CN106631776A - Green preparation process for synthesizing 12-carbon alcohol ester by double catalytic system - Google Patents
Green preparation process for synthesizing 12-carbon alcohol ester by double catalytic system Download PDFInfo
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- CN106631776A CN106631776A CN201611004524.3A CN201611004524A CN106631776A CN 106631776 A CN106631776 A CN 106631776A CN 201611004524 A CN201611004524 A CN 201611004524A CN 106631776 A CN106631776 A CN 106631776A
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- Prior art keywords
- catalyst
- load
- alcohol ester
- hydroxide
- isobutylaldehyde
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- 229910052799 carbon Inorganic materials 0.000 title abstract description 5
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 230000003197 catalytic effect Effects 0.000 title abstract 2
- 230000002194 synthesizing effect Effects 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002608 ionic liquid Substances 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- -1 Lauryl Alcohol ester Chemical class 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 11
- 239000002585 base Substances 0.000 claims description 10
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 10
- 230000009977 dual effect Effects 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 5
- 239000001639 calcium acetate Substances 0.000 claims description 5
- 235000011092 calcium acetate Nutrition 0.000 claims description 5
- 229960005147 calcium acetate Drugs 0.000 claims description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- DHCLVZWYPTWJSA-UHFFFAOYSA-N CCN1CN(C=C1)C.O Chemical class CCN1CN(C=C1)C.O DHCLVZWYPTWJSA-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- RBFHQWDOZCHFBI-UHFFFAOYSA-N CN1C=CN(C)C1.O Chemical class CN1C=CN(C)C1.O RBFHQWDOZCHFBI-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical group [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims 2
- 150000003851 azoles Chemical class 0.000 claims 1
- 239000003610 charcoal Substances 0.000 claims 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000011734 sodium Substances 0.000 abstract description 7
- 229910052708 sodium Inorganic materials 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 238000009833 condensation Methods 0.000 description 12
- 230000005494 condensation Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000011949 solid catalyst Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000005292 vacuum distillation Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 10
- SQPFPKSOPRMSDP-UHFFFAOYSA-N C(CCC)N1CN(C=C1)C.O Chemical class C(CCC)N1CN(C=C1)C.O SQPFPKSOPRMSDP-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- KSBOQWWDFBYHGC-UHFFFAOYSA-N butylbenzene ethene Chemical compound C=C.C(CCC)C1=CC=CC=C1 KSBOQWWDFBYHGC-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B01J35/19—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
Abstract
The invention relates to a preparation method of 12-carbon alcohol ester. The method is characterized in that the 12-carbon alcohol ester is directly prepared from isobutyraldehyde by one step under the action of a catalyst; the catalyst is a double catalytic system consisting of supported type solid alkali and alkaline ionic liquid. The process effectively overcome the defect that the catalyst which is sodium alcoholate or sodium hydroxide is removed from the reaction system difficultly, and has the advantages that the catalyst is easy to separate and recover, the selectivity is high, the yield is high and waste water is basically not generated in production.
Description
Technical field
The invention belongs to the synthetically prepared field of fine chemical product.Prepare film forming under specially a kind of dual catalyst system to help
The preparation technology of agent Lauryl Alcohol ester.
Technical background
Lauryl Alcohol ester is also referred to as alcohol ester 12 or Texanol alcohol esters, entitled 2,2,4- trimethyl -1 of chemistry, 3- pentanediols
Mono isobutyrate, is a kind of water-insoluble high boiling colourless transparent liquid, is emerging green coalescents, and application is increasingly
Extensively, get the attention primarily as the coalescents of emulsion paint.Compared with common coalescents, Lauryl Alcohol ester has
Plurality of advantages：Resin intermiscibility is good, and consumption is few, and film-forming temperature is low, and film levelability, color developing are good, and freezing point is low, hydrolytic stability
Good, toxicity is low, is a kind of fabulous emulsion paint coalescents, can be efficiently used for polyvinyl acetate homopolymers, copolymer and
In trimer, and in the latex such as pure acrylic acid, styrene/acrylic, poly- butylbenzene ethene and ethylene vinyl acetate.Additionally,
Lauryl Alcohol ester is alternatively arranged as high boiling solvent and plasticizer to use.
The production of Lauryl Alcohol ester at present can be divided into indirect method and direct method two is planted greatly, because of indirect method complex process, raw material
Utilization rate is low, using little.Direct method process is simple, equipment investment is few, and raw material is easy to get, for the producer being currently mainly used
Method.Direct method under base catalyst catalysis, through isobutylaldehyde itself aldol reaction is carried out mainly with isobutylaldehyde as raw material
2,2,4- trimethyl -3- hydrogenation of hydroxypentylaldehyd is generated, is then proceeded to further react with isobutylaldehyde in the basic conditions and is obtained crude product,
The crude product is separated again to purify to obtain the standard compliant product of high-purity.The catalyst for adopting at present is mainly alkali or alkaline-earth metal
Oxide and hydroxide, in use catalyst reclaim more difficult, the poor selectivity of product, can also produce in addition
Substantial amounts of waste water, in addition the reaction time is long, the shortcomings of yield is undesirable, governs a large amount of productions of Lauryl Alcohol ester.Also report
Road is using sodium alkoxide as catalyst, although the technique is simpler, and yield has been lifted, but catalyst sodium alkoxide is not easy point
From, to obtain highly purified Lauryl Alcohol ester needs harsher purification condition, during can produce a large amount of waste water so that cost
Greatly promote, affect the sales volume in market.
The content of the invention
Present invention is generally directed to the current weak point of existing production technology, there is provided a kind of with load-type solid to sponsor
There is agent, the production technology of the Lauryl Alcohol ester being aided with the dual catalyst system of alkali ionic liquid, technique catalyst to hold
Easily reclaim, repeat and utilize, it is selective preferably, high income, the advantages of substantially do not produce waste water in production.
Specifically, with isobutylaldehyde as raw material, direct reaction generates Lauryl Alcohol ester to this technique under catalyst, its
Catalyst is characterised by for solid base and alkali ionic liquid dual catalyst system.Solid base catalyst is NaOH, hydrogen-oxygen
Change potassium, potassium carbonate, calcium nitrate, calcium carbonate, calcium acetate and calcium chloride, (carrier is aluminum oxide, activated carbon and montmorillonite)；Oxidation
Potassium, calcium oxide, triethylamine, sodium methoxide and caustic alcohol (carrier be molecular sieve, silica gel), ionic liquid be hydroxide 1- butyl-
3- methylimidazoles, the methylimidazole of hydroxide 1- ethyls -3 and the methylimidazole of hydroxide 1- methyl -3.
In this technique the consumption of catalyst for isobutylaldehyde 1%-5% (mass percent, come by sodium alkoxide or NaOH in terms of
Amount), ionic liquid consumption is the 5%-20% of isobutylaldehyde, and reaction temperature is 40-100 DEG C, and the reaction time is 2-10h.
The dual catalyst system that the present invention is adopted compares single inorganic base or sodium alkoxide has a more preferable catalysis activity, therefore catalysis
Agent consumption is less, further, since the solid base catalyst for support type for using, reaction terminates rear directly filtration just can be realized
The separation of catalyst, and catalyst can reuse, and make production technology simpler, and can substantially prevent waste water
Generation so that production technology more environmental protection.
The invention provides
1. a kind of method for preparing Lauryl Alcohol ester, it is characterised in that next in catalyst action with isobutylaldehyde as raw material
Step directly prepares Lauryl Alcohol ester, and catalyst is the dual catalyst system that load-type solid and alkali ionic liquid are constituted.
2. the method according to item 1, wherein the support type base catalyst is selected from NaOH, potassium hydroxide, carbon
Sour potassium, calcium nitrate, calcium carbonate, calcium acetate and calcium chloride, load on the load being selected from the group：Alundum (Al2O3), activated carbon
And montmorillonite；Or support type base catalyst is selected from potassium oxide, calcium oxide, triethylamine, sodium methoxide and caustic alcohol, loads to
On the load being selected from the group：Silica gel, molecular sieve.
3. the method according to item 1, wherein the alkali ionic liquid selected from hydroxide 1- butyl -3- methylimidazoles,
Hydroxide 1- ethyl-3-methylimidazoles and hydroxide 1- methyl -3- methylimidazoles.
4. the method according to item 1, it is characterised in that in mass the consumption of load type solid body base catalyst is isobutyl
The 1%-5% of aldehyde.
5. the method according to item 1, it is characterised in that in mass the consumption of alkali ionic liquid is isobutylaldehyde
5%-20%.
6. the method according to item 1, it is characterised in that at 40-100 DEG C, the reaction time is 2-10h to reaction temperature.
7. the method according to item 1, it is characterised in that reaction temperature is 80 DEG C or 90 DEG C.
Specific embodiment
Embodiment 1
By 72g isobutylaldehydes, load NaOH solid catalyst (carrier：Montmorillonite, m (NaOH):M (montmorillonite)=
0.7) 2.2g and hydroxide 1- butyl -3- methylimidazole 7.2g are added to the 500mL four-hole bottles for being furnished with condensation pipe heating device
In, 60 DEG C are heated to, stirring reaction 4h is cooled to room temperature, and filtration separates catalyst from reaction system, and analytical reactions are mixed
Compound, isobutylaldehyde conversion rate 90%, selective 94%, vacuum distillation removes unreacted isobutylaldehyde, continues to collect content
More than 99.5% product Lauryl Alcohol ester.
Embodiment 2
By 72g isobutylaldehydes, load potassium hydroxide solid catalyst (carrier：Activated carbon, m (KOH):M (activated carbon)=
0.5), 1.5g and hydroxide 1- butyl -3- methylimidazole 10g are added to the 500mL four-hole bottles for being furnished with condensation pipe heating device
In, 50 DEG C are heated to, stirring reaction 3h is cooled to room temperature, and filtration separates catalyst from reaction system, and analytical reactions are mixed
Compound, isobutylaldehyde conversion rate 95%, selective 97%, vacuum distillation removes unreacted isobutylaldehyde, continues to collect content
More than 99.5% product Lauryl Alcohol ester.
Embodiment 3
By 72g isobutylaldehydes, load potash solid catalyst (carrier：Aluminum oxide, m (KCO3):M (aluminum oxide)=
0.25), 3.6g and hydroxide 1- methyl -3- methylimidazole 8g are added to the 500mL four-hole bottles for being furnished with condensation pipe heating device
In, 80 DEG C are heated to, stirring reaction 6h is cooled to room temperature, and filtration separates catalyst from reaction system, and analytical reactions are mixed
Compound, isobutylaldehyde conversion rate 88%, selective 93%, vacuum distillation removes unreacted isobutylaldehyde, continues to collect content
More than 99.5% product Lauryl Alcohol ester.
Embodiment 4
By 72g isobutylaldehydes, load calcium nitrate solid catalyst (carrier：Aluminum oxide, m (calcium nitrate)：M (aluminum oxide)=
0.2), 3g and hydroxide 1- ethyl-3-methylimidazole 9g add to be furnished with condensation pipe heating device 500mL four-hole bottles in,
80 DEG C are heated to, stirring reaction 7h is cooled to room temperature, and filtration separates catalyst from reaction system, analytical reactions mixing
Thing, isobutylaldehyde conversion rate 90%, selective 94%, vacuum distillation removes unreacted isobutylaldehyde, continues to collect content 99.5%
Product Lauryl Alcohol ester above.
Embodiment 5
By 72g isobutylaldehydes, load calcium oxide solid catalyst (carrier：Aluminum oxide, m (CaO)：M (aluminum oxide)=0.2),
3.6g and hydroxide 1- butyl -3- methylimidazole 10g add to be furnished with condensation pipe heating device 500mL four-hole bottles in, plus
To 80 DEG C, stirring reaction 5h is cooled to room temperature to heat, and filtration separates catalyst from reaction system, analytical reactions mixture,
Isobutylaldehyde conversion rate 95%, selective 98%, vacuum distillation removes unreacted isobutylaldehyde, continues to collect content more than 99.5%
Product Lauryl Alcohol ester.
Embodiment 6
By 72g isobutylaldehydes, load calcium acetate solid catalyst (carrier：Aluminum oxide, m (calcium acetate)：M (aluminum oxide)=
0.3), 3.6g and hydroxide 1- ethyl-3-methylimidazole 14g are added to the 500mL four-hole bottles for being furnished with condensation pipe heating device
In, 90 DEG C are heated to, stirring reaction 8h is cooled to room temperature, and filtration separates catalyst from reaction system, and analytical reactions are mixed
Compound, isobutylaldehyde conversion rate 90%, selective 95%, vacuum distillation removes unreacted isobutylaldehyde, continues to collect content
More than 99.5% product Lauryl Alcohol ester.
Embodiment 7
By 72g isobutylaldehydes, the compounding solid catalyst (carrier of the sodium alkoxide of load：Molecular sieve, m (sodium methoxides/ethanol
Sodium)：M (molecular sieve)=1), 3g and hydroxide 1- butyl -3- methylimidazole 9g is added to being furnished with condensation pipe heating device
In 500mL four-hole bottles, 85 DEG C are heated to, stirring reaction 3h is cooled to room temperature, and filtration isolates catalyst from reaction system
Go, analytical reactions mixture, isobutylaldehyde conversion rate 98%, selective 90% vacuum distillation removes unreacted isobutylaldehyde, continues
Collect the product Lauryl Alcohol ester of content more than 99.5%.
Embodiment 8
By 72g isobutylaldehydes, the triethylamine compounding solid catalyst (carrier of load：Silica gel, m (triethylamine)：M (silica gel)
=0.8), 3g and hydroxide 1- butyl -3- methylimidazole 9g is added to the 500mL four-hole bottles for being furnished with condensation pipe heating device
In, 85 DEG C are heated to, stirring reaction 3h is cooled to room temperature, and filtration separates catalyst from reaction system, and analytical reactions are mixed
Compound, isobutylaldehyde conversion rate 91%, selective 90% vacuum distillation removes unreacted isobutylaldehyde, continues to collect content 99.5%
Product Lauryl Alcohol ester above.
Comparative example
72g isobutylaldehydes, sodium hydrate solid catalyst 2.2g are added to tetra- mouthfuls of 500mL for being furnished with condensation pipe heating device
In bottle, 60 DEG C are heated to, stirring reaction 4h is cooled to room temperature, and vacuum distillation removes unreacted isobutylaldehyde, and reactant liquor is washed,
It is dried, analytical reactions mixture, isobutylaldehyde conversion rate 70%, selective 75%, continues the product 12 for collecting content 90.5%
Carbon alcohol ester.
By 72g isobutylaldehydes, sodium hydrate solid catalyst 2.2g, hydroxide 1- butyl -3- methylimidazole 7.2g add to
In being furnished with the 500mL four-hole bottles of condensation pipe heating device, 60 DEG C are heated to, stirring reaction 4h is cooled to room temperature, filtering will catalysis
Agent is separated from reaction system, analytical reactions mixture, isobutylaldehyde conversion rate 90%, and selective 85%, vacuum distillation is removed
Unreacted isobutylaldehyde, continues the product Lauryl Alcohol ester for collecting content 97.5%.
72g isobutylaldehydes, sodium methoxide solid catalyst 2.2g are added to the 500mL four-hole bottles for being furnished with condensation pipe heating device
In, 60 DEG C are heated to, stirring reaction 4h is cooled to room temperature, and vacuum distillation removes unreacted isobutylaldehyde, and reactant liquor washing is done
It is dry, analytical reactions mixture, isobutylaldehyde conversion rate 80%, selective 75%, continue the product Lauryl Alcohol for collecting content 91%
Ester.
By 72g isobutylaldehydes, sodium methoxide solid catalyst 2.2g, hydroxide 1- butyl -3- methylimidazole 7.2g are added to matching somebody with somebody
In there are the 500mL four-hole bottles of condensation pipe heating device, 60 DEG C are heated to, stirring reaction 4h is cooled to room temperature, and vacuum distillation is removed
Unreacted isobutylaldehyde, reactant liquor washing, is dried, analytical reactions mixture, isobutylaldehyde conversion rate 90%, and selective 85%, after
The continuous product Lauryl Alcohol ester for collecting content 98.5%.
Claims (7)
1. a kind of method for preparing Lauryl Alcohol ester, it is characterised in that straight in catalyst action next step with isobutylaldehyde as raw material
Connect and prepare Lauryl Alcohol ester, catalyst is the dual catalyst system that load-type solid and alkali ionic liquid are constituted.
2. method according to claim 1, wherein the support type base catalyst selected from NaOH, potassium hydroxide,
Potassium carbonate, calcium nitrate, calcium carbonate, calcium acetate and calcium chloride, load on the load being selected from the group：Alundum (Al2O3), activity
Charcoal and montmorillonite；Or support type base catalyst is selected from potassium oxide, calcium oxide, triethylamine, sodium methoxide and caustic alcohol, load
To on the load being selected from the group：Silica gel, molecular sieve.
3. method according to claim 1, wherein the alkali ionic liquid is selected from hydroxide 1- butyl -3- methyl miaows
Azoles, hydroxide 1- ethyl-3-methylimidazoles and hydroxide 1- methyl -3- methylimidazoles.
4. method according to claim 1, it is characterised in that in mass the consumption of load type solid body base catalyst is different
The 1%-5% of butyraldehyde.
5. method according to claim 1, it is characterised in that in mass the consumption of alkali ionic liquid is isobutylaldehyde
5%-20%.
6. method according to claim 1, it is characterised in that at 40-100 DEG C, the reaction time is 2-10h to reaction temperature.
7. method according to claim 1, it is characterised in that reaction temperature is 80 DEG C or 90 DEG C.
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Cited By (7)
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| CN107382717A (en) * | 2017-07-21 | 2017-11-24 | 邹平县嘉源复合材料厂 | A kind of micro passage reaction prepares the continuous process of Lauryl Alcohol ester |
| CN107673975A (en) * | 2017-06-20 | 2018-02-09 | 兰州石化职业技术学院 | A kind of method for synthesizing the pentanediol mono isobutyrate of 2,2,4 trimethyl 1,3 |
| CN109174176A (en) * | 2018-08-01 | 2019-01-11 | 沈阳工业大学 | Alkaline ionic liquid catalyst and preparation method thereof |
| CN109305912A (en) * | 2018-06-12 | 2019-02-05 | 中溶科技股份有限公司 | The method for preparing 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate is condensed by isobutylaldehyde |
| CN111943842A (en) * | 2020-06-05 | 2020-11-17 | 姜鹏 | Method for preparing dodecyl alcohol ester |
| CN111992247A (en) * | 2020-08-20 | 2020-11-27 | 润泰化学（泰兴）有限公司 | Preparation method of graft catalyst for continuous catalytic synthesis of isobutyl isobutyrate |
| CN113385163A (en) * | 2021-06-16 | 2021-09-14 | 西南林业大学 | Foam carbon heterogeneous solid base catalyst for grease transesterification and preparation method thereof |
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| CN107673975A (en) * | 2017-06-20 | 2018-02-09 | 兰州石化职业技术学院 | A kind of method for synthesizing the pentanediol mono isobutyrate of 2,2,4 trimethyl 1,3 |
| CN107382717A (en) * | 2017-07-21 | 2017-11-24 | 邹平县嘉源复合材料厂 | A kind of micro passage reaction prepares the continuous process of Lauryl Alcohol ester |
| CN109305912A (en) * | 2018-06-12 | 2019-02-05 | 中溶科技股份有限公司 | The method for preparing 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate is condensed by isobutylaldehyde |
| CN109174176A (en) * | 2018-08-01 | 2019-01-11 | 沈阳工业大学 | Alkaline ionic liquid catalyst and preparation method thereof |
| CN109174176B (en) * | 2018-08-01 | 2021-07-06 | 沈阳工业大学 | Basic ionic liquid catalyst and preparation method thereof |
| CN111943842A (en) * | 2020-06-05 | 2020-11-17 | 姜鹏 | Method for preparing dodecyl alcohol ester |
| CN111992247A (en) * | 2020-08-20 | 2020-11-27 | 润泰化学（泰兴）有限公司 | Preparation method of graft catalyst for continuous catalytic synthesis of isobutyl isobutyrate |
| CN111992247B (en) * | 2020-08-20 | 2022-11-22 | 润泰化学（泰兴）有限公司 | Preparation method of graft catalyst for continuous catalytic synthesis of isobutyl isobutyrate |
| CN113385163A (en) * | 2021-06-16 | 2021-09-14 | 西南林业大学 | Foam carbon heterogeneous solid base catalyst for grease transesterification and preparation method thereof |
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