WO2020057356A1 - 具有亲电亲核双功能的有机无金属催化剂及其制备方法和应用 - Google Patents

具有亲电亲核双功能的有机无金属催化剂及其制备方法和应用 Download PDF

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WO2020057356A1
WO2020057356A1 PCT/CN2019/103919 CN2019103919W WO2020057356A1 WO 2020057356 A1 WO2020057356 A1 WO 2020057356A1 CN 2019103919 W CN2019103919 W CN 2019103919W WO 2020057356 A1 WO2020057356 A1 WO 2020057356A1
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carbon atoms
branched
independently selected
aromatic
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伍广朋
杨贯文
张瑶瑶
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Zhejiang University
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Definitions

  • the invention relates to the field of catalyst synthesis, in particular to an organic metal-free catalyst having an electrophilic and nucleophilic dual function, and a preparation method and application thereof.
  • Polymer materials can be prepared by polymerization using different reaction monomers.
  • the use of different polymerization methods and reaction monomers can produce polymer materials with different properties, which have a wide range of applications in people's clothing, food, housing, transportation, and various sectors of the national economy.
  • catalysts are often added to the reaction system.
  • transition metal organic catalysts for olefin polymerization titanium catalyst for polyester materials, etc.
  • titanium catalyst for polyester materials etc.
  • these organometallic catalysts can efficiently prepare polymer materials, the residual metal catalysts in the materials often cause problems such as toxicity, discoloration, and degradation, limiting their applications, such as applications in the fields of packaging, biomedicine, and microelectronics.
  • organic non-metallic polymerization catalysts mainly include carboxylic acid-based catalyst systems, pyridine base-based catalyst systems, nitrogen heterocyclic carbene catalysts, nitrogen-containing base catalysts (guanidine and amine catalysts), thiourea / amine, and thiourea / nitrogen-based base catalysts. , Phosphazene base catalysts, etc.
  • These catalysts can be used in the copolymerization of alkylene oxide and carbon dioxide to prepare polycarbonate, the ring-opening polymerization of alkylene oxide to prepare polyether materials, the ring-opening polymerization of cyclic lactone monomers to prepare polyester polymer materials, and cyclic phosphate monomers Ring-opening polymerization to prepare polyphosphate polymer materials, ring-opening polymerization to replace cyclopropane to prepare functional polypropylene polymer materials, ring-opening polymerization of cyclic carbonates to prepare polycarbonate materials, and ring-opening polymerization of lactams to prepare polymers Amide polymer material, polysiloxane polymer material prepared by ring-opening polymerization of cyclosiloxane, catalyzed preparation of polymethyl methacrylate polymer material by methyl methacrylate monomer, catalyzed preparation of vinyl ether monomer by functionality Polyethylene materials and other fields.
  • the polymerization mechanisms involved in the above catalysts mainly include: polymerization mechanisms such as electrophilic activation reaction monomers, nucleophilic activation reaction monomers, nucleophilic activation of initiators, and synergistic activation of monomers and initiators.
  • polymerization mechanisms such as electrophilic activation reaction monomers, nucleophilic activation reaction monomers, nucleophilic activation of initiators, and synergistic activation of monomers and initiators.
  • Protonic acid is a classical monomer electrophilic activation mechanism.
  • Didier Bourissou et al. Reported the use of trifluoromethanesulfonic acid as a catalyst and alcohol compounds as initiators to catalyze the ring-opening polymerization of lactide [Macromolecules, 2005, 38, 9993-9998].
  • a protonic acid is used as an electrophilic reagent to first electrophilically activate the carbonyl group of lactide, and then an alcohol compound is used as an initiator.
  • a nucleophilic attack on the carbonyl group causes a ring-opening polymerization reaction to obtain a polylactide polymer material.
  • Guanidine compounds (such as: N-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, MTBD) [Macromolecules2006, 39,8574-8583], fluorene compounds (such as: 1,8-diazabicyclo [5.4.0] undec-7-ene), phosphazene base compounds [Macromol.Chem.Phys. 2003,204,1056-1071; J.Am.Chem.Soc. 129,42,12610-12611; Macrom.RapidComm. 1995,16,449-453] is mainly the polymerization mechanism of the activation initiator.
  • the catalyst nucleophilically activates the alcohol compound, deprotonates the initiator to form an alkoxide, and the alkoxide attacks the monomer to initiate the polymerization reaction.
  • This type of catalyst is mainly used to catalyze ring-opening polymerization of monomers such as cyclic lactones, alkylene oxides, and cyclosiloxanes.
  • the above-mentioned organic catalyzed polymerization reaction involves electrophilic or nucleophilic activation of the monomer, and nucleophilic activation of the initiator.
  • Different catalysts, cocatalysts and initiators need to be added to jointly promote the occurrence of the polymerization reaction. Therefore, the development of synergistic catalysis of monomers and initiators has gradually gained widespread acceptance.
  • Typical examples of these catalysts are thiourea-amine-alcohol catalytic systems [J.Am.Chem.Soc.2005,127,13798-13799; Macromolecules, 2006,39,7863-7871], [Macromolecules, 2014,47,1277 -1284] and 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) -alcohol catalytic system [J.Am.Chem.Soc.128,14,4556-4557; US8367796 B2] and so on.
  • TBD dec-5-ene
  • thiourea in the thiourea-amine-alcohol catalytic system, can act as a weak electrophile to activate monomers, and amine can act as a nucleophile to activate initiator alcohol compounds.
  • trialkyl boron can be used as an electrophilic reagent to form a multi-component catalytic system with compounds such as quaternary ammonium salts, quaternary phosphonium salts or phosphazene / alcohols for polymerization reactions.
  • triethylboron is used as an electrophile to activate cyclic monomers, quaternary ammonium salts, quaternary phosphonium salts, oxymetal salts, phosphazene / alcohol compounds as initiators, and can be used for carbon dioxide.
  • organic catalysts have become an ideal substitute for traditional metal-organic catalysts for the synthesis and preparation of a variety of polymer materials.
  • organic catalytic systems often need to add multiple electrophiles, nucleophiles or co-catalysts to achieve the purpose of activating the reaction monomers and initiators, thereby achieving the smooth implementation of the polymerization reaction.
  • Amount and batch addition often lead to poor experimental operability; in addition, the above-mentioned catalytic system also involves complex synthesis steps, which increases the polymerization cost.
  • An object of the present invention is to provide an organic metal-free catalyst having an electrophilic and nucleophilic dual function in view of the shortcomings of the prior art.
  • each of Y 1 to Y 3 is independently selected from one or more of the following structural formulas 1 to 5:
  • N is a nitrogen atom
  • P is a phosphorus atom, Represented as a connection key
  • a, b are independently selected from integers of 0-20, but not 0 at the same time; c, d, e are independently selected from integers of 0-20; when a is 0, c and d cannot be 0 at the same time ; When b is 0, each e cannot take 0 at the same time;
  • Each Z 1 to Z 4 , R 1 , R 2 , and E 1 to E 4 are independently selected from the following unsubstituted or substituted groups: C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl One or more of C 3 -C 30 alkenyl, C 3 -C 30 alkynyl, C 6 -C 30 aromatic, C 3 -C 30 heterocyclyl, C 5 -C 30 heteroaryl, Or the group containing one or more of O, S, N, Si, and P atoms; wherein the substituent is selected from a halogen atom, a branched or linear chain having 1 to 20 carbon atoms Hydrocarbyl, branched or linear alkoxy group of 1 to 20 carbon atoms, branched or linear cycloalkyl group of 3 to 20 carbon atoms, aromatic group of 6 to 30 carbon atoms, 5 to 30 One or more of heteroaromatic groups of carbon atoms; wherein two or more of each of Z
  • the invention also provides an organic metal-free catalyst having an electrophilic and nucleophilic dual function.
  • the technical solutions provided are:
  • the organic metal-free catalyst has one of the following structures:
  • Each i is independently selected from 1 or 2;
  • Each f is independently selected from an integer of 0 to 3, but f cannot be 0 at the same time in any structure;
  • g is selected from any integer from 3 to 20;
  • Each h is independently selected from an integer of 0 to 3, but h cannot be 0 at the same time in any structure;
  • n is independently selected from an integer from 0 to 2;
  • Each K 1 is independently selected from the following unsubstituted or substituted groups: C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl, C 3 -C 30 alkyne One or more of C 7 -C 30 aromatic group, C 3 -C 30 heterocyclic group, C 5 -C 30 heteroaryl group, or those containing O, S, N, Si, P atoms One or more of said groups; wherein said substituent is selected from the group consisting of a halogen atom, a branched or straight chain hydrocarbon group having 1 to 20 carbon atoms, a branched or straight chain group of 1 to 20 carbon atoms One or more of an alkoxy group, a branched or straight-chain cycloalkyl group of 3 to 20 carbon atoms, an aromatic group of 6 to 30 carbon atoms, and a heteroaryl group of 5 to 30 carbon atoms;
  • Each of R 3 to R 6 , R 3 ′ to R 6 ′, K 2 to K 4 , K 1 ′ to K 3 ′ is independently selected from the following unsubstituted or substituted groups: C 1 -C 30 alkane Group, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl, C 3 -C 30 alkynyl, C 6 -C 30 aryl, C 3 -C 30 heterocyclyl, C 5 -C 30 hetero One or more of an aromatic group, or the group containing one or more of O, S, N, Si, and P atoms; wherein the substituent is selected from a halogen atom having 1 to 20 Branched or linear hydrocarbon group of 1 carbon atom, branched or linear alkoxy group of 1 to 20 carbon atoms, branched or linear cycloalkyl group of 3 to 20 carbon atoms, 6 to 30 One or more of an aromatic group of carbon atoms and a heteroaryl group of 5
  • K 1 to K 4 , K 1 ′ to K 3 ′, R 3 to R 6 , and R 3 ′ to R 6 ′ may form a bond or form a ring;
  • R 3 to R 5 cannot be aromatic or heteroaromatic at the same time, and R 3 ′ to R 5 'cannot be aromatic or hetero aromatic at the same time;
  • A is selected from N or P atoms
  • Each G 1 ′, G 2 ′ is independently selected from the following unsubstituted or substituted groups: C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl, C One or more of 3 -C 30 alkynyl, C 6 -C 30 aromatic, C 3 -C 30 heterocyclyl, C 5 -C 30 heteroaryl, or O, S, N, Si One or more of P groups, wherein the substituent is selected from a halogen atom, a branched or straight chain hydrocarbon group having 1 to 20 carbon atoms, a branch of 1 to 20 carbon atoms One of a chain or linear alkoxy group, a branched or linear cycloalkyl group of 3 to 20 carbon atoms, an aromatic group of 6 to 20 carbon atoms, a heteroaromatic group of 5 to 20 carbon atoms Or more; wherein each G 1 ′, G 2 ′ may form a bond or form a
  • the invention also provides an organic metal-free catalyst having an electrophilic and nucleophilic dual function.
  • the technical solutions provided are:
  • the organic metal-free catalyst is obtained from a reaction raw material W1 containing nitrogen or phosphorus containing at least one unsaturated bond, and a reaction raw material W2 containing at least one boron-hydrogen bond through a borohydride reaction;
  • reaction raw material W1 The structural formula of the reaction raw material W1 is expressed as one or more of the following:
  • Each f is independently selected from an integer of 0 to 3, but f cannot be 0 at the same time in any structure;
  • g is selected from any integer from 3 to 20;
  • Each p is independently selected from an integer of 0 to 3
  • each j is independently selected from an integer of 0 to 2, but p and j cannot be 0 at the same time in any structure;
  • Each h is independently selected from an integer of 0 to 3, but h cannot be 0 at the same time in any structure;
  • Each K 1 is independently selected from the following unsubstituted or substituted groups: C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl, C 3 -C 30 alkyne One or more of C 7 -C 30 aromatic group, C 3 -C 30 heterocyclic group, C 5 -C 30 heteroaryl group, or those containing O, S, N, Si, P atoms One or more of said groups; wherein said substituent is selected from the group consisting of a halogen atom, a branched or straight chain hydrocarbon group having 1 to 20 carbon atoms, a branched or straight chain group of 1 to 20 carbon atoms One or more of an alkoxy group, a branched or straight-chain cycloalkyl group of 3 to 20 carbon atoms, an aromatic group of 6 to 30 carbon atoms, and a heteroaryl group of 5 to 30 carbon atoms;
  • Each of R 3 to R 6 , R 3 ′ to R 6 ′, K 2 to K 4 , K 1 ′ to K 3 ′ is independently selected from the following unsubstituted or substituted groups: C 1 -C 30 alkane Group, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl, C 3 -C 30 alkynyl, C 6 -C 30 aryl, C 3 -C 30 heterocyclyl, C 5 -C 30 hetero One or more of an aromatic group, or the group containing one or more of O, S, N, Si, and P atoms; wherein the substituent is selected from a halogen atom having 1 to 20 Branched or linear hydrocarbon group of 1 carbon atom, branched or linear alkoxy group of 1 to 20 carbon atoms, branched or linear cycloalkyl group of 3 to 20 carbon atoms, 6 to 30 One or more of an aromatic group of carbon atoms and a heteroaryl group of 5
  • K 1 to K 4 , K 1 ′ to K 3 ′, R 3 to R 6 , and R 3 ′ to R 6 ′ may form a bond or form a ring;
  • R 3 to R 5 cannot be aromatic or heteroaromatic at the same time
  • A is selected from N or P atoms
  • reaction raw material W2 The structural formula of the reaction raw material W2 is expressed as one or more of the following:
  • Each G 1 , G 2 is independently selected from the following unsubstituted or substituted: H, halogen, C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl One or more of C 3 -C 30 alkynyl, C 6 -C 30 aromatic, C 3 -C 30 heterocyclyl, C 5 -C 30 heteroaryl, or containing O, S, N One or more of the above, Si, and P atoms; wherein the substituent is selected from the group consisting of a halogen atom, a branched or linear hydrocarbon group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms Branched or linear alkoxy, branched or linear cycloalkyl of 3 to 20 carbon atoms, aromatic group of 6 to 20 carbon atoms, heteroaromatic group of 5 to 20 carbon atoms One or more; wherein each of G 1 and G 2 may form a bond or form a
  • An object of the present invention is to provide a method for preparing an organic metal-free catalyst having an electrophilic and nucleophilic dual function in view of the shortcomings of the prior art.
  • reaction raw material W1 containing nitrogen or phosphorus containing at least one unsaturated bond and the reaction raw material W2 containing at least one boron-hydrogen bond are obtained by a borohydride reaction;
  • reaction raw material W1 The structural formula of the reaction raw material W1 is expressed as one or more of the following:
  • Each f is independently selected from an integer of 0 to 3, but f cannot be 0 at the same time in any structure;
  • g is selected from any integer from 3 to 20;
  • Each p is independently selected from an integer of 0 to 3
  • each j is independently selected from an integer of 0 to 2, but p and j cannot be 0 at the same time in any structure;
  • Each h is independently selected from an integer of 0 to 3, but h cannot be 0 at the same time in any structure;
  • Each K 1 is independently selected from the following unsubstituted or substituted groups: C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl, C 3 -C 30 alkyne One or more of C 7 -C 30 aromatic group, C 3 -C 30 heterocyclic group, C 5 -C 30 heteroaryl group, or those containing O, S, N, Si, P atoms One or more of said groups; wherein said substituent is selected from the group consisting of a halogen atom, a branched or straight chain hydrocarbon group having 1 to 20 carbon atoms, a branched or straight chain group of 1 to 20 carbon atoms One or more of an alkoxy group, a branched or straight-chain cycloalkyl group of 3 to 20 carbon atoms, an aromatic group of 6 to 30 carbon atoms, and a heteroaryl group of 5 to 30 carbon atoms;
  • Each of R 3 to R 6 , R 3 ′ to R 6 ′, K 2 to K 4 , K 1 ′ to K 3 ′ is independently selected from the following unsubstituted or substituted groups: C 1 -C 30 alkane Group, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl, C 3 -C 30 alkynyl, C 6 -C 30 aryl, C 3 -C 30 heterocyclyl, C 5 -C 30 hetero One or more of an aromatic group, or the group containing one or more of O, S, N, Si, and P atoms; wherein the substituent is selected from a halogen atom having 1 to 20 Branched or linear hydrocarbon group of 1 carbon atom, branched or linear alkoxy group of 1 to 20 carbon atoms, branched or linear cycloalkyl group of 3 to 20 carbon atoms, 6 to 30 One or more of an aromatic group of carbon atoms and a heteroaryl group of 5
  • K 1 to K 4 , K 1 ′ to K 3 ′, R 3 to R 6 , and R 3 ′ to R 6 ′ may form a bond or form a ring;
  • R 3 to R 5 cannot be aromatic or heteroaromatic at the same time
  • A is selected from N or P atoms
  • reaction raw material W2 The structural formula of the reaction raw material W2 is expressed as one or more of the following:
  • Each G 1 , G 2 is independently selected from the following unsubstituted or substituted: H, halogen, C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl One or more of C 3 -C 30 alkynyl, C 6 -C 30 aromatic, C 3 -C 30 heterocyclyl, C 5 -C 30 heteroaryl, or containing O, S, N One or more of the above, Si, and P atoms; wherein the substituent is selected from the group consisting of a halogen atom, a branched or linear hydrocarbon group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms Branched or linear alkoxy, branched or linear cycloalkyl of 3 to 20 carbon atoms, aromatic group of 6 to 20 carbon atoms, heteroaromatic group of 5 to 20 carbon atoms One or more; wherein each of G 1 and G 2 may form a bond or form a
  • the purpose of the present invention is to address the shortcomings of the prior art, and also provides an application of an organic metal-free catalyst in preparing a polymer material.
  • One or more cyclic monomers undergo a homopolymerization reaction or a copolymerization reaction under the contact of an organic metal-free catalyst having an electrophilic and nucleophilic dual function to obtain a polymer material.
  • one or more cyclic monomers are copolymerized with one or more of carbon dioxide, carbon disulfide, and carbon sulfide in contact with an organic metal-free catalyst having an electrophilic and nucleophilic dual function to obtain a polymer material.
  • the purpose of the present invention is to address the shortcomings of the prior art, and also to provide an application of an organic metal-free catalyst in preparing polymer materials, including: catalyzing the copolymerization of carbon dioxide and alkylene oxide to prepare aliphatic polycarbonate, and catalyzing epoxy.
  • Polyethers are prepared by ring-opening polymerization of alkanes, polyesters are catalyzed by alkylene oxides and cyclic acid anhydrides, and polythiocarbonates are produced by catalyzed copolymerization of carbon thiooxide and alkylene oxides.
  • the beneficial effects of the present invention are: compared with the existing metal-free organic polymerization catalyst systems, it has the advantages of simple preparation, high activity, convenient use, low cost, and wide applicability, and is very suitable for industrialization produce.
  • FIG. 11 is a 1 H NMR spectrum chart of the polyphosphate-polycarbonate block copolymer prepared in Application Example 44.
  • FIG. 11 is a 1 H NMR spectrum chart of the polyphosphate-polycarbonate block copolymer prepared in Application Example 44.
  • Alkyl refers to a saturated aliphatic hydrocarbon group, including straight and branched chain groups of 1 to 30 carbon atoms. It preferably contains 1 to 15 carbon atoms, more preferably a medium-sized alkyl group containing 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, Amyl, hexyl, etc. More preferred are lower alkyl groups containing 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like.
  • Cycloalkyl means a full-carbon monocyclic, fused ring or polycyclic fused ring group comprising 1 to 30 carbon atoms. It is preferably a 3- to 8-membered full-carbon monocyclic, full-carbon 5-membered / 6-membered or 6-membered / 6-membered fused ring or polycyclic fused ring group, in which one or more rings may contain one or more double bonds . More preferred are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexadienyl, adamantyl, cycloheptatrienyl, and the like.
  • Alkenyl refers to an unsaturated aliphatic hydrocarbon group having a carbon-carbon double bond, and includes straight and branched chain groups of 1 to 30 carbon atoms. Preferred are straight and branched chain groups containing 2 to 10 (further 2 to 6) carbon atoms.
  • the alkynyl group refers to an unsaturated aliphatic hydrocarbon group having a carbon-carbon triple bond, and includes straight and branched chain groups of 1 to 30 carbon atoms. Preferred are straight and branched chain groups containing 2 to 10 (further 2 to 6) carbon atoms.
  • the aromatic group refers to a group having at least one aromatic ring structure, and is preferably a carbocyclic aromatic group or a heteroaromatic group.
  • a heteroaromatic group is an aromatic group having one heteroatom as a ring-forming atom and the remaining ring-forming atoms as carbon.
  • the ring structure satisfies the Hockel rule, and the heteroatoms include O, S, N, Si, and P atoms. It is preferably a 5-, 6- or 7-membered ring.
  • the heteroaromatic group includes, but is not limited to, furyl, thienyl, benzofuranyl, benzothienyl, pyridyl, pyrrolyl, and N-alkylpyrrolyl.
  • Heterocyclyl refers to a group that contains at least one heteroatom in addition to the carbon atom.
  • the heteroatom includes O, S, N, Si, and P atoms. It is preferably a 5-, 6- or 7-membered alicyclic or aromatic heterocyclic ring.
  • Halogen refers to fluorine, chlorine, bromine or iodine.
  • connection key Represented as a connection key.
  • Each refers to each.
  • Y 1 to Y 3 is independently selected", specifically Y 1 , Y 2, and Y 3.
  • the structural formula contains a plurality of Y 1 , it also refers to each Y 1 without affecting each other and independently.
  • Each structure is shown as being the same or different.
  • the organic metal-free catalyst having an electrophilic and nucleophilic dual function has a chemical structure represented by formula (I):
  • each of Y 1 to Y 3 is independently selected from one or more of the following structural formulas 1 to 5:
  • N is a nitrogen atom
  • P is a phosphorus atom, Represented as a connection key
  • a, b are independently selected from integers of 0-20, but not 0 at the same time; c, d, e are independently selected from integers of 0-20; when a is 0, c and d cannot be 0 at the same time ; When b is 0, each e cannot take 0 at the same time;
  • Each Z 1 to Z 4 , R 1 , R 2 , and E 1 to E 4 are independently selected from the following unsubstituted or substituted groups: C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl One or more of C 3 -C 30 alkenyl, C 3 -C 30 alkynyl, C 6 -C 30 aromatic, C 3 -C 30 heterocyclyl, C 5 -C 30 heteroaryl, Or the group containing one or more of O, S, N, Si, and P atoms; wherein the substituent is selected from a halogen atom, a branched or linear chain having 1 to 20 carbon atoms Hydrocarbyl, branched or linear alkoxy group of 1 to 20 carbon atoms, branched or linear cycloalkyl group of 3 to 20 carbon atoms, aromatic group of 6 to 30 carbon atoms, 5 to 30 One or more of heteroaromatic groups of carbon atoms; wherein two or more of each of Z
  • each of Z 1 to Z 4 or other Z 1 to Z 4 in the same structural formula may form a bond or a ring, in the form of a monocyclic, bicyclic, tricyclic, polycyclic or spirocyclic structure.
  • each R 1 , R 2 or other R 1 or R 2 in the same structural formula may form a bond or a ring, and exist in the form of a monocyclic, bicyclic, tricyclic, polycyclic or spirocyclic structure; each E 1 ⁇ E 4 or between the same and the other structural formula E 1 ⁇ E 4 may be bonded to form a ring, is present in monocyclic, bicyclic, tricyclic, polycyclic, or spiro cyclic structure form.
  • each refers to each of a, e.g., "each R 1, R 2 'represents R as 1, R 2, and R contains a plurality of the same structural formulas 1 and R 2, R 1 i.e. It may form a bond or a ring with R 2 , or may form a bond or a ring with other R 1 or R 2 in the structural formula.
  • each of Z 1 to Z 4 , R 1 , R 2 , E 1 to E 4 is independently selected from the following unsubstituted or substituted groups: C 1 -C 18 alkyl, C 3 -C 18 cycloalkyl, C 3 -C 18 alkenyl, C 3 -C 18 alkynyl, C 6 -C 18 aryl, C 3 -C 18 heterocyclyl, C 5 -C 18 heteroaryl Or one or more of said groups containing one or more of O, S, N, Si, and P atoms; wherein said substituent is selected from a halogen atom having 1 to 10 carbon atoms Branched or straight chain hydrocarbon group, branched or straight chain alkoxy group of 1 to 10 carbon atoms, branched or straight chain cycloalkyl group of 3 to 10 carbon atoms, 6 to 18 carbon atoms One or more of an aromatic group and a heteroaryl group having 5 to 18 carbon atoms.
  • the organic metal-free catalyst having an electrophilic and nucleophilic dual function has one of the following structures:
  • Each i is independently selected from 1 or 2;
  • Each f is independently selected from an integer of 0 to 3, but f cannot be 0 at the same time in any structure;
  • g is selected from any integer from 3 to 20;
  • Each h is independently selected from an integer of 0 to 3, but h cannot be 0 at the same time in any structure;
  • n is independently selected from an integer from 0 to 2;
  • Each K 1 is independently selected from the following unsubstituted or substituted groups: C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl, C 3 -C 30 alkyne One or more of C 7 -C 30 aromatic group, C 3 -C 30 heterocyclic group, C 5 -C 30 heteroaryl group, or those containing O, S, N, Si, P atoms One or more of said groups; wherein said substituent is selected from the group consisting of a halogen atom, a branched or straight chain hydrocarbon group having 1 to 20 carbon atoms, a branched or straight chain group of 1 to 20 carbon atoms One or more of an alkoxy group, a branched or straight-chain cycloalkyl group of 3 to 20 carbon atoms, an aromatic group of 6 to 30 carbon atoms, and a heteroaryl group of 5 to 30 carbon atoms;
  • Each of R 3 to R 6 , R 3 ′ to R 6 ′, K 2 to K 4 , K 1 ′ to K 3 ′ is independently selected from the following unsubstituted or substituted groups: C 1 -C 30 alkane Group, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl, C 3 -C 30 alkynyl, C 6 -C 30 aryl, C 3 -C 30 heterocyclyl, C 5 -C 30 hetero One or more of an aromatic group, or the group containing one or more of O, S, N, Si, and P atoms; wherein the substituent is selected from a halogen atom having 1 to 20 Branched or linear hydrocarbon group of 1 carbon atom, branched or linear alkoxy group of 1 to 20 carbon atoms, branched or linear cycloalkyl group of 3 to 20 carbon atoms, 6 to 30 One or more of an aromatic group of carbon atoms and a heteroaryl group of 5
  • K 1 to K 4 , K 1 ′ to K 3 ′, R 3 to R 6 , and R 3 ′ to R 6 ′ may form a bond or form a ring;
  • R 3 to R 5 cannot be aromatic or heteroaromatic at the same time, and R 3 ′ to R 5 'cannot be aromatic or hetero aromatic at the same time;
  • A is selected from N or P atoms
  • Each G 1 ′, G 2 ′ is independently selected from the following unsubstituted or substituted groups: C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl, C One or more of 3 -C 30 alkynyl, C 6 -C 30 aromatic, C 3 -C 30 heterocyclyl, C 5 -C 30 heteroaryl, or O, S, N, Si One or more of P groups, wherein the substituent is selected from a halogen atom, a branched or straight chain hydrocarbon group having 1 to 20 carbon atoms, a branch of 1 to 20 carbon atoms One of a chain or linear alkoxy group, a branched or linear cycloalkyl group of 3 to 20 carbon atoms, an aromatic group of 6 to 20 carbon atoms, a heteroaromatic group of 5 to 20 carbon atoms Or multiple types; wherein each of G 1 ′, G 2 ′ may form a bond or
  • each Independently selected One or more of sulfonate, perchlorate, chlorate, phosphate, carboxylate, alkoxylate, and phenoxylate; wherein phenolate, carboxylate, sulfonate, alkoxide, including but not limited to O-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2,4-dinitrophenol oxyanion, 3,5-dinitrophenol oxyanion, 2,4,6-tri Nitrophenol oxygen anion, 3,5-dichlorophenol oxygen anion, 3,5-difluorophenol oxygen anion, 3,5-di-trifluoromethylphenol oxygen anion, pentafluorophenol oxygen anion, acetate, propionate Acid, butyrate, trifluoroacetate, trichloroacetate, benzenesulfonate, p-methylbenzenesulfonate, p-trifluoromethylbenzenesulfonate, methoxy
  • connection key Represented as a connection key
  • Each m is independently selected from an arbitrary integer of 1 to 18.
  • connection key Represented as a connection key
  • Each m is independently selected from an arbitrary integer of 1 to 18.
  • each of R 3 to R 6 and R 3 ′ to R 6 ′ is independently selected from the following unsubstituted or substituted groups: C 1 -C 18 alkyl, C 3 -C One of 18 cycloalkyl, C 3 -C 18 alkenyl, C 3 -C 18 alkynyl, C 6 -C 18 aryl, C 3 -C 18 heterocyclyl, C 5 -C 18 heteroaryl Or more, or the group containing one or more of O, S, N, Si, P atoms; wherein the substituent is selected from a halogen atom, a branched chain having 1 to 10 carbon atoms Or straight-chain hydrocarbon groups, branched or straight-chain alkoxy groups of 1 to 10 carbon atoms, branched or straight-chain cycloalkyl groups of 3 to 10 carbon atoms, aromatic groups of 6 to 18 carbon atoms, One or more of heteroaromatic groups of 5 to 18 carbon atom
  • each of K 1 to K 4 and K 1 ′ to K 3 ′ is independently selected from one or more of the following;
  • Each R 7 to R 25 is independently selected from the following unsubstituted or substituted groups: C 1 -C 18 alkyl, C 3 -C 18 cycloalkyl, C 3 -C 18 alkenyl, C 3- One or more of C 18 alkynyl, C 6 -C 18 aryl, C 3 -C 18 heterocyclyl, C 5 -C 18 heteroaryl, or those containing O, S, N, Si, P One or more of said groups; wherein said substituent is selected from a halogen atom, a branched or straight chain hydrocarbon group having 1 to 10 carbon atoms, a branched One or more of a linear alkoxy group, a branched or linear cycloalkyl group of 3 to 10 carbon atoms, an aromatic group of 6 to 12 carbon atoms, a heteroaryl group of 5 to 12 carbon atoms Species.
  • the organic metal-free catalyst has one of the following structures:
  • the organic metal-free catalyst having an electrophilic and nucleophilic dual function is hydrogenated by borohydride from a reaction raw material W1 containing nitrogen or phosphorus containing at least one unsaturated bond and a reaction raw material W2 containing at least one boron-hydrogen bond Get reaction
  • reaction raw material W1 The structural formula of the reaction raw material W1 is expressed as one or more of the following:
  • Each f is independently selected from an integer of 0 to 3, but f cannot be 0 at the same time in any structure;
  • g is selected from any integer from 3 to 20;
  • Each p is independently selected from an integer of 0 to 3
  • each j is independently selected from an integer of 0 to 2, but p and j cannot be 0 at the same time in any structure;
  • Each h is independently selected from an integer of 0 to 3, but h cannot be 0 at the same time in any structure;
  • Each K 1 is independently selected from the following unsubstituted or substituted groups: C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl, C 3 -C 30 alkyne One or more of C 7 -C 30 aromatic group, C 3 -C 30 heterocyclic group, C 5 -C 30 heteroaryl group, or those containing O, S, N, Si, P atoms One or more of said groups; wherein said substituent is selected from the group consisting of a halogen atom, a branched or straight chain hydrocarbon group having 1 to 20 carbon atoms, a branched or straight chain group of 1 to 20 carbon atoms One or more of an alkoxy group, a branched or straight-chain cycloalkyl group of 3 to 20 carbon atoms, an aromatic group of 6 to 30 carbon atoms, and a heteroaryl group of 5 to 30 carbon atoms;
  • Each of R 3 to R 6 , R 3 ′ to R 6 ′, K 2 to K 4 , K 1 ′ to K 3 ′ is independently selected from the following unsubstituted or substituted groups: C 1 -C 30 alkane Group, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl, C 3 -C 30 alkynyl, C 6 -C 30 aryl, C 3 -C 30 heterocyclyl, C 5 -C 30 hetero One or more of an aromatic group, or the group containing one or more of O, S, N, Si, and P atoms; wherein the substituent is selected from a halogen atom having 1 to 20 Branched or linear hydrocarbon group of 1 carbon atom, branched or linear alkoxy group of 1 to 20 carbon atoms, branched or linear cycloalkyl group of 3 to 20 carbon atoms, 6 to 30 One or more of an aromatic group of carbon atoms and a heteroaryl group of 5
  • K 1 to K 4 , K 1 ′ to K 3 ′, R 3 to R 6 , and R 3 ′ to R 6 ′ may form a bond or form a ring;
  • R 3 to R 5 cannot be aromatic or heteroaromatic at the same time
  • A is selected from N or P atoms
  • each Independently selected One or more of sulfonate, perchlorate, chlorate, phosphate, carboxylate, alkoxylate, and phenoxylate; wherein phenolate, carboxylate, sulfonate, alkoxide, including but not limited to O-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2,4-dinitrophenol oxyanion, 3,5-dinitrophenol oxyanion, 2,4,6-tri Nitrophenol oxygen anion, 3,5-dichlorophenol oxygen anion, 3,5-difluorophenol oxygen anion, 3,5-di-trifluoromethylphenol oxygen anion, pentafluorophenol oxygen anion, acetate, propionate Acid, butyrate, trifluoroacetate, trichloroacetate, benzenesulfonate, p-methylbenzenesulfonate, p-trifluoromethylbenzenesulfonate, methoxy
  • reaction raw material W2 The structural formula of the reaction raw material W2 is expressed as one or more of the following:
  • Each G 1 , G 2 is independently selected from the following unsubstituted or substituted: H, halogen, C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl One or more of C 3 -C 30 alkynyl, C 6 -C 30 aromatic, C 3 -C 30 heterocyclyl, C 5 -C 30 heteroaryl, or containing O, S, N One or more of the above, Si, and P atoms; wherein the substituent is selected from the group consisting of a halogen atom, a branched or linear hydrocarbon group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms Branched or linear alkoxy, branched or linear cycloalkyl of 3 to 20 carbon atoms, aromatic group of 6 to 20 carbon atoms, heteroaromatic group of 5 to 20 carbon atoms One or more types, wherein each of G 1 and G 2 may form a bond or a
  • a method for preparing an organic metal-free catalyst having an electrophilic and nucleophilic dual function comprises a reaction raw material W1 containing nitrogen or phosphorus containing at least one unsaturated bond and a reaction raw material containing at least one boron-hydrogen bond.
  • W2 is obtained by borohydride reaction;
  • reaction raw material W1 The structural formula of the reaction raw material W1 is expressed as one or more of the following:
  • Each f is independently selected from an integer of 0 to 3, but f cannot be 0 at the same time in any structure;
  • g is selected from any integer from 3 to 20;
  • Each p is independently selected from an integer of 0 to 3
  • each j is independently selected from an integer of 0 to 2, but p and j cannot be 0 at the same time in any structure;
  • Each h is independently selected from an integer of 0 to 3, but h cannot be 0 at the same time in any structure;
  • Each K 1 is independently selected from the following unsubstituted or substituted groups: C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl, C 3 -C 30 alkyne One or more of C 7 -C 30 aromatic group, C 3 -C 30 heterocyclic group, C 5 -C 30 heteroaryl group, or those containing O, S, N, Si, P atoms One or more of said groups; wherein said substituent is selected from the group consisting of a halogen atom, a branched or straight chain hydrocarbon group having 1 to 20 carbon atoms, a branched or straight chain group of 1 to 20 carbon atoms One or more of an alkoxy group, a branched or straight-chain cycloalkyl group of 3 to 20 carbon atoms, an aromatic group of 6 to 30 carbon atoms, and a heteroaryl group of 5 to 30 carbon atoms;
  • Each of R 3 to R 6 , R 3 ′ to R 6 ′, K 2 to K 4 , K 1 ′ to K 3 ′ is independently selected from the following unsubstituted or substituted groups: C 1 -C 30 alkane Group, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl, C 3 -C 30 alkynyl, C 6 -C 30 aryl, C 3 -C 30 heterocyclyl, C 5 -C 30 hetero One or more of an aromatic group, or the group containing one or more of O, S, N, Si, and P atoms; wherein the substituent is selected from a halogen atom having 1 to 20 Branched or linear hydrocarbon group of 1 carbon atom, branched or linear alkoxy group of 1 to 20 carbon atoms, branched or linear cycloalkyl group of 3 to 20 carbon atoms, 6 to 30 One or more of an aromatic group of carbon atoms and a heteroaryl group of 5
  • K 1 to K 4 , K 1 ′ to K 3 ′, R 3 to R 6 , and R 3 ′ to R 6 ′ may form a bond or a ring, and may be a single ring or a double ring.
  • Tricyclic, polycyclic or spirocyclic structure exists;
  • R 3 to R 5 cannot be aromatic or heteroaromatic at the same time
  • A is selected from N or P atoms
  • each Independently selected One or more of sulfonate, perchlorate, chlorate, phosphate, carboxylate, alkoxylate, and phenoxylate; wherein phenolate, carboxylate, sulfonate, alkoxide, including but not limited to O-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2,4-dinitrophenol oxyanion, 3,5-dinitrophenol oxyanion, 2,4,6-tri Nitrophenol oxygen anion, 3,5-dichlorophenol oxygen anion, 3,5-difluorophenol oxygen anion, 3,5-di-trifluoromethylphenol oxygen anion, pentafluorophenol oxygen anion, acetate, propionate Acid, butyrate, trifluoroacetate, trichloroacetate, benzenesulfonate, p-methylbenzenesulfonate, p-trifluoromethylbenzenesulfonate, methoxy
  • reaction raw material W2 The structural formula of the reaction raw material W2 is expressed as one or more of the following:
  • Each G 1 , G 2 is independently selected from the following unsubstituted or substituted: H, halogen, C 1 -C 30 alkyl, C 3 -C 30 cycloalkyl, C 3 -C 30 alkenyl One or more of C 3 -C 30 alkynyl, C 6 -C 30 aromatic, C 3 -C 30 heterocyclyl, C 5 -C 30 heteroaryl, or containing O, S, N One or more of the above, Si, and P atoms; wherein the substituent is selected from the group consisting of a halogen atom, a branched or linear hydrocarbon group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms Branched or linear alkoxy, branched or linear cycloalkyl of 3 to 20 carbon atoms, aromatic group of 6 to 20 carbon atoms, heteroaromatic group of 5 to 20 carbon atoms One or more types, wherein each of G 1 and G 2 may form a bond or a
  • reaction formula (II) is only one of the preparation methods of the organic metal-free catalyst, and is not limited to the reaction formula (II).
  • the reaction raw materials in the reaction formula (II) include, but are not limited to, W1 And W2, more preparation methods can be found in specific examples.
  • a method for preparing an organic metal-free catalyst having an electrophilic and nucleophilic dual function includes: mixing any reaction raw material W1 and any reaction raw material W2 under the protection of nitrogen or an inert gas, and adding an organic solvent
  • the borohydride reaction was carried out at -20 to 150 ° C. for 1 to 500 hours. After the reaction, the temperature was lowered to room temperature, and impurities and organic solvents were removed to obtain an organic metal-free catalyst having an electrophilic and nucleophilic dual function.
  • the organic solvent is selected from tetrahydrofuran, benzene, toluene, chloroform, hexane, ether, dichloromethane, ethyl acetate, dimethyl sulfoxide, carbon tetrachloride, 1,4- One or more of dioxane and pyridine.
  • the application of the organic metal-free catalyst in the preparation of polymer materials includes that one or more cyclic monomers are uniformly contacted under the contact of an organic metal-free catalyst having an electrophilic and nucleophilic dual function. Polymerization reaction or copolymerization reaction to obtain a polymer material. Among them, by adjusting the structure and amount of the catalyst and adding different cyclic monomers and amounts, it is sufficient to selectively modify the obtained polymer material.
  • the application of the organic metal-free catalyst in preparing a polymer material includes one or more cyclic monomers and one or more of carbon dioxide, carbon disulfide, and carbon sulfide.
  • a polymer material is obtained by a copolymerization reaction under the contact of an electro-nucleophilic bifunctional organic metal-free catalyst.
  • by adjusting the structure and amount of the catalyst, adding different cyclic monomers and amounts, and the amount of carbon dioxide, carbon disulfide, or carbon sulfur oxide a polymer material with a desired structure can be selectively obtained.
  • the cyclic monomer is selected from the following structures:
  • one or more alcohol compounds, acid compounds, amine compounds, polyhydric alcohols, and polyhydric alcohols can be added to the polymerization reaction system.
  • Carboxylic acid, polyalcoholic acid, and water were used as chain transfer agents to prepare corresponding polymer polyols.
  • the chain transfer agent is selected from the following structures:
  • an application of the organic metal-free catalyst in preparing a polymer material is to add one or more polymers having an alcoholic hydroxyl group, a phenolic hydroxyl group, an amino group, and a carboxyl group to the polymerization reaction system.
  • a macromolecular chain transfer agent a corresponding block copolymer or graft copolymer is prepared.
  • the chain transfer agent is selected from the following structures:
  • the specific number of functional groups such as alcoholic hydroxyl group, phenolic hydroxyl group, amino group, and carboxyl group shown in the figure may be any number from 1 to 50000 in theory.
  • Polymerization with a chain transfer agent is generally performed in an inert solvent, such as chloroform, dichloromethane, toluene, tetrahydrofuran or an alkylene oxide bulk, preferably toluene or an alkylene oxide bulk as a solvent; the polymerization temperature is generally maintained at -50 to 200 ° C. Degree, preferably 50 to 150 ° C; carbon dioxide pressure is between 0.1 to 200 MPa, preferably 1 to 5 MPa; catalyst concentration can be used within 10 -6 to 10 -2 M, preferably within 10 -5 to 10 -3 M; chain transfer The ratio of the agent and the reaction monomer ranges from 10 -5 to 10 5 , and is preferably used within 10 -3 to 10 3 .
  • an inert solvent such as chloroform, dichloromethane, toluene, tetrahydrofuran or an alkylene oxide bulk, preferably toluene or an alkylene oxide bulk as a solvent
  • the polymerization temperature is generally maintained at
  • the organic metal-free catalyst in the application of the organic metal-free catalyst in preparing a polymer material, is supported on an inorganic carrier or an organic carrier for use.
  • the application of the organic metal-free catalyst in preparing polymer materials includes: catalyzing the copolymerization of carbon dioxide and alkylene oxide to prepare aliphatic polycarbonate, and catalyzing the ring-opening polymerization of alkylene oxide.
  • Preparation of aliphatic polycarbonates for catalytic copolymerization of carbon dioxide and alkylene oxides The polymerization is generally carried out in an inert solvent, such as chloroform, dichloromethane, toluene, tetrahydrofuran or an alkylene oxide bulk polymerization, preferably toluene or alkylene oxide bulk
  • an inert solvent such as chloroform, dichloromethane, toluene, tetrahydrofuran or an alkylene oxide bulk polymerization, preferably toluene or alkylene oxide bulk
  • the catalyst and one or more alkylene oxides are dissolved in the above inert solvent, adjusted to the required temperature, and filled with the required carbon dioxide to efficiently prepare polycarbonate. After a certain period of reaction, it is cooled, precipitated, and weighed.
  • Polycarbonate polymer materials can be prepared by weight.
  • the polymerization temperature is generally maintained at -50 ⁇ 200 °C, preferably 50 ⁇ 150 °C; pressure of carbon dioxide is between 0.1 ⁇ 200MPa, preferably 1 ⁇ 5MPa; catalyst concentration can be 10 -6 ⁇ 10 -2 M, preferably at 10 - Used within 5 to 10 -3 M; the alkylene oxide monomer is as described above.
  • the molecular weight of the prepared polymer is between 500-1500000Da and the polydispersity is between 1.01-10.00.
  • the selectivity ratio of polycarbonate and cyclic carbonate can be 1% to 100%. It can be adjusted arbitrarily, and the content of polyether in polycarbonate can be arbitrarily adjusted between 0% and 99%.
  • Preparation of polyethers for catalytic ring-opening polymerization of alkylene oxides The polymerization is generally carried out in an inert solvent, such as chloroform, dichloromethane, toluene, tetrahydrofuran or an alkylene oxide bulk polymerization, preferably toluene or an alkylene oxide bulk is used as the solvent;
  • the catalyst is dissolved in the above-mentioned solvent, adjusted to the required temperature, and reacted for a certain time, then cooled, precipitated, and weighed to efficiently prepare the polyether polymer material.
  • the polymerization temperature is generally maintained at -50 to 200 ° C, preferably 50 to 150 ° C; the catalyst concentration can be used within 10 -8 to 10 -2 M, preferably within 10 -5 to 10 -3 M; the alkylene oxide used The monomer is as described above.
  • the polymerization is generally carried out in an inert solvent, such as chloroform, dichloromethane, toluene, tetrahydrofuran or an alkylene oxide bulk polymerization, preferably toluene or an alkylene oxide bulk is used as the solvent;
  • an inert solvent such as chloroform, dichloromethane, toluene, tetrahydrofuran or an alkylene oxide bulk polymerization, preferably toluene or an alkylene oxide bulk is used as the solvent
  • the catalyst, acid anhydride, and alkylene oxide are dissolved in the above-mentioned solvent, adjusted to the required temperature, and reacted for a certain time, and then cooled, precipitated, and weighed to efficiently prepare the polyether polymer material.
  • the polymerization temperature is generally maintained at -50 to 200 ° C, preferably 50 to 150 ° C; the catalyst concentration can be used within 10 -6 to 10 -2 M, preferably within 10 -5 to 10 -3 M; the epoxy used
  • Polymerization is generally carried out in an inert solvent, such as chloroform, dichloromethane, toluene, tetrahydrofuran or an alkylene oxide bulk polymerization, preferably toluene or alkylene oxide bulk
  • an inert solvent such as chloroform, dichloromethane, toluene, tetrahydrofuran or an alkylene oxide bulk polymerization, preferably toluene or alkylene oxide bulk
  • dissolve the catalyst and alkylene oxide in the above-mentioned solvent adjust to the required temperature, and fill one or more of the required carbon dioxide, carbon disulfide, and carbon oxysulfide. After reacting for a certain period of time, cool, precipitate, and weigh. Heavy weight can efficiently prepare thiocarbonate.
  • the polymerization temperature is generally maintained at -50 to 200 ° C, preferably 50 to 150 ° C; the carbon dioxide pressure is between 0.1 MPa to 200 MPa, preferably 1 to 5 MPa; the catalyst concentration may be 10 -6 to 10 -2 M, preferably at Used within 10 -5 to 10 -3 M; the alkylene oxide monomer used is as described above.
  • the catalyst B1 is synthesized as in Example 1;
  • the catalyst B1 is synthesized as in Example 1;
  • Application Example 1 Catalyze the copolymerization of propylene oxide (PO) and carbon dioxide with catalyst B7
  • Example 7 In a glove box, take the catalyst B7 (0.01 mmol) prepared in Example 7 into an autoclave, add propylene oxide (0.01 mol), fill it with 1.5 MPa of CO 2 , and react at 80 ° C for 2 h . Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity.
  • the polymer was precipitated from ethanol, and the polymer was characterized by gel permeation chromatography (GPC), nuclear magnetic and GPC. The results are shown in Table 1.
  • Application Example 3 Catalyze the copolymerization of ethylene oxide (EO) and carbon dioxide by using catalyst B7
  • Example 7 In the glove box, take the catalyst B7 (0.01 mmol) prepared in Example 7 into an autoclave, add ethylene oxide (0.01 mol), fill it with 1.5 MPa of CO 2 , and react at 80 ° C. 2h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity. The polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • the catalyst B7 (0.01 mmol) prepared in Example 7 was added to the autoclave, limonene oxide (0.01 mol) was added, 1.5 MPa of CO 2 was charged, and the reaction was performed at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity.
  • the polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • Example 1 In a glove box, take the catalyst B1 (0.01 mmol) prepared in Example 1 into an autoclave, and add 4-vinyl epoxycyclohexane (0.01 mol), fill with 1.5 MPa of CO 2 , and The reaction was performed at 2 ° C for 2h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity. The polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • Example 2 In a glove box, take the catalyst B2 (0.01 mmol) prepared in Example 2 into an autoclave, add CHO (0.01 mol), fill it with 1.5 MPa of CO 2 , and react at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity. The polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • the catalyst B3 (0.01 mmol) prepared in Example 3 was added to the autoclave, CHO (0.01 mol) was added, 1.5 MPa of CO 2 was charged, and the reaction was performed at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity.
  • the polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • the catalyst B4 (0.01 mmol) prepared in Example 4 was added to the autoclave, CHO (0.01 mol) was added, 1.5 MPa of CO 2 was charged, and the reaction was performed at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity.
  • the polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • the catalyst B5 (0.01 mmol) prepared in Example 5 was added to the autoclave, CHO (0.01 mol) was added, 1.5 MPa of CO 2 was charged, and the reaction was performed at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity.
  • the polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • Example 6 In a glove box, take the catalyst B6 (0.01 mmol) prepared in Example 6 into an autoclave, add CHO (0.01 mol), fill it with 1.5 MPa of CO 2 , and react at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity. The polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • Example 7 In a glove box, take the catalyst B7 (0.01 mmol) prepared in Example 7 into an autoclave, add CHO (0.01 mol), fill it with 1.5 MPa of CO 2 , and react at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity. The polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • the catalyst B8 (0.01 mmol) prepared in Example 8 was added to the autoclave, CHO (0.01 mol) was added, 1.5 MPa of CO 2 was charged, and the reaction was performed at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity.
  • the polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • Example 9 In a glove box, take the catalyst B9 (0.01 mmol) prepared in Example 9 into an autoclave, add CHO (0.01 mol), fill it with 1.5 MPa of CO 2 , and react at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity. The polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • the catalyst B10 (0.01 mmol) prepared in Example 10 was added to the autoclave, CHO (0.01 mol) was added, 1.5 MPa of CO 2 was charged, and the reaction was performed at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity.
  • the polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • the catalyst B11 (0.01 mmol) prepared in Example 11 was added to the autoclave, CHO (0.01 mol) was added, 1.5 MPa of CO 2 was charged, and the reaction was performed at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity.
  • the polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • the catalyst B12 (0.01 mmol) prepared in Example 12 was added to the autoclave, CHO (0.01 mol) was added, 1.5 MPa of CO 2 was charged, and the reaction was performed at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity.
  • the polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • Example 2 In a glove box, take the catalyst B2 (0.1 mmol) prepared in Example 2 into an autoclave, add CHO (0.01 mol), fill it with 1.5 MPa of CO 2 , and react at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity. The polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • Example 2 In a glove box, take the catalyst B2 (0.01 mmol) prepared in Example 2 into an autoclave, add CHO (0.05 mol), fill it with 1.5 MPa of CO 2 , and react at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity. The polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • Example 2 In a glove box, take the catalyst B2 (0.01 mmol) prepared in Example 2 into an autoclave, add CHO (0.1 mol), fill it with 1.5 MPa of CO 2 , and react at 80 ° C. for 8 hours. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity. The polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • Example 2 In a glove box, take the catalyst B2 (0.01 mmol) prepared in Example 2 into an autoclave, add CHO (0.5 mol), fill it with 1.5 MPa of CO 2 , and react at 80 ° C. for 16 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity. The polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • the catalyst B3 (0.01 mmol) prepared in Example 3 was added to the autoclave, PO (0.01 mol) was added, 1.5 MPa of CO 2 was charged, and the reaction was performed at 0 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity.
  • the polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1. The NMR of the obtained polymer is shown in Fig. 4.
  • the catalyst B3 (0.01 mmol) prepared in Example 3 was taken into an autoclave, PO (0.01 mol) was added, 1.5 MPa of CO 2 was charged, and the reaction was performed at 25 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity.
  • the polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • the catalyst B3 (0.01 mmol) prepared in Example 3 was added to the autoclave, PO (0.01 mol) was added, 1.5 MPa of CO 2 was charged, and the reaction was performed at 60 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity.
  • the polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • the catalyst B3 (0.01 mmol) prepared in Example 3 was added to the autoclave, PO (0.01 mol) was added, 1.5 MPa of CO 2 was charged, and the reaction was performed at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity.
  • the polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • the catalyst B3 (0.01 mmol) prepared in Example 3 was added to the autoclave, PO (0.01 mol) was added, 1.5 MPa of CO 2 was charged, and the reaction was performed at 120 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity.
  • the polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • Example 4 In a glove box, take the catalyst B4 (0.01 mmol) prepared in Example 4 into an autoclave, add CHO (0.01 mol), fill it with 1.5 MPa of CO 2 , and react at 80 ° C. for 0.5 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity. The polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • Example 4 In a glove box, take the catalyst B4 (0.01 mmol) prepared in Example 4 into an autoclave, add CHO (0.01 mol), fill it with 1.5 MPa of CO 2 , and react at 80 ° C. for 1 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity. The polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • the catalyst B4 (0.01 mmol) prepared in Example 4 was added to the autoclave, CHO (0.01 mol) was added, 1.5 MPa of CO 2 was charged, and the reaction was performed at 80 ° C. for 4 h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity.
  • the polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • Example 5 In a glove box, take the catalyst B5 (0.01 mmol) prepared in Example 5 into an autoclave, and add CHO (0.01 mol). Add 1 ml of chloroform (CHCl 3 ) and fill it with 1.5 MPa of CO 2 . The reaction was performed at 2 ° C for 2h. Carbon dioxide was then released, and the reaction solution was tested for nuclear magnetic resonance to characterize the monomer conversion and product selectivity. The polymer was precipitated from ethanol, and after drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • the catalyst B6 (0.01 mmol) prepared in Example 6 was added to the autoclave, and PO (0.01 mol) was added without carbon dioxide, and the reaction was performed at 80 ° C. for 2 h.
  • the reaction solution was tested by NMR to characterize the conversion of the monomer and the selectivity of the product.
  • the polymer was obtained by directly drying the residual PO. After drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • the 1 H NMR spectrum of the obtained polyether is shown in FIG. 5.
  • Example 6 In a glove box, take the catalyst B6 (0.01 mmol) prepared in Example 6 into an autoclave, add PO (0.01 mol), fill it with 0.5 MPa of CO 2 and react at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for NMR to characterize the monomer conversion and product selectivity. The residual PO was directly dried to obtain the polymer. After drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • Example 6 In a glove box, take the catalyst B6 (0.01 mmol) prepared in Example 6 into an autoclave, add PO (0.01 mol), fill it with 1.5 MPa of CO 2 and react at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for NMR to characterize the monomer conversion and product selectivity. The residual PO was directly dried to obtain the polymer. After drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • Example 6 In a glove box, take the catalyst B6 (0.01 mmol) prepared in Example 6 into an autoclave, add PO (0.01 mol), fill with 3.0 MPa of CO 2 and react at 80 ° C. for 2 h. Carbon dioxide was then released, and the reaction solution was tested for NMR to characterize the monomer conversion and product selectivity. The residual PO was directly dried to obtain the polymer. After drying, the polymer was characterized by GPC. NMR and GPC characterization results are shown in Table 1.
  • Table 1 shows the test results of the polymerization products of Application Examples 1 to 35.
  • 1 M n data molecular weight, measured by gel permeation chromatography
  • 2 PDI molecular weight distribution, measured by gel permeation chromatography.
  • Application Example 37 Preparation of a block copolymer of polycyclohexene carbonate and polypropylene glycol by using catalyst B7 and polypropylene glycol as a macromolecular chain transfer agent
  • Example 7 In a glove box, take the catalyst B7 (0.02 mmol) prepared in Example 7 and put it in an autoclave. Add polypropylene glycol (0.20 mmol) as a chain transfer agent and epoxy cyclohexene (0.02 mol). Charge 1.5 MPa. CO 2 and react at 80 ° C. for 24 h. Carbon dioxide was then released, and the polymer was precipitated in ethanol. After drying, the polymer was characterized by nuclear magnetic resonance and gel permeation chromatography (GPC).
  • Example 10 In a glove box, take the catalyst B10 (10.01 mmol) prepared in Example 10 and put it into a pressure bottle, add propylene oxide (0.01 mol), add maleic anhydride (0.01 mol), and react at 60 ° C. 24h. The polymer is precipitated in petroleum ether and dried to obtain poly (propylene maleate).
  • Application Example 40 Preparation of a polycyclohexene carbonate-polycyclohexene ester block copolymer using a catalyst B10
  • Example 10 In a glove box, take the catalyst B10 (0.02 mmol) prepared in Example 10 and put it into the autoclave, add epoxycyclohexene (0.01 mol), fill it with 1.0 MPa of COS, and react at 70 ° C. 2h. Then the COS is released, the polymer is precipitated in ethanol, and the monothio polycyclohexene carbonate is obtained after drying.
  • Example 12 In a glove box, take the catalyst B12 (0.02 mmol) prepared in Example 12 into an autoclave, add phosphate ester (0.01 mol), add 5 ml of chloroform, and react at 50 ° C. for 3 h. The polymer was precipitated in ethanol, and a polyphosphate was obtained after drying. The nuclear magnetic resonance of the obtained polyphosphate is shown in FIG. 10.
  • Example 12 In a glove box, take the catalyst B12 (0.01 mmol) prepared in Example 12 and put it in an autoclave, add propylene oxide (0.01 mol), fill it with 1.5 MPa of CO 2 , and react at 80 ° C for 2 h . Then, carbon dioxide was released, and phosphate ester (0.01 mol) was sequentially added to the glove box, and reacted at 50 ° C for 3 hours. The reaction solution was tested for nuclear magnetic resonance to characterize the conversion of the monomer, and the polymer was precipitated from petroleum ether. After drying, the polymer was characterized by GPC. The nuclear magnetic properties of the obtained polyphosphate-polycarbonate block copolymer are shown in FIG. 11.

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Abstract

本发明涉及一种具有亲电亲核双功能的有机无金属催化剂及其制备方法和应用。本发明中的有机无金属催化剂具有式(I)所示的化学结构: (I) 与目前存在的无金属有机聚合催化体系相比，具有制备简单、活性高、使用方便、成本低、适用性广的优点，非常适合工业化生产。

Description

具有亲电亲核双功能的有机无金属催化剂及其制备方法和应用 技术领域
本发明涉及催化剂合成领域，具体涉及一种具有亲电亲核双功能的有机无金属催化剂及其制备方法和应用。
背景技术
高分子材料可以利用不同的反应单体通过聚合反应制备得到。使用不同的聚合方法和反应单体可以制备性能各异的高分子材料，在人们的衣、食、住、行，国民经济各部门都具有广泛的应用。
高分子材料的聚合过程，需要考虑到聚合反应的速率、转化率和收率问题，同时还要兼顾简单、安全、环保等因素。要想达到理想的聚合要求，往往需要在反应体系中加入催化剂。如：过渡金属有机催化剂用于烯烃聚合、钛催化剂制备聚酯材料等。这些有机金属催化剂虽然可以高效的制备高分子材料，但材料内残留的金属催化剂，往往导致毒性、变色、降解等问题，限制了它们的应用，比如在包装、生物医学和微电子领域的应用。因此，随着人们逐渐开始关注化学反应的绿色化和对环境的影响，使用无金属的有机催化剂成为了有机化学、高分子化学和高分子材料科学的重要研究领域，尤其是在聚酯、聚碳酸酯、聚醚、聚酰胺、聚氨酯等高分子材料的应用上。
目前有机非金属聚合催化剂主要包括羧酸类催化体系、吡啶碱类催化体系、氮杂环卡宾类催化剂、含氮碱催化剂(胍和胺催化剂)、硫脲/胺、硫脲/含氮碱催化剂、膦腈碱催化剂等。这些催化剂可以应用于环氧烷烃和二氧化碳共聚合制备聚碳酸酯、环氧烷烃的开环聚合制备聚醚材料、环内酯单体的开环聚合制备聚酯高分子材料、环磷酸酯单体的开环聚合制备聚磷酸酯高分子材料、取代环丙烷的开环聚合制备功能性聚丙烯高分子材料、环状碳酸酯的开环聚合制备聚碳酸酯材料、内酰胺的开环聚合制备聚酰胺高分子材料、环硅氧烷的开环聚合制备聚硅氧烷高分子材料、催化甲基丙烯酸甲酯单体制备聚甲基丙烯酸甲酯高分子材料、催化乙烯基醚单体制备功能性聚乙烯材料等领域。
根据有机催化的聚合反应机理，上述催化剂涉及到的聚合机理主要包括：亲电活化反应单体、亲核活化反应单体、引发剂的亲核活化、单体和引发剂协同活化等聚合机理。下面以具体的例子加以说明：
质子酸是经典的单体亲电活化机理。2005年，Didier Bourissou等人报道了利用三氟甲 磺酸作为催化剂，醇化合物作为引发剂用于催化丙交酯的开环聚合[Macromolecules,2005,38,9993-9998]。反应中，质子酸作为亲电试剂首先亲电活化丙交酯的羰基，随后醇化合物作为引发剂，亲核进攻羰基发生开环聚合反应，得到聚丙交酯高分子材料。
吡啶类、叔膦类[J.Polym.Sci.Part A:Polym.Chem.2002,40,844-851]及氮杂环卡宾类[J.Am.Chem.Soc.2002,124,914-915]催化体系作为亲核试剂可以活化反应单体进行聚合反应。反应中，催化剂活化环状单体形成两性反应中间体，此中间体再和引发剂醇化合物作用进而引发聚合反应。如Hedrick等报道的以4-N,N-二甲氨基吡啶(DMAP)为催化剂，乙醇为引发剂催化环内酯单体的开环聚合反应(Angew.Chem.Int.Ed.,2001,40,2712-2715)。
胍类化合物(如：N-甲基-1,5,7-三氮杂双环[4.4.0]癸-5-烯,MTBD)[Macromolecules2006,39,8574-8583]、脒类化合物(如：1,8-二氮杂双环[5.4.0]十一碳-7-烯)、膦腈碱类化合物[Macromol.Chem.Phys.2003，204，1056-1071；J.Am.Chem.Soc.129,42,12610-12611；Macrom.Rapid Comm.1995,16,449-453]主要是活化引发剂的聚合反应机理。聚合反应中，上述催化剂亲核活化醇类化合物，使引发剂去质子化形成醇盐，醇盐再进攻单体引发聚合反应。这类催化剂主要可用于催化环内酯、环氧烷烃、环硅氧烷等单体的开环聚合反应等。
上述有机催化聚合反应涉及到单体的亲电或亲核活化，引发剂的亲核活化，需要加入不同的催化剂、助催化剂和引发剂共同促进聚合反应的发生。因此，发展单体和引发剂的协同催化逐渐得到了广泛认可。这些催化剂的典型代表有硫脲-胺-醇催化体系[J.Am.Chem.Soc.2005,127,13798-13799；Macromolecules,2006,39,7863-7871]、[Macromolecules,2014,47,1277-1284]和1,5,7-三氮杂双环[4.4.0]癸-5-烯(TBD)-醇催化体系[J.Am.Chem.Soc.128,14,4556-4557；US 8367796 B2]等。如硫脲-胺-醇催化体系中，硫脲作为弱的亲电试剂可以活化单体，胺可以作为亲核试剂活化引发剂醇类化合物。同理，三烷基硼作为亲电试剂可与季铵盐、季鏻盐或膦腈类/醇等化合物组成多组分催化体系用于聚合反应。在这些聚合反应体系中，三乙基硼作为亲电试剂用于活化环状单体，季铵盐、季鏻盐、氧基金属盐、膦腈/醇类化合物作为引发剂，可以用于二氧化碳和环氧烷烃共聚合制备聚碳酸酯[J.Am.Chem.Soc.2016,138,11117-11120；CN 107849233 A；US 2018/0118884 A1]、环氧烷烃和硫氧化碳共聚制备硫代聚碳酸酯[CN 106866952 A；Macromolecules,2018,51,3126-3134]、环氧烷烃和酸酐共聚合制备聚酯[Green Chem.2018,20,3963-3973]等聚合反应中。
综上可知，有机催化剂目前已经成为传统的金属有机催化剂的理想替代品，用于多种高分子材料的合成制备。但有机催化体系往往需要加入多种亲电试剂、亲核试剂或助催化剂以达到活化反应单体和引发剂的目的，进而实现聚合反应的顺利实施，但聚合反应时催 化体系多组分的称量和分批加入往往导致实验可操作性变差；此外，上述催化体系还涉及到复杂的合成步骤，使得聚合成本增加。
发明内容
本发明的目的在于针对现有技术的不足，提供一种具有亲电亲核双功能的有机无金属催化剂。
本发明所提供的技术方案为：
具有亲电亲核双功能的有机无金属催化剂，具有式(I)所示的化学结构：
Figure PCTCN2019103919-appb-000001
式(I)中，各Y 1～Y 3独立地选自下列结构式1～5中的一种或多种：
Figure PCTCN2019103919-appb-000002
结构式1～3中各D 1～D 6独立地表示为:
Figure PCTCN2019103919-appb-000003
其中，B为硼原子，N为氮原子，P为磷原子，
Figure PCTCN2019103919-appb-000004
表示为连接键；
a、b各自独立地选自0-20的整数，但不可同时取0；各c、d、e独立地选自0-20的整数；当a为0时，各c与d不可同时取0；当b为0时，各e不可同时取0；
各Z 1～Z 4、R 1、R 2、E 1～E 4独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；其中，各Z 1～Z 3、R 1、R 2、Z 4、E 1～E 4中的两个或两个以上可成键或成环；
附加条件是：当a＝1时，Z 1不可为C 6的芳香基；当c＝1时，Z 2不可为C 6的芳香基；当d＝1时，Z 3不可为C 6的芳香基；各Z 1～Z 3或R 1、R 2、Z 4不可同时为取代或非取代的芳香基、取代或非取代的杂芳香基的一种或多种；各D 1～D 3和D 4～D 6不可同时为取代或非取代的C 6-C 10芳香基；
各
Figure PCTCN2019103919-appb-000005
表示为负离子；各
Figure PCTCN2019103919-appb-000006
独立地以单独负离子形式存在，或者各
Figure PCTCN2019103919-appb-000007
与D 1～D 6中的一种或多种以共价键形式相连。
本发明还提供一种具有亲电亲核双功能的有机无金属催化剂。所提供的技术方案为：
所述有机无金属催化剂具有如下所示的结构中的一种：
Figure PCTCN2019103919-appb-000008
Figure PCTCN2019103919-appb-000009
其中：
各i独立地选自1或2；
各f独立地选自0～3的整数，但任一结构中f不可同时为0；
g选自3～20的任意整数；
各h独立地选自0～3的整数，但任一结构中h不可同时为0；
各n独立地选自0～2的整数；
各K 1独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 7-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
各R 3～R 6、R 3’～R 6’、K 2～K 4、K 1’～K 3’独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
其中，各K 1～K 4、K 1’～K 3’、R 3～R 6、R 3’～R 6’中的两个或两个以上可成键或成环；
附加条件是：在同一结构中，R 3～R 5不可同时为芳香基或杂芳香基，R 3’～R 5’不可同时为芳香基或杂芳香基；
A选自N或P原子；
各G 1’、G 2’独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至20个碳原子的芳香基、5至20个碳原子的杂芳香基中的一种或多种；其中，各G 1’、G 2’可成键或成环，且G 1’、G 2’与K 1或K 2不可同时为取代或非取代的芳香基或杂芳香基；
各
Figure PCTCN2019103919-appb-000010
表示为负离子；各
Figure PCTCN2019103919-appb-000011
独立地以单独负离子形式存在，或者各
Figure PCTCN2019103919-appb-000012
与R 3～R 6、R 3’～R 6’中的一种或多种以共价键形式相连。
本发明还提供一种具有亲电亲核双功能的有机无金属催化剂。所提供的技术方案为：
所述有机无金属催化剂由至少含一个不饱和键的含氮或磷的反应原料W1，与至少含有一个硼氢键的反应原料W2通过硼氢化反应得到；
所述反应原料W1的结构式表示为如下的一种或多种：
Figure PCTCN2019103919-appb-000013
Figure PCTCN2019103919-appb-000014
其中：
各f独立地选自0～3的整数，但任一结构中f不可同时为0；
g选自3～20的任意整数；
各p独立地选自0～3的整数，各j独立地选自0～2的整数，但任一结构中p和j不可同时为0；
各h独立地选自0～3的整数，但任一结构中h不可同时为0；
各K 1独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 7-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
各R 3～R 6、R 3’～R 6’、K 2～K 4、K 1’～K 3’独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
其中，各K 1～K 4、K 1’～K 3’、R 3～R 6、R 3’～R 6’中的两个或两个以上可成键或成环；
附加条件是：在同一结构中，R 3～R 5不可同时为芳香基或杂芳香基；
A选自N或P原子；
各
Figure PCTCN2019103919-appb-000015
独立地表示为碳碳双键或碳碳三键；
各
Figure PCTCN2019103919-appb-000016
表示为负离子；各
Figure PCTCN2019103919-appb-000017
独立地以单独负离子形式存在，或者各
Figure PCTCN2019103919-appb-000018
与R 3～R 6、R 3’～R 6’中的一种或多种以共价键形式相连；
所述反应原料W2的结构式表示为如下的一种或多种：
Figure PCTCN2019103919-appb-000019
各G 1、G 2独立地选自未取代的或具有取代基的以下基团：H、卤素、C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至20个碳原子的芳香基、5至20个碳原子的杂芳香基中的一种或多种；其中，各G 1、G 2可成键或成环。
本发明的目的在于针对现有技术的不足，还提供一种具有亲电亲核双功能的有机无金属催化剂的制备方法。
本发明所提供的技术方案为：
反应式如下：
Figure PCTCN2019103919-appb-000020
由至少含一个不饱和键的含氮或磷的反应原料W1，与至少含有一个硼氢键的反应原料W2通过硼氢化反应得到；
所述反应原料W1的结构式表示为如下的一种或多种：
Figure PCTCN2019103919-appb-000021
其中：
各f独立地选自0～3的整数，但任一结构中f不可同时为0；
g选自3～20的任意整数；
各p独立地选自0～3的整数，各j独立地选自0～2的整数，但任一结构中p和j不可 同时为0；
各h独立地选自0～3的整数，但任一结构中h不可同时为0；
各K 1独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 7-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
各R 3～R 6、R 3’～R 6’、K 2～K 4、K 1’～K 3’独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
其中，各K 1～K 4、K 1’～K 3’、R 3～R 6、R 3’～R 6’中的两个或两个以上可成键或成环；
附加条件是：在同一结构中，R 3～R 5不可同时为芳香基或杂芳香基；
A选自N或P原子；
各
Figure PCTCN2019103919-appb-000022
独立地表示为碳碳双键或碳碳三键；
各
Figure PCTCN2019103919-appb-000023
表示为负离子；各
Figure PCTCN2019103919-appb-000024
独立地以单独负离子形式存在，或者各
Figure PCTCN2019103919-appb-000025
与R 3～R 6、R 3’～R 6’中的一种或多种以共价键形式相连；
所述反应原料W2的结构式表示为如下的一种或多种：
Figure PCTCN2019103919-appb-000026
各G 1、G 2独立地选自未取代的或具有取代基的以下基团：H、卤素、C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至20个碳原子的芳香基、5至20个碳原子的杂芳香基中的一种或多种；其中，各G 1、G 2可成键或成环。
本发明的目的在于针对现有技术的不足，还提供一种有机无金属催化剂在制备高分子材料中的应用。
本发明所提供的技术方案为：
一种或多种环状单体在具有亲电亲核双功能的有机无金属催化剂的接触下发生均聚合反应或共聚合反应得到高分子材料。
或者，一种或多种环状单体与二氧化碳、二硫化碳、硫氧化碳中的一种或多种在具有亲电亲核双功能的有机无金属催化剂的接触下发生共聚合反应得到高分子材料。
本发明的目的在于针对现有技术的不足，还提供一种有机无金属催化剂在制备高分子材料中的应用，包括：催化二氧化碳与环氧烷烃的共聚合制备脂肪族聚碳酸酯、催化环氧烷烃的开环聚合制备聚醚、催化环氧烷烃和环状酸酐制备聚酯以及催化硫氧化碳和环氧烷烃共聚制备聚硫代碳酸酯。
同现有技术相比，本发明的有益效果体现在：与目前存在的无金属有机聚合催化体系相比，具有制备简单、活性高、使用方便、成本低、适用性广的优点，非常适合工业化生产。
附图说明
图1为实施例1中制备的催化剂B1的 1H NMR谱图；
图2为应用例2制备的聚环己烯碳酸酯的 1H NMR谱图；
图3为应用例2制备的聚环己烯碳酸酯的GPC图；
图4为应用例21制备的聚碳酸丙烯酯PPC的 1H NMR谱图；
图5为应用例32制备的聚醚的 1H NMR谱图；
图6为应用例36制备的聚环己烯碳酸酯的GPC图；
图7为应用例38制备的聚丁二酸环己烯酯的 1H NMR谱图；
图8为应用例40制备聚环己烯碳酸酯-聚丁二酸环己烯酯嵌段共聚物的GPC图；
图9为应用例42制备的聚丙交酯的 1H NMR谱图；
图10为应用例43制备的聚磷酸酯的 1H NMR谱图；
图11为应用例44制备的聚磷酸酯-聚碳酸酯嵌段共聚物的 1H NMR谱图。
具体实施方式
下面的实例将更好地说明本发明，但须强调的是本发明绝不仅限于这几个实例所表述的内容，对于本技术领域的技术人员或普通技术人员来说，在不脱离本发明原理的前提下，对本发明进行的若干改进和修饰，也落入本发明权利要求的保护范围内。
除非有特别说明，下列用在说明书和权利要求书中的术语具有下述含义：
烷基是指饱和的脂族烃基团，包括1至30个碳原子的直链和支链基团。优选含有1至15个碳原子，进一步优选含有1至6个碳原子的中等大小烷基，例如甲基、乙基、丙基、异丙基、正丁基、异丁基、叔丁基、戊基、己基等。更优选的是含有1至4个碳原子的低级烷基，例如甲基、乙基、丙基、异丙基、正丁基、异丁基、叔丁基等。
环烷基是指包括1至30个碳原子的全碳单环、稠合环或多环稠合环基团。优选为3至8元全碳单环、全碳5元/6元或6元/6元稠合环或多环稠合环基团，其中一个或多个环可以含有一个或多个双键。更优选为环丙基、环丁基、环戊基、环己基、环己二烯基、金刚烷基、环庚三烯基等。
烯基是指具有碳碳双键的不饱和脂族烃基团，包括1至30个碳原子的直链和支链基团。优选为含2-10个(进一步为2-6个)碳原子的直链和支链基团。
炔基是指具有碳碳三键的不饱和脂族烃基团，包括1至30个碳原子的直链和支链基团。优选为含2-10个(进一步为2-6个)碳原子的直链和支链基团。
芳香基是指具有至少一个芳环结构的基团，优选为碳环芳香基、杂芳香基。
杂芳香基是指具有1个杂原子作为成环原子，其余的成环原子为碳的芳香基，环结构满足休克尔规则，杂原子包括O、S、N、Si、P原子。优选为5元、6元或7元环。进一步优选，杂芳香基团包括但不限于呋喃基、噻吩基、苯并呋喃基、苯并噻吩基、吡啶基、吡咯基、N-烷基吡咯基。
杂环基是指构成环的原子除碳原子外，还至少含有一个杂原子的基团，杂原子包括O、S、N、Si、P原子。优选为5元、6元或7元环的脂杂环、芳杂环。
卤素指氟、氯、溴或碘。
Figure PCTCN2019103919-appb-000027
表示为连接键。
Figure PCTCN2019103919-appb-000028
表示为结构式中基团与基团之间的连接键，连接两侧的基团，在某一结构式中一根
Figure PCTCN2019103919-appb-000029
并不仅仅表示只有一根连接键，也可以表示为连接于一侧基团上几个原子的多根连接键。
“各”指的是每一个。例如“各Y 1～Y 3独立地选自”，具体指Y 1、Y 2和Y 3，当结构式中含有多个Y 1时，同样指每个Y 1，相互之间不影响，独立地表示为各自的结构，可以相同也可以不同。
作为本发明的一个实例，具有亲电亲核双功能的有机无金属催化剂具有式(I)所示的化学结构：
Figure PCTCN2019103919-appb-000030
式(I)中，各Y 1～Y 3独立地选自下列结构式1～5中的一种或多种：
Figure PCTCN2019103919-appb-000031
结构式1～3中各D 1～D 6独立地表示为:
Figure PCTCN2019103919-appb-000032
其中，B为硼原子，N为氮原子，P为磷原子，
Figure PCTCN2019103919-appb-000033
表示为连接键；
a、b各自独立地选自0-20的整数，但不可同时取0；各c、d、e独立地选自0-20的整数；当a为0时，各c与d不可同时取0；当b为0时，各e不可同时取0；
各Z 1～Z 4、R 1、R 2、E 1～E 4独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；其中，各Z 1～Z 3、R 1、R 2、Z 4、E 1～E 4中的两个或两个以上可成键或成环；
附加条件是：当a＝1时，Z 1不可为C 6的芳香基；当c＝1时，Z 2不可为C 6的芳香基；当d＝1时，Z 3不可为C 6的芳香基；各Z 1～Z 3或R 1、R 2、Z 4不可同时为取代或非取代的芳香基、取代或非取代的杂芳香基的一种或多种；各D 1～D 3和D 4～D 6不可同时为取代或非取代的C 6-C 10芳香基；
各
Figure PCTCN2019103919-appb-000034
表示为负离子；各
Figure PCTCN2019103919-appb-000035
独立地以单独负离子形式存在，或者各
Figure PCTCN2019103919-appb-000036
与D 1～D 6中的一种或多种以共价键形式相连。
作为本发明其中一个实例，各Z 1～Z 4之间或者与同一个结构式中其他Z 1～Z 4可成键或成环，以单环、双环、三环、多环或螺环结构形式存在；各R 1、R 2之间或者与同一个结构 式中其他R 1或R 2可成键或成环，以单环、双环、三环、多环或螺环结构形式存在；各E 1～E 4之间或者与同一个结构式中其他E 1～E 4可成键成环，以单环、双环、三环、多环或螺环结构形式存在。此处再次说明，其中的“各”指的是每一个，例如“各R 1、R 2”表示为R 1、R 2以及同一个结构式中含有的多个R 1和R 2，即R 1可以与R 2成键或成环，也可以与结构式中的其它R 1或R 2成键或成环。
作为本发明其中一个实例，各Z 1～Z 4、R 1、R 2、E 1～E 4独立地选自未取代的或具有取代基的以下基团：C 1-C 18烷基、C 3-C 18环烷基、C 3-C 18烯基、C 3-C 18炔基、C 6-C 18芳香基、C 3-C 18杂环基、C 5-C 18杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至10个碳原子的支链或直链的烃基、1至10个碳原子的支链或直链的烷氧基、3至10个碳原子的支链或直链的环烷基、6至18个碳原子的芳香基、5至18个碳原子的杂芳香基中的一种或多种。
作为本发明其中一个实例，所述各
Figure PCTCN2019103919-appb-000037
独立地选自
Figure PCTCN2019103919-appb-000038
Figure PCTCN2019103919-appb-000039
磺酸根、高氯酸根、氯酸根、磷酸根、羧酸根、烷氧根、酚氧根中的一种或多种。
具体地，所述各
Figure PCTCN2019103919-appb-000040
独立地选自
Figure PCTCN2019103919-appb-000041
Figure PCTCN2019103919-appb-000042
磺酸根、高氯酸根、氯酸根、磷酸根、羧酸根、烷氧根、酚氧根中的一种或多种；其中酚氧根、羧酸根、磺酸根、烷氧根、包括但不限于邻硝基苯酚氧负离子、对硝基苯酚氧负离子、间硝基苯酚氧负离子、2,4-二硝基苯酚氧负离子、3,5-二硝基苯酚氧负离子、2,4,6-三硝基苯酚氧负离子、3,5-二氯苯酚氧负离子、3,5-二氟苯酚氧负离子、3,5-二-三氟甲基苯酚氧负离子、五氟酚氧负离子、乙酸根、丙酸根、丁酸根、三氟乙酸根、三氯乙酸根、苯磺酸根、对甲基苯磺酸根、对三氟甲基苯磺酸根、甲氧基、乙氧基、丙氧基、异丙氧基、叔丁氧基负离子中的一种或多种。
作为本发明的一个实例，具有亲电亲核双功能的有机无金属催化剂具有如下所示的结构中的一种：
Figure PCTCN2019103919-appb-000043
Figure PCTCN2019103919-appb-000044
其中：
各i独立地选自1或2；
各f独立地选自0～3的整数，但任一结构中f不可同时为0；
g选自3～20的任意整数；
各h独立地选自0～3的整数，但任一结构中h不可同时为0；
各n独立地选自0～2的整数；
各K 1独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 7-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
各R 3～R 6、R 3’～R 6’、K 2～K 4、K 1’～K 3’独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
其中，各K 1～K 4、K 1’～K 3’、R 3～R 6、R 3’～R 6’中的两个或两个以上可成键或成环；
附加条件是：在同一结构中，R 3～R 5不可同时为芳香基或杂芳香基，R 3’～R 5’不可同时为芳香基或杂芳香基；
A选自N或P原子；
各G 1’、G 2’独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至20个碳原子的芳香基、5至20个碳原子的杂芳香基中的一种或多种；其中，各G 1’、G 2’可成键或成环，以单环、双环、三环、多环或螺环结构形式存在，且G 1’、G 2’与K 1或K 2不可同时为取代或非取代的芳香基或杂芳香基；
各
Figure PCTCN2019103919-appb-000045
表示为负离子；各
Figure PCTCN2019103919-appb-000046
独立地以单独负离子形式存在，或者各
Figure PCTCN2019103919-appb-000047
与R 3～R 6、 R 3’～R 6’中的一种或多种以共价键形式相连；
具体地，各
Figure PCTCN2019103919-appb-000048
独立地选自
Figure PCTCN2019103919-appb-000049
Figure PCTCN2019103919-appb-000050
磺酸根、高氯酸根、氯酸根、磷酸根、羧酸根、烷氧根、酚氧根中的一种或多种；其中酚氧根、羧酸根、磺酸根、烷氧根、包括但不限于邻硝基苯酚氧负离子、对硝基苯酚氧负离子、间硝基苯酚氧负离子、2,4-二硝基苯酚氧负离子、3,5-二硝基苯酚氧负离子、2,4,6-三硝基苯酚氧负离子、3,5-二氯苯酚氧负离子、3,5-二氟苯酚氧负离子、3,5-二-三氟甲基苯酚氧负离子、五氟酚氧负离子、乙酸根、丙酸根、丁酸根、三氟乙酸根、三氯乙酸根、苯磺酸根、对甲基苯磺酸根、对三氟甲基苯磺酸根、甲氧基、乙氧基、丙氧基、异丙氧基、叔丁氧基负离子中的一种或多种。
作为本发明的一个具体实例，所述各结构中的
Figure PCTCN2019103919-appb-000051
和
Figure PCTCN2019103919-appb-000052
各自独立地表示为如下的任意一种或多种：
Figure PCTCN2019103919-appb-000053
Figure PCTCN2019103919-appb-000054
表示为连接键；
各m独立地选自1～18的任意整数。
作为本发明的一个具体实例，所述各结构中的
Figure PCTCN2019103919-appb-000055
各自独立地表示为如下的任意一种或多种：
Figure PCTCN2019103919-appb-000056
Figure PCTCN2019103919-appb-000057
Figure PCTCN2019103919-appb-000058
表示为连接键；
各m独立地选自1～18的任意整数。
作为本发明的一个具体实例，各R 3～R 6、R 3’～R 6’独立地选自未取代的或具有取代基的以下基团：C 1-C 18烷基、C 3-C 18环烷基、C 3-C 18烯基、C 3-C 18炔基、C 6-C 18芳香基、C 3-C 18杂环基、C 5-C 18杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至10个碳原子的支链或直链的烃基、1至10个碳原子的支链或直链的烷氧基、3至10个碳原子的支链或直链的环烷基、6至18个碳原子的芳香基、5至18个碳原子的杂芳香基中的一种或多种。
作为本发明的一个具体实例，各K 1～K 4、K 1’～K 3’独立地选自下列的一种或多种；
Figure PCTCN2019103919-appb-000059
各R 7～R 25独立地选自未取代的或具有取代基的以下基团：C 1-C 18烷基、C 3-C 18环烷基、C 3-C 18烯基、C 3-C 18炔基、C 6-C 18芳香基、C 3-C 18杂环基、C 5-C 18杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至10个碳原子的支链或直链的烃基、1至10个碳原子的支链或直链的烷氧基、3至10个碳原子的支链或直链的环烷基、6至12个碳原子的芳香基、5至12个碳原子的杂芳香基中的一种或多种。
作为本发明的一个具体实例，有机无金属催化剂具有如下所示的结构中的一种：
Figure PCTCN2019103919-appb-000060
Figure PCTCN2019103919-appb-000061
作为本发明的一个实例，具有亲电亲核双功能的有机无金属催化剂由至少含一个不饱和键的含氮或磷的反应原料W1，与至少含有一个硼氢键的反应原料W2通过硼氢化反应得到；
所述反应原料W1的结构式表示为如下的一种或多种：
Figure PCTCN2019103919-appb-000062
Figure PCTCN2019103919-appb-000063
其中：
各f独立地选自0～3的整数，但任一结构中f不可同时为0；
g选自3～20的任意整数；
各p独立地选自0～3的整数，各j独立地选自0～2的整数，但任一结构中p和j不可同时为0；
各h独立地选自0～3的整数，但任一结构中h不可同时为0；
各K 1独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 7-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
各R 3～R 6、R 3’～R 6’、K 2～K 4、K 1’～K 3’独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
其中，各K 1～K 4、K 1’～K 3’、R 3～R 6、R 3’～R 6’中的两个或两个以上可成键或成环；
附加条件是：在同一结构中，R 3～R 5不可同时为芳香基或杂芳香基；
A选自N或P原子；
各
Figure PCTCN2019103919-appb-000064
独立地表示为碳碳双键或碳碳三键；其中“各
Figure PCTCN2019103919-appb-000065
”不仅指上述不同结构式中的
Figure PCTCN2019103919-appb-000066
同时还指的是同一个结构式中
Figure PCTCN2019103919-appb-000067
各个
Figure PCTCN2019103919-appb-000068
可相同或不同。
各
Figure PCTCN2019103919-appb-000069
表示为负离子；各
Figure PCTCN2019103919-appb-000070
独立地以单独负离子形式存在，或者各
Figure PCTCN2019103919-appb-000071
与R 3～R 6、R 3’～R 6’中的一种或多种以共价键形式相连；
具体的，各
Figure PCTCN2019103919-appb-000072
独立地选自
Figure PCTCN2019103919-appb-000073
Figure PCTCN2019103919-appb-000074
磺酸根、高氯酸根、氯酸根、磷酸根、羧酸根、烷氧根、酚氧根中的一种或多种；其中酚氧根、羧酸根、磺酸根、烷氧根、包括但不限于邻硝基苯酚氧负离子、对硝基苯酚氧负离子、间硝基苯酚氧负离子、2,4-二硝基苯酚氧负离子、3,5-二硝基苯酚氧负离子、2,4,6-三硝基苯酚氧负离子、3,5-二氯苯酚氧负离子、3,5-二氟苯酚氧负离子、3,5-二-三氟甲基苯酚氧负离子、五氟酚氧负离子、乙酸根、丙酸根、丁酸根、三氟乙酸根、三氯乙酸根、苯磺酸根、对甲基苯磺酸根、对三氟甲基苯磺酸根、甲氧基、乙氧基、丙氧基、异丙氧基、叔丁氧基负离子中的一种或多种；
所述反应原料W2的结构式表示为如下的一种或多种：
Figure PCTCN2019103919-appb-000075
各G 1、G 2独立地选自未取代的或具有取代基的以下基团：H、卤素、C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至20个碳原子的芳香基、5至20个碳原子的杂芳香基中的一种或多种；其中，各G 1、G 2可成键或成环，以单环、双环、三环、多环或螺环结构形式存在。
作为本发明的一个实例，具有亲电亲核双功能的有机无金属催化剂的制备方法，由至少含一个不饱和键的含氮或磷的反应原料W1，与至少含有一个硼氢键的反应原料W2通过硼氢化反应得到；
具体的反应式如下：
Figure PCTCN2019103919-appb-000076
所述反应原料W1的结构式表示为如下的一种或多种：
Figure PCTCN2019103919-appb-000077
其中：
各f独立地选自0～3的整数，但任一结构中f不可同时为0；
g选自3～20的任意整数；
各p独立地选自0～3的整数，各j独立地选自0～2的整数，但任一结构中p和j不可同时为0；
各h独立地选自0～3的整数，但任一结构中h不可同时为0；
各K 1独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 7-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
各R 3～R 6、R 3’～R 6’、K 2～K 4、K 1’～K 3’独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
其中，各K 1～K 4、K 1’～K 3’、R 3～R 6、R 3’～R 6’中的两个或两个以上可成键或成环，以单环、双环、三环、多环或螺环结构形式存在；
附加条件是：在同一结构中，R 3～R 5不可同时为芳香基或杂芳香基；
A选自N或P原子；
各
Figure PCTCN2019103919-appb-000078
独立地表示为碳碳双键或碳碳三键；其中“各
Figure PCTCN2019103919-appb-000079
”不仅指上述不同结构式中的
Figure PCTCN2019103919-appb-000080
同时还指的是同一个结构式中
Figure PCTCN2019103919-appb-000081
各个
Figure PCTCN2019103919-appb-000082
可相同或不同。
各
Figure PCTCN2019103919-appb-000083
表示为负离子；各
Figure PCTCN2019103919-appb-000084
独立地以单独负离子形式存在，或者各
Figure PCTCN2019103919-appb-000085
与R 3～R 6、R 3’～R 6’中的一种或多种以共价键形式相连；
具体地，各
Figure PCTCN2019103919-appb-000086
独立地选自
Figure PCTCN2019103919-appb-000087
Figure PCTCN2019103919-appb-000088
磺酸根、高氯酸根、氯酸根、磷酸根、羧酸根、烷氧根、酚氧根中的一种或多种；其中酚氧根、羧酸根、磺酸根、烷氧根、包括但不限于邻硝基苯酚氧负离子、对硝基苯酚氧负离子、间硝基苯酚氧负离子、2,4-二硝基苯酚氧负离子、3,5-二硝基苯酚氧负离子、2,4,6-三硝基苯酚氧负离子、3,5-二氯苯酚氧负离子、3,5-二氟苯酚氧负离子、3,5-二-三氟甲基苯酚氧负离子、五氟酚氧负离子、乙酸根、丙酸根、丁酸根、三氟乙酸根、三氯乙酸根、苯磺酸根、对甲基苯磺酸根、对三氟甲基苯磺酸根、甲氧基、乙氧基、丙氧基、异丙氧基、叔丁氧基负离子中的一种或多种；
所述反应原料W2的结构式表示为如下的一种或多种：
Figure PCTCN2019103919-appb-000089
各G 1、G 2独立地选自未取代的或具有取代基的以下基团：H、卤素、C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至20个碳原子的芳香基、5至20个碳原子的杂芳香基中的一种或多种；其中，各G 1、G 2可成键或成环，以单环、双环、三环、多环或螺环结构形式存在。
需要说明的是，反应式(II)所提供的制备方法仅是有机无金属催化剂的其中一种制备方法，不限于反应式(II)，反应式(II)中的反应原料包括但不限于W1和W2，更多制备方法可见具体实施例。
作为本发明的一个优选实例，具有亲电亲核双功能的有机无金属催化剂的制备方法包括：将任一反应原料W1和任一反应原料W2在氮气或惰性气体的保护下混合，加入有机溶剂，在-20～150℃下，搅拌1～500小时进行硼氢化反应，反应结束后，降至室温，去除杂质和有机溶剂，得到具有亲电亲核双功能的有机无金属催化剂。
作为本发明的一个优选实例，所述有机溶剂选自四氢呋喃、苯、甲苯、氯仿、己烷、乙醚、二氯甲烷、乙酸乙酯、二甲基亚砜、四氯化碳、1,4-二氧六环、吡啶中的一种或多种。
作为本发明的一个实例，所述有机无金属催化剂在制备高分子材料中的应用，包括一种或多种环状单体在具有亲电亲核双功能的有机无金属催化剂的接触下发生均聚合反应或共聚合反应得到高分子材料。其中，通过调控催化剂的结构和用量、加入不同的环状单体和用量，足以选择性修改所得到的高分子材料。
作为本发明的一个实例，所述有机无金属催化剂在制备高分子材料中的应用，包括一种或多种环状单体与二氧化碳、二硫化碳、硫氧化碳中的一种或多种在具有亲电亲核双功能的有机无金属催化剂的接触下发生共聚合反应得到高分子材料。其中，通过调控催化剂的结构和用量、加入不同的环状单体和用量、二氧化碳、二硫化碳或硫氧化碳的用量，可以选择性得到所需结构的高分子材料。
作为本发明的一个优选实例，所述环状单体选自如下结构：
Figure PCTCN2019103919-appb-000090
Figure PCTCN2019103919-appb-000091
作为本发明的一个优选实例，所述有机无金属催化剂在制备高分子材料中的应用，在所述聚合反应体系中可加入一种或多种醇化合物、酸化合物、胺化合物、多元醇、多元羧酸、多元醇酸、水作为链转移剂制备相应的聚合物多元醇。
作为本发明的一个具体实例，所述链转移剂选自如下结构：
Figure PCTCN2019103919-appb-000092
作为本发明的一个优选实例，所述有机无金属催化剂在制备高分子材料中的应用，在所述聚合反应体系中加入带有醇羟基、酚羟基、氨基、羧基的一种或多种聚合物作为大分 子链转移剂制备相应的嵌段共聚物或接枝共聚物。
作为本发明的一个优选实例，所述链转移剂选自如下结构：
Figure PCTCN2019103919-appb-000093
其中，
Figure PCTCN2019103919-appb-000094
表示大分子链转移剂主链，图中所示醇羟基、酚羟基、氨基、羧基等不代表官能团的具体个数，可以为理论上的1～50000中的任意数值。
加入链转移剂的聚合一般在惰性溶剂中进行，如氯仿、二氯甲烷、甲苯、四氢呋喃或环氧烷烃本体，优选为甲苯或环氧烷烃本体作为溶剂；聚合温度一般维持在-50～200℃度，优选50～150℃；二氧化碳压力为0.1～200MPa之间，优选1～5MPa；催化剂浓度可在10 -6～10 -2M，优选在10 -5～10 -3M内使用；链转移剂和反应单体的比例范围为10 -5～10 5，优选在10 -3～10 3内使用。
作为本发明的一个优选实例，所述有机无金属催化剂在制备高分子材料中的应用中，将有机无金属催化剂负载在无机载体或有机载体上进行使用。
作为本发明的一个优选实例，所述的有机无金属催化剂在制备高分子材料中的应用包括：催化二氧化碳与环氧烷烃的共聚合制备脂肪族聚碳酸酯、催化环氧烷烃的开环聚合制备聚醚、催化环氧烷烃和环状酸酐制备聚酯以及催化硫氧化碳和环氧烷烃共聚制备聚硫代碳酸酯。将链转移剂、催化剂加入到催化二氧化碳与环氧烷烃的共聚合制备脂肪族聚碳酸酯、环氧烷烃的开环聚合制备聚醚、环氧烷烃和环状酸酐制备聚酯、硫氧化碳和环氧烷烃共聚制备聚硫代碳酸酯等高分子材料的聚合反应中，调节至所需温度，反应一定时间后，冷却，沉淀、称重即可高效制备相应的聚合物多元醇、嵌段共聚物或接枝共聚物。
针对催化二氧化碳与环氧烷烃的共聚合制备脂肪族聚碳酸酯：聚合一般在惰性溶剂，如氯仿、二氯甲烷、甲苯、四氢呋喃或环氧烷烃本体聚合中进行，优选为甲苯或环氧烷烃本体作为溶剂；将催化剂、一种或多种环氧烷烃溶解于上述惰性溶剂中，调节至所需温度，充入所需二氧化碳即可高效制备聚碳酸酯，反应一定时间后，冷却，沉淀、称重即可制备聚碳酸酯高分子材料。其中：聚合温度一般维持在-50～200℃，优选50～150℃；二氧化碳压力为0.1～200MPa之间，优选1～5MPa；催化剂浓度可在10 -6～10 -2M，优选在10 -5～10 -3M内使用；环氧烷烃单体如上所述。
通过调控催化剂结构和聚合条件，制备的聚合物的分子量在500-1500000Da之间，多分散性在1.01-10.00之间，聚碳酸酯和环状碳酸酯的选择性比例可以在1％～100％之间进行任意的调控，聚碳酸酯中聚醚的含量可在0％～99％之间进行任意的调控。
针对催化环氧烷烃的开环聚合制备聚醚：聚合一般在惰性溶剂，如氯仿、二氯甲烷、 甲苯、四氢呋喃或环氧烷烃本体聚合中进行，优选为甲苯或环氧烷烃本体作为溶剂；将催化剂溶解于上述溶剂中，调节至所需温度，反应一定时间后，冷却，沉淀、称重即可高效制备聚醚高分子材料。其中：聚合温度一般维持在-50～200℃，优选50～150℃；催化剂浓度可在10 -8～10 -2M，优选在10 -5～10 -3M内使用；所用的环氧烷烃单体如上所述。
针对催化环氧烷烃和环状酸酐制备聚酯：聚合一般在惰性溶剂，如氯仿、二氯甲烷、甲苯、四氢呋喃或环氧烷烃本体聚合中进行，优选为甲苯或环氧烷烃本体作为溶剂；将催化剂、酸酐、环氧烷烃，溶解于上述溶剂中，调节至所需温度，反应一定时间后，冷却，沉淀、称重即可高效制备聚醚高分子材料。其中：聚合温度一般维持在-50～200℃度，优选50～150℃；催化剂浓度可在10 -6～10 -2M，优选在10 -5～10 -3M内使用；所用的环氧烷烃单体如上所述；所用的环状酸酐单体如上所述。
针对催化硫氧化碳和环氧烷烃共聚制备聚硫代碳酸酯：聚合一般在惰性溶剂，如氯仿、二氯甲烷、甲苯、四氢呋喃或环氧烷烃本体聚合中进行，优选为甲苯或环氧烷烃本体作为溶剂；将催化剂、环氧烷烃溶解于上述溶剂中，调节至所需温度，充入所需二氧化碳、二硫化碳、硫氧化碳中的一种或多种，反应一定时间后，冷却，沉淀、称重即可高效制备硫代聚碳酸酯。其中：聚合温度一般维持在-50～200℃度，优选50～150℃；二氧化碳压力为0.1MPa～200MPa之间，优选1～5MPa；催化剂浓度可在10 -6～10 -2M，优选在10 -5～10 -3M内使用；所用的环氧烷烃单体如上所述。
应当指出，在聚合时加入一定量的路易斯碱、路易斯酸或其它催化剂及助催化剂等也都落在本专利的保护范围。
下面通过具体的实施例对本发明进行具体介绍：
实施例1：催化剂B1的合成
Figure PCTCN2019103919-appb-000095
在手套箱中，将各0.1mol的原料r1-1(12.2g)和r1-2(8.5g)，加入到100ml四氢呋喃中，室温下反应6h，抽干溶剂，用己烷洗涤，可得目标产物B1，收率为95％。利用核磁对B1进行了表征，催化剂B1的 1H NMR图见附图1。
实施例2：催化剂B2的合成
Figure PCTCN2019103919-appb-000096
在手套箱中，将各0.1mol的原料r2-1(12.2g)和r2-2(31.8g)，加入到100ml四氢呋喃中，室温下搅拌36h，抽干溶剂，用己烷洗涤，可得目标产物B2，收率为91％。
实施例3：催化剂B3的合成
Figure PCTCN2019103919-appb-000097
(1)在手套箱中，将各0.1mol的原料r3-1(17.8g)和r3-2(14.5g)加入到100ml乙醚中，室温下搅拌6h，可得r3-3；
(2)向上述反应液中加入0.1mol的r3-4(13.3g)，50℃反应8h，可得r3-5；
(3)向上述反应液中加入0.1mol的r3-6(13.7g)，80℃反应24h，抽干溶剂，用己烷洗涤，可得目标产物B3，收率为90％。
实施例4：催化剂B4的合成
Figure PCTCN2019103919-appb-000098
(1)在手套箱中，将各0.1mol的原料r4-1(17.8g)和r4-2(14.3g)加入到100ml乙醚中，室温下反应6h，可得r4-3；
(2)向上述反应液中加入0.1mol的r4-4(11.4g)，室温反应8h，可得r4-5；
(3)向上述反应液中加入0.1mol的r4-6(13.7g)，80℃反应24h，抽干溶剂，用己 烷洗涤，可得目标产物B4，收率为90％。
实施例5：催化剂B5的合成
Figure PCTCN2019103919-appb-000099
(1)如实施例1先合成得到催化剂B1；
(2)在手套箱中，取0.1mol的B1(2.99g)溶于50ml二氯甲烷中，并向其中加入0.1mol的CF 3COOAg(2.20g)室温下搅拌12h，过滤除去沉淀，抽干溶剂，用己烷洗涤，可得目标产物B5收率为85％，利用核磁对B5进行进一步表征。
实施例5：催化剂B6的合成
Figure PCTCN2019103919-appb-000100
(1)在手套箱中，将0.1mol的原料r6-1(12.2g)和16.7mmol的r6-2(2.4g)加入到100ml四氢呋喃中，室温下搅拌48h，可得r6-3；
(2)向(1)的反应液中加入16.7mmol的r6-4(3.3g)并室温反应24h抽干溶剂，用己烷洗涤，可得目标产物B6，收率为75％，利用核磁对B6进行表征。
实施例7：催化剂B7的合成
Figure PCTCN2019103919-appb-000101
(1)在手套箱中，将0.1mol的原料r7-1(15.8g)和0.1mol的r7-2(15.8g)加入到100ml四氢呋喃中，60℃下搅拌24h，可得r7-3；
(2)向(1)的反应液中加入0.1mol的r7-4(17.0g)并室温反应24h抽干溶剂，用己烷洗涤，可得目标产物B7，收率为81％。
实施例8：催化剂B8的合成
Figure PCTCN2019103919-appb-000102
(1)在手套箱中，将0.1mol的原料r8-1(17.1g)和0.3mol(21.0g)的r8-2加入到100ml甲苯中，100℃下反应8h，可得r8-3；
(2)向(1)的反应液中加入0.2mol的r8-4(21.8g)并室温反应12h抽干溶剂，用己烷洗涤，可得目标产物B8，收率为68％。
实施例9：催化剂B9的合成
Figure PCTCN2019103919-appb-000103
(1)在手套箱中，将0.4mol的原料r9-1(28.0g)和0.1mol的r9-2(22.0g)加入到100ml甲苯中，100℃下反应24h，可得r9-3；
(2)向(1)的反应液中加入0.2mol的r9-4(27.4g)，并100℃下反应12h，抽干溶剂，用己烷洗涤，可得目标产物B9，收率为72％。
实施例10：催化剂B10的合成
Figure PCTCN2019103919-appb-000104
(1)在手套箱中，将各0.1mol的原料r10-1(14.9g)和r10-2(7.0g)加入到100ml四氢呋喃中，室温下反应12h，可得r10-3；
(2)向上述反应液中加入0.1mol的实施例4中的中间产物r10-4(86.3g)，60℃反应8h，可得B10。
实施例11：催化剂B11的合成
Figure PCTCN2019103919-appb-000105
(1)如实施例1先合成得到催化剂B1；
(2)在手套箱中，取0.1mol的B1(29.9g)溶于50毫升二氯甲烷中，并向其中加入0.1mol的r11-1(18.9g)，50℃下搅拌6h，抽干溶剂，用己烷洗涤，可得目标产物B11收率为86％。
实施例12：催化剂B12的合成
Figure PCTCN2019103919-appb-000106
在手套箱中，将各0.1mol的原料r12-1(12.2g)和r12-2(17.9g)，加入到100ml四氢呋喃中，50℃下反应12h，抽干溶剂，用己烷洗涤，可得目标产物B12，收率为95％。
应用例1：利用催化剂B7催化环氧丙烷(PO)与二氧化碳共聚
Figure PCTCN2019103919-appb-000107
在手套箱中，取实施例7中制备的催化剂B7(0.01mmol)加入高压釜中，并加入环氧丙烷(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，并对聚合物进行凝胶渗透色谱(GPC)的表征，核磁及GPC的表征结果见表1。
应用例2：利用催化剂B1催化环氧环己烷(CHO)与二氧化碳共聚
Figure PCTCN2019103919-appb-000108
在手套箱中，取实施例1中制备的催化剂B1(0.01mmol)加入高压釜中，并加入环氧环己烷(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，核磁谱图见图2。从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。所得聚合物的GPC谱图见图3。
应用例3：利用催化剂B7催化环氧乙烷(EO)与二氧化碳共聚
Figure PCTCN2019103919-appb-000109
在手套箱中，取实施例7中制备的催化剂B7(0.01mmol)加入高压釜中，并加入环氧乙烷(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例4：利用催化剂B7催化氧化柠檬烯(LO)与二氧化碳共聚
Figure PCTCN2019103919-appb-000110
在手套箱中，取实施例7中制备的催化剂B7(0.01mmol)加入高压釜中，并加入氧化柠檬烯(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例5：利用催化剂B1催化4-乙烯基环氧环己烷(VCHO)与二氧化碳共聚
Figure PCTCN2019103919-appb-000111
在手套箱中，取实施例1中制备的催化剂B1(0.01mmol)加入高压釜中，并加入4-乙烯基环氧环己烷(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出 聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例6：利用催化剂B2催化CHO与二氧化碳共聚
在手套箱中，取实施例2中制备的催化剂B2(0.01mmol)加入高压釜中，并加入CHO(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例7：利用催化剂B3催化CHO与二氧化碳共聚
在手套箱中，取实施例3中制备的催化剂B3(0.01mmol)加入高压釜中，并加入CHO(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例8：利用催化剂B4催化CHO与二氧化碳共聚
在手套箱中，取实施例4中制备的催化剂B4(0.01mmol)加入高压釜中，并加入CHO(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例9：利用催化剂B5催化CHO与二氧化碳共聚
在手套箱中，取实施例5中制备的催化剂B5(0.01mmol)加入高压釜中，并加入CHO(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例10：利用催化剂B6催化CHO与二氧化碳共聚
在手套箱中，取实施例6中制备的催化剂B6(0.01mmol)加入高压釜中，并加入CHO(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例11：利用催化剂B7催化CHO与二氧化碳共聚
在手套箱中，取实施例7中制备的催化剂B7(0.01mmol)加入高压釜中，并加入CHO(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例12：利用催化剂B8催化CHO与二氧化碳共聚
在手套箱中，取实施例8中制备的催化剂B8(0.01mmol)加入高压釜中，并加入CHO(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例13：利用催化剂B9催化CHO与二氧化碳共聚
在手套箱中，取实施例9中制备的催化剂B9(0.01mmol)加入高压釜中，并加入CHO(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例14：利用催化剂B10催化CHO与二氧化碳共聚
在手套箱中，取实施例10中制备的催化剂B10(0.01mmol)加入高压釜中，并加入CHO(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例15：利用催化剂B11催化CHO与二氧化碳共聚
在手套箱中，取实施例11中制备的催化剂B11(0.01mmol)加入高压釜中，并加入CHO(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例16：利用催化剂B12催化CHO与二氧化碳共聚
在手套箱中，取实施例12中制备的催化剂B12(0.01mmol)加入高压釜中，并加入CHO(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例17：利用催化剂B2催化CHO与二氧化碳共聚
在手套箱中，取实施例2中制备的催化剂B2(0.1mmol)加入高压釜中，并加入CHO(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例18：利用催化剂B2催化CHO与二氧化碳共聚
在手套箱中，取实施例2中制备的催化剂B2(0.01mmol)加入高压釜中，并加入CHO(0.05mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例19：利用催化剂B2催化CHO与二氧化碳共聚
在手套箱中，取实施例2中制备的催化剂B2(0.01mmol)加入高压釜中，并加入CHO(0.1mol)，充入1.5MPa的CO 2，并在80℃的条件下反应8h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例20：利用催化剂B2催化CHO与二氧化碳共聚
在手套箱中，取实施例2中制备的催化剂B2(0.01mmol)加入高压釜中，并加入CHO(0.5mol)，充入1.5MPa的CO 2，并在80℃的条件下反应16h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例21：利用催化剂B3催化PO与二氧化碳共聚
在手套箱中，取实施例3中制备的催化剂B3(0.01mmol)加入高压釜中，并加入PO(0.01mol)，充入1.5MPa的CO 2，并在0℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。所得聚合物的核磁见图4。
应用例22：利用催化剂B3催化PO与二氧化碳共聚
在手套箱中，取实施例3中制备的催化剂B3(0.01mmol)加入高压釜中，并加入PO(0.01mol)，充入1.5MPa的CO 2，并在25℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例23：利用催化剂B3催化PO与二氧化碳共聚
在手套箱中，取实施例3中制备的催化剂B3(0.01mmol)加入高压釜中，并加入PO(0.01mol)，充入1.5MPa的CO 2，并在60℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例24：利用催化剂B3催化PO与二氧化碳共聚
在手套箱中，取实施例3中制备的催化剂B3(0.01mmol)加入高压釜中，并加入PO (0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例25：利用催化剂B3催化PO与二氧化碳共聚
在手套箱中，取实施例3中制备的催化剂B3(0.01mmol)加入高压釜中，并加入PO(0.01mol)，充入1.5MPa的CO 2，并在120℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例26：利用催化剂B4催化CHO与二氧化碳共聚
在手套箱中，取实施例4中制备的催化剂B4(0.01mmol)加入高压釜中，并加入CHO(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应0.5h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例27：利用催化剂B4催化CHO与二氧化碳共聚
在手套箱中，取实施例4中制备的催化剂B4(0.01mmol)加入高压釜中，并加入CHO(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应1h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例28：利用催化剂B4催化CHO与二氧化碳共聚
在手套箱中，取实施例4中制备的催化剂B4(0.01mmol)加入高压釜中，并加入CHO(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应4h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例29：利用催化剂B5催化CHO与二氧化碳共聚
在手套箱中，取实施例5中制备的催化剂B5(0.01mmol)加入高压釜中，并加入CHO(0.01mol)，加入1毫升四氢呋喃(THF)充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例30：利用催化剂B5催化CHO与二氧化碳共聚
在手套箱中，取实施例5中制备的催化剂B5(0.01mmol)加入高压釜中，并加入CHO (0.01mol)，加入1毫升甲苯(Tol)充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例31：利用催化剂B5催化CHO与二氧化碳共聚
在手套箱中，取实施例5中制备的催化剂B5(0.01mmol)加入高压釜中，并加入CHO(0.01mol)，加入1毫升氯仿(CHCl 3)充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，从乙醇中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例32：利用催化剂B6催化PO开环聚合聚合
Figure PCTCN2019103919-appb-000112
在手套箱中，取实施例6中制备的催化剂B6(0.01mmol)加入高压釜中，并加入PO(0.01mol)，不充入二氧化碳，并在80℃的条件下反应2h。反应液测核磁以表征单体的转化率以及产物的选择性，直接抽干残余的PO即可得聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。所得聚醚的 1H NMR谱图见图5。
应用例33：利用催化剂B6催化PO与二氧化碳共聚
在手套箱中，取实施例6中制备的催化剂B6(0.01mmol)加入高压釜中，并加入PO(0.01mol)，充入0.5MPa的CO 2并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，直接抽干残余的PO即可得聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例34：利用催化剂B6催化PO与二氧化碳共聚
在手套箱中，取实施例6中制备的催化剂B6(0.01mmol)加入高压釜中，并加入PO(0.01mol)，充入1.5MPa的CO 2并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，直接抽干残余的PO即可得聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
应用例35：利用催化剂B6催化PO与二氧化碳共聚
在手套箱中，取实施例6中制备的催化剂B6(0.01mmol)加入高压釜中，并加入PO(0.01mol)，充入3.0MPa的CO 2并在80℃的条件下反应2h。而后释放二氧化碳，取反应液测核磁以表征单体的转化率以及产物的选择性，直接抽干残余的PO即可得聚合物，干燥后，对聚合物进行GPC的表征。核磁及GPC的表征结果见表1。
表1 为应用例1～35的聚合产物的测试结果
Figure PCTCN2019103919-appb-000113
Figure PCTCN2019103919-appb-000114
1M n:数据分子量，由凝胶渗透色谱法测得； 2PDI:分子量分布，由凝胶渗透色谱法测得。
应用例36：利用催化剂B7及链转移剂制备聚环己烯碳酸酯
Figure PCTCN2019103919-appb-000115
在手套箱中，取实施例7中制备的催化剂B7(0.02mmol)加入高压釜中，加入环己二醇(0.20mmol)作为链转移剂并加入环氧环己烯(0.02mol)，充入1.5MPa的CO 2，并在80℃的条件下反应24h。而后释放二氧化碳，将聚合物在乙醇中沉淀出来，干燥后对聚合物进行核磁和凝胶渗透色谱(GPC)的表征，所得聚碳酸酯的GPC谱图见图6，其数均分子量为11.5kg/mol，多分散性在1.02。
应用例37：利用催化剂B7及聚丙二醇作大分子链转移剂制备聚环己烯碳酸酯-聚丙二醇的嵌段共聚物
Figure PCTCN2019103919-appb-000116
在手套箱中，取实施例7中制备的催化剂B7(0.02mmol)加入高压釜中，加入聚丙二醇(0.20mmol)作为链转移剂并加入环氧环己烯(0.02mol)，充入1.5MPa的CO 2，并在80℃的条件下反应24h。而后释放二氧化碳，将聚合物在乙醇中沉淀出来，干燥后对聚合物进行核磁和凝胶渗透色谱(GPC)的表征。
应用例38：利用催化剂B10制备聚丁二酸环己烯酯
Figure PCTCN2019103919-appb-000117
在手套箱中，取实施例10中制备的催化剂B10(0.01mmol)加入耐压瓶中，加入环氧环己烷(0.01mol)，加入丁二酸酐(0.01mol)，并在60℃的条件下反应24h。将聚合物于石油醚中沉淀，干燥后，可得聚丁二酸环己烯酯。所得聚合物的核磁见图7。
应用例39：利用催化剂B10制备聚马来酸丙烯酯
Figure PCTCN2019103919-appb-000118
在手套箱中，取实施例10中制备的催化剂B10(10.01mmol)加入耐压瓶中，加入环氧丙烷(0.01mol)，加入马来酸酐(0.01mol)，并在60℃的条件下反应24h。将聚合物于石油醚中沉淀，干燥后，可得聚马来酸丙烯酯。
应用例40：利用催化剂B10制备聚环己烯碳酸酯-聚丁二酸环己烯酯嵌段共聚物
Figure PCTCN2019103919-appb-000119
在手套箱中，取实施例10中制备的催化剂B10(0.02mmol)加入高压釜中，并加入环氧环己烯(0.01mol)，丁二酸(2mmol)加入充入0.8MPa的CO 2，并在100℃的条件下反应12h。而后释放二氧化碳，将聚合物在乙醇中沉淀出来，干燥后对聚合物进行核磁和凝胶渗透色谱(GPC)的表征，所得嵌段共聚物的GPC谱图见图8，其数均分子量为15.6kg/mol，多分散性在1.19。
应用例41：利用催化剂B10制备单硫代聚环己烯碳酸酯
Figure PCTCN2019103919-appb-000120
在手套箱中，取实施例10中制备的催化剂B10(0.02mmol)加入高压釜中，并加入环氧环己烯(0.01mol)，充入1.0MPa的COS，并在70℃的条件下反应2h。而后释放COS，将聚合物在乙醇中沉淀出来，干燥后可得单硫代聚环己烯碳酸酯。
应用例42：利用催化剂B12制备聚丙交酯
Figure PCTCN2019103919-appb-000121
在手套箱中，取实施例12中制备的催化剂B12(0.02mmol)加入高压釜中，并加入丙交酯(0.01mol)，加入5毫升氯仿，50℃下反应2h。将聚合物在乙醇中沉淀出来，干燥后可得聚丙交酯。所得聚丙交酯的核磁见图9。
应用例43：利用催化剂B12制备聚磷酸酯
Figure PCTCN2019103919-appb-000122
在手套箱中，取实施例12中制备的催化剂B12(0.02mmol)加入高压釜中，并加入磷酸酯(0.01mol)，加入5ml氯仿，50℃下反应3h。将聚合物在乙醇中沉淀出来，干燥后可得聚磷酸酯，所得聚磷酸酯的核磁见图10。
应用例44：利用催化剂B12制备聚磷酸酯-聚碳酸丙烯酯嵌段共聚物
Figure PCTCN2019103919-appb-000123
在手套箱中，取实施例12中制备的催化剂B12(0.01mmol)加入高压釜中，并加入环氧丙烷(0.01mol)，充入1.5MPa的CO 2，并在80℃的条件下反应2h。而后释放二氧化碳，在手套箱中顺序加入磷酸酯(0.01mol)，50℃下反应3h。取反应液测核磁以表征单体的转化率，从石油醚中沉淀出聚合物，干燥后，对聚合物进行GPC的表征。所得聚磷酸酯-聚碳酸丙烯酯嵌段共聚物的核磁见图11。

Claims (21)

  1. 具有亲电亲核双功能的有机无金属催化剂，其特征在于，具有式(I)所示的化学结构：
    Figure PCTCN2019103919-appb-100001
    式(I)中，各Y 1～Y 3独立地选自下列结构式1～5中的一种或多种：
    Figure PCTCN2019103919-appb-100002
    结构式1～3中各D 1～D 6独立地表示为:
    Figure PCTCN2019103919-appb-100003
    其中，B为硼原子，N为氮原子，P为磷原子，
    Figure PCTCN2019103919-appb-100004
    表示为连接键；
    a、b各自独立地选自0-20的整数，但不可同时取0；各c、d、e独立地选自0-20的整数；当a为0时，各c与d不可同时取0；当b为0时，各e不可同时取0；
    各Z 1～Z 4、R 1、R 2、E 1～E 4独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；其中，各Z 1～Z 3、R 1、R 2、Z 4、E 1～E 4中的两个或两个以上可成键或成环；
    附加条件是：当a＝1时，Z 1不可为C 6的芳香基；当c＝1时，Z 2不可为C 6的芳香基；当d＝1时，Z 3不可为C 6的芳香基；各Z 1～Z 3或R 1、R 2、Z 4不可同时为取代或非取代的芳香基、取代或非取代的杂芳香基的一种或多种；各D 1～D 3和D 4～D 6不可同时为取代或非取代的C 6-C 10芳香基；
    各
    Figure PCTCN2019103919-appb-100005
    表示为负离子；各
    Figure PCTCN2019103919-appb-100006
    独立地以单独负离子形式存在，或者各
    Figure PCTCN2019103919-appb-100007
    与D 1～D 6中 的一种或多种以共价键形式相连。
  2. 根据权利要求1所述的具有亲电亲核双功能的有机无金属催化剂，其特征在于，所述各
    Figure PCTCN2019103919-appb-100008
    独立地选自
    Figure PCTCN2019103919-appb-100009
    磺酸根、高氯酸根、氯酸根、磷酸根、羧酸根、烷氧根、酚氧根中的一种或多种。
  3. 具有亲电亲核双功能的有机无金属催化剂，其特征在于，所述有机无金属催化剂具有如下所示的结构中的一种：
    Figure PCTCN2019103919-appb-100010
    Figure PCTCN2019103919-appb-100011
    其中：
    各i独立地选自1或2；
    各f独立地选自0～3的整数，但任一结构中f不可同时为0；
    g选自3～20的任意整数；
    各h独立地选自0～3的整数，但任一结构中h不可同时为0；
    各n独立地选自0～2的整数；
    各K 1独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 7-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
    各R 3～R 6、R 3’～R 6’、K 2～K 4、K 1’～K 3’独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
    其中，各K 1～K 4、K 1’～K 3’、R 3～R 6、R 3’～R 6’中的两个或两个以上可成键或成环；
    附加条件是：在同一结构中，R 3～R 5不可同时为芳香基或杂芳香基，R 3’～R 5’不可同时为芳香基或杂芳香基；
    A选自N或P原子；
    各G 1’、G 2’独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至20个碳原子的芳香基、5至20个碳原子的杂芳香基中的一种或多种；其中，各G 1’、G 2’可成键或成环，且G 1’、G 2’与K 1或K 2不可同时为取代或非取代的芳香基或杂芳香基；
    各
    Figure PCTCN2019103919-appb-100012
    表示为负离子；各
    Figure PCTCN2019103919-appb-100013
    独立地以单独负离子形式存在，或者各
    Figure PCTCN2019103919-appb-100014
    与R 3～R 6、R 3’～R 6’中的一种或多种以共价键形式相连。
  4. 根据权利要求3所述的具有亲电亲核双功能的有机无金属催化剂，其特征在于，所述各结构中的
    Figure PCTCN2019103919-appb-100015
    各自独立地表示为如下的任意一种或多种：
    Figure PCTCN2019103919-appb-100016
    Figure PCTCN2019103919-appb-100017
    表示为连接键；
    各m独立地选自1～18的任意整数。
  5. 根据权利要求3所述的具有亲电亲核双功能的有机无金属催化剂，其特征在于，所述各结构中的
    Figure PCTCN2019103919-appb-100018
    各自独立地表示为如下的任意一种或多种：
    Figure PCTCN2019103919-appb-100019
    Figure PCTCN2019103919-appb-100020
    表示为连接键；
    各m独立地选自1～18的任意整数。
  6. 根据权利要求3所述的具有亲电亲核双功能的有机无金属催化剂，其特征在于，所述各R 3～R 6、R 3’～R 6’独立地选自未取代的或具有取代基的以下基团：C 1-C 18烷基、C 3-C 18环烷基、C 3-C 18烯基、C 3-C 18炔基、C 6-C 18芳香基、C 3-C 18杂环基、C 5-C 18杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代 基选自卤素原子、具有1至10个碳原子的支链或直链的烃基、1至10个碳原子的支链或直链的烷氧基、3至10个碳原子的支链或直链的环烷基、6至18个碳原子的芳香基、5至18个碳原子的杂芳香基中的一种或多种。
  7. 根据权利要求3所述的具有亲电亲核双功能的有机无金属催化剂，其特征在于，所述各K 1～K 4、K 1’～K 3’独立地选自下列的一种或多种；
    Figure PCTCN2019103919-appb-100021
    各R 7～R 25独立地选自未取代的或具有取代基的以下基团：C 1-C 18烷基、C 3-C 18环烷基、C 3-C 18烯基、C 3-C 18炔基、C 6-C 18芳香基、C 3-C 18杂环基、C 5-C 18杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至10个碳原子的支链或直链的烃基、1至10个碳原子的支链或直链的烷氧基、3至10个碳原子的支链或直链的环烷基、6至12个碳原子的芳香基、5至12个碳原子的杂芳香基中的一种或多种。
  8. 根据权利要求3所述的具有亲电亲核双功能的有机无金属催化剂，其特征在于，所述有机无金属催化剂具有如下所示的结构中的一种：
    Figure PCTCN2019103919-appb-100022
    Figure PCTCN2019103919-appb-100023
  9. 具有亲电亲核双功能的有机无金属催化剂，其特征在于，由至少含一个不饱和键的含氮或磷的反应原料W1，与至少含有一个硼氢键的反应原料W2通过硼氢化反应得到；
    所述反应原料W1的结构式表示为如下的一种或多种：
    Figure PCTCN2019103919-appb-100024
    Figure PCTCN2019103919-appb-100025
    其中：
    各f独立地选自0～3的整数，但任一结构中f不可同时为0；
    g选自3～20的任意整数；
    各p独立地选自0～3的整数，各j独立地选自0～2的整数，但任一结构中p和j不可同时为0；
    各h独立地选自0～3的整数，但任一结构中h不可同时为0；
    各K 1独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 7-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
    各R 3～R 6、R 3’～R 6’、K 2～K 4、K 1’～K 3’独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团； 其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
    其中，各K 1～K 4、K 1’～K 3’、R 3～R 6、R 3’～R 6’中的两个或两个以上可成键或成环；
    附加条件是：在同一结构中，R 3～R 5不可同时为芳香基或杂芳香基；
    A选自N或P原子；
    各
    Figure PCTCN2019103919-appb-100026
    独立地表示为碳碳双键或碳碳三键；
    各
    Figure PCTCN2019103919-appb-100027
    表示为负离子；各
    Figure PCTCN2019103919-appb-100028
    独立地以单独负离子形式存在，或者各
    Figure PCTCN2019103919-appb-100029
    与R 3～R 6、R 3’～R 6’中的一种或多种以共价键形式相连；
    所述反应原料W2的结构式表示为如下的一种或多种：
    Figure PCTCN2019103919-appb-100030
    各G 1、G 2独立地选自未取代的或具有取代基的以下基团：H、卤素、C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至20个碳原子的芳香基、5至20个碳原子的杂芳香基中的一种或多种；其中，各G 1、G 2可成键或成环。
  10. 具有亲电亲核双功能的有机无金属催化剂的制备方法，其特征在于，由至少含一个不饱和键的含氮或磷的反应原料W1，与至少含有一个硼氢键的反应原料W2通过硼氢化反应得到；
    所述反应原料W1的结构式表示为如下的一种或多种：
    Figure PCTCN2019103919-appb-100031
    Figure PCTCN2019103919-appb-100032
    其中：
    各f独立地选自0～3的整数，但任一结构中f不可同时为0；
    g选自3～20的任意整数；
    各p独立地选自0～3的整数，各j独立地选自0～2的整数，但任一结构中p和j不可同时为0；
    各h独立地选自0～3的整数，但任一结构中h不可同时为0；
    各K 1独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 7-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂 芳香基中的一种或多种；
    各R 3～R 6、R 3’～R 6’、K 2～K 4、K 1’～K 3’独立地选自未取代的或具有取代基的以下基团：C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至30个碳原子的芳香基、5至30个碳原子的杂芳香基中的一种或多种；
    其中，各K 1～K 4、K 1’～K 3’、R 3～R 6、R 3’～R 6’中的两个或两个以上可成键或成环；
    附加条件是：在同一结构中，R 3～R 5不可同时为芳香基或杂芳香基；
    A选自N或P原子；
    各
    Figure PCTCN2019103919-appb-100033
    独立地表示为碳碳双键或碳碳三键；
    各
    Figure PCTCN2019103919-appb-100034
    表示为负离子；各
    Figure PCTCN2019103919-appb-100035
    独立地以单独负离子形式存在，或者各
    Figure PCTCN2019103919-appb-100036
    与R 3～R 6、R 3’～R 6’中的一种或多种以共价键形式相连；
    所述反应原料W2的结构式表示为如下的一种或多种：
    Figure PCTCN2019103919-appb-100037
    各G 1、G 2独立地选自未取代的或具有取代基的以下基团：H、卤素、C 1-C 30烷基、C 3-C 30环烷基、C 3-C 30烯基、C 3-C 30炔基、C 6-C 30芳香基、C 3-C 30杂环基、C 5-C 30杂芳香基中的一种或多种，或者为含有O、S、N、Si、P原子中的一种或多种的所述基团；其中所述取代基选自卤素原子、具有1至20个碳原子的支链或直链的烃基、1至20个碳原子的支链或直链的烷氧基、3至20个碳原子的支链或直链的环烷基、6至20个碳原子的芳香基、5至20个碳原子的杂芳香基中的一种或多种；其中，各G 1、G 2可成键或成环。
  11. 根据权利要求10所述的具有亲电亲核双功能的有机无金属催化剂的制备方法，其特征在于，包括：将任一反应原料W1和任一反应原料W2在氮气或惰性气体的保护下混合，加入有机溶剂，在-20～150℃下，搅拌1～500小时进行硼氢化反应，反应结束后，降至室温，去除杂质和有机溶剂，得到具有亲电亲核双功能的有机无金属催化剂。
  12. 根据权利要求11所述的具有亲电亲核双功能的有机无金属催化剂的制备方法，其特征在于，所述有机溶剂选自四氢呋喃、苯、甲苯、氯仿、己烷、乙醚、二氯甲烷、乙酸乙酯、二甲基亚砜、四氯化碳、1,4-二氧六环、吡啶中的一种或多种。
  13. 如权利要求1～9任一所述的有机无金属催化剂在制备高分子材料中的应用，其特征在于，一种或多种环状单体在具有亲电亲核双功能的有机无金属催化剂的接触下发生均 聚合反应或共聚合反应得到高分子材料。
  14. 如权利要求1～9任一所述的有机无金属催化剂在制备高分子材料中的应用，其特征在于，一种或多种环状单体与二氧化碳、二硫化碳、硫氧化碳中的一种或多种在具有亲电亲核双功能的有机无金属催化剂的接触下发生共聚合反应得到高分子材料。
  15. 根据权利要求13或者14所述的有机无金属催化剂在制备高分子材料中的应用，其特征在于，所述环状单体选自如下结构：
    Figure PCTCN2019103919-appb-100038
    Figure PCTCN2019103919-appb-100039
  16. 根据权利要求13或者14所述的有机无金属催化剂在制备高分子材料中的应用，其特征在于，在所述聚合反应体系中可加入一种或多种醇化合物、酸化合物、胺化合物、多元醇、多元羧酸、多元醇酸、水作为链转移剂制备相应的聚合物多元醇。
  17. 根据权利要求16所述的有机无金属催化剂在制备高分子材料中的应用，其特征在于，所述链转移剂选自如下结构：
    Figure PCTCN2019103919-appb-100040
    Figure PCTCN2019103919-appb-100041
  18. 根据权利要求13或者14所述的有机无金属催化剂在制备高分子材料中的应用，其特征在于，在所述聚合反应体系中加入带有醇羟基、酚羟基、氨基、羧基的一种或多种聚合物作为大分子链转移剂制备相应的嵌段共聚物或接枝共聚物。
  19. 根据权利要求18所述的有机无金属催化剂在制备高分子材料中的应用，其特征在于，所述链转移剂选自如下结构：
    Figure PCTCN2019103919-appb-100042
    其中，
    Figure PCTCN2019103919-appb-100043
    表示大分子链转移剂主链。
  20. 根据权利要求13或者14所述的有机无金属催化剂在制备高分子材料中的应用，其特征在于，所述具有亲电亲核双功能的有机无金属催化剂负载在无机载体或有机载体上。
  21. 如权利要求1～9任一所述的有机无金属催化剂在制备高分子材料中的应用，其特征在于，包括：催化二氧化碳与环氧烷烃的共聚合制备脂肪族聚碳酸酯、催化环氧烷烃的开环聚合制备聚醚、催化环氧烷烃和环状酸酐制备聚酯以及催化硫氧化碳和环氧烷烃共聚制备聚硫代碳酸酯。
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