CN106117532A - The synthetic method of a kind of stereoregularity polyester and bimetallic catalyst - Google Patents
The synthetic method of a kind of stereoregularity polyester and bimetallic catalyst Download PDFInfo
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- CN106117532A CN106117532A CN201610542576.XA CN201610542576A CN106117532A CN 106117532 A CN106117532 A CN 106117532A CN 201610542576 A CN201610542576 A CN 201610542576A CN 106117532 A CN106117532 A CN 106117532A
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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
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Abstract
The present invention relates to synthetic method and the bimetallic catalyst of a kind of stereoregularity polyester.This catalyst is the dual-nuclei structure model coupled together by two metal centers by biphenyl or dinaphthalene skeleton.This catalyst, under nucleophilicity co-catalyst effect, can prepare polyester with meso epoxyalkane polyreaction by high efficiency catalysis cyclic acid anhydride under compared with temperate condition and relatively low catalyst concn, and catalytic efficiency is 103~106Gram polymer/mol catalyst, polymer molecular weight is 103~105In the range of adjustable, its molecular weight distribution be less than 2, steric regularity is adjustable between 60~100%, and alternating structure is more than 98%, and can be degraded into micromolecular compound under certain condition.Using the catalyst system and catalyzing of chiral ligand, selectivity of product and the alternating structure selectivity of polymer are above 98%, and the enantiomeric excess value of the glycol obtained after degraded is higher than 70%, provides prospect widely for commercial Application.
Description
Technical field
The present invention relates to synthetic method and the catalyst thereof of a kind of stereoregularity polyester, particularly to one by meso
The method that epoxyalkane becomes stereoregularity polyester with cyclic acid anhydride alternating copolymerization, and it is catalyzed the bimetallic of this polyreaction
Catalyst.
Background technology
Disposable plastic packing material and plastics article of everyday use consume bulk petroleum resource the most aborning, and with rear
It is not easily recycled recycling, it is also difficult to by environment degradable, causes environmental pollution.So, formulate Biodegradable Materials and be correlated with
Product is one of important research target of whole world scientific circles.Wherein, aliphatic polyester is due to its good biocompatibility, life
The advantages such as thing degradability and workability and receive significant attention.The polyester product of commercialization the most has poly-succinic ethylene glycol
Ester (PES), poly butylene succinate (PBS), polylactic acid (PLA), poly 3-hydroxy butyrate (PHB), polycaprolactone (PCL)
Deng.But, these monomers used by commercialization polyester material depend on biotechnology wholly or in part and produce, thus there is cost
Universal higher, efficiency is low, it is difficult to large-scale production.Therefore, developing low-cost may replace Nondegradable polyolefin general-purpose plastics
Degradable property new material just becomes particularly important.
It is a class novel degradable polymer material that epoxyalkane and the ring opening copolymer of cyclic acid anhydride react the polyester formed.
Two kinds of substrates of this kind of reaction are very easy to the most inexpensively be obtained by chemical means, have the highest Economic competitive.This
Outward, one of reaction substrate epoxyalkane has abundant type, has spatial chemistry problem in ring opening process, thus make with
There is many stereochemical structures in the polyester that cyclic acid anhydride copolymerization is formed.And the polyester of steric order is likely to be crystallization, it should
There is higher heat stability, it will be greatly improved the range of application of this kind of material.Therefore, completely can be by controlling polyester
Stereochemical structure carrys out heat stability and the mechanical property of controlled material.Obviously, the key during catalyst is polyester production process
Factor.Efficiently, the catalyst of low toxicity can not only improve the molecular weight of polymerizate, reduce the energy consumption in polymerization process, promote
Product quality and range of application, additionally it is possible to improve the safety of polyester product, to adapt to the need in the field such as environment, bio-medical
Ask.
The bicomponent system just reporting porphyrin aluminum and quaternary ammonium () salt composition as far back as Inoue in 1985 is used for being catalyzed epoxy
Ethane and benzoic anhydride copolymerization (Aida T.;Inoue S.J.Am.Chem.Soc.1985,107,1358), but reaction is very slow, generally
Needing could convert completely for 4~7 days, molecular weight is about 3000.After 12 years, Maeda et al. finds simple diethoxy magnesium
Can also catalytic epoxyethane and succinic anhydrides copolymerization, 100 DEG C long-time (2 days) reaction obtain 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 be Cornell University Coates professor seminar find itrile group take
It is higher with cyclic acid anhydride copolymerization that the β in generation-diamidogen zinc acetate can be catalyzed various epoxyalkane under the temperate condition of 50 DEG C
Molecular weight and polyester (the Jeske R.C. in alternating structure;DiCiccio A.M.;Coates
G.W.J.Am.Chem.Soc.2007,129,11330).Additionally, Salen symmetrically or non-symmetrically or porphyrin metal complex (as
Chromium, cobalt, aluminum and zinc etc.) polyreaction of epoxyalkane and cyclic acid anhydride can also be catalyzed.Sectional interest is catalyzed altogether at nucleophilicity
In the presence of agent, can be catalyzed epoxyalkane, cyclic acid anhydride telomerizes conjunction (DiCiccio A.M. with 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 catalysis end position epoxyalkane such as epoxy
Chloropropane, phenyl glycidyl ether and the copolyreaction of maleic anhydride, find Catalyzed by Pt/M Bimetallic Nano the two polyreaction
Catalysis 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).Find that bimetallic catalyst is at catalysis (s)-phenyl glycidyl
When ether and maleic anhydride, the epoxyalkane of more than 99% selects to participate in polyreaction in the open loop of methylene position, obtains first
Obtain the optically active polyester of retention of configuration.Recently, Coates et al. find with optical activity (R, R)-salenCo (III) or (S,
S)-salenCo (III) complex-catalyzed chiral epoxy propane and succinic anhydrides copolymerization, it is thus achieved that up to 97% head-tail phase order
Optically active polyester (the Longo J.M. of unit;DiCiccio A.M.;Coates G.W.J.Am.Chem.Soc.2014,136,
15897).What is more important author finds that these optically active polyesters can slowly crystallize after placing under certain condition, and
The polyester of two kinds of opposite configuration can quickly crystallize after mixing with 1:1, and degree of crystallinity is higher, and fusing point improves 40 DEG C, is a class knot
The stereo complex of crystalline substance.
Although epoxyalkane is the green polyreaction that a class is novel with the ring opening copolymer synthesis polyester of cyclic acid anhydride, but high
Effect realizing this process there is also problems.First, catalyst activity is the highest, key issue be epoxyalkane with
Cyclic acid anhydride reactivity matching problem in polymerization process.Secondly, high stereoregularity catalyst does not the most occur how
Realize the epoxyalkane high enantioselective ring-opening in polymerization process.It is crucial that design the catalysis of high activity high stereoregularity
System, by controlling the chemical constitution of polymer, including polymer molecular weight and distribution, region and stereoregularity, copolymerization
The insertion rate of comonomer and sequence distribution etc. in thing, it is desirable to realize cutting out to obtain ad hoc structure and performance to macromolecular chain
Macromolecular material;Utilize electronic effect and the space confinement effect at metal catalytic activity center, cause in propagation process single
The directivity that body coordination is inserted.
Be previously reported by is prepared polyester process by epoxyalkane and cyclic acid anhydride copolymerization, mostly exist catalyst activity low,
Response time is long, severe reaction conditions;Seldom relate to polyester spatial chemistry, be not directly directly synthesized vertical from achirality substrate
Structure regularity polyester.
Summary of the invention
The present invention proposes a kind of new method synthesizing stereoregularity polyester, by the chirality bimetallic catalytic of design
Agent, catalysis meso epoxyalkane and the stereoregularity polyester of cyclic acid anhydride asymmetric 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 obtains stereoregularity polyester in alternating structure completely by copolymerization;As follows:
If using chirality bimetallic catalyst, meso epoxyalkane and cyclic acid anhydride are obtained by asymmetric alternating copolymerization
The polyester that main chain is chirality obtained;As follows:
In formula, meso epoxyalkane is:
Cyclic acid anhydride is:
For be catalyzed the bimetallic catalyst of meso epoxyalkane and cyclic acid anhydride alternating copolymerization be by by biphenyl or
The dual-nuclei structure model of dinaphthalene skeleton connection and nucleophile R5R6 3YX1Bi-component catalytic body as promoter composition
System;
The structure of dual-nuclei structure model is:
In formula, M is 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, onitrophenol oxygen, paranitrophenol oxygen, metanitrophenol oxygen, 2,4-dinitrophenol,DNP oxygen,
3,5-dinitrophenol,DNP oxygen, 2,4,6-trinitrophenol oxygen, 3,5-chlorophenesic acid oxygen, 3,5-difluorophenol oxygen, 3,5-bis--trifluoro
Methylphenol oxygen or pentafluranol negative oxygen ion;
Promoter nucleophile R5R6 3YX1Middle R5R6 3Y is the cationic moiety of promoter;
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 connected by biphenyl or dinaphthalene skeleton and nucleophile
R5R6 3YX1Mol ratio be 1 1~5.
The described part in dual-nuclei structure model be by the salicylide containing substituted radical, containing substituted radical 3,3 '-
Diformyl-2,2 '-hydroxyl-1,1 '-biphenyl and the reaction of Diamines mono-hydrochloric salts compound prepare.
Such as
Described Diamines mono-hydrochloric salts compound be diamine compounds be 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
Diamidogen, (S, S)-cyclohexanediamine, (rac)-diphenyl ethylene diamine, (R, R)-diphenyl ethylene diamine or (S, S)-diphenyl second two
Amine.
The mol ratio of bimetallic catalyst and meso epoxyalkane is 1:1000~200000, meso epoxyalkane with
The mol ratio of cyclic acid anhydride is 1:1~10, and reaction temperature is 0~60 DEG C, reacts 0.5~48 hour.
Beneficial effects of the present invention:
(1) the stereoregularity polyester of backbone chiral it is directly synthesized from achirality substrate;
(2) under low catalyst concentration, still there is higher catalytic activity;
(3) reaction condition is relatively mild, and process is easy;
(4) catalyst activity is high, and polymerizate selectivity is high;
(5) in polyester product, alternating structure is higher than 98%, and molecular weight distribution is narrower;Part stereoregularity polyester has
Crystallizable performance;
(6) copolymerization of chiral catalyst catalysis cyclic acid anhydride and meso epoxyalkane is used, polymerizate
Selectivity and alternating structure selectivity are above 98%, and the enantiomeric excess value of the glycol obtained after degraded is higher than 70%.
Detailed description of the invention
Below in conjunction with technical scheme and table, further illustrate the detailed description of the invention of the present invention.
In 100mL reactor, add in the following order under ambient temperature: a certain amount of major catalyst (claim
In book Article 1 describe any metal complex), promoter R1R2 3YX1, it is separately added into a certain amount of epoxyalkane
And cyclic acid anhydride.Reactor was kept at a proper temperature and after the rule response time, stops stirring.Polymerization product chlorine
Imitative/methanol extraction washs three times, is dried to constant weight under vacuum, and application gel permeation chromatography measures polymer molecular weight and divides
Cloth;Application Varian INOVA-400MHz measures it1HNMR, calculates the carbonate unit content of polymerizate.Use 500MHz core
Magnetic-measurement its13CNMR, calculates the steric regularity of polyester.For using chiral catalyst, then by polymerizate NaOH
Weak solution is hydrolyzed into glycol, measures its enantioselectivity with chiral chromatogram.
Table 1 is the alternating copolymerization of the complex-catalyzed 7-oxa-bicyclo[4.1.0 of trivalent metal and phthalic anhydride
Note 1: all of catalytic reaction is all polymerisation in bulk, because anhydride is good at epoxyalkane solute effect, therefore epoxy
Alkane excess, anhydride can realize converting completely.
Note 2:Entry 1, polymer is polyalkylene oxide homopolymers, produces without polyester, and remaining reaction obtains the chemical constitution of polyester
Selectivity > 99%, polymerization process does not have polyethers formed.
Note 3: except specified otherwise, all catalyst are all without chirality or racemic.
Note 4: if application has the catalyst of chirality, the ee value of the diol product after the polyester obtained degraded is at 70-
Between 99% adjustable.
Note 5:Entry 46, reacts with 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 alternating copolymerization of the complex-catalyzed 7-oxa-bicyclo[4.1.0 of trivalent metal and various cyclic acid anhydrides
Note 1: all of catalytic reaction is all polymerisation in bulk, because anhydride is good at epoxyalkane solute effect, therefore epoxy
Alkane excess, anhydride can realize converting completely.
Note 2: catalyst/co-catalyst/epoxyalkane mol ratio is 1/2/250/1000.
Note 3: polyreaction obtains the chemical constitution selectivity of polyester > 99%, polymerization process does not have polyethers formed.
Note 4: except specified otherwise, all catalyst are all without chirality or racemic.
Note 5: if application has the catalyst of chirality, the ee value of the diol product after the polyester obtained degraded is at 70-
Between 99% adjustable.
Note 6:PPN is double (dihalotriphenylphosphoranes base) ammonium cations.
Note 7: as with toluene as solvent, toluene/epoxyalkane=1/2 (volume ratio), polyreaction still can be carried out, and
Realizing epoxyalkane and anhydride converts completely, activity and molecular weight are suitable with the condition with epoxyalkane as solvent.
Claims (5)
1. the synthetic method of a stereoregularity polyester, it is characterised in that under bimetallic catalyst effect, by meso ring
Oxygen alkane and cyclic acid anhydride obtain stereoregularity polyester in alternating structure completely by copolymerization;
As follows:
If using chirality bimetallic catalyst, meso epoxyalkane and cyclic acid anhydride are obtained by asymmetric alternating copolymerization
Main chain is the polyester of chirality;As follows:
In formula, meso epoxyalkane is:
Cyclic acid anhydride is:
Synthetic method the most according to claim 1, it is characterised in that bimetallic catalyst rubs with meso epoxyalkane
You are than being 1:1000~200000, and the mol ratio of meso epoxyalkane and cyclic acid anhydride is 1:1~10, reaction temperature be 0~
60 DEG C, react 0.5~48 hour.
3. bimetallic catalyst used in the synthetic method described in claim 1 or 2, it is characterised in that be used for being catalyzed meso
The bimetallic catalyst of epoxyalkane and cyclic acid anhydride alternating copolymerization is by the dinuclear metal connected by biphenyl or dinaphthalene skeleton
Coordination compound and nucleophile R5R6 3YX1Bi-component catalyst system and catalyzing as promoter composition;
The structure of dual-nuclei structure model is:
In formula, M is 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, onitrophenol oxygen, paranitrophenol oxygen, metanitrophenol oxygen, 2,4-dinitrophenol,DNP oxygen, 3,5-
Dinitrophenol,DNP oxygen, 2,4,6-trinitrophenol oxygen, 3,5-chlorophenesic acid oxygen, 3,5-difluorophenol oxygen, 3,5-di-trifluoromethyl
Phenol oxygen or pentafluranol negative oxygen ion;
Promoter nucleophile R5R6 3YX1Middle R5R6 3Y is the cationic moiety of promoter;
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 connected by biphenyl or dinaphthalene skeleton and nucleophile R5R6 3YX1's
Mol ratio is 1 1~5.
Bimetallic catalyst the most according to claim 3, it is characterised in that the described part in dual-nuclei structure model
Be by the salicylide containing substituted radical, 3,3 '-diformyl-2,2 containing substituted radical '-hydroxyl-1,1 '-biphenyl and Diamines
The reaction of mono-hydrochloric salts compound prepares.
Bimetallic catalyst the most according to claim 4, it is characterised in that described Diamines mono-hydrochloric salts compound is
Diamine compounds is 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)-cyclohexanediamine, (S, S)-cyclohexanediamine, (rac)-diphenyl second two
Amine, (R, R)-diphenyl ethylene diamine or (S, S)-diphenyl ethylene diamine.
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CN109705350A (en) * | 2019-01-12 | 2019-05-03 | 大连理工大学 | A kind of preparation method of the poly- monothioester of semi-aromatic |
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