(12) United States Patent (10) Patent No.: US 7,205,349 B2 Koch Et Al
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USOO7205349B2 (12) United States Patent (10) Patent No.: US 7,205,349 B2 Koch et al. (45) Date of Patent: Apr. 17, 2007 (54) ISODECYL BENZOATE MIXTURES, 5,268,514 A 12/1993 Bahrmann et al. PREPARATION, AND THEIR USE 5,463,147 A 10, 1995 Bahrmann et al. 6,340,778 B1 1/2002 Bueschken et al. (75) Inventors: Jirgen Koch, Haltern am See (DE); 2004/O138358 A1 7/2004 Koch et al. Michael Grass, Haltern am See (DE) 2005.0049.341 A1 3/2005 Grass et al. FOREIGN PATENT DOCUMENTS (73) Assignee: Oxeno Olefinchemie GmbH, Marl DE 1962 500 7, 1970 (DE) DE 196 17 178 11, 1996 DE 19957 522 5, 2001 (*) Notice: Subject to any disclaimer, the term of this EP O 094 456 11, 1983 patent is extended or adjusted under 35 EP O 326 674 8, 1989 U.S.C. 154(b) by 79 days. EP O 470 344 2, 1992 EP O 562 451 9, 1993 (21) Appl. No.: 10/692,753 WO WO 89.00173 * 1 1989 WO WO 93/20034 10, 1993 (22) Filed: Oct. 27, 2003 WO WO 97.39060 * 10/1997 (65) Prior Publication Data OTHER PUBLICATIONS U.S. Appl. No. 10/418, 103, filed Apr. 18, 2003, Grass, et al. US 2004/O138358 A1 Jul. 15, 2004 U.S. Appl. No. 10/692,753, filed Oct. 27, 2003, Koch, et al. U.S. Appl. No. 10/570,199, filed Mar. 2, 2006, Grass, et al. (30) Foreign Application Priority Data U.S. Appl. No. 10/575,100, filed Apr. 10, 2006, Grass, et al. Oct. 26, 2002 (DE) ................................ 102 49912 U.S. Appl. No. 10/692,753, filed Oct. 27, 2003, Koch, et al. * cited by examiner (51) Int. Cl. CSK 5/IOI (2006.01) Primary Examiner Robert D. Harlan (52) U.S. Cl. ....................................... 524/284; 526/344 (74) Attorney, Agent, or Firm Oblon, Spivak, McClelland, (58) Field of Classification Search ................ 524/284; Maier & Neustadt, P.C. 526/344 See application file for complete search history. (57) ABSTRACT (56) References Cited The invention relates to isomeric nonylbenzoates, processes for their preparation, mixtures of the same with alkyl phtha U.S. PATENT DOCUMENTS late, alkyl adipate, or alkyl cyclohexanedicarboxylate, and 4,968,849 A 11/1990 Lueken et al. also to the use of these mixtures. 5,093,534 A 3/1992 Ludwig et al. 5,236,987 A * 8/1993 Arendt ....................... 524/287 12 Claims, 1 Drawing Sheet U.S. Patent Apr. 17, 2007 US 7.205,349 B2 O. Z. 6 OO4 1.00E --06 1.00E +0.5 s' 1.00E --04 A 1.00E --O3 / 1.00E --01 --21 1.OOE +OO re se-Net 1.OOE-01 40 Fig 1: Gelling curves of plastisols 1-3 US 7,205,349 B2 1. 2 ISODECYL BENZOATE MIXTURES, in low-temperature flexibility, and in storage stability. When PREPARATION, AND THEIR USE preparing plasticized PVC, gelling capability has to be good and the volatility of the plasticizer has to be low. This is BACKGROUND OF THE INVENTION affected by the interactions between plasticizer and PVC polymer chain, and even slight structural changes in the 1. Field of the Invention molecular structure of the plasticizer molecule can therefore The invention relates to benzoic esters of 2-propylhep bring about large changes in performance characteristics. tanol, of 2-propyl-4-methylhexanol, of 2-propyl-5-methyl hexanol, of 2-isopropyl-4-methyl-hexanol and/or of 2-iso SUMMARY OF THE INVENTION propyl-5-methylhexanol, to mixtures of these with alkyl 10 phthalates, with alkyl adipates, or with alkyl cyclohexanedi An object of the present invention is to find new plasti carboxylates, and also to the use of these mixtures. cizers for plastics, e.g. for PVC, which are based on low-cost 2. Discussion of the Related Art raw materials and have equivalent or improved plasticizer Polyvinyl chloride (PVC) is one of the most important properties. Such as improved low-temperature-flexibilizing industrial polymers. It is used in a wide variety of applica 15 capability, while the corresponding plastisols have low vis tions, in the form of either unplasticized PVC or plasticized cosity. PVC. One embodiment of the present invention provides a To produce a plasticized PVC, plasticizers are added to mixture of isomeric decyl benzoates, which includes the PVC, and phthalates are used in the majority of cases, in from 50 to 99% of 2-propylheptylbenzoate and particular di-2-ethylhexyl phthalate (DEHP), diisononyl from 1 to 50% of at least one selected from the group phthalate (DINP), or diisodecyl phthalate (DIDP). As the including 2-isopropyl-4-methylhexylbenzoate, 2-isopropyl chain length of the esters increases, the solution or gelling 5-methylhexyl benzoate, 2-propyl-4-methylhexyl benzoate, temperatures rise, and therefore the processing temperatures 2-propyl-5-methylhexyl benzoate, and mixtures thereof. of the plasticized PVC rise. The processing temperatures can Another embodiment of the present invention provides a be reduced again by adding what are known as fast-gellers, 25 process for preparing the above mixture, which includes such as the short-chain phthalates dibutyl phthalate (DBP), esterifying, with benzoic acid, disobutyl phthalate (DIBP), benzylbutyl phthalate (BBP), 2-propylheptanol, and or diisoheptyl phthalate (DIHP). In addition to the short at least one selected from the group including 2-isopro chain phthalates, dibenzoates, such as dipropylene glycol pyl-4-methylhexanol, 2-isopropyl-5-methylhexanol, dibenzoates or the like, may also be used for the same 30 2-propyl-4-methylhexanol. 2-propyl-5-methylhexanol, purposes. and mixtures thereof. A property frequently exhibited by these fast-gellers in Another embodiment of the present invention provides a PVC plastisols, owing to their high Solvating power, consists process for preparing the above mixture, by trans-esterifying in causing a marked rise in Viscosity with time. In many at least one selected from the group including methyl cases this rise in Viscosity must be compensated by adding 35 benzoate, ethyl benzoate, propyl benzoate, butylbenzoate, Viscosity-reducers. and mixtures thereof, When PVC plastisols are prepared, the general require with 2-propylheptanol and at least one selected from the ment is low viscosity and minimum gelling temperature. In group including 2-isopropyl-4-methylhexanol, 2-isopropyl addition to these, a high storage stability is desirable, i.e., a 5-methylhexanol, 2-propyl-4-methylhexanol. 2-propyl-5- low rise in viscosity of the plastisol with time. 40 methythexanol, and mixtures thereof. A high viscosity is burdensome on the machinery during Another embodiment of the present invention provides a processing of the plastisol. Excessively high gelling tem polymer, plastic, PVC, or PVC plastisol, which includes the peratures reduce the production rate. above mixture as a plasticizer. Currently, there is little knowledge of plasticizers which Another embodiment of the present invention provides a significantly lower the gelling temperature in a formulation 45 paint, ink or coating material, which includes the above and also retain a low level of viscosity of the plastisol even mixture. after storage for a number of days. 2-Ethylhexyl benzoate Another embodiment of the present invention provides an was recently proposed as a product which could fulfill these adhesive, component thereof, or sealing compound, which requirements (Bohnert, Stanhope, J. Vinyl Addit, Technol. includes the above mixture. (2000), 6(3), 146-149). However, this compound has a 50 Another embodiment of the present invention relates to a comparatively high vapor pressure, which often leads to composition, which includes from 5 to 90% by weight of the unacceptable losses during processing. above-identified mixture and from 10 to 95% by weight of DE 1962 500 discloses the use of a mixture of relatively one or more di-C-C-alkyl phthalates. long-chain esters of benzoic and phthalic acid for preparing Another embodiment of the present invention relates to a plastisols. 3.5.5-Trimethylhexanol is preferably used to pre 55 composition, which includes from 5 to 90% by weight of the pare the benzoic esters. No precise information is given above-identified mixture and from 10 to 95% by weight of concerning the phthalic diesters to be used. U.S. Pat. No. one or more di-C-C-alkyl adipates. 5,236,987 discloses the use of benzoic esters of isodecanols Another embodiment of the present invention relates to a which have exclusively methyl branching as plasticizers or composition, which includes from 5 to 90% by weight of the gelling agents for PVC. 60 above-identified mixture and from 10 to 95% by weight of The use of alkylbenzoates whose alkyl group has from 11 one or more C-C alkyl cyclohexanedicarboxylates. to 14 carbon atoms is disclosed in WO97/39060. Although relatively long-chain esters have low volatility, they have DESCRIPTION OF THE DRAWINGS poorer gelling properties. In PVC, the abovementioned plasticizer systems are not 65 Various other objects, features and attendant advantages completely satisfactory, and there is room for improvement of the present invention will be more fully appreciated as the not only in their volatility but also in their gelling properties, same becomes better understood from the following detailed US 7,205,349 B2 3 4 description when considered in connection with the accom The hydroformylation of linear butenes or mixtures of panying drawings in which like reference characters desig these is disclosed by way of example in the publications EP nate like or corresponding parts throughout the several 0 094. 456, DE 196 17 178, EP 0562 451 or EP 0 646563, views and wherein FIG. 1 shows a plot of that section of the each incorporated herein by reference. viscosity/temperature curve (“gelling curve') relevant for 5 The usual method for the aldol condensation of n-valer the onset of gelling.