CN114308120A - Phosphorus salt amphiphilic dual-functional organic catalyst and preparation method and application thereof - Google Patents

Phosphorus salt amphiphilic dual-functional organic catalyst and preparation method and application thereof Download PDF

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CN114308120A
CN114308120A CN202111661001.7A CN202111661001A CN114308120A CN 114308120 A CN114308120 A CN 114308120A CN 202111661001 A CN202111661001 A CN 202111661001A CN 114308120 A CN114308120 A CN 114308120A
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phosphorus salt
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CN114308120B (en
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李志波
王晓武
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Qingdao University of Science and Technology
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Abstract

The invention discloses a phosphorus salt amphiphilic dual-functional organic catalyst and a preparation method and application thereof, belonging to the field of synthesis and application of organic catalysts. The invention solves the problem that the existing organic catalytic system is characterized in that the polymerization reaction can be realized only by mixing two or more components of nucleophilic reagent and electrophilic reagent and even adding a cocatalyst or an initiator. The phosphorus salt amphiphilic bifunctional organic catalyst provided by the invention mixes nucleophilic electrophilic groups and initiating species into a catalytic system, has nucleophilic and electrophilic bifunctional sites, and avoids the use of a complex multicomponent catalytic system. The catalyst can be used for the preparation of high molecular materials such as polyether, polyester, polycarbonate, polythiocarbonate, polythioether and the like, and the synthesis of block or random copolymers thereof, can also be used for carrying out organic small molecule coupling reaction to prepare fine chemicals such as cyclic carbonate, lactone and thio-cyclic carbonate, and has the characteristics of high efficiency, high selectivity, controllability and the like.

Description

Phosphorus salt amphiphilic dual-functional organic catalyst and preparation method and application thereof
Technical Field
The invention relates to a phosphorus salt amphiphilic dual-functional organic catalyst, and a preparation method and application thereof, and belongs to the field of synthesis and application of organic catalysts.
Background
Organic catalysts have attracted attention of researchers due to low cost, easy availability, low biotoxicity and the like, but compared with the application of organic catalysts in organic methodology, organic catalysts are still in the infancy stage in the field of polymer synthesis and preparation, and currently prepared polymer materials comprise: polyesters, polycarbonates, polyethers, polyamides, polysiloxanes, polyurethanes, and the like.
Currently, the commonly used organic catalytic systems mainly comprise the following types: carboxylic acid catalytic systems, pyridine base catalytic systems, nitrogen heterocyclic carbene catalytic systems, nitrogen-containing organic base (guanidino, amidino, amine) catalytic systems, thiourea/urea + amine or thiourea/urea + base (organic strong base or other bases), phosphazene base catalytic systems, etc., which have been used for preparing polycarbonate from alkylene oxide and carbon dioxide, preparing polyester from alkylene oxide and epoxy anhydride, preparing polyether from alkylene oxide by ring-opening polymerization, preparing polyester high molecular material from cyclic lactone by ring-opening polymerization, preparing polycarbonate from cyclic carbonate by ring-opening polymerization, obtaining polyamide from lactam by ring-opening polymerization, preparing polysiloxane from cyclic siloxane by ring-opening polymerization, catalyzing (meth) acrylate polymerization to obtain poly (meth) acrylate, and catalyzing vinyl ether polymerization to obtain functionalized polyethylene.
The polymerization mechanism mainly includes: electrophilic activation of monomer, nucleophilic activation of initiator, synergistic activation of monomer and initiator, and the like. Thiourea/urea + organic bases, phosphazene bases, carbenes and nitrogen-containing organic bases have been reported in literature as ring-opening polymerization of cyclic lactone, alkylene oxide, epoxy silane, cyclic carbonate and other monomers, and active species are obtained by activating an initiator to initiate polymerization reaction, so as to realize chain growth.
The onium salt can be used in polymerization reaction with Lewis acid trialkyl boron to construct acid-base pair or phosphonitrile/alcohol/trialkyl boron to construct multi-component catalytic system. Trialkylboron is used as Lewis acid and electrophilic reagent, can activate monomer to stabilize the chain end of active species of polymer, onium salt and phosphazene/alcohol have nucleophilicity as initiator, and the bi-component or multi-component system can effectively improve the activity and controllability of polymerization reaction. The triethylboron and the phosphazene compounds are used for ring-opening polymerization of alkylene oxide, copolymerization of carbon dioxide and alkylene oxide to prepare polycarbonate, copolymerization of alkylene oxide and heteroatom allene to prepare polycarbonate, copolymerization of epoxy and acid anhydride to prepare polyester and the like as reported in the literature.
However, the existing organic catalytic system is characterized in that the polymerization reaction can be realized only by mixing two or more components of nucleophilic reagent and electrophilic reagent or even adding a cocatalyst or an initiator, which brings difficulty to the reagent operation, accuracy and mechanistic research of the polymerization reaction; the weighing and quantity of the multiple components adds to the error of the experimental operation.
Disclosure of Invention
The invention provides a phosphorus salt amphiphilic dual-functional organic catalyst, a preparation method and application thereof, aiming at solving the problems in the prior art.
The technical scheme of the invention is as follows:
a phosphorus salt amphiphilic dual-functional organic catalyst has the following structural formula:
Figure BDA0003447493990000021
wherein X is an anion, R1And R2Are identical or different substituents, or R1And R2Forming a bond or a ring through a covalent bond, wherein n is an integer of more than 1; y is
Figure BDA0003447493990000022
Wherein R is1、R2And R3Respectively is one or a combination of more than two of hydrogen atoms or substituted/unsubstituted C1-C50 alkyl, C3-C50 cycloalkyl, C3-C50 alkenyl, C3-C50 alkynyl, C6-C50 aryl, C3-C50 heterocyclic radical, C5-C50 hetero or all-carbon aromatic radical containing one or more than two of N, O, P, Si and S atoms.
Further defined, Y is BR3 and the organic catalyst is of the structure:
Figure BDA0003447493990000023
n is an integer of 1 or more, and the kind of the chain is not limited to a carbon chain, but may be other heteroatom carbon chains containing heteroatoms such as Si, N, O, P, S; BR (BR)3Being cyclic boranes or aliphatic or aromatic boranes, R3The structure of (A) is as follows:
Figure BDA0003447493990000024
wherein
Figure BDA0003447493990000031
Is a connecting bond, and m is an integer of 1 to 30.
Further, X is a combination of two or more of a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a hydroxide ion, a nitrate ion, an azide ion, a tetrafluoroborate anion, a lithium tetrakis (pentafluorophenyl) borate anion, a nickel tetracarbonyl anion, a carbonate ion, a sulfonate ion, a phosphate ion, a hypochlorite ion, a carboxylate ion, an alkoxide ion, and a phenoxide ion.
More particularly, the organic catalyst is of the structure:
Figure BDA0003447493990000032
further, the substituents on the phosphine are not limited to benzene rings, and can be substituents of 1-substituted, 2-substituted, 3-substituted, 4-substituted, 5-substituted or multi-ring bridged benzene rings.
Further defined, PhO-May be a mono-substituted phenol or a poly-substituted phenol.
Further, the length of the carbon chain is not limited to 3, and an integer greater than 3 may be used.
Further defined, the organic catalyst has the following structure:
Figure BDA0003447493990000041
further, the substituents on the phosphine are not limited to methyl, but may be ethyl, propyl, butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, or methyl 1-substituted, 2-substituted, 3-substituted, 4-substituted, 5-substituted or other polycycloalkyl and substituted polycycloalkyl substituents.
Further defined, PhO-May be a mono-substituted phenol or a poly-substituted phenol.
Further, the length of the carbon chain is not limited to 3, and an integer greater than 3 may be used.
The amphiphilic bifunctional phosphorus salt is prepared by carrying out hydroboration reaction on SM containing two unsaturated double bonds and a hydroboration reagent containing at least one boron hydrogen bond.
Further limited, the preparation method of the organic catalyst comprises the following steps: mixing SM and a hydroboration reagent in an inert atmosphere, adding an organic solvent, stirring for 1-144 h at-78-100 ℃, and removing organic matters and impurities after the reaction is finished to obtain the phosphorus salt amphiphilic dual-functional organic catalyst.
Further defined, the molar ratio of quaternary phosphonium salt to hydroboration reagent in SM is 1: (2-3).
More particularly, the structure of the SM is as follows:
Figure BDA0003447493990000051
wherein X is an anion, R1And R2Are identical or different substituents, or R1And R2Bonded or cyclized by a covalent bond.
Further, N is an integer of 1 or more, and the kind of the chain is not limited to a carbon chain, and may be other heteroatom carbon chains including heteroatoms such as Si, N, O, P, and S.
In a further definition, R1、R2And R3Respectively is one or a combination of more than two of hydrogen atoms or substituted/unsubstituted C1-C50 alkyl, C3-C50 cycloalkyl, C3-C50 alkenyl, C3-C50 alkynyl, C6-C50 aryl, C3-C50 heterocyclic radical, C5-C50 hetero or all-carbon aromatic radical containing one or more than two of N, O, P, Si and S atoms.
More specifically, X is a combination of two or more of fluoride ion, chloride ion, bromide ion, iodide ion, hydroxide ion, nitrate ion, azide ion, tetrafluoroborate anion, lithium tetrakis (pentafluorophenyl) borate anion, nickel tetracarbonyl anion, carbonate ion, sulfonate ion, phosphate ion, hypochlorite ion, carboxylate ion, alkoxide ion, and phenoxide ion.
More particularly, the hydroboration reagent is a cyclic, aliphatic or aromatic borane containing one or a combination of two or more of the following structures:
Figure BDA0003447493990000052
Figure BDA0003447493990000061
wherein
Figure BDA0003447493990000062
Is a connecting bond, and m is an integer of 1 to 30.
More particularly, the hydroboration reagent is 9-borabicyclo (3,3,1) -nonane.
Further, the organic solvent is one or more of tetrahydrofuran, benzene, toluene, chloroform, dichloromethane, hexane, diethyl ether, carbon tetrachloride, N-dimethylformamide, ethyl acetate, and 1, 4-dioxane, and is mixed in an arbitrary ratio.
The phosphorus salt amphiphilic dual-functional organic catalyst is applied to preparation of organic micromolecules or high molecular materials, wherein the organic micromolecules or the high molecular materials are obtained by ring opening polymerization reaction of one or more than two cyclic monomers under the action of the catalyst, or are obtained by coupling the cyclic monomers with carbon dioxide, carbon disulfide, carbon oxysulfide, isothiocyanate, isocyanate or carbon monoxide under the action of the catalyst.
Further limiting, the specific application method is as follows: mixing a catalyst and a cyclic monomer according to a molar ratio of 1: (200-10000) and reacting for 0.16-6 h at-40-25 ℃, wherein the molecular weight of the obtained polymer is within the range of 1-4640 kg/mol, and the molecular weight distribution is
Figure BDA0003447493990000063
In the range of 1.02 to 1.3.
Further defined, the cyclic monomer comprises one or a combination of more than one of the following structures:
Figure BDA0003447493990000064
Figure BDA0003447493990000071
Figure BDA0003447493990000081
further limiting, the organic small molecule product is carbon dioxide/carbon disulfide and alkylene oxide/episulfide alkane which are subjected to catalytic coupling reaction by a catalyst to obtain cyclic carbonate.
Further limiting, the organic micromolecule product is cyclic lactone obtained by catalytic coupling reaction of CO and alkylene oxide through a catalyst.
Further limiting, the organic small molecule product is sulfur carbon oxide and alkylene oxide/episulfide alkane which are catalyzed and coupled by a catalyst to obtain cyclic thiocarbonate.
More limited, the polymer is aliphatic polycarbonate or polyether obtained by catalytic copolymerization of carbon dioxide and alkylene oxide through a catalyst.
Further limited, the polymer is polyether obtained by catalyzing ring-opening polymerization of alkylene oxide by a catalyst; the polythioether is obtained by the ring-opening polymerization of the episulfide under the catalysis of a catalyst; polyester obtained by catalyzing alkylene oxide and cyclic anhydride by a catalyst; polyester obtained by catalyzing poly-heteroatom carbonate obtained by copolymerizing heteroatom allene and heteroatom cyclic compound by using a catalyst; the polyester is obtained by catalytic polymerization of alkylene oxide and carbon monoxide in the presence of a catalyst.
More particularly, polyether-polyester, polyester-polycarbonate, polyether-polycarbonate diblock, triblock, multiblock, gradient, or random copolymers are prepared by adjusting the order of addition of alkylene oxide, anhydride, cyclic lactone, carbon dioxide.
More particularly, the organic catalysts CAT1-CAT6 and CAT13-CAT18 are used for catalyzing homopolymerization or copolymerization of Ethylene Oxide (EO), Propylene Oxide (PO), Butylene Oxide (BO), epoxycyclohexyl (CHO), Limonene Oxide (LO), 4-vinylcyclohexene oxide (CVHO) or Allyl Glycidyl Ether (AGE) to obtain polyether, or used for catalyzing copolymerization of Ethylene Oxide (EO), Propylene Oxide (PO), Butylene Oxide (BO), epoxycyclohexyl (CHO), Limonene Oxide (LO), 4-vinylcyclohexene oxide (CVHO) or Allyl Glycidyl Ether (AGE) and CO2 to obtain polycarbonate or cyclic carbonate.
More particularly, the organic catalysts CAT1-CAT6 and CAT13-CAT18 are used to catalyze the copolymerization of Ethylene Oxide (EO), Propylene Oxide (PO), Butylene Oxide (BO), cyclohexyl oxide (CHO), Limonene Oxide (LO), 4-vinylcyclohexene oxide (CVHO) or Allyl Glycidyl Ether (AGE) with cyclic Maleic Anhydride (MA), Succinic Anhydride (SA), Diethylene Glycol Anhydride (DGA) or Phthalic Anhydride (PA) to give polyesters.
More particularly, the organic catalysts CAT1-CAT2 and CAT6 are used for catalyzing EO, PO, BO or AGE homopolymerization or copolymerization to obtain polyether, and the polymerization reaction is active polymerization.
More particularly, the organic catalysts CAT1-CAT2 and CAT6 are used for catalyzing ring-opening polymerization or copolymerization of Lactide (LA), beta-butyrolactone (beta-BL), gamma-butyrolactone (gamma-BL), delta-valerolactone (delta-VL) or epsilon-caprolactone (epsilon-CL) to obtain the polyester.
More particularly, the organic catalysts CAT1-CAT2 and CAT6 are used for catalyzing the copolymerization of Ethylene Sulfide (ES), Propylene Sulfide (PS), cyclohexane sulfide (CHS) and carbon dioxide to obtain polythiocarbonate; or for catalyzing 2-phenylthiirane (SS) or PS with CO2Copolymerization to obtain cyclic thiocarbonate.
More particularly, the organic catalysts CAT1-CAT2 and CAT6 are used for catalyzing the copolymerization of Propylene Oxide (PO) with carbon oxysulfide to obtain polythiocarbonate, or for catalyzing the copolymerization of Ethylene Sulfide (ES) with carbon oxysulfide or carbon disulfide to obtain polythiocarbonate, or for catalyzing the copolymerization of Propylene Oxide (PO) with carbon disulfide to obtain polyether.
More specifically, when the organic catalyst is used for preparing the polymer, the preparation can be carried out in the presence of a chain transfer agent, so that the molecular weight of the prepared polymer can be regulated (both high and low molecular weight polymers can be prepared), the dosage of the catalyst is reduced, the molecular weight distribution of the polymer is reduced, and the polymer with functional terminal functional groups (such as ester groups, phenol groups, amino groups, hydroxyl groups, azide groups and the like) is prepared.
More particularly, the method comprises the steps of adding one or more alcohol compounds, acid compounds, amine compounds, polyols, polycarboxylic acids, polyols and water into a polymerization reaction system to serve as a chain transfer agent to prepare corresponding polymer polyols or poly-thiol; or adding one or more polymers with alcoholic hydroxyl, phenolic hydroxyl, amino and carboxyl as macromolecular chain transfer agents into a polymerization reaction system to prepare the corresponding block copolymer or graft copolymer.
Further defined, the chain transfer agent comprises one or a combination of more than one of the following structures:
Figure BDA0003447493990000091
Figure BDA0003447493990000101
wherein
Figure BDA0003447493990000102
Represents the main chain of a macromolecular chain transfer agent, and
Figure BDA0003447493990000103
the alcoholic hydroxyl group, phenolic hydroxyl group, amino group or carboxylic acid group shown in the main chain does not represent the actual number of functional groups, and the actual number is an arbitrary integer of 1 or more.
Further, in the preparation of the polymer by the organic catalyst, a Lewis acid, a Lewis base, or other multi-component catalyst or cocatalyst may be added to the polymerization system.
The phosphorus salt amphiphilic dual-functional organic catalyst is loaded on inorganic or organic substances and used for preparing organic micromolecules or high molecular materials, so that the catalyst can be recycled, and the loss of the catalyst to the maximum extent is avoided.
The invention has the following beneficial effects:
(1) the phosphorus salt amphiphilic bifunctional organic catalyst provided by the invention mixes nucleophilic electrophilic groups and initiating species into a catalytic system, has nucleophilic and electrophilic bifunctional sites, and avoids the use of a complex multicomponent catalytic system.
(2) The phosphorus salt amphiphilic bifunctional organic catalyst provided by the invention also has the characteristics of definite structure, accurate components and synergistic catalysis, which is difficult to achieve by the conventional diversified system.
(3) The preparation method of the phosphorus salt amphiphilic bifunctional organic catalyst provided by the invention has the characteristics of easily available raw materials, short and simple synthetic route and the like.
(4) The organic catalyst with double functions of phosphorus salt amphipathy provided by the invention is used for preparing high polymer materials such as polyether, polyester, polycarbonate, polythiocarbonate, polythioether and the like and synthesizing a block or random copolymer thereof, can also be used for preparing fine chemicals such as cyclic carbonate, lactone and thio-cyclic carbonate by carrying out organic micromolecule coupling reaction, and has the characteristics of high efficiency, high selectivity, controllability and the like.
Drawings
FIG. 1 is a drawing of CAT11H NMR spectrum;
FIG. 2 shows CAT21H NMR spectrum;
FIG. 3 of pure PPO1H NMR spectrum;
FIG. 4 is a GPC chart of Effect example 1;
FIG. 5 is a drawing of Poly (AGE)1H NMR spectrum;
FIG. 6 is of Poly (BO)1H NMR spectrum.
Detailed Description
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
Example 1
The synthesis of catalyst CAT1 is as follows:
Figure BDA0003447493990000111
wherein,
Figure BDA0003447493990000112
the molecular structural formula of (A) is as follows:
Figure BDA0003447493990000121
the preparation process comprises the following steps:
in a flame-dried Schlenk vessel, diallyl diphenyl phosphine bromide (173.6mg, 0.5mmol, 1 eq.) and 9-borabicyclo [3.3.1 ]]Nonane (9-BBN) (122mg, 1.0mmol, 2.0 equiv.) is dissolved in 10mL of chloroform. The reaction mixture was allowed to stir at 80 ℃ for 12 hours. Removing all volatiles and washing the resulting with hexaneWhite solid 3 times (10mL) to give the desired product in quantitative yield1The H NMR spectrum is shown in FIG. 1 (400MHz, CDCl)3，298K)。
Example 2
The synthesis of catalyst CAT2 is as follows:
Figure BDA0003447493990000122
wherein,
Figure BDA0003447493990000131
the molecular structural formula of (A) is as follows:
Figure BDA0003447493990000132
the preparation process comprises the following steps:
in a flame-dried Schlenk vessel, diallyl diphenyl phosphine iodide (307mg, 0.78mmol, 1 eq.) and 9-borabicyclo [3.3.1 ] were placed]Nonane (9-BBN) (190.4mg, 1.56mmol, 2 equiv.) is dissolved in 10mL CHCl3In (1). The reaction mixture was allowed to stir at 80 ℃ for 12 hours. All volatiles were removed and the resulting white solid was washed 3 times with hexanes (10mL) to give the desired product in quantitative yield, product1The H NMR spectrum is shown in FIG. 2 (400MHz, CDCl)3，298K)。
Example 3
The synthesis of catalyst CAT4 is as follows:
Figure BDA0003447493990000133
the preparation process comprises the following steps:
CAT1(118.3mg, 0.2mmol, 1 equiv.) and sodium benzoate (115.3mg, 0.8mmol, 4 equiv.) were dissolved in 8ml of CHCl in a flame-dried Schlenk vessel3In (1). The reaction mixture was allowed to stir at room temperature for 48 hours. Filtering under nitrogen atmosphere to collect filtrate, and removing all volatile componentsThe resulting white oil was washed 3 times with hexane (10mL) to obtain the desired white quantitative product.
Example 4
The synthesis of catalyst CAT5 is as follows:
Figure BDA0003447493990000141
the preparation process comprises the following steps:
CAT1(118.3mg, 0.2mmol, 1 equiv.) and sodium acetate (65.6mg, 0.8mmol, 4 equiv.) were dissolved in 8ml of chloroform in a flame-dried Schlenk vessel. The reaction mixture was allowed to stir at room temperature for 48 hours. The filtrate was collected by filtration under a nitrogen atmosphere, all volatiles were removed, and the resulting white oil was washed 3 times with hexane (10mL) to obtain the desired white quantitative product.
Example 5
The synthesis of catalyst CAT6 is as follows:
Figure BDA0003447493990000142
the preparation process comprises the following steps:
CAT1(118.3mg, 0.2mmol, 1 equiv.) and sodium trifluoroacetate (108.8mg, 0.8mmol, 4 equiv.) were dissolved in 8ml of chloroform in a flame-dried Schlenk vessel. The reaction mixture was allowed to stir at room temperature for 48 hours. The filtrate was collected by filtration under a nitrogen atmosphere, all volatiles were removed, and the resulting white oil was washed 3 times with hexane (10mL) to obtain the desired white quantitative product.
Effect example 1
The catalyst CAT1-CAT6 is used for catalyzing the homopolymerization of the propylene oxide, and the synthetic route is as follows:
Figure BDA0003447493990000151
the preparation process comprises the following steps:
in a glove box, weighing PO and a catalyst into a small bottle of a pressure-resistant bottle which is provided with a magnetic stirrer and is flame-dried in advance and is 5mL, taking out the small bottle in a sealed mode, setting the temperature to be 20-25 ℃ as a reaction temperature, controlling the molar ratio of the PO to the catalyst to be 200: 1-10000: 1, and controlling the reaction time to be 10-120 min. The key data of application examples 1-12 are collated in Table 1.
Figure BDA0003447493990000152
Effect example 2
Catalyst CAT1-CAT6 is used for catalyzing alkylene oxide and CO2The copolymerization reaction is carried out by the following synthetic route:
Figure BDA0003447493990000161
the preparation process comprises the following steps:
in a glove box, alkylene oxide and a catalyst are added into a reaction kettle, the reaction kettle is flushed with carbon dioxide with certain pressure, the reaction is carried out under the set temperature condition, and the monomer conversion rate and the selectivity of the product (the proportion of polycarbonate, polyether and cyclic carbonate) are represented by nuclear magnetism. The key data of application examples 13-36 are collated in tables 2-5.
TABLE 2
Figure BDA0003447493990000162
TABLE 3
Figure BDA0003447493990000163
TABLE 4
Figure BDA0003447493990000171
TABLE 5
Figure BDA0003447493990000172
Effect example 3
The catalyst CAT1-CAT6 is used for catalyzing the copolymerization of alkylene oxide and cyclic anhydride, and the synthetic route is as follows:
Figure BDA0003447493990000173
the preparation process comprises the following steps:
in a glove box, taking a proper amount of cyclic anhydride, alkylene oxide and a catalyst, placing the cyclic anhydride, the alkylene oxide and the catalyst in a pressure-resistant bottle, and reacting for 10min-12h at the temperature of 60-180 ℃. Taking reaction liquid to test nuclear magnetism to characterize monomer conversion rate and selectivity of products. Precipitated from methanol, filtered and dried, and the polymer was analyzed by GPC. The key data of application examples 37 to 53 are summarized in tables 6 to 7.
TABLE 6
Figure BDA0003447493990000174
Figure BDA0003447493990000181
TABLE 7
Figure BDA0003447493990000182
Effect example 4
The catalyst CAT1-CAT6 is used for catalyzing the homopolymerization of the cyclic lactone, and the synthetic route is as follows:
Figure BDA0003447493990000183
the preparation process comprises the following steps:
in a glove box, adding a proper amount of cyclic lactone monomer and a catalyst into a pressure-resistant bottle, adding a certain amount of organic solvent, and reacting for 2-12h at the temperature of-10-80 ℃. Taking reaction liquid, testing the conversion rate of nuclear magnetism characterization monomers and the selectivity of the product, filtering the polymer, drying to obtain a polyester target product, and performing GPC test analysis on the polyester target product. The key data of application examples 54 to 55 are collated in Table 8.
TABLE 8
Figure BDA0003447493990000184
Effect example 5
The catalyst CAT7-CAT24 is used for catalyzing the homopolymerization of the cyclic lactone, and the synthetic route is as follows:
Figure BDA0003447493990000191
the catalysts CAT7-CAT24 were prepared in the same manner as CAT1-CAT 6.
The preparation process comprises the following steps:
in a glove box, a proper amount of propylene oxide monomer and a catalyst are added into a pressure-resistant bottle and react for 2 to 12 hours at the temperature of between 25 and 100 ℃. Taking reaction liquid, and testing the conversion rate of nuclear magnetism characterization monomers and the selectivity of products. The key data of application examples 56-61 are collated in Table 9.
TABLE 9
Figure BDA0003447493990000192

Claims (10)

1. A phosphorus salt amphiphilic dual-functional organic catalyst is characterized in that the structural formula of the organic catalyst is as follows:
Figure FDA0003447493980000011
wherein X is an anion, R1And R2Are identical or different substituents, or R1And R2Forming a bond or a ring through a covalent bond, wherein n is an integer of more than 1; y is
Figure FDA0003447493980000012
Wherein R is1、R2And R3Respectively is one or a combination of more than two of hydrogen atoms or substituted/unsubstituted C1-C50 alkyl, C3-C50 cycloalkyl, C3-C50 alkenyl, C3-C50 alkynyl, C6-C50 aryl, C3-C50 heterocyclic radical, C5-C50 hetero or all-carbon aromatic radical containing one or more than two of N, O, P, Si and S atoms.
2. The amphiphilic bifunctional organic catalyst as claimed in claim 1, wherein Y is BR3，BR3Being cyclic boranes or aliphatic or aromatic boranes, R3The structure of (A) is as follows:
Figure FDA0003447493980000013
wherein
Figure FDA0003447493980000014
Is a connecting bond, and m is an integer of 1 to 30.
3. The phosphonium salt amphiphilic bifunctional organic catalyst as claimed in claim 1, wherein X is a combination of two or more of fluoride, chloride, bromide, iodide, hydroxide, nitrate, azide, tetrafluoroborate, lithium tetrakis (pentafluorophenyl) borate, nickel tetracarbonyl, carbonate, sulfonate, phosphate, hypochlorite, carboxylate, alkoxide, phenoxide.
4. The amphiphilic bifunctional organic catalyst of any one of claims 1 to 3, wherein the organic catalyst has the following structure:
Figure FDA0003447493980000021
Figure FDA0003447493980000031
5. the preparation method of the amphiphilic bifunctional organic phosphorus salt catalyst as claimed in any one of claims 1 to 4, wherein the organic phosphorus salt catalyst is obtained by carrying out a hydroboration reaction on SM containing two unsaturated double bonds and a hydroboration reagent containing at least one boron hydrogen bond;
the structure of the SM is as follows:
Figure FDA0003447493980000032
wherein X is an anion, R1And R2Are identical or different substituents, or R1And R2Forming a bond or a ring through a covalent bond, wherein n is an integer of more than 1;
the hydroboration reagent is ring, aliphatic or aromatic borane containing one or more than two of the following structures:
Figure FDA0003447493980000041
wherein
Figure FDA0003447493980000042
Is a connecting bond, and m is an integer of 1 to 30.
6. The method for preparing the amphiphilic bifunctional organic catalyst containing phosphorus salt as claimed in claim 5, wherein the method for preparing the organic catalyst comprises: mixing SM and a hydroboration reagent in an inert atmosphere, adding an organic solvent, stirring for 1-144 h at-78-100 ℃, and removing organic matters and impurities after the reaction is finished to obtain the phosphorus salt amphiphilic dual-functional organic catalyst;
the organic solvent is one or more than two of tetrahydrofuran, benzene, toluene, chloroform, dichloromethane, hexane, diethyl ether, carbon tetrachloride, N-dimethylformamide, ethyl acetate and 1, 4-dioxane which are mixed in any proportion.
7. The application of the phosphorus salt amphiphilic dual-functional organic catalyst in preparation of organic micromolecules or high molecular materials according to any one of claims 1 to 4 is characterized in that the organic micromolecules or high molecular materials are obtained by ring opening polymerization reaction of one or more than two cyclic monomers under the action of a catalyst, or are obtained by coupling the cyclic monomers with carbon dioxide, carbon disulfide, carbon oxysulfide, isothiocyanate, isocyanate or carbon monoxide under the action of a catalyst;
the specific application method comprises the following steps: mixing a catalyst and a cyclic monomer according to a molar ratio of 1: (200-10000) and reacting for 0.16-6 h at-40-25 ℃.
8. The use of the phosphonium salt amphiphilic bifunctional organic catalyst as claimed in claim 7, wherein the cyclic monomer comprises one or more of the following structures:
Figure FDA0003447493980000043
Figure FDA0003447493980000051
Figure FDA0003447493980000061
9. the use of the phosphorus salt amphiphilic bifunctional organic catalyst as claimed in claim 7, wherein the catalyst is used for preparing polymer in the presence of chain transfer agent; the chain transfer agent comprises one or more of the following structures:
Figure FDA0003447493980000062
Figure FDA0003447493980000071
wherein
Figure FDA0003447493980000072
Represents the main chain of a macromolecular chain transfer agent, and
Figure FDA0003447493980000073
the alcoholic hydroxyl group, phenolic hydroxyl group, amino group or carboxylic acid group shown in the main chain does not represent the actual number of functional groups, and the actual number is an arbitrary integer of 1 or more.
10. The phosphorus salt amphiphilic bifunctional organic catalyst as claimed in claim 1 is loaded on inorganic or organic substances for preparing organic small molecule or high molecular material.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114716481A (en) * 2022-05-10 2022-07-08 青岛科技大学 Catalyst and preparation method of functionalized polyether polyol
CN114716660A (en) * 2022-05-10 2022-07-08 青岛科技大学 Method for preparing catalyst and dihydroxy terminated polyether polyol
CN115260241A (en) * 2022-05-10 2022-11-01 青岛科技大学 Organic catalyst, polyester polyol and preparation method of polycarbonate polyol

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160108181A1 (en) * 2013-05-17 2016-04-21 Imperial Innovations Limited Method and catalyst system for preparing polymers and block copolymers
CN109096481A (en) * 2018-08-28 2018-12-28 浙江大学 A kind of preparation method of the catalyst system for being used to prepare the polymer containing polyethers and a variety of polymer containing polyethers
CN110938087A (en) * 2018-09-21 2020-03-31 浙江大学 Organic metal-free catalyst with electrophilic nucleophilic bifunctional, preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160108181A1 (en) * 2013-05-17 2016-04-21 Imperial Innovations Limited Method and catalyst system for preparing polymers and block copolymers
CN109096481A (en) * 2018-08-28 2018-12-28 浙江大学 A kind of preparation method of the catalyst system for being used to prepare the polymer containing polyethers and a variety of polymer containing polyethers
CN110938087A (en) * 2018-09-21 2020-03-31 浙江大学 Organic metal-free catalyst with electrophilic nucleophilic bifunctional, preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114716481A (en) * 2022-05-10 2022-07-08 青岛科技大学 Catalyst and preparation method of functionalized polyether polyol
CN114716660A (en) * 2022-05-10 2022-07-08 青岛科技大学 Method for preparing catalyst and dihydroxy terminated polyether polyol
CN115260241A (en) * 2022-05-10 2022-11-01 青岛科技大学 Organic catalyst, polyester polyol and preparation method of polycarbonate polyol

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