CN101973884A - Method for preparing triisononyl trimellitate (TINTM) - Google Patents
Method for preparing triisononyl trimellitate (TINTM) Download PDFInfo
- Publication number
- CN101973884A CN101973884A CN2010102912719A CN201010291271A CN101973884A CN 101973884 A CN101973884 A CN 101973884A CN 2010102912719 A CN2010102912719 A CN 2010102912719A CN 201010291271 A CN201010291271 A CN 201010291271A CN 101973884 A CN101973884 A CN 101973884A
- Authority
- CN
- China
- Prior art keywords
- preparation
- trimellitic acid
- weight
- heavenly stems
- reactor
- 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.)
- Pending
Links
- 0 CC(C)*=CCCCC=ClO Chemical compound CC(C)*=CCCCC=ClO 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing triisononyl trimellitate (TINTM), comprising the following steps: adding trimellitic acid anhydride and isononyl alcohol with a mole ratio of 1:3.5-1:4.5 as well as activated carbon the weight of which is 0.1-0.3% of the weight of the trimellitic acid anhydride into a reaction kettle; stirring the mixture and raising the temperature to 185-195 DEG C; then, adding catalyst the weight of which is 0.05-0.2% of the weight of the trimellitic acid anhydride, continuing to raise the temperature to 185-245 DEG C and reacting for 3-4 hours; controlling the acid value to be below 0.50mgKOH/g, and carrying out negative pressure dealcoholization until no return liquid exists; adding sodium hydroxide solution with the mass percent concentration of 10-15%, and controlling the acid value to be below 0.07mgKOH/g; introducing water into the reaction kettle to serve as an entrainer, and carrying out dealcoholization refining; and lowering the temperature to 150 DEG C, adding dried atlapulgite the weight of which is 0.07-0.2% of the total mass of the end product, evenly mixing and filtering. The method of the invention has the characteristics of no pollution, low energy consumption, short process time, high efficiency and good product quality.
Description
Technical field
The present invention relates to a kind of preparation method of softening agent, the preparation method of particularly a kind of trimellitic acid three ester in the different ninth of the ten Heavenly Stems.
Background technology
The volatility of trimellitate, anti-extractable and resistance to migration all have the advantage of similar polyester plasticizer, simultaneously, its consistency, processibility and low-temperature performance etc. are similar to monomeric phthalic acid esters again, so it has the advantage of monomeric plasticizer and polymeric plasticiser concurrently, it is as heat-resisting, the weather resistance softening agent is widely used, be mainly used at present in 105 ℃ of level CABLE MATERIALS, and as the representative trioctyl trimellitate (TOTM) of trimellitate in some field particularly UL62 or UL1581 desired possess can't meet the demands in aging property and the stable on heating electric wire goods, and trimellitic acid three different esters in the ninth of the ten Heavenly Stems (TINTM) have following characteristics with respect to trioctyl trimellitate (TOTM):
1. trimellitic acid three different esters in the ninth of the ten Heavenly Stems (TINTM) are similar to the processing conditions of trioctyl trimellitate (TOTM), can be used as primary plasticizer and use;
2. the molecular weight ratio trioctyl trimellitate (TOTM) of trimellitic acid three different esters in the ninth of the ten Heavenly Stems (TINTM) is big, and evaporation rate is lower than trioctyl trimellitate (TOTM);
3. the thermotolerance of trimellitic acid three different esters in the ninth of the ten Heavenly Stems (TINTM) and aging resistance are better than trioctyl trimellitate (TOTM);
Therefore trimellitic acid three different esters in the ninth of the ten Heavenly Stems (TINTM) more are suitable for requiring to possess in anti-aging characteristic and the stable on heating electric wire goods, yet energy consumption is bigger in the production of trimellitic acid three different esters in the ninth of the ten Heavenly Stems (TINTM) at present, reaction produces large amount of sewage, and environmental pollution is serious.
Summary of the invention
In order to remedy above deficiency, the invention provides the preparation method of a kind of trimellitic acid three ester in the different ninth of the ten Heavenly Stems, its method is simple, and is easy to operate, save energy, environmental pollution is little.
The present invention for the technical scheme that solves its technical problem and adopt is: the preparation method of a kind of trimellitic acid three ester in the different ninth of the ten Heavenly Stems, and its preparation method is as follows:
Step 1: with trimellitic anhydride and isononyl alcohol in 1: the material that the ratio of 3.5mol～1: 4.5mol forms, and add in the reactor by 0.1%～0.3% gac of trimellitic anhydride weight, stir and heat up, in reaction process, just decolour, deduct the energy dissipation that the decolouring step is brought
Step 2: when mixture continues to be warmed up to 185 ℃～195 ℃, the mixture that adds 0.05%～0.2% tetrabutyl titanate of trimellitic anhydride weight and titanium isopropylate is as catalyzer, and the mass ratio of tetrabutyl titanate and titanium isopropylate is: 1: 1～1: 4;
Step 3: continue temperature reaction, when temperature rise reaches 185 ℃～245 ℃, reacted 3～4 hours, make fully thoroughly reaction in the still, the reactant acid number is controlled at below the 0.50mgKOH/g;
Step 4: the negative pressure dealcoholysis does not have backflow to visor;
Step 5: the preparation mass percent concentration is 10%～15% sodium hydroxide solution, and the acid number of material is controlled at below the 0.07mgKOH/g;
Step 6: water is fed reactor, and to carry out dealcoholysis as entrainer refining;
Step 7: cool to 150 ℃, the atlapulgite after the oven dry of adding finished product total mass 0.07%～0.2% mixes in reactor;
Step 8: filter soil trimellitic acid three ester in the different ninth of the ten Heavenly Stems.
Chemical reaction mechanism of the present invention is as follows:
The first step: at first a part trimellitic anhydride and a part isononyl alcohol form monoesters, and this reaction does not need catalyzer, and this step chemical equation is as follows:
Second step: monoesters generates dibasic acid esters with another different reaction in the ninth of the ten Heavenly Stems under catalyst action, this step chemical equation is as follows:
The 3rd step: dibasic acid esters generates three esters with another different reaction in the ninth of the ten Heavenly Stems under catalyst action, this step chemical equation is as follows:
As a further improvement on the present invention, esterification water that generates with reaction in the described step 5 and sodium hydroxide preparation mass percent concentration is 10%～15% sodium hydroxide solution.
As a further improvement on the present invention, the esterification water that should generate in the described step 6 carries out layering and removes oil reservoir, and the esterification water that layering is removed behind the oil reservoir feeds reactor as entrainer.
As water stripping, utilize the temperature of reaction mass self to make water become steam with esterification water, save the energy that water is become steam, avoided the increase of the wastewater flow rate that brings because of the stripping process for refining simultaneously, also saved the consumption of water.
As a further improvement on the present invention, in the described step 8, the diatomite with finished product total mass 0.08%～0.2% before filtering adds fully stirring in the reactor, and filtration velocity is fast like this, saves filtration time.
Useful technique effect of the present invention is: the present invention adopts no sulfuric acid catalysis synthesis technique, sulfuric acid catalysis that need not be traditional, and with titanic acid ester as catalyzer, pollution-free, good product quality, excessive alcohol can reuse; The present invention adopts solvent-free band water law, utilizes the hydrogen bond action of alcohol excess and water to form binary azeotrope apace and will generate water and break away from reactive system; The present invention merges decolouring step and reactions steps, saves the decolouring step, shortens the process time and raises the efficiency, and cuts down the consumption of energy; The present invention by replace with sodium hydroxide yellow soda ash come as alkali in and work in-process, atlapulgite comes the adjusted volume specific resistance, the finished-product volume specific resistance is regulated and is easy to operate; The present invention is with reacting in the esterification water conduct that generates and water and water stripping, reduce the wastewater flow rate that increases with steam stripped, utilized the temperature of reaction system self to make the esterification instant water vaporization that enters reduce the heat energy consumption that makes water become steam and cause as water stripping.
Embodiment
Embodiment one: at 16m
3Stainless steel cauldron in drop into trimellitic anhydride 3000Kg, (ingredient proportion is 1 to isononyl alcohol 7875Kg: 3.5mol), gac 4.5Kg, stir and heat up, when mixture is warmed up to 185 ℃, the adding mass ratio is 1: 1 tetrabutyl titanate and titanium isopropylate mixed catalyst 3Kg, continuation was 185 ℃～240 ℃ reactions 4 hours, the negative pressure dealcoholysis, adding mass percent concentration and be 10% sodium hydroxide solution neutralizes, the mixture acidic value is reached below the 0.07mgKOH/g, esterification water is removed oil reservoir through layering and is handled, and the esterification water after handling is fed the reactor dealcoholysis as entrainer make with extra care, and reactant cools to 150 ℃, the atlapulgite and the 20Kg diatomite that add after the 10Kg oven dry stirred 30 minutes, filter finished product.
Example example two: at 16m
3Stainless steel cauldron in drop into trimellitic anhydride 3000Kg, (ingredient proportion is 1 to isononyl alcohol 9000Kg: 4.0mol), gac 4.5Kg, stir and heat up, when mixture is warmed up to 190 ℃, the adding mass ratio is 1: 2.5 tetrabutyl titanate and titanium isopropylate mixed catalyst 4Kg, continuation was 190 ℃～240 ℃ reactions 3.5 hours, the negative pressure dealcoholysis, with mass percent concentration is that 10% sodium hydroxide solution neutralizes, the mixture acidic value is reached below the 0.07mgKOH/g, esterification water is removed oil reservoir through layering and is handled, and the esterification water after handling is fed the reactor dealcoholysis as entrainer make with extra care, and cools to 150 ℃, the atlapulgite and the 20Kg diatomite that add after the 10Kg oven dry stirred 30 minutes, filter finished product.
Example example three: at 16m
3Stainless steel cauldron in drop into trimellitic anhydride 3000Kg, (ingredient proportion is 1 to isononyl alcohol 10125Kg: 4.5mol), gac 4.5Kg, stir and heat up, when mixture is warmed up to 195 ℃, the adding mass ratio is 1: 4 tetrabutyl titanate and titanium isopropylate mixed catalyst 5Kg, continuation was 195 ℃～240 ℃ reactions 3.0 hours, the negative pressure dealcoholysis, with mass percent concentration is that 10% sodium hydroxide solution neutralizes, the mixture acidic value is reached below the 0.07mgKOH/g, esterification water is removed oil reservoir through layering and is handled, and the esterification water after handling is fed the reactor dealcoholysis as entrainer make with extra care, and cools to 150 ℃, the atlapulgite and the 20Kg diatomite that add after the 10Kg oven dry stirred 30 minutes, filter finished product.
Claims (4)
1. the preparation method of a trimellitic acid three ester in the different ninth of the ten Heavenly Stems, it is characterized by: its preparation method is as follows:
Step 1: with trimellitic anhydride and isononyl alcohol in 1: the material that the ratio of 3.5mol～1: 4.5mol forms, and add in the reactor by 0.1%～0.3% gac of trimellitic anhydride weight, stir and heat up;
Step 2: when mixture continues to be warmed up to 185 ℃～195 ℃, the mixture that adds 0.05%～0.2% tetrabutyl titanate of trimellitic anhydride weight and titanium isopropylate is as catalyzer, and the mass ratio of tetrabutyl titanate and titanium isopropylate is: 1: 1～1: 4;
Step 3: continue temperature reaction, when temperature rise reaches 185 ℃～245 ℃, reacted 3～4 hours, make fully thoroughly reaction in the still, the reactant acid number is controlled at below the 0.50mgKOH/g;
Step 4: the negative pressure dealcoholysis does not have backflow to visor;
Step 5: the preparation mass percent concentration is 10%～15% sodium hydroxide solution, and the acid number of material is controlled at below the 0.07mgKOH/g;
Step 6: water is fed reactor, and to carry out dealcoholysis as entrainer refining;
Step 7: cool to 150 ℃, the atlapulgite after the oven dry of adding finished product total mass 0.07%～0.2% mixes in reactor;
Step 8: filter soil trimellitic acid three ester in the different ninth of the ten Heavenly Stems.
2. the preparation method of trimellitic acid according to claim 1 three ester in the different ninth of the ten Heavenly Stems, it is characterized by: esterification water that generates with reaction in the described step 5 and sodium hydroxide preparation mass percent concentration are 10%～15% sodium hydroxide solution.
3. the preparation method of trimellitic acid according to claim 1 three ester in the different ninth of the ten Heavenly Stems, it is characterized by: the esterification water that should generate in the described step 6 carries out layering and removes oil reservoir, and the esterification water that layering is removed behind the oil reservoir feeds reactor as entrainer.
4. the preparation method of trimellitic acid according to claim 1 three ester in the different ninth of the ten Heavenly Stems is characterized by: in the described step 8, before filtering the diatomite of finished product total mass 0.08%～0.2% added in the reactor and fully stir.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102912719A CN101973884A (en) | 2010-09-26 | 2010-09-26 | Method for preparing triisononyl trimellitate (TINTM) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102912719A CN101973884A (en) | 2010-09-26 | 2010-09-26 | Method for preparing triisononyl trimellitate (TINTM) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101973884A true CN101973884A (en) | 2011-02-16 |
Family
ID=43573802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102912719A Pending CN101973884A (en) | 2010-09-26 | 2010-09-26 | Method for preparing triisononyl trimellitate (TINTM) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101973884A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214372A (en) * | 2013-05-10 | 2013-07-24 | 范强 | Synthesis method of tridecyl trimellitate |
| CN105330543A (en) * | 2015-10-19 | 2016-02-17 | 中国石油化工股份有限公司 | Refining processing method of polyol esters |
| CN106751876A (en) * | 2016-11-28 | 2017-05-31 | 江苏森禾化工科技有限公司 | A kind of production method of high temperature resistant composite elasticizer |
| CN108117666A (en) * | 2018-01-26 | 2018-06-05 | 江苏森禾化工科技有限公司 | A kind of high-low temperature resistant plasticizer TINTM |
| CN108892614A (en) * | 2018-08-30 | 2018-11-27 | 江苏正丹化学工业股份有限公司 | A kind of synthetic method of triisononyl trimellitate plasticizer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257472A (en) * | 1997-05-22 | 2000-06-21 | 塞拉尼斯有限公司 | Method for producing ester plasticizers |
| CN1636962A (en) * | 2003-03-26 | 2005-07-13 | 蒋平平 | Production method of multi-variety low-consumption plasticizer |
| CN1769260A (en) * | 2005-11-08 | 2006-05-10 | 江南大学 | Trimellitic tri(C8-9 ol)ester preparation method |
| CN101805263A (en) * | 2010-03-22 | 2010-08-18 | 江苏雷蒙化工科技有限公司 | Cleaning production method of phthalic acid di-(2-ethyl) ethyl ester |
-
2010
- 2010-09-26 CN CN2010102912719A patent/CN101973884A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257472A (en) * | 1997-05-22 | 2000-06-21 | 塞拉尼斯有限公司 | Method for producing ester plasticizers |
| CN1636962A (en) * | 2003-03-26 | 2005-07-13 | 蒋平平 | Production method of multi-variety low-consumption plasticizer |
| CN1769260A (en) * | 2005-11-08 | 2006-05-10 | 江南大学 | Trimellitic tri(C8-9 ol)ester preparation method |
| CN101805263A (en) * | 2010-03-22 | 2010-08-18 | 江苏雷蒙化工科技有限公司 | Cleaning production method of phthalic acid di-(2-ethyl) ethyl ester |
Non-Patent Citations (2)
| Title |
|---|
| 文艺等: "邻苯二甲酸810酯的催化合成", 《河北化工》, no. 3, 31 December 2005 (2005-12-31) * |
| 谢海涛等: "偏苯三酸三(2-乙基)己醋连续化生产工艺的研究", 《青岛科技大学学报》, vol. 25, no. 5, 31 October 2004 (2004-10-31) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214372A (en) * | 2013-05-10 | 2013-07-24 | 范强 | Synthesis method of tridecyl trimellitate |
| CN105330543A (en) * | 2015-10-19 | 2016-02-17 | 中国石油化工股份有限公司 | Refining processing method of polyol esters |
| CN106751876A (en) * | 2016-11-28 | 2017-05-31 | 江苏森禾化工科技有限公司 | A kind of production method of high temperature resistant composite elasticizer |
| CN108117666A (en) * | 2018-01-26 | 2018-06-05 | 江苏森禾化工科技有限公司 | A kind of high-low temperature resistant plasticizer TINTM |
| CN108892614A (en) * | 2018-08-30 | 2018-11-27 | 江苏正丹化学工业股份有限公司 | A kind of synthetic method of triisononyl trimellitate plasticizer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104610063A (en) | Novel preparation method of dioctyl terephthalate | |
| CN101029122B (en) | Production and use for acrylic ester modified polyester resin | |
| CN103665385A (en) | Olefine acid ester contained organic silicon polyether copolymer and preparing method thereof. | |
| CN101973884A (en) | Method for preparing triisononyl trimellitate (TINTM) | |
| CN101700885A (en) | Method for preparing activated carbon with high specific surface area | |
| CN106397368A (en) | Fatty alcohol-polyoxyethylene ether glycidyl ether and preparation method thereof | |
| CN103435642B (en) | Production method of trioctyl phosphate | |
| CN113477260B (en) | Catalyst and method for preparing biodiesel by using same | |
| CN101177617B (en) | Process for preparing biodiesel | |
| CN101967098A (en) | Preparation method of bis(2-propylheptyl) phthalate | |
| CN101195759B (en) | Technique for producing Chinese tallow tree stillingia oil biological diesel oil with solid base catalyst catalysis | |
| CN104694255B (en) | A kind of method that low-temperature negative-pressure prepares biodiesel | |
| CN102633640B (en) | Integrated production technique of acetyl tributyl citrate (ATBC) | |
| CN101785992B (en) | Preparation method of catalyst used for cracking and de-acidification of high-acid crude oil | |
| CN100460482C (en) | Method of preparing organism diesel oil from mixing plant oil | |
| CN110669583B (en) | Vegetable insulating oil refining process with rapeseed oil as raw material | |
| CN106635432A (en) | Method for preparing vegetable insulating oil by utilizing swill oil | |
| CN105505521A (en) | Method for preparing silicon-based biological lubricant base oil by adopting pipeline-type recycle reactor | |
| CN108586252A (en) | A kind of efficient esterification process of trioctyl trimellitate (TOTM) | |
| CN107723087A (en) | A kind of preparation method of biodiesel | |
| CN104120039B (en) | A kind of method that multistage ester exchange prepares fatty acid methyl ester | |
| CN103484258A (en) | Method for preparing biodiesel by using nano hydroxyapatite to catalyze triglyceride | |
| CN102627561A (en) | Preparation process for plasticizer-tributyl citrate | |
| CN111234934A (en) | Method for producing biodiesel by continuous ester exchange of waste oil | |
| CN101186597A (en) | Method for preparing epoxy soybean acidified oil (C1-4) without protonic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110216 |