CN102060983B - Preparation method of cyclic polyester oligomer - Google Patents
Preparation method of cyclic polyester oligomer Download PDFInfo
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- CN102060983B CN102060983B CN201010568899A CN201010568899A CN102060983B CN 102060983 B CN102060983 B CN 102060983B CN 201010568899 A CN201010568899 A CN 201010568899A CN 201010568899 A CN201010568899 A CN 201010568899A CN 102060983 B CN102060983 B CN 102060983B
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- alcohol esters
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Abstract
The invention relates to a preparation method of a cyclic polyester oligomer. The traditional method has the problems of difficulty in recycling halogen and side products of ammonium salts, and the like, thereby being difficult to be used in production. The preparation method comprises the steps of: firstly, dissolving linear poly dihydricalcohol terephthalate into a high-boiling point organic solvent, heating and stirring to form a transparent solution of the poly dihydricalcohol terephthalate; then adding an organic tin catalyst into the transparent solution of the poly dihydricalcohol terephthalate, cracking and cyclizing to form a solution of the poly dihydricalcohol terephthalate; and cooling the solution, filtering and drying to obtain the poly dihydricalcohol terephthalate, removing remained organic tin catalyst from the solution through column chromatography, and drying to obtain the cyclic polyester oligomer without containing the organic tin catalyst. The cyclic polyester oligomer prepared by using the method can not generate self-polymerizing side reactions in a normal temperature storage period and a processing temperature-raising process.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of method for preparing the cyclic polyester oligopolymer, be specifically related to a kind of linear polyester organic solution prepares the cyclic polyester oligopolymer in the presence of organotin catalysts method.
Background technology
Aromatic polyester is the one type of synthesized polymer material that grows up the 1950's; They have good mechanical performance, thermostability height, resistance to chemical attack, numerous advantages such as cheap; Be used widely in fields such as fiber, film, engineering plastics, it mainly is represented as PET (polyethylene terephthalate), PTT (PTT) and PBT (polybutylene terephthalate).The aromatic polyester mainly verivate through aromatic acid or ester and aliphatics or alicyclic divalent alcohol obtains through polycondensation.The machine-shaping in several ways of this polyester, for example injection molding is extruded etc.
The cyclic polyester oligopolymer that occurred in recent years, viscosity is very low at a certain temperature owing to it, and wetting ability is strong during use, filling capacity strong, processing viscosity is low, and good with the consistency of various fillers, strongthener and macromolecular material.These characteristics make ring-type terephthalic acid binary alcohol esters resin have unique effect in different Application Areass.In addition, the fusing point of cyclic polyester oligopolymer and polymerization temperature all under the fusing point of resulting polymers, can have been saved time and energy consumption in polymeric crystallization simultaneously, have reduced cost simultaneously.
A kind of typical method of preparation cyclic polyester oligopolymer is in the presence of amine catalyst, utilizes divalent alcohol and have corrosive carboxylic acid halides reaction to make for example butyleneglycol and terephthalyl chloride reaction.This kind method makes it be difficult to be used for produce because the disagreeableness halogen of environment has been introduced in existence and the by product ammonium salt is difficult to problems such as recycling.Usually use organotin or organic titanium catalyzer in cyclic polyester oligopolymer production process; These catalyzer can cause cyclic polyester oligopolymer ring-opening polymerization under the situation of being heated; In injection moulding processing, further accelerate set time, be unfavorable for controlling product performance.In addition, in the prolonged preservation process, catalyst residue can cause the monomer autohemagglutination in the cyclic polyester oligopolymer, shortens the product retention period.
Summary of the invention
The object of the invention is exactly the deficiency to prior art, and a kind of preparation method of cyclic polyester oligopolymer is provided, and the cyclic polyester oligopolymer of preparation does not contain residual catalyst.
The concrete steps of the inventive method are:
Step 1. at first is dissolved in linear poly terephthalic acid binary alcohol esters in the high boiling organic solvent, is heated to 140～240 ℃, stirs 10～60 minutes, forms the clear solution of poly terephthalic acid binary alcohol esters;
Described linear poly terephthalic acid binary alcohol esters is monocycle di-substituted aryl perfume base diacid and aliphatic dialcohol esterifying polycondensation product, has the structural unit that is described below:
Wherein A is a monocycle di-substituted aryl perfume base, is 1,3 or 1, the substituted di-substituted aryl perfume base of 4-; Aliphatic dialcohol is the linear diols that contains 2～10 methylene radical.
Described high boiling organic solvent be boiling point at the solvent more than 110 ℃, comprising: chlorobenzene, naphthalene, tetramethyl-benzene, methylnaphthalene, orthodichlorobenzene, trichlorobenzene or their mixed solvent; Add 5～50g poly terephthalic acid binary alcohol esters in every rising boiling point organic solvent.
Step 2. joins organotin catalysts in the clear solution of poly terephthalic acid binary alcohol esters; Under 140～220 ℃ of conditions, reacted 30～240 minutes; Linear poly terephthalic acid binary alcohol esters forms the solution of poly terephthalic acid binary alcohol esters through cracking, Cheng Huan.
The molecule of described organotin catalysts comprises one or two tin atom at least, and two carbon atoms link to each other with tin atom with one or two Sauerstoffatom, and molecular formula is:
Wherein the structural formula of R and R ' is CH
3(CH
2)
i, i=0～5; R " structural formula be (CH
2)
j, j=1～6.
The solution that step 3. obtains step 2 is cooled to 25～100 ℃, and after the filtration, it is dry under 30～100 ℃, will to filtrate, and obtains the poly terephthalic acid binary alcohol esters.
Step 4. obtains product with step 3 and is dissolved in formation product solution in the low boiling point organic solvent, and product solution is removed residual organotin catalysts through column chromatography method, is not contained the cyclic polyester oligopolymer of organic tin catalyst after the drying.
Described low boiling point organic solvent be boiling point at the solvent below 100 ℃, comprising: methylene dichloride, trichloromethane, ether, acetone, normal hexane, sherwood oil or their mixed solvent.
The present invention is directed to the shape polyester oligomer and prepare the problem of residual meeting meeting initiation side reaction in purification of shape polyester oligomer and polymerization process of organotin catalysts in the process; Disclose a kind of preparation method of high purity shape polyester oligomer, the autohemagglutination side reaction does not take place in products therefrom between the normal temperature preservation period with in the processing temperature-rise period.
Embodiment
Embodiment 1
In three mouthfuls of reaction flasks of the 50ml that mechanical stirring device is housed, add 20 milliliters of dry chlorobenzenes and 0.15 gram polybutylene terephthalate (PBT, Mw=45000, vinylbenzene standard); Nitrogen replacement three times is heated with stirring to 140 ℃, makes the PBT dissolution system become clear solution; Add the 0.02g dimethyl tin oxide again, react after 240 minutes, be cooled to 25 ℃; Heat filtering, filtrate decompression is drained solvent, obtains white solid.White solid is dissolved in the methylene dichloride, solution is removed residual organotin catalysts through column chromatography method, obtain final product after the drying.This reaction yield is 24%.
Embodiment 2
In three mouthfuls of reaction flasks of the 100ml that mechanical stirring device is housed, add 40 milliliters of dry orthodichlorobenzenes and 0.5 gram PTT (PTT, Mw=128000, vinylbenzene standard); Nitrogen replacement three times is heated with stirring to 190 ℃, makes the PTT dissolution system become clear solution; Add the 0.25g Dibutyltin oxide again, react after 180 minutes, be cooled to 50 ℃; Heat filtering, filtrate decompression is drained solvent, obtains white solid.White solid is dissolved in the trichloromethane, solution is removed residual organotin catalysts through column chromatography method, obtain final product after the drying.This reaction yield is 37%.
Embodiment 3
In three mouthfuls of reaction flasks of the 500ml that mechanical stirring device is housed, add 250 milliliters of dry naphthalenes and 3 gram polyethylene terephtalates (Mw=82000, vinylbenzene standard), nitrogen replacement three times is heated with stirring to 210 ℃; Make the PET dissolution system become clear solution, add 0.3g 1,1,6 again, 6-four positive methyl isophthalic acids; 6-two tin-2,5,7,10-four oxygen cyclodecane react after 45 minutes; Be cooled to 100 ℃, heat filtering, filtrate decompression is drained solvent, obtains white solid.White solid is dissolved in the ether, solution is removed residual organotin catalysts through column chromatography method, obtain final product after the drying.This reaction yield is 83%.
Embodiment 4
In three mouthfuls of reaction flasks of the 1000ml that mechanical stirring device is housed, add 500 milliliters of dry methylnaphthalenes and 12 gram polybutylene terephthalate PBT (Mw=95000, vinylbenzene standard); Nitrogen replacement three times is heated with stirring to 240 ℃, makes the PBT dissolution system become clear solution; Add 1.24g dibutyl dibutoxy tin again, react after 30 minutes, be cooled to 75 ℃; Heat filtering, filtrate decompression is drained solvent, obtains white solid.White solid is dissolved in the methylene dichloride, solution is removed residual organotin catalysts through column chromatography method, obtain final product after the drying.This reaction yield is 62%.
Embodiment 5
In three mouthfuls of reaction flasks of the 1000ml that mechanical stirring device is housed, add 500 milliliters of dry trichlorobenzene and 16 gram PBT (Mw=125000, vinylbenzene standard), nitrogen replacement three times is heated with stirring to 200 ℃; Make the PBT dissolution system become clear solution, add 1.5g 1,1,6 again, 6-tetra-n-butyl-1; 5-two tin-2,4,6,8-four oxygen cyclooctane react after 45 minutes; Be cooled to 80 ℃, heat filtering, filtrate decompression is drained solvent, obtains white solid.White solid is dissolved in the acetone, solution is removed residual organotin catalysts through column chromatography method, obtain final product after the drying.This reaction yield is 75%.
Embodiment 6
In three mouthfuls of reaction flasks of the 500ml that mechanical stirring device is housed, add 250 milliliters of dryings 1,2,4; 5-tetramethyl-benzene and 4.5 grams gather phthalic acid butanediol ester (Mw=45000, vinylbenzene standard), and nitrogen replacement three times is heated with stirring to 195 ℃; Make the PBT dissolution system become clear solution, add 0.36g dihexyl White tin oxide again, react after 60 minutes, be cooled to 85 ℃; Heat filtering, filtrate decompression is drained solvent, obtains white solid.White solid is dissolved in the normal hexane, solution is removed residual organotin catalysts through column chromatography method, obtain final product after the drying.This reaction yield is 42%.
Embodiment 7
In three mouthfuls of reaction flasks of the 500ml that mechanical stirring device is housed, add 150 milliliters of dry orthodichlorobenzenes and 100 milliliters of trichlorobenzene and 10 gram PBT (Mw=95000, vinylbenzene standard); Nitrogen replacement three times is heated with stirring to 190 ℃, makes the PBT dissolution system become clear solution; Add 0.8g diethylammonium White tin oxide again, react after 75 minutes, be cooled to 75 ℃; Heat filtering, filtrate decompression is drained solvent, obtains white solid.White solid is dissolved in the sherwood oil, solution is removed residual organotin catalysts through column chromatography method, obtain final product after the drying.This reaction yield is 32%.
Embodiment 8.
In three mouthfuls of reaction flasks of the 500ml that mechanical stirring device is housed, add 250 milliliters of dry orthodichlorobenzenes and 12 gram poly terephthalic acid certain herbaceous plants with big flowers diol esters (Mw=65000, vinylbenzene standard), nitrogen replacement three times is heated with stirring to 190 ℃; Making it dissolution system becomes clear solution, adds 1.2g 1,1,6 again, 6-four n-hexyls-1; 6-two tin-2,5,7,10-four oxygen cyclodecane react after 75 minutes; Be cooled to 75 ℃, heat filtering, filtrate decompression is drained solvent, obtains white solid.White solid is dissolved in the normal hexane, solution is removed residual organotin catalysts through column chromatography method, obtain final product after the drying.This reaction yield is 75%.
Embodiment 9.
In three mouthfuls of reaction flasks of the 500ml that mechanical stirring device is housed, add 250 milliliters of dry orthodichlorobenzenes and 5 gram PET (polyethylene terephthalate) (Mw=65000, vinylbenzene standard), nitrogen replacement three times is heated with stirring to 190 ℃; Make the PBT dissolution system become clear solution, add 0.45g 1,1,6 again, 6-tetraethyl--1; 6-two tin-2,5,7,10-four oxygen cyclodecane react after 75 minutes; Be cooled to 75 ℃, heat filtering, filtrate decompression is drained solvent, obtains white solid.White solid is dissolved in the methylene dichloride, solution is removed residual organotin catalysts through column chromatography method, obtain final product after the drying.This reaction yield is 82%.
Embodiment 10.
In three mouthfuls of reaction flasks of the 5000ml that mechanical stirring device is housed, add 2500 milliliters of dry orthodichlorobenzenes and 50 gram poly terephthalic acid pinakon esters (Mw=76000, vinylbenzene standard); Nitrogen replacement three times is heated with stirring to 190 ℃, makes the PBT dissolution system become clear solution; Add 5.5g dibutyl diethoxy tin again, react after 75 minutes, be cooled to 75 ℃; Heat filtering, filtrate decompression is drained solvent, obtains white solid.White solid is dissolved in the ether, solution is removed residual organotin catalysts through column chromatography method, obtain final product after the drying.This reaction yield is 68%.
Embodiment 11.
In three mouthfuls of reaction flasks of the 2000ml that mechanical stirring device is housed, add 1000 milliliters of dry orthodichlorobenzenes and 32 gram PBT (Mw=95000, vinylbenzene standard), nitrogen replacement three times is heated with stirring to 190 ℃; Make the PBT dissolution system become clear solution, add 3.92g 1,1,8 again, 8-tetra-n-butyl-1; 8-two tin-2,10,12,18-four oxygen ring octadecanes react after 75 minutes; Be cooled to 75 ℃, heat filtering, filtrate decompression is drained solvent, obtains white solid.White solid is dissolved in the acetone, solution is removed residual organotin catalysts through column chromatography method, obtain final product after the drying.This reaction yield is 78%.
Embodiment 12
With the silica-filled long 1m of pH=6.5, diameter is the glass column of 0.025m, is dissolved in methylene dichloride (10ml) to the CBT that obtains among the embodiment 1 (2g), is moving phase with methylene chloride mixed solvent (volume ratio 100: 1), and normal pressure is crossed post.Collect solution,, obtain the 1.76g white solid product solution evaporation.Using emission spectrometer to detect tin element content is 0.(in the CBT raw material tin element content account for the mass ratio of inorganic element content be 77.8%)
Embodiment 13
With the silica-filled long 1m of pH=6.5, diameter is the glass column of 0.025m, is dissolved in methylene dichloride (10ml) to the CBT that obtains among the embodiment 1 (2g), is moving phase with methylene dichloride/ether mixed solvent (volume ratio 50: 1), and normal pressure is crossed post.Collect solution,, obtain the 1.65g white solid product solution evaporation.Using emission spectrometer to detect tin element content is 0.
Claims (1)
1. the preparation method of a cyclic polyester oligopolymer is characterized in that the concrete steps of this method are:
Step (1) at first is dissolved in linear poly terephthalic acid binary alcohol esters in the high boiling organic solvent, is heated to 140～240 ℃, stirs 10～60 minutes, forms the clear solution of poly terephthalic acid binary alcohol esters; Described high boiling organic solvent is one or more mixed solvents in chlorobenzene, naphthalene, tetramethyl-benzene, methylnaphthalene, orthodichlorobenzene, the trichlorobenzene, adds 5～50g poly terephthalic acid binary alcohol esters in every rising boiling point organic solvent;
Described linear poly terephthalic acid binary alcohol esters is monocycle di-substituted aryl perfume base diacid and aliphatic dialcohol esterifying polycondensation product, has the structural unit that is described below:
Wherein A is a monocycle di-substituted aryl perfume base, is 1,3 or 1, the substituted di-substituted aryl perfume base of 4-; Aliphatic dialcohol is the linear diols that contains 2～10 methylene radical;
Step (2) joins organotin catalysts in the clear solution of poly terephthalic acid binary alcohol esters; Under 140～220 ℃ of conditions, reacted 30～240 minutes; Linear poly terephthalic acid binary alcohol esters forms the solution of poly terephthalic acid binary alcohol esters through cracking, Cheng Huan;
The molecule of described organotin catalysts comprises one or two tin atom at least, and two carbon atoms link to each other with tin atom with one or two Sauerstoffatom, and molecular formula is:
Wherein the structural formula of R and R ' is CH
3(CH
2)
i, i=0～5; R " structural formula be (CH
2)
j, j=1～6;
Step (3) is cooled to 25～100 ℃ with the solution that step (2) obtains, and after the filtration, it is dry under 30～100 ℃, will to filtrate, and obtains the poly terephthalic acid binary alcohol esters;
Step (4) obtains product with step (3) and is dissolved in formation product solution in the low boiling point organic solvent, and product solution is removed residual organotin catalysts through column chromatography method, is not contained the cyclic polyester oligopolymer of organic tin catalyst after the drying; Described low boiling point organic solvent is one or more mixed solvents in methylene dichloride, trichloromethane, ether, acetone, normal hexane, the sherwood oil.
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| CN201010568899A CN102060983B (en) | 2010-11-30 | 2010-11-30 | Preparation method of cyclic polyester oligomer |
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| CN201010568899A CN102060983B (en) | 2010-11-30 | 2010-11-30 | Preparation method of cyclic polyester oligomer |
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| CN102060983B true CN102060983B (en) | 2012-09-19 |
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| CN115260150B (en) * | 2022-08-26 | 2024-01-09 | 浙江理工大学 | Preparation method of polyethylene terephthalate cyclic trimer |
| CN116693497B (en) * | 2023-08-01 | 2023-10-10 | 苏州大学 | Depolymerization cyclization method of aromatic polyester |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0699701A2 (en) * | 1994-08-31 | 1996-03-06 | General Electric Company | Process for preparing macrocyclic polyester oligomers |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0699701A2 (en) * | 1994-08-31 | 1996-03-06 | General Electric Company | Process for preparing macrocyclic polyester oligomers |
Non-Patent Citations (1)
| Title |
|---|
| 张红娟等.新型环形对苯二甲酸丁二醇酯低聚物的合成、应用与研究进展.《中国塑料》.2007,第21卷(第3期),第1-4页. * |
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