EP1299452A1

EP1299452A1 - Novel multifunctionalised polyorganosiloxanes comprising groups derived from maleic acid and/or fumaric acid, and methods for preparing same

Info

Publication number: EP1299452A1
Application number: EP01945438A
Authority: EP
Inventors: Nathalie Guennouni; Gérard Mignani
Original assignee: Rhodia Chimie SAS
Current assignee: Rhodia Chimie SAS
Priority date: 2000-06-16
Filing date: 2001-06-14
Publication date: 2003-04-09
Also published as: FR2810327B1; WO2001096444A1; AR028955A1; JP2004503636A; AU2001267660A1; FR2810327A1

Abstract

The invention concerns novel organosilicon compounds comprising a multifunctional polyorganosiloxane (POS) comprising, per molecule, and bound to silicon atoms, at least a hydroxyl radical and/or at least an alkoxyl radical and at least a group containing an activated double ethylene bond selected among groups derived from maleic acid (maleic acid, maleic ester, maleamic acid, maleamic ester, maleic amide) and groups derived from fumaric acid (fumaric acid, fumaric ester, fumaramic acid, fumaramic ester, fumaric amide). The invention also concerns functionalising methods leading to said POS, consisting in particular: in the case of an acid type POS in carrying out a coupling reaction between an amino POS precursor and maleic anhydride or one of its derivatives; and in the case of an ester type POS, in carrying out an esterification reaction of an acid type POS precursor. The compounds comprising a multifunctional POS as described above are capable of exhibiting interesting properties, for example, as coupling agent (white filler-elastomer) in rubber compositions based on isoprene elastomer(s) comprising a white filler as reinforcing filler.

Description

NOVEL MULTIFUNCTIONALIZED POLYORGANOSILOXANES COMPRISING GROUPS DERIVED FROM MALEIC ACID AND / OR FUMARIC ACID, AND

THEIR PREPARATION PROCESSES

The field of the present invention is that of new organosilicon compounds comprising a multifunctional polyorganosiloxane (abbreviated POS) comprising, per molecule, and attached to silicon atoms, on the one hand at least one hydroxyl radical and / or at least one radical alkoxyl and on the other hand at least one group containing an activated ethylenic double bond chosen from groups derived from maleic acid and groups derived from fumaric acid. The present invention also relates to functionalization methods making it possible to lead to the POSs referred to above.

The compounds comprising a multifunctional POS as referred to above, are capable of exhibiting advantageous properties, for example, as a coupling agent (white filler-elastomer) in rubber compositions based on isoprene elastomer (s) ) including a white filler as a reinforcing filler.

In the present specification, the expression "is intended to be defined:

- "groups derived from maleic acid": the groups or functions consisting of the following residues: maleic acid itself; a maleic acid diester (or maleic ester); maleamic acid; an ester of maleamic acid (or maleic ester); a maleic acid diamide (or maleic amide or maleamide);

- "groups derived from fumaric acid": the groups or functions consisting of the following residues: fumaric acid itself; a fumaric acid diester (or fumaric ester); fumaramic acid; a fumaramic acid ester (or fumaramic ester); a diamide of fumaric acid (or fumaric amide or fumaramide).

The principle of multifunctionalization of POS is described, for example, in document WO-A-96/16125 in the name of the Applicant who discloses the preparation of

Multifunctional POS carrying functional units sSi-O-alkyl and functional units ≡Si-W where W is in particular a C ₂ -C ₃₀ hydrocarbon group, a simple alkenyl group, an unsaturated cycloaliphatic group or a mercaptoalkyl group.

Continuing work in the field of multifunctionalization, the Applicant has now found, and this is what constitutes the first object of the invention, new multifunctional POSs carrying, in addition to at least one hydroxyl and / or alkoxyl radical, at least one group chosen from groups derived from maleic acid and groups derived from fumaric acid.

Each of the aforementioned groups, derived from maleic acid and / or fumaric acid, proves to be an interesting function in the chemical processes in which in particular reactions take place with respect to active species such as for example a hydrocarbon radical C ", a mercaptoalkyl radical RS", a mercaptoalkyl anion

RS ", and cycloaddition reactions (" reactions ").

The review of the prior art shows that the synthetic methods allowing access to the functions deriving from maleic acid and / or fumaric acid. However, the Applicant has found that the synthesis methods usually proposed, when applied to silicone chemistry, may not offer satisfactory functionalization yields in the case, which is frequent, where the operating conditions used come to modify so important the silicone skeleton and correspondingly minimize, therefore, the selectivity of the synthesis method. Another object of the present invention is therefore to provide methods for preparing POSs carrying functions derived from maleic acid and / or fumaric acid which are easy to implement and provide the undeniable advantage of being able to lead to POS functionalized with selectivities and yields at a level of excellence not yet achieved so far.

FIRST SUBJECT OF THE INVENTION

Consequently, the present invention, taken in its first object, relates to organosilicon compounds which comprise multifunctional POSs containing similar or different units of formula:

( ^R2 ) a ^γ b ^x c ^si0 4 - (a + b + cv) 0

2

in which :

(1) the symbols R ² , identical or different, each represent a monovalent hydrocarbon group chosen from an alkyl radical, linear or branched, having

1 to 6 carbon atoms, a cycloalkyl radical having 5 to 8 carbon atoms, and a phenyl radical; preferably, the symbols R ² are chosen from the radicals: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, cyclohexyl and phenyl; more preferably, the symbols R ² are methyl radicals; (2) the symbols Y, identical or different, each represent a hydroxyl or alkoxyl function R ¹ O where R ¹ represents an alkyl radical, linear or branched, having from 1 to 15 carbon atoms; preferably, the symbols Y are chosen from a hydroxyl radical and an alkoxyl radical, linear or branched, having from 1 to 6 carbon atoms; more preferably, the symbols Y are chosen from a hydroxyl radical and an alkoxyl radical, linear or branched having from 1 to 3 carbon atoms (that is to say methoxyl, ethoxyl, propoxyl and / or isopropoxyl);

(3) the symbols X, identical or different, each represent a function carrying an activated ethylenic double bond, chosen from the radicals having the following formulas (11/1), (H / 2), and their mixtures:

R 'CO— V R-

^ C

(H / 2)

formulas in which:

+ the symbol V represents a divalent radical -O- or -NR ⁶ -; preferably, the symbol V is a radical -O- or -NR ⁶ - where R ⁶ has the preferred definition indicated below; more preferably, the symbol V is a radical -O- or -NR ⁶ - where R ⁶ has the more preferred definition indicated below; + the symbol W represents a monovalent group COOR ⁷ or a monovalent group

CONR ⁸ R ⁹ ; preferably, the symbol W is a COOR ⁷ group or a group

CONR ⁸ R ⁹ where the radicals R ⁷ , R ⁸ and R ⁹ have the preferred definitions indicated below; more preferably, the symbol W is a COOR ⁷ group or a CONR ⁸ R ^{9 group in} which the radicals R ⁷ , R ⁸ and R ⁹ have the more preferred definitions indicated below; + R ³ is a divalent alkylene radical, linear or branched, comprising from 1 to 15 carbon atoms whose free valence is carried by a carbon atom and is linked to a silicon atom, said radical R ³ being able to be interrupted within of the alkylene chain by at least one heteroatom (such as oxygen and nitrogen) or at least one divalent group comprising at least one heteroatom (such as oxygen and nitrogen), and in particular by at least one divalent residue of general formula —rest- chosen from: -O-, -CO-, -CO-O-, -COO-cyclohexylene (optionally substituted by an OH radical) -, -O-alkylene (linear or branched C ₂ -C ₆ , optionally substituted by an OH or COOH radical) -, -O-CO-alkylene (linear or branched C ₂ -C ₆ , optionally substituted by an OH or COOH radical) -, -CO-NH-,

-O-CO-NH-, and -NH-alkylene (linear or branched C ₂ -C ₆ ) -CO-NH-; R ^{3 also} represents a divalent aromatic radical of general formula —radical— chosen from: -phenylene (ortho, meta or para) -alkylene (linear or branched in C ₂ -C ₆ ) -, -phenylene (ortho, meta or para) -O-alkylene (linear or branched C ₂ -C ₆ ) -, -alkylene (linear or branched C ₂ -C ₆ ) - phenylene (ortho, meta or para) -alkylene

(linear or branched in CC ₆ -, and -alkylene (linear or branched in C ₂ -C ₆ ) -phenylene (ortho, meta or para) -O-alkylene (linear or branched in C ^ Ce) -; preferably , the symbol R ³ represents an alkylene radical which corresponds to the following formulas: - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, -CH ₂ -CH (CH ₃ ) -, - (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ -, - (CH ₂ ) ₃ -O- (CH ₂ ) ₃ -, - (CH ₂ ) ₃ -O-CH ₂ -CH (CH ₃ ) -CH ₂ -, - (CH ₂ ) ₃ -O-CH ₂ CH (OH) -CH ₂ -; more preferably, R ³ is a radical - (CH ₂ ) ₂ - or - (CH ₂ ) ₃ - ; with the precision according to which, in the definitions of R ³ which precede, the divalent residues and radicals mentioned when they are not symmetrical, can be positioned with the valence v1 on the left and with the valence v2 on the right or vice versa with the valence v2 on the left and valence v1 on the right;

+ the symbols R ⁴ and R ⁵ , identical or different, each represent a hydrogen atom, a halogen atom, a cyano radical or an alkyl radical, linear or branched, having from 1 to 6 carbon atoms, R ⁵ can also represent a monovalent group COOR ⁷ ; preferably, the symbols R ⁴ and R ⁵ are chosen from a hydrogen atom, a chlorine atom, and the methyl, ethyl, n-propyl, n-butyl radicals, R ⁵ can also represent a COOR ⁷ group where the radical R ⁷ has the preferred definition indicated below; more preferably, these symbols are chosen from a hydrogen atom and a methyl radical, R ⁵ possibly also representing a COOR ⁷ group where the radical R ⁷ has the more preferred definition indicated below;

+ the symbols R ⁶ , R ⁷ , R ⁸ and R ⁹ , identical or different, each represent a hydrogen atom, an alkyl radical, linear or branched, having from 1 to 6 atoms carbon or a phenyl radical, the symbols R ⁸ and R ^{9 being} able, in addition, to form together and with the nitrogen atom, to which they are linked, a single saturated ring having from 3 to 8 carbon atoms in the ring; preferably, the symbols R ⁶ , R ⁷ , R ⁸ and R ⁹ are chosen from a hydrogen atom, and the methyl, ethyl, n-propyl, n-butyl radicals, the symbols R ⁸ and R ^{9 being} able, in addition, forming together and with the nitrogen atom a pyrrolidinyl or piperidyl ring; more preferably, these symbols are chosen from a hydrogen atom and a methyl radical, the symbols R ⁸ and R ^{9 being} able, in addition, to form together and with the nitrogen atom a piperidyl ring; (4) the symbols a, b and c each represent whole or fractional numbers chosen from: + a: 0, 1, 2 or 3; + b: 0, 1, 2 or 3; + c: 0 or 1; + the sum a + b + c being different from zero and <3;

(5) the rate of R ¹⁰ SiO _{32 units} ("T" units) where R ¹⁰ is chosen from the radicals corresponding to the definitions of R ² , Y and X, this rate being expressed by the number, per molecule, of these units per 100 silicon atoms, is 30% or less and preferably 20%; (6) the rate of Y functions, expressed by the number, per molecule, of Y functions per 100 silicon atoms, is at least 0.8% and, preferably, is in the range from 1 to 100 %; (7) the rate of X functions, expressed by the number, per molecule, of X functions per 100 silicon atoms, is at least 0.4% and, preferably, is in the range from 0.8 100 %.

Given the values that the symbols a, b and c can take and the details given in point (5), it should be understood that each multifunctional POS of formula (I) can have either a linear structure or a cyclic structure, or a mixture of these structures, which structures may also have a certain molar amount of ramifications ("T" motifs).

Given the meanings given above to the expressions "groups derived from maleic acid" and "groups derived from fumaric acid", it should be understood that a multifunctional POS conforming to formula (I) is carrier in particular:

- of function (s) X maleamic acid and / or fumaramic acid, when, in formulas (11/1) and / or (II / 2), the symbol V = -NR ⁶ - and the symbol W = COOR ⁷ where R ⁷ = H; - of function (s) X maleic ester and / or fumaric ester, when, in formulas (11/1) and / or (II / 2), the symbol V = -O- and the symbol W = COOR ⁷ where R ⁷ is different from H;

- of function (s) X malamic ester and / or fumaramic acid, when, in formulas (11/1) and / or (II / 2), either the symbol V = -NR ⁶ - and the symbol W = COOR ⁷ or R ⁷ is different from H, ie the symbol V = -O- and the symbol W = CONR ⁸ R ⁹ ;

- of function (s) X maleic amide and / or fumaric amide, when, in formulas (11/1) and / or (II / 2), the symbol V = -NR ⁶ - and the symbol W = COOR ⁸ R ⁹ .

It has been written above that the invention relates to compounds "which comprise multifunctional POS"; this expression should be interpreted to mean that each organosilicon compound forming part of the present invention may be in the form of a multifunctional POS in the pure state or in the form of a mixture of such POS with a variable quantity by weight (generally much lower 50% in the mixture) of another (or other) compound (s) which may (may) consist in: (i) one and / or the other of the starting reagents from which are prepared multifunctional POS, when the transformation rate of said reagents is not complete; and / or (ii) the product (s) resulting from a complete or incomplete modification of the silicone skeleton of the starting reagent (s); and / or (iii) the product (s) resulting from a modification of the silicone skeleton of the desired multifunctional POS, carried out by a condensation reaction, a hydrolysis and condensation reaction and / or a redistribution reaction. To be more precise, the scope of the invention includes organosilicon compounds which comprise multifunctional POSs, chosen from the family of POSs in accordance with formula (I), which are essentially linear and have the following average formula:

(III)

in which (1 ') the symbols T ¹ are chosen from the units HO _{1 2} and R Oι / ₂ , where the radical R ¹ is as defined above; (2 ') the symbols T ² , identical or different from the symbols T ¹ , are chosen from the units HO _{1 2} , R ¹ Oι ₂ and the unit (R ² ) ₃ SiO _{1 2} , where the radicals R ¹ and R ² are as defined above in points (2) and (1) relating to formula (I);

(3 ') the symbols R ² , X and Y are as defined above in points (1), (3) and (2) relating to formula (I); (4 ') the symbols R ¹⁰ are chosen from the radicals corresponding to the definitions of R ² , X and Y; (5 ') the symbols m, n, p, q, r, s and t each represent whole or fractional numbers which meet the following cumulative conditions:

• m and t are both numbers always different from zero whose sum is equal to 2 + s,

• n is in the range from 0 to 100, • p is in the range from 0 to 100,

• q is in the range from 0 to 100,

• r is in the range from 0 to 100, "s is in the range from 0 to 75,

• when n = 0, p is always a number different from zero and when p = 0, n is always a number different from zero,

The sum n + p + q + r + s + t giving the total number of silicon atoms is in the range from 3 to 250,

• the ratio 100 s / (n + p + q + r + s + t) giving the rate of patterns "T" is <30 and, preferably, 20, • the ratio 100 (m + p + r + s [when R ¹⁰ = Y] + 1) / (n + p + q + r + s + t) giving the rate of functions Y is> 1 and, preferably, ranges from 4 to 100,

• the ratio 100 (n + p + s [when R ¹⁰ = X]) / (n + p + q + r + s + 1) giving the rate of functions X is> 1 and, preferably, ranges from 2 to 100.

As organosilicon compounds which are preferably used, mention may be made of those comprising oligomers and essentially linear POS / 1 polymers which correspond to formula (III) in which (we will then speak, abbreviated, in this case, POS / 1 polymers acid type):

(1 ") the symbols T ¹ are defined as indicated above in point (1 ');

(2 ") the symbols T ² , identical or different from the symbols T ¹ , are chosen from the pattern HO _{1 2} and the pattern RO _{1 2} as defined above in point (1 '); (3 ") • the functions X, identical or different, are chosen from the radicals of formulas (11/1), (H / 2) and their mixtures, where:

- on the one hand the symbol V = -NR ⁶ -, R ⁵ is different from a group COOR ⁷ and the symbol W = COOR ⁷ where R ⁷ = H, and - on the other hand the symbols R ³ , R ⁴ , R ⁵ (different from a COOR ⁷ group) and

R ⁶ are chosen as indicated above in point (3) concerning the formula (I), • the symbols R ² and Y are as defined above in point (3 '); (4 ") the symbols R ¹⁰ are defined as indicated above in point (4 ');(5") the symbols m, n, p, q, r, s and t meet the following cumulative conditions: "m + 1 = 2 + s, ^» n is in the range from 0 to 50,

• p is in the range from 0 to 20,

• when n = 0, p is at least equal to 1 and when p = 0, n is at least equal to 1, • q lies in the interval going from 0 to 48,

"R is in the range from 0 to 10,

• s is in the range from 0 to 1,

• the sum n + p + q + r + s giving the total number of silicon atoms is in the range from more than 3 to 50, • the ratio 100 s / (n + p + q + r + s) giving the rate of reasons "T" is <10,

• the ratio 100 (m + p + r + s [when R ¹⁰ = Y] + 1) / (n + p + q + r + s) giving the rate of functions Y (provided by the patterns represented by the symbols T ¹ , T ² and Y) goes from 4 to 100 and better from 10 to 100,

- the ratio 100 (n + p + s [when R ¹⁰ = X]) / (n + p + q + r + s) giving the rate of functions X goes from 10 to 100, and better still from 20 to 100.

As organosilicon compounds which are still preferably targeted, mention may be made of those comprising oligomers and essentially linear POS / 2 polymers which correspond to formula (III) in which (we will then speak, abbreviated, in this case, of POS / 2 of ester type): (1 "') the symbols T ¹ are defined as indicated above in point (1');

(2 '") the symbols T ² , identical or different from the symbols T ¹ , are chosen from the pattern HO _{1 2} and the pattern R ¹ O _{1 2} as defined above in point (1'); (3 '") • the functions X, identical or different, are chosen from the radicals of formulas (11/1), (H / 2) and their mixtures, where: - on the one hand the symbol V = -NR ⁶ -, R ⁵ is different from a group COOR ⁷ and the symbol W = COOR ⁷ where R ⁷ different from H is a radical as defined above in point (3 ) regarding formula (I), and

- on the other hand the symbols R ³ , R ⁴ , R ⁵ (different from a COOR ⁷ group) and R ⁶ are chosen as indicated above in point (3) concerning the formula (I), • the symbols R ² and Y are as defined above in point (3 '); (4 "') the symbols R ¹⁰ are defined as indicated above point (4');(5"') the symbols m, n, p, q, r, s and t meet the following cumulative conditions: • m + t = 2 + s,

• n is in the range from 0 to 50, ^" p is in the range from 0 to 20,

• when n = 0, p is at least equal to 1 and when p = 0, n is at least equal to 1,

• q is in the range from 0 to 48, ^» r is in the range from 0 to 10,

• s is in the range from 0 to 1,

The sum n + p + q + r + s giving the total number of silicon atoms is in the range from more than 3 to 50,

• the ratio 100 s / (n + p + q + r + s) giving the rate of patterns "T" is <to 10, • the ratio 100 (m + p + r + s [when R ¹⁰ = Y] + 1) / (n + p + q + r + s) giving the rate of functions Y (provided by the patterns represented by the symbols T ¹ , T ² and Y) goes from 4 to 100 and better still from 10 to 100,

• the ratio 100 (n + p + s [when R ¹⁰ = X]) / (n + p + q + r + s) giving the rate of functions X goes from 10 to 100, and better still from 20 to 100. Are still included within the scope of the invention, the organosilicon compounds which comprise multifunctional POSs, chosen from the family of POSs in accordance with formula (I), which are cyclic and have the following average formula:

(III ')

in which (3 "") the symbols R ² , X and Y are as defined above in points (1), (3) and (2) relating to formula (I); (5 "") the symbols n ', p', q 'and r' each represent whole or fractional numbers which meet the following cumulative conditions: • rï lies in the range from 0 to 9,

- p 'is in the range from 0 to 9,

• when n '= 0, p' is at least equal to 1,

• when p '= 0, n' is at least equal to 1 and r 'is also at least equal to 1,

• q 'is in the range from 0 to 9, • r' is in the range from 0 to 2,

• the sum n '+ p' + q '+ r' is in the range from 3 to 10,

The ratio 100 (p ¹ + r ') / (n' + p '+ q' + r ") giving the rate of function Y goes from 4 to 100,

• the ratio 100 (n '+ p') / (n '+ p' + q '+ r') giving the rate of function X goes from 10 to 100.

Note that these cyclic multifunctional POSs can be obtained in admixture with the essentially linear multifunctional POSs of formula (III).

SECOND OBJECT OF THE INVENTION The second object of the present invention relates to the processes by which the organosilicon compounds according to the invention, comprising the multifunctional POSs in accordance with formulas (I), (III) and (III ') given above, can be prepared. These processes involve in particular:

a hydrolysis and condensation reaction of a dihalosilane or a dialkoxysilane carrying an X function, optionally in the presence of a dihalosilane or a dialkoxysilane,

a condensation reaction between an organosilane carrying a function X and at least two functions Y, and a linear POS α, ω-dihydroxylated,

a redistribution and equilibration reaction between an organosilane carrying an X function and at least two Y and / or halo functions, and an organocyclosiloxane which may optionally carry one or more Y functions in the chain,

- a coupling reaction between a precursor POS, linear or cyclic, carrying at least one Y function and functionalized with at least one motif attached to a silicon atom, in particular of the -alkylene type (linear or branched C ₂ -C ₆ ) -OH, -alkylene (linear or branched C ₂ -C ₆ ) -NR ⁶ H or -alkylene (linear or branched C ₂ -C ₆ ) -COOH, and a reactive compound capable of reacting with the abovementioned motif (s) to give rise to the desired function X, - an esterification reaction of a precursor POS, linear or cyclic, carrying at least at least one function Y and at least one function X of formula (H / 1) and / or (H / 2) where the symbol W represents a COOH group.

More specifically, the organosilicon compounds comprising the multifunctional POSs in accordance with formulas (I), (III) and (III ′) are prepared by a process which consists, for example: (a) in hydrolyzing an aqueous organosilane of formula:

R ²

CI— Si-Ci (IV) I X

where the symbols R ² and X have the definitions already given above, possibly operating in the presence of an organosilane of formula:

R ² Cl— S ι i-Ci (V)

R ²

Such a process is well suited for preparing organosilicon compounds comprising multifunctional POSs of formula (III) where the symbols T ¹ and T ^{2 both} represent the motif HO _{1 2} and where on the one hand p = r = s = 0 and on the other hand q is either equal to zero [when the silane (IV) is hydrolyzed in the absence of the silane (V)], or a number different from zero [when the silane (IV) is hydrolyzed in presence of silane (V)]. With regard to the practical way of implementing this method, reference will be made to the content of FR-A-2,514,013 for more details;

(b) to condense, optionally in the presence of a catalyst based for example on a tin carboxylate, an organosilane of formula:

(R ¹ O) - Si- (R ² ) ₃ ^ (VI)

X in which the symbols R1, R2 and X are as defined above and d is a number chosen from 2 or 3, with a POS of formula:

in which the symbol R ² is as defined above and e is an integer or fraction ranging from 2 to 50. Such a process is well suited for preparing compounds comprising multifunctional POSs of formula (III) where the symbols T ¹ and T ² reside in a mixture of patterns HOι ₂ with patterns R ¹ 0 _{1 2} and where the symbols p, r and s can be different from zero when d = 3, while, whatever the value of d, q is different from zero. With regard to the practical manner of implementing this method, one can refer for more details to the contents of US-A-3J55.351; (c) carrying out a redistribution and equilibration reaction, in the presence of an appropriate catalyst and of water, between on the one hand an organosilane of formula:

(Z) _f - Si- (R ² ) ₃ _ _f (VIII) X

in which the symbol R ² and X are as defined above, the symbol Z is chosen from hydroxyl radicals, R ¹ 0 and halo (such as for example chlorine) and f is a number chosen from 2 or 3, and on the other hand an organocyclosiloxane of formula:

in which the symbols R2 are as defined above and g is a number ranging from 3 to 8, and optionally a dihydroxy POS of formula (VII). Such a process is well suited to further prepare organosilicon compounds comprising POSs of formula (III) where the symbols T ¹ and T ² represent the motifs H0 _{1 2} and the symbol q is different from zero. The organosilicon compounds which are preferably targeted in the context of the invention are those comprising POS / 1 polymers of acid type and those comprising POS / 2 polymers of ester type.

An advantageous procedure which can be used to prepare organosilicon compounds comprising POS / 1 polymers of the acid type corresponds to a process (d) consisting in carrying out a coupling reaction between:

on the one hand, an essentially linear amino POS having the same formula (III) as that given above with regard to the definition of the POS / 1 polymers, but in which the symbol X is now an amino function of formula - R ³ -NR ⁶ H where the symbols R ³ and R ⁶ are as defined above in point (3) concerning the formula (I); said amino POS is represented for short, in the following, by the simplified formula:

= Si-R ³ -NR ⁶ H (X)

- and on the other hand maleic anhydride or one of its derivatives of formula:

in which the symbols R ⁴ and R ⁵ are as defined above in point (3) concerning the formula (I).

The amino POS of formula (X) can be prepared, in a manner known per se, by carrying out for example a redistribution and equilibration reaction between on the one hand a POS which results from a hydrolysis of an aikoxysilane carrying a function amine formula:

in which the symbols R ¹ , R ² , d, R ³ and R ⁶ are as defined above with regard to formulas (VI) and (X), and on the other hand a POS α, ω-dihydroxylated of formula (VII).

As regards the practical manner of carrying out the coupling reaction between the amino POS (X) and maleic anhydride (XI), this is a reaction known in itself, usually carried out at a temperature ranging from room temperature (23 ° C) to 80 ° C by operating in the presence of a solvent or a mixture of solvents. Reference may be made to the content of document US-A-3701,795 for more details.

The organosilicon compounds comprising the POS / 2 polymers of ester type, which constitute another category of organosilicon compounds which are also preferentially targeted within the framework of the present invention, can be prepared by applying the advantageous procedures defined below.

According to a first process (e), the organosilicon compounds comprising the POS / 2 polymers of the ester type can be prepared by esterification of an intermediate maleamic acid POS by carrying out the following steps: (e1) coupling reaction, as explained above concerning process (d), between the amino POS (X) and maleic anhydride (XI), then (e2) reaction of esterification of the medium comprising POS / 1 of the acid type formed, to lead to the compound comprising POS / 2 of desired ester type, applying the following synthesis scheme:

POS / 1 acid type

esterification

Ester type POS / 2

With regard to the practical way of implementing step (e2), reference will be made for more details to the contents of the following documents which describe, possibly starting from other reagents, procedures applicable to carrying out this step. step:

(i) reaction of the ammonium salt of the carboxylic acid with an agent such as the organic sulfate of formula (R ⁷ ) ₂ SO ₄ or organic piodide of formula R ⁷ I: cf. especially Can. J. Chem., 65, 1987, pages 2179-2181 and Tetrahedron Letters No. 9, pages 689-692, 1973; (ii) reaction of the carboxylic acid chloride with the alcohol of formula R ⁷ OH in the presence of an amino base: cf. in particular Heterocycles, 39, 2, 1994, pages 767-778 and J. Org. Chem., 26, 1961, pages 697-700; (3i) transesterification reaction in the presence of an ester such as the formate of formula H-COOR ⁷ : cf. including Justus Liebigs Ann. Chem., 640, 1961, pages 142-144 and J. Chem. Soc, 1950, pages 3375-3377; (4i) methylation reaction with diazomethane which makes it possible to easily prepare the methyl ester: cf. including Justus Liebigs Ann. Chem., 488, 1931, pages 211-227; (5i) direct esterification reaction with alcohol R ⁷ -OH: cf. including Org. Syn. Coll., Vol 1, pages 237 and 451, 1941 and J. Org. Chem., 52, 1987, page 4689. According to a second method (f), which corresponds to a preferred synthetic route, the organosilicon compounds comprising the POS / 2 polymers of ester type can be prepared by formation of an amide function by adding the amino POS (X) to an ester derivative (XIV) obtained from a mono-ester of maleic acid (XIII), by carrying out the following stages: (f1) alcoholysis of maleic anhydride ( XI) with alcohol R ⁷ -OH, (f2) activation of the carboxylic acid function of the mono-ester of maleic acid (XIII) obtained, using the various activation methods described in the field of peptide synthesis , to lead to the activated ester derivative (XIV), then (f3) addition of the amino POS (X) to said activated ester derivative (XIV) to lead to the compound comprising POS / 2 of the desired ester type, by applying the synthesis scheme next :

Amino POS (X) where the symbol Ac of the derivative (XIV) represents an activating function. With regard to the practical manner of implementing steps (f1) to (f3), reference will be made for more details to the contents of the following documents which describe, possibly starting from other reagents, procedures applicable to the conduct of the various stages of the process considered:

- for step (f1): cf. in particular J. Med. Chem., 1983, 26, pages 174-181;

- for stages (f2) and (f3): cf. John JONES, Amino Acid and Peptide-Synthesis, pages 25-41, Oxford University Press, 1994.

In order to allow the addition of the amino function to the carboxylic acid function of the maleic acid monoester (XIII), it is first necessary to carry out the activation of said carboxylic acid function and this activation can be done by in particular by implementing the following methods:

(j) activation by reaction with an alkyl chloroformate, according to the scheme:

T-COOH CI-CO-OR » _T. _CQ _Q. _C Q. _{0R / + HCI} activating function Ac

where T represents the residue -R ⁴ C = CR ⁵ -COOR ⁷ and R represents a linear alkyl radical having for example 1 to 3 carbon atoms;

(2d) activation by reaction with dicyclohexylcarbodiimide (DCCI) in the presence preferably of N-hydroxysuccinimide (HO-SN), according to the scheme:

activating function Ac

(3d) activation by reaction with a chlorinated compound such as for example thionyl chloride, phosphorus pentachloride, according to the scheme:

chlorine compound T-COOH T-CO-CI + POCI ₃ + HCI

ac

Activation methods (j) and (2j) are especially preferred.

To return to the general processes (b) and (c) for preparing multifunctional POS-based compounds, they can advantageously be carried out starting, for example, from an organosilane of formula:

in which the symbols R ¹ , R ² , d, R ³ , R ⁶ , R ⁴ , R ⁵ and R ⁷ (different from H) are as defined above with respect to the formula (VI) and the point ( 3) concerning formula (I).

Such organosilanes are products which can be prepared by applying either of the methods (e1) and (e2) described above, in the conduct of which the amino POS (X) will be replaced by the amino alkoxysilane of formula (XII).

Carrying out methods (d), (e) and (f) leads to the production of an organosilicon compound which can be in the form of a multifunctional POS in the pure state or in the form of a mixture of a multifunctional POS with a variable quantity by weight (generally much less than 50% in the mixture) of another (or other) compound (s) which can (can) consist for example in a small quantity of the monofunctional POS cyclic of formula:

in which :

+ the symbols R ² are as defined above in points (1) concerning the formula

0), + the symbols X are as defined above in points (3) relating to formula (I),

+ the symbols n "and q" are whole or fractional numbers satisfying the following cumulative conditions:

• n "is in the range from 1 to 9,

• q "is in the range from 1 to 9,

• the sum n "+ q" is in the range from 3 to 10, said cyclic monofunctional POS being derived from a modification of the silicone skeleton of the desired multifunctional POS.

APPLICATION

The organosilicon compounds according to the invention, comprising the multifunctional POSs in accordance with formulas (I), (III) and (III ¹ ) given above, can be advantageously used as coupling agent for white filler-elastomer in elastomer compositions (s) of rubber type, natural (s) or synthetic (s), based on isoprene elastomer (s), comprising a white filler, in particular a siliceous material, as reinforcing filler, compositions which are intended the manufacture of articles or elastomer (s).

The types of elastomeric article (s), where the use of a coupling agent is most useful, are those subject in particular to the following constraints: variations in temperature and / or variations in high frequency stress in regime dynamic; and / or a significant static stress; and / or significant flexion fatigue in dynamic regime. Types of articles are for example: conveyor belts, power transmission belts, flexible hoses, expansion joints, seals of household appliances, supports acting as engine vibration extractors either with metal fittings, either with a hydraulic fluid inside the elastomer, cables, cable sheaths, shoe soles and rollers for cable cars.

It is known to those skilled in the art that it is necessary to use a coupling agent, also called a binding agent, which has the function of ensuring the connection between the surface of the white filler particles and the elastomer, while facilitating the dispersion of this white charge within the elastomeric matrix.

The Applicant discovered during its research that:

- specific coupling agents consisting of a compound comprising a multifunctional POS in accordance with formulas (I), (III) and (III '), carrying on the one hand at least one OH radical and / or at least one alkoxyl radical and on the other hand at least one group containing an activated ethylenic double bond chosen from groups derived from maleic acid and groups derived from fumaric acid,

offer coupling performances which are close to those linked to the use of polyisulphurized alkoxysilanes, in particular TESPT or bis 3-triethoxysilylpropyl tetrasulphide which is generally considered today as the product providing, for vulcanizates charged with silica, the best compromise in terms of safety in roasting, ease of implementation and reinforcing power, but the known disadvantage of which is that it is very expensive (see for example patents US-A-5,652,310, US-A- 5 684 171, US-A-5 684 172), when said specific coupling agents are used in rubber compositions based on isoprene elastomer (s). The elastomer (s) compositions include:

- at least one isoprene elastomer,

- a reinforcing white filler, and - an adequate amount of coupling agent consisting of the organosilicon compound comprising the multifunctional POS which has been defined above, carrying on the one hand at least one hydroxyl radical and / or at least one alkoxyl radical and on the other hand at least one group containing an activated ethylenic double bond chosen from groups derived from maleic acid and groups derived from fumaric acid.

More specifically, these compositions include (the parts are given by weight):

• for 100 parts of isoprene elastomer (s),

From 10 to 150 parts of white filler, preferably from 30 to 100 parts and more preferably from 30 to 80 parts, • an amount of coupling agent or organosilicon compound which provides 0.5 to 15 parts of multifunctional POS in the composition, preferably 0.8 to 10 parts and more preferably 1 to 8 parts.

Advantageously, the amount of coupling agent, chosen from the aforementioned general and preferred areas, is determined so that it represents from 1% to 20%, preferably from 2 to 15%, more preferably from 3 at 8%, relative to the weight of the reinforcing white filler.

We will return in the following to the definitions, in turn, of isoprene elastomers, and of reinforcing white filler. By isoprene elastomers which are used for the rubber compositions, we mean more precisely:

(1) synthetic polyisoprenes obtained by homopolymerization of isoprene or 2-methyl-1,3-butadiene;

(2) synthetic polyisoprenes obtained by copolymerization of isoprene with one or more ethylenically unsaturated monomers chosen from:

- (2J) conjugated diene monomers, other than isoprene, having from 4 to 22 carbon atoms, such as for example: 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, chloro- 2 1,3-butadiene (or chloroprene), 1-phenyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene; - (2.2) vinyl aromatic monomers having 8 to 20 carbon atoms, such as for example: styrene, ortho-, meta- or paramethylstyrene, the commercial "vinyl-toluene" mixture, paratertiobutylstyrene, methoxystyrenes, chlorostyrenes, vinyl mesitylene, divinylbenzene, vinylnaphthalene;

- (2.3) vinyl nitrile monomers having from 3 to 12 carbon atoms, such as for example acrylonitrile, methacrylonitrile;

- (2.4) the acrylic ester monomers derived from acrylic acid or from methacrylic acid with alkanols having from 1 to 12 carbon atoms, such as, for example, methyl acrylate, ethyl acrylate, sodium acrylate propyl, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate ;

- (2.5) a mixture of several of the aforementioned monomers (2J) to (2.4) with one another; copolymer polyisoprenes containing between 99% and 20% by weight of isoprenic units and between 1% and 80% by weight of diene units, aromatic vinyls, vinyl nitriles and / or acrylic esters, and consisting for example in poly (isoprene -butadiene), poly (isoprene-styrene) and poly (isoprene-butadiene-styrene); (3) natural rubber;

(4) the copolymers obtained by copolymerization of isobutene and isoprene (butyl rubber), as well as the halogenated, in particular chlorinated or brominated, versions of these copolymers; (5) a mixture of several of the aforementioned elastomers (1) to (4) with one another;

(6) a mixture containing a majority quantity (ranging from 51% to 99.5% and preferably from 70% to 99% by weight) of the abovementioned elastomer (1) or (3) and a minority quantity (ranging from 49% to 0.5% and preferably from 30% to 1% by weight) of one or more diene elastomers other than isoprene. By diene elastomer other than isoprene, is understood in a manner known per se: the homopolymers obtained by polymerization of one of the conjugated diene monomers defined above in point (2J), such as for example polybutadiene and polychloroprene; the copolymers obtained by copolymerization of at least two of the above-mentioned conjugated dienes (2.1) together or by copolymerization of one or more of the above-mentioned conjugated dienes (2J) with one or more of the above-mentioned unsaturated monomers (2.2), (2.3) and / or (2.4), such as for example poly (butadiene-styrene) and poly (butadiene-acrylonitrile).

As a preference, use is made of one or more isoprenic elastomers chosen from: (1) synthetic polyisoprenes homopolymers; (2) synthetic polyisoprenes copolymers consisting of poly (isoprene-butadiene), poly (isoprene-styrene) and poly (isoprene-butadiene-styrene); (3) natural rubber; (4) butyl rubber; (5) a mixture of the above-mentioned elastomers (1) to (4) with one another; (6) a mixture containing a majority quantity of the abovementioned elastomer (1) or (3) and a minority quantity of diene elastomer other than isoprene consisting of polybutadiene, polychloroprene, poly (butadiene-styrene) and poly (butadiene-acrylonitrile).

More preferably, use is made of one or more isoprenic elastomers chosen from: (1) synthetic polyisoprenes homopolymers; (3) natural rubber; (5) a mixture of the above-mentioned elastomers (1) and (3); (6) a mixture containing a majority quantity of the abovementioned elastomer (1) or (3) and a minority quantity of diene elastomer other than isoprene consisting of polybutadiene and poly (butadiene-styrene).

In the present specification, the expression "reinforcing white charge" is understood to define a "white" charge (that is to say inorganic or mineral), sometimes called "clear" charge, capable of reinforcing on its own, without other means than that of a coupling agent, an elastomer composition (s) of rubber type, natural (s) or synthetic (s). The physical state under which the reinforcing white filler is present is immaterial, that is to say that said filler can be in the form of powder, micro pearls, granules or beads.

Preferably, the reinforcing white filler consists of silica, alumina or a mixture of these two species.

More preferably, the reinforcing white filler consists of silica, taken alone or as a mixture with alumina.

As silica capable of being used, all precipitated or pyrogenic silicas known to those skilled in the art having a BET specific surface area <450 m ² / g are suitable. Precipitation silicas are preferred, these can be conventional or highly dispersible.

By highly dispersible silica is meant any silica having an ability to disaggregate and to disperse in a very large polymer matrix observable by electron or optical microscopy, on fine sections. As nonlimiting examples of highly dispersible silicas, mention may be made of those having a specific CTAB surface of 450 m ² / g or less and particularly those described in patent US-A-5,403,570 and patent applications WO-A-95 / 09127 and WO-A-95/09128 the content of which is incorporated here. Also suitable are treated precipitated silicas such as for example silicas "doped" with aluminum described in patent application EP-A-0 735 088, the content of which is also incorporated here.

More preferably, precipitation silicas having:

- a CTAB specific surface ranging from 100 to 240 m ² / g, preferably from 100 to 180 m ² / g,

- a BET specific surface area ranging from 100 to 250 m ² / g, preferably from 100 to 190 m ² / g,

- a DOP oil intake of less than 300 ml / 100 g, preferably ranging from 200 to 295 ml / 100 g,

- a specific BET / CTAB specific surface ratio ranging from 1.0 to 1.6.

Of course, silica also means blends of different silicas. The CTAB specific surface is determined according to the NFT 45007 method of November 1987. The BET specific surface is determined according to the method of BRUNAUER, EMMET, TELLER described in "The Journal of the American Chemical Society, vol. 80, page 309 (1938) "corresponding to standard NFT 45007 of November 1987. The DOP oil intake is determined according to standard NFT 30-022 (March 1953) by using dioctylphthalate. As reinforcing alumina, a highly dispersible alumina is advantageously used having:

- a BET specific surface area ranging from 30 to 400 m ² / g, preferably from 80 to 250 m ² / g,

an average particle size at most equal to 500 nm, preferably at most equal to 200 nm, and

a high rate of reactive AI-OH surface functions, as described in document EP-A-0810 258.

As nonlimiting examples of such reinforcing aluminas, mention may be made in particular of aluminas A125, CR125, D65CR from the company BAIKOWSKI. It may be advantageous, if necessary, depending on the particular conditions of use of the coupling agents and the final destination of the rubber compositions, to add to the rubber composition at least one coupling activator.

The coupling activator, when one is used, is preferably chosen from the group consisting of peroxides, hydroperoxides, azido compounds, bis (azo) compounds, peracids, peresters or a mixture of two or more more than two of these compounds. According to a particularly preferential mode, the radical initiator, when one is used, is chosen from peroxide of 1.1 bis (t-butyl) -3,3,5- trimethylcyclohexane, 1,1'-azobis (isobutyronitrιïe ) and their mixture. The radical initiator, when one is used, is used in very small proportion in rubber compositions, namely at a rate ranging from 0.05 to 1 part, preferably from 0.05 to 0.5 parts, and more preferably still from 0.1 to 0.3 parts, per 100 parts of elastomer (s).

Of course, the rubber-type compositions also contain all or part of the other constituents and auxiliary additives usually used in the field of elastomer (s) and rubber (s) compositions.

Thus, all or part of the following other constituents and additives can be used:

• as regards the vulcanization system, there may be mentioned for example: - vulcanization agents chosen from sulfur or sulfur-donor compounds, such as for example thiuram derivatives; vulcanization accelerators, such as, for example, guanidine derivatives, thiazole derivatives or sulfenamide derivatives; vulcanization activators such as, for example, zinc oxide, stearic acid and zinc stearate;

• in the case of other additive (s), mention may be made, for example: a conventional reinforcing filler such as carbon black (in this case, the reinforcing white filler used constitutes more than 50% of the weight of the whole reinforcing white filler + carbon black); a conventional white filler with little or no reinforcing, such as, for example, clays, bentonite, talc, chalk, kaolin, titanium dioxide or a mixture of these species; antioxidants; antiozonants, such as, for example, N-phenyl-N '- (1,3-dimethyl butyl) -p-phenylene diamine; - plasticizing agents and implementation aid agents.

The vulcanization (or baking) of the rubber-type compositions is carried out in a known manner at a temperature generally ranging from 130 ° C. to 200 ° C., for a sufficient time which can vary for example between 5 and 90 minutes depending in particular on the temperature. curing, the vulcanization system adopted and the vulcanization kinetics of the composition considered.

The following examples illustrate the present invention. EXAMPLE 1

This example illustrates the preparation of an organosilicon compound according to the invention, comprising a POS / 1 polymer of acid type.

This compound is prepared by implementing method (d) which has been explained above in the present specification, consisting in reacting an amino POS of formula (X) with maleamic anhydride.

1.- Preparation of the starting amino POS:

In a glass reactor of 2 liters, fitted with a mechanical stirring system and an ascending coolant, is introduced γ-aminopropylsilane of formula (C ₂ H ₅ 0) ₂ CH ₃ Si (CH ₂ ) ₃ NH ₂ (858.1 g, or 4.484 moles), an α, ω-dihydroxylated polydimethylsiloxane oil (346.51 g) having a viscosity of 50 mPa.s at 25 ° C and titrating 12% by weight of OH, l water (46.92 g, or 2.608 moles), as well as potassium siliconate catalyst (0.105 g). The reaction medium is heated at 95 ° C for 6 hours. At the end of this time, the reaction medium is left for 15 hours at room temperature (23 ° C.), then it is neutralized using 0.241 g of a mixture based on phosphoric acid and polydimethylsiloxane oligomers, operating at 90 ° C for 1 hour. The reaction medium obtained is then devolatilized by operating at 180 ° C and under a reduced pressure of 3J0 ² Pa, for 30 minutes. The amino POS was subjected to proton and silicon NMR analyzes. The results of these analyzes reveal a mixture of linear (85% molar) and cyclic (15% molar) structures having the following average formulas:

The amino POS thus obtained contains 0.5 mole of amino functions per 100 g of product.

2.- Preparation of the organosilicon compound comprising a POS / 1 polymer of the acid type by setting in process (d):

A solution of maleic anhydride (30.67 g, or 0.3128 mole) in CH ₂ CI is introduced into a 1 I glass reactor, fitted with a stirring system and a dropping funnel. ₂ as solvent (400 cm ³ ), then the temperature of the reaction medium is lowered to 8 ° C., and the amine POS (62.11 g) is then poured gradually over a period of 1 hour 15 minutes while maintaining the temperature reaction medium at 8 ° C during casting. At the end of addition, the reaction medium is left for 15 hours at room temperature ^(23C C). The solvent is then removed under reduced pressure, operating at a temperature which does not exceed 30 ° C.

An oil is thus obtained which has been subjected to analyzes by proton NMR and by silicon NMR ( ²⁹ Si). The results of these analyzes reveal that the reaction product or organosilicon compound obtained at the end of process (d) contains: • 91.3% by weight of the POS / 1 polymer of acid type of average formula:

and 8J% by weight of the cyclic monofunctional POS of average formula:

EXAMPLE 2

This example illustrates the preparation of an organosilicon compound according to the invention, comprising a POS / 2 polymer of ester type.

This compound is prepared by implementing method (f) [with activation method (2d)] which has been explained above in this memo.

1.- Alcohol from maleic anhydride: In a 2 liter tetracol reactor, maleic anhydride is introduced (698.1 g, or 7.12 moles), then it is melted by heating the reactor using '' an oil bath brought to 70 ° C. Once all of the anhydride has melted, methanol (221.4 g, or 6.92 moles) is introduced, with stirring, via a dropping funnel. The medium is then left under stirring for 20 hours at 23 ° C, then it is devolatilized by establishing a reduced pressure of 10.10 ² Pa for 1 hour, and finally it is filtered on filter paper. 786.9 g of monomethyl ester of maleic acid of formula (86% yield) are thus recovered:

2.- Preparation of the activated ester derivative according to the activation method (20:

Into a 2 liter glass reactor, equipped with mechanical stirring and a dropping funnel, are introduced: N-hydroxysuccinimide (39.20 g, or 0.3406 mole), tetrahydrofuran as solvent (200 cm ³ ) and the monomethyl ester of maleic acid (40.1 g, or 0.3085 mole). The reaction medium is stirred, and the dicyclohexylcarbodiimide (69.3 g, or 0.3363 mole) is poured in gradually, at room temperature (23 ° C.), over a period of 10 minutes. The medium becomes heterogeneous due to the precipitation of dicyclohexylurea. After a reaction period of 50 minutes, the reaction medium is filtered through

"bϋchner" and the filtrate is concentrated by evaporation at a temperature not exceeding

35 ° C. The residual reaction medium is left at a temperature of 4 ° C. for

15 hours, then it is again filtered through a sintered glass containing 10 cm of silica. The second filtrate obtained is completely devolatilized under reduced pressure to remove the remaining solvent and the solid finally obtained is then recrystallized from a mixture

CH ₂ CI ₂ / ethylenic ether; the mother liquors of this recrystallization are recovered, concentrated and a second recrystallization is carried out.

41 g (55% yield) of the activated ester derivative of formula:

3.- Preparation of the amino POS:

In a 4 liter glass reactor fitted with mechanical stirring and an ascending cooler, γ-aminopropylsilane of formula is introduced.

(C ₂ H ₅ O) ₂ CH ₃ Si (CH ₂ ) ₃ NH ₂ (1700.3 g, i.e. 8.9 moles). The pouring of water (1442.5 g, or 80.13 moles) is done using a pouring pump having a flow rate of 10 cm ³ / hour. The reaction is exothermic throughout the casting and the temperature is not controlled. After 3 hours of reaction, a water-ethanol mixture is removed under reduced pressure of 10.10 ¹ Pa, first at 40 ° C, then at 70 ° C to completely remove the ethanol and thus lead to an amino oil intermediate.

350.24 g of the intermediate amino oil obtained at the end of the preceding step, a polydimethylsiloxane oil α, ω, are introduced into another 1 liter reactor, also provided with mechanical stirring and with a condenser. -dihydroxylated (230.92 g) having a viscosity of 50 mPa.s at 25 ° C and titrating 12% by weight of OH, as well as catalyst based on potassium siliconate (0.0416 g). The reaction medium is heated at 90 ° C for 6 hours. At the end of this time, the reaction medium is left for 15 hours at room temperature (23 ° C), then it is neutralized using 0.0974 g of a mixture based on phosphoric acid and polydimethylsiloxane oligomers , operating at 90 ° C for 1 hour. The reaction medium obtained is filtered through a microporous filter of 0.5 μm.

The amino POS obtained was subjected to proton and silicon NMR analyzes. The results of these analyzes reveal a mixture of linear (74% molar) and cyclic (26% molar) structures having the following average formulas:

The POS thus obtained contains 0.51 amino function per 100 g of product.

4.- Preparation of the organosilicon compound comprising a POS / 2 polymer of the ester type by coupling the activated ester derivative with the amino POS: The activated ester derivative as prepared in point 2 above (39.83 g, ie 0.175 mole) is introduced into a tetracol reactor with 200 cm ³ of CH ₂ CI ₂ as solvent. The POS amine as prepared in point 3, above (30.82 g) is dissolved in 200 cm ³ of CH ₂ CI ₂ , then the solution is introduced into a dropping funnel. The casting is carried out gradually over a period of 1 hour, on a reaction medium which has been cooled beforehand to 5 ° C. by an ice-water bath.

When the casting is complete, the reaction medium is reacted at room temperature (23 ° C) for 15 hours. At the end of this time, the medium is transferred to a separating funnel, then it is washed 4 times in succession with water. The addition of a saturated aqueous NaCl solution is necessary to aid in the separation of the phases. The residual organic phase is recovered, dried over MgSO ₄ , then filtered through filter paper and finally the solvent is removed under reduced pressure and at room temperature (23 ° C).

An oil is thus obtained which has been subjected to analyzes by proton NMR and by silicon NMR ( ²⁹ Si). The results of these analyzes reveal that the reaction product or organosilicon compound obtained at the end of process (f) contains: • 94.8% by weight of POS / 2 polymer of ester type of average formula:

and 5.2% by weight of the cyclic monofunctional POS of average formula:

EXAMPLES 3 and 4

The purpose of these examples is to demonstrate the coupling performance (white filler-isoprene elastomer) of an organosilicon compound comprising a multifunctional POS which has been defined above, carrying on the one hand at least one hydroxyl radical and / or at least one alkoxyl radical and on the other hand at least one group containing an activated ethylenic double bond chosen from groups derived from maleic acid and groups derived from fumaric acid. These performances are compared with those of a conventional coupling agent based on a TESPT silane. We compare 4 isoprene elastomer compositions representative of shoe sole formulations. These 4 compositions are identical except for the following differences:

- composition No. 1 (control 1): absence of coupling agent;

- composition No. 2 (control 2): coupling agent based on TESPT silane (4 pce); - Composition No. 3 (Example 3): coupling agent or organosilicon compound, providing in the composition 4.66 phr of the POS / 1 polymer of the acid type, prepared in Example 1;

- Composition No. 4 (Example 4): coupling agent or organosilicon compound, providing in the composition 5.02 phr of the POS / 2 polymer of the ester type, prepared in Example 2.

1) Composition of isoprene elastomer compositions:

In an internal mixer of the BRABENDER type, the following compositions are prepared, the constitution of which, expressed in parts by weight, is indicated in Table I given below:

Board

(1) Natural rubber, of Malaysian origin, marketed by SAFIC-ALCAN under the reference SMR 5L;

(2) Polybutadiene rubber with a high rate of cis-1,4 adducts, sold by the company SHELL;

(3) Silica Zéosil 1165 MP, marketed by RHODIA - Silices;

(4) and (5) Vulcanization activators;

(6) Bis 3-triethoxysilylpropyl tetrasulfide, sold by the company DEGUSSA under the name Si-69;

(7) N-tertiobutyl-2-benzothiazyl-sulfenamide (vulcanization accelerator);

(8) Diphenyl guanidine (vulcanization accelerator);

(9) Vulcanizing agent.

2) Preparation of the compositions:

In an internal BRABENDER type mixer, the various constituents are introduced in the order, at the times and at the temperatures indicated below: Time Temperature Constituents

0 minute 80 ° C NR rubber

1 minute 90 ° C BR rubber

2 minutes 100 ° C 2/3 silica + coupling agent

4 minutes 120 ° C 1/3 silica + stearic acid + zinc oxide

5 minutes 140 to 150 ° C drain

The contents of the mixer are drained or dropped after 5 minutes. The temperature reached is around 145 ° C.

The mixture obtained is then introduced on a roller mixer, maintained at 30 ° C, and TBBS, DPG and sulfur are introduced. After homogenization, the final mixture is calendered in the form of sheets 2.5 to 3 mm thick.

3) Rheological properties of the compositions:

The measurements are carried out on the compositions in the raw state. The results relating to the rheology test, which is carried out at 160 ° C. for 30 minutes using a MONSANTO 100 S rheometer, are shown in Table II below.

According to this test, the composition to be tested is placed in the test chamber regulated at a temperature of 160 ° C., and the resistive torque, opposed by the composition, to a low amplitude oscillation of a biconical rotor included in the measurement is measured. test chamber, the composition completely filling the chamber in question. From the curve of variation of the torque as a function of time, the following is determined: the minimum torque which reflects the viscosity of the composition at the temperature considered; the maximum torque and the delta-torque which reflect the rate of crosslinking caused by the action of the vulcanization system; the time T-90 necessary to obtain a vulcanization state corresponding to 90% of the complete vulcanization (this time is taken as the optimum vulcanization); and the TS-2 roasting time corresponding to the time necessary to have a rise of 2 points above the minimum torque at the temperature considered (160 ° C) and which reflects the time during which it is possible to use raw mixtures at this temperature without having initiation of vulcanization. The results obtained are shown in Table II.

Table II

4) Mechanical properties of vulcanizates:

The measurements are carried out on the uniformly vulcanized compositions for 20 minutes at 160 ° C.

The properties measured and the results obtained are collated in the following Table III:

Table III

(1) The tensile tests are carried out in accordance with the indications of standard NF T 46-002 with H2 type test pieces. The modules 10%, 100%, 300%, and the breaking strength are expressed in MPa; the elongation at break is expressed in%.

(2) The measurement is carried out according to the indications in standard ASTM D 3240. The given value is measured at 15 seconds. (3) The measurement is carried out according to the indications in standard NF T 46-012 using method 2 with a rotating test tube holder. The measured value is the loss of substance (in mm ³ ) on abrasion; the lower it is, the better the abrasion resistance.

We note that, after baking, the compositions of Examples 3 and 4 have higher modulus values (M 300%), higher reinforcement and abrasion resistance indices than those obtained with the control mixture without coupling agent (witness 1). The improvement in these indicators is known to those skilled in the art as demonstrating a significant improvement in the coupling between white filler and elastomer due to an indisputable coupling effect of the coupling agents introduced into the compositions of Examples 3 and 4.

It should also be emphasized that the coupling agents used in Examples 3 and 4 lead to an interesting compromise of properties since they make it possible to obtain everything at the same time:

- viscosities close to those reached with TESPT (control 2),

- a reinforcement index substantially close to that obtained with the TESPT,

- an excellent level of abrasion resistance substantially close to that provided by the TESPT.

Claims

CLAIMS 1. New organosilicon compounds which comprise multifunctional POSs, characterized in that said multifunctional POSs contain similar or different motifs of formula:

< ^R '> -w ⁱ⁰ _4. , _A , _{b + e)} <"

2

in which :

(1) the symbols R ² , identical or different, each represent a monovalent hydrocarbon group chosen from an alkyl radical, linear or branched, having from 1 to 6 carbon atoms, a cycloalkyl radical having from 5 to 8 carbon atoms, and a phenyl radical;

(2) the symbols Y, which are identical or different, each represent a hydroxyl or alkoxyl function R ¹ 0 where R ¹ represents an alkyl radical, linear or branched, having from 1 to 15 carbon atoms; (3) the symbols X, identical or different, each represent a function carrying an activated ethylenic double bond, chosen from the radicals having the following formulas (H / 1), (II / 2), and their mixtures:

formulas in which: + the symbol V represents a divalent radical -O- or -NR ⁶ + the symbol W represents a monovalent group COOR ⁷ or a monovalent group

CONR ⁸ R ⁹ ; + R ³ is a divalent alkylene radical, linear or branched, comprising from 1 to 15 carbon atoms whose free valence is carried by a carbon atom and is linked to a silicon atom, said radical R ³ being able to be interrupted within of the alkylene chain by at least one heteroatom (such as oxygen and nitrogen) or at least one divalent group comprising at least one heteroatom (such as oxygen and nitrogen), and in particular by at least one divalent residue of general formula —rest- chosen from: -O-, -CO-, -CO-O-, -COO-cyclohexylene (optionally substituted by an OH radical) -, -O-alkylene (linear or branched C ₂ -C ₆ , optionally substituted by an OH or COOH radical) -, -O-CO-alkylene (linear or branched C ₂ -C ₆ , optionally substituted by an OH or COOH radical) -, -CO-NH-, -O- CO-NH-, and -NH-alkylene (linear or branched C ₂ -C ₆ ) -CO-NH-; R ^{3 also} represents a divalent aromatic radical of general formula —radical— chosen from: -phenylene (ortho, meta or para) -alkylene (linear or branched C ₂ -C ₆ ) -,

-phenylene (ortho, meta or para) -0-alkylene (linear or branched C ₂ -C ₆ ) -,

-alkylene (linear or branched C ₂ -C ₆ ) - phenylene (ortho, meta or para) -alkylene

(linear or branched in Cι-C ₆ -, and -alkylene (linear or branched in C ₂ -C ₆ ) -phenylene

(ortho, meta or para) -0-alkylene (linear or branched in CC ₆ ) -; preferably, the symbol R ³ represents an alkylene radical which corresponds to the following formulas: - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, -CH ₂ -CH (CH ₃ ) -, - (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ -, - (CH ₂ ) ₃ -O- (CH ₂ ) ₃ -, - (CH ₂ ) ₃ -0-CH ₂ -CH ( CH ₃ ) -CH ₂ -, - (CH ₂ ) ₃ -0-CH ₂ CH (OH) -CH ₂ -; more preferably, R ³ is a radical - (CH ₂ ) ₂ - or - (CH ₂ ) ₃ -; with the precision according to which, in the definitions of R ³ which precede, the divalent residues and radicals mentioned when they are not symmetrical, can be positioned with the valence v1 on the left and with the valence v2 on the right or vice versa with the valence v2 on the left and valence v1 on the right;

+ the symbols R ⁴ and R ⁵ , identical or different, each represent a hydrogen atom, a halogen atom, a cyano radical or an alkyl radical, linear or branched, having from 1 to 6 carbon atoms, R ⁵ can also represent a monovalent group COOR ⁷ ;

+ the symbols R ⁶ , R ⁷ , R ⁸ and R ⁹ , identical or different, each represent a hydrogen atom, an alkyl radical, linear or branched, having from 1 to 6 carbon atoms or a phenyl radical, the symbols R ⁸ and R ^{9 being} able, in addition, to form together and with the nitrogen atom to which they are linked, a single saturated ring having from 3 to 8 carbon atoms in the ring; (4) the symbols a, b and c each represent whole or fractional numbers chosen from:

+ a: 0, 1, 2 or 3; + b: 0, 1, 2 or 3; + c: 0 or 1;

+ the sum a + b + c being different from zero and <3;

(5) the content of units R ¹⁰ SiO _{_3/2} (motif "T") where R ¹⁰ is chosen from radicals corresponding to the definitions of R ^2, Y and X, the rate being expressed by the number, per molecule, these units for 100 silicon atoms, is equal to or less than 30%; (6) the rate of Y functions, expressed by the number, per molecule, of Y functions per 100 silicon atoms, is at least 0.8%; (7) the rate of X functions, expressed by the number, per molecule, of X functions per 100 silicon atoms, is at least 0.4%. 2. Compounds according to claim 1, characterized in that in formula (I): (1) the symbols R ² are chosen from the radicals: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, cyclohexyl and phenyl;

(2) the symbols Y are chosen from a hydroxyl radical and an alkoxyl radical, linear or branched, having from 1 to 6 carbon atoms;

(3) the functions represented by the symbol X are chosen from the functions of formulas (H / 1), (H / 2) and their mixtures in which:

+ the symbol V is a radical -O- or -NR ⁶ - where R ⁶ has the preferred definition indicated below; + the symbol W is a COOR ⁷ group or a CONR ⁸ R ^{9 group in} which the radicals R ⁷ , R ⁸ and R ⁹ have the preferred definitions indicated below; + the symbol R ³ represents an alkylene radical which corresponds to the following formulas: -

(CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, -CH ₂ -CH (CH ₃ ) -, - (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - , - (CH ₂ ) ₃ -O- (CH ₂ ) ₃ -,

- (CH ₂ ) 3-0-CH ₂ -CH (CH ₃ ) -CH ₂ -, - (CH ₂ ) ₃ -0-CH ₂ CH (OH) -CH ₂ -; + the symbols R ⁴ and R ⁵ are chosen from a hydrogen atom, a chlorine atom, and the methyl, ethyl, n-propyl, n-butyl radicals, R ⁵ can also represent a COOR ⁷ group where the radical R ⁷ has the preferred definition indicated below;

+ the symbols R ⁶ , R ⁷ , R ⁸ and R ⁹ are chosen from a hydrogen atom, and the methyl, ethyl, n-propyl, n-butyl radicals, the symbols R ⁸ and R ⁹ can, in addition, form together and with the nitrogen atom a pyrrolidinyl or piperidyl ring; (5) the rate of 'T' reasons is equal to or less than 20%; (6) the rate of Y functions is in the range from 1 to 100%; (7) the rate of X functions is in the range from 0.8 to 100%.

3. Compounds according to claim 1 or 2, characterized in that they comprise multifunctional POSs chosen from: • POSs which are essentially linear and have the mean formula

(III) next

in which: (1 ') the symbols T ¹ are chosen from the units H0 _{1 2} and R ¹ 0 ₂ , where the radical R ¹ is as defined above; (2 ') the symbols T ² , identical or different from the symbols T ¹ , are chosen from the units H0 _{1 / 2l} R ¹ 0 _1/2 and the unit (R ² ) ₃ Si0 _{1 2} , where the radicals R ¹ and R ² are as defined above in points (2) and (1) relating to formula (I); (3 ') the symbols R ² , X and Y are as defined above in points (1), (3) and (2) relating to formula (I); (4 ') the symbols R ¹⁰ are chosen from the radicals corresponding to the definitions of R ² , X and Y; (5 ') the symbols m, n, p, q, r, s and t each represent whole or fractional numbers which meet the following cumulative conditions:

• n is in the range from 0 to 100,

• p is in the range from 0 to 100,

• q is in the range from 0 to 100,

• r is in the range from 0 to 100, »s is in the range from 0 to 75,

"The sum n + p + q + r + s + t giving the total number of silicon atoms is in the range from 3 to 250, The ratio 100 s / (n + p + q + r + s + t) giving the rate of patterns "T" is <30,

• the ratio 100 (m + p + r + s [when R ¹⁰ = Y] + 1) / (n + p + q + r + s + 1) giving the rate of functions Y is> 1,

• the ratio 100 (n + p + s [when R ¹⁰ = X]) / (n + p + q + r + s + 1) giving the rate of functions X is>1; POSs which are cyclical and have the following average formula:

(IIP)

in which: (3 "") the symbols R ² , X and Y are as defined above in points (1), (3) and (2) concerning the formula (I); (5 "") the symbols n ', p', q 'and r' each represent whole or fractional numbers which meet the following cumulative conditions:

• n 'is in the range from 0 to 9, • p' is in the range from 0 to 9,

^» When n '= 0, p' is at least equal to 1,

• when p - 0, n 'is at least equal to 1 and r' is also at least equal to 1,

• q 'is in the range from 0 to 9,

• r 'is in the range from 0 to 2, ^" the sum n' + p '+ q' + r 'is in the range from 3 to 10,

- the ratio 100 (p '+ r') / (n '+ p' + q '+ r ") giving the rate of function Y goes from 4 to 100,

• the ratio 100 (n '+ p') / (n '+ p' + q '+ r') giving the rate of function X goes from 10 to 100; • and mixtures of POSs of formulas (III) and (III).

4. Compounds according to claim 3, characterized in that they comprise multifunctional POSs chosen from oligomers and essentially linear POS / 1 polymers which correspond to formula (III) in which: (1 ") the symbols T ¹ are defined as indicated above in point (1 '); (2 ") the symbols T ² , identical or different from the symbols T ¹ , are chosen from the pattern HO _{1 2} and the pattern R ¹ O _{1 2} as defined above -before at point (1 '); (3 ") • the functions X, identical or different, are chosen from the radicals of formulas (H / 1), (H / 2) and their mixtures, where:

- on the one hand the symbol V = -NR ⁶ -, R ⁵ is different from a group COOR ⁷ and the symbol W = COOR ⁷ where R ⁷ = H, and

- on the other hand, the symbols R ³ , R ⁴ , R ⁵ (different from a COOR ⁷ group) and R ⁶ are chosen as indicated above in point (3) concerning the formula (I),

• the symbols R ² and Y are as defined above in point (3 '); (4 ") the symbols R ¹⁰ are defined as indicated above in point (4 ');

(5 ") the symbols m, n, p, q, r, s and t meet the following cumulative conditions:

• m + t = 2 + s,

• n is in the range from 0 to 50, - p is in the range from 0 to 20, • when n = 0, p is at least 1 and when p = 0, n is at less than 1,

"Q is in the range from 0 to 48,

• r is in the range from 0 to 10,

• s is in the range from 0 to 1,

The ratio 100 s / (n + p + q + r + s) giving the rate of patterns "T" is <to 10,

The ratio 100 (m + p + r + s [when R ¹⁰ = Y] + 1) / (n + p + q + r + s) giving the rate of functions Y goes from 4 to 100,

• the ratio 100 (n + p + s [when R ¹⁰ = X]) / (n + p + q + r + s) giving the rate of functions X goes from 10 to 100.

5. Compounds according to claim 3, characterized in that they comprise multifunctional POSs chosen from oligomers and essentially linear POS / 2 polymers which correspond to formula (III) in which: (1 '") the symbols T ¹ are defined as indicated above in point (1 ¹ ); (2 "') the symbols T ² , identical or different from the symbols T ¹ , are chosen from the pattern HO _{1 2} and the pattern R ¹ 0 _{1 2} as defined above in point (1');(3"') • the functions X, identical or different, are chosen from the radicals of formulas (H / 1), (H / 2) and their mixtures, where: - on the one hand the symbol V = -NR ⁶ -, R ⁵ is different from a group COOR ⁷ and the symbol W = COOR ⁷ where R ⁷ different from H is a radical as defined above in point (3) concerning the formula (I), and - on the other hand the symbols R ³ , R ⁴ , R ⁵ (different from a COOR ⁷ group) and R ⁶ are chosen as indicated above in point (3) concerning formula (I),

• the symbols R ² and Y are as defined above in point (3 '); (4 '") the symbols R ¹⁰ are defined as indicated above point (4 ¹ ); (5"') the symbols m, n, p, q, r, s and t meet the following cumulative conditions: m + 1 = 2 + s, • n is in the range from 0 to 50, p is in the range from 0 to 20, when n = 0, p is at least 1 and when p = 0 , n is at least equal to 1, q is in the range from 0 to 48, r is in the range from 0 to 10, ^" s is in the range from 0 to 1, the sum n + p + q + r + s giving the total number of silicon atoms is in the range from more than 3 to 50, the ratio 100 s / (n + p + q + r + s) giving the rate of patterns 'T' is ≤ 10, the ratio 100 (m + p + r + s [when R ¹⁰ = Y] + 1) / (n + p + q + r + s) giving the rate of functions Y goes from 4 to 100,

- the ratio 100 (n + p + s [when R ¹⁰ = X]) / (n + p + q + r + s) giving the rate of functions X goes from 10 to 100.

6. Process for the preparation of organosilicon compounds according to any one of claims 1 to 5, characterized in that it involves in particular:

a condensation reaction between an organosilane carrying a function X and at least two functions Y, and a linear POS α, ω-dihydroxylated, a redistribution and equilibration reaction between an organosilane carrying a function X and at least two functions Y and or halo, and an organocyclosiloxane which may optionally carry one or more Y functions in the chain,

- a coupling reaction between a precursor POS, linear or cyclic, carrying at least one Y function and functionalized with at least one motif attached to a silicon atom, in particular of the -alkylene type (linear or branched C ₂ -C ₆ ) -OH, -alkylene (linear or branched C ₂ -C ₆ ) -NR ⁶ H or -alkylene (linear or branched C ₂ -C ₆ ) -COOH, and a reactive compound capable of reacting with (or ) motif (s) mentioned above to give rise to the desired function X, - an esterification reaction of a precursor POS, linear or cyclic, carrying at least one Y function and at least one X function of formula (11/1) and / or (H / 2) where the symbol W represents a COOH group.

7. Preparation process according to claim 6, making it possible to prepare organosilicon compounds according to claim 4 comprising POS / 1 polymers of acid type, characterized in that it consists in carrying out a coupling reaction between:

on the one hand, an essentially linear amino POS having the same formula (III) as that given above with regard to the definition of the POS / 1 polymers, but in which the symbol X is now an amino function of formula - R ³ -NR ⁶ H where the symbols R ³ and R ⁶ are as defined in point (3 ") of claim 4; said amino POS being represented by the simplified formula:

≡Si-R ³ -NR ⁶ H (X)

- and on the other hand maleic anhydride or one of its derivatives of formula:

in which the symbols R ⁴ and R ⁵ are as defined in point (3 ') of claim 4.

8. Preparation process according to claim 6, making it possible to prepare organosilicon compounds according to claim 5 comprising the POS / 2 polymers of ester type, characterized in that said compounds are prepared by esterification of a

POS intermediate maleamic acid by performing the following steps: (e1) coupling reaction between the amino POS (X) and maleic anhydride (XI), then (e2) reaction of esterification of the medium comprising POS / 1 of the acid type formed, to yield the compound comprising POS / 2 of the desired ester type, by applying the following synthetic scheme:

RC = CR ⁵

≡Si-R-NR— CC ^ ^' COOH

POS / 1 acid type

esterification

Ester type POS / 2

where the symbols R ³ to R ⁷ have the meanings given above in point (3 '") of claim 5.

9. The preparation method according to claim 6, making it possible to prepare organosilicon compounds according to claim 5 comprising POS / 2 polymers of ester type, characterized in that said compounds are prepared by formation of an amide function by adding the amine POS (X) on an ester derivative (XIV) obtained from a mono-ester of maleic acid (XIII), by carrying out the steps the following steps: (f1) alcoholysis of maleic anhydride (XI) by l alcohol R ⁷ -OH, (f2) activation of the carboxylic acid function of the maleic acid monoester (XIII) obtained, using the various activation methods described in the field of peptide synthesis, to lead to the activated ester derivative (XIV), then (f3) addition of the amino POS (X) to said activated ester derivative (XIV) to yield the compound comprising POS / 2 of the desired ester type, by applying the following synthetic scheme: Amino POS (X)

where the symbol Ac of the derivative (XIV) represents an activating function and where the symbols R ³ to R ⁷ have the meanings given above in point (3 '") of claim 5.

10. Method according to claim 9, characterized in that the activation of the carboxylic acid function of the mono-ester of maleic acid (XIII) is carried out by implementing the following methods:

T-COOH CI-CO-OR, -. T-CQ_O_ _CO _Q _{R /} + _{HC |} activating function Ac

where T represents the residue -R ⁴ C = CR ⁵ -COOR ⁷ and R represents a linear alkyl radical having for example 1 to 3 carbon atoms; (2d) activation by reaction with dicyclohexylcarbodiimide (DCCI) in the presence of N-hydroxysuccinimide (HO-SN), according to the scheme:

activating function Ac

(3d) activation by reaction with a chlorinated compound according to the scheme

chlorinated compound T-COOH - T-CO-CI + POCI ₃ + HCI

ac