CN114015031A - Lewis acid-base pair catalyst, preparation method and method for catalytically synthesizing polyester - Google Patents

Lewis acid-base pair catalyst, preparation method and method for catalytically synthesizing polyester Download PDF

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CN114015031A
CN114015031A CN202111468780.9A CN202111468780A CN114015031A CN 114015031 A CN114015031 A CN 114015031A CN 202111468780 A CN202111468780 A CN 202111468780A CN 114015031 A CN114015031 A CN 114015031A
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catalyst
phosphonium salt
lewis acid
quaternary phosphonium
phthalic anhydride
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CN114015031B (en
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王晓武
李志波
孙阿斌
李笋
杜娟
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Qingdao University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
    • C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The present invention relates to the field of catalyst synthesis. Aiming at the problems of the existing catalyst such as deficient types, low polymer molecular weight, low initiation efficiency, side reaction and low monomer conversion rate in the polyester generated by the copolymerization of phthalic anhydride and cyclohexene oxide, the Lewis acid-base pair catalyst is provided, and has the structure that:

Description

Lewis acid-base pair catalyst, preparation method and method for catalytically synthesizing polyester
Technical Field
The invention relates to the field of catalyst synthesis, in particular to a Lewis acid-base pair catalyst, a preparation method and a method for catalytically synthesizing polyester.
Background
Polyester is an important high polymer material and can be applied to the fields of fibers, packaging materials, photosensitive materials, insulating materials, biomedical materials and the like. With the increasingly prominent white pollution problem, degradable plastics become one of effective solutions to the problem.
The greatest advantage of ring-opening polymerization of epoxides and cyclic anhydrides is the wide source of raw materials, the wide variety and the possibility of controlled polymerization. Common epoxide monomers are Ethylene Oxide (EO), PO, Butylene Oxide (BO), CHO, etc., and common anhydride monomers are Phthalic Anhydride (PA), Succinic Anhydride (SA), Norbornene Anhydride (NA), Maleic Anhydride (MA), etc. Thus, polyesters having different structures and properties can be obtained,
in 1960, Fischer first reported that organic small-molecule tertiary amine and quaternary ammonium salt catalyze ring-opening copolymerization of various cyclic acid anhydrides and epoxides [ J.Polym.Sci.,1960.44(143):155-172 ].
Liu and Kim used triphenylphosphine (PPh3), Dimethylaminopyridine (DMAP), tetrabutylammonium chloride (TBACl), N-methylimidazole (N-MeIm), TBD and 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) to catalyze the ring-opening alternating copolymerization of nadic anhydride (exo-NA) and CHO [ Macromolecules,2015.48(11):3431- ]3437 ] at 110 ℃.
2017
Figure BDA0003390746030000011
PPNCl, DMAP, PPh3 have also been reported to catalyze the PA and CHO copolymerization reactions. Among them, PPNCl is the most effective catalyst, and the resulting polymer is a highly alternating copolyester (C:)>99%) of polyester with a molecular weight of up to 21kg mol-1. PPNCl is also used for copolymerization of epoxy monomers such as PO, CHO, SO, and MUO, and anhydride monomers such as CHA, SA, and MADGA [ Eur.Polym.J.,2017.88:433-447 ].
2017, Zhao Junpeng et al, first reported the use of phosphazene bases in alternating copolymerization of epoxides and anhydrides. They found the ultrastrong phosphazene base t-BuP4The alternating copolymerization of epoxy and acid anhydride can be achieved, but occurs easily due to the strong basicityIntramolecular or intermolecular transesterification side reactions [ ACS Macro Lett.,2017.6(10): 1094-.
Zhang Xinghong topic group finds that binary acid-base pair systems consisting of TEB and TPB and various onium salts can efficiently catalyze the copolymerization of PO and MA, and the used onium salts comprise: DTMeAB, NBu4Br, NBu4Cl, PPh4Br, PPh4Cl, PPNCl [ prog.Polymer.Sci., 2018.80: 163-.
Recently, a series of metal-free catalysts with electrophilic boron centres coordinated to nucleophilic quaternary ammonium salts were developed by Wuchong et al and used for PA and CHO copolymerisation [ Angew. chem. int. Ed.10.1002/anie.202104981 ].
The existing catalysts are relatively deficient, and when the catalysts are used for catalyzing the bulk copolymerization of phthalic anhydride and cyclohexene oxide to generate polyester, the existing polymers have the problems of low molecular weight, low initiation efficiency, side reaction and low monomer conversion rate.
Disclosure of Invention
The invention aims to provide a Lewis acid-base pair catalyst, a preparation method and a method for catalytically synthesizing polyester, aiming at the problems that the existing catalyst is relatively deficient in types, the molecular weight of a polymer generated by bulk copolymerization of phthalic anhydride and cyclohexene oxide is not high, the initiation efficiency is low, side reactions exist and the monomer conversion rate is low.
The technical scheme provided by the invention is as follows:
in one aspect, the invention provides a lewis acid-base pair catalyst having a bridged phosphonium salt functionalized organoboron having the structure:
Figure BDA0003390746030000021
wherein n is 1, 2, 3 or 4, and X is Cl, Br or I.
In another aspect, the present invention provides a process for preparing the above lewis acid-base pair catalyst, comprising the steps of:
(1) dissolving triphenylphosphine and halogenated olefin in toluene, heating at 70 ℃ for 48h, adding ether with volume being three times that of the solvent into the reaction mixture, freezing in a refrigerator, filtering white solid in vacuum when cooling, washing with ether, and drying the white solid in vacuum at 40 ℃ to obtain quaternary phosphorus salt;
(2) the quaternary phosphonium salt and 9-borabicyclo [3.3.1] nonane were added in a glove box to a previously dried pressure-resistant flask equipped with a stirring magneton, chloroform was added and heated at 80 ℃ for 24 hours, and the reaction mixture was concentrated in vacuo to obtain a crude solid product, which was further purified by washing with n-hexane and then dried in vacuo at 40 ℃ for 12 hours.
Further, the halogenated olefin in the step (1) has a structural formula:
Figure BDA0003390746030000022
wherein n is 1, 2, 3 or 4, and X is Cl, Br or I.
Further, the quaternary phosphonium salt in the step (1) has a structural formula:
Figure BDA0003390746030000023
wherein n is 1, 2, 3 or 4, and X is Cl, Br or I.
Further, the quaternary phosphonium salt in the step (1) has a structural formula of any one of the following 1-6:
Figure BDA0003390746030000024
Figure BDA0003390746030000031
further, the molar ratio of triphenylphosphine to halogenated olefin for synthesizing the quaternary phosphonium salt in the step (1) is 1: 1.5.
Further, the molar ratio of the quaternary phosphonium salt synthesized by the step (2) to the 9-borabicyclo [3.3.1] nonane is 1: 1.05-1: 1.35.
Further, the catalysts synthesized in the step (2) are respectively a C3 phosphorus salt catalyst, a C4 phosphorus salt catalyst, a C5 phosphorus salt catalyst or a C6 phosphorus salt catalyst, and the structural formula is as follows:
Figure BDA0003390746030000032
the invention also provides a method for catalytically synthesizing polyester, which takes anhydride and epoxy monomers as raw materials and carries out ring-opening polymerization under the catalysis of the Lewis acid-base on a catalyst to generate an alternating copolymer.
Further, the acid anhydride is phthalic anhydride PA, exo-NA, THPA, CA, SA, MA or DGA;
Figure BDA0003390746030000041
the epoxy monomer is cyclohexene oxide and is CHO, EO, PO, HO, AGE, LO, BO, NBGE, SO, AGE, FGE, PGE, BGE or ECH.
Figure BDA0003390746030000042
Further, phthalic anhydride, a catalyst and cyclohexene oxide are weighed in a pressure-resistant bottle which is provided with a magnetic stirrer and is subjected to flame drying in advance, the molar ratio of the cyclohexene oxide to the phthalic anhydride to the catalyst is (400-15000): 200-10000): 1, the pressure-resistant bottle is sealed and then taken out for heating reaction, the reaction temperature is controlled to be 100-150 ℃, and the reaction time is controlled to be 0.3-6 h.
Further, the mol ratio of the cyclohexene oxide, phthalic anhydride and the catalyst is (1500-4000) to (1000-3000): 1.
further, the molar ratio of cyclohexene oxide, phthalic anhydride and catalyst is 1000:1000: 1. 1500: 1000: 1. 2000: 2000: 1. 2500: 2000: 1. 3000: 2000: 1. 4000: 3000: 1 or 6000: 5000: 1.
further, the reaction temperature for catalytically synthesizing the polyester is 100-120 ℃.
By adopting the scheme, when the catalyst generated by reacting the quaternary phosphonium salt with 9-BBN is used for catalyzing the copolymerization of phthalic anhydride and cyclohexene oxide, the problems of poor reaction controllability, low initiation efficiency, side reaction, low monomer conversion rate and the like can be solved. Moreover, the catalyst generated by the reaction does not contain metal, and belongs to metal-free catalysis, so that the poly (CHO-alt-PA) obtained by the method can be applied to many fields.
The molecular weight of the polymer obtained by the invention is within 3800-34000 g/mol, and the molecular weight distribution
Figure BDA0003390746030000043
In the range of 1.2 to 1.4.
Has the advantages that:
(1) compared with the existing organic catalytic system, the catalytic system has the advantages of simple preparation, high activity, convenient use, low cost and wide applicability, and is very suitable for industrial production.
(2) The catalyst system of the invention has the advantages of easily available raw materials, low price, rapid reaction, good controllability of the reaction process, higher initiation efficiency which is 1.5 times of the polymerization rate of the prior reported system, and polymer molecular weight distribution
Figure BDA0003390746030000051
Is relatively narrow (<1.4) high monomer conversion rate>99%) without polyether formation.
(3) In the alternating copolymerization reaction of the epoxy monomer and the acid anhydride, the polymerization reaction is carried out at 120 ℃, and the molecular weight distribution of the prepared polymer
Figure BDA0003390746030000052
Between 1.2 and 1.3, the initiation efficiency can reach 99 percent, the monomer conversion rate can reach 99 percent, and the selectivity can reach 99 percent. Greatly improves the problems of poor reaction control, low initiation efficiency, side reaction, low monomer conversion rate and the like.
Drawings
FIG. 1 is a diagram of a catalyst of the phosphorus salt C3 prepared in preparation example 2.11H NMR spectrum;
FIG. 2 is a diagram of the preparation of the C4 phosphonium salt catalyst prepared in preparation example 2.21H NMR spectrum;
FIG. 3 is a scheme for the preparationPreparation of C5 phosphonium salt catalyst prepared in example 2.31H NMR spectrum;
FIG. 4 is a diagram of the preparation of the C6 phosphonium salt catalyst prepared in preparation example 2.41H NMR spectrum;
FIG. 5 is a preparation of C5 phosphorus salt Cl catalyst1H NMR spectrum;
FIG. 6 is a preparation of C5 phosphorus salt I catalyst1H NMR spectrum;
FIG. 7 is a drawing of the poly (cyclohexene-alt-phthalate) ester prepared in example 121H NMR spectrum;
FIG. 8 is a drawing of the poly (cyclohexene-alt-phthalate) ester prepared in example 1213C NMR spectrum;
FIG. 9 is a representative GPC chart of poly (cyclohexene-alt-phthalate) ester prepared in example 6;
FIGS. 9-11 are representative GPC charts of poly (cyclohexene-alt-phthalate) esters prepared in example 11;
FIGS. 9-11 are representative GPC charts of poly (cyclohexene-alt-phthalate) esters prepared in example 13;
FIG. 12 shows the polymerization mechanism of anhydride and epoxy monomers in the presence of a catalyst according to an example.
FIG. 13 is a comparison of the activity of the synthesized C5 phosphonium salt catalyst of preparative example 2.3 and the reported ammonium salt catalyst;
FIG. 14 shows the kinetics of alternate phthalic anhydride/cyclohexene oxide copolymerization initiated by a phosphonium salt catalyst C5;
FIG. 15 is the kinetics of ammonium salt bridged functionalized boron R3 initiated alternating phthalic anhydride/cyclohexene oxide copolymerization.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments and the accompanying drawings.
Preparation examples 1.1 to 1.5 preparation of Quaternary phosphonium salts
Triphenylphosphine and halogenated olefin are selected to prepare the quaternary phosphonium salt, and the specific operation of the preparation examples 1.1-1.5 is as follows.
Preparation example 1.1
Triphenylphosphine (0.262g, 1mmol, 1 equiv.) and 3-bromopropane (0.13mL, 1.5mmol, 1.5 equiv.) were dissolved in toluene (5mL) and heated at 70 ℃ for 48 h. The reaction mixture was concentrated in vacuo to afford the crude product, which was further purified by washing three times with diethyl ether. The white solid was collected by vacuum filtration and dried under vacuum at 40 ℃ for 12 hours.
Preparation example 1.2
Triphenylphosphine (0.262g, 1mmol, 1 eq.) and 4-bromo-1-butene (0.15mL, 1.5mmol, 1.5 eq.) were dissolved in toluene (5mL) and heated at 70 ℃ for 48 h. The reaction mixture was added to three times the volume of the solvent in ether, and frozen in a refrigerator. The white solid was filtered through vacuum while cooling and washed three times with diethyl ether. The white solid was dried under vacuum at 40 ℃ for 12 h.
Preparation example 1.3
Triphenylphosphine (0.262g, 1mmol, 1 equiv.) and 5-bromo-1-pentene (0.18mL, 1.5mmol, 1.5 equiv.) were dissolved in toluene (5mL) and heated at 70 ℃ for 48 h. To the reaction mixture was added three times the volume of the solvent of diethyl ether, and the mixture was frozen in a refrigerator. The white solid was filtered through vacuum while cooling and washed three times with diethyl ether. The white solid was dried under vacuum at 40 ℃ for 12 h.
Preparation example 1.4
Triphenylphosphine (0.262g, 1mmol, 1 eq.) and 6-bromo-1-hexene (0.2mL, 1.5mmol, 1.5 eq.) were dissolved in toluene (5mL) and heated at 70 ℃ for 48 h. To the reaction mixture was added three times the volume of the solvent of diethyl ether, and the mixture was frozen in a refrigerator. The white solid was filtered through vacuum while cooling and washed three times with diethyl ether. The white solid was dried under vacuum at 40 ℃ for 12 h.
Preparation example 1.5
Triphenylphosphine (0.089g, 0.34mmol, 1 equiv.) and 5-iodo-1-pentene (0.065mL, 0.51mmol, 1.5 equiv.) were dissolved in toluene (3mL) and heated at 70 ℃ for 48 h. To the reaction mixture was added three times the volume of the solvent of diethyl ether, and the mixture was frozen in a refrigerator. The white solid was filtered through vacuum while cooling and washed three times with diethyl ether. The white solid was dried in vacuo at 40 ℃ for 24 hours.
Preparation example 1.6
The product of preparation 1.3 (300mg, 0.8mmol) was dissolved in methanol (10mL) and added to ion exchange resin Amberlite IRA-400(Cl) (3g) and stirred at room temperature for 24 h. Filtration, spin-drying of the solvent, washing with hexane (20mL) and filtration of the resulting white solid under vacuum while cooling and washing three times with ether (10 mL). The white solid was dried in vacuo at 40 ℃ for 24 hours.
TABLE 1 preparation examples 1.1 to 1.6 product structures
Figure BDA0003390746030000071
Preparation examples 2.1 to 2.4 preparation of phosphonium salt catalysts
The preparation method of the phosphorus salt catalyst comprises the following specific operations of preparation examples 2.1-2.4 by selecting a quaternary phosphonium salt and 9-borabicyclo [3.3.1] nonane (9-BBN).
Preparation example 2.1
C3 phosphonium salt (0.192g, 0.5mmol, 1 equiv.) and 9-borabicyclo [3.3.1] nonane (0.823g, 0.675mmol, 1.35 equiv.) were added in a glove box to a previously dried pressure-resistant flask equipped with a stirring magneton. Chloroform (8mL) was added and heated at 80 ℃ for 24 hours. The reaction mixture was concentrated in vacuo to obtain a crude solid product, which was further purified by washing three times with n-hexane. The white solid product was dried under vacuum at 40 ℃ for 12 h.
Preparation example 2.2
C4 phosphonium salt (0.25g, 0.63mmol, 1 equiv.) and 9-borabicyclo [3.3.1] nonane (0.081g, 0.662mmol, 1.05 equiv.) were added in a glove box to a previously dried pressure-resistant flask equipped with a stirring magneton. Chloroform (10mL) was added and heated at 80 ℃ for 24 h. The reaction mixture was concentrated in vacuo to obtain a crude solid product, which was further purified by washing three times with n-hexane. The white solid product was dried under vacuum at 40 ℃ for 12 h.
Preparation example 2.3
C5 phosphonium salt (0.103g, 0.25mmol, 1 equiv.) and 9-borabicyclo [3.3.1] nonane (0.032g, 0.2625mmol, 1.05 equiv.) were added in a glove box to a previously dried pressure-resistant flask equipped with a stir magneton. Chloroform (5ml) was added and heated at 80 ℃ for 24 h. The reaction mixture was concentrated in vacuo to obtain a crude solid product, which was further purified by washing three times with n-hexane. The white solid product was dried under vacuum at 40 ℃ for 12 h.
Preparation example 2.4
C6 phosphonium salt (0.120g, 0.24mmol, 1 equiv.) and 9-borabicyclo [3.3.1] nonane (0.04g, 0.36mmol, 1.5 equiv.) were added in a glove box to a previously dried pressure-resistant flask equipped with a stirring magneton. Chloroform (5mL) was added and heated at 80 ℃ for 72 h. The reaction mixture was concentrated in vacuo to obtain a crude solid product, which was further purified by washing three times with n-hexane. The white solid product was dried under vacuum at 40 ℃ for 12 h.
In addition, a C5 phosphorus salt Cl catalyst and a C5 phosphorus salt I catalyst are synthesized.
TABLE 2 phosphonium salt catalyst structures
Figure BDA0003390746030000081
EXAMPLES 1 to 14 preparation of polyesters
Setting Phthalic Anhydride (PA), a catalyst and cyclohexene oxide (CHO) in a glove box, weighing into a small bottle of a pressure-resistant bottle which is provided with a magnetic stirrer and is flame-dried in advance, sealing the small bottle, taking out, heating and reacting, setting the temperature of 100-150 ℃ as a reaction temperature, controlling the molar ratio of the catalyst to the PA and the CHO to be 1:200: 400-1: 10000:15000, and controlling the reaction time to be 0.3-6 h. The specific operation of examples 1 to 14 is as follows, the key data being collated in Table 1.
Example 1
A10 mL pressure bottle was charged with C3 phosphonium salt catalyst (20.38. mu. mol, 10.3mg), then PA (4.08mmol, 603mg, 200 equiv.), CHO (8.15mmol,0.83mL,400 equiv.) and the reaction mixture stirred for 0.3h at 120 ℃ with a molecular weight distribution of 6700g/mol Mn determined by GPC and a molecular weight distribution of 6700g/mol
Figure BDA0003390746030000082
Is 1.2.
Example 2
A10 mL pressure bottle was charged with C4 phosphonium salt catalyst (20.38. mu. mol, 10.6mg), then PA (4.08mmol, 603mg, 200 equivalents), CHO (8.15mmol,0.83mL,400 equivalents) were added and the reaction mixture was stirred for 0.67h at 120 ℃ with a number average molecular weight Mn of 11000g/mol as determined by GPC and a molecular weight distribution of 11000g/mol
Figure BDA0003390746030000091
Is 1.2.
Example 3
A10 mL pressure bottle was charged with C6 phosphonium salt catalyst (20.38. mu. mol, 10.9mg), then PA (4.08mmol, 603mg, 200 equivalents), CHO (8.15mmol,0.83mL,400 equivalents) were added and the reaction mixture was stirred for 0.67h at 120 ℃ C, a GPC measured molecular weight Mn of 9600g/mol, molecular weight distribution
Figure BDA0003390746030000092
Is 1.2.
Example 4
A10 mL pressure bottle was charged with C4 phosphonium salt catalyst (20.38. mu. mol, 10.6mg), then PA (4.08mmol, 603mg, 200 equivalents), CHO (8.15mmol,0.83mL,400 equivalents) were added and the reaction mixture was stirred for 0.67h at 100 ℃ with a number average molecular weight Mn of 4700g/mol and a molecular weight distribution by GPC
Figure BDA0003390746030000093
Is 1.2.
Example 5
A10 mL pressure bottle was charged with C5 phosphonium salt catalyst (20.38. mu. mol, 10.9mg), then PA (4.08mmol, 603mg, 200 equivalents), CHO (8.15mmol,0.83mL,400 equivalents) were added and the reaction mixture was stirred for 0.67h at 100 ℃ with a number average molecular weight Mn of 9800g/mol as determined by GPC and a molecular weight distribution
Figure BDA0003390746030000094
Is 1.2.
Example 6
Withstand voltage of 10mLInto a bottle, C5 phosphonium salt catalyst (4.76. mu. mol, 2.2mg) was added, then PA (4.08mmol, 603mg, 1000 equiv.), CHO (4.08mmol,0.42mL,1000 equiv.) were added and the reaction mixture was stirred for 2.5h at 100 ℃ with a number average molecular weight Mn of 19000g/mol, molecular weight distribution by GPC, molecular weight distribution
Figure BDA0003390746030000095
Is 1.2.
Example 7
A10 mL pressure bottle was charged with C5 phosphonium salt catalyst (4.76. mu. mol, 2.2mg), then PA (4.08mmol, 603mg, 1000 equiv.), CHO (4.08mmol,0.42mL,1000 equiv.) and the reaction mixture stirred for 0.33h at 150 ℃ C. and a number average molecular weight Mn of 26800g/mol as determined by GPC, molecular weight distribution
Figure BDA0003390746030000096
Is 1.2.
Example 8
A10 mL pressure bottle was charged with C5 phosphonium salt catalyst (4.76. mu. mol, 2.2mg), then PA (4.08mmol, 603mg, 1000 equiv.), CHO (4.08mmol,0.42mL,1000 equiv.) and the reaction mixture stirred for 0.33h at 150 ℃ with a molecular weight distribution of 25000g/mol Mn determined by GPC and a number average molecular weight of 25000g/mol
Figure BDA0003390746030000097
Is 1.2.
Example 9
A10 mL pressure bottle was charged with C5 phosphonium salt catalyst (4.76. mu. mol, 2.2mg), then PA (4.08mmol, 603mg, 1000 equiv.), CHO (6.12mmol,0.62mL,1500 equiv.) and the reaction mixture stirred for 0.5h at 150 ℃ with a molecular weight Mn of 22700g/mol, molecular weight distribution by GPC, and
Figure BDA0003390746030000098
is 1.2.
Example 10
A10 mL pressure bottle was charged with C5 phosphonium salt catalyst (2.04. mu. mol, 1.1mg) followed by PA (4.08mmol, 603 mg)2000 equiv.), CHO (5.1mmol,0.52mL,2500 equiv.), stirring the reaction mixture for 1.17h at a reaction temperature of 150 ℃ with a number average molecular weight Mn of 30500g/mol, molecular weight distribution by GPC
Figure BDA0003390746030000102
Is 1.2.
Example 11
A10 mL pressure bottle was charged with C5 phosphonium salt catalyst (2.04. mu. mol, 1.1mg), then PA (4.08mmol, 603mg, 2000 equiv.), CHO (6.12mmol,0.62mL,3000 equiv.) and the reaction mixture stirred for 1.17h at 150 ℃ with a molecular weight distribution of 28500g/mol Mn as determined by GPC and a number average molecular weight of 28500g/mol
Figure BDA0003390746030000103
Is 1.2.
Example 12
A10 mL pressure bottle was charged with C5 phosphonium salt catalyst (2.04. mu. mol, 1.1mg), then PA (6.12mmol, 906mg, 3000 equivalents), CHO (8.16mmol,0.83mL,3000 equivalents) was added and the reaction mixture was stirred for 2h at 150 ℃ with a number average molecular weight Mn of 34000g/mol and a molecular weight distribution by GPC
Figure BDA0003390746030000104
Is 1.3.
Example 13
A10 mL pressure bottle was charged with C5 phosphonium salt catalyst (2.04. mu. mol, 1.1mg), then PA (10.2mmol, 1510mg, 5000 equivalents), CHO (12,24mmol,1.25mL,6000 equivalents) were added and the reaction mixture was stirred for 2h at 150 ℃ with a number average molecular weight Mn of 30500g/mol, molecular weight distribution determined by GPC
Figure BDA0003390746030000105
Is 1.3.
Example 14
A10 mL pressure bottle was charged with C5 phosphonium salt catalyst (2.04. mu. mol, 1.1mg), then PA (20.4mmol, 3020mg, 10000 equiv.), CHO (30.6mmol,3.12mL,15000 equiv.) and the reaction mixture was stirred for 6h to reactAt a temperature of 150 ℃, the number average molecular weight Mn measured by GPC was 24400g/mol, the molecular weight distribution
Figure BDA0003390746030000106
Is 1.4.
TABLE 3 summary of Key data from examples 1-16
Figure BDA0003390746030000101
Figure BDA0003390746030000111
From the results of experiment 2, the C4 phosphonium salt catalyst has a very good catalytic effect, becomes sticky within about 20min, reacts completely within 40min and has a conversion rate of 97%, and in the subsequent polymerization attempts, the C5 phosphonium salt catalyst in experiment 3 can react completely within about 15min, and the conversion rate reaches 99% within 40 min.
As can be seen from the nuclear magnetic conversion rate of the product, the activity of the phosphorus salt catalyst is improved along with the increase of carbon chains, under the same reaction conditions, the conversion rate of the C5 phosphorus salt catalyst is far higher than that of the C4 phosphorus salt catalyst, and the activity of the C5 catalyst is the best compared with that of the phosphorus salt catalysts with other carbon chain lengths, so that the C5 phosphorus salt catalyst is mainly concentrated.
In polymerization experiment 5, the C5 phosphonium salt catalyst reached 96% conversion at 100 ℃ at a CHO/PA/Cat ratio of 400:200: 1.
In an attempt to amplify the equivalents in experiment 7, at a molar ratio of CHO/PA/Cat 1000:1000:1, the conversion was not high enough to reach 150 ℃ and analysis suggested that too high a polymer viscosity affected mass transfer leading to incomplete final reaction.
Experiment 8 prolonged the reaction time and found that although the conversion rate was increased, the molecular weight distribution was broadened.
Experiment 9 the amount of CHO was subsequently increased to a 1.5-fold excess, and the conversion was found to reach 96%. Increasing the amount of CHO allows a portion of the CHO to act as a solvent, enhancing mass transfer and allowing the reaction to proceed more completely.
Experiments 10-14 continued to scale up the monomer to initiator ratio and from the results it was found that when the molar ratio of CHO/PA/Cat 15000:10000:1, the reaction still proceeded well and that at 150 ℃ for 6h the conversion still reached 96%. The catalyst amounts are used in ppm order.
FIG. 13 is a graph comparing the activities of the C5 phosphonium salt catalyst synthesized in preparative example 2.3 with the reported ammonium salt catalyst, the apparent rate constant for the reaction of the C5 phosphonium salt catalyst is-0.0741, and the apparent rate constant of the ammonium salt catalyst is-0511, by which the phosphonium salt catalyst synthesized is 1.5 times the polymerization rate of the reported ammonium salt catalyst. (catalyst/PA/CHO ═ 1:200:1000, in bulk,120 ℃ C.).
FIG. 14 shows the kinetics of alternate phthalic anhydride/cyclohexene oxide copolymerization initiated by catalyst C5 phosphonium salt catalyst (catalyst/phthalic anhydride/cyclohexene oxide ═ 1:200:1000, bulk polymerization, 120 ℃ C.).
Figure 15 ammonium salt bridged functionalized boron R3 initiated phthalic anhydride/epoxycyclohexane alternating copolymerization kinetics (initiator/phthalic anhydride/epoxycyclohexane ═ 1:200:1000, bulk polymerization, 120 ℃).
Figure BDA0003390746030000121
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.

Claims (10)

1. A lewis acid-base pair catalyst having a bridging phosphonium salt functionalityAn organoboron having the structure:
Figure FDA0003390746020000011
wherein n is 1, 2, 3 or 4, and X is Cl, Br or I.
2. A process for preparing the lewis acid-base pair catalyst of claim 1, comprising the steps of:
(1) dissolving triphenylphosphine and halogenated olefin in toluene, heating at 70 ℃ for 48h, adding ether with volume being three times that of the solvent into the reaction mixture, freezing in a refrigerator, filtering white solid in vacuum when cooling, washing with ether, and drying the white solid in vacuum at 40 ℃ to obtain quaternary phosphorus salt;
(2) the quaternary phosphonium salt and 9-borabicyclo [3.3.1] nonane were added in a glove box to a previously dried pressure-resistant flask equipped with a stirring magneton, chloroform was added and heated at 80 ℃ for 24 hours, and the reaction mixture was concentrated in vacuo to obtain a crude solid product, which was further purified by washing with n-hexane and then dried in vacuo at 40 ℃ for 12 hours.
3. The process of claim 2 wherein the haloolefin of step (1) is of the formula:
Figure FDA0003390746020000012
wherein n is 1, 2, 3 or 4, X is Cl, Br or I;
the quaternary phosphonium salt has the structural formula:
Figure FDA0003390746020000013
wherein n is 1, 2, 3 or 4, and X is Cl, Br or I.
4. The method according to claim 2, wherein the quaternary phosphonium salt of step (1) has a structural formula of any one of the following 1 to 6:
Figure FDA0003390746020000014
5. the method of claim 2, wherein the quaternary phosphonium salt synthesized in step (1) has a molar ratio of triphenylphosphine to halogenated olefin of 1: 1.5.
6. The method of claim 2, wherein the molar ratio of the quaternary phosphonium salt of the catalyst synthesized in step (2) to the 9-borabicyclo [3.3.1] nonane is 1:1.05 to 1: 1.35.
7. A method for catalytically synthesizing polyester is characterized in that epoxy monomers and acid anhydrides are used as raw materials, and ring-opening polymerization is carried out under the catalysis of the Lewis acid-base catalyst of claim 1 to generate an alternating copolymer.
8. The method of claim 7, wherein the anhydride is phthalic anhydride, exo-NA, THPA, CA, SA, MA, or DGA; the epoxy monomer is cyclohexene oxide and is CHO, EO, PO, HO, ECH, AGE, LO, BO, NBGE, SO, AGE, FGE, PGE, BGE or ECH.
9. The method according to claim 7, wherein phthalic anhydride, a catalyst and cyclohexene oxide are weighed in a glove box into a pressure bottle which is equipped with a magnetic stirrer and is subjected to flame drying in advance, the molar ratio of the cyclohexene oxide, the phthalic anhydride and the catalyst is (400-15000): 200-10000): 1, the pressure bottle is sealed and then taken out for heating reaction, the reaction temperature is controlled to be 100-150 ℃, and the reaction time is controlled to be 0.3-6 h.
10. The method of claim 7, wherein the molar ratio of cyclohexene oxide, phthalic anhydride and catalyst is (1500-4000) to (1000-3000): 1.
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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
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WO2020144293A1 (en) * 2019-01-09 2020-07-16 Universität Stuttgart Catalyst system for the preparation of high-molecular weight polyether and application thereof

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CN114573962A (en) * 2022-04-01 2022-06-03 安徽海铭塑业有限公司 Degradable food packaging material
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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
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