CN110922331A - Di-fatty acid o-dimethyl phthalate plasticizer and preparation method thereof - Google Patents
Di-fatty acid o-dimethyl phthalate plasticizer and preparation method thereof Download PDFInfo
- Publication number
- CN110922331A CN110922331A CN201911068490.8A CN201911068490A CN110922331A CN 110922331 A CN110922331 A CN 110922331A CN 201911068490 A CN201911068490 A CN 201911068490A CN 110922331 A CN110922331 A CN 110922331A
- Authority
- CN
- China
- Prior art keywords
- acid
- phthalic
- plasticizer
- fatty acid
- alcohol
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/12—Acetic acid esters
- C07C69/16—Acetic acid esters of dihydroxylic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/28—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with dihydroxylic compounds
-
- 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
Abstract
The invention provides a difatty acid o-phthalic dimethyl ester plasticizer and a preparation method thereof, wherein o-phthalic alcohol and fatty acid are added into a four-neck flask according to the molar ratio of (0.5-0.8): 1, a cesium copper tungstate catalyst accounting for 0.8-1.5% of the total mass of the o-phthalic alcohol and the fatty acid is added, nitrogen with the flow rate of 5-10 mL/min is introduced for protection, the mixture is heated to 70-100 ℃, the heating and stirring are stopped after the mixture is stirred for 2-4 hours, the residual o-phthalic alcohol is removed through reduced pressure distillation, and the catalyst is removed through filtration, so that difatty acid o-phthalic dimethyl ester is obtained. The invention adopts the esterification reaction of the phthalic acid glycol and the fatty acid to synthesize the difatty acid phthalic acid dimethyl ester plasticizer, replaces the prior production process for preparing the phthalate plasticizer by the alcoholysis reaction of the phthalic acid anhydride and the fatty alcohol, can obviously reduce the reaction temperature, and obtains the novel plasticizer which is easy to degrade and has light color.
Description
Technical Field
The invention relates to the technical field of plasticizers, in particular to a difatty acid o-dimethyl phthalate plasticizer and a preparation method thereof.
Background
The plasticizer is a polymer material assistant widely used in industry, and the flexibility of the plasticizer is enhanced and the plasticizer is easy to process by adding the plasticizer in plastic processing. The plasticizer is various, and the currently most widely used phthalic ester compound is mainly prepared by the alcoholysis reaction of phthalic anhydride and fatty alcohol. The plasticizer has the advantages of good compatibility, high plasticizing efficiency, low volatility and the like. However, the plasticizer is not chemically bonded in the polymer, so that the plasticizer is easily released under the influence of external conditions, and the emission is not easily degraded in the environment to cause pollution; in addition, the reaction temperature of the existing production process is higher, the color of the product is darker, and the use range of the plasticizer is limited. Therefore, the development of a novel plasticizer which is easy to degrade and light in color is of great significance.
Disclosure of Invention
The invention provides a preparation method of a novel plasticizer which is easy to degrade and light in color, wherein phthalic alcohol and fatty acid are used as raw materials, and cesium copper tungstate (H) is used as a plasticizer1.5Cs4.5CuW2O10) Esterification reaction is carried out under the action of a catalyst to prepare the corresponding difatty acid phthalate plasticizer.
The technical scheme adopted by the invention is as follows:
the structure of the plasticizer is that the plasticizer is di-fatty acid o-phthalate ester plasticizer
Wherein R is an alkyl group.
Preferably, R is CH3、C3H7、C7H15。
The preparation method of the difatty acid o-dimethyl phthalate plasticizer comprises the following steps:
step 1: mixing o-xylene glycol with fatty acid;
step 2: adding a copper cesium tungstate catalyst into the mixture obtained in the step 1, and introducing nitrogen to perform an esterification reaction;
and step 3: and (3) removing the residual phthalic alcohol and the copper cesium tungstate catalyst in the reactant obtained in the step (2) to obtain the difatty acid phthalate plasticizer.
Preferably, in the step 1, the molar ratio of the o-xylene glycol to the fatty acid is (0.5-0.8): 1.
Preferably, in the step 2, the cesium copper tungstate catalyst accounts for 0.8-1.5% of the total mass of the o-xylene glycol and the fatty acid.
Preferably, in the step 2, the flow rate of the nitrogen is 5-10 mL/min.
Preferably, in the step 2, the reaction temperature of the esterification reaction is 70-100 ℃, and the stirring time is 2-4 hours.
Preferably, the fatty acid is acetic acid, butyric acid or isooctanoic acid.
Has the advantages that: the invention adopts the esterification reaction of the phthalic acid glycol and the fatty acid to synthesize the difatty acid phthalic acid dimethyl ester plasticizer, and replaces the prior production process for preparing the phthalate plasticizer by the alcoholysis reaction of the phthalic anhydride and the fatty alcohol. As can be seen from the molecular structural formula, no conjugated structure exists between the ester group and the benzene ring in the structure of the difatty acid o-phthalic ester plasticizer, which is beneficial to improving the degradation performance; and the reaction temperature is lower, byproducts are less in the reaction process, and the color of the final product is light.
Detailed Description
The invention will be better understood from the following examples.
In the following examples, the copper cesium tungstate catalyst was prepared according to the method disclosed in CN 201910676585.1.
Example 1
Adding 6.9g of o-xylene glycol and 6.0g of acetic acid (the molar ratio is 0.5:1) into a four-neck flask, then adding 0.1g (0.8%) of copper cesium tungstate catalyst, introducing nitrogen with the flow rate of 5mL/min for protection, heating to 70 ℃, stirring for 4 hours, stopping heating and stirring, carrying out reduced pressure distillation to remove residual o-xylene glycol, filtering to remove the catalyst to obtain dimethyl phthalate diacetate, and obtaining the esterification rate of the o-xylene glycol of 95.8% and the yield of the dimethyl phthalate diacetate of 87.3% by high performance liquid chromatography analysis.
Example 2
Adding 9.7g of o-xylene glycol and 6.0g of acetic acid (the molar ratio is 0.7:1) into a four-neck flask, then adding 0.16g (1.0%) of copper cesium tungstate catalyst, introducing nitrogen with the flow rate of 8mL/min for protection, heating to 90 ℃, stirring for 2 hours, stopping heating and stirring, carrying out reduced pressure distillation to remove residual o-xylene glycol, filtering to remove the catalyst to obtain dimethyl phthalate diacetate, and obtaining the dimethyl phthalate diacetate with the esterification rate of 97.5% and the yield of 89.8% by high performance liquid chromatography analysis.
Example 3
Adding 11.0g of phthalic alcohol and 8.8g of butyric acid (the molar ratio is 0.8:1) into a four-neck flask, then adding 0.3g (1.5%) of copper cesium tungstate catalyst, introducing nitrogen with the flow rate of 6mL/min for protection, heating to 100 ℃, stirring for 2 hours, stopping heating and stirring, carrying out reduced pressure distillation to remove residual phthalic alcohol, filtering to remove the catalyst to obtain dibutyrate dimethyl phthalate, and obtaining the phthalic alcohol esterification rate of 98.3% and the dibutyrate dimethyl phthalate yield of 91.5% by high performance liquid chromatography analysis calculation.
Example 4
Adding 8.3g of phthalic alcohol and 8.8g of butyric acid (the molar ratio is 0.6:1) into a four-neck flask, then adding 0.17g (1.0%) of copper cesium tungstate catalyst, introducing nitrogen with the flow rate of 6mL/min for protection, heating to 90 ℃, stirring for 3 hours, stopping heating and stirring, carrying out reduced pressure distillation to remove residual phthalic alcohol, filtering to remove the catalyst to obtain dibutyrate dimethyl phthalate, and obtaining the phthalic acid dimethyl ester with the esterification rate of 96.7% and the yield of the dibutyrate dimethyl ester of 90.1% by high performance liquid chromatography analysis.
Example 5
Adding 6.9g of o-xylene glycol and 14.4g of isooctanoic acid (molar ratio is 0.5:1) into a four-neck flask, then adding 0.21g (1.0%) of copper cesium tungstate catalyst, introducing nitrogen with the flow rate of 5mL/min for protection, heating to 80 ℃, stirring for 3 hours, stopping heating and stirring, carrying out reduced pressure distillation to remove residual o-xylene glycol, filtering to remove the catalyst to obtain diisooctanoic acid dimethyl phthalate, and calculating by high performance liquid chromatography analysis to obtain the o-xylene glycol esterification rate of 97.9% and the diisooctanoic acid dimethyl phthalate yield of 92.0%.
Example 6
Adding 11.0g of o-xylene glycol and 14.4g of isooctanoic acid (molar ratio is 0.8:1) into a four-neck flask, then adding 0.38g (1.5%) of copper cesium tungstate catalyst, introducing nitrogen with the flow rate of 7mL/min for protection, heating to 100 ℃, stirring for 4 hours, stopping heating and stirring, carrying out reduced pressure distillation to remove residual o-xylene glycol, filtering to remove the catalyst, obtaining diisooctanoic acid dimethyl phthalate, and obtaining the o-xylene glycol esterification rate of 98.3% and the yield of the diisooctanoic acid dimethyl phthalate of 93.7% by high performance liquid chromatography analysis.
The ultimate biodegradability of the plasticizer is measured by GB/T21856-2008 chemical rapid biodegradability carbon dioxide generation test method, and the chromaticity of the plasticizer is measured by a CS-10 precision color difference meter. The biodegradation performance and the chroma of the difatty acid dimethyl phthalate are compared with those of phthalate plasticizer products in the current market. The comparison result shows that: the difatty acid phthalate plasticizer prepared by the invention has better biodegradability and lighter color.
TABLE 1
The present invention provides a method for preparing difatty acid phthalate plasticizer, and a plurality of methods and ways for implementing the technical scheme, and the above description is only a preferred embodiment of the present invention, it should be noted that, for those skilled in the art, a plurality of modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (8)
1. A difatty acid o-dimethyl ester plasticizer is characterized in that the structure is
2. The difatty acid phthalate dimethyl ester plasticizer according to claim 1, wherein R is CH3、C3H7、C7H15。
3. The process for producing a difatty acid phthalate ester plasticizer according to claim 1, which comprises the steps of:
step 1: mixing o-xylene glycol with fatty acid;
step 2: adding a copper cesium tungstate catalyst into the mixture obtained in the step 1, and introducing nitrogen to perform an esterification reaction;
and step 3: and (3) removing the residual phthalic alcohol and the copper cesium tungstate catalyst in the reactant obtained in the step (2) to obtain the difatty acid phthalate plasticizer.
4. The method according to claim 3, wherein the molar ratio of the o-xylene glycol to the fatty acid in the step 1 is (0.5 to 0.8): 1.
5. The preparation method according to claim 3, wherein in the step 2, the cesium copper tungstate catalyst accounts for 0.8-1.5% of the total mass of the o-xylene glycol and the fatty acid.
6. The method according to claim 3, wherein the flow rate of the nitrogen gas in the step 2 is 5 to 10 mL/min.
7. The preparation method according to claim 3, wherein in the step 2, the reaction temperature of the esterification reaction is 70-100 ℃, and the stirring time is 2-4 h.
8. The method according to any one of claims 3 to 7, wherein the fatty acid is acetic acid, butyric acid or isooctanoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911068490.8A CN110922331A (en) | 2019-11-05 | 2019-11-05 | Di-fatty acid o-dimethyl phthalate plasticizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911068490.8A CN110922331A (en) | 2019-11-05 | 2019-11-05 | Di-fatty acid o-dimethyl phthalate plasticizer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110922331A true CN110922331A (en) | 2020-03-27 |
Family
ID=69852261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911068490.8A Pending CN110922331A (en) | 2019-11-05 | 2019-11-05 | Di-fatty acid o-dimethyl phthalate plasticizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110922331A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB926607A (en) * | 1959-11-10 | 1963-05-22 | Geigy Co Ltd | Saturated aliphatic carboxylic ester compositions and lubricants consisting of or containing them |
| US5164436A (en) * | 1987-05-19 | 1992-11-17 | Hoechst Aktiengesellschaft | Waxy compounds of aromatic alcohols, their preparation and their use |
| CN102030637A (en) * | 2009-10-08 | 2011-04-27 | 奥克塞有限公司 | Method for brightening the colour of polyol esters |
| US20150126655A1 (en) * | 2013-11-01 | 2015-05-07 | Exxonmobil Research And Engineering Company | Catechol based diesters for general purpose plasticizers |
| CN110292933A (en) * | 2019-07-25 | 2019-10-01 | 盐城工学院 | A kind of catalyst and the preparation method and application thereof for the synthesis of diisooctyl phthalate plasticizer |
-
2019
- 2019-11-05 CN CN201911068490.8A patent/CN110922331A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB926607A (en) * | 1959-11-10 | 1963-05-22 | Geigy Co Ltd | Saturated aliphatic carboxylic ester compositions and lubricants consisting of or containing them |
| US5164436A (en) * | 1987-05-19 | 1992-11-17 | Hoechst Aktiengesellschaft | Waxy compounds of aromatic alcohols, their preparation and their use |
| CN102030637A (en) * | 2009-10-08 | 2011-04-27 | 奥克塞有限公司 | Method for brightening the colour of polyol esters |
| US20150126655A1 (en) * | 2013-11-01 | 2015-05-07 | Exxonmobil Research And Engineering Company | Catechol based diesters for general purpose plasticizers |
| CN110292933A (en) * | 2019-07-25 | 2019-10-01 | 盐城工学院 | A kind of catalyst and the preparation method and application thereof for the synthesis of diisooctyl phthalate plasticizer |
Non-Patent Citations (5)
| Title |
|---|
| COLUMBUS，OHIO: "US REGISTRY[Online]", 《REGISTRY》 * |
| IOANNIS CONSTANTINIDES ET AL: "Reactions of molecules with two equivalent functional groups. 2. Acetylation of the isomers of bis(hydroxymethyl)benzene", 《JOURNAL OF PHYSICAL ORGANIC CHEMISTRY》 * |
| 叶彦春 等: "《有机化学实验》", 31 January 2018, 北京理工大学出版社 * |
| 吴清 等: "《物理药剂学》", 30 November 2018, 中国中医药出版社 * |
| 张付利 等: "《有机化学》", 31 January 2010, 河南大学出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2014209065A1 (en) | Method for producing acrylic acid from glycerol | |
| CN1824640A (en) | Method for preparing hydroxyalkyl acrylate using lewis acid catalyst | |
| Bhuniya et al. | Synthesis of versatile intermediates for cyclopentanoid natural products via enantioselective deprotonation of substituted cyclopentene oxide | |
| CN110922331A (en) | Di-fatty acid o-dimethyl phthalate plasticizer and preparation method thereof | |
| WO2014050810A1 (en) | Method for producing ester compound and palladium catalyst used in method for producing ester compound | |
| JPS59212495A (en) | Preparation of 1,2,3,4-cyclobutanetetracarboxylic acid-1, 2:3,4-dianhydride | |
| EP2297082A1 (en) | Method for preparing polymer bioplasticizers | |
| CN1187309C (en) | Method of esterifying in ion liquid [Hmim]+ BF4- | |
| EP1620515A1 (en) | Reactive diluents in coating formulation | |
| CN107540520B (en) | Method for preparing pyromellitic acid or trimellitic acid from pinacol | |
| CN112939780B (en) | Synthetic method of indanone derivatives | |
| KR102599901B1 (en) | Method for producing cis,cis-1,2,4-cyclohexanetricarboxylic acid crystals | |
| JP5754133B2 (en) | Method for producing carboxylic acid tertiary butyl ester | |
| CN112694430A (en) | Preparation method of 1, 5-dihydro-2H-pyrrole-2-ketone compound | |
| CN112521278B (en) | Method for preparing carboxylic ester compound | |
| CN111138279A (en) | Mixed ester derived from PTA residue and preparation method thereof | |
| EP3898584A1 (en) | Improved process to produce specific alpha,beta-unsaturated carboxylates | |
| CN1162391C (en) | Process to separate linear alkyl 5-formylvalerate | |
| CN109970552B (en) | Coproduction method of methyl benzoate and ethyl benzoate | |
| CN1390212A (en) | Method for producing of benzofuranone oximes | |
| KR20230039328A (en) | LIGAND COMPOUND, METHOD FOR PREPRARING THEREOF AND METHOD FOR PREPARING α,β-UNSATURATED CARBOXYLATE BY USING THE SAME | |
| CN110790661A (en) | Method for converting benzyl borate compounds into phenylacetic acid and derivatives thereof by using carbon dioxide | |
| CN1663944A (en) | Process for preparing acetamides compounds | |
| CN116730785A (en) | Method for synthesizing ester compound by light promotion | |
| CN115286628A (en) | Preparation method of indolo [2,1a ] isoquinoline compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200327 |