Production of ester mixtures

Patent metadata

Field	Value
Publication number	US-2016237244-A1
Application number	US-201615047051-A
Country	US
Kind code	A1
Filing date	Feb 18, 2016
Priority date	Feb 18, 2015
Publication date	Aug 18, 2016
Grant date	—

Abstract

Ester mixtures comprising the esters A(COOR 1 )(COOR 1 ) x , A(COOR 1 )(COOR 2 ) x , A(COOR 2 )(COOR 1 ) x and A(COOR 2 )(COOR 2 ) x , can be produced in a targeted way by processes in which acids A(COOH) x+1 or derivatives thereof are reacted with an amount (m 1 +s 1 ) of R 1 OH and an amount m 2 of R 2 OH, the reaction mixture being heated at boiling, the alcohol R 1 OH having a lower boiling point than the alcohol R 2 OH, A being an aromatic, alicyclic or aliphatic radical, x being 1 or 2, and R 1 and R 2 independently of one another being substituted or unsubstituted aryl radicals or linear or branched, substituted or unsubstituted alkyl radicals having 3 to 20 carbon atoms, m 1 and m 2 corresponding to the mole equivalents of the alcohol radicals OR 1 and OR 2 to be introduced into A(COOH) x+1 or derivatives thereof, and s 1 being greater than 0.

First claim

1 . A process for producing an ester mixture, comprising:
reacting A(COOH) x+1 or derivatives thereof which contain no ester group COOR having a radical R whose alcohol ROH has a higher boiling point at a defined pressure than the alcohol R 1 OH of the radical R 1 at the same pressure, with an amount (m 1 +s 1 ) of R 1 OH and an amount m 2 of R 2 OH in a reaction mixture, heating the reaction mixture at boiling, to obtain the ester mixture comprising A(COOR 1 )(COOR 1 ) x , A(COOR 1 )(COOR 2 ) x , A(COOR 2 )(COOR 1 ) x and A(COOR 2 )(COOR 2 ) x , wherein A is an aromatic, alicyclic or aliphatic radical, x is 1 or 2, R 1 and R 2 independently of one another are substituted or unsubstituted aryl radicals or linear or branched, substituted or unsubstituted alkyl radicals having 3 to 20 carbon atoms, the alcohol R 1 OH having a lower boiling point at a defined pressure than the alcohol R 2 OH at the same pressure, m 1 and m 2 correspond to the mole equivalents of the alcohol radicals OR 1 and OR 2 to be introduced into A(COOH) x+1 or derivatives thereof, and s 1 is greater than 0.

2 . The process according to claim 1 , wherein the ester mixture is a mixture of at least one member selected from the group consisting of phthalic acid, terephthalic acid, isophthalic acid, 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, maleic acid, succinic acid, furandicarboxylic acid and citric acid.

3 . The process according to claim 1 , wherein R 1 and R 2 independently of one another are selected from the group consisting of alkyl radicals which contain 3 to 20 carbon atoms.

4 . The process according to claim 1 , wherein R 1 and R 2 independently of one another are selected from the group consisting of alkyl radicals which contain 3 to 20 carbon atoms, and wherein the alkyl radicals have no other functional group including a multiple bond.

5 . The process according to claim 3 , wherein R 1 and R 2 independently of one another are selected from the group consisting of propyl, butyl, tert-butyl, isobutyl, 2-methylbutyl, 3-methylbutyl, n-pentyl, isopentyl, hexyl, heptyl, isoheptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, n-nonyl, isononyl, decyl, isodecyl, 2-propylheptyl, undecyl and tridecyl radicals.

6 . The process according to claim 1 , wherein the boiling points of the alcohols R 1 OH and R 2 OH differ by at least 10° C.

7 . The process according to claim 1 , wherein the amount s 1 is less than m 1 +m 2 , and/or the amount s 1 is greater than 0.05·(m 1 +m 2 ).

8 . The process according to claim 1 , wherein a catalyst is used in the process and the amount of R 1 OH in the reaction mixture has been lowered to less than 20 mol %, based on the excess amount s 1 of the alcohol R 1 OH, before the catalyst is destroyed.

9 . The process according to claim 1 , which provides an ester mixture in which the molar ratio of the esters A(COOR 1 )(COOR 1 ) x , A(COOR 1 )(COOR 2 ) x , A(COOR 2 )(COOR 1 ) x and A(COOR 2 )(COOR 2 ) x for x=1 deviates by less than 15 points from the statistically determined expectation value which arises on assumption of complete incorporation of the alcohol radicals OR 2 , this points value corresponding to the sum total of all amounts of the differences between statistical expectation value and actual molar fraction of each individual ester in the ester mixture in the event that the sum total of the molar fractions of the esters in the ester mixture adds up to 100.

10 . The process according to claim 1 , which provides an ester mixture in which the molar ratio of the esters A(COOR 1 )(COOR 1 ) x , A(COOR 1 )(COOR 2 ) x , A(COOR 2 )(COOR 1 ) x and A(COOR 2 )(COOR 2 ) x for x=2 deviates by less than 25 points from the statistically determined expectation value which arises on assumption of complete incorporation of the alcohol radicals OR 2 , this points value corresponding to the sum total of all amounts of the differences between statistical expectation value and actual molar fraction of each individual ester in the ester mixture in the event that the sum total of the molar fractions of the abovementioned esters in the ester mixture adds up to 100.

11 . The process according to claim 1 , wherein the ester mixture is a mixture of phthalic acid, terephthalic acid or isophthalic acid and after optional work-up the ester mixture is hydrogenated in a subsequent process step.

12 . An ester mixture produced by the process according to claim 1 .

13 . The process according to claim 1 , comprising:
controlling the quantitative distribution of the esters in the ester mixture in order to set processing-relevant and/or application-relevant properties of the resulting ester mixture.

14 . A polymer plasticizer, comprising:
mixture according to claim 12 .

15 . The polymer plasticizer according to claim 14 , wherein said polymer is PVC.

16 . An adhesive, sealant, coating material, paint, ink, plastisol, foam, synthetic leather, floorcovering, roofing membrane, underbody protection, fabric coating, cable, wire insulation, hose, extruded article, film, automotive interior article, wallcovering, liquid ink, toy, contact sheet, food packaging or medical article, comprising:
the polymer plasticizer according to claim 14 .

17 . A composition, comprising:
the ester mixture according to claim 12 ; and one or more polymers selected from the group consisting of polyvinyl chloride, copolymers of vinyl chloride with vinyl acetate or with butyl acrylate, polyalkyl methacrylate (PAMA), polyvinyl butyral (PVB), polyurethane, polysulphides, polylactic acid (PLA), polyhydroxybutyral (PHB) and nitrocellulose.

Assignees

• Boeck Florian Sebastian
• Gehlen Carsten
• Grass Michael
• Woldt Benjamin
• Evonik Degussa Gmbh

Inventors

• Boeck Florian Sebastian
• Gehlen Carsten
• Grass Michael
• Woldt Benjamin

Classifications

• C08K5/12 Primary

  of cyclic polycarboxylic acids · CPC title

• C09D127/06

  Homopolymers or copolymers of vinyl chloride · CPC title

• C08L2203/16

  used for films · CPC title

• C09D7/63

  organic · CPC title

• C08K2201/014

  Additives containing two or more different additives of the same subgroup in C08K · CPC title