CN106750331B - High-adsorbability polyester material and preparation method thereof - Google Patents

High-adsorbability polyester material and preparation method thereof Download PDF

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CN106750331B
CN106750331B CN201611025656.4A CN201611025656A CN106750331B CN 106750331 B CN106750331 B CN 106750331B CN 201611025656 A CN201611025656 A CN 201611025656A CN 106750331 B CN106750331 B CN 106750331B
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pet
polyester
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cyclodextrin
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CN106750331A (en
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李发学
刘银丽
田梅香
吴德群
王学利
俞建勇
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Donghua University
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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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • 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
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6856—Dicarboxylic acids and dihydroxy compounds

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Abstract

The invention discloses a high-adsorbability polyester material and a preparation method thereof. The polyester is modified PET polyester with amino side groups, and the cyclodextrin or the derivative thereof is chemically immobilized on the molecular chain of the cyclodextrin. The preparation method comprises the following steps: using terephthalic acid, ethylene glycol and diatomic alcohol with amino protecting group as raw materials, preparing modified polyethylene glycol terephthalate through esterification polycondensation, and obtaining polyester with free amino side group through deamination protecting group reaction; and carrying out chemical grafting reaction on the cyclodextrin or the derivative thereof and the amino side group of the N-PET polyester to prepare the modified PET polyester with high adsorbability. The polyester material prepared by the invention has a cyclodextrin annular cavity structure with hydrophilic outside and hydrophobic inside, can form a host-guest inclusion complex with a series of organic and inorganic molecules in a water phase, and is used for adsorbing dye, heavy metal ions and the like in printing and dyeing wastewater and terylene alcoholysis products.

Description

High-adsorbability polyester material and preparation method thereof
Technical Field
The invention belongs to the field of functional polyester materials, and particularly relates to a modification method of polyethylene terephthalate (PET).
Background
The cyclodextrin has the special structure and properties of 'hydrophobic inner cavity and hydrophilic outer wall', and is a 'truncated cone' shaped cyclic oligosaccharide in appearance. Because the cyclodextrin is cheap and easy to obtain and has special structure and property, the cyclodextrin and a series of organic molecules in a water phase can form a host-guest inclusion complex, and the cyclodextrin and the organic molecules can be applied to the fields of adsorption, extraction and the like of environmental pollutants, wherein the chemical immobilization of the cyclodextrin and derivatives thereof becomes an important direction for application and expansion of the cyclodextrin and derivatives thereof. Because the cyclodextrin or the derivative thereof is chemically immobilized, the inherent cavity structure and the excellent properties of the cyclodextrin or the derivative thereof can be well maintained, the violent change and even damage of the cavity structure of the cyclodextrin caused by crosslinking polymerization are avoided, and the defects of good water solubility and difficult recovery of the cyclodextrin can be overcome.
The polyester fiber is low in production cost and easy to obtain, the PET polyester is polyester with short production and processing period and excellent thermodynamic property, is commonly used in the field of engineering plastics, can realize chemical immobilization with cyclodextrin and derivatives thereof by modifying the PET polyester and introducing functional side groups on a polyester macromolecular chain, and is used for adsorbing environmental pollutants and dyes, impurities, heavy metal ions and the like in a polyester alcoholysis product.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-efficiency adsorptive polyester material and a preparation method thereof, synthesizing modified polyester with amino side groups, realizing chemical immobilization of cyclodextrin or derivatives thereof on macromolecular chains thereof, and enabling the polyester to have good mechanical property, chemical reagent resistance and high adsorbability.
In order to solve the problems, the invention provides a high-efficiency adsorption polyester material which is characterized in that the polyester is modified PET polyester (NP-PET) with amino side groups, and cyclodextrin or a derivative thereof is chemically immobilized on a molecular chain of the cyclodextrin or the derivative thereof.
Preferably, the functional side group of the modified PET polyester with the amino side group is an amino group with a protecting group.
The invention also provides a preparation method of the efficient adsorptive polyester material, which is characterized by comprising the following steps:
step 1): placing Terephthalic Acid (PTA), Ethylene Glycol (EG) and a catalyst I in a container under the protection of nitrogen, and carrying out esterification reaction at 220-260 ℃ under the condition of 0.1-0.3 MPa to prepare an ester I, wherein the reaction time is 1.5-3 h; the molar ratio of the addition amount of the terephthalic acid to the addition amount of the ethylene glycol is 1: 1.2-1: 1.5, and the addition amount of the first catalyst is 0.01-0.1% of the mole number of the terephthalic acid;
step 2): placing terephthalic acid, amino-protecting group-containing diatomic alcohol and a catalyst I in a container under the protection of nitrogen, and carrying out esterification reaction at 140-200 ℃ and normal pressure to prepare an esterified substance II, wherein the reaction time is 2-4 h, and the molar ratio of the addition amount of the terephthalic acid to the amino-protecting group-containing diatomic alcohol is 1: 1.2-1: 3; the addition amount of the first catalyst is 0.01-0.1% of the mole number of the terephthalic acid;
step 3): placing the first esterified substance, the first esterified substance and the first catalyst in a container under the protection of nitrogen, and carrying out condensation polymerization reaction at a reaction temperature of 270-290 ℃ to prepare NP-PET polyester, wherein the reaction pressure in the pre-polycondensation stage is 1-50 KPa, the reaction time is 30-60 min, and then entering a high vacuum reaction stage, the reaction pressure is 10-150 Pa, and the reaction time is 2-4 h; the addition amount of the second ester is 5-20% of the mole number of the first ester, and the addition amount of the first catalyst is 0.01-0.1% of the sum of the mole numbers of the two esters;
step 4): selecting a proper amino deprotection reagent, and carrying out deamination protecting group reaction on NP-PET polyester for 10-120 min to obtain N-PET polyester;
step 5): placing the N-PET solution, the cyclodextrin or the derivative thereof and the catalyst II into a container, and reacting for 12-24 h at normal temperature and normal pressure to obtain N-PET-g-CD polyester with high adsorbability; wherein the mass ratio of the cyclodextrin or the derivative thereof to the N-PET is 1: 125-1: 500, and the molar ratio of the cyclodextrin or the derivative thereof to the catalyst II is 1: 1.5-1: 2.
Preferably, the catalyst one in the steps 1) to 3) adopts an organic antimony compound, an organic tin compound or an organic aluminum compound.
Preferably, the diol having an amino protecting group in the step 2) is Boc-aminopropanediol compound, Fmoc-aminopropanediol compound, Boc-aminobutanediol compound or Fmoc-aminobutanediol compound.
Preferably, the amino deprotection reagent in the step 4) adopts HCl gas or trifluoroacetic acid (TFA) solution.
Preferably, the solvent of the N-PET solution in the step 5) is Hexafluoroisopropanol (HFIP).
Preferably, the cyclodextrin or the derivative thereof in the step 5) is carboxymethyl beta-cyclodextrin.
Preferably, the catalyst II in the step 5) adopts a composite catalyst of N-hydroxysuccinimide (NHS) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC. HCl).
Preferably, after the reaction in step 5) is finished, if the product is liquid, the product is precipitated and separated out from excessive ice methanol, and the filtration, washing and vacuum drying are repeated; if the product is solid, the product is repeatedly washed by excessive deionized water and dried in vacuum to obtain the final product N-PET-g-CD.
The esterification product is prepared by direct esterification reaction, and the esterification product needs to be cooled to room temperature under the protection of nitrogen, so as to avoid oxidation. And selecting a proper deprotection reaction reagent according to the amino protecting group, and rapidly and effectively removing the amino protecting group on the NP-PET under the condition of not damaging the molecular structure of a main chain, so that free amino appears on an NP-PET macromolecular chain, and the N-PET with the amino side group is prepared.
The invention adopts a two-step method to prepare the modified PET polyester (NP-PET), the circuit can effectively avoid the damage of the amino protecting group of the dihydric alcohol in the reaction process, and the modified PET copolyester (N-PET) with the amino side group is successfully prepared.
The invention realizes the chemical immobilization of the cyclodextrin or the derivative thereof on the N-PET macromolecular chain, and the finally synthesized product has a complete cyclodextrin special cavity structure and high adsorption performance and can be used for adsorbing dye, impurities, heavy metal ions and the like in printing and dyeing wastewater and polyester alcoholysis products.
Drawings
FIGS. 1a-b are schematic diagrams of the synthesis of an esterified compound according to the present invention;
FIG. 2 is a schematic diagram of the synthesis of the polyester materials (NP-PET and N-PET) provided by the present invention;
in the figure: r1 is an alkyl backbone and R2 is an amino protecting group.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
The chemical structural formula of the synthetic modified PET copolyester (N-PET) provided by the invention is as follows:
Figure BDA0001157581420000031
in the above polyester macromolecular structure, R1Is an alkyl main chain, X is 5 to 20, Y is 100 to 200; the weight average molecular weight is 1-5 ten thousand.
The molecular weight and the molecular weight distribution of the finally synthesized modified PET polyester (N-PET) are tested and analyzed by a Gel Permeation Chromatograph (GPC), and the molecular structure and the composition of the polyester are measured and analyzed by a nuclear magnetic resonance apparatus (N-PET)1HNMR) and Fourier transform infrared spectrometer (FTIR), the intrinsic viscosity of the polyester is tested by an intrinsic viscometer, the melting point of the polyester is tested by a Differential Scanning Calorimeter (DSC), the thermal decomposition temperature of the polyester is tested by a thermogravimetric analyzer (TGA), and the adsorption performance of the polyester in rhodamine b solution is tested by a fluorescence spectrophotometer.
Example 1
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.6mol of Ethylene Glycol (EG) and 0.15mmol of antimony trioxide (Sb)2O3) Placing in a container, carrying out direct esterification reaction at 220 ℃ and 0.2MPa to prepare an ester 1, wherein the reaction time is 1.5h, the feeding molar ratio of PTA to EG is 1:1.2, and the addition amount of the catalyst is 0.03 mol% of PTA; under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 1mol of N-BOC-serinol and 0.1mmol of antimony trioxide (Sb)2O3) Placing in a container, performing direct esterification reaction at 175 deg.C under normal pressure to obtain ester 2, wherein the reaction time is 3h, and the feeding molar ratio of PTA and N-BOC-serinol is 1: 2; wherein the addition amount of the catalyst is 0.02 mol% of the PTA;
(2) after the reaction in the step (1) is finished, 0.2mol of the ester 1, 0.01mol of the ester 2 and 0.105mol of antimony trioxide (Sb) are added under the protection of nitrogen2O3) Placing in a container, performing condensation polymerization at 270 deg.C to obtain modified PET polyester (NP-PET), wherein the reaction pressure in the pre-polycondensation stage is 10KPa, the reaction time is 60min, then entering into high vacuum reaction stage, the reaction pressure is 50Pa, the reaction time is 4h, the addition amount of the ester 2 is 5 mol% of that of the ester 1, and the addition amount of the catalyst is 5 mol% of that of the ester 1Is 0.05 percent of the sum of the two molar esters;
(3) after the reaction in the step (2) is finished, carrying out deamination protection reaction on 10g of NP-PET by using HCl gas under the ambient conditions of normal temperature and pressure for 120min to obtain modified PET polyester (N-PET) with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.05 × 10-4mol of carboxymethyl β -cyclodextrin, 1.58 × 10-4mol NHS and 1.58 × 10-4Putting mol EDC & HCl into a container, and realizing a chemical combination reaction between carboxymethyl β -cyclodextrin and amino side groups on the modified polyester in a Hexafluoroisopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1:500, the feeding molar ratio of carboxymethyl β -cyclodextrin to a catalyst is 1:1.5, and the reaction time is 12h under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.16 × 104The molecular weight distribution is 1.8, the melting point of polyester is 259 ℃, after carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is as high as 95.5%, and the sample can adsorb mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution is as high as 97.5%.
Example 2
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.6mol of Ethylene Glycol (EG) and 0.4mmol of antimony trioxide (Sb)2O3) Placing in a container, performing direct esterification reaction at 230 ℃ and 0.25MPa to prepare an esterified product 1, wherein the reaction time is 2h, the feeding molar ratio of PTA to EG is 1:1.2, and the addition amount of a catalyst is 0.08 mol% of PTA; under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.6mol of N-BOC-serinol and 0.5mmol of antimony trioxide (Sb)2O3) Placing in a container, performing direct esterification reaction at 175 deg.C under normal pressure to obtain ester 2, wherein the reaction time is 3h, and the feeding molar ratio of PTA and N-BOC-serinol is 1: 1.2; wherein the addition amount of the catalyst is 0.1 mol% of the PTA;
(2) after the reaction in the step (1) is finished, 0.2mol of the ester 1, 0.01mol of the ester 2 and 0.168mmol of antimony trioxide (Sb) are added under the protection of nitrogen2O3) Placing the mixture in a container, carrying out condensation polymerization reaction at the reaction temperature of 275 ℃ to prepare NP-PET, wherein the reaction pressure in the pre-polycondensation stage is 20KPa, the reaction time is 60min, then entering a high vacuum reaction stage, the reaction pressure is 40Pa, the reaction time is 5h, the addition amount of the ester 2 is 5 mol% of that of the ester 1, and the addition amount of the catalyst is 0.08% of the sum of the two ester mol%;
(3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using HCl gas under the ambient conditions of normal temperature and normal pressure for 90min to obtain modified PET polyester (N-PET) with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.15 × 10-4mol carboxymethyl β -cyclodextrin, 1.84 × 10-4mol NHS and 1.84 × 10-4Putting mol EDC & HCl into a container, and realizing a chemical combination reaction between carboxymethyl β -cyclodextrin and amino side groups on the modified polyester in a Hexafluoroisopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1: 420, the feeding molar ratio of carboxymethyl β -cyclodextrin to a catalyst is 1: 1.6, and the reaction time is 16h under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.17 × 104The molecular weight distribution is 2.1, the melting point of the polyester is 260 ℃, after the carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is up to 96.6 percent, and the sample on mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution was 97.3%.
Example 3
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.75mol of Ethylene Glycol (EG) and 1mmol of antimony trioxide (Sb)2O3) Placing in a container, and performing direct esterification reaction at 230 deg.C under 0.18MPa to obtain ester1, the reaction time is 3h, the feeding molar ratio of PTA to EG is 1:1.5, and the addition amount of the catalyst is 0.2mol percent of PTA; under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.75mol of N-BOC-serinol and 0.3mmol of antimony trioxide (Sb)2O3) Placing in a container, performing direct esterification reaction at 190 deg.C under normal pressure to obtain ester 2, wherein the reaction time is 3.5h, and the feeding molar ratio of PTA and N-BOC-serinol is 1: 1.5; wherein the addition amount of the catalyst is 0.02 mol% of the PTA;
(2) after the reaction in step (1) is finished, 0.2mol of ester 1, 0.014mol of ester 2 and 0.1712mmol of antimony trioxide (Sb) are added under the protection of nitrogen2O3) Placing the mixture in a container, carrying out condensation polymerization reaction at the reaction temperature of 280 ℃ to prepare NP-PET, wherein the reaction pressure of a pre-polycondensation stage is 20KPa, the reaction time is 60min, then entering a high vacuum reaction stage, the reaction pressure is 30Pa, the reaction time is 6h, the addition amount of an ester 2 is 7 mol% of that of an ester 1, and the addition amount of a catalyst is 0.08% of the sum of the mol% of the two esters;
(3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using HCl gas under the ambient conditions of normal temperature and normal pressure, wherein the reaction time is 120min, and obtaining the N-PET with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.25 × 10-4mol of carboxymethyl β -cyclodextrin, 2.0 × 10-4mol NHS and 2.0 × 10-4Putting mol EDC & HCl into a container, and realizing a chemical combination reaction between carboxymethyl β -cyclodextrin and amino side groups on the modified polyester in a Hexafluoroisopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1: 280, the feeding molar ratio of carboxymethyl β -cyclodextrin to a catalyst is 1: 1.6, and the reaction time is 18h under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.20 × 104The molecular weight distribution is 2.0, the melting point of the polyester is 255 ℃, after the carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is up to 97.5 percent, and the sample on mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution was 97.8%.
Example 4
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.65mol of Ethylene Glycol (EG) and 2mmol of aluminum ethylene glycol (Al-EG) are placed in a container, direct esterification reaction is carried out at the reaction temperature of 230 ℃ and under the pressure of 0.16MPa to prepare an esterified product 1, the stirring speed is 210rpm, the reaction time is 3h, the feeding molar ratio of the PTA to the EG is 1: 1.3, and the adding amount of a catalyst is 0.4 mol% of the PTA; under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.75mol of N-BOC-threoninol and 0.1mmol of aluminum ethylene glycol (Al-EG) are placed in a container, direct esterification reaction is carried out at the reaction temperature of 195 ℃ and normal pressure to prepare an esterified product 2, the reaction time is 3h, and the molar ratio of the PTA to the N-BOC-threoninol is 1: 1.5; wherein the addition amount of the catalyst is 0.02 mol% of the PTA;
(2) after the reaction in the step (1) is finished, placing 0.2mol of ester 1, 0.014mol of ester 2 and 0.214mmol of aluminum ethylene glycol (Al-EG) in a container under the protection of nitrogen, and carrying out condensation polymerization reaction at the reaction temperature of 280 ℃ to prepare NP-PET, wherein the reaction pressure in the pre-condensation polymerization stage is 30KPa, the reaction time is 40min, then entering a high vacuum reaction stage, the reaction pressure is 30Pa, the reaction time is 5h, the addition amount of the ester 2 is 7 mol% of that of the ester 1, and the addition amount of the catalyst is 0.1% of the sum of the mole numbers of the two esters;
(3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using a 10% trifluoroacetic acid (TFA) solution under the ambient conditions of normal temperature and normal pressure for 30min to obtain modified PET polyester (N-PET) with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.35 × 10-4mol of carboxymethyl β -cyclodextrin, 2.3 × 10-4mol NHS and 2.3 × 10-4Putting mol EDC & HCl into a container, and carrying out a chemical combination reaction between carboxymethyl β -cyclodextrin and amino side groups on the modified polyester in a Hexafluoroisopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1: 260The feeding molar ratio of the carboxymethyl β -cyclodextrin to the catalyst is 1: 1.7, and the reaction time is 18 hours under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.19 × 104The molecular weight distribution is 1.9, the melting point of the polyester is 256.5 ℃, after the carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is up to 96.8 percent, and the sample on mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution was 97%.
Example 5
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.75mol of Ethylene Glycol (EG) and 1.5mmol of aluminum ethylene glycol (A1-EG) are placed in a container, direct esterification reaction is carried out at the reaction temperature of 240 ℃ and under the pressure of 0.2MPa to prepare an esterified product 1, the reaction time is 2h, the feeding molar ratio of the PTA to the EG is 1:1.5, and the adding amount of a catalyst is 0.3 mol% of the PTA; under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.6mol of N-BOC-threoninol and 2mmol of aluminum ethylene glycol (A1-EG) are placed in a container, direct esterification reaction is carried out at the reaction temperature of 195 ℃ and normal pressure to prepare an esterified product 2, the reaction time is 4h, and the molar ratio of the PTA to the N-BOC-threoninol is 1: 1.2; wherein the addition amount of the catalyst is 0.4 mol% of the PTA;
(2) after the reaction in the step (1) is finished, placing 0.2mol of ester 1, 0.014mol of ester 2 and 0.428mmol of aluminum ethylene glycol (Al-EG) in a container under the protection of nitrogen, and carrying out condensation polymerization reaction at the reaction temperature of 280 ℃ to prepare NP-PET, wherein the reaction pressure in the pre-condensation polymerization stage is 30KPa, the reaction time is 50min, then entering a high vacuum reaction stage, the reaction pressure is 20Pa, the reaction time is 4h, the addition amount of the ester 2 is 7 mol% of that of the ester 1, and the addition amount of the catalyst is 0.2% of the sum of the mole numbers of the two esters;
(3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using a 10% trifluoroacetic acid (TFA) solution under the ambient conditions of normal temperature and normal pressure, wherein the reaction time is 15min, and obtaining modified PET (N-PET) with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.15 × 10-4mol of carboxymethyl β -cyclodextrin, 1.96 × 10-4mol NHS and 1.96 × 10-4Putting mol EDC & HCl into a container, and realizing a chemical combination reaction between carboxymethyl β -cyclodextrin and amino side groups on the modified polyester in a Hexafluoroisopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1: 320, the feeding molar ratio of carboxymethyl β -cyclodextrin to a catalyst is 1: 1.7, and the reaction time is 24h under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.18 × 104The molecular weight distribution is 1.9, the melting point of the polyester is 256 ℃, after the carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is up to 96.5 percent, and the sample on mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution was 98%.
Example 6
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.7mol of Ethylene Glycol (EG) and 2.5mmol of antimony acetate are placed in a container, direct esterification reaction is carried out at the reaction temperature of 245 ℃ and under the pressure of 0.2MPa to prepare an esterified product 1, the reaction time is 2.5h, the feeding molar ratio of the PTA to the EG is 1: 1.4, and the adding amount of a catalyst is 0.5 mol% of the PTA; under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.8mol of N-BOC-threoninol and 2.5mmol of antimony acetate are placed in a container, direct esterification reaction is carried out at the reaction temperature of 180 ℃ and under normal pressure to prepare an esterified substance 2, the reaction time is 4h, and the molar ratio of PTA to the dihydric alcohol with an amino protecting group is 1: 1.6; wherein the addition amount of the catalyst is 0.5 mol% of the PTA;
(2) after the reaction in the step (1) is finished, placing 0.2mol of ester 1, 0.014mol of ester 2 and 1.07mmol of antimony acetate in a container under the protection of nitrogen, and carrying out condensation polymerization reaction at 285 ℃ to prepare NP-PET, wherein the reaction pressure in the pre-polycondensation stage is 20KPa, the reaction time is 60min, then entering a high vacuum reaction stage, the reaction pressure is 20Pa, the reaction time is 4h, the addition amount of the ester 2 is 7 mol% of that of the ester 1, and the addition amount of the catalyst is 0.5% of the sum of the mole numbers of the two esters;
(3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using a 10% trifluoroacetic acid (TFA) solution under the ambient conditions of normal temperature and normal pressure, wherein the reaction time is 40min, and obtaining modified PET polyester (N-PET) with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.25 × 10-4mol of carboxymethyl β -cyclodextrin, 2.25 × 10-4mol NHS and 2.25 × 10-4Putting mol EDC & HCl into a container, and realizing a chemical combination reaction between carboxymethyl β -cyclodextrin and amino side groups on the modified polyester in a Hexafluoroisopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1: 280, the feeding molar ratio of carboxymethyl β -cyclodextrin to a catalyst is 1: 1.8, and the reaction time is 20h under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.14 × 104The molecular weight distribution is 1.9, the melting point of the polyester is 256.5 ℃, after the carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is up to 97.1 percent, and the sample on mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution was 98.1%.
Example 7
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.6mol of Ethylene Glycol (EG) and 0.15mmol of antimony acetate are placed in a container, direct esterification reaction is carried out at the reaction temperature of 240 ℃ and under the pressure of 0.2MPa to prepare an esterified product 1, the reaction time is 2h, the feeding molar ratio of PTA to EG is 1:1.2, and the addition amount of a catalyst is 0.03 mol% of PTA; under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 1mol of N-BOC-threoninol and 0.1mmol of antimony acetate are placed in a container, direct esterification reaction is carried out at 185 ℃ and normal pressure to prepare an esterified substance 2, the reaction time is 3h, and the molar ratio of the PTA to the N-BOC-threoninol is 1: 2; wherein the addition amount of the catalyst is 0.02 mol% of the PTA;
(2) after the reaction in the step (1) is finished, placing 0.2mol of ester 1, 0.01mol of ester 2 and 0.105mmol of antimony acetate in a container under the protection of nitrogen, and carrying out condensation polymerization reaction at the reaction temperature of 270 ℃ to prepare NP-PET, wherein the reaction pressure in the pre-polycondensation stage is 30KPa, the reaction time is 60min, then entering a high vacuum reaction stage, the reaction pressure is 30Pa, the reaction time is 4h, the addition amount of the ester 2 is 5 mol% of the ester 1, and the addition amount of the catalyst is 0.05% of the sum of the mole numbers of the two esters;
(3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using a 10% trifluoroacetic acid (TFA) solution under normal temperature and pressure environment for 10min to obtain modified PET polyester (N-PET) with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.05 × 10-4mol of carboxymethyl β -cyclodextrin, 1.58 × 10-4mol NHS and 1.58 × 10-4Putting mol EDC & HCl into a container, and realizing a chemical combination reaction between carboxymethyl β -cyclodextrin and amino side groups on the modified polyester in a Hexafluoroisopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1: 480, the feeding molar ratio of carboxymethyl β -cyclodextrin to a catalyst is 1:1.5, and the reaction time is 24h under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.22 × 104The molecular weight distribution is 1.9, the melting point of polyester is 258.5 ℃, after carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is as high as 95.7 percent, and the sample can adsorb mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution was 98.2%.
Example 8
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.65mol of Ethylene Glycol (EG) and 1.5mmol of antimony acetate are placed in a container, direct esterification reaction is carried out at the reaction temperature of 250 ℃ and under the pressure of 0.2MPa to prepare an esterified product 1, the reaction time is 2h, the feeding molar ratio of PTA to EG is 1: 1.3, and the addition amount of a catalyst is 0.3 mol% of PTA; under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.9mol of Fmoc-serinol and 1mmol of antimony acetate are placed in a container, direct esterification reaction is carried out at the reaction temperature of 180 ℃ and under normal pressure to prepare an ester 2, the reaction time is 3h, and the molar ratio of the PTA to the dihydric alcohol with an amino protecting group is 1: 1.8; wherein the addition amount of the catalyst is 0.2 mol% of the PTA;
(2) after the reaction in the step (1) is finished, placing 0.2mol of ester 1, 0.01mol of ester 2 and 1.05mmol of antimony acetate in a container under the protection of nitrogen, and carrying out condensation polymerization reaction at 275 ℃ to prepare NP-PET, wherein the reaction pressure in the pre-polycondensation stage is 10KPa, the reaction time is 90min, and then entering a high vacuum reaction stage, the reaction pressure is 10Pa, the reaction time is 4h, the addition amount of the ester 2 is 5 mol% of the ester 1, and the addition amount of the catalyst is 0.5% of the sum of the mole numbers of the two esters:
(3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using HCl gas under the ambient conditions of normal temperature and normal pressure for 120min to obtain modified PET polyester (N-PET) with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.15 × 10-4mol of carboxymethyl β -cyclodextrin, 2.07 × 10-4mol NHS and 2.07 × 10-4Putting mol EDC & HCl into a container, and realizing a chemical combination reaction between carboxymethyl β -cyclodextrin and amino side groups on the modified polyester in a Hexafluoroisopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1: 420, the feeding molar ratio of carboxymethyl β -cyclodextrin to a catalyst is 1: 1.8, and the reaction time is 12h under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.11 × 104The molecular weight distribution is 1.9, the melting point of the polyester is 254 ℃, after the carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is up to 96.8 percent, and the sample on mixed heavy metal ions (Cu 2)+、Ag+) SolutionThe adsorption rate of heavy metal ions in the solution was 97%.
Example 9
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.6mol of Ethylene Glycol (EG) and 2mmol of antimony acetate are placed in a container, direct esterification reaction is carried out at the reaction temperature of 230 ℃ and under the pressure of 0.2MPa to prepare an esterified product 1, the stirring reaction time is 2h, the feeding molar ratio of PTA to EG is 1:1.2, and the addition amount of a catalyst is 0.4 mol% of PTA; under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 1mol of N-BOC-serinol and 2.5mmol of antimony acetate are placed in a container, direct esterification reaction is carried out at the reaction temperature of 190 ℃ and under normal pressure to prepare an esterified substance 2, the reaction time is 3h, and the feeding molar ratio of the PTA to the N-BOC-serinol is 1: 2; wherein the addition amount of the catalyst is 0.5 mol% of the PTA;
(2) after the reaction in the step (1) is finished, placing 0.2mol of ester 1, 0.01mol of ester 2 and 1.26mmol of antimony acetate in a container under the protection of nitrogen, and carrying out condensation polymerization reaction at 290 ℃ to prepare NP-PET, wherein the reaction pressure in the pre-polycondensation stage is 10KPa, the reaction time is 60min, then entering a high vacuum reaction stage, the reaction pressure is 50Pa, the reaction time is 4h, the addition amount of the ester 2 is 5 mol% of that of the ester 1, and the addition amount of the catalyst is 0.6% of the sum of the mole numbers of the two esters;
(3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using a 10% trifluoroacetic acid (TFA) solution under the ambient conditions of normal temperature and normal pressure, wherein the reaction time is 30min, and the stirring speed is 150rpm, so as to obtain modified PET polyester (N-PET) with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.25 × 104mol of carboxymethyl β -cyclodextrin, 1.88 × 10-4mol NHS and 1.88 × 10-4Putting mol EDC & HCl into a container, and realizing the combination reaction between carboxymethyl β -cyclodextrin and amino side groups on the modified polyester in a Hexafluoroisopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1: 400, and the feeding molar ratio of carboxymethyl β -cyclodextrin to the catalyst is 1: 1.5: 11.5, reacting for 20 hours under the conditions of normal temperature and normal pressure to obtain the N-PET-g-CD polyester with high adsorbability.
The weight average molecular weight of the synthetic N-PET polyester was 4.25 × 104The molecular weight distribution is 1.8, the melting point of polyester is 259 ℃, after carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is as high as 97.1%, and the sample can adsorb mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution was 97.5%.
Example 10
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.6mol of Ethylene Glycol (EG) and 2.5mmol of antimony acetate are placed in a container, direct esterification reaction is carried out at the reaction temperature of 250 ℃ and under the pressure of 0.18MPa to prepare an esterified product 1, the stirring reaction time is 2.5h, the feeding molar ratio of PTA to EG is 1:1.2, and the adding amount of a catalyst is 0.5 mol% of PTA; under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 1mol of N-BOC-serinol and 0.4mmol of antimony acetate are placed in a container, direct esterification reaction is carried out at the reaction temperature of 190 ℃ and under normal pressure to prepare an esterified substance 2, the reaction time is 3h, and the feeding molar ratio of the PTA to the N-BOC-serinol is 1: 2; wherein the addition amount of the catalyst is 0.08 mol% of the PTA;
(2) after the reaction in the step (1) is finished, placing 0.2mol of ester 1, 0.014mol of ester 2 and 4.28mmol of antimony acetate in a container under the protection of nitrogen, and carrying out condensation polymerization reaction at 275 ℃ to prepare NP-PET, wherein the reaction pressure in the pre-polycondensation stage is 10KPa, the reaction time is 60min, then entering a high vacuum reaction stage, the reaction pressure is 50Pa, the reaction time is 6h, the addition amount of the ester 2 is 7 mol% of the ester 1, and the addition amount of the catalyst is 0.2% of the sum of the mole numbers of the two esters;
(3) and (3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using a 10% trifluoroacetic acid (TFA) solution under the ambient conditions of normal temperature and normal pressure, wherein the reaction time is 30min, and obtaining the modified PET polyester (N-PET) with the amino side group. (ii) a
(4) After the reaction of the step (3) is finishedThereafter, 5g of N-PET, 1.25 × 10-4mol of carboxymethyl β -cyclodextrin, 1.88 × 10-4mol NHS and 1.88 × 10-4Putting mol EDC & HCl into a container, and realizing a chemical combination reaction between carboxymethyl β -cyclodextrin and amino side groups on the modified polyester in a Hexafluoroisopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1: 280, the feeding molar ratio of carboxymethyl β -cyclodextrin to a catalyst is 1:1.5, and the reaction time is 16h under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.15 × 104The molecular weight distribution is 2.0, the melting point of the polyester is 258 ℃, after the carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is up to 96.5 percent, and the sample on mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution was 98.3%.
Example 11
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.7mol of Ethylene Glycol (EG) and 3mmol of antimony trioxide (Sb)2O3) Placing in a container, carrying out direct esterification reaction at 230 ℃ and 0.19MPa to prepare an esterified product 1, wherein the reaction time is 2h, the feeding molar ratio of PTA to EG is 1: 1.4, and the addition amount of a catalyst is 0.6 mol% of PTA; under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.6mol of N-BOC-serinol and 1mmol of antimony trioxide (Sb)2O3) Placing in a container, performing direct esterification reaction at 185 deg.C under normal pressure to obtain ester 2, wherein the reaction time is 3h, and the feeding molar ratio of PTA and N-BOC-serinol is 1: 1.2; wherein the addition amount of the catalyst is 0.2 mol% of the PTA;
(2) after the reaction in the step (1) is finished, 0.2mol of the ester 1, 0.02mol of the ester 2 and 0.11mmol of antimony trioxide (Sb) are added under the protection of nitrogen2O3) Placing in a container, performing condensation polymerization at 280 deg.C to obtain NP-PET, wherein the reaction pressure in the pre-polycondensation stage is 20KPa, the reaction time is 50min, and then entering high vacuumIn the empty reaction stage, the reaction pressure is 30Pa, the reaction time is 6h, the addition amount of the ester 2 is 10mol percent of that of the ester 1, and the addition amount of the catalyst is 0.05 percent of the sum of the mole numbers of the two esters;
(3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using a 10% trifluoroacetic acid (TFA) solution under the ambient conditions of normal temperature and normal pressure for 20min to obtain modified PET polyester (N-PET) with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.05 × 10-4mol of carboxymethyl β -cyclodextrin, 1.58 × 10-4mol NHS and 1.58 × 10-4Putting mol EDC & HCl into a container, and realizing a chemical combination reaction between carboxymethyl β -cyclodextrin and amino side groups on the modified polyester in a Hexafluoroisopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1:125, the feeding molar ratio of carboxymethyl β -cyclodextrin to a catalyst is 1:1.5, and the reaction time is 20h under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.12 × 104The molecular weight distribution is 1.9, the melting point of the polyester is 256 ℃, after the carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is up to 96.8 percent, and the sample on mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution was 97.9%.
Example 12
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.75mol of Ethylene Glycol (EG) and 1.5mmol of antimony trioxide (Sb)2O3) Placing in a container, performing direct esterification reaction at 240 deg.C under 0.2MPa to obtain ester 1, wherein the reaction time is 3h, the feeding molar ratio of PTA and EG is 1:1.5, and the catalyst addition is 0.3 mol% of PTA; under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 1mol of Fmoc-serinol and 0.2mmol of antimony trioxide (Sb)2O3) Placing in a container, and performing direct esterification reaction at 175 deg.C under normal pressure to obtain esterified product2, the reaction time is 3h, and the molar ratio of PTA to Fmoc-serinol is 1: 2; wherein the addition amount of the catalyst is 0.04 mol% of the PTA;
(2) after the reaction in the step (1) is finished, 0.2mol of the ester 1, 0.04mol of the ester 2 and 0.12mmol of antimony trioxide (Sb) are added under the protection of nitrogen2O3) Placing the mixture in a container, carrying out condensation polymerization reaction at the reaction temperature of 275 ℃ to prepare NP-PET, wherein the reaction pressure in the pre-polycondensation stage is 10KPa, the reaction time is 60min, then entering a high vacuum reaction stage, the reaction pressure is 50Pa, the reaction time is 6h, the addition amount of the ester 2 is 7 mol% of that of the ester 1, and the addition amount of the catalyst is 0.05% of the sum of the two ester mol%;
(3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using HCl gas under the ambient conditions of normal temperature and normal pressure for 90min to obtain modified PET polyester (N-PET) with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.25 × 10-4mol of carboxymethyl β -cyclodextrin, 1.88 × 10-4mol NHS and 1.88 × 10-4Putting mol EDC & HCl into a container, and realizing a chemical combination reaction between carboxymethyl β -cyclodextrin and amino side groups on the modified polyester in a Hexafluoroisopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1: 280, the feeding molar ratio of carboxymethyl β -cyclodextrin to a catalyst is 1:1.5, and the reaction time is 16h under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.21 × 104The molecular weight distribution is 2.0, the melting point of the polyester is 254 ℃, after the carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is as high as 97.9 percent, and the sample can adsorb mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution was 98.5%.
Example 13
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.6mol of Ethylene Glycol (EG) and1.5mmol of antimony trioxide (Sb)2O3) Placing in a container, carrying out direct esterification reaction at the reaction temperature of 240 ℃ and under the pressure of 0.2MPa to prepare an ester 1, wherein the reaction time is 2h, the feeding molar ratio of PTA to EG is 1:1.2, and the addition amount of a catalyst is 0.3 mol% of PTA; 0.5mol of terephthalic acid (PTA), 0.9mol of Fmoc-serinol and 1mmol of antimony trioxide (Sb) under the protection of nitrogen2O3) Placing in a container, performing direct esterification reaction at 195 deg.C under normal pressure to obtain ester 2, wherein the reaction time is 3h, and the molar ratio of PTA and Fmoc-serinol is 1: 1.8; wherein the addition amount of the catalyst is 0.2 mol% of the PTA;
(2) after the reaction in the step (1) is finished, 0.2mol of the ester 1, 0.01mol of the ester 2 and 1.05mmol of antimony trioxide (Sb) are added under the protection of nitrogen2O3) Placing the mixture in a container, carrying out condensation polymerization reaction at the reaction temperature of 280 ℃ to prepare NP-PET, wherein the reaction pressure in the pre-polycondensation stage is 30KPa, the reaction time is 60min, then entering a high vacuum reaction stage, the reaction pressure is 50Pa, the reaction time is 6h, the addition amount of the ester 2 is 5 mol% of that of the ester 1, and the addition amount of the catalyst is 0.5% of the sum of the two ester mol%;
(3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using HCl gas under the ambient conditions of normal temperature and normal pressure for 60min to obtain modified PET polyester (N-PET) with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.05 × 10-4mol of carboxymethyl β -cyclodextrin, 1.58 × 10-4mol NHS and 1.58 × 10-4Putting mol EDC & HCl into a container, and realizing a chemical combination reaction between carboxymethyl β -cyclodextrin and amino side groups on the modified polyester in a Hexafluoroisopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1:500, the feeding molar ratio of carboxymethyl β -cyclodextrin to a catalyst is 1:1.5, and the reaction time is 22h under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.24 × 104The molecular weight distribution was 1.8,the melting point of the polyester is 255 ℃, after the carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is up to 96.2%, and the sample on mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution was 97.1%.
Example 14
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.65mol of Ethylene Glycol (EG) and 3mmol of antimony trioxide (Sb)2O3) Placing in a container, carrying out direct esterification reaction at 220 ℃ and 0.25MPa to prepare an ester 1, wherein the reaction time is 2h, the feeding molar ratio of PTA to EG is 1: 1.3, and the addition amount of a catalyst is 0.6 mol% of PTA; under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.6mol of Fmoc-threoninol and 5mmol of antimony trioxide (Sb)2O3) Placing in a container, performing direct esterification reaction at 200 deg.C under normal pressure to obtain ester 2, wherein the reaction time is 3h, and the molar ratio of PTA and Fmoc-threoninol is 1: 1.2; wherein the addition amount of the catalyst is 0.1 mol% of the PTA;
(2) after the reaction in the step (1) is finished, 0.2mol of the ester 1, 0.014mol of the ester 2 and 2.14mmol of antimony trioxide (Sb) are added under the protection of nitrogen2O3) Placing the mixture in a container, carrying out condensation polymerization reaction at the reaction temperature of 285 ℃ to prepare NP-PET, wherein the reaction pressure in the pre-polycondensation stage is 20KPa, the reaction time is 50min, then entering a high vacuum reaction stage, the reaction pressure is 20Pa, the reaction time is 5h, the addition amount of the ester 2 is 7 mol% of that of the ester 1, and the addition amount of the catalyst is 0.1% of the sum of the two ester mol%;
(3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using HCl gas under the ambient conditions of normal temperature and normal pressure for 90min to obtain modified PET polyester (N-PET) with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.25 × 10-4mol of carboxymethyl β -cyclodextrin, 1.88 × 10-4mol NHS and 1.88 × 10-4Placing mol EDC & HCl into a containerThe method is characterized in that chemical combination reaction between carboxymethyl β -cyclodextrin and amino side groups on modified polyester is realized in a fluorine isopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1: 280, the feeding molar ratio of carboxymethyl β -cyclodextrin to a catalyst is 1:1.5, and the reaction time is 16h under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.17 × 104The molecular weight distribution is 1.9, the melting point of the polyester is 257 ℃, after the carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is up to 96.8 percent, and the sample on mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution was 98.2%.
Example 15
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.75mol of Ethylene Glycol (EG) and 4mmol of antimony trioxide (Sb)2O3) Placing in a container, carrying out direct esterification reaction at 255 ℃ and 0.18MPa to prepare an ester 1, wherein the reaction time is 2h, the feeding molar ratio of PTA to EG is 1:1.5, and the addition amount of a catalyst is 0.8 mol% of PTA; under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 1.5mol of Fmo-threoninol and 3mmol of antimony trioxide (Sb)2O3) Placing in a container, performing direct esterification reaction at 175 deg.C under normal pressure to obtain ester 2, wherein the reaction time is 3h, and the molar ratio of PTA and amino-protecting group-containing diatomic alcohol is 1: 3; wherein the addition amount of the catalyst is 0.6 mol% of the PTA;
(2) after the reaction in the step (1) is finished, 0.2mol of the ester 1, 0.02mol of the ester 2 and 1.1mmol of antimony trioxide (Sb) are added under the protection of nitrogen2O3) Placing in a container, performing condensation polymerization at 290 deg.C to obtain NP-PET, wherein the reaction pressure in the pre-polycondensation stage is 10KPa, the reaction time is 60min, then entering into high vacuum reaction stage, the reaction pressure is 30Pa, the reaction time is 4h, the addition amount of the ester 2 is 10 mol% of that of the ester 1, and the addition amount of the catalyst is two esters0.5% of the sum of the mole numbers;
(3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using HCl gas under the ambient conditions of normal temperature and normal pressure for 120min to obtain modified PET polyester (N-PET) with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.15 × 10-4mol of carboxymethyl β -cyclodextrin, 1.73 × 10-4mol NHS and 1.73 × 10-4Putting mol EDC & HCl into a container, and realizing a chemical combination reaction between carboxymethyl β -cyclodextrin and amino side groups on the modified polyester in a Hexafluoroisopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1: 220, the feeding molar ratio of carboxymethyl β -cyclodextrin to a catalyst is 1:1.5, and the reaction time is 22h under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.23 × 104The molecular weight distribution is 2.0, the melting point of the polyester is 257 ℃, after the carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is as high as 94.9 percent, and the sample on mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution was 96.9%.
Example 16
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.6mol of Ethylene Glycol (EG) and 4mmol of antimony trioxide (Sb)2O3) Placing in a container, carrying out direct esterification reaction at 230 ℃ and 0.2MPa to prepare an esterified product 1, wherein the reaction time is 2h, the feeding molar ratio of PTA to EG is 1:1.2, and the addition amount of a catalyst is 0.8 mol% of PTA; 0.5mol of terephthalic acid (PTA), 1mol of Fmoc-threoninol and 2.5mmol of antimony trioxide (Sb) under the protection of nitrogen2O3) Placing in a container, performing direct esterification reaction at 175 deg.C under normal pressure to obtain ester 2, wherein the reaction time is 3h, and the molar ratio of PTA and Fmoc-threoninol is 1: 2; wherein the addition amount of the catalyst is 0.5 mol% of the PTA;
(2) after the step (1) is reversedAfter the reaction, 0.2mol of ester 1, 0.02mol of ester 2 and 1.76mmol of antimony trioxide (Sb) were added under the protection of nitrogen2O3) Placing the mixture in a container, carrying out condensation polymerization reaction at the reaction temperature of 270 ℃ to prepare NP-PET, wherein the reaction pressure in the pre-polycondensation stage is 10KPa, the reaction time is 50min, then entering a high vacuum reaction stage, the reaction pressure is 20Pa, the reaction time is 5h, the addition amount of the ester 2 is 10 mol% of that of the ester 1, and the addition amount of the catalyst is 0.8% of the sum of the two ester mole numbers;
(3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using HCl gas under the ambient conditions of normal temperature and normal pressure for 100min to obtain modified PET polyester (N-PET) with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.1 × 10-4mol of carboxymethyl β -cyclodextrin, 1.65 × 10-4mol NHS and 1.65 × 10-4Putting mol EDC & HCl into a container, and realizing a chemical combination reaction between carboxymethyl β -cyclodextrin and amino side groups on the modified polyester in a Hexafluoroisopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1: 230, the feeding molar ratio of carboxymethyl β -cyclodextrin to a catalyst is 1:1.5, and the reaction time is 24h under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.13 × 104The molecular weight distribution is 2.0, the melting point of the polyester is 254 ℃, after the carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is up to 96.9 percent, and the sample on mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution was 97.1%.
Example 17
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.6mol of Ethylene Glycol (EG) and 4mmol of antimony trioxide (Sb)2O3) Placing in a container, performing direct esterification reaction at 230 deg.C under 0.18MPa to obtain ester 1, wherein the reaction time is 2h, and PTThe feeding molar ratio of A to EG is 1:1.2, and the addition amount of the catalyst is 0.8mol percent of PTA; 0.5mol of terephthalic acid (PTA), 1mol of Fmoc-threoninol and 2.5mmol of antimony trioxide (Sb) under the protection of nitrogen2O3) Placing in a container, performing direct esterification reaction at 180 deg.C under normal pressure to obtain ester 2, wherein the reaction time is 3h, and the molar ratio of PTA and Fmoc-threoninol is 1: 2; wherein the addition amount of the catalyst is 0.5 mol% of the PTA;
(2) after the reaction in the step (1) is finished, 0.2mol of the ester 1, 0.02mol of the ester 2 and 1.76mmol of antimony trioxide (Sb) are added under the protection of nitrogen2O3) Placing the mixture in a container, carrying out condensation polymerization reaction at the reaction temperature of 270 ℃ to prepare NP-PET, wherein the reaction pressure in the pre-polycondensation stage is 10KPa, the reaction time is 50min, then entering a high vacuum reaction stage, the reaction pressure is 20Pa, the reaction time is 4h, the addition amount of the ester 2 is 10 mol% of that of the ester 1, and the addition amount of the catalyst is 0.8% of the sum of the two ester mole numbers;
(3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using a 10% trifluoroacetic acid (TFA) solution under the ambient conditions of normal temperature and normal pressure for 30min to obtain modified PET polyester (N-PET) with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.3 × 10-4mol of carboxymethyl β -cyclodextrin, 1.95 × 10-4mol NHS and 1.95 × 10-4Putting mol EDC & HCl into a container, and realizing a chemical combination reaction between carboxymethyl β -cyclodextrin and amino side groups on the modified polyester in a Hexafluoroisopropanol (HFIP) solution, wherein the mass ratio of carboxymethyl β -cyclodextrin to N-PET is 1: 200, the feeding molar ratio of carboxymethyl β -cyclodextrin to a catalyst is 1:1.5, and the reaction time is 24h under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.15 × 104The molecular weight distribution is 2.0, the melting point of the polyester is 254.5 ℃, after the carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is up to 96.8 percent, and the sample on mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution was 97.5%.
Example 18
A preparation method of a high-efficiency adsorptive polyester material comprises the following steps:
(1) under the protection of nitrogen, 0.5mol of terephthalic acid (PTA), 0.6mol of Ethylene Glycol (EG) and 4mmol of antimony trioxide (Sb)2O3) Placing in a container, carrying out direct esterification reaction at 230 ℃ and 0.2MPa to prepare an esterified product 1, wherein the reaction time is 2h, the feeding molar ratio of PTA to EG is 1:1.2, and the addition amount of a catalyst is 0.8 mol% of PTA; 0.5mol of terephthalic acid (PTA), 1mol of Fmoc-threoninol and 2.5mmol of antimony trioxide (Sb) under the protection of nitrogen2O3) Placing in a container, performing direct esterification reaction at 180 deg.C under normal pressure to obtain ester 2, wherein the reaction time is 3h, and the molar ratio of PTA and Fmoc-threoninol is 1: 2; wherein the addition amount of the catalyst is 0.5 mol% of the PTA;
(2) after the reaction in the step (1) is finished, 0.2mol of the ester 1, 0.02mol of the ester 2 and 1.76mmol of antimony trioxide (Sb) are added under the protection of nitrogen2O3) Placing the mixture in a container, carrying out condensation polymerization reaction at the reaction temperature of 270 ℃ to prepare NP-PET, wherein the reaction pressure in the pre-polycondensation stage is 10KPa, the reaction time is 50min, then entering a high vacuum reaction stage, the reaction pressure is 20Pa, the reaction time is 5h, the addition amount of the ester 2 is 10 mol% of that of the ester 1, and the addition amount of the catalyst is 0.8% of the sum of the two ester mole numbers;
(3) after the reaction in the step (2) is finished, carrying out deamination protecting group reaction on 10g of NP-PET by using a 10% trifluoroacetic acid (TFA) solution under normal temperature and pressure environment for 10min to obtain modified PET polyester (N-PET) with amino side groups;
(4) after the reaction of the step (3) is finished, 5g of N-PET and 1.2 × 10-4mol of carboxymethyl β -cyclodextrin, 1.8 × 10-4mol NHS and 1.8 × 10-4Putting EDC & HCl into container, and carrying out chemical combination reaction between carboxymethyl β -cyclodextrin and amino side group on modified polyester in Hexafluoroisopropanol (HFIP) solution, wherein carboxymethyl β -cyclodextrin and NThe mass ratio of PET is 1: 200, the feeding molar ratio of carboxymethyl β -cyclodextrin to catalyst is 1:1.5, and the reaction time is 18h under the conditions of normal temperature and normal pressure, so that the N-PET-g-CD polyester with high adsorbability is obtained.
The weight average molecular weight of the synthetic N-PET polyester was 4.16 × 104The molecular weight distribution is 2.0, the melting point of the polyester is 254 ℃, after the carboxymethyl β -cyclodextrin is chemically immobilized, the adsorption rate of a sample on rhodamine b is up to 97 percent, and the sample on mixed heavy metal ions (Cu)2+、Ag+) The adsorption rate of heavy metal ions in the solution was 98.2%.

Claims (8)

1. The preparation method of the high-efficiency adsorptive polyester material is characterized by comprising the following steps of:
step 1): placing terephthalic acid, ethylene glycol and a catalyst I in a container under the protection of nitrogen, and carrying out esterification reaction at 220-260 ℃ and 0.1-0.3 MPa to prepare an ester I, wherein the reaction time is 1.5-3 h; the molar ratio of the addition amount of the terephthalic acid to the addition amount of the ethylene glycol is 1: 1.2-1: 1.5, and the addition amount of the first catalyst is 0.01-0.1% of the mole number of the terephthalic acid;
step 2): placing terephthalic acid, amino-protecting group-containing diatomic alcohol and a catalyst I in a container under the protection of nitrogen, and carrying out esterification reaction at 140-200 ℃ and normal pressure to prepare an esterified substance II, wherein the reaction time is 2-4 h, and the molar ratio of the addition amount of the terephthalic acid to the amino-protecting group-containing diatomic alcohol is 1: 1.2-1: 3; the addition amount of the first catalyst is 0.01-0.1% of the mole number of the terephthalic acid;
step 3): placing the first esterified substance, the second esterified substance and the first catalyst in a container under the protection of nitrogen, and carrying out condensation polymerization reaction at a reaction temperature of 270-290 ℃ to prepare NP-PET polyester, wherein the reaction pressure in the pre-polycondensation stage is 1-50 KPa, the reaction time is 30-60 min, and then entering a high vacuum reaction stage, the reaction pressure is 10-150 Pa, and the reaction time is 2-4 h; the addition amount of the second ester is 5-20% of the mole number of the first ester, and the addition amount of the first catalyst is 0.01-0.1% of the sum of the mole numbers of the two esters;
step 4): selecting an amino deprotection reagent, and carrying out deamination protecting group reaction on NP-PET polyester for 10-120 min to obtain N-PET polyester;
step 5): placing the N-PET solution, the cyclodextrin derivative and the catalyst II into a container, and reacting for 12-24 hours at normal temperature and normal pressure to obtain N-PET-g-CD polyester with high adsorbability; wherein the mass ratio of the cyclodextrin derivative to the N-PET is 1: 125-1: 500, and the molar ratio of the cyclodextrin derivative to the catalyst II is 1: 1.5-1: 2.
2. The method for preparing super absorbent polyester material as claimed in claim 1, wherein the first catalyst in the steps 1) -3) is organic antimony compound, organic tin compound or organic aluminum compound.
3. The method for preparing super absorbent polyester material as claimed in claim 1, wherein the diamine alcohol having amino protecting group in step 2) is t-butyloxycarbonyl-aminopropanediol compound, fluorenylmethoxycarbonyl-aminopropanediol compound, t-butyloxycarbonyl-aminobutanediol compound or fluorenylmethoxycarbonyl-aminobutanediol compound.
4. The method for preparing super absorbent polyester material as claimed in claim 1, wherein the reagent for amino deprotection in step 4) is HCl gas or trifluoroacetic acid solution.
5. The method for preparing super absorbent polyester material as set forth in claim 1, wherein the solvent of the N-PET solution in the step 5) is hexafluoroisopropanol.
6. The method for preparing super absorbent polyester material as claimed in claim 1, wherein said cyclodextrin derivative of step 5) is carboxymethyl β -cyclodextrin.
7. The method for preparing the super absorbent polyester material as set forth in claim 1, wherein the catalyst II in the step 5) is a composite catalyst of N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
8. The method for preparing super absorbent polyester material as claimed in claim 1, wherein after the reaction in step 5), if the product is liquid, the product is precipitated in excess ice methanol, and the filtration, washing and vacuum drying are repeated; if the product is solid, the product is repeatedly washed by excessive deionized water and dried in vacuum to obtain the final product N-PET-g-CD.
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