CN115433077B - Preparation of 11-bromoundecanoic acid from 10-undecanoic acid and preparation method thereof - Google Patents
Preparation of 11-bromoundecanoic acid from 10-undecanoic acid and preparation method thereof Download PDFInfo
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- IUDGNRWYNOEIKF-UHFFFAOYSA-N 11-bromo-undecanoic acid Chemical compound OC(=O)CCCCCCCCCCBr IUDGNRWYNOEIKF-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000003999 initiator Substances 0.000 claims abstract description 72
- 239000002904 solvent Substances 0.000 claims abstract description 54
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 52
- 239000007789 gas Substances 0.000 claims abstract description 48
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims description 90
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- 239000012295 chemical reaction liquid Substances 0.000 claims description 34
- 238000004821 distillation Methods 0.000 claims description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 14
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000007259 addition reaction Methods 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 6
- 230000031709 bromination Effects 0.000 claims description 5
- 238000005893 bromination reaction Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002826 coolant Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- -1 organic peroxide compound Chemical class 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 5
- PZRZUJZXSTZDBZ-UHFFFAOYSA-N 11-bromoundec-10-enoic acid Chemical compound OC(=O)CCCCCCCCC=CBr PZRZUJZXSTZDBZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 11
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- 238000005915 ammonolysis reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 4
- 229920000571 Nylon 11 Polymers 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- FPVSUJTZRASPAK-UHFFFAOYSA-N (2,3-dimethylbenzoyl) 2,3-dimethylbenzenecarboperoxoate Chemical compound CC1=CC=CC(C(=O)OOC(=O)C=2C(=C(C)C=CC=2)C)=C1C FPVSUJTZRASPAK-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- RECMXUUCYFGBEZ-UHFFFAOYSA-N cyclohexyl cyclohexyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC1CCCCC1 RECMXUUCYFGBEZ-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- AMEVLYGGLRIBIO-UHFFFAOYSA-N octoxycarbonyloxy octyl carbonate Chemical compound CCCCCCCCOC(=O)OOC(=O)OCCCCCCCC AMEVLYGGLRIBIO-UHFFFAOYSA-N 0.000 description 2
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229960002703 undecylenic acid Drugs 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
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 11-bromoundecanoic acid from 10-undecanoic acid, which comprises the following raw materials: 10-undecylenic acid, solvent, initiator and hydrogen bromide gas; the initiator consists of a main initiator and a co-initiator, wherein the main initiator is an organic peroxide compound, the co-initiator is a tertiary amine compound, the mass ratio of the main initiator to the co-initiator is 0.2-5:1, the total use amount of the initiator is 0.5-4% of the mass of 10-undecylenic acid, and the selectivity of 11-bromoundecylenic acid is improved by adopting a composite initiator, so that the yield of 11-bromoundecylenic acid is improved. The method adopts a reactor form of tower type and kettle type series connection, fully utilizes the advantages of the two reactors, and improves the yield of 11-bromoundecanoic acid.
Description
Technical Field
The invention belongs to the technical field of long carbon chain nylon production, and particularly relates to a method for preparing 11-bromoundecanoic acid from 10-undecanoic acid.
Background
The 11-bromoundecanoic acid is mainly used for synthesizing nylon 11 monomer-11-aminoundecanoic acid, nylon 11 is also called polyamide 11 (poly-omega-aminoundecanoic), is produced by taking bio-based castor oil as a raw material, belongs to bio-based long carbon chain special nylon, has the excellent characteristics of low density, high mechanical strength, good shock resistance, low temperature resistance, oil resistance and the like, and is widely applied to the fields of automobiles, electronic appliances, military industry and the like.
Nylon 11 is a kind of special engineering plastic, and has the advantages of high lubricity, wear resistance, compression resistance, easy processing, toughness, softness, low water absorption, high size stability, excellent dielectric property, high wear resistance, low density, etc.
The domestic 11-bromoundecanoic acid is prepared by the bromoaddition of 10-undecanoic acid and hydrogen bromide usually takes benzene or a mixture of benzene and toluene as a solvent, benzoyl peroxide or azodiisobutyronitrile as an initiator, firstly, the 10-undecanoic acid is dissolved in the solvent, then the reaction product is subjected to the anti-Mahalation with hydrogen bromide gas to generate the 11-bromoundecanoic acid, and then the 11-bromoundecanoic acid is obtained through water washing and freezing crystallization. The Chinese patent CN1100030C mixes undecylenic acid, toluene liquid and catalyst according to the proportion of 1:2-4:0.005-0.01, and makes them react in two reaction kettles at-5-15 deg.C, and the reaction time is long, its reaction time is about 8 hr, and its reaction efficiency is low. Chinese patent CN200810055093.2 prepares 10-undecylenic acid and toluene solution into toluene solution of 10-undecylenic acid according to the mass ratio of 1:3-4, and then reacts with hydrogen bromide gas in a packed tower with jacket cooling in a continuous reverse contact manner to generate 11-bromoundecylenic acid. The bromoaddition reaction of 10-undecylenic acid is free radical addition reaction, and the satisfactory yield can be achieved only by the participation of an initiator, and the patent does not use the initiator, and the reaction is completed only in a packed tower, so that the reaction time is short, and a good effect is difficult to obtain. The bromination addition reaction of 10-undecylenic acid in Chinese patent CN103804209B adopts a mixture of toluene and benzene as a solvent, azodiisobutyronitrile or benzoyl peroxide as an initiator, and hydrogen bromide is reacted in two kettle reactors, the bromination addition reaction of 10-undecylenic acid and hydrogen bromide is a gas-liquid contact reaction, and a contact mass transfer interface is required to be as large as possible, but the patent adopts the kettle reactors, the contact interface of hydrogen bromide gas and 10-undecylenic acid is small, the reaction speed is slow, the hydrogen bromide waste is large, benzene is adopted as a solvent, and benzene is an extremely harmful medium and is easy to cause cancer, and the application is limited.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and providing a method for preparing 11-bromoundecanoic acid from 10-undecanoic acid, which can improve the yield of 11-bromoundecanoic acid.
To achieve the above object, the present invention provides a process for preparing 11-bromoundecanoic acid from 10-undecanoic acid, which comprises the steps of: 10-undecylenic acid, solvent, initiator and hydrogen bromide gas; the initiator consists of a main initiator and a co-initiator, wherein the main initiator is an organic peroxide compound, the co-initiator is a tertiary amine compound, and the mass ratio of the main initiator to the co-initiator is 0.2-5: 1, the total usage amount of the initiator is 0.5-4% of the mass of 10-undecylenic acid.
Further, the mass ratio of the solvent to the 10-undecylenic acid is 4-6:1.
Further, the molar ratio of the hydrogen bromide gas to the 10-undecylenic acid is 1.05-1.5:1.
Further, the organic peroxide compound is one or a mixture of more of benzoyl peroxide, lauroyl peroxide, dimethylbenzoyl peroxide, dicyclohexyl peroxycarbonate, dipropyl peroxydicarbonate, dioctyl peroxydicarbonate, dicumyl peroxide and di-tert-butyl peroxide; the tertiary amine compound is one or a mixture of more of N, N-dimethylaniline, N-dimethyl-p-toluidine, N-diethylaniline, N-methylmorpholine and N-ethylmorpholine.
Further, the solvent is one or a mixture of toluene, benzene, chlorobenzene, methylcyclohexane, cyclohexane, petroleum ether, 1, 4-dioxane, cyclohexanone, N-dimethylformamide and cycloheptane.
Also provided is a process for preparing 11-bromoundecanoic acid from 10-undecanoic acid as described above as follows:
after 10-undecylenic acid is sent into a batching kettle, a solvent is added, and meanwhile, an initiator is added into the batching kettle to be mixed and prepared into a reaction solution;
cooling the reaction liquid through a discharge hole of a batching kettle, pumping into a feed inlet at the top of a charging hopper Cheng Da through an addition feeding pump, filling filler in the charging hopper Cheng Da, and simultaneously introducing hydrogen bromide gas from the bottom of the charging hopper Cheng Da; the reaction liquid is in countercurrent contact with hydrogen bromide gas, and a bromination addition reaction is carried out on the surface of a filler in the addition tower;
the reaction solution automatically flows into the reaction kettle from the bottom of the adding Cheng Da, meanwhile, hydrogen bromide gas is introduced into the bottom of the reaction kettle, and the reaction solution stays in the reaction kettle to further react with the hydrogen bromide;
the reaction liquid at the outlet of the bottom of the reaction kettle flows to the solvent distillation kettle, the solvent is distilled out for recycling under the vacuum condition, and the kettle bottom liquid of the solvent distillation kettle is 11-bromoundecanoic acid.
Further, the reaction liquid is cooled to 0-10 ℃ through a discharge hole of the batching kettle.
Further, a jacket is arranged on the outer surface of the addition tower, and the reaction temperature of the addition tower is controlled to be 10-30 ℃ by adjusting the flow of a cooling medium in the jacket; the reaction kettle is provided with a stirrer and a jacket, the temperature in the reaction kettle is controlled to be 30-50 ℃ by adjusting the flow of a heating medium in the jacket, and the reaction liquid is further reacted with hydrogen bromide under the stirring action of the reaction kettle.
Further, the hydrogen bromide gas is introduced in two ways: firstly, introducing hydrogen bromide gas to the bottom of a reaction kettle, and allowing a part of hydrogen bromide gas to enter an addition tower from a feed inlet at the top of the reaction kettle through a discharge outlet at the bottom of an addition Cheng Da; and secondly, two branches are respectively introduced into the bottom of the adding Cheng Da and the bottom of the reaction kettle.
Further, the solvent distillation kettle is provided with a stirrer and a jacket, and the temperature in the solvent distillation kettle is controlled to be 80-110 ℃ and the absolute pressure is controlled to be 50-80 KPa.
Compared with the prior art, the invention has the following advantages: the invention adopts the composite initiator to improve the selectivity of 11-bromoundecanoic acid, thereby improving the yield of 11-bromoundecanoic acid; the method adopts a reactor form of tower type and kettle type series connection, fully utilizes the advantages of the two reactors, and improves the yield of 11-bromoundecanoic acid; and the process is reliable, the product yield is high, the operation cost is low, the environmental pollution is less, and the continuous and stable industrial production can be realized.
Drawings
FIG. 1 is a schematic diagram of the process flow for preparing 11-bromoundecanoic acid from 10-undecanoic acid according to the present invention.
Detailed Description
The invention will now be described in further detail with reference to the drawings and to specific examples.
Preparation of 11-bromoundecanoic acid from 10-undecanoic acid as shown in FIG. 1, starting materials include: 10-undecylenic acid, solvent, initiator and hydrogen bromide gas; the mass ratio of the solvent to the 10-undecylenic acid is 4-6:1, and the molar ratio of the hydrogen bromide gas to the 10-undecylenic acid is 1.05-1.5:1. The key points of the invention are as follows: the initiator consists of a main initiator and a co-initiator, wherein the main initiator is an organic peroxide compound, the co-initiator is a tertiary amine compound, the mass ratio of the main initiator to the co-initiator is 0.2-5:1, and the total dosage of the initiator is 0.5-4% of the mass of 10-undecylenic acid. The solvent is one or more of toluene, benzene, chlorobenzene, methylcyclohexane, cyclohexane, petroleum ether, 1, 4-dioxane, cyclohexanone, N-dimethylformamide and cycloheptane; the organic peroxide compound is one or more of benzoyl peroxide, lauroyl peroxide, dimethylbenzoyl peroxide, dicyclohexyl peroxycarbonate, dipropyl peroxydicarbonate, dioctyl peroxydicarbonate, dicumyl peroxide and di-tert-butyl peroxide; the tertiary amine compound is one or a mixture of more of N, N-dimethylaniline, N-dimethyl-p-toluidine, N-diethylaniline, N-methylmorpholine and N-ethylmorpholine. The selectivity of 11-bromoundecanoic acid is improved by adopting a composite initiator, so that the yield of 11-bromoundecanoic acid is improved.
The process flow of 11-bromoundecanoic acid prepared from 10-undecanoic acid as shown in fig. 1 comprises a batching kettle 1, an addition feeding pump 2, an addition Cheng Da 3, a reaction kettle 4, a solvent distillation kettle 5 and a bromoacid delivery pump 6 which are connected in sequence. The discharge gate of batching cauldron 1 links to each other with the top feed inlet of addition tower 3 through addition feed pump 2, and the discharge gate of adding Cheng Da 3 bottom links to each other with the feed inlet at reation kettle 4 top, and the discharge gate at reation kettle 4 bottom links to each other with the feed inlet at solvent distillation cauldron 5 top, and the discharge gate at solvent distillation cauldron 5 bottom links to each other with bromoacid delivery pump 6, carries material 11-bromoundecanoic acid downstream process through bromoacid delivery pump 6.
10-undecylenic acid is sent into a batching kettle 1, a solvent is added at the same time, the mass part ratio of the solvent addition amount to the 10-undecylenic acid is 4-6:1, and a composite initiator is added into the batching kettle 1 to be mixed to prepare a reaction liquid.
The reaction liquid is cooled to 0-10 ℃ through a discharge hole of a batching kettle 1, then is sent into a feed inlet at the top of a adding Cheng Da through an addition feed pump 2, a filler is filled in the adding Cheng Da, a jacket is arranged on the outer surface of the adding Cheng Da, the reaction temperature of the adding tower 3 is controlled to be 10-30 ℃ (preferably 10-20 ℃) by adjusting the flow of a cooling medium in the jacket, and meanwhile, hydrogen bromide gas is introduced from the bottom of the adding tower 3; the reaction liquid is in countercurrent contact with hydrogen bromide gas, and a bromination addition reaction is carried out on the surface of the filler in the addition tower 3;
the reaction solution automatically flows into the reaction kettle 4 from the bottom of the addition tower 3, meanwhile, hydrogen bromide gas is introduced into the bottom of the reaction kettle 4, the reaction kettle 4 is provided with a stirrer and a jacket, the temperature in the reaction kettle 4 is controlled to be 30-50 ℃ (preferably 30-40 ℃) by adjusting the flow of a heating medium in the jacket, the reaction solution stays in the reaction kettle 4 for 0.5-1 h, and the reaction solution further reacts with the hydrogen bromide under the stirring action of the reaction kettle 4, so that the reaction solution can stay in the reaction kettle 4 for a long time, and the conversion rate of 10-undecylenic acid is improved.
The hydrogen bromide gas can be introduced in two ways: firstly, introducing hydrogen bromide gas into the bottom of the reaction kettle 4, wherein a part of the hydrogen bromide gas enters the addition tower 3 from a feed inlet at the top of the reaction kettle 4 through a discharge hole at the bottom of the addition tower 3, and secondly, introducing the hydrogen bromide gas into the bottom of the addition tower 3 and the bottom of the reaction kettle 4 in two ways respectively.
The reaction liquid at the bottom outlet of the reaction kettle 4 automatically flows to the solvent distillation kettle 5, the solvent distillation kettle 5 is provided with a stirrer and a jacket, the temperature in the solvent distillation kettle 5 kettle is controlled to be 80-110 ℃, the absolute pressure is controlled to be 50-80 KPa, the solvent is distilled out for recycling under the vacuum condition, the stirring can accelerate the solvent evaporation, the kettle bottom liquid of the solvent distillation kettle 5 is 11-bromoundecanoic acid, and the 11-bromoundecanoic acid is sent to the subsequent ammonolysis process for treatment through a bromoacid conveying pump 6.
The 10-undecylenic acid, the initiator and the solvent are prepared into a reaction solution, the reaction solution contacts with hydrogen bromide gas in a reactor formed by connecting an addition tower and a reaction kettle in series, and the reaction solution is generated by anti-Mahalanobis addition reaction. The method adopts a reactor form of tower type and kettle type series connection, fully utilizes the advantages of the two reactors, and improves the yield of 11-bromoundecanoic acid; the selectivity of 11-bromoundecanoic acid is improved by adopting a composite initiator, so that the yield of 11-bromoundecanoic acid is improved.
Example 1
10-undecylenic acid is fed into a batching kettle 1, toluene is added, the mass part ratio of toluene to 10-undecylenic acid is 4:1, an initiator is added and mixed to form a reaction liquid, the initiator consists of lauroyl peroxide as a main initiator and N, N-diethylaniline as a co-initiator, the mass part ratio of lauroyl peroxide to N, N-diethylaniline is 1:0.5, and the use amount of the initiator is 1% of the mass of 10-undecylenic acid.
Cooling the reaction liquid to 10 ℃ through a discharge hole of a batching kettle 1, then sending the reaction liquid into a feed inlet at the top of a adding Cheng Da through an adding feed pump 2, simultaneously introducing hydrogen bromide gas from the bottom of an adding tower 3, and regulating the temperature of the adding tower 3 to be controlled at 10-15 ℃; the reaction liquid flows into the reaction kettle 4 from the bottom of the addition tower 3, and meanwhile, hydrogen bromide gas is introduced into the bottom of the reaction kettle 4, and the temperature of the reaction kettle 4 is controlled at 32 ℃.
The hydrogen bromide gas is respectively introduced into the bottom of the addition tower 3 and the bottom of the reaction kettle 4 in two ways, and the volume flow of the hydrogen bromide gas introduced into the addition tower 3 is 70-75% of the total volume flow of the hydrogen bromide gas. The reaction liquid of the reaction kettle 4 overflows to a solvent distillation kettle 5, low-pressure steam is introduced into a jacket of the solvent distillation kettle 5, the temperature in the kettle is controlled to be 92-96 ℃, the pressure in the kettle is 50KPa (absolute pressure), the solvent is distilled out for recycling, and the kettle bottom liquid is 11-bromoundecanoic acid and is sent to an ammonolysis process. The content of 11-bromoundecanoic acid and the content of 10-undecanoic acid in the product are measured by a gas chromatograph, the conversion rate of the raw material and the selectivity of the target product are calculated, the conversion rate of the 10-undecanoic acid is 98.8%, the selectivity of the 11-bromoundecanoic acid is 96.7% and the yield of the 11-bromoundecanoic acid is 95.5% through detection.
Example 2
10-undecylenic acid is fed into a batching kettle 1, toluene is added, the mass part ratio of toluene to 10-undecylenic acid is 4:1, an initiator is added and mixed to form a reaction liquid, the initiator consists of lauroyl peroxide as a main initiator and N, N-diethylaniline as a co-initiator, the mass part ratio of lauroyl peroxide to N, N-diethylaniline is 1:1, and the use amount of the initiator is 1% of the mass of 10-undecylenic acid.
The reaction liquid is cooled to 15 ℃ through a discharge hole of the batching kettle 1, then is fed into a feed inlet at the top of a feeding pump Cheng Da 3 through an addition feeding pump 2, and the temperature of the feeding pump Cheng Da is regulated to be controlled between 15 and 20 ℃; simultaneously, hydrogen bromide gas is introduced into the reaction kettle 4, and enters the addition tower 3 through a connecting pipeline of the addition tower 3 and the reaction kettle 4, and the temperature of the reaction kettle 4 is controlled at 35 ℃.
The reaction liquid of the reaction kettle 4 overflows to a solvent distillation kettle 5, low-pressure steam is introduced into a jacket of the solvent distillation kettle 5, the temperature in the kettle is controlled to be 92-96 ℃, the pressure in the kettle is 50KPa (absolute pressure), the solvent is distilled out for recycling, and the kettle bottom liquid is 11-bromoundecanoic acid and is sent to an ammonolysis process. The content of 11-bromoundecanoic acid and the content of 10-undecanoic acid in the product are measured by a gas chromatograph, the conversion rate of the raw material and the selectivity of the target product are calculated, the conversion rate of the 10-undecanoic acid is 99.0% by detection, the selectivity of the 11-bromoundecanoic acid is 95.4%, and the yield of the 11-bromoundecanoic acid is 94.4%.
Example 3
10-undecylenic acid is fed into a batching kettle 1, toluene is added, the mass part ratio of toluene to 10-undecylenic acid is 4:1, an initiator is added and mixed to form a reaction liquid, the initiator consists of lauroyl peroxide as a main initiator and N, N-diethylaniline as a co-initiator, the mass part ratio of lauroyl peroxide to N, N-diethylaniline is 1:0.5, and the use amount of the initiator is 1.5% of the mass of 10-undecylenic acid.
Cooling the reaction liquid to 10 ℃ through a discharge hole of a batching kettle 1, then sending the reaction liquid into a feed inlet at the top of a adding Cheng Da through an adding feed pump 2, simultaneously introducing hydrogen bromide gas from the bottom of the adding tower 3, and regulating the temperature of the adding tower 3 to be controlled at 18-22 ℃; the reaction liquid flows into the reaction kettle 4 from the bottom of the addition tower 3, and meanwhile, hydrogen bromide gas is introduced into the bottom of the reaction kettle 4, and the temperature of the reaction kettle 4 is controlled at 30 ℃.
The hydrogen bromide gas is respectively introduced into the bottom of the addition tower 3 and the bottom of the reaction kettle 4 in two ways, and the volume flow of the hydrogen bromide gas introduced into the addition tower 3 is 70-75% of the total volume flow of the hydrogen bromide gas. The reaction liquid of the reaction kettle 4 overflows to a solvent distillation kettle 5, low-pressure steam is introduced into a jacket of the solvent distillation kettle 5, the temperature in the kettle is controlled to be 92-96 ℃, the pressure in the kettle is 50KPa (absolute pressure), the solvent is distilled out for recycling, and the kettle bottom liquid is 11-bromoundecanoic acid and is sent to an ammonolysis process. The content of 11-bromoundecanoic acid and the content of 10-undecanoic acid in the product are measured by a gas chromatograph, the conversion rate of the raw material and the selectivity of the target product are calculated, the conversion rate of the 10-undecanoic acid is 98.6 percent, the selectivity of the 11-bromoundecanoic acid is 97.4 percent, and the yield of the 11-bromoundecanoic acid is 96.04 percent.
Comparative example 1
And (3) feeding 10-undecylenic acid into a batching kettle 1, simultaneously adding a solvent toluene, wherein the mass part ratio of the toluene addition amount to the 10-undecylenic acid is 4:1, simultaneously adding an initiator, mixing to form a reaction solution, wherein the initiator is lauroyl peroxide, no auxiliary initiator is added, and the use amount of the initiator is 1% of the mass of the 10-undecylenic acid.
The reaction liquid is cooled to 10 ℃ through a discharge hole of the batching kettle 1, then is fed into a feed inlet at the top of a feeding pump Cheng Da 3 through an addition feeding pump 2, and the temperature of the feeding pump Cheng Da is regulated to be controlled between 10 and 15 ℃; the reaction liquid flows into the reaction kettle 4 from the bottom of the addition tower 3, and meanwhile, hydrogen bromide gas is introduced into the reaction kettle 4, and enters the addition tower 3 through a connecting pipeline of the addition tower 3 and the reaction kettle 4, and the temperature of the reaction kettle 4 is controlled at 32 ℃.
The reaction liquid of the reaction kettle 4 overflows to a solvent distillation kettle 5, low-pressure steam is introduced into a jacket of the solvent distillation kettle 5, the temperature in the kettle is controlled to be 92-96 ℃, the pressure in the kettle is 50KPa (absolute pressure), the solvent is distilled out for recycling, and the kettle bottom liquid is 11-bromoundecanoic acid and is sent to an ammonolysis process. The content of 11-bromoundecanoic acid and the content of 10-undecanoic acid in the product are measured by a gas chromatograph, the conversion rate of the raw material and the selectivity of the target product are calculated, the conversion rate of the 10-undecanoic acid is 93.6% by detection, the selectivity of the 11-bromoundecanoic acid is 94.7%, and the yield of the 11-bromoundecanoic acid is 88.64%.
Comparative example 2
And (3) feeding 10-undecylenic acid into a batching kettle 1, simultaneously adding a solvent toluene, wherein the mass part ratio of the toluene to the 10-undecylenic acid is 4:1, simultaneously adding an initiator, mixing to form a reaction liquid, wherein the initiator is lauroyl peroxide, no auxiliary initiator is added, and the use amount of the initiator is 1% of the mass of the 10-undecylenic acid.
The reaction liquid is cooled to 10 ℃ through a discharge hole of the batching kettle 1, then is fed into a feed inlet at the top of a feeding pump Cheng Da 3 through an addition feeding pump 2, and the temperature of the feeding pump Cheng Da is regulated to be controlled between 30 and 32 ℃; the reaction liquid flows into the reaction kettle 4 from the bottom of the addition tower 3, and meanwhile, hydrogen bromide gas is introduced into the reaction kettle 4, and enters the addition tower 3 through a connecting pipeline of the addition tower 3 and the reaction kettle 4, and the temperature of the reaction kettle 4 is controlled at 32 ℃.
The reaction liquid of the reaction kettle 4 overflows to a solvent distillation kettle 5, low-pressure steam is introduced into a jacket of the solvent distillation kettle 5, the temperature in the kettle is controlled to be 92-96 ℃, the pressure in the kettle is 50KPa (absolute pressure), the solvent is distilled out for recycling, and the kettle bottom liquid is 11-bromoundecanoic acid and is sent to an ammonolysis process. The content of 11-bromoundecanoic acid and the content of 10-undecanoic acid in the product are measured by a gas chromatograph, the conversion rate of the raw material and the selectivity of the target product are calculated, the conversion rate of the 10-undecanoic acid is detected to be 95.3%, the selectivity of the 11-bromoundecanoic acid is detected to be 89.2%, and the yield of the 11-bromoundecanoic acid is detected to be 85.0%.
Claims (9)
1. 11-bromoundecanoic acid is prepared from 10-undecanoic acid, characterized in that: the starting materials for preparing 11-bromoundecanoic acid from 10-undecanoic acid include: 10-undecylenic acid, solvent, initiator and hydrogen bromide gas; the initiator consists of a main initiator and a co-initiator, wherein the initiator consists of lauroyl peroxide as the main initiator and N, N-diethylaniline as the co-initiator, and the mass ratio of the main initiator to the co-initiator is 0.2-5: 1, the total usage amount of the initiator is 0.5-4% of the mass of 10-undecylenic acid.
2. The preparation of 11-bromoundecanoic acid from 10-undecanoic acid according to claim 1, characterized in that: the mass ratio of the solvent to the 10-undecylenic acid is 4-6:1.
3. The preparation of 11-bromoundecanoic acid from 10-undecanoic acid according to claim 1, characterized in that: the molar ratio of the hydrogen bromide gas to the 10-undecylenic acid is 1.05-1.5:1.
4. The preparation of 11-bromoundecanoic acid from 10-undecanoic acid according to claim 1, characterized in that: the solvent is one or more of toluene, benzene, chlorobenzene, methylcyclohexane, cyclohexane, petroleum ether, 1, 4-dioxane, cyclohexanone, N-dimethylformamide and cycloheptane.
5. A process for preparing 11-bromoundecanoic acid from 10-undecanoic acid according to claim 1, characterized in that: the preparation method comprises the following steps:
after 10-undecylenic acid is sent into a batching kettle (1), a solvent is added, and meanwhile, an initiator is added into the batching kettle (1) to be mixed and prepared into a reaction solution;
the reaction liquid is fed into a feed inlet at the top of a charging Cheng Da (3) through an addition feed pump (2) after being cooled through a discharge hole of a batching kettle (1), a filler is filled in the charging Cheng Da (3), and hydrogen bromide gas is introduced from the bottom of the charging Cheng Da (3); the reaction liquid is in countercurrent contact with hydrogen bromide gas, and a bromination addition reaction is carried out on the surface of the filler in the adding Cheng Da (3);
the reaction solution automatically flows into the reaction kettle (4) from the bottom of the adding Cheng Da (3), meanwhile, hydrogen bromide gas is introduced into the bottom of the reaction kettle (4), and the reaction solution stays in the reaction kettle (4) to further react with the hydrogen bromide;
the reaction liquid at the bottom outlet of the reaction kettle (4) automatically flows to the solvent distillation kettle (5), the solvent is distilled out for recycling under the vacuum condition, and the kettle bottom liquid of the solvent distillation kettle (5) is 11-bromoundecanoic acid.
6. The process for preparing 11-bromoundecanoic acid from 10-undecanoic acid according to claim 5, characterized in that: the reaction liquid is cooled to 0-10 ℃ through a discharge hole of the batching kettle (1).
7. The process for preparing 11-bromoundecanoic acid from 10-undecanoic acid according to claim 5, characterized in that: the outer surface of the adding Cheng Da (3) is provided with a jacket, and the reaction temperature of the adding tower (3) is controlled to be 10-30 ℃ by adjusting the flow of a cooling medium in the jacket; the reaction kettle (4) is provided with a stirrer and a jacket, the temperature in the reaction kettle (4) is controlled to be 30-50 ℃ by adjusting the flow of a heating medium in the jacket, and the reaction liquid is further reacted with hydrogen bromide under the stirring action of the reaction kettle (4).
8. The process for preparing 11-bromoundecanoic acid from 10-undecanoic acid according to claim 5, characterized in that: the hydrogen bromide gas is introduced in two ways: firstly, introducing hydrogen bromide gas to the bottom of a reaction kettle (4), and allowing a part of the hydrogen bromide gas to enter a charging Cheng Da (3) from a feeding hole at the top of the reaction kettle (4) through a discharging hole at the bottom of the charging Cheng Da (3); secondly, two flows are respectively introduced into the bottom of the adding Cheng Da (3) and the bottom of the reaction kettle (4).
9. The process for preparing 11-bromoundecanoic acid from 10-undecanoic acid according to claim 5, characterized in that: the solvent distillation kettle (5) is provided with a stirrer and a jacket, and the temperature in the solvent distillation kettle (5) is controlled to be 80-110 ℃ and the absolute pressure is controlled to be 50-80 KPa.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1010519B (en) * | 1952-08-07 | 1957-06-19 | Perfogit Societa Per Azioni | Process for the preparation of 11-bromundecanoic acid |
| CN1218793A (en) * | 1997-12-04 | 1999-06-09 | 范拥军 | Process for producing bromo-undecylic acid |
| CN103804209A (en) * | 2014-02-08 | 2014-05-21 | 中北大学 | Method for preparing 11-aminoundecanoic acid by utilizing 10-undecenoic acid |
| WO2021255387A1 (en) * | 2020-06-18 | 2021-12-23 | Arkema France | Method for producing aminoundecanoic acid and aminodecanoic acid |
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- 2022-09-19 CN CN202211136892.9A patent/CN115433077B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1010519B (en) * | 1952-08-07 | 1957-06-19 | Perfogit Societa Per Azioni | Process for the preparation of 11-bromundecanoic acid |
| CN1218793A (en) * | 1997-12-04 | 1999-06-09 | 范拥军 | Process for producing bromo-undecylic acid |
| CN103804209A (en) * | 2014-02-08 | 2014-05-21 | 中北大学 | Method for preparing 11-aminoundecanoic acid by utilizing 10-undecenoic acid |
| WO2021255387A1 (en) * | 2020-06-18 | 2021-12-23 | Arkema France | Method for producing aminoundecanoic acid and aminodecanoic acid |
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