CN104058968A - Manufacturing method of bis(2-ethylhexyl) terephthalate - Google Patents
Manufacturing method of bis(2-ethylhexyl) terephthalate Download PDFInfo
- Publication number
- CN104058968A CN104058968A CN201310093629.0A CN201310093629A CN104058968A CN 104058968 A CN104058968 A CN 104058968A CN 201310093629 A CN201310093629 A CN 201310093629A CN 104058968 A CN104058968 A CN 104058968A
- Authority
- CN
- China
- Prior art keywords
- water
- reaction
- alcohol
- ethylhexyl
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a manufacturing method of bis(2-ethylhexyl) terephthalate, which comprises: performing an esterification reaction of terephthalic acid and 2-ethyl hexanol in the presence of a chelating catalyst. The method of the invention can increase the reaction speed, improve the filtering efficiency of the esterified product, and prepare bis(2-ethylhexyl) terephthalate with low hue (APHA).
Description
Technical field
The present invention is about the method for a kind of manufacture terephthalic acid two (2-ethylhexyl); Especially in regard to a kind of method of utilizing the chelating type catalyst manufacture terephthalic acid two (2-ethylhexyl) of titanium or zirconium.
Background technology
Terephthalic acid two (2-ethylhexyl) (is also called terephthalic acid di-isooctyl, referred to as DOTP) for being used in the nontoxic plasticizer of food product containers, its have good with the polymeric material consistency such as polyvinyl chloride (PVC), be the feature of low volatility and electrical property excellence.Can, by 2-Ethylhexyl Alcohol and terephthalic acid (TPA), in pressurized conditions and catalyzer, there is lower preparation and obtain in DOTP.
In known techniques in order to promote the reaction efficiency of the esterification of terephthalic acid, in Japanese patent application case publication number JP2004300078A for example, be disclosed in the esterification reaction process of manufacturing bis--terephthalate, use high boiling solvent, promote esterification temperature, and can accelerate the technology of esterification.
The esterification of above-mentioned terephthalic acid is a balanced reaction again, if the by product-water that can continuously reaction be produced, from reaction, remove, it is mobile that balance can be partial to product side (being ester side), if water is not removed from reactive system in reaction, not only catalyst can passivation, also can balance move reach certain transformation efficiency after reaction become very slow.For head it off, in China Patent No. CN1225455C for example, disclose a kind of method of producing polybasic ester, it lies in reaction zone under esterifying catalyst exists, add hot acid or its acid anhydrides and alcohol composition, and in reaction process, use steam distillation that the steam that contains alcohol and water is separated into respectively to rich alcohol cut and rich aqueous distillate, and this richness alcohol cut is returned to reaction zone and make rich aqueous distillate leave reaction process, and can adjust rapidly the transformation efficiency of basal ration.
At present, for DOTP preferably preparation method still have ardenter demand, and need further exploitation.
Summary of the invention
Main purpose of the present invention is to provide a kind of simple equipments, promotes the manufacture method of the terephthalic acid two (2-ethylhexyl) of esterification reaction rate and lifting filtration efficiency, to solve in aforesaid method, still have the problem that need to promote speed of reaction, improve gained carboxylate filtration efficiency.
In view of the foregoing, the invention provides the manufacture method of a kind of terephthalic acid two (2-ethylhexyl), it comprises: in reactor, in rare gas element with gauge pressure 1.0～4.0kg/cm
2pressure, and temperature of reaction is under the condition of 180 to 260 ℃, under the chelating type catalyst of following formula (I) exists, make terephthalic acid and 2-Ethylhexyl Alcohol carry out esterification, wherein 2-Ethylhexyl Alcohol is 2.6: 1 to 4.0: 1 with respect to the mol ratio of terephthalic acid:
(RO)
mT-(O-Y-X)
n(I)，
Wherein, in formula (I), R is hydrogen or C
1-C
8straight or branched alkyl, T is titanium or zirconium, Y is C
2-C
3stretch alkyl or divalence phosphate radical, X is the functional group containing aerobic or nitrogen, and m is 1 or 2 integer and n is free 2 or 3 the integer of choosing.By utilizing this chelating type catalyst, method of the present invention can promote the speed of reaction of esterification, and improves carboxylate filtration efficiency, and can make the terephthalic acid two (2-ethylhexyl) of low form and aspect (for example form and aspect (platinum-cobalt)≤30).
According to preferred embodiment of the present invention, wherein this chelating type catalyst is phosphoric acid ester titanate chelate, trolamine titanic acid ester or tri-alkoxy butyl phosphate titanium dipolymer; Wherein the content in titanium or zirconium metal in this chelating type catalyst adds up to heavy 20ppm to 400ppm with respect to acid and the reactant of alcohol.
Moreover, implement the reactor that method of the present invention used and be provided with a condenser and a water-and-oil separator, and must be by the water generating in reaction process and alcohol mixture condensation separated in this water-and-oil separator; In a preferred embodiment, this reactor is provided with again a return line, make the alcohol mixed solution of gained be back to reactor via this return line cycling stream, therefore, can keep the molar ratio of alcohol and terephthalic acid in reactor at certain proportion, and the water shifting out by metering autoreactor and can calculate the transformation efficiency of terephthalic acid.
The method according to this invention, the 2-Ethylhexyl Alcohol that wherein used can be pure 2-Ethylhexyl Alcohol and also can be the 2-Ethylhexyl Alcohol reclaiming in reaction, is the latter's situation, when it contains water, can without dewatering, be directly used in the inventive method; This 2-Ethylhexyl Alcohol is 2.6: 1 to 4.0: 1 with respect to the mol ratio of terephthalic acid, is preferably 3.0: 1 to 3.5: 1; The reaction pressure of method of the present invention is preferably 1.0 to 4.0kg/cm
2gauge pressure, the mode of pressure initiation can be utilized nitrogen pressurization or under inert environments, heat and naturally improve the method for pressure, better system use nitrogen pressurization.
In preferred embodiment of the present invention, this esterification reaction temperature is 180 to 260 ℃, is preferably 200 to 250 ℃.
The manufacture method of terephthalic acid two of the present invention (2-ethylhexyl), used the chelating type catalyst shown in above-mentioned formula (I), not only can promote speed of reaction, also the filtering rate of terephthalic acid two (2-ethylhexyl) can be improved, the terephthalic acid two (2-ethylhexyl) of low form and aspect can be obtained.In addition, utilize method of the present invention, reactor does not need to set complicated fractionation tubing string, only need to use simple condenser and a water-and-oil separator, can the water generating in reaction process and alcohol mixture condensation in this water-and-oil separator is also separated, further reach and avoid catalyst to meet water passivation, the effect in minimizing reaction times.Certainly in not undermining the scope of effect of the present invention, also can optionally install fractionation tubing string additional.
Embodiment
Main purpose of the present invention is to provide a kind of simple equipments, promotes the manufacture method of the terephthalic acid two (2-ethylhexyl) of esterification reaction rate and lifting filtration efficiency.The manufacture method of terephthalic acid two of the present invention (2-ethylhexyl) is carried out in comprising the reaction zone of pressurized vessel, simultaneously for esterification is carried out smoothly, alcohol composition is better to surpass the excessive use of molar weight of sour composition, the mol ratio of 2-Ethylhexyl Alcohol and terephthalic acid is 2.6: 1 to 4.0: 1, and preferably mol ratio is 3.0: 1 to 3.5: 1.
A feature of the present invention is in this manufacture method, uses the chelating type catalyst of following formula (I), makes terephthalic acid and 2-Ethylhexyl Alcohol carry out esterification,
(RO)
mT-(O-Y-X)
n(I)，
Wherein, in formula (I), R is hydrogen or C
1-C
8straight or branched alkyl, T is titanium or zirconium, Y is C
2-C
3stretch alkyl or divalence phosphate radical, X is the functional group containing aerobic or nitrogen, and m is that 1 or 2 positive integer and n are 2 or 3 integer.
Representational
As representational chelating catalyst, have for example: phosphoric acid ester titanate chelate, three (trolamine) sec.-propyl titanate chelate, tri-alkoxy phosphoric acid butyltitanate dimer, dihydroxyl (2 hydroxy propanoic acid ammonium) titanate chelate, two (dioctyl phosphoric acid ester) di-isopropyl titanate chelate, two (dioctylphyrophosphoric acid ester groups) stretch ethyl titanate chelate, three (dioctyl phosphoric acid ester) sec.-propyl titanate chelate, two (glutarate) dipropyl titanate chelate, two (trolamine) diisobutyl titanate chelate, two (methyl ethyl diketone) di-isopropyl titanate chelate, two (ethyl acetopyruvate) dibutyl titanate chelate, two (trolamine) di-isopropyl titanate chelate, two (Acetyl Acetone acid esters) butyl sec.-propyl titanate chelate, two (methyl aceto acetate) dibutyl titanate chelate, two (methyl aceto acetate) di-isopropyl titanate chelate, three (dioctyl phosphate radical) sec.-propyl titanate chelate, three (dioctylphyrophosphoric acid ester) sec.-propyl titanate chelate, two (trolamine) di-isopropyl titanate chelate, two (citric acid diethyl ester) di-isopropyl zirconate inner complex, two (trolamine) di-isopropyl zirconate inner complex, three (trolamine) sec.-propyl zirconate inner complex, dihydroxyl (2 hydroxy propanoic acid ammonium) zirconate inner complex.
As the catalyzer of significant quantity, titanium or zirconium content in the chelating type catalyst of its Chinese style (I) are the 20ppm to 400ppm of reactant weight, enable to continue to esterification reaction section and even processing procedure and finally all do not need neutralization; And the product yield height that the high conversion of can take obtains the excellent form and aspect of form and aspect (platinum-cobalt)≤30 and the low acid value of acid value < 0.1mgKOH/g is its feature.
In the method for the invention, esterification, under 180-260 ℃ of temperature condition, better at 200-250 ℃, is preferably at the temperature of 230-250 ℃ and carries out.If esterification is lower than the temperature of 200 ℃ of its lower limit, speed is crossed slow and esterification is incomplete; If reaction is higher than the temperature of 260 ℃ of its upper limits, alcohol easy inferior solution in unit causes side reaction to produce.Esterification reaction section is at least pressed and is greater than 1.0kg/cm at still
2under gauge pressure, carry out, more fortunately 1.0-4.0kg/cm
2under gauge pressure, carry out; Pressure initiation mode can be pressurizeed or the nature hoisting way of heating under nitrogenize environment by nitrogen, is suitable for nitrogen pressuring method.About 120-360 minute of time, preferably 150-250 minute are carried out in esterification.
Anyly normally usedly can all be applicable to method of the present invention by reactor heating, as stirred-tank reactor.In addition, the water producing for thorough separated esterification, to avoid catalyst passivation and to improve conversion rate, another feature of method of the present invention is not need to arrange complicated fractionation tubing string, and be provided with water-and-oil separator in this reactor, make the steam condensation separated in this water-and-oil separator that contains alcohol and water; In a preferred embodiment, this reactor is provided with a return line, and this esterification, and alcohol liquid flows back to reactor via this return line, the molar ratio that can keep alcohol and terephthalic acid in reactor, continue to participate in esterification, and isolated water can shift out metering in reactor, to weigh the transformation efficiency of terephthalic acid.
Another feature of the present invention is the thick ester articles in above-mentioned esterification, via obtaining the goods that a purity is high, form and aspect are good, acid value is low after decompression and purifying.This purifying manufacturing process can be in above-mentioned transesterification reactor or is separately connect a distillation tower, evaporates purifying in thin-film evaporator or use filter paper to filter purifying.Depressor response continues to carry out under the condition of 240 ℃ of vacuum tightness < 2 mmhg and temperature <; If vacuum tightness > 2 mmhg, reclaim speed slow; 240 ℃ of temperature >, terephthalic acid two (2-ethylhexyl) Yin Gaowen inferior solution causes goods form and aspect variation, acid value to raise, and processing characteristics is not good.
In sum, known method of the present invention is characterised in that uses terephthalic acid and 2-Ethylhexyl Alcohol, under the catalyst shown in above-mentioned formula (I) exists, carry out esterification, decompression and purifying procedure, not only can promote speed of reaction, and improve carboxylate filtration efficiency, and can obtain terephthalic acid two (2-ethylhexyl) goods of the low form and aspect of form and aspect (platinum-cobalt)≤30 and the low acid value of acid value < 0.1mgKOH/g.
The present invention will explain detailedly with the following example, only these embodiment only for the purpose of illustration, but not in order to limit the scope of the invention.
Embodiment 1
In one be furnished with have agitator, in the 3L autoclave of thermometer, back pressure valve pressure warning unit, water-and-oil separator, return line, nitrogen flow controller, condenser and 30cm filling fractionation tubing string, by the isooctyl alcohol of 1333.2g (10.24mole), (claim again 2-Ethylhexyl Alcohol, 2-EH), TyzorPC-64 (the phosphoric acid ester titanate chelate of the pure terephthalic acid (PTA) (PTA) of 531.5g (3.20mole), 3.07g (being that the total restatement of alcohol and acid reaction is equivalent to Ti=82ppm with respect to reaction), Ti=5.0%, purchased from DORF KETAL CO.) catalyst drops in reactor.It is 4.0kg/cm that reactor fully stirs and be forced into gauge pressure under nitrogen gas stream
2make temperature in 1 hour, be warming up to 232 ℃ (starting esterification recovered temperature), by water outlet that nitrogen gas stream is with and alcohol mixture, start after filling fractionation tubing string and condenser condensation in water-and-oil separator, upper strata alcohol mixture is led back reactor to guarantee that reacting 2-EH/PTA maintains 3.2/1 fixed molar ratio by return line, and lower layer of water continues to distillate in water-and-oil separator and shifts out and measured.After continuing 0.6 hour, the reactions of 232 ℃ are warming up to again 250 ℃, react again after 5 hours that by separator, to shift out water be 114.0 milliliters (theoretical values 99.0%) through metering, start pressure release slowly to normal pressure, temperature of reaction is 235 ℃ and the 2-EH that collects 205.9g through condenser, the acid value of the diester of gained crude reaction thing is 0.05mg KOH/g, and esterification amounts to lasts 5.6 hours.Secondly crude product ester is reduced pressure, by 100 mmhg, be decompressed to gradually vacuum tightness < 1 mmhg and distillation temperature continues to distillate unreacted alcohol under 180-190 ℃ of condition, distill last 0.5 hour after vacuum tightness reaches < 1 mmhg after and carry out decompress(ion), obtain the DOTP raw product of 1208g, get 500g through Whatman#5 filter paper, filtration time 45 minutes 19 seconds, the odorless product of form and aspect (platinum-cobalt) (according to the value of ASTM D-1209 test determines) 12, acid value 0.03.
Embodiment 2
Use reactor and the compound of reaction identical with embodiment 1, but replace filling fractionation tubing string with 30cm single tube, and catalyst system is used Tyzor TE (two (trolamine) di-isopropyl titanate chelate), and Ti=8.2%, purchased from DORF KETAL CO. product).The Tyzor TE (Ti=82ppm) of the PTA of the 2-EH of 1333.2g (10.24mole), 531.5g (3.20mole) and 1.87g is dropped in reactor.It is .4.0kg/cm that reactor fully stirs and be forced into gauge pressure under nitrogen gas stream
2and be warming up to 233 ℃ in 1 hour, by nitrogen gas stream with water outlet and alcohol mixture, start after single tube (meaning the tubing string of non-filler) and condenser condensation in water-and-oil separator, upper strata alcohol mixture is led back reactor to guarantee that reacting 2-EH/PTA maintains 3.2/1 fixed molar ratio by return line, and lower layer of water continues to distillate in water-and-oil separator and shifts out metering.The reactions of 232 ℃, continue 0.6 hour, be warming up to subsequently 250 ℃, react again after 3 hours and shift out water through measuring 114 milliliters (theoretical values 99.0%) by separator, start pressure release slowly to normal pressure, temperature of reaction is 236 ℃ and the 2-EH that collects 225g through condenser, this surveys to such an extent that gained crude product ester acid value is 0.10mg KOH/g, esterification course 3.7 hours.Secondly crude product ester is reduced pressure, by 100 mmhg, be decompressed to gradually vacuum tightness < 2 mmhg and distillation temperature continues to distillate unreacting alcohol under 180-190 ℃ of condition, distill in vacuum tightness and reach < 2 mmhg decompress(ion) after 0.5 hour, after filtration, time is 9 minutes 17 seconds, obtain the DOTP of 1233g, the odorless product of form and aspect (platinum-cobalt) 22, acid value 0.08.
Embodiment 3
Use as enforcement 1 reactor, but catalyst is used Tyzor IAM (tri-alkoxy phosphoric acid butyltitanate dimer, Ti=8.8%, purchased from DORF KETAL CO.).The Tyzor IAM (Ti=82ppm) of the PTA of the 2-EH of 1333.2g (10.24mole), 531.5g (3.20mole) and 1.68g is dropped in reactor.It is 3.0kg/cm that reactor fully stirs and be forced into gauge pressure under nitrogen gas stream
2and in 1 hour, be warming up to 227 ℃, by water outlet that nitrogen gas stream is with and alcohol mixture, start after filling fractionation tubing string and condenser condensation in water-and-oil separator, upper strata alcohol mixture is led back reactor to guarantee that reacting 2-EH/PTA maintains 3.2/1 fixed molar ratio by return line, and lower layer of water continues to distillate in water-and-oil separator and shifts out metering.React persistently overheating to 250 ℃, after 3.7 hours, by separator, shift out water through measuring 116 milliliters (theoretical values 100.7%) again, start pressure release slowly to normal pressure, temperature of reaction is 242 ℃ and the 2-EH that collects 175g through condenser, this surveys to such an extent that the acid value of reacting coarse product ester is 0.08mg KOH/g, esterification course 4.0 hours.Secondly crude product ester is reduced pressure, by 100 mmhg, be decompressed to gradually vacuum tightness < 2 mmhg and temperature of reaction continues to distillate alcohol excess under 180-190 ℃ of condition, react on vacuum tightness < 2 mmhg decompress(ion) after 0.5 hour, after filtration, filtration time is 4 minutes 5 seconds, obtain DOTP 1227g, the odorless product of its form and aspect (platinum-cobalt) 25, acid value 0.08.
Embodiment 4
One be furnished with have agitator, in the 3L autoclave of thermometer, back pressure valve pressure warning unit, water-and-oil separator, return line, nitrogen flow controller, condenser and 30cm filling fractionation tubing string, by the terephthalic acid two of 746g (2.70mole)-(2-ethylhexyl) (DOTP), the PTA of 2-EH, the 319g (1.92mole) of 800g (6.15mole) and the Tyzor PC-64 catalyst of 3.07g (Ti=82ppm) drop in reactor.It is 4.0kg/cm that reactor fully stirs and be forced into gauge pressure under nitrogen gas stream
2and be warming up to 248 ℃ in 1 hour, the water of being taken out of by nitrogen gas stream and alcohol mixture start after filling fractionation tubing string and condenser condensation in water-and-oil separator, upper strata alcohol mixture is led back reactor to guarantee that reacting 2-EH/PTA maintains 3.2/1 fixed molar ratio by return line, lower layer of water continue to distillate in water-and-oil separator shift out with metering.Temperature of reaction maintains 250 ℃, after 3.8 hours, by separator, shifting out water is again 69.0 milliliters (theoretical values 99.7%) through metering, start pressure release slowly to normal pressure, temperature of reaction is 235 ℃ and the 2-EH that collects 205.9g through condenser, this surveys to such an extent that the acid value of reacting coarse product ester is 0.06mg KOH/g, and esterification is lasted 4.3 hours.Secondly crude product ester is reduced pressure, by 100 mmhg, be decompressed to gradually vacuum tightness < 2 mmhg and temperature of reaction continues to distillate alcohol excess under 180-190 ℃ of condition, react on vacuum tightness < 2 mmhg decompress(ion) after 0.5 hour, obtain the DOTP raw product of 1528g, get 500g through Whatman#5 filter paper, filtration time 10 minutes 12 seconds is the odorless product of form and aspect (platinum-cobalt) 20, acid value 0.06.
Embodiment 5
Use as embodiment 1 reactor, but replace filling fractionation tubing string with 30cm single tube, catalyst is used TyzorIAM.The Tyzor TE of the PTA of the 2-EH of 1333.2g (10.24mole), 531.5g (3.20mole), 1.68g (Ti=82ppm) is dropped in reactor.It is .4.0kg/cm that reactor fully stirs and be forced into gauge pressure under nitrogen gas stream
2and be warming up to 230 ℃ in 0.8 hour, by water outlet that nitrogen gas stream is with and alcohol mixture, start after single tube and condenser condensation in water-and-oil separator, upper strata alcohol mixture is led back reactor to guarantee that reacting 2-EH/PTA maintains 3.2/1 fixed molar ratio by return line, and lower layer of water continues to distillate in water-and-oil separator and shifts out metering.Reaction continues to be warming up to 250 ℃ after 0.5 hour, after 2.7 hours, by separator, shift out water through measuring 114.5 milliliters (theoretical values 99.4%) again, start pressure release slowly to normal pressure, temperature of reaction is 242 ℃ and the 2-EH that collects 188g through condenser, this surveys to such an extent that the acid value of reacting coarse product ester is 0.10mg KOH/g, and esterification is lasted 2.7 hours.Secondly crude product ester is reduced pressure, by 100 mmhg, be decompressed to gradually vacuum tightness < 2 mmhg and distillation temperature continues to distillate alcohol excess under 180-190 ℃ of condition, react on after vacuum tightness reaches < 2 mmhg and within 0.5 hour, give decompress(ion), after filtration, filtration time is 6 minutes 43 seconds, obtain the DOTP of 1235g, the odorless product of its form and aspect (platinum-cobalt) 35, acid value 0.08.
Comparative example 1
In a 3L glass reaction still of being furnished with agitator, thermometer, water-and-oil separator, return line, nitrogen flow meter, condenser and 30cm filling fractionation tubing string, by the PTA of the 2-EH of 1000.0g (7.68mole), 531.5g (3.20mole), Tytan TBT catalyst 3.14g (tetra-n-butyl titanate, Ti=280ppm, purchased from Borica company) drop in reactor.Reactor fully stirs under normal pressure and heats up under nitrogen gas stream, in 0.7 hour, be warming up to 178 ℃, by water outlet that nitrogen gas stream is with and alcohol mixture, start after filling fractionation tubing string and condenser condensation in water-and-oil separator, upper strata alcohol mixture is led back reactor to guarantee that reacting 2-EH/PTA maintains 2.4/1 fixed molar ratio by return line, lower layer of water continue to distillate in water-and-oil separator shift out with metering.Reaction continues to be warming up to 240 ℃ after 5 hours, by separator, shifts out water through measuring 116 milliliters (theoretical values 100.7%), and this surveys to such an extent that the acid value of reacting coarse product ester is 0.11mg KOH/g, and esterification is lasted 5.0 hours.Secondly crude product ester is reduced pressure, by 100 mmhg, be decompressed to gradually vacuum tightness < 2 mmhg temperature of reaction and continue to distillate alcohol excess under 180-190 ℃ of condition, react on after vacuum tightness arrives < 2 mmhg and within 0.5 hour, give decompress(ion), obtain the DOTP crude product of 1235g, get 500g through Whatman#5 filter paper, filtration time is 57 minutes 38 seconds, is the odorless product of form and aspect (platinum-cobalt) 45, acid value 0.10.
Comparative example 2
One be furnished with have agitator, in the 3L glass reaction still of thermometer, water-and-oil separator, return line, nitrogen flow meter, condenser and 30cm filling fractionation tubing string, by the Tytan TBT catalyst (tetra-n-butyl titanate of the PTA of the 2-EH of the DOTP of 613g (2.22mole), 600.2g (4.61mole), 319g (1.92mole) and 1.81g (Ti=165ppm), Ti=280ppm, purchased from Borica company) drop in reactor.Reactor fully stirs in normal pressure and heats up under nitrogen gas stream, temperature was also warming up to 192 ℃ in 0.5 hour, by water outlet that nitrogen gas stream is with and alcohol mixture, start after filling fractionation tubing string and condenser condensation in water-and-oil separator, upper strata alcohol mixture is led back reactor to guarantee that reacting 2-EH/PTA maintains 2.4/1 fixed molar ratio by return line, lower layer of water continue to distillate in water-and-oil separator shift out with metering.After water and alcohol mixture start to distillate, in 3 hours, make temperature be warming up to 250 ℃, after 1.4 hours, by separator, shift out water through measuring 68.5 milliliters (theoretical values 100.1%) again, this surveys to such an extent that the acid value of reacting coarse product ester is 0.11mg KOH/g, and esterification is lasted 4.4 hours.Secondly crude product ester is reduced pressure, by 100 mmhg, be decompressed to gradually vacuum tightness < 2 mmhg and temperature of reaction continues to distillate alcohol excess under 180-190 ℃ of condition, react on after vacuum tightness arrives < 2 mmhg and within 0.5 hour, give decompress(ion), obtain DOTP 1235g crude product, get 500g through Whatman#5 filter paper, filtration time is 135 minutes 30 seconds, is the micro-turbid product of form and aspect (platinum-cobalt) 45, acid value 0.11.
Comparative example 3
Use and implement 1 identical reactor, by the Tytan TBT catalyst (tetra-n-butyl titanate of the PTA of the 2-EH of 1333.2g (10.24mole), 531.5g (3.20mole) and 3.73g (Ti=280ppm), Ti=280ppm, purchased from Borica company) drop in reactor.It is 4.0kg/cm that reactor fully stirs and be forced into gauge pressure under nitrogen gas stream
2and in 1 hour, be warming up to 228 ℃, by water outlet that nitrogen gas stream is with and alcohol mixture, start after filling fractionation tubing string and condenser condensation in water-and-oil separator, upper strata alcohol mixture is led back reactor to guarantee that reacting 2-EH/PTA maintains 3.2/1 fixed molar ratio by return line, and lower layer of water continues to distillate in water-and-oil separator and shifts out metering.React persistently overheating to 250 ℃, after 5.0 hours, by separator, shift out water through measuring 112 milliliters (theoretical values 97.2%), start pressure release normal pressure slowly, temperature of reaction is 242 ℃ and the 2-EH that collects 168g through condenser, this surveys to such an extent that the acid value of reacting coarse product ester is 2.58mg KOH/g, and esterification is lasted 6.0 hours.Reaction continues reaction at normal pressure, the acid value recording after 1 hour is 0.08mg KOH/g, secondly crude product ester is reduced pressure, by 100 mmhg, be decompressed to gradually vacuum tightness < 2 mmhg and temperature of reaction continues to distillate alcohol excess under 180-190 ℃ of condition, react on after vacuum tightness arrives < 2 mmhg and within 0.5 hour, give decompress(ion), after filtration, filtration time is 131 minutes 4 seconds, obtain DOTP 1227g, it is the micro-turbid product of form and aspect (platinum-cobalt) 35, acid value 0.05.
The raw material of embodiment and comparative example and catalyst, process conditions and result are shown in following table 1:
By the above embodiments and comparative example, can understand according to method of the present invention, utilize chelating type catalyst as alcoholization reaction catalyst, not only promote esterification reaction rate and promoted filtration efficiency, in addition, can obtain again form and aspect and lower than APHA30 and acid value, be less than the terephthalic acid two (2-ethylhexyl) of 0.1mg KOH/g, and in comparative example, do not use oxalate of the present invention as alcoholysis catalyst, the form and aspect of the terephthalic acid two of gained (2-ethylhexyl) are higher, and esterification and filtration time longer; In addition, by embodiment 2 and 5 and embodiment 1,3 and 4 relatively, known method of the present invention is applicable to easy equipment, and do not need to use fractionation tubing string, still can reach identical effect.
Owing to setting up fractionating tube, will improve the about 20-30% of reactor manufacturing cost, and the use Ti (OR) of prior art
4the acid that catalyst carries out and alcohol esterification must be carried out in having the reactor of fractionating tube, otherwise catalyst can be hydrolyzed passivation and esterification time will reach 30-40hr.Review the present invention, utilize chelating type catalyst to carry out the esterification of acid and alcohol, can omit fractionating tube and can obtain form and aspect and the equal excellent terephthalic acid two (2-ethylhexyl) of acid value, so can save manufacturing cost.
Claims (9)
1. a manufacture method for terephthalic acid two (2-ethylhexyl), it comprises:
Under inert environments, in reaction pressure, higher than 1 normal atmosphere, temperature of reaction is under the condition of 180 to 260 ℃, under the chelating type catalyst of following formula (I) exists, makes terephthalic acid and 2-Ethylhexyl Alcohol carry out esterification,
(RO)
mT-(O-Y-X)
n(I)，
Wherein, in formula (I), R is hydrogen or C
1-C
8straight or branched alkyl, T is titanium or zirconium, Y is C
2-C
3stretch alkyl or divalence phosphate radical, X is the functional group containing aerobic or nitrogen, and m is that 1 or 2 integer and n are 2 or 3 integer.
2. method as claimed in claim 1, is characterized in that, this 2-Ethylhexyl Alcohol is without the recovery 2-Ethylhexyl Alcohol dewatering in pure 2-Ethylhexyl Alcohol or reaction.
3. method as claimed in claim 1, is characterized in that, the mol ratio of this 2-Ethylhexyl Alcohol and terephthalic acid is 2.6: 1 to 4.0: 1.
4. method as claimed in claim 1, is characterized in that, the titanium in this chelating type catalyst or zirconium content are the 20ppm to 400ppm of reactant gross weight.
5. method as claimed in claim 1, is characterized in that, this reaction pressure is 1.0 to 4.0kg/cm
2gauge pressure.
6. method as claimed in claim 3, is characterized in that, the mol ratio of this 2-Ethylhexyl Alcohol and terephthalic acid is 3.0: 1 to 3.5: 1.
7. method as claimed in claim 1, is characterized in that, this chelating type catalyst is phosphoric acid ester titanate chelate, trolamine titanic acid ester or tri-alkoxy butyl phosphate titanium dipolymer.
8. as the method for any one in claim 1 to 7, it is characterized in that, this reactor is provided with a condenser and a water-and-oil separator.
9. method as claimed in claim 8, is characterized in that, this reactor is provided with a return line, and the water that this esterification generates and alcohol mixture condensation separated in this water-and-oil separator, and alcohol liquid flows back to reactor via this return line.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310093629.0A CN104058968B (en) | 2013-03-22 | 2013-03-22 | The manufacture method of terephthalic acid two (2-ethylhexyl) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310093629.0A CN104058968B (en) | 2013-03-22 | 2013-03-22 | The manufacture method of terephthalic acid two (2-ethylhexyl) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104058968A true CN104058968A (en) | 2014-09-24 |
| CN104058968B CN104058968B (en) | 2016-04-06 |
Family
ID=51546942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310093629.0A Active CN104058968B (en) | 2013-03-22 | 2013-03-22 | The manufacture method of terephthalic acid two (2-ethylhexyl) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104058968B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037161A (en) * | 2015-07-08 | 2015-11-11 | 中山联成化学工业有限公司 | Continuous synthesis method of cyclohexane polyacid ester |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6303738B1 (en) * | 2000-08-04 | 2001-10-16 | E. I. Du Pont De Nemours And Company | Esterification process |
| CN1441769A (en) * | 2000-07-15 | 2003-09-10 | 埃克森美孚化学专利公司 | Optimized catalyst addition to enhance esterification catalyst performance |
| US20050215426A1 (en) * | 2004-03-26 | 2005-09-29 | Putzig Donald E | Esterification catalyst and process therewith |
| US20050215425A1 (en) * | 2004-03-26 | 2005-09-29 | Clair Jerry D S | Esterification catalyst and process therewith |
| CN101157615A (en) * | 2007-10-31 | 2008-04-09 | 无锡双象化学工业有限公司 | Method for producing plasticizer phthalic acid dinonyl |
| CN101238091A (en) * | 2005-08-12 | 2008-08-06 | 伊士曼化工公司 | Production of di-(2-ethylhexyl) terephthalate |
| CN101234355A (en) * | 2008-03-06 | 2008-08-06 | 郭立耀 | High-efficiency catalyst for synthesizing di(2-ethylhexyl) terephthalate |
-
2013
- 2013-03-22 CN CN201310093629.0A patent/CN104058968B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1441769A (en) * | 2000-07-15 | 2003-09-10 | 埃克森美孚化学专利公司 | Optimized catalyst addition to enhance esterification catalyst performance |
| US6303738B1 (en) * | 2000-08-04 | 2001-10-16 | E. I. Du Pont De Nemours And Company | Esterification process |
| US20050215426A1 (en) * | 2004-03-26 | 2005-09-29 | Putzig Donald E | Esterification catalyst and process therewith |
| US20050215425A1 (en) * | 2004-03-26 | 2005-09-29 | Clair Jerry D S | Esterification catalyst and process therewith |
| CN101238091A (en) * | 2005-08-12 | 2008-08-06 | 伊士曼化工公司 | Production of di-(2-ethylhexyl) terephthalate |
| CN101157615A (en) * | 2007-10-31 | 2008-04-09 | 无锡双象化学工业有限公司 | Method for producing plasticizer phthalic acid dinonyl |
| CN101234355A (en) * | 2008-03-06 | 2008-08-06 | 郭立耀 | High-efficiency catalyst for synthesizing di(2-ethylhexyl) terephthalate |
Non-Patent Citations (2)
| Title |
|---|
| DORF KETAL: "Dupont Tyzor Organic Titanates and Zirconates – Effective Catalyst for Esterification and Transesterification Reactions", 《HTTP://WWW2. DUPONT.COM/TYZOR/ES_MX/ASSETS/DOWNLOADS/K17592_TYZOR_ESTERIFICATION_FINAL.PDF》 * |
| DUPONT: "DuPont TM Tyzor Organic Titanates General Brochure", 《HTTP://SNF. STANFORD. EDU/PIPERMAIL/SPECMAT/ATTACHMENTS/20050518/4F890D57/ATTACHMENT-0002.PDF》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037161A (en) * | 2015-07-08 | 2015-11-11 | 中山联成化学工业有限公司 | Continuous synthesis method of cyclohexane polyacid ester |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104058968B (en) | 2016-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI466863B (en) | Method for producing di(2-ethylhexyl) terephthalate | |
| CN102356058B (en) | Addition of methyl hydrogen terephthalate reactor to dimethyl terephthalate process | |
| CN1225455C (en) | Method for producing esters of multibasic acids | |
| CN102256922A (en) | Production of carboxylic acid esters by stripping with alcohol vapor | |
| CN100473639C (en) | Method of preparing conjugated linolenate from plant oil | |
| CN101250259B (en) | Method for preparing terephthalic acid-1,3-trimethylene glycol ester | |
| CN102015615A (en) | Method for preparing fatty acid alkyl ester using fatty acid | |
| CN107567470A (en) | The continuation method of polybutylene terephthalate (PBT) is prepared using the terephthalic acid (TPA) and 1,4 butanediols of purifying | |
| CN101357887A (en) | Ethyl acetate synthetic process and apparatus thereof | |
| US9796651B2 (en) | Method for continuous production of light acrylates by esterification of a raw ester-grade acrylic acid | |
| CN106749118A (en) | The smooth caprylate emulsifying agent of sorb | |
| CN106588830B (en) | A kind of synthetic method of the smooth caprylate emulsifier of sorb | |
| CN103951793A (en) | Method for producing unsaturated polyester resin by using glycerinum | |
| CN104058968B (en) | The manufacture method of terephthalic acid two (2-ethylhexyl) | |
| CN103387495B (en) | Method for the continuous production of carboxylic acid esters | |
| CN103159591A (en) | Technique of synthesizing ethanol with acetic acid | |
| CA1213901A (en) | Process of manufacturing diaryl esters of dicarboxylic acids | |
| CN104640835A (en) | Hydroxyalkyl acrylate and method for producing same | |
| CN103819659A (en) | Long carbon chain binary acid polyester, and preparation method and application thereof | |
| CN102649743B (en) | Method for synthesizing glycollic acid ester | |
| CN105435791B (en) | Catalyst for preparing 1, 3-propanediol by hydrogenating dialkyl malonate and preparation method and application thereof | |
| CN104024195B (en) | Prepare the method for synthetic ester | |
| CN105705482A (en) | Production of terephthalic acid di-esters using alcohol-amine promoters | |
| CN106103402B (en) | The method that aliphatic dialkyl ester is synthesized by vegetable oil | |
| CN103183609B (en) | Preparation method of ethylene glycol monoacetate and ethylene glycol diacetate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |