CN110092892B - Preparation method of polyester - Google Patents
Preparation method of polyester Download PDFInfo
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- CN110092892B CN110092892B CN201910336910.XA CN201910336910A CN110092892B CN 110092892 B CN110092892 B CN 110092892B CN 201910336910 A CN201910336910 A CN 201910336910A CN 110092892 B CN110092892 B CN 110092892B
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- monomer
- thiourea
- lactide
- substituted
- carbonate
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- 229920000728 polyester Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 29
- -1 cyclic ester Chemical class 0.000 claims abstract description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 150000001408 amides Chemical class 0.000 claims abstract description 13
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 6
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 5
- 150000002596 lactones Chemical group 0.000 claims description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims description 3
- HSONPEIWAFGLCA-UHFFFAOYSA-N 4-chloro-1,3-dioxan-2-one Chemical compound ClC1CCOC(=O)O1 HSONPEIWAFGLCA-UHFFFAOYSA-N 0.000 claims description 3
- SFUJFSPYIQTVGJ-UHFFFAOYSA-N 4-hydroxy-1,3-dioxan-2-one Chemical compound OC1OC(OCC1)=O SFUJFSPYIQTVGJ-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 claims description 2
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 229940067107 phenylethyl alcohol Drugs 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 4
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 19
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 12
- 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 description 10
- 238000003760 magnetic stirring Methods 0.000 description 9
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 8
- 235000019445 benzyl alcohol Nutrition 0.000 description 7
- 238000001542 size-exclusion chromatography Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- VSCBATMPTLKTOV-UHFFFAOYSA-N 2-tert-butylimino-n,n-diethyl-1,3-dimethyl-1,3,2$l^{5}-diazaphosphinan-2-amine Chemical compound CCN(CC)P1(=NC(C)(C)C)N(C)CCCN1C VSCBATMPTLKTOV-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 3
- 229920001610 polycaprolactone Polymers 0.000 description 3
- 239000004632 polycaprolactone Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- OEBXWWBYZJNKRK-UHFFFAOYSA-N 1-methyl-2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine Chemical compound C1CCN=C2N(C)CCCN21 OEBXWWBYZJNKRK-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JJTUDXZGHPGLLC-QWWZWVQMSA-N (3r,6r)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@@H](C)OC1=O JJTUDXZGHPGLLC-QWWZWVQMSA-N 0.000 description 1
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013501 data transformation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229960001945 sparteine Drugs 0.000 description 1
- SLRCCWJSBJZJBV-AJNGGQMLSA-N sparteine Chemical compound C1N2CCCC[C@H]2[C@@H]2CN3CCCC[C@H]3[C@H]1C2 SLRCCWJSBJZJBV-AJNGGQMLSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
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Classifications
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the technical field of organic polymer materials, and particularly relates to a preparation method of polyester. In the presence of an initiator, thiourea or amide catalyst with three hydrogen bonds and alkali are adopted to catalyze the ring-opening polymerization of a cyclic ester monomer to obtain the polyester compound. The method has the advantages of simple process, low cost, high reaction rate, controllable process and narrow molecular weight distribution of the obtained product.
Description
Technical Field
The invention belongs to the technical field of organic polymer materials, and particularly relates to a preparation method of polyester.
Background
Among many synthetic polymer materials, aliphatic polyesters are important for their excellent biodegradability, bioabsorbability, and biocompatibility, and have been a research hotspot in recent years. The polyester contains easily hydrolyzed ester group in the molecular structure, and is easy to be gradually decomposed into oligomer or monomer in the presence of water and microorganism, and further metabolized into carbon dioxide and water, so that the polyester can show certain biodegradability and compatibility, and has great application potential in the fields of biomedicine, tissue engineering and the like.
The traditional method for preparing polyester is mainly a polycondensation method, which usually needs higher temperature and has large energy consumption, and the obtained product has lower molecular weight, wide molecular weight distribution and uncontrollable reaction process, thus being not beneficial to the stability of materials. In addition, the preparation of aliphatic polyesters by ring-opening polymerization of cyclic monomers is one of the active, controllable processes. The polyester prepared by the ring-opening polymerization method has the characteristics of high molecular weight and narrow molecular weight distribution, not only can accurately control the chemical composition of a polymerization product, but also can improve the stability of the material performance, so that the property and the application of the material are milder, and the application field of the aliphatic polyester is widened. Compared with the traditional high polymer material synthesis method by the ring-opening polymerization method, the method has the characteristics of low energy consumption and environmental friendliness, and conforms to the idea of green chemistry. In the field, different catalytic systems are utilized to realize the ring-opening polymerization of cyclic monomers to prepare biodegradable polyester, which is an important way for the development of environment-friendly polymers.
Over the past decade, research into the preparation of polyesters using thioureas has been extensive, e.g., j.am.chem.soc.2005,127, 13798-13799; J.am.chem.Soc.2006,128, 4556-4557; macromolecules, 2006,39,7863, 7871, and the like. Although these catalytic systems have high activity, these catalytic systems cannot achieve both high catalytic speed and controllable molecular weight. Therefore, it is necessary to find a catalyst which is easy and convenient to operate, efficient in reaction and controllable in process.
Disclosure of Invention
The invention aims to provide a method for preparing polyester by catalyzing ring-opening polymerization of cyclic monomers based on thiourea amide with three hydrogen bonds. The method has the advantages of simple and convenient process, low cost, high reaction rate, controllable process and narrow molecular weight distribution.
In order to solve the technical problems, the idea of the invention is as follows:
(1) combining hydrogen with the strongest acidity in thiourea amide with three hydrogen bonds with organic base through ionic bonds to obtain the organic Lewis acid-base pair.
(2) Under reaction conditions, the two remaining hydrogens in the thiourea amide activate the cyclic monomer and the Lewis acid base pair double activates the initiator.
(3) In the presence of an alcohol initiator, thiourea amide and organic base are combined to catalyze the ring-opening polymerization of a cyclic monomer to obtain the polyester.
According to the invention, researches show that the catalytic efficiency is influenced by the difference of side chain substituent groups in the thiourea amide with three hydrogen bonds. The ring-opening polymerization reaction needs to determine the proper temperature and the temperature variation range according to the property requirements of the polymerization product and the process conditions of the polymerization reaction device, so as to ensure that the polymerization reaction is effectively carried out in a certain temperature range.
The controllable distribution of the end structure and molecular weight of the polylactone, for example, the narrow molecular weight distribution, can be solved by adding a compound containing active hydrogen (R-O-H) as an initiator in the ring-opening polymerization reaction, wherein the end structures of initiated monomers are respectively R-O-and-OH, and the ratio of the lactone monomer to the initiator determines the target molecular weight of the obtained polylactone. Under the condition of an initiator, the three-hydrogen bond thiourea amide catalyzes ring-opening polymerization to be active polymerization, and the obtained polymer has controllable molecular weight and terminal structure and narrow molecular weight distribution.
The technical scheme of the invention is as follows:
a preparation method of polyester comprises the following steps of catalyzing ring opening polymerization of a cyclic ester monomer by adopting a thiourea or amide catalyst with three hydrogen bonds and alkali in the presence of an initiator to obtain a polyester compound, wherein the thiourea or amide catalyst with three hydrogen bonds and the alkali are matched as shown in formula I, formula II, formula III or formula IV:
b is selected from NyMe 2, (-) -spark, PMDETA, DMAP, DBU, DABCO, DIEA, TMEDA, MTBD, BEMP, t-BuP2BEMP organic catalyst;
R1selected from: phenyl or substituted phenyl;
R2selected from: phenyl or substituted phenyl, benzyl or substituted benzyl, substituted or unsubstituted binaphthyl or 1, 3-dione-4-cyclopentenyl;
x is selected from: oxygen or sulfur;
y is selected from: nitrogen;
R3is phenyl or substituted unsubstituted phenylsulfonyl;
the "substitution" in each of the above-mentioned groups includes mono-or polysubstitution. The above alkali, (-) -sparteine is eagleCalpain, PMDETA as pentamethyldiethylenetriamine, DMAP as 4-dimethylaminopyridine, DBU as 1, 8-diazabicycloundec-7-ene, and DABCO as 1, 4-diazabicyclo [2.2.2]Octane, DIEA as N, N-diisopropylethylamine, TMEDA as tetramethylethylenediamine and NcyMe2MTBD, BEMP and t-BuP2Structural formulas are respectively
Preferably, R is1Selected from hydroxy substituted phenyl, trifluoromethyl substituted phenyl; r2Selected from phenyl, alkyl substituted phenyl containing 1-3 carbon atoms, benzyl, binaphthyl or 1, 3-diketone-4-cyclopentenyl; r3Selected from phenylsulfonyl or phenyl; the base is selected from: DMAP, DBU, MTBD or BEMP; the cyclic ester monomer is a lactone monomer, an lactide monomer or a carbonate monomer. The "substitution" mentioned above includes mono-or poly-substitution.
Preferably, the thiourea or amide catalyst is of the following structure:
the base has the following structure:
preferably, the cyclic ester monomer has the following structure:
the lactone monomer is selected from the structures shown in formula II:
wherein A is [ - (CR)4R5)—]n and n are integers of 2-10; r4、R5The same or different groups selected from H, an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms and substituted with a halogen atom or a hydroxyl group;
the lactide monomer is selected from a structure shown in a formula III:
wherein A, B is [ - (-) - (CR)6R7)—]n and n are integers of 0-10, and A and B are the same or different; r6、R7The same or different groups selected from H, alkyl having 1 to 5 carbon atoms and substituted with a halogen atom or a hydroxyl group; z is oxygen or sulfur;
the carbonate monomer is selected from the structures shown in formula IV:
wherein R is1、R2The same or different groups selected from H, alkyl groups having 1 to 5 carbon atoms and substituted with a halogen atom or a hydroxyl group.
Preferably, the cyclic ester monomer is D-lactide, L-lactide, glycolide, L-lactide, trimethylene carbonate, hydroxytrimethylene carbonate, chlorotrimethylene carbonate, delta-valerolactone, gamma-chloro-delta-valerolactone or epsilon-caprolactone.
Preferably, the initiator is methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, benzyl alcohol, phenethyl alcohol, phenylpropyl alcohol, ethylene glycol, pentaerythritol or benzylamine.
Preferably, the molar ratio of the thiourea or amide catalyst to the cyclic ester compound after being compounded with the base is 1: 3-5000, and the optimal molar ratio is 1: 10-97.
Preferably, the preparation method comprises the following specific steps: cyclic lactone monomer or cyclic lactide monomer or cyclic carbonate monomer, initiator alcohol or amine, thiourea or amide catalyst and alkali are reacted, good solvent is added, and polymer is precipitated in precipitation solvent.
Preferably, the reaction temperature is 40 to 150 ℃, preferably 60 to 140 ℃, and more preferably 90 ℃.
Preferably, the good solvent is dichloromethane, toluene, tetrahydrofuran, dichloroethane or chloroform, and the precipitation solvent is methanol, ethanol, diethyl ether, n-hexane or n-pentane.
The technical scheme adopted by the invention has the beneficial effects that:
firstly, the catalyst provided by the invention has high catalysis speed and controllable molecular weight. Secondly, the catalyst is used for catalyzing the synthesis of polyester, so that the operation is simple and convenient, the reaction is efficient, and the process is controllable. And the molecular weight and the end structure of the obtained polymer are controllable, and the molecular weight distribution is narrow. Furthermore, differences in side chain substituents in thiourea amides with three hydrogen bonds will affect catalytic efficiency. The ring-opening polymerization reaction determines the proper temperature and the temperature variation range according to the property requirements of the polymerization product and the process conditions of the polymerization reaction device, and ensures that the polymerization reaction is effectively carried out in a certain temperature range.
Drawings
Embodiments of the present invention will be described in detail with reference to the accompanying drawings, in which
FIG. 1 preparation of polylactic acid obtained in example 31H NMR spectrum;
FIG. 2 is a spectrum of polylactic acid of example 3 in size exclusion chromatography;
FIG. 3 preparation of polytrimethylene carbonate obtained in example 61H NMR spectrum;
FIG. 4 shows the spectrum obtained in example 6 in size exclusion chromatography of polytrimethylene carbonate;
FIG. 5 preparation of the polypentanolides obtained in example 91H NMR spectrum;
FIG. 6 shows the chromatogram obtained in the size exclusion chromatography analysis of the polyglutarilactone obtained in example 9.
FIG. 7 preparation of polycaprolactone obtained in example 111H NMR spectrum;
FIG. 8 is a spectrum of size exclusion chromatography analysis of polycaprolactone obtained in example 11.
FIG. 9 Hydrogen Spectrum of Thiourea catalyst, feed No. 3, used in the example
Detailed Description
The invention is further illustrated by the following examples, which are intended to be illustrative and not limiting. It will be understood by those of ordinary skill in the art that these examples are not intended to limit the present invention in any way and that suitable modifications and data transformations may be made without departing from the spirit and scope of the present invention. The starting materials referred to in the description are commercially available or synthesized from the literature, and the NMR spectrometer model is Bruker Ascend TM-400, the conversions and the number-average molecular weights Mn in the examples are determined by nuclear magnetism. The Size Exclusion Chromatography (SEC) instrument model was Wyatt Optilab T-rEX, and the dispersity PDI in the examples was determined by SEC.
The tri-hydrogen bonded thiourea or amide catalysts used in the examples have the following structure:
wherein, the hydrogen spectrum of the thiourea catalyst of number 3 is shown in fig. 9.
The base used in the examples has the following structure:
example 1
D-lactide (0.432g, 3mmol), compound (9) (0.109g, 0.3mmol), DMAP (13.5. mu.L, 0.1mmol), pentaerythritol (9.7. mu.L, 0.1mmol) were added to a 10mL polymerization tube, and magnetic stirring was carried out at 140 ℃ for 4 hours to stop the reaction, a small amount of methylene chloride was dropped into the obtained mixture to dissolve it, and then cold methanol was slowly dropped into the obtained solution to precipitate a white polymer, which was centrifuged and vacuum-dried to obtain 0.28g of a product having a conversion of 97.2%, a number-average molecular weight Mn of poly D-lactide of 4610g/mol and a molecular weight distribution PDI of 1.21.
Example 2
D-lactide (0.0432g, 0.3mmol), compound (3) (0.115g, 0.3mmol), DBU (15.0. mu.L, 0.1mmol), pentaerythritol (9.7. mu.L, 0.1mmol) were added to a 10mL polymerization tube, and magnetic stirring was carried out at 40 ℃ for 5 hours to stop the reaction, a small amount of methylene chloride was added dropwise to the resulting mixture to dissolve it, and then cold methanol was slowly added dropwise to the resulting solution to precipitate a white polymer, which was centrifuged and vacuum-dried to obtain 0.03g of the product, the conversion of which was 97.6%, and the number-average molecular weight M of poly-d-lactide was 0.03gn500g/mol, molecular weight distribution PDI was 1.11.
Example 3
To a 10mL polymerization tube were added L-lactide (0.432g, 3mmol), compound (4) (0.109g, 0.3mmol), DBU (15.0. mu.L, 0.1mmol), benzyl alcohol (10.0. mu.L, 0.1mmol), and the reaction was stopped by magnetic stirring at 130 ℃ for 1.5 hours, and the resulting mixture was dissolved by dropwise addition of a small amount of methylene chloride, and the resulting solution was slowly added dropwise to cold methanol to precipitate a white polymer, which was centrifuged and vacuum-dried to obtain 0.36g of a product having a conversion of 99.5% and a number-average molecular weight M of poly (L-lactide)n5389g/mol and a molecular weight distribution PDI of 1.19. (FIGS. 1 and 2)
Example 4
Glycolide (0.348g, 3mmol), the compound (3) (0.110g, 0.3mmol), DMAP (13.5. mu.L, 0.1mmol), benzyl alcohol (10.0. mu.L, 0.1mmol) were added to a 10mL polymerization tube, and magnetic stirring was carried out at 130 ℃ for 5 hours to stop the reaction, a small amount of tetrahydrofuran was dropped into the obtained mixture to dissolve it, and then cold methanol was slowly dropped into the obtained solution to precipitate a white polymer, which was centrifuged and vacuum-dried to obtain 0.30g of a product having a conversion of 91.13% and a number-average molecular weight M of polyglycoliden3800g/mol, molecular weight distribution PDI 1.21.
Example 5
Into a 10mL polymerization tube were added l-butyllactide (1.512g, 9mmol), compound (12) (0.167g, 0.3mmol), DMAP(13.5. mu.L, 0.1mmol) and benzyl alcohol (10.0. mu.L, 0.1mmol), magnetically stirring at 150 deg.C for 11 hr, stopping reaction, adding small amount of tetrahydrofuran dropwise to the obtained mixture to dissolve, slowly adding cold methanol dropwise to precipitate white polymer, centrifuging, and vacuum drying to obtain 1.0g product with conversion rate of 98.6%, and number average molecular weight M of poly L-lactidenIt was 14900g/mol, and the molecular weight distribution PDI was 1.21.
Example 6
Into a 10mL polymerization tube, trimethylene carbonate (0.306g, 3mmol), compound (3) (0.115g, 0.3mmol), DBU (15.0. mu.L, 0.1mmol), benzyl alcohol (10.0. mu.L, 0.1mmol) were charged, and magnetic stirring was carried out at 60 ℃ for 3 hours to stop the reaction, a small amount of chloroform was dropped into the resulting mixture to dissolve it, and then cold ethanol was slowly dropped into the resulting solution to precipitate a white polymer, which was centrifuged and vacuum-dried to obtain 0.21g of a product having a conversion of 89.5% and a number-average molecular weight M of polytrimethylene carbonaten2200g/mol and a molecular weight distribution PDI of 1.06. (FIGS. 3 and 4)
Example 7
Into a 10mL polymerization tube, hydroxytrimethylene carbonate (0.714g, 6mmol), compound (7) (0.122g, 0.3mmol), DBU (15.0. mu.L, 0.1mmol), isopropanol (7.6. mu.L, 0.1mmol) were added, and the reaction was stopped by magnetic stirring at 60 ℃ for 5 hours, and a small amount of chloroform was added dropwise to the resulting mixture to dissolve it, and then cold ethanol was added dropwise slowly to precipitate a white polymer, which was centrifuged and vacuum-dried to obtain 0.61g of a product having a conversion of 94.5% and a number-average molecular weight M of polyhydroxytrimethylene carbonaten6200g/mol, the molecular weight distribution PDI was 1.19.
Example 8
Chlorotrimethylene carbonate (68.75g, 500mmol), compound (7) (0.122g, 0.3mmol), DMAP (13.5. mu.L, 0.1mmol), n-butanol (9.1. mu.L, 0.1mmol) were added to a 10mL polymerization tube, and magnetic stirring was carried out at 60 ℃ for 120 hours to stop the reaction, a small amount of chloroform was dropped into the obtained mixture to dissolve it, and then cold ethanol was slowly dropped into the obtained solution to precipitate a white polymer, which was centrifuged and vacuum-dried to obtain 44g of a product, which was converted to convert the compound into a white polymerThe ratio was 90.3%, and the number average molecular weight M of polychloro-trimethylene carbonaten500000g/mol and a molecular weight distribution PDI of 1.35.
Example 9
Delta-valerolactone (0.27mL, 3mmol), compound (9) (0.109g, 0.3mmol), DBU (15.0. mu.L, 0.1mmol), benzyl alcohol (10.0. mu.L, 0.1mmol) were added to a 10mL polymerization tube, and magnetic stirring was carried out at 90 ℃ for 3 hours to stop the reaction, a small amount of methylene chloride was added dropwise to the resulting mixture to dissolve it, and then cold ethanol was slowly added dropwise to the resulting solution to precipitate a white polymer, which was centrifuged and vacuum-dried to obtain 0.12g of a product having a conversion of 93.2% and a number-average molecular weight M of polypentanolactonen3523g/mol, molecular weight distribution PDI 1.03. (FIGS. 5 and 6)
Example 10
Gamma-chloro-delta-valerolactone (5.50mL, 29mmol), compound (1) (0.068g, 0.3mmol), DMAP (13.5. mu.L, 0.1mmol) and benzyl alcohol (10. mu.L, 0.1mmol) were added to a 10mL polymerization tube, and magnetic stirring was carried out at 90 ℃ for 24 hours to stop the reaction, a small amount of methylene chloride was dropped into the obtained mixture to dissolve it, and then cold ethanol was slowly dropped into the obtained solution to precipitate a white polymer, which was centrifuged and vacuum-dried to obtain 4.2g of a product with a conversion rate of 85.2%, and the obtained polymer had a number average molecular weight Mn26000g/mol and a molecular weight distribution PDI of 1.11.
Example 11
Adding epsilon-caprolactone (0.36mL, 3mmol), compound (3) (0.109g, 0.3mmol), DBU (15.0. mu.L, 0.1mmol), benzyl alcohol (10. mu.L, 0.1mmol) into a 10mL polymerization tube, magnetically stirring at 90 deg.C for 7 hours to stop the reaction, dropping a small amount of dichloromethane into the obtained mixture to dissolve, slowly dropping cold ethanol into the obtained solution to precipitate a white polymer, centrifuging, and vacuum drying to obtain 0.22g of product with a conversion rate of 96.2%, wherein the number-average molecular weight M of polycaprolactone isn3523g/mol, molecular weight distribution PDI 1.04. (FIGS. 7 and 8)
Claims (13)
1. A preparation method of polyester is characterized in that under the existence of an initiator, a thiourea or amide catalyst with three hydrogen bonds and a base are adopted to catalyze a cyclic ester monomer to carry out ring-opening polymerization to obtain a polyester compound, wherein the thiourea or amide catalyst with three hydrogen bonds and the base are matched as shown in formula I, formula II, formula III or formula IV:
b is selected from organic catalysts;
R1selected from: phenyl or trifluoromethyl substituted phenyl;
R2selected from: phenyl or substituted phenyl, benzyl or substituted benzyl, substituted or unsubstituted binaphthyl or 1, 3-dione-4-cyclopentenyl;
x is selected from: oxygen;
y is selected from: nitrogen;
R3is a benzenesulfonyl group;
the "substitution" in each of the above-mentioned groups includes mono-or polysubstitution.
2. The method of claim 1, wherein R is2Selected from phenyl, alkyl substituted phenyl containing 1-3 carbon atoms, benzyl, binaphthyl or 1, 3-diketone-4-cyclopentenyl; the cyclic ester monomer is a lactone monomer, an lactide monomer or a carbonate monomer.
3. The method of claim 2, wherein the thiourea or amide catalyst is of the structure:
the base has the following structure:
4. the method of claim 3, wherein the cyclic ester monomer has the structure:
the lactone monomer is selected from the structures shown in formula II:
wherein A is [ - (CR)4R5)—]n and n are integers of 2-10; r4、R5The same or different groups selected from H, an alkyl group having 1 to 5 carbon atoms and substituted with a halogen atom or a hydroxyl group;
the lactide monomer is selected from a structure shown in a formula III:
wherein A, B is [ - (-) - (CR)6R7—]n and n are integers of 0-10, and A and B are the same or different; r6、R7The same or different groups selected from H, alkyl having 1 to 5 carbon atoms and substituted with a halogen atom or a hydroxyl group; z is oxygen or sulfur;
the carbonate monomer is selected from the structures shown in formula IV:
wherein R is1、R2The same or different groups selected from H, alkyl groups having 1 to 5 carbon atoms and substituted with a halogen atom or a hydroxyl group.
5. The method of claim 4, wherein the cyclic ester monomer is D-lactide, L-lactide, glycolide, L-lactide, trimethylene carbonate, hydroxytrimethylene carbonate, chlorotrimethylene carbonate, delta-valerolactone, gamma-chloro delta-valerolactone, or epsilon-caprolactone.
6. The method of claim 1, wherein the initiator is methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, benzyl alcohol, phenylethyl alcohol, phenylpropyl alcohol, ethylene glycol, pentaerythritol or benzylamine.
7. The method according to claim 1, wherein the molar ratio of the thiourea or amide catalyst to the cyclic ester compound after the complex with the base is 1: 3-5000.
8. The method according to claim 7, wherein the molar ratio of the thiourea or amide catalyst to the cyclic ester compound after the complex with the base is 1: 10-97.
9. The method according to any one of claims 1 to 8, wherein the preparation method comprises the following specific steps: cyclic lactone monomer or cyclic lactide monomer or cyclic carbonate monomer, initiator alcohol or amine, thiourea or amide catalyst and alkali are reacted, good solvent is added, and polymer is precipitated in precipitation solvent.
10. The process of claim 9, wherein the reaction temperature is 40 to 150 ℃.
11. The process of claim 10, wherein the reaction temperature is 60 to 140 ℃.
12. The process of claim 11, wherein the reaction temperature is 90 ℃.
13. The method as claimed in claim 9, wherein the good solvent is dichloromethane or toluene or tetrahydrofuran or dichloroethane or chloroform, and the precipitation solvent is methanol or ethanol or diethyl ether or n-hexane or n-pentane.
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| CN112259736A (en) * | 2020-10-27 | 2021-01-22 | 成都新柯力化工科技有限公司 | Lithium titanate negative electrode for relieving flatulence of lithium battery and preparation method |
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| CN114276524B (en) * | 2021-12-27 | 2023-04-21 | 青岛科技大学 | Preparation method of high molecular weight degradable recyclable polyester containing double bond side group |
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