CN106938970B - A kind of method of 1,2- cyclohexane cyclohexanedimethanodibasic dinonyl purification - Google Patents
A kind of method of 1,2- cyclohexane cyclohexanedimethanodibasic dinonyl purification Download PDFInfo
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- CN106938970B CN106938970B CN201710160052.9A CN201710160052A CN106938970B CN 106938970 B CN106938970 B CN 106938970B CN 201710160052 A CN201710160052 A CN 201710160052A CN 106938970 B CN106938970 B CN 106938970B
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- cyclohexane cyclohexanedimethanodibasic
- dinonyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/52—Sorbents specially adapted for preparative chromatography
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- Chemical & Material Sciences (AREA)
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- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Furan Compounds (AREA)
Abstract
The method of one kind 1,2- cyclohexane cyclohexanedimethanodibasic dinonyl purification is added phenyl high-resolution agarose microbeads in a stirring kettle, ethyl difluoro, furandicarboxylic acid, 1- carboxymethyl -3- butyl imidazole nitrate, and water is kept the temperature after being warming up to preference temperature, obtains absorption resin；Step 1 is added in exchange column and obtains absorption resin, 1, the 2- cyclohexane cyclohexanedimethanodibasic dinonyl that crude product 1,2- cyclohexane cyclohexanedimethanodibasic dinonyl are purified through absorption resin purification.
Description
Technical field
The present invention relates to a kind of methods of 1,2- cyclohexane cyclohexanedimethanodibasic dinonyl purification.
Background technique
Plasticizer is a kind of plastic additive being widely used, and the flexibility of plastics can be made to enhance, be easily worked, and is met each
Kind purposes.Plasticizer is to produce the maximum plastic additive kind of consumption, and wherein phthalic ester plasticizer occupies in plasticizers
In ascendancy.Phthalic acid ester is mainly used for pvc material, and polyvinyl chloride is enabled to become flexible modeling from hard plastic
Glue plays the role of plasticizer.It is widely used in toy, packaging material for food, medical blood bag and sebific duct, vinyl flooring and
Wallpaper, detergent, lubricating oil, personal-care supplies (such as nail polish, hair spray, perfumed soap and shampoo) hundreds of products
In, but have serious harm to the health of human body.
CN105254501A discloses the preparation method of hexamethylene -1,2- dioctyl phthalate dinonyl, puts into a kettle
Isononyl alcohol, hexamethylene -1,2- dicarboxylic acid anhydride, catalyst, water entrainer；End of reaction removes water entrainer, unreacted isononyl alcohol,
After alcohol purifies, filter solvents, filtering is added in cooling reactant to room temperature；Silica gel H is added into resulting filtrate, filters, filter
Liquid removes solvent, obtains the sterling of hexamethylene -1,2- dioctyl phthalate dinonyl.Low energy consumption by the present invention, and " three wastes " discharge is few, operation
Simply, catalyst and reactant recoverable are arranged by reducing reaction temperature, shortening reaction time, reduction raw material proportioning etc.
It applies and improves production technology, carry out reacting balance, superior product quality, purity is high.
CN101417950 discloses a kind of method for preparing 1,2- cyclohexane cyclohexanedimethanodibasic dibasic ester, and reaction system is by adjacent benzene
Cyclohexanedimethanodibasic dibasic ester, hydrogen and catalyst composition;Reaction temperature is 100~250 DEG C, and reaction pressure is 3.0~12.0MPA, H2
Molar ratio with phthalic acid dibasic ester is 50~450, and the liquid air speed of phthalic acid dibasic ester is 0.1~2.5H-1;
Catalyst be using AL2O3, ZRO2, TIO2 or SIO2-AL2O3 as carrier, load active component can for RU, PT, PD, RH, FE,
CO,NI, CU;Phthalic acid dibasic ester is diisononyl phthalate, diisooctyl phthalate or phthalic acid
Dibutyl ester;Its product 1,2- cyclohexane cyclohexanedimethanodibasic dibasic ester is 1,2- cyclohexane cyclohexanedimethanodibasic dinonyl, 1,2- hexamethylene diformazan
Sour di-isooctyl or 1,2- cyclohexane cyclohexanedimethanodibasic dibutyl ester.
Existing patent and the used purifying technique of technical literature are all made of the absorption such as technique or silica gel of distillation or evaporation
Agent, complex process, adsorption efficiency are low.
Summary of the invention
In order to solve the above technical problems, present invention employs the following technical solutions: one kind 1,2- cyclohexane cyclohexanedimethanodibasic
The method of dinonyl purification, comprising the following steps:
Step 1. carboxylic acid reaction
By weight, in a stirring kettle be added 100 parts of phenyl high-resolution agarose microbeads, 1-5 parts of ethyl difluoros,
1-5 parts of furandicarboxylic acids, 0.01-0.1 parts of 1- carboxymethyl -3- butyl imidazole nitrate, 100-400 parts of water are warming up to 50-80
DEG C, 30-60h is kept the temperature, absorption resin is obtained.
Step 2, the purifying of 1,2- cyclohexane cyclohexanedimethanodibasic dinonyl
By weight, step 1 is added in exchange column and obtains 100 parts of naval stores of absorption, by technical grade 1,2- hexamethylene
Alkane dioctyl phthalate dinonyl is added above exchange column, flow velocity 50-150L/h, and efflux is 1,2- hexamethylene after purification
Dioctyl phthalate dinonyl.
It is commercial product that phenyl high-resolution agarose microbeads, which are commercial product, described in step 1, as indigo plant dawn science and technology in Xi'an is new
The product of material limited liability company production；Ethyl difluoro is commercial product, as Hubei Ju Sheng Science and Technology Ltd. produces
Product；Furandicarboxylic acid is commercial product, such as Hubei giant dragon hall medication chemistry Co., Ltd；1- carboxylic butyl -3- methylimidazole
Nitrate is commercial product, the product produced such as lark prestige Science and Technology Ltd..
Technical grade 1 described in step 2,2- cyclohexane cyclohexanedimethanodibasic dinonyl are commercial product, as Guangzhou woods wins chemical industry
The product of Co., Ltd's production.
Compared with prior art, the invention has the following advantages:
Contain carboxyl, imidazoles, in 1,2- cyclohexane cyclohexanedimethanodibasic dinonyl in phenyl high-resolution agarose microbeads skeleton
Containing carboxyl, the adsorbance of heterocycle low-molecular material as main component is improved；The 1,2- of available mass percent concentration 99.9%
Cyclohexane cyclohexanedimethanodibasic dinonyl product.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is furture elucidated, but these the examples are only for explaining the invention, without
It is for limiting the scope of the invention.
Embodiment 1
Step 1. carboxylic acid reaction
In 1000L stirred tank, phenyl high-resolution agarose microbeads 100Kg, ethyl difluoro 3Kg, furans two is added
Formic acid 3Kg, 1- carboxymethyl -3- butyl imidazole nitrate 0.05Kg, water 300Kg are warming up to 60 DEG C, keep the temperature 45h, are adsorbed
Resin.
Step 2, the purifying of 1,2- cyclohexane cyclohexanedimethanodibasic dinonyl
The absorption naval stores 100Kg that step 1 obtains is added in exchange column, by technical grade 1,2- cyclohexane cyclohexanedimethanodibasic
Dinonyl is added above exchange column, flow velocity 100L/h, and efflux is the different nonyl of 1,2- cyclohexane cyclohexanedimethanodibasic two after purification
Ester.Product purity is shown in Table 1.
Embodiment 2
Step 1. carboxylic acid reaction
In 1000L stirred tank, phenyl high-resolution agarose microbeads 100Kg, ethyl difluoro 1Kg, furans two is added
Formic acid 1Kg, 1- carboxymethyl -3- butyl imidazole nitrate 0.01Kg, water 100Kg are warming up to 50 DEG C, keep the temperature 30h, are adsorbed
Resin.
Step 2, the purifying of 1,2- cyclohexane cyclohexanedimethanodibasic dinonyl
The absorption naval stores 100Kg that step 1 obtains is added in exchange column, by technical grade 1,2- cyclohexane cyclohexanedimethanodibasic
Dinonyl is added above exchange column, flow velocity 50L/h, and efflux is the different nonyl of 1,2- cyclohexane cyclohexanedimethanodibasic two after purification
Ester.Product purity is shown in Table 1.
Embodiment 3
Step 1. carboxylic acid reaction
In 1000L stirred tank, phenyl high-resolution agarose microbeads 100Kg, ethyl difluoro 5Kg, furans two is added
Formic acid 5Kg, 1- carboxymethyl -3- butyl imidazole nitrate 0.1Kg, water 400Kg are warming up to 80 DEG C, keep the temperature 60h, obtain absorption tree
Rouge.
Step 2, the purifying of 1,2- cyclohexane cyclohexanedimethanodibasic dinonyl
The absorption naval stores 100Kg that step 1 obtains is added in exchange column, by technical grade 1,2- cyclohexane cyclohexanedimethanodibasic
Dinonyl is added above exchange column, flow velocity 150L/h, and efflux is the different nonyl of 1,2- cyclohexane cyclohexanedimethanodibasic two after purification
Ester.Product purity is shown in Table 1.
Comparative example 1
Step 1 is added without ethyl difluoro, the other the same as in Example 1, and product purity is shown in Table 1.
Comparative example 2
Step 1 is added without furandicarboxylic acid, the other the same as in Example 1, and product purity is shown in Table 1.
Comparative example 3
Step 1 is added without 1- carboxymethyl -3- butyl imidazole nitrate, and product purity is shown in Table 1.
Table 1: the 1,2- cyclohexane cyclohexanedimethanodibasic dinonyl purity of embodiment 1-3 and comparative example 1-3 is shown in Table 1.
Claims (1)
1. one kind 1, the method for 2- cyclohexane cyclohexanedimethanodibasic dinonyl purification, it is characterised in that the following steps are included:
Step 1. carboxylic acid reaction
By weight, 100 parts of phenyl high-resolution agarose microbeads, 1-5 parts of ethyl difluoros, 1-5 are added in a stirring kettle
Part furandicarboxylic acid, 0.01-0.1 parts of 1- carboxymethyl -3- butyl imidazole nitrate, 100-400 parts of water are warming up to 50-80 DEG C, protect
Warm 30- 60h obtains absorption resin；
Step 2, the purifying of 1,2- cyclohexane cyclohexanedimethanodibasic dinonyl
By weight, step 1 is added in exchange column and obtains 100 parts of naval stores of absorption, by crude product 1,2- hexamethylene diformazan
Sour dinonyl is added above exchange column, flow velocity 50-150L/h, and efflux is 1,2- cyclohexane cyclohexanedimethanodibasic two after purification
Different nonyl ester.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2016103600726 | 2016-05-27 | ||
| CN201610360072.6A CN105949064A (en) | 2016-05-27 | 2016-05-27 | Purification method of 1,2-cyclohexane diisononyl phthalate |
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| Publication Number | Publication Date |
|---|---|
| CN106938970A CN106938970A (en) | 2017-07-11 |
| CN106938970B true CN106938970B (en) | 2019-09-24 |
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|---|---|---|---|
| CN201610360072.6A Withdrawn CN105949064A (en) | 2016-05-27 | 2016-05-27 | Purification method of 1,2-cyclohexane diisononyl phthalate |
| CN201710160052.9A Expired - Fee Related CN106938970B (en) | 2016-05-27 | 2017-03-17 | A kind of method of 1,2- cyclohexane cyclohexanedimethanodibasic dinonyl purification |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610360072.6A Withdrawn CN105949064A (en) | 2016-05-27 | 2016-05-27 | Purification method of 1,2-cyclohexane diisononyl phthalate |
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| CN107082884A (en) * | 2017-06-04 | 2017-08-22 | 王金桢 | A kind of method for adsorbing purification dimethicone |
| CN107286348A (en) * | 2017-07-31 | 2017-10-24 | 王艺霖 | A kind of preparation method of antistatic additive polyether modified silicon oil processed |
| CN107233862A (en) * | 2017-08-02 | 2017-10-10 | 王艺霖 | A kind of preparation method of methyl phenyl silicone oil adsorbent |
| CN107243329A (en) * | 2017-08-02 | 2017-10-13 | 王金桢 | A kind of preparation method of synthetic textiles dimethyl hydroxyl silicon oil adsorbent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254501A (en) * | 2015-10-23 | 2016-01-20 | 淮阴师范学院 | Preparation method of cyclohexane-1,2-diisononyl phthalate |
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2016
- 2016-05-27 CN CN201610360072.6A patent/CN105949064A/en not_active Withdrawn
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254501A (en) * | 2015-10-23 | 2016-01-20 | 淮阴师范学院 | Preparation method of cyclohexane-1,2-diisononyl phthalate |
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| CN105949064A (en) | 2016-09-21 |
| CN106938970A (en) | 2017-07-11 |
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Address after: 432000, 11 business street, Danyang office, hi tech Zone, Hubei, Xiaogan Applicant after: Zhang Ling Address before: 432000 Hubei city of Xiaogan province high tech Zone Qun Sheng Cun Nan Qu Bian min Lu 5 floor, room 91 Applicant before: Zhang Ling |
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Effective date of registration: 20210305 Address after: No.35 Fengguan Road, Qilu Chemical Industrial Zone, Linzi District, Zibo City, Shandong Province, 255400 Patentee after: SHANDONG YONGHAO NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: 432000 11th Business Street, Danyang Office, Xiaogan High-tech Zone, Hubei Province Patentee before: Zhang Ling |
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