CN107840946A - 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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- CN107840946A CN107840946A CN201610831213.8A CN201610831213A CN107840946A CN 107840946 A CN107840946 A CN 107840946A CN 201610831213 A CN201610831213 A CN 201610831213A CN 107840946 A CN107840946 A CN 107840946A
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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
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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, furandicarboxylic acid carboxylate or its combination；Component (b)：Furans dimethyl chloride；With component (c)：Aliphatic dihydroxy alcohol.The high-molecular compound of the present invention not only have molecular weight is high, stretch modulus is high, tensile strength is high, heat-resist (glass transition temperature may be up to about 90 DEG C), oxygen-barrier property and dioxide barrier properties it is good, and solve 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；With
Component (c)：Aliphatic dihydroxy alcohol；
Wherein, the content of component (b) is 0.005mol%-49.5mol%, by component (a)+(b)+(c) integral molar quantity
Meter.
In another preference, described component (a), (b) and (c) sum account for the pact of the high-molecular compound total amount
70-100wt%, preferably 80-99.5wt%, more preferably 90-99wt%.
In another preference, described component (a) is selected from the group：Furandicarboxylic acid, furandicarboxylic acid dimethyl ester, furans
Dicarboxylate or its combination.
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 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, 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, 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；Preferably it is selected from the group：Antimony oxide, iso-butyl titanate, butyl titanate, antimony glycol, acetic acid
Antimony 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) and (c)；
(ii) component (b) in first mixture and (c) are subjected to nucleophilic substitution, are formed among first and produced
Thing；
(iii) in the presence of esterification catalyst, the component (a) in first intermediate product and component (c) are subjected to ester
Change 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 the present invention
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 0.6-1.2dL/g, and fusing point is 190-
270℃。
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 80-90 DEG C, 50-60 DEG C, 35-45 DEG C, or 20-30 DEG C；
(2) oxygen gas barrier is 1.0 × 10-13-2.0×10-12cm3·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 80-90MPa, 20-40MPa or 65-75MPa；
(5) stretch modulus is 2.0-3.5GPa, 1.3-1.8GPa or 0.5-1.0GPa；
(6) elongation at break is 4-10%, or 20-80%, or 100-300%.
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) and (c)；
(ii) component (b) in first mixture and (c) are subjected to nucleophilic substitution, are formed among first and produced
Thing；
(iii) in the presence of esterification catalyst, the component (a) in first intermediate product and component (c) are subjected to ester
Change 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, with component (c) esterification occurs for described component (a)
And/or ester exchange reaction removing H2O and/or low-boiling point alcohol.
In another preference, in described nucleophilic substitution, described component (b) reacts with component (c)
And remove HCl.
The third aspect of the present invention provides a kind of product, and the product includes biology as described in the first aspect of the invention
Based 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
Fig. 1 is the sample photo for the poly- 2,5- furandicarboxylic acids glycol ester that comparative example 1 obtains.
Fig. 2 is the sample photo for the bio-based high-molecular compound that embodiment 1 obtains.
Fig. 3 is the FTIR collection of illustrative plates for the bio-based high-molecular compound that embodiment 1 obtains.
Fig. 4 is the bio-based high-molecular compound that embodiment 1 obtains1H-NMR collection of illustrative plates.
Fig. 5 is the DSC collection of illustrative plates for the bio-based high-molecular compound that embodiment 1 obtains.
Fig. 6 is the TGA collection of illustrative plates for the bio-based high-molecular compound that embodiment 1 obtains.
Embodiment
The present inventor by extensively and in depth study, unexpectedly develop 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 and component (c) aliphatic dihydroxy alcohol.Pass through
The polymer of nucleophilic substitution, esterification and polycondensation reaction synthesis has premium properties (colourless or light, Yi Jiji
Tool excellent performance etc.) bio-based high-molecular 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 participates in polymerization, such as furans dimethyl chloride is formed into blend together with furandicarboxylic acid or furandicarboxylic acid dimethyl ester
It is copolymerized with aliphatic dihydroxy alcohol.Present inventors have surprisingly found that when adding a certain amount of furans dimethyl chloride, can not only solve
The problem of certainly existing furans polyester product color is deeper, and molecular weight can be further improved, lift the mechanics of polymer
Performance.
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) aliphatic dihydroxy alcohol, pass through nucleophilic substitution, esterification
Gained is synthesized with polycondensation reaction.The bio-based high-molecular compound has higher molecular weight, modulus and intensity, and preferably
Heat resistance, the premium properties such as oxygen-barrier property and dioxide barrier properties.
Component (a) of the present invention includes (but being not limited to)：Furandicarboxylic acid, furandicarboxylic acid dimethyl ester or its
Composition.Described component (b) includes (but being not limited to)：2,5 furans dimethyl chlorides, 2,4- furans dimethyl chlorides, 3,4- furans
Mutter dimethyl chloride.Described aliphatic dihydroxy alcohol includes (but being not limited to)：Ethylene glycol, 1,3- propane diols, 1,4- butanediols, 1,
6- hexylene glycols, 1,8- ethohexadiols or its combination.
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, the present invention is sent out (such as -10-80 DEG C) at a lower temperature using furans dimethyl chloride with aliphatic dihydroxy alcohol
Raw nucleophilic substitution removing HCl reaction mechanism, and existed using furandicarboxylic acid or its carboxylate with aliphatic dihydroxy alcohol
Esterification and/or ester exchange reaction removing H occur for (such as 120-200 DEG C) under higher temperature2O and/or low-boiling point alcohol reaction
Mechanism implements the synthetic reaction of the high-molecular compound, finally in high temperature (such as 200-260 DEG C), certain vacuum degree (such as 3-
1000Pa, preferably 10-500Pa) under by polycondensation reaction, so as to obtain colourless or light HMW macromolecule chemical combination
Thing.
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) 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；With
(5) polycondensation catalyst, stabilizer and antioxidant are added in the 3rd intermediate product, and in the basis of step (4)
Upper further rise temperature, control vacuum continue reaction a period of time in below 200Pa, obtained such as first aspect present invention institute
The bio-based high-molecular compound stated.
In the step (2), reaction temperature is -10-80 DEG C, reaction time 0.5-2h.
In the step (3), reaction temperature is -10-80 DEG C, and vacuum is below 2000Pa, reaction time 0.5-
2h。
In the step (4), 120-240 DEG C is warming up to, reaction time 0.5-8h.
In the step (5), 200-260 DEG C is warming up to, 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 methods
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。
The measure of inherent viscosity is with phenol/tetrachloroethanes (1:1m/m) it is solvent, at 30 ± 0.05 DEG C, uses Ubbelohde viscometer
Tested, 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 esterification temperature is reduced, relatively low with nucleophilic substitution occurs under alcohol low temperature using furans dimethyl chloride
At a temperature of furan ring structure is formed the polyester of oligomer, the relative molecular mass of polymer can be effectively improved.
2. obtaining colourless or light bio-based high-molecular compound, meet packaging material, film, fiber, engineering plastics
Deng 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 dimethyl ester, 0.30mol ethylene glycol, 0.0004mol anhydrous zinc acetate
Together be added in 1000mL reactors, vacuumize, inflated with nitrogen displacement three times, open stirring, be progressively warming up to 160 DEG C, continue
React 4h.Antimony oxide, triphenyl phosphate and antioxidant are added in system, is warming up to 240 DEG C, control vacuum 200Pa
4-5h is reacted below, obtains polyester.
Described polyester is the poly- FDCA glycol ester of dark yellow, as shown in figure 1, inherent viscosity
0.78dL/g, glass transition temperature, 81.1 DEG C, 207.4 DEG C of fusing point.Tensile strength 68.1MPa, stretch modulus 2.3GPa, break
Split elongation 4.2%.
Embodiment 1
By 0.10mol 2,5- furans dimethyl chlorides, 0.10mol FDCA dimethyl ester, 0.30mol second
Glycol, 0.0004mol anhydrous zinc acetate are together added in 1000mL reactors, are vacuumized, inflated with nitrogen is replaced three times, unlatching
Stirring, 20 DEG C of reaction 3h, is evacuated to pressure 0.01-0.03MPa, reacts 1h, stop vacuum, be passed through nitrogen and be progressively warming up to
160 DEG C, continue to react 4h.Antimony oxide, triphenyl phosphate and antioxidant are added in system, is warming up to 240 DEG C, control is true
Below reciprocal of duty cycle 200Pa reacts 4-5h, obtains bio-based furans polyester.
As a result：The bio-based furans polyester sample photo is as shown in Figure 2.After measured, FTIR as shown in figure 3,1H-NMR
As shown in figure 4, inherent viscosity 0.94dL/g, 88.6 DEG C of glass transition temperature, 217.4 DEG C of fusing point, as shown in Figure 5.TD, 5%Heat
Decomposition temperature is 372 DEG C, as shown in Figure 6.Oxygen gas barrier is 1.4 × 10-12cm3·cm/cm2ScmHg, titanium dioxide
Carbon barrier properties for gases is 4.0 × 10-12cm3·cm/cm2ScmHg, tensile strength 85.4MPa, stretch modulus 2.8GPa, break
Split elongation 5.2%.
Embodiment 2
By 0.02mol 2,5- furans dimethyl chlorides, 0.18mol FDCA dimethyl ester, 0.30mol second
Glycol, 0.0004mol anhydrous zinc acetate are together added in 1000mL reactors, are vacuumized, inflated with nitrogen is replaced three times, unlatching
Stirring, 10 DEG C of reaction 3h, 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, is warming up to 250 DEG C, control is true
Below reciprocal of duty cycle 200Pa reacts 4-5h, obtains bio-based furans polyester.
As a result：The inherent viscosity 0.88dL/g of the bio-based furans polyester, 86.4 DEG C of glass transition temperature, fusing point
216.4℃.Oxygen gas barrier is 1.3 × 10-12cm3·cm/cm2ScmHg, carbon dioxide barrier are 3.7
×10-12cm3·cm/cm2ScmHg, tensile strength 80.2MPa, stretch modulus 2.7GPa, elongation at break 4.7%.
Embodiment 3
By 0.002mol 2,5- furans dimethyl chlorides, 0.198mol FDCA dimethyl ester, 0.30mol's
Ethylene glycol, 0.0004mol anhydrous zinc acetate are together added in 1000mL reactors, vacuumize, inflated with nitrogen displacement three times, open
Stirring is opened, -5 DEG C of reaction 3h, pressure 0.01-0.03MPa is evacuated to, reacts 1h, stop vacuum, be passed through nitrogen and be progressively warming up to
180 DEG C, continue to react 4h.Antimony oxide, triphenyl phosphate and antioxidant are added in system, is warming up to 235 DEG C, control is true
Below reciprocal of duty cycle 200Pa reacts 4-5h, obtains bio-based furans polyester.
As a result：The inherent viscosity 1.14dL/g of the bio-based furans polyester, 89.7 DEG C of glass transition temperature, fusing point
220.4℃.Oxygen gas barrier is 1.0 × 10-12cm3·cm/cm2ScmHg, carbon dioxide barrier are 3.2
×10-12cm3·cm/cm2ScmHg, tensile strength 88.7MPa, stretch modulus 2.9GPa, elongation at break 5.4%.
Embodiment 4
By 0.04mol 2,5- furans dimethyl chlorides, 0.16mol FDCA dimethyl ester, the 1 of 0.30mol,
4- butanediols, 0.0004mol anhydrous zinc acetate are together added in 1000mL reactors, vacuumize, inflated with nitrogen displacement three times,
Stirring is opened, 35 DEG C of reaction 3h, pressure 0.01-0.03MPa is evacuated to, reacts 1h, stop vacuum, be passed through nitrogen and progressively heat up
To 145 DEG C, continue to react 4h.Antimony oxide, triphenyl phosphate and antioxidant are added in system, is warming up to 225 DEG C, control
Below vacuum 200Pa reacts 4-5h, obtains bio-based furans polyester.
As a result：The inherent viscosity 1.03dL/g of the bio-based furans polyester, 37.8 DEG C of glass transition temperature, stretching are strong
Spend 32.3MPa, stretch modulus 1.4GPa, elongation at break 212%.
Embodiment 5
By 0.08mol 2,5- furans dimethyl chlorides, 0.12mol FDCA dimethyl ester, the 1 of 0.40mol,
4- butanediols, 0.0006mol anhydrous zinc acetate are together added in 1000mL reactors, vacuumize, inflated with nitrogen displacement three times,
Stirring is opened, 15 DEG C of reaction 3h, pressure 0.01-0.03MPa is evacuated to, reacts 1h, stop vacuum, be passed through nitrogen and progressively heat up
To 170 DEG C, continue to react 4h.Antimony oxide, triphenyl phosphate and antioxidant are added in system, is warming up to 255 DEG C, control
Below vacuum 200Pa reacts 4-5h, obtains bio-based furans polyester.
As a result：The inherent viscosity 1.08dL/g of the bio-based furans polyester, 38.2 DEG C of glass transition temperature, stretching are strong
Spend 35.1MPa, stretch modulus 1.4GPa, elongation at break 237%.
Embodiment 6
By 0.08mol 2,5- furans dimethyl chlorides, 0.12mol FDCA dimethyl ester, the 1 of 0.30mol,
Ammediol, 0.0006mol anhydrous zinc acetate are together added in 1000mL reactors, vacuumize, inflated with nitrogen displacement three times,
Stirring is opened, 15 DEG C of reaction 3h, pressure 0.01-0.03MPa is evacuated to, reacts 1h, stop vacuum, be passed through nitrogen and progressively heat up
To 170 DEG C, continue to react 4h.Antimony oxide, triphenyl phosphate and antioxidant are added in system, is warming up to 255 DEG C, control
Below vacuum 200Pa reacts 4-5h, obtains bio-based furans polyester.
As a result：The inherent viscosity 1.08dL/g of the bio-based furans polyester, 57.9 DEG C of glass transition temperature, stretching are strong
Spend 68.1MPa, stretch modulus 1.6GPa, elongation at break 5.7%.
Embodiment 7
By 0.06mol 2,5- furans dimethyl chlorides, 0.14mol FDCA dimethyl ester, the 1 of 0.30mol,
6- hexylene glycols, 0.0002mol anhydrous zinc acetate are together added in 1000mL reactors, vacuumize, inflated with nitrogen displacement three times,
Stirring is opened, 0 DEG C of reaction 3h, pressure 0.01-0.03MPa is evacuated to, reacts 1h, stop vacuum, be passed through nitrogen and progressively heat up
To 150 DEG C, continue to react 4h.Antimony oxide, triphenyl phosphate and antioxidant are added in system, is warming up to 230 DEG C, control
Below vacuum 200Pa reacts 4-5h, obtains bio-based furans polyester.
As a result：The inherent viscosity 0.87dL/g of the bio-based furans polyester, 28.1 DEG C of glass transition temperature, stretching are strong
Spend 35.7MPa, stretch modulus 0.8GPa, elongation at break 130%.
Embodiment 8
By 0.16mol 2,5- furans dimethyl chlorides, 0.04mol FDCA, 0.40mol 1,8- pungent two
Alcohol, 0.0004mol anhydrous zinc acetate are together added in 1000mL reactors, vacuumize, inflated with nitrogen displacement three times, unlatching is stirred
Mix, 45 DEG C of reaction 3h, be evacuated to pressure 0.01-0.03MPa, react 1h, stop vacuum, be passed through nitrogen and be progressively warming up to 165
DEG C, continue to react 4h.Antimony oxide, triphenyl phosphate and antioxidant are added in system, is warming up to 220 DEG C, controls vacuum
Degree below 200Pa reacts 4-5h, obtains bio-based furans polyester.
As a result：The inherent viscosity 1.18dL/g of the bio-based furans polyester.22.4 DEG C of glass transition temperature, stretching are strong
Spend 21.2MPa, stretch modulus 0.5GPa, elongation at break 180%.
Embodiment 9
By 0.18mol 2,5- furans dimethyl chlorides, 0.02mol FDCA, 0.36mol ethylene glycol,
0.0004mol anhydrous zinc acetate is together added in 1000mL reactors, vacuumize, inflated with nitrogen displacement three times, open stirring,
23 DEG C of reaction 3h, are evacuated to pressure 0.01-0.03MPa, react 1h, stop vacuum, be passed through nitrogen and be progressively warming up to 180 DEG C,
Continue to react 4h.Antimony oxide, triphenyl phosphate and antioxidant are added in system, is warming up to 255 DEG C, controls vacuum
Below 200Pa reacts 4-5h, obtains bio-based furans polyester.
As a result：The inherent viscosity 1.08dL/g of the bio-based furans polyester, tensile strength 84.1MPa, stretch modulus
2.7GPa, elongation at break 5.9%.
The partial properties of comparative example 1 and each embodiment are summarized in table 1.
The mechanical property of polyester in the embodiment of table 1
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；With
Component (c)：Aliphatic dihydroxy alcohol；
Wherein, the content of component (b) is 0.005mol%-49.5mol%, by component (a)+(b)+(c) 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) and (c)；
(ii) component (b) in first mixture and (c) are subjected to nucleophilic substitution, form the first intermediate product；
(iii) in the presence of esterification catalyst, the component (a) in first intermediate product and component (c) be esterified instead
Should, 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. high-molecular compound as claimed in claim 1, it is characterised in that the furans in described component (a) and component (b)
Carbon contained by ring comes from biomass raw material.
6. high-molecular compound as claimed in claim 1, it is characterised in that described high-molecular compound inherent viscosity is
0.6-1.2dL/g, and fusing point is 190-270 DEG C.
7. high-molecular compound as claimed in claim 1, it is characterised in that described high-molecular compound color for light color or
It is colourless.
A kind of 8. preparation method of bio-based high-molecular compound as described in claim any one of 1-7, it is characterised in that bag
Include step：
(i) the first mixture is provided, first mixture contains component (a), (b) and (c)；
(ii) component (b) in first mixture and (c) are subjected to nucleophilic substitution, form the first intermediate product；
(iii) in the presence of esterification catalyst, the component (a) in first intermediate product and component (c) be esterified instead
Should, 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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Application publication date: 20180327 Assignee: SUZHOU YACOO SCIENCE Co.,Ltd. Assignor: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES Contract record no.: X2023980041223 Denomination of invention: A Biobased Polymer Compound and Its Preparation Method Granted publication date: 20200207 License type: Exclusive License Record date: 20230905 |