CN102070456B - Method for preparing novel environmentally-friendly plasticizer - Google Patents
Method for preparing novel environmentally-friendly plasticizer Download PDFInfo
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- CN102070456B CN102070456B CN2011100032066A CN201110003206A CN102070456B CN 102070456 B CN102070456 B CN 102070456B CN 2011100032066 A CN2011100032066 A CN 2011100032066A CN 201110003206 A CN201110003206 A CN 201110003206A CN 102070456 B CN102070456 B CN 102070456B
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000004014 plasticizer Substances 0.000 title abstract description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011552 falling film Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000011973 solid acid Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000004902 Softening Agent Substances 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 14
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000008096 xylene Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 2
- 239000011265 semifinished product Substances 0.000 abstract 2
- 239000005711 Benzoic acid Substances 0.000 abstract 1
- -1 benzoate glycerol ester Chemical class 0.000 abstract 1
- 235000010233 benzoic acid Nutrition 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 150000003504 terephthalic acids Chemical class 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 49
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- 150000001298 alcohols Chemical class 0.000 description 3
- 229960004365 benzoic acid Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- PDZPRYRBZQQMLH-UHFFFAOYSA-N 2-ethylbutanoic acid;phthalic acid Chemical compound CCC(CC)C(O)=O.OC(=O)C1=CC=CC=C1C(O)=O PDZPRYRBZQQMLH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing a novel environmentally-friendly plasticizer, which comprises the following steps of: adding glycerol, benzoic acid and xylene into a reactor, performing reaction under 70 to 180 DEG C and 0.1 to 0.6 MPa to prepare a semi-finished product, treating the semi-finished product by using a falling film evaporator, adding a solid acid catalyst to continuously perform the reaction, and finally adding activated carbon for absorptive filtration to obtain a liquid benzoate glycerol ester plasticizer finished product. The method ensures less investment, low energy consumption, low production cost and high market competitiveness of the product, is favorable for safety production and environmental protection, shortens a production process flow and reaction time due to the adoption of raw materials with low cost instead of downstream petrochemical raw materials phthalate, terephthalic acids and octanol, and meets the advocacy of promoting the development of enterprises by scientific and technical innovations in China.
Description
Technical field
The present invention relates to chemical industry fine chemical product field, is mainly for common in the market softening agent product technology route, by a kind of new production technique provided after technological innovation, a kind of preparation method of novel environment friendly softening agent specifically.
Background technology
At present, softening agent be on domestic and international market the consumption maximum mould one of agent aid.In recent years, China has become softening agent size of capacity maximum in the world, is also the country that demand is maximum.For a long time, more domestic manufacturer production softening agent generally adopt o-Xylol as main raw material(s), but along with phthalic acid diethylacetic acid (being called for short DOP) applying in the industries such as food, medicine, people also more and more pay attention to its toxicity, also cause the concern of countries in the world health organizations, and taked corresponding restriction.The states such as America and Europe have promulgated new permit standard for this reason, have stopped the industrial production of 6 kinds of O-phthalic lipids, and forbid using on food, toy and medical packaging the plastics that contain the DOP composition.In the plastic components such as the bottled edible oil adopted, soy sauce, vinegar, all contain harmful DOP a plasticiser component on China existing market.Therefore; no matter be the safety and sanitation from diet; or from going home, protect angle; particularly current national is advocated and is greatly developed green economy; under the opportune time of transforming mode of economic growth; in the urgent need to by technological innovation, Speeding up development goes out nontoxic and a kind of novel environment-friendly softening agent of applied range product and replaces existing traditional product, improves the people's quality of life.
Plasticizer production process mainly contains adjacent benzene first diacid and to two kinds of technical recipes of benzene first diacid in the market, although adopt, take adjacent benzene first diacid and to benzene first diacid as the situation that quality product and the user of main material production softening agent uses feedback all better, but it is high that these production technique exist energy consumption, the waste gas particularly produced when acidification reaction has had a strong impact on surrounding environment, also affect operative employee's physical and mental health, more than required vapor pressure should reach 10kg when distilling dealcoholysis and esterification due to above production technique simultaneously, temperature is 260 degrees centigrade of left and right, both increased the management difficulty of safety in production, short easy damage of having held production unit again, brought enterprise's production run cost high, the situation that competitive power is poor.
Summary of the invention
The objective of the invention is the deficiency for above-mentioned existing production technology, provide that a kind of energy consumption is low, investment is little, running cost is low, the uncorruptible normal temperature of equipment, normal pressure, be conducive to the preparation method of a kind of novel environment-friendly softening agent of production safety management.
Purpose of the present invention can reach by following measures:
A kind of preparation method of novel environment-friendly softening agent, it is: glycerine, phenylformic acid and dimethylbenzene are added in reactor, at 70～180 ℃ and react below 0.1～0.6MPa, make work in-process, through falling-film evaporator, process again, then add solid acid catalyst to continue reaction, finally add gac to carry out adsorption filtration, obtain liquid benzene formic acid glyceride type softening agent finished product.
Reaction of the present invention can, from normal pressure, need in reaction process to stir.The temperature that wherein adds solid acid catalyst to continue reaction is 70～180 ℃, and pressure is 0.1～0.6MPa, and described glycerine and benzoic mol ratio are 1: 1～4, and the consumption of dimethylbenzene is quantity of solvent (being the common solvent consumption).
Half-finished preparation feedback temperature is preferably 100～110 ℃, and preparing half-finished reaction times is 3～6 hours.In falling-film evaporator, adopt the mode of negative-pressure vacuum suction to remove raw material excessive in work in-process.
The preparation method of this novel environment-friendly softening agent, prepare the softening agent product except the process stream formula is different from adjacent benzene or to benzene, also is that it not only has the Preparation equipment adopted energy-conservation, and will stablizes quality product.For vaporizer, this process using falling-film evaporator, other techniques adopt thin-film evaporator.
The preparation method of this novel environment-friendly softening agent, the general temperature and pressure of whole process using, its top temperature is no more than 180 ℃, vapor pressure is no more than 6kg (0.6MPa), and adopts adjacent benzene or to benzene, be the preparation method of main raw material, because its material boiling point used is high, therefore required temperature of reaction will reach 210-230 ℃, vapor pressure needs 8-10kg (0.8-1MPa), and not only energy consumption is large, and the waste gas that when reaction produces is also larger to surrounding environment influence.
The characteristics of this its preparation process also are: from former, expect product out, the whole reaction times is than with adjacent benzene or to benzene, be main raw material the preparation method will shorten 4 hours at least, have that technical process is short, reaction temperature and, the advantage such as low, the easy handling of energy consumption.
This explained hereafter danger little (normal temperature and pressure), on surrounding environment substantially without the impact, adopt adjacent benzene or to the benzene process preparation method, another kind of main raw material octanol due to its employing, after whole building-up reactions, can produce certain gas that contains benzene and alcohols, not only can affect the work on the spot environment, and the waste gas distributed will also can bring certain impact to surrounding environment.
The novel environment-friendly softening agent that present method obtains is phenylformic acid glyceride type softening agent, and it not only has the characteristic of environmental protection, and performance and DOP are quite or better, its upper alternative existing traditional product.
Beneficial effect of the present invention:
The present invention is different from the adjacent benzene of traditional in the market use or is the main material production softening agent to benzene; not only have the investment little, energy consumption is low, be conducive to the safety in production and environment protection; and adopt with the adjacent benzene of cheap starting material petroleum replacing chemical industry downstream raw material, to benzene and octanol; the technological process of production and reaction times have been shortened; have that production cost is low, the product market competition ability is strong, also meet current country and advocate with scientific and technical innovation and promote enterprise development.This technique prepares the environment-friendly type softening agent simultaneously, makes in product not contain benzene and alcohols, can be by range of application from electric wire, and chemical industry and engineering plastics, the leatherware industry, expand medicine, food service industry to, also promoted the class of China's traditional product.
Embodiment
Embodiment 1
After metering, successively join glycerine and phenylformic acid (mol ratio 1: 4) and xylene solvent in reactor, under normal pressure, progressively be warming up to 180 ℃ since 70 ℃, and continuously stirring, react (vapor pressure is 6kg) after 4 hours, just obtain work in-process, pass through again falling-film evaporator, simultaneously by negative-pressure vacuum suction mode, excess raw material is joined to the transfer still, add wherein again solid acid catalyst to continue at synthesis under normal pressure below 180 ℃ about half an hour, after finally adding gac to carry out adsorption filtration, namely obtain liquid benzene formic acid glyceride type softening agent finished product, by pump, finished product is driven in storage tank.
Infrared spectra shows: 3066cm
-1Place is the unsaturated C-H vibration of phenyl ring, 1452-1602cm
-1Place is the C-C vibration of phenyl ring, 1746cm
-1Place is the ester group vibration.After testing, in product, do not contain benzene and alcohols (or lower than detectability).
Embodiment 2
With embodiment 1, change glycerine and benzoic mol ratio into 1: 4.5, the work in-process reaction is warming up to 160 ℃, and the reaction times is adjusted to 4.5 hours, preparation liquid benzene formic acid glyceride type softening agent finished product.
In polyvinyl chloride resin, add respectively embodiment 1 softening agent that accounts for resin quality 20% or 30%, and add the one package stabilizer of resin quality 5%, mixing print A and the B of making.Test respectively its tensile strength and shore hardness, the tensile strength of A is the 65MPa left and right, and the tensile strength of B is the 52MPa left and right, and the shore hardness D of A is for being 83 left and right, and the shore hardness D of B is for being 70 left and right.The increase of plasticizer consumption of the present invention as can be seen here, plasticizing efficiency increases.
Claims (1)
1. the preparation method of a novel environment-friendly softening agent, it is characterized in that: glycerine, phenylformic acid and dimethylbenzene are added in reactor, and glycerine and benzoic mol ratio are 1:1～4; At 100～110 ℃ and below 0.1～0.6MPa, reacted 3～6 hours, make work in-process, through falling-film evaporator, process again, in falling-film evaporator, adopt the mode of negative-pressure vacuum suction to remove raw material excessive in work in-process, then add solid acid catalyst under 70～180 ℃ of temperature and pressure 0.1～0.6MPa, to continue reaction, finally add gac to carry out adsorption filtration.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100032066A CN102070456B (en) | 2011-01-07 | 2011-01-07 | Method for preparing novel environmentally-friendly plasticizer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100032066A CN102070456B (en) | 2011-01-07 | 2011-01-07 | Method for preparing novel environmentally-friendly plasticizer |
Publications (2)
| Publication Number | Publication Date |
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| CN102070456A CN102070456A (en) | 2011-05-25 |
| CN102070456B true CN102070456B (en) | 2013-11-27 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106674006A (en) * | 2016-12-20 | 2017-05-17 | 广州印田新材料有限公司 | Benzoate preparation process |
| CN107055733A (en) * | 2017-04-07 | 2017-08-18 | 苏州安利化工有限公司 | Plasticizer waste water administering method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1604950A (en) * | 2001-12-20 | 2005-04-06 | 费罗公司 | Glycerin triester plasticizer |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH023002A (en) * | 1988-06-17 | 1990-01-08 | Sumitomo Electric Ind Ltd | Positioning method for butt end face of optical fiber |
| JPH093002A (en) * | 1995-06-16 | 1997-01-07 | Dainippon Ink & Chem Inc | Method for esterifying polyhydric alcohol |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1604950A (en) * | 2001-12-20 | 2005-04-06 | 费罗公司 | Glycerin triester plasticizer |
Non-Patent Citations (3)
| Title |
|---|
| 王淑荣等.苯甲酸酯类增塑剂.《山西化工》.1987,(第4期),30-33. |
| 石万聪等.《增塑剂及其应用》.《增塑剂及其应用》.化学工业出版社,2002, * |
| 苯甲酸酯类增塑剂;王淑荣等;《山西化工》;1987(第4期);30-33 * |
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| CN102070456A (en) | 2011-05-25 |
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Granted publication date: 20131127 Termination date: 20140107 |