TEPZZ_9_ 9 9B_T

(19)

(11) EP 1 912 929 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: B01J 31/04 (2006.01) C07C 67/08 (2006.01)
08.01.2014 Bulletin 2014/02
(86) International application number:
(21) Application number: 06788502.0 PCT/US2006/028942

(22) Date of filing: 26.07.2006 (87) International publication number:

WO 2007/021475 (22.02.2007 Gazette 2007/08)

(54) PRODUCTION OF DI-(2-ETHYLHEXYL) TEREPHTHALATE

HERSTELLUNG VON DI-(2-ETHYLHEXYL)-TEREPHTHALAT
PRODUCTION DE DI-(2-ETHYLHEXYLE) TEREPHTHALATE

(84) Designated Contracting States: (56) References cited:

AT BE BG CH CY CZ DE DK EE ES FI FR GB GR • DATABASE WPI Week 200142 Derwent
HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI Publications Ltd., London, GB; AN 2001-392553
SK TR XP002413852 & JP 2001 031794 A (HOKOKU
SEIYU KK) 6 February 2001 (2001-02-06)
(30) Priority: 12.08.2005 US 202975 • DATABASE CA [Online] CHEMICAL ABSTRACTS
SERVICE, COLUMBUS, OHIO, US; ZENG,
(43) Date of publication of application: CHONGYU: "Study on esterification rule in DOTP
23.04.2008 Bulletin 2008/17 preparation" XP002413815 retrieved from STN
Database accession no. 1995:468078 & "Study on
(73) Proprietor: EASTMAN CHEMICAL COMPANY esterification rule in DOTP preparation"
Kingsport TN 37660 (US) NANJING HUAGONG XUEYUAN XUEBAO , 1
CODEN: NAXUEI; ISSN: 1000-5994, vol. 16, no. 4,
(72) Inventors: 1994, pages 69-72,
• COOK, Steven, Leroy • DATABASE CA [Online] CHEMICAL ABSTRACTS
Kingsport, TN 37660 (US) SERVICE, COLUMBUS, OHIO, US; JIANG,
• TOMLIN, Christopher, Fletcher PINPING: "Synthesis of DOTP plasticizer by
Kingsport, TN 37660-5630 (US) esterification" XP002413816 retrieved from STN
• TURNER, Philip, Wayne Database accession no. 1995:454573 &
Blountville, TN 37617 (US) "Synthesis of DOTP plasticizer by esterification"
HUAXUE SHIJIE , CODEN: HUAKAB; ISSN:
(74) Representative: Brown, Fraser Gregory James et 0367-6358, vol. 35, no. 8, 1994, pages 411-415,
al • DATABASE WPI Week 200003 Derwent
Cleveland Publications Ltd., London, GB; AN 2000-036530
10 Fetter Lane XP002413844 & RU 2 114 100 C1 (KHIMPLAST
London EC4A 1BR (GB) STOCK CO) 27 June 1998 (1998-06-27)
EP 1 912 929 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
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 1 EP 1 912 929 B1
Description
FIELD OF THE INVENTION
[0001] This invention pertains to the preparation of
di-(2-ethylhexyl) terephthalate from terephthalic acid
(TPA). More specifically, this invention pertains to a proc-
ess for the preparation of di-(2-ethylhexyl) terephthalate
by the esterification of TPA with 2-ethylhexanol (EH) at
elevated temperature and pressure while removing the
water of reaction from the reaction mixture.
BACKGROUND OF THE INVENTION
[0002] Di-(2-ethylhexyl) terephthalate, also known as
dioctyl terephthalate or DOTP, is used as a plasticizer in
a variety of polymeric materials such as polyvinyl chlo-
ride. DOTP can be prepared by the titanate-catalyzed
transesterification of dimethyl terephthalate (DMT) with
EH. Direct esterifications of TPA with EH under condi-
tions similar to those used for the transesterification of
DMT have produced slow reaction rates and sporadic
problems with foaming. US-2002028963-A1 discloses
an esterification process wherein water is removed by
azeotropic distillation together with an alcohol. JP-
60004151-A (JP-03004052-B) discloses the reaction of
TPA and EH under elevated pressures and tempera-
tures. JP-2001031794-A discloses the preparation of
terephthalic acid esters by reacting at least one of C9-C
18 monohydric alcohol and 2-ethylhexanol with tereph-
thalic acid. Water formed during the reaction was re-
moved and the alcohol was separated and recirculated
to the system. Finally, US-5,532,495 discloses a multi-
step esterification process that includes removing water
and a portion of the alcohol reactant from the reaction
mixture.
BRIEF SUMMARY OF THE INVENTION
[0003] We have developed a process for the prepara-
tion of di-(2-ethylhexyl) terephthalate by the esterification
of TPA with EH at elevated pressure and temperature
wherein the water of reaction and some of the EH is re-
moved during the esterification process. The present
invention therefore provides a process
for the preparation of di-(2-ethylhexyl) terephthalate
which comprises contacting TPA with EH in the presence
of a titanium catalyst in a reaction zone wherein the total
pressure is maintained at 100 to 400 kPa gauge (1 to 4
bar gauge), the temperature is maintained at 180° to
270°C, the EH:TPA mole ratio is maintained at 2:1 to 2.5:
1, and an inert gas is passed through the TPA/EH reac-
tion mixture in the reaction zone to cause a mixture of
water and EH to be removed from the reaction zone dur-
ing the preparation of di-(2-ethylhexyl) terephthalate. Our
novel process provides the desired diester product at
good reaction rates with high conversions of the TPA
reactant with no observable foaming problems.
2
DETAILED DESCRIPTION
[0004] The esterification process of the present inven-
tion is carried out in a reaction zone comprising a pres-
5 sure vessel while maintaining the EH:TPA mole ratio at
2:1 to 2.5:1 The pressure and temperature within the re-
action zone are maintained at 100 to 400 kPa gauge (1
to 4 bar gauge (barg)) and 180 to 270°C. Preferred pres-
sure and temperature ranges are 200 to 350 kPa gauge
10 (2 to 3.5 barg) and 180 to 260°C.
[0005] An important feature of the present invention is
the removal of water of reaction along with EH during the
esterification process. The maintenance of the EH:TPA
mole ratio at 2:1 to 2.5:1 requires the addition of EH to
15 the reaction vessel during the process. The EH/water
mixture or azeotrope removed from the reaction zone
may be allowed to separate into an EH-rich organic phase
and an aqueous phase and the EH-rich organic phase
can be returned to the reaction zone. Alternatively, the
20 EH:TPA mole ratio may be maintained at 2:1 to 2.5: by
the addition of fresh EH.
[0006] The removal of water of reaction from the reac-
tion zone is assisted by passing an inert gas through the
TPA/EH reaction mixture in the reaction zone. Nitrogen
25 is the least expensive and thus is the preferred inert gas.
The inert gas typically is fed below the surface of the
TPA/EH reaction mixture by means of a conventional
conduit or via a gas sparging device. While the inert gas
may be fed intermittently or discontinuously, it preferably
30 is fed continuously at the commencement of the esteri-
fication reaction. The amount of gas passed through the
TPA/EH reaction mixture may vary significantly but typ-
ically is in the range of 2 to 5 volumes of gas per volume
of reaction mixture per hour.
35 [0007] The titanium catalyst may be any titanium com-
pound soluble in the reaction mixture, i.e., soluble in EH
and the di-(2-ethylhexyl) terephthalate product. An ex-
ample of suitable titanium compounds include titanium
tetraalkoxides having the formula Ti(OR)4 wherein R is
40 an alkyl group of 1 to 8 carbon atoms. The catalytically-
effective amount of the titanium compound generally is
an amount which provides a titanium [Ti] concentration
of 50 to 200 parts per million by weight in the reaction
mixture. The process of the present invention may be
45 carried out in a batch, semi-continuous or continuous
mode. In the batch mode, an agitated pressure vessel is
charged with TPA, EH and catalyst, heated and pressu-
rized and the esterification is carried out while passing
an inert gas through the reaction mixture. An EH/water
50 mixture is removed and EH is fed to the reaction vessel
over the course of the process. At the conclusion of the
process, the di-(2-ethylhexyl) terephthalate product is re-
covered from the vessel and purified according to con-
ventional procedures. Continuous operation involves
55 continuously or intermittently feeding TPA, EH and cat-
alyst to and continuously or intermittently removing EH,
water and product-containing reaction mixture from a
pressure vessel maintained at a predetermined temper-
2
 3 EP 1 912 929 B1
ature, pressure and liquid level. The product-containing
reaction mixture may be fed to one or more secondary
reaction vessels wherein conversion of TPA and/or TPA
half-ester to the diester product is completed.
[0008] In the simplest embodiment, the reaction vessel
may be fitted with one inlet for EH reactant return and a
control valve to remove volatiles in lieu of a fractionation
column. The reactor is charged with terephthalic acid,
excess 2-ethylhexanol, and a catalytic amount of a tita-
nium catalyst such as titanium tetraisopropoxide (TIPT).
Heating and stirring of the mixture results in both an in-
crease in pressure and esterification of the TPA to DOTP
and the release of volatiles including EH and water. The
volatile components consist primarily of the water of re-
action and unreacted EH. These components can be
swept out of the reactor with the aid of an inert gas purge,
condensed and the 2-ethylhexanol separated from the
water and returned to the autoclave via a pump. The prod-
uct of this reaction typically is refined by filtering out un-
reacted TPA for recycle. The crude product (filtrate) is
then neutralized with 2.5 weight percent aqueous NaOH,
washed with water and filtered. Excess 2-ethylhexanol
is stripped off at reduced pressure and the residue is then
steam stripped. The stripped product is treated with ac-
tivated carbon for one hour then filtered through a filter
aid to give the final product.
[0009] In a preferred embodiment, the process may be
practiced in a continuous mode by adding the TPA to a
suitable reaction vessel by means of a screw feeder and
the EH/catalyst as a pump-fed mixture to a stirred, pres-
surized reaction vessel equipped with a reflux condenser/
decanter combination such that the water of reaction can
be removed and the unreacted EH returned to the reac-
tor. The effluent from this reactor can be passed to a
chain of one or more polishing reactors wherein the con-
version to DOTP with removal of water is continued. The
product of this reaction can be further processed and
refined by steps that are compatible with those listed for
the batch example.
EXAMPLES
[0010] The process provided by the present invention
is further illustrated by the following examples wherein
all percentages given are by weight unless specified oth-
erwise.
[0011] A 500 milliliter autoclave was charged with
137.9 g (0.83 mole) TPA, 250 g (1.92 moles) EH and 125
ppm (0.048 g) TIPT catalyst. The autoclave was
equipped with a stirrer, a conduit for feeding EH and ni-
trogen below the surface of the TPA/EH catalyst mixture,
a pressure relief conduit and a conduit fitted with a control
valve (backpressure regulator) for the removal of water
and EH. The autoclave then was sealed and heated to
approximately 180°C to generate a pressure of 100 kPa
gauge (1 barg) within the autoclave. As the reaction pro-
ceeded, a mixture of water and EH was removed and the
EH was pumped back to the autoclave. Nitrogen was fed
4
with the recycled EH to facilitate removal of water. Total
reaction time was 10.5 hours at a maximum temperature
of 260°C and a maximum autoclave pressure of approx-
imately 300 kPa gauge (3 barg). Unreacted TPA (14 g)
5 was recovered by filtration. The crude product then was
neutralized with 2.5% aqueous NaOH, washed with wa-
ter and filtered. Excess EH was stripped off at reduced
pressure and the residue then steam stripped. The
stripped product was treated with activated carbon at
10 90°C for one hour then filtered through a filter aid to give
136.6 g of product (∼80% conversion). Analysis (Gas
Chromatography, area percentages): 0.04% EH; 0.07%
di-(2-ethylhexyl) phthalate, 0.13% methyl (2-ethylhexyl)
terephthalate; 0.02% unknown; 99.42% DOTP. Color
15 (PCS): 20.
[0012] A comparative experiment was performed at at-
mospheric pressure. To a 2-liter, round-bottom flask
equipped with overhead stirrer, thermometer, heating
mantel and vapor decanter was added 350 g (2.107 mol)
20 of TPA, 687 g (5.28 mol) of EH and 0.208 g (200 ppm)
of TIPT. Upon heating, the reaction began at ∼180°C.
The temperature slowly reached 189°C in 6 hours. A tem-
perature of 202°C was achieved after 10 hours reaction
time. The temperature was held at 205°C until ∼14 hours
25 of reaction time were completed. The temperature then
reached 210°C at 15 hours, 222°C at 18 hours and the
final temperature was 230°C, where it was held for 2
hours. A reaction time of 21.5 hours was therefore re-
quired before water evolution slowed to the point that the
30 reaction was discontinued. A total of 73.5 g of water-
containing distillate was collected out of a theoretical
amount of 75.8 g. The crude product was stripped of vol-
atiles, giving a total of 125.3 g. The residue weighed
733.7 g for a yield of 88.9%. Analysis (Gas Chromatog-
35 raphy, area percentages): 0.04% EH; 0.04% di-(2-ethyl-
hexyl) phthalate, 0.36% DOTP Isomer; 99.39% DOTP.
Color (PCS): 40.
40 Claims
1. Process for the preparation of di-(2-ethylhexyl)
terephthalate which comprises contacting tereph-
thalic acid (TPA) with 2-ethylhexanol (EH) in the
45 presence of a titanium catalyst in a reaction zone
wherein, the temperature is maintained at 180° to
270°C, the EH:TPA mole ratio is maintained at 2:1
to 2.5:1, characterized in that the total pressure in
the reaction zone is maintained at 100 to 400 kPa
50 gauge (1 to 4 bar gauge (barg)) and an inert gas is
passed through the TPA/EH reaction mixture in the
reaction zone to cause a mixture of water and EH to
be removed from the reaction zone during the prep-
aration of di-(2-ethylhexyl) terephthalate.
55
2. Process according to Claim I wherein the inert gas
is passed through the TPA/EH reaction mixture at a
rate of 2 to 5 volumes of gas per volume of reaction
3
 5 EP 1 912 929 B1
mixture per hour.
3. Process according to Claim 2 wherein the titanium
catalyst is a titanium tetraalkoxide having the formula
Ti(OR)4 wherein R is an alkyl group of I to 8 carbon
atoms.
4. Process according to Claim 3 wherein the total pres-
sure is maintained at 200 to 350 kPa gauge (2 to 3.5
bar gauge (barg)), the temperature is maintained at
180° to 260°C.
5. Process according to Claim 3 or Claim 4 wherein the
concentration of the catalyst in the reaction mixture
is an amount which provides a titanium [Ti] concen-
tration of 50 to 200 parts per million by weight.
Patentansprüche
1. Verfahren zur Herstellung von Di-(2-ethylhexyl)ter-
ephthalat, das das Kontaktieren von Terephthalsäu-
re (TPA) mit 2-Ethylhexanol (EH) in Gegenwart eines
Titankatalysators in einer Reaktionszone umfasst,
wobei die Temperatur bei 180° bis 270°C gehalten
wird und das EH:TPA-Molverhältnis bei 2:1 bis 2,5:
1 gehalten wird, dadurch gekennzeichnet dass der
Gesamtdruck in der Reaktionszone bei 100 bis 400
kPa gauge [Relativdruck] (1 bis 4 bar gauge (barg))
gehalten wird und ein Edelgas durch das TPA/EH-
Reaktionsgemisch in der Reaktionszone geleitet
wird, um ein Gemisch aus Wasser und EH zu erzeu-
gen, das während der Herstellung von Di-(2-ethyl-
hexyl)terephthalat aus der Reaktionszone entfernt
wird.
2. Verfahren nach Anspruch 1, wobei das Edelgas mit
einer Rate von 2 bis 5 Volumen Gas pro Volumen
Reaktionsgemisch pro Stunde durch das TPA/EH-
Reaktionsgemisch geleitet wird.
3. Verfahren nach Anspruch 2, wobei der Titankataly-
sator ein Titantetraalkoxid mit der Formel Ti(OR)4
ist, worin R eine Alkylgruppe mit 1 bis 8 Kohlenstoffa-
tomen ist.
4. Verfahren nach Anspruch 3, wobei der Gesamtdruck
bei 200 bis 350 kPa gauge (2 bis 3,5 bar gauge
(barg)) gehalten wird und die Temperatur bei 180°
bis 260°C gehalten wird.
5. Verfahren nach Anspruch 3 oder Anspruch 4, wobei
die Konzentration des Katalysators im Reaktionsge-
misch ein Betrag ist, der eine Titan [Ti]-Konzentrati-
on von 50 bis 200 ppm an Gewicht vorsieht.
6
Revendications
1. Procédé pour la préparation de di-(2-éthylhexyl) té-
réphtalate qui comprend la mise en contact d’acide
5 téréphtalique (TPA) avec du 2-éthylhexanol (EH) en
présence d’un catalyseur au titane dans une zone
de réaction, dans lequel la température est mainte-
nue de 180°C à 270°C, le rapport molaire EH:TPA
est maintenu de 2:1 à 2,5:1, caractérisé en ce que
10 la pression totale dans la zone de réaction est main-
tenue de 100 à 400 kPa effectifs (1 à 4 bars effectifs
(barg)) et un gaz inerte est passé à travers le mé-
lange réactionnel TPA/EH dans la zone de réaction
pour faire en sorte qu’un mélange d’eau et d’EH soit
15 éliminé de la zone de réaction durant la préparation
du di-(2-éthylhexyl) téréphtalate.
2. Procédé selon la revendication 1, dans lequel le gaz
inerte est passé à travers le mélange réactionnel
20 TPA/EH à un débit de 2 à 5 volumes de gaz par
volume de mélange réactionnel par heure.
3. Procédé selon la revendication 2, dans lequel le ca-
talyseur au titane est un tétra-alcoxyde de titane de
25 formule Ti(OR)4 dans laquelle R est un groupe alkyle
de 1 à 8 atomes de carbone.
4. Procédé selon la revendication 3, dans lequel la
pression totale est maintenue de 200 à 350 kPa ef-
30 fectifs (2 à 3,5 bars effectifs (barg)), la température
est maintenue de 180°C à 260°C.
5. Procédé selon la revendication 3 ou la revendication
4, dans lequel la concentration du catalyseur dans
35 le mélange réactionnel est une quantité qui fournit
une concentration en titane [Ti] de 50 à 200 parties
par million en poids.
40
45
50
55
4
 EP 1 912 929 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• US 2002028963 A1 [0002] • JP 2001031794 A [0002]

• JP 60004151 A [0002] • US 5532495 A [0002]
• JP 03004052 B [0002]