CN101613273A - A kind of preparation method of dimeric acid methyl ester - Google Patents
A kind of preparation method of dimeric acid methyl ester Download PDFInfo
- Publication number
- CN101613273A CN101613273A CN200910159634A CN200910159634A CN101613273A CN 101613273 A CN101613273 A CN 101613273A CN 200910159634 A CN200910159634 A CN 200910159634A CN 200910159634 A CN200910159634 A CN 200910159634A CN 101613273 A CN101613273 A CN 101613273A
- Authority
- CN
- China
- Prior art keywords
- acid
- methyl ester
- acid methyl
- functionalization
- alkylsulphonic
- 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.)
- Granted
Links
- -1 dimeric acid methyl ester Chemical class 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000002253 acid Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002608 ionic liquid Substances 0.000 claims abstract description 19
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 17
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 235000012976 tarts Nutrition 0.000 claims abstract description 6
- 150000001449 anionic compounds Chemical class 0.000 claims abstract description 5
- 229910001412 inorganic anion Inorganic materials 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- ZWPUSIPAMUKNJR-UHFFFAOYSA-N [Br].[Cu] Chemical compound [Br].[Cu] ZWPUSIPAMUKNJR-UHFFFAOYSA-N 0.000 claims description 2
- LYVWMIHLNQLWAC-UHFFFAOYSA-N [Cl].[Cu] Chemical compound [Cl].[Cu] LYVWMIHLNQLWAC-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000006471 dimerization reaction Methods 0.000 abstract description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- 238000000605 extraction Methods 0.000 description 21
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 10
- 230000006837 decompression Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 5
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- 239000011592 zinc chloride Substances 0.000 description 5
- HGGLDADJQQPKKC-UHFFFAOYSA-N 2-butyl-1-methylimidazole Chemical compound CCCCC1=NC=CN1C HGGLDADJQQPKKC-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- IYVYLVCVXXCYRI-UHFFFAOYSA-N 1-propylimidazole Chemical compound CCCN1C=CN=C1 IYVYLVCVXXCYRI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- CVOYGOGNURBWIP-UHFFFAOYSA-N [Br+].C(CCC)[N+]1=CC=CC=C1 Chemical compound [Br+].C(CCC)[N+]1=CC=CC=C1 CVOYGOGNURBWIP-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229940055858 aluminum chloride anhydrous Drugs 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JQRYUMGHOUYJFW-UHFFFAOYSA-N pyridine;trihydrobromide Chemical compound [Br-].[Br-].[Br-].C1=CC=[NH+]C=C1.C1=CC=[NH+]C=C1.C1=CC=[NH+]C=C1 JQRYUMGHOUYJFW-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the method that the ionic liquid-catalyzed unsaturated fatty acids methyl esters of a kind of Br φ nsted-Lewis bisgallic acid dimerization prepares dimeric acid methyl ester, it is characterized in that adopting 1 of the pyridylium of alkylsulphonic acid functionalization or alkylsulphonic acid functionalization, the Br φ nsted-Lewis bisgallic acid ionic liquid that the quaternary ammonium salt cationic of 3-dialkylimidazolium positively charged ion or alkylsulphonic acid functionalization and Lewis tart inorganic anion constitute is as catalyzer; Under nitrogen protection, 220～280 ℃ of temperature of reaction, reaction times 2～8 hours catalysis fatty acid methyl esters polyreaction prepare dimeric acid methyl ester, compared with prior art: 1. have higher polymerizing power, it is short to need not pressurization and reaction times.2. dimeric acid methyl ester product and ionic-liquid catalyst are miscible and layering voluntarily makes sepn process more easy.3. the catalyst ion liquid properties is stable, can be recycled.
Description
Technical field
The present invention relates to a kind of
The application of-Lewis bisgallic acid ionic liquid in unsaturated fatty acids methyl esters polyreaction promptly relates to a kind of
The ionic liquid-catalyzed unsaturated fatty acids methyl esters of-Lewis bisgallic acid dimerization prepares the novel method of dimeric acid methyl ester.
Background technology
Dimeric acid methyl ester is the intermolecular generation of two or more unsaturated fatty acid esters Diels-Alder reaction, the oligomeric compound of the dicarboxylic esters that generates, it is actually by 36 carbon dimers, a small amount of 54 carbon tripolymers and the mixture formed of polymer polymer more.Dimeric acid methyl ester can be used to produce polyamide resin, and its snappiness is good, adhesive power is high and antiseptic and rustproof characteristic is arranged, and can be used for making coating, tamanori etc., is widely used in industries such as boats and ships, machinery, motor, automobile, civil construction.The polymkeric substance of dimeric acid methyl ester has good snappiness, sticking power, stopping property and water tolerance, can be used for industries such as electronics, coating, printing ink.Dimeric acid methyl ester and petroleum product, organic solvent have good intermiscibility, thermostability, can be used as metal processing machining oil, lubricating oil, antirust wet goods additive, also can be used as tensio-active agent and be used for washing composition, flow agent, levelling agent, dispersion agent, static inhibitor etc.Bao Dao lipid acid polymerization method is hot dimerization method the earliest, this arts demand high-temperature pressurizing reaction.At present carclazyte catalysis fatty acid methyl ester dimerization reactions that adopt prepare dimeric acid methyl ester more, are catalyzer as US 3873585 with the wilkinite that contains 75% above polynite; It is catalyzer that US 6187903 and US 3632822 adopt the carclazyte of alkali-metal oxyhydroxide and oxide modifying respectively; And CN101293829A employing Aluminum chloride anhydrous or Zinc Chloride Anhydrous are catalyzer, and the vitriol oil is a promotor.There is following shortcoming mostly in these technologies: the consumption of heterogeneous catalyst is excessive, and the meeting entrained product, causes the loss of product; Generally need to carry out under the high pressure, reaction conditions is relatively harsher, and is also higher to the requirement of conversion unit and operation.
Because of having traditional molecular solvent and fused salt dual nature, ionic liquid at room temperature has been widely used in catalysis or the uncatalyzed reaction as eco-friendly green solvent of a class or catalyzer.In recent years, the acid functionalization ionic liquid has become the focus in the research, and its advantage is: compare favourably with solid acid, and the tart modulation is easier, meticulousr, thereby helps the research and the screening of catalyst of catalytic mechanism more; Similar with conventional acid, have the advantage of fluent material, as: good fluidity, acidic site density height and strength of acid are evenly distributed; By changing and modified ion liquid yin, yang ionic structure, can realize the optimization of heterogeneous reaction system, as: simplify the separation of product, promote ion liquid recycling.Therefore, the acid functionalization ionic liquid can replace the conventional acid catalyzer, has great application potential.
Summary of the invention
The objective of the invention is to replace the method that traditional acid catalysis fatty acid methyl polyisocyanate polyaddition prepares dimeric acid methyl ester, a kind of efficient and eco-friendly catalysts is provided, under the reaction conditions of gentleness, catalysis fatty acid methyl ester polyreaction prepares the novel method of dimeric acid methyl ester, for dimeric acid methyl ester synthetic provides an eco-friendly operational path.
The present invention relates to a kind of preparation method of dimeric acid methyl ester, it is characterized in that adopting 1 of the pyridylium of alkylsulphonic acid functionalization or alkylsulphonic acid functionalization, the quaternary ammonium salt cationic of 3-dialkylimidazolium positively charged ion or alkylsulphonic acid functionalization and Lewis tart inorganic anion constitute
-Lewis bisgallic acid ionic liquid is as catalyzer; Reaction conditions is under the nitrogen protection, 200～280 ℃ of temperature of reaction, 2～8 hours reaction times, and catalysis fatty acid methyl ester polyreaction prepares dimeric acid methyl ester.
1 of pyridylium of alkylsulphonic acid functionalization used herein (1) or alkylsulphonic acid functionalization, the general structure of the quaternary ammonium salt cationic (3) of 3-dialkylimidazolium positively charged ion (2) or alkylsulphonic acid functionalization is as follows:
N=3～4 wherein, R
1Be C
1～C
3, R
2Be C
1～C
3
Lewis tart inorganic anion used herein is a kind of in chlorine zincic acid root, bromine zincic acid root, chlorine copper acid group, bromine copper acid group, chlorine ferrous acid root, the bromine ferrous acid root.
Ionic liquid quality used in the present invention is 1: 30 to 1: 4 with the total quality of material ratio of reaction
The present invention solves this technical problem by the following technical programs:
1.
The ion liquid typical production of-Lewis bisgallic acid is: with a certain amount of 1,3-propane sultone or 1, it is in 5～10 times the ethyl acetate that the 4-butane sultone is dissolved in its total mass number, be warming up to 40～60 ℃, drip equimolar N-Methylimidazole, or the N-ethyl imidazol(e), or the N-propyl imidazole, or pyridine, or Trimethylamine 99, or triethylamine, or tripropyl amine, dropwise, after the insulation reaction 3～5 hours, filter, filter cake washs with ethyl acetate, and, obtain corresponding white solid inner salt in 100 ℃ times dry 2 hours; Get a certain amount of inner salt that makes, be dissolved in the deionized water of 2～4 times of its total mass numbers, dripping equimolar mass concentration and be 37% hydrochloric acid or mass concentration is 40% Hydrogen bromide acidification reaction, after dropwising, is warming up to 70～90 ℃ and insulation reaction 2～3 hours; After reaction finished, decompression dehydration obtained light yellow viscous liquid acidifying inner salt; Get a certain amount of acidifying inner salt that makes, with mol ratio be 1: 1.1～3.0 zinc chloride, or zinc bromide, or cupric chloride; or cupric bromide, or iron(ic) chloride, or the iron bromide mixing, under nitrogen protection; be warming up to 90～110 ℃, insulation reaction to solid all dissolves, and promptly obtains being under the room temperature heavy-gravity liquid
-Lewis bisgallic acid ionic liquid.
The typical case of dimeric acid methyl ester preparation be (with
-Lewis bisgallic acid ionic liquid 1-(4-sulfonic acid) butyl-3-Methylimidazole chlorozincate; acidifying inner salt and zinc chloride mol ratio 1: 2.5): get the ionic liquid of 1.0～2.5 parts of weight and the fatty acid methyl ester of 10～30 parts of weight; under nitrogen protection; in 200～280 ℃ of following polyreactions after 2～8 hours; cooling also adds proper amount of solvent toluene extraction product, topples over and tells the upper strata extraction phase.The supernatant liquid solvent that reduces pressure obtains the dimeric acid methyl ester product.
3. the employed ionic liquid of method of the present invention is reusable, ionic liquid multiple canonical process is after the reaction solution extraction with esterification last time, because of under the ionic liquid low temperature very thickness and density greater than extraction phase, can directly topple over easily and the upper strata extraction phase, lower floor's ionic liquid need not any processing and promptly can be used for next polyreaction, when the ionic liquid consumption is reaction solution total mass 20%, to reuse 6 times, the yield of polymerisate dimeric acid methyl ester is not seen obvious decline.
The present invention compares with traditional catalyst, is characterized in:
1. have higher polymerizing power, it is short to need not pressurization and reaction times.
2. product dimeric acid methyl ester look shallow, matter good, and layering voluntarily makes the separation of product and aftertreatment more easy with ionic-liquid catalyst is not miscible.
3. the catalyst ion liquid properties is stable, and reaction is with promptly can be used for reaction next time without any processing later, and catalytic performance do not see reduction, and it is good to recycle performance, genus environmentally friendly technology route.
Specific implementation method
Below in conjunction with embodiment method of the present invention being described further, is not limitation of the invention.
Embodiment one: with 1.0g 1-(4-sulfonic acid) butyl-3-Methylimidazole chlorozincate (wherein the mol ratio of chlorination 1-(4-sulfonic acid) butyl-3-methylimidazole salt and zinc chloride is 1: 3.0) and 30g fatty acid methyl ester under nitrogen protection; in 230 ℃ of reactions 6 hours; be cooled to room temperature; add toluene 30g extraction polymerisate and unreacted raw material; tell upper layer of extraction liquid; and the decompression (5mmHg) 240 ℃ deviate from toluene and unreacting material, obtain the polymerisate dimeric acid methyl ester, yield is 67%.
Embodiment two: with 2.0g 1-(3-sulfonic acid) propyl group-3-propyl imidazole chloro-cuprate (wherein the mol ratio of chlorination 1-(3-sulfonic acid) butyl-3-methylimidazole salt and cupric chloride is 1: 2.0) and 10g fatty acid methyl ester under nitrogen protection; in 200 ℃ of reactions 5 hours; be cooled to room temperature; add toluene 20g extraction polymerisate and unreacted raw material; tell upper layer of extraction liquid; and the decompression (5mmHg) 240 ℃ deviate from toluene and unreacting material, obtain the polymerisate dimeric acid methyl ester, yield is 71%.
Embodiment three: with 3.0g 1-(4-sulfonic acid) butyl-3-ethyl imidazol(e) bromine cuprate (wherein the mol ratio of bromination 1-(4-sulfonic acid) butyl-3-ethyl imidazol(e) salt and cupric bromide is 1: 1.1) and 12g fatty acid methyl ester under nitrogen protection; in 280 ℃ of reactions 4 hours; be cooled to room temperature; add toluene 25g extraction polymerisate and unreacted raw material; tell upper layer of extraction liquid; and the decompression (5mmHg) 240 ℃ deviate from toluene and unreacting material, obtain the polymerisate dimeric acid methyl ester, yield is 53%.
Embodiment four: with 1.5g 4-sulfonic acid butyl-pyridinium bromine zincate (wherein the mol ratio of bromination 4-sulfonic acid butyl-pyridinium salt and zinc chloride is 1: 2.0) and 20g fatty acid methyl ester under nitrogen protection; in 200 ℃ of reactions 8 hours; be cooled to room temperature; add toluene 35g extraction polymerisate and unreacted raw material; tell upper layer of extraction liquid; and the decompression (5mmHg) 240 ℃ deviate from toluene and unreacting material, obtain the polymerisate dimeric acid methyl ester, yield is 76%.
Embodiment five: with 1.5g 3-sulfonic acid propyl group pyridinium tribromide wustite (wherein the mol ratio of bromination 3-sulfonic acid propyl group pyridinium salt and iron bromide is 1: 2.5) and 20g fatty acid methyl ester under nitrogen protection; in 250 ℃ of reactions 5 hours; be cooled to room temperature; add toluene 35g extraction polymerisate and unreacted raw material; tell upper layer of extraction liquid; and the decompression (5mmHg) 240 ℃ deviate from toluene and unreacting material, obtain the polymerisate dimeric acid methyl ester, yield is 74%.
Embodiment six: with 1.0g 3-sulfonic acid oxypropyl trimethyl amine ferricyanide (wherein the mol ratio of chlorination 3-sulfonic acid oxypropyl trimethyl amine salt and iron(ic) chloride is 1: 2.0) and 10g fatty acid methyl ester under nitrogen protection; in 280 ℃ of reactions 2 hours; be cooled to room temperature; add toluene 15g extraction polymerisate and unreacted raw material; tell upper layer of extraction liquid; and the decompression (5mmHg) 240 ℃ deviate from toluene and unreacting material, obtain the polymerisate dimeric acid methyl ester, yield is 52%.
Embodiment seven: with 1.5g 3-sulfonic acid propyl group triethylamine ferricyanide (wherein the mol ratio of chlorination 3-sulfonic acid propyl group triethyl amine salt and iron(ic) chloride is 1: 2.0) and 20g fatty acid methyl ester under nitrogen protection; in 260 ℃ of reactions 4 hours; be cooled to room temperature; add toluene 15g extraction polymerisate and unreacted raw material; tell upper layer of extraction liquid; and the decompression (5mmHg) 240 ℃ deviate from toluene and unreacting material, obtain the polymerisate dimeric acid methyl ester, yield is 64%.
Embodiment eight: with 3.0g 4-sulfonic acid butyl tripropylamine ferricyanide (wherein the mol ratio of chlorination 4-sulfonic acid butyl tripropyl amine salt and iron(ic) chloride is 1: 1.5) and 30g fatty acid methyl ester under nitrogen protection; in 230 ℃ of reactions 6 hours; be cooled to room temperature; add toluene 50g extraction polymerisate and unreacted raw material; tell upper layer of extraction liquid; and the decompression (5mmHg) 240 ℃ deviate from toluene and unreacting material, obtain the polymerisate dimeric acid methyl ester, yield is 73%.
Claims (4)
1. the preparation method of a dimeric acid methyl ester, tool is characterised in that 1 of the pyridylium that adopts the alkylsulphonic acid functionalization or alkylsulphonic acid functionalization, the quaternary ammonium salt cationic of 3-dialkylimidazolium positively charged ion or alkylsulphonic acid functionalization and Lewis tart inorganic anion formation
The bisgallic acid ionic liquid is as catalyzer; Reaction conditions is under the nitrogen protection, 200～280 ℃ of temperature of reaction, 2～8 hours reaction times, and catalysis fatty acid methyl ester polyreaction prepares dimeric acid methyl ester.
2. preparation method as claimed in claim 1, it is characterized in that 1 of the pyridylium (1) of described alkylsulphonic acid functionalization or alkylsulphonic acid functionalization, the general structure of the quaternary ammonium salt cationic (3) of 3-dialkylimidazolium positively charged ion (2) or alkylsulphonic acid functionalization is as follows:
N=3～4 wherein, R
1Be C
1～C
3, R
2Be C
1～C
3
3. preparation method as claimed in claim 1 is characterized in that described Lewis tart inorganic anion is a kind of in chlorine zincic acid root, bromine zincic acid root, chlorine copper acid group, bromine copper acid group, chlorine ferrous acid root, the bromine ferrous acid root.
4. preparation method as claimed in claim 1 is characterized in that described ionic liquid quality and the total quality of material ratio of reaction are 1: 30 to 1: 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910159634.0A CN101613273B (en) | 2009-07-25 | 2009-07-25 | Method for preparing dimeric acid methyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910159634.0A CN101613273B (en) | 2009-07-25 | 2009-07-25 | Method for preparing dimeric acid methyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101613273A true CN101613273A (en) | 2009-12-30 |
| CN101613273B CN101613273B (en) | 2014-04-16 |
Family
ID=41493184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910159634.0A Expired - Fee Related CN101613273B (en) | 2009-07-25 | 2009-07-25 | Method for preparing dimeric acid methyl ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101613273B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382015A (en) * | 2011-08-02 | 2012-03-21 | 常州大学 | Method for preparing sulfated methyl ester by ionic liquid catalysis method |
| CN102516128A (en) * | 2011-12-19 | 2012-06-27 | 河北工业大学 | Synthetic technology of diphenylmethane dicarbamate by adopting Bronsted-Lewis acidic ionic liquid catalysis |
| CN102557928A (en) * | 2011-12-29 | 2012-07-11 | 北京国力源高分子科技研发中心 | Method for preparing dimeric acid methyl ester by using microwaves |
| CN103204836A (en) * | 2013-03-31 | 2013-07-17 | 青岛科技大学 | Method for preparing 5-hydroxymethyl furfural |
| CN104785297A (en) * | 2015-03-25 | 2015-07-22 | 中国人民解放军空军油料研究所 | Catalyst for preparing antiwear agent of aviation fuel |
| CN104789298A (en) * | 2015-03-25 | 2015-07-22 | 中国人民解放军空军油料研究所 | Method for preparing antiwear agent of aviation fuel |
| CN104817521A (en) * | 2015-03-03 | 2015-08-05 | 中国林业科学研究院林产化学工业研究所 | Epoxy dimeric fatty acid methyl ester, preparation method and applications thereof |
| CN106220464A (en) * | 2016-07-05 | 2016-12-14 | 青岛科技大学 | A kind of method being catalyzed α pinene dimerization reaction |
| CN111153799A (en) * | 2020-01-20 | 2020-05-15 | 浙江本立科技股份有限公司 | Preparation method of methyl 3-methoxyacrylate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191035A (en) * | 2007-11-16 | 2008-06-04 | 青岛科技大学 | Brphinsted-Lewis acidic ionic liquid and application thereof in rosin polymerization reaction |
| CN101293829A (en) * | 2008-06-12 | 2008-10-29 | 江苏工业学院 | Method for preparing polydiallyl itaconate and dimer acid |
| CN101391956A (en) * | 2008-11-05 | 2009-03-25 | 江南大学 | Method for synthesizing methyl oleate and epoxy methyl oleate in ion liquid medium |
-
2009
- 2009-07-25 CN CN200910159634.0A patent/CN101613273B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191035A (en) * | 2007-11-16 | 2008-06-04 | 青岛科技大学 | Brphinsted-Lewis acidic ionic liquid and application thereof in rosin polymerization reaction |
| CN101293829A (en) * | 2008-06-12 | 2008-10-29 | 江苏工业学院 | Method for preparing polydiallyl itaconate and dimer acid |
| CN101391956A (en) * | 2008-11-05 | 2009-03-25 | 江南大学 | Method for synthesizing methyl oleate and epoxy methyl oleate in ion liquid medium |
Non-Patent Citations (3)
| Title |
|---|
| CARLOS W.LEE,: "Diels-Alder Reactions in Chloroaluminate Ionic Liquids:Acceleration and Selectivity Enhancement", 《TETRAHEDRON LETTERS》 * |
| T.FISCHER,ET AL.,: "Diels-Alder Reaction in Room-Temperature Ionic Liquids", 《TETRAHEDRON LETTERS》 * |
| TOM WELTON,: "Ionic liquids in catalysis", 《COORDINATION CHEMISTRY REVIEWS》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382015A (en) * | 2011-08-02 | 2012-03-21 | 常州大学 | Method for preparing sulfated methyl ester by ionic liquid catalysis method |
| CN102516128A (en) * | 2011-12-19 | 2012-06-27 | 河北工业大学 | Synthetic technology of diphenylmethane dicarbamate by adopting Bronsted-Lewis acidic ionic liquid catalysis |
| CN102516128B (en) * | 2011-12-19 | 2014-03-19 | 河北工业大学 | Synthetic technology of diphenylmethane dicarbamate by adopting Bronsted-Lewis acidic ionic liquid catalysis |
| CN102557928A (en) * | 2011-12-29 | 2012-07-11 | 北京国力源高分子科技研发中心 | Method for preparing dimeric acid methyl ester by using microwaves |
| CN103204836A (en) * | 2013-03-31 | 2013-07-17 | 青岛科技大学 | Method for preparing 5-hydroxymethyl furfural |
| CN103204836B (en) * | 2013-03-31 | 2017-10-10 | 青岛科技大学 | A kind of method for preparing 5 hydroxymethylfurfurals |
| CN104817521A (en) * | 2015-03-03 | 2015-08-05 | 中国林业科学研究院林产化学工业研究所 | Epoxy dimeric fatty acid methyl ester, preparation method and applications thereof |
| CN104785297A (en) * | 2015-03-25 | 2015-07-22 | 中国人民解放军空军油料研究所 | Catalyst for preparing antiwear agent of aviation fuel |
| CN104789298A (en) * | 2015-03-25 | 2015-07-22 | 中国人民解放军空军油料研究所 | Method for preparing antiwear agent of aviation fuel |
| CN104789298B (en) * | 2015-03-25 | 2017-10-17 | 中国人民解放军空军油料研究所 | A kind of method for preparing aviation fuel antiwear additive |
| CN106220464A (en) * | 2016-07-05 | 2016-12-14 | 青岛科技大学 | A kind of method being catalyzed α pinene dimerization reaction |
| CN111153799A (en) * | 2020-01-20 | 2020-05-15 | 浙江本立科技股份有限公司 | Preparation method of methyl 3-methoxyacrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101613273B (en) | 2014-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101613273B (en) | Method for preparing dimeric acid methyl ester | |
| CN101191035B (en) | Brphinsted-Lewis acidic ionic liquid and application thereof in rosin polymerization reaction | |
| Wei-Li et al. | Polymer grafted with asymmetrical dication ionic liquid as efficient and reusable catalysts for the synthesis of cyclic carbonates from CO2 and expoxides | |
| Liu et al. | Dimerization of fatty acid methyl ester using Brönsted–Lewis acidic ionic liquid as catalyst | |
| CN102603532B (en) | Method for preparing plasticizer terephthalate by alcoholysis of waste polyester PET | |
| CN102701955B (en) | Application of acidic ionic liquid in catalyzing and synthesizing diphenolic acid and/or diphenolic acid ester | |
| Liu et al. | Asymmetric transfer hydrogenation of ketones with a polyethylene glycol bound Ru catalyst in water | |
| CN108525703B (en) | Ionic liquid catalyst for preparing high-carbon-chain alkylbenzene and preparation method thereof | |
| CN101168493B (en) | Preparation method for fluorochlorobenzene | |
| CN112920218B (en) | Tert-butylphenyl phosphate and preparation method and application thereof | |
| CN104178092A (en) | High-temperature organic heat carrier and production technology thereof | |
| CN101955849B (en) | Biological lubricant prepared with ionic liquid as catalyst and preparation method | |
| CN103508881A (en) | Alkyl salicylic acid synthesis method | |
| CN103706404B (en) | For catalysis CO 2with magnetic composite microsphere of epoxide cycloaddition reaction and its preparation method and application | |
| KR101416706B1 (en) | Method for preparing glycidol | |
| CN100432041C (en) | Method for producing oxygen-containing compound | |
| CN102399134B (en) | Method for preparing cyclohexanol by cyclohexene hydration | |
| CN108117474B (en) | Method for preparing JP-10 aviation fuel from furfuryl alcohol | |
| CN105646171A (en) | 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone synthesis process | |
| CN102040608B (en) | Preparation method and application of 2-imine-1,10-phenanthroline ligand | |
| CN113493377B (en) | Continuous synthesis method of diphenyl ketone compound | |
| CN102964569A (en) | Method for producing terpene-phenolic resins | |
| IT201800004226A1 (en) | Improved process for the transformation of primary aliphatic alcohols into higher aliphatic alcohols | |
| CN105777537B (en) | A kind of alkylation of salicylic acid method | |
| CN107952479B (en) | Functionalized polyacid ionic liquid catalyst, preparation method and method for catalyzing direct esterification of cyclohexene by functionalized polyacid ionic liquid catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140416 Termination date: 20170725 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |