CN105732371A - Method for preparing colorless and transparent ethylhexyl benzoate - Google Patents
Method for preparing colorless and transparent ethylhexyl benzoate Download PDFInfo
- Publication number
- CN105732371A CN105732371A CN201610164177.4A CN201610164177A CN105732371A CN 105732371 A CN105732371 A CN 105732371A CN 201610164177 A CN201610164177 A CN 201610164177A CN 105732371 A CN105732371 A CN 105732371A
- Authority
- CN
- China
- Prior art keywords
- benzoic acid
- preparation
- octyl nitrite
- acid octyl
- reaction products
- 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
- 238000000034 method Methods 0.000 title abstract description 8
- UADWUILHKRXHMM-UHFFFAOYSA-N 2-ethylhexyl benzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1 UADWUILHKRXHMM-UHFFFAOYSA-N 0.000 title abstract 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 14
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 10
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 6
- 230000000694 effects Effects 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract 2
- 230000007935 neutral effect Effects 0.000 claims abstract 2
- OYHHVCLUCNXBGV-UHFFFAOYSA-N N(=O)OCCCCCCCC.C(C1=CC=CC=C1)(=O)O Chemical compound N(=O)OCCCCCCCC.C(C1=CC=CC=C1)(=O)O OYHHVCLUCNXBGV-UHFFFAOYSA-N 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical group CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 3
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000007127 saponification reaction Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 abstract 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 description 14
- 229960004365 benzoic acid Drugs 0.000 description 10
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- -1 phosphate ester Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 239000004597 plastic additive Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000013517 stratification Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- PKJBRKTYYNRVSN-UHFFFAOYSA-N 10-(aminomethyl)-9,10-dihydroanthracene-1,2-diol Chemical compound OC1=CC=C2C(CN)C3=CC=CC=C3CC2=C1O PKJBRKTYYNRVSN-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002620 method output Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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)
Abstract
The invention discloses a method for preparing ethylhexyl benzoate. The method includes particular steps of continuously carrying out reaction on benzoic acid and 2-ethyl hexanol under the effects of catalysts at the reaction temperature of 140-150 DEG C under the control for 5-15 hours to obtain reaction products; adding alkali liquid into the reaction products and regulating a pH (potential of hydrogen) value of the reaction products until the reaction products are neutral; washing the reaction products by the aid of pure water and sodium sulfate; layering the reaction products and acquiring oil layers to obtain the ethylhexyl benzoate. The method has the advantages that reaction conditions are mild, and the method is convenient to implement and low in corrosiveness on equipment; the method is high in yield, and the ethylhexyl benzoate prepared by the aid of the method is colorless, clear and transparent.
Description
Technical field
The invention belongs to fine chemicals preparing technical field, relate to the preparation method of a kind of plasticizer, be specifically related to one
Plant the preparation method of benzoic acid Octyl Nitrite.
Background technology
Benzoic acid Octyl Nitrite can make environment-friendly type film former, mainly applies with the film former that benzoic acid Octyl Nitrite is made
In water-based polished dose, binding agent, plasticizer, ink and coating.
During it is demonstrated experimentally that be used for the wearing layer of PVC floor with the formula containing this benzoic acid Octyl Nitrite plasticizer, its
Advection better than with the phosphate ester of same concentration with outward appearance.Benzoic acid Octyl Nitrite performance certain herbaceous plants with big flowers more different than benzoic acid ester excellent performance
Many, and can substitute for dibenzoic acid binary alcohol esters or the dibenzoic acid polybinary alcohol ester of 60%, it is more suitable for strictly
The formula of the V.O.C required uses.
Containing the coating of benzoic acid Octyl Nitrite, through EPA, (Environmental Protection Agency USA TEST24 tests, organic volatilization
Degree is more much lower than the coating volatility containing benzene alcohol.
Benzoic acid Octyl Nitrite is the primary plasticizer of a kind of superior performance and the multipurpose being applied to PVC and other resin
Modifying agent, be mainly used in the conveyer belt of PVC, glove etc. are moulded in cable, electric wire, flexible pipe, leaching, play plasticizer and
The effect of modifying agent, due to European Union and the U.S. etc., at packaging for foodstuff, medical supplies, toy for children and other is close with human body
On the PVC articles for use that cut-grafting is touched, the multiple phthalates such as DOP/DBP are carried out restriction and has used, and benzoic acid
Octyl Nitrite is a kind of non-neighboring benzene environment-friendly plasticizer, and product can mark detection (SGS) being led to by the world of safety.DOP
Application it is only limitted in industrial plastic goods as plastic additive.At present, the whole world has accelerated nontoxic plasticizer product
Research and development, accelerate the plastic base application research that hygienic requirements is high especially.And in China, abroad eliminated
The plasticizers such as DOP have the most greatly market, and plasticizer production enterprise for the exploitation of nontoxic new plasticizer and promotes also
Do not cause and enough pay close attention to.On domestic market, the plasticizer of 80% is all DOP, DBP (dibutyl phthalate) etc.
Plasticizer.Along with expanding economy and country are increasingly stricter to the requirement of environmental protection, novel environment-friendlyplasticizer plasticizer (benzoic acid second
The own ester of base) will gradually replace the plastic additive that DOP, DBP etc. are poisonous；Benzoic acid Octyl Nitrite is nontoxic as one
Novel environment-friendlyplasticizer plasticizer will capture domestic market, drive the plastic additive development of international market.
Summary of the invention
Goal of the invention: present invention aim at providing the preparation side of a kind of high yield water white benzoic acid Octyl Nitrite
Method, by process optimization output yield carboxylate high, water white.
Technical scheme: the preparation method of benzoic acid Octyl Nitrite of the present invention, concretely comprises the following steps: with benzoic acid and
2-Ethylhexyl Alcohol is raw material, reacts under the effect of catalyst, and reaction temperature controls to continue 5～15h at 140～150 DEG C,
Add alkali liquor afterwards and adjust pH value extremely neutrality, be eventually adding pure water and sodium sulfate washing, take oil reservoir after layering, obtain benzene
Formic acid Octyl Nitrite.
Concrete, the mass ratio that feeds intake of described benzoic acid and 2-Ethylhexyl Alcohol is 1:1～3.
Concrete, described catalyst is the mixture of p-methyl benzenesulfonic acid and hypophosphorous acid, toluenesulfonic acid and hypophosphorous acid
Mass ratio be 2～4:1, especially when both mass ratioes are 2～3:1, colourity and yield are more preferable, and optimum proportioning is
2:1.The addition of described catalyst is the 0.1～10% of benzoic acid Mass.Comprehensive colourity and yield consider, the present invention is
Suitably catalyst charge is 1～1.5%..
Concrete, described alkali liquor is the KOH aqueous solution of 45%.
Further, a key operation in operating procedure of the present invention is: before washing, acid value (A.V) controls
Below 3mgKOH/g.Another key operation is: washing after saponification valency (S.V) controls 232～242mgKOH/g
Between.
The benzoic acid ethyl hexyl fat prepared according to aforesaid operations step of the present invention, through surveying, acid value is less than
0.5KOH/g, colourity (platinum-cobalt value) is less than or equal to 3.
Beneficial effect: the preparation method proposing a kind of benzoic acid Octyl Nitrite of the invention, reaction condition temperature
With, easy to operate, little to equipment corrosion, and this method output yield is high, and products obtained therefrom is colourless, and clarifies thoroughly
Bright.
Detailed description of the invention:
Embodiment 1:
Benzoic acid 130g and 2-Ethylhexyl Alcohol 150g, p-methyl benzenesulfonic acid 1.2g and hypophosphorous acid 0.65g are put into four-hole boiling flask
In, warming while stirring, temperature controls to continue 12h at 140 DEG C, and lowering the temperature afterwards and adding alkali liquor adjusts during pH value is
Property, after water knockout drum separates water layer, add stratification after 30g pure water and 0.2g sodium sulfate washing 5h, obtain oil reservoir and be
Benzoic acid Octyl Nitrite, parameters obtained is shown in Table 1.
Table 1
Embodiment 2:
Benzoic acid 700g and 2-Ethylhexyl Alcohol 800g, p-methyl benzenesulfonic acid 6.0g and hypophosphorous acid 3.2g are put into four-hole boiling flask
In, warming while stirring, temperature controls to continue 12h at 140 DEG C, and lowering the temperature afterwards and adding alkali liquor adjusts during pH value is
Property, after water knockout drum separates water layer, add stratification after 160g pure water and 0.9g sodium sulfate washing 5h, obtain oil reservoir and be
Benzoic acid Octyl Nitrite, parameters obtained is shown in Table 2.
Table 2
Embodiment 3:
Benzoic acid 900g and 2-Ethylhexyl Alcohol 1020g, p-methyl benzenesulfonic acid 8.2g and hypophosphorous acid 4.2g are put into four-hole boiling flask
In, warming while stirring, temperature controls to continue 12h at 140 DEG C, and lowering the temperature afterwards and adding alkali liquor adjusts during pH value is
Property, after water knockout drum separates water layer, add stratification after 195g pure water and 1.2g sodium sulfate washing 5h, obtain oil reservoir and be
Benzoic acid Octyl Nitrite, parameters obtained is shown in Table 3.
Table 3
Product purity and the yield data of above-described embodiment 1～3 are listed in table 4
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Yield (%) | 92 | 90.3 | 90.2 |
| Purity (%) | 99 | 98.2 | 98 |
| Purity (%) after rectification | 99.9 | 99.9 | 99.9 |
It can be seen that through the above purity of benzoic acid Octyl Nitrite of reacting all more than 98%, purity after rectification
Even can reach 99.9%.Yield reaches more than 90%.Especially colourity, embodiment 1～3 is all colourless, and clarification is thoroughly
Bright, this feature is not reached in prior art.
Above several embodiments of the present invention are described in detail, but described content has been only the preferable real of the present invention
Example, it is impossible to be considered the practical range for limiting the present invention.All impartial changes done according to the present patent application scope with
Improve, within the patent covering scope of the present invention all should be belonged to.
Claims (8)
1. the preparation method of a benzoic acid Octyl Nitrite, it is characterised in that: it is former with benzoic acid and 2-Ethylhexyl Alcohol
Material, reacts under the effect of catalyst, and reaction temperature controls to continue 5～15h at 140～150 DEG C, adds alkali afterwards
It is the most neutral that liquid adjusts pH value, is eventually adding pure water and sodium sulfate washing, takes oil reservoir, obtain benzoic acid ethyl hexyl after layering
Ester.
The preparation method of benzoic acid Octyl Nitrite the most according to claim 1, it is characterised in that described benzoic acid
It is 1:1～3 with the mass ratio that feeds intake of 2-Ethylhexyl Alcohol.
The preparation method of benzoic acid Octyl Nitrite the most according to claim 1, it is characterised in that described catalyst
Addition is benzoic acid Mass 0.1～10%.
The preparation method of benzoic acid Octyl Nitrite the most according to claim 1, it is characterised in that described catalyst
For the mixture of p-methyl benzenesulfonic acid Yu hypophosphorous acid, both mass ratioes are 2～4:1.
The preparation method of benzoic acid Octyl Nitrite the most according to claim 1, it is characterised in that described alkali liquor is
The KOH aqueous solution of 45%.
The preparation method of benzoic acid Octyl Nitrite the most according to claim 1, it is characterised in that acid value before washing
(A.V) control at below 3mgKOH/g.
The preparation method of benzoic acid Octyl Nitrite the most according to claim 1, it is characterised in that washing after saponification
Valency (S.V) controls between 232～242mgKOH/g.
The preparation method of benzoic acid Octyl Nitrite the most according to claim 1, it is characterised in that gained benzoic acid
Ethyl hexyl fat: acid value is less than 0.5KOH/g, colourity (platinum-cobalt value) is less than or equal to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610164177.4A CN105732371B (en) | 2016-03-22 | 2016-03-22 | A kind of preparation method of the benzoic acid ethylhexyl of water white transparency |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610164177.4A CN105732371B (en) | 2016-03-22 | 2016-03-22 | A kind of preparation method of the benzoic acid ethylhexyl of water white transparency |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105732371A true CN105732371A (en) | 2016-07-06 |
| CN105732371B CN105732371B (en) | 2018-04-13 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610164177.4A Active CN105732371B (en) | 2016-03-22 | 2016-03-22 | A kind of preparation method of the benzoic acid ethylhexyl of water white transparency |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105732371B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1849369A (en) * | 2003-09-09 | 2006-10-18 | 奥克森诺奥勒芬化学股份有限公司 | Use of isononyl benzoate as a film-forming agent |
| WO2008107470A1 (en) * | 2007-03-08 | 2008-09-12 | Lanxess Deutschland Gmbh | Use of proton-supplying and/or proton-accepting polymer particles |
| CN104529778A (en) * | 2014-12-30 | 2015-04-22 | 安徽香枫新材料有限公司 | Preparation method of benzoic acid (2-ethyl) hexyl ester |
-
2016
- 2016-03-22 CN CN201610164177.4A patent/CN105732371B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1849369A (en) * | 2003-09-09 | 2006-10-18 | 奥克森诺奥勒芬化学股份有限公司 | Use of isononyl benzoate as a film-forming agent |
| WO2008107470A1 (en) * | 2007-03-08 | 2008-09-12 | Lanxess Deutschland Gmbh | Use of proton-supplying and/or proton-accepting polymer particles |
| CN104529778A (en) * | 2014-12-30 | 2015-04-22 | 安徽香枫新材料有限公司 | Preparation method of benzoic acid (2-ethyl) hexyl ester |
Non-Patent Citations (1)
| Title |
|---|
| 郝强等: "松香催化酯化反应研究进展", 《林产化学与化工》 * |
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| Publication number | Publication date |
|---|---|
| CN105732371B (en) | 2018-04-13 |
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| CB03 | Change of inventor or designer information |
Inventor after: Hamada Nobuichi Inventor after: Hamada Michiko Inventor before: Hamada Nobuichi Inventor before: Hamada Michiko Inventor before: Guo Xiaoye Inventor before: Wan Chao |
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Effective date of registration: 20190703 Address after: 31 Liuhe Town, Taicang City, Jiangsu Province, Gaocheng Shanghai Holiday Garden Phase I Patentee after: Hamada Michiko Address before: 215433 No. 17 East Huasu Road, Petrochemical Park, Taicang Port Development Zone, Suzhou City, Jiangsu Province Patentee before: YWK Chemicals (Taicang) Co., Ltd. |
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Effective date of registration: 20190821 Address after: 215431 Liuhe Town, Taicang City, Jiangsu Province, 31 Holiday Gardens in Gaocheng Shanghai Patentee after: Hamada Michiko Address before: Taicang City, Suzhou City, Jiangsu province 215433 HuaSu East Port Development Zone Petrochemical Park No. 17 Patentee before: YWK Chemicals (Taicang) Co., Ltd. |
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