CN101596464B - Circular type esterification reaction polymer catalyst and preparation method and application thereof - Google Patents
Circular type esterification reaction polymer catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a circular type esterification reaction polymer catalyst, belonging to the field of environmentally friendly macromolecule; the solid macromolecule obtained by synthesis can not only serve as catalyst which can be applied to esterification reaction but also achieve the purposes of recycling and easy separation. The polymer catalyst has the structural formula as shown in the right, wherein f, m is any integer from 1 to 1000, R1 is selected from -C6H4-,-COO(CH2CH2O)nOCO-,-COO(CH2CHCH3O)nOCO- or -COOCH2CH2OCOC6H4COOCH2CH2OCO-, and n is any integer from 2 to 10. R2 is selected from -H or -CH3, R3 is selected from -OCOCH3, -COOCH2C2H3O, -COOR4 or -COOR5OH, and R4 and R5 are both alkyl groups with 1-12 carbon atoms.
Description
Technical field
The invention belongs to environmentally friendly macromolecule and application thereof.
Background technology
Carboxylate is a kind of important organic compound, not only can be used as the organic synthesis raw material, and is important fine chemical product, is widely used in industries such as spices, daily use chemicals, food, medicine, rubber, coating.But in the preparation process of these ester type compounds, contain the esterification that takes place between compound and the carboxylic acid of the hydroxyl step that is absolutely necessary, in this course of reaction, catalyst is necessary.But because esterification is the higher reaction of a kind of degree of reversibility, if there is not appropriate catalyst to participate in, its reaction speed is very slow; Analyze from its reaction mechanism, acidity or alkali compounds all can play catalytic action, but in actual production, generally use acid compound; Such as the concentrated sulfuric acid and p-methyl benzenesulfonic acid etc.; Wherein the concentrated sulfuric acid select so p-methyl benzenesulfonic acid is most important catalyst, but p-methyl benzenesulfonic acid also can have certain side effect to product corrosion on Equipment property and bigger to the side effect of product; Especially must pass through purifying process it is removed, this certainly will cause a large amount of industrial wastewaters.Yet in general, within the specific limits, bigger catalyst concn can add the speed of fast response, and this will make commercial production more economically and efficiently.
Therefore a kind of catalyst that can conveniently separate can be separated them after reaction finishes easily from reaction system, thereby can be implemented in the purpose that adds the catalyst of big concentration when reacting and do not influence product quality.The method of taking mainly concentrates on catalyst field capable of circulation, and the carrier such as the various solid catalysts of exploitation is adsorbed on catalyst in the carrier then, thereby realizes separable catalyst; Also there is the researcher to adopt heteropoly acid to realize identical purpose as catalyst.But, in the former, because catalyst is to be adsorbed on the carrier; Its fixed effect is limited, and the catalyst ratio is easier to from wherein spinning off, so its number of times that can reach effective catalysis is very limited; And the latter's price and building-up process complexity are higher; And its many employing precious metal ions are central ion, and its toxicity is also bigger, so its application prospect is relatively poor.
Therefore a kind of novel solid macromolecule with functional group of catalytic action can be realized capable of circulation, segregative purpose easily.
Summary of the invention:
The purpose of this invention is to provide a kind of macromolecular compound, its synthetic method and the catalytic applications in esterification shown in general formula (I).
A kind of polymer catalyst of circular type esterification reaction, its structural formula is:
F, m are 1～1000 arbitrary integer in its Chinese style;
R in the formula
1Be selected from :-C
6H
4-,-COO (CH
2CH
2O)
nOCO-,-COO (CH
2CHCH
3O)
nOCO-or-COOCH
2CH
2OCOC
6H
4COOCH
2CH
2OCO-, wherein n is 2～10 arbitrary integer;
R
2Be selected from-H or-CH
3
R
3Be selected from-OCOCH
3,-COOCH
2C
2H
3O ,-COOR
4Or-COOR
5OH
R
4And R
5All be selected from the carbon atom number and be 1～12 alkyl.
The preparation method of the macromolecular compound shown in general formula (I) according to the invention is:
The first step: adopt the method for dispersin polymerization or precipitation polymerization to prepare macromolecular compound.
A, dispersin polymerization: under nitrogen protection; The SSS of one molar part and the vinyl monomer of a molar part are joined in the reaction dissolvent; The olefines organic compound that adds the polyfunctionality of monomer mass 0.5～15% is again done the dispersant of organic peroxy class or the azo-initiator and the reaction dissolvent gross mass 0.5～8.0% of crosslinking agent and monomer mass 0.1～10%; Under agitation carry out thermal polymerization, product obtains the white solid microballoon a of cross-linked polymer through centrifugation.Wherein, polymerization temperature is 80～110 ℃, and polymerization time is 2～6 hours; Used vinyl monomer is any in vinylacetate, GMA, alkyl acrylate, acrylic acid hydroxyalkyl acrylate, alkyl methacrylate or the methacrylic acid hydroxyl Arrcostab, and the mass concentration of monomer in whole polymerization reaction system is 3%～40%; Used reaction dissolvent is dimethyl sulfoxide (DMSO), N-methyl pyrrolidone or N, dinethylformamide; Used initator is the organic peroxy class: dibenzoyl peroxide, cumyl peroxide, di-tert-butyl peroxide, dilauroyl peroxide, the special butyl ester of peroxidating benzoic acid, peroxy dicarbonate diethyl propyl diester or di-cyclohexylperoxy di-carbonate, perhaps azo class: azodiisobutyronitrile or ABVN; Crosslinking agent is any in divinylbenzene, diethylene glycol class diacrylate (DEGDA), triethylene glycol class diacrylate (TEGDA), trimethylol-propane trimethacrylate (TMPTMA), polyethyleneglycol diacrylate class (PEGDA), propandiols diacrylate or the phthalic acid glycol diacrylate (PDDA); Used dispersant is PVP, CMC or polyvinyl alcohol.
B, precipitation polymerization: under nitrogen protection; The SSS of one molar part and the vinyl monomer of a molar part are joined in the reaction dissolvent; The olefines organic compound of polyfunctionality that adds precipitating reagent and the monomer mass 0.5～12% of reaction dissolvent volume 25～80% is again made the initator of crosslinking agent and monomer mass 0.1～10%; Under agitation carry out thermal polymerization, product obtains the white solid microballoon a ' of cross-linked polymer through centrifugation.Wherein, polymerization temperature is 80～110 ℃, and polymerization time is 2～6 hours; Used reaction dissolvent is water, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone or N, and dinethylformamide, used precipitating reagent are acetone, butanone, ethanol, butanols, toluene or xylenes; Used vinyl monomer is any in vinylacetate, GMA, alkyl acrylate, acrylic acid hydroxyalkyl acrylate, alkyl methacrylate or the methacrylic acid hydroxyl Arrcostab, and the mass concentration of monomer in whole polymerization reaction system is 3%～40%; Used initator is the organic peroxy class: dibenzoyl peroxide, cumyl peroxide, dilauroyl peroxide, the special butyl ester of peroxidating benzoic acid, peroxy dicarbonate diethyl propyl diester or di-cyclohexylperoxy di-carbonate, perhaps azo class: azodiisobutyronitrile or ABVN; Crosslinking agent is any in divinylbenzene, diethylene glycol class diacrylate (DEGDA), triethylene glycol class diacrylate (TEGDA), trimethylol-propane trimethacrylate (TMPTMA), polyethyleneglycol diacrylate class (PEGDA), propandiols diacrylate or the phthalic acid glycol diacrylate (PDDA).
Second step: it is that the saturated aqueous common salt that is processed cross-linked polymer microspheres with solid volume twice soaked 12～20 hours that the cross-linked polymer microspheres with solid a (or a ') that the first step is made places its volume; Using mass concentration after the clear water rinsing 3～5 times again is that 2%～10% sodium hydroxide solution soaked 3～6 hours; Filter and take out microsphere particle and wash the cross-linked polymer microspheres with solid until the approaching neutrality of discharge water; Using mass concentration again is that 3%～8% hydrochloric acid solution soaked 4～8 hours; After draining solution, be washed till neutrality, promptly obtain the macromolecule shown in claim 1 with clear water.The wherein used sodium hydroxide solution and the volume of hydrochloric acid solution are 2～5 times of the cross-linked polymer microspheres with solid volume that is processed.
The solid macromolecule microballoon that the present invention makes, particle diameter have good catalytic effect, and have certain performance capable of circulation at 1～150 μ m in esterification is used.
Said macromolecule can make through the method for dispersin polymerization or precipitation polymerization; And adjustable grain; Prepared macromolecule normal temperature is insoluble to acid, pure and mild ester down for solid-state-microspherical simultaneously, can be as the catalyst of esterification; When doing the catalyst use, can improve catalytic effect through regulating addition; After reaction finishes, can remove the solid macromolecule in the product, realize capable of circulation, segregative purpose and the purpose that reduces pollutant emission in the ester type compound production process easily, and the solid macromolecule that makes under the different condition have different catalytic efficiencies through the method for filtering.
Description of drawings
The infrared figure of Fig. 1 macromolecular compound
Fig. 2 particle diameter distribution map
The specific embodiment:
Synthetic embodiment:
Embodiment 1: dispersion copolymerization method
(1) under nitrogen protection; The SSS of 2.58g and the vinylacetate of 1.08g are joined in the there-necked flask that 100mL dimethyl sulfoxide (DMSO) reaction dissolvent is housed; Add the divinyl benzene crosslinked agent of 0.0183g and the initator benzoyl peroxide of 0.0037g and the PVP of 0.02g again and do dispersant; Polymerisation there are being under the stirring state 2 hours under 100 ℃ then; Obtain the dispersion of cross-linked polymer microsphere, obtain the white solid microballoon of cross-linked polymer again through centrifugation.
(2) above-mentioned cross-linked polymer microsphere being placed volume is that the saturated aqueous common salt that is processed cross-linked polymer microsphere volume twice soaked 12 hours; With soaking 6 hours with the sodium hydroxide solution of mass concentration 2% again after the clear water rinsing 3 times; The flushing cross-linked polymer microsphere till discharge water is near neutrality after again with 3% hydrochloric acid solution immersion 8 hours; Drain solution, to neutral, promptly obtain macromolecular compound a shown in general formula (I) with the flushing with clean water cross-linked polymer microsphere
1The wherein used sodium hydroxide solution and the volume of hydrochloric acid solution are 2 times of the cross-linked polymer microspheres with solid volume that is processed.
Product must be macromolecular compound (I) through infrared analysis, shown in accompanying drawing 1.
Product is analyzed particle diameter with HORIB LA-300 Particle Size Analyzer after disperseing 30min with ethanol, and grain size mainly is distributed in 6～20 μ m, shown in accompanying drawing 2.
Embodiment 2: dispersion copolymerization method
(1) under nitrogen protection; The SSS of 25.75g and the vinylacetate of 10.75g are joined in the there-necked flask that 100mL N-methyl pyrrolidone reaction dissolvent is housed; Add 5.47g diethylene glycol class diacrylate (DEGDA) crosslinking agent and the initator azodiisobutyronitrile of 3.65g and the PVP of 2.92g again and do dispersant; Polymerisation there are being under the stirring state 6 hours under 80 ℃ then; Obtain the dispersion of cross-linked polymer microsphere, obtain the white solid microballoon of cross-linked polymer again through centrifugation.
(2) above-mentioned cross-linked polymer microsphere being placed volume is that the saturated aqueous common salt that is processed cross-linked polymer microsphere volume twice soaked 20 hours; With soaking 3 hours with the sodium hydroxide solution of mass concentration 10% again after the clear water rinsing 5 times; The flushing cross-linked polymer microsphere till discharge water is near neutrality after again with 8% hydrochloric acid solution immersion 4 hours; Drain solution, to neutral, promptly obtain macromolecular compound a shown in general formula (I) with the flushing with clean water cross-linked polymer microsphere
2The wherein used sodium hydroxide solution and the volume of hydrochloric acid solution are 3 times of the cross-linked polymer microspheres with solid volume that is processed.
Product a
2Behind ethanol dispersion 30min, with HORIB LA-300 Particle Size Analyzer particle diameter to be analyzed, grain size mainly is distributed in 80～100 μ m.
Embodiment 3: dispersion copolymerization method
(1) under nitrogen protection; The SSS of 5.15g and the vinylacetate of 2.15g are joined in the there-necked flask that 100mLN-methyl pyrrolidone reaction dissolvent is housed; Add 1.09g polyethylene glycol (600) diacrylate class (PEG (600) DA) crosslinking agent and the initator dilauroyl peroxide of 0.73g and the CMC of 5.60g again and do dispersant; Polymerisation there are being under the stirring state 4 hours under 110 ℃ then; Obtain the dispersion of cross-linked polymer microsphere, obtain the white solid microballoon of cross-linked polymer again through centrifugation.
(2) above-mentioned cross-linked polymer microsphere being placed volume is that the saturated aqueous common salt that is processed cross-linked polymer microsphere volume twice soaked 16 hours; With soaking 5 hours with the sodium hydroxide solution of mass concentration 6% again after the clear water rinsing 4 times; The flushing cross-linked polymer microsphere till discharge water is near neutrality after again with 5% hydrochloric acid solution immersion 5 hours; Drain solution, to neutral, promptly obtain macromolecular compound a shown in general formula (I) with the flushing with clean water cross-linked polymer microsphere
3The wherein used sodium hydroxide solution and the volume of hydrochloric acid solution are 5 times of the cross-linked polymer microspheres with solid volume that is processed.
Product a
3After disperseing 30min with ethanol, particle diameter is analyzed grain size 15～30 μ m that mainly distribute with HORIB LA-300 Particle Size Analyzer.
Embodiment 4: dispersion copolymerization method
The quality of reacting each raw material is respectively:
Monomer: SSS 5.15g
Monomer: ethyl acrylate 2.50g
Initator: ABVN 0.46g
Dispersant: polyvinyl alcohol 6.20g
Crosslinking agent: triethylene glycol base diacrylate (TEGDA) 0.77g
Reaction dissolvent: N-methyl pyrrolidone 100mL
Reaction temperature: 90 ℃
Reaction time: 5 hours
Method for making and other processing method such as embodiment 1.
Product a
4After disperseing 30min with ethanol, particle diameter is analyzed grain size 13～30 μ m that mainly distribute with HORIB LA-300 Particle Size Analyzer.
Embodiment 5: dispersion copolymerization method
The quality of reacting each raw material is respectively:
Monomer: SSS 6.87g
Monomer: butyl acrylate 4.27g
Initator: cumyl peroxide 0.66g
Dispersant: polyvinyl alcohol 5.60g
Crosslinking agent: trimethylol-propane trimethacrylate (TMPTMA) 0.82g
Reaction dissolvent: dimethyl sulfoxide (DMSO) 100mL
Reaction temperature: 100 ℃
Reaction time: 3 hours
Method for making and other processing method such as embodiment 3.
Product a
5After disperseing 30min with ethanol, particle diameter is analyzed grain size 20～35 μ m that mainly distribute with HORIB LA-300 Particle Size Analyzer.
Embodiment 6: dispersion copolymerization method
The quality of reacting each raw material is respectively:
Monomer: SSS 6.87g
Monomer: GMA 4.73g
Initator: the special butyl ester 0.83g of peroxidating benzoic acid
Dispersant: PVP 7.20g
Crosslinking agent: tripropylene glycol base diacrylate (TPGDA) 1.02g
Reaction dissolvent: N-methyl pyrrolidone 100mL
Reaction temperature: 90 ℃
Reaction time: 3 hours
Method for making and other processing method such as embodiment 2.
Product a
6After disperseing 30min with ethanol, particle diameter is analyzed grain size 30～55 μ m that mainly distribute with HORIB LA-300 Particle Size Analyzer.
Embodiment 7: dispersion copolymerization method
The quality of reacting each raw material is respectively:
Monomer: SSS 8.24g
Monomer: hydroxy-ethyl acrylate 4.64g
Initator: peroxy dicarbonate diethyl propyl diester 1.13g
Dispersant: CMC 4.20g
Crosslinking agent: phthalic acid glycol diacrylate (PDDA) 0.72g
Reaction dissolvent: N, dinethylformamide 100mL
Reaction temperature: 90 ℃
Reaction time: 5 hours
Method for making and other processing method such as embodiment 1.
Product a
7After disperseing 30min with ethanol, particle diameter is analyzed grain size 40～55 μ m that mainly distribute with HORIB LA-300 Particle Size Analyzer.
Embodiment 8: dispersion copolymerization method
The quality of reacting each raw material is respectively:
Monomer: SSS 5.15g
Monomer: hydroxy propyl methacrylate 3.60g
Initator: di-cyclohexylperoxy di-carbonate 0.26g
Dispersant: CMC 3.60g
Crosslinking agent: pentaerythritol triacrylate (PETA) 0.72g
Reaction dissolvent: dimethyl sulfoxide (DMSO) 100mL
Reaction temperature: 90 ℃
Reaction time: 5 hours
Method for making and other processing method such as embodiment 3.
Product a
8After disperseing 30min with ethanol, particle diameter is analyzed grain size 20～40 μ m that mainly distribute with HORIB LA-300 Particle Size Analyzer.
Embodiment 9: precipitation polymerization method
(1) under nitrogen protection; The SSS of 2.58g and the vinylacetate of 1.08g are joined in the mixed reaction solvent that 50mL dimethyl sulfoxide (DMSO) and 50mL acetone are housed; Add crosslinking agent divinylbenzene 0.0183g and 0.027g benzoyl peroxide initator again; 90 ℃ of following polymerisations 2 hours, obtain the dispersion of cross-linked polymer microsphere then, obtain the white microballoon of cross-linked polymer again through centrifugation.
(2) above-mentioned cross-linked polymer microsphere being placed volume is that the saturated aqueous common salt that is processed cross-linked polymer microsphere volume twice soaked 20 hours; With soaking 3 hours with 4% sodium hydroxide solution again after the clear water rinsing 3 times; The flushing cross-linked polymer microsphere till discharge water is near neutrality after again with 5% hydrochloric acid solution immersion 8 hours; Drain solution, be washed till neutrality, promptly obtain macromolecular compound a ' shown in general formula (I) with clear water
9The wherein used sodium hydroxide solution and the volume of hydrochloric acid solution are the twice of the cross-linked polymer microspheres with solid volume that is processed.
Product must be the macromolecular compound shown in the general formula (I) through infrared analysis.
Product a '
9After disperseing 30min with ethanol, particle diameter is analyzed grain size 3～9 μ m that mainly distribute with HORIB LA-300 Particle Size Analyzer.
Embodiment 10: precipitation polymerization method
The quality of reacting each raw material is respectively:
Monomer: SSS 25.75g
Monomer: methyl acrylate 10.75g
Initator: azodiisobutyronitrile 1.825g
Crosslinking agent: diethylene glycol class diacrylate (DEGDA) 5.47g
Reaction dissolvent: N-methyl pyrrolidone 80ml
Precipitating reagent: acetone 20ml
Reaction temperature: 80 ℃
Reaction time: 6 hours
Method for making and other processing method such as embodiment 9.
Product a '
10After disperseing 30min with ethanol, particle diameter is analyzed grain size 60～90 μ m that mainly distribute with HORIB LA-300 Particle Size Analyzer.
Embodiment 11: precipitation polymerization method
React the operation parameter of each raw material:
Monomer: SSS 5.15g
Monomer: vinylacetate 2.15g
Initator: dilauroyl peroxide 0.73g
Crosslinking agent: polyethylene glycol (600) diacrylate class (PEG (600) DA) 1.09g
Reaction dissolvent: N, dinethylformamide 25ml
Precipitating reagent: butanone 75ml
Reaction temperature: 110 ℃
Reaction time: 4 hours
Method for making and other processing method such as embodiment 1.
Product a '
11After disperseing 30min with ethanol, particle diameter is analyzed grain size 17～28 μ m that mainly distribute with HORIB LA-300 Particle Size Analyzer.
Embodiment 12: precipitation polymerization method
React the operation parameter of each raw material:
Monomer: SSS 5.15g
Monomer: ethyl acrylate 2.50g
Initator: ABVN 0.46g
Crosslinking agent: triethylene glycol base diacrylate (TEGDA) 0.77g
Reaction dissolvent: N, dinethylformamide 35ml
Precipitating reagent: ethanol 65ml
Reaction temperature: 90 ℃
Reaction time: 5 hours
Method for making and other processing method such as embodiment 1.
Product a '
12After disperseing 30min with ethanol, particle diameter is analyzed grain size 15～26 μ m that mainly distribute with HORIB LA-300 Particle Size Analyzer.
Embodiment 13: precipitation polymerization method
React the operation parameter of each raw material:
Monomer: SSS 6.87g
Monomer: butyl acrylate 4.27g
Initator: cumyl peroxide 0.66g
Crosslinking agent: trimethylol-propane trimethacrylate (TMPTMA) 0.82g
Reaction dissolvent: dimethyl sulfoxide (DMSO) 60ml
Precipitating reagent: butanols 40ml
Reaction temperature: 100 ℃
Reaction time: 3 hours
Method for making and other processing method such as embodiment 1.
Product a '
13After disperseing 30min with ethanol, particle diameter is analyzed grain size 30～47 μ m that mainly distribute with HORIB LA-300 Particle Size Analyzer.
Embodiment 14: precipitation polymerization method
React the operation parameter of each raw material:
Monomer: SSS 6.87g
Monomer: GMA 4.73g
Initator: the special butyl ester 0.83g of peroxidating benzoic acid
Crosslinking agent: tripropylene glycol base diacrylate (TPGDA) 1.02g
Reaction dissolvent: N-methyl pyrrolidone 55ml
Precipitating reagent: acetone 45ml
Reaction temperature: 90 ℃
Reaction time: 3 hours
Method for making and other processing method such as embodiment 1.
Product a '
14After disperseing 30min with ethanol, particle diameter is analyzed grain size 12～25 μ m that mainly distribute with HORIB LA-300 Particle Size Analyzer.
Embodiment 15: precipitation polymerization method
React the operation parameter of each raw material:
Monomer: SSS 8.24g
Monomer: hydroxy-ethyl acrylate 4.64g
Initator: peroxy dicarbonate diethyl propyl diester 1.13g
Crosslinking agent: pentaerythritol triacrylate (PETA) 0.72g
Reaction dissolvent: N, dinethylformamide 60ml
Precipitating reagent: toluene 35ml
Reaction temperature: 90 ℃
Reaction time: 5 hours
Method for making and other processing method such as embodiment 1.
Product a '
15After disperseing 30min with ethanol, particle diameter is analyzed grain size 35～55 μ m that mainly distribute with HORIB LA-300 Particle Size Analyzer.
Embodiment 16: precipitation polymerization method
React the operation parameter of each raw material:
Monomer: SSS 5.15g
Monomer: hydroxy propyl methacrylate 3.60g
Initator: di-cyclohexylperoxy di-carbonate 0.26g
Crosslinking agent: pentaerythritol triacrylate (PETA) 0.72g
Reaction dissolvent: dimethyl sulfoxide (DMSO) 70ml
Precipitating reagent: xylenes 30ml
Reaction temperature: 90 ℃
Reaction time: 5 hours
Method for making and other processing method such as embodiment 1.
Product a '
16After disperseing 30min with ethanol, particle diameter is analyzed grain size 17～30 μ m that mainly distribute with HORIB LA-300 Particle Size Analyzer.
Embodiment 17: precipitation polymerization method
The quality of reacting each raw material is respectively:
Monomer: SSS 25.75g
Monomer: methyl acrylate 10.75g
Initator: azodiisobutyronitrile 1.825g
Crosslinking agent: divinylbenzene 5.47g
Reaction dissolvent: water 60ml
Precipitating reagent: acetone 40ml
Reaction temperature: 80 ℃
Reaction time: 6 hours
Method for making and other processing method such as embodiment 9.
Product a '
17After disperseing 30min with ethanol, particle diameter is analyzed grain size 85～130 μ m that mainly distribute with HORIB LA-300 Particle Size Analyzer.
The application implementation example:
Embodiment 1:
In the container of mixing plant is housed, add n-octyl alcohol, the acrylic acid of 32.55g, the described solid macromolecule compound a of 5.40g claim 1 of 21.62g
1, the hydroquinones of 0.54g, the toluene of 55g, stirring and dissolving and mix after, be heated to 100 ℃, with water rate check esterification effect, be 92.6% through measuring water rate.
Post reaction mixture is filtered; Obtain microspheres with solid,, join after the oven dry in the reaction of toluene container of acrylic acid, 0.54g hydroquinones and 55g of n-octyl alcohol that 21.62g is housed, 32.55g with acetone rinsing 3 times; Stirring and dissolving and mix after; Being heated to 100 ℃, with water rate check secondary esterification effect, is 91.4% through measuring water rate.
Use the same method check for the third time, the 4th time, until the 17 time, all more than 71%, the 18 time water rate is 69.2% to its water rate, promptly the number of times capable of circulation before the water rate 70% is 17 times.
Embodiment 2:
Acrylic acid: 21.62g
N-octyl alcohol: 32.55g
Hydroquinones: 0.54g
Solid macromolecule microballoon a
3: 1.67g
Toluene: 55g
Reaction temperature: 100 ℃,
All the other are with embodiment 1, and mensuration water rate for the first time is 77.2%, and its number of times capable of circulation is 7 times.
Embodiment 3:
Acrylic acid: 21.62g
N-octyl alcohol: 32.55g
Hydroquinones: 0.54g
Solid macromolecule microballoon a
7: 3.60g
Toluene: 55g
Reaction temperature: 100 ℃,
All the other are with embodiment 1, and mensuration water rate for the first time is 82.1%, and its number of times capable of circulation is 12 times.
Embodiment 4:
N-butyric acie: 24.21g
N-hexyl alcohol: 25.55g
Hydroquinones: 0.50g
Solid macromolecule microballoon a '
11: 3.60g
Toluene: 50g
Reaction temperature: 100 ℃,
All the other are with embodiment 1, and mensuration water rate for the first time is 94.2%, and its number of times capable of circulation is 19 times.
Embodiment 5:
Positive valeric acid: 28.09g
N-butanol: 18.53g
Hydroquinones: 0.47g
Solid macromolecule microballoon a '
15: 3.60g
Toluene: 46.5g
Reaction temperature: 100 ℃,
All the other are with embodiment 1, and mensuration water rate for the first time is 85.8%, and its number of times capable of circulation is 15 times.
Claims (4)
1. the polymer catalyst of a circular type esterification reaction, its structural formula is:
F, m are 1～1000 arbitrary integer in its Chinese style;
R in the formula
1Be selected from :-C
6H
4-,-COO (CH
2CH
2O)
nOCO-,-COO (CH
2CHCH
3O)
nOCO-or-COOCH
2CH
2OCOC
6H
4COOCH
2CH
2OCO-, wherein n is 2～10 arbitrary integer;
R
2Be selected from-H or-CH
3
R
3Be selected from-OCOCH
3,-COOCH
2C
2H
3O ,-COOR
4Or-COOR
5OH
R
4And R
5All be selected from the carbon atom number and be 1～12 alkyl.
2. the preparation method of the polymer catalyst of circular type esterification reaction according to claim 1 is characterized in that, makes through two-step method:
The first step: it is characterized in that adopting the method preparation of dispersin polymerization or precipitation polymerization, be specially:
A, dispersin polymerization: under nitrogen protection; The SSS of one molar part and the vinyl monomer of a molar part are joined in the reaction dissolvent; Add initator, crosslinking agent and dispersant again, after the dissolving, under condition of stirring, reacting 2～6 hours under 80～110 ℃; Obtain the dispersion of cross-linked polymer microsphere, obtain the white solid a of cross-linked polymer microsphere again through centrifugation; Wherein said SSS and the vinyl monomer mass concentration in whole polymerization reaction system is 3%～40%; Initator is organic peroxide or azo-compound, and the quality of initator is 0.1%～10% of a reaction monomers gross mass; Used crosslinking agent is the olefines organic compound of polyfunctionality, and the quality of crosslinking agent is 0.5%～15% of a reaction monomers gross mass; Dispersant is PVP, CMC or polyvinyl alcohol, and quality is 0.5%～8.0% of a reaction system gross mass; Reaction dissolvent is dimethyl sulfoxide (DMSO), N-methyl pyrrolidone or N, dinethylformamide;
B, precipitation polymerization: under nitrogen protection; The SSS of one molar part and the vinyl monomer of a molar part are joined in the reaction dissolvent; The precipitating reagent that adds initator, crosslinking agent and reaction dissolvent volume 25%～80% again; The dissolving back obtains the dispersion of cross-linked polymer microsphere under condition of stirring, reacting 2～6 hours under 80～110 ℃, obtains the white solid a ' of cross-linked polymer microsphere again through centrifugation; Wherein said SSS and the vinyl monomer mass concentration in whole polymerization reaction system is 3%～40%; Initator is organic peroxide or azo-compound, and the quality of initator is 0.1%～10% of a reaction monomers gross mass; Used crosslinking agent is the olefines organic compound of polyfunctionality, and the quality of crosslinking agent is 0.5%～12% of a reaction system gross mass; Reaction dissolvent is water, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone or N, dinethylformamide, and precipitating reagent is: acetone, butanone, ethanol or toluene;
Second step: it is that the saturated aqueous common salt that is processed cross-linked polymer microspheres with solid volume twice soaked 12～20 hours that cross-linked polymer microspheres with solid a that the first step is made or a ' place its volume; Using mass concentration after the clear water rinsing 3～5 times again is that 2%～10% sodium hydroxide solution soaked 3～6 hours; Filter and take out microspheres with solid and wash the cross-linked polymer microspheres with solid until the approaching neutrality of discharge water; Using mass concentration again is that 3%～8% hydrochloric acid solution soaked 4～8 hours; After draining solution, be washed till neutrality, promptly get the polymer catalyst of circular type esterification reaction with clear water; The wherein used sodium hydroxide solution and the volume of hydrochloric acid solution are 2～5 times of the cross-linked polymer microspheres with solid volume that is processed
Used vinyl monomer is vinylacetate, GMA, alkyl acrylate, acrylic acid hydroxyalkyl acrylate, alkyl methacrylate or methacrylic acid hydroxyl Arrcostab; Used initator is the organic peroxy class: dibenzoyl peroxide, cumyl peroxide, dilauroyl peroxide, the special butyl ester of peroxidating benzoic acid, peroxy dicarbonate diethyl propyl diester or di-cyclohexylperoxy di-carbonate, perhaps azo class: azodiisobutyronitrile or ABVN; Used crosslinking agent is divinylbenzene, diethylene glycol class diacrylate, triethylene glycol class diacrylate, trimethylol-propane trimethacrylate, polyethyleneglycol diacrylate class, propandiols diacrylate or phthalic acid glycol diacrylate.
3. the application of polymer catalyst according to claim 1, it is characterized in that: described polymer catalyst is as catalyst for esterification reaction.
4. like the application of the said polymer catalyst of claim 3; It is characterized in that: described polymer catalyst is as catalyst for esterification reaction; After reaction finished, through removing by filter the solid phase cross-linked polymer microsphere in the product, resulting cross-linked polymer microsphere continued catalytic esterification.
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