Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
  • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
  • C07C69/716—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/77—Preparation of chelates of aldehydes or ketones
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/92—Ketonic chelates
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
• • 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
  • C08K5/0091—Complexes with metal-heteroatom-bonds

Definitions

• the present invention relates to the use of zinc acetylacetonate, mostly crystallized in the form of a monohydrate compound, as a stabilizing agent for halogenated polymers. It also relates to a process for the preparation of said zinc acetylacetonate.
• Anhydrous zinc acetylacetonate is a product known in the literature, as is its role in stabilizing halogenated polymers, and in particular chlorinated polymers, such as polyvinyl chloride.
• chlorinated polymers such as polyvinyl chloride.
• the object of the present invention is to provide another type of zinc acetylacetonate which can be used as an agent for stabilizing halogenated polymers, which does not have the above drawback.
• the present invention therefore has for first object the use of zinc acetylacetonate comprising at least 4.4% by weight of water, as stabilizer of halogenated polymers. Note that for reasons of simplification and clarity of the description which follows, zinc acetylacetonate, the use of which constitutes one of the objects of the invention, will be qualified as "monohydrate", to distinguish it from the zinc acetylacetonate
• It also relates to a process for the preparation of zinc acetylacetonate monohydrate, in which a zinc oxide and / or hydroxide and acetylacetone are brought into contact, in the presence of a solvent; said solvent being used with an amount of between 20 and 200 parts by weight, per 100 parts by weight of acetylacetone.
• the monohydrate compound is stable over time and does not solidify, even if it is stored in an ambient atmosphere, that is to say with a certain humidity.
• the compound used in the invention is therefore zinc acetylacetonate comprising at least 4.4% by weight of water. More particularly, the water content is between 4.4 and 8.8% by weight.
• the compound used has a water content of between 4.75% and 8.15% by weight.
• the compound has a structure close to that of zinc acetylacetonate monohydrate.
• the compound according to the invention corresponds to the following average formula:
• the zinc acetylacetonate used in the invention is such that the aforementioned coefficient x is between 0.65 and 1, 3. According to a more particular embodiment, said coefficient x is between 0.7 and 1.2.
• a compound mainly crystallized in the form of a monohydrate compound is used.
• the coefficient x is of the order of 1.
• the hydrated zinc acetylacetonate crystals according to the invention have a limited acicular character (morphology different from that of a needle).
• this product can be in the form of a powder but also in a granulated or compacted form if necessary, by means of an appropriate shaping step.
• Zinc acetylacetonate can be obtained by implementing conventional methods with or without solvent.
• a second object of the present invention resides in another method allowing access to hydrated zinc acetylacetonate.
• This process consists in bringing into contact a zinc oxide and / or a hydroxide and acetyiacetone, in the presence of a solvent; the solvent being used in an amount between 20 and 200 parts by weight, per 100 parts by weight of acetylacetone.
• the solvent content is less than or equal to 100 parts by weight relative to the same reference.
• the amount of solvent used is at least 40 parts by weight relative to the same reference, and preferably at least 50 parts by weight.
• one embodiment of the method according to the invention consists in using an amount of solvent of between 20 and 100 parts by weight per 100 parts by weight of acetylacetone, more particularly between 40 and 100 parts by weight, and of preferably between 50 and 100 parts by weight.
• the solvent used in the reaction is more particularly a compound capable of solubilizing acetyiacetone and it is preferably inert with respect to the constituents of the reaction mixture, under the conditions of the reaction.
• the solvent is chosen from compounds whose boiling point is at most 100 ° C., measured at atmospheric pressure.
• the compounds capable of being used as solvents mention may be made, without intending to be limited, of Ci-Ce aliphatic alcohols, such as methanol, ethanol, propanol.
• ketones such as acetone; compounds comprising amide functions, such as formamide, dimethylformamide; aromatic compounds, such as benzene, or optionally comprising one or more alkyl substituents.
• the contacting is also carried out in the presence of an acetylacetone / zinc oxide and / or hydroxide molar ratio of between 2/1 and 2.4 / 1.
• the method according to the invention is implemented in the presence of a molar ratio of between 2/1 and 2.2 / 1.
• the contacting is carried out with an acetylacetone / oxide and / or zinc hydroxide molar ratio close to the stoichiometry.
• the contacting is carried out with stirring.
• the reaction is carried out in a turbosphere type reactor, or any other device provided with mechanical stirring means allowing good homogenization of a heterogeneous reaction mixture.
• the contacting is carried out by introducing the acetyiacetone into a mixture of zinc oxide and / or hydroxide and solvent.
• the reactants are brought into contact preferably maintaining the temperature between room temperature and around 100 ° C. More particularly, the contacting takes place at a temperature below 80 ° C. According to a preferred embodiment of the invention, the contacting of acetyiacetone with the oxide and / or the hydroxide is carried out at a temperature lower than or equal to that of reflux of the solvent used (or the mixture of solvent ).
• the contacting can be carried out under an inert atmosphere (such as nitrogen or a rare gas) or even in air.
• the duration of the operation is typically from one hour to 4 hours.
• the stirring and the temperature are preferably maintained for one to two hours. After this preferred finishing step, the solvent is removed from the reaction mixture.
• An advantageous embodiment of the invention consists in carrying out the removal of the solvent in two successive stages.
• the first takes place at atmospheric pressure, regularly increasing the temperature so as to distil the solvent without removing the water present.
• the second step takes place under reduced pressure to remove the remaining traces of solvent.
• the procedure is carried out so that the water content in the hydrated zinc acetylacetonate obtained remains within the range indicated above.
• the method according to the invention makes it possible to limit the acicular nature of the crystals obtained, that is to say not to promote the growth of the crystals in the form of a needle. Without wishing to be limited by any theory, it was 5
• a product is obtained in the form of a finely divided powder, which can be envisaged to be shaped, in particular by means of a granulation or compaction step.
• the advantage of the process according to the invention is that it makes it possible to combine, very advantageously, the advantages of the conventional processes without solvent and with solvent, without having the disadvantages.
• the process according to the invention is not only a productive process, but also it allows correct control of the heat of reaction.
• the zinc acetylacetonate monohydrate which has just been described is used as a stabilizing agent for halogenated polymers, which are more particularly chlorinated polymers.
• Zinc acetylacetonate monohydrate has an effect on the thermal stability of the polymer, but also on its stability against light.
• the content of zinc acetylacetonate monohydrate is more precisely between 0.01 and 2 g per 100 g of halogenated polymer. More particularly, the content of this compound is between 0.05 and 1 g relative to the same reference.
• the invention is particularly well suited for the stabilization of formulations based on polyvinyl chloride (PVC).
• PVC polyvinyl chloride
• polyvinyl chloride compositions in which the polymer is a homopolymer of vinyl chloride.
• the homopolymer can be chemically modified, for example by chlorination.
• copolymers of vinyl chloride can also be stabilized using the composition according to the invention.
• These are in particular polymers obtained by copolymerization of vinyl chloride with monomers having an ethylenically polymerizable bond, such as for example vinyl acetate, vinylidene chloride; maleic, fumaric acids or their esters; olefins such as ethylene, propylene, hexene; acrylic or methacrylic esters; styrene; vinyl ethers such as vinyldodecyl ether.
• the copolymers contain at least 50% by weight of vinyl chloride units and preferably at least 80% by weight of such units.
• PVC alone or in admixture with other polymers is the most widely used chlorinated polymer in stabilized formulations according to the invention.
• any type of polyvinyl chloride is suitable, whatever its method of preparation.
• the polymers obtained for example by using bulk, suspension or emulsion processes can be stabilized using the composition according to the invention, regardless of the intrinsic viscosity of the polymer.
• the formulations may contain the stabilizing additives conventionally used in the field.
• hydrochloric acid sensing compounds which can be of organic type or of mineral type, and can be present alone or in mixtures.
• organic hydrochloric acid sensors there may be mentioned more particularly the compounds comprising an alkaline earth metal or a metal chosen from the columns MB, MA, IVB of the periodic classification of the elements (published in the supplement to the Bulletin of the French Chemical Society, no. 1, January 1966).
• the cations are more particularly preferably chosen from calcium, barium, magnesium, strontium, zinc, cadmium, tin or even lead.
• associations are possible, such as for example a mixture of hydrochloric acid sensor based on calcium and zinc, barium and zinc, barium and cadmium, the first association being preferred.
• hydrochloric acid sensing compounds of organic type comprising at least one of the elements of columns MB and MA
• the most commonly used are, for example, the salts of elements IIA or MB of maleic, acetic, diacetic, propionic, hexanoic, 2-ethyl hexanoic, 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.
• alkaline earth metal propionate the alkali metal oleate earthy, alkaline earth metal stearate, alkaline earth metal laurate, alkaline earth metal ricinoleate, alkaline earth metal docosanoate, alkaline earth metal benzoate, alkaline earth metal benzoate, alkaline earth metal salicylate, alkaline earth metal maleate and 2-mono-ethylhexyl), alkaline earth metal nonylphenates, alkaline earth metal naphthenate and among the cadmium organic compounds mentioned above, cadmium propionate, cadmium 2-ethyl hexanoate, cadmium laurate, cadmium stearate, cadmium salicylate, cadmium and mono (2-ethylhexyl) maleate, cadmium nonylphenates, naphth
• dibasic lead carbonate tribasic lead sulfate, tetrabasic lead sulfate, dibasic lead phosphite
• lead orthosilicate basic lead silicate, coprecipitate.
• silicate and lead sulphate basic lead chlorosilicate, silica gel and lead orthosilicate coprecipitate, lead dibasic phatalate, lead neutral stearate, lead dibasic stearate, lead tetrabasic fumarate , dibasic lead maleate, 2-ethyl lead hexanoate, lead laurate.
• tin-based compounds As regards tin-based compounds, one can in particular refer to the work "PLASTICS AUDITIVES HANDBOOK" by GACHTER / MULLER (1985) pages 204-210 or in ENCYCLOPEDIA OF PVC by Léonard I. NASS (1976 ) pages 313-325.
• They are more particularly mono- or di-alkyltin carboxylates and mono- or di-alkyltin mercaptides.
• di-n-methyltin of di-n-butyltin or of di-n-octyltin
• dibutyltin dilaurate dibutyltin maleate, dibutyltin laurate-maleate
• dibutyltin bis dibutyltin bis (mono-C 4 -C 8 -alkyl maleate)
• dibutyltin bis dibutyltin bis (lauryl-mercaptide)
• dibutyltin ⁇ -mercapto propionate maleate of polymeric di-n-octyltin, bis-S- S '(isooctyl mercaptoacetate) di-n-octyltin, di-n-octyltin ⁇ -mercapto-propionate.
• the monoalkyl derivatives of the compounds mentioned above
• hydrochloric acid sensor of the mineral type mention may also be made of sulphates, and / or carbonates, of aluminum and / or magnesium, of the hydrotalcite type. 8
• the compounds of the hydrotalcite type correspond to the following formula: Mg 1 . x Al x (OH) 2 A n - ⁇ / n . mH 2 O, in which x is between 0 excluded and 0.5, A n " represents an anion such as carbonate in particular, n varies from 1 to 3 and m is positive. It is also possible to use essentially amorphous compounds of formula
• the content of the abovementioned mineral type sensor is more particularly between 0.1 and 10 g per 100 g of halogenated polymer.
• this content is between 0.3 and 3 g relative to the same reference. According to an even more particular embodiment of the invention, this content is between 0.3 and
• the content of organic type sensor is more particularly between 0.1 and 10 g per 100 g of halogenated polymer, preferably between 0.1 and 3 g with respect to the same reference.
• At least one hydrochloric acid sensor in addition to zinc acetylacetonate monohydrate, at least one hydrochloric acid sensor is used, comprising at least one mineral type sensor and at least one organic type sensor chosen from calcium salts and / or zinc of carboxylic acids. All the hydrochloric acid sensors of the mineral type mentioned above are suitable for implementing the invention.
• the mineral type sensor is chosen from the compounds of the following formula: Mg 1 _ x Al x (OH) 2 A n - ⁇ / n . mH 2 O, in which x is between 0 excluded and 0.5, A n " represents an anion such as carbonate in particular, n varies from 1 to 3 and m is positive.
• the composition according to this first variant comprises at least one calcium-based sensor, optionally combined with a zinc-based sensor.
• the content of the abovementioned mineral type sensor is more particularly between 0.1 and 10 g per 100 g of halogenated polymer. Preferably, this content is between 0.3 and 3 g relative to the same reference.
• this content is between 0.3 and 1 g relative to 100 g of halogenated polymer.
• the content of organic type sensor defined for this first variant is more particularly between 0.1 and 4 g per 100 g of halogenated polymer, preferably between 0.3 and 2 g relative to the same reference.
• a second variant consists of a composition comprising, in addition to zinc acetylacetonate monohydrate, as a hydrochloric acid sensor, at least one organic sensor chosen from compounds based on lead.
• Lead salts are used more particularly from those described above.
• the lead salts used are chosen from lead phosphites combined with neutral or dibasic lead stearates, tri- or tetra-basic lead sulfates optionally combined with at least one neutral stearate or lead dibasic.
• the composition comprises a content of sensor of organic type based on lead is between 1 and 10 g per 100 g of halogenated polymer.
• the composition further comprises at least one organic type sensor chosen from the salts of calcium carboxylic acids, described above.
• the content of the abovementioned organic type sensor is between 0.1 and 3 g per 100 g of halogenated polymer.
• a third variant consists of a composition comprising, in addition to zinc acetylacetonate monohydrate, at least one organic sensor chosen from tin salts. All the tin-based compounds described above can be chosen as constituent elements of the composition according to this third variant.
• the stabilizing composition has a content of sensor of the abovementioned organic type, between 0.1 and 3 g per 100 g of halogenated polymer, preferably between 0.2 and 2 g with respect to the same reference.
• the content of tin-based sensor is between 0.3 and 1 g per 100 g of halogenated polymer.
• the formulations according to the invention can also comprise, if necessary, at least one free ⁇ -diketone.
• the ⁇ -diketones are chosen from compounds corresponding to the formula (I) R 1 COCHR 2 COR 3 , formula in which, R 2 and R 3 , identical or different, represent a C ⁇ -C 30 and R hydrocarbon radical 2 represents a hydrogen atom or a C- alkyl radical
• the radicals R 1 or R 3 of said ⁇ -diketone represent an alkyl, alkenyl, linear or branched, C 1 -C 24 radical; a C 6 -C 30 aryl radical, substituted or not substituted by at least one alkyl radical and / or a halogen atom and / or a silicon atom; a C 3 -C 14 cycloaliphatic radical and which may optionally contain carbon-to-carbon double bonds.
• the radicals R 1 and R 3 represent an alkyl radical, linear or branched at C r C 8 ; a C 6 -C 10 aryl radical, substituted or not substituted by at least one alkyl radical and / or a halogen atom; or a cycloaliphatic radical as defined above.
• the radicals mentioned above can optionally be modified by the presence in the aliphatic chain of one or more groups of formula -O-, -CO-O-, -CO-.
• the radicals do not include such functions.
• radicals R 1 and R 3 can be linked together so that the ⁇ -diketone forms a cycle.
• the radical R 2 can be either a hydrogen atom or a C r alkyl radical
• R 2 represents a hydrogen atom or a methyl radical.
• R 2 represents a hydrogen atom or a methyl radical.
• octanoylbenzoylmethane stearoyibenzoyimethane, dibenzoyimethane or even acetylbenzoylmethane.
• the content of free ⁇ -diketone is usually between 0.05 and 1 g per 100 g of halogenated polymer.
• the formulation may likewise comprise a ⁇ -diketone in the form of calcium, magnesium or zinc chelate (with the exception of zinc acetylacetonate).
• the content of this compound is between 0.05 and 1 g per 100 g of halogenated polymer.
• the formulation can also comprise at least one polyol comprising 2 to 32 carbon atoms and having two to nine hydroxyl groups.
• C 3 -C 30 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 with 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, mannito
• Another family of polyols which can be suitably used is constituted by partially acetylated polyvinyl alcohols. 11
• hydroxylated compounds comprising isocyanurate groups, alone or in combination with the abovementioned polyols, such as for example tris (2-hydroxyethyl) isocyanurate.
• the amount of polyol 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.
• composition according to the invention compounds of the organic phosphite type, such as, for example, trialkyl, aryl, triaryl, dialkylaryl, or diarylalkyl phosphites, for which the term alkyl denotes groups hydrocarbons of mono-alcohols or of C 8 -C 22 polyols, and the term aryl denotes aromatic groups of phenol or of phenol substituted by C 6 -C 12 alkyl groups.
• calcium phosphites such as for example compounds of the Ca (HPO 3 ) (H 2 O) type as well as phosphite - hydroxy - aluminum - calcium complexes.
• the additive content of this type is usually between 0.1 and 2 g for
• the stabilizing compositions according to the invention can likewise comprise at least one aluminosilicate of alkali metal, crystalline, synthetic, having a water content of between 13 and 25% by weight, of composition 0.7-1 M 2 O.AI 2 O 3 .1, 3-2,4SiO 2 in which M represents an alkali metal such as in particular sodium.
• NaA type zeolites are particularly suitable, as described in US Pat. No. 4,590,233.
• composition according to the invention can also comprise compounds of the epoxide type. These compounds are generally chosen from epoxidized polyglycerides, or esters of epoxy fatty acids, such as epoxidized linseed, soybean or fish oils.
• the amount of compounds of this type usually varies between 0.5 and 10 g per 100 g of halogenated polymer.
• the formulation can include white or colored pigments.
• colored pigments mention may be made of compounds based on rare earths, in particular cerium sulphide.
• the composition comprises a white pigment which is most often titanium dioxide. 12
• titanium dioxide is chosen in the rutile form.
• the particle size of the titanium dioxide particles is generally between 0.1 and 0.5 ⁇ m.
• titanium dioxide is used in rutile form having undergone a surface treatment, preferably mineral.
• titanium dioxide Rhoditan RL18 sold by Millenium
• titanium dioxides Kronos 2081 and 2220 sold by Kronos.
• the amount of pigment introduced into the formulation comprising the polymer varies within wide limits and depends on the coloring power of the pigment and on the desired final coloration. However, by way of example, the amount of pigment can vary from 0.5 to 15 g per 100 g of chlorinated polymer.
• the content may more particularly be between 0.1 and 20 g per 100 g of halogenated polymer, preferably between 2 and 15 g with respect to the same reference.
• the formulation may include phenolic antioxidants, UV stabilizers such as 2-hydroxybenzophenones, 2-hydroxybenzotriazoles or sterically hindered amines, commonly known as Hais.
• the content of this type of additive generally varies between 0.05 and 3 g per 100 g of resin.
• 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 resin.
• the formulation can also comprise plasticizers chosen from alkyl phthalates.
• the most generally used compounds are chosen from di (ethyl-2-hexyl) phthalate, esters of linear C 6 -C ⁇ 2 diacids, trimellitates or even phosphate esters.
• 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 5 to 100 g per 100 g of halogenated polymer. 13
• the preparation of the formulations can be done by any means known to those skilled in the art.
• the temperature at which the constituents of the formulation are incorporated is less than 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.
• Example 2 The procedure is as for Example 1 except that the solvent consists of 300 g of methanol. In addition, the reflux period following the introduction of the reagents is 2 hours.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (5)

Publications (1)

Family

ID=26234203

Family Applications (1)

Country Status (12)

Cited By (1)

Families Citing this family (6)

Family Cites Families (3)

• 1999
  • 1999-03-12 RU RU2000125688/04A patent/RU2216534C2/ru not_active IP Right Cessation
  • 1999-03-12 JP JP2000535695A patent/JP2002506101A/ja active Pending
  • 1999-03-12 TR TR2000/03427T patent/TR200003427T2/xx unknown
  • 1999-03-12 AU AU27346/99A patent/AU734455B2/en not_active Ceased
  • 1999-03-12 CN CN99805696A patent/CN1299392A/zh active Pending
  • 1999-03-12 EP EP99907704A patent/EP1062269A1/fr not_active Withdrawn
  • 1999-03-12 BR BR9908725-1A patent/BR9908725A/pt not_active Application Discontinuation
  • 1999-03-12 WO PCT/FR1999/000568 patent/WO1999046322A1/fr not_active Application Discontinuation
  • 1999-03-12 CA CA002322984A patent/CA2322984A1/fr not_active Abandoned
  • 1999-03-12 KR KR1020007010090A patent/KR20010034596A/ko active IP Right Grant
  • 1999-03-12 PL PL99342854A patent/PL342854A1/xx not_active Application Discontinuation
• 2000
  • 2000-09-11 NO NO20004532A patent/NO20004532L/no not_active Application Discontinuation

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events