CN103588640B - A kind of preparation method of glycol ether dicarboxylic ester - Google Patents
A kind of preparation method of glycol ether dicarboxylic ester Download PDFInfo
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- CN103588640B CN103588640B CN201210290785.1A CN201210290785A CN103588640B CN 103588640 B CN103588640 B CN 103588640B CN 201210290785 A CN201210290785 A CN 201210290785A CN 103588640 B CN103588640 B CN 103588640B
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 150000002148 esters Chemical class 0.000 title abstract description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 90
- 238000000034 method Methods 0.000 claims abstract description 45
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 18
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 76
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 47
- 239000003054 catalyst Substances 0.000 claims description 34
- 238000007792 addition Methods 0.000 claims description 25
- 238000009835 boiling Methods 0.000 claims description 19
- 238000004821 distillation Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- -1 carboxylate ester Chemical class 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 21
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 14
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 14
- 239000012535 impurity Substances 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 10
- 239000004014 plasticizer Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- HJRDNARELSKHEF-CLFAGFIQSA-N 2-[2-[(z)-octadec-9-enoyl]oxyethoxy]ethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCOCCOC(=O)CCCCCCC\C=C/CCCCCCCC HJRDNARELSKHEF-CLFAGFIQSA-N 0.000 description 8
- YKDMBTQVKVEMSA-UHFFFAOYSA-N diethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOCCOC(=O)CCCCCCCCCCCCCCCCC YKDMBTQVKVEMSA-UHFFFAOYSA-N 0.000 description 8
- 229940111071 diethylene glycol distearate Drugs 0.000 description 8
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 8
- 238000004566 IR spectroscopy Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 7
- 238000004949 mass spectrometry Methods 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 238000009776 industrial production Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- HNBDRPTVWVGKBR-UHFFFAOYSA-N methyl pentanoate Chemical compound CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 description 5
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 4
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical compound CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 description 4
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 4
- 229940073769 methyl oleate Drugs 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 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 description 4
- WGNKWSUGROGRKR-UHFFFAOYSA-N 2-(2-butanoyloxyethoxy)ethyl butanoate Chemical compound CCCC(=O)OCCOCCOC(=O)CCC WGNKWSUGROGRKR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- XSTGQVSZAOQMPN-UHFFFAOYSA-N 2-(2-hexanoyloxyethoxy)ethyl hexanoate Chemical compound CCCCCC(=O)OCCOCCOC(=O)CCCCC XSTGQVSZAOQMPN-UHFFFAOYSA-N 0.000 description 2
- YMMVCTFOVNOGFQ-UHFFFAOYSA-N 2-(2-propanoyloxyethoxy)ethyl propanoate Chemical compound CCC(=O)OCCOCCOC(=O)CC YMMVCTFOVNOGFQ-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- ZQWPRMPSCMSAJU-UHFFFAOYSA-N methyl cyclohexanecarboxylate Chemical compound COC(=O)C1CCCCC1 ZQWPRMPSCMSAJU-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BKUSIKGSPSFQAC-RRKCRQDMSA-N 2'-deoxyinosine-5'-diphosphate Chemical compound O1[C@H](CO[P@@](O)(=O)OP(O)(O)=O)[C@@H](O)C[C@@H]1N1C(NC=NC2=O)=C2N=C1 BKUSIKGSPSFQAC-RRKCRQDMSA-N 0.000 description 1
- IVUAQTKKOWDNQO-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2-methylpropanoate Chemical compound CC(C)C(=O)OCCOCCO IVUAQTKKOWDNQO-UHFFFAOYSA-N 0.000 description 1
- CKQNDABUGIXFCL-UHFFFAOYSA-N 2-(2-octanoyloxyethoxy)ethyl octanoate Chemical compound CCCCCCCC(=O)OCCOCCOC(=O)CCCCCCC CKQNDABUGIXFCL-UHFFFAOYSA-N 0.000 description 1
- MNBUMRSEKNGNCN-UHFFFAOYSA-N 2-[2-(2-methylpropanoyloxy)ethoxy]ethyl 2-methylpropanoate Chemical compound CC(C)C(=O)OCCOCCOC(=O)C(C)C MNBUMRSEKNGNCN-UHFFFAOYSA-N 0.000 description 1
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 1
- 102100035474 DNA polymerase kappa Human genes 0.000 description 1
- 101710108091 DNA polymerase kappa Proteins 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229920006239 diacetate fiber Polymers 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the preparation method that a kind of structural formula is the glycol ether dicarboxylic ester of (I), wherein, structural formula is glycol ether and the carboxylicesters RCOOR of (II) under being included in the catalyzer existence containing Anhydrous potassium carbonate by described method
1react, generate and comprise the glycol ether dicarboxylic ester and corresponding alcohol HOR that structural formula is (I)
1product; Wherein, R is selected from the C of straight chain
2-C
17the C of aliphatic group, side chain
3-C
17alkyl and C
4-C
8one in cycloalkyl; R
1for methyl or ethyl.The inventive method is beneficial to environment protection; Product yield is high, and purity is good.
Description
Technical Field
The invention relates to a preparation method of an ester plasticizer, in particular to a preparation method of diethylene glycol dicarboxylate.
Background
The plasticizer is a plastic auxiliary agent used in the process of forming and processing plastics such as polyvinyl chloride, and can reduce the glass transition temperature of the polymer and increase the plasticity when added into a polymer system, so that the polymer is easy to process. The yield of the plasticizer accounts for about 60 percent of the total amount of the plastic additives, and the plasticizer is mainly used for polyvinyl chloride products, and the consumption accounts for 80 percent. The plasticizer is various, most of which are esters, wherein the yield of phthalate esters (including DOP, DBP, BBP, DINP, DIDP, DnOP and the like) accounts for about 85%. However, phthalate esters are environmentally affecting hormones, the preparation and use of phthalate plasticizers will be further limited and the call for the use of alternative non-toxic plasticizers will be higher and higher.
CN1863858A discloses a non-phthalate plasticizer and a preparation method thereof, wherein the plasticizer component contains diethylene glycol dicarboxylate (commonly known as diethylene glycol dicarboxylate), and the preparation method of the plasticizer takes tetraisopropyl titanate as a catalyst to catalyze the esterification reaction of diethylene glycol (i.e. diethylene glycol) and carboxylic acid to generate diethylene glycol dicarboxylate. Different types and different contents of diethylene glycol dicarboxylate components can be obtained with different types and different proportions of acid. The method needs the procedures of neutralization, water washing, dehydration and adsorbent addition filtration after the esterification reaction is finished, which brings the problems of sewage and waste residue treatment to the production process.
CN1126219A discloses a preparation method of diethylene glycol dipropionate and application thereof as a plasticizer of diacetate fiber tows. The preparation method uses sulfuric acid or p-toluenesulfonic acid as a catalyst to catalyze diethylene glycol and propionic acid to carry out esterification reaction to generate diethylene glycol dipropionate. The method also needs procedures such as neutralization after the esterification reaction and the like, and needs to treat sewage generated in the production process.
The Chinese journal application chemical (2007, V36 (3), P277-278, 282) reports the preparation method of the medicine sustained-release agent diethylene glycol distearate. The method selects a corrosive phosphoric acid and sulfuric acid compounded catalyst, the reaction time is 4 hours, the reaction temperature is 140 ℃, and the yield of the product diethylene glycol distearate is 92%. The product obtained by the method is recrystallized by ethanol, and impurities such as catalyst and the like are removed.
Disclosure of Invention
The object of the present invention is to overcome the disadvantages of the prior art and to provide a novel process for the preparation of diethylene glycol dicarboxylate.
In order to achieve the above object, the present invention provides a process for preparing diethylene glycol dicarboxylate of formula (I), wherein the process comprises reacting diethylene glycol of formula (II) with a carboxylate RCOOR in the presence of a catalyst comprising anhydrous potassium carbonate1Reacting to form diethylene glycol dicarboxylate of formula (I) and the corresponding alcohol HOR1The product of (a);
wherein,
r is selected from linear C2-C17Aliphatic hydrocarbon radical, branched C3-C17Alkyl and C4-C8One of cycloalkyl groups;
R1is methyl or ethyl.
The invention provides a process for the preparation of diethylene glycol dicarboxylate esters using carboxylate RCOOR1As an acylating agent in place of a carboxylic acid; the catalyst containing anhydrous potassium carbonate is used for replacing corrosive sulfuric acid or replacing a tetraisopropyl titanate catalyst which influences the product quality and the like, so that the method is beneficial to environmental protection or safe production and is suitable for large-scale industrial production; the product is easy to separate from the reactant and the catalyst, the yield is high, the purity is good, and the procedures of neutralization, water washing, dehydration or filtering by adding an adsorbent and the like are not needed. The method of the invention can be widely applied to industrial production.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a process for the preparation of diethylene glycol dicarboxylate of formula (I), wherein the process comprises reacting diethylene glycol of formula (II) with a carboxylate RCOOR in the presence of a catalyst comprising anhydrous potassium carbonate1Reacting to form diethylene glycol dicarboxylate of formula (I) and the corresponding alcohol HOR1The product of (a);
wherein R is selected from linear C2-C17Aliphatic hydrocarbon radical, branched C3-C17Alkyl and C4-C8One of cycloalkyl groups;
R1is methyl or ethyl.
According to the invention, diethylene glycol of the formula (II) is reacted with a carboxylic acid ester RCOOR in the presence of a catalyst containing anhydrous potassium carbonate1Reacting to form diethylene glycol dicarboxylate of formula (I) and the corresponding alcohol HOR1The product of (a); wherein R is1The invention can be realized by methyl or ethyl, which is beneficial to environmental protection, and the product is easy to separate from reactants and catalyst, and has high yield and good purity. Preferably, however, the transesterification reaction comprises carrying out the reaction under distillation or rectification conditions with simultaneous removal of the alcohol HOR formed1(ii) a Further preferably, the reaction is carried out for 5 to 7.5 hoursAdding alcohol HOR into the reaction solution1By removing alcohol HOR formed by the reaction by azeotropic distillation or azeotropic distillation1. This preferred embodiment further improves the yield and purity of the product of formula (I).
In the present invention, in order to allow the above-mentioned preferred embodiment to proceed smoothly and continuously, the reaction was started using a "dispenser" equipped with a condenser at the upper end thereof as a distillation apparatus, which means a Dean and Stark apparatus with a stopcock at the lowertend at the bottom thereof.
After 5 to 7.5 hours of the reaction, the entrainer is preferably added to the reaction mixture in 5 to 7 portions, the time interval between two consecutive additions is 1.1 to 2 hours, and the amount of the entrainer added per one portion is 60 to 240mL relative to 1 mole of diethylene glycol at the start of the reaction. The increase of the addition amount of the entrainer each time is beneficial to improving the yield and the purity of the product with the structural formula (I), but simultaneously increases the energy consumption of the reaction.
Another way of adding the entrainer is to start the reaction by using a distillation apparatus or a rectification apparatus, after 5 to 7.5 hours of the transesterification reaction under distillation or rectification conditions, continuously add the entrainer to the reaction solution under distillation or rectification conditions at a rate of 60 to 240 mL/hour and for a time of 5 to 7 hours relative to 1 mole of diethylene glycol at the start of the reaction. Increasing the flow rate of the entrainer is beneficial to improving the yield and the purity of the product with the structural formula (I), but simultaneously increases the energy consumption of the reaction.
It should be understood by those skilled in the art that, when the temperature of the reaction solution is controlled to be not lower than the boiling point of the entrainer after the entrainer is added, the temperature of the reaction solution may be cooled to be lower than the boiling point of the entrainer without cooling the entrainer when the entrainer is added in portions, the temperature of the reaction solution is preferably cooled to be lower than the boiling point of the entrainer in a laboratory, and the time required for cooling is generally not more than half an hour, preferably 0.1 to 0.5 hour; in the case of continuous flow, the reaction temperature should be controlled between the boiling point of the azeotropic agent and the boiling point of the azeotrope formed by the azeotropic agent and the alcohol produced by the reaction, and the flow rate can be adjusted according to the reaction rate, the kind and amount of the azeotropic agent. The mode of adding the continuous flow of the entrainer to the reaction liquid under the distillation or rectification condition is particularly suitable for large-scale production.
In the invention, the entrainer is preferably a solvent with a boiling point of 79-145 ℃, is more preferably one or more of aromatic hydrocarbon with a boiling point of 79-145 ℃ and carboxylic ester with a boiling point of 79-145 ℃, and the aromatic hydrocarbon is more preferably one or more of xylene, toluene and benzene; further preferred is toluene. When the carboxylic acid ester of the present invention RCOOR1The entrainer can also be selected from the carboxylic acid esters RCOOR used as starting materials for the reaction when the boiling point is in the range of 79-145 ℃ at a pressure of 760mm Hg1I.e. the carboxylic acid ester RCOOR1The entrainer and the carboxylic ester RCOOR of the starting material for the reaction have a boiling point in the range from 79 to 145 ℃ at a pressure of 760mm Hg1Are the same substance; preferably, the carboxylic acid ester RCOOR1The entrainer and the carboxylic ester RCOOR of the starting material for the reaction have a boiling point in the range from 90 to 128 ℃ at a pressure of 760mm Hg1Are the same substance.
In the present invention, the carboxylic acid ester RCOOR1Boiling point of (2) is higher than that of alcohol HOR1Of formula (II) with a carboxylic acid ester RCOOR1The transesterification reaction of (a) may be carried out under distillation or rectification conditions to remove the alcohol HOR formed during the reaction1。
In the present invention, the amount of the reactant is preferably, carboxylic ester RCOOR1Is at least 2 times the moles of diethylene glycol of formula (II); more preferably, diethylene glycol of formula (II) and a carboxylic acid ester RCOOR1The molar ratio of (A) to (B) is 1: 2-10; more preferably, diethylene glycol of the formula (II) and a carboxylic acid ester RCOOR1The molar ratio of (A) to (B) is 1: 2-5. It will be understood by those skilled in the art that as the molar amount of carboxylic ester is increased, the reaction rate is increased and the yield is increased, but the isolation of the product is also affected. When the carboxylic acid ester of the present invention RCOOR1Selected from the group consisting of mercury at a pressure of 760mm HgCarboxylic acid esters RCOOR having a boiling point in the range from 79 ℃ to 145 ℃1When the entrainer is selected from the carboxylic ester RCOOR1Then carboxylic acid ester RCOOR1In an amount other than diethylene glycol and a carboxylic acid ester RCOOR according to formula (II)1In addition to the molar ratio of 1:2-10, the amount and manner of addition of the entrainer as described above may be used.
The catalyst containing anhydrous potassium carbonate is not particularly limited in kind, and the object of the invention can be achieved as long as anhydrous potassium carbonate is contained in the catalyst. The catalyst can be anhydrous potassium carbonate per se, can also be a supported catalyst formed by loading anhydrous potassium carbonate on an inorganic heat-resistant metal oxide carrier, can also be a mixture of anhydrous potassium carbonate and an inorganic heat-resistant metal oxide, or can be used in two or more forms. In the above case, the catalytically active component is anhydrous potassium carbonate. When the catalyst is a supported catalyst formed by loading anhydrous potassium carbonate on an inorganic heat-resistant metal oxide carrier or a mixture of anhydrous potassium carbonate and the inorganic heat-resistant metal oxide carrier, the content of the anhydrous potassium carbonate is 5-95% by weight, preferably 10-30% by weight, based on the total weight of the catalyst. In the present invention, the inorganic refractory metal oxide support may be alumina, molecular sieve or zirconia. Whichever form of catalyst is used, it is preferred that the molar ratio of diethylene glycol of formula (II) to anhydrous potassium carbonate contained in the catalyst is from 1:0.001 to 0.5; more preferably, the molar ratio of the diethylene glycol of formula (II) to anhydrous potassium carbonate contained in the catalyst is 1:0.01 to 0.2. It will be appreciated by those skilled in the art that as the amount of catalyst is increased, the reaction rate increases, but product separation is also affected.
The preparation of the supported catalyst formed by loading the potassium carbonate on the alumina can adopt the conventional method in the field, and preferably, the preparation method comprises the following steps:
(1) roasting the powdery alumina carrier at the roasting temperature of 550-600 ℃ for 1-5 hours;
(2) soaking the powdery alumina carrier roasted in the step (1) in a potassium carbonate aqueous solution;
(3) and (3) removing water in the mixture obtained in the step (2), and then roasting at the roasting temperature of 550-600 ℃ for 1-5 hours.
In the present invention, the temperature of the reaction solution is not less than the HOR of the alcohol to be produced1The boiling point of (c). The reaction temperature is 65-170 ℃; when an azeotropic agent is used, the temperature of the reaction solution is not less than the boiling point of the azeotropic agent. In practical operation, the reaction temperature is changed along with the removal of the low-boiling by-product alcohol HOR generated in the reaction process1(e.g., bp65 ℃ boiling point of methanol). In laboratory, a conventional glass flask is used as a reactor, a water bath or an oil bath is used as a heating source, when the temperature of the water bath or the oil bath is controlled to be 80-160 ℃, and when the reactant ester RCOOR is preferred1R of (A) to (B)1When the methyl group is used, and the entrainer is preferably toluene, the reaction temperature can be controlled to be in the range of 65 to 120 ℃. In industrial production, the heat source required to control the reaction temperature may be provided by various methods known in the art, for example, 100 ℃ may be provided by heating with a steam or oil bath, and the temperature range of 100 ℃ and 160 ℃ may be provided by heating with a pressurized steam or oil bath. In the present invention, the reaction may be heated by a conventional heating method, for example, a heating method of raising the temperature in stages may be used.
It will be appreciated by those skilled in the art that, in order to obtain a diethylene glycol dicarboxylate of formula (I) in a higher purity, the process of the present invention preferably further comprises, after termination of the reaction, separating the diethylene glycol dicarboxylate of formula (I) from the mixture obtained after the reaction. A process for separating diethylene glycol dicarboxylate of the formula (I) from the mixture obtained after the reaction, which comprises reacting the alcohol HOR in the mixture obtained1Catalyst containing anhydrous potassium carbonate, unreacted carboxylic ester RCOOR1And diethylene glycol of the formula (II), and a small amount of the intermediate 2- (2-acyloxyethyl group)Etc.) ethanol and impurities, and removing them from the reaction mixture, and there is no particular need for the method of removal, and various methods conceivable to those skilled in the art can be employed1Removing catalyst containing anhydrous potassium carbonate from the mixture obtained by the reaction by filtration, centrifugal separation or extraction, and distilling under reduced pressure or rectifying under reduced pressure to obtain unreacted carboxylic ester RCOOR1Diethylene glycol of the formula (II) and a small amount of intermediate 2- (2-acyloxyethyl) ethanol and impurities are removed from the reaction mixture.
In the present invention, R is preferably C2-C8One of aliphatic hydrocarbon groups; r1Preferably methyl.
The following examples further illustrate the invention but are not intended to limit the invention thereto. Examples the "dispenser" refers to a Dean and Starkappaatus with a stopcock at the lower end of a Dean and Starkappaatus Starpcock at the lower end of a Dean and Starkappaatus.
Example 1
This example illustrates the preparation of diethylene glycol di-n-caprylate according to the present invention.
A150 mL round bottom flask equipped with a condenser, a liquid separator and a stirrer was charged with 15.92g (0.15 mol) of diethylene glycol, 94.94g (0.6 mol) of methyl n-octanoate and 4.15g (0.03 mol) of anhydrous potassium carbonate, an oil bath contacting the round bottom flask was heated to 160 ℃ and reacted at 0.1MPa while evaporating the resulting alcohol to the liquid separator by distillation and removing it, after 6 hours of reaction, toluene was added to the round bottom flask, 6 times in total were added in the round bottom flask, the time interval between two consecutive additions was 2 hours, 12mL each was added, after 1.5 hours of reaction after each addition of toluene and while distilling toluene and azeotrope out of the round bottom flask, and the next toluene was added after the reaction liquid was cooled for about 30 minutes. After the reaction, the mixture in the round-bottom flask was cooled and filtered to remove anhydrous potassium carbonate, and the filtrate was distilled under reduced pressure at 380Pa at 65 ℃ to remove unreacted methyl n-octanoate and other impurities, to give 53.60g of diethylene glycol di-n-octanoate in a yield of 99.7%, which was analyzed by gas chromatography-mass spectrometry (GC-MS) to have a purity of 98.4%. The results are shown in Table 1. Mass spectrometry, infrared spectrometry and hydrogen nuclear magnetic resonance spectroscopy were performed, and the results are as follows.
MS（EI，m/z）：232（M-126）+，201（M-157）+，190，171，148，141，127，113，98，86，57，55，43，41，29，28。
IR（cm-1）：2929，2857，1739，1458，1379，1252，1170，1139，1106，1050，963，864，725。
1H NMR（CDCl3/TMS，300MHZ）（ppm）:0.857-0.902（t，6H，2CH3（CH2）5CH2COO），1.280-1.305（m，16H，2CH3（CH2）4CH2CH2COO），1.602-1.651（m，4H，2CH3（CH2）4CH2CH2COO），2.306-2.357（t，4H，2CH3（CH2）5CH2COO），3.678-3.710（m，4H，2CH2CH2OCOCH2（CH2）5CH3），4.214-4.246（m，4H，2CH2CH2OCOCH2（CH2）5CH3）。
Example 2
This example illustrates the preparation of diethylene glycol di-n-hexanoate according to the present invention.
A150 mL round bottom flask with a condenser, a liquid separator and a stirrer was charged with 15.92g (0.15 mol) of diethylene glycol, 78.11g (0.6 mol) of methyl hexanoate and 4.15g (0.03 mol) of anhydrous potassium carbonate, an oil bath contacting the round bottom flask was heated to 150 ℃ and reacted at 0.1MPa while evaporating the resulting alcohol to the liquid separator by a distillation method and removing it, after 6 hours of reaction, toluene was added to the round bottom flask, 6 times were added in total, the time interval between two consecutive additions was 2 hours, 12mL each time was added, after 1.5 hours of reaction after each addition of toluene and while distilling toluene and azeotrope out of the round bottom flask, and after about 30 minutes of cooling the reaction solution, the next toluene was added. After the reaction is finished, the mixture in the round-bottom flask is cooled, anhydrous potassium carbonate is removed by filtration, and unreacted methyl hexanoate and other impurities are removed by vacuum distillation of the filtrate under 140Pa by using a 120 ℃ oil bath to obtain 44.83g of diethylene glycol di-n-hexanoate, the yield is 99%, and the purity is 100% by analyzing through gas chromatography-mass spectrometry (GC-MS). The results are shown in Table 1. Mass spectrometry, infrared spectrometry and hydrogen nuclear magnetic resonance spectroscopy were performed, and the results are as follows.
MS（EI，m/z）：173（M-129）+，144，143（M-159）+，117，113，101，99，88，87，86，72，71，69，56，55，43，41，39，29。
IR（cm-1）：2957，2933，2873，1739，1457，1380，1247，1174，1139，1100，1047，965，868，734。
1H NMR（CDCl3/TMS，300MHZ）（ppm）：0.874-0.919（t，6H，2CH3（CH2）3CH2COO），1.284-1.334（m，8H，2CH3（CH2）2CH2CH2COO），1.609-1.659（m，4H，2CH3（CH2）2CH2CH2COO），2.307-2.357（t，4H，2CH3（CH2）3CH2COO），3.680-3.712（m，4H，2CH2CH2OCOCH2（CH2）3CH3），4.215-4.247（m，4H，2CH2CH2OCOCH2（CH2）3CH3）。
Example 3
This example illustrates the preparation of diethylene glycol di-n-valerate according to the present invention.
A100 mL round-bottom flask equipped with a condenser, a liquid separator and a stirrer was charged with 15.92g (0.15 mol) of diethylene glycol, 69.7g (0.6 mol) of methyl n-valerate and 4.15g (0.03 mol) of anhydrous potassium carbonate, an oil bath in contact with the round-bottom flask was heated to 125 ℃ and reacted under 0.1MPa, the alcohol formed was distilled off to the liquid separator and removed at the same time as the reaction, after 6 hours of reaction, the oil bath was heated to 165 ℃ and methyl n-valerate was added to the round-bottom flask, the total of 6 times of addition were carried out, the time interval between two consecutive additions was 2 hours, 12mL each time of addition was carried out, after 1.9 hours of reaction was carried out after each addition of methyl n-valerate and the azeotrope was distilled out of the round-bottom flask, and the next addition of methyl n-valerate was carried out after the reaction liquid was cooled for about 6 minutes. After the reaction was complete, the flask was cooled. Anhydrous potassium carbonate is removed by filtration, and the filtrate is subjected to reduced pressure distillation by using a 120 ℃ oil bath to remove methyl n-valerate and other impurities, so that 30.58g of diethylene glycol di-n-valerate is obtained, the yield is 98%, and the purity is 99% by analysis of gas chromatography-mass spectrometry (GC-MS). The results are shown in Table 1. Mass spectrometry, infrared spectrometry and hydrogen nuclear magnetic resonance spectroscopy were performed, and the results are as follows.
MS（EI，m/z）：159（M-115）+，130，129（M-145）+，113，100，99，86，85，73，70，58，57，55，45，41，29。
IR（cm-1）：2960，2874，1736，1456，1381，1342，1257，1178，1139，1110，1044，958，859，755，734。
1H NMR（CDCl3/TMS，300MHZ）（ppm）:0.892-0.941（t，6H，2CH3（CH2）2CH2COO），1.292-1.415（m，4H，2CH3CH2CH2CH2COO），1.568-1.668（m，4H，2CH3CH2CH2CH2COO），2.316-2.366（t，4H，2CH3（CH2）2CH2COO），3.680-3.712（m，4H，2CH2CH2OCOCH2（CH2）2CH3），4.216-4.248（m，4H，2CH2CH2OCOCH2（CH2）2CH3）。
Example 4
This example illustrates the preparation of diethylene glycol dioleate using anhydrous potassium carbonate supported on a carrier alumina as a catalyst according to the present invention.
Preparation of anhydrous potassium carbonate supported alumina catalyst
Neutral alumina (alpha-alumina, 100-200 mesh) was calcined at 550 ℃ for 4 hours for use. The anhydrous potassium carbonate is dried in a 105 ℃ forced air drying oven for 3 hours, 6g of the dried anhydrous potassium carbonate is taken to be dissolved in 40mL of deionized water, 24g of neutral alumina is added after full dissolution, and the mixture is kept stand for 24 hours after full stirring. The mixture was placed in an evaporating dish to evaporate the water and then dried in a forced air drying cabinet for 24 hours at 105 ℃. The obtained solid was calcined at 600 ℃ for 5 hours in a muffle furnace to obtain 28.89g of a catalyst powder in which anhydrous potassium carbonate was supported on alumina.
Preparation of diethylene glycol dioleate
A150 mL round bottom flask equipped with a condenser, a liquid separator and a stirrer was charged with 10.61g (0.1 mol) of diethylene glycol, 59.3g (0.2 mol) of methyl oleate, and 2.76g (about 0.004 mol) of the anhydrous potassium carbonate-containing catalyst powder obtained above, the oil bath contacting the round bottom flask was heated to 155 ℃ and reacted at 0.1MPa, and the alcohol formed while the reaction was carried out was distilled off to the liquid separator and removed by a distillation method, and reacted for 5 hours. After cooling for about 6 minutes, xylene was added to the round bottom flask for a total of 6 additions, back and forth, with the interval between two consecutive additions being 1.6 hours, 12mL each, and after each addition, the reaction was carried out at 170 ℃ for 1.5 hours while distilling off the xylene and azeotrope from the round bottom flask and adding the next xylene after the reaction had cooled for about 6 minutes. After completion of the reaction, the mixture in the round-bottomed flask was cooled and filtered to remove anhydrous potassium carbonate, the filtered solid was washed with xylene, and the filtrate was first subjected to rotary evaporation under reduced pressure at 80 ℃ to remove xylene, and then subjected to distillation under reduced pressure at 260Pa to remove impurities, whereby 62.15g of diethylene glycol dioleate was obtained in a yield of 98%. Since diethylene glycol dioleate has a large molecular weight and a small volatility, it is difficult to analyze the purity by gas chromatography-mass spectrometry (GC-MS). The results are shown in Table 1. The infrared spectrum and the nuclear magnetic resonance hydrogen spectrum analysis were carried out, and the results are as follows.
IR（cm-1）：3009，2925，2854，1740，1465，1378，1245，1175，1137，723。。
1H NMR（CDCl3/TMS，300MHZ）（ppm）：0.857-0.902（m，6H，2CH3（CH2）6CH2CH=CHCH2（CH2）4CH2CH2COO），1.256-1.311（m，40H，2CH3（CH2）6CH2CH=CHCH2（CH2）4CH2CH2COO），1.601-1.647（m，4H，2CH3（CH2）6CH2CH=CHCH2（CH2）4CH2CH2COO），2.000-2.059（m，8H，2CH3（CH2）6CH2CH=CHCH2（CH2）4CH2CH2COO），2.304-2.354（t，J=7.5Hz,4H，2CH3（CH2）6CH2CH=CHCH2（CH2）4CH2CH2COO），3.664-3.694（m，4H，2CH2CH2OCO（CH2）7CH=CH（CH2）7CH3），4.211-4.244（m，4H，2CH2CH2OCO（CH2）7CH=CH（CH2）7CH3），5.317-5.379（m，4H，2CH2CH2OCO（CH2）7CH=CH（CH2）7CH3）。
By comparing the NMR spectra of the product diethylene glycol dioleate and the reactant methyl oleate: (1HNMR), and the infrared spectrogram of the product diethylene glycol dioleate does not see the stretching vibration characteristic absorption band of OH, thereby confirming that the obtained product diethylene glycol dioleate is consistent with the structure.
Example 5
This example illustrates the preparation of diethylene glycol di-n-propionate according to the present invention.
A100 mL round bottom flask equipped with a condenser, a liquid separator and a stirrer was charged with 15.92g (0.15 mol) of diethylene glycol, 52.87g (0.6 mol) of methyl n-propionate and 4.15g (0.03 mol) of anhydrous potassium carbonate, an oil bath in contact with the round bottom flask was heated to 80 ℃ to react under 0.1MPa, and the formed alcohol was distilled off to the liquid separator and removed by distillation at the same time as the reaction, and reacted for 2.5 hours. To the round bottom flask was added 7g of methyl propionate and the reaction was continued for 5 hours at 75 ℃ in an oil bath. Heating the oil bath to 90 ℃, reacting for 1.4 hours at the temperature, cooling for about 6 minutes, adding methyl n-propionate into the round bottom flask, adding the methyl n-propionate into the round bottom flask for 6 times in total, wherein the time interval between two adjacent times of adding is 1.5 hours, adding 12mL of the methyl n-propionate into the round bottom flask each time, reacting for 1.4 hours after adding the methyl n-propionate and the azeotrope out of the round bottom flask, and adding the next methyl n-propionate after cooling the reaction liquid for about 6 minutes. After the reaction, the mixture in the round-bottomed flask was cooled and filtered to remove anhydrous potassium carbonate, and the filtrate was subjected to vacuum distillation to remove unreacted methyl n-propionate and other impurities to obtain 31.23g of diethylene glycol di-n-propionate, which was analyzed by gas chromatography-mass spectrometry (GC-MS) and had a purity of 97% (3% methyl n-propionate contained in gas chromatography). Mass spectrometry, infrared spectrometry and hydrogen nuclear magnetic resonance spectroscopy were performed, and the results are as follows.
MS（EI，m/z）：131（M-87）+，102，101（M-117）+，99，87，75，70，58，57，55，45，43，42，29，27。
IR（cm-1）：2982，2946，2884，1739，1463，1380，1345，1276，1190，1137，1085，1040，997，947，864，808。
1H NMR（CDCl3/TMS，300MHZ）（ppm）：1.123-1.174（t，J=7.5Hz，6H，2CH3CH2COO），2.326-2.401（q，J=7.5Hz，4H，2CH3CH2COO），3.674-3.717（m，4H，2CH2CH2OCOCH2CH3），4.221-4.253（m，4H，2CH2CH2OCOCH2CH3）。
30.02g of 97% pure diethylene glycol di-n-propionate was taken, methyl n-propionate was distilled off under reduced pressure at 260Pa, and the purity was 29.05g of 99.6% diethylene glycol di-n-propionate, yield = (29.05/30.02) × (31.23/32.74) × 100% =92% by gas chromatography-mass spectrometry (GC-MS) analysis. The results are shown in Table 1.
Example 6
This example illustrates the preparation of diethylene glycol diisobutyrate according to the present invention.
A150 mL round bottom flask equipped with a condenser, a liquid separator and a stirrer was charged with 15.92g (0.15 mol) of diethylene glycol, 91.92g (0.9 mol) of methyl isobutyrate and 6.22g (0.045 mol) of anhydrous potassium carbonate, an oil bath in contact with the round bottom flask was heated to 90 ℃ to react at 0.1MPa, the resulting alcohol was distilled off to the liquid separator and removed by distillation at the same time as the reaction, after 6 hours of reaction, methyl isobutyrate was added to the round bottom flask, a total of 6 times were added in the round bottom flask, the time interval between two consecutive additions was 1.5 hours, 27mL each time was added, after each addition of methyl isobutyrate, the reaction was carried out at 105 ℃ for 1.4 hours while distilling methyl isobutyrate and an azeotrope out of the round bottom flask, and after the reaction liquid was cooled for about 6 minutes, the next addition of methyl isobutyrate was added. After completion of the reaction, the mixture in the round-bottomed flask was cooled and filtered to remove anhydrous potassium carbonate, and the filtrate was subjected to distillation under reduced pressure at 360Pa at 80 ℃ in an oil bath to remove unreacted methyl isobutyrate and other impurities to obtain 30.79g of diethylene glycol isobutyrate in a yield of 83%, which was analyzed by gas chromatography-mass spectrometry (GC-MS) and was 93% pure. The results are shown in Table 1. Mass spectrometry, infrared spectrometry and hydrogen nuclear magnetic resonance spectroscopy were performed, and the results are as follows.
MS（EI,m/z）：145（M-101）+，116，115，99，89，86，72，71，55，44，43，41，29，28，27，26。
IR（cm-1）：2975，2878，1736，1471，1389，1343，1259，1194，1162，1136，1082，955，870，754，518。
1H NMR（CDCl3/TMS，300MHZ）（ppm）：1.164-1.187（d，J=6.9Hz，12H，2（CH3）2CHCOO），2.533-2.626（m，2H，2（CH3）2CHCOO），3.682-3.714（m，4H，2CH2CH2OCOCH（CH3）2），4.211-4.244（m，4H，2CH2CH2OCOCH（CH3））。
Example 7
This example illustrates the preparation of diethylene glycol dicyclohexylformate according to the present invention.
A150 mL round bottom flask equipped with a condenser, a liquid separator and a stirrer was charged with 10.61g (0.10 mol) of diethylene glycol, 56.88g (0.4 mol) of methyl cyclohexylformate and 2.76g (0.02 mol) of anhydrous potassium carbonate, an oil bath contacting the round bottom flask was heated to 155 ℃ and reacted at 0.1MPa while evaporating the resulting alcohol to the liquid separator by distillation and removing it, after 6 hours of reaction, toluene was added to the round bottom flask, the total of 7 times of addition were carried out, the time interval between two consecutive additions was 1.5 hours, 6mL of each addition was added, 1.4 hours of reaction was carried out after each addition of toluene while distilling off the toluene and azeotrope, and the next round bottom toluene was added after the reaction liquid was cooled for about 6 minutes. After the reaction, the mixture in the round-bottom flask was cooled and filtered to remove anhydrous potassium carbonate, and the filtrate was subjected to distillation under reduced pressure at 48 ℃ under 350Pa to remove unreacted methyl cyclohexylformate and other impurities, to give 32.04g of diethylene glycol dicyclohexylformate, yield 98%, and purity 100% by gas chromatography-mass spectrometry (GC-MS). The results are shown in Table 1. Mass spectrometry, infrared spectrometry and hydrogen nuclear magnetic resonance spectroscopy were performed, and the results are as follows.
MS（EI,m/z）：185（M-141）+，156，155，125，112，111，99，87，84，83，81，73，67，55，53，41，39，31，28，27。
IR（cm-1）:2933，2856，1736，1452，1382，1353，1312，1275，1248，1171，1132，1077，1045，956，896，864，753，509。
1H NMR（CDCl3/TMS，300MHZ）（ppm）：1.150-1.933（m，20H，2（CH2）5CHCOO），2.280-2.378（m，2H，2（CH2）5CHCOO），3.667-3.699（m，4H，2CH2CH2OCOCH（CH2）5），4.200-4.232（m，4H，2CH2CH2OCOCH（CH2）5）。
Example 8
This example illustrates the preparation of diethylene glycol di-n-butyrate according to the present invention.
Diethylene glycol di-n-butyrate was prepared according to the procedure of example 5, except that 52.87g (0.6 mol) of methyl n-propionate was replaced with 69.69g (0.6 mol) of ethyl n-butyrate, and after 6 hours of reaction at 115 ℃ in an oil bath, the oil bath was heated to 140 ℃ and 15mL of ethyl n-butyrate as an entrainer was added thereto a total of 5 times, and finally ethyl n-butyrate and other impurities were distilled off under reduced pressure at 260Pa to give 34.7g of diethylene glycol dibutyrate in a yield of 94%. 99.9% by gas chromatography-mass spectrometry (GC-MS). The results are shown in Table 1. Mass spectrometry, infrared spectrometry and hydrogen nuclear magnetic resonance spectroscopy were performed, and the results are as follows.
MS（EI,m/z）：145（M-101）+，116，115，100，99，86，72，71，55，45，43，41，28，27。
IR（cm-1）：2966，2877，1737，1458，1382，1256，1182，1138，1094，1052，963，863，751。
1H NMR（CDCl3/TMS，300MHZ）（ppm）：0.929-0.978（t，J=7.5Hz，6H，2CH3CH2CH2COO），1.601-1.752（m，4H，2CH3CH2CH2COO）2.294-2.344（t，J=7.5Hz，4H，2CH3CH2CH2COO），3.680-3.712（m，4H，2CH2CH2OCOCH2CH2CH3），4.218-4.250（m，4H，2CH2CH2OCOCH2CH2CH3）。
Example 9
This example illustrates the preparation of diethylene glycol distearate using anhydrous potassium carbonate supported on a carrier alumina as a catalyst according to the invention.
Diethylene glycol distearate was prepared according to the procedure of example 4 except that 5.31g (0.05 mol) of diethylene glycol was used instead of 10.61g (0.1 mol) of diethylene glycol, 29.85g (0.1 mol) of methyl stearate was used instead of 59.3g (0.2 mol) of methyl oleate, 1.38g (about 0.002 mol) of the catalyst powder containing anhydrous potassium carbonate prepared by the procedure of (1) in example 4 was used instead of 2.76g (about 0.004 mol) of the catalyst powder containing anhydrous potassium carbonate, xylene was added after 6 hours of the reaction instead of xylene after 5 hours of the reaction, and finally impurities were distilled off under reduced pressure at 260Pa to give 29.37g of diethylene glycol distearate in 92% yield. Since diethylene glycol distearate has a large molecular weight and a small volatility, it is difficult to analyze the purity by gas chromatography-mass spectrometry (GC-MS). The results are shown in Table 1. The infrared spectrum and the nuclear magnetic resonance hydrogen spectrum analysis were carried out, and the results are as follows.
IR（cm-1）：2955，2916，2850，1730，1473，1426，1398，1235，1215，1196，1138，1101，718。
1H NMR（CDCl3/TMS，300MHZ）（ppm）：0.857-0.902（m，6H，2CH3（CH2）14CH2CH2COO），1.256-1.311（m，56H，2CH3（CH2）14CH2CH2COO），1.569-1.646（m，4H，2CH3（CH2）14CH2CH2COO），2.302-2.353（t，J=7.5Hz，4H，2CH3（CH2）14CH2CH2COO），3.622-3.723（m，4H，2CH2CH2OCO（CH2）16CH3），4.212-4.244（m，4H，2CH2CH2OCO（CH2）16CH3）。
By comparing the NMR spectra of the product diethylene glycol dioleate and the reactant methyl oleate: (1HNMR), and the infrared spectrum of the product diethylene glycol distearate does not see the stretching vibration characteristic absorption band of OH, confirming that the obtained product diethylene glycol distearate is consistent with the structure.
TABLE 1
Injecting: calculated as a percentage of actual to theoretical yield
As can be seen from Table 1, examples 1 to 3 and examples 5, 7 and 8, diethylene glycol dicarboxylate obtained by the process of the present invention has high yield and good purity.
As can be seen from examples 3, 6 and 8, carboxylic esters having a boiling point in the range of 90 to 128 ℃ at 760mm Hg can themselves be used as entrainers in the reaction.
As is clear from comparison between example 6 and example 8, methyl isobutyrate containing a substituent at the α -position of a carboxylic ester is superior to ethyl n-butyrate, which is a linear carboxylic ester, in the yield and purity of the ester interchange reaction of the carboxylic ester having no steric hindrance at the α -position.
In conclusion, the preparation method of diethylene glycol dicarboxylate provided by the invention is beneficial to environmental protection and suitable for large-scale industrial production; the product is easy to separate from the reactant and the catalyst, and has high yield and good purity. The method is safe and environment-friendly, and can be widely applied to industrial production.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (13)
1. A process for the preparation of diethylene glycol dicarboxylate of formula (I), characterized in that it comprises reacting diethylene glycol of formula (II) with a carboxylate RCOOR in the presence of anhydrous potassium carbonate as catalyst1Reacting to form diethylene glycol dicarboxylate of formula (I) and the corresponding alcohol HOR1The product of (a);
wherein,
r is selected from linear C2-C17Aliphatic hydrocarbon radical, branched C3-C17Alkyl and C4-C8One of cycloalkyl groups;
R1is methyl or ethyl.
2. The method of claim 1, wherein R is selected from C2-C8One kind of aliphatic hydrocarbon group.
3. The process according to claim 1, wherein the reaction is carried out under distillation or rectification conditions to remove alcohol HOR formed during the reaction1。
4. The process according to claim 3, wherein the alcohol HOR is added to the reaction solution after the reaction for 5 to 7.5 hours1Further removing alcohol HOR generated by the reaction by distillation or rectification1。
5. The process as claimed in claim 4, wherein the entrainer is added to the reaction mixture in 5 to 7 portions, the time interval between two consecutive additions is 1.1 to 2 hours, and the amount of the entrainer added is 60 to 240mL each, relative to 1 mole of diethylene glycol at the start of the reaction.
6. The process according to claim 4 or 5, wherein the azeotroping agent is selected from the carboxylic acid esters RCOOR1One or more of xylene, toluene and benzene.
7. The method according to claim 4 or 5, wherein the carboxylate RCOOR1Boiling point in the range of 79-145 ℃ at a pressure of 760mm Hg, with the carboxylic ester RCOOR used in the reaction1Are the same substance.
8. The process of any one of claims 1 to 5, wherein the diethylene glycol of formula (II) and the carboxylic acid ester RCOOR1The molar ratio of (A) to (B) is 1: 2-10.
9. The process of claim 8 wherein said diethylene glycol of formula (II) and said carboxylate ester RCOOR1The molar ratio of (A) to (B) is 1: 2-5.
10. The process of claim 1, wherein the molar ratio of the diethylene glycol of formula (ii) to the anhydrous potassium carbonate is 1: 0.001-0.5.
11. The process of claim 1, wherein the molar ratio of the diethylene glycol of formula (ii) to the anhydrous potassium carbonate is 1: 0.01-0.2.
12. The process according to any one of claims 1 to 5, wherein the temperature of the reaction is 65 to 170 ℃.
13. The process according to any one of claims 1 to 5, further comprising separating the diethylene glycol dicarboxylate of formula (I) from the mixture obtained after the reaction is terminated.
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