MXPA00010266A - High performance plasticizers from branched oxo alcohols - Google Patents

Abstract

A plasticizer ester prepared from the catalytic reaction of (1) at least one branched C7-C11 oxo alcohol prepared from C6-C10 olefins via hydroformylation and having at least 50%methyl branching at the beta carbon, and (2) at least one acid or anhydride.

Description

HIGH PERFORMANCE PLASTICIZERS FROM OXO BRANCHED ALCOHOLS Field of the Invention The present invention is directed primarily to a series of plasticizing esters and a method for making such esters for use in the formulation of polyvinyl chloride (PVC), such as phthalates, adipates and trimellitates. These plasticizing esters are prepared by the reaction of a dihydric, triacid or aromatic or aliphatic acid anhydride with an alcohol prepared by the hydroformylation of C6-Cl0 olefins using a catalyst based on titanium, zirconium or tin, or an acid catalyst, with the provided that the olefin contains at least 50% mono-methyl branching at the beta carbon, for example -methyl octene-1 or -methyl sctene-. It has been found that such novel plasticizers are especially useful in the manufacture of automotive interior trim applications of flexible, low-fog polyvinyl chloride (PVC). BACKGROUND OF THE INVENTION Since its introduction in the late 1960s, esters of branched C9 alcohols have continued to gain prominence as plasticizers for PVC. PVC compounds prepared with phthalate esters of branched C9 alcohols are used in many different market segments; these They include electrical cable insulation, flexible vinyl flooring, vinyl coated wallpaper, vmilo shower curtains, synthetic leather, vmilo boat covers, vmilo pool liners, vmilo stationery products or notebook covers, and waxes Esters of branched C9 alcohols are preferred over esters prepared from 2-ethexanol, because when used in PVC compounds, C9 esters yield performance advantages over C8 esters in terms of superior, improved performance resistance to water extraction, lower emissions during processing, lower specific gravity, and low temperature flexibility However, these products are slightly defensive to Cß esters as they require higher processing temperatures from 1 to 3'C and mixing times dry slightly higher Although the C9 esters offer advantages over the C8 esters with lower emissions, the level of missions is often not acceptable for certain end-uses For products used in the interior passenger compartment of automobiles, manufacturers often develop specifications on the level of emissions or "fog" that can be released when the car is in the sun. Currently, no Cß phthalate ester or branched C9 phthalate satisfies the specifications that require a minimum fog formation observed after 3 hours at 100 ° C, in a fog test apparatus To satisfy these test performance criteria, phthalate esters of branched or linear C10 and C alcohols, phthalate esters of the more costly linear C9 alcohols or trimellitic anhydride esters should be used. According to Adey and collaborators, "The Nonyl Phthalate Ester and Its Use in Flexible PVC ", Journal of Vinyl Technology, December 1990, Vol 12, No., pp. 208-11, various esters of phthalate di-nonyl, di-methyl-ethyl (alpha-branched) are currently known. ) which vary in the degree of branching, which are not yet commercially available.These include moderately branched phthalate esters (Jayflex DINP), slightly branched (Palatinol N), highly branched (type 3, 5, 5-trimethyl hexyl phthalate) , and linear C9 phthalate (70% n-nonyl, 30% various alpha-branched isomers) It is known in the industry that typical branched C9 phthalates fail in the automotive fog specifications The inventors hereof have demonstrated in the examples which are included hereinafter, which the novel phthalate esters C, - ^, trimellitate and adipate (for example, branched C9 phthalate esters, trimellitate and adipate) of the present invention, which are formed from branched Oj-Cn oxo alcohols , inesper they pass the fog test. The branched nature of these plasticizers will make them slightly more compatible than the conventional Jayflex L9P, and in this way they will perform even better in compounds of PVC These unique branched C7-C11 oxeta phthalate, tpmelitato and adipate esters have low fog properties that are highly desirable for use in automotive interior applications. Phthalate esters prepared from oxo alcohols C7-C11 according to the present invention produce a plasticizer for flexible PVC, which has all the performance advantages associated with branched, conventional phthalate C9 esters, while dry blending more quickly, that is, they are processed more quickly, than DOP. When compared to other known branched phthalate esters, phthalate esters of branched C9 oxo alcohols according to the present invention provide improved efficiency, better performance at room temperature, and lower emission release (i.e., fog) during processing. Additionally, the inventors of the present have discovered that the trimellitate esters formed in accordance with the present invention tend to mix dry more quickly than Jayflex TINTM. { tpisononil tpmelitato prepared from three moles of C9 alcohol and one mole of trimellitic anhydride). They also tend to be more efficient. The oxo tpmelitato esters according to the present invention can also replace TOTM (tr? -2-et? L hexyl tpmelitato) in automotive instrument applications and in wire and cable formulations where conventional tpmelitate esters do not They have been successful. Further, because the oxo trimellitate esters of the present invention have lower volatility, they will also have a longer useful product life. Moreover, the oxo tpmelitate esters can be used in future cable applications at l25 ' C where low volatility, improved plasticizer efficiency, and improved processability are desired The present invention also provides many additional advantages that will be apparent as described below. Compound of the Invention The present invention includes a novel series of plasticizing esters and a method for making such esters for use in the formulation of polyvinyl chloride (PVC), such as phthalates, adipates and tpmelitates Plasticizing esters according to the present invention are prepared by the reaction of at least one oxo alcohol C, -Cu prepared by hydroformylation of C6-C10 olefms comprising at least 50% methyl branching in beta carbon with at least one acid and / or anhydride, in the presence of a catalyst The present invention also includes a process for preparing a plasticizing ester comprising reacting a branched C7-C11 oxo alcohol, prepared from C6 ~ C10 defines By hydroformylation with at least one acid and / or anhydride in the presence of a catalyst, wherein said olefins comprise at least 50% methyl branching at the beta carbon The present invention also includes a polyvinyl chloride ream composition comprising polyvinyl chloride and the plasticizing esters of the present invention and, optionally, stabilizers, fillers and other well-known additives which are commonly used in the art. The polyvinyl chloride ream compositions can be used to prepare films, sheets or extruded, molded or cast products that are suitable for use in all areas of polyvinyl chloride applications. Other and further objects, advantages and aspects of the present invention will be understood by reference to the following description, in conjunction with the accompanying drawings, where similar numbers have been given to similar parties. DESCRIPTION OF THE PREFERRED EMBODIMENTS The plasticizing esters according to the present invention are prepared by esterification of acids and / or anhydrides with at least one branched C-Cn oxo alcohol. The stepping process comprises the following steps: (a) adding an excess of acid and / or anhydride and at least one branched C7-C11 oxo alcohol to a reaction vessel, with the proviso that the olefin used to form the oxo alcohol comprise at least 50% methyl branching at the beta carbon; and (b) heating the reaction mixture to a temperature around or above the boiling point of the oxo alcohol and maintaining a sufficient pressure to obtain boiling. of the reaction mixture, thereby converting the acid and / or anhydride and the oxo alcohol C, -Cu branched into a phthalate ester, tpmelite or adipate, and removing water and a portion of the alcohol from the reaction vessel. The esterification process may also include one or more of the following steps: remove the excess acid by stripping with nitrogen or water vapor; add adsorbents such as alumina, silica gel, activated carbon, clay and / or filtration aid to the reaction mixture after stamping but before further treatment, add water and base to simultaneously neutralize the residual organic acids and hydrolyze the catalyst (if present); filtering the solids from the ester mixture containing the bulk of the excess acid by stripping with steam or nitrogen or vacuum and recycling the acid to the reaction vessel; and removing solids from the stripped ester in a final filtration.

In certain cases, the treatment with adsorbent can occur later in the process following the stripping with water vapor. In other cases, the step of treatment with adsorbent can be eliminated from the whole process. Preferably, the plasticizing esters of the present invention are prepared by means of a reaction catalyzed with metal or acid of an aromatic or phatic acid, such as a benzene, acid or anhydrides with an oxo alcohol prepared by hydroformylation of C6 olefins. -C10. From According to the present invention, the olefin must contain at least 50% mono methyl branching at the beta carbon (for example, 2-methylene octene-1 and 2-methylene octene-2 formed by the "oxo" process). ). Preferred plasticizing esters are those which can be used for polyvinyl chloride resins. They include esters prepared from the reaction of an aliphatic oxo alcohol and an aromatic acid, wherein the aliphatic oxo alcohol is prepared by hydroformylation of a mixture of olefins which includes at least 50% of isomers having methyl substitution at the beta carbon. The aromatic acid is preferably selected from the group consisting of italic acid, tpmethyl acid, its anhydrides, and mixtures thereof. The most preferred esters are those in which the aromatic acid is italic anhydride or trimellitic anhydride and the aliphatic oxo alcohol is a branched C9 oxo alcohol prepared by hydroformylation of 2-ethyl octene-1 and / or 2-methyl-2-octene. Esterification Catalyst The process of estepfication is preferably conducted in the presence of a catalyst. Typical carboxylation catalysts are titanium, zirconium and tin catalysts such as alcoholates, carboxylates and chelates of titanium, zirconium and tin. See U.S. Patent No. 3, 056, 818 (Werber), issued October 2, 1962, and which is incorporated herein by reference.

Typical titanium alcoholates which can be used as catalysts include tetramethyl titanates, tetraethyl titanates, tetrapropyl titanates, tetraisopropyl titanates, tetrabutyl titanates, tetrapentyl titanates, tetrahexyl titanates; tetra-octyl titanates, tetranonyl titanates, tetradodecyl titanates, tetrahexa-decyl titanates, tetra-octadecyl titanates, tetradecyl titanates, tetraheptyl titanates and tetraphenyl titanates. The alkoxy groups in the titanium atom may be the same or may be different. The zircomo counterparts of the above alcoholates can be substituted in part or totally as catalysts. The titanium carboxylates which serve as esterification catalysts are polymeric materials having at least one acyl group for each titanium atom. Typical titanium acylates that can be employed as catalysts include acylates of 2 to 18 carbon atoms, such as titanium hydroxy acetate, titanium hydroxy butyrate, titanium hydroxy pentanoate, titanium hydroxy hexanoate, titanium hydroxy octanoate, hydroxy decanoate titanium, titanium hydroxy dodecanoate, titanium hydroxy tetradecanoate, titanium hydroxy hexadeca-noate, titanium hydroxy octadecanoate, titanium hydroxy oleate, soy titanium hydroxy acylate, linseed hydroxy titanium acylate, castor titanium hydroxy acylate , tallow oil, titanium hydroxy acylate, acylate coconut titanium hydroxy, titanium methoxy acetate, titanium ethoxy butyrate, titanium isopropoxy pentanoate, titanium butoxy hexanoate, titanium isopropoxy octanoate, titanium isopropoxy decanoate, titanium isopropyl dodecanoate, titanium isopropoxy tetradecanoate, titanium isopropoxy hexadecanoate , isopropoxy titanium octadecanoate, isopropoxy titanium oleate, isopropoxy acylate of soy titanium, isopropoxy acylate of linseed, acylate isopropoxy of coconut The alkoxy group of the acylate can vary from 1 to 20 carbon atoms The corresponding zirconium carboxylates can be used as catalysts The titanium chelates are formed by reacting a titanium compound with a polyfunctional molecule, including polyols, such as glycols and glycerin and ring alcohols, amino acids, hydroxy acids and polycarboxylic acids. Typical chelate esters serving as catalysts include tetra-ethylene glycol titanate, tetra-propylene glycol tita nato, tetra-butylene glycol titanate, tetra-octylene glycol titanate, and tetra-polyethylene glycol titanate, d? - (et? lylene glycol) titanate, di-isopropoxy di- (octylene glycol) titanates, dimethoxy di- (octylene glycol) titanates, dietoxy di- (octylene glycol) titanates, tetra-tethanol amine titanate, tetra-triethanol amine-N-oleate titanate, tethanol amma-N-stearate titanate, tpetanol amine-N-acid salt of linseed titanate, dibutoxy titanate, dipropoxy titanate, dimethoxy titanate, diethoxy titanate, other dialkoxy dipropoxy, dimethoxy, diethoxy titanates, and other dialkoxy di- (ammo alcohol) titanates The corresponding zirconium chelates are also useful as catalysts Selected acid catalysts can also be used in this process of esterification. Some examples of the acid catalysts are sulfuric acid, sulphonic benzene, p-toluene sulphonic acid, naphthalene sulphonic acid, aluminum sulfate, aluminum powder, n-decylbenzenesulfonic acid, n-dodecylbenzenesulphonic acid, n-nonylbenzenesulphonic acid, n-octylbenzenesulphonic acid, n-heptylbenzenesulphonic acid , n-hexylbenzenesulphonic acid, n-dodecano sulfonic acid, n-tpdecano sulfonic acid, n-tetradecano sulfonic acid, n-pentadecano sulfonic acid, n-hexadecano sulfonic acid, n-heptadecano sulfonic acid, n-octadecano sulfonic acid, acid n-nonadecane sulfonic acid, n-eicosane sulphonic acid, 3-methododecane sulfonic acid, 3-methoxy acid -5-ethyldecano sulphonic acid, 3-methodecyl-benzene sulphonic acid, 4-ethoxyl-benzene sulfonic acid, phosphoric acid, aromatic phosphonic acids (eg, organic disulfonic acids, 1,2-ethanedosulfon acid) , 1,3-propanedisulfonyl acid, m-benzene disulfonic acid, 2,5-, 2,6- or 2,7-naphthalene disulfonic acids or mixtures of these isomers, and 3, 5-oxobenodic acid sulfon? -co), formaldehyde acid reams prepared by reacting an aromatic hydrocarbon, an aldehyde, and sulfuric acid, methane disulfonic acid, methane t-sulphonic acid, hydrochloric acid, dichloride, perfluorinated resin sulphonic acid, acid ion exchange reams, chlorosulfonic acid, thionyl chloride, boron trifluoride, dihydroxy fluoride, dihydroxy fluoboric acid, and silicon tetrafluoride. Acids Carboxylic acids that undergo esterification (ie mono- or poly-basic acids, preferably d-basic or tribasic acids) can be aliphatic, cycloaliphatic or aromatic, can be substituted or unsubstituted, saturated or unsaturated, or can be physical mixtures of acids. Representative acids include acetic, hydroxyacetic, chloroacetic, bromoacetic, cyanoacetic, 5-phenylacetic, tpphenyl acetic, propionic, halopropionic, lactic, beta-hydroxy propionic, n-butyl, isobutyric, n-valépco, isovaleric, 5-phenol- valépco, n-heptanoico, caproic, pelargonic, caprylic, lauric, palmitic, lignocépco, alpha-hydroxy lignocépco, malonic, succinic, glutaric, adipic, pimelic, azelaic, sebacic, decane-1, 10-d? carboxyl? co, pentadecane -1, 15-d? Carboxyl? Co, pentacosane-1, 25-d? Carboxyl? Co, 1, 2, 3-propane t-carboxylic acid, citric acid, acrylic, alpha-chloro acrylic, beta-chloro acrylic, beta-bromo acrylic , beta-phenyl acrylic, methacrylic, vinyl acetic, crotonic, angelic, tíglico, undecilénico, oleic, erucic, linoleic, lmolénico, maleic, fumaric, mesaconic, citracónico, itacoico, mucónico, aconítico, mirístico, esteárico, isostearic, C5 and C10 branch- two (for example, 3, 5, 5-tmetmethexane? co) and C17, C19, C21, etc. branched Among the alicyclic acids are cyclopropano-carboxylic acids, cyclobutane carboxylic acids, cyclopentane carboxylic acids, cycloheptane carboxylic acids, cyclohexane carboxylic acids, 2-hydroxy cyclohexane carboxylic acids, 1,1-c-chloroppane dicarboxylic acids, 1,2-c-chlorobutane dicarboxylic acids, 1,3-c-Clobutane-dicarboxylic acid, 1,4-c-clohexane-dicarboxylic acid, c-clohexane-1, 2,3,4,5,6-hexacarb-xyloxy, cyclopentene-2-carboxylic acid, 1-c-clohexene- l-carboxylic, hydrocarbic, c-clohexadiene-1, 2-d-carboxylic acid, and 1,3-c-clohexadiene-1,4-dicarboxylic acid. Aromatic acids include benzoic acids, o-, m-, and p-chloro and bromo benzoic, o-, m- and p-hydroxy benzoic, o-, and p-nitrobenzoic, o-, m- and p-methoxy benzoic , alpha-naphthoic, beta-naphthoic, o-, m- and p-methyl benzoic, o-, m- and p-ethyl benzoic, p-phenyl benzoic, italic, isophthalic, terephthalic, italic hydroxy, 2, 3-d benzoic acid, benzene-1,2,4-carboxylic acid, benzene- 1, 3, 5-t-carboxylic acid, benzene-1, 2,4,5-tetracarboxylic acid, naphthalene benzenes and trimellitic Anhydrides Anhydrides of mono and polybasic acids can be used in place of the acids, especially when plasticizing esters are being formed. These include acetic anhydride, propionic anhydride, n-butyric anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride, maleic anhydride, mesaconic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, phthalic anhydride, benzoic anhydride, nadic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, tmethyl anhydride and mixed anhydrides of monobasic acids. Another anhydride is pyromellitic dianhydride. Alcohols Among the alcohols that can be reacted with acids and anhydrides with oxo alcohols 0, -0 ^ derived from branched C6-C10 olefins, such as 2-meth? Octene-1 and 2-meth? Octene-2 via oxo process. Among the monohydric alcohols which can be reacted with acids and anhydrides according to the present invention are, by way of example, most of the primary or unsubstituted C-Cn monohydric alkanols and alkenols, such as 3-met? l octanol and 7-met? loctanol. The term "iso" is intended to refer to a multiple isomer product made by the oxo process. It is desirable to have a branched oxo alcohol comprising multiple isomers, preferably at least two isomers. The branched oxo alcohol can be produced in the so-called "oxo" process by hydroformylation of commercial C6-C10 olefin fractions in a corresponding branched 0, -0 ^ alcohol-containing oxanation product, followed by the conversion of the oxidizing product containing oxo alcohol raw in an oxo alcohol. In order to produce oxo-alcohol commercially, the hydroformylation process is adjusted to maximize the formation of oxo-alcohol. This can be achieved by controlling the temperature, the pressure, the catalyst concentration and / or the reaction time. Subsequently, the oxalation product containing crude, demetallized alcohol is hydrogenated to convert residual oxo aldehydes into oxo alcohols. The production of branched oxo alcohols from the cobalt-catalyzed hydroformylation of an olefric feed stream preferably comprises the following steps: (a) hydroformylating an olefin feed stream by reaction with carbon monoxide and hydrogen (i.e. synthesis) in the presence of a hydroformylation catalyst or reaction conditions that promote the formation of a crude reaction product, rich in alcohol; (b) demetallizing the crude reaction product, rich in alcohol to recover therefrom the hydroformylation catalyst and a crude reaction product, rich in alcohol, substantially free of catalyst; (c) separating the crude, alcohol-free, catalyst-free reaction product into a concentrated product, rich in alcohol and an alcohol-poor product; and (d) hydrogenate the concentrated product, rich in alcohol, thereby forming an oxo alcohol. The olefinic feed stream is preferably any C6 to C10 olefin, more preferably a branched Cβ olefin. Moreover, the olefinic feed stream is preferably a branched olefin, where at least 50% of the methyl branching occurs at the beta carbon atom. The hydroformylation and subsequent hydrogenation of the reaction of the crude hydroformylation product is capable of producing branched C7 to Cn alcohols, more preferably branched C9 oxo alcohol. Each of the branched C7 to Cxl oxo alcohols typically comprises, for example, a mixture of branched oxo alcohol isomers, for example the branched C9 oxo alcohol comprises 2-methyl octene-1 and 2-methyl octene-2. The performance of several C9 phthalate esters has been compared to the performance of the phthalate ester Cg of the present invention which is prepared from the branched C9 oxo alcohol made from 2-methyl octene-1 and 2-methyl octene-2 via the oxo process, with the condition that at least 50% of the olefins have methyl branching at the beta carbon atom. The phthalate ester of the present invention demonstrated certain performance advantages in several key areas on both Jayflex DINP and Palatinol N, which are two commercial phthalate esters that are also derived from branched C9 alcohol. Jayflex DINP is prepared from a mixture that is predominantly dimethyl heptanols and trimethyl hexanols. Palatinol N is prepared from a mixture of methyl octanols and di-ethyl heptanols prepared by hydroformylation of dimethyl butenes. A branched C9 oxo alcohol was prepared from a mixture of 2-methylene octene-1 and 2-methylene octene-2 having the distribution of isomers indicated in Table 1. This table was developed from data from alcohol and compositional isomers predicted based on known oxo selectivity model studies carried out on selected olefms. These data are based on the assumption that 2-methylene octene-1 and 2-methylene octene-2 will exhibit the same selectivity in the oxo process. If the selectivity is different, then the percentages reported for 3-methylene octanol and 7-methylene octanol in Table 1 can be reversed. Table 1 Predicted Compositions of Oxo Alcohol C9 Branched Compound% 1-nonanol 6.4 2-methylene octanol 2.4 2-et? L heptanol 0.8 2-prop? L hexanol 0.3 2-but? L pentanol 0.1 3-met? L octanol 42.3 7-methylene octanol 27.9 2,6-d? Met? L heptanol 13 5 2-et? L-5-met? L hexanol 3 6 2,2-d? Methanol heptanol 0.9 2-? Soprop? L hexanol 0.9 2-secbut? Pentanol 0.9 Gas chromatography data were generated for three C9 alcohols, ie (1) branched C9 oxo alcohol (isononyl alcohol , di heptanoles ethyl and tpmetil hexanoles); (2) linear, slightly branched C9 alcohol (ie, a 65-75% mixture of n-nonanol, with lower amounts of 2-methylene octanol, 2-ethanol heptanol and 2-propyl hexanol Jayflex L9P), and (3) slightly branched C9 alcohol, prepared by hydroformylation of butene dimer (Palatinol N) Additionally, a theoretical GC chromatogram was generated for the branched C9 oxo alcohol according to the present invention (i.e. different scale of retention time.) It has been found that the 2-meth and 6-methylene heptanols had the same retention times It is assumed that the 2-methy and 7-methylene octanols similarly will have the same Retention Times Unexpectedly, the GC pattern of the branched C9 oxo alcohols was different from the GC pattern of the other known C9 alcohols Table 2 lists a branching summary of the three reference alcohols, as compared to the value for the branched C9 oxo alcohol formed according to the present invention The branching index refers to the number of branches per average molecule. Alcohol derived from The branched C ole olef of the present invention, with a composite branching index of 1 1 is significantly lower than that reported for the slightly branched C 9 -based alcohol This reduced branching results in some notable performance differences It is found that the plasticizing viscosity for the phthalate ester of the present invention it is between that of Palat ol N (ie, a phthalate ester C9 slightly branched) and Jayflex L9P (ie, a linear C9 phthalate) Table 2 Alcohol Data C9 C9 Slightly Branched Octens Branches Palat. Nol N Jayflex DINP Jayflex L9P Oxo Ale Alcohol branch of Straight Chain 4 < 1 72 6 % of Branched Monkey 50 15 28 74 % of branched out 44 66 < 1 20 % of Tri branched 2 18 < 1 < 1 branching index 1 44 2 01 0 28 1 14 Plast ficante v? ST20 C cSt 80 100 54 67 Plasticizer gr esp 0 975 0 973 0 969 0 976 'a BASF data for C9 alcohol Dimersol bPredec? Do cComparac? On with data from Palatinol N and Jayflex DINP only Moreover, the esterification of phthalic anhydride with the branched C9 oxo alcohol of the present invention demonstrated reactivity similar to that of the conventional C9 primary alcohols, although no problems of quality with the phthalate ester were anticipated. The COPPCO database, which is a computer model used to predict plasticizer performance in flexible PVC, contains plasticizer performance information about four C9 phthalates: Jayflex DINP, Jayflex L9P, Palati-Nol N, and a -n-nonyl phthalate. The COPPCO performance predictions for these phthalates (at 50 phr) as well as that of Palatinol 711P are listed in Table 3. These data show that, as the branching rate is reduced, the efficiency of the plasticizer is increased, the performance is increased to low temperature, and the weight loss observed with oven aging and extraction with soapy water is reduced. These observations are consistent with those noted by Wadey et al., "The Nonyl Phthalate Ester and Its Use in Flexible PVC", Journal of Vinil Technology, December 1990, vol. 12, No. 4, p. 642. The performance of the phthalate ester derived from isooctene according to the present invention (ie, iso-C9 DINP) is estimated by correlating the plasticizing performance of these C9 phthalates with the branching index. These data are also displayed in Table 3.

Table 3 Performance COPPCO of Esters Ftalato C9 in flexible PVC Property Jayflex Palatmol Palatmol Jayflex Dl-n- Iso-C9 DINPa 711P N L9P C9P DINPb Shore A hardness 84 81 83 80 80 82 Hardness Shore D 31 29 30 28 27 29 Module at 100%, N / m2 12 5 11 8 11 8 10 7 10 8 11 5 Elongac? On% 329 342 365 335 332 335 Clash-Berg Tf C 24 -32 -26 33 -36 -28 Temp Quebr C 32 41 35 -43 -46 -38 Weight loss (7d @ 100 C) 5 4 5 6 4 0 3 4 2 4 4 0 Volatile, carbon black,% 1 0 1 1 1 3 0 9 0 9 0 9 Loss of water "soapy,% 2 0 3 4 1 8 1 6 1 4 1 7 Composite gravity 1 221 1 221 1 222 1 220 1 216 1 221 Dry mix time, ram 1 9 1 0 1 6 1 0 1 0 1 2 aPCOPCO predicted values, PVC, 100 parts, plasticizer, 50 phr, stabilizer, 2 phr b Extrapolated data, from COPPCO data versus branching index (ie, a plasticizer formed from branched C9 oxo alcohol) In terms of performance ranges, Palatinol N falls in the middle range between Jayflex DINP and DINP isocyte derived from the present invention. DINP derived from isooctene shows performance advantages over Palatmol N with higher efficiency, better performance at low temperature, and reduced weight loss, but in a manufacturing environment these differences can be difficult to quantify. However, the differences between Jayflex DINP and DINP derived from isooctene are statistically significant (but still lower than the performance differences between DOP (di-2-ethylhexyl phthalate) and Jayflex DINP) both in the laboratory and in a manufacturing environment, the isocyte-derived plasticizer having several areas of improved plasticizer performance. Jayflex DINP is less efficient, which translates into a slight advantage in volume coating, assuming that the specific gravity projections are correct and that the cost ratios between the PVC resin and the plasticizer are favorable. The Wadey data shows that there are small differences between the performance of phthalate esters prepared from 1-nonanol phthalate and 2-methyl nonanol. In this way, it would be expected that if a linear C9 alcohol is physically mixed, slightly branched (i.e., a 65-75% mixture of n-nonanol, with lower amounts of 2-methyl octanol, 2-ethyl heptanol and 2-propyl hexanol) with the branched C9 oxo alcohol of the present invention, will a reduction in plasticizer performance. A 10% addition of the branched C9 oxo alcohol to linear C9 alcohol, slightly branched, would give a reduction of l'C in the low temperature performance of the plasticizers. Other performance properties must remain unaffected. In this way, it may be desirable to intentionally intentionally mix significant levels of linear, slightly branched C9 alcohol with the branched C9 oxo alcohol before esterification.

The present invention also includes a polyvinyl chloride resin composition comprising polyvinyl chloride and the plasticizing esters of the present invention. The plasticizing esters of the present invention are formed from the reaction of an aliphatic oxo alcohol and an aromatic acid, wherein the aliphatic oxo alcohol is prepared by hydroformylation of a mixture of olefins, wherein the olefins comprise at least 50% methyl branching in the beta carbon. The polyvinyl chloride resin composition comprises a polyvinyl chloride, typically unplasticized, in an amount of about 25 to 99.99% by weight of the composition and a plasticizing ester of the present invention in an amount of about 0.01 to 75. % by weight of the composition. The polyvinyl chloride resin formulation containing the unique plasticizers of the present invention is exemplified by the following basic formulations: Reagent Ex. 1 Ex. 2 PVC (suspension grade, K 69), parts 100 PVC (dispersion grade, K 74), parts - 100 Plasticizer, phr resin 25,35,50 50,70,90 Liquid stabilizer Ba / Cd / Zn (phr) 2.0 2.0 Stearic acid (phr) 0.25 0.25 The polyvinyl chloride resin composition can further comprising stabilizers, fillers and other well-known additives that are commonly used in the art. Preferably, the polyvinyl chloride resin composition comprises 0.01 to 7% by weight of a stabilizer selected from compounds of calcium, barium, cadmium, zinc, lead, and mixtures thereof; and / or 0.01 to 6% by weight of a selected filler of calcium carbonate, clay, and mixtures thereof. The polyvinyl chloride resin composition of the present invention can be used to prepare films, sheets or extruded, molded or cast products which are suitable for use in all areas of polyvinyl chloride applications. The molded or cast products of the present invention are particularly suitable for use in automotive applications such as automotive interior parts. Although various embodiments according to the invention have been shown and described, it should be clearly understood that they are susceptible to numerous obvious changes to a person skilled in the art. Therefore, it is not desired to be limited by the details shown and described, but it is intended that all changes and modifications fall within the scope of the appended claims.

Claims (8)

1. CLAIMS 1. A process for preparing at least one plasticizing ester, comprising: (a) hydroformylating an olefin feed stream to form an aldehyde product comprising at least one aldehyde, wherein said olefin feed stream comprises at least one olefin selected from the group consisting of C6, C7, C7, C9, C10 aliphatic olefins, and combinations thereof, and said olefin feed stream contains at least 50% by weight of olefins having methyl branching at the beta carbon; (b) hydrogenating at least a portion of the aldehyde product of step (a) to form an alcohol product comprising at least one alcohol selected from the group consisting of a monohydric aliphatic alcohol C7, C8, C9, C10, C11 # and their combinations; and (c) reacting, in the presence of an esterification catalyst, at least a portion of said alcohol product of step (b) with an esterification reagent selected from the group consisting of an organic acid, an organic anhydride, and its combinations, to form said at least one plasticizing ester.
2. 2. The process according to claim 1, wherein said at least one alcohol is a branched C9 oxo alcohol and said at least one olefin is selected from the group that consists of 2-methyl octene-1; 2-methyl octene-2; and its combinations.
3. 3. The process according to claim 1 or 2, wherein said plasticizing ester is selected from the group consisting of phthalate esters, adipate esters, trimellitate esters, and mixtures thereof, and said esterification reagent is selected from the group consisting of bicarbides , triazides, their anhydrides and their mixtures.
4. 4. A plasticizing ester prepared by the process of claim 1, 2 or 3.
5. 5. A plasticizing ester prepared by a process comprising: (a) hydroformylating an olefin feed stream to form an aldehyde product comprising at least an aldehyde, wherein said olefin feed stream comprises at least 50% by weight of olefins having methyl branching at the beta carbon; (b) hydrogenating at least a portion of the aldehyde product of step (a) to form an alcohol product comprising at least one alcohol selected from the group consisting of a monohydric aliphatic alcohol; and (c) reacting, in the presence of an esterification catalyst, at least a portion of said alcohol product of step (b) with an esterification reagent selected from the group consisting of an aromatic acid, an aromatic anhydride, and combinations thereof, to form said at least one plasticizing ester.
6. 6. The plasticizing ester of claim 5, wherein said aromatic acid is selected from the group consisting of phthalic acid, trimellitic acid, its anhydrides, and mixtures thereof. The plasticizing ester according to claim 5 or 6, wherein said anhydride is selected from the group consisting of phthalic anhydride and trimellitic anhydride, said at least one aliphatic monohydric alcohol is a branched C9 oxo alcohol, and said feed stream of Olefins comprise olefins selected from the group consisting of 2-methyl octene-1; 2-methyl octene-2; and its combinations. 8. A polyvinyl chloride resin composition, comprising the plasticizing ester according to claim 5 and polyvinyl chloride. The polyvinyl chloride resin composition according to claim 8, further comprising: 0.01 to
7. 7.0% by weight of a stabilizer selected from the group consisting of calcium, barium, cadmium, zinc, lead, and mixtures thereof; and / or 0.01 to 6.0% by weight of a filler selected from the group consisting of calcium carbonate, clay, and mixtures thereof. 10. A film, sheet or extruded product, molding or pouring prepared from the polyvinyl chloride resin composition according to claim
8. 8.