CN1073549C - Method for preparing mixed ester terephthalate - Google Patents
Method for preparing mixed ester terephthalate Download PDFInfo
- Publication number
- CN1073549C CN1073549C CN98113828A CN98113828A CN1073549C CN 1073549 C CN1073549 C CN 1073549C CN 98113828 A CN98113828 A CN 98113828A CN 98113828 A CN98113828 A CN 98113828A CN 1073549 C CN1073549 C CN 1073549C
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- CN
- China
- Prior art keywords
- alcohol
- terephthalic acid
- mixed ester
- preparation
- acid mixed
- 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.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title abstract description 5
- -1 ester terephthalate Chemical class 0.000 title description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000002148 esters Chemical class 0.000 claims abstract description 15
- 239000006227 byproduct Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000005886 esterification reaction Methods 0.000 claims abstract description 8
- 230000032050 esterification Effects 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 5
- 238000009833 condensation Methods 0.000 claims abstract description 4
- 230000005494 condensation Effects 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 7
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 7
- 239000004014 plasticizer Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 5
- 239000003054 catalyst Substances 0.000 abstract 2
- 238000005086 pumping Methods 0.000 abstract 2
- 238000009835 boiling Methods 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 7
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing terephthalic acid mixed ester by terephthalic acid by-products and the esterification of monohydric alcohol and dihydric alcohol in a fatty group. Products obtained by the method are particularly suitable to be used as plasticizers of polyvinylchloride. The present invention is characterized in that the terephthalic acid by-products, the monohydric alcohol, the dihydric alcohol, catalyst and activated carbon are thrown into a reactor with a stirring, a condensation and a reflux devices; esterification reactions are carried out to the terephthalic acid by-products, the monohydric alcohol, the dihydric alcohol, the catalyst and the activated carbon under stirring and heating conditions; after the esterification reactions are completed, slow vacuum pumping is carried out; the temperature in the reactor is maintained as 220 to 230 DEG C, and excess alcohol and low-boiling materials are removed; when the vacuum gradually increases to 700mm Hg and has no distillate, the vacuum pumping is stopped; the materials are filtered so as to remove active carbon and impurities.
Description
The present invention relates to a kind ofly produce the method for terephthalic acid mixed ester, be particularly suitable as the softening agent of polyvinyl chloride with the product of this method gained with terephthalic acid by product and aliphatic monobasic alcohol and dibasic alcohol ester.
It is reported that the plasticizer for polyvinyl chloride that generally uses is dioctyl phthalate (DOP) (DOP) and dibutyl phthalate (DBP) at present.Though dioctyl terephthalate has the excellent electric insulation performance and thermal stability is used widely on CABLE MATERIALS gradually, but owing to be subjected to the restriction in terephthalic acid source, so output is few, the price height, and relatively poor with the intermiscibility of polyvinyl chloride, can not use separately.
The purpose of this invention is to provide a kind of have electrical insulation capability, thermal stability, low-temperature performance and with the polyvinyl chloride intermiscibility good and also output many, terephthalic acid mixed ester (ME) that price is low and preparation method thereof.
Technical solution of the present invention is, adopts industrially to produce a large amount of terephthalic acid by products that contains terephthalic acid 50～60%, phthalic acid 5～10%, phenylformic acid 25～35% and aliphatic monobasic alcohol and dibasic alcohol ester when getting terephthalic acid with the p xylene oxidation legal system and produce the terephthalic acid mixed ester.
Its preparation method is, terephthalic acid by product, monohydroxy-alcohol, dibasic alcohol, catalyzer and gac are put in the reactor that has stirring and condensation, reflux, under the condition that stirs, heats, make it to carry out esterification, after esterification ends, slowly vacuumize, make reactor temperature remain on 220～230 ℃ and remove alcohol excess and low-boiling-point substance, stop to vacuumize when 700mmHg no longer includes overhead product when vacuum tightness rises to gradually, then material is removed by filter gac and impurity.The mass ratio of its terephthalic acid by product and monohydroxy-alcohol and dibasic alcohol is respectively 1: 0.8～2.0,1: 0.1～0.3, catalyzer accounts for 0.1～1% of material total mass, gac accounts for 1～3% of material total mass, temperature of reaction is 140～230 ℃, reaction times is 4～10 hours, and stirring velocity is 60～100 commentaries on classics parts.Said monohydroxy-alcohol is 2-Ethylhexyl Alcohol or n-Octanol or isooctyl alcohol or propyl carbinol or n-Heptyl alcohol.Said dibasic alcohol is ethylene glycol or a diethyl acetal or Triethylene glycol or propylene glycol or dipropylene glycol, and said catalyzer is Cobaltous diacetate or manganese acetate or zinc acetate or tetrabutyl titanate or titanium isopropylate or dibutyl tin laurate.
The present invention and background technology relatively, one, because the raw material that adopts is the terephthalic acid by product, therefore the terephthalic acid mixed ester price comparison of producing is low.Two, owing to adopted monohydroxy-alcohol and dibasic alcohol and better suited catalyzer and technology, therefore not only shortened the reaction times, and improved production efficiency.Three, because the terephthalic acid mixed ester is the mixture of several esters, therefore not only has excellent electric insulating, thermostability and low-temperature performance, and good intermiscibility is arranged with polyvinyl chloride.
Terephthalic acid mixed ester (ME) and widely used dioctyl phthalate (DOP) (DOP) comparative result such as following table:
| The softening agent performance | PVC test piece performance | ||||||||||||
| Moisture content | Volume electricity group coefficient Ω M | 180℃ 20 Min | 200℃ 60 Min | Pour point ℃ | Tensile strength Mpa | Elongation at break % | Thermal ageing 100 ℃ * 7 days | Impact embrittlement temperature ℃ | Thermal change type % | Volume resistivity Ω M | |||
| Tensile strength MPa | Elongation at break % | Thermal weight loss g/m 2 | |||||||||||
| DOP | 4.7 | 1×10 10 | The color no change | No acidic gas is separated out | -45 | 21.5 | 267 | 21.5 | 210 | 17.0 | -25 | 28 | 2.1×10 11 |
| ME | 3.5 | 1.09×10 3 | The color no change | No acidic gas is separated out | -47 | 21 | 250 | 21 | 240 | 15.9 | -25 | 25 | 4.3×10 11 |
Below by a specific embodiment the present invention is described in detail.
Embodiment
With 300 kilograms of terephthalic acid by products, 75 kilograms of glycol ethers, 525 kilograms of octanols, 0.3 kilogram of Cobaltous diacetate, gac is put into for 14.5 kilograms to have and is stirred and condensation, in the reactor of reflux, stir then and heat up, stirring velocity is 80 rev/mins, when being warming up to 140 ℃, begin there are flowing out, be warming up to 180 ℃ gradually, prolong flows out obvious 1.5 kilograms of the tetrabutyl titanates that add when slack-off of water speed, continue there are flowing out this moment, be warming up to 220 ℃ gradually, when no longer there are flowing out, esterification ends, and the sampling and measuring acid number is 0.45mgKOH/g, reaction times is 6 hours, dewaters 67.5 kilograms altogether.Begin then slowly to vacuumize, make reactor temperature remain on 220 ℃ and remove alcohol excess and low-boiling-point substance, when being raised to gradually, vacuum tightness stops to vacuumize when 700mmHg no longer includes overhead product, reclaim 277.5 kilograms of alcohol, adopt vacuum filtration that material is removed by filter gac and impurity then, obtain 445 kilograms of terephthalic acid mixed esters.193 ℃ of its ester number 316.79mgKOH/g, acid number 0.53mgKOH/g, flash-points (open cup).
Claims (4)
1, a kind of preparation method of terephthalic acid mixed ester, it is characterized in that the terephthalic acid by product, monohydroxy-alcohol, dibasic alcohol, catalyzer and gac are put into to have and are stirred and condensation, in the reactor of reflux, stirring, make it to carry out esterification under the condition of heating, after esterification ends, slowly vacuumize, make reactor temperature remain on 220～230 ℃ and remove alcohol excess and low-boiling-point substance, when rising to, vacuum tightness stops to vacuumize when 700mmHg no longer includes overhead product, then material is removed by filter gac and impurity, the mass ratio of its terephthalic acid by product and monohydroxy-alcohol and dibasic alcohol is respectively 1: 0.8～2.0,1: 0.1～0.3, catalyzer accounts for 0.1～1% of material total mass, gac accounts for 1～3% of material total mass, temperature of reaction is 140～230 ℃, reaction times is 4～10 hours, and stirring velocity is 60～100 commentaries on classics parts.
2, the preparation method of terephthalic acid mixed ester according to claim 1 is characterized in that said monohydroxy-alcohol is 2-Ethylhexyl Alcohol or n-Octanol or isooctyl alcohol or propyl carbinol or n-Heptyl alcohol.
3, the preparation method of terephthalic acid mixed ester according to claim 1 is characterized in that said dibasic alcohol is di-alcohol or glycol ether or Triethylene glycol or propylene glycol or dipropylene glycol.
4, the preparation method of terephthalic acid mixed ester according to claim 1 is characterized in that said catalyzer is Cobaltous diacetate or manganese acetate or zinc acetate or tetrabutyl titanate or titanium isopropylate or dibutyl tin laurate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113828A CN1073549C (en) | 1998-03-10 | 1998-03-10 | Method for preparing mixed ester terephthalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113828A CN1073549C (en) | 1998-03-10 | 1998-03-10 | Method for preparing mixed ester terephthalate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1228411A CN1228411A (en) | 1999-09-15 |
| CN1073549C true CN1073549C (en) | 2001-10-24 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98113828A Expired - Fee Related CN1073549C (en) | 1998-03-10 | 1998-03-10 | Method for preparing mixed ester terephthalate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1073549C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400498C (en) * | 2003-10-31 | 2008-07-09 | 中国石油化工股份有限公司 | Terephthalic acid and water scrubbing residue recovery and utilization method |
| DE102009048771A1 (en) * | 2009-10-08 | 2011-04-21 | Oxea Deutschland Gmbh | Process for the preparation of polyol esters |
| DE102009048775A1 (en) * | 2009-10-08 | 2011-04-21 | Oxea Deutschland Gmbh | Process for the preparation of polyol esters |
| CN102206156B (en) * | 2011-03-08 | 2013-04-03 | 福建天大化工有限公司 | Method of Comprehensive Utilization of CTA Residue Resource |
| CN102659599B (en) * | 2012-04-19 | 2014-04-16 | 中国林业科学研究院林产化学工业研究所 | Method for comprehensively improving utilization rate of raw supplementary material in polyester waste preparation DOPT (Dioctyl Terephthalate) process |
| CN103539664B (en) * | 2013-10-15 | 2016-02-24 | 中国石油化工股份有限公司 | A kind of preparation method of pentaerythritol ester |
| CN106045857A (en) * | 2015-04-24 | 2016-10-26 | 中国科学院大连化学物理研究所 | Preparation method for dicyclohexyl dihydric alcohol formate plasticizer |
| WO2018167718A1 (en) * | 2017-03-15 | 2018-09-20 | Sabic Global Technologies B.V. | Method of making dialkyl terephthalate from terephthalic acid |
| KR102236923B1 (en) * | 2017-12-04 | 2021-04-07 | 주식회사 엘지화학 | Plasticizer composition and resin composition comprising the same |
| CN113321882A (en) * | 2021-07-22 | 2021-08-31 | 河南科圣新材料科技有限公司 | Plasticizing system for PVDC product |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6089448A (en) * | 1983-10-21 | 1985-05-20 | Nippon Ester Co Ltd | Continuous production of terephthalic acid glycol ester |
-
1998
- 1998-03-10 CN CN98113828A patent/CN1073549C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6089448A (en) * | 1983-10-21 | 1985-05-20 | Nippon Ester Co Ltd | Continuous production of terephthalic acid glycol ester |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1228411A (en) | 1999-09-15 |
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