(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual Property

Organization
International Bureau
(10) International Publication Number
(43) International Publication Date WO 2014/185872 Al
20 November 2014 (20.11.2014) PO PCT

(51) International Patent Classification: HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR,
C07C 67/08 (2006.01) C07C 69/82 (2006.01) KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME,
MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ,
(21) International Application Number: OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA,
PCT/TR20 14/000096 SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM,
(22) International Filing Date: TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM,
27 March 2014 (27.03.2014) ZW.

(25) Filing Language: English(84) Designated States (unless otherwise indicated, for every
(26) Publication Language: English
(30) Priority Data:
2013/05713 13 May 2013 (13.05.2013) TR
(71) Applicant: CEY KIMYA GERI DONUSUM MARINE
VE TICARET LIMITED SIRKETI [TR/TR]; Sekerpin-
ar Mahallesi Marmara Geri Donuijumculer Koop., Marmara
Cad. No. 4, Cayirova, Kocaeli (TR).
(72) Inventor: YILDIRIM, Cahit; Sekerpinar Mahallesi M ar
mara Geri Donii§umculer Koop., Marmara Cad. No. 4,
Cayirova, Kocaeli (TR).
(74) Agent: TIRYAKIOGLU, Yavuz; Istek Patent ve Danis-
manlik Hizmetleri Ltd. Sti., Kisikli Alemdag Caddesi Published:
No :77/03, Qamlica Istanbul (TR).
(81) Designated States (unless otherwise indicated, for every
kind of national protection available): AE, AG, AL, AM,
AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY,
BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM,
DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,
kind of regional protection available): ARIPO (BW, GH,
GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ,
UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ,
TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,
EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV,
MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM,
TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW,
KM, ML, MR, NE, SN, TD, TG).
Declarations under Rule 4.17 :
— as to applicant's entitlement to apply for and be granted a
patent (Rule 4.1 7(H))
— of inventorship (Rule 4. 1 7(iv))
— with international search report (Art. 21(3))
— before the expiration of the time limit for amending the
claims and to be republished in the event of receipt of
amendments (Rule 48.2(h))

(54) Title: DOTP (DI-OCTLY TEREPHTHALATE)PRODUCTION METHOD

(57) Abstract: The invention is DOTP (Di octly terephthalate) production method at normal atmospheric pressure without using any
© inert gas by separating the water formed in the reaction by means of column in PVC plastic production industry.
 DESCRIPTION
DOTP (DI-OCTLY TEREPHTHALATE)PRODUCTION METHOD

TECHNICAL FIELD
The invention is DOTP (Di octly terephthalate) production method at normal
atmospheric pressure without using any inert gas by separating the water formed in
the reaction by means of column in PVC plastic production industry.

BACKGROUND OF THE ART

DOTP (Di octly terephthalate) is used in the production of PVC plastic used in
many fields such as artificial leather, shoes, slippers, cable, car parts.
DOTP (Di octly terephthalate), can be obtained from the reaction of di methyl
terephthalate, and 2-ethyl hexanol with a titanium catalyst. However, the reaction
proceeds very slowly and there are foaming problems.
In other known DOTP (Di octly terephthalate) production methods, DOTP (Di

octly terephthalate) is produced by reacting terephthalic acid and 2-ethyl hexanol with
a titanium catalyst, with or without pressure in the environment open to the
atmosphere. However, the reaction time is too long in all these methods and as the
reaction could not be fully completed, acid number of the product does not fall below
0.1 mm g OH. Therefore, the product after reaction is washed with 2.5% NaOH and
acid number is reduced to below 0.1 mm g KOH. Despite all these procedures, as
the colour of DOTP produced is around 40 hazen, generated product is treated with
activated carbon and filtered for the second time. All this extra processes lead to
environmental pollution and at the same time as it lead to loss of product. Also
excess alcohol used in the reaction begins to turn yellow after use a few times.

BRIEF DESCRIPTION OF THE INVENTION

PTA and 2-EH are reacted with a catalyst with or without pressure in the
environment open to the atmosphere. Carbon number of the alcohol used is at least
6 up to 10. The reaction temperature is between 170 and 220 °C. There is a tower in
the system independent from the reactor. The reactor is connected to towers with a
total of 4 pipelines in different diameters. Alcohol and water formed during the
reaction vapour go to the tower from both of these lines. From other two lines,
completely water-free alcohol in the tower returns back to the reactor. DOTP
produced by this method need to be washed with the 2.5% NaOH, and only washing
with water is sufficient. After washing with water, Although the product is sent directly
to the filter without being processed with active carbon, colour of the product is 10
hazen. Even if the excess alcohol used in the reaction is used for hundreds of times,
it definitely does not turn yellow, and does not lose its properties.

DETAILED DESCRIPTION OF THE INVENTION

DESCRIPTION OF FIGURES
Figure 1: Figure 2:various views of the tower and reactor from which the present is
produced
Reference numbers
10- Reactor
20- Small columns (which alcohol and water vapour into the tower)
30- The main column (alcohol and water vapour carrying the tower)
40- The column bearing water-free alcohol to the tower
50- Spare line (when the column 40 used to bearing water-free alcohol to
the tower is not enough)
60- Platform
70- Collecting tank (Water vapour and alcohol escaping from the tower
without condensing)
80- Collecting boiler(which pumps the alcohol that cannot be returned to
the reactor into the reactor due to pressure differences)
90- The Tower
100- The water line that cools exchangers
110- The water line that cools exchangers

The catalyst used in the production method of DOTP (Di octly terephthalate) is
selected from the group consisting of TIPT (Titanium (IV) isopropoxide (97+%)
(Tetraisopropyltitanate, tetrapropylorthotitanate), TIBT (Titanium (IV) n-butoxide
(98+%) (Tetraisobutyltitanate), TNBT (Titanium (IV) n-butoxide (98+%) (Tetra n-butyl
titanate), MSA (Methanesulfonic acid), tin(ll) oxalate ( stannous oxalate ) .
To achieve the mentioned objectives, the present invention is the use of Di
octyl terephthalate (DOTP) esters obtained according to the above considerations as
plasticizers.
Water and alcohol carried formed in the reaction with small columns (20) and
the main column (30) which is the connection between the reactor (10) and the tower
(90); and carrying alcohol, and water vapour to the tower is sent to the tower. The
reason why there are two lines carrying alcohol and water vapour formed between
the reactor (10) and the tower (90) is to prevent foaming and pressure generation in
the reactor (10).
In the tower (90), there are at least 2 and maximum of 12 heat exchangers

and at least 2 but no more than 12 rooms. Water and alcohol condensing in the tower
(90) are separated from each other due to the difference intensity. Condensed water
is collected at the bottom of the tower (90). The completely water-free alcohol carried
in the tower (90) together with water returns to reactor ( 0) from the column carrying
water-free alcohol to the tower (40) and from the spare line (50). Albeit in very small
amounts, water or alcohol not condensing in the tower (90) passes through the top of
tower, water vapour and alcohol escaping from the tower without condensing is
collected in the collection tank (70). Excess alcohol that cannot be returned to the
tower due to pressure differences is collected collecting boiler (80) and is pumped to
the tower (90).
A reactor (10)used in the production of Di-Octyl terephthalate (DOTP) ester of
the present invention is illustrated in Figs. The reactor (10) has a structure having a
simple stirrer and a heater which is controlled by a temperature control element. The
reactor ( 0) is connected to the tower by two columns, a small column (20) carrying
alcohol and water vapour in the tower and a main column (30) carrying alcohol, and
water vapour in the tower. The tower (90) is open to atmosphere from the collecting
tank (70) where the escaping alcohol and water vapour are deposited, and
accordingly, the system works at atmospheric pressure. PTA, the alcohol and a
catalytic amount of catalyst are introduced in the reactor (10). The reactor (10) is
heated by the heater. When the reactor (10) temperature rises, excess alcohol and
the water formed in the reaction begins to mobilize along the tower (90). Alcohol
condensed by means of heat exchangers located in the tower (90) is separated from
water and returns through the column (40) and spare lines (50) carrying alcohol-free
water to the tower and which are the columns for returning to the reactor (10). The
condensed water is collected at the bottom of the tower (90) before returning the
reactor (10). PTA; alcohol molar ratios is 1; 2 . However, excess alcohol is used in
production. Excess alcohol content is 10% to 80%. Excess alcohol is taken back at
the end of the production. The reaction time is between 4 to 6 hours. The amount of
the resulting water and acid number of the product is followed, when acid number
falls below 0.1 mg / KOH, the production is terminated. Under vacuum, excess
alcohol is taken back. The crude product is washed with water, filtered and the
production is ended.
 CLAIMS

The present invention is a production method DOTP (Di-Octyl Terephthalate),

and characterized in comprising the process steps in which;
tereftalatic acid (PTA) reacts with at least one alcohol and at least one
catalyst i a reactor (10) in a pressureless operation open to the
atmosphere, without using any inert gas,
the reactor (10) began to be heated with the heater,
when the reactor (10) temperature rises, excess alcohol and the water
formed in the reaction begins to mobilize along the tower (90)
The water and the alcohol formed in the reaction is sent to the tower by
small column (20) and the main column (30) which are the connection
between reactor (10) and the tower (90); and carrying alcohol, and
water vapour to the tower in order to prevent foaming and pressure in
the reactor (10),
Water condensed in the tower (90), and separated from alcohol due to
difference of intensity is collected at the bottom of the tower (90),
the totally water-free alcohol located in the tower return to the reactor
(10) from column (40) and the spare line (50) carrying alcohol to the
tower by means of heat exchangers,
Noncondensing water or alcohol passes through the upper part of the
tower (70), and collected in the collecting tank
excess alcohol that cannot return to the tower due to pressure
differences is collected in the collecting boiler (80) and is pumped to the
tower (90),
excess alcohol is taken under vacuum after the production,
resulting water content and acid number of the product is monitored
and when the acid number falls below 0.1 mg / KOH, production is
ended,
crude product is washed with water, filtered and the production is
ended,
DOTP produced by this method does not need to be washed with 2.5%
NaOH and washed with water only,
after washing with water, it is sent directly to the filter without being
 processed with active carbon or bleaching earth.
A method of production DOTP (Di-Octyl Terephthalate) according to claim 1 ,
characterized in that the colour of the product is at most 10 Hazen and the
excess alcohol does not turn yellow even if used hundred times.
A method of production DOTP (Di-Octyl Terephthalate) according to claim 1,
characterized in that carbon number of the alcohol used is at least 6 up to 0 .
A method of production DOTP (Di-Octyl Terephthalate) according to claim 1 ,
characterized in that PTA; alcohol molar ratio is 1; 2 .
A method of production DOTP (Di-Octyl Terephthalate) according to claim 3 ,
characterized in that in production, the use of excess alcohol is 80% to 10%.
A method of producing DOTP (Di-Octyl Terephthalate) according to one of the
preceding claims, characterized in that the reactor (10) has a structure having
a simple stirrer and a heater which is controlled by a temperature control
element.
A method of producing DOTP (Di-Octyl Terephthalate) according to one of the
preceding claims, characterized in that the tower (90) is open to the
atmosphere through collecting tank (70) where escaping alcohol and water
vapour are collected and pressure is normal atmospheric pressure.
A method of producing DOTP (Di-Octyl Terephthalate) according to one of the
preceding claims, characterized in that the reaction temperature is between
170 °C and 220 °C.
A method of producing DOTP (Di-Octyl Terephthalate) according to one of the
preceding claims, characterized in that the tower (90) comprises at least two
and a maximum of 12 heat exchangers and at least 2 and no more than 12
rooms.
A method of producing DOTP (Di-Octyl Terephthalate) according to one of the
preceding claims, characterized in that the catalyst used is a catalyst selected
from the group of TIPT (Titanium (IV) isopropoxide (97+%)
(Tetraisopropyltitanate, tetrapropylorthotitanate), TIBT (Titanium (IV) n-
butoxide (98+%) (Tetraisobutyltitanate), TNBT (Titanium (IV) n-butoxide
(98+%) (Tetra n-butyl titanate), MSA (Methanesulfonic acid), tin(ll) oxalate (
stannous oxalate ) .
A method of producing DOTP (Di-Octyl Terephthalate) according to one of the
preceding claims, characterized in that terephthalate (DOTP) esters are used
 INTERNATIONAL SEARCH REPORT
International application No

PCT/TR2014/0OQ096
A . CLASSIFICATION O F SUBJECT MATTER
INV. C07C67/08 C07C69/82

According to International Patent Classification (IPC) or to both national classification and IPC

B. FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols
C07C

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

EPO-Internal

C . DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

US 2007/161815 Al (OSBORNE VICKI E H [US] 1-11

ET AL OSBORNE VICKI E HAYGOOD [US] ET AL)
12 July 2007 (2007-07-12)
paragraphs [0006] , [0010] , [0018] ,
[0019]
f i gures 1 , 2
exampl e s 3 , 4

US 2008/183012 Al (COOK STEVEN LER0Y [US] 1-11

ET AL) 3 1 July 2008 (2008-07-31)
paragraphs [0016] , [0033] , [0035]
pages 1 , 2

□ Further documents are listed in the continuation of Box C . See patent family annex.

* Special categories of cited documents :

"A" document defining the general state of the art which is not considered
to be of particular relevance
"E" earlier application or patent but published o n or after the international
filing date
"L" document which may throw doubts on priority claim(s) orwhich is
cited to establish the publication date of another citation or other
special reason (as specified)
"O" document referring to a n oral disclosure, use, exhibition or other
means
"P" document published prior to the international filing date but later than
the priority date claimed
"T" later document published after the international filing date or priority
date and not in conflict with the application but cited to understand
the principle or theory underlying the invention
"X" document of particular relevance; the claimed invention cannot be
considered novel or cannot be considered to involve an inventive
step when the document is taken alone
" document of particular relevance; the claimed invention cannot be
considered to involve an inventive step when the document is
combined with one or more other such documents, such combination
being obvious to a person skilled in the art
"&" document member of the same patent family

Date of the actual completion of the international search Date of mailing of the international search report

12 September 2014 19/09/2014

Name and mailing address of the ISA/ Authorized officer
European Patent Office, P.B. 5818 Patentlaan 2
NL - 2280 HV Rijswijk
Tel. (+31-70) 340-2040,
Fax: (+31-70) 340-3016 Panday, Narendra
 INTERNATIONAL SEARCH REPORT
International application No
Information on patent family members
PCT/TR2014/0OQ096
Patent document Publication Patent family Publication
cited in search report date member(s) date

US 2007161815 Al 12-07-2007 BR PIQ806244 A2 0 6 -09--2011

CN 101600680 A 09--12·-2009
EP 2114854 Al 11--11--2009
ES 2399301 T3 27--03·-2013
P 2010516809 A 20--05--2010
KR 20090115125 A 04--11--2009
MX 297669 B 29--03--2012
T 200846315 A 01--12·-2008
US 2007161815 Al 12--07--2007
O 2008094396 Al 07--08·-2008

US 2008183012 Al 31-07-2008 BR PI0808031 A2 17--06·-2014

CN 101652343 A 17--02--2010
EP 2139844 Al 0 6 -01--2010
P 2010523560 A 15--07--2010
KR 20100014672 A 10--02·-2010
TW 200904795 A 01--02·-2009
US 2008183012 Al 31--07·-2008
WO 2008123928 Al 16--10·-2008