CN113087882B - Organic catalytic system with polyboron center and application - Google Patents

Organic catalytic system with polyboron center and application Download PDF

Info

Publication number
CN113087882B
CN113087882B CN202010018753.0A CN202010018753A CN113087882B CN 113087882 B CN113087882 B CN 113087882B CN 202010018753 A CN202010018753 A CN 202010018753A CN 113087882 B CN113087882 B CN 113087882B
Authority
CN
China
Prior art keywords
catalyzing
groups
carbon atoms
alkylene oxide
atoms
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.)
Active
Application number
CN202010018753.0A
Other languages
Chinese (zh)
Other versions
CN113087882A (en
Inventor
伍广朋
张瑶瑶
杨贯文
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 CN202010018753.0A priority Critical patent/CN113087882B/en
Publication of CN113087882A publication Critical patent/CN113087882A/en
Application granted granted Critical
Publication of CN113087882B publication Critical patent/CN113087882B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0264—Phosphorus acid amides
    • B01J31/0265—Phosphazenes, oligomers thereof or the corresponding phosphazenium salts
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • 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
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • 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
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
    • 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
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
    • 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
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J35/19—
    • 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
    • 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
    • C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
    • C08G63/42—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
    • 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
    • C08G63/87—Non-metals or inter-compounds thereof
    • 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
    • C08G65/08—Saturated oxiranes
    • C08G65/10—Saturated oxiranes characterised by the catalysts used
    • 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
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
    • C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
    • 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
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C08G65/24—Epihalohydrins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • 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
    • C08G75/02—Polythioethers
    • C08G75/06—Polythioethers from cyclic thioethers
    • C08G75/08—Polythioethers from cyclic thioethers from thiiranes
    • 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

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)
  • Catalysts (AREA)

Abstract

The invention discloses an organic catalytic system with a polyborosity center, which comprises a main catalyst with a polyborosity center and a cocatalyst; the invention also discloses a preparation method and application of the organic catalytic system with the polyboronic center. The organic catalytic system disclosed by the invention has the advantages of high activity and easiness in preparation, and shows excellent reaction activity when applied to the preparation of small organic molecules and polymers.

Description

Organic catalytic system with polyboron center and application
Technical Field
The invention relates to the field of catalyst synthesis, in particular to an organic catalytic system with a polyboron center and application thereof.
Background
Sustainable development is a major concern in the international society today, and green and environmental protection of chemical reactions are also becoming increasingly important. The organic catalyst has the characteristics of low toxicity, low cost and the like, so that the organic catalyst is focused in the fields of organic chemistry, polymer chemistry, preparation of polymer materials and the like, and becomes an important research field under the strategy of sustainable development. The reactions involved in current organic catalysts include polyesters, polycarbonates, polyethers, polyamides, polyurethanes, some small molecule syntheses, and the like. The materials have very wide application prospects in the fields of packaging, bio-pharmaceuticals, microelectronic processing and the like. However, organic catalysts also face some challenges. For example, the catalytic activity is not high, so that a large amount of catalyst is often required to be added when the catalyst is used, and even a stoichiometric amount of organic catalyst is required to be added in some catalytic reactions, which is an important factor for limiting the large-scale application of the organic catalyst at present.
Among the metal organic catalysts, bimetallic catalysts tend to exhibit more excellent reaction properties than single metal catalysts due to their synergistic effect, such as [ j.am. Chem. Soc.2013,135,18901-18911; chemSuschem 2016,9,791-794]. Since the outermost layer of boron atoms has only 3 electrons, has very good electrophilicity, and boron and Al are the same as main groups and exhibit characteristics similar to metals, if a double-center or multi-center boron-containing organic catalyst is designed, it is expected to exhibit more excellent reactivity in application.
The catalyst system with trialkyl boron as catalyst and organic base as promoter may be used in ring opening homo-polymerization of alkylene oxide; copolymerization of carbon dioxide with alkylene oxide to produce polycarbonate [ J.Am.chem.Soc.2016,138,11117-11120; CN 107849233a; US 2018/011884 A1]; copolymerization of alkylene oxide and carbon oxysulfide to produce a thiopolycarbonate [ CN 106866952A; macromolecules,2018,51,3126-3134), alkylene oxide and acid anhydride to prepare polyester [ Green chem.2018,20,3963-3973 ].
Therefore, how to further increase the reactivity of the organic catalytic system is a research hotspot in the field at present.
Disclosure of Invention
The invention aims to provide an organic catalytic system with a polyboron center, which has the advantages of high activity and easiness in preparation, and shows excellent reactivity when applied to the preparation of small organic molecules and polymers.
The technical scheme provided by the invention is as follows:
an organic catalytic system having a polyboronic center, the organic catalytic system comprising a procatalyst having a polyboronic center and a cocatalyst; the main catalyst with the polyborosity center has a chemical structure shown in a formula I or a formula II:
wherein X representsB is boron atom;
each Y is independently selected from one or more of the following structures:
p, O, S, N, C, si each represents a phosphorus, oxygen, sulfur, nitrogen, carbon, and silicon atom;
wherein R is 1 ～R 24 Each independently selected from H, halogen, unsubstituted, substituted, C with or without O, S, N, si, P atoms 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 3 -C 30 Heterocyclyl, C 5 -C 30 One or more of the heteroaromatic groups; the substituent is selected from one or more of halogen atom, branched or straight chain hydrocarbon group with 1 to 20 carbon atoms, branched or straight chain alkoxy with 1 to 20 carbon atoms, branched or straight chain cycloalkyl with 3 to 20 carbon atoms, aromatic group with 6 to 20 carbon atoms, heteroaromatic group with 5 to 20 carbon atoms, each R 1 ～R 24 Two or more of which may form a bond or a ring;
x and Y are defined as R 1 ～R 3 Any one or more of and R 4 ～R 24 Any one or more of which are covalently linked;
wherein a in formula I and formula II is independently selected from integers of 2-100000; in the formula II, b and c are integers from 0 to 20, but are not 0 at the same time; each a, b and c are independent, each a can be the same or different, each b can be the same or different, and each c can be the same or different;
the cocatalysts include, but are not limited to, one or more of organic bases, imidazoles and imidazolium salts, quaternary ammonium salts, quaternary phosphonium salts, bis (triphenylphosphine) ammonium salts, aminocyclopropene salts, or metal salts.
Preferably, the procatalyst having a polyborocenter has the structure shown below:
wherein each i is independently selected from integers of 0 to 10000, and the sum of each i in the same molecule is more than or equal to 2;
each K is 1 ～K 4 Independently selected from unsubstituted, substituted, with or without O, S, N, si, P atoms C 0 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 3 -C 30 Heterocyclyl or C 5 -C 30 One or more of the heteroaromatic groups; the substituents are selected from halogen atoms, branched or straight-chain hydrocarbon groups having 1 to 20 carbon atomsOne or more of a branched or straight chain alkoxy group of 1 to 20 carbon atoms, a branched or straight chain cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, a heteroaryl group of 5 to 20 carbon atoms;
each R is 1 、R 2 Independently selected from H, halogen, unsubstituted, substituted C with or without O, S, N, si, P atoms 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 3 -C 30 Heterocyclyl or C 5 -C 30 One or more of the heteroaromatic groups; the substituent is selected from one or more of halogen atoms, branched or straight-chain hydrocarbon groups with 1 to 20 carbon atoms, branched or straight-chain alkoxy groups with 1 to 20 carbon atoms, branched or straight-chain cycloalkyl groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms and heteroaromatic groups with 5 to 20 carbon atoms;
wherein each K is 1 ～K 4 、R 1 、R 2 May form a bond or a ring.
Preferably, when R in the procatalyst 1 、R 2 And R is 3 R when not bonded to each other to form a ring 1 、R 2 And R is 3 Each independently selected from any one or more of the following structures:
when R is 1 And R is 2 R when bonded to each other to form a ring 1 And R is 2 The structure is shown as follows:
when R is 1 、R 2 And R is 3 The bonds form a ring, and can be expressed as the following structure:
represented as covalent linkages.
Preferably, the procatalyst having a polyborocenter has the structure shown below:
the cocatalysts are preferably but not limited to small molecule compounds, or linear, branched or crosslinked polymers, as described below:
wherein each R 25 ～R 43 Independently selected from H, substituted, unsubstituted, with or without C of O, S, N, si, P atoms 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 3 -C 30 Heterocyclyl or C 5 -C 30 One or more of the heteroaromatic groups; the substituent is selected from any one or more of halogen atoms, branched or straight-chain hydrocarbon groups with 1 to 20 carbon atoms, branched or straight-chain alkoxy groups with 1 to 20 carbon atoms, branched or straight-chain cycloalkyl groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms and heteroaromatic groups with 5 to 20 carbon atoms; each R is 25 ～R 43 Two or more of which may form a bond or a ring;
r' is selected from the group consisting ofSubstituted, C with substituents, containing or not containing O, S, N, si, P atoms 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 3 -C 30 Heterocyclyl, C 5 -C 30 One or more of the heteroaromatic groups; the substituent is selected from any one or more of halogen atoms, branched or straight-chain hydrocarbon groups with 1 to 20 carbon atoms, branched or straight-chain alkoxy groups with 1 to 20 carbon atoms, branched or straight-chain cycloalkyl groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms and heteroaromatic groups with 5 to 20 carbon atoms; v represents the number of corresponding effective functional groups in the organic base molecule, v effective functional groups pass through R 25 ～R 30 Is connected by one or more covalent bonds, v is an integer of more than or equal to 1 and less than 10000; u represents the number of carboxylate radicals and corresponding ammonium salts or phosphine salts, and is an integer more than or equal to 2 and less than 10000;
each of which is provided withIndependently selected from-> One or more of ortho-nitrophenoxy anions, para-nitrophenoxy anions, meta-nitrophenoxy anions, 2, 4-dinitrophenol oxy anions, 3, 5-dinitrophenol oxy anions, 2,4, 6-trinitrophenol oxy anions, 3, 5-dichlorophenol oxy anions, 3, 5-difluorophenol oxy anions, 3, 5-di-trifluoromethylphenoxy anions, pentafluorophenol oxy anions, carboxylate, bicarbonate, alkoxide, phenoxide, trifluoroacetate, hydroxide, benzoate, p-toluenesulfonate, trichloroacetate, benzenesulfonate, p-trifluoromethylphensulfonate, perchlorate, chlorate, phosphate anions.
In addition, it should be noted that if the promoter is selected from metal salts such as lithium salts (e.g., lithium methoxide, lithium ethoxide, lithium isopropoxide, lithium tert-butoxide, lithium hydroxide, etc.), potassium salts (potassium methoxide), sodium salts (sodium methoxide, sodium ethoxide, etc.), and aluminum salts (aluminum triisopropoxide, aluminum trimethoxy), etc., it is also within the scope of the present patent.
In the organic catalytic system with the polyborosity provided by the invention, the preparation method of the main catalyst with the polyborosity comprises the following steps: a small molecular compound, linear polymer, branched polymer or crosslinked polymer obtained by a hydroboration reaction of a reaction raw material W1 containing at least one unsaturated bond and a reaction raw material W2 containing at least one boron hydrogen bond;
the reaction raw material W1 is selected from one or more of the following structural formulas:
wherein each Q 1 ～Q 4 Independently selected from unsubstituted, substituted, with or without O, S, N, si, P atoms C 0 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 3 -C 30 Heterocyclyl or C 5 -C 30 One or more of the heteroaromatic groups; wherein the substituent is selected from one or more of halogen, branched or straight chain hydrocarbon group of 1 to 20 carbon atoms, branched or straight chain alkoxy of 1 to 20 carbon atoms, branched or straight chain cycloalkyl of 3 to 20 carbon atoms, aromatic group of 6 to 30 carbon atoms or heteroaromatic group of 5 to 30 carbon atoms;
wherein each T 1 ～T 4 Independently selected from unsubstituted, substituted, with or without O, S, N, si, P atoms C 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 3 -C 30 Heterocyclyl, C 5 -C 30 One or more of the heteroaromatic groups; wherein the substituents are selected from one or more of halogen atoms, branched or straight chain hydrocarbon groups having 1 to 20 carbon atoms, branched or straight chain alkoxy groups having 1 to 20 carbon atoms, branched or straight chain cycloalkyl groups having 3 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, heteroaromatic groups having 5 to 30 carbon atoms;
wherein each Q 1 ～Q 4 And each T 1 ～T 4 Two or more of which may form a bond or a ring;
each of which is provided withIndependently represent a carbon-carbon single bond (or a hydrocarbon single bond when T is hydrogen), a carbon-carbon double bond or a carbon-carbon triple bond, but not all may be single bonds at the same time;
the structural formula of the reaction raw material W2 is as follows:
G 1 、G 2 independently selected from H, halogen, unsubstituted, substituted C with or without O, S, N, si, P atoms 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 3 -C 30 Heterocyclyl or C 5 -C 30 One or more of the heteroaromatic groups; the substituent is selected from one or more of halogen atoms, branched or straight-chain hydrocarbon groups with 1 to 20 carbon atoms, branched or straight-chain alkoxy groups with 1 to 20 carbon atoms, branched or straight-chain cycloalkyl groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms and heteroaromatic groups with 5 to 20 carbon atoms; wherein each G 1 、G 2 May be bonded or looped.
The preparation route of the organic catalysis is as follows:
specifically, the preparation method of the electrophilic nucleophilic bifunctional organic catalyst comprises the following steps: mixing the reaction raw material W1 and the reaction raw material W2 under the protection of nitrogen or other inert gases, adding an organic solvent, stirring for 1-500 hours at the temperature of-20-150 ℃ to carry out hydroboration reaction, and removing impurities and the organic solvent after the reaction is finished to obtain the organic catalyst with electrophilic nucleophilic double functions. Wherein the organic solvent is selected from one or a combination of at least two of tetrahydrofuran, benzene, toluene, chloroform, hexane, diethyl ether, dichloromethane, ethyl acetate, dimethyl sulfoxide, carbon tetrachloride, 1, 4-dioxane or pyridine.
The invention also provides application of the organic catalytic system with the polyborosity, which is used for preparing small organic molecules or polymers, wherein the molar ratio of the main catalyst with the polyborosity to the cocatalyst is between 1: 10000-10000: 1.
Preferably, whether a chain transfer agent or an initiator is added or not can be selected in the use process to further improve the catalytic efficiency, and the use amount of the chain transfer agent or the initiator is 0-10000000 of the mole number of the main catalyst; the chain transfer agent or the initiator can be arbitrarily selected from one or more small molecules or macromolecular polymers containing amino groups, mercapto groups, hydroxyl groups, phenolic hydroxyl groups and carboxyl groups with active hydrogen.
Preferably, the polymer is aliphatic polycarbonate obtained by catalyzing copolymerization of carbon dioxide and alkylene oxide, polyether obtained by catalyzing ring-opening polymerization of alkylene oxide, polythiocarbonate obtained by catalyzing ring-opening polymerization of carbon dioxide and cyclothioalkane, polythioether obtained by catalyzing ring-opening of cyclic thioether, polyester obtained by catalyzing copolymerization of alkylene oxide and cyclic anhydride, polythiocarbonate obtained by catalyzing copolymerization of carbon oxysulfide and alkylene oxide or polyester obtained by catalyzing copolymerization of alkylene oxide and carbon monoxide, polypeptide obtained by catalyzing ring-opening polymerization of lactone, polyester obtained by catalyzing ring-opening of O-carboxyanhydride, and the like.
The small organic molecules are cyclic carbonate obtained by catalyzing the reaction of carbon dioxide or carbon disulfide and alkylene oxide or cyclothioalkane, cyclic lactone obtained by catalyzing the reaction of carbon monoxide and alkylene oxide, and cyclic thiocarbonate obtained by catalyzing the copolymerization of carbon oxysulfide and alkylene oxide or cyclothioalkane.
Preferably, the alkylene oxides, sulfolane, cyclic anhydrides, lactones include, but are not limited to, the following structures:
wherein R is 44 And R is 45 Selected from H, halogen, substituted, unsubstituted, C with or without O, S, N, si, P atoms 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 3 -C 30 Heterocyclyl or C 5 -C 30 One or a combination of at least two of the heteroaromatic groups; the substituent is selected from one or more of halogen atoms, branched or straight-chain hydrocarbon groups with 1 to 20 carbon atoms, branched or straight-chain alkoxy groups with 1 to 20 carbon atoms, branched or straight-chain cycloalkyl groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms and heteroaromatic groups with 5 to 20 carbon atoms; wherein each R 44 And R is 45 May be bonded or looped.
Preferably, the cyclic monomer includes, but is not limited to, the following structure:
/>
/>
preferably, when the organic catalytic system with the polyboron center provided by the invention is applied to the preparation of small organic molecules or polymers, the organic main catalyst and the cocatalyst can be loaded on an inorganic carrier or an organic carrier for use, or can be used as heterogeneous catalysts due to the self cross-linked structure. The use method is beneficial to catalyst removal, recovery and reuse.
Compared with the prior art, the invention has the following advantages: the organic catalytic system with the polyborosity center has the advantages of high activity, easiness in preparation, easiness in storage (difficult in spontaneous combustion), high efficiency and low cost. The catalyst and the cocatalyst can be selectively used together with a chain transfer agent or an initiator, and the formed catalytic system can be controlled in a large range, so that the catalyst has excellent reactivity in the preparation of high polymer materials such as polyether, polyester, polycarbonate, polythiocarbonate, polythioether and the preparation of compounds such as cyclic lactone, cyclic carbonate or small thio cyclic carbonate molecules.
Detailed Description
The invention is described in detail below by way of specific examples:
example 1: synthesis of procatalyst B1
In a glove box, 0.2mol of raw material r1-1 and 0.1mol of r1-2 are added into 100ml of ethyl acetate to react for 1h at room temperature, the solvent is pumped out, and the mixture is washed with hexane, so that the target product B1 can be obtained with the yield of 99%.
Example 2: synthesis of procatalyst B2
In a glove box, 0.2mol of r2-1 (8.4 g) and 0.1mol of r2-2 (16.8 g) were added to 100ml of tetrahydrofuran, stirred at-20℃for 36 hours, and the solvent was drained off and washed with hexane to give the objective product B2 in a yield of 91%.
Example 3: synthesis of procatalyst B3
In a glove box, 0.2mol of each of the starting materials r3-1 and 0.1mol of r3-2 was added to 100ml of tetrahydrofuran, stirred at room temperature for 6 hours, the solvent was drained off, and washed with hexane to give the objective product B3 in a yield of 93%.
Example 4: synthesis of procatalyst B4
In a glove box, 0.3mol of raw material r4-1 and 0.1mol of r4-2 are added into 100ml of diethyl ether to react for 6 hours at room temperature, the solvent is pumped out, and the mixture is washed by hexane, so that the target product B4 is obtained, and the yield is 90%.
Example 5: synthesis of procatalyst B5
In a glove box, 0.2mol of raw material r5-1 and 0.1mol of r5-2 are added into 100ml of dichloromethane, the mixture is reacted for 12 hours at room temperature, the solvent is pumped out, the mixture is washed by hexane, and a target product B5 can be obtained, the yield is 85 percent, and the characteristic of the B5 is performed by using nuclear magnetism.
Example 6: synthesis of procatalyst B6
In a glove box, 0.2mol of raw material r6-1 and 0.1mol of r6-2 are added into 100ml of tetrahydrofuran, stirred at room temperature for 48 hours, the solvent is pumped out, the solvent is washed with hexane, and the target product B6 can be obtained, the yield is 75 percent, and the characteristic of the B6 is performed by using nuclear magnetism.
Example 7: synthesis of procatalyst B7
In a glove box, 0.2mol of raw material r7-1 and 0.1mol of r7-2 are added into 100ml of tetrahydrofuran, stirred for 24 hours at 60 ℃, the solvent is pumped out, and the solvent is washed with hexane, so that the target product B7 is obtained, and the yield is 89%.
Example 8: synthesis of procatalyst B8
In a glove box, 0.4mol of raw material r8-1 and 0.1mol of r8-2 are added into 300ml of toluene to react for 36 hours at room temperature, the solvent is pumped out, and the solvent is washed by hexane, so that the target product B8 is obtained with the yield of 78 percent.
Example 9: synthesis of procatalyst B9
In a glove box, 0.2mol of raw material r9-1 and 0.1mol of r9-2 are added into 100ml of toluene to react for 200 hours at 130 ℃, the solvent is pumped out, and the mixture is washed by hexane, so that the target product B9 can be obtained with the yield of 72 percent.
Example 10: synthesis of procatalyst B10
/>
In a glove box, 0.2mol of starting material r10-1 and 0.2mol of starting material r10-2 (as measured by Si) were added to 200ml of tetrahydrofuran, and reacted at 60℃for 8 hours to obtain B10.
Example 11: synthesis of procatalyst B11
In a glove box, 0.1mol of raw material r11-1 and 0.1mol of raw material r11-2 are added into 200ml of tetrahydrofuran, reacted for 8 hours at 60 ℃, then heated to 120 ℃ to carry out free radical polymerization, and reacted for 24 hours to obtain B11.
In addition, the main catalyst B11 can be regulated and controlled by selecting one or more strategies as follows, 1) styrene is added after the hydroboration reaction, and the B content of the polymer is regulated and controlled; 2) After the borohydride reaction, the excess reaction raw material r11-2 is added or added at the beginning of the reaction, and radical polymerization is further performed, whereby a crosslinked organic catalyst can be obtained.
Example 12: synthesis of procatalyst B12
In a glove box, 0.1mol of raw material r12-1 and 0.1mol of raw material r12-2 were added to 200ml of tetrahydrofuran, and reacted at 60℃for 24 hours to obtain B12.
Cocatalysts used in the following application examples and abbreviations thereof:
alkylene oxide/sulfolane and abbreviations thereof used in the following application examples:
the cyclic anhydride used in the following application examples is abbreviated as follows:
the cyclic lactones used in the following application examples are abbreviated as follows:
application examples 1-6: the main catalysts B1-B4 and the cocatalyst are utilized to catalyze the copolymerization of the alkylene oxide and the carbon dioxide (the catalyst in the reaction equation is an organic catalytic system)
In a glove box, the cocatalyst, chain transfer agent and procatalyst prepared in examples 1-4 were added in the corresponding proportions to the autoclave and 0.01mol of alkylene oxide was added and 1.5MPa of CO was charged 2 And reacted at 80℃for 2 hours. Then carbon dioxide is released, the reaction solution is taken to measure nuclear magnetism to characterize the conversion rate of the monomer and the selectivity of the product (the ratio of polycarbonate, polyether and cyclic carbonate), and the test results are shown in table 1.
TABLE 1 test results of catalytic products of application examples 1 to 6 a
Wherein the test results a : after 2 hours, the conversion rate of the alkylene oxide is more than 99 percent, and the selectivity of the polymer is more than 99 percent; proportion of b : alkylene oxide: the main catalyst: and (3) a cocatalyst: molar ratio of chain transfer agent; m is M n c : number average molecular weight as measured by gel permeation chromatography; p (P)DI d : molecular weight distribution, as measured by gel permeation chromatography.
Application examples 7-12: copolymerization of alkylene oxide and cyclic anhydride catalyzed by main catalyst B2 and cocatalyst
In a glove box, the procatalyst B2 prepared in example 2 was taken and added to Xu Linke, and alkylene oxide (0.05 mol) and cyclic anhydride (0.01 mol) were added and reacted at 80℃for 6h. The reaction solution is taken to measure nuclear magnetism so as to characterize the conversion rate of the monomer and the selectivity of the product. The polymer was precipitated from petroleum ether and, after drying, the polymer was characterized by GPC. The polymerization results and characterization are shown in Table 2.
TABLE 2 test results of catalytic products of application examples 7 to 12 a
Wherein the test results a : after 6 hours, the conversion rate of the cyclic anhydride reaches more than 99 percent, and the selectivity of the polymer reaches more than 99 percent; proportion of b : alkylene oxide: the main catalyst: and (3) a cocatalyst: molar ratio of chain transfer agent; m is M n c : number average molecular weight as measured by gel permeation chromatography; PDI (PDI) d : molecular weight distribution, as measured by gel permeation chromatography.
Application examples 13-21: homo-polymerization of alkylene oxide by using main catalysts B4 and B5 and cocatalyst
In a glove box, the main catalyst prepared in examples 4 and 5 was taken into a serum bottle, and an alkoxyalkane (0.1 mol) was added thereto and reacted at 5℃for 2 hours. And taking the reaction liquid to measure nuclear magnetism to represent the conversion rate of the monomer and the selectivity of the product, and drying to obtain the target polyether. The polymer was characterized by GPC. The polymerization results and characterization are shown in Table 3.
TABLE 3 test results for catalytic products of application examples 13-18 a
Wherein the test results a : after 2 hours, the conversion rate of the alkylene oxide is more than 99 percent, and the selectivity of the polymer is more than 99 percent; proportion of b : alkylene oxide: the main catalyst: and (3) a cocatalyst: molar ratio of chain transfer agent; m is M n c : number average molecular weight as measured by gel permeation chromatography; PDI (PDI) d : molecular weight distribution, as measured by gel permeation chromatography.
Application examples 19-24: cyclothiane homopolymerization catalyzed by main catalysts B4 and B5 and cocatalyst
In a glove box, the main catalyst prepared in examples 4, 5 was taken into a liquid storage bottle, and alkylthio alkane (0.1 mol) was added thereto for reaction at 50℃for 4 hours. And taking the reaction liquid to measure nuclear magnetism to represent the conversion rate of the monomer and the selectivity of the product, and drying to obtain the target polythioether. The polymer was characterized by GPC. The polymerization results and characterization are shown in Table 4.
TABLE 4 test results of the catalytic products of application examples 19 to 24 a
Wherein the test results a : after 4 hours, the conversion rate of the cyclosulfanyl alkane is more than 99 percent, and the selectivity of the polymer is more than 99 percent; proportion of b : alkylene oxide: alkylene oxide: the main catalyst: and (3) a cocatalyst: molar ratio of chain transfer agent; m is M n c : number average molecular weight as measured by gel permeation chromatography; PDI (PDI) d : molecular weight distributionAs measured by gel permeation chromatography.
Application examples 25-29: method for catalyzing homo-polymerization of cyclic lactone by using main catalyst B3 and cocatalyst
In a glove box, the main catalyst prepared in example 3 was taken into a serum bottle, and cyclic lactone (0.01 mol), 1 ml of toluene was added and reacted at 80℃for 12 hours. And taking the reaction liquid to measure nuclear magnetism to represent the conversion rate of the monomer and the selectivity of the product, and drying to obtain the target polyester. The polymer was characterized by GPC. The polymerization results and characterization are shown in Table 5.
TABLE 5 test results of the catalytic products of application examples 23-29
Wherein the ratio is a : cyclic lactones: the main catalyst: and (3) a cocatalyst: molar ratio of chain transfer agent; m is M n b : number average molecular weight as measured by gel permeation chromatography; PDI (PDI) c Molecular weight distribution, as measured by gel permeation chromatography.
Application examples 30-34: catalysis of the copolymerization of Cyclothiane and carbon dioxide with the main catalyst B5
/>
In a glove box, the procatalyst B5 (0.01 mmol) prepared in example 5 was taken and introduced into an autoclave, and 0.01mol of the corresponding cyclosulfane was added and 1.5MPa of CO was charged 2 And reacted at 80℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product (the ratio of polythiocarbonate to polythioether to cyclic thiocarbonate). The polymerization results and characterization are shown in Table 6.
TABLE 6 test results of catalytic products of application examples 30-34
Wherein the ratio is a : cyclothiane: the main catalyst: and (3) a cocatalyst: molar ratio of chain transfer agent; m is M n b : number average molecular weight as measured by gel permeation chromatography; PDI (PDI) c Molecular weight distribution, as measured by gel permeation chromatography.
Application example 35: catalytic alkylene oxide/carbonyl sulfide copolymerization reaction using main catalyst B6 and cocatalyst
In a glove box, the procatalyst B6 prepared in example 6 and propylamine (0.01 mmol each) were taken and charged into an autoclave, and 0.01mol of PO was added, and 1.5MPa of COS was charged and reacted at 80℃for 2 hours. Then releasing the carbonyl sulfide, taking the reaction liquid to measure the nuclear magnetism to represent the conversion rate of the monomer and the selectivity of the product, wherein the conversion rate is 98%, the selectivity of the polythiocarbonate is 70%, the polyether accounts for 30%, the oxygen-sulfur exchange is avoided, and the product is in a ring-free state.
Application example 36: catalytic copolymerization of cyclothioalkane/carbonyl sulfide with main catalyst B7 and cocatalyst
In a glove box, the procatalyst B7 prepared in example 7 and PPNCl (0.01 mmol each) were taken and charged into an autoclave, and 0.01mol of PS was added, and 1.5MPa of COS was charged and reacted at 80℃for 2 hours. Then releasing the carbonyl sulfide, taking the reaction liquid to measure the nuclear magnetism to represent the conversion rate of the monomer and the selectivity of the product, wherein the conversion rate is 90%, the selectivity of the polythiocarbonate is 80%, the polythioether accounts for 20%, and the reaction liquid has no oxygen-sulfur exchange and no ring-shaped product.
Application example 37: method for catalyzing copolymerization of cyclothioalkane/carbon disulfide by using main catalyst B8 and cocatalyst
In a glove box, the procatalyst B8 prepared in example 8 and PPNCl (0.01 mmol each) were taken and charged into an autoclave, and 0.01mol of PS,0.02mol of CS were added 2 And reacted at 80℃for 6 hours. The reaction solution is taken to measure nuclear magnetism to represent the conversion rate of the monomer and the selectivity of the product, wherein the conversion rate is 95%, the selectivity of the polythiocarbonate is 55%, the polythioether accounts for 30%, and the cyclic product accounts for 15%.
Application example 38: catalytic alkylene oxide/carbon disulphide copolymerization using a primary catalyst B9 and a co-catalyst
In a glove box, the procatalyst B9 prepared in example 9 and PPNCl (0.01 mmol each) were taken and introduced into an autoclave, and 0.02mol of PO,0.04mol of CS were added 2 And reacted at 60℃for 5 hours. The reaction solution is taken to measure nuclear magnetism to represent the conversion rate of the monomer and the selectivity of the product, wherein the conversion rate is 99%, the selectivity of the polythiocarbonate is 20%, the polythioether accounts for 60%, and the cyclic product accounts for 20%.
Application example 39: catalytic polypeptide production using procatalyst B10 and cocatalyst
In a glove box, the procatalyst B10 prepared in example 10 and PPNCl (0.01 mmol each) were taken in a reservoir and 0.02mol of monomer was added and reacted at 60℃for 5h. The reaction solution is taken to measure nuclear magnetism to represent the conversion rate of the monomer and the selectivity of the product, and the conversion rate is 99%.
Application example 40: catalytic polypeptide production using procatalyst B10 and cocatalyst
In a glove box, the procatalyst B10 prepared in example 10 and PPNCl (0.01 mmol each) were taken in a reservoir and 0.02mol of monomer was added and reacted at 60℃for 5h. The reaction solution is taken to measure nuclear magnetism to represent the conversion rate of the monomer and the selectivity of the product, and the conversion rate is 99%.
Application example 41: catalytic alkylene oxide carbonylation reaction using procatalyst B11 and cocatalyst
In a glove box, the procatalysts B11 and (Bu) prepared in example 11 were taken 4 N + Co(CO) 4 - (0.1 mmol each) was charged into an autoclave, and 0.01mol of PO was added thereto, CO was charged at 3MPa, and reacted at 80℃for 24 hours. And then releasing the carbonyl sulfide, taking the reaction liquid to measure the nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, wherein the conversion rate is 90%, and obtaining the high-purity beta-butyrolactone.
Application example 42: catalytic alkylene oxide and CO using a procatalyst B12 and a cocatalyst 2 Reaction to form cyclic carbonates
In a glove box, the procatalyst B12 prepared in example 12 and TBAI (0.1 mmol,10 mmol) were taken and introduced into an autoclave, and 0.5mol of PO was added and 3MPa of CO was charged 2 And reacted at 120℃for 6 hours. Then releasing carbon dioxide, taking out the reaction liquid to measure the coreThe magnetism is used for representing the conversion rate of the monomer and the selectivity of the product, the conversion rate is 99%, and the propylene carbonate with high purity is obtained.

Claims (6)

1. An organic catalytic system having a polyborogenic center, wherein the organic catalytic system comprises a procatalyst having a polyborogenic center and a cocatalyst;
the procatalyst having a polyborocenter has the structure shown below:
wherein each i is independently selected from integers of 0 to 10000, and the sum of each i in the same molecule is more than or equal to 2;
K 1 selected from unsubstituted C 1 -C 30 An alkyl group;
each K is 2 ～K 4 Independently selected from unsubstituted or substituted C with or without O, S, N, si, P atoms 1 -C 30 An alkyl group; the substituents are selected from halogen atoms, branched or straight chain hydrocarbon groups having 1 to 20 carbon atoms;
when R is 1 、R 2 R when not bonded or looped 1 、R 2 Each independently selected from any one or more of the following structures:
when R is 1 、R 2 R when bonded to each other to form a ring 1 And R is 2 The structure is shown as follows:
represented by covalent linkages
Each Y is independently selected from one or more of the following structures:
wherein R is 16 ～R 23 Each independently selected from H, halogen, unsubstituted, substituted C with or without O, S, N, si, P atoms 1 -C 30 Alkyl, C 6 -C 30 One or more of the aromatic groups; the substituent is selected from one or more of halogen atoms, branched or straight-chain hydrocarbon groups with 1 to 20 carbon atoms and aromatic groups with 6 to 20 carbon atoms;
each Y and B is R 16 ～R 23 Any one or more of the groups of (a) are covalently linked;
wherein a is independently selected from integers from 2 to 100000; each a in different chemical formulas is independent, and each a can be the same or different;
the cocatalyst is one or more of the following general formulas:
wherein each R 25 ～R 43 Independently selected from H, substituted, unsubstituted, with or without C of O, S, N, si, P atoms 1 -C 30 Alkyl, C 6 -C 30 Aromatic radicals, C 3 -C 30 One or more of the heterocyclic groups; the substituent is selected from any one or more of halogen atoms, branched or straight-chain hydrocarbon groups having 1 to 20 carbon atoms; each R is 25 ～R 43 Two or more of which may form a bond or a ring;
r' is selected from unsubstituted, substituted, with or without O, S, N, si,C of P atoms 1 -C 30 Alkyl, C 6 -C 30 One or more of the aromatic groups; the substituent is selected from any one or more of halogen atoms, branched or straight-chain hydrocarbon groups with 1 to 20 carbon atoms, and aromatic groups with 6 to 20 carbon atoms; u represents the number of carboxylate groups and the number of corresponding ammonium salts;
each of which is provided withIndependently selected from-> One or more of the benzoate ions.
2. The organic catalytic system having a polyborocenter according to claim 1, wherein the procatalyst having a polyborocenter has the structure shown below:
3. use of an organic catalytic system with polyborogenic centres according to any of claims 1-2, for the preparation of small organic molecules or polymers, said main catalyst with polyborogenic centres having a molar ratio to co-catalyst of between 1: 10000-10000: 1.
4. The use of an organic catalytic system having a polyborocenter according to claim 3, wherein the polymer is an aliphatic polycarbonate obtained by catalyzing the copolymerization of carbon dioxide with alkylene oxide, a polyether obtained by catalyzing the ring-opening polymerization of alkylene oxide, a polythiocarbonate obtained by catalyzing the ring-opening polymerization of carbon dioxide with alkylene oxide, a polythioether obtained by catalyzing the ring-opening polymerization of cyclic thioether, a polyester obtained by catalyzing the copolymerization of alkylene oxide and cyclic anhydride, a polythiocarbonate obtained by catalyzing the copolymerization of carbon oxysulfide and alkylene oxide, or a polyester obtained by catalyzing the ring-opening polymerization of alkylene oxide and carbon monoxide, a polyester obtained by catalyzing the ring-opening polymerization of lactone, a polyester obtained by catalyzing the ring-opening of O-carboxyanhydride, a polypeptid obtained by catalyzing the ring-opening of N-carboxyanhydride;
the small organic molecules are cyclic carbonate obtained by catalyzing the reaction of carbon dioxide or carbon disulfide and alkylene oxide or cyclothioalkane, cyclic lactone obtained by catalyzing the reaction of carbon monoxide and alkylene oxide, and cyclic thiocarbonate obtained by catalyzing the copolymerization of carbon oxysulfide and alkylene oxide or cyclothioalkane.
5. The use of an organic catalytic system having a polyborogenic center according to claim 4, wherein the alkylene oxide, the sulfolane, the cyclic anhydride, the lactone are selected from the structures:
wherein R is 44 And R is 45 Selected from H, halogen, substituted, unsubstituted, C with or without O, S, N, si, P atoms 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 3 -C 30 One or more of the heterocyclic groups; the substituent is selected from one or more of halogen atoms, branched or straight-chain hydrocarbon groups with 1 to 20 carbon atoms, branched or straight-chain alkoxy groups with 1 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms and heteroaromatic groups with 5 to 20 carbon atoms; wherein each R 44 And R is 45 May be bonded or looped.
6. Use of an organic catalytic system with polyborogenic centres according to claim 3, characterized in that the procatalyst, cocatalyst is used supported on an inorganic or organic support or as heterogeneous catalyst due to the cross-linked structure itself.
CN202010018753.0A 2020-01-08 2020-01-08 Organic catalytic system with polyboron center and application Active CN113087882B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010018753.0A CN113087882B (en) 2020-01-08 2020-01-08 Organic catalytic system with polyboron center and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010018753.0A CN113087882B (en) 2020-01-08 2020-01-08 Organic catalytic system with polyboron center and application

Publications (2)

Publication Number Publication Date
CN113087882A CN113087882A (en) 2021-07-09
CN113087882B true CN113087882B (en) 2023-08-01

Family

ID=76663322

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010018753.0A Active CN113087882B (en) 2020-01-08 2020-01-08 Organic catalytic system with polyboron center and application

Country Status (1)

Country Link
CN (1) CN113087882B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114479022B (en) * 2022-01-14 2024-03-29 浙江大学 Organoboron nonmetallic catalyst for polymerization and preparation method and application thereof
CN114605621B (en) * 2022-03-25 2024-01-30 中国科学院长春应用化学研究所 Hydrogen bond donor-boron organic catalyst and preparation method and application thereof
WO2023192759A1 (en) * 2022-03-30 2023-10-05 Exxonmobil Chemical Patens Inc. Phosphine-borane catalyst compounds and use thereof
CN115873029A (en) * 2022-12-28 2023-03-31 中国科学院长春应用化学研究所 Catalyst and preparation method and application thereof
CN117887059A (en) * 2024-03-15 2024-04-16 中国科学院过程工程研究所 Method for selectively synthesizing polycarbonate or cyclic carbonate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101628974A (en) * 2009-08-11 2010-01-20 华南师范大学 Polyether glycol or polyether monohydric alcohol preparation method
CN106083906A (en) * 2016-07-12 2016-11-09 安徽红太阳新材料有限公司 The miaow borazol metal complex of catalysis cyclic ester polymerization and application thereof
CN109046447A (en) * 2018-08-27 2018-12-21 南开大学 C2The synthesis of symmetrical bicyclic double B catalysts
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
CN110498916A (en) * 2019-05-30 2019-11-26 华南理工大学 A kind of method of cyclic ester and the copolymerization of epoxy monomer sequence controlled block

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101628974A (en) * 2009-08-11 2010-01-20 华南师范大学 Polyether glycol or polyether monohydric alcohol preparation method
CN106083906A (en) * 2016-07-12 2016-11-09 安徽红太阳新材料有限公司 The miaow borazol metal complex of catalysis cyclic ester polymerization and application thereof
CN109046447A (en) * 2018-08-27 2018-12-21 南开大学 C2The synthesis of symmetrical bicyclic double B catalysts
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
CN110498916A (en) * 2019-05-30 2019-11-26 华南理工大学 A kind of method of cyclic ester and the copolymerization of epoxy monomer sequence controlled block

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
high efficiency organic lewis pair catalyst for ring-opening polymerization of epoxides with chemoselectivity;Ye Chen;《Macromolecules》;20181231;第51卷;第8286-8297页 *
highly active organic lewis pairs for the copolymerization of epoxides with cyclic anhydride;Lan-Fang Hu;《Macromolucules》;20181231;第51卷;第3126-3134页 *
metal-free alternating copolymerization of CO2 with epoxides;Dongyue Zhang;《J.Am.Chem.Soc》;20161231;第138卷;第11117-11120页 *
trans-vinylboranes from 9-borabicyclo[3.3.1]noname through dehydroborylation;Juan C.Colberg;《J.Am.Chem.Soc》;19931231;第115卷;第6065-6071页 *

Also Published As

Publication number Publication date
CN113087882A (en) 2021-07-09

Similar Documents

Publication Publication Date Title
CN113087882B (en) Organic catalytic system with polyboron center and application
AU2009239767B2 (en) Bimetallic catalytic complexes for the copolymerisation of carbon dioxide and an epoxide
Lu et al. Cobalt catalysts for the coupling of CO 2 and epoxides to provide polycarbonates and cyclic carbonates
RU2630688C2 (en) Method of polycrarbonate synthesis in presence of bimetallic catalyst and polymerization degree regulator
CN110105321B (en) Method for synthesizing cyclic carbonate by catalyzing carbon dioxide through eutectic ionic liquid
JP2019048994A (en) Method and catalyst system for preparing polymers and block copolymers
CN112390819B (en) Organic catalyst, preparation method and application
EP3286201B1 (en) Process to prepare aluminoxanes
EP1775301A1 (en) Novel supported phosphazene catalysts, novel compounds for the catalysts, and use thereof
EP1485422B1 (en) Catalytic systems
Zhang et al. Synthesis and characterization of lanthanide amides bearing aminophenoxy ligands and their catalytic activity for the polymerization of lactides
TW201038521A (en) Alkoxylation processes and catalysts therefor
Muñoz et al. Metal complexes bearing ONO ligands as highly active catalysts in carbon dioxide and epoxide coupling reactions
CN112409317B (en) Synthesis method of cyclic carbonate and derivatives thereof
CN110386954B (en) Asymmetric fused ring pyridine imino containing complex and preparation method and application thereof
Zhang et al. Facile syntheses of bimetallic ytterbium bisamides stabilized by a flexible bridged bis (phenolato) ligand and the high activity for the polymerization of L-lactide
Liu et al. SalenCr catalyst immobilized on amino-functionalized cellulose for the copolymerization of SO2 with cyclohexene oxide
CN107721858B (en) Method for catalyzing asymmetric alpha-benzoylation of beta-keto ester by phase transfer
CN111454222B (en) Synthesis method of 2,4- (1H, 3H) -quinazolinedione and derivatives thereof
KR102046244B1 (en) Phenolic organocatalyts and method of manufacturing cyclic alkylene carbonates using the same
CN114315915A (en) Binuclear Schiff base cobalt complex and preparation method and application thereof
SU891679A1 (en) Bis-(chelate)-bis-(hydroxyalkylenoxy)titanium as catalysts for producing polyethyleneterephthalate
KR100531132B1 (en) Method for the preparation of alkylene carbonate using imidazolium zinctetrahalide catalysts
KR20020066819A (en) Production method of alkylene carbonates
CN114292292B (en) Transition metal complex containing monoanionic ligand, and preparation method and application 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
GR01 Patent grant
GR01 Patent grant