CN101613282A - A kind of environment-friendly plasticizer cyclohexane alkane-1, the preparation method of 2-2-dicarboxylic acid diethylhexyl ester - Google Patents
A kind of environment-friendly plasticizer cyclohexane alkane-1, the preparation method of 2-2-dicarboxylic acid diethylhexyl ester Download PDFInfo
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- CN101613282A CN101613282A CN200910101045A CN200910101045A CN101613282A CN 101613282 A CN101613282 A CN 101613282A CN 200910101045 A CN200910101045 A CN 200910101045A CN 200910101045 A CN200910101045 A CN 200910101045A CN 101613282 A CN101613282 A CN 101613282A
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Abstract
The invention discloses a kind of environment-friendly plasticizer cyclohexane alkane-1, the preparation method of 2-2-dicarboxylic acid diethylhexyl ester.Comprise the steps: 1) with 1 mole of hexanaphthene-1,2-dicarboxylic anhydride, 2.4～2.6 moles of 2-Ethylhexyl Alcohols and catalyst mix, heating is warmed up to 220 ℃ of reaction 3～4h from 185 ℃, and dealcoholysis obtains hexanaphthene-1, the thick product of 2-2-dicarboxylic acid diethylhexyl ester; 2) with hexanaphthene-1, the cooling of the thick product of 2-dicarboxylic acid adds the neutralization of the NaOH aqueous solution, washing, and the refining 3～4h of stripping again adds relative material total amount per-cent and is 0.1%～0.2% charcoal absorption decolouring, obtains purified product through press filtration.Products obtained therefrom of the present invention is the susceptibility application of a kind of suitable PVC, safe non-phthalate environment-friendly plasticizer, can be used for low peculiar smell automobile cable, automotive upholstery, medical facilities such as medical nutrition supply pipe, Food Contact based articles such as domestic food contact gloves, antistaling film, food suction pipe, the indoor wallpaper of environment-friendly type, decorative sheets of material and toy for children etc.
Description
Technical field
The present invention relates to technical field of chemical engineering, relate in particular to a kind of environment-friendly plasticizer cyclohexane alkane-1, the preparation method of 2-2-dicarboxylic acid diethylhexyl ester.
Background technology
Softening agent is the auxiliary agent kind of application quantity maximum in the plastics industry, to promoting particularly polyvinyl chloride (PVC) industrial expansion decisive role of plastics industry.Present various novel plastic has been penetrated into every field such as industrial or agricultural, transportation, traffic, medicine, food, clothes, building, national defence.Raising along with the countries in the world environmental consciousness, plastics such as medicine parcel, medicine equipment, food product pack, daily necessities, toy processing have proposed higher hygienic requirements to primary plasticizer, and the whole world has been accelerated the environment-friendly plasticizer product and met the applied research of the plastics of hygienic requirements.But particularly wholesomeness, nontoxicity etc. all are difficult to satisfy environmental protection requirement to the primary plasticizer of domestic enterprise's production at present on many performances.The hexanaphthene-1 of the inventive method preparation, 2-2-dicarboxylic acid diethylhexyl ester softening agent is that the susceptibility that aims at PVC is used (as medical facilities, food product pack, toy for children etc.) and the exploitation a kind of non-phthalic ester plasticizer, it has dioctyl phthalate (DOP) (DOP) and the similar structure of diisononyl phthalate (DINP), the performance that possesses DOP and DINP, and function is more outstanding, be embodied in: transport property is little, water white transparency, environmental protection fully, can hold mutually with common organic solvent and common plasticizers, its elasticity, the transparency, low-temperature performance is much better than primary plasticizers such as DOP and DINP, prior hexanaphthene-1,2-2-dicarboxylic acid diethylhexyl ester product has excellent toxicological characteristics, possesses outstanding processing characteristics simultaneously, can be medicine equipment, food product pack, medical treatment product, toy for children and other provide the desirable solution that reaches safety requirements with the PVC product manufacturer that human body contacts closely, and product meets every strict demand of REACH comprehensively, is that the product of raw material also can easily be tackled the challenge of REACH with it.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of environment-friendly plasticizer cyclohexane alkane-1, the preparation method of 2-2-dicarboxylic acid diethylhexyl ester.
Environment-friendly plasticizer cyclohexane alkane-1, the preparation method of 2-2-dicarboxylic acid diethylhexyl ester comprises the steps:
1) with 1 mole of hexanaphthene-1,2-dicarboxylic anhydride, 2.4～2.6 moles of 2-Ethylhexyl Alcohols and catalyst mix, heating is warmed up to 220 ℃ of reaction 3～4h from 185 ℃, and dealcoholysis obtains hexanaphthene-1, the thick product of 2-2-dicarboxylic acid diethylhexyl ester;
2) with hexanaphthene-1, the thick product of 2-dicarboxylic acid is cooled to 85 ℃～90 ℃, add the neutralization of the NaOH aqueous solution, wash under 90 ℃～95 ℃, again with the refining 3～4h of steam stripped, add relative material total amount per-cent and be 0.1%～0.2% charcoal absorption decolouring, obtain hexanaphthene-1 through press filtration, 2-2-dicarboxylic acid diethylhexyl ester purified product.
Described catalyzer is a titanium isopropylate, and add-on is a hexanaphthene-1,0.2%～0.3% of 2-dicarboxylic anhydride quality.
The add-on of described NaOH is:
The technical process that the present invention adopts is applicable to the production of other types of plasticizer, can obtain high-quality softening agent product.Strict process control, the production technology of optimization can be guaranteed the high purity and the wholesomeness of product.The hexanaphthene-1 that adopts the inventive method to make; 2-2-dicarboxylic acid diethylhexyl ester softening agent is when granulation or plasticising production; compatibleness with the PVC material is good; applicable to specific injection mould, even can be used for very accurate careful design, thereby prolong the life cycle of plastified prod; hexanaphthene-1; 2-2-dicarboxylic acid diethylhexyl ester plastifying the finished product transport property is very low, can combine with resin material safety such as ABS, SAN, PC, guarantees that product has long work-ing life and excellent properties.
Embodiment
The technical process that the present invention adopts is: feed intake → esterification → dealcoholysis → neutralization washing → refining → adsorption bleaching → press filtration → finished product.
Hexanaphthene among the present invention-1, hexanaphthene-1 is adopted in the preparation of 2-dicarboxylester di-isooctyl, and the method for 2-dicarboxylic anhydride and 2-Ethylhexyl Alcohol direct esterification is carried out.With hexanaphthene-1,2-dicarboxylic anhydride, 2-Ethylhexyl Alcohol and catalyzer join in the reactor, and heated and stirred heats up, and are warmed up to 220 ℃ from 185 ℃ and react 3～4h, remove alcohol excess, obtain hexanaphthene-1, the thick product of 2-2-dicarboxylic acid diethylhexyl ester.
With hexanaphthene-1, the thick product of 2-2-dicarboxylic acid diethylhexyl ester neutralizes with the NaOH aqueous solution down at 85 ℃～90 ℃, 90 ℃～95 ℃ washings, stripping is made with extra care 3～4h, adding still material total amount per-cent is charcoal absorption decolouring 20～30min of 0.1%～0.2%, get hexanaphthene-1 through press filtration, the purified product of 2-2-dicarboxylic acid diethylhexyl ester.
The hexanaphthene-1 that adopts above method to make, the purity of 2-2-dicarboxylic acid diethylhexyl ester softening agent product can be tested by gas chromatograph, and product purity is more than or equal to 99.5%.
Embodiment 1
With hexanaphthene-1,2-dicarboxylic anhydride and 2-Ethylhexyl Alcohol mol ratio are 1/2.4, total mass is the hexanaphthene-1 of 4720kg, heat in 2-dicarboxylic anhydride and the 2-Ethylhexyl Alcohol adding reactor, add relative hexanaphthene-1 again, the titanium isopropylate catalyzer of 2-dicarboxylic anhydride quality 0.2%, heating, be warmed up to dealcoholysis behind 220 ℃ of reaction 4h from 185 ℃, be cooled to 85 ℃～90 ℃ NaOH aqueous solution that add 80kg 1.0wt% and neutralize 90 ℃～95 ℃ washings, again with the refining 4h of steam stripped, add the charcoal absorption decolouring 20min of still material total amount 0.1%, get hexanaphthene-1 through press filtration, the 2-2-dicarboxylic acid diethylhexyl ester, its yield is 97.1%, and purity is 99.0%.
Embodiment 2
With hexanaphthene-1,2-dicarboxylic anhydride and 2-Ethylhexyl Alcohol mol ratio are 1/2.5, total mass is the hexanaphthene-1 of 4720kg, heat in 2-dicarboxylic anhydride and the 2-Ethylhexyl Alcohol adding reactor, add relative hexanaphthene-1 again, the titanium isopropylate catalyzer of 2-dicarboxylic anhydride quality 0.2%, heating, from 185 ℃ be warmed up to 220 ℃ the reaction 3.8h after dealcoholysis, being cooled to 85 ℃～90 ℃ NaOH aqueous solution that add 75kg 1.0wt% neutralizes, 90 ℃～95 ℃ washings, again with the refining 4h of steam stripped, add the charcoal absorption decolouring 20min of still material total amount 0.1%, get hexanaphthene-1 through press filtration, the 2-2-dicarboxylic acid diethylhexyl ester, its yield is 98.3%, and purity is 99.1%.
Embodiment 3
With hexanaphthene-1,2-dicarboxylic anhydride and 2-Ethylhexyl Alcohol mol ratio are 1/2.6, total mass is the hexanaphthene-1 of 4720kg, heat in 2-dicarboxylic anhydride and the 2-Ethylhexyl Alcohol adding reactor, add relative hexanaphthene-1 again, the titanium isopropylate catalyzer of 2-dicarboxylic anhydride quality 0.2%, heating, from 185 ℃ be warmed up to 220 ℃ the reaction 3.5h after dealcoholysis, being cooled to 85 ℃～90 ℃ NaOH aqueous solution that add 75kg 1.0wt% neutralizes, 90 ℃～95 ℃ washings, again with the refining 4h of steam stripped, add the charcoal absorption decolouring 20min of still material total amount 0.1%, get hexanaphthene-1 through press filtration, the 2-2-dicarboxylic acid diethylhexyl ester, its yield is 98.2%, and purity is 99.0%.
Embodiment 4
With hexanaphthene-1,2-dicarboxylic anhydride and 2-Ethylhexyl Alcohol mol ratio are 1/2.4, total mass is the hexanaphthene-1 of 4720kg, heat in 2-dicarboxylic anhydride and the 2-Ethylhexyl Alcohol adding reactor, add relative hexanaphthene-1 again, the titanium isopropylate catalyzer of 2-dicarboxylic anhydride quality 0.25%, heating, from 185 ℃ be warmed up to 220 ℃ the reaction 3h after dealcoholysis, being cooled to 85 ℃～90 ℃ NaOH aqueous solution that add 70kg 1.0wt% neutralizes, 90 ℃～95 ℃ washings, again with the refining 3.5h of steam stripped, add the charcoal absorption decolouring 20min of still material total amount 0.15%, get hexanaphthene-1 through press filtration, the 2-2-dicarboxylic acid diethylhexyl ester, its yield is 98.5%, and purity is 99.1%.
Embodiment 5
With hexanaphthene-1,2-dicarboxylic anhydride and 2-Ethylhexyl Alcohol mol ratio are 1/2.5, total mass is the hexanaphthene-1 of 4720kg, heat in 2-dicarboxylic anhydride and the 2-Ethylhexyl Alcohol adding reactor, add relative hexanaphthene-1 again, the titanium isopropylate catalyzer of 2-dicarboxylic anhydride quality 0.25%, heating, from 185 ℃ be warmed up to 220 ℃ the reaction 3.5h after dealcoholysis, be cooled to 85 ℃～90 ℃ NaOH aqueous solution neutralizations that add 75kg 1.0wt%, 90 ℃～95 ℃ washings, again with the refining 3.5h of steam stripped, add the charcoal absorption decolouring 20min of still material total amount 0.15%, get hexanaphthene-1 through press filtration, the 2-2-dicarboxylic acid diethylhexyl ester, its yield is 99.5%, and purity is 99.5%.
Embodiment 6
With hexanaphthene-1,2-dicarboxylic anhydride and 2-Ethylhexyl Alcohol mol ratio are 1/2.6, total mass is the hexanaphthene-1 of 4720kg, and 2-dicarboxylic anhydride and 2-Ethylhexyl Alcohol add in the reactor and heat, and add relative hexanaphthene-1 again, the titanium isopropylate catalyzer of 2-dicarboxylic anhydride quality 0.25%, heating.From 185 ℃ be warmed up to 220 ℃ the reaction 3.5h after dealcoholysis, be cooled to 85 ℃～90 ℃ NaOH aqueous solution neutralizations that add 75kg 1.0wt%, 90 ℃～95 ℃ washings, again with the refining 3.5h of open steam stripping, add the charcoal absorption decolouring 20min of still material total amount 0.15%, get hexanaphthene-1 through press filtration, the 2-2-dicarboxylic acid diethylhexyl ester, its yield is 99.2%, and purity is 99.3%.
Embodiment 7
With hexanaphthene-1,2-dicarboxylic anhydride and 2-Ethylhexyl Alcohol mol ratio are 1/2.4, total mass is the hexanaphthene-1 of 4720kg, heat in 2-dicarboxylic anhydride and the 2-Ethylhexyl Alcohol adding reactor, add relative hexanaphthene-1 again, the titanium isopropylate catalyzer of 2-dicarboxylic anhydride quality 0.3%, heating, be warmed up to dealcoholysis behind 220 ℃ of reaction 3.5h from 185 ℃, be cooled to 85 ℃～90 ℃ NaOH aqueous solution neutralizations that add 80kg 1.0wt%, 90 ℃～95 ℃ washings, again with the refining 3h of steam stripped, add the charcoal absorption decolouring 20min of still material total amount 0.2%, get hexanaphthene-1 through press filtration, the 2-2-dicarboxylic acid diethylhexyl ester, its yield is 98.3%, and purity is 99.0%.
Embodiment 8
With hexanaphthene-1,2-dicarboxylic anhydride and 2-Ethylhexyl Alcohol mol ratio are 1/2.5, total mass is the hexanaphthene-1 of 4720kg, and 2-dicarboxylic anhydride and 2-Ethylhexyl Alcohol add in the reactor and heat, and add relative hexanaphthene-1 again, the titanium isopropylate catalyzer of 2-dicarboxylic anhydride quality 0.3%, heating.From 185 ℃ be warmed up to 220 ℃ the reaction 3h after dealcoholysis, be cooled to 85 ℃～90 ℃ NaOH aqueous solution neutralizations that add 75kg 1.0wt%, 90 ℃～95 ℃ washings, again with the refining 3h of steam stripped, add the charcoal absorption decolouring 30min of still material total amount 0.2%, get hexanaphthene-1 through press filtration, the 2-2-dicarboxylic acid diethylhexyl ester, its yield is 99.5%, and purity is 99.5%.
Embodiment 9
With hexanaphthene-1,2-dicarboxylic anhydride and 2-Ethylhexyl Alcohol mol ratio are 1/2.6, total mass is the hexanaphthene-1 of 4720kg, heat in 2-dicarboxylic anhydride and the 2-Ethylhexyl Alcohol adding reactor, add relative hexanaphthene-1 again, the titanium isopropylate catalyzer of 2-dicarboxylic anhydride quality 0.3%, heating, be warmed up to dealcoholysis behind 220 ℃ of reaction 3h from 185 ℃, be cooled to 85 ℃～90 ℃ NaOH aqueous solution neutralizations that add 70kg 1.0wt%, 90 ℃～95 ℃ washings, again with the refining 3h of steam stripped, add the charcoal absorption decolouring 30min of still material total amount 0.2%, get hexanaphthene-1 through press filtration, the 2-2-dicarboxylic acid diethylhexyl ester, its yield is 99.0%, and purity is 99.2%.
Claims (3)
1, a kind of environment-friendly plasticizer cyclohexane alkane-1, the preparation method of 2-2-dicarboxylic acid diethylhexyl ester is characterized in that comprising the steps:
1) with 1 mole of hexanaphthene-1,2-dicarboxylic anhydride, 2.4～2.6 moles of 2-Ethylhexyl Alcohols and catalyst mix, heating is warmed up to 220 ℃ of reaction 3～4h from 185 ℃, and dealcoholysis obtains hexanaphthene-1, the thick product of 2-2-dicarboxylic acid diethylhexyl ester;
2) with hexanaphthene-1, the thick product of 2-dicarboxylic acid is cooled to 85 ℃～90 ℃, add the neutralization of the NaOH aqueous solution, wash under 90 ℃～95 ℃, stripping is made with extra care 3～4h again, add relative material total amount per-cent and be 0.1%～02% charcoal absorption decolouring, obtain hexanaphthene-1 through press filtration, 2-2-dicarboxylic acid diethylhexyl ester purified product.
2, a kind of environment-friendly plasticizer cyclohexane alkane-1 according to claim 1, the preparation method of 2-2-dicarboxylic acid diethylhexyl ester is characterized in that described catalyzer is a titanium isopropylate, add-on is a hexanaphthene-1,0.2%～0.3% of 2-dicarboxylic anhydride quality.
3, according to the described a kind of environment-friendly plasticizer cyclohexane alkane-1 of claim, the preparation method of 2-2-dicarboxylic acid diethylhexyl ester is characterized in that the add-on of described NaOH is:
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391122A (en) * | 2011-10-09 | 2012-03-28 | 浙江商通科技有限公司 | Method for preparing hexahydro phthalic acid bis(2-ethyl hexyl)ester serving as environment-friendly plasticizer |
| CN102675109A (en) * | 2012-05-24 | 2012-09-19 | 江苏康恒化工有限公司 | Method for preparing plasticizer of cyclohexane-1,2-diisooctyl phthalate |
| CN105254501A (en) * | 2015-10-23 | 2016-01-20 | 淮阴师范学院 | Preparation method of cyclohexane-1,2-diisononyl phthalate |
| CN110713439A (en) * | 2019-10-31 | 2020-01-21 | 濮阳市盛源能源科技股份有限公司 | Preparation method of cyclohexane-1, 2-dicarboxylate environment-friendly plasticizer |
| CN113603590A (en) * | 2021-08-23 | 2021-11-05 | 濮阳市盛源能源科技股份有限公司 | Method for decoloring cyclohexane-1, 2-dicarboxylic acid diisooctyl ester crude product |
-
2009
- 2009-07-30 CN CN200910101045A patent/CN101613282A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391122A (en) * | 2011-10-09 | 2012-03-28 | 浙江商通科技有限公司 | Method for preparing hexahydro phthalic acid bis(2-ethyl hexyl)ester serving as environment-friendly plasticizer |
| CN102675109A (en) * | 2012-05-24 | 2012-09-19 | 江苏康恒化工有限公司 | Method for preparing plasticizer of cyclohexane-1,2-diisooctyl phthalate |
| CN105254501A (en) * | 2015-10-23 | 2016-01-20 | 淮阴师范学院 | Preparation method of cyclohexane-1,2-diisononyl phthalate |
| CN110713439A (en) * | 2019-10-31 | 2020-01-21 | 濮阳市盛源能源科技股份有限公司 | Preparation method of cyclohexane-1, 2-dicarboxylate environment-friendly plasticizer |
| CN113603590A (en) * | 2021-08-23 | 2021-11-05 | 濮阳市盛源能源科技股份有限公司 | Method for decoloring cyclohexane-1, 2-dicarboxylic acid diisooctyl ester crude product |
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Application publication date: 20091230 |