Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
  • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring

Definitions

• the present invention relates to a stabilizing composition for halogenated polymer comprising one or more compounds having at least one ethylenic unsaturation (C ⁇ C) and at least one heterocycle.
• Halogenated polymers and in particular chlorinated polymers, require the use of stabilization additives, which act during the shaping of the polymers, or even after the shaping of the latter (aging). Indeed, these polymers are sensitive to heat and light. The sensitivity to heat is noted by a degradation of the coloration of the polymer part, which then changes from an initial light color (white to light yellow) to brown, then to black.
• halogenated polymers Many additives have been developed so far in order to stabilize halogenated polymers. Thus, it is known to. using alkaline earth metal (calcium) and / or transition (zinc) carboxylates, compounds of the organotin type, or also based on lead. These additives have also been used in combination with other compounds such as, for example, organic compounds of the type of ⁇ -diketones or ⁇ -ketoesters, phosphites, etc., or even mineral compounds such as hydrotalcites, etc.
• One of the objectives of the present invention is to provide a stabilizing composition for halogenated polymers, comprising new compounds.
• Another object of the invention is to provide a means for stabilizing halogenated polymers which do not use additives comprising metals, or a lower content than that usually used in the field.
• the subject of the present invention is a stabilizing composition for halogenated polymer comprising at least one compound of formula (I) or (II) below:
• X, Y, Z identical or not, represent an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom; ,
• R 1 represents a radical comprising 1 to 20 carbon atoms of alkyl type; alkenyl carrying one or more ethylenic unsaturations, conjugated or not; cyclic carrying one or more ethylenic unsaturations, conjugated or not; aromatic optionally substituted;
• R2 represents a hydrogen atom; a radical comprising 1 to 20 carbon atoms, of alkyl type; alkenyl carrying one or more ethylenic unsaturations, conjugated or not; cyclic carrying one or more ethylenic unsaturations, conjugated or not; aromatic, substituted or not, optionally condensed with an aromatic ring or not; a radical -COR with R representing an alkyl radical comprising 1 to 20 carbon atoms;
• R 1 and R 2 are optionally linked together so as to form a cycle which optionally carries one or more ethylenic unsaturations, conjugated or not;
• R3 and R4 identical or not, represent a hydrogen atom; a radical comprising 1 to 20 alkyl type carbon atoms; alkenyl, carrying one or more ethylenic unsaturations, conjugated or not; cyclic optionally carrying one or more ethylenic unsaturations, conjugated or not; aromatic optionally substituted; said radicals Ri, R2, R3 and R4, being optionally interrupted by one or more groups -O-, -S-, -CO-, -NR-, -NRCO-, and / or optionally carrying at least one group - OH, -OR, -R'OH, with R and R 'representing a hydrogen atom or an alkyl radical comprising 1 to 20 carbon atoms; at least one of the radicals R2 or R3 being a hydrogen atom; n is 1 to 3 depending on the valence of X; m is 0 to 2 depending on the valence of Y; p is 0 to 2 depending on the valence
• the radical R1 is an alkyl radical comprising 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, optionally carrying at least one group -OH, -OR, -R'OH, with R representing a monovalent alkyl radical comprising 1 to 20 carbon atoms, and R ′ representing a divalent alkyl radical comprising 1 to 20 carbon atoms.
• radicals By way of example of such radicals, mention may be made of methyl, ethyl, propyl,
• the compounds of formula (I) and / or (II) are such that the coefficient q is 2 or 3.
• a first family of compounds is constituted by those of formula (I). More particularly, within the framework of this first family, a type of advantageous compounds is represented by those in which, X and Y, identical or not, represent nitrogen or sulfur, and preferably nitrogen. According to this variant, Z preferably represents oxygen or nitrogen.
• R2 preferably represents an aromatic radical comprising 4 to 6 carbon atoms optionally condensed with an aromatic radical comprising 6 carbon atoms, a -COR radical with R representing an alkyl radical comprising 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, or an alkyl radical comprising 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, optionally interrupted by an -O- or -S- group.
• R2 can be an aromatic cyclic radical including or not including the nitrogen atom.
• the atom X is itself part of the pyrrole or indole radical, if R2 is condensed with an aromatic ring.
• radical R2 represents hydrogen.
• an ⁇ , ⁇ unsaturated aldehyde such as aminocrotonate
• hydrogen sulfide is reacted with hydrogen sulfide.
• the reaction is carried out by introducing the aldehyde into a solvent, chosen in particular from chlorinated solvents (chloroform), saturated with hydrogen sulfide.
• a solvent chosen in particular from chlorinated solvents (chloroform), saturated with hydrogen sulfide.
• Said solvent can also comprise a tertiary amine.
• reaction medium is maintained under a flow of hydrogen sulfide.
• the introduction of the aldehyde is preferably carried out drop by drop.
• the duration of introduction is generally between 2 and 10 hours.
• This first step is carried out at a temperature below 0 ° C, and more particularly of the order of -20 to -10 ° C. Once the aldehyde has been added, the reaction medium is kept under stirring at a temperature of the order of -25 ° C.
• reaction product is separated by conventional means.
• a second step consists in reacting the compound resulting from the preceding step, with a compound of formula HO- (CH2) q-OH (for example ethylene glycol), or with HO- (CH2) q-NH2 (by example ethanolamine), or with H2N- (CH2) q-NH2 (for example ethylene diamine), in the presence of a catalyst such as paratoluene sulfonic acid in particular.
• a compound of formula HO- (CH2) q-OH for example ethylene glycol
• HO- (CH2) q-NH2 by example ethanolamine
• H2N- (CH2) q-NH2 for example ethylene diamine
• the molar ratio of the compound from the previous step and the glycol is around 1/2.
• the reaction preferably takes place in the presence of a solvent, such as, for example, toluene.
• a solvent such as, for example, toluene.
• the reaction temperature is close to the reflux of the solvent used.
• the product is then separated by conventional methods.
• the acetal obtained is reacted with a chlorinating agent such as, for example, N-chlorosuccinimide.
• a chlorinating agent such as, for example, N-chlorosuccinimide.
• the operation can take place in the presence of a chlorinated solvent.
• the reaction can advantageously be carried out at a temperature close to room temperature.
• the resulting product once the solvent has been removed, is brought into contact with a solution of an alkali metal alcoholate, preferably potassium tert-butoxide, in an anhydrous medium.
• an alkali metal alcoholate preferably potassium tert-butoxide
• the solvent used is preferably an ether such as tetrahydrofuran.
• the contacting and the reaction are preferably carried out at a temperature below ambient temperature, more particularly below 10 ° C., preferably of the order of 0 ° C.
• the resulting product corresponding to the compound of formula (I) as described above, is isolated in a conventional manner. It is specified that the resulting compound can undergo a dehydrogenation step, in the case where one or both heteroatoms of the ring are nitrogen atoms. This step leads to a compound of formula (II).
• the dehydrogenation can in particular take place by implementing a heat treatment in the presence of a catalyst chosen for example from manganese oxide, or terbutylhydroperoxide combined with a ruthenium salt.
• a catalyst chosen for example from manganese oxide, or terbutylhydroperoxide combined with a ruthenium salt.
• a compound of formula (II) By way of example of synthesis of a compound of formula (II), one can exemplify that giving access to a compound for which X represents a nitrogen atom, Z represents an oxygen or nitrogen atom, R1 an alkyl radical.
• an ⁇ , ⁇ unsaturated ester (for example an alkyl aminocrotonate, the alkyl part comprising more particularly 1 to 4 carbon atoms), with other part, an amino alcohol of formula HO- (CH2) q-NH2 or also with a diamine of formula H2N- (CH2) q-NH2.
• the reaction is usually carried out with stirring and at a temperature generally between 150 and 250 ° C.
• the molar ratio of the ester to the amino alcohol or the diamine is between approximately 0.5 and 1.2.
• This reaction can be carried out in the presence of an appropriate solvent.
• the solvent is more particularly chosen from those whose boiling point is higher than that of the alcohol eliminated during the reaction.
• chlorobenzene is an example of a suitable solvent. But advantageously, a solvent is not necessary.
• the compound obtained is then put under conditions such that the cycle is formed.
• Such conditions can be achieved for example in the presence of thionyl chloride. It should be noted that, depending on the nature of the atoms, an agent which aids in cyclization is not necessary.
• the temperature is usually between 50 to 80 ° C, in the presence of compounds such as thionyl chloride. If this type of compound is not used, the temperature is then usually between 150-250 ° C.
• this reaction can also be carried out in the presence of an appropriate solvent such as for example alkylated or aromatic chlorinated solvents, aromatic solvents, such as in particular toluene, xylene).
• an appropriate solvent such as for example alkylated or aromatic chlorinated solvents, aromatic solvents, such as in particular toluene, xylene.
• aromatic solvents such as in particular toluene, xylene.
• no solvent is used.
• the compounds which have just been described are used in stabilizing compositions for halogenated polymers.
• halogenated polymer forming part of the composition according to the invention is intended to denote more particularly, chlorinated polymers, such as polyvinyl chloride (PVC).
• PVC polyvinyl chloride
• any type of PVC is suitable, whatever its method of preparation: bulk, suspension, emulsion or any other type polymerization and whatever its intrinsic viscosity.
• Homopolymers of vinyl chloride can also be modified chemically, for example by chlorination.
• copolymers of vinyl chloride can also be stabilized against the effects of heat, i.e. yellowing and degradation.
• these are in particular the copolymers obtained by copolymerization of vinyl chloride with other monomers having a polymerizable ethylenic bond, such as for example vinyl acetate or vinylidene chloride; maleic, fumaric acids, and / or their esters; olefins such as ethylene, propylene, hexene; acrylic or methacrylic esters; styrene; vinyl ethers such as vinyldodecyl ether.
• copolymers contain at least 50% by weight of vinyl chloride units and preferably at least 80% by weight of vinyl chloride units.
• compositions capable of being stabilized according to the process of the invention may also contain mixtures based on chlorinated polymer containing minority amounts of other polymers, such as halogenated polyolefins or acrylonitrile / butadiene / styrene copolymers.
• the total content of compounds (I) and / or (II) used is more particularly between 0.005 and 5% by weight relative to the weight of halogenated polymer (s), preferably between 0.5 and 5% by weight relative to the weight of halogenated polymer (s).
• the formulations comprising the halogenated polymer can be rigid formulations, that is to say without plasticizer, or semi-rigid, that is to say with reduced plasticizer contents, such as for applications in the building the manufacture of various profiles or electrical cables, or formulations containing only additives approved for food contact, for the manufacture of bottles.
• These formulations most often contain an impact enhancer, such as a methacrylate / butadiene / styrene copolymer for example.
• They can also be plasticized formulations such as for the manufacture of films for agricultural use.
• compositions of halogenated polymers comprising the stabilizing composition according to the invention may also contain stabilizing additives conventional in the field, whether they are of mineral or organic nature.
• a mineral type stabilizer By way of example of a mineral type stabilizer, mention may be made of sulphates, and / or carbonates, of aluminum and / or magnesium, in particular of the hydrotalcite type. It is recalled that the compounds of the hydrotalcite type correspond to the following formula: Mgi- ⁇ Al ⁇ (OH) 2A n " ⁇ / n • mH2 ⁇ , in which x is between 0 excluded and 0.5, A n" represents an anion such that carbonate in particular, n varies from 1 to 3 and m is positive. It should be noted that products of this type can be used, having undergone a surface treatment with an organic compound.
• stabilizer of organic type mention may likewise be made of polyols comprising 2 to 32 carbon atoms and having 2 to 9 hydroxyl groups.
• C3-C30 diols such as propylene glycol, butanediol, hexanediol, dodecanediol, neopentyl glycol, polyols such as trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, xylitol, mannitol, sorbitol, glycerin, mixtures of glycerol oligomers having a degree of polymerization from 2 to 10.
• diols such as propylene glycol, butanediol, hexanediol, dodecanediol, neopentyl glycol, polyols such as trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, xylitol, mannitol
• Another family of polyols which can be suitably used is constituted by partially acetylated polyvinyl alcohols.
• hydroxyl compounds comprising isocyanurate groups, alone or in combination with the abovementioned polyols, such as for example tris (2-hydroxyethyl) isocyanurate.
• the quantity of polyol and / or of hydroxylated compound used is generally between 0.05 and 5 g per 100 g of halogenated polymer. More particularly, it is less than 2 g per 100 g of halogenated polymer.
• halogenated polymer compounds of the organic phosphite type, such as, for example, trialkyl, aryl, triaryl, dialkylaryl phosphites, or diarylalkyl, for which the term alkyl denotes hydrocarbon groups of monoalcohols or of C8-C22 polyols. and the term aryl denotes aromatic groups of phenol or of phenol substituted by C group-Ci 2- alkyl groups.
• calcium phosphites such as for example compounds of the Ca (HP ⁇ 3) type. (H2 ⁇ ) thus than phosphite - hydroxy - aluminum - calcium complexes.
• the additive content of this type is usually between 0.1 and 2 g per 100 g of halogenated polymer. It is likewise conceivable to use at least one alkali, crystalline, synthetic metal aluminosilicate having a water content of between 13 and
• NaA type zeolites are particularly suitable, as described in US Pat. No. 4,590,233.
• the content of this type of compound generally varies between 0.1 and 5 g per 100 g of halogenated polymer.
• epoxide type can likewise be used. These compounds are generally chosen from epoxidized polyglycerides, or esters of epoxidized fatty acids, such as epoxidized linseed, soybean or fish oils.
• the amount of these compounds, if present, usually varies between 0.5 and 10 g per 100 g of halogenated polymer.
• titanium dioxide is in the rutile form.
• particle size of the titanium dioxide used in the compositions according to the invention is between 0.1 and 0.5 ⁇ m.
• titanium dioxide is used in rutile form having undergone a surface treatment, preferably mineral, such as titanium dioxide Rhoditan® RL18, Rhoditan® RL90, marketed by Rhodia Chimie, Kronos 2081® and 2220® titanium dioxides marketed by
• Formulations based on halogenated polymers may include other white or colored pigments.
• the colored pigments there may be mentioned in particular cerium sulfide.
• the quantity of pigment introduced into the formulation varies within wide limits and depends in particular on the coloring power of the pigment and on the desired final coloration. However, by way of example and if the polymer composition contains it, the amount of pigment may vary from 0.1 to 20 g per 100 g of halogenated polymer, preferably from 0.5 to 15 g relative to the same reference. .
• Additives such as phenolic antioxidants, anti-UV agents such as
• 2-hydroxybenzophenones 2-hydroxybenzotriazoles or sterically hindered amines, usually known as Hais, can be included in the halogenated polymer composition.
• the content of this type of additive generally varies between 0.05 and 3 g per 100 g of halogenated polymer.
• lubricants can also be used which will facilitate implementation, chosen in particular from glycerol monostearates or even propylene glycol, fatty acids or their esters, montanate waxes, poylethylene waxes or their oxidized derivatives, paraffins, metallic soaps, functionalized polymethylsiloxane oils such as, for example, ⁇ -hydroxypropylenated oils.
• the amount of lubricant entering the halogenated polymer formulation generally varies between 0.05 and 2 g per 100 g of halogenated polymer.
• the formulation can also comprise plasticizers chosen from alkyl phthalates.
• the most generally used compounds are chosen from di (ethyl-2-hexyl) phthalate, the esters of linear C 6 -C 12 diacids. 'es triméllitates or ester phosphates.
• the amount of plasticizer used in the formulations varies over a wide range, depending on the rigid or flexible nature of the final polymer. As an indication, the content varies from 0 to 100 g per 100 g of polymer.
• composition according to the invention does not require the use of metallic type stabilizers, or in lower contents than those usually used.
• metallic stabilizers examples include compounds comprising an alkaline earth metal or a metal chosen from columns IIB, MA, IVB of the periodic table of the elements (published in the supplement to the Bulletin of the Company Chimique de France, no. 1, January 1966).
• the metals are more particularly chosen from calcium, barium, magnesium, strontium, zinc, cadmium, tin or even lead.
• the most commonly used are for example the salts of elements IIA or IIB of maleic, acetic, diacetic, propionic, hexanoic, 2-ethylhexanoic, decanoic, undecanoic, lauric, myristic, palmitic, stearic, oleic, ricinoleic, behenic (docosanoic) acids. ), hydroxystearic, hydroxy- undecanoic, benzoic, phenylacetic, paratertiobutylbenzoic and salicylic, phenolates, alcoholates derived from naphthol or phenols substituted by one or more alkyl radicals, such as nonylphenols.
• dibasic lead carbonate tribasic lead sulfate, tetrabasic lead sulfate, dibasic lead phosphite, lead porthosilicate, basic lead silicate, silicate and lead sulfate coprecipitate, basic lead chlorosilicate, silica gel and lead orthosilicate coprecipitate, dibasic lead phatalate, neutral lead stearate, dibasic stearate lead, tetrabasic lead fumarate, dibasic lead maleate, 2-ethyl lead hexanoate, lead laurate (see in particular ENCYCLOPEDIA of PVC by Léonard I. NASS (1976) page 299-303).
• tin-based compounds mention may in particular be made of mono- or di-alkyltin carboxylates and mercaptides of mono- or di-alkyltin; but also more commonly, the derivatives of di-n-methyltin, of di-n-butyltin or of di-n-octyltin such as, for example, dibutyltin dilaurate.
• dibutyltin maleate dibutyltin laurate-maleate, bis dibutyltin (mono-C ⁇ Cs-alkyl maleate), dibutyltin bis (lauryl-mercaptide), dibutyltin SS '(isooctyl mercatoacetate), dibutyltin ⁇ -mercapto propionate, di-n- maleate octyltin polymer, bis-S-S '(isooctyl mercaptoacetate) di-n-octyltin, ⁇ -mercapto-propionate di-n-octyltin.
• the content of metallic stabilizer can vary between 0 and 100 ppm, expressed relative to the metal, per 100 g of halogenated polymer. More particularly, this content can be between 0 and 50 ppm per 100 g of halogenated polymer.
• the preparation of the halogenated polymer formulation can be done by any means known to those skilled in the art.
• this operation can be carried out in a mixer fitted with a blade and counter-blade system operating at a high speed.
• the mixing operation is carried out at a temperature below 130 ° C.
• the composition is formed according to the usual methods in the field such as injection, extrusion blow molding, extrusion, calendering or even rotational molding.
• the temperature at which the shaping is carried out generally varies from 150 to 220 ° C.

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  • 2000-07-17 FR FR0009311A patent/FR2811673B1/fr not_active Expired - Fee Related
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