CN107840948B - Bio-based polymer compound and preparation method thereof - Google Patents
Bio-based polymer compound and preparation method thereof Download PDFInfo
- Publication number
- CN107840948B CN107840948B CN201610831226.5A CN201610831226A CN107840948B CN 107840948 B CN107840948 B CN 107840948B CN 201610831226 A CN201610831226 A CN 201610831226A CN 107840948 B CN107840948 B CN 107840948B
- Authority
- CN
- China
- Prior art keywords
- component
- bio
- polymer compound
- based polymer
- furan
- 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
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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
-
- 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
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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 provides a bio-based polymer compound and a preparation method thereof. The bio-based high molecular compound is bio-based furan polyester containing a furan structure, wherein the components for synthesizing the bio-based high molecular compound comprise: furan dicarboxylic acid or an esterified product thereof as a component (a), furan diformyl chloride as a component (b), aromatic or aliphatic dibasic acid or an esterified product thereof as a component (c), and cyclic diol or aliphatic diol as a component (d). The high molecular compound of the invention not only has high molecular weight, high tensile modulus, high tensile strength, good heat resistance, good oxygen barrier property and carbon dioxide barrier property, but also solves the problem of dark color of the prior furan ring-containing polyester. The bio-based polymer compound can meet the application requirements in the fields of packaging materials, films, fibers, engineering plastics and the like.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a bio-based high polymer compound and a preparation method thereof. The macromolecular compound can be widely applied to the production and manufacture of packaging materials, films, fibers, engineering plastics and the like.
Background
At present, the bio-based polymer materials widely used mainly include polylactic acid (PLA), Polyhydroxyalkanoate (PHA), polyglycolic acid (PGA), polybutylene succinate (PBS), and the like. They all belong to aliphatic polymers, and because of lack of rigid aromatic ring structure in the molecular structure, the mechanical properties (such as strength, modulus, creep resistance and the like) and heat resistance (such as thermal mechanical properties, thermal deformation temperature and the like) of the aliphatic polymers are obviously lower than petroleum-based high polymer materials such as polyethylene terephthalate (PET), Polycarbonate (PC), aromatic nylon (PA), bisphenol A type Epoxy resin (Epoxy) and the like, and the application range of the aliphatic polymers is severely limited.
The molecular structure of the 2, 5-furandicarboxylic acid (2,5-FDCA) contains aromatic rings, so that the heat resistance and the mechanical property of the synthetic bio-based polymer material can be effectively improved, and the oxygen barrier property of the polyester material containing the furan rings can be improved by 5-10 times compared with that of a large amount of PET used for packaging materials, so that the quality guarantee period of agricultural products, fish products and meat products can be effectively prolonged.
However, the polyester materials currently produced using 2, 5-furandicarboxylic acid tend to have some disadvantages, such as darker color, low tensile modulus, low tensile strength, low heat resistance, and the like. For example, the polyester synthesized by furan dicarboxylic acid or its ester at present is often dark in color, yellow, dark yellow or black, thereby seriously affecting the application in the fields of packaging, fiber and the like.
Therefore, there is a need in the art for new bio-based polymer compounds that are colorless or light-colored and have excellent properties such as high tensile modulus.
Disclosure of Invention
The present invention aims to provide a bio-based polymer compound which is colorless or pale in color and has excellent properties such as high tensile modulus.
The first aspect of the present invention provides a bio-based polymer compound, wherein the bio-based polymer compound is a bio-based furan polyester, and the components for synthesizing the bio-based polymer compound include:
component (a): furan dicarboxylic acid, furan dicarboxylate, or a combination thereof;
a component (b): furan diformyl chloride;
optional component (c): an aromatic dibasic acid, an aliphatic dibasic acid, an aromatic dibasic acid ester, an aliphatic dibasic acid ester, or a combination thereof; and
a component (d): a cyclic diol, an aliphatic diol, or a combination thereof,
wherein the content of the component (b) is 0.001mol percent to 35mol percent based on the total molar weight of the components (a), (b), (c) and (d).
In another preferred embodiment, the sum of said components (a), (b), (c) and (d) is about 70 to 100 wt%, preferably 80 to 99.5 wt%, more preferably 90 to 99 wt% of the total amount of said polymeric compound.
In another preferred embodiment, the molar ratio of the component (a) to the component (b) is 0.001 to 1000. Preferably, the molar ratio of component (a) to component (b) is from 0.01 to 100, more preferably from 0.05 to 50, most preferably from 0.1 to 10.
In another preferred embodiment, the component (a) + (b) accounts for 70mol-100 mol% of the total content of the components (a) + (b) + (c).
In another preferred embodiment, the component (c) accounts for 0mol-30 mol% of the total content of the components (a) + (b) + (c).
In another preferred embodiment, the cyclic diol accounts for 15 mol% to 100 mol% of the total diol content.
In another preferred embodiment, the aliphatic diol accounts for 0mol-85 mol% of the total diol content.
In another preferred embodiment, the component (a) is selected from the group consisting of: furan dicarboxylic acid, furan dicarboxylic acid dimethyl ester, or a combination thereof.
In another preferred embodiment, the component (a) is dimethyl furandicarboxylate.
In another preferred embodiment, the component (b) is selected from the group consisting of: 2,5 furandicarboxylic acid dichloride, 2, 4-furandicarboxylic acid dichloride, 3, 4-furandicarboxylic acid dichloride, or a combination thereof.
In another preferred embodiment, said component (c) is selected from the group consisting of: 2, 6-naphthalenedicarboxylic acid, dimethyl 2, 6-naphthalenedicarboxylate, terephthalic acid, dimethyl terephthalate, succinic acid, dimethyl succinate, or combinations thereof.
In another preferred embodiment, the component (c) is dimethyl 2, 6-naphthalenedicarboxylate.
In another preferred embodiment, the cyclic diol is selected from the group consisting of: 1, 4-cyclohexanedimethanol, 2,4, 4-tetramethyl-1, 3-cyclobutanol, or a combination thereof.
In another preferred embodiment, the cyclic diol is 1, 4-cyclohexanedimethanol.
In another preferred embodiment, the aliphatic diol is selected from the group consisting of: ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, or combinations thereof.
In another preferred embodiment, the aliphatic diol is ethylene glycol.
In another preferred embodiment, the components for synthesizing the polymer compound further comprise additives, wherein the additives are selected from the following group: an esterification catalyst, a polycondensation catalyst, a stabilizer, an antioxidant, or a combination thereof.
In another preferred embodiment, the esterification catalyst is selected from the group consisting of: anhydrous zinc acetate, anhydrous cobalt acetate, anhydrous manganese acetate, dibutyl tin oxide, or a combination thereof.
In another preferred embodiment, the polycondensation catalyst is selected from the group consisting of: antimony-based catalyst, titanium-based catalyst, germanium-based catalyst, tin-based catalyst, preferably, the polycondensation catalyst is selected from the group consisting of: antimony trioxide, isobutyl titanate, tetrabutyl titanate, ethylene glycol antimony, antimony acetate, or combinations thereof.
In another preferred embodiment, the stabilizer is selected from the group consisting of: phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium dihydrogen phosphate, or combinations thereof.
In another preferred embodiment, the antioxidant is selected from the group consisting of: the phenolic antioxidant is preferably antioxidant-1010, antioxidant-1076, or a combination thereof.
In another preferred embodiment, the bio-based polymer compound is prepared by a method comprising the following steps:
(i) providing a first mixture comprising components (a), (b), (c), and (d);
(ii) subjecting components (b) and (d) of the first mixture to a nucleophilic substitution reaction to form a first intermediate product;
(iii) subjecting component (a) and component (d), and/or component (c) and component (d) in the first intermediate product to an esterification reaction and/or transesterification reaction in the presence of an esterification catalyst, thereby forming a second intermediate product; and
(iv) and carrying out polycondensation reaction on the second intermediate product in the presence of a polycondensation catalyst to obtain the bio-based polymer compound.
In another preferred embodiment, in step (i), the first mixture further contains an esterification catalyst.
In another preferred example, in the step (iv), the method comprises the steps of: and mixing a polycondensation catalyst, a stabilizer and an antioxidant with the second intermediate, and then carrying out polycondensation reaction.
In another preferred embodiment, in steps (ii), (iii) and/or (iv), the reaction is carried out under an inert atmosphere.
In another preferred embodiment, the inert atmosphere comprises nitrogen, argon, or a combination thereof.
In another preferred embodiment, between steps (ii) and (iii), further comprising: HCl generated in the nucleophilic substitution reaction is removed or neutralized.
In another preferred embodiment, in step (ii), the reaction temperature is from-20 ℃ to 90 ℃; and/or the reaction time is 0.2 to 24 hours.
In another preferred embodiment, in step (iii), the reaction temperature is from 120 ℃ to 240 ℃; and/or the reaction time is 0.2 to 36 hours.
In another preferred embodiment, in step (iv), the reaction temperature is from 180 ℃ to 280 ℃; and/or the reaction time is 0.2 to 48 hours.
In another preferred example, the carbon contained in the furan ring in the component (a) and the component (b) is derived from biomass raw materials.
In another preferred embodiment, the biomass raw material is selected from the group consisting of: cellulose, fructose, glucose, furoic acid, or combinations thereof.
In another preferred embodiment, the high molecular compound has an intrinsic viscosity of 0.7-1.4dL/g and a melting point of 190-280 ℃.
In another preferred embodiment, the color of the macromolecular compound is light color or colorless.
In another preferred embodiment, the polymer compound has one or more characteristics selected from the group consisting of:
(1) the glass transition temperature is 60-95 ℃;
(2) oxygen gas barrier property of 1.0X 10-13-5.0×10-12cm3·cm/cm2·s·cmHg；
(3) The carbon dioxide gas barrier property was 2.0X 10-13-5.0×10-12cm3·cm/cm2·s·cmHg；
(4) The tensile strength is 50-90 MPa;
(5) the tensile modulus is 2.0-3.5 GPa;
(6) the elongation at break is 10-50% or 80-300%.
A second aspect of the present invention provides a method for producing a bio-based polymer compound, the method comprising the steps of:
(i) providing a first mixture comprising components (a), (b), (c), and (d);
(ii) subjecting components (b) and (d) of the first mixture to a nucleophilic substitution reaction to form a first intermediate product;
(iii) subjecting component (a) and component (d), and/or component (c) and component (d) in the first intermediate product to an esterification reaction and/or transesterification reaction in the presence of an esterification catalyst, thereby forming a second intermediate product; and
(iv) subjecting the second intermediate product to a polycondensation reaction in the presence of a polycondensation catalyst, thereby obtaining the bio-based polymer compound according to the first aspect of the present invention.
In another preferred embodiment, in the esterification reaction, the component (a) and the component (d), and/or the component (c) and the component (d) undergo esterification reaction and/or transesterification reaction to remove H2O and/or low boiling alcohols.
In another preferred embodiment, in the nucleophilic substitution reaction, the component (b) reacts with the component (d) and removes HCl.
In a third aspect of the present invention, there is provided an article comprising or consisting of the bio-based polymer compound according to the first aspect of the present invention.
In another preferred embodiment, the article comprises: packaging materials, films, fibers, bottles, and/or engineering plastics.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Drawings
FIG. 1 photographs of dark yellow specimens and film samples of polyethylene 2, 5-furandicarboxylate obtained from comparative example 1.
FIG. 2 is a drawing of the bio-based furan copolyester obtained in example 11H-NMR spectrum.
FIG. 3 is a DSC spectrum of bio-based furan copolyester obtained in example 1.
FIG. 4 is a TGA profile of the bio-based furan copolyester obtained in example 1.
FIG. 5 is a photograph of a sample of a colorless film of the bio-based furan copolyester obtained in example 1.
Detailed Description
The present inventors have conducted extensive and intensive studies and have unexpectedly found a bio-based polymer compound and a method for preparing the same. The bio-based polymer compound of the present invention is prepared using the following components (monomers): furan dicarboxylic acid or an esterified product thereof as a component (a), furan diformyl chloride as a component (b), aromatic or aliphatic dibasic acid or an esterified product thereof as a component (c), and cyclic diol or aliphatic diol as a component (d). The polymer synthesized by nucleophilic substitution reaction, esterification reaction and polycondensation reaction can be used to prepare bio-based high molecular compound with excellent performance (colorless or light color, excellent mechanical property and the like), i.e. bio-based furan polyester. On the basis of this, the present invention has been completed.
Term(s) for
As used herein, "bio-based polymeric compound of the present invention", "bio-based furanpolyester of the present invention", "polyester of the present invention", "furanpolyester of the present invention" are used interchangeably and refer to a polymeric polyester compound containing a furanic structure as described in the first aspect of the present invention.
Bio-based polymer compound
The invention provides a bio-based high molecular compound, which is bio-based furan polyester.
The high molecular compound of the present invention has the main characteristic that in the preparation process, the high activity furan dicarboxylic acid chloride and furan dicarboxylic acid or furan dicarboxylic acid dimethyl ester are adopted to form a blend, and the blend is copolymerized with 1, 4-cyclohexanedimethanol, 2,4,4, -tetramethyl-1, 3-cyclobutanol, ethylene glycol, butanediol and other cyclic diols or aliphatic diols. The inventor unexpectedly finds that when a certain amount of furan diformyl chloride is added, the problem that the existing furan polyester product is dark in color can be solved, the molecular weight can be further improved, and the mechanical property of the polymer can be improved.
The bio-based high molecular compound, namely the bio-based furan polyester, is synthesized by a component (a) furan dicarboxylic acid or an esterified product thereof, a component (b) furan diformyl chloride, a component (c) aromatic or aliphatic dibasic acid or an esterified product thereof, and a component (d) cyclic dihydric alcohol or aliphatic dihydric alcohol through nucleophilic substitution reaction, esterification reaction and polycondensation reaction. The bio-based polymer compound has high molecular weight, modulus and strength, and good heat resistance, oxygen barrier property, carbon dioxide barrier property and other excellent properties.
In the present invention, the component (a) includes (but is not limited to): furan dicarboxylic acid, furan dicarboxylic acid dimethyl ester, or a combination thereof. Preferably, the component (a) is dimethyl furandicarboxylate. The component (b) includes (but is not limited to): 2,5 furandicarboxylic acid dichloride, 2, 4-furandicarboxylic acid dichloride, 3, 4-furandicarboxylic acid dichloride, or a combination thereof. The component (c) includes (but is not limited to): 2, 6-naphthalenedicarboxylic acid, dimethyl 2, 6-naphthalenedicarboxylate, terephthalic acid, dimethyl terephthalate, succinic acid, dimethyl succinate, or combinations thereof. Preferably, the component (c) is dimethyl 2, 6-naphthalenedicarboxylate. The cyclic diols include (but are not limited to): 1, 4-cyclohexanedimethanol, 2,4, 4-tetramethyl-1, 3-cyclobutanol, or a combination thereof. Preferably, the cyclic diol is 1, 4-cyclohexanedimethanol. The aliphatic diols include (but are not limited to): ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, or combinations thereof. Preferably, the aliphatic diol is ethylene glycol.
Synthesis method
The invention also provides a preparation method of the bio-based polymer compound.
Generally, firstly, furan diformyl chloride and dihydric alcohol (such as aliphatic dihydric alcohol) are subjected to nucleophilic substitution reaction at a certain temperature to generate white ester; then, the temperature is further increased to perform esterification reaction and polycondensation reaction, thereby obtaining a colorless or light-colored high molecular weight bio-based compound.
Typically, the present invention utilizes the reaction mechanism of nucleophilic substitution reaction between furandicarboxylic acid dichloride and dihydric alcohol at lower temperature (such as-10-80 ℃) to remove HCl, and utilizes the esterification reaction and/or ester exchange reaction between furandicarboxylic acid or its esterified product and dihydric alcohol at higher temperature (such as 120-200 ℃) to remove H2O and/or low boiling point alcohol, and finally obtaining colorless or light-colored high molecular weight compound through polycondensation reaction at high temperature (such as 200-260 ℃) and vacuum (such as 3-1000 Pa).
In a preferred embodiment, the method for preparing the polymer compound of the present invention comprises the steps of:
(1) providing a mixture of components (a), (b), (c), (d) and an esterification catalyst;
(2) reacting the mixture obtained in the step (1) in a nitrogen environment at a certain temperature for a period of time to obtain a first intermediate product;
(3) pumping out the nitrogen in the step (2), and reacting the first intermediate product in a vacuum environment for a period of time to obtain a second intermediate product;
(4) stopping vacuum, introducing nitrogen, raising the temperature, and continuing to react for a period of time to obtain a third intermediate product;
(5) adding a polycondensation catalyst, a stabilizer and an antioxidant into the third intermediate product, further raising the temperature on the basis of the step (4), and slowly vacuumizing for pre-polycondensation for a period of time to obtain a fourth intermediate product; and
(6) controlling the vacuum degree to be within a certain range, and continuously reacting for a period of time to obtain the bio-based polymer compound.
In the step (2), the reaction temperature is-10-80 ℃, and the reaction time is 0.5-2 h.
In the step (3), the vacuum degree is less than 2000Pa, and the reaction time is 0.5-2 h.
In the step (4), the temperature is 120-240 ℃, and the reaction time is 0.5-8h
In the step (5), the temperature is raised to 200 ℃ and 260 ℃, and the reaction time is 0.5-2 h.
In the step (6), the vacuum degree is controlled below 200Pa, and the reaction time is 0.5-10 h.
Applications of
The bio-based polymer compound has colorless or light-colored appearance, and has the characteristics of high molecular weight, high tensile modulus, high tensile strength, good heat resistance, good oxygen barrier property, good carbon dioxide barrier property and the like, so the bio-based polymer compound is particularly suitable for the fields of packaging materials, films, fibers, engineering plastics and the like.
Preferably, the present invention provides an article comprising or consisting of the bio-based polymer compound of the present invention. Representative articles of manufacture include (but are not limited to): packaging materials, films, fibers, bottles, and/or engineering plastics.
Performance testing
In the present invention and examples, the polymer compound of the present invention can be subjected to the property measurement by the conventional method and the conventional apparatus. For example, with reference to the GB standard or other standards.
The glass transition temperature, tensile strength, tensile modulus and elongation at break were measured by a conventional method.
Hydrogen spectrum of nuclear magnetic resonance1H-NMR was measured on a Bruker 400AVANCE III Spectrometer type instrument at 400MHz, CF3COOD。
In the examples, the intrinsic viscosity of polyesters and copolyesters was determined by measuring the intrinsic viscosity of the polyesters and copolyesters using phenol/tetrachloroethane (1:1m/m) as a solvent at 30. + -. 0.05 ℃ using a Ubbelohde viscometer according to the formulae (1), (2) and (3) [ η ].
ηsp＝(t1-t0)/t0(1)
[η]＝[(1+1.4ηsp)1/2-1]/0.7c (2)
Wherein: t is t0The flow time(s) of the solvent; t is t1The flow time(s) of the solution; c is the concentration of the solution, 5 g/L.
Thermal analysis was performed using differential scanning calorimetry (Mettler Toledo DSC) at a ramp rate of 20 deg.C/min in N2The atmosphere is carried out, and the temperature range is 25-300 ℃. Thermogravimetric analysis (TGA) was performed on a Perkin-Elmer Diamond TG/DTA with a heating rate of 10 ℃/min and a temperature range of 50-800 ℃.
Oxygen and carbon dioxide barrier Properties permeability tests were performed using Labthink VAC-V2, respectively as CO2And O2As an air source, under the conditions of 23 ℃ and 50% RH of temperature and humidity respectively, the sample size phi of 97mm and the transmission area of 38.5cm are selected2。
The main advantages of the invention include:
1. the high activity of the furan diformyl chloride is effectively utilized to perform nucleophilic substitution reaction with alcohol, so that the relative molecular mass of the polymer can be effectively improved.
2. The colorless or light-colored bio-based furan copolyester is obtained, meets the application requirements in the fields of packaging materials, films, fibers, engineering plastics and the like, and can assist in improving the manufacturing level of high-performance engineering plastics.
3. Can promote the bio-based polymer material industry to get rid of the high dependence on petroleum resources.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
Comparative example 1
Adding 0.2mol of 2, 5-furandicarboxylic acid, 0.15mol of ethylene glycol, 0.15mol of 1, 4-cyclohexanedimethanol and 0.0004mol of anhydrous zinc acetate into a 1000mL reaction kettle, vacuumizing, filling nitrogen for replacement for three times, starting stirring, gradually heating to 180 ℃, and reacting for 4 hours. Adding antimony trioxide, triphenyl phosphate and an antioxidant into the system, heating to 240 ℃, slowly vacuumizing for pre-polycondensation for 0.5H, controlling the vacuum degree to be below 200Pa, and reacting for 3H to obtain dark yellow poly (ethylene-2, 5-furandicarboxylate) with the intrinsic viscosity of 0.72dL/g, the glass transition temperature of 82.0 ℃, the melting point of 207.4 ℃ and the crystallization melting enthalpy of delta Hm7.2J/g, the extruded bars and films were dark yellow and the photographs of the samples are shown in FIG. 1. The tensile strength of the sample strip is 58.0MPa, the tensile modulus is 2.2GPa, and the breaking elongation is 88.1 percent.
Example 1
Adding 0.10mol of 2, 5-furandicarboxylic acid dichloride, 0.1mol of 2, 5-furandicarboxylic acid, 0.15mol of ethylene glycol, 0.15mol of 1, 4-cyclohexanedimethanol and 0.0004mol of anhydrous zinc acetate into a 1000mL reaction kettle, vacuumizing, filling nitrogen for three times for replacement, starting stirring, reacting for 2 hours at 25 ℃, vacuumizing to 0.01-0.03MPa, reacting for 1 hour, stopping vacuum, introducing nitrogen, gradually heating to 160 ℃, and continuing to react for 4 hours. Adding antimony trioxide, triphenyl phosphate and an antioxidant into a system, heating to 240 ℃, slowly vacuumizing for pre-polycondensation for 0.5h, and then controlling the vacuum degree to be below 200Pa for reaction for 3h to obtain a bio-based polymer compound: the copolymer of furan with a high degree of polymerization,1H-NMR is shown in FIG. 2, which shows an intrinsic viscosity of 0.98dL/g, a glass transition temperature of 80.6 ℃, a melting point of 225.4 ℃ and a crystal melting enthalpy Δ HmIt was 27.2J/g, as shown in FIG. 3. T isd,5％The thermal decomposition temperature was 365 ℃ as shown in FIG. 4. Oxygen gas barrier property of 3.1X 10-12cm3·cm/cm2s.cmHg, carbon dioxide gas barrier property of 3.5X 10- 12cm3·cm/cm2s.cmHg, tensile strength 68.0MPa, tensile modulus 2.2GPa, elongation at break greatly improved to 180%, and toughness. A photograph of a colorless furan copolyester film obtained by extrusion bar and melt molding method is shown in FIG. 5.
Example 2
Adding 0.08mol of 2, 5-furandicarboxylic acid dichloride, 0.12mol of 2, 5-furandicarboxylic acid, 0.30mol of 1, 4-cyclohexanedimethanol and 0.0008mol of anhydrous zinc acetate into a 1000mL reaction kettle, vacuumizing, filling nitrogen for replacement for three times, starting stirring, reacting for 2 hours at 50 ℃, vacuumizing to 0.01-0.03MPa, reacting for 1 hour, stopping vacuum, introducing nitrogen, gradually heating to 140 ℃, and continuing to react for 4 hours. Adding antimony trioxide, triphenyl phosphate and an antioxidant into a system, heating to 240 ℃, slowly vacuumizing for pre-polycondensation for 0.5h, and then controlling the vacuum degree to be below 200Pa for reaction for 3h to obtain a nearly colorless bio-based polymer compound: furan copolyester with intrinsic viscosity of 1.12dL/g, glass transition temperature of 79.6 ℃, melting point of 260.4 ℃ and crystallization melting enthalpy Delta HmIt was 42.1J/g. T isd,5％The thermal decomposition temperature was 368 ℃. Oxygen gas barrier property of 3.2X 10-12cm3·cm/cm2s.cmHg, carbon dioxide gas barrier property of 3.3X 10-12cm3·cm/cm2s.cmHg, tensile strength 75.1MPa, tensile modulus 2.2GPa, and elongation at break 24%.
Example 3
Adding 0.002mol of 2, 5-furandicarboxylic acid dichloride, 0.198mol of 2, 5-furandicarboxylic acid, 0.12mol of ethylene glycol, 0.18mol of 1, 4-cyclohexanedimethanol and 0.0001mol of anhydrous zinc acetate into a 1000mL reaction kettle, vacuumizing, filling nitrogen for three times for replacement, starting stirring, reacting for 2 hours at 10 ℃, vacuumizing to 0.01-0.03MPa, reacting for 1 hour, stopping vacuum, introducing nitrogen, gradually heating to 180 ℃, and continuing to react for 4 hours. Adding antimony trioxide, triphenyl phosphate and an antioxidant into a system, heating to 260 ℃, slowly vacuumizing for pre-polycondensation for 0.5h, and then controlling the vacuum degree to be below 200Pa for reaction for 3h to obtain a nearly colorless bio-based macromolecular compound: furan copolyester, intrinsic viscosity 0.87dL/g, glass transition temperature 84 ℃. Oxygen gas barrierThe barrier property is 2.7 multiplied by 10-12cm3·cm/cm2s.cmHg, carbon dioxide gas barrier property of 3.6X 10-12cm3·cm/cm2s.cmHg, tensile strength 75.1MPa, tensile modulus 2.2GPa, and elongation at break 24%.
Example 4
Adding 0.06mol of 2, 5-furan diformyl chloride, 0.14mol of 2, 5-furan dicarboxylic acid dimethyl ester, 0.12mol of ethylene glycol, 0.18mol of 1, 4-cyclohexanedimethanol and 0.0002mol of anhydrous zinc acetate into a 1000mL reaction kettle, vacuumizing, filling nitrogen for replacement for three times, starting stirring, reacting for 2 hours at the temperature of minus 5 ℃, vacuumizing to the pressure of 0.01-0.03MPa, reacting for 1 hour, stopping vacuum, introducing nitrogen, gradually heating to 160 ℃, and continuing to react for 4 hours. Adding antimony trioxide, triphenyl phosphate and an antioxidant into a system, heating to 220 ℃, slowly vacuumizing for pre-polycondensation for 0.5h, and then controlling the vacuum degree to be below 200Pa for reaction for 3h to obtain a nearly colorless bio-based polymer compound: furan copolyester, intrinsic viscosity 0.82dL/g, glass transition temperature 82.6 ℃.
Example 5
Adding 0.04mol of 2, 5-furan diformyl chloride, 0.16mol of 2, 5-furan dimethyl diformate, 0.09mol of ethylene glycol, 0.21mol of 1, 4-cyclohexanedimethanol and 0.0004mol of anhydrous zinc acetate into a 1000mL reaction kettle, vacuumizing, filling nitrogen for replacement for three times, starting stirring, reacting for 2 hours at 30 ℃, vacuumizing to 0.01-0.03MPa, reacting for 1 hour, stopping vacuum, introducing nitrogen, gradually heating to 180 ℃, and continuing to react for 4 hours. Adding antimony trioxide, triphenyl phosphate and an antioxidant into a system, heating to 240 ℃, slowly vacuumizing for pre-polycondensation for 0.5h, and then controlling the vacuum degree to be below 200Pa for reaction for 3h to obtain a nearly colorless bio-based polymer compound: furan copolyester with intrinsic viscosity of 1.03dL/g and glass transition temperature of 84.4 ℃.
Example 6
Adding 0.02mol of 2, 5-furan diformyl chloride, 0.18mol of 2, 5-furan dicarboxylic acid dimethyl ester, 0.045mol of ethylene glycol, 0.255mol of 1, 4-cyclohexanedimethanol and 0.0008mol of anhydrous zinc acetate into a 1000mL reaction kettle, vacuumizing, filling nitrogen for replacement for three times, starting stirring, reacting for 2 hours at 12 ℃, vacuumizing to 0.01-0.03MPa, reacting for 1 hour, stopping vacuum, introducing nitrogen, gradually heating to 200 ℃, and continuing to react for 4 hours. Adding antimony trioxide, triphenyl phosphate and an antioxidant into a system, heating to 270 ℃, slowly vacuumizing for pre-polycondensation for 0.5h, and then controlling the vacuum degree to be below 200Pa for reaction for 3h to obtain a nearly colorless bio-based polymer compound: furan copolyester with intrinsic viscosity of 1.12dL/g and glass transition temperature of 85.1 ℃.
Example 7
Adding 0.002mol of 2, 5-furandicarboxylic acid dichloride, 0.198mol of 2, 5-furandicarboxylic acid dimethyl ester, 0.225mol of ethylene glycol, 0.075mol of 1, 4-cyclohexanedimethanol and 0.001mol of anhydrous zinc acetate into a 1000mL reaction kettle, vacuumizing, filling nitrogen for three times for replacement, starting stirring, reacting at 5 ℃ for 2 hours, vacuumizing to 0.01-0.03MPa, reacting for 1 hour, stopping vacuum, introducing nitrogen, gradually heating to 160 ℃, and continuing to react for 4 hours. Adding antimony trioxide, triphenyl phosphate and an antioxidant into a system, heating to 250 ℃, slowly vacuumizing for pre-polycondensation for 0.5h, and then controlling the vacuum degree to be below 200Pa for reaction for 3h to obtain a nearly colorless bio-based polymer compound: furan copolyester, intrinsic viscosity 0.79dL/g, glass transition temperature 86.2 ℃.
Example 8
Adding 0.2mol of 2, 5-furandicarboxylic acid dichloride and 0.3mol of 1, 4-cyclohexanedimethanol into a 1000mL reaction kettle, vacuumizing, filling nitrogen for replacing three times, starting stirring, reacting for 4 hours at 0 ℃, vacuumizing to 0.01-0.03MPa, reacting for 1 hour, stopping vacuumizing, adding antimony trioxide, triphenyl phosphate and an antioxidant into a system, gradually heating to 260 ℃, controlling the vacuum degree to be below 200Pa, and reacting for 3 hours to obtain a nearly colorless bio-based high molecular compound: furan copolyester with intrinsic viscosity of 1.20dL/g, glass transition temperature of 80.1 ℃ and melting point of 262.3 ℃.
Example 9
Adding 0.10mol of 2, 5-furandicarboxylic acid dichloride, 0.1mol of 2, 5-furandicarboxylic acid, 0.15mol of ethylene glycol, 0.15mol of 2,2,4, 4-tetramethyl-1, 3-cyclobutanol and 0.0004mol of anhydrous zinc acetate into a 1000mL reaction kettle, vacuumizing, filling nitrogen for replacement for three times, starting stirring, reacting for 2 hours at 25 ℃, vacuumizing to 0.01-0.03MPa, reacting for 1 hour, stopping vacuum, introducing nitrogen, gradually heating to 160 ℃, and continuing to react for 4 hours. Adding tetrabutyl titanate, triphenyl phosphate and an antioxidant into the system, heating to 240 ℃, slowly vacuumizing for pre-polycondensation for 0.5h, and then controlling the vacuum degree to be below 200Pa for reaction for 3h to obtain a nearly colorless bio-based polymer compound: furan copolyester with intrinsic viscosity of 0.96dL/g, glass transition temperature of 70.6 ℃ and melting point of 216.7 ℃.
Example 10
Adding 0.01mol of 2, 5-furandicarboxylic acid dichloride, 0.19mol of 2, 5-furandicarboxylic acid, 0.30mol of 2,2,4, 4-tetramethyl-1, 3-cyclobutanol and 0.0004mol of anhydrous zinc acetate into a 1000mL reaction kettle, vacuumizing, filling nitrogen for replacement for three times, starting stirring, reacting at 5 ℃ for 2 hours, vacuumizing to 0.01-0.03MPa, reacting for 1 hour, stopping vacuum, introducing nitrogen, gradually heating to 165 ℃, and continuing to react for 4 hours. Adding isobutyl titanate, triphenyl phosphate and an antioxidant into the system, heating to 245 ℃, slowly vacuumizing for pre-polycondensation for 0.5h, and then controlling the vacuum degree to be below 200Pa for reaction for 3h to obtain a nearly colorless bio-based polymer compound: furan copolyester, intrinsic viscosity 0.88 dL/g.
Example 11
Adding 0.10mol of 2, 5-furan diformyl chloride, 0.06mol of 2, 5-furan dicarboxylic acid, 0.04mol of dimethyl naphthalenedicarboxylate, 0.15mol of ethylene glycol, 0.15mol of 1, 4-cyclohexanedimethanol and 0.0004mol of anhydrous zinc acetate into a 1000mL reaction kettle, vacuumizing, filling nitrogen for replacement three times, starting stirring, reacting for 2 hours at 25 ℃, vacuumizing to 0.01-0.03MPa, reacting for 1 hour, stopping vacuum, introducing nitrogen, gradually heating to 160 ℃, and continuing to react for 4 hours. Adding antimony trioxide, triphenyl phosphate and an antioxidant into a system, heating to 260 ℃, slowly vacuumizing for pre-polycondensation for 0.5h, and then controlling the vacuum degree to be below 200Pa for reaction for 3h to obtain a nearly colorless bio-based macromolecular compound: furan copolyester with intrinsic viscosity of 1.02dL/g, glass transition temperature of 90.6 deg.C, Td,5％The thermal decomposition temperature was 370 ℃. Oxygen gas barrier property of 0.010X 10-10cm3·cm/cm2s.cmHg, carbon dioxide gas barrier property 0.009×10-10cm3·cm/cm2s.cmHg, tensile strength 56.0MPa, tensile modulus 2.0GPa, and elongation at break 80%.
Example 12
Adding 0.10mol of 2, 5-furan diformyl chloride, 0.06mol of 2, 5-furan dicarboxylic acid, 0.04mol of dimethyl naphthalenedicarboxylate, 0.15mol of ethylene glycol, 0.15mol of 1, 4-cyclohexanedimethanol and 0.0004mol of anhydrous zinc acetate into a 1000mL reaction kettle, vacuumizing, filling nitrogen for replacement three times, starting stirring, reacting for 2 hours at 25 ℃, vacuumizing to 0.01-0.03MPa, reacting for 1 hour, stopping vacuum, introducing nitrogen, gradually heating to 160 ℃, and continuing to react for 4 hours. Adding antimony trioxide, triphenyl phosphate and an antioxidant into a system, heating to 260 ℃, slowly vacuumizing for pre-polycondensation for 0.5h, and then controlling the vacuum degree to be below 200Pa for reaction for 3h to obtain a nearly colorless bio-based macromolecular compound: furan copolyester with intrinsic viscosity of 1.02dL/g, glass transition temperature of 90.6 deg.C, Td,5％The thermal decomposition temperature was 370 ℃. Oxygen gas barrier property of 0.010X 10-10cm3·cm/cm2s.cmHg, carbon dioxide gas barrier property 0.009X 10-10cm3·cm/cm2s.cmHg, tensile strength 56.0MPa, tensile modulus 2.0GPa, and elongation at break 80%.
Example 13
Adding 0.10mol of 2, 5-furan diformyl chloride, 0.1mol of 2, 5-furan dicarboxylic acid, 0.15mol of butanediol, 0.15mol of 1, 4-cyclohexanedimethanol and 0.0004mol of anhydrous zinc acetate into a 1000mL reaction kettle, vacuumizing, filling nitrogen for three times for replacement, starting stirring, reacting for 2 hours at 25 ℃, vacuumizing to 0.01-0.03MPa, reacting for 1 hour, stopping vacuum, introducing nitrogen, gradually heating to 160 ℃, and continuing to react for 4 hours. Adding antimony trioxide, triphenyl phosphate and an antioxidant into a system, heating to 240 ℃, slowly vacuumizing for pre-polycondensation for 0.5h, and then controlling the vacuum degree to be below 200Pa for reaction for 3h to obtain a nearly colorless bio-based polymer compound: furan copolyester, intrinsic viscosity 0.74 dL/g.
Example 14
Adding 0.10mol of 2, 5-furandicarboxylic acid dichloride, 0.1mol of 2, 5-furandicarboxylic acid, 0.15mol of hexanediol, 0.15mol of 1, 4-cyclohexanedimethanol and 0.0004mol of anhydrous zinc acetate into a 1000mL reaction kettle, vacuumizing, filling nitrogen for three times for replacement, starting stirring, reacting at 25 ℃ for 2 hours, vacuumizing to 0.01-0.03MPa, reacting for 1 hour, stopping vacuum, introducing nitrogen, gradually heating to 160 ℃, and continuing to react for 4 hours. Adding antimony trioxide, triphenyl phosphate and an antioxidant into a system, heating to 240 ℃, slowly vacuumizing for pre-polycondensation for 0.5h, and then controlling the vacuum degree to be below 200Pa for reaction for 3h to obtain a nearly colorless bio-based polymer compound: furan copolyester, intrinsic viscosity 0.92 dL/g.
Example 15
Adding 0.10mol of 2, 5-furandicarboxylic acid dichloride, 0.1mol of 2, 5-furandicarboxylic acid, 0.15mol of 1, 8-octanediol, 0.15mol of 1, 4-cyclohexanedimethanol and 0.0004mol of anhydrous zinc acetate into a 1000mL reaction kettle, vacuumizing, filling nitrogen for replacement for three times, starting stirring, reacting at 25 ℃ for 2 hours, vacuumizing to the pressure of 0.01-0.03MPa, reacting for 1 hour, stopping vacuum, introducing nitrogen, gradually heating to 160 ℃, and continuing to react for 4 hours. Adding antimony trioxide, triphenyl phosphate and an antioxidant into a system, heating to 240 ℃, slowly vacuumizing for pre-polycondensation for 0.5h, and then controlling the vacuum degree to be below 200Pa for reaction for 3h to obtain a nearly colorless bio-based polymer compound: furan copolyester, intrinsic viscosity 0.97 dL/g.
Example 16
Adding 0.10mol of 2, 5-furan diformyl chloride, 0.06mol of 2, 5-furan dicarboxylic acid dimethyl ester, 0.04mol of terephthalic acid dimethyl ester, 0.15mol of ethylene glycol, 0.15mol of 1, 4-cyclohexanedimethanol and 0.0004mol of anhydrous zinc acetate into a 1000mL reaction kettle, vacuumizing, filling nitrogen for replacement for three times, starting stirring, reacting for 2 hours at 25 ℃, vacuumizing to 0.01-0.03MPa, reacting for 1 hour, stopping vacuum, introducing nitrogen, gradually heating to 160 ℃, and continuing to react for 4 hours. Adding antimony trioxide, triphenyl phosphate and an antioxidant into a system, heating to 240 ℃, slowly vacuumizing for pre-polycondensation for 0.5h, and then controlling the vacuum degree to be below 200Pa for reaction for 3h to obtain a nearly colorless bio-based polymer compound: furan copolyester, intrinsic viscosity 1.02 dL/g.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (10)
1. A bio-based polymer compound, wherein the bio-based polymer compound is a bio-based furan polyester, and the components for synthesizing the bio-based polymer compound comprise:
component (a): furan dicarboxylic acid, furan dicarboxylate, or a combination thereof;
a component (b): furan diformyl chloride;
optional component (c): an aromatic dibasic acid, an aliphatic dibasic acid, an aromatic dibasic acid ester, an aliphatic dibasic acid ester, or a combination thereof; and
a component (d): a cyclic diol, an aliphatic diol, or a combination thereof,
wherein the content of the component (b) is 0.4mol percent to 35mol percent based on the total molar weight of the components (a), (b), (c) and (d);
the bio-based polymer compound is prepared by a method comprising the following steps:
(i) providing a first mixture comprising components (a), (b), (c), and (d);
(ii) subjecting components (b) and (d) of the first mixture to a nucleophilic substitution reaction to form a first intermediate product;
(iii) subjecting component (a) and component (d), and/or component (c) and component (d) in the first intermediate product to an esterification reaction and/or transesterification reaction in the presence of an esterification catalyst, thereby forming a second intermediate product; and
(iv) performing a polycondensation reaction on the second intermediate product in the presence of a polycondensation catalyst to obtain the bio-based polymer compound;
wherein, in step (iv), the reaction temperature is from 180 ℃ to 280 ℃;
the intrinsic viscosity of the high molecular compound is 0.7-1.4dL/g, and the melting point is 190-280 ℃;
the molar ratio of the component (a) to the component (b) is 0.6-100.
2. The bio-based polymer compound according to claim 1, wherein: the molar ratio of the component (a) to the component (b) is 0.6-10.
3. The bio-based polymer compound according to claim 1, wherein the components for synthesizing said polymer compound further comprise an additive, wherein said additive is selected from the group consisting of: an esterification catalyst, a polycondensation catalyst, a stabilizer, an antioxidant, or a combination thereof.
4. The bio-based polymer compound according to claim 1, wherein said polymer compound has one or more properties selected from the group consisting of:
(1) the glass transition temperature is 60-95 ℃;
(2) oxygen gas barrier property of 1.0X 10-13-5.0×10-12cm3·cm/cm2·s·cmHg；
(3) The carbon dioxide gas barrier property was 2.0X 10-13-5.0×10-12cm3·cm/cm2·s·cmHg；
(4) The tensile strength is 50-90 MPa;
(5) the tensile modulus is 2.0-3.5 GPa;
(6) the elongation at break is 10-50% or 80-300%.
5. The bio-based polymer compound according to claim 1, wherein the carbon contained in the furan ring in the component (a) and the component (b) is derived from a biomass raw material.
6. The bio-based polymer compound according to claim 1, wherein the molar ratio of the component (a) to the component (b) is 0.1 to 10.
7. The bio-based polymer compound according to claim 1, wherein said polymer compound is colorless.
8. A method for producing a bio-based polymer compound according to any one of claims 1 to 7, comprising the steps of:
(i) providing a first mixture comprising components (a), (b), (c), and (d);
(ii) subjecting components (b) and (d) of the first mixture to a nucleophilic substitution reaction to form a first intermediate product;
(iii) subjecting component (a) and component (d), and/or component (c) and component (d) in the first intermediate product to an esterification reaction and/or transesterification reaction in the presence of an esterification catalyst, thereby forming a second intermediate product; and
(iv) subjecting the second intermediate product to a polycondensation reaction in the presence of a polycondensation catalyst to obtain the bio-based polymer compound according to claim 1;
wherein, in step (iv), the reaction temperature is 180 ℃ to 280 ℃.
9. An article comprising or consisting of the bio-based polymer compound of claim 1.
10. The article of claim 9, wherein the article comprises: packaging materials, films, fibers, bottles, and/or engineering plastics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610831226.5A CN107840948B (en) | 2016-09-19 | 2016-09-19 | Bio-based polymer compound and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610831226.5A CN107840948B (en) | 2016-09-19 | 2016-09-19 | Bio-based polymer compound and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107840948A CN107840948A (en) | 2018-03-27 |
| CN107840948B true CN107840948B (en) | 2020-02-07 |
Family
ID=61657015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610831226.5A Active CN107840948B (en) | 2016-09-19 | 2016-09-19 | Bio-based polymer compound and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107840948B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499846B (en) * | 2019-01-31 | 2023-04-07 | 财团法人工业技术研究院 | Polyester and fiber |
| CN110128797A (en) * | 2019-05-13 | 2019-08-16 | 无锡风鹏新材料科技有限公司 | A kind of biaxially oriented polyester film that high temperature dimensional stability is excellent and its production method |
| CN113493561A (en) * | 2020-03-20 | 2021-10-12 | 中国科学院大连化学物理研究所 | 2, 6-naphthalenedicarboxylic acid based copolyester material and preparation method thereof |
| WO2022004811A1 (en) * | 2020-07-01 | 2022-01-06 | キリンホールディングス株式会社 | Polyethylene furanoate, highly-viscous polyethylene furanoate manufacturing method, polyester composition, polyester bottle, polyester bottle manufacturing method, and beverage product |
| WO2023120596A1 (en) * | 2021-12-23 | 2023-06-29 | キリンホールディングス株式会社 | Masterbatch, preform, blow-molded bottle, beverage product, film, method for producing preform, and method for producing blow-molded bottle |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899145A (en) * | 2010-07-28 | 2010-12-01 | 江南大学 | Preparation method of 2, 5-furan diformyl polyester |
| CN102372845A (en) * | 2010-08-18 | 2012-03-14 | 东丽纤维研究所（中国）有限公司 | Macromolecular compound and production method thereof |
| CN102516513A (en) * | 2011-12-08 | 2012-06-27 | 江南大学 | Preparation method of low-yellowing 2,5-furandicarboxylic acid-based polyester |
| CN105189603A (en) * | 2013-03-15 | 2015-12-23 | 苏舍化学技术有限公司 | A process to prepare a cyclic oligomer and a cyclic oligomer obtainable thereby |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015060827A1 (en) * | 2013-10-22 | 2015-04-30 | Empire Technology Development Llc | Methods and compounds for producing nylon 6,6 |
-
2016
- 2016-09-19 CN CN201610831226.5A patent/CN107840948B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899145A (en) * | 2010-07-28 | 2010-12-01 | 江南大学 | Preparation method of 2, 5-furan diformyl polyester |
| CN102372845A (en) * | 2010-08-18 | 2012-03-14 | 东丽纤维研究所（中国）有限公司 | Macromolecular compound and production method thereof |
| CN102516513A (en) * | 2011-12-08 | 2012-06-27 | 江南大学 | Preparation method of low-yellowing 2,5-furandicarboxylic acid-based polyester |
| CN105189603A (en) * | 2013-03-15 | 2015-12-23 | 苏舍化学技术有限公司 | A process to prepare a cyclic oligomer and a cyclic oligomer obtainable thereby |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107840948A (en) | 2018-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107840948B (en) | Bio-based polymer compound and preparation method thereof | |
| CN107840946B (en) | Bio-based polymer compound and preparation method thereof | |
| CN110734542B (en) | Novel thiophene diformate copolyester and preparation method and application thereof | |
| TWI494367B (en) | Blend of polylactic acid resin and copolyester resin and articles using the same | |
| KR20120088209A (en) | Copolymerized polyester resin composition and preparing method thereof | |
| EP2848639B1 (en) | Method for producing polyester resin having cyclic acetal skeleton | |
| CN110563937A (en) | High-barrier thiophene polyester and preparation method and application thereof | |
| CN110183633B (en) | 1, 4; 3, 6-diglycidyl hexachloro-hexane modified furan diformyl random copolymer and preparation method and application thereof | |
| CN109810248B (en) | Furan dicarboxylic acid copolyester and preparation method thereof | |
| KR20120110477A (en) | Polyester resin copolymerized with lactic acid and isosorbide and preparing method thereof | |
| TW201731908A (en) | Polyester resin, preparation method thereof and resin article formed therefrom | |
| KR20150002624A (en) | Polymers, the process for the synthesis thereof and compositions comprising same | |
| CN102643419A (en) | Preparation method of aliphatic-aromatic copolyester | |
| JP5079226B2 (en) | Polybutylene terephthalate | |
| US10072118B2 (en) | Polycyclohexylenedimethylene terephthalate resin having enhanced crystallization speed and method for preparing same | |
| KR101515823B1 (en) | A transparent copolyester, preparing method thereof and articles made from the same | |
| CN114456565B (en) | Carbon dioxide-based polylactic acid copolymer modified cellulose material and preparation method thereof | |
| JP5902776B2 (en) | Copolyester carbonate and method for producing the same | |
| KR102236319B1 (en) | A preparation method of High molecular weight aliphatic carbonate and aromatic ester copolymer resin | |
| CN111116883B (en) | Biodegradable copolyester and preparation method thereof | |
| CN1931893A (en) | Prepn process of PET/PTT copolyester | |
| EP3523349B1 (en) | Process for the production of a solid-state polymerized poly (tetramethylene-2, 5-furan dicarboxylate) polymer and polymer thus produce | |
| CN114057998A (en) | 2, 5-furandicarboxylic acid copolyester and preparation method thereof | |
| JP4691934B2 (en) | High molecular weight polyoxalate resin and method for producing the same | |
| CN113321793B (en) | Low-end carboxyl aliphatic polyester and 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 |