CN116655585A - Poly (epsilon-caprolactone-epsilon-caprolactam) with controllable main chain sequence and preparation method and application thereof - Google Patents
Poly (epsilon-caprolactone-epsilon-caprolactam) with controllable main chain sequence and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 50
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- -1 cyano, nitroAmino Chemical group 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 claims description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- IOVVFSGCNWQFQT-UHFFFAOYSA-N bis(2,3,4,5,6-pentafluorophenyl) carbonate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1OC(=O)OC1=C(F)C(F)=C(F)C(F)=C1F IOVVFSGCNWQFQT-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 6
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 239000003456 ion exchange resin Substances 0.000 claims description 5
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 5
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 claims description 5
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- HDWGYZHUKPOUMU-UHFFFAOYSA-N azepan-2-one;oxepan-2-one Chemical compound O=C1CCCCCN1.O=C1CCCCCO1 HDWGYZHUKPOUMU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 229960002684 aminocaproic acid Drugs 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- KWTSXDURSIMDCE-QMMMGPOBSA-N (S)-amphetamine Chemical compound C[C@H](N)CC1=CC=CC=C1 KWTSXDURSIMDCE-QMMMGPOBSA-N 0.000 claims description 2
- 229940025084 amphetamine Drugs 0.000 claims description 2
- 239000002657 fibrous material Substances 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 150000001412 amines Chemical class 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 40
- 229920000642 polymer Polymers 0.000 description 22
- 238000002390 rotary evaporation Methods 0.000 description 17
- 238000004440 column chromatography Methods 0.000 description 14
- 239000003208 petroleum Substances 0.000 description 14
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- BNSOYWDFFBDEFB-UHFFFAOYSA-L hydroxy-(hydroxy(dioxo)chromio)oxy-dioxochromium;pyridine Chemical compound C1=CC=NC=C1.O[Cr](=O)(=O)O[Cr](O)(=O)=O BNSOYWDFFBDEFB-UHFFFAOYSA-L 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
-
- 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
- C08G69/44—Polyester-amides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The application discloses poly (epsilon-caprolactone-epsilon-caprolactam) with a controllable main chain sequence, a preparation method and application thereof, wherein the poly (epsilon 0-caprolactone-epsilon 1-caprolactam) is prepared by reacting a monomer compound of a formula A or a monomer compound of a formula B; poly (epsilon-caprolactone-epsilon-caprolactam) shown in formula II is prepared by reaction. The monomer compound of the formula A or the monomer compound of the formula B provided by the application can prepare poly (epsilon-caprolactone-epsilon-caprolactam) at a lower temperature in the presence of weak base, the number average molecular weight of the poly (epsilon-caprolactone-epsilon-caprolactam) is more than 2 ten thousand, the main chain structure of the poly (epsilon-caprolactone-epsilon-caprolactam) is orderly arranged, the PDI is controlled below 1.2, which is obviously superior to the preparation method in the prior art, and the application can prepare the poly (epsilon-caprolactone-epsilon-caprolactam with high precisionAn amine).
Description
Technical Field
The application belongs to the technical field of preparation of functional high molecular compounds, and particularly relates to poly (epsilon-caprolactone-epsilon-caprolactam) with a controllable main chain sequence, and a preparation method and application thereof.
Background
Polyester amides are important polymer materials (Macromolecules 2014, 47, 2471-2478) which retain excellent mechanical properties while also having environmentally friendly properties, and which have better biodegradability and biocompatible degradation products, and thus are of interest and widespread interest to the modern engineering plastics industry.
As a common polyesteramide, the synthesis of poly (epsilon-caprolactone-epsilon-caprolactam) is currently limited to the following several methods: (a) Anionic copolymerization of different initiators, (b) interfacial copolymerization; (c) anionic ring-opening copolymerization. The three methods can be used for preparing high molecular weight random polymers, but the content of ester bonds and amide bonds in the polymer cannot be controlled because the polymer method has inherent problems for monomer sequence synthesis. Researchers (polym. Chem.2020, 11, 1211-1219) have studied the thermal stability, phase transition behavior, crystallinity, wettability and thermal responsiveness of polymers by solution polycondensation of synthetic sequence monomers to give backbones of different contents (ester and amide linkages), but their sequences remain undefined in practice and the dispersibility of the polymers cannot be controlled (PDI > 1.4). The polymer obtained by the traditional anion ring-opening copolymerization has the problems of undefined sequence, difficult control of dispersibility and severe reaction conditions (high temperature and high pressure). At present, no related realization method for synthesizing poly (epsilon-caprolactone-epsilon-caprolactam) with controllable main chain sequence exists.
Disclosure of Invention
In order to solve the above problems, the present application provides a monomer compound of the following formula a or a monomer compound of the following formula B:
wherein p is an integer of 0 to 3; when p is 2 or 3, each R 1 Identical or different, independently of one another, from H, C 1-12 Alkyl, C 1-12 Alkoxy, halogen, cyano, nitro, amino or formyl.
According to an embodiment of the application, p is an integer from 0 to 3, preferably p is 1,2 or 3; more preferably, p is 1 or 2, most preferably, p is 1.
According to an embodiment of the application, when p is 2 or 3, each R 1 Identical or different, independently of one another, from H, C 1-6 Alkyl, C 1-6 Alkoxy, halogen, cyano, nitro, amino or formyl.
According to an embodiment of the application, each R 1 The radicals are identical or different and are selected independently of one another from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or n-hexyl, preferably tert-butyl.
Preferably, the monomer compound of formula a has the following structure:
preferably, the monomer compound of formula B has the following structure:
the application also provides a preparation method of the monomer compound of the formula A or the monomer compound of the formula B, which comprises the following steps:
(K1) Reacting a compound shown in a formula C with pentafluorophenyl carbonate in a solvent to prepare an intermediate 6;
(K2) Reacting intermediate 6, trifluoroacetic acid (TFA) and a basic catalyst in a solvent to prepare a monomer compound of formula A;
or, (P1) reacting a compound shown in a formula D with pentafluorophenyl carbonate in a solvent to prepare an intermediate 10;
(P2) reacting intermediate 10, trifluoroacetic acid (TFA) and a basic catalyst in a solvent to prepare the monomer compound of formula B.
According to an embodiment of the application, the solvent is Dichloromethane (DCM), tetrahydrofuran (THF), chloroform (CHCl) 3 ) At least one kind or a combination of two or more kinds of acetonitrile.
According to an embodiment of the present application, the basic catalyst is at least one or a combination of two or more of triethylamine, diisopropylethylamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD).
According to an embodiment of the present application, the method for preparing the compound represented by formula C includes the steps of:
(1) Reacting a compound shown in a formula E with tert-butyldimethylchlorosilane (TBSCl) to prepare an intermediate 1;
(2) Reacting 1-aminocaproic acid, di-tert-butyl dicarbonate (boc anhydride) and triethylamine to prepare an intermediate 2;
(3) Reacting intermediate 2 with hexanediol to prepare intermediate 3;
(4) Reacting intermediate 3 with intermediate 1 to prepare intermediate 4;
(5) Intermediate 4 was reacted with ion exchange resin (Amberlyst 15) to prepare a compound of formula C, intermediate 5.
According to an embodiment of the present application, the method for preparing the compound represented by formula D includes the steps of:
(S1) reacting the above intermediate 3 with hexanediol to prepare an intermediate 7;
(S2) reacting intermediate 7 with intermediate 1 to prepare intermediate 8;
(S3) reacting intermediate 8 with ion exchange resin (Amberlyst 15) to prepare a compound represented by formula D, namely intermediate 9.
The application also provides poly (epsilon-caprolactone-epsilon-caprolactam) shown in the following formula I or formula II, wherein the poly (epsilon-caprolactone-epsilon-caprolactam) shown in the formula I is prepared by reacting the monomer compound shown in the formula A; poly (epsilon-caprolactone-epsilon-caprolactam) shown in formula II is prepared by reacting the monomer compound shown in formula B;
wherein n is the same or different and is independently selected from the group consisting of numbers 1 to 100;
preferably, n is the same or different and is independently selected from a number from 15 to 50; illustratively 15, 20, 25, 20, 30, 35, 40, 45 or 50.
According to an embodiment of the application, the poly (epsilon-caprolactone-epsilon-caprolactam) of formula I or formula II has a number average molecular weight of 20000 or more, such as 22000 to 200000.
The application also provides a method for preparing poly (epsilon-caprolactone-epsilon-caprolactam) shown in a formula I or a formula II, which comprises the following steps:
reacting a monomer compound shown in a formula A with an initiator to prepare poly (epsilon-caprolactone-epsilon-caprolactam) shown in a formula I;
alternatively, the monomer compound of formula B is reacted with an initiator to produce poly (ε -caprolactone- ε -caprolactam) of formula II.
According to an embodiment of the present application, the initiator is at least one or a combination of two or more of n-hexylamine, n-propylamine, amphetamine.
Illustratively, when in the monomeric compound of formula A or formula B, p is 1, R 1 In the case of tert-butyl, the poly (epsilon-caprolactone-epsilon-caprolactam) of formula I or formula II is prepared as follows:
or alternatively, the first and second heat exchangers may be,
according to an embodiment of the application, the molar ratio of the monomer compound of formula a or the compound of formula B to the initiator is 30-60:1, for example 30:1, 40:1, 45:1, 50:1, 55:1 or 60:1.
According to an embodiment of the application, the process is carried out in a polar solvent, such as DMSO and/or DMF.
According to an embodiment of the application, the method is performed in the presence of a capture agent, such as N-methylaniline.
According to an embodiment of the application, the process is also carried out under catalysis of an organic amine, such as at least one or a combination of two or more of triethylamine, diisopropylethylamine, DBU, TBD.
According to an embodiment of the application, the molar ratio of the monomer compound of formula A or formula B, the organic amine, the scavenger, the initiator is (30-60): (3-6): (75-120): 1, for example 30:3:75:1 or 30:3:120:1.
According to an embodiment of the application, the process is carried out at 30-70 ℃, illustratively 30 ℃, 40 ℃,50 ℃,60 ℃, 70 ℃.
According to an embodiment of the application, the reaction time is 1 to 72 hours.
According to an embodiment of the application, the reaction further comprises a post-treatment step after completion of the reaction: the reaction product was settled in diethyl ether and unreacted monomer and initiator were removed.
The application also provides application of the monomer compound of the formula A, the monomer compound of the formula B, the poly (epsilon-caprolactone-epsilon-caprolactam) of the formula I or the poly (epsilon-caprolactone-epsilon-caprolactam) of the formula II in preparing plastic and fiber materials.
The application has the beneficial effects that:
the monomer compound of the formula A or the monomer compound of the formula B provided by the application can be used for preparing poly (epsilon-caprolactone-epsilon-caprolactam) at a lower temperature in the presence of weak base (such as TEA), the number average molecular weight of the poly (epsilon-caprolactone-epsilon-caprolactam) is more than 2 ten thousand, the main chain structure of the poly (epsilon-caprolactone-epsilon-caprolactam) is orderly arranged (i.e. the ester groups and the amide bonds on the main chain are orderly arranged according to the sequence of-ABBABBABB-or-ABABABBABAB-, and the PDI is controlled below 1.2, so that the poly (epsilon-caprolactone-epsilon-caprolactam) can be prepared with high precision.
Definition and description of terms
The numerical ranges referred to herein are meant to include all numbers at the endpoints of the range and intermediate to the endpoints, e.g., "1-100" numbers refer to endpoints 1 and 100 and all numbers intermediate to the endpoints, e.g., 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 … …. Other numerical ranges have the same definition, e.g., 1-6, etc.
The term "C 1-12 Alkyl "denotes straight-chain and branched alkyl having 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms," C 1-6 Alkyl "means straight and branched alkyl groups having 1,2, 3, 4, 5 or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 3-dimethylbutyl, or 1, 2-dimethylbutyl, or the like, or an isomer thereof.
The term "C 1-12 Alkoxy "means C as described above 1-12 The alkyl group is directly linked to O to form a group, and the group is linked to the rest of the molecule by an O atom.
Drawings
FIG. 1 is a nuclear magnetic pattern of monomer A prepared in example 1 (deuterated reagent used is deuterated dimethyl sulfoxide);
FIG. 2 is a nuclear magnetic spectrum of monomer B prepared in example 1 (deuterated reagent used is deuterated dimethyl sulfoxide);
FIG. 3 is an in situ nuclear magnetic spectrum of polymer I prepared in example 2 (deuterated reagent used was deuterated dimethyl sulfoxide, calculated conversion, polymer insoluble after settling);
FIG. 4 is a nuclear magnetic resonance spectrum of polymer II prepared in example 2 (deuterated reagent used is deuterated dimethyl sulfoxide);
FIG. 5 is a GPC chart of polymer I prepared in example 2;
FIG. 6 is a GPC chart of polymer II prepared in example 2;
FIG. 7 is a DSC of polymers I and II of example 2.
FIG. 8 is a TGA plot of polymers I and II of example 2.
Detailed Description
The technical scheme of the application will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the application. All techniques implemented based on the above description of the application are intended to be included within the scope of the application.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
The instrumentation or conditions for the tests performed in examples 1-2 are as follows:
liquid nuclear magnetic resonance spectrometer model: bruker Avance 400;
DSC differential scanning calorimeter model: DSC Q2000;
TGA thermogravimetric analyzer model: perkinElmer Pyris 1TGA;
gel Permeation Chromatography (GPC) characterization conditions: the mobile phase DMF, column incubator 50 ℃, flow rate 1ml/min, chromatographic column Agilent PL Mixed C, mixed D two in series.
Example 1
1.1 monomer Compounds of formula A (p is 1, R 1 2-tert-butyl), i.e. the preparation route of monomer A is shown below,
the method comprises the following specific steps:
1) 2- (tert-butyl) -4- (hydroxymethyl) -6-nitrophenol (6 g) and TBSCl (4.4 g), imidazole (2 g) were mixed and dissolved in 30ml DMF, stirred at room temperature for 1h, then diluted with diethyl ether, washed with water to remove DMF, the organic phase dried over anhydrous magnesium sulfate and the solvent removed by rotary evaporation. The residue was purified by column chromatography (V Petroleum ether ：V Acetic acid ethyl ester =20:1) to afford intermediate 1 (9 g, 95% yield).
2) 1-aminocaproic acid (5 g) and boc anhydride (16.6 g) were mixed and dissolved in 380ml of methanol, triethylamine (8 ml) was added, stirred at 60 ℃ for 1h, then adjusted to ph=4 with dilute hydrochloric acid, the organic phase was collected, dried, and the solvent was removed by rotary evaporation; intermediate 2 (8.6 g, 98% yield) was obtained.
3) Intermediate 2 (9 g) of the above step and hexanediol (18 g), 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC hydrochloride) (15 g) were mixed and dissolved in 150ml of THF, 4-Dimethylaminopyridine (DMAP) (950 mg) was added, stirred overnight at room temperature, then saturated ammonium chloride solution was added, extracted with ethyl acetate, the organic phase was collected, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The residue was purified by column chromatography (V Petroleum ether ：V Acetic acid ethyl ester =2:1) to afford intermediate 3 (9.5 g, 74% yield).
4) Intermediate 3 (8 g) from the previous step and Pyridine Dichromate (PDC) (32 g) were mixed and dissolved in 120ml DMF and stirred overnight at room temperature after which the celite was filtered, extracted with diethyl ether, the organic phase was collected, dried and the solvent was removed by rotary evaporation. The residue was purified by column chromatography (V Petroleum ether ：V Acetic acid ethyl ester =1:1) to give the crude product. The crude product was again mixed with intermediate 1 (6.4 g), EDC hydrochloride (6 g) in 80ml THF, DMAP (380 mg) was added and stirred overnight at room temperature, after which saturated ammonium chloride solution was added, extracted with ethyl acetate, the organic phase was collected, dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation. The residue was purified by column chromatography (V Petroleum ether ：V Acetic acid ethyl ester Purification was performed to give intermediate 4 (12 g, 73% yield).
5) Intermediate 4 (12 g) from the previous step and Amberlyst 15 (16 g) from the ion exchange resin were mixed and dissolved in 170ml of methanol, stirred at room temperature for 2h, filtered and the solvent was removed by rotary evaporation. The residue was purified by column chromatography (V Petroleum ether ：V Acetic acid ethyl ester =1:1) to afford intermediate 5 (9 g, 93% yield).
6) Intermediate 5 (5 g) from the previous step and pentafluorophenyl carbonate (7.1 g), TEA (2.5 ml) were mixed and dissolved in 90ml DCM and stirred at room temperature for 1h and the solvent was removed by rotary evaporation. The residue was purified by column chromatography (V Petroleum ether ：V Acetic acid ethyl ester =3:1) to intermediate 6 (6.7 g, 97% yield).
7) Intermediate 6 (6.7 g) from the previous step, trifluoroacetic acid (TFA) (30 ml) was dissolved in 30ml of DCM, stirred for 15min, the trifluoroacetic acid and DCM were removed by rotary evaporation, dissolved in 100ml of DCM, and the solvent was removed by rotary evaporation by dropwise addition of a syringe pump to a 500ml of DCM solution of 10ml of TEA for 3 h. The residue was purified by column chromatography (V Petroleum ether ：V Acetic acid ethyl ester Purification to give monomer a (3 g, 71% yield) with a nuclear magnetic profile shown in figure 1.
1.2 the preparation route of the monomer compound of formula B, namely monomer B, is shown below,
the method comprises the following specific steps:
1) Intermediate 3 (11 g) and PDC (44 g) from the previous step were mixed and dissolved in 150ml DMF and stirred at room temperature overnight, after which it was filtered through celite, extracted with diethyl ether, the organic phase was collected, dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation. The residue was purified by column chromatography (V Petroleum ether ：V Acetic acid ethyl ester =1:1), the crude product was prepared, and the crude product was mixed with hexanediol (15 g), EDC hydrochloride (9.7 g) and dissolved in 120ml THF, DMAP (622 mg) was added, stirred overnight at room temperature, then saturated ammonium chloride solution was added, extracted with ethyl acetate, the organic phase was collected, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. Column chromatography (V) Petroleum ether ：V Acetic acid ethyl ester =2:1) to afford intermediate 7 (8 g,yield 54%).
2) Intermediate 7 (7.3 g) from the previous step and PDC (37 g) were mixed and dissolved in 90ml DMF and stirred overnight at room temperature after which the celite was filtered, extracted with diethyl ether, the organic phase was collected, dried and the solvent was removed by rotary evaporation. The residue was purified by column chromatography (V Petroleum ether ：V Acetic acid ethyl ester =1:1) to give a crude product, which was mixed with intermediate 1 (5.6 g), EDC hydrochloride (5.3 g) and dissolved in 60ml THF, DMAP (330 mg) was added, stirred overnight at room temperature, then saturated ammonium chloride solution was added, extracted with ethyl acetate, the organic phase was collected, and dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The residue was purified by column chromatography (V Petroleum ether ：V Acetic acid ethyl ester =2:1) to afford intermediate 8 (8.3 g, 65% yield).
3) Intermediate 8 (8.7 g) from the previous step and Amberlyst 15 (7.2 g) were mixed and dissolved in 60ml of methanol, stirred at room temperature for 2h, filtered and the solvent was removed by rotary evaporation. The residue was purified by column chromatography (V Petroleum ether ：V Acetic acid ethyl ester =1:1) to afford intermediate 9 (6.2 g, 83% yield).
4) Intermediate 9 (5.5 g) from the previous step and pentafluorophenyl carbonate (6.5 g), TEA (2.3 ml) were mixed and dissolved in 80ml DCM and stirred at room temperature for 1h and the solvent was removed by rotary evaporation. The residue was purified by column chromatography (V Petroleum ether ：V Acetic acid ethyl ester =3:1) to afford intermediate 10 (7 g, 97% yield).
7) Intermediate 10 (7 g) from the previous step, TFA (30 ml) were dissolved in 30ml DCM, stirred for 15min, trifluoroacetic acid (TFA) and DCM were removed by rotary evaporation, dissolved in 100ml DCM, and the solvent was removed by rotary evaporation by dropwise addition of a syringe pump to a 500ml DCM solution of 10ml TEA for 3 h. The residue was purified by column chromatography (V Petroleum ether ：V Acetic acid ethyl ester Purified to give monomer B (4.2 g, 89% yield) =1:1%). The nuclear magnetic spectrum of monomer B is shown in FIG. 2.
Example 2
2.1 preparation of Poly (ε -caprolactone- ε -caprolactam) of formula I, i.e. Polymer I, comprising the following steps:
to 1ml of DMSO was added monomer A (287 mg,0.6 mmol), TEA (6.1 mg,0.06 mmol), N-methylaniline (161 mg,1.5 mmol) and N-hexylamine (2 mg,0.02 mmol) to initiate polymerization, the reaction was carried out in an oil bath at 50℃for 72 hours, and the residue was settled in diethyl ether to remove unreacted monomer and small molecules to give a polymer I having the structural formula shown in formula I. The GPC test results are shown in FIG. 5. As is clear from FIG. 5, the number average molecular weight was 24000 and the PDI was 1.07. FIG. 3 shows an in situ nuclear magnetic resonance spectrum of the polymer I, and the degree of polymerization is 19 as seen in FIG. 3.
2.2 preparation of Poly (ε -caprolactone- ε -caprolactam) of formula II, namely Polymer II, comprising the following steps:
monomer B (710 mg,0.6 mmol), TEA (12.2 mg,0.06 mmol), N-methylaniline (257 mg,2.4 mmol) and N-hexylamine (2 mg,0.02 mmol) were added to 1ml DMSO, polymerization was initiated, the reaction was carried out in an oil bath at 50℃for 72 hours, and the residue was settled in an ether solvent to remove unreacted monomer and small molecules, to give polymer II, the nuclear magnetic characterization result being shown in FIG. 4; the GPC measurement results are shown in FIG. 6, and as shown in FIG. 6, the number average molecular weight was 33000 and the PDI was 1.07. FIG. 4 shows the nuclear magnetic resonance spectrum of Polymer II, and the degree of polymerization was 22 as shown in FIG. 4.
By detection, DSC and TGA spectra of polymers I and II were obtained, FIG. 7 is a DSC of polymers I and II; FIG. 8 is a TGA plot of polymers I and II.
The embodiments of the present application have been described above by way of example. However, the scope of the present application is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art, which fall within the spirit and principles of the present application, are intended to be included within the scope of the present application.
Claims (10)
1. A monomer compound of the following formula A or a monomer compound of the following formula B,
wherein p is an integer of 0 to 3; when p is 2 or 3, each R 1 Identical or different, independently of one another, from H, C 1-12 Alkyl, C 1-12 Alkoxy, halogen, cyano, nitroAmino or formyl.
2. The compound of claim 1, wherein p is 1,2 or 3. Preferably, p is 1 or 2, more preferably 1.
3. A compound according to claim 1 or 2, wherein when p is 2 or 3, each R 1 Identical or different, independently of one another, from H, C 1-6 Alkyl, C 1-6 Alkoxy, halogen, cyano, nitro, amino or formyl.
Preferably, each R 1 The same or different, independently of one another, from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or n-hexyl. More preferably t-butyl.
Preferably, the monomer compound of formula a has the following structure:
preferably, the monomer compound of formula B has the following structure:
4. a process for the preparation of a monomeric compound of formula a or a monomeric compound of formula B according to any one of claims 1 to 3, characterized in that it comprises the steps of:
(K1) Reacting a compound shown in a formula C with pentafluorophenyl carbonate in a solvent to prepare an intermediate 6;
(K2) Reacting intermediate 6, trifluoroacetic acid (TFA) and a basic catalyst in a solvent to prepare a monomer compound of formula A;
or, (P1) reacting a compound shown in a formula D with pentafluorophenyl carbonate in a solvent to prepare an intermediate 10;
(P2) reacting intermediate 10, trifluoroacetic acid (TFA) and a basic catalyst in a solvent to prepare the monomer compound of formula B.
5. The method according to claim 4, wherein the solvent is at least one of dichloromethane, tetrahydrofuran, chloroform, acetonitrile, or a combination of two or more thereof.
Preferably, the basic catalyst is at least one or a combination of more than two of triethylamine, diisopropylethylamine, DBU and TBD.
6. The method according to claim 4 or 5, wherein the method for preparing the compound represented by formula C comprises the steps of:
(1) Reacting a compound shown in a formula E with tert-butyldimethylchlorosilane (TBSCl) to prepare an intermediate 1;
(2) Reacting 1-aminocaproic acid, di-tert-butyl dicarbonate (boc anhydride) and triethylamine to prepare an intermediate 2;
(3) Reacting intermediate 2 with hexanediol to prepare intermediate 3;
(4) Reacting intermediate 3 with intermediate 1 to prepare intermediate 4;
(5) Intermediate 4 was reacted with ion exchange resin (Amberlyst 15) to prepare a compound of formula C, intermediate 5.
Preferably, the preparation method of the compound shown in the formula D comprises the following steps:
(S1) reacting the above intermediate 3 with hexanediol to prepare an intermediate 7;
(S2) reacting intermediate 7 with intermediate 1 to prepare intermediate 8;
(S3) reacting intermediate 8 with ion exchange resin (Amberlyst 15) to prepare a compound represented by formula D, namely intermediate 9.
7. Poly (epsilon-caprolactone-epsilon-caprolactam) shown in formula I or formula II, which is characterized in that the poly (epsilon-caprolactone-epsilon-caprolactam) shown in formula I is prepared by reacting the monomer compound of formula A as defined in any one of claims 1-3; poly (epsilon-caprolactone-epsilon-caprolactam) of formula II is prepared by reacting a monomer compound of formula B according to any one of claims 1-3;
wherein n is the same or different and is independently selected from the group consisting of numbers 1 to 100.
8. The poly (epsilon-caprolactone-epsilon-caprolactam) according to claim 7, characterized in that n are identical or different and are independently chosen from the numbers 15 to 50.
Preferably, the poly (epsilon-caprolactone-epsilon-caprolactam) of formula I or formula II has a number average molecular weight of 20000 or more, preferably 22000 to 200000.
9. A process for preparing poly (epsilon-caprolactone-epsilon-caprolactam) as claimed in claim 7 or 8, comprising the steps of:
reacting a monomer compound shown in a formula A with an initiator to prepare poly (epsilon-caprolactone-epsilon-caprolactam) shown in a formula I;
alternatively, the monomer compound of formula B is reacted with an initiator to produce poly (ε -caprolactone- ε -caprolactam) of formula II.
Preferably, the initiator is at least one or a combination of more than two of n-hexylamine, n-propylamine and amphetamine.
10. Use of a monomer compound of formula a or a monomer compound of formula B according to any one of claims 1 to 3, poly (epsilon-caprolactone-epsilon-caprolactam) according to claim 7 or 8 for the preparation of plastics, fibrous materials.
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