ΙΓ) and (ΙΙΓ) from unsaturated compounds.

The invention also relates to the use as adhesive of the hydrocarbon polymer comprising two end groups 2-oxo-1,3-dioxolan-4-carboxylate, as defined above, in a mixture with an amino compound comprising at least two amino groups, by example chosen from diamines, triamines and higher homologs. The amounts of the hydrocarbon polymer and the amine compound correspond to stoichiometric amounts, that is to say that the molar ratio of the number of 2-oxo-1,3-dioxolan-4-carboxylate groups on the number of amine groups is 0.8 to 1.2, preferably 0.9 to 1.1, or even about 1.0.

In practice, the hydrocarbon polymer and the amine compound, used as hardener, are advantageously each included in a component of a bi-component composition which is made available to the user. The latter thus proceeds, at the time of the use of the adhesive, to the mixture of these 2 components, possibly hot, so as to obtain a liquid adhesive composition. The invention also relates to a method of assembling two substrates by gluing, comprising:

coating on at least one of the two substrates to be assembled with a liquid adhesive composition obtained by mixing an amine compound comprising at least two amino groups with the hydrocarbon polymer comprising two terminal groups 2-oxo-1,3-dioxolan -4-carboxylate as defined above; then

the effective contact of the two substrates.

The liquid adhesive composition is either the adhesive composition comprising said compound and polymer in the liquid state at room temperature, or the hot melt adhesive composition. The skilled person is able to proceed so that the adhesive composition used is in liquid form at the time of use.

The coating of the liquid adhesive composition is preferably made in the form of a layer of thickness in a range of 0.3 to 5 mm, preferably 1 to 3 mm, on at least one two surfaces which belong respectively to the two substrates to be assembled, and which are intended to be brought into contact with one another according to a tangent surface. The effective contact of the two substrates is then implemented according to their tangency surface.

Of course, the coating and the contacting must be carried out within a compatible time interval, as is well known to those skilled in the art, that is to say before the adhesive layer applied to the substrate does not lose its ability to fix by bonding this substrate to another substrate. In general, the polycondensation of the hydrocarbon polymer with the amino compound begins to occur during the coating, and then continues to occur during the step of contacting the two substrates.

Suitable substrates are, for example, inorganic substrates such as glass, ceramics, concrete, metals or alloys (such as alloys). aluminum, steel, non-ferrous metals and galvanized metals); or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; metal substrates and paint-coated composites (as in the automotive field).

The following examples are given purely by way of illustration of the invention, and can not be interpreted to limit its scope.

EXAMPLE 1 Polymerization of Cyclooctene (Compound C of Formula (C2)) in the Presence of CTA:

Commercially available cyclooctene (hereinafter referred to as COE) is used and the CTA of formula:

The WCC (10.8 mmol) and 1, 2-dichloroethane dry (5 ml) were introduced into a flask of 20 ml in which was also placed a magnetic stirring bar coated with Teflon ^®. The balloon and its contents are then put under argon.

The CTA compound (0.216 mmol) is then added with stirring to the flask by syringe. The ratio of the reagents expressed in number of moles: CTA COE is 0.020.

The flask is then immersed in an oil bath at 60 ° C., and then the cannulated catalyst G2 defined previously (5.4 μιτιοΙ) in solution in 1.2 is immediately added with a cannula. dichloroethane (2 ml).

The reaction mixture becomes very viscous in the course of 10 minutes. The viscosity then decreases slowly during the following hours.

After 8 hours from the addition of the catalyst, the product present in the flask is removed after evaporation of the solvent in vacuo. The product is then recovered in the form of colorless solid powder, after precipitation in methanol, filtration and drying at 20 ° C under vacuum, with a CTA conversion rate of 50%.

The ¹ H / ¹³ C NMR analysis of the polymer obtained gives the following values:

1 H NMR (CDCl3, 400 MHz, 298 K) δ (ppm) = - repeat unit: 1.29 (8H ^* n), 1.96 (4H ^* n), 5.39 (2H ^* n); terminal group = 5.0 (dd, -O (O) C-CHO-1,3-dioxolan-2-one), 4,6-4,5 (m, -CH2O-1,3-dioxolan-2- one), 4.7 (s, -CH ₂ -O (O) C-), 5.5 (m, -CH = CH-CH ₂ -O (O) C-), 5.6 (m, -CH = CH-CH) ₂ -O (O) C-)

13 C NMR (CDCl3, 100 MHz, 298 K) δ (ppm) = repeat unit: 130.34 (trans), 129.88 (cis), 32.63, 29.77, 29.69, 29.24, 29.20, 29.07, 27.26; terminal group = 171.5 (-CH-C (O) -CH2-ester), 154.81 (-C (O) -cyclocarbonate), 74.16 (-CH-C (O) O-), 68, (-CH2-CH-C (O) O-), 64.04 (-C (O) O-CH2-CH = CH-)

These values confirm the following structure:

This structure is well covered by the formula (ΙΓ) defined previously. The number average molecular weight Mn, measured by NMR, is 5900 g / mol.

The polymolecularity index equal to the Mw / Mn ratio (measured by steric exclusion chromatography with polystyrene standard) is 1, 4.

EXAMPLE 2 Polymerization of 1,5,9-Cyclododecatriene (Compound C of Formula (C1)) in the Presence of CTA:

Example 1 is repeated, replacing the 10.8 mmol of COE with 10.8 mmol of 1,5,9-cyclododecatriene (also called CDT), of formula:

and available from Sigma Aldrich.

The ratio of the reagents expressed in number of moles: CTA / (CDT + norbornene) is 0.020.

A polymer is also recovered in the form of a solid, with a CTA conversion rate of 100%, whose ¹ H / ¹³ C NMR analysis gives the following values:

¹³ C NMR (CDCl3, 100 MHz, 298 K): δ (ppm) repeat unit 27.4, 32.7, 131, 4, terminal group = 171, 5 (-CH-C (O) -CH2-ester ), 154.81 (-C (O) -cyclocarbonate), 74.16 (-CH-C (O) O-), 68.39 (-CH2-CH-C (O) O-), 64.04 (-C (O) O-CH 2 -CH = CH-)

These values confirm the structure below:

This structure is well covered by the formula (ΙΙΓ) defined previously. The number-average molecular weight Mn and the polydispersity index are, respectively, 8400 g / mol and 1.5.

EXAMPLE 3 Polymerization of 1,5,9-Cyclododecatriene (Compound C of Formula (C1)) and Norbornene (Compound C of Formula (C3)) in the Presence of CTA:

Example 2 is repeated, replacing the 10.8 mmol of CDT with a mixture of 5.4 mmol of 1,5,9-cyclododecatriene (also called CDT) and 5.4 mmol of norbornene, of formula: and available from Sigma Aldrich.

A polymer is also recovered in the form of a colorless viscous liquid, with a CTA conversion rate of 100%, whose ¹ H / ¹³ C NMR analysis gives the following values:

13C NMR: δ (ppm) repeating unit: 27.4, 33.1, 42.1, 43.4, 130.4, 133.1, terminal group = terminal group = 171, 5 (-CH-C (O) -CH2-ester), 154.81 ( -C (O) -cyclocarbonate), 74.16 (-CH-C (O) O-), 68.39 (-CH2-CH-C (O) O-), 64.04 (-C (O) O-CH2-CH = CH-)

These values confirm the structure below

This structure is well covered by the formula (ΙΙΓ) defined previously. The number average molecular weight Mn and the polydispersity index are, respectively, 6700 g / mol and 1.5. Example 4 Synthesis of a Polyurethane from the Solid Unsaturated Polyolefin of Example 1

The polyolefin of Example 1 was reacted at 80 ° C. in a stoichiometric ratio with a primary diamine of the polyether diamine type (JEFFAMINE EDR 176, Huntsman) until complete disappearance of the infrared band. characteristic of 1, 3-dioxolan-2-one groups (at 1800 cm-1) and appearance of characteristic bands of the carbamate bond (1700 cm-1 band).

The reaction time recorded during the complete disappearance of the infrared band characteristic of the 1,3-dioxolan-2-one groups was about 3 hours at 80 ° C.

Claims

A hydrocarbon polymer comprising two terminal groups 2-oxo-1,3-dioxolan-4-carboxylate, said hydrocarbon polymer having the formula (I):

(I)

in which :

F ¹ represents a radical of formula (Ma) and F ² represents a radical of formula (Mb):

in which g and d, which are identical or different, represent an integer equal to 1, 2 or 3;

each carbon-carbon bond of the main chain of the polymer, denoted == represents a double bond or a single bond, in accordance with the valence rules of organic chemistry;

- R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ , identical or different, represent:

a hydrogen or halogen atom; or

at least one of the groups R ¹ to R ⁸ can form, with at least one other groups R ¹ to R ⁸ and with the carbon atom (s) to which said groups are connected, a saturated or unsaturated hydrocarbon ring or heterocycle, optionally substituted, and comprising from 3 to 10 members; and

at least one of the pairs (R ¹ , R ² ), (R ³ , R ⁴ ), (R ⁵ , R ⁶ ) and (R ⁷ , R ⁸ ) can form, with the carbon atom to which said pair is connected, a carbonyl group

C = O or a group of 2 carbon atoms connected by a double bond C = C, whose carbon atom other door 2 substituents selected from a hydrogen atom or a Ci-C ₄ alkyl; x and y are integers, identical or different, in a range from 0 to 6, the sum x + y being in the range 0 to 6;

- R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , identical or different, represent:

a hydrogen or halogen atom; or

at least one of the groups R ⁹ to R ¹² may form, with at least one other of the groups R ⁹ to R ¹² and with the carbon atom or atoms to which the said groups are connected, a saturated or unsaturated hydrocarbon ring or heterocycle, optionally substituted, and comprising from 3 to 10 members; and

at least one of the pairs (R ⁹ , R ¹⁰ ) and (R ¹¹ , R ¹² ) can form with the carbon atom to which said pair is linked a group of 2 carbon atoms connected by a double bond: C = C , the other carbon atom has two substituents selected from a hydrogen atom or a Ci-C ₄ alkyl; and

the carbon atom carrying one of the groups of the pair (R ⁹ , R ¹⁰ ) can be connected to the carbon atom bearing one of the groups of the pair (R ¹¹ , R ¹² ) by a double bond, it being understood that, according to the valence rules, only one of the groups of each of these 2 pairs is then present; R ¹³ represents:

an oxygen or sulfur atom, or

a divalent radical -CH 2 -, -C (= O) - or -NR ° - in which R ° is an alkyl or alkenyl radical comprising from 1 to 22 carbon atoms;

m is an integer or equal to 0;

in which :

q is an integer or equal to 0; and

z is an integer ranging from 1 to 5; and - n1, n2, m, p1 and p2 being further such that the number-average molecular weight Mn of the polymer of formula (I) is in the range of 400 to 100,000 g / mol and its polymolecularity index is within a range of 1.0 to 3.0.

2. Hydrocarbon polymer according to claim 1, characterized in that:

- g and d included in the definition of F ¹ and F ² are identical;

- R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom or an alkyl radical comprising 1 to 14 carbon atoms;

x is 1 and y is 1;

- R ⁹ , R ¹⁰ , R ^{1 1} and R ¹² represent a hydrogen atom or a radical whose hydrocarbon portion comprises 1 to 14 carbon atoms, and even more preferably 1 to 8;

R ¹³ represents the divalent radical -CH 2 -,

z is an integer equal to 1 or 2; and or the number-average molecular mass Mn lies in the range from 3000 to 50 000 g / mol, and the polydispersity index is in a range from 1.4 to 2.0.

3. Hydrocarbon polymer according to one of claims 1 or 2, characterized in that the meaning of q is different from 0.

4. Hydrocarbon polymer according to one of claims 1 to 3, characterized in that:

when m is not zero, that p1 and p2 are non-zero and that n1 and n2 are each equal to 0, then the ratio:

m / (p1 + p2 + m)

is in the range of 30 to 70%, or

when m is equal to 0, that p1 and p2 are non-zero and that the sum n1 + n2 is non-zero, then at least one of the groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is other than a hydrogen atom, and the ratio:

(n1 + n2) / (p1 + p2 + n1 + n2)

is in the range of 30 to 70%, or

when m is different from 0, that p1 and p2 are each equal to 0, that the sum n1 + n2 is non-zero, and that each of the groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and

R ⁸ is a hydrogen atom, then the ratio:

m / (m + n1 + n2)

is in the range of 30 to 70%, or

when m is non-zero, that p1 and p2 are non-zero, that the sum n1 + n2 is non-zero and that each of the groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is a hydrogen atom, then the ratio:

m / (p1 + p2 + n1 + n2 + m)

is in the range of 30 to 70%, or

when m is not zero, that p1 and p2 are non-zero, that the sum n1 + n2 is non-zero and that at least one of the groups R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is other than a hydrogen atom, then the ratio:

(m + n1 + n2) / (p1 + p2 + n1 + n2 + m) is in the range of 30 to 70%.

5. Hydrocarbon polymer according to one of claims 1 to 4, characterized in that it has the formula (Γ):

(Γ)

wherein the bond is a geometrically oriented bond on one side or the other with respect to the double bond.

6. Hydrocarbon polymer according to one of claims 1 to 5, characterized in that it has the formula (ΙΓ):

I ')

7. Hydrocarbon polymer according to one of claims 1 to 5, characterized in that it has for formula (III "):

8. Process for preparing a hydrocarbon polymer comprising two end groups 2-oxo-1,3-dioxolan-4-carboxylate of formula (I), as defined in one of claims 1 to 7, comprising at least one metathesis ring opening polymerization reaction, in the presence of:

(a) a metathesis catalyst;

(b) a chain transfer agent (or CTA) comprising 2 2-OXO-1,3-dioxolan-4-carboxylate groups of the following formula (B):

wherein the bond is a geometrically oriented bond on one side or the other with respect to the double bond; and

(c) at least one compound C selected from:

the compound of formula C1):

the compound of formula (C2):

and

the compound of formula C3):

said polymerization reaction being further implemented - for a time ranging from 2 to 24 hours and at a temperature in the range of 20 to 70 ° C; and

with a ratio r, equal to the ratio of the number of moles of said CTA to the total number of moles of compound C, in a range from 0.0010 to 1.0.

9. Use as adhesive of the hydrocarbon polymer as defined in one of claims 1 to 7, in admixture with an amine compound

comprising at least two amino groups.

10. A method of assembling two substrates by gluing, comprising:

coating on at least one of the two substrates to be assembled with a liquid adhesive composition obtained by mixing an amine compound comprising at least two amino groups with the hydrocarbon polymer comprising two terminal groups 2-oxo-1,3-dioxolan -4-carboxylate, as defined in one of claims 1 to 7; then

the effective contact of the two substrates.