FR2905952A1 - New functionalized poly(phenylene-ether) comprising macromolecular chains containing phenolic terminals, useful e.g. in dyes, pigments, reinforcing fillers, refilling fillers and stabilizing additives for protection against light - Google Patents

Abstract

Functionalized poly(phenylene-ether) (I) comprising macromolecular chains containing phenolic terminals, is new. Functionalized poly(phenylene-ether) (I) comprising macromolecular chains containing phenolic terminals of formula (II), is new. R11-6C linear hydrocarbon, preferably methylene, ethylene or propylene; and R2, R2aaryl (optionally substituted) or 1-6C alkyl (optionally containing heteroatoms), preferably methyl or ethyl. Independent claims are included for: (1) the preparation of (I); and (2) a poly(phenylene-ether)-polyester copolymer comprising blocks containing recurring polymeric units of formula -(OC-R3-CO-O-R4-O)- and (III) and/or (IV). R3alkyl or aromatic group, preferably 1,4-phenyl-diyl; R42-6C alkylene radical, preferably -CH2-CH2-; and n : 10-300. [Image] [Image] [Image].

Description

2905952 1 Poly (phenylene ether) functionalized, poly copolymer

  (phenylene ether) - (polyester), compositions containing these copolymers and methods of preparation. The present invention relates to functionalized poly (phenylene ether), poly (phenylene ether) / polyester copolymers, compositions based on these copolymers and processes for the manufacture of these products. Poly (phenylene ether) are thermoplastic polymers characterized by excellent hydrolytic stability, dimensional stability and dielectric properties. They are also resistant to high temperatures. However, they have a mechanical fragility. Certain types of poly (phenylene ether) are synthesized from 2,6-dimethyl phenol by oxidative coupling to form a linear polymer having a non-reactive end and a reactive end comprising a phenol function. Other types of poly (phenylene ether) may have two reactive ends including a phenol function. Because of its mechanical fragility, poly (phenylene ether) is often used in admixture with other polymers. Its low resistance to polar solvents also requires mixing with polymers having a high crystallinity and a high resistance to solvents. As high crystallinity polymers, polyesters and in particular poly (ethylene terephthalate), generally referred to as PET, may be advantageously chosen. However, blends of PET and poly (phenylene ether) are generally characterized by phase separation and delamination phenomena can occur. Indeed, these mixtures contain large particles of poly (phenylene ether) (of size equal to about 2 to 3 microns) poorly dispersed in the polyester and exhibiting no interaction or binding with the polyester matrix. To improve the bonding between the two polymers, means of compatibilizing these polymers have been proposed. Thus, the compatibilization of the two phases can be carried out in different ways, for example, the synthesis of block copolymers comprising poly (phenylene ether) blocks and polyester blocks, making it possible to improve the interface between the phases and to reduce the size of the particles or nodules of the dispersed phase. The synthesis of the block copolymers requires the addition or formation of a polyester-poly (phenylene ether) binder which promotes the reaction between the polyester and the poly (phenylene ether 2905952) and the ensure a connection between the blocks. This binding agent can be obtained, for example, by functionalizing a terminus or chain end of the polyester or a terminus or chain end of the poly (phenylene ether).

  In WO 87/07279, numerous functionalizations of the chain ends of poly (phenylene ether) are described. These modifications are intended to increase the reactivity of the poly (phenylene ether) with the polyester. Compatibilization between the poly (phenylene ether) and the polyester is all the better as the level of block copolymer above is large. The reactivity of the polyphenylene ether with the polyester should be as great as possible to more easily form copolymers between the polyphenylene ether and the polyester. A reduction in the particle size of the dispersed phase is then obtained as the reaction rate between the poly (phenylene ether) and the polyester increases.

  However, it is necessary that this bond between the polyester and the poly (phenylene ether) is stable, that is to say that the bond between the poly (phenylene ether) blocks and the polyester blocks and that the functionalization of the poly ( phenylene ether) used to form the bonding agent is not destroyed and resists the different aggressions when using the material or the composition. By way of example, the binding of a linking agent on the phenol function by an ester function will be sensitive to hydrolysis. One of the aims of the present invention is to overcome these disadvantages by providing a poly (phenylene ether) functionalised, capable of reacting with the functions of the polyester and resistant to different attacks during its use. For this purpose, the invention provides a functionalized poly (phenylene ether) characterized in that it comprises macromolecular chains comprising at least one end of structure corresponding to the following general formula I: ## STR2 ## wherein: , represents a linear or branched hydrocarbon chain comprising from 1 to 6 carbon atoms. R2 and R'2 represent a substituted or unsubstituted aryl radical or a linear or branched alkyl radical comprising from 1 to 6 carbon atoms, the said radicals possibly comprising heteroatoms. According to one characteristic of the invention, the radical R, advantageously represents the methylene, ethylene or propylene radical. According to another characteristic of the invention, the radicals R 2 and R '2 which are identical or different represent, advantageously, a methyl or ethyl radical. In a preferred embodiment of the invention, all of the reactive terminal functions of the poly (phenylene ether) are functionalized and have a structure corresponding to the general formula (I) as defined above.

According to the invention, the preferred poly (phenylene ether) of the invention are those having a number-average molecular weight Mn of between 1000 and 30000 g / mol and a molecular weight of Mw of between 1000 and 90000 g / mol. They have a glass transition temperature of between 120 ° C. and about 220 ° C. The poly (phenylene ether) suitable for the invention are especially those described in pages 3 to 5 of patent WO87 / 07279, and more particularly the polymers described. page 6 of this same document and comprising phenolic terminal functions. The processes for preparing these poly (phenylene ether) are also described in WO87 / 07279 (page 5).

According to another object of the invention, the functionalized polyphenylenes of the invention are obtained by reaction of an alkylene carbonate or alkylene oxide with a polyphenylene ether comprising macromolecular chain ends comprising a phenol function to obtain macromolecular chain ends having a structure according to the general formula I, namely a hydroxyalkyl ether structure. Advantageously, the alkylene carbonates or alkylene oxides are chosen from the group comprising ethylene carbonate, propylene carbonate and ethylene oxide.

This reaction is preferably carried out in the presence of a catalyst and a solvent.

Suitable catalysts for the reaction include alkali or alkaline earth metal hydroxides, carbonates, hydrogenocarbonates, for example, potassium carbonate.

This reaction is conveniently carried out at a temperature of from about 50 ° C to about 300 ° C and in the presence of a polar solvent. Preferably, the poly (phenylene ether), the alkylene carbonate or the alkylene oxide are dissolved in a polar solvent such as, for example, 1,3-dimethyl-2-imidazolidinone, n-10 methylpyrrolidinone, dimethylsulfoxide, dimethylformamide or the like. The solution is then heated under an inert atmosphere at a temperature of between 50 ° C. and 300 ° C., advantageously between 75 ° C. and 200 ° C. The alkylene carbonate or alkylene oxide is advantageously used in excess with respect to the quantity stoichiometric calculated from the number of phenol terminal functions. Other details and characteristics of the manufacturing process will appear more clearly from the examples described below.

According to another object of the invention, the poly (phenylene ether) functionalized above are used for the manufacture of block copolymers comprising poly (phenylene ether) blocks and polyester blocks. Thus, the invention relates to poly (phenylene ether) / polyester block copolymers comprising blocks consisting respectively of recurring units of general formulas II and (III and / or IV). (II) (OC 1 R 3 C, wherein R 4 O + R 'R' 2 '2 (III) wherein R 5 represents a linear or branched hydrocarbon chain containing from 1 to 6 carbon atoms R2 and R'2 represent a substituted or unsubstituted aryl radical or a linear or branched alkyl radical comprising from 1 to 6 carbon atoms, said radicals possibly comprising heteroatoms R3 represents an alkyl or aromatic radical R4 represents an alkylene radical comprising from 2 to 6 carbon atoms n represents a number between 10 and 300. The polyesters which are suitable for the invention are polyesters obtained from diol monomers and diacid monomers or their derivatives such as, acid chlorides, Thus, the diols are generally linear, branched or cycloaliphatic aliphatic diols, by way of example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6 hexanediol, the 1,10-decanediol, 1,4-cyclohexanedimethanol. The diacids or derivatives are preferably aromatic and may be selected from the group consisting of isophthalic acid, terephthalic acid, naphthenic acid, orthophthalic acid or their methyl esters.

The aromatic diacid monomers may be used in admixture with aliphatic diacid monomers such as adipic acid, succinic acid, glutaric acid, maleic acid. According to a preferred embodiment of the invention, the polyester blocks of the copolymer 30 predominantly have repeating units of structure V: These polyesters are polyethylenesterephthalates, often referred to as "polyethylene terephthalate". the abbreviation PET in the field of plastics and the manufacture of plastic bottles. This polyester is obtained by polymerization of the monomers ethylene glycol and terephthalic acid or dimethyl terephthalate. Such polyesters have been known for a very long time and are described in numerous documents.

It is another object of the invention to provide processes for making such poly (phenylene ether) / polyester block copolymers. According to one embodiment of the invention, the functionalized poly (phenylene ether) is added to the monomers of the polyester or to the medium obtained after the esterification or transesterification step containing the bis-hydroxyethyl terephthalate monomer or oligomer. The process for manufacturing the copolymer is then carried out according to the conventional conditions and operations for manufacturing the polyesters. Thus, this embodiment of the process comprises: a) Introduction into a mixture of at least one diol with at least one dicarboxylic acid or a dicarboxylic acid ester, poly (phenylene ether) functionalized 2-hydroxyethyl b) Esterification or transesterification of the acid or acid ester with the diol; c) Vacuum polycondensation of the esterification product. This method of making the polymers is conventional except for the introduction of the 2-hydroxyethyl functionalized poly (phenylene ether). Such methods are, for example, described in the book Techniques de l'Ingénieur vol. J 6020. 2151-2160. Step b) esterification or transesterification is a step commonly performed in industrial processes for the manufacture of polyesters. These two routes are, for example, mainly used for the manufacture of poly (ethylene terephthalate).

Thus the first way of obtaining, known as "methyl terephthalate" (DMT) is a transesterification reaction. The molten DMT is solubilized in ethylene glycol (EG) present in excess, the molar ratio EG / DMT being about 1.9 to 2.2, and the reaction is carried out at atmospheric pressure at temperatures of about 130 ° C. to 250 ° C. It requires the presence of a catalyst such as, for example, manganese acetate. The methanol released by the reaction is removed by distillation. Ethylene glycol present in excess is removed by evaporation after the transesterification reaction. The catalyst which is also a catalyst for the degradation of the polyester is blocked with phosphorus compounds after the reaction. The product resulting from the transesterification is a mixture of bis-2-hydroxyethyl terephthalate (BHET) and oligomers.

The second path is called "direct esterification". This is an esterification reaction of terephthalic acid with ethylene glycol. It is carried out at temperatures of 130 ° C. to 280 ° C. Terephthalic acid, melted at these temperatures, is not soluble in ethylene glycol (EG) but is in the ester product of the reaction. The solubilization of the reagent in the medium is therefore progressive. Ethylene glycol is present with a molar ratio of EG / Terephthalic acid of about 1 to 1.5. The result of this reaction is a mixture of oligomers having terminal functions in the form of terephthalic acid or 2-hydroxyethyl terephthalate. The use of these methods is the subject of numerous publications. The conditions set out above do not constitute a limitation to the scope of the present invention. Subsequent stages of polycondensation are generally catalyzed with the aid of metal compounds, for example with antimony, titanium or germanium compounds. They can be catalyzed by any polycondensation catalyst of polyesters. They are generally carried out under reduced pressure in order to promote the departure of the ethylene glycol formed during the condensation reaction. The polymer is then shaped, for example by extrusion of a rod through an orifice, cooling, and granulation by cutting the rod. The shaping is usually preceded by melt-phase filtering. The melt phase polycondensation and shaping steps may be followed by a solid phase post-condensation step. According to another embodiment of manufacture of the copolymers of the invention, the functionalized poly (phenylene ether) is added in molten polyester. The medium is advantageously mixed by shearing, for example, in single-screw or multi-screw extruders, in particular twin screw extruders, to obtain a uniform dispersion of poly (phenylene ether) functionalized in the polyester and a reaction between the hydroxyls of the polyphenylene ether and the functions. polyester acids. The copolymer thus obtained can be used in many applications, in particular for the manufacture of molded, injected, blown or extruded parts. The copolymers of the invention have a bond between the blocks of poly (phenylene ether) and stable polyester and in particular to obtain a dispersion of poly (phenylene ether) 2905952 8 homogeneous and in the form of particles or nodules of very small size , in particular nodules smaller than 500 nm. This result demonstrates that the functionalization of the poly (phenylene ether) according to the invention makes it possible to achieve a high degree of bonding between the polyester blocks and poly (phenylene ether).

This very good dispersion of the poly (phenylene ether) in the material or composition obtained according to the principle of the invention is illustrated by the photographs resulting from the Transmission Electron Microscopy analyzes appended to the present description and which will be described and commented on above. after.

Advantageously, the copolymer of the invention is used as a single element or component or associated with other polymers of a polymer matrix of a composition to be shaped for the manufacture of articles. This is also an object of the present invention. These compositions may contain numerous additives such as, for example, additives selected from the group consisting of dyes, pigments, reinforcing fillers, fillers, light-stabilizing additives, heat-stabilizing additives, antioxidants, molding agents, release agents, flame retardant additives. Other advantages, details of the invention will emerge more clearly in the light of the examples given below solely for information purposes and the appended figures in which: FIG. 1 represents the photographs obtained by transmission electron microscopy analysis. a section of the polymer of Example 2, FIG. 2 represents the photographs obtained by Transmission Electron Microscope analysis of a section of the polymer of Example 3, FIG. 3 represents the photographs obtained by electron microscope analysis. The characteristics of the polymers and copolymers are determined according to the following methods: • Viscosity index (IV, in ml / g): measured according to the method described in the ISO standard. 1628/5: This measurement is carried out with a solution of the polymer or copolymer at 0.5% by weight in a mixture phenol / orthodichlorobenzene 50/50 by weight to C. • Measurement of reaction rates by 1H NMR analysis on Brücker DRX 400 400 MHz spectrometer. The solvent used is deuterated chloroform CDCl3 for polyphenylene ether and deuterated tetrachloroethane TCE-d2 for the copolymers. 2905952 9 • JEOL 200CX Transmission Electron Microscopy which makes it possible to determine the size of the nodules in the copolymers. Ultramicrotome sections are labeled with Ruthenium tetraoxide (RuO4) in the vapor phase. Poly (phenylene ether) appears darker than PET. Crystallinity rate: thermal measurement carried out on a measuring apparatus by the DSC method marketed under the name DSC 7 by Perkin Elmer by applying a heating rate of 10 C / min, from 35 ° C. to 290 ° C. of crystallinity is determined by the ratio of the enthalpy of fusion on the enthalpy of fusion of a pure crystal of PET (120 J / g). The calculation takes into account the presence of polyphenylene ether in the composition. • Measurement of molar masses by Steric Exclusion Chromatography (SEC) at 2 mg / ml in tetrahydrofuran (THF) at 35 C. with a Viscotek VE1121 pump (THF at 1 ml.min-, a Rheodyne injector and three columns Styragel HR5E The calibration is carried out on the basis of polystyrene standards The detection is carried out with a VE3580 refractometer Example 1: synthesis of the EPP functionalized with a 2-hydroxyethyl structure (hereinafter referred to as PPE-EtOH) 11, provided with magnetic stirring and connected to a nitrogen sweeping system, is introduced with magnetic stirring: • 760 g of 1,3-dimethyl-2-imidazolidinone (solvent) • 5.9 g of potassium carbonate (85 mmol potassium ion) 20 • 200 g (85 mmol of phenol function) of PPO SA 120 poly (phenylene ether) marketed by General Electric Plastics (molar mass Mn = 2350 g.mol "', polydispersity index Ip = 2.7 and concentration chain ends including a fon phenol concentration equal to 425 gmol / g) 16.8 g of ethylene carbonate (in excess) (191 mmol, excess 2.2) The reaction medium is heated at 140 ° C. for 15 hours under a nitrogen sweep. The reaction medium is cooled to room temperature. The poly (phenylene ether) functionalized 2-hydroxyethyl is recovered by precipitation in 8 liters of distilled water and then washed with distilled water. The excess of ethylene carbonate and the solvent, both soluble in water, are removed during washing.

The 1 H NMR measurements indicate a functionalization rate of 100%. Steric Exclusion Chromatography (SEC) measurements indicate a slightly higher molar mass than unmodified poly (phenylene ether).

COMPARATIVE EXAMPLE 2 Synthesis of the PET / PEP Block Copolymer in a PET Synthesis Reactor In a Polymerization Reactor of 7.5 liters, Which makes it possible to obtain 3 kg of polymer by polycondensation, provided with stirring with torque-meter for monitoring the viscosity of the reaction medium, a distillation column for removing the water formed during the esterification, as well as the excess of ethylene glycol, and a vacuum circuit for the polycondensation step, 1190 g of ethylene glycol 10 - 2595 g of purified terephthalic acid 61.1 g of isophthalic acid 153.6 g of poly (phenylene ether) PPO SA 120 (see example 1) After purging with the reaction medium is heated to 275 ° C. with stirring and under an absolute pressure of 6.6 bar. The esterification time is 42 minutes (time required for the distillation of water). The pressure is then reduced to atmospheric pressure in 20 minutes. A glycolic solution of antimony oxide is introduced into the reaction medium (250 ppm Sb, relative to the polymer).

The pressure is maintained for 5 minutes at atmospheric pressure, before evacuating progressively from 1 bar to less than 1 mbar in 90 minutes. The reaction mass is brought to 285 C when the pressure is less than 1 mbar. The polycondensation time is defined as the time required to reach the target viscosity level from the moment when the pressure is less than 1 mbar.

The polycondensation time is 97 minutes. When the target viscosity level is reached, the stirring is stopped and the reactor is pressurized to 3 bar to pour the polymer into a tub of water in the form of rods which are cut into pellets.

Photographs of the copolymer obtained are taken with a Transmission Electron Microscope corresponding respectively to a magnification of 10000 and 30000 and are represented in FIG. 1. A dispersion of the PPE nodules is observed, with an average size of 1 micron. The reaction rate between PET and poly (phenylene ether) determined by 1 H NMR is 18% +/- 5%.

EXAMPLE 3 Synthesis of the PET-b-PPEEtOH Copolymer in a PET Synthesis Reactor A composition is prepared according to Example 2, except that the following compounds are introduced: 5 - 1190 g of ethylene glycol 2595 g d purified terephthalic acid 61.1 g of isophthalic acid - 153.6 g of poly (phenylene ether) functionalized 2-hydroxyethyl (example 1) The esterification time is 61 minutes, the polycondensation time is 46 minutes.

Photographs of the copolymer obtained are taken with a Transmission Electron Microscope corresponding respectively to a magnification of 10000 and 30000 and are represented in FIG. 2. A homogeneous dispersion of the functionalized EPP nodules with an average size of 300 nm is observed. The average size of the nodules of the dispersed phase is much smaller than that observed in Example 2 above. The reaction rate between the PET and the 2-hydroxyethyl functionalised poly (phenylene ether) determined in 1 H NMR is 100% +/- 5%. Comparative Example 4: Mixing PET with EPP in a Micro-Extruder The PET and EPP samples were pre-dried at 130 ° C under vacuum overnight. A bi-screw micro-extruder sold under the name DSM microl5 compounder (maximum capacity 15 cm3) is preheated to 280 C. The two screws are driven at a speed of 50 rpm. Using a hopper, introduced in one minute: 15gPET 30 - 1 g poly (phenylene ether) PPO SA 120 After introduction, the hopper is removed, the mold is closed, a nitrogen sweep is assured and the speed of the screws is increased to 100 rpm. After 30 minutes, the polymer is poured into a tray of water.

Photographs of the material obtained are taken with a Transmission Electron Microscope corresponding respectively to a magnification of 10000 and 30000 and are represented in FIG. 3. A dispersion of the PPE nodules is observed, with an average size of 700 nm.

The reaction rate between PET and the poly (phenylene ether) determined in 1 H NMR is 0% +/- 5/0.

EXAMPLE 5 Blend of PET with PPE-EtOH by Microformer A composition according to Example 4 was prepared except that the following compounds were introduced: 15 g of PET-1 g of polyphenylene ether functionalized 2-hydroxyethyl (Example 1) The mixture is made for a period of 30 minutes. Photographs of the material obtained are taken with a Transmission Electron Microscope corresponding respectively to a magnification of 10,000 and 30000 and are represented in FIG. 4. A dispersion of the PPE nodules is observed, with an average size of 200 nm.

This nodule size is significantly smaller than that observed in Example 4 above. The reaction rate between PET and the 2-hydroxyethyl functionalised poly (phenylene ether) determined by 1 H NMR is 55% + 1-5%.

Claims (13)

claims   Functionalized poly (phenylene ether) characterized in that it comprises at least macromolecular chains comprising at least one end of structure corresponding to the following general formula I: ## STR2 ## wherein: R represents a linear chain or branched hydrocarbon comprising from 1 to 6 carbon atoms. R2 and R'2 represent a substituted or unsubstituted aryl radical or a linear or branched alkyl radical comprising from 1 to 6 carbon atoms, said radicals possibly comprising heteroatoms;   2. Poly (phenylene ether) according to claim 1, characterized in that R, represents a methylene, ethylene or propylene radical.   3. Poly (phenylene ether) according to claim 1 or 2, characterized in that the radicals R2 and R'2 are methyl or ethyl radicals.   4. Poly (phenylene ether) according to one of the preceding claims, characterized in that all the ends of the macromolecular chains of the poly (phenylene ether) comprising a phenol function are functionalized and have a structure according to formula (I ).   5. Process for producing poly (phenylene ether) functionalized according to one of claims 1 to 4, characterized in that it consists in reacting an alkylene carbonate or alkylene oxide with a poly (phenylene ether) ) in the presence of a catalyst and a solvent.   6. Process according to claim 5, characterized in that the catalyst is potassium carbonate. 5 10 2905952 14   7. Method according to one of claims 5 or 6, characterized in that the solvent is a polar solvent selected from the group consisting of 1,3-dimethyl-2-imidazolidinone, methyl-pyrrolidinone, dimethylsufoxide, dimethylformamide.   8. Poly (phenylene ether) polyester copolymer characterized in that it comprises blocks consisting respectively of recurring units of the following general formulas II and III and / or IV (II) (OC 1 R 3 CO 2 O R + O - R O O - R O Where in: R, represents a linear or branched hydrocarbon chain comprising from 1 to 6 carbon atoms R2 and R'2 represent a substituted or unsubstituted aryl radical or a linear or branched alkyl radical comprising from 1 to 6 carbon atoms, the said radicals being able to comprise heteroatoms R 3 represents an alkyl radical or aromatic radical R 4 represents an alkylene radical comprising from 2 to 6 carbon atoms, n represents a number between 10 and 300. 2905952   9. Copolymer according to claim 8 characterized in that the recurring unit is: -COùOù {CH + O) 2 (V) OC 5   10. A method of manufacturing the copolymer according to one of claims 8 or 9, characterized in that it consists in adding to the monomers diols and diacids or synthetic diesters of the polyester, the poly (phenylene ether) functionalized according to one of the following: Claims 1 to 4, to perform the esterification or transesterification between the diol and the diacid or the diester and optionally the poly (phenylene ether) functionalized, to achieve the polycondensation of the mixture.   11. A method of manufacturing the copolymer according to one of claims 8 or 9, characterized in that it consists in adding to the molten polyester, a poly (phenylene-ether) 15 functionalized according to one of claims 1 to 4, mixing the medium to obtain a dispersion of the functionalized poly (phenylene ether).   12. The method of claim 11, characterized in that the mixture is obtained by shear in a device with at least one worm. 20   13. Composition comprising as polymer material comprising as a single component or element or associated with other polymers, a copolymer according to one of claims 8 or 9 and additives chosen from the group comprising pigment dyes, reinforcing fillers, filling, light stabilizing additives, heat stabilizing additives, antioxidants, molding agents, release agents, flame retardant additives