CN115043725A - Method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid - Google Patents
Method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid Download PDFInfo
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- CN115043725A CN115043725A CN202210931037.0A CN202210931037A CN115043725A CN 115043725 A CN115043725 A CN 115043725A CN 202210931037 A CN202210931037 A CN 202210931037A CN 115043725 A CN115043725 A CN 115043725A
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 95
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000000593 degrading effect Effects 0.000 title claims abstract description 33
- MONMFXREYOKQTI-UHFFFAOYSA-N 2-bromopropanoic acid Chemical class CC(Br)C(O)=O MONMFXREYOKQTI-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 150000003893 lactate salts Chemical class 0.000 title claims 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 111
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 17
- -1 2-bromopropionate compound Chemical class 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 25
- MNZMECMQTYGSOI-UHFFFAOYSA-N acetic acid;hydron;bromide Chemical compound Br.CC(O)=O MNZMECMQTYGSOI-UHFFFAOYSA-N 0.000 claims description 20
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 abstract description 42
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 abstract description 42
- 229940057867 methyl lactate Drugs 0.000 abstract description 42
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 abstract description 28
- 229940116333 ethyl lactate Drugs 0.000 abstract description 14
- 150000003903 lactic acid esters Chemical class 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- FBSPHFKZJKWNEC-UHFFFAOYSA-N 2-bromoethyl propanoate Chemical compound CCC(=O)OCCBr FBSPHFKZJKWNEC-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000013341 scale-up Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 112
- 239000011521 glass Substances 0.000 description 51
- ACEONLNNWKIPTM-UHFFFAOYSA-N methyl 2-bromopropanoate Chemical compound COC(=O)C(C)Br ACEONLNNWKIPTM-UHFFFAOYSA-N 0.000 description 28
- 238000004458 analytical method Methods 0.000 description 27
- 230000032050 esterification Effects 0.000 description 21
- 238000005886 esterification reaction Methods 0.000 description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 20
- 238000009423 ventilation Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 239000011541 reaction mixture Substances 0.000 description 16
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 9
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 8
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 8
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000686 essence Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 description 1
- 244000099147 Ananas comosus Species 0.000 description 1
- 235000007119 Ananas comosus Nutrition 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 235000003717 Boswellia sacra Nutrition 0.000 description 1
- 240000007551 Boswellia serrata Species 0.000 description 1
- 235000012035 Boswellia serrata Nutrition 0.000 description 1
- 239000004863 Frankincense Substances 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 235000011430 Malus pumila Nutrition 0.000 description 1
- 235000015103 Malus silvestris Nutrition 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000013736 caramel Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of polylactic acid utilization, and relates to a method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid. The synthesis method comprises the following steps: carrying out a first-stage reaction on polylactic acid and a hydrogen bromide solution or hydrogen bromide gas in a closed environment to obtain a reaction solution; then adding low molecular alcohol to carry out second stage reaction, and obtaining the 2-bromopropionate compound and the lactate compound after the reaction is finished. The preparation method takes green renewable polylactic acid as a raw material, realizes the preparation of 2-bromopropionate compounds (such as 2-bromomethyl propionate and 2-bromoethyl propionate) and lactate compounds (such as methyl lactate and ethyl lactate) by a simple reaction process at a mild temperature, has the highest yield of the 2-bromomethyl propionate up to 123 percent and the highest yield of the methyl lactate up to 135 percent based on the quality of the raw material polylactic acid, and is suitable for industrial scale-up production.
Description
Technical Field
The invention belongs to the technical field of polylactic acid utilization, and relates to a method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid.
Background
Polylactic acid is a renewable polymer polymerized by fermenting a carbohydrate into lactic acid, and is a renewable biomass resource. At present, the polylactic acid has realized large-scale production and application, and has become the most mature, the largest yield and the most widely applied biodegradable plastic in the industrialization in the global scope.
The 2-bromopropionate compounds (such as methyl 2-bromopropionate and ethyl 2-bromopropionate) are compounds containing both bromine atom and ester bond. Based on the bromine atom and ester bond functional group with reaction activity, the 2-bromopropionate compound is widely applied to the fields of organic synthesis, pharmaceutical chemistry and the like, for example, the 2-bromopropionate compound can be used as an initial raw material to synthesize derivatives such as ester, acyl halide, amide and the like; the active group bromine can perform a series of reactions and can be used for synthesizing pesticides. Lactate compounds (such as methyl lactate, ethyl lactate and the like) are compounds containing hydroxyl and ester bonds at the same time, and have wider application, for example, the methyl lactate and the ethyl lactate can be used as solvents of cellulose, paint and dyeing pigment; the ethyl lactate can also be used for blending edible essences such as apple, pineapple, caramel, frankincense and the like, and can also be used in liquor essences such as rum, white spirit and the like.
The low-carbon environment-friendly renewable bio-based materials are degraded and recycled to become a market hotspot. Although polylactic acid can be degraded in nature, the process usually requires a long time and special degradation conditions, and the degradation products are carbon dioxide and water, so that direct and rapid recycling cannot be realized. Prior patents disclose related contents of preparing lactate by alcoholysis of polylactic acid with catalyst, for example, patent CN110003009A discloses a method for preparing immobilized ionic liquid [ Bmim [ ]][OAc]-Zn(OAc) 2 The method for recovering methyl lactate by using the SBA-15 as the catalyst to alcoholyze the waste polylactic acid material (PLA for short) comprises the following steps: according to the mass ratio mPLA m catalyst 1:0.002-0.1, mol ratio nPLA: n methanol 1:1-10, PLA, methanol and catalyst [ Bmim][OAc]-Zn(OAc) 2 Adding SBA-15 into a reaction kettle, carrying out alcoholysis reaction at 90-130 ℃, filtering and recovering a catalyst after the reaction is finished, carrying out rotary evaporation to recover unreacted methanol, and carrying out reduced pressure distillation to collect a product methyl lactate, wherein the conversion rate of PLA can reach 100%, the yield of the product methyl lactate can reach more than 95%, the purity can reach 99%, and the catalyst is immobilized with an ionic liquid [ Bmim ]][OAc]-Zn(OAc) 2 the/SBA-15 can be directly recycled. However, in the patent, both the ionic liquid and the carrier need to be prepared, and the preparation method is complex, long in time consumption and high in cost, is not suitable for industrial production, and does not fully exert the value of polylactic acid. Therefore, the development of a new high-efficiency technology has important significance for converting the polylactic acid or the polylactic acid solid waste into high-value chemicals (such as 2-bromopropionate compounds and lactate compounds).
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid. The invention takes green renewable polylactic acid as a raw material to prepare the 2-bromopropionate compound and the lactate compound with high yield. The preparation method has the characteristics of simplicity, mild reaction conditions and high yield.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid comprises the steps of carrying out a first-stage reaction on polylactic acid and a hydrogen bromide solution or a hydrogen bromide gas in a closed environment to obtain a reaction solution; then adding low molecular alcohol into the reaction solution to carry out the second stage reaction, and obtaining the 2-bromopropionic acid ester compound (such as 2-bromopropionic acid methyl ester or 2-bromopropionic acid ethyl ester) and the lactate compound after the reaction is finished.
Further, the hydrogen bromide solution is a hydrogen bromide acetic acid solution or a hydrobromic acid solution.
Further, when the hydrogen bromide solution is a hydrogen bromide acetic acid solution, the mass fraction of the hydrogen bromide acetic acid solution is 33%.
Further, when the hydrogen bromide solution is a hydrobromic acid solution, the mass fraction of the hydrobromic acid solution is 48%.
Further, the mass-volume ratio of the polylactic acid to the hydrogen bromide acetic acid solution is 0.4g (1-4) mL.
Further, the mass-to-volume ratio of the polylactic acid to the hydrobromic acid solution is 0.4g (1-4) mL.
Furthermore, the mass-volume ratio of the polylactic acid to the hydrogen bromide gas is 0.2g (10-20) mL.
Further, the temperature of the first stage reaction is 70-120 ℃.
Further, the time of the first stage reaction is 1-48 h.
Further, excessively low reaction temperatures (e.g., 50 ℃) require excessively long reaction times; an excessively high reaction temperature (e.g., 120 ℃) is high in energy consumption, a vapor pressure of a reaction solvent is large, and other by-products are easily generated.
Furthermore, the reaction temperature is controlled to be between 70 and 110 ℃, and the synthesis of the 2-bromopropionate compound is facilitated by raising the temperature and prolonging the time moderately.
Further, the low molecular alcohol comprises methanol or ethanol.
Further, the mass-volume ratio of the polylactic acid to the low molecular alcohol is 0.4g (2-4) mL.
Further, the temperature of the second stage reaction is 40-50 ℃.
Further, the time of the second stage reaction is 1-2 h.
The invention has the following beneficial effects:
the invention provides a method for preparing 2-bromopropionate compounds (such as 2-bromomethyl propionate and 2-bromoethyl propionate) and lactate compounds (such as methyl lactate and ethyl lactate) by taking green renewable polylactic acid as a raw material and adopting a simple reaction process at a mild temperature. The preparation method realizes the purpose of preparing the 2-bromopropionate compound and the lactate compound from the polylactic acid in high yield, and realizes the high added value conversion of the polylactic acid. In addition, according to the preparation method provided by the invention, when the product yield is calculated based on the mass of the raw material polylactic acid, the yield of the prepared 2-bromomethyl propionate can reach 123% at most, and the yield of the methyl lactate can reach 135% at most.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a diagram showing a sample before the reaction in example 1 of the present invention.
FIG. 2 is a diagram showing a sample after the first-stage reaction of example 1 of the present invention.
FIG. 3 is a diagram showing a sample after the second-stage reaction in example 1 of the present invention.
FIG. 4 is a gas chromatography-mass spectrometry (GC-MS) analysis chart of the methyl ester product obtained after the second stage reaction of example 1 of the present invention.
FIG. 5 is a gas chromatography-hydrogen ion flame detector (GC-FID) analysis chart of a methyl ester product obtained after the second-stage reaction in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
This example is a method for preparing methyl 2-bromopropionate and methyl lactate by degrading polylactic acid, comprising the following steps:
0.4g of polylactic acid was charged into a 10mL glass reaction tube, and 2mL of a 33% hydrogen bromide acetic acid solution was further added, and the glass reaction tube was sealed (see FIG. 1), and reacted at 90 ℃ for 11 hours. After the reaction was complete, a yellow transparent solution was obtained after cooling to room temperature (see FIG. 2). Placing the obtained yellow transparent solution in a ventilation cabinet to volatilize a part of hydrogen bromide acetic acid solution for 24 hours; then, 3mL of methanol was added to the glass reaction tube and the reaction was further carried out at 50 ℃ for 2 hours to obtain a yellow methyl esterification solution (see FIG. 3). To the resulting yellow methyl esterification solution was added an internal standard, dimethyl succinate, for qualitative (gas chromatography-mass spectrometry (GC-MS) analysis, see fig. 4)) and quantitative (gas chromatography-hydrogen ion flame detector (GC-FID) analysis, see fig. 5). The analysis result shows that: the obtained mixed solution contains 2-bromomethyl propionate and methyl lactate; and the content of methyl 2-bromopropionate was 0.36g (90% based on the mass yield of polylactic acid) and the content of methyl lactate was 0.19g (48% based on the mass yield of polylactic acid).
Example 2
This example is a method for preparing methyl 2-bromopropionate and methyl lactate by degrading polylactic acid, comprising the following steps:
0.4g of polylactic acid was added to a 10mL glass reaction tube, and 2mL of a 33% hydrogen bromide acetic acid solution was further added, and the glass reaction tube was sealed and reacted at 100 ℃ for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a yellow transparent solution. Placing the obtained yellow transparent solution in a ventilation cabinet to volatilize a part of hydrogen bromide acetic acid solution for 24 hours; then, 3mL of methanol was added to the glass reaction tube, and the mixture was further reacted at 50 ℃ for 2 hours to obtain a yellow methyl esterification solution. To the resulting yellow methyl esterification solution was added an internal standard, dimethyl succinate, for qualitative (gas chromatography-mass spectrometry (GC-MS)) and quantitative (gas chromatography-hydrogen ion flame detector (GC-FID)) analysis. The analysis result shows that: the obtained mixed solution contains 2-bromomethyl propionate and methyl lactate; and the content of methyl 2-bromopropionate was 0.49g (123% based on the mass yield of polylactic acid) and the content of methyl lactate was 0.07g (18% based on the mass yield of polylactic acid).
Example 3
This example is a method for preparing methyl 2-bromopropionate and methyl lactate by degrading polylactic acid, comprising the following steps:
0.4g of polylactic acid was added to a 10mL glass reaction tube, and 2mL of a 33% hydrogen bromide acetic acid solution was further added, and the glass reaction tube was sealed and reacted at 90 ℃ for 1 hour. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a yellow transparent solution. Placing the obtained yellow transparent solution in a ventilation hood to volatilize a part of hydrogen bromide acetic acid solution for 24 hours; then, 3mL of methanol was added to the glass reaction tube, and the mixture was further reacted at 50 ℃ for 2 hours to obtain a yellow methyl esterification solution. To the resulting yellow methyl esterification solution was added an internal standard, dimethyl succinate, for qualitative (gas chromatography-mass spectrometry (GC-MS)) and quantitative (gas chromatography-hydrogen ion flame detector (GC-FID)) analysis. The analysis result shows that: the obtained mixed solution contains 2-bromomethyl propionate and methyl lactate; and the content of methyl 2-bromopropionate was 0.012g (3% based on the mass yield of polylactic acid) and the content of methyl lactate was 0.54g (135% based on the mass yield of polylactic acid).
Example 4
This example is a method for preparing methyl 2-bromopropionate and methyl lactate by degrading polylactic acid, comprising the following steps:
0.4g of polylactic acid was added to a 10mL glass reaction tube, and 2mL of a 33% hydrogen bromide acetic acid solution was further added, and the glass reaction tube was sealed and reacted at 80 ℃ for 36 hours. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a yellow transparent solution. Placing the obtained yellow transparent solution in a ventilation cabinet to volatilize a part of hydrogen bromide acetic acid solution for 24 hours; then, 3mL of methanol was added to the glass reaction tube, and the mixture was further reacted at 50 ℃ for 2 hours to obtain a yellow methyl esterification solution. To the resulting yellow methyl esterification solution was added an internal standard, dimethyl succinate, for qualitative (gas chromatography-mass spectrometry (GC-MS)) and quantitative (gas chromatography-hydrogen ion flame detector (GC-FID)) analysis. The analysis result shows that: the obtained mixed solution contains 2-bromomethyl propionate and methyl lactate; and the content of methyl 2-bromopropionate was 0.44g (110% based on the mass yield of polylactic acid) and the content of methyl lactate was 0.16g (40% based on the mass yield of polylactic acid).
Example 5
This example is a method for preparing methyl 2-bromopropionate and methyl lactate by degrading polylactic acid, comprising the following steps:
0.4g of polylactic acid was added to a 10mL glass reaction tube, and 2mL of a 48% hydrobromic acid solution was added thereto, and the glass reaction tube was sealed and reacted at 110 ℃ for 1 hour. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a yellow transparent solution. Placing the obtained yellow transparent solution in a ventilation cabinet to volatilize a part of hydrobromic acid solution for 24 hours; then, 3mL of methanol was added to the glass reaction tube and the mixture was further reacted at 50 ℃ for 2 hours to obtain a yellow methyl esterification solution. To the resulting yellow methyl esterification solution was added an internal standard, dimethyl succinate, for qualitative (gas chromatography-mass spectrometry (GC-MS)) and quantitative (gas chromatography-hydrogen ion flame detector (GC-FID)) analysis. The analysis result shows that: the obtained mixed solution contains 2-bromomethyl propionate and methyl lactate; and the content of methyl 2-bromopropionate was 0.02g (5% based on the mass yield of polylactic acid) and the content of methyl lactate was 0.54g (135% based on the mass yield of polylactic acid).
Example 6
This example is a method for preparing methyl 2-bromopropionate and methyl lactate by degrading polylactic acid, comprising the following steps:
0.4g of polylactic acid was added to a 10mL glass reaction tube, and 2mL of a 48% hydrobromic acid solution was further added, and the glass reaction tube was sealed and reacted at 110 ℃ for 6 hours. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a yellow transparent solution. Placing the obtained yellow transparent solution in a ventilation cabinet to volatilize a part of hydrobromic acid solution for 24 hours; then, 3mL of methanol was added to the glass reaction tube, and the mixture was further reacted at 50 ℃ for 2 hours to obtain a yellow methyl esterification solution. To the resulting yellow methyl esterification solution was added an internal standard, dimethyl succinate, for qualitative (gas chromatography-mass spectrometry (GC-MS)) and quantitative (gas chromatography-hydrogen ion flame detector (GC-FID)) analysis. The analysis result shows that: the obtained mixed solution contains 2-bromomethyl propionate and methyl lactate; and the content of methyl 2-bromopropionate was 0.12g (30% based on the mass yield of polylactic acid) and the content of methyl lactate was 0.49g (123% based on the mass yield of polylactic acid).
Example 7
This example is a method for preparing methyl 2-bromopropionate and methyl lactate by degrading polylactic acid, comprising the following steps:
0.4g of polylactic acid was added to a 10mL glass reaction tube, and 2mL of a 48% hydrobromic acid solution was added thereto, and the glass reaction tube was sealed and reacted at 80 ℃ for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a yellow transparent solution. Placing the obtained yellow transparent solution in a ventilation cabinet to volatilize a part of hydrobromic acid solution for 24 hours; then, 3mL of methanol was added to the glass reaction tube, and the mixture was further reacted at 50 ℃ for 2 hours to obtain a yellow methyl esterification solution. To the resulting yellow methyl esterification solution was added an internal standard, dimethyl succinate, for qualitative (gas chromatography-mass spectrometry (GC-MS)) and quantitative (gas chromatography-hydrogen ion flame detector (GC-FID)) analysis. The analysis result shows that: the obtained mixed solution contains 2-bromomethyl propionate and methyl lactate; and the content of methyl 2-bromopropionate was 0.02g (125% by mass based on polylactic acid) and the content of methyl lactate was 0.50g (125% by mass based on polylactic acid).
Example 8
This example is a method for preparing methyl 2-bromopropionate and methyl lactate by degrading polylactic acid, comprising the following steps:
0.4g of polylactic acid was taken and added to a 10mL glass reaction tube, and 1mL of 48% hydrobromic acid solution was further added, and the glass reaction tube was sealed and reacted at 100 ℃ for 10 hours. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a yellow transparent solution. Placing the obtained yellow transparent solution in a ventilation cabinet to volatilize a part of hydrobromic acid solution for 24 hours; then, 3mL of methanol was added to the glass reaction tube, and the mixture was further reacted at 50 ℃ for 2 hours to obtain a yellow methyl esterification solution. The analysis result shows that: the resulting solution contained methyl 2-bromopropionate and methyl lactate.
Example 9
This example is a method for preparing methyl 2-bromopropionate and methyl lactate by degrading polylactic acid, comprising the following steps:
0.2g of polylactic acid was added to a 20mL glass reaction tube, 10mL of hydrogen bromide gas was added, the glass reaction tube was sealed, and the reaction was carried out at 80 ℃ for 24 hours. After the reaction, the reaction mixture was cooled to room temperature to obtain a yellow transparent solution. Placing the obtained yellow transparent solution in a ventilation cabinet to volatilize a part of hydrogen bromide gas for 24 hours; then, 3mL of methanol was added to the glass reaction tube, and the mixture was further reacted at 50 ℃ for 2 hours to obtain a yellow methyl esterification solution. The analysis result shows that: the resulting solution contained methyl 2-bromopropionate and methyl lactate.
Example 10
This example is a method for preparing ethyl 2-bromopropionate and ethyl lactate by degrading polylactic acid, comprising the following steps:
0.1g of polylactic acid was added to a 20mL glass reaction tube, 10mL of hydrogen bromide gas was added, the glass reaction tube was sealed, and the reaction was carried out at 90 ℃ for 18 hours. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a yellow transparent solution. Placing the obtained yellow transparent solution in a ventilation cabinet to volatilize a part of hydrogen bromide gas for 24 hours; then, 2mL of ethanol was added to the glass reaction tube, and the mixture was further reacted at 50 ℃ for 1 hour to obtain a yellow ethylated solution. The analysis result shows that: the resulting mixed solution contained ethyl 2-bromopropionate and ethyl lactate.
Example 11
This example is a method for preparing methyl 2-bromopropionate and methyl lactate by degrading polylactic acid, comprising the following steps:
0.4g of polylactic acid was added to a 10mL glass reaction tube, 1mL of 33% hydrogen bromide acetic acid solution was further added, the glass reaction tube was sealed, and the reaction was carried out at 70 ℃ for 48 hours. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a yellow transparent solution. Placing the obtained yellow transparent solution in a ventilation hood to volatilize a part of hydrogen bromide acetic acid solution for 24 hours; then, 3mL of methanol was added to the glass reaction tube, and the mixture was further reacted at 50 ℃ for 2 hours to obtain a yellow methyl esterification solution. The analysis result shows that: the resulting solution contained methyl 2-bromopropionate and methyl lactate.
Example 12
This example is a method for preparing methyl 2-bromopropionate and methyl lactate by degrading polylactic acid, comprising the following steps:
0.4g of polylactic acid was added to a 10mL glass reaction tube, 4mL of 33% hydrogen bromide in acetic acid was added thereto, the glass reaction tube was sealed, and the reaction was carried out at 100 ℃ for 18 hours. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a yellow transparent solution. Placing the obtained yellow transparent solution in a ventilation cabinet to volatilize a part of hydrogen bromide acetic acid solution for 24 hours; then, 3mL of methanol was added to the glass reaction tube and the mixture was further reacted at 50 ℃ for 2 hours to obtain a yellow methyl esterification solution. The analysis result shows that: the resulting solution contained methyl 2-bromopropionate and methyl lactate.
Example 13
This example is a method for preparing methyl 2-bromopropionate and methyl lactate by degrading polylactic acid, comprising the following steps:
0.4g of polylactic acid was taken and added to a 10mL glass reaction tube, and 2mL of a 48% hydrobromic acid solution was further added, and the glass reaction tube was sealed and reacted at 120 ℃ for 1 hour. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a yellow transparent solution. Placing the obtained yellow transparent solution in a ventilation cabinet to volatilize a part of hydrobromic acid solution for 24 hours; then, 3mL of methanol was added to the glass reaction tube, and the mixture was further reacted at 50 ℃ for 2 hours to obtain a yellow methyl esterification solution. The analysis result shows that: the resulting solution contained methyl 2-bromopropionate and methyl lactate.
Example 14
This example is a method for preparing ethyl 2-bromopropionate and ethyl lactate by degrading polylactic acid, comprising the following steps:
0.4g of polylactic acid was taken and added to a 10mL glass reaction tube, and 2mL of a 48% hydrobromic acid solution was further added, and the glass reaction tube was sealed and reacted at 90 ℃ for 5 hours. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a yellow transparent solution. Placing the obtained yellow transparent solution in a ventilation cabinet to volatilize a part of hydrobromic acid solution for 24 hours; then, 3mL of ethanol was added to the glass reaction tube, and the mixture was further reacted at 40 ℃ for 2 hours to obtain a yellow ethylated solution. The analysis result shows that: the resulting solution contained ethyl 2-bromopropionate and ethyl lactate.
Example 15
This example is a method for preparing ethyl 2-bromopropionate and ethyl lactate by degrading polylactic acid, comprising the following steps:
0.4g of polylactic acid was added to a 10mL glass reaction tube, and 2mL of a 48% hydrobromic acid solution was further added, and the glass reaction tube was sealed and reacted at 110 ℃ for 6 hours. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a yellow transparent solution. Placing the obtained yellow transparent solution in a ventilation cabinet to volatilize a part of hydrobromic acid solution for 24 hours; then, 3mL of ethanol was added to the glass reaction tube, and the mixture was further reacted at 50 ℃ for 2 hours to obtain a yellow ethylated solution. The analysis result shows that: the resulting solution contained ethyl 2-bromopropionate and ethyl lactate.
Example 16
This example is a method for preparing ethyl 2-bromopropionate and ethyl lactate by degrading polylactic acid, comprising the following steps:
0.4g of polylactic acid was added to a 10mL glass reaction tube, and 2mL of a 33% hydrogen bromide acetic acid solution was further added, and the glass reaction tube was sealed and reacted at 100 ℃ for 11 hours. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a yellow transparent solution. Placing the obtained yellow transparent solution in a ventilation cabinet to volatilize a part of hydrobromic acid solution for 24 hours; then, 2mL of ethanol was added to the glass reaction tube, and the mixture was further reacted at 50 ℃ for 1 hour to obtain a yellow ethylated solution. And adding an internal standard substance dimethyl succinate into the obtained yellow ethyl esterification solution for qualitative and quantitative analysis. The analysis result shows that: the resulting mixed solution contained ethyl 2-bromopropionate and ethyl lactate, and the yield of ethyl 2-bromopropionate was 79% and the yield of ethyl lactate was 26%.
Example 17
This example is a method for preparing methyl 2-bromopropionate and methyl lactate by degrading polylactic acid, comprising the following steps:
0.4g of polylactic acid was taken and added to a 10mL glass reaction tube, and 4mL of 48% hydrobromic acid solution was further added, and the glass reaction tube was sealed and reacted at 100 ℃ for 16 hours. After the reaction was completed, the reaction mixture was cooled to room temperature to obtain a yellow transparent solution. Placing the obtained yellow transparent solution in a ventilation cabinet to volatilize a part of hydrogen bromide acetic acid solution for 24 hours; then, 4mL of methanol was added to the glass reaction tube, and the mixture was further reacted at 40 ℃ for 2 hours to obtain a yellow methyl esterification solution. The analysis result shows that: the resulting solution contained methyl 2-bromopropionate and methyl lactate.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (10)
1. A method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid is characterized in that: carrying out a first-stage reaction on polylactic acid and a hydrogen bromide solution or hydrogen bromide gas in a closed environment to obtain a reaction solution; then adding low molecular alcohol into the reaction liquid to carry out second stage reaction, and obtaining the 2-bromopropionate compound and the lactate compound after the reaction is finished.
2. The method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid according to claim 1, wherein: the hydrogen bromide solution is a hydrogen bromide acetic acid solution or a hydrobromic acid solution.
3. The method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid according to claim 2, wherein: when the hydrogen bromide solution is a hydrogen bromide acetic acid solution, the mass fraction of the hydrogen bromide acetic acid solution is 33%.
4. The method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid according to claim 2, wherein: when the hydrogen bromide solution is a hydrobromic acid solution, the mass fraction of the hydrobromic acid solution is 48%.
5. The method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid according to claim 3, wherein: the mass-to-volume ratio of the polylactic acid to the hydrobromic acid solution is 0.4g (1-4) mL, and the mass-to-volume ratio of the polylactic acid to the hydrobromic acid solution is 0.4g (1-4) mL.
6. The method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid according to claim 1, wherein: the mass volume ratio of the polylactic acid to the hydrogen bromide gas is 0.2g (10-20) mL.
7. The method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid according to any one of claims 1-6, wherein: the temperature of the first stage reaction is 70-120 ℃, and the time of the first stage reaction is 1-48 h.
8. The method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid according to claim 7, wherein: the low molecular alcohol is methanol or ethanol.
9. The method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid according to claim 8, wherein: the mass-volume ratio of the polylactic acid to the low molecular alcohol is 0.4g (2-4) mL.
10. The method for preparing 2-bromopropionate compounds and lactate compounds by degrading polylactic acid according to claim 8 or 9, wherein: the temperature of the second stage reaction is 40-50 ℃, and the time of the second stage reaction is 1-2 h.
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