CN114316287B - Preparation method of lignin-containing polyester polyol - Google Patents
Preparation method of lignin-containing polyester polyol Download PDFInfo
- Publication number
- CN114316287B CN114316287B CN202111550793.0A CN202111550793A CN114316287B CN 114316287 B CN114316287 B CN 114316287B CN 202111550793 A CN202111550793 A CN 202111550793A CN 114316287 B CN114316287 B CN 114316287B
- Authority
- CN
- China
- Prior art keywords
- lignin
- reaction
- polyester polyol
- containing polyester
- visible light
- 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.)
- Active
Links
Images
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a preparation method of lignin-containing polyester polyol, which comprises the steps of taking cyclic ester and lignin as raw materials, and reacting under the protection of inert gas under the condition of an organic catalyst and visible light. Compared with the prior art, the invention adopts the visible light mediated polymerization reaction to regulate and control the polymerization process, and has simple operation and no pollution. Meanwhile, the invention selects a one-pot method to prepare the product, does not need to activate or acylate lignin, simplifies the reaction and saves the operation time; the solubility of lignin is greatly different before and after the reaction, so that the separation of products is facilitated.
Description
Technical Field
The invention belongs to the field of high molecular compounds, and particularly relates to a preparation method of lignin-containing polyester polyol.
Background
As a natural biopolymer with reserves inferior to cellulose, lignin is formed by randomly combining three monomers of p-hydroxyphenyl propane, guaiacyl propane and syringyl propane. The method has the advantages of low price, abundant reserves, high thermal stability, good biodegradability, strong oxidation resistance and the like. In the lignin produced in the current industry, only less than 2% of the lignin is reasonably utilized, and the rest lignin is directly combusted or is discharged randomly. Not only wastes resources, but also brings great pressure to the environment. The lignin is effectively and reasonably utilized, which is beneficial to reducing the consumption of fossil energy and environmental pollution. The current reasons for limiting lignin use are mainly the complex and variable lignin structure, high polydispersity, brittle material and immiscibility with other polymer matrices.
Polycaprolactone is a popular bio-plastic, is in a rubbery state at normal temperature, and has good thermal stability. Meanwhile, the polycaprolactone regular molecular chain brings good flexibility and processability to the polycaprolactone regular molecular chain. In addition, caprolactone is also widely used in the synthesis of polyester polyols and in the subsequent preparation of polyurethanes. The thermoplastic polyurethane synthesized by taking polycaprolactone as a soft segment not only has excellent water resistance similar to polyether polyurethane, but also has good oil resistance. Polycaprolactone differs from a structurally similar polyadipate in that it has better hydrolytic stability and hydrophobicity when used as a soft segment in a polyurethane system.
CN102070891a discloses a lignin-filled polyester composite material and a preparation method thereof. Mixing 60-95% of polyester and 5-40% of lignin uniformly; and (3) melting, extruding and granulating the mixed material by a double-screw machine to obtain the lignin-filled polyester composite material. CN102924893a discloses an environment-friendly lignin/polycaprolactone degradable film and a preparation method thereof, wherein lignin, polycaprolactone, a plasticizer, a solubilizer and other materials are mixed and stirred uniformly; and adding the obtained blend into a double-screw extruder, extruding and blow molding to obtain the lignin/polycaprolactone environment-friendly degradable film. CN106700460a discloses a preparation method of lignin modified PCL biodegradable plastic. Adding polycaprolactone, lignin, a chain extender, an antioxidant, a plasticizer, a lubricant and a heat stabilizer into a high mixing machine for fully mixing; and then extruding and granulating the obtained mixture through a double screw, and performing injection molding to obtain the lignin modified PCL biodegradable plastic. However, the prior art achieves the aim of adding lignin into materials by physical blending, and the obtained product has low general strength. If the polycaprolactone chain segment is introduced on the lignin skeleton through grafting modification, the morphology or structure of lignin can be controlled, the blending property of lignin and a polymer matrix can be improved, and the physical properties of the material can be effectively enhanced.
CN108117650a discloses a preparation method of a bio-plastic film of polycaprolactone grafted lignin. Firstly, activating lignin under the action of isocyanate and a catalyst; then grafting polycaprolactone, and preparing the grafted product into the bio-plastic film by a tape casting method or a blow molding method. The catalysts involved in the polymerization are tin catalysts or amine catalysts. Although these catalysts have excellent catalytic activity, transition metal catalysts tend to oxidize to black, causing discoloration of the material. Meanwhile, the metal catalyst also has certain toxicity, which is unfavorable for biological utilization.
Disclosure of Invention
The invention aims to: aiming at the problems existing in the prior art, for example, the material prepared by a physical blending method of caprolactone and lignin has lower performance; the invention provides a method for synthesizing lignin-containing polyester polyol by photocatalysis through metal catalysis, which has the problems of toxicity, easiness in residue and the like of a catalyst when grafting caprolactone on lignin.
The technical scheme is as follows: in order to solve the technical problems, the invention discloses a preparation method of lignin-containing polyester polyol, which comprises the following steps:
the preparation method comprises the steps of taking cyclic ester and lignin as raw materials, and reacting under the protection of inert gas under the condition of an organic catalyst and visible light.
Preferably, the preparation method of the lignin-containing polyester polyol comprises the following steps:
(1) Reacting the cyclic ester, lignin and an organic catalyst under the protection of inert gas under the condition of visible light;
(2) And (3) after the reaction liquid obtained in the step (1) is cooled, turning off the visible light lamp source. Taking out the reaction solution, centrifuging and collecting supernatant; washing the precipitate with dichloromethane for three times, centrifuging, and collecting supernatant; combining the obtained supernatants, and concentrating under reduced pressure; adding cold methanol into the concentrated solution for precipitation, filtering and separating to obtain white solid, and transferring the white solid into a vacuum drying oven for drying to obtain the polymer.
Preferably, in the step (1), the cyclic ester, lignin and organic catalyst are moisture-free materials obtained by drying; more preferably, the cyclic ester is treated with calcium hydride overnight to remove water and purified by distillation under reduced pressure; the lignin is placed in a vacuum drying oven for overnight dehydration before reaction.
Preferably, the cyclic ester is selected from six-or seven-membered cyclic esters, the polymers of which are biodegradable.
Preferably, in step (1), the cyclic ester is any one or a combination of epsilon-caprolactone, delta-valerolactone, lactide and trimethylene carbonate, more preferably epsilon-caprolactone.
Preferably, in step (1), the lignin includes, but is not limited to, any one or a combination of alkali lignin, organosolv lignin and kraft lignin, more preferably alkali lignin.
Preferably, in the step (1), the organic catalyst is thiocyanate photoacid, and its structural formula is as follows:
preferably, in the step (1), the mass ratio of the cyclic ester, lignin and organic catalyst is 60-98: 1 to 40 (preferably 2 to 10): 1 to 10; more preferably, the mass ratio of the three is 90:10:4.
preferably, in the step (1), the wavelength of the visible light is 420-630 nm, the power is 4-20W, more preferably, the wavelength of the visible light is 460nm, and the power is 8W.
Preferably, in the step (1), an organic solvent can be added in the reaction process, so that materials are mixed more uniformly, the molecular weight distribution of a product is lower, and solution polymerization is performed; if no organic solvent is added, the polymerization is bulk polymerization, grafting is more facilitated, and the molecular weight of the product is higher; the solvent is not particularly required, and the monomer concentration may be 0.8 to 1.4mol/L.
Wherein the organic solvent is required to be dehydrated through a solvent redistilling device; wherein the organic solvent comprises one or more of N, N-dimethylformamide, tetrahydrofuran, dichloromethane and toluene; preferably, the organic solvent is N, N-dimethylformamide.
Preferably, the temperature of the reaction is 25-100 ℃ and the time is 1-48 hours.
Lignin prepared by the above method was dissolved in Tetrahydrofuran (THF), while unmodified lignin was insoluble in THF, indicating that the solubility properties of lignin were significantly altered (fig. 1).
The invention adopts the following ideas: the cyclic ester monomer is grafted onto the lignin skeleton in a grafting-to-backbone method (graft from) to synthesize the star polymer taking lignin macromolecules as cores, so that the solubility of lignin is improved and the blending property of lignin and a polymer matrix is enhanced after grafting. The molecular weight of the polymer can be controlled by changing the molar ratio of the initiator (i.e., lignin macromolecules) to the monomer, and the ring-opening polymerization of caprolactone is initiated by the hydroxyl groups on lignin. In addition, the adoption of the metal-free catalyst not only maintains high catalytic activity, but also shortens the reaction time, and is more environment-friendly.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
1. the invention adopts the organic catalyst, has simple preparation, no toxicity of the metal catalyst and is environment-friendly.
2. The progress of the polymerization reaction is conveniently controlled by adjusting the visible light.
3. The invention selects a one-pot method to prepare the product, does not need to activate or acylate lignin, simplifies the reaction and saves the operation time; the solubility of lignin is greatly different before and after the reaction, so that the separation of products is facilitated.
4. The invention synthesizes a new lignin grafting product with a star structure, the hydroxyl value and the reactivity of lignin are increased by grafting of polyester, the hydroxyl value of the obtained lignin-containing polyester polyol is 33-57 mg KOH/g, and the minimum acid value is 0.9mg KOH/g.
5. The invention prepares the lignin-containing polyester polyol by grafting polyester on a lignin skeleton, and the obtained product has a novel star-shaped structure and good solubility in common organic solvents. The polyurethane paint is synthesized by subsequent reaction or is added into the composite material as a plasticizer, and has better reactivity and processability than pure lignin, and has good guidance and application value for industrialized application of lignin.
Drawings
FIG. 1 is a graph of lignin solubility versus unmodified lignin to the left and grafted product to the right, solvent THF.
FIG. 2 is an infrared spectrum (FTIR) of the lignin grafted product of example 1.
FIG. 3 is a thermogravimetric analysis (TGA) of the grafted product of example 1.
FIG. 4 is a Differential Scanning Calorimetry (DSC) profile of lignin, caprolactone and grafted products of example 1.
FIG. 5 is a lignin graft product of example 1 1 H NMR spectrum.
FIG. 6 is a GPC chart of the graft products in examples 2, 4, 6, and 7, respectively.
FIG. 7 is a graph of an embodiment of a visible light-mediated polymerization reaction
Detailed Description
The invention will be better understood from the following examples. However, it will be readily appreciated by those skilled in the art that the description of the embodiments is provided for illustration only and should not limit the invention as described in detail in the claims.
In the following examples:
the monomer conversion rate calculation method comprises the following steps: in the nuclear magnetic resonance hydrogen spectrum of the reaction mixture, the integral of the polyester is divided by the integral of the polymer and the monomer.
The number average molecular weight and molecular weight distribution of the grafted product are obtained by gel permeation chromatography, wherein THF is used as an eluent, the flow rate is 0.7mL/min, the column temperature is 25 ℃, the sample injection volume is 0.4mL, and polystyrene is used as a standard sample to calibrate the chromatographic column.
The method for detecting the hydroxyl value comprises the following steps: hydroxyl number according to GB/T12008.3-2009;
the method for detecting the acid value comprises the following steps: acid number was measured according to HG/T2708-1995;
example 1
The first step: mixing caprolactone monomer with calcium hydride and stirring overnight to remove residual moisture; placing lignin in a vacuum drying oven for overnight dewatering; the organic solvent needed by the reaction is dehydrated through a solvent redistilling device.
And a second step of: caprolactone (1.80 g), alkali lignin (0.20 g) and thiocyanate photoacid (0.04 g) were weighed into a reaction tube under nitrogen protection with a magnetic stirrer. The reaction was carried out in visible light (wavelength 460nm, power 5W) for 24h. The visible light source is turned off to stop the reaction. The remaining reaction solution was taken out and added to a cold methanol solution, whereby a polymer was precipitated. And filtering and separating to obtain a white solid, and transferring the white solid into a vacuum drying oven for drying to obtain the polycaprolactone polyol containing lignin. Conversion is also achieved by the reaction solution 1 H NMR calculation of the polymer structure by 1 H NMR was carried out to determine the molecular weight and the dispersity of the polymer by GPC. The infrared, thermogravimetric, DSC and hydrogen spectra of the obtained lignin-containing polycaprolactone polyols are shown in FIG. 1-FIG. 5. Caprolactone conversion was 98%, the number average molecular weight of the product was 5140g/mol, the dispersion coefficient was 1.44, the hydroxyl value was 57mg KOH/g, and the acid value was 0.9mg KOH/g.
Example 2
The first step: mixing caprolactone monomer with calcium hydride and stirring overnight to remove residual moisture; placing lignin in a vacuum drying oven for overnight dewatering; the organic solvent needed by the reaction is dehydrated through a solvent redistilling device.
And a second step of: caprolactone (1.70 g), alkali lignin (0.30 g) and thiocyanate photoacid (0.02 g) were weighed and added to the reaction tube together with a magnetic stirrer under nitrogen protection. In the visible (wave460nm long, 4W power) for 36h. The visible light source is turned off to stop the reaction. The remaining reaction solution was taken out and added to a cold methanol solution, whereby a polymer was precipitated. And filtering and separating to obtain a white solid, and transferring the white solid into a vacuum drying oven for drying to obtain the polycaprolactone polyol containing lignin. Conversion is also achieved by the reaction solution 1 H NMR calculation of the polymer structure by 1 H NMR was carried out to determine the molecular weight and the dispersity of the polymer by GPC. Caprolactone conversion was 98.2%, the number average molecular weight of the product was 4500g/mol, the dispersion coefficient was 1.97, the hydroxyl value was 53mg KOH/g, and the acid value was 1.0mg KOH/g.
Example 3
The first step: mixing caprolactone monomer with calcium hydride and stirring overnight to remove residual moisture; placing lignin in a vacuum drying oven for overnight dewatering; the organic solvent needed by the reaction is dehydrated through a solvent redistilling device.
And a second step of: caprolactone (1.84 g), alkali lignin (0.16 g) and thiocyanate photoacid (0.04 g) were weighed into a reaction tube under nitrogen protection with a magnetic stirrer. The reaction was carried out in visible light (wavelength 460nm, power 4W) for 24h. The visible light source is turned off to stop the reaction. Taking out the reaction solution, centrifuging and collecting supernatant; washing the precipitate with dichloromethane for three times, centrifuging, and collecting supernatant; combining the obtained supernatants, and concentrating under reduced pressure; adding cold methanol into the concentrated solution for precipitation, filtering and separating to obtain white solid, transferring to a vacuum drying oven for drying to obtain polycaprolactone polyol containing lignin. Conversion is also achieved by the reaction solution 1 H NMR calculation of the polymer structure by 1 H NMR was carried out to determine the molecular weight and the dispersity of the polymer by GPC. Caprolactone conversion was 94.6%, the number average molecular weight of the product was 5590g/mol, the polydispersity was 2.04, the hydroxyl number was 47mg KOH/g, and the acid number was 3.2mg KOH/g.
Example 4:
the first step: mixing valerolactone monomer with calcium hydride, and stirring overnight to remove residual moisture; placing lignin in a vacuum drying oven for overnight dewatering; the organic solvent needed by the reaction is dehydrated through a solvent redistilling device.
And a second step of: valerolactone (1.6 g) was weighed,alkali lignin (0.4 g) and thiocyanate photoacid (0.04 g) were added to the reaction tube under nitrogen with a magnetic stirrer. The reaction was carried out in visible light (wavelength 460nm, power 6W) for 12h. The visible light source is turned off to stop the reaction. Taking out the reaction solution, centrifuging and collecting supernatant; washing the precipitate with dichloromethane for three times, centrifuging, and collecting supernatant; combining the obtained supernatants, and concentrating under reduced pressure; adding cold methanol into the concentrated solution for precipitation, filtering and separating to obtain white solid, transferring to a vacuum drying oven for drying to obtain the lignin-containing polypentanolide polyol. Conversion is also achieved by the reaction solution 1 H NMR calculation of the polymer structure by 1 H NMR was carried out to determine the molecular weight and the dispersity of the polymer by GPC. Valerolactone conversion was 97.4%, the number average molecular weight of the product was 3730g/mol, the polydispersity was 1.66, the hydroxyl number was 42mg KOH/g, and the acid number was 2.6mg KOH/g.
Example 5
The first step: mixing valerolactone monomer with calcium hydride, and stirring overnight to remove residual moisture; placing lignin in a vacuum drying oven for overnight dewatering; the organic solvent needed by the reaction is dehydrated through a solvent redistilling device.
And a second step of: valerolactone (1.96 g), alkali lignin (0.04 g) and thiocyanic acid (0.06 g) were weighed and added to a reaction tube together with a magnetic stirrer under nitrogen protection. The reaction was carried out in visible light (wavelength 460nm, power 6W) for 24h. The visible light source is turned off to stop the reaction. Taking out the reaction solution, centrifuging and collecting supernatant; washing the precipitate with dichloromethane for three times, centrifuging, and collecting supernatant; combining the obtained supernatants, and concentrating under reduced pressure; adding cold methanol into the concentrated solution for precipitation, filtering and separating to obtain white solid, transferring to a vacuum drying oven for drying to obtain the lignin-containing polypentanolide polyol. Conversion is also achieved by the reaction solution 1 H NMR calculation of the polymer structure by 1 H NMR was carried out to determine the molecular weight and the dispersity of the polymer by GPC. Valerolactone conversion was 91.2%, the number average molecular weight of the product was 8920g/mol, the polydispersity was 1.68, the hydroxyl number was 48mg KOH/g, and the acid number was 1.7mg KOH/g.
Example 6
The first step: trimethylene carbonate is used directly after purchase; placing lignin in a vacuum drying oven for overnight dewatering; the organic solvent needed by the reaction is dehydrated through a solvent redistilling device.
And a second step of: trimethylene carbonate (1.40 g), organic solvents lignin (0.60 g), thiocyanate photoacid (0.04 g) and N, N-dimethylformamide (10 mL) were weighed and added to the reaction flask with a magnetic stirrer under nitrogen. The reaction was carried out in visible light (wavelength 460nm, power 6W) for 24h. The visible light source is turned off to stop the reaction. Taking out the reaction solution, centrifuging and collecting supernatant; washing the precipitate with dichloromethane for three times, centrifuging, and collecting supernatant; combining the obtained supernatants, and concentrating under reduced pressure; adding cold methanol into the concentrated solution for precipitation, filtering and separating to obtain white solid, transferring the white solid into a vacuum drying oven for drying, and obtaining the lignin-containing polycarbonate polyol. Trimethylene carbonate conversion was 84.6%, product number average molecular weight was 3135g/mol, polydispersity was 1.40, hydroxyl number 33mg KOH/g, acid number 1.5mg KOH/g.
Example 7
The first step: lactide is directly used after purchase; placing lignin in a vacuum drying oven for overnight dewatering; the organic solvent needed by the reaction is dehydrated through a solvent redistilling device.
And a second step of: lactide (1.20 g), kraft lignin (0.8 g) and thiocyanic acid (0.04 g) and tetrahydrofuran (10 mL) were weighed and added to a reaction flask with a magnetic stirrer under nitrogen protection. The reaction was carried out in visible light (wavelength 460nm, power 6W) for 48h. The visible light source is turned off to stop the reaction. Taking out the reaction solution, centrifuging and collecting supernatant; washing the precipitate with dichloromethane for three times, centrifuging, and collecting supernatant; combining the obtained supernatants, and concentrating under reduced pressure; adding cold methanol into the concentrated solution for precipitation, filtering and separating to obtain white solid, transferring the white solid into a vacuum drying oven for drying to obtain lignin-containing polylactide polyol. The lactide conversion was 72.5%, the number average molecular weight of the product was 2890g/mol, the polydispersity was 1.43, the hydroxyl number was 34mg KOH/g, and the acid number was 1.9mg KOH/g.
Comparative example 1
The preparation and operating conditions were the same as in example 1, except that stannous octoate (0.04 g) was used as catalyst. Caprolactone conversion was 97.2%, the number average molecular weight of the product was 3520g/mol, the PDI of the product was 2.542, the hydroxyl number was 33mg KOH/g, and the acid number was 1.1mg KOH/g. In contrast, example 1 has a higher hydroxyl number and molecular weight, a lower acid number and molecular weight distribution. Therefore, the organic catalyst has better catalytic efficiency than the metal catalyst and is more environment-friendly.
Example of visible light controlled polymerization
The first step: mixing caprolactone monomer with calcium hydride and stirring overnight to remove residual moisture; placing lignin in a vacuum drying oven for overnight dewatering; the organic solvent needed by the reaction is dehydrated through a solvent redistilling device.
And a second step of: caprolactone (1.80 g), alkali lignin (0.20 g) and thiocyanate photoacid (0.04 g) were weighed into a reaction tube under nitrogen protection with a magnetic stirrer. And (3) reacting for 4 hours in visible light (wavelength 460nm, power 5W), turning off a visible light lamp source, and taking out part of reaction liquid to measure the monomer conversion rate. The reaction was carried out in the dark for 4 hours, and a part of the reaction solution was taken out to measure the monomer conversion. According to the mode, the on-off experiment of the lamp source is carried out every 4 hours. As can be seen from FIG. 7, the polymerization reaction was performed only under visible light conditions, and the reaction was stopped under dark conditions. Therefore, the polymerization reaction can be controlled and carried out through an on-off experiment, and the operation convenience is great.
The invention provides a lignin-containing polyester polyol, a method for preparing the lignin-containing polyester polyol and a method for preparing the lignin-containing polyester polyol, and the method for realizing the technical scheme are more than one, and the above description is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made by one of ordinary skill in the art without departing from the principle of the invention, and the improvements and modifications are also considered as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (6)
1. A preparation method of lignin-containing polyester polyol is characterized in that cyclic ester and lignin are used as raw materials, and the lignin-containing polyester polyol is obtained through reaction under the protection of inert gas under the condition of an organic catalyst and visible light; the cyclic ester is lactide and/or trimethylene carbonate; the organic catalyst is thiocyanate base photoacid, and the structural formula is as follows:
the wavelength of the visible light is 420-630 nm, and the power is 4-20W.
2. The method for producing lignin-containing polyester polyol according to claim 1, wherein the lignin is selected from any one or a combination of several of alkali lignin, organic solvent lignin and kraft lignin.
3. The method for preparing lignin-containing polyester polyol according to claim 1, wherein the mass ratio of the cyclic ester, lignin and organic catalyst is 60-98: 1-40: 1-10.
4. The method for producing lignin-containing polyester polyol according to claim 1 wherein the reaction is performed by adding an organic solvent during the reaction.
5. The method for producing lignin-containing polyester polyol according to claim 4 wherein the organic solvent comprises one or more of N, N-dimethylformamide, toluene, tetrahydrofuran, and methylene chloride.
6. The method for preparing lignin-containing polyester polyol according to claim 1 wherein the reaction temperature is 25 to 100 ℃ for 1 to 48 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111550793.0A CN114316287B (en) | 2021-12-17 | 2021-12-17 | Preparation method of lignin-containing polyester polyol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111550793.0A CN114316287B (en) | 2021-12-17 | 2021-12-17 | Preparation method of lignin-containing polyester polyol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114316287A CN114316287A (en) | 2022-04-12 |
| CN114316287B true CN114316287B (en) | 2023-06-30 |
Family
ID=81053614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111550793.0A Active CN114316287B (en) | 2021-12-17 | 2021-12-17 | Preparation method of lignin-containing polyester polyol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114316287B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117986585B (en) * | 2024-04-07 | 2024-06-04 | 山东理工大学 | Method for preparing polysiloxane emulsion by photoinduction ring-opening polymerization |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180002125A (en) * | 2016-06-28 | 2018-01-08 | 경희대학교 산학협력단 | Production of biopolyol derived from lignin residue through solvothermal liquefaction using butanediol and synthesis of biopolyurethane |
| WO2018210106A1 (en) * | 2017-05-19 | 2018-11-22 | 南京工业大学 | Method for preparing polylactone by ring opening |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117650B (en) * | 2016-11-29 | 2020-07-07 | 中国石油化工股份有限公司 | Biological plastic film of polycaprolactone grafted lignin and preparation method thereof |
| US11117117B2 (en) * | 2017-07-13 | 2021-09-14 | Board Of Trustees Of The University Of Arkansas | Doped carbonaceous materials for photocatalytic removal of pollutants under visible light, making methods and applications of same |
| CN112280263B (en) * | 2020-10-26 | 2022-11-25 | 怀化学院 | Lignin-based biodegradable polymer composite film and preparation method thereof |
-
2021
- 2021-12-17 CN CN202111550793.0A patent/CN114316287B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180002125A (en) * | 2016-06-28 | 2018-01-08 | 경희대학교 산학협력단 | Production of biopolyol derived from lignin residue through solvothermal liquefaction using butanediol and synthesis of biopolyurethane |
| WO2018210106A1 (en) * | 2017-05-19 | 2018-11-22 | 南京工业大学 | Method for preparing polylactone by ring opening |
Non-Patent Citations (1)
| Title |
|---|
| 二元醇对合成木质素基聚酯多元醇性能的影响;来雅;邸明伟;孔宪志;;化学与黏合(第03期);第149-152页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114316287A (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108250415B (en) | Poly (gamma-butyrolactone) -b-polylactic acid block copolymer and preparation method thereof | |
| US9365672B2 (en) | Polylactic acid block copolymers and preparation methods thereof | |
| CN103030766B (en) | Carbon dioxide-based poly (carbonic ester-ether) polyurethane and preparation method thereof | |
| CN114316287B (en) | Preparation method of lignin-containing polyester polyol | |
| Wu et al. | Synthesization and characterization of lignin-graft-poly (lauryl methacrylate) via arget atrp | |
| Ryu et al. | Precisely controlled two-step synthesis of cellulose-graft-poly (L-lactide) copolymers: Effects of graft chain length on thermal behavior | |
| JP5223347B2 (en) | Resin composition, method for producing the same, and copolymer | |
| CN1935871B (en) | Biodegradable high-molecular-weight aliphatic/aromatic copolymer preparing method | |
| CN115322350B (en) | Degradable bio-based polyester and preparation method and application thereof | |
| CN114292388B (en) | Preparation method of degradable PET-based copolyester | |
| CN114230750B (en) | Lignin-based polyurethane and preparation method thereof | |
| CN102942687A (en) | Flame-retardant aliphatic-aromatic copolyester and preparation method thereof | |
| CN102020773A (en) | Biodegradable copolymer and preparation method thereof | |
| Schneider | Design of biobased and biodegradable-compostable engineered plastics based on poly (lactide) | |
| CN1243033C (en) | Method for preparing film poly-L-lactic acid copolymer by inner plasticizing | |
| Lei et al. | Synthesis of high molecular weight polylactic acid from aqueous lactic acid co-catalyzed by tin (II) chloride dihydrate and succinic anhydride | |
| CN114349945B (en) | Modified lignin polyol and preparation method thereof | |
| US8633294B2 (en) | Lactic acid-isosorbide copolyesters and process for the preparation thereof | |
| Jiang et al. | Catalyst free synthesis of poly (l‐lactic acid)–poly (propylene glycol) multiblock copolymers and their properties | |
| CN114133508B (en) | High-performance lignin-based polyurethane and preparation method thereof | |
| CN117843938B (en) | Polyolefin-like long carbon chain polyester elastomer, preparation method and application thereof | |
| CN113004499B (en) | Biodegradable polyester elastomer and preparation method and application thereof | |
| CN102863626B (en) | Biomass modified polymer and preparation method and application thereof | |
| Sun et al. | Ultra‐Strong and Tough Bio‐Based Polyester Elastomer with Excellent Photothermal Shape Memory Effect and Degradation Performance | |
| Xu et al. | Biobased polyesters and crosslinked polyester films derived from 10-hydroxy-2-decenoic acid: Synthesis and characterization |
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 |