CN116354829A - Preparation method and application of pentyenediamine adipate - Google Patents
Preparation method and application of pentyenediamine adipate Download PDFInfo
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- CN116354829A CN116354829A CN202310368706.2A CN202310368706A CN116354829A CN 116354829 A CN116354829 A CN 116354829A CN 202310368706 A CN202310368706 A CN 202310368706A CN 116354829 A CN116354829 A CN 116354829A
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- adipate
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- adipic acid
- lysine
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 title description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 76
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims abstract description 38
- 239000001361 adipic acid Substances 0.000 claims abstract description 38
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 38
- -1 pentylene diamine adipate Chemical compound 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000004472 Lysine Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 19
- 235000019766 L-Lysine Nutrition 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000011541 reaction mixture Substances 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 230000000911 decarboxylating effect Effects 0.000 claims abstract description 4
- 229920006118 nylon 56 Polymers 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 12
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- HXPLANLCFWPRIG-UHFFFAOYSA-N 5-azaniumylpentylazanium;hexanedioate Chemical compound NCCCCCN.OC(=O)CCCCC(O)=O HXPLANLCFWPRIG-UHFFFAOYSA-N 0.000 claims description 7
- DIELDZAPFMXAHA-UHFFFAOYSA-N 3-phenylcyclohex-2-en-1-one Chemical compound O=C1CCCC(C=2C=CC=CC=2)=C1 DIELDZAPFMXAHA-UHFFFAOYSA-N 0.000 claims description 6
- SHOJXDKTYKFBRD-UHFFFAOYSA-N 4-Methyl-3-penten-2-one, 9CI Chemical compound CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 claims description 6
- 239000005973 Carvone Substances 0.000 claims description 6
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 6
- OLNJUISKUQQNIM-UHFFFAOYSA-N indole-3-carbaldehyde Chemical compound C1=CC=C2C(C=O)=CNC2=C1 OLNJUISKUQQNIM-UHFFFAOYSA-N 0.000 claims description 6
- ZSKGQVFRTSEPJT-UHFFFAOYSA-N pyrrole-2-carboxaldehyde Chemical compound O=CC1=CC=CN1 ZSKGQVFRTSEPJT-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000004753 textile Substances 0.000 claims description 4
- LTYLUDGDHUEBGX-UHFFFAOYSA-N 1-(cyclohexen-1-yl)ethanone Chemical compound CC(=O)C1=CCCCC1 LTYLUDGDHUEBGX-UHFFFAOYSA-N 0.000 claims description 3
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical compound C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 claims description 3
- IITQJMYAYSNIMI-UHFFFAOYSA-N 3-Methyl-2-cyclohexen-1-one Chemical compound CC1=CC(=O)CCC1 IITQJMYAYSNIMI-UHFFFAOYSA-N 0.000 claims description 3
- SNWQUNCRDLUDEX-UHFFFAOYSA-N inden-1-one Chemical compound C1=CC=C2C(=O)C=CC2=C1 SNWQUNCRDLUDEX-UHFFFAOYSA-N 0.000 claims description 3
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 claims description 3
- MTZWHHIREPJPTG-UHFFFAOYSA-N phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims 1
- RKLJSFSLDCKWPH-UHFFFAOYSA-N C(CCCCC(=O)O)(=O)O.C(CCCC)(N)N Chemical compound C(CCCCC(=O)O)(=O)O.C(CCCC)(N)N RKLJSFSLDCKWPH-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 39
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 22
- 239000000706 filtrate Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- WPLOVIFNBMNBPD-ATHMIXSHSA-N subtilin Chemical compound CC1SCC(NC2=O)C(=O)NC(CC(N)=O)C(=O)NC(C(=O)NC(CCCCN)C(=O)NC(C(C)CC)C(=O)NC(=C)C(=O)NC(CCCCN)C(O)=O)CSC(C)C2NC(=O)C(CC(C)C)NC(=O)C1NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C1NC(=O)C(=C/C)/NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)CNC(=O)C(NC(=O)C(NC(=O)C2NC(=O)CNC(=O)C3CCCN3C(=O)C(NC(=O)C3NC(=O)C(CC(C)C)NC(=O)C(=C)NC(=O)C(CCC(O)=O)NC(=O)C(NC(=O)C(CCCCN)NC(=O)C(N)CC=4C5=CC=CC=C5NC=4)CSC3)C(C)SC2)C(C)C)C(C)SC1)CC1=CC=CC=C1 WPLOVIFNBMNBPD-ATHMIXSHSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 4
- 235000018977 lysine Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- PJLODCSPQGTOTJ-UHFFFAOYSA-N 1-(2-methoxyphenyl)butane-1,3-dione Chemical compound COC1=CC=CC=C1C(=O)CC(C)=O PJLODCSPQGTOTJ-UHFFFAOYSA-N 0.000 description 2
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
Abstract
The invention provides a preparation method and application of pentylene diamine adipate. The preparation method comprises the following steps: a) Decarboxylating L-lysine under the action of a catalyst; b) And C), carrying out in-situ reaction on the reaction mixture obtained in the step A) and adipic acid to obtain the pentylene diamine adipate. According to the invention, low-cost L-lysine is used as a raw material, and a reaction mixture containing the pentanediamine is obtained after chemical decarboxylation reaction in the presence of a catalyst, and the reaction mixture is directly reacted with adipic acid without further purification post-treatment, so that the pentanediamine adipate can be obtained, the steps are simple and convenient, complicated post-treatment operation is not needed, the realization is convenient, the environment is friendly, and the method is suitable for large-scale production, wherein the yield of the pentanediamine adipate can reach 82% and the purity can reach 99%.
Description
Technical Field
The invention belongs to the technical field of biological base materials, and particularly relates to a preparation method and application of pentanediamine adipate.
Background
Nylon has non-substitutability in chemical fiber due to its advantages of good rebound resilience, light weight, softness, high mechanical strength, antistatic property, easy dyeing, etc. Of these, nylon 6 and nylon 66 yield is greatest, accounting for about 90% of the total nylon yield. It has been reported that the 2022 worldwide nylon 6 and nylon 66 market scale is up to 1975.92 gigabytes and continues to grow at an average acceleration of 6.22%. However, the raw materials for producing nylon at present mainly comprise fossil resources, and along with the exhaustion of the fossil resources and the increasing of atmospheric pollution, the development of bio-based materials has important significance for green environmental protection and sustainable development.
Nylon 56 (poly (pentylene diamine) adipic acid) is used as a bio-based material and is polymerized by bio-based pentylene diamine and petroleum-based adipic acid, and is gradually paid attention to because of the advantages of high strength, wear resistance, flame retardance, moisture absorption, excellent rebound resilience and the like, which are similar to those of nylon 66 products.
At present, nylon 56 is generally prepared by preparing a pure 1, 5-pentanediamine (also called "pentanediamine") product, and then carrying out salt-forming polymerization or direct polymerization on the product and adipic acid. However, the preparation method of the pentanediamine mainly comprises the steps of preparing the lysine by enzyme catalysis decarboxylation or preparing the lysine by a chemical method through a bioengineering technology, wherein the enzyme catalysis method has the problems of complicated fermentation process, difficult purification of the 1, 5-pentanediamine, difficult separation of products after fermentation, low productivity, high industrial cost and the like, so that the production of the nylon 56 is greatly limited. Likewise, the chemical process for preparing the pentylene diamine generally first yields the pentylene diamine hydrochloride, and then undergoes cumbersome purification operations to yield a pure pentylene diamine product. Therefore, the current method for preparing nylon 56 has the problems of high cost and complicated steps, and is unfavorable for realizing large-scale production.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method and application of pentylene diamine adipate. The preparation method is low in cost, simple to operate, environment-friendly and suitable for large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a process for the preparation of pentamethylenediamine adipate, comprising the steps of:
a) Decarboxylating L-lysine under the action of a catalyst;
b) And C), carrying out in-situ reaction on the reaction mixture obtained in the step A) and adipic acid to obtain the pentylene diamine adipate.
Preferably, the decarboxylation reaction is carried out at a temperature of 100-200 ℃ for a time of 0.5-48 hours.
Preferably, the temperature of the in-situ reaction is 30-80 ℃ and the time is 0.5-48 h.
Preferably, the catalyst is selected from any one or more of acetophenone, 2-bromoacetophenone, 4-methyl-3-penten-2-one, 2, 4-pentanedione, 2, 6-dimethyl-2, 5-heptadien-4-one, methylcyclohexenone, isophorone, 3-phenyl-2-cyclohexen-1-one, R-carvone, cyclohexanone, 1-acetyl-1-cyclohexene, 2-acetoacetyl anisole, 1-tetralone, 1-indenone, cyclododecanone, indole-3-carbaldehyde or pyrrole-2-carbaldehyde.
Preferably, the molar ratio of the catalyst to L-lysine is (0.05-10): 1.
Preferably, the molar ratio of adipic acid to L-lysine is (0.5-2): 1.
Preferably, the decarboxylation reaction is carried out in the presence of a solvent.
Preferably, the solvent is selected from any one or more of dimethyl sulfoxide, N-dimethylacetamide, N-methylpyrrolidone, N-propanol, isopropanol, N-butanol, isobutanol, tert-butanol, cyclohexanol or sulfolane.
In a second aspect, the present invention provides a biobased nylon 56 obtained by polymerizing the pentylene diamine adipate obtained in the above-mentioned technical scheme.
In a third aspect, the present invention provides a textile comprising biobased nylon 56 as referred to in the above-described aspects.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for preparing 1, 5-pentanediamine by organic catalysis of chemical decarboxylation of L-lysine, which further comprises the steps of reacting the L-lysine with adipic acid to prepare pentanediamine adipate. The invention does not need to carry out post-treatment on the mixture of 1, 5-pentanediamine to obtain a pure pentanediamine product, but directly mixes the mixture of 1, 5-pentanediamine with adipic acid to carry out in-situ reaction to obtain pentanediamine adipate, and the biology-based nylon 56 can be obtained after the pentanediamine adipate is polymerized. Compared with the prior art for preparing the pure 1, 5-pentanediamine product by adopting enzymatic decarboxylation or chemical decarboxylation, the method provided by the invention has the advantages of low economic cost, simple steps, no need of complex post-treatment operation for obtaining the pure pentanediamine product, convenience for realization, environmental friendliness, high yield of the prepared pentanediamine adipate which can reach 82%, suitability for large-scale production and important practical significance for preparing the bio-based nylon 56 salt.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of pentamethylenediamine adipate obtained in example 1;
FIG. 2 is a nuclear magnetic resonance spectrum of pentamethylenediamine adipate obtained in example 1.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Because the bio-based nylon 56 salt is generally prepared by preparing a pure 1, 5-pentanediamine product and then carrying out salt-forming polymerization or direct polymerization on the pure 1, 5-pentanediamine product and adipic acid in the prior art. The pure 1, 5-pentanediamine product is generally prepared by an enzyme catalytic decarboxylation method or a chemical method, but has the problems of higher cost, lower yield and complicated steps. Based on this, the present invention provides a process for the preparation of pentamethylenediamine adipate, which does not require the production of a pure pentamethylenediamine product, but rather, directly reacts a mixture comprising pentamethylenediamine with adipic acid in situ to produce the desired product, comprising the steps of:
a) Decarboxylating L-lysine under the action of a catalyst;
b) And C), carrying out in-situ reaction on the reaction mixture obtained in the step A) and adipic acid to obtain the pentylene diamine adipate.
According to the invention, L-lysine is first subjected to decarboxylation under the action of a catalyst to obtain a reaction mixture comprising pentylene diamine. The L-lysine is not particularly limited and may be a general commercial product. The catalyst is specifically preferably selected from any one or more of acetophenone, 2-bromoacetophenone, 4-methyl-3-penten-2-one, 2, 4-pentanedione, 2, 6-dimethyl-2, 5-heptadien-4-one, methylcyclohexenone, isophorone, 3-phenyl-2-cyclohexen-1-one, R-carvone, cyclohexanone, 1-acetyl-1-cyclohexene, 2-acetoacetylanisole, 1-tetralone, 1-indenone, cyclododecanone, indole-3-carbaldehyde or pyrrole-2-carbaldehyde, more preferably from any one or more of isophorone, 3-phenyl-2-cyclohexen-1-one, R-carvone or cyclohexanone. In some embodiments of the invention, the decarboxylation reaction occurs after mixing, preferably in a molar ratio of catalyst to L-lysine of (0.05 to 10): 1, which may be 0.05:1, 0.1:1, 0.5:1, 1:1, 3:1, 0.05:1, 5:1, 8:1 or 10:1, preferably (0.1 to 8): 1. The decarboxylation reaction is carried out at a temperature of 100 to 200 ℃, preferably 120 to 180 ℃, more preferably 140 to 160 ℃ for a time of 0.5 to 48 hours, preferably 8 to 36 hours, more preferably 12 to 24 hours. In some embodiments of the present invention, the decarboxylation reaction is carried out in the presence of a solvent, i.e., a catalyst is mixed with L-lysine in the proportions described above with the solvent and the decarboxylation reaction occurs, with the solvent being specifically preferably selected from any one or more of dimethyl sulfoxide (DMSO), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-propanol, isopropanol, N-butanol, isobutanol, tert-butanol, cyclohexanol or sulfolane, more preferably from any one or more of N-propanol, isopropanol, N-butanol, isobutanol, tert-butanol or cyclohexanol. The solvent is used in an amount of 0.01 to 10g/mL, preferably 0.1 to 5g/mL, more preferably 0.2 to 1g/mL, based on the mass of lysine. In the present invention, the decarboxylation reaction is preferably performed under stirring.
After the decarboxylation reaction is completed, the obtained reaction mixture comprising the pentanediamine is reacted with adipic acid, and then the pentanediamine adipate is obtained. The source of adipic acid is not particularly limited, and it is a general commercial product. In the present invention, the adipic acid is used in an amount of (0.5-2): 1, specifically 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.8:1 or 2:1, based on L-lysine, and preferably (1-2): 1. In some embodiments of the present invention, to avoid having a small residual amount of the reactant L-lysine, after the decarboxylation reaction is completed, the resulting reaction mixture is preferably suction filtered to obtain a filtrate comprising pentylene diamine and mixed with a first solvent to facilitate the performance of subsequent experiments; while the adipic acid solid is dissolved in a second solvent. Wherein the first and second solvents, which may be the same or different, are each independently selected from any one or more of water, methanol, ethanol, acetonitrile, ethyl acetate, acetone, tetrahydrofuran or DMSO, preferably both with the same reagent, in one embodiment of the present invention, the first and second solvents are preferably methanol. The amounts of the first solvent and the second solvent used in the present invention are not particularly limited, and may be added as needed. The solution of the pentylene diamine-containing filtrate is then mixed with the adipic acid solution, preferably by slowly dropping the solution of the pentylene diamine-containing filtrate into the adipic acid solution and reacting at 30 to 80 c for 0.5 to 48 hours, preferably at 50 to 80 c for 2 to 36 hours, more preferably at 50 to 60 c for 4 to 24 hours, preferably with stirring. In some embodiments of the invention, after the reaction is completed, the resulting reaction solution is preferably filtered while hot to prevent excessive adipic acid from precipitating, affecting the yield of pentylenediamine adipate. After the filtration is completed, the precipitate is taken and washed to remove impurities from the surface, which may be an alcohol reagent, preferably methanol. After the washing is finished, the washing method preferably further comprises a drying treatment, wherein the drying can be performed by adopting a drying mode which is well known to a person skilled in the art, and the washing method is preferably used for drying under vacuum at 50-70 ℃ for 4-48 hours, more preferably at 60 ℃ for 4-48 hours.
According to the preparation method of the pentylene diamine adipate, provided by the invention, the L-lysine with severely excessive productivity and low price is taken as a raw material, and the reaction mixture comprising pentylene diamine is obtained after the chemical decarboxylation reaction in the presence of a catalyst, and the pentylene diamine adipate can be directly reacted with adipic acid without further purification and post-treatment, so that the pentylene diamine adipate is obtained, the steps are simple, the complex post-treatment operation is not needed, the realization is convenient, the environment is friendly, and the preparation method is suitable for large-scale production.
The obtained pentylene diamine adipate by the preparation method has the highest yield of 82 percent and the purity of 99 percent. The preparation method provided by the invention can realize high-purity and high-yield production of the p-phenylenediamine adipate.
The bio-based nylon 56 can be obtained by polymerizing the pentylene diamine adipate prepared by the method as a monomer, and the method is not particularly limited in the polymerization process and can be carried out according to technical means well known to those skilled in the art.
The bio-based nylon 56 can be applied to various fields, such as textile, filtering membrane or automobile engineering material, and based on the bio-based nylon 56, the invention also provides a textile comprising the bio-based nylon 56.
In order to further illustrate the present invention, the following examples are provided. The experimental raw materials used in the following examples of the present invention can be purchased from the market and are general commercial products; or prepared according to conventional techniques well known to those skilled in the art. Among them, acetophenone, cyclohexanone, R-carvone, 4-bromoacetophenone, 3-phenyl-2-cyclohexen-1-one, 2, 4-pentanedione and isophorone used in the following examples were all reagents of chemically pure grade.
The yield in the examples below is the mass of the actual pentylene diamine adipate obtained/the mass of the theoretical lysine all decarboxylated to pentylene diamine and reacted with adipic acid to give pentylene diamine adipate.
Example 1
0.73-g L-lysine, 1mL of acetophenone are added into 3mL of DMSO under nitrogen atmosphere, stirring is carried out for 8h at 160 ℃, the reaction is cooled to room temperature after the completion of the reaction, the filtrate is obtained through suction filtration, and the filtrate and 0.73g of adipic acid are respectively added into two parts of 30mL of anhydrous methanol. Slowly dripping the methanol solution into the methanol solution dissolved with adipic acid, stirring and reacting for 2 hours at 40 ℃, filtering while the solution is hot, washing with methanol, and drying in vacuum at 60 ℃ for 8 hours to obtain the pentylene diamine adipate (0.91 g, 73% yield and 99% purity). 1 HNMR(D 2 O,300MHz)δ2.94(t,4H),2.12(t,4H),1.56-1.72(m,4H),1.48(t,4H),1.31-1.43(m,2H). 13 CNMR(D 2 O,100MHz)δ183.68,39.11,37.44,26.24,25.86,22.66.
The nuclear magnetic hydrogen spectrum and the nuclear magnetic carbon spectrum of the pentylene diamine adipate obtained in example 1 are shown in fig. 1 and 2 respectively, and the product is pentylene diamine adipate.
Example 2
0.73-g L-lysine and 0.4mL cyclohexanone are added into 3mL DMAc under nitrogen atmosphere and stirred for reaction for 8h at 160 ℃, the reaction is cooled to room temperature after the completion of the reaction, filtrate is obtained through suction filtration, and the filtrate and 0.73g adipic acid are respectively added into two parts of 30mL anhydrous methanol. Slowly dripping the methanol solution into the methanol solution dissolved with adipic acid, stirring and reacting for 4 hours at 40 ℃, filtering while the solution is hot, washing with methanol, and drying in vacuum at 60 ℃ for 8 hours to obtain the pentylene diamine adipate (0.88 g, yield 71%, purity 99%). The nuclear magnetic results were consistent with example 1.
Example 3
0.73g of L-lysine and 0.4mL of R-carvone are added into 5mL of cyclohexanol under nitrogen atmosphere, stirring is carried out for 8 hours at 160 ℃, the reaction is cooled to room temperature after the reaction is finished, the filtrate is obtained through suction filtration, and the filtrate and 0.73g of adipic acid are respectively added into two parts of 30mL of anhydrous methanol. Slowly dripping the methanol solution into the methanol solution dissolved with adipic acid, stirring and reacting for 4 hours at 40 ℃, filtering while the solution is hot, washing with methanol, and drying in vacuum at 60 ℃ for 8 hours to obtain the pentylene diamine adipate (0.97 g, yield 78% and purity 99%). The nuclear magnetic results were consistent with example 1.
Example 4
0.73-g L-lysine, 0.4mL of 4-bromoacetophenone are added into 6mL of NMP under nitrogen atmosphere, stirred and reacted for 12h at 160 ℃, the reaction is cooled to room temperature after the completion of the reaction, the filtrate is obtained through suction filtration, and the filtrate and 0.73g of adipic acid are respectively added into two parts of 30mL of absolute ethanol. The ethanol solution dropped into the reaction liquid is slowly dropped into the ethanol solution dissolved with adipic acid to react for 2 hours at 60 ℃ with stirring, the hot filtration, ethanol washing and vacuum drying for 8 hours at 60 ℃ to obtain the pentylene diamine adipate (0.86 g, 69 percent yield and 99 percent purity). The nuclear magnetic results were consistent with example 1.
Example 5
0.73-g L-lysine, 0.4mL of 3-phenyl-2-cyclohexene-1-one are added into 6mL of n-butanol under the nitrogen atmosphere, the mixture is stirred and reacted for 12 hours at 160 ℃, the reaction is cooled to room temperature after the completion of the reaction, the filtrate is obtained through suction filtration, and the filtrate and 0.73g of adipic acid are respectively added into two parts of 30mL of absolute ethanol. The ethanol solution dropped into the reaction liquid is slowly dropped into the ethanol solution dissolved with adipic acid to react for 8 hours at 60 ℃ with stirring, the hot filtration, ethanol washing and vacuum drying for 8 hours at 60 ℃ to obtain the pentylene diamine adipate (0.98 g, yield 79% and purity 99%). The nuclear magnetic results were consistent with example 1.
Example 6
0.73-g L-lysine, 1.5mL acetophenone is added into 6mL DMAc under nitrogen atmosphere, stirred and reacted for 24h at 130 ℃, the reaction is cooled to room temperature after the completion of the reaction, the filtrate is obtained through suction filtration, and the filtrate and 0.73g adipic acid are respectively added into two parts of 30mL absolute ethanol. The ethanol solution dropped into the reaction liquid is slowly dropped into the ethanol solution dissolved with adipic acid to react for 8 hours at 60 ℃, the mixture is filtered while the mixture is hot, the mixture is washed by ethanol, and the mixture is dried for 8 hours at 60 ℃ in vacuum, thus obtaining the pentylene diamine adipate (0.89 g, yield 72 percent, purity 99 percent). The nuclear magnetic results were consistent with example 1.
Example 7
0.73-g L-lysine, 1.5mL of 2, 4-pentanedione are added into 6mL of normal propyl alcohol under nitrogen atmosphere, stirred and reacted for 24 hours at 130 ℃, the reaction is cooled to room temperature after the completion of the reaction, the filtrate is obtained through suction filtration, and the filtrate and 0.73g of adipic acid are respectively added into two parts of 30mL of absolute ethanol. The ethanol solution dropped into the reaction liquid is slowly dropped into the ethanol solution dissolved with adipic acid to react for 8 hours at 60 ℃ with stirring, the hot filtration, ethanol washing and vacuum drying for 8 hours at 60 ℃ to obtain the pentylene diamine adipate (1.01 g, yield 81% and purity 99%). The nuclear magnetic results were consistent with example 1.
Example 8
0.73-g L-lysine, 0.3mL of isophorone are added into 6mL of cyclohexanol under nitrogen atmosphere, stirring is carried out for 4 hours at 130 ℃, the reaction is cooled to room temperature after the reaction is finished, the filtrate is obtained through suction filtration, and the filtrate and 0.73g of adipic acid are respectively added into two parts of 30mL of absolute ethanol. The ethanol solution dropped into the reaction liquid is slowly dropped into the ethanol solution dissolved with adipic acid to react for 8 hours at 60 ℃ with stirring, the hot filtration, ethanol washing and vacuum drying for 8 hours at 60 ℃ to obtain the pentylene diamine adipate (1.02 g, yield 82 percent and purity 99 percent). The nuclear magnetic results were consistent with example 1.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A process for the preparation of pentamethylenediamine adipate comprising the steps of:
a) Decarboxylating L-lysine under the action of a catalyst;
b) And C), carrying out in-situ reaction on the reaction mixture obtained in the step A) and adipic acid to obtain the pentylene diamine adipate.
2. The preparation method according to claim 1, wherein the decarboxylation reaction is carried out at a temperature of 100 to 200 ℃ for a time of 0.5 to 48 hours.
3. The method according to claim 1, wherein the in-situ reaction is carried out at a temperature of 30 to 80 ℃ for a time of 0.5 to 48 hours.
4. The process according to claim 1, wherein the molar ratio of the catalyst to L-lysine is from (0.05 to 10): 1.
5. The process according to claim 1, wherein the molar ratio of adipic acid to L-lysine is (0.5-2): 1.
6. The preparation method according to claim 1, wherein the catalyst is selected from any one or more of acetophenone, 2-bromoacetophenone, 4-methyl-3-penten-2-one, 2, 4-pentanedione, 2, 6-dimethyl-2, 5-heptadien-4-one, methylcyclohexenone, isophorone, 3-phenyl-2-cyclohexen-1-one, R-carvone, cyclohexanone, 1-acetyl-1-cyclohexene, 2-anisole, 1-tetralone, 1-indenone, cyclododecanone, indole-3-carbaldehyde or pyrrole-2-carbaldehyde.
7. The process of claim 1, wherein the decarboxylation reaction is carried out in the presence of a solvent.
8. The method according to claim 7, wherein the solvent is selected from any one or more of dimethyl sulfoxide, N-dimethylacetamide, N-methylpyrrolidone, N-propanol, isopropanol, N-butanol, isobutanol, t-butanol, cyclohexanol, and sulfolane.
9. A biobased nylon 56, characterized in that it is obtained by polymerizing a pentylene diamine adipate obtained by the preparation method according to any one of claims 1 to 8.
10. A textile comprising the biobased nylon 56 of claim 9.
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| CN107001625A (en) * | 2014-12-17 | 2017-08-01 | 上海凯赛生物技术研发中心有限公司 | A kind of nylon salt and preparation method thereof |
| US20180002272A1 (en) * | 2014-12-17 | 2018-01-04 | Cathay R&D Center Co., Ltd. | Method for purifying 1,5-pentanediamine and 1,5-pentanediamine |
| CN111217710A (en) * | 2020-02-27 | 2020-06-02 | 中国科学院长春应用化学研究所 | Method for preparing 1, 5-pentanediamine by organic catalysis of L-lysine chemical decarboxylation |
| CN111321481A (en) * | 2018-12-14 | 2020-06-23 | 优纤科技（丹东）有限公司 | Production method of antistatic nylon 56 fiber |
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| CN107001625A (en) * | 2014-12-17 | 2017-08-01 | 上海凯赛生物技术研发中心有限公司 | A kind of nylon salt and preparation method thereof |
| US20180002272A1 (en) * | 2014-12-17 | 2018-01-04 | Cathay R&D Center Co., Ltd. | Method for purifying 1,5-pentanediamine and 1,5-pentanediamine |
| CN111321481A (en) * | 2018-12-14 | 2020-06-23 | 优纤科技（丹东）有限公司 | Production method of antistatic nylon 56 fiber |
| CN111217710A (en) * | 2020-02-27 | 2020-06-02 | 中国科学院长春应用化学研究所 | Method for preparing 1, 5-pentanediamine by organic catalysis of L-lysine chemical decarboxylation |
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