CN109438684A - A kind of 2,5- thiophenedicarboxylic acid base polyester and preparation method thereof - Google Patents
A kind of 2,5- thiophenedicarboxylic acid base polyester and preparation method thereof Download PDFInfo
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- CN109438684A CN109438684A CN201811352583.9A CN201811352583A CN109438684A CN 109438684 A CN109438684 A CN 109438684A CN 201811352583 A CN201811352583 A CN 201811352583A CN 109438684 A CN109438684 A CN 109438684A
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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
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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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
- C08G63/78—Preparation processes
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Abstract
The present invention provides 2 of the structure as shown in formula (I), 5- thiophenedicarboxylic acid base polyester, the principal monomer 2 of the structure, 5- thiophenedicarboxylic acid or 2, two ester type compound of 5- thiophenedicarboxylic acid can be obtained from biomass resource, on the one hand good mechanical property can be had both to avoid the problem of petroleum resources shortage, another aspect material.Bio-based monomer 2,5- thiophenedicarboxylic acid and 2, two ester type compound of 5- thiophenedicarboxylic acid are prepared for biological poly ester material instead of petroleum-based feedstock terephthalic acid (TPA), are conducive to the dependence for getting rid of polyester material to petroleum resources by the present invention.
Description
Technical field
The present invention relates to material and technical field of macromolecules, more particularly, to 2,5- of one kind thiophenedicarboxylic acid base polyester and its
Preparation method.
Background technique
Bio-based materials can be increasingly valued by people due to it from biomass source.Due to petroleum resources
In short supply, bio-based materials have become research hotspot.Document report 2,5- thiophenedicarboxylic acid can be reacted by adipic acid with thionyl chloride
It synthesizes (Fluid Phase Equil.375 (2014) 110-114 and Thermochim.Acta 592 (2014) 52-57).And oneself
Diacid can be synthesized (J.Biotechnol.167 (2013) 75-84) by biomass resource glucaric acid or muconic acid.
And polyethylene terephthalate disclosed in the prior art is very widely used in fiber and packaging field, but its
Main synthon terephthalic acid (TPA) derives from petroleum resources.Therefore, developing one kind can obtain from biomass resource, can keep away
Exempt from shortage of resources, at the same mechanical property it is good polymer it is very necessary.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing one kind 2,5- thiophenedicarboxylic acid base polyester, this hair
2, the 5- thiophenedicarboxylic acid base polyester mechanical property of bright offer is good, while its synthon can be obtained from biomass resource.
The present invention provides a kind of 2, the 5- thiophenedicarboxylic acid base polyester of formula (I) structure, comprising:
Wherein, n is 1~10000；R is that dihydric alcohol removes the remaining group of hydroxyl；The dihydric alcohol includes C5~C20's
The cycloalkane glycol or diethylene glycol (DEG) of straight diol, C3~C20.
Preferably, the straight diol of the C5~C20 is selected from 2,2-dimethyl-1,3-propanediol, 1,5-PD, 1,6-
Hexylene glycol, 1,7- heptandiol, 1,8- ethohexadiol, 1,9- nonanediol, 1,10- decanediol, 11 carbon glycol of 1,11-, 1,12- 12
One or more of carbon glycol, the pure and mild 20 carbon glycol of 1,20- of 13 carbon of 1,13- two；The cycloalkane glycol of the C3~C20
Selected from one or more of 1,4 cyclohexane dimethanol, 1,4- cyclohexanediol and 2,2,4,4- tetramethyl -1,3- cyclobutanediol.
The present invention provides a kind of preparation methods of 2, the 5- thiophenedicarboxylic acid base polyester of formula (I) structure, comprising:
A) 2,5- thiophenedicarboxylic acid and dihydric alcohol carry out esterification under the effect of the catalyst, obtain prepolymer；
Or 2, two ester type compound of 5- thiophenedicarboxylic acid and dihydric alcohol carry out ester exchange reaction under the effect of the catalyst, obtain
To prepolymer；
B the prepolymer) is subjected to polycondensation reaction, obtains 2,5- thiophenedicarboxylic acid base polyester；
Preferably, step A) catalyst is antimony class, tin class or titanium class catalyst.
Preferably, the antimony class catalyst is antimony oxide, antimony glycol or antimony acetate；The tin catalyst is oxygen
Change stannous, stannous octoate, stannous chloride, stannous bromide, stannous iodide, stannous acetate, stannous oxalate, stannous sulfate or hydroxide
Stannous；The titanium class catalyst is butyl titanate, isopropyl titanate or tetraethyl titanate；
Two ester type compound of 2,5- thiophenedicarboxylic acid is selected from 2,5- thiophenedicarboxylic acid dimethyl ester, 2,5- thiophenedicarboxylic acid
Diethylester, 2,5- thiophenedicarboxylic acid dipropyl or 2,5- thiophenedicarboxylic acid dibutyl ester.
Preferably, it is 0.1%~0.3% that the catalyst, which accounts for the mass percent of 2,5- thiophenedicarboxylic acid,；The catalysis
The mass percent that agent accounts for two ester type compound of 2,5- thiophenedicarboxylic acid is 0.1%~0.3%.
Preferably, the esterification reaction temperature is 60~300 DEG C；The reaction time is 1~10h；The transesterification is anti-
Answering temperature is 60~300 DEG C；The reaction time is 1~10h.
Preferably, the dihydric alcohol includes the cycloalkane glycol or diethylene glycol (DEG) of the straight diol of C5~C20, C3~C20.
Preferably, the molar ratio of 2, the 5- thiophenedicarboxylic acid and dihydric alcohol is (1~100): 10；The 2,5- thiophene two
The molar ratio of two ester type compound of formic acid and dihydric alcohol is (1~100): 10.
Preferably, step B) the polycondensation reaction temperature is 80~300 DEG C, the reaction time is 1~10 hour；The polycondensation
Reaction is the polycondensation reaction under vacuum condition；The vacuum degree is 50~100Pa.
Compared with prior art, the present invention provides 2, the 5- thiophenedicarboxylic acid base polyester of the structure as shown in formula (I), the knots
The principal monomer 2 of structure, 5- thiophenedicarboxylic acid or 2, two ester type compound of 5- thiophenedicarboxylic acid can be obtained from biomass resource, a side
Face can have both good mechanical property to avoid the problem of petroleum resources shortage, another aspect material.The present invention is by biology base list
Body 2,5- thiophenedicarboxylic acid and 2, two ester type compound of 5- thiophenedicarboxylic acid are prepared for instead of petroleum-based feedstock terephthalic acid (TPA)
Biological poly ester material is conducive to the dependence for getting rid of polyester material to petroleum resources.
Detailed description of the invention
Fig. 1 is the poly-2,5-thiophene dioctyl phthalate 2,2- dimethyl -1,3- propylene glycol ester that the embodiment of the present invention 1 is prepared
Nucleus magnetic hydrogen spectrum figure；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure for the poly-2,5-thiophene dioctyl phthalate hexylene glycol ester that the embodiment of the present invention 2 is prepared；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure for the poly-2,5-thiophene dioctyl phthalate decanediol ester that the embodiment of the present invention 3 is prepared.
Specific embodiment
The present invention provides one kind 2,5- thiophenedicarboxylic acid base polyester and preparation method thereof, and those skilled in the art can borrow
Reflect present disclosure, is suitably modified realization of process parameters.In particular, it should be pointed out that all similar substitutions and modifications are to this field
It is it will be apparent that they shall fall within the protection scope of the present invention for technical staff.Method and application of the invention has been led to
Preferred embodiment is crossed to be described, related personnel obviously can not depart from the content of present invention, in spirit and scope to this paper's
Methods and applications are modified or appropriate changes and combinations, carry out implementation and application the technology of the present invention.
The present invention provides a kind of 2, the 5- thiophenedicarboxylic acid base polyester of formula (I) structure, comprising:
Wherein, n is 1~10000；Preferably, the n is 1~9000；
R is that dihydric alcohol removes the remaining group of hydroxyl；The dihydric alcohol includes the straight diol of C5~C20, C3~C20
Cycloalkane glycol or diethylene glycol (DEG).
Wherein, the straight diol of the C5~C20 is preferably selected from 2,2-dimethyl-1,3-propanediol, 1,5-PD, 1,
6- hexylene glycol, 1,7- heptandiol, 1,8- ethohexadiol, 1,9- nonanediol, 1,10- decanediol, 11 carbon glycol of 1,11-, 1,12- ten
One or more of two carbon glycol, the pure and mild 20 carbon glycol of 1,20- of 13 carbon of 1,13- two；
The cycloalkane glycol of the C3~C20 is preferably selected from 1,4 cyclohexane dimethanol, 1,4- cyclohexanediol and 2,2,4,
One or more of 4- tetramethyl -1,3- cyclobutanediol.
The 2,5- thiophenedicarboxylic acid base polyester of formula (I) structure of the present invention is preferably specifically including but not limited to tie as follows
Structure:
The present invention provides 2, the 5- thiophenedicarboxylic acid base polyester of the structure as shown in formula (I), the principal monomer 2 of the structure,
5- thiophenedicarboxylic acid or 2, two ester type compound of 5- thiophenedicarboxylic acid can be obtained from biomass resource, on the one hand can be to avoid petroleum
The problem of shortage of resources, another aspect material have both good mechanical property.
The present invention provides a kind of preparation methods of 2, the 5- thiophenedicarboxylic acid base polyester of formula (I) structure, comprising:
A) 2,5- thiophenedicarboxylic acid and dihydric alcohol carry out esterification under the effect of the catalyst, obtain prepolymer；
Or 2, two ester type compound of 5- thiophenedicarboxylic acid and dihydric alcohol carry out ester exchange reaction under the effect of the catalyst, obtain
To prepolymer；
B the prepolymer) is subjected to polycondensation reaction, obtains 2,5- thiophenedicarboxylic acid base polyester；
The preparation method of the 2,5- thiophenedicarboxylic acid base polyester of formula (I) structure provided by the invention is first by 2,5- thiophene two
Formic acid and dihydric alcohol carry out esterification under the effect of the catalyst, obtain prepolymer.
Under the effect of the catalyst, 2,5- thiophenedicarboxylic acid and dihydric alcohol direct esterification, obtain prepolymer.
According to the present invention, the catalyst is antimony class, tin class or titanium class catalyst.
Specifically, the antimony class catalyst is preferably antimony oxide, antimony glycol or antimony acetate；
The tin catalyst is preferably stannous oxide, stannous octoate, stannous chloride, stannous bromide, stannous iodide, acetic acid
Stannous, stannous oxalate, stannous sulfate or stannous hydroxide；
The titanium class catalyst is preferably butyl titanate, isopropyl titanate or tetraethyl titanate.
According to the present invention, the dihydric alcohol includes that the straight diol of C5~C20, the cycloalkane glycol of C3~C20 or two are sweet
Alcohol.
Wherein, the straight diol of the C5~C20 is preferably selected from 2,2-dimethyl-1,3-propanediol, 1,5-PD, 1,
6- hexylene glycol, 1,7- heptandiol, 1,8- ethohexadiol, 1,9- nonanediol, 1,10- decanediol, 11 carbon glycol of 1,11-, 1,12- ten
One or more of two carbon glycol, the pure and mild 20 carbon glycol of 1,20- of 13 carbon of 1,13- two；
The cycloalkane glycol of the C3~C20 is preferably selected from 1,4 cyclohexane dimethanol, 1,4- cyclohexanediol and 2,2,4,
One or more of 4- tetramethyl -1,3- cyclobutanediol.
The present invention to the sources of said components without limiting, it is commercially available.
The mass percent that catalyst of the present invention accounts for 2,5- thiophenedicarboxylic acid is preferably 0.1%~0.3%.
The molar ratio of 2,5- thiophenedicarboxylic acid and dihydric alcohol of the present invention is preferably (1~100): 10；More preferably (1
~80): 10；Most preferably (1~50): 10；It is the most preferably (1~30): 10；Can also be (1~20): 10；Can also be
(1~10): 10.
The above-mentioned reaction of the present invention carries out preferably in reaction flask；More preferably carried out under the protection of inert gas；It is described lazy
Property gas includes but is not limited to nitrogen.The esterification reaction temperature is preferably 60~300 DEG C；More preferably 100~300 DEG C；Most
Preferably 150~290 DEG C.The reaction is preferably stirred to react, the present invention to the concrete operations of the stirring without limiting,
It is well known to those skilled in the art；It is described that be stirred to react the time be preferably 1~10h；More preferably 2~9h；Most preferably 3
~8h.
When raw material of the present invention is 2,5- thiophenedicarboxylic acid, two ester type compound, above-mentioned reaction can also be carried out, i.e., are as follows:
2,5- thiophenedicarboxylic acid, two ester type compound and dihydric alcohol carry out ester exchange reaction under the effect of the catalyst, obtain
Prepolymer.
Under the effect of the catalyst, 2,5- thiophenedicarboxylic acid, two ester type compound and dihydric alcohol carry out ester exchange reaction, obtain
To prepolymer.
Wherein, the catalyst is antimony class, tin class or titanium class catalyst.
Specifically, the antimony class catalyst is preferably antimony oxide, antimony glycol or antimony acetate；
The tin catalyst is preferably stannous oxide, stannous octoate, stannous chloride, stannous bromide, stannous iodide, acetic acid
Stannous, stannous oxalate, stannous sulfate or stannous hydroxide；
The titanium class catalyst is preferably butyl titanate, isopropyl titanate or tetraethyl titanate.
According to the present invention, the dihydric alcohol includes that the straight diol of C5~C20, the cycloalkane glycol of C3~C20 or two are sweet
Alcohol.
Wherein, the straight diol of the C5~C20 is preferably selected from 2,2-dimethyl-1,3-propanediol, 1,5-PD, 1,
6- hexylene glycol, 1,7- heptandiol, 1,8- ethohexadiol, 1,9- nonanediol, 1,10- decanediol, 11 carbon glycol of 1,11-, 1,12- ten
One or more of two carbon glycol, the pure and mild 20 carbon glycol of 1,20- of 13 carbon of 1,13- two；
The cycloalkane glycol of the C3~C20 is preferably selected from 1,4 cyclohexane dimethanol, 1,4- cyclohexanediol and 2,2,4,
One or more of 4- tetramethyl -1,3- cyclobutanediol.
The present invention to the sources of said components without limiting, it is commercially available.
Catalyst of the present invention account for the mass percent of two ester type compound of 2,5- thiophenedicarboxylic acid be preferably 0.1%~
0.3%.
The molar ratio of two ester type compound of 2,5- thiophenedicarboxylic acid and dihydric alcohol of the present invention is preferably (1~100):
10；More preferably (1~80): 10；Most preferably (1~50): 10；It is the most preferably (1~30): 10；Can also be (2~
20):10；Can also be (2~10): 10.
Two ester type compound of 2,5- thiophenedicarboxylic acid of the present invention is preferably selected from 2,5- thiophenedicarboxylic acid dimethyl ester, 2,5-
Thiophenedicarboxylic acid diethylester, 2,5- thiophenedicarboxylic acid dipropyl or 2,5- thiophenedicarboxylic acid dibutyl ester.The present invention is to its specific behaviour
Make without limiting, those skilled in the art are known.
The above-mentioned reaction of the present invention carries out preferably in reaction flask；More preferably carried out under the protection of inert gas；It is described lazy
Property gas includes but is not limited to nitrogen.The esterification reaction temperature is preferably 60~300 DEG C；More preferably 100~300 DEG C；Most
Preferably 150~290 DEG C.The reaction is preferably stirred to react, the present invention to the concrete operations of the stirring without limiting,
It is well known to those skilled in the art；It is described that be stirred to react the time be preferably 1~10h；More preferably 2~9h；Most preferably 3
~8h.
After obtaining prepolymer, prepolymer is subjected to polycondensation reaction, obtains 2,5- thiophenedicarboxylic acid base polyester；
Polycondensation reaction of the present invention is preferably the polycondensation reaction under vacuum condition；The vacuum degree is preferably 50~
100Pa.The polycondensation reaction temperature is preferably 80~300 DEG C, more preferably 100~300 DEG C, most preferably 150~300 DEG C,
The reaction time is preferably 1~10 hour；More preferably 2~9 hours；Most preferably 3~8 hours.
The present invention provides 2, the 5- thiophenedicarboxylic acid base polyester of the structure as shown in formula (I), the principal monomer 2 of the structure,
5- thiophenedicarboxylic acid or 2, two ester type compound of 5- thiophenedicarboxylic acid can be obtained from biomass resource, on the one hand can be to avoid petroleum
The problem of shortage of resources, another aspect material have both good mechanical property.The present invention is by bio-based monomer 2,5- thiophene diformazan
Acid and 2,5- thiophenedicarboxylic acid, two ester type compound are prepared for biology base polyester material instead of petroleum-based feedstock terephthalic acid (TPA)
Material, is conducive to the dependence for getting rid of polyester material to petroleum resources.
In order to further illustrate the present invention, with reference to embodiments to a kind of 2,5- thiophenedicarboxylic acid base provided by the invention
Polyester and preparation method thereof is described in detail.
Embodiment 1
(1) under the action of stannous oxalate, 2,5- thiophenedicarboxylic acid dimethyl ester and 2,2-dimethyl-1,3-propanediol are added
Enter into reaction flask, the molar ratio of 2,5- thiophenedicarboxylic acid dimethyl esters and 2,2-dimethyl-1,3-propanediol is 6:10, and oxalic acid is sub-
Tin accounts for the 0.3% of diester mass percent, and under nitrogen protection, 200 DEG C are stirred to react 3h, generates prepolymer.
(2) it in above-mentioned prepolymer, will be evacuated down to 80Pa, 235 DEG C are stirred to react 8h, poly- 2,5- thiophenedicarboxylic acid 2 is obtained,
2- dimethyl-1,3-propylene glycol ester.Structural formula is such as shown in (I-1):
The poly-2,5-thiophene dioctyl phthalate 2,2- dimethyl -1,3- propylene glycol ester nucleus magnetic hydrogen spectrum figure that embodiment 1 is prepared is such as
Shown in Fig. 1.
Embodiment 2
(1) under the action of stannous oxalate, by 2,5- thiophenedicarboxylic acid and 1,6- hexylene glycol is added in reaction flask, and 2,
The molar ratio of 5- thiophenedicarboxylic acid and 1,6- hexylene glycol is 7:10, and stannous oxalate accounts for 2,5- thiophenedicarboxylic acid mass percent
0.1%, under nitrogen protection, 230 DEG C are stirred to react 1h, generate prepolymer.
(2) 70Pa in above-mentioned prepolymer, will be evacuated down to, 230 DEG C are stirred to react 5h, obtain poly- 2,5- thiophenedicarboxylic acid oneself
Diol ester.Structural formula such as formula (I-2):
The poly-2,5-thiophene dioctyl phthalate hexylene glycol ester nucleus magnetic hydrogen spectrum figure that embodiment 2 is prepared is as shown in Figure 2.
Embodiment 3
(1) under the action of butyl titanate, by 2,5- thiophenedicarboxylic acid diethylester and 1,10- decanediol is added to reaction
In bottle, the molar ratio of 2,5- thiophenedicarboxylic acid diethylesters and 1,10- decanediol is 8:10, and butyl titanate accounts for 2,5- thiophene diformazan
The 0.1% of diethyl phthalate mass percent, under nitrogen protection, 200 DEG C are stirred to react 3h, generate prepolymer.
(2) it in above-mentioned prepolymer, will be evacuated down to 70Pa, 300 DEG C are stirred to react 6h, obtain poly- 2, the 5- thiophenedicarboxylic acid last of the ten Heavenly stems
Diol ester.Structural formula such as formula (I-3):
The poly-2,5-thiophene dioctyl phthalate decanediol ester nucleus magnetic hydrogen spectrum figure that embodiment 3 is prepared is as shown in Figure 3.
The mechanical property of 1 2,5- thiophenedicarboxylic acid base polyester of table
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of 2,5- thiophenedicarboxylic acid base polyester of formula (I) structure characterized by comprising
Wherein, n is 1~10000；R is that dihydric alcohol removes the remaining group of hydroxyl；The dihydric alcohol includes the straight chain of C5~C20
The cycloalkane glycol or diethylene glycol (DEG) of glycol, C3~C20.
2. 2,5- thiophenedicarboxylic acid base polyester according to claim 1, which is characterized in that the straight chain two of the C5~C20
Alcohol is selected from 2,2- dimethyl -1,3- propylene glycol, 1,5- pentanediol, 1,6-HD, 1,7- heptandiol, 1,8- ethohexadiol, 1,9-
Nonanediol, 1,10- decanediol, 11 carbon glycol of 1,11-, 12 carbon glycol of 1,12-, the pure and mild 1,20- 20 of 13 carbon of 1,13- two
One or more of carbon glycol；The cycloalkane glycol of the C3~C20 is selected from 1,4 cyclohexane dimethanol, 1,4- cyclohexanediol
One or more of with 2,2,4,4- tetramethyl -1,3- cyclobutanediol.
3. a kind of preparation method of 2, the 5- thiophenedicarboxylic acid base polyester of formula (I) structure characterized by comprising
A) 2,5- thiophenedicarboxylic acid and dihydric alcohol carry out esterification under the effect of the catalyst, obtain prepolymer；
Or 2, two ester type compound of 5- thiophenedicarboxylic acid and dihydric alcohol carry out ester exchange reaction under the effect of the catalyst, obtain pre-
Polymers；
B the prepolymer) is subjected to polycondensation reaction, obtains 2,5- thiophenedicarboxylic acid base polyester；
4. preparation method according to claim 3, which is characterized in that step A) catalyst is antimony class, tin class or titanium
Class catalyst.
5. preparation method according to claim 3, which is characterized in that the antimony class catalyst is antimony oxide, second two
Alcohol antimony or antimony acetate；The tin catalyst is stannous oxide, stannous octoate, stannous chloride, stannous bromide, stannous iodide, second
Sour stannous, stannous oxalate, stannous sulfate or stannous hydroxide；The titanium class catalyst is butyl titanate, isopropyl titanate
Or tetraethyl titanate；
Two ester type compound of 2,5- thiophenedicarboxylic acid is selected from 2,5- thiophenedicarboxylic acid dimethyl ester, 2,5- thiophenedicarboxylic acid diethyl
Ester, 2,5- thiophenedicarboxylic acid dipropyl or 2,5- thiophenedicarboxylic acid dibutyl ester.
6. preparation method according to claim 3, which is characterized in that the catalyst accounts for the quality of 2,5- thiophenedicarboxylic acid
Percentage is 0.1%~0.3%；The mass percent that the catalyst accounts for two ester type compound of 2,5- thiophenedicarboxylic acid is
0.1%~0.3%.
7. preparation method according to claim 3, which is characterized in that the esterification reaction temperature is 60~300 DEG C；It is described
Reaction time is 1~10h；The transesterification reaction temperature is 60~300 DEG C；The reaction time is 1~10h.
8. preparation method according to claim 3, which is characterized in that the dihydric alcohol include C5~C20 straight diol,
The cycloalkane glycol or diethylene glycol (DEG) of C3~C20.
9. preparation method according to claim 7, which is characterized in that mole of 2, the 5- thiophenedicarboxylic acid and dihydric alcohol
Than for (1~100): 10；The molar ratio of two ester type compound of 2,5- thiophenedicarboxylic acid and dihydric alcohol is (1~100): 10.
10. preparation method according to claim 3, which is characterized in that step B) the polycondensation reaction temperature is 80~300
DEG C, the reaction time is 1~10 hour；The polycondensation reaction is the polycondensation reaction under vacuum condition；The vacuum degree be 50~
100Pa。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110734542A (en) * | 2019-10-24 | 2020-01-31 | 中国科学院宁波材料技术与工程研究所 | novel thiophene diformate copolyester and preparation method and application thereof |
| CN112375214A (en) * | 2020-11-06 | 2021-02-19 | 彤程化学（中国）有限公司 | Heteroatom-containing high-barrier biodegradable copolyester and preparation method and application thereof |
| CN113121805A (en) * | 2021-03-09 | 2021-07-16 | 武汉科技大学 | Preparation and application of sulfur-containing copolyester based on 2, 5-thiophenedicarboxylic acid |
| CN113292712A (en) * | 2021-05-25 | 2021-08-24 | 吉林建筑大学 | 1, 4-succinic acid-based copolyester material and preparation method and application thereof |
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| CN112375214A (en) * | 2020-11-06 | 2021-02-19 | 彤程化学（中国）有限公司 | Heteroatom-containing high-barrier biodegradable copolyester and preparation method and application thereof |
| CN113121805A (en) * | 2021-03-09 | 2021-07-16 | 武汉科技大学 | Preparation and application of sulfur-containing copolyester based on 2, 5-thiophenedicarboxylic acid |
| CN113121805B (en) * | 2021-03-09 | 2023-11-28 | 武汉科技大学 | Preparation and application of sulfur-containing copolyester based on 2, 5-thiophene dicarboxylic acid |
| CN113292712A (en) * | 2021-05-25 | 2021-08-24 | 吉林建筑大学 | 1, 4-succinic acid-based copolyester material and preparation method and application thereof |
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