CN101298492B - Synthetic method of polyester - Google Patents
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- CN101298492B CN101298492B CN2007101077994A CN200710107799A CN101298492B CN 101298492 B CN101298492 B CN 101298492B CN 2007101077994 A CN2007101077994 A CN 2007101077994A CN 200710107799 A CN200710107799 A CN 200710107799A CN 101298492 B CN101298492 B CN 101298492B
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Abstract
The invention relates to a method for synthesizing polyester with dibasic acid or dibasic acid anhydride or dibasic acid ester and dibasic alcohol. The method comprises the steps of synthesizing the dibasic acid or dibasic acid anhydride or dibasic acid ester and dibasic alcohol bulks into an oligoester, and then carrying out polycondensation to the loligoester in ionic liquid. The method realizes excellent effects of increasing molecular weight of the polyester, cycle using of reaction medium ionic liquid, reducing energy consumption as well as shortening reaction time. The invention also relates to the polyester products obtained by the method of the invention.
Description
Technical field
The present invention relates to the Polymer Synthesizing field, relate in particular to the condensation polymerization reaction in this field.More particularly, the present invention relates to a kind of method of ionic liquid stepwise synthesis polyester and polyester that obtains by this method of adopting.
Background technology
The condensation polymerization reaction of tradition synthesizing polyester has temperature of reaction height, the time is long, energy consumption is big shortcoming.In addition, the equilibrium polycondensation reaction just is difficult to further move to the positive reaction direction after proceeding to a certain degree, therefore is difficult to obtain high molecular weight polymers.In order to improve the molecular weight of resulting polymers, remove the small molecules that produces in the polycondensation system with decompression usually, to disequilibrate and reaction is constantly moved to the positive reaction direction.Yet the increase in the reaction later stage along with system viscosity is even take decompression also to be difficult to get rid of small molecules.The tradition solution is to add organic solvent to come the diluting reaction system, makes small molecules be easy to discharge.Yet organic solvent is often volatile, taken away easily under decompression state, so this has not only increased operation easier, but also environment is polluted.
Replace conventional organic solvents to come the diluting reaction system to have outstanding advantage with ionic liquid, for example it is not volatile, and vapour pressure is almost nil, and Heat stability is good is convenient to recycle.In addition, because its structure of matter and character have designability, therefore be applicable to different polyester condensation polymerization systems.But, in ionic liquid, carry out the condensation polymerization reaction at present and still have some problems, for example the partial ion liquid chemical property is stable inadequately, wet fastness is bad, can make poisoning of catalyst etc.In Chinese patent ZL02130963.9 reported method, some ionic liquid exists in the polyester synthetic reacts in earlier stage and is unfavorable for getting rid of water vapour, decomposition easily, perhaps makes the shortcoming of poisoning of catalyst easily.At last, the molecular weight of the polyester of this direct condensation gained in ionic liquid is not high enough.
Summary of the invention
The objective of the invention is to overcome above-mentioned shortcoming of the prior art, a kind of novel method of synthesizing polyester is provided, to reach the molecular weight that improves polyester product, the effect that reduces energy consumption.Find that surprisingly this purpose is by at first by mass polymerization synthesis of oligonucleotides ester, in ionic liquid, carry out the polycondensation of oligomer ester then and the method for stepwise synthesis polyester is achieved.The concrete scheme of the inventive method is as follows:
A kind of method of using diprotic acid or dibasic acid anhydride or diester and dibasic alcohol synthesizing polyester comprises the steps:
A) mass polymerization synthesis of oligonucleotides ester:
Make diprotic acid or dibasic acid anhydride or diester and dibasic alcohol under nitrogen protection, under 140-200 ℃ temperature, react, obtain oligomer ester;
B) in ionic liquid, carry out the polycondensation of oligomer ester:
The oligopolymer that obtains in the step a) is reacted in the presence of the catalyzer that the equilibrium polycondensation reaction is used always in ionic liquid.Described catalyzer for example is strong protonic acid and metal simple-substance and compound thereof, wherein strong protonic acid preferably sulfuric acid, tosic acid and hydrate thereof, simple substance and oxide compound, alkoxide, halogenide and hydrate thereof, oxygen-containing inorganic acid salt, organic acid salt and the hydrate thereof of metal simple-substance and compound preferred elements periodictable IB thereof, IIB, IIIB, IVB, VIII, IVA, VA family metal, the wherein more preferably inferior tin of tin protochloride and hydrate thereof, lauric acid, two stannous iso caprylates, tetrabutyl titanate, zinc acetate and hydrate thereof.
Another object of the present invention provides the polyester that obtains by synthetic method of the present invention.
Adopt synthetic method of the present invention to have molecular weight, minimizing energy consumption, the excellent results in shortening reaction times of raising polyester product.The weight-average molecular weight of gained polyester product even can reach more than 200,000 is preferably 1-21 ten thousand.
Description of drawings
Fig. 1 is the infrared spectrogram of the poly-sebacic acid hexylene glycol ester of embodiment 10 preparations;
Fig. 2 is the poly-sebacic acid hexylene glycol ester of embodiment 10 preparation
1The H-NMR spectrogram.
Embodiment
In the methods of the invention, operable diprotic acid, dibasic acid anhydride, diester comprise C
2-C
12Diprotic acid, C
2-C
12Dibasic acid anhydride, C
2-C
12Diester.
In the methods of the invention, operable dibasic alcohol comprises C
2-C
12Dibasic alcohol.
In the methods of the invention, used ionic liquid can comprise the ionic liquid with following general formula in the step b):
M
+A
-，
M wherein
+Be to be selected from following positively charged ion:
[NR
xH
4-x]
+, [PR
xH
4-x]
+,
Or
Wherein x is the integer of 1-4, R and R
1Mutually identical or different and represent C respectively
1-C
18Alkyl or C
6-C
12Aryl, R
2Be hydrogen atom or C
1-C
4Alkyl; With
A
-Be to be selected from following negatively charged ion: BF
4 -, PF
6 -, [SbF
6]
-, [CF
3SO
3]
-, [AlCl
4]
-, CF
3CF
2CF
2CF
2SO
3 -, (CF
3SO
2)
2N
-, CF
3COO
-, (CF
3SO
2)
3C
-And CF
3CF
2CF
2COO
-
In the methods of the invention, the mol ratio of used diprotic acid or dibasic acid anhydride or diester and dibasic alcohol is 1:1-1:1.2 in the step a).
In the methods of the invention, wherein in the step b) mass ratio of oligopolymer, ionic liquid, catalyzer be 1 part of oligopolymer, 0.05-10 part ionic liquid, 0.0001-0.05 part catalyzer.
In the methods of the invention, the pressure that wherein reacts in the step a) is normal pressure.
In the methods of the invention, the temperature of wherein reacting in the step a) is 140-200 ℃.
In the methods of the invention, the time of wherein reacting in the step a) is 1-12 hour.
In the methods of the invention, wherein used catalyzer is a catalyzer commonly used in the equilibrium polycondensation reaction in the step b), for example is selected from tin protochloride and hydrate thereof, the inferior tin of lauric acid, glass putty, stannic oxide, two stannous iso caprylates, zinc acetate and hydrate, tetrabutyl titanate, tosic acid and hydrate thereof; Wherein preferred tin protochloride and hydrate thereof, the inferior tin of lauric acid, two stannous iso caprylates, hydration zinc acetate.
In the methods of the invention, the pressure that wherein reacts in the step b) is 30-1000Pa.
In the methods of the invention, the temperature of wherein reacting in the step b) is 100-220 ℃.
In the methods of the invention, the time of wherein reacting in the step b) is 1-24 hour.
In the methods of the invention, wherein the product of step b) gained is purified by the following method: 1 mass parts product is directly added in 5-20 mass parts methyl alcohol or ethanol or ether or the water, suction filtration, and with methyl alcohol or ethanol or ether or water washing, preferably 45 ℃ of following vacuum-dryings.
Method of the present invention can be used for synthetic this area equilibrium polycondensation reaction commonly used synthetic polyester.Can be used for by diprotic acid or derivatives thereof such as dibasic acid anhydride or diester and dibasic alcohol synthesizing polyester as method of the present invention.The example of operable diprotic acid is among the present invention: terephthalic acid, m-phthalic acid, phthalic acid, oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid etc.; The example of dibasic acid anhydride is: Tetra hydro Phthalic anhydride, hydrogenation of benzene dicarboxylic acid anhydride, tetrachloro-phthalic acid acid anhydride etc.; The example of diester is: dimethyl terephthalate (DMT), diglycol terephthalate etc.; The example of dibasic alcohol is: ethylene glycol, glycol ether, propylene glycol, butyleneglycol, dipropylene glycol, hexylene glycol, ethohexadiol, decanediol, neopentyl glycol, dihydroxyphenyl propane, Hydrogenated Bisphenol A etc.
Embodiment
The present invention is further illustrated below with reference to embodiment.Should be pointed out that these embodiment only are the exemplary illustrated to the inventive method, and should not think limitation of the scope of the invention.
Reagent among the present invention is the commercially available prod, and purity is analytical pure, uses preceding through conventional method purification process.
The model of used gel permeation chromatography (GPC), nucleus magnetic resonance (NMR) and infrared gear (FTIR): the GPC model is PL-GPC50 (a Polymer Laboratories company), the NMR model is BrukerAdvance DRX-500 (a Bruker company), and infrared model is OMNIC AVATAR360 (Thermo Electron Corporation).Wherein the moving phase of GPC is tetrahydrofuran (THF) (embodiment 1-19 and 21) or chloroform (embodiment 20), and calibration curve monodisperse polystyrene standard specimen (PolymerLaboratories company, molecular weight is respectively 5,000,000,1,730,000,591,000,238,700,70,950,24,600,8,450,2,900,1,050,220) draw.
Embodiment 1: synthetic poly-sebacic acid hexylene glycol ester
A) mass polymerization synthesis of oligonucleotides ester:
12.54g (0.062mol) sebacic acid and 7.77g (0.066mol) hexylene glycol are added in the 100mL three neck round-bottomed flasks, under the nitrogen gas stream protection of gentleness,, reacted 10-11 hour 160 ℃ of following mechanical stirring.Reaction obtains the fragility white solid after finishing, and it is pressed into fritter is used for follow-up reaction.
B) in ionic liquid, carry out the polycondensation of oligomer ester:
With the oligomeric sebacic acid hexylene glycol ester that the 2.15g step a) obtains, two (trifluoromethyl sulphonyl) inferior amine salt ([bmim] Tf of 4.00g1-butyl-3-Methylimidazole
2N) and 0.01g hydrated stannous chloride (SnCl
22H
2O) add in the 10mL reaction flask.To find time under the reaction flask vacuum, and charge into nitrogen, triplicate.Be reflected at vacuum (about 50Pa), 160 ℃ of following mechanical stirring reactions were used the ice-water bath cooling reaction system after 24 hours.With GPC determining molecular weight and distribution thereof, the weight-average molecular weight of product is not 49,637 during purifying, and polydispersity coefficient is 1.89.
Embodiment 2:
Repeat embodiment 1 described method, difference is that ionic liquid adopts 1-butyl-3-Methylimidazole hexafluorophosphate ([bmim] PF
6).The weight-average molecular weight of product is not 24,850 during purifying, and polydispersity coefficient is 2.64.
Embodiment 3:
Repeat embodiment 1 described method, difference is that ionic liquid adopts 1-butyl-3-methyl imidazolium tetrafluoroborate ([bmim] BF
4).The weight-average molecular weight of product is not 12,643 during purifying, and polydispersity coefficient is 1.88.
Embodiment 4:
Repeat embodiment 1 described method, difference is that ionic liquid adopts two (trifluoromethyl sulphonyl) the inferior amine salt ([C of 1-hexyl-3-Methylimidazole
6Mim] Tf
2N).The weight-average molecular weight of product is not 48,439 during purifying, and polydispersity coefficient is 1.79.
Embodiment 5:
Repeat embodiment 1 described method, difference is that ionic liquid adopts 1-hexyl-3-Methylimidazole hexafluorophosphate ([C
6Mim] PF
6).The weight-average molecular weight of product is not 21,596 during purifying, and polydispersity coefficient is 2.21.
Embodiment 6:
Repeat embodiment 1 described method, difference is that ionic liquid adopts two (trifluoromethyl sulphonyl) the inferior amine salt ([C of 1-octyl group-3-Methylimidazole
8Mim] Tf
2N).The weight-average molecular weight of product is not 59,589 during purifying, and polydispersity coefficient is 1.74.
Embodiment 7:
Repeat embodiment 1 described method, difference is that ionic liquid adopts 1-octyl group-3-Methylimidazole hexafluorophosphate ([C
8Mim] PF
6).The weight-average molecular weight of product is not 20,221 during purifying, and polydispersity coefficient is 2.11.
Embodiment 8:
Repeat embodiment 1 described method, difference is that ionic liquid adopts 1-octyl group-3-methyl imidazolium tetrafluoroborate ([C
8Mim] BF
4).The weight-average molecular weight of product is not 12,360 during purifying, and polydispersity coefficient is 1.76.
Embodiment 9:
Repeat embodiment 1 described method, difference is that ionic liquid adopts two (trifluoromethyl sulphonyl) the inferior amine salt ([C of 1-decyl-3-Methylimidazole
10Mim] Tf
2N).The weight-average molecular weight of product is not 97,449 during purifying, and polydispersity coefficient is 2.19.
Embodiment 10:
Repeat embodiment 1 described method, difference is that ionic liquid adopts two (trifluoromethyl sulphonyl) the inferior amine salt ([C of 1-dodecyl-3-Methylimidazole
12Mim] Tf
2N).The weight-average molecular weight of product is not 97,592 during purifying, and polydispersity coefficient is 1.96.
Embodiment 11:
Repeat embodiment 1 described method, wherein in the step b) with the oligomeric sebacic acid hexylene glycol of 1.752g ester, 0.092g[C
12Mim] Tf
2N and 0.009g SnCl
22H
2O adds in the 7mL reaction flask.To find time under the reaction flask vacuum, and charge into nitrogen, triplicate.Be reflected at vacuum (about 50Pa), 160 ℃ of following mechanical stirring were reacted after 12 hours, used the ice-water bath cooling reaction system.Obtain tough and tensile white solid.The weight-average molecular weight of product is not 203,349 during purifying, and polydispersity coefficient is 2.31.
Embodiment 12:
As method as described in the embodiment 11, wherein in the step b) with the oligomeric sebacic acid hexylene glycol of 1.247g ester, 0.220gIC
12Mim] Tf
2N and 0.006g SnCl
22H
2O adds in the 7mL reaction flask.Obtain tough and tensile white solid.The weight-average molecular weight of product is not 167,142 during purifying, and polydispersity coefficient is 2.19.
Embodiment 13:
As method as described in the embodiment 11, wherein in the step b) with the oligomeric sebacic acid hexylene glycol of 1.116g ester, 0.372g[C
12Mim] Tf
2N and 0.006g SnCl
22H
2O adds in the 7mL reaction flask.Obtain tough and tensile white solid.The weight-average molecular weight of product is not 139,667 during purifying, and polydispersity coefficient is 2.06.
Embodiment 14:
As method as described in the embodiment 11, wherein in the step b) with the oligomeric sebacic acid hexylene glycol of 0.882g ester, 0.476g[C
12Mim] Tf
2N and 0.004g SnCl
22H
2O adds in the 7mL reaction flask.Obtain flexible white solid.The weight-average molecular weight of product is not 124,236 during purifying, and polydispersity coefficient is 1.96.
Embodiment 15:
As method as described in the embodiment 11, wherein in the step b) with the oligomeric sebacic acid hexylene glycol of 0.675g ester, 0.825g[C
12Mim] Tf
2N and 0.007g SnCl
22H
2O adds in the 7mL reaction flask.Obtain flexible white solid.The weight-average molecular weight of product is not 125,950 during purifying, and polydispersity coefficient is 1.98.
Embodiment 16:
As method as described in the embodiment 1, wherein in the step b) with the oligomeric sebacic acid hexylene glycol of 0.733g ester, 0.489g[C
12Mim] Tf
2N and 0.004g SnCl
22H
2O adds in the 7mL reaction flask.To find time under the reaction flask vacuum, and charge into nitrogen, triplicate.Be reflected at vacuum (about 50Pa),, react after 6 hours, use the ice-water bath cooling reaction system 180 ℃ of following mechanical stirring.Obtain flexible white solid.The weight-average molecular weight of product is not 120,564 during purifying, and polydispersity coefficient is 1.99.
Embodiment 17: synthetic poly-hexanodioic acid hexylene glycol ester
A) mass polymerization synthesis of oligonucleotides ester:
10.00g (0.068mol) hexanodioic acid and 8.58g (0.073mol) hexylene glycol are added in the 100mL three neck round-bottomed flasks, under the nitrogen gas stream protection of gentleness,, reacted 10-11 hour 160 ℃ of following mechanical stirring.Reaction obtains the fragility white solid after finishing, and it is pressed into fritter is used for follow-up reaction.
B) in ionic liquid, carry out the polycondensation of oligomer ester:
With the oligomeric hexanodioic acid hexylene glycol of 0.9220g ester, 0.6148g[C
12Mim] Tf
2N and 0.0046gSnCl
22H
2O adds in the 7mL reaction flask.To find time under the reaction flask vacuum, and charge into nitrogen, triplicate.Be reflected at vacuum (about 50Pa),, react after 12 hours, use the ice-water bath cooling reaction system 160 ℃ of following mechanical stirring.With GPC determining molecular weight and distribution thereof, the weight-average molecular weight of product is not 60,898 during purifying, and polydispersity coefficient is 1.80.
Embodiment 18: synthetic poly-hexanodioic acid hexylene glycol ester
As method as described in the embodiment 17, the oligomeric hexanodioic acid hexylene glycol ester that in step b), 0.8694g embodiment 17 step a) is obtained wherein, 0.5794g[bmim] Tf
2N and 0.0044g SnCl
22H
2O adds in the 7mL reaction flask.With GPC determining molecular weight and distribution thereof, the weight-average molecular weight of product is not 51,744 during purifying, and polydispersity coefficient is 1.86.
Embodiment 19: synthetic polyethylene glycol sebacate
A) mass polymerization synthesis of oligonucleotides ester:
14.29g (0.071mol) sebacic acid and 4.65g (0.075mol) ethylene glycol are added in the 100mL three neck round-bottomed flasks, under the nitrogen gas stream protection of gentleness,, reacted 10-11 hour 160 ℃ of following mechanical stirring.Reaction obtains the fragility white solid after finishing, and it is pressed into fritter is used for follow-up reaction.B) in ionic liquid, carry out the polycondensation of oligomer ester:
With the oligomeric sebacic acid glycol ester of 0.8582g, 0.5723g[bmim] Tf
2N and 0.0043gSnCl
22H
2O adds in the 7mL reaction flask.Under the vacuum reaction flask is found time, and charge into nitrogen, triplicate.Be reflected at vacuum (about 50Pa),, react after 12 hours, use the ice-water bath cooling reaction system 160 ℃ of following mechanical stirring.With GPC determining molecular weight and distribution thereof, the weight-average molecular weight of product is not 25,798 during purifying, and polydispersity coefficient is 2.13.
Embodiment 20: synthetic polyethylene glycol succinate
A) mass polymerization synthesis of oligonucleotides ester:
13.15g (0.111mol) Succinic Acid and 7.33g (0.118mol) ethylene glycol are added in the 100mL three neck round-bottomed flasks, under the nitrogen gas stream protection of gentleness,, reacted 6 hours 185 ℃ of following mechanical stirring.Reaction obtains the fragility white solid after finishing, and it is pressed into fritter is used for follow-up reaction.
B) polycondensation of oligomer ester in ionic liquid:
With the low polyethylene glycol succinate of 0.8947g, 0.5967g[bmim] Tf
2N and 0.0045gSnCl
22H
2O adds in the 7mL reaction flask.Under the vacuum reaction flask is found time, and charge into nitrogen, triplicate.Be reflected at vacuum (about 50Pa),, react after 12 hours, use the ice-water bath cooling reaction system 160 ℃ of following mechanical stirring.With GPC determining molecular weight and distribution thereof, the weight-average molecular weight of product is not 58,609 during purifying, and polydispersity coefficient is 1.88.
Embodiment 21: synthetic poly-phthalic acid hexylene glycol ester
A) mass polymerization synthesis of oligonucleotides ester:
9.10g (0.061mol) Tetra hydro Phthalic anhydride and 7.70g (0.065mol) hexylene glycol are added in the 100mL three neck round-bottomed flasks; under the nitrogen gas stream protection of gentleness,, reacted 4 hours 185-200 ℃ of following mechanical stirring; reaction obtains the water white transparency thick liquid after finishing.
B) polycondensation of oligomer ester in ionic liquid:
With the oligomeric phthalic acid hexylene glycol of 0.7464g ester, 0.5028g[bmim] Tf
2N and 0.0075g hydration zinc acetate Zn (OAc)
22H
2O adds in the 7mL reaction flask.To find time under the reaction flask vacuum, and charge into nitrogen, triplicate.Be reflected at vacuum (about 50Pa),, react after 20 hours, use the ice-water bath cooling reaction system 180 ℃ of following mechanical stirring.With GPC determining molecular weight and distribution thereof, the weight-average molecular weight of product is not 27,523 during purifying, and polydispersity coefficient is 1.92.
Embodiment 22: the purifying of product and aftertreatment
To directly add (methyl alcohol/product=10mL/1g), obtain white solid in a large amount of methyl alcohol by the product that embodiment 10 obtains.Suction filtration, and with methanol wash for several times after, 45 ℃ of following vacuum-drying 20 hours, yield 96.3%.
1H-NMR proves the wherein ion liquid residual 1 weight % (as shown in Figure 2) that is lower than.
Claims (11)
1. a method of using diprotic acid or dibasic acid anhydride or diester and dibasic alcohol synthesizing polyester comprises the steps:
A) mass polymerization synthesis of oligonucleotides ester:
Make diprotic acid or dibasic acid anhydride or diester and dibasic alcohol under nitrogen protection, under 140-200 ℃ temperature, react, obtain oligomer ester;
B) in ionic liquid, carry out the polycondensation of oligomer ester:
The oligopolymer that obtains in the step a) is reacted in the presence of the catalyzer that the equilibrium polycondensation reaction is used always in ionic liquid,
Wherein said ionic liquid comprises the ionic liquid with following general formula:
M
+A
-
M wherein
+Be to be selected from following positively charged ion:
[NR
XH
4-X]
+，[PR
XH
4-X]
+，
Wherein x is the integer of 1-4, R and R
1Mutually identical or different and represent C respectively
1-C
18Alkyl or C
6-C
12Aryl, R
2Be hydrogen atom or C
1-C
4Alkyl; With
A
-Be to be selected from following negatively charged ion: BF
4 -, PF
6 -, [SbF
6]
-, [CF
3SO
3]
-, [AlCl
4]
-, CF
3CF
2CF
2CF
2SO
3 -, (CF
3SO
2)
2N
-, CF
3COO
-, (CF
3SO
2)
3C
-And CF
3CF
2CF
2COO
-And
Wherein used catalyzer is strong protonic acid and metal simple-substance and compound thereof in the step b).
2. the method for claim 1 is characterized in that the mol ratio of diprotic acid in the described step a) or dibasic acid anhydride or diester and dibasic alcohol is 1: 1-1: 1.2.
3. the method for claim 1 is characterized in that described diprotic acid, dibasic acid anhydride, diester comprise C
2-C
12Diprotic acid, C
2-C
12Dibasic acid anhydride, C
2-C
12Diester.
4. the method for claim 1 is characterized in that described dibasic alcohol comprises C
2-C
12Dibasic alcohol.
5. the method for claim 1, wherein ion liquid negatively charged ion is (CF
3SO
2)
2N
-
6. as each described method among the claim 1-4, the mass ratio that it is characterized in that oligopolymer in the step b), ionic liquid, catalyzer is 1 part of oligopolymer, 0.05-10 part ionic liquid, 0.0001-0.05 part catalyzer.
7. as each described method among the claim 1-4, it is characterized in that catalyst system therefor is selected from tin protochloride and hydrate, the inferior tin of lauric acid, glass putty, stannic oxide, two stannous iso caprylates, zinc acetate and hydrate, tetrabutyl titanate, tosic acid and hydrate thereof in the step b).
8. method as claimed in claim 7 is characterized in that in the step b) that catalyst system therefor is selected from tin protochloride and hydrate thereof, the inferior tin of lauric acid, two stannous iso caprylates, hydration zinc acetate.
9. as each described method among the claim 1-4, it is characterized in that the pressure that reacts in the step b) is 30-1000Pa.
10. as each described method among the claim 1-4, it is characterized in that the temperature of reacting in the step b) is 100-220 ℃.
11. as each described method among the claim 1-4, it is characterized in that the product that step b) obtains purifies by the following method: 1 mass parts product is directly added in 5-20 mass parts methyl alcohol or ethanol or ether or the water, suction filtration, and with methyl alcohol or ethanol or ether or water washing, vacuum-drying then.
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|---|---|---|---|
| CN2007101077994A CN101298492B (en) | 2007-04-30 | 2007-04-30 | Synthetic method of polyester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101077994A CN101298492B (en) | 2007-04-30 | 2007-04-30 | Synthetic method of polyester |
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|---|---|
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| CN101298492B true CN101298492B (en) | 2011-02-16 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229419A (en) * | 1996-09-04 | 1999-09-22 | 株式会社日立制作所 | Method and apparatus for continuous polycondensation |
| CN1485357A (en) * | 2002-09-23 | 2004-03-31 | 北京师范大学 | Method for manufacturing polyesters with ion liquid and such products |
-
2007
- 2007-04-30 CN CN2007101077994A patent/CN101298492B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1229419A (en) * | 1996-09-04 | 1999-09-22 | 株式会社日立制作所 | Method and apparatus for continuous polycondensation |
| CN1485357A (en) * | 2002-09-23 | 2004-03-31 | 北京师范大学 | Method for manufacturing polyesters with ion liquid and such products |
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| Publication number | Publication date |
|---|---|
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