US 20070027244A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2007/0027244 A1 Schar et al. (43) Pub. Date: Feb. 1, 2007 (54) ESTER BLENDS BASED ON BRANCHED (86). PCT No.: PCT/EPO4/O1147 ALCOHOLS AND/OR BRANCHED ACDS AND THEIR USE AS POLYMERADDITIVES S 371(c)(1), (2), (4) Date: Sep. 11, 2006 (76) Inventors: Dirk Schar, Klaus-Groth-Strasse (DE); (30) Foreign Application Priority Data Michael Gode, Andornsteig (DE) Feb. 10, 2003 (DE)..................................... 103 05 562.2 Publication Classification Correspondence Address: C. JAMES BUSHMAN (51) Int. Cl. 5718 WESTHEMER CSK 5/10 (2006.01) SUTE 18OO (52) U.S. Cl. ........................... 524/306; 524/284; 524/296 HOUSTON, TX 77057 (US) (57) ABSTRACT (21) Appl. No.: 10/545,101 The present invention relates to ester blends, their use as polymer additives, and to polymer compositions containing (22) PCT Filed: Feb. 9, 2004 said ester blends. US 2007/0027244 A1 Feb. 1, 2007 ESTER BLENDS BASED ON BRANCHED ALCOHOLS AND/OR BRANCHED ACDS AND TABLE 1. THEIR USE AS POLYMER ADDITIVES Structures of Typical Oxoalcohols 0001. The present invention relates to ester blends and Conventional Modified Fischer-Tropsch their use as polymer additives. Furthermore, this invention relates to polymer compositions containing said ester Linear alcohols 45% --80% -50% blends. Branched alcohols --55% -20% -50% R—CH2—CH2—OH 45% --80% --95% 0002 Commercially available fatty alcohols and -acids R.RCH CH-OH --55% -20% --5% have very different structures, depending on the raw mate rials source or the manufacturing process. Linear, Saturated 0008. It is the object of the present invention to provide fatty alcohols of the chain lengths Cs to C can be obtained novel ester blends which are particularly suitable as polymer from natural fats and oils by hydrolysis or methanolysis additives. In addition, said blends ought to be very compat followed by hydrogenation of the resultant acids or methyl ible with polymers and have excellent emission character esters. Longer-chained, linear, saturated fatty alcohols (C. istics besides the advantage of a low melting temperature in to Cao) are present in natural waxes, e.g. in beeswax or comparison with esters based on linear alcohols. montan waxes. Linear, Saturated fatty alcohols having chain 0009. The novel ester blends exhibiting surprising prop lengths from C to Co. can be obtained petrochemically by erties can be prepared from the alcohols and acids obtained the Ziegler process using aluminium, hydrogen, and ethyl in the Fischer-Tropsch process. Said ester blends are sub ene. In addition, products with chain lengths in the range stantially composed of from C to Cao can be produced by ethylene polymerisation and conversion of the resultant C.-olefins into alcohols and 0010) esters with 1 to 4 carboxyl groups and 12 to 60 acids (Unilin alcohols and -acids). carbon atoms, which can be prepared by reaction of 0003) Semilinear fatty alcohols, such as NEODOLTM 00.11 one or more carboxylic acid(s) which are alcohols, can be synthesised by ethylene oligomerisation optionally halogenated, wholly or in part, and/or one and subsequent selective hydroformylation of the C-olefins or more phosphoric acid(s) with thus obtained. Such alcohols (modified oxoalcohols, termed 0012 one or more alcohol(s), MO) comprise approx. 80% primary, linear and saturated 0013 wherein the carboxylic acids, the alcohols, or alcohols. The remainder is predominantly comprised of both (but at least one) are present as a mixture and alcohols which are alkyl-branched in the 2-position to the the carboxylic acid mixture and/or the alcohol mix alcohol group. ture comprise(s) 0004 Conventional oxoalcohols (termed NO) are gen 0014 alcohols according to the formula RCHOH erally based on kerosene. Here, first the stream of paraffins and/or carboxylic acids according to the formula is isolated, which then are dehydrogenated to olefins and RCOOH, wherein finally hydroformylated. The fatty alcohols thus obtained comprise approximately 50% primary, linear and Saturated 0015) (a) in more than 20 wt % to 80 wt % of the fatty alcohols. alcohols and/or acids used, preferably 40 to 70 wt %, the hydrocarbon radical R is linear and ali 0005 Almost all the resultant branched alcohols are phatic, preferably Saturated, and comprises 4 to 20 branched in the 2-position. Besides, it is known that this carbon atoms, preferably 7 to 12, and product stream can be split into linear and branched por 0016 (b) in more than 10 wt % to 80 wt % of the tions. alcohols and/or acids used, preferably 20 to 60 wt %, the hydrocarbon radical R is aliphatic, prefer 0006. In addition to these fatty alcohols most of which ably saturated, and comprises 4 to 20 carbon are only monobranched, multibranched ones are also known. atoms, preferably 7 to 12, of which up to 3, Such fatty alcohols are obtained by oligomerisation of preferably 1 or 2, are tertiary ones and none of the propene and/or butenes plus hydroformylation. Typical tertiary carbon atoms is in the 2- or 3-position to chain lengths of Such alcohols are in the range from C to the —OH group of the alcohol or acid, and Cs, e.g. isononanol, isodecanol, and isotridecanol (modified wherein at least 80% of the tertiary carbon atoms, fatty alcohols). The corresponding acids of the alcohols most preferably at least 95%, referring to the total described hereinabove are known as well. of tertiary carbon atoms in the mixture, is not directly adjacent, 0007 Lately, a new class of fatty alcohols has became accessible by hydroformylation of olefins obtained in the 0017 and, optionally, Fischer-Tropsch (FT) process using synthesis gas. In con trast to known fatty alcohols, the latter ones have special 0018 (c) up to 10 wt % other alcohols or acids are structural features. For example, there may be comprised comprised, preferably up to 5 wt %, which have 5 approx. 50% branched molecules on the average, which is to 21 carbon atoms, preferably 8 to 13, the same as for conventional oxoalcohols, but the majority 0.019 wherein the alcohols, the acids, or both of these molecules are not branched in the 2-position to the according to (a), (b), and (c) Supplement one hydroxyl group, contrary to prior-art alcohols. another to 100 wt %. US 2007/0027244 A1 Feb. 1, 2007 0020 Preferred embodiments of the present invention are terephthalic acid, malic acid, tartaric acid, 1.2-cyclohexane set out in the subordinate claims or are described in the dicarboxylic acid, trimelitic acid, citric acid, pyrromellitic following. It is preferable that the radicals R comprise on the acid, or tetrachlorophthalic acid. average 11 to 12 carbon atoms, each referring to all the radicals R. The ester blends are blends of mixed esters. The 0026. In addition, the present invention relates to esters percent by weight stated hereinabove refer to the composi based on acids having a chain length from Cs to Cs. tion of the ester blend. preferably Cs to C, most preferably C2 to C, comprising 0021. The ester blends of the invention are prepared by for example aliphatic or cyclic or aromatic, branched or reaction of mono-, di-, tri-, and tetraacids or phosphoric acid linear, saturated or unsaturated C- to C monoalcohols, with monols, or of mono-, di-, tri-, and tetraols with mono Such as ethanol, propanol, isopropanol, butanol, isobutanol, carboxylic acids, wherein the carboxylic acid, the alcohol, or pentanol, hexanol, heptanol, octanol, nonanol, decanol, both are present as blends. If both are blends, these are the dodecanol, tetradecanol, hexadecanol, octadecanol, reaction products of monocarboxylic acids with monoalco eicosanol, tallow fatty alcohol, coconut fatty alcohol, palm hols. fatty alcohol, castor-oil alcohol, oleyl alcohol, linolyl alco hol, linolenyl alcohol, behenyl alcohol, isostearyl alcohol, 0022. By the term “polymer additives” as used herein is isooctanol, isononanol, isodecanol, 2-ethylhexane alcohol, meant for example plasticisers, lubricants, release agents, 2-propylheptanol, 2-butyloctanol, 2-butyldecanol, 2-hexy Viscosity reducers, antioxidants, and solvents. Their func loctanol, 2-hexyldecanol, 2-hexyldodecanol, 2-octylde tions are contingent on both the ester structure and the type canol, 2-octyldodecanol, 2-decyltetradecanol, 2-dodecyl of polymer. hexadecanol, 2-tetradecyloctadecanol, benzyl alcohol, 0023. With respect to phthalate esters which, according to cyclohexanol, vinyl alcohol, lactic acid, hydroxylbutyric the instant invention, are particularly useful as PVC plasti acid, mandelic acid, glycerolic acid, citric acid, phenols, or cisers, the compatibility limit averages out to about 13 di-, tri- or polyols, such as ethyleneglycol, diethyleneglycol, carbon atoms in the alcohol residue. For example, a com triethyleneglycol, propyleneglycol, butyleneglycol, pentyle monly known plasticiser is diisotridecylphthalate (DTDP), neglycol, hexyleneglycol, neopentylglycol, malic acid, tar taric acid, cyclohexane diols or glycerol, trimethylolpropane but there also exist plasticisers based on C-C alcohol or alditols, diglycerides, triglycerides, polyglycerides, pen mixtures. taerythritol or dipentaerythritol. 0024. Owing to the limited compatibility of long-chain alcohol residues as such, it has been suggested in the art to 0027 Said esters are useful as additives for various use alcohol blends, wherein prior to the esterification, the polymers, such polyvinyl chloride (PVC), polyvinylidene long-chain C and/or C alcohol(s) is/are mixed with chloride (PVDC), polyacrylates (e.g. polymethylmethacry