CN111606803A - Production method of trioctyl trimellitate plasticizer with high volume resistivity - Google Patents
Production method of trioctyl trimellitate plasticizer with high volume resistivity Download PDFInfo
- Publication number
- CN111606803A CN111606803A CN202010569198.0A CN202010569198A CN111606803A CN 111606803 A CN111606803 A CN 111606803A CN 202010569198 A CN202010569198 A CN 202010569198A CN 111606803 A CN111606803 A CN 111606803A
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- CN
- China
- Prior art keywords
- trioctyl trimellitate
- volume resistivity
- plasticizer
- trimellitate plasticizer
- trimellitic anhydride
- 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.)
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 27
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000010992 reflux Methods 0.000 claims abstract description 18
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002148 esters Chemical class 0.000 claims abstract description 14
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 230000032050 esterification Effects 0.000 claims abstract description 11
- 238000005886 esterification reaction Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005070 sampling Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 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 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000005591 trimellitate group Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003809 water extraction 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of plasticizer synthesis, and particularly discloses a production method of a trioctyl trimellitate plasticizer with high volume resistivity, which comprises the following steps: adding trimellitic anhydride and isooctyl alcohol into an esterification kettle under the protection of nitrogen, adding activated carbon, and stirring and refluxing; adding tetraisopropyl titanate, continuously reacting, stirring at constant temperature, refluxing to separate water generated in the esterification process, sampling, detecting and then closing the reflux; dealcoholizing; balancing vacuum, reducing temperature at normal pressure, filtering to obtain clean trioctyl trimellitate product, and filtering again to obtain trioctyl trimellitate product. The production method of the trioctyl trimellitate plasticizer is prepared by the steps of esterification, acidity detection, high-vacuum dealcoholization and impurity removal of ester and the like, and the obtained plasticizer has the characteristics of light color and high quality, and has the advantages of low acid value, high volume resistivity, short and simple operation process, no corrosion to equipment, short reaction time, environmental protection, safety and easy industrial production.
Description
Technical Field
The invention relates to the technical field of plasticizers, in particular to a production method of a trioctyl trimellitate plasticizer with high volume resistivity.
Background
Plasticizers are polymeric additives that are widely used in industry. The plasticizer is used in plastic processing, and can modify or soften the plastic and increase the plasticity, flexibility, stretchability or expansibility and the like of the plastic. At present, the plasticizer industry has been developed into a plasticizer based on petrochemical industry and taking phthalate as a core, which is widely applied to the plastic and paint industries. However, the phthalate-containing plastic products can cause the dissolution of phthalate and have certain harm in the processes of processing, heating, packaging and containing. The trimellitate plasticizer has a plurality of excellent performances such as compatibility, electrical property, plasticizing performance, low-temperature performance, migration resistance, water extraction resistance, thermal stability and the like, and the plasticizing efficiency and the processing performance are similar to those of phthalate plasticizers. The product is widely used for 105 ℃ and 125 ℃ heat-resistant wire and cable materials, automotive interior materials and other products requiring heat resistance and durability, such as plates, sheets, gaskets and the like. Therefore, research and development of more trimellitate plasticizers with excellent performance have very important significance in the future plastic manufacturing industry.
Disclosure of Invention
The invention aims to improve the performance index of trioctyl trimellitate by improving the existing production process, and solves the problems of poor product performance such as acid reversion, low resistivity and the like in the production process of trioctyl trimellitate.
In order to solve the technical problems, the invention provides a production method of a trioctyl trimellitate plasticizer with high volume resistivity, which comprises the following steps:
s1, introducing nitrogen into the esterification kettle, adding trimellitic anhydride and isooctyl alcohol, adding activated carbon, and stirring and refluxing to react to 160-170 ℃;
s2, adding tetraisopropyl titanate, continuing to react to 210 ℃, stirring at constant temperature and refluxing for 1-1.5h, separating water generated in the esterification process, sampling to detect that the acid value of the crude ester is 0.05mgKOH/g, and closing reflux;
s3, removing excessive alcohol under the condition of vacuum 0.05-0.1 MPa;
s4, balancing vacuum, stopping heating, reducing the temperature to 90 ℃ under normal pressure, filtering by a plate frame to obtain a clean trioctyl trimellitate product, and filtering by a sand stick for the second time to obtain a trioctyl trimellitate finished product.
Further, the mole ratio of trimellitic anhydride to isooctanol in S1 is 1: 3.5-4.
Furthermore, the adding amount of the activated carbon in the S1 accounts for 0.3-0.5% of the mass of the trimellitic anhydride.
Further, the tetraisopropyl titanate in the S2 is added with 0.05-0.15% of the amount of the partial anhydride.
Furthermore, the content of trioctyl trimellitate in S4 is more than or equal to 99.5%, the acid value is 0.05-0.1mgKOH/g, the color number is less than or equal to 30, and the volume resistivity is more than or equal to 15 x 109 omega m.
The invention has the beneficial effects that: the production method of the trioctyl trimellitate plasticizer comprises the steps of esterification, acidity detection, high-vacuum dealcoholization and impurity removal of ester, and the like, and the obtained plasticizer has the characteristics of light color and high quality, and has the advantages of low acid value, high volume resistivity, short and simple operation process, no corrosion to equipment, short reaction time, environmental protection, safety and easy industrial production.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
A production method of trioctyl trimellitate plasticizer comprises the following specific steps: adding a mixture of 1: 3.5 of trimellitic anhydride and isooctyl alcohol, and adding activated carbon accounting for 0.3 percent of the mass of the trimellitic anhydride. Stirring and refluxing to react to 160-170 ℃, adding tetraisopropyl titanate with the amount of 0.05 of the meta anhydride, continuing to react to 210 ℃, stirring and refluxing at constant temperature for 1-1.5h, separating out water generated in the esterification process, sampling and detecting that the acid value of the crude ester is 0.05mgKOH/g, closing reflux, and removing excessive alcohol under the condition of vacuum of 0.05-0.1 MPa. And then balancing vacuum, stopping heating, reducing the temperature to 90 ℃ at normal pressure, filtering by using a plate frame to obtain a clean trioctyl ester product, and filtering by using a sand rod for the second time to obtain a finished product with the ester content of 99.55%, the acid value of 0.04mgKOH/g, the color number of 25 and the volume resistivity of 25 x 109 omega m.
Example two
A production method of trioctyl trimellitate plasticizer comprises the following specific steps: adding a mixture of 1: 4.2 of trimellitic anhydride and isooctyl alcohol, and adding activated carbon accounting for 0.45 percent of the mass of the trimellitic anhydride. Stirring and refluxing to react to 160-170 ℃, adding tetraisopropyl titanate with 0.1 percent of the amount of the metaanhydride, continuing to react to 210 ℃, stirring and refluxing at constant temperature for 1-1.5h, separating water generated in the esterification process, sampling and detecting that the acid value of the crude ester is 0.05mgKOH/g, closing reflux, and removing excessive alcohol under the vacuum condition of 0.05-0.1 MPa. And then balancing vacuum, stopping heating, reducing the temperature to 90 ℃ at normal pressure, filtering by a plate frame to obtain a clean trioctyl ester product, and filtering by a sand rod for the second time to obtain a finished product with the ester content of 99.6%, the acid value of 0.06mgKOH/g, the color number of 25 and the volume resistivity of 37 x 109 omega m.
EXAMPLE III
A production method of trioctyl trimellitate plasticizer comprises the following specific steps: adding a mixture of 1: 4, trimellitic anhydride and isooctyl alcohol, and active carbon accounting for 0.4 percent of the mass of the trimellitic anhydride is added. Stirring and refluxing to react to 160-170 ℃, adding tetraisopropyl titanate with 0.1 percent of the amount of the metaanhydride, continuing to react to 210 ℃, stirring and refluxing at constant temperature for 1-1.5h, separating water generated in the esterification process, sampling and detecting that the acid value of the crude ester is 0.05mgKOH/g, closing reflux, and removing excessive alcohol under the vacuum condition of 0.05-0.1 MPa. And then balancing vacuum, stopping heating, reducing the temperature to 90 ℃ at normal pressure, filtering by using a plate frame to obtain a clean trioctyl ester product, and filtering by using a sand rod for the second time to obtain a finished product with the ester content of 99.51%, the acid value of 0.08mgKOH/g, the color number of 30 and the volume resistivity of 17 x 109 omega m.
The above disclosure is only one preferred embodiment of the present invention, and certainly should not be construed as limiting the scope of the invention, which is defined by the claims and their equivalents.
Claims (5)
1. The production method of the trioctyl trimellitate plasticizer with high volume resistivity is characterized by comprising the following steps:
s1, introducing nitrogen into the esterification kettle, adding trimellitic anhydride and isooctyl alcohol, adding activated carbon, and stirring and refluxing to react to 160-170 ℃;
s2, adding tetraisopropyl titanate, continuing to react to 210 ℃, stirring at constant temperature and refluxing for 1-1.5h, separating water generated in the esterification process, sampling to detect that the acid value of the crude ester is 0.05mgKOH/g, and closing reflux;
s3, removing excessive alcohol under the condition of vacuum 0.05-0.1 MPa;
s4, balancing vacuum, stopping heating, reducing the temperature to 90 ℃ under normal pressure, filtering by a plate frame to obtain a clean trioctyl trimellitate product, and filtering by a sand stick for the second time to obtain a trioctyl trimellitate finished product.
2. The method for producing the trioctyl trimellitate plasticizer according to claim 1, wherein the molar ratio of trimellitic anhydride to isooctanol in S1 is 1: 3.5-4.
3. The method for producing the trioctyl trimellitate plasticizer according to claim 1, wherein the amount of the activated carbon added in S1 is 0.3-0.5% by mass of trimellitic anhydride.
4. The method for producing trioctyl trimellitate plasticizer with high volume resistivity as claimed in claim 1, wherein the amount of added trimellitic anhydride of tetraisopropyl titanate in S2 is 0.05-0.15%.
5. The method for producing trioctyl trimellitate plasticizer according to claim 1, wherein the trioctyl trimellitate plasticizer in S4 has an ester content of 99.5% or more, an acid value of 0.05 to 0.1mgKOH/g, a color number of 30 or less, and a volume resistivity of 15 x 109 Ω m or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010569198.0A CN111606803A (en) | 2020-06-20 | 2020-06-20 | Production method of trioctyl trimellitate plasticizer with high volume resistivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010569198.0A CN111606803A (en) | 2020-06-20 | 2020-06-20 | Production method of trioctyl trimellitate plasticizer with high volume resistivity |
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| Publication Number | Publication Date |
|---|---|
| CN111606803A true CN111606803A (en) | 2020-09-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010569198.0A Pending CN111606803A (en) | 2020-06-20 | 2020-06-20 | Production method of trioctyl trimellitate plasticizer with high volume resistivity |
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| CN (1) | CN111606803A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012092074A (en) * | 2010-10-28 | 2012-05-17 | Mitsubishi Gas Chemical Co Inc | Method for producing ester plasticizer |
| CN103007920A (en) * | 2012-10-16 | 2013-04-03 | 江苏正丹化学工业股份有限公司 | Catalyst for synthesizing trioctyl trimellitate from trimellitic anhydride or trimellitic acid and octanol through esterification and application thereof |
| 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 |
| CN110372504A (en) * | 2019-08-16 | 2019-10-25 | 南通百川新材料有限公司 | A method of polybasic ester is produced using inclined acid anhydride by-product recycling lighter component |
| WO2019239294A1 (en) * | 2018-06-11 | 2019-12-19 | Sabic Global Technologies B.V. | Methods of manufacture of trialkyl tricarboxylates, and trialkyl tricarboxylates made by the methods |
-
2020
- 2020-06-20 CN CN202010569198.0A patent/CN111606803A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012092074A (en) * | 2010-10-28 | 2012-05-17 | Mitsubishi Gas Chemical Co Inc | Method for producing ester plasticizer |
| CN103007920A (en) * | 2012-10-16 | 2013-04-03 | 江苏正丹化学工业股份有限公司 | Catalyst for synthesizing trioctyl trimellitate from trimellitic anhydride or trimellitic acid and octanol through esterification and application thereof |
| WO2019239294A1 (en) * | 2018-06-11 | 2019-12-19 | Sabic Global Technologies B.V. | Methods of manufacture of trialkyl tricarboxylates, and trialkyl tricarboxylates made by the methods |
| 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 |
| CN110372504A (en) * | 2019-08-16 | 2019-10-25 | 南通百川新材料有限公司 | A method of polybasic ester is produced using inclined acid anhydride by-product recycling lighter component |
Non-Patent Citations (1)
| Title |
|---|
| 韩长日等: "《橡塑助剂生产工艺与技术》", 30 November 2015, 科学技术文献出版社 * |
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Application publication date: 20200901 |