CN107226902A - A kind of degradable sulfofatty race aromatic polyester and preparation method thereof - Google Patents
A kind of degradable sulfofatty race aromatic polyester and preparation method thereof Download PDFInfo
- Publication number
- CN107226902A CN107226902A CN201710408458.4A CN201710408458A CN107226902A CN 107226902 A CN107226902 A CN 107226902A CN 201710408458 A CN201710408458 A CN 201710408458A CN 107226902 A CN107226902 A CN 107226902A
- Authority
- CN
- China
- Prior art keywords
- sulfofatty
- aromatic polyester
- degradable
- preparation
- race
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C08G63/88—Post-polymerisation treatment
- C08G63/90—Purification; Drying
-
- 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
- C08G2230/00—Compositions for preparing biodegradable polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a kind of degradable sulfofatty race aromatic polyester and preparation method thereof, methods described includes：By thio-2 acid, aromatic diol and catalyst, 150 DEG C~190 DEG C and the lower progress esterification of nitrogen protection are placed in, intermediate product is obtained；Stopping is passed through nitrogen, the intermediate product is placed in 190 DEG C~230 DEG C and vacuumized polycondensation reaction is carried out under state, obtains polymer；Organic solvent is added in the polymer, the polymer largely dissolves, obtain clear liquid, the clear liquid is instilled in alcohols solvent, white depositions are generated, centrifuges, obtains white solid, white solid progress alcohol is washed and dried, a kind of degradable sulfofatty race aromatic polyester is obtained.The inventive method, which has been synthesized, a kind of has good performance concurrently and the sulfofatty race aromatic polyester material of excellent degradation property.
Description
Technical field
The invention belongs to technical field of organic synthesis, more particularly to a kind of degradable sulfofatty race aromatic polyester and
Its preparation method.
Background technology
Plastics are widely used in work, agricultural and daily life due to cheap and with versatility.
But plastics are caused " white pollution " using natural degradation is difficult to after discarding.Polyester is the widely used high polymer material of a class,
Polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) (PBT) are common are, with good physical machine
Tool performance, is widely used in varieties of food items and the packaging of beverage.But the extremely difficult degraded of this kind polyester, easily turns into white pollution after discarding
Thing.Therefore, the polyester with excellent performance and degradation property is found, one as synthesis of polymer material field grinds greatly
Study carefully focus.
In recent years, many scientists are devoted to the research for the polyester that can be degraded under natural environmental condition.At present can be certainly
The polyester polymer so degraded, its main chain is mostly formed by connecting by aliphatic structure unit by the ester bond of facile hydrolysis, main chain
It is submissive thus in compost or easily decomposes in its natural state.
Slowly displayed however as deepening continuously for research, the drawbacks of aliphatic polyester itself, decomposition temperature it is low and
Hot property is poor, so that actual hot-working requirement can not be met.And aromatic polyester has higher decomposition temperature, good heat is steady
Qualitative energy, it is cheap, but its degradation property is very poor.Therefore, suitable aliphatic and aromatic monomer are found, synthesis has fat concurrently
The polyester product of the respective advantage of fat adoption ester and aromatic polyester, the focus studied as macromolecule polyester materials synthesis.
The content of the invention
For above mentioned problem of the prior art, it is a primary object of the present invention to provide a kind of degradable sulfofatty
Race's aromatic polyester and preparation method thereof, methods described has synthesized the aliphatic-aromatic polyester material with good degradation property
Material.
In order to solve the above problems, the present invention is adopted the following technical scheme that：A kind of degradable sulfofatty race aromatic series
The preparation method of polyester, methods described includes：
By thio-2 acid, aromatic diol and catalyst, 150 DEG C~190 DEG C and the lower progress ester of nitrogen protection are placed in
Change reaction, obtain intermediate product；
Stopping be passed through nitrogen, by the intermediate product be placed in 190 DEG C~230 DEG C and vacuumize under state carry out polycondensation it is anti-
Should, obtain polyester crude product.
As further preferred, include the purification of the polyester crude product, the purification includes：Add in the polyester
Enter organic solvent, the polyester is largely dissolved, and obtains clear liquid, and the clear liquid is instilled in alcohols solvent, generates white precipitate
Thing, is centrifuged, obtains white solid, and solid progress alcohol is washed and dried, and obtains the fragrant adoption of the sulfofatty race
Ester.
As further preferably, the pressure (absolute pressure, similarly hereinafter) of the esterification is 101KPa, the esterification
Time is 2~3h.
As further preferably, the pressure in the polycondensation reaction stage is 50Pa~1000Pa, the polycondensation reaction
Time is 2-4h.
As further preferably, the polycondensation reaction stage includes：By the intermediate product be evacuated to 500Pa~
1000Pa, under the conditions of 190 DEG C~200 DEG C, reacts 1~2 hour, under the vacuum and temperature conditionss, removes polycondensation reaction
The small molecule by-product of generation, promotes reversible reaction to be carried out to polycondensation reaction direction；200 DEG C~230 DEG C are then raised temperature to, takes out true
Sky is to 50Pa~500Pa, to remove unreacted excess monomer, while accelerating the speed of polycondensation reaction, reacts 1~2 hour.
As further preferably, the mol ratio of the thio-2 acid and aromatic diol is 1 ﹕ 1~1.1.
As further preferably, the aromatic diol is selected from resorcinol two (2- ethoxys) ether, catechol
Two (2- ethoxys) ethers, hydroquinones two (2- ethoxys) ether.
As further preferably, the catalyst is selected from antimony oxide, antimony glycol, tetrabutyl titanate and antimony acetate
One kind.
As further preferably, the mass ratio of the catalyst and thio-2 acid is (0.3~1)：100.
As further preferably, the organic solvent is selected from chloroform, tetrahydrofuran and dichloromethane.
As further preferably, the alcohols solvent is selected from methanol, ethanol and propyl alcohol.
A kind of degradable sulfofatty race aromatic polyester as made from above-mentioned preparation method, with following structure list
Member：
Thio-2 acid, aromatic diol and catalyst are placed under 160 DEG C~190 DEG C and nitrogen protection by the present invention
Esterification is carried out, intermediate product is obtained；Stopping is passed through nitrogen, and the intermediate product is placed in into 190 DEG C~230 DEG C and pressure is
50Pa~1000Pa carries out polycondensation reaction, obtains a kind of sulfofatty race aromatic polyester.
This kind polyester beneficial effect is：It is single as one kind required for synthesizing polyester invention introduces thio-2 acid
Body, introduces C-S polar bonds, compared to original C-C nonpolar bonds, chemical bond energy is weakened to a certain extent, is made in the polyester
It is easily broken off, and is conducive to the degraded of polyester.When thio-2 acid kind polyester is degraded, the degraded of the low molecule amount of sulfur-bearing is obtained
Product, can be swallowed by thiophilic bacterial strain in environment etc., decompose, digestion, this kind of bacterium be often distributed in soil, fresh water, salt water,
In hot spring and sulphur ore deposit.So, on the one hand this kind of polyester material has good thermal stability, on the other hand also has excellent
Degradation property, the exploitation and application of this kind of product can effectively solve " white pollution " problem after this kind of polyester discarded.
Brief description of the drawings
Fig. 1 is the nuclear-magnetism of poly- (thio-2 acid-resorcinol two (2- ethoxys) ether) ester made from the embodiment of the present invention 1
Hydrogen spectrogram.
Fig. 2 is the TG of poly- (thio-2 acid-resorcinol two (2- ethoxys) ether) ester made from the embodiment of the present invention 1
Figure.
Fig. 3 is the degraded of poly- (thio-2 acid-resorcinol two (2- ethoxys) ether) ester made from the embodiment of the present invention 1
Curve synoptic diagram.
Embodiment
The present invention is solved existing by providing a kind of degradable sulfofatty race aromatic polyester and preparation method thereof
The defects such as polyester material degradation property difference.
In order to solve drawbacks described above, the main thought of the embodiment of the present invention is：
The preparation method of aliphatic-aromatic polyester of the embodiment of the present invention, methods described includes：
By thio-2 acid, aromatic diol and catalyst, 150 DEG C~190 DEG C and the lower progress ester of nitrogen protection are placed in
Change reaction, obtain intermediate product；
Stopping is passed through nitrogen, and it is anti-that the intermediate product is placed in into progress polycondensation under 190 DEG C~230 DEG C and 50Pa~1000Pa
Should, obtain polyester.
Polyester obtained above is crude product, and the purification step of polyester crude product also can be set.
In order to which the objects, technical solutions and advantages of the present invention are more clearly understood, with reference to embodiments, to the present invention
It is further elaborated.Specific data involved by specific example described herein are only to explain the present invention, not
For limiting the present invention.
Embodiment 1
The preparation method of poly- (thio-2 acid-resorcinol two (2- ethoxys) ether) ester is as follows：
Added in 50ml single-necked flasks 2.673g thio-2 acids and (2- ethoxys) ether of 2.973g resorcinols two and
0.020g antimony oxides, in 101KPa, 170 DEG C, progress esterification 2.5 hours under nitrogen environment.Above-mentioned esterification knot
Shu Hou, stops logical nitrogen, under the conditions of 190 DEG C, is evacuated to 600Pa, polycondensation reaction 1.5 hours then raises temperature to 215 DEG C,
70Pa is evacuated to, polycondensation reaction 2 hours obtains polyester crude product.Polyester is purified afterwards：19mL chlorine is added in polyester crude product
It is imitative, after after the dissolving of most of polyester, clear liquid is taken with syringe, is instilled in methanol, is centrifuged after solution has precipitation to generate, mistake
Filter, alcohol is washed, and is dried, is obtained poly- (thio-2 acid-resorcinol two (2- ethoxys) ether) ester material.
Fig. 1 is poly- (thio-2 acid-resorcinol two (2- ethoxys) ether) ester that the embodiment of the present invention 1 is prepared
Nucleus magnetic hydrogen spectrum figure, poly- (thio-2 acid-resorcinol two (2- ethoxys) ether) ester hydrogen spectrum ownership is shown below：
Fig. 2 is poly- (thio-2 acid-resorcinol two (2- ethoxys) ether) ester that the embodiment of the present invention 1 is prepared
TG schemes, and can be drawn from figure, and the temperature of 50% mass of loss is 401.5 DEG C, therefore, it can show that the embodiment of the present invention 1 is closed
Into polyester material there is preferable heat endurance.
Fig. 3 is the simulation degradation experiment that the polyester material for synthesizing the embodiment of the present invention 1 is positioned in fresh water, is gathered
The degradation curve that the equal relative molecular weight of weight (Mw) of (thio-2 acid-resorcinol two (2- ethoxys) ether) ester is changed over time
Figure.It can be obtained from figure line trend, over time, the molecular weight of polyester material constantly reduces, and in 1 year, macromolecular piece
Section resolves into small molecule segment, and Mw is changed into 1558.0g/mol from original 21207.6g/mol, and commodity PET in contrast divides
Son amount is held essentially constant.
Embodiment 2
The preparation method of poly- (thio-2 acid-resorcinol two (2- ethoxys) ether) ester is as follows：
Added in 50ml single-necked flasks 2.673g thio-2 acids and (2- ethoxys) ether of 2.973g resorcinols two and
0.020g tetrabutyl titanates, at 160 DEG C, esterification 2.5 hours under nitrogen environment.After esterification terminates, stop logical nitrogen,
Under the conditions of 200 DEG C, 600Pa is evacuated to, polycondensation reaction 2 hours then raises temperature to 220 DEG C, is evacuated to 50Pa, polycondensation is anti-
Answer 2 hours, obtain polyester crude product.By polyester purifying crude：18mL chloroforms are added in polyester crude product, most of polyester dissolving is treated
Afterwards, clear liquid is taken with syringe, instilling has precipitation to generate in ethanol, be then centrifuged for, filter, alcohol is washed, dried, and obtains polyester material.
Embodiment 3
The preparation method of poly- (thio-2 acid-hydroquinones two (2- ethoxys) ether) ester is as follows：
Added in 50ml single-necked flasks 3.561g thio-2 acids and (2- ethoxys) ether of 4.363g hydroquinones two and
0.020g tetrabutyl titanates, at 160 DEG C, esterification 2.5 hours under nitrogen environment.After esterification terminates, stop logical nitrogen,
Under the conditions of 190 DEG C, 600Pa is evacuated to, polycondensation reaction 2 hours then raises temperature to 225 DEG C, and be evacuated to 70Pa, polycondensation
Reaction 1.5 hours, obtains polyester crude product.Polyester purifying crude：24mL tetrahydrofurans are added in polyester crude product, treat most of poly-
After ester dissolving, clear liquid is taken with syringe, instilling has precipitation to generate in methanol, be then centrifuged for, filter, alcohol is washed, dried, obtaining polyester material
Material.
Embodiment 4
Poly- (thio-2 acid-catechol two (2- ethoxys) ether) ester preparation method is as follows：
Added in 50ml single-necked flasks 2.673g thio-2 acids and (2- ethoxys) ether of 3.263g catechols two and
0.010g antimony glycols, at 150 DEG C, esterification 2.5 hours under nitrogen environment.After esterification terminates, stop logical nitrogen,
Under the conditions of 200 DEG C, 600Pa is evacuated to, polycondensation reaction 2 hours then raises temperature to 230 DEG C, and is evacuated to 80Pa, and polycondensation is anti-
Answer 2 hours, obtain polyester crude product.By polyester purifying crude：18mL tetrahydrofurans are added in polyester crude product, most of polyester is treated
After dissolving, clear liquid is taken with syringe, instilled in methanol, have precipitation to generate, the step such as wash, dry through centrifugation, filtering, alcohol, being gathered
Ester material.
Embodiment 5
The preparation method of poly- (thio-2 acid-resorcinol two (2- ethoxys) ether) ester is as follows：
Added in 50ml single-necked flasks 2.673g thio-2 acids and (2- ethoxys) ether of 2.973g resorcinols two and
0.0267g antimony acetates, esterification are carried out at 190 DEG C, under nitrogen environment 2.5 hours.After above-mentioned esterification terminates, stop logical
Nitrogen, under the conditions of 190 DEG C, is evacuated to 1000Pa, polycondensation reaction 1 hour then raises temperature to 205 DEG C, is evacuated to 60Pa,
Polycondensation reaction 1 hour, obtains polyester crude product.Polyester is purified afterwards：19mL dichloromethane is added in polyester crude product, major part is treated
After polyester dissolving, clear liquid is taken with syringe, instilled in propyl alcohol, have precipitation to generate, the step such as wash, dry through centrifugation, filtering, alcohol, obtaining
To poly- (thio-2 acid-resorcinol two (2- ethoxys) ether) ester material.
The hot property data of degradable sulfofatty race aromatic polyester prepared by 1-5 of the embodiment of the present invention are by thermogravimetric point
Analyse (STA 449F3) detection；By nuclear magnetic resonance chemical analyser, (Bruker (600MHz) characterizes the chemical constitution of polyester；By GPC
(Waters 2695) determines the molecular weight and its distribution PDI of polyester.Test data is shown in Table 1.
The polyester physical data of table 1.
M in table 1WFor the weight average molecular weight of polyester, MnFor the number-average molecular weight of polyester, PDI is the molecular weight distribution of polyester,
T50%For the temperature required for heat resolve half quality, MW1And MW2Respectively degrade before weight average molecular weight and degraded 1 year after
Weight average molecular weight, Mn1And Mn2Respectively degrade before number-average molecular weight and degraded 1 year after number-average molecular weight.
Data comparison can be obtained from table 1, the degradable sulfofatty race aromatic polyester that the present invention is synthesized, in 1 year
Small-molecular-weight fragment is become by HMW fragment, and the PET of commercialization molecular weight is then held essentially constant, therefore contrast knot
Fruit shows：This kind of sulfofatty race aromatic polyester polyester has good degradation property, while also having well hot
Can, can effectively it alleviate " white pollution " that waste plastic is caused as environment-friendly polyester material.
Technical scheme in above-mentioned the embodiment of the present application, at least has the following technical effect that or advantage：
Thio-2 acid is introduced in preparation method of the embodiment of the present invention as a kind of monomer of synthesizing polyester, in the polyester
C-S polar bonds are introduced, compared to original C-C nonpolar bonds, chemical bond energy is weakened to a certain extent, it is easily broken off,
Be conducive to the degraded of polyester.When thio-2 acid kind polyester is degraded, the catabolite of the low molecule amount of sulfur-bearing is obtained, can be by
The phagocytosis such as thiophilic bacterial strain in environment, decomposition, digestion, this kind of bacterium are often distributed in soil, fresh water, salt water, hot spring and sulphur ore deposit.
So, on the one hand this kind of polyester material has good performance, on the other hand again with excellent degradation property, this kind of production
The exploitation of product can effectively solve " white pollution " problem after this kind of polyester discarded with application.
, but those skilled in the art once know basic creation although preferred embodiments of the present invention have been described
Property concept, then can make other change and modification to these embodiments.So, appended claims are intended to be construed to include excellent
Select embodiment and fall into having altered and changing for the scope of the invention.Obviously, those skilled in the art can be to the present invention
Carry out various changes and modification without departing from the spirit and scope of the present invention.So, if these modifications and variations of the present invention
Belong within the scope of the claims in the present invention and its equivalent technologies, then the present invention is also intended to exist comprising these changes and modification
It is interior.
Claims (10)
1. a kind of preparation method of degradable sulfofatty race aromatic polyester, it is characterised in that：Methods described includes：
By thio-2 acid, aromatic diol and catalyst, it is placed in 150 DEG C~190 DEG C and the lower progress of nitrogen protection is esterified instead
Should, obtain intermediate product；
Stopping is passed through nitrogen, the intermediate product is placed in 190 DEG C~230 DEG C and vacuumized polycondensation reaction is carried out under state, obtains
To the sulfofatty race aromatic polyester crude product.
2. a kind of preparation method of degradable sulfofatty race aromatic polyester according to claim 1, it is characterised in that：
Also include the purification of the polyester crude product, the purification includes：Organic solvent is added in the polyester, the polyester is most of
Dissolving, obtains clear liquid, and the clear liquid is instilled in alcohols solvent, generates white depositions, is centrifugally separating to obtain white solid, will
The solid carries out alcohol and washes and dry, and obtains sulfofatty race aromatic polyester.
3. the preparation method of degradable sulfofatty race aromatic polyester according to claim 1, it is characterised in that：Institute
The absolute pressure for stating the esterification stage is 101Kpa, and the time in the esterification stage is 2~3h.
4. the preparation method of degradable sulfofatty race aromatic polyester according to claim 1, it is characterised in that：Institute
State polycondensation reaction and vacuumize the control of state finger pressure in 50Pa~1000Pa, the time of the polycondensation reaction is 2~4h.
5. the preparation method of degradable sulfofatty race aromatic polyester according to claim 4, it is characterised in that：Institute
Stating polycondensation reaction includes：The intermediate product is evacuated to 500Pa~1000Pa, under the conditions of 190 DEG C~200 DEG C, reaction 1
~2 hours；200 DEG C~230 DEG C are then raised temperature to, 50Pa~500Pa is evacuated to, reacted 1~2 hour.
6. the preparation method of degradable sulfofatty race aromatic polyester according to claim 1, it is characterised in that：Institute
State aromatic diol and be selected from resorcinol two (2- ethoxys) ether, (2- ethoxys) ether of catechol two and hydroquinones two
(2- ethoxys) ether.
7. the preparation method of degradable sulfofatty race aromatic polyester according to claim 1, it is characterised in that：Institute
State one kind that catalyst is selected from antimony oxide, antimony glycol, tetrabutyl titanate and antimony acetate.
8. the preparation method of degradable sulfofatty race aromatic polyester according to claim 1, it is characterised in that：Institute
The mass ratio for stating catalyst and thio-2 acid is (0.3~1)：100.
9. the preparation method of degradable sulfofatty race aromatic polyester according to claim 1, it is characterised in that：Institute
State organic solvent and be selected from chloroform, tetrahydrofuran and dichloromethane；The alcohols solvent is selected from methanol, ethanol or propyl alcohol.
10. the sulfofatty race aromatic polyester made from preparation method as described in claim any one of 1-9, with following structure
Unit：
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710408458.4A CN107226902B (en) | 2017-06-02 | 2017-06-02 | A kind of degradable sulfofatty race aromatic polyester and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710408458.4A CN107226902B (en) | 2017-06-02 | 2017-06-02 | A kind of degradable sulfofatty race aromatic polyester and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107226902A true CN107226902A (en) | 2017-10-03 |
| CN107226902B CN107226902B (en) | 2019-04-05 |
Family
ID=59934044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710408458.4A Active CN107226902B (en) | 2017-06-02 | 2017-06-02 | A kind of degradable sulfofatty race aromatic polyester and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107226902B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129646A (en) * | 2018-01-26 | 2018-06-08 | 武汉科技大学 | A kind of polyester, the Preparation method and use of the high molecular weight of imido- |
| CN116333276A (en) * | 2022-12-19 | 2023-06-27 | 江苏达美瑞新材料有限公司 | Polyester resin containing alkyl sulfide main chain, powder coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250357A (en) * | 2011-06-09 | 2011-11-23 | 苏州科技学院 | polyphenyl thiophosphonic gylcol ester compound and preparation method thereof |
| CN106700052A (en) * | 2015-08-10 | 2017-05-24 | 姹ゅ浆 | Modified polyester polyol |
-
2017
- 2017-06-02 CN CN201710408458.4A patent/CN107226902B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250357A (en) * | 2011-06-09 | 2011-11-23 | 苏州科技学院 | polyphenyl thiophosphonic gylcol ester compound and preparation method thereof |
| CN106700052A (en) * | 2015-08-10 | 2017-05-24 | 姹ゅ浆 | Modified polyester polyol |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129646A (en) * | 2018-01-26 | 2018-06-08 | 武汉科技大学 | A kind of polyester, the Preparation method and use of the high molecular weight of imido- |
| CN108129646B (en) * | 2018-01-26 | 2020-12-29 | 武汉科技大学 | Imino-containing high molecular weight polyester, preparation method and application |
| CN116333276A (en) * | 2022-12-19 | 2023-06-27 | 江苏达美瑞新材料有限公司 | Polyester resin containing alkyl sulfide main chain, powder coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107226902B (en) | 2019-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112300372B (en) | Preparation and application of sulfur-containing copolyester partially derived from biomass | |
| CN111978531B (en) | Cellulose grafted full-biodegradable high polymer material and preparation method thereof | |
| CN108752506B (en) | Sulfydryl biomass-based monomer internal plasticization PVC material and preparation method thereof | |
| CN107226902A (en) | A kind of degradable sulfofatty race aromatic polyester and preparation method thereof | |
| CN112142963B (en) | Biodegradable high molecular weight polyester synthesis method and application | |
| CN110408180A (en) | Lignin-starch combined master batch compounded biodegradable polyester material and preparation method thereof | |
| CN113121805B (en) | Preparation and application of sulfur-containing copolyester based on 2, 5-thiophene dicarboxylic acid | |
| JP2014528502A (en) | Rapidly degradable polyester polymer and process for its production and use thereof | |
| CN115418085A (en) | Biodegradable PBAT/PLA blending film | |
| KR101396110B1 (en) | Aliphatic polycarbonate and its aromatic polyester copolymers having long chain branches | |
| CN108219121A (en) | A kind of biology base high barrier polyester material and its synthetic method | |
| CN106146817B (en) | Hydroxy alkanoic acid zinc polyester catalyst, the application of preparation method and the catalyst | |
| CN102020773B (en) | Biodegradable copolymer and preparation method thereof | |
| CN106751568A (en) | A kind of antibacterial PBAT/PLA composite membranes and preparation method thereof | |
| KR20140037628A (en) | Modified polylactide resin with cadanol and preparation method thererof | |
| CN113801423B (en) | Degradable lignin grafted polylauryl methacrylate-low density polyethylene composite material and preparation method thereof | |
| CN114409886A (en) | Purification method of polyhydroxy fatty acid ester | |
| CN114395139A (en) | Modified lignin suitable for fully-degradable membrane bags and preparation method thereof | |
| CN113372543A (en) | Low-crystallinity PBS (Poly Butylene succinate) and preparation method thereof | |
| CN112321999A (en) | Preparation method of hyperbranched polybutylene adipate terephthalate material | |
| CN115558264B (en) | Non-reactive compatibilized PLA/PBAT composite material and preparation method thereof | |
| Gu et al. | Tunable Boc modification of lignin and its impact on microbial degradation rate | |
| KR20190062042A (en) | Polylactic acid copolymer having excellent transparency and method for preparing the same | |
| Fang et al. | Synthesis, characterization and degradation of well-defined crosslinkable aliphatic polyesters end-capped by biomesogenic units | |
| CN102250451A (en) | Modified polylactic acid, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20171003 Assignee: Wuhan University of science and Technology Business Incubator Co.,Ltd. Assignor: WUHAN University OF SCIENCE AND TECHNOLOGY Contract record no.: X2020420000004 Denomination of invention: A biodegradable thioaliphatic aromatic polyester and its preparation method Granted publication date: 20190405 License type: Common License Record date: 20201021 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211231 Address after: 213000 Building 1, gounan industrial concentration zone, HUTANG Town, Wujin District, Changzhou City, Jiangsu Province Patentee after: Changzhou Dingen biodegradable material Co.,Ltd. Address before: 430030 No. 1063, building 13, urban industrial zone, Hanzheng Street, No. 21 Jiefang Avenue, Qiaokou District, Wuhan City, Hubei Province Patentee before: Wuhan Tuozhijia Information Technology Co.,Ltd. Effective date of registration: 20211231 Address after: 430030 No. 1063, building 13, urban industrial zone, Hanzheng Street, No. 21 Jiefang Avenue, Qiaokou District, Wuhan City, Hubei Province Patentee after: Wuhan Tuozhijia Information Technology Co.,Ltd. Address before: 430080 947 Peace Avenue, Qingshan District, Wuhan, Hubei Patentee before: WUHAN University OF SCIENCE AND TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Wuhan University of science and Technology Business Incubator Co.,Ltd. Assignor: WUHAN University OF SCIENCE AND TECHNOLOGY Contract record no.: X2020420000004 Date of cancellation: 20230505 |
|
| EC01 | Cancellation of recordation of patent licensing contract |