Mixed S-alkylthiopropionic acid esters with pentaerythritol

Abstract: Mixed esters of pentaerythritol and the like with at least two different 3-alkylthiopropionic acids are provided. Each acid from which the ester is prepared has a different alkyl group. This facilitates tailoring the mixed ester for use as a stabilizer which is especially compatible with a particular polymer resin material. Preferably, each 3-alkylthiopropionic acid is prepared by a direct addition reaction between an alkylmercaptan and acrylic acid or an alkali metal salt thereof, the reaction being carried out by heating the reactants in the presence of an aqueous alkaline solution.

Description: The present invention generally relates to S-alkylthiopropionic acids which are esterified with pentaerythritol, as well as to methods for making same. More particularly, the invention relates to so-called mixed esters. The mixed esters contain multiple 3-alkylthiopropionic acid groups, at least two of the alkyl chains thereof being of different carbon chain lengths. These mixed esters are useful as stabilizers of organic materials such as polymer resins and the like, and the mixed esters can be tailored to provide properties that are especially suitable for specific stabilizer needs. Alkyl esters derived from alkylthioalkanoic acids and the like are, in general, known to be useful as stabilizers of organic materials such as polymer resins and the like which are otherwise subject to thermal and oxidative deterioration during processing, extrusion or molding, as well as during use. Esters having this general utility have been proposed and/or prepared in the past. Examples include Dexter et al US-A-3,758,549, which teaches transesterification procedures for preparation of these general types of products. Included is pentaerythritol tetrakis (3-n-dodecylthiopropionate) formed by a transesterification procedure between methyl 3-n-dodecylthiopropionate and pentaerythritol. Formation of a mixed ester is not suggested. Prior approaches such as those suggested in Kauder et al US-A-4,080,364 and Nakahara et al US-A-4,349,468 and US-A-4226991 teach the preparation of stabilizers for polyolefins by reacting an alpha-olefin with a mercaptocarboxylic acid or an ester of a mercaptocarboxylic acid. Pentaerythritol esters thereof are also described. It is mentioned that the alpha-olefins can take the form of a mixture of alpha-olefins. Typically alpha-olefin reaction schemes such as these produce unwanted isomer byproducts that, if not removed in a separate purification step, lower the quality of the pentaerythritol ester product which is produced. Alkylthiopropionic acids prepared by approaches such as these do not typically directly produce, without special purification, an alkylthiopropionic acid which exhibits a high purity characteristic which will, when reacted with pentaerythritol or the like, form an ester composition which contains a minimum of unwanted byproducts. Even when ester stabilizers are prepared as esters of pentaerythritol that have exceptional purity, the compatibility thereof with the polymers to be stabilized therewith can be limited. While, for example, the 3-dodecylthiopropionic tetraester of pentaerythritol is solid at room temperature, whereas the 3-octylthiopropionic tetraester of pentaerythritol is liquid at room temperature, compatibility of such esters with a polymer to be stabilized is not readily predictable from this or any other physical property. Compatibility is a useful property usually defined in terms of manifestations of incompatibility which develop during blending of the stabilizer with the polymer, during storage, and/or during extrusion or other formation procedures to which the stabilized polymer is subjected, and can only be determined by experiment. A stabilizer that is especially compatible with a particular polymer or polymer blend will exhibit the absence or at least minimization of any manifestation of incompatibility such as exudation of a liquid or crystallization of a solid additive on the polymer surface. A valuable consequence is that a more compatible stabilizer can be used in greater concentrations, thus resulting in enhanced stabilizing effectiveness. Variations in physical properties of the alkylthiopropionate tetraesters of pentaerythritol can be achieved by forming esters having alkyl groups of intermediate carbon chain lengths. For example, the 3-decylthiopropionate tetraester with pentaerythritol will tend to have properties generally midway between the dodecyl and octyl tetraesters, and the decyl ester would typically be less volatile than esters prepared from the octyl mercaptan, while being less waxy than esters prepared from the dodecyl mercaptan. However, because each ester molecule has alkyl mercaptan groups of the same carbon chain length, the tailorability of these stabilizers for achieving desired physical and compatibility properties for a specific polymer or polymer blend is limited. These properties can be varied on a somewhat gross scale, but it is not possible to more precisely vary or fine tune the compatibility properties of these types of stabilizers. Accordingly, it would be desirable to provide stabilizing mixed alkylthiopropionic acid esters of pentaerythritol which incorporate in the same molecule alkyl mercaptan groups which have at least two different alkyl carbon chain lengths. It is further desirable that these mixed esters be prepared in a manner such that the structure of the mixed ester thus produced can be controlled and can be reproduced on a substantially consistent basis. Achieving this objective includes the need to avoid the formation of any undesirable byproducts so that the mixed ester is still a high purity stabilizer product that can be reliably produced as one which provides desired compatibility properties. By the present invention, stabilizers for extrudable thermoplastic polymers and polymer resin blends are prepared. The stabilizers are mixed esters which are tailored to exhibit specific selected properties for providing excellent compatibility with the polymer resin or polymer resin composition. Each mixed ester has at least two different alkyl groups provided by the alkyl mercaptan from which the mixed ester stabilizer is prepared. In preparing these stabilizers, preferably a 3-alkylthiopropionic acid having an alkyl group of one carbon chain length is prepared by directly reacting the desired alkyl mercaptan with an alkali metal acrylate, the reaction being carried out in the presence of strong base catalyst, followed by acidification and collection. A different 3-alkylthiopropionic acid is prepared in the same manner by using a different alkyl mercaptan having a different alkyl carbon chain length. Additional, different 3-alkylthiopropionic acids can likewise be prepared. The thus prepared different 3-alkylthiopropionic acids are reacted with pentaerythritol, thereby forming the mixed ester stabilizer. When desired, the mixed ester product can be solvent refined. It is accordingly a general object of the present invention to provide alkylthiopropionate mixed esters and an improved process for preparing same. Another object of this invention is to provide an improved process for preparation of an improved mixed ester from at least two different S-alkylthiopropionic acids which are prepared by a direct addition reaction mechanism, as well as the mixed ester produced thereby. Another object of the present invention is to provide improved alkyl mercaptan mixed ester stabilizers which are tailorable to achieve enhanced compatibility with any one of a wide variety of extrudable thermoplastic polymer resins or polymer resin compositions. Another object of this invention is to provide an improved process for preparing mixed ester stabilizers which includes an improved work-up purification procedure. Another object of the present invention is to provide a process and product produced thereby wherein a mixed ester stabilizer is prepared from a plurality of 3-alkylthiopropionic acids which are formed without requiring a substantially high excess of acid reagent, thereby minimizing the cost and inefficiency of having to remove excess acid therefrom so as to minimize or eliminate purification at an intermediate stage in the preparation of the mixed ester stabilizer Description of Embodiment of the Invention The esters prepared according to the present invention are esters of 3-alkylthiopropionic acids with pentaerythritol wherein the esters contain at least two different alkylthiopropionic acid groups in the molecule. These so-called mixed esters are formed by charging at least two different 3-alkylthiopropionic acids into a reaction vessel with pentaerythritol. The two or more acids are selected and are charged at a predetermined ratio in order to form the desired mixed ester(s) having properties that are tailored to fulfil the needs of a stabilizer for a particular polymer resin or polymer resin blend or the like. The mole ratio of the charge can be varied between, for example, 5:1 and 1:5 in order to provide an additional measure of tailorability to the extent that the mixed esters will exhibit an increase in the proportion of one particular alkyl group as the ratio of the S-alkylthiopropionic acid having that particular alkyl group is increased in the reaction charge. A typical mixed ester prepared by the process according to this invention will have the following structure when same is a pentaerythritol ester which is fully esterified to the tetraester structure according to Formula (I) below: wherein R is an alkyl group having a carbon chain length of between 4 and 20 carbon atoms, wherein R' is an alkyl group different from R and which also has a carbon chain length of between 4 and 20 carbon atoms, and wherein a is 1, 2 or 3. As discussed in more detail hereinafter, mixed esters having similar alkyl groups (R'' and R''') which are each different from R and R' are also possible. Other mixed ester structures may be formed as well. For example, a mixed triester with pentaerythritol would exhibit the structure according to Formula (II) below: wherein R and R' are as previously defined, and wherein b is 1 or 2. It will be appreciated that, when a is 0 or 4 a symmetrical tetraester (and not a mixed tetraester) is formed, and when b is 0 or 3 a symmetrical triester (and not a mixed triester) is formed. It will further be appreciated that formation of the mixed esters is statistically favored. In fact, when the procedures according to the invention are followed, mixed esters of the type wherein a is 1, 2 and 3 are the primary esters which are formed. Variations in reactant charges, for example, can be useful in effecting small changes in the properties of the mixed ester reaction product. Preferably, the 3-alkylthiopropionic acids are each formed from a mercaptan having the desired alkyl group R, R', R'' or R'''. With more particular reference to these mercaptans, they will have the formula RSH, R'SH, R''SH or R'''SH, wherein R, R', R'' or R''' each has a different carbon chain length of between 4 and 20 carbon atoms. Exemplary mercaptans in this regard include n-butyl mercaptan, n-octyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan and the like. In accordance with the preferred aspects of this invention, each 3-alkylthiopropionic acid is prepared by a direct addition reaction procedure whereby each selected mercaptan undergoes an addition reaction with an acid reactant or salt thereof to add the propionic acid component of the 3-alkylthiopropionic acid to the mercaptan. The acid reactant or salt which reacts with the mercaptan may be characterized as an acid reactant which is charged to the reaction vessel as acrylic acid or as a derivative, typically an alkali metal salt thereof. Generally, equimolar charges of each selected mercaptan and of the acid reactant are utilized, although the acid component may be present at a concentration slightly in excess of the equimolar level. This addition reaction is run under strongly basic conditions, and the acid reactant is perhaps more properly characterized as an alkali metal acrylate, with the alkali metal being that of the base component which catalyzes the addition reaction. A 3-alkylthiopropionic acid thus prepared will have the formula RSCH₂CH₂COOH, wherein R is as previously defined herein. Two or more of these acids are utilized in accordance with the present invention, with each acid having a different alkyl group, which may be designated as R, R', R'' or R''' as defined herein. In preparing the two or more 3-alkylthiopropionic acids, any strong base can be utilized as the catalyst, provided an aqueous solution thereof will impart a pH of at least about 11 to the reaction composition. The strength of the base can be generally defined as one wherein a 1% aqueous solution thereof has a pH of at least 13. Typical strong bases in this regard include aqueous potassium hydroxide, aqueous sodium hydroxide and the like. When this procedure is followed, it is important that the reaction composition incorporate an adequate concentration of this strong base. The amount is to be adequate to convert any charged acrylic acid to its alkali salt, while still providing enough strong base to act as a catalyst for the addition reaction. For example, the reaction composition should typically include at least 1.05 mole of strong base per mole of acrylic acid charged into the reaction vessel. When this base catalyzed addition reaction is followed, it is carried out with a sufficient quantity of solvent within the reaction composition. Preferably, the solvent is a mixture of organic solvent and water. Water alone may be suitable for acids made from mercaptans with short chain lengths such as those having four carbon atoms, but using the solvent mixture is believed to be important in most cases. For example, the reaction is faster and less subject to foaming when the solvent is water combined with an organic solvent. Preferred organic solvents in this regard are oxygenated organic solvents, typically ones that are water-soluble oxygenated compounds exhibiting a ratio of from one to four carbon atoms for every oxygen atom. Exemplary solvents in this regard include 2-propanol, tert -butyl alcohol, tetrahydrofuran, ethanol, methanol, 2-ethoxyethanol, and the like. An especially preferred solvent is a mixture of water and 2-propanol (isopropyl alcohol). A typical ratio of water to oxygenated organic solvent is between 9 to 1 and 1 to 9. In a preferred aspect of this process, the mercaptan is added to the reactant composition after it already contains the alkali metal acrylate. It has been determined that, even when the reaction is carried out in the presence of oxygen, the incidence of undesirable disulfide formation is reduced significantly with this order of addition of reactants, when compared with the reverse order of addition, which can be characterized as the addition of acrylic acid to the reaction composition which already contains sodium mercaptide. When the reverse order of addition is desired, typically adequate control of disulfide formation can be attained by blanketing the reaction mixture with nitrogen, when this is feasible. After the addition reaction has progressed to the desired extent, the 3-alkylthiopropionic acid is isolated from the reaction composition by proceeding first with acidification of the reaction mixture, typically with a suitable aqueous mineral acid. The acidification step is preferably carried out at a pH of 4 or below. Aqueous and organic layers thereby defined are then separated. If necessary, depending upon the carbon chain length of the mercaptan reactant, the layers are maintained at a temperature high enough to keep the alkylthiopropionic acid molten. After separation has been completed, the collected organic phase is preferably vacuum stripped in order to remove and recover the organic solvent and thereby provide the 3-alkylthiopropionic acid addition reaction product. Once formed, the two or more 3-alkylthiopropionic acids are esterified with pentaerythritol. Usually this esterification to form the mixed ester product is carried out at an elevated temperature and under acid catalysis. Typically suitable catalysts in this regard are para-toluenesulfonic acid, xylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, and the like. It is especially preferred that this esterification procedure be followed by a work-up operation wherein excess acid is removed by solvent refining the organic phase with an organic solvent. The solvent refining medium is a single organic solvent or a blend of at least two organic solvents, depending upon the specific alkylthiopropionic mixed ester being prepared. Exemplary components of this type include low molecular weight alcohols and low molecular weight esters, including materials such as methanol, ethanol, isopropyl alcohol, ethyl acetate, isopropyl acetate, and the like. It has been found that a suitable solvent will improve work-up purification procedures, when desired, in a manner that minimizes the expense thereof. Typically preferred solvents include methanol and methanol blended with isopropyl alcohol. An exemplary blend is a 4:1 mixture of methanol and isopropyl alcohol. A typical two-component solvent blend would be at a ratio of between about 9 to 1 and about 1 to 9. When greater than two different 3-alkylthiopropionic acids are used to prepare the esters according to the process of the present invention, esters of pentaerythritol would include three or more different alkylmercaptan chains. When three different alkylthiopropionic acids are used, the ester would exhibit the following structure: wherein R and R' are as previously defined herein, wherein R'' is in alkyl group different from R and R' and which also has a carbon chain length of between 4 and 20, and wherein each of x, y and z are 1 or 2 such that x plus y plus z totals 4. When four different 3-alkylthiopropionic acids are used, the ester will have the following structure: wherein R, R' and R'' are as defined herein, and wherein R''' is another alkyl group having a carbon chain length between 4 and 20, which alkyl group is different from that of each of the alkyl groups of the other three alkylthiopropionic acids. Some of these mixed esters, namely those wherein R, R', R'' and R''' are each alkyl groups having from 4 to 12 carbon atoms, and R is different from at least one of R', R'' and R''', are novel and also form part of the present invention. Esters of the type discussed herein are typically suitable for use as stabilizers for extrudable thermoplastic polymers, polymer resins and polymer compositions or blends. Included are various crystalline or rubbery olefin polymers prepared from olefin monomers including ethylene, propylene, 1-butene, 1-hexene, 1-decene, and 4-methyl-1-pentene used singly or in combination; copolymers of ethylene with oxygenated carboxylic acid or ester monomers illustrated by ethyl acrylate, vinyl acetate, and methacrylic acid; styrene polymers including styrene homopolymer and styrene polymer systems incorporating additional monomers such as butadiene, isoprene, acrylonitrile, methyl methacrylate, maleic anhydride, or maleate esters; extrudable thermoplastic polyesters including polycarbonates, polyarylates, glycol terephthalates and proprietary polymers and polymer blends having a terephthalate ester component and a rubbery type of component. Various mixed ester stabilizers prepared according to this invention have different physical properties, thereby enabling exceptionally precise tailoring of the stabilizer to best suit the particular polymer material being stabilized. This provides the advantage of improved compatibility with the particular polymer material leading to the substantial absence of any manifestations of incompatibility such as exudation of a liquid or crystallization of a solid additive on the polymer surface. For example some mixed ester stabilizers take on the consistency of a wax at room temperature and start to melt above room temperature. Others may be solid masses at room temperature which do not begin to melt until above room temperature, such as 32° C. Others can be liquid at room temperature. Also, a wide variety of melting profiles can be tailored as desired. Advantageous use levels of the ester stabilizers of this invention in extrudable thermoplastic polymers range from about 0.01 to about 5% by weight of the polymer, preferably from about 0.2% to about 2% by weight. The following examples illustrate the preparation of mixed esters according to embodiments of the present invention. Example 1 To a stirred solution of 0.50 mole of 1-dodecylmercaptan in isopropanol under a nitrogen atmosphere at 25° C., 0.58 mole of 50% sodium hydroxide aqueous solution was added in one portion. The mixture exothermed to 70° C., and a white precipitate formed. Isopropyl alcohol was added to the slurry, which was cooled to 32° C. with a water bath. Next, 0.525 mole of acrylic acid was added dropwise over a 15 minute period. Additional isopropyl alcohol (in two aliquots) was added, the exothermal reaction proceeded at 40° C., and after 20 minutes of stirring, additional water was added. The solid components slowly dissolved in order to provide a homogeneous solution, which was refluxed for two hours. After standing overnight at 25° C., the sample was analyzed to have 0.03% dodecylmercaptan. Acidification was carried out by heating the reaction composition to 45° C. and adding 50% aqueous sulfuric acid, after which same was poured into a separatory funnel, and the aqueous layer was drained. Washing was next carried out with three portions of water, with the third wash including a small amount of sodium sulfate. The washed organic layer was then vacuum stripped with a Roto-Vap rotary evaporator to give 3-dodecylthiopropionic acid product having a melting point of 59-62° C. The yield by GLC was 99.0% having an acid value of 204.2 (theory 204.4). A charge of 1.00 mole of n-octylmercaptan in an isopropyl alcohol and water 1:1 blend was added to a vessel. At room temperature, 1.16 mole of sodium hydroxide in an equal volume of water was added to the vessel, and an exotherm proceeded at 50 to 60° C. Over a 30-minute period, 1.05 mole of acrylic acid was added dropwise, the temperature was then raised to 85° C., and the mixture was allowed to reflux for 2 hours. After cooling to 55° C., 70% aqueous sulfuric acid (0.59 mole) was added, with stirring for 30 minutes, followed by pouring into a separatory device. The aqueous layer was drained off, and the organic layer was washed with an equal volume of water containing 2% sodium sulfate. After vacuum stripping at 60° C., the reaction product was analyzed to contain 0.04% octylmercaptan and a yield of 98.6% of 3-octylthiopropionic acid product. Slightly in excess of two moles of 3-dodecylthiopropionic acid, slightly in excess of two moles of 3-octylthiopropionic acid, one mole of pentaerythritol, and 20 grams (0.105 mole) of para-toluenesulfonic acid monohydrate catalyst were added to a reaction vessel. A vacuum of approximately 25 mmHg was applied, and the temperature was raised to 135° C. and held there for 7 hours, with stirring. In the work-up, the excess acid was removed by repeated hot washes of a 4:1 blend of methanol and isopropyl alcohol until the acid value of the product was below 1. The product was thoroughly vacuum stripped at 90° C. and filtered hot. The product was a white wax at room temperature, and starts to melt above 25° C. The reaction product was analyzed to contain 0.022% mercaptan and a yield of 91.2% of mixed ester product at an acid value of 0.255. IR analysis (neat) showed peaks at 1744, 1466, 1238 and 1140 cm⁻¹. The product is a mixture of mixed esters. Liquid chromatography shows many peaks. A product following a statistical distribution of esters that could be prepared from the reactants according to this Example could show nine peaks including the two symmetrical tetraesters not in accordance with the present invention and which can be described by Formula I hereinabove when a is 0 and 4. Three mixed esters according to the present invention are defined by Formula I when a is 1, 2 and 3. Triesters are also statistically possible, including two symmetrical triesters, which can be represented by Formula II hereinabove wherein b is 0 and 3. Two statistically possible mixed triesters are defined when b is 1 and 2. Liquid chromatography analysis of the reaction product does show that the reaction product is different from a simple blend of the two statistically possible symmetrical tetraesters. This is readily determined because the symmetrical tetraesters have known, characteristic retention times alone or blended with each other or as components of the reaction product. Retention times of the symmetrical triesters are also known. Confirmation of the inclusion of the mixed esters within the reaction product is achieved (and peaks can be at least tentatively assigned) for the mixed esters of the invention by observing which peaks are increased by the use of increased proportions of one of the alkylthiopropionic acids charged to the reaction vessel. Example 2 The procedure of Example 1 was followed, except in this Example, slightly in excess of six moles of the 3-dodecylthiopropionic acid were charged to the reaction vessel, all other reactants and quantities thereof and process conditions remaining the same as Example 1. The product was a white solid mass at room temperature which melts above 32° C. The reaction product was analyzed to contain 0.025% mercaptan and a yield of 91% of reaction product. The IR spectra peaks (neat) were at 1733, 1467, 1239 and 1138 cm⁻¹. The acid value was 0.31. Example 3 The procedure of Example 1 was followed, except in this Example, slightly in excess of six moles of the 3-octylthiopropionic acid were charged to the reaction vessel, all other reactants and quantities thereof and process conditions remaining the same as Example 1. The reaction product was a clear colorless liquid at room temperature having an n D ²⁵ of 1.4890 and an acid value of 0.856. The percentage of mercaptan in the reaction product was 0.004%, and the yield was 90.1%. The specific gravity was 0.98. The IR spectra peaks (neat) were at 1744, 1466, 1238 and 1140 cm⁻¹. Example 4 A 3-liter, 4-necked round bottom flask was charged with 530.8 grams (3.008 moles) of 98.8% n-decylmercaptan, 600 ml. of isopropyl alcohol and 600 ml. of water. The flask was equipped with a heating mantle, a thermometer, a reflux condenser, an additional funnel and a mechanical stirrer. Nitrogen (900 ml./min.) was introduced through the top of the condenser by way of a Firestone valve. 140.6 grams (3.459 moles) of 98.4% sodium hydroxide in a 50% aqueous solution were added to the stirred mixture over one hour. The temperature rose to 38° C., and 227.6 grams (3.158 moles) of acrylic acid were then added over 55 minutes, raising the temperature to 62° C. The mixture was refluxed at 86° C. for four hours, and the nitrogen flow rate of 900 ml./min. continued overnight. The mercaptan value at this time was analyzed at less than 0.02%. Next, 190.9 grams (1.907 moles) of 98% sulfuric acid was dissolved in a 50% aqueous solution and added to the stirred mixture at 60° C. Stirring continued for 15 minutes, after which the layers were permitted to separate. The lower layer had a pH of 3. The mixture was transferred to a separatory funnel where the lower layer was removed. The product was then washed with two aliquots of 500 ml. of hot (approximately 60° C.) sodium sulfate solution at a concentration of about 2 to 3%. The washed product was stripped with a rotary evaporator. The yield was 734.0 grams, or 99.0%. The acid value analyzed at 227.0. According to gas chromatography analysis, the product was at least 97.4% pure, with only 0.2% isopropyl acetate ester. A mixed ester product of Bis-(3-n-dodecylthiopropionoxy Bis-(3-n-decylthiopropionoxy) neopentane was prepared. 134.7 grams (0.547 mole) of the 3-n-decylthiopropionic acid prepared as specified herein was mixed with 150.0 grams (0.547 mole) of 3-n-dodecylthiopropionic acid within a 1-liter, 4-necked round bottom flask, with agitation by a mechanical stirrer. Next, 35.0 grams (0.26 mole) of pentaerythritol were added, followed by 3.9 grams (0.021 mole) of para-toluenesulfonic acid catalyst. The flask was also equipped with a thermometer, a heating mantle, a vacuum take-off adaptor and a pressure relief valve. Vacuum was applied immediately, and while the temperature rose to 110° C., the pressure was carefully lowered to 38 torr, during which water was driven off. Thereafter, the temperature was raised to 135° C., and the mixture was heated for five hours during which time the pressure dropped to 25 torr. An acid value analysis indicated 10.9. The product was washed with 500 ml. of hot 2 to 3% sodium sulfate, followed by stripping with a rotary evaporator, after which the product was washed with four 300 ml. aliquots of hot methanol, the acid value thereafter being 1.1. An acid value of 0.3 was achieved after washing with three additional 300 ml. aliquots of hot methanol. The product was stripped again to remove methanol, and the yield was 258.4 grams (89.9%) of a product having a melting point of 36-38° C. Liquid chromatography testing showed a distribution of tetraester products, including a substantial percentage of mixed tetraester products, within the product yield. The analyzed product distribution correlated well with the expected theoretical product distribution. These data can be summarized as follows: The Formula (I) tetraester reported upon is one wherein R has a carbon chain length of 10 and is from the decyl mercaptan, while R' has a carbon chain length of 12 and is from the dodecyl mercaptan, and wherein "a" in Formula I is as indicated hereinabove. Example 5 A Bis-(3-n-decylthiopropionoxy) Bis-(3-n-octylthiopropionoxy) neopentane was prepared. 150 grams (0.609 mol) of 3-n-decylthiopropionic acid and 132.9 grams (0.609 mol) of 3-n-octylthiopropionic acid were mixed, rendered molten and stirred within a reaction vessel, to which 39.5 grams (0.290 mol) of pentaerythritol were added, followed by 4.4 grams (0.023 mol) of para-toluenesulfonic acid catalyst. A vacuum of 40 torr was applied, and the mixture was heated to 135° C. Heating was continued for five hours, after which a liquid product having an acid value of 11.4 was obtained. This product was washed with 500 ml. of hot 3% sodium sulfate and then vacuum stripped. It was washed with six 300 ml. aliquots of hot methanol, after which the acid value was 0.4. The yield was 250.9 grams, or 87.1 percent. A comparison of the actual product distribution versus the statistical distribution can be summarized as follows: Formula (I) Tetraester Theoretical Percentage LC Analysis Percentage a=4 6.25 5.5 a=3 25.00 24.2 a=2 37.50 37.8 a=1 25.00 25.4 a=0 6.25 7.1 In this Formula (I) product, R had a carbon chain length of 8, R' had a carbon chain length of 10, and "a" is as indicated.

Claims: A process for preparing a mixed ester of pentaerythritol with a plurality of 3-alkylthiopropionic acids wherein each alkyl group thereof has between 4 and 20 carbon atoms, comprising: (a) reacting an alkyl mercaptan of the formula RSH, wherein R is an alkyl group having from 4 to 20 carbon atoms by a direct addition reaction with an acrylic acid component selected from the group consisting of acrylic acid and an alkali metal acrylate, and recovering a 3-alkylthiopropionic acid having R as its alkyl group; (b) reacting an alkyl mercaptan of the formula R'SH , wherein R' is an alkyl group different from R and having from 4 to 20 carbon atoms by a direct addition reaction with an acrylic acid component selected from the group consisting of acrylic acid and an alkali metal acrylate, and recovering a 3-alkylthiopropionic acid having R' as its alkyl group; (c) optionally reacting an alkyl mercaptan of the formula R''SH wherein R'' is an alkyl group different from R and R' and having from 4 to 20 carbon atoms by a direct addition reaction with an acrylic acid component selected from the group consisting of acrylic acid and an alkali metal acrylate, and recovering a 3-alkylthiopropionic acid having R'' as its alkyl group; (d) optionally reacting an alkyl mercaptan of the formula R''', wherein R''' is an alkyl group different from R, R' and R'' and having from 4 to 20 carbon atoms by a direct addition reaction with an acrylic acid component selected from the group consisting of acrylic acid and an alkali metal acrylate, and recovering a 3-alkylthiopropionic acid having R''' as its alkyl group; and (e) reacting together said 3-alkylthiopropionic acid having R as its alkyl group, said 3-alkylthiopropionic acid having R' as its alkyl group, optionally said 3-alkylthiopropionic acid having R'' as its alkyl group, optionally said 3-alkylthiopropionic acid having R''' as its alkyl group, and pentaerythritol in order to form a mixed ester product having a molecular structure containing both R and R' groups, optionally R'' groups and optionally R''' groups. The process according to claim 1, wherein said reacting steps (a) to (d) are carried out in an alkaline reaction solution and in the presence of an aqueous alkaline catalyst. The process according to claim 2, further including acidifying said reaction solution prior to recovery of each said 3-alkylthiopropionic acid. The process according to claim 2 or claim 3, wherein said reaction solution is at a pH of at least about 11. The process according to any one of claims 2 to 4, wherein said reaction solution is an aqueous alkaline solution including a solvent mixture of water and an organic solvent. The process according to claim 3, wherein said acidifying step is carried out at a pH of 4 or below. The process according to any one of claims 2 to 6, wherein said catalyst of the reacting steps is a base which is present at a molar concentration in excess of that of any acrylic acid, wherein a 1% aqueous solution of the base has a pH of at least 13. The process according to claim 2 or claim 7, wherein said alkaline catalyst is an alkali metal hydroxide. The process according to claim 2, claim 7 or claim 8, wherein at least 1.05 mole of the alkaline catalyst is added per mole of charged acrylic acid component. The process according to any one of the preceding claims, wherein said alkyl mercaptan and said acrylic acid component are at substantially equimolar concentrations. The process according to any one of the preceding claims, further including solvent refining said mixed ester product with an organic solvent. The process according to claim 11, wherein said organic solvent is a blend of one or more of methanol, ethanol, isopropyl alcohol, ethyl acetate or isopropyl acetate. The process according to claim 2, wherein said alkaline reaction solution is at a pH of at least about 11, each said alkyl mercaptan and each said acrylic component are at substantially equimolar concentrations, and said alkaline catalyst is an alkali metal hydroxide added at a concentration of at least 1.05 mole per mole of charged acrylic acid. The process according to any one of the preceding claims, wherein said reacting step (e) includes charging said 3-alkylthiopropionic acids and pentaerythritol at a mole ratio between 5:1 and 1:5. The process according to claim 1, wherein at least one of said 3-alkylthiopropionic acids is 3-butylthiopropionic acid, 3-octylthiopropionic acid, 3-decylthiopropionic acid or 3-dodecylthiopropionic acid. The process according to claim 1, wherein R has a carbon chain length of 8 and R' has a carbon chain length of 12. The process according to claim 1, wherein R has a carbon chain length of 8 and R' has a carbon chain length of 10. The process according to claim 1, wherein R has a carbon chain length of 10 and R' has a carbon chain length of 12. A mixed tetraester of pentaerythritol formed from a plurality of 3-alkylthiopropionic acids, said mixed tetraester comprising at least one tetraester component having the formula: wherein R, R', R'' and R''' are each alkyl groups having from 4 to 12 carbon atoms, and R is different from at least one of R', R'' and R'''. An ester according to claim 19, wherein at least one of said 3-alkylthiopropionic acids is 3-butylthiopropionic acid, 3-octylthiopropionic acid, 3-decylthiopropionic acid or 3-dodecylthiopropionic acid. An ester according to claim 19, wherein R has a carbon chain length of 8 and at least one of R', R'' and R''' has a carbon chain length of 12. An ester according to claim 19, wherein R has a carbon chain length of 8 and at least one of R', R'' and R''' has a carbon chain length of 10. An ester according to claim 19, wherein R has a carbon chain length of 10 and at least one of R', R'' and R''' has a carbon chain length of 12. A stabilized polymer composition including an extrudable polymer resin component and a stabilizer component, wherein said stabilizer component comprises a mixed ester according to any one of claims 19 to 23. A process of making a stabilized composition as defined in claim 24 which includes the step of selecting the values of R, R', R'' and R''' such that the mixed tetraester is compatible with the specific extrudable resin component.

Inventors: FISCH MICHAEL H, PEVELER RICHARD DAVID, FISCH, MICHAEL H., PEVELER, RICHARD DAVID
Applicants: WITCO CORP, WITCO CORPORATION
Application year: 1990
Main classification: C07C323
IPC codes: C08K5, C07C323, C07C319