CN102050739B - Process for producing polyol benzoate (DEDB) - Google Patents
Process for producing polyol benzoate (DEDB) Download PDFInfo
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- CN102050739B CN102050739B CN 201010555356 CN201010555356A CN102050739B CN 102050739 B CN102050739 B CN 102050739B CN 201010555356 CN201010555356 CN 201010555356 CN 201010555356 A CN201010555356 A CN 201010555356A CN 102050739 B CN102050739 B CN 102050739B
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- Prior art keywords
- dedb
- reduced
- phenylformic acid
- production
- toluene
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- 238000000034 method Methods 0.000 title claims abstract description 17
- FJRUWRJAJNEIKD-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-6,7-diamine Chemical compound O1CCOC2=C1C=C(N)C(N)=C2 FJRUWRJAJNEIKD-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229920005862 polyol Polymers 0.000 title abstract description 3
- -1 polyol benzoate Chemical class 0.000 title abstract description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 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 3
- 239000000047 product Substances 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 8
- 230000032050 esterification Effects 0.000 abstract description 7
- 238000005886 esterification reaction Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000006386 neutralization reaction Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 239000005711 Benzoic acid Substances 0.000 abstract 2
- 235000010233 benzoic acid Nutrition 0.000 abstract 2
- 150000005846 sugar alcohols Polymers 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 5
- 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 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 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
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of production technologies of plasticizer, particularly relates to a process for producing polyol benzoate (DEDB). In the process, polyalcohol and benzoic acid are used as raw materials for performing esterification, and then separation and purification are carried out, wherein overdose of the raw material polyalcohol is added. The process is simple, short in production cycle and is 1-2h shorter than that of a traditional process; moreover, the consumption of alkali for neutralization is reduced by more than 50%, the generated wastewater is reduced by more than 25%, the production cost is reduced by 10-20%, byproducts generated by benzoic acid are reduced, and the quality of the finished product is improved.
Description
Technical field
The invention belongs to the production technical field of softening agent, particularly a kind of production technique of DEDB.
Background technology
DEDB is the novel environment friendly softening agent that China developed in recent years.Be characterized in good with the PVC consistency, winter hardiness is good, and is antistatic remarkable with the resistance to crocking effect, has outstanding thermostability and low volatility, and toxicity is low, and performance is close with o-phthalic acid dibutyl ester (DOP), and alternative DOP is as the primary plasticizer of PVC.
At present, the synthesis technique of DEDB class mainly contains three synthetic routes with the difference of raw material: alkyd direct esterification, transesterify and acyl chlorides condensation.Though the route of transesterify (temperature of reaction is below 150 ℃) and acyl chlorides condensation (temperature of reaction is about 120 ℃) carries out than direct esterification is easy, productive rate is lower, and the production cost height.In industrial production, consider that synthetic DEDB raw material is easy to get, production cost is low, adopts a step esterification process synthetic usually.Synthetic DEDB adopts synthetic its pure product of method of esterification, neutralization, washing, dehydration and solvent, decolouring, filtration mostly in the industry at present.But because DEDB is polyvalent alcohol and benzoic carboxylate, in order to increase dibasic acid esters content, to reduce monoester content, must make the excessive 5-10% of phenylformic acid.There is following shortcoming in such technology owing to phenylformic acid is excessive: (1) phenylformic acid boiling point and fusing point are all very high, be difficult to separate with product DEDB, can not recycle, the washing that can only neutralize at present separates, therefore all very big with alkali charge and washing water consumption in, the wastewater flow rate of producing is big, and product per ton generates about 1 ton of waste water; (2) benzoic price exceeds more than 1 times than polyvalent alcohol, thereby has increased product cost greatly; (3) phenylformic acid excessive product yield is lower, generally at 80-90%, has wasted phenylformic acid, has increased production cost, and is difficult for removing by the by product of phenylformic acid generation, finally influences the quality of product.Therefore such technology and be not suitable for suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of DEDB production technique, to overcome existing method or cost height or yield is low or the defective of not environmental protection.
The technical solution used in the present invention is as follows:
The DEDB production technique is that raw material carries out esterification with polyvalent alcohol and phenylformic acid, and separation and purification then wherein, adds excessive raw polyol.So-called excessive, refer to the consumption at the basis increasing polyvalent alcohol that waits quantitative response.
Further, the described polyvalent alcohol excessive 5-10% of amount of substance that feeds intake.
Described polyvalent alcohol is one or more the mixture in glycol ether, ethylene glycol, triglycol, the neopentyl glycol.
Described separation and purification is: neutralization after the esterification, washing, distillation dehydration and solvent, refining decolouring, filter at last the DEDB finished product.
For solving the problem that exists in original DEDB synthesis technique, the present invention adopts the excessive excessive novel process of polyvalent alcohol that changes into of phenylformic acid, follow-up through over-churning, neutralization is washed, is sloughed water and is with aqua, the synthetic DEDB finished product of decolorization filtering then.Though after technology changed the excessive 5-10% of phenylformic acid into polyvalent alcohol excessive 5-10%, the product flash-point decreased, but still was higher than dioctyl phthalate (DOP) (DOP).After the process modification, in and alkali charge reduce more than 50%, the waste water growing amount reduces more than 25%, has reduced the production cost of 10-20%, other index of product (as color and luster and acid number) all is greatly improved, and is that dibasic acid esters content slightly reduces.
Compared with prior art, the present invention has following beneficial effect:
Technology of the present invention is simple, and is with short production cycle, reduces 1-2h than traditional technology; In and alkali charge reduces 50% or more, the waste water growing amount reduces more than 25%, production cost reduction 10-20% has reduced the by product by the phenylformic acid generation, thereby has improved the quality of product.
Embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Following embodiment 1 adopts technology of the present invention, and embodiment 2 adopts original production process to compare:
Embodiment 1
In the reactor of 2000ml, by glycol ether: phenylformic acid (mol ratio) feeds intake for 1.1:2, add 349.8g glycol ether, 732g phenylformic acid, 124ml toluene and 1.08g activated carbon, add the titanium isopropylate that accounts for total quality of material 0. 14%, under agitation in the 180-210 ℃ of about 3h of back flow reaction, sampling detecting acid number, acid number 0.36mgKOH/g, the alkaline solution of preparation 3-5% neutralizes, temperature remains on 70-80 ℃ of washing 2 times, water and toluene are sloughed in underpressure distillation, and press filtration gets the diglycol benzoate finished product then.
Embodiment 2
In the reactor of 2000ml, by glycol ether: phenylformic acid (mol ratio) feeds intake for 1:2.1, add 318g glycol ether, 768.6g phenylformic acid, 125ml toluene and 1.08g activated carbon, add the titanium isopropylate that accounts for total quality of material 0.14%, under agitation in the 180-210 ℃ of about 4h of back flow reaction, sampling detecting acid number, acid number 18.51mgKOH/g, the alkaline solution of preparation 3-5% neutralizes, temperature remains on 70-80 ℃ of washing 2 times, water and toluene are sloughed in underpressure distillation, and press filtration gets the diglycol benzoate finished product then.
The diglycol benzoate end properties contrast that embodiment 1,2 obtains sees Table 1.
Claims (1)
1. DEDB production technique, it is characterized in that, in the reactor of 2000ml, by glycol ether: the phenylformic acid mol ratio is that 1.1:2 feeds intake, add the 349.8g glycol ether, the 732g phenylformic acid, 124ml toluene and 1.08g activated carbon, add the titanium isopropylate that accounts for total quality of material 0. 14%, under agitation in the 180-210 ℃ of about 3h of back flow reaction, sampling detecting acid number, acid number 0.36mgKOH/g, the alkaline solution of preparation 3-5% neutralizes, and temperature remains on 70-80 ℃ of washing 2 times, water and toluene are sloughed in underpressure distillation, and press filtration gets the diglycol benzoate finished product then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010555356 CN102050739B (en) | 2010-11-23 | 2010-11-23 | Process for producing polyol benzoate (DEDB) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010555356 CN102050739B (en) | 2010-11-23 | 2010-11-23 | Process for producing polyol benzoate (DEDB) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102050739A CN102050739A (en) | 2011-05-11 |
| CN102050739B true CN102050739B (en) | 2013-09-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 201010555356 Active CN102050739B (en) | 2010-11-23 | 2010-11-23 | Process for producing polyol benzoate (DEDB) |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775310B (en) * | 2012-08-06 | 2015-04-08 | 南京林业大学 | Synthesis method of dibasic alcohol bi-benzoate |
| CN103739494B (en) * | 2013-12-19 | 2016-01-27 | 广州正道环保新材料有限公司 | The method of High-efficient Production triethylene glycol dibenzoate |
| CN103804718B (en) * | 2014-01-11 | 2016-04-13 | 广州正道环保新材料有限公司 | Glycol ether and triglycol mixture and benzoic acid produce composite elasticizer method |
| CN113402386B (en) * | 2021-05-28 | 2024-05-03 | 武汉亿科德精细化工有限公司 | Synthesis method of neopentyl glycol dibenzoate |
| CN114085144B (en) * | 2021-12-09 | 2023-12-29 | 上海汇得科技股份有限公司 | Synthetic method of plasticizer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376631A (en) * | 2008-10-07 | 2009-03-04 | 杭州临安商通塑化有限公司 | Environment-protective preparation of diglycol ethylene dibenzoate plasticiser |
| CN101492372A (en) * | 2008-12-01 | 2009-07-29 | 无锡双象化学工业有限公司 | Method for producing elasticizer diethylene glycol dibenzoate |
-
2010
- 2010-11-23 CN CN 201010555356 patent/CN102050739B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376631A (en) * | 2008-10-07 | 2009-03-04 | 杭州临安商通塑化有限公司 | Environment-protective preparation of diglycol ethylene dibenzoate plasticiser |
| CN101492372A (en) * | 2008-12-01 | 2009-07-29 | 无锡双象化学工业有限公司 | Method for producing elasticizer diethylene glycol dibenzoate |
Non-Patent Citations (2)
| Title |
|---|
| 二(3,5-二硝基苯甲酸)二甘醇酯的合成研究;宋日 等;《爆破器材》;20080215;第37卷(第1期);第1-3页 * |
| 宋日等.二(3 5-二硝基苯甲酸)二甘醇酯的合成研究.《爆破器材》.2008 |
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| CN102050739A (en) | 2011-05-11 |
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Effective date of registration: 20231114 Granted publication date: 20130925 |