CN101333161B - Method for preparing alpha-chloro-fatty acid - Google Patents
Method for preparing alpha-chloro-fatty acid Download PDFInfo
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- CN101333161B CN101333161B CN2008100212885A CN200810021288A CN101333161B CN 101333161 B CN101333161 B CN 101333161B CN 2008100212885 A CN2008100212885 A CN 2008100212885A CN 200810021288 A CN200810021288 A CN 200810021288A CN 101333161 B CN101333161 B CN 101333161B
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- chlorine
- fatty acid
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- 239000000194 fatty acid Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 30
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000460 chlorine Substances 0.000 claims abstract description 29
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 29
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 10
- 229930195729 fatty acid Natural products 0.000 claims abstract description 10
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229940123457 Free radical scavenger Drugs 0.000 claims description 11
- 239000002516 radical scavenger Substances 0.000 claims description 11
- 150000002632 lipids Chemical class 0.000 claims description 10
- 238000005260 corrosion Methods 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000010907 mechanical stirring Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000012805 post-processing Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000003963 antioxidant agent Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000000295 complement effect Effects 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 6
- 229940033355 lauric acid Drugs 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- LDQUHRSWFMWRNG-UHFFFAOYSA-N 2-chlorohexadecanoic acid Chemical class CCCCCCCCCCCCCCC(Cl)C(O)=O LDQUHRSWFMWRNG-UHFFFAOYSA-N 0.000 description 4
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 3
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 2
- -1 Bromo lipid Chemical class 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011430 maximum method Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001802 myricyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([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 1
- 238000010606 normalization Methods 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000011064 split stream procedure Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
An alpha-chloro-fatty acid preparation method belongs to the organic compound synthesis technical field. The invention takes chlorosulfonic acid as main catalyst, sulfur trioxide as complementary catalyst which is added in a continuous flow way, and uses oxygen in the air to replace pure oxygen to serve as free radical capture agent; the method enables fatty acid and chlorine to be reacted in an atmospheric pressure reactor so as to develop an ideal industrial production method for alpha-chloro-fatty acid production. The alpha-chloro of the invention has high reactivity, good reaction selectivity, high conversion rate, less side reaction products, as well as high purity of products so as to guarantee the catalytic activity in the reaction process and effectively prevent the increasing of the using amount of catalyst caused by decomposition of the main catalyst to result in waste; the method can reduce the insecure factors brought about by pure oxygen in industrial production and can avoid the increase of post-processing steps of products due to the introduction of chemical antioxidants.
Description
Technical field
A kind of preparation method of alpha-chloro-fatty acid; A kind of specifically is main catalyzer with chlorsulfonic acid; Even flow adds sulphur trioxide as cocatalyst; Replace pure oxygen as free radical scavenger with airborne oxygen, in normal pressure reactor, react the synthetic method that obtains alpha-chloro-fatty acid, belong to the organic cpds synthesis technical field with lipid acid and chlorine.
Background technology
Alpha-halogen lipid acid is because its high chemically reactive and as the important intermediate of fine chemicals such as synthetic dyestuff, agricultural chemicals, spices and medicine.Bromo lipid acid in the alpha-halogen lipid acid owing to be easy to preparation use more, chlorinated fatty acid synthetic and using then because low being restricted of chlorination activity.Acetate is as the simplest aliphatic acid that contains α-hydrogen.The reaction of its alpha-chloro early by broad research and application, the method for synthetic Monochloro Acetic Acid has a lot, the maximum method of the employing of industriallization at present prepares Mono Chloro Acetic Acid for catalysis acetate: promptly be raw material with acetate; Use sulphur, red phosphorus, acetic anhydride, Acetyl Chloride 98Min., chloroacetyl chloride, phosphorus trichloride etc. to be catalyzer, under certain temperature of reaction, chlorine is fed in the acetate; The control chlorination degree of depth; Acetate is become Mono Chloro Acetic Acid by chlorination, and chlorated liquid passes through crystallization again and gets rid of and filters the Mono Chloro Acetic Acid product, and this method advantage is that raw acetic acid is in liberal supply; Production technique is simple, the production less investment; Weak point is to control reaction well, and chloroacetic yield is lower, and the product of gained is the mixture of acetate, Mono Chloro Acetic Acid and dichloro acetic acid etc.
Though monochloro is for the study on the synthesis of acetate comparatively deeply and suitability for industrialized production; But longer chain fatty acid is because the chlorination activity is relatively low, and research report is less relatively, and priorities such as Yoshiro Ogata are catalyzer with Lewis acid such as sulfuric acid, hydrochloric acid or iron trichloride and chlorsulfonic acid; Meta-dinitrobenzene and oxygen are free radical scavenger; Reaction is studied to the alpha-chloro of laurostearic acid, but is to remove relatively difficulty of free radical scavenger after the free radical scavenger reaction with the Meta-dinitrobenzene, and the catalyzer usage quantity is on the high side; The productive rate of title product is lower, has brought difficulty for the aftertreatments such as purification of product; It is free radical scavenger that Robert J. has attempted with four cyano quinone bismethane (TCNQ), and chlorsulfonic acid is the alpha-chloro reaction of the longer chain fatty acid under the catalyzer condition, but the TCNQ synthesis step is comparatively loaded down with trivial details, is not to be the ideal free radical scavenger; Cost really also once reported with lipid acid to be raw material; N-chlorosuccinimide (NCS) is made chlorizating agent; Make the alpha-chloro longer chain fatty acid of sad, capric acid, laurostearic acid, though this compound method has good position specificity to the α-chlorination reaction of carboxylic acid, its catalyzer loses easily; And price comparison is expensive, also nonideal catalyzer; Fang Yun etc. is a catalyzer with the chlorsulfonic acid at the beginning of the nineties in 20th century and 21 century; Oxygen is that comparatively systematic research was done in the alpha-chloro reaction of free radical scavenger centering longer chain fatty acid (laurostearic acid, TETRADECONIC ACID, palmitic acid, stearic acid); Synthesized highly purified alpha-chloro longer chain fatty acid; But owing to be easy to decomposition failure behind the moisture in the chlorsulfonic acid ingress of air, thereby there are problems such as catalyst levels is on the high side equally.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of alpha-chloro-fatty acid; Selecting chlorsulfonic acid for use is main catalyzer; Even flow adds sulphur trioxide as cocatalyst; Replace pure oxygen as free radical scavenger with airborne oxygen, successfully solved the problem of above-mentioned several respects of present existence, developed a kind of method of comparatively ideal industrially producing alpha-chlorinated fatty acid.
The object of the invention can reach through following technical scheme: a kind of preparation method of alpha-chloro-fatty acid; With chlorsulfonic acid is main catalyzer; Even flow adds sulphur trioxide as cocatalyst, replaces pure oxygen as free radical scavenger with airborne oxygen, reacts in normal pressure reactor with lipid acid and chlorine; Synthetic obtain alpha-chloro-fatty acid, synthetic route is following:
R is C in the formula
0～C
30The alkyl of saturated, straight or branched.
Concrete building-up process is following:
In having the high length-diameter ratio reaction kettle of acid corrosion-resistant gas distributor, mechanical stirring and jacketed; Drop into drying fatty acid, heating makes it to melt and be warming up to 70～150 ℃ of temperature of reaction of setting, drips main catalyzer chlorsulfonic acid; Feed chlorine and Air mixing gas; Even flow adds sulphur trioxide behind the reaction 0.5-1.5h, and constant temperature stirs 3-5h under temperature of reaction again, and reaction finishes the back and drives residual chlorine gas with nitrogen; Cool to 50 ℃ of dischargings and remove catalyzer, obtain the thick product of alpha-chloro-fatty acid with the whizzer separation;
Described main catalyzer chlorsulfonic acid amount accounts for 0.1%～5% of lipid acid mass ratio, and cocatalyst sulphur trioxide amount accounts for 0.1%～5% of lipid acid mass ratio;
Described lipid acid: the molar ratio of chlorine is 1: 1～1: 3;
Chlorine in described chlorine and the Air mixing gas: the volume ratio of air is 10～1: 1.
Advantage of the present invention:
1. to select chlorsulfonic acid for use be main catalyzer in the present invention; Even flow adds sulphur trioxide as cocatalyst; Compare with several kinds of catalyzer of having reported that are used to prepare alpha-chloro-fatty acid, both can effectively prevent to make catalyst levels increase, cause the three wastes, can in reaction process, guarantee catalyst activity again because of Primary Catalysts decomposes; Have easy being easy to get; Advantage such as cheap, and its consumption can be controlled in the rational suitability for industrialized production scope, can make the post-processing steps such as purification of product relatively easy.
2. the present invention selects for use airborne oxygen as free radical scavenger; Be easy to get and reduce cost; Not only can reduce the unsafe factor that purity oxygen brought in the suitability for industrialized production; And can avoid increasing the post-processing step of product because of the introducing of chemical antioxidants, simplified the post-processing step of product.
3. reaction conditions of the present invention is gentle, and the alpha-chloro reaction has very high activity under normal pressure and lower temperature, good reaction selectivity, and transformation efficiency is high, and side reaction product is few, and the productive rate of title product is more than 95%.
Embodiment
Carry out the description of embodiment in the face of the present invention down, embodiment is following:
Synthesizing of embodiment 1 alpha-chloro caproic acid
In having the high length-diameter ratio reaction kettle of acid corrosion-resistant gas distributor, mechanical stirring and jacketed, drop into the dry caproic acid of 30g (0.26mol), heating makes it fusing and is warming up to 70 ℃; Drip the chlorsulfonic acid of 1.0g, feed the mixed gas of chlorine and air (chlorine is 1: 1 with volume of air flow ratio), the chlorine consumption is about 0.4mol; Even flow adds the 0.5g sulphur trioxide behind the reaction 1h; Constant temperature stirs 3h under temperature of reaction again, and reaction finishes the back and drives residual chlorine gas with nitrogen, cools to 50 ℃ of dischargings; Remove catalyzer with the whizzer separation, obtain the thick product of 40g alpha-chloro caproic acid.
Content analysis method is following:
Gc (GC) condition: the PEG-20000 capillary column (30m * 0.32mm); Fid detector; 200 ℃ of column temperatures; 280 ℃ of sampler temperature; 280 ℃ of detector temperatures; Carrier gas (N
2) flow 35mL/min; Split stream sampling not, sample size: 0.1 μ L.Adopt the quantitative analysis of peak area normalization method.
Take out 0.05～0.1g alpha-chloro caproic acid sample and put into the exsiccant test tube, add 1mL boron trifluoride/methanol solution, in boiling water bath, heat 5min.Be cooled to room temperature, add the 1mL anhydrous diethyl ether, thermal agitation makes methyl esters change the ether layer over to, adds an amount of saturated aqueous common salt, leaves standstill.After treating the solution layering, get upper strata ether layer sample, solvent evaporated is subsequent use.
With esterification product break into portions, keep 1 part of former state, all the other add the corresponding methyl caproate of different ratios, form one group of sample sets.Peak area ratio calculates the content of alpha-chloro methyl caproate in the esterification sample in the group per sample, thereby draws the productive rate of alpha-chloro caproic acid.Through gas chromatographic analysis, the alpha-chloro productive rate of acid is 95.7%.
Synthesizing of embodiment 2 alpha-chloro laurostearic acids
In having the high length-diameter ratio reaction kettle of acid corrosion-resistant gas distributor, mechanical stirring and jacketed; Drop into the dry laurostearic acid of 100g (0.5mol), heating makes it fusing and is warming up to 120 ℃, drips the chlorsulfonic acid of 1.0g; Feed the mixed gas of chlorine and air (chlorine is 2: 1 with volume of air flow ratio); The chlorine consumption is about 1.5mol, and even flow adds the 1.0g sulphur trioxide behind the reaction 0.5h, again constant temperature 3h under temperature of reaction; Reaction finishes the back and drives residual chlorine gas with nitrogen, cools to 50 ℃ of dischargings; Remove catalyzer with the separation of whizzer high speed centrifugation, obtain the thick product of 119g alpha-chloro laurostearic acid.Content analysis method is with embodiment 1, and the productive rate of alpha-chloro laurostearic acid is 96.4%.
Synthesizing of embodiment 3 alpha-chloro palmitic acids
In having the high length-diameter ratio reaction kettle of acid corrosion-resistant gas distributor, mechanical stirring and jacketed; Drop into the dry palmitic acid of 500g (1.95mol), heating makes it fusing and is warming up to 100 ℃, drips the chlorsulfonic acid of 3.0g; Feed the mixed gas of chlorine and air (chlorine is 5: 1 with volume of air flow ratio); The chlorine consumption is about 2.5mol, and even flow adds the 2.0g sulphur trioxide behind the reaction 1.5h, and constant temperature stirs 4h under temperature of reaction again; Reaction finishes the back and drives residual chlorine gas with nitrogen, cools to 50 ℃ of dischargings; Remove catalyzer with the whizzer separation, obtain the thick product of 570g alpha-chloro palmitic acid.Content analysis method is with embodiment 1, and the productive rate of alpha-chloro palmitic acid is 97.3%.
Synthesizing of embodiment 4 alpha-chloro Triple Pressed Stearic Acid (1840)
In having the high length-diameter ratio reaction kettle of acid corrosion-resistant gas distributor, mechanical stirring and jacketed; Drop into the dry Triple Pressed Stearic Acid of 600g (2.14mol), heating makes it fusing and is warming up to 130 ℃, drips the chlorsulfonic acid of 4.0g; Feed the mixed gas of chlorine and air (chlorine is 4: 1 with volume of air flow ratio); The chlorine consumption is about 4.3mol, and even flow adds the 5.0g sulphur trioxide behind the reaction 1.0h, and constant temperature stirs 3.5h under temperature of reaction again; Reaction finishes the back and drives residual chlorine gas with nitrogen, cools to 50 ℃ of dischargings; Remove catalyzer with the whizzer separation, obtain the thick product of 683g alpha-chloro Triple Pressed Stearic Acid (1840).The stearic overall yield of alpha-chloro palmitic acid and alpha-chloro is 96.8%.
Synthesizing of embodiment 5 alpha-chloro myricyl acids
In having the high length-diameter ratio reaction kettle of acid corrosion-resistant gas distributor, mechanical stirring and jacketed; Drop into the dry myricyl acid of 20g (0.043mol) (myricinic acid), heating makes it fusing and is warming up to 85 ℃, drips the chlorsulfonic acid of 0.5g; Feed the mixed gas of chlorine and air (chlorine is 1: 1 with volume of air flow ratio); The chlorine consumption is about 0.1mol, and even flow adds the 0.5g sulphur trioxide behind the reaction 0.5h, and constant temperature stirs 4h under temperature of reaction again; Reaction finishes the back and drives the chlorine that has neither part nor lot in reaction with nitrogen, cools to 50 ℃ of dischargings; Remove catalyzer with the whizzer separation, obtain the thick product of 21.7g alpha-chloro myricyl acid.Alpha-chloro myricyl acid productive rate is 95.3%.
Claims (1)
1. the preparation method of an alpha-chloro-fatty acid; It is characterized in that with chlorsulfonic acid be main catalyzer; Even flow adds sulphur trioxide as cocatalyst, replaces pure oxygen as free radical scavenger with airborne oxygen, reacts in normal pressure reactor with lipid acid and chlorine; Synthetic obtain alpha-chloro-fatty acid, synthetic route is following:
R is C in the formula
0～C
30The alkyl of saturated, straight or branched;
In having the high length-diameter ratio reaction kettle of acid corrosion-resistant gas distributor, mechanical stirring and jacketed; Drop into drying fatty acid, heating makes it to melt and be warming up to 70～150 ℃ of temperature of reaction of setting, drips main catalyzer chlorsulfonic acid; Feed chlorine and Air mixing gas; Even flow adds sulphur trioxide behind the reaction 0.5-1.5h, and constant temperature stirs 3-5h under temperature of reaction again, and reaction finishes the back and drives residual chlorine gas with nitrogen; Cool to 50 ℃ of dischargings and remove catalyzer, obtain the thick product of alpha-chloro-fatty acid with the whizzer separation;
Described main catalyzer chlorsulfonic acid amount accounts for 0.1%～5% of lipid acid mass ratio, and cocatalyst sulphur trioxide amount accounts for 0.1%～5% of lipid acid mass ratio;
Described lipid acid: the molar ratio of chlorine is 1: 1～1: 3;
Chlorine in described chlorine and the Air mixing gas: the volume ratio of air is 10～1: 1.
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