CN106588628B - Preparation method of carboxylic acid - Google Patents
Preparation method of carboxylic acid Download PDFInfo
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- CN106588628B CN106588628B CN201611139651.4A CN201611139651A CN106588628B CN 106588628 B CN106588628 B CN 106588628B CN 201611139651 A CN201611139651 A CN 201611139651A CN 106588628 B CN106588628 B CN 106588628B
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims abstract description 31
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 239000002841 Lewis acid Substances 0.000 claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 17
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 17
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 1
- 239000010970 precious metal Substances 0.000 claims 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 22
- -1 carboxylic acid compound Chemical class 0.000 abstract description 14
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000007327 hydrogenolysis reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 description 22
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 125000000217 alkyl group Chemical group 0.000 description 14
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 14
- 238000007210 heterogeneous catalysis Methods 0.000 description 10
- 238000003760 magnetic stirring Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 235000019260 propionic acid Nutrition 0.000 description 7
- 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 7
- 239000002904 solvent Substances 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 7
- WHBMMWSBFZVSSR-UHFFFAOYSA-M 3-hydroxybutyrate Chemical compound CC(O)CC([O-])=O WHBMMWSBFZVSSR-UHFFFAOYSA-M 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- WHBMMWSBFZVSSR-UHFFFAOYSA-N R3HBA Natural products CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 description 5
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000005015 poly(hydroxybutyrate) Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- HPMGFDVTYHWBAG-UHFFFAOYSA-N 3-hydroxyhexanoic acid Chemical compound CCCC(O)CC(O)=O HPMGFDVTYHWBAG-UHFFFAOYSA-N 0.000 description 4
- NDPLAKGOSZHTPH-UHFFFAOYSA-N 3-hydroxyoctanoic acid Chemical compound CCCCCC(O)CC(O)=O NDPLAKGOSZHTPH-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N beta-hydroxy propionic acid Natural products OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006315 carbonylation Effects 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 230000003834 intracellular effect Effects 0.000 description 2
- OSHOQERNFGVVRH-UHFFFAOYSA-K iron(3+);trifluoromethanesulfonate Chemical compound [Fe+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F OSHOQERNFGVVRH-UHFFFAOYSA-K 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JWWVWJOIKZNCSU-UHFFFAOYSA-N methanesulfonic acid;2,2,2-trifluoroacetic acid Chemical compound CS(O)(=O)=O.OC(=O)C(F)(F)F JWWVWJOIKZNCSU-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001020 poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Polymers 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- WJPWYVWFKYPSJS-UHFFFAOYSA-J trifluoromethanesulfonate;zirconium(4+) Chemical compound [Zr+4].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F WJPWYVWFKYPSJS-UHFFFAOYSA-J 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- YKVIWISPFDZYOW-UHFFFAOYSA-N 6-Decanolide Chemical compound CCCCC1CCCCC(=O)O1 YKVIWISPFDZYOW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 description 1
- 238000007065 Kolbe-Schmitt synthesis reaction Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000012691 depolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005911 haloform reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- UQGPCEVQKLOLLM-UHFFFAOYSA-N pentaneperoxoic acid Chemical compound CCCCC(=O)OO UQGPCEVQKLOLLM-UHFFFAOYSA-N 0.000 description 1
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229940005605 valeric acid Drugs 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
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供了一种羧酸的制备方法，包括：如式(I)所示的聚羟基脂肪酸酯在复合催化剂的存在下，与氢气发生反应，得到羧酸；所述复合催化剂包括加氢催化剂和路易斯酸；其中，a、b独立的选自1～10的整数；m、n独立的选自1～30000的整数；R1、R2独立的选自H和C1～C12的烷基中的一种或几种。本发明式(I)所示的聚羟基脂肪酸酯在加氢催化剂和路易斯酸复合催化剂的条件下，氢解解聚，得到羧酸类化合物。本发明提供的反应条件温和、收率高，与传统的方法相比副产物少，符合绿色化学的要求，更具有工业价值。The invention provides a method for preparing a carboxylic acid, comprising: reacting a polyhydroxyalkanoate represented by formula (I) with hydrogen in the presence of a composite catalyst to obtain a carboxylic acid; the composite catalyst comprises hydrogenation A catalyst and a Lewis acid; wherein a and b are independently selected from integers from 1 to 10; m and n are independently selected from integers from 1 to 30000; R 1 and R 2 are independently selected from H and C1-C12 alkyl groups one or more of them. The polyhydroxyalkanoate represented by the formula (I) of the present invention undergoes hydrogenolysis and depolymerization under the conditions of a hydrogenation catalyst and a Lewis acid composite catalyst to obtain a carboxylic acid compound. Compared with the traditional method, the reaction conditions provided by the invention are mild, the yield is high, and the by-products are less, which meets the requirements of green chemistry and has more industrial value.
Description
Technical field
The present invention relates to compound synthesis technical fields, more particularly, to a kind of preparation method of carboxylic acid.
Background technique
Polyhydroxyalkanoate (PHA) is a kind of Biodegradable high-molecular compound synthesized in bacterial cell, very
It is multi-field to have a wide range of applications.Current main research direction concentrates in the development and application of PHA.As one kind by
The Biopolvester intracellular of Microbe synthesis, PHA are the deposits of energy and carbon source of the multiple-microorganism in energy and carbon source surplus
Substance.The prior art is mostly using PHA as the deposit substance of energy, by reacting PHA with excessive methanol, through transesterification solution
Poly-, obtained hydroxy fatty acid methyl esters can be directly as bio-fuel.
Carboxylic acid is a kind of important compound, is the final product of many oxidation operations.It is generally existing in nature,
It has a wide range of applications in industry, agricultural and field of medicaments.
The method of prior art preparation carboxylic acid mainly has oxidizing process, carbonylation method, Hydrolyze method and CO2Prize law etc.；Specifically
Say, oxidizing process be the oxidation of hydrocarbon, the oxidation of primary alconol or aldehyde compound, the oxidation of methyl ketone；Carbonylation method is alcohols chemical combination
The hydrated carbonyl of the carbonylation of object, alkene；Hydrolyze method is cyanides hydrolysis, lipoid substance hydrolysis, amides chemical combination
Object hydrolysis；CO2Prize law is organometallic reagent and CO2Reaction, Kolbe-Schmitt reaction；Additionally pass through including methyl ketone
Haloform reaction prepares carboxylic acid.But the above method prepares carboxylic acid reaction condition harshness, and by-product is more, and yield is low.
Summary of the invention
In view of this, the present invention provides the technical problem to be solved in the present invention is that providing a kind of preparation method of carboxylic acid
Carboxylic acid preparation method by-product it is few, high income.
The present invention provides a kind of preparation methods of carboxylic acid, comprising:
The polyhydroxyalkanoate as shown in formula (I) reacts with hydrogen in the presence of composite catalyst, obtains carboxylic
Acid；
The composite catalyst includes hydrogenation catalyst and lewis acid；
Wherein, a, b it is independent be selected from 1~10 integer；
M, n it is independent be selected from 1~30000 integer；
R1、R2Independent one or more of the alkyl selected from H and C1~C12.
Preferably, described a, b it is independent be selected from 1~8 integer；M, n it is independent be selected from 1~20000 integer；R1、R2Solely
Vertical one or more of the alkyl selected from H and C1~C8.
Preferably, the hydrogenation catalyst is noble metal carrier catalyst.
Preferably, the noble metal carrier catalyst carrier is active carbon, and metal is selected from one of palladium, platinum, rhodium, ruthenium
Or it is several.
Preferably, the lewis acid is metal trifluoroacetate mesylate.
Preferably, the lewis acid is selected from AgOTf, Cu (OTf)2、Al(OTf)3、Fe(OTf)3、Zr(OTf)4、Hf
(OTf)4、Nb(OTf)5、Ta(OTf)5With W (OTf)6One or more of.
Preferably, the mole of the hydrogenation catalyst is the 0.01%~5% of polyhydroxyalkanoate mole.
Preferably, the lewis acidic mole is the 0.5%~10% of polyhydroxyalkanoate mole.
Preferably, the pressure of the hydrogen is 1~100atm.
Preferably, the reaction temperature be 80 DEG C~250 DEG C, the reaction time be 0.5~for 24 hours.
Compared with prior art, the present invention provides a kind of preparation methods of carboxylic acid, comprising: the poly- hydroxyl as shown in formula (I)
Base aliphatic ester reacts in the presence of composite catalyst with hydrogen, obtains carboxylic acid；The composite catalyst includes adding hydrogen
Catalyst and lewis acid；Wherein, a, b it is independent be selected from 1~10 integer；M, n it is independent be selected from 1~30000 integer；
R1、R2Independent one or more of the alkyl selected from H and C1~C12.Polyhydroxyalkanoate shown in formula (I) of the present invention
Under conditions of hydrogenation catalyst and lewis acid composite catalyst, hydrogenolysis depolymerization obtains carboxylic acid compound.The present invention provides
Reaction condition is mild, high income, by-product is few with traditional method compared with, the requirement of composite green chemistry, has more industrial
Value.
Specific embodiment
The present invention provides a kind of preparation methods of carboxylic acid, comprising:
The polyhydroxyalkanoate as shown in formula (I) reacts with hydrogen in the presence of composite catalyst, obtains carboxylic
Acid；
The composite catalyst includes hydrogenation catalyst and lewis acid；
Wherein, a, b it is independent be selected from 1~10 integer；
M, n it is independent be selected from 1~30000 integer；
R1、R2Independent one or more of the alkyl selected from H and C1~C12.
The present invention in the presence of composite catalyst, reacts polyhydroxyalkanoate with hydrogen, obtains carboxylic acid.It is excellent
Choosing is specially in the reactor to mix polyhydroxyalkanoate and composite catalyst, under the atmosphere of hydrogen, is stirred to react, obtains
To carboxylic acid.
For the present invention for the reactor without limiting, reactor well known to those skilled in the art is of the invention
For the stirring without limiting, stirring well known to those skilled in the art, preferably magnetic agitation.The stirring
Speed is preferably 400~600r/min；More preferably 500~600r/min.
Polyhydroxyalkanoate of the present invention is polyhydroxyalkanoate well known to those skilled in the art, is by very much
A kind of polyester intracellular of bacterium synthesis, exists primarily as the Stored Matter of carbon source and the energy in vivo, it has
There are biodegradability not available for physicochemical characteristic and synthetic plastic similar to synthetic plastic, biocompatibility, optics living
Property, piezoelectricity, gas phase are every many excellent in performance such as property.
Shown in polyhydroxyalkanoate of the present invention such as formula (I):
Wherein, a, b it is independent be selected from 1~10 integer；Preferably 1~8 integer；More preferably 1~6 integer.
M, n it is independent be selected from 1~30000 integer；It is preferably selected from 1~20000 integer；The polyhydroxyalkanoate
Number-average molecular weight be preferably 1.0 × 105~2.0 × 105。
R1、R2Independent one or more of the alkyl selected from H and C1~C12.It is preferably selected from the alkyl of H and C1~C8
One or more of；It is more preferably selected from one or more of the alkyl of H and C1~C6；The alkyl include straight chained alkyl and
Branched alkyl；The alkyl includes substituted or unsubstituted alkyl, and the present invention is to the substituent group for replacing alkyl without limit
It is fixed, it can be ester group well known to those skilled in the art, cyano, halogen.
In the present invention, described a, b；m,n；R1、R2It can be identical or different；That is, above-mentioned polyhydroxyalkanoate
It can be homopolymer or copolymer；
Polyhydroxyalkanoate of the present invention includes but is not limited to following particular compounds:
Homopolymer: poly- 3- hydracrylic acid, poly- 3-hydroxybutyrate, poly- 3- hydroxypentanoic acid, poly- 3- hydroxycaproic acid, poly- 3- hydroxyl heptan
Sour, poly- 3- Hydroxyoctanoic acid；
Copolymer: poly- hydracrylic acid hydroxypentanoic acid, polyhydroxybutyrate hydroxycaproic acid, polyhydroxybutyrate hydroxypentanoic acid, poly- hydroxyl
Base butyric acid hydroxypentanoic acid hydroxycaproic acid.
The polyhydroxyalkanoate that the present invention meets above-mentioned condition can carry out hydrogenolysis depolymerization reaction of the invention, obtain carboxylic
Acid.
The present invention for the polyhydroxyalkanoate source without limit, it is commercially available.
Composite catalyst of the present invention includes hydrogenation catalyst and lewis acid.
In the present invention, the hydrogenation catalyst is preferably noble metal carrier catalyst.The noble metal support type is urged
Agent carrier is preferably active carbon, and metal is preferably selected from one or more of palladium, platinum, rhodium, ruthenium；The noble metal support type is urged
Agent is more preferably Pd/C, Pt/C or Ru/C.
In the present invention, the lewis acid is preferably metal trifluoroacetate mesylate；More preferably AgOTf, Cu (OTf)2、
Al(OTf)3、Fe(OTf)3、Zr(OTf)4、Hf(OTf)4、Nb(OTf)5、Ta(OTf)5With W (OTf)6One or more of.
In the present invention, the mole of the hydrogenation catalyst be preferably polyhydroxyalkanoate mole 0.01%~
5%；More preferably 0.1%~3%；Most preferably 0.5%~2%；The lewis acidic mole is preferably poly- hydroxyl rouge
The 0.5%~10% of fat acid esters mole；More preferable 1%~8%；Most preferably 2%~6%.The hydrogenation catalyst and road
The mass ratio of Lewis acid is preferably (1~100): (1~100).
In the present invention, the atmosphere of the hydrogen be using the air in hydrogen metathesis reactor, preferably under normal pressure into
Row.Hydrogen balloon is more preferably connect above reactor.The pressure of the hydrogen is preferably 1~100atm；It is more preferably 1~50 big
Air pressure；Most preferably 1~20 atmospheric pressure；It is the most preferably 1~10 atmospheric pressure.
In the present invention, the reaction temperature is preferably 80 DEG C~250 DEG C, more preferably 100 DEG C~200 DEG C；Most preferably
It is 110 DEG C~180 DEG C；It is the most preferably 120 DEG C~150 DEG C；The reaction time is preferably 0.5~for 24 hours；More preferably 2~
20h；Most preferably 4~16h；It is the most preferably 8~14h.
The present invention is by the control of the parameters such as above-mentioned reaction temperature, reaction raw materials molar ratio, Hydrogen Vapor Pressure, so that final system
Standby obtained carboxylic acid high income.
In the present invention, according to the selection of reaction temperature and the selection of specific polyhydroxyalkanoate, solvent also has not
Same selection:
When reaction temperature is more than the fusing point of polyhydroxyalkanoate, it is not necessarily to reaction dissolvent；
When fusing point of the reaction temperature lower than polyhydroxyalkanoate is, it is preferable to use reaction dissolvent.
In the present invention, the solvent is preferably one or more of carboxylic acids, hydro carbons and ether solvent；Including but not
It is limited to for methylene chloride, acetic acid, acetic acid, propionic acid, dioxane, tetrahydrofuran or normal octane.
In the present invention, after completion of the reaction, preferably through isolated carboxylic acid sterling.
The separation is preferably with solvent dissolution, filtering, vacuum distillation, tool of the present invention for the filtering, vacuum distillation
Body mode is well known to those skilled in the art to filter, be evaporated under reduced pressure without limiting.The solvent includes but is not limited to be
Methylene chloride, acetic acid, acetic acid, propionic acid, dioxane, tetrahydrofuran or normal octane.
After the completion of the present invention separates carboxylic acid, it is preferably also included in the catalyst system of separation carboxylic acid and rejoins the poly- hydroxyl of raw material
Base aliphatic ester is passed through hydrogen, carries out catalytic hydrogenolytic cleavage again, can reuse to catalyst system.
The present invention provides a kind of preparation methods of carboxylic acid, comprising: the polyhydroxyalkanoate as shown in formula (I) is compound
It in the presence of catalyst, reacts with hydrogen, obtains carboxylic acid；
The composite catalyst includes hydrogenation catalyst and lewis acid；Wherein, a, b it is independent be selected from 1~10 integer；
M, n it is independent be selected from 1~30000 integer；R1、R2Independent one or more of the alkyl selected from H and C1~C12.This hair
Polyhydroxyalkanoate shown in bright formula (I) is under conditions of hydrogenation catalyst and lewis acid composite catalyst, hydrogenolysis depolymerization,
Obtain carboxylic acid compound.Reaction condition provided by the invention is mild, high income, and by-product is few with traditional method compared with, accords with
The requirement of Green Chemistry is closed, industrial value is had more.
Gas-chromatography is carried out to the carboxylic acid being prepared present invention preferably employs following manner and nuclear-magnetism is identified:
Gas chromatograph: GC-2014C, chromatographic column: DM-wax column (30m*0.32mm*0.25 μm)；Temperature program: 100 DEG C
(5min) → 10 DEG C/min → 180 DEG C (3min) → 20 DEG C/min → 240 DEG C (10min) injector temperature: 260 DEG C of detector temperature
Degree: 280 DEG C
Nuclear-magnetism: 400 spectrometer of model Bruker Avance is detected at room temperature.
In order to further illustrate the present invention, with reference to embodiments to the preparation side of carboxylic acid compound provided by the invention
Method is described in detail.
Examples 1 to 3
Raw material uses poly- hydroxymethylbutyrate ester (PHB), the i.e. homopolymer of 3-hydroxybutyrate, purity 99.9%, the degree of polymerization
It is 1500.To be put into after 10g raw material break process in the schlenk bottle of 100ml, be added the propionic acid of 15ml, 0.5% Pd/C and
2% W (OTf)6, apply the hydrogen pressure of 1atm, 100 DEG C~135 DEG C be heated in magnetic stirring apparatus, reaction keeps 8~12
Hour, revolving speed 500r/min.It is then cooled down, is filtered to remove heterogeneous catalysis.Finally use inspection of the present invention
Survey mode is measured.Specific experimental temperature, reaction time and testing result are listed in Table 1 below, and table 1 is the embodiment of the present invention 1
~15 reaction conditions and yield results.The nuclear magnetic data of product n-butyric acie is as follows:1H NMR(400MHz,CDCl3) δ=
2.34 (t, J=7.4,2H), 1.74-1.60 (m, 2H), 0.98 (t, J=7.4,3H)13C NMR(101MHz,CDCl3) δ=
180.59,35.97,18.12,13.53.
Embodiment 4~9
Raw material uses poly- hydroxymethylbutyrate ester (PHB), purity 99.9%, the degree of polymerization 1500.By the broken place of 10g raw material
It is put into miniature high pressure reaction still after reason, the W (OTf) of 0.5% Pd/C and 2% is added6, solvent using 15ml acetic acid, third
Acid, dioxane, tetrahydrofuran or normal octane apply the hydrogen pressure of 1,5 or 10atm, 135 are heated in magnetic stirring apparatus
DEG C, reaction is kept for 12 hours, revolving speed 500r/min.It is then cooled down, is filtered to remove heterogeneous catalysis.It is final to use this
The invention detection mode is measured.Testing result is listed in Table 1 below, and table 1 is the reaction item of the embodiment of the present invention 1~15
Part and yield results.
Embodiment 10~15
Raw material uses poly- hydroxymethylbutyrate ester (PHB), purity 99.9%, the degree of polymerization 1500.By the broken place of 10g raw material
Be put into after reason in the schlenk bottle of 100ml, solvent use 15ml propionic acid, hydrogenation catalyst select 0.5% Pd/C or
0.5% Pt/C, fluoroform sulphonate select W (OTf)6、Hf(OTf)4、Al(OTf)3、Ta(OTf)5、Nb(OTf)5Or Zr
(OTf)4, apply the hydrogen pressure of 1atm, 135 DEG C be heated in magnetic stirring apparatus, reaction is kept for 12 hours, revolving speed 500r/
min.It is then cooled down, is filtered to remove heterogeneous catalysis.Finally it is measured using detection mode of the present invention.Inspection
The results are shown in Table 1 for survey, and table 1 is the reaction condition of the embodiment of the present invention 1~15 and yield results.
The reaction condition of 1 embodiment of the present invention of table 1~15 and yield results
Embodiment 16
Raw material is changed to polyhydroxybutyrate hydroxyl valerate (PHBV), the as copolymerization of 3-hydroxybutyrate and 3- hydroxypentanoic acid
Ester, wherein ratio shared by 3-hydroxybutyrate is that the ratio of 12%, 3- hydroxypentanoic acid is 88%, purity 99.9%, the degree of polymerization
It is 10000.It will be put into after 10g raw material break process in the schlenk bottle of 100ml, the propionic acid of 15ml, 0.5% Pd/C be added
With 2% W (OTf)6, apply the hydrogen pressure of 1atm, 135 DEG C be heated in magnetic stirring apparatus, reaction is kept for 12 hours, revolving speed
For 500r/min.It is then cooled down, is filtered to remove heterogeneous catalysis.Finally carried out using detection mode of the present invention
Measurement.Testing result is listed in Table 2 below, and table 2 is the reaction condition of the embodiment of the present invention 16~22 and yield results.
Embodiment 17
Raw material is changed to polyhydroxybutyrate hydroxycaproate (PHBHHx), as 3-hydroxybutyrate and 3- hydroxycaproic acid is total to
Polyester, wherein ratio shared by 3-hydroxybutyrate is that the ratio of 14%, 3- hydroxycaproic acid is 86%, purity 99.9%, polymerization
Degree is 10000.It will be put into after 10g raw material break process in the schlenk bottle of 100ml, the propionic acid of 15ml, 2% Pd/C be added
With 4% W (OTf)6, apply the hydrogen pressure of 1atm, 135 DEG C be heated in magnetic stirring apparatus, reaction is kept for 12 hours, revolving speed
For 500r/min.It is then cooled down, is filtered to remove heterogeneous catalysis.Finally carried out using detection mode of the present invention
Measurement.Testing result is listed in Table 2 below, and table 2 is the reaction condition of the embodiment of the present invention 16~22 and yield results.
Embodiment 18
Raw material is changed to another polyhydroxybutyrate hydroxycaproate (PHBHHx), wherein ratio shared by 3-hydroxybutyrate
Example is that the ratio of 29%, 3- hydroxycaproic acid is 71%, purity 99.9%, the degree of polymerization 15000.By 10g raw material break process
After be put into miniature high pressure reaction device, the W (OTf) of 0.5% Pd/C and 1% is added in solvent-free system6, apply the hydrogen of 5atm
Pressure is heated to 150 DEG C in magnetic stirring apparatus, and reaction is kept for 6 hours, revolving speed 500r/min.It is then cooled down, is filtered
Remove heterogeneous catalysis.Finally it is measured using detection mode of the present invention.Testing result is listed in Table 2 below, and table 2 is
The reaction condition of the embodiment of the present invention 16~22 and yield results.
Embodiment 19
Raw material is changed to poly- Hydroxyoctanoic acid ester (PHO), the i.e. homopolymer of 3- Hydroxyoctanoic acid, purity 99.9%, the degree of polymerization
It is 3000.To be put into miniature high pressure reaction still after 10g raw material break process, solvent-free system, be added 0.5% Pd/C and
2% W (OTf)6, apply the hydrogen pressure of 10atm, 135 DEG C be heated in magnetic stirring apparatus, reaction is kept for 6 hours, and revolving speed is
500r/min.It is then cooled down, is filtered to remove heterogeneous catalysis.Finally surveyed using detection mode of the present invention
It is fixed.Testing result is listed in Table 2 below, and table 2 is the reaction condition of the embodiment of the present invention 16~22 and yield results.Product caprylic acid
Nuclear magnetic data it is as follows:1H NMR(400MHz,CDCl3) δ=2.35 (t, J=7.5,2H), 1.67-1.59 (m, 2H), 1.36-
1.25 (m, 8H), 0.88 (t, J=6.9,3H)13C NMR(101MHz,CDCl3) δ=180.48,34.11,31.64,29.02,
28.91,24.68,22.60,14.07.
Embodiment 20
Raw material is changed to poly- valerolactone (PVL), purity 99.9%, the degree of polymerization 6000.After 10g raw material break process
Be put into miniature high pressure reaction still, be added 15ml acetic acid, 0.5% Pd/C and 2% W (OTf)6, apply the hydrogen pressure of 1atm,
180 DEG C are heated in magnetic stirring apparatus, reaction is kept for 9 hours, revolving speed 500r/min.It is then cooled down, is filtered to remove
Heterogeneous catalysis.Finally it is measured using detection mode of the present invention.Testing result is listed in Table 2 below, and table 2 is this hair
Bright embodiment 16~22 reaction condition and yield results.The nuclear magnetic data of product valeric acid is as follows:1H NMR(400MHz,
CDCl3) δ=2.36 (t, J=7.5,2H), 1.68-1.57 (m, 2H), 1.43-1.32 (m, 2H), 0.93 (t, J=7.4,3H)
.13C NMR(101MHz,CDCl3) δ=180.75,33.86,26.71,22.17,13.68.
Embodiment 21
Raw material is changed to polycaprolactone (PCL), purity 99.9%, the degree of polymerization 8000.After 10g raw material break process
Be put into miniature high pressure reaction still, be added 15ml propionic acid, 0.5% Pd/C and 2% W (OTf)6, apply the hydrogen pressure of 1atm,
135 DEG C are heated in magnetic stirring apparatus, reaction is kept for 12 hours, revolving speed 500r/min.It is then cooled down, is filtered to remove
Heterogeneous catalysis.Finally it is measured using detection mode of the present invention.Testing result is listed in Table 2 below, and table 2 is this hair
Bright embodiment 16~22 reaction condition and yield results.The nuclear magnetic data of product n-caproic acid is as follows:1H [NMR(400MHz,
CDCl3) δ=2.35 (t, J=7.5,2H), 1.70-1.58 (m, 2H), 1.41-1.27 (m, 4H), 0.90 (t, J=6.9,3H)
.13C NMR(101MHz,CDCl3) δ=180.57,34.10,31.20,24.36,22.29,13.86.
Embodiment 22
Raw material is changed to poly- ε-decalactone (PDL), purity 99.9%, the degree of polymerization 5000.By 10g raw material break process
Be put into the schlenk bottle of 100ml afterwards, be added 15ml butyric acid, 0.5% Pd/C and 2% W (OTf)6, apply the hydrogen of 1atm
Pressure is heated to 135 DEG C in magnetic stirring apparatus, and reaction is kept for 12 hours, revolving speed 500r/min.It is then cooled down, mistake
Filter out heterogeneous catalysis.Finally it is measured using detection mode of the present invention.Testing result is listed in Table 2 below, table 2
For the reaction condition of the embodiment of the present invention 16~22 and yield results.The nuclear magnetic data of product n-capric acid is as follows:1H NMR
(400MHz,CDCl3) δ=2.35 (t, J=7.5,2H), 1.67-1.59 (m, 2H), 1.22-1.36 (m, 14H), 0.88 (t, J
=6.8,3H)13C NMR(101MHz,CDCl3) δ=180.59,34.14,31.90,29.56,29.45,29.32,29.25,
29.07,24.67,22.69,14.11.
The reaction condition of 2 embodiment of the present invention of table 16~22 and yield results
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59108738A (en) * | 1982-12-13 | 1984-06-23 | Daicel Chem Ind Ltd | Preparation of caproic acid |
| CN1449371A (en) * | 2000-08-24 | 2003-10-15 | 巴斯福股份公司 | Method for the catalytic decomposition of lactones |
| CN105873895A (en) * | 2013-12-31 | 2016-08-17 | Bp北美公司 | Method for forming an aromatic diacid and/or an aromatic diacid precursor from a polyester-containing feedstock |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59108738A (en) * | 1982-12-13 | 1984-06-23 | Daicel Chem Ind Ltd | Preparation of caproic acid |
| CN1449371A (en) * | 2000-08-24 | 2003-10-15 | 巴斯福股份公司 | Method for the catalytic decomposition of lactones |
| CN105873895A (en) * | 2013-12-31 | 2016-08-17 | Bp北美公司 | Method for forming an aromatic diacid and/or an aromatic diacid precursor from a polyester-containing feedstock |
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