CN114854005B - Method for synthesizing polyamide by olefin hydroamine carbonylation - Google Patents
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Abstract
The invention discloses a method for synthesizing polyamide by olefin hydroamine carbonylation, which realizes the diversity synthesis of polyamide in one step through olefin relay hydroamine carbonylation process under the combined action of palladium catalyst, ligand and alkali. The invention provides a novel method for preparing polyamide, which has the advantages of simple and easily obtained raw materials, low price, simple operation and wide application, and can simultaneously realize the preparation of aromatic polyamide and aliphatic polyamide.
Description
Technical Field
The invention belongs to the technical field of polyamide, and relates to a novel catalytic synthesis method for preparing polyamide.
Background
The polyamide as a polymer compound with wide application has good comprehensive properties including mechanical property, heat resistance, abrasion resistance, chemical resistance and self-lubricity, has low friction coefficient and certain flame retardance, is easy to process, is suitable for filling, reinforcing and modifying glass fibers and other fillers, improves the performance and expands the application range. Therefore, it is of great importance to develop a new and efficient catalytic process for the synthesis of different types of polyamides.
At present, polyamide is mainly synthesized by polycondensation, lactam ring-opening polymerization, amine carbonylation, alcohol catalytic dehydrogenation and the like. The monomers for polycondensation reaction may be amino acids, diamines, dicarboxylic acids and their derivatives (CN 112920400A, CN114349956A, CN114369238A, etc.). Notably, in such reactions, the carboxylic acid generally needs to be pre-activated to form the acid chloride or ester, and the reaction conditions are harsh and associated with stoichiometric generation of toxic waste, which is not environmentally friendly.
Condensation polymerization of amino acid:
condensation polymerization of diamine and dicarboxylic acid:
lactams are also commonly used as monomers for preparing polyamides by ring-opening polymerization, and the industry mainly includes hydrolytic ring-opening polymerization methods (CN 103772643A, CN104327266A, CN104629044A, etc.) and anionic ring-opening polymerization methods (CN 109851778A, CN111295410A, CN111448238A, CN113166400A, etc.). The hydrolytic ring-opening polymerization method takes water as an initiator, the obtained product has narrow relative molecular weight distribution and wide application, but the method needs higher polymerization temperature and longer reaction time. The anion ring-opening polymerization method needs to add strong base as an initiator, the reaction requires low temperature and high reaction speed, but the reaction process is not easy to control due to the excessively high reaction speed, so that the product has poor repeatability, the molecular weight and the molecular weight distribution fluctuate greatly, and a large number of generated byproducts are generated.
Ring-opening polymerization of lactam:
in addition, palladium catalyzed amine carbonylation of aromatic dihalides as a method of amide synthesis can also be used to prepare polyamides. The synthesis of polyamides by the carbonylation polycondensation of aromatic dihalides, aromatic diamines and carbon monoxide catalyzed by palladium has been extensively studied since the eighties of the twentieth century (Macromolecules 1988,21,1908-1911, polymer Chemistry 1989,27,1985-1992, polymer Chemistry 1994,32,2065-2071, polymer Bulletin 2020,77, 1951-1968. The method utilizes carbon monoxide as a cheap and easily-obtained carbon source, and has the advantages of simple and easily-obtained raw materials, mild reaction conditions and almost no environmental pollution. However, the reaction usually requires the addition of a large amount of ligand to inhibit the generation of palladium black, and the substrate application range is relatively small, so that only aromatic polyamide can be synthesized.
Palladium catalyzed amine carbonylation polycondensation of aromatic dihalides:
more recently, guan and Milstein et al reported a new process for the direct synthesis of polyamides by catalytic dehydrogenation using a Milstein catalyst (j.am.chem.soc.2011, 133,1159-1161, polymer Chemistry 2012,50, 1755-1765. The method takes dihydric alcohol and diamine as raw materials, not only can synthesize aromatic polyamide, but also can synthesize aliphatic polyamide, but the catalyst is sensitive to oxygen and has harsh reaction conditions.
Catalytic dehydrogenation of diols and diamines:
in earlier research works, the subject group develops palladium-catalyzed hydroaminocarbonylation of simple olefins and hydroxylamine hydrochloride, the reaction system has high atom utilization rate, good selectivity and strong substrate adaptability, and can realize high-efficiency synthesis of series of secondary amides (Communications Chemistry 2019,2, 14). On this basis, we envisage that if starting from symmetrical dienes, a highly efficient synthesis of polyamides can be achieved by a relay hydroamine carbonylation process. However, to implement the above process, three key scientific issues must be addressed: 1. the alkyl palladium intermediate generated by the insertion of the palladium hydrogen species by the olefin continuously reacts with the olefin to form a polyolefin by-product through a migration insertion process; 2. the acyl palladium species generated by the insertion of carbon monoxide on the alkyl palladium intermediate also can generate a side product of polyketone by the migration insertion process with olefin; 3. if the activity of the catalyst can support the symmetric diene substrate to complete the continuous relay hydroamine carbonylation process, the high-efficiency synthesis of the high molecular product is realized. Therefore, how to regulate the catalytic reaction system to realize the high-efficiency preparation of the specificity of the polyamide is the key of the prior art.
Disclosure of Invention
The invention aims to provide a novel synthesis method for preparing polyamide, which has simple process and low cost, takes diene monomer, hydroxylamine hydrochloride and carbon monoxide as raw materials, and realizes the diversity synthesis of polyamide in one step through the olefin relay hydroamine carbonylation process under the combined action of palladium catalyst, ligand and alkali. The method has the advantages of simple and easily obtained raw materials, low price, simple operation and wide application, can simultaneously realize the preparation of the aromatic polyamide and the aliphatic polyamide, and adopts a one-pot process.
The reaction route of the invention is shown as follows:
route 1:
route 2:
in the formula (II) wherein R is a substituent 1 Independently selected from H, linear or branched chain aliphatic group of C1-C40, aromatic group or heterocyclic group of C4-C12.
In route 1:
the palladium catalyst is selected from one or more of palladium catalysts such as palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium acetylacetonate, bis-acetonitrile palladium chloride, bis-tri-tert-butylphosphine palladium, allyl palladium chloride and the like; preferably, the bis-acetonitrile palladium chloride is used as the catalyst.
The ligand is selected from one or more of monophosphine ligands such as triphenylphosphine, benzyldiadamantylphosphine, dicyclohexyl- (2, 6-diisopropylphenyl) phosphine, 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 2-dicyclohexylphosphine-2 '6' -bis (N, N-dimethylamino) -1,1' -biphenyl, 2-dicyclohexylphosphine-2 ',6' -diisopropoxy-1, 1' -biphenyl, 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl and the like; 2-dicyclohexylphosphonium-2 ',6' -diisopropoxy-1, 1' -biphenyl is preferably used as a ligand.
In route 2:
the palladium catalyst is selected from one or more of palladium catalysts such as palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium acetylacetonate, bis-acetonitrile palladium chloride, bis-tri-tert-butylphosphine palladium, allyl palladium chloride and the like; allyl palladium chloride is preferred as the catalyst.
The ligand is selected from one or more of diphosphine ligands such as 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene, 1' -bis (diphenylphosphino) ferrocene, bis (2-diphenylphosphino) ether, 1, 2-bis (di-tert-butylphosphinomethyl) benzene, 1, 3-bis (dimethylcyclopentylphosphino) benzene, 4, 6-bis (diphenylphosphino) phenazine, bis (diphenylphosphinomethane), 1, 4-bis (diphenylphosphino) butane and the like; preferably 4, 5-bis diphenylphosphino-9, 9-dimethylxanthene is used as ligand.
The method specifically comprises the following steps:
adding a diene monomer, hydroxylamine hydrochloride, a palladium catalyst, a ligand, an alkali additive and a solvent into a reaction kettle in sequence, replacing air in the kettle with carbon monoxide for three times, filling carbon monoxide with a certain pressure, and heating to a set temperature for reacting for a certain time; after the reaction is finished, slowly releasing carbon monoxide in the autoclave after the autoclave is cooled, pouring the reaction liquid into methanol, centrifugally separating the mixture to obtain a crude product, sequentially washing the crude product with methanol and water, and drying the crude product in vacuum to obtain a polyamide product.
The diene monomer is selected from at least one of the following structural compounds:
substituent R 2 、R 3 、R 4 、R 5 、R 6 Independently selected from H, straight chain or branched chain C1-C40 aliphatic group, C4-C12 aromatic group or heterocyclic group; m is 1 、m 2 、m 3 、m 4 Represents the chain length and independently takes a value of 1-20.
The alkali is selected from one or more of sodium acetate, sodium phosphate, sodium benzoate, potassium acetate, potassium phosphate, triethylamine, N-diisopropylethylamine, 1, 8-diazohetero-bis-spiro [5.4.0] undec-7-ene, triethylene diamine, pyridine, 4-dimethylamino pyridine, 2-cyano-6-methyl pyridine and the like. Preferably 2-cyano-6-methylpyridine is the base.
The solvent is one or more selected from anisole, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and the like. Anisole or N-methylpyrrolidone is preferred as solvent.
In the preparation process of the invention, the reaction temperature is generally controlled at 100-200 ℃, preferably 120 ℃; the reaction time is generally controlled to 12 to 72 hours, preferably 24 hours.
In the preparation process of the invention, the carbon monoxide pressure is generally controlled to be 10-60 atm, and preferably 20atm.
In the preparation process, the molar ratio of the diene monomer to the hydroxylamine hydrochloride is 1.5. Preferably 1.2.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention directly uses the diene, the hydroxylamine hydrochloride and the carbon monoxide as reactants, and the raw materials are simple, cheap and easy to obtain.
2. The invention adopts a one-pot process, can convert the diene into the corresponding polyamide compound in one step without additional steps such as pre-activation and the like, and has the advantages of high economic step and environmental friendliness.
3. The method can be used for preparing aromatic polyamide and is also suitable for synthesizing aliphatic polyamide, and the substrate has wide application range and strong practicability.
Drawings
FIG. 1 is a characteristic infrared absorption peak of a polyamide.
Detailed Description
The invention is further illustrated by the examples given below. It should be noted that the present invention is not limited to these examples.
Example 1: without addition of alkali as an additive
In a strictly dry ampoule, aryldiene (213.1 mg), hydroxylamine hydrochloride (55.6 mg), bis-acetonitrile palladium (II) chloride (10.4 mg), 2-dicyclohexylphosphonium-2 ',6' -diisopropoxy-1, 1' -biphenyl (41.1 mg) and anisole (2.0 mL) were added in this order. Putting the ampoule bottle into an autoclave, replacing air in the autoclave with carbon monoxide for three times, filling carbon monoxide with 20atm, heating to 120 ℃ and reacting for 24 hours. After the autoclave is cooled, carbon monoxide in the autoclave is slowly released. The reaction solution was poured into methanol, and the mixture was centrifuged to give a crude product, which was then washed with methanol and water in this order and dried under vacuum to give a polyamide product with a yield of 11%.
Example 2: 2-cyano-6-methylpyridine as base
In a strictly dry ampoule were added sequentially aryldiene (213.1 mg), hydroxylamine hydrochloride (55.6 mg), bis-acetonitrile palladium (II) chloride (10.4 mg), 2-dicyclohexylphosphonium-2 ',6' -diisopropoxy-1, 1' -biphenyl (41.1 mg), 6-methyl-2-pyridinecarbonitrile (18.9 mg) and anisole (2.0 mL). Putting the ampoule bottle into an autoclave, replacing air in the autoclave with carbon monoxide for three times, filling 20atm of carbon monoxide, heating to 120 ℃ and reacting for 24 hours. After the autoclave is cooled, carbon monoxide in the autoclave is slowly released. The reaction solution was poured into methanol, and the mixture was centrifuged to give a crude product, which was subsequently washed with methanol and water in this order and dried under vacuum to give a polyamide product in a yield of 62% and having a number average molecular weight of 3.1X 10 4 The polymer dispersity index was 1.84.
Example 3: preparation of polyamides from aryldienes
To a strictly dry ampoule were added sequentially aryldiene (240.1 mg), hydroxylamine hydrochloride (34.7 mg), bis-acetonitrile palladium (II) chloride (6.5 mg), 2-dicyclohexylphosphonium-2 ',6' -diisopropoxy-1, 1' -biphenyl (25.7 mg) and N-methylpyrrolidinone (4.0 mL). Putting the ampoule bottle into an autoclave, replacing the air in the autoclave with carbon monoxide for three times, filling 20atm of carbon monoxide, heating to 120 ℃ and reacting for 12 hours. After the autoclave is cooled, carbon monoxide in the autoclave is slowly released. The reaction solution was poured into methanol, and the mixture was centrifuged to give a crude product, which was subsequently washed with methanol and water in this order and dried under vacuum to give a polyamide product in a yield of 73% and having a number average molecular weight of 9X 10 3 The polymer dispersity index was 3.79.
Example 4: preparation of polyamides from triaryldienes
In a strictly dry ampoule, aryldiene (410.6 mg), hydroxylamine hydrochloride (34.7 mg), bis-acetonitrile palladium (II) chloride (6.5 mg), 2-dicyclohexylphosphonium-2 ',6' -diisopropoxy-1, 1' -biphenyl (25.7 mg) and N-methylpyrrolidone (4.0 mL) were added in this order. Putting the ampoule bottle into an autoclave, replacing air in the autoclave with carbon monoxide for three times, filling carbon monoxide with 20atm, heating to 120 ℃ and reacting for 12 hours. After the autoclave is cooled, carbon monoxide in the autoclave is slowly released. Pouring the reaction solution into methanol, centrifuging the mixture to obtain a crude product, subsequently washing with methanol and water in sequence, and drying in vacuum to obtain a polyamide product with a yield of 80% and a number average molecular weight of 1.8X 10 4 The polymer dispersity index was 4.40.
Example 5: preparation of polyamides from aryldienes
In a strictly dry ampoule, aryldiene (405.8 mg), hydroxylamine hydrochloride (34.7 mg), bis-acetonitrile palladium chloride (g/l) were added in this orderII) (6.5 mg), 2-dicyclohexylphosphonium-2 ',6' -diisopropyloxy-1, 1' -biphenyl (25.7 mg) and N-methylpyrrolidone (4.0 mL). Putting the ampoule bottle into an autoclave, replacing the air in the autoclave with carbon monoxide for three times, filling 20atm of carbon monoxide, heating to 120 ℃ and reacting for 12 hours. After the autoclave is cooled, carbon monoxide in the autoclave is slowly released. The reaction solution was poured into methanol, and the mixture was centrifuged to give a crude product, which was subsequently washed with methanol and water in this order and dried under vacuum to give a polyamide product in a yield of 78% and having a number average molecular weight of 8.4X 10 4 The polymer dispersity index was 2.58.
Example 6: preparation of polyamides from arylfluorenedienes
To a strictly dry ampoule were added sequentially aryldiene (424.7 mg), hydroxylamine hydrochloride (55.6 mg), bis-acetonitrile palladium (II) chloride (10.4 mg), 2-dicyclohexylphosphonium-2 ',6' -diisopropoxy-1, 1' -biphenyl (41.1 mg), 6-methyl-2-pyridinecarbonitrile (18.9 mg) and anisole (2.0 mL). Putting the ampoule bottle into an autoclave, replacing air in the autoclave with carbon monoxide for three times, filling 20atm of carbon monoxide, heating to 120 ℃ and reacting for 24 hours. After the autoclave is cooled, carbon monoxide in the autoclave is slowly released. Pouring the reaction solution into methanol, centrifuging the mixture to obtain a crude product, subsequently washing with methanol and water in sequence, and drying in vacuum to obtain a polyamide product with a yield of 76% and a number average molecular weight of 6.4X 10 3 The polymer dispersibility index was 3.06.
Example 7: preparation of polyamides from norbornene
Allyl palladium (II) chloride (4.6 mg), 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene (17.4 mg), hydroxylamine hydrochloride (34.7 mg), norbornene (184.1 mg) and anisole (4.0 mL) were sequentially added to a strictly dried ampoule, and the ampoule was placed in an autoclave and carbon monoxide was substituted for the air in the autoclaveThree times and charging 20atm carbon monoxide, heating to 140 deg.C and reacting for 24 hours. After the autoclave is cooled, carbon monoxide in the autoclave is slowly released. The reaction solution was poured into methanol, and the mixture was centrifuged to give a crude product, which was then washed with methanol and water in this order and dried under vacuum to give a polyamide product in a yield of 54% and having a number average molecular weight of 6.2X 10 3 The polymer dispersity index was 5.23.
Example 8: preparation of polyamides from quaternary carbon-linked alkadienes
Allyl palladium (II) chloride (4.6 mg), 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene (17.4 mg), hydroxylamine hydrochloride (34.7 mg), alkyldiene (336.4 mg), 6-methyl-2-pyridinenitrile (11.8 mg) and anisole (4.0 mL) were added in this order to a strictly dry ampoule, and the ampoule was placed in an autoclave, and carbon monoxide was introduced into the autoclave three times and 20atm carbon monoxide was charged, and heated to 120 ℃ for 24 hours. After the autoclave is cooled, carbon monoxide in the autoclave is slowly released. Pouring the reaction solution into methanol, centrifuging the mixture to obtain a crude product, subsequently washing with methanol and water in sequence, and drying in vacuum to obtain a polyamide product with a yield of 58% and a number average molecular weight of 1.3X 10 3 The polymer dispersity index was 1.64.
Example 9: preparation of polyamides from 1, 7-octadiene
To a strictly dried ampoule were added in this order allylpalladium (II) chloride (4.6 mg), 4, 5-bis-diphenylphosphino-9, 9-dimethylxanthene (17.4 mg), hydroxylamine hydrochloride (34.7 mg), 1, 7-octadiene (220.2 mg), 6-methyl-2-pyridinecarbonitrile (11.8 mg) and anisole (4.0 mL), the ampoule was placed in an autoclave, carbon monoxide was introduced into the autoclave three times to replace the air in the autoclave and 20atm carbon monoxide was charged, and the mixture was heated to 120 ℃ to react for 24 hours. After the autoclave is cooled, carbon monoxide in the autoclave is slowly released. Dissolving the reaction solutionPouring the solution into methanol, centrifuging the mixture to obtain crude product, washing with methanol and water sequentially, and vacuum drying to obtain polyamide product with yield of 66% and number average molecular weight of 2.4 × 10 3 The polymer dispersibility index was 1.00.
Example 10: preparation of polyamides from 1, 3-butadiene
To a strictly dried ampoule were added in this order allyl palladium (II) chloride (7.3 mg), 4, 5-bis-diphenylphosphino-9, 9-dimethylxanthene (27.8 mg), hydroxylamine hydrochloride (55.6 mg), 1, 3-butadiene (1.0 mL,2.8 mol/Linanisole), 6-methyl-2-pyridinecarbonitrile (11.8 mg) and anisole (2.0 mL), the ampoule was placed in an autoclave, carbon monoxide was introduced into the autoclave three times to replace the air in the autoclave and 20atm carbon monoxide was charged, and the mixture was heated to 140 ℃ to react for 24 hours. After the autoclave is cooled, carbon monoxide in the autoclave is slowly released. The reaction solution was poured into methanol, and the mixture was centrifuged to give a crude product, which was subsequently washed with methanol and water in this order and dried under vacuum to give a polyamide product in a yield of 61% and having a number average molecular weight of 3.1X 10 3 The polymer dispersity index was 2.16.
From the above examples, the catalytic synthesis method for preparing polyamide provided by the invention has the advantages of cheap and easily available raw materials, simple synthesis process and capability of simultaneously preparing aromatic polyamide and aliphatic polyamide. The invention not only provides a new thought and a new process for preparing the polyamide, but also promotes the diversity synthesis of the functionalized polyamide.
The above examples are merely provided to facilitate an understanding of the method and core concepts of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (5)
1. A method for synthesizing polyamide by olefin hydroamine carbonylation is characterized in that:
taking a diene monomer, hydroxylamine hydrochloride and carbon monoxide as raw materials, and under the combined action of a palladium catalyst, a ligand and alkali, realizing the diversity synthesis of polyamide in one step through an alkene relay hydroamine carbonylation process, wherein the synthetic route is shown as a route 1 or a route 2;
route 1:
route 2:
in the formula (II) wherein R is a substituent 1 Independently selected from H, straight chain or branched chain C1-C40 aliphatic group, C4-C12 aromatic group or heterocyclic group;
in the synthesis process, the pressure of the carbon monoxide is controlled to be 10-60 atm;
in scheme 1:
the palladium catalyst is selected from one or more of palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium acetylacetonate, bis-acetonitrile palladium chloride, bis-tri-tert-butylphosphine palladium and allyl palladium chloride;
the ligand is selected from one or more of triphenylphosphine, benzyldiadamantylphosphine, dicyclohexyl- (2, 6-diisopropylphenyl) phosphine, 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 2-dicyclohexylphosphine-2 '6' -bis (N, N-dimethylamino) -1,1' -biphenyl, 2-dicyclohexylphosphine-2 ',6' -diisopropoxy-1, 1' -biphenyl, and 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl monophosphine ligand;
in route 2:
the palladium catalyst is selected from one or more of palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, palladium acetylacetonate, bis-acetonitrile palladium chloride, bis-tri-tert-butylphosphine palladium and allyl palladium chloride;
the ligand is selected from one or more of 4, 5-bis (diphenylphosphino) -9, 9-dimethyl xanthene, 1' -bis (diphenylphosphino) ferrocene, bis (2-diphenylphosphino) ether, 1, 2-bis (di-tert-butylphosphinomethyl) benzene, 1, 3-bis (dimethylcyclopentylphosphino) benzene, 4, 6-bis (diphenylphosphino) phenazine, bis (diphenylphosphinomethane) and 1, 4-bis (diphenylphosphino) butane diphosphine ligand;
the alkali is selected from one or more of sodium acetate, sodium phosphate, sodium benzoate, potassium acetate, potassium phosphate, triethylamine, N-diisopropylethylamine, 1, 8-diazohetero-bis-spiro [5.4.0] undec-7-ene, triethylene diamine, pyridine, 4-dimethylamino pyridine and 2-cyano-6-methyl pyridine;
the molar ratio of the diene monomer to the hydroxylamine hydrochloride is 1.5.
2. The method of claim 1, wherein:
the diene monomer is selected from at least one of the following structural compounds:
substituent R 2 、R 3 、R 4 、R 5 、R 6 Independently selected from H, straight chain or branched chain C1-C40 aliphatic group, C4-C12 aromatic group or heterocyclic group; m is 1 、m 2 、m 3 、m 4 Represents the chain length and independently takes a value of 1-20.
3. A method according to claim 1 or 2, characterized by comprising the steps of:
adding a diene monomer, hydroxylamine hydrochloride, a palladium catalyst, a ligand, an alkali additive and a solvent into a reaction kettle in sequence, replacing air in the kettle with carbon monoxide for three times, filling carbon monoxide with a certain pressure, and heating to a set temperature for reacting for a certain time; after the reaction is finished, slowly releasing carbon monoxide in the autoclave after the autoclave is cooled, pouring the reaction liquid into methanol, centrifugally separating the mixture to obtain a crude product, then washing the crude product with methanol and water in sequence, and drying the crude product in vacuum to obtain the polyamide product.
4. The method of claim 3, wherein:
the solvent is one or more selected from anisole, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
5. The method of claim 3, wherein:
the reaction temperature is controlled between 100 and 200 ℃, and the reaction time is controlled between 12 and 72 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106029781A (en) * | 2014-03-10 | 2016-10-12 | 英派尔科技开发有限公司 | Methods for producing nylon 7 |
| CN109293522A (en) * | 2018-11-08 | 2019-02-01 | 中国科学院兰州化学物理研究所 | A kind of preparation method of fatty acid amide |
| CN113788748A (en) * | 2021-09-15 | 2021-12-14 | 华东师范大学 | Method for preparing straight-chain carbonyl compound by catalyzing unsaturated hydrocarbon with multidentate phosphine ligand modified palladium combined catalyst |
-
2022
- 2022-06-13 CN CN202210661409.2A patent/CN114854005B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106029781A (en) * | 2014-03-10 | 2016-10-12 | 英派尔科技开发有限公司 | Methods for producing nylon 7 |
| CN109293522A (en) * | 2018-11-08 | 2019-02-01 | 中国科学院兰州化学物理研究所 | A kind of preparation method of fatty acid amide |
| CN113788748A (en) * | 2021-09-15 | 2021-12-14 | 华东师范大学 | Method for preparing straight-chain carbonyl compound by catalyzing unsaturated hydrocarbon with multidentate phosphine ligand modified palladium combined catalyst |
Non-Patent Citations (4)
| Title |
|---|
| Palladium-catalyzed highly regioselective hydroaminocarbonylation of aromatic alkenes to branched amides;Jinping Zhu et al.,;《Org.Biomol.Chem》;20170322;第15卷;第2910-2913页 * |
| Palladium-catalyzed regiodivergent hydroaminocarbonylation of alkenes to primary amides with ammonium chloride;Bao Gao et al.,;《Chem.Sci》;20171024;第9卷;第380-386页 * |
| Palladium-catalyzed relay hydroaminocarbonylation of alkenes with hydroxylamine hydrochloride as an ammonia equivalent;Jiawen Li et al.,;《COMMUNICATIONS CHEMISTRY》;20190201;第2卷(第14期);第1-9页 * |
| Photodecomposition of formohydroxamic acid. Matrix isolation FTIR and DFT studies;Magdalena Sałdyka et al.,;《Phys. Chem. Chem. Phys》;20030929;第5卷;第4790-4797页 * |
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