FR2547304A1 - Process for the preparation of block copolymers containing hydroxyl functional groups along their chain - Google Patents

Abstract

This process consists in reacting a polysiloxane containing at least two epoxy functional groups with a polyphenol in the presence of a basic catalyst. The polyphenol may be bisphenol A, an alpha , omega -diphenol polysulphone or an alpha , omega -diphenol polycarbonate and the polysiloxane may be an alpha , omega -1-dipropyloxy-2,3-epoxypropane polydimethylsiloxane.

Description

 The present invention relates to a process for the preparation of block polymers comprising hydroxyl functions along their chain. More specifically, it relates to the preparation of such copolymers from polyphenols and polysiloxanes comprising at least two epoxy functions.

 These block copolymers which can optionally be grafted and / or crosslinked, can be used for the production of hydrophobic and ther ruostable adhesives, reinforced plastics or parts having to resist high temperature.

 The process according to the invention for the preparation of these copolymers is characterized in that it consists in reacting a polyphenol with a polysiloxane comprising at least two epoxy functions, in the presence of a basic catalyst.

 The basic catalysts which can be used are tertiary amines such as dimethyldodecylamine or triethanolamine, alkali metal hydroxides or quaternary ammonium salts.

During the copolymerization reaction which is a polycondensation reaction, the phenol function of the polyphenol is reacted with the epoxide function of the polysiloxane, according to the following reaction scheme

 Preferably, the reaction is carried out in the absence of solvent, at a temperature sufficient to obtain the melting of the polyphenol, and the operation is carried out at a temperature above 800C, generally at a temperature of 140 to 1500C.

 However, this reaction can be carried out in the presence of an inert solvent such as ethylene glycol dimethyl ether (monoglyme) or di ethylene glycol dimethyl ether (diglyme). In general, the reaction is chosen in the presence of a minimum of solvent.

dans laquelle R1 et R2 qui peuvent être identiques ou différents, représentent un radical alkyle en C1 à C4, un radical alkoxy en C1 à C4, un radical aryle ou un radical aryîoxy, X représente un radical comportant une fonction époxyde en bout de channe et éventuellement une fonction éther-oxyde dans la channe , x est égal à zéro ou est un nombre positif et et W représente un motif monomère de formule ::

dans laquelle R3 et R4 qui peuvent être identiques ou différents, représentent un radical alkyle en C1 à C4, un radical alkoxy en Cl à C4, un radical aryle, un radical aryloxy ou un radical comportant une fonction époxyde en bout de chaîne et éventuellement une fonction éther-oxyde dans la chaîne, et, dans les x motifs W, R3 et R4 pouvant etre différents d'un motif à l'autre
A titre de radicaux comportant une fonction époxyde en bout de chaîne susceptibles d'être utilisés, on peut citer des radicaux de formule

dans laquelle i est égal à 0 ou est un nombre entier allant de 1 à 6 et j est un nombre entier allant de 1 à 6, par exemple le radical

The polysiloxanes comprising at least two epoxy functions, used as starting material in the process of the invention, correspond to the following general formula

in which R1 and R2 which may be identical or different, represent a C1 to C4 alkyl radical, a C1 to C4 alkoxy radical, an aryl radical or an aryoxy radical, X represents a radical comprising an epoxy function at the end of the chain and optionally an ether-oxide function in the chain, x is equal to zero or is a positive number and and W represents a monomer unit of formula:

in which R3 and R4 which may be identical or different, represent a C1 to C4 alkyl radical, a C1 to C4 alkoxy radical, an aryl radical, an aryloxy radical or a radical comprising an epoxide function at the chain end and optionally a ether-oxide function in the chain, and, in the x units W, R3 and R4 which may be different from one unit to another
As radicals comprising an epoxy function at the end of the chain which can be used, there may be mentioned radicals of formula

in which i is equal to 0 or is an integer ranging from 1 to 6 and j is an integer ranging from 1 to 6, for example the radical

The poiysiioxanes corresponding to the formula (I) given above can be prepared by conventional methods, in particular by reacting an epoxidized derivative comprising an allylic function with a polysiloxane according to the following reaction scheme

dans laquelle R1, R2 et x ont la signification donnée ci-dessus, et W' représente un motif monomère de formule

dans laquelle R5 et R6 qui peuvent être identiques ou différents, représentent l'hydrogène, un radical allyle en C1 à C4, un radical alkoxy en C1 à C4, un radical aryle ou un radical aryloxy, et dans les x motifs W', R5 et R6 pouvant être différents d'un motif à l'autre.This reaction can be carried out in particular by reacting the allyloxy-l epoxy-2, 3 propane on a polysiloxane corresponding to the following formula

in which R1, R2 and x have the meaning given above, and W 'represents a monomer unit of formula

in which R5 and R6 which may be identical or different, represent hydrogen, a C1 to C4 allyl radical, a C1 to C4 alkoxy radical, an aryl radical or an aryloxy radical, and in the x units W ', R5 and R6 can be different from one motif to another.

 This reaction can be carried out according to known methods, for example at temperatures from 50 to 150 ° C. in the presence of a catalyst such as hexachloroplatinic acid H2PtCl6, 6H20.

 By way of example of polysiloxanes corresponding to formula (I) capable of being used in the process of the invention, mention may be made of tetramethyldisiloxane alpha, omega dipropyloxy-2,3-epoxy propane and polydimethyl siloxanes, n dipropyloxy-2,3-epoxy propane designated below under the term of alpha polysiloxanes, omega diepoxy.

dans laquelle R représente un atome d'hydrogène, un atome d'halogène, un radical nitré; un radical alkyle en C1 à C5 ou un radical alcoxy en Cl à C5 et in est un nombre entier de 2 à 6.According to a first embodiment of the process of the invention, the polyphenol used as starting material corresponds to the formula:

wherein R represents a hydrogen atom, a halogen atom, a nitro radical; a C1 to C5 alkyl radical or a C1 to C5 alkoxy radical and in is an integer from 2 to 6.

dans laquelle R représente un atome d'hydrogène, un atome d'halogène, un radical nitré, un radical alkyle en-C1 à C5 ou un radical alcoxy en Cl à C5, Y1 représente :

According to a second embodiment of the process of the invention, the polyphenol used as starting material corresponds to the formula:

in which R represents a hydrogen atom, a halogen atom, a nitrated radical, a C1-C5 alkyl radical or a C1-C5 alkoxy radical, Y1 represents:

où A1 et A2 qui peuvent être identiques ou différents, représentent un atome d'hydrogène, un atome d'halogène, un radical alkyle en Cl à C4, un radical alcoxy en Cl à Cd, un radical cycloalkyle en C3 à C6 ou le groupe

et n est un nombre entier de 1 à 5.S or the group

where A1 and A2 which may be the same or different, represent a hydrogen atom, a halogen atom, a C1-C4 alkyl radical, a C1-Cd alkoxy radical, a C3-C6 cycloalkyl radical or the group

and n is an integer from 1 to 5.

As an example of a polyphenol corresponding to this formula (III), mention may be made of bisphenol A.

dans laquelle Al et A2, qui peuvent être identiques ou différents, représentent comme précédemment un éa atome d'hydrogène, un atome d'halogène, un radical alkyle en
C1 à C4, un radical alcoxy en C1 à C4, un radical cycloalkyle en C3 à C6 ou le groupement

According to a third embodiment of the process of the invention, the polyphenol used as starting material corresponds to the formula:

in which Al and A2, which may be the same or different, represent, as before, a hydrogen atom, a halogen atom, an alkyl radical in
C1 to C4, a C1 to C4 alkoxy radical, a C3 to C6 cycloalkyl radical or the group

avec M représentant -CO ou :

R represents a hydrogen atom, a halogen atom, a nitrated radical, a C1 to C5 alkyl radical or a C1 to alkoxy radical
Z represents a single bond or the group

with M representing -CO or:

avec A1 et A2 ayant la signification donnée ci-dessus, et p est égal à zéro ou est un nombre positif.Y2 represents a single bond or the radical

with A1 and A2 having the meaning given above, and p is zero or is a positive number.

dans laquelle p est un nombre positif ou un polycarbonate alpha oméga diphénol de formule

dans laquelle r est un nombre positif.Preferably, the polyphenol is bisphenol
A or a bisphenol A derivative such as a polysulfone α# diphenol of formula

where p is a positive number or an alpha omega diphenol polycarbonate of the formula

where r is a positive number.

 The polysulfones of formula (V) can be obtained by reaction of bisphenol A with ge dichlorodi phenylsulfone by conventional methods. Similarly, the polycarbonates of formula (VI) can be obtained by reaction of bisphenol A with COCl2 by conventional methods.

dans laquelle p est un nombre positif.According to a fourth mode of implementation of the proned of the invention, the polyphenol used as starting material is a phenol-formaldehyde resin of formula:

where p is a positive number.

 Advantageously, the polyphenol is chosen from the group comprising bisphenol A, 1,1-bis (4 hydroxyphenylcyclohexane) (bisphenol C), bisphenol S, 4,4 '-dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfone , resorcinol, hydroquinone, catechol and phloroglucinol.

 Other characteristics of the invention will appear better on reading the following examples given, of course, by way of illustration and not limitation.

EXAMPLE 1
This example relates to the preparation of a polymer corresponding to the following formula

 228 g (1 mol) of bisphenol A are melted in a reactor equipped with a stirring system, a system allowing nitrogen to be swept, a condenser and an introduction bulb. 5.3 g (0.025 mol) of a tertiary amine constituted by N, N-dimethyldodecylamine are then introduced and 362 g (1 mol) of tetramethyldisiloxane ars-diepoxy are gradually poured in, the temperature is maintained at a value close to 1500C. The viscosity of the reaction medium increases rapidly and a copolymer having the appearance of a translucent gum is obtained after 24 hours. Analysis by gel permeation chromatography reveals a number-average molar mass greater than 10,000. Analyzes by nuclear magnetic resonance of the proton and of carbon 13 confirm the structure expected and described above. The solubilization of this polymer is very rapid in many organic solvents.

EXAMPLE 2
This example concerns the preparation of a polymer corresponding to the formula

228 g of bisphenol A (1 mol) are melted in a reactor, equipped with a stirring system, a system allowing a sweeping of inert gas, a condenser and an introduction bulb. 5.3 g (0.025 mol) of a tertiary amine constituted by N, Ndimethyldodecyl amine are introduced and gradually added 1300 g (1 mol) of a polysiloxanena,> J-diepoxy of formula

 The temperature is maintained at a value greater than 100 ° C., generally close to 1500 ° C. The viscosity of the reaction medium increases rapidly and a polymer having the appearance of a translucent and slightly yellowish gum is obtained after 24 hours. The analysis by gel permeation chromatography reveals a number average molar mass greater than 12,000. Analyzes by nuclear magnetic resonance of the proton and of carbon 13 confirm the structure described above.

The solubilization of this polymer is very rapid in many organic solvents. The thermal properties of the polymer are superior to those of the starting oligomers.

EXAMPLE 3
This example concerns the preparation of a polymer corresponding to the formula

 670 g (1 mol) of polysulfone α,# are placed in a reactor equipped with a stirring system, a system allowing an inert gas to be swept, a condenser and an introduction bulb. -diphenol of formula (V) with p = l. This oligomer is dissolved in approximately 500 ml of an inert solvent constituted by the diglyme. 5.3 g (0.025 mol) of a tertiary amine constituted by N, N-dimethyldodecylamine are introduced, then 362 g (1 mol) of tetramethyldisiloxane α,# - diepoxy are gradually poured in. As in the previous examples, the temperature is maintained above 100 C. The temperature of the reaction medium is increased during the reaction, but always remains below 2500C at the end of the reaction. After drying under high vacuum (13.5 Pa, 150 ° C., 24 hours), the polymer has the appearance of an opaque gum of orange color.

 Analysis by gel permeation chromatography reveals a number average molar mass greater than 15,000. Analyzes by nuclear magnetic resonance of the proton and of carbon 13 confirm the structure expected and described above. The solubilization of this polymer is rapid. in many organic solvents The thermal properties of this polymer are superior to those of the starting oligomers.

EXAMPLE 4
This example concerns the preparation of a polymer corresponding to the formula

 670 g (1 mol) of the polysulfone α,# - are placed in a reactor equipped with a stirring system, a system allowing a sweeping of inert gas, a condenser and an introduction bulb. diphenol of Example 3. This oligomer is dissolved in 500 ml of an inert solvent consisting of monoglyme. 5.3 g (0.025 mol) of a tertiary amine constituted by N, N-dimethyldcdecylamine are introduced and 1400 g (1 mol) of polysiloxane α,# - diepoxy are gradually poured in. The temperature is maintained above 80 C. The temperature of the reaction medium is increased during the reaction, but remains constantly below 250 C at the end of the reaction. The appearance of the polymer obtained is that of an opaque reddish-brown gum, after drying (13.5 Pa, 150 ° C., 24 hours). Analysis by gel permeation chromatography (GPC) reveals a number-average molar mass greater than 15,000. Heap analyzes by nuclear magnetic resonant of the proton and of carbon 13 confirm the expected structure and described in the above formula The solubilization of the polymer is rapid in many organic solvents. your thermal properties of the polymer are superior to those of the starting oligomers.

EXAMPLE 5
This example relates to the preparation of the same polymer as that of Example 4 but the inert solvent consists of dimethyl ether, diethylene glycol or diglyme. The procedure remains the same except for the temperature which is kept above 100: C. The appearance of the final polymer is, after thorough drying (13.5 Pa, 150 ° C., 24 hours) that of a brittle gum of dark brown color. The proton and carbon 13 nuclear magnetic resonance spectra confirm the expected structure and the GPC chromatograms reveal a mass greater than 20,000. The degree of polymerization is therefore higher than that of Example 4. On the other hand, the thermal properties are similar to those of Example 4.

EXAMPLE 6
This example concerns the preparation of a polymer corresponding to the formula

 1110 g (l mol) of polysulfone a are placed in a reactor equipped with a stirring system, a system allowing an inert gas to be swept, a condenser and an introduction bulb. , u'-diphenoî of formula (V) with p = 2. This oligomer is dissolved in 1 liter of an inert solvent consisting of monoglyme.

The temperature rose to 800C. 5.3 g (O, Q25 mol) of a tertiary amine constituted by N, N-dimethyldodecylamine are then introduced and 1700 g (1 mol) of a polysiloxane α# diepoxy are gradually poured in. The temperature is maintained above 80 C. The appearance of the polymer is that of a fairly brittle brown paste after thorough drying (13.5 Pa, 1500C, 24 hours). analysis by gel permeation chromatography shows a number average molar mass greater than 20,000. The nuclear magnetic resonance spectra of the proton and carbon 13 confirm the expected structure. Solubilization of the polymer is rapid in many organic solvents. The thermal properties of the polymer are superior to those of oligomers and comparable to those of the polymers obtained in the two previous examples.

Dans un réacteur équipé d d'un système d'agita- tion, d'un système permettant un balayage de gaz inerte, d'un condenseur et d'une ampoule d'introduction, on place 1550 g (1 mol) de la polysulfone α,#-diphénol de formule (V) avec p=3. On dissout celle-ci dans un solvant inerte constitué par du diméthyléthar de diéthylène glycol ou diglyrua. La température est portée à 800C et on introduit alors 5,3 g (0S025 mol) d'une amine tertiaire constituée par la diméthyldodécylamine.On ajoute ensuite goutte à goutte 1700 g (l mol) d'un polysiloxane α,#-diépoxy. La température est maintenue supérieure à 80 C pendant toute la réaction. L'aspect du polymère obtenu après séchage poussé (13,5 Pa, 1500C, 24 heures) est celui d'une pâte opaque. L'analyse par chromatographie par perméation de gel donne une masse molaire moyenne en nombre supérieure à 20 000 Les spectres de résonance magnétique nucléaire du proton et du carbone 13 confirment la structure attendue. La solubilisation du polymère est rapide dans de nombreux solvants organiques courants.Les propriétés thermiques sont supérieures à celles des oligomêres de départ
EXEMPLE 8
Cet exemple concerne la préparation d'un polymère répondant à la formule

EXAMPLE 7
This example concerns the preparation of a polymer corresponding to the formula

1550 g (1 mol) of the polysulfone are placed in a reactor equipped with a stirring system, a system allowing an inert gas to be swept, a condenser and an introduction bulb. α,# - diphenol of formula (V) with p = 3. It is dissolved in an inert solvent consisting of dimethylethar of diethylene glycol or diglyrua. The temperature is brought to 800C and 5.3 g (0SO25 mol) of a tertiary amine constituted by dimethyldodecylamine are then introduced. 1700 g (l mol) of a polysiloxane α,# - diepoxy are then added dropwise . The temperature is maintained above 80 ° C. throughout the reaction. The appearance of the polymer obtained after thorough drying (13.5 Pa, 1500C, 24 hours) is that of an opaque paste. Analysis by gel permeation chromatography gives a number average molar mass greater than 20,000. The nuclear magnetic resonance spectra of the proton and of carbon 13 confirm the expected structure. The polymer dissolves quickly in many common organic solvents. The thermal properties are superior to those of the starting oligomers.
EXAMPLE 8
This example concerns the preparation of a polymer corresponding to the formula

 3,100 g (2 mol) of a polymer are placed in a reactor equipped with an agitation system, a system allowing an inert gas to be swept, a condenser and an introduction bulb. consisting of a polysulfone α w-diphenol of formula (V) with p = 3. This oligomer is dissolved in approximately 2500 ml of an inert solvent constituted by the dimethyl ether of diethylene glycol (diglyme). The temperature is brought to 800C. 5.3 g (0.025 mol) of a tertiary amine consisting of N, N-dimethyldodecylamine are introduced. 362 g (l mol) of tetramethyldisiloxane a, w-diepoxy are then gradually added. The temperature is maintained above 80 ° C. throughout the reaction. The appearance of the polymer after thorough drying obtained is that of an opaque paste.

Analysis by gel permeation chromatography reveals a number average molar mass of approximately 3500, which is in accordance with the expected mass. The proton and carbon 13 nuclear magnetic resonance spectra confirm the expected structure. The solubilization of this polymer is rapid in many organic solvents.

EXAMPLE 9
This example concerns the preparation of a polymer of formula

In a reactor equipped with a stirring system of a system allowing a sweeping of inert gas, of a condenser and of an introductory funnel, 750 grams gl mol) of a polymer are placed. by a polycarbonate α,# - diphenol of formula

 The polycarbonate is brought to its melting temperature (around 1400C) and then 5.3 g (0.025 mol) of a catalyst consisting of dimethyldecylamine is introduced. During the whole reaction, the temperature is maintained higher than the melting temperature of the polycarbonate. 1300 g (1 mol) of a polydiméghylsiloxane α,# - diepoxy are then introduced dropwise. The appearance of the polymer obtained is that of a light brown paste. the gel permeation chromatography of this copolymer shows a number-average molar mass greater than 12,000. As for the preceding copolymers, the nuclear magnetic resonance spectra of the proton and of carbon 13 confirm the structure expected. The solubilization of the copolymer is rapid in many organic solvents. The thermal properties of the copolymer are superior to those of the starting materials.

EXAMPLE 10
This example concerns the preparation of a polymer corresponding to the formula

 930 g (0.2 mol) of polysulfone a, -dipheno1 are placed in a reactor equipped with a stirring system, a system allowing a sweeping of inert gas, a condenser and an introduction bulb. of formula (V) with p = 10. The polysulfone is dissolved in an inert solvent consisting of diethylene glycol dimethyl ether. The temperature rose to 100 ° C. and Don introduced 1.06 g (0.005 mol) of a tertiary amine constituted by dimethyldodecylamine. During the whole reaction, the temperature is maintained above 100 C. 485 g (Q, 1 mol) of a polysiloxane a, un-diepoxyO are added dropwise. The triblock copolymer, after thorough drying (13.5 Pa, 1500C, 24 hours), has the appearance of an opaque brown paste. Gel permeation chromatography gives a number average molar mass close to 15,000. The nuclear magnetic resonance spectra of the proton and carbon 13 confirm the expected structure. The solubilization of the final copolymer is rapid in many organic solvents.

Claims (15)

 1. Process for the preparation of block copolymers comprising hydroxyl functions along their chain, characterized in that it consists in reacting a polysiloxane comprising at least two epoxy functions with a polyphenol in the presence of a basic catalyst.  2. Method according to claim 1, characterized in that the polysiloxane comprising at least two epoxy functions corresponds to the formula

 in which R1 and R2, which may be identical or different, represent a C1 to C4 alkyl radical, a C1 to C4 alkoxy radical, an aryl radical or an aryloxy radical, X represents a radical comprising an epoxy function at the end of the chain and optionally an ether-oxide function in the chain; x is zero or is a positive number; and W represents a monomer unit of formula

 in which R3 and R4, which may be identical or different, represent a C1 to C4 alkyl radical, a C1 to C4 alkoxy radical, an aryl radical, an aryloxy radical or a radical comprising an epoxy function at the end of the chain and optionally a function ether-oxide in the chain, and, in the x units W, R3 and R4 which may be different from one unit to another.  3. Method according to claim 2, characterized in that X represents the radical

 4. Method according to claim 2, characterized in that the polysiloxane comprising at least two epoxy functions is tetramethyldisiloxane a, w -dipropyloxy-l epoxy-2,3 propane of formula:

 5. Method according to claim 2, characterized in that the polysiloxane comprising at least two epoxy functions corresponds to the formula

 6. Method according to any one of claims 1 to 5, characterized in that the low catalyst i- that is constituted by a tertiary amine or by an alkali metal hydroxide.  7. Method according to claim 6, characterized in that the tertiary amine is N, -dimethyl- dodecylamine or triethanolamine.  8. Method according to any one of the resells i- cations 1 to 7, characterized in that the polyphenol corresponds to the formula

 in which R represents a hydrogen atom, a halogen atom, a nitro radical, a C1 to C5 alkyl radical or a C1 to C5 alkoxy radical and m is an integer from 2 to 6.  9. Method according to any one of claims l to 7, characterized in that the polyphenol corresponds to the formula

 in which R represents a hydrogen atom, a halogen atom, a nitro radical, a C1 to C5 alkyl radical or a C1 to C5 alkoxy radical, Y1 represents C, CO, OCOO, SO2,

 and n is an integer from 1 to 5.

C4, a C3 to C6 cycloalkyl radical or the group  where A1 and A2 which may be identical or different, represent a hydrogen atom, a halogen atom, a C1 to C4 alkyl radical, a C1 to C alkoxy radical

S or the group  10. Method according to any one of claims l to 7, characterized in that the polyphenol corresponds to the formula:

 in which A1 and A2, which may be identical or different, represent a hydrogen atom, a halogen atom, a C1 to C4 alkyl radical, a C1 to C4 alkoxy radical, a C3 to C6 cycloalkyl radical or the group

  with M representing -CO or

Z represents a single bond or the group: R represents a hydrogen atom, a halogen atom, a nitro radical, a C1 to C5 alkyl radical or a C1 to C5 alkoxy radical;  with A1 and A2 having the meaning given above, and p is zero or is a positive number.

Y2 represents a single bond or the radical  11. Method according to any one of claims 1 to 7, characterized in that the polyphenol corresponds to the formula

 where p is a positive number.  12. Method according to any one of claims 1 to 7, characterized in that the polyphenol is chosen from the group comprising bisphenol A, 1,1bis (4-hydroxyphenylcyclohexane) or bisphenol C, bisphenol S, la 4, 41-dihydroxybenzophenone, 4,4'-di hydroxydiphenylsulfone, resorcinol, 1 hydroquinone, catechol and phloroglucinol.  13. Method according to any one of claims 1 to 7, characterized in that the polyphenol corresponds to the formula

 where p is a positive number.  14. Method according to any one of claims 1 to 7, characterized in that the polyphenol corresponds to the formula

 in which is a positive number.  15. Method according to any one of claims 1 to 14, characterized in that the reaction is carried out in the presence of an inert solvent consisting of dimethyl ether of ethylene glycol or dimethyl ether of diethylene glycol.