CN113292413A - Preparation method of 3-chloropropionic acid - Google Patents
Preparation method of 3-chloropropionic acid Download PDFInfo
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- CN113292413A CN113292413A CN202110637352.8A CN202110637352A CN113292413A CN 113292413 A CN113292413 A CN 113292413A CN 202110637352 A CN202110637352 A CN 202110637352A CN 113292413 A CN113292413 A CN 113292413A
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- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical compound OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 50
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 36
- 239000000047 product Substances 0.000 claims abstract description 34
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims abstract description 29
- 239000012043 crude product Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 26
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 17
- 239000012153 distilled water Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 25
- 230000035484 reaction time Effects 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 238000004042 decolorization Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- GAWAYYRQGQZKCR-REOHCLBHSA-N (S)-2-chloropropanoic acid Chemical compound C[C@H](Cl)C(O)=O GAWAYYRQGQZKCR-REOHCLBHSA-N 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000005660 chlorination reaction Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000012159 carrier gas Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 238000009834 vaporization Methods 0.000 description 6
- 230000008016 vaporization Effects 0.000 description 6
- LAMUXTNQCICZQX-UHFFFAOYSA-N 3-chloropropan-1-ol Chemical compound OCCCCl LAMUXTNQCICZQX-UHFFFAOYSA-N 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 238000005917 acylation reaction Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- -1 carbenium ion Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- INUNLMUAPJVRME-UHFFFAOYSA-N 3-chloropropanoyl chloride Chemical compound ClCCC(Cl)=O INUNLMUAPJVRME-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003556 anti-epileptic effect Effects 0.000 description 1
- 239000001961 anticonvulsive agent Substances 0.000 description 1
- VPSLGSSVPWVZFG-UHFFFAOYSA-N butan-2-yl propanoate Chemical compound CCC(C)OC(=O)CC VPSLGSSVPWVZFG-UHFFFAOYSA-N 0.000 description 1
- VAIZTNZGPYBOGF-UHFFFAOYSA-N butyl 2-(4-{[5-(trifluoromethyl)pyridin-2-yl]oxy}phenoxy)propanoate Chemical group C1=CC(OC(C)C(=O)OCCCC)=CC=C1OC1=CC=C(C(F)(F)F)C=N1 VAIZTNZGPYBOGF-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007337 electrophilic addition reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
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- 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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Abstract
The invention discloses a preparation method of 3-chloropropionic acid, and belongs to the technical field of chloropropionic acid preparation. Adding acrylic acid and distilled water into a reaction vessel, simultaneously adding a phase transfer catalyst, slowly introducing hydrogen chloride gas at 35-40 ℃ to obtain 3-chloropropionic acid, and then separating and purifying a crude product obtained by reaction to obtain a 3-chloropropionic acid product with the purity higher than 99%. Acrylic acid and distilled water are used as reaction solvents, TEBA is used as a catalyst, the reaction activation energy is reduced due to the reduction of the reaction temperature, and the acrylic acid can quickly absorb hydrogen chloride at a lower reaction temperature, so that the adverse factor that the acrylic acid is self-polymerized when the temperature is high is solved; the purity of the directly reacted crude product is up to more than 99 percent, a small amount of acrylic acid remained in the crude product is easy to remove from the crude product, a high-purity product can be obtained by rectification, the reaction steps are simple and easy to control, and the purity and the quality of the product are also improved.
Description
Technical Field
The invention belongs to the technical field of chloropropionic acid preparation, and particularly relates to a preparation method of 3-chloropropionic acid.
Background
The 3-chloropropionic acid is an important organic synthetic raw material, is an intermediate of pesticide, medicine and dye, can be used for synthesizing beta-butyl propionate, is used for producing antiepileptic medicine, is also used for preparing pesticide fluazifop-butyl and is used as a synthetic reagent, such as 3-chloropropionyl chloride and the like used for synthesizing the intermediate of dye.
At present, the synthesis method of 3-chloropropionic acid mainly comprises an acrylonitrile addition chlorination hydrolysis method, a propionic acid illumination chlorination method, an acrolein chlorination addition oxidation method, a 3-chloropropanol oxidation method, an acrylic acid chlorination addition method and the like. The acrylonitrile addition chlorination hydrolysis method uses a highly flammable, explosive and highly toxic raw material acrylonitrile, and has the advantages of long process flow, complex operation, serious corrosion to equipment, more three wastes and serious environmental pollution; the propionic acid photo-chlorination method has low selectivity of only 50 percent, releases a large amount of HCl gas, causes serious environmental pollution, is accompanied by a large amount of 2-chloropropionic acid, and is difficult to separate products and obtain high-purity products because the 2-chloropropionic acid and the 3-chloropropionic acid are isomers; the acrolein chlorination addition oxidation method can generate 3-chloropropionic acid only by two-step reaction, the process flow is longer, the yield of the 3-chloropropionic acid is low, and the discharged NO2The environment is seriously polluted; the 3-chloropropanol oxidation method uses 3-chloropropanol as a raw material, and the price of the 3-chloropropanol oxidation method is much higher than that of 3-chloropropionic acid, so the 3-chloropropanol oxidation method is unreasonable in economic consideration and has environmental pollution; the acrylic acid chlorination addition method is used for synthesizing 3-chloropropionic acid by taking acrylic acid and dried HCl as raw materials, but actually, due to the particularity of an acrylic acid product, when the reaction temperature is high (over 40 ℃), the acrylic acid product can be polymerized, the temperature is low, and the addition cannot be carried out, and the reaction also has side reactions such as symmetrical addition and asymmetrical addition, so that the purity of the 3-chloropropionic acid on the market is generally not high, and is generally about 95-96%.
The specific examples are patent application numbers: 200410017891.8, filing date: 4, 23 days 2004, the name of the invention is: a method for synthesizing and purifying 3-chloropropionic acid comprises two steps, firstly, in a reaction kettle, acrylic acid is chloridized to synthesize the 3-chloropropionic acid, and the reaction equation is as follows: CH (CH)2＝CHCOOH+HCI→CICH2CH2COOH; then the crude product obtained by the reaction is separated and purified,to prepare the high-purity 3-chloropropionic acid product. Again as in patent application No.: 201710892937.8, filing date: in 2017, 9 and 27 months, the invention and creation name is: a production method of 3-chloropropionic acid comprises the following steps: assembling a continuous reactor; preparation of 3-chloropropionic acid: purifying 3-chloropropionic acid; 3-chloropropionic acid continuous production. With the increasing market demand of 3-chloropropionic acid, the significance of developing an environment-friendly, efficient and economic preparation method of 3-chloropropionic acid is great.
Disclosure of Invention
1. Technical problem to be solved by the invention
Aiming at the problem that the existing acrylic acid product is easy to generate polymerization reaction under the high-temperature reaction condition (namely the self-polymerization temperature of the acrylic acid product is higher than 40 ℃) to cause low product content, the invention provides a preparation method of 3-chloropropionic acid, which reduces the polymerization reaction of the acrylic acid product and improves the product purity of the 3-chloropropionic acid.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the preparation method of 3-chloropropionic acid comprises the steps of adding acrylic acid and distilled water into a reaction container, adding a phase transfer catalyst, slowly introducing hydrogen chloride gas at 35-40 ℃, stopping introducing the hydrogen chloride gas when the content of the acrylic acid is detected to be less than or equal to 0.5%, obtaining the 3-chloropropionic acid, and then separating and purifying a crude product obtained by reaction to obtain a 3-chloropropionic acid product with the purity higher than 99%.
The hydrogen chloride gas can also use a by-product of acylation reaction of 3-chloropropionic acid, the hydrogen chloride gas carries part of water and can be used for preparing the 3-chloropropionic acid from the acrylic acid without drying, in the traditional reaction, under the condition of water, the addition of the acrylic acid and the hydrogen chloride can generate more by-product 2-chloropropionic acid, but after a small amount of water is added, the selectivity of the 3-chloropropionic acid is improved, probably because the acrylic acid and the hydrogen chloride are subjected to ionic reaction by the small amount of water, the generation of electrophilic addition reaction is promoted, and in the reaction process, H+Attack the position with larger electron cloud density in the acrylic acid to form more stable carbenium ion, and then 3-chloropropionic acid is more prone to be generated。
In one possible embodiment of the invention, the phase transfer catalyst is TEBA, and polyethylene glycol + TEBA or polyether + TEBA may also be used.
In one possible embodiment of the invention, the mass ratio of acrylic acid, distilled water and phase transfer catalyst TEBA is 300: 50: 3. the reaction is fully performed by accurately controlling the ratio of the raw materials.
In one possible embodiment of the invention, the reaction temperature is preferably 40 ℃. The carbonyl in the chloropropionic acid has strong electron withdrawing property, electrons on the double bond are pulled to one end close to the carbonyl, so that polarization is performed, the other end of the double bond is positively charged, and the double bond of the acrylic acid is easily attacked by free radicals generated by heating the double bond, so that the self-polymerization phenomenon is generated. The invention takes 40 ℃ as the preferred temperature, avoids the self-polymerization of acrylic acid as much as possible, simultaneously has the highest reaction temperature as much as possible, increases the reaction rate and improves the reaction activity.
In one possible embodiment of the invention, the reaction pressure of the preparation method is preferably normal pressure, and the reaction can be rapidly carried out under the normal pressure state, so that the requirements on equipment are reduced, and the unsafe problem caused by high-pressure reaction is avoided.
In one possible embodiment of the present invention, the reaction time is 8-10 h. Compared with the traditional production process, the method saves the reaction time and effectively improves the reaction efficiency.
In one possible embodiment of the invention, the purification of the crude product is carried out by one or more of vacuum distillation, adsorbent decolorization, recrystallization and solvent extraction.
The invention adopts hydrogen chloride gas which is dissolved in water phase and dissociated into H+And Cl-The Cl-is transported into the organic phase by the action of a phase transfer catalyst.
The invention adds TEBA as phase transfer catalyst, on one hand, interface energy between hydrogen chloride gas (gas phase), acrylic acid (organic phase) and water phase is reduced, on the other hand, the mixing degree between the organic phase such as acrylic acid and the water phase is limited, and the invention has the capability of dissolving in the water phase and the organic phase simultaneously, positive and negative ions in quaternary ammonium salt form ion pairs in the water phase, and the positive ions have large steric hindrance due to large volume, so the distance between the positive and negative ions is large, the interaction is weak, the negative ions are easy to dissociate, and the water phase is transferred to the organic phase, thereby increasing reaction rate and improving reaction activity; the addition of the phase transfer catalyst reduces the interfacial energy between phases, and meanwhile, the negative ions do not generate solvent effect in the organic phase, thereby reducing the activation energy of the reaction and further reducing the temperature required by the reaction.
Meanwhile, the phase transfer catalyst such as quaternary ammonium salt positive ions in TEBA is dissolved in an organic phase, so that the polarization of acrylic acid is promoted and the activity of a substrate is improved in the initial stage of reaction.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) according to the preparation method of the 3-chloropropionic acid, the acrylic acid and the distilled water are used as reaction solvents, the TEBA is used as a catalyst, the reaction activation energy is reduced due to the reduction of the reaction temperature, the acrylic acid can quickly absorb hydrogen chloride at a lower reaction temperature, and the adverse factor that the acrylic acid is self-polymerized when the temperature is high is solved; the purity of the directly reacted crude product is up to more than 99 percent, a small amount of acrylic acid is left in the crude product and is easy to remove from the crude product, a high-purity product can be obtained by rectification, the reaction step is simple and easy to control, and the purity and the quality of the product are also improved;
(2) compared with the traditional method in which water is present, the method for preparing 3-chloropropionic acid can generate more byproduct 2-chloropropionic acid by adding acrylic acid and hydrogen chloride, and the selectivity of 3-chloropropionic acid is improved after a small amount of water is added;
(3) the hydrogen chloride adopts the by-product of the acylation reaction of the 3-chloropropionic acid, so that the discharge of hydrogen chloride gas in the acylation reaction process of the 3-chloropropionic acid is reduced; the discharged hydrogen chloride gas does not need to be dried, and the carried small amount of water promotes the preparation of 3-chloropropionic acid;
(4) compared with the method of directly adding the hydrogen chloride aqueous solution, the method of the invention has the advantages that the concentration of the hydrogen chloride aqueous solution is 36.5% at most, the hydrogen chloride concentration in the solution is gradually reduced along with the reaction process, the reaction rate and the yield are influenced, and the HCl gas is continuously added, so that the reactants can be kept in relatively stable concentration;
(5) the product obtained by the preparation method of the 3-chloropropionic acid has high purity and good color.
Drawings
FIG. 1 is a chromatogram of example 1 of the present invention.
Detailed Description
For a further understanding of the invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings and examples. Although these exemplary embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, it should be understood that other embodiments may be realized and that various changes to the invention may be made without departing from the spirit and scope of the present invention. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. Accordingly, the scope of the invention is to be limited only by the following claims.
Wherein tables 1 to 6 show the results of detection of 3-chloropropionic acid obtained in examples 1 to 6.
Example 1
In the preparation method of 3-chloropropionic acid of this embodiment, 300g of acrylic acid and 50g of distilled water are added into a 1000mL reaction kettle, and 3g of a phase transfer catalyst TEBA (benzyltriethylammonium chloride) is added at the same time, hydrogen chloride gas is slowly introduced at 35 ℃, the reaction time under normal pressure is 8 hours, the introduction of hydrogen chloride gas is stopped when the content of acrylic acid is detected to be 0.5%, 3-chloropropionic acid is obtained, then the crude product obtained by the reaction is separated and purified, and the purification of the crude product adopts reduced pressure distillation, so that a 3-chloropropionic acid product with the purity higher than 99.67% is obtained.
And (3) analyzing the finally obtained 3-chloropropionic acid product by using an analyzer: linghua GC9890B, column type: SE-5430m 0.32mm 0.4 um;
A. the instrument conditions were as follows:
a. column temperature: 140 ℃; a detector: 280 ℃; vaporization temperature: 280 ℃; sensitivity: 3;
b. hydrogen gas: 0.1 Mpa; air: 0.1 Mpa; carrier gas (nitrogen): 0.08 MPa;
B. temperature programming:
keeping at 140 deg.C for 1min, heating to 280 deg.C at 20 deg.C/min, and keeping for 5 min.
C. Sample treatment:
a sample is taken, a 10uL sample injector is used for injecting 0.1uL sample, the sample is sampled for 15min, the content of the sample is measured by an area normalization method, a chromatogram is shown in figure 1, the purity of the product is as high as 99.67 percent, the purity is very high, the requirement of a medical intermediate is met, and the problem that the purity of the product is not high enough in the prior art is solved.
It should be noted that, in the invention, acrylic acid and distilled water are used as reaction solvents, TEBA is used as a catalyst, and the TEBA can effectively reduce the reaction temperature in the reaction process, so that the reaction temperature is maintained at 35-40 ℃, the acrylic acid can quickly absorb hydrogen chloride, and the problem of polymerization caused by high acrylic acid temperature (the self-polymerization critical temperature is 40 ℃, and a severe self-polymerization phenomenon can occur above the temperature) is solved; the purity of the directly reacted crude product is up to more than 99 percent, a small amount of acrylic acid remained in the crude product is easy to remove from the crude product, a high-purity product can be obtained by refining, the reaction step is simple and easy to control, and the purity and the quality of the product are also improved.
The data for detecting the obtained 3-chloropropionic acid are as follows:
TABLE 1 detection results of 3-chloropropionic acid obtained in example 1
Example 2
In the preparation method of 3-chloropropionic acid of this embodiment, 300g of acrylic acid and 50g of distilled water are added into a 1000mL reaction kettle, and 3g of a phase transfer catalyst TEBA (benzyltriethylammonium chloride) is added at the same time, hydrogen chloride gas is slowly introduced at 38 ℃, the reaction time under normal pressure is 9 hours, the introduction of hydrogen chloride gas is stopped when the content of acrylic acid is detected to be 0.45%, 3-chloropropionic acid is obtained, then the crude product obtained by the reaction is separated and purified, and the crude product is purified by vacuum distillation, so that a 3-chloropropionic acid product with the purity higher than 99% is obtained.
And (3) analyzing the finally obtained 3-chloropropionic acid product by using an analyzer: linghua GC9890B, column type: SE-5430m 0.32mm 0.4 um;
A. the instrument conditions were as follows:
a. column temperature: 140 ℃; a detector: 280 ℃; vaporization temperature: 280 ℃; sensitivity: 3;
b. hydrogen gas: 0.1 Mpa; air: 0.1 Mpa; carrier gas (nitrogen): 0.08 MPa;
B. temperature programming:
keeping at 140 deg.C for 1min, heating to 280 deg.C at 20 deg.C/min, and keeping for 5 min.
The data for detecting the obtained 3-chloropropionic acid are as follows:
TABLE 2 detection results of 3-chloropropionic acid obtained in example 2
Example 3
In the preparation method of 3-chloropropionic acid of this embodiment, 300g of acrylic acid and 50g of distilled water are added into a 1000mL reaction tank, and 3g of a phase transfer catalyst TEBA (benzyltriethylammonium chloride) is added at the same time, hydrogen chloride gas is slowly introduced at 40 ℃, the reaction time at normal pressure is 10 hours, the introduction of hydrogen chloride gas is stopped when the content of acrylic acid is detected to be 0.4%, 3-chloropropionic acid is obtained, then the crude product obtained by the reaction is separated and purified, and the purification of the crude product is performed by adopting an adsorbent to decolor, so that a 3-chloropropionic acid product with the purity higher than 99% is obtained.
And (3) analyzing the finally obtained 3-chloropropionic acid product by using an analyzer: linghua GC9890B, column type: SE-5430m 0.32mm 0.4 um;
A. the instrument conditions were as follows:
a. column temperature: 140 ℃; a detector: 280 ℃; vaporization temperature: 280 ℃; sensitivity: 3;
b. hydrogen gas: 0.1 Mpa; air: 0.1 Mpa; carrier gas (nitrogen): 0.08 MPa;
B. temperature programming:
keeping at 140 deg.C for 1min, heating to 280 deg.C at 20 deg.C/min, and keeping for 5 min.
The data for detecting the obtained 3-chloropropionic acid are as follows:
TABLE 3 detection results of 3-chloropropionic acid obtained in example 3
Example 4
In the preparation method of 3-chloropropionic acid of this embodiment, 300g of acrylic acid and 50g of distilled water are added into a 1000mL reaction kettle, and 3g of a phase transfer catalyst TEBA (benzyltriethylammonium chloride) is added at the same time, hydrogen chloride gas is slowly introduced at 40 ℃, the reaction time at normal pressure is 8 hours, the introduction of hydrogen chloride gas is stopped when the content of acrylic acid is detected to be 0.45%, 3-chloropropionic acid is obtained, then the crude product obtained by the reaction is separated and purified, and recrystallization is adopted for the purification of the crude product, so as to obtain a 3-chloropropionic acid product with the purity higher than 99%.
And (3) analyzing the finally obtained 3-chloropropionic acid product by using an analyzer: linghua GC9890B, column type: SE-5430m 0.32mm 0.4 um;
A. the instrument conditions were as follows:
a. column temperature: 140 ℃; a detector: 280 ℃; vaporization temperature: 280 ℃; sensitivity: 3;
b. hydrogen gas: 0.1 Mpa; air: 0.1 Mpa; carrier gas (nitrogen): 0.08 MPa;
B. temperature programming:
keeping at 140 deg.C for 1min, heating to 280 deg.C at 20 deg.C/min, and keeping for 5 min.
The data for detecting the obtained 3-chloropropionic acid are as follows:
TABLE 4 detection results of 3-chloropropionic acid obtained in example 4
Example 5
In the preparation method of 3-chloropropionic acid of this embodiment, 300g of acrylic acid and 50g of distilled water are added into a 1000mL reaction kettle, and 3g of a phase transfer catalyst TEBA (benzyltriethylammonium chloride) is added at the same time, hydrogen chloride gas is slowly introduced at 35 ℃, the reaction time under normal pressure is 10 hours, the introduction of hydrogen chloride gas is stopped when the content of acrylic acid is detected to be 0.46%, 3-chloropropionic acid is obtained, then the crude product obtained by the reaction is separated and purified, and the crude product is purified by vacuum distillation, so that a 3-chloropropionic acid product with the purity higher than 99% is obtained.
And (3) analyzing the finally obtained 3-chloropropionic acid product by using an analyzer: linghua GC9890B, column type: SE-5430m 0.32mm 0.4 um;
A. the instrument conditions were as follows:
a. column temperature: 140 ℃; a detector: 280 ℃; vaporization temperature: 280 ℃; sensitivity: 3;
b. hydrogen gas: 0.1 Mpa; air: 0.1 Mpa; carrier gas (nitrogen): 0.08 MPa;
B. temperature programming:
keeping at 140 deg.C for 1min, heating to 280 deg.C at 20 deg.C/min, and keeping for 5 min.
The data for detecting the obtained 3-chloropropionic acid are as follows:
TABLE 5 detection results of 3-chloropropionic acid obtained in example 5
Example 6
In the preparation method of 3-chloropropionic acid of this embodiment, 300g of acrylic acid and 50g of distilled water are added into a 1000mL reaction kettle, and 3g of a phase transfer catalyst TEBA (benzyltriethylammonium chloride) is added at the same time, hydrogen chloride gas is slowly introduced at 35 ℃, the reaction time under normal pressure is 10 hours, the introduction of hydrogen chloride gas is stopped when the content of acrylic acid is detected to be 0.48%, 3-chloropropionic acid is obtained, then the crude product obtained by the reaction is separated and purified, and the purification of the crude product adopts solvent extraction, so as to obtain a 3-chloropropionic acid product with the purity higher than 99%.
And (3) analyzing the finally obtained 3-chloropropionic acid product by using an analyzer: linghua GC9890B, column type: SE-5430m 0.32mm 0.4 um;
A. the instrument conditions were as follows:
a. column temperature: 140 ℃; a detector: 280 ℃; vaporization temperature: 280 ℃; sensitivity: 3;
b. hydrogen gas: 0.1 Mpa; air: 0.1 Mpa; carrier gas (nitrogen): 0.08 MPa;
B. temperature programming:
keeping at 140 deg.C for 1min, heating to 280 deg.C at 20 deg.C/min, and keeping for 5 min.
The data for detecting the obtained 3-chloropropionic acid are as follows:
TABLE 6 detection results of 3-chloropropionic acid obtained in example 6
The present invention and its embodiments have been described above schematically, without limitation, and what is shown in the drawings is only one of the embodiments of the present invention, and the actual structure is not limited thereto. Therefore, if the person skilled in the art receives the teaching, without departing from the spirit of the invention, the person skilled in the art shall not inventively design the similar structural modes and embodiments to the technical solution, but shall fall within the scope of the invention.
Claims (7)
1. A preparation method of 3-chloropropionic acid is characterized in that acrylic acid and distilled water are added into a reaction vessel, a phase transfer catalyst is added at the same time, hydrogen chloride gas is slowly introduced at the temperature of 35-40 ℃, the introduction of the hydrogen chloride gas is stopped when the content of the acrylic acid is detected to be less than or equal to 0.5%, 3-chloropropionic acid is obtained, and then a crude product obtained by the reaction is separated and purified, so that a 3-chloropropionic acid product is obtained.
2. The process for the preparation of 3-chloropropionic acid according to claim 1, characterized in that the phase transfer catalyst is TEBA.
3. The process for preparing 3-chloropropionic acid according to claim 1, characterized in that the mass ratio of acrylic acid to distilled water to the phase transfer catalyst is 300: 50: 3.
4. 3-chloropropionic acid production process according to claim 1, characterized in that the reaction temperature is preferably 40 ℃.
5. The process for producing 3-chloropropionic acid according to claim 1, characterized in that the reaction pressure is normal pressure.
6. The method for preparing 3-chloropropionic acid according to claim 1, characterized in that the reaction time is 8-10 h.
7. The method of claim 1, wherein the crude product is purified by one or more of distillation under reduced pressure, decolorization with adsorbent, recrystallization, and solvent extraction.
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| CN1569799A (en) * | 2004-04-23 | 2005-01-26 | 上海华谊丙烯酸有限公司 | Process for preparing high-purity 3-chloropropionic acid |
| CN107573231A (en) * | 2017-09-27 | 2018-01-12 | 荆楚理工学院 | A kind of production method of 3 chloropropionic acid |
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