CN106750331A - A kind of high adsorption polyester material and preparation method thereof - Google Patents
A kind of high adsorption polyester material and preparation method thereof Download PDFInfo
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- CN106750331A CN106750331A CN201611025656.4A CN201611025656A CN106750331A CN 106750331 A CN106750331 A CN 106750331A CN 201611025656 A CN201611025656 A CN 201611025656A CN 106750331 A CN106750331 A CN 106750331A
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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
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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
- C08G63/02—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
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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
- C08G63/68—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 kind of high adsorption polyester material and preparation method thereof.The polyester is the modified PET polyester with amino side base, and cyclodextrin or derivatives thereof the chemistry on its strand is immobilized.Preparation method is：With terephthalic acid (TPA), ethylene glycol, the binary ammonia alcohol with amino protecting group is raw material, and modified polyethylene terephthalate is prepared through esterifying polycondensation reaction, is reacted through deaminizating protection group, obtains the polyester with free amino group side base；Cyclodextrin or derivatives thereof and the amino side base of N PET polyester are carried out into chemical graft reaction, the modified PET polyester with high adsorption is prepared.Polyester material prepared by the present invention has the ring cavity structure of cyclodextrin external hydrophilic, inner hydrophobic, host-guest inclusion complex compound can be formed with water phase by a series of organic and inorganic molecules, for the absorption of dyestuff, heavy metal ion in dyeing waste water, terylene alcoholysis product etc..
Description
Technical field
The invention belongs to functional polyester Material Field, and in particular to a kind of polyethylene terephthalate (PET's) changes
Property method.
Background technology
Cyclodextrin has the special construction and property of " inner chamber is hydrophobic, and outer wall is hydrophilic ", and is in " truncated cones " in external form
The cyclic oligosaccharide of shape.Due to cheap and easy to get, and with special structure and property, cyclodextrin can be a series of organic with water phase
Molecule formed host-guest Inclusion Complexes, be applied to the fields such as the absorption and extraction of environmental contaminants, wherein, cyclodextrin and
A chemical immobilized important directions as its application extension of its derivative.Due to chemical bearing cyclodextrin or derivatives thereof,
Not only can well keep cyclodextrin or derivatives thereof intrinsic cavity structure and advantageous property, it is to avoid what cross-linked polymeric was caused
The acute variation of cyclodextrin cavity structure is even destroyed, moreover it is possible to overcome cyclodextrin good water solubility, reclaims difficult defect.
Polyester fiber low production cost, easily obtain, PET polyester is excellent a kind of production and processing cycle is short, thermodynamic property
Good polyester, is usually used in engineering plastics field, function side base can be introduced on its polyester macromolecule chain by modified to it,
Realize it is chemical immobilized with cyclodextrin and its derivative, for environmental contaminants adsorb and dacron polyester alcoholysis product in dyestuff,
The absorption of impurity, heavy metal ion etc..
The content of the invention
The technical problems to be solved by the invention are to provide a kind of efficient absorption polyester material and preparation method thereof, synthesis
Modified poly ester with amino side base, realizes that cyclodextrin or derivatives thereof is chemical immobilized on its macromolecular chain, makes the polyester
Possess good mechanical property, chemical reagent resistance and high adsorption.
In order to solve the above problems, the invention provides a kind of efficient absorption polyester material, it is characterised in that described poly-
Ester is the modified PET polyester (NP-PET) with amino side base, and cyclodextrin or derivatives thereof the chemistry on its strand is immobilized.
Preferably, the function side base of the modified PET polyester with amino side base is the amino with protection group.
Present invention also offers the preparation method of above-mentioned efficient absorption polyester material, it is characterised in that including following step
Suddenly：
Step 1)：Terephthalic acid (TPA) (PTA), ethylene glycol (EG) and catalyst one are placed in container under nitrogen protection,
Esterification is carried out at 220~260 DEG C, under the conditions of 0.1~0.3MPa and prepares carboxylate one, the reaction time is 1.5~3h；To benzene
Dioctyl phthalate is 1: 1.2~1: 1.5 with the mol ratio of ethylene glycol addition, and the addition of catalyst one is terephthalic acid (TPA) molal quantity
0.01~0.1%；
Step 2)：Terephthalic acid (TPA), the binary ammonia alcohol with amino protecting group and catalyst one are put under nitrogen protection
In container, esterification is carried out under 140~200 DEG C, condition of normal pressure and prepares carboxylate two, the reaction time is 2~4h, to benzene
Dioctyl phthalate is 1: 1.2~1: 3 with the mol ratio of the binary ammonia alcohol addition with amino protecting group；The addition of catalyst one is
The 0.01~0.1% of terephthalic acid (TPA) molal quantity；
Step 3)：Carboxylate one, carboxylate one and catalyst one are placed in container under nitrogen protection, in reaction temperature
NP-PET polyester is prepared to carry out condensation polymerization reaction under conditions of 270~290 DEG C, wherein, the pressure of precondensation stage reaction
It is 1~50KPa, the reaction time is 30~60min, afterwards into the high vacuum stage of reaction, reaction pressure is 10~150Pa, instead
It is 2~4h between seasonable；The addition of carboxylate two is the 5~20% of the molal quantity of carboxylate one, and the addition of catalyst one is
Two kinds the 0.01~0.1% of carboxylate molal quantity sum；
Step 4)：Suitable amino deprotecting regent is selected, deaminizating protection group reaction is carried out to NP-PET polyester, reacted
Time is 10~120min, obtains N-PET polyester；
Step 5)：N-PET solution, cyclodextrin or derivatives thereof and catalyst two are inserted into container, is reacted under normal temperature and pressure
12~24h, obtains the N-PET-g-CD polyester with high adsorption；Wherein, the mass ratio of cyclodextrin or derivatives thereof and N-PET
It is 1: 125~1: 500, cyclodextrin or derivatives thereof is 1: 1.5~1: 2 with the mol ratio of catalyst two.
Preferably, the step 1)~3) in catalyst one using organo-antimony compound, organo-tin compound or organo-aluminium
Compound.
Preferably, the step 2) in have amino protecting group binary ammonia alcohol using Boc- aminopropane diol compounds,
Fmoc- aminopropane diol compounds, Boc- amino butanediol compounds or Fmoc- amino butanediol compounds.
Preferably, the step 4) in amino deprotecting regent use HCl gases or trifluoroacetic acid (TFA) solution.
Preferably, the step 5) in N-PET solution solvent use hexafluoroisopropanol (HFIP).
Preferably, the step 5) cyclodextrin or derivatives thereof uses carboxymethyl-β-cyclodextrin.
Preferably, the step 5) in catalyst two using N-hydroxy-succinamide (NHS) and 1- (3- dimethylaminos third
Base) both -3- ethyl-carbodiimide hydrochlorides (EDCHCl) composite catalyst.
Preferably, the step 5) reaction terminate after, if product is liquid, need to be through precipitating analysis in excessive ice methyl alcohol
Go out, filter repeatedly, wash and be vacuum dried；If product is solid, need to through excessive deionized water cyclic washing, be vacuum dried
To final product N-PET-g-CD.
Carboxylate is prepared through direct esterification reaction, carboxylate room temperature need to be cooled under nitrogen protection, it is to avoid it is by oxygen
Change.Suitable deprotection reaction reagent is selected according to amino protecting group, can be quick in the case where backbone molecule structure is not destroyed
Effectively the amino protecting group on NP-PET is sloughed, makes occur free amino group on NP-PET macromolecular chains, prepare band amino side
The N-PET of base.
The present invention prepares modified PET polyester (NP-PET) using two-step method, and the circuit can be prevented effectively from during the course of the reaction
The destruction of binary ammonia alcohol amino protecting group, successfully prepares the modified PET copolyesters (N-PET) with amino side base.
The present invention realizes the product that cyclodextrin or derivatives thereof is chemical immobilized on N-PET macromolecular chains, finally synthesizes
Thing has the special cavity structure of complete cyclodextrin, and with high absorption property, can be used for dyeing waste water and dacron polyester alcoholysis
The absorption of dyestuff, impurity, heavy metal ion etc. in product.
Brief description of the drawings
Fig. 1 a-b are carboxylate composition principle figure of the present invention；
Polyester material (NP-PET and N-PET) composition principle figure that Fig. 2 is provided for the present invention；
In figure：R1 is alkyl backbones, and R2 is amino protecting group.
Specific embodiment
To become apparent the present invention, hereby with preferred embodiment, and accompanying drawing is coordinated to be described in detail below.
The chemical structural formula of synthesis modification PET copolyesters (N-PET) provided by the present invention is as follows：
In above-mentioned polyester macromolecule structure, R1It is alkyl backbones, X is that 5~20, Y is 100~200；Weight average molecular weight is 1
~5 ten thousand.
Modified PET polyester (N-PET) molecular weight and molecular weight distribution of final synthesis of the invention pass through gel permeation chromatography
Instrument (GPC) test analysis, the molecular structure and composition of polyester by NMR (1) and Fourier transform infrared spectroscopy HNMR
Instrument (FTIR) test analysis, the inherent viscosity of polyester is tested by inherent viscosity instrument, is tested by differential surface sweeping calorimeter (DSC)
The fusing point of polyester, the heat decomposition temperature of polyester is tested by thermogravimetric analyzer (TGA), and polyester is tested by sepectrophotofluorometer
Absorption property in rhodamine b solution.
Embodiment 1
A kind of preparation method of efficient absorption polyester material：
(1) under nitrogen protection by 0.5mol terephthalic acid (TPA)s (PTA), 0.6mol ethylene glycol (EG) and the oxygen of 0.15mmol tri-
Change two antimony (Sb2O3) be placed in container, in 220 DEG C of reaction temperature, direct esterification reaction is carried out under 0.2MPa pressure and prepares carboxylate
1, the reaction time is that the molar ratio of 1.5h, PTA and EG is 1: 1.2, and catalyst loading is the 0.03mol% of PTA；In nitrogen
0.5mol terephthalic acid (TPA)s (PTA), 1mol had into N-BOC- serinols and 0.1mmol antimony oxides (Sb under gas shielded2O3)
It is placed in container, is 175 DEG C in reaction temperature, direct esterification reaction is carried out under normal pressure and prepares carboxylate 2, the reaction time is 3h,
PTA is 1: 2 with the molar ratio of N-BOC- serinols；Wherein, catalyst loading is the 0.02mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.01mol carboxylates 2 and
0.105mol antimony oxides (Sb2O3) be placed in container, carry out condensation polymerization reaction under conditions of being 270 DEG C in reaction temperature
Modified PET polyester (NP-PET) is prepared, wherein, the pressure of precondensation stage reaction is 10KPa, and the reaction time is 60min, afterwards
Into the high vacuum stage of reaction, reaction pressure is 50Pa, and the reaction time is 4h, and the addition of carboxylate 2 is carboxylate 1
5mol%, the addition of catalyst is two kinds the 0.05% of carboxylate molal quantity sum；
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, 10g NP-PET are entered using HCl gases
The protection reaction of row deaminizating, the reaction time is 120min, obtains the modified PET polyester (N-PET) with amino side base；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.05 × 10-4The carboxymethyl-β-cyclodextrin of mol, 1.58
×10-4The NHS of mol and 1.58 × 10-4The EDCHCl of mol inserts container, and carboxylic is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on methyl beta-cyclodextrin and modified poly ester between amino side base, wherein, the matter of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 500, carboxymethyl-β-cyclodextrin is 1: 1.5: 1.5 with the molar ratio of catalyst to amount, under normal temperature and pressure conditionses, instead
It is 12h between seasonable, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.16 × 104, molecular weight distribution is 1.8, the fusing point of polyester
It it is 259 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 95.5% to the adsorption rate of rhodamine b, to mixture-metal
Ion (Cu2+、Ag+) adsorption rate of heavy metal ion is up to 97.5% in solution.
Embodiment 2
A kind of preparation method of efficient absorption polyester material：
(1) under nitrogen protection by 0.5mol terephthalic acid (TPA)s (PTA), 0.6mol ethylene glycol (EG) and the oxygen of 0.4mmol tri-
Change two antimony (Sb2O3) be placed in container, in 230 DEG C of reaction temperature, direct esterification reaction is carried out under 0.25MPa pressure and prepares esterification
Thing 1, the reaction time is that the molar ratio of 2h, PTA and EG is 1: 1.2, and catalyst loading is the 0.08mol% of PTA；In nitrogen
By 0.5mol terephthalic acid (TPA)s (PTA), 0.6molN-BOC- serinols and 0.5mmol antimony oxides (Sb under gas shielded2O3) put
It is 175 DEG C in reaction temperature in container, direct esterification reaction is carried out under normal pressure and prepares carboxylate 2, the reaction time is 3h, PTA
It is 1: 1.2 with the molar ratio of N-BOC- serinols；Wherein, catalyst loading is the 0.1mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.01mol carboxylates 2 and
0.168mmol antimony oxides (Sb2O3) be placed in container, carry out condensation polymerization reaction under conditions of being 275 DEG C in reaction temperature
NP-PET is prepared, wherein, the pressure of precondensation stage reaction is 20KPa, and the reaction time is 60min, anti-into high vacuum afterwards
Answer the stage, reaction pressure is 40Pa, the reaction time is 5h, and the addition of carboxylate 2 is the 5mol% of carboxylate 1, catalyst
Addition is two kinds the 0.08% of carboxylate molal quantity sum；
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, 10gNP-PET is entered using HCl gases
Row deaminizating protection group is reacted, and the reaction time is 90min, obtains the modified PET polyester (N-PET) with amino side base；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.15 × 10-4Mol carboxymethyl-β-cyclodextrins, 1.84 ×
10-4The NHS of mol and 1.84 × 10-4The EDCHCl of mol inserts container, and carboxylic first is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on base beta-schardinger dextrin and modified poly ester between amino side base, wherein, the quality of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 420, carboxymethyl-β-cyclodextrin is 1: 1.6: 1.6 with the molar ratio of catalyst, under normal temperature and pressure conditionses, reaction
Time is 16h, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.17 × 104, molecular weight distribution is 2.1, the fusing point of polyester
It it is 260 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 96.6% to the adsorption rate of rhodamine b, to mixture-metal
Ion (Cu2+、Ag+) adsorption rate of heavy metal ion is 97.3% in solution.
Embodiment 3
A kind of preparation method of efficient absorption polyester material：
(1) 0.5mol terephthalic acid (TPA)s (PTA), 0.75mol ethylene glycol (EG) and 1mmol tri- are aoxidized under nitrogen protection
Two antimony (Sb2O3) be placed in container, in 230 DEG C of reaction temperature, direct esterification reaction is carried out under 0.18MPa pressure and prepares carboxylate
1, the reaction time is that the molar ratio of 3h, PTA and EG is 1: 1.5, and catalyst loading is the 0.2mol% of PTA；In nitrogen
By 0.5mol terephthalic acid (TPA)s (PTA), 0.75molN-BOC- serinols and 0.3mmol antimony oxides (Sb under protection2O3) put
It is 190 DEG C in reaction temperature in container, direct esterification reaction is carried out under normal pressure and prepares carboxylate 2, the reaction time is 3.5h,
PTA is 1: 1.5 with the molar ratio of N-BOC- serinols；Wherein, catalyst loading is the 0.02mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.014mol carboxylates 2 and
0.1712mmol antimony oxides (Sb2O3) be placed in container, it is anti-to carry out condensation polymerization under conditions of being 280 DEG C in reaction temperature
NP-PET should be prepared, wherein, the pressure of precondensation stage reaction is 20KPa, and the reaction time is 60min, afterwards into high vacuum
The stage of reaction, reaction pressure is 30Pa, and the reaction time is 6h, and the addition of carboxylate 2 is the 7mol% of carboxylate 1, catalyst
Addition be two kinds the 0.08% of carboxylate molal quantity sum；
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, 10g NP-PET are entered using HCl gases
Row deaminizating protection group is reacted, and the reaction time is 120min, obtains the N-PET with amino side base；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.25 × 10-4The carboxymethyl-β-cyclodextrin of mol, 2.0 ×
10-4The NHS of mol and 2.0 × 10-4The EDCHCl of mol inserts container, and carboxylic first is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on base beta-schardinger dextrin and modified poly ester between amino side base, wherein, the quality of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 280, carboxymethyl-β-cyclodextrin is 1: 1.6: 1.6 with the molar ratio of catalyst, under normal temperature and pressure conditionses, reaction
Time is 18h, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.20 × 104, molecular weight distribution is 2.0, the fusing point of polyester
It it is 255 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 97.5% to the adsorption rate of rhodamine b, to mixture-metal
Ion (Cu2+、Ag+) adsorption rate of heavy metal ion is 97.8% in solution.
Embodiment 4
A kind of preparation method of efficient absorption polyester material：
(1) under nitrogen protection by 0.5mol terephthalic acid (TPA)s (PTA), 0.65mol ethylene glycol (EG) and 2mmol ethylene glycol
Aluminium (Al-EG) is placed in container, in 230 DEG C of reaction temperature, direct esterification reaction is carried out under 0.16MPa pressure and prepares carboxylate 1,
Stir speed (S.S.) is 210rpm, and the reaction time is that the molar ratio of 3h, PTA and EG is 1: 1.3, and catalyst loading is PTA's
0.4mol%；Under nitrogen protection by 0.5mol terephthalic acid (TPA)s (PTA), 0.75molN-BOC- Soviet Unions ammonia alcohol and 0.1mmol second two
Aluminium alcoholates (Al-EG) is placed in container, is 195 DEG C in reaction temperature, direct esterification reaction is carried out under normal pressure and prepares carboxylate 2, instead
For the mol ratio of 3h, PTA and N-BOC- Soviet Union ammonia alcohol is 1: 1.5 between seasonable；Wherein, catalyst loading is PTA's
0.02mol%；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.014mol carboxylates 2 and
0.214mmol ethylene glycol aluminium (Al-EG) is placed in container, and condensation polymerization reaction is carried out under conditions of being 280 DEG C in reaction temperature
NP-PET is prepared, wherein, the pressure of precondensation stage reaction is 30KPa, and the reaction time is 40min, anti-into high vacuum afterwards
Answer the stage, reaction pressure is 30Pa, the reaction time is 5h, and the addition of carboxylate 2 is the 7mol% of carboxylate 1, catalyst
Addition is two kinds the 0.1% of carboxylate molal quantity sum；
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, using 10% trifluoroacetic acid (TFA) solution
Deaminizating protection group reaction is carried out to 10g NP-PET, the reaction time is 30min, obtains the modified PET polyester with amino side base
(N-PET)；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.35 × 10-4The carboxymethyl-β-cyclodextrin of mol, 2.3 ×
10-4The NHS of mol and 2.3 × 10-4The EDCHCl of mol inserts container, and carboxylic first is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on base beta-schardinger dextrin and modified poly ester between amino side base, wherein, the quality of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 260, carboxymethyl-β-cyclodextrin is 1: 1.7: 1.7 with the molar ratio of catalyst, under normal temperature and pressure conditionses, reaction
Time is 18h, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.19 × 104, molecular weight distribution is 1.9, the fusing point of polyester
It it is 256.5 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 96.8% to the adsorption rate of rhodamine b, to a mixing huge sum of money
Category ion (Cu2+、Ag+) adsorption rate of heavy metal ion is 97% in solution.
Embodiment 5
A kind of preparation method of efficient absorption polyester material：
(1) under nitrogen protection by 0.5mol terephthalic acid (TPA)s (PTA), 0.75mol ethylene glycol (EG) and 1.5mmol second two
Aluminium alcoholates (A1-EG) is placed in container, in 240 DEG C of reaction temperature, direct esterification reaction is carried out under 0.2MPa pressure and prepares carboxylate
1, the reaction time is that the molar ratio of 2h, PTA and EG is 1: 1.5, and catalyst loading is the 0.3mol% of PTA；In nitrogen
0.5mol terephthalic acid (TPA)s (PTA), 0.6molN-BOC- Soviet Union's ammonia alcohol and 2mmol ethylene glycol aluminium (A1-EG) are placed in appearance under protection
It is 195 DEG C in reaction temperature in device, direct esterification reaction is carried out under normal pressure and prepares carboxylate 2, the reaction time is 4h, PTA and N-
The mol ratio of BOC- Soviet Unions ammonia alcohol is 1: 1.2；Wherein, catalyst loading is the 0.4mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.014mol carboxylates 2 and
0.428mmol ethylene glycol aluminium (Al-EG) is placed in container, and condensation polymerization reaction is carried out under conditions of being 280 DEG C in reaction temperature
NP-PET is prepared, wherein, the pressure of precondensation stage reaction is 30KPa, and the reaction time is 50min, anti-into high vacuum afterwards
Answer the stage, reaction pressure is 20Pa, the reaction time is 4h, and the addition of carboxylate 2 is the 7mol% of carboxylate 1, catalyst
Addition is two kinds the 0.2% of carboxylate molal quantity sum；
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, using 10% trifluoroacetic acid (TFA) solution
Deaminizating protection group reaction is carried out to 10g NP-PET, the reaction time is 15min, obtain the modified PET (N- with amino side base
PET)；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.15 × 10-4The carboxymethyl-β-cyclodextrin of mol, 1.96
×10-4The NHS of mol and 1.96 × 10-4The EDCHCl of mol inserts container, and carboxylic is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on methyl beta-cyclodextrin and modified poly ester between amino side base, wherein, the matter of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 320, carboxymethyl-β-cyclodextrin is 1: 1.7: 1.7 with the molar ratio of catalyst to amount, under normal temperature and pressure conditionses, instead
It is 24h between seasonable, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.18 × 104, molecular weight distribution is 1.9, the fusing point of polyester
It it is 256 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 96.5% to the adsorption rate of rhodamine b, to mixture-metal
Ion (Cu2+、Ag+) adsorption rate of heavy metal ion is 98% in solution.
Embodiment 6
A kind of preparation method of efficient absorption polyester material：
(1) under nitrogen protection by 0.5mol terephthalic acid (TPA)s (PTA), 0.7mol ethylene glycol (EG) and 2.5mmol acetic acid
Antimony is placed in container, in 245 DEG C of reaction temperature, direct esterification reaction is carried out under 0.2MPa pressure and prepares carboxylate 1, reaction time
It is that the molar ratio of 2.5h, PTA and EG is 1: 1.4, catalyst loading is the 0.5mol% of PTA；Under nitrogen protection will
0.5mol terephthalic acid (TPA)s (PTA), 0.8molN-BOC- Soviet Union's ammonia alcohol and 2.5mmol antimony acetates are placed in container, in reaction temperature
Be to carry out direct esterification reaction under 180 DEG C, normal pressure to prepare carboxylate 2, the reaction time is 4h, PTA with there is amino protecting group
The mol ratio of binary ammonia alcohol is 1: 1.6；Wherein, catalyst loading is the 0.5mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.014mol carboxylates 2 and
1.07mmol antimony acetates are placed in container, condensation polymerization reaction is carried out under conditions of being 285 DEG C in reaction temperature and prepares NP-PET,
Wherein, the pressure of precondensation stage reaction is 20KPa, and the reaction time is 60min, afterwards into the high vacuum stage of reaction, reaction
Pressure is 20Pa, and the reaction time is 4h, and the addition of carboxylate 2 is the 7mol% of carboxylate 1, and the addition of catalyst is two kinds
The 0.5% of carboxylate molal quantity sum；
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, using 10% trifluoroacetic acid (TFA) solution
Deaminizating protection group reaction is carried out to 10g NP-PET, the reaction time is 40min, obtains the modified PET polyester with amino side base
(N-PET)；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.25 × 10-4The carboxymethyl-β-cyclodextrin of mol, 2.25
×10-4The NHS of mol and 2.25 × 10-4The EDCHCl of mol inserts container, and carboxylic is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on methyl beta-cyclodextrin and modified poly ester between amino side base, wherein, the matter of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 280, carboxymethyl-β-cyclodextrin is 1: 1.8: 1.8 with the molar ratio of catalyst to amount, under normal temperature and pressure conditionses, instead
It is 20h between seasonable, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.14 × 104, molecular weight distribution is 1.9, the fusing point of polyester
It it is 256.5 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 97.1% to the adsorption rate of rhodamine b, to a mixing huge sum of money
Category ion (Cu2+、Ag+) adsorption rate of heavy metal ion is 98.1% in solution.
Embodiment 7
A kind of preparation method of efficient absorption polyester material：
(1) under nitrogen protection by 0.5mol terephthalic acid (TPA)s (PTA), 0.6mol ethylene glycol (EG) and 0.15mmol acetic acid
Antimony is placed in container, in 240 DEG C of reaction temperature, direct esterification reaction is carried out under 0.2MPa pressure and prepares carboxylate 1, reaction time
It is that the molar ratio of 2h, PTA and EG is 1: 1.2, catalyst loading is the 0.03mol% of PTA；Under nitrogen protection will
0.5mol terephthalic acid (TPA)s (PTA), 1molN-BOC- Soviet Union's ammonia alcohol and 0.1mmol antimony acetates are placed in container, are in reaction temperature
185 DEG C, direct esterification reaction is carried out under normal pressure and prepares carboxylate 2, the reaction time be 3h, PTA and N-BOC- Soviet Union ammonia alcohol mole
Than being 1: 2；Wherein, catalyst loading is the 0.02mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.01mol carboxylates 2 and
0.105mmol antimony acetates are placed in container, condensation polymerization reaction is carried out under conditions of being 270 DEG C in reaction temperature and prepares NP-
PET, wherein, the pressure of precondensation stage reaction is 30KPa, and the reaction time is 60min, afterwards into the high vacuum stage of reaction,
Reaction pressure is 30Pa, and the reaction time is 4h, and the addition of carboxylate 2 is the 5mol% of carboxylate 1, and the addition of catalyst is
Two kinds the 0.05% of carboxylate molal quantity sum；
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, using 10% trifluoroacetic acid (TFA) solution
Deaminizating protection group reaction is carried out to 10g NP-PET, the reaction time is 10min, obtains the modified PET polyester with amino side base
(N-PET)；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.05 × 10-4The carboxymethyl-β-cyclodextrin of mol, 1.58
×10-4The NHS of mol and 1.58 × 10-4The EDCHCl of mol inserts container, and carboxylic is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on methyl beta-cyclodextrin and modified poly ester between amino side base, wherein, the matter of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 480, carboxymethyl-β-cyclodextrin is 1: 1.5: 1.5 with the molar ratio of catalyst to amount, under normal temperature and pressure conditionses, instead
It is 24h between seasonable, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.22 × 104, molecular weight distribution is 1.9, the fusing point of polyester
It it is 258.5 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 95.7% to the adsorption rate of rhodamine b, to a mixing huge sum of money
Category ion (Cu2+、Ag+) adsorption rate of heavy metal ion is 98.2% in solution.
Embodiment 8
A kind of preparation method of efficient absorption polyester material：
(1) under nitrogen protection by 0.5mol terephthalic acid (TPA)s (PTA), 0.65mol ethylene glycol (EG) and 1.5mmol acetic acid
Antimony is placed in container, in 250 DEG C of reaction temperature, direct esterification reaction is carried out under 0.2MPa pressure and prepares carboxylate 1, reaction time
It is that the molar ratio of 2h, PTA and EG is 1: 1.3, catalyst loading is the 0.3mol% of PTA；Under nitrogen protection will
0.5mol terephthalic acid (TPA)s (PTA), 0.9molFmoc- serinols and 1mmol antimony acetates are placed in container, are in reaction temperature
180 DEG C, direct esterification reaction is carried out under normal pressure and prepares carboxylate 2, the reaction time is 3h, PTA and two with amino protecting group
The mol ratio of first ammonia alcohol is 1: 1.8；Wherein, catalyst loading is the 0.2mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.01mol carboxylates 2 and
1.05mmol antimony acetates are placed in container, condensation polymerization reaction is carried out under conditions of being 275 DEG C in reaction temperature and prepares NP-PET,
Wherein, the pressure of precondensation stage reaction is 10KPa, and the reaction time is 90min, afterwards into the high vacuum stage of reaction, reaction
Pressure is 10Pa, and the reaction time is 4h, and the addition of carboxylate 2 is the 5mol% of carboxylate 1, and the addition of catalyst is two kinds
The 0.5% of carboxylate molal quantity sum：
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, 10g NP-PET are entered using HCl gases
Row deaminizating protection group is reacted, and the reaction time is 120min, obtains the modified PET polyester (N-PET) with amino side base；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.15 × 10-4The carboxymethyl-β-cyclodextrin of mol, 2.07
×10-4The NHS of mol and 2.07 × 10-4The EDCHCl of mol inserts container, and carboxylic is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on methyl beta-cyclodextrin and modified poly ester between amino side base, wherein, the matter of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 420, carboxymethyl-β-cyclodextrin is 1: 1.8: 1.8 with the molar ratio of catalyst to amount, under normal temperature and pressure conditionses, instead
It is 12h between seasonable, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.11 × 104, molecular weight distribution is 1.9, the fusing point of polyester
It it is 254 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 96.8% to the adsorption rate of rhodamine b, to mixture-metal
Ion (Cu2+、Ag+) adsorption rate of heavy metal ion is 97% in solution.
Embodiment 9
A kind of preparation method of efficient absorption polyester material：
(1) under nitrogen protection by 0.5mol terephthalic acid (TPA)s (PTA), 0.6mol ethylene glycol (EG) and 2mmol antimony acetates
It is placed in container, in 230 DEG C of reaction temperature, direct esterification reaction is carried out under 0.2MPa pressure and prepares carboxylate 1, stirs the reaction time
It is that the molar ratio of 2h, PTA and EG is 1: 1.2, catalyst loading is the 0.4mol% of PTA；Under nitrogen protection will
0.5mol terephthalic acid (TPA)s (PTA), 1molN-BOC- serinols and 2.5mmol antimony acetates are placed in container, are in reaction temperature
190 DEG C, direct esterification reaction is carried out under normal pressure and prepares carboxylate 2, the reaction time is feeding intake for 3h, PTA and N-BOC- serinol
Mol ratio is 1: 2；Wherein, catalyst loading is the 0.5mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.01mol carboxylates 2 and
1.26mmol antimony acetates are placed in container, condensation polymerization reaction is carried out under conditions of being 290 DEG C in reaction temperature and prepares NP-PET,
Wherein, the pressure of precondensation stage reaction is 10KPa, and the reaction time is 60min, afterwards into the high vacuum stage of reaction, reaction
Pressure is 50Pa, and the reaction time is 4h, and the addition of carboxylate 2 is the 5mol% of carboxylate 1, and the addition of catalyst is two kinds
The 0.6% of carboxylate molal quantity sum；
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, using 10% trifluoroacetic acid (TFA) solution
Deaminizating protection group reaction is carried out to 10g NP-PET, the reaction time is 30min, and stir speed (S.S.) is 150rpm, obtain band amino
The modified PET polyester (N-PET) of side base；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.25 × 104The carboxymethyl-β-cyclodextrin of mol, 1.88
×10-4The NHS of mol and 1.88 × 10-4The EDCHCl of mol inserts container, and carboxylic is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on methyl beta-cyclodextrin and modified poly ester between amino side base, wherein, the matter of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 400, carboxymethyl-β-cyclodextrin is 1: 1.5: 1.5 with the molar ratio of catalyst to amount, under normal temperature and pressure conditionses, instead
It is 20h between seasonable, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.25 × 104, molecular weight distribution is 1.8, the fusing point of polyester
It it is 259 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 97.1% to the adsorption rate of rhodamine b, to mixture-metal
Ion (Cu2+、Ag+) adsorption rate of heavy metal ion is 97.5% in solution.
Embodiment 10
A kind of preparation method of efficient absorption polyester material：
(1) under nitrogen protection by 0.5mol terephthalic acid (TPA)s (PTA), 0.6mol ethylene glycol (EG) and 2.5mmol acetic acid
Antimony is placed in container, in 250 DEG C of reaction temperature, direct esterification reaction is carried out under 0.18MPa pressure and prepares carboxylate 1, stirs reaction
Time is that the molar ratio of 2.5h, PTA and EG is 1: 1.2, and catalyst loading is the 0.5mol% of PTA；In nitrogen protection
It is lower that 0.5mol terephthalic acid (TPA)s (PTA), 1molN-BOC- serinols and 0.4mmol antimony acetates are placed in container, in reaction temperature
It is to carry out direct esterification reaction under 190 DEG C, normal pressure to prepare carboxylate 2 to spend, and the reaction time is 3h, PTA and N-BOC- serinol
Molar ratio is 1: 2；Wherein, catalyst loading is the 0.08mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.014mol carboxylates 2 and
4.28mmol antimony acetates are placed in container, condensation polymerization reaction is carried out under conditions of being 275 DEG C in reaction temperature and prepares NP-PET,
Wherein, the pressure of precondensation stage reaction is 10KPa, and the reaction time is 60min, afterwards into the high vacuum stage of reaction, reaction
Pressure is 50Pa, and the reaction time is 6h, and the addition of carboxylate 2 is the 7mol% of carboxylate 1, and the addition of catalyst is two kinds
The 0.2% of carboxylate molal quantity sum；
(3) it is right under normal temperature and pressure environmental condition after step (2) reaction terminates, it is molten using 10% trifluoroacetic acid (TFA)
Liquid carries out deaminizating protection group reaction to 10g NP-PET, and the reaction time is 30min, obtains the modified PET with amino side base and gathers
Ester (N-PET).；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.25 × 10-4The carboxymethyl-β-cyclodextrin of mol, 1.88
×10-4The NHS of mol and 1.88 × 10-4The EDCHCl of mol inserts container, and carboxylic is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on methyl beta-cyclodextrin and modified poly ester between amino side base, wherein, the matter of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 280, carboxymethyl-β-cyclodextrin is 1: 1.5: 1.5 with the molar ratio of catalyst to amount, under normal temperature and pressure conditionses, instead
It is 16h between seasonable, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.15 × 104, molecular weight distribution is 2.0, the fusing point of polyester
It it is 258 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 96.5% to the adsorption rate of rhodamine b, to mixture-metal
Ion (Cu2+、Ag+) adsorption rate of heavy metal ion is 98.3% in solution.
Embodiment 11
A kind of preparation method of efficient absorption polyester material：
(1) 0.5mol terephthalic acid (TPA)s (PTA), 0.7mol ethylene glycol (EG) and 3mmol tri- are aoxidized under nitrogen protection
Two antimony (Sb2O3) be placed in container, in 230 DEG C of reaction temperature, direct esterification reaction is carried out under 0.19MPa pressure and prepares carboxylate
1, the reaction time is that the molar ratio of 2h, PTA and EG is 1: 1.4, and catalyst loading is the 0.6mol% of PTA；In nitrogen
By 0.5mol terephthalic acid (TPA)s (PTA), 0.6molN-BOC- serinols and 1mmol antimony oxides (Sb under protection2O3) it is placed in appearance
It is 185 DEG C in reaction temperature in device, direct esterification reaction is carried out under normal pressure and prepares carboxylate 2, the reaction time is 3h, PTA and N-
The molar ratio of BOC- serinols is 1: 1.2；Wherein, catalyst loading is the 0.2mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.02mol carboxylates 2 and
0.11mmol antimony oxides (Sb2O3) be placed in container, carry out condensation polymerization reaction under conditions of being 280 DEG C in reaction temperature
NP-PET is prepared, wherein, the pressure of precondensation stage reaction is 20KPa, and the reaction time is 50min, anti-into high vacuum afterwards
Answer the stage, reaction pressure is 30Pa, the reaction time is 6h, and the addition of carboxylate 2 is the 10mol% of carboxylate 1, catalyst
Addition is two kinds the 0.05% of carboxylate molal quantity sum；
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, using 10% trifluoroacetic acid (TFA) solution
Deaminizating protection group reaction is carried out to 10g NP-PET, the reaction time is 20min, obtains the modified PET polyester with amino side base
(N-PET)；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.05 × 10-4The carboxymethyl-β-cyclodextrin of mol, 1.58
×10-4The NHS of mol and 1.58 × 10-4The EDCHCl of mol inserts container, and carboxylic is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on methyl beta-cyclodextrin and modified poly ester between amino side base, wherein, the matter of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 125, carboxymethyl-β-cyclodextrin is 1: 1.5: 1.5 with the molar ratio of catalyst to amount, under normal temperature and pressure conditionses, instead
It is 20h between seasonable, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.12 × 104, molecular weight distribution is 1.9, the fusing point of polyester
It it is 256 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 96.8% to the adsorption rate of rhodamine b, to mixture-metal
Ion (Cu2+、Ag+) adsorption rate of heavy metal ion is 97.9% in solution.
Embodiment 12
A kind of preparation method of efficient absorption polyester material：
(1) under nitrogen protection by 0.5mol terephthalic acid (TPA)s (PTA), 0.75mol ethylene glycol (EG) and the oxygen of 1.5mmol tri-
Change two antimony (Sb2O3) be placed in container, in 240 DEG C of reaction temperature, direct esterification reaction is carried out under 0.2MPa pressure and prepares carboxylate
1, the reaction time is that the molar ratio of 3h, PTA and EG is 1: 1.5, and catalyst loading is the 0.3mol% of PTA；In nitrogen
By 0.5mol terephthalic acid (TPA)s (PTA), 1molFmoc- serinols and 0.2mmol antimony oxides (Sb under protection2O3) it is placed in appearance
Be 175 DEG C in reaction temperature in device, direct esterification reaction carried out under normal pressure and prepares carboxylate 2, the reaction time is 3h, PTA with
The mol ratio of Fmoc- serinols is 1: 2；Wherein, catalyst loading is the 0.04mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.04mol carboxylates 2 and
0.12mmol antimony oxides (Sb2O3) be placed in container, carry out condensation polymerization reaction under conditions of being 275 DEG C in reaction temperature
NP-PET is prepared, wherein, the pressure of precondensation stage reaction is 10KPa, and the reaction time is 60min, anti-into high vacuum afterwards
Answer the stage, reaction pressure is 50Pa, the reaction time is 6h, and the addition of carboxylate 2 is the 7mol% of carboxylate 1, catalyst
Addition is two kinds the 0.05% of carboxylate molal quantity sum；
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, 10g NP-PET are entered using HCl gases
Row deaminizating protection group is reacted, and the reaction time is 90min, obtains the modified PET polyester (N-PET) with amino side base；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.25 × 10-4The carboxymethyl-β-cyclodextrin of mol, 1.88
×10-4The NHS of mol and 1.88 × 10-4The EDCHCl of mol inserts container, and carboxylic is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on methyl beta-cyclodextrin and modified poly ester between amino side base, wherein, the matter of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 280, carboxymethyl-β-cyclodextrin is 1: 1.5: 1.5 with the molar ratio of catalyst to amount, under normal temperature and pressure conditionses, instead
It is 16h between seasonable, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.21 × 104, molecular weight distribution is 2.0, the fusing point of polyester
It it is 254 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 97.9% to the adsorption rate of rhodamine b, to mixture-metal
Ion (Cu2+、Ag+) adsorption rate of heavy metal ion is 98.5% in solution.
Embodiment 13
A kind of preparation method of efficient absorption polyester material：
(1) under nitrogen protection by 0.5mol terephthalic acid (TPA)s (PTA), 0.6mol ethylene glycol (EG) and the oxygen of 1.5mmol tri-
Change two antimony (Sb2O3) be placed in container, in 240 DEG C of reaction temperature, direct esterification reaction is carried out under 0.2MPa pressure and prepares carboxylate
1, the reaction time is that the molar ratio of 2h, PTA and EG is 1: 1.2, and catalyst loading is the 0.3mol% of PTA；In nitrogen
By 0.5mol terephthalic acid (TPA)s (PTA), 0.9molFmoc- serinols and 1mmol antimony oxides (Sb under protection2O3) it is placed in appearance
Be 195 DEG C in reaction temperature in device, direct esterification reaction carried out under normal pressure and prepares carboxylate 2, the reaction time is 3h, PTA with
The mol ratio of Fmoc- serinols is 1: 1.8；Wherein, catalyst loading is the 0.2mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.01mol carboxylates 2 and
1.05mmol antimony oxides (Sb2O3) be placed in container, carry out condensation polymerization reaction under conditions of being 280 DEG C in reaction temperature
NP-PET is prepared, wherein, the pressure of precondensation stage reaction is 30KPa, and the reaction time is 60min, anti-into high vacuum afterwards
Answer the stage, reaction pressure is 50Pa, the reaction time is 6h, and the addition of carboxylate 2 is the 5mol% of carboxylate 1, catalyst
Addition is two kinds the 0.5% of carboxylate molal quantity sum；
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, 10g NP-PET are entered using HCl gases
Row deaminizating protection group is reacted, and the reaction time is 60min, obtains the modified PET polyester (N-PET) with amino side base；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.05 × 10-4The carboxymethyl-β-cyclodextrin of mol, 1.58
×10-4The NHS of mol and 1.58 × 10-4The EDCHCl of mol inserts container, and carboxylic is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on methyl beta-cyclodextrin and modified poly ester between amino side base, wherein, the matter of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 500, carboxymethyl-β-cyclodextrin is 1: 1.5: 1.5 with the molar ratio of catalyst to amount, under normal temperature and pressure conditionses, instead
It is 22h between seasonable, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.24 × 104, molecular weight distribution is 1.8, the fusing point of polyester
It it is 255 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 96.2% to the adsorption rate of rhodamine b, to mixture-metal
Ion (Cu2+、Ag+) adsorption rate of heavy metal ion is 97.1% in solution.
Embodiment 14
A kind of preparation method of efficient absorption polyester material：
(1) 0.5mol terephthalic acid (TPA)s (PTA), 0.65mol ethylene glycol (EG) and 3mmol tri- are aoxidized under nitrogen protection
Two antimony (Sb2O3) be placed in container, in 220 DEG C of reaction temperature, direct esterification reaction is carried out under 0.25MPa pressure and prepares carboxylate
1, the reaction time is that the molar ratio of 2h, PTA and EG is 1: 1.3, and catalyst loading is the 0.6mol% of PTA；In nitrogen
By 0.5mol terephthalic acid (TPA)s (PTA), 0.6molFmoc- Soviet Unions ammonia alcohol and 5mmol antimony oxides (Sb under protection2O3) it is placed in appearance
Be 200 DEG C in reaction temperature in device, direct esterification reaction carried out under normal pressure and prepares carboxylate 2, the reaction time is 3h, PTA with
The mol ratio of Fmoc- Soviet Unions ammonia alcohol is 1: 1.2；Wherein, catalyst loading is the 0.1mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.014mol carboxylates 2 and
2.14mmol antimony oxides (Sb2O3) be placed in container, carry out condensation polymerization reaction under conditions of being 285 DEG C in reaction temperature
NP-PET is prepared, wherein, the pressure of precondensation stage reaction is 20KPa, and the reaction time is 50min, anti-into high vacuum afterwards
Answer the stage, reaction pressure is 20Pa, the reaction time is 5h, and the addition of carboxylate 2 is the 7mol% of carboxylate 1, catalyst
Addition is two kinds the 0.1% of carboxylate molal quantity sum；
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, 10g NP-PET are entered using HCl gases
Row deaminizating protection group is reacted, and the reaction time is 90min, obtains the modified PET polyester (N-PET) with amino side base；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.25 × 10-4The carboxymethyl-β-cyclodextrin of mol, 1.88
×10-4The NHS of mol and 1.88 × 10-4The EDCHCl of mol inserts container, and carboxylic is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on methyl beta-cyclodextrin and modified poly ester between amino side base, wherein, the matter of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 280, carboxymethyl-β-cyclodextrin is 1: 1.5: 1.5 with the molar ratio of catalyst to amount, under normal temperature and pressure conditionses, instead
It is 16h between seasonable, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.17 × 104, molecular weight distribution is 1.9, the fusing point of polyester
It it is 257 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 96.8% to the adsorption rate of rhodamine b, to mixture-metal
Ion (Cu2+、Ag+) adsorption rate of heavy metal ion is 98.2% in solution.
Embodiment 15
A kind of preparation method of efficient absorption polyester material：
(1) 0.5mol terephthalic acid (TPA)s (PTA), 0.75mol ethylene glycol (EG) and 4mmol tri- are aoxidized under nitrogen protection
Two antimony (Sb2O3) be placed in container, in 255 DEG C of reaction temperature, direct esterification reaction is carried out under 0.18MPa pressure and prepares carboxylate
1, the reaction time is that the molar ratio of 2h, PTA and EG is 1: 1.5, and catalyst loading is the 0.8mol% of PTA；In nitrogen
By 0.5mol terephthalic acid (TPA)s (PTA), 1.5molFmo- Soviet Unions ammonia alcohol and 3mmol antimony oxides (Sb under protection2O3) it is placed in container
In, be 175 DEG C in reaction temperature, direct esterification reaction is carried out under normal pressure and prepares carboxylate 2, the reaction time is 3h, PTA with have
The mol ratio of the binary ammonia alcohol of amino protecting group is 1: 3；Wherein, catalyst loading is the 0.6mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.02mol carboxylates 2 and
1.1mmol antimony oxides (Sb2O3) be placed in container, condensation polymerization reaction system is carried out under conditions of being 290 DEG C in reaction temperature
Standby NP-PET, wherein, the pressure of precondensation stage reaction is 10KPa, and the reaction time is 60min, high vacuum is entered afterwards and is reacted
In the stage, reaction pressure is 30Pa, and the reaction time is 4h, the addition of carboxylate 2 is the 10mol% of carboxylate 1, and catalyst adds
Dosage is two kinds the 0.5% of carboxylate molal quantity sum；
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, 10g NP-PET are entered using HCl gases
Row deaminizating protection group is reacted, and the reaction time is 120min, obtains the modified PET polyester (N-PET) with amino side base；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.15 × 10-4The carboxymethyl-β-cyclodextrin of mol, 1.73
×10-4The NHS of mol and 1.73 × 10-4The EDCHCl of mol inserts container, and carboxylic is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on methyl beta-cyclodextrin and modified poly ester between amino side base, wherein, the matter of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 220, carboxymethyl-β-cyclodextrin is 1: 1.5: 1.5 with the molar ratio of catalyst to amount, under normal temperature and pressure conditionses, instead
It is 22h between seasonable, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.23 × 104, molecular weight distribution is 2.0, the fusing point of polyester
It it is 257 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 94.9% to the adsorption rate of rhodamine b, to mixture-metal
Ion (Cu2+、Ag+) adsorption rate of heavy metal ion is 96.9% in solution.
Embodiment 16
A kind of preparation method of efficient absorption polyester material：
(1) 0.5mol terephthalic acid (TPA)s (PTA), 0.6mol ethylene glycol (EG) and 4mmol tri- are aoxidized under nitrogen protection
Two antimony (Sb2O3) be placed in container, in 230 DEG C of reaction temperature, direct esterification reaction is carried out under 0.2MPa pressure and prepares carboxylate 1,
Reaction time is that the molar ratio of 2h, PTA and EG is 1: 1.2, and catalyst loading is the 0.8mol% of PTA；Protected in nitrogen
By 0.5mol terephthalic acid (TPA)s (PTA), 1molFmoc- Soviet Unions ammonia alcohol and 2.5mmol antimony oxides (Sb under shield2O3) it is placed in container
In, be 175 DEG C in reaction temperature, direct esterification reaction is carried out under normal pressure and prepares carboxylate 2, the reaction time is 3h, PTA with
The mol ratio of Fmoc- Soviet Unions ammonia alcohol is 1: 2；Wherein, catalyst loading is the 0.5mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.02mol carboxylates 2 and
1.76mmol antimony oxides (Sb2O3) be placed in container, carry out condensation polymerization reaction under conditions of being 270 DEG C in reaction temperature
NP-PET is prepared, wherein, the pressure of precondensation stage reaction is 10KPa, and the reaction time is 50min, anti-into high vacuum afterwards
Answer the stage, reaction pressure is 20Pa, the reaction time is 5h, and the addition of carboxylate 2 is the 10mol% of carboxylate 1, catalyst
Addition is two kinds the 0.8% of carboxylate molal quantity sum；
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, 10g NP-PET are entered using HCl gases
Row deaminizating protection group is reacted, and the reaction time is 100min, obtains the modified PET polyester (N-PET) with amino side base；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.1 × 10-4The carboxymethyl-β-cyclodextrin of mol, 1.65 ×
10-4The NHS of mol and 1.65 × 10-4The EDCHCl of mol inserts container, and carboxylic first is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on base beta-schardinger dextrin and modified poly ester between amino side base, wherein, the quality of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 230, carboxymethyl-β-cyclodextrin is 1: 1.5: 1.5 with the molar ratio of catalyst, under normal temperature and pressure conditionses, reaction
Time is 24h, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.13 × 104, molecular weight distribution is 2.0, the fusing point of polyester
It it is 254 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 96.9% to the adsorption rate of rhodamine b, to mixture-metal
Ion (Cu2+、Ag+) adsorption rate of heavy metal ion is 97.1% in solution.
Embodiment 17
A kind of preparation method of efficient absorption polyester material：
(1) 0.5mol terephthalic acid (TPA)s (PTA), 0.6mol ethylene glycol (EG) and 4mmol tri- are aoxidized under nitrogen protection
Two antimony (Sb2O3) be placed in container, in 230 DEG C of reaction temperature, direct esterification reaction is carried out under 0.18MPa pressure and prepares carboxylate
1, the reaction time is that the molar ratio of 2h, PTA and EG is 1: 1.2, and catalyst loading is the 0.8mol% of PTA；In nitrogen
By 0.5mol terephthalic acid (TPA)s (PTA), 1molFmoc- Soviet Unions ammonia alcohol and 2.5mmol antimony oxides (Sb under protection2O3) it is placed in appearance
Be 180 DEG C in reaction temperature in device, direct esterification reaction carried out under normal pressure and prepares carboxylate 2, the reaction time is 3h, PTA with
The mol ratio of Fmoc- Soviet Unions ammonia alcohol is 1: 2；Wherein, catalyst loading is the 0.5mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.02mol carboxylates 2 and
1.76mmol antimony oxides (Sb2O3) be placed in container, carry out condensation polymerization reaction under conditions of being 270 DEG C in reaction temperature
NP-PET is prepared, wherein, the pressure of precondensation stage reaction is 10KPa, and the reaction time is 50min, anti-into high vacuum afterwards
Answer the stage, reaction pressure is 20Pa, the reaction time is 4h, and the addition of carboxylate 2 is the 10mol% of carboxylate 1, catalyst
Addition is two kinds the 0.8% of carboxylate molal quantity sum；
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, using 10% trifluoroacetic acid (TFA) solution
Deaminizating protection group reaction is carried out to 10g NP-PET, the reaction time is 30min, obtains the modified PET polyester with amino side base
(N-PET)；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.3 × 10-4The carboxymethyl-β-cyclodextrin of mol, 1.95 ×
10-4The NHS of mol and 1.95 × 10-4The EDCHCl of mol inserts container, and carboxylic first is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on base beta-schardinger dextrin and modified poly ester between amino side base, wherein, the quality of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 200, carboxymethyl-β-cyclodextrin is 1: 1.5: 1.5 with the molar ratio of catalyst, under normal temperature and pressure conditionses, reaction
Time is 24h, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.15 × 104, molecular weight distribution is 2.0, the fusing point of polyester
It it is 254.5 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 96.8% to the adsorption rate of rhodamine b, to a mixing huge sum of money
Category ion (Cu2+、Ag+) adsorption rate of heavy metal ion is 97.5% in solution.
Embodiment 18
A kind of preparation method of efficient absorption polyester material：
(1) 0.5mol terephthalic acid (TPA)s (PTA), 0.6mol ethylene glycol (EG) and 4mmol tri- are aoxidized under nitrogen protection
Two antimony (Sb2O3) be placed in container, in 230 DEG C of reaction temperature, direct esterification reaction is carried out under 0.2MPa pressure and prepares carboxylate 1,
Reaction time is that the molar ratio of 2h, PTA and EG is 1: 1.2, and catalyst loading is the 0.8mol% of PTA；Protected in nitrogen
By 0.5mol terephthalic acid (TPA)s (PTA), 1molFmoc- Soviet Unions ammonia alcohol and 2.5mmol antimony oxides (Sb under shield2O3) it is placed in container
In, be 180 DEG C in reaction temperature, direct esterification reaction is carried out under normal pressure and prepares carboxylate 2, the reaction time is 3h, PTA with
The mol ratio of Fmoc- Soviet Unions ammonia alcohol is 1: 2；Wherein, catalyst loading is the 0.5mol% of PTA；
(2) after step (1) reaction terminate after, under nitrogen protection by 0.2mol carboxylates 1,0.02mol carboxylates 2 and
1.76mmol antimony oxides (Sb2O3) be placed in container, carry out condensation polymerization reaction under conditions of being 270 DEG C in reaction temperature
NP-PET is prepared, wherein, the pressure of precondensation stage reaction is 10KPa, and the reaction time is 50min, anti-into high vacuum afterwards
Answer the stage, reaction pressure is 20Pa, the reaction time is 5h, and the addition of carboxylate 2 is the 10mol% of carboxylate 1, catalyst
Addition is two kinds the 0.8% of carboxylate molal quantity sum；
(3) after step (2) reaction terminates, under normal temperature and pressure environmental condition, using 10% trifluoroacetic acid (TFA) solution
Deaminizating protection group reaction is carried out to 10g NP-PET, the reaction time is 10min, obtains the modified PET polyester with amino side base
(N-PET)；
(4) after step (3) reaction terminates, by the N-PET of 5g, 1.2 × 10-4The carboxymethyl-β-cyclodextrin of mol, 1.8 ×
10-4The NHS of mol and 1.8 × 10-4The EDCHCl of mol inserts container, and carboxylic first is realized in hexafluoroisopropanol (HFIP) solution
Combination reaction on base beta-schardinger dextrin and modified poly ester between amino side base, wherein, the quality of carboxymethyl-β-cyclodextrin and N-PET
Than being 1: 200, carboxymethyl-β-cyclodextrin is 1: 1.5: 1.5 with the molar ratio of catalyst, under normal temperature and pressure conditionses, reaction
Time is 18h, obtains the N-PET-g-CD polyester with high adsorption.
The weight average molecular weight of the N-PET polyester of above-mentioned synthesis is 4.16 × 104, molecular weight distribution is 2.0, the fusing point of polyester
Be 254 DEG C, after chemical immobilized carboxymethyl-β-cyclodextrin, sample is up to 97% to the adsorption rate of rhodamine b, to mixture-metal from
Son (Cu2+、Ag+) adsorption rate of heavy metal ion is 98.2% in solution.
Claims (10)
1. a kind of efficient absorption polyester material, it is characterised in that the polyester is the modified PET polyester (NP- with amino side base
), and cyclodextrin or derivatives thereof the chemistry on its strand is immobilized PET.
2. efficient absorption polyester material as claimed in claim 1, it is characterised in that the modified PET with amino side base
The function side base of polyester is the amino with protection group.
3. the preparation method of the efficient absorption polyester material described in a kind of claim 1 or 2, it is characterised in that including following
Step：
Step 1)：Terephthalic acid (TPA), ethylene glycol and catalyst one are placed in container under nitrogen protection, at 220~260 DEG C,
Esterification is carried out under the conditions of 0.1~0.3MPa and prepares carboxylate one, the reaction time is 1.5~3h；Terephthalic acid (TPA) and second two
The mol ratio of alcohol addition is 1: 1.2~1: 1.5, the addition of catalyst one for terephthalic acid (TPA) molal quantity 0.01~
0.1%；
Step 2)：Terephthalic acid (TPA), the binary ammonia alcohol with amino protecting group and catalyst one are placed in appearance under nitrogen protection
In device, esterification is carried out under 140~200 DEG C, condition of normal pressure and prepares carboxylate two, the reaction time is 2~4h, terephthaldehyde
Acid is 1: 1.2~1: 3 with the mol ratio of the binary ammonia alcohol addition with amino protecting group；The addition of catalyst one is to benzene
The 0.01~0.1% of dioctyl phthalate molal quantity；
Step 3)：Carboxylate one, carboxylate one and catalyst one are placed in container under nitrogen protection, are in reaction temperature
Condensation polymerization reaction is carried out under conditions of 270~290 DEG C and prepares NP-PET polyester, wherein, the pressure of precondensation stage reaction is 1
~50KPa, the reaction time is 30~60min, and afterwards into the high vacuum stage of reaction, reaction pressure is 10~150Pa, during reaction
Between be 2~4h；The addition of carboxylate two is the 5~20% of the molal quantity of carboxylate one, and the addition of catalyst one is two kinds
The 0.01~0.1% of carboxylate molal quantity sum；
Step 4)：Suitable amino deprotecting regent is selected, deaminizating protection group reaction, reaction time are carried out to NP-PET polyester
It is 10~120min, obtains N-PET polyester；
Step 5)：N-PET solution, cyclodextrin or derivatives thereof and catalyst two are inserted into container, under normal temperature and pressure react 12~
24h, obtains the N-PET-g-CD polyester with high adsorption；Wherein, cyclodextrin or derivatives thereof and the mass ratio of N-PET are 1:
125~1: 500, cyclodextrin or derivatives thereof is 1: 1.5~1: 2 with the mol ratio of catalyst two.
4. the preparation method of efficient absorption polyester material as claimed in claim 3, it is characterised in that the step 1)~3)
Middle catalyst one is using organo-antimony compound, organo-tin compound or organo-aluminum compound.
5. the preparation method of efficient absorption polyester material as claimed in claim 3, it is characterised in that the step 2) in tool
The binary ammonia alcohol for having amino protecting group uses Boc- aminopropane diol compounds, Fmoc- aminopropane diol compounds, Boc- amino
Butanediol compound or Fmoc- amino butanediol compounds.
6. the preparation method of efficient absorption polyester material as claimed in claim 3, it is characterised in that the step 4) in ammonia
Base deprotecting regent uses HCl gases or trifluoroacetic acid solution.
7. the preparation method of efficient absorption polyester material as claimed in claim 3, it is characterised in that the step 5) in N-
The solvent of PET solution uses hexafluoroisopropanol.
8. the preparation method of efficient absorption polyester material as claimed in claim 3, it is characterised in that the step 5) middle ring
Dextrin or derivatives thereof uses carboxymethyl-β-cyclodextrin.
9. the preparation method of efficient absorption polyester material as claimed in claim 3, it is characterised in that the step 5) in urge
Agent two is using the compound of both N-hydroxy-succinamide and 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides
Catalyst.
10. the preparation method of efficient absorption polyester material as claimed in claim 3, it is characterised in that the step 5)
After reaction terminates, if product is liquid, need to repeatedly filter, wash and be vacuum dried through Precipitation in excessive ice methyl alcohol；If
Product is solid, need to obtain final product N-PET-g-CD through excessive deionized water cyclic washing, vacuum drying.
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Cited By (8)
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| CN107759779A (en) * | 2017-11-13 | 2018-03-06 | 东华大学 | A kind of bacteria resistant polyester material and preparation method thereof |
| CN109594145A (en) * | 2018-12-13 | 2019-04-09 | 上海德福伦化纤有限公司 | Flame-proof antibiotic master batch and preparation method thereof containing metal-modified cross carboxylate |
| CN111636145A (en) * | 2020-06-15 | 2020-09-08 | 邓颖菁 | Polyester fiber film for adsorbing heavy metals and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107759779B (en) * | 2017-11-13 | 2020-04-07 | 东华大学 | Antibacterial polyester material and preparation method thereof |
| CN109594145A (en) * | 2018-12-13 | 2019-04-09 | 上海德福伦化纤有限公司 | Flame-proof antibiotic master batch and preparation method thereof containing metal-modified cross carboxylate |
| CN111636145A (en) * | 2020-06-15 | 2020-09-08 | 邓颖菁 | Polyester fiber film for adsorbing heavy metals and preparation method thereof |
| CN111728837A (en) * | 2020-07-22 | 2020-10-02 | 万贤能 | Exercise massage belt capable of rubbing abdomen and chest and throwing butterfly sleeves and preparation method thereof |
| CN112176446A (en) * | 2020-10-16 | 2021-01-05 | 邓颖菁 | Antibacterial polyester fiber and preparation method thereof |
| CN113882152A (en) * | 2021-12-09 | 2022-01-04 | 天津市职业大学 | Preparation method of antibacterial easily-regenerated fiber material for treating oily sewage |
| CN114874422A (en) * | 2022-06-16 | 2022-08-09 | 上海云沂生物医药科技有限公司 | Polyalkylamine, and synthesis method, particle and application thereof |
| US11939246B1 (en) | 2023-05-10 | 2024-03-26 | King Saud University | Method of removing pollutants from water using waste polyethylene terephthalate |
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