CN114904579A - Crown ether-based Lewis acid-base concerted catalysis system and application thereof - Google Patents

Crown ether-based Lewis acid-base concerted catalysis system and application thereof Download PDF

Info

Publication number
CN114904579A
CN114904579A CN202110178661.3A CN202110178661A CN114904579A CN 114904579 A CN114904579 A CN 114904579A CN 202110178661 A CN202110178661 A CN 202110178661A CN 114904579 A CN114904579 A CN 114904579A
Authority
CN
China
Prior art keywords
crown
groups
lewis acid
catalyzing
crown ether
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110178661.3A
Other languages
Chinese (zh)
Inventor
伍广朋
张瑶瑶
杨贯文
齐欢
王宇晖
杨莉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN202110178661.3A priority Critical patent/CN114904579A/en
Publication of CN114904579A publication Critical patent/CN114904579A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D205/00—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D205/02—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D205/06—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D205/08—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with one oxygen atom directly attached in position 2, e.g. beta-lactams
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/10—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having one or more double bonds between ring members or between ring members and non-ring members
    • C07D305/12—Beta-lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/04—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/02—Five-membered rings
    • C07D339/06—Five-membered rings having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates
    • 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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C08G63/56—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds other than from esters thereof
    • C08G63/58—Cyclic ethers; Cyclic carbonates; Cyclic sulfites ; Cyclic orthoesters
    • 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
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/26—Polythioesters
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/28—Polythiocarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/11—Lithium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/12—Sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/13—Potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/14—Rubidium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/15—Caesium
    • 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
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Polyethers (AREA)

Abstract

The invention discloses a crown ether-based Lewis acid-base synergistic catalytic system, which comprises Lewis acid and a metal crown ether complex; the metal crown ether complex has a structure shown in a formula I:
Figure DDA0002940822820000011
the invention also discloses the application of the binary catalytic system in preparing macromolecules and preparing organic micromolecules through ring-opening polymerization. The binary catalytic system has the advantages of high catalytic activity, controllable reaction and the like.

Description

Crown ether-based Lewis acid-base concerted catalysis system and application thereof
Technical Field
The invention relates to the field of polymer synthesis, in particular to a crown ether-based Lewis acid-base concerted catalysis system and application thereof.
Background
Polymer materials with different properties can be prepared by using different reaction monomers and polymerization methods, and the polymer materials play an indispensable and important role in the fields of clothes, eating and housing of people and the like [ chemical communication, 1978,2,54-57 ]. Since the 1940 s, a large number of synthetic polymer materials were invented and rapidly commercialized. The advent of ziegler-natta catalysts in the 1950 s has greatly promoted the rapid development of polymer synthesis chemistry. In 1960 s, the development of the petrochemical industry also provided a new and richer raw material source for high polymer materials. Since then, the annual production of polymeric materials has grown at an unusual rate and rapidly over other man-made materials. The total amount of resins and fibers produced globally has reached 78 million tons from 1950 to 2015, with a total amount of 39 million tons from 2002 to 2015 alone, and by 2050, the annual production of global resins and fibers will reach an astonishing 320 million tons [ Science Advances,2017,3, e1700782 ]. Therefore, the polymer material plays an increasingly important role in the life of people.
The synthesis of macromolecules typically requires the involvement of catalysts to increase production efficiency. The catalyst with high catalytic efficiency, low cost, environmental protection, safety and good product performance is the most ideal catalyst. The catalysts used at present usually involve complex synthesis, and the catalysts of some metal ligands have high cost and toxicity, so that the obtained materials have problems of toxicity, discoloration, degradation and the like, thereby limiting the applications of the catalysts, such as the applications in the fields of packaging, biomedicine and microelectronics. Therefore, the development of a catalytic system with low toxicity, low cost, high activity and simple preparation for the synthesis of macromolecules has important significance.
Disclosure of Invention
The invention aims to provide a crown ether-based Lewis acid-base concerted catalysis system and application thereof, and the system has the advantages of high catalytic activity, easiness in preparation, controllable reaction and the like.
A crown ether based lewis acid-base concerted catalysis system, the binary catalysis system comprising lewis acid and a metallic crown ether complex; the metal crown ether complex has a structure shown in a formula I:
Figure BDA0002940822800000021
each Z in the structural formula is independently selected from the group consisting of O, S, Se elements or NR '"groups, N is a nitrogen element, R'" is H or the following unsubstituted or substituted group: c 1 -C 30 Aliphatic radical, C 6 -C 30 Aryl radical, C 3 -C 30 Heterocyclic group, C 5 -C 30 One or more of heteroaromatic groups, or the group containing one or more of O, S, N, Si and P atoms; wherein the substituents are selected from halogen atoms, branched or straight chain aliphatic groups having 1 to 20 carbon atoms, 6 to 30One or more of an aromatic group of carbon atoms, a heteroaromatic group of 5 to 30 carbon atoms;
20≥j≥0；
each M i+ Represents a metal cation with charge i, which is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Ag, Cu, Ni, Hg, Pd, Zr, La, yttrium and ammonium cations.
Each A is (i/g)- Represents a metal M i+ The balancing negative ion of (3); each A is (i/g)- Is independently selected from
Figure BDA0002940822800000022
Figure BDA0002940822800000023
One or more of sulfonate, perchlorate, chlorate, phosphate, carboxylate, carbonate, alkoxide, phenoxide, sulfate and nitrate. g represents a counterion A (i/g)- In order to maintain charge balance.
Each R' and R "may be the same or different and is independently selected from the following unsubstituted or substituted groups: independently selected from H, or the following unsubstituted or substituted groups: c 1 -C 30 Aliphatic radical, C 6 -C 30 Aryl radical, C 3 -C 30 Heterocyclic group, C 5 -C 30 One or more of heteroaromatic groups, or the group containing one or more of O, S, N, Si and P atoms; wherein the substituents are selected from one or more of halogen atoms, branched or straight chain aliphatic groups having 1 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, heteroaromatic groups having 5 to 30 carbon atoms; any two or more groups in each of R 'and R' may be linked by a covalent bond to form a ring.
The Lewis acid is selected from: r is 3 Al，R 3 B，R 2 Mg，R 2 One or more of Zn;
wherein the subscript of R represents the number of R groups;
each R group may be the same or different and is independently selected from H, unsubstituted or substituted withThe following groups: c 1 -C 30 Aliphatic radical, C 6 -C 30 Aryl radical, C 3 -C 30 Heterocyclic group, C 5 -C 30 One or more of heteroaromatic groups, or the group containing one or more of O, S, N, Si and P atoms; wherein the substituents are selected from one or more of halogen atoms, branched or straight chain aliphatic groups having 1 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, heteroaromatic groups having 5 to 30 carbon atoms; the R groups may be bonded to each other to form a ring.
Preferably, the Lewis acid is selected from the group consisting of tributylaluminum, triisobutylaluminum, triethylborane, trimethylborane, triisobutylborane, tributylborane, triphenylborane, trisperfluorophenylborane, triisopropyl borate, 9-hexyl-9-borabicyclo (3,3,1) -nonane, diethyl zinc and diethyl magnesium.
The Lewis acid has the following structure:
Figure BDA0002940822800000041
preferably, the crown ether moiety, i.e., structure, of said metallacrown complex
Figure BDA0002940822800000042
One or more selected from the following structures: 12-crown-4, 15-crown-5, 18-crown-6, benzo-15-crown-5, dibenzo-18-crown-6, dibenzo-30-crown-10, dibenzo-24-crown-8, cyclohexyl-15-crown-5, dicyclohexyl-18-crown-6, dicyclohexyl-24-crown-8, diaza-18-crown-6, aza-18-crown-6, dibenzo pit [2,2]2-hydroxymethyl-12-crown-4; the metal in the metal crown ether exists in a cation form and has a corresponding counter ion;
the metal cation is selected from one or more of the following: li, Na, K, Rb, Cs, Be, Mg, Ca, Ag, Cu, Ni, Hg, Pd, Zr, La, yttrium, ammonium cations;
the counter ion is selected from one or more of the following:
Figure BDA0002940822800000052
Figure BDA0002940822800000053
one or more of sulfonate, perchlorate, chlorate, phosphate, carboxylate, carbonate, alkoxide, phenoxide, sulfate and nitrate.
Preferably, the metallocrown complex is selected from the following structures:
Figure BDA0002940822800000051
preferably, the ratio of the two components of the Lewis acid and the metal crown ether complex used is between 1: 1000-1000: 1.
The invention also provides application of the crown ether-based Lewis acid-base concerted catalysis system in ring-opening polymerization preparation of macromolecules, which comprises that one or more alkylene oxides or episulfide alkanes react with any one or more of carbon dioxide, carbon disulfide, sulfur oxide, carbon monoxide, isocyanate, isothiocyanate, sulfur dioxide and cyclic anhydride under the contact of the crown ether-based Lewis acid-base concerted catalysis system to obtain macromolecular catalytic products; ring-opening polymerization of small molecular lactone, thio-or seleno-lactone, N-hetero-or O-hetero-carboxylic anhydride, N-hetero-thiocarboxylic anhydride and cyclic carbonate.
Preferably, the catalytic reaction for preparing a macromolecule comprises the following reactions: catalyzing carbon dioxide (sulfur) to react with epoxy (sulfur) alkane to prepare poly (sulfur-containing) carbonate, catalyzing carbon oxysulfide to react with epoxy (sulfur) alkane to prepare poly (sulfur-containing) carbonate, catalyzing cyclic lactone (including sulfo-selenolactone) to prepare polyester by ring-opening polymerization, catalyzing epoxy (sulfur) alkane to react with cyclic (sulfo) anhydride to prepare (sulfo) polyester, catalyzing carbon monoxide to react with epoxy alkane to prepare polyester, catalyzing carbon monoxide to react with cyclic nitrogen alkane to prepare polyamide, catalyzing epoxy alkane to react with isocyanate to prepare polyurethane, catalyzing epoxy alkane to react with isothiocyanate to prepare sulfo-polyurethane, and catalyzing cyclic sulfur alkane to react with isothiocyanate to prepare poly (diimine disulfide).
Preferably, the alkylene oxide, epithioalkane, cyclic carbonate, thio-or seleno-lactone, cyclic anhydride, lactone, N-or O-heterocarboxylic anhydride, isocyanate, isothiocyanate is selected from the following structures:
Figure BDA0002940822800000061
wherein R is 1 And R 2 Selected from H, halogen, substituted, unsubstituted, C with or without O, S, N, Si, P atoms 1 -C 30 Alkyl radical, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl radical, C 2 -C 30 Alkynyl, C 6 -C 30 Aryl radical, C 3 -C 30 Heterocyclyl or C 5 -C 30 One or more of heteroaromatic groups; the substituent is selected from one or more of halogen atoms, branched or linear alkyl with 1 to 20 carbon atoms, branched or linear alkoxy with 1 to 20 carbon atoms, branched or linear cycloalkyl with 3 to 20 carbon atoms, aryl with 6 to 20 carbon atoms and heteroaryl with 5 to 20 carbon atoms; wherein each R is 1 And R 2 Can form a bond or a ring.
When the crown ether-based Lewis acid-base concerted catalysis system is applied to preparation of macromolecules through ring-opening polymerization, one or more alcohol compounds, acid compounds, amine compounds, polyols, polycarboxylic acids, polyol acids and water can be added into the polymerization reaction system to be used as chain transfer agents to prepare corresponding polymer polyols, or one or more polymers with alcoholic hydroxyl groups, phenolic hydroxyl groups, amino groups and carboxyl groups are added into the polymerization reaction system to be used as macromolecule chain transfer agents to prepare corresponding block copolymers or graft copolymers or polymers with specific terminal functional groups.
The invention also provides an application of the crown ether-based Lewis acid-base concerted catalysis system in preparation of organic micromolecules, which comprises the steps that one or more alkylene oxides or epithio-alkanes react with any one or more of carbon dioxide, carbon disulfide, carbon oxysulfide, carbon monoxide, isocyanate, isothiocyanate, sulfur dioxide and cyclic anhydride under the contact of the crown ether-based Lewis acid-base concerted catalysis system to obtain a micromolecule catalysis product; the catalytic reaction comprises the following reactions: catalyzing carbon dioxide (sulfur) to react with epoxy (sulfur) alkane to prepare cyclic (thio) carbonate, catalyzing carbon monoxide to react with epoxy alkane to prepare cyclic lactone, catalyzing carbon sulfur oxide to copolymerize with epoxy (sulfur) alkane to prepare cyclic thiocarbonate, and catalyzing carbon monoxide to react with cyclic azaalkane to prepare lactam.
The crown ether-based Lewis acid-base concerted catalysis system provided by the invention has the advantages of simple preparation, high yield, small dosage, low cost and the like; when the catalyst is used as a catalyst, the catalyst has the advantages of easy weighing, high catalytic activity, controllable reaction and the like, and the catalyst of the system has good performance in synthesizing various micromolecules and macromolecules by changing the composition and the proportion of a reaction system.
Drawings
FIG. 1 shows the nuclear magnetic hydrogen spectrum of the polyether (PPO) obtained in example 1;
FIG. 2 is a nuclear magnetic carbon spectrum of propylene carbonate obtained in example 2;
FIG. 3 shows CHO and CO in example 8 2 During copolymerization, nuclear magnetic spectrum of reaction liquid;
FIG. 4 is a GPC chart of polylactide obtained in example 14.
Detailed Description
The invention is described below by means of specific examples:
the following heterocycloalkanes and their abbreviations are used:
Figure BDA0002940822800000081
the cyclic (thio) anhydrides and their abbreviations used below:
Figure BDA0002940822800000082
O-Carboxylic anhydrides (N-Carboxylic anhydrides) and their abbreviations are used below:
Figure BDA0002940822800000083
the cyclic lactones used below and their abbreviations are:
Figure BDA0002940822800000091
iso (thio) cyanates and their abbreviations are used below:
Figure BDA0002940822800000092
example 1: preparation of polyether by catalyzing PO copolymerization
Figure BDA0002940822800000093
In the glove box, take L 2 (0.50mmol) and M 3 (0.01mmol) is added into a serum bottle, 1mol of PO is added, the reaction is carried out for 6h at the temperature of 0 ℃, reaction liquid is taken for nuclear magnetism to represent the conversion rate of the monomer, wherein the conversion rate of the PO is 96%. After drying, the polymer was characterized by GPC. Wherein the number average molecular weight M n 66.4kg/mol and a molecular weight distribution PDI of 1.13. The nuclear magnetic spectrum of the obtained polyether (PPO) is shown in figure 1.
Example 2: catalyzing PO and CO 2 Preparation of cyclic carbonates by reaction
Figure BDA0002940822800000094
In the glove box, take L 2 (0.01mmol) and M 14 (0.1mmol) was added to the autoclave, and 0.1mol of PO was charged and 1.5MPa of CO was charged 2 And reacting for 6 hours at 60 ℃. Then release CO 2 Taking reaction liquid to test nucleusMagnetism is used to characterize the conversion of the monomers and the selectivity of the products (polycarbonate, polyether, cyclic carbonate). Wherein the conversion of the monomer is 84% and the selectivity to cyclic carbonate is 100%. The nuclear magnetic carbon spectrum of the obtained cyclic carbonate is shown in FIG. 2.
Example 3: catalyzing SO and CS 2 Preparation of cyclic thiocarbonates by reaction
Figure BDA0002940822800000101
In the glove box, take L 3 (0.01mmol) and M 4 (0.01mmol) was charged into the autoclave, and 0.01mol of SO was charged into the autoclave, followed by charging 1.5MPa of CS 2 And reacting for 6 hours at 60 ℃. Then release the CS 2 Taking reaction liquid to measure nuclear magnetism to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of the thiopolycarbonate, the polyether and the cyclic thiocarbonate). Wherein the conversion rate of the monomer is 78%, the selectivity of the thiopolycarbonate is 0%, the selectivity of the polyether is 0%, and the selectivity of the cyclic thiocarbonate is 100%.
Example 4: catalysis of PS and CO 2 Preparation of cyclic thiocarbonates by reaction
Figure BDA0002940822800000102
In the glove box, take L 4 (0.01mmol) and M 5 (0.01mmol) was charged into the autoclave, and 0.01mol of PS was charged, and 1.5MPa of CO was charged 2 And reacting for 6h at 60 ℃. Then release CO 2 Taking reaction liquid to measure nuclear magnetism to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of the thiopolycarbonate, the polythioether and the cyclic thiocarbonate). Wherein the conversion of the monomer is 80% and the selectivity of the cyclic thiocarbonate is 100%.
Example 5: catalysis of SS and CS 2 Preparation of cyclic thiocarbonates by reaction
Figure BDA0002940822800000103
In the glove box, take L 5 (0.01mmol) and M 6 (0.01mmol) was added to the autoclave, and 0.01mol of SS was added thereto, and 1.5MPa of CS was charged 2 And reacting for 6 hours at 60 ℃. Then release the CS 2 Taking the reaction liquid to measure nuclear magnetism to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of the thiopolycarbonate, the polythioether and the cyclic thiocarbonate). Wherein the conversion of the monomer is 73% and the selectivity of the cyclic thiocarbonate is 100%.
Example 6: preparation of cyclic thiocarbonate by catalyzing reaction of CHO and COS
Figure BDA0002940822800000111
In the glove box, take L 6 (0.01mmol) and M 6 (0.01mmol) was charged into the autoclave, and 0.01mol of CHO was added, and 1.5MPa of COS was charged and reacted at 60 ℃ for 6 hours. Then releasing COS, and measuring nuclear magnetism of the reaction liquid to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of the thiopolycarbonate, the polyether and the cyclic thiocarbonate). Wherein the conversion of the monomer is 90% and the selectivity of the cyclic thiocarbonate is 100%.
Example 7: preparation of cyclic thiocarbonate by catalytic reaction of CHS and COS
Figure BDA0002940822800000112
In a glove box, take L 6 (0.01mmol) and M 6 (0.01mmol) was charged into the autoclave, and 0.01mol of CHS was added, followed by charging 1.5MPa of COS and reacting at 60 ℃ for 6 hours. Then releasing COS, and measuring nuclear magnetism of the reaction liquid to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of the thiopolycarbonate, the polythioether and the cyclic thiocarbonate). Wherein the conversion of the monomer is 83% and the selectivity to the cyclic thiocarbonate is 100%.
Example 8: catalysis of CHO and CO 2 Preparation of polycarbonates by copolymerization
Figure BDA0002940822800000121
In the glove box, take L 2 (0.02mmol) and M 3 (0.01mmol) was added to the autoclave, and 0.20mol of PO was charged and 1.5MPa of CO was charged 2 And reacting for 6 hours at 60 ℃. Then CO is released 2 The reaction solution was taken for nuclear magnetism to characterize the conversion of the monomer and the selectivity of the product (ratio of polycarbonate, polyether, cyclic carbonate, see FIG. 3). Wherein the monomer conversion was 49.3% and the polycarbonate selectivity was 100%. The polymer was precipitated from ethanol and, after drying, characterized by GPC. Wherein the number average molecular weight M n 45.6kg/mol and a molecular weight distribution PDI of 1.12.
Example 9: catalyzing SO and CS 2 Preparation of thiopolycarbonates by copolymerization
Figure BDA0002940822800000122
In a glove box, take L 7 (0.02mmol) and M 9 (0.01mmol) was charged into the autoclave, and 0.01mol of SO was charged into the autoclave, followed by charging 1.5MPa of CS 2 And reacting for 6 hours at 60 ℃. Then release the CS 2 Taking reaction liquid to measure nuclear magnetism to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of the thiopolycarbonate, the polyether and the cyclic thiocarbonate). Wherein the conversion of the monomer is 83%, the selectivity of the thiopolycarbonate is 91%, the selectivity of the polyether is 9%, and the selectivity of the cyclic thiocarbonate is 0%. The polymer was precipitated from ethanol and, after drying, characterized by GPC. Wherein the number average molecular weight M n 60.3kg/mol and a molecular weight distribution PDI of 1.17.
Example 10: catalysis of PS and CO 2 Preparation of thiopolycarbonates by copolymerization
Figure BDA0002940822800000123
In the glove box, take L 9 (0.01mmol) and M 12 (0.01mmol) was charged into the autoclave, and 0.01mol of PS was charged, and 1.5MPa of CO was charged 2 And reacting for 6 hours at 60 ℃. Then CO is released 2 Taking reaction liquid to measure nuclear magnetism to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of the thiopolycarbonate, the polythioether and the cyclic thiocarbonate). Wherein the monomer conversion is 76%, the thiopolycarbonate selectivity is 99%, the polythioether selectivity is 1%, and the cyclic thiocarbonate selectivity is 0%. The polymer was precipitated from ethanol and, after drying, characterized by GPC. Wherein the number average molecular weight M n 47.8kg/mol and a molecular weight distribution PDI of 1.14.
Example 11: catalysis of SS and CS 2 Copolymerization for the preparation of thiopolycarbonates
Figure BDA0002940822800000131
In the glove box, take L 9 (0.02mmol) and M 2 (0.01mmol) was charged into the autoclave, and 0.01mol of SS was added thereto, followed by charging 1.5MPa of CS 2 And reacting for 6h at 60 ℃. Then release the CS 2 Taking reaction liquid to measure nuclear magnetism to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of the thiopolycarbonate, the polythioether and the cyclic thiocarbonate). Wherein the conversion of monomer is 73%, the selectivity for thiopolycarbonate is 98%, the selectivity for polythioether is 2%, and the selectivity for cyclic thiocarbonate is 0%. The polymer was precipitated from ethanol and, after drying, characterized by GPC. Wherein the number average molecular weight M n 67.8kg/mol and a molecular weight distribution PDI of 1.15.
Example 12: preparation of thiopolycarbonate by catalyzing reaction of LO and COS
Figure BDA0002940822800000132
In the glove box, take L 7 (0.02mmol) and M 2 (0.01mmol) was added to the autoclave, and 0.01mol of LO was added, and 1.5MPa of COS was charged and reacted at 60 ℃ for 6 hours.Then releasing COS, and measuring nuclear magnetism of the reaction liquid to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of the thiopolycarbonate, the polyether and the cyclic thiocarbonate). Wherein the conversion rate of the monomer is 86%, the selectivity of the thiopolycarbonate is 99%, the selectivity of the polyether is 1%, and the selectivity of the cyclic thiocarbonate is 0%. The polymer was precipitated from ethanol and, after drying, characterized by GPC. Wherein the number average molecular weight M n 73.2kg/mol and a molecular weight distribution PDI of 1.12.
Example 13: preparation of thiopolycarbonate by catalytic reaction of CHS and COS
Figure BDA0002940822800000141
In the glove box, take L 7 (0.02mmol) and M 2 (0.01mmol) was charged into the autoclave, and 0.01mol of CHS was added, followed by charging 1.5MPa of COS and reacting at 60 ℃ for 6 hours. Then releasing COS, and measuring nuclear magnetism of the reaction liquid to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of the thiopolycarbonate, the polythioether and the cyclic thiocarbonate). Wherein the conversion of the monomer is 68%, the selectivity of the thiopolycarbonate is 96%, the selectivity of the polyether is 4%, and the selectivity of the cyclic thiocarbonate is 0%. The polymer was precipitated from ethanol and, after drying, characterized by GPC. Wherein the number average molecular weight M n 69.8kg/mol and a molecular weight distribution PDI of 1.14.
Example 14: preparation of polyester by catalyzing LA ring-opening polymerization
Figure BDA0002940822800000142
In a glove box, take L 7 (0.01mmol) and M 13 (0.02mmol) was added to a serum bottle and LA (0.01mol), 1ml toluene, reacted at 80 ℃ for 6 h. Taking reaction liquid to measure nuclear magnetism to characterize the conversion rate of the monomer. The conversion of LA was 97%. The polymer was precipitated from ethanol and, after drying, characterized by GPC. Wherein the number average molecular weight M n 23.5kg/mol, molecular weight fractionThe cloth PDI was 1.18. The GPC chart of the obtained polymer is shown in FIG. 4.
Example 15: preparation of polyester by catalyzing ring-opening polymerization of PO and MA
Figure BDA0002940822800000151
In the glove box, take L 4 (0.01mmol) and M 12 (0.01mmol) was added to a serum bottle, and PO (0.05mol) and MA (0.01mol) were added and reacted at 80 ℃ for 6 h. Taking reaction liquid for nuclear magnetism detection to characterize the conversion rate of the monomer, wherein the conversion rate of MA is 84%. The polymer was precipitated from ethanol and, after drying, characterized by GPC. Wherein the number average molecular weight M n 86.8kg/mol and a molecular weight distribution PDI of 1.05.
Example 16: preparation of thio-polyester by ring-opening polymerization of PS and SA
Figure BDA0002940822800000152
In a glove box, take L 7 (0.01mmol) and M 16 (0.01mmol) was added to a serum bottle, and PS (0.05mol) and SA (0.01mol) were added and reacted at 80 ℃ for 6 h. Taking reaction liquid to measure nuclear magnetism to represent the conversion rate of the monomer, wherein the conversion rate of SA is 76%. The polymer was precipitated from ethanol and, after drying, characterized by GPC. Wherein the number average molecular weight M n 78.6kg/mol and a molecular weight distribution PDI of 1.17.
Example 17: preparation of thio-polyester by catalyzing ring-opening polymerization of PO and TA
Figure BDA0002940822800000153
In the glove box, take L 6 (0.01mmol) and M 9 (0.01mmol) was added to a serum bottle, and PO (0.05mol) and TA (0.01mol) were added and reacted at 80 ℃ for 6 h. Taking reaction liquid to measure nuclear magnetism to characterize the conversion rate of the monomer, wherein the conversion rate of TA is 100%. Precipitation of the polymer from ethanolThe polymer, after drying, was characterized by GPC. Wherein the number average molecular weight M n 89.3kg/mol and a molecular weight distribution PDI of 1.12.
Example 18: preparation of thio-polyester by ring-opening polymerization of PS and TA
Figure BDA0002940822800000154
In the glove box, take L 7 (0.01mmol) and M 11 (0.01mmol) was added to a serum bottle, and PS (0.05mol) and TA (0.01mol) were added and reacted at 80 ℃ for 6 h. Taking reaction liquid to measure nuclear magnetism to represent the conversion rate of the monomer, wherein the conversion rate of the thiohydroxy acetic anhydride is 79 percent. The polymer was precipitated from ethanol and, after drying, characterized by GPC. Wherein the number average molecular weight M n 87.6kg/mol and a molecular weight distribution PDI of 1.09.
Example 19: preparation of polyester by catalyzing reaction of CHO and CO
Figure BDA0002940822800000161
In the glove box, take L 8 (0.02mmol) and M 17 (0.01mmol) was added to the autoclave and 0.01mol of PO was charged and reacted at 80 ℃ for 6h with 1.5MPa of CO. Then releasing CO, and measuring nuclear magnetism by using reaction liquid to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of polyester, polyether and cyclic lactone). Wherein the monomer conversion is 89% and the polyester selectivity is 100%. The polymer was precipitated from petroleum ether and, after drying, characterized by GPC. Wherein the number average molecular weight M n 12.6kg/mol and a molecular weight distribution PDI of 1.13.
Example 20: preparation of polyurethane by catalyzing reaction of PO and CHI
Figure BDA0002940822800000162
In the glove box, take L 10 (0.02mmol) and M 2 (0.01mmol) was added to a serum bottle, and PO (0.05mol) and CHI (0.01mol) were added and reacted at 60 ℃ for 6 h. Taking reaction liquid for nuclear magnetism detection to characterize the conversion rate of the monomer, wherein the conversion rate of CHI is 79%. The polymer was precipitated from ethanol and, after drying, characterized by GPC. Wherein the number average molecular weight M n 33.6kg/mol and a molecular weight distribution PDI of 1.15.
Example 21: preparation of thiopolyurethane by catalyzing CHO and PIS reaction
Figure BDA0002940822800000171
In a glove box, take L 2 (0.02mmol) and M 3 (0.01mmol) was added to a serum bottle, and CHO (0.05mol) and PIS (0.01mol) were added and reacted at 60 ℃ for 6 h. Taking reaction liquid to measure nuclear magnetism to characterize the conversion rate of the monomer and the selectivity of the product (the ratio of thiopolyurethane to polyether). Wherein the conversion of PIS is 79%, the selectivity of thiopolyurethane is 98% and the selectivity of polyether is 2%. The polymer was precipitated from ethanol and, after drying, characterized by GPC. Wherein the number average molecular weight M n 44.3kg/mol and a molecular weight distribution PDI of 1.12.
Example 22: preparation of polydisulfimide by catalyzing SS and CHIS reaction
Figure BDA0002940822800000172
In the glove box, take L 7 (0.02mmol) and M 3 (0.01mmol) was added to a serum bottle, and SS (0.05mol) and CHIS (0.01mol) were added and reacted at 60 ℃ for 6 h. Taking reaction liquid to measure nuclear magnetism to characterize the conversion rate of the monomer and the selectivity of the product (the ratio of thiopolyurethane, polythioether and polydisulfimide). Wherein the conversion of CHIS is 86%, the selectivity for thiopolyurethane is 5%, the selectivity for polythioether is 3%, and the selectivity for polydisulfimide is 92%. The polymer was precipitated from ethanol and, after drying, characterized by GPC. Wherein the number average molecular weight M n 65.8kg/mol, molecular weight distribution PDI 1.19.
Example 23: preparation of cyclic lactone by catalyzing reaction of EO and CO
Figure BDA0002940822800000173
In the glove box, take L 2 (0.03mmol) and M 17 (0.03mmol) was charged into the autoclave, and 0.03mol of EO and 1mL of ethylene glycol dimethyl ether were added, and 1.5MPa of CO was charged and reacted at 80 ℃ for 6 hours. Then CO is released, reaction liquid is subjected to nuclear magnetism measurement to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of polyester, polyether and cyclic lactone). Wherein the conversion of the monomer is 87% and the selectivity to the cyclic lactone is 100%.
Example 24: preparation of polyester by catalyzing EO and CO reaction
Figure BDA0002940822800000181
In the glove box, take L 1 (0.03mmol) and M 17 (0.03mmol) was placed in an autoclave and 0.03mol of EO was added, and 1.5MPa of CO was charged and reacted at 80 ℃ for 6 hours. Then releasing CO, and measuring nuclear magnetism by using reaction liquid to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of polyester, polyether and cyclic lactone). Wherein the monomer conversion is 90% and the polyester selectivity is 100%. The polymer was precipitated from ether and, after drying, characterized by GPC. Wherein the number average molecular weight M n 2.7kg/mol and a molecular weight distribution PDI of 1.20.
Example 25: preparation of polyester by catalyzing ring-opening homopolymerization reaction of epsilon-CL
Figure BDA0002940822800000182
In the glove box, take L 7 (0.01mmol) and M 12 (0.02mmol) was added to a serum bottle, and ε -CL (0.01mol), 1ml toluene were added and reacted at 80 ℃ for 6 h. Taking reaction liquid to detect nuclear magnetism to represent the conversion rate of the monomer. It is provided withThe conversion of epsilon-CL in (E-CL) was 98%. The polymer was precipitated from ethanol and, after drying, characterized by GPC. Wherein the number average molecular weight M n 18.3kg/mol and a molecular weight distribution PDI of 1.16.
Example 26: preparation of polyamide by catalyzing EI and CO ring-opening copolymerization reaction
Figure BDA0002940822800000183
In a glove box, take L 1 (0.03mmol) and M 17 (0.03mmol) was charged into the autoclave, and 0.03mol of EI was added, and 1.5MPa of CO was charged and reacted at 80 ℃ for 6 hours. Then CO is released, nuclear magnetism is measured in a reaction solution to characterize the conversion rate of the monomer and the selectivity of the product (the ratio of polyamide to lactam). Wherein the monomer conversion was 93%, the polyamide selectivity was 100%, and the lactam selectivity was 0%. The polymer was precipitated from ether and, after drying, characterized by GPC. Wherein the number average molecular weight M n 13.6kg/mol, a molecular weight distribution PDI of 1.20
Example 27: method for preparing lactam by catalyzing EI and CO ring-opening copolymerization reaction
Figure BDA0002940822800000191
In the glove box, take L 3 (0.03mmol) and M 17 (0.03mmol) was added to the autoclave, and 0.03mol of EI and 1mL of ethylene glycol dimethyl ether were added, charged with 1.5MPa of CO, and reacted at 80 ℃ for 6 hours. Then CO is released, nuclear magnetism is measured in a reaction solution to characterize the conversion rate of the monomer and the selectivity of the product (the ratio of polyamide to lactam). Wherein the monomer conversion was 89%, the polyamide selectivity was 4% and the lactam selectivity was 96%.
Example 28: preparation of polyester by catalyzing LOCA ring-opening homopolymerization
Figure BDA0002940822800000192
In the glove box, take L 7 (0.01mmol) and M 11 (0.02mmol) was charged into the autoclave, and LOCA (0.01mol), 1ml toluene were added and reacted at 80 ℃ for 6 hours. Then release CO 2 Taking reaction liquid to measure nuclear magnetism to characterize the conversion rate of the monomer. Wherein the conversion of LOCA is 94%. The polymer was precipitated from ethanol and, after drying, characterized by GPC. Wherein the number average molecular weight M n 67.8kg/mol and a molecular weight distribution PDI of 1.10.
Example 29: preparation of polyamide by ring-opening homopolymerization of catalytic ANCA (ANCA)
Figure BDA0002940822800000193
In the glove box, take L 7 (0.01mmol) and M 6 (0.01mmol) was added to the autoclave and ANCA (0.01mol), 1ml toluene was added and reacted at 80 ℃ for 6 h. Then release CO 2 Taking reaction liquid to measure nuclear magnetism to characterize the conversion rate of the monomer. Wherein the conversion of LOCA is 96%. The polymer was precipitated from ethanol and, after drying, characterized by GPC. Wherein the number average molecular weight M n 70.6kg/mol and a molecular weight distribution PDI of 1.16.
The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only the most preferred embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.

Claims (10)

1. A Lewis acid-base concerted catalysis system based on crown ether is characterized in that the binary catalysis system comprises Lewis acid and metal crown ether complex; the metal crown ether complex has a structure shown in formula I:
Figure FDA0002940822790000011
each Z in the structural formula is independently selected from the group consisting of O, S, Se elements or NR '"groups, N is a nitrogen element, and R'" is H or the following unsubstituted or substituted groups: c 1 -C 30 Aliphatic radical, C 6 -C 30 Aryl radical, C 3 -C 30 Heterocyclic group, C 5 -C 30 One or more of heteroaromatic groups, or the group containing one or more of O, S, N, Si and P atoms; wherein the substituents are selected from one or more of halogen atoms, branched or straight chain aliphatic groups having 1 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, heteroaromatic groups having 5 to 30 carbon atoms;
20≥j≥0；
each M i+ Represents a metal cation with charge i, which is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Ag, Cu, Ni, Hg, Pd, Zr, La, yttrium and ammonium cations.
Each A is (i/g)- Represents a metal M i+ The balancing negative ion of (3); each A is (i/g)- Is independently selected from
Figure FDA0002940822790000012
Figure FDA0002940822790000013
One or more of sulfonate, perchlorate, chlorate, phosphate, carboxylate, carbonate, alkoxide, phenoxide, sulfate and nitrate. g represents a counterion A (i/g)- In order to maintain charge balance.
Each R' and R "may be the same or different and is independently selected from the following unsubstituted or substituted groups: independently selected from H, or the following unsubstituted or substituted groups: c 1 -C 30 Aliphatic radical, C 6 -C 30 Aryl radical, C 3 -C 30 Heterocyclic group, C 5 -C 30 One or more of heteroaromatic groups, or the group containing one or more of O, S, N, Si and P atoms; wherein the substituents are selected from halogen atoms, branched or straight chain having 1 to 20 carbon atomsOne or more of a chain aliphatic group, an aromatic group of 6 to 30 carbon atoms, a heteroaromatic group of 5 to 30 carbon atoms; any two or more groups in each of R 'and R' may be linked by a covalent bond to form a ring.
2. The crown ether-based lewis acid-base concerted catalytic system of claim 1 wherein the lewis acid is selected from the group consisting of: r 3 Al，R 3 B，R 2 Mg，R 2 One or more of Zn;
wherein the subscript of R represents the number of R groups;
each R group, which may be the same or different, is independently selected from H, unsubstituted or substituted: c 1 -C 30 Aliphatic radical, C 6 -C 30 Aryl radical, C 3 -C 30 Heterocyclic group, C 5 -C 30 One or more of heteroaromatic groups, or the group containing one or more of O, S, N, Si and P atoms; wherein the substituents are selected from one or more of halogen atoms, branched or straight chain aliphatic groups having 1 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, heteroaromatic groups having 5 to 30 carbon atoms; the R groups may be bonded to each other to form a ring.
3. A crown ether based lewis acid-base concerted catalytic system according to claim 2, characterised in that the lewis acid is selected from one or more of tributyl aluminium, triisobutyl aluminium, triethylborane, trimethyl borane, triisobutyl borane, tributylborane, triphenylborane, trisperfluorophenyl borane, triisopropyl borate, 9-hexyl-9-borabicyclo (3,3,1) -nonane, diethyl zinc or diethyl magnesium.
4. The crown ether-based lewis acid-base concerted catalytic system of claim 1 wherein the structure of the crown ether moiety in the metallic crown ether complex
Figure FDA0002940822790000021
One or more selected from the following structures: 12-crown-4, 15-crown-5, 18-crown-6, benzo-15-crown-5, dibenzo-18-crown-6, dibenzo-30-crown-10, dibenzo-24-crown-8, cyclohexyl-15-crown-5, dicyclohexyl-18-crown-6, dicyclohexyl-24-crown-8, diaza-18-crown-6, aza-18-crown-6, dibenzo pit [2,2]2-hydroxymethyl-12-crown-4; the metal in the metal crown ether complex exists in a cation form and has a corresponding counter ion; the metal cation is selected from one or more of the following: li, Na, K, Rb, Cs, Be, Mg, Ca, Ag, Cu, Ni, Hg, Pd, Zr, La, yttrium, ammonium cations; the counter ion is selected from one or more of the following:
Figure FDA0002940822790000031
Figure FDA0002940822790000032
one or more of sulfonate, perchlorate, chlorate, phosphate, carboxylate, carbonate, alkoxide, phenoxide, sulfate and nitrate.
5. The crown ether-based lewis acid-base concerted catalysis system according to claim 1, wherein the metallic crown ether complex is selected from one or more of the following structures:
Figure FDA0002940822790000033
Figure FDA0002940822790000041
6. a crown ether based lewis acid-base concerted catalysis system according to claim 1, characterised in that the ratio of the two components of lewis acid and metallacrown complex is between 1: 1000-1000: 1.
7. The application of the crown ether-based Lewis acid-base concerted catalysis system in the ring-opening polymerization preparation of macromolecules, which is disclosed by any one of claims 1-6, is characterized in that the ring-opening polymerization preparation of macromolecules comprises a reaction of one or more alkylene oxides or episulfide alkanes and any one or more of carbon dioxide, carbon disulfide, carbon oxysulfide, carbon monoxide, isocyanate, isothiocyanate, sulfur dioxide and cyclic anhydride under the contact of the crown ether-based Lewis acid-base concerted catalysis system to obtain a macromolecular catalytic product; ring-opening polymerization of alkylene oxides, episulfide alkanes, small molecular lactones, thio-or seleno-lactones, N-hetero-or O-hetero-carboxylic anhydrides, N-hetero-thiocarboxylic anhydrides, cyclic carbonates.
8. Use of a crown ether based lewis acid-base concerted catalysis system in ring opening polymerization preparation of macromolecules according to claim 7, wherein the ring opening polymerization preparation of macromolecules comprises the following reactions: catalyzing carbon dioxide or carbon disulfide to react with alkylene oxide or sulfocycloalkane to prepare polycarbonate or polythiocarbonate, catalyzing carbon oxysulfide to react with alkylene oxide or sulfocycloalkane to prepare polycarbonate or polythiocarbonate, catalyzing cyclolactone thio or selenolactone to prepare polyester by ring-opening polymerization, catalyzing alkylene oxide or sulfocycloalkane to react with cyclic anhydride or cyclic thioanhydride to prepare polyester or thiopolyester, catalyzing carbon monoxide to react with alkylene oxide to prepare polyester, catalyzing carbon monoxide to react with cycloazacycloalkane to prepare polyamide, catalyzing alkylene oxide to react with isocyanate to prepare polyurethane, catalyzing alkylene oxide to react with isothiocyanate to prepare thiopolyurethane, catalyzing cyclothioalkane to react with isothiocyanate to prepare polydisulfimide, catalyzing alkylene oxide to ring-opening polymerization to prepare polyether, and catalyzing cyclothioalkane to ring-opening polymerization to prepare polythioether; or a combination of two or more of the above ring-opening reactions.
9. Use of a crown ether-based lewis acid-base concerted catalysis system in ring-opening polymerization for preparing macromolecules according to claim 7 or 8, wherein one or more alcohol compounds, acid compounds, amine compounds, polyols, polycarboxylic acids, polyol acids, water can be added into the polymerization reaction system as a chain transfer agent to prepare corresponding polymer polyols, or one or more polymers with alcoholic hydroxyl groups, phenolic hydroxyl groups, amino groups, carboxyl groups can be added into the polymerization reaction system as a macromolecular chain transfer agent to prepare corresponding block copolymers or graft copolymers or polymers with specific terminal functional groups.
10. The application of the crown ether-based Lewis acid-base concerted catalysis system in the preparation of organic micromolecules according to any one of claims 1 to 6, wherein the preparation of the organic micromolecules comprises the reaction of one or more alkylene oxides or episulfide alkanes and any one or more of carbon dioxide, carbon disulfide, carbon oxysulfide, carbon monoxide, isocyanate, isothiocyanate, sulfur dioxide and cyclic anhydride under the contact of the crown ether-based Lewis acid-base concerted catalysis system to obtain a micromolecule catalysis product; the catalytic reaction comprises the following reactions: catalyzing carbon dioxide or carbon disulfide to react with alkylene oxide or cyclic sulfanilamide to prepare cyclic carbonate or cyclic thiocarbonate, catalyzing carbon monoxide to react with alkylene oxide to prepare cyclic lactone, catalyzing carbon oxysulfide to copolymerize with alkylene oxide or cyclic sulfanilamide to prepare cyclic thiocarbonate, and catalyzing carbon monoxide to react with cyclic nitroalkane to prepare lactam.
CN202110178661.3A 2021-02-09 2021-02-09 Crown ether-based Lewis acid-base concerted catalysis system and application thereof Pending CN114904579A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110178661.3A CN114904579A (en) 2021-02-09 2021-02-09 Crown ether-based Lewis acid-base concerted catalysis system and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110178661.3A CN114904579A (en) 2021-02-09 2021-02-09 Crown ether-based Lewis acid-base concerted catalysis system and application thereof

Publications (1)

Publication Number Publication Date
CN114904579A true CN114904579A (en) 2022-08-16

Family

ID=82761271

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110178661.3A Pending CN114904579A (en) 2021-02-09 2021-02-09 Crown ether-based Lewis acid-base concerted catalysis system and application thereof

Country Status (1)

Country Link
CN (1) CN114904579A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114907390A (en) * 2021-02-09 2022-08-16 浙江大学 Organic boron-metal crown ether heteronuclear catalyst and preparation method and application thereof
CN115819787A (en) * 2022-12-02 2023-03-21 新疆农业大学 Propane diamine thiocyano type supermolecule ferroelectric phase change functional material and preparation method thereof

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000086755A (en) * 1998-09-11 2000-03-28 Japan Chemical Innovation Institute Catalyst composition for polymerizing propylene oxide
JP2000256457A (en) * 1999-03-09 2000-09-19 Japan Chemical Innovation Institute Propylene oxide polymerization catalyst composition and preparation of poly(propylene oxide)
US20040132936A1 (en) * 2003-01-03 2004-07-08 Tagge Christopher D. Transition metal complexes in the controlled synthesis of polyolefins substituted with functional groups
CN101130537A (en) * 2007-08-03 2008-02-27 中国科学院过程工程研究所 Method for producing ring carbonic acid ester with hydroxyl ion liquid
CN109096481A (en) * 2018-08-28 2018-12-28 浙江大学 A kind of preparation method of the catalyst system for being used to prepare the polymer containing polyethers and a variety of polymer containing polyethers
CN109705331A (en) * 2018-12-25 2019-05-03 浙江大学 A kind of Lewis Acids and Bases are to catalysis initiator and its application
CN110156970A (en) * 2019-06-26 2019-08-23 西北师范大学 A method of the Lewis Acids and Bases that are obstructed are to catalysis cyclic acid anhydride and epoxide copolymerization aliphatic polyester
CN110483753A (en) * 2019-05-20 2019-11-22 北京化工大学 The method of Lewis Acid-Base System controlled catalytic O- carboxylic acid anhydride monomer's ring-opening polymerisation based on metal salt and organic base
WO2020057356A1 (en) * 2018-09-21 2020-03-26 浙江大学 Organic metal-free catalyst having both electrophilic and nucleophilic functions, preparation method therefor, and application thereof
CN112225666A (en) * 2020-11-10 2021-01-15 江苏八巨药业有限公司 Preparation method of (R) -3-amino-4- (2,4, 5-trifluorophenyl) methyl butyrate

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000086755A (en) * 1998-09-11 2000-03-28 Japan Chemical Innovation Institute Catalyst composition for polymerizing propylene oxide
JP2000256457A (en) * 1999-03-09 2000-09-19 Japan Chemical Innovation Institute Propylene oxide polymerization catalyst composition and preparation of poly(propylene oxide)
US20040132936A1 (en) * 2003-01-03 2004-07-08 Tagge Christopher D. Transition metal complexes in the controlled synthesis of polyolefins substituted with functional groups
CN101130537A (en) * 2007-08-03 2008-02-27 中国科学院过程工程研究所 Method for producing ring carbonic acid ester with hydroxyl ion liquid
CN109096481A (en) * 2018-08-28 2018-12-28 浙江大学 A kind of preparation method of the catalyst system for being used to prepare the polymer containing polyethers and a variety of polymer containing polyethers
WO2020057356A1 (en) * 2018-09-21 2020-03-26 浙江大学 Organic metal-free catalyst having both electrophilic and nucleophilic functions, preparation method therefor, and application thereof
CN109705331A (en) * 2018-12-25 2019-05-03 浙江大学 A kind of Lewis Acids and Bases are to catalysis initiator and its application
CN110483753A (en) * 2019-05-20 2019-11-22 北京化工大学 The method of Lewis Acid-Base System controlled catalytic O- carboxylic acid anhydride monomer's ring-opening polymerisation based on metal salt and organic base
CN110156970A (en) * 2019-06-26 2019-08-23 西北师范大学 A method of the Lewis Acids and Bases that are obstructed are to catalysis cyclic acid anhydride and epoxide copolymerization aliphatic polyester
CN112225666A (en) * 2020-11-10 2021-01-15 江苏八巨药业有限公司 Preparation method of (R) -3-amino-4- (2,4, 5-trifluorophenyl) methyl butyrate

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
YATAO LIANG,: "Lewis acidic ionic liquids of crown ether complex cations: preparation and applications in organic reactions", 《RSC ADVANCES》, vol. 6, pages 1 *
YI-JUN HUANG: "Controlled Ring-Opening Polymerization of Propylene Oxide Catalyzed by Double Metal-Cyanide Complex", 《PROPYLENE OXIDE》 *
YINGYING SONG: "Aza-Crown Ether Complex Cation Ionic Liquids: Preparation and Applications in Organic Reactions", 《CHEM. EUR. J.》, pages 12895 *
胡岚方;张兴宏;: "有机小分子催化环醚与环状酸酐共聚研究进展", 功能高分子学报, no. 03 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114907390A (en) * 2021-02-09 2022-08-16 浙江大学 Organic boron-metal crown ether heteronuclear catalyst and preparation method and application thereof
CN115819787A (en) * 2022-12-02 2023-03-21 新疆农业大学 Propane diamine thiocyano type supermolecule ferroelectric phase change functional material and preparation method thereof
CN115819787B (en) * 2022-12-02 2023-09-08 新疆农业大学 Propanediamine thiocyanato type supermolecule ferroelectric phase change functional material and preparation method thereof

Similar Documents

Publication Publication Date Title
CN114904579A (en) Crown ether-based Lewis acid-base concerted catalysis system and application thereof
Ree et al. A new copolymerization process leading to poly (propylene carbonate) with a highly enhanced yield from carbon dioxide and propylene oxide
Kricheldorf et al. Polylactones, 8. Mechanism of the cationic polymerization of L, L‐dilactide
Zhao et al. From competition to cooperation: a highly efficient strategy towards well-defined (co) polypeptides
US4665136A (en) Process for producing novel block alkylene polycarbonate copolymers
US20110245424A1 (en) Precise Control of Molecular Weight and Chain Shape Control in Carbon Dioxide/Epoxide Alternating Copolymerization and Preparation of Low Molecular Weight Poly(alkylene Carbonate) Thereby
KR20090090154A (en) Method for recovering catalysts from a copolymerization process
CN112390819B (en) Organic catalyst, preparation method and application
Liu et al. PPC-based reactive hot melt polyurethane adhesive (RHMPA)—Efficient glues for multiple types of substrates
WO2002031023A1 (en) Copolymer comprising alkylene carbonate and method of preparing same
CN113105611A (en) Polymerization method for ring-opening alternating copolymerization of anhydride compound and epoxy compound
Peng et al. A facile route to realize the copolymerization of l-lactic acid and ε-caprolactone: sulfonic acid-functionalized Brønsted acidic ionic liquids as both solvents and catalysts
CN113336932B (en) Metal coordination catalyst for synthesizing carbon dioxide-based biodegradable material and application thereof
JPS6330524A (en) Branched polycarbonate containing methylene-bis-naphthalene compound and its production
US5091507A (en) Polymerization of carbon monoxide/olefin with polyalkoxyalkane
CN112387307A (en) Electrophilic nucleophilic bifunctional organic catalyst, preparation method and application
KR101476378B1 (en) Modified polylactide resin with cadanol and preparation method thererof
Zhou et al. Highly efficient strategies toward sustainable monomers and polymers derived from fatty acids via tetramethylguanidine promoted esterification
Li et al. Homoleptic lanthanide amidinate complexes: A single‐component initiator for ring‐opening polymerization of trimethylene carbonate and copolymerization with ϵ‐caprolactone
CN104829848A (en) Dissoluble nitrogenous hyperbranched polymer and manufacturing method and application therefor
CN112851924A (en) Recyclable nitrogen-containing polycarbonate plastic synthesis method
CN111925508A (en) Preparation method of polycaprolactone and product thereof
US3784517A (en) Preparation of polybenzimidazoles in the presence of a sulfone solvent
Rabani et al. Synthesis of poly (ether‐esteramide) elastomers by a palladium‐catalyzed polycondensation of aromatic diiodides with telechelic diamines and carbon monoxide
KR20140073433A (en) Lactide copolymer, its preparation method and resin composition comprising thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination