CN104230710A - Preparation method for trimethylolpropane tricarboxylate - Google Patents
Preparation method for trimethylolpropane tricarboxylate Download PDFInfo
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- CN104230710A CN104230710A CN201310228434.2A CN201310228434A CN104230710A CN 104230710 A CN104230710 A CN 104230710A CN 201310228434 A CN201310228434 A CN 201310228434A CN 104230710 A CN104230710 A CN 104230710A
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- carboxylicesters
- trimethylolpropane
- structural formula
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- potassium carbonate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OBFVMFPYFRZRTE-UHFFFAOYSA-N tris(hydroxymethyl) propane-1,1,1-tricarboxylate Chemical compound CCC(C(=O)OCO)(C(=O)OCO)C(=O)OCO OBFVMFPYFRZRTE-UHFFFAOYSA-N 0.000 title abstract 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 96
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 63
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 48
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 58
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 53
- 235000011181 potassium carbonates Nutrition 0.000 claims description 46
- 239000007983 Tris buffer Substances 0.000 claims description 26
- 238000009835 boiling Methods 0.000 claims description 22
- 238000004821 distillation Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 125000005233 alkylalcohol group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 18
- -1 fatty acid ester Chemical class 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 239000003921 oil Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000003870 refractory metal Substances 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 2-(6-amino-1h-indol-3-yl)acetonitrile Chemical compound NC1=CC=C2C(CC#N)=CNC2=C1 ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- HNBDRPTVWVGKBR-UHFFFAOYSA-N n-pentanoic acid methyl ester Natural products CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- QRSVZLZEJCFUCB-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol 2-methylpropanoic acid Chemical compound C(C(C)C)(=O)O.C(C(C)C)(=O)O.C(C(C)C)(=O)O.C(O)C(CC)(CO)CO QRSVZLZEJCFUCB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229940070710 valerate Drugs 0.000 description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 3
- ORQCRWZGCJXCHJ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol pentanoic acid Chemical compound CCCCC(O)=O.CCCCC(O)=O.CCCCC(O)=O.CCC(CO)(CO)CO ORQCRWZGCJXCHJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 108010084311 Novozyme 435 Proteins 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 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
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method for trimethylolpropane tricarboxylate with a structural formula (I). The method comprises the steps of reacting 1,1,1-trimethylolpropane with a structural formula (II) with carboxylic ester R1COOR, R2COOR, R3COOR in presence of an anhydrous potassium carbonate-containing catalyst to generate products of trimethylolpropane tricarboxylate with the structural formula (I) and corresponding alcohol HOR, wherein R1, R2 and R3 are identical or different and are independently selected from one of a linear chain C2-C17 alkyl, a branch chain C3-C17 alkyl and C4-C8 cycloalkyl; and R is selected from C1-C5 alkayl. The method provided by the invention is beneficial to environment protection; and the product has high yield and good purity. The structural formula (I) and (II) are shown in the description.
Description
Technical field
The present invention relates to the preparation method of ester plasticizer or lubricating oil, be specifically related to the preparation method of trimethylolpropane tris carboxylicesters.
Background technology
Softening agent refers to the additives for plastics used in the plastics processing processes such as polyvinyl chloride, and it adds in polymeric system can make polymer glass temperature reduce, and plasticity increases, and makes it to be easy to processing.Trimethylolpropane tris carboxylicesters is the softening agent that a class is applicable to polyvinyl chloride (PVC) and processes.Another purposes of trimethylolpropane tris carboxylicesters is as lubricating oil.
US6673959B2 discloses a kind of carboxylicesters synthetic method comprising trimethylolpropane tris carboxylicesters, the method uses alkylsulphonic acid to be catalyzer, directly carries out 1,1, the esterification of 1-TriMethylolPropane(TMP) and carboxylic acid, generates trimethylolpropane tris carboxylicesters.The method adopts carboxylic acid to be that raw material carries out esterification, result in and has reacted the step that rear needs carry out neutralizing, washing the excessive carboxylic acid of removal, adds energy consumption and needs process aqueous phase waste liquid.
CN101456813A discloses a kind of manufacture method comprising the polyhydric alcohol fatty acid ester of trimethylolpropane tris fatty acid ester, the method adopts 1,1,1-TriMethylolPropane(TMP) and lipid acid, using functionalized ion liquid as catalyzer, react under normal pressure, 80 ~ 200 DEG C of conditions.The functionalized ion liquid cost that the method uses is relatively high, and the esterification yield of reactant 1,1,1-TriMethylolPropane(TMP) is 70-85%.
CN101475467A discloses a kind of novel process of synthesizing polyatomic alcohol ester by lipase catalysis, use immobilized lipase Novozym435 as catalyzer, be that raw material carries out transesterification reaction synthesizing trimethylol propane fatty acid ester with fatty acid ester and 1,1,1-TriMethylolPropane(TMP).The method needs to react under vacuum, and the reaction times is longer, and enzyme catalyst is responsive for envrionment conditions.
Summary of the invention
The object of the invention is to overcome the inadequate environmental protection of preparation method of prior art, be unsuitable for industrial defect, a kind of preparation method of new trimethylolpropane tris carboxylicesters is provided.
To achieve these goals, the invention provides the preparation method that a kind of structural formula is the trimethylolpropane tris carboxylicesters of (I), structural formula is (II's) 1 under being included in the catalyzer existence containing Anhydrous potassium carbonate by the method, 1,1-TriMethylolPropane(TMP) and carboxylicesters R
1cOOR, R
2cOOR, R
3cOOR reacts, and it is the trimethylolpropane tris carboxylicesters of (I) and the product of corresponding alcohol HOR that generation comprises structural formula;
Wherein, R
1, R
2, R
3identical or different, be independently selected from the C of straight chain separately
2-C
17the C of alkyl, side chain
3-C
17alkyl and C
4-C
8one in cycloalkyl, is preferably independently selected from the C of straight chain separately
2-C
8the C of alkyl and side chain
3-C
8one in alkyl; R is selected from C
1-C
5one in alkyl, is preferably methyl or ethyl.
The preparation method of trimethylolpropane tris carboxylicesters provided by the invention utilizes the object reaching invention containing the catalyzer of Anhydrous potassium carbonate and the mating reaction of carboxylicesters; namely protection of the environment or safety in production is conducive to; product and reactant and catalyzer easily separated; yield is high; purity is good, without the need to neutralizing, wash, dewater or adding the operations such as absorbent filtering.Particularly; with employing carboxylic acid as acylating agent and with compared with alkylsulphonic acid, ionic liquid, lipase-catalyzed technology; method provided by the invention can overcome inadequate environmental protection, be unsuitable for industrial defect, makes the inventive method to be widely used in large-scale commercial production.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
1,1,1-TriMethylolPropane(TMP) is referred to as TriMethylolPropane(TMP) below.
The invention provides the preparation method that a kind of structural formula is the trimethylolpropane tris carboxylicesters of (I), structural formula is TriMethylolPropane(TMP) and the carboxylicesters R of (II) under being included in the catalyzer existence containing Anhydrous potassium carbonate by the method
1cOOR, R
2cOOR, R
3cOOR reacts, and it is the trimethylolpropane tris carboxylicesters of (I) and the product of corresponding alcohol HOR that generation comprises structural formula;
Wherein, R
1, R
2, R
3identical or different, be independently selected from the C of straight chain separately
2-C
17the C of alkyl, side chain
3-C
17alkyl and C
4-C
8one in cycloalkyl, is preferably independently selected from the C of straight chain separately
2-C
8the C of alkyl and side chain
3-C
8one in alkyl; R is selected from C
1-C
5one in alkyl, is preferably methyl or ethyl.
Preparation in accordance with the present invention, works as R
1, R
2, R
3time identical, carboxylicesters R
1cOOR, R
2cOOR, R
3cOOR represents same material, hereinafter referred to as carboxylicesters R
1cOOR.
Structural formula, under only need existing at the catalyzer containing Anhydrous potassium carbonate, is TriMethylolPropane(TMP) and the carboxylicesters R of (II) by preparation in accordance with the present invention
1there is transesterification reaction in COOR, can realize object of the present invention, namely be beneficial to environment protection, product and reactant and catalyzer easily separated, yield is high, and purity is good.But under preferable case, described transesterification reaction carries out reacting under being included in distillation or rectifying condition, and (now distillation or rectifying condition are equal to described is TriMethylolPropane(TMP) and the carboxylicesters R of (II) by structural formula
1cOOR carries out the reaction conditions reacted), reaction removes the alcohol HOR of generation simultaneously; Preferred scheme is further, is reacting 5-7.5 hour with the rear entrainer adding alcohol HOR in reaction solution, with the alcohol HOR generated except dereaction by the mode of component distillation or azeotropic distillation.This preferred version can further improve yield and the purity of the product that structural formula is (I).
Usually, due to carboxylicesters R
1the boiling point of COOR higher than the boiling point of alcohol HOR, therefore, when structural formula is TriMethylolPropane(TMP) and the carboxylicesters R of (II)
1the alcohol HOR produced in ester-exchange reaction, when distilling or carry out under rectifying condition, can remove, carry out to impel transesterification reaction to positive dirction by the transesterification reaction of COOR.
In the present invention, what steadily continue to enable above-mentioned preferred version carries out forward, reaction brings into use upper end " skimmer " of prolong to be housed as water distilling apparatus, and described " skimmer " refers to that the Dean and Stark apparatus (Dean-Stark apparatus) of piston switch is arranged at bottom.
After reaction 5-7.5 hour, the feed postition of entrainer is preferably to divide and joins for 5-7 time in reaction solution, the adjacent timed interval added for twice is 1.5-2 hour, and the structural formula relative to 1 mole is the consumption of the TriMethylolPropane(TMP) of (II), and each add-on of entrainer is 60-240mL.Increase each add-on of entrainer to be conducive to improving yield and the purity that structural formula is the product of (I), but add the energy consumption of reaction simultaneously.
Another mode of adding entrainer is: first with water distilling apparatus or rectifier unit, under distillation or rectifying condition after transesterification reaction 5-7.5 hour, then is joined continuously in reaction solution by described entrainer under distillation or rectifying condition.Structural formula relative to 1 mole is the consumption of the TriMethylolPropane(TMP) of (II), and flow acceleration can be 60-240mL/ hour, and it can be 5-7 hour that stream adds the time.The speed that adds increasing entrainer is conducive to improving yield and the purity that structural formula is the product of (I), but adds the energy consumption of reaction simultaneously.
It will be understood by those skilled in the art that when adding entrainer, preferably controlling the boiling point of the temperature >=entrainer of reaction solution.Entrainer gradation adds fashionable, in the process adding entrainer, can not lower the temperature, also first the temperature of reaction solution can be cooled under the boiling point of entrainer, then add entrainer.The mode preferably adding entrainer according to gradation when laboratory operation is implemented, and the mode particularly preferably adopting gradation again of first lowering the temperature to add entrainer is implemented.Time required under the boiling point temperature of reaction solution being reduced to entrainer is generally no more than half an hour, preferred 0.1-0.5 hour.Preferably implement according to mode that is semicontinuous or that add entrainer continuously in Industrial processes, add entrainer particularly preferably in Continuous Flow under distillation or rectifying condition.Add in the process of entrainer in Continuous Flow, carry out between the boiling point of the azeotrope that the alcohol that the temperature of reaction system should control to generate at the boiling point of entrainer and entrainer and reaction is formed, flow acceleration can regulate according to the kind of speed of response, entrainer and consumption.
In the present invention, entrainer is preferably the solvent that boiling point is 79-145 DEG C, more preferably boiling point to be the aromatic hydrocarbon of 79-145 DEG C and boiling point be in the carboxylicesters of 79-145 DEG C one or more.Described aromatic hydrocarbon be more preferably in dimethylbenzene, toluene and benzene one or more; More preferably toluene.When the boiling point of described carboxylicesters R1COOR is in 79-145 DEG C of (preferred 79-128 DEG C) scope, described entrainer can also select the starting carboxylic acid's ester R for reacting
1cOOR, i.e. described carboxylicesters R
1when the boiling point of COOR is in 79-145 DEG C of (preferred 79-128 DEG C) scope, entrainer and the starting carboxylic acid's ester R for reacting
1cOOR is same material.In the present invention, boiling point typically refers to the boiling point under pressure is 760mm mercury column.
In the present invention, the amount of reactant is preferably, carboxylicesters R
1at least 3 times of the mole number of COOR to be structural formula the be mole number of the TriMethylolPropane(TMP) of (II); Be more preferably, structural formula is TriMethylolPropane(TMP) and the carboxylicesters R of (II)
1the mol ratio of COOR is 1:3-15; More preferably, structural formula is TriMethylolPropane(TMP) and the carboxylicesters R of (II)
1the mol ratio of COOR is 1:3-7.5.It will be understood by those skilled in the art that the mole dosage along with carboxylicesters increases, speed of response is accelerated, and yield improves, but also affects product separation.As carboxylicesters R of the present invention
1cOOR is selected from the carboxylicesters R of boiling point within the scope of 79 DEG C-145 DEG C under pressure is 760mm mercury column
1during COOR a kind of, if described carboxylicesters R selected by entrainer
1cOOR, so carboxylicesters R
1the consumption of COOR, except pressing the TriMethylolPropane(TMP) and carboxylicesters R that structural formula is (II)
1the mol ratio of COOR is beyond 1:3-15, also can add by the consumption of entrainer noted earlier and mode.
The kind of the present invention to the catalyzer containing Anhydrous potassium carbonate is not particularly limited, as long as just can realize goal of the invention containing Anhydrous potassium carbonate in catalyzer.Particularly, described catalyzer can be Anhydrous potassium carbonate, also can contain Anhydrous potassium carbonate and inorganic refractory metal oxide.When described catalyzer contains Anhydrous potassium carbonate and inorganic refractory metal oxide, described catalyzer can be carried on the form use of inorganic refractory metal oxide with Anhydrous potassium carbonate.Preferably, described catalyzer is that Anhydrous potassium carbonate and/or Anhydrous potassium carbonate load to the loaded catalyst (namely catalytic active component is Anhydrous potassium carbonate) that inorganic refractory metal oxide carrier is formed.When described catalyzer be Anhydrous potassium carbonate load at the loaded catalyst that inorganic refractory metal oxide carrier is formed time, or when Anhydrous potassium carbonate and described carrier are mixed to form catalyzer, with the gross weight of this catalyzer for benchmark, the content of described Anhydrous potassium carbonate is 5-95%, and the content of preferred Anhydrous potassium carbonate is 10-30%.In the present invention, described inorganic refractory metal oxide carrier can be aluminum oxide, molecular sieve or zirconium white.No matter use the catalyzer of which kind of form, equal preferred structure formula is that in the TriMethylolPropane(TMP) of (II) and catalyzer, the mol ratio of contained Anhydrous potassium carbonate is 1:0.01-0.5; More preferably structural formula is that in the TriMethylolPropane(TMP) of (II) and catalyzer, the mol ratio of contained Anhydrous potassium carbonate is 1:0.04-0.2.It will be understood by those skilled in the art that the consumption along with catalyzer increases, although can fast reaction speed, also affect product separation simultaneously.
The described catalyzer containing Anhydrous potassium carbonate can be prepared according to this area ordinary method.Such as, when described catalyzer is the catalyzer containing Anhydrous potassium carbonate and aluminum oxide, preferred described catalyzer is that Anhydrous potassium carbonate loads to the loaded catalyst that aluminum oxide is formed, and the preparation of this catalyzer can comprise the following steps:
(1) by powdery aluminum carrier calcination, maturing temperature is 550 DEG C-600 DEG C, and roasting time is 1-5 hour;
(2) by the powdery aluminum carrier impregnation after step (1) roasting in wet chemical;
(3) carrier through dipping is carried out drying and roasting, maturing temperature is 550 DEG C-600 DEG C, and roasting time is 1-5 hour.
In the present invention, the temperature of reaction only need ensure the boiling point of the alcohol HOR of the temperature >=generation of reaction solution.The temperature of reaction can be 65-170 DEG C, is preferably 90-155 DEG C; When using entrainer, the boiling point of the temperature >=entrainer of reaction solution.In actually operating, the temperature of reaction is along with the boiling point bp65 DEG C removing the lower boiling by-product alcohol HOR(such as methyl alcohol that dereaction generates in reaction process) and increase.In laboratory, adopt conventional glass flask as reactor, with water-bath or the oil bath thermal source as heating, when the temperature controlling water-bath or oil bath is 80-160 DEG C, and as preferred reactant ester R
1when the R of COOR is methyl, preferably entrainer is toluene, temperature of reaction can be made to control 65-120 DEG C of scope.In the industrial production, control thermal source needed for temperature of reaction to be provided by the various known method in this area, such as 100 DEG C provide by water vapor bath or oil bath heating, and the temperature range of 100-160 DEG C provides by pressured steam bath or oil bath heating.In the present invention, the type of heating of reaction adopts conventional heating mode, such as, can adopt the type of heating etc. of temperature-gradient method.
What those skilled in the art should understand that is, in order to obtain the trimethylolpropane tris carboxylicesters that the higher structural formula of purity is (I), the inventive method preferably also comprises after termination of the reaction, is that the trimethylolpropane tris carboxylicesters of (I) is separated from the rear gained mixture of reaction by structural formula.Be the method that the trimethylolpropane tris carboxylicesters of (I) is separated from the rear gained mixture of reaction by structural formula, comprise alcohol HOR, the catalyzer containing Anhydrous potassium carbonate, the unreacted carboxylicesters R that will react in gained mixture
1cOOR and structural formula are the TriMethylolPropane(TMP) of (II), and a small amount of intermediate product trimethylolpropane tris carboxylicesters and impurity, remove from reaction gained mixture, for the method removed without particular requirement, the thinkable various method of those skilled in the art can be adopted, in the present invention, preferably first by the method for distillation or rectifying, the alcohol HOR of reaction generation is removed from reaction gained mixture, pass through activated carbon decolorizing again, filter, catalyzer containing Anhydrous potassium carbonate removes by the method for centrifugation or extraction from reaction gained mixture, finally by the method for underpressure distillation or rectification under vacuum, by unreacted carboxylicesters R
1cOOR and structural formula are the TriMethylolPropane(TMP) of (II), and a small amount of intermediate product trimethylolpropane tris carboxylicesters and impurity, remove from reaction gained mixture.
Preparation in accordance with the present invention, works as R
1, R
2, R
3in have at least 2 different time, under only need existing at the catalyzer containing Anhydrous potassium carbonate, be TriMethylolPropane(TMP) and the carboxylicesters R of (II) by structural formula
1cOOR, R
2cOOR, R
3cOOR reacts; Described structural formula is the TriMethylolPropane(TMP) of (II) and described carboxylicesters R
1cOOR, R
2cOOR and R
3the mol ratio of COOR sum is 1:3-15; Be preferably 1:3-6, wherein, described carboxylicesters R
1cOOR, R
2cOOR and R
3ratio between COOR can adjust according to needs of production, preferably, and R
1cOOR, R
2cOOR and R
3the mol ratio of COOR is 1:(1-2): the temperature of (1-3) described reaction can be 65-170 DEG C, is preferably 90-155 DEG C.The product that reaction is produced may be mixture, and in order to improve the productive rate of structural formula for the trimethylolpropane tris carboxylicesters of (I), following discloses one preferred embodiment.
Assuming that carboxylicesters boiling point order is as follows: R
1cOOR>=R
2cOOR>R
3cOOR; Wherein R
1cOOR, R
2cOOR and R
3cOOR mol ratio is 1:1-2:1-3.First, TriMethylolPropane(TMP) and carboxylicesters R
1cOOR reacts 5-7.5 hour, and this reaction is carried out under distillation or rectifying condition, to remove the alcohol HOR that dereaction generates in reaction process; Add carboxylicesters R again
2cOOR, reaction 5-7.5 hour, carries out under distillation or rectifying condition, to remove the alcohol HOR that dereaction generates in reaction process; Add carboxylicesters R again
3cOOR, reaction 5-7.5 hour, carries out under distillation or rectifying condition, to remove the alcohol HOR that dereaction generates in reaction process; Wherein, described structural formula is the TriMethylolPropane(TMP) of (II) and described carboxylicesters R
1the mol ratio of COOR is 1:1-2, is preferably 1:1; Described structural formula is the TriMethylolPropane(TMP) of (II) and described carboxylicesters R
2the mol ratio of COOR is 1:1-3, is preferably 1:1-2; Described structural formula is the TriMethylolPropane(TMP) of (II) and described carboxylicesters R
3the mol ratio of COOR is 1:1-8, is preferably 1:1-3; Described catalyzer is Anhydrous potassium carbonate, and described structural formula is the TriMethylolPropane(TMP) of (II) and the mol ratio of described Anhydrous potassium carbonate is 1:0.01-0.5, is preferably 1:0.04-0.2.
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
" skimmer " described in embodiment refers to that the Dean and Stark apparatus of piston switch is arranged at bottom.
Embodiment 1
This embodiment is for illustration of the preparation method of trimethylolpropane tris valerate provided by the invention.
At band condenser, skimmer, 9.84g(0.075mol is added in the 100mL round-bottomed flask of agitator) TriMethylolPropane(TMP) (98%), 50.55g(0.44mol) positive methyl valerate, 2.01g(0.015mol) Anhydrous potassium carbonate, the oil bath of contact round-bottomed flask is heated to 118 DEG C, react under 0.1MPa, by distillating method the methyl alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 6 hours, toluene is added in round-bottomed flask, front and back add 6 times altogether, the adjacent timed interval added for twice is 1.5 hours, add 10mL at every turn, react 1 hour after adding toluene at every turn and toluene and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds toluene next time after about 30 minutes again.By the mixture cold filtration removing Anhydrous potassium carbonate in round-bottomed flask after reaction terminates, again by filtrate 250Pa and at 95 DEG C underpressure distillation removing unreacted positive methyl valerate and other impurity, obtain trimethylolpropane tris valerate 27.36g, yield 96%, the results are shown in Table 1.
Embodiment 2
This embodiment is for illustration of the preparation method of trimethylolpropane tris butanic acid ester provided by the invention.
At band condenser, skimmer, 10.66g(0.08mol is added in the 100mL round-bottomed flask of agitator) TriMethylolPropane(TMP) (98%), 51.78g(0.50mol) methyl butyl, 2.22g(0.016mol) Anhydrous potassium carbonate, the oil bath of contact round-bottomed flask is heated to 98 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 6 hours, methyl butyl is added in round-bottomed flask, front and back add 6 times altogether, the adjacent timed interval added for twice is 2 hours, add 10mL at every turn, under 100 DEG C oil bath react 1.5 hour after adding methyl butyl at every turn and methyl butyl and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds methyl butyl next time after about 30 minutes again.By the mixture cooling in round-bottomed flask after reaction terminates, cross and filter Anhydrous potassium carbonate, again by first for filtrate underpressure distillation removing methyl butyl etc., again 200Pa and at 95 DEG C underpressure distillation remove unreacted methyl butyl and other impurity, obtain trimethylolpropane tris butanic acid ester, 25.92g, yield 94%.The results are shown in Table 1.
Embodiment 3
This embodiment is for illustration of the preparation method of trimethylolpropane tris isobutyrate provided by the invention.
Trimethylolpropane tris isobutyrate is prepared according to the method for embodiment 1, unlike, with 42.51g(0.42mol) methyl isobutyrate substitutes 50.55g(0.44mol) positive methyl valerate, use methyl isobutyrate is entrainer.
At band condenser, skimmer, 9.28g(0.07mol is added in the 100mL round-bottomed flask of agitator) TriMethylolPropane(TMP) (98%), 42.51g(0.42mol) methyl isobutyrate, 1.95g(0.014mol) Anhydrous potassium carbonate, the oil bath of contact round-bottomed flask is heated to 90 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 7 hours, methyl isobutyrate is added in round-bottomed flask, front and back add 9 times altogether, the adjacent timed interval added for twice is 3 hours, add 7mL at every turn, under 95 DEG C oil bath react 2.9 hour after adding methyl isobutyrate at every turn and methyl isobutyrate and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds methyl isobutyrate next time after about 6 minutes again.By the mixture cooling in round-bottomed flask after reaction terminates, cross and filter Anhydrous potassium carbonate, again by first for filtrate underpressure distillation removing methyl isobutyrate etc., again 200Pa and at 80 DEG C underpressure distillation remove unreacted methyl isobutyrate and other impurity, obtain trimethylolpropane tris isobutyrate, 22.72g, yield 95%.The results are shown in Table 1.
Embodiment 4
This embodiment is for illustration of the preparation method of trimethylolpropane tris hexahydrobenzoic acid ester provided by the invention.
At band condenser, skimmer, 8.08g(0.06mol is added in the 100mL round-bottomed flask of agitator) TriMethylolPropane(TMP) (98%), 51.37g(0.36mol) methyl cyclohexanecarboxylaand, 1.66g(0.012mol) Anhydrous potassium carbonate, the oil bath of contact round-bottomed flask is heated to 155 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 6 hours, toluene is added in round-bottomed flask, front and back add 6 times altogether, the adjacent timed interval added for twice is 2 hours, add 10mL at every turn, under 155 DEG C oil bath react 1.5 hour after adding toluene at every turn and toluene and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds toluene next time after about 30 minutes again.After reaction terminates, the mixture in round-bottomed flask cooled and add about 100mL toluene solvant, cross and filter Anhydrous potassium carbonate, again by first for filtrate underpressure distillation removing toluene etc., again 200Pa and at 95 DEG C underpressure distillation remove unreacted methyl cyclohexanecarboxylaand and other impurity, obtain trimethylolpropane tris hexahydrobenzoic acid ester, 20.90g, yield 74%.The results are shown in Table 1.
Embodiment 5
This embodiment loads to Anhydrous potassium carbonate the method that alumina catalyst support makes catalyzer prepare the positive valerate of trimethylolpropane tris for illustration of provided by the invention.
Anhydrous potassium carbonate loads to the preparation of the catalyzer of aluminum oxide
By stand-by for neutral alumina (Alpha-alumina, 100-200 order) roasting 4 hours at 550 DEG C.By Anhydrous potassium carbonate 105 DEG C of air dry oven inner dryings 3 hours, the Anhydrous potassium carbonate getting 6g drying is dissolved in 40mL deionized water, adds 24g neutral alumina after fully dissolving, after fully stirring static 24 hours.Mixture is put into furnace pot evaporating water, then put into air dry oven at 105 DEG C dry 24 hours.By the roasting 5 hours at 600 DEG C in retort furnace of gained solid, obtain the catalyst fines 28.89g that Anhydrous potassium carbonate loads to aluminum oxide.
The preparation of the positive valerate of trimethylolpropane tris
At band condenser, skimmer, 9.30g (0.07mol) TriMethylolPropane(TMP) (98%) is added in the 100mL round-bottomed flask of agitator, 52.85g(0.45mol) positive methyl valerate 9.66g (containing salt of wormwood 0.014mol) above-mentioned Anhydrous potassium carbonate loads to the catalyzer of aluminum oxide, the oil bath touching round-bottomed flask is heated to 120 DEG C, react under 0.1MPa, by distillating method the alcohol of generation be distilled to skimmer in reaction simultaneously and remove, react after 6 hours, toluene is added in round-bottomed flask, front and back add 6 times altogether, the adjacent timed interval added for twice is 2 hours, add 10mL at every turn, add toluene react 1.7 hours and toluene and azeotrope distilled out round-bottomed flask simultaneously at every turn, question response cooling adds toluene next time after about 18 minutes again.After reaction terminates, the mixture cold filtration in round-bottomed flask is removed above-mentioned supported catalyst, again by filtrate the underpressure distillation unreacted positive methyl valerate of removing and other magazines at 280Pa and 110 DEG C, obtain the positive valerate 20.21g of trimethylolpropane tris, yield 75%, the results are shown in Table 1.
Table 1
Note: by the percentage calculation of actual output and theoretical yield.
As can be seen from the experimental result of table 1, adopt the inventive method to prepare trimethylolpropane tris carboxylicesters, yield is high.
As can be seen from embodiment 2 and 3, under 760mm mercury column, boiling point is that the carboxylicesters of 79-145 DEG C of scope itself can be used as entrainer in the reaction.
To sum up, the product of the preparation method of trimethylolpropane tris carboxylicesters provided by the invention and reactant and catalyzer easily separated, yield is high.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (12)
1. structural formula is a preparation method for the trimethylolpropane tris carboxylicesters of (I), it is characterized in that, structural formula is 1,1,1-TriMethylolPropane(TMP) and the carboxylicesters R of (II) under being included in the catalyzer existence containing Anhydrous potassium carbonate by the method
1cOOR, R
2cOOR, R
3cOOR reacts, and it is the trimethylolpropane tris carboxylicesters of (I) and the product of corresponding alcohol HOR that generation comprises structural formula;
Wherein, R
1, R
2, R
3identical or different, be independently selected from the C of straight chain separately
2-C
17the C of alkyl, side chain
3-C
17alkyl and C
4-C
8one in cycloalkyl, is preferably independently selected from the C of straight chain separately
2-C
8the C of alkyl and side chain
3-C
8one in alkyl;
R is selected from C
1-C
5one in alkyl, is preferably methyl or ethyl.
2. method according to claim 1, wherein, described reaction is carried out under distillation or rectifying condition, to remove the alcohol HOR that dereaction generates in reaction process.
3. method according to claim 1 and 2, wherein, the temperature of described reaction is 65-170 DEG C, preferred 90-155 DEG C.
4. method according to claim 2, wherein, adds the entrainer of alcohol HOR in reaction solution after 5-7.5 hour in reaction.
5. method according to claim 4, wherein, described entrainer divides and joins for 5-7 time in reaction solution, the adjacent timed interval added for twice is 1.5-2 hour, structural formula relative to 1 mole is (II's) 1, the consumption of 1,1-TriMethylolPropane(TMP), each add-on of entrainer is 60-240mL.
6. the method according to claim 4 or 5, wherein, described entrainer is selected from C
1-C
5one or more in the carboxylicesters of alkyl alcohol, dimethylbenzene, toluene and benzene.
7. the method according to claim 4 or 5, wherein, the boiling point of described carboxylicesters under pressure is 760mm mercury column is within the scope of 79-145 DEG C, and described entrainer is identical with the carboxylicesters for reacting.
8. method according to claim 1 and 2, wherein, described structural formula is 1,1, the 1-TriMethylolPropane(TMP) of (II) and the mol ratio of described carboxylicesters is 1:3-15; Be preferably 1:4-7.5.
9. method according to claim 1 and 2, wherein, described catalyzer is Anhydrous potassium carbonate.
10. method according to claim 1 and 2, wherein, described catalyzer contains Anhydrous potassium carbonate and aluminum oxide; Preferably, the form that described catalyzer loads to aluminum oxide with Anhydrous potassium carbonate uses.
11. methods according to claim 10, wherein, with the gross weight of this catalyzer for benchmark, the content of described salt of wormwood is 10-30 % by weight.
12. according to the method in claim 9-11 described in any one, and wherein, described structural formula is 1,1, the 1-TriMethylolPropane(TMP) of (II) and the mol ratio of described Anhydrous potassium carbonate is 1:0.01-0.5, is preferably 1:0.04-0.2.
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| Title |
|---|
| 汪勇等: "棕榈油甲酯制备生物润滑油三羟甲基丙烷脂肪酸三酯的工艺研究", 《中国粮油学报》 * |
| 郭晓昕等: "三羟甲基丙烷类酯的合成及应用进展", 《广州化工》 * |
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