CN107840948A - A kind of bio-based high-molecular compound and preparation method thereof - Google Patents
A kind of bio-based high-molecular compound and preparation method thereof Download PDFInfo
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- CN107840948A CN107840948A CN201610831226.5A CN201610831226A CN107840948A CN 107840948 A CN107840948 A CN 107840948A CN 201610831226 A CN201610831226 A CN 201610831226A CN 107840948 A CN107840948 A CN 107840948A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- 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
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- 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
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a kind of bio-based high-molecular compound and preparation method thereof.The bio-based high-molecular compound of the present invention is the bio-based furans polyester containing furan structure, wherein including for the component for synthesizing described bio-based high-molecular compound：Component (a) furandicarboxylic acid or its carboxylate, component (b) furans dimethyl chloride, component (c) aromatic series or aliphatic dibasic acid or its carboxylate, component (d) cyclic diols or aliphatic dihydroxy alcohol.The high-molecular compound of the present invention not only has molecular weight height, stretch modulus is high, tensile strength is high, heat-resist, oxygen-barrier property and dioxide barrier properties are good, and solves the problems, such as the current depth of polyester color containing furan nucleus.The bio-based high-molecular compound of the present invention can meet the application demand in the fields such as packaging material, film, fiber, engineering plastics.
Description
Technical field
The present invention relates to polymeric material field, in particular it relates to a kind of bio-based high-molecular compound and its preparation side
Method.The high-molecular compound can be widely applied to the manufacturing of packaging material, film, fiber, engineering plastics etc..
Background technology
At present, widely used bio-based high polymer material mainly has PLA (PLA), poly-hydroxy fatty acid (PHA), gathered
Hydroxyacetic acid (PGA), polybutylene glycol succinate (PBS) etc..They belong to fats polymer, due to being lacked in molecular structure
Weary rigid aromatic ring structure, its mechanical property (such as intensity, modulus, creep resistant) and heat resistance (such as thermomechanical property, thermal change
Shape temperature etc.) significantly lower than polyethylene terephthalate (PET), makrolon (PC), aramid fiber (PA), bisphenol-A
The petroleum base high polymer materials such as type epoxy resin (Epoxy), seriously limit their application.
Contain aromatic rings in the molecular structure of FDCA (2,5-FDCA), for synthesising biological based high molecular material
Material can effectively improve its heat resistance and mechanical performance, and the oxygen-barrier property of the polyester material containing furan nucleus is relative to big simultaneously
5-10 times can be improved for the PET of packaging material by measuring, and can effectively improve the shelf-life of agricultural product, fish, meat products.
However, use polyester material often some shortcomings, such as with deeper made from FDCA at present
Color, stretch modulus are low, tensile strength is low, heat resistance is low etc..For example, synthesized at present with furandicarboxylic acid or its carboxylate poly-
Ester color is often relatively deep, is yellow, dark yellow or black, so as to have a strong impact on that it is applied in fields such as packaging, fibers.
Therefore, this area needs new bio-based high score that is colourless or light and having the excellent performances such as high stretch modulus
Sub- compound.
The content of the invention
It is an object of the invention to provide a kind of colourless or light and with the biology of the excellent performance such as high stretch modulus
Based high molecular compound.
The first aspect of the present invention provides a kind of bio-based high-molecular compound, described bio-based high-molecular compound
For bio-based furans polyester, the component for synthesizing described bio-based high-molecular compound includes：
Component (a)：Furandicarboxylic acid, furandicarboxylic acid carboxylate or its combination；
Component (b)：Furans dimethyl chloride；
Optional component (c)：Aromatic acid, aliphatic dibasic acid, aromatic acid carboxylate, binary aliphatic
Acid esters compound or its combination；With
Component (d)：Cyclic diols, aliphatic dihydroxy alcohol or its combination,
Wherein, the content of component (b) is 0.001mol%-35mol%, by component (a)+(b)+(c)+(d) total moles
Gauge.
In another preference, described component (a), (b), (c) and (d) sum account for the high-molecular compound total amount
About 70-100wt%, preferably 80-99.5wt%, more preferably 90-99wt%.
In another preference, the mol ratio of described component (a) and component (b) is 0.001-1000.It is it is preferred that described
The mol ratio of component (a) and component (b) be 0.01-100, more preferably 0.05-50, most preferably 0.1-10.
In another preference, described component (a)+(b) accounts for the 70mol- of component (a)+(b)+(c) total contents
100mol%.
In another preference, described component (c) accounts for the 0mol-30mol% of component (a)+(b)+(c) total contents.
In another preference, described cyclic diols account for the 15mol-100mol% of whole glycol contents.
In another preference, described aliphatic dihydroxy alcohol accounts for the 0mol-85mol% of whole glycol contents.
In another preference, the component (a) is selected from the group：Furandicarboxylic acid, furandicarboxylic acid dimethyl ester or its group
Close.
In another preference, described component (a) is furandicarboxylic acid dimethyl ester.
In another preference, described component (b) is selected from the group：2,5 furans dimethyl chlorides, the formyl of 2,4- furans two
Chlorine, 3,4- furans dimethyl chloride or its combination.
In another preference, described component (c) is selected from the group：2,6- naphthalenes diacid, 2,6- naphthalenes acid dimethyl, to benzene
Dioctyl phthalate, dimethyl terephthalate (DMT), succinic acid, dimethyl succinate or its combination.
In another preference, described component (c) is 2,6- naphthalene acid dimethyls.
In another preference, described cyclic diols are selected from the group：1,4- cyclohexanedimethanols, 2,2,4,4- tetramethyls
Base -1,3- cyclobutanols or its combination.
In another preference, described cyclic diols are Isosorbide-5-Nitrae-cyclohexanedimethanol.
In another preference, described aliphatic dihydroxy alcohol is selected from the group：Ethylene glycol, 1,3- propane diols, 1,4- fourths two
Alcohol, 1,6-HD, 1,8- ethohexadiols or its combination.
In another preference, described aliphatic dihydroxy alcohol is ethylene glycol.
In another preference, additive, wherein institute are also included in the component for synthesizing described high-molecular compound
Additive is stated to be selected from the group：Esterification catalyst, polycondensation catalyst, stabilizer, antioxidant or its combination.
In another preference, described esterification catalyst is selected from the group：Anhydrous zinc acetate, anhydrous cobalt acetate, anhydrous second
Sour manganese, Dibutyltin oxide or its combination.
In another preference, described polycondensation catalyst is selected from the group：Antimony-based catalyst, Titanium series catalyst, germanium system urge
Agent, tin series catalysts, it is preferred that the polycondensation catalyst is selected from the group：Antimony oxide, iso-butyl titanate, the fourth of metatitanic acid four
Ester, antimony glycol, antimony acetate or its combination.
In another preference, described stabilizer is selected from the group：Phosphoric acid, phosphorous acid, ortho phosphorous acid, pyrophosphoric acid, phosphoric acid
Ammonium, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, phosphorous
Sour ammonium, ammonium dihydrogen phosphate or its combination.
In another preference, described antioxidant is selected from the group：Phenolic antioxidant, preferably antioxidant -1010, antioxygen
Agent -1076 or its combination.
In another preference, described bio-based high-molecular compound is prepared with the method comprised the following steps：
(i) the first mixture is provided, first mixture contains component (a), (b), (c) and (d)；
(ii) component (b) in first mixture and (d) are subjected to nucleophilic substitution, are formed among first and produced
Thing；
(iii) in the presence of esterification catalyst, by the component (a) in first intermediate product and component (d), and/or
Component (c) and component (d) carry out esterification and/or ester exchange reaction, so as to form to obtain the second intermediate product；With
(iv) in the presence of polycondensation catalyst, polycondensation reaction is carried out to second intermediate product, so as to obtain such as this hair
Bright described bio-based high-molecular compound.
In another preference, in step (i), the first described mixture also contains esterification catalyst.
In another preference, in step (iv), including step：By polycondensation catalyst, stabilizer and antioxidant and institute
State the second intermediate to be mixed, then carry out polycondensation reaction.
In another preference, in step (ii), (iii) and/or (iv), the reaction is carried out under an inert atmosphere.
In another preference, described inert atmosphere includes nitrogen, argon gas or its combination.
In another preference, between step (ii) and (iii), in addition to：Remove or neutralize in nucleophilic substitution
Caused HCl.
In another preference, in step (ii), reaction temperature is -20 DEG C to 90 DEG C；And/or the reaction time is 0.2-
24 hours.
In another preference, in step (iii), reaction temperature is 120 DEG C to 240 DEG C；And/or the reaction time is
0.2-36 hours.
In another preference, in step (iv), reaction temperature is 180 DEG C to 280 DEG C；And/or the reaction time is
0.2-48 hours.
In another preference, the carbon contained by furan nucleus in described component (a) and component (b) comes from biomass former material
Material.
In another preference, described biomass raw material are selected from the group：Cellulose, fructose, glucose, furancarboxylic acid or
It is combined.
In another preference, described high-molecular compound inherent viscosity is 0.7-1.4dL/g, and fusing point is 190
℃-280℃。
In another preference, described high-molecular compound color is light or colourless.
In another preference, described high-molecular compound has the one or more characteristics being selected from the group：
(1) glass transition temperature is 60-95 DEG C；
(2) oxygen gas barrier is 1.0 × 10-13-5.0×10-12cm3·cm/cm2·s·cmHg；
(3) carbon dioxide barrier is 2.0 × 10-13-5.0×10-12cm3·cm/cm2·s·cmHg；
(4) tensile strength is 50-90MPa；
(5) stretch modulus is 2.0-3.5GPa；
(6) elongation at break is 10-50% or 80-300%.
The second aspect of the present invention provides a kind of preparation method of bio-based high-molecular compound, the preparation method bag
Include step：
(i) the first mixture is provided, first mixture contains component (a), (b), (c) and (d)；
(ii) component (b) in first mixture and (d) are subjected to nucleophilic substitution, are formed among first and produced
Thing；
(iii) in the presence of esterification catalyst, by the component (a) in first intermediate product and component (d), and/or
Component (c) and component (d) carry out esterification and/or ester exchange reaction, so as to form to obtain the second intermediate product；With
(iv) in the presence of polycondensation catalyst, polycondensation reaction is carried out to second intermediate product, so as to obtain such as this hair
Bio-based high-molecular compound described in bright first aspect.
In another preference, in described esterification, described component (a) and component (d), and/or component (c)
Esterification and/or ester exchange reaction removing H occurs with component (d)2O and/or low-boiling point alcohol.
In another preference, in described nucleophilic substitution, described component (b) reacts with component (d)
And remove HCl.
The third aspect of the present invention provides a kind of product, and the product includes the bio-based described in first aspect present invention
High-molecular compound, or the product are made up of the bio-based high-molecular compound described in first aspect present invention.
In another preference, described product includes：Packaging material, film, fiber, bottle, and/or engineering plastics.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and have in below (eg embodiment)
It can be combined with each other between each technical characteristic of body description, so as to form new or preferable technical scheme.As space is limited, exist
This no longer tires out one by one states.
Brief description of the drawings
The dark yellow batten and film sample photo for the poly- 2,5- furandicarboxylic acids glycol ester that Fig. 1 comparative examples 1 obtain.
Fig. 2 is the bio-based furans copolyesters that embodiment 1 obtains1H-NMR collection of illustrative plates.
Fig. 3 is the DSC collection of illustrative plates for the bio-based furans copolyesters that embodiment 1 obtains.
Fig. 4 is the TGA collection of illustrative plates for the bio-based furans copolyesters that embodiment 1 obtains.
Fig. 5 is the colorless film sample photo for the bio-based furans copolyesters that embodiment 1 obtains.
Embodiment
The present inventor by extensively and in depth study, have unexpectedly discovered that first a kind of bio-based high-molecular compound and
Its preparation method.The bio-based high-molecular compound of the present invention prepares described macromolecule chemical combination using following components (monomer)
Thing：Component (a) furandicarboxylic acid or its carboxylate, component (b) furans dimethyl chloride, component (c) aromatic series or binary aliphatic
Acid or its carboxylate, component (d) cyclic diols or aliphatic dihydroxy alcohol.Pass through nucleophilic substitution, esterification and polycondensation
The polymer of reaction synthesis has the biological based high molecular of premium properties (colourless or light and mechanical performance excellent etc.)
Compound, i.e. bio-based furans polyester.On this basis, the present invention is completed.
Term
As used herein, " bio-based high-molecular compound of the invention ", " bio-based furans polyester of the invention ", " this
The polyester of invention ", " furans polyester of the invention " are used interchangeably, refer to it is described in first aspect present invention, containing furans knot
The polyphosphazene polymer ester compounds of structure.
Bio-based high-molecular compound
The invention provides a kind of bio-based high-molecular compound, described bio-based high-molecular compound is bio-based furan
Mutter polyester.
One in the high-molecular compound of the present invention is mainly characterized by preparation process, employs the furans two of high activity
Formyl chloride and furandicarboxylic acid or furandicarboxylic acid dimethyl ester composition blend and 1,4- cyclohexanedimethanols, 2,2,4,4 ,-tetramethyl
The cyclic diols such as base -1,3- cyclobutanols, ethylene glycol, butanediol or aliphatic dihydroxy alcohol copolymerization.Present inventors have surprisingly found that
When adding a certain amount of furans dimethyl chloride, can not only solve the problems, such as that existing furans polyester product color is deeper, and
And molecular weight can be further improved, lift the mechanical property of polymer.
Bio-based high-molecular compound of the present invention, i.e. bio-based furans polyester are by component (a) furandicarboxylic acid
Or its carboxylate, component (b) furans dimethyl chloride, component (c) aromatic series or aliphatic dibasic acid or its carboxylate, component (d)
Cyclic diols or aliphatic dihydroxy alcohol, as obtained by nucleophilic substitution, esterification and polycondensation reaction synthesis.The biology
Based high molecular compound has higher molecular weight, modulus and intensity, and preferable heat resistance, oxygen-barrier property and titanium dioxide
The premium properties such as carbon barrier.
In the present invention, the component (a) includes but is not limited to：Furandicarboxylic acid, furandicarboxylic acid dimethyl ester or its
Combination.Preferably, the component (a) is furandicarboxylic acid dimethyl ester.The component (b) is including but not limited to：2,5 furans two
Formyl chloride, 2,4- furans dimethyl chloride, 3,4- furans dimethyl chloride or its combination.The component (c) is including but not limited to：
2,6- naphthalenes diacid, 2,6- naphthalenes acid dimethyl, terephthalic acid (TPA), dimethyl terephthalate (DMT), succinic acid, dimethyl succinate,
Or its combination.Preferably, the component (c) is 2,6- naphthalene acid dimethyls.The cyclic diols include but is not limited to：1,
4- cyclohexanedimethanols, 2,2,4,4- tetramethyl -1,3- cyclobutanols or its combination.Preferably, the cyclic diols are Isosorbide-5-Nitrae-ring
Own dimethanol.The aliphatic dihydroxy alcohol includes but is not limited to：Ethylene glycol, 1,3- propane diols, 1,4- butanediols, 1,6- oneself two
Alcohol, 1,8- ethohexadiols or its combination.Preferably, the aliphatic dihydroxy alcohol is ethylene glycol.
Synthetic method
Present invention also offers the preparation method of bio-based high-molecular compound of the present invention.
Generally, first at a certain temperature, furans dimethyl chloride and described dihydric alcohol (such as aliphatic dihydroxy alcohol) are sent out
Raw nucleophilic substitution generates white carboxylate；Then, further rise temperature carries out esterification, and carries out polycondensation reaction,
So as to obtain colourless or light HMW bio-based compounds.
Typically, (such as -10-80 DEG C) nucleophilic occurs for the present invention at a lower temperature using furans dimethyl chloride with dihydric alcohol
Substitution reaction removes HCl reaction mechanism, and using furandicarboxylic acid or its carboxylate and dihydric alcohol at relatively high temperatures (such as
120-200 DEG C) esterification and/or ester exchange reaction removing H occurs2The reaction mechanism of O and/or low-boiling point alcohol is described to implement
The synthetic reaction of high-molecular compound, finally pass through polycondensation reaction under high temperature (such as 200-260 DEG C), vacuum (such as 3-1000Pa)
Obtain colourless or light HMW high-molecular compound.
In a preference, the method for the high-molecular compound described in preparation of the invention includes step：
(1) mixture of a component (a), (b), (c), (d) and esterification catalyst is provided；
(2) mixture of step (1) is reacted to a period of time in the nitrogen environment of certain temperature, obtains producing among first
Thing；
(3) nitrogen in step (2) is pumped, the first intermediate product is reacted a period of time under vacuum conditions, obtains the
Two intermediate products；
(4) stop vacuum, be passed through nitrogen, and raise temperature, continue reaction a period of time, so as to obtain being produced among the 3rd
Thing；
(5) polycondensation catalyst, stabilizer and antioxidant are added in the 3rd intermediate product, and in the basis of step (4)
Upper further rise temperature, then slowly vacuumize precondensation for a period of time, obtains the 4th intermediate product；With
(6) control vacuum continues reaction a period of time within the specific limits, and it is high to obtain bio-based as described in the present invention
Molecular compound.
In the step (2), reaction temperature is -10-80 DEG C, reaction time 0.5-2h.
In the step (3), vacuum is below 2000Pa, reaction time 0.5-2h.
In the step (4), temperature is 120-240 DEG C, reaction time 0.5-8h
In the step (5), 200-260 DEG C is warming up to, reaction time 0.5-2h.
In the step (6), vacuum degree control is in below 200Pa, reaction time 0.5-10h.
Using
The bio-based high-molecular compound of the present invention because it has a colourless or light outward appearance, and with molecular weight it is high,
The features such as stretch modulus is high, tensile strength is high, heat-resist, oxygen-barrier property and dioxide barrier properties are good, it is therefore, especially suitable
For fields such as packaging material, film, fiber, engineering plastics.
Preferably, the invention provides a kind of product, it includes the bio-based high-molecular compound of the present invention, or by this hair
Bright bio-based high-molecular compound is formed.Representational product includes (but being not limited to)：Packaging material, film, fiber, bottle
Son, and/or engineering plastics.
Performance test
In the present invention and embodiment, conventional method and conventional equipment can be used, the high-molecular compound of the present invention is entered
Row performance measurement.It is measured referring for example to GB standards or other standards.
Glass transition temperature, tensile strength, stretch modulus and elongation at break are measured with conventional method.
Proton nmr spectra1H-NMR is used to be determined on the Spectrometer type instruments of Bruker 400AVANCE III,
400MHz, CF3COOD。
In embodiment, the measure of inherent viscosity is with phenol/tetrachloroethanes (1:1m/m) it is solvent, at 30 ± 0.05 DEG C, uses
Ubbelohde viscometer is tested, and the intrinsic viscosity [η] of polyester and copolyesters is calculated by formula (1), (2) and (3).
ηsp=(t1-t0)/t0 (1)
[η]=[(1+1.4 ηsp)1/2-1]/0.7c (2)
Wherein：t0For the flow time (s) of solvent；t1For the flow time (s) of solution；C is solution concentration, 5g/L.
Heat analysis uses means of differential scanning calorimetry (Mettler Toledo DSC) with 20 DEG C/min heating rate, in N2Gas
Atmosphere is carried out, and temperature range is 25-300 DEG C.Thermogravimetic analysis (TGA) (TGA) is carried out on Perkin-Elmer Diamond TG/DTA,
The rate of heat addition is 10 DEG C/min, and temperature range is 50-800 DEG C.
The barrier of oxygen and carbon dioxide, permeability test is carried out using Labthink VAC-V2, respectively with CO2And O2
It is respectively under conditions of 23 DEG C and 50%RH, from sample size Ф=97mm, transmission area in temperature and humidity for source of the gas
38.5cm2。
Main advantages of the present invention include：
1. effectively utilizing the high activity of furans dimethyl chloride, nucleophilic substitution occurs with alcohol, polymerization can be effectively improved
The relative molecular mass of thing.
2. obtaining colourless or light bio-based furans copolyesters, meet packaging material, film, fiber, engineering plastics etc.
The application demand in field, it is capable of the manufacture level of service hoisting high performance engineering plastics.
3. bio-based Polymer Material Industry can be promoted to break away from the height dependence to petroleum resources.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.The experimental method of unreceipted actual conditions in the following example, generally according to conventional strip
Part, or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise percentage and number are calculated by weight.
Comparative example 1
By 0.2mol FDCA, 0.15mol ethylene glycol, 0.15mol Isosorbide-5-Nitrae-cyclohexanedimethanol,
0.0004mol anhydrous zinc acetate is added in 1000mL reactors, vacuumize, inflated with nitrogen displacement three times, open stirring, progressively
180 DEG C are warming up to, reacts 4h.Antimony oxide, triphenyl phosphate and antioxidant are added in system, is warming up to 240 DEG C, slowly
Precondensation 0.5h is vacuumized, then controls below vacuum 200Pa to react 3h, obtains the poly- FDCA second of dark yellow
Diol ester, inherent viscosity 0.72dL/g, 82.0 DEG C of glass transition temperature, 207.4 DEG C of fusing point, crystalline fusion enthalpy Δ HmFor
7.2J/g, it is dark yellow to extrude batten and film, and sample photo is as shown in Figure 1.Batten tensile strength 58.0MPa, stretch modulus
2.2GPa, elongation at break 88.1%.
Embodiment 1
By 0.10mol 2,5- furans dimethyl chlorides, 0.1mol FDCA, 0.15mol ethylene glycol,
0.15mol Isosorbide-5-Nitrae-cyclohexanedimethanol, 0.0004mol anhydrous zinc acetate are together added in 1000mL reactors, vacuumize,
Inflated with nitrogen is replaced three times, is opened stirring, 25 DEG C of reaction 2h, is evacuated to pressure 0.01-0.03MPa, reacts 1h, stop vacuum,
It is passed through nitrogen and is progressively warming up to 160 DEG C, continues to react 4h.Antimony oxide, triphenyl phosphate and antioxidant are added in system,
240 DEG C are warming up to, slowly vacuumizes precondensation 0.5h, then controls below vacuum 200Pa to react 3h, obtains bio-based high score
Sub- compound：Furans copolyesters,1H-NMR 80.6 DEG C of glass transition temperature, melts as shown in Fig. 2 inherent viscosity 0.98dL/g
225.4 DEG C of point, crystalline fusion enthalpy Δ HmFor 27.2J/g, as shown in Figure 3.TD, 5%Heat decomposition temperature is 365 DEG C, as shown in Figure 4.
Oxygen gas barrier is 3.1 × 10-12cm3·cm/cm2ScmHg, carbon dioxide barrier are 3.5 × 10- 12cm3·cm/cm2ScmHg, tensile strength 68.0MPa, stretch modulus 2.2GPa, elongation at break increase substantially
180%, toughness enhancing.The colourless furans copolyester film photo that extrusion batten and melting mould pressing method obtain is as shown in Figure 5.
Embodiment 2
By 0.08mol 2,5- furans dimethyl chlorides, 0.12mol FDCA, 0.30mol1,4- hexamethylenes two
Methanol, 0.0008mol anhydrous zinc acetate are together added in 1000mL reactors, are vacuumized, inflated with nitrogen is replaced three times, unlatching
Stirring, 50 DEG C of reaction 2h, is evacuated to pressure 0.01-0.03MPa, reacts 1h, stop vacuum, be passed through nitrogen and be progressively warming up to
140 DEG C, continue to react 4h.Antimony oxide, triphenyl phosphate and antioxidant are added in system, 240 DEG C is warming up to, slowly takes out
Vacuum precondensation 0.5h, then control below vacuum 200Pa to react 3h, obtain connecing subdiaphanous bio-based macromolecule chemical combination
Thing：Furans copolyesters, inherent viscosity 1.12dL/g, 79.6 DEG C of glass transition temperature, 260.4 DEG C of fusing point, crystalline fusion enthalpy Δ
HmFor 42.1J/g.TD, 5%Heat decomposition temperature is 368 DEG C.Oxygen gas barrier is 3.2 × 10-12cm3·cm/cm2·s·
CmHg, carbon dioxide barrier are 3.3 × 10-12cm3·cm/cm2ScmHg, tensile strength 75.1MPa, stretching die
Measure 2.2GPa, elongation at break 24%.
Embodiment 3
By 0.002mol 2,5- furans dimethyl chlorides, 0.198mol FDCA, 0.12mol second two
Alcohol, 0.18mol Isosorbide-5-Nitrae-cyclohexanedimethanol, 0.0001mol anhydrous zinc acetate are together added in 1000mL reactors, are taken out true
Empty, inflated with nitrogen displacement three times, opens stirring, 10 DEG C of reaction 2h, is evacuated to pressure 0.01-0.03MPa, reacts 1h, stop true
Sky, it is passed through nitrogen and is progressively warming up to 180 DEG C, continues to react 4h.Antimony oxide, triphenyl phosphate and antioxygen are added in system
Agent, is warming up to 260 DEG C, slowly vacuumizes precondensation 0.5h, then controls below vacuum 200Pa to react 3h, obtains close to nothing
The bio-based high-molecular compound of color：Furans copolyesters, inherent viscosity 0.87dL/g, 84 DEG C of glass transition temperature.Oxygen gas
Body barrier is 2.7 × 10-12cm3·cm/cm2ScmHg, carbon dioxide barrier are 3.6 × 10-12cm3·cm/
cm2ScmHg, tensile strength 75.1MPa, stretch modulus 2.2GPa, elongation at break 24%.
Embodiment 4
By 0.06mol 2,5- furans dimethyl chlorides, 0.14mol FDCA dimethyl ester, 0.12mol second
Glycol, 0.18mol Isosorbide-5-Nitrae-cyclohexanedimethanol, 0.0002mol anhydrous zinc acetate are together added in 1000mL reactors, taken out
Vacuum, inflated with nitrogen displacement three times, open stirring, -5 DEG C of reaction 2h, are evacuated to pressure 0.01-0.03MPa, react 1h, stop
Vacuum, it is passed through nitrogen and is progressively warming up to 160 DEG C, continues to react 4h.Antimony oxide, triphenyl phosphate are added in system and is resisted
Oxygen agent, is warming up to 220 DEG C, slowly vacuumizes precondensation 0.5h, then controls below vacuum 200Pa to react 3h, is approached
Colourless bio-based high-molecular compound：Furans copolyesters, inherent viscosity 0.82dL/g, 82.6 DEG C of glass transition temperature.
Embodiment 5
By 0.04mol 2,5- furans dimethyl chlorides, 0.16mol FDCA dimethyl ester, 0.09mol second
Glycol, 0.21mol Isosorbide-5-Nitrae-cyclohexanedimethanol, 0.0004mol anhydrous zinc acetate are together added in 1000mL reactors, taken out
Vacuum, inflated with nitrogen displacement three times, open stirring, 30 DEG C of reaction 2h, are evacuated to pressure 0.01-0.03MPa, react 1h, stop
Vacuum, it is passed through nitrogen and is progressively warming up to 180 DEG C, continues to react 4h.Antimony oxide, triphenyl phosphate are added in system and is resisted
Oxygen agent, is warming up to 240 DEG C, slowly vacuumizes precondensation 0.5h, then controls below vacuum 200Pa to react 3h, is approached
Colourless bio-based high-molecular compound：Furans copolyesters, inherent viscosity 1.03dL/g, 84.4 DEG C of glass transition temperature.
Embodiment 6
By 0.02mol 2,5- furans dimethyl chlorides, 0.18mol FDCA dimethyl ester, 0.045mol's
Ethylene glycol, 0.255mol Isosorbide-5-Nitrae-cyclohexanedimethanol, 0.0008mol anhydrous zinc acetate are together added to 1000mL reactors
In, vacuumize, inflated with nitrogen displacement three times, open stirring, 12 DEG C of reaction 2h, be evacuated to pressure 0.01-0.03MPa, react 1h,
Stop vacuum, be passed through nitrogen and be progressively warming up to 200 DEG C, continue to react 4h.Antimony oxide, triphenyl phosphate are added in system
And antioxidant, 270 DEG C are warming up to, slowly vacuumizes precondensation 0.5h, then controls below vacuum 200Pa to react 3h, obtains
Connect subdiaphanous bio-based high-molecular compound：Furans copolyesters, inherent viscosity 1.12dL/g, glass transition temperature 85.1
℃。
Embodiment 7
By 0.002mol 2,5- furans dimethyl chlorides, 0.198mol FDCA dimethyl ester, 0.225mol
Ethylene glycol, 0.075mol Isosorbide-5-Nitrae-cyclohexanedimethanol, 0.001mol anhydrous zinc acetate is together added to 1000mL reactors
In, vacuumize, inflated with nitrogen displacement three times, open stirring, 5 DEG C of reaction 2h, be evacuated to pressure 0.01-0.03MPa, react 1h,
Stop vacuum, be passed through nitrogen and be progressively warming up to 160 DEG C, continue to react 4h.Antimony oxide, triphenyl phosphate are added in system
And antioxidant, 250 DEG C are warming up to, slowly vacuumizes precondensation 0.5h, then controls below vacuum 200Pa to react 3h, obtains
Connect subdiaphanous bio-based high-molecular compound：Furans copolyesters, inherent viscosity 0.79dL/g, glass transition temperature 86.2
℃。
Embodiment 8
By 0.2mol 2,5- furans dimethyl chlorides, 0.3mol Isosorbide-5-Nitrae-cyclohexanedimethanol, 1000mL reactors are added to
In, vacuumize, inflated with nitrogen displacement three times, open stirring, 0 DEG C of reaction 4h, be evacuated to pressure 0.01-0.03MPa, react 1h,
Stop vacuum, antimony oxide, triphenyl phosphate and antioxidant are added in system, be progressively warming up to 260 DEG C, control vacuum
Below 200Pa reacts 3h, obtains connecing subdiaphanous bio-based high-molecular compound：Furans copolyesters, inherent viscosity 1.20dL/g,
80.1 DEG C of glass transition temperature, 262.3 DEG C of fusing point.
Embodiment 9
By 0.10mol 2,5- furans dimethyl chlorides, 0.1mol FDCA, 0.15mol ethylene glycol,
The 2 of 0.15mol, 2,4,4- tetramethyl -1,3- cyclobutanols, 0.0004mol anhydrous zinc acetate are together added to 1000mL reactions
In kettle, vacuumize, inflated with nitrogen displacement three times, open stirring, 25 DEG C reaction 2h, be evacuated to pressure 0.01-0.03MPa, react
1h, stop vacuum, be passed through nitrogen and be progressively warming up to 160 DEG C, continue to react 4h.Butyl titanate, tricresyl phosphate are added in system
Phenyl ester and antioxidant, are warming up to 240 DEG C, slowly vacuumize precondensation 0.5h, then control below vacuum 200Pa to react 3h,
Obtain connecing subdiaphanous bio-based high-molecular compound：Furans copolyesters, inherent viscosity 0.96dL/g, glass transition temperature
70.6 DEG C, 216.7 DEG C of fusing point.
Embodiment 10
By 0.01mol 2,5- furans dimethyl chlorides, 0.19mol FDCA, the 2,2,4,4- of 0.30mol
Tetramethyl -1,3- cyclobutanol, 0.0004mol anhydrous zinc acetate are together added in 1000mL reactors, vacuumized, inflated with nitrogen
Displacement three times, opens stirring, 5 DEG C of reaction 2h, is evacuated to pressure 0.01-0.03MPa, reacts 1h, stop vacuum, be passed through nitrogen
165 DEG C are progressively warming up to, continues to react 4h.Iso-butyl titanate, triphenyl phosphate and antioxidant are added in system, is warming up to
245 DEG C, precondensation 0.5h is slowly vacuumized, then controls below vacuum 200Pa to react 3h, obtains connecing subdiaphanous bio-based
High-molecular compound：Furans copolyesters, inherent viscosity 0.88dL/g.
Embodiment 11
By 0.10mol 2,5- furans dimethyl chlorides, 0.06mol FDCA, 0.04mol naphthalenedicarboxylic acid
Dimethyl ester, 0.15mol ethylene glycol, 0.15mol Isosorbide-5-Nitrae-cyclohexanedimethanol, 0.0004mol anhydrous zinc acetate together add
Into 1000mL reactors, vacuumize, inflated with nitrogen displacement three times, open stirring, 25 DEG C reaction 2h, be evacuated to pressure 0.01-
0.03MPa, 1h is reacted, stop vacuum, be passed through nitrogen and be progressively warming up to 160 DEG C, continue to react 4h.Three oxidations are added in system
Two antimony, triphenyl phosphate and antioxidant, are warming up to 260 DEG C, slowly vacuumize precondensation 0.5h, then control vacuum 200Pa
3h is reacted below, obtains connecing subdiaphanous bio-based high-molecular compound：Furans copolyesters, inherent viscosity 1.02dL/g, glass
Change 90.6 DEG C of transition temperature, TD, 5%Heat decomposition temperature is 370 DEG C.Oxygen gas barrier is 0.010 × 10-10cm3·cm/
cm2ScmHg, carbon dioxide barrier are 0.009 × 10-10cm3·cm/cm2ScmHg, tensile strength
56.0MPa, stretch modulus 2.0GPa, elongation at break 80%.
Embodiment 12
By 0.10mol 2,5- furans dimethyl chlorides, 0.06mol FDCA, 0.04mol naphthalenedicarboxylic acid
Dimethyl ester, 0.15mol ethylene glycol, 0.15mol Isosorbide-5-Nitrae-cyclohexanedimethanol, 0.0004mol anhydrous zinc acetate together add
Into 1000mL reactors, vacuumize, inflated with nitrogen displacement three times, open stirring, 25 DEG C reaction 2h, be evacuated to pressure 0.01-
0.03MPa, 1h is reacted, stop vacuum, be passed through nitrogen and be progressively warming up to 160 DEG C, continue to react 4h.Three oxidations are added in system
Two antimony, triphenyl phosphate and antioxidant, are warming up to 260 DEG C, slowly vacuumize precondensation 0.5h, then control vacuum 200Pa
3h is reacted below, obtains connecing subdiaphanous bio-based high-molecular compound：Furans copolyesters, inherent viscosity 1.02dL/g, glass
Change 90.6 DEG C of transition temperature, TD, 5%Heat decomposition temperature is 370 DEG C.Oxygen gas barrier is 0.010 × 10-10cm3·cm/
cm2ScmHg, carbon dioxide barrier are 0.009 × 10-10cm3·cm/cm2ScmHg, tensile strength
56.0MPa, stretch modulus 2.0GPa, elongation at break 80%.
Embodiment 13
By 0.10mol 2,5- furans dimethyl chlorides, 0.1mol FDCA, 0.15mol butanediol,
0.15mol Isosorbide-5-Nitrae-cyclohexanedimethanol, 0.0004mol anhydrous zinc acetate are together added in 1000mL reactors, vacuumize,
Inflated with nitrogen is replaced three times, is opened stirring, 25 DEG C of reaction 2h, is evacuated to pressure 0.01-0.03MPa, reacts 1h, stop vacuum,
It is passed through nitrogen and is progressively warming up to 160 DEG C, continues to react 4h.Antimony oxide, triphenyl phosphate and antioxidant are added in system,
240 DEG C are warming up to, slowly vacuumizes precondensation 0.5h, then controls below vacuum 200Pa to react 3h, obtains connecing subdiaphanous
Bio-based high-molecular compound：Furans copolyesters, inherent viscosity 0.74dL/g.
Embodiment 14
By 0.10mol 2,5- furans dimethyl chlorides, 0.1mol FDCA, 0.15mol hexylene glycol,
0.15mol Isosorbide-5-Nitrae-cyclohexanedimethanol, 0.0004mol anhydrous zinc acetate are together added in 1000mL reactors, vacuumize,
Inflated with nitrogen is replaced three times, is opened stirring, 25 DEG C of reaction 2h, is evacuated to pressure 0.01-0.03MPa, reacts 1h, stop vacuum,
It is passed through nitrogen and is progressively warming up to 160 DEG C, continues to react 4h.Antimony oxide, triphenyl phosphate and antioxidant are added in system,
240 DEG C are warming up to, slowly vacuumizes precondensation 0.5h, then controls below vacuum 200Pa to react 3h, obtains connecing subdiaphanous
Bio-based high-molecular compound：Furans copolyesters, inherent viscosity 0.92dL/g.
Embodiment 15
By 0.10mol 2,5- furans dimethyl chlorides, 0.1mol FDCA, 0.15mol 1,8- pungent two
Alcohol, 0.15mol Isosorbide-5-Nitrae-cyclohexanedimethanol, 0.0004mol anhydrous zinc acetate are together added in 1000mL reactors, are taken out true
Empty, inflated with nitrogen displacement three times, opens stirring, 25 DEG C of reaction 2h, is evacuated to pressure 0.01-0.03MPa, reacts 1h, stop true
Sky, it is passed through nitrogen and is progressively warming up to 160 DEG C, continues to react 4h.Antimony oxide, triphenyl phosphate and antioxygen are added in system
Agent, is warming up to 240 DEG C, slowly vacuumizes precondensation 0.5h, then controls below vacuum 200Pa to react 3h, obtains close to nothing
The bio-based high-molecular compound of color：Furans copolyesters, inherent viscosity 0.97dL/g.
Embodiment 16
By 0.10mol 2,5- furans dimethyl chlorides, 0.06mol FDCA dimethyl ester, 0.04mol pair
Rutgers, 0.15mol ethylene glycol, 0.15mol Isosorbide-5-Nitrae-cyclohexanedimethanol, 0.0004mol anhydrous zinc acetate
Together be added in 1000mL reactors, vacuumize, inflated with nitrogen displacement three times, open stirring, 25 DEG C reaction 2h, be evacuated to pressure
Power 0.01-0.03MPa, 1h is reacted, stop vacuum, be passed through nitrogen and be progressively warming up to 160 DEG C, continue to react 4h.Add in system
Enter antimony oxide, triphenyl phosphate and antioxidant, be warming up to 240 DEG C, slowly vacuumize precondensation 0.5h, then control vacuum
Degree below 200Pa reacts 3h, obtains connecing subdiaphanous bio-based high-molecular compound：Furans copolyesters, inherent viscosity 1.02dL/
g。
All it is incorporated as referring in this application in all documents that the present invention refers to, it is independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after the above-mentioned instruction content of the present invention has been read, those skilled in the art can
To be made various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Claims (10)
1. a kind of bio-based high-molecular compound, it is characterised in that described bio-based high-molecular compound is bio-based furans
Polyester, the component for synthesizing described bio-based high-molecular compound include：
Component (a)：Furandicarboxylic acid, furandicarboxylic acid carboxylate or its combination；
Component (b)：Furans dimethyl chloride；
Optional component (c)：Aromatic acid, aliphatic dibasic acid, aromatic acid carboxylate, fatty group dibasic acid
Compound or its combination；With
Component (d)：Cyclic diols, aliphatic dihydroxy alcohol or its combination,
Wherein, the content of component (b) is 0.001mol%-35mol%, by component (a)+(b)+(c)+(d) total moles gauge.
2. bio-based high-molecular compound as claimed in claim 1, it is characterised in that：Described component (a) and component (b)
Mol ratio is 0.001-1000.
3. bio-based high-molecular compound as claimed in claim 1, it is characterised in that for synthesizing described macromolecule chemical combination
Additive is also included in the component of thing, wherein the additive is selected from the group：It is esterification catalyst, polycondensation catalyst, stabilizer, anti-
Oxygen agent or its combination.
4. bio-based high-molecular compound as claimed in claim 1, it is characterised in that described bio-based high-molecular compound
It is to be prepared with the method comprised the following steps：
(i) the first mixture is provided, first mixture contains component (a), (b), (c) and (d)；
(ii) component (b) in first mixture and (d) are subjected to nucleophilic substitution, form the first intermediate product；
(iii) in the presence of esterification catalyst, by the component (a) in first intermediate product and component (d), and/or component
(c) and component (d) carries out esterification and/or ester exchange reaction, so as to form to obtain the second intermediate product；With
(iv) in the presence of polycondensation catalyst, polycondensation reaction is carried out to second intermediate product, so as to obtain such as claim 1
Described bio-based high-molecular compound.
5. bio-based high-molecular compound as claimed in claim 1, it is characterised in that in described component (a) and component (b)
Furan nucleus contained by carbon come from biomass raw material.
6. bio-based high-molecular compound as claimed in claim 1, it is characterised in that described high-molecular compound characteristic is glued
Spend for 0.7-1.4dL/g, and fusing point is 190 DEG C -280 DEG C.
7. bio-based high-molecular compound as claimed in claim 1, it is characterised in that described high-molecular compound color is
It is light or colourless.
A kind of 8. preparation method of bio-based high-molecular compound as any one of claim 1-7, it is characterised in that
Including step：
(i) the first mixture is provided, first mixture contains component (a), (b), (c) and (d)；
(ii) component (b) in first mixture and (d) are subjected to nucleophilic substitution, form the first intermediate product；
(iii) in the presence of esterification catalyst, by the component (a) in first intermediate product and component (d), and/or component
(c) and component (d) carries out esterification and/or ester exchange reaction, so as to form to obtain the second intermediate product；With
(iv) in the presence of polycondensation catalyst, polycondensation reaction is carried out to second intermediate product, so as to obtain such as claim 1
Described bio-based high-molecular compound.
A kind of 9. product, it is characterised in that the product includes bio-based high-molecular compound as described in claim 1,
Or the product is made up of the bio-based high-molecular compound described in claim 1.
10. product as claimed in claim 9, it is characterised in that described product includes：Packaging material, film, fiber, bottle
Son, and/or engineering plastics.
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| 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 |
| CN111499846A (en) * | 2019-01-31 | 2020-08-07 | 财团法人工业技术研究院 | Polyester and fiber |
| 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 |
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