CN106117532B - A kind of synthetic method and bimetallic catalyst of stereoregularity polyester - Google Patents
A kind of synthetic method and bimetallic catalyst of stereoregularity polyester Download PDFInfo
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- AYKYXWQEBUNJCN-UHFFFAOYSA-N CC(C(O1)=O)=CC1=O Chemical compound CC(C(O1)=O)=CC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- SQTDRNGQUMCVKG-UHFFFAOYSA-N O=C(C(C12)C3C4C#CC14C2C(CC(O1)=O)CC1=O)OC3=O Chemical compound O=C(C(C12)C3C4C#CC14C2C(CC(O1)=O)CC1=O)OC3=O SQTDRNGQUMCVKG-UHFFFAOYSA-N 0.000 description 1
- 0 O=C(C1*2C1)OC2=O Chemical compound O=C(C1*2C1)OC2=O 0.000 description 1
- NMSRALOLNIBERV-UHFFFAOYSA-N O=C(C1C2CCC1)OC2=O Chemical compound O=C(C1C2CCC1)OC2=O NMSRALOLNIBERV-UHFFFAOYSA-N 0.000 description 1
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N O=C(CCC1)NC1=O Chemical compound O=C(CCC1)NC1=O KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 description 1
- MXAJVDHGJCYEKL-UHFFFAOYSA-N O=C(COC1)NC1=O Chemical compound O=C(COC1)NC1=O MXAJVDHGJCYEKL-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N O=C(c1ccccc11)OC1=O Chemical compound O=C(c1ccccc11)OC1=O LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- NQVIYXLKFQDIDP-UHFFFAOYSA-N OC(C1C2COC1)OC2=O Chemical compound OC(C1C2COC1)OC2=O NQVIYXLKFQDIDP-UHFFFAOYSA-N 0.000 description 1
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- 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
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
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- 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
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- 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
- C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
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- 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
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
Abstract
The present invention relates to a kind of synthetic method and bimetallic catalyst of stereoregularity polyester.The catalyst is the dual-nuclei structure model for being connected two metal centers by biphenyl or dinaphthalene skeleton.The catalyst can prepare polyester by high efficiency catalysis cyclic acid anhydride, catalytic efficiency is 10 under compared with temperate condition and relatively low catalyst concn under the effect of nucleophilicity co-catalyst with meso epoxyalkane polymerisation3~106Gram polymer/mol catalyst, polymer molecular weight is 103~105In the range of it is adjustable, its molecular weight distribution be less than 2, steric regularity is adjustable between 60~100%, and alternating structure can be degraded into micromolecular compound under certain condition more than 98%.Using the catalyst system and catalyzing of chiral ligand, the selectivity of product and alternating structure of polymer are selectively above 98%, and the enantiomeric excess value for the glycol obtained afterwards of degrading is higher than 70%, and extensive prospect is provided for commercial Application.
Description
Technical field
The present invention relates to a kind of synthetic method and its catalyst of stereoregularity polyester, and more particularly to one kind is by meso
Method of the epoxyalkane with cyclic acid anhydride alternating copolymerization into stereoregularity polyester, and it is catalyzed the bimetallic of the polymerisation
Catalyst.
Background technology
Disposable plastic packing material and plastics daily necessities not only consume bulk petroleum resource in production, but also with rear
It is not easily recycled recycling, it is also difficult to by environment degradable, cause environmental pollution.So initiative Biodegradable Materials and correlation
Product is one of important research target of whole world scientific circles.Wherein, aliphatic polyester is due to its good biocompatibility, life
The advantages that thing degradability and workability and receive significant attention.The polyester product of current commercialization has poly-succinic ethylene glycol
Ester (PES), poly butylene succinate (PBS), polylactic acid (PLA), poly 3-hydroxy butyrate (PHB), polycaprolactone (PCL)
Deng.But the monomer used in these commercialization polyester materials is produced dependent on biotechnology completely or partially, thus there are cost
Universal higher, efficiency is low, it is difficult to mass produces.Therefore, developing low-cost may replace nondegradation polyolefin general-purpose plastics
It is particularly important that degradable property new material just becomes.
It is a kind of new degradable polymer material that the ring opening copolymer of epoxyalkane and cyclic acid anhydride, which reacts the polyester to be formed,.
Two kinds of substrates of this kind of reaction are very easy to inexpensively obtain on a large scale by chemical means, have very high Economic competitive.This
Outside, one of reaction substrate epoxyalkane has abundant type, has spatial chemistry problem in ring opening process, so allow for and
Cyclic acid anhydride is copolymerized the polyester to be formed, and there are many stereochemical structures.And the polyester of steric order is likely to be crystallization, it should
Heat endurance with higher, it will greatly improve the application range of this kind of material.Therefore, completely can be by controlling polyester
Stereochemical structure carrys out the heat endurance and mechanical property of controlled material.Obviously, catalyst is the key in polyester production process
Factor.Efficiently, less toxic catalyst can not only improve the molecular weight of polymerizate, reduce the energy consumption in polymerization process, lifting
Product quality and application range, additionally it is possible to the security of polyester product is improved, to adapt to the need in the fields such as environment, bio-medical
Ask.
Just report porphyrin aluminium and quaternary ammonium (Phosphonium early in Inoue in 1985) salt composition bicomponent system be used for be catalyzed epoxy
Ethane and benzoic anhydride copolymerization (Aida T.；Inoue S.J.Am.Chem.Soc.1985,107,1358), but react very slow, usually
Need to convert completely within 4~7 days, molecular weight is 3000 or so.After 12 years, Maeda et al. has found simple diethoxy magnesium
Can also catalytic epoxyethane and succinic anhydride copolymerization, the reaction in (2 days) of 100 DEG C of long-times obtains high alternate degree polyester, molecular weight
Reach 13000 (Maeda Y.；Nakayama A.；Kawasaki N.；Hayashi K.；Aiba S.；Yamamoto
N.Polymer 1997,38,4719).Most important progress is that the Coates professors seminar of Cornell University finds that itrile group takes
The β in generation-diamines zinc acetate can be catalyzed various epoxyalkane under 50 DEG C of temperate condition and cyclic acid anhydride copolymerization is higher
Molecular weight and polyester (the Jeske R.C. in alternating structure；DiCiccio A.M.；Coates
G.W.J.Am.Chem.Soc.2007,129,11330).In addition, Salen or porphyrin metal complex symmetrically or non-symmetrically are (such as
Chromium, cobalt, aluminum and zinc etc.) polymerisation of epoxyalkane and cyclic acid anhydride can also be catalyzed.Sectional interest is catalyzed altogether in nucleophilicity
In the presence of agent, (DiCiccio A.M. are closed in the telomerization that can be catalyzed epoxyalkane, cyclic acid anhydride and carbon dioxide；Coates
G.W.J.Am.Chem.Soc.2011,133,10724；Zhu L.Q.；Liu D.F.；Wu L.Y.；Feng W.X.；Zhang
X.M.；Wu J.；Fan D.D.；Lu X.Q.；Lu R.；Shi Q.Inorg.Chem.Commun.2013,37,182；Saini
P.K.；Romain C.；Zhu Y.Q.；Williams C.K.Polym.Chem.2014,5,6068).2013, applicant's class
The design of topic group has synthesized the bimetallic SalanCrCl catalyst with binaphthyl structure, by being catalyzed end position epoxyalkane such as epoxy
The copolyreaction of chloropropane, phenyl glycidyl ether and maleic anhydride, finds the two polymerisations of Catalyzed by Pt/M Bimetallic Nano
Catalytic activity be 4.1 times and 7.1 times of (Liu J. of corresponding single-metal reforming catalyst respectively；Bao Y.-Y.；Liu Y.；Ren
W.-M.；Lu X.-B.Polym.Chem.2013,4,1439).It was found that bimetallic catalyst is in catalysis (s)-phenyl glycidyl
When ether is with maleic anhydride, more than 99% epoxyalkane selection participates in polymerisation in the open loop of methylene base location, obtains first
Obtain the optically active polyester of Formation keeping.Recently, Coates et al. find with optical activity (R, R)-salenCo (III) or (S,
S) the complex-catalyzed chiral epoxy propane of-salenCo (III) is copolymerized with succinic anhydride, obtains up to 97% head-tail phase order
Optically active polyester (the Longo J.M. of member；DiCiccio A.M.；Coates G.W.J.Am.Chem.Soc.2014,136,
15897).What is more important author has found that these optically active polyesters can be crystallized slowly after placing under certain condition, and
The polyester of two kinds of opposite configurations is with 1:It can be crystallized quickly after 1 mixing, and crystallinity higher, fusing point improve 40 DEG C, are a kind of knots
The stereo complex of crystalline substance.
It is a kind of novel green polymerisation that although epoxyalkane, which synthesizes polyester with the ring opening copolymer of cyclic acid anhydride, high
Realizing this process to effect, also there are problems.First, catalyst activity is high not enough, key issue be epoxyalkane with
Reactivity matching problem of the cyclic acid anhydride in polymerization process.Secondly, high stereoregularity catalyst does not occur also how
Realize high enantioselective ring-opening of the epoxyalkane in polymerization process.Key is to design the high stereoregularity catalysis of high activity
System, by controlling the chemical constitution of polymer, including polymer molecular weight and its distribution, region and stereoregularity, copolymerization
The insertion rate of comonomer and sequence distribution etc. in thing, it is expected to realize cutting out to obtain specific structure and performance to macromolecular chain
High molecular material；Acted on, caused single in propagation process using the electronic effect at metal catalytic activity center and space confinement
The directionality of body coordination insertion.
What is be previously reported by prepares polyester process by epoxyalkane and cyclic acid anhydride copolymerization, mostly there are catalyst activity it is low,
Reaction time is grown, severe reaction conditions；Seldom it is related to polyester spatial chemistry, is directly synthesized more not directly from achirality substrate vertical
Structure regularity polyester.
The content of the invention
The present invention proposes a kind of new method for synthesizing stereoregularity polyester, passes through the chiral bimetallic catalytic of design
Agent, is catalyzed the stereoregularity polyester of meso epoxyalkane and cyclic acid anhydride asymmetry alternating copolymerization synthesis backbone chiral.
Technical scheme：
A kind of synthetic method of stereoregularity polyester, under bimetallic catalyst effect, by meso epoxyalkane and
Cyclic acid anhydride is obtained completely in the stereoregularity polyester of alternating structure by being copolymerized；It is as follows：
If using chiral bimetallic catalyst, obtained by meso epoxyalkane and cyclic acid anhydride by asymmetric alternating copolymerization
The main chain obtained is chiral polyester；It is as follows：
In formula, meso epoxyalkane is：
Cyclic acid anhydride is：
Bimetallic catalyst for being catalyzed meso epoxyalkane and cyclic acid anhydride alternating copolymerization be by by biphenyl or
The dual-nuclei structure model and nucleophile R of dinaphthalene skeleton connection5R6 3YX1Bi-component catalytic body as co-catalyst composition
System；
The structure of dual-nuclei structure model is：
In formula, M Al3+、Fe3+、Co3+、Ni3+、Cr3+、Mn3+Or Ru3+；
R1For H, CH3、CH2CH3、CH(CH3)2、C(CH3)3、OCH3、OCH2CH3、(adamantyl), F, Cl, Br,
I or NO2；
R2For H, CH3、CH2CH3、CH(CH3)2、C(CH3)3、OCH3、OCH2CH3, adamantyl, F, Cl, Br, I or NO2；
R3=
R4For H, CH3、CH2CH3、CH(CH3)2、C(CH3)3、OCH3、OCH2CH3, F, Cl, Br, I or NO2；
R5For H, CH3、CH2CH3、CH(CH3)2、C(CH3)3、OCH3、OCH2CH3, Cl, Br, I or NO2；
X is F-、Cl-、Br-、I-、NO3 -、CH3COO-、CCl3COO-、CF3COO-、ClO4 -、BF4 -、BPh4 -、N3 -, to methylbenzene
Formate, p-methyl benzenesulfonic acid root, o-nitrophenol oxygen, p-nitrophenol oxygen, metanitrophenol oxygen, 2,4- dinitrophenol oxygen,
3,5- dinitrophenol oxygen, 2,4,6- trinitrophenols oxygen, 3,5- chlorophenesic acids oxygen, 3,5- difluorophenols oxygen, bis--trifluoros of 3,5-
Methylphenol oxygen or pentafluranol negative oxygen ion；
Co-catalyst nucleophile R5R6 3YX1Middle R5R6 3Y is the cationic moiety of co-catalyst；
R5R6 3For tetramethyl, tetraethyl, the tetrabutyl, tetrapropyl, benzyl triethyl ammonium, benzyl tripropyl, benzyl tributyl, ten
Six alkyl trimethyls, trimethyl, double-(dihalotriphenylphosphoranes base), butyl triphenyl, benzyltriphenyl phosphonium or propyl group triphen
Base；
Y is nitrogen or P elements；
X1For Cl-1、Br-1、I-1、NO3 -1、CH3COO-1、ClO4 -1、BF4 -1、OH-1、BPh4 -1Or N3 -1Monovalence anion；
In bimetallic catalyst, the dual-nuclei structure model and nucleophile that are connected by biphenyl or dinaphthalene skeleton
R5R6 3YX1Molar ratio be 1 ﹕ 1~5.
Ligand in the dual-nuclei structure model be by the salicylide containing substituted radical, 3,3 ' containing substituted radical-
Diformyl -2,2 '-hydroxyl -1,1 '-biphenyl and the reaction of Diamines mono-hydrochloric salts compound are made.
Such as
The Diamines mono-hydrochloric salts compound is that diamine compounds are ethylenediamine, 1,2- propane diamine, (rac) -2,
3- butanediamine, (R, R) -2,3- butanediamine, (S, S) -2,3- butanediamine, o-phenylenediamine, (rac)-cyclohexanediamine, (R, R)-hexamethylene
Diamines, (S, S)-cyclohexanediamine, (rac)-diphenyl ethylene diamine, (R, R)-diphenyl ethylene diamine or (S, S)-diphenyl second two
Amine.
The molar ratio of bimetallic catalyst and meso epoxyalkane is 1:1000~200000, meso epoxyalkane with
The molar ratio of cyclic acid anhydride is 1:1~10, reaction temperature is 0~60 DEG C, when reaction 0.5~48 is small.
Beneficial effects of the present invention：
(1) the stereoregularity polyester of backbone chiral is directly synthesized from achirality substrate；
(2) under low catalyst concentration, still with higher catalytic activity；
(3) reaction condition is relatively mild, and process is easy；
(4) catalyst activity is high, polymerizate high selectivity；
(5) alternating structure is higher than 98% in polyester product, and molecular weight distribution is relatively narrow；Part stereoregularity polyester has
Crystallizability energy；
(6) copolymerization of cyclic acid anhydride and meso epoxyalkane is catalyzed using chiral catalyst, polymerizate
Selectivity and alternating structure are selectively above 98%, and the enantiomeric excess value for the glycol obtained afterwards of degrading is higher than 70%.
Embodiment
Below in conjunction with technical solution and table, embodiment of the invention is further illustrated.
In 100mL reaction kettles, added in the following order under environment temperature：A certain amount of major catalyst (claim
In book first description any type metal complex), co-catalyst R1R2 3YX1, it is separately added into a certain amount of epoxyalkane
And cyclic acid anhydride.Reaction kettle is kept at a proper temperature and after the regular reaction time, stops stirring.Polymerization product chlorine
Imitative/methanol extraction washing is dried to constant weight three times, under vacuum, is measured polymer molecular weight using gel permeation chromatography and its is divided
Cloth；It is measured using Varian INOVA-400MHz1HNMR, calculates the carbonate unit content of polymerizate.With 500MHz cores
Magnetic-measurement its13CNMR, calculates the steric regularity of polyester.For using chiral catalyst, then by polymerizate NaOH
Weak solution is hydrolyzed into glycol, its enantioselectivity is measured with chiral chromatogram.
Table 1 is the complex-catalyzed 7-oxa-bicyclo[4.1.0 of trivalent metal and the alternating copolymerization of phthalic anhydride
Note 1：All catalytic reactions are all polymerisation in bulks, because acid anhydrides is good in epoxyalkane solute effect, therefore epoxy
Alkane is excessive, and acid anhydrides can realize complete conversion.
Note 2：Entry 1, polymer are polyalkylene oxide homopolymers, and no polyester produces, and remaining reaction obtains the chemical constitution of polyester
Selectivity>99%, there is no polyethers to be formed in polymerization process.
Note 3：Except specified otherwise, all catalyst are all without chiral or racemic.
Note 4：If application is with chiral catalyst, the ee values of the diol product after obtained polyester degraded are in 70-
It is adjustable between 99%.
Note 5：Entry 46, reacts using toluene as solvent, toluene/epoxyalkane=1/2 (volume ratio).
Note 6：PPN is double (dihalotriphenylphosphoranes base) ammonium cations, and DNP is 2,4-DNP negative oxygen ion.
Table 2 is the complex-catalyzed 7-oxa-bicyclo[4.1.0 of trivalent metal and the alternating copolymerization of various cyclic acid anhydrides
Note 1：All catalytic reactions are all polymerisation in bulks, because acid anhydrides is good in epoxyalkane solute effect, therefore epoxy
Alkane is excessive, and acid anhydrides can realize complete conversion.
Note 2：Catalyst/co-catalyst/epoxyalkane molar ratio is 1/2/250/1000.
Note 3：Polymerisation obtains the chemical constitution selectivity of polyester>99%, there is no polyethers to be formed in polymerization process.
Note 4：Except specified otherwise, all catalyst are all without chiral or racemic.
Note 5：If application is with chiral catalyst, the ee values of the diol product after obtained polyester degraded are in 70-
It is adjustable between 99%.
Note 6：PPN is double (dihalotriphenylphosphoranes base) ammonium cations.
Note 7：Such as using toluene as solvent, toluene/epoxyalkane=1/2 (volume ratio), polymerisation can still carry out, and
Realize that epoxyalkane and acid anhydrides convert completely, activity and molecular weight are suitable as the condition of solvent with using epoxyalkane.
Claims (4)
1. a kind of synthetic method of stereoregularity polyester, it is characterised in that under bimetallic catalyst effect, by meso ring
Oxygen alkane and cyclic acid anhydride are obtained completely in the stereoregularity polyester of alternating structure by being copolymerized；It is as follows：
Using chiral bimetallic catalyst, the master obtained by meso epoxyalkane and cyclic acid anhydride by asymmetric alternating copolymerization
Chain is chiral polyester；It is as follows：
In formula, meso epoxyalkane is：
Cyclic acid anhydride is：
Bimetallic catalyst for being catalyzed meso epoxyalkane and cyclic acid anhydride alternating copolymerization is by by biphenyl or dinaphthalene
The dual-nuclei structure model and nucleophile R of skeleton connection5R6 3YX1Bi-component catalyst system and catalyzing as co-catalyst composition；
The structure of dual-nuclei structure model is：
In formula, M Al3+、Fe3+、Co3+、Ni3+、Cr3+、Mn3+Or Ru3+；
R1For H, CH3、CH2CH3、CH(CH3)2、C(CH3)3、OCH3、OCH2CH3、(adamantyl), F, Cl, Br, I or
NO2；
R2For H, CH3、CH2CH3、CH(CH3)2、C(CH3)3、OCH3、OCH2CH3, adamantyl, F, Cl, Br, I or NO2；
R4For H, CH3、CH2CH3、CH(CH3)2、C(CH3)3、OCH3、OCH2CH3, F, Cl, Br, I or NO2；
R5For H, CH3、CH2CH3、CH(CH3)2、C(CH3)3、OCH3、OCH2CH3, Cl, Br, I or NO2；
X is F-、Cl-、Br-、I-、NO3 -、CH3COO-、CCl3COO-、CF3COO-、ClO4 -、BF4 -、BPh4 -、N3 -, p-methylbenzoic acid
Root, p-methyl benzenesulfonic acid root, o-nitrophenol oxygen, p-nitrophenol oxygen, metanitrophenol oxygen, 2,4- dinitrophenol oxygen, 3,5-
Dinitrophenol oxygen, 2,4,6- trinitrophenols oxygen, 3,5- chlorophenesic acids oxygen, 3,5- difluorophenols oxygen, 3,5- di-trifluoromethyls
Phenol oxygen or pentafluranol negative oxygen ion；
Co-catalyst nucleophile R5R6 3YX1Middle R5R6 3Y is the cationic moiety of co-catalyst；
R5R6 3For tetramethyl, tetraethyl, the tetrabutyl, tetrapropyl, benzyl triethyl ammonium, benzyl tripropyl, benzyl tributyl, hexadecane
Base trimethyl, trimethyl, double-(dihalotriphenylphosphoranes base), butyl triphenyl, benzyltriphenyl phosphonium or propyl group triphenyl；
Y is nitrogen or P elements；
X1For Cl-1、Br-1、I-1、NO3 -1、CH3COO-1、ClO4 -1、BF4 -1、OH-1、BPh4 -1Or N3 -1Monovalence anion；
In bimetallic catalyst, the dual-nuclei structure model and nucleophile R that are connected by biphenyl or dinaphthalene skeleton5R6 3YX1's
Molar ratio is 1 ﹕ 1~5.
2. synthetic method according to claim 1, it is characterised in that bimetallic catalyst rubs with meso epoxyalkane
You are than being 1:1000~200000, the molar ratio of meso epoxyalkane and cyclic acid anhydride is 1:1~10, reaction temperature for 0~
60 DEG C, when reaction 0.5~48 is small.
3. synthetic method according to claim 1 or 2, it is characterised in that the ligand in the dual-nuclei structure model
It is by the salicylide containing substituted radical, 3,3 ' containing substituted radical-diformyl -2,2 '-hydroxyl -1,1 '-biphenyl and Diamines
The reaction of mono-hydrochloric salts compound is made.
4. synthetic method according to claim 3, it is characterised in that the Diamines mono-hydrochloric salts compound is diamines
Class compound is ethylenediamine, 1,2- propane diamine, (rac) -2,3- butanediamine, (R, R) -2,3- butanediamine, (S, S) -2,3- fourths two
Amine, o-phenylenediamine, (rac)-cyclohexanediamine, (R, R)-cyclohexanediamine, (S, S)-cyclohexanediamine, (rac)-diphenyl ethylene diamine,
(R, R)-diphenyl ethylene diamine or (S, S)-diphenyl ethylene diamine.
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| CN113845661A (en) * | 2021-10-18 | 2021-12-28 | 天津大学 | Method for preparing polythioester by ring-opening alternating copolymerization of thiophenic anhydride and alkylene oxide |
| CN114163627A (en) * | 2021-11-09 | 2022-03-11 | 大连理工大学 | Double-function double-metal catalyst and its application |
| CN114479055B (en) * | 2022-02-28 | 2023-04-11 | 大连理工大学 | Bifunctional catalyst for copolymerization of alkylene oxide, cyclic anhydride and carbon dioxide and application method |
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