Note: Within nine months from the publication of the mention of the grant of the European patent, any person may givenotice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed ina written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art.99(1) European Patent Convention).

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(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention of the grant of the patent: 21.03.2007 Bulletin 2007/12

(21) Application number: 03741907.4

(22) Date of filing: 06.06.2003

(51) Int Cl.:C07C 45/77 (2006.01) C08K 5/07 (2006.01)

C09K 15/06 (2006.01)

(86) International application number: PCT/US2003/018250

(87) International publication number: WO 2004/005232 (15.01.2004 Gazette 2004/03)

(54) COMPLEXES OF METAL SALTS OF ORGANIC ACIDS AND BETA-DIKETONES AND METHODS FOR PRODUCING SAME

KOMPLEXE VOM METALLSALZEN MIT ORGANISCHEN SÄUREN UND BETA-DIKETONEN UND METHODEN ZU DEREN DARSTELLUNG

COMPLEXES DE SELS METALLIQUES D’ACIDES ORGANIQUES ET DE BETA-DICETONES ET METHODES DE PRODUCTION

(84) Designated Contracting States: AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

(30) Priority: 03.07.2002 US 190130

(43) Date of publication of application: 30.03.2005 Bulletin 2005/13

(73) Proprietor: Chemtura CorporationMiddlebury, CT 06749 (US)

(72) Inventors: • KRAINER, Edward

Lynbrook, NY 11563 (US)• FISCH, Michael, H.

Wayne, NJ 07470 (US)

• STEWEN, Ulrich58239 Schwerte (DE)

• BACALOGLU, RaduHamburg, NY 07419 (US)

• BACALOGLU, IlzeHamburg, NY 07419 (US)

(74) Representative: Wibbelmann, JobstWuesthoff & Wuesthoff, Patent- und Rechtsanwälte, Schweigerstrasse 281541 München (DE)

(56) References cited: EP-A- 1 229 073 WO-A-98/55542WO-A-99/46229 US-A- 4 102 839US-A- 5 672 646 US-A- 5 714 095

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Description

[0001] This invention relates to complexes useful inthe formation of stabilizer additives for halogen-contain-ing polymers such as polyvinyl chloride (PVC).[0002] Metal salts of organic acids complexed with β-diketone compounds, such as calcium benzoate 1,3-diphenylpropane-1,3-dionate (CBDBM), are useful in theformulation of stabilizers for halogenated resins and,when used jointly with other low toxic intermediates, suchas zinc or magnesium intermediates, can form effectivestabilizers with low toxicity and better performance thanother known stabilizers, including those containing toxicheavy metals such as cadmium and lead. Pursuant tothe present invention, these stabilizer complexes are pre-pared utilizing a Claisen condensation reaction and pre-cipitation with water and heptane.[0003] Halogen-containing resins, particularly polyvi-nyl chloride resins, are inherently unstable to heat anddecompose through a dehydrohalogenation reaction atthe time of processing, when exposed to high tempera-ture, or upon exposure to sunlight, etc. The result of thisdecomposition includes discoloration, degrading of me-chanical properties, and other objectionable changes inthe physical properties of the finished product.[0004] Attempts have been made to improve the ther-mal stability of halogenated resins by adding stabilizerssuch as metal salts of organic acids, inorganic basic met-al compounds, organotin compounds, organic phos-phites, epoxy compounds or β-diketones thereto. Stabi-lizers ensure satisfactory thermal stability duringprocessing at high output rates.[0005] Many stabilizers used in the past contained bar-ium, cadmium and/or lead. Due to their toxicity, there isa strong interest in replacing these heavy metals withnon-toxic stabilizers, such as those containing calciumand zinc. Non-toxic stabilizers that have been used in-clude combinations of organic acid zinc salts, organicacid alkaline earth metal salts, organotin compounds, or-ganic phosphite esters, epoxy compounds, antioxidants,polyols, etc. Among these non-toxic stabilizers, potassi-um, calcium or magnesium salts of organic acids havebeen used as a fundamental stabilizer for halogenatedresins.[0006] Although stabilizers comprising potassium, cal-cium or magnesium salts of organic acids are effectivein avoiding fast degradation of a halogenated resin overa prolonged period of time insuring good long term sta-bility, they are less effective with respect to discoloration,particularly discoloration in the initial stage of heating.[0007] β-diketone compounds are known co-stabiliz-ers in the presence of zinc compounds which overcomeobjectionable discoloration of halogenated resins. Meth-ods for producing β-diketones are also known in the art.For example, U.S. Patent No. 4,482,745 discloses amethod for synthesizing 1,3-diphenyl-1,3-propanedioneby reacting acetophenone with methyl benzoate in thepresence of calcium oxide. The 1,3-diphenyl-1,3-propan-

edione may then be utilized to produce herbicidal agentssuch as 1,2-dimethyl-3,5-diphenylpyrazolium methyl sul-fate.[0008] β-diketones are also used in conjunction withzinc carboxylates in a series of chlorinated polymer sta-bilizers.[0009] For example, U.S. Patent No. 5,756,570, thecontents of which are incorporated by reference herein,discloses an electrical grade polyvinyl chloride resin com-position which avoids the use of lead-based stabilizers.U.S. Patent No. 5,756,570 discloses many heat stabiliz-ers that exclude cadmium and lead and includes epox-ides, salts of monocarboxylic acids (including zinc salts),phenolic antioxidants, organic phosphates, and β-dike-tones.[0010] U.S. Pat. No. 4,252,698, the contents of whichare incorporated by reference herein, provides an anti-yellowing additive for PVC resins which includes at leastone overbased sulfonate or phenolate compound of lith-ium, sodium, potassium, magnesium, calcium, strontium,barium, zinc, titanium, aluminum, zirconium, or tin, anda 1,3-diketone compound having 5 to 30 carbon atomsor a lithium, sodium, potassium, magnesium, calcium,strontium, barium, zinc, aluminum, tin or zirconium saltthereof. Other stabilizers may also be employed with thestabilizer composition disclosed in the ’698 patent to im-prove the overall effectiveness of the final stabilizer com-position.[0011] In addition, U.S. Patent No. 5,880,189, the con-tents of which are incorporated by reference herein, dis-closes liquid PVC stabilizers and lubricants which arebariumzinc carboxylate salt mixtures.[0012] U.S. Patent No. 6,362,264, the contents ofwhich are incorporated by reference herein, discloses astabilizer for food contact and medical grade PVC thatcontains about 10-40 parts by weight of a zinc carboxy-late, about 50-80 parts by weight of an alkyl ester of thi-odipropionic acid and about 5-20 parts by weight of aphenolic antioxidant.[0013] The non-toxic stabilizers noted above have cer-tain disadvantages. The most significant disadvantageis their lower efficiency, as demonstrated by their unsat-isfactory early color. The lower efficiency of calcium/zincstabilizers results in a higher cost than lead or barium/zinc stabilizers because they require expensive additivesas antioxidants, radical scavengers and others.[0014] Moreover, the use of halogenated resins hasrecently become more diversified and thus the process-ing conditions and the environment for their use havebecome more and more severe, which makes the stabi-lizing effect of known stabilizers insufficient.[0015] Thus it would be desirable to utilize a stabilizersystem for a halogenated resin whereby the heat stabilityof the halogenated resin can be improved avoiding dis-coloration with greater efficiency utilizing non-toxic sta-bilizers.[0016] Complexes of metal salts of organic acids incombination with β-diketone compounds, such as calci-

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um benzoate 1,3-diphenylpropane-1,3-dionate (CB-DBM), are efficient solid intermediates for halogenatedresin stabilizers. When used jointly with other low toxicityintermediates, such as zinc or magnesium intermediates,these stabilizer complexes can replace previously usedmixed metal stabilizers containing cadmium, lead and/orother heavy metal compounds.[0017] The process for preparing these stabilizer com-plexes consists of a Claisen condensation of low costraw materials, which include the following:

a) a ketone of structure:

where R1 and R2 can be selected from the groupconsisting of H, methyl, C1-C20 alkyl, C2-C20 alkenyl,aryl, aryl that is mono or poly substituted with C1-C15alkyl, C1-C4 alkoxy, or arylalkyl;b) an ester of structure:

where R4 is selected from the group consisting ofC1-C5 alkyl, aryl, and aryl that is substituted withC1-C4 alkyl, and R3 is selected from the group con-sisting of aryl, substituted aryl, C1-C20 alkyl, andC2-C20 alkenyl;c) a base such as calcium oxide, calcium hydroxide,barium oxide, barium hydroxide, potassium hydrox-ide, potassium oxide, sodium hydroxide, or sodiumoxide; andd) a solvent such as an aromatic hydrocarbon, alkylor aryl ether, dialkylsulfoxide, or the same ester usedfor the condensation.

[0018] The process does not involve the use of toxicor corrosive catalysts such as sodium methoxide, sodiumamide, sodium hydride, and other similar compoundsnormally used in the manufacture of β-diketones.[0019] The resulting stabilizer complexes can be com-bined with other low-toxic intermediates, such as thosebased on zinc. The resulting stabilizers are more efficientthan known heavy metal stabilizers, without the toxicity

associated with heavy metals. Another advantage of us-ing the stabilizer complexes formed in accordance withthe present invention in the formulation of halogenatedresin stabilizers is that there is no need to add additionalβ-diketones such as 1,3-diphenylpropane-1,3-dione (al-so known as dibenzoylmethane (DBM)) to the stabilizer,which reduces costs of production.[0020] Resins obtained with these stabilizers have en-hanced heat stability and resistance to discoloration with-out the toxicity associated with other known stabilizers.[0021] FIG. 1 shows the thermal stability of a PVC com-pound formulated for wire and/or cable insulation thatcontains 5 parts per hundred (phr) of a calcium/zinc sta-bilizer based on CBDBM. The same PVC compound con-taining a barium based stabilizer was used as a control.[0022] FIG. 2 shows the dielectric strength of a PVCcompound formulated for wire and/or cable insulationthat contains 5 phr of calcium/zinc stabilizer based onCBDBM. The same PVC compound containing a bariumbased stabilizer was used as a control.[0023] FIG. 3 shows the thermal stability of a PVC com-pound formulated for wire jacketing that contains 3 phrof calcium/zinc stabilizer based on CBDBM. The samePV C compound treated with a barium based stabilizerwas used as a control.[0024] FIG. 4 shows the dielectric strength of a PVCcompound formulated for wire jacketing that contains 3phr of calcium/zinc stabilizer based on CBDBM. Thesame PVC compound containing a barium based stabi-lizer was used as a control.[0025] FIG. 5 shows the thermal stability of a PVC com-pound formulated for use in an automotive interior thatcontains 2 phr of calcium/zinc stabilizer based on CB-DBM. The same PVC compound containing a bariumbased stabilizer was used as a control.[0026] FIG. 6 shows the thermal stability of a PVC com-pound formulated for use in automotive interiors havinglow fog characteristic that contains 2 phr of calcium/zincstabilizers based on CBDBM. The same PVC compoundcontaining a barium based stabilizer was used as a con-trol.[0027] FIG. 7 shows the dielectric strength of a PVCcompound formulated for wire and THWN cable (Ther-moplastic High temperature Wet Nylon-coated) flame re-tardant, moisture and heat resistant thermoplastic insu-lation that contains 5 phr of CBDBM based stabilizers.Barium and calcium based stabilizers were used as con-trols.[0028] FIG. 8 shows the dielectric strength of a PVCcompound formulated for wire and cable insulation thatcontains 4.5 phr of a CBDBM based stabilizer. Bariumand two calcium based stabilizers were used as controls.[0029] In accordance with the present disclosure, hal-ogen resins stabilized with a complex based stabilizer,the stabilizer complexes themselves, and methods fortheir production are disclosed.[0030] The general process for the production of thecomplexes is a Claisen condensation of certain starting

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components and precipitation with water and heptane,utilizing:

a) a ketone of structure:

where R1 and R2 can be selected from the groupconsisting of H, methyl, C1-C20 alkyl, C2-C20 alkenyl,aryl, aryl that is mono or poly substituted with C1-C15alkyl, C1-C4 alkoxy, or arylalkyl ;

b) an ester of structure:

where R4 is selected from the group consisting ofC1-C5 alkyl, aryl, and aryl that is substituted withC1-C4 alkyl, and R3 is selected from the group con-sisting of aryl, substituted aryl, C1-C20 alkyl, andC2-C20 alkenyl;

c) a base selected from the group consisting of cal-cium oxide, calcium hydroxide, barium oxide, bariumhydroxide, potassium hydroxide, potassium oxide,sodium hydroxide and sodium oxide in the presenceof a solvent selected from the group consisting of anaromatic hydrocarbon, alkyl or aryl ether, dialkylsu-foxide, or the same ester used for the reaction, toform a reaction mixture containing a stabilizer com-plex;

d) contacting the reaction mixture containing the sta-bilizer complex with water, organic solvent or com-bination thereof to precipitate the stabilizer complexfrom the reaction mixture; and

e) recovering the stabilizer complex, which is a saltof a metal selected from the group consisting of so-dium, potassium, calcium and barium.

[0031] In some embodiments, the reaction mixture iswashed with water to remove any excess base or unde-sirable by-products formed during the reaction. The re-

action mixture may also be washed with an organic sol-vent, such as heptane, to remove any excess ester fromthe stabilizer complex. Washing with water and an or-ganic solvent will also help precipitate the stabilizer com-plex from the reaction mixture.[0032] Preferably, the ketone is a methyl ketone pos-sessing aliphatic or aromatic radicals such as acetophe-none, stearylmethyl ketone, laurylmethylketone, palmit-ylmethylketone, caprylmethylketone, capronilmethylke-tone, caprilylmethylketone; the ester is a substituted alkylbenzoate or naphthenate, such as methyl benzoate, ethylbenzoate, an aliphatic ester, such as methyl stearate,and the base is calcium oxide, calcium hydroxide, bariumhydroxide, barium oxide, potassium hydroxide, potassi-um oxide, sodium hydroxide, or sodium oxide.[0033] In a preferred embodiment, the stabilizer com-plex is CBDBM. CBDBM can be prepared by mixing fromabout 0.25 to about 3.5 moles of acetophenone with fromabout 1 to about 20 moles of methyl benzoate in the pres-ence of from about 0.25 to about 7 moles of calcium oxideat a temperature range of from about 150° to about 250°C for from about two to about six hours under a nitrogenatmosphere. Methyl alcohol is continuously removed asit is formed. The CBDBM produced by this reaction isthen precipitated by a successive addition of 0 to about800 mL of water, 0 to about 800 mL of heptane, and 0mL to about 550 mL of water. Washing with water re-moves Ca(OH)2 formed during the reaction. Washingwith a solvent such as heptane will remove any methylbenzoate from the CBDBM. Methyl benzoate is undesir-able because it is volatile and therefore is inappropriatein a PVC stabilizer. The precipitate is then filtered undervacuum, washed with heptane, and dried to provide aCBDBM complex which is substantially free of unreactedcalcium oxide and methyl benzoate.[0034] Instead of calcium oxide, barium hydroxide, po-tassium hydroxide or sodium hydroxide may be utilizedto form barium complexes, potassium complexes andsodium complexes respectively. Because of environ-mental concerns with respect to the use of barium, com-plexes utilizing other bases are preferred, with calciumoxide and/or calcium hydroxide being most preferred. Inaddition, similar stabilizer complexes can be obtained bythe condensation of other esters, such as substitutedalkyl benzoates and naphthenates, or aliphatic esterssuch as alkyl stearate, with methyl ketones possessingaliphatic or aromatic radicals. For example, an ethyl ben-zoate and a stearylmethyl ketone, or methyl stearate withacetophenone may be combined to produce a stearyl-benzoylmethane complex.[0035] The stabilizer complexes produced in accord-ance with the present invention are a multifunctional com-ponent of a halogenated resin, e.g. PVC, stabilizer. So,for example, where the complex is CBDBM, the calciumbenzoate portion of the complex can act as an acid scav-enger (e.g., HCl scavenger); the CaDBM portion of thecomplex can act as an HCl scavenger, an allylic chlorinescavenger, and a complexing agent for zinc or other met-

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al stabilizer. In addition, since a β-diketone, DBM, is partof the CBDBM complex, there is no need to separatelyadd β-diketone to the halogenated resin stabilizer, there-by reducing costs.[0036] The stabilizer complexes produced in accord-ance with the present invention may then be combinedwith other components to form stabilizers useful for im-parting enhanced heat stability and resistance to discol-oration to a halogenated resin. These usually used com-ponents include low or non-toxic intermediates such asorganic acid metallic salts, organic phosphites, organotincompounds, metal hydroxides, metal oxides, polyols, ni-trogen-containing nonmetallic compounds, epoxy com-pounds, etc. Further, it causes no inconvenience to com-pound, according to necessity, plasticizers, pigments,dyes, fillers, foaming agents, antistatic agents, anti-fog-ging agents, plate-out preventing agents, surface treat-ing agents, lubricants, flame retardants, antioxidants, ul-traviolet absorbers, crosslinking agents, fluorescencepigments, brighteners, fungicides, germicides, process-ing aids, impact modifiers, etc. The resulting stabilizershave better efficiency than heavy metal stabilizers with-out the toxicity associated with the heavy metals.[0037] In general and for most applications, as a mix-ture with other low toxic intermediates, such amount ofthe complex can vary from about 2% to about 70%, pref-erably from about 4% to about 20%, and most preferablyfrom about 5% to about 10% weight parts per hundredweight parts of the stabilizer. Those stabilizers may beused from about 0.5 to about 10, preferably from about1 to about 7, and more preferably from about 1 to about5 weight parts per hundred parts of halogen-containingresin (phr).[0038] Examples of additional stabilizers that may becompounded with the stabilizer complexes of this inven-tion are low toxicity stabilizers including metal soaps ofrelatively long-chain carboxylic acids. Familiar examplesare stearates and oleates. Alkyl benzoic acids are alsoincluded under metal soaps. Metals that may be men-tioned are Li, Na, K, Mg, Zn, and Al. Use is often madeof what are known as synergistic mixtures, such as mag-nesium/zinc, calcium/zinc, or calcium/magnesium/zincstabilizers. The metal soaps can be employed individu-ally or in mixtures.[0039] Specific examples which may be mentioned arethe zinc and magnesium salts of monovalent carboxylicacids such as acetic, propionic, butyric, valeric, hexanoic,enanthic, octanoic, neodecanoic, 2-ethylhexanoic, pel-argonic, decanoic, undecanoic, dodecanoic, tridecanoic,myristic, palmitic, isostearic, stearic, 12-hydroxystearic,behenic, benzoic, p-tert-butylbenzoic, 3,5-di-tert-butyl-4-hydroxybenzoic, toluic, dimethylbenzoic, ethylbenzoic,n-propylbenzoic, salicylic, p-tert-octysalicylic; magnesi-um and zinc salts of the monoesters of divalent, carbox-ylic acids such as malonic, succinic, glutaric, adipic, fu-maric, pentane-1,5-dicarboxylic, hexane-1,6-dicarboxy-lic, heptane-1,7-dicarboxylic, octane-1,8-dicarboxylic,sorbic, phthalic, isophthalic, terephthalic and hydroxyph-

thalic acid; and of the di- or triesters of the tri- or tetrav-alent carboxylic acids such as hemimellitic, trimellitic, py-romellitic and citric acid. Preference is given to magne-sium and zinc carboxylates of carboxylic acids having 7to 18 carbon atoms (metal soaps in the narrow sense),such as, for example, benzoates or alkanoates, prefer-ably stearate, oleate, laureate, palmitate, behenate, hy-droxystrearates, dihydroxystearates or 2-ethylhex-anoate. Particular preference is given to stearate, oleateand p-tert-butylbenzoate. Overbased carboxylates, suchas overbased zinc octoate may also be used. If desired,it is also possible to employ a mixture of carboxylates ofdifferent structures. Preference is given to compositionscontaining a zinc compound. Alkyltin mercapto carboxy-lates or carboxylates can also be used as additional heatstabilizers, preferably mono or di methyl, butyl, octyl tinderivatives with alkyl thioglycolates, alkyl mercaptopro-pionates and carboxylates.[0040] The additive herein may also be advantageous-ly combined with metal perchlorates, preferred perchlo-rates being sodium, lithium, potassium, calcium, alumi-num, zinc and magnesium perchlorates, in known andconventional amounts.[0041] Examples of fillers can be one or more of thegroup consisting of calcium carbonate, dolomite, wollas-tonite, magnesium oxide, magnesium hydroxide, sili-cates, clay, talc, glass fibers, glass beads, wood flour,mica, metal oxides, metal hydroxides, carbon black,graphite, rock flour, heavy spar, glass fibers, talc, kaolinand chalk. The fillers can be employed in an amount ofpreferably at least 1 part, for example, from 5 to 200,judiciously from 10 to 150 and in particular, from 15 to100 parts by weight per 100 parts by weight of PVC.[0042] Examples of lubricants can be selected fromthe group consisting of montan wax, fatty acids, fatty acidesters, PE waxes, amide waxes, chlorinated paraffins,glycerol esters, fatty ketones, silicone-based lubricantsand combinations thereof. Calcium stearate is preferred.[0043] Examples of plasticizers can be selected fromthe group consisting of phthalates, esters of aliphatic di-carboxylic acids, trimellitates, citrates, epoxy plasticiz-ers, polymer placticizers, phosphoric esters, paraffins,hydrocarbons, monoesters, pentaerythritol esters andglycol esters.[0044] Examples of pigments can be selected from thegroup consisting of TiO2 zirconium oxide-based pig-ments, BaSO4, zinc oxide (zinc white) and lithopones(zinc sulfide/barium sulfate), carbon black, carbon black/titanium dioxide mixtures, iron oxide pigments, Sb2O3,(Ti, Ba, Sb) O2, Cr2O3 spinels, such as cobalt blue andcobalt green, Cd (S, Se), ultramarine blue, organic pig-ments for example, azo pigments, phthalo-cyanine pig-ments, quinacridone pigments, perylene pigments, diket-opyrrolopyrrole pigments and anthraquinone pigments.[0045] The polymers or resins to which the complexesof this invention are added, optionally in combination withone or more known or conventional additives, are thehalogen-containing organic polymers. These polymers

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include homopolymers such as the polyvinyl chloride-type polymers, e.g., polyvinyl chloride and polyvinylidenechloride. These polymers can also include copolymersformed by the copolymerization of vinyl chloride with oth-er unsaturated monomers. Unsaturated monomers canbe compounds which contain polymerizable carbon-to-carbon double bonds and include alpha olefins such asethylene, propylene and 1-hexene; acrylates, such asacrylic acid, ethyl acrylate, acrylonitrile; vinyl monomers,such as styrene, vinyl acetate and/or maleates such asmaleic acid, maleic anhydride and maleic esters. Partic-ularly preferred resins to which the compounds of thisinvention are added are the chlorine-containing poly-mers, particularly PVC, and compositions containingthese resins. These polymers also include chlorinatedpolyolefins or chlorinated PVC.[0046] The stabilized halogenated resins can then beemployed as components of known products including,but not limited to, flexible PVC products such as insulationfor wire and cable products and skin compositions for thesurfaces of automotive interior panels, including thoseexhibiting low fog characteristics, i.e., a reduced tenden-cy of the resin to volatilize, by which is meant that theresin emits a reduced amount of, and preferably little orno, compounds into the ambient atmosphere when theresin is exposed to moderate heat, typically temperaturesranging from about 60°C to about 130°C (140°F to270°F). The resins can be also used in, but not limitedto, rigid PVC products such as window profiles, pipes,and siding.[0047] In order for the invention to be better under-stood, the following examples are given by way of illus-tration only.

EXAMPLE 1

[0048] CBDBM was prepared by a Claisen condensa-tion of acetophenone and methylbenzoate using calciumoxide as the base. The condensation procedure consist-ed of heating acetophenone (270.3 g; 2.25 mol), methylbenzoate (183 g; 13.5 mol), and calcium oxide (168.24g; 2.7 mol) at 195-200°C with stirring for 3.5 hours, in a5 L round bottom flask, under a stream of nitrogen. Duringthe reaction, methanol was collected by distillation. CB-DBM was precipitated by successive addition, under vig-orous stirring, of water (700 mL), heptane (700 mL), andafter several minutes, 450 mL more of water. The pre-cipitate was filtered under vacuum through a Buchnerfunnel with paper filter, and the material was washed sev-eral times with heptane (4,355 mL total washes) and driedunder vacuum. 962.0 g of CBDBM was obtained, with acontent of 42 % DBM (measured by UV absorption of asolution in DMSO). This represents a yield of 80% for thecondensation reaction, based on acetophenone. Thecontent of calcium was 10.7%. The ratio of benzoate toDBM was 1.17 mol/mol.[0049] 80% of the heptane used was recovered by dis-tillation. 1045.22 g of unreacted methyl benzoate was

recovered by vacuum distillation (100-110°C @ 15-20mmHg) (85.3% recovery).

EXAMPLE 2

[0050] The reaction was carried out as in Example 1,on a 0.5 L scale. Acetophenone (30.05 g; 0.25 mol), me-thyl benzoate (204.2 g; 1.5 mol), and calcium oxide (18.7g; 0.3 mol) were heated at 195-200°C with stirring for 3.5hours, in a 0.5 L round bottom flask, under a stream ofnitrogen. During the reaction, methanol was collected bydistillation. After the condensation, the reaction mixture(136.9 g) was stirred for a few minutes with heptane (250mL). After decanting and separating the heptane, treatingagain with heptane (200 mL), filtering under vacuum, andwashing three times with heptane (250 mL, 75 mL, 75mL), 67.42 g of calcium DBM complex was obtained. UVanalysis showed 40.17. weight % of DBM, which corre-sponds to a yield for the condensation of 83 % based onacetophenone.[0051] In Examples 3-8 below, the heat stability of sev-eral PVC formulations was examined using CBDBM asa replacement for barium intermediates. PVC sheetswere milled at 170°C and strips were tested using a Ma-this oven at 190°C and 204°C. Red, green and blue(RGB) reflectances were measured with a scanner, usingFloScan software (Dr. Stapfer GmbH., Germany). RGBextinctions, which are proportional to the molar concen-trations of double bonds, were calculated as previouslydescribed (R. Bacaloglu, U. Stewen, J. Vinyl AdditiveTechnol. vol. 7, No. 3, 149-155 (2001)). The test controlswere barium based commercial stabilizers available fromCrompton Corp.[0052] Dielectric strength measurements were carriedout on dry and wet (soaked in water for 24 hours) presspolished sheets.

EXAMPLE 3

Wire and Cable Application.

[0053] 5 phr of a calcium/zinc stabilizer based on CB-DBM was added to PVC compound. A barium based sta-bilizer was used as a control. PVCs treated with thesestabilizers were heated to a temperature of 204°C anddiscoloration (Ergb) of the PVC compounds was deter-mined over time; the results of these measurements areset forth in Fig. 1. The dielectric strengths of the PVCcompounds containing these stabilizers are set forth inFig. 2.

EXAMPLE 4

Wire Jacketing Application.

[0054] 3 phr of two calcium/zinc stabilizers based onCBDBM Stabilizer were added to PVC compound. A bar-ium based stabilizer was used as a control. PVC com-

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pounds containing these stabilizers were heated to atemperature of 204°C and the discoloration (Ergb) of thePVCs was determined over time; the results of thesemeasurements are set forth in Fig. 3. The dielectricstrengths of the PVC compounds containing these sta-bilizers are set forth in Fig. 4.

EXAMPLE 5

Automotive Interior Application.

[0055] 2 phr of two calcium/zinc stabilizers based onCBDBM Stabilizer were added to PVC compound. A bar-ium based stabilizer was used as a control. PVC com-pounds containing these stabilizers were heated to atemperature of 190°C and the discoloration (Ergb) of thePVCs was determined over time; the results of thesemeasurements are set forth in Fig. 5.

EXAMPLE 6

Automotive Low Fog Application.

[0056] 2 phr of two calcium/zinc stabilizers based onCBDBM Stabilizer were added to a PVC compound. Abarium based stabilizer was used as a control. PVC com-pounds containing these stabilizers were heated to atemperature of 204°C and the discoloration of the PVCs(Ergb) was determined over time; the results of thesemeasurements are set forth in Fig. 6.

EXAMPLE 7

Wire and Cable THWN Insulation Application.

[0057] 5 phr of three calcium/zinc stabilizers based onCBDBM Stabilizer were added to a PVC compound. Abarium based stabilizer and a calcium based stabilizerwere used as controls. The dielectric strengths of PVCstreated with these stabilizers are set forth in Fig. 7.

EXAMPLE 8

Wire and Cable Application.

[0058] 4.5 phr of a stabilizer based on CBDBM wasadded to a PVC compound. A barium based stabilizerand two calcium based stabilizers were used as controls.The dielectric strengths of PVCs treated with these sta-bilizers are set forth in Fig. 8.[0059] It will be understood that various modificationsmay be made to the embodiments disclosed herein.Therefore, the above description should not be construedas limiting, but merely as exemplifications of preferredembodiments. Those skilled in the art will envision othermodifications within the scope and spirit of the claimsappended hereto.

Claims

1. A method of preparing a stabilizer complex whichcomprises reacting:

a) a ketone of the structure:

where R1 and R2 are selected from the groupconsisting of H, methyl, C1-C20 alkyl, C2-C20alkenyl, aryl, aryl that is mono or poly substitutedwith C1-C15 alkyl, C1-C4 alkoxy, and phenyla-lkyl;b) an ester of the structure:

where R4 is selected from the group consistingof C1-C5 alkyl, aryl, and aryl that is substitutedwith C1-C4 alkyl, and R3 is selected from thegroup consisting of aryl, substituted aryl, C1-C20 alkyl, and C2-C20 alkenyl;c) a base selected from the group consisting ofcalcium oxide, calcium hydroxide, barium oxide,barium hydroxide, potassium hydroxide, potas-sium oxide, sodium hydroxide and sodium oxidein the presence of a solvent selected from thegroup consisting of an aromatic hydrocarbon,alkyl or aryl ether, dialkylsufoxide, or the sameester used for the reaction, to form a reactionmixture containing a stabilizer complex;d) contacting the reaction mixture containing thestabilizer complex with water, organic solvent orcombination thereof to precipitate the stabilizercomplex from the reaction mixture; ande) recovering the stabilizer complex, which is asalt of a metal selected from the group consistingof sodium, potassium, calcium and barium.

2. The method according to Claim 1 wherein the reac-tion mixture containing the stabilizer complex is con-tacted with water to dissolve unreacted componentsand precipitate the stabilizer complex from the reac-

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tion mixture.

3. The method according to Claim 1 wherein the reac-tion mixture containing the stabilizer complex is con-tacted with organic solvent to remove unreactedcomponents and to precipitate the stabilizer complexfrom the reaction mixture.

4. The method according to Claim 3 wherein the organ-ic solvent is heptane.

5. A method of preparing a stabilizer complex whichcomprises:

a) reacting acetophenone with methyl benzoateand calcium oxide to provide a stabilizer com-plex precipitate;b) contacting the reaction mixture containing thestabilizer complex with water to dissolve unre-acted calcium oxide as Ca(OH)2 and precipitateadditional stabilizer complex from the reactionmixture;c) contacting the reaction mixture containing thestabilizer complex with organic solvent to re-move methyl benzoate present on the stabilizercomplex and precipitate additional the stabilizercomplex from the reaction mixture; and,d) recovering the stabilizer complex which issubstantially free of unreacted Ca(OH)2 andmethyl benzoate.

6. A method according to claim 5 wherein the organicsolvent is heptane.

7. The method according to claim 1 wherein the reac-tion mixture containing the stabilizer complex is con-tacted with water and organic solvent.

Patentansprüche

1. Verfahren zur Herstellung eines Stabilisatorkomple-xes, umfassend das Umsetzen:

a) eines Ketons der Struktur:

worin R1 und R2 gewählt sind aus der Gruppebestehend aus H, Methyl, C1-C20-Alkyl,C2-C20-Alkenyl, Aryl, Aryl, welches mit

C1-C15-Alkyl, C1-C4-Alkoxy und Phenylalkylmono- oder polysubstituiert ist;b) eines Esters der Struktur:

worin R4 gewählt ist aus der Gruppe bestehendaus C1-C5-Alkyl, Aryl und Aryl, welches mitC1-C4-Alkyl substituiert ist, und R3 gewählt istaus der Gruppe bestehend aus Aryl, substitu-iertem Aryl, C1-C20-Alkyl und C2-C20-Alkenyl;c) einer Base, gewählt aus der Gruppe beste-hend aus Calciumoxid, Calciumhydroxid, Bari-umoxid, Bariumhydroxid, Kaliumhydroxid, Kali-umoxid, Natriumhydroxid und Natriumoxid, inGegenwart eines Lösungsmittels, gewählt ausder Gruppe bestehend aus einem aromatischenKohlenwasserstoff, Alkyl- oder Arylether, Dial-kylsulfoxid oder dem gleichen Ester, der für dieUmsetzung verwendet wird, um eine einen Sta-bilisatorkomplex enthaltende Reaktionsmi-schung zu bilden.d) Kontaktieren der den Stabilisatorkomplexenthaltenden Reaktionsmischung mit Wasser,organischem Lösungsmittel oder einer Kombi-nation davon zur Ausfällung des Stabilisator-komplexes aus der Reaktionsmischung; unde) Rückgewinnen des Stabilisatorkomplexes,welcher ein Salz eines aus der Gruppe, die ausNatrium, Kalium, Calcium und Barium besteht,gewählten Metalls ist.

2. Verfahren nach Anspruch 1, wobei die den Stabili-satorkomplex enthaltende Reaktionsmischung mitWasser kontaktiert wird zur Auflösung von nicht um-gesetzten Komponenten und zur Ausfällung desStabilisatorkomplexes aus der Reaktionsmischung.

3. Verfahren nach Anspruch 1, wobei die den Stabili-satorkomplex enthaltende Reaktionsmischung mitorganischem Lösungsmittel kontaktiert wird, umnicht umgesetzte Komponenten zu entfernen undum den Stabilisatorkomplex aus der Reaktionsmi-schung auszufällen.

4. Verfahren nach Anspruch 3, wobei das organischeLösungsmittel Heptan ist.

5. Verfahren zur Herstellung eines Stabilisatorkomple-xes, umfassend:

a) Umsetzen von Acetophenon mit Methylben-zoat und Calciumoxid zur Vorsehung eines Sta-

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bilisatorkomplexpräzipitats;b) Kontaktieren der den Stabilisatorkomplexenthaltenden Reaktionsmischung mit Wasserzur Auflösung von nicht umgesetztem Calcium-oxid als Ca(OH)2 und Ausfällung von zusätzli-chem Stabilisatorkomplex aus der Reaktionsmi-schung;c) Kontaktieren der den Stabilisatorkomplex ent-haltenden Reaktionsmischung mit organischemLösungsmittel zur Entfernung von auf dem Sta-bilisatorkomplex vorhandenem Methylbenzoatund weiterhin Ausfällung des Stabilisatorkom-plexes aus der Reaktionsmischung; undd) Rückgewinnen des Stabilisatorkomplexes,welcher im Wesentlichen frei von nicht umge-setztem Ca(OH)2 und Methylbenzoat ist.

6. Verfahren nach Anspruch 5, wobei das organischeLösungsmittel Heptan ist.

7. Verfahren nach Anspruch 1, wobei die den Stabili-satorkomplex enthaltende Reaktionsmischung mitWasser und organischem Lösungsmittel kontaktiertwird.

Revendications

1. Procédé de préparation d’un complexe stabilisateurqui comprend de faire réagir :

a) une cétone de structure :

où R1 et R2 sont choisis parmi le groupe con-sistant en H, le méthyle, un alkyle en C1-C20,un alkényle en C2-C20, un aryle, un aryle quiest mono ou poly substitué avec un alkyle enC1-C15, un alkoxy en C1-C4 et un phénylalkyle ;b) un ester de structure :

où R4 est choisi parmi le groupe consistant enun alkyle en C1-Cs, un aryle, et un aryle qui estsubstitué avec un alkyle en C1-C4, et R3 estchoisi parmi le groupe consistant en un aryle,un aryle substitué, un alkyle en C1-C20, et unalkényle en C2-C20 ;c) une base choisie parmi le groupe consistanten l’oxyde de calcium, l’hydroxyde de calcium,l’oxyde de baryum, l’hydroxyde de baryum, l’hy-droxyde de potassium, l’oxyde de potassium,l’hydroxyde de sodium et l’oxyde de sodium enprésence d’un solvant choisi parmi le groupeconsistant en un hydrocarbure aromatique, unéther alkylique ou arylique, un dialkylsulfoxyde,ou le même ester utilisé pour la réaction, pourformer un mélange de réaction contenant uncomplexe stabilisateur ;d) de mettre le mélange de réaction contenantle complexe stabilisateur en contact avec del’eau, un solvant organique ou une combinaisonde ceux-ci pour faire précipiter le complexe sta-bilisateur du mélange de réaction ; ete) de récupérer le complexe stabilisateur qui estun sel d’un métal choisi parmi le groupe consis-tant en le sodium, le potassium, le calcium et lebaryum.

2. Procédé selon la revendication 1, dans lequel le mé-lange de réaction contenant le complexe stabilisa-teur est mis en contact avec de l’eau pour dissoudreles composants n’ayant pas réagi et faire précipiterle complexe stabilisateur du mélange de réaction.

3. Procédé selon la revendication 1, dans lequel le mé-lange de réaction contenant le complexe stabilisa-teur est mis en contact avec un solvant organiquepour éliminer les composants n’ayant pas réagi etfaire précipiter le complexe stabilisateur du mélangede réaction.

4. Procédé selon la revendication 3, dans lequel le sol-vant organique est l’heptane.

5. Procédé de préparation d’un complexe stabilisateurqui comprend:

a) de faire réagir une acétophénone avec dubenzoate de méthyle et de l’oxyde de calciumpour donner un précipité de complexestabilisateur ;b) de mettre le mélange de réaction contenantle complexe stabilisateur en contact avec del’eau pour dissoudre l’oxyde de calcium n’ayantpas réagi en tant que Ca(OH)2 et faire précipiterle complexe stabilisateur additionnel du mélan-ge de réaction ;c) de mettre le mélange de réaction contenantle complexe stabilisateur en contact avec un sol-

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vant organique pour éliminer le benzoate de mé-thyle présent sur le complexe stabilisateur et fai-re précipiter le complexe stabilisateur addition-nel du mélange de réaction ; etd) de récupérer le complexe stabilisateur qui estsubstantiellement exempt de Ca(OH)2 n’ayantpas réagi et de benzoate de méthyle.

6. Procédé selon la revendication 5, dans lequel le sol-vant organique est l’heptane.

7. Procédé selon la revendication 1, dans lequel le mé-lange de réaction contenant le complexe stabilisa-teur est mis en contact avec de l’eau et un solvantorganique.

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