CN103012152B - Production technique of diethylene glycol dibenzoate - Google Patents
Production technique of diethylene glycol dibenzoate Download PDFInfo
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- CN103012152B CN103012152B CN201310017137.3A CN201310017137A CN103012152B CN 103012152 B CN103012152 B CN 103012152B CN 201310017137 A CN201310017137 A CN 201310017137A CN 103012152 B CN103012152 B CN 103012152B
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Abstract
The invention discloses a production technique of diethylene glycol dibenzoate, which comprises the following steps: putting benzoic acid, diethylene glycol and catalyst into a reactor to carry out esterification reaction, neutralizing the synthesized crude product, washing with water, stripping, decolorizing, and carrying out pressure filtration to obtain the finished product. The invention is characterized in that a vegetable oil plasticizer, which accounts for 10-30% of the finished product, is added to the decolorization product, and after the vegetable oil plasticizer and the decolorization product are evenly mixed, pressure filtration is carried out on the mixture; the weight ratio of the benzoic acid to the diethylene glycol is (1.8-2.5):1; and the catalyst accounts for 0.5-0.8% of the total amount of the benzoic acid and the diethylene glycol. Compared with the prior art, the invention lowers the production cost and reduces the environmental pollution; and oxidation technique and low-cost low-color-number vegetable oil plasticizer are added to the after-treatment process to obtain the light-color low-cost low-freezing-point diethylene glycol dibenzoate, thereby further widening the application range of the product.
Description
Technical field
The present invention relates to additives for plastics manufacturing technology field, concrete upper saying is a kind of producing and manufacturing technique of elasticizer diethylene glycol dibenzoate.
Background technology
Softening agent is a kind of additive that can increase the flexibility of plastic material, and what be most widely used in the market is dioctyl phthalate (DOP) (DOP) and dibutyl phthalate (DBP).As primary plasticizer DOP by american cancer institute (NCI) suspect have carcinogenesis after, its use range is restricted.The American-European western developed country that waits puts into effect restriction already.In February, 2011, DOP, DBP, butyl phthalate benzene methyl (BBP) three kinds of phthalic esters are directly listed in chemical and are eliminated list by European Union.At present, China just specifies that in toy coating limits of harmful substances standard the content summation of three class phthalate DOP, DBP and BBP must not more than 0.1%.According to news, China is formulating new infant article and toys standard, and wherein specify the Limited Doses of 6 class phthalic esters, its Limited Doses is identical with European Union.The products such as DOP, DBP will exit softening agent market gradually.Softening agent industrial adjustment is extremely urgent with upgrading, and some DOP enterprises have started to change the line of production at present.The better surrogate diethylene glycol dibenzoate (DEDB) of, performance more safer than DOP, is taken seriously day by day.Diethylene glycol dibenzoate and polyvinyl chloride (PVC) consistency good, it can shorten kneading time and fusion time, under equal processing conditions, have energy-saving effect than DOP, DBP, simultaneously tool gives the better luminance brightness of goods and stability and volatility is little, oil-proofness, water tolerance, stain resistance and resistance to photomodification is good, flash-point is high, use safety environmental protection; Its resistance to low temperature is better than DOP, is the softening agent being applicable to the various kinds of resin such as polyvinyl chloride.
At present, the method of industrial synthesis diethylene glycol dibenzoate mainly adopts phenylformic acid and glycol ether to be raw material, use toluene as water entrainer, make catalyzer to prepare with sulfuric acid or heteropolyacid or toluene sulfonic acide or alkali alumina, its preparation method generally includes following steps: phenylformic acid, glycol ether, water entrainer and catalyzer are put into reactor and carries out esterification, obtain diethylene glycol dibenzoate crude product, then alkali neutralization is added, catalyzer is removed, carry out successively again decolouring and press filtration, obtain diethylene glycol dibenzoate.But the diethylene glycol dibenzoate that this technical scheme is produced is generally in flaxen oily liquids, product color is comparatively dark, and its zero pour is about 20 DEG C, below 20 DEG C, meeting crystallization, does not have mobility, is used in winter hardiness on plastics poor, cannot directly use, the scope of application is restricted.
Summary of the invention
The object of this invention is to provide a kind of producing and manufacturing technique of of light color, diethylene glycol dibenzoate that zero pour is lower.
In order to achieve the above object, the technical solution used in the present invention is: the producing and manufacturing technique of this diethylene glycol dibenzoate includes with the next stage: phenylformic acid, glycol ether and catalyzer are put into reactor and carries out esterification, synthesize the crude product obtained and obtain finished product through neutralization, washing, stripping, decolouring and press filtration operation, obtain in product in decolouring and add vegetables oil softening agent, described vegetables oil softening agent is 10% ~ 30% of configuration finished product total amount, after mixing, then press filtration is carried out to mixture; The weight ratio of described phenylformic acid and described glycol ether is 1.8 ~ 2.5:1; Described catalyst levels is 0.5% ~ 0.8% of described phenylformic acid and described glycol ether total amount.
In the technical scheme of the producing and manufacturing technique of above-mentioned diethylene glycol dibenzoate, technical scheme can also be more specifically: described vegetables oil softening agent is plam oil.
Further, described vegetables oil softening agent is lipid acid.
Further, synthesize the described crude product that obtains through oxidizing, then neutralize, being oxidized the oxygenant used is aqueous hydrogen peroxide solution, and its concentration is 35% ~ 50%, and its consumption is that described phenylformic acid and described glycol ether feed intake 2% ~ 5% of total amount.
Further, the discoloring agent that described bleaching process uses is gac, and its consumption is that phenylformic acid and glycol ether feed intake 0.08% ~ 0.1% of total amount; Described catalyzer is stannic oxide.
Owing to have employed technique scheme, the present invention compared with prior art has following beneficial effect:
1, glycol ether content is in the feed higher, and the part by weight of phenylformic acid and glycol ether is 1.8 ~ 2.5:1, can increase whiteness, coloured product is shoaled;
2, after synthesizing the crude product obtained, carry out oxide treatment and desolventing technology, the color and luster of product can be reduced further, produce the softening agent product of light color.
3, the later stage adds low look low cost vegetables oil softening agent, and reduce cost and zero pour, range of application is wider.
Embodiment
Embodiment 1:
At 6m
3reactor in drop into phenylformic acid 3000Kg, glycol ether 1500Kg, stannic oxide 28Kg, stir and heat up, at 190-210 DEG C, insulation reaction obtains crude product in 6 hours, in crude product, add concentration is that 35% aqueous hydrogen peroxide solution 150kg is oxidized, and then add alkali neutralization, add water washing, in stripping process, add 4Kg gac decolour, add 400kg plam oil to mix, press filtration finally obtains the light-coloured prods of 4000kg, and the zero pour of products obtained therefrom is 10 DEG C.
Embodiment 2:
Phenylformic acid 3000Kg, glycol ether 1200Kg, stannic oxide 21Kg is dropped in the reactor of 6m3, stir and heat up, at 190-210 DEG C, insulation reaction obtains crude product in 7 hours, in crude product, add 35% aqueous hydrogen peroxide solution 210kg be oxidized, then add alkali neutralization, add water washing, in stripping process, add gac 3.36Kg decolour, add 495kg plam oil to mix, press filtration finally obtains the light-coloured prods of 3300kg, and the zero pour of products obtained therefrom is 10 DEG C.
Embodiment 3:
Phenylformic acid 3000Kg, glycol ether 1667Kg, stannic oxide 37.35Kg is dropped in the reactor of 6m3, stir and heat up, at 190-210 DEG C, insulation reaction obtains crude product in 8 hours, in crude product, add 50% aqueous hydrogen peroxide solution 93.34kg be oxidized, then add alkali neutralization, add water washing, in stripping process, add gac 4.67Kg decolour, add 1260kg plam oil to mix, press filtration finally obtains the light-coloured prods of 4200kg, and the zero pour of products obtained therefrom is 10 DEG C.
Embodiment 4:
At 6m
3reactor in drop into phenylformic acid 3000Kg, glycol ether 1360Kg, stannic oxide 25Kg, stir and heat up, at 190-210 DEG C, insulation reaction obtains crude product in 6 hours, in crude product, add concentration is that 35% aqueous hydrogen peroxide solution 150kg is oxidized, and then add alkali neutralization, add water washing, in stripping process, add 4Kg gac decolour, add 380kg lipid acid to mix, press filtration finally obtains the light-coloured prods of 3800kg, and the zero pour of products obtained therefrom is 10 DEG C.
Embodiment 5:
Phenylformic acid 3000Kg, glycol ether 1200Kg, stannic oxide 21Kg is dropped in the reactor of 6m3, stir and heat up, at 190-210 DEG C, insulation reaction obtains crude product in 7 hours, in crude product, add 35% aqueous hydrogen peroxide solution 210kg be oxidized, then add alkali neutralization, add water washing, in stripping process, add gac 3.36Kg decolour, add 495kg lipid acid to mix, press filtration finally obtains the light-coloured prods of 3300kg, and the zero pour of products obtained therefrom is 10 DEG C.
Embodiment 6:
Phenylformic acid 3000Kg, glycol ether 1667Kg, stannic oxide 37.35Kg is dropped in the reactor of 6m3, stir and heat up, at 190-210 DEG C, insulation reaction obtains crude product in 8 hours, in crude product, add 50% aqueous hydrogen peroxide solution 93.34kg be oxidized, then add alkali neutralization, add water washing, in stripping process, add gac 4.67Kg decolour, add 1260kg lipid acid to mix, press filtration finally obtains the light-coloured prods of 4200kg, and the zero pour of products obtained therefrom is 10 DEG C.
Claims (6)
1. a producing and manufacturing technique for diethylene glycol dibenzoate, is characterized in that including with the next stage: at 6m
3reactor in drop into phenylformic acid 3000Kg, glycol ether 1500Kg, stannic oxide 28Kg, stir and heat up, at 190-210 DEG C, insulation reaction obtains crude product in 6 hours, in crude product, add concentration is that 35% aqueous hydrogen peroxide solution 150kg is oxidized, and then add alkali neutralization, add water washing, in stripping process, add 4Kg gac decolour, add 400kg plam oil to mix, press filtration finally obtains the light-coloured prods of 4000kg, and the zero pour of products obtained therefrom is 10 DEG C.
2. a producing and manufacturing technique for diethylene glycol dibenzoate, is characterized in that including with the next stage: at 6m
3reactor in drop into phenylformic acid 3000Kg, glycol ether 1200Kg, stannic oxide 21Kg, stir and heat up, at 190-210 DEG C, insulation reaction obtains crude product in 7 hours, in crude product, add 35% aqueous hydrogen peroxide solution 210kg be oxidized, then add alkali neutralization, add water washing, in stripping process, add gac 3.36Kg decolour, add 495kg plam oil to mix, press filtration finally obtains the light-coloured prods of 3300kg, and the zero pour of products obtained therefrom is 10 DEG C.
3. a producing and manufacturing technique for diethylene glycol dibenzoate, is characterized in that including with the next stage: at 6m
3reactor in drop into phenylformic acid 3000Kg, glycol ether 1667Kg, stannic oxide 37.35Kg, stir and heat up, at 190-210 DEG C, insulation reaction obtains crude product in 8 hours, in crude product, add 50% aqueous hydrogen peroxide solution 93.34kg be oxidized, then add alkali neutralization, add water washing, in stripping process, add gac 4.67Kg decolour, add 1260kg plam oil to mix, press filtration finally obtains the light-coloured prods of 4200kg, and the zero pour of products obtained therefrom is 10 DEG C.
4. a producing and manufacturing technique for diethylene glycol dibenzoate, is characterized in that including with the next stage: at 6m
3reactor in drop into phenylformic acid 3000Kg, glycol ether 1360Kg, stannic oxide 25Kg, stir and heat up, at 190-210 DEG C, insulation reaction obtains crude product in 6 hours, in crude product, add concentration is that 35% aqueous hydrogen peroxide solution 150kg is oxidized, and then add alkali neutralization, add water washing, in stripping process, add 4Kg gac decolour, add 380kg lipid acid to mix, press filtration finally obtains the light-coloured prods of 3800kg, and the zero pour of products obtained therefrom is 10 DEG C.
5. a producing and manufacturing technique for diethylene glycol dibenzoate, is characterized in that including with the next stage: at 6m
3reactor in drop into phenylformic acid 3000Kg, glycol ether 1200Kg, stannic oxide 21Kg, stir and heat up, at 190-210 DEG C, insulation reaction obtains crude product in 7 hours, in crude product, add 35% aqueous hydrogen peroxide solution 210kg be oxidized, then add alkali neutralization, add water washing, in stripping process, add gac 3.36Kg decolour, add 495kg lipid acid to mix, press filtration finally obtains the light-coloured prods of 3300kg, and the zero pour of products obtained therefrom is 10 DEG C.
6. a producing and manufacturing technique for diethylene glycol dibenzoate, is characterized in that including with the next stage: at 6m
3reactor in drop into phenylformic acid 3000Kg, glycol ether 1667Kg, stannic oxide 37.35Kg, stir and heat up, at 190-210 DEG C, insulation reaction obtains crude product in 8 hours, in crude product, add 50% aqueous hydrogen peroxide solution 93.34kg be oxidized, then add alkali neutralization, add water washing, in stripping process, add gac 4.67Kg decolour, add 1260kg lipid acid to mix, press filtration finally obtains the light-coloured prods of 4200kg, and the zero pour of products obtained therefrom is 10 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103848742B (en) * | 2013-12-19 | 2016-04-27 | 广州正道环保新材料有限公司 | The method of High-efficient Production diethylene glycol dibenzoate |
| CN105712811B (en) * | 2016-04-08 | 2018-05-01 | 于丽 | A kind of zero-emission efficiently synthesizes ester process units and production technology |
| EA202090807A1 (en) | 2017-09-21 | 2020-07-07 | Публичное акционерное общество "СИБУР Холдинг" | METHOD FOR OBTAINING ESTERS BASED ON GLYCOLS WITH REDUCED COLOR AND PEROXIDES CONTENT |
| CN109776316A (en) * | 2019-03-06 | 2019-05-21 | 杭州多向流化学科技有限公司 | A kind of production method of environment-friendly plasticizer dibenzoic diglycol laurate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1379014A (en) * | 2002-04-29 | 2002-11-13 | 王伟松 | Process for synthesizing tricarboxymethyl propane oleate |
| 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 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1379014A (en) * | 2002-04-29 | 2002-11-13 | 王伟松 | Process for synthesizing tricarboxymethyl propane oleate |
| 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 |
Non-Patent Citations (1)
| Title |
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| 改进二甘醇二苯甲酸酯增塑剂性能的研究;侯国利等;《河南化工》;19971231(第5期);第13页左栏第1-6行和表3，右栏第4行 * |
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